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CAS No. : | 112-62-9 | MDL No. : | MFCD00009578 |
Formula : | C19H36O2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | QYDYPVFESGNLHU-KHPPLWFESA-N |
M.W : | 296.49 | Pubchem ID : | 5364509 |
Synonyms : |
Methyl octadecenoate (cis-9);C18:1 (cis-9) Methyl ester
|
Num. heavy atoms : | 21 |
Num. arom. heavy atoms : | 0 |
Fraction Csp3 : | 0.84 |
Num. rotatable bonds : | 16 |
Num. H-bond acceptors : | 2.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 94.26 |
TPSA : | 26.3 Ų |
GI absorption : | High |
BBB permeant : | No |
P-gp substrate : | No |
CYP1A2 inhibitor : | Yes |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -2.82 cm/s |
Log Po/w (iLOGP) : | 4.75 |
Log Po/w (XLOGP3) : | 7.45 |
Log Po/w (WLOGP) : | 6.2 |
Log Po/w (MLOGP) : | 4.8 |
Log Po/w (SILICOS-IT) : | 6.54 |
Consensus Log Po/w : | 5.95 |
Lipinski : | 1.0 |
Ghose : | None |
Veber : | 1.0 |
Egan : | 1.0 |
Muegge : | 2.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -5.32 |
Solubility : | 0.00143 mg/ml ; 0.00000483 mol/l |
Class : | Moderately soluble |
Log S (Ali) : | -7.83 |
Solubility : | 0.00000434 mg/ml ; 0.0000000146 mol/l |
Class : | Poorly soluble |
Log S (SILICOS-IT) : | -6.09 |
Solubility : | 0.00024 mg/ml ; 0.000000811 mol/l |
Class : | Poorly soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 2.0 |
Synthetic accessibility : | 3.16 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P264-P273-P280-P302+P352-P337+P313-P305+P351+P338-P362+P364-P332+P313 | UN#: | N/A |
Hazard Statements: | H315-H319-H413 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With Mesoscopically Assembled SulfatedZirconia Nanoparticles at 49.84℃; for 8h; | |
100% | With sulfuric acid; trimethyl orthoformate for 10h; Reflux; | |
99% | With CAN at 20℃; for 2h; |
99.9% | at 80℃; for 18h; Ionic liquid; | |
99% | With sodium iodide at 20℃; for 2h; Green chemistry; | |
99% | With Glu-Fe3O4-SO3H at 20℃; for 4h; | Procedure for Esterification General procedure: 1 mmol of acid, 3 mmol of alcohol and Glu-Fe3O4-SO3H catalyst were stirred together at rt for required time. The reaction was monitored by TLC. After completion of the reaction, the reaction mixture was diluted with DCM and the catalyst separated using external magnetic field. DCM layer was then concentrated, loaded on silica gel and purified by column chromatography to obtain pure ester. |
99% | With C12H29N3*9H2O4S at 60℃; for 1h; | |
98% | With sulfuric acid | 4.14. Synthesis of methyl oleate (13) Oleic acid (2 g, 7.09 mmol) was dissolved in 2% MeOHeH2SO4solution (50 mL) and the reaction mixture was refluxed on waterbath for 6 h. The reaction was monitored with micro TLC. Aftercompletion of the reaction, the organic solvent was evaporatedunder reduced pressure. The mixture was portioned in water andethyl acetate and the organic phase was washed with water untilthe acidic nature was disappeared. The organic layer was dried overanhydrous sodium sulphate and evaporated. The crude reactionmixture was purified by silica gel column chromatography using asolvent mixture of hexane: EtOAc (97: 3, v/v) to give the titlecompound (2.05 g, 98%). 1H NMR (500 MHz, CDCl3) d 5.37e5.32 (m,2H), 3.64 (s, 3H), 2.3 (t, J 7.6 Hz, 2H), 2.01 (m, 4H), 1.63 (p, 2H), 1.3(m, 20H), 0.89 (t, J 6.7 Hz, 3H); 13C NMR (125 MHz, CDCl3) d 173.8,129.7,129.5, 51.1, 33.8, 31.7, 29.6, 29.5, 29.4, 29.1, 29.03, 28.99, 28.94,27.05, 27, 24.8, 22.5, 13.9; IR (CHCl3) 2926, 2855, 1744,1463,1436,1196,1170 cm1. |
98% | With 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione at 70℃; for 5h; | 3.2.1. General Procedure for the Esterification between Carboxylic Acids and Alcohols General procedure: The mixture of carboxylic acid, alcohol, and 1,3-dibromo-5,5-dimethylhydantoin was stirredin a 25 mL reactor tube at 70 °C for 2-40 h. After reaction completion, the mixture was cooled toroom temperature and the alcohol was evaporated under reduced pressure. The isolation procedurewas as follows, except where noted dierently in the Supporting Information. The residue wasdissolved in 10 mL ethyl acetate and washed with a mixture of 1 mL saturated NaHCO3(aq), 1 mLsaturated Na2S2O3(aq), and 10 mL distilled water, and the water phase was extracted with ethyl acetate(2 10 mL). The organic layers were combined, dried over Na2SO4, and the solvent was evaporatedunder reduced pressure |
97.7% | With 1-sulfobutyl-3-methylimidazolium hydrosulfate at 130℃; for 4h; Green chemistry; | 2.4. Operational stability of the [BHSO3MIM]HSO4 catalyst Oleic acid (2.82 g, 0.01 mol), methanol (1.28 g), and 0.28 g [BHSO3MIM]HSO4 catalyst were mixed in a 10 ml round bottomflask at 130 °C for 4 h (reflux condensation, magnetic stirring at500 r/min). After completion of the reaction, the by-product water and excess methanol were removed from the mixture by evaporation, and then the IL catalyst [BHSO3MIM]HSO4 was further separated from the product by centrifugation. After thorough washing with n-hexane followed by air-drying, the ILcatalyst obtained was used in the next cycle. The activity of the[BHSO3MIM]HSO4 catalyst in the first reaction cycle was assigneda relative activity of 100%. Samples (100 μl) were with drawn from the reaction mixture at specified times for each batch and centrifuged, and the supernatant liquid (5 μl) was mixed with 200 μl methylheptadecanoate (internal standard)prior to GC analysis. |
97% | With SO3H and NH2+ functional carbon-based solid acid at 80℃; for 2h; | |
97% | With asparaginium nitrate In chloroform at 70℃; for 5h; Green chemistry; | |
97% | With N-Bromosuccinimide at 70℃; for 15h; | 3.2.1. General Procedure for the Esterification between Carboxylic Acids and Alcohols General procedure: The mixture of carboxylic acid, alcohol and N-bromosuccinimide was stirred in a 25 mL reactortube at 70 °C for 2-40 h. After the completion of the reaction, the mixture was cooled to roomtemperature and alcohol was evaporated under reduced pressure. The isolation procedure was as follows, except where noted differently in Section 3.2.6. The residue was dissolved in ethyl acetate andconsecutively washed with 10 mL of 10% Na2S2O3 (aq), 5 mL of saturated NaHCO3 (aq) and 10 mL ofdistilled water. The water phase was extracted with ethyl acetate (3Χ5 mL). The organic layers were combined, dried over Na2SO4 and the solvent was evaporated under reduced pressure. |
97.05% | With p-toluenesulfonic acid impregnated on activated biochar at 65℃; for 2h; | |
96% | With sulfuric acid | |
96% | With sulfuric acid | |
96.9% | With Zn0.4Cu0.6Al2O4 at 180℃; for 6h; | 2.3. Catalyst testing The activity of the fabricated catalysts was discussed inthe esterification reaction of OA to the correspondingmethyl ester form. This reaction was conducted in a batchsystem composed of an 80 ml stainless steel reactor; thereactor was operated at 180 ± 3 C (set by using a type Kthermocouple) for 6 h. The molar ratio of methanol to oleicacidwas about 9, and the weight percent of the catalystwas3 wt.% with a fixed stirring speed of 600 rpm. Once thereaction had completed, the obtained mixture was filteredto remove the catalyst. The biodiesel was then heated to80 C and held for 90 min to eliminate water and any extramethanol content. The yield of conversion of OA to methylesterwas calculated based on acidity reduction of OA by thestandard titration method using potassium hydroxide |
96% | With sulfuric acid | |
96% | With 1-(4-Nitrophenyl)-1H-imidazole-3-ium trifluoromethanesulfonate at 80℃; for 4h; Sealed tube; Green chemistry; | 2.2. General procedure for the synthesis of biodiesel General procedure: A magnetic stir bar placed in a sealed tube, Free Fatty Acids (FFAs), methanol, and ionic liquids were added. The esterification was then carried out for a length of time at a specific temperature with vigorous stirring. After the reaction was completed, the residue was cooled to room temperature and kept at the same temperature until phase separation. The reaction mixture was extracted with ether and water. The upper phase (volume) mainly containing the desired ester could be isolated simply by liquid/liquid phase separation, concentrated, and column chromatography; the bottom phase ionic liquid in water from the reaction could be reused after removal of water under reduced pressure. For several experiments separated organic phase was directly concentrated and the product was confirmed by NMR spectrometry/ mass spectrometry. |
95% | With vanadium phosphate impregnated ammonium metatungstate at 100℃; for 10h; Reflux; neat (no solvent); | |
95.4% | With sulfuric acid at 79.84℃; for 2h; | |
95% | With porous phenol sulfonic acid-formaldehyde resin In neat (no solvent) at 50℃; for 6h; | General Esterification Procedure General procedure: The esterification reaction was carried out in a 20 mL glass vialwith a magnetic bar. Oleic acid (10 mmol), alcohol substrate (12mmol), and PSF catalyst (1.4 mol%) were added at 90 °C. Thereaction mixture was analyzed by diluting a sample 5 timeswith heptane using an internal standard (methyl heptadecanoate),and analyzed via gas chromatography (GC) and massspectrometry (GC-MS). After reaction was complete, the catalystwas separated from the reaction products by filtration andwas dried in vacuo. |
95% | With sulfuric acid at 70℃; | Methyl Oleate . A solution containing 2.00 g (7.08 mmol) of oleic acid in 50 mL of 2% H2SO4MeOH was heated at 70 oC overnight, then the solvent was concentrated and aq NaHCO3 was added. The aqueous layer was extracted with EtOAc, and the organic phase was dried over MgSO4, filtered and concentrated to provide methyl oleate as a colorless oil: yield 2.0 g (95%); silica gel TLC Rf 0.45 (6:1 hexaneEtOAc); 1H NMR (CDCl3) δ 0.87 (t, 3H, J = 8.0 Hz), 1.25-1.29 (br m, 20H), 1.58-1.62 (m, 2H), 1.97-2.02 (m, 4H), 2.29 (t, 2H, J = 8.0 Hz), 3.65 (s, 3H) and 5.31-5.34 (m, 2H); 13C NMR (CDCl3) δ 14.2, 25.1, 27.3, 27.3, 29.2, 29.3, 29.3, 29.4, 29.8, 34.2, 51.5, 129.9, 130.1 and 174.4; mass spectrum (MALDI), m/z 335 [M+K]+ (theoretical m/z 335). |
94% | With modification of hypercrosslinked supermicroporous polymer (HMP-1) via sulfonation (HMP-1-SO3H) at 24.84℃; for 12h; Green chemistry; | |
93% | With bromine; triphenylphosphine for 0.25h; Ambient temperature; | |
93% | With sulfuric acid for 24h; Reflux; | |
93.3% | With sulfonated organosilica mesocellular foam at 100℃; for 6h; | |
92.2% | With sulfonic/carboxylic dual-acid on sulfur rich graphene oxide at 64.84℃; for 8h; | |
91% | With sulfuric acid In benzene at 80℃; for 5h; Cooling with ice; | Synthesis of methyl oleate (1) 0.25 mol of oleic acid and 1.24 mol of methanol in 100 ml of benzene were taken in a three neck 250 ml RBF on a magnetic stirrer. The ends of the condenser were added with glass tube containing Na2SO4 anhydrate and the cotton was added. To this mixture 2 ml of H2SO4 was added drop by drop through separating funnel while keeping ice around the flask with continuous shaking. When all of H2SO4 was mixed, the solution was refluxed for 5 h at 80°C on water bath. The product was vaporized using rotary evaporator to eliminate solvent and methanol. The residue thus obtained was mixed with 100 ml of n-hexane. This solution was washed 3 times in separating funnel with water. Water left in washing was dried by Na2SO4 anhydrous by keeping for 24 h prior to filtering. The product was filtered to remove Na2SO4 anhydrous. Then again the residue was purified using rotary evaporator to evaporate n-hexane and gave methyl oleate as a product in liquid form. The yield of methyloleate was 91%, m.p. 15°C and b.p. 350°C, IR: (KBr, cm-1) 2925, 2854 (C-H), 1742 (C=O), 1658 (C=C), 1169 (C-OC), 722 [(CH2)n]. 1H NMR: (CDCl3, δ, ppm): 5.42 (2H, m, CH=CH), 3.5 (3H, s, OCH3), 2.2 (2H, t, CH2), 1.96 (4H, m, 2×CH2), 1.59 (2H, m, CH2), 1.31 (20H, m, 10×CH2), 0.96 (3H, s, CH3). ESI-MS: m/z 297 (M+H). Anal. calcd. for C19H36O2: C, 76.97; H, 12.24%. Found: C, 76.84; H, 12.07%. |
90% | at 220 - 280℃; for 0.666667h; | |
90% | With polysiloxane acidic ionic liquids containing pyridinium trifluoroacetate salts for 4h; Reflux; | 2.6 General procedure for biodiesel production using PMO-Py-IL materials General procedure: In a typical reaction, fatty acids (10 mmol), methanol or ethanol (5 mL), and PMO-Py-IL (0.1 g) as nanocatalyst were mixed in a 50 mL single-necked round bottomed flask and stirred under reflux conditions for 4 h. Upon reaction completion, the mixture was cooled down at RT, PMO-Py-IL was recovered and washed with ethyl acetate for the next run. The combined filtrate and ethyl acetate washings were washed with water and the organic layer was separated and dried over sodium sulfate, filtered, and concentrated under vacuum to provide the desired methyl esters as pure products. |
89.6% | With mesoporous silica modified Fe3O4 nanoparticle fabricated by 3-sulfopropyl-1-(3-propyltrimethoxysilane) imida-zolium hydrogen sulfate at 109.84℃; for 4h; Green chemistry; | 2.3 Catalytic activity measurement General procedure: Biodiesel production from oleic acid with alcohol was carried out with FSS-IL as catalyst. In a typical run, oleic acid (10mmol), alcohol (60mmol), and catalyst (0.2g) were added in a flask (50ml) and kept under 373K for 4h. When the reaction was finished, a magnet was put at the bottom of the reaction flask and the catalyst would be totally adsorbed to the magnet. The upper layer was dumped out for analysis and the yield of biodiesel was calculated based on oleic acid referring to previous publication [11]. The left catalyst was washed with acetone for three times, setting in vacuum at 323K for 6h for recycling experiment. The recovered catalyst was also weighted by electronic balance (d=0.0001g) for calculating catalyst mass loss data. |
89.2% | With corncob-based solid acid at 79.84℃; for 2h; | |
89% | With zirconocene bis(perfluorooctanesulfonate) trihydrate*(tetrahydrofuran) In neat (no solvent) at 80℃; Sealed tube; Green chemistry; chemoselective reaction; | |
88% | With trifluoroacetic anhydride In benzene at 25℃; for 0.666667h; | |
87.3% | With sulfonated carbon prepared via thermal treatment of mixture of furfural-sodium dodecylbenzenesulfonate-sulfuric acid at 64.84℃; for 4h; | |
81% | With dmap; oxalyl dichloride; Tropone; triethylamine In dichloromethane at 20℃; for 14h; | |
80% | With 1-methyl-3-dodecylimidazolium hydrogen sulfate In water monomer at 60℃; for 10h; | |
72% | With sulfonated petroleum coke at 80℃; | |
71% | With sulfuric acid at 5 - 72℃; for 4h; | 2 Embodiment 2: synthesis of oleic acid methyl ester Equipped with oleic acid of centrifuge bottles in 5 °C under low-temperature centrifugal, bottom with a white solid separated out, after the solid filter, the liquid can be used for the subsequent reaction. The oleic acid (200 g 0.71 µM), anhydrous methanol (160 g 5 µM) and concentrated sulfuric (3 g) is added to a 500 ml single-port in the bottle, in the 72 °C reaction under 4 hours, after the reaction, steaming and to remove the methanol. Then use the water washing of the organic layer, the final drying of the organic layer for magnesium sulfate, after filtering, is distilled under reduced pressure to obtain the pure oleic acid methyl ester. 172 °C -175 °C/5 mmHg. Yield 71%. |
62.4% | With sulfuric acid Reflux; Inert atmosphere; | 1 Methyl Oleate. Methyl oleate was prepared from oleic acid (Aldrich) and a 50 fold excess of HPLC grade methanol. The oleic acid (7 g, 0.0247 mol) was added to a 1 K 2-neck flask, equipped with a thermometer and a reflux condenser. A nitrogen adapter was connected to the condenser and the reaction vessel was purged of air in vacuo, and then refilled with dry N2. The methanol (50.25 ml, 1.235 mol) along with 10 drops of 18 M H2SO4 and the mixture refluxed for 36-48 hrs. The crude product was extracted with ether, washed with water and dried over MgSO4 and filtered. The solvent was removed in vacuo. The crude material was chromatographed on silica gel (eluting with 3% ether: petroleum ether) to give 4.5762 g (62.4%) as a colorless oil. |
15% | In benzene at 30℃; for 192h; Corynebacterium sp. S-401; | |
at 37℃; studied reacion order in heterogenous media, swelling of solid enzyme; also with other alcohol in the esterification reactions; | ||
at 25℃; in reactor with or without ion exchange membranes; other acids as catalyst; | ||
With sulfuric acid | ||
With ricinuslipase | ||
With hydrogenchloride | ||
With toluene-4-sulfonic acid | ||
With sodium hydroxide (electrolysis); | ||
With toluene-4-sulfonic acid | ||
With sulfuric acid Heating; | ||
With sulfuric acid | ||
With sulfuric acid at 30℃; | ||
at 95℃; for 2h; | ||
at 200℃; | 2 EXAMPLE 2 The operating procedure was that described in Example 1, however the nature of the rapeseed oil used differed by its acid number, which in this case was 11. This oil was reconstituted from a weighed mixture of distilled oleic acid and semi-refined rapeseed oil, identical to that used in Example 1. Three kilograms of said oil were produced as follows: a mixture of 165 g of distilled oleic acid and 2835 g of semi-refined rapeseed oil. The acid number of this mixture was determined using French standard NF ISO 660 and gave an AN of 11. Two catalysis steps were carried out under the conditions given for Example 1. The results are shown in Table 2. TABLE 2 Composition of esters produced from acid oil Rapeseed DG + oil AN = 11 TG sterols MG RME + fatty acids AN first catalysis 4.10 4.90 4.20 86.80 1.6 step second catalysis 0.05 0.95 0.60 98.40 0.35 step TG: triglycerides (oil) DG: diglycerides MG: monoglycerides RME: rapeseed methyl esters AN: acid number | |
94 - 98 %Chromat. | at 270 - 400℃; for 0.0333333 - 0.333333h; | 3.7; 3.8; 3.9; 3.3; 5.3 (Esterification Reaction of Fatty Acid) An esterification reaction of a fatty acid and methanol was conducted using, as a raw material, palmitic acid, stearic acid, oleic acid, linoleic acid and linolenic acid (all manufactured by Nacalai Tesque) commercially available as a reagent, and under conditions of volume ratio, temperature, pressure and reaction time shown in Table 5. For the esterification reaction of a fatty acid and methanol, a fatty acid and methanol were filled at a mole ratio of 1:42 in a Inconel-625 reaction tube having a content volume of 5 ml, and the same procedure as in the methyl-esterification reaction in Example 1 was conducted. After removal of unreacted methanol and produced water in the same manner as in Example 1, the reaction product was dissolved in fresh methanol and HPLC analysis was conducted. From the HPLC analysis result, the conversion from a fatty acid into a fatty acid alkyl ester (=yield of methyl ester) was obtained. The results are shown in Table 5 together with reaction conditions. TABLE 5 Reac- Tem- tion Fatty Fatty acid (ml)/ perature Pressure time Yield Example acid methanol (ml) (° C.) (Mpa) (min) (%) Example 3-1C16-0 0.91:4.09 270 17 20 90 Example 3-2C16-0 0.91:4.09 300 24 7 88 Example 3-3C16-0 0.91:4.09 350 43 4 75 ComparativeC16-0 0.91:4.09 400 75 2 92 example 3-1 Example 3-4C18-0 0.91:4.09 270 17 20 98 Example 3-5C18-0 0.91:4.09 300 24 7 98 Example 3-6C18-0 0.91:4.09 350 43 4 100 ComparativeC18-0 0.91:4.09 400 75 2 100 example 3-2 Example 3-7C18-1 0.91:4.09 270 17 20 98 Example 3-8C18-1 0.91:4.09 300 24 7 98 Example 3-9C18-1 0.91:4.09 350 43 4 98 ComparativeC18-1 0.91:4.09 400 75 2 94 example 3-3 Example 3-10C18-2 0.91:4.09 270 17 20 98 Example 3-11C18-2 0.91:4.09 300 24 7 98 Example 3-12C18-2 0.91:4.09 350 43 4 87 ComparativeC18-2 0.91:4.09 400 75 2 80 example 3-4 Example 3-13C18-3 0.91:4.09 270 17 20 99 Example 3-14C18-3 0.91:4.09 300 24 7 96 Example 3-15C18-3 0.91:4.09 350 43 4 93 ComparativeC18-3 0.91:4.09 400 75 2 61 example 3-5 C16-0: palmitic acid, C18-0: stearic acid, C18-1: oleic acid, C18-2: linoleic acid, C18-3: linolenic acid An esterification reaction of a fatty acid and alcohol or a transesterification of rapeseed oil and alcohol was conducted using, as a raw material, fats and oils and alcohols shown in Table 7, under conditions of mole ratio, temperature, pressure and reaction time shown in Table 7. Since about 98.5% of rapeseed oil is composed of a tri-glyceride, the reaction from rapeseed oil can be judged to be a transesterification. The reaction product was subjected to HPLC analysis in the same manner as in Example 1, from the HPLC analysis result, conversion into a fatty acid alkyl ester from a fatty acid or rapeseed oil (=yield of alkyl ester) was obtained. The results are shown in Table 7 together with the reaction conditions. TABLE 7 Alcohol/fats and oils Temperature Pressure Reaction Example (mole ratio) Fats and oils Alcohol (° C.) (Mpa) time (min) Yield (%) Example 42/1C18-3 Methanol 300 20 8 96.2 5-1 Example 42/1C18-2 300 20 8 95.1 5-2 Example 42/1C18-1 300 20 8 95.8 5-3 Example 42/1C18-0 300 20 8 94.7 5-4 Example 42/1C16-0 300 20 8 94.0 5-5 Example 42/1 Rapeseed 300 20 15 98.0 5-6 oil Example 42/1 Rapeseed 350 43 4 98.0 5-7 oil Example 42/1C18-3 Ethanol 300 15 12 94.6 5-8 Example 42/1C18-2 300 15 14 97.4 5-9 Example 42/1C18-1 300 15 14 95.9 5-10 Example 42/1C18-0 300 15 15 91.2 5-11 Example 42/1C16-0 300 15 14 91.7 5-12 Example 42/1 Rapeseed 300 15 45 96.7 5-13 oil Example 42/1 Rapeseed 350 25 10 97.1 5-14 oil Example 42/1C18-3 1-propanol 300 10 15 97.0 5-15 Example 42/1C18-2 300 10 14 92.7 5-16 Example 42/1C18-1 300 10 14 92.3 5-17 Example 42/1C18-0 300 10 14 89.6 5-18 Example 42/1C16-0 300 10 14 90.1 5-19 Example 42/1 Rapeseed 300 10 45 96.1 5-20 oil Example 42/1 Rapeseed 350 23 14 98.8 5-21 oil Example 42/1C18-3 1-butonal 300 9 15 97.3 5-22 Example 42/1C18-2 300 9 14 92.4 5-23 Example 42/1C18-1 300 9 14 86.1 5-24 Example 42/1C18-0 300 9 14 82.5 5-25 Example 42/1C16-0 300 9 14 81.1 5-26 Example 42/1 Rapeseed 300 9 45 87.1 5-27 oil Example 42/1 Rapeseed 350 23 14 95.3 5-28 oil Example 42/1 Rapeseed 1-octanol 300 6 45 68.7 5-29 oil Example 42/1 Rapeseed 350 19 20 90.7 5-30 oil C16-0: palmitic acid, C18-0: stearic acid, C18-1: oleic acid, C18-2: linoleic acid, C18-3: linolenic acid |
at 100℃; for 0.166667 - 1.16667h; autogeneous pressure; Microwave irradiation; | 19 Example 19 - Microwave Enhanced Homogeneous Acid Esterification for 100%FreeFatty Acid Feed; For this sample, the CSB system shown in Figure 7 was used to process 100% oleic acid feed. Sulfuric acid was the homogeneous acid catalyst tested. It was added to the methanol so that a concentration of 0.25 wt% sulfuric acid by the weight of the oleic acid (FFA) was obtained. The acidified methanol was added to FFA to obtain a 6:1 molar methanol to FFA ratio. The target operating temperature was 100°C. The fluid velocity was 0.208 m/s and the operating pressure was 20 psig above autogeneous.One major change was implemented to the test procedures using heterogeneous catalysts, presented in Example 2. Instead of sending the feed through the by-pass loop to pre-heat, the feed was sent immediately through the flow through microwave reactor. Thus at time zero, the feed with homogeneous catalyst was at room temperature as indicated in Figure 20.Also at time zero, 20 watts of microwave power (2 W/cc) were applied to the flow through microwave reactor (without heterogeneous catalyst) as the feed/product mixture flowed.Samples were collected every ten minutes and the fluid temperature was recorded. The samples were centrifuged and analyzed using the gas chromatograph. Figure 20 is a plot of the FFA conversion and fluid temperature with time. Within 70 minutes of the start of the test and after 40 minutes at operating temperature of 100°C, 100% of the oleic acid was converted. This is a WHSV of over 340.This example demonstrates that lower catalyst content and lower bulk operating temperature can be used with emulsification and microwaves. | |
With zirconium doped MCM-41 silica supported WO3 at 65℃; | ||
99.1 %Chromat. | With hydrogenchloride In water monomer; toluene at 45℃; for 1h; | |
With sulfuric acid | ||
100 %Chromat. | With scandium trifluoromethanesulphonate at 150℃; for 0.0166667h; Microwave irradiation; | |
> 99 %Chromat. | With silica SBA-15 supported diphenylammonium triflate at 95℃; for 2h; | |
With hydrogenchloride | ||
With boron trifluoride at 90℃; for 0.166667h; | ||
With SO42-/ZrO2-MoO3-Nd2O3 solid acid catalyst at 65℃; for 4h; | ||
With mesoporous perovskite at 59.84℃; for 18h; Acidic conditions; Molecular sieve; | ||
With 12-tungstophosphoric acid anchored to SBA-15 at 40℃; for 4h; | ||
Stage #1: methanol With tungstophosphoric acid3 immoblized on SBA-15 mesoporous silica at 60℃; Stage #2: cis-Octadecenoic acid | ||
With recombinant Thermomyces lanuginosus HSAU(800)P0306 extracellular lipase; mesoporous silica; glycine; sodium hydroxide In water monomer at 45℃; for 24h; Enzymatic reaction; | ||
With porous carbon-based acid catalyst for 4h; | ||
With iodine for 12h; Reflux; | 1 Example 1 - Esterification of oleic acid to make methyl oleate (MO); Oleic acid (200.0 g, 354.0 mmol), methanol (200.0 ml) and iodine (2.0 g, 1.0%), were reflux ed for 12 hr. The progress of the reaction was monitored by thin layer chromatography (TLC). After the reaction, excess methanol was removed under reduced pressure and the residue was extracted with ethyl acetate. The ethyl acetate was washed with a solution of sodium thiosulfate and subsequently washed the organic layer with water, NaHC03 and brine, dried over Na2S04 and concentrated with rotary evaporator to give the desired methyl oleate (210.5 g). | |
With carbon-coated alumina | ||
With 3-(N,N-dimethyldodecylammonium)propanesulfonic acid p-toluenesulfonate at 60℃; for 3h; | ||
With lipase from Candida sp. 99-125 In neat (no solvent) at 20℃; for 24h; Molecular sieve; Enzymatic reaction; | 2.2.1 General procedures of esterification General procedure: All the esterification experiments were carried out in a 50 mL round bottom flask. The reaction procedure was described as follows: To a mixture of 0.05 mol oleic acid and corresponding alcohol, catalyst was added at the given temperature. Normally, the reactants mixture kept stirring for 24 h until the reaction completed. The samples were taken out every 1 h in the first 12 h, and the acid value was determined according to the standard GB1668-81. In the end, the chromaticity of the oleates was recorded on PFX-i Series from Tintometer Ltd. | |
With diphenylammonium hydrogen sulphate at 125℃; for 1h; | ||
With sulphated zirconia at 80℃; for 4h; | ||
With mesoporous nanocrystalline sulfated zirconia catalyst at 60℃; | 2.4. Catalyst testing The catalytic activity/performance of the prepared sulfated zirconiacatalyst was determined by testing it for the esterification ofoleic acid in soybean oil (10% oleic acid) as model reactant for usedoil hereafter mentioned as acid oil. The reaction was carried out ina cylindrical jacketed glass reactor with four necks. It was equippedwith condenser to reflux the methanol evaporated during the reaction.A thermocouple with digital temperature indicator was usedto measure the temperature of the reaction mixture. The stirringwas carried out using a magnetic stirrer (396 W, StableTemp, ColeParmer) at 1000 rpm. To start the experiments, 42 ml acid oil and18 ml methanol (methanol/oil: 9/1) were added to the reactor. Themixture was heated to 60 C by circulating the hot water througha reactor jacket with continuous stirring. Then 2% (wt % of acid oil)of catalyst was added to start the reaction. Samples (2 ml aliquot)were removed from the reaction mixture at specified times duringthe progress of reaction and immediately cooled to 10-12 C temperature.The cooled sample was then centrifuged to separate thesolid catalyst from the liquid reaction mixture. Approximately, 1 gof the separated liquid phase was dissolved in 5 ml of 2-propanolto make a homogeneous solution which was then titrated against0.05 N KOH solution in the presence of phenolphthalein indicatorto determine the acid value (mg of KOH required to neutralize 1 gof the sample). | |
With boron trifluoride at 70℃; for 0.0833333h; | 13 Procedures for Preparing Methyl Esters of Fatty Acids and Oleoyl Ethanolamide Derivative One drop oleic acid of commercial or purified product was mixed with 14% boron trifluoride-methanol solution in 5 mL glass vial at 70° C. for 5 minutes. 2 mL hexane was then added to the reaction mixture to extract the fatty acid methyl esters. The anhydrous reaction product of the oleoyl ethanolamide (about 5 mg) was placed into 2 ml, glass vial for producing its ether derivative for GC quantification. Pyridine (0.5 mL) was added followed by hexamethyldisilazane (0.15 mL) and trimethylchlorosilane (0.05 mL). The mixture was shaken for 15-30 seconds and allowed to stand for 1 hour or stored in a freezer (0° C.) overnight to allow the upper layer phase turn clear (Wood et al., J. Am. Oil. Chem. Soc. 42:161-65 (1965), which is hereby incorporated by reference in its enirety). GC was used to quantify oleoyl ethanolamide. The purity of oleoyl ethanolamide was calculated according to the peak area ratio. | |
With Fe3O4 on SiO2-NH2/H3PW12O40 on CS/H3PW12O40 at 40℃; for 4h; | ||
90.8 %Chromat. | With Candida antarctica lipase B In water monomer at 32℃; for 24h; Enzymatic reaction; | |
With porous p-phenolsulfonic acid-formaldehyde resin at 80℃; Flow reactor; | ||
With sulfuric acid Reflux; | ||
With tin(II) bromide monohydrate at 59.84℃; for 0.0833333h; | ||
With 30percent undecasilicotungstate anchored to mesoporous MCM-41 at 65℃; for 16h; Dean-Stark; | ||
With aluminium trifluoromethanesulphonate at 165℃; for 1h; | ||
With tin alginate at 60℃; for 2h; | ||
With sulfuric acid | ||
With 1-hexyl-3-methylimidazolium hydrogen sulfate at 99.84℃; for 6h; Ionic liquid; Inert atmosphere; Green chemistry; | ||
With sulfuric acid at 20℃; Flow reactor; | ||
With boron trifluoride at 90℃; for 1h; | ||
With monolacunary silicotungstate anchored to zeolite beta at 60℃; for 10h; Dean-Stark; Green chemistry; | ||
47.7 %Spectr. | With mesoporous 1-butyl-3-methylimidazolium supported sulfated zirconia nanocrystal at 59.84℃; for 8h; Inert atmosphere; Green chemistry; | 2.4. Esterifiaction of long chain fatty acids and transesterificationreactions General procedure: 2.4. Esterifiaction of long chain fatty acids and transesterificationreactionsFor each of the catalytic reaction 1 mmol of the reactant fattyacid was dissolved in 0.96 g methanol taken in a 50 ml round bottomflask. Then 80 mg of M-IL-SZO-1C catalyst was added into the RBflask. The reaction mixture was refluxed at 333 K for 8 h under thenitrogen atmosphere. To study the progress of the reaction, thereaction mixtures were collected at different time intervals and theprogress of the reactions were monitored by TLC. |
With hydrogenchloride In chloroform at 90℃; for 1h; | ||
With sulfonated carbonized β-cyclodextrin CD-3 at 60 - 80℃; for 12h; | Catalytic Testing Catalytic esterification of oleic acid with methanol was performed in a flask equipped with a water condenser. The reaction mixture was 100 mmol of methanol and 10 mmolof oleic acid with carbon solid acid catalyst (5 wt% on the basis of the oleic acid weight). The reaction temperature was 60-80 °C for 12 h. Aliquots (0.2 mL) were taken at regular intervals. After the reaction was completed, the mixture was centrifuged (16,000 rpm, 10 min) to separate the spent solid catalyst and then dried under vacuum at 70 °C for 10 min to remove the methanol, followed byaddition of 200 μL of anhydrous n-hexane with 1.0 mM of n-dodecane for the GC analyses. | |
With SO42-/ZrO2 catalyst at 100℃; for 2h; | ||
With toluene-4-sulfonic acid at 59.84℃; Sealed tube; | ||
With propylsulfonic acid functionalized mesoporous silica at 60℃; | Esterification of oleic acid with either methanol or glycerol The esterification of oleic acid with either methanol or glycerolwas performed in a 100-mL round-bottom flask equipped with amagnetic stirrer and a water-cooled condenser. The oleic acid andmethanol esterification was performed with a 1:9 molar ratio ofoleic acid: methanol at 60C, whereas the esterification of oleicacid and glycerol was carried out with a 6:1 molar ratio of oleicacid:glycerol at 110C. The reaction time was varied in the rangeof 15-180 min for methanol or 15-1440 min for glycerol with 0.5%(w/w) of catalyst (based on the reactant mass). After completion ofthe reaction, the used catalyst was separated from the liquid phaseby centrifugation. | |
With boron trifluoride at 20℃; for 0.25h; | 3 2.2 Sample preparation General procedure: The procedure to convert fatty acids (FA) to fatty acid methyl esters (FAME) was described previously and is summarized in Eq. (1) [20]. Briefly, the FA (∼1mg) was treated with BF3 in a 10% methanol solution at room temperature (RT) and then extracted into a non-polar solvent (e.g., n-pentane). Fresh samples were prepared for mass spectrometry by collecting the upper n-pentane layer (∼3mM) and diluting in methanol to yield of final solution of 10-20μM in the resulting FAME. Then, each iodine-containing reagent was added to a sample of this solution to a final concentration of 5-10μM before adding 0.05% formic acid to aid the formation of protonated 4-iodoaniline (pIA) for charge adducting.Deuterium-exchanged experiments were undertaken as summarized in Eq. (2), whereby a mixture of D1-methanol and D2O (2:1) was used to dilute 1μL of the n-pentane layer to exchange all three protons in protonated amine group (-ND3+).Preparation of the D3-labeled FAME 1,1,1-trideuteromethyl (Z)-octadec-9-enoate is summarized in Eq. (3). In this procedure, 9Z-ocatadecanoic acid (1mg, 4μmol) placed in D3-methanol (CD3OH, 100μL), with the addition of sulfuric acid (2%), was heated at 70°C for 15min in an oil bath and then allowed to cool for 15min. Milli-Q water (1mL) and n-pentane (1mL) were added to the solution. After vigorous shaking, to ensure thorough mixing, the mixture was left for 30min at 4°C to allow the separation of the aqueous and organic layers. The n-pentane layer was collected with a Pasteur pipette and was prepared for mass spectrometric analysis as described above. Methyl (Z)-2,2-dideutero-octadec-9-enoate was prepared by adapting a procedure previously used to synthesize methyl 2,2-dideuteropentanoate and is summarized in Eq. (4) [21]. D1-Methanol (CH3OD, 8.13g, 246mmol) was cooled in an ice-bath under a nitrogen atmosphere and sodium metal (75.4mg, 3.28mmol) was added. After the metal had dissolved, 3.25mL of the solution was added to methyl (Z)-octadec-9-enoate (1.00g, 3.71mmol) and the resulting mixture heated at reflux under nitrogen for 48h. The solvent was removed in vacuo to yield the product as brown oil. The sample was then prepared for mass spectrometric analysis as described above. | |
With magnetic porous carbons-0.8-SO3H at 80℃; for 2h; | ||
With C34H74N2O6S2(2+)*2C7H7O3S(1-) at 60℃; for 4h; Ionic liquid; Green chemistry; | 2.3. Esterification reaction The esterification reactions were carried out in a 10-ml tubewith a reflux condenser. Portions of the catalyst (0.020-0.316mmol) and of oleic acid (7.9 mmol, 2.23 g) were transferredinto the reactor and preheated prior to the addition of the alcohol.Upon reaching the desired reaction temperature (25-70°C), methanol (0.32-1.28 ml) was added into the reactor andthe reaction was initiated. The reaction mixture was vigorouslystirred at a constant rate for all runs. The oleic acid-methanolmolar ratio, reaction time and temperature were all varied according to an experimental design. Upon reaction completion,the reactor was cooled to room temperature and phaseseparation was observed. Excess methanol was evaporatedunder vacuum and the IL settled to the bottom of the flask becauseit was immiscible with the ester, which formed the upperlayer. Thus, the biodiesel could be separated by simple decantationand the catalyst was easily recycled by removal ofwater. The conversion of oleic acid was determined by acid-base titration [18]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 100% 2: 100% | Stage #1: Methyl oleate With ozone In dichloromethane at -78℃; Stage #2: With triphenylphosphine In dichloromethane at -78 - 23℃; for 18h; | 4 A solution of methyl oleate ( 10.0 g, 33.7 mmol) in anhydrous CH2Cl2 ( 100 mL) was cooled to -78 °C and a stream of O3 was bubbled through the reaction mixture until the solution became lightly blue ( 10 min). Argon was bubbled through the mixture and a solution of PPh3 (19.7 g, 75.1 mmol) in CH2Cl2 (100 mL) was added slowly. The reaction mixture was warmed to 23 0C and stirred for 18 hours. The solvent was evaporated to dryness and the solid was triturated with cold hexane (80 mL). The EPO filtrated was evaporated to give a yellow oil. The oil was purified by chromatography on silica gel (CH2Cl2:Hex, 1 : 1 and then CH2Cl2:Et2θ, 1 : 1) to provide the two expected aldehydes, nonanal (4.80 g, 100%) and methyl 8-formyloctanoate 12 (6.28 g, 100%), both as colourless oils. 1H NMR (300 MHz, CDCl3) δ 9.76 (s, IH), 3.66 (s, 3H), 2.41 (t, J= 7.3 Hz, 2H), 2.30 (t, J= 7.3 Hz, 2H), 1.61 (m, 4H), 1.31 (m, 6H). 13C NMR (75 MHz, CDCl3) δ 202.4, 173.8, 51.1 , 43.5, 33.7, 28.7, 28.6, 28.5, 24.5, 21.7. MS (APCI): 187 (M+ l)+. Rf= 0.2 (CH2Cl2). |
1: 96% 2: 74% | With N-methyl-2-indolinone; ozone at 0℃; | |
75% | Stage #1: Methyl oleate With ozone In methanol; dichloromethane at -78℃; Inert atmosphere; Stage #2: With acetic acid; zinc In methanol; dichloromethane for 0.5h; Inert atmosphere; |
With ozone; acetic acid; zinc 1.) MeOH, CH2Cl2, -78 deg C, 2.) MeOH, CH2Cl2, 30 min; Multistep reaction. Yields of byproduct given; | ||
With ozone at 200℃; for 0.0833333h; | ||
With ozone In hexane at -78℃; | ||
With ozone; acetic acid Behandlung der Reaktionsloesung mit Zinkstaub und Wasser; | ||
With ozone; acetic acid; zinc 1.) MeOH, CH2Cl2, -78 deg C, 2.) MeOH, CH2Cl2, 30 min; Yield given. Multistep reaction; | ||
With sodium tungstate; alkylated polyethyleneimine; dihydrogen peroxide at 22℃; for 24h; | ||
With sodium periodate; ruthenium In water; 1,2-dichloro-ethane at 20℃; for 12h; | ||
Stage #1: Methyl oleate With ozone In dichloromethane at -78℃; for 1h; Stage #2: With dimethylsulfide In dichloromethane at 25℃; for 6h; | 1 Example: 1Preparation of Hexadecyl cis-9-Tetradecenoate: Preparation of hexadecyl cis-9-tetradecenoate, 4 was carried out according to the Scheme 1. Oleic acid methyl ester, 1 (12.0 g, 0.0314 mol) in dichloromethane (100 ml) was cooled to -78 degree. C and ozone gas was bubbled into the reaction mixture for 1 hr. After reaction, the reaction was quenched by adding dimethyl sulphide (DMS, 8 ml) and was stirred for 6 hr at 25° C. The solvents were removed under vacuum and the residue 2 thus obtained (4.25 g, 0.022 mol) was used directly for the preparation of cis-9-myristoleate, 3. n-Pentyl-triphenyl phosphonium salt (11.16 g, 0.027 mol) was taken in 50 ml of dry THF and cooled to 0° C. To this slurry, n-butyl lithium (17.0 ml, 1.6 M in hexane) was added, stirred the reaction mixture for 0.5 hr to obtain an orange solution. 1-Al-methyl nonanoate containing crude product 2 (5.0 g, 0.027 mol) dissolved in dry THF (20 ml) was added to the above contents slowly and allowed the reaction mixture to reach to 25 degree. C and then heated to reflux temperature to reflux for 4 hr. The reaction was monitored by TLC and after completion of the reaction, THF was removed from the reaction mixture under reduced pressure, and to the residue distilled water 825 ml) was added and extracted with ether (25 ml×3 times). The combined ether layer was dried over anhydrous sodium sulphate and solvent was removed and dried under vacuum to get the residue and was purified by column chromatography using hexane and ethyl acetate (98:2) as eluent to get cis-9-myristoleate, 3 (4.2 g, 0.0175 mol) in 65% yield with 66% purity by GC. cis-9-Myristoleate, 3 (4.2 g, 0.0175 mol) was enzymatically transesterified with cetyl alcohol (5.08 g 0.021-mol) in the presence of Lipozyme TL IM (0.930 g, 10 wt % of the total substrate) at 68° C. for 8 hr. The reaction was monitored by TLC and after completion of the reaction, hexane (50 ml) was added and the lipase was separated by filtration and the solvent was evaporated to get the crude product and was purified by column chromatography to obtain hexadecyl cis-9-tetradecenoate, 4 (7.48 g, 0.0166 mol) in 95% yield with 92% purity by GC. The structure of hexadecyl cis-9-tetradecenoate, 4 was confirmed by 1H NMR, IR, and GC-MS.Spectral Data:1H NMR: (600 MHz, CDCl3): δ 5.36-5.33 (m, 2H, J=3 Hz, -CHCH-), 4.01 1.99 (m, 4H, -CH2-CHCH-CH2-), 1.60 (m, 4H, -CH2-CH2-CHCH-CH2-CH2-), 1.30-1.20 (br, d, 38H, -CH2-CH2-CH2-), 0.90 (q, 6H, -CH2-CH3).IR (neat/NaCl): 2926, 1738, 1654, 1242, 721 Cm-1.GC-MS: m/z: C30H5802 (M+): 450. | |
With ozone In water; propionic acid for 1h; | 1 Example 1Comparative ExampleOzonolysis and Oxidation without Addition of Acid20 g of a 0.182 molal solution of methyl oleate (95% pure) in a solvent mixture of propionic acid and water (15 equivalents based on moles of double bond) were initially charged in a two-neck flask with gas inlet tube and reflux condenser. The feed gas, consisting of 5% by volume of oxygen in carbon dioxide was passed through an ozone generator at a flow rate of 40 ml/min. The ozone generator was set to maximum power. The ozone-containing gas mixture was passed into the reaction mixture with stirring. The offgas stream was passed by means of gas wash bottles into a 5% aqueous potassium iodide solution. After 60 minutes, the substrate was converted, and the gas introduction was then stopped. According to GC analysis, the reaction mixture had a content of 39.5 wt % of 9-nonanal and 38.2 wt % of methyl 9-oxononanoate.After adding hydrogen peroxide (0.454 g of a 30% aqueous solution), the reaction mixture was then heated to 100° C. in an oil bath. After 120 minutes, nonanal and methyl 9-oxononanoate were converted completely to the respective carboxyl compounds. GC analysis: 41.05% pelargonic acid, 39.65% monomethyl azelate (FID signal, figure in area percent, uncorrected). | |
Multi-step reaction with 3 steps 1: [((S,S)-N,N′-bis(2-pyridylmethyl)-(S,S)-2,2′-bipyrrolidine)FeII(OTf)2]; dihydrogen peroxide / acetic acid; acetonitrile / 2.5 h / 0 °C 2: sulfuric acid / acetic acid; acetonitrile; water / 16 h / 20 °C 3: sodium periodate; sodium hydrogencarbonate / acetic acid; acetonitrile; water / 1.5 h / 20 °C | ||
With oxygen at 85℃; for 6h; | ||
Multi-step reaction with 3 steps 1: formic acid; dihydrogen peroxide / neat (no solvent) / 8 h / 20 - 30 °C / Cooling with ice 2: boron trifluoride diethyl etherate / dimethyl sulfoxide / 22 h / 80 °C / Inert atmosphere 3: N-methyl-4,5-dimethylthiazolium iodide; potassium carbonate / acetonitrile / 0.5 h / 130 °C / Microwave irradiation; Inert atmosphere | ||
With oxygen at 85℃; for 6h; | ||
With sodium periodate; C24H28ClN4O2Ru(1+)*F6P(1-) In dichloromethane; water; acetonitrile at 65℃; for 8h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With tributyl-amine; titanium tetrachloride In toluene at -5 - 0℃; for 1h; Inert atmosphere; | |
93% | With tributyl-amine; titanium tetrachloride In toluene at 0 - 5℃; for 1h; Inert atmosphere; | methyl 3-oxo-2-((Z)-hexadec-7-en-1 -yl)-(Z)-1 1 -eikosate (D27) TiCI4 (1 .5 eq.) dissolved in 4 mL of dry toluene was added dropwise under an inert gas atmosphere to a mixture of methyl oleate (1 .0 eq.) and NBu3 (18 eq.) in 16 mL of dry toluene at 0 to (0795) 5°C. The temperature was maintained for one hour after the dropwise addition was over, and then 20 mL of water was added and washed twice with diethyl ether. The combined ether layers were dried over Na2S04. The product was purified by chromatography using 2.5% Et20 in n-hexane. A yellow oil was obtained. 93% yield. (0796) 1 H NMR (400 MHz, CDCI3) δ 5.40 - 5.27 (m, 4H), 3.71 (s, 3H), 3.43 (t, J = 7.4 Hz, 1 H), 2.61 - 2.39 (m, 2H), 2.07 - 1 .95 (m, 8H), 1 .90 - 1 .74 (m, 2H), 1 .64 - 1 .50 (m, 2H), 1 .40 - 1 .17 (m, 40H), 0.93 - 0.83 (m, 6H); 13C NMR (101 MHz, CDCI3) δ 205.63, 170.58, 130.19, 130.14, 129.87, 129.79, 59.16, 52.43, 42.02, 32.06, 29.91 , 29.85, 29.77, 29.68, 29.48, 29.44, 29.42, 29.26, 29.16, 29.12, 28.43, 27.63, 27.37, 27.32, 27.27, 23.59, 22.84, 14.28. |
With sodium hydride; xylene |
With sodium hydride In 1,2-dimethoxyethane |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With isopropyl alcohol In hexane at 0℃; for 0.0833333h; Inert atmosphere; | |
98% | With C32H36ClNO2P2Ru; potassium <i>tert</i>-butylate; hydrogen In tetrahydrofuran at 120℃; for 20h; Autoclave; Green chemistry; | 59; 76 Example 48: Hydrogenation of methyl benzoate catalyzed by two thousandths of a molar equivalent of ruthenium complex 1c General procedure: In a glove box in a nitrogen atmosphere, 3.33 mg of ruthenium complex 1c (0.005 mmol) Add to a 125-mL Parr autoclave, After adding 11.2 mg of potassium t-butoxide (0.1 mmol), Then take 2mL of tetrahydrofuran and add it to the kettle for a while. Finally, methyl benzoate (1.3615 g, 10 mmol) was added. After the autoclave is sealed, it is taken out of the glove box. Charge hydrogen to 50 atm. The mixture in the reaction kettle was heated and stirred in an oil bath at 120 ° C for 10 hours, The reactor was cooled to room temperature in a water bath and the remaining gas was slowly drained from the fume hood. Tridecane (50 μL) was added to the mixture as an internal standard, and the yield of methyl benzoate was determined by gas chromatography to be 99%. |
97% | With lithium aluminium tetrahydride In tetrahydrofuran at 0 - 20℃; for 24h; |
95% | With lithium aluminium tetrahydride In diethyl ether at 35℃; for 2h; | |
95% | With C17H16BrMnNO3P; potassium <i>tert</i>-butylate; hydrogen In 1,4-dioxane at 100℃; for 6h; Autoclave; chemoselective reaction; | |
95% | With [Ru(2-(methylthio)-N-[(pyridin-2-yl)methyl]ethan-1-amine)(triphenylphosphine)Cl2]; potassium <i>tert</i>-butylate; hydrogen In toluene at 80℃; for 3h; | |
92% | With lithium aluminium tetrahydride In diethyl ether for 1h; Heating; | |
90% | With lithium aluminium tetrahydride In diethyl ether | |
89% | With C15H29MnNO3P2(1+)*Br(1-); potassium <i>tert</i>-butylate; hydrogen In 1,4-dioxane at 120℃; for 48h; Inert atmosphere; Autoclave; | |
83% | With ethandithiol; sodium tetrahydroborate In tetrahydrofuran for 24h; Heating; | |
80% | With lithium aluminium tetrahydride In tetrahydrofuran at -10 - 30℃; for 3.5h; Cooling with ethanol-dry ice; | 3 Embodiment 3: synthesis of oleyl alcohol The lithium aluminum hydride (12 g, 0.316 µM), tetrahydrofuran 220 ml into a 500 ml single-port in the bottle, and then putting ethanol in ice, then oleic acid methyl ester (90 g, 0.3 µM) constant voltage used in the separatory funnel is slowly added to the reaction system, after adding in the -10 °C under stirring for half an hour, and then the system temperature to rise to 30 °C reaction 3 hours, cool the reactant to -10 °C, adding 12 g water, 12 g sodium hydroxide dilute solution, 40 g of anhydrous sodium sulfate. After the thorough mixing filtration, then the filtrate is steaming and to remove the solvent, vested oleyl alcohol. Yield 80%. |
78% | With lithium aluminium tetrahydride In diethyl ether for 3h; Heating; | |
68% | With aluminum oxide; sodium; <i>tert</i>-butyl alcohol In toluene Heating; | |
51% | Stage #1: Methyl oleate With [CpFe(CO)2(PCy3)][BF4]; phenylsilane at 100℃; for 45h; Irradiation; Neat (no solvent); Inert atmosphere; Stage #2: With hydrogenchloride; water In tetrahydrofuran at 20℃; for 1h; | |
47% | With sodium tetrahydroborate In 1,4-dioxane; water at 70℃; for 4h; | |
With sodium; butan-1-ol | ||
With lithium aluminium tetrahydride; diethyl ether | ||
With lithium aluminium tetrahydride In diethyl ether Yield given; | ||
With lithium aluminium tetrahydride In diethyl ether | ||
With titanium(IV) isopropylate; sodium hydroxide; Triethoxysilane 1.) heating, 5 h, 2.) THF, room temperature; Yield given. Multistep reaction; | ||
With titanium(IV) isopropylate; sodium hydroxide; polymethylhydrosiloxane 1.) 65 deg C, 2 h, 2.) THF, 12 h; Yield given. Multistep reaction; | ||
With sodium hydroxide; sodium tetrahydroborate; zinc 2-ethylhexanoate 1.) THF, 70 deg C, 4 h, 2.) 40 deg, 1 h; Yield given; Multistep reaction; | ||
With lithium aluminium tetrahydride | ||
With hydrogen at 300℃; | 4; 5 Examples 4 and 5 [0034] Hydrogenation of technical oleic acid methyl ester. 4*4 mm pellets 1,000 ml in volume of the catalyst of Example 1 were introduced into a fixed-bed reactor. Hydrogenation was carried out with technical unsaturated methyl esters (A and B) at a temperature of 300[deg.] C., under a pressure of 250 bar and at an LHSV (liquid hourly space velocity) of 0.5 h. The characteristic data of the hydrogenation products are set out in Table 1. | |
With hydrogen at 300℃; | C1; C2 Comparison Examples C1 and C2 [0035] Hydrogenation was carried out as in Examples 4 and 5 using a conventional chromium/zinc hydrogenation catalyst. The reaction conditions were the same as in Examples 4 and 5. The characteristic data of the hydrogenation products are set out in Table 1. | |
With {OsH(CO)[PyCH2N(CH2)2PiPr2]2; hydrogen In tetrahydrofuran at 100℃; for 4h; Autoclave; | ||
With OsHCl(CO)[(iPr)2PNH(CH2)2NHCH2Py]; potassium <i>tert</i>-butylate; hydrogen In tetrahydrofuran at 100℃; for 4h; Autoclave; regioselective reaction; | 15 EXAMPLE 15. TYPICAL PROCEDURE FOR HYDROGENATION OF ESTERS USINGCOMPLEXES (la), AND (3).A solution of catalyst 1 (5.2 mg/mL) and a base (0.2 mmol) in THF was mixed with 0.02 mol of the ester substrate in 6 mL of THF. The mixture was then transferred into a 75 mL stainless-steel reactor (Parr 4740) equipped with a magnetic stir bar. The reactor was purged by two cycles of pressurization/venting with H2 (150 psi, 10 Bar), pressurized with H2 (725 psi, 50 Bar), and was disconnected from the H2 source. The hydrogenation was conducted at 40-100 °C. At the end of the required reaction time, the reactor was placed into a cold-water bath and depressurized afier cooling to the ambient temperature. | |
90 %Chromat. | With [RuCl2(2-(diphenylphosphino)-N-((6-((diphenylphosphino)methyl)pyridin-2-yl)methyl)ethan-1-amine)]; potassium <i>tert</i>-butylate; hydrogen In tetrahydrofuran at 80℃; for 5h; Autoclave; chemoselective reaction; | |
With carbonylhydrido(tetrahydroborato)[bis(2-dicyclohexylphosphinoethyl)amino]ruthenium(II); hydrogen at 100℃; for 18h; Autoclave; Inert atmosphere; | 1a Synthesis of Oleyl Oleate (a Ceride) from a MethylEster Using the Catalyst lc [0072] The catalyst ic (4.7 mg; 7.7 jtmol) is introduced into an autoclave containing a stirrer bar. 2.3 g of methyl oleate (7.7 mmol) is introduced via a syringe under an argon atmosphere. The autoclave is then purged three times byvacuum/hydrogen cycle and then around 20 bar of hydrogen are introduced. The system is heated to 100° C. with theof an oil bath and is stirred magnetically for 18 hours. Methanol and also oleyl alcohol are obtained. It is noted that the unsaturations of the fatty chain are not hydrogenated during this process. | |
With carbonylhydrido(tetrahydroborato)[bis(2-diphenylphosphinoethyl)amino]ruthenium(II); hydrogen at 110℃; for 2h; Inert atmosphere; Autoclave; Sealed tube; | ||
With diisobutylaluminium hydride In tetrahydrofuran; hexane at 0℃; for 2h; Inert atmosphere; | ||
With sodium ethanolate at 30 - 60℃; | 1 In a typical preparation, methyl oleate is combined with a base (i.e., sodium ethoxide), optionally a solvent (i.e., tetrahydrofuran), and a catalytic amount of an ester hydrogenation catalyst (i.e., [Ru-SNS] or [Ru-PNP]) in a reactor. The reactor is then heated to 30-60 °C and pressurized with hydrogen gas to 5-30 bar. When the reaction is complete, the reactor is depressurized and the contents washed with water or aqueous solutions (i.e., aqueous hydrochloric acid) to remove reaction by-products. The product may be further purified by methods such as distillation, if required. Oleyl alcohol produced using Ru-SNS and Ru-PNP provides >98% Z-selectivity with <1.0% over-reduction of the double bond. | |
With hydrogen; sodium ethanolate at 30 - 60℃; | 1 In a typical preparation, methyl oleate is combined with a base (i.e., sodium ethoxide), optionally a solvent (i.e., tetrahydrofuran), and a catalytic amount of an ester hydrogenation catalyst (i.e., [Ru-SNS] or [Ru-PNP]) in a reactor. The reactor is then heated to 30-60 °C and pressurized with hydrogen gas to 5-30 bar. When the reaction is complete, the reactor is depressurized and the contents washed with water or aqueous solutions (i.e., aqueous hydrochloric acid) to remove reaction by-products. The product may be further purified by methods such as distillation, if required. Oleyl alcohol produced using Ru-SNS and Ru-PNP provides >98% Z-selectivity with <1.0% over-reduction of the double bond. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | Stage #1: Methyl oleate With sodium hydride In 5,5-dimethyl-1,3-cyclohexadiene; hexane at 150℃; for 5h; Stage #2: With sodium hydroxide In tetrahydrofuran; water at 100℃; for 5.5h; | 6 (9Z,26Z)-Pentatriaconta-9,26-dien-18-one To a solution of methyl oleate (10.0 g, 33.4 mmol) in xylene (18 mL), a suspension of sodium hydride (1.65 g, 63%, 43.4 mmol) washed in advance with hexane in xylene (3 mL) was added over 5 minutes, and the mixture was then reacted at 150°C for 5 hours. The reaction mixture was cooled to room temperature, then treated with water, and subjected to extraction with a hexane-ethyl acetate mixed solution. The obtained organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain an oil. To this oil, tetrahydrofuran (135 mL) and a 5 N aqueous sodium hydroxide solution (33 mL) were added, and the mixture was reacted at 100°C for 5.5 hours. The reaction mixture was cooled to room temperature, then treated with water, and subjected to extraction with a hexane-ethyl acetate mixed solution. The obtained organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure, followed by the formation of a solid with an acetone-hexane solvent. After removal of the solid by filtration, the solvent was distilled off from the resulting solution under reduced pressure, and the residue was then subjected to silica gel column chromatography to obtain the compound of interest as a colorless liquid (7.50 g, 89%). 1H-NMR (500 MHz, CDCl3) δ: 0.89 (6H, t, J = 6.8 Hz), 1.21 - 1.36 (40H, m), 1.52 - 1.60 (4H, m), 1.97 - 2.04 (8H, m), 2.38 (4H, t, J = 7.6 Hz), 5.30 - 5.39 (4H, m). |
With sodium ethanolate; xylene Erwaermen des Reaktionsprodukts mit wss.-aethanol.Kalilauge; | ||
Multi-step reaction with 2 steps 1: titanium tetrachloride; tributyl-amine / toluene / 1 h / -5 - 0 °C / Inert atmosphere 2: sodium hydroxide / tetrahydrofuran; water; methanol / 5 h / 70 °C |
Multi-step reaction with 2 steps 1.1: titanium tetrachloride; tributyl-amine / toluene / 1 h / 0 - 5 °C / Inert atmosphere 2.1: sodium hydroxide / tetrahydrofuran; methanol / 5 h / 70 °C 2.2: 0 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With hydrazine hydrate | |
82% | With hydrazine hydrate In ethanol for 8h; Reflux; | Synthesis of stearohydrazide (2) RBF having 0.1mol 80% hydrazine hydrate was added with Methyl oleate (1) (0.1M) which was continuously stirred and refluxed in ethanol for 8 hours. The solution which was formed by the reaction was taken in a beaker and was kept on ice box. The resulting precipitate was filtered and recrystallization was done from ethanol to get stearohydrazide10. The yield was 82%, m.p. 105°C, IR: (KBr, cm-1) 3316-3100 (NH-NH2), 2921, 2853 (C-H), 1629 (O=C-NH), 1160 (C-O-C), 720 [(CH2)n]. 1H NMR: (CDCl3, δ, ppm): 8.41 (1H, s, NH), 3.66 (2H, s, NH2), 2.27 (2H, t, CH2-CONH), 1.63 (2H, m, CH2CH2-CO), 1.25 (28H, s, 14×CH2), 0.88 (3H, t, CH3). ESI-MS: m/z 299 (M+H). Anal. Calcd. for C18H38N2O: C, 72.42; H, 12.83; N, 9.38%. Found: C, 72.80; H, 12.65; N, 9.14%. |
With ethanol; water; hydrazine hydrate |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98.8% | With formic acid; dihydrogen peroxide In water at 0 - 23℃; for 24h; | |
97% | With tris(2,4-pentanedionato)ruthenium(III); Pyridine-2,6-dicarboxylic acid; dihydrogen peroxide In water; acetonitrile at 25℃; for 4h; | |
97% | With tert.-butylhydroperoxide In decane for 2h; Reflux; |
91% | With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 20℃; for 5h; | |
89% | With oxone||potassium monopersulfate triple salt; sodium hydrogencarbonate In water; acetone at 0 - 20℃; | |
85% | With diphenylphosphinic anhydride; dihydrogen peroxide; potassium carbonate In tetrahydrofuran at -5℃; for 20h; | |
84% | With 2,4-bisperfluorooctylphenyl butyl selenide; water; dihydrogen peroxide In benzene at 70℃; | |
84% | With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 20℃; for 21h; | |
76% | With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 0℃; | Methyl cis-9,10-Epoxyoctadecanoate. To a solution containing 1.10 g (3.71 mmol) of methyl oleate in 20 mL of CH2Cl2 was added 1.02 g (4.45 mmol) of m-chloroperoxybenzoic acid portionwise at 0 oC. The reaction mixture was stirred overnight, then extracted with EtOAc. The organic phase was washed with aq NaHCO3, then dried over MgSO4, filtered and concentrated to provide methyl cis-9,10-epoxyoctadecanoate as a colorless oil: yield 0.88 g (76%); silica gel TLC Rf 0.35 (6:1 hexaneEtOAc); 1H NMR (CDCl3) δ 0.86 (t, 3H, J = 8.0 Hz), 1.25-1.30 (br m, 24H), 1.56-1.62 (m, 2H), 2.28 (t, 2H, J = 8.0 Hz), 2.87 (s, 2H) and 3.64 (s, 3H); 13C NMR (CDCl3, 100 MHz) δ 14.2, 25.0, 26.7, 26.7, 27.9, 27.9, 29.1, 29.6, 29.7, 32.0, 51.5,57.3, 57.3 and 174.3; mass spectrum (MALDI), m/z 312 [M]+ (theoretical m/z 312) and m/z 335 [M+Na]+ (theoretical m/z 335). |
75% | With sulfuric acid; dihydrogen peroxide; acetic acid In hexane; water at 57 - 58℃; for 19h; Green chemistry; | |
67% | With tert.-butylhydroperoxide; [(Me3tacn)Ru(CF3CO2)2(H2O)]CF3CO2-SiO2 In dichloromethane at 20℃; for 14h; | |
With peracetic acid; acetic acid | ||
With Perbenzoic acid; acetone | ||
> 99 %Chromat. | With dihydrogen peroxide; bis[3,5-bis(trifluoromethyl)diphenyl] diselenide In 1,1,1,3',3',3'-hexafluoro-propanol; water at 25℃; for 0.166667h; | |
91 %Chromat. | With tert.-butylhydroperoxide; {VO(C3N2O(CH3)(C6H5)(COCH3))2} In decane; chloroform at 70℃; for 10h; Inert atmosphere; | Catalytic oxidations General procedure: All catalytic experiments were carried out in a 10 mL glass flask fitted with a water condenser. In a typical experiment, 2.0 mol% of the proper catalyst were dissolved in 3.0 mL of chloroform and 2.0 equivalents per double bond of oxidant were added, followed by 0.1 mmol of the selected substrate. The reaction mixture was stirred (600 rpm) at 50 °C for the chosen time and the reaction progress was monitored and evaluated by GC analysis by taking, at regular time intervals, aliquots of the crude (50 L). Methyl palmitate was used as internal standard. At the end of reaction the mixture was quenched with 1.0 mL of a 5% aqueous solution of Na2S2O5 and the organic phase recovered with 2.0 mL of chloroform, dried over anhydrous MgSO4 and analyzed by GC after evaporation of the solvent. |
With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 0 - 20℃; for 12h; | ||
With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 0 - 23℃; for 15.1667h; Inert atmosphere; | ||
With sodium persulfate; sodium bis(1,2-dicarbollyl)cobaltate(III); water; potassium carbonate at 20℃; for 1h; UV-irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | Stage #1: Methyl oleate With ozone In dichloromethane Stage #2: With dimethylsulfane In dichloromethane | |
96% | With oxygen; ozone; N-Methylmorpholine N-oxide In dichloromethane at 0℃; | |
93% | With oxygen; ozone; N-Methylmorpholine N-oxide In dichloromethane at -78 - 20℃; for 2.41667h; | Synthesis of methyl 9-oxononanoate 4-Methylmorpholine N-oxide monohydrate (5.9 g, 50.6mmol,3.0 equiv) was dehydrated by heating at 90 °C under high vacuum overnight. Following the ozonolysis conditions of Drussault [12], a 250mL round-bottom flask equipped with stir bar was charged with methyl oleate (5.0 g, 16.9 mmol, 1.0equiv), the anhydrous 4-methylmorpholine N-oxide monohydrate prepared above, and anhydrous DCM (100 mL). Stirring was initiated, affording a clear solution. The reaction mixture was cooled to -78 °C for 15min before bubbling in amixture of ozone/oxygen. Conversion was complete within 10 min. The ozone generator was turned off and oxygen was bubbled through the solution for additional 10 min. The reaction mixture was allowed to warm to room temperature and aged for 2 h. The reaction was concentrated and the residue was dissolved in ethyl acetate (200 mL) and washed with water (80 mL) and brine (50 mL), dried over sodium sulfate, filtered, and concentrated to give a yellow oil. The oil was purified by chromatography on silica gel (hexane:EtOAc2:1) to provide methyl 9-oxononanoate (2.9 g, 93% yield) as a colorless oil. The spectral data were same with the one in published literature [9, 10]. |
81% | Stage #1: Methyl oleate With ozone In methanol at -60℃; Stage #2: With dimethylsulfane In methanol at -60 - 20℃; for 4h; | |
64% | With oxygen In methanol at -65℃; for 3.5h; | |
57% | With 2,3-dimercapto-succinic acid; ozone In methanol 1.) -60 deg C, 2.) -10 deg C, 1 h, 3.) 0 deg C, 1.5 h, 4.) 20 deg C, 1 h; | |
43% | Stage #1: Methyl oleate With anhydrous sodium carbonate; ozone In methanol; dichloromethane at -78℃; Stage #2: With triethylamine In methanol; dichloromethane at 0 - 20℃; for 6h; | |
41% | Stage #1: Methyl oleate With ozone In methanol at -30℃; Stage #2: With acetic acid; zinc powder In methanol at 30℃; | |
33% | Stage #1: Methyl oleate With ozone In dichloromethane at -78℃; for 4.5h; Stage #2: With triphenylphosphine In dichloromethane at 20℃; for 13h; | |
(i) O3, CH2Cl2, (ii) Ph3P; Multistep reaction; | ||
With ozone; triphenylphosphine Yield given. Multistep reaction; | ||
With sodium dihydrosulfite; ozone 1) methanol, -78 deg C, 15 min, 2) room temperature, 30 min; Multistep reaction; | ||
With lead tetraacetate; osmium(VIII)-tetroxide; hydrogen; manganese(II) oxide 1.) acetone, 23 deg C, 8 h, 2.) CH2Cl2, -40 deg C, 0.5 h; Yield given. Multistep reaction; | ||
Stage #1: Methyl oleate With ozone In methanol; dichloromethane at -17℃; Stage #2: With dimethylsulfane In methanol; dichloromethane at -17℃; | ||
Multi-step reaction with 3 steps 1: formic acid; dihydrogen peroxide / 5 h / 60 °C 2: anhydrous phosphorous acid / water monomer / 3 h / 90 °C 3: sodium (meta)periodate / water monomer; acetonitrile; dichloromethane / 2 h / 20 °C | ||
Multi-step reaction with 4 steps 1: formic acid; dihydrogen peroxide / 5 h / 60 °C 2: anhydrous phosphorous acid / water monomer / 3 h / 90 °C 3: 2.9-dimethyl-1,10-phenanthroline; palladium diacetate; acetic acid / methanol / 1.5 h / 50 °C 4: 3-butyl-4,5-dimethylthiazol-3-ium trifluoromethanesulfonate; potassium carbonate / 0.25 h / 180 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With oxygen; ozone Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | Stage #1: diiodomethane With 2,4,6-Cl3C6H2OZnEt In dichloromethane at -40℃; Stage #2: Methyl oleate In dichloromethane at 20℃; | |
20% | With copper In 1,2-dimethoxyethane at 80 - 90℃; for 4h; Irradiation; ultrasound; | |
Stage #1: Methyl oleate With diethylzinc In hexane; dichloromethane at -5 - 0℃; Stage #2: diiodomethane In hexane; dichloromethane at 20℃; |
With diethylzinc In dichloromethane |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With toluene-4-sulfonic acid | ||
With sodium ethanolate at 25℃; for 1.5h; | ||
With CpLIP2 from Candida parapsilosis In aq. phosphate buffer at 30℃; for 0.25h; Enzymatic reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With iron(III)-acetylacetonate In n-heptane at 105℃; for 22h; Inert atmosphere; | Representative procedure for transesterification reactions catalyzed by Fe(acac)3 in the absence of Na2CO3 General procedure: To a dry 25 mL, bottomed flask equipped with a Dean-Stark trap containing a plug of 4Å molecular sieves (pellets) and topped with a reflux condenser was added of Fe(acac)3 ( 36 mg, 0.10 mmol, 5 mol%) and a solution of methyl bezoate (272 mg, 256 .L, 2.0 mmol), benzyl alcohol (216 mg, 208 .L, 2.0 mmol) and triphenyl methane (488 mg, 2 mmol, as internal standard) in heptane (20 mL). The mixture was heated to reflux (105 ° C) for an indicated time periods. After completion of the reaction as monitored by TLC, 1H NMR and GC, the reaction mixture was cooled to room temperature and the solvent was evaporated. The crude product was purified by column chromatography on silica gel to afforded benzyl benzoate 403 mg, 95% yield. The product obtained was characterized by 1H, 13C NMR, ESI-MS or GC-MS spectroscopic methods. The conversions of the products determined by GC are based on triphenyl methane as an internal standard and are response-corrected based on authentic samples. |
16% | In hexane at 30℃; for 72h; Corynebacterium sp. S-401; | |
With Candida rugosa lipase at 40℃; for 48h; |
With Lipozyme IM at 80℃; for 48h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With oxygen; ozone 1.) methanol; 2.) methanol; Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 42.7% 2: 45.4% | With tungsten(VI) oxychloride; dimethyltitanocene In benzene at 70℃; for 10h; | |
1: 38.6% 2: 43.3% | With tetramethylstannane; tungsten(VI) chloride In benzene at 70℃; for 17h; | |
1: 41% 2: 42% | With tetramethylstannane; tungsten(VI) chloride In benzene at 70℃; for 22h; |
With tetramethylstannane; tungsten(VI) chloride In benzene at 70℃; for 20h; Yield given. Yields of byproduct given; | ||
With [Ru(dmf)3(1,3-dimesitylimidazolin-2-ylidene)(=CH-2-(2-PrO)-C6H4)][(BF4)2] In toluene at 100℃; for 4h; | ||
In hexane at 45℃; for 5h; Inert atmosphere; | Metathesis reaction Metathesis reactions were carried out in small quartz batch reactor containing inert atmosphere. Typically, methyloleate (50 μL) in 500 μL hexane was added to the catalyst (50 mg) in dry conditions at the investigated temperature (45 °C) with stirring at 400 rpm for 5 h. The reaction was then stopped by addition of acetone enabling desorption of the reactants and products from the catalytic surface | |
1: 18 %Chromat. 2: 10 %Chromat. | With tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride In dichloromethane at 50℃; for 1h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
EXAMPLE 1; Step a); The following substances were fed continuously to a CSTR with a working capacity of 80 1, equipped with stirrer and with an adequate temperature regulation system:methyl oleate (technical purity approximately 85%; flow rate 10 kg/h);an aqueous solution of hydrogen peroxide at 60%> (flow rate 2.3 kg/h);- tungstic acid (H2W04) (flow rate 48 g/h).The reaction was conducted at a constant temperature of 62C under vacuum (absolute pressure of 0.10-0.20* 105 Pa) to evaporate the water fed together with the hydrogen peroxide; the evaporated gas was collected and condensed (approximately 1 kg/h of water).FIG. 3 shows the hydrogen peroxide over-all concentration during step a).As can be seen in Fig. 3, the over-all hydrogen peroxide concentration in the reactor was constant at about 1.5 g/kg.The intermediate product containing vicinal diols was continuously discharged from the reactor and fed to step b) by means of a gear pump, adjusted to maintain a constant level in the reactor, with a flow rate of approximately 11.4 kg.; Step b; Step b) was performed in a jet loop reactor with a working capacity of 80 1 equipped with a 3 m3/h recirculation pump and heat exchanger. The intermediate product of step a) was continuously fed with a flow rate of 11.4 kg/h together with:cobalt acetate (Co(CH3COOH)2»4H20, dissolved at 1.5% in an aqueous current(approximately 2 kg/h);- pressurized air (20* 105 Pa; flow rate 12 to 15 kg/h).The air flow rate was adjusted to maintain a constant 02 content (approximately 10%) at the reactor outlet.The reaction was conducted at 60C, keeping constant the reaction volume to 50 1. The reaction time was about 3.5h.The reaction mixture of step b) was continuously discharged from the jet loop reactor and fed to a decanter to separate the oily phase from the aqueous phase. Approximately 13 kg/h of oily product was obtained.; Step (c); The separated oily phase was dried and degassed, and then transferred to a distillation column which allowed fractioning of the monocarboxylic acids, to separate the pelargonic acid from the lighter monocarboxylic acids. The main component of the lighter monocarboxylic acids fraction (byproducts of the oxidative cleavage reaction) was octanoic acid.Approximately 3.8 kg/h of vapor phase containing monocarboxylic acids (raw pelargonic acid), of which 3.5 kg/h are pelargonic acid with a titer of over 99%, was obtained. The 3.8 kg/h current of raw pelargonic acid contained approximately 3.3% of octanoic acid.An organic current of approximately 9 kg/h, containing as major component mono-methyl azelate, together with methyl palmitate, methyl stearate and esters of methyl dihydroxy stearate, was extracted from the bottom of the distillation column.Said organic current was then continuously fed to an emulsifier together with 18 kg/h of water. The emulsion was hydro lyzed by feeding it to three consecutive columns filled with acid ion exchange resin and heated at the temperature of 100C. The total reaction time was 6 h.Each column was provided with a fractionating column on the top, to separate 1.1 kg/h of methanol from water. Approximately 8.5 kg/h of carboxylic acids were obtained from the bottom of the column, of which about 4.3 kg was azelaic acid. | ||
Example 1Comparative ExampleOzonolysis and Oxidation without Addition of Acid20 g of a 0.182 molal solution of methyl oleate (95% pure) in a solvent mixture of propionic acid and water (15 equivalents based on moles of double bond) were initially charged in a two-neck flask with gas inlet tube and reflux condenser. The feed gas, consisting of 5% by volume of oxygen in carbon dioxide was passed through an ozone generator at a flow rate of 40 ml/min. The ozone generator was set to maximum power. The ozone-containing gas mixture was passed into the reaction mixture with stirring. The offgas stream was passed by means of gas wash bottles into a 5% aqueous potassium iodide solution. After 60 minutes, the substrate was converted, and the gas introduction was then stopped. According to GC analysis, the reaction mixture had a content of 39.5 wt % of 9-nonanal and 38.2 wt % of methyl 9-oxononanoate.After adding hydrogen peroxide (0.454 g of a 30% aqueous solution), the reaction mixture was then heated to 100 C. in an oil bath. After 120 minutes, nonanal and methyl 9-oxononanoate were converted completely to the respective carboxyl compounds. GC analysis: 41.05% pelargonic acid, 39.65% monomethyl azelate (FID signal, figure in area percent, uncorrected). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With phosphotungstic acid; dihydrogen peroxide In water at 80℃; chemoselective reaction; | |
92% | With dihydrogen peroxide; magnesium sulfate In <i>tert</i>-butyl alcohol at 25℃; for 24h; | |
85% | With osmium(VIII) oxide; 4-methylmorpholine N-oxide In tetrahydrofuran; water at 20℃; for 2h; | 2 Preparation of Compound 2-A Methyl oleate (10 g, 1 eq) containing a double bond, as a start material, a mixture solvent of tetrahydrofuran (THF) and water (a volume ratio of THF/H2O=3/1) (80 mL), OsO4 (Osmium tetraoxide, 4% in H2O) (21.43 g, 0.1 eq), and NMP (4-Methylmorpholine N-Oxide) (5.12 g, 1.5 eq) were reacted at room temperature for 2 hours. When the reaction was completed, an aqueous NaHCO3 solution (100 mL) was added thereto, and then the organic layer was extracted with ethyl acetate (100 mL× three times), followed by column chromatography, thereby separating and purifying Compound 2-A (9.36 g, yield: 85%).[0039]1H-NMR (400 MHz, CDCl3); δ 3.68 (s, 3H), 3.60 (bs, 2H), 2.30 (t, 2H), 1.83 (t, 2H), 1.62 (t, 2H), 1.51-1.22 (m, 24H), 0.88 (t, 3H)[0040]13C-NMR (100 MHz, CDCl3); δ 174.6, 74.9, 74.8, 34.2, 32.1, 31.4, 31.3, 29.9, 29.8, 29.6, 29.5, 29.4, 29.3, 29.2, 26.3, 26.2, 25.0, 22.8, 14.2 |
85% | With phosphotungstic acid; dihydrogen peroxide at 30 - 60℃; for 4h; | 1-2; 6-8 Example 1 Mix 5.0 g of methyl oleate (85%) and 0.2 g of phosphotungstic acid and stir uniformly, slowly add 6 g of 30% hydrogen peroxide solution dropwise at 30°C, and react at 60°C for about 4 hours after dropping. After the completion of the reaction, the reaction solution was allowed to stand for stratification, and the water layer was separated. The oil layer was washed with water and dried to obtain the target product of 9,10-dihydroxystearate methyl ester, the conversion rate was 91%, and the yield of the target product was 85%. |
Multi-step reaction with 2 steps 1: tris(2,4-pentanedionato)ruthenium(III); Pyridine-2,6-dicarboxylic acid; dihydrogen peroxide / <i>tert</i>-butyl alcohol; water / 16 h / 20 °C / pH 2.9 2: sulfuric acid; water / <i>tert</i>-butyl alcohol / 4 h / 80 °C / pH 2.4 | ||
Multi-step reaction with 2 steps 1: tris(2,4-pentanedionato)ruthenium(III); Pyridine-2,6-dicarboxylic acid; dihydrogen peroxide; water / <i>tert</i>-butyl alcohol / 16 h / 40 °C / pH 2.9 2: sulfuric acid; water / <i>tert</i>-butyl alcohol / 4 h / 80 °C / pH 2.4 | ||
Multi-step reaction with 2 steps 1: tris(2,4-pentanedionato)ruthenium(III); Pyridine-2,6-dicarboxylic acid; dihydrogen peroxide; water / <i>tert</i>-butyl alcohol / 16 h / 80 °C 2: sulfuric acid; water / <i>tert</i>-butyl alcohol / 4 h / 80 °C / pH 2.4 | ||
Multi-step reaction with 2 steps 1: tris(2,4-pentanedionato)ruthenium(III); Pyridine-2,6-dicarboxylic acid; dihydrogen peroxide; water / <i>tert</i>-butyl alcohol / 24 h / 80 °C / pH 2.92 2: sulfuric acid; water / <i>tert</i>-butyl alcohol / 4 h / 80 °C / pH 2.4 | ||
Multi-step reaction with 2 steps 1: tris(2,4-pentanedionato)ruthenium(III); Pyridine-2,6-dicarboxylic acid; dihydrogen peroxide; water / <i>tert</i>-butyl alcohol / 6 h / 80 °C 2: sulfuric acid; water / <i>tert</i>-butyl alcohol / 4 h / 80 °C / pH 2.4 | ||
Multi-step reaction with 2 steps 1: [((S,S)-N,N′-bis(2-pyridylmethyl)-(S,S)-2,2′-bipyrrolidine)FeII(OTf)2]; dihydrogen peroxide / acetic acid; acetonitrile / 2.5 h / 0 °C 2: sulfuric acid / acetic acid; acetonitrile; water / 16 h / 20 °C | ||
Multi-step reaction with 2 steps 1: formic acid; dihydrogen peroxide / 13 h / 35 - 57 °C 2: phosphotungstic acid / water / 0.5 h / 150 °C | ||
Multi-step reaction with 2 steps 1: formic acid; dihydrogen peroxide / 5 h / 60 °C 2: phosphorous acid / water / 3 h / 90 °C | ||
Multi-step reaction with 2 steps 1: 3-chloro-benzenecarboperoxoic acid / dichloromethane / 0 °C 2: perchloric acid / tetrahydrofuran; water / 0 - 20 °C | ||
Multi-step reaction with 2 steps 1: dihydrogen peroxide; formic acid 2: water / Acidic conditions |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With bromine In chloroform | |
With bromine | ||
With bromine at 0℃; |
With bromine In diethyl ether for 0.25h; | ||
With bromine In tetrachloromethane at 0℃; | 2.2.1. General procedure for preparation of dibromoderivative of fatty acid esters (1a-d) General procedure: Fatty acid ester (.1 mol) was dissolved in carbon tetrachlorideand an equimolar amount of bromine (addeddropwise to the reaction mixture) at 0°C. The reactionwas stirred until all the fatty acid ester was used. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With 3-chloro-benzenecarboperoxoic acid In dichloromethane for 12h; | |
99% | With tert.-butylhydroperoxide; [MoO<SUB>3</SUB>(2,2'-bipyridine)] In 1,2-dichloro-ethane at 75℃; for 24h; | |
97% | With formic acid; dihydrogen peroxide at 20℃; |
97% | With formic acid; dihydrogen peroxide | |
96% | With Oxone; edetate disodium; sodium hydrogencarbonate; 1,1-dioxotetrahydrothiopyran-4-one In acetonitrile for 3h; Ambient temperature; | |
96% | With tris(2,4-pentanedionato)ruthenium(III); Pyridine-2,6-dicarboxylic acid; dihydrogen peroxide In acetonitrile at 25℃; for 4h; Autoclave; | |
96% | With formic acid; dihydrogen peroxide In neat (no solvent) at 20 - 30℃; for 8h; Cooling with ice; | |
96% | With formic acid; dihydrogen peroxide at 60℃; for 5h; | |
96% | With formic acid; dihydrogen peroxide | |
95% | With Rf2Bimpy; oxygen; isobutyraldehyde In chlorobenzene; acetone at 40℃; for 1h; | |
93% | With formic acid; dihydrogen peroxide at 0 - 20℃; for 5h; | Epoxidation of Methyl Oleate; The epoxidation reaction was based on a Swern epoxidation19,20 which has been modified for oleochemical use by Bunker and Wool29 and used by our laboratory in the past.32 First, 420.0 g (1.4 mol) of methyl oleate is placed in a heavy duty separatory funnel type 500 mL roundbottom flask equipped with an overhead stirrer. Next, 15 g (0.3 mol) of formic acid was slowly added forming a layered mixture. The reaction flask was cooled in an ice bath and 254 g of 30% hydrogen peroxide (2.2 mol) is added over about 5 min while monitoring the temperature of the solution. The peroxide was added slowly enough such that the temperature of the solution remained below room temperature. Gas bubbles were evident as the hydrogen peroxide was added. The reaction was allowed to proceed at room temperature and alliquots were taken and analyzed by GC. The reaction was judged to be complete after 5 hrs. The product was purified in the reaction flask by stirring with 100 mL of hexanes and discarding the aqueous/formic acid layer. Then, 110 mL of saturated sodium bicarbonate solution was stirred with the hexane layer and removed. This sodium bicarbonate washing was repeated leaving the solution slightly basic. The hexane layer was dried over 80 g of anhydrous sodium sulfate, filtered through a fritted funnel. The hexane was removed with rotary evaporation (60° C.; overnight). Molecular sieves were added to ensure the product remained dry. The isolated yield was 410 g (1.3 mol: 93% yield). |
92% | With dihydrogen peroxide for 0.166667h; Irradiation; | |
92% | With ((4-(methacryloyloxy)phenyl)dimethylsulfonium)4[Mo8O26]; dihydrogen peroxide In methanol at 60℃; for 6h; | |
89% | With Amano A. lipase; 1-n-butyl-3-methylimidazolium tetrafluoroborate; dihydrogen peroxide at 30℃; for 1h; Enzymatic reaction; | |
85% | With dihydrogen peroxide; 3C25H54N(1+)*O24PW4(3-) In water at 60℃; for 5h; Green chemistry; | Cyclooctene and methyl oleate epoxidation. General procedure: In a typical catalytic run, an aqueous hydrogen peroxide solution (30-33%, 18 mmol) was placed into the 20 ml glass thermostated reactor with a magnetic stirrer.Then the catalyst (9 μmol) was added and the resulting solution was stirred for 10 min at room temperature. To initiate the reaction, the substrate (9 mmol for [Sub]/[Cat] ratio of 1000) was carefully added without stirring and then both stirring and heating of the reactor were activated simultaneously. The agitation rate was 1200 rpm. The samples were taken during the reaction at regular intervals without interruption of the stirring using an automatic micropipette. Bi-phasic samples were then diluted with ethyl acetate (190 μl) and analyzed using gas chromatography (GC) |
75% | With tert.-butylhydroperoxide In water; acetonitrile at 70℃; for 24h; | |
50.4% | With peracetic acid In diethyl ether at 20℃; for 20h; | |
24% | With oxygen at 60℃; for 72h; | |
With tert.-butylhydroperoxide at 70℃; for 80h; Yield given; | ||
100 % Spectr. | With 3-chloro-benzenecarboperoxoic acid In chloroform at 19.85℃; for 0.333333h; | |
With dihydrogen peroxide; acetic acid In water; toluene at 70℃; for 9h; | 1.1 Methyl oleate (100 parts) was epoxidized using 30% hydrogen peroxide (54.68 parts), catalyzed by Amberlite IR- 120H (16.85 parts) and acetic acid (10.1 1 parts). Toluene (47.90 parts) was added in order to improve the miscibility between the fatty acid methyl esters and the hydrogen peroxide. The epoxidation was carried out at 70°C for 9 hours. The product was then washed multiple times with water until the pH of the aqueous phase was approximately 7. The epoxidized methyl oleate was dried at 90°C under reduced pressure (<3 Torr). | |
With tert.-butylhydroperoxide In decane | ||
With formic acid; dihydrogen peroxide | ||
With tert.-butylhydroperoxide; titania nanoparticles supported on silica In dichloromethane at 89.84℃; for 24h; Inert atmosphere; | ||
With formic acid; dihydrogen peroxide In water at 0 - 20℃; for 19h; | 3 Example 3 Epoxidation of methyl oleate (EMO); To a stirred solution of methyl oleate (MO) (200.00 g, 675 mmol) and formic acid (62.09 g, 1.35 mol) cooled in an ice bath (0°C), H202 (30.0% in H20, 306.00 mL, 2.70 mol) was added slowly. The reaction was then allowed to proceed at room temperature with vigorous stirring until LC/MS analysis indicated that MO had been consumed (around 19 hr). The reaction was then transferred to a separatory funnel, and ethyl acetate (500 mL) was added and the lower aqueous phase was removed. The organic phase was then washed with water, NaHC03 and brine, dried with Na2S04, filtered, concentrated using a rotary evaporator, and placed under vacuum until constant weight was achieved to yield epoxidized oleic acid (EMO) as a clear light yellow oil (225.0 g). | |
100 %Chromat. | With C18H43Mn2N6O3(2+)*2F6P(1-); dihydrogen peroxide; oxalic acid In water; acetonitrile at 25℃; | |
With dihydrogen peroxide In water at 60℃; for 3h; | ||
74 %Chromat. | With tris(2,4-pentanedionato)ruthenium(III); Pyridine-2,6-dicarboxylic acid; dihydrogen peroxide In water; <i>tert</i>-butyl alcohol at 20℃; for 16h; | |
With 1H-imidazole; sodium periodate In water; acetonitrile at 20℃; for 48h; Molecular sieve; | ||
47 %Chromat. | With oxygen; benzaldehyde at 80℃; for 6h; | 2; 5 Example 2 Example 2 [0115] This example describes the synthesis of functionalized compounds starting from the methyl oleate. Several aldehydic reagents were tested, comprising hexanal, decanal and benzaldehyde. These three tests lead to the formation of the following products, respectively: methyl 9-(hexanoyloxy)-10-hydroxyoctadecanoate and methyl 10-(hexanoyloxy)-9-hydroxyoctadecanoate if hexanal is used; methyl 9-(decanoyloxy)-10-hydroxyoctadecanoate and methyl 10-(decanoyloxy)-9-hydroxyoctadecanoate for decanal; and lastly methyl 9-(benzoyloxy)-10-hydroxyoctadecanoate and methyl 10-(benzoyloxy)-9-hydroxyoctadecanoate when benzaldehyde was used. These three reactions are presented in Diagrams 3, 4 and 5. [0116] The reaction was carried out in a 100 ml glass reactor with mechanical agitation. In all cases, a weight of 25.0 g of methyl ester of sunflower oil HTO (high oleic content-purity: 85% methyl oleate) was placed in the reactor. A quantity of aldehyde was added; the quantity is equivalent to approximately one and one-half the number of moles of methyl oleate used. So, for the hexanal presence test, a quantity equal to 7.1 g of hexanal (purity: 98%-Sigma-Aldrich-ref.: 115606) was placed in the reactor. For decanal, this quantity was equivalent to 11.2 g (purity: 98% 0 Sigma-Aldrich-ref. D7384) and in the case of benzaldehyde, 8.6 g of benzaldehyde (purity: 99%-Sigma-Aldrich-ref.: B 1334) were added. The solid ruthenium on silica catalyst, containing 1.5% by weight of ruthenium, was added to the reaction mix at a ratio of 2% by weight of the quantity of methyl oleate used, i.e. 500 mg. [0117] Then, the medium was heated to 80° C. by a continuous bubbling air flow at atmospheric pressure. The air flow rate was controlled by a ball flow meter and was 30 ml/min. In the case of hexanal and benzaldehyde, after 6 hours of reaction, the air flow rate was stopped and the reaction medium was placed in an inert atmosphere (nitrogen). In the case of decanal, the same operation was carried out after 10 hours of reaction time. In all cases, the time necessary for total conversion of the aldehyde was allotted. Then, the reaction temperature was increased to 150° C. These parameters were maintained for 20 additional hours in the case of hexanal, 15 hours for decanal and 9 hours for benzaldehyde. Samples of the reaction medium were taken at regular intervals in order to determine the progress of the reactions. The composition of the various reaction media after each reaction step is shown in Table 2: [TABLE-US-00002] Function- alized Conversion Conversion products Type of Time to methyl to aldehyde Epoxide yield aldehyde (hours) oleate (%) (%) yield (%) (%) hexanal 6 63 100 47 0 20 76 100 11 10 decanal 10 92 100 45 2 25 95 100 10 7 benz- 6 100 93 56 0 aldehyde 15 100 96 7 17 [0118] The composition of the reaction medium was determined by gas phase chromatographic analysis. The Agilent Technologies 6870N chromatograph used is as described in Example 1. [0119] Two different temperature programs were used. The first was as follows: 50° C. (5 min.)-10° C./min.-100° C. (5 min.)-10° C./min.-150° C. (5 min.)-10° C./min.-220° C. (5 min.)-10° C./min.-250° C. (5 min.). [0120] This program allowed hexanal in particular to be detected. The hold time of the various products under the conditions described above, with a pressure level at the head of the column equal to 16.32 psi were as follows: hexanal (6.9 min.); dodecane (8.1 min.); methyl oleate (30.0 min.); methyl trans-9,10-epoxy-stearate (34.5 min); methyl cis-9,10-epoxy-stearate (34.9 min). [0121] The conversion of the reagents at time t is expressed as described in Example 1. The epoxide yield at time t was calculated as described in Example 1. [0122] The second temperature program for the furnace was as follows: 80° C. (0 min.)-13° C./min.-180° C. (6 min.)-13° C./min.-220° C. (6 min.)-17° C./min.-250° C. (10 min.). The functionalized products were detected upon completion of the analysis. [0123] The hold time for the various products at the conditions described above were as follows: dodecane (2.9 min.); decanal (5.2 min.); benzaldehyde (5.4 min.); methyl oleate (12.6 min.); methyl trans-9,10-epoxy-stearate (18.9 min.); methyl cis-9,10-epoxy-stearate (19.2 min.); methyl 9-(hexanoyloxy)-10-hydroxyoctadecanoate and methyl methyl 10-(hexanoyloxy)-9-hydroxyoctadecanoate (29.8 et 29.9 min.); methyl 9-(decanoyloxy)-10-hydroxyoctadecanoate and methyl 10-(decanoyloxy)-9-hydroxyoctadecanoate (34.4 et 34.5 min.); methyl 9-(benzoyloxy)-10-hydroxyoctadecanoate and methyl 10-(benzoyloxy)-9-hydroxyoctadecanoate (38.7 et 38.9 min.). [0124] Yields of functionalized products were calculated by assigning a response factor equal to one to a surface area of the corresponding chromatographic peaks related to that of the initial methyl oleate. [0125] All functionalized products were identified by gas phase chromatographic analysis coupled with a mass spectrometer as well as steric exclusion chromatograph. |
With [((S,S)-N,N′-bis(2-pyridylmethyl)-(S,S)-2,2′-bipyrrolidine)FeII(OTf)2]; dihydrogen peroxide In acetic acid; acetonitrile at 0℃; for 2.5h; | ||
13 %Chromat. | With plant peroxygenase from tomato (Solanum lycopersicum); dihydrogen peroxide In glycerol at 20℃; for 1h; Enzymatic reaction; | 2.5. Screening of fatty acids as substrates for SlPXG General procedure: Microsomal protein containing SlPXG (50μg) was incubated with 2mmol/l fatty acid (1μmol in 10μl methanol) and 2.5mmol/l H2O2 (1.25μmol) in 500μl sodium acetate buffer (10mmol/l, pH 6, 2% glycerol) for 20 min at 40°C. Three controls were performed with microsomal proteins from empty vector yeast cells, without proteins and without H2O2, respectively. The products were extracted twice with each 500μl CH2Cl2, the organic layer was separated and dried under a stream of nitrogen. For methylation of free carboxyl groups, the pellet was solved in 300μl MeOH, mixed with 150ml trimethylsilyldiazomethane (2mol/l) and incubated for 60min at room temperature. The samples were dried by Speedvac, re-dissolved in 200ml n-hexane and analyzed by Trace GC Ultra gas chromatograph connected to a Trace DSQ mass spectrometer (2.12). Samples containing oleyl alcohol 3a were solved in 60μl MeOH (30%) and analyzed by LC-MS (2.13). The pH optimum was determined by varying the pH values of the reaction in steps of 1 between pH 4 and 6 in sodium acetate buffer (10mmol/l, 2% glycerol) and between 7 and 9 in Tris buffer (10mmol/l, 2% glycerol), whereas 1a and H2O2 served as substrates. The temperature optimum was determined by varying the reaction temperature in steps of 10°C between 0 and 80°C in sodium acetate buffer (10mmol/l, pH 6, 2% glycerol). For determination of saturating curves the substrate concentrations were varied between 0.02 and 2mmol/l in sodium acetate buffer (10mmol/l, pH 6, 2% glycerol) with 50μg microsomal protein containing SlPXG. The values of saturating curves were used for apparent Km value calculation with excel solver (Microsoft). |
With formic acid; dihydrogen peroxide for 5h; Reflux; | ||
With formic acid; dihydrogen peroxide at 30℃; Cooling with ice; | 1 Synthesis of Epoxidized Methyl Oleate (EMO) EMO was synthesized according to prior literature methods (Bunker and Wool, 2002. Synthesis and characterization of monomers and polymers for adhesives from methyl oleate. J. Polym. Sci., Part A: Polym. Chem. 40, 451-458; Doll and Erhan, 2005. Synthesis of carbonated fatty methyl esters using supercritical carbon dioxide. J. Agric. Food Chem. 53, 9608-9614; Findley et al., 1945. Epoxidation of Unsaturated Fatty Materials with Peracetic Acid in Glacial Acetic Acid Solution. J. Am. Chem. Soc. 67, 412-414; Schmits and Wallace, 1954. Epoxidation of Methyl Oleate with Hydrogen Peroxide. J. Amer. Oil Chem. Soc. 31, 363-365). In short, methyl oleate was placed into a roundbottom flask and 4 equivalents of formic acid was added. The reaction was cooled in an ice bath, and 2 equivalents of 30% hydrogen peroxide solution was added dropwise over about 5 minutes with continuous stirring of the solution. The ice bath was removed and the reaction allowed to proceed. The temperature was monitored and the reaction was not allowed to get above 30° C. Reaction progress was monitored by taking aliquots, dissolving in heptane and injecting into the GC-MS. After the reaction was done, 1 volume of heptane was added to help layer the solution with and a separatory funnel was used to remove the acid/peroxide layer. Sodium bicarbonate solution was added, shaken with the product layer, then removed. This was repeated until the solution was no longer acidic as measured by pH paper. A saturated sodium chloride solution was shaken with the product layer, removed, and the product was dried by rotary evaporation and then on a short path drying apparatus. | |
With Isopropylbenzene; oxygen In toluene at 100℃; for 8h; | 2 Experimental CuO/γ-Al2O3 and CuO/PVPy (PVPy=polyvinylpyridine) catalysts, with an 8% metal loading, were prepared by chemisorption-hydrolysis [9]. The support (γ-Al2O3 or PVPy, 10g) was added to a [Cu(NH3)4]2+ solution obtained by the addition of NH4OH to a Cu(NO3)2·H2O water solution (4g in 20ml) until pH9. After 20min under stirring, the slurry, held in an ice bath at 0°C, was slowly diluted in order to allow hydrolysis of the copper complex and deposition of the finely dispersed product to occur. The solid was separated by filtration, washed with 0.5l of water, dried in oven overnight at 120°C. Finally, CuO/Al2O3 was calcined in static in air at 350°C for 4h, while CuO/PVPy was not treated at high temperature, in order to preserve the polymer. (0008) Metal loadings were determined by ICP-OES (ICAP6300 Duo purchased from Thermo Fisher Scientific) and an external calibration methodology, after microwave digestion of fresh and used catalysts in HNO3. (0009) High-resolution transmission electron microscopy (HRTEM) analysis of CuO/PVPy was operated at 200kV with a LIBRA 200FE analytical transmission electron microscope, equipped with FEG source and purchased from Zeiss. Samples were deposited on holey carbon-coated grids from alcohol suspensions. Samples, in the form of powders, were ultrasonically dispersed in isopropyl alcohol, and a drop of the suspension was deposited on a holey carbon film grid (300mesh). Histograms of the metal particle size distribution for the Cu samples were obtained by counting at least 300 particles onto different high resolution micrographs; the mean particle diameter (dm) was calculated by using the formula dm=Σdini/Σni where ni was the number of particles of diameter di. (0010) Reactions were performed at 100°C and under stirring (1250rpm) in a 50ml glass flask provided of a condenser, operating at atmospheric pressure, without the use of radical initiators, by bubbling molecular oxygen (30-35ml/min), in the presence of cumene as both solvent and reactant, and eventually a co-solvent (cumene+co-solvent=20ml, olefin 10 or 5mmol, catalyst 250mg). All the products were analyzed by GC-MS HP-5890 series, equipped with HP5 (5% phenyl)-methyl-polysiloxane capillary column, length 30m (initial temperature=60°C and 3min hold, then 15°C/min to 280°C and 20min hold). Conversion was calculated by using the following equation: C(%)=molMOreactedStartingmolMO100C%=molMOreactedStartingmolMO100, while selectivity was calculated as C(%)=molMOreactedStartingmolMO100.C%=molMOreactedStartingmolMO100. (0011) X-ray powder diffraction patterns were recorded within the range of 10° to 70° 2θ, with a step of 0.02° 2θ and counting time 1 or 4s/step on Philips PW-3020 powder diffractometer Ni-filtered Cu Kα radiation. The peak of CuO (111) at 2θ=35.5° was used for line-broadening determinations. (0012) Copper leaching was measured after a sulfonitric digestion of a sample of 100mg of the reaction mixture, after catalyst filtration at the end of the reaction. | |
With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 0℃; for 3h; | 2.4. Preparation of fatty diol from methyloleate (diol 2) To a solution of methyloleate (17.7 mmol) in 100 mL of dichloromethane, in an erlenmeyer with magnetic stirring at 0 C,were added m-chloroperoxybenzoic acide (m-CPBA, 26.6 mmol).After stirring for 3 h at 0° C, the reaction mixture was washed with water and this aqueous phase was extracted with dichloromethane. All organic phases were washed with warm water and dried(MgSO4). The solvent was evaporated to afford epoxidized methyloleate in 90-95 % yield. To a solution of lithium aluminohydride(1.83 g, 48.1 mmol) in 75 mL of anhydrous diethyl ether, in a two necked round bottom flask with magnetic stirring under nitrogen atmosphere, epoxidized methyl oleate (9.6 mmol) in 50 mL of anhydrous diethyl ether was added. After stirring for 6 h at room temperature, hydrolysis of lithioaluminate complexes was performed by dropwise addition of water. The reaction mixture was washed with saturated aqueous NaCl and dried (MgSO4). The solvent was evaporated to afford the fatty diol in 80-85% yields. 1HNMR (300 MHz, CDCl3,δ /ppm): 0.88 (s, 3H, J 6.72 Hz, CH3);1.24-1.59 (m, 30H, alkyl chain); 3.58 (m, 1H, CH-OH); 3.64 (m, 2H,CH2-OH). 13C NMR (75 MHz, CDCl3,δ /ppm): 13.2, 21.8, 25.3, 26.0,28.4-28.9, 31.0, 32.8, 37.1, 62.2, 71.2. IR (ATR): ν 3338 cm1(s,νOH), disappearance of ester band at 1740 cm-1. | |
With dihydrogen peroxide In acetonitrile at 80℃; for 5h; | 2.3. Methyl oleate epoxidation The catalytic performance of the niobium oxide-based mate-rials was evaluated in methyl oleate epoxidation with hydrogenperoxide as oxidant.Epoxidation reactions were carried out in a round-bottom glassbatch reactor, put in an oil bath, equipped with a condenser andthermometer, and a magnetic bar for vigorous stirring (300 rpm).In a typical experiment, 600 mg of catalyst, 20 cm3of acetonitrile,5 g of methyl oleate (25 mmol) and 6.9 g of hydrogen peroxide54.9 wt% (111 mmol) were used. The temperature was kept con-stant (≈80C) with solvent refluxing. All reagents were added inone pot at the beginning of the reaction. | |
With tert.-butylhydroperoxide; (H3biim)4[β-Mo8O26]; 1-butyl-3-methylimidazolium trifluoromethanesulfonimide at 70℃; for 24h; | 2.3 Catalytic Tests Epoxidation reactions were carried out under autogenous pressure using 5 mL borosilicate reactors equipped with a Teflon valve and a magnetic stirrer. The reactors were charged with an amount of 1 equivalent to 18 lmol Mo, 1.8 mmol of olefin [cis-cyclooctene (Cy) or methyloleate (Ole)] and co-solvent (2 mL organic solvent or 0.3 mL IL), and immersed in an oil bath set at 55 or 70 °C. The organic solvent was CH3CN or α,α,α-trifluorotoluene (TFT), and the IL was 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([bmim]NTf2).The reaction mixtures were stirred at 1000 rpm at the reaction temperature for 10 min prior to addition of the oxidant [2.75 mmol of tert-butylhydroperoxide (TBHP) or H2O2]. This instant was taken as time zero for kinetics tudies.For reactions with TBHP as oxidant, samples were taken periodically, while for reactions with H2O2, individual experiments were performed for a given reaction time. The evolution of the reactions was monitored by gas chromatography using a Varian 3900 GC equipped with a DB-5 capillary column (30 m x 0.25 mm x 0.25 lm) and a FID detector, with H2 as carrier gas. Undecane and methyl decanoate were used as internal standards for Cy and Ole reactions, respectively. The reaction products were identifiedby GC-MS (Trace GC 2000 Series Thermo Quest CE Instruments GC; Thermo Scientific DSQ II) using He as carrier gas. | |
With formic acid; dihydrogen peroxide In water at 20℃; for 14h; Cooling with ice; | ||
With tert.-butylhydroperoxide; [Mo2O6((S)-4-(1-phenylpropyl)-1,2,4-triazole)2]*H2O In decane at 70℃; for 6h; | ||
With 3C41H72N2(2+)*2O24PW4(3-); dihydrogen peroxide In water at 60℃; for 3h; | ||
With tert.-butylhydroperoxide; molybdenum(IV) dioxide In chloroform; chlorobenzene at 60℃; for 6h; | ||
With tert.-butylhydroperoxide In 1,2-dichloro-ethane at 80℃; for 24h; | ||
With dihydrogen peroxide; acetic acid In neat (no solvent) at 50 - 85℃; Ionic liquid; | 2 Embodiment 2 epoxidation under same conditions (feeding ratio and temperature) and sampling analyses at distinct reaction time. Methyl oleate and acetic acid (the molar ratio of methyl oleate to acetic acid=1:0.5) are added into a reaction bottle, mixed with 8% acidic ionic liquids, and agitated and heated to 50° C. 30% hydrogen peroxide solutions (the mole of hydrogen peroxide is 1.5 times as many as that of methyl oleate) are controllably instilled in the reaction bottle within 1 hour and heated to 7085° C. for generation of raw products in 15 hours. The raw products are kept at a standing condition for separation of the aqueous phase and the oil phase. The oil phase in the upper layer is rinsed with sodium bicarbonate solutions and deioned water to derive epoxidized oleates after removal of water. It can be seen from outcomes that both productivity and selectivity of epoxidized oleates in longer reaction time are decreased. As shown in FIG. 2, productivity of epoxidized oleates is 74.5% (reaction temperature: 70° C.; best reaction time: 4 hours) and 84.8% (reaction temperature: 85° C.; best reaction time: 3 hours), respectively. | |
92 %Chromat. | With tert.-butylhydroperoxide; bis(3,5-dimethylanilinium) trimolybdate In decane at 70℃; for 24h; | 2.4. Catalytic tests General procedure: The IPH catalysts were tested for the epoxidation the olefins methyloleate (Ole), methyl linoleate (LinOle), R-(+)-limonene (Lim), and ciscyclooctene(Cy), using tert-butylhydroperoxide (tbhp) as oxidant, andα,α,α-trifluorotoluene (tft) as solvent. Hydrogen peroxide was used (forselected catalytic system) as oxidant instead of tbhp, with acetonitrile(acn) as cosolvent allowing the miscibility of the substrate and oxidant.For the reaction of Ole with tbhp, different cosolvents were tested,namely, 1.2-dichloroethane (dce), toluene (tol), and acn, besides tft.The catalytic reactions were carried out in 10 ml borosilicate reactorsequipped with a Teflon valve (for sampling) and a magnetic stirrer. Thereactor was loaded with catalyst (18 μmol Mo), co-solvent (1 ml) andolefin (1.8 mmol), and then immersed in a temperature-controlled oilbath at 55 or 70 °C, under stirring (1000 rpm), for 10 min. The oxidant(2.75 mmol for Cy, Lim and Ole, and 2.75 mmol or 4.80 mmol forMeOle reactions) was pre-heated in a separate flask for 10 min at thesame temperature, and then added to the reactor. The instant that thepre-heated oxidant was added to the reactor was taken as the initialinstant of the catalytic reaction. The reaction mixtures were analyzedusing a Varian 3900 GC equipped with a DB-5 capillary column(30m×0.25mm×0.25 μm) and a FID detector, with H2 as the carriergas, and quantifications were based on calibrations. The internal standardsused were undecane for the Cy and Lim reactions, and methyldecanoate for the Ole and LinOle reactions. The experimental range oferror was less than 6%, based on replicates carried out for selectedexperimental conditions. The material balance considering all reactionproducts quantified by GC closed in: 100% for Cy at 24 h reaction,100% for Ole at 6 h, 98% for Lime and 98% LinOle at 24 h reaction,70 °C. The reaction products were identified by GC-MS (Trace GC 000Series Thermo Quest CE Instruments GC; Thermo Scientific DSQ II),using He as the carrier gas. The product identifications were based oncommercial mass spectrometry databases (Wiley6, NIST2.0, NISTChemistry WebBook, MAINLIB), and mass spectral matching data. |
With unspecific peroxygenases from Chaetomium globosum; dihydrogen peroxide In acetone at 40℃; for 1h; Enzymatic reaction; | ||
57 %Chromat. | With tert.-butylhydroperoxide; [Mo<SUB>2</SUB>O<SUB>6</SUB>(2,2'-bipyridine)] In decane at 55℃; for 24h; Sealed tube; chemoselective reaction; | |
With formic acid; dihydrogen peroxide at 10℃; for 12h; Inert atmosphere; | 1.3; 2.3; 3.3; 4.3; 5.3; 6.3; 7.3 3) Epoxidation reaction: Take the above 2) Methyl oleate obtained reaction product was 11.86g (0.04 mol)Add to the magnetic stirrer,Condenser tube,A three-neck round bottom flask of nitrogen gas introduction tube was charged with 13.60 g (0.12 mol) of 30% hydrogen peroxide solution and 10.46 g of 88% formic acid according to methyl oleate: hydrogen peroxide: formic acid = 1:3:5 (molar ratio). (0.20 mol),Under a nitrogen atmosphere,The reaction was stirred at 10 ° C for 12 h.The obtained reaction solution was extracted with ethyl acetate.Saturated with sodium bicarbonate solution,Drying over anhydrous sodium sulfate and concentrating in vacuo to give 11.24 g of methyl 9,10-epoxystearate.The purity of the product was determined by gas chromatography to be 93%. | |
With C20H26N4*2CF3O3S(1-)*Mn(2+); dihydrogen peroxide; acetic acid In water; acetonitrile at 20℃; for 1.25h; Green chemistry; | ||
99 %Chromat. | With tert.-butylhydroperoxide In aq. phosphate buffer at 25℃; for 1h; | In the test for peroxygenase activity, defatted oat flour (2 g) or thesuitable enzyme preparation deriving from 2 g of flour was suspendedin 7 mL of 50mM potassium phosphate buffer at pH 7.5. To this suspensionmethyl oleate (13 μL, 11.4 mg, 38 μmol) and t-BuOOH (70 wt%in H2O, 13 μL, 8.5 mg, 95 μmol) were added and the reaction mixturewas maintained under vigorous stirring at 25 °C. The reaction progresswas monitored by GC analysis of aliquots (0.4 mL) of the reaction takenat regular intervals and extracted with MeOH:Et2O 1:9 v/v (0.4 mL);3 μL of the dried organic solution were injected for the GC analyses. |
With formic acid; dihydrogen peroxide In toluene at 0 - 80℃; for 8h; | Synthesis of Epoxy Methyloleate The obtained methyl oleate (MO) was epoxidized with the help of in-situ-generated performic acid using toluene as a solvent (Campanella et al., 2008). A solution of MO (5 g) in toluene (25 mL) was taken in a 25 mL two-neck roundbottomed flask kept at 0 °C. To the above solution, H2O2 (6.20 mL, 202.364 mmol) and formic acid (1.90 mL, 50.59 mmol) were added sequentially as catalyst. Initially, the reaction mixture was stirred at 0 °C as the reaction is exothermic in nature. After 15 min, the reaction mixture was stirred at 80 °C for 8 hours. After completion (as monitored by TLC), the reaction mixture was cooled to room temperature and quenched with 5 % (w/w) NaHCO3 to neutralize the acid. The organic layer (containing EMO) was extracted using ethylacetate (3 × 30 mL) from above biphasic mixture (toluene and water), collected, dried over anhydrous Na2SO4, and concentrated in vacuo; further the obtained residue was purified by flash chromatography (EtOAc/hexane 0.5: 9.5) to afford epoxy methyl oleate (~97% pure) as colorless liquid. [Rf = 0.7, EtOAc/hexane 0.5: 9.5 v/v]. | |
With dihydrogen peroxide at 50℃; for 4h; | Catalytic Oxidation and Product Analysis General procedure: Catalytic experiments were carried out in thermostaticallycontrolled glass vessels with vigorous stirring(500 rpm). Typical conditions for oxidation reactionswere the following: 0.1 M alkene, 0.1-0.2 M H2O2,10 mg of 15 wt % PW4/N-CNT, 1 mL of MeCN, and50°C. The reaction conditions were chosen based onthe results of earlier studies of heterogeneous catalystsbased on PW4 [24, 25]. Reactions started with theaddition of H2O2. The reaction products were identifiedby gas chromatography-mass spectrometry(GC-MS) and 1H NMR spectroscopy and quantitativelydetermined on a gas chromatograph usingbiphenyl as an internal standard | |
With tert.-butylhydroperoxide; MoO3*H2O*C6H6N4 at 70℃; for 24h; | ||
With dihydrogen peroxide; <i>tert</i>-butyl alcohol at 80℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70.6% | With aluminum oxide; C36H44Cl3NORu In toluene at 43℃; for 6h; Inert atmosphere; Autoclave; | 10 General procedure: Ethylene with a purity of 99.995% was used to carry out the ethenolysis reaction. Appropriate ester or mixture of fatty acid esters (15.0 ml, 44.0 mmol) stored over alumina under argon was filtered through a syringe filter (0.2 μm) and degassed with stirring for 30 minutes under high vacuum conditions (p<10-2 mbar). The appropriate amount of the appropriate catalyst (1 ppm, 0.5 ppm, 0.25 ppm or 0.1 ppm) in dry toluene (0.2 ml) was added under argon, where 1 ppm corresponds to 0.000001 molar equivalent of catalyst per 1.0 molar equivalent of an unsaturated fatty acid ester molecule. The mixture was immediately placed in an autoclave equipped with a magnetic stirring device and the atmosphere was changed to ethylene (purging 3 times). Ethylene was introduced into the reactor at a pressure of 11 bar, and then the reactor was placed in an oil bath (on a magnetic stirrer, 700 rpm), and heated to a temperature of 43 °C (the temperature of the reaction mixture measured by a thermocouple inside the reactor was 40 °C). The reaction was carried out for 6 hours with continuous ethylene feed so that its pressure did not drop below 11 bar. After 6 hours the oil bath was removed, the reactor was cooled to room temperature, and the pressure was normalized to atmospheric pressure by removing excess ethylene from the reactor. A sample (about 0.05 ml) of the reaction mixture was collected and diluted with ethyl acetate to 1.5 ml, and a drop of ethyl vinyl ether was added. The solution thus obtained was analyzed using gas chromatography. |
In dichloromethane at 50℃; for 2h; | ||
at 50℃; for 2h; |
1: 18 %Chromat. 2: 19.9 %Chromat. | In toluene at 30℃; for 4h; | Preparation of Olefin Metathesis Product Mixture In a dry box, a solution was prepared of a catalytic ruthenium complex (0.01 M) in toluene, the ruthenium complex being bis (tricyclohexylphosphine) benzylidene ruthenium dichloride (Grubb's catalyst). Methyloleate (Aldrich Company) was degassed with nitrogen and passed through a column of activated alumina prior to use. In a dry box, a reactor was charged with the following reagents: methyloleate (3.50 g, purified as described above), tetradecane (0.50 g, used as an internal standard for gas chromatography analysis), and the catalyst solution (265 microliters, 0.01 M solution). The molar ratio of methyloleate to ruthenium was 4452/1. The reactor was sealed, removed from the dry box, and attached to an ethylene manifold (ethylene, 99.8 percent purity, polymer grade). An olefin metathesis reaction was effected at 60 psig ethylene (413.7 kPa) and 30°C for 4 hours. Aliquot samples were removed from the reactor and analyzed by gas chromatography. An olefin metathesis product mixture was obtained comprising 1-decene (19.9 area percent) and methyl 9- decenoate (18 area percent), and other components including solvent, methyl oleate and homo-metathesis by-products (62.1 area percent). |
In 3-butyl-1,2-dimethylimidazolium bis-triflylamide at 20℃; for 2h; | 1; 2 EXAMPLE 1 Metathesis by Ethenolysis of Methyl Oleate Catalyzed by a Type 3 Complex (FIG. 1) in an Ionic Liquid; 1 ml of 3-butyl-1,2-dimethylimidazolium bis-triflylamide with formula [BMMI]+[N(CF3SO2)2]- pre-dried overnight at 80° C., 148 mg of methyl oleate (source: Fluka, with a purity higher than 98%) and 15 mg of the complex with formula Cl2Ru(CH-o-O-iPrC6H4)PCy3 (synthesized by reacting the 1st generation Grubbs complex with formula Cl2Ru(CHC6H5)(PCy3)2 with 1-isopropoxy-2-vinylbenzene in the presence of CuCl), this corresponding to 5% molar of catalyst with respect to methyl oleate, were introduced, in an inert atmosphere of argon, into an autoclave reactor provided with an agitation system and a pressure sensor. The autoclave was then placed under vacuum and pressurized to obtain a pressure of 10 bars (1 MPa) of ethylene (origin: Alphagas, quality N25). The temperature was kept constant at 20° C. The medium was stirred at ambient temperature for 2 hours, then the excess ethylene was slowly purged by returning to atmosphere pressure at a temperature not exceeding 20° C. and the autoclave was again placed under an atmosphere of argon. The products were separated from the ionic liquid by adding 2 to 3 ml of heptane distilled over CaH2 and degassed. An aliquot (100 μl) of the extracted solution was passed through a short silica column (2 cm) eluted with diethyl ether. It was analyzed by gas phase chromatography (ZB-1 column, 100% dimethylpolysiloxane, 30 metres, helium vector gas 2 ml/min, temperature programming: 60° C. then 5° C./min to 220° C.) coupled to a mass spectrometer. The methyl oleate conversion was 95%. It was calculated using decane as an internal reference. The reaction products were composed of 1-decene (fraction A) and methyl decenoate (fraction B). The presence of 1-decene isomers was not detected. Homo-metathesis products were present in trace amounts and could not be quantified.; EXAMPLE 2 Recycling Ionic Liquid Containing Catalyst After the first cycle carried out in accordance with Example 1, the autoclave containing the ionic liquid and the catalyst was placed under vacuum to eliminate traces of heptane. In an argon atmosphere, 148 mg of methyl oleate was added then the reactor was pressurized to obtain a pressure of 10 bars (1 MPa) of ethylene. The temperature was kept at 20° C. The same procedure as that described in Example 1 was carried out to analyze the products formed. 3 successive cycles were carried out without adding catalyst or ionic liquid. The methyl oleate conversion and the composition of the products formed were determined for each cycle (Table 1 below). | |
With Mo[N(2,6-(i-Pr)2Ph)](CHCMe2Ph)(Me2Pyr)(OBitet) at 20℃; for 15h; Inert atmosphere; | ||
Stage #1: Methyl oleate for 2.08333h; Stage #2: ethene Stage #3: In toluene at 25 - 26℃; for 4.58333h; | 4 Example 4 illustrates on a large scale the purification of a fatty acid ester composition and its subsequent metathesis with ethylene to a reduced chain a-olefin and a reduced chain (x, co-unsaturated ester. A reactor vessel was assembled comprising a 316 stainless steel Pfaulder reactor (50 gallon) fitted with two beaver tail baffles and agitated by an overhead drive with twin 12" diameter, four inclined bladed, stainless steel impellers, ~20"apart, operating at 337 rpm. A methyl oleate feed (Witco brand methyl oleate) was purified by passing it through a stainless steel column [14 inch diameter (35.6 cm) x 8 foot length (2.5 m) ] containing alumina (UOP A2 brand alumina, 12 x 32 mesh). The peroxide concentration of the purified feed was 0.2 meq/kg. The purified feed was fed to the reactor vessel. Using agitation (60-100 rpm), the full reactor (300 lbs, 136.1 kg, 1.1 lb-moles methyl oleate) was sparged with nitrogen gas at atmospheric pressure overnight via a' inch sparge line and vent line. The vent was closed and a vacuum (2.5 psia) (17.2 kPa) was applied for 2 h with the sparge still running. The nitrogen sparge was shut off, and the reactor was evacuated to 1. 5 psia (10. 3 kPa) for 5 min. The vacuum was shut off; the reactor was filled with ethylene and allowed to reach ethylene saturation at 75 psia (517 kPa) under full agitation. Ethylene was fed on demand during the metathesis reaction to maintain a reaction pressure of 74-75 psia (510-517 kPa) ethylene. Three catalyst shot tanks, each containing Grubbs catalyst [bis (tricyclohexylphosphine) benzylidene ruthenium (IV) dichloride] in anhydrous toluene (Aldrich, 1 liter,, 300 ppm by weight water), were prepared in a dry box, and one at a time attached to the reactor catalyst feed port. The secured shot tank was pressurized with nitrogen (80 psia) (552 kPa), and a feed valve was opened to allow the catalyst solution to be blown into the reactor. The feed valve was closed; the empty cylinder removed, and the next full cylinder secured in place. This procedure was repeated for each of the three shot cylinders. About 35 minutes of reaction time elapsed between catalyst additions. The methyl oleate : total catalyst mole ratio was 4,500 : 1. The reaction was agitated for 4 h after the first shot of catalyst with the temperature being maintained at 25-26°C via jacket cooling. At the end of the 4 h reaction time, the product mixture was pumped from the reactor to a tank inerted with nitrogen at atmospheric pressure. A gas chromatographic sample taken of the product mixture indicated a methyl oleate conversion of 39.5 mole percent with a 95 percent selectivity to each of 1-decene and methyl-9-decenoate. The catalyst turnover number was found to be 1,689. | |
In toluene at 50℃; for 2h; autoclave; | 2 In an autoclave of 50 mL, the required quantity of catalyst was introduced as obtained in example 1 (green powder) to obtain a specific concentration of Ru in the medium, which was placed in solution in 1 mL of toluene.1.05 mL (or 3.46 mmol) of methyl oleate in 20 mL of toluene was then added into the autoclave.The reactor was then brought to the desired temperature and pressure at time t=0.Samples were taken over time using a plunger tube to monitor the reaction. Each sample of reaction medium taken in this manner was neutralized using butylvinylether, filtered over a column of celite before being analyzed using gas phase chromatography.The results obtained after variable reaction times under different conditions of concentration, temperature (T) and pressures in ethylene (PC2H2) used are set out in the tables 1 and 2 below, where the abbreviations used have the following meanings: OM: methyl oleate % mol Ru: concentration of ruthenium (reflecting the quantity of catalyst introduced), calculated using the following ratio: % mol Ru=(nRu)/(nOMi)×100 wherein nRu and nOMi refer, respectively, to the quantities, in mole, of Ru and methyl oleate initially present in the reaction medium. PC2H2: pressure of ethylene used in the ethenolysis reaction T: temperature at which the ethenolysis reaction is carried out tR: duration of the ethenolysis reaction COM: conversion of methyl oleate, calculated using the following ratio: COM=(nOMi-nOMf)/(nOMi)×100 where nOMi and nOMf refer, respectively, to the molar quantities of methyl oleate present initially and at the end of the reaction in the reaction medium. Salt: selectivity of the ethenolysis reaction carried out, calculated using the ratio below (the formation of 2 moles of ethenolysis product require one mole of reagent OM): salt=[(n1-decenef+n9-methyl decenoatef)/2]/(nOMi-nOMf)×100 where n1-decenef and n9-methyl decenoatef are, respectively, the molar quantities of 1 -decene and 9-methyl decenoate present in the medium following the reaction, and where nOMi and nOMf have the above-mentioned selectivities. | |
In toluene at 40 - 55℃; | 2 Example 2; Metathesis using complex (12) in the ethenolysis of methyl oleate to 1 -decene and 9-methyldecenoateMethyl oleate (99%) was purchased from Aldrich and passed through a short (2 cm) pad of alumina before use. In a 50 ml_ stainless-steel autoclave fitted with dip-tube for sampling was charged methyl oleate (12 g, 40.0 mmol). EPO Tetradecane (2.5 g, internal standard) was added and the catalyst (12) of example 1 (0.010 mmol) was weighed and transferred into a Schlenk flask under argon. Toluene (5 ml_, degassed) was added to the Schlenk flask and an aliquot (1 ml_) of this stock solution was transferred to the autoclave. The autoclave was pressurized (4-20 bar (400 to 2000 kPa) of ethylene) and heated via computerized temperature controller to the desired temperature. Samples were taken at regular intervals using a dip-tube apparatus, and analyzed by GC with an MDN column.The results below in figure 1 show the productive turonover obtained using catalyst (12) (S/C = 10 000:1) at 10 bar ethylene pressure at various temperatures.Figure 1TON = Turnover number (number of moles of substrate consumed per mole of catalyst employed). Deg = degrees Celsiu | |
In 1,3,5-trimethyl-benzene at 20℃; for 15h; Inert atmosphere; Sealed system; | 1.4 Ethenolysis (employing 99.5% pure ethylene) of methyl oleate (Table 1) initiated by 1a at room temperature yielded essentially only 1-decene (1D) and methyl-9-decenoate (M9D) with a selectivity of >99% and yields up to 95% (entries 1-4). (The other possible products are 1,18-dimethyl-9-octadecenedioate and 9-octadecene.) The highest turnovers are found at the higher pressures (see entries 3 and 4). Without wishing to be bound by theory, all results may be consistent with time dependent catalyst decomposition and a (low) solubility of ethylene in methyl oleate that limits conversion at low pressures. The catalysts shown in entries 5-7 produce product with lower selectivities and yields. An OBitet catalyst that contains the adamantylimido ligand (1b, entry 8) is almost as successful as 1a.; General Ethenolysis Procedure. Ethenolysis reactions were set up under an inert atmosphere in a glovebox: a Fisher-Porter bottle or a high pressure vessel equipped with a stir bar was charged with the appropriate amount of olefin (methyl oleate, cyclooctene, or cyclopentene) and with a mesitylene solution of the olefin metathesis catalyst of the desired concentration and volume. The mesitylene was used as internal standard. The head of the Fisher-Porter bottle equipped with a pressure gauge was adapted on the bottle. The system was sealed and taken out of the glovebox to an ethylene line. The vessel was then pressurized to the desired pressure. The reaction mixture was stirred at room temperature overnight. The reactions were then quenched with 10 uL (microliters) of 2-bromo-benzaldehyde and analyzed by gas chromatography (GC). Benzene was used as solvent for the ethenolysis reactions with 50 and 500 equiv of substrate. All the other runs were performed neat. For each entry, two identical reactions were performed and the data were averaged. | |
1: 55 %Chromat. 2: 55 %Chromat. | In dichloromethane at 55℃; for 6h; | 1 EXAMPLE ; 1This example illustrates the first stage of ethenolysis of methyl oleate according to the process which is a subject matter of the invention. Use is made, for this reaction, of the complex catalyst [RuCl2(CHPh)(IMesH2)(PCy3)], the formula (A) of which is given below. The reaction is carried out in CH2Cl2, at a methyl oleate concentration of 0.05M and an ethylene concentration of 0.2M, at a temperature of 55° C., at atmospheric pressure, for 6 hours, in the presence of the catalyst at a concentration of 5 mol %, with respect to the methyl oleate. The yields are determined by chromatographic analysis. A yield of methyl 9-decenoate CH2CH-(CH2)7-COOCH3 and of 1-decene of 55 mol % can be measured. |
With Hoveyda-Grubbs catalyst first generation In carbonic acid dimethyl ester at 20℃; for 3h; Inert atmosphere; | ||
With dichloro(3-phenyl-1H-inden-1-ylidene)bis(tricyclohexylphosphine)ruthenium(II) In dichloromethane for 6h; Schlenk technique; Inert atmosphere; | ||
With tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride at 30℃; for 24h; High pressure; Overall yield = 51 %Chromat.; | 2.4 Typical procedure for catalytic tests General procedure: In a drybox, a stainless steel reactor was charged with the standard substrate (1g, 3.2mmol of MO) and catalyst (0.1mol% of Ru). Next, the reactor was pressurised with ethylene (constant pressure of 20bar) and the reaction mixture was stirred for 24h at 30°C. Samples were analysed by GC and the reaction products were identified by GC-MS. When biphasic system was employed the reactor was charged also with the IL (0.5g). For reactions with supported catalysts the amount of SILP employed was based on Ru content. | |
With tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride In dichloromethane at 55℃; for 6h; | 1 EXAMPLE 1 EXAMPLE 1 [0083] This example illustrates the first step of ethenolysis of methyl oleate according to the process that is the subject of the invention. For this reaction, the complex catalyst [RuCl2(═CHPh)(IMesH2)(PCy3)] is used, whose formula (A) is given below. The reaction is carried out in CH2Cl2, at a concentration of 0.05 M methyl oleate and 0.2 Methylene, at a temperature of 55° C. and at atmospheric pressure, and for 6 hours, in the presence of the catalyst at a concentration of 5 mol % relative to the methyl oleate. The yields are determined by chromatographic analysis. It is possible to measure a yield of methyl 9-decenoate, CH2═CH-(CH2)7-COOCH3, and of 1-decene of 55 mol %. | |
With C28H39Cl2NORu In toluene at 40℃; for 3h; Sealed tube; Overall yield = 54 %Chromat.; | ||
With tricyclohexylphosphine[4,5-dimethyl-1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene][2-thienylmethylene]ruthenium(II) dichloride at 60℃; for 1h; Microwave irradiation; Sealed tube; | 4.5. Cross-metathesis of methyl oleate To a 10-mL capacity glass microwave tube equipped with aTeflon-coated magnetic stir bar was placed methyl oleate (139 mg,0.47 mmol), C (2 mg, 0.5 mol%), and toluene (1 mL, 0.47 M). Thereaction vessel was placed into the microwave cavity, the gasloadingaccessory connected. The tube was loaded with a pressure of 7 bar of ethene. The reaction mixture was heated to60 °C using an initial microwave power of 100 W and setting apressure cut-off of 250 psi for safety purposes. Once at temperature,the contents of the tube were maintained at 80 °C for 20 min. Aftercompletion of the heating time, the reaction vessel was cooled toroom temperature before releasing the pressure, removing the tubefrom the microwave unit, and transferring the contents to a roundbottomflask. The reaction tube was then rinsed twice with diethylether (2 mL), adding the washings to the round bottom flask. Thesolvents were removed in vacuo by rotary evaporation. The residuewas dissolved in CDCl3 and filtered in to a clean round-bottom flaskthrough a pipet filled with a small volume of Celite. The productmixture was analyzed by GC-MS. | |
With monopodal tungsten oxo catalyst In dichloromethane; pentane at 100℃; for 1h; Glovebox; | 3 In a glove box, S1O2-380 D200 is suspended in dry and degassed pentane (6 mL/g) then under gentle stirring AliBu3 is slowly added (0.782 mmol/g). The reaction is gently stirred in the glove box at RT overnight then the solvent is removed under vacuum. TON (Turn Over Number) = Conversion x (molar ratio = mol of methyl oleate/mol of W or Mo) (0389) Conversion = mol of methyl oleate converted / mol of methyl oleate introduced x 100 Selectivity in ethenolysis = [mol of 1-decene + mol of methyl 9-decenoate] / mol of reaction products x 100. Reaction products comprise 1-decene and methyl 9- decenoate but also products from homometathesis reaction : 9-octadecene and dimethyl 9-octadecene- 1,18-dioate as well as isomerization products of for example 1- decene and methyl 9-decenoate. | |
With C43H59Cl2NORu at 40℃; Overall yield = 68 %; | 2.2.11 2.11 Comparison of CAAC catalysts of this invention with prior art for ethenolysis. Reaction conditions: ethene 10 atm., 99.9% from Matheson) , 40 °C | |
With Hoveyda-Grubbs catalyst first generation In carbon dioxide at 45℃; Supercritical conditions; liquid CO2; | ||
With C33H41Cl2NORu In dichloromethane; toluene at 30℃; for 1h; Glovebox; Inert atmosphere; Overall yield = 87 percentSpectr.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With lithium diisopropyl amide In tetrahydrofuran at -78℃; for 2h; | |
64.1% | Stage #1: Methyl oleate With lithium diisopropyl amide In tetrahydrofuran; octane; n-heptane at -50 - -40℃; for 0.75h; Stage #2: methyl iodide In tetrahydrofuran; octane; n-heptane for 1.5h; | 1 Methyl 2-Methyl Oleate. Methyl oleate (3 gm, 10.13 mmol) in 30 ml dry THF was added dropwise to 2 equivalents of LDA solution (10.13 ml, 20.27 mmol of a 2.0M LDA solution in THF/heptane/ethylhexane) in 6 ml dry THF at (-40)-(-50)°C for 45 min. It is critical that the reaction mixture was kept low during anion formation to avoid cis-trans isomerization of the double bonds. A ten fold excess of the methyl iodide was then added (101.3 mmol, 6.29 ml)rapidly with vigorous stirring and the red mixture immediately turned yellow. The reaction mixture was stirred for 90 min., allowing the bath and the reaction mixture to warm to room temperature and then poured into water and extracted with ether. The ether layers were washed with brine, dried (MgSO4) and the solvent evaporated under reduced pressure. The rude material was chromatographed on silica gel (eluting with 1% ether: petroleum ether) to give 2.0118 g (64.1%) as a yellowish oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
39% | With [1,3-bis(2,4,5-Me3Ph)-2-imidazolidinylidene]Ru=CHPh(PCy3)Cl2 at 45℃; | |
39% | at 45℃; for 72h; Neat (no solvent); | 1 For comparison, we carried out a control experiment with methyl oleate under similar conditions (Entry 1 in Table 1); the self-metathesis of methyl oleate (3a) resulted in an equilibrium distribution of products (50% conversion of 3a) and an isolated yield (39%) of 1,18-dimethyl-9-octadecenedioate (5a) as obtained by silica-gel column chromatography of the crude reaction mixture. The surprisingly significant difference in conversion between oleic acid and methyl oleate was a result of the surprisingly low solubility of diacid 5b in the oleic acid and octadec-9-ene reaction mixture. As self-metathesis of 3b proceeded, diacid 5b precipitated out of the solution and the equilibrium was shifted to the right (FIG. 2, Eq. 1); without being bound by theory, we believe this was because of Le Chatelier's Principle. |
1: 24% 2: 24% | at 20℃; for 96h; |
at 50℃; for 3h; | ||
In dichloromethane for 4h; | ||
at 55℃; for 24h; | ||
In 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)amide; n-heptane at 55℃; for 2h; | 1 EXAMPLE 1 Biphasic Homometathesis of Methyl Oleate in Ionic Liquid; To a glass reaction flask were added (30 mg, 0.036 mmol, 0.004 eq.) benzylidene-bis(tricyclohexylphosphine)dichlororuthenium, (3mL, 8.84 mmol, 1 eq.) methyl oleate, 1 mL 1-butyl-1-methylpyrrolidinium bisttrifluoromethanesulfonyl)amide with formula [BMPyrr] [NTf2], 2 mL heptane and 0.1 mL of dodecane as internal standard. The mixture was biphasic. It was stirred and heated at 55° C. After 2 hours reaction time, a small aliquot of the liquid upper phase was removed for FID GC analysis. GC analysis indicated that the metathesis reaction had proceeded cleanly, yielding 9-octadecene and dimethyloctadecene-1,18-dioate products. Conversion of methyl oleate to these products was 46 wt %. | |
In 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)amide; n-heptane at 20℃; for 2 - 15h; | 2.1; 2.2; 2.3; 2.4 EXAMPLE 2 Recycling Experiments.; To a glass reaction flask were added (50 mg, 0.059 mmol, 0.01 eq,) (1,3-Bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene) dichloro(benzylidene)(tricyclohexylphosphine) ruthenium, (1.5 mL, 4.42 mmol, 1 eq.) methyl oleate, 1 mL 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)amide, 2 mL heptane and 0.1 mL of dodecane as internal standard. The mixture was biphasic. It was stirred at room temperature After 2 hours reaction time, the mixture was decanted. The upper layer was removed and the resulting ionic liquid solution was washed with 2 mL of heptane. A small aliquot of the combined organic liquid was analyzed by GC (entry 1). Fresh methyl oleate (1.5 mL, 4.42 mmol, 1 eq.), 2 mL of heptane and 0.1 mL of dodecane were added to the ionic liquid after each recycle and reaction was allowed to restart at room temperature. GC analysis indicated that the metathesis reaction had proceeded yielding mainly 9-octadecene and dimethyloctadecene-1,18-dioate products. Recycle of the ionic phase was performed 3 times successively without addition of Ru catalyst neither ionic liquid. Conversion of methyl oleate to 9-octadecene and dimethyloctadecene-1,18-dioate products was described in the Table 1. | |
1: 2.76 g 2: 3.75 g | With magnetic nanoparticle-supported second generation of Hoveyda-Grubbs catalyst at 50℃; for 3h; Inert atmosphere; | |
With Zhan catalyst-1B on MCM-41 molecular sieve at 30℃; Inert atmosphere; chemoselective reaction; | ||
With [Ru(=CH(2-C6H4OiPr))Cl2(IMesH2)] immobilized in BMIM*NTf2 on silica gel at 50℃; | ||
at 50℃; for 0.5h; Inert atmosphere; | 2 EXAMPLE 2; This example illustrates the first stage carried out by homometathesis of oleic acid to give the symmetrical diacid of formula HOOC-(CH2)7-CHCH-(CH2), -COOH 9-octa-decenedioic acid.For this stage, use is made of metathesis catalyst obtained from Sigma Aldrich, catalogue reference 569747, corresponding to the following formula benzylidene[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(tricyclohexylphosphine)-ruthenium. This catalyst is known under the name of Grubbs catalyst, second generation, and Hoveyda-Grubbs catalyst, second generation.In the experiment, 2.5 g of fatty acid ester of oleic acid (methyl oleate) are used. Tetradecane is used as internal standard. The reaction mixture is stirred at 50° C. and degassed with argon. The catalyst (1 mol %) is added to the solution, without addition of solvent. The samples of reaction products are analyzed by chromatography. After reacting for half an hour, a conversion of 98 mol % with a homometathesis yield of 100% is obtained. | |
With tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride; ethene at 30℃; for 24h; High pressure; | 2.4 Typical procedure for catalytic tests General procedure: In a drybox, a stainless steel reactor was charged with the standard substrate (1g, 3.2mmol of MO) and catalyst (0.1mol% of Ru). Next, the reactor was pressurised with ethylene (constant pressure of 20bar) and the reaction mixture was stirred for 24h at 30°C. Samples were analysed by GC and the reaction products were identified by GC-MS. When biphasic system was employed the reactor was charged also with the IL (0.5g). For reactions with supported catalysts the amount of SILP employed was based on Ru content. | |
With silica-supported second generation Hoveyda-Grubbs complex In cyclohexane at 29.84℃; Inert atmosphere; | 2.2. Catalytic reactions General procedure: reactionsThe cross-metathesis of methyl oleate (Sigma-Aldrich, 99%)with 1-hexene (Sigma-Aldrich, 99%) was carried out at 303 K and101.3 kPa in a glass batch reactor under Ar atmosphere. Cyclo-hexane (Sigma-Aldrich, anhydrous 99.5%) previously dehydratedwith metallic Na and benzophenone under reflux was used as sol-vent. The reactor was loaded at room temperature with variableamounts of MO, C6 and catalyst together with cyclohexane (10 ml)and n-dodecane (internal standard). Then the reaction mixture was stirred and heated to the reaction temperature in a ther-mostatic bath. Reaction products were analyzed by ex-situ gaschromatography in an Agilent 6850 GC chromatograph equippedwith a flame ionization detector and a 50 m HP-1 capillary col-umn (50 m × 0.32 mm ID, 1.05 m film). Samples from the reactionsystem were collected periodically for 40-250 min. Product iden-tification was carried out using gas chromatography coupled withmass spectrometry (Varian Saturn 2000) a VF5-HT capillary col-umn. Besides the cross-metathesis reaction products (1-DC, 9-TDE,5-TDC and 9-DCE) it was detected the formation of 9-OD and 9-OCT from the self-metathesis of MO, and 5-DC from the self-metathesisof C6. All the product yields were calculated in carbon basis. | |
With [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene][2-[[(2-methylphenyl)imino]methyl]phenolyl][3-phenyl-1H-inden-1-ylidene](chloro)ruthenium(II); Phenyltrichlorosilane In toluene | ||
With titanium(IV) isopropylate; tert-butylhydroquinone In tetrahydrofuran at 100℃; Inert atmosphere; | A Preparation example of a mixture of unsaturated dicarboxylic acids of the invention by metathesis For the metathesis reaction, 50 grams of methyl oleate purified to more than 90%, preferably stabilized with 100 ppm of tert-butylhydroquinone, were heated to a temperature of 100°C under nitrogen. 200ppm (final) of titanium isopropoxide (catalyst activator) are added under stirring. Umicore M73SIMES, ruthenium-based complex catalyst (5ppm final in ΙΟΟμΙ of tetrahydrofuran) is then added. After about 5 minutes of reaction, the theoretical equilibrium (previously determined by gas chromatography) is reached. 2g of activated bentonite are added to the reaction mixture to entrap the catalyst and the catalyst activator. The mixture is then filtered through a cellulose filter to remove the catalyst and enhancer, and the filtrate is recovered. Purification- Fractional distillation is then conducted to separate the two reaction products (9-octadecene and dimethyl octadecenedioate) and the untransformed substrate (methyl oleate). This distillation is done under a vacuum of 1 to lOmbar. Dimethyl octadecenedioate is collected/purified at a temperature between 210°C and 220°C. This fraction has a purity greater than 85% (determined by gas chromatography) . | |
With C61H68Cl2N2Ru In toluene at 55℃; for 1h; Inert atmosphere; Overall yield = 45 %Chromat.; | ||
With C46H44Cl2N3O4Ru In toluene at 50℃; for 1h; Inert atmosphere; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With Dowex 50WX8-100 at 70℃; for 96h; | ||
With CpLIP2 from Candida parapsilosis In aq. phosphate buffer at 30℃; for 0.25h; Enzymatic reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With methanesulfonic acid at 80℃; | |
95% | With SO3H and NH2+ functional carbon-based solid acid at 100℃; for 8h; Sealed tube; | |
With sulfuric acid at 30℃; |
With CaO/mordenite at 50℃; for 0.5h; Inert atmosphere; | ||
92 %Chromat. | With scandium tris(trifluoromethanesulfonate) at 150℃; for 0.333333h; Microwave irradiation; | |
92 %Chromat. | With scandium tris(trifluoromethanesulfonate) at 150℃; for 0.333333h; Microwave irradiation; | |
With 1-hexadecyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide at 60℃; for 12h; Enzymatic reaction; | ||
at 70℃; for 2h; Inert atmosphere; | 1.b b) Oleic acid methyl ester; 300.00 g (338.98 mmol) of high oleic sunflower oil with an oleic acid content of 91.4 % (commercially obtainable from Emery Oleochemicals GmbH) are dried under 1 · 10"3 mbar at 120 °C for 30 minutes, while stirring, cooled and then stirred with 35.79 g (1,118.64 mmol; 3 eq.) of absolute methanol (99.8 %, extra dry, Acros Organics) and with 5.59 g (103.14 mmol) of 30 wt.% strength sodium methanolate solution (pure, 5.4 M in methanol, Acros Organics) at 70 °C under an argon atmosphere for two hours. After cooling to room temperature, the glycerol phase formed is drained off and a further 5.42 g (189.16 mmol) of absolute methanol (99.8 %, extra dry, Acros Organics) are added to the phase which remains, containing oleic acid methyl ester. After stirring at a temperature of 70 °C for one hour, the excess methanol is removed under reduced pressure. After a glycerol phase which has formed again has been separated off, the phase containing oleic acid methyl ester is washed twice with 150 ml of hot doubly distilled water each time. The oleic acid methyl ester is obtained with a purity of 98 % by a fractional vacuum distillation at 160 °C under 1 10"3 mbar. 88.49 g (298.32 mmol; 88 %) of a clear, colourless liquid were obtained. The oleic acid methyl ester is percolated over neutral aluminium oxide (neutral, 50-200 μϖι, Acros Organics) under argon and stored in a refrigerator under an argon atmosphere. | |
With Celite R632-supported NS44035 lipase sol-gel at 40℃; for 6h; Enzymatic reaction; | ||
With divinylbenzene - p-styrene sulfonate copolymer at 65℃; for 16h; | ||
With 5 wtpercent Mg-HT/Al2O3 In butan-1-ol at 60℃; | ||
With hydrotalcite-coated macroporous-mesoporous SBA-15 silica In butan-1-ol at 90℃; | ||
With potassium hydroxide Electrochemical reaction; | ||
With octadecyltrimethylammonium bis((trifluoromethyl)sulfonyl)imide; Novozym 435 (immobilized Candida antarctica lipase B) at 60℃; for 8h; Green chemistry; Enzymatic reaction; | Lipase-catalyzed methyl oleate synthesis in switchable ILs For each IL (i.e. [C12tma][NTf2], [C14tma][NTf2], [C16tma][NTf2], or [C18tma][NTf2]), triolein (0.36, 0.23 or 0.11mmol) was added into three different screw-capped vials (1.0mL total capacity) containing SLIL and methanol (2.18, 1.37 or 0.69mmol). The resulting mixtures at a 1/6 (mol/mol) triolein-methanol ratio gave the following SLIL/triolein/methanol ratios (w/w/w): 16.4/68.7/14.9; 47.7/43.0/9.3; 73.9/21.4/4.7, respectively. For each case, the mixture was previously incubated for 30min at 60°C, resulting in fully clear monophasic liquid systems. The reaction was started by adding Novozym 435 (18% w/w with respect to the amount of triolein) and the reaction mixture was maintained at 60°C for 8h. At selected times, 20μL aliquots were taken and suspended in 480mL of a dodecane/isopropanol (95/5, v/v) solution, and the resulting biphasic mixtures were shaken for 3min, and then centrifuged at 15,000rpm for 10min to extract methyl oleate. Finally, 350mL of dodecane/isopropanol extracts (upper phase) were added to 150mL of a 100mM ethyl decanoate and 100mM tributyrin (internal standards) solution in dodecane/isopropanol (95/5, v/v), and the final solution was analyzed by CG. All experiments were carried out in duplicate. |
Yield | Reaction Conditions | Operation in experiment |
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Multi-step reaction with 2 steps 1: (i) H2, Co(OAc)2, (ii) /BRN= 385737/ 2: (saponification) |
Yield | Reaction Conditions | Operation in experiment |
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Multi-step reaction with 2 steps 1: AlCl3 / Heating 2: CrO3 / acetic acid / 100 °C |
Yield | Reaction Conditions | Operation in experiment |
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Stage #1: trioleoylglycerol; methyl 2-ethylhexanoate at 80℃; for 0.5h; Stage #2: With water for 0.00833333h; | 3 Example 3; General Transesterification Procedure; Short chain fatty acids, in the form of TMP or methyl esters, were transesterified with IMC-130 (Intermountain Canola, Idaho Falls, Id.) using the following procedure. FIG. 2 describes the transesterification of methyl esters (A) and TMP-esters (B) with IMC-130. It should be noted that when the short chain fatty acids were in the form of methyl esters, the long and short chain fatty acid methyl ester byproducts were removed by vacuum distillation after transesterification. Approximately 80 g of IMC-130 were poured into a 250 ml round bottom flask. To prevent deactivation of the catalyst, the oil was heated to 100° C. under high vacuum to remove traces of moisture. Separately, one g of a 30% sodium methoxide solution (in methanol) was placed into a 20 ml scintillation vial and the methanol was evaporated using a stream of nitrogen gas. Care was taken not to overheat the catalyst, since this can result in decomposition and deactivation. The dried sodium methoxide was gently broken up into a fine powder with a metal spatula. Alternatively, powdered sodium methoxide is commercially available. Twenty g of the short chain fatty acid ester (methyl or TMP ester) were added to the reaction flask along with the catalyst. If a TMP ester was being used, the temperature was increased to 100° C. under high vacuum. In the case of methyl esters, which were volatile under these conditions, a temperature of 80° C. with a nitrogen atmosphere was used. After reaching 70°-80° C., the mixture darkened, indicating that transesterification had begun. The reaction was allowed to continue for an additional 30 minutes before being brought back to room temperature. Catalyst was neutralized by adding 5 g of water and stirring rapidly for 30 seconds. Deactivated catalyst and soaps that formed were removed by centrifugation at 7000 rpm for 10 minutes. The oil phase was decanted and washed with 5 g of water for 5 minutes, and then separated using the same centrifugation procedure. Five g of anhydrous magnesium sulfate were added to the oil phase and rapidly stirred for 5 minutes, then removed by vacuum filtration. The trace amount of water that remained was removed by placing the oil in a flask and heating to 60° C. under high vacuum. If methyl esters were used in the transesterification, remaining methyl esters were removed by using a Kugel-Rohr short path distillation unit (Aldrich, Milwaukee, Wis.). The distillation procedure consisted of slowly heating the oil to 200° C. in a hot air bath, maintaining this temperature for 20 minutes, and collecting the fatty acid methyl esters in a distillate trap. |
Yield | Reaction Conditions | Operation in experiment |
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With ozone In dichloromethane at -75 - 0℃; for 0.5 - 2h; | 1; 4 Example 1 Example 1 Methyl soyate (15 g), methanol (60 mL), triethylamine (3 g), and dichloromethane (120 mL) were added to a reaction vessel equipped with a glass tube that was tipped with a fritted glass disk. The reaction mixture was cooled to about -75° C. by immersing the reaction vessel into a dewar surrounded by a dry ice/propanol bath. Ozone was produced by passing oxygen through a Praxair Trailigaz OZOBLOC Model OZC-1001 ozone generator (Cincinnati, Ohio). The concentration of ozone in the feed gas was maintained within the range of 6-10 wt %. The pressure of the generator was operated at about 83 KPa. The exit port of the ozone generator was connected with Tygon tubing to the inlet of the glass tube, and the gaseous oxygen/ozone mixture was delivered to the reaction mixture through the fritted disk at a flow rate of 165 cm3/s. The exhaust outlet was connected to a potassium iodide aqueous solution trap, in which excess ozone was rapidly decomposed. After 30 min. reaction time, the generator was shutdown and the reactor was flushed for 10 min with oxygen to remove excess ozone. The mixture was allowed to warm to room temperature, and dichloromethane was evaporated under a vacuum at 40° C. The solution was transferred to a separatory funnel, triethylamine was neutralized with a 2 M hydrochloric acid aqueous solution and the aqueous layer was discarded. Example 4 Methyl soyate (15 g), methanol (60 mL), and triethylamine (120 g) were added to a reaction vessel equipped with a glass tube that was tipped with a fritted glass disk and the reaction mixture was cooled in an ice/water bath to a constant temperature of 0° C. Ozone was introduced as described in Example 1. Samples were taken after 40, 60, 80, 100 and 120 min. reaction times. Each of these samples was then allowed to warm to room temperature, triethylamine was neutralized with a 2 M hydrochloric acid aqueous solution and the aqueous layer was discarded. Trace unreacted methanol that did not dissolve in the aqueous phase was removed by heating the organic phase under vacuum at 60° C. The oxygenate product mixture was dried over anhydrous calcium sulfate and filtered and characterized by GS-MS and FTIR. The formation of the oxygenated species as a function of reaction time is shown in Table 1: TABLE 1 Concentration of oxygenates as a function of ozonation time Component 0 min 40 min 60 min 80 min 100 min 120 min Dimethyl 0 0.002 0.003 0.004 0.005 0.008 Malonate Methyl 0 0.029 0.031 0.047 0.067 0.104 Hexanoate Methyl 0 0.025 0.027 0.043 0.062 0.099 Nonanoate Dimethyl 0 0.050 0.084 0.100 0.128 0.197 Azelate Methyl 0.924 0.948 1.027 0.937 0.907 1.004 Palmitate Methyl 3.307 1.110 1.107 0.979 0.418 0.186 Linoleate and Methyl Linolenate* Methly Oleate 0.483 0.483 0.480 0.444 0.230 0.130 Methyl Stearate 0.299 0.274 0.316 0.298 0.241 0.298 (*Methyl linoleate and methyl linolenate could not be separated in the GC column) | |
With ozone In dichloromethane at 0℃; for 1.5h; | 3 Example 3; Methyl soyate (50 g), methanol (200 mL) and CaCO3 (20 gr) were added to a reaction vessel equipped with a glass tube that was tipped with a fritted glass disk and the reaction mixture was cooled in an ice/water bath to a constant temperature of 0° C. Ozone was introduced as described in Example 1. After 90 min. reaction time, the generator was shutdown and the reactor was flushed for 10 min. with oxygen to remove excess ozone. The product mixture was allowed to warm to room temperature, triethylamine was neutralized with a 2 M hydrochloric acid aqueous solution and the aqueous layer was discarded. Trace unreacted methanol that did not dissolve in the aqueous phase was removed by heating the organic phase under vacuum at 60° C. The oxygenate product mixture was dried over anhydrous calcium sulfate and filtered. The product mixture was then characterized by GS-MS and FTIR. It was found that the product distribution was similar to that obtained in Example 1. The results further indicated almost complete cleavage of the double bonds and the formation of the desired new metyl esters and diesters. |
Yield | Reaction Conditions | Operation in experiment |
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68% | With sodium methylate; In ethyl acetate-water; benzene; | REFERENCE EXAMPLE 26 Preparation of trans-2-(Oleoylamino)cyclohexylamine Sodium methoxide (0.60 g) was added to a solution of 1.14 g of trans-1,2-diaminocyclohexane and 2.96 g of methyl oleate in 15 ml of benzene, and the mixture was heated under reflux for 20 hours. After completion of the reaction, the solvent was distilled off under reduced pressure and the residue was dissolved in ethyl acetate-water. The organic layer was washed with saturated saline, and dried over anhydrous sodium sulfate. After drying it over anhydrous sodium sulfate, the residue obtained was purified by silica gel column chromatography to obtain 2.54 g of the objective compound (yield: 68%). Property: Oily. Mass Spectrometric Analysis: Molecular formula: C24 H46 N2 O, Calculated: 378.3610, Found: 378.3611. NMR(delta, CDCl3): 0.88 (3H,t,J=7Hz), 1.12-1.48 (24H,m), 1.53-1.79 (4H,m), 1.91 (6H,m), 2.18-2.35 (2H,m), 2.52-2.95 (3H,m), 3.62-3.78 (1H,m), 5.28-5.40 (2H,m), 6.08-6.20 (1H,m). |
68% | With sodium methylate; In ethyl acetate-water; benzene; | Reference Example 26 Preparation of trans-2-(Oleoylamino)cyclohexylamine Sodium methoxide (0.60 g) was added to a solution of 1.14 g of trans-1,2-diaminocyclohexane and 2.96 g of methyl oleate in 15 ml of benzene, and the mixture was heated under reflux for 20 hours. After completion of the reaction, the solvent was distilled off under reduced pressure and the residue was dissolved in ethyl acetate-water. The organic layer was washed with saturated saline, and dried over anhydrous sodium sulfate. After drying it over anhydrous sodium sulfate, the residue obtained was purified by silica gel column chromatography to obtain 2.54 g of the objective compound (yield: 68%). Property: Oily Mass Spectrometric Analysis: Molecular formula: C24H46N2O Calculated: 378.3610 Found: 378.3611 NMR(delta, CDCl3): 0.88 (3H,t,J=7Hz), 1.12-1.48 (24H,m), 1.53-1.79 (4H,m), 1.91 (6H,m), 2.18-2.35 (2H,m), 2.52-2.95 (3H,m), 3.62-3.78 (1H,m), 5.28-5.40 (2H,m), 6.08-6.20 (1H,m) |
65% | REFERENCE EXAMPLE 27 Preparation of (S,S)-2-(Oleoylamino)cyclohexylamine (S,S)-1,2-Diaminocyclohexane (1.14 g) and 2.96 g of methyl oleate were reacted in the same manner as in Reference Example 26 to obtain 2.41 g of the objective compound (yield: 65%) Property: Oily. Mass Spectrometric Analysis: Molecular formula: C24 H46 N2 O, Calculated: 378.3610, Found: 378.3612. NMR(delta, CDCl3): 0.88 (3H,t,J=7Hz), 1.12-1.48 (24H,m), 1.53-1.79 (4H,m), 1.91 (6H,m), 2.18-2.35 (2H,m), 2.52-2.95 (3H,m), 3.62-3.78 (1H,m), 5.28-5.40 (2H,m), 6.08-6.20 (1H,m). |
65% | Reference Example 27 Preparation of (S,S)-2-(Oleoylamino)cyclohexylamine (S,S)-1,2-Diaminocyclohexane (1.14 g) and 2.96 g of methyl oleate were reacted in the same manner as in Reference Example 26 to obtain 2.41 g of the objective compound (yield: 65%) Property: Oily Mass Spectrometric Analysis: Molecular formula: C24H46N2O Calculated: 378.3610 Found: 378.3612 NMR(delta, CDCl3): 0.88 (3H,t,J=7Hz), 1.12-1.48 (24H,m), 1.53-1.79 (4H,m), 1.91 (6H,m), 2.18-2.35 (2H,m), 2.52-2.95 (3H,m), 3.62-3.78 (1H,m), 5.28-5.40 (2H,m), 6.08-6.20 (1H,m) |
Yield | Reaction Conditions | Operation in experiment |
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With potassium hydroxide; at 48 - 52℃; for 4h; | A 500 g quantity of soybean oil was added into temperature- and pressure- controlled water-jacketed reactor 2L all stainless steel pressure Reactor (Parr Instrument Company, Moline, IL, USA). The soybean oil was dried by a negative pressure of 110 mmHg(A) applied by vacuum, and then heating and maintaining the oil at 1000C + 50C under negative pressure while being maintained in a turbulent flow by agitation until there was no trace of bubbling at the oil surface after which, the oil was cooled to 500C + 2C.While the soybean oil was being dewatered, 100 g of absolute methanol (20% w/w of the oil) was added to a stirred vessel and then 5 g of KOH (1% w/w of the oil) was added while the methanol was vigorously agitated until the KOH was completely dissolved. The KOH-methanol mixture was added under vacuum to the 500 g dewatered soybean oil maintained in a turbulent flow by agitation after which, the negative pressure within the reactor was broken with nitrogen gas which was used to flush and then maintain the headspace within the reactor. Addition of the KOH-methanol mixture to the dewatered oil initiated an exothermic esterifcation reaction and therefore, the temperature within the water- jacketed reactor was carefully maintained at 500C + 20C during the reaction period. The esterifcation reaction proceeded for 4 hrs while the oil was maintained in a turbulent flow by agitation. At the end of this time period, agitation was ceased and the methylated soybean oil was transferred to a separation funnel where it was maintained for 18 hrs to allow the reaction mixture to separate into two phases comprising a top layer containing the methyl ester reaction product above a bottom layer containing the reaction by products, i.e., spent methanol and crude glycerol.After the phase separation was complete, the bottom layer containing the reaction by-products was removed from the separation funnel after which, the top methyl ester layer was removed into a separate container. The temperature of the methyl ester product was adjusted to about 75 after which water heated to 95C was added to the methyl ester phase until a ratio of 85 : 10 methyl ester: water was reached. The mixture was then vigorously agitated for 10 min and then EPO <DP n="19"/>centrifuged at 4,200 rpm for 10 min to separate the mixture into 2 phases comprising a top layer containing washed methyl ester reaction product above a bottom layer containing water-soluble by-products removed from the methyl ester reaction product. The top layer containing the washed methyl ester product was decanted and transferred to rotary evaporator flasks wherein any remaining water was removed.After dewatering was completed, the temperature of the methyl ester reaction product was adjusted to 600C +/- 3C after which, 2 % (w/w) TriSyl 615 adsorbent was added to the reaction product and mixed for 15 min to remove any remaining impurities. The adsorbent was removed from the methyl ester reaction product by recycling the methyl esters through a pressure filter apparatus until clarity was achieved. The methyl ester reaction product was then packaged and analyzed.Results: The data in Tables 5 and 6 show that the process of the present invention provided a 100 % conversion of the triglyceride compounds present in soybean oil into methyl esters, the purity of the final methyl ester product was 100%, and the recovery was 88.6 %, i.e., 500 g of soybean oil yielded 443 g of methyl ester product containing 443 g methyl esters. EPO <DP n="20"/>Table 5: Analysis of soybean methyl ester reaction product.Component ConcentrationSoap 0 ppmAcid value 0.04 mg KOH/gKarl Fisher moisture value 74 ppmFree glycerol <0.01 %Total glycerol <0.08 %Total methylated fatty acid content 1,000.0 mg/g productIndividual methylated fatty acidsC 14 - Myristic acid 0.7 mg/g productC16 - Palmitic acid 103.5 mg/g productC16:ln7 - Palmitoleic acid 1.0 mg/g productC 17:0 Margaric acid 1.0 mg/g productC 18 - Steric acid 45.0 mg/g productC18:ln9 - Oleic acid 218.6 mg/g productC 18:1 - Octadecenoic acid 12.7 mg/g productC18:2n6 - Linoleic acid 530.7 mg/g productC18:3n3 - alpha-linoleic acid 75.1 mg/g productC20 - Arachidic acid 3.7 mg/g productC20:ln9 - Eicosenoic acid 2.8 mg/g productC20:2n6 - Eicosadienoic acid - mg/g productC20:3n3 - Mead's acid - mg/g productC22 - Behenic acid 3.4 mg/g productC22: ln9 - Erucic acid - mg/g productC22:2n6 - Docosadienoic acid - mg/g productC21 :5n3 - Heneicosapentaenoic acid - mg/g productC22:4n6 - Docosatetraenoic acid - mg/g productC22:5n6 - Docosapentaenoic acid - mg/g productC24 - Lignoceric acid 0.8 mg/g productC24:ln9 - Nervonic acid - mg/g productOther fatty acids 3.8 mg/g productTable 6: Mass Balance calculation.Input: 500 g soybean oilOutput: 443 g washed and purified soybean methyl ester reaction productPercent recovery: 88.6 % |
Yield | Reaction Conditions | Operation in experiment |
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With potassium hydroxide; at 48 - 52℃; for 4h; | A 500 g quantity of canola oil was added into temperature- and pressure- controlled water-jacketed reactor 2L all Stainless Steel Pressure Reactor (Parr Instrument Company, Moline, IL, USA). The canola oil was dried by a negative pressure of 110 mmHg(A) applied by vacuum, and the oil was dewatered by heating to and maintenance at 1000C + 5C under negative pressure while being maintained in a turbulent flow by agitation until there was no trace of bubbling at the oil surface after which, the oil was cooled to 5O0C + 2C.While the oil was being dewatered, 100 g of absolute methanol (20% w/w of the oil) was added to a stirred vessel and then 5 g of KOH (1% w/w of the oil) was added while the methanol was vigorously agitated until the KOH was completely dissolved. The KOH-methanol mixture was added under vacuum to the 500 g dewatered oil maintained in a turbulent flow by agitation after which, the negative pressure within the reactor was broken with nitrogen gas which was used to flush and then maintain the headspace within the reactor. Addition of the KOH-methanol mixture to the dewatered oil initiated an exothermic esterifcation reaction and therefore, the temperature within the water-jacketed reactor was carefully maintained at 500C + 2C during the reaction period. The esterification reaction proceeded for 4 hrs while the oil was maintained in a turbulent flow by agitation. At the end of this time period, agitation was ceased and the methylated canola oil was transferred to a separation funnel where it was maintained for 18 hrs to allow the reaction mixture to separate into two phases comprising a top layer containing the methyl ester reaction product above a bottom layer containing the reaction by products, i.e., spent methanol and crude glycerol.After the phase separation was complete, the bottom layer containing the reaction by-products was removed from the separation funnel after which, the top methyl ester layer was removed into a separate container. The temperature of the methyl ester product was adjusted to about 75 after which water heated to 95C was added to the methyl ester phase until a ratio of 85: 10 methyl ester.water was reached. The mixture was then vigorously agitated for 10 min and then EPO <DP n="16"/>centrifuged at 4,200 rpm for 10 min to separate the mixture into 2 phases comprising a top layer containing washed methyl ester reaction product above a bottom layer containing water-soluble by-products removed from the methyl ester reaction product. The top layer containing the washed methyl ester product was decanted and transferred to rotary evaporator flasks wherein any remaining water was removed.After dewatering was completed, the temperature of the methyl ester reaction product was adjusted to 6O0C +/- 30C after which, 0.5 2% (w/w) TriSyl 615 adsorbent was added to the reaction product and mixed for 15 min to remove any remaining impurities. The adsorbent was removed from the methyl ester reaction product by recycling the methyl esters through a pressure filter apparatus until clarity was achieved. The methyl ester reaction product was then packaged and analyzed.Results: The data in Tables 3 and 4 show that the process of the present invention provided a 99% conversion of the triglyceride compounds present in canola oil into methyl esters, the purity of the final methyl ester product was 100 %, and the recovery was 85 % i.e., 500 g of canola oil yielded 425 g of methyl ester product containing 421 g methyl esters. EPO <DP n="17"/>Table 3 : Analysis of canola methyl ester reaction product.Component ConcentrationSoap O ppmAcid value 0.03 mg KOH/gKarl Fisher moisture value 65 ppmFree glycerol <0.01 %Total glycerol <0.10 %Total methylated fatty acid content 993.5 mg/g productIndividual methylated fatty acidsC 14 - Myristic acid 0.3 mg/g productCl 6 - Palmitic acid 41.5 mg/g productC16: ln7 - Palmitoleic acid 2.6 mg/g productC 17:0 Margaric acid 1.6 mg/g productC18 - Steric acid 17.0 mg/g productC18: ln9 - Oleic acid 558.7 mg/g productC 18: 1 - Octadecenoic acid 30.1 mg/g productC18:2n6 - Linoleic acid 1 19.6 mg/g productC18:3n3 - alpha-linoleic acid 106.1 mg/g productC20 - Arachidic acid 6.6 mg/g productC20: ln9 - Eicosenoic acid 15.1 mg/g productC20:2n6 - Eicosadienoic acid 0.6 mg/g productC20:3n3 - Mead's acid - mg/g productC22 - Behenic acid 3.6 mg/g productC22:ln9 - Erucic acid 1.4 mg/g productC22:2n6 - Docosadienoic acid - mg/g productC21 :5n3 - Heneicosapentaenoic acid - mg/g productC22:4n6 - Docosatetraenoic acid - mg/g productC22:5n6 - Docosapentaenoic acid - mg/g productC24 - Lignoceric acid 1.2 mg/g productC24: In9 - Nervonic acid 2.0 mg/g productOther fatty acids 5.4 mg/g productTable 4: Mass Balance calculation. Input: 50O g canola oilOutput: 425 g washed and purified canola methyl ester reaction productPercent recovery: 85 % |
Yield | Reaction Conditions | Operation in experiment |
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With potassium hydroxide; at 48 - 52℃; for 4.5h; | A 1 ,700 kg quantity of mustard oil was sprayed with a nozzle pressure of 10.0 + 5.0 psi into a temperature- and pressure-controlled water-jacketed reactor. After the mustard oil was added to the reactor, a negative pressure of 110 mmHg(A) was applied by vacuum, and the oil was dewatered by heating to and maintenance at 1000C + 5C under negative pressure while being maintained in a turbulent flow by agitation until there was no trace of bubbling at the oil surface after which, the oil was cooled to 5O0C +/- 20C.While the oil was being dewatered, 340.0 kg of absolute methanol (20% w/w of the oil) was added to a stirred vessel and then 17.0 kg of KOH (1% w/w of the oil) was added while the methanol was vigorously agitated until the KOH was completely dissolved. The KOH-methanol mixture was added under vacuum to the 1,700 kg of dewatered oil maintained in a turbulent flow by agitation after which, the negative pressure within the reactor was broken with nitrogen gas which was used to flush and then maintain the headspace within the reactor. Addition of the KOH-methanol mixture to the dewatered oil initiated an exothermic esterification reaction and therefore, the temperature within the water- jacketed reactor was carefully maintained at 5O0C + 2C during the reaction period. The esterification reaction proceeded for 4.5 hrs while the oil was maintained in a turbulent flow by agitation. At the end of this time period, agitation was ceased and the methylated mustard oil was maintained in the reactor for 2 hrs to allow the reaction mixture to separate into two phases comprising a top layer containing the methyl ester reaction product above a bottom layer containing the reaction by products, i.e., spent methanol and crude glycerol.After the phase separation was complete, the bottom layer containing the reaction by-products was removed from the reaction vessel after which the temperature of the retained methyl ester product was adjusted to 500C. Then, 500 L of water heated to 95C was added to the methyl ester phase under vacuum after which, the negative pressure was released and the mixture was agitated for 30 min at atmospheric pressure to wash water-soluble impurities out of the methyl ester reaction product after which, agitation was stopped. The mixture was allowed to EPO <DP n="13"/>separate over an 8-hr period into 2 phases comprising a top layer containing washed methyl ester reaction product above a bottom layer containing water- soluble by-products removed from the methyl ester reaction product.After the second phase separation was complete, the bottom layer was removed. A negative pressure of 110 mmHg(A) was then applied by vacuum to the washed methyl ester reaction product remaining in the reactor while the temperature of the reaction product was raised to 95C + 5C under agitation to dewater the washed methyl ester water product. After dewatering was completed, the temperature of the methyl ester reaction product was adjusted to 600C + 3C after which, 2 % (w/w) TriSyl 615 adsorbent (TriSyl is a registered trademark of W.R. Grace & Co.) was added to the reaction product and mixed for 30 min to remove any remaining impurities. The adsorbent was removed from the methyl ester reaction product by recycling the methyl esters through a pressure filter apparatus until clarity was achieved. The methyl ester reaction product was then packaged and analyzed.Results:The data in Table 1 show that the process of the present invention provided a 99% conversion of the triglyceride compounds present in mustard oil into methyl esters, the purity of the final methyl ester product was 98.95%, and the recovery was 91.8%, i.e., 1,700 kg of mustard oil yielded 1,560 kg of methyl ester product containing 1,531 kg methyl esters. The data in Table 2 show that the 91.8% of the starting raw material (i.e., crude mustard oil) was recovered and purified methyl ester reaction product. EPO <DP n="14"/>Table 1; Analysis of mustard methyl ester reaction product.Component ConcentrationSoap O ppmAcid value 0.12 mg KOH/gKarl Fisher moisture value 666 ppmFree glycerol O.001 %Total glycerol <0.01 %Total methylated fatty acid content 989.5 mg/g productIndividual methylated fatty acidsC14 - Myristic acid 0.5 mg/g productCl 6 - Palmitic acid 29.0 mg/g productC16:ln7 - Palmitoleic acid 1.5 mg/g productC17:0 Margaric acid - mg/g productC18 - Steric acid 14.4 mg/g productC18:ln9 - Oleic acid 216.2 mg/g productC 18:1 - Octadecenoic acid 11.1 mg/g productC18:2n6 - Linoleic acid 202.7 mg/g productC18:3n3 - alpha-linoleic acid 110.6 mg/g productC20 - Arachidic acid 8.3 mg/g productC20: ln9 - Eicosenoic acid 1 18.3 mg/g productC20:2n6 - Eicosadienoic acid 9.7 mg/g productC20:3n3 - Mead's acid 1.7 mg/g productC22 - Behenic acid 4.6 mg/g productC22:ln9 - Erucic acid 231.6 mg/g productC22:2n6 - Docosadienoic acid 1.7 mg/g productC21 :5n3 - Heneicosapentaenoic acid 4.2 mg/g productC22:4n6 - Docosatetraenoic acid 1.1 mg/g productC22:5n6 - Docosapentaenoic acid... |
Yield | Reaction Conditions | Operation in experiment |
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90% | With sulfonated carbonized β-cyclodextrin CD-3 at 80℃; for 12h; Autoclave; | Catalytic transesterification of triolein with methanol under high pressure was performed in a 50-mL Teflon-lined autoclave. The reaction mixture of 300 mmol methanol and 10 mmol triolein with 5 wt.% catalyst based on the weight of triolein was reacted at 80 °C for 12 h. Samples for GCanalysis were prepared as described above. |
1: 88% 2: 32% | at 150℃; for 24h; | 9 EXAMPLES 5 to 12; The reaction was carried out in the same manner as in Example 4 except that one of the catalysts C to J was used instead of the catalyst A. The results are shown in Table 1. In the “elution” column, “N.D.” means that the elution level is not higher than 1 ppm. |
1: 87% 2: 49% | With manganese titanate at 200℃; for 24h; Flow reactor; |
1: 80% 2: 56% | at 200℃; for 24h; | 13 EXAMPLES 13 to 16; The reaction was carried out in the same manner as in Example 4 except that the catalyst B, K, L or M was used instead of the catalyst A and that the reaction temperature was changed from 150° C. to 200° C. The results are shown in Table 2. In the “elution” column, “N.D.” means that the elution level is not higher than 1 ppm. |
1: 51% 2: 79% | at 150℃; for 24h; | 4 EXAMPLE 4; A 200 mL autoclave was charged with triolein (60 g), methanol (20 g) and the catalyst A (TiVO4) (2.5 g). After nitrogen replacement, the reaction was allowed to proceed at a reaction temperature of 150° C. for 24 hours with internal stirring. The yield of methyl oleate was 79%, and the yield of glycerine was 51%. XRF analysis was performed and ensured that the total concentration of active metal components Ti and V was not more than 1,000 ppm. Furthermore, when ICP analysis was performed, no elution was observed, that is the vanadium content in the ester phase was not higher than 1 ppm. |
1: 63% 2: 77% | at 150℃; for 24h; | 1 COMPARATIVE EXAMPLE 1; The reaction was carried out in the same manner as in Example 4 except that hydrotalcite was used as the catalyst. The yield of methyl oleate was 77%, and the yield of glycerine was 63%. As a result of XRF analysis of the ester phase, it was revealed that almost the whole amount of magnesium constituting hydrotalcite and about half of the amount of aluminum had been eluted as described in Table 1. |
1: 76% 2: 53% | at 200℃; for 24h; | 14 EXAMPLES 13 to 16; The reaction was carried out in the same manner as in Example 4 except that the catalyst B, K, L or M was used instead of the catalyst A and that the reaction temperature was changed from 150° C. to 200° C. The results are shown in Table 2. In the “elution” column, “N.D.” means that the elution level is not higher than 1 ppm. |
1: 74% 2: 21% | at 200℃; for 24h; | 15 EXAMPLES 13 to 16; The reaction was carried out in the same manner as in Example 4 except that the catalyst B, K, L or M was used instead of the catalyst A and that the reaction temperature was changed from 150° C. to 200° C. The results are shown in Table 2. In the “elution” column, “N.D.” means that the elution level is not higher than 1 ppm. |
1: 66% 2: 20% | at 150℃; for 24h; | 5 EXAMPLES 5 to 12; The reaction was carried out in the same manner as in Example 4 except that one of the catalysts C to J was used instead of the catalyst A. The results are shown in Table 1. In the “elution” column, “N.D.” means that the elution level is not higher than 1 ppm. |
1: 66% 2: 31% | at 150℃; for 24h; | 6 EXAMPLES 5 to 12; The reaction was carried out in the same manner as in Example 4 except that one of the catalysts C to J was used instead of the catalyst A. The results are shown in Table 1. In the “elution” column, “N.D.” means that the elution level is not higher than 1 ppm. |
1: 65% 2: 24% | at 150℃; for 24h; | 7 EXAMPLES 5 to 12; The reaction was carried out in the same manner as in Example 4 except that one of the catalysts C to J was used instead of the catalyst A. The results are shown in Table 1. In the “elution” column, “N.D.” means that the elution level is not higher than 1 ppm. |
1: 50% 2: 18% | at 150℃; for 24h; | 11 EXAMPLES 5 to 12; The reaction was carried out in the same manner as in Example 4 except that one of the catalysts C to J was used instead of the catalyst A. The results are shown in Table 1. In the “elution” column, “N.D.” means that the elution level is not higher than 1 ppm. |
1: 49% 2: 2% | at 150℃; for 24h; | 12 EXAMPLES 5 to 12; The reaction was carried out in the same manner as in Example 4 except that one of the catalysts C to J was used instead of the catalyst A. The results are shown in Table 1. In the “elution” column, “N.D.” means that the elution level is not higher than 1 ppm. |
1: 45% 2: 9% | at 200℃; for 24h; | 16 EXAMPLES 13 to 16; The reaction was carried out in the same manner as in Example 4 except that the catalyst B, K, L or M was used instead of the catalyst A and that the reaction temperature was changed from 150° C. to 200° C. The results are shown in Table 2. In the “elution” column, “N.D.” means that the elution level is not higher than 1 ppm. |
1: 45% 2: 14% | at 150℃; for 24h; | 10 EXAMPLES 5 to 12; The reaction was carried out in the same manner as in Example 4 except that one of the catalysts C to J was used instead of the catalyst A. The results are shown in Table 1. In the “elution” column, “N.D.” means that the elution level is not higher than 1 ppm. |
1: 43% 2: 15% | at 150℃; for 24h; | 8 EXAMPLES 5 to 12; The reaction was carried out in the same manner as in Example 4 except that one of the catalysts C to J was used instead of the catalyst A. The results are shown in Table 1. In the “elution” column, “N.D.” means that the elution level is not higher than 1 ppm. |
98.8 %Chromat. | With hydrogenchloride In water; toluene at 45℃; for 8h; | |
With Amberlyst 15 hydrogen In butan-1-ol at 60℃; | ||
With magnetic mesoporous SiO2/CoFe2O4 nanoparticles supported 1-allyl-dodecylimidazolium hydroxide at 170℃; for 6h; Autoclave; | 2.4 Transesterification procedure The catalytic activities of the catalysts were evaluated using the transesterification of glycerol trioleate (TG) with methanol. 16.10 g of methanol, a 1/30 equimolar amount of TG and the catalyst that contained 0.0278 mmol OH- were added into a 40 mL rotating autoclave and reacted at 170 °C for 6 h. A high performance liquid chromatography (HPLC, Techcomp LC2000) equipped with an ultraviolet photometric detector was used for analyzing the components. A Kromasil 100-5C18 column (4.6 mm × 5 μm × 250 mm) was used and the mobile phase was a mixture of acetone and acetonitrile in the volumetric ratio of 1:1 at a flow rate of 1.0 ml/min. The column temperature was 25 °C and the detection wavelength was 210 nm. The samples were diluted with HPLC grade acetone. The yield of ME (YME) and the selectivities of products (Si, i = 1 (DG), 2 (MG), and 3 (ME)) were calculated according to the equations list as follows: In the equations, nTG,0 is the molar amount of TG before reaction; ni is the molar amount of i; j is the number of ester group in i. | |
With zinc trifluoromethanesulfonate at 165℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
at 55℃; for 1.5h;Product distribution / selectivity; | Freeze-dried tissue samples were uniformly distributed by grinding for 10 -15 sec in a room-temperature coffee bean grinder. Samples of freeze-dried tissue (0.25g), or oils (20 mul) were placed into a 16 x 125 mm screw- cap Pyrex culture tube to which 1.0 ml methyl Cl 3:0 internal standard (0.5mg methyl C13:0/ml methanol) was added. Two ml of sodium methoxide (0.5 M) or 2 ml of boron trifluoride in methanol (14%, wt/vol) were added to the Pyrex tubes containing the samples. The tubes were incubated in a 55 0C water bath for 1.5 h with vigorous 5 sec hand-shaking every 20 min. Two ml of a saturated solution Of NaHCO3 and 3 ml hexane were then added and the tubes were vortex-mixed. After centrifugation, the hexane layer containing the FAME was placed into a GC vial. The vial was capped and placed at -20 C until GC analysis; A comparison was made between the base catylyst sodium methoxide, the acid catylyst boron trifluoride, and direct synthesis, on FAME production from fish oil commercially obtained as a human nutritional supplement. The results are shown in Table 2.Twenty fatty acids were identified in the fish oil sample. Direct FAME synthesis recovered more total amount of fatty acid than did either of the other two methods as would be expected if direct FAME synthesis generated methyl esters of all the fatty acids in the sample. In comparison, base catalysis with sodium methoxide methylated esterified fatty acids, but not free fatty acid anions (Kramer et al., 1997), whereas, acid catalysis by boron trifluoride should have methylated all fatty acids, including esterified, unesterified, and those in salt form (Carrapiso and Garcia, 2000).In analyzing the total fatty acids methylated, direct FAME synthesis converted 22% more fatty acids to FAME than did sodium methoxide and 14% more than did boron trifluoride indicating that there must be groups of fatty acids present that the latter two methods did not recognize. Such limitations with these two reagents have been previously noted (Kramer et al., 1997; Christie, 2003). The direct FAME synthesis method apparently methylates all of the fatty acids present, which explains why the direct FAME synthesis recoveries were higher than the other two methods. When the peak areas were expressed as % of total fatty acid (% FA) present by each method, the % FAs were similar for all three methods even though total recovery among the three methods was somewhat different. This indicates that the fatty acids not methylated by sodium methoxide or boron trifluoride were present in similar ratios for all of the fatty acids present. The results with sodium methoxide, which does not methylate free fatty acid anions, <n="22"/>indicates that because it methylated only 82% of the total fatty acids present the other 18% of the fatty acids present may have been free fatty acid anions. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
at 55℃; for 1.5h;Product distribution / selectivity; | Freeze-dried tissue samples were uniformly distributed by grinding for 10 -15 sec in a room-temperature coffee bean grinder. Samples of freeze-dried tissue (0.25g), or oils (20 mul) were placed into a 16 x 125 mm screw- cap Pyrex culture tube to which 1.0 ml methyl Cl 3:0 internal standard (0.5mg methyl C13:0/ml methanol) was added. Two ml of sodium methoxide (0.5 M) or 2 ml of boron trifluoride in methanol (14%, wt/vol) were added to the Pyrex tubes containing the samples. The tubes were incubated in a 55 0C water bath for 1.5 h with vigorous 5 sec hand-shaking every 20 min. Two ml of a saturated solution Of NaHCO3 and 3 ml hexane were then added and the tubes were vortex-mixed. After centrifugation, the hexane layer containing the FAME was placed into a GC vial. The vial was capped and placed at -20 C until GC analysis; The analysis of freeze-dried beef longissimus muscle fatty acids using sodium methoxide, boron trifluoride and direct FAME synthesis is presented in Table 4. Once again, there were striking differences among the three methods. Direct FAME synthesis recovered more fatty acids than did sodium methoxide and much more than did boron trifluoride. Since most of the fatty acids were esterified in longissimus muscle, as opposed to unesterified in the CLA capsule (Table 3), it was not surprising that sodium methoxide performed much better <n="23"/>in FAME synthesis of this sample, although it methylated only 78% of the fatty acids present. This sample also shows that boron trifluoride performed much better with the free fatty acid anions in the CLA sample (Table 3) than with the esterified fatty acids in muscle tissue. This latter result was surprising since boron trifluoride can methylate all families of fatty acids (Carrapiso and Garcia, 2000). Although boron trifluoride did methylate all of the different fatty acids present, as all of the peaks were identical to direct FAME synthesis, it did not do so quantitatively. It is unclear at this time why boron trifluoride gave such poor results. It can be mentioned that Bolte et al. reports satisfactory FAME synthesis results using boron trifluoride on freeze-dried lamb muscle tissue fatty acids by using much higher temperature and more concentrated effort, i.e., by incubating at 8O0C and vortex-mixing two to three times/min. However, our results do not seem to be due to the fact that boron trifluoride cannot permeate the meat sample, because similar results were observed when using a chloroform :methanol extract according to the method of Folch et al.(1956), where extraction of fatty acids by boron trifluoride would no longer be an issue (data not shown). Apparently, and unexpectedly, there are fatty acid structures in beef longissimus muscle that can be easily methylated by direct synthesis but not by boron trifluoride.When expressed as % FA, sodium methoxide and direct FAME synthesis were quite similar in their results, but boron trifluoride was different, and in this latter case the %FA values were higher when the concentration of fatty acid was lower. This difference could be explained by the fact that boron trifluoride methylated only 46% of the fatty acids present in longissimus muscle, and did so preferentially. With boron trifluoride, long chain unsaturated fatty acids appeared to be methylated more efficiently than short chain or saturated fatty acids, whereas, direct FAME synthesis methylated fatty acids without bias to chain length or structure. As a result, direct FAME synthesis consistently methylated more fatty acid, averaging 1.3 times that of sodium methoxide and 2.2 times that of boron trifluoride. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Samples were uniformly distributed by grinding for 10 -15 sec in a room-temperature coffee bean grinder. Samples could be processed in the state obtained, e.g., wet, dry, freeze- dried, or semi-frozen. Samples (0.5g wet, dry, or semi-frozen sample), (0.25g freeze-dried sample), or oils (20 mul) were placed into a 16 x 125 mm screw-cap Pyrex culture tube to which 1.0 ml Cl 3:0 internal standard (0.5mg C13:0/ml methanol), 0.7 ml 10 N KOH in water, and 5.3 ml methanol was added. The tube was incubated in a 55 C water bath for 1.5 h with vigorous 5 sec hand-shaking every 20 min to properly permeate, dissolve and hydrolyze the sample. After cooling below room temperature in a cold tap water bath, 0.58 ml of 24 N H2SO4 in water was added. (Care is taken in the preparation of the stock solutions IO N KOH and 24 N H2SO4, especially as the H2SO4 solution is extremely exothermic.) The tube was mixed by inversion, and with precipitated K2SO4 present, was incubated again in a 55 C water bath for 1.5 h with 5 sec hand-shaking every 20 min. After FAME synthesis, the tube was cooled in a cold tap water bath. Three ml of hexane was added and the tube was vortex-mixed for 5 min on a multi-tube vortex. The tube was centrifuged for 5 min in a tabletop centrifuge and the hexane layer, containing the FAME, was placed into a gas chromatography (GC) vial. The vial was capped and placed at -20 0C until GC analysis; It is of great interest to know what the limiting concentration of water might be for the direct FAME synthesis method. There has to be such a limit, for no other reason than the fact there has to be a certain concentration of methylating reagents. In Figure 1, we show the effect of water concentration on the direct FAME synthesis method. As the percentage of water was increased, the total amount of fatty acids methylated decreased (data not shown), but this was easily corrected for by the internal standard. Most importantly, the percentage of each fatty acid remained constant up to 33% water. Only above 33% water do the FAME production results become problematic. In comparison, our reagents, without any sample present, constitute only 13% water in a final reaction volume of 7.58 ml. Thus, from a practical standpoint, one can replace 1.5 ml of MeOH with a 1.5 ml aqueous sample for a <n="25"/>final concentration of 33% water. For example, using the protocol as given, 1.5 ml of milk can be analyzed directly by our method. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Samples were uniformly distributed by grinding for 10 -15 sec in a room-temperature coffee bean grinder. Samples could be processed in the state obtained, e.g., wet, dry, freeze- dried, or semi-frozen. Samples (0.5g wet, dry, or semi-frozen sample), (0.25g freeze-dried sample), or oils (20 mul) were placed into a 16 x 125 mm screw-cap Pyrex culture tube to which 1.0 ml Cl 3:0 internal standard (0.5mg C13:0/ml methanol), 0.7 ml 10 N KOH in water, and 5.3 ml methanol was added. The tube was incubated in a 55 C water bath for 1.5 h with vigorous 5 sec hand-shaking every 20 min to properly permeate, dissolve and hydrolyze the sample. After cooling below room temperature in a cold tap water bath, 0.58 ml of 24 N H2SO4 in water was added. (Care is taken in the preparation of the stock solutions IO N KOH and 24 N H2SO4, especially as the H2SO4 solution is extremely exothermic.) The tube was mixed by inversion, and with precipitated K2SO4 present, was incubated again in a 55 C water bath for 1.5 h with 5 sec hand-shaking every 20 min. After FAME synthesis, the tube was cooled in a cold tap water bath. Three ml of hexane was added and the tube was vortex-mixed for 5 min on a multi-tube vortex. The tube was centrifuged for 5 min in a tabletop centrifuge and the hexane layer, containing the FAME, was placed into a gas chromatography (GC) vial. The vial was capped and placed at -20 0C until GC analysis; A comparison was made between the base catylyst sodium methoxide, the acid catylyst boron trifluoride, and direct synthesis, on FAME production from fish oil commercially obtained as a human nutritional supplement. The results are shown in Table 2.Twenty fatty acids were identified in the fish oil sample. Direct FAME synthesis recovered more total amount of fatty acid than did either of the other two methods as would be expected if direct FAME synthesis generated methyl esters of all the fatty acids in the sample. In comparison, base catalysis with sodium methoxide methylated esterified fatty acids, but not free fatty acid anions (Kramer et al., 1997), whereas, acid catalysis by boron trifluoride should have methylated all fatty acids, including esterified, unesterified, and those in salt form (Carrapiso and Garcia, 2000).In analyzing the total fatty acids methylated, direct FAME synthesis converted 22% more fatty acids to FAME than did sodium methoxide and 14% more than did boron trifluoride indicating that there must be groups of fatty acids present that the latter two methods did not recognize. Such limitations with these two reagents have been previously noted (Kramer et al., 1997; Christie, 2003). The direct FAME synthesis method apparently methylates all of the fatty acids present, which explains why the direct FAME synthesis recoveries were higher than the other two methods. When the peak areas were expressed as % of total fatty acid (% FA) present by each method, the % FAs were similar for all three methods even though total recovery among the three methods was somewhat different. This indicates that the fatty acids not methylated by sodium methoxide or boron trifluoride were present in similar ratios for all of the fatty acids present. The results with sodium methoxide, which does not methylate free fatty acid anions, <n="22"/>indicates that because it methylated only 82% of the total fatty acids present the other 18% of the fatty acids present may have been free fatty acid anions. | ||
Freeze-dried tissue samples were uniformly distributed by grinding for 10 -15 sec in a room-temperature coffee bean grinder. Samples of freeze-dried tissue (0.25g), or oils (20 mul) were placed into a 16 x 125 mm screw- cap Pyrex culture tube to which 1.0 ml methyl Cl 3:0 internal standard (0.5mg methyl C13:0/ml methanol) was added. Two ml of sodium methoxide (0.5 M) or 2 ml of boron trifluoride in methanol (14%, wt/vol) were added to the Pyrex tubes containing the samples. The tubes were incubated in a 55 0C water bath for 1.5 h with vigorous 5 sec hand-shaking every 20 min. Two ml of a saturated solution Of NaHCO3 and 3 ml hexane were then added and the tubes were vortex-mixed. After centrifugation, the hexane layer containing the FAME was placed into a GC vial. The vial was capped and placed at -20 C until GC analysis; A comparison was made between the base catylyst sodium methoxide, the acid catylyst boron trifluoride, and direct synthesis, on FAME production from fish oil commercially obtained as a human nutritional supplement. The results are shown in Table 2.Twenty fatty acids were identified in the fish oil sample. Direct FAME synthesis recovered more total amount of fatty acid than did either of the other two methods as would be expected if direct FAME synthesis generated methyl esters of all the fatty acids in the sample. In comparison, base catalysis with sodium methoxide methylated esterified fatty acids, but not free fatty acid anions (Kramer et al., 1997), whereas, acid catalysis by boron trifluoride should have methylated all fatty acids, including esterified, unesterified, and those in salt form (Carrapiso and Garcia, 2000).In analyzing the total fatty acids methylated, direct FAME synthesis converted 22% more fatty acids to FAME than did sodium methoxide and 14% more than did boron trifluoride indicating that there must be groups of fatty acids present that the latter two methods did not recognize. Such limitations with these two reagents have been previously noted (Kramer et al., 1997; Christie, 2003). The direct FAME synthesis method apparently methylates all of the fatty acids present, which explains why the direct FAME synthesis recoveries were higher than the other two methods. When the peak areas were expressed as % of total fatty acid (% FA) present by each method, the % FAs were similar for all three methods even though total recovery among the three methods was somewhat different. This indicates that the fatty acids not methylated by sodium methoxide or boron trifluoride were present in similar ratios for all of the fatty acids present. The results with sodium methoxide, which does not methylate free fatty acid anions, <n="22"/>indicates that because it methylated only 82% of the total fatty acids present the other 18% of the fatty acids present may have been free fatty acid anions. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Samples were uniformly distributed by grinding for 10 -15 sec in a room-temperature coffee bean grinder. Samples could be processed in the state obtained, e.g., wet, dry, freeze- dried, or semi-frozen. Samples (0.5g wet, dry, or semi-frozen sample), (0.25g freeze-dried sample), or oils (20 mul) were placed into a 16 x 125 mm screw-cap Pyrex culture tube to which 1.0 ml Cl 3:0 internal standard (0.5mg C13:0/ml methanol), 0.7 ml 10 N KOH in water, and 5.3 ml methanol was added. The tube was incubated in a 55 C water bath for 1.5 h with vigorous 5 sec hand-shaking every 20 min to properly permeate, dissolve and hydrolyze the sample. After cooling below room temperature in a cold tap water bath, 0.58 ml of 24 N H2SO4 in water was added. (Care is taken in the preparation of the stock solutions IO N KOH and 24 N H2SO4, especially as the H2SO4 solution is extremely exothermic.) The tube was mixed by inversion, and with precipitated K2SO4 present, was incubated again in a 55 C water bath for 1.5 h with 5 sec hand-shaking every 20 min. After FAME synthesis, the tube was cooled in a cold tap water bath. Three ml of hexane was added and the tube was vortex-mixed for 5 min on a multi-tube vortex. The tube was centrifuged for 5 min in a tabletop centrifuge and the hexane layer, containing the FAME, was placed into a gas chromatography (GC) vial. The vial was capped and placed at -20 0C until GC analysis; The analysis of freeze-dried beef longissimus muscle fatty acids using sodium methoxide, boron trifluoride and direct FAME synthesis is presented in Table 4. Once again, there were striking differences among the three methods. Direct FAME synthesis recovered more fatty acids than did sodium methoxide and much more than did boron trifluoride. Since most of the fatty acids were esterified in longissimus muscle, as opposed to unesterified in the CLA capsule (Table 3), it was not surprising that sodium methoxide performed much better <n="23"/>in FAME synthesis of this sample, although it methylated only 78% of the fatty acids present. This sample also shows that boron trifluoride performed much better with the free fatty acid anions in the CLA sample (Table 3) than with the esterified fatty acids in muscle tissue. This latter result was surprising since boron trifluoride can methylate all families of fatty acids (Carrapiso and Garcia, 2000). Although boron trifluoride did methylate all of the different fatty acids present, as all of the peaks were identical to direct FAME synthesis, it did not do so quantitatively. It is unclear at this time why boron trifluoride gave such poor results. It can be mentioned that Bolte et al. reports satisfactory FAME synthesis results using boron trifluoride on freeze-dried lamb muscle tissue fatty acids by using much higher temperature and more concentrated effort, i.e., by incubating at 8O0C and vortex-mixing two to three times/min. However, our results do not seem to be due to the fact that boron trifluoride cannot permeate the meat sample, because similar results were observed when using a chloroform :methanol extract according to the method of Folch et al.(1956), where extraction of fatty acids by boron trifluoride would no longer be an issue (data not shown). Apparently, and unexpectedly, there are fatty acid structures in beef longissimus muscle that can be easily methylated by direct synthesis but not by boron trifluoride.When expressed as % FA, sodium methoxide and direct FAME synthesis were quite similar in their results, but boron trifluoride was different, and in this latter case the %FA values were higher when the concentration of fatty acid was lower. This difference could be explained by the fact that boron trifluoride methylated only 46% of the fatty acids present in longissimus muscle, and did so preferentially. With boron trifluoride, long chain unsaturated fatty acids appeared to be methylated more efficiently than short chain or saturated fatty acids, whereas, direct FAME synthesis methylated fatty acids without bias to chain length or structure. As a result, direct FAME synthesis consistently methylated more fatty acid, averaging 1.3 times that of sodium methoxide and 2.2 times that of boron trifluoride. | ||
Freeze-dried tissue samples were uniformly distributed by grinding for 10 -15 sec in a room-temperature coffee bean grinder. Samples of freeze-dried tissue (0.25g), or oils (20 mul) were placed into a 16 x 125 mm screw- cap Pyrex culture tube to which 1.0 ml methyl Cl 3:0 internal standard (0.5mg methyl C13:0/ml methanol) was added. Two ml of sodium methoxide (0.5 M) or 2 ml of boron trifluoride in methanol (14%, wt/vol) were added to the Pyrex tubes containing the samples. The tubes were incubated in a 55 0C water bath for 1.5 h with vigorous 5 sec hand-shaking every 20 min. Two ml of a saturated solution Of NaHCO3 and 3 ml hexane were then added and the tubes were vortex-mixed. After centrifugation, the hexane layer containing the FAME was placed into a GC vial. The vial was capped and placed at -20 C until GC analysis; The analysis of freeze-dried beef longissimus muscle fatty acids using sodium methoxide, boron trifluoride and direct FAME synthesis is presented in Table 4. Once again, there were striking differences among the three methods. Direct FAME synthesis recovered more fatty acids than did sodium methoxide and much more than did boron trifluoride. Since most of the fatty acids were esterified in longissimus muscle, as opposed to unesterified in the CLA capsule (Table 3), it was not surprising that sodium methoxide performed much better <n="23"/>in FAME synthesis of this sample, although it methylated only 78% of the fatty acids present. This sample also shows that boron trifluoride performed much better with the free fatty acid anions in the CLA sample (Table 3) than with the esterified fatty acids in muscle tissue. This latter result was surprising since boron trifluoride can methylate all families of fatty acids (Carrapiso and Garcia, 2000). Although boron trifluoride did methylate all of the different fatty acids present, as all of the peaks were identical to direct FAME synthesis, it did not do so quantitatively. It is unclear at this time why boron trifluoride gave such poor results. It can be mentioned that Bolte et al. reports satisfactory FAME synthesis results using boron trifluoride on freeze-dried lamb muscle tissue fatty acids by using much higher temperature and more concentrated effort, i.e., by incubating at 8O0C and vortex-mixing two to three times/min. However, our results do not seem to be due to the fact that boron trifluoride cannot permeate the meat sample, because similar results were observed when using a chloroform :methanol extract according to the method of Folch et al.(1956), where extraction of fatty acids by boron trifluoride would no longer be an issue (data not shown). Apparently, and unexpectedly, there are fatty acid structures in beef longissimus muscle that can be easily methylated by direct synthesis but not by boron trifluoride.When expressed as % FA, sodium methoxide and direct FAME synthesis were quite similar in their results, but boron trifluoride was different, and in this latter case the %FA values were higher when the concentration of fatty acid was lower. This difference could be explained by the fact that boron trifluoride methylated only 46% of the fatty acids present in longissimus muscle, and did so preferentially. With boron trifluoride, long chain unsaturated fatty acids appeared to be methylated more efficiently than short chain or saturated fatty acids, whereas, direct FAME synthesis methylated fatty acids without bias to chain length or structure. As a result, direct FAME synthesis consistently methylated more fatty acid, averaging 1.3 times that of sodium methoxide and 2.2 times that of boron trifluoride. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | Stage #1: Methyl oleate With tetraethylammonium iodide In toluene at 20℃; for 1h; Inert atmosphere; Glovebox; Stage #2: ethene With C50H59Br2Cl2N3O2SiW In toluene; benzene at 50℃; for 18h; Autoclave; Inert atmosphere; | 10 Compounds according to the invention were tested in ethenolysis of methyl oleate.The substrate was purified using triethylaluminum (TEAI) according to methods known from WO 2014/139679 (XiMo). Methyl oleate was mixed with 700 ppmwt TEAI and the mixture was stirred at room temperature for 4 hours.In a nitrogen gas filled glovebox, fatty acid methyl ester was measured into 30 mL glass vials and mixed with the stock solution of triethylaluminum (23 %wt in toluene). The optimal triethylaluminum amount was determined previously and was found to be 700ppm. Mixtures were stirred at r.t. for 1 hour. Catalysts were added as a stock solution (0.01 M in benzene) The vial was placed into a stainless steel autoclave equipped with an alublock and was stirred at 50°C under 10 atm of ethylene gas overpressure for 18 hours. Five reactions were performed in the same autoclave with common gas space. The excess of ethylene was let out. From the reaction mixture 2.0 pi was taken out and diluted to 1.5 ml with n-pentane and analyzed by GCMS-FID, (Shimadzu 2010 Plus, column: Zebron ZB-35FIT INFERNO, 30 m x 0.25 mm x 0.25 pm.reaction with 12-rac was prepared in 250 ml_ scale as the catalyst was portioned to it as a powder due to its insolubilityQuantification of the liquid phase by GC indicated the conversion given in Table 3 below:Under comparable conditions, the ethenolysis of methyl oleate using the Mo analog of compound 4 resulted in a yield of 9-DAME of around 30 % and a total conversion of around 40 % |
In dichloromethane at 40℃; for 4h; | 1 Ethenolyses of olefinic substrates were set up under an inert atmosphere in a glove box. As an example reaction procedure, a Fisher-Porter bottle equipped with a stir bar was charged with methyl oleate (> 99%) from Nu-Check-Prep (Elysian, MN) (15.0 g; 50.6 mmol). A solution of olefin metathesis catalyst of an appropriate concentration was prepared in anhydrous dichloromethane (from Aldrich) and the desired volume of this solution added to the methyl oleate. The head of the Fisher-Porter bottle was equipped with a pressure gauge and a dip-tube was adapted on the bottle. The system was sealed and taken out of the glove box to an ethylene line. The vessel was then purged 3 times with ethylene (Polymer purity 99.9 % from Matheson Tri Gas), pressurized to the indicated pressure and placed in an oil bath at the indicated temperature. The reaction was monitored by collecting samples into vials at different reaction times via the dip-tube. Immediately after collecting a sample, the reaction was stopped by adding 1 mL of a 1.0 M isopropanol solution of tris-hydroxymethylphopshine (THMP) to the vial. The samples were then heated for at least 1 hour at 6O0C, diluted with 1 mL of distilled water, extracted with 1 mL of hexanes and analyzed by gas chromatography (GC). If the olefinic substrate is a glyceride, it is transesterified prior to GC analysis using a method similar to the transesterification of metathesized SBO described below. Different triglycerides and fatty acid methyl esters (FAMEs) were subjected to the ethenolysis procedure (vide supra). Methyl oleate (MO), > 99% was obtained from Nu- Check-Prep (Elysian, MN). Soybean oil (SBO), salad-grade (i.e., refined, bleached, deodorized) was obtained from Cargill. Soy FAME, not distilled and canola FAME, distilled were obtained from Cognis. All oils were degassed by sparging with argon for 1 hour/L prior to being stored over activated alumina in a glove box under an argon atmosphere. The results are provided in Table 2. | |
In dichloromethane at 40 - 60℃; for 2 - 4h; | 1 Ethenolyses of olefinic substrates were set up under an inert atmosphere in a glove box. As an example reaction procedure, a Fisher-Porter bottle equipped with a stir bar was charged with methyl oleate (> 99%) from Nu-Check-Prep (Elysian, MN) (15.0 g; 50.6 mmol). A solution of olefin metathesis catalyst of an appropriate concentration was prepared in anhydrous dichloromethane (from Aldrich) and the desired volume of this solution added to the methyl oleate. The head of the Fisher-Porter bottle was equipped with a pressure gauge and a dip-tube was adapted on the bottle. The system was sealed and taken out of the glove box to an ethylene line. The vessel was then purged 3 times with ethylene (Polymer purity 99.9 % from Matheson Tri Gas), pressurized to the indicated pressure and placed in an oil bath at the indicated temperature. The reaction was monitored by collecting samples into vials at different reaction times via the dip-tube. Immediately after collecting a sample, the reaction was stopped by adding 1 mL of a 1.0 M isopropanol solution of tris-hydroxymethylphopshine (THMP) to the vial. The samples were then heated for at least 1 hour at 6O0C, diluted with 1 mL of distilled water, extracted with 1 mL of hexanes and analyzed by gas chromatography (GC). If the olefinic substrate is a glyceride, it is transesterified prior to GC analysis using a method similar to the transesterification of metathesized SBO described below. Different triglycerides and fatty acid methyl esters (FAMEs) were subjected to the ethenolysis procedure (vide supra). Methyl oleate (MO), > 99% was obtained from Nu- Check-Prep (Elysian, MN). Soybean oil (SBO), salad-grade (i.e., refined, bleached, deodorized) was obtained from Cargill. Soy FAME, not distilled and canola FAME, distilled were obtained from Cognis. All oils were degassed by sparging with argon for 1 hour/L prior to being stored over activated alumina in a glove box under an argon atmosphere. The results are provided in Table 2. |
Yield | Reaction Conditions | Operation in experiment |
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62% | (Example 5) Synthesis of 9Z-N-[2-(1-methylpyrrolidin-2-yl)ethyl]oleamide (Compound 5) toluene (18 ml), dried using MS 4A, was mixed with 12.3 ml of a n-hexane solution of 15% Me3Al. With the mixture being cooled in an ice-methanol bath, 2.42 ml (16.7 mmols) of 2-(2-aminoethyl)-1-methylpyrrolidine was added dropwise over about 5 minutes.. The 2-(2-aminoethyl)-1-methylpyrrolidine was finally washed using 2 ml of toluene.. After stirring for 20 minutes, the temperature was raised to room temperature, and 7 ml of a toluene solution of 5.0 g (16.9 mmols) of oleic acid methyl ester was added dropwise over 2 minutes.. After stirring for 2.5 hours at 70C, the mixture was cooled with ice, and 30 ml of 0.67N hydrochloric acid was added dropwise.. An aqueous solution of 1N NaOH (about 100 ml) was added, and the mixture was extracted with about 100 ml of ethyl acetate.. At this time, the PH of the aqueous layer was 9 to 10.. The organic layer was washed twice with 20 ml of a saturated aqueous solution of sodium chloride.. After this layer was dried over anhydrous sodium sulfate, it was concentrated under reduced pressure on a 32C water bath to obtain the captioned compound.. This compound was subjected to silica gel column chromatography (BW·80S 150 g, FUJISILYSIA, mobile phase: CHCl3:MeOH (9:14:13:1 (V/V))) for purification.. The purified compound was concentrated under reduced pressure on a 35C water bath to obtain 4.09 g of a pale yellow liquid (10.4 mmols, yield 62%). NMR confirmed this product to have the following structure: |
Yield | Reaction Conditions | Operation in experiment |
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57% | With Candida antarctica lipase B In toluene at 110℃; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
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Stage #1: trioleoylglycerol at 300℃; for 120h; Inert atmosphere; Stage #2: methanol With sodium hydroxide at 60℃; for 0.25h; Stage #3: With boron trifluoride at 60℃; for 0.166667h; |
Yield | Reaction Conditions | Operation in experiment |
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at 83℃; for 0.25h; | 1 253 g/h of a mixture of oleic acid and linoleic acid with a content of free fatty acids of 100% by weight was passed with 605 g/h of methanol at a temperature of 83° C. and a pressure of 4 bar once with a residence time of 15 min over a fixed catalyst bed composed of 650 ml of acidic ion exchange resin (corresponds to 121 g of catalyst mass (dry)). The catalyst particles had a diameter of 0.8 mm and were immobilized in a fixed bed reactor with a catalyst bed length of 2.08 m. This gives rise to a catalyst hourly space velocity of 2.1 kg of free fatty acid per kg of catalyst and hour, and a superficial velocity of 2.3 mm/s. In the reaction product, an acid content of 2.8% by weight was determined, i.e. a fatty acid conversion of 97.2% was achieved. This gives rise to a space-time yield of fatty-acid methyl ester of 397.1 g per litre of reactor volume and hour. |
Yield | Reaction Conditions | Operation in experiment |
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With scandium tris(trifluoromethanesulfonate) at 150℃; for 0.333333h; Microwave irradiation; |
Yield | Reaction Conditions | Operation in experiment |
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With dihydrogen peroxide In water; acetonitrile at 85℃; for 24h; Inert atmosphere; stereoselective reaction; | ||
With dihydrogen peroxide; stearic acid In icosane; acetic acid methyl ester; water at 37℃; for 22h; Green chemistry; Enzymatic reaction; Overall yield = 25 %; | 2 Enzymatic epoxidation reactions 20 mg of Novozym 435 were added to a solution of methyl oleate (1 mmol, 297 mg), stearic acid (0.05 mmol, 14 mg) and eicosane (0.15 mmol, 42 mg) used as an internal standard, in methyl acetate(3 ml). Then H2O2 (60 % in water, 0.7-1.2 eq., 35-60 μl) was added drop wise. The solution was shaken at 500 u.p.m. for 6 h at 37 °C. 10 mg of CALB-silica A or 11 mg CALB-silica B were added to asolution of methyl oleate (1 mmol, 297 mg), stearic acid (0.05 mmol,14 mg) and eicosane (0.15 mmol, 42 mg) used as an internal standard, in methyl acetate (3 ml). Then H2O2 (60% in water, 0.95 eq.,48 l) was slowly added. The solution was shaken at 500 u.p.m. for24 h at 40 C. In all cases, samples were withdrawn at regular times, catalyst was filtered off, and reaction progress was monitored by gas chromatography. When the reaction was complete, the immobilized lipase was separated by filtration and washed with ethyl acetate (3× 1 ml) and acetone (3×1 ml). Before reutilization, solids were dried in vacuo at room temperature. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With lithium doped magnesium oxide at 219.84℃; Inert atmosphere; chemoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
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In glycerol at 180℃; | 2.2. Heating procedure General procedure: An aliquot of 2 +/- 0.01 g of MO or ML were weighed directly into standard glass tubes (200 mm x 12 mm i.d.). The tubes were introduced into a Rancimat vessel containing 8 g of glycerol to facilitate heat transfer, and in turn inserted in the heating block of a Rancimat device previously heated at 180 +/- 1 °C. The reaction vessels were left open during heating and bubbling of air was not applied. After 15 h-heating, samples were taken out, shaken, and kept at -20 °C until analyses. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With dihydrogen peroxide In 1,3-diethoxy-isopropanol; water for 22h; Reflux; | ||
70 % de | With dihydrogen peroxide In water; acetonitrile at 90℃; for 6h; Inert atmosphere; Overall yield = 34 %Chromat.; stereoselective reaction; | 2.3. Catalytic tests General procedure: The epoxidation reaction tests on (R)-(+)-limonene (97%, Sigma)and methyl oleate (99% Aldrich) were carried out in a round-bottomed glass batch reactor, in an oil bath set at 90 °C, with magnetic stirring(ca. 800 rpm) under dry nitrogen atmosphere. The W/SiO2 catalystswere pre-treated in dry air at 500 °C and cooled down to room temperaturein vacuo prior to use. WO3 was pre-treated either at 120 °C indry air for 1 h and then in vacuo for 1 h or at 500 °C in dry air andcooled down to room temperature in vacuo prior to use.The catalyst (100 mg) was dispersed in 5 ml of acetonitrile (Aldrich,HPLC grade), as solvent, in the presence of 1 mmol of substrate (eitherlimonene or methyl oleate) and 2 or 4 mmol of aqueous hydrogenperoxide (H2O2; 50% Aldrich), as oxidant (oxidant to substrate molarratio of 2 : 1 or 4 : 1). Tert-butylhydroperoxide, TBHP (Sigma-Aldrich;5.5M anhydrous solution in decane) was used in one test with anoxidant to substrate molar ratio of 1.1 : 1. Samples were withdrawnfrom the reaction medium at regular intervals and analysed by GC(Agilent 6890 Series; SP-5 column, 30m ×0.25 mm; FID detector), byusing mesitylene (puriss.≥99%, Fluka,) or methyl palmitate (≥ 99%,Sigma) as internal standards, for limonene or methyl oleate epoxidation,respectively. Gas-chromatographic peaks were identified bycomparison with peaks of genuine samples of standard compounds andconfirmed by means of GC-MS. For both limonene epoxide and methylepoxystearate, cis:trans ratios were determined by 1H-NMR analysis(Bruker DRX 300) of the 6 h reaction mixture, after solvent removal invacuo. A standard deviation of±2%,±4% and±2 h-1 has to beconsidered on average for the conversion, yield and specific activityvalues, respectively. All tests were replicated at least two times. Nosignificant oxidation reactivity was recorded in the absence of solidcatalyst or in the presence of the pure silica support (in the absence oftungsten loading). A maximum limonene conversion of ca. 5-6% wasobserved after 6 h of reaction, but with no noteworthy formation ofepoxide products. Analogously, a maximum methyl oleate conversionof ca. 7% was recorded after 6 h, with very minor traces of the relatedepoxide, methyl epoxystearate. After each test, the presence of residualhydrogen peroxide was checked and confirmed by iodometric assays.In order to check the possible leaching of tungsten species, the solidcatalyst was removed from the liquid mixture after 45 min by hotcentrifugation (at the same temperature of the reaction mixture) andthe filtered liquid solution was tested for further reaction [49]. In thetests for the recovery of the catalyst, the solid was separated by filtrationand thoroughly washed with acetonitrile and then with methanol(Fluka, HPLC grade). The filtered solid was dried gently at 110 °C,weighed, activated again at 500 °C under dry air and then reused in anew catalytic cycle as described above. In one limonene epoxidationtest, hydroquinone (Carlo Erba; p.a.) was used as a free-radical scavengerin a quasi-equimolar amount (0.8 : 1 mol/mol) with respect tothe total tungsten content in the catalyst and added to the reactionmixture under the same conditions reported above. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: Methyl oleate With ozone In water; propionic acid for 1h; Stage #2: With dihydrogen peroxide In water; propionic acid at 100℃; for 1.25h; | 2 Example 2Ozonolysis and Oxidation with Addition of Acid20 g of a 0.182 molal solution of methyl oleate (95% pure) in a solvent mixture of propionic acid and water (15 equivalents based on moles of double bond) were initially charged in a two-neck flask with gas inlet tube and reflux condenser. The feed gas, consisting of 5% by volume of oxygen in carbon dioxide was passed through an ozone generator at a flow rate of 40 ml/min. The ozone generator was set to maximum power. The ozone-containing gas mixture was passed into the reaction mixture with stirring. The offgas stream was passed by means of gas wash bottles into a 5% aqueous potassium iodide solution. After 60 minutes, the substrate was converted, and the gas introduction was then stopped. According to GC analysis, the reaction mixture has a content of 39.5% of 9-nonanal and 38.2% of methyl 9-oxononanoate.After adding hydrogen peroxide (0.454 g of a 30% aqueous solution) and sulphuric acid (0.019 g, 95%) the reaction mixture was then heated to 100° C. in an oil bath. After 75 minutes, nonanal and methyl 9-oxononanoate were converted completely to the respective carboxyl compounds. GC analysis: 40.22% pelargonic acid, 38.50% azelaic acid derivative (21.90% monomethyl azelate+16.6% azelaic acid) (FID signal, figure in area percent, uncorrected). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With di-tert-amyl peroxide; hypophosphorous acid at 140℃; for 5h; Inert atmosphere; | S31 9-{Hydroxy-[1-(7-methoxycarbonyl-heptyl)-decyl]-phosphinoyl}-octadecanoic acid methyl ester (mixture of isomers) (131) 3.1 mL (0.03 moles) of 50% aqueous hypophosphorous acid and 16.92 g (0.06 moles) of methyl oleate (CE-1897 from P&G Chemical; iodine value=90) are mixed in a 100 mL single neck flask equipped with a distillation head. The mixture is purged with argon to remove oxygen and is heated under argon at 140° C. to remove water. After water is removed the mixture is cooled and 0.5 mL (0.0023 moles) of di-tert-amylperoxide are added and the mixture is purged with argon to remove oxygen and is heated under argon for 5 hours at 140° C. Tert-amyl alcohol is removed by distillation and 18.9 g (quantitative yield) of 9-{hydroxy-[1-(7-methoxycarbonyl-heptyl)-decyl]-phosphinoyl}-octadecanoic acid methyl ester (mixture of isomers) is obtained as a colorless wax melting near ambient temperature. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With di-tert-amyl peroxide; at 140℃; for 5h;Inert atmosphere; | A 100 mL round bottom flask, equipped with a reflux condenser connected to an argon inlet through a firestone valve and a magnetic stir bar is charged with 4.45 grams (15 mmol) of methyl oleate and 2.13 grams (15 mmol) of <strong>[1779-48-2]phenylphosphinic acid</strong>. Into the resultant stirred suspension is added 0.16 mL (0.75 mmol) of di-tert-amyl peroxide. The flask is flushed with argon 5 times then the oil bath temperature is raised to 140 C. and kept at 140 C. for 5 hours. The flask is put under vacuum to remove any tert-amyl alcohol that formed during the reaction. A clear light yellow viscous liquid is obtained at 6.36 grams (97% of theory). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen at 325℃; | Hydroconversion of methyl oleate General procedure: To elucidate the reaction mechanism of hydroconversion of Jatropha oil, a model study with methyl oleate over Catalyst C was conducted under the following conditions: 200-325C,LHSV = 40 h-1, 3 MPa, and H2/oil = 1200 mL/mL. The detailed product distributions of methyl oleate hydroconversion are presented in Table 8.Methyl oleate was almost completely converted, even at the rel-atively low temperature of 200C. Oxygenated compounds werethe main products at temperatures below 275C, while the deoxygenation rate was higher than 90% at temperatures above 275C.Hydrocarbons with carbon number of 17 and 18 (C17-18) were themain products, and were regarded as products of hydrodeoxygena-tion, as well as decarbonylation or decarboxylation, respectively.The C17/C18ratios at various reaction temperatures were similarly close to 1.15, which indicated that the reaction temperature didnot strongly affect the reaction pathway. The ratio of iso-C17+18/n-C17+18increased along with the reaction temperature because high temperatures might activate the acidic function of Pt/SAPO-11 cat-alyst to enhance the isomerization activity. All of the oxygenated compounds had straight chains, indicating that they were deoxy-genated to form n-alkanes before isomerization. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen at 275℃; | Hydroconversion of methyl oleate General procedure: To elucidate the reaction mechanism of hydroconversion of Jatropha oil, a model study with methyl oleate over Catalyst C was conducted under the following conditions: 200-325C,LHSV = 40 h-1, 3 MPa, and H2/oil = 1200 mL/mL. The detailed product distributions of methyl oleate hydroconversion are presented in Table 8.Methyl oleate was almost completely converted, even at the rel-atively low temperature of 200C. Oxygenated compounds werethe main products at temperatures below 275C, while the deoxygenation rate was higher than 90% at temperatures above 275C.Hydrocarbons with carbon number of 17 and 18 (C17-18) were themain products, and were regarded as products of hydrodeoxygena-tion, as well as decarbonylation or decarboxylation, respectively.The C17/C18ratios at various reaction temperatures were similarly close to 1.15, which indicated that the reaction temperature didnot strongly affect the reaction pathway. The ratio of iso-C17+18/n-C17+18increased along with the reaction temperature because high temperatures might activate the acidic function of Pt/SAPO-11 cat-alyst to enhance the isomerization activity. All of the oxygenated compounds had straight chains, indicating that they were deoxy-genated to form n-alkanes before isomerization. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen at 250℃; | Hydroconversion of methyl oleate General procedure: To elucidate the reaction mechanism of hydroconversion of Jatropha oil, a model study with methyl oleate over Catalyst C was conducted under the following conditions: 200-325C,LHSV = 40 h-1, 3 MPa, and H2/oil = 1200 mL/mL. The detailed product distributions of methyl oleate hydroconversion are presented in Table 8.Methyl oleate was almost completely converted, even at the rel-atively low temperature of 200C. Oxygenated compounds werethe main products at temperatures below 275C, while the deoxygenation rate was higher than 90% at temperatures above 275C.Hydrocarbons with carbon number of 17 and 18 (C17-18) were themain products, and were regarded as products of hydrodeoxygena-tion, as well as decarbonylation or decarboxylation, respectively.The C17/C18ratios at various reaction temperatures were similarly close to 1.15, which indicated that the reaction temperature didnot strongly affect the reaction pathway. The ratio of iso-C17+18/n-C17+18increased along with the reaction temperature because high temperatures might activate the acidic function of Pt/SAPO-11 cat-alyst to enhance the isomerization activity. All of the oxygenated compounds had straight chains, indicating that they were deoxy-genated to form n-alkanes before isomerization. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
13%Chromat. | With 5% Ru/SiO2; oxygen; at 80 - 150℃; for 12h; | Example 1 [0105] This example presents a comparison of various catalysts consisting of a metal deposited on a silicon media. All catalysts were prepared using ionic exchange starting from a colloidal silica stabilized with ammonium ions and metal chloride corresponding to the active species. These items were tested in regards to the functionalization reaction of methyl oleate by hydroxycitronellal which lead to the synthesis of 9-hydroxy-10-(7-hydroxy-3,7-dimethyloctanoyloxy)methyl octadecanoate and of 10-hydroxy-9-(7-hydroxy-3,7-dimethyloctanoyloxy)methyl octadecanoate as illustrated in Diagram 2. [0106] The reaction was carried out in a 100 ml glass reactor with mechanical agitation. Twenty-five grams (25.0 g) of methyl ester of sunflower oil HTO (high oleic content-purity: 85% methyl oleate) as well as 13.0 g of hydroxycitronellal (FCC Grade: Purity?95%-Sigma-Aldrich, Ref. W258318) were introduced into the reactor. The solid catalyst of the metal type supported on silica contains 5% by weight of the quantity of methyl oleate engaged, i.e. 250 mg. The environment was heated to 80 C. with continuous air bubbling. The air flow was controlled by a ball flow meter at 70 ml/min. After 7 hours of reaction time, the air flow was stopped and the reaction medium was raised to 150 C. These parameters were maintained for 5 additional hours. Samples of the reaction medium were taken at regular intervals in order to determine the status of the reaction. The reagent conversion rates and the yield rates of the desired products after 7 and 12 hours of reaction time are shown in Table 1: [TABLE-US-00001] Conversion Function- into alized Conversion hydroxy- Epoxide products Type of Reaction into methyl citronellala yield yield catalyst time (hr.) oleate (%) (%) (%) (%) no catalyst 7 37 70 27 11 12 46 92 9 24 Ru/SiO2 7 75 95 52 24 12 80 100 13 39 Co/SiO2 7 76 100 31 19 12 77 100 16 29 Zn/SiO2 7 66 99 30 20 12 69 100 10 27 Ni/SiO2 7 51 90 34 15 12 59 98 13 25 Cr/SiO2 7 49 89 31 15 12 56 97 13 25 Cu/SiO2 7 34 90 24 16 12 38 97 11 22 Rh/SiO2 7 34 86 18 17 12 40 96 8 26 [0107] The composition of the reaction medium was determined by gas phase chromatographic analysis. The Agilent Technologies 6870N chromatograph is equipped with a capillary column (SGE-BPX-70-length: 30 m, inside diameter: 0.25 mm, film thickness: 0.25 mum), of a split/splitless injector and a flame ionization detector (temperature of the injector and the detector: 280 C.). The temperature program of the furnace was as follows: 80 C. (0 min.)-13 C./min.-180 C. (6 min.)-13 C./min.-220 C. (6 min.)-17 C./min.-250 C. (10 min.). [0108] The hold time for the various products under the conditions described above are as follows: dodecane (2.9 min.); hydroxycitronellal (8.9 min.); methyl oleate (12.6 min.); methyl trans-9,10epoxy-stearate (18.9 min.); methyl cis-9,10-epoxy-stearate (19.2 min). [0109] The conversion of reagents at time t is expressed as follows: (number of initial moles of reagent-number of moles of reagent at time t)/number of initial moles of reagent*100. [0110] The epoxide yield at time t was calculated as follows: number of moles of epoxide at time t/(number of initial moles of methyl oleate*relative response coefficient of 9,10-epoxystearate in relation to methyl oleate)*100. [0111] The functionalized products, i.e. the methyl octadecanoate 9-hydroxy-10-(7-hydroxy-3,7-dimethyloctanoyloxy) and the methyl octadecanoate 10-hydroxy-9-(7-hydroxy-3,7-dimethyloctanoyloxy), were analyzed by steric exclusion chromatography. [0112] The Waters Alliance 2695 chromatograph is equipped with a refraction index detector (RI 410) and with two different columns (Styrage-HR 0.5 and Styragel-HR 1). The temperature of the furnace containing the columns is set at 30 C. and tetrahydrofurane (THF) is used as an eluent at a flow rate of 0.8 ml/min. [0113] Under these conditions, the hold times were as follows: products with high molecular weight (>1000 uma; 15.1 min); functionalized products (16.2 min.); methyl oleate and methyl 9,10-epoxy-stearate (18.1 min.); hydroxycitronellal (19.0 min.). [0114] The functionalized products yield is the relative surface area of the chromatographic peak expressed as a percentage of the total of all peaks. |
52%Chromat. | With 5% Ru/SiO2; oxygen; at 80℃; for 7h; | Example 1 [0105] This example presents a comparison of various catalysts consisting of a metal deposited on a silicon media. All catalysts were prepared using ionic exchange starting from a colloidal silica stabilized with ammonium ions and metal chloride corresponding to the active species. These items were tested in regards to the functionalization reaction of methyl oleate by hydroxycitronellal which lead to the synthesis of 9-hydroxy-10-(7-hydroxy-3,7-dimethyloctanoyloxy)methyl octadecanoate and of 10-hydroxy-9-(7-hydroxy-3,7-dimethyloctanoyloxy)methyl octadecanoate as illustrated in Diagram 2. [0106] The reaction was carried out in a 100 ml glass reactor with mechanical agitation. Twenty-five grams (25.0 g) of methyl ester of sunflower oil HTO (high oleic content-purity: 85% methyl oleate) as well as 13.0 g of hydroxycitronellal (FCC Grade: Purity?95%-Sigma-Aldrich, Ref. W258318) were introduced into the reactor. The solid catalyst of the metal type supported on silica contains 5% by weight of the quantity of methyl oleate engaged, i.e. 250 mg. The environment was heated to 80 C. with continuous air bubbling. The air flow was controlled by a ball flow meter at 70 ml/min. After 7 hours of reaction time, the air flow was stopped and the reaction medium was raised to 150 C. These parameters were maintained for 5 additional hours. Samples of the reaction medium were taken at regular intervals in order to determine the status of the reaction. The reagent conversion rates and the yield rates of the desired products after 7 and 12 hours of reaction time are shown in Table 1: [TABLE-US-00001] Conversion Function- into alized Conversion hydroxy- Epoxide products Type of Reaction into methyl citronellala yield yield catalyst time (hr.) oleate (%) (%) (%) (%) no catalyst 7 37 70 27 11 12 46 92 9 24 Ru/SiO2 7 75 95 52 24 12 80 100 13 39 Co/SiO2 7 76 100 31 19 12 77 100 16 29 Zn/SiO2 7 66 99 30 20 12 69 100 10 27 Ni/SiO2 7 51 90 34 15 12 59 98 13 25 Cr/SiO2 7 49 89 31 15 12 56 97 13 25 Cu/SiO2 7 34 90 24 16 12 38 97 11 22 Rh/SiO2 7 34 86 18 17 12 40 96 8 26 [0107] The composition of the reaction medium was determined by gas phase chromatographic analysis. The Agilent Technologies 6870N chromatograph is equipped with a capillary column (SGE-BPX-70-length: 30 m, inside diameter: 0.25 mm, film thickness: 0.25 mum), of a split/splitless injector and a flame ionization detector (temperature of the injector and the detector: 280 C.). The temperature program of the furnace was as follows: 80 C. (0 min.)-13 C./min.-180 C. (6 min.)-13 C./min.-220 C. (6 min.)-17 C./min.-250 C. (10 min.). [0108] The hold time for the various products under the conditions described above are as follows: dodecane (2.9 min.); hydroxycitronellal (8.9 min.); methyl oleate (12.6 min.); methyl trans-9,10epoxy-stearate (18.9 min.); methyl cis-9,10-epoxy-stearate (19.2 min). [0109] The conversion of reagents at time t is expressed as follows: (number of initial moles of reagent-number of moles of reagent at time t)/number of initial moles of reagent*100. [0110] The epoxide yield at time t was calculated as follows: number of moles of epoxide at time t/(number of initial moles of methyl oleate*relative response coefficient of 9,10-epoxystearate in relation to methyl oleate)*100. [0111] The functionalized products, i.e. the methyl octadecanoate 9-hydroxy-10-(7-hydroxy-3,7-dimethyloctanoyloxy) and the methyl octadecanoate 10-hydroxy-9-(7-hydroxy-3,7-dimethyloctanoyloxy), were analyzed by steric exclusion chromatography. [0112] The Waters Alliance 2695 chromatograph is equipped with a refraction index detector (RI 410) and with two different columns (Styrage-HR 0.5 and Styragel-HR 1). The temperature of the furnace containing the columns is set at 30 C. and tetrahydrofurane (THF) is used as an eluent at a flow rate of 0.8 ml/min. [0113] Under these conditions, the hold times were as follows: products with high molecular weight (>1000 uma; 15.1 min); functionalized products (16.2 min.); methyl oleate and methyl 9,10-epoxy-stearate (18.1 min.); hydroxycitronellal (19.0 min.). [0114] The functionalized products yield is the relative surface area of the chromatographic peak expressed as a percentage of the total of all peaks. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With dihydrogen peroxide; stearic acid In icosane; acetic acid methyl ester; water at 40℃; Green chemistry; Enzymatic reaction; | 2 Enzymatic epoxidation reactions 20 mg of Novozym 435 were added to a solution of methyl oleate (1 mmol, 297 mg), stearic acid (0.05 mmol, 14 mg) and eicosane (0.15 mmol, 42 mg) used as an internal standard, in methyl acetate(3 ml). Then H2O2 (60 % in water, 0.7-1.2 eq., 35-60 μl) was added drop wise. The solution was shaken at 500 u.p.m. for 6 h at 37 °C. 10 mg of CALB-silica A or 11 mg CALB-silica B were added to asolution of methyl oleate (1 mmol, 297 mg), stearic acid (0.05 mmol,14 mg) and eicosane (0.15 mmol, 42 mg) used as an internal standard, in methyl acetate (3 ml). Then H2O2 (60% in water, 0.95 eq.,48 l) was slowly added. The solution was shaken at 500 u.p.m. for24 h at 40 C. In all cases, samples were withdrawn at regular times, catalyst was filtered off, and reaction progress was monitored by gas chromatography. When the reaction was complete, the immobilized lipase was separated by filtration and washed with ethyl acetate (3× 1 ml) and acetone (3×1 ml). Before reutilization, solids were dried in vacuo at room temperature. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With methanol; water; triphenylphosphine; at 260℃; under 8250.83 Torr; for 6h;Inert atmosphere;Catalytic behavior; | General procedure: The key parameters for all experiments are summarised in Table 2. Catalyst testing was carried out in an RC1 high-pressure reactor from Mettler Toledo, using the following amounts: 1000 g OA or its methyl ester MO, 50.0 g H-Fer, 3.75 g TPP and 10.0 g demineralised water (or/and methanol). After purging with nitrogen 3 times, the reactor was pressurised to about 1 bar and heated to (a maximum of) 260 C at a rate of 6 C/min, resulting in a pressure of about 11 bar. Reaction temperature was typically held for 6 h (unless otherwise stated), before the mixture was cooled to 80 C and filtered under nitrogen for a minimum of 4 h. Spent catalyst from experiment 15 was collected and reused in experiment 16 after acetone washing; for practical reasons, the catalyst loading was reduced to 1.5 wt% and the promoter was omitted in both runs 15 and 16. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With bis{rhodium[3,3'-(1,3-phenylene)bis(2,2-dimethylpropanoic acid)]; O-(2,4-dinitrophenyl)hydroxylamine In 2,2,2-trifluoroethanol at 20℃; for 3h; Inert atmosphere; | Methyl (Z)-8-(3-octylaziridin-2-yl)octanoate: (42, 43) Following the general aziridination procedure, methyl oleate 7 (0.148 g, 0.5 mmol), aminating agent la (0.1 19 g, 0.6 mmol), and Rh2(esp)2 (3.8 mg, 5 /mol) were stirred in CF3CH2OH (5 mL) at rt for 3 h. Chromatographic purification of the crude product using 50-70% EtOAc/hexanes as eluent afforded the title aziridine as a viscous oil which solidified upon standing (0.130 g, 83%), mp 51.4-51.7 °C. TLC: Rf ~ 0.3 (60% EtOAc/hexanes); 'H NMR (400 MHz, CDC13) δ 3.63 (s, 3H), 2.27 (t, J= 7.5 Hz, 2H), 1.93-1.90 (m, 2H), 1.66-1.53 (m, 2H), 1.49-1.19 (m, 25H), 0.85 (t, J= 7.0 Hz, 3H); 13C MR (101 MHz, CDC13) δ 174.24, 51.39, 34.94, 34.90, 34.05, 31.84, 29.60, 29.58, 29.37, 29.24, 29.21, 29.05, 28.87, 28.82, 28.04, 27.97, 24.89, 22.63, 14.07; HRMS (ESI+) Calcd. for [Ci9H37N02+H]+ 312.2897, Found 312.2887. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With dirhodium tetraacetate; In acetonitrile; at 20 - 60℃; for 12h;Inert atmosphere; | Methyl 9-amino-10-(2,4-dinitrophenoxy)octadecanoate/10-amino-9-(2,4- dinitrophenoxy)octadecanoate: Following the general aminoaryloxylation procedure, methyl oleate 7 (10 mg, 34 munualphaomicron), aminating agent la (10 mg, 51 munualphaomicron), and Rh2(OAc)4 (0.8 mg, 1.7 munualphaomicron) were stirred in dry CH3CN (0.5 mL) at rt for 2 h, then at 60 C for 10 h. Chromatographic purification of the crude product by preparative TLC using 40% EtOAc/hexanes as eluent afforded the title aminoaryloxylated regioisomers (1 : 1) as a viscous oil (2.5 mg, 15%). TLC: Rf ~ 0.5 (30% EtOAc/hexanes); XH NMR (500 MHz, CDC13) delta 9.16 (d, J= 2.7 Hz, 1H), 8.93 (dd, J = 9.0, 2.4 Hz, 1H), 8.24 (dd, J= 9.6, 2.7 Hz, 1H), 6.94 (dd, J= 9.7, 3.5 Hz, 1H), 3.87-3.83 (m, 1H), 3.67 (s, 1.5H), 3.66 (s, 1.5H), 3.65-3.61 (m, 1H), 2.30 (t, J= 7.4 Hz, 1H), 2.29 (t, J= 7.4 Hz, 1H), 1.96 (br s, 1H), 1.80-1.77 (m, 1H), 1.76-1.14 (m, 30H), 0.87 (t, J= 6.9 Hz, 1.5H), 0.86 (t, J= 6.9 Hz, 1.5H); 13C NMR (101 MHz, CDCI3) delta 174.25, 174.24, 148.68, 148.66, 135.58, 130.31, 130.25, 124.77, 1 14.06, 1 14.03, 72.17, 57.40, 57.31, 51.51, 51.49, 34.50, 34.44, 33.96, 33.93, 32.13, 32.06, 31.77, 29.54, 29.43, 29.42, 29.40, 29.25, 29.17, 29.15, 29.12, 29.03, 28.96, 28.86, 26.19, 26.04, 25.79, 25.65, 24.74, 22.62, 22.61, 14.07; HRMS (ESI+) Calcd. for [C25H41N307+Na]+ 518.2837, Found 518.2827. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With bis{rhodium[3,3'-(1,3-phenylene)bis(2,2-dimethylpropanoic acid)] In 2,2,2-trifluoroethanol at 20℃; for 6h; Inert atmosphere; | Methyl (Z)-8-(l-methyl-3-octylaziridin-2-yl)octanoate: Following the general aziridination procedure, methyl oleate 7 (89 mg, 0.3 mmol), N-methylaminating agent lb (77 mg, 0.36 mmol), and Rh2(esp)2 (2.3 mg, 3 μηαο) were stirred in CF3CH2OH (3 mL) at rt for 2 h. Thereafter, two more portions of catalyst (1.1 mg, 0.5 mol%) and aminating agent (13 mg, 0.06 mmol, 0.2 equiv) were added after every 2 h and stirred for a total of 6 h. Chromatographic purification on a CombiFlash system over S1O2 to give the title aziridine as an oil (78 mg, 80%). TLC: Rf ~ 0.5 (50% EtOAc/hexanes); XH NMR (500 MHz, CDC13) δ 3.64 (s, 3H), 2.31 (s, 3H), 2.27 (t, J= 7.6 Hz, 2H), 1.64-1.54 (m, 2H), 1.46-1.19 (m, 24H), 1.19- 1.14 (m, 2H), 0.85 (t, J= 6.9 Hz, 3H); 13C MR (126 MHz, CDC13) δ 174.28, 51.42, 48.12, 45.46, 45.41, 34.05, 31.86, 29.62, 29.61, 29.39, 29.27, 29.26, 29.07, 28.22, 28.18, 28.12, 28.05, 24.90, 22.67, 14.1 1; HRMS (ESI+) Calcd. for [C2oH39N02+Na]+ 348.2873, Found 348.2863. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene][2-[[(2-methylphenyl)imino]methyl]phenolyl][3-phenyl-1H-inden-1-ylidene](chloro)ruthenium(II); Phenyltrichlorosilane In toluene at 80℃; for 0.5h; | Cross Metathesis with cis-1,4-Diacetoxy-2-Butene 5 General procedure: When using 0.20 g (1.0 mmol) of methyl 10-undecenoate 1 [or 0.30 g (1.0 mmol) methyl oleate 6], 0.87 g (5.0 mmol) cis-1,4-diacetoxy-2-butene 5, 9.63 g toluene (10.53 g) and an appropriate amount of catalyst was added (1.0 mol%, e.g. [Ru]-4 = 0.009 g/0.01 mmol). The reaction, the sample preparation and the product isolation occurred analogous to the cross metathesis described above. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | Stage #1: Methyl oleate With diethylzinc In hexane; dichloromethane at -5 - 0℃; for 1h; Inert atmosphere; Stage #2: diiodomethane In hexane; dichloromethane at 20℃; Inert atmosphere; | 4.15. Synthesis of methyl dihydrosterculate (14) To a stirred solution of oleic acid methyl ester (13) (2 g,6.77 mmol), in DCM (40 mL), 1 M n-hexane solution of diethyl zinc(4.17 mL, 40.54 mmol), was added under N2 atmosphere, wereplaced in a cooling ice bath (5 Ce0 C) and stirred for 1 h. Thendiiodomethane (6.53 mL, 81.08 mmol) was added. After 10 min, amilky solution was formed. Then the reaction mixture was stirredfor overnight at RT. After completion of the reaction, saturatedNH4Cl (20 mL) was added to the reaction mixture to break the whitesolid. After this quenching process, the reaction mixture wastransferred to a separating funnel. The two layers were separated,from this the organic layer was separated and the aqueous layer wasextracted with CHCl3 (30 mL 2). The combined organic layers werewashed with brine solution and dried over anhydrous Na2SO4 andconcentrated under vacuum. Here the 100% starting material wasconverted to the product. The crude product contained excessdiiodomethane only. This was purified by silica gel column chromatography using pure hexane followed by a solvent mixture ofhexane: EtOAc (97:3, v/v) to give title compound as oil (2.09 g,100%).1H NMR (500 MHz, CDCl3) d 3.66 (s, 3H), 2.3 (t, J 7.6 Hz, 2H),1.59e1.64 (p, 2H), 1.23e1.37 (m, 22H), 1.11e1.17 (m, 2H), 0.88 (t,J 6.7 Hz, 3H), 0.63e0.66 (m, 2H), 0.53e0.57 (m, 1H), -0.33 (q,J 4.12 Hz,1H); 13C NMR (75 MHz, CDCl3) d 174.1, 51.3, 34, 31.9, 30.16,30.07, 29.63, 29.47, 29.39, 29.26, 29.1, 28.6, 27.13, 24.8, 22.6, 15.6, 14,10.8; IR (CHCl3) 2926, 2855, 1736, 1460, 1437, 1215, 759 cm1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 86% 2: 91% | With C52H57F5MoN2O In benzene at 22℃; for 4h; stereoselective reaction; | |
1: 91% 2: 86% | With C52H57F5MoN2O In benzene at 22℃; for 4h; Glovebox; Inert atmosphere; | (Z)-methyl 10-chloro-9-decenoate (17) & (Z)-l-chloro-l-decene (18) [00304] (Z)-methyl 10-chloro-9-decenoate (17) & (Z)-l-chloro-l-decene (18): Following the general procedure, a solution of Mo-4 in benzene (0.1 M, 30 μ, 3.0 μιηο, 3 mol %) was transferred by syringe to an oven-dried vial containing Z-l ,2-dichloroethylene (48.5 mg, 0.5 mmol, 5.00 equiv), methyl oleate (29.7 mg, 0.1 mmol, 1.00 equiv) and benzene (470 uL). The resulting solution was allowed to stir for 4 hours at 22 °C. The reaction was quenched by addition of wet CDCI3 and analysis of the unpurified mixture revealed 94% consumption of methyl oleate. The resulting orange oil was purified by silica gel chromatography (100% hexanes to 10% Et20 in hexanes) to afford 17 (20.0 mg, 0.0914 mmol, 91% yield) in 97:3 Z:E ratio as colorless oil and 18 (15.0 mg, 0.0859 mmol, 86%> yield) in 97:3 Z:E ratio as colorless oil. The spectral data for 18 were identical to those reported in the literature.16 1H NMR (400 MHz, CDCI3) for 17: Z-isomer (major): δ 6.01 (1H, dd, J = 7.1 , 1.6 Hz), 5.74 (1H, q, J = 7.1 Hz), 3.67 (3H, s), 2.30 (2H, t, J = 7.5 Hz), 2.21 (2H, qd, J = 7.2, 1.4 Hz), 1.67-1.58 (2H, m), 1.43-1.35 (2H, m), 1.34-1.30 (6H, m). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With (acetylacetonato)dicarbonylrhodium (l); tris[(S)-2'-(benzyloxy)-1,1'-binaphthyl-2-yl] phosphite; hydrogen In toluene at 60℃; for 24h; Autoclave; chemoselective reaction; | 2.3. General procedure of Rh(I)/monophosphite-catalysedhydroformylation General procedure: A stainless steel autoclave, containing a 40 mL glass vessel, wascharged with the monophosphite ligand. Then, the rhodium pre-cursor [Rh(acac)(CO)2], dissolved in toluene, was added via cannula(see relative amounts, for each experiment, in Tables 1 and 2). Thesystem was purged with three cycles of vacuum and an equimolarmixture of CO/H2(syngas). The autoclave was pressurised with syn-gas (30 bar), the temperature was set to 80C and the mixture wasmagnetically stirred for 1 h (external stirring rate of 450 rpm). Afterthis incubation period, the autoclave was slowly depressurisedand the substrate, dissolved in toluene, was introduced throughthe inlet cannula (see relative amounts, for each experiment, inTables 1 and 2). Then, the autoclave was pressurised with CO/H2(25 bar) and the temperature was set on the desired value. Reaction kinetics was followed by taking and analysing GC aliquots of thereaction mixture at regular intervals. At the end, the autoclave wascooled, slowly depressurised and the solvent was evaporated underreduced pressure. Identification and characterisation of productswere performed by GC-MS,1H and13C NMR spectroscopy. Con-versions, chemo-, regio- and diasteroselectivity were determinedby GC analysis. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 95% 2: 67% | With C47H71ClMoN2O In benzene at 22℃; for 4h; Glovebox; Inert atmosphere; stereoselective reaction; | General procedure for cross-metathesis with a MAC complex. General procedure: In a N2-filled glove box, an oven-dried 8-ml vial equipped with a magnetic stir bar was charged with alkene substrate and the corresponding organohalogen reagent (Z-1,1,1,4,4,4-hexafluoro-2-butene, Z-1,2-dichloroethene or 1,2-dibromoethene). A solution of an appropriate MAC complex in benzene was then added. The resulting mixture was allowed to stir for 15 min-12 h at 22 °C, after which the reaction was quenched by the addition of wet (undistilled) CDCl3 (per cent conversion was determined by 1H NMR analysis of the unpurified mixture). Purification was performed through silica gel chromatography, preparative thin-layer chromatography and/or Kugelrohr distillation. |
1: 95% 2: 67% | With C52H73ClMoN2O In benzene at 22℃; for 0.25h; Inert atmosphere; Glovebox; | (Z)-methyl 11,11,11-trifluoro-9-undecenoate (9) & (Z)-1,1,1-trifluoro-2-undecene (10) General procedure: Following the general procedure, a solution of Mo-2d in benzene (0.1M, 8 1-1L, 0.8 1-1mol, 2 mol %) was transferred by syringe to an oven-dried vial containingZ-1, 1,1 ,4,4,4-hexafluoro-2-butene (32.8 mg, 0.200 mmol, 5.0 equiv) and Z-methyl oleate(11.9 mg, 0.0400 mmol, 1.0 equiv). The resulting solution was allowed to stir for 15 minat 22 °C. The reaction was quenched by addition of wet CDCI3 and analysis of theunpurified mixture revealed >98% consumption of Z-methyl oleate. The resulting greenoil was purified by silica gel chromatography (1 00% pentane to 4% Et20/pentane) toafford 9 (9.6 mg, 0.0381 mmol, 95% yield) in >98:98:2 Z:E ratio as colorless oil. Spectral data for 9:1 H NMR (400 MHz, CDCb): Z isomer (major): c5 5.97 (1 H, dt, J = 11.5, 7.9 Hz), 5.64 (1 H,m), 3.67 (3H, s), 2.33 (4H, m), 1.67 (2H, m), 1.45-1.37 (2H, m), 1.34-1.29 (6H, m).Spectral data for 10: 1H NMR (400 MHz, CDCl3): Z isomer (major): δ 5.98 (1H, dt, J =11.6, 7.9 Hz), 5.64 (1 H, m), 2.35 (2H, m), 1.47 (2H, m), 1.33-1.23 (1 OH, m), 0.88 (3H, t,J = 6.9 Hz). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 90% 2: 85% | With C58H79ClMoN2O In benzene at 22℃; for 4h; Glovebox; Inert atmosphere; stereoselective reaction; | General procedure for cross-metathesis with a MAC complex. General procedure: In a N2-filled glove box, an oven-dried 8-ml vial equipped with a magnetic stir bar was charged with alkene substrate and the corresponding organohalogen reagent (Z-1,1,1,4,4,4-hexafluoro-2-butene, Z-1,2-dichloroethene or 1,2-dibromoethene). A solution of an appropriate MAC complex in benzene was then added. The resulting mixture was allowed to stir for 15 min-12 h at 22 °C, after which the reaction was quenched by the addition of wet (undistilled) CDCl3 (per cent conversion was determined by 1H NMR analysis of the unpurified mixture). Purification was performed through silica gel chromatography, preparative thin-layer chromatography and/or Kugelrohr distillation. |
1: 10 mg 2: 85% | With C58H79ClMoN2O In benzene at 22℃; for 2h; Inert atmosphere; Glovebox; | (Z)-methyl 10-bromodec-9-enoate (5) & (Z)-1-bromodec-1-ene (6) General procedure: Following the general procedure, a solution of Mo-2b in benzene (0.1 M, 12 1-1L, 1.21-1mol, 3 mol %) was transferred by syringe to an oven-dried vial containing 1,2-dibromoethene (59.5 mg, 0.320 mmol, 8.0 equiv) and Z-methyl oleate (11.9 mg, 0.0400mmol, 1.0 equiv). The resulting solution was allowed to stir for 2 h at 22 °C. The reactionwas quenched by addition of wet CDCI3 and analysis of the unpurified mixture revealed95% consumption of Z-methyl oleate. The resulting green oil was purified by silica gelchromatography (100% hexane to 4% Et20/hexane) to afford 5 (10.0 mg, 0.0380 mmol,95% yield) in >98:98:2 Z:E ratio as colorless oil. Spectral data for 5: 1H NMR (500 MHz, CDCl3): Z isomer(major): δ 6.14 (1 H, d, J = 6.9 Hz), 6.08 (1 H, q, J = 6.9 Hz), 3.67 (3H, s), 2.30 (2H, t, J =7.5 Hz), 2.18 (2H, dt, J = 7.6, 4.0 Hz), 1.61 (2H, dd, J = 14.2, 7.1 Hz), 1.43 (2H, m), 1.32(6H, brs). The spectral data for 6 were identical to those reported previously (Millar, J.G.; Underhill, E. W. J. Org. Chern. 1986, 51, 4726-4728). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With iodine at 60℃; for 24h; Inert atmosphere; | Synthesis of bis(alkylthio)alkanoates. General procedure: All fatty acid methyl esters (1 mol) were reacted with dialkyl disulfide (6 mol) elemental iodine (0.01 mol) for 24 h at 60 °C under N2. Then the reaction mixture was cooled to room temperature. Volatile dialkyl disulfides were removed by a stream of nitrogen from the reaction mixture. Equal amounts (3 mL) of hexane and 5% aqueous sodium thiosulfate solution were added, and the mixture was washed with further aliquots of the sodium thiosulfate solution until the iodine color disappeared. The product was then dried with a sodium sulfate column and hexane removed under a stream of nitrogen, which also removed any additional remaining dialkyl disulfide. Further removal of less volatile dialkyl disulfide and unreacted starting material was carried out by high-performance liquid chromatography on a silica column using a 20:1 hexane/ethyl acetate solvent system. After removal of the solvent system by rotary evaporation, the products were obtained as colorless liquids. Yields as determined by NMR prior to HPLC purification decrease with increasing size of the dialkyl disulfide employed, ranging from quantitative or near-quantitative with DMDS to 50-60% when using DiPDS or dibutyl disulfide (DBDS). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 71 %Chromat. 2: 27 %Chromat. | With C46H43N7OPRu(1+)*BF4(1-); potassium <i>tert</i>-butylate; hydrogen In 1,4-dioxane at 100℃; for 2h; Inert atmosphere; Autoclave; chemoselective reaction; | General procedure for catalytic ester hydrogenation reactions General procedure: The catalyst (3,75 μmol), KOtBu (11 mg, 0.1 mmol for 20 mol%), Me3NO (if applicable, 1.9 mg) and the substrate (if solid; 0.5 mmol) were weighed in a 4 mL GC-vial with a septum screw-cap charged with a stirring bar under an N2 atmosphere. Subsequently, p-xylene (23.2 μL), the substrate (if liquid; 0.5 mmol) and THF (2 mL) were added. A needle was used to puncture the cap and a set of four vials was placed in a stainless steel autoclave (200 mL) under argon gas. The autoclave was flushed 2 times with 10 bar of H2 and then pressurized to the desired pressure (5 or 50 bar), after which it was placed in a preheated oil bath (140 °C; built-in thermometer indicated 100 °C as the internal temperature of the autoclave). After allowing the autoclaveto warm up (approximately 30 min.) the mixture was stirred for 2h after which the autoclave was cooled in an ice bath and the pressure was released. The conversions were determined by GC analysis as described in the general experimental details above. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
General procedure for the preparation of crude PBC-FAs (i.e., oleic-phenol BCFAs): Detailed procedures to convert a potassium-containing zeolite to a protonated cation form (H-ferrierite zeolite) by acid washing were reported previously (Ngo, H. L., et al., Eur. J. Lipid Sci. Technol., 108: 214-224 (2007); Ngo, H. L., et al., Eur. J. Lipid Sci. Technol., 2012, 114, 213-221 (2012)). In general, crude PBC-FAs were prepared by adding a mixture of unsaturated fatty acids or alkyl esters thereof (e.g., OLA; 30 g), phenolic compound(s) (e.g., phenol). 60 g, 6 molar equivalents to, for example, OLA), modified H+-Ferrierite-K zeolite (4.5 g, 15 wt % to, for example, OLA), and deionized water (3.25 mL, 73% to H+-Ferrierite-K) to a 300 mL high pressure stainless steel reactor equipped with a temperature controller and mechanical stirrer. The reactor head had a cooling sleeve (i.e., condenser) attached which allowed the temperature to be set between -5 C. and -20 C. The vessel was sealed, purged with N2 (80 psi, 3×), the headspace was filled with N2 (80 psi), and the mixture was heated with stirring to the desired temperature. Small fractions of the reaction mixture were removed from the reactor at 6 and 24 h for hydrogenation, methylation, and analysis. After 48 h, the heating was discontinued, the mixture was allowed to cool to room temperature, and the system was vented. After removal of the zeolite catalyst by vacuum filtration, samples of the crude mixture (oleic-phenolic BCFAs (FIG. 1)) were subjected to hydrogenation and methylation. It is important to note that the phenolic-branched-chain fatty acid products (FIG. 1, structures 7 and 8) in the crude mixture obtained upon removal of the zeolite catalyst were actually in the saturated form. The subsequent reactions (i.e., hydrogenation and methylation) were performed only for the purpose of analysis. Thus only small amounts of the crude phenolic product were carried on to these next two steps: Hydrogenation was performed with small amounts (approximately 1 wt %) of 5% palladium on carbon (Pd/C) catalyst (Pressure Chemical Co., Pittsburg, Pa.) and hydrogen gas (20 psi, room temperature, 3 h) to give the crude saturated form of the FA mixture. The saturated fatty acid product was then converted to fatty acid methyl esters (FAME) by methylation, which involved treating the product with excess methanol (100 fold molar excess) and a catalytic amount of sulphuric acid at 100 C. for 2 h. After heating, the excess methanol was evaporated and the crude product was diluted with 20 mL hexanes:ethyl acetate (95:5) and neutralized with 20 mL saturated sodium bicarbonate solution. The mixture was transferred to a separatory funnel for extraction. The aqueous phase was back-extracted with hexanes:ethyl acetate (95:5) after which the two solvent phases were combined and washed with the distilled water one more time. The organic phase was dried with magnesium sulfate and solvent was evaporated to give quantitative yield of the desired crude PBC-FAME product. The structures of the crude PBC-FAME mixture can be found in FIG. 1 but in the fatty acid form. The methylated products were then subjected to analysis by various analytical techniques described below. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 27.5% 2: 17.5% 3: 6.8% 4: 17.6% 5: 11.4% | With 7CeO2*7Nb2O5*3La2O3*K2O*2Bi2O3; oxygen at 120℃; for 15h; Autoclave; | 5 Example 5. Catalytic oxidation of methyl oleate (>99%) with the mixed oxide 7(CeO2) 7(Nb2O5) 3(La2O3) 1(K2O) 2(Bi2O3) under P02 = 9 bar. In order to improve the stability of the catalyst and its activity, multiple mixed oxides were prepared. The mixed oxide 7(CeO2) 7(Nb2O5) 3(La2O3) 1(K2O) 2(Bi2O3), prepared according to Example 1 , showed excellent stability in catalysis and good reaction rate and selectivity. The catalyst (50 mg) was placed in a glass reactor, kept in vacuo for 30 min to eliminate humidity and added with methyl oleate (1 mL ) under N2. The reactor was placed in a stainless steel autoclave that was closed, evacuated, charged with O2 (9 bar) and heated to T=120 °C for a time variable between t=0,66 and 15h. At the end the catalyst was recovered by centrifugation and the liquid processed as reported in Example 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium hydroxide In 2,2,4-trimethylpentane for 10h; Reflux; | 3.2 (2) Potassium hydroxide catalyst, the glycerol monoacetate in isooctane with a mixture of fatty acid methyl ester (methyl oleate, methyl linoleate) was heated at reflux for 10 hours, to obtain a triglyceride; monoacetate quality glyceride and fatty acid methyl ester mixture ratio of 1: 8. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tin (II) oxalate; at 230℃; for 4h;Inert atmosphere; | In a 250 mL four-neck flask equipped with a stirrer,Add 6.00g of pentaerythritol, 62.20g of methyl oleate,0.41g of stannous oxalate, 0.12g of sodium oleate, heated to 230C under nitrogen protection for 4h, after the reaction was completed,The catalyst was removed by filtration to obtain a crude product of Chinese name pentaerythritol tetraoleate (PETTO). The crude product was distilled under reduced pressure to remove unreacted methyl oleate to obtain a PETTO product.The hydroxyl value was 2.56 mg KOH/g, the PETTO content was 96.32%, the esterification rate was 98.9%, the color was 0.8 (Gardner), and the anti-emulsification was (40-39-1) 13 min. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With Cp2Zr(H2O)3(OSO2C8F17)2·THF at 100℃; for 24h; | 2.4 Typical procedure for transesterification of alcohol with triolein using catalyst 1 To a round-bottom flask was added ethanol (138mg, 3.0mmol) and 1 equivalent of triolein (885mg, 1.0mmol) and catalyst 1 (37.8mg, 0.03mmol, 1.0mol% relative to ethanol). The mixture was stirred at 100°C for 24h and monitored by TLC. Then the mixture was diluted with petroleum ether (10mL×3). By means of filtration, the catalyst was separated and used for the next cycle, and the filtrate was washed twice with 10mL of saturated brine, and extracted by petroleum ether (10mL×2). Subsequently the portions of petroleum ether were combined together, dried by sodium sulfate, and evaporated to obtain the crude ester. Finally, the ester was subject to short flash column chromatography on silica gel (petroleum ether: ethyl acetate=20:1, Rf=0.4) to afford the colorless liquid, yield, 85%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With Novozym 435 In <i>tert</i>-butyl alcohol at 50℃; for 24h; | 2.3. Synthesis of (hydroxyl)tyrosyl esters The synthesis of hydroxytyrosyl acetate (HtyAce) was on a previously reported enzymatic procedure with modifications (Fazio et al., 2017). Briefly, hydroxytyrosol (1.6 mmol), was stirred in an orbital shaker at 50 °C in the presence of ethyl acetate (2 mL), as the acyl donor and solvent, and Novozym435 (immobilized Candida antarctica lipase B, CALB, 200 mg), as the catalyst. The synthesis of the other esters was carried out using hydroxytyrosol or tyrosol (1.6 mmol), the appropriate fatty acid methyl ester (3.2 mmol) as acyl donor, in the presence of CALB (200 mg), in t-butanol as the solvent (2 mL) in an orbital shaker at 50 °C. In both procedures, the enzyme was filtered off after 24 h, and the solvent evaporated under reduced pressure. Subsequently, products were purified by column chromatography (SiO2, using n-hexane-acetone as the eluent). Characterization data of the purified compounds were in agreement with those available in the literature (Mateos et al., 2008; Trujillo et al., 2006). The purity of Hty esters was assessed by HPLC and found to be as ≥ 98 % in all cases. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With sodium formate; palladium diacetate In tert-butyl methyl ether at 80℃; for 36h; | 1.1; 2-3 The first step: 200ml of solvent tert-butyl methyl ether, 29.7g (0.1mol) of methyl oleate, 0.36g (0.002mol) of palladium chloride, 0.68g (0.01mol) of sodium formate, 80 °C after 36 hours of reaction, extract three times with water and ethyl acetate, remove the aqueous layer, and dry the organic layer over anhydrous sodium sulfate. Remove the solvent with a rotary evaporator, extract the product with dichloromethane and evaporate the solvent, 23.5 g of Intermediate 1 was obtained with a yield of 79%. Repeated times to obtain a sufficient amount of Intermediate 1; |
Tags: 112-62-9 synthesis path| 112-62-9 SDS| 112-62-9 COA| 112-62-9 purity| 112-62-9 application| 112-62-9 NMR| 112-62-9 COA| 112-62-9 structure
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