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CAS No. : | 97-54-1 | MDL No. : | MFCD00009285 |
Formula : | C10H12O2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | BJIOGJUNALELMI-ONEGZZNKSA-N |
M.W : | 164.20 | Pubchem ID : | 853433 |
Synonyms : |
4-Propenylguaiacol
|
Num. heavy atoms : | 12 |
Num. arom. heavy atoms : | 6 |
Fraction Csp3 : | 0.2 |
Num. rotatable bonds : | 2 |
Num. H-bond acceptors : | 2.0 |
Num. H-bond donors : | 1.0 |
Molar Refractivity : | 49.86 |
TPSA : | 29.46 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | Yes |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -5.14 cm/s |
Log Po/w (iLOGP) : | 2.38 |
Log Po/w (XLOGP3) : | 3.04 |
Log Po/w (WLOGP) : | 2.33 |
Log Po/w (MLOGP) : | 2.01 |
Log Po/w (SILICOS-IT) : | 2.31 |
Consensus Log Po/w : | 2.41 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 1.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -3.01 |
Solubility : | 0.16 mg/ml ; 0.000974 mol/l |
Class : | Soluble |
Log S (Ali) : | -3.32 |
Solubility : | 0.0778 mg/ml ; 0.000474 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -2.42 |
Solubility : | 0.627 mg/ml ; 0.00382 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.81 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P264-P270-P271-P272-P280-P301+P312+P330-P302+P352+P312-P304+P340+P312-P305+P351+P338-P333+P313-P337+P313-P403+P233-P405-P501 | UN#: | N/A |
Hazard Statements: | H302+H312-H315-H317-H319-H335 | 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 |
---|---|---|
at 275 - 280℃; unter Druck; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With rhodium(III) chloride; ethanol at 140 - 145℃; | 2 (2) isomerization of eugenol: the isomerization reaction of eugenol by preparing isoeugenol In a 25 ml flask was added4.2 mg of rhodium trichloride (RhCl3),And add about 3 drops of absolute ethanol to dissolve,Then 20.0 mmol (3.284 g)The eugenol obtained in step (1)The reaction at 140-145 ° C for 3-5h,The reaction liquid gradually changed from pale yellow to bright orange then dark orange,Detection of each section of the reaction liquid,Structural analysis with UV - Vis spectroscopy,After the reaction, stop heating,Cooled to room temperature; suction filtered,Rhodium trichloride catalyst was separated and recovered; Extraction of isoeugenol in the filtrate with ether,The combined organic layers,Evaporate the ether in the water bath,Get isoeugenol,The yield of isoeugenol is about 99%; |
99% | With tris(triphenylphosphine)ruthenium(II) chloride at 50 - 60℃; for 4h; | 1.1; 2.1; 3.1 Heterogeneous reaction: 500g of eugenol and 4.0g of triphenylphosphine ruthenium chloride as a catalyst are added into the reaction kettle and mixed uniformly, heated to 50-60°C and kept at the temperature for 4h until the eugenol content is less than 1%. Then, it was directly distilled under reduced pressure to obtain 495 g of isoeugenol with a content of 98.5%, with a mass yield of 99%. |
82% | In methanol; water at 100℃; for 20h; |
78% | With potassium fluoride on basic alumina In ethylene glycol at 200℃; for 1.5h; | |
69.72% | With potassium hydroxide at 140℃; for 4h; | |
64% | With cholin hydroxide; potassium hydroxide In water at 220℃; for 2.5h; | 1.1; 2.1 step 1: Preparation of isoeugenol (3a) form eugenol (2a) (a) In a round bottom flask, eugenol (0.1 g, 0.61 mmol), choline hydroxide (46% assay w/win aqueous solution, 0.5 g, 4.27 mmol), and potassium hydroxide (0.2 g, 3.65 mmol) was taken and was allowed to reflux for 2.5 h at temp 220°C. The progress of the reaction was monitored by GC analysis. After completion of the reaction, the reaction mixture was neutralized with con. HC1 (0.5 mL) followed by its extraction with ethyl acetate and water. The organic layer was dried over anhydrous sodium sulfate and concentrated to an oily crude material. The crude material was purified by column chromatography on silica gel (100-200 mesh size) using ethyl acetate-hexane as eluent which yielded pure isoeugenol (3a, a mixture of cis and trans) as oil. The conversion from eugenol to isoeugenol was 64% (GC analysis; cis: trans = 21:43). |
With platinum on activated charcoal at 300℃; im Kohlendioxyd-Strom; | ||
With potassium hydroxide; diethylene glycol at 160 - 180℃; | ||
With potassium hydroxide; glycerol at 180℃; | ||
With potassium hydroxide; pentan-1-ol at 140℃; | ||
With potassium hydroxide at 130 - 140℃; | ||
With pentan-1-ol; sodium | ||
With potassium hydroxide at 220℃; | ||
With potassium hydroxide; water at 220℃; Loesen in Wasser und Ansaeuern; | ||
With potassium hydroxide beim Schmelzen; | ||
With potassium hydroxide; sodium hydroxide beim Schmelzen; | ||
With 10% KOH/alumina | ||
With hexaaquaruthenium(II) tosylate In ethanol at 20℃; | ||
99 %Chromat. | 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); di-μ-bromobis(tri-tertbutylphosphine)dipalladium(I) In toluene at 50℃; for 1h; Inert atmosphere; | |
With potassium hydroxide at 130 - 140℃; | ||
With potassium hydroxide; pentan-1-ol at 140℃; | ||
With MCM-22 zeolites dispersed on palladium In N,N-dimethyl-formamide at 200℃; for 6h; Autoclave; | 2.3a Isomerisation of Eugenol To understand thesurface basicity, the cations exchanged MCM-22 catalystswere studied for the isomerization of eugenol in a liquid phaseautoclave reactor at 200 °C for 6 h. All the alkali metal ionexchangedsamples were applied for the isomerisation ofeugenol. Prior to the reaction, the catalysts were activated byheating in an air oven at 70 °C for 1 h. Approximately 0.2 g ofeugenol (*0.188 mL) was introduced into the autoclavereactor having 2.5 mL of DMF as a solvent. Then, 0.05 g ofthe alkali and alkaline earth metal-containing MCM-22catalyst was added into the reactor. The temperature of thereactor was set to 200 °C and the reaction was continued for6 h. After the reaction, the catalyst was separated by filtrationand the products were analysed by gas chromatography (GC)equipped with ZB-5 capillary column (non-polar column)and a flame ionization detector. The products were confirmedbased on the retention time of the authentic samples receivedcommercially. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99.9% | With hydrogen In toluene at 100℃; for 0.25h; Flow reactor; | |
98.2% | With methanol; nickel boride; diborane for 0.5h; Ambient temperature; | |
98% | With hydrogen In methanol at 20℃; for 20h; chemoselective reaction; | 4.3. Typical procedure for the chemoselective hydrogenation General procedure: The mixture of the substrate (0.250 mmol), 0.5% Pd/MS3A or 0.5% Pd/MS5A (10 wt % of the substrate) and MeOH (1 mL) was stirred under H2 atmosphere (balloon) at room temperature. After a given period, the reaction mixture was filtered through a membrane filter (Millipore, Millex-LH, 0.45 mm), and the filtrate was concentrated in vacuo to produce the corresponding reduced product. |
95% | With Wilkinson's catalyst; hydrogen In dichloromethane at 125℃; | |
91% | With cobalt In tetrahydrofuran Heating; High pressure; | |
87% | With formic acid; tri-tert-butyl phosphine In tetrahydrofuran at 20℃; for 12h; | |
87% | With formic acid; tri-tert-butyl phosphine In tetrahydrofuran at 20 - 60℃; for 12h; | |
With nickel at 100℃; Hydrogenation; | ||
With ethanol; nickel at 20℃; Hydrogenation; | ||
With methanol; Pd-BaSO4 Hydrogenation; | ||
With nickel Hydrogenation; | ||
With palladium on activated charcoal; ethanol Hydrogenation; | ||
With diethyl ether; platinum Hydrogenation; | ||
With nickel at 92℃; Hydrogenation.unter erhoehtem Druck; | ||
With nickel at 20℃; Hydrogenation; | ||
With hydrogen | ||
With hydrogen In ethanol at 20℃; for 1h; | ||
With formic acid; ammonium formate; silica gel; palladium dichloride In water at 120℃; Microwave irradiation; | ||
With 5%-palladium/activated carbon; hydrogen In methanol for 2h; | ||
With Pt-H-Beta-300 zeolite In dodecane at 200℃; for 0.5h; Autoclave; | ||
With hydrogen In methanol; water at 140℃; for 3h; Autoclave; | ||
With sodium dithionite In water; butan-1-ol at 200℃; for 3h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95.3% | With dihydrogen peroxide; horseradish peroxidase In aq. phosphate buffer; water; acetone at 50℃; for 2h; | 2 2.2. Synthesis of lignin model compound Isoeugenol (2.4630 g), phosphate buffer solution (60 mL, pH 5.83), acetone (45 mL) and 10 g/L horseradish peroxidase (4.5 mL) were added into a flask equipped with a magnetic stirrer, and then 30% hydrogen peroxide (1.8700 g) was dropwise added. After reaction at 50 °C for 2 h, the crude product was extracted with ethyl acetate and dried under vacuum. The resulting product was further purified by column chromatography with silica gel using dichloromethane/n-hexane (1/5, v/v) as the mobile phase. The purified compound 2 was obtained with the yield of 95.3% after evaporation under vacuum. 1H NMR (400 MHz, DMSO-d6): δ 1.32 (d, 3H, J = 8.0 Hz, γ-CH3), 1.83 (d, 3H, J = 4.0 Hz, γ'-CH3), 3.81 (s, 6H, 2 x OCH3), 3.41 (m, 1H, Hβ), 5.11 (d, 1H, J = 8.0 Hz, Hα), 6.16 (m, 1H, Hβ'), 6.35 (d, 1H, J = 12.0 Hz, Hα'), 6.87-7.12 (m, 5H, aromatics), 9.06 (s, 1H, OH); HRMS calculated for C20H22O4 [M+H]+ 327.1591, found 327.1599. |
32% | With urea hydrogen peroxide adduct; horseradish peroxidase In water; acetone at 20℃; for 1h; Enzymatic reaction; | |
23% | With calli of Bouvardia ternifolia In acetone at 25℃; for 120h; |
19% | With dihydrogen peroxide In methanol for 25h; Ambient temperature; horseradish peroxidase, phosphoric buffer pH 6; | |
With ethanol; iron(III) chloride Hinzugeben von Wasser; | ||
With TiO2 In N,N-dimethyl-formamide for 4h; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With dihydrogen peroxide In acetonitrile at 90℃; for 2h; | The reaction was carried out in a carousel with a Pyrex tube. For the oxidation reaction ofisoeugenol, 8 mL acetonitrile, 1.2 mL H2O2 (hydrogen peroxide) solution (20 mmol H2O2), and 0.8 mLisoeugenol (5 mmol) were poured into a Pyrex tube with 0.1 g of catalyst. Products were analyzedat dierent time intervals by a Gas chromatograph (7890A model, Agilent Technologies, Santa Clara,CA, USA) fitted with a capillary column Petrocol 100 m 0.25 mm and 0.5 m and a flame ionizationdetector (FID). The results were finally confirmed by GC-MS. |
70% | Stage #1: 2-methoxy-4-propenylphenol With 2,6-dimethylpyridine; osmium(VIII) oxide In tetrahydrofuran; water for 0.916667h; Cooling with ice; Stage #2: With sodium periodate In tetrahydrofuran; water at 25℃; for 3h; Cooling with ice; | 1.2; 2.1 (b) On ice bath, isoeugenol (3a, 10.00g, 60.97 mmol) was taken in around bottom flask and dissolved in 300 mL mixture of tetrahydrofuran (THF) and water (4: 1). After 15 min, osmium tetroxide (OsO4, 0.2% aqueous solution, 100mL) was dropwise added to the solution (in about 20- 30 min). After 10 min, 2,6-dimethylpyridine (6.80g, 60.97 mmol) was added to the reaction mixture which was stirred further for 30 min. Subsequently, sodium metaperiodate (NalO4, 32.49 g, 152.43 mmol) was added to the reaction mixture portion- wise (in about 20 min) and stirring was continued for 3h at 25°C. The progress of the reaction was monitored by TLC (20% ethyl acetate- hexane). After completion of the reaction, it was worked up using ethyl acetate and water. The organic layer was separated, dried over anhydrous sodium sulfate (Na2SO4), and concentrated. The crude material was purified by column chromatography over silica gel 100-200 mesh size using ethyl acetate-hexane (10:90) as eluent which yielded pure vanillin (la) as a white solid in 70% yield. |
58% | With Rhodococcus rhodochrous MTCC 289 at 30℃; for 72h; |
49% | With water; ozone In ethyl acetate at 0℃; for 0.00277778h; Flow reactor; | Standard ozonolysis procedure. General procedure: The syringe pumps and the lm-shear reactorwere primed by running 50 mL EtOAc at 10 mL/min and 50 mL deionized H2O at 10 ml/min with the rotor running at 2000 RPM. This procedure was repeated with pure oxygen also owing at 0.8 L/min The lm-shear reaction chamberwas cooled to 0 C with a recirculator. Both a 0.10 M solution of alkene in EtOAc at 0 °C and deionized water at 0 °C were pumped into a ‘T’ valve (10 mL/min each) generating the plug-ow mixture that entered the film-shear reactor. Ozone was sparged through the reaction chamber at 0.8 L/min. Aproduct ask was primed with 2 mol equiv of a sodium sulte solution toquench any hydrogen peroxide produced. The resulting product mixture was collected in a fume hood (CAUTION residual ozone, formaldehyde, andhydrogen peroxide may be present as an aerosol; perform only in a well ventilated hood). The pH was adjusted to 3 using 3 M HCl (aq) . The two resulting layers were separated. The aqueous layer was washed three times with 15 mLof EtOAc, then the organic layers were combined, dried over Na2SO4, filtered,and the solvent was removed under vacuum. The products were puried asnoted in Supplemental information. |
39% | With 1-hydroxy-pyrrolidine-2,5-dione; graphitic carbon nitride In acetonitrile Inert atmosphere; Irradiation; | |
With dihydrogen peroxide; <i>tert</i>-butyl alcohol Reagens 4: CrO3; | ||
With air durch Ueberleiten des Dampfes ueber eine gluehende Platinspirale; | ||
With aqueous alkali elektrolytische Oxydation an Bleidioxyd-Anoden; | ||
With terpentine oil; air | ||
With sodium disulfite; ozone | ||
With alkali Electrolysis; | ||
With peroxidene | ||
With dihydrogen peroxide; <i>tert</i>-butyl alcohol Reagens 4: V2O5; | ||
With tert-Amyl alcohol; dihydrogen peroxide Reagens 4: V2O5; | ||
With tert-Amyl alcohol; dihydrogen peroxide Reagens 4: CrO3; | ||
With peroxidase-substance; dihydrogen peroxide; 4-aminobenzene sulfonic acid | ||
With ozone | ||
With aqueous alkali elektrolytische Oxydation an Platin-Anoden; | ||
With aqueous alkali at 0 - 12℃; elektrolytische Oxydation an Bleidioxyd-Anoden; | ||
With oxygen; acetic acid | ||
With air; acetic acid at 50 - 60℃; Irradiation.mit ultraviolettem Licht; | ||
With ozone; acetic acid | ||
With acetic acid ester; ozone man reduziert das entstandene Ozonid in Aether mit Zink und Eisessig; | ||
With osmium(VIII) oxide; alkali chlorate | ||
With aqueous alkali elektrolytische Oxydation an Eisen-Anoden; | ||
Multi-step reaction with 2 steps 1: alcoholic KOH-solution 2: durch Oxydation zu Vanillin-<2.4-dinitro-phenyl>-aether und Verseifung des letzteren durch Kochen mit alkoh. Kali | ||
Multi-step reaction with 2 steps 1: NaOH-solution 2: sulfuric acid; potassium dichromate / Behandeln des dadurch erhaltenen 2-Methoxy-4-formyl-phenoxessigsaeures mit PCl5 bei 130grad und Zersetzen des Reaktionsproduktes mit kochendem Wasser | ||
With dihydrogen peroxide In acetonitrile at 90℃; for 5h; | Catalytic activity tests General procedure: In a typical experiment, isoeugenol (5 mmol) and 0.1 g catalyst, H2O2(1.2 mL) and acetonitrile (8 mL) were heated at 90 °C under continuous stirring in a carrusel place reaction station. Products were analyzed at different time interval by GC Aligent7890 fitted with a capillary column Petrocol 100 m × 0.25 nm ×0.5 μm and a flame ionization detector (FID). The results were finally confirmed by GC-MS | |
Multi-step reaction with 3 steps 1: triethylamine / dichloromethane / 4 h / 0 °C 2: potassium permanganate / 1.5 h / 40 °C 3: hydrogenchloride / water / 0.33 h / 45 °C / Acidic conditions | ||
With dihydrogen peroxide In acetonitrile at 90℃; for 0.0833333h; Microwave irradiation; | ||
With 9-cis-epoxycarotenoid dioxygenase gene from Serratia sp. ATCC 39,006 (SeNCED) In chloroform; water for 8h; Enzymatic reaction; | ||
With manganese saltene | ||
With tert-Amyl alcohol; dihydrogen peroxide Reagens 4: CrO3; | ||
With tert-Amyl alcohol; dihydrogen peroxide Reagens 4: V2O5; | ||
With dihydrogen peroxide; <i>tert</i>-butyl alcohol Reagens 4: CrO3; | ||
With dihydrogen peroxide; <i>tert</i>-butyl alcohol Reagens 4: V2O5; | ||
With ozone; acetic acid | ||
With osmium(VIII) oxide; alkali chlorate | ||
With hydrogenchloride; ethanol; oxygen; recombinant isoeugenol monooxygenase; 2-amino-2-hydroxymethyl-1,3-propanediol In water; dimethyl sulfoxide at 30℃; for 8h; Enzymatic reaction; | ||
With dihydrogen peroxide In acetonitrile at 80℃; for 6h; Green chemistry; | 2.4. Catalytic activity The catalytic activity of the synthesized materials was investigated inthe wet peroxide oxidation of isoeugenol to vanillin using hydrogenperoxide as oxidant. The reaction was carried out in a parallel reactionstation Carrousel Reaction Station TM (Radleys Discovery Technologies).The reaction conditions were: 0.8 mL of isoeugenol, 1.2 mL ofhydrogen peroxide, 8 mL of acetonitrile as solvent and 0.1 g of catalystat 80 °C for 6 h. Moreover, the reaction was carried out adding the hydrogen peroxide by two steps (0 min and 30 min reaction-time) tostudy the possible improve of catalytic rate. The samples were analysedin a gas chromatograph Agilent Technologies 7890 A using a PetrocolDH (100 m×0,25 mm×0,50 μm) capillary column and a flame ionisationdetector (FID). | |
With dihydrogen peroxide In water; acetonitrile at 90℃; for 0.05h; Microwave irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With phosphoric acid | ||
With sulfuric acid | ||
With acetyl chloride |
With sulfuric acid | ||
With pyridine | ||
With zinc(II) chloride |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | In 1,4-dioxane at 60℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | With tin(IV) chloride In dichloromethane at -78℃; for 0.25h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With formic acid Heating; | ||
With sulfuric acid In methanol for 2h; Reflux; | 150 g of isoeugenol was added to a 1000 mL three-necked flask,350 g of methanol, 95 g of concentrated sulfuric acid,After heating to reflux for 2 hours, the temperature was lowered to 3 ± 2 ° C,To the reaction product, 200 g of water was added, stirred,Drying the cake to obtain dry goods; adding 600 g of methanol to the dried product,Dimethyl sulfate 450g, cooled to 3 ± 2 ,And then dropping 10% sodium hydroxide solution, adjust the pH to 7, filter,The filter cake is dry,To give 210 g of 1- (3,4-dimethoxy-phenyl) -3-ethyl-5,6-dimethoxy-2-methyl-indane. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With sodium hydroxide at 80℃; for 3h; | |
With sodium hydroxide In ethanol | ||
With sodium hydroxide In ethanol for 4h; Heating / reflux; | 1 Epichlorohydrin 100 ml was mixed with isoeugenol 20 ml and NaOH 10 g dissolved in ethanol 10 ml, boiled to reflux for 4 hours. Obtained mixture was removed the included ethanol and passed through silica gel column chromatography, eluated with n-hexane and ethyl acetate (9:1), dryed with reduced pressure and obtained 4-epoxy isoeugenol (63 g). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With sodium carbonate at 100 - 150℃; for 3h; | 1.2; 2.2; 3.2 Esterification reaction: Add 10g of anhydrous sodium carbonate and 390g of acetic anhydride to a 1000ml three-necked flask with a thermometer and reflux condenser, stir and raise the temperature; when the temperature of the system rises to 100, start to add 400g isoeugenol dropwise; continue to heat up to 120 after the drop ; At this time, reflux occurs in the reaction flask, and atmospheric distillation continuously distills out the acetic acid produced by the reaction, so that the reaction temperature is maintained between 130 and 150° C. to continue the reaction for 3 hours. After the reaction is over, 250 g of water is added to quench the reaction and the esterified product is washed. After cooling, 500 g of white crystal isoeugenol acetate with a content of 98.5% is obtained, with a mass yield of 99%. |
95% | at 20℃; for 0.25h; | |
63.08% | With sodium acetate at 120℃; for 1.5h; |
With triethylamine In dichloromethane at 0℃; for 4h; | 3 (3) Phenolic hydroxyl protection Due to the activity of phenolic hydroxyl group, easy to be oxidized,In order to avoid the active phenolic hydroxyl group is also oxidized when the carbon-carbon double bond is oxidized,So step (2)In the obtained eugenol and acetic anhydride reaction of isoeugenol acetate, specifically:Add in a 10 ml dry round bottom flask1.0 g of the isoeugenol,An additional 3 ml of dichloromethane and 0.87 ml of triethylamine were added,Get isoeugenol solution;Add in another large dry test tube0.58 ml of acetic anhydride and 2 ml of dichloromethane,Get acetic anhydride solution;The acetic anhydride solution was slowly added dropwise to the isoeugenol solution in an ice-water bath,The reaction was stirred at 0 ° C for 4 h,After the reaction solution becomes clear,Isoeugenol acetate was obtained,Cryopreservation of the isoeugenol acetate; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With boron trifluoride diethyl etherate; water In dichloromethane; acetonitrile at -15℃; for 0.02h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With boron trifluoride diethyl etherate; water In dichloromethane; acetonitrile at -15℃; for 0.3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | Stage #1: 1,4-divinyloxybutane; 2-methoxy-4-propenylphenol With 4-methoxy-phenol for 0.25h; Stage #2: With benzene-1,2-dicarboxylic acid at 20 - 125℃; for 18h; | 6 To a 250 nriL round bottom flask, equipped with a thermometer and stir bar, were added butanediol divinyl ether (20 ml_, 126 mmol) and isoeugenol (42.6 g, 260 mmol). This solution was stirred for 15 minutes; then, phthalic acid (1.06 g, 6.4 mmol) was added. The reaction flask was placed into a 125°C oil bath. After stirring at 125°C for eight hours and at ambient temperature for another ten hours, the reaction mixture was diluted with toluene (200 mL). Amberlyst A21 resin (10Og) was added and the reaction mixture stirred for one hour. A small amount of isoeugenol still remained as indicated by NMR. NaOH (solid) was added to the mixture and stirred for one hour until no excess amount of isoeugenol was detected. The reaction mixture turned from yellow to dark red after addition of NaOH. The solvent was removed under vacuum to give 35g (60%) dark red viscous liquid with viscosity of 17,000 mPa.s (25°C). ). 1H-NMR (DMSO-d6, in ppm): δ 7.0 (S, 2H)1 6.9 (d, 2H), 6.8 (d, 2H), 6.4 (d, 2H), 6.2 (m, 2H), 5.3 (q, 2H), 3.3-3.7 (m, 10H), 1.8 (d, 6H), 1.3-1.5 (m, 10H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
for 0.333333h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 60% 2: 21 %Chromat. | With acetylacetonatodicarbonylrhodium(l); phosphoric acid; hydrogen; methoxybenzene; triphenylphosphine In dichloromethane at 110℃; for 2h; Autoclave; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | Stage #1: 2-amino-phenol With nitrosyl hexafluorophosphate In tetradecane; acetonitrile at 0℃; for 0.5h; Stage #2: 2-methoxy-4-propenylphenol With tris-(dibenzylideneacetone)dipalladium(0); zinc(II) carbonate In tetradecane; acetonitrile at 20℃; for 20h; diastereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With copper diacetate at 20℃; for 3h; | |
41.5% | With oxygen In water; ethyl acetate at 25℃; for 1.16667h; aq. sodium acetate buffer; Enzymatic reaction; | |
1.12 g | With [bis(acetoxy)iodo]benzene In dichloromethane at 20℃; for 52h; | 1 Synthesis and Identification of K20 The solution of isoeugenol (10 g in 100 mL dichloromethane) was added in drop to the solution of iodobenzene diacetate (IDA; 10 g) in 100 mL of dichloromethane (dry with CaH2) under room temperature (RT) for 4 h. After 48 h, NaHCO3 (3 g) was added to the solution and stirred for 1 h. The mixture was filtrated and the filtrate was evaporated under reduced pressure to give the intermediate 1. The intermediate 1 (1.12 g) and dichlorodicyano-benzoquinone (DDQ; 3.24 g) were resolved in 50 mL of 1,4-dioxane. The solution was then refluxed. After 48 h, the solution was filtrated and the filtrate was evaporated under reduced pressure to give the intermediate 2. The solution of the intermediate 2 (1.33 g in 20 mL of CH3OH) with 10% PtO2 (96.3 mg in H2O) was stirred under H2 at RT. After 6 h, the mixture was filtrated and the filtrate was evaporated under reduced pressure to give the intermediate 3. The solution of the intermediate 3 (0.64 g in 20 mL ethanol) with SeO2 (0.42 g) was refluxed. After 12 h, the mixture was evaporated under reduced pressure and then adds 30 mL of ethyl acetate (EtOAc). The mixture was filtrated by celite and the filtrate was evaporated under reduced pressure and then the residue was purified by silica gel column chromatography (Silica gel 60, Merck 70-230 mesh) eluting with EtOAc/hexane (1:5) to give compound K20. H1-NMR (CDCl3) δ 10.25 (s, 1H, CHO), 7.64 (s, 1H, H-2’), 7.37 (d, J=8.0 Hz, 1H, H-6’), 7.35 (s, 1H, H-4), 7.04 (d, J=8.0 Hz, 1H, H-5’), 6.73 (s, 1H, H-6), 6.11 (broad s, 1H, Ph-OH), 4.00 (s, 3H, OMe), 3.97 (s, 3H, OMe), 3.69 (t, J=6.5 Hz, 2H, H-3”),2.80 (t, J=7.3 Hz, 2H, H-1”), 1.94 (m, 2H, H-2”); C13-NMR (CDCl3) δ 186.8, 165.9, 148.7, 146.9, 144.6, 141.6, 139.9, 127.3, 123.7, 120.6, 116.7, 115.0, 113.5, 111.0, 108.8, 62.2, 56.3, 56.1, 34.7, 32.5; IR (KBr) vmax: 3513, 3435, 2940, 2864, 1637, 1601, 1522, 1490, 1409, 1273, 1139, 1061, 818 cm-1; ELMS m/z (%) (70 eV) 356 (M+, 60; C20H20O6), 312 (100), 269 (7), 197 (6), 152 (6), 137 (6), 126 (4), 105 (4), 91(4), 55 (4); |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40% | With aluminum isopropoxide; at 140℃; for 3h;Inert atmosphere; | General procedure: A two-necked flask equipped with a thermometer and N2 gas inlet was charged with phenols (2 equiv.) and heated up to 140 C and added Al(O-i-Pr)3 (20% mol). After catalyst and phenol were completely dissolved, the solution was treated with isoeugenol (1 equiv.). The reaction was carried out through keeping the temperature at 140 C for 3 h. When the reaction was complete, the mixture was cooled, diluted with ethyl acetate, and treated with HCl solution (5%) to compose the catalyst. Then, the mixture was washed with saturated NaHCO3 solution and water until rinsing was neutral. The organic layer was dried over anhydrous Na2SO4. The solvent was evaporated, and the crude products were purified by column chromatography (on a silica gel column) using n-hexane/EtOAc (9:1) as eluent. The products were crystallized from n-hexane/EtOAc (9:1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | With aluminum isopropoxide at 140℃; for 3h; Inert atmosphere; | 5.1.1. General procedure for the synthesis of compounds 7-12 General procedure: A two-necked flask equipped with a thermometer and N2 gas inlet was charged with phenols (2 equiv.) and heated up to 140 °C and added Al(O-i-Pr)3 (20% mol). After catalyst and phenol were completely dissolved, the solution was treated with isoeugenol (1 equiv.). The reaction was carried out through keeping the temperature at 140 °C for 3 h. When the reaction was complete, the mixture was cooled, diluted with ethyl acetate, and treated with HCl solution (5%) to compose the catalyst. Then, the mixture was washed with saturated NaHCO3 solution and water until rinsing was neutral. The organic layer was dried over anhydrous Na2SO4. The solvent was evaporated, and the crude products were purified by column chromatography (on a silica gel column) using n-hexane/EtOAc (9:1) as eluent. The products were crystallized from n-hexane/EtOAc (9:1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 35% 2: 55% | With aluminum isopropoxide at 140℃; for 3h; Inert atmosphere; | 5.1.1. General procedure for the synthesis of compounds 7-12 General procedure: A two-necked flask equipped with a thermometer and N2 gas inlet was charged with phenols (2 equiv.) and heated up to 140 °C and added Al(O-i-Pr)3 (20% mol). After catalyst and phenol were completely dissolved, the solution was treated with isoeugenol (1 equiv.). The reaction was carried out through keeping the temperature at 140 °C for 3 h. When the reaction was complete, the mixture was cooled, diluted with ethyl acetate, and treated with HCl solution (5%) to compose the catalyst. Then, the mixture was washed with saturated NaHCO3 solution and water until rinsing was neutral. The organic layer was dried over anhydrous Na2SO4. The solvent was evaporated, and the crude products were purified by column chromatography (on a silica gel column) using n-hexane/EtOAc (9:1) as eluent. The products were crystallized from n-hexane/EtOAc (9:1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With aluminum isopropoxide at 140℃; for 3h; Inert atmosphere; | 5.1.1. General procedure for the synthesis of compounds 7-12 General procedure: A two-necked flask equipped with a thermometer and N2 gas inlet was charged with phenols (2 equiv.) and heated up to 140 °C and added Al(O-i-Pr)3 (20% mol). After catalyst and phenol were completely dissolved, the solution was treated with isoeugenol (1 equiv.). The reaction was carried out through keeping the temperature at 140 °C for 3 h. When the reaction was complete, the mixture was cooled, diluted with ethyl acetate, and treated with HCl solution (5%) to compose the catalyst. Then, the mixture was washed with saturated NaHCO3 solution and water until rinsing was neutral. The organic layer was dried over anhydrous Na2SO4. The solvent was evaporated, and the crude products were purified by column chromatography (on a silica gel column) using n-hexane/EtOAc (9:1) as eluent. The products were crystallized from n-hexane/EtOAc (9:1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
25% | With aluminum isopropoxide at 140℃; for 3h; Inert atmosphere; | 5.1.1. General procedure for the synthesis of compounds 7-12 General procedure: A two-necked flask equipped with a thermometer and N2 gas inlet was charged with phenols (2 equiv.) and heated up to 140 °C and added Al(O-i-Pr)3 (20% mol). After catalyst and phenol were completely dissolved, the solution was treated with isoeugenol (1 equiv.). The reaction was carried out through keeping the temperature at 140 °C for 3 h. When the reaction was complete, the mixture was cooled, diluted with ethyl acetate, and treated with HCl solution (5%) to compose the catalyst. Then, the mixture was washed with saturated NaHCO3 solution and water until rinsing was neutral. The organic layer was dried over anhydrous Na2SO4. The solvent was evaporated, and the crude products were purified by column chromatography (on a silica gel column) using n-hexane/EtOAc (9:1) as eluent. The products were crystallized from n-hexane/EtOAc (9:1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 62 %Chromat. 2: 32 %Chromat. 3: 6 %Chromat. | With C44H34N4O8P2Rh2S2(2-)*2Na(1+); hydrogen; cetyltrimethylammonium chloride In water; toluene at 80℃; for 8h; chemoselective reaction; | |
1: 62 %Chromat. 2: 31 %Chromat. 3: 6 %Chromat. | With C44H34N4O8P2Rh2S2(2-)*2Na(1+); hydrogen; cetyltrimethylammonium chloride In water; toluene at 80℃; for 3h; chemoselective reaction; | |
With hydrogen In toluene at 70℃; for 17h; Inert atmosphere; Schlenk technique; | Catalytic runs General procedure: A mechanically stirred stainless steel Parr 4560 bomb coupled with a 4282 control module with a PID temperature controller and tachometer was employed as the reaction vessel. The bomb was loaded with the solid catalyst and three cycles of vacuum/argon were made. The solvent (15 mL) and the substrate (5 mmol) were introduced with a syringe through a valved port under argon. The vessel was pressurized with carbon monoxide followed by hydrogen up to the reported pressure. Stirring and heating were then started, and the desired temperature was attained in about 5 min. At appropriate time intervals, stirring was stopped and liquid samples were taken through a valved dip tube after quick catalyst settling. Recycling experiments were performed maintaining the catalyst in the vessel and washing it with the same solvent employed in the reaction before a new cycle to remove product residues. |
With methoxy(cyclooctadiene)rhodium(I) dimer; hydrogen In toluene at 80℃; for 0.5h; Autoclave; Inert atmosphere; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With iron(III) p-toluenesulfonate hexahydrate In methanol at 20℃; for 2h; | Representative procedures General procedure: Method A: A solution of the THP ether of cinnamyl alcohol (entry 5) (1.00 g, 4.58 mmol) in CH3OH (10 mL) was stirred at room temperature as Fe(OTs)3·6H2O (0.0621 g, 0.0916 mmol, 2.0 mol %) was added. The reaction progress was monitored by TLC (EtOAc/heptane, 30/70). After 4 h 30 min, water (15 mL) was added and methanol was removed on a rotary evaporator. The resulting mixture was extracted with EtOAc (2 × 20 mL). The organic layer was washed with saturated aqueous NaHCO3 (15 mL), saturated aqueous NaCl (15 mL), dried (Na2SO4), and concentrated on a rotary evaporator to yield 0.59 g of the crude product. The crude product was purified by flash chromatography (35 g silica gel, EtOAc/heptane, 30/70) to yield 0.49 g (80%) of a white solid that was identified to be cinnamyl alcohol. The purity was estimated to be >98% by 1H and 13C NMR spectroscopy, and GC analysis. Method B: A solution of the THP ether of 1-ethynyl-1-cyclohexanol (entry 10) (0.50 g, 2.40 mmol) in CH3OH (5 mL) was stirred at room temperature as Fe(OTs)3·6H2O (0.0325 g, 0.0480 mmol, 2.0 mol %) was added. The reaction progress was monitored by TLC (EtOAc/heptane, 30/70). After 2 h, CH3OH was removed on a rotary evaporator and the residue was purified by flash chromatography (35 g silica gel, EtOAc/pentane, 30/70) to yield 0.23 g (77%) of a colorless liquid that was identified to be 1-ethynyl-1-cyclohexanol. The purity was estimated to be >98% by 1H and 13C NMR spectroscopy, and GC analysis. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | With 2-pyrazylcarboxylic acid; dihydrogen peroxide; [n-Bu4N]VO3 In water; acetonitrile at 80℃; for 2h; | All reagents were purchased from commercial sources and used as received. Isoeugenol (a mixture of cis and trans isomers) from Aldrich was used as the substrate. Catalyst [42] and co-catalyst (PCA) were used as stock solutions. The oxidations of 1 were carried out in MeCN in air in thermostated Pyrex vessels with vigorous stirring. The total volume of the reaction solution was 5 mL. Initially, a portion of H2O2 (a 29% aqueous solution from Synth) was added to the solution of the catalyst, co-catalyst and substrate. After certain time intervals samples (about 0.2 mL) were taken. The samples of reaction solutions were analyzed by GC using a Shimadzu 17A instrument fitted with a Carbowax 20M capillary column and a flame ionization detector. The details of the experiments are given in the captions for figures. The structures of the products were confirmed by GC/MS (Shimadzu QP2010-PLUS instrument, 70 eV). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With methoxy(cyclooctadiene)rhodium(I) dimer; trifluorormethanesulfonic acid; hydrogen; triphenylphosphine In toluene at 120℃; for 24h; | 2.2 Catalytic runs The pre-catalyst [Rh(cod)(μ-OMe)]2 (5.0 × 10-3 mmol), the phosphorus ancillary (if any) and a PTFE-covered magnetic stirring bar were placed in a stainless steel bomb, which was closed and purged with three cycles of vacuum and argon. In a Schlenk tube, a solution was prepared by adding toluene (30 mL), eugenol (10 mmol), di-n-butylamine (10 mmol) and then the acid (if any). The solution was transferred under inert atmosphere to the bomb, which was pressurized with carbon monoxide (10-20 atm) and then with hydrogen (to 40-80 atm). The bomb was placed in a pre-heated silicone bath over magnetic stirring. Liquid samples were taken periodically through a dip tube. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With methoxy(cyclooctadiene)rhodium(I) dimer; sulfuric acid; hydrogen; triphenylphosphine In toluene at 120℃; for 24h; | 2.2 Catalytic runs The pre-catalyst [Rh(cod)(μ-OMe)]2 (5.0 × 10-3 mmol), the phosphorus ancillary (if any) and a PTFE-covered magnetic stirring bar were placed in a stainless steel bomb, which was closed and purged with three cycles of vacuum and argon. In a Schlenk tube, a solution was prepared by adding toluene (30 mL), eugenol (10 mmol), di-n-butylamine (10 mmol) and then the acid (if any). The solution was transferred under inert atmosphere to the bomb, which was pressurized with carbon monoxide (10-20 atm) and then with hydrogen (to 40-80 atm). The bomb was placed in a pre-heated silicone bath over magnetic stirring. Liquid samples were taken periodically through a dip tube. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With water;HUSY (Si/Al=15); at 250℃; under 5250.53 Torr; for 2h;Inert atmosphere;Product distribution / selectivity; | In an autoclave (batch reactor) lignin (0.5 g), HUSY (Si/Al=15) (0.5 g) and mixture of water and organic solvent (30 g) were charged. After flushing the reactor with nitrogen gas for 3 times, nitrogen (7 bar) was charged. Reactor was heated up to 230° C. under the stirring (100 rpm). After attaining the desired temperature of 230° C. stirring was increased up to 500 rpm. Reaction was stopped after 30 minutes. Analysis of reaction mixture was done by GC, GC-MS. The lignin used in these examples were organosolv or dealkaline.Yield: >25percentMass balance: >90percent.The effect of reaction temperature and reaction time on depolymerization reaction is demonstrated by the results presented in Table 8 using SiO2-Al2O3 as catalyst*. TABLE 8 Exp. Time Lignin Product yield, Mass balance, No. (min.) conversion percentpercentNo. percent 1. 30 85 26 80 2. 60 85 41 86 3. 90 92 50 84 4. 120 95 70 85 Lignin, 0.5 g; HUSY (Si/Al = 15), 0.5 g; N2 Pressure, 7 bar (at)RT; Temperature, 250° C.No.Monomer and dimer products soluble in water/organic solvents. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 5% palladium on Al2O3; hydrogen; In water; at 25 - 310℃; under 37503.8 Torr; for 1h;Autoclave; | The lignin used in Examples 4 to 13 is of the Acetosolv type for Examples 4, 5 and 6 (comparative) and for Examples 9, 10, 11 and 13 (invention), of the Organosolv type for Examples 7 and 8 (invention) and of the Kraft type for Example 12 (invention). [0154] The lignin of the Acetosolv type was obtained from a mixture of fir/pine wood, operating as described in the article of X. Pan et al. ?Acetic acid pulping of wheat straw under atmospheric pressure?, published in ?Journal of Wood Science? (1999), Vol. 45 (4), pages 319-325. The lignins of the Organosolv and Kraft types used are commercial products from the Aldrich catalogue cod. 371017 (batch 10228TC) and cod. 471003 (batch 09724CE), respectively. [0155] The lignins of the Acetosolv type, of the Organosolv type and of the Kraft type used have the following elemental composition: The lignins of the Acetosolv type, of the Organosolv type and of the Kraft type used have the following elemental composition: [0156] C % 67.1; H % 5.3; N % 0.1; S % 0.0; O % 27.6 (lignin of the Acetosolv type); [0157] C % 66.7; H % 5.3; N % 0.2; S % 0.0; O % 28.9 (lignin of the Organosolv type); [0158] C % 63.3; H % 6.9; N % 0.2; S % 4.3; O % 25.4; inorganic ashes 17.5% (lignin of the Kraft type). [0159] 10 g of lignin were added to a stirred 0.5 1 Hastelloy C autoclave containing 100 g of a solvent (the type of solvent is reported in Table 1) and a catalyst (the type of catalyst is reported in Table 1). The autoclave was closed and pressurized with about 5 MPa of hydrogen at room temperature (25 C.). [0160] The autoclave was then stirred at 600 rpm and heated to the temperature and for the time reported in Table 1. At the end, the autoclave was left to cool to room temperature (25 C.), again under stirring, and the gas released was measured by means of a liters counter and analyzed by means of gas chromatography in order to determine the content of C1-C4 hydrocarbons and carbon monoxide and carbon dioxide. [0161] The mixture obtained, comprising a first liquid phase and a solid phase, was filtered obtaining a first liquid phase comprising part of the depolymerized lignin and a solid phase comprising the catalyst and the remaining part of the depolymerized lignin. [0162] Said liquid phase was subjected to evaporation in order to recover the depolymerized lignin (fraction 1) and the solvent which can be re-used for the hydrogenolysis of lignin. [0163] Said solid phase was subjected to extraction with 200 ml of acetone obtaining a solution comprising depolymerized lignin and catalyst. Said solution was filtered so as to obtain a solid residue comprising the catalyst and a second liquid phase comprising depolymerized lignin and acetone. [0164] The depolymerized lignin was recovered by evaporation of the acetone (fraction 2). Said fraction 2 and said fraction 1 were joined and sent to the hydrotreating reactor. [0165] The above solid residue comprising the catalyst was dried in an oven, at 110 C., for 24 hours and subsequently calcined at about 500 C., for 6 hours, in the air. The difference in weight between the dried catalyst and the calcined catalyst in relation to the starting lignin provides the residue reported in Table 1. The calcined catalyst can be re-used for the hydrogenolysis of lignin. [0166] As reported above, FIG. 1 indicates a gas chromatography/mass spectrometry (GC-MS) typical of the depolymerized lignin, obtained operating as described in Example 9 reported in Table 1, where, in the abscissa is reported the analysis time and in the ordinate is reported the abundance of the various compounds present. The gas chromatography/mass spectrometry (GC-MS) was carried out using an Agilent gas chromatograph mod. 7890 equipped with a Mass Spectrometry Detector MSD 5975C. As can be seen in FIG. 1, the depolymerized lignin obtained as described above comprises phenols, alkyl phenols and methoxy alkyl phenols. [0167] The depolymerized lignin obtained after joining said fraction 1 and said fraction 2 was weighed and subjected to elemental analysis by means of a Thermo Scientific Flash CHNS-O analyzer, in order to determine its content of carbon, hydrogen, nitrogen, sulphur and, by difference, oxygen: the data obtained are reported in Table 2. From the data reported in Table 2, it can be deduced that during the hydrogenolysis, a partial deoxygenation of lignin is obtained. [0168] From the data reported in Table 1, it can also be deduced that the lignin of the Acetosolv type and the lignin of the Organosolv type, after hydrogenolysis, are completely soluble in acetone, the solvent used for recovering them (Examples 7-11 and 13), whereas, for the lignin of the Kraft type, an insoluble residue equal to 4% by weight with respect to the total weight of the starting lignin (Example 12) can be observed. It can also be deduced that the presence of the catalyst is essential: Example 4 carried out in the absence of the catalyst, in fact, shows a residue of lignin (33% by weight with respe... |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90.6% | With potassium carbonate In N,N-dimethyl-formamide at 80℃; for 0.5h; Microwave irradiation; | 5 3-Methoxy-4-benzyloxy-α-(2-methoxy-4-(1-propenyl)phenol)-acetophenone (4) 0.720 g (2.15 mmol) compound 3, 0.492 g (3 mmol) isoeugenol, and 0.414 g (3 mmol) powdered potassium carbonate in 10 mL dimethyl formamide were added to a microwave accelerated reaction system. After reacting at 80 °C for 30 min, the reaction mixture was purified using the same processes of compound 3. The resulting yellow crystals were washed with a small amount of petroleum ether and dried at 25 °C under vacuum to give compound 4 in 90.6% yield. 1H NMR (400 MHz, CDCl3): δ 1.83 (s, 3H, CH3), 3.86-3.92 (2 * s, 6H, OCH3), 5.21-5.24 (2 * s, 4H, CH2), 6.06-6.13 (m, 1H, Hβ''), 6.28-6.33 (m, 1 H, Hα''), 6.72-6.89 (m, 4 H, aromatics), 7.29-7.60 (m, 7 H, aromatics); 13C NMR (100 MHz, CDCl3): δ 18.5(Cγ), 56.1 (2 * OCH3), 70.8 (Cα), 72.2 (Cβ'), 122.9 (Cβ''), 128.5 (Cα''), 109.4.7-152.9 (C, aromatics), 193.3 (Cα'). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With 3,5-dinitrobenzoic acid In dichloromethane at 20℃; for 8h; | General procedure for tetrahydropyranylation: General procedure: A solution of alcohol or phenol (1 mmol), dihydro-2H-pyran (1 mmol), and 3,5-dinitrobenzoic acid (0.2 mmol, 20 mol%) in CH2Cl2 (5 mL) were stirred at ambient temperaturea period of time mentioned in Table 2 and monitored by TLC or GC. After completion of thereaction, the organic layer was washed twice with 10 mL of saturated NaHCO3 solution, dried(anhyd. Na2SO4), and concentrated under reduced pressure to yield almost pure product. Theproduct was further purified by column chromatography on silica gel (ethyl acetate/hexanes,1/19, as the eluent). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With methoxy(cyclooctadiene)rhodium(I) dimer; trisodium tris(3-sulfophenyl)phosphine; hydrogen; cetyltrimethylammonim bromide In water at 100℃; for 1h; Autoclave; Schlenk technique; Inert atmosphere; regioselective reaction; | 2.2. Catalytic runs General procedure: The catalytic runs were performed in a mechanically stirredstainless steel Parr 4560 bomb coupled with a 4282 control mod-ule with a PDI temperature controller, tachometer, and a pressuretransducer connected to a field logger apparatus. In a typical exper-iment the catalyst precursor [Rh(COD)(-OMe)]2(2.5 × 10-6mol),TPPTS (5.0 × 10-5mol) and the phase transfer agent cetyltrimethy-lammonium bromide (CTAB, 0.0-2.0 × 10-4mol) were dissolvedin 20 mL of deoxygenated water in a Schlenk tube under argon.The solution was transferred into the bomb, and the substrate(1.0-2.0 × 10-2mol) was placed in a pressure-equalized reservoiron the top of the bomb. The reactor was pressurized with thedesired carbon monoxide pressure (5-20 bar) and then with hydro-gen (5-20 bar) up to the desired total pressure. The bomb washeated to the desired temperature (80-120C) and kept for onehour under mechanical stirring (750 rpm). The substrate was thenadded and the register of the syngas pressure drop was initiated.After pressure drop stopped, the reactor was cooled, vented, theorganic phase was extracted with toluene (20 mL) and analysed by GC. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With iron(III) trifluoromethanesulfonate; 2-((4R,5R)-1-((4-(tert-butyl)phenyl)sulfonyl)-4,5-diphenylimidazolidin-2-yl)-6-((4R,5R)-1-((4-(tert-butyl)phenyl)sulfonyl)-4,5-diphenylimidazolidin-2-yl)pyridine; oxygen In 1,2-dichloro-ethane at 78℃; for 16h; Green chemistry; chemoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride In neat (no solvent) at 90℃; for 1.33333h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen at 70℃; for 5h; Inert atmosphere; Schlenk technique; | Catalytic runs General procedure: A mechanically stirred stainless steel Parr 4560 bomb coupled with a 4282 control module with a PID temperature controller and tachometer was employed as the reaction vessel. The bomb was loaded with the solid catalyst and three cycles of vacuum/argon were made. The solvent (15 mL) and the substrate (5 mmol) were introduced with a syringe through a valved port under argon. The vessel was pressurized with carbon monoxide followed by hydrogen up to the reported pressure. Stirring and heating were then started, and the desired temperature was attained in about 5 min. At appropriate time intervals, stirring was stopped and liquid samples were taken through a valved dip tube after quick catalyst settling. Recycling experiments were performed maintaining the catalyst in the vessel and washing it with the same solvent employed in the reaction before a new cycle to remove product residues. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With 1,8-diazabicyclo[5.4.0]undec-7-ene In N,N-dimethyl-formamide at 80℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With bis(1,5-cyclooctadiene)iridium(I) tetrafluoroborate; anhydrous Sodium acetate In 2-methyltetrahydrofuran at 100℃; for 5h; Schlenk technique; Inert atmosphere; Sealed tube; | |
37% | With di-μ-chlorobis[(1,2,5,6-η)-1,5-cyclooctadiene]diiridium; anhydrous sodium carbonate In toluene at 100℃; for 2h; Inert atmosphere; | 11 Synthesis of Isoeugenol Vinyl Ether To a mixture of [IrCl(cod)]2 (0.656 mmol) and Na2CO3 (39.36 mmol) in toluene (66 mL) were added isoeugenol (65.6 mmol) and vinyl acetate (131.18 mmol) under N2. The reaction mixture was stirred at 100° C. for 2 h. After quenching with wet ether, the product was isolated by silica gel column chromatography using hexane as the eluent. Isoeugenol vinyl ether was obtained as colorless liquid in 37% yield. 1H NMR (400 MHz, CDCl3) δ 1.89 (m, 3H), 3.85 (s, 3H), 4.35 (m, 1H), 4.64 (m, 1H), 6.13 (m, 1H), 6.34 (dd, J=15.6, 1.2 Hz, 1H), 6.57 (m, 1H), 6.82-6.90 (m, 2H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With silver trifluoromethanesulfonate; gold(I) chloride at 20℃; for 4.5h; Ionic liquid; Overall yield = 79 %; Overall yield = 80 mg; stereoselective reaction; | Gold(III)-Catalyzed Dimerization of 1-Phenylpropenes 1, 3, and 5to 2,3-Dihydro-1H-indenes 2, 4, and 6 in Ionic Liquid; General Procedure Gold catalyst (2 mol% of AuCl) and silver catalyst (2 mol% of AgOTf)were added at r.t. to a solution of 1-phenylpropene (1, 3, or 5) in[EMIM][NTf2] and the mixture was stirred at the same temperature.After complete consumption of the 1-phenylpropenes (the reactionwas monitored by TLC), the product was extracted with Et2O and thesolvent was removed in vacuo. The crude product was subjected tocolumn chromatography on silica gel (hexane-EtOAc, 2:1) to give thecorresponding 2,3-dihydro-1H-indenes 2, 4, and 6, respectively.α-Diisoeugenol (2)Isoeugenol (1; 102 mg, 0.622 mmol), AuCl (3.5 mg, 0.015 mmol, 2mol%), and AgOTf (3.6 mg, 0.014 mmol, 2 mol%) in [EMIM][NTf2] (1mL) furnished α-diisoeugenol (2) (80.0 mg, 79%, α/γ = 9:1) as a colorlesssolid; mp 179-180 °C.11cIR (KBr): 3649, 3364, 2872, 1596, 1499, 1375, 1339, 1288, 1261, 1227,1207, 1151, 1088, 1059, 1034, 866, 845, 818, 773, 760 cm-1.1H NMR (300 MHz, CDCl3): δ = 0.98 (t, J = 7.5 Hz, 3 H), 1.03 (d, J = 6.9Hz, 3 H), 1.38 (ddq, J = 13.5, 6.3, 4.5 Hz, 1 H), 1.70 (ddq, J = 13.2, 7.8,5.4 Hz, 1 H), 2.46 (ddq, J = 9.6, 7.2, 6.9 Hz, 1 H), 2.91 (ddd, J = 8.7, 7.5,5.4 Hz, 1 H), 3.74 (d, J = 9.6 Hz, 1 H), 3.82 (s, 3 H), 3.90 (s, 3 H), 5.46 (s,1 H), 5.49 (s, 1 H), 6.47 (d, J = 0.6 Hz, 1 H), 6.61 (d, J = 1.8 Hz, 1 H), 6.65(dd, J = 8.4, 1.8 Hz, 1 H), 6.77 (s, 1 H), 6.84 (d, J = 8.4 Hz, 1 H).13C NMR (75 MHz, CDCl3): δ = 12.7, 14.2, 22.8, 49.0, 49.7, 56.4, 56.6,57.2, 107.9, 111.1, 111.4, 114.4, 121.9, 136.2, 139.1, 139.6, 144.5,145.0, 145.6, 146.9.HRMS (FAB): m/z [M + H]+ calcd for C20H24O4: 328.1675; found:328.1670. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94.8% | With hydrogen In water at 120℃; for 12h; Autoclave; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 72% 2: 25 %Spectr. | With trimethylaluminum; cesium fluoride; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; cobalt acetylacetonate In N,N-dimethyl acetamide; toluene at 60℃; for 12h; Inert atmosphere; Sealed tube; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With aluminium(III) iodide; diisopropyl-carbodiimide In acetonitrile at 80℃; for 18h; | Hydroxychavicol (4-Allylbenzene-1,2-diol, 2); General Procedure General procedure: To a suspension of AlI3 (5.5 mmol, 1.1 equiv) in hot CH3CN (40 mL) were added sequentially DIC (0.379 g, 3 mmol, 0.6 equiv) and eugenol (1, 0.821 g, 5.0 mmol). The mixture was stirred for 18 h at 80 °C, and then it was cooled to r.t., acidified with HCl (2 mol/L, 10 mL), and extracted with EtOAc (3 × 50 mL). The organic phases were combined, washed with sat. aq Na2S2O3 (10 mL) and brine (10 mL), and was dried (MgSO4). The solvent was removed on a rotary evaporator and the residue was purified by flash column chromatography (PE/EtOAc, 4:1) to afford 2 (0.750 g, 99%) as a white solid |
94% | With aluminium(III) iodide; diisopropyl-carbodiimide In acetonitrile at 80℃; for 18h; | 20 Example 20 (isoeugenol demethylation) To a 100 ml eggplant flask were added aluminum triiodide (2.252 g), acetonitrile (40 ml) DIC (0.379 g) and isoeugenol (0.821 g) were heated to 80 ° C and the reaction was continued for 18 hours. After cooling to room temperature, 2 mol / L dilute hydrochloric acid (10 ml) was added to the eggplant flask and acidified with ethyl acetate (50 ml X) The combined organic phases were washed with saturated aqueous sodium thiosulfate (10 ml), washed with saturated brine (10 ml), dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated to dryness on a rotary evaporator and the residue was passed through a flash column Chromatography (eluent for ethyl acetate / petroleum ether = 1: 4, volume ratio) 0.708 g of 4-propenyl catechol (white waxy solid in 94% yield) |
43% | With aluminium(III) iodide In dimethyl sulfoxide; acetonitrile at 80℃; for 18h; | 16 Example 16 (Demethylation of 4-propenyl-2-methoxyphenol) Add aluminum triiodide (2·242g, 5·5mmol), acetonitrile (40ml) and DMSO (0.977g, 12.5mmol) to a 100ml eggplant bottle, heat to 80 ° C with stirring, and stir for 0.5 hour. Then, 4-propenyl-2-methoxyphenol (0.821 g, 5.0 mmol) was added, and the reaction was further stirred (80 ° C), the reaction was stopped after 18 hours, and the mixture was cooled to room temperature and added to the eggplant bottle. 2mol/L of dilute hydrochloric acid (10ml), acidified with ethyl acetate (50ml X3), and the organic phase was combined, washed with a saturated aqueous solution of sodium thiosulfate (10ml), then washed with saturated brine (10ml), no The water was dried over magnesium sulfate, filtered, and the filtrate was evaporated to dryness. The residue was purified by flash column chromatography (eluent to ethyl acetate / petroleum ether = 1:4, volume ratio) to give Catechol (white solid, yield 43%). |
43% | With aluminium(III) iodide; dimethyl sulfoxide In acetonitrile at 80℃; for 18h; | Cleavage of Catechol Monoalkyl Ethers by Aluminum Triiodide- Dimethyl Sulfoxide; General Procedure General procedure: To a suspension of AlI3 (5.5 mmol, 1.1 equiv) in MeCN was added anhyd DMSO (0.430 g, 5.5 mmol, 1.1 equiv). After stirring for 0.5 h at 80 °C, the selected substrate (5 mmol) was added in one portion. The mixture was stirred overnight (18 h) at that temperature before quenching with aq 2 M HCl (10 mL). After extraction with EtOAc (3 50 mL), the organic phases were combined, washed with sat. aq Na2S2O3 and brine, and dried (MgSO4). The solvents were removed on a rotary evaporator, and the residue was purified by column chromatography to give the relevant catechol or phenol. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With dihydrogen peroxide In acetonitrile at 90℃; for 2h; | Catalytic activity tests General procedure: In a typical experiment, isoeugenol (5 mmol) and 0.1 g catalyst, H2O2(1.2 mL) and acetonitrile (8 mL) were heated at 90 °C under continuous stirring in a carrusel place reaction station. Products were analyzed at different time interval by GC Aligent7890 fitted with a capillary column Petrocol 100 m × 0.25 nm ×0.5 μm and a flame ionization detector (FID). The results were finally confirmed by GC-MS |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | at 20 - 100℃; for 4.5h; | E-ffa 3. General procedure: The procedure for the preparation of eugenol furfurylamine based benzoxazine was adapted from literature.1 A mixture of eugenol 1 (5.00 g, 30.45 mmol), paraformaldehyde (1.82 g, 60.90 mmol), furfurylamine (2.81 mL, 30.45 mmol) was stirred at room temperature for 2 h followed by heating at 100 oC for 2h and 30 mins. The reaction initiation was indicated by evolution of water and colour changed from turbid pink to orange. On cooling, water (100 mL) was added and the organic layer was extracted with chloroform (3 x 100 mL). The organic layers were combined and washed with aq. sodium hydroxide (2 N, 100 mL) followed by washing with water (3 x 100 mL), dried over sodium sulphate and filtered. The solvent was removed under reduced pressure and the residue obtained was purified by column chromatography using ethylacetate: hexane mixture (3:7) as eluent to give E-ffa [6-allyl-3-(furan-2-ylmethyl)-8-methoxy-3,4-dihydro-2H-benzo[e][1,3]oxazine] 3 as a white solid (7.38 g, 85%). nmax(CH3CN)/nm log10)/dm3mol-1cm-1): 209 (4.60), 283 (2.68); λmax (ATR, cm-1): 2903, 2838, 1641, 1594, 1494, 1297, 1142, 1011, 920, 833, and 737; 1H-NMR (500 MHz, CDCl3, δ ppm): 3.28 (2H, d, J = 5 Hz, ArCH2), 3.86 (3H, s, ArOCH3), 3.93 (2H, s, N-CH2-CO), 3.98 (2H, s, ArCH2N), 4.95 (2H, s, OCH2N), 5.06 (2H, m, CH2-CH=CH2), 5.89-5.98 (1H, m, CH2-CH=CH2), 6.24 (1H, m, O-CH=CH), 6.31 (1H, d, J = 5 Hz, OC=CH-), 6.39 (1H, s, ArH), 6.58 (1H, s, ArH), 7.39 (1H, d, J = 5 Hz, O-CH=CH); δC (CDCl3, 125 MHz): 40.01, 48.35, 49.21, 55.85, 82.37, 109.16, 110.01, 110.22, 115.83, 119.07, 119.94, 132.06, 137.64, 141.65, 142.62, 147.67, 151.62; m/z (EI+) 286 (MH+, 100%); HRMS (ESI) calcd. for C17H20NO3 [M + H]+ 286.1365, found 286.1455. |
70% | In water at 90℃; for 2.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With triethylamine In dichloromethane at 25℃; for 4h; | 2 Preparation of methyl 4-propenyl-2-methoxyphenylfuran-2-carboxylate (I2) Intermediate 2 was stirred with 10 ml of dichloromethane, 1.52 g (8.92 mmol) of eugenol, 1 ml of triethylamine in a three-necked flask at 25 ° C for 4 h.Then concentrated under reduced pressure, column chromatography column chromatography (V eluent: V ethyl acetate: V petroleum ether = 1:1: 2)1.97 g of a white powder (I2) was obtained in a yield of 66%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With triethylamine In dichloromethane at 25℃; for 12h; | 3 Preparation of methyl 4-propenyl-2-methoxyphenylfuran-2-acetate (I3) The intermediate product 3 was stirred with 10 ml of dichloromethane, 1.36 g (8.33 mmol) of eugenol, 1 ml of triethylamine in a three-necked flask at 25 ° C for 12 h.Concentration under reduced pressure, column chromatography column chromatography (V eluent: V ethyl acetate: V petroleum ether = 1: 6: 2)1.84 g of a white liquid (I3) was obtained in a yield of 85%, and the results are shown in Table 1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With triethylamine In dichloromethane at 25℃; for 3h; | 1 Preparation of phenyl 4-propenyl-2-methoxybenzoate Intermediate 1 (8.19 mmol), 10 ml of dichloromethane, 1.34 g (8.19 mmol) of eugenol, 1 ml of triethylamine were stirred at 25 ° C for 3 h.Concentration under reduced pressure, column chromatography (V eluent: V ethyl acetate: V petroleum ether = 1:3:2)Yielding 1.97 g of a white solid (I1),The yield was 90%, and the results are shown in Table 1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | In chloroform for 2h; Reflux; regioselective reaction; | 3-(4-Hydroxy-3-methoxyphenyl)-2-methyl-2H,3H-[1,3]thiazolo[3,2-a]pyridin-4-ium chloride(4). To a solution of 0.207 g (0.94 mmol) of 2,2'-disulfandiyldipyridine 1 in 10 mL of chloroform wasadded dropwise a solution of 0.127 g (0.94 mmol) ofsulfuryl chloride in 10 mL of chloroform. After 5 min asolution of 0.311 g (1.89 mmol) of isoeugenol 3 wasadded dropwise, and the reaction mixture was stirredfor 2 h at refluxing of the solvent. On cooling the formedprecipitate was filtered off and dried in a vacuum.Yield 0.410 g (70%). Fine white powder, mp 235-237°C.1H NMR spectrum, δ, ppm: 1.56 d (3H, CH3, J 6.7 Hz),3.86 s (3H, OCH3), 4.54-4.62 m (1H, CHCH3), 5.81 d(1H, CHN, J 11.2 Hz), 6.98-7.04 m (2Harom), 7.14 s(1Harom), 7.54-7.60 m (1HPy), 7.98 d (1HPy, J 8.6 Hz),8.11 d (1HPy, J 6.3 Hz), 8.24-8.30 m (1HPy). 13C NMRspectrum, δ, ppm: 17.58 (CH3), 51.37 (OCH3), 57.94(SCH), 83.56 (CHN), 114.01 (C6H3), 118.12 (C6H3),124.64, 124.71, 125.39, 126.52 (C6H3, Py), 143.22(Py), 146.75 (Py), 149.11 (CO, C6H3), 150.45 (CO,C6H3), 161.81 (SCN, Py). Found, %: 58.21; 5.10;Cl 11.71; N 4.37; S 10.18. C15H16ClNO2S. Calculated,%: 58.15; 5.21; Cl 11.44; N 4.52; S 10.35. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | With H-CBV78O at 80℃; for 2.5h; | 2 5.07 g (40 mmol) 2-methoxyphenol (Sigma-Aldrich, 98%) and 0.25 g (0.1 mmol) H-CBV78O (Zeolyst,Si/Al2 ratio of 80) were placed in a 10 mL round-bottom flask. The vessel was heated to 80°C under airand continuous magnetic stirring (375 rpm). At reaction temperature, 0.33 g (2 mmol) 2-methoxy-4-(prop-1-en-1-yl)phenol (Sigma-Aldrich, 99%, mixture of cis and trans) was gradually introduced via aPerfusor Space Syringe Pump (B Braun) over 2 hours and stirred for an additional 30 minutes. Thenormalized addition factor for this semi-batch configuration was 0.25. After the reaction, the hot reaction mixture was filtered and excess unreacted 2-methoxyphenol removed via vacuum distillation (90 °C at 20 mbar). The solid GGP product was characterized by GC(-MS), ETIR and ‘H and ‘3C NMR. A full conversion of 2-methoxy-4-(prop-1-en-1-yl)phenol was achieved yielding 79.8 wt% GGP (82% p,p’17% m,p’-isomer). Highly pure transparent crystals of p,p’-GGP were grown from hot heptane and/orslow evaporation of an acetone/heptane solution at room temperature (isolated yield: 0.36 g, 63%).M.p. 119-120 °C; 1H NMR (300 MHz, CDCI3, 25 °C, TMS): 6 = 0.89 (t, 3i(H,H)= 7.3 Hz, 3H; -CH2CH3), 1.98(quin, 3i(H,H)= 7.3 Hz, 2H; -CHCH2CH3), 3.64 (t, 3i(H,H)= 7.5 Hz, 1H; -CHCH2), 3.83 (s, 6H; -OCH3), 5.47(s, 2H; -ArOH), 6.67 (d, 4i(H,H)= 1.9 Hz, 2H; -m-ArH), 6.74 (dd, 3i(H,H)= 8.1, 4J(H,H)= 1.9 Hz, 2H; -m-ArH),6.84 ppm (d, 3i(H,H)= 8.1 Hz, 2H; -o-ArH); 13C NMR (100 MHz, CDCI3, 25 °C, TMS): 6 = 146.4, 143.8,137.5, 120.2, 114.1, 110.5, 55.8, 52.5, 29.0, 12.8 ppm; MS (70 eV, El): m/z (%): 288 (15) [M9, 259 (100) [M-CH3], 229 (8) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With hydrogenchloride In water at 250℃; for 3h; Sealed tube; Inert atmosphere; | I.2 Example 2. Synthesis of catechol from isoeugenol (2-methoxy-4-prop-1-enylphenol) [JBO-307] This experiment was performed according to General procedure A. Isoeugenol (164 mg, 1 mmol) was used as the substrate, cone. HCI (17 μΙ_, 0.2 mmol, 0.2 equiv.) as acidic catalyst and H20 (2 mL) as the solvent. The reaction was performed at 250 °C for 3 h under 50 bar of N2 pressure. Catechol was obtained in 85% isolated yield (94 mg, 0.85 mmol). General procedure A (0233) A 4 mL glass vial was charged with a magnetic stirring bar, the substrate for the experiment, the acid or alkaline reagent and 2 mL of the appropriate solvent or solvent mixture. The vial was closed properly with the correct cap and septum and the septum was pierced with a syringe needle. This vial was brought to the 4620 Parr reactor and the reactor was closed properly. The reactor was flushed with the appropriate gas (3 x 10 bar) and then filled with this gas (with the reported pressure). The reactor was heated to the reaction temperature and this temperature was maintained for the reported reaction time (it takes approx. 60 min to reach 250 °C). After cooling down (from 250 °C to 170 °C in the air and from 170 °C to r.t. in an ice bath), the gas was released and the reactor was opened. (0234) After opening the reactor, the crude reaction mixture was brought to a roundbottomed flask and the vial was rinsed with H20 (3 mL). This aqueous reaction mixture was freezed by gently rotating the flask in liq. N2. Subsequently, vacuum was applied until all volatiles were removed. If necessary, this freeze drying step was repeated multiple times. The residue was redissolved in acetone, filtered over a silica plug and the filtrate was concentrated under reduced pressure by using a rotary evaporator. The residue was analysed with NMR and MS (APCI) or LC-MS. |
62% | With hydrogenchloride; water at 250℃; for 3h; Sealed tube; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With potassium carbonate In N,N-dimethyl-formamide at 70℃; for 48h; | 2.1. Synthesis of 4-(2-methoxy-4-(prop-1-enyl)phenoxy)phthalonitrile (MPPP) Isoeugenol (1.64 g, 10 mmol) and 4-nitro phthalonitrile (1.73 g, 10 mmol) were dissolvedin DMF (15 mL) and finely ground anhydrous K2CO3 (2.02 g, 14.67 mmol) was addedto this solution. The reaction mixture was stirred at 70 C for 2 days then poured into100 ml of water. The resulting precipitate was filtered and dried. Single crystals wereobtained by slow evaporation from ethanol (Scheme 1). Yield: 1.07g; 92%; m.p. 160 C.FT-IR (mmax/cm21) 3079, 3065, 3037 (Ar-CH), 2972, 2942, 2920, 2842 (AliphaticCH), 2230 (CN), 1656 (Aliphatic CC), 1605, 1587 (Ar-C-C), 1260, 1243 (O-CH3).1H-NMR shifts (DMSO-d6) d, ppm: 8.019-7.103 (1H, d, ArCH), 7.221-6.996 (1H, d.d,ArCH), 6.452-6.305 (2H, m, CH), 3.725 (3H, s, OCH3), 1.853-1.838 (3H, d, -CH3).13C-NMR shifts (DMSO-d6) d, ppm: 161.839, 151.430, 140.186, 137.461, 136.537,130.520, 126.967, 122.804, 121.507, 120.696, 119.336, 116.878, 116.398, 115.868, 111.077,107.864, 56.180, 18.682.Scheme |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
43% | With silver tetrafluoroborate In dichloromethane at 40℃; for 24h; Inert atmosphere; Sealed tube; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
32 % de | With aluminum (III) chloride In dichloromethane for 0.5h; Cooling with ice; Overall yield = 35 percent; Overall yield = 70 mg; diastereoselective reaction; | General experimental procedure for the preparation of tetrahydrofurans General procedure: To an ice-bath cold solution of alkene (0.56 mmol) in dichloromethane (1 mL) was addedthe corresponding epoxide (0.56 mmol, 1 equiv), and then aluminum chloride (0.168mmol, 0.3 equiv). The resulting mixture was stirred cold with an ice-bath for 30 minutes.An indicating color change was observed after this time. Then water (10 mL) was addedand extracted with dichloromethane (3 x 20 mL). Combined organic layers were dried(Na2SO4), filtered and concentrated to afford an oil which was purified through silica gelcolumn. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85.6% | With potassium carbonate In N,N-dimethyl-formamide at 20℃; | 2.3.1. Preparation of 4-aryloxy phthalonitrile The intermediates of 4-(4-methyl formate) phenoxy phthalonitrileand (4-(4-butyl formate) phenoxy phthalonitrile were prepared and characterized as reported before [49]. 2-Methoxy-4-(2-propenyl) phenoxyphthalonitrile was obtained as follows. 4-propenyl-2-methoxyphenol (isoeugenol, 8.26 mmol, 1.354 g) and redistilled DMF (40 mL)were put in a two-neck round bottom flask. Under vigorously stirring,4-nitrophthalonitrile (5.9 mmol, 1.021 g) was added and dissolved.Anhydrous potassium carbonate fine powder (8.26 mmol, 1.140 g) wasadded portion wise. The reaction was stirred at room temperature till4-nitrophthalonitrile disappeared completely. The crude product wasobtained by disposing the mixture into ice water and dealed with 1%sodium hydroxide for 12 h. The yellowish white product was obtainedby recrystallization in methanol. Yield: 1.46 g, 85.6%, m.p. 74-76 °C. IR νmax/cm -1 (KBr pellet): 3069 (CHar), 2228 (C ≡ N), 1592, 1510, 1481,1410 (C = C), 1246 (Ph-O-Ar) (Fig. S1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
7 %Chromat. | With HY-1 zeolite In ethanol; water at 200℃; for 0.5h; Microwave irradiation; | 1. General procedure for reactions of model compounds with zeolites in vial General procedure: A 2-5 mL microwave vial (Biotage) equipped with a stir bar was loaded with the corresponding model compound and catalyst. Solvent (standard solution of dodecane in Ethanol/ water) was added and the vial was sealed. The reaction mixture was stirring for specified time at specified temperature. After the completing of the reaction the reaction mixture was filtrated and analyzed by GC-FID and GC-MS. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
16 %Chromat. | With beta-1 zeolite In ethanol; water at 200℃; for 0.5h; Microwave irradiation; | 1. General procedure for reactions of model compounds with zeolites in vial General procedure: A 2-5 mL microwave vial (Biotage) equipped with a stir bar was loaded with the corresponding model compound and catalyst. Solvent (standard solution of dodecane in Ethanol/ water) was added and the vial was sealed. The reaction mixture was stirring for specified time at specified temperature. After the completing of the reaction the reaction mixture was filtrated and analyzed by GC-FID and GC-MS. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With beta-1 zeolite In water; isopropyl alcohol at 200℃; for 0.5h; Microwave irradiation; Overall yield = 70 percentChromat.; | 1. General procedure for reactions of model compounds with zeolites in vial General procedure: A 2-5 mL microwave vial (Biotage) equipped with a stir bar was loaded with the corresponding model compound and catalyst. Solvent (standard solution of dodecane in Ethanol/ water) was added and the vial was sealed. The reaction mixture was stirring for specified time at specified temperature. After the completing of the reaction the reaction mixture was filtrated and analyzed by GC-FID and GC-MS. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With methoxy(cyclooctadiene)rhodium(I) dimer; hydrogen; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In toluene at 80℃; for 4h; Autoclave; Inert atmosphere; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With methoxy(cyclooctadiene)rhodium(I) dimer; hydrogen In toluene at 80℃; for 4h; Autoclave; Inert atmosphere; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With methoxy(cyclooctadiene)rhodium(I) dimer; hydrogen; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene at 80℃; for 4h; Autoclave; Inert atmosphere; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With methoxy(cyclooctadiene)rhodium(I) dimer; hydrogen In toluene at 80℃; for 0.5h; Autoclave; Inert atmosphere; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With tetrakis(triphenylphosphine) palladium(0); (S)-Mandelic acid; water-d2; tricyclohexylphosphine In toluene at 120℃; for 16h; Inert atmosphere; | Catalytic Deuteration of Styrenes; General Procedure General procedure: In a glass tube, alkene 1 (0.20 mmol), Pd(PPh3)4 (0.01 mmol), PCy3 (0.02 mmol) and (+)-mandelic acid (0.06 mmol) were added sequentially and the tube was then purged with nitrogen three times. Subsequently, toluene (2.0 mL, 0.1 M) and D2O (10 mmol) were added under a N2 atmosphere and the tube was placed in a pre-heated oil bath at 120 °C and the contents stirred overnight (16 h). The reaction mixture was then cooled to room temperature and diluted with CH2Cl2 (10 mL). The mixture was directly concentrated under reduced pressure and the crude residue was purified by chromatography on silica gel. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | Stage #1: 2,2'-dipyridyldisulphide With sulfuryl dichloride In chloroform at 20℃; for 0.166667h; Stage #2: 2-methoxy-4-propenylphenol In chloroform at 20℃; for 12h; Reflux; regioselective reaction; | trans-3-(4-Hydroxy-3-methoxyphenyl)-2-methyl-2H,3H-[1,3]thiazolo[3,2-]pyridin-4-ium chloride(1) A solution of sulfuryl chloride (0.135 g, 1 mmol) in chloroform (10 mL) was added dropwise to a solution of di(2-pyridine) disulfide (0.218 g, 1 mmol) in chloroform (10 mL) and the mixture was stirred for 10 min at room temperature. A solution of isoeugenol (0.328 g, 2 mmol) in chloroform (10 mL) was added dropwise and the reaction mixture stirred for 4 h at room temperature and 8 h at reflux temperature. On cooling the formed precipitate was filtered off and dried in vacuum giving the product (0.527 g, 85% yield) as a white powder, mp 235-237 °C.1H-NMR (400 MHz, D2O): δ 1.56 (d,J= 6.7 Hz, 3H, CH3), 3.86 (s, 3H, OCH3), 4.58 (dq,J= 11.3, 6.7 Hz, 1H, SCH), 5.81 (d,J= 11.3 Hz, 1H, NCH), 6.99-7.04 (m, 2H, Ar), 7.14 (s, 1H, Ar), 7.55-7.59 (m, 1H, Py), 7.97-7.99 (m, 1H, Py), 8.10-8.12 (m, 1H, Py), 8.25-8.29 (m, 1H, Py).13C-NMR (101 MHz, D2O): δ 17.58 (CH3), 51.37 (SCH), 57.94 (OCH3), 83.56 (NCH), 114.01 (Ar), 118.12 (Ar), 124.64 (Py), 125.39 (Py), 126.52(Ar), 143.22 (Py), 146.75 (Py), 149.11 (CO, Ar), 150.45 (CO, Ar), 161.81 (Py). Anal. Calcd for C15H16NClO2S: C 58.15, H 5.21, Cl 11.44, N 4.52, S 10.35. Found: C 57.91, H 5.07, Cl 11.63, N 4.34, S 10.13. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | Stage #1: 2-pyridineselenenyl chloride With sulfuryl dichloride In chloroform at 20℃; for 0.166667h; Stage #2: 2-methoxy-4-propenylphenol In chloroform at 20℃; for 12h; Reflux; regioselective reaction; | trans-3-(4-Hydroxy-3-methoxyphenyl)-2-methyl-2H,3H-[1,3]thiazolo[3,2-]pyridin-4-ium chloride(1) General procedure: A solution of sulfuryl chloride (0.135 g, 1 mmol) in chloroform (10 mL) was added dropwise to a solution of di(2-pyridine) disulfide (0.218 g, 1 mmol) in chloroform (10 mL) and the mixture was stirred for 10 min at room temperature. A solution of isoeugenol (0.328 g, 2 mmol) in chloroform (10 mL) was added dropwise and the reaction mixture stirred for 4 h at room temperature and 8 h at reflux temperature. On cooling the formed precipitate was filtered off and dried in vacuum giving the product (0.527 g, 85% yield) as a white powder. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With potassium carbonate In N,N-dimethyl-formamide; toluene for 12h; | 5 Synthesis of the Propargylated Isoeugenol 20 g (0.130 mol) of isoeugenol (Sigma Aldrich) are solubilized in 100 ml (5 eqm) of DMF. 33.67 g (2 eq.) of finely ground potassium carbonate (K2CO3) are added with magnetic stirring. 20.35 ml (1.5 eq.) of propargyl bromide (Alfa Aesar) (80 m % in toluene) are added by means of a dropping funnel. The magnetic stirring is maintained for 12 h. The completion of the reaction is monitored by TLC with a 70:30 petroleum ether:ethyl acetate (volume) eluent. After filtration of the K2CO3 and washing with ethyl acetate, 100 ml of ethyl acetate are added to the medium for the extraction. The organic phase is washed 3 times with distilled water (3×100 ml) and once with brine (1×100 ml). The organic phase is dried over MgSO4, filtered and concentrated under reduced pressure. The yield is 91% |
73% | With potassium carbonate In N,N-dimethyl-formamide; toluene for 12h; | 4 Synthesis of Propargylated Isoeugenol 20 g (0.130 mol) of isoeugenol ( Sigma-Aldrich) are dissolved in 100 mL (5 eq.) of DMF. 33.67 g (2 eq.) of finely ground potassium carbonate (K2CO3) are added with magnetic stirring. 20.35 mL (1.5 eq.) of propargyl bromide (Alfa Aesar) (80 mol % in toluene) are added via the dropping funnel. Magnetic stirring is continued for 12 hours. Completion of the reaction is monitored by TLC, eluting with 70/30 (volume) petroleum ether/ethyl acetate. After filtering off the K2CO3 and washing with ethyl acetate, 100 mL of ethyl acetate are added to the medium for the extraction. The organic phase is washed three times with distilled water (3×100 mL) and once with brine (1×100 mL). The organic phase is dried over MgSO4, filtered and concentrated under reduced pressure. The yield is 91%.The compound is purified by vacuum distillation in a Kugelrohr glass oven (p=15 Pa and heating T° C.=140° C.). The compound is recovered in the form of white crystals. The overall yield after purification is 73%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | With Grubbs catalyst first generation at 90℃; Inert atmosphere; | 8 Synthesis of the Coupled Isoeugenol 0.0181 g (0.017%) of Grubs II catalyst (Umicore M2a) is placed in a 50 mL round-bottomed flask with a magnetic stirrer, and 20 g (0.122 mol) of isoeugenol ( Sigma-Aldrich) are then added. The medium is placed under a stream of argon and heated at 90° C. The medium turns solid after 3 minutes of reaction. After cooling, a 1H NMR spectrum of the crude product is taken to determine the conversion of the isoeugenol to stilbene. The degree of conversion is 90%. Only the trans-compound is observed. The product is recovered by suspension in 4 volumes of DCM. The medium is refluxed for 1 hour until dissolution is complete, and is then left to stand at room temperature overnight. The suspension is filtered through a sinter and washed with 1 volume of cyclohexane. The isolated yield is 67%. |
67% | With tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride at 90℃; for 0.05h; Inert atmosphere; | 5 Synthesis of the Coupled Isoeugenol 0.0181 g (0.017%) of Grubbs II catalyst (UMICORE M2a) is introduced into a 50 ml round-bottomed flask with a magnetic stirrer, then 20 g (0.122 mol) of isoeugenol (Sigma Aldrich) are added. The medium is placed under an argon stream and heated to 90° C. The medium becomes solid after 3 minutes of reaction. After cooling, a 1H NMR spectrum of the crude product is performed in order to determine the conversion of the isoeugenol into stilbene. The degree of conversion is 90%. Only the trans-compound is observed. The product is recovered by suspension in 4 vol. of DCM, and the medium is refluxed for 1 hour until complete solubilization and then left to stand at ambient temperature overnight. The suspension is filtered on a frit and washed with 1 vol. of cyclohexane. The isolated yield is 67%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen; platinum(II) chloride In ethanol at 60℃; for 6h; | 12 Example 9. PtCl2 catalyzed hydrogenation and hydrodeoxygenation reaction and reaction products of monocyclic aromatic hydrocarbons and polycyclic aromatic hydrocarbons. General procedure: 0.15mmol reaction substrate (e.g., phenol 14.11mg) was placed 20ml pressure reaction flask, 10ml to a reaction solvent (ethanol and tert-butanol) was dissolved, then adding the catalyst PtCl2 4mg (0.015 mmol). After replacing the air with H2 gas, stabilize the H2 pressure at 0.1-0.2Mpa. Stir the reaction at an appropriate temperature (e.g. 60°C). When the reaction proceeds to 2h and 6h (if the reaction conversion rate is low, the reaction proceeds for 22h), respectively take 1ml of the reaction solution and filter. Samples were taken and processed according to the method of Example 3, and the reaction products were analyzed by GC-MS.The specific results are shown in Table 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen In hexane at 300℃; for 4h; Autoclave; | 2.4. Catalytic activity measurements General procedure: The catalytic performance was performed in a 50 mL autoclave(Kemi, China). In a typical experiment, 10 mL n-hexane with 1.25 mmol reactant and 1.25 mmol dodecane (internal standard),and a certain amount of as-prepared catalyst were charged intothe reactor. After purging with H2 3 times, the reactor was filledwith a certain initial H2 pressure at room temperature and stirredwith 1000 rpm/min. Then the reaction mixture was heated to acertain temperature at a rate of 5 C/min and maintained at the targettemperature for a certain time. After the reaction, the productswere analyzed by GC (SP-7890) and GC-MS (Agilent 6890A-5975C). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With N-ethyl-N,N-diisopropylamine In tetrahydrofuran at 40℃; for 4h; Irradiation; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
35% | With tris isopropylate aluminium at 140℃; for 3h; Inert atmosphere; | Procedure for the synthesis of compounds 3a, 3b. General procedure: The flask was charged with phenols (2a, 2b) (2 Equiv.) and heated up to 140 oC, and added Al(O-i-Pr)3 (20% mol). After phenolic reagent and catalyst were completely dissolved, the solution was added isoeugenol (1 Equiv.). The reaction was performed by keeping the temperature at 140 oC for 3 h. The mixture was cooled, diluted with ethyl acetate, and treated with HCl solution (5%) to compose the catalyst when the reaction was complete. Then, the mixture was elutriated with saturated NaHCO3 solution and water until rinsing was neutral and the organic layer was dried over anhydrous Na2SO4. The solvent was evaporated, and the crude products were purified by column chromatography (on a silica gel column) using n-hexane/EtOAc (9:1) as eluent. The products were crystallized from n-hexane/EtOAc (9:1). |
With tris isopropylate aluminium at 140℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With tris isopropylate aluminium at 140℃; for 3h; | |
86% | With tris isopropylate aluminium at 140℃; for 3h; Inert atmosphere; | Procedure for the synthesis of compounds 3a, 3b. General procedure: The flask was charged with phenols (2a, 2b) (2 Equiv.) and heated up to 140 oC, and added Al(O-i-Pr)3 (20% mol). After phenolic reagent and catalyst were completely dissolved, the solution was added isoeugenol (1 Equiv.). The reaction was performed by keeping the temperature at 140 oC for 3 h. The mixture was cooled, diluted with ethyl acetate, and treated with HCl solution (5%) to compose the catalyst when the reaction was complete. Then, the mixture was elutriated with saturated NaHCO3 solution and water until rinsing was neutral and the organic layer was dried over anhydrous Na2SO4. The solvent was evaporated, and the crude products were purified by column chromatography (on a silica gel column) using n-hexane/EtOAc (9:1) as eluent. The products were crystallized from n-hexane/EtOAc (9:1). |
Tags: 97-54-1 synthesis path| 97-54-1 SDS| 97-54-1 COA| 97-54-1 purity| 97-54-1 application| 97-54-1 NMR| 97-54-1 COA| 97-54-1 structure
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