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CAS No. : | 124-19-6 | MDL No. : | MFCD00007030 |
Formula : | C9H18O | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | GYHFUZHODSMOHU-UHFFFAOYSA-N |
M.W : | 142.24 | Pubchem ID : | 31289 |
Synonyms : |
|
Num. heavy atoms : | 10 |
Num. arom. heavy atoms : | 0 |
Fraction Csp3 : | 0.89 |
Num. rotatable bonds : | 7 |
Num. H-bond acceptors : | 1.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 45.58 |
TPSA : | 17.07 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -4.85 cm/s |
Log Po/w (iLOGP) : | 2.44 |
Log Po/w (XLOGP3) : | 3.26 |
Log Po/w (WLOGP) : | 2.94 |
Log Po/w (MLOGP) : | 2.39 |
Log Po/w (SILICOS-IT) : | 2.88 |
Consensus Log Po/w : | 2.78 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 2.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -2.31 |
Solubility : | 0.691 mg/ml ; 0.00486 mol/l |
Class : | Soluble |
Log S (Ali) : | -3.29 |
Solubility : | 0.0725 mg/ml ; 0.00051 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -3.02 |
Solubility : | 0.135 mg/ml ; 0.000946 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.52 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P264-P273-P280-P302+P352-P332+P313-P362+P364 | UN#: | N/A |
Hazard Statements: | H315-H412 | 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 |
---|---|---|
0.487 g | Stage #1: With ammonium chloride In 1,2-dimethoxyethane; water at 50℃; for 20 h; Autoclave Stage #2: at 40℃; for 6 h; |
General procedure: Following the typical procedure described above, Rh(acac)(CO)2 (2.6 mg, 0.01 mmol), xantphos (28.9 mg, 0.05 mmol) were placed in the autoclave. Then a solution of olefin (5 mmol) in DME (8 mL) was added via cannula, the autoclave was pressurized with 20 bar of CO/H2 equimolar mixture and the reaction was conducted for 18 h, upon stirring, at 80°C. After this period, the reactor was cooled to room temperature, an aqueous solution (2 mL) of NH4Cl (5.5 mmol) and NaCN (5.5 mmol) was added via inlet cannula and the reaction was kept at 50°C for 20 h. After work-up and purification, the resulting α-aminonitrile (4.1 mmol) was suspended in a concentrated HCl solution and stirred for 6 h at 40°C. The product was dissolved in methanol. After adjustment of the pH to the isoelectric point, using NH4OH (aq), the solvent was evaporated and the amino acid was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | at 90℃; for 0.5 h; Microwave irradiation | General procedure: A 10 mL reaction vessel was charged in air with Pd(PPh3)4 (6 mg, 1 mol percent), aldehyde (0.5 mmol), K2CO3 (207 mg, 1.5 mmol), benzyl chloride (70 μL, 0.6 mmol) and EtOH (1 mL). The vessel was sealed and submitted to microwave irradiation for 30 min at 90 °C, using an initial power of 30 W. (Microwave reactions were carried out with a CEM Discover 300 W monomode microwave instrument. The closed vessels used were special glass tubes with self-sealing septa that controlled pressure with appropriate sensors on the top (outside the vial). The temperature was monitored through a non-contact infrared sensor centrally located beneath the cavity floor.) The mixture was then allowed to cool to room temperature, filtered over a pad of Celite.(R). and rinsed with EtOH (5 mL). The filtrate was concentrated in vacuo and the product was purified by flash chromatography on silica gel (CH2Cl2/hexane). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With pyridine zuletzt bei Siedetemperatur; | ||
710 mg | With pyrrolidine; pyridine In tetrahydrofuran at 0 - 20℃; Inert atmosphere; optical yield given as %de; stereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With ozone; acetic acid Behandeln der Reaktionsloesung mit Zinkstaub und Wasser; | ||
Stage #1: oleic acid ethyl ester With osmium(VIII) oxide; 4-methylmorpholine N-oxide In water; acetone at 20℃; for 6h; Stage #2: With sodium periodate In water; acetone for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64%Chromat.; 74% | With sodium periodate; tetra(n-butyl)ammonium hydrogen sulfate; In dichloromethane; water; at 20℃; | Oxononanoic acid 7 was prepared by oxidative cleavage of 5 or 6. To a stirred solution of 5 (404mg, 1.276 mmol) or 6 (150 mg, 0.433 mmol) in 15 ml DCM at room temperature, NaIO4 (3 eq)in15 ml water and tetrabutylammonium hydrogensulphate (0.5 eq) as phase transfer catalyst were added. The mixture was stirred at room temperature overnight, until reaction completion. The mixture was transferred into a separating funnel and the two layers were separated. The aqueous layer was extracted with DCM (x 2). The organic layers were combined, washed with water, brine and dried over Na2SO4. The solvent was removed under reduced pressure, yielding a 1:1 mixture of 7 and nonanal which was then purified by flash column chromatography (1:1 hexanes:ethyl acetate)for 154 mg (0.89 mmol, 74%) as colorless oil. 7 was purified by flash column chromatography in 64% yield. IR spectrum (cm-1): 3500, 2720, 1750, 1720. 1H NMR (300 MHz, CDCl3) delta 9.75 (s, 1H,CHO), 2.41 (t, 2H, J = 8.2 Hz, CH2CHO), 2.34 (t, 2H, J = 82 Hz, CH2COOH), 1.62 (m, 4H,CH2CH2CHO and CH2CH2COOH), 1.25-1.32 (m, 6H, CH2). 13C NMR (75 MHz, CDCl3): delta 203.1(s, -CHO), 180.2 (s, COOH), 34.2, 32.8, 30.0, 29.4, 29.1, 26.2, 25.1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
30.2% | With di-tert-butyl peroxide; C52H80CoN2O10; oxygen; In tetrahydrofuran; at 140℃; under 5250.53 Torr; for 5h;Autoclave; | 3.4 g (0.01 mol) of erucic acid and 0.095 g (0.0001 mol) were added to the autoclave.a cobalt complex of an isosteric alcohol derivative, 34.0 g of tetrahydrofuran,1.6 g (0.012 mol) of t-butanol peroxide,Passing oxygen to the reactor pressure of 0.7 MPa, the reaction temperature is 140 C,The reaction time is 300 minutes. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With manganese(II) oxide Hydrogenation; | ||
With sodium amalgam | ||
With formic acid; carbon dioxide; manganese(II) oxide |
With formic acid; titanium(IV) oxide at 250 - 260℃; unter Druck; | ||
With formic acid; titanium(IV) oxide at 300℃; | ||
With formic acid; manganese(II) oxide at 300 - 360℃; | ||
With glycerol-3-Phosphate Dehydrogenase; D-glucose; NADP<SUP>+</SUP>; Nocardia PPTase; Segniliparus CAR; ATP; coenzyme A; magnesium chloride In dimethyl sulfoxide at 35℃; for 16h; Enzymatic reaction; | 2.4. Standard reduction procedure General procedure: The His-CAR (1.5 mg) was incubated with His-PPTase (295 g) in the presence of CoA (1 mM) as a cofactor for 1 h at 28°C in a final volume of 600 L of sodium phosphate buffer (100 mM, pH 7.5) containing 10 mM of MgCl2. The resulting enzyme mixture (holo-CAR, 50 g) was mixed with NADP+ (0.9 mM), GDH (1 U, one unitcorresponds to the amount of enzyme which could reduce 1 molNADP+ to NADPH per minute), glucose (60 mM), MgCl2 (10 mM), substrate (5 or 10 mM, from 1 M stock solution in DMSO), and ATP (15 mM) in Tris-HCl buffer (100 mM, pH 9) with a nal volume of 1 mL. The reaction mixture was incubated at 100 rpm in a rotaryshaker at 35C for 16 h, and extracted with 1 mL of ethyl acetateafter the pH was adjusted to 2-3 with 1 M HCl solution. The organicextracts were dried over anhydrous sodium sulfate and analyzedby gas chromatography (GC) and gas chromatography-mass spec-trometry (GC-MS) to determine the amount of substrate (a) andproducts (aldehyde b, alcohol c) in the mixture. All experimentswere conducted in triplicate. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With 4-methoxy-TEMPO; sodium hypochlorite; potassium bromide In dichloromethane; water at 0℃; for 0.05h; pH = 8.6; other primary and secondary alcohols, var. temp., time, pH, and catalytic species; | |
98% | With tert.-butylhydroperoxide In water at 60℃; for 3h; | |
92% | With 4-methoxy-TEMPO; sodium hypochlorite; potassium bromide In dichloromethane; water at 0℃; for 0.05h; pH = 8.6; |
92% | With silica gel; pyridinium chlorochromate In dichloromethane at 18℃; for 0.333333h; | |
90% | With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; hydroxylamine; oxygen In water; 1,2-dichloro-ethane at 80℃; for 6h; Autoclave; | |
89% | With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; sodium hypochlorite pentahydrate; sodium hydrogencarbonate; potassium bromide In water for 0.333333h; Milling; | General procedure for the oxidation of primary alcohols 1a-10b (procedure A) General procedure: NaOCl·5H2O (247 mg, 1.5 mmol), NaHCO3 (185 mg, 2.2 mmol), and KBr (3.6mg, 0.03 mmol, 3 mol%) were placed in an Ertalyte jar (15 mL, 40.6 g) equippedwith six zirconia balls (5 mm ). The jar was ball-milled at 1800 rpm (30 Hz) for1 min. Following this initial grinding period, primary alcohol 1a-10a (1.0 mmol),and 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO, 7.8 mg, 0.05 mmol, 5 mol %),were added and the reaction mixture was subjected to further grinding at 30 Hzfor 20 minutes. The progress of the reaction was monitored by GC-MS analysisand TLC analysis (heptane/AcOEt 9:1, v/v) of an aliquot of crude. The millingwas stopped, Na2SO3 (189 mg, 1.5 mmol) added to the jar, and milling continuedat 30 Hz for further 3 minutes. Then, AcOEt (2 × 1.5 mL) was added into the jarand the crude was transferred into a round-bottomed flask together with silica gel(350 mg). The combined organic layers were concentrated in vacuo. The resultingresidue was purified through a short column on silica gel with ethylacetate/hexane 1:9 (v/v) as the eluent to afford the corresponding aldehydes 1b-10b |
88% | With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; copper diacetate In water; acetonitrile at 20℃; for 4h; Green chemistry; | General procedure: A mixture of alcohol (5.0 mmol), Cu(OAc)2 (9.1 mg, 0.05 mmol), and TEMPO (7.8 mg, 0.05 mmol) in CH3CN/H2O (5/10 mL) was stirred at room temperature for specified time. After completion of the reaction (monitored by TLC, eluents: petroleum ether/ethyl acetate = 4/1), dichloromethane (10 mL) was added to the resulting mixture. The dichloromethane phase was separated, and the aqueous phase was further extracted with dichloromethane (10 mL × 2). The combined organic layers were dried over anhydrous sodium sulfate and concentrated to give a residue, which was purified by column chromatography (eluents: petroleum ether/ethyl acetate = 10/1) to provide the desired product. |
87% | With 2,4,6-trimethyl-pyridine; 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinoxy; iodine; sodium hydrogencarbonate In dichloromethane; water at 20 - 22℃; for 3h; | 1.10 Preparative synthesis of compounds 2a,b,d-al (general procedure) General procedure: A solution of corresponding alcohol 1a,b,d-al (8 mmol), nitroxide 4a (0.085 g, 0.4 mmol) and compound 6d (0.097 g, 0.8 mmol) in CH2Cl2 (10 mL) was added to a vigorously stirred solution of NaHCO3 (2.016 g, 24 mmol) in water (10 mL) at 20 °C. Then I2 (4.06 g, 16 mmol) powder was added in one portion to the formed reaction mixture at vigorous stirring and temperature 20-22 °C. The reaction mixture was stirred at 20-22 °C for appropriate time (see Table 1 in the article). Then, a saturated solution of sodium thiosulfate was added to the stirred reaction mixture for discoloration. Organic and aqueous phases were separated and the aqueous phase was then extracted with CH2Cl2 (3×5 mL). Organic phase and the extracts were combined and washed subsequently with saturated aqueous solution of NaCl (5 mL), aqueous solutionof HCl (1%) saturated with NaCl (3 mL), and then with water (5 mL). The washed extract was dried with anhydrous Na2SO4 and evaporated to dryness to give crude product, which was then purified by vacuum distillation under argon atmosphere or by recrystallization. |
85% | With sodium hypochlorite; water; potassium bromide In dichloromethane at 0℃; for 0.5h; | |
85% | With 2,2,6,6-tetramethyl-piperidine-N-oxyl; sodium hypochlorite; silica gel; potassium bromide In dichloromethane at 0℃; for 1h; | |
82% | With dihydrogen peroxide In acetonitrile at 80℃; for 3h; | |
81% | With trimethylsilyl chromates In dichloromethane at 25℃; for 3h; | |
81% | With oxygen; cyclopenta-1,3-diene In toluene at 70℃; | 6 In the reaction kettle, add 10 mL of toluene and add 5 mmol.1-nonanol and 15 mmol of cyclopentadiene,Charged with 2.0 MPa of oxygen, stirred at 70 ° C, and detected by gas chromatography.The yield of the original product was 81%. |
78% | With 1-butyl-3-methylimidazolium hydrogen sulfate; sodium bromate In water at 60℃; for 0.75h; Green chemistry; | General procedure for the oxidation of 1,2-diols, a-hydroxyketones and alcohols to 1,2-diketones and aldehydes/ketones General procedure: In a typical experiment, a mixture of 1,2-diols/a-hydroxyketones/alcohols (1 mmol), sodium bromate (3 mmol),and bmim[HSO4]:H2O 3:1 (v/v) along with a stir bar was placed in a RB flask fitted with a condenser. The reaction mixture was stirred magnetically in an oil-bath maintained at 60 C for an appropriate time as mentioned in Tables 3,4, and 5, respectively. After completion of the reaction, as monitored by TLC using petroleum ether:ethyl acetate(80:20, v/v) as eluent, the reaction mixture was cooled to room temperature and worked up as mentioned above. The product obtained was identified by m.p (wherever applicable), IR and NMR spectra. |
74% | With gold(III) chloride In neat (no solvent) at 60℃; for 16h; Green chemistry; | General Procedure for the Oxidation of Alcohols General procedure: To a 10 mL round-bottom flask, Imim-PEG1000-TEMPO (0.5mmol), AuCl3 (0.5 mmol) and benzyl alcohol (10 mmol) were successively added with vigorous stiring. The reaction was allowed to proceed at 60 °C and monitored by TLC. Upon completion, the reaction mixture was cooled to r.t. and extracted three times by adding Et2O. The organic phase was dried over anhydrous MgSO4, filtered, and evaporated under reduced pressure to give benzaldehyde (95% yield). All products had spectroscopic data consistent with the as signed structures. |
73% | With potassium carbonate at 20℃; for 22h; Neat (no solvent); | |
73% | With tert.-butylhydroperoxide; vanadyl(IV) sulphate pentahydrate In water; acetonitrile at 20℃; for 8h; Green chemistry; | General procedure for oxidation of alcohol: General procedure: In a typical experiment, 1 mmol 1-phenyl ethanol and 10 mol % (25.30 mg) VOSO4.5H2O (purchased from Loba Chemie, molecular weight 253.08) in 2 ml CH3CN/H2O (1:1) in a round bottomed flask. To this mixture 2 equiv 70% TBHP (aqueous) was added and stirred at room temperature for the time specified in Table 1. The progress of the reaction was monitored by TLC. After the completion of the reaction, the mixture was extracted with ethyl acetate (3 x 20 mL) three times. The ethyl acetate layer was dried with anhydrous Na2SO4 and evaporated under reduced pressure. The crude product was purified by column chromatography using ethyl acetate-hexane as the eluent. Formation of the product was confirmed by comparing FTIR spectra, 1H NMR spectra, 13C NMR spectra, melting point measurement and GC-MS with authentic compounds. |
72% | With chromium (VI) oxide on aluminium silicate at 20℃; for 1h; | |
72% | With bismuth(III) bromide; dihydrogen peroxide In water at 70℃; for 0.5h; Green chemistry; | General Experimental Procedure for the Oxidation of Alcohols: General procedure: To a solution of the alcohol (1.0 mmol) and hydrogen peroxide(5.0 mmol, 30% aq) was added BiBr3 (10 mol%). The reactionmixture was stirred at 70 °C for 10-40 min, and thereaction mixture was extracted with dichloromethane (2 × 5mL). The combined organic layers were washed with saturatedbrine (2 × 5 mL) and dried with anhydrous MgSO4. After evaporationof the solvent, the residue was purified by flash columnchromatography (SiO2; CH2Cl2-hexane, 3:2) to afford the purecarbonyl compound. |
71% | With quinolinium monofluorochromate(VI) In hexane for 4h; Heating; | |
71% | With air; potassium carbonate at 20℃; for 18h; | |
71% | With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In water at 25℃; for 24h; Micellar solution; | General procedure for the oxidation of alcohols General procedure: A vial was charged with alcohol (1 mmol), IBX (1.2 mmol, 1.2 equiv) and 2 wt % GMPGS-2000/H2O solution (5 mL). The mixture was stirred for 24 h at 25 °C and filtered. The solid was washed with CH2Cl2 and the filtrate was extracted with CH2Cl2 (3×10 mL). Then, the organic phase was combined and dried with anhydrous Na2SO4, evaporated to dryness. The crude product was purified was purified by column chromatography on silica gel eluted with (petroleum ether/EtOAc) to afford the desired product. |
63% | With oxygen at 30℃; for 24h; Irradiation; | |
62% | With chromium(VI) oxide for 8h; | |
61% | With aluminum oxide; quinolinium monofluorochromate(VI) In hexane for 6h; Ambient temperature; | |
60% | With silica gel; ferric nitrate In hexane for 5h; Heating; | |
53% | With quinolinium monofluorochromate(VI) In dichloromethane for 6.5h; Heating; | |
50% | With 2,2,6,6-tetramethyl-piperidine-N-oxyl In water; ethylene glycol at 20℃; for 17h; | |
41% | With C17H25N2Se(1+)*Cl(1-); dihydrogen peroxide In water at 60℃; for 24h; | |
36% | With oxygen at 60℃; for 24h; Irradiation; | |
With 4-methylmorpholine N-oxide In acetonitrile at 25℃; | ||
With copper at 240 - 300℃; | ||
With dipyridinium dichromate In dichloromethane | ||
67 % Chromat. | With 2,2,6,6-tetramethyl-piperidine-N-oxyl; Oxone; tetrabutylammomium bromide In dichloromethane at 20℃; for 12h; | |
With sodium hypochlorite; sodium hydrogencarbonate; potassium bromide In dichloromethane at 0℃; for 0.25h; | ||
Multi-step reaction with 2 steps 1: 1.) lead tetraacetate, Mn(OAc)2*4H2O / 1.) benzene, reflux, 1 h | ||
Multi-step reaction with 2 steps 1: 1.) NaH / 1.) THF, 2.) room temp., 2 d 2: 15 percent / KBr, KOH / cyclohexane; H2O / Heating; anodic oxidation | ||
Ca. 45 %Chromat. | With acetaldehyde at 30℃; for 24h; aq. phosphate buffer; Microbiological reaction; Combinatorial reaction / High throughput screening (HTS); chemoselective reaction; | |
With potassium phosphate; recombinant rat brain aldo-keto reductase R1B10; nicotinamide adenine dinucleotide phosphate In methanol Enzymatic reaction; | ||
With oxygen In toluene at 20℃; for 12h; chemoselective reaction; | ||
Stage #1: nonyl alcohol In dichloromethane at 10℃; for 0.05h; Sonication; Stage #2: With sodium hypochlorite; sodium bromide In dichloromethane; water at 10℃; for 0.0833333h; | ||
91 %Chromat. | With C23H35N3O3(1+)*Br(1-); copper In chlorobenzene at 80℃; for 15h; | |
With rabbit 3-hydroxyhexobarbital dehydrogenase (AKR1C29); NADP In aq. phosphate buffer; ethyl acetate at 37℃; for 0.5h; Enzymatic reaction; | 2.6 Product identification General procedure: The reaction was conducted at 37°C in a 2.0-mL reaction mixture, containing coenzyme (1-mM NADP+ or 0.1-mM NADPH), substrate (0.05-0.1mM), enzyme (0.1-0.3mg), and 0.1-M potassium phosphate, pH 7.4. The substrate and products were extracted into 4-mL ethyl acetate 30min after the reaction was started at 37°C. The products of oxidoreduction of steroids [25] and reduction of PGD2 [28], farnesal [29] and 4-oxo-2-nonenal [18] were analyzed by TLC, as described. The reduced products of TBE were identified by the HPLC methods [23]. The products of 3HB oxidation, 3OB reduction, 5β-androstane-3α,17β-diol oxidation and 5β-androstan-3α-ol-17-one reduction were analyzed by the liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS) using a Hewlett-Packard HP 1100 Series LC/MSD system attached with a diode array detector and a column (Mightysil RP-18 GP 5μm, 4.6mm×250mm, Kanto Chemical Co., Tokyo, Japan). Separations were carried out at a flow rate of 0.5mL/min and 40°C using the following mobile phases: 25% acetonitrile aqueous solution containing 0.1% formic acid for 3OB and α/β-3HBs, and 80% acetonitrile aqueous solution containing 0.1% formic acid for the two steroids. 3OB, α-3HB, β-3HB, 5β-androstan-3α-ol-17-one and 5β-androstane-3α,17β-diol were detected by monitoring their total ions (m/z 249.1, 251.1, 251.1, 289.4 and 291.4, respectively) in the negative ESI mode, and eluted at the retention times of 20.1, 17.6, 16.8, 14.9 and 12.7min, respectively. The detection limits of 3OB, α/β-3HBs and the two steroids were 0.1, 0.1 and 1nmol, respectively. | |
79 %Chromat. | With pyridine; Tributylphosphine oxide; oxygen; palladium diacetate In toluene at 80℃; Molecular sieve; | |
Stage #1: nonyl alcohol In dichloromethane for 0.00833333h; Sonication; Micellar solution; Stage #2: With sodium hypochlorite; sodium bromide In dichloromethane at 10℃; for 0.05h; Micellar solution; | ||
0.2 g | Stage #1: nonyl alcohol With oxalyl dichloride; dimethyl sulfoxide In dichloromethane at -78℃; for 1h; Inert atmosphere; Stage #2: With triethylamine In dichloromethane at -78 - 20℃; Inert atmosphere; | |
> 99 %Chromat. | Stage #1: nonyl alcohol With dimethyl sulfoxide; p-toluenesulfonyl chloride In toluene at 0 - 20℃; for 1.5h; Stage #2: With triethylamine In toluene at 20℃; for 0.583333h; chemoselective reaction; | General Procedure General procedure: The DMSO (0.23 g; 3 mmol) was added dropwise to the stirred mixture of tosyl chloride (0.29 g; 1.5 mmol) and dry toluene (2.0 ml) at °C for 10 min and stirring was continued for another 15 min. A solution of alcohol (1.0 mmol) in dry toluene (1 ml) was then injected into the solution, and the temperature of the resulting mixture was brought to the ambient temperature. The mixture was stirred at ambient temperature for 90 min before triethylamine (0.30 g; 3.0 mmol) was added dropwisein ca. 10 min. Once the reaction was complete, the complex was treated with water (5 mL) and the mixture was extracted using toluene (25 mL). The organic layer was dried over sodium sulfate (Na2SO4). Samples of the reaction mixture were monitored by GC. The products of the reaction were determined via comparison with those of authentic samples of carbonyl compounds.[26] Full experimental data are available in the online supplemental section. |
With pyridine; oxygen In water at 65℃; for 12h; | ||
98 %Chromat. | With oxygen; potassium carbonate In water at 25℃; for 1.5h; | |
With sodium hypochlorite; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; sodium bromide In dichloromethane at 10℃; for 0.0166667h; Green chemistry; | ||
With potassium hydrogencarbonate; potassium bromide In dichloromethane at 0℃; for 0.166667h; | ||
Stage #1: nonyl alcohol With oxalyl dichloride In dichloromethane; dimethyl sulfoxide at -78℃; for 1.33333h; Stage #2: With triethylamine In dichloromethane; dimethyl sulfoxide at -78 - 20℃; for 2h; | ||
With sodium hypochlorite; sodium bromide In dichloromethane; water at 10℃; for 0.0166667h; | 4 2.6. PIC-mediated Montanari oxidation of alcohols General procedure: alcohol substrate (1.0 mmol), TEMPO(0.001 mmol, 0.068 mg) or PES-im-TEMPO (0.001 mmol, 5.0 mg), and CH2Cl2 (3.5 mL) were charged into a 25-mL round-bottom flask. The mixture was cooled to 10 °C, and NaBr (1.0 M, 0.15 mL) and NaClO(0.37M, 3.35mL, pH≈9.1) were added sequentially. The resulting mixture was magnetically stirred at 1400 rpm. After a certain period of time,the reaction was quenched by consuming hypochlorite with excess sodium sulfite, and the supernatant was analyzed by gas chromatography(GC) after dried with anhydrous sodium sulfate. The catalyst precipitated after adding HCl (1.0M) to adjust the pH to 2, and was collected by centrifugation and used for next cycles after drying in vacuum. The organic layer was separated and dried over anhydrous Na2SO4. The solvent was removed under reduced pressure to result in the crude product, which was purified by silica gel column chromatography (ethyl acetate/petroleum ether 10/1). The yield of the product was calculated by 1H NMR spectroscopy after careful determination of its weight. | |
60 %Spectr. | With (2,9-dimethyl-1,10-phenanthroline)-palladium(II) acetate; 2,6-dimethoxy-p-quinone; tetrabutylammonium tetrafluoroborate; acetic acid In dimethyl sulfoxide at 20℃; for 8h; Electrolysis; Inert atmosphere; | 2.5. Electrolysis General procedure: A homemade airtight electrolysis cell was used equipped with areticulated vitreous carbon (RVC) as working electrode (basi, USA),a bridged Ag/AgCl reference electrode with 2 M LiCl ethanol solution as inner solution and a 0.1 M Bu4NBF4 DMSO as bridge solution was used and the counter electrode, a platinum rod electrode, was put in a divided cell separated from the anodic partby a ceramic frit. In a typical electrolysis experiment 4 mL of a 0.2 MBu4NBF4 DMSO solution was added to the divided part followed bythe addition of 200 mL of acetic acid. In the anodic part neocuproinePd(OAc)2 (0.1 equivalent), 2,6-dimethoxybenzoquinone(0.6 equivalent) and the alcohol (0.7 mmol) was added to a 14 mL solution of 0.2 M Bu4NBF4 in DMSO. The cell was closed andput under an argon atmosphere. Stirring was started, next apotential of 0.7 V was applied. After the appropriate reaction time30 mL of water was added to the reaction mixture. The resultingmixture was extracted with tert-butylmethylether (3 times 25 mL).The collected organic layer was washed with 15 mL of water tofurther remove DMSO. Next the organic layer was dried withMgSO4 filtered and evaporated. The resulting solution wasexamined with NMR. Isolated products were obtained usingcolumn chromatography with heptane/ethylacetate (7/3) aseluent. |
With 2,2'-azinobis(3-ethylbenzthiazolinesulfonate); horse-radish peroxidase; choline oxidase from Arthrobacter cholorphenolicus, mutant S101A/D250G/F253R/V355T/F357R/M359R In aq. phosphate buffer at 30℃; for 24h; Enzymatic reaction; | ||
With Bi24O31Br10(OH)(x) In acetonitrile at 20℃; for 24h; Irradiation; | ||
Stage #1: nonyl alcohol With oxalyl dichloride; dimethyl sulfoxide In dichloromethane at -78℃; for 0.75h; Stage #2: With triethylamine In dichloromethane at -78℃; for 0.5h; | ||
With sodium hypochlorite; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; sodium bromide In dichloromethane; water at 10℃; for 0.00416667h; | ||
With dihydrogen peroxide; C11H18Br2FeN4(1+)*Br(1-) In acetonitrile at 30℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With toluene-4-sulfonic acid In benzene Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium phosphate buffer; 2-alkenal reductase of Mucor griseo-cyanus AHU6044; NADPH; Triton X-100 at 37℃; for 0.166667h; relative rate; | ||
With recombinant barley alkenal hydrogenase 1; NADPH In phosphate buffer; ethanol at 30℃; | ||
> 99 %Chromat. | With D-glucose; glucose dehydrogenase (GDH; 10U); holo-(flavin free double bond reductase from Nicotiana tabacum); nicotinamide adenine dinucleotide phosphate In aq. phosphate buffer at 30℃; for 24h; Enzymatic reaction; |
With recombinant Cyclocybe aegerita ene/yne-reductase CaEnR1; NADPH In aq. phosphate buffer at 24℃; for 3h; Enzymatic reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With bis(acetylacetonate)nickel(II); triphenylphosphine In tetrahydrofuran; hexane at 0℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With carbon dioxide; hydrogen at 80℃; | ||
With hydrogen In tetrahydrofuran; propan-1-ol; diethylene glycol dimethyl ether at 65℃; for 0.75h; | 32 In a glove box, the following solutions were prepared: a hydrogenation catalyst solution containing a MePh4P3Pr (0.0903 g, 0.1804 mmol) and Rh(CO)2acac (0.0357 g, 0.1384 mmol) in THF (15.0 g) and 1-propanol (9.0 g); a hydroformylation catalyst solution containing Ligand T (0.250 g, 0.2976 mmol) and Rh(CO)2acac (0.0359 g, 0.1391 mmol) in 10.0 g of THF; and a substrate solution containing 1-octene (4.500 g, 40.10 mmol), 1-butanal (4.20 g, 58.2 mmol) and diglyme (1.055 g, 11.5 mmol, as internal GC standard). An initial GC sample was taken from the substrate solution (0.10 ml) and diluted with THF. Under nitrogen, the hydrogenation catalyst solution was transferred into the reactor and the hydroformylation catalyst solution into a sample cylinder. The olefin solution was added into the substrate addition cylinder. The solutions in the reactor and the cylinders were purged three times with 300 psi 2:1 hydrogen and CO. The reactor was then sealed, stirred and heated under 300 psi 2:1 hydrogen and CO. After stirring at 65° C. for 15 minutes, the pressure in the reactor was reduced to 200 psi and then the hydroformylation catalyst solution was forced into the reactor under 300 psi 2:1 hydrogen and CO. After 30 minutes, the pressure in the reactor was reduced to 240 psi and then the olefin was forced into the reactor with 300 psi 2:1 hydrogen and CO. The reactor was then fed with 300 psi 2:1 hydrogen and CO with a slow purge to maintain 2:1 hydrogen and CO ratio in the reactor. Five GC samples were taken during the course of the reaction and the results are shown in Table 7. TABLE 1 Results of reductive hydroformylation of 1-octene and 1-butanal using Ligand B and Ligand T. Time Min- 6.25 16.00 32.75 174 1280 utes Octene Mol % 39.63 67.72 83.37 96.73 99.07 consumption Aldehyde Mol % 21.83 43.30 61.93 92.29 98.85 conversion Ave. rate of Mol/ 2.23 1.58 0.97 0.23 0.03 oxo reaction L/hr Ave. rate of Mol/ 2.75 2.46 1.88 0.58 0.08 hydrogenation L/hr N:I of Mol/ 55.47 46.76 35.70 12.70 No.DIV/0. aldehydes mol N:I of Mol/ No.DIV/0. 136.49 159.02 56.79 39.37 alcohols mol n-Nonanol Mol % 12.6 29.3 46.9 78.1 86.9 selectivity | |
With dicarbonyl(acetylacotonato)rhodium(I); hydrogen; (2-oxo-1,2-dihydro-6-pyridyl)diphenylphosphine In toluene at 80℃; for 72h; Inert atmosphere; Autoclave; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With N,N,N,N,N,N-hexamethylphosphoric triamide; samarium diiodide In tetrahydrofuran at 0℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With molecular sieve In methanol at 4℃; for 24h; | |
for 0.166667h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; benzyl chloride; at 90℃; for 0.5h;Microwave irradiation; | General procedure: A 10 mL reaction vessel was charged in air with Pd(PPh3)4 (6 mg, 1 mol %), aldehyde (0.5 mmol), K2CO3 (207 mg, 1.5 mmol), benzyl chloride (70 muL, 0.6 mmol) and EtOH (1 mL). The vessel was sealed and submitted to microwave irradiation for 30 min at 90 C, using an initial power of 30 W. (Microwave reactions were carried out with a CEM Discover 300 W monomode microwave instrument. The closed vessels used were special glass tubes with self-sealing septa that controlled pressure with appropriate sensors on the top (outside the vial). The temperature was monitored through a non-contact infrared sensor centrally located beneath the cavity floor.) The mixture was then allowed to cool to room temperature, filtered over a pad of Celite and rinsed with EtOH (5 mL). The filtrate was concentrated in vacuo and the product was purified by flash chromatography on silica gel (CH2Cl2/hexane). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
43% | With strontium In tetrahydrofuran at -15℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
48.7% | Example 2; Reductive Ozonolysis of Oleic Acid; The same micro falling-film reactor, as described above, was used for the first reaction step of the reductive ozonolysis, the operating parameters, listed in column 4 (Table 1), being adjusted. The ozonization products were again directly reacted in a following microreactor. The reactor used for the reduction was a palladium-coated film reactor. The reactor consisted of 64 channels with a width of 300 mum, a depth of 100 mum, and a length of 75 mm. Hydrogen was used in countercurrent for the hydrogenating cleavage of the ozonides. Azelaic acid semialdehyde and pelargonic aldehyde were mainly formed as products. The products were analyzed by GC. The second reaction step was carried out at 30 C./5 bar pressure. A test was carried out with 0.25 Nl/h hydrogen, the yield of azelaic acid semialdehyde being on average 48.7%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 18% 2: 1.2% | With water In acetone at 120℃; for 140h; | |
With bis(trifluoromethanesulfonyl)amide at 70℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: -78 °C 2: 1.)9-Borabicyclononan, 2.)H2O2/OH(-) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
palladium; In methanol; | EXAMPLE 13 STR13 1,5-(Nonylimino)-1,5-dideoxy-D-glucitol A solution of <strong>[19130-96-2]1,5-dideoxy-1,5-imino-D-glucitol</strong> (0.5 g, 0.0031 mole); nonyl aldehyde (0.52 g, 0.0037 mole) and 5% Pd black (0.1 g) in methanol (100 ml) was hydrogenated (60 psi/25 C./46 hrs.). After filtering the resulting mixture, the filtrate was concentrated with a gentle flow of nitrogen to an oily solid. This material was stirred with a small amount of acetone and the solid filtered. Recrystallization from ethanol--acetone gave the title compound, DSC ca. 109 C. Structure assignment was supported by NMR, infrared spectra and elemental analysis. Analysis calcd. for C15 H31 NO4: C, 62.25; H, 10.80; N, 4.84. Found: C, 62.15; H, 10.86; N, 4.79. | |
palladium; In methanol; | EXAMPLE 13 STR13 1,5-(Nonylimino)-1,5-dideoxy-D-glucitol A solution of <strong>[19130-96-2]1,5-dideoxy-1,5-imino-D-glucitol</strong> (0.5 g, 0.0031 mole), nonyl aldehyde (0.52 g, 0.0037 mole) and 5% Pd black (0.1 g) in methanol (100 ml) was hydrogenated (60 psi/25 C./46 hrs.). After filtering the resulting mixture, the filtrate was concentrated with a gentle flow of nitrogen to an oily solid. The material was stirred with a small amount of acetone and the solid filtered. Recrystallization from ethanol-acetone gave the title compound, DSC ca. 109 C. Structure assignment was supported by NMR, infrared spectra and elemental analysis. Analysis calcd. for C15 H31 NO4: C, 62.25; H, 10.80; N, 4.84. Found: C, 62.15; H, 10.86; N, 4.79. | |
palladium; In methanol; | EXAMPLE 13 STR14 1,5-(Nonylimino)-1,5-dideoxy-D-glucitol A solution of <strong>[19130-96-2]1,5-dideoxy-1,5-imino-D-glucitol</strong> (0.5 g, 0.0031 mole); nonyl aldehyde (0.52 g, 0.0037 mole) and 5% Pd black (0.1 g) in methanol (100 ml) was hydrogenated (60 psi/25 C./46 hrs.). After filtering the resulting mixture, the filtrate was concentrated with a gentle flow of nitrogen to an oily solid. This material was stirred with a small amount of acetone and the solid filtered. Recrystallization from ethanol-acetone gave the title compound, DSC ca. 109 C. Structure assignment was supported by NMR, infrared spectra and elemental analysis. Analysis calcd. for C15 H31 NO4: C, 62.25; H, 10.80; N, 4.84. Found: C, 62.15; H, 10.86; N, 4.79. |
palladium; In methanol; | EXAMPLE 3 1,5(Nonylimino)-1,5-dideoxy-D-glucitol A solution of <strong>[19130-96-2]1,5-dideoxy-1,5-imino-D-glucitol</strong> (0.5 g, 0.0031 mole), nonyl aldehyde (0.52 g, 0.0037 mole) and 5% Pd black (0.1 g) in methanol (100 ml) was hydrogenated (60 psi/25 C./46 hrs.). After filtering the resulting mixture, the filtrate was concentrated with a gentle flow of nitrogen to an oily solid. This material was stirred with a small amount of acetone and the solid filtered by reduced pressure. Recrystallization from ethanol-acetone gave the title compound, DSC ca. 109 C. Structure assignment was supported by NMR, infrared spectra and elemental analysis (289.4). Analysis calcd. for C15 H31 NO4: C, 62.25; H, 10.80; N, 4.84. Found: C, 62.15; H, 10.86; N, 4.79. | |
palladium; In methanol; | EXAMPLE 13 STR13 1,5-(Nonylimino)-1,5-dideoxy-D-glucitol A solution of <strong>[19130-96-2]1,5-dideoxy-1,5-imino-D-glucitol</strong> (0.5 g, 0.0031 mole); nonyl aldehyde (0.52 g, 0.0037 mole) and 5% Pd black (0.1 g) in methanol (100 ml) was hydrogenated (60 psi/25 C./46 hrs.). After filtering the resulting mixture, the filtrate was concentrated with a gentle flow of nitrogen to an oily solid. This material was stirred with a small amount of acetone and the solid filtered. Recrystallization from ethanol - acetone gave the title compound, DSC ca. 109 C. Structure assignment was supported by NMR, infrared spectra and elemental analysis. Analysis calcd. for C15 H31 NO4: C, 62.25; H, 10.80; N, 4.84. Found: C, 62.15; H, 10.86; N, 4.79. | |
Working Examples 1. Synthesis of N-Nonyl DNJTable 1. Materials for NN-DNJ synthesisProcedure: A 50-mL, one-necked, round-bottom flask equipped with a magnetic stirrer was charged with DNJ (500 mg), ethanol (100 mL), nonanal (530 mg), and acetic acid (0.5 mL ) at room temperature. The reaction mixture was heated to 40-45 C and stirred for 30-40 minutes under nitrogen. The reaction mixture was cooled to ambient temperature and Pd/C was added. The reaction flask was evacuated and replaced by hydrogen gas in a balloon. This process was repeated three times. Finally, the reaction mixture was stirred at ambient temperature overnight. The progress of reaction was monitored by TLC (Note 1). The reaction mixture was filtered through a pad of Celite and washed with ethanol. The filtrate was concentrated in vacuo to get the crude product. The crude product was purified by column chromatography (230-400 mesh silica gel). A solvent gradient of methanol in dichloromethane (10-25%) was used to elute the product from the column. All fractions containing the desired product were combined, and concentrated in vacuo to give the pure product (420mg). Completion of the reaction was monitored by thin layer chromatography (TLC) using a thin layer silica gel plate; eluent; methanol : dichloromethane = 1 :2 | ||
420 mg | 1. Synthesis of N-Nonyl DNJ [tabl0001-en] Table 1. Materials for NN-DNJ synthesisName Amount DNJ 500 mg Nonanal 530 mg Ethanol 100 mL AcOH 0.5 mL Pd/C 500 mg (0042) Procedure: A 50-mL, one-necked, round-bottom flask equipped with a magnetic stirrer was charged with DNJ (500 mg), ethanol (100 mL), nonanal (530 mg), and acetic acid (0.5 mL) at room temperature. The reaction mixture was heated to 40-45 C and stirred for 30-40 minutes under nitrogen. The reaction mixture was cooled to ambient temperature and Pd/C was added. The reaction flask was evacuated and replaced by hydrogen gas in a balloon. This process was repeated three times. Finally, the reaction mixture was stirred at ambient temperature overnight. The progress of reaction was monitored by TLC (Note 1). The reaction mixture was filtered through a pad of Celite and washed with ethanol. The filtrate was concentrated in vacuo to get the crude product. The crude product was purified by column chromatography (230-400 mesh silica gel). A solvent gradient of methanol in dichloromethane (10-25%) was used to elute the product from the column. All fractions containing the desired product were combined, and concentrated in vacuo to give the pure product (420mg). Completion of the reaction was monitored by thin layer chromatography (TLC) using a thin layer silica gel plate; eluent; methanol: dichloromethane = 1:2 | |
Procedure: A 50-mL, one-necked, round-bottom flask equipped with a magnetic stirrer was charged with DNJ (500 mg), ethanol (100 mL), nonanal (530 mg), and acetic acid (0.5 mL ) at room temperature. The reaction mixture was heated to 40-45 C and stirred for 30-40 minutes under nitrogen. The reaction mixture was cooled to ambient temperature and Pd/C was added. The reaction flask was evacuated and replaced by hydrogen gas in a balloon. This process was repeated three times. Finally, the reaction mixture was stirred at ambient temperature overnight. The progress of reaction was monitored by TLC (Note 1). The reaction mixture was filtered through a pad of Celite and washed with ethanol. The filtrate was concentrated in vacuo to get the crude product. The crude product was purified by column chromatography (230-400 mesh silica gel). A solvent gradient of methanol in dichloromethane (10-25%) was used to elute the product from the column. All fractions containing the desired product were combined, and concentrated in vacuo to give the pure product (420mg). Completion of the reaction was monitored by thin layer chromatography (TLC) using a thin layer silica gel plate; eluent; methanol : dichloromethane = 1 :2 | ||
Working Examples 1. Synthesis of N-Nonyl DNJTable 1. Materials for NN-DNJ synthesisProcedure: A 50-mL, one-necked, round-bottom flask equipped with a magnetic stirrer was charged with DNJ (500 mg), ethanol (100 mL), nonanal (530 mg), and acetic acid (0.5 mL ) at room temperature. The reaction mixture was heated to 40-45 C and stirred for 30-40 minutes under nitrogen. The reaction mixture was cooled to ambient temperature and Pd/C was added. The reaction flask was evacuated and replaced by hydrogen gas in a balloon. This process was repeated three times. Finally, the reaction mixture was stirred at ambient temperature overnight. The progress of reaction was monitored by TLC (Note 1). The reaction mixture was filtered through a pad of Celite and washed with ethanol. The filtrate was concentrated in vacuo to get the crude product. The crude product was purified by column chromatography (230-400 mesh silica gel). A solvent gradient of methanol in dichloromethane (10-25%) was used to elute the product from the column. All fractions containing the desired product were combined, and concentrated in vacuo to give the pure product (420mg). Completion of the reaction was monitored by thin layer chromatography (TLC) using a thin layer silica gel plate; eluent; methanol : dichloromethane = 1 :2 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: trioleoylglycerol; trilinolenin With ozone In water at 27℃; for 5h; Stage #2: With hydrogen In tetrahydrofuran at 20 - 135℃; for 5.5h; | 2.A; 2.B; 2.C; 2.D; 2.E; 2.F Example 2: Preparation of Polyols from Canola Oil (GII-Polyol); Ozonolysis Reactor; [00297] The reactor 10 presently disclosed offers an improvement over prior art ozonolysis vessels, such as those utilized by Lin, S. H. and Wang, C. H. (Industrial wastewater treatment in a new gas-induced ozone reactor, Journal of Hazardous Materials *** 295-309,(2003)) illustrated in Figure 41 (Prior Art). The reactor of the present invention is fed with a motor 28, such as a Direct Current Permanent Magnet 1 HP Motor from Leeson electric-corporation, USA. The water, which temperature is controlled by a chiller, is rushed into the outer layer 14 of the reactor (entry labelled "H2O in"; 16), circulated around the reaction vessel 12 and evacuated (labelled "H2O out"; 18). The water is kept flowing during the reaction to keep the reaction system at a constant temperature. Ozone is generated in an ozone generator (such as Azcozon Model RMV16-16 from Azco Industries Ltd, Canada) with oxygen or air as the feed gas, and introduced into the reactor from the two apertures for ozone input at opposing ends of an ozone inlet channel 24 (the apertures being labelled as "O3, O2 in" (20) and "O3, air in" (22) in Figure 39). The ozone inlet channel 24 is disposed at the lower end of the reaction vessel 12 and extends across the diameter thereof. The gas is released from the ozone inlet channel 24 into the reaction vessel 12 through a plurality of pores 26, which are evenly spaced across the length of the ozone inlet channel 24. The nonreturn valves 36 prevent backflow of the reaction solution to the two apertures for ozone input (20, 22) and the aperture for nitrogen input, 38.[00298] The two apertures for ozone input, 20 and 22, and the pores 26 in the ozone inlet channel 24, provide for substantially uniform distribution of ozone throughout the reaction vessel 12. This improved distribution of ozone increases the effectiveness of the ozonolysis reaction, allowing for shorter reaction times, higher reaction temperatures, and increased homogeneity of end products. This arrangement differs from prior art ozonolysis vessels, such as the embodiment illustrated in Figure 41, which only have a single aperture for ozone input. [00299] The magnet motor 28 is connected to a longitudinally disposed agitator 30 which extends into the reaction vessel 12. The motor 28 is kept rotating at high speed during the reaction. The agitator 30 comprises a plurality of pitched blades 32, which may be fixedly mounted or releasably mounted to the agitator 30 by means known to those skilled in the art. In one embodiment, the blades 32 may be welded to the agitator 30. In one embodiment, the blades 32 are trapezoidal in shape, which reduces the resistance. In another embodiment, the blades 32 are attached to the agitator 30 at an angle of from about 30 degrees to about 60 degrees. Such an angle of attachment has been found to reduce vortex formation and increase the rate of reaction. In yet another embodiment, the blades 32 contain a plurality of holes 34, which increase contact areas between the reagents and further reduce vortex formation. Figures 40(a) and 40(b) illustrate the blades 32. in greater detail in accordance with one embodiment of the invention. The plurality of pitched blades are oriented such as to direct the contents of said reaction vessel downward toward the ozone inlet channel.[00300] Thus, in the reactor vessel of the current invention, the apertures for ozone input 20 and 22, the ozone inlet channel 24, the pores 26 within the ozone inlet channel 24, as well as the rotating blades 32 have been designed to ensure thorough contact and full reaction of ozone with the starting material.[0030I]In one embodiment, the blades 32, agitator 30, and reaction vessel 12 may be made of stainless steel, such as SS 316 L.[00302] Li one embodiment of the present invention, the reactor has the following characteristics, which are presently described by way of example and should not be interpreted as limiting. It has been found that a reaction vessel 12 having a volume of 1727 cm3 (diameter = 10 cm; height = 22 cm) can accommodate 200 g of starting material (vegetable oil) in 1000 mL of solvent. The ozone inlet channel 24 comprises twelve pores 26 evenly spaced at 0.8 cm apart, wherein the pores have a diameter of 0.8 mm. The agitator 30 has six blades 32 having the dimensions illustrated in the embodiment shown in Figure 40(a), and the blades 32 contain six holes 34 having a diameter of 0.3 cm. The angle of attachment of the blades 32 to the agitator 30 can vary from about 30 degrees to about 60 degrees. The blades 32,. agitator 30, and reaction vessel 12 are made of SS 316 L.; Step A - Ozonolysis; [00303] Canola oil (10Og) and deionized water (40Og) were poured into a specially designed reactor (schematic shown in Figure 39 and described above). The reaction was performed at 270C, at 5 L/min O2 flow rate and 80 rpm agitation rate. After 5 hours, the ozone generator was stopped and the reaction vessel was purged with N2 for 10 minutes to remove the unreacted ozone from the vessel. 400ml of tetrahydrofuran (THF) was then added into the vessel to dissolve the ozonide product. The product was then transferred to a separatory funnel where the organic part was collected for the hydrogenation step.; Step B - Hydrogenation; [00304] 10.5 g of Raney nickel catalyst were added to the ozonide (490.8g) in THF in a hydrogenation vessel (2L, Parr Instrument Co, USA) fitted with a magnetic drive. The reaction vessel was flushed 3 times with nitrogen at 200 psi pressure to remove the air and then was charged with hydrogen gas at 350 psi at room temperature. The temperature was increased over 30 minutes to 1350C with a concomitant increase in pressure to 520 psi. The hydrogenation reaction was carried for 5 hours at this temperature and the pressure decreased with the consuming of hydrogen. The temperature was then reduced to room temperature with cooling water and to a final pressure of 290 psi. The unreacted hydrogen gas was removed from the reaction vessel with nitrogen gas. The remaining mixture was filtered over Celite and the aqueous layer removed in a separatory funnel[00305] To insure complete hydrogenation of the double bonds and ozonolysis products, the above procedure was repeated on the remaining organic material from the separatroy funnel. The final hydrogenation product was kept for distillation.; Step C - Gas Chromatography (GC); [00306] To determine the amounts of short chain compounds present as by-products from the hydrogenation reaction, a Varian 3500 Capillary Gas Chromatograph equipped with a Flame Ionization Detector (GC-FID), a Varian 8200 Auto Sampler and a BP20025 column (30-m long, 0.25-mm internal diameter, and 0.25-μm thick silica wall) was used. The system was controlled with Varian' s "Star Chromatography Workstation" software V.5.51. The injector and the detector temperature were fixed at 250°C. The temperature of the column initially set at 50°C was increased to 250°C in two successive steps: from 500C to 9O0C at a rate of 25°C/minute and from 900C to 2500C at a rate of 10°C/minute.; Step D - Wiped- blade Molecular Distillation; [00307] The solvent was removed on a rotary evaporator (Heidolph Laborota 4001, UK) to yield a viscous yellow oil. GC analysis showed that the removed THF was 100% pure and no product was also removed with THF. The wiped blade molecular distillation unit (Model VKL 70/ICL-04, from rncon Processing) was set up at a jacket temperature of 1150C, and the temperature of the condenser 3O0C. The pressure of the distillation system was reduced to 20 mTorr and the viscous oily product added into the distillation system through an addition funnel at a speed of lmL/min. After all the product had been added to the distillation system, the unit was kept running for 30 minutes, to allow the complete collection of the residue and distillate. Finally, distillate (31.Ig) and residue (47.Og) were obtained. The distillate fractions from the flash evaporator and distillation were analyzed by GC, and the residue fraction analyzed by HPLC.; Step E - Flash Chromatography; [00308] A column of dimensions 3 id x 30cm was packed with 40Og (about 212 mL volume) of silica gel (230-400 mesh). Material from the residue fraction of distillation (4.3g) was added. The column was then eluted under air pressure with gradient flow phase composed of hexane and ethyl acetate. The ratios (v/v) of hexane to ethyl acetate was started with 50:1, then gradually decreased to 20:1, 17:1, 10:1, 8:1, 5:1, 3:1, 2:1, 1:1, followed by 1 :2, 1 :3, 1 :4. Finally pure ethyl acetate was used and the fractions were collected in 30mL-test tubes. Ratios of flow phase of 20:1, 8:1, 2:1 and 1:4 were used on fractions 28-50, 131-143, 264-289, and 366-389 respectively. Thin layer chromatography (TLC) was run on each fraction using hexane and ethyl acetate as the developing system with ratios (v/v) of hexane and ethyl acetate of 3:1, 2:1, and 1:1. The glycerides and related compounds were detected by spraying the plates first with methanol containing 10% sulphuric acid (concentration 98%) and then heating them at 2000C for 5 minutes.; Step F - High Performance Liquid Chromatography (HPLC); [00309] The HPLC analysis protocol used was a modification of the procedure developed by Elfman-Borjesson and Harrod (Elfman-Borjesson, I. and M. Harrod, Analysis of Non-Polar Lipids by HPLC on a Diol Column. J. High Resol. Chromatogr. 20: 516-518 (1997)) for analysis of lipid derivatives. The HPLC system consisted of a dual Milton Roy pump with a 20 μL auto-injector. The column was packed by Betasil Diol-100 (5 μm particle size) 250x4 mm produced by Thermo Hypersi-Keytone and maintained at 5O0C with a Biorad column heater. The detector was an Alltech EDSL 2000 evaporative light scattering system maintained at 1000C with a gain setting of 10 (on the 12 unit scale) and a nitrogen pressure of 2 bar. Two solvents were connected to the pump as the mobile phase. A was 100% heptane and B 50% heptane with 50% isopropyl alcohol (IPA). A run consisted of a linear gradient of 100% A to 83% A and 17% B in 30 min; then back to 100% A in 1 minute at a flow rate of 3 mL/min. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
710 mg | With pyrrolidine; pyridine In tetrahydrofuran at 0 - 20℃; Inert atmosphere; stereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
4,6-bis(diphenylphosphino)-9,9'-dimethyl-2,8-disodiumdisulfonatoxanthene in 5 mL 1-butyl-3-methylimidazolium-hexafluorophosphate (BMIM-PF6) and 0.86 g dibutylether as internal standard was preformed in the autoclave for 0.5 h at 120 C. with synthesis gas (CO/H2=1:1) at a total pressure of 1.1 MPa. After the preforming, 2.37 g 1-octene were added and hydroformylated for 2 h at 1.1 MPa. The reactor content was cooled to ambient temperature, removed and the phases were separated. The organic phase was analyzed by gas chromatography and the rhodium content was determined by ICP measurements. Conversion: 17%, n/i=33.1, TOF=85 h'1, sum of hydration and isomerization products: 3.0%, [Rh]=0.027 ppm. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | General procedure: To a stirring suspension of phosphonium salts (5a-e) (1 equiv) in THF (250 mL) was added slowly 40% solution of sodium hexamethyldisilylamide (2 equiv) THF at room temperature in argon and stirring continued for 2 h. Aldehyde (1 equiv) was dissolved in THF (25 mL) and introduced drop wise. The mixture was stirred for further 3 h and then poured into 150 mL of water to get a clear solution. The resulting solution was concentrated in vacuum and the residue was extracted with diethyl ether (3 x 250 mL). The aqueous layer was acidified with 10% HCl and extracted with ether (3 x 200 mL). The organic layer obtained from the aqueous extract was dried and concentrated to afford the corresponding unsaturated carboxylic acids (6a-m). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With dodecacarbonyl-triangulo-triruthenium; water; hydrogen; lithium chloride In 1-methyl-pyrrolidin-2-one at 160℃; for 5h; Autoclave; regioselective reaction; | ||
With cobalt(III) oxide; hydrogen In tetrahydrofuran at 140℃; for 16h; High pressure; | 2.3 General procedure for reductive hydroformylation of 1-octene General procedure: In a typical experiment procedure, a 100mL high-pressure reactor was charged with 1-octene (15mmol), Co3O4(4mol%) and 12mL of dry THF. Then the reactor flushed three times with nitrogen to remove unnecessary gas contains and pressurized to 800psi by CO/H2 (1:2) gas. A reactor was then heated to 150°C for 12h with a constant stirring speed i.e. 700rpm. After completion of the reaction time, the heater was stopped and the reactor was allowed to cool to room temperature. The existing synthesis gas was carefully released. The reaction mixture was then filtered using filter paper and the crude product was analyzed by gas chromatography and mass spectrometry [28]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tert.-butylhydroperoxide; copper(II) acetate monohydrate In water; acetonitrile for 0.666667h; Inert atmosphere; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With [Rh(CO){P(CH2CH2PPh2)3}]Cl; hydrogen In dichloromethane at 80℃; for 5h; Overall yield = 71 %; regioselective reaction; | Catalytic activity towards hydroformylation reaction Catalytic activity towards hydroformylation reactionThe hydroformylation reactions were carried out in a Parr reac-tor. 2.5 mmol of the alkene and 0.005 mmol of the catalyst in 5 cm3DCM were placed in a 50 cm3reaction vessel. The reaction mixturewas purged with CO/H2(1:1) for about 5 min. The CO/H2pressurewas increased to 35 bar (actual pressure) at 25C in the closed reac-tor. The hydroformylation reactions were carried out at 80 ± 2C for3-8 h at 35 ± 2 bar. The reaction mixture was analyzed by GC andproducts were isolated by column chromatography taking hexaneand ethyl acetate as eluents. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 13.1% 2: 85.9% | With pyridine; 4-acetylamino-2,2,6,6-tetramethylpiperidine-N-oxyl; iodine; sodium hydrogencarbonate In dichloromethane; water at 20 - 25℃; for 3h; | Oxidation of alcohols with the 4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxyl-iodine system. General procedure: A mixture of 10 mL of 0.1 mol/L solution of sodium hydrocarbonate and 0.084 g (0.4 mmol) of compound 1 were charged into a 50 mL flat-bottom flask equipped with a reflux condenser and a magnetic stirrer. 4 mmol of an alcohol dissolved in 10 mL of methylene chloride (alcohol-nitroxyl 1 molar ratio1 : 0.1) was added to the solution, and then 0.4 mmolof an amine was introduced (alcohol-amine 1 : 0.1; 1-amine 1 : 1). 2.0 g (8 mmol) of crystalline iodine was added at vigorous stirring to the two-phase system; the mixture was stirred during 3 h at 20-25° and then treated with 20% solution of sodium thiosulfate for elimination of excess iodine. Aqueous and organic layers were separated, and the product was additionally extracted from the aqueous layer with methylene chloride (2×10 mL). The organic phases were combined and analyzed by means of chromatography. |
1: 34% 2: 8% | With oxygen at 60℃; for 24h; Irradiation; Darkness; | |
1: 30 %Chromat. 2: 18 %Chromat. | With 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinoxy; iodine; sodium hydrogencarbonate In dichloromethane; water at 20 - 22℃; for 3h; | 1.5 Oxidation of alcohols 1a-z with I2 catalyzed by nitroxide 4a in the absence of pyridine co-catalysts in a two-phase system CH2Cl2/NaHCO3(aq.) General procedure: A solution of alcohol 1a-z (4.0 mmol) and nitroxide 4a (42.6 mg, 0.2 mmol) in CH2Cl2 (10 mL) was added to a magnetically stirred solution of NaHCO3 (1.0 g, 11.94 mmol) in water (10 mL) at 20-22 °C, then I2 (2.02 g, 7.96 mmol) powder was added in one portion to the formed two-phase mixture. The reaction mixture was stirred at 20-22 °C for appropriate time (Table S05). Then a saturated solution of sodium thiosulfate (3 mL) was added and the resulted mixture was stirred for 5 min, organic and aqueous phases were separated and analyzed by GC-MS or HPLC (Table S05). |
1: 6 %Chromat. 2: 10 %Chromat. | With iodine; sodium hydrogencarbonate In dichloromethane; water at 20 - 22℃; for 3h; | 1.6 Oxidation of alcohols 1a,b,h,k with I2 in a two-phase system CH2Cl2/NaHCO3(aq.) in the absence of nitroxides and pyridine co-catalysts General procedure: A solution of alcohol 1a,b,h,k (4.0 mmol) in CH2Cl2 (10 mL) was added to a magnetically stirred solution of NaHCO3 (1.0 g, 11.94 mmol) in water (10 mL) at 20-22 °C, then I2 (2.02 g, 7.96 mmol) powder was added in one portion to the formed two-phase mixture. The reaction mixture was stirred at 20-22 °C for 3 h. Then a saturated solution of sodium thiosulfate (3 mL) was added and the resulted mixture was stirred for 5 min, organic and aqueous phases were separated and analyzed by GC-MS (Table S06). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1.07 g | Stage #1: (3-ethoxycarbonylpropyl)triphenylphosphonium bromide With 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone; potassium hexamethylsilazane In tetrahydrofuran at -78℃; Inert atmosphere; Stage #2: nonan-1-al In tetrahydrofuran at -78 - 20℃; Inert atmosphere; | (Z)-ethyltridec-4-enoate Triphenylphosphine (8.0g, 30.4 mmol)was added in dry toluene (20 mL) under argon atmosphere. Ethyl 4-bromobutanoate (2.0g, 10.3 mmol) was added and the mixture was stirred at 120°C for 24 h. After cooling down to room temperature, white solid was formed. The toluene was decanted off and the solid washed with hot toluene to give the crude phosphonium salt (4.2g) which was dried under vacuum over P2O5 overnight and used without further purification. 1H NMR (400 MHz, CDCl3):δ 1.22 (t, J = 7.2Hz, 3H); 1.91 (m, 2H); 2.90 (m, 2H); 4.04-4.16 (m, 4H); 7.64-7.71 (m, 6H);7.74-7.80 (m, 3H); 7.85-7.93 (m, 6H). The phosphonium salt (4.1 g, 8.95 mmol) was dissolved in dry 1,3-Dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (30 mL) underargon and then dry THF (80 mL) was added. At -78°C, a 0.5M solution of potassium bis(trimethylsilyl)amide (17.9 mL, 8.95 mmol) was added dropwise over 15 min.The reaction mixture was stirred at -78°Cfor 1 h. Then nonanal (1.6 mL, 8.95 mmol) was added dropwise over 30 min. The reaction mixture was stirred at the same temperature for 2 h, and then allowed to come to room temperature over night while stirring. The reaction was quenched with water (20 mL) and extracted withEtOAc. The organic layers were combined and washed with brine,dried over MgSO4, filtered and concentrated under reduced pressure. The residue was purified by flash column chromatography on silica gel (ethyl acetate/hexane = 1:7)to afford 2 (1.07 g, 50% for 2 steps) as a colorless oil. 1HNMR (400 MHz, CDCl3):δ 0.87 (t, J = 7.2Hz, 3H); 1.20-1.38 (m, 15H); 2.02 (apparent q, J = 6.8 Hz, 2H); 2.28-2.38 (m, 4H); 4.13 (q, J = 7.2 Hz, 2H); 5.27-5.35 (m, 1H);5.36-5.45 (m, 1H); 13C NMR (100MHz, CDCl3): δ 14.18, 14.33, 22.75, 22.91,27.28, 29.38, 29.59, 29.72, 31.97, 34.53, 60.37, 127.41, 131.63, 173.36. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With oxygen; isobutyraldehyde In methanol at 55℃; for 8h; Autoclave; Green chemistry; | Catalytic aerobic oxidation with AgFeO2-graphene General procedure: The oxidation processes were performed in a glass inlay of a 32ml steel autoclave. The autoclave was conditioned by discharge and replenish with dioxygen. All autoclave loading was carried out under air and heated to the required temperature (55°C) in an oil bath. In a generic test, 2.0mmol of substrate was added to the reactor with 0.01g AgFeO2-G, 3.0mmol isobutyraldehyde as a co-oxidant. After purgation with O2, the reactor was pressurized to 1.5bar. The stirring rate was 350rpm. At the end of 8h the reactor was depressurized, the catalyst deleted via an external magnet (1.2T) and the product mixture was analyzed by gas chromatography and 1H NMR. The products were identified with authentic samples and 1H NMR. Conversions and yields were computed about the starting substrate. The reaction products were measured by gas chromatography and recognized by comparison with the retention time and spectral data to those of an authentic sample. To ensure reproducibility, each catalytic reaction was performed at least three times. For recycling experiments, after finishing the process, the nanocomposite was recollected using a magnet, washed with acetonitrile, dried and reused. GC circumstances with column Hp-5: carrier gas N2 flow=0.7mlmin-1, inlet temp 250°C, initial column temp 90°C, final column temp 190°C, sleep 10°C min-1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With 1,4-diaza-bicyclo[2.2.2]octane In water at 40℃; for 24h; Sonication; | 4.2.1. General procedure for the synthesis of isoxazoline N-oxides (2a-z) and dihydroisoxazoles (3u-w) General procedure: 1,4-Diazabicyclo[2.2.2]octane (DABCO) (20 mol %) was added toa mixture of aldehyde (1.0 mmol, 1.0 eq.) and ethyl nitroacetate (1.68 mmol, 2.0 eq.) at 0 C dissolved in water (2 mL). The reaction mixture was stirred for 5 min at 0 C and then ultrasonicated for 24 h at 40 C. After the completion of the reaction as indicated by TLC, the reaction was quenched with ethyl acetate (3 x 6 mL). The combined organic extract was washed with water (2 x 5 mL) and 5 % HCl (1 x 3 mL), dried over anhydrous MgSO4 and concentrated in vacuo. The residue was loaded on to a silica gel column and eluted with hexane: ethyl acetate to afford isoxazoline N-oxides 2a-z, and dihydroisoxazoles 3u-w. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
0.02 g; 0.02 g | General procedure: Triethylamine and aldehyde were sequentially added to a solution of [(2,8-dimethyl-4H-[1,3]dioxino[4,5-c]pyridin-5-yl)methyl]triphenylphosphonium chloride (2) in dichloromethane (30 mL), and the reaction mixture was stirred with heating. Then, the solvent was removed in vacuo, the dry residue was dissolved in ethyl acetate, a precipitate was filtered off. Then, the filtrate was concentrated and purified using column chromatography. The product (E)-4b was recrystallized from ethyl acetate. Reaction conditions are given in Table 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
0.487 g | General procedure: Following the typical procedure described above, Rh(acac)(CO)2 (2.6 mg, 0.01 mmol), xantphos (28.9 mg, 0.05 mmol) were placed in the autoclave. Then a solution of olefin (5 mmol) in DME (8 mL) was added via cannula, the autoclave was pressurized with 20 bar of CO/H2 equimolar mixture and the reaction was conducted for 18 h, upon stirring, at 80C. After this period, the reactor was cooled to room temperature, an aqueous solution (2 mL) of NH4Cl (5.5 mmol) and NaCN (5.5 mmol) was added via inlet cannula and the reaction was kept at 50C for 20 h. After work-up and purification, the resulting alpha-aminonitrile (4.1 mmol) was suspended in a concentrated HCl solution and stirred for 6 h at 40C. The product was dissolved in methanol. After adjustment of the pH to the isoelectric point, using NH4OH (aq), the solvent was evaporated and the amino acid was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With 2,2'-azobis-(2,4-dimethylvaleronitrile); potassium carbonate; In benzene; at 60℃; for 1h;Inert atmosphere; | To a 20 mL two-necked round-bottom flask attached with areflux condenser were added V-65 (25 mg, 0.1 mmol) and K2CO3(138 mg, 1.0 mmol), and this flask was purged with argon.Then, 1-nonanal (1a, 71 mg, 0.5 mmol), <strong>[4224-69-5]methyl 2-(bromomethyl)acrylate</strong> (2a, 269 mg, 1.5 mmol), and degassedbenzene (5 mL) were added. The mixture was stirred at 60 C for1 h. The reaction mixture was filtered through a short plug ofCelite, and the filtrate was concentrated under reduced pressure.The residue was purified by flash column chromatographyon SiO2 (hexane/EtOAc = 1:0 to 30:1) and preparative HPLC(chloroform) to give methyl 2-methylene-4-oxododecanoate(3b, 101 mg, 84%). Colorless oil; Rf = 0.55 (hexane/EtOAc = 5:1).1H NMR (500 MHz, CDCl3): delta = 0.87 (t, J = 6.9 Hz, 3 H), 1.20-1.33(m, 10 H), 1.55-1.65 (m, 2 H), 2.47 (t, J = 7.4 Hz, 2 H), 3.40 (s, 2H), 3.74 (s, 3 H), 5.63 (s, 1 H), 6.33 (s, 1 H). 13C NMR (125 MHz,CDCl3): delta = 14.02, 22.58, 23.67, 29.10, 29.30, 31.76, 42.63, 45.63,52.00, 128.53, 134.25, 166.78, 207.42. IR (neat): 2953, 2926,2855, 1720, 1638 cm-1. MS (EI): m/z (relative intensity): 240(12) [M]+, 209 (5) [M - OMe]+, 141 (100), 82 (14), 71 (25), 57(26), 55 (11). HRMS (EI): m/z calcd for C14H23O3 [M]+: 240.1725;found: 240.1725. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With air at 120℃; for 10h; | Oxidation of triolein with Rancimat General procedure: The triolein oil samples were subjected to oxidation in aRancimat (679, Metrohm, Herisau, Switzerland). Elevengrammes of sample was used for the oxidation experiments.The temperature was set to 120 C and the air flowto 20 dm3/h. Triolein was treated for up to 10 h. Theoxidized samples were cooled immediately after the oxidationand stored under nitrogen below -18 C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
First, 48 g of <strong>[52829-07-9]bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate</strong>, 31.3 g of n-decanal, and 0.15 g of cuprous chloride were added to 96 ml of n-octane. The <strong>[52829-07-9]bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate</strong> was completely dissolved in n-octane with stirring at 60C.Then, 51 ml of 30% hydrogen peroxide was slowly added dropwise to the above solution for 6-7 hours. After the completion of the dropwise addition, the reaction was continued for 10 hours. The progress of the reaction was monitored by TLC and the liquid phase. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
27% | at 140℃; for 8h; | I.I.3 I.3-Compound ODEHDEHANP: The title compound, which corresponds to thegeneral formula (I) in which R’rrrR2=2-ethylhexyl, R3=n-octyl, R4=H, R5rrrR6=2-ethylhexyl, is synthesised byimplementing step A, from di(2-ethylhexyl)phosphine oxide(2.7 mmol), n-nonanal and di(2-ethylhexyl)amine (reflux for8 hours at 140° C.).10089] Yield: 27% (0.65 mmol)10090] 3’PNMR (162 MHz, CDC13, 25° C.) ö(ppm): 51.610091] ‘H NMR (400 MHz, CDC13, 25° C.) ö (ppm): 2.84(m, 2H, PCH(CH(C2H5)-C5H,3)---N); 2.34 (m, 2H);1.88-1.07 (m, 55H); 0.92-0.78 (m, 27H, CH3) HR-ESI-MS:calculated for C4,H87NOP=640.6525. found=640.65 13. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | at 140℃; for 24h; | I.I.2 I.2-Compound ODODEHANP: The title compound, which corresponds to the general formula (I) in which R’rrrR2rrrR3=n-octyl, R4=H, R5rrrR62-ethylhexyl, is synthesised by implementing step A, from di-n-octylphosphine oxide (4.4 mmol), n-nonanaland di(2-ethylhexyl)amine (reflux for 24 hours at 140° C.).10082] Yield: 69% (3.2 mmol)10083] 3’P NMR (162 MHz, CDC13, 25° C.) ö(ppm): 53.010084] ‘H NMR (400 MHz, CDC13, 25° C.) ö(ppm): 2.44(m, JFH=8.4 Hz, 1H, P-CH(Oct)-N); 2.58 (m, 2H,N-CH2-CH); 2.37 (m, 2H, N-CH2---CH); 1.90 (m, 2H);1.86-1.50 (m, 1OH); 1.42-1.11 (m, 48H); 0.91-0.78 (m, 21H,CH3)10085] ‘3C NMR (100 MHz, CDC13, 25° C.) ö (ppm): 60.3& 59.7 (d, J=66.7 Hz, P-CH---N); 57.2 (N-CH2); 38.2(CH-CH2-N); 31.9; 31.4; 31.3; 31.2; 31.1; 29.9; 29.6;29.5; 29.3; 29.1; 25.6; 24.5; 24.3; 24.1; 23.3; 23.1; 22.7;22.1; 21.9 (CH2); 14.1; 10.9; 10.7 (CH3)10086] HR-ESI-MS: calculated for C4,H87NOP=640.6525. found=640.6495. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
28.6% | With sodium tris(acetoxy)borohydride; In 1,2-dichloro-ethane; at 20℃;Inert atmosphere; | General procedure: Alkylaldehyde (RCHO) (1.1 equiv) was added into a solution of deacetyl linezolid (1 equiv., 300mg) and NaBH(OAc)3 (1.3 equiv.) in 7.5mL 1,2-dichloroethane in a round-bottom flask. The mixture solution with N2 protected was stirred at room temperature for 12-24h. Then saturated NaHCO3 was used to quench the reaction and alkalified to pH=8. The reaction solution was then extracted with dichloromethane (DCM). The organic layer was subsequently washed with H2O (2-3 times) and brine (1-2 times). Then the organic layer was dried over anhydrous Na2SO4, filtrated, and concentrated under reduced pressure and the residue was purified using column chromatography (petroleum ether: ethyl acetate=5:1 to 1:1 v/v and with 0.5% triethylamine) to obtain the product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40 mg | Step 1: commercially available <strong>[1404-90-6]vancomycin</strong> (100 mg) and DIPEA (30 muL) were dissolved in 3 mL of DMF to give an opaque solution, which was heated to 50 C to become clear. 1-nonanal (30 muL) was added, and the reaction was heated and stirred for 4h. Then, NaCNBH3 (8 mg), 1 mL of methanol and 30 muL of TFA were added at room temperature, and the reaction was stirred overnight and monitored by HPLC. The reaction mixture was added with diethyl ether (50 mL) to generate precipitates, which was filtered to give a crude. The crude was purified by reverse-phase C18 HPLC and lyophilized to give Van-f (40 mg) as a white solid. HPLC: C18 column (5 mum, 4.6 x 250 mm), UV detection at 214 nm, elution conditions: a gradient of 2-90% acetonitrile containing 0.1% v/v TFA over 30 min. HRMS (ESI+) calculated for C75H93Cl2N9O24 1573.5711, found 787.7856[M+2H]2+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
21.6% | With di-tert-butyl peroxide; C52H80MnN2O10; oxygen; In 1,4-dioxane; at 100℃; under 1500.15 Torr; for 1h;Autoclave; | Add 3.5 g (0.01 mol) of methyl erucinate to the autoclave, 0.083 g (0.0001 mol) of a manganese complex of an isostrethol derivative,10.5 g of 1,4-dioxane, 1.0 g (0.008 mol) of t-butanol peroxide,Passing oxygen to the reactor pressure of 0.2 MPa, the reaction temperature is 100 C,The reaction time was 60 minutes. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With propionic acid; In ethanol; for 2.5h;Reflux; | General procedure: 1H-Indole-3-carboxylate methylester 2 (1.0 mmol-equiv.) was refluxed with hydrazine hydrate(12.5 g, 0.25 M) in appropriate ethanol (30 mL) for 2 h. The progressof the reaction was monitored by TLC. After cooling the reactionmixture to room temperature, the mixtures were filtered to givewhite solid crude products without purification. Next, indolehydrazide(3, 1.0 mmol) in ethanol (30 mL) was added dropwiseinto the appropriate aldehyde (1.5 mmol-equiv.) and a few drops ofpropionic acid; the mixture was stirred and refluxed for 2.5 h. Aftercooling, the precipitates were filtered and washed several times bymethanol to yield the crystal substances 4aeu. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: sodium hydride / mineral oil; tetrahydrofuran / 0.25 h / 20 °C / Inert atmosphere 1.2: 2 h 2.1: lithium hydroxide / water; acetone / 24 h |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58% | General procedure: A dry and argon-flushed round bottom flask equipped with a magnetic stirrer and a septum was charged with a solution of 3 or 5 (1 equiv.) in dry THF (20 mL) and was cooled at -78 C. A solution of iPrMgCl·LiCl (1.3 equiv.) was added dropwise and the reaction mixture was stirred for 30 minutes at -78 C. The corresponding aldehyde was added and the reaction mixture was slowly warmed to room temperature and stirred overnight. The reaction mixture was hydrolysed with water (20 mL) and extracted with EtOAc (3 × 20 mL). The combined organic layers were washed with brine (20 mL), dried over MgSO4, and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen; sodium hydroxide In water at 140℃; for 216h; Overall yield = 88 percent; | 3 Use Example 1: Hydrogenation of 1,4-butynediol (BID) to 1,4-butanediol (BDO) An apparatus comprising a tube reactor having an internal diameter of 25 mm was used. 35 ml of the nickel-aluminum foam from Production Example 1 was cut into round disks having a diameter of 25 mm using a laser cutter. The disks were stacked on top of one another and installed in the tube reactor. In order for the disks not to have any empty space between them and the reactor wall, a PTFE (polytetrafluoroethylene) sealing ring was installed after every 5 disks. The reactor and the circulating stream were filled with deionized water and a 0.5% strength by weight NaOH solution was then fed in in the upflow mode and the catalyst fixed bed was activated at 100° C. over a period of 7 hours. The feed rate of the NaOH solution was 0.54 ml/min per ml of foam. The circulation rate was set to 18 kg/h, so that a feed-to-recycle ratio of 1:16 was obtained. The flow velocity of the aqueous base through the reactor was 37 m/h. During the activation, no active Raney nickel in the form of fine free particles was detected in the circulating stream or in the reactor output. The elemental analysis of the activation solution gave a nickel content of less than 1 ppm. The aluminum content in the activation solution was about 3.8% at the beginning of the activation and decreased to 0.05% over the duration of the activation. The maximum temperature gradient of the catalyst fixed bed during activation was 10 K. After activation for about 7 hours, the evolution of hydrogen decreased noticeably and the introduction of sodium hydroxide solution was stopped and the reactor was subsequently flushed with deionized water at 60° C. until a sample of the circulated liquid had a pH of 7.5 at 20° C. The flow rate of the deionized water was 380 ml/h at a circulation rate of 18 kg/h, i.e. a feed-to-recycle ratio of 1:47 was obtained. The flow velocity of the washing solution through the reactor was 37 m/h. Doping: An aqueous solution of 0.40 g of (NH4)Mo7O24×4 H2O in 20 ml of water was subsequently fed in in the downflow mode at 25° C. over a period of 1 hour. After all the solution had been introduced, the liquid was circulated by pumping in the circulating stream at a circulation rate of 15 kg/h for 3 hours. Hydrogenation: No BID solutions comprising more than 50% by weight of BID in water were used in the following. The aqueous BID starting material was prepared as described in Example 1 of EP 2 121 549 A1. The starting material was brought to a pH of 7.5 using sodium hydroxide solution and comprised, apart from BID and water, about 1% by weight of propynol, 1.2% by weight of formaldehyde and a series of other by-products in proportions of significantly less than 1% by weight. The hydrogenation was carried out using an aqueous 50% strength by weight BID solution at 155° C., a hydrogen pressure of 45 bar of hydrogen and a space velocity over the catalyst of 0.5 kgBID/(lcatalyst foam×h) at a circulation flow of 23 kg/h in the upflow mode. The hydrogenation gave 94.6% of BDO, 1.6% of n-butanol, 1.4% of methanol, 1.8% of propanol and 1900 ppm of 2-methylbutane-1,4-diol in the output over a period of 12 days. The space velocity over the catalyst was subsequently increased to 1.0 kgBID/(lcatalyst foam×h) at the same circulation flow. The product stream consisted of (calculated on a water-free basis) 94.0% of BDO, 2.2% of n-butanol, 1.4% of methanol, 1.0% of propanol, 2000 ppm of 2-methylbutane-1,4-diol and about 1% of further secondary components. |
Tags: 124-19-6 synthesis path| 124-19-6 SDS| 124-19-6 COA| 124-19-6 purity| 124-19-6 application| 124-19-6 NMR| 124-19-6 COA| 124-19-6 structure
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P261 | Avoid breathing dust/fume/gas/mist/vapours/spray. |
P262 | Do not get in eyes, on skin, or on clothing. |
P263 | Avoid contact during pregnancy/while nursing. |
P264 | Wash hands thoroughly after handling. |
P265 | Wash skin thouroughly after handling. |
P270 | Do not eat, drink or smoke when using this product. |
P271 | Use only outdoors or in a well-ventilated area. |
P272 | Contaminated work clothing should not be allowed out of the workplace. |
P273 | Avoid release to the environment. |
P280 | Wear protective gloves/protective clothing/eye protection/face protection. |
P281 | Use personal protective equipment as required. |
P282 | Wear cold insulating gloves/face shield/eye protection. |
P283 | Wear fire/flame resistant/retardant clothing. |
P284 | Wear respiratory protection. |
P285 | In case of inadequate ventilation wear respiratory protection. |
P231 + P232 | Handle under inert gas. Protect from moisture. |
P235 + P410 | Keep cool. Protect from sunlight. |
Response | |
Code | Phrase |
P301 | IF SWALLOWED: |
P304 | IF INHALED: |
P305 | IF IN EYES: |
P306 | IF ON CLOTHING: |
P307 | IF exposed: |
P308 | IF exposed or concerned: |
P309 | IF exposed or if you feel unwell: |
P310 | Immediately call a POISON CENTER or doctor/physician. |
P311 | Call a POISON CENTER or doctor/physician. |
P312 | Call a POISON CENTER or doctor/physician if you feel unwell. |
P313 | Get medical advice/attention. |
P314 | Get medical advice/attention if you feel unwell. |
P315 | Get immediate medical advice/attention. |
P320 | |
P302 + P352 | IF ON SKIN: wash with plenty of soap and water. |
P321 | |
P322 | |
P330 | Rinse mouth. |
P331 | Do NOT induce vomiting. |
P332 | IF SKIN irritation occurs: |
P333 | If skin irritation or rash occurs: |
P334 | Immerse in cool water/wrap n wet bandages. |
P335 | Brush off loose particles from skin. |
P336 | Thaw frosted parts with lukewarm water. Do not rub affected area. |
P337 | If eye irritation persists: |
P338 | Remove contact lenses, if present and easy to do. Continue rinsing. |
P340 | Remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P341 | If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P342 | If experiencing respiratory symptoms: |
P350 | Gently wash with plenty of soap and water. |
P351 | Rinse cautiously with water for several minutes. |
P352 | Wash with plenty of soap and water. |
P353 | Rinse skin with water/shower. |
P360 | Rinse immediately contaminated clothing and skin with plenty of water before removing clothes. |
P361 | Remove/Take off immediately all contaminated clothing. |
P362 | Take off contaminated clothing and wash before reuse. |
P363 | Wash contaminated clothing before reuse. |
P370 | In case of fire: |
P371 | In case of major fire and large quantities: |
P372 | Explosion risk in case of fire. |
P373 | DO NOT fight fire when fire reaches explosives. |
P374 | Fight fire with normal precautions from a reasonable distance. |
P376 | Stop leak if safe to do so. Oxidising gases (section 2.4) 1 |
P377 | Leaking gas fire: Do not extinguish, unless leak can be stopped safely. |
P378 | |
P380 | Evacuate area. |
P381 | Eliminate all ignition sources if safe to do so. |
P390 | Absorb spillage to prevent material damage. |
P391 | Collect spillage. Hazardous to the aquatic environment |
P301 + P310 | IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician. |
P301 + P312 | IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell. |
P301 + P330 + P331 | IF SWALLOWED: Rinse mouth. Do NOT induce vomiting. |
P302 + P334 | IF ON SKIN: Immerse in cool water/wrap in wet bandages. |
P302 + P350 | IF ON SKIN: Gently wash with plenty of soap and water. |
P303 + P361 + P353 | IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower. |
P304 + P312 | IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell. |
P304 + P340 | IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing. |
P304 + P341 | IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P305 + P351 + P338 | IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. |
P306 + P360 | IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes. |
P307 + P311 | IF exposed: call a POISON CENTER or doctor/physician. |
P308 + P313 | IF exposed or concerned: Get medical advice/attention. |
P309 + P311 | IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician. |
P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
P333 + P313 | IF SKIN irritation or rash occurs: Get medical advice/attention. |
P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
P337 + P313 | IF eye irritation persists: Get medical advice/attention. |
P342 + P311 | IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician. |
P370 + P376 | In case of fire: Stop leak if safe to Do so. |
P370 + P378 | In case of fire: |
P370 + P380 | In case of fire: Evacuate area. |
P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
P403 | Store in a well-ventilated place. |
P404 | Store in a closed container. |
P405 | Store locked up. |
P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
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