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CAS No. : | 1193-81-3 | MDL No. : | MFCD00001475 |
Formula : | C8H16O | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | JMSUNAQVHOHLMX-UHFFFAOYSA-N |
M.W : | 128.21 | Pubchem ID : | 137829 |
Synonyms : |
|
Num. heavy atoms : | 9 |
Num. arom. heavy atoms : | 0 |
Fraction Csp3 : | 1.0 |
Num. rotatable bonds : | 1 |
Num. H-bond acceptors : | 1.0 |
Num. H-bond donors : | 1.0 |
Molar Refractivity : | 39.62 |
TPSA : | 20.23 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) : | -5.42 cm/s |
Log Po/w (iLOGP) : | 2.22 |
Log Po/w (XLOGP3) : | 2.34 |
Log Po/w (WLOGP) : | 1.95 |
Log Po/w (MLOGP) : | 1.83 |
Log Po/w (SILICOS-IT) : | 1.96 |
Consensus Log Po/w : | 2.06 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 2.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -2.04 |
Solubility : | 1.16 mg/ml ; 0.00905 mol/l |
Class : | Soluble |
Log S (Ali) : | -2.4 |
Solubility : | 0.505 mg/ml ; 0.00394 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -1.14 |
Solubility : | 9.33 mg/ml ; 0.0728 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.98 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P210-P264-P280-P370+P378-P302+P352-P305+P351+P338-P312-P362+P364-P403+P235-P501 | UN#: | N/A |
Hazard Statements: | H315-H319-H335-H227 | 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 |
---|---|---|
78% | With hydrogenchloride; sodium hypochlorite; sodium thiosulfate In dichloromethane | (a) The mixed solution of a 15percent sodium hypochlorite aqueous solution 540 ml and a saturated sodium hydrogencarbonate aqueous solution 540 ml was dropwise added to a methylene chloride solution of 500 ml containing cyclohexylethanol 128 g and 2,2,6,6-tetramethyl-piperidine-1-oxyl 500 mg at 25° C. or lower and stirred for 30 minutes. A 20percent sodium thiosulfate aqueous solution 150 ml was added and shaken, and then the aqueous layer is separated from the organic layer and further extracted twice with methylene chloride 200 ml. The organic layers are put together and washed once with a 10percent sodium thiosulfate aqueous solution 150 ml, twice with 10percent hydrochloric acid 200 ml, twice with a satrated sodium hydrogencarbonate aqueous solution 200 ml and once with saturated brine 200 ml in order. After drying on sodium sulfate anhydrous, the solvent is distilled off under reduced pressure, and the residue is distilled under reduced pressure, whereby a pale yellow liquid of cyclohexylacetaldehyde 98.5 g is obtained. The yield: 78percent bp: 50 to 55° C./7 mmHg 1 H-NMR (CDCI3, δ): 0.7 to 2.5 (13H, m), 9.75 (1H, t, J=2.4 Hz) MS (m/z): 125 (M+ -l) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With aluminum oxyhydroxide; ruthenium In toluene at 110℃; for 12h; | |
99% | With nickel(II) triflate; cyclohexanone; 1,2-bis-(dicyclohexylphosphino)ethane In toluene at 110℃; for 12h; Schlenk technique; | |
97% | In toluene at 110℃; for 8h; |
96% | With bromopentacarbonylmanganese(I); N-methyl-N,N-di(2-pyridylmethyl)amine; acetone; sodium t-butanolate In toluene at 90℃; for 24h; Inert atmosphere; Schlenk technique; Darkness; | |
94% | With air In various solvent(s) at 100℃; for 10h; | |
93% | With aluminium trichloride; silver bromate In acetonitrile for 0.5h; Heating; | |
91% | With 1-hydroxytetraphenylcyclopentadienyl(tetraphenyl-2,4-cyclopentadien-1-one)-μ-hydrotetracarbonyldiruthenium(II) In 1,3,5-trimethyl-benzene at 165℃; for 24h; Inert atmosphere; | |
89% | With air; (1,3-diarylimidazol-2-ylidene)-based Pd; Trimethylacetic acid In toluene at 20℃; for 14h; | |
89% | In toluene at 110℃; for 20h; | |
89% | With Dess-Martin periodane In dichloromethane at 20℃; for 3h; Inert atmosphere; | |
88% | With manganese (VII)-oxide In tetrachloromethane; acetone at -70℃; | |
85% | With nickel In benzene for 20h; Heating; | |
84% | With N-Bromosuccinimide; 1,3-bis(3,5-bis(trifluoro-ethyl)phenyl)thiourea In dichloromethane at -20℃; for 48h; Inert atmosphere; | |
82% | With trichloroisocyanuric acid; silica gel; potassium bromide In dichloromethane at 20℃; for 1h; | |
80% | With oxygen In hexane at 68.84℃; for 24h; Molecular sieve; | 2.4. Catalytic test General procedure: Pd-STO (12.5 mg), 1-phenylethanol (25 mg, 0.204 mmol), n-decaneas an internal standard and n-hexane (2 mL) as the solvent were placedin a Schlenk flask equipped with reflux condenser, mechanical stirrerand balloon. The reaction was carried out at approximately the refluxtemperature of n-hexane (342 K) under an O2 atmosphere (0.1 MPa) for24 h. In some cases, molecular sieves 3A (MS3A) were placed into thereaction mixture. |
71% | With 2,2,6,6-tetramethyl-piperidine-N-oxyl; Oxone; tetrabutylammomium bromide In toluene at 20℃; for 12h; | |
70% | With [Rh(η4-C8H12)]2(μ-OH){μ-Niso,Npy-(BMePHI)} In toluene at 100℃; for 24h; Inert atmosphere; Schlenk technique; | |
64% | With oxygen In toluene at 110℃; for 16h; | |
21% | With [bis({2‐[bis(propan‐2‐yl)phosphanyl]ethyl})amine](borohydride)(carbonyl)(hydride)iron(II); potassium <i>tert</i>-butylate; acetone In n-heptane at 80℃; for 24h; Schlenk technique; Inert atmosphere; | |
With chromium(III) oxide; sulfuric acid | ||
With chromic acid | ||
4 % Chromat. | at 30℃; for 168h; by Corynebacterium equi IFO 3730; | |
52 % Chromat. | With dihydrogen peroxide; methyltrioxorhenium(VII) In <i>tert</i>-butyl alcohol at 60℃; for 10h; | |
With tert.-butylhydroperoxide; triethylamine In decane at 55℃; for 24h; | ||
With pyridinium chlorochromate | ||
With magnesium hypobromite | ||
100 % Chromat. | With trimethylaluminum In toluene at 20℃; for 0.5h; | |
With sodium dichromate; sulfuric acid In water | II Preparation of Cyclohexyl Methyl Ketone EXAMPLE II Preparation of Cyclohexyl Methyl Ketone Into a two-liter, round bottom, three-necked flask equipped with a condenser, a mechanical stirrer, thermometer and a liquid addition funnel were placed 900 ml. of water, 200 g. (0.67 mole) of technical grade sodium dichromate followed by 176 g. (1.8 mole) of concentrated sulfuric acid. The contents were cooled to 55°-60° C. and 120 g. (0.94 mole) of 1-hydroxyethylcyclohexane was added over a period of 1 hour, holding the temperature between 55°-50° C. by means of external cooling. After the alcohol had been added, the reaction mixture was allowed to stir for an additional 30 minutes and then 600 ml. of water was added and the contents heated to remove the ketone by steam distillation. When no more ketone was being steam distilled, the heat was removed, the distillate of water and ketone separated and the upper organic layer was distilled under vacuum collecting the fraction boiling at 115°-116° C. There was obtained 76 g. of ketone representing a 64% yield. | |
With N,N'-dibromo-N,N'-1,2-ethanediylbis(benzenesulphonamide) In dichloromethane at 20℃; for 1.5h; | ||
With Oxone; C26H20N2O3V; tetrabutylammomium bromide In dichloromethane; water at 20℃; for 0.0833333h; | ||
82 %Chromat. | With C48H45As2Cl2N2ORuS; 4-methylmorpholine N-oxide In dichloromethane at 27℃; for 12h; | |
74 %Chromat. | With Cu/AlO(OH); periodic acid In water at 27℃; for 24h; chemoselective reaction; | |
90 %Chromat. | With Oxone; [Mn(2,4,6-tri-(2-pyridyl)-1,3,5-triazine)Cl2(H2O)]*H2O; tetrabutylammomium bromide In dichloromethane; water at 20℃; for 0.0833333h; | |
96 %Chromat. | With C51H51ClN2O2P2RuS; 4-methylmorpholine N-oxide In acetonitrile at 27℃; for 12h; | |
93 %Chromat. | With [CuCl(N-(diethylcarbamothioyl)benzamide)(PPh3)2]; dihydrogen peroxide In acetonitrile at 27℃; for 7h; | |
51 %Chromat. | With tert.-butylhydroperoxide; [Co(III)(N-(dibenzylcarbamothioyl)benzamide(-H))3] In acetonitrile at 80℃; for 48h; | |
68 %Chromat. | With [Ru(S(C6H4)NCH(C6H4)O(Br))(CO)(PPh3)2]; 4-methylmorpholine N-oxide In dichloromethane at 27℃; for 12h; | 2.5. Catalytic oxidation of alcohols General procedure: To a solution of alcohol (1 mmol) in dichloromethane (20 mL),ruthenium(II) complex (1 mol%) and NMO (351 mg; 3 mmol) were added. The mixture was stirred at 27 °C for 12 h. Then the solution was concentrated and the alcohol and aldehyde/ketone were obtained by passing the solution through a short silica gel column (hexane/ethyl acetate). The extract was then analyzed by GC. |
With tert.-butylhydroperoxide; (Ph2PRuCl2(η6-p-cymene))(ferrocene-1,1'-diyl)C(O)NHCH2COOCH3 In water at 20℃; for 24h; | ||
> 99 %Chromat. | With potassium peroxymonosulfate; C72H58IN12O6Ru2 In dichloromethane; water at 40℃; for 4h; | |
81 %Chromat. | With C50H40Cl2NO2P2Ru; 4-methylmorpholine N-oxide In dichloromethane at 20℃; for 9h; Inert atmosphere; Schlenk technique; | 2.4. Procedure for catalytic oxidation of alcohols General procedure: Oxidation of primary alcohols to aldehydes and secondary ones to ketones with NMO were catalyzed in the presence of [RuCl(κ2-N,O-L-Cl)(CO)(PPh3)2] (1), [RuCl(κ2-N,O-L-Me)(CO)(PPh3)2] (2), or [RuCl(κ2-N,O-L-NO2)(CO)(PPh3)2] (3). A typical reaction using 1, 2 or 3 as catalyst is as follows. A solution of 1, 2 or 3 (1 M%) in 20 mL of CH2Cl2 was added to the mixture of substrate (1 mM) and NMO (2 mM). The mixture was stirred at room temperature for 9 h and the solvent was evaporated under reduced pressure with a rotary evaporator resulting in a solid mass. It was shaken with petroleum ether (30-40 °C)(20 mL). The oxidized product extracted into petroleum ether was analyzed by GC. |
100 %Chromat. | With periodic acid In water at 27℃; for 3h; | |
With benzophenone; sodium t-butanolate In toluene at 90℃; for 18h; | 2.2 General procedures for the oxidation of alcohols with NaOtBu General procedure: A Radley tube (Carousel RR98030) with a magnetic stirring bar was charged with NaOtBu (Aldrich (99.9%) and Alfa Aesar (97%), 0.2 mmol), benzophenone (2 mmol), alcohol (1 mmol) and toluene (2 mL). The tube was closed, stirred and heated. After cooling, dichloromethane (10 mL) and 1,3-dimethoxybenzene (130 μL) were added. The mixture was filtrated, the filtrate washed twice with water, further dried over Na2SO4 and analyzed by GC-MS and 1H NMR (after concentration) for the determination of yields or directly concentrated under vacuum to yield the crude product. Ketones can be purified by distillation of the crude and subsequent column chromatography (when necessary). All products (previously described and commercial) were analyzed by 1H NMR and GC-MS; coadditions of authentic samples were performed | |
88 %Chromat. | With pyridine; Tributylphosphine oxide; oxygen; palladium diacetate In toluene at 80℃; Molecular sieve; | |
71 %Chromat. | With dihydrogen peroxide In water; acetonitrile at 90℃; for 19h; Green chemistry; | General procedure for oxidation of alcohols to the correspondingcarbonyl compound with 30% H2O2 General procedure: In a two necked flask equipped with a condenser, alcohol (1 mmol), 30% H2O2 (5 mmol) were added to an equal mixture of water and acetonitrile (1.5 ml). Then, WO4PMO-IL (0.23 g, ~1.5 mol %) was added to the above solution and the resulting mixture was stirred at 90 °C for requisite time. The progress of the reaction was monitored by gas chromatography using standard addition method. After completion of the reaction, the mixture was allowed to cool down to the room temperature and the catalyst was successfully isolated with centrifugation and washed with CH2Cl2 (310 ml) and dried under the vacuum for 12 h. Then, the collected CH2Cl2 phase was first washed with water, dried over Na2SO4, and the solvent was concentrated with evaporation under the reduced pressure to give the corresponding carbonyl compounds. The recovered catalyst was used in the recycling procedure in the same manner as reported in the first run. |
71 %Chromat. | With dihydrogen peroxide In water; acetonitrile at 90℃; for 19h; Green chemistry; chemoselective reaction; | 4.5 General procedure for oxidation of alcohols to the corresponding carbonyl compound with 30% H2O2 General procedure: In a two necked flask equipped with a condenser, alcohol (1 mmol), 30% H2O2 (5mmol) were added to an equal mixture of water and acetonitrile (1.5ml). Then, WO4=PMO-IL (0.23g, ∼1.5 mol%) was added to the above solution and the resulting mixture was stirred at 90°C for requisite time. The progress of the reaction was monitored by gas chromatography using standard addition method. After completion of the reaction, the mixture was allowed to cool down to the room temperature and the catalyst was successfully isolated with centrifugation and washed with CH2Cl2 (3×10ml) and dried under the vacuum for 12 h. Then, the collected CH2Cl2 phase was first washed with water, dried over Na2SO4, and the solvent was concentrated with evaporation under the reduced pressure to give the corresponding carbonyl compounds. The recovered catalyst was used in the recycling procedure in the same manner as reported in the first run. |
> 99 %Chromat. | With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; iodine In aq. buffer at 30℃; for 1h; Sonication; | |
95 %Chromat. | With tert.-butylnitrite; oxygen; acetic acid In toluene at 50℃; for 5h; | |
45 %Chromat. | With C39H59N5OOsP2 In toluene at 100℃; for 24h; Schlenk technique; | |
With C35H31ClN2O2PRu*CH2Cl2; 4-methylmorpholine N-oxide In dichloromethane at 20℃; for 12h; Inert atmosphere; Schlenk technique; | 2.11. Procedure for catalytic oxidation of alcohols General procedure: Oxidations of primary alcohols to aldehydes and secondary ones to ketones were catalyzed by complexes 1-8 in the presence of N-methylmorpholine-N-oxide (NMO) as co-oxidant. A typical reaction using complexes 1-8 as catalysts is as follows. A solution of each of complexes 1-8 (0.01 mmol) in 10 mL of CH2Cl2 was added to the mixture of substrate (1 mmol) and NMO (2 mmol). The mixture was stirred at room temperature for 12 h and the solvent was evaporated under reduced pressure with a rotary evaporator resulting in a solid mass. Then it was shaken with petroleum ether (30 ~ 40 °C) (20 mL). The oxidized product extracted into petroleum ether was analyzed by GC. | |
42 %Spectr. | With C34H51CeN5O8(1-)*C6H15N*H(1+); oxygen In N,N-dimethyl-formamide at 120℃; for 20h; Molecular sieve; | |
With tert.-butylhydroperoxide; O3V(1-)*C6H15Sn(1+) at 55℃; for 24h; | ||
40 %Spectr. | With C44H51IrN9OsP In toluene at 100℃; for 18h; Schlenk technique; | |
With poly(2-oxazoline)-based shell cross-linked micelles-supported 7-TEMPO In water at 20℃; | ||
98 %Chromat. | With dihydrogen peroxide In water for 2h; Reflux; | Typical procedure for oxidation of alcohols in the presence of PW11ZnDowex catalyst General procedure: Catalytic experiments were carried out in a 25 mL roundbottomedflask equipped with a reflux condenser. At first,an appropriate amount of catalyst, 3 mL water and 1 mmolof alcohol were added. After adding 1 mL of 30% H2O2the mixture was refluxed for appropriate time with stirring.The progress of the reaction was monitored by GC equippedwith a flame ionization detector. At the end of the reaction,the catalyst and reaction solution were simply separated bydecantation.For recycling experiments, after the request reaction timethe round-bottom flask was cooled to room temperature andthe catalyst was separated by decantation. The catalyst wasthen thoroughly washed with acetonitrile and acetone followedby drying in vacuum at room temperature |
With acetone at 80℃; for 20h; Green chemistry; | ||
With (PiPr3)2H2Ir{μ-(κ2-Npy,Nimine-BMePI-κ2-Nimine,C4iso)}OsH3(PiPr3)2 In toluene at 100℃; for 24h; Schlenk technique; Inert atmosphere; | ||
95 %Chromat. | With hydrogenchloride; tert.-butylnitrite; oxygen In water; toluene at 50℃; for 8h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | Stage #1: Cyclohexyl methyl ketone With formic acid; tricarbonyl (4S,7S)-4,7-bis(benzyloxy)-1,3-diphenyl-4,5,6,7-tetrahydro-2H-inden-2-one iron; triethylamine for 0.166667h; Inert atmosphere; Stage #2: With trimethylamine-N-oxide at 60℃; for 48h; | |
91% | With sodium isopropanolate; isopropanol for 5h; | |
88% | With methanol; sodium tetrahydridoborate at 0 - 20℃; for 0.666667h; Inert atmosphere; |
83% | Stage #1: Cyclohexyl methyl ketone With 2-phenyl-6,7-dihydro-5H-pyrrolo[2,1-c][1,2,4]triazol-2-ium chloride; diphenylsilane; sodium hydride In N,N-dimethyl-formamide; mineral oil at 20℃; for 24h; Stage #2: With N,N,N-tributylbutan-1-aminium fluoride In tetrahydrofuran; N,N-dimethyl-formamide for 0.5h; | |
82% | With sodium tetrahydridoborate In ethanol at 20℃; Inert atmosphere; | |
77% | With (S)-(+)-1-(5-phenyl-4,5-dihydro-1,3-oxazol-2-yl)isoquinoline; trichlorosilane In chloroform at -20℃; for 24h; Inert atmosphere; | |
67% | With (S)-(+)-2-(5-phenyl-4,5-dihydro-1,3-oxazol-2-yl)pyridine; trichlorosilane In chloroform at -20℃; for 24h; | |
65% | With formic acid; C18H24ClIrN3 In lithium hydroxide monohydrate at 80℃; for 8h; Schlenk technique; Inert atmosphere; chemoselective reaction; | |
58% | Stage #1: Cyclohexyl methyl ketone With ferrous acetate; tricyclohexylphosphine In tetrahydrofuran at 65℃; Inert atmosphere; Stage #2: In tetrahydrofuran at 65℃; Inert atmosphere; Stage #3: With lithium hydroxide monohydrate; sodium hydroxide In tetrahydrofuran; methanol at 0 - 20℃; Inert atmosphere; | |
With methanol; diethyl ether; natrium | ||
With platinum on activated charcoal Hydrogenation; | ||
With sodium tetrahydridoborate In methanol Ambient temperature; | ||
With hydrogenchloride; borane N,N-diethylaniline complex 1.) THF, 25 h, reflux; Yield given. Multistep reaction; | ||
With hydrogen In cyclohexane at 79.85℃; ΔE(a); | ||
With sodium tetrahydridoborate In methanol at 20℃; | ||
With hydrogen; potassium isopropoxide In isopropanol at 60℃; for 3h; | ||
89 % Chromat. | With dodecacarbonyltri-iron; sodium isopropanolate; 5,10,15,20-tetra(pyridin-4-yl)-21H,23H-porphyrin In isopropanol at 100℃; for 7h; | |
77 % Chromat. | With 1H-imidazol-3-ium; sodium isopropanolate In isopropanol at 100℃; for 12h; | |
With sodium tetrahydridoborate | ||
With borane-THF; (R)-tetrahydro-1-methyl-3,3-diphenyl-1H,3H-pyrrolo[1,2-c]-[1,3,2]oxazaborole In tetrahydrofuran; toluene at 20℃; | ||
With hydrogen; potassium isopropoxide In isopropanol at 60℃; for 3h; | ||
With sodium tetrahydridoborate | ||
With lithium isopropoxide In isopropanol at 180℃; for 0.333333h; microwave irradiation; | ||
Multi-step reaction with 2 steps 1: Rh catalyst / benzene 2: NaOMe / methanol | ||
With hydrogen In toluene at 20℃; for 2h; Autoclave; chemoselective reaction; | ||
With sodium tetrahydridoborate | ||
With lithium aluminium hydride Inert atmosphere; | General remarks General procedure: All reactions were carried out using Schlenk techniques. Proline derived ligands 3a-3c and 3e-k were prepared from Boc-L-proline and the corresponding commercially available amines, as described in the literature[i]. [RuCl2 (p-cymene)]2 and (1R,2S)-(+)-cis-1-amino-indanol 3d were purchased. Racemic alcohols 2a-m were prepared by LiAlH4 reductions of the corresponding ketone. Other reagents are commercially available. Products were purified by preparative thin layer chromatography using plates prepared from silica gel. Bruker AM 250 spectrometer, operating at 250 MHz for 1H, and at 62.5 MHz for 13C, was used for the NMR spectra which are referenced to the solvent as internal standard. Infrared spectra were recorded in CHCl3 solution using CaF2 cells on a Perkin-Elmer 1000 FT-IR spectrometer. HRMS were measured with a Thermo-Finnigan-Mat 95 spectrometer. Optical rotations were determined using a Perkin-Elmer 241 Polarimeter at room temperature using a cell of 1 dm length and l = 589 nm. Data are reported as follows: [a]D20 (concentration in g/100 mL, solvent). Reactions were monitored by gas chromatography analysis on apparatus Fisons 8000 equipped with column β-P1. Enantiomeric excesses of alcohols were determined by gas chromatograph analysis on Fisons 9000 apparatus equipped with Chiraldex β-PM column. For the separation of the enantiomers of the mixture of alcohols 2a-g, the program was as follows: oven temperature was maintained at 50°C during 30 min, then heated to 100°C (5°C/min) maintained at 100°C during 65 min, then heated to 120°C (5°C/min) and maintained at 120°C during 100 min. | |
75 %Chromat. | Stage #1: Cyclohexyl methyl ketone With n-butyllithium; ferrous acetate; 1,3-bis(2,6-diisopropylphenyl)imidazolinium chloride In tetrahydrofuran; hexane at 65℃; Inert atmosphere; Stage #2: With sodium hydroxide In tetrahydrofuran; methanol; hexane; lithium hydroxide monohydrate at 20℃; for 3h; Inert atmosphere; | |
With di-μ-chlorobis-[(η6-p-cymene)chlororuthenium(II)]; (S)-N-[(1S,2S)-2-(4-methylphenylsulfonamido)-1,2-diphenylethyl]pyrrolidine-2-carboxamide; anhydrous sodium formate In lithium hydroxide monohydrate at 60℃; for 24h; Inert atmosphere; | ||
98 %Chromat. | Stage #1: Cyclohexyl methyl ketone With (THF)Zr(MesNP<SUP>i</SUP>Pr2)<SUB>3</SUB>CoN<SUB>2</SUB>; phenylsilane In tetrahydrofuran at 20℃; for 6h; Inert atmosphere; Glovebox; Stage #2: With hydrogenchloride In tetrahydrofuran; lithium hydroxide monohydrate at 20℃; | |
95 %Chromat. | With Triethoxysilane; C27H56FeN2P4Si In tetrahydrofuran at 100℃; for 24h; Inert atmosphere; Schlenk technique; | |
With sodium tetrahydridoborate In methanol at 20℃; Schlenk technique; | Racemic: General procedure: The ketone (1mmol) was dissolved in MeOH (5cm3) in a schlenk tube, then NaBH4 (3mmol) was added slowly and the mixture was stirred at r.t. for o/n. The solvent was removed and the mixture was dissolved in DCM (10 cm3), washed with water (10cm3), filtered and solvent removed. a small amount of the residue was dilluted inEtOAc and then injected on the GC to determine the conversion. | |
95 %Chromat. | With isopropanol; sodium hydroxide at 80℃; for 21h; | |
74 %Chromat. | With sodium hydroxide In isopropanol at 82℃; for 1.5h; | 2.3. Transfer hydrogenation of carbonyl compounds General procedure: In a typical procedure, a 5 mg (0.77 mol%) of RuO2/MWCNT and 80 mg (2 mmol) of NaOH were stirred with 5 mL of i-PrOH taken in an ace pressure tube equipped with a stirring bar. Then the substrate (1 mmol) was added to the stirring solution and then the mixture was heated at 82°C. The completion of the reaction was monitored by GC. After the reaction, the catalyst was separated out from the reaction mixture by simple centrifugation and the products and unconverted reactants were analyzed by GC without any purification. Selectivity of the product for each reaction was alsocalculated. Finally, the separated RuO2/MWCNT was washed well with diethyl ether followed by drying in an oven at 60°C for 5 h and it was reused for the subsequent transfer hydrogenation of carbonyl compounds to investigate the reusability of the RuO2/MWCNT. |
40 %Spectr. | With [Zn(CpMe4)2(1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene)]; hydrogen In benzene at 25℃; for 72h; Inert atmosphere; | |
78 %Chromat. | With potassium methylate In lithium hydroxide monohydrate; N,N-dimethyl-formamide at 100℃; for 24h; Inert atmosphere; Green chemistry; | 2.3. Catalytic testing For a typical reduction, 2 mmol of the aldehyde substrate,0.504 g (6 mmol) potassium formate, 0.54 mL (30 mmol) water and5 mL (65 mmol) dimethylformamide (DMF) were added to a 25 mLround-bottom flask. After heating the reaction mixture to 100Cunder a flow of nitrogen, 100 mg of 1 wt.% Ru/AlO(OH) (0.5 mol %of Ru) was added. Samples were taken at regular intervals and ana-lyzed by gas chromatography (GC) and gas chromatography massspectrometry (GC-MS). For comparison, the direct hydrogenationof benzaldehyde using molecular H2at 0.5 MPa was carried out in a Parr autoclave at 100C. Due to their lower reactivity, the catalytictransfer hydrogenation of ketones was carried out using 200 mg of2 wt.% Ru/AlO(OH). For recycling tests, the used catalyst was recov-ered by centrifugation, washed with water followed by ethanol anddried at room temperature before use |
100 %Chromat. | With (x)C4H8O*(x)C18H15P*Ru; hydrogen In tetrahydrofuran at 30℃; for 16h; Autoclave; Glovebox; | |
97 %Chromat. | With C37H28Cl2N5PRu; isopropanol; sodium hydroxide at 82℃; for 0.5h; Inert atmosphere; | |
With sodium tetrahydridoborate In methanol; lithium hydroxide monohydrate at 28℃; for 3.5h; | ||
With tris(pentafluorophenyl)borate; hydrogen In toluene at 60℃; for 12h; Molecular sieve; | ||
With tris(pentafluorophenyl)borate; hydrogen In diethyl ether at 70℃; for 12h; Glovebox; | ||
With samarium diiodide | ||
75 %Spectr. | With C13H12BrMnN4O3; potassium-t-butoxide; isopropanol at 80℃; for 20h; | |
90 %Spectr. | With chloro-trimethyl-silane; samarium diiodide; Tetraethylene glycol dimethyl ether; magnesium In 2,2,2-trifluoroethanol for 3h; Glovebox; | |
With sodium tetrahydridoborate In methanol at 0 - 20℃; for 6h; | General procedure for1-(2-chloro-5-fluorophenyl)ethan-1-ol 8k General procedure: To a solution of 1-(2-chloro-5-fluorophenyl)ethan-1-one (1.000 g, 5.8mmol) in anhydrous Methanol (10 mL) at 0 oC was added Sodiumborohydride (331 mg, 8.7 mmol) slowly in batches. The reaction solution wasstirred for 6 h at room temperature. Then, water wasadded to quench the reaction in an ice bath and the solution was concentratedwith a rotary evaporator. The crude product was added towater and extracted with CH2Cl2 (3 × 30 mL). The organiclayer was washed with saturated aqueous NaCl, dried over anhydrous Na2SO4,and concentrated in vacuo to give the product as a colorless oil (0.960 g, 95%). | |
With hydrogen | ||
> 99 %Chromat. | With mer-[MnI(CO)3((S,S)-HN(CH2CH2P((Me)tBu))2)]Br; hydrogen; potasssium hydride In toluene at 80℃; for 16h; Autoclave; | |
63 %Spectr. | Stage #1: Cyclohexyl methyl ketone With phenylsilane; C20H16BrMnN4O3 In tetrahydrofuran at 80℃; for 1h; Stage #2: With lithium hydroxide monohydrate In tetrahydrofuran | |
With hydrogen In ethanol at 120℃; | ||
With methanol; sodium tetrahydridoborate In dichloromethane at 0 - 20℃; for 1h; | ||
With [Fe((R)-1-phenyl-N-(pyridin-2-ylmethylene)ethanamine)3]2[PF6]; potassium hydroxide In isopropanol at 82℃; for 48h; Inert atmosphere; | 2.3 General Procedure forAsymmetric TransferHydrogenation ofKetones General procedure: For catalytic asymmetric transfer hydrogenation of ketones,a typical procedure was as follows. A solution of 5mL of0.4M base (KOH (1.12 × 102mg, 100mol %) in iPrOH(5mL) and the complexes Fe1 (6.14mg, 0.25mol%) weremixed and refluxed at 82°C for 30min. This was followedby addition of acetophenone substrate (0.23mL,2.00 × 10-3mol) drop-wise into the reaction mixture. Thesolubility of the Na2CO3and tBuOK in iPrOH was ensuredby refluxing the respective mixtures at 82°C for 15minbefore the catalyst was added. During the course of the reaction,about 0.10mL of the mixture was sampled at regulartime intervals (about 4h intervals over the 48h period) andcooled. The samples were then prepared for NMR and GCanalyses by dissolving about 0.1mL in 3.5mL of CDCl3or iPrOH solvents respectively and filtered using syringefilter of pore size 0.25μm to remove precipitates and traceof metal particles in the analyte. Percentage conversions ofacetophenone to 1-phenylethanol were determined using 1HNMR spectroscopy, while enantiomeric excess (ee%) weredetermined using gas chromatography. Kinetic data wereanalysed using 64-bit OriginPro 9.1 [24]. | |
Multi-step reaction with 2 steps 1: lithium bromide / tetrahydrofuran / 1 h / 24 - 25 °C / Inert atmosphere 2: sodium hydroxide; lithium hydroxide monohydrate / tetrahydrofuran; lithium hydroxide monohydrate / 1 h / 20 °C | ||
Multi-step reaction with 2 steps 1: C44H52FeN2(1-)*0.5C4H8O*C12H24KO6(1+) / tetrahydrofuran / 0.5 h / 25 °C / Inert atmosphere 2: sodium hydroxide; dihydrogen peroxide / Inert atmosphere | ||
99 %Chromat. | With potassium-t-butoxide; hydrogen; tetracarbonyl(2-(diphenylphosphino)-ethylamine)chromium(0) In diethylene glycol dimethyl ether at 120℃; for 20h; Autoclave; | |
With sodium tetrahydridoborate; ethanol at 20℃; for 16h; Inert atmosphere; | ||
With galactose; Bacillus megaterium glucose dehydrogenase; recombinant Hansenula polymorpha ketoreductase; nicotinamide adenine dinucleotide In aq. phosphate buffer at 37℃; for 24h; Enzymatic reaction; | Biotransformations with purified KRED General procedure: Small-scale screening reactions were carried out in 1.5 mL plastic testtubes with a total volume of 1 mL of reaction mixture containingcarbonyl substrate (20-46 mM, Table 2), glucose (0.1 M), NADP+ (1mM), KRED (0.06-4.8 mg mL-1), GDH (0.03-0.072 mg mL-1) and potassiumphosphate buffer (0.1 M, pH 6.5). Reductions were performed at37 C and 550 rpm in a thermomixer (Eppendorf, Germany) for 24 h.Reaction aliquots (50 μL) were taken during biotransformations atvarious time intervals and extracted with ethyl acetate (200 μL) by 10 sof vortexing, followed by centrifugation (13,300g, 1 min), the extractswere analysed by gas chromatography (GC). | |
98 %Chromat. | Stage #1: Cyclohexyl methyl ketone With C44H44CuN2P2(1+)*F6P(1-) In toluene at 25℃; for 1h; Inert atmosphere; Stage #2: With sodium hydroxide In methanol; lithium hydroxide monohydrate Inert atmosphere; | 3. Typical procedure for catalytic hydrosilylation of ketones General procedure: Under nitrogen atmosphere the copper based catalyst 1 (8 7 mmg0.01 mmol), tBuOK ( 5 6 mmg0.05 mmol) and toluene (3 mL) were placed in a tube equipped with a Teflon coated magnetic stirring bar. T he mixture was stirred at 25 °C for 15 min and then polymethylhydrosiloxane (PMHS, 0.0 9 m L, 1.5 mmol mmol) was injected. After 15mins, ketone (0.5 mmol) was introduced and the mixture was stirred at 25 °C for therequired reaction time. The mixture was quenched with MeOH (1 mL) and 10%NaOH solution (3 mL), and the mixture was stirred for 4 h. T he mixture was extractedwith ethyl acetate (5 mL × 3) and the combined organic layer was washed with waterand saturated sodium chloride solution, dried over anhydrous Na2SO4. the solvent was removed under vacuum and the residue was purified by flash chromatography (silica gel) to afford the desired product. All the product alcohols were analyzed by 1H NMR, 13C NMR, or GC analysis. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 92% 2: 1.5% 3: 0.9% | With bis(cyclopentadienyl)titanium (III) chloride; cyclohexa-1,4-diene In tetrahydrofuran Ambient temperature; other epoxides, reaction without cyclohexa-1,4-diene; | |
1: 1.5% 2: 0.9% 3: 92% | With bis(cyclopentadienyl)titanium (III) chloride; cyclohexa-1,4-diene In tetrahydrofuran Ambient temperature; | |
1: 0.9% 2: 64% 3: 1.5% | With bis(cyclopentadienyl)titanium (III) chloride; cyclohexa-1,4-diene In tetrahydrofuran for 0.666667h; other epoxides; other H-atom donors; var. temperature, var. time; |
1: 0.9% 2: 64% | With bis(cyclopentadienyl)titanium (III) chloride; cyclohexa-1,4-diene In tetrahydrofuran for 0.25h; | |
0.9% | With bis(cyclopentadienyl)titanium (III) chloride; cyclohexa-1,4-diene In tetrahydrofuran for 0.25h; Yields of byproduct given; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 43% 2: 14% 3: 43 % Chromat. | With hydrogen; Aliquat 336 In water; 1,2-dichloro-ethane at 30℃; for 5h; | |
1: 43% 2: 43% 3: 14 % Chromat. | With hydrogen; Aliquat 336 In water; 1,2-dichloro-ethane at 30℃; for 5h; | |
1: 43% 2: 14% 3: 43 % Chromat. | With hydrogen; Aliquat 336 In water; 1,2-dichloro-ethane at 30℃; for 5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 20% 2: 27% 3: 52% | With hydrogen In water chemoselective reaction; | |
52% | With hydrogen In ethanol at 40℃; for 12h; Schlenk technique; Green chemistry; chemoselective reaction; | |
1: 64.8 % Chromat. 2: 25.2 % Chromat. 3: 10.0 % Chromat. | With hydrogen In water at 19.9℃; Title compound not separated from byproducts; |
1: 50 % Spectr. 2: 26 % Spectr. 3: 19 % Spectr. | With hydrogen at 100℃; for 50h; Title compound not separated from byproducts; | |
1: 82.3 % Chromat. 2: 5.1 % Chromat. 3: 6.3 % Chromat. | With hydrogen In water at 19.9℃; other catalysts; | |
1: 5.1 % Chromat. 2: 6.3 % Chromat. 3: 82.3 % Chromat. | With hydrogen In water at 19.9℃; Title compound not separated from byproducts; | |
With hydrogen In cyclohexane at 79.85℃; ΔH; | ||
With ruthenium nanoparticles at 60℃; for 1h; Ionic liquid; Autoclave; | ||
1: 75 %Chromat. 2: 15 %Chromat. 3: 9 %Chromat. | With hydrogen In ethanol at 50℃; for 16h; chemoselective reaction; | |
With ruthenium trichloride; hydrogen; sodium hydroxide In methanol at 40℃; for 48h; Inert atmosphere; | ||
With hydrogen In 2,2,4-trimethylpentane; water at 40℃; for 3.33333h; | ||
With hydrogen In 2,2,4-trimethylpentane; water at 40℃; for 3.13333h; | ||
With hydrogen In water at 20℃; for 20h; Autoclave; | ||
1: 30 %Chromat. 2: 13 %Chromat. | With hydrogen chemoselective reaction; | |
1: 23 %Chromat. 2: 53 %Chromat. 3: 24 %Chromat. | With (x)C4H8O*(x)C18H15P*Ru; hydrogen In pentane at 30℃; for 5h; Autoclave; Glovebox; | |
1: 43 %Chromat. 2: 41 %Chromat. 3: 16 %Chromat. | With (x)C4H8O*(x)C28H28P2*Ru; hydrogen In tetrahydrofuran at 30℃; for 5h; Autoclave; Glovebox; | |
1: 28 %Chromat. 2: 46 %Chromat. 3: 26 %Chromat. | With (x)C4H8O*(x)C28H28P2*Rh; hydrogen In tetrahydrofuran at 30℃; for 5h; Autoclave; Glovebox; | |
With ruthenium; hydrogen In water at 30℃; for 1h; Autoclave; chemoselective reaction; | ||
With hydrogen In hexane at 25℃; for 72h; Autoclave; | ||
With hydrogen In water at 20℃; for 1.5h; Autoclave; | ||
With hydrogen at 75℃; for 10h; Autoclave; Sealed tube; Ionic liquid; Overall yield = 19.8 %; chemoselective reaction; | ||
With hydrogen In 1,4-dioxane at 89.84℃; for 6h; Inert atmosphere; Glovebox; Autoclave; | ||
With hydrogen In ethanol at 120℃; | ||
With hydrogen In toluene at 100℃; for 2h; | ||
With hydrogen In tetrahydrofuran at 130℃; for 20h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 36% 2: 64% | With hydrogen In tetrahydrofuran at 24.84℃; for 6h; chemoselective reaction; | |
1: 62% 2: 19% | With hydrogen In n-heptane at 30℃; for 4h; | |
1: 5.9 % Chromat. 2: 94.2 % Chromat. | With hydrogen In water at 19.9℃; Title compound not separated from byproducts; |
1: 65 % Chromat. 2: 35 % Chromat. | With hydrogen In hexane at 20℃; for 4.5h; | |
With ruthenium nanoparticles at 60℃; for 1.5h; Ionic liquid; Autoclave; | ||
With hydrogen In water at 149.84℃; for 5h; Autoclave; chemoselective reaction; | ||
1: 57 %Chromat. 2: 39 %Chromat. | With (x)C4H8O*(x)C18H15P*Ru; hydrogen In tetrahydrofuran at 30℃; for 2.5h; Autoclave; Glovebox; | |
1: 13 %Chromat. 2: 87 %Chromat. | With (x)C4H8O*(x)C18H15P*Ru; hydrogen In tetrahydrofuran at 30℃; for 5h; Autoclave; Glovebox; | |
With ruthenium; hydrogen In n-heptane at 50℃; for 16h; Autoclave; Inert atmosphere; | ||
With ruthenium; hydrogen In water at 30℃; for 1h; Autoclave; Overall yield = 74 %Chromat.; | 4.2.4. Hydrogenation of substituted benzenes General procedure: In a typical example, a substituted benzene (1.0mmol), as shown in Table 6, was treated with H2 (30atm) with stirring at 30 or 50°C in the presence of Ru-1 (Ru=0.003mmol, S/C=333, in 1mL of H2O) in an autoclave with an inner glass tube. The product was extracted with EtOAc (3mL×5) and the combined extracts were dried over Na2SO4 and concentrated under reduced pressure. The crude product was purified using a short silica gel column. The hydrogenation of anisole on a large scale [toluene=24mmol (S/C=1400)] is described in the Supplementary data. | |
With hydrogen In water at 20℃; for 3h; Autoclave; | ||
With C21H23ClNORh; hydrogen at 150℃; for 24h; | 5 3.5 Dehydrogenation of 1-phenylethanol to acetophenone Complex 1a (42.8 μmol) and acetophenone (4.28 mmol, 500 μL) were mixed in a 500 mL round bottom flask. The sample was placed under 1 atm H2 heated at 150 °C for ∼24 h. After the reaction, the solution was cooled to room temperature. The mixture was filtered through Celite in a glass pipette, and the filtrate diluted with THF. Examination of the product by GC showed the complete disappearance of acetophenone and the appearance of both cyclohexyl methyl ketone and 1-cyclohexylethanol in a 1:1 ratio. Complex 1a (12.8 μmol) and acetophenone (1.28 mmol, 150 μL) were mixed with 0.25 mL of p-xylene in a Teflon-lined Parr bomb reactor (50 mL). The sample was placed under 5 atm H2 and heated at 150 °C for ∼2 h. After the reaction, the solution was cooled to room temperature and the reactor vented. The mixture was filtered through Celite in a glass pipette, and the filtrate diluted with THF. Examination of the product by GC showed the complete disappearance of acetophenone and the appearance of both cyclohexyl methyl ketone and 1-cyclohexylethanol in a 6:1 ratio. | |
1: 55 %Chromat. 2: 42 %Chromat. | With hydrogen In tetrahydrofuran at 30℃; for 5h; Autoclave; Glovebox; | 3.3 General procedure for the catalytic hydrogenation reactions General procedure: Autoclave Par 477 equipped with PID control temperature and reservoir for kinetic measurements and HEL 24 Cat reactor for substrate scope were used as reactors for the hydrogenation reactions. In a typical experiment, the autoclave was charged in the glove-box with the desired Rh NPs (1.25 or 0.625mol%; the catalyst concentration was calculated based on the total number of metallic Rh atoms in the surface of the NPs) and the substrate (0.124M) in THF. Molecular hydrogen was then introduced until the desired pressure was reached and the reaction was stirred for the desired reaction time at the selected temperature. At the end of the reaction, the autoclave was depressurised and the solution was filtered through silica for subsequent analysis by GC. The conversion and selectivities for each reaction product were determined by GC-FID on an Agilent Technologies 7890A spectrometer, with a HP-5 column (30m×0.25mm×0.25μm) using undecane as internal standard. TOF was defined as moles of products per mol Rh at the surface of the NPs per hour. |
1: 45 %Chromat. 2: 55 %Chromat. | With hydrogen In tetrahydrofuran at 30℃; for 5h; Autoclave; Glovebox; | 3.3 General procedure for the catalytic hydrogenation reactions General procedure: Autoclave Par 477 equipped with PID control temperature and reservoir for kinetic measurements and HEL 24 Cat reactor for substrate scope were used as reactors for the hydrogenation reactions. In a typical experiment, the autoclave was charged in the glove-box with the desired Rh NPs (1.25 or 0.625mol%; the catalyst concentration was calculated based on the total number of metallic Rh atoms in the surface of the NPs) and the substrate (0.124M) in THF. Molecular hydrogen was then introduced until the desired pressure was reached and the reaction was stirred for the desired reaction time at the selected temperature. At the end of the reaction, the autoclave was depressurised and the solution was filtered through silica for subsequent analysis by GC. The conversion and selectivities for each reaction product were determined by GC-FID on an Agilent Technologies 7890A spectrometer, with a HP-5 column (30m×0.25mm×0.25μm) using undecane as internal standard. TOF was defined as moles of products per mol Rh at the surface of the NPs per hour. |
With hydrogen In tetrahydrofuran at 20℃; for 20h; Schlenk technique; | ||
With acetylacetonato(1,5-cyclooctadiene)rhodium(I); hydrogen In 2,2,2-trifluoroethanol at 100℃; for 10h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; Candida antarctica B lipase; [RuCl2(p-cymene)]2; (E)-2-((1-hydroxy-2-methylpropan-2-ylimino)methyl)phenol In toluene at 70℃; for 72h; Inert atmosphere; Enzymatic reaction; optical yield given as %ee; enantioselective reaction; | 4.3. General procedure for the dynamic kinetic resolution of alcohols 1-9 General procedure: The reaction was carried out under an argon atmosphere at 70 °C for 72 h in a dry Schlenk tube with 2.5 mol % of [RuCl2(p-cymene)2]2 (15 mg), 5 mol % of ligand, 150 μmol of TEMPO (23 mg) and 40 mg of CAL-B in 2 mL of toluene. After 5 min, 1 mmol of racemic alcohol was added. The mixture took a red color. After 15 min, 3 mmol of p-chlorophenylacetate were added to the red reaction mixture. The reaction conversion and enantiomeric excess of the alcohol were monitored by taking samples for CG analysis. The samples were diluted with diethyl ether and washed with a saturated solution of NH4Cl, and filtered on silica. After 72 h, the dark reaction mixture was filtered on Celite, washed with a saturated solution of NH4Cl and extracted with ether. The organic layers were dried over Na2SO4, and concentrated in vacuo. |
With Novozym 435; <Ru2(CO)4(μ-H)(C4Ph4COHOCC4Ph4)> In toluene at 70℃; for 48h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With hydrogenchloride; sodium hypochlorite; sodium thiosulfate In dichloromethane | 1.a Example 1 (a) The mixed solution of a 15% sodium hypochlorite aqueous solution 540 ml and a saturated sodium hydrogencarbonate aqueous solution 540 ml was dropwise added to a methylene chloride solution of 500 ml containing cyclohexylethanol 128 g and 2,2,6,6-tetramethyl-piperidine-1-oxyl 500 mg at 25° C. or lower and stirred for 30 minutes. A 20% sodium thiosulfate aqueous solution 150 ml was added and shaken, and then the aqueous layer is separated from the organic layer and further extracted twice with methylene chloride 200 ml. The organic layers are put together and washed once with a 10% sodium thiosulfate aqueous solution 150 ml, twice with 10% hydrochloric acid 200 ml, twice with a satrated sodium hydrogencarbonate aqueous solution 200 ml and once with saturated brine 200 ml in order. After drying on sodium sulfate anhydrous, the solvent is distilled off under reduced pressure, and the residue is distilled under reduced pressure, whereby a pale yellow liquid of cyclohexylacetaldehyde 98.5 g is obtained. The yield: 78% bp: 50 to 55° C./7 mmHg 1 H-NMR (CDCI3, δ): 0.7 to 2.5 (13H, m), 9.75 (1H, t, J=2.4 Hz) MS (m/z): 125 (M+ -l) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | (step 1) To a solution of 1-cyclohexylethanol (0.23 g) in toluene (4 mL) was added sodium hydride (0.14 g), and the resulting mixture was stirred at 100C for 15 min under a nitrogen atmosphere. A mixture of tert-butyl 8-chloro-2,3-dihydropyrido[3,2-f][1,4]oxazepine-4(5H)-carboxylate (0.50 g), BINAP (0.033 g), Pd2(dba)3 (0.024 g) and toluene (4 mL) was added, and the resulting mixture was stirred at 100C for 2 hr under an argon atmosphere. The reaction solution was poured into water, and the resulting product was extracted with ethyl acetate. The organic layer was washed with water and saturated brine and dried, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (solvent gradient; 0?40% ethyl acetate/hexane) to give tert-butyl 8-(1-cyclohexylethoxy)-2,3-dihydropyrido[3,2-f][1,4]oxazepine-4(5H)-carboxylate (0.49 g, 74%) as a yellow oil. 1H-NMR(CDCl3):delta1.23(3H,t,J=6.2Hz), 1.03-1.40(6H,m), 1.42(9H,s), 1.42-1.95(5H,m), 3.79-3.82(2H,m), 4.20(2H,brs), 4.33-4.45(2H,m), 4.97(1H,brs), 6.38(1H,d,J=7.9Hz), 7.30-7.50(1H,m) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With C19H33MnNO3P2(1+)*Br(1-); hydrogen; sodium t-butanolate In isopropyl alcohol at 50℃; for 3h; Autoclave; Optical yield = 50 %ee; | 3.1.12 3.1 Hydrogenation of ketones or ketoesters with Manganese Complex of example 2.1 General procedure: General Procedure: All catalytic hydrogenation experiments using molecular hydrogen were carried out in a Parr Instruments autoclave (300 mL) advanced with an internal alloy plate include up to 8 uniform reaction vials (4 mL) equipped with a cap and needle penetrating the septum. Representative experiment: Under an argon atmosphere, a vial was charged with Manganese Complex of example 2.1 and base which were dissolved in 2 mL of dried solvent. The resulting red solution was stirred briefly before the ketone or ketoester (0.5 or 1 mmol) was added. The vial was placed in the alloy plate which was then placed into the autoclave. Once sealed, the autoclave was purged 5 times with hydrogen, then pressurized to 30 bar and heated to desired temperature. Afterwards, the autoclave was cooled to RT, depressurized, and the reaction mixture was analyzed by GC-FID or HPLC as well as GC-MS. Product isolation was performed via column chromatography using silica gel as stationary phase and w-pentane / ethylacetate or w-pentane / acetone mixture as eluent. Individual reaction conditions: [a] 2 mol cat., 5 mol NaOiBu, 0.5 mmol substrate, 30 bar, 3h, 50 °C, EtOH (1,5 mL) [b] 2 mol cat., 5 mol NaOiBu, 0.5 mmol substrate, 30 bar, 3h, 70 °C, EtOH (1,5 mL) [c] 2 mol% cat., 5 mol% NaOiBu, 0.5 mmol substrate, 30 bar, 3h, 50 °C, toluene (1,5 mL) [d] 2 mol% cat., 5 mol% NaOiBu, 0.5 mmol substrate, 30 bar, 3h, 50 °C, z'PrOH (1,5 mL) [e] 2 mol% cat., 5 mol% NaOiBu, 0.5 mmol substrate, 30 bar, 3h, 50 °C, /PrOH (1,5 mL) [f] 1 mol% cat., 5 mol% KOiBu, 0.5 mmol substrate, 30 bar, 4-5h, 40 °C, tert-amyl alcohol (1,5 mL) [g] 1 mol% cat., 5 mol% KOiBu, 0.5 mmol substrate, 30 bar, 16h, 50 °C, toluene (1,5 mL) [h] 2 mol% cat., 5 mol% KOiBu, 0.5 mmol substrate, 30 bar, 8h, 100 °C, dioxan (1,5 mL) [i] 1 mol% cat., 5 mol% KOiBu, 1 mmol substrate, 30 bar, 4h, 30 °C, 1,4-dioxane (2 mL) [j] 1 mol% cat., 5 mol% KOiBu, 1 mmol substrate, 30 bar, 4h, 40 °C, tert-amyl alcohol (2 mL) [k] 1 mol% cat., 5 mol% KOiBu, 1 mmol substrate, 30 bar, 4h, 80 °C, tert-amyl alcohol (2 mL) [1] 2 mol% cat., 5 mol% KOiBu, 1 mmol substrate, 30 bar, 4h, 50 °C, toluene (2 mL) [m] 2 mol% cat., 5 mol% KOiBu, 1 mmol substrate, 30 bar, 4h, 80 °C, tert-amyl alcohol(2 mL) [n] 2 mol% cat., 5 mol% NaOiBu, 0.5 mmol substrate, 30 bar, 3h, 70 °C, PrOH (1,5 mL) [o] 2 mol% cat., 5 mol% NaOiBu, 0.5 mmol substrate, 30 bar, lh, 50 °C, /PrOH (1 mL) SP = side product (Hydrogenation of double bond) Table 1: | |
25 %Chromat. | With C19H33MnNO3P2(1+)*Br(1-); potassium <i>tert</i>-butylate; hydrogen at 40℃; for 4h; Autoclave; Optical yield = 51 %ee; enantioselective reaction; |
Tags: 1193-81-3 synthesis path| 1193-81-3 SDS| 1193-81-3 COA| 1193-81-3 purity| 1193-81-3 application| 1193-81-3 NMR| 1193-81-3 COA| 1193-81-3 structure
[ 2216-52-6 ]
(1S,2S,5R)-2-Isopropyl-5-methylcyclohexanol
Similarity: 1.00
[ 2216-52-6 ]
(1S,2S,5R)-2-Isopropyl-5-methylcyclohexanol
Similarity: 1.00
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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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