CN104496749B - A kind of preparation method replacing styryl carbinol - Google Patents

A kind of preparation method replacing styryl carbinol Download PDF

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CN104496749B
CN104496749B CN201410453583.3A CN201410453583A CN104496749B CN 104496749 B CN104496749 B CN 104496749B CN 201410453583 A CN201410453583 A CN 201410453583A CN 104496749 B CN104496749 B CN 104496749B
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preparation
phenylacrolein
derivative
styryl carbinol
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CN104496749A (en
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冯秀娟
巴拉拉姆·塔卡勒
包明
于晓强
王善强
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Dalian University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention belongs to pharmaceutical-chemical intermediate and related chemistry technical field, relate to a kind of preparation method replacing styryl carbinol.The present invention is with phenylacrolein and derivative thereof for raw material, using nanoporous Au catalyst be catalyzer, organosilane is hydrogen source, alkali as additive, selective hydrogenation preparation replaces styryl carbinol.Wherein, the mol ratio of phenylacrolein and derivative and hydrogen source used is 1:0.1 ~ 1:15; The mol ratio of phenylacrolein and derivative and alkali is 1:0.1 ~ 1:15; Phenylacrolein and derivative thereof volumetric molar concentration is in a solvent 0.01mmol/mL ~ 2mmol/mL.Selectivity of product of the present invention is high, catalyzer favorable reproducibility, and reuses repeatedly catalytic effect and obviously do not reduce, and provides possibility for it realizes industrialization.

Description

A kind of preparation method replacing styryl carbinol
Technical field
The invention belongs to pharmaceutical-chemical intermediate and related chemistry technical field, relate to a kind of preparation method replacing styryl carbinol.
Background technology
Styryl carbinol, as essence and flavoring agent, is mainly used in preparation fruit type essence, cosmetic essence and soap compound, also because it has lasting gentle fragrance, is used as fixative.Meanwhile, styryl carbinol is the synthesis material of synthesis cardio-cerebralvascular medicine, and the lung knurl that can effectively suppress virus to cause is clinical in the illness such as leukemia, the esophageal carcinoma, has wide market outlook.
Traditional method preparing styryl carbinol is mainly divided into two large classes, one is the homogeneous catalyst by Ru, Ir and other transition metal and ligand binding, such catalyzer has high reactivity and selectivity, but these transition metal and part have the shortcoming [OHKUMAT such as expensive, difficult separation and recycling, not reproducible use, OOKAH, IKARIYAT, etal.Preferentialhydrogenationofaldehydesandketones.J.Am .Chem.Soc., 1995,117 (41): 10417-10418, WUX, LIUJ, LIX, etal.Onwaterandinair:fastandhighlychemoselectivetransfer hydrogenationofaldehydeswithiridiumcatalysts.Angew.Chem. Int.Ed., 2006,45 (40): 6718-6722.], two is study more heterogeneous catalyst, the factor affecting such catalyst effect is comparatively complicated, mainly comprise catalyst activity component, auxiliary agent, carrier and different method of reducing etc. influence factor, and load heterogeneous catalyst on an metal oxide, after repeatedly recycling, deactivation phenomenom [the BUSE because of the cohesion of metal nanoparticle can be there is, PRINSR, VANBOKHOVENJA.Originofthecluster-sizeeffectinthehydrogen ationofcinnamaldehydeoversupportedAucatalysts.CatalysisC ommunications, 2007, 8 (9): 1397-1402, LIUL, QIAOB, MAY, etal.Ferrichydroxidesupportedgoldsubnanoclustersorquantu mdots:enhancedcatalyticperformanceinchemoselectivehydrog enation.Daltontransactions, 2008,19:2542-2548.].Nanoporous gold copper-base alloy, it is a class novel nano structure catalyzer, it is made up of the pore of nanoscale and ligament, there is great specific surface area, excellent conduction and heat conductivility, the diverse physicochemical property with reguline metal can be shown, be subject to extensive concern in catalyticing research field.Nanoporous Au catalyst (AuNPore) has the advantage [YANM such as catalytic activity is high, stable, recycling is convenient, JINT, CHENQ, HoHE, FUJITAT, CHENL-Y, BAOM, CHENM-W, ASAON, YAMAMOTOY.Unsupportednanoporousgoldcatalystforhighlysele ctivehydrogenationofquinolines.Org.Lett., 2013,15 (7): 1484-1487].
Summary of the invention
The invention provides a kind of preparation method replacing styryl carbinol, the most highly selective of the method reaches 100%, and selected catalyzer has the active advantage such as high, stable, reuses repeatedly to have not yet to see catalytic activity and obviously reduce.
The present invention be using phenylacrolein and derivative thereof be raw material, nanoporous Au catalyst (AuNPore) is catalyzer, organosilane be hydrogen source, alkali as additive, selective hydrogenation preparation replaces styryl carbinol, and synthetic route is as follows:
Temperature of reaction is-50 DEG C ~ 150 DEG C, and the reaction times is 12h ~ 36h;
R 1be selected from hydrogen, alkyl, methoxyl group, hydroxyl, halogen, trifluoromethyl; R 2be selected from hydrogen, alkyl.
Hydrogen source is selected from organosilane, comprising: tri isopropyl silane, triethyl silicane, dimethylphenylsilaneand, diphenyl silane, three normal-butyl silane, and the mol ratio of phenylacrolein and derivative and hydrogen source used is 1:0.1 ~ 1:15.
The mol ratio of phenylacrolein and derivative and alkali is 1:0.1 ~ 1:15.
Phenylacrolein and derivative thereof volumetric molar concentration is in a solvent 0.01 ~ 2mmol/mL.
The catalyzer adopted is nanoporous Au catalyst (AuNPore), and hole on framework size is between 5nm ~ 50nm; Phenylacrolein and derivative thereof and used catalyst mol ratio are 1:0.01 ~ 1:0.1.
Solvent is one or more mixing in tetrahydrofuran (THF), toluene, glycol dimethyl ether, trichloromethane, methylene dichloride, ether, acetonitrile, dimethyl sulfoxide (DMSO), tetracol phenixin, acetone, DMF, hexanaphthene, normal hexane, normal heptane.
Alkali is one or more mixing in sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, sodium bicarbonate, quadrol, triethylamine, diethylamine, pyridine, piperidines, triphenylamine, tri-n-butylamine.
Separation method comprises: recrystallization, column chromatography etc.Recrystallization method use solvent as, benzene, toluene, ethanol, sherwood oil, acetonitrile, tetrahydrofuran (THF), chloroform, hexanaphthene, dioxane, ethyl acetate, DMF; With column chromatography method, silica gel or aluminum oxide can be used as stationary phase, developping agent is generally polarity and nonpolar mixed solvent, as ethyl acetate-light petrol, ethyl acetate-hexane, dichloromethane-petroleum ether, methyl alcohol-sherwood oil.
The invention has the beneficial effects as follows that this selectivity of product is high, catalyzer favorable reproducibility, and reuse repeatedly catalytic effect and obviously do not reduce, provide possibility for it realizes industrialization.
Accompanying drawing explanation
Fig. 1 is embodiment 1, Alpha-Methyl styryl carbinol in 2 1h nuclear magnetic spectrogram.
Fig. 2 is embodiment 3,4-methyl cinnamyl alcohol in 4 1h nuclear magnetic spectrogram.
Fig. 3 is embodiment 5,6, and 3-trifluoromethyl styryl carbinol in 7 1h nuclear magnetic spectrogram.
Fig. 4 is embodiment 8,9, and 2-methoxycinnamate alcohol in 10 1h nuclear magnetic spectrogram.
Embodiment
The preparation method of replacement styryl carbinol of the present invention, most highly selective and reaction yield reach 100% and 79% respectively, select catalyst to react favorable reproducibility, and reuse repeatedly catalytic effect and obviously do not reduce, for its suitability for industrialized production provides favourable condition.
Below in conjunction with specific embodiment, set forth the present invention further.The simple replacement done the present invention those skilled in the art or improve all belongs within the technical scheme that the present invention protects.
Embodiment 1: the synthesis of Alpha-Methyl styryl carbinol
To being added with AuNPore (10.0mg, in methyl alcohol (5mL) solvent of 10mol%) catalyzer, add substrate α-methylcinnamaldehyde (74.07mg, 0.5mmol), sodium hydroxide (200mg, 5mmol) and tri isopropyl silane (791.8mg, 5.0mmol), be placed on magnetic stirring apparatus and react 24h at 50 DEG C, column chromatography (silica gel, 200-300 order; Developping agent, sherwood oil: ethyl acetate=20:1) obtain Alpha-Methyl styryl carbinol 45.91mg, productive rate 62%.
Yellow liquid; 1hNMR (CDCl 3, 400MHz) and δ: 7.32 (d, J=7.6Hz, 2H), 7.27 (d, J=7.2Hz, 2H), 7.23 – 7.20 (m, 1H), 6.52 (s, 1H), 4.17 (s, 2H), 1.99 (brs, 1H, OH), 1.89 (s, 3H).
Embodiment 2: the synthesis of Alpha-Methyl styryl carbinol
To being added with AuNPore (10.0mg, in methyl alcohol (5mL) solvent of 10mol%) catalyzer, add substrate α-methylcinnamaldehyde (74.07mg, 0.5mmol), potassium hydroxide (280mg, 5mmol) and tri isopropyl silane (791.8mg, 5.0mmol), be placed on magnetic stirring apparatus and react 24h at 60 DEG C, column chromatography (silica gel, 200-300 order; Developping agent, sherwood oil: ethyl acetate=20:1) obtain Alpha-Methyl styryl carbinol 48.13mg, productive rate 65%.
Yellow liquid; 1hNMR (CDCl 3, 400MHz) and δ: 7.32 (d, J=7.6Hz, 2H), 7.27 (d, J=7.2Hz, 2H), 7.23 – 7.20 (m, 1H), 6.52 (s, 1H), 4.17 (s, 2H), 1.99 (brs, 1H, OH), 1.89 (s, 3H).
The synthesis of embodiment 3:4-methyl cinnamyl alcohol
To being added with AuNPore (10.0mg, in acetone (5mL) solvent of 10mol%) catalyzer, add substrate 4-methyl cinnamic aldehyde (74.07mg, 0.5mmol), sodium hydroxide (200mg, 5mmol) and tri isopropyl silane (791.8mg, 5.0mmol), be placed on magnetic stirring apparatus and react 24h at 50 DEG C, column chromatography (silica gel, 200-300 order; Developping agent, sherwood oil: ethyl acetate=20:1) obtain 4-methyl cinnamyl alcohol 45.91mg, productive rate 70%.
Colorless solid; 1hNMR (CDCl 3, 400MHz) and δ: 7.32 (d, J=8.0Hz, 2H), 7.16 (d, J=8.0Hz, 2H), 6.62 (d, J=16.0Hz, 1H), 6.35 (dt, J=16.0,4.0Hz, 1H), 4.33 (dd, J=4.0,2.0Hz, 2H), 2.38 (s, 3H), 1.94 (brs, 1H, OH); M.p., 50 – 52 DEG C.
The synthesis of embodiment 4:4-methyl cinnamyl alcohol
To being added with AuNPore (10.0mg, in THF (5mL) solvent of 10mol%) catalyzer, add substrate 4-methyl cinnamic aldehyde (74.07mg, 0.5mmol), sodium carbonate (415mg, 5mmol) and tri isopropyl silane (791.8mg, 5.0mmol), be placed on magnetic stirring apparatus and react 24h at 60 DEG C, column chromatography (silica gel, 200-300 order; Developping agent, sherwood oil: ethyl acetate=20:1) obtain 4-methyl cinnamyl alcohol 44.59mg, productive rate 68%.
Colorless solid; 1hNMR (CDCl 3, 400MHz) and δ: 7.32 (d, J=8.0Hz, 2H), 7.16 (d, J=8.0Hz, 2H), 6.62 (d, J=16.0Hz, 1H), 6.35 (dt, J=16.0,4.0Hz, 1H), 4.33 (dd, J=4.0,2.0Hz, 2H), 2.38 (s, 3H), 1.94 (brs, 1H, OH); M.p., 50 – 52 DEG C.
The synthesis of embodiment 5:3-trifluoromethyl styryl carbinol
To being added with AuNPore (10.0mg, in DMF (5mL) solvent of 10mol%) catalyzer, add substrate 4-methyl cinnamic aldehyde (74.07mg, 0.5mmol), sodium bicarbonate (416mg, 5mmol) and tri isopropyl silane (791.8mg, 5.0mmol), be placed on magnetic stirring apparatus and react 24h at 50 DEG C, column chromatography (silica gel, 200-300 order; Developping agent, sherwood oil: ethyl acetate=20:1) obtain 3-trifluoromethyl styryl carbinol, productive rate 50%.
Colourless liquid; 1hNMR (CDCl 3, 400MHz) and δ: 7.61 (s, 1H), 7.53 (d, J=7.6Hz, 1H), 7.48 (d, J=7.6Hz, 1H), 7.43 – 7.39 (m, 1H), 6.64 (d, J=16.0Hz, 1H), 6.43 (dt, J=15.6,5.6Hz, 1H), 4.35 (d, J=5.2Hz, 2H), 1.97 (brs, 1H, OH).
The synthesis of embodiment 6:3-trifluoromethyl styryl carbinol
To being added with AuNPore (10.0mg, in DMA (5mL) solvent of 10mol%) catalyzer, add substrate 4-methyl cinnamic aldehyde (74.07mg, 0.5mmol), salt of wormwood (690mg, 5mmol) and tri isopropyl silane (791.8mg, 5.0mmol), be placed on magnetic stirring apparatus and react 24h at 50 DEG C, column chromatography (silica gel, 200-300 order; Developping agent, sherwood oil: ethyl acetate=20:1) obtain 3-trifluoromethyl styryl carbinol, productive rate 54%.
Colourless liquid; 1hNMR (CDCl 3, 400MHz) and δ: 7.61 (s, 1H), 7.53 (d, J=7.6Hz, 1H), 7.48 (d, J=7.6Hz, 1H), 7.43 – 7.39 (m, 1H), 6.64 (d, J=16.0Hz, 1H), 6.43 (dt, J=15.6,5.6Hz, 1H), 4.35 (d, J=5.2Hz, 2H), 1.97 (brs, 1H, OH).
The synthesis of embodiment 7:2-methoxycinnamate alcohol
To being added with AuNPore (10.0mg, in toluene (5mL) solvent of 10mol%) catalyzer, add substrate 4-methyl cinnamic aldehyde (74.07mg, 0.5mmol), calcium hydroxide (370mg, 5mmol) and tri isopropyl silane (791.8mg, 5.0mmol), be placed on magnetic stirring apparatus and react 24h at 50 DEG C, column chromatography (silica gel, 200-300 order; Developping agent, sherwood oil: ethyl acetate=20:1) obtain 3-trifluoromethyl styryl carbinol, productive rate 71%.
Yellow liquid; 1hNMR (CDCl 3, 400MHz) and δ: 7.44 (dd, J=7.6,1.6Hz, 1H), 7.24 – 7.21 (m, 1H), 6.95 – 6.91 (m, 2H), 6.87 (d, J=8.4Hz, 1H), 6.39 (dt, J=16.0,5.6Hz, 1H), 4.33 (d, J=5.2Hz, 2H), 3.85 (s, 3H), 1.50 (brs, 1H, OH).
The synthesis of embodiment 8:2-methoxycinnamate alcohol
To being added with AuNPore (10.0mg, in DMSO (5mL) solvent of 10mol%) catalyzer, add substrate 4-methyl cinnamic aldehyde (74.07mg, 0.5mmol), calcium hydroxide (370mg, 5mmol) and tri isopropyl silane (791.8mg, 5.0mmol), be placed on magnetic stirring apparatus and react 24h at 70 DEG C, column chromatography (silica gel, 200-300 order; Developping agent, sherwood oil: ethyl acetate=20:1) obtain 3-trifluoromethyl styryl carbinol, productive rate 70%.
Yellow liquid; 1hNMR (CDCl 3, 400MHz) and δ: 7.44 (dd, J=7.6,1.6Hz, 1H), 7.24 – 7.21 (m, 1H), 6.95 – 6.91 (m, 2H), 6.87 (d, J=8.4Hz, 1H), 6.39 (dt, J=16.0,5.6Hz, 1H), 4.33 (d, J=5.2Hz, 2H), 3.85 (s, 3H), 1.50 (brs, 1H, OH).
The synthesis of embodiment 9:3-trifluoromethyl styryl carbinol
To being added with AuNPore (10.0mg, in methyl alcohol (5mL) solvent of 10mol%) catalyzer, add substrate 4-methyl cinnamic aldehyde (74.07mg, 0.5mmol), ammoniacal liquor (0.13ml, 5mmol) and tri isopropyl silane (791.8mg, 5.0mmol), be placed on magnetic stirring apparatus and react 24h at 50 DEG C, column chromatography (silica gel, 200-300 order; Developping agent, sherwood oil: ethyl acetate=20:1) obtain 3-trifluoromethyl styryl carbinol, productive rate 56%.
Colourless liquid; 1hNMR (CDCl 3, 400MHz) and δ: 7.61 (s, 1H), 7.53 (d, J=7.6Hz, 1H), 7.48 (d, J=7.6Hz, 1H), 7.43 – 7.39 (m, 1H), 6.64 (d, J=16.0Hz, 1H), 6.43 (dt, J=15.6,5.6Hz, 1H), 4.35 (d, J=5.2Hz, 2H), 1.97 (brs, 1H, OH).
The synthesis of embodiment 10:4-methyl cinnamyl alcohol
To being added with AuNPore (10.0mg, in ethanol (5mL) solvent of 10mol%) catalyzer, add substrate 4-methyl cinnamic aldehyde (74.07mg, 0.5mmol), sodium hydroxide (200mg, 5mmol) and tri isopropyl silane (791.8mg, 5.0mmol), be placed on magnetic stirring apparatus and react 24h at 70 DEG C, column chromatography (silica gel, 200-300 order; Developping agent, sherwood oil: ethyl acetate=20:1) obtain 4-methyl cinnamyl alcohol 45.90mg, productive rate 70%.
Colorless solid; 1hNMR (CDCl 3, 400MHz) and δ: 7.32 (d, J=8.0Hz, 2H), 7.16 (d, J=8.0Hz, 2H), 6.62 (d, J=16.0Hz, 1H), 6.35 (dt, J=16.0,4.0Hz, 1H), 4.33 (dd, J=4.0,2.0Hz, 2H), 2.38 (s, 3H), 1.94 (brs, 1H, OH); M.p., 50 – 52 DEG C.

Claims (6)

1. replace a preparation method for styryl carbinol, it is characterized in that, using phenylacrolein and derivative thereof be raw material, nano-porous gold is catalyzer, organosilane for hydrogen source and alkali are as additive, selective hydrogenation preparation replaces styryl carbinol, and synthetic route is as follows:
Temperature of reaction is-50 DEG C ~ 150 DEG C, and the reaction times is 12h ~ 36h;
R 1be selected from hydrogen, alkyl, methoxyl group, hydroxyl, halogen, trifluoromethyl; R 2be selected from hydrogen, alkyl;
Wherein, the mol ratio of phenylacrolein and derivative and hydrogen source is 1:0.1 ~ 1:15;
The mol ratio of phenylacrolein and derivative and alkali is 1:0.1 ~ 1:15;
Phenylacrolein and derivative thereof volumetric molar concentration is in a solvent 0.01 ~ 2mmol/mL;
The catalyzer adopted is nanoporous Au catalyst, and phenylacrolein and derivative thereof and used catalyst mol ratio are 1:0.01 ~ 1:0.1.
2. preparation method according to claim 1, is characterized in that, described hydrogen source is selected from organosilane.
3. preparation method according to claim 2, is characterized in that, described organosilane is tri isopropyl silane, triethyl silicane, dimethylphenylsilaneand, diphenyl silane or three normal-butyl silane.
4. the preparation method according to claim 1 or 2 or 3, it is characterized in that, described solvent is one or more mixing in tetrahydrofuran (THF), toluene, glycol dimethyl ether, trichloromethane, methylene dichloride, ether, acetonitrile, dimethyl sulfoxide (DMSO), tetracol phenixin, acetone, DMF, hexanaphthene, normal hexane, normal heptane.
5. the preparation method according to claim 1 or 2 or 3, is characterized in that, described alkali is one or more mixing in sodium hydroxide, potassium hydroxide, quadrol, triethylamine, diethylamine, pyridine, piperidines, triphenylamine, tri-n-butylamine.
6. preparation method according to claim 4, is characterized in that, described alkali is one or more mixing in sodium hydroxide, potassium hydroxide, quadrol, triethylamine, diethylamine, pyridine, piperidines, triphenylamine, tri-n-butylamine.
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