CN104058943A - Synthetic method of [beta]-hydroxyalkoxy component - Google Patents

Synthetic method of [beta]-hydroxyalkoxy component Download PDF

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Publication number
CN104058943A
CN104058943A CN201410089212.1A CN201410089212A CN104058943A CN 104058943 A CN104058943 A CN 104058943A CN 201410089212 A CN201410089212 A CN 201410089212A CN 104058943 A CN104058943 A CN 104058943A
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China
Prior art keywords
synthetic method
reaction
beta
alkene
alkoxy compound
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CN201410089212.1A
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Chinese (zh)
Inventor
宋国强
张文楠
曹引梅
罗九艳
姚昶旭
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Changzhou University
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Changzhou University
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Publication of CN104058943A publication Critical patent/CN104058943A/en
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    • 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
    • C07C41/02—Preparation of ethers from oxiranes
    • C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

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

Abstract

The invention discloses a synthetic method of a [beta]-hydroxyalkoxy component and belongs to the technical field of organic synthesis. The synthetic method is carried out by following steps: filling a container with an alkene, a cation exchange resin and an alcoholic solution, carrying out a stirring process and a heating process in a constant-temperature oil bath pot with a temperature being 0-100 DEG C; measuring a hydrogen dioxide solution through a constant-pressure dropping funnel according to an usage amount of the added alkene, adding slowly the reaction solution when a preset temperature is reached and carrying out a reaction for 0.5-24 h and adding a small amount of Na2S2O3 for quenching the reaction after the reaction being finished. The synthetic method is good in repeatability, is free of any complex separation process and can improve purity of a product. Chemical purity of the product can reach 95%. The synthetic method is simple in technology, is low in environmental pollution, is wide in application range, is low in production cost and is suitable for industrial production.

Description

A kind of synthetic method of beta-hydroxy alkoxy compound
Technical field
The present invention relates to a kind of synthetic method of beta-hydroxy alkoxy compound, belong to organic synthesis field.
Background technology
The addition reaction of alkene and alcohol is to prepare one of important channel of beta-hydroxy alkoxy compound.Its product beta-hydroxy alkoxy compound is extensively present in occurring in nature, it is the integral part of natural product, the reaction intermediate of organic synthesis, the structural unit of bioactive molecules, in pharmaceutical chemistry field extensive application, its a synthetic important topic that has become organic chemistry filed.The addition reaction of alkene and alcohol, under common acidity or alkaline condition, is generally not easy to carry out, and reaction conditions is comparatively harsh, and the selectivity of product is also difficult to control, and needs the target product that obtains of catalyzer ability highly selective.At present, common catalyst system mainly contains the hydrogen alkylated reaction of protonic acid, nonmetal system, transistion metal compound, catalysis of rare-earth compound alkene.But these class methods exist mostly, and catalyzer is expensive, manufacture craft is loaded down with trivial details, air is polluted or the shortcoming such as toxicity is larger.Therefore, select a kind of inexpensive, be easy to get, environment amenable catalyzer can not only make reaction conditions become gentle, and can improve selectivity and the yield of reaction product, for industrialization provides favourable reference, has higher economic and social benefit.
Summary of the invention
The synthetic method of beta-hydroxy alkoxy compound of the present invention, carry out in the steps below:
(1) in container, add alkene, Zeo-karb and alcoholic solution, stir and use the heating of thermostatical oil bath, temperature is 0-100 DEG C;
(2) according to adding the consumption of alkene, measure superoxol with constant pressure funnel, slowly add reaction solution, reaction 0.5-24h after reaching design temperature;
(3) after reaction finishes, add a small amount of Na 2s 2o 3the essence reaction of going out.Leach Zeo-karb, use 5-10mL washed with methanol, reclaim.Reaction solution is with after ethyl acetate and water extraction, and organic layer concentrates to obtain oily product, and purity is 90% ~ 100%, and yield is 70% ~ 83%.Recovery resin is added to next batch reaction, and reactions steps is identical.Through 1-12 revision test, product purity all reaches 90% ~ 100%, and productive rate all remains on 70% ~ 83%.
Wherein, in step (1), alkene structures formula is , R 1, R 2, R 3, R 4can be identical or different be selected from the alkyl such as hydrogen, methyl, ethyl, propyl group.
Wherein, described in step (1), the molecular formula of alcohol is C nh 2n+1oH, the fatty alcohol such as particular methanol, ethanol.
Wherein, described in step (1), resin is strongly acidic cation-exchange, preferably H type, Na type etc.
Wherein, in step (1), the mol ratio of alkene and Zeo-karb is 1:0.1-1:5.
Wherein, in step (1), the mol ratio of alkene and alcohol is 1:0.1-1:99.
Wherein, in step (2), the mol ratio of alkene and superoxol is 1:0.5-1:30.
Its reaction formula as shown in the formula:
R 1, R 2, R 3, R 4can be identical or different be selected from the alkyl such as hydrogen, methyl, ethyl, propyl group.
The molecular formula of described alcohol is C nh 2n+1oH, the fatty alcohol such as particular methanol, ethanol.
Described resin is strongly acidic cation-exchange, preferably H type, Na type etc.
Above-mentioned advantage, makes the present invention reproducible, without loaded down with trivial details sepn process, has improved the purity of product, and chemical purity reaches 95%; Preparation technology is simple, low in the pollution of the environment, and scope on probation is wide, and production cost is low, is suitable for suitability for industrialized production.
Embodiment
Describe the present invention with specific embodiment.Protection scope of the present invention is not limited with embodiment, but is limited by claim.
embodiment 1
1.00g tetrahydrobenzene (0.012mol), 1g H type D001 resin catalyst (0.0012mol), 0.04g methyl alcohol (0.0012mol) are joined in single necked round bottom flask, maintain the temperature at 60 DEG C, slowly drip the hydrogen peroxide of 0.68g (0.006mol) 30%, reaction 0.5-24h, adds a small amount of Na 2s 2o 3the essence reaction of going out.Remove by filter resin, with layering after 10mL × 4 ethyl acetate and the extraction of 10mL × 3 water, after organic phase is concentrated, obtain the oily liquids 1.09g of 2-methoxyl group hexalin, yield 69.69%.
embodiment 2
1.00g tetrahydrobenzene (0.012mol), 5g H type D001 resin catalyst (0.06mol), 38.02g methyl alcohol (1.19mol) are joined in single necked round bottom flask, maintain the temperature at 60 DEG C, slowly drip the hydrogen peroxide of 40.81g (0.36mol) 30%, reaction 0.5-24h, adds a small amount of Na 2s 2o 3the essence reaction of going out.Remove by filter resin, with layering after 10mL × 4 ethyl acetate and the extraction of 10mL × 3 water, after organic phase is concentrated, obtain the oily liquids 1.10g of 2-methoxyl group hexalin, yield 70.32%.
embodiment 3
1.00g tetrahydrobenzene (0.012mol), 1g H type D001 resin catalyst (0.0012mol), 11.52g methyl alcohol (0.36mol) are joined in single necked round bottom flask, maintain the temperature at 60 DEG C, slowly drip the hydrogen peroxide of 2.72g (0. 024mol) 30%, reaction 0.5-24h, adds a small amount of Na 2s 2o 3the essence reaction of going out.Remove by filter resin, with layering after 10mL × 4 ethyl acetate and the extraction of 10mL × 3 water, after organic phase is concentrated, obtain the oily liquids 1.30g of 2-methoxyl group hexalin, yield 83.00%.
embodiment 4
1.00g tetrahydrobenzene (0.012mol), 1g Na type D001 resin catalyst (0.0012mol), 0.06g ethanol (0.0012mol) are joined in single necked round bottom flask, maintain the temperature at 40 DEG C, slowly drip the hydrogen peroxide of 0.68g (0.006mol) 30%, reaction 0.5-24h, adds a small amount of Na 2s 2o 3the essence reaction of going out.Remove by filter resin, with layering after 10mL × 4 ethyl acetate and the extraction of 10mL × 3 water, after organic phase is concentrated, obtain the oily liquids 1.21g of 2-oxyethyl group hexalin, yield 70.11%.
embodiment 5
1.00g tetrahydrobenzene (0.012mol), 5g Na type D001 resin catalyst (0.06mol), 54.65g ethanol (1.19mol) are joined in single necked round bottom flask, maintain the temperature at 100 DEG C, slowly drip the hydrogen peroxide of 40.81g (0.36mol) 30%, reaction 0.5-24h, adds a small amount of Na 2s 2o 3the essence reaction of going out.Remove by filter resin, with layering after 10mL × 4 ethyl acetate and the extraction of 10mL × 3 water, after organic phase is concentrated, obtain the oily liquids 1.35g of 2-oxyethyl group hexalin, yield 78.19%.
embodiment 6
1.00g tetrahydrobenzene (0.012mol), 1g H type D001 resin catalyst (0.0012mol), 11.52g methyl alcohol (0.36mol) are joined in single necked round bottom flask, maintain the temperature at 60 DEG C, slowly drip the hydrogen peroxide of 2.72g (0.024mol) 30%, reaction 0.5-24h, adds a small amount of Na 2s 2o 3the essence reaction of going out.Remove by filter resin, with being incorporated to solution after the washed with methanol resin of 5mL × 2, resin reclaims.
embodiment 7
H type D001 resin catalyst, the 11.52g methyl alcohol (0.36mol) of recycling use in 1.00g tetrahydrobenzene (0.012mol), 1g embodiment 61 time are joined in single necked round bottom flask, maintain the temperature at 60 DEG C, slowly drip the hydrogen peroxide of 2.72g (0.024mol) 30%, reaction 0.5-24h, adds a small amount of Na 2s 2o 3the essence reaction of going out.Remove by filter resin, with being incorporated to solution after the washed with methanol resin of 5mL × 2, resin reclaims.Layering after 10mL for reaction solution × 4 ethyl acetate and the extraction of 10mL × 3 water, organic phase obtains the oily liquids 1.30g of 2-methoxyl group hexalin, yield 83.0% after concentrating.
embodiment 8
H type D001 resin catalyst, the 11.52g methyl alcohol (0.36mol) of recycling use in 1.00g tetrahydrobenzene (0.012mol), 1g embodiment 7 12 times are joined in single necked round bottom flask, maintain the temperature at 60 DEG C, slowly drip the hydrogen peroxide of 2.72g (0.024mol) 30%, reaction 0.5-24h, adds a small amount of Na 2s 2o 3the essence reaction of going out.Layering after 10mL for reaction solution × 4 ethyl acetate and the extraction of 10mL × 3 water, organic phase obtains the oily liquids 1.16g of 2-methoxyl group hexalin, yield 74.01% after concentrating.

Claims (7)

1. the synthetic method of beta-hydroxy alkoxy compound, is characterized in that carrying out in the steps below:
(1) in container, add alkene, Zeo-karb and alcoholic solution, stir and use the heating of thermostatical oil bath, temperature is 0-100 DEG C;
(2) according to adding the consumption of alkene, measure superoxol with constant pressure funnel, slowly add reaction solution, reaction 0.5-24h after reaching design temperature;
(3) after reaction finishes, add a small amount of Na 2s 2o 3the essence reaction of going out;
Leach Zeo-karb, use a small amount of washed with methanol, reclaim: after reaction solution ethyl acetate and water extraction, organic layer concentrates to obtain oily product, and purity is 90% ~ 100%, and yield is 70% ~ 83%; Recovery resin is added to next batch reaction, and reactions steps is identical; Through 1-12 revision test, product purity all reaches 90% ~ 100%, and productive rate all remains on 70% ~ 83%.
2. the synthetic method of beta-hydroxy alkoxy compound according to claim 1, is characterized in that wherein, and in step (1), alkene structures formula is , R 1, R 2, R 3, R 4can be identical or different, be hydrogen, methyl, ethyl or propyl group.
3. the synthetic method of beta-hydroxy alkoxy compound according to claim 1, is characterized in that wherein, and described in step (1), the molecular formula of alcohol is C nh 2n+1oH, the fatty alcohol such as particular methanol, ethanol.
4. the synthetic method of beta-hydroxy alkoxy compound according to claim 1, is characterized in that wherein, and described in step (1), resin is strongly acidic cation-exchange, preferably H type, Na type etc.
5. the synthetic method of beta-hydroxy alkoxy compound according to claim 1, is characterized in that wherein, and in step (1), the mol ratio of alkene and Zeo-karb is 1:0.1-1:5.
6. the synthetic method of beta-hydroxy alkoxy compound according to claim 1, is characterized in that wherein, and in step (1), the mol ratio of alkene and alcohol is 1:0.1-1:99.
7. the synthetic method of beta-hydroxy alkoxy compound according to claim 1, is characterized in that wherein, and in step (2), the mol ratio of alkene and superoxol is 1:0.5-1:30.
CN201410089212.1A 2014-03-12 2014-03-12 Synthetic method of [beta]-hydroxyalkoxy component Pending CN104058943A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5808115A (en) * 1996-03-08 1998-09-15 University Of Georgia Research Foundation Carbodiimide-promoted epoxidation of olefins
CN1552684A (en) * 2003-05-29 2004-12-08 浙江联盛化学工业有限公司 Preparing method for 1,2-pentadiol
CN1923777A (en) * 2005-08-31 2007-03-07 中国科学院大连化学物理研究所 Preparation method of 1,2-aliphatic glycol
CN101967082A (en) * 2010-04-12 2011-02-09 宁波中化化学品有限公司 Method for preparing 1,2-pentadiol

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5808115A (en) * 1996-03-08 1998-09-15 University Of Georgia Research Foundation Carbodiimide-promoted epoxidation of olefins
CN1552684A (en) * 2003-05-29 2004-12-08 浙江联盛化学工业有限公司 Preparing method for 1,2-pentadiol
CN1923777A (en) * 2005-08-31 2007-03-07 中国科学院大连化学物理研究所 Preparation method of 1,2-aliphatic glycol
CN101967082A (en) * 2010-04-12 2011-02-09 宁波中化化学品有限公司 Method for preparing 1,2-pentadiol

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Application publication date: 20140924