CN101628873B - Method for synthesizing beta-hydroxymethyl butyrate - Google Patents
Method for synthesizing beta-hydroxymethyl butyrate Download PDFInfo
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- CN101628873B CN101628873B CN 200810012427 CN200810012427A CN101628873B CN 101628873 B CN101628873 B CN 101628873B CN 200810012427 CN200810012427 CN 200810012427 CN 200810012427 A CN200810012427 A CN 200810012427A CN 101628873 B CN101628873 B CN 101628873B
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Abstract
The invention discloses a method for synthesizing beta-hydroxymethyl butyrate, which mainly comprises the step of adding methyl formate with a concentration of between 125 and 625mmol/lL into a methanol solution containing propylene oxide with a concentration of between 250 and 1,000mmol/lL and a cobalt acetate and cadmium iodide catalyst with a concentration of between 8 and 16mmol/lL, wherein the molar ratio of cobalt acetate to cadmium iodide is 1: 9, a high-voltage mercury lamp with the power of between 100 and 400W is used to irradiate a reaction liquid for 15 to 55 hours, and the reaction temperature is between 25 and 60 DEG C. Preferably, sodium acetate with a concentration of between 300 and 900mmol/lL is also added into the methanol solution containing the propylene oxide with the concentration of between 250 and 1,000mmol/lL and the catalyst with the concentration of between 8 and 16mmol/lL. The method ensures that a carbonylation reaction gets simple and easy and has safe operation; and a non-precious metal compound adopted as the catalyst is easy to obtain and is also convenient to store and use. The product has low cost, and is suitable for the synthesis of the beta-hydroxymethyl butyrate with small scale and high added value.
Description
Technical field
The present invention relates to a kind of synthetic method of methyl beta-hydroxybutyrate.
Background technology
In recent years, along with the demand of beta-hydroxy acid esters at material, medicine and the aspect such as industrial strengthens gradually, people also constantly strengthen its research.The prior synthesizing method of beta-hydroxy acid esters is the Reformatsky reaction.This method reaction substrate is the alpha-halogen acid esters, is a kind of commodity compound that is not easy to obtain, and needs a large amount of Zn powder in the reaction, and beta-hydroxy acid esters productive rate is low, and the method that forces people to seek other is synthesized the beta-hydroxy acid esters.So someone invents the carbonylation reaction with propylene oxide and carbon monoxide and the synthetic methyl beta-hydroxybutyrate of methyl alcohol, it is with Co
2(CO)
8Be catalyzer, under 24.5MPa, 130 ℃ of conditions, reacted 4 hours.Although the method is better than above-mentioned traditional synthetic method, the yield of methyl beta-hydroxybutyrate is low only to be 40%.For improving yield, the someone proposes to Co
2(CO)
8Add 3-OH-Py in the catalyzer, reacted 9 hours under 4.2MPa, 75 ℃ of conditions, the yield of methyl beta-hydroxybutyrate can reach 92%.But the drawback of the oxo reaction method maximum of this routine is reaction will under high pressure be finished (〉=6.0MPa), and catalyzer is difficult for preserving and using, in addition, also need use the large CO gas of toxicity, this method is subject to certain restrictions in the application of small-scale fine product.
Summary of the invention
The purpose of this invention is to provide a kind of advantages of nontoxic raw materials, catalyzer and easily preserve the method for on a small scale synthetic methyl beta-hydroxybutyrate under use, the normal pressure.
Technical scheme of the present invention mainly is: make raw material with propylene oxide and methyl-formiate, with Cobaltous diacetate Co (OAc)
2, cadmium iodide CdI
2Make catalyzer, the method for synthetic methyl beta-hydroxybutyrate under normal pressure and light promotion condition.
Reaction equation of the present invention is as follows:
Raw material of the present invention is propylene oxide and methyl-formiate, and wherein substrate is propylene oxide, and methyl-formiate is as C
1The source.
Synthetic method of the present invention is as follows:
One, the preparation of reaction solution
1 with propylene oxide and methanol mixed, is mixed with the methanol solution that concentration is 250～1000mmol/L.
2 with catalyst acetic acid cobalt Co (OAc)
2, cadmium iodide CdI
2With methanol mixed, be mixed with the methanol solution that concentration is 8～16mmol/L, wherein the catalyst acetic acid cobalt: cadmium iodide=1: 9 (mol ratio).
3 mix above-mentioned catalyzer methanol solution with above-mentioned propylene oxide methanol solution.
4 preferably add the sodium-acetate that improves Cobaltous diacetate and cadmium iodide catalytic activity in above-mentioned mixed solution, its concentration in mixed solution is 300～900mmol/L.
Two, synthetic
1 at room temperature, contains 250～1000mmol/L propylene oxide, 8～16mmol/L catalyzer or the methyl-formiate of disposable direct adding 125～625mmol/L in the above-mentioned methanol solution that contains 250～1000mmol/L propylene oxide, 8～16mmol/L catalyzer and 300～900mmol/L sodium-acetate to above-mentioned.
2 use 100～400W high voltage mercury lamp radiation reaction solution 15～55 hours simultaneously, and temperature of reaction is controlled at 25～60 ℃.
3 products that adopt aforesaid method to obtain are the methyl beta-hydroxybutyrate methanol solution.This product can directly be used, and does interior mark with n-decane in such cases, and product carries out gas chromatographic analysis, and calculates yield 13%-55% with the result that gas-chromatography records, and carries out Product Identification with gas chromatograph-mass spectrometer again.
The present invention compared with prior art has following advantage:
1 carbonylation reaction of the present invention can carry out under the condition of normal temperature, normal pressure, non-noble metal simple salt catalysis substantially smoothly, regulate and control the process of reaction by the opening and closing of light source, neither adopt the large carbon monoxide of toxicity, do not need again the harsh reaction conditionss such as high pressure, but under the reaction conditions of gentleness, finish, make this carbonylation reaction simple, operational safety that becomes.
2 the present invention adopt non-noble metal compound Co (OAc)
2And CdI
2Make catalyzer, not only be simple and easy to but also be convenient to preserve and use.
3 because raw material of the present invention and catalyzer are inexpensive, and the simultaneous reactions condition is gentle again, and product cost of the present invention is reduced greatly.
4 the present invention are suitable for the synthetic of small scale, methyl beta-hydroxybutyrate that added value is high.
Description of drawings
Fig. 1 is the gas-chromatography spectrogram of the inventive example 1 product.
Fig. 2 is the spectrogram that the gas chromatograph-mass spectrometer of the inventive example 1 product records.
Fig. 3 is the gas-chromatography spectrogram of the inventive example 2 products.
Fig. 4 is the spectrogram that the gas chromatograph-mass spectrometer of the inventive example 2 products records.
Fig. 5 is the gas-chromatography spectrogram of the inventive example 3 products.
Fig. 6 is the spectrogram that the gas chromatograph-mass spectrometer of the inventive example 3 products records.
Embodiment
Example 1
With propylene oxide (analytical pure) and methanol mixed, be mixed with the methanol solution that concentration is 250mmol/L.With catalyst acetic acid cobalt, cadmium iodide and methanol mixed, be mixed with the methanol solution that concentration is 8mmol/L, wherein Cobaltous diacetate and cadmium iodide total concn are 8mmol/L, the mol ratio of Cobaltous diacetate and cadmium iodide is 1: 9.Above-mentioned catalyzer methanol solution is mixed with above-mentioned propylene oxide methanol solution.Add sodium-acetate in above-mentioned mixed solution, its concentration in mixed solution is 300mmol/L.Place the quartzy photoreactor of hollow sandwich inner the 100W high voltage mercury lamp, pass into recirculated water in the interlayer, the tank of simultaneously whole reactor being put into filled with water comes the cool down lamp source.The methanol solution 4ml that will contain 250mmol/L propylene oxide, 8mmol/L catalyst acetic acid cobalt and cadmium iodide, 300mmol/L sodium-acetate adds in the quartz test tube, quartz test tube is close on the outer wall of photoreactor.At room temperature, the disposable methyl-formiate that directly adds 125mmol/L was opened the high voltage mercury lamp radiation reaction solution 15 hours simultaneously in the above-mentioned mixing solutions, and temperature of reaction is controlled at 25～60 ℃.The product that obtains is done interior mark with n-decane, carries out gas chromatographic analysis, and the result who records with gas-chromatography, ask for an interview accompanying drawing 1, calculate methyl beta-hydroxybutyrate yield 13%, carry out Product Identification with gas chromatograph-mass spectrometer again, ask for an interview accompanying drawing 2, determine that it is methyl beta-hydroxybutyrate.
Example 2
With propylene oxide (analytical pure) and methanol mixed, be mixed with the methanol solution that concentration is 1000mmol/L.With catalyst acetic acid cobalt, cadmium iodide and methanol mixed, be mixed with the methanol solution that concentration is 16mmol/L, wherein Cobaltous diacetate and cadmium iodide total concn are 16mmol/L, the mol ratio of Cobaltous diacetate and cadmium iodide is 1: 9.Above-mentioned catalyzer methanol solution is mixed with above-mentioned propylene oxide methanol solution.Add sodium-acetate in above-mentioned mixed solution, its concentration in mixed solution is 900mmol/L.Place the quartzy photoreactor of hollow sandwich inner the 400W high voltage mercury lamp, pass into recirculated water in the interlayer, the tank of simultaneously whole reactor being put into filled with water comes the cool down lamp source.The methanol solution 4ml that will contain 1000mmol/L propylene oxide, 16mmol/L catalyst acetic acid cobalt and cadmium iodide, 900mmol/L sodium-acetate adds in the quartz test tube, quartz test tube is close on the outer wall of photoreactor.At room temperature, the disposable methyl-formiate that directly adds 625mmol/L was opened the high voltage mercury lamp radiation reaction solution 55 hours simultaneously in the above-mentioned mixing solutions, and temperature of reaction is controlled at 25～60 ℃.The product that obtains is done interior mark with n-decane, carries out gas chromatographic analysis, and with the result that gas-chromatography records, asks for an interview accompanying drawing 3, and calculating yield is 27%.Carry out Product Identification with gas chromatograph-mass spectrometer, ask for an interview accompanying drawing 4, determine that it is methyl beta-hydroxybutyrate.
Example 3
With propylene oxide (analytical pure) and methanol mixed, be mixed with the methanol solution that concentration is 250mmol/L.With catalyst acetic acid cobalt, cadmium iodide and methanol mixed, be mixed with the methanol solution that concentration is 12mmol/L, wherein Cobaltous diacetate and cadmium iodide total concn are 12mmol/L, the mol ratio of Cobaltous diacetate and cadmium iodide is 1: 9.Above-mentioned catalyzer methanol solution is mixed with above-mentioned propylene oxide methanol solution.Add sodium-acetate in above-mentioned mixed solution, its concentration in mixed solution is 900mmol/L.Place the quartzy photoreactor of hollow sandwich inner the 400W high voltage mercury lamp, pass into recirculated water in the interlayer, the tank of simultaneously whole reactor being put into filled with water comes the cool down lamp source.The methanol solution 4ml that will contain 250mmol/L propylene oxide, 12mmol/L catalyst acetic acid cobalt and cadmium iodide, 900mmol/L sodium-acetate adds in the quartz test tube, quartz test tube is close on the outer wall of photoreactor.At room temperature, the disposable methyl-formiate that directly adds 625mmol/L was opened the high voltage mercury lamp radiation reaction solution 45 hours simultaneously in the above-mentioned mixing solutions, and temperature of reaction is controlled at 25～60 ℃.The product that obtains is done interior mark with n-decane, carries out gas chromatographic analysis, and with the result that gas-chromatography records, asks for an interview accompanying drawing 5, and calculating yield is 55%.Carry out Product Identification with gas chromatograph-mass spectrometer, ask for an interview accompanying drawing 6, determine that it is methyl beta-hydroxybutyrate.
Claims (1)
1. the method for a synthetic methyl beta-hydroxybutyrate, it is characterized in that: at room temperature, the methyl-formiate of disposable direct adding 125～625mmol/L in the methanol solution that contains 250～1000mmol/L propylene oxide and 8～16mmol/L Cobaltous diacetate and cadmium iodide catalyzer and 300～900mmol/L sodium-acetate, wherein the mol ratio of Cobaltous diacetate and cadmium iodide is 1: 9, with 100～400W high voltage mercury lamp radiation reaction solution 15～55 hours, temperature of reaction was 25～60 ℃.
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| CN 200810012427 CN101628873B (en) | 2008-07-17 | 2008-07-17 | Method for synthesizing beta-hydroxymethyl butyrate |
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| CN101628873B true CN101628873B (en) | 2013-01-09 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1082540A (en) * | 1992-06-29 | 1994-02-23 | 国际壳牌研究有限公司 | The carbonylation of epoxy compounds |
| CN1401625A (en) * | 2001-08-13 | 2003-03-12 | 中国科学院兰州化学物理研究所 | Process for preparing methyl beta-hydroxybutyrate by carbonylation of epoxy propane |
| CN101143823A (en) * | 2006-09-11 | 2008-03-19 | 中国科学院兰州化学物理研究所 | Method for preparing optical activity 3-hydroxycarboxylate |
-
2008
- 2008-07-17 CN CN 200810012427 patent/CN101628873B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1082540A (en) * | 1992-06-29 | 1994-02-23 | 国际壳牌研究有限公司 | The carbonylation of epoxy compounds |
| CN1401625A (en) * | 2001-08-13 | 2003-03-12 | 中国科学院兰州化学物理研究所 | Process for preparing methyl beta-hydroxybutyrate by carbonylation of epoxy propane |
| CN101143823A (en) * | 2006-09-11 | 2008-03-19 | 中国科学院兰州化学物理研究所 | Method for preparing optical activity 3-hydroxycarboxylate |
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