CN101391939A - Method for preparing 3-methyl-2butenol - Google Patents
Method for preparing 3-methyl-2butenol Download PDFInfo
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- CN101391939A CN101391939A CNA2007100715057A CN200710071505A CN101391939A CN 101391939 A CN101391939 A CN 101391939A CN A2007100715057 A CNA2007100715057 A CN A2007100715057A CN 200710071505 A CN200710071505 A CN 200710071505A CN 101391939 A CN101391939 A CN 101391939A
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- butene
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Abstract
The invention discloses a preparing method of 3-methyl-2-butenol. The existing method has low yield, high production cost and heavy pollution to the environment. The method is characterized in that: 2-methyl-3-butane-2-alcohol is chloridized to obtain 1-chloro-3-methyl-2-butane which is carried out with condensation reaction with organic acid salt to obtain organic acid 3-methyl-2-butenyl ester; and then the 3-methyl-2-butenyl ester is hydrolyzed in alkaline liquor to obtain the 3-methyl-2-butenol. The method has the advantages of less secondary reaction, environmental friendliness and high yield and purity.
Description
Technical field
The present invention relates to the preparation method of a kind of spices, medicine and pesticide intermediate 3-methyl-2-butene alcohol.
Background technology
3-methyl-2-butene alcohol claims prenol again, can be used as spices; 3-methyl-2-butene alcohol is mainly used in produces citral, different vegetable alcohol (main intermediate of vitamin-E), 3,3-dimethyl-4-pentenoic acid methyl ester, DV chrysanthemumic acid methyl esters (chrysanthemum ester intermediate), the intermediate of synthesise vitamins A, carotenoid, synthetic rubber monomer also is used for other organic synthesis.
The method of at present synthetic 3-methyl-2-butene alcohol mainly contains following three kinds:
1, is raw material with 2-methyl-3-butene-2-alcohol, under the catalyzer condition, is converted into 3-methyl-2-butene alcohol.The transformation efficiency that 2-methyl-3-butene-2-alcohol is converted into 3-methyl-2-butene alcohol is low, poor yields, no industrial application value.
2, U.S. Pat 4028424 is that the raw material condensation makes 3-methyl-2-butene alcohol with iso-butylene and formaldehyde, but about 80-90% is 3-methyl-3-butenol in the resultant, and the amount of 3-methyl-2-butene alcohol is about 5%.3-methyl-3-butenol can further be converted into 3-methyl-2-butene alcohol, and U.S. Pat 4219683 transformation efficiency under hydrogen and palladium condition is 39-54% selectivity 82-99%; The transformation efficiency that Japanese Patent JP08268939 3-methyl-3-butenol under the magnesium oxide condition is converted into 3-methyl-2-butene alcohol is 57%.The transformation efficiency that 3-methyl-3-butenol is converted into 3-methyl-2-butene alcohol is low, the conversion reaction conditions harshness, and separating difficulty is big, the technical requirements height.
3, with the isoprene be raw material, obtain isopentene group chlorine through chlorination, resterification obtains prenyl acetate, obtains 3-methyl-2-butene alcohol through alkaline hydrolysis again.The esterification of this method, alkaline hydrolysis yield height, reaction is easy to control, but the yield of isoprene and hcl reaction is lower, and about 78%, cause the production cost of 3-methyl-2-butene alcohol higher.
Summary of the invention
Technical problem to be solved by this invention is to overcome the defective that above-mentioned prior art exists, and the preparation method of a kind of purity height, the total recovery 3-methyl-2-butene alcohol about 90% is provided.
For this reason, the present invention adopts following technical scheme: the preparation method of 3-methyl-2-butene alcohol, it is characterized in that earlier 2-methyl-3-butene-2-pure chlorination being got 1-chloro-3-methyl-2-butene, then 1-chloro-3-methyl-2-butene and organic acid salt condensation get organic acid 3-methyl-2-butene ester, with the hydrolysis in alkali lye of organic acid 3-methyl-2-butene ester, obtain 3-methyl-2-butene alcohol then.
The preparation method of described 3-methyl-2-butene alcohol, the used chlorination reagent of chlorination is two (trichloromethyl) carbonic ethers, phosphorus oxychloride or phosphorus trichloride, be preferably two (trichloromethyl) carbonic ethers, its mole dosage is the 17-18% of 3-methyl-2-butene alcohol mole dosage.Two (trichloromethyl) carbonic ethers of chlorination reagent that the present invention is used are commonly called as triphosgene, solid phosgene, are a kind of industrial chemicals of environmental protection, and toxicity is little, storing, safe in utilization, convenient.In the chlorination reaction of two (trichloromethyl) carbonic ether to alcohol, when generating hydrochloric ether, only generate carbonic acid gas and water, environmentally friendly.
The present invention makes isopentene group chlorine with 2-methyl-3-butene-2-alcohol with two (trichloromethyl) carbonic ether chlorinations earlier, and yield reaches 95%;
Then with isopentene group chlorine and organic acid salt
R＝H，CH
3，CH
3CH
2
X＝Na，K
Condensation gets organic acid isopentene ester
R＝H，CH
3，CH
3CH
2
Again this organic acid isopentene ester hydrolysis in alkali lye is obtained 3-methyl-2-butene alcohol.The total recovery that 2-methyl-3-butene-2-pure chlorination, esterification, three steps of hydrolysis obtain 3-methyl-2-butene alcohol adds up to 90%.
The synthetic route of 3-methyl-2-butene alcohol is as follows:
Raw material 2-methyl of the present invention-3-butene-2-alcohol can be made by oneself, also can buy to obtain.
The preparation method of described 3-methyl-2-butene alcohol, the used catalyzer of chlorination is pyridine, N, accelerine, N, dinethylformamide, triethylamine, Tri-n-Propylamine, tri-n-butylamine or triphenylphosphine, preferred pyridine.
The preparation method of described 3-methyl-2-butene alcohol, organic acid salt is sodium formiate, potassium formiate, sodium acetate, potassium acetate, Sodium Propionate or potassium propionate, with obtained formic acid isopentene ester, prenyl acetate, propionic acid isopentene ester respectively after the condensation of 1-chloro-3-methyl-2-butene, preferred sodium acetate.
The preparation method of described 3-methyl-2-butene alcohol, alkali lye is yellow soda ash, salt of wormwood, sodium hydroxide or potassium hydroxide.
The preparation method of described 3-methyl-2-butene alcohol, the temperature of chlorination reaction are 0-20 ℃, and the temperature of condensation reaction is 80-150 ℃, and condensation reaction is carried out under nitrogen protection, makes condensation reaction complete, the yield height.
The present invention has following beneficial effect: the reaction conditions gentleness, and technological operation is easy to control, and side reaction is few; Chlorination reagent toxicity is little, storing, safe in utilization, convenient, environmentally friendly; Yield height (total recovery reaches 90%, and 2-methyl-3-butene-2-pure one step of chlorination reaction system 1-chloro-3-methyl-2-butene yield reaches 95%), the purity height.
The invention will be further described below in conjunction with embodiment.
Embodiment
The preparation of embodiment 1 1-chloro-3-methyl-2-butene
In having the 1000ml there-necked flask of mechanical stirring, thermometer, drop into 430g (5.0mol) 2-methyl-3-butene-2-alcohol, be cooled to 0 ℃ with the cryosel bath, add two (trichloromethyl) carbonic ether 252g (0.85mol) under stirring in batches, drip pyridine 0.4g (0.0056mol), in 0-10 ℃ of reaction 3 hours, standing demix, twice back distillation of oil reservoir washing obtains 1-chloro-3-methyl-2-butene 497g (4.75mol), yield 95%.
The preparation of embodiment 2 1-chloro-3-methyl-2-butenes
In having the 1000ml there-necked flask of mechanical stirring, thermometer, drop into 430g (5.0mol) 2-methyl-3-butene-2-alcohol, be cooled to 10 ℃ with the cryosel bath, add two (trichloromethyl) carbonic ether 252g (0.85mol) under stirring in batches, drip pyridine 2.0g (0.028mol), in 10-20 ℃ of reaction 1.5 hours, standing demix, twice back distillation of oil reservoir washing obtains 1-chloro-3-methyl-2-butene 471g (4.5mol), yield 90%.
The preparation of embodiment 3 prenyl acetates
In 2000ml glass reaction still, drop into 523g (5.0mol) 1-chloro-3-methyl-2-butene, 430g (5.25mol) sodium acetate, charge into nitrogen to 0.2MPa, stir and heat up, in 110-120 ℃ of reaction 2 hours, reaction finished, shed pressure, be cooled to 20 ℃ with 500ml * 2 dichloromethane extractions 2 times, concentrating under reduced pressure, distillation, obtain prenyl acetate 615g (4.8mol), yield 96%.
The preparation of embodiment 4 prenyl acetates
In 2000ml glass reaction still, drop into 523g (5.0mol) 1-chloro-3-methyl-2-butene, 515g (5.25mol) potassium acetate, charge into nitrogen to 0.2MPa, stir and heat up, in 80-90 ℃ of reaction 2 hours, reaction finished, shed pressure, be cooled to 20 ℃ with 500ml * 2 dichloromethane extractions 2 times, concentrating under reduced pressure, distillation, obtain prenyl acetate 628g (4.9mol), yield 98%.
The preparation of embodiment 5 3-methyl-2-butene alcohol
In having the 3000ml there-necked flask of mechanical stirring, thermometer, drop into 641g (5.0mol) prenyl acetate, 10% aqueous sodium hydroxide solution 2100g (5.25mol) stirs and heats up, in 95-100 ℃ of reaction 5 hours, be cooled to 20 ℃, layering, water layer 500ml dichloromethane extraction, merge the organic layer concentrating under reduced pressure, distillation obtains 3-methyl-2-butene alcohol 426g (4.95mol), yield 99%.
The preparation of embodiment 6 3-methyl-2-butene alcohol
In having the 3000ml there-necked flask of mechanical stirring, thermometer, drop into 641g (5.0mol) prenyl acetate, 20% potassium hydroxide aqueous solution 1470g (5.25mol) stirs and heats up, in 65-70 ℃ of reaction 3 hours, be cooled to 20 ℃, layering, water layer 500ml dichloromethane extraction, merge the organic layer concentrating under reduced pressure, distillation obtains 3-methyl-2-butene alcohol 426g (4.95mol), yield 99%.
The above only is preferred embodiment of the present invention.Every foundation technical spirit of the present invention all falls within the scope of protection of the present invention any simple modification, equivalent variations and modification that above embodiment did.
Claims (9)
1, the preparation method of 3-methyl-2-butene alcohol, it is characterized in that earlier 2-methyl-3-butene-2-pure chlorination being got 1-chloro-3-methyl-2-butene, then 1-chloro-3-methyl-2-butene and organic acid salt condensation get organic acid 3-methyl-2-butene ester, with the hydrolysis in alkali lye of organic acid 3-methyl-2-butene ester, obtain 3-methyl-2-butene alcohol then.
2, the preparation method of 3-methyl-2-butene alcohol according to claim 1 is characterized in that the used chlorination reagent of chlorination is two (trichloromethyl) carbonic ethers, phosphorus oxychloride or phosphorus trichloride.
3, the preparation method of 3-methyl-2-butene alcohol according to claim 2 is characterized in that the used chlorination reagent of chlorination is two (trichloromethyl) carbonic ethers, and its mole dosage is the 17-18% of 3-methyl-2-butene alcohol mole dosage.
4, the preparation method of 3-methyl-2-butene alcohol according to claim 1 and 2 is characterized in that the used catalyzer of chlorination is pyridine, N, accelerine, N, dinethylformamide, triethylamine, Tri-n-Propylamine, tri-n-butylamine or triphenylphosphine.
5, the preparation method of 3-methyl-2-butene alcohol according to claim 4 is characterized in that the used catalyzer of chlorination is a pyridine.
6, the preparation method of 3-methyl-2-butene alcohol according to claim 1 and 2 is characterized in that described organic acid salt is sodium formiate, potassium formiate, sodium acetate, potassium acetate, Sodium Propionate or potassium propionate.
7, the preparation method of 3-methyl-2-butene alcohol according to claim 6 is characterized in that described organic acid salt is a sodium acetate.
8, the preparation method of 3-methyl-2-butene alcohol according to claim 1 and 2 is characterized in that described alkali lye is yellow soda ash, salt of wormwood, sodium hydroxide or potassium hydroxide.
9, the preparation method of 3-methyl-2-butene alcohol according to claim 1 and 2, the temperature that it is characterized in that chlorination reaction is 0-20 ℃, and the temperature of condensation reaction is 80-150 ℃, and condensation reaction is carried out under nitrogen protection.
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| CN2007100715057A CN101391939B (en) | 2007-09-20 | 2007-09-20 | Method for preparing 3-methyl-2butenol |
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| CN2007100715057A CN101391939B (en) | 2007-09-20 | 2007-09-20 | Method for preparing 3-methyl-2butenol |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040469A (en) * | 2009-10-23 | 2011-05-04 | 中国石油化工股份有限公司 | Method for preparing tetraenol from production waste liquid of 1-chloro prenyl |
| CN102432434A (en) * | 2011-11-17 | 2012-05-02 | 洛阳师范学院 | Method for synthesizing 3-methyl-3-butene-1-ol |
| CN102924227A (en) * | 2012-11-02 | 2013-02-13 | 南通天泽化工有限公司 | Production technology of isopentenyl alcohol |
| CN103224444A (en) * | 2013-05-23 | 2013-07-31 | 南京工业大学 | Method for synthesizing 3-methyl-3-butenyl-1-ol by two-step process |
| CN105175220A (en) * | 2015-09-08 | 2015-12-23 | 山东成泰化工有限公司 | Hydrogenation catalytic synthesis method of isopentenol |
| CN109879718A (en) * | 2017-12-06 | 2019-06-14 | 中国科学院大连化学物理研究所 | A kind of synthetic method of 5,5,5- trichloro-2-methyl-2-pentene |
| CN110372505A (en) * | 2019-08-30 | 2019-10-25 | 锦西化工研究院有限公司 | A kind of preparation method of dibutyl oxalate |
| CN111393275A (en) * | 2020-04-28 | 2020-07-10 | 上海现代哈森（商丘）药业有限公司 | Method for synthesizing intermediate farnesyl acetone and method for synthesizing phytol, isophytol and geranylgeraniol by using intermediate farnesyl acetone |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH572874A5 (en) * | 1972-05-09 | 1976-02-27 | Hoffmann La Roche |
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2007
- 2007-09-20 CN CN2007100715057A patent/CN101391939B/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040469A (en) * | 2009-10-23 | 2011-05-04 | 中国石油化工股份有限公司 | Method for preparing tetraenol from production waste liquid of 1-chloro prenyl |
| CN102432434A (en) * | 2011-11-17 | 2012-05-02 | 洛阳师范学院 | Method for synthesizing 3-methyl-3-butene-1-ol |
| CN102924227A (en) * | 2012-11-02 | 2013-02-13 | 南通天泽化工有限公司 | Production technology of isopentenyl alcohol |
| CN103224444A (en) * | 2013-05-23 | 2013-07-31 | 南京工业大学 | Method for synthesizing 3-methyl-3-butenyl-1-ol by two-step process |
| CN105175220A (en) * | 2015-09-08 | 2015-12-23 | 山东成泰化工有限公司 | Hydrogenation catalytic synthesis method of isopentenol |
| CN109879718A (en) * | 2017-12-06 | 2019-06-14 | 中国科学院大连化学物理研究所 | A kind of synthetic method of 5,5,5- trichloro-2-methyl-2-pentene |
| CN109879718B (en) * | 2017-12-06 | 2021-09-17 | 中国科学院大连化学物理研究所 | Synthetic method of 5,5, 5-trichloro-2-methyl-2-pentene |
| CN110372505A (en) * | 2019-08-30 | 2019-10-25 | 锦西化工研究院有限公司 | A kind of preparation method of dibutyl oxalate |
| CN111393275A (en) * | 2020-04-28 | 2020-07-10 | 上海现代哈森（商丘）药业有限公司 | Method for synthesizing intermediate farnesyl acetone and method for synthesizing phytol, isophytol and geranylgeraniol by using intermediate farnesyl acetone |
| CN111393275B (en) * | 2020-04-28 | 2023-08-04 | 上海现代哈森（商丘）药业有限公司 | Method for synthesizing intermediate farnesyl acetone and method for synthesizing plant alcohol, isophytol and geranylgeraniol by using same |
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| CN101391939B (en) | 2012-04-25 |
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