CN103044249A - New method for compounding maleic diacid single low-carbon alcohol ester - Google Patents
New method for compounding maleic diacid single low-carbon alcohol ester Download PDFInfo
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- CN103044249A CN103044249A CN2012105887347A CN201210588734A CN103044249A CN 103044249 A CN103044249 A CN 103044249A CN 2012105887347 A CN2012105887347 A CN 2012105887347A CN 201210588734 A CN201210588734 A CN 201210588734A CN 103044249 A CN103044249 A CN 103044249A
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Abstract
A new method for compounding maleic diacid single low-carbon alcohol ester comprises the following steps: mixing maleic diacid anhydride and low-carbon alcohol; adding alkali or alkalinous inorganic salt into the mixture to form a solution; at the room temperature to a temperature below 110 DEG C, agitating the solution until the solution is clear; filtering after reaction of 0-6 hr and obtaining maleic diacid single ester salt by renewedly crystallizing filtrate; and obtaining maleic diacid single low-carbon alcohol ester via acidification, refrigeration, drying, solid liquid separation and reduced pressure distillation, wherein the mole ratio of maleic diacid anhydride to low-carbon alcohol to alkali or alkalinous inorganic salt is 1:(5-15):(1.6-2). The method has the characteristics of very kindly process conditions, simple operation and high production purity and yield.
Description
Technical field
The present invention relates to a kind of maleic acid list ester of low-carbon alcohol new synthetic method, belong to the organic chemical synthesis field.
Background technology
Maleic acid list ester of low-carbon alcohol is raw material important in the chemical field.
Traditional method is synthesized the maleic acid monoesters take br dilute anhydride (maleic anhydride) and alcohol under the raw material reflux conditions, raw material butadiene dilute acid anhydride reactant often to occur incomplete when the reaction times is too short, reaction times is long will to generate by product butadiene dilute acid diester, so that control during the reaction times and the later separation purifying all very difficult, therefore be difficult to obtain highly purified product.The present invention is to overcome above difficulty as purpose for this reason, after preparing the maleic acid monoester salt take br dilute anhydride (maleic anhydride), low-carbon alcohol (monohydroxy-alcohols such as methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, amylalcohol and primary isoamyl alcohol) and alkaline, inorganic salts as raw material, obtain sterling maleic acid monoester salt through recrystallization, then obtain highly purified maleic acid list ester of low-carbon alcohol through acidifying, below be reaction equation (alkali or alkaline, inorganic salts are take carbonate and calcium hydroxide as example):
Summary of the invention
The present invention is directed to the deficiencies in the prior art part, proposed the method for the synthetic maleic acid list ester of low-carbon alcohol that a kind of processing condition are very gentle, synthetic method is simple, cost is low, reaction yield is high, product purity is high, easy to operate.
A kind of maleic acid list ester of low-carbon alcohol new synthetic method provided by the invention, MALEIC ANHYDRIDE is mixed with low-carbon alcohol, add alkali or alkaline, inorganic salts, under room temperature to 110 ℃, be stirred to solution and be clarification, reacted 0～6 hour, and after filtration, the filtrate recrystallization is obtained the maleic acid monoester salt, then got maleic acid list ester of low-carbon alcohol through acidifying, lyophilize, solid-liquid separation and underpressure distillation; Wherein, the mol ratio of br dilute anhydride, low-carbon alcohol and alkali or alkaline, inorganic salts is 1:(5～15): (1.6～2).
In above-mentioned, low-carbon alcohol is monohydroxy-alcohol, preferably, and methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, amylalcohol or primary isoamyl alcohol.
Described alkali is potassium hydroxide, sodium hydroxid or calcium hydroxide, and alkaline, inorganic salts is salt of wormwood or yellow soda ash.
Recrystallization operates as follows: filtrate is controlled under-3 ℃～5 ℃, adds solvent, stir, leave standstill rear filtration, can get white solid maleic acid monoester salt.
The solvent that recrystallization adopts is a kind of or any two kinds and the two or more mixed liquid in tetrahydrofuran (THF), ether and the acetone.
Acidifying is first under-3 ℃～5 ℃, and (0.5～1mol/L) joins in the maleic acid monoester salt, must contain the mixture of maleic acid list ester of low-carbon alcohol with the dilute hydrochloric acid of equimolar amount.
The solvent that solid-liquid separation adopts is ether or acetone.
In the present invention, the reaction of br dilute anhydride and methyl alcohol is at room temperature carried out in the salinization; The reaction of br dilute anhydride and ethanol is carried out under 30～50 ℃; The reaction of br dilute anhydride and propyl alcohol is carried out under 60～80 ℃; The reaction of br dilute anhydride and butanols is carried out under 80～100 ℃; The reaction of br dilute anhydride and amylalcohol is carried out under 90～110 ℃.
Beneficial effect:Compare with traditional method, the present invention adds inorganic salt in the reaction of br dilute anhydride and low-carbon alcohol, so that after the salinization of maleic acid monoesters, overcome and reacted Raw butadiene dilute acid anhydride reactant not exclusively and the generation of having avoided the by product maleic acid ester, behind the organic solvent recrystallization, obtain pure maleic acid monoester salt crystal, then after acidifying, obtain the product of higher degree.
Embodiment:
Embodiment 1
10.01g (0.102mol) br dilute anhydride is dissolved in the 50mL anhydrous methanol, add 5.4g (0.51mol) anhydrous sodium carbonate behind the dissolve complete, at room temperature, be stirred to react when solution is clarification and finish, then add 60mL acetone recrystallization under 0 degree centigrade of lower slowly stirring and cotton-shaped white solid occurs, filtration drying obtains white solid monomethyl cis-butenedioic acid sodium salt 14.6g, then adding concentration is the dilute hydrochloric acid 192mL of 0.5mol/L, after lyophilize, after the tetrahydrofuran (THF) dissolving with 3 times of volumes, cross and filter out sodium-chlor, filtrate through underpressure distillation to colourless oil liquid monomethyl cis-butenedioic acid 11.8g, purity is more than 99%.
Embodiment 2
5g (0.051mol) br dilute anhydride is dissolved in the 30mL dehydrated alcohol, add 2.7g (0.0255mol) anhydrous sodium carbonate behind the dissolve complete, under 40 ℃, after being stirred to solution and being when clarification, react end in 30 minutes, then add 50mL acetone 0 degree centigrade lower slowly stir under recrystallization cotton-shaped white solid appears half an hour, filtration drying obtains white solid cis-butenedioic acid mono ethyl maleate sodium salt 7.7g, then adding concentration is the dilute hydrochloric acid 62mL of 0.75mol/L, after lyophilize, after the tetrahydrofuran (THF) dissolving with 4 times of volumes, cross and filter out sodium-chlor, filtrate through underpressure distillation to colourless oil liquid cis-butenedioic acid mono ethyl maleate 6.2g, purity is more than 99%.
Embodiment 3
5g (0.051mol) br dilute anhydride is dissolved in the anhydrous propyl alcohol of 30mL, add 2.7g (0.0255mol) anhydrous sodium carbonate behind the dissolve complete, under 50 ℃, after being stirred to solution and being when clarification, back flow reaction finished in 2.5 hours, then add 50mL acetone 0 degree centigrade lower slowly stir under recrystallization cotton-shaped white solid appears half an hour, filtration drying obtains white solid maleic acid list propyl ester sodium salt 8.2g, then adding concentration is the dilute hydrochloric acid 46mL of 1mol/L, after lyophilize, after the tetrahydrofuran (THF) dissolving with 5 times of volumes, cross and filter out sodium-chlor, filtrate through underpressure distillation to colourless oil liquid maleic acid list propyl ester 6.5g, purity is more than 99%.
It should be noted that at last above what enumerate is specific embodiments of the invention, obviously the invention is not restricted to above-described embodiment, also have many combination operations.The combination operation of associating from the present invention all belongs within the protection domain of this patent.
Claims (8)
1. maleic acid list ester of low-carbon alcohol new synthetic method, it is characterized in that, MALEIC ANHYDRIDE is mixed with low-carbon alcohol, add alkali or alkaline, inorganic salts, under room temperature to 110 ℃, be stirred to solution and be clarification, reacted 0～6 hour, after filtration, the filtrate recrystallization is obtained the maleic acid monoester salt, then get maleic acid list ester of low-carbon alcohol through acidifying, lyophilize, solid-liquid separation and underpressure distillation; Wherein, the mol ratio of br dilute anhydride, low-carbon alcohol and alkali or alkaline, inorganic salts is 1:(5～15): (1.6～2).
2. a kind of maleic acid list ester of low-carbon alcohol new synthetic method according to claim 1 is characterized in that low-carbon alcohol is methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, amylalcohol or primary isoamyl alcohol.
3. a kind of maleic acid list ester of low-carbon alcohol new synthetic method according to claim 1 is characterized in that described alkali is potassium hydroxide, sodium hydroxid or calcium hydroxide.
4. a kind of maleic acid list ester of low-carbon alcohol new synthetic method according to claim 1 is characterized in that alkaline, inorganic salts is salt of wormwood or yellow soda ash.
5. a kind of maleic acid list ester of low-carbon alcohol new synthetic method according to claim 1, it is characterized in that recrystallization operates as follows: filtrate is controlled under-3 ℃～5 ℃, adds solvent, stir, leave standstill rear filtration, can get white solid maleic acid monoester salt.
6. a kind of maleic acid list ester of low-carbon alcohol new synthetic method according to claim 1 or 5 is characterized in that, the solvent that recrystallization adopts is a kind of or any two kinds and the two or more mixed liquid in tetrahydrofuran (THF), ether and the acetone.
7. a kind of maleic acid list ester of low-carbon alcohol new synthetic method according to claim 1, it is characterized in that, acidifying is first under-3 ℃～5 ℃, (0.5～1mol/L) joins in the maleic acid monoester salt, must contain the mixture of maleic acid list ester of low-carbon alcohol with the dilute hydrochloric acid of equimolar amount.
8. a kind of maleic acid list ester of low-carbon alcohol new synthetic method according to claim 1 is characterized in that, the solvent that solid-liquid separation adopts is ether or acetone.
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| CN2012105887347A CN103044249A (en) | 2012-12-31 | 2012-12-31 | New method for compounding maleic diacid single low-carbon alcohol ester |
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| CN2012105887347A CN103044249A (en) | 2012-12-31 | 2012-12-31 | New method for compounding maleic diacid single low-carbon alcohol ester |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1616400A (en) * | 2004-09-23 | 2005-05-18 | 李文佳 | Process for preparing monomethyl fumerate |
| CN101831662A (en) * | 2010-05-17 | 2010-09-15 | 淮安苏瑞精细化工有限公司 | Method for preparing monomethyl succinate |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1616400A (en) * | 2004-09-23 | 2005-05-18 | 李文佳 | Process for preparing monomethyl fumerate |
| CN101831662A (en) * | 2010-05-17 | 2010-09-15 | 淮安苏瑞精细化工有限公司 | Method for preparing monomethyl succinate |
Non-Patent Citations (1)
| Title |
|---|
| S.N. ZLATANOS, ET AL.: "A new method of synthesis of alkyl-glycidyl esters of dicarboxylic acids in high yields", 《JAOCS》, vol. 67, no. 10, 31 October 1990 (1990-10-31), pages 661 - 664 * |
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Application publication date: 20130417 |