CN1059430C - Process for prodn. of malonate - Google Patents
Process for prodn. of malonate Download PDFInfo
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- CN1059430C CN1059430C CN97105969A CN97105969A CN1059430C CN 1059430 C CN1059430 C CN 1059430C CN 97105969 A CN97105969 A CN 97105969A CN 97105969 A CN97105969 A CN 97105969A CN 1059430 C CN1059430 C CN 1059430C
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- acetic acids
- halogenated acetic
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- alcohol
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Abstract
The present invention relates to an improvement of a technique for preparing a malonic ester by using chloroacetic acid as a raw material and by the steps of neutralization, cyanidation, acidification (hydrochloric acid), dehydration, hydrolyzation, esterification, etc. The present invention is characterized in that the steps of the hydrolyzationand, the esterification and extraction are carried out at the same time. The selectivity of the malonic ester can be up to 88 to 92%, and the technique has the advantages of short process, simple operation, easy implementation, low cost and high benefit.
Description
The present invention relates to a kind of production method of malonic ester.
As the intermediate malonic ester of industries such as agricultural chemicals, medicine, spices, dyestuff, be example with the dimethyl malonate, traditional production technique is to be raw material with industrial Mono Chloro Acetic Acid, realizes by steps such as neutralization, cyaniding, acidifying, dehydration, hydrolysis, esterifications.But yield is lower, in order to improve yield, carries out improvement on each step.As US2,337,858, the preparation of malonic ester class.Hydrolysis wherein, esterification, carry out simultaneously, and added benzene, the effect one of benzene is to add 0.5% of amount of alcohol in early stage to make the ethanol modification as denaturing agent; The 2nd, add repeatedly benzene so that solid salt separates with liquid ester in the reaction end of a period, reaction product is repeatedly extracted, use the alkali liquid washing extraction liquid at last, underpressure distillation obtains malonic ester then.Its defective is, is the product of separating reaction terminal point with the purpose of extraction agent, carry out degree for reaction and do not improve, and repeatedly extraction, multiple times of filtration, unavoidably to lose benzene, and cause environmental pollution.Its process implementing difficulty is quite big.The applicant once did confirmatory experiment, and it is when residual 10% moisture content, and the esterification degree of depth is difficult to reach 87.8% yield.Day disclosure special permission: clear 58-65, the manufacture method of 247 malonic ester, its process characteristic is that the cyanoacetic acid sodium water solution after the cyaniding directly dewaters, obtain cyanoacetic acid sodium melts, in the presence of organic solvent, drip sulfuric acid then, realize acidifying, hydrolysis, treat that HCl fully volatilizees after, add the alcohol reaction and obtain ester.Its defective is, forms viscous pastes (checking by experiment) in the dehydration later stage, is enough to make whipping device malfunctioning, can't implement aborning.At the dispersed extreme difference of the formed system of the acid, alcohol and the extraction agent that add subsequently, except that dripping sulfuric acid time length, prolonged esterification time greatly." Zhengzhou Polytechnical College's journal " 1994 the 15th volume first phases disclose one piece of paper " research of dimethyl malonate synthetic ", what it adopted is cyanoacetic acid sodium water solution hcl acidifying, back dehydration drips the sulfuric acid hydrolysis of going ahead of the rest then, adds methyl alcohol esterification in the presence of toluene again.Long in time limit relatively, complex operation.And the process of independent hydrolysis, controlled temperature should be very careful, and dropping sulfuric acid speed is very slow, otherwise causes the peracidity material to boil easily, and is dangerous big.Unless for up to 3-5 hour.
The objective of the invention is to improve the production method of malonic ester, the selectivity height, flow process is short, implements easily.
Technical characterstic of the present invention is:: with the aqueous solution that obtains with cyano group an alkali metal salt cyanogenation again after halogenated acetic acids and the alkali lye neutralization reaction with hcl acidifying, dehydration after, directly add alcohol, extraction agent also drips H
2SO
4The esterification that is hydrolyzed simultaneously obtains thick ester, then the refining malonic ester that obtains from thick ester.
The present invention is suitable for the production method of following general formula compound malonic ester,
Wherein R1, R2 be the alkyl of C1-8 or cyclohexyl or
(R5-R9 is alkyl or the H of C1-3), R3, R4 be H, C1-3 alkyl ,-the OR10 base, R10 be selected from C1-3 alkyl, cyclohexyl or
Be halogen.
Last general formula compound is preferably:
R3, R4 are the H atom, and R5-R9 is the H atom.
R1, R2 are preferably the alkyl of 1-6 for the C atomicity is 1-8, comprise straight chain, branched-chain alkyl.R1, R2 can be simultaneously identical, also can be different.
Last general formula compound most preferably is: R3, R4 are the H atom, and R1, R2 are C
1-4Alkyl.
The above method, halogenated acetic acids is chloracetic acid preferably.
The above method, alkali lye are yellow soda ash or sodium hydroxide solution, and the cyano group an alkali metal salt is a sodium cyanide.
Extraction agent is preferably toluene, dimethylbenzene.
Alcohol, the vitriolic add-on gets final product than calculated value is excessive, and the best is: alcohol with the mol ratio of halogenated acetic acids is: 2.3～2.7: 1, and the oleum of the vitriol oil or various concentration and the mol ratio of halogenated acetic acids are: 1.4～1.7: 1, when dripping sulfuric acid, the control solution temperature is no more than 70 ℃.The mol ratio of extraction agent toluene and halogenated acetic acids is: 0.3～3.0: 1, and the mol ratio of dimethylbenzene and halogenated acetic acids is: 0.3～2.5: 1.
After R1, R2 determined, esterification adopted corresponding alcohol.Neutralization, cyaniding, acidification reaction, dehydration all are to adopt prior art, do not change.Wherein the NaX of acidification reaction generation does not separate.The thick ester that esterification obtains after finishing is that organic layer, elder generation reclaim extraction agent, adopt the method for underpressure distillation to make with extra care the also same prior art of malonic ester then.
The inventive method characteristics are that hydrolysis, esterification, extraction are carried out simultaneously, reaction product is in time separated with reaction solution, thereby impel reaction to carry out improving the selectivity of purpose product (malonic ester) to generating purpose product direction.The purpose product selectivity is up to 88-92% in the therefore thick ester.Shortened technical process, simple to operate, to implement easily, cost is low.
Embodiment 1: the preparation of dimethyl malonate
With industrial Mono Chloro Acetic Acid 290 grams (pure amount is in 3 moles), use the 300ml water dissolution.Under stirring and cooling, be neutralized to PH=6.5～7.5, obtain the sodium chloroacetate aqueous solution with 30% aqueous sodium hydroxide solution.30% sodium cyanide solution is heated to 50-55 ℃, drop into the above-mentioned sodium chloroacetate aqueous solution, under stirring and heating condition, cause cyanogenation, when reaching 80-95 ℃, temperature stops to heat and beginning to cool down, when the cyaniding temperature reaches 105～115 ℃, cool and reduced to below 40 ℃ to 90-100 ℃ of constant temperature 10-60 minute, promptly obtain the cyanoacetic acid sodium solution.The content 305 that calculates cyanoacetic acid sodium according to analytical results restrains, and the cyaniding rate reaches about 95%.Add 30% technical hydrochloric acid, 365 grams, obtain the mixture aqueous solution of cyanoacetic acid and NaCl.Under the vacuum water is taken off to remaining moisture content below 6%, obtain cyanoacetic acid and NaCl mixture, be cooled to 60-70 ℃, stirring down still is flowable material.Stir and drop into methyl alcohol (with 100% densitometer) 240 grams down, extraction agent toluene 425 grams, slowly splash into 98% industrial sulphuric acid, 460 grams under 60-70 ℃, after dripping, in 5 hours, make temperature of charge reach 100 ℃ and be hydrolysis-esterification time, be cooled to 60-70 ℃ then, add entry 1000mlization salt, organic phase is told in the sedimentation layering, through neutralization, sedimentation layering, tell neutral organic phase.Get 316.3 gram finished products through underpressure distillation, through gas chromatographic analysis dimethyl malonate content 98.10%.
Embodiment 2-7: repeat embodiment 1, the content of dimethyl malonate is between 98.10-98.16% by analysis, and in cyanoacetic acid sodium, average selectivity is 88.2～91.9%.
Embodiment 8: the preparation of diethyl malonate
With the method preparation dehydration cyanoacetic acid sodium of embodiment 1 and the mixture (water content is below 6%) of NaCl.Replacing methyl alcohol with industrial alcohol (100% densitometer) 345 grams, get finished product 411.2 grams at last, is 98.23% through gas chromatographic analysis content.Obtain three batches of finished products again with present method, the average content of analyzing diethyl malonate is 98.25%, and in cyanoacetic acid sodium, average selectivity is 90.5%.
Embodiment 9: the preparation of dipropyl malonate
With the method for embodiment 1, replace methyl alcohol with propyl alcohol with (100% densitometer) 450 grams, get finished product 451.5 grams at last through gas chromatographic analysis, the content of dipropyl malonate is 98.41%.Obtain three batches of finished products again with present method, the average content of analyzing dipropyl malonate is 98.40%, and in cyanoacetic acid sodium, average selectivity is 89.8%.
Embodiment 10: the preparation of Diisopropyl malonate
With the method for embodiment 1, replace methyl alcohol with Virahol (with 100% densitometer) 450 gram, at last finished product 457.0 grams, be 98.81% through the content of gas chromatographic analysis Diisopropyl malonate.Obtain three batches of finished products again with present method, the average content of analyzing Diisopropyl malonate is 98.76%, and in cyanoacetic acid sodium, average selectivity is 90.0%.
Embodiment 11: the preparation of butyl ethyl malonate
With the method for embodiment 1, replace methyl alcohol with propyl carbinol (with 100% densitometer) 555 gram, at last finished product 511.7 grams, be 98.46% through the content of gas chromatographic analysis butyl ethyl malonate.Obtain three batches of finished products again with present method, the average content of analyzing butyl ethyl malonate is 98.30%, and in cyanoacetic acid sodium, average selectivity is 88.5%.
Claims (8)
1. the production method of malonic ester is characterized in that: with the aqueous solution that obtains with cyano group an alkali metal salt cyanogenation again after halogenated acetic acids and the alkali lye neutralization reaction with hcl acidifying, dehydration after, directly add alcohol, extraction agent also drips H
2SO
4The esterification that is hydrolyzed simultaneously obtains thick ester, then the refining malonic ester that obtains from thick ester.
2. method according to claim 1 is characterised in that malonic ester is suitable for following general formula compound,
Wherein R1, R2 are the alkyl of C1-4, and R3, R4 are H, and halogenated acetic acids is following general formula compound:
-COOH, X are halogen.
3. method according to claim 2 is characterized in that X is Cl.
4. method according to claim 1 is characterised in that alkali lye is yellow soda ash or sodium hydroxide solution, and the cyano group an alkali metal salt is a sodium cyanide.
5. method according to claim 1 is characterised in that extraction agent is toluene, dimethylbenzene.
6. method according to claim 1, be characterised in that extraction agent is a toluene, the mol ratio of toluene and halogenated acetic acids is 0.3～3.0: 1, and alcohol with the mol ratio of halogenated acetic acids is: 2.3～2.7: 1, and the mol ratio of the vitriol oil and halogenated acetic acids is: 1.4～1.7: 1.
7. method according to claim 1, be characterised in that extraction agent is a dimethylbenzene, the mol ratio of dimethylbenzene and halogenated acetic acids is: 0.3～2.5: 1 alcohol with the mol ratio of halogenated acetic acids is: 2.3～2.7: 1, and the mol ratio of the vitriol oil and halogenated acetic acids is: 1.4～1.7: 1.
8. according to the described method of claim 1, be characterised in that when dripping sulfuric acid that the control solution temperature is no more than 70 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97105969A CN1059430C (en) | 1997-05-27 | 1997-07-11 | Process for prodn. of malonate |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97105879.2 | 1997-05-27 | ||
| CN97105879 | 1997-05-27 | ||
| CN97105969A CN1059430C (en) | 1997-05-27 | 1997-07-11 | Process for prodn. of malonate |
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| Publication Number | Publication Date |
|---|---|
| CN1200368A CN1200368A (en) | 1998-12-02 |
| CN1059430C true CN1059430C (en) | 2000-12-13 |
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|---|---|---|---|
| CN97105969A Expired - Fee Related CN1059430C (en) | 1997-05-27 | 1997-07-11 | Process for prodn. of malonate |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100424066C (en) * | 2006-04-20 | 2008-10-08 | 重庆紫光化工股份有限公司 | Process of preparing malonic ester |
| CN103420834B (en) * | 2013-08-12 | 2015-06-17 | 重庆紫光化工股份有限公司 | Environment-friendly clean method for preparing dimethyl malonate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS597135A (en) * | 1982-07-05 | 1984-01-14 | Daicel Chem Ind Ltd | Preparation of malonic acid ester |
| JPS597136A (en) * | 1982-07-05 | 1984-01-14 | Daicel Chem Ind Ltd | Preparation of malonic acid ester |
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1997
- 1997-07-11 CN CN97105969A patent/CN1059430C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS597135A (en) * | 1982-07-05 | 1984-01-14 | Daicel Chem Ind Ltd | Preparation of malonic acid ester |
| JPS597136A (en) * | 1982-07-05 | 1984-01-14 | Daicel Chem Ind Ltd | Preparation of malonic acid ester |
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| CN1200368A (en) | 1998-12-02 |
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