CN102786436A - Method for synthesizing cyanoacetate - Google Patents
Method for synthesizing cyanoacetate Download PDFInfo
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- CN102786436A CN102786436A CN2011101327943A CN201110132794A CN102786436A CN 102786436 A CN102786436 A CN 102786436A CN 2011101327943 A CN2011101327943 A CN 2011101327943A CN 201110132794 A CN201110132794 A CN 201110132794A CN 102786436 A CN102786436 A CN 102786436A
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- ionic liquid
- cyanoacetate
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Abstract
A method for synthesizing cyanoacetate. Cyanoacetic acid is catalyzed to react with alcohol in an esterification reaction to obtain cyanoacetate; the method is characterized in that ionic liquid is used as a reaction medium and a catalyst of the esterification reaction; the ionic liquid is selected from one of the following molecular structural formulae, such as imidazole ionic liquid in molecular structural formula I-1, pyrrolidone ionic liquid in molecular structural formula I-2, or pyridine sulfonic acid ionic liquid in molecular structural formula I-3; compared with a traditional concentrated sulfuric acid catalytic method, the method of the invention has the advantages of simple operation, easy product separation, capability of ionic liquid recycle, environment friendliness and the like, and has very good industrial application prospects; wherein, R1 is H or a sulfopropyl group; X is HSO4, or BF4.
Description
Technical field
The present invention relates to a kind of method that belongs to catalysis cyanoacetic acid and pure esterification reaction in the organic chemical reactions method.
Background technology
The cyanoacetate compounds is important organic synthesis raw material and medical dyestuff intermediate, especially ethyl cyanoacetate, as a kind of important chemical midbody, is mainly used in synthetic fast binder 502 glue.It carries out condensation reaction with formaldehyde under the effect of basic catalyst, obtain a-TK 201 monomer through dehydration, drying, cracking and rectification under vacuum.
The existing method for preparing the cyanoacetate class has sulfuric acid catalysis method (Journal of Agricultural and Food Chemistry, 58 (5), 2730-2735; 2010), organic solvent adds method (European Journal of Organic Chemistry, (14), the 2356-2362 of dewatering agent in addition as the method (Faming Zhuanli Shenqing, 101544669,30 Sep 2009) of band aqua; 2002) etc.In industry, traditional cyanoacetic acid esterification technology uses the vitriol oil as catalyzer usually, needs to use a large amount of alcohol as reactant with as solvent.This method exists that complicated operation (need repeatedly add acid and add pure esterification), selectivity are low, long reaction time, product are difficult to separate, equipment corrosion is serious, and causes spent acid solution to handle difficult problems such as trouble.Therefore, a kind of green synthesis method with novel cyanoacetate class of good environment benefit and economic benefit of exploitation is of great practical significance.
At present, ionic liquid obtains broad research as novel green reaction medium and catalyzer in organic reaction fields such as Diels-Alder reaction, Heck reaction, redox reaction, organometallic reaction, esterification.Ionic liquid is at catalysis RCH
2COOH (R is H or alkyl or phenyl) all has more report (Zhao, G.Y. at home and abroad with the esterification of alcohol; Jiang, T.; Gao, H.X..Green Chem., 2004,6:75-77; Zhu, H.P.; Yang, F.; Tang, J.; He, M.Y..B.Green Chem., 2003,5:38-39; Zhang, H.; Xu, F.; Zhou, X.; Zhang, G.; Wang, C..Green Chem, 2007,9:1208).People such as Qiu Tao disclose a kind of with hydrotalcite or houghite as catalyzer; Catalysis methyl cyanoacetate and ethanol carry out the process method (publication number CN 101245034A) of the synthetic ethyl cyanoacetate of esterification exchange process, and people such as Douglas J.Raber have reported cyanoacetic acid and alkylating reagent [Et
3O]
+BF
4 3+Method (Journal of Organic Chemistry, 44 (7), the 1149-54 of the synthetic ethyl cyanoacetate of reaction; 1979), do not see the report of the universal method of relevant novel, environmental protection, green a series of cyanoacetate compounds of preparation as yet.
Summary of the invention
Technical problem to be solved by this invention provides a kind of method that in acidic ion liquid, prepares the cyanoacetate compounds, and this method has environmental friendliness, selectivity and transformation efficiency height, technology characteristic of simple.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: a kind of method of synthetic cyanoacetate; Catalysis cyanoacetic acid and alcohol carry out esterification and obtain cyanoacetate; It is characterized in that: ionic liquid is as the reaction medium and the catalyzer of esterification; Described ionic liquid is selected the wherein a kind of of following molecular structural formula for use; The glyoxaline ion liquid of molecular structural formula I-1, the pyridine-sulfonic acid class ionic liquid of the pyrrolidinone compounds ionic liquid of molecular structural formula I-2 or molecular structural formula I-3;
Wherein, R
1Implication be H, or sulfonic acid propyl group; The implication of X is HSO
4, perhaps BF
4
As preferably, described alcohol is C
1～C
8Monobasic saturated fatty alcohol, hexalin or the benzylalcohol of straight or branched.
Accordingly, described cyanoacetate is any one of following molecular structural formula: the cyanoacetic acid alkyl ester of molecular structural formula II-1, the cyanoacetic acid cycloalkyl ester of molecular structural formula II-2, the cyanoacetic acid benzyl ester of molecular structural formula II-3;
R wherein
2Be C
1～C
8The straight or branched saturated alkyl in a kind of.
As preferably; Described esterification condition is: ionic liquid, cyanoacetic acid, alcohol are mixed into mol ratio are (0.1～5): 1: the mixture of (1～5); Stirring reaction under 40～100 degrees centigrade the temperature of reaction reacted after 2～15 hours, isolated reaction system upper strata ester layer and just could; For not stratified reaction system, add less water and make the layering of ester layer, separate obtaining ester.
Further improve, described reaction system is told ionic liquid layer, through the water extracting and washing, heat decompression dehydration, take off organism after, ionic liquid can be reused.
At last, described ionic liquid, cyanoacetic acid, alcohol mix order in no particular order.
The present invention compares with reaction process with the described traditional catalyst of background technology, the invention has the advantages that:
1. operation and technology are simple, need not add a large amount of alcohol;
2. the reaction times lacks, and energy waste is low;
3. separate easily,, can directly obtain esterification products through toppling over or the water extraction;
4. ionic liquid can be recycled after simply dewatering, and environmental pollution is little.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.
Following embodiment further specifies of the present invention, is not limitation of the present invention.Used ionic liquid Methylimidazole propanesulfonic acid-bisulfate ion negative ion [(CH in the embodiment
2)
3SO
3Hmin] HSO
4, protonated Methylimidazole-bisulfate ion negative ion [Hmin] HSO
4, protonated pyrrolidone acidic ion liquid [Hnmp] HSO
4, according to method preparation (Cole, the A.C. of public reported; Jensen, J.L.; Ntai, I.; Tran, K.L.T.; Weaver, K.J.; Forbes, D.C.; Davis, J.H..J.Am.Chem.Soc., 2002,124:5962-5963.Yue Caibo, Wei Yuanyang, Lv Minjie, applied chemistry 2006,23:1282-1285.Xie，C.；Li，H.L.；Li，L.；Yu，S.T.；Liu，F.S..J.Hazard.Mater.，2008，151：847.)。
Embodiment 1:
With 3.02g (10mmol) ionic liquid [(CH
2)
3SO
3Hmin] HSO
4And 4.339g (50mmol) cyanoacetic acid and 1.6g (50mmol) methyl alcohol puts into reaction flask, stirs heating; Controlled temperature is 60 ℃; Reaction 4h, reaction solution leaves standstill, homogeneous phase; Add less water and tell lower floor's esterification products methyl cyanoacetate through the extraction separatory, it is 80.36% that, quantitative analysis qualitative through GC-MS obtains productive rate.Behind ionic liquid layer process water extracting and washing, heating decompression dehydration, the organic matter removal, reuse.
Embodiment 2:
With 3.02g (10mmol) ionic liquid [(CH
2)
3SO
3Hmin] HSO
4And 4.339g (50mmol) cyanoacetic acid and 2.3g (50mmol) ethanol puts into reaction flask, stirs heating; Controlled temperature is 80 ℃, reaction 4h, and reaction solution leaves standstill; Layering is told upper strata esterification products ethyl cyanoacetate through separatory, and it is 79.05% that, quantitative analysis qualitative through GC-MS obtains productive rate.Ionic liquid layer is reused behind process water extracting and washing, heating decompression dehydration, organic matter removal.
Embodiment 3:
With 3.02g (10mmol) ionic liquid [(CH
2)
3SO
3Hmin] HSO
4And 4.339g (50mmol) cyanoacetic acid and 3g (50mmol) n-propyl alcohol put into reaction flask, stirs heating; Controlled temperature is 80 ℃, reaction 4h, and reaction solution leaves standstill; Layering is told upper strata esterification products cyanoacetic acid propyl ester through separatory, and it is 81.32% that, quantitative analysis qualitative through GC-MS obtains productive rate.Ionic liquid layer is reused behind process water extracting and washing, heating decompression dehydration, organic matter removal.
Embodiment 4:
With 3.02g (10mmol) ionic liquid [(CH
2)
3SO
3Hmin] HSO
4And 4.339g (50mmol) cyanoacetic acid and 3g (50mmol) Virahol put into reaction flask, stirs heating; Controlled temperature is 80 ℃, reaction 4h, and reaction solution leaves standstill; Layering is told upper strata esterification products cyanoacetic acid isopropyl ester through separatory, and it is 82.09% that, quantitative analysis qualitative through GC-MS obtains productive rate.Behind ionic liquid layer process water extracting and washing, heating decompression dehydration, the organic matter removal, reuse.
Embodiment 5:
With 3.02g (10mmol) ionic liquid [(CH
2)
3SO
3Hmin] HSO
4And 4.339g (50mmol) cyanoacetic acid and 3.7g (50mmol) propyl carbinol put into reaction flask, stirs heating; Controlled temperature is 80 ℃, reaction 4h, and reaction solution leaves standstill; Layering is told upper strata esterification products n-butyl cyanoacetate through separatory, and it is 84.27% that, quantitative analysis qualitative through GC-MS obtains productive rate.Behind ionic liquid layer process water extracting and washing, heating decompression dehydration, the organic matter removal, reuse 5 times,, quantitative analysis qualitative through GC-MS, productive rate is respectively 82.49%, 80.09%, and 78.69%, 78.38%.
Embodiment 6:
With 3.02g (10mmol) ionic liquid [(CH
2)
3SO
3Hmin] HSO
4And 4.339g (50mmol) cyanoacetic acid and 6.5g (50mmol) n-Octanol put into reaction flask, stirs heating; Controlled temperature is 80 ℃, reaction 4h, and reaction solution leaves standstill; Layering is told upper strata esterification products cyanoacetic acid monooctyl ester through separatory, and it is 84.94% that, quantitative analysis qualitative through GC-MS obtains productive rate.Behind ionic liquid layer process water extracting and washing, heating decompression dehydration, the organic matter removal, reuse.
Embodiment 7:
With 3.02g (10mmol) ionic liquid [(CH
2)
3SO
3Hmin] HSO
4And 4.339g (50mmol) cyanoacetic acid and 5g (50mmol) hexalin put into reaction flask, stirs heating; Controlled temperature is 80 ℃, reaction 4h, and reaction solution leaves standstill; Layering is told upper strata esterification products cyanoacetic acid cyclohexyl through separatory, and it is 79.66% that, quantitative analysis qualitative through GC-MS obtains productive rate.Ionic liquid layer is reused behind process water extracting and washing, heating decompression dehydration, organic matter removal.
Embodiment 8:
With 3.02g (10mmol) ionic liquid [(CH
2)
3SO
3Hmin] HSO
4And 4.339g (50mmol) cyanoacetic acid and 5.4g (50mmol) phenylcarbinol put into reaction flask, stirs heating; Controlled temperature is 80 ℃; Reaction 4h, reaction solution leaves standstill, layering; Tell upper strata esterification products cyanoacetic acid benzyl ester through separatory, it is 72.79% that, quantitative analysis qualitative through GC-MS obtains productive rate.Behind ionic liquid layer process water extracting and washing, heating decompression dehydration, the organic matter removal, reuse.
Embodiment 9:
With 1.8g (10mmol) ionic liquid [Hmin] HSO
4And 4.339g (50mmol) cyanoacetic acid and 2.3g (50mmol) ethanol puts into reaction flask, stirs heating; Controlled temperature is 80 ℃; Reaction 4h, reaction solution leaves standstill, homogeneous phase; Add less water and tell lower floor's esterification products ethyl cyanoacetate through the extraction separatory, it is 54.91% that, quantitative analysis qualitative through GC-MS obtains productive rate.Behind ionic liquid layer process water extracting and washing, heating decompression dehydration, the organic matter removal, reuse.
Embodiment 10:
With 1.97g (10mmol) ionic liquid [Hnmp] HSO
4And 4.339g (50mmol) cyanoacetic acid and 2.3g (50mmol) ethanol puts into reaction flask, stirs heating; Controlled temperature is 80 ℃; Reaction 4h, reaction solution leaves standstill, homogeneous phase; Add less water and tell lower floor's esterification products ethyl cyanoacetate through the extraction separatory, it is 58.65% that, quantitative analysis qualitative through GC-MS obtains productive rate.Behind ionic liquid layer process water extracting and washing, heating decompression dehydration, the organic matter removal, reuse.
Claims (6)
1. the method for a synthetic cyanoacetate; Catalysis cyanoacetic acid and alcohol carry out esterification and obtain cyanoacetate; It is characterized in that: ionic liquid is as the reaction medium and the catalyzer of esterification; Described ionic liquid is selected the wherein a kind of of following molecular structural formula for use, the glyoxaline ion liquid of molecular structural formula I-1, the pyridine-sulfonic acid class ionic liquid of the pyrrolidinone compounds ionic liquid of molecular structural formula I-2 or molecular structural formula I-3;
Wherein, R
1Implication be H, or sulfonic acid propyl group; The implication of X is HSO
4, perhaps BF
4
2. the method for synthetic cyanoacetate according to claim 1 is characterized in that described alcohol is C
1～C
8Monobasic saturated fatty alcohol, hexalin or the benzylalcohol of straight or branched.
3. the method for synthetic cyanoacetate according to claim 1; It is characterized in that described cyanoacetate is any one of following molecular structural formula: the cyanoacetic acid alkyl ester of molecular structural formula II-1; The cyanoacetic acid cycloalkyl ester of molecular structural formula II-2, the cyanoacetic acid benzyl ester of molecular structural formula II-3;
R wherein
2Be C
1～C
8The straight or branched saturated alkyl in a kind of.
4. the method for synthetic cyanoacetate according to claim 1; It is characterized in that described esterification condition is: ionic liquid, cyanoacetic acid, alcohol are mixed into mol ratio are (0.1～5): 1: the mixture of (1～5); Stirring reaction under 40～100 degrees centigrade the temperature of reaction; React after 2～15 hours, isolate reaction system upper strata ester layer and just can; For not stratified reaction system, add less water and make the layering of ester layer, separate obtaining ester.
5. the method for synthetic cyanoacetate according to claim 4 is characterized in that described reaction system tells ionic liquid layer, through the water extracting and washing, heat decompression dehydration, take off organism after, ionic liquid can be reused.
6. the method for synthetic cyanoacetate according to claim 4 is characterized in that described ionic liquid, cyanoacetic acid, alcohol mix order in no particular order.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467519A (en) * | 2017-09-07 | 2019-03-15 | 汪忠华 | A kind of preparation method of malonic acid single pair p-Nitrobenzyl |
| CN112645843A (en) * | 2020-12-25 | 2021-04-13 | 复旦大学 | Synthesis method of tert-butyl cyanoacetate |
| CN114907304A (en) * | 2022-05-27 | 2022-08-16 | 上海克琴科技有限公司 | Preparation method of tocopherol retinoic acid ester |
| CN116199577A (en) * | 2022-12-27 | 2023-06-02 | 甘肃省化工研究院有限责任公司 | Method for synthesizing UV-120 by ionic liquid catalysis |
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|---|---|---|---|---|
| US6271410B1 (en) * | 2000-06-06 | 2001-08-07 | Creanova Inc. | Higher alkyl esters of cyanoacetic acid |
| CN1880295A (en) * | 2005-06-17 | 2006-12-20 | 广东工业大学 | Method for catalyzing alcohol acid esterification using ion liquid |
| CN101137437A (en) * | 2005-01-04 | 2008-03-05 | 贝尔法斯特女王大学 | Basic ionic liquids |
| CN101982453A (en) * | 2010-09-10 | 2011-03-02 | 周峰岩 | Preparation method of nipagin ester compound under promotion of sulfonic acidic ionic liquid |
-
2011
- 2011-05-19 CN CN201110132794.3A patent/CN102786436B/en not_active Expired - Fee Related
Patent Citations (4)
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| US6271410B1 (en) * | 2000-06-06 | 2001-08-07 | Creanova Inc. | Higher alkyl esters of cyanoacetic acid |
| CN101137437A (en) * | 2005-01-04 | 2008-03-05 | 贝尔法斯特女王大学 | Basic ionic liquids |
| CN1880295A (en) * | 2005-06-17 | 2006-12-20 | 广东工业大学 | Method for catalyzing alcohol acid esterification using ion liquid |
| CN101982453A (en) * | 2010-09-10 | 2011-03-02 | 周峰岩 | Preparation method of nipagin ester compound under promotion of sulfonic acidic ionic liquid |
Non-Patent Citations (3)
| Title |
|---|
| 《J. AM. CHEM. SOC.》 20020705 Amanda C. Cole等 Novel Br�nsted Acidic Ionic Liquids and Their Use as Dual Solvent-Catalysts 第5962-5963页 1-6 第124卷, 第21期 * |
| AMANDA C. COLE等: "Novel Brønsted Acidic Ionic Liquids and Their Use as Dual Solvent-Catalysts", 《J. AM. CHEM. SOC.》 * |
| AMANDA C. COLE等: "Novel Brønsted Acidic Ionic Liquids and Their Use as Dual Solvent-Catalysts", 《J. AM. CHEM. SOC.》, vol. 124, no. 21, 5 July 2002 (2002-07-05), pages 5962 - 5963 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467519A (en) * | 2017-09-07 | 2019-03-15 | 汪忠华 | A kind of preparation method of malonic acid single pair p-Nitrobenzyl |
| CN112645843A (en) * | 2020-12-25 | 2021-04-13 | 复旦大学 | Synthesis method of tert-butyl cyanoacetate |
| CN112645843B (en) * | 2020-12-25 | 2022-05-20 | 复旦大学 | Synthesis method of tert-butyl cyanoacetate |
| CN114907304A (en) * | 2022-05-27 | 2022-08-16 | 上海克琴科技有限公司 | Preparation method of tocopherol retinoic acid ester |
| CN114907304B (en) * | 2022-05-27 | 2024-02-13 | 上海克琴科技有限公司 | Preparation method of tocopherol retinoic acid ester |
| CN116199577A (en) * | 2022-12-27 | 2023-06-02 | 甘肃省化工研究院有限责任公司 | Method for synthesizing UV-120 by ionic liquid catalysis |
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