CN102786436B - A kind of method of synthesizing cyanoacetate - Google Patents

A kind of method of synthesizing cyanoacetate Download PDF

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Publication number
CN102786436B
CN102786436B CN201110132794.3A CN201110132794A CN102786436B CN 102786436 B CN102786436 B CN 102786436B CN 201110132794 A CN201110132794 A CN 201110132794A CN 102786436 B CN102786436 B CN 102786436B
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ionic liquid
cyanoacetate
structural formula
molecular structural
cyanoacetic acid
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CN102786436A (en
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陈金才
张婷婷
梁洪泽
余波
姚江
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ZHEJIANG JIURJIU CHEMICALS CO Ltd
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ZHEJIANG JIURJIU CHEMICALS CO Ltd
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Abstract

A kind of method of synthesizing cyanoacetate, catalysis cyanoacetic acid and alcohol carry out esterification and obtain cyanoacetate, it is characterized in that: ionic liquid is as the reaction medium of esterification and catalyzer, described ionic liquid selects the wherein a kind of of following molecular structural formula, the glyoxaline ion liquid of molecular structural formula I-1, the pyrrolidinone compounds ionic liquid of molecular structural formula I-2 or the pyridine-sulfonic acid class ionic liquid of molecular structural formula I-3; The present invention is compared with traditional sulphuric acid catalysis method, and have simple to operate, product is easily separated, and ionic liquid can be recycled, advantages of environment protection, has good prospects for commercial application; wherein, R 1implication be H, or propyl sulfonic acid; The implication of X is HSO 4, or BF 4.

Description

A kind of method of synthesizing cyanoacetate
Technical field
The present invention relates to a kind of method belonging to catalysis cyanoacetic acid and alcohol esterification in organic chemical reactions method.
Background technology
Cyanoacetate compounds is important organic synthesis raw material and medical dyestuff intermediate, especially ethyl cyanoacetate, as a kind of important chemical intermediate, is mainly used in synthesis fast binder 502 glue.It carries out condensation reaction with formaldehyde under the effect of basic catalyst, obtains a-ethyl cyanoacrylate monomer through dehydration, drying, cracking and rectification under vacuum.
The existing method preparing cyanoacetate class has sulfuric acid catalysis method (Journal of Agricultural and FoodChemistry, 58 (5), 2730-2735; 2010), organic solvent is as method (Faming ZhuanliShenqing, 101544669 of water entrainer, 30 Sep 2009), add method (European Journal of OrganicChemistry, (14), the 2356-2362 of dewatering agent in addition; 2002) etc.Industrially, traditional cyanoacetic acid esterification techniques uses the vitriol oil as catalyzer usually, needs to use a large amount of alcohol as reactant with as solvent.The method also exists complicated operation (need carry out adding acid for many times and add alcohol esterification), selectivity is low, long reaction time, product are difficult to separation, equipment corrosion is serious, and causes the difficult problems such as spent acid solution process trouble.Therefore, develop a kind of green synthesis method with the New cyanide acetate esters of good environment benefit and economic benefit to be of great practical significance.
At present, ionic liquid, as novel green reaction medium and catalyzer, obtains extensively research in the 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).The people such as Qiu Tao disclose one hydrotalcite or houghite as catalyzer, catalysis methyl cyanoacetate and ethanol carry out the processing method (publication number CN101245034A) that esterification exchange process synthesizes ethyl cyanoacetate, and the people such as Douglas J.Raber report cyanoacetic acid and alkylating reagent [Et 3o] +bF 4 3+method (Journal of Organic Chemistry, 44 (7), 1149-54 of Reactive Synthesis ethyl cyanoacetate; 1979), there is not yet the report of the universal method about novel, environmental protection, the green a series of cyanoacetate compounds of preparation.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method preparing cyanoacetate compounds in acidic ion liquid, and the method has that environmental friendliness, selectivity and transformation efficiency are high, the simple feature of technique.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of method of synthesizing cyanoacetate, catalysis cyanoacetic acid and alcohol carry out esterification and obtain cyanoacetate, it is characterized in that: ionic liquid is as the reaction medium of esterification and catalyzer, described ionic liquid selects the wherein a kind of of following molecular structural formula, the glyoxaline ion liquid of molecular structural formula I-1, the pyrrolidinone compounds ionic liquid of molecular structural formula I-2 or the pyridine-sulfonic acid class ionic liquid of molecular structural formula I-3;
Wherein, R 1implication be H, or propyl sulfonic acid; The implication of X is HSO 4, or BF 4.
As preferably, described alcohol is C 1~ C 8the unitary saturated fatty alcohol of straight or branched, hexalin or benzylalcohol.
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;
Wherein R 2for C 1~ C 8straight or branched saturated alkyl in one.
As preferably, described esterification condition is: ionic liquid, cyanoacetic acid, alcohol are mixed into mol ratio for (0.1 ~ 5): 1: the mixture of (1 ~ 5), stirring reaction from the temperature of reaction of 40 ~ 100 degrees Celsius, react after 2 ~ 15 hours, isolate reaction system upper strata ester layer and just can; For not stratified reaction system, add a small amount of water and make ester layer layering, be separated and obtain ester.
Further improvement, described reaction system separates ionic liquid layer, and after water extracting and washing, heating decompression dehydration, de-organism, ionic liquid can be reused.
Finally, described ionic liquid, cyanoacetic acid, alcohol mix order in no particular order.
The present invention compares with reaction process with the traditional catalyst described in background technology, the invention has the advantages that:
1. operation and technique simply, do not need to add a large amount of alcohol;
2. the reaction times is short, and energy waste is low;
3. be separated easily, by toppling over or with water extraction, directly can obtaining esterification products;
4. ionic liquid is after simply dewatering, and can be recycled, and environmental pollution is little.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment further illustrates of the present invention below, is not limitation of the present invention.Ionic liquid Methylimidazole propanesulfonic acid used in embodiment-bisulfate ion negative ion [(CH 2) 3sO 3hmin] HSO 4, protonated methyl imidazoles-bisulfate ion negative ion [Hmin] HSO 4, protonated pyrrolidone acidic ion liquid [Hnmp] HSO 4, according to method preparation (Cole, the A.C. of open report; 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:
By 3.02g (10mmol) ionic liquid [(CH 2) 3sO 3hmin] HSO 4reaction flask is put into 4.339g (50mmol) cyanoacetic acid and 1.6g (50mmol) methyl alcohol, stir, heating, control temperature is 60 DEG C, reaction 4h, reaction solution leaves standstill, homogeneous phase, add a small amount of water and separate lower floor's esterification products methyl cyanoacetate by extraction separatory, obtaining productive rate through GC-MS qualitative and quantitative analysis is 80.36%.Ionic liquid layer, after water extracting and washing, heating decompression dehydration, organic matter removal, is reused.
Embodiment 2:
By 3.02g (10mmol) ionic liquid [(CH 2) 3sO 3hmin] HSO 4reaction flask is put into 4.339g (50mmol) cyanoacetic acid and 2.3g (50mmol) ethanol, stir, heating, control temperature is 80 DEG C, reaction 4h, reaction solution leaves standstill, layering, separate upper strata esterification products ethyl cyanoacetate by separatory, obtaining productive rate through GC-MS qualitative and quantitative analysis is 79.05%.Ionic liquid layer, through after water extracting and washing, heating decompression dehydration, organic matter removal, is reused.
Embodiment 3:
By 3.02g (10mmol) ionic liquid [(CH 2) 3sO 3hmin] HSO 4reaction flask is put into 4.339g (50mmol) cyanoacetic acid and 3g (50mmol) n-propyl alcohol, stir, heating, control temperature is 80 DEG C, reaction 4h, reaction solution leaves standstill, layering, separate upper strata esterification products cyanoacetic acid propyl ester by separatory, obtaining productive rate through GC-MS qualitative and quantitative analysis is 81.32%.Ionic liquid layer, through after water extracting and washing, heating decompression dehydration, organic matter removal, is reused.
Embodiment 4:
By 3.02g (10mmol) ionic liquid [(CH 2) 3sO 3hmin] HSO 4reaction flask is put into 4.339g (50mmol) cyanoacetic acid and 3g (50mmol) Virahol, stir, heating, control temperature is 80 DEG C, reaction 4h, reaction solution leaves standstill, layering, separate upper strata esterification products cyanoacetic acid isopropyl ester by separatory, obtaining productive rate through GC-MS qualitative and quantitative analysis is 82.09%.Ionic liquid layer, after water extracting and washing, heating decompression dehydration, organic matter removal, is reused.
Embodiment 5:
By 3.02g (10mmol) ionic liquid [(CH 2) 3sO 3hmin] HSO 4reaction flask is put into 4.339g (50mmol) cyanoacetic acid and 3.7g (50mmol) propyl carbinol, stir, heating, control temperature is 80 DEG C, reaction 4h, reaction solution leaves standstill, layering, separate upper strata esterification products n-butyl cyanoacetate by separatory, obtaining productive rate through GC-MS qualitative and quantitative analysis is 84.27%.Ionic liquid layer is after water extracting and washing, heating decompression dehydration, organic matter removal, and reuse 5 times, through GC-MS qualitative and quantitative analysis, productive rate is respectively 82.49%, and 80.09%, 78.69%, 78.38%.
Embodiment 6:
By 3.02g (10mmol) ionic liquid [(CH 2) 3sO 3hmin] HSO 4reaction flask is put into 4.339g (50mmol) cyanoacetic acid and 6.5g (50mmol) n-Octanol, stir, heating, control temperature is 80 DEG C, reaction 4h, reaction solution leaves standstill, layering, separate upper strata esterification products cyanoacetic acid monooctyl ester by separatory, obtaining productive rate through GC-MS qualitative and quantitative analysis is 84.94%.Ionic liquid layer, after water extracting and washing, heating decompression dehydration, organic matter removal, is reused.
Embodiment 7:
By 3.02g (10mmol) ionic liquid [(CH 2) 3sO 3hmin] HSO 4reaction flask is put into 4.339g (50mmol) cyanoacetic acid and 5g (50mmol) hexalin, stir, heating, control temperature is 80 DEG C, reaction 4h, reaction solution leaves standstill, layering, separate upper strata esterification products cyanoacetic acid cyclohexyl by separatory, obtaining productive rate through GC-MS qualitative and quantitative analysis is 79.66%.Ionic liquid layer, through after water extracting and washing, heating decompression dehydration, organic matter removal, is reused.
Embodiment 8:
By 3.02g (10mmol) ionic liquid [(CH 2) 3sO 3hmin] HSO 4reaction flask is put into 4.339g (50mmol) cyanoacetic acid and 5.4g (50mmol) phenylcarbinol, stir, heating, control temperature is 80 DEG C, reaction 4h, reaction solution leaves standstill, layering, separate upper strata esterification products cyanoacetic acid benzyl ester by separatory, obtaining productive rate through GC-MS qualitative and quantitative analysis is 72.79%.Ionic liquid layer, after water extracting and washing, heating decompression dehydration, organic matter removal, is reused.
Embodiment 9:
By 1.8g (10mmol) ionic liquid [Hmin] HSO 4reaction flask is put into 4.339g (50mmol) cyanoacetic acid and 2.3g (50mmol) ethanol, stir, heating, control temperature is 80 DEG C, reaction 4h, reaction solution leaves standstill, homogeneous phase, add a small amount of water and separate lower floor's esterification products ethyl cyanoacetate by extraction separatory, obtaining productive rate through GC-MS qualitative and quantitative analysis is 54.91%.Ionic liquid layer, after water extracting and washing, heating decompression dehydration, organic matter removal, is reused.
Embodiment 10:
By 1.97g (10mmol) ionic liquid [Hnmp] HSO 4reaction flask is put into 4.339g (50mmol) cyanoacetic acid and 2.3g (50mmol) ethanol, stir, heating, control temperature is 80 DEG C, reaction 4h, reaction solution leaves standstill, homogeneous phase, add a small amount of water and separate lower floor's esterification products ethyl cyanoacetate by extraction separatory, obtaining productive rate through GC-MS qualitative and quantitative analysis is 58.65%.Ionic liquid layer, after water extracting and washing, heating decompression dehydration, organic matter removal, is reused.

Claims (5)

1. one kind is synthesized the method for cyanoacetate, catalysis cyanoacetic acid and alcohol carry out esterification and obtain cyanoacetate, it is characterized in that: ionic liquid is as the reaction medium of esterification and catalyzer, described ionic liquid selects the wherein a kind of of following molecular structural formula, the glyoxaline ion liquid of molecular structural formula I-1;
Wherein, R 1implication be H, or propyl sulfonic acid; The implication of X is HSO 4, or BF 4
Described esterification condition is: ionic liquid, cyanoacetic acid, alcohol are mixed into mol ratio for (0.1 ~ 5): 1: the mixture of (1 ~ 5), stirring reaction from the temperature of reaction of 40 ~ 100 degrees Celsius, react after 2 ~ 15 hours, isolate reaction system upper strata ester layer and just can; For not stratified reaction system, add a small amount of water and make ester layer layering, be separated and obtain ester.
2. the method for synthesis cyanoacetate according to claim 1, is characterized in that described alcohol is C 1~ C 8the unitary saturated fatty alcohol of straight or branched, hexalin or benzylalcohol.
3. the method for synthesis 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;
Wherein R 2for C 1~ C 8straight or branched saturated alkyl in one.
4. the method for synthesis cyanoacetate according to claim 1, is characterized in that described reaction system separates ionic liquid layer, and after water extracting and washing, heating decompression dehydration, de-organism, ionic liquid can be reused.
5. the method for synthesis cyanoacetate according to claim 4, is characterized in that described ionic liquid, cyanoacetic acid, alcohol mix order in no particular order.
CN201110132794.3A 2011-05-19 2011-05-19 A kind of method of synthesizing cyanoacetate Expired - Fee Related CN102786436B (en)

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CN109467519A (en) * 2017-09-07 2019-03-15 汪忠华 A kind of preparation method of malonic acid single pair p-Nitrobenzyl
CN112645843B (en) * 2020-12-25 2022-05-20 复旦大学 Synthesis method of tert-butyl cyanoacetate
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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CN101137437A (en) * 2005-01-04 2008-03-05 贝尔法斯特女王大学 Basic ionic liquids
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