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Preparation method of cyanomethyl ester

A technology of cyanomethyl ester and cyanoacetic acid, applied in the field of preparing cyanomethyl ester, can solve the problems of low atom economy, environmental pollution, low system universality, etc. Wide range of effects

Inactive Publication Date: 2016-02-03
SUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] Under the action of triethylamine, cyanomethyl ester compounds can be constructed in one step through nucleophilic substitution reactions between chloroacetonitrile and carboxylic acid compounds (HelmutM.Hugel, K.VijavaBhashai, RobertW.Longmore, Synthetic Communication, 1992, 22, 693-697); but The system produces equivalent halides, which has serious environmental pollution
Under the action of electron reducing agent, cyanomethyl ester compound can be constructed by using benzoyl nitrile (Mitsuhiro Okimoto, Toshiaki Itoh, Toshiro Chiba, J.Org.Chem., 1996, 61, 4835-4837); this system cannot generate cyanide alone Methyl compounds, often accompanied by by-products of 1,2-diketones, the atom economy of the reaction is not high
Under the condition of Lewis base, benzoylnitrile and cyclohexanone can construct cyanohydrin compounds (WenZhang, MinShi, Org. Biomol. Chem., 2006, 4, 1671-1674); this system can only construct cyclic cyanohydrin compounds, the universality of the system is not high

Method used

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  • Preparation method of cyanomethyl ester
  • Preparation method of cyanomethyl ester
  • Preparation method of cyanomethyl ester

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026]

[0027] The reaction bottle was loaded with TBAI (0.3mmol, 111mg) sequentially, and the compound 1a (2mmol, 247mg), compound 2 (4mmol, 341mg), NaOAc (4mmol, 164mg), TBHP (0.6mL), water (4.0mL), tetrahydrofuran (4.0mL). Then the system was heated in the air at 80°C for about 12 hours, quenched with saturated sodium sulfite solution, extracted with ethyl acetate (40mL×3), adsorbed on silica gel, and the product was obtained by simple column chromatography 3a , the yield is 78%. The main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.

[0028] 1 HNMR (400MHz, CDCl 3 )δ8.07–8.04(m,2H),7.65–7.61(m,1H),7.50–7.46(m,2H),4.96(s,2H); 13 CNMR (100MHz, CDCl 3 )δ164.9, 134.1, 129.9, 128.6, 127.8, 114.4, 48.8; MS (ESI-quadrupole): Anal.Calcd.ForC 9 h 7 NO 2 +H + :162,Found:162(M+H + );IR(neat,cm -1 ):υ2957, 2918, 2240, 1729, 1494, 1252.

Embodiment 2

[0030]

[0031] The reaction bottle was loaded with TBAI (0.3mmol, 111mg) sequentially, and the compound 1a (2mmol, 247mg), compound 2 (4mmol, 341mg), NaOAc (4mmol, 164mg), TBHP (0.6mL), water (4.0mL), tetrahydrofuran (4.0mL). Then the system was heated at 90°C in the air for about 12 hours, quenched with saturated sodium sulfite solution, extracted with ethyl acetate (40mL×3), adsorbed on silica gel, and the product was obtained by simple column chromatography 3a , the yield is 77%. The main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.

[0032] 1 HNMR (400MHz, CDCl 3 )δ8.07–8.04(m,2H),7.65–7.61(m,1H),7.50–7.46(m,2H),4.96(s,2H); 13 CNMR (100MHz, CDCl 3 )δ164.9, 134.1, 129.9, 128.6, 127.8, 114.4, 48.8; MS (ESI-quadrupole): Anal.Calcd.ForC 9 h 7 NO 2 +H + :162,Found:162(M+H + );IR(neat,cm -1 ):υ2957, 2918, 2240, 1729, 1494, 1252.

Embodiment 3

[0034]

[0035] The reaction bottle was loaded with TBAI (0.3mmol, 111mg) sequentially, and the compound 1a (2mmol, 247mg), compound 2(4mmol, 341mg), NaOAc (4mmol, 164mg), TBHP (0.6mL), water (4.0mL), tetrahydrofuran (4.0mL). Then the system was heated in the air at 100°C for about 12 hours, quenched with saturated sodium sulfite solution, extracted with ethyl acetate (40mL×3), adsorbed on silica gel, and the product was obtained by simple column chromatography 3a , the yield is 74%. The main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.

[0036] 1 HNMR (400MHz, CDCl 3 )δ8.07–8.04(m,2H),7.65–7.61(m,1H),7.50–7.46(m,2H),4.96(s,2H); 13 CNMR (100MHz, CDCl 3 )δ164.9, 134.1, 129.9, 128.6, 127.8, 114.4, 48.8; MS (ESI-quadrupole): Anal.Calcd.ForC 9 h 7 NO 2 +H + :162,Found:162(M+H + );IR(neat,cm -1 ):υ2957, 2918, 2240, 1729, 1494, 1252.

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Abstract

The invention discloses a preparation method of cyanomethyl ester. In the presence of an oxidizing agent, a carboxylic acid compound and cyanoacetic acid are used as reactants, iodide is used as a catalyst, and sodium acetate is used as alkali, so as to prepare the cyanomethyl ester in a mixed solvent through nucleophilic substitution. According to the method, the reactivity of the catalyst is high, reaction conditions are mild, the application range of substrates is wide, the postprocessing is convenient, the yield of target products is high, a preparation process is simple, green and environmentally friendly, and the sources of used raw material are wide.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a method for preparing cyanomethyl esters. Background technique [0002] The cyanation of carboxylic acid to prepare cyanomethyl ester has a very important application in organic synthetic chemistry, because cyanomethyl ester is a common drug structural unit, which is widely used in biology, medicine, pesticide, food, etc. . Cyanomethyl esters can be converted into many useful functional groups such as α-hydroxy acids, β-amino alcohols, α-hydroxy esters, α-sulfonyl nitriles, α-aminonitriles, α-fluorinated nitriles, 3-amino- 2-alkenoic acids and various substituted azacycloalkenes. [0003] Under the action of triethylamine, cyanomethyl ester compounds can be constructed in one step through nucleophilic substitution reactions between chloroacetonitrile and carboxylic acid compounds (HelmutM.Hugel, K.VijavaBhashai, RobertW.Longmore, Synthetic Communication, ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C255/16C07C255/57C07C253/30C07D333/38C07D231/56
Inventor 陆新华万小兵王宏祥张杰
Owner SUZHOU UNIV
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