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A kind of synthetic method of methylene malononitrile compound

A technology of methylene malononitrile and synthesis method, which is applied in the preparation of organic compounds, chemical instruments and methods, organic chemistry, etc., and can solve problems such as polluted environment and a large amount of alkaline wastewater

Active Publication Date: 2020-11-13
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The synthetic method of traditional aryl methylene malononitrile compounds is formed by condensation and dehydration of aldehyde and malononitrile under alkaline conditions. The disadvantage of this method is to use an equivalent amount of alkali, and the reaction Post-treatment produces a large amount of alkaline wastewater, seriously polluting the environment

Method used

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  • A kind of synthetic method of methylene malononitrile compound
  • A kind of synthetic method of methylene malononitrile compound
  • A kind of synthetic method of methylene malononitrile compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0034] Embodiment 1: the preparation of methylene malononitrile compound (III-1)

[0035] The reaction formula is as follows:

[0036]

[0037] Add 4.908g (50mmol) of cyclohexanone (I-1), 0.5g (Ru molar weight is (I-1) 5‰) Ru / C catalyst, 3.303g (50mmol) of malononitrile II in the reaction flask With 100mL ethanol, stirred and reacted at 78°C for 12h, GC-MS detected that the reaction of raw materials was complete, and the reaction was stopped. The reaction solution is filtered once to obtain a filtrate and a filter cake. After washing the filter cake once with 5mL ethanol, filter it twice to obtain a second filter cake and a second filtrate. The second filter cake is the Ru / C catalyst, which can be used In the next batch of reactions; the first filtrate and the second filtrate were combined to recover ethanol (which can be used in the next batch of reactions) by a rotary evaporator to simultaneously obtain 7.163 g of liquid products, with a yield of 98.0% and a GC-MS purity...

Embodiment 2

[0039] Embodiment 2: the preparation of methylene malononitrile compound (III-2)

[0040] The reaction formula is as follows:

[0041]

[0042] Add 7.713g (50mmol) of p-tert-butylcyclohexanone (I-2), 0.5g (Ru molar weight is (I-2) 5‰) Ru / C catalyst, 3.303g (50mmol) of propylene glycol in the reaction flask Nitrile II and 80mL ethanol were reacted with stirring at 78°C for 14h, and the following operations were the same as in Example 1. Finally, 9.892 g of liquid product was obtained, the yield was 97.8%, and the GC-MS purity was 99.0%. The structural representation of compound formula (III-2) is as follows:

[0043] 1 H NMR (CDCl 3 ,600MHz)δ3.11-3.07(m,2H),2.33-2.27(m,2H),2.15-2.11(m,2H),1.37-1.34(m,1H),1.31-1.24(m,2H), 0.89(s,9H); 13 C NMR (CDCl 3,150MHz)δ185.1,111.7,82.3,46.9,34.7,32.5,28.8,27.5; GC-MS(EI):m / z 202[M + ].

Embodiment 3

[0044] Embodiment 3: the preparation of methylene malononitrile compound (III-3)

[0045] The reaction formula is as follows:

[0046]

[0047] In the reaction flask, add 2.905g (50mmol) of acetone (I-3), 0.5g (Ru molar weight is (I-3) 5‰) Ru / C catalyst, 3.303g (50mmol) of malononitrile II and 80mL Ethanol, stirred and reacted at 56°C for 24h, the following operations were the same as in Example 1. Finally, 4.723 g of liquid product was obtained, with a yield of 89.0% and a GC-MS purity of 98.0%. The structural representation of compound formula (III-3) is as follows:

[0048] 1 H NMR (CDCl 3 ,600MHz)δ2.32(s,6H); 13 C NMR (CDCI 3 ,150MHz)δ178.6,111.8,86.3,24.6; GC-MS(EI):m / z 106[M] +

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Abstract

The invention discloses a synthesis method of methylene malononitrile compounds. According to the method, in the air atmosphere, a ketone compound and malononitrile are taken as raw materials, Ru / C istaken as a catalyst, the raw materials and the catalyst are subjected to a reaction in ethanol at 25-78 DEG C, after the complete reaction, a reaction solution is separated and purified, and the methylene malononitrile compounds are obtained. The Ru / C catalyst used in the method is cheap and easily available, the catalyst and a solvent are quite convenient to recover and can be repeatedly used due to the fact that the catalyst is in a heterogeneous catalysis system in the reaction; the reaction raw materials are diversified, cheap and easily available, thereby being suitable for synthesis ofvarious substituted ene nitrile compounds; aftertreatment is simple, and product purity and yield are high.

Description

[0001] (1) Technical field [0002] The invention relates to a method for synthesizing methylene malononitrile compounds. [0003] (2) Background technology [0004] Malononitrile compounds are rich in variety and have good chemical and biological activities, and are used in pesticides, medicines, dyes, polyurethane stabilizers, etc. Methylene malononitriles, as their derivatives, are a class of prodrugs with potential biological activity, and they are also important intermediates for the synthesis of various heterocyclic compounds. Methylene malononitrile compounds are an important class of bulk chemical intermediates, and many compounds can be prepared from them, which are widely used in chemical industry, materials, medicine, pesticides and other industries. For example, in 2007, Bauer J.D. reported that cyclooxygenase inhibitors could be synthesized using methylene malononitrile compounds as raw materials (Med Chem Res, 2007, 16, 119-129.). The synthetic method of traditi...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C253/30C07C255/31C07C255/34C07C255/37C07C255/09
CPCC07C253/30C07C255/31C07C255/34C07C255/37C07C255/09
Inventor 王宇光胡芬张程
Owner ZHEJIANG UNIV OF TECH