malononitril | 64512-18-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: malononitril
• 英文别名: 2-[di(pyrrolidin-1-yl)methylene]malononitrile；(di-pyrrolidin-1-yl-methylene)-malononitrile；2-(Dipyrrolidin-1-ylmethylidene)propanedinitrile
• CAS: 64512-18-1
• 化学式: C₁₂H₁₆N₄
• 分子量: 216.286
• InChiKey: YOYNBNHDTGKMKI-UHFFFAOYSA-N

物化性质

• 沸点：
  323.3±42.0 °C(Predicted)
• 密度：
  1.206±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  54.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3,4-二氯-3-环丁烯-1,2-二酮 、 malononitril 反应 8.0h， 以43%的产率得到N-(2-Chloro-3,4-dioxo-cyclobut-1-enyl)-2-cyano-3,3-di-pyrrolidin-1-yl-acrylimidoyl chloride
  参考文献：
  名称：

  Eine einfache Synthese von Carbamimidoyl-halogeniden (Haloformamidinen) und von (dazu vinylogen) 2-Cyano-3,3-diaminopropenimidoyl-halogeniden

  摘要：

  DOI：

  10.1055/s-1980-29140
• 作为产物：
  描述：

  四氢吡咯 、 3-bromoisothiazole-4,5-dicarbonitrile 反应 0.08h， 以85%的产率得到malononitril
  参考文献：
  名称：

  Reactions of selected 3-bromoisothiazole-5-carbonitriles with the secondary dialkylamines pyrrolidine and morpholine

  摘要：

  Readily available 3-bromoisothiazole-5-carbonitriles bearing various C-4 substituents [H, CO2R C N and halogen (CI or Br)], react with either pyrrolidine or morpholine to give, in most cases, the 3-amino-substituted derivatives in high yields. The reaction of 3-bromoisothiazole-4,5-dicarbonitrile, however, varied with the nucleophilicity of the dialkylamine: pyrrolidine led to cleavage of the isothiazole ring to give 2-[di(pyrrolidin-1-yl)methylene]malononitrile while morpholine led to the expected 3-(morpholin-4-yl)isothiazole-4,5-dicarbonitrile. By comparison, 3-chloroisothiazole-4,5-dicarbonitrile reacted with pyrrolidine to give surprisingly, 3-chloro-5-(pyrrolidin-1-yl)isothiazole-4-carbonitrile as the major product, while with morpholine the major product was the expected 3-(morpholin-4-yl)isothiazole-4,5-dicarbonitrile. The mechanisms of the transformations are discussed, together with rationalization for the formation of side products. Furthermore, the hydrolytic decarboxylation of methyl and ethyl esters of 3-dialkylaminoisothiazoles using both conventional heating and microwave irradiation is reported. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2014.06.012

文献信息

• Eine einfache Synthese von Carbamimidoyl-halogeniden (Haloformamidinen) und von (dazu vinylogen) 2-Cyano-3,3-diaminopropenimidoyl-halogeniden
  作者：Walter Ried、Hans Dietschmann、Hanns-Eberhard Erle

  DOI：10.1055/s-1980-29140

  日期：——
• Ried, Walter; Schoepke, Klaus, Liebigs Annalen der Chemie, 1986, # 2, p. 389 - 394
  作者：Ried, Walter、Schoepke, Klaus

  DOI：——

  日期：——
• RIED, W.;SCHOEPKE, K., LIEBIGS ANN. CHEM., 1986, N 2, 389-394
  作者：RIED, W.、SCHOEPKE, K.

  DOI：——

  日期：——
• Ried, Walter; Dietschmann, Hans, Liebigs Annalen der Chemie, 1981, # 6, p. 1009 - 1014
  作者：Ried, Walter、Dietschmann, Hans

  DOI：——

  日期：——
• Reactions of selected 3-bromoisothiazole-5-carbonitriles with the secondary dialkylamines pyrrolidine and morpholine
  作者：Andreas S. Kalogirou、Panayiotis A. Koutentis

  DOI：10.1016/j.tet.2014.06.012

  日期：2014.10

  Readily available 3-bromoisothiazole-5-carbonitriles bearing various C-4 substituents [H, CO2R C N and halogen (CI or Br)], react with either pyrrolidine or morpholine to give, in most cases, the 3-amino-substituted derivatives in high yields. The reaction of 3-bromoisothiazole-4,5-dicarbonitrile, however, varied with the nucleophilicity of the dialkylamine: pyrrolidine led to cleavage of the isothiazole ring to give 2-[di(pyrrolidin-1-yl)methylene]malononitrile while morpholine led to the expected 3-(morpholin-4-yl)isothiazole-4,5-dicarbonitrile. By comparison, 3-chloroisothiazole-4,5-dicarbonitrile reacted with pyrrolidine to give surprisingly, 3-chloro-5-(pyrrolidin-1-yl)isothiazole-4-carbonitrile as the major product, while with morpholine the major product was the expected 3-(morpholin-4-yl)isothiazole-4,5-dicarbonitrile. The mechanisms of the transformations are discussed, together with rationalization for the formation of side products. Furthermore, the hydrolytic decarboxylation of methyl and ethyl esters of 3-dialkylaminoisothiazoles using both conventional heating and microwave irradiation is reported. (C) 2014 Elsevier Ltd. All rights reserved.