(1E)-4,4-bis(methylthio)-2-nitro-1-pyrrolidino-1,3-butadiene | 389838-05-5

• 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: (1E)-4,4-bis(methylthio)-2-nitro-1-pyrrolidino-1,3-butadiene
• 英文别名: (E)-1,1-di(methylthio)-4-pyrrolidinyl-3-nitro-1,3-butadiene；(E)-1,1-bis(methylthio)-3-nitro-4-pyrrolidino-1,3-butadiene；1-[(1E)-4,4-bis(methylsulfanyl)-2-nitrobuta-1,3-dienyl]pyrrolidine
• CAS: 389838-05-5
• 化学式: C₁₀H₁₆N₂O₂S₂
• 分子量: 260.381
• InChiKey: KEUAJMMOFMWTKT-CMDGGOBGSA-N

物化性质

• 沸点：
  333.3±42.0 °C(Predicted)
• 密度：
  1.307±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  99.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (1E)-4,4-bis(methylthio)-2-nitro-1-pyrrolidino-1,3-butadiene 在 lead 作用下， 以 四氢呋喃 、 溶剂黄146 、 N,N-二甲基甲酰胺 为溶剂， 生成 4-(3-chlorophenyl)-3-hydroxyimino-1,1-bis(methylthio)-1-butene
  参考文献：
  名称：

  Access to 3-arylmethyl-5-(methylthio)isoxazoles via an initial ring-opening of 2-methylthio-4-nitrothiophene

  摘要：

  The reactions of 1, 1 -bis(methylthio)-3-nitro-4-pyrrolidino-1.3-butadiene (deriving from the initial ring-opening of 2-methylthio-4-nitrothiophene with pyrrolidine and silver nitrate in EtOH) with arylmagnesium bromides result in the chemoselective replacement of the pyrrolidino group with the aryl moiety of the Grignards. The 4-aryl-1,1-bis(methylthio)-3-nitro-1,3-butadienes thus obtained are the key intermediates for the effective synthesis, through the corresponding reduction products 4-aryl-3-hydroximino-1, 1-bis(methylthio)-1-butenes, of the previously unknown 3-arylmethyl-5-(methylthio)isoxazoles. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(02)00292-2
• 作为产物：
  描述：

  四氢吡咯 、 2-methylthio-4-nitrothiophene 、 碘甲烷 在 silver nitrate 作用下， 以 乙醇 为溶剂， 反应 2.0h， 以52%的产率得到(1E)-4,4-bis(methylthio)-2-nitro-1-pyrrolidino-1,3-butadiene
  参考文献：
  名称：

  Ring opening of 2-substituted 4-nitrothiophenes with pyrrolidine. Access to new functionalized nitro-unsaturated building blocks

  摘要：

  The reaction conditions of the ring-opening processes of 3-nitrothiophene 7a and of 3-nitrobenzo[b]thiophene 7b with pyrrolidine and silver nitrate were optimized as well as those of the subsequent S-methylation of the ensuing silver enethiolates 8a and 8b to 4-methylthio-2-nitro-1-pyrrolidino-1,3-butadiene 9a and 1-(2-methylthiophenyl)-1-nitro-2-pyrrolidinoethylene 9b. Under such conditions 2-X-substituted 4-nitrothiophenes 7c-i consistently gave good yields of the corresponding 4-methylthio-2-nitro-1-pyrrolidino-4-X-1,3-butadienes 9c-i. The nitroenamine derivatives 9a-i were then reacted with p-tolylmagnesium bromide to furnish moderate to good yields of 4-methylthio-2-nitro-1-(p-tolyl)-4-X-1,3-butadienes 10a,c-i and 1-(2-methylthiophenyl)-1-nitro-2-(p-tolyl)ethylene 10b. Stereochemistry of the interesting building blocks 9a-i and 10a-i was assigned on the grounds of H-1 NMR data and NOE experiments. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(01)00765-7

文献信息

• Nitroalkylation and nitroalkenylation reactions of γ-lactone enolates. A facile ring switch from polysubstituted γ-lactones to polysubstituted γ-lactams
  作者：C. Forzato、P. Nitti、G. Pitacco、E. Valentin、S. Morganti、E. Rizzato、D. Spinelli、C. Dell'Erba、G. Petrillo、C. Tavani

  DOI：10.1016/j.tet.2004.07.084

  日期：2004.11

  Michael addition of lithium enolates of gamma-butyrolactone 1 and alpha-methyl-gamma-butyrolactone 1' to (E)-1-nitropropene 2, (E)-beta-nitrostyrene 3 and (E)-2-vitro-1-phenylpropene 4 is described. Reactions of the lithium enolate of 1' with 2 and 4 occurred with high diasteroselectivity (80 and 92% d.e., respectively). Reactions of the zinc enolate of 1' with two beta-nitroenamines and two methylthiosubstituted 1-amino-2-vitro-1,3-dienes were also examined. Catalytic reduction of the nitroalkylated and nitroalkenylated products allowed the achievement of functionalized gamma-lactams and/or cyclic hydroxamic acids. (C) 2004 Elsevier Ltd. All rights reserved.
• Access to 3-arylmethyl-5-(methylthio)isoxazoles via an initial ring-opening of 2-methylthio-4-nitrothiophene
  作者：Lara Bianchi、Carlo Dell'Erba、Antonella Gabellini、Marino Novi、Giovanni Petrillo、Cinzia Tavani

  DOI：10.1016/s0040-4020(02)00292-2

  日期：2002.4

  The reactions of 1, 1 -bis(methylthio)-3-nitro-4-pyrrolidino-1.3-butadiene (deriving from the initial ring-opening of 2-methylthio-4-nitrothiophene with pyrrolidine and silver nitrate in EtOH) with arylmagnesium bromides result in the chemoselective replacement of the pyrrolidino group with the aryl moiety of the Grignards. The 4-aryl-1,1-bis(methylthio)-3-nitro-1,3-butadienes thus obtained are the key intermediates for the effective synthesis, through the corresponding reduction products 4-aryl-3-hydroximino-1, 1-bis(methylthio)-1-butenes, of the previously unknown 3-arylmethyl-5-(methylthio)isoxazoles. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Ring opening of 2-substituted 4-nitrothiophenes with pyrrolidine. Access to new functionalized nitro-unsaturated building blocks
  作者：Carlo Dell'Erba、Antonella Gabellini、Marino Novi、Giovanni Petrillo、Cinzia Tavani、Barbara Cosimelli、Domenico Spinelli

  DOI：10.1016/s0040-4020(01)00765-7

  日期：2001.9

  The reaction conditions of the ring-opening processes of 3-nitrothiophene 7a and of 3-nitrobenzo[b]thiophene 7b with pyrrolidine and silver nitrate were optimized as well as those of the subsequent S-methylation of the ensuing silver enethiolates 8a and 8b to 4-methylthio-2-nitro-1-pyrrolidino-1,3-butadiene 9a and 1-(2-methylthiophenyl)-1-nitro-2-pyrrolidinoethylene 9b. Under such conditions 2-X-substituted 4-nitrothiophenes 7c-i consistently gave good yields of the corresponding 4-methylthio-2-nitro-1-pyrrolidino-4-X-1,3-butadienes 9c-i. The nitroenamine derivatives 9a-i were then reacted with p-tolylmagnesium bromide to furnish moderate to good yields of 4-methylthio-2-nitro-1-(p-tolyl)-4-X-1,3-butadienes 10a,c-i and 1-(2-methylthiophenyl)-1-nitro-2-(p-tolyl)ethylene 10b. Stereochemistry of the interesting building blocks 9a-i and 10a-i was assigned on the grounds of H-1 NMR data and NOE experiments. (C) 2001 Elsevier Science Ltd. All rights reserved.