(1Z,3E)-1-methylthio-4-pyrrolidinyl-3-nitro-1,3-butadiene | 193144-29-5

• 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: (1Z,3E)-1-methylthio-4-pyrrolidinyl-3-nitro-1,3-butadiene
• 英文别名: (1E,3Z)-4-methylthio-2-nitro-1-pyrrolidino-1,3-butadiene；1-[(1E,3Z)-4-methylsulfanyl-2-nitrobuta-1,3-dienyl]pyrrolidine
• CAS: 193144-29-5
• 化学式: C₉H₁₄N₂O₂S
• 分子量: 214.288
• InChiKey: XQMVNSJMUKTHSZ-NKUJDFQBSA-N

物化性质

• 沸点：
  306.4±42.0 °C(Predicted)
• 密度：
  1.269±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  74.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1Z,3E)-1-methylthio-4-pyrrolidinyl-3-nitro-1,3-butadiene 在 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 (1E,3Z)-2-(4-methanesulfonyl-2-nitrobuta-1,3-dien-1-yl)thiophene
  参考文献：
  名称：

  从β-硝基噻吩到稠合的硝基苯：通过简便，芳香化驱动，热6π电环化的整个环扩大过程1

  摘要：

  在对先前关于1-芳基-4-甲磺酰基-2-硝基-3-苯基磺酰基-1,3-丁二烯的热环化的研究中（7），由3的初始开环衍生而来的3-未取代的衍生物8 -硝基噻吩（2），在本文中同样被发现在类似温和的实验条件下进行环化，然后进行芳构化，导致环稠合的均-或杂芳族硝基衍生物10。基于溶剂极性或8芳基上电子密度变化的测试结果强烈支持了该方法的协调一致的电环性质。因此，该方法成功地应用于非苯磺酰基活化的图8显着拓宽了由硝基噻吩合成的有价值的总的开环/闭环方法的范围。此外，提供了对最近对热6π电环化的新兴趣的支持，所述热6π电环化是用于构建苯环的工具。

  DOI：

  10.1021/jo051059x
• 作为产物：
  描述：

  四氢吡咯 、 3-硝基噻吩 、 碘甲烷 在 silver nitrate 作用下， 以 乙醇 为溶剂， 反应 2.0h， 生成 (1Z,3E)-1-methylthio-4-pyrrolidinyl-3-nitro-1,3-butadiene
  参考文献：
  名称：

  A new route to thiopyran S,S-dioxide derivatives via an overall ring-enlargement protocol from 3-nitrothiophene

  摘要：

  从 3-硝基噻吩（5）的初始开环反应中得到的（1E,3Z)-1-芳基-4-甲磺酰基-2-硝基-1,3-丁二烯（8），已被发现会在碱性条件下发生简便的环化反应，生成噻二吡喃S,S-二氧化物（9），从而为由5元硫杂环扩大为6元硫杂环提供了一个有效的范例。化合物9以单一外消旋混合物的形式获得，且收率满意：它们仍然含有一个硝基乙烯基部分，可进一步进行修饰以制备具有合成或药理学潜力的新衍生物，如在L型钙离子通道阻滞剂领域中的应用。© 2008 Elsevier Ltd. 保留所有权利。

  DOI：

  10.1016/j.tet.2008.10.046

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.
• 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.
• Synthesis and characterization of 1-amino-4-methylthio-2-nitro-1,3-butadienes
  作者：Sheetal S. Surange、Govindaraj Kumaran、Srinivasachari Rajappa、K. Rajalakshmi、Vasantha Pattabhi

  DOI：10.1016/s0040-4020(97)00511-5

  日期：1997.6

  Treatment of 3-nitrothiophene with prim. and sec. amines, followed by S-methylation leads to (Z,Z)-1- amino-4-methylthio-2-nitro-1,3-butadienes (3). Oxidation of these with LTA yields a mixture of the 2-methylthio-4-nitropyrroles (6) and the acetoxylated butadienes (8). (C) 1997 Elsevier Science Ltd.
• From β-Nitrothiophenes to Ring-Fused Nitrobenzenes:  An Overall Ring-Enlargement Process via a Facile, Aromatization-Driven, Thermal 6π Electrocyclization¹
  作者：Lara Bianchi、Carlo Dell'Erba、Massimo Maccagno、Giovanni Petrillo、Egon Rizzato、Fernando Sancassan、Elda Severi、Cinzia Tavani

  DOI：10.1021/jo051059x

  日期：2005.10.1

  the 3-unsubstituted derivatives 8, deriving from the initial ring opening of 3-nitrothiophene (2), have been likewise found herein to undergo cyclization, followed by aromatization, in analogous mild experimental conditions, leading to the ring-fused homo- or heteroaromatic nitro derivatives 10. The concerted electrocyclic nature of the process is strongly supported by the outcome of tests based on

  在对先前关于1-芳基-4-甲磺酰基-2-硝基-3-苯基磺酰基-1,3-丁二烯的热环化的研究中（7），由3的初始开环衍生而来的3-未取代的衍生物8 -硝基噻吩（2），在本文中同样被发现在类似温和的实验条件下进行环化，然后进行芳构化，导致环稠合的均-或杂芳族硝基衍生物10。基于溶剂极性或8芳基上电子密度变化的测试结果强烈支持了该方法的协调一致的电环性质。因此，该方法成功地应用于非苯磺酰基活化的图8显着拓宽了由硝基噻吩合成的有价值的总的开环/闭环方法的范围。此外，提供了对最近对热6π电环化的新兴趣的支持，所述热6π电环化是用于构建苯环的工具。
• A new route to thiopyran S,S-dioxide derivatives via an overall ring-enlargement protocol from 3-nitrothiophene
  作者：Lara Bianchi、Massimo Maccagno、Giovanni Petrillo、Egon Rizzato、Fernando Sancassan、Elda Severi、Domenico Spinelli、Marco Stenta、Andrea Galatini、Cinzia Tavani

  DOI：10.1016/j.tet.2008.10.046

  日期：2009.1

  (1E,3Z)-1-Aryl-4-methanesulfonyl-2-nitro-1,3-butadienes (8), derived from the initial ring-opening of 3-nitrothiophene (5), have been found to undergo a facile base-induced cyclization leading to thiopyran S,S-dioxides (9), thus furnishing a further example of effective ring-enlargement from 5- to 6-membered sulfur heterocycles. Compounds 9 are obtained as single racemic mixtures in satisfactory yields: they still contain a nitrovinylic moiety, which can be exploited for further modifications targeted to new derivatives endowed with either synthetic or pharmacological potentialities e.g., in the field of L-type Ca2+-channel blockers. (C) 2008 Elsevier Ltd. All rights reserved.

  从 3-硝基噻吩（5）的初始开环反应中得到的（1E,3Z)-1-芳基-4-甲磺酰基-2-硝基-1,3-丁二烯（8），已被发现会在碱性条件下发生简便的环化反应，生成噻二吡喃S,S-二氧化物（9），从而为由5元硫杂环扩大为6元硫杂环提供了一个有效的范例。化合物9以单一外消旋混合物的形式获得，且收率满意：它们仍然含有一个硝基乙烯基部分，可进一步进行修饰以制备具有合成或药理学潜力的新衍生物，如在L型钙离子通道阻滞剂领域中的应用。© 2008 Elsevier Ltd. 保留所有权利。