methyl 2-(1-(thiophen-2-yl)ethylidene)hydrazine-1-carboxylate | 303148-60-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: methyl 2-(1-(thiophen-2-yl)ethylidene)hydrazine-1-carboxylate
• 英文别名: N'-[1-(thiophen-2-yl)ethylidene]methoxycarbohydrazide；methyl N-(1-thiophen-2-ylethylideneamino)carbamate
• CAS: 303148-60-9
• 化学式: C₈H₁₀N₂O₂S
• 分子量: 198.246
• InChiKey: SASRIILNMYDXHF-UHFFFAOYSA-N

物化性质

• 熔点：
  150-152°C

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  78.9
• 氢给体数：
  1
• 氢受体数：
  4

安全信息

• 危险等级：
  IRRITANT

反应信息

• 作为反应物：
  描述：

  methyl 2-(1-(thiophen-2-yl)ethylidene)hydrazine-1-carboxylate 在 potassium hydroxide 作用下， 以 三乙二醇 为溶剂， 反应 4.0h， 生成 2-乙基噻吩
  参考文献：
  名称：

  肼基羧酸甲酯作为 Wolff-Kishner 反应中肼的实用替代品

  摘要：

  在这里，我们描述了一个简单的协议，用于将芳香酮和醛还原为相应的亚甲基单元。该过程涉及分离碳甲氧基腙中间体，该中间体很容易分解为还原产物，而不需要大量有害的肼。

  DOI：

  10.1055/s-0035-1560805

文献信息

• Synthesis and Crystal Structure Determination of Methyl 2-acetyl-5′-phenyl-2H-spiro[benzo[d]isothiazole-3,3′-pyrazole]-1,1-dioxide-2′(4′H)-carboxylate and Methyl 2-acetyl-5′-(2-thienyl)-2H-spiro[benzo[d]isothiazole-3,3′-pyrazole]-1,1-dioxide-2′(4′H)-carboxylate
  作者：Clyde R. Metz、John D. Knight、Anna C. Dawsey、William T. Pennington、Donald G. VanDerveer、Jordan B. Brown、Kevin J. Bigham、Charles F. Beam

  DOI：10.1007/s10870-009-9649-2

  日期：2010.4

  Dilithiated C(α), N-carbomethoxyhydrazones were condensed with lithiated methyl 2-(aminosulfonyl)benzoate to afford intermediates that were isolated and not characterized but cyclized with acetic anhydride, which also resulted in N-acetylation. The X-ray crystal structure determinations of methyl 2-acetyl-5′-phenyl-2H-spiro[benzo[d]isothiazole-3,3′-pyrazole]-1,1-dioxide-2′(4′H)-carboxylate and methyl 2-acetyl-5′-(2-thienyl)-2H-spiro[benzo[d]isothiazole-3,3′-pyrazole]-1,1-dioxide-2′(4′H)-carboxylate products were a follow up for absorption spectra, and they confirmed their structures. Mechanistic intermediates to describe the reaction may include C-acylated intermediates that cyclize to spiro(N-benzoisothiazole dioxide-pyrazole) instead of N-carbomethoxypyrazole-ortho-benzenesulfonamides. Crystals of C19H17N3O5S 7 are monoclinic, P21/c, a = 11.899(2) Å, b = 17.562(4) Å, c = 9.484(2) Å, β = 111.03(3)°, Z = 4, V = 1849.9(6) Å3, R 1 = 0.0857 and wR 2 = 0.2216 for reflections with I > 2σ(I); crystals of C17H15N3O5S2 8 are orthorhombic, Pbca, a = 16.045(3) Å, b = 10.746(2) Å, c = 20.389(4) Å, Z = 8, V = 3516(1) Å3, R 1 = 0.0841 and wR 2 = 0.2179 for all reflections with I > 2σ(I). X-ray crystal analysis was important for determining the conformation of the structure of N-acetyl-N′-carbomethoxy-spiro(benzoisothiazole–pyrazole)dioxides prepared by the condensation and twofold cyclization of dilithiated C(α), N-carbomethoxyhydrazones and methyl 2-(aminosulfonyl)benzoate.

  二锂化的C(α), N-羧甲基酰肼与甲基2-(氨基磺酰基)苯甲酸锂反应生成中间体，这些中间体被分离出来但未进行表征，但在乙酸酐的作用下环化，并导致N-乙酰化。甲基2-乙酰基-5′-苯基-2H-螺[苯并[d]异噻唑-3,3′-吡唑]-1,1-二氧化物-2′(4′H)-羧酸酯和甲基2-乙酰基-5′-(2-噻吩基)-2H-螺[苯并[d]异噻唑-3,3′-吡唑]-1,1-二氧化物-2′(4′H)-羧酸酯的X射线晶体结构测定是对吸收光谱的后续研究，并确认了它们的结构。描述反应的机制中间体可能包括环化为螺(N-苯并异噻唑二氧化物-吡唑)而不是N-羧甲基吡唑-邻苯并磺酰胺的C-酰化中间体。C19H17N3O5S 7的晶体为单斜晶系，P21/c，a = 11.899(2) Å，b = 17.562(4) Å，c = 9.484(2) Å，β = 111.03(3)°，Z = 4，V = 1849.9(6) Å3，R 1 = 0.0857，wR 2 = 0.2216（对于I > 2σ(I)的反射）；C17H15N3O5S2 8的晶体为正交晶系，Pbca，a = 16.045(3) Å，b = 10.746(2) Å，c = 20.389(4) Å，Z = 8，V = 3516(1) Å3，R 1 = 0.0841，wR 2 = 0.2179（对于所有I > 2σ(I)的反射）。X射线晶体分析对于确定由二锂化的C(α), N-羧甲基酰肼与甲基2-(氨基磺酰基)苯甲酸酯的缩合和双环化反应制备的N-乙酰-N′-羧甲基螺(苯并异噻唑-吡唑)二氧化物的结构构型非常重要。
• Methyl Hydrazinocarboxylate as a Practical Alternative to Hydrazine in the Wolff–Kishner Reaction
  作者：Philippa Cranwell、Andrew Russell、Christopher Smith

  DOI：10.1055/s-0035-1560805

  日期：——

  Herein we describe a facile protocol for the reduction of aromatic ketones and aldehydes to the corresponding methylene unit. The procedure involves isolation of a carbomethoxyhydrazone intermediate that is easily decomposed to the reduced product without the requirement for large quantities of pernicious hydrazine.

  在这里，我们描述了一个简单的协议，用于将芳香酮和醛还原为相应的亚甲基单元。该过程涉及分离碳甲氧基腙中间体，该中间体很容易分解为还原产物，而不需要大量有害的肼。