甲硫代酰胺,N,N-二乙基- | 13839-14-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 硫代羧酸及其衍生物
• 中文名称: 甲硫代酰胺,N,N-二乙基-
• 英文名称: N,N-diethylthioformamide
• 英文别名: N,N-diethyl-thioformamide；N,N-Diaethyl-thioformamid；Thioameisensaeure-diaethylamid；Thioformyldiaethylamin；N,N-Diaethylthioformamid；N,N-diethylmethanethioamide
• CAS: 13839-14-0
• 化学式: C₅H₁₁NS
• 分子量: 117.215
• InChiKey: QLDXGBQOCBVQMY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  7
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  35.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  甲硫代酰胺,N,N-二乙基- 在 aluminum oxide 、 sodium hydroxide 作用下， 反应 0.67h， 生成 N,N-二乙基乙酰胺
  参考文献：
  名称：

  Jonczyk, Andrzej; Owczarczyk, Zbyslaw; Makosza, Mieczyslaw, Bulletin des Societes Chimiques Belges, 1987, vol. 96, # 4, p. 303 - 310

  摘要：

  DOI：
• 作为产物：
  描述：

  N,N-二乙基甲酰胺 在 三苯基硅烷硫醇 作用下， 以 neat liquid 为溶剂， 反应 12.0h， 以51%的产率得到甲硫代酰胺,N,N-二乙基-
  参考文献：
  名称：

  使用Ph3SiSH（A至T）和Ph3SnOH（T至A）试剂进行酰胺（A）-硫酰胺（T）相互转化

  摘要：

  Ph 3 SiSH将酰胺转化为硫代酰胺，Ph 3 SnOH进行相反的过程，同时形成Ph 3 SiOH（或Ph 3 SiOSiPh 3）和Ph 3 SnSSnPh 3。化学性质很好地说明了硅的亲氧性与锡的亲硫性相比，并且发生在相对温和的条件下，对于酰胺到硫酰胺的转化，不需要酰胺活化。化学与用于硅可用数据一致（S）（O），锡（O）（S）和C（O）（S）键能。版权所有©2016 John Wiley＆Sons，Ltd.

  DOI：

  10.1002/aoc.3462

文献信息

• Novel Thiofomylation of Primary and Secondary Amines Using <i>N</i>-Aryl-1,2,3,4,5,7-Pentathiazocanes
  作者：Kazuaki Shimada、Hiroki Shibuya、Kenshiro Makino、Tatsuya Otsuka、Yuki Onuma、Shigenobu Aoyagi、Yuji Takikawa

  DOI：10.1080/10426501003773407

  日期：2010.5.27

  in the presence of primary and secondary amines afforded N-Alkyl or N,N-dialkylthioformamides 5, and similar heating of 1 in the absence of amines afforded an inseparable mixture of acyclic polysulfides 4 bearing a thioformanilide moiety on each terminal. Bisthioformanilides 4 were also converted into 5 by treating with these amines, and the thioformylation was assumed to proceed through a pathway

  在伯胺和仲胺存在下加热 N-芳基-1,2,3,4,5,7-五噻唑烷 1 得到 N-烷基或 N,N-二烷基硫代甲酰胺 5，并在不存在胺的情况下对 1 进行类似加热提供了在每个末端带有硫代甲酰苯胺部分的无环多硫化物 4 的不可分离的混合物。双硫甲酰苯胺 4 也通过用这些胺处理转化为 5，并且假定硫甲酰化通过涉及 1 的环裂变和随后这些胺亲核攻击 4 的硫甲酰基的途径进行。
• Sulfur‐ and Amine‐ Promoted Multielectron Autoredox Transformation of Nitromethane: Multicomponent Access to Thiourea Derivatives
  作者：Supasorn Phaenok、Le Anh Nguyen、Darunee Soorukram、Thi Thanh Tam Nguyen、Pascal Retailleau、Thanh Binh Nguyen

  DOI：10.1002/chem.202303703

  日期：2024.2

  Thiourea derivatives are in‐demand motifs in organic synthesis, medicinal chemistry and material science, yet redox methods for the synthesis that start from safe, simple, inexpensive and readily available feedstocks are scarce. In this article, we disclose the synthesis of these motifs using elemental sulfur and nitromethane as the starting materials. The method harnesses the multi‐electron auto‐redox property of nitromethane in the presence of sulfur and amines, delivering thiourea products without any added oxidant or reductant. Extension of this reaction to cyclizable amines and/or higher homologues of nitromethane led to a wide range of nitrogen heterocycles and thioamides. Operationally simple, the reactions are scalable, tolerate a wide range of functional groups, and can be employed for the direct functionalization of natural products. Mechanistically, the nitro group was found to act as an oxidant leaving group, being reduced to ammonia whereas sulfur, along with the role of a sulfur building block for the thiocarbonyl group, behaved as a complementary reductant, being oxidized to sulfate.

  摘要 硫脲衍生物是有机合成、药物化学和材料科学中炙手可热的基团，然而以安全、简单、廉价和易于获得的原料为起始原料的氧化还原合成方法却十分稀缺。本文披露了以元素硫和硝基甲烷为起始原料合成这些基团的方法。该方法利用了硝基甲烷在硫和胺存在下的多电子自动氧化还原特性，在不添加任何氧化剂或还原剂的情况下生成硫脲产品。将这一反应扩展到可环化胺和/或硝基甲烷的更高同系物，可得到多种氮杂环和硫代酰胺。该反应操作简单，可扩展性强，可容忍多种官能团，可用于天然产物的直接官能化。从机理上讲，硝基可作为氧化剂离去基团，被还原成氨，而硫作为硫代羰基的硫构件，可作为互补还原剂，被氧化成硫酸盐。
• Syntheses and Stability of Alkynyl <i>S,N</i>-Acetals Derived from 2-Propynals
  作者：Toshiaki Murai、Kozue Fukushima、Yukiyasu Ohta、Yuichiro Mutoh

  DOI：10.1080/10426500902947765

  日期：2009.6.23

  Two types of synthetic methods for S, N-acetals derived from 2-propynals were described. Thioformamides, lithium acetylides, and alkylating agents were the key substrates. In the first method, methylation of thioformamides with MeOTf followed by reacting with lithium acetylides led to the title compounds. As an alternative method, the direct addition of lithium acetylides to thioformamides gave lithium thiolates, which was then alkylated. With these two methods, a wide range of derivatives including bis-S, N-acetals were provided, and their stability was influenced by the substituents at the alkynyl carbon atom. The introduction of silyl group enhanced the stability effectively.
• Kuliev, A. B.; Abdullaeva, M. I.; Akhadov, N. O., Journal of applied chemistry of the USSR, 1984, vol. 57, # 8, p. 1699 - 1701
  作者：Kuliev, A. B.、Abdullaeva, M. I.、Akhadov, N. O.

  DOI：——

  日期：——
• Seebach,D. et al., Chemische Berichte, 1976, vol. 109, p. 1309 - 1323
  作者：Seebach,D. et al.

  DOI：——

  日期：——

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