4,5-dimethyl-2-trimethylsilylthiophene-3-carboxylic acid | 175217-23-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻吩类
• 英文名称: 4,5-dimethyl-2-trimethylsilylthiophene-3-carboxylic acid
• 英文别名: 2-trimethylsilyl-4,5-dimethyl-3-thiophenecarboxylic acid；4,5-Dimethyl-2-(trimethylsilyl)-3-thiophenecarboxylic acid
• CAS: 175217-23-9
• 化学式: C₁₀H₁₆O₂SSi
• 分子量: 228.387
• InChiKey: VTNSLLAJPABUFM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.61
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  65.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4,5-dimethyl-2-trimethylsilylthiophene-3-carboxylic acid 在 氯化亚砜 作用下， 以 正庚烷 为溶剂， 生成
  参考文献：
  名称：

  Process Research on the Synthesis of Silthiofam:  A Novel Fungicide for Wheat

  摘要：

  The development of an efficient, low-cost synthesis of the novel wheat fungicide silthiofam (1) is described. Improvements to the original Discovery route allowed 300 kg of material to be prepared in two, overlapping pilot-plant campaigns. Thereafter, efforts were focused on further optimizing the pilot-plant route, and on devising alternate, lower cost routes to silthiofam. One potential new route involved a cycloaddition reaction between 3-mereapto-2-butanone and N-(2-propenyl)-3-trimethylsilyipropynamide. The cyclic product could be directly dehydrated to silthiofam, however the overall yield was modest, raw material costs were high, and there were purification problems. The route ultimately selected for development proceeds in 6 chemical steps and about 60% yield from the inexpensive precursors 3-chloro-2-butanone and methyl 3-methoxyacrylate. Key features of the route are a novel thiophene-3-carboxylate synthesis involving cycloaddition of 3-mercapto-2-butanone with the acrylate followed by acid catalyzed aromatization, the room temperature formation and silylation of a thiophene-3-carboxylate dianion, and conversion of the resulting carboxylic acid into silthiofam with negligible loss of the silyl group. The process involves isolation of just two intermediates, only one of which is purified, and uses only three organic solvents, all of which are recycled. It can be run safely on large scale to give high-purity silthiofam.

  DOI：

  10.1021/op020206f
• 作为产物：
  描述：

  4,5-二甲基噻吩-3-羧酸甲酯 在 正丁基锂 、 2,6-二叔丁基-4-甲基苯酚 、 N,N-二异丙基乙胺 、 lithium hydroxide 作用下， 以 四氢呋喃 、 正庚烷 、 水 为溶剂， 反应 2.0h， 生成 4,5-dimethyl-2-trimethylsilylthiophene-3-carboxylic acid
  参考文献：
  名称：

  Process Research on the Synthesis of Silthiofam:  A Novel Fungicide for Wheat

  摘要：

  The development of an efficient, low-cost synthesis of the novel wheat fungicide silthiofam (1) is described. Improvements to the original Discovery route allowed 300 kg of material to be prepared in two, overlapping pilot-plant campaigns. Thereafter, efforts were focused on further optimizing the pilot-plant route, and on devising alternate, lower cost routes to silthiofam. One potential new route involved a cycloaddition reaction between 3-mereapto-2-butanone and N-(2-propenyl)-3-trimethylsilyipropynamide. The cyclic product could be directly dehydrated to silthiofam, however the overall yield was modest, raw material costs were high, and there were purification problems. The route ultimately selected for development proceeds in 6 chemical steps and about 60% yield from the inexpensive precursors 3-chloro-2-butanone and methyl 3-methoxyacrylate. Key features of the route are a novel thiophene-3-carboxylate synthesis involving cycloaddition of 3-mercapto-2-butanone with the acrylate followed by acid catalyzed aromatization, the room temperature formation and silylation of a thiophene-3-carboxylate dianion, and conversion of the resulting carboxylic acid into silthiofam with negligible loss of the silyl group. The process involves isolation of just two intermediates, only one of which is purified, and uses only three organic solvents, all of which are recycled. It can be run safely on large scale to give high-purity silthiofam.

  DOI：

  10.1021/op020206f

文献信息

• Fungicides for the control of take-all disease of plants
  申请人：Monsanto Company

  公开号：US05486621A1

  公开（公告）日：1996-01-23

  This invention relates to 4,5-dimethyl-N-2-propenyl-2-(trimethylsilyl)-3-thiophenecarboxamide, a method for the control of Take-All disease (Gaeumannomyces species) in plants by the use of this compound, and to fungicidal compostions for carrying out the method.

  本发明涉及4,5-二甲基-N-2-丙烯基-2-(三甲基硅基)-3-噻吩羧酰胺，一种通过使用该化合物控制植物中“全枯病”（Gaeumannomyces物种）的方法，以及用于执行该方法的杀菌组合物。
• Process Research on the Synthesis of Silthiofam:  A Novel Fungicide for Wheat
  作者：Phillips、Thomas L. Fevig、Patrick H. Lau、George H. Klemm、Michael K. Mao、Chun Ma、James A. Gloeckner、Art S. Clark

  DOI：10.1021/op020206f

  日期：2002.7.1

  The development of an efficient, low-cost synthesis of the novel wheat fungicide silthiofam (1) is described. Improvements to the original Discovery route allowed 300 kg of material to be prepared in two, overlapping pilot-plant campaigns. Thereafter, efforts were focused on further optimizing the pilot-plant route, and on devising alternate, lower cost routes to silthiofam. One potential new route involved a cycloaddition reaction between 3-mereapto-2-butanone and N-(2-propenyl)-3-trimethylsilyipropynamide. The cyclic product could be directly dehydrated to silthiofam, however the overall yield was modest, raw material costs were high, and there were purification problems. The route ultimately selected for development proceeds in 6 chemical steps and about 60% yield from the inexpensive precursors 3-chloro-2-butanone and methyl 3-methoxyacrylate. Key features of the route are a novel thiophene-3-carboxylate synthesis involving cycloaddition of 3-mercapto-2-butanone with the acrylate followed by acid catalyzed aromatization, the room temperature formation and silylation of a thiophene-3-carboxylate dianion, and conversion of the resulting carboxylic acid into silthiofam with negligible loss of the silyl group. The process involves isolation of just two intermediates, only one of which is purified, and uses only three organic solvents, all of which are recycled. It can be run safely on large scale to give high-purity silthiofam.