methyl 2'-phenylspiro[2-ethylcyclopropane-1,5'(4'H)-thiazoline]-4'-carboxylate

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: methyl 2'-phenylspiro[2-ethylcyclopropane-1,5'(4'H)-thiazoline]-4'-carboxylate
• 英文别名: Methyl 2-ethyl-5-phenyl-4-thia-6-azaspiro[2.4]hept-5-ene-7-carboxylate
• 化学式: C₁₅H₁₇NO₂S
• 分子量: 275.371
• InChiKey: XMVGZBJRRXNJIH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  64
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  methyl 2-chloro-2-(2'-ethylcyclopropylidene)acetate 、 硫代苯甲酰胺 在 碳酸氢钠 作用下， 以 乙腈 为溶剂， 反应 5.0h， 以58%的产率得到methyl 2'-phenylspiro[2-ethylcyclopropane-1,5'(4'H)-thiazoline]-4'-carboxylate
  参考文献：
  名称：

  A New and Efficient Access to Thiazoline-4-carboxylates and Cysteine Derivatives Incorporating Cyclopropyl Groups

  摘要：

  Under basic conditions (NaHCO3, MeCN), thiocarboxamides 2, including NN-thioureas, cleanly undergo Michael addition onto 2-chloro-2-cyclopropylideneacetates 1, attacking through the sulfur, and this is followed by an intramolecular substitution to afford 5-spirocyclopropane-annelated thiazoline-4-carboxylates 4 in 37-92% yields. The thiazolines 4 are cysteine derivatives that possess a cyclopropyl or substituted cyclopropyl group in place of the gem-dimethyl-substituted beta -carbon atom of penicillamine; they can be hydrolyzed to the hydrochloride salt of the amino acid 5 by heating in acid. Under acidic conditions (CH2Cl2, HCl), the Michael adducts 7 of thioamides 2 onto 1 are formed in high to virtually quantitative yields. When treated with NaHCO3 in MeCN, the adducts 7 cyclize to thiazolinecarboxylates 4 (51-82%), but in the presence of Ti(OiPr)(4) they form spirocyclopropane-annelated thiazinones 8 (19-88%).

  DOI：

  10.1002/1099-0690(200108)2001:16<3025::aid-ejoc3025>3.0.co;2-k

文献信息

• A New and Efficient Access to Thiazoline-4-carboxylates and Cysteine Derivatives Incorporating Cyclopropyl Groups
  作者：Marcus W. Nötzel、Thomas Labahn、Mazen Es-Sayed、Armin de Meijere

  DOI：10.1002/1099-0690(200108)2001:16<3025::aid-ejoc3025>3.0.co;2-k

  日期：2001.8

  Under basic conditions (NaHCO3, MeCN), thiocarboxamides 2, including NN-thioureas, cleanly undergo Michael addition onto 2-chloro-2-cyclopropylideneacetates 1, attacking through the sulfur, and this is followed by an intramolecular substitution to afford 5-spirocyclopropane-annelated thiazoline-4-carboxylates 4 in 37-92% yields. The thiazolines 4 are cysteine derivatives that possess a cyclopropyl or substituted cyclopropyl group in place of the gem-dimethyl-substituted beta -carbon atom of penicillamine; they can be hydrolyzed to the hydrochloride salt of the amino acid 5 by heating in acid. Under acidic conditions (CH2Cl2, HCl), the Michael adducts 7 of thioamides 2 onto 1 are formed in high to virtually quantitative yields. When treated with NaHCO3 in MeCN, the adducts 7 cyclize to thiazolinecarboxylates 4 (51-82%), but in the presence of Ti(OiPr)(4) they form spirocyclopropane-annelated thiazinones 8 (19-88%).