1-Chloro-1-(trichloroethenyl)spiropentane | 72853-07-7

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 乙烯基卤化物
• 英文名称: 1-Chloro-1-(trichloroethenyl)spiropentane
• 英文别名: 1-Chlor-1-(trichlorvinyl)spiropentan；2-Chloro-2-(1,2,2-trichloroethenyl)spiro[2.2]pentane
• CAS: 72853-07-7
• 化学式: C₇H₆Cl₄
• 分子量: 231.937
• InChiKey: SWRDNYMHHIMEIV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1-Chloro-1-(trichloroethenyl)spiropentane 在 acidic ion-exchange resin (BAYER LEWATIT 118) 作用下， 以 甲醇 为溶剂， 反应 120.0h， 生成 (E)-Methyl 2-chloro-2-spiropentylideneacetate
  参考文献：
  名称：

  Cyclopropyl building blocks for organic synthesis. Part 22. Facile synthesis of stable analogs of 2-oxocyclobutanecarboxylates: 2-[(diphenylmethylene)amino]cyclobutenecarboxylates, derivatives and reactions

  摘要：

  An efficient two-step synthesis of 2-[(diphenylmethylene)amino]cyclobutenecarboxylate (4a) and some analogous derivatives from 2-chloro-2-cyclopropylideneacetates 2, 17, 22, and 25 and nonenolizable ketimines, especially diphenylmethyleneamine (DPMA-H), is described. A likely mechanism for the formation of 4a from the primary Michael adduct 3 of DPMA-H to 2 and its substituted analogues is presented. The unique neighboring group effect of the DPMA moiety to allow formation of an azaspiropentane intermediate and its regioselective rearrangement to cyclobutenamine derivatives is discussed and further exemplified by an extremely facile SET alpha-chlorination. Compound 4a and derivatives undergo a thermal ring-opening reaction to the corresponding butadienes with subsequent formation of 1,3-disubstituted 3,4-dihydroisoquinolines 39. Further transformations of 4a and some derivatives include transesterification, hydrolysis to methyl 2-oxocyclobutanecarboxylates, and addition of N-phenyltriazolinedione.

  DOI：

  10.1021/jo00075a047
• 作为产物：
  描述：

  四氯环丙烯 、 亚甲基环丙烷 在 potassium carbonate 作用下， 反应 336.0h， 以64%的产率得到1-Chloro-1-(trichloroethenyl)spiropentane
  参考文献：
  名称：

  Cyclopropyl building blocks for organic synthesis. Part 22. Facile synthesis of stable analogs of 2-oxocyclobutanecarboxylates: 2-[(diphenylmethylene)amino]cyclobutenecarboxylates, derivatives and reactions

  摘要：

  An efficient two-step synthesis of 2-[(diphenylmethylene)amino]cyclobutenecarboxylate (4a) and some analogous derivatives from 2-chloro-2-cyclopropylideneacetates 2, 17, 22, and 25 and nonenolizable ketimines, especially diphenylmethyleneamine (DPMA-H), is described. A likely mechanism for the formation of 4a from the primary Michael adduct 3 of DPMA-H to 2 and its substituted analogues is presented. The unique neighboring group effect of the DPMA moiety to allow formation of an azaspiropentane intermediate and its regioselective rearrangement to cyclobutenamine derivatives is discussed and further exemplified by an extremely facile SET alpha-chlorination. Compound 4a and derivatives undergo a thermal ring-opening reaction to the corresponding butadienes with subsequent formation of 1,3-disubstituted 3,4-dihydroisoquinolines 39. Further transformations of 4a and some derivatives include transesterification, hydrolysis to methyl 2-oxocyclobutanecarboxylates, and addition of N-phenyltriazolinedione.

  DOI：

  10.1021/jo00075a047

文献信息

• Weber, Walter; Meijere, Armin de, Chemische Berichte, 1985, vol. 118, # 6, p. 2450 - 2471
  作者：Weber, Walter、Meijere, Armin de

  DOI：——

  日期：——
• Weber, Walter; Meijere, Armin de, Angewandte Chemie, 1980, vol. 92, # 2, p. 135 - 136
  作者：Weber, Walter、Meijere, Armin de

  DOI：——

  日期：——
• Coudret; Ernst; De Meijere, Synthesis, 1994, # 9, p. 920 - 922
  作者：Coudret、Ernst、De Meijere、Waegell

  DOI：——

  日期：——
• WEBER W.; MEIJERE ARMIN, ANGEW. CHEM., 1980, 92, NO 2, 135-136
  作者：WEBER W.、 MEIJERE ARMIN

  DOI：——

  日期：——
• WEBER, W.;MEIJERE, A. DE, CHEM. BER., 1985, 118, N 6, 2450-2471
  作者：WEBER, W.、MEIJERE, A. DE

  DOI：——

  日期：——