1-Chlor-1-(1-hexinyl)-2,2,3,3-tetramethylcyclopropan | 80631-37-4

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机氯化物
• 英文名称: 1-Chlor-1-(1-hexinyl)-2,2,3,3-tetramethylcyclopropan
• 英文别名: Cyclopropane, 1-chloro-1-(1-hexynyl)-2,2,3,3-tetramethyl-；1-chloro-1-hex-1-ynyl-2,2,3,3-tetramethylcyclopropane
• CAS: 80631-37-4
• 化学式: C₁₃H₂₁Cl
• 分子量: 212.763
• InChiKey: HJKMNEIIJCWUNQ-UHFFFAOYSA-N

物化性质

• 沸点：
  245.1±19.0 °C(Predicted)
• 密度：
  0.96±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.85
• 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：

  二氧化碳 、 1-Chlor-1-(1-hexinyl)-2,2,3,3-tetramethylcyclopropan 在 正丁基锂 、 盐酸 作用下， 以 四氢呋喃 、 正己烷 、 水 为溶剂， 反应 0.5h， 以47%的产率得到1-(hex-1-ynyl)-2,2,3,3-tetramethylcyclopropanecarboxylic acid
  参考文献：
  名称：

  1-炔基-1-氯环丙烷的锂化和随后与亲电试剂的反应：功能化炔基-和亚乙烯基环丙烷的合成

  摘要：

  1-炔基-1-氯环丙烷在-40—0°C 的THF 中用BunLi 处理后发生氯-锂交换。由此产生的有机锂物质与二氧化碳（干冰）和丙酮反应，以高达 74% 的产率选择性地产生迄今为止未知的 1-炔基环丙烷羧酸和相应的醇。涉及氯甲酸甲酯的类似反应产生环丙基乙炔酯和亚乙烯基环丙酸酯的混合物，而使用脂肪醛作为亲电子试剂提供仲丙醇，产率高达 64%。

  DOI：

  10.1007/s11172-019-2566-4
• 作为产物：
  描述：

  2,3-二甲基-2-丁烯 、 3-bromo-1,1,1-trichloroheptane 在 potassium tert-butylate 作用下， 以 正己烷 为溶剂， 反应 3.0h， 以52%的产率得到1-Chlor-1-(1-hexinyl)-2,2,3,3-tetramethylcyclopropan
  参考文献：
  名称：

  摘要：

  When treated with KOH under phase-transfer catalysis or with (BuOK)-O-t, 3-substituted (alkyl or phenyl) 1, 1, 3-tribromo-1-fluoropropanes 1a-c exclusively generate previously unknown (alk-1-ynyl)fluorocarbenes 5a-c, which react with olefins to give 1-(alk-1-ynyl)-1-fluorocyclopropanes 6a-h in 12-69% yields. Under analogous conditions, 3-alkyl- and 3-aryl-3-bromo-1, 1, 1-trichloropropanes 2a-c selectively afford (alk-1-ynyl)chlorocarbenes 7a-c, which are trapped by olefins to form the corresponding 1-(alk-1-ynyl)-1-chlorocyclopropanes 8a-k in 35-70% yields. (Phenylethynyl)chlorocarbene 7a is also selectively generated from 1, 1, 1, 3-tetrachloro-3-phenylpropane (3a) upon its treatment with (BuOK)-O-t. With an excess of 2,3-dimethylbut-2-ene or 2-methylpropene, carbene 7a yields 1-chloro-1-(phenylethynyl)cyclopropanes 8a or 8c, respectively. In contrast, 1, 1, 1, 3-tetrachloroheptane 3b and 3-alkyl- and 3-phenyl-1, 1, 1, 3-tetrabromopropanes 4a,c,f react with bases in the presence of olefins to give, along with the corresponding 1-(alk-1-ynyl)-1-halocyclopropanes 8a,c,d and 11a-f, vinylidenecyclopropanes 12a,c-g, which suggests the generation, under these conditions; both (alk-1-ynyl)halocarbenes 7b and 9a-c and vinylidenecarbenes 10 and 11a-c. The composition and structures of intermediate products in the reactions of tetrahalides 1b, 2a, 2b, 3a, and 3b with (BuOK)-O-t were determined and the mechanisms for carbene generation in these reactions were proposed.

  DOI：

  10.1023/a:1020952513679

文献信息

• Liese, Thomas; Meijere, Armin de, Angewandte Chemie, 1982, vol. 94, # 1, p. 65 - 66
  作者：Liese, Thomas、Meijere, Armin de

  DOI：——

  日期：——
• Liese, Thomas; Meijere, Armin de, Chemische Berichte, 1986, vol. 119, # 10, p. 2995 - 3026
  作者：Liese, Thomas、Meijere, Armin de

  DOI：——

  日期：——
• LIESE, T.;DE, MEIJERE, A., ANGEW. CHEM., 1982, 94, N 1, 65-66
  作者：LIESE, T.、DE, MEIJERE, A.

  DOI：——

  日期：——
• LIESE T.; MEIJERE A. DE, CHEM. BER., 119,(1986) N 10, 2995-3026
  作者：LIESE T.、 MEIJERE A. DE

  DOI：——

  日期：——
• ——
  作者：K. N. Shavrin、V. D. Gvozdev、O. M. Nefedov

  DOI：10.1023/a:1020952513679

  日期：——

  When treated with KOH under phase-transfer catalysis or with (BuOK)-O-t, 3-substituted (alkyl or phenyl) 1, 1, 3-tribromo-1-fluoropropanes 1a-c exclusively generate previously unknown (alk-1-ynyl)fluorocarbenes 5a-c, which react with olefins to give 1-(alk-1-ynyl)-1-fluorocyclopropanes 6a-h in 12-69% yields. Under analogous conditions, 3-alkyl- and 3-aryl-3-bromo-1, 1, 1-trichloropropanes 2a-c selectively afford (alk-1-ynyl)chlorocarbenes 7a-c, which are trapped by olefins to form the corresponding 1-(alk-1-ynyl)-1-chlorocyclopropanes 8a-k in 35-70% yields. (Phenylethynyl)chlorocarbene 7a is also selectively generated from 1, 1, 1, 3-tetrachloro-3-phenylpropane (3a) upon its treatment with (BuOK)-O-t. With an excess of 2,3-dimethylbut-2-ene or 2-methylpropene, carbene 7a yields 1-chloro-1-(phenylethynyl)cyclopropanes 8a or 8c, respectively. In contrast, 1, 1, 1, 3-tetrachloroheptane 3b and 3-alkyl- and 3-phenyl-1, 1, 1, 3-tetrabromopropanes 4a,c,f react with bases in the presence of olefins to give, along with the corresponding 1-(alk-1-ynyl)-1-halocyclopropanes 8a,c,d and 11a-f, vinylidenecyclopropanes 12a,c-g, which suggests the generation, under these conditions; both (alk-1-ynyl)halocarbenes 7b and 9a-c and vinylidenecarbenes 10 and 11a-c. The composition and structures of intermediate products in the reactions of tetrahalides 1b, 2a, 2b, 3a, and 3b with (BuOK)-O-t were determined and the mechanisms for carbene generation in these reactions were proposed.