cis-1-(p-chlorobenzoyl)-2-phenylcyclopropane | 137595-86-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: cis-1-(p-chlorobenzoyl)-2-phenylcyclopropane
• 英文别名: (4-chlorophenyl)-[(1S,2R)-2-phenylcyclopropyl]methanone
• CAS: 137595-86-9
• 化学式: C₁₆H₁₃ClO
• 分子量: 256.732
• InChiKey: SESAUKNQPZECGG-GJZGRUSLSA-N

物化性质

• 沸点：
  400.0±35.0 °C(Predicted)
• 密度：
  1.243±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  trans-1-(p-chlorobenzoyl)-2-phenylcyclopropane 在 二-叔-丁基过氧草酸酯 、 1,3-二甲基-2-苯基-2H-苯并咪唑 作用下， 以 乙腈 为溶剂， 反应 23.0h， 以0.28%的产率得到(1SR,2SR)-phenyl(2-phenylcyclopropyl)ketone
  参考文献：
  名称：

  Reversible cyclopropyl ring opening of 1-aroyl-2-phenylcyclopropane radical anions. Determination of the ring opening and closure rates of the intermediate ketyls

  摘要：

  The phenylcyclopropylketyl ring opening has been used as a mechanistic probe for the detection of radical intermediates. The reaction is of limited use since the ring-opening reaction is reversible. 1-Benzoyl-2-phenylcyclopropane (II) was considered to be a better probe since the ring opening of its radical anion was believed to be irreversible. In this study, the ring opening of II.- is also found to be reversible since the radical-initiated reduction of (+)-trans-1-benzoyl-2-phenylcyclopropane ((+)-trans-II) with 1,3-dimethyl-2-phenylbenzimidazoline (DMBI) leads to racemized and isomerized products ((+)-trans-11 and (+/-)-cis-II). The rate constants (k(o)) for the ring opening of both trans- and cis-II ketyls have been estimated from the intramolecular competitive reduction of both trans- and cis-1-(p-chlorobenzoyl)-2-phenylcyclopropane with DMBI (k(o,trans) = (2.8 +/- 0. 1) x 10(5) s-1, k(o, cis) = (1.6 +/- 0.2) x 10(6) s-1, 22-degrees-C). The rate constants for the ring closure (k(c)) of the opened radical to give the trans and cis ketyls were estimated from the DMBI reduction of trans-II using dicyclohexylphosphine as a hydrogen atom donor (k(c,trans) = 4 x 10(2) s-1, k(c,cis) = 23 +/- 9 s-1, 61-degrees-C).

  DOI：

  10.1021/ja00028a045

文献信息

• Reversible cyclopropyl ring opening of 1-aroyl-2-phenylcyclopropane radical anions. Determination of the ring opening and closure rates of the intermediate ketyls
  作者：Dennis D. Tanner、Jian Jeffrey Chen、Christine Luelo、Pollyanna M. Peters

  DOI：10.1021/ja00028a045

  日期：1992.1

  The phenylcyclopropylketyl ring opening has been used as a mechanistic probe for the detection of radical intermediates. The reaction is of limited use since the ring-opening reaction is reversible. 1-Benzoyl-2-phenylcyclopropane (II) was considered to be a better probe since the ring opening of its radical anion was believed to be irreversible. In this study, the ring opening of II.- is also found to be reversible since the radical-initiated reduction of (+)-trans-1-benzoyl-2-phenylcyclopropane ((+)-trans-II) with 1,3-dimethyl-2-phenylbenzimidazoline (DMBI) leads to racemized and isomerized products ((+)-trans-11 and (+/-)-cis-II). The rate constants (k(o)) for the ring opening of both trans- and cis-II ketyls have been estimated from the intramolecular competitive reduction of both trans- and cis-1-(p-chlorobenzoyl)-2-phenylcyclopropane with DMBI (k(o,trans) = (2.8 +/- 0. 1) x 10(5) s-1, k(o, cis) = (1.6 +/- 0.2) x 10(6) s-1, 22-degrees-C). The rate constants for the ring closure (k(c)) of the opened radical to give the trans and cis ketyls were estimated from the DMBI reduction of trans-II using dicyclohexylphosphine as a hydrogen atom donor (k(c,trans) = 4 x 10(2) s-1, k(c,cis) = 23 +/- 9 s-1, 61-degrees-C).