高等学校化学学报

高等学校化学学报 ›› 1998, Vol. 19 ›› Issue (S1): 97.

• Organic Synthesis Chemistry • 上一篇    下一篇

Novel Enone-benzene Rearrangement of 4,4-Dialkylcholest-5-en-3-ones to Ring-B Aromatic Steroidal Hydrocarbons Catalysed by p-Toluenesulfonic acid

Hui-Yun Duan1,2, Tong-Shuang Li1,2   

  1. 1. Department of Chemistry, Hebei University, Baoding 071002, Hebei Province, National Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, Gansu Province
  • 出版日期:1998-12-31 发布日期:1998-12-31
  • 通讯作者: Tong-Shuang Li,e-mail:orgsyn@hbu.edu.cn E-mail:orgsyn@hbu.edu.cn

Novel Enone-benzene Rearrangement of 4,4-Dialkylcholest-5-en-3-ones to Ring-B Aromatic Steroidal Hydrocarbons Catalysed by p-Toluenesulfonic acid

Hui-Yun Duan1,2, Tong-Shuang Li1,2   

  1. 1. Department of Chemistry, Hebei University, Baoding 071002, Hebei Province, National Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, Gansu Province
  • Online:1998-12-31 Published:1998-12-31
  • Contact: Tong-Shuang Li,e-mail:orgsyn@hbu.edu.cn E-mail:orgsyn@hbu.edu.cn

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摘要： Under acidic conditions, α,α-dimethyl-β,γ-unsaturated cyclohexanones undergoes an enone-benzene rearrangement leading to aromatic derivatives1-4. We recently run an enone-benzene rearrangement of 4,4-dimethyl-cholest-5-en-3-one (1a) catalysed by montmorillonite K-10 to give 1,3,4-trimethyl-19-norcholesta-1,3,5(10)-triene (2a) in moderate yield accompanying intractable mixture of hydrocarbons as by products5. Repetition of this reaction by employing TsOH as a catalyst, 2a was obtained in 65% yield and a new product, 6-methyl-3-isopropyl-A,19-dinorcholesta-6,8,10(5)-triene (3a), was also isolated in 25% yield. The formation of 3a has not been reported in earlier studies1-5. Herein we report the novel enone-benzene rearrangement of 4,4-dialkylcholest-5-en-3-ones (1a~d) leading to ring-B aromatic steroidal hydrocarbons (3a~d) catalysed by TsOH (Scheme 1).

Abstract: Under acidic conditions, α,α-dimethyl-β,γ-unsaturated cyclohexanones undergoes an enone-benzene rearrangement leading to aromatic derivatives1-4. We recently run an enone-benzene rearrangement of 4,4-dimethyl-cholest-5-en-3-one (1a) catalysed by montmorillonite K-10 to give 1,3,4-trimethyl-19-norcholesta-1,3,5(10)-triene (2a) in moderate yield accompanying intractable mixture of hydrocarbons as by products5. Repetition of this reaction by employing TsOH as a catalyst, 2a was obtained in 65% yield and a new product, 6-methyl-3-isopropyl-A,19-dinorcholesta-6,8,10(5)-triene (3a), was also isolated in 25% yield. The formation of 3a has not been reported in earlier studies1-5. Herein we report the novel enone-benzene rearrangement of 4,4-dialkylcholest-5-en-3-ones (1a~d) leading to ring-B aromatic steroidal hydrocarbons (3a~d) catalysed by TsOH (Scheme 1).

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