1-methoxy-1,2,3,4-tetrahydroazulene | 331686-37-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-methoxy-1,2,3,4-tetrahydroazulene
• CAS: 331686-37-4
• 化学式: C₁₁H₁₄O
• 分子量: 162.232
• InChiKey: MCRBWHXZCJLVKL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-methoxy-1,2,3,4-tetrahydroazulene 在 tetraphenylporphyrin 、 三乙胺 作用下， 以 四氯化碳 、 二氯甲烷 为溶剂， 反应 20.0h， 生成 3-methoxy-1,2,3,5-tetrahydroazulen-5-one
  参考文献：
  名称：

  Synthesis and Chemistry of Endoperoxides Derived from 3,4-Dihydroazulen-1(2H)-one: An Entry to Cyclopentane-Anellated Tropone Derivatives

  摘要：

  Reduction of trienone 1 and subsequent treatment with acid in MeOH furnished 1-methoxy-1,2,3,4-tetrahydroazulene (13). Photo-oxygenation of 13 provided the two bicyclic endoperoxides 14 and 15. Pyrolysis of 14 and 15 gave the corresponding bis-epoxides 17 and 18, which have been synthesized also upon treatment with a catalytic amount of CoTPP (TPP = tetraphenylporphyrin). That an unusual endoperoxide-endoperoxide rearrangement has not been observed strongly supports the assumption that the carbonyl group in 2-4 is responsible for this unprecedented endoperoxide-endoperoxide rearrangement. Treatment of the endoperoxides 14 and 15 with a catalytic amount of Et3N at 0 degrees provided the azulenones 22 and 23 in high yield. Attempted cleavage of the O-O peroxide linkage in 14 and 15 with thiourea resulted, contrary to our expectation, in the formation of 22 and 23. That thiourea acts as a base instead of a reducing reagent has been observed for the first time in peroxide chemistry.

  DOI：

  10.1002/1522-2675(20001220)83:12<3131::aid-hlca3131>3.0.co;2-6
• 作为产物：
  描述：

  3,4-二氢-1(2H)-奥酮 在 盐酸 、 sodium tetrahydroborate 、 cerium(III) chloride 作用下， 以 甲醇 为溶剂， 反应 0.33h， 生成 1-methoxy-1,2,3,4-tetrahydroazulene
  参考文献：
  名称：

  Synthesis and Chemistry of Endoperoxides Derived from 3,4-Dihydroazulen-1(2H)-one: An Entry to Cyclopentane-Anellated Tropone Derivatives

  摘要：

  Reduction of trienone 1 and subsequent treatment with acid in MeOH furnished 1-methoxy-1,2,3,4-tetrahydroazulene (13). Photo-oxygenation of 13 provided the two bicyclic endoperoxides 14 and 15. Pyrolysis of 14 and 15 gave the corresponding bis-epoxides 17 and 18, which have been synthesized also upon treatment with a catalytic amount of CoTPP (TPP = tetraphenylporphyrin). That an unusual endoperoxide-endoperoxide rearrangement has not been observed strongly supports the assumption that the carbonyl group in 2-4 is responsible for this unprecedented endoperoxide-endoperoxide rearrangement. Treatment of the endoperoxides 14 and 15 with a catalytic amount of Et3N at 0 degrees provided the azulenones 22 and 23 in high yield. Attempted cleavage of the O-O peroxide linkage in 14 and 15 with thiourea resulted, contrary to our expectation, in the formation of 22 and 23. That thiourea acts as a base instead of a reducing reagent has been observed for the first time in peroxide chemistry.

  DOI：

  10.1002/1522-2675(20001220)83:12<3131::aid-hlca3131>3.0.co;2-6