2-hydroxymethylene-3-(3-hexynyl)cyclohexanone | 144713-06-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-hydroxymethylene-3-(3-hexynyl)cyclohexanone
• 英文别名: 3-hex-3-ynyl-2-(hydroxymethylidene)cyclohexan-1-one
• CAS: 144713-06-4
• 化学式: C₁₃H₁₈O₂
• 分子量: 206.285
• InChiKey: SRQMMUWTPNTFLR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.99
• 重原子数：
  15.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  37.3
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  2-hydroxymethylene-3-(3-hexynyl)cyclohexanone 在 三乙胺 、 甲烷磺酰基叠氮化物 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以70%的产率得到2-diazo-3-(3-hexynyl)cyclohexanone
  参考文献：
  名称：

  Rhodium(II)-catalyzed cyclization of 2-alkynyl 2-diazo-3-oxobutanoates as a method for synthesizing substituted furans

  摘要：

  A series of 2-alkynyl 2-diazo-3-oxobutanoates, when treated with a catalytic quantity of rhodium(II) acetate, were found to produce furo[3,4-c]furans in good yield. The reaction proceeds by addition of a rhodium-stabilized carbenoid onto the acetylenic pi-bond to give a vinyl carbenoid which subsequently cyclizes onto the neighboring carbonyl group to produce the furan ring. In a similar manner, indeno[1,2-c]furans were produced from 2-butynyl 2-diazoarylacetates. Compounds substituted with methyl groups on the propargylic carbon atom cyclized at a slower rate. This rate diminution is attributed to the fact that the unsubstituted propargyl group can more easily achieve the required conformation for cyclization. C-H insertion was found to compete with furan formation when an alkyl group was attached to the keto functionality of the starting diazo acetoacetate. Diazo alkynyl sulfones undergo a novel oxygen transfer reaction when treated with rhodium(II) acetate at 80-degrees-C. The cyclized product is formed by sulfone oxygen attack onto the vinyl carbenoid producing a dipolar species which subsequently collapses to give the butenolide sulfoxide.

  DOI：

  10.1021/jo00053a009
• 作为产物：
  描述：

  2-环己烯-1-酮 、 1-溴-3-己炔 、 甲酸乙酯 生成 2-hydroxymethylene-3-(3-hexynyl)cyclohexanone
  参考文献：
  名称：

  Rhodium(II)-catalyzed cyclization of 2-alkynyl 2-diazo-3-oxobutanoates as a method for synthesizing substituted furans

  摘要：

  A series of 2-alkynyl 2-diazo-3-oxobutanoates, when treated with a catalytic quantity of rhodium(II) acetate, were found to produce furo[3,4-c]furans in good yield. The reaction proceeds by addition of a rhodium-stabilized carbenoid onto the acetylenic pi-bond to give a vinyl carbenoid which subsequently cyclizes onto the neighboring carbonyl group to produce the furan ring. In a similar manner, indeno[1,2-c]furans were produced from 2-butynyl 2-diazoarylacetates. Compounds substituted with methyl groups on the propargylic carbon atom cyclized at a slower rate. This rate diminution is attributed to the fact that the unsubstituted propargyl group can more easily achieve the required conformation for cyclization. C-H insertion was found to compete with furan formation when an alkyl group was attached to the keto functionality of the starting diazo acetoacetate. Diazo alkynyl sulfones undergo a novel oxygen transfer reaction when treated with rhodium(II) acetate at 80-degrees-C. The cyclized product is formed by sulfone oxygen attack onto the vinyl carbenoid producing a dipolar species which subsequently collapses to give the butenolide sulfoxide.

  DOI：

  10.1021/jo00053a009