8-ethynyl-4,4,8-trimethyl-1-[(trimethylsilyl)ethynyl]bicyclo[4.2.0]octan-2-one

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 8-ethynyl-4,4,8-trimethyl-1-[(trimethylsilyl)ethynyl]bicyclo[4.2.0]octan-2-one
• 英文别名: 8-Ethynyl-4,4,8-trimethyl-1-(2-trimethylsilylethynyl)bicyclo[4.2.0]octan-2-one
• 化学式: C₁₈H₂₆OSi
• 分子量: 286.489
• InChiKey: VSHWXAXWYSSTFU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.72
• 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：

  5,5-Dimethyl-2-trimethylsilanylethynyl-cyclohex-2-enone 、 2-甲基-1-丁烯-3-炔 以 苯 为溶剂， 以57%的产率得到cis-3,4,4a,5,6,8a-hexahydro-3,3-dimethyl-6-methylidene-8a-[(trimethylsilyl)ethynyl]naphthalen-1-(2H)-one
  参考文献：
  名称：

  摘要：

  Irradiation (350 nm) of 2-alkynylcyclohex-2-enones 1 in benzene in the presence of an excess of 2-methylbut-1-en-3-yne (2) affords in each case a mixture of a cis-fused 3,4,4a,5,6,8a-hexahydronaphthalen-1(2H)-one 3 and a bicyclo[4.2.0]octan-2-one 4 (Scheme 2), the former being formed as main product via 1,6-cyclization of the common biradical intermediate. The (parent) cyclohex-2-enone and other alkylcyclohex-2-enones 7 also give naphthalenones 8, albeit in lower yields, the major products being bicyclo[4.2.0]octan-2-ones (Scheme 4). No product derived from such a 1,6-cyclization is observed in the irradiation of 3-alkynylcyclohexenone 9 in the presence of 2 (Scheme 4). Irradiation of the 2-cyano-substituted cyclohexenone 12 under these conditions again affords only traces of naphthalenone 13, the main product now being the substituted bicyclo[4.2.0]oct-7-ene 16 (Scheme 5), resulting from [2 + 2] cycloaddition of the acetylenic C-C bond of 2 to excited 12.

  DOI：

  10.1002/(sici)1522-2675(20000315)83:3<554::aid-hlca554>3.0.co;2-i

文献信息

• Photochemical Formation of 3,4,4a,5,6,8a-Hexahydro-2<i>H</i>-naphthalen-1-ones from Cyclohex-2-enones and 2-Methylbut-1-en-3-yne
  作者：Birgit Witte、Paul Margaretha

  DOI：10.1021/ol990003k

  日期：1999.7.1

  Irradiation of 2-alkynylcyclohex-2-enones 1a and 1b in the presence of 2-methylbut-1-en-3-yne in benzene affords 6-methylenehexahydronaph-thalen-1-ones 2 as main products while photolysis in methanol gives predominantly 1:1 diastereomeric mixtures of 6-methoxy-6-methylnaphthalenones 4 and 5, respectively, The key step in this stepwise [4 + 2]-cycloaddition is the 1,6-cyclization of biradical 6 to 1,2-cyclohexadiene 7.