1-Phenyl-8-(trimethylsilyl)-7-octyne-1,3-dione | 141726-25-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-Phenyl-8-(trimethylsilyl)-7-octyne-1,3-dione
• 英文别名: 1-phenyl-8-trimethylsilyloct-7-yne-1,3-dione
• CAS: 141726-25-2
• 化学式: C₁₇H₂₂O₂Si
• 分子量: 286.446
• InChiKey: UTCGDBRBGBYCCW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.88
• 重原子数：
  20.0
• 可旋转键数：
  6.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  34.14
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  1-Phenyl-8-(trimethylsilyl)-7-octyne-1,3-dione 在 manganese triacetate 作用下， 以 溶剂黄146 为溶剂， 反应 24.0h， 以71%的产率得到3,4,3',4'-Tetrahydro-9,9'-dihydroxy-<10,10'-bianthracene>-1,1'-(2H,2'H)-dione
  参考文献：
  名称：

  Control of the regioselectivity of oxidative free-radical cyclizations by addition to haloalkenes

  摘要：

  Chlorine substituents on the alkene control the regioselectivity of the cyclization of 5-hexenyl or 6-heptenyl radicals generated by oxidation of an acetoacetate ester or 1,3-diketone with Mn(OAc)3.2H2O. 6-Exo-cyclization of the radicals obtained by oxidation of benzoylacetone derivatives 10 and 13, containing a chlorine on the terminal double bond carbon, gives alpha-chloroalkyl radicals that add to the aromatic ring to give 11 and 16, respectively. Loss of HCl leads to naphthols 8 and 17 indicating that this reaction may be useful for aureolic acid synthesis. Exo-cyclization is the exclusive process with acetoacetates 28b, 44, 55b, and 59 containing a chlorine on the terminal double bond carbon. 6-Endo-cyclization is the exclusive process with acetoacetates 18c and 51b containing a chlorine on the internal double bond carbon. Intra- and intermolecular competition experiments indicate that these effects are primarily steric. The chlorine substituent controls the regioselectivity of the cyclization by sterically hindering attack of the radical on the chlorine bearing double bond carbon thereby retarding formation of the beta-chloroalkyl radical. The chlorine substituent does not electronically accelerate attack on the other end of the double bond to give the alpha-chloroalkyl radical.

  DOI：

  10.1021/jo00041a026
• 作为产物：
  描述：

  4-bromo-1-trimethylsilylbut-1-yne 、 1-苯基-1,3-丁二酮 在 N,N-二甲基丙烯基脲 、 lithium diisopropyl amide 作用下， 生成 1-Phenyl-8-(trimethylsilyl)-7-octyne-1,3-dione
  参考文献：
  名称：

  Control of the regioselectivity of oxidative free-radical cyclizations by addition to haloalkenes

  摘要：

  Chlorine substituents on the alkene control the regioselectivity of the cyclization of 5-hexenyl or 6-heptenyl radicals generated by oxidation of an acetoacetate ester or 1,3-diketone with Mn(OAc)3.2H2O. 6-Exo-cyclization of the radicals obtained by oxidation of benzoylacetone derivatives 10 and 13, containing a chlorine on the terminal double bond carbon, gives alpha-chloroalkyl radicals that add to the aromatic ring to give 11 and 16, respectively. Loss of HCl leads to naphthols 8 and 17 indicating that this reaction may be useful for aureolic acid synthesis. Exo-cyclization is the exclusive process with acetoacetates 28b, 44, 55b, and 59 containing a chlorine on the terminal double bond carbon. 6-Endo-cyclization is the exclusive process with acetoacetates 18c and 51b containing a chlorine on the internal double bond carbon. Intra- and intermolecular competition experiments indicate that these effects are primarily steric. The chlorine substituent controls the regioselectivity of the cyclization by sterically hindering attack of the radical on the chlorine bearing double bond carbon thereby retarding formation of the beta-chloroalkyl radical. The chlorine substituent does not electronically accelerate attack on the other end of the double bond to give the alpha-chloroalkyl radical.

  DOI：

  10.1021/jo00041a026