N-(4-methyl-4-penten-1-oxy)-4-(p-chlorophenyl)thiazole-2(3H)thione

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N-(4-methyl-4-penten-1-oxy)-4-(p-chlorophenyl)thiazole-2(3H)thione
• 英文别名: 4-(4-Chlorophenyl)-3-(4-methylpent-4-enoxy)-1,3-thiazole-2-thione；4-(4-chlorophenyl)-3-(4-methylpent-4-enoxy)-1,3-thiazole-2-thione
• 化学式: C₁₅H₁₆ClNOS₂
• 分子量: 325.883
• InChiKey: CJYGVGXHFWPSRH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  69.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-(4-methyl-4-penten-1-oxy)-4-(p-chlorophenyl)thiazole-2(3H)thione 在 三(三甲基硅基)硅烷 作用下， 以 氘代苯 为溶剂， 反应 0.42h， 以56%的产率得到2,2-dimethyltetrahydrofuran
  参考文献：
  名称：

  On the 6-endo Selectivity in 4-Penten-1-oxyl Radical Cyclizations

  摘要：

  Regioselectivities in cyclizations of 4-substituted 4-penten-1-oxyl radicals have been investigated in a combined experimental and computational study (density functional theory). The progressive increase of the 6-endo-trig selectivity along the series of 4-substituents H < CH3 < C(CH3)(3) < C6H5 has been interpreted to originate from a balance between strain and FMO interactions. Torsional strain, which is associated with geometrical changes upon an approach of the reacting entities, is relevant for the 6-endo-trig but not for the 5-exo-trig reactions, as seen, for instance, in selective tetrahydrofuran formation from the 4-penten-1-oxyl radical and its 4-methyl derivative. The preference for tetrahydropyran formation in cyclizations of the 4-tert-butyl and the 4-phenyl-4-penten-1-oxyl radical has been attributed to FMO interactions between the terminal carbon atom of the pi bond and the O-radical center thus favoring the 6-endo-trig reaction on the basis of lower transition state energies.

  DOI：

  10.1021/ja049010g
• 作为产物：
  描述：

  4-methyl-4-pentenyl-1-tosylate 、 N-(hydroxy)-4-(p-chlorophenyl)thiazole-2(3H)-thione tetrabutylammonium salt 以 N,N-二甲基甲酰胺 为溶剂， 以67%的产率得到N-(4-methyl-4-penten-1-oxy)-4-(p-chlorophenyl)thiazole-2(3H)thione
  参考文献：
  名称：

  On the 6-endo Selectivity in 4-Penten-1-oxyl Radical Cyclizations

  摘要：

  Regioselectivities in cyclizations of 4-substituted 4-penten-1-oxyl radicals have been investigated in a combined experimental and computational study (density functional theory). The progressive increase of the 6-endo-trig selectivity along the series of 4-substituents H < CH3 < C(CH3)(3) < C6H5 has been interpreted to originate from a balance between strain and FMO interactions. Torsional strain, which is associated with geometrical changes upon an approach of the reacting entities, is relevant for the 6-endo-trig but not for the 5-exo-trig reactions, as seen, for instance, in selective tetrahydrofuran formation from the 4-penten-1-oxyl radical and its 4-methyl derivative. The preference for tetrahydropyran formation in cyclizations of the 4-tert-butyl and the 4-phenyl-4-penten-1-oxyl radical has been attributed to FMO interactions between the terminal carbon atom of the pi bond and the O-radical center thus favoring the 6-endo-trig reaction on the basis of lower transition state energies.

  DOI：

  10.1021/ja049010g

文献信息

• On the 6-<i>e</i><i>ndo</i> Selectivity in 4-Penten-1-oxyl Radical Cyclizations
  作者：Jens Hartung、Rainer Kneuer、Christian Rummey、Gerhard Bringmann

  DOI：10.1021/ja049010g

  日期：2004.9.1

  Regioselectivities in cyclizations of 4-substituted 4-penten-1-oxyl radicals have been investigated in a combined experimental and computational study (density functional theory). The progressive increase of the 6-endo-trig selectivity along the series of 4-substituents H < CH3 < C(CH3)(3) < C6H5 has been interpreted to originate from a balance between strain and FMO interactions. Torsional strain, which is associated with geometrical changes upon an approach of the reacting entities, is relevant for the 6-endo-trig but not for the 5-exo-trig reactions, as seen, for instance, in selective tetrahydrofuran formation from the 4-penten-1-oxyl radical and its 4-methyl derivative. The preference for tetrahydropyran formation in cyclizations of the 4-tert-butyl and the 4-phenyl-4-penten-1-oxyl radical has been attributed to FMO interactions between the terminal carbon atom of the pi bond and the O-radical center thus favoring the 6-endo-trig reaction on the basis of lower transition state energies.