trans-2-chloro-3-(triphenylmethyldithio)-1,4-dioxane

• 分子结构分类: 有机化合物 - 苯类化合物 - 三苯基化合物
• 英文名称: trans-2-chloro-3-(triphenylmethyldithio)-1,4-dioxane
• 英文别名: (2S,3S)-2-chloro-3-(trityldisulfanyl)-1,4-dioxane
• 化学式: C₂₃H₂₁ClO₂S₂
• 分子量: 429.004
• InChiKey: FETCTYWPGHYKNI-YADHBBJMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  69.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  1,4-二氧杂-2-己烯 、 氯化三苯基甲基二硫化物 以 二氯甲烷 为溶剂， 反应 7.0h， 以78%的产率得到trans-2-chloro-3-(triphenylmethyldithio)-1,4-dioxane
  参考文献：
  名称：

  Sulfenyl Chloride Chemistry. New Precursors for Diatomic Sulfur Transfer

  摘要：

  When triphenylmethanesulfenyl chloride (1) (or its thio homologue 2) are treated with various bicycles, norbornene (5), or bicyclo[2.2.2]octene (6), dithio adducts 7 and 8 were produced in good isolated yields. Final products were obtained via an episulfide intermediate. The stereochemistry of addition has been determined by X-ray analysis. Treatment of thiosulfenyl chloride 2 (or its dithio homologue 3) with other olefins, cyclopentene (10), cyclohexene (11), or 1,4-dioxene (12), leads to the formation of disulfides (13-15 from 2) and trisulfides (16 and 17 from 3) in high isolated yields (ca. 92%). The structures of 7, 8, and 13-17 were established by H-1 and C-13 NMR and elemental analysis as well as by X-ray determination. When these adducts are warmed with a 1,3-diene 42, they deliver diatomic sulfur-trapped derivatives, cyclic di-49 and tetrasulfide adducts 46. A variety of solvents, temperatures, times, and concentrations were employed to optimize the yield of 46 and 49. The tetrasulfide adduct 46 is quantitatively converted to disulfide 49 with triphenylphosphine; this affords cyclic disulfides in >50% isolated yield from the diene. In addition, evidence has been obtained implicating dithietane intermediate 4.

  DOI：

  10.1021/jo9710792
• 作为试剂：
  描述：

  2,3-二甲基-1,3-丁二烯 在 trans-2-chloro-3-(triphenylmethyldithio)-1,4-dioxane 作用下， 以 乙酸乙酯 为溶剂， 反应 13.0h， 以7%的产率得到1,2-二硫杂-4,5-二甲基-4-环己烯
  参考文献：
  名称：

  Sulfenyl Chloride Chemistry. New Precursors for Diatomic Sulfur Transfer

  摘要：

  When triphenylmethanesulfenyl chloride (1) (or its thio homologue 2) are treated with various bicycles, norbornene (5), or bicyclo[2.2.2]octene (6), dithio adducts 7 and 8 were produced in good isolated yields. Final products were obtained via an episulfide intermediate. The stereochemistry of addition has been determined by X-ray analysis. Treatment of thiosulfenyl chloride 2 (or its dithio homologue 3) with other olefins, cyclopentene (10), cyclohexene (11), or 1,4-dioxene (12), leads to the formation of disulfides (13-15 from 2) and trisulfides (16 and 17 from 3) in high isolated yields (ca. 92%). The structures of 7, 8, and 13-17 were established by H-1 and C-13 NMR and elemental analysis as well as by X-ray determination. When these adducts are warmed with a 1,3-diene 42, they deliver diatomic sulfur-trapped derivatives, cyclic di-49 and tetrasulfide adducts 46. A variety of solvents, temperatures, times, and concentrations were employed to optimize the yield of 46 and 49. The tetrasulfide adduct 46 is quantitatively converted to disulfide 49 with triphenylphosphine; this affords cyclic disulfides in >50% isolated yield from the diene. In addition, evidence has been obtained implicating dithietane intermediate 4.

  DOI：

  10.1021/jo9710792

文献信息

• Sulfenyl Chloride Chemistry. New Precursors for Diatomic Sulfur Transfer
  作者：Imad A. Abu-Yousef、David N. Harpp

  DOI：10.1021/jo9710792

  日期：1998.11.1

  When triphenylmethanesulfenyl chloride (1) (or its thio homologue 2) are treated with various bicycles, norbornene (5), or bicyclo[2.2.2]octene (6), dithio adducts 7 and 8 were produced in good isolated yields. Final products were obtained via an episulfide intermediate. The stereochemistry of addition has been determined by X-ray analysis. Treatment of thiosulfenyl chloride 2 (or its dithio homologue 3) with other olefins, cyclopentene (10), cyclohexene (11), or 1,4-dioxene (12), leads to the formation of disulfides (13-15 from 2) and trisulfides (16 and 17 from 3) in high isolated yields (ca. 92%). The structures of 7, 8, and 13-17 were established by H-1 and C-13 NMR and elemental analysis as well as by X-ray determination. When these adducts are warmed with a 1,3-diene 42, they deliver diatomic sulfur-trapped derivatives, cyclic di-49 and tetrasulfide adducts 46. A variety of solvents, temperatures, times, and concentrations were employed to optimize the yield of 46 and 49. The tetrasulfide adduct 46 is quantitatively converted to disulfide 49 with triphenylphosphine; this affords cyclic disulfides in >50% isolated yield from the diene. In addition, evidence has been obtained implicating dithietane intermediate 4.