1-O-[(2,2-diphenylcyclopropyl)methyl] 2-O-(2-sulfanylidenepyridin-1-yl) oxalate | 202815-02-9

• 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: 1-O-[(2,2-diphenylcyclopropyl)methyl] 2-O-(2-sulfanylidenepyridin-1-yl) oxalate
• CAS: 202815-02-9
• 化学式: C₂₃H₁₉NO₄S
• 分子量: 405.474
• InChiKey: GYXSOHIVXNSNNG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  29
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  87.9
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1-O-[(2,2-diphenylcyclopropyl)methyl] 2-O-(2-sulfanylidenepyridin-1-yl) oxalate 在 三正丁基氢锡 作用下， 以 四氢呋喃 为溶剂， 生成 1,1'-(丁-1-烯-4,4-二基)二苯 、 (2,2-Diphenylcyclopropyl)methyl formate
  参考文献：
  名称：

  Absolute Rate Constants for Alkoxycarbonyl Radical Reactions

  摘要：

  PTOC oxalates (anhydrides of an oxalic acid monoester and N-hydroxypyridine-2-thione) were used in laser flash photolysis (LFP) kinetic studies, Irradiation of the PTOC oxalates gave the following alkoxycarbonyl radicals ROC(.) = O: 2a, R = PhCH2; 2b, R = (trans-2-phenylcyclopropyl)methyl; 2c, R = (2,2-diphenylcyclopropyl)methyl. Rate constants for decarboxylation of radical 2a measured by LFP were in agreement with those obtained previously by indirect kinetic methods, Rate constants for decarboxylation of radical 2c were measured by LFP over the temperature range 3-48 degrees C, the reaction is described by log k = 12.2-9.6/2.3RT (kcal/mol). Reactions of Bu3SnH with radical 2c produced from the corresponding phenylseleno carbonate gave inconsistent kinetic results apparently due to the production of small amounts of PhSeH that reacted rapidly with 2c. An approximate rate constant at 2 degrees C for reaction of Bu3SnH with 2C produced from the PTOC oxalate was obtained, Tin hydride. reacts with the alkoxycarbonyl radical approximately 1 order of magnitude less rapidly than it reacts with alkyl radicals. Rate constants for 5-exo cyclizations of simple alkoxycarbonyl radicals were estimated from previous results and the approximate rate constant for tin hydride trapping; the cyclizations are slightly Easter than 5-exo cyclizations of structurally related alkyl radicals.

  DOI：

  10.1021/jo971774+
• 作为产物：
  描述：

  2,2-diphenylcyclopropylmethanol 在 4-二甲氨基吡啶 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 25.5h， 生成 1-O-[(2,2-diphenylcyclopropyl)methyl] 2-O-(2-sulfanylidenepyridin-1-yl) oxalate
  参考文献：
  名称：

  Absolute Rate Constants for Alkoxycarbonyl Radical Reactions

  摘要：

  PTOC oxalates (anhydrides of an oxalic acid monoester and N-hydroxypyridine-2-thione) were used in laser flash photolysis (LFP) kinetic studies, Irradiation of the PTOC oxalates gave the following alkoxycarbonyl radicals ROC(.) = O: 2a, R = PhCH2; 2b, R = (trans-2-phenylcyclopropyl)methyl; 2c, R = (2,2-diphenylcyclopropyl)methyl. Rate constants for decarboxylation of radical 2a measured by LFP were in agreement with those obtained previously by indirect kinetic methods, Rate constants for decarboxylation of radical 2c were measured by LFP over the temperature range 3-48 degrees C, the reaction is described by log k = 12.2-9.6/2.3RT (kcal/mol). Reactions of Bu3SnH with radical 2c produced from the corresponding phenylseleno carbonate gave inconsistent kinetic results apparently due to the production of small amounts of PhSeH that reacted rapidly with 2c. An approximate rate constant at 2 degrees C for reaction of Bu3SnH with 2C produced from the PTOC oxalate was obtained, Tin hydride. reacts with the alkoxycarbonyl radical approximately 1 order of magnitude less rapidly than it reacts with alkyl radicals. Rate constants for 5-exo cyclizations of simple alkoxycarbonyl radicals were estimated from previous results and the approximate rate constant for tin hydride trapping; the cyclizations are slightly Easter than 5-exo cyclizations of structurally related alkyl radicals.

  DOI：

  10.1021/jo971774+

文献信息

• Absolute Rate Constants for Alkoxycarbonyl Radical Reactions
  作者：Pavel A. Simakov、Felix N. Martinez、John H. Horner、Martin Newcomb

  DOI：10.1021/jo971774+

  日期：1998.2.1

  PTOC oxalates (anhydrides of an oxalic acid monoester and N-hydroxypyridine-2-thione) were used in laser flash photolysis (LFP) kinetic studies, Irradiation of the PTOC oxalates gave the following alkoxycarbonyl radicals ROC(.) = O: 2a, R = PhCH2; 2b, R = (trans-2-phenylcyclopropyl)methyl; 2c, R = (2,2-diphenylcyclopropyl)methyl. Rate constants for decarboxylation of radical 2a measured by LFP were in agreement with those obtained previously by indirect kinetic methods, Rate constants for decarboxylation of radical 2c were measured by LFP over the temperature range 3-48 degrees C, the reaction is described by log k = 12.2-9.6/2.3RT (kcal/mol). Reactions of Bu3SnH with radical 2c produced from the corresponding phenylseleno carbonate gave inconsistent kinetic results apparently due to the production of small amounts of PhSeH that reacted rapidly with 2c. An approximate rate constant at 2 degrees C for reaction of Bu3SnH with 2C produced from the PTOC oxalate was obtained, Tin hydride. reacts with the alkoxycarbonyl radical approximately 1 order of magnitude less rapidly than it reacts with alkyl radicals. Rate constants for 5-exo cyclizations of simple alkoxycarbonyl radicals were estimated from previous results and the approximate rate constant for tin hydride trapping; the cyclizations are slightly Easter than 5-exo cyclizations of structurally related alkyl radicals.