CBZ(0.30-0.60g/d)

• 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: CBZ(0.30-0.60g/d)
• 英文别名: [CBZ]_d；CBZ-solution；dihydro-CBZ；racemic CBZ；CBZ10,11E；(2H)-CBZ
• 化学式: C₈H₇O₂
• 分子量: 135.142
• InChiKey: XTXDLRODXSNGHD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  CBZ(0.30-0.60g/d) 以 环己烷 为溶剂， 生成 癸酸苄酯
  参考文献：
  名称：

  Kinetics of Reactions of Cyclopropylcarbinyl Radicals and Alkoxycarbonyl Radicals Containing Stabilizing Substituents: Implications for Their Use as Radical Clocks

  摘要：

  The rate constants for rearrangement of alpha-substituted cyclopropylcarbinyl radicals have been measured by nitroxide radical-trapping (NPT). Those bearing methyl, dimethyl, or cyclopropyl substituents undergo ring opening 2-3 times more slowly than does cyclopropylmethyl radical, but the reaction is essentially irreversible under the conditions used. Phenyl and tert-butoxycarbonyl alpha-substituents retard the rate of ring opening more strongly and enhance the rate of ring closure of the corresponding substituted but-3-enyl radicals. Thus for c-C(3)H(5)CHPh at 60 degrees C, k(ring open) = 5.4 x 10(5) s(-1), k(ring close) = 1.5 x 10(7) s(-1), and the equilibrium favors the ring closed form (K-equil = 0.04). The implications of the possible reversibility of the ring opening of substituted cyclopropylcarbinyl radicals for cyclopropane probe studies of metal hydride reduction and other chemical/biochemical reactions are assessed. Most of the cyclopropylcarbinyl radicals were generated from tert-butyl peroxyglyoxaletes (ROC(O)CO(3)Bu(t)) via alkoxycarbonyl radicals (ROCO). This method allowed the determination of the rate constants for decarboxylation of ROCO when R is t-Bu, PhCH(2), c-C(3)H(5)CMe(2), c-C(3)H(5)CHMe, (c-C3H5)(2)CH, or c-C3H5CHC6H(5).

  DOI：

  10.1021/ja00086a003

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.