1,2,2-trimethylcyclopropanemethanol | 133753-26-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,2,2-trimethylcyclopropanemethanol
• 英文别名: (1,2,2-Trimethylcyclopropyl)methanol
• CAS: 133753-26-1
• 化学式: C₇H₁₄O
• 分子量: 114.188
• InChiKey: MTMSHFLYHMLPTP-UHFFFAOYSA-N

物化性质

• 沸点：
  131.2±8.0 °C(Predicted)
• 密度：
  0.887±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  8
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1,2,2-trimethylcyclopropanemethanol 、 乙酰氯 生成 (1,2,2-Trimethylcyclopropyl)methylacetat
  参考文献：
  名称：

  Acetolysis of (3,5,5-trimethyl-1-pyrazolin-3-yl)methyl p-bromobenzenesulfonate. Elimination of nitrogen from an azo compound via cationic intermediates

  摘要：

  DOI：

  10.1021/ja00836a024
• 作为产物：
  描述：

  1,1,2,2-四甲基环丙烷 在 cytochrome P₄₅₀ reductase 、 cytochrome b5 、 rat CYP₂B₁ enzyme 、 还原型辅酶II(NADPH)四钠盐 作用下， 反应 0.5h， 生成 1,2,2-trimethylcyclopropanemethanol
  参考文献：
  名称：

  细胞色素P450机制的分子探针。氧捕获底物自由基中间体。

  摘要：

  诊断底物四甲基环丙烷 (TMCP) 已被重新检查为三种药物和异生素代谢细胞色素 P450 酶（人 CYP2E1、CYP3A4 和大鼠 CYP2B1）的底物。在所有情况下，主要的羟基化产物是未重排的伯醇以及少量的重排的叔醇。值得注意的是，还观察到另一种开环产物双丙酮醇。 CYP2E1 该产品占总营业额的 20%。双丙酮醇也被检测为 TMCP 的产物，使用仿生模型催化剂 FeTMPyP，但不使用钌卟啉催化剂。根据重排和未重排产物的比例确定中间自由基的寿命，CYP2E1、CYP3A4和CYP2B1分别为120、13和1ps，对应的反弹率为0.9×10(10)s(-1)、7.2× 10(10)s(-1)和1.0×10(12)s(-1)。对于模型铁卟啉，FeTMPyP，测得自由基寿命为81ps，反弹率为1.2×10(10)s(-1)。这些表观自由基寿命与早期报道的各种 CYP 酶和自由基时钟底物一致，然而，大量的双丙酮醇与

  DOI：

  10.1016/j.abb.2010.11.001

文献信息

• A radical clock investigation of microsomal cytochrome P-450 hydroxylation of hydrocarbons. Rate of oxygen rebound
  作者：Vincent W. Bowry、K. U. Ingold

  DOI：10.1021/ja00015a025

  日期：1991.7

  A number of alkyl-substituted cyclopropanes for which the rates of ring opening of the corresponding cyclopropylcarbinyl radicals have been determined (see preceding paper in this issue) have been used as substrates for hydroxylation by phenobarbital-induced, rat liver microsomal cytochrome P-450 at 37-degrees-C. Three of these compounds gave both ring-closed and ring-opened alcohols, thus allowing the rate constant, k(OH), for ''oxygen rebound'' onto the corresponding carbon-centered radicals to be determined. In particular, both trans- (1bH) and cis- (1cH) 1,2-dimethylcyclopropane gave 4-penten-2-ol (2bOH) and 2-methyl-3-buten-1-ol (3bOH) together with the corresponding trans- (1bOH) or cis-(1cOH) 2-methylcyclopropanemethanols. Of much greater importance, for both 1bH and 1cH the ratios of the yields of the secondary-to-primary ring-opened alcohols, i.e., [2bOH]/[3bOH], were the same, within experimental error as the ratio of the rates of ring opening of the corresponding trans- (1b.) and cis- (1c.) methylcyclopropylmethyl radicals in solution at 37-degrees-C. This indicates that when lb. and lc. are formed from their parent hydrocarbons by H-atom abstraction in the hydrophobic pocket of cytochrome P-450 they are not detectably constrained in their subsequent reactions by their unusual environment. From the ratio of the yields of the unrearranged alcohol to each of the rearranged alcohols we calculate k(OH) values of 1.5 and 1.6 x 10(10) s-1 for lbH as substrate and values of 1.9 and 1.8 x 10(10) s-1 for 1cH as substrate. Consistent with these values we have obtained k(OH) = 2.2 x 10(10) s-1 for bicyclo[2.1.0]pentane as substrate. Substrates such as methylcyclopropane and 1,1-dimethylcyclopropane, for which the corresponding cyclopropylmethyl radicals undergo relatively slow ring opening, yielded only the ring-closed alcohols on oxidation with cytochrome P-450. 1,1,2,2-Tetramethylcyclopropane gave only a trace of a ring-opened alcohol, corresponding to k(OH) = 2.5 x 10(11) s-1 for this substrate. Hexamethylcyclopropane gave no detectable ring-opened alcohol from which observation a limit for k(OH) > 5 X 10(11) s-1 can bc calculated. Possible explanations for the unexpected behavior of these last two, relatively bulky, substrates are discussed.