(1,1,3,3-2H4)-2-propanol | 112925-56-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1,1,3,3-2H4)-2-propanol
• CAS: 112925-56-1
• 化学式: C₃H₈O
• 分子量: 64.0642
• InChiKey: KFZMGEQAYNKOFK-LNLMKGTHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.39
• 重原子数：
  4.0
• 可旋转键数：
  2.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  20.23
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  (1,1,3,3-2H4)-2-propanol 在 三溴化磷 作用下， 反应 17.0h， 以34%的产率得到(1,1,3,3-2H4)-2-bromopropane
  参考文献：
  名称：

  Regiospecificity and isotope effects associated with the methyl-methylene eliminations in the enzyme-catalyzed biosynthesis of (R)- and (S)-limonene

  摘要：

  [8-H-3]-, [8,8,9,9-H-2(4)]-, and [1-H-3,8,9-H-2(6)] geranyl diphosphates (1-t, 1-d4, and 1-d6,t) were synthesized and used as substrates for several monoterpene cyclases to determine the regiospecificity and isotope effects attending the terminating proton transfers in the enzyme-catalyzed biosynthesis of (R)- and (S)-limonene. Degradation of enantiomeric [H-3]limonenes produced by cyclization Of 1-t with the (+)- and (-)-pinene cyclases (synthases) from Salvia officinalis demonstrated that the eliminations occur at both the cis- (55-65%) and trans-methyl (45-35%) groups. In contrast, the terminating eliminations in the formation of (+)- and (-)-limonene catalyzed by limonene cyclasses from Citrus sinensis and Perilla frutescens, respectively, were shown by degradation to occur exclusively (greater-than-or-equal-to 97-98%) at the cis terminal methyl group. The intramolecular isotope effects for the methyl-methylene elimination in limonene biosynthesis catalyzed by (+)- and (-)-pinene cyclases from S. officinalis were found to be k(H)/k(D) = 2.3 +/- 0.2 and 5.9 +/- 0.5, respectively, by GC/MS determinations of [H-2]-limonene derived from enzymatic cyclizations of 1-d4. Similar experiments with (-)-limonene cyclase from Mentha spicata resulted in k(H)/k(D) = 4.0 +/- 0.4. Incubations of 1-d6,t with pinene and bornyl PP cyclases from S. officinalis exhibited significant remote isotope effects (k(H)/k(D) = 1.16-1.27) on the total rate of monoterpene formation which suggest that the initial cyclization step of the enzyme-bound linalyl diphosphate intermediate is an important component of the overall rate of the enzymatic reactions. The isotope effects on the partitioning of the alpha-terpinyl carbocation intermediate between bicyclization and elimination to limonene were determined from the effects of deuterium substitution on the product ratios derived from enzymatic cyclization of 1-d6,t. The small size of these product isotope effects (k(H)/k(D)) = 1.2-1.7) is attributed to a conformational inversion of the alpha-terpinyl ion to a half-chair conformer prior to proton elimination to limonene, thereby rendering the bicyclizations relatively immune to the intrinsic deuterium isotope effect. The regiospecific proton transfers from the cis terminal methyl group effected by the limonene cyclases from Citrus and Perilla are attributed to the minimization of charge separation in the transition state.

  DOI：

  10.1021/jo00067a037
• 作为产物：
  描述：

  1,3-二氯丙酮-D4 在 lithium aluminium tetrahydride 作用下， 生成 (1,1,3,3-2H4)-2-propanol
  参考文献：
  名称：

  n-和i-C3 H7 Fe（OH）+配合物在H / D平衡中组成上等效的甲基的固有不对称性。

  摘要：

  在Fe +介导的丙醇脱水中进行的正丙基⇄异丙基异构化过程中，瞬态形成的结构相同的甲基保持不等价。通过使用串联质谱法检查Fe +与一组选择性氘化的丙醇的亚稳络合物中的H / D平衡，可以解决β氢转移步骤的可逆性。

  DOI：

  10.1002/1521-3773(20010716)40:14<2708::aid-anie2708>3.0.co;2-1