1-Adamantyl propan-2-yl carbonate | 37994-88-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机碳酸及其衍生物
• 英文名称: 1-Adamantyl propan-2-yl carbonate
• 英文别名: 1-adamantyl propan-2-yl carbonate
• CAS: 37994-88-0
• 化学式: C₁₄H₂₂O₃
• 分子量: 238.327
• InChiKey: YWBMWPKLNRNIPD-UHFFFAOYSA-N

物化性质

• 沸点：
  333.7±9.0 °C(Predicted)
• 密度：
  1.10±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  1-金刚烷基氟甲酸 、 异丙醇 生成 1-氟金刚烷 、 1-金刚烷醇 、 1-adamantyl-isopropyl ether 、 1-Adamantyl propan-2-yl carbonate 、 alkaline earth salt of/the/ methylsulfuric acid
  参考文献：
  名称：

  Multiple pathways in the solvolysis of 1-adamantyl fluoroformate

  摘要：

  Reactions of 1-adamantyl fluoroformate in hydroxylic solvents have been studied. In solvents of high ionizing power and relatively low nucleophilicity, such as 2,2,2-trifluoroethanol-water mixtures, the reactions parallel those of 1-adamantyl chloroformate, and only solvolysis-decomposition reaction is observed. However, differing from the reactions of the corresponding chloroformate, in other solvents appreciable amounts of attack at acyl carbon occur, more than 90% in greater-than-or-equal-to 80% aqueous ethanol. Entropies of activation for attack at acyl carbon are considerably more negative than for solvolysis-decomposition. For the solvolysis-decomposition, a Grunwald-Winstein m value of 0.70 is observed. The k(Cl)/k(F) ratios for solvolysis-decomposition are in the range of 10(4)-10(5), suggesting appreciable C-X bond breaking in the transition state of the rate-determining step and arguing against rate-determining formation of a 1-Ad+(OCOX)-ion pair. Attack at acyl carbon is analyzed in terms of the two-term Grunwald-Winstein equation, and sensitivities toward changes in nucleophilicity and ionizing power are identical to those for solvolyses of n-octyl fluoroformate, which are believed to proceed via a tetrahedral intermediate. For each of the major pathways, selectivities toward the components of binary hydroxylic solvents are reported and discussed.

  DOI：

  10.1021/jo00027a046

文献信息

• PRODRUG OF FLUORINE-CONTAINING AMINO ACID
  申请人：Taisho Pharmaceutical Co., Ltd.

  公开号：EP2857385B1

  公开（公告）日：2017-08-02
• US9428483B2
  申请人：——

  公开号：US9428483B2

  公开（公告）日：2016-08-30
• Multiple pathways in the solvolysis of 1-adamantyl fluoroformate
  作者：Dennis N. Kevill、Jin Burm Kyong

  DOI：10.1021/jo00027a046

  日期：1992.1

  Reactions of 1-adamantyl fluoroformate in hydroxylic solvents have been studied. In solvents of high ionizing power and relatively low nucleophilicity, such as 2,2,2-trifluoroethanol-water mixtures, the reactions parallel those of 1-adamantyl chloroformate, and only solvolysis-decomposition reaction is observed. However, differing from the reactions of the corresponding chloroformate, in other solvents appreciable amounts of attack at acyl carbon occur, more than 90% in greater-than-or-equal-to 80% aqueous ethanol. Entropies of activation for attack at acyl carbon are considerably more negative than for solvolysis-decomposition. For the solvolysis-decomposition, a Grunwald-Winstein m value of 0.70 is observed. The k(Cl)/k(F) ratios for solvolysis-decomposition are in the range of 10(4)-10(5), suggesting appreciable C-X bond breaking in the transition state of the rate-determining step and arguing against rate-determining formation of a 1-Ad+(OCOX)-ion pair. Attack at acyl carbon is analyzed in terms of the two-term Grunwald-Winstein equation, and sensitivities toward changes in nucleophilicity and ionizing power are identical to those for solvolyses of n-octyl fluoroformate, which are believed to proceed via a tetrahedral intermediate. For each of the major pathways, selectivities toward the components of binary hydroxylic solvents are reported and discussed.