n-pentyl chlorosulfite | 62101-23-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: n-pentyl chlorosulfite
• 英文别名: n-Amylchlorsulfinat, Chlorsulfinsaeure-pentylester；chlorosulfurous acid pentyl ester；Chloroschwefligsaeure-pentylester；Pentyl sulfurochloridoite；1-chlorosulfinyloxypentane
• CAS: 62101-23-9
• 化学式: C₅H₁₁ClO₂S
• 分子量: 170.66
• InChiKey: JFKAOBVXROFNLH-UHFFFAOYSA-N

物化性质

• 沸点：
  73 °C(Press: 15 Torr)
• 密度：
  1.1399 g/cm3(Temp: 14.5 °C)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  9
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  45.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  n-pentyl chlorosulfite 以 丙酮 为溶剂， 生成 1-氯戊烷
  参考文献：
  名称：

  Reinvestigation of the SNi reaction. The ionization of chlorosulfites

  摘要：

  The decomposition of alkyl chlorosulfites (ROSOCl) has been investigated both computationally and experimentally. Semiempirical (AM1 and PM3) as well as ab initio (HF/3-21G(*), HF/6-31G*, and MP2(full)/6-31G*//MP2(full)/6-31G*) methods were employed, and the results were confirmed experimentally by NMR spectroscopy. The computations indicated that certain alkyl sulfinyl cations (ROSO+) are stable and might be involved in the decomposition of chlorosulfites. Detection of these ions by H-1 and C-13 NMR spectroscopy in polar solvents such as acetone-d6 and acetonitrile-d3 as well as kinetic studies allowed important conclusions to be drawn about the mechanistic details of the S(N)i reaction. We conclude that primary alkyl chlorosulfites ionize to yield a sulfinyl cation (ROSO+) and Cl-, whereas tertiary chlorosulfites preferentially give a carbenium ion and a chlorosulfinyl anion (OSOCl-). The generation of these ion pairs is facilitated in polar solvents where the rates of decomposition of chlorosulfites are largely accelerated. The decomposition of neopentyl chlorosulfite without rearrangement and the substitution at the bridgehead position of 7,7-dimethylbicyclo[2.2.1]-heptyl 1-chlorosulfite show that the loss Of SO2 from ROSO+ must be accompanied by the attack of the chloride ion from the front side.

  DOI：

  10.1021/jo00062a028
• 作为产物：
  描述：

  戊醇 在 氯化亚砜 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以88%的产率得到n-pentyl chlorosulfite
  参考文献：
  名称：

  Reinvestigation of the SNi reaction. The ionization of chlorosulfites

  摘要：

  The decomposition of alkyl chlorosulfites (ROSOCl) has been investigated both computationally and experimentally. Semiempirical (AM1 and PM3) as well as ab initio (HF/3-21G(*), HF/6-31G*, and MP2(full)/6-31G*//MP2(full)/6-31G*) methods were employed, and the results were confirmed experimentally by NMR spectroscopy. The computations indicated that certain alkyl sulfinyl cations (ROSO+) are stable and might be involved in the decomposition of chlorosulfites. Detection of these ions by H-1 and C-13 NMR spectroscopy in polar solvents such as acetone-d6 and acetonitrile-d3 as well as kinetic studies allowed important conclusions to be drawn about the mechanistic details of the S(N)i reaction. We conclude that primary alkyl chlorosulfites ionize to yield a sulfinyl cation (ROSO+) and Cl-, whereas tertiary chlorosulfites preferentially give a carbenium ion and a chlorosulfinyl anion (OSOCl-). The generation of these ion pairs is facilitated in polar solvents where the rates of decomposition of chlorosulfites are largely accelerated. The decomposition of neopentyl chlorosulfite without rearrangement and the substitution at the bridgehead position of 7,7-dimethylbicyclo[2.2.1]-heptyl 1-chlorosulfite show that the loss Of SO2 from ROSO+ must be accompanied by the attack of the chloride ion from the front side.

  DOI：

  10.1021/jo00062a028

文献信息

• Process for the preparation of phosphorothioate triesters
  申请人：——

  公开号：US20030099981A1

  公开（公告）日：2003-05-29

  A process for the synthesis of a phosphorothioate triester is provided. The process comprises the coupling of an H-phosphonate with an alcohol in the presence of a solution comprising both a coupling agent and a sulfur transfer agent. Preferably, the H-phosphorate and alcohol are protected nucleosides or oligonucleotides.

  提供一种合成磷酸硫酯三酯的过程。该过程包括在存在耦合剂和硫转移剂的溶液中，将H-膦酸酯与醇耦合。最好，H-膦酸酯和醇是受保护的核苷酸或寡核苷酸。
• Synthesis of oligonucleotides
  申请人：Avecia Limited

  公开号：EP1325927A2

  公开（公告）日：2003-07-09

  A process for the synthesis in solution phase of a phosphorothioate triester is provided. The process comprises the solution phase coupling of an H-phosphonate with an alcohol in the presence of a coupling agent to form an H-phosphonate diester. The H-phosphonate diester is oxidised in situ with a sulfur transfer agent to produce the phosphorothioate triester. Preferably, the H-phosphonate and alcohol are protected nucleosides or oligonucleotides. Oligonucleotide H-phosphonates which can be used in the formation of phosphorothioate triesters are also provided.

  本发明提供了一种在溶液相中合成硫代磷酸酯三酯的工艺。该工艺包括在偶联剂存在下，将 H-膦酸盐与醇进行溶液相偶联，形成 H-膦酸盐二酯。H-phosphonate 二酯与硫转移剂原位氧化，生成硫代磷酸酯三酯。H-phosphonate 和醇最好是受保护的核苷或寡核苷酸。还提供了可用于形成硫代磷酸三酯的寡核苷酸 H-膦酸盐。
• Solution phase synthesis of oligonucleotides
  申请人：Avecia Limited

  公开号：US20030083490A1

  公开（公告）日：2003-05-01

  A process for the synthesis in solution phase of a phosphorothioate triester is provided. The process comprises the solution phase coupling of an H-phosphonate with an alcohol in the presence of a coupling agent to form an H-phosphonate diester. The H-phosphonate diester is oxidised in situ with a sulfur transfer agent to produce the phosphorothioate triester. Preferably, the H-phosphonate and alcohol are protected nucleosides or oligonucleotides. Oligonucleotide H-phosphonates which can be used in the formation of phosphorothioate triesters are also provided.

  本发明提供了一种在溶液相中合成硫代磷酸酯三酯的工艺。该工艺包括在偶联剂存在下，将 H-膦酸盐与醇进行溶液相偶联，形成 H-膦酸盐二酯。H-phosphonate 二酯与硫转移剂原位氧化，生成硫代磷酸酯三酯。H-phosphonate 和醇最好是受保护的核苷或寡核苷酸。还提供了可用于形成硫代磷酸三酯的寡核苷酸 H-膦酸盐。
• Libermann,C., Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1960, vol. 250, p. 2223 - 2225
  作者：Libermann,C.

  DOI：——

  日期：——
• Gerrard; Kenyon; Phillips, Journal of the Chemical Society, 1937, p. 155
  作者：Gerrard、Kenyon、Phillips

  DOI：——

  日期：——