(R)P(+)-O-ethyl phenylphosphonothioic acid | 70269-57-7

• 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: (R)P(+)-O-ethyl phenylphosphonothioic acid
• 英文别名: (R)_P(+)-O-ethyl phenylphosphonothioic acid；(R_P)-O-ethyl phenylphosphonothioic acid；(R)-O-ethyl hydrogen phenylphosphonothioate；(RP)-O-ethyl phenylphosphonothioic acid；(R)-O-ethyl phenylphosphonothioic acid
• CAS: 70269-57-7
• 化学式: C₈H₁₁O₂PS
• 分子量: 202.214
• InChiKey: HBFNIDYFNYYMOB-LLVKDONJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.65
• 重原子数：
  12.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  29.46
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (R)P(+)-O-ethyl phenylphosphonothioic acid 在 草酰氯 作用下， 以 四氯化碳 为溶剂， 反应 0.5h， 以68%的产率得到(S)-(+)-O-ethyl phenylphosphonochloridothioate
  参考文献：
  名称：

  Hirashima, Akinori; Eto, Morifusa, Agricultural and Biological Chemistry, 1983, vol. 47, # 4, p. 829 - 838

  摘要：

  DOI：
• 作为产物：
  描述：

  二乙基苯基硫代磷酸酯 在 sodium hydroxide 、 R(+)-alpha-甲基苄胺 作用下， 以 乙醚 、 乙醇 为溶剂， 反应 25.0h， 生成 (R)P(+)-O-ethyl phenylphosphonothioic acid
  参考文献：
  名称：

  一个新的氢键基序，用于外消旋的1-苯基乙胺衍生物与对映体纯的O-乙基苯基膦硫酸的非对映体盐中的手性识别。

  摘要：

  对映体纯的膦酰基硫代酸通过其非对映异构性结晶，对于外消旋的1-苯基乙胺衍生物显示出独特且优异的手性识别能力，这归因于其对映异构性。由氢键和CH / pi相互作用引起的球形分子簇在不易溶的非对映异构盐中以高度对称性聚集。

  DOI：

  10.1021/ol0483145

文献信息

• New Synthesis of Optically Active<i>O</i>-Aryl<i>O</i>-Ethyl Phenylphosphonothionates
  作者：Hiromichi YOSHIKAWA

  DOI：10.1271/bbb.63.424

  日期：1999.1

  The mixed anhydride method was applied to synthesize O-aryl O-ethyl phenylphosphonothionate. The reaction of O, O-diethyl phosphorochloridate with O-ethyl phenylphosphonothioic acid afforded O, O-diethyl phosphoric O-ethyl phenylphosphonothioic anhydride in a good yield. This anhydride was converted to O-aryl O-ethyl phenylphosphonothionates by reacting with the appropriate sodium phenoxide. This esterification

  采用混合酸酐法合成了O-芳基O-乙基苯基膦酸酯。O，O-二乙基磷酰氯与O-乙基苯基膦酰硫代酸的反应以良好的收率得到了O，O-二乙基磷酸O-乙基苯基膦酰硫代酸酐。通过与适当的苯甲酸钠反应，将该酸酐转化为O-芳基O-乙基苯基膦酸酯。该酯化反应没有外消旋作用，产生了光学纯的O-乙基O-（4-硝基苯基）苯基膦酰硫酸酯（EPN）和O-（4-氰基苯基）O-乙基苯基膦酸酯（氰基磷）。
• Enantiopure <i>O</i>-Substituted Phenylphosphonothioic Acids:  Chiral Recognition Ability during Salt Crystallization and Chiral Recognition Mechanism
  作者：Yuka Kobayashi、Fumi Morisawa、Kazuhiko Saigo

  DOI：10.1021/jo052020v

  日期：2006.1.1

  The chiral recognition ability of enantiopure O-methyl, O-ethyl, O-propyl, and O-phenyl phenylphosphonothioic acids (1a−d) for various kinds of racemic amines during salt crystallization and the chiral recognition mechanism were thoroughly investigated. The chiral recognition abilities of enantiopure 1a−d for a wide variety of racemic amines varied in a range of 6 to >99% enantiomeric selectivity.

  深入研究了对映体纯的O-甲基，O-乙基，O-丙基和O-苯基苯基膦硫酸（1a - d）在盐结晶过程中对各种外消旋胺的手性识别能力和手性识别机理。对映体1a - d对多种外消旋胺的手性识别能力在6％至> 99％对映体选择性范围内变化。沉积的非水溶性非对映异构盐分为两类：棱柱形和针状晶体；第二类为非晶体。棱柱型晶体由球状分子簇组成，而存在一个2 1柱状针状晶体。与在手性伯胺与手性羧酸的难溶非对映异构盐晶体中相似的2 1柱的一般观察结果相反，球形分子簇是非常独特的氢键基序，从未在非对映异构盐晶体中构建。当难溶的非对映异构盐是棱柱型晶体时，总是可以实现出色的手性识别。发现与1a - d的手性识别度，难溶非对映异构盐的晶体形状和氢键基序（分子簇/ 2 1柱）之间存在显着相关性。通过分子簇和2的手性识别机制在X射线晶体学分析的基础上，对1列的形成进行了详细讨论。
• Chemoselective and Stereoselective Alcoholysis of Binaphthyl Phosphonothioates: Straightforward Access to Both Stereoisomers of Biologically Relevant <i>P</i>-Stereogenic Phosphonothioates
  作者：Kazuma Kuwabara、Yuuki Maekawa、Mao Minoura、Toshifumi Maruyama、Toshiaki Murai

  DOI：10.1021/acs.joc.0c00687

  日期：2020.11.20

  P-Stereogenic phosphonothioates have attracted great attention due to their potent biological activities as analogues of phosphoric acids and phosphorothioates. We demonstrate here straightforward access to P-stereogenic phosphonothioates through the use of binaphthyl phosphonothioates as a chiral template. The first-step alcoholysis of binaphthyl phosphonothioates proceeded via a transfer of the axial chirality of a binaphthyl group to the central chirality of a phosphorus atom to give only monoalcohol adducts with moderate to excellent diastereoselectivities. Further alcoholysis of the obtained products in the presence of a small excess of alcohol and base proceeded with complete elimination of a binaphthyl group to give the corresponding P-stereogenic phosphonothioates with high enantiomeric excess. A DFT study of the reaction mechanisms in first-step alcoholysis indicated that the coordination of a sulfur atom to a sodium cation is the key factor in controlling the diastereoselectivities. This method can be applied to prepare both stereoisomers of a G6P analogue with high diastereomeric purity.
• JP2005/75760
  申请人：——

  公开号：——

  公开（公告）日：——
• HIRASHIMA, AKINORI;ETO, MORIFUSA, AGR. AND BIOL. CHEM., 1983, 47, N 4, 829-838
  作者：HIRASHIMA, AKINORI、ETO, MORIFUSA

  DOI：——

  日期：——