diethoxyoxophosphoranesulfenyl chloride | 1186-08-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: diethoxyoxophosphoranesulfenyl chloride
• 英文别名: O,O-diethyl chlorothiophosphonate；chlorothiophosphoric acid diethyl ester；O,O'-diethyl-phosphoric hypochlorous thioanhydride；chloro-diethoxyphosphoryl-sulfane；Chlor-diaethoxyphosphoryl-sulfan；diethylchlorothiophosphonate；O,O-diethyl S-chloro thiophosphate；diethoxyphosphoryl thiohypochlorite
• CAS: 1186-08-9
• 化学式: C₄H₁₀ClO₃PS
• 分子量: 204.614
• InChiKey: LIMPRBWQNDVVEY-UHFFFAOYSA-N

物化性质

• 沸点：
  61-62 °C(Press: 0.4 Torr)
• 密度：
  1.27031 g/cm3(Temp: 25 °C)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  10
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  60.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  diethoxyoxophosphoranesulfenyl chloride 在 三(二甲胺基)膦 作用下， 生成 氯磷酸二乙酯
  参考文献：
  名称：

  Skowronska, Aleksandra; Krawczyk, Ewa; Burski, Janusz, Phosphorus and Sulfur and the Related Elements, 1983, vol. 18, p. 233 - 236

  摘要：

  DOI：
• 作为产物：
  描述：

  Thiophosphorsaeure-tris-triaethylsilylester 在 磺酰氯 作用下， 以 二氯甲烷 为溶剂， 反应 0.33h， 生成 diethoxyoxophosphoranesulfenyl chloride
  参考文献：
  名称：

  高度取代的共轭三烯炔的通用和方便合成

  摘要：

  描述了一种方便合成高度取代的非线性共轭三烯炔。我们的策略涉及容易获得的硫代磷酸盐与二烯的钠衍生物的反应，其中形成新的单碳-碳键和双碳-碳键。

  DOI：

  10.1055/s-2003-38078
• 作为试剂：
  描述：

  trans-2-Methoxy-4-methyl-1,3,2-dioxaphosphorinan 在 diethoxyoxophosphoranesulfenyl chloride 作用下， 以 二氯甲烷 为溶剂， 生成 trans-2-mercapto-2-methoxy-4-methyl-1,3,2-dioxaphosphorinane
  参考文献：
  名称：

  Reaction of tricoordinate phosphorus compounds with organophosphorus pseudohalogens. 1. Desulfurization and deoxygenation of oxophosphoranesulfenyl chlorides. Scope and mechanism

  摘要：

  The reaction of oxophosphoranesulfenyl chlorides RR'P(O)SCl 2 with P(III) compounds has been investigated. Its mechanistic features have been elucidated by variable-temperature P-31 NMR spectroscopy and stereochemical changes at P(IV) and P(III) phosphorus centers. These studies show that in all cases phosphonium intermediates containing the sulfur bridge >P(O)-S-P+ less than or similar to Cl- are formed. Depending on electronic and steric factors and reaction conditions, this primary phosphonium salt either decomposes by nucleophilic attack of the chloride counterion on the phosphoryl center (desulfurization pathway) or is transformed into the isomeric phosphonium salt >P(S)-O-P+ less than or similar to Cl-. The latter decomposes by the attack of the chloride anion on the thiophosphoryl center (deoxygenation pathway). P-31 NMR studies fully corroborated the observed stereochemical changes.

  DOI：

  10.1021/jo00044a035

文献信息

• A general convenient synthesis of conjugated dieneynes
  作者：Iwona Maciągiewicz、Piotr Dybowski、Aleksandra Skowrońska

  DOI：10.1016/s0022-328x(01)01275-x

  日期：2002.2

  A convenient synthesis of dieneynes 1 is described. Our strategy involves reaction of readily available thiophosphates with sodium acetylides, in which new single and double carbon–carbon bonds are formed.

  描述了二烯酮1的方便合成。我们的策略涉及容易获得的硫代磷酸酯与乙炔酸钠的反应，在其中形成新的单碳和双碳-碳键。
• A Convenient Synthesis of Episulfides and Their Conversion into Alkenes
  作者：Piotr Dybowski、Aleksandra Skowrońska

  DOI：10.1055/s-1997-1329

  日期：1997.10

  A convenient and stereoselective synthesis of episulfides based on the reaction of readily available S-(β-oxoalkyl) thiophosphate with sodium borohydride and their conversion into alkenes is described.

  描述了一种方便且立体选择性的episulfides合成方法，该方法基于易得的S-(β-氧烷基)硫代磷酸盐与氢化钠的反应以及它们转化为烯烃的过程。
• A new strategy for the stereoselective synthesis of olefins
  作者：Piotr Dybowski、Aleksandra Skowrońska

  DOI：10.1016/s0040-4039(00)92177-4

  日期：1991.1

  Highly stereoselective conversion of ketones into (Z)-olefins, via intermediate S-(β-oxoalkyl)thiophosphates and their seleno analogues is described.

  描述了经由中间体S-（β-氧代烷基）硫代磷酸酯及其硒代类似物将酮高度立体选择性地转化为（Z）-烯烃。
• Novel synthesis of symmetrical tetra-alkyl monothiopyrophosphates
  作者：Aleksandra Skowrońska、Roman Dembiński、Rafał Kamiński、Jan Michalski

  DOI：10.1016/s0040-4039(00)95581-3

  日期：——

  The novel highly efficient synthesis of sym-tetra-alkyl monothiopyrophosphates (RO)2P(O)SP(O) (OR′)2 based on the condensation of dialkoxyoxophosphoranesulphenyl chlorides with dialkyltrimethylsilyl phosphites is described.

  描述了基于二烷氧基氧代膦酰基磺酰苯氯与亚磷酸二烷基三甲基甲硅烷基酯缩合的新型高效合成的对四烷基单硫代焦磷酸盐（RO）2 P（O）SP（O）（OR'）2。
• An expedient, stereoselective synthesis of highly functionalized cyclic compounds
  作者：Ewa Krawczyk、Krzysztof Owsianik、Aleksandra Skowrońska、Michał Wieczorek、Wiesław Majzner

  DOI：10.1039/b207700k

  日期：——

  New thiophosphates containing functionalized cyclic ketone derivatives as ligands have been stereoselectively prepared from readily available starting materials. Full axial stereoselectivity of the NaBH4 reduction of the carbonyl group in thiophosphates providing the corresponding thiols or sulfides has been demonstrated. The sulfides have been transformed into new functionalized cyclic Baylis–Hillman type adducts of defined configuration. The prospects for the useful synthetic application of these adducts appear to be very promising.

  含有官能化环酮衍生物作为配体的新硫磷酸酯已从易得的起始材料中立体选择性地合成。已经证明，NaBH4对硫磷酸酯中羰基的还原反应具有完全的轴向立体选择性，生成相应的硫醇或硫化物。这些硫化物已被转化为具有明确定型的新型官能化环状Baylis–Hillman型加合物。这些加合物在有用合成应用方面的前景看起来非常可观。