trans-2-mercapto-2-methoxy-4-methyl-1,3,2-dioxaphosphorinane | 103959-34-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机硫代磷酸及其衍生物
• 英文名称: trans-2-mercapto-2-methoxy-4-methyl-1,3,2-dioxaphosphorinane
• 英文别名: trans-2-methoxy-2-thioxo-4-methyl-1,3,2-dioxaphosphorinan；trans-2-methoxy-2-thio-4-methyl-1,3,2-dioxaphosphorinane；2-methoxy-4r-methyl-[1,3,2]dioxaphosphinane 2t-sulfide；cis-2-Methoxy-4-methyl-1.3-dioxa-2-phosphorinan-2-thion；trans-2-Methoxy-2-thio-4-methyl-1,3,2-dioxaphosphorinan；cis-2-Methoxy-4-methyl-1,3,2-dioxaphosphorinon-2-thion；(2S*,4S*)-2-Methoxy-4-methyl-[1,3,2]dioxaphosphinane 2-sulfide；(2S,4S)-2-methoxy-4-methyl-2-sulfanylidene-1,3,2λ5-dioxaphosphinane
• CAS: 103959-34-8
• 化学式: C₅H₁₁O₃PS
• 分子量: 182.18
• InChiKey: FHQQAGWHBNMDDE-CDUCUWFYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  59.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  trans-2-mercapto-2-methoxy-4-methyl-1,3,2-dioxaphosphorinane 在 臭氧 作用下， 以 二氯甲烷 为溶剂， 以94%的产率得到cis-2-methoxy-4-methyl-1,3,2-dioxaphosphinane 2-oxide
  参考文献：
  名称：

  A General Method for the Conversion of Thiophosphoryl and Selenophosphoryl Groups into Phosphoryl Groups by Ozone Oxidation

  摘要：

  DOI：

  10.1055/s-1983-30407
• 作为产物：
  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

• The stereochemistry of 2-alkoxy-4-methyl-1,3,2-dioxaphosphorinans
  作者：C. L. Bodkin、P. Simpson

  DOI：10.1039/j29710001136

  日期：——

  The stereochemistry of a series of 2-alkoxy-4-methyl-1,3,2-dioxaphosphorinans has been investigated by n.m.r. and dipole-moment studies. For a given alkoxy-group (MeO, EtO, or PriO), the more-stable member of the isomeric pair adopts a chair conformation, having the trans-configuration, with equatorial methyl and axial alkoxy-group. The less-stable isomers, having the cis-configuration, adopt rapidly

  已经通过核磁共振和偶极矩研究研究了一系列2-烷氧基-4-甲基-1,3,2-二氧杂膦酰喃的立体化学。对于给定的烷氧基的基团（的MeO，环氧乙烷，或Pr我O），同分异构的双更稳定的构件采用了椅式构象中，具有反式-构型，与赤道甲基和轴向烷氧基的基团。具有顺式构型的较不稳定的异构体采用快速翻转的椅子构象。构型稳定性取决于溶剂。
• Stereochemistry of organophosphorus cyclic compounds—I
  作者：M. Mikołajczyk、J. Łuczak

  DOI：10.1016/s0040-4020(01)93865-7

  日期：1972.1

  Geometrical isomers of 2-hydroxy-2-thio-4-methyl-1,3,2-dioxaphosphorinan (I) and 2- hydroxy-2-seleno-4-methyl-1,3,2-dioxaphosphorinan (V) have been prepared stereospecifically by : (a) demethylation of cis- and trans-2-methoxy-2-thio-4-methyl-1,3,2-dioxaphosphorinan (IV) and 2-methoxy- 2-seleno-4-methyl-1,3,2-dioxaphosphorinan (VI) with trimethylamine, and (b) addition of sulphur and selenium to geometrical

  2-羟基-2-硫代-4-甲基-1,3,2-二氧杂磷酰胺基（I）和2-羟基-2-硒代-4-甲基-1,3,2-二氧杂磷酸酯（V）的几何异构体立体定向地通过以下方法制备：（a）顺式和反式-2-甲氧基-2-硫代-4-甲基-1,3,2-二氧杂磷酰胺（IV）和2-甲氧基-2-硒代-4-甲基-1的甲基化，3，2-二氧杂磷酰胺（VI）与三甲胺，和（b）将硫和硒加到2-氢-2-氧代-4-甲基-1，3，2-二氧杂磷酰胺（VIII）的几何异构体中。已经证明，将硫和硒添加到P（O）H基团中会继续保持P原子上的构型。
• Stereochemistry of organophosphorus cyclic compounds—III
  作者：W. Stec、A. Łopusiński

  DOI：10.1016/0040-4020(73)80007-9

  日期：1973.1

  On the basis of chemical transformations and spectroscopic data the cis- and trans-geometry was assigned to the previously reported diastereoisomeric 2-N-phenylamino-2-oxo-4-methyl-1,3,2-dioxaphosphorinans (1). The addition of phenyl azide to cyclic phosphite (3) as well as the reaction of the resulting adduct (4) with carbon disulphide or benzoic acid takes place with overall retention of configuration

  根据化学转化和光谱数据，将顺式和反式几何结构分配给先前报道的非对映异构体2-N-苯基氨基-2-氧代-4-甲基-1,3,2-二氧杂磷烷基膦酸酯（1）。在环亚磷酸酯（3）中加入叠氮化苯，以及所得的加合物（4）与二硫化碳或苯甲酸的反应在P原子上总体上保持构型。在两个-1,3,2- dioxaphosphorinanyl环系统的构象顺式和-反式- 1建议。
• Krawczyk, Ewa; Skowronska, Aleksandra; Michalski, Jan, Journal of the Chemical Society. Perkin transactions I, 1994, # 1, p. 89 - 100
  作者：Krawczyk, Ewa、Skowronska, Aleksandra、Michalski, Jan

  DOI：——

  日期：——
• Organophosphorus compounds: the first applications of sulfuryl chloride fluoride SO2FCl in synthesis
  作者：Andrzej Lopusinski、Jan Michalski

  DOI：10.1021/ja00365a054

  日期：1982.1