1,3-Dithian-2-yl-methyl-methylsulfanyl-phenylphosphanium;trifluoromethanesulfonate

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: 1,3-Dithian-2-yl-methyl-methylsulfanyl-phenylphosphanium;trifluoromethanesulfonate
• 化学式: CF₃O₃S*C₁₂H₁₈PS₃
• 分子量: 438.517
• InChiKey: VOXTVXIBRGWOTR-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  4.44
• 重原子数：
  24
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  142
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  1,3-Dithian-2-yl-methyl-methylsulfanyl-phenylphosphanium;trifluoromethanesulfonate 在 三(二甲胺基)膦 作用下， 以 二氯甲烷-D2 为溶剂， 生成 1,3-Dithian-2-yl-methyl-phenylphosphane
  参考文献：
  名称：

  Synthesis and Conformational Behavior of 2-Phosphonio- and 2-Phosphinyl-1,3-dithianes. Operation of the Generalized Anomeric Effect in the S-C-P+ System

  摘要：

  A stereoselective preparation of various 2-phosphinyl- and 2-phosphonio-1,3-dithianes by desulfurization of the appropriate 2-thiophosphoryl-1,3-dithianes was described. The structure of the title compounds was studied by means of H-1, C-13, and P-31 NMR methods. Configurational assignments were also based on chemical correlation and X-ray structure determination. Both the NMR studies of conformationally labile models and equilibration of diastereomeric compounds showed an increased preference of the phosphinyl and phosphonium groups for the axial orientation. Magnitude of the anomeric effect found varies in the range from ca. 6 kJ/mol in phosphines to more than 10 kJ/mol in phosphonium salts. The anomeric effect could stem from the n(s)-sigma*(c-p) hyperconjugative interaction. If phenyl groups are connected with phosphorus, overlap repulsion involving lone electron pairs of the endocyclic sulfur atoms and pi-electrons of phenyl rings should also be taken into account. The reverse anomeric effect was not observed. No manifestation of the exo anomeric effect in 2-phosphinyl-1,3-dithianes was found.

  DOI：

  10.1021/jo00121a043
• 作为产物：
  描述：

  硫化膦,1,3-二硫烷-2-基甲基苯基- 、 三氟甲烷磺酸甲酯 以 二氯甲烷-D2 为溶剂， 反应 0.23h， 生成 1,3-Dithian-2-yl-methyl-methylsulfanyl-phenylphosphanium;trifluoromethanesulfonate
  参考文献：
  名称：

  Synthesis and Conformational Behavior of 2-Phosphonio- and 2-Phosphinyl-1,3-dithianes. Operation of the Generalized Anomeric Effect in the S-C-P+ System

  摘要：

  A stereoselective preparation of various 2-phosphinyl- and 2-phosphonio-1,3-dithianes by desulfurization of the appropriate 2-thiophosphoryl-1,3-dithianes was described. The structure of the title compounds was studied by means of H-1, C-13, and P-31 NMR methods. Configurational assignments were also based on chemical correlation and X-ray structure determination. Both the NMR studies of conformationally labile models and equilibration of diastereomeric compounds showed an increased preference of the phosphinyl and phosphonium groups for the axial orientation. Magnitude of the anomeric effect found varies in the range from ca. 6 kJ/mol in phosphines to more than 10 kJ/mol in phosphonium salts. The anomeric effect could stem from the n(s)-sigma*(c-p) hyperconjugative interaction. If phenyl groups are connected with phosphorus, overlap repulsion involving lone electron pairs of the endocyclic sulfur atoms and pi-electrons of phenyl rings should also be taken into account. The reverse anomeric effect was not observed. No manifestation of the exo anomeric effect in 2-phosphinyl-1,3-dithianes was found.

  DOI：

  10.1021/jo00121a043

文献信息

• Synthesis and Conformational Behavior of 2-Phosphonio- and 2-Phosphinyl-1,3-dithianes. Operation of the Generalized Anomeric Effect in the S-C-P+ System
  作者：Marian Mikolajczyk、Piotr P. Graczyk

  DOI：10.1021/jo00121a043

  日期：1995.8

  A stereoselective preparation of various 2-phosphinyl- and 2-phosphonio-1,3-dithianes by desulfurization of the appropriate 2-thiophosphoryl-1,3-dithianes was described. The structure of the title compounds was studied by means of H-1, C-13, and P-31 NMR methods. Configurational assignments were also based on chemical correlation and X-ray structure determination. Both the NMR studies of conformationally labile models and equilibration of diastereomeric compounds showed an increased preference of the phosphinyl and phosphonium groups for the axial orientation. Magnitude of the anomeric effect found varies in the range from ca. 6 kJ/mol in phosphines to more than 10 kJ/mol in phosphonium salts. The anomeric effect could stem from the n(s)-sigma*(c-p) hyperconjugative interaction. If phenyl groups are connected with phosphorus, overlap repulsion involving lone electron pairs of the endocyclic sulfur atoms and pi-electrons of phenyl rings should also be taken into account. The reverse anomeric effect was not observed. No manifestation of the exo anomeric effect in 2-phosphinyl-1,3-dithianes was found.