2-Chloro-5,5-dimethyl-1,3-dithiane | 167866-78-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 硫杂环丁烷
• 英文名称: 2-Chloro-5,5-dimethyl-1,3-dithiane
• CAS: 167866-78-6
• 化学式: C₆H₁₁ClS₂
• 分子量: 182.738
• InChiKey: XBKACWZXWOISQZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  50.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-Chloro-5,5-dimethyl-1,3-dithiane 、 4-二(4-二甲基氨基苯基)膦基-N,N-二甲基苯胺 以 苯 为溶剂， 以60.2%的产率得到Tris<4-(dimethylamino)phenyl>(5,5-dimethyl-1,3-dithian-2-yl)phosphonium chloride
  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：

  5,5-Dimethyl-1,3-dithiane 在 N-氯代丁二酰亚胺 作用下， 以 苯 为溶剂， 反应 0.33h， 生成 2-Chloro-5,5-dimethyl-1,3-dithiane
  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

• MIKOLAJCZVK, MARIAN;GRACZYK, PIOTR;WIECZOREK, MICHAL W.;BUJACZ, GRZEGORZ, ANGEW. CHEM., 103,(1991) N, C. 604-606
  作者：MIKOLAJCZVK, MARIAN、GRACZYK, PIOTR、WIECZOREK, MICHAL W.、BUJACZ, GRZEGORZ

  DOI：——

  日期：——
• Mikolajczyk, Marian; Graczyk, Piotr; Wieczorek, Michael W., Angewandte Chemie, 1991, vol. 103, # 5, p. 604 - 606
  作者：Mikolajczyk, Marian、Graczyk, Piotr、Wieczorek, Michael W.、Bujacz, Grzegorz

  DOI：——

  日期：——