1,4-dithiane 1-oxide | 19087-70-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二噻烷
• 英文名称: 1,4-dithiane 1-oxide
• 英文别名: 1λ⁴-dithiane 1-oxide；1,4-Dithiane monosulfoxide；1,4-dithiane-1-oxide；1,4-dithian-1-oxide；[1,4]dithiane-1-oxide；[1,4]Dithian-1-oxid；1,4-Dithiane, 1-oxide
• CAS: 19087-70-8
• 化学式: C₄H₈OS₂
• 分子量: 136.239
• InChiKey: VBDLSQFQIUGPSA-UHFFFAOYSA-N

物化性质

• 熔点：
  125-126 °C
• 沸点：
  357.8±31.0 °C(Predicted)
• 密度：
  1.35±0.1 g/cm3(Predicted)
• 保留指数：
  1389.4

计算性质

• 辛醇/水分配系数(LogP)：
  -0.3
• 重原子数：
  7
• 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：
  61.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1,4-dithiane 1-oxide 在 potassium permanganate 、 magnesium sulfate 作用下， 以 丙酮 为溶剂， 反应 1.5h， 生成 1,4-dithiacyclohexane 1,1-dioxide
  参考文献：
  名称：

  Comparison of the photooxidations of 1,5-dithiacyclooctane, 1,4-dithiane, and pentamethylene sulfide. Another example of remote participation during photooxidation at sulfur?

  摘要：

  The photooxidations of 1,5-dithiacyclooctane (1,5-DTCO), 1,4-dithiane, and pentamethylene sulfide have been compared. The photooxidation of 1,5-DTCO differs significantly from the other substrates in several respects: (1) the ratio of chemical quenching to total quenching of singlet oxygen during photooxidation of 1,5-DTCO is 70%, in comparison to 5% for 1,4-dithiane and 2.9% for pentamethylene sulfide; (2) a sulfone is produced in all of the photooxidations except in that of 1,5-DTCO; and (3) the value of k(T) is larger for 1,5-DTCO than for any previously reported sulfide. A novel sulfur-sulfur interaction during photooxidation of 1,5-DTCO is utilized in order to explain these results. A cis-bissulfoxide was isolated from the photooxidation of 1,5-DTCO. It crystallizes in space group P1BAR of the triclinic system with two molecules in a cell of the following dimensions: a = 5.348 (3), b = 6.755 (5), c = 11.677 (7) angstrom, alpha = 90.46 (6), beta = 97.04 (5), gamma = 101.88 (6)-degrees. The structure has been refined to a final value of 0.0477 for the conventional R factor on the basis of 951 independent observed intensities.

  DOI：

  10.1021/ja00034a039
• 作为产物：
  描述：

  1-乙烯基亚磺酰乙烯 在 碳酸氢钠 作用下， 以 水 为溶剂， 反应 0.17h， 以31%的产率得到1,4-dithiane 1-oxide
  参考文献：
  名称：

  An unexpected reaction pattern of divinyl sulfoxide with potassium O-alkyl carbonodithioates under microwave assistance

  摘要：

  DOI：

  10.1134/s1070363208040270

文献信息

• Chemoselective Oxidation of Sulfides to Sulfoxides Using<i>N</i>-<i>t</i>-Butyl-<i>N</i>-chlorocyanamide
  作者：Vinod Kumar、Mahabir Parshad Kaushik

  DOI：10.1246/cl.2005.1230

  日期：2005.9

  A simple, efficient and highly chemoselective method has been developed for the synthesis of sulfoxides from sulfides using N-t-butyl-N-chlorocyanamide as an oxidant in a mixed acetonitrile–water solution with a 1:1 mol ratio of oxidant to sulfides. N-t-butyl-N-chlorocyanamide, a source of positive chlorine, has been used for conversion of the variety of sulfides into their corresponding sulfoxides in quantitative yields.

  已开发出一种简单、高效且具有高度化学选择性的方法，以N-t-butyl-N-chlorocyanamide作为氧化剂，在1:1摩尔比的氧化剂与硫化物的混合乙腈-水溶液中合成亚砜。N-t-butyl-N-chlorocyanamide作为阳性氯源，已用于将多种硫化物转化为相应的亚砜，产率为定量。
• Gold(III) catalyzed oxidation of sulfides to sulfoxides by nitric acid under phase-transfer conditions: a new synthesis of sulfoxides
  作者：F. Gasparrini、M. Giovannoli、D. Misiti、G. Natile、G. Palmieri

  DOI：10.1016/s0040-4020(01)91563-7

  日期：1983.1

  Gold(III) halides catalyze the oxidation of sulfides to sulfoxides in a phase-transfer process. The organic sulfides, dissolved in nitromethane, are treated with (Bu4N+AuCl4−) in catalytic amount and aqueous nitric acid which acts as oxidant. The oxidation of the thio-group is selective and can be carried out also in the presence of other oxidizable groups, such as vinyl, tertiary amino, hydroxy, diol

  卤化金（III）在相转移过程中催化硫化物氧化为亚砜。所述有机硫化物，溶解在硝基甲烷，都与（BU处理4 Ñ + AUCL 4 -在催化量的硝酸水溶液用作氧化剂）。硫基的氧化是选择性的，并且也可以在其他可氧化基团如乙烯基，叔氨基，羟基，二醇等保持不变的情况下进行。此外，在不对称的二硫化物的情况下，该反应是区域特异性的，导致形成单个单亚砜。
• Synthetic potentialities of sulfonylsulfonium salts: A new approach to the preparation of disulfonium dications
  作者：N. E. Shevchenko、V. G. Nenaidenko、E. S. Balenkova

  DOI：10.1007/bf02495089

  日期：2000.8

  A new efficient method for the generation of disulfonium dications whose subsequent hydrolysis selectively affords monosulfoxides was developed based on the oxidation of bissulfides by trifluoromethanesulfonic anhydride.

  基于三氟甲磺酸酐氧化二硫化物，开发了一种新的有效方法，用于生成二锍二磺酸盐，其随后的水解选择性地提供单亚砜。
• Formation of Chlorosulfonium Salt of 1,5-Dithiacyclooctane and Transannular Sulfur–Sulfur Interaction in Hydrolysis of Its Salt
  作者：Hisashi Fujihara、Ryouichi Akaishi、Naomichi Furukawa

  DOI：10.1246/bcsj.60.4451

  日期：1987.12

  The reaction of 1,5-dithiacyclooctane 1-oxide (2) with thionyl chloride afforded the corresponding chlorosulfonium chloride as a stable salt and an evidence for the intermediary formation of the bis-sulfide dication with an equilibrium mixture of the chlorosulfonium salt was found. In contrast to 2, 1,4-dithiacyclohexane 1-oxide (6) reacts with thionyl chloride like a simple sulfoxide.

  1,5-二硫杂环辛烷 1-氧化物 (2) 与亚硫酰氯的反应得到相应的氯锍氯化物，为稳定的盐，并且发现了双硫化物双阳离子与氯锍盐的平衡混合物中间形成的证据。与 2 相比，1,4-二硫代环己烷 1-氧化物 (6) 与亚硫酰氯反应就像一个简单的亚砜。
• The First Example of Addition of a 1,2-Dication to a C−C Multiple Bond. Reaction of S−S Dications with Alkenes and Alkynes
  作者：Valentine G. Nenajdenko、Nikolai E. Shevchenko、Elizabeth S. Balenkova

  DOI：10.1021/jo971801w

  日期：1998.4.1

  The reactions of a bicyclic dithioether dication, generated from 1,4-dithiane 1-oxide, with a carbon-carbon multiple bond proceed as conjugated addition of two sulfonium groups and gives rise to derivatives of dithioniabicyclo[2.2.2]octane. The reaction is sensitive to electronic and steric factors. In all cases investigated the reactions of 1,2-disubstituted arylalkene proceed with retention of the relative arrangement of substituents at the double bond of the original alkene. A possible explanation of the obtained results is discussed.