S,S-dimethyl-N-p-tolylsulfonylsulfimine | 13150-75-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: S,S-dimethyl-N-p-tolylsulfonylsulfimine
• 英文别名: S,S-Dimethyl-N-p-tolylsulfonyl-sulfilimin；S,S-Dimethyl-N-p-toluolsulfonyl-sulfilimin；N-Tosyldimethylsulfilimin；benzenesulfonamide, N-(dimethylsulfanylidene)-4-methyl-；N-(dimethyl-λ4-sulfanylidene)-4-methylbenzenesulfonamide
• CAS: 13150-75-9
• 化学式: C₉H₁₃NO₂S₂
• 分子量: 231.34
• InChiKey: XXOIGDFCELVFFJ-UHFFFAOYSA-N

物化性质

• 熔点：
  154-155 °C
• 沸点：
  389.4±35.0 °C(Predicted)
• 密度：
  1.26(20.0000℃)
• 闪点：
  189.3℃

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  74.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  S,S-dimethyl-N-p-tolylsulfonylsulfimine 在 二氯二甲基硅烷 、 锌 作用下， 生成 二甲基硫
  参考文献：
  名称：

  Nagasawa, Kazuo; Umezawa, Toshiyuki; Itoh, Kei-ichi, Heterocycles, 1984, vol. 21, # 2, p. 463

  摘要：

  DOI：
• 作为产物：
  描述：

  三甲基-(4-甲基苯基)锡烷 以 二氯甲烷 为溶剂， 反应 20.0h， 生成 S,S-dimethyl-N-p-tolylsulfonylsulfimine
  参考文献：
  名称：

  Tin for organic synthesis. 10. Unconventional regiospecific syntheses of aromatic carbonamides and thiocarbonamides by means of tin-mediated Friedel-Crafts reactions

  摘要：

  Friedel-Crafts reactions of stannylarenes 1 with tosyl isocyanate (TsNCO, 2) give N-tosylcarbonamides 3 via ipso substitution of the stannyl group. Thus, unconventionally substituted aromatic carbonamides can be obtained. The combination of the reaction of 1 and 2 with that of 1 and chlorosulfonyl isocyanate (14) allows one-pot syntheses of N-(arylsulfonyl)-substituted aromatic carbonamides with optional substitution patterns on both aromatic rings. The known ipso-specific substitutions of stannylarenes with 14 are extended to bi- and tricyclic arenes as well as to thiophenes 6 and 22. One stannyl group can serve as a leaving group for two aromatic systems, as shown with diaryldialkyltins 29. Also, stannylalkanes such as 27 react with 14 to afford alkylsulfonyl isocyanates and products of further reactions, such as 28. From the reactions of 1 with ethoxycarbonyl isothiocyanate (32), ortho- and meta-substituted aromatic thiocarbonamides 33 which are potential precursors for further syntheses, are accessible. The scope, limitations, and mechanism of these electrophilic substitutions are outlined.

  DOI：

  10.1021/jo00077a020

文献信息

• Copper-catalyzed imination of sulfoxides and sulfides
  作者：Yuanyuan Liu、Hanying Wang、Xianjin Yang

  DOI：10.1016/j.tet.2019.07.020

  日期：2019.8

  and sulfilimines have attracted considerable interest among organic chemists. The Cu(II)-catalyzed imination of sulfoxides and sulfides using various N-fluoro benzenesulfonamides was investigated in this study. The scope of the reaction was demonstrated by using several substituted sulfides and sulfoxides. The flow strategy for the preparation of NH-sulfoximines was also examined. By trapping nitrene

  磺胺嘧啶和亚磺胺在有机化学家中引起了相当大的兴趣。在这项研究中，研究了使用各种N-氟苯磺酰胺的Cu（II）催化的亚砜和硫化物的亚胺化。通过使用几种取代的硫化物和亚砜来证明反应的范围。还检查了制备NH-磺胺嘧啶的流动策略。通过三苯膦截留腈中间体，我们发现该反应是通过金属-氮化物中间体机理进行的。
• Dibenzothiophenesulfilimines: A Convenient Approach to Intermolecular Rhodium‐Catalysed C−H Amidation
  作者：Patrick W. Antoni、Alexandra V. Mackenroth、Florian F. Mulks、Matthias Rudolph、Günter Helmchen、A. Stephen K. Hashmi

  DOI：10.1002/chem.202002371

  日期：2020.7.2

  transition‐metal‐catalysed C−H amidation procedure is reported. Dibenzothiophene‐based sulfilimines were shown to constitute a class of novel amidation reagents which enable the transfer of a wide range of N‐sulfonyl and N‐acyl moieties. It was demonstrated that sulfilimines, which are easily accessible from cheap reagents, are safe‐to‐handle and represent broadly applicable amidation reagents. The dibenzothiophene

  据报道，基于亚硫胺的第9族过渡金属催化的CH 3酰胺化过程。研究表明，基于二苯并噻吩的硫亚胺可构成一类新型的酰胺化试剂，可转移各种N-磺酰基和N-酰基部分。事实证明，可以从便宜的试剂中容易获得的亚硫胺类，操作安全，代表着广泛适用的酰胺化试剂。使用后可以将二苯并噻吩回收。CH-H酰胺化反应具有很高的选择性，可以得到单酰胺化的产物，大部分收率良好。
• Mechanism of the reaction of N-p-tosylsulphilimine and related compounds with thiophenolate ion
  作者：Shigeru Oae、Tetsuo Aida、Masashi Nakajima、Naomichi Furukawa

  DOI：10.1016/s0040-4020(01)97480-0

  日期：1974.1

  reaction of alkyl aryl N-p-tosylsulphilimines with thiophenolate ion was found to afford quantitatively the sulphide that arises by an SN2 like reaction on the carbon atom adjacent to the tri-valent sulphur atom. This reaction was also found to proceed smoothly with such compounds as sulphoxides and sulphones and sulphoxmanes. The kinetic study on the reaction between aryl methyl N-p-tosylsulphilimine

  发现烷基芳基N-对甲苯磺酰基亚胺与硫酚盐离子的反应定量地提供了由类似于S N 2的反应在邻近三价硫原子的碳原子上产生的硫化物。还发现该反应在诸如亚砜，砜和亚砜基的化合物中可顺利进行。在DMF中对芳基甲基N-对甲苯磺酰亚氨基亚胺与硫酚酸根离子之间反应的动力学研究表明，该反应是二级的，即对于每个硫酚酸根离子和亚硫亚胺而言是一级的。反应的活化焓和熵为ΔH ≠ = -17·kcal / mol和ΔS ≠分别等于-5·7 eu。取代基在反应中的作用-p -XC 6 H 4 +（- SO 2 C 6 H 4 Y- p）CH 3 + p -ZC 6 H 4 SK与Hammettσ值很好相关，得到ϱ x = + 2 ·4，y = + 1·2，z = -1·8。同时，观察到烷基苯基N-对甲苯磺酰亚胺基亚胺中的大体积烷基显着的空间延迟。此外，根据使用旋光秒的反应的立体化学研究-辛基苯基N-对甲苯磺酰亚胺与硫酚
• The Reaction of Elemental Sulfur with Organic Compounds. IV. The Reactions of<i>N</i>-Arenesulfonylsulfilimine and Sulfoximine with Sulfur and Diaryl Disulfide
  作者：Shigeru Oae、Yoshiyuki Tsuchida、Kenji Tsujihara、Naomichi Furukawa

  DOI：10.1246/bcsj.45.2856

  日期：1972.9

  The reactions of elemental sulfur and diaryl disulfide with the compounds bearing a semipolar S→N linkage were investigated. Elemental sulfur was found to react with N-arenesulfonylsulfilimine and sulfoximine affording the corresponding sulfide and the sulfoxide respectively. Diaryl disulfide also was found to undergo similar reactions with these compounds. In the reaction of diaryl disulfide with

  研究了元素硫和二芳基二硫化物与带有半极性 S→N 键的化合物的反应。发现元素硫与 N-芳烃磺酰基硫亚胺和亚砜亚胺反应，分别得到相应的硫化物和亚砜。还发现二芳基二硫化物与这些化合物发生类似的反应。二芳基二硫化物与N-芳烃磺酰基硫亚胺反应，除相应的硫化物外，主要产物为N,N-双-(芳硫基)芳烃磺酰胺。讨论了这些反应的机制。
• AN YLID EXCHANGE REACTION OF SULFILIMINE
  作者：Tamotsu Yamamoto、Yasuji Harigaya、Makoto Okawara

  DOI：10.1246/cl.1972.1009

  日期：1972.10.5

  p-toluenesulfonamide gave N-p-toluenesulfonyl-S,S-dimethylsulfilimine 2. The reaction of 1 with carbon acids 3 having active methylene gave stable S-C ylids (exchange of S-N ylid for S-C ylid), while 2 reacted with malonitrile to give S-C ylid only in low yield. Thus, the ylid exchange mechanism based on the equilibrium including the protonated sulfonium salts has been assumed.

  新的硫亚胺 N-2,4-二硝基苯基-S,S-二甲基硫亚胺 1 与对甲苯磺酰胺反应得到 Np-甲苯磺酰基-S,S-二甲基硫亚胺 2。1 与具有活性亚甲基的碳酸 3 反应得到稳定的SC ylids（SN ylid 交换 SC ylid），而 2 与丙二腈反应仅以低产率得到 SC ylid。因此，假设了基于包括质子化锍盐在内的平衡的叶立德交换机制。