S.S-Diphenyl-N-p-toluoylsulfimid | 62701-77-3

• 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-Diphenyl-N-p-toluoylsulfimid
• 英文别名: N-p-Toluoyl-S,S-diphenylsulfinilimin；N-(diphenyl-lambda4-sulfanylidene)-4-methylbenzamide；N-(diphenyl-λ4-sulfanylidene)-4-methylbenzamide
• CAS: 62701-77-3
• 化学式: C₂₀H₁₇NOS
• 分子量: 319.427
• InChiKey: UMEOKXFXVSAFSN-UHFFFAOYSA-N

物化性质

• 熔点：
  119-120 °C
• 沸点：
  511.5±43.0 °C(Predicted)
• 密度：
  1.13±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  23
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  48.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2-溴苯酚 在 正丁基锂 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 正己烷 为溶剂， 反应 5.33h， 生成 S.S-Diphenyl-N-p-toluoylsulfimid
  参考文献：
  名称：

  通过芳炔和环己炔中间体合成硫亚胺

  摘要：

  开发了一种有效且无金属的方法，用于从次磺酰胺与芳炔和环己炔前体合成硫亚胺。该反应通过不寻常的 S-C 键形成进行，这为以中等至良好的产率和优异的化学选择性获得各种硫亚胺提供了新颖且实用的途径。此外，该方案适合克级合成，并且适用于将产品转化为有用的亚砜亚胺。

  DOI：

  10.1021/acs.orglett.3c01918

文献信息

• Thermal Curtius Rearrangement of<i>N</i>-Acyl-<i>S</i>,<i>S</i>-diphenylsulfilimine
  作者：Naomichi Furukawa、Mitsuo Fukumura、Takehiko Nishio、Shigeru Oae

  DOI：10.1246/bcsj.51.3599

  日期：1978.12

  Several N-acyl-S,S-arylphenylsulfilimines were prepared and subjected to thermal decomposition. They decomposed readily at 130–190 °C to give isocyanates together with diphenyl sulfide, quantitatively. However, N-tosyl-S,S-diphenylsulfilimine did not decompose even upon heating at 200 °C for 24 h. A kinetic study revealed that the rates of pyrolysis of N-aroyl-S,S-arylphenylsulfilimines (p-Y–C6H4(Ph)S→NCOC6H4–X-p) are nicely correlated with the Hammett σ-values, ρX=−1.2 and ρY=+0.92, respectively, being obtained. The activation enthalpies and entropies were ΔH\eweq=38.7 kcal/mol and ΔS\eweq=6.0 e.u. for Ph2S→NCOPh and ΔH\eweq=32.3 kcal/mol and ΔS\eweq=5.5 e.u. for (Remark: Graphics omitted.), respectively. The rearrangement was accelerated considerably by o-methyl substituent in the aryl group. The effect of solvent on the rate of pyrolysis was small. The results indicate that the pyrolysis of sulfilimine proceeds via a concerted migration of the R group from carbonyl carbon to imino nitrogen similar to the Curtius type rearrangement of acid azide.

  制备了几种N-酰基-S,S-二苯基亚砜亚胺，并进行了热分解实验。它们在130-190°C下容易分解，定量地生成异氰酸酯和二苯基硫醚。然而，N-对甲苯磺酰基-S,S-二苯基亚砜亚胺即使在200°C下加热24小时也不分解。动力学研究表明，N-芳酰基-S,S-芳基苯基亚砜亚胺（p-Y-C6H4(Ph)S→NCO -X-p）的热解速率与Hammett σ值很好地相关，分别得到ρX=-1.2和ρY=+0.92。活化焓和熵分别为ΔH\eweq=38.7 kcal/mol和ΔS\eweq=6.0 e.u.（对于Ph2S→NCOPh）以及ΔH\eweq=32.3 kcal/mol和ΔS\eweq=5.5 e.u.（注：图形省略）。芳基的邻位甲基取代基明显加速了重排反应。溶剂对热解速率的影响很小。结果表明，亚砜亚胺的热解是通过R基团从羰基碳向亚胺氮的协同迁移进行的，类似于酸叠氮的Curtius型重排。
• Metal-Free Chemoselective <i>S</i>-Arylation of Sulfenamides To Access Sulfilimines
  作者：Xianda Wu、Yuqing Li、Minghong Chen、Fu-Sheng He、Jie Wu

  DOI：10.1021/acs.joc.3c00961

  日期：2023.7.7

  A novel and efficient S-arylation of sulfenamides with diaryliodonium salts for the synthesis of sulfilimines is developed. The reaction proceeds smoothly under transition-metal-free and air conditions, giving rapid access to sulfilimines in good to excellent yields via selective S–C bond formation. This protocol is scalable and exhibits a broad substrate scope, good functional group tolerance, and

  开发了一种新颖且有效的亚磺酰胺与二芳基碘鎓盐的S-芳基化反应，用于合成硫亚胺。该反应在无过渡金属和空气条件下顺利进行，通过选择性 S-C 键形成，以良好至优异的产率快速获得硫亚胺。该方案具有可扩展性，具有广泛的底物范围、良好的官能团耐受性和出色的化学选择性。
• Synthesis of Sulfilimines via Multicomponent Reaction of Arynes, Sulfamides, and Thiosulfonates
  作者：Pei Xie、Yating Zheng、Yuping Luo、Jinyun Luo、Leifang Wu、Zhihua Cai、Lin He

  DOI：10.1021/acs.orglett.3c02217

  日期：2023.8.25

  In this work, a facile and efficient method for the synthesis of sulfilimines through multicomponent reaction of arynes, sulfamides, and thiosulfonates was developed. A variety of structurally diverse substrates and functional groups were very compatible in the reaction, giving the corresponding sulfilimines in good to high yields. This protocol could be conducted on a gram scale, and the product was

  在这项工作中，开发了一种通过芳炔、磺酰胺和硫代磺酸盐的多组分反应合成硫亚胺的简便有效的方法。各种结构多样的底物和官能团在反应中非常相容，从而以良好到高的产率产生相应的硫亚胺。该方案可以在克规模上进行，并且产物很容易转化为硫化物和亚砜亚胺。机理研究表明，原位生成的次磺酰胺是该反应的关键中间体。
• Selective S-Arylation of Sulfenamides with Arynes: Access to Sulfilimines
  作者：Yifeng Guo、Zhe Zhuang、Xiaoying Feng、Quanyu Ma、Ningning Li、Chaochao Jin、Hiroto Yoshida、Jiajing Tan

  DOI：10.1021/acs.orglett.3c02785

  日期：2023.10.6

  Sulfilimines, the aza analogues of sulfoxides, are of increasing interest in medicinal and agrochemical research programs. However, the development of efficient routes for their synthesis has remained relatively unexplored. In this study, we report a transition metal-free, selective S-arylation reaction between sulfenamides and arynes, enabling the facile preparation of structurally diverse sulfilimines

  磺亚胺是亚砜的氮杂类似物，在医药和农业化学研究项目中越来越受到人们的关注。然而，其有效合成路线的开发相对尚未探索。在这项研究中，我们报道了次磺酰胺和芳炔之间的无过渡金属、选择性S-芳基化反应，使得能够在温和和氧化还原中性条件下以良好的收率轻松制备结构多样的硫亚胺。通过放大合成、下游衍生化和稳健性筛选进一步证明了我们方法的应用价值。