S,S-diphenyl-N-acetylsulfilimine | 42397-41-1

• 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-acetylsulfilimine
• 英文别名: N-acetyl diphenylsulfimide；N-Acetyl-S,S-diphenylsulfinilimin；N-Acetyldiphenylsulfilimin；N-(diphenyl-lambda4-sulfanylidene)acetamide；N-(diphenyl-λ4-sulfanylidene)acetamide
• CAS: 42397-41-1
• 化学式: C₁₄H₁₃NOS
• 分子量: 243.329
• InChiKey: PBKLLEJILVTIQU-UHFFFAOYSA-N

物化性质

• 熔点：
  89 °C(Solv: ethanol (64-17-5))
• 沸点：
  409.1±28.0 °C(Predicted)
• 密度：
  1.13±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  48.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  S,S-diphenyl-N-acetylsulfilimine 在 potassium carbonate 、 间氯过氧苯甲酸 作用下， 以 乙醇 为溶剂， 生成 N-acetyl-S,S-diphenylsulfoximine
  参考文献：
  名称：

  Oxidation of N-acyl-, N-sulfonyl-, and N-arylsulfilimines to sulfoximines by m-chloroperoxybenzoate anion

  摘要：

  DOI：

  10.1021/jo01328a039
• 作为产物：
  描述：

  N-[(4-methylphenyl)sulfonyl]-S,S-diphenyl-sulfilimine 以 苯 为溶剂， 生成 S,S-diphenyl-N-acetylsulfilimine
  参考文献：
  名称：

  Free sulfilimines. 5. Preparation and physical and chemical properties of "free" sulfilimines

  摘要：

  DOI：

  10.1021/jo00872a013

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。
• Light-Induced Ruthenium-Catalyzed Nitrene Transfer Reactions: A Photochemical Approach towards N-Acyl Sulfimides and Sulfoximines
  作者：Vincent Bizet、Laura Buglioni、Carsten Bolm

  DOI：10.1002/anie.201310790

  日期：2014.5.26

  photochemical conditions, thus yielding N‐acyl nitrenes. Described herein is a light‐induced ruthenium‐catalyzed N‐acyl nitrene transfer to sulfides and sulfoxides by decarboxylation of 1,4,2‐dioxazol‐5‐ones at room temperature, thus providing direct access to N‐acyl sulfimides and sulfoximines under mild reaction conditions. In addition, a one‐pot sulfur imidation/oxidation sequence catalyzed by a single

  1,4,2-二恶唑-5-酮是五元杂环，已知在热或光化学条件下会脱羧，从而生成N-酰基腈。本文描述了一种光诱导的钌催化的N-酰基氮烯在室温下通过1,4,2-二氧杂唑-5-酮的脱羧反应转化为硫化物和亚砜的化合物，因此可以在温和的条件下直接接触N-酰基磺酰亚胺和亚磺酰亚胺反应条件。此外，还报道了由单个钌络合物催化的一锅硫酰亚胺化/氧化序列。
• Reaction of N-acylsulfilimines with diphenyl ketene. A new synthesis of 2-oxazolin-4-ones
  作者：Daniel M. Ketcha、Magid Abou-Gharbia、Francis X. Smith、Daniel Swern

  DOI：10.1016/s0040-4039(00)88030-2

  日期：1983.1

  2-Substituted-5,5-diphenyl-2-oxazolin-4-ones1 are prepared in good to high yields by reaction of diphenyl ketene and N-acylsulfilimes.

  通过二苯乙烯酮与N-酰基硫基硅氧烷的反应，以高至高产率制备2-取代的5，5-二苯基-2-恶唑啉-4-酮1。
• Photo SN-bond cleavage and related reactions of thianthrene sulfilimine derivatives
  作者：Tomoyuki Fujita、Hideo Kamiyama、Yasushi Osawa、Hiroyuki Kawaguchi、Bung Ju Kim、Atsushi Tatami、Wataru Kawashima、Tetsuo Maeda、Atsushi Nakanishi、Hiroyuki Morita

  DOI：10.1016/j.tet.2007.05.004

  日期：2007.8

  Several 1- and 2-substituted thianthrene sulfilimine derivatives were prepared and the selectivity toward oxidation and N-tosylimination under several conditions was studied. In the photolysis of trans-5-(N-p-tosyl) iminothianthrene 10-oxide (trans-10), photo isomerization to cis-10 was observed. Further, photoimino-transferreaction of sulfilimines and their 10-mono- and -dioxide derivatives to sulfides was intensively studied to make clear the ability as nitrene precursors. (c) 2007 Elsevier Ltd. All rights reserved.
• Reactions of ketenes with sulfilimines. Synthetic routes to oxazolinones and indolinones
  作者：Magid Abou-Gharbia、Daniel M. Ketcha、David E. Zacharias、Daniel Swern

  DOI：10.1021/jo00213a005

  日期：1985.6