S-p-nitrophenyl-S-phenylsulfilimine | 36744-95-3

• 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-p-nitrophenyl-S-phenylsulfilimine
• 英文别名: p-Nitrophenylsulfilimin；Imino-(4-nitrophenyl)-phenyl-lambda4-sulfane；imino-(4-nitrophenyl)-phenyl-λ4-sulfane
• CAS: 36744-95-3
• 化学式: C₁₂H₁₀N₂O₂S
• 分子量: 246.29
• InChiKey: KNLRJFPBGOJPLR-UHFFFAOYSA-N

物化性质

• 熔点：
  98-99 °C
• 沸点：
  421.5±47.0 °C(Predicted)
• 密度：
  1.34±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  88.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  S-p-nitrophenyl-S-phenylsulfilimine 在 sodium hypochlorite 、 亚硝酸特丁酯 作用下， 以 甲醇 、 氯仿 、 水 为溶剂， 反应 0.25h， 生成 1-(benzenesulfinyl)-4-nitrobenzene
  参考文献：
  名称：

  Akutagawa, Kunihiko; Furukawa, Naomichi; Oae, Shigeru, Phosphorus and Sulfur and the Related Elements, 1984, vol. 19, p. 369 - 374

  摘要：

  DOI：
• 作为产物：
  描述：

  4-硝基苯基苯硫 在 N-羟基-2,4,6-三甲基苯磺酰胺 作用下， 以 二氯甲烷 为溶剂， 生成 S-p-nitrophenyl-S-phenylsulfilimine
  参考文献：
  名称：

  N-未取代的硫亚胺的合成及某些性质

  摘要：

  多种S-aminosulfonium mesitylenesulfonates的，R 1 - [R 2小号+ NH 2 ·X - ，分别以高收率由硫化物用O- mesitylenesulfonylhydroxylamine（MSH）的反应来制备。检查了衍生的亚硫亚胺的热稳定性。烯丙基硫化物与MSH的反应直接提供了烯丙基胺的盐，收率很高，大概是通过可溶的烯丙基硫亚胺的[2,3]-σ重排，然后是SN键断裂。还描述了二硫化物和硫酮与MSH的反应。

  DOI：

  10.1016/0040-4020(75)80143-8

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。
• Synthesis, Structure, and Thermolysis Mechanism of<i>S</i>-Alkoxythiazynes
  作者：Toshiaki Yoshimura、Masanori Ohkubo、Takayoshi Fujii、Hiroshi Kita、Youko Wakai、Shin Ono、Hiroyuki Morita、Choichiro Shimasaki、Ernst Horn

  DOI：10.1246/bcsj.71.1629

  日期：1998.7

  S-Alkoxy-S,S-diarylthiazynes were prepared by two methods: the alkaline hydrolysis of S,S-diaryl-N-halosulfilimines in aqueous alcohols and the reaction of S,S-diaryl-S-fluorothiazynes with sodium alkoxides. The structure of S,S-diphenyl-S-propoxythiazyne was determined by an X-ray crystallographic analysis, which showed a short SN bond length of 1.441(3) Å. The thermolysis of S-alkoxythiazynes gave elimination products, which were identified as the corresponding carbonyl compounds and N-unsubstituted S,S-diarylsulfilimines. Kinetic experiments for the thermolysis of the S-alkoxy-S,S-diarylthiazynes were carried out. The first-order kinetic behavior, a large kinetic isotope effect (kH/kD = 6.1) using S,S-diphenyl-S-[1,1-2H2]propoxythiazyne, a negative activation entropy (ΔS‡ = −30 J K−1mol−1), and a negative Hammett ρ-value (ρ = −0.35) on the phenyl group were obtained, suggesting that the reaction proceeds via a concerted five-membered cyclic transition state. A deviation from the ideal concerted transition state is discussed in comparison with that for sulfoxides.

  通过两种方法制备了 S-烷氧基-S,S-二芳基噻嗪：S,S-二芳基-N-卤代磺酰亚胺在水醇中的碱性水解以及 S,S-二芳基-S-氟噻嗪与烷氧基化钠的反应。通过 X 射线晶体学分析确定了 S,S-二苯基-S-丙氧基噻嗪的结构，其 SN 键长度较短，为 1.441(3) Å。对 S-烷氧基-S,S-二芳基噻嗪的热分解进行了动力学实验。实验结果表明，S,S-二苯基-S-[1,1-2H2]丙氧基噻嗪具有一阶动力学行为、较大的动力学同位素效应（kH/kD = 6.1）、负活化熵（ΔS‡ = -30 J K-1mol-1）以及苯基上的负 Hammett ρ 值（ρ = -0.35），这表明反应是通过一个协同的五元环过渡态进行的。通过与硫氧化物的协同过渡态进行比较，讨论了与理想协同过渡态的偏差。
• FACILE DEIMINATION OF SULFIMIDES AND SULFODIIMIDES WITH ELEMENTAL SULFUR CATALYZED OR UNCATALYZED BY AMINES
  作者：Ryu Sato、Nobushige Saito、Minoru Saito

  DOI：10.1246/cl.1983.1603

  日期：1983.10.5

  Sulfimides and sulfodiimides were readily deiminated with elemental sulfur catalyzed or uncatalyzed by amines affording corresponding sulfides and its derivatives under mild conditions in excellent yields.

  在温和的条件下，亚硫酰亚胺和二亚硫酰亚胺很容易在元素硫的催化或胺的非催化下脱亚胺，并以极好的收率得到相应的硫化物及其衍生物。
• A new method for the preparation of fluoro-λ6-sulfanenitriles: reaction of sulfimides with Selectfluor™
  作者：Takayoshi Fujii、Shinsuke Asai、Tomoyuki Okada、Wei Hao、Hiroyuki Morita、Toshiaki Yoshimura

  DOI：10.1016/s0040-4039(03)01547-8

  日期：2003.8

  Several diaryl(fluoro)-λ6-sulfanenitriles 3 were synthesized by the reaction of S,S-diarylsulfimides 1 with Selectfluor™. This reaction also allows the first preparation of heterocyclic fluoro-λ6-sulfanenitrile, 5-fluoro-10,10-dioxo-5,10-dihydro-5λ6,10λ6-thianthren-5-nitrile (5) and its molecular structure was determined by X-ray crystallographic analysis.

  几个芳基（氟）-λ 6 -sulfanenitriles 3由反应合成小号，小号-diarylsulfimides 1与的Selectfluor™。该反应也允许杂环氟λ的第一准备6 -sulfanenitrile，5-氟-10,10-二氧代-5,10-二氢5λ 6，10λ 6 -thianthren -5-腈（5）和其分子结构通过X射线晶体学分析确定。
• Oae, Shigeru; Iida, Kazuyuki; Takata, Toshikazu, Phosphorus and Sulfur and the Related Elements, 1981, vol. 12, p. 103 - 114
  作者：Oae, Shigeru、Iida, Kazuyuki、Takata, Toshikazu

  DOI：——

  日期：——