(4-Chlorophenyl)-imino-phenyl-lambda4-sulfane | 36744-94-2

• 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: (4-Chlorophenyl)-imino-phenyl-lambda4-sulfane
• 英文别名: (4-chlorophenyl)-imino-phenyl-λ4-sulfane
• CAS: 36744-94-2
• 化学式: C₁₂H₁₀ClNS
• 分子量: 235.737
• InChiKey: DLNUILMADNBNLO-UHFFFAOYSA-N

物化性质

• 熔点：
  48-49 °C
• 沸点：
  365.0±44.0 °C(Predicted)
• 密度：
  1.26±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  15
• 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：
  43.1
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (4-Chlorophenyl)-imino-phenyl-lambda4-sulfane 在 sodium hypochlorite 作用下， 以 甲醇 、 水 为溶剂， 生成 phenyl p-chlorophenyl sulfoximide
  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：

  S-(p-chlorophenyl)-S-phenyl-N-(p-tolylsulfonyl)sulfilimine 生成 (4-Chlorophenyl)-imino-phenyl-lambda4-sulfane
  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。
• 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。
• Biomolecule-Compatible Dehydrogenative Chan–Lam Coupling of Free Sulfilimines
  作者：Tingting Meng、Lucille A. Wells、Tianxin Wang、Jinyu Wang、Shishuo Zhang、Jie Wang、Marisa C. Kozlowski、Tiezheng Jia

  DOI：10.1021/jacs.2c04627

  日期：2022.7.13

  Here, we report a terminal oxidant-free copper-catalyzed dehydrogenative Chan–Lam coupling of free diaryl sulfilimines with arylboronic acids with excellent chemoselectivity and broad substrate compatibility. The mild reaction conditions and biomolecule-compatible nature allow the employment of this protocol in the late-stage functionalization of complex peptides, and more importantly, as an effective

  受到 IV 型胶原蛋白网络中 S=N 键的发现及其在稳定基底膜中的重要作用的启发，硫亚胺在化学和生物学领域引起了广泛关注。然而，由于缺乏在生物分子相容条件下构建硫亚胺的温和、有效和环境友好的方案，阻碍了它们的进一步吸收。在这里，我们报道了游离二芳基硫亚胺与芳基硼酸的无末端氧化剂铜催化脱氢 Chan-Lam 偶联，具有优异的化学选择性和广泛的底物兼容性。温和的反应条件和生物分子相容性允许该方案在复杂肽的后期功能化中使用，更重要的是，作为模型蛋白质中展示的有效的生物共轭方法。实验和计算机制相结合的研究表明，内球电子转移过程规避了传统 Chan-Lam 偶联反应中使用的牺牲氧化剂。找到了一条能量上可行的协同途径，其中氢化铜促进氢原子从异丙醇溶剂中提取，从而通过四元过渡态产生氢气。