S,S-Diphenyl-N-chlorosulfilimine | 42787-33-7

• 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-chlorosulfilimine
• 英文别名: diphenyl-N-chlorosulfilimine；Diphenyl-N-chlorosulfilimin；Diphenyl-N-chlorsulfilimin；Diphenyl-N-chlorsulfimid；(N-chloro-S-phenylsulfinimidoyl)benzene；chloroimino(diphenyl)-λ4-sulfane
• CAS: 42787-33-7
• 化学式: C₁₂H₁₀ClNS
• 分子量: 235.737
• InChiKey: OZWGXZRYJNOCEA-UHFFFAOYSA-N

物化性质

• 沸点：
  382.0±25.0 °C(Predicted)
• 密度：
  1.21±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 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：
  31.6
• 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-chlorosulfilimine 在 sodium hydroxide 作用下， 以 水 、 苯 为溶剂， 反应 39.28h， 生成 S,S-diphenylsulphoximine
  参考文献：
  名称：

  Synthesis, Structure, and Thermolysis Mechanism ofS-Alkoxythiazynes

  摘要：

  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。

  DOI：

  10.1246/bcsj.71.1629
• 作为产物：
  描述：

  N-(iminodiphenyl-λ⁶-sulfanylidene)-4-methylbenzenesulfonamide 在 硫酸 、 sodium p-toluenesulfonamide 作用下， 反应 48.08h， 生成 S,S-Diphenyl-N-chlorosulfilimine
  参考文献：
  名称：

  Furukawa, Naomichi; Akutagawa, Kunihiko; Oae, Shigeru, Phosphorus and Sulfur and the Related Elements, 1984, vol. 20, p. 1 - 14

  摘要：

  DOI：

文献信息

• A convenient preparation of N- (arenesulfonyl) sulfoximines by oxidation of N- (arenesulfonyl) sulfilimines with sodium hypochlorite in a two phase system
  作者：Naomichi Furukawa、Kunihiko Akutagawa、Toshiaki Yoshimura、Shigeru Oae

  DOI：10.1016/s0040-4039(01)82045-1

  日期：1981.1

  N-(Arenesulfonyl) sulfilimines can be oxidized to the corresponding sulfoximes in high yields with sodium hypochlorite in an AcOEt-H2O two phase system in the presence of quaternary ammonium salts as catalysts.

  在季铵盐作为催化剂的存在下，在AcOEt-H 2 O两相系统中，可以用次氯酸钠将N-（戊烯磺酰基）亚砜亚胺氧化成相应的磺肟。
• Diphenyl N-halosulfilimines
  作者：Toshiaki Yoshimura、Naomichi Furukawa、Takeshi Akasaka、Shigeru Oae

  DOI：10.1016/0040-4020(77)80226-3

  日期：1977.1

  Compound 1 decomposed in benzene at room temperature. The decomposition of 1 is a chain reaction since the reaction was induced by chlorine or t-butyl hypochlorite affording diphenyl(diphenylsulfilimino) sulfonium chloride(4a) while it was inhibited by styrene or stilbene. Compound 4a was also obtained by the reaction of 1 with diphenyl sulfide in benzene. Decomposition of 1 in acetic acid proceeded smoothly

  通过卤化不含二苯基的亚硫亚胺来制备二苯基N氯（1）-N溴（2）和N-碘代亚硫亚胺（3）。化合物1在室温下在苯中分解。1的分解是链式反应，因为该反应是由氯或次氯酸叔丁酯引发的，提供了二苯基（二苯基硫代亚氨基）氯化（（4a），同时被苯乙烯或抑制了。还通过1与二苯硫醚在苯中的反应获得化合物4a。1在乙酸中的分解顺利进行，得到各种产物。化合物1与硫化物亚砜三芳基膦和三乙胺反应，得到N-取代的亚氨基ulf盐。用氢氧化钠水解化合物1和2，得到二苯基亚磺酰亚胺。1与氰化钠的反应，得到二苯基N-氰基硫亚胺（17）。的反应1与格氏试剂，得到二苯基硫亚胺自由。化合物2和3比1更稳定。2在苯或乙酸中的分解产生二溴（二苯基硫代氨基）溴化per（4c）
• Kinetic Study on the Alkaline Hydrolysis of<i>S</i>,<i>S</i>-Diaryl-<i>N</i>-halosulfilimines
  作者：Toshiaki Yoshimura、Eiichi Tsukurimichi、Hiroshi Kita、Hiroshi Fujii、Choichiro Shimasaki

  DOI：10.1246/bcsj.63.1764

  日期：1990.6

  Kinetics for the alkaline hydrolysis of S,S-diaryl-N-bromosulfilimines were carried out in aqueous methanol. The observed pseudo-first-order rate constants were found to give a linear correlation with the concentration of sodium hydroxide, k=k1+k2[NaOH]. The first-order rate constants k1 showed a large negative Hammett ρ value (−2.43) for the substituent effect on the phenyl group, nearly zero activation

  S,S-二芳基-N-溴亚硫亚胺的碱性水解动力学在甲醇水溶液中进行。发现观察到的伪一级速率常数与氢氧化钠浓度呈线性相关，k=k1+k2[NaOH]。一级速率常数 k1 显示出较大的负 Hammett ρ 值 (-2.43)，用于取代基对苯基的影响，几乎为零的活化熵 (-0.9±13.1 JK-1mol-1) 和相对较大的 m 值 (0.638 ) 对溶剂电离能力 Y 值表明反应过程为 k1 接近 SNl。盐效应、氘溶剂同位素效应和空间效应也符合SNl机理。另一方面，二阶速率常数 k2 显示出较小的 Hammett ρ 值、负的激活熵（-44.0±4.0 JK-1mol-1）、较小的 m 值（0. 153) 和邻位取代基的空间减速表明 k2 的反应类似于 SN2。盐效应和溶剂同位素效应也是相容的...
• Formation of S,S-diphenyl-S-methoxythiazyne Ph2S(OMe)(≡N) in the alkaline hydrolysis of S,S-diphenyl-N-halosulfilimines
  作者：Toshiaki Yoshimura、Eiichi Tsukurimichi、Hiroshi Kita、Hiroshi Fujii、Choichiro Shimasaki

  DOI：10.1016/s0040-4039(01)93888-2

  日期：1989.1

  The structure of a compound formed during the alkaline hydrolysis of S,S-diphenyl-N-halosulfilimines to the corresponding sulfoximine in methanol was assigned to PhS(OMe)(≡N)Ph, S,S-diphenyl-S-methoxythiazyne, on the basis of spectroscopic analyses and chemical reactions.

  在甲醇中将S，S-二苯基-N-卤代亚硫胺碱水解为相应的亚砜亚胺期间形成的化合物的结构分配为PhS（OMe）（≡N）Ph，S，S-二苯基-S-甲氧基硫代ia光谱分析和化学反应的基础。
• Reaction of chromium (Fischer) carbenes and sulfilimines
  作者：Benito Alcaide、Luis Casarrubios、Gema Dominguez、Miguel A. Sierra

  DOI：10.1021/jo00067a020

  日期：1993.7

  The photochemical reactions of alkoxychromium (Fischer) carbenes and sulfilimines lead to imidates in fair to excellent yields. Aromatic, heteroaromatic, and alkylsulfilimines, the latter bearing functional groups such as cyano, sulfone, ether, ester, and dioxolane groups, gave the corresponding imidates in good to excellent yield. However, acyl- and sulfonyl-substituted sulfilimines did not react with chromium carbenes, except for sulfilimines bearing ethoxycarbonyl and phtalimidylamino groups. A variety of differently substituted chromium carbene complexes bearing alkyl, cycloalkyl, styryl, allyl, and alkynyl groups attached either at the carbene carbon or at the oxygen also gave imidates in good yields. For alpha,beta-unsaturated carbenes, the exclusive 1,2-addition of the sulfilimine nitrogen was observed at room temperature, in contrast to the behavior of other nitrogen nucleophiles which are reported to add in 1,4-fashion under these reaction conditions. In turn, optically active imidates of the type ArN=C(OR*)Me [R* = chiral substituent derived from (R)-(+)-1-phenyl-1-butanol, l-(-)-menthol, (1S)-endo-(-)-borneol, and (1R)-(-)-myrtenol] can be prepared efficiently by utilizing the corresponding chiral alkoxy group on the earbene moiety. The reactions above also occur in the dark but reaction times are considerably longer. N-Halosulfilimines reacted with alkoxychromium carbenes to yield N-acylsulfilimines instead of the expected N-haloimidates. Based upon a set of thermal and photochemical reactions between N-haloimidates and diphenyl sulfide in the absence of chromium complexes, the complex (CO)5CrNCMe is proposed to be responsible for this novel reaction of N-haloimidates and diphenyl sulfide.