o-(PhS(=NH))(PhS)C6H4

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: o-(PhS(=NH))(PhS)C6H4
• 英文别名: 1,2-PhS(NH)C6H4SPh；Imino-phenyl-(2-phenylsulfanylphenyl)-lambda4-sulfane；imino-phenyl-(2-phenylsulfanylphenyl)-λ4-sulfane
• 化学式: C₁₈H₁₅NS₂
• 分子量: 309.456
• InChiKey: GXXPXERNWDHYSA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.1
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  68.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  o-(PhS(=NH))(PhS)C6H4 以 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  Preparation of the First Complexes of Bidentate Sulfimides; the X‐ray Crystal Structures of [PdBr ₂ {1,4‐(PhS{NH}) ₂ C ₆ H ₄ }] ₂ , [PdCl ₂ {1,2‐(PhS{NH})(PhS)C ₆ H ₄ }] and trans ‐[PdCl ₂ {1,2‐(PhS{NH})(PhS)C ₆ H ₄ }PPh ₃ ]

  摘要：

  AbstractReaction of [PPh4]2[Pd2X6] (where X = Cl, Br or I) with 1,4‐(PhS{NH})2C6H4 (1) in dichloromethane results in the formation of [Pd{1,4‐(PhS{NH})2C6H4}X2]2 (2). X‐ray crystallography (performed using a synchrotron source) confirms that in the case where X = Br (2a) both the bis‐sulfimides act as bridging ligands through N−Pd bonds producing an 18‐membered ring system linking the four sulfur atoms into an almost perfect square. Changing the reaction solvent to methanol/dichloromethane results in the formation of a polymeric material. Reaction of [PdCl2(PhCN)2] with 1,2‐(PhS{NH})(PhS)C6H4 (3) results in the formation of [PdCl2{1,2‐(PhS{NH})(PhS)C6H4}] (4) in which 3 acts as a bidentate ligand, bound by N−Pd and S−Pd bonds to form a unique MSCCSN metallacycle. The Pd−S bond is broken upon reaction with one equivalent of PPh3, generating trans‐[PdCl2{1,2‐(PhS{NH})(PhS)C6H4}PPh3] (5); further reaction with PPh3 results in complete removal of 3 from the system and formation of trans‐[PdCl2(PPh3)2]. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

  DOI：

  10.1002/ejic.200390012
• 作为产物：
  描述：

  在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以67%的产率得到o-(PhS(=NH))(PhS)C6H4
  参考文献：
  名称：

  新型亚磺酰亚胺体系的制备和结构；1,4-（PhS {NH}）2 C 6 H 4（和二水合物），1,2-（PhS {NH}）（PhS）C 6 H 4 ·H 2 O和[ Ph 2 SNH]及其水合物

  摘要：

  用适当量的1,4-（PhS）2 C 6 H 4和1,2-（PhS）2 C 6 H 4处理邻甲基磺酰基羟胺（MSH）产生相应的质子化的亚磺酰亚胺，两者都可以用DBU去质子化，得到水合的游离亚磺酰亚胺1,4-（PhS {NH}）2 C 6 H 4 ·2H 2 O 1a和1-（PhS {NH }）-2-（PhS）C 6 H 4 ·H 2 O 2a。1a和2a的X射线晶体结构以及众所周知的硫化亚胺Ph 2 SNH·H 2 O 3a的X射线晶体结构都揭示了扩展的氢键阵列，涉及N–H单元和水结晶化。的晶体1B，的脱水形式1A，也容易形成，同时除去水从图3a真空，接着缓慢蒸发 解决方案 乙醚在厌氧条件下产生Ph 2 SNH 3b晶体; 1b和3b的X射线晶体结构也揭示了由N–H⋯N相互作用形成的扩展阵列。相反，2a的脱水破坏了延伸的结构，导致形成油。

  DOI：

  10.1039/b103502a

文献信息

• Reactions of mono- and bis-N-bromosulfimides with thio-ether crowns, phosphines and selenides
  作者：Stephen M. Aucott、Mark R. Bailey、Mark R. J. Elsegood、Liam M. Gilby、Kathryn E. Holmes、Paul F. Kelly、Michael J. Papageorgiou、Sarah Pedrón-Haba

  DOI：10.1039/b316850f

  日期：——

  The brominated sulfimide Ph2SNBr reacts with diphosphines 1,2-(PPh2)2C2H4 and 1,4-(Ph2P)2(C6H4) to give the bis-N-phosphoniosulfimidium cations [1,2-(Ph2PNSPh2)2C2H4]2+ and [1,4-(Ph2PNSPh2)2(C6H4)]2+, respectively. Treatment of the bis-sulfimide 1,4-[PhSNH]2C6H4 with N-bromosuccinimide results in 1,4-[PhSNBr]2C6H4, which in turn reacts with triphenylphosphine to generate [1,4-(PhSNSPPh3})2C6H4]Br2. Both Ph2SNBr and 1,4-[PhSNBr]2C6H4 react with the thio-ether crown [9-ane]S3, giving [9[ane]S3NSPh2]Br and [1,4-[9-ane]S2S(NSPh)2C6H4]Br2, respectively. The first examples of seleniosulfimidium salts have been isolated from the reactions of Ph2SNBr and 1,4(PhSNBr})2C6H4 with Ph2Se and the structures of the [Ph2SNSePh2]+ and [1,4-(PhSNSePh2)2C6H4]2+ cations confirmed by X-ray crystallography. Reaction of 1,2-PhS(NH)C6H4SPh with one equivalent of N-bromosuccinimide followed by addition of Na[BPh4] results in [1,2-(PhS)2(μ-N)C6H4][BPh4] in which a CCSNS ring is observed; two forms of this material may be isolated upon crystallisation—X-ray crystallography reveals them to differ by the relative orientations of the phenyl rings.

  溴化亚硫酰亚胺 Ph2SNBr 与二膦 1,2-(PPh2)2C2H4 和 1,4-(Ph2P)2(C6H4) 反应，分别生成双 N-膦亚硫酰亚胺阳离子 [1,2-(Ph2PNSPh2)2C2H4]2+ 和 [1,4-(Ph2PNSPh2)2( )]2+。用 N-溴琥珀酰亚胺处理双亚硫酰 1,4-[PhSNH]2 会生成 1,4-[PhSNBr]2 ，然后与三苯基膦反应生成 [1,4-(PhSNSPPh3})2 ]Br2。Ph2SNBr 和 1,4-[PhSNBr]2 都会与硫醚冠 [9-ane]S3 反应，分别生成 [9[ane]S3NSPh2]Br 和 [1,4-[9-ane]S2S(NSPh)2 ]Br2。从 Ph2SNBr 和 1,4(PhSNBr})2 与 Ph2Se 的反应中分离出了首例硒亚硫鎓盐，并通过 X 射线晶体学证实了 [Ph2SNSePh2]+ 和 [1,4-(PhSNSePh2)2 ]2+ 阳离子的结构。1,2-PhS(NH) SPh 与一个当量的 N-溴代琥珀酰亚胺反应，然后加入 Na[BPh4] 会产生[1,2-(PhS)2(μ-N) ][BPh4]，其中观察到一个 CCSNS 环；结晶后可分离出两种形式的这种物质--X 射线晶体学显示它们因苯基环的相对取向而不同。
• Nucleophilic addition of bifunctional sulfimidosulfides to platinum(IV)-coordinated nitriles
  作者：A. V. Makarycheva-Mikhailova、S. I. Selivanov、N. A. Bokach、V. Yu. Kukushkin、P. F. Kelly、A. J. L Pombeiro

  DOI：10.1007/s11172-005-0017-x

  日期：2004.8

  Reactions of the platinum(IV) nitrile complexes [PtCl4(RCN)2] (R = Me, CH2Ph, Ph) with 1,2- and 1,4-PhS(=NH)C6H4SPh in CH2Cl2 afforded addition products of sulfimides and coordinated nitriles, viz., the [PtCl4NH=C(R)N=S(Ph)(C6H4SPh)}2] complexes. The latter were isolated in 75—90% yields and characterized by elemental analysis, positive-ion FAB mass spectrometry, IR spectroscopy, and 1H and 13C1H NMR spectroscopy. The temperature dependence of the 1H NMR spectra of the model [PtCl4NH=C(R)N=SPh2}2] complexes (R = Me, Et) in CD2Cl2 studied in a temperature range from +40 to -70 °C demonstrated that E—Z isomerization of the ligands is a dynamic process in a range from +40 to -10 °C. The activation free energy of this process was calculated.

  铂(IV)腈络合物[PtCl4(RCN)2] (R = Me, CH2Ph, Ph)与1,2-和1,4-PhS(=NH)C6H4SPh在CH2Cl2中反应，得到硫酰亚胺和配位化合物的加成产物腈，即 [PtCl4NH=C(R)N=S(Ph)( SPh)}2] 配合物。后者的分离产率为 75-90%，并通过元素分析、正离子 FAB 质谱、红外光谱以及 1H 和 13C1H NMR 光谱进行表征。在 +40 至 -70 °C 的温度范围内研究的 CD2Cl2 中模型 [PtCl4NH=C(R)N=SPh2}2] 配合物 (R = Me, Et) 的 1H NMR 光谱的温度依赖性配体的E—Z异构化是+40至-10°C范围内的动态过程。计算了该过程的活化自由能。
• Platinum(IV)-Mediated Nitrile−Sulfimide Coupling:  A Route to Heterodiazadienes
  作者：Anastassiya V. Makarycheva-Mikhailova、Nadezhda A. Bokach、Vadim Yu. Kukushkin、Paul F. Kelly、Liam M. Gilby、Maxim L. Kuznetsov、Kathryn E. Holmes、Matti Haukka、Jonathan Parr、Julia M. Stonehouse、Mark R. J. Elsegood、Armando J. L. Pombeiro

  DOI：10.1021/ic025960w

  日期：2003.1.1

  heterodiazadiene ligands, formed upon Pt(IV)-mediated RCN/sulfimide coupling, can be liberated from their platinum(IV) complexes [PtCl4[NH=C(R)N=SR'Ph]2] by reaction with Ph2PCH2CH2PPh2 (dppe) giving free NH=C(R)=SR'Ph and the dppe oxides, which constitutes a novel route for such rare types of heterodiazadienes whose number has also been extended. The hybrid sulfide/sulfimide species o- and p-[PhS(=NH)](PhS)C6H4

  由Pt（IV）介导的S = NH基团将硫化亚胺Ph2S = NH和混合硫化物/硫化亚胺o-和p- [PhS（= NH）]（PhS）-C6H4加到金属键合的腈中铂（IV）配合物[PtCl4（RCN）2]在室温下于CH2Cl2中平稳进行，并导致杂二氮杂二烯化合物[PtCl4 [NH = C（R）N = SR'Ph] 2]的形成（R'= Ph ，R ＝ Me，Et，CH 2 Ph，Ph； R′＝ o-和p-（PhS）C 6 H 4； R ＝ Et）。反式-[PtCl4（RCN）2]（R = Et，CH2Ph，Ph）与Ph2S = NH的反应仅导致反式-[PtCl4 [NH = C（R）N = SPh2] 2]，顺式/反式-[ PtCl4（MeCN）2]生成[PtCl4 [NH = C（Me）N = SPh2] 2]的顺式/反式混合物，后者已通过柱色谱分离。[PtCl4 [NH = C（Me）N =