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(C6H4)]2+。用 N-溴琥珀酰亚胺处理双亚硫酰 1,4-[PhSNH]2C6H4 会生成 1,4-[PhSNBr]2C6H4，然后与三苯基膦反应生成 [1,4-(PhSNSPPh3})2C6H4]Br2。Ph2SNBr 和 1,4-[PhSNBr]2C6H4 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)2C6H4]Br2。从 Ph2SNBr 和 1,4(PhSNBr})2C6H4 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)2C6H4]2+ 阳离子的结构。1,2-PhS(NH)C6H4SPh 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)C6H4][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)(C6H4SPh)}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 =
• 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 <i>trans</i> ‐[PdCl ₂ {1,2‐(PhS{NH})(PhS)C ₆ H ₄ }PPh ₃ ]
  作者：Mark R. J. Elsegood、Kathryn E. Holmes、Paul F. Kelly、Elizabeth J. MacLean、Jonathon Parr、Julia M. Stonehouse

  DOI：10.1002/ejic.200390012

  日期：2003.1

  AbstractReaction of [PPh4]2[Pd2X6] (where X = Cl, Br or I) with 1,4‐(PhSNH})2C6H4 (1) in dichloromethane results in the formation of [Pd1,4‐(PhSNH})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‐(PhSNH})(PhS)C6H4 (3) results in the formation of [PdCl21,2‐(PhSNH})(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‐[PdCl21,2‐(PhSNH})(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)
• The preparation and structure of novel sulfimide systems; X-ray crystal structures of 1,4-(PhS{NH})2C6H4 (and dihydrate), 1,2-(PhS{NH})(PhS)C6H4·H2O and of [Ph2SNH] and its hydrate
  作者：Mark R. J. Elsegood、Kathryn E. Holmes、Paul F. Kelly、Jonathan Parr、Julia M. Stonehouse

  DOI：10.1039/b103502a

  日期：2002.2.11

  hydrated free sulfimides 1,4-(PhSNH})2C6H4·2H2O 1a and 1-(PhSNH})-2-(PhS)C6H4·H2O 2a. The X-ray crystal structures of both 1a and 2a, together with that of the well-known sulfimide Ph2SNH·H2O 3a, all reveal extended hydrogen-bonded arrays involving the N–H units and the waters of crystallisation. Crystals of 1b, the dehydrated form of 1a, also readily form, while removal of the water from 3ain vacuo

  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。