triphenylmethanedithiosulfenyl chloride | 152216-81-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 三苯基化合物
• 英文名称: triphenylmethanedithiosulfenyl chloride
• 英文别名: chloro(triphenylmethyl)trisulfane；chloro(triphenylmethyl)trisulfide；(Trityldisulfanyl) thiohypochlorite
• CAS: 152216-81-4
• 化学式: C₁₉H₁₅ClS₃
• 分子量: 374.979
• InChiKey: NPQCEUKGLORTHC-UHFFFAOYSA-N

物化性质

• 沸点：
  495.2±55.0 °C(Predicted)
• 密度：
  1.310±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  23
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  75.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  triphenylmethanedithiosulfenyl chloride 在 sodium hydrogensulfide 作用下， 以 乙醚 为溶剂， 反应 24.0h， 以46%的产率得到Bis(triphenylmethyl)heptasulfane
  参考文献：
  名称：

  Structure and chemistry of chloro(triphenylmethyl)sulfanes

  摘要：

  The structures of chloro(triphenylmethyl)mono-, di-, and -trisulfanes were obtained. The monosulfane displayed a triclinic (P1) space group, a = 10.792(2) Angstrom, b = 15.090(2) Angstrom, c = 10.027(2) Angstrom, alpha = 100.15(1)degrees, beta 103.13(1)degrees, gamma = 88.80(1)degrees, Z = 4. The disulfane gave a triclinic (P1) space group, a = 9.758(1) Angstrom, b = 10.426(2) Angstrom, c = 9.1691(6) Angstrom, alpha = 97.52(1)degrees, beta = 90.116(1)degrees, gamma = 116.750(1)degrees, Z = 2. The trisulfane gave an orthorhombic space group (Pna2(1)), a = 9.224(1) Angstrom, b = 19.196(3) Angstrom, c = 10.308(1) Angstrom, Z = 4. The sulfenyl chlorides decompose above their melting points to mixtures consisting primarily of triphenylchloromethane and sulfur. The sulfur was determined to consist of several allotropes (S-6, S-7, S-8, and S-9). The di- and trisulfanes slowly decompose to the same products at room temperature; the decompositions are enhanced by light. The decomposition of the trisulfane in the presence of dienes gave adducts consistent with the transfer of a two-sulfur species. The disulfane and trisulfane undergo the normal nucleophilic substitution reactions of the monosulfanes.

  DOI：

  10.1021/jo00083a022
• 作为产物：
  描述：

  三苯甲硫醇 在 二氯化二硫 作用下， 以 乙醚 为溶剂， 以61%的产率得到triphenylmethanedithiosulfenyl chloride
  参考文献：
  名称：

  Structure and chemistry of chloro(triphenylmethyl)sulfanes

  摘要：

  The structures of chloro(triphenylmethyl)mono-, di-, and -trisulfanes were obtained. The monosulfane displayed a triclinic (P1) space group, a = 10.792(2) Angstrom, b = 15.090(2) Angstrom, c = 10.027(2) Angstrom, alpha = 100.15(1)degrees, beta 103.13(1)degrees, gamma = 88.80(1)degrees, Z = 4. The disulfane gave a triclinic (P1) space group, a = 9.758(1) Angstrom, b = 10.426(2) Angstrom, c = 9.1691(6) Angstrom, alpha = 97.52(1)degrees, beta = 90.116(1)degrees, gamma = 116.750(1)degrees, Z = 2. The trisulfane gave an orthorhombic space group (Pna2(1)), a = 9.224(1) Angstrom, b = 19.196(3) Angstrom, c = 10.308(1) Angstrom, Z = 4. The sulfenyl chlorides decompose above their melting points to mixtures consisting primarily of triphenylchloromethane and sulfur. The sulfur was determined to consist of several allotropes (S-6, S-7, S-8, and S-9). The di- and trisulfanes slowly decompose to the same products at room temperature; the decompositions are enhanced by light. The decomposition of the trisulfane in the presence of dienes gave adducts consistent with the transfer of a two-sulfur species. The disulfane and trisulfane undergo the normal nucleophilic substitution reactions of the monosulfanes.

  DOI：

  10.1021/jo00083a022

文献信息

• Sulfenyl chloride chemistry. Precursors for diatomic sulfur transfer
  作者：Imad A. Abu-Yousef、David N. Harpp

  DOI：10.1016/0040-4039(94)85351-7

  日期：1994.9

  [(C6H5)3CSSCl] (and its dithio homolog 2 [(C6H5)3CSSSCl]) give stable addition products (ca. 85% yield) with cyclopentene and cyclohexene. When these adducts are warmed with a diene, they deliver diatomic sulfur-trapped derivatives. These tetrasulfides are quantitatively converted to the corresponding disulfide 3 with triphenylphosphine; this affords cyclic disulfides in & 50% isolated yield from the

  三苯基甲硫基亚硫酰氯1 [（C 6 H 5）3 CSSCl]（及其二硫代同系物2 [（C 6 H 5）3 CSSSCl]）与环戊烯和环己烯形成稳定的加成产物（产率约85％）。当这些加合物被二烯加热时，它们会释放出双原子的硫捕获的衍生物。用三苯基膦将这些四硫化物定量转化为相应的二硫化物3。这提供了环状二硫化物，从二烯分离出的产率为50％。此外，已经获得了涉及二硫杂环戊烷中间体4的证据。
• Three sulfur atom insertion into the SS bond—pentasulfide preparation
  作者：Yihua Hou、Imad A Abu-Yousef、David N Harpp

  DOI：10.1016/s0040-4039(00)01357-5

  日期：2000.10

  Chloro(triphenylmethyl)trisulfide (1) reacts under mild conditions with symmetric primary dialkyl disulfides and aromatic disulfides giving pentasulfides as the main products in good yield and selectivity. A mechanism involving a triphenylmethyl alkyl/phenyl tetrasulfide intermediate is discussed.

  氯（三苯基甲基）三硫化物（1）在温和的条件下与对称的伯二烷基二硫化物和芳族二硫化物反应，以高收率和选择性得到五硫化物作为主要产物。讨论了涉及三苯基甲基烷基/苯基四硫化物中间体的机理。
• Preparation of 17 Sulfur‐Rich Chain‐Like Thiaalkanes R−S _<i>x</i> −R′−S _<i>y</i> −R and R−S _<i>x</i> −R′−S _<i>y</i> −R′−S _<i>z</i> −R ( <i>x</i> , <i>y</i> , <i>z</i>  &gt; 2) from Titanocene Thiolate Complexes
  作者：Vera Münchow、Ralf Steudel

  DOI：10.1002/ejic.200300591

  日期：2004.2

  AbstractTwo novel Cp2Ti(Cl)S3R′S3Tr complexes have been prepared by reaction of the six‐membered metallacycles Cp2TiS4R′ (Cp = η5‐C5H5, R′ = CMe2, 1,1‐C6H10) with the sulfenyl chloride TrSCl (Tr = CPh3) at 20 °C. These complexes were treated with: (a) sulfenyl chlorides (RSCl or RSSCl) to obtain 11 new thiaalkanes of the type R−Sx−R′−Sy−R (R = Tr, 4‐ClC6H4, 2‐C10H7; x = 3, y > 2), or (b) with SO2Cl2, SCl2 or S2Cl2 to prepare six sulfur‐rich species of the type Tr−Sx−R′−Sy−R′−Sz−Tr (x, z = 3, y > 3), as well as Cp2TiCl2. The thiaalkanes decompose upon heating to give mixtures of various linear and cyclic polysulfanes R2Sn and R′Sm. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
• Sulfenyl Chloride Chemistry. New Precursors for Diatomic Sulfur Transfer
  作者：Imad A. Abu-Yousef、David N. Harpp

  DOI：10.1021/jo9710792

  日期：1998.11.1

  When triphenylmethanesulfenyl chloride (1) (or its thio homologue 2) are treated with various bicycles, norbornene (5), or bicyclo[2.2.2]octene (6), dithio adducts 7 and 8 were produced in good isolated yields. Final products were obtained via an episulfide intermediate. The stereochemistry of addition has been determined by X-ray analysis. Treatment of thiosulfenyl chloride 2 (or its dithio homologue 3) with other olefins, cyclopentene (10), cyclohexene (11), or 1,4-dioxene (12), leads to the formation of disulfides (13-15 from 2) and trisulfides (16 and 17 from 3) in high isolated yields (ca. 92%). The structures of 7, 8, and 13-17 were established by H-1 and C-13 NMR and elemental analysis as well as by X-ray determination. When these adducts are warmed with a 1,3-diene 42, they deliver diatomic sulfur-trapped derivatives, cyclic di-49 and tetrasulfide adducts 46. A variety of solvents, temperatures, times, and concentrations were employed to optimize the yield of 46 and 49. The tetrasulfide adduct 46 is quantitatively converted to disulfide 49 with triphenylphosphine; this affords cyclic disulfides in >50% isolated yield from the diene. In addition, evidence has been obtained implicating dithietane intermediate 4.
• Total Synthesis of (+)-MPC1001B
  作者：Taichi Kurogi、Shun Okaya、Hideto Fujiwara、Kentaro Okano、Hidetoshi Tokuyama

  DOI：10.1002/anie.201507830

  日期：2016.1.4

  AbstractThe first total synthesis of an epidithiodiketopiperazine alkaloid, (+)‐MPC1001B, was accomplished. This synthesis features a tetra‐n‐butylammonium fluoride mediated intramolecular aldol reaction for forming the 15‐membered macrolactone ring, and the construction of an epidithiodiketopiperazine substructure through a stepwise sulfenylation reaction involving a novel trityl trisulfide (TrSSS)‐group transfer.