(4-Chlorophenyl) benzenecarbodithioate | 77069-61-5

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: (4-Chlorophenyl) benzenecarbodithioate
• CAS: 77069-61-5
• 化学式: C₁₃H₉ClS₂
• 分子量: 264.799
• InChiKey: DWRMIRCOWHXKOR-UHFFFAOYSA-N

物化性质

• 沸点：
  388.0±44.0 °C(Predicted)
• 密度：
  1.34±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  57.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (4-Chlorophenyl) benzenecarbodithioate 、 苯胺 以 乙腈 为溶剂， 生成 硫苯甲醯胺苯
  参考文献：
  名称：

  Oh, Hyuck Keun; Shin, Chul Ho; Lee, Ikchoon, Journal of the Chemical Society. Perkin transactions II, 1995, # 6, p. 1169 - 1174

  摘要：

  DOI：
• 作为产物：
  描述：

  S-(4-chlorophenyl) benzothioate 在 劳森试剂 作用下， 以 甲苯 为溶剂， 生成 (4-Chlorophenyl) benzenecarbodithioate
  参考文献：
  名称：

  Oh, Hyuck Keun; Shin, Chul Ho; Lee, Ikchoon, Journal of the Chemical Society. Perkin transactions II, 1995, # 6, p. 1169 - 1174

  摘要：

  DOI：

文献信息

• Phosphorus Pentasulfide:  A Mild and Versatile Catalyst/Reagent for the Preparation of Dithiocarboxylic Esters
  作者：Arumugam Sudalai、Subbareddy Kanagasabapathy、Brian C. Benicewicz

  DOI：10.1021/ol006407q

  日期：2000.10.1

  The reaction of carboxylic acids (1) with a variety of thiols or alcohols in the presence of phosphorus pentasulfide (P(4)S(10)) as a catalyst and reagent (20-40 mol %) proceeded effectively to afford the corresponding dithiocarboxylic esters (2) in high yields.

  在作为催化剂和五硫化二磷（P（4）S（10））和试剂（20-40 mol％）的五硫化二磷（P（4）S（10））存在下，羧酸（1）与多种硫醇或醇的反应有效进行，得到了相应的二硫代羧酸酯（2），收率高。
• Effect of modification of the electrophilic center on the α effect
  作者：Ik-Hwan Um、Ji-Youn Lee、Sun-Young Bae、Erwin Buncel

  DOI：10.1139/v05-157

  日期：2005.9.1

  We report on a nucleophilic study of esters R-C(=X)-Y-Ar in which the electrophilic center has been modified by replacing O by S in the leaving group or carbonyl center: 4-nitrophenyl acetate (1), S-4-nitrophenyl thioacetate (2), 4-nitrophenyl benzoate (3), and O-4-nitrophenyl thionobenzoate (4). The studies include O^– and S^– nucleophiles as well as α nucleophiles in H₂O at 25.0 ± 0.1 °C. The sulfur nucleophile (4-chlorothiophenoxide, 4-ClPhS^–) exhibits significant enhanced reactivity for the reactions with thiol and thione esters 2 and 4 compared with their oxygen analogues 1 and 3. On the contrary, the common nucleophile OH^– is much less reactive towards 2 and 4 compared with 1 and 3. The effect of changing both the electrophilic center and the nucleofugic center on the reactivity of the other oxygen nucleophiles is not so significant: 4-chlorophenoxide (4-ClPhO^–) is four to six times more reactive in the reactions with thiol and thione esters 2 and 4 compared with their oxygen analogues 1 and 3. The α effects exhibited by butan-2,3-dione monoximate (Ox^–) and HOO^– are strongly dependent on the nature of the electrophilic center of the substrates, indicating that the difference in the ground-state solvation energy cannot be fully responsible for the α effect. Our results clearly emphasize the strong dependence of the α effect on the substrate structure, notably, the nature of the electrophilic center. The impact of change in the nucleofuge (1→2) and the electrophilic center (3→4) on reactivity indicates that α nucleophiles will need to be “purpose built” for decontamination and nucleophilic degradation of specific biocides.Key words: α effect, nucleophilicity, nucleofuge effect, electrophilicity, polarizability.

  我们报道了对酯R-C(=X)-Y-Ar的亲核研究，其中亲电中心通过将离去基团或羰基中的O替换为S而被修改：4-硝基苯乙酸酯(1)，S-4-硝基苯硫代酸酯(2)，4-硝基苯甲酸酯(3)和O-4-硝基苯硫代苯甲酸酯(4)。这些研究包括O-和S-亲核试剂以及H₂O中的α-亲核试剂，在25.0 ± 0.1°C下进行。硫亲核试剂(4-氯硫代苯氧根离子，4-ClPhS^–)对与硫醇和硫酮酯2和4的反应表现出明显增强的反应性，与它们的氧类似物1和3相比。相反，常见的亲核试剂OH^–对2和4的反应性要比1和3低得多。改变亲电中心和离去基团对其他氧亲核试剂的反应性的影响并不那么显著：4-氯苯氧根离子(4-ClPhO^–)在与硫醇和硫酮酯2和4的反应中比它们的氧类似物1和3更具有四到六倍的反应性。丁二酮单羟胺盐(Ox^–)和HOO^–所表现出的α效应强烈依赖于底物亲电中心的性质，表明基态溶剂化能量的差异不能完全解释α效应。我们的结果清楚地强调了α效应对底物结构的强烈依赖，特别是亲电中心的性质。改变离去基团(1→2)和亲电中心(3→4)对反应性的影响表明，α亲核试剂将需要针对特定生物杀虫剂的去污和亲核降解而“定制”。关键词：α效应，亲核性，离去基团效应，亲电性，极化率。
• Kinetics and mechanism of the pyridinolysis of aryl dithiobenzoates in acetonitrile
  作者：Hyuck Keun Oh、Jae Myon Lee、Hai Whang Lee、Ikchoon Lee

  DOI：10.1002/kin.20000

  日期：2004.8

  the zwitterionic tetrahedral intermediate, T±, at pKa = 5.2 as the pyridine basicity is increased. Rates are compared with those corresponding values for aryl dithioacetates (R = Me). The faster rates for R = Me than for R = Ph, for the rate-limiting formation of T±, can be attributed to the hyperconjugative charge transfer effect of the Me group, pseudo-πMe π*C=S. Clear-cut change in the cross-interaction

  研究了二硫代苯甲酸芳基酯 (RC(S)SC6H4Z; R = Ph) 与吡啶 (XC5H4N) 在乙腈中在 60.0°C 下氨解的动力学和机理。在 pKa° = 5.2 时，斜率从大值 (βX ≅ 0.7–0.8) 变为小值 (βX ≅ 0.2) 得到双相布朗斯特图，这被解释为表明速率决定步骤的变化随着吡啶碱度的增加，在 pKa = 5.2 时从分解到形成两性离子四面体中间体 T±。将速率与芳基二硫代乙酸酯 (R = Me) 的相应值进行比较。对于 T± 的限速形成，R = Me 比 R = Ph 更快的速率可归因​​于 Me 基团的超共轭电荷转移效应，伪 πMe π*C=S。交叉相互作用常数 ρXZ 从 +1.47 到 -0 的明显变化。20 支持提议的机制更改。目前工作中 R = Ph 的 pKa° = 5.2 处的断点与 R = Me 和 2-呋喃基的吡啶解的断点一致，并证明了酰基 R
• Polyvalent Iodine in Synthesis; 3. An Efficient Method for the Synthesis of Aryl Arenedithiocarboxylates
  作者：Zhen-Chu Chen、You-Yuan Jin、Rui-Yang Yang

  DOI：10.1055/s-1988-27688

  日期：——

  A new method for the synthesis of aryl arenedithiocarboxylates consists of the S-arylation of sodium arenedithiocarboxylates with diaryliodonium chlorides or bromides in tert-butyl alcohol.

  一种合成芳香二硫代羧酸盐的新的方法是将钠芳香二硫代羧酸盐与二芳基碘鎂或溴化物在叔丁醇中进行S-芳基化反应。
• Esterification of Thioamides via Selective N–C(S) Cleavage under Mild Conditions
  作者：Xinhao Zhu、Kerou Wan、Jin Zhang、Hui Zhao、Yang He、Yangmin Ma、Xiufang Yang、Michal Szostak

  DOI：10.1021/acs.orglett.3c02238

  日期：2023.8.25

  Herein, we report an exceedingly mild method for the direct, transition-metal-free esterification of thioamides through the selective generation of tetrahedral intermediates. The method represents the first transition-metal-free approach to the thioamide to thionoester transformation in organic synthesis. This reactivity has been accomplished through N,N-Boc2-thioamides that engage in ground-state

  在此，我们报告了一种极其温和的方法，通过选择性生成四面体中间体来直接、无过渡金属酯化硫代酰胺。该方法代表了有机合成中第一个无过渡金属的硫代酰胺向硫代酸酯转化的方法。这种反应性是通过N,N -Boc 2 -硫代酰胺实现的，其参与 n N → π* C=S共轭的基态不稳定。“单原子”生物等排硫代酰胺的基态不稳定将扩大有价值的酰胺键功能化反应的库。