tetramethylammonium phenylthiolate | 1559-67-7

• 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: tetramethylammonium phenylthiolate
• 英文别名: tetramethylammonium benzenethiolate；Tetramethyl-ammonium thiophenolate；benzenethiolate;tetramethylazanium
• CAS: 1559-67-7
• 化学式: C₄H₁₂N*C₆H₅S
• 分子量: 183.318
• InChiKey: YGNLYPMMDVNYFZ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  1.91
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  、 tetramethylammonium phenylthiolate 以 氘代二甲亚砜 为溶剂， 反应 2.0h， 以88%的产率得到
  参考文献：
  名称：

  镍 (II/IV) 歧管可实现室温 C(sp3)–H 功能化

  摘要：

  本文展示了高价 Ni 中心的轻度氧化诱导 C(sp3)-H 活化。与 NiII 的大多数 C(sp3)-H 活化反应相反，转化在室温下进行并生成可分离的 NiIV σ-烷基配合物。密度泛函理论研究表明，这种 CH 活化过程有两种可能的机制，包括在 NiIV 或 NiIII 中间体处三氟甲磺酸盐辅助 CH 裂解。前一种途径比后者略受青睐（约 3 kcal/mol）。CH 裂解的 NiIV σ-烷基产物与各种亲核试剂反应形成 C(sp3)-X 键（X = 卤化物、氧、氮、硫或碳）。这些化学计量转化可以使用 N-fluoro-2,4,

  DOI：

  10.1021/jacs.9b11999
• 作为产物：
  描述：

  四甲基氢氧化铵 、 苯硫酚 以 苯 为溶剂， 反应 1.0h， 以97.8%的产率得到tetramethylammonium phenylthiolate
  参考文献：
  名称：

  Synthesis of tetraalkylammonium thiolates

  摘要：

  A convenient method has been developed for the preparation of tetraalkylammonium thiolates by the reaction of tetraalkylammonium hydroxides with various thiols in benzene.

  DOI：

  10.1007/bf00960427
• 作为试剂：
  描述：

  1-吲哚金刚烷 、 在 tetrabutylammonium tetrafluoroborate 、 tetramethylammonium phenylthiolate 作用下， 以 乙腈 为溶剂， 以45%的产率得到1-adamantyl naphthyl sulfide
  参考文献：
  名称：

  Nonchain Processes in Nucleophilic Substitutions Triggered by Electron Transfer (SRN1). Photochemical and Electrochemical Induction of the Substitution of 1-Iodoadamantane by Arenethiolate Ions

  摘要：

  Photochemical induction of the reaction of 1-iodoadamantane with arenethiolate ions provides a clear-cut example of nonchain S(RN)1 substitutions. With 4-methoxy-, 4-methyl-, and 4-cyanobenzene and benzenethiolate ions, excellent yields (over 85%) are obtained in spite of efficient electron transfer quenching of the very easily oxidized anion radical of the substituted product by quaternary ammonium countercations. The production of the corresponding disulfides is used to determine the number of chains. Absorption and fluorescence spectroscopy and laser pulse irradiation experiments indicate that the electron which triggers the substitution process is generated by photoejection from the nucleophile, with an efficiency that decreases in the order 4-methoxybenzene > 4-methylbenzene > 4-benzene > 4-cyanobenzenethiolate. Electron photoejection does not occur with naphthalenethiolate ions. However substitution can be entrained by addition of benzenethiolate ions. The two nucleophiles were found to have comparable reactivities toward the 1-adamantyl radical. Rather than the formation of its anion radical, the first step of the S(RN)1 process is a dissociative electron transfer to 1-iodoadamantane, yielding directly the adamantyl radical. This is the reason that direct electrochemical induction of the substitution was not observed. Induction by electrogenerated aromatic anion radicals could be observed. It was much less efficient than photoinduction because the amount of electron donor species required to trigger the reaction is much larger.

  DOI：

  10.1021/ja00151a012

文献信息

• Experimental and Computational Studies of High-Valent Nickel and Palladium Complexes
  作者：Nicole M. Camasso、Allan J. Canty、Alireza Ariafard、Melanie S. Sanford

  DOI：10.1021/acs.organomet.7b00613

  日期：2017.11.27

  The accessibility of the MIII and MIV oxidation states with each metal is investigated through electrochemical and chemical oxidation of the MII precursors. These studies show that the NiII precursor readily undergoes both one- and two-electron oxidations to generate stable NiIII and NiIV products. In contrast, under the conditions examined, the PdII analogue undergoes exclusively two-electron-oxidation

  本文介绍了由三（吡唑基）硼酸酯和环新叶生物配体支撑的高价镍和钯模型配合物的有机金属化学的详细比较。通过M II前体的电化学和化学氧化研究了M III和M IV氧化态与每种金属的可及性。这些研究表明，Ni II前体易于经历一电子和二电子氧化，以生成稳定的Ni III和Ni IV产物。相反，在所检查的条件下，Pd II类似物仅进行两次电子氧化反应以形成Pd IV。分离的Ni IV和Pd IV配合物的反应性研究表明，它们都参与C（sp 3）-杂原子偶联反应，并且Ni IV处的反应比Pd IV处的反应快约2个数量级。实验和计算机制研究暗示了这些过程的外球S N 2型途径。对于大多数亲核试剂（例如酚盐，乙酸盐，噻吩氧化物），C（sp 3）-杂原子偶联反应可产生TpM II（σ-芳基）产物。但是，以叠氮化物为亲核试剂，初始C（sp 3）–N 3的Ni II产物偶合随后发生C（sp 2）–N插入反应。计算结果表明，该过程中涉及阴离子Ni
• Electrochemically induced aromatic substitution. The 2-nitropropane anion, a powerful nucleophile in SRN1 aromatic substitution
  作者：Christian Amatore、Monique Gareil、Mehmet A. Oturan、Jean Pinson、Jean Michel Saveant、Andre Thiebault

  DOI：10.1021/jo00370a003

  日期：1986.10