N,N-bis(acetylthiomethyl)-p-chloroaniline | 127099-06-3

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: N,N-bis(acetylthiomethyl)-p-chloroaniline
• 英文别名: S-[[N-(acetylsulfanylmethyl)-4-chloroanilino]methyl] ethanethioate
• CAS: 127099-06-3
• 化学式: C₁₂H₁₄ClNO₂S₂
• 分子量: 303.834
• InChiKey: WTLWSBFZJQSMKT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  18
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  88
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  N,N-bis(acetylthiomethyl)-p-chloroaniline 在 sodium t-butanolate 作用下， 以 四氢呋喃 、 丙酮 为溶剂， 反应 9.0h， 生成 [[4-ClC₆H₄N(CH₂S)₂]Fe(CO)2(1,2-bis(diphenylphosphino)ethene)]
  参考文献：
  名称：

  异双核镍 (II)-铁 (II) 氮杂二硫醇盐作为 [NiFe]-氢化酶活性位点的结构和功能模型

  摘要：

  为开发[NiFe]-H 2酶的仿生化学，第一个氮杂二硫醇桥联的NiFe模型配合物[CpNi{(μ-SCH 2 ) 2 NR}Fe(CO)(diphos)]BF 4 ( 5 , R = Ph , diphos = dppv; 6 , 4-ClC 6 H 4 , dppv; 7 , 4-MeC 6 H 4 , dppv; 8 , CO 2 CH 2 Ph, dppe; 9 , H, dppe) 已通过精心设计合成合成路线。因此，用t处理 RN[CH 2 S(O)CMe] 2-BuONa，然后将所得中间体 RN(CH 2 SNa) 2与 (dppv)Fe(CO) 2 Cl 2或 (dppe)Fe(CO) 2 Cl 2反应，得到 N-取代的氮杂二硫醇基螯合的 Fe 配合物 [RN (CH 2 S) 2 ]Fe(CO) 2 (diphos) ( 1 , R = Ph, diphos = dppv; 2

  DOI：

  10.1039/d0ra04344c
• 作为产物：
  描述：

  聚合甲醛 、 对氯苯胺 、 硫代乙酸 以 乙醇 、 水 为溶剂， 反应 3.0h， 以78%的产率得到N,N-bis(acetylthiomethyl)-p-chloroaniline
  参考文献：
  名称：

  镍（II）镍（II）Azadithiolates：合成，结构表征，及其电ħ 2生产

  摘要：

  Azadithiolato桥接双核的Ni 2种配合物的通式[（η 5 -C 5 H ^ 5）的Ni {（μ-SCH 2）2 NC 6 H ^ 4 R-4}的Ni（DIPHOS）] BF 4（8 - 11， R = H，Cl，MeO; diphos = dppv，dppe）已通过精心设计的合成方法制备，包括以下三个独立的反应步骤。在第一反应步骤涉及制备双（硫代酯）的前体4-RC 6 H ^ 4 N（CH 2 S（O）CME）2（1 - 3（R ＝ H，Cl，MeO），通过苯胺或其取代的衍生物4-RC 6 H 4 NH 2与37％的甲醛水溶液和硫代乙酸的缩聚反应。第二步涉及制备单核Ni前体（diphos）Ni [（SCH 2）2 NC 6 H 4 R-4]（4 – 7，R = H，Cl，MeO； diphos = dppv，dppe）双一锅反应（硫酯）的前体1 - 3与吨-BuONa接着处理所得到的中间体二钠4-RC

  DOI：

  10.1021/acs.organomet.0c00130

文献信息

• Syntheses of optically active γ-ketothiols and the esters by lipase-catalyzed hydrolysis via α-acetylthiomethylation of ketones
  作者：Tomohiko Izawa、Yoshiyasu Terao、Kunio Suzuki

  DOI：10.1016/s0957-4166(97)00281-4

  日期：1997.8

  The alpha-acetylthiomethylation of ketones was achieved by the reaction of ketones or the enamines with N,N-bis-(acetylthiomethyl)-p-chloroaniline in the presence of trifluoroacetic acid. The resulting thiolesters were hydrolyzed enantioselectively by catalysis of lipases. (C) 1997 Elsevier Science Ltd.
• N-Substituted Derivatives of the Azadithiolate Cofactor from the [FeFe] Hydrogenases: Stability and Complexation
  作者：Raja Angamuthu、Chi-Shian Chen、Tyler R. Cochrane、Danielle L. Gray、David Schilter、Olbelina A. Ulloa、Thomas B. Rauchfuss

  DOI：10.1021/acs.inorgchem.5b00290

  日期：2015.6.15

  Experiments are described that probe the stability of N-substituted derivatives of the azadithiolate cofactor recently confirmed in the [FeFe] hydrogenases (Berggren, G., et al. Nature 2013, 499, 66). Acid-catalyzed hydrolysis of bis(thioester) BnN(CH2SAc)(2) gives [BnNCH2SCH2](2) rather than azadithiol BnN(CH2SH)(2). Treatment of BnN(CH2SAc)(2) with (NaOBu)-Bu-t generates BnN(CH2SNa)(2), which was trapped with NiCl2(diphos) (diphos = 1,2-C2H4(PR2)(2); R = Ph (dppe) and Cy (dcpe)) to give fully characterized complexes Ni[(SCH2)(2)NBn](diphos). The related N-aryl derivative Ni[(SCH2)(2)NC6H4Cl](diphos) was prepared analogously from 4-ClC6H4N(CH2SAc)(2), (NaOBu)-Bu-t, and NiCl2(dppe). Crystallographic analysis confirmed that these rare nonbridging [adt(R)](2-) complexes feature distorted square planar Ni centers. The analogue Pd[(SCH2)(2)NBn](dppe) was also prepared. P-31 NMR analysis indicates that Ni[(SCH2)(2)NBn](dppe) has basicity comparable to typical amines. As shown by cyclic voltammetry, the couple [M[(SCH2)(2)NBn](dppe)](+/0) is reversible near -2.0 V versus Fc(+/0). The wave shifts to 1.78 V upon N-protonation. In the presence of CF3CO2H, Ni[(SCH2)(2)NBn](dppe) catalyzes hydrogen evolution at rate of 22 s(-1) in the acid-independent regime, at room temperature in CH2Cl2 solution. In contrast to the instability of RN(CH2SH)(2) (R = alkyl, aryl), the dithiol of tosylamide TsN(CH2SH)(2) proved sufficiently stable to allow full characterization. This dithiol reacts with Fe-3(CO)(12) and, in the presence of base, NiCl2(dppe) to give Fe-2[(SCH2)(2)NTs](CO)(6) and Ni[(SCH2)(2)NTsi(dPPe), respectively.
• Nickel(II)–Nickel(II) Azadithiolates: Synthesis, Structural Characterization, and Electrocatalytic H₂ Production
  作者：Li-Cheng Song、Wen-Bo Liu、Bei-Bei Liu

  DOI：10.1021/acs.organomet.0c00130

  日期：2020.4.27

  Azadithiolato-bridged dinuclear Ni2 complexes with the general formula [(η5-C5H5)Ni(μ-SCH2)2NC6H4R-4}Ni(diphos)]BF4 (8–11, R = H, Cl, MeO; diphos = dppv, dppe) have been prepared by a well-designed synthetic method including the following three separate reaction steps. The first reaction step involves preparation of the bis(thioester) precursors 4-RC6H4N(CH2S(O)CMe)2 (1–3, R = H, Cl, MeO) by a cocondensation

  Azadithiolato桥接双核的Ni 2种配合物的通式[（η 5 -C 5 H ^ 5）的Ni （μ-SCH 2）2 NC 6 H ^ 4 R-4}的Ni（DIPHOS）] BF 4（8 - 11， R = H，Cl，MeO; diphos = dppv，dppe）已通过精心设计的合成方法制备，包括以下三个独立的反应步骤。在第一反应步骤涉及制备双（硫代酯）的前体4-RC 6 H ^ 4 N（CH 2 S（O）CME）2（1 - 3（R ＝ H，Cl，MeO），通过苯胺或其取代的衍生物4-RC 6 H 4 NH 2与37％的甲醛水溶液和硫代乙酸的缩聚反应。第二步涉及制备单核Ni前体（diphos）Ni [（SCH 2）2 NC 6 H 4 R-4]（4 – 7，R = H，Cl，MeO； diphos = dppv，dppe）双一锅反应（硫酯）的前体1 - 3与吨-BuONa接着处理所得到的中间体二钠4-RC
• Heterodinuclear nickel(<scp>ii</scp>)–iron(<scp>ii</scp>) azadithiolates as structural and functional models for the active site of [NiFe]-hydrogenases
  作者：Li-Cheng Song、Bei-Bei Liu、Wen-Bo Liu、Zheng-Lei Tan

  DOI：10.1039/d0ra04344c

  日期：——

  with (dppv)Fe(CO)2Cl2 or (dppe)Fe(CO)2Cl2 gave the N-substituted azadithiolato-chelated Fe complexes [RN(CH2S)2]Fe(CO)2(diphos) (1, R = Ph, diphos = dppv; 2, 4-ClC6H4, dppv; 3, 4-MeC6H4, dppv; 4, CO2CH2Ph, dppe). Further treatment of 1–4 with nickelocene in the presence of HBF4·Et2O afforded the corresponding N-substituted azadithiolato-bridged NiFe model complexes 5–8, while treatment of 8 with HBF4·Et2O

  为开发[NiFe]-H 2酶的仿生化学，第一个氮杂二硫醇桥联的NiFe模型配合物[CpNi(μ-SCH 2 ) 2 NR}Fe(CO)(diphos)]BF 4 ( 5 , R = Ph , diphos = dppv; 6 , 4-ClC 6 H 4 , dppv; 7 , 4-MeC 6 H 4 , dppv; 8 , CO 2 CH 2 Ph, dppe; 9 , H, dppe) 已通过精心设计合成合成路线。因此，用t处理 RN[CH 2 S(O)CMe] 2-BuONa，然后将所得中间体 RN(CH 2 SNa) 2与 (dppv)Fe(CO) 2 Cl 2或 (dppe)Fe(CO) 2 Cl 2反应，得到 N-取代的氮杂二硫醇基螯合的 Fe 配合物 [RN (CH 2 S) 2 ]Fe(CO) 2 (diphos) ( 1 , R = Ph, diphos = dppv; 2