(4)N-methyl-2-[1-(pyrrol-2-yl)ethylidene]hydrazine carbothiamide | 344778-31-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: (4)N-methyl-2-[1-(pyrrol-2-yl)ethylidene]hydrazine carbothiamide
• 英文别名: 2-acetylpyrrole-N-methylthiosemicarbazone；1-methyl-3-[1-(1H-pyrrol-2-yl)ethylideneamino]thiourea
• CAS: 344778-31-0
• 化学式: C₈H₁₂N₄S
• mdl: MFCD22192246
• 分子量: 196.276
• InChiKey: PABJOMXOYVOCPH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  84.3
• 氢给体数：
  3
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (4)N-methyl-2-[1-(pyrrol-2-yl)ethylidene]hydrazine carbothiamide 、 trans-bis(triphenylphosphine)palladium dichloride 在 N(C₂H₅)3 作用下， 以 乙腈 为溶剂， 以69%的产率得到Pd(κ3-C4,N3,S-2-acetylpyrrole-N-methylthiosemicarbazonato)
  参考文献：
  名称：

  Thiosemicarbazonates of palladium(II): The presence of methyl/phenyl substituents (R2) at C2 carbon atom induces C–H activation of R1 rings of thiosemicarbazones {R1R2C2N3–N2H–C1(S)–N1HR3}

  摘要：

  A series of palladium(II) complexes involving C-H and N-H bond activations of the R-1 rings of thiosemicarbazones {R-1(R-2)C-2-N-3-N-2(H)-C-1(=S)-(NHR3)-H-1; R-1, R-2: thiopheneyl, Me, H2L1 (R-3 = Me), H2L2 (R-3 = Ph); R-1, R-2: Ph, Me, H2L3 (R-3 = Me), H2L4 (R-3 = Ph); R-1, R-2: Ph, Ph, H2L5 (R-3 = Me), H2L6 (R-3 = Ph) and R-1, R-2: pyrrole, Me, H2L7 (R-3 = Me), H2L8 (R-3 = Ph)} are described. Methyl group (R-2) at C-2 carbon in H2L1 and H2L2 induced C-H bond activation of the thiopheneyl ring and formed cyclometallated complexes, [Pd(kappa(3)-C-4,N-3,S-L)(PPh3)] (L - L-1, 1; L-2, 2). Similarly, phenyl rings (R-1) in H2L3, H2L4, H2L5, H2L6 at C-2 carbon have shown C-H activations forming cyclometallated complexes, [Pd(kappa(3)-C-4,N-3, S-L)(PPh3)] (L = L-3, 3; L-4, 4; L-5, 5; L-6, 6). However, pyrrole ring did not exhibit similar C-H activation behavior, rather involved N-H activation and formed complexes, [Pd(kappa(3)-N-4,N-3, S-L)(PPh3)] {L = L-7, 7; L-8, 8}. All these complexes have been characterized with the help of analytical data, spectroscopic techniques (IR, H-1 and P-31 NMR), and single crystal X-ray crystallography (1, 2, 4, 5, 7 and 8). The thiosemicarbazone ligands behave as dinegative C-4, N-3, S-chelating in 1-6 and N-4, N-3, S-chelating in complexes 7 and 8. Interestingly, complexes 2, 4 and 8, with phenyl substituent at N-1 atom, have two independent molecules in their respective crystal lattices. (C) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2011.11.028

文献信息

• Synthesis and Structural Characterization of Metal Complexes of 2-Formylpyrrole ⁴N-Methylthiosemicarbazone (4ML₁) and 2-Acetyl- pyrrole ⁴N-Methylthiosemicarbazone (4ML₂). The X-Ray Crystal Structures of [Ni(4ML₁-H)₂], [Pd(4ML₁-H)₂] and [Cd(4ML₂)₂I₂]
  作者：Ruben Alonso、Elena Bermejo、Rosa Carballo、Alfonso astiñeiras、Teresa Pérez

  DOI：10.1515/znb-2001-0301

  日期：2001.3.1

  Reaction of ⁴N-methyl-2-[1-(pyrrol-2-yl)methylidene]hydrazinecarbothioamide (4ML₁ and ⁴N-methyl-2-[1-(pyrrol-2-yl)-ethylidene]hydrazine carbothioamide (4ML₁) with zinc(II), cadmium(II) and mercury(II) halides afforded complexes with formulas [M(L)X₂] [(L; M; X) =(4ML₁; Cd; Cl) (4), (4ML₁; Hg; Cl, Br, I) (7 - 9), (4ML₂; Cd; Cl) (17), (4ML₂; Hg; Cl, Br, I) (20 - 22)] or [M(L)₂X₂] [(L; M; X) = (4ML₁; Zn; Cl, Br, I) (1 - 3), (4ML₁; Cd; Br, I) (5, 6), (4ML₂; Zn; Cl, Br, I) (14 - 16), (4ML₂; Cd; Br, I) (18, 19)]. Reaction of 4ML₁ with salts of copper(II), nickel(II), palladium(II) and platinum(II) afforded complexes of formula [M(4ML₁-H)₂] (10 -13). Crystals of 11, 12 and 19 were studied by X-ray diffractometry, and all new compounds were characterized by elemental analysis, mass spectrometry, and IR, electronic and ¹H and ¹³C NMR spectroscopy and, when pertinent and allowed by the solubility of the compound, ¹¹³Cd or ¹⁹⁹Hg NMR spectroscopy. In the complexes of Group 12 metals, both ligands are neutral and S-monodentate. In the complexes of copper or Group 10 metals, 4ML₁ is monodeprotonated and S,N-bidentate.

  将⁴N-甲基-2-[1-(吡咯-2-基)甲基亚氨基]羧硫酰胺(4ML₁)和⁴N-甲基-2-[1-(吡咯-2-基)乙基亚氨基]羧硫酰胺(4ML₂)与锌(II)、镉(II)和汞(II)卤化物反应，得到的配合物的化学式为[M(L)X₂] [(L; M; X) =(4ML₁; Cd; Cl) (4), (4ML₁; Hg; Cl, Br, I) (7 - 9), (4ML₂; Cd; Cl) (17), (4ML₂; Hg; Cl, Br, I) (20 - 22)]或[M(L)₂X₂] [(L; M; X) =(4ML₁; Zn; Cl, Br, I) (1 - 3), (4ML₁; Cd; Br, I) (5, 6), (4ML₂; Zn; Cl, Br, I) (14 - 16), (4ML₂; Cd; Br, I) (18, 19)]。将4ML₁与铜(II)、镍(II)、钯(II)和铂(II)的盐反应，得到的配合物的化学式为[M(4ML₁-H)₂] (10 -13)。11、12和19的晶体结构经过X射线衍射研究，所有新的化合物均通过元素分析、质谱、红外、电子和¹H和¹³C NMR光谱表征，当适用并且化合物的溶解度允许时，还使用¹¹³Cd或¹⁹⁹Hg NMR光谱。在12族金属的配合物中，两个配体均为中性的S-单齿配体。在铜或10族金属的配合物中，4ML₁为单去质子化的S、N-双齿配体。