ethyl 2-ethylacetoacetate thiosemicarbazone | 87610-70-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: ethyl 2-ethylacetoacetate thiosemicarbazone
• 英文别名: Ethyl 3-(carbamothioylhydrazinylidene)-2-ethylbutanoate
• CAS: 87610-70-6
• 化学式: C₉H₁₇N₃O₂S
• 分子量: 231.319
• InChiKey: VFIMOLCAPQODTD-UHFFFAOYSA-N

物化性质

• 熔点：
  72 °C
• 沸点：
  335.8±44.0 °C(Predicted)
• 密度：
  1.19±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  109
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ethyl 2-ethylacetoacetate thiosemicarbazone 、 lead acetate 以 甲醇 为溶剂， 生成 Pb(4-ethyl-2,5-dihydro-3-methyl-5-oxo-1H-pyrazole-1-carbothiamidate)2
  参考文献：
  名称：

  New lead(II) complexes with N,S-ligands, including a lead pyrazolonate with unusual packing flexibility

  摘要：

  The reaction of lead(II) acetate in methanol with thiosemicarbazones derived from beta-keto esters and beta-keto amides (HTSCs) afforded two lead(II) thiosernicarbazonates and numerous homoleptic ([PbL2]) and/or heteroleptic ([Pb(OAc)L]) complexes containing deprotonated pyrazolones L- formed by metal-induced cyclization of the starting HTSC ligands. All the complexes isolated were characterized by IR spectroscopy in the solid state and by H-1 and 13 C NMR spectroscopy in DMSO solution; in addition, crystals containing [Pb(L 6)21 and [Pb(L-7)(2)] were examined by X-ray crystallography. [Pb(L-6)(2)] center dot 0.5H(2)O center dot 0.3MeOH (HL6 = 4-ethyl-2,5-dihydro-3-methyl-5-oxo-1Hpyrazole- I-carbothiamide) showed three types of molecule with significant structural differences that appear to be determined by packing interactions. In all three molecules the Pb...Ph distances are very short [3.6096(8)-3.7562(8) angstrom], but den sity-functional-theoretic calculations at the B3LYP level do not support the existence of Pb-Pb bonds. In [Pb(L-7)(2)] (HL7 = N-ethyl-2,5-dihydro-3-methyl-5-oxo-1Hpyrazole-1-carbothiamide) all the molecules are of a single type, and they are linked in a three-dimensional network by weak intermolecular Ph...O bonds. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2007.05.016

文献信息

• Diphenyllead(IV) thiosemicarbazonates and pyrazolonates: Synthesis and characterization
  作者：José S. Casas、Eduardo E. Castellano、Javier Ellena、María S. García-Tasende、Agustín Sánchez、José Sordo、Ángeles Touceda

  DOI：10.1016/j.poly.2009.01.004

  日期：2009.4

  Cyclization of thiosemicarbazones derived from beta-keto esters and beta-keto amides (HTSC) in the presence of diphenyllead(IV) acetate was explored in methanol solution at room temperature and under reflux. All beta-keto ester TSCs underwent cyclization to give the corresponding pyrazolone (HL), which, except in one case, deprotonated and coordinated the PbPh22+ moiety to form homoleptic [PbPh2(L)(2)] or heteroleptic [PbPh2(OAc)(L)] derivatives. Cyclization did not occur with beta-keto amide TSCs and only [Pbph(2)(TSC)(2)] or [PbPh2(OAc)(TSC)] thiosernicarbazonates were isolated. The complexes were characterized by IR spectroscopy in the solid state and by H-1, C-13 and Pb-207 NMR spectroscopy in DMSO-d(G) solution, in which they evolve and decompose with time. Additionally, crystals of p-acetoacetanisidide thiosemicarbazone (HTSC10), [PbPh2(OAc)(L-5)] center dot MeOH (HL5 = 2,5-dihydro-3,4-dimethyl-5-oxo-1H-pyrazolone-1-carbothioamide), [PbPh2Cl(L-2)] (HL2 = 2,5-dihydro-5-oxo-3-phenyl-1H-pyrazolone-1-carbothioamide), [PbPh2(OAc)(TSC8)]center dot 2MeOH (HTSC8 = acetoacetanilide thiosemicarbazone), [PbPh2(OAc)(TSC10)]center dot H2O and [PbPh2(OAc)(TSC11)] center dot 0.75MeOH (HTSO11 = o-acetoacetotoluidide) were studied by X-ray crystallography. The complexes, monomers or dimers with almost linear C-Pb-C moieties, are compared with the corresponding derivatives of Pb(II). (C) 2009 Elsevier Ltd. All rights reserved.
• Zn(II) pyrazolonate complexes obtained by metal-induced cyclization of thiosemicarbazones: Crystal structures and spectroscopic properties
  作者：J.S. Casas、M.V. Castaño、M.S. García-Tasende、A. Sánchez、J. Sordo、A. Touceda

  DOI：10.1016/j.poly.2005.06.040

  日期：2005.12

  The reaction of zinc(II) acetate with thiosemicarbazones derived from P-keto esters (methyl propionylacetate thiosemicarbazone, ethyl benzoylacetate thiosemicarbazone, ethyl 2-ethylacetoacetate thiosemicarbazone and methyl acetoacetate N-1-ethylthiosemicarbazone) induces the cyclization of the thiosemicarbazone to afford [ZnL2] and (in one case) [ZnL2(MeOH)] complexes, where HL is a substituted 2,5-dihydro-5-oxo-1H-pyrazolone-1-carbothioamide. The four complexes were studied by X-ray diffraction, which showed that the pyrazolonate ligand binds with the metal through the S and N(3) atoms. The influence of cyclization and metallation on the H-1 and C-13 NMR spectra of the starting thiosemicarbazones is also discussed. (c) 2005 Elsevier Ltd. All rights reserved.
• New lead(II) complexes with N,S-ligands, including a lead pyrazolonate with unusual packing flexibility
  作者：José S. Casas、Eduardo E. Castellano、Javier Ellena、María S. García-Tasende、Agustín Sánchez、José Sordo、Ángeles Touceda、Saulo Vázquez Rodríguez

  DOI：10.1016/j.poly.2007.05.016

  日期：2007.9

  The reaction of lead(II) acetate in methanol with thiosemicarbazones derived from beta-keto esters and beta-keto amides (HTSCs) afforded two lead(II) thiosernicarbazonates and numerous homoleptic ([PbL2]) and/or heteroleptic ([Pb(OAc)L]) complexes containing deprotonated pyrazolones L- formed by metal-induced cyclization of the starting HTSC ligands. All the complexes isolated were characterized by IR spectroscopy in the solid state and by H-1 and 13 C NMR spectroscopy in DMSO solution; in addition, crystals containing [Pb(L 6)21 and [Pb(L-7)(2)] were examined by X-ray crystallography. [Pb(L-6)(2)] center dot 0.5H(2)O center dot 0.3MeOH (HL6 = 4-ethyl-2,5-dihydro-3-methyl-5-oxo-1Hpyrazole- I-carbothiamide) showed three types of molecule with significant structural differences that appear to be determined by packing interactions. In all three molecules the Pb...Ph distances are very short [3.6096(8)-3.7562(8) angstrom], but den sity-functional-theoretic calculations at the B3LYP level do not support the existence of Pb-Pb bonds. In [Pb(L-7)(2)] (HL7 = N-ethyl-2,5-dihydro-3-methyl-5-oxo-1Hpyrazole-1-carbothiamide) all the molecules are of a single type, and they are linked in a three-dimensional network by weak intermolecular Ph...O bonds. (c) 2007 Elsevier Ltd. All rights reserved.