ethyl 2-methylacetoacetate thiosemicarbazone | 73937-86-7

• 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-methylacetoacetate thiosemicarbazone
• 英文别名: Ethyl 3-(carbamothioylhydrazinylidene)-2-methylbutanoate
• CAS: 73937-86-7
• 化学式: C₈H₁₅N₃O₂S
• 分子量: 217.292
• InChiKey: IMPQYMOPTCHZIH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.625
• 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：

  五羰基溴铼(I) 、 ethyl 2-methylacetoacetate thiosemicarbazone 以 甲苯 为溶剂， 生成
  参考文献：
  名称：

  hen（I）诱导的衍生自β-酮酯的硫代半咔唑的环化反应。

  摘要：

  乙酰乙酸甲酯和2-甲基乙酰乙酸乙酯的硫代半咔唑酮（分别为H（2）L（A）和H（2）L（B））与[ReX（CO）（5）]和[ReX（CO）（3） （CH（3）CN）（2）]（X = Cl，Br）在各种实验条件下进行了探索。除了加合物fac- [ReX（CO）（3）（H（2）L）]（其中is与三个羰基，X阴离子和N，S-双齿硫代半碳酰胺配体配位）外，还存在以下配合物还分离了：fac- [ReBr（CO）（3）（Hpyz（B））]，四聚体复合物fac- [Re（pyz（A））（CO）（3）]（4）和fac- [Re （pyz（B））（CO）（3）]（4）和fac- [Re（pyz（B））（CO）（3）（H（2）O）]（其中Hpyz（A）和Hpyz （B）是分别通过H（2）L（A）和H（2）L（B）的环化衍生的吡唑啉酮。通过（1）H NMR光谱监测环化反应，并通过元素分析，质谱，IR和（1）H N

  DOI：

  10.1021/ic030154q

文献信息

• Reactions of thiosemicarbazones derived from β-keto amides and β-keto esters with Zn(<scp>ii</scp>) and Cd(<scp>ii</scp>) acetates: influence of metal, substitution, reagent ratio and temperature on metal-induced cyclization
  作者：José S. Casas、María V. Castaño、María S. García-Tasende、Enrique Rodríguez-Castellón、Agustín Sánchez、Luisa M. Sanjuán、José Sordo

  DOI：10.1039/b401674b

  日期：——

  Surprisingly, the reactions of zinc(II) acetate with HTSC in 1 ∶ 1 mol ratio usually gave a third, previously unreported type of complex with a dideprotonated ligand, [Zn(L − H)], which was also formed when [ZnL2] and Zn(OAc)2 interacted at room temperature in 1 ∶ 1 mol ratio. These L − H complexes are highly insoluble in all common solvents, which hinders their characterization but suggests that they are

  乙酸锌（II）和乙酸镉（II）在甲醇 在各种实验条件下，使用衍生自β-酮酰胺或β-酮的硫代半氨基唑 酯类（HTSC）。这些反应中的一些反应提供了硫代半氨基甲酸酯配合物[M（TSC）2 ]，其中红外 和 核磁共振谱与N，S-配位相容，但多数可得到络合物[ML 2 ]，其中HL是由以下物质产生的取代的2,5-二氢-5-氧代-1 H-吡唑-1-碳硫酰胺环化HTSC。这些吡唑啉酸酯中的一些和HL中的两种配体 被研究 X射线衍射，并讨论了它们的结构。令人惊讶的是，锌（II）乙酸盐 HTSC的摩尔比为1：1时，通常会生成第三种先前未报道的双去质子化的复合物 配体，[Zn（L-H）]，也是当[ZnL 2 ]和Zn（OAc）2在室温下以1：1摩尔比相互作用时形成的。这些L-H络合物在所有常见情况下均高度不溶溶剂，这阻碍了它们的表征，但表明它们本质上是聚合的。
• 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.
• Metal-Induced Cyclization of Thiosemicarbazones Derived from β-Keto Amides and β-Keto Esters:  Open-Chain and Cyclized Ligands in Zinc(II) Complexes
  作者：José S. Casas、María V. Castaño、Eduardo E. Castellano、Javier Ellena、María S. García-Tasende、Ángeles Gato、Agustín Sánchez、Luisa M. Sanjuán、José Sordo

  DOI：10.1021/ic0111942

  日期：2002.3.1

  The reactions of Zn(OAc)(2) with acetoacetanilide, methyl acetoacetate, o-acetoacetanisidide, and ethyl 2-methylacetoacetate thiosemicarbazones (HTSC1, HTSC2, HTSC3, and HTSC4, respectively) were explored in methanol. With HTSC1, HTSC2, and HTSC3, following isolation of the corresponding zinc(II) thiosemicarbazonates [Zn(TSCx)(2)] (x = 1, 2, 3), the mother liquors afforded pyrazolonate complexes [ZnL21(H2O)] (HL1 = 2,5-dihydro-3-methyl-5-oxo-1H-pyrazole-1-carbothioamide) that had been formed by cyclization of the corresponding TSC-. The reaction of HTSC4 with zinc(II) acetate gave only the pyrazolonate complex [ZnL22(H2O)] (HL2 = 2,5-dihydro-3,4-dimethyl5-oxo-1H-pyrazole-1-carbothioamide). All compounds were studied by IR and NMR spectroscopy, and HTSC3, [Zn(TSC3)(2)]-DMSO, [ZnL21(H2O)](.)2DMSO, and [ZnL22(H2O)](.)2DMSO were also studied by X-ray diffractometry, giving a thorough picture of the cyclization process. In preliminary tests of the effects of HL1 and [ZnL21(H2O)] on rat paw inflammatory edema induced by carrageenan, HL1 showed antiinflammatory activity.
• 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.
• Rhenium(I)-Induced Cyclization of Thiosemicarbazones Derived from β-Keto Esters
  作者：Rosa Carballo、José S. Casas、Emilia García-Martínez、Gumersindo Pereiras-Gabián、Agustín Sánchez、José Sordo、Ezequiel M. Vázquez-López

  DOI：10.1021/ic030154q

  日期：2003.10.1

  the tetrameric complexes fac-[Re(pyz(A))(CO)(3)](4) and fac-[Re(pyz(B))(CO)(3)](4), and fac-[Re(pyz(B))(CO)(3)(H(2)O)] (where Hpyz(A) and Hpyz(B) are pyrazolones derived by cyclization of H(2)L(A) and H(2)L(B), respectively). The cyclization reactions were monitored by (1)H NMR spectroscopy and the complexes isolated were identified by elemental analysis, mass spectrometry, IR and (1)H NMR spectroscopy

  乙酰乙酸甲酯和2-甲基乙酰乙酸乙酯的硫代半咔唑酮（分别为H（2）L（A）和H（2）L（B））与[ReX（CO）（5）]和[ReX（CO）（3） （CH（3）CN）（2）]（X = Cl，Br）在各种实验条件下进行了探索。除了加合物fac- [ReX（CO）（3）（H（2）L）]（其中is与三个羰基，X阴离子和N，S-双齿硫代半碳酰胺配体配位）外，还存在以下配合物还分离了：fac- [ReBr（CO）（3）（Hpyz（B））]，四聚体复合物fac- [Re（pyz（A））（CO）（3）]（4）和fac- [Re （pyz（B））（CO）（3）]（4）和fac- [Re（pyz（B））（CO）（3）（H（2）O）]（其中Hpyz（A）和Hpyz （B）是分别通过H（2）L（A）和H（2）L（B）的环化衍生的吡唑啉酮。通过（1）H NMR光谱监测环化反应，并通过元素分析，质谱，IR和（1）H N