diacetyl-2-(4-methyl-3-thiosemicarbazone)-3-(2-hydrazonepyridine) | 876661-43-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: diacetyl-2-(4-methyl-3-thiosemicarbazone)-3-(2-hydrazonepyridine)
• 英文别名: diacetyl-2-(4-methyl-3-thiosemicarbazone)-3-(2-pyridinehydrazone)；diacetyl-2-(4-methyl-thiosemicarbazone)-3-(2-hydrazinopyridine)；H₂L¹；1-Methyl-3-[3-(pyridin-2-ylhydrazinylidene)butan-2-ylideneamino]thiourea
• CAS: 876661-43-7
• 化学式: C₁₁H₁₆N₆S
• 分子量: 264.354
• InChiKey: UGBRMXRCWUIJOV-UHFFFAOYSA-N

物化性质

• 沸点：
  396.3±34.0 °C(Predicted)
• 密度：
  1.22±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  106
• 氢给体数：
  3
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  diacetyl-2-(4-methyl-3-thiosemicarbazone)-3-(2-hydrazonepyridine) 以 甲醇 、 乙醇 为溶剂， 生成
  参考文献：
  名称：

  Ni(II) 和 Pd(II)DMTH 的配体中心析氢

  摘要：

  在这项研究中，我们报道了一对基于非无辜配体 diacetyl-2-(4-methyl-3-thiosemicarbazone)-3-(2-pyridinehydrazone) (H 2 DMTH, H ) 的析氢反应 (HER) 电催化剂。2升1 )。通过光谱和电化学方法合成并表征了中性配合物NiL 1和PdL 1 。配合物含有在 HER 过程中质子化的非配位碱性肼氮。通过在乙腈中分光光度滴定测定该氮的p Ka 对于NiL 1为12.71，对于PdL 1为13.03。NiL 1和 PdL的循环伏安图NiL 1和 PdL 1在乙腈中的1分别在 -1.83 和 -1.79 V（相对于二茂铁/二茂铁）下表现出扩散控制的可逆配体中心事件。NiL 1和PdL 1分别在-2.43 和-2.34 V 处观察到准可逆、以配体为中心的事件。对每种催化剂使用一系列中性酸和阳离子酸评估乙腈中的 HER 活性。动力学同位素效应

  DOI：

  10.1021/acs.inorgchem.2c01326
• 作为产物：
  描述：

  2-肼吡啶 、 diacetyl mono-4-methyl-3-thiosemicarbazone 以 甲醇 为溶剂， 反应 24.0h， 以54%的产率得到diacetyl-2-(4-methyl-3-thiosemicarbazone)-3-(2-hydrazonepyridine)
  参考文献：
  名称：

  Complexes of group 12 metals containing a hybrid thiosemicarbazone-pyridylhydrazone ligand

  摘要：

  The reaction of diacetyl-2-(4-methyl-3-thiosemicarbazone) with 2-hydrazinopyridine leads to the formation of two products, LH2 and [LH3]Cl depending on the amount of HCl present in the reaction mixture. The reactivity of these molecules towards zinc(II), cadmium(II) and mercury(II) nitrates has been investigated under different reaction conditions. The new complexes have been fully characterized by Cd-113 and Hg-199 NMR, as well as C-13 and Cd-113 CP/MAS NMR and by X-ray diffraction. All the complexes have the same 1: 1 ligand to metal ratio, but the protonation state of the ligand depends on the reaction conditions, from neutral to double deprotonated. The coordination numbers in the complexes depend on the metal preferences leading to the formation of complexes with different structural characteristics. (C) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2011.10.023

文献信息

• The Reactivity of Diphenyllead(IV) Dichloride with Dissymmetric Thiosemicarbazone Ligands: Obtaining Monomers, Coordination Polymers, and an Organoplumboxane
  作者：Ester Sesmero、David G. Calatayud、Josefina Perles、Elena López‐Torres、M. Antonia Mendiola

  DOI：10.1002/ejic.201501245

  日期：2016.3

  The reaction of PbPh2Cl2 with two dissymmetric thiosemicarbazone ligands containing diacetyl 4-methyl-3-thiosemicarbazone and hydrazonepyridine or hydrazonequinoline arms led to four new mononuclear complexes, [PbPh2(L)] (1 and 3) and [PbPh2Cl(HL)] (2 and 4). Reactions with the hydrazonequinoline ligand strongly depend on the reaction conditions and several unexpected compounds were isolated. At room

  PbPh2Cl2 与包含二乙酰 4-甲基-3-氨基硫脲和腙吡啶或腙喹啉臂的两个不对称缩氨基硫脲配体的反应产生了四种新的单核配合物，[PbPh2(L)]（1 和 3）和 [PbPh2Cl(HL)] (2和 4）。与腙喹啉配体的反应强烈依赖于反应条件，并且分离出几种意想不到的化合物。在室温下，除了配合物 4 外，聚合化合物 [PbPh2Cl2CH3OH]n (5) 被分离出来，而在回流加热下发生对称化和含有二乙酰双（4-甲基-3-氨基硫脲）的聚合物，[PbPh2Cl2 (H2ATSM)]n (6) 得到。当 PbPh2Cl2 在含有 LiOH·H2O 的湿二氯甲烷中回流加热时，​​四核有机铂烷 [Pb4Ph8Cl4O2] (7) 被分离出来，据我们所知，是第一个被结晶学表征的有机铂烷。所有化合物都经过彻底表征，包括通过 207Pb NMR 和单晶 XRD。此外，腙喹啉配体已证明其作为有机铅 (IV)
• Utilizing Charge Effects and Minimizing Intramolecular Proton Rearrangement to Improve the Overpotential of a Thiosemicarbazonato Zinc HER Catalyst
  作者：Steve P. Cronin、Abdullah Al Mamun、Megan J. Toda、Mark S. Mashuta、Yaroslav Losovyj、Pawel M. Kozlowski、Robert M. Buchanan、Craig A. Grapperhaus

  DOI：10.1021/acs.inorgchem.9b01912

  日期：2019.10.7

  addition of acetic acid. Addition of methyl iodide to 1 yields the corresponding methylated derivative ZnL2I (3). In solution, partial dissociation of the coordinated iodide yields the cationic derivative 3′. Complexes 1–3 were characterized by 1H NMR, FT-IR, and UV–visible spectroscopies. The solid-state structures of 2 and 3 were determined by single crystal X-ray diffraction. HER studies conducted in

  制备了二乙酰基-2-（4-甲基-3-硫代半碳酰胺）-3-（2-hydr吡啶吡啶）的锌（II）配合物ZnL 1（1）并作为制氢反应（HER）的前催化剂进行了评估在均匀条件下在乙腈中。将配合物1在the吡啶部分的非配位氮上质子化，从而在添加乙酸后产生活性催化剂Zn（HL 1）OAc（2）。甲基碘加到1产生相应的甲基化衍生物ZnL 2 I（3）。在溶液中，配位碘化物的部分解离产生阳离子衍生物3'。配合物1- 3通过其特征在于1 H NMR，FT-IR，和紫外-可见光谱。通过单晶X射线衍射确定2和3的固态结构。在乙腈中以乙酸作为质子源进行的HER研究表明，在1.27 V的超电势下，溶液1的周转频率（TOF）为7700 s –1，对于在3的超电势下溶液3的TOF为6700 s –1。 0.56V。对于两种络合物，催化所需的电势E cat / 2均大于热力学还原电势E 1/2表示分子内质子重排的动力学障碍。1（+440
• Metal–Ligand Cooperativity Promotes Reversible Capture of Dilute CO₂ as a Zn(II)-Methylcarbonate
  作者：Christine A. Phipps、Dillon T. Hofsommer、Calian D. Zirilli、Bailee G. Duff、Mark S. Mashuta、Robert M. Buchanan、Craig A. Grapperhaus

  DOI：10.1021/acs.inorgchem.2c03868

  日期：2023.2.13

  (H2L1) yielded ML1 (M = Ni(II), Pd(II)), ML1(CH3OH) (M = Cu(II), Zn(II)), and [ML1(PPh3)2]BF4 (M = Co(III)) complexes. The ML1(CH3OH) complexes reversibly capture CO2 with equilibrium constants of 88 ± 9 and 6900 ± 180 for Cu(II) and Zn(II), respectively. Ligand effects were evaluated with Zn(II) through variation of the 4-methyl-thiosemicarbazone with 4-ethyl (H2L2), 4-phenethyl (H2L3), and 4-benzyl

  在这项研究中，评估了一系列作为 CO 2捕获剂的氨基硫脲-肼基吡啶金属络合物。这些配合物包含一个非配位的碱性肼基吡啶氮，它非常接近路易斯酸性金属离子，从而实现金属-配体协同作用。各种金属离子与 (diacetyl-2-(4-methyl-thiosemicarbazone)-3-(2-hydrazinopyridine) (H 2 L 1 ) 的配位产生 ML 1 (M = Ni(II), Pd(II)), ML 1 (CH 3 OH) (M = Cu(II), Zn(II)), and [ML 1 (PPh 3 ) 2 ]BF 4 (M = Co(III)) 络合物。ML 1 (CH 3OH) 复合物可逆地捕获 CO 2，Cu(II) 和 Zn(II) 的平衡常数分别为 88 ± 9 和 6900 ± 180。通过改变 4-甲基-缩氨基硫脲与 4-乙基 (H 2 L 2 )、4-苯乙基 (H
• Copper Complexes of Thiosemicarbazone−Pyridylhydrazine (THYNIC) Hybrid Ligands:  A New Versatile Potential Bifunctional Chelator for Copper Radiopharmaceuticals
  作者：Andrew R. Cowley、Jonathan R. Dilworth、Paul S. Donnelly、Jonathan M. White

  DOI：10.1021/ic0514492

  日期：2006.1.1

  Two new thiosemicarbazone-pyridylhydrazine (THYNIC) hybrid ligands have been synthesized. Copper(II) and copper(I) complexes of the ligands have been prepared and characterized by X-ray crystallography. Cyclic voltammetry measurements show that the copper(II) complexes undergo quasi-reversible reductions at biologically accessible potentials. One of the ligands, bearing a pendant carboxylate arm, has been conjugated to N-alpha-(tert-butoxycarbonyl)-L-lysine.
• Technetium Nitrido Complexes of Tetradentate Thiosemicarbazones: Kit-Based Radiolabeling, Characterization, and <i>In Vivo</i> Evaluation
  作者：Cormac A. A. Kelderman、Rachel C. Maclean、Ingebjørg N. Hungnes、Patrick R. W. J. Davey、Ekaterina Salimova、Michael de Veer、Natasha Patel、Michelle T. Ma、Brett M. Paterson

  DOI：10.1021/acs.inorgchem.3c02650

  日期：2023.12.18