pyridoxal 4-methyl-3-thiosemicarbazone hydrochloride | 955953-04-5

• 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: pyridoxal 4-methyl-3-thiosemicarbazone hydrochloride
• 英文别名: pyridoxal 4-N-methylthiosemicarbazone hydrochloride；pydridoxal-4-methylthiosemicarbazone hydrochloride；pyridoxal-4-methylthiosemicarbazide hydrochloride；pyridoxal-4-methylthiosemicarbazone hydrochloride；H2mthpy*HCl
• CAS: 955953-04-5
• 化学式: C₁₀H₁₅N₄O₂S*Cl
• 分子量: 290.774
• InChiKey: HLQAVBCHVOTFIQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.44
• 重原子数：
  18.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  89.77
• 氢给体数：
  4.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  Iron(III) nitrate nonahydrate 、 pyridoxal 4-methyl-3-thiosemicarbazone hydrochloride 在 ammonia 、 NH₄Cl 作用下， 以 水 为溶剂， 以54.1%的产率得到[Fe(pyridoxal4-methylthiosemicarbazone(-1H))(pyridoxal-4-methylthiosemicarbazone(-2H)] dihydrate
  参考文献：
  名称：

  Study of Neutral Fe(III) Complexes of Pyridoxal-N-Substituted Thiosemicarbazone with Desolvation-Induced Spin-State Transformation above Room Temperature

  摘要：

  The preparation and characterization of two new neutral ferric complexes with desolvation-induced discontinuous spin-state transformation above room temperature are reported. The compounds, [Fe(Hthpy)(thpy)]-CH3OH center dot 3H(2)O (1) and [Fe(Hmthpy)(mthpy)]-2H(2)O (2), are low-spin (LS) at room temperature and below, whereas their nonsolvated forms are high-spin (HS), exhibiting zero-field splitting, In these complexes, Hthpy, Hmthpy, and thpy, mthpy are the deprotonated forms of pyridoxal thiosemicarbazone and pyridoxal methylthiosemicarbazone, respectively; each is an O,N,S-tridentate ligand. The molecular structures have been determined at 100(1) K using single-crystal X-ray diffraction techniques and resulted in a triclinic system (space group (P1) over tilde) and monoclinic unit cell (space group P2(1)/c) for 1 and 2, respectively. Structures were refined to the final error indices, where R-F = 0.0560 for 1 and R-F = 0.0522 for 2. The chemical inequivalence of the ligands was clearly established, for the "extra" hydrogen atom on the monodeprotonated ligands (Hthpy, Hmthpy) was found to be bound to the nitrogen of the pyridine ring. The ligands are all of the thiol form; the doubly deprotonated chelates (thpy, mthpy) have C-S bond lengths slightly longer than those of the singly deprotonated forms. There is a three-dimensional network of hydrogen bonds in both compounds. The discontinuous spin-state transformation is accompanied with liberation of solvate molecules. This is evidenced also from DSC analysis. Heat capacity data for the LS and HS phases are tabulated at selected temperatures, the values of the enthalpy and entropy changes connected with the change of spin state were reckoned at Delta H = 12.5 +/- 0.3 kJ mol(-1) and AS = 33.3 +/- 0.8 J mol(-1) K-1, respectively, for 1 and Delta H 6.5 +/- 0.3 kJ mol(-1) and AS = 17.6 +/- 0.8 J mol(-1) K-1, respectively, for 2.

  DOI：

  10.1021/ic701695b
• 作为产物：
  描述：

  吡哆醛盐酸盐 、 4-甲基氨基硫脲 以 乙醇 为溶剂， 反应 0.5h， 以73%的产率得到pyridoxal 4-methyl-3-thiosemicarbazone hydrochloride
  参考文献：
  名称：

  吡ido醛N（4）-取代的硫代氨基脲钴（III）配合物的合成，结构和体外生物学活性

  摘要：

  摘要合成了含有吡咯醛N（4）-取代的硫代半碳酰胺配体的钴（III）配合物，其组成为[Co（HL 1−2·Cl）（HL 1−2·H 2 O）]（1-2）。 [CoCl 2（PPh 3）2]与吡ido醛N-甲基-硫代半碳酸盐盐酸盐（H 3 L 1·Cl）/吡rid醛N-苯基-硫代半碳酸盐盐酸盐（H 3 L 2·Cl）的反应。该配体从中性（H 3 L·Cl）（L）变为双阴离子（HL·Cl）（L 2−）和单阴离子形式（HL·H 2 O）的电荷调节，突出了其配位化学的丰富性。 ）（L-）并通过形成中性络合物在钴（III）离子周围配成三齿二元负离子模式。通过各种分析和光谱技术（红外，电子，1 H NMR和ESI-Mass）对新配合物进行了表征。配合物2的X射线晶体结构 演示了金属中心周围扭曲的八面体配位几何形状。此外，对取代基（CH 3或C 6 H 5）对硫半脲的末端N（4）-氮的影响的研究显示出其对

  DOI：

  10.1016/j.ica.2014.05.035

文献信息

• Gold complexes with thiosemicarbazones: reactions of bi- and tridentate thiosemicarbazones with dichloro[2-(dimethylaminomethyl)phenyl-C 1,N ]gold(III), [Au(damp-C 1,N )Cl2]
  作者：Ulrich Abram、Kirstin Ortner、Ronald Gust、Klaus Sommer

  DOI：10.1039/a908712e

  日期：——

  Dichloro[2-(N,N-dimethylaminomethyl)phenyl-C1,N]gold(III), [Au(damp-C1,N)Cl2] (1), reacts with salicylaldehyde thiosemicarbazone (H2saltsc), vanilline thiosemicarbazone (Hvantsc), N-methylpyrrole aldehyde thiosemicarbazone (Hmepyrtsc), pyridoxal methylthiosemicarbazone (H2pydoxmetsc), 2-diphenylphosphinobenzaldehyde thiosemicarbazone (HPtsc) or variously substituted acetylpyridine thiosemicarbazones (HapRtsc; R = H, Me, Ph) with cleavage of the Au–N bond and protonation of the dimethylamino group. Compounds of general formulae [Au(Hdamp-C1)Cl(L)]+ (L = Hsaltsc−, vantsc−, mepyrtsc−), [Au(Hdamp-C1)Cl(L)]2+ (L = H2pydoxmetsc) or [Au(Hdamp-C1)(L)]2+ (L = Ptsc−, apRtsc−, R = H, Me, Ph) have been isolated and characterized. The presence of the σ-bonded 2-(dimethylaminomethyl)phenyl ligand is mandatory to prevent reduction of the gold(III) centre. The crystal structures of [Au(Hdamp-C1)Cl(Hsaltsc)](PF6) (3a), [Au(Hdamp-C1)Cl(mepyrtsc)]Cl (3c), [Au(Hdamp-C1)Cl(H2pydoxmetsc)]Cl2·MeOH (4), [Au(Hdamp-C1)(apPhtsc)]Cl2·2 MeOH (5c) and [Au(Hdamp-C1)(Ptsc)]Cl2· 1.5MeOH (6) have been elucidated, showing the gold atoms in distorted square-planar co-ordination environments. The potentially O,N,S-tridentate ligands H2saltsc and H2pydoxmetsc co-ordinate in a bidentate fashion and do not incorporate the OH groups in the chelating framework, whereas HapRtsc or HPtsc co-ordinate in a tridentate manner. Generally, one or more hydrogen atoms of the heterocyclic ligands and/or the NMe2H+ group form hydrogen bridges in the solid state structures. The preliminary results of antiproliferation tests on tumor cells demonstrate the considerable cytotoxicity of these new gold complexes. p

  二氯[2-(N,N-二甲氨基甲基)苯-C1,N]金(III), [Au(damp-C1,N)Cl2] (1), 与水杨醛缩氨基硫脲(H2saltsc), 香草醛缩氨基硫脲(Hvantsc), N-甲基吡咯醛缩氨基硫脲(Hmepyrtsc), 吡哆醛缩甲基氨基硫脲(H2pydoxmetsc), 2-二苯基膦基苯甲醛缩氨基硫脲(HPtsc)或者各种取代的乙酰吡啶缩氨基硫脲(HapRtsc; R = H, Me, Ph)反应, 导致Au–N键断裂并使二甲氨基质子化. 根据通式[Au(Hdamp-C1)Cl(L)]+(L = Hsaltsc−, vantsc−, mepyrtsc−), [Au(Hdamp-C1)Cl(L)]2+(L = H2pydoxmetsc), 或者[Au(Hdamp-C1)(L)]2+(L = Ptsc−, apRtsc−, R = H, Me, Ph)分离并表征得到化合物. 为了防止金(III)中心的还原, 必须存在σ键合的2-(二甲氨基甲基)苯配体. 通过测定[Au(Hdamp-C1)Cl(Hsaltsc)](PF6) (3a), [Au(Hdamp-C1)Cl(mepyrtsc)]Cl (3c), [Au(Hdamp-C1)Cl(H2pydoxmetsc)]Cl2·MeOH (4), [Au(Hdamp-C1)(apPhtsc)]Cl2·2 MeOH (5c)和[Au(Hdamp-C1)(Ptsc)]Cl2· 1.5MeOH (6)的晶体结构, 发现金原子处于扭曲的平面四边形配位环境. 潜在的O,N,S-三齿配体H2saltsc和H2pydoxmetsc以二齿的形式配位, 没有把羟基包含在螯合骨架中, 然而HapRtsc或HPtsc以三齿的形式配位. 通常, 杂环配体的一个或者多个氢原子和/或者NMe2H+形成氢键出现在固态结构中. 对肿瘤细胞的抗增殖试验的初步结果表明这些新金配合物具有较大的细胞毒性.
• Ruthenium(II) carbonyl complexes containing pyridoxal thiosemicarbazone and trans-bis(triphenylphosphine/arsine): Synthesis, structure and their recyclable catalysis of nitriles to amides and synthesis of imidazolines
  作者：Rajendran Manikandan、Panneerselvam Anitha、Govindan Prakash、Paranthaman Vijayan、Periasamy Viswanathamurthi、Ray Jay Butcher、Jan Grzegorz Malecki

  DOI：10.1016/j.molcata.2014.12.017

  日期：2015.3

  hydrochloride ligands (L1–3) were synthesized and reacted with the ruthenium(II) starting complexes [RuHCl(CO)(EPh3)3] (EP or As). The resulting complexes [Ru(CO)(L1–3)(EPh3)2] (1–6) were characterized by elemental analyses and spectroscopic techniques. The molecular structure of complex 5 was identified by means of single crystal X-ray diffraction analysis. The catalytic activity of the new complexes

  合成了吡咯醛N（4）取代的盐酸替米卡巴zone配体（L 1-3），并与钌（II）起始配合物[RuHCl（CO）（EPh 3）3 ]（EP或As）反应。生成的络合物[Ru（CO）（L 1–3）（EPh 3）2]（1-6）通过元素分析和光谱技术表征。配合物5的分子结构通过单晶X射线衍射分析鉴定。评价了新配合物的催化活性，用于腈在无溶剂条件下的选择性水合为伯酰胺，以及腈与乙二胺的缩合反应。该过程适用于芳族，杂芳族和脂族腈，并能耐受多个取代基。为了寻找在该系列配合物中的最佳催化剂和良好的反应条件，进行了对硫代半脲的取代作用，反应时间，温度，溶剂和催化剂负载量的研究。还提出了两种腈催化反应的可能机理。
• Synthesis, spectral characterization and crystal structure of Ni(II) pyridoxal thiosemicarbazone complexes and their recyclable catalytic application in the nitroaldol (Henry) reaction in ionic liquid media
  作者：Rajendran Manikandan、Panneerselvam Anitha、Govindan Prakash、Paranthaman Vijayan、Periasamy Viswanathamurthi

  DOI：10.1016/j.poly.2014.07.018

  日期：2014.10

  The molecular structure of the complex [Ni(L2)PPh3] (2) was determined by single-crystal X-ray diffraction, which reveals a distorted square planar geometry around the nickel(II) ion. The nitroaldol reaction was studied in detail using the nickel(II) complexes as catalysts in a homogeneous solution formed by an ionic liquid and methanol. The effect of solvent, ionic liquid, time, temperature, catalyst

  摘要由[NiCL2（PPh3）2]与三齿席夫碱配体，吡ido醛硫代半碳zone（L1），吡ido醛N-甲基硫代半碳carb（L2）反应合成了新型方形平面镍（II）配合物1、2和3。乙醇中的吡-醛和吡ido醛N-苯基硫代半碳酮（L3）。这些配合物已通过元素分析，IR，UV-Vis，1H NMR，31P NMR和ESI-MS光谱进行了表征。配合物[Ni（L2）PPh3]（2）的分子结构是通过单晶X射线衍射确定的，该结构揭示了镍（II）离子周围扭曲的正方形平面几何形状。在由离子液体和甲醇形成的均相溶液中，使用镍（II）配合物作为催化剂，对硝基羟醛反应进行了详细的研究。溶剂，离子液体，时间，温度，还研究了催化剂的负载量和反应中配体部分的取代基。以高达97％的高产率获得β-硝基醇产物。根据反应质量的ESI-MS光谱监测，初步提出了一种两步的底物添加机理。
• Palladium(II) pyridoxal thiosemicarbazone complexes as efficient and recyclable catalyst for the synthesis of propargylamines by a three‐component coupling reactions in ionic liquids
  作者：Rajendran Manikandan、Panneerselvam Anitha、Periasamy Viswanathamurthi、Jan Grzegorz Malecki

  DOI：10.1016/j.poly.2016.09.005

  日期：2016.11

  The palladium(II) complexes ( 1 and 2 ) were obtained from the reaction of [PdCl 2 (PPh 3 ) 2 ] with the tridentate Schiff base ligands, pyridoxal thiosemicarbazone (L 1 ), and pyridoxal N-methyl thiosemicarbazone (L 2 ), respectively in ethanol. These complexes were characterized by elemental analyses, IR, UV–Vis, 1 H NMR, 31 P NMR and ESI-MS spectroscopy. The molecular structure of the complex [Pd(L

  摘要由[PdCl 2（PPh 3）2]与三齿席夫碱配体，吡ido醛硫代半碳酰胺（L 1）和吡pyr醛N-甲基硫代半碳酰胺（L 2）反应制得钯（II）配合物（1和2）。 ）分别放在乙醇中。这些配合物的特征在于元素分析，IR，UV-Vis，1 H NMR，31 P NMR和ESI-MS光谱。复合物[Pd（L 2）PPh 3]（2）的分子结构是通过单晶X射线衍射确定的，该结构揭示了钯（II）离子周围扭曲的正方形平面几何形状。为了筛选合成的配合物的催化性能，在无溶剂条件下，钯（II）配合物在80°C的离子液体中催化醛，胺和苯乙炔的三组分偶联反应，以高产率合成炔丙基胺。还研究了溶剂，时间，温度，催化剂负载量和取代基对配体部分反应的影响。结果表明，低负载量（1.0 mol％）的负载型催化剂显示出较高的稳定性，也可以回收并至少重复使用5次，而不会显着降低其活性。
• Charged dioxomolybdenum(VI) complexes with pyridoxal thiosemicarbazone ligands as molybdenum(V) precursors in oxygen atom transfer process and epoxidation (pre)catalysts
  作者：Jana Pisk、Biserka Prugovečki、Dubravka Matković-Čalogović、Rinaldo Poli、Dominique Agustin、Višnja Vrdoljak

  DOI：10.1016/j.poly.2011.12.003

  日期：2012.2

  (3). New dinuclear molybdenum(V) complexes [Mo2O3(HL1–3)2]Cl2 (4–6) were obtained by oxygen atom abstraction from 1–3 with triphenylphosphine. All compounds were characterized by chemical analysis, IR spectroscopy, one- and two-dimensional NMR methods, TGA and in selected cases by DSC measurements. In addition, the crystal and molecular structure of 1a was determined by single crystal X-ray diffraction

  摘要[ （acac）2]与吡ido醛硫半碳鎓配体的盐酸盐H2L1-3·HCl在干燥的甲醇或乙腈中反应，形成单核络合物[ （HL1）（CH3OH）] Cl·1.5 CH3OH（1a）或多核络合物[MoO2（HL1-3）} Cl] n（1-3），在N-硫脲片段的氮原子上包含不同的取代基：Ph（1和1a），Me（2）或H（3）。新的双核钼（V）络合物[Mo2O3（HL1-3）2] Cl2（4-6）是通过用三苯基膦从1-3原子上夺取氧原子而获得的。所有化合物均通过化学分析，红外光谱，一维和二维NMR方法，TGA以及在某些情况下通过DSC测量进行表征。另外，通过单晶X射线衍射确定1a的晶体和分子结构。