1,2,4-三嗪类化合物的研究XXI.3-甲硫基-5-氧代-2.5-二氧-1,2,4-三嗪的取代苯磺铣化反应及6- 碳的亲电特性

3-甲硫基-5-氧代-2.5-二氧-1,2,4-三嗪(Ic)与取代的苯磺铣氯反应,在无水吡啶中生成N-[6-(3-甲硫基-5-负氧基)-1,2,4-三嗪基]吡啶内嗡盐(4);在NaOH-H~2O-Ch~3COCH~3中生成3-甲硫基-4-(取代苯磺铣基)-5-氧化-6-羟基-1,4,5,6-四氢- 12,4-(6);资Naoh-Ch~3O中则生成1-(对甲苯磺铣基)-3-甲硫基-6-甲氧基-1,4,5,6-四氢-三嗪(7)显示了其6-C具有不寻常的亲电特性.     

1,2,4-三嗪类化合物的研究——XXI.3-甲硫基-5-氧代-2,5-二氢-1,2,4-三嗪的取代苯磺酰化反应及6-碳的亲电特性

3-甲硫基-5-氧代-2,5-二氢-1,2,4-嗪(lc)与取代的苯磺酰氯反应,在无水吡啶中生成N-[6-(3-甲硫基-5-负氧基)-1,2,4-三嗪基]吡啶内(钅翁)盐(4);在NaOH-H_(2)O-CH_(3)COCH_(3)中生成3-甲硫基-4-(取代苯磺酰基)-5-氧代-6-羟基-1,4,5,6-四氢-1,2,4-三嗪(6);在NaOH-CH_3OH中则生成1-(对甲苯磺酰基)-3-甲硫基-5-氧代-6-甲氧基-1,4,5,6-四氢-1,2,4-三嗪(7),显示了其6-C具有不寻常的亲电特性.     

1,2,4-三嗪类化合物的研究 XVI. 3-甲硫基-5-氧代-2,5-二氢-1,2,4-三嗪的不正常对甲苯磺酰化反应及其产物的性质

本文报道了N-[6-(3-甲硫基-5-负氧基)-1,2,4-三嗪基]吡啶内 盐(4a)的制备、结构测定及性质的研究。     

1,2,4-三嗪类化合物的研究(ⅩⅩ)——利用波谱分析确定3-甲硫基-5-羟基-1,2,4-三嗪的取代苯磺酰化反应及其产物的结构

为寻找有效的抗肿瘤药物,作者对1,2,4-三嗪类化合物(6-氮杂尿嘧啶)的化学性质进行了研究,发现3-甲硫基-5-羟基-1,2,4-三嗪(1)在无水吡啶中与对甲苯磺酰氯发生不正常的对甲苯磺酰化反应,生成N-[6-(3-甲硫基-5-负氧基)-1,2,4-三嗪基]吡啶内鎓盐以及对甲苯磺酸对甲苯硫酚酯。为了研究其反应机理,把溶剂改为等摩尔NaOH的CH_3COCH_3-H_2O溶液,重复文献的实验。反应产物分离提纯后,确定其结构为3-甲硫基-4-对甲苯磺酰基-5-氧代-6-羟基-1,4,5,6-四氢-1,2,4-三嗪(2a)。此反应特点是:在1,2,4-三嗪环的4-氮上     

1,2,4-三嗪类化合物的研究 XVI. 3-甲硫基-5-氧代-2,5-二氢-1,2,4-三嗪的不正常对甲苯磺酰化反应及其产物的性质

本文报道了N-[6-(3-甲硫基-5-负氧基)-1,2,4-三嗪基]吡啶内 盐(4a)的制备、结构测定及性质的研究。     

3-氨基-5-取代苯氨基-6-苯基-1,2,4-三嗪的合成

3-氨基-1,2,4-三嗪化合物具有广泛的生理活性,如:治疗支气管扩张、抑制乳酸菌和症原虫繁殖杀菌等,因此,研究这类化合物合成方法应运而生。本文以苯甲酰基硫代甲酰胺为原料,进一步合成了氨基-5-取代苯氨基-6-苯基-1,2,4-三嗪。     

5-取代苯氨基-6-苯基-1,2,4-三嗪-3-酮的合成

苯甲铣基-N-取代茜基硫代甲酰胺与氨基脲缩合后,环化可何成4,6-二取代-5-硫酮-1,2,4-三嗪-3-酮.本文报道将其缩氨基脲中硫甲基化,然后在碱性条件下, 改变成环方式,合成九个5-取代苯氨基-6-苯基-1,1,4-三嗪1-3-酮.它们的结构经元素分析,红外,核磁,质谱等予以证实.探讨了两种不同成环原因.     

1,2,4-三嗪类化合物的研究 VIII: 3-甲硫基-5-羟基-1,2,4-三嗪-6-羧酸乙酯和N^2-[5'-(3'-甲硫基-6'-乙氧羰基)-1',2',4'-三嗪基]-3-甲硫基-5-氧代-1,2,4-三嗪-6-羧酸乙酯的氧化及其取代反应

本文报道3-甲硫基-5-羟基-1,2,4-三嗪-6-羧酸乙酯(4)及N^2-[5'-(3'-甲硫基-6'-乙氧羰基)-1',2',4'-三嗪基]-3-甲硫基-5-氧代-1,2,4-三嗪-6-羧酸乙酯(8)分子内,甲硫基的氧化及其就地与取代芳胺进行亲核取代反应.3-甲砜基和N^2-[5'-(3'-甲硫基-6'-乙氧羰基)-1',2',4'-三嗪基]作为离去基,其离去能力相近.     

5-取代苯氨基-6-甲基-1,2,4-三嗪-3-硫酮的合成

含有 1 ,2 ,4 三嗪结构的化合物具有广泛的生理活性。我们曾用α 乙酰基硫代甲酰芳胺为原料 ,合成了一系列三嗪类和其它杂环化合物 ,其中1 ,2 ,4 三嗪类有 4,6 二取代 5 硫酮 1 ,2 ,4三嗪 3 酮[1 ,2 ] ,3 氨基 5 取代苯氨基 6 苯基 1 ,2 ,4 三嗪[3] 等化合物。本文以α 乙酰基硫代甲酰芳胺为原料 ,进一步合成 5 取代苯氨基 6 甲基 1 ,2 ,4 三嗪 3 硫酮。当乙酰基硫代甲酰芳胺 1 (ａ ｇ)与氨基硫脲 2反应时 ,首先生成缩氨基硫脲 3(ａ ｇ) ,然后环化得到 5 取代苯氨基 6 甲基 1 ,2 ,4 三嗪 3硫酮 4(ａ ｇ) ,合成中发现 ,4(ａ ｇ)可…     

Reaction of 4-Amino-3-methylthio-5-oxo-6-R-4,5-dihydro-1,2,4-triazines with Sulfonylacetic Acid Nitriles

The reactions of 4-amino-3-methylthio-5-oxo-6-R-4,5-dihydro-1,2,4-triazines with arylsulfonylacetonitriles and with dinitriles of sulfonyldiacetic acid and methylenebis(sulfonylacetic) acid have been studied. 7-Amino-3-R-8-(R'-sulfonyl)-1,4-dihydropyrazolo[5,1-c][1,2,4]triazin-4-ones have been synthesized and these are the first representatives of geminal sulfones in which the heterocyclic ring is bound directly to the sulfur atoms of the sulfonyl groups.     

四氯化碳和吡啶对苯和环己烷中正子素生成的影响

研究了在含不同浓度电子清除剂CCL_4或正穴清除剂吡啶的苯溶液和环己烷溶液中o-Ps强度的变化。结果表明,环己烷中电子和正离子的迁移率是很高的,苯中的迁移率也较高,但比环己烷中的小些。由我们导出的有关正穴清除剂使o-Ps强度增加的关系式表明,o-Ps强度的增强或抑制是电子清除和正穴清除这两个过程竞争的结果。     

Heterocyclization of 6-tert-Butyl-3-hydrazino-2,5-dihydro-1,2,4-triazin-5-one with Benzoyl Chloride and Formic Acid

Reaction of 6-tert-butyl-3-hydrazino-2,5-dihydro-1,2,4-triazin-5-one with excess benzoyl chloride or formic acid afforded 6-tert-butyl-[1,2,4]triazolo[4,3-b][1,2,4]triazin-7(8H)-ones.     

1,2,4-triazines. 1. A convenient synthesis of 4,5-dihydro-1,2,4-triazin-3-(2H)one and its 6-substituted derivatives

A facile synthesis of 4,5-dihydro-1,2,4-triazin-3-(2H)one (2a) from 5-methylthio-1,2,4-triazin-3-(2H)one (1a) with sodium borohydride is described. The reaction provides a convenient method for its 6-substituted derivatives (2b-h).     

Regioselectivity of cyclization of 1-(6-methyl-5-oxo-2,5-dihydro-1,2,4-triazin-3-yl)-4-arylthiosemicarbazides by treating with methyl iodide and dicyclohexylcarbodiimide

1-(6-Methyl-5-oxo-2,5-dihydro-1,2,4-triazin-3-yl)-4-arylthiosemicarbazides treated with methyl iodide in the presence of sodium acetate in ethanol convert into 6-methyl-3-arylamino[1,2,4]-triazolo[4,3-b][1,2,4]triazin-7(1H)-ones. In reaction with dicyclohexylcarbodiimide 6-methyl-3-arylamino[1,2,4]triazolo[3,4-c][1,2,4]triazin-5(1H)-ones were obtained which at heating in alcohol solution in the presence of sodium acetate or at 262–272°C underwent the Dimroth rearrangement to give 3-methyl-7-arylamino[1,2,4]triazolo[5,1-c][1,2,4]-triazin-4(8H)-ones.     

Coordination compounds of hydrazine derivatives with transition metals. Part 27. Coordination chemistry of 4-amino-3-alkyl-5-thio-1,2,4-triazolines and 4-amino-5-oxo-3-thioxo-6-alkyl-2,3,4,5-tetrahydro-1,2,4-triazines

Summary Mono-, bis- and tris-ligand nickel(II) and cobalt(II) complexes with 4 amino-3-alkyl-5-thio-1,2,4-triazolines (HRL) (R=H, Me, or Et) and 4-amino-5-oxo-3-thioxo-6-methyl-2,3,4,5-tetrahydro-1,2,4-triazine (HL') have been prepared and characterized. In these complexes both HRL and HL' are in the neutral thione form. Nickel(II) and cobalt(II) complexes with mononegative thiolate ligands have been also isolated.The reaction of HL' with copper(II) salts in a molar ration of 11 results in the formation of [Cu(HL')X] (X=Cl or Br) and Cu(L')X (X=NO₃ or CH₃COO). However, in the presence of a large excess of HL' the reaction proceeds with partial reduction of Cu^II and both [Cu(HL')X₂] and [Cu(HL')₂]X have been isolated and characterized. The mechanism of copper(II) reduction by HL' is discussed.     

蛋氨酸合成酶催化反应研究VII.5-氨基-6-甲基尿嘧啶的合成研究

报道了5-氨基-6-甲基尿嘧啶简便的合成方法。该化合物以6-甲基尿嘧啶（2） 为起始物，经硝化或重氮化分别得到了中间体5-硝基-6-甲基尿嘧啶（3）和5-偶氮 苯基-6-甲基尿嘧啶(4)，化合物3和4经Na_S_2O_4还原，合成产物5-氨基-6-甲基尿 嘧啶（1）。