1,2,4-三唑并[3,4-b]-1,3,4-噻二唑的合成

近年来稠杂环化合物的合成及其生物活性的研究日益成为杂环化学研究的热门课题。3,6-二取代-1,2,4-三唑并噻二唑衍生物是具有广谱生物活性的稠杂环化合物,如抗菌、消炎、杀微生物、调节植物生长、除草等,因而引起各国化学家的广泛兴趣。此类化合物的生物活性,     

3,6-二苯氧甲基-1,2,4-三唑并[3,4-b]- 1,3,4-噻二唑衍生物的合成及生物活性

以4-氨基-5-苯氧甲基-3-巯基-1,2,4-三唑与取代苯氧乙酸为原料,三氯氧磷为溶剂,回流反应, 合成了3,6-二苯氧甲基-1,2,4-三唑并[3,4-b]-1,3,4-噻二唑衍生物。通过IR、1H NMR和元素分析确定了各化合物分子结构,并对其进行了室内毒力测试,结果表明此类化合物具有较好的杀菌、抑菌活性。     

Synthesis of 6-aryl-3-cinchophenyl-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazoles

In recent years, fused heterocycles have been found to possess many unique properties in synthesis and pharmacology. Especially, 1,2,4-triazolo[3,4-b]-1,3,4-thiadiazoles derivatives have been attracting much attention of chemists and pharmacologists because of their broad-spectrum biological activities such as antibacterial¹, hypotensive and CNS depressant² activities. We have prepared some 3,6-substituted 1,2,4-triazolo[3,4-b]-1,3,4-thiadiazoles and found that these compounds exhibited antimacrobial, insecticidal and promote plant growth.^3-5 Cinchophen had been used widely as medicine in clinic,but has been obsolete in recent years due to its by-effect. In order to seek for other uses of cinchophen, as a continuation of our preceeding studies, we used cinchophen as the starting material to synthesize ten new 6-aryl-3-cinchophenyl-l,2,4-triazolo[3,4-b]-l,3,4-thiadiazoles 5a-j. Compound 1 was prepared by the reaction of cinchophen and ethanol in the presence of sulfuric acid. 1 then reacted with hydrazine hydrate in absolute ethanol to give 2 which yielded 3 on treatment with CS₂ and KOH. On refluxing of 3 with excess hydrazine hydrate, 4 was obtained. 4 reacted with various substituted benzoic acids in the presence of POCl₃ to afifort 5a-j.     

3-取代-6-吡唑基-1,2,4-三唑并[3,4-b]-1,3,4-噻二唑类衍生物的合成及生物活性

将5-取代吡唑-3-甲酸乙酯1位甲基化,经水解反应得到3种中间体1-甲基-5-取代1H-吡唑-3-甲酸（2a~2c）;以不同取代的羧酸为原料经一系列反应合成6种中间体3-取代4-氨基-5-巯基-1,2,4-均三唑（3a~3f）;将中间体（2a~2c）和（3a~3f）在三氯氧磷条件下反应,合成出18种1,2,4-三唑并[3,4-b]-1,3,4-噻二唑类化合物(4a~4r),均未见文献报道。 通过IR、1H NMR、13C NMR和元素分析表征了化合物结构。 初步的生物活性测试结果显示,所合成的化合物均表现出不同程度的生长素活性和抑菌活性。 并选取抑菌活性较好的两个化合物进行抗菌药物最低抑菌浓度(MIC)的测定。     

6-取代-3-（3，4，5-三甲氧基苯基）-1，2，4-三唑[3,4-b][1,3,4]噻二唑的合成与生物活性

以3,4,5-三甲氧基苯甲酸为原料,通过4步反应得到4-氨基-5-(3,4,5-三甲氧基苯基)-3-巯基-1,2,4-三唑,再与取代芳酸反应,得到11个6-取代-3-(3,4,5-三甲氧基苯基)-1,2,4-三唑[3,4-b][1,3,4]噻二唑衍生物5a～5k。其结构经IR,1H NMR,MS和元素分析确证。初步生物活性测试结果表明部分化合物有一定的杀菌活性。     

On the preparation of substituted 4H- 1,3,4-thiadiazolo[2,3-c]-1,2,4-triazin-4-ones and 1,2,4-triazolo[3,4-b]-1,3,4-thiadiazoles

The reaction of benzoyl isothiocyanates and methoxycarbonyl isothiocyanate with 4-amino-4,5-dihydro-3-(methylthio)-1,2,4-triazin-5-ones in acetonitrile gave several substituted 4H-1,3,4-thiadiazolo[2,3-c]-1,2,4-triazin-4-ones VIa-h instead of the expected thioureas. In addition, benzoyl isothiocyanate reacted with 4-amino-3-(methylthio)-5-(trifluoromethyl)-4H-1,2,4-triazole to give the benzoyl thiourea IX and with 4-amino-3-mercapto-5-(trifluoromethyl)-4H-1,2,4-triazole to give the bicyclic compound N-[3-(trifluoromethyl)-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazol-6-yl]benzamide IX .     

A new synthesis of 3-alkyl-6-alkylthio-1,2,4-triazolo[3,4-b]1,3,4-thiadiazoles

4-Amino-5-R-1,2,4-triazole-3-thiones react with alkyl(alkylaryl)thiocyanates in polyphosphoric acid to give the title compounds.Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 230–231, January, 1993.     

Studies on the Syntheses and Biological Activities of 3-Aryl-6-(1,1'-biphenyl-4-yl)-7H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazines

IntroductionAmongst various heterocycles 3 ,6 -disubstituted- 7H- 1 ,2 ,4- triazolo[3 ,4- b][1 ,3 ,4]thiadiazines have received considerable attentionduring the lasttwo decades as potentially biologicalactive agents[1,2 ] . A literature survey indicated thatthis kind of N - bridged heterocycles displayed awide spectrum of biological properties,such asantimicrobial[3] ,antibacterial,antifungal[4 ] ,antiinflammatory[5] ,diuretic[6 ] ,anthelmintic,andanalgesic[7] . They can also be used as the p…     

A Convenient Synthesis and Herbicidal Activity of N-phosphonoalkylpyrazolo[4,3-e][1,2,4]-triazolo[1,5-d]pyrimidines

An important building block, diethyl [(5-amino-4-cyano-3-methylsulfanyl-pyrazol-1-yl)–(4-fluorophenyl)methyl] phosphonate (3) was efficiently synthesized via the condensation of 1-hydrazino-1-(4-fluorophenyl)methyl phosphonate (1) with 2-[bis(methylthio)methylene]malononitrile (2).3 reacted with triethyl orthoformate to afford diethyl [(4-cyano-5-ethoxymethyleneamino-3-methylsulfanyl-pyrazol-1-yl)-(4-fluorophenyl)methyl] phosphonate (4), which reacted with various acyl hydrazines in refluxing 2-methoxyethanol to provide the target compounds (5) in good yields directly. The results of preliminary bioassay indicated that compounds 5 possess potent herbicidal activity against the roots of monocotyledonous (barnyard grass) and dicotyledonous (oil rape) plants, and could be further developed as potential herbicides.     

3-芳氧甲基/芳基-6-芳基-1,2,4-三唑并[3,4-b]-1,3,4-噻二唑衍生物的合成及生物活性

报道了3-芳氧甲基/芳基-4-氨基-5-巯基-1,2,4-三唑和芳酸在三氯氧磷作用下合成了16个标题化合物.其结构经元素分析、IR,1HNMR和MS确证.同时研究了反应条件.抗菌试验表明部分化合物具有较强的生物活性.     

Synthesis and properties of 1,2,4-triazolo[4,3-d]-1,2,4-triazolo-[3,4-f]furazano[3,4-b]pyrazines

New methods for the synthesis of 1,2,4-triazolo[4,3-d]-1,2,4-triazolo[3,4-f]furazano[3,4-b]pyrazines with functional substituents of various types are proposed and some properties of these compounds are studied. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1776–1778, October, 1993.     

Preparation and Electrochemical Properties of 3-Phenyl-6-aryl-1,2,4-triazolo[3,4-b][1,3,4]-thiadiazoles

Since Tang firstly reported the electroluminescence of 8-hydroxyquinoline aluminium, much attention has been paid to the organic compound as electro-luminescent material. Especially, electron transport materials play an important role in organic light-emitting diode (OLED).2-(4-Biphenyl)-5-(t-butylphenyl)-1, 3,4-oxadiazole (PBD), as a kind of popular electron injection/transport materials, can improve remarkably the     

Stereospecific synthesis of 6,7-dihydro-5H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazines

The reaction of 3-mercapto-4-arylideneamino-1,2,4-triazoles 2b-d , 3a-d with ethyl bromoacetate and/or phenacyl bromide in hot DMF and triethylamine affords the stereochemically pure 7-acyl-6-aryl-6,7-dihydro-5H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazines 4b-d , 5a-d , 6b , d in which the consecutive hydrogen atoms N(5)H-C(6)H-C(7)H are cis to each other. This stereochemistry was determined by ¹H NMR spectroscopy and confirmed by comparison with the spectrum of 3,6-diphenyl-6,7-dihydro-5H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazine 10 . The latter was prepared by NaBH₄ reduction of 3,6-diphenyl-5H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazine 9 . The reported reactions offer two interesting stereospecific syntheses of the condensed heterocyclic compounds.     

Preparation and Electrochemical Properties of 3-Phenyl-6-aryl-1,2,4-triazolo[3,4-b][1,3,4]-thiadiazoles

Introduction Since Tang[1] firstly reported the electroluminescence of 8-hydroxyquinoline aluminium, much attention has been paid to the organic compound as electro-luminescent material. Especially, electron transport materials play an important role in organic light-emitting diode(OLED). 2-(4-Biphenyl)-5-(t-butylphenyl)-1,3,4-oxadiazole(PBD), as a kind of popular electron injection/transport materials, can improve remarkably the injection balance of electrons and holes. As a result, it can amend the properties of OLED[2,3].     

5,6-2H-1,2,4-三唑[3,4-b][1,3,4]噻二嗪衍生物的合成及抗癌活性测定

取代苯甲醛与4-氨基-5-(3,4,5-三甲氧基苯基)-1,2,4-三唑-3-硫酮(2)缩合生成5-(3,4,5-三甲氧基苯基)-4-取代苯基亚胺基-1,2,4-三唑-3-硫酮(3),再烷基加成化为新型5,6-2H-1,2,4-三唑[3,4-b][1,3,4]噻二嗪衍生物4.化合物结构经1HNMR 13C NMR,IR以及元素分析确认.采用噻唑兰(MTT)比色法进行化合物抑制人体前列腺癌细胞(PC3)体外活性测试,结果表明所合成的化合物具有不同程度的抑制PC3活性,其中化合物4a在10μmol·L-1浓度下对PC3的抑制率为75.9%.     

双－（3－烷基／芳基）－7H－1，2，4－三唑并[3,4-b]-1,3,4-噻二嗪类化合物的合成及波谱性质

利用1，4－二溴丁二酮（1）分别与3－烷基／芳基－4－氨基－5－巯基－1， 2，4－三唑（2a-2n）反应，合成了14种新的双－（3－烷基／芳基）－7H－1，2， 4－三唑并[3,4-b]－1，3，3-噻二嗪类化合物（3a-3n），并利用EA、IR，~1H NMR和MS确定了其结构。     

3－苄基－6－（1－氨基烃基）－1，2，4－三唑并[3,4-b]-1,3,4-噻二唑的合成与波谱表征

3－苄基－4－氨基－5－巯基－1，2，4－三唑与氨基酸在三氯氧磷存在下反应 ，合成3－苄基－6－（1－氨基烃基）－1，2，4－三唑并[3,4-b]－1，3，4－噻二 唑，其结构经元素分析、红外光谱、核磁共振氢谱、碳谱、质谱等确证。这是稠杂 环接氨基酸残基的首次报道。     

3,6-二取代苯基-二-1,2,4-三唑并[3,4-b]-1,3,4-噻二唑衍生物的合成

以2,5-二巯基-1,3,4-噻二唑为原料, 与水合肼缩合, 生成2,5-二肼基-1,3,4-噻二唑. 2,5-二肼基-1,3,4-噻二唑与苯甲酰氯反应生成2,5-二酰肼基-1,3,4-噻二唑, 以POCl₃为环合剂环合酰肼基-1,3,4-噻二唑, 合成3,6-二取代苯基- 二-1,2,4-三唑并[3,4-b]-1,3,4-噻二唑衍生物, 合成的新化合物的结构通过元素分析、红外光谱、核磁共振氢谱和质谱予以证实, 并提出了环化反应机理.     

Synthesis of 3,6-bisubstituted phenyl-bi-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazole derivatives

2,5-Bihydrazino-1,3,4-thiadiazole (2) was synthesized by condensation of 2,5-bimercapto-1,3,4-thiadiazole (1) with hydrazine hydrate, and compound 2 reacted with acyl chloride to give 2,5-biacylhydrazino-1,3,4-thiadiazole derivatives (3a–3e). Ring closure of compounds 3a–3e was achieved with POCl3 as the cyclization agent giving 3,6-bisubstituted phenyl-bi-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazole derivatives (4a–4e), respectively. The novel compounds were identified by elemental analysis, and by infrared (IR), 1H-nuclear magnetic resonance (NMR), and mass (MS) spectrometry. The mechanism of the cyclization is also discussed. __________ Translated from Organic Chemistry, 2006, 26(12): 1720–1722 [译自: 有机化学]     

3-（4′-吡啶基）/苯基-6-芳基-1,2,4-三唑并[3,4-b]-1,3,4-噻二唑的合成及电化学性质表征

由化合物3-（4＇-吡啶基）／苯基4氨基-5-巯基-1，2，4-三唑与芳香酸在三氯氧磷作用下脱水、闭环得到3-（4＇-吡啶基）／苯基-6-芳基-1，2，4-三唑并[3，4-b]-1，3，4-噻二唑类新型化合物，产率为42％～72％。该化合物具有较大的共轭平面，其结构经红外光谱、核磁共振氢谱、元素分析测试技术确证。电化学测试的工作窗口为-1.4～1.0V.负向扫描，循环伏安图中显示标题化合物均有还原峰，还原起始电位为-0.35～-0.95V.借鉴有机材料能带表征的方法，结合其紫外-可见光谱计算出了被测化合物的电子亲和势、电离势、带隙等电化学参数。结果表明，与常用的有机电子传输材料PBD相比，标舾化合物具有较高的电子亲和势（3.79～4.39ev）和电离势（6.95～7.84eV），较高的电子亲和势有利于电子的传输。