3-取代苯氧甲基-4-氨基-1,2,4-三唑-5-硫酮席夫碱的合成、结构表征和生物活性研究

以醋酸为反应溶剂和催化剂,用自制的4-氨基-4,5-二氢-3-取代苯氧甲基-1,2,4-三唑-5-硫酮与4-氟苯甲醛反应合成了5个4-氨基-4,5-二氢-3-取代苯氧甲基-1,2,4-三唑-5-硫酮席夫碱化合物,通过1HNMR、IR和元素分析对所有化合物进行了结构表征.初步生物活性测试结果表明所有化合物具有优良的杀菌活性,并对席夫碱结构与活性的关系进行了探讨.     

3-(3＇-芳基-5＇-硫酮-1＇,2＇,4＇-三唑-4＇-基)-氨甲酰基色酮类化合物的合成

报道3-甲酰基色酮经Jones试剂氧化后得到3-羧基色酮,再与3-芳基-4-氨基-5-硫酮-1,2,4-三唑在POl3作用下,得到一系列3-(3＇-芳基-5＇-硫酮-1＇,2＇,4＇-三唑-4-＇-基)-氨甲酰基色酮类化合物.所有化合物的结构均经IR,LCMS,1H NMR,元素分析确证.     

1-苯基-5-芳基-1,2-二氢-1,2,4-三唑-3-硫酮的合成

将取代苯甲酰氯1a～1f与硫氰酸钾反应, 得到的中间体不需纯化直接与苯肼反应, 成功地合成了1-苯基-5-芳 基-1,2-二氢-1,2,4-三唑-3-硫酮(2a～2f). 化合物2的结构通过红外光谱、核磁共振光谱和高分辨质谱进行了表征.     

新型含1,2,4-三唑基的1,5-苯并硫氮杂的合成和表征

以α-溴代苯乙酮为原料,在三乙胺作用下制备α-(1,2,4-三唑-1-基)-芳基乙酮(1a～1c),再与芳香醛发生羟醛缩合反应制备相应的含三唑基的查尔酮2a～2l,将中间体2a～2l同邻氨基硫酚合成新型的2,4-二芳基-3-(1,2,4-三唑-1-基)-2,3-二氢-1,5-苯并硫氮杂(3a～3l).所得化合物的结构经元素分析,IR,MS和1HNMR确认,同时用X射线衍射法测定了化合物2a和3a的晶体结构.     

2-多氟烷基取代和葡萄糖基取代的2,4-二氢-1,2,4-三唑-3-硫酮类席夫碱的合成及其杀虫活性

为改善三唑类化合物的生物活性,以5-苯基-4-氨基-1,2,4-三唑-3-硫酮为原料,将其与芳香醛在冰醋酸体系中反应,得到5-苯基-4-芳基亚甲氨基-1,2,4-三唑-3-硫酮类席夫碱(4a～4i).在此基础上,化合物4a～4i分别与多氟烷基碘代烷和溴代乙酰基葡萄糖反应合成了一系列2,4-二氢-1,2,4-三唑-3-硫酮类席夫碱的多氟烷基取代物5a～5r和葡萄糖基取代物6a～6d,并用1H NMR,19F NMR,IR和MS谱以及元素分析表征了它们的结构.初步生物活性测试结果表明,部分目标化合物具有明显的杀虫活性.     

酰胺基硫脲及其相关杂环化合物的研究 VI:3-(4'-吡啶基)-4-芳基-1,2,4-三唑-5-烃硫醚类化合物的合成

在碱性介质中, 用碘甲烷对3-(4'-吡啶基)-4-芳基-1,2,4-三唑-5-硫酮进行亲核取代反应, 合成了3-(4'-吡啶基)-4-芳基-1,2,4-三唑-5-烃硫醚类化合物. 用元素分析, 红外光谱, 核磁氢谱和紫外光谱研究了合成化合物的结构.     

3-取代胺甲基-5-连三唑基-1,3,4-噁二唑-2-硫酮的合成

2-苯基-1,2,3-三唑-4-甲酰肼(1)在CS_2/KOH作用下环化得到5-(2-本基-1,2,3-连三唑-4-基)-1,3,4-噁二唑-2-硫酮(2),2经Mannich反应合成得到标题化合物3-取代胺甲基-5-(2-本基-1,2,3-连三唑-4-基)-1,3,4-噁二唑-2-硫酮(3)。     

3-取代胺甲基-5-连三唑基-1, 3, 4-恶二唑-2-硫酮的合成

2-苯基-1,2,3-三唑-4-甲酰肼(1)在CS~2/KOH作用下环化得到5-(2-苯基-1,2,3-连三唑-4-基)-1,3,4-恶二唑-2-硫酮(2),2经Mannich反应合成得到标题化合物3-(取代胺甲基-5-(2-苯基-1,2,3-连三唑-4-基)-1,3,4-恶二唑-2-硫酮(3)。     

3-芳基-4-[4′(2,2,6,6-四甲基哌啶-1-氧)]-1,2,4-三唑啉-5-硫酮类的合成

前文指出,各种1,4-二取代的酰氨基硫脲可在碱性物质催化下脱水环化形成1,2,4-三唑啉-5-硫酮类杂环化合物,然而连接2,2,6,6-四甲基哌啶-1-氧自由基的酰氨基硫脲类化合物能否在相同条件下环化脱水形成类似结构的杂环化合物,迄今未见文献报道。各种3,4-二取代的1,2,4-三唑啉-5-硫酮杂环化合物具有广泛的生物活性,如抗菌,杀虫等,而2,2,6,6-四甲基哌啶-1-     

3-(3′-芳基-5′-硫酮-1′,2′,4′-三唑-4′-基)-氨甲酰基色酮类化合物的合成

报道 3 甲酰基色酮经Jones试剂氧化后得到 3 羧基色酮 ,再与 3 芳基 4 氨基 5 硫酮 1,2 ,4 三唑在POCl3 作用下 ,得到一系列 3 (3′ 芳基 5′ 硫酮 1′ ,2′,4′ 三唑 4′ 基 ) 氨甲酰基色酮类化合物 .所有化合物的结构均经IR ,LC MS ,1HNMR ,元素分析确证     

Microwave‐assisted synthesis of some 1,2,4‐triazol‐5‐one derivatives

A series of 3‐alkyl(aryl)‐4‐(p‐hydroxy‐phenyl)‐4,5‐dihydro‐1H‐1,2,4‐triazol‐5‐ones 2 were obtained from the reaction of alkyl (aryl) ester ethoxycarbonyl hydrazones 1 with p‐hydroxy aniline. The reaction of 1 with 1,4‐diamino benzene (1:1) to afford 3‐alkyl(aryl)‐4‐(p‐aminophenyl)‐4,5‐dihydro‐1H‐1,2,4‐triazol‐5‐ones 3 . The reaction of 3 with benzaldehyde gave 3‐alkyl(aryl)‐4‐(4′‐benzilidenamino)‐4,5‐dihydro‐1H‐1,2,4‐triazol‐5‐ones 4 . All of the above reactions occurred under microwave heating and conventional methods. Their structures were confirmed by ¹H NMR, ¹³C NMR, IR, and elemental analyses. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:38–42, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20381     

Reactions of 3‐benzylindole‐2‐carbohydrazides: Synthesis of new 10‐Benzyl‐1,2‐dihydro‐1‐oxo‐1,2,4‐triazino[4,5‐a]indoles and 3‐Benzyl‐2‐(1,3,4‐oxadiazol‐2‐yl)indoles

3‐Benzylindole‐2‐carbohydrazides (4) on reaction with triethylorthoformate in a polar solvent like DMF yielded only 10‐benzyl‐1,2‐dihydro‐1‐oxo‐1,2,4‐triazino[4,5‐a]indoles (5) while (4) on reaction with triethylorthoacetate in DMF yielded both 10‐benzyl‐4‐methyl‐1,2‐dihydro‐1‐oxo‐1,2,4‐triazino[4,5‐a]indoles (5) and 3‐benzyl‐2‐(5‐methyl‐1,3,4‐oxadiazol‐2‐yl)indoles (6) instead of only the triazinoindoles as expected. The oxadiazolylindoles (6) were also synthesized by refluxing (4) with excess of orthoesters. The structures of the compounds formed were characterized by their analytical and spectral data.     

Green One‐Pot Solvent‐Free Synthesis of Pyrazolo[1,5‐a]pyrimidines,Azolo[3,4‐d]pyridiazines,and Thieno[2,3‐b]pyridines Containing Triazole Moiety

Synthesis of pyrazolo[1,5‐a]pyrimidines, [1,2,4]triazolo[1,5‐a]pyrimidine, 8,10‐dimethyl‐2‐(5‐methyl‐1‐phenyl‐4,5‐dihydro‐1H‐1,2,3‐triazol‐4‐yl)pyrido[2′,3′:3,4]‐pyrazolo[1,5‐a]pyrimidine, benzo[4,5]imidazo[1,2‐a]pyrimidine via heterocyclic amines, and sodium 3‐hydroxy‐1‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazole‐4‐yl)prop‐2‐en‐1‐one were carried out. Also, synthesis of isoxazoles, and pyrazoles from sodium 3‐hydroxy‐1‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazole‐4‐yl)prop‐2‐en‐1‐one and hydroxymoyl chlorides and hydrazonoyl halides, respectively, were made. Analogously, (1,2,3‐triazol‐4‐yl)thieno[2,3‐b]pyridine derivatives were obtained from sodium 3‐hydroxy‐1‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐ triazole‐4‐yl)prop‐2‐en‐1‐one and cyanothioacetamide followed by its reacting with active methylene compounds. In addition to full characterization of all synthesized compounds, they were tested to evaluate their antimicrobial activities, and some compounds showed competitive activities to those of tetracycline, the typical antibacterial drug, and clotrimazole, the typical antifungal drug.     

3-氨基-1H-1,2,4三唑类席夫碱的合成和生物活性

以醋酸为催化剂,用3-氨基-1H-1, 2, 4-三唑与取代苯甲醛反应合成了8个3-氨基-1H-1, 2, 4-三唑类席夫碱,化合物结构经1H NMR,IR和元素分析证实,并对其进行了生物活性测试,初步生物活性结果表明此类化合物具有良好的杀菌活性。     

Diastereoselective Synthesis of (Z)‐6‐(2‐Oxo‐1,2‐dihydro‐3H‐indol‐3‐ylidene)‐3,3a,9,9a‐tetrahydroimidazo[4,5‐e]thiazolo[3,2‐b]‐1,2,4‐triazin‐2,7(1H,6H)‐diones

Two efficient and diastereoselective procedures for the synthesis of (Z)‐6‐(2‐oxo‐1,2‐dihydro‐3H‐indol‐3‐ylidene)‐3,3a,9,9a‐tetrahydroimidazo[4,5‐e]thiazolo[3,2‐b]‐1,2,4‐triazin‐2,7(1H,6H)‐diones by aldol‐crotonic condensation of 1,3‐dimethyl‐3a,9a‐diphenyl‐3,3a,9,9a‐tetrahydroimidazo[4,5‐e]thiazolo[3,2‐b]‐1,2,4‐triazin‐2,7(1H,6H)‐dione with isatins under acidic or basic catalysis are reported. Isomerization in (Z)‐7‐(1‐allyl‐2‐oxo‐1,2‐dihydro‐3H‐indol‐3‐ylidene)‐1,3‐dimethyl‐3a,9a‐diphenyl‐1,3a,4,9a‐tetrahydroimidazo[4,5‐e]thiazolo[2,3‐c]‐1,2,4‐triazin‐2,8(3H,7H)‐dione was observed under basic conditions.     

Synthesis and Structure Determination of Some New N‐Glycosides of 4,5‐Disubstituted‐1,2,4‐Triazole‐3‐Thiones

Some new N‐glycosides of 4‐(2‐phenylethyl)‐5‐pyridyl‐1,2,4‐triazole‐3‐thiones were synthesised by the coupling reaction of halo sugar with 4,5‐disubstituted 3H‐1,2,4‐triazole‐3‐thiones in the presence of mercuric cyanide and dry nitromethane as solvent, followed by deprotection using dry ammonia in methanol. All of the above compounds were fully characterized by means of infrared, ¹H NMR spectroscopy, mass spectroscopy and elemental analysis.     

Synthesis,structure and biological activity studies of 2‐[(1H‐1,2,4‐triazol‐1‐yl)methyl]‐1‐aryl)‐3‐ferrocenyl prop‐2‐en‐1‐one derivatives

Fifteen new ferrocene derivatives containing 1H‐1,2,4‐triazole moiety were synthesized in various yields by the condensation of ferrocenecarboxaldehyde with 1‐aryl‐3‐(1H‐1,2,4‐triazo‐1‐yl)‐propen‐1‐ones in toluene. Their structures have been confirmed by ¹H NMR, IR, MS and elemental analysis. In addition, the crystal structure of 4l was determined. The antifungal and plant growth regulatory activities of the title compounds are discussed. Copyright © 2005 John Wiley & Sons, Ltd.     

On triazoles XLIX. Synthesis of 5,6‐dihydrothiazolo[3,2‐b]‐[1,2,4]triazol‐2‐yl‐, 6,7‐dihydro‐5H‐[1,2,4]triazolo[5,1‐b][1,3]thiazin‐2‐yl‐, and 5,6,7,8‐tetrahydro[1,2,4]triazolo[5,1‐b] [1,3]thiazepin‐2‐yl‐isoquinolinium salts

5′‐Mercapto‐1′H‐1,2,4‐triazol‐3′‐yl‐isoquinolinium salts (6) were synthesised by the reaction of ortho‐acyl phenylacetones (2) or the corresponding pyrylium salts (3) and 5‐amino‐2,3‐dihydro‐1H‐1,2,4‐triazole‐3‐thione (5) . Treatment of thioles 6 withα,ω‐dibromoalkanes led to type 15, 16 and 17 isoquinolinium salts condensed with thiazole, thiazine and thiazepine rings. When 6 are reacted with dibromomethane (10) 11 type dimeric structures are obtained.     

8‐Fluoro‐4‐hydroxy‐1H‐[1,2,4]triazino[4,5‐a]quinoline‐1,6(2H)‐dione: Synthesis and reactivity

A simple and versatile methodology to synthesise 4‐hydroxy‐1H‐[1,2,4]triazino[4,5‐a]quinoline‐1,6(2H)‐dione from methyl 6‐fluoro‐4‐oxo‐1,4‐dihydro‐2‐quinolinecarboxylate has been developed. It involves car‐bohydrazide formation followed by a condensation with triphosgene to form the fused [1,2,4]triazino ring. In addition, the reactivity of the [1,2,4]triazino ring has been studied.     

Structural,Magnetic, and Computational Correlations of Some Imidazolo‐Fused 1,2,4‐Benzotriazinyl Radicals

1,3,7,8‐Tetraphenyl‐4,8‐dihydro‐1H‐imidazolo[4,5g][1,2,4]benzotriazin‐4‐yl ( 5 ), 8‐(4‐bromophenyl)‐1,3,7‐triphenyl‐4,8‐dihydro‐1H‐imidazolo[4,5g][1,2,4]benzotriazin‐4‐yl ( 6 ), and 8‐(4‐methoxyphenyl)‐1,3,7‐triphenyl‐4,8‐dihydro‐1H‐imidazolo[4,5g][1,2,4]benzotriazin‐4‐yl ( 7 ) were characterized by using X‐ray diffraction crystallography, variable‐temperature magnetic susceptibility studies, and DFT calculations. Radicals 5 – 7 pack in 1 D π stacks made of radical pairs with alternate short and long interplanar distances. The magnetic susceptibility (χ vs. T) of radicals 5 and 6 exhibit broad maxima at (50±2) and (50±4) K, respectively, and are interpreted in terms of an alternating antiferromagnetic Heisenberg linear chain model with average exchange‐interaction values of J=?31.3 and ?35.4 cm^?1 (g_solid=2.0030 and 2.0028) and an alternation parameter a=0.15 and 0.38 for 5 and 6 , respectively. However, radical 7 forms 1 D columns of radical pairs with alternating distances; one of the interplanar distances is significantly longer than the other, which decreases the magnetic dimensionality and leads to discrete dimers with a ferromagnetic exchange interaction between the radicals (2J=23.6 cm^?1, 2zJ′=?2.8 cm^?1, g_solid=2.0028). Magnetic exchange‐coupling interactions in 1,2,4‐benzotriazinyl radicals are sensitive to the degree of slippage and inter‐radical separation, and such subtle changes in structure alter the fine balance between ferro‐ and antiferromagnetic interactions.