N-(3-苯基-2,3,4-三唑甲酰氨基)-N＇-芳酰基硫脲及其环化产物的合成

以PEG-400为相转移催化剂,通过2-苯基-1,2,3-三唑-4-甲酰基肼与芳酰基异硫氰酸酯的加成反应,合成了系列新的酰胺基硫脲衍生物(3),3分别在酸性和碱性条件下环化制得相应的1,3,4-噻二唑衍生物和1,2,4-三唑啉-5-硫酮衍生物,并经元素分析、IR,1H NMR和MS确证结构.     

1-(2′-苯基-1′,2′,3′-三唑-4′-甲酰基)-4-芳基氨基硫脲及其环化产物的合成

以2-苯基-1,2,3-三唑-4甲酰肼为原料合成了几种新的1-(2′-苯基-1′,2′,3′-三唑-4′-甲酰基)-4芳基氨基硫脲,在不同条件下环化,制得一系列新的1,3,4-噻二唑、1,3,4- 二唑和1,2,4-均三唑衍生物.化合物的结构经元素分析、IR、1HMR和MS确证,并对其波谱性质进行了讨论.     

新型3-取代-6-(4-氯苯基)-7-(1H-1,2,4-三唑-1-基)-1',2',4'-三唑[3,4-b]-1",3",4"-噻二嗪衍生物的合成及抗菌活性

通过3-取代-4-氨基-5-巯基-1,2,4-三唑(3a～3m)和2-溴-2-(1H–1,2,4-三唑-1-基)-4′-氯代苯乙酮(2)的缩合反应,合成了13个新型3-取代-6-(4-氯苯基)-7-(1H-1,2,4-三唑-1-基)-1',2',4'-三唑[3,4-b]-1",3",4"-噻二嗪衍生物4a～4m.化合物结构经元素分析,1HNMR,IR和MS进行了表征.抗菌试验表明所合成的化合物对细菌表现出中等程度的抑制活性.     

1-(4-取代苯基)-4-苯基-5-(2-羟基苄基)氨基-1,2,3-三唑类衍生物的合成及抑菌活性

将邻羟苯基引入1,2,3-三唑结构中, 设计合成了10个1-(4-取代苯基)-4-苯基-5-取代-1,2,3-三唑类衍生物. 首先, 以对位取代的芳胺为原料, 经重氮化、叠氮化、闭环和缩合反应制得1-(4-取代苯基)-4-苯基-5-水杨醛亚胺-1,2,3-三唑类衍生物(3a~3e), 再用硼氢化钠还原制得1-(4-取代苯基)-4-苯基-5-(2-羟基苄基)氨基-1,2,3-三唑类衍生物(4a~4e). 目标化合物的结构经核磁、IR及元素分析确认. 抑菌活性测试表明, 当质量浓度为0.1 mg/L时, 除化合物3e和4e外, 所有化合物对白色念球菌的抑菌率均达95%以上, 对大肠杆菌的抑菌率达85%以上, 具有强抑菌活性, 表明该类化合物在抗菌药物开发方面有重要应用价值.     

新型含2-苯基-1,2,3-三唑基的1,5-苯并硫氮杂及其β-内酰胺衍生物的合成

α ,β 不饱和酮 (1a～ 1e)与邻氨基苯硫酚反应 ,得到含 2 苯基 1,2 ,3 三唑基的 1,5 苯并硫氮杂 (2a～ 2e) ,然后以其为原料与烯酮“现场”进行 [2 +2 ]环加成 ,合成出一系列含 2 苯基 1,2 ,3 三唑基的 β 内酰胺并合的 1,5 苯并硫氮杂衍生物 (3a～ 3j) .产物经1 HNMR ,IR ,元素分析及MS加以确证     

酰氨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

1,2,4-三唑类衍生物具有多种生物活性。如抗菌、抗痉挛、消炎、抗血吸虫、抗血糖过低或抗血小板凝聚等。有趣的是它与某些致癌物质联用时,还具有抗癌活性。Pathak和 Sharma 又曾指出,1,2,4-三唑-5-硫醇的硫醚类衍生物较其母体硫醇化合物具有更高的生物活性。受此启发,作者将前文3-(4′-吡     

1,3-偶极环加成合成新型含2-苯基-1,2,3-三唑基的1,2,4-噁二唑啉衍生物

Schiff碱 3和肟或氯代肟在三乙胺作用下通过 1,3 偶极环加成生成一系列含 2 苯基 1,2 ,3 三唑基的 1,2 ,4 二唑啉类化合物 4a～ 4g ,5a～ 5g和 6a～ 6g .2 1个新化合物的结构经元素分析 ,1 HNMR ,IR和MS谱确证 .     

含有异(口恶)唑的S-三唑[3,4-b]-1,3,4-噻二嗪、咪唑[2,1-b]-1,3,4-噻二唑和咪唑[2,1-b]-1,3,4-(口恶)二唑衍生物的合成

异噁唑衍生物作为一类重要的生物活性物质[1,2],其合成一直受到人们的关注,其中德国HMR公司开发研制的新型抗内风湿性关节炎药来氟米特(Leftunomide)已于1998年在美国率先上市,该药还具有很好的免疫调节作用[3].7H-均三唑[3,4-b]-1,3,4-噻二嗪、咪唑并[2,1-b]噻唑和咪唑并[2,1-b]-1,3,4-噻二唑衍生物均表现出广谱的生物活性[4～6].     

1-取代芳基-4-乙氧羰基-5-二甲氨基亚甲基氨基-1,2,3-三唑衍生物的新法合成

以1-取代芳基-4-乙氧羰基-5-氨基-1,2,3-三唑衍生物为原料,用简单有效的方法在非常温和的条件下以较好的收率合成了一系列新型的1-取代芳基-4-乙氧羰基-5-二甲氨基亚甲基氨基-1,2,3-三唑及其衍生物,所得化合物未见文献报道.新化合物的结构用红外光谱、核磁共振、质谱和元素分析确证,同时初步研究了这些化合物的抑菌性能.     

(3-苄基-4-芳酰基-1,2,4-三唑-5-基)(5-本基-1,3,4-噁二唑-2-基)硫醚的合成

通过3-苄基-4-芳酰基-1,2,4-三唑-5-巯基负离子在2-甲磺酰基-5-苯基-1,3,4-噁二唑环2-位上的亲核取代反应,制得13个新的(3-苄基-4-芳酰基-1,2,4-三唑-5-基)(5-苯基-1,3,4-噁二唑-2-基)硫醚衍生物.经元素分析、IR、~1H NMR和MS裂解碎片分析确认结构.初步观察了它们在0.01％浓度时对大肠杆菌繁殖的抑制作用.     

Synthesis of heierocyclic compounds from 2-phenyl-1, 2,3-triazole-4-formylhydrazine

2-Phenyl-1, 2, 3-triazole-4-formylhydrazine (2) was prepared by hydrazinolysis of the corresponding ester 1. Reaction of 2 with CS2/KOH gave the oxadiazole derivatives (3) which via, Mannich reaction with different dialkyl amines furnished 3-N, N-dialkyl derivatives (4a-c). Also, condensation of 2 with appropriate aromatic acid in POCl3 yielded oxadiazole derivatives (5a-c), or with aldehydes and ketones afforded hydrazones (6a-c). Cyclization of (6a-c) with acetic anhydride gave the desired dihydroxadiazole derivatives (7a-c). On the other hand, reaction of dithiocarbazate (8) with hydrazine hydrate gave the corresponding triazole derivative (9) which on treatment with carboxylic acids in refluxing POCl3 yielded s-triazole[3,4-b]-1, 3, 4-thiadiazole derivatives (10a-b). The structures of all the above compounds were confirmed by means of IR, 1H NMR, MS and elemental analysis.     

Synthesis of heterocyclic compounds from 2-phenyl-1,2,3-triazole-4-formylhydrazine

2-Phenyl-1, 2, 3-triazole-4-formylhydrazine (2) was prepared by hydrazinolysis of the corresponding ester 1. Reaction of 2 with CS₂/KOH gave the oxadiazole derivatives (3) which via Mannich reaction with different dialkyl amines furnished 3-N, N-dialkyl derivatives (4a–c). Also, condensation of 2 with appropriate aromatic acid in POCI₃ yielded oxadiazole derivatives (5a–c), or with aldehydes and ketones afforded hydrazones (6a–c). Cyclization of (6a–c) with acetic anhydride gave the desired dihydroxadiazole derivatives (7a–c). On the other hand, reaction of dithiocarbazate (8) with hydrazine hydrate gave the corresponding triazole derivative (9) which on treatment with carboxylic acids in refluxing POCI₃ yielded s-triazole [3, 4–b]-1, 3, 4-thiadiazole derivatives (10a–b). The structures of all the above compounds were confirmed by means of IR, ¹H NMR, MS and elemental analysis.     

1-芳酰基-4-取代吡唑甲酰基氨基硫脲和环化产物的合成及生物活性

利用1-苯基-3-甲基-5-氯-4-吡唑甲酰基异硫氰酸酯(Ⅰ)与芳酰肼(Ⅱ)的加成反应合成了系列新的酰胺基硫脲衍生物(Ⅲ),并将Ⅲ在酸性条件下进行环化反应得到2-取代吡唑甲酰基氨基-5-芳基-1,3,4-噻二唑(Ⅳ).生物活性测定结果表明部分化合物Ⅲ和Ⅳ具有较好的除草活性.     

均三唑并噻二唑衍生物的微波合成

在无溶剂无催化剂微波辐射下,羧酸与1,3-二氨基硫脲快速反应高产率得到了3-取代基-4-氨基-5-巯基-1,2,4-三唑,该化合物与苯甲酰氯在无溶剂无催化剂微波促进下可以方便地制备化合物3-取代基-6-苯基-1,2,4-三唑[3,4-b][1,3,4]噻二唑。该方法具有反应时间短、环境友好、易于纯化及高产率的优点。产物结构经IR和1HNMR谱进行了表征。     

微波辐射下合成2-(未)取代苯甲酰胺基-5-(1-苯基-3-甲基-5-氯吡唑- 4-基)-1,3,4-噻二唑衍生物

分别在微波辐射和常规加热条件下, 通过2-氨基-5-(1-苯基-3-甲基-5-氯吡唑-4-基)-1,3,4-噻二唑(1)与(未)取代苯甲酰氯(2a～2j)反应, 合成了一系列未见文献报道的2-(未)取代苯甲酰胺基-5-(1-苯基-3-甲基-5-氯吡唑-4-基)-1,3,4-噻二唑衍生物(3a～3j). 标题化合物的结构经元素分析, IR, 1H NMR确证.     

Preparation of 2-amino-5,7-dimethoxy-4-aryl/alkyl-4H-chromene-3-carbonitriles using Na_2O-Al_2O_3-P_2O_5 glass–ceramic system

A highly efficient and environmentally benign protocol for the synthesis of 2-amino-5,7-dimethoxy-4-aryl/alkyl-4H-chromene-3-carbonitrile derivatives by one-pot three-component coupling reacting of aromatic aldehydes, malononitrile and 3,5-dimethoxy phenol under reflux condition has been developed in aqueous Et OH media using Na2O-Al2O3-P2O5glass–ceramic system.     

1，2，4－三嗪类化合物研究（XXIV）──吡唑并－（5，4－e）－1，2，4－三嗪衍生物的合成

先合成１，２，４－三嗪环，然后并接吡唑环，对标题化合物进行了合成研究。对１，２，４－三嗪环上的硫化反应进行了改进，解决了３个反应活性相近部位的选择性肼解问题；并发现了肼基与乙酸乙酯于室温下反应生成１，３，４－　二唑环的新反应。     

三氯化铟高效催化3-(1-吡咯基)吲哚-2-酮类化合物的合成方法

使用三氯化铟在乙醇中回流的条件下催化不同的靛红衍生物与4-羟基脯氨酸反应,以较高的产率(83-99%)和纯度合成得到了相应的产物3-(1-吡咯基)吲哚-2-酮化合物,并对这个反应做了一个比较全面系统的研究.     

Synthesis of 5-(6-Methyl-2,4-dioxo-1,2,3,4-tetrahydro-3-pyrimidinyl)-methyl-4-amino-1,2,4-triazole-3-thione and its Reactions with Polyfunctional Electrophiles

Summary.  In the reaction of 5-(6-methyl-2,4-dioxo-1,2,3,4-tetrahydro-3-pyrimidinyl)-methyl-1,3,4-oxadiazole-2-thione with hydrazine hydrate, 5-(6-methyl-2,4-dioxo-1,2,3,4-tetrahydro-3-pyrimidinyl)-methyl-4-amino-1,2,4-triazole-3-thione was formed. The reactions of the latter with ethyl bromoacetate and chloroacetonitrile in the presence of triethylamine proceeded under formation of the corresponding S-alkylated derivatives, whereas from its reaction with ω-bromoacetophenone and ethyl 4-chloroacetoacetate triazolothiadiazines were obtained. Treatment of the title compound with ethyl 2-chloroacetoacetate led to the formation of 5-(6-methyl-2,4-dioxo-1,2,3,4-tetrahydro-3-pyrimidinyl)-methyl-4-N-acetylamino-(3-ethoxy-carbonylmethylthio)-1,2,4-triazole. Performing of the latter reaction without basic catalyst gave a triazolothiadiazine. Treatment of the S-alkylated derivatives with sodium methoxide resulted in triazolothiadiazines via a cyclocondensation reaction. Received November 20, 2000. Accepted January 15, 2001     

Synthesis of (1H)-3,4-Dihydropyrrolo[2,1-c][1,4]oxazin-1-one Derivatives

It has been found that some acyl derivatives of 1,2,3,4-tetrahydro-1-indolizin-1-one 1and (1H)-3,4-dihydropyrrolo[1,2-a]pyrazin-1-one 2 show remarkable anti-inflammatory and analgesic activities1,2. The interest in extending the study of structure-activity relationships and search of new potent anti-inflammatory and analgesic agents led us to design and synthesize (1H)-3,4-dihydropyrrolo[2,1-c][1,4]oxazin-1-one 3 derivatives. NO 1 NNHO2 87654321ONO3 A few examples of the p…