新型1,2,4-三氮唑类化合物的合成及其杀菌活性

以α-乙酰基-γ-丁内酯为原料,经亲核取代、开环、闭环和亲核取代反应制得1-氯-1-氯乙酰基环丙烷（5); 5与1,2,4-三氮唑反应制得1-三唑基乙酰-1-氯代环丙烷(6); 6与一系列卤代化合物进行亲核取代反应制得6个新化合物(7a~7f); 7a~7f经还原反应合成了6个新型的1,2,4 三氮唑类化合物(8a~8f),其结构经¹H NMR, ¹³C NMR, LC-MS和元素分析表征。采用生长速率法研究了化合物的杀菌活性。结果表明：用药量为50 μg·mL^-1时,化合物8f对立枯丝核菌和禾谷镰孢菌的抑制率分别为56.8%和43.8%,化合物8e对黄瓜枯萎病菌的抑制率为57.9%。     

苯并三氮唑类化合物的合成及生物活性

设计并合成了6种新的苯并三氮唑类化合物,其结构均经^1H NMR和IR确认。初步测定了其生物活性．结果表明6种化合物对小白菜的胚根、根和苗的生长均具有一定的调节作用。     

新型含1,2,3-三氮唑的染料木素糖缀合物的合成

以染料木素为起始原料,经两步反应制得中间体7-O-炔丙基染料木素(3);以CuI为催化剂,3与叠氮乙酰基糖经Click反应合成了7-O-［1-(2,3,4,6-四-O-乙酰基-β-D-糖苷)1H-1,2,3-三氮唑-4-甲基］-染料木素(5a~5c); 5a~5c经去乙酰基制得三种含1,2,3-三氮唑的氮苷染料木素糖缀合物(6a~6c)。3, 5和6均为新化合物,其结构经¹H NMR, ¹³C NMR和HR-MS表征。     

新型三氮唑席夫碱吡唑衍生物的合成

以乙醇为溶剂,乙酸为催化剂,1-苯基-3-甲基-5-氯-4-吡唑甲醛与4-氨基-5-取代苯基-1,2,4-三唑-3-硫酮于65℃反应4 h合成了7个新型的三氮唑席夫碱吡唑衍生物,收率74%~87%,其结构经1H NMR,IR和元素分析表征。     

N-取代-1,2,3-三氮唑化合物的合成研究进展

N-取代-1,2,3-三氮唑是一类重要的含氮杂环化合物,在药物化学、合成化学及材料等领域都具有广泛的应用价值.因此,N-取代-1,2,3-三氮唑的构建方法备受人们的关注.归纳总结了近年来N-取代-1,2,3-三氮唑的合成研究进展,主要介绍了以叠氮化合物、腙、Ts NHNH2和重氮为氮源以及NH-1,2,3-三氮唑为前体合成N-取代-1,2,3-三氮唑化合物的合成路线及其反应机理,并对该领域未来的发展进行了展望.     

由1,1-二溴烯烃一锅法合成1,4-二取代-1,2,3-三氮唑

以1,1-二溴乙烯和芳基叠氮化合物为原料,碘化亚铜为催化剂,室温下通过一锅法合成了1,4-二取代-1,2,3-三氮唑衍生物。考察了催化剂用量、反应溶剂、反应温度对产品收率的影响。通过IR,MS,_¹H NMR及_¹³C NMR等对目标产物结构进行确证,并提出了可能的反应机理。该合成方法具有环境友好、条件温和、操作简单、收率高等特点。     

4-单取代-1H-1,2,3-三氮唑的合成研究

以甲氧基聚乙二醇(mPEG)为起始原料通过磺酰化、叠氮化反应合成叠氮基甲氧基聚乙二醇(mPEG-N_3,2);在铜催化下和芳香炔、脂肪炔发生1,3-偶极环加成反应合成甲氧基聚乙二醇-1,2,3-三氮唑(mPEG-1,2,3-triazoles,3);再于酸性条件下脱除甲氧基聚乙二醇(mPEG)制备4-单取代-1H-1,2,3-三氮唑(4),其结构经过MS及~1H NMR、~(13)C NMR确证。     

5-氨基-1H-1,2,4-三氮唑-3-硫代-2''''-丙酸乙酯类Schiff碱的合成与表征

用氨基三氮唑硫代丙酸乙酯与取代苯甲醛反应,合成了6个新型的5-氨基-1H-1,2,4-三氮唑-3-硫代-2′-丙酸乙酯类Schiff碱,其结构经1H NMR, IR, MS和元素分析表征.     

Sm/CdCl_2体系促进的α-苯并三氮唑硫醚的合成

尽管有机镉试剂已于十九世纪就被发现 ,但由于其反应性低 ,在有机合成应用中受到一定的限制 ,而采用活性金属镉促进的有机反应的报道更是为数不多。我们采用了Ｓｍ/ＣｄＣｌ2 体系 ,还原生成活性金属镉 ,以促进其它的有机反应。实验表明 ,活性金属镉具有较好的反应活性 ,它可以促进一些反应的发生[1～ 4] ,它突出的优点在于反应可在含水介质中进行 ,操作简便 ,产率理想。α 苯并三氮唑硫醚是一重要的有机合成中间体 ,Ａ .Ｒ .Ｋａｔｒｉｔｚｋｙ等人利用α 苯并三氮唑硫醚与格氏试剂反应制得叔烷基硫醚[5] ,乙烯基硫醚[6] ,另外 ,该分子中含…     

含1,2,3-苯并三氮唑及嘧啶衍生物醚类化合物的合成及除草活性

嘧啶氧醚类化合物是一类新型除草剂,对其进行结构修饰以寻求具有更高活性的先导化合物是当前乙酰乳酸合成酶(ALS)类除草剂研究中的一大热点.近年来对嘧啶氧醚类化合物修饰主要集中在苯环部分取代基的变化上,而杂环部分为稠杂环的醚类化合物报道很少[1～3].在对嘧啶醚类除草剂构效关系研究中发现其与ALS相互作用时,杂环部分主要起供电子作用,其供电子能力越强化合物的活性越高[4].另外,许多二芳醚类化合物又是原卟啉原氧化酶(PPO)抑制剂,我们初步研究发现,1,2,3-苯并三氮唑是一类很好的活性单元,若在醚类化合物中引入这种稠杂环有可能找到高活性的先导化合物.     

Synthesis and Crystal Structure of 4-Salicylimine-3,5-bis(2-hydroxyphenyl)-1,2,4-triazole

1 INTRODUCTION 1, 2, 4-Triazole and its derivatives have gained great attention as ligands to transition metals by the fact that they unite the coordination geometry of both pyrazoles and imidazoles, and in addition exhibit a strong and typical property of acting as bridging ligands between two metal centers. In this bridging capacity, the 1, 2, 4-triazole ligands show a great coordination diversity, especially when the triazole nucleus are substituted with additional donor groups[1]. In…     

Synthesis of Asymmetric 4H-1, 3, 2-Benzodioxaphosphorin 2-Sulfides from Intramolecular Cyclization Reaction

Avarietyofbiologicalactivitiesofsome4H-l,3,2-benzodioxaphosphorin2-sulfideshavebeenreported,forexampletheinsecticideSalithionl.Thecyclicphosphonothionateshavebeenpreparedbyintermolecularcondensationofphosphorodichloridothioateswithsalicylalcoholoritsderivativesinthepresenceofabase=,andbyintramolecularcyclizationreactionofthesalicylalasthestartingmaterial3.However,theintramolecularcyclizationreactionofthe2-hydrobenzophenonesandstereochemicalstudieshavenotbeenreported.Wenowdescribeanewsynthesis…     

1-茚满酮合成方法研究进展

1-茚满酮类化合物是许多药物和天然产物合成中的中间体, 有关这类化合物的合成方法仍然不断得到更新. 按照关环位点对于这些合成方法进行了综述, 着重介绍了2000以来的合成新进展.     

Synthesis of some substituted 1,2,4-triazole and 1,3,4-thiadiazole derivatives

New S-substituted 1,2,4-triazole and 1,3,4-thiadiazole derivatives have been prepared. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1712–1715, November, 2008.     

Synthesis of dimethyl 3-perfluoroalkyl-4-(3-oxo-2-triphenyl-phosphoranylidenbutanylidene)-pent-2-enedioate and its cyclization

The title compounds 5a-5c were prepared via the reaction of methyl 2-perfluoroal-kynoates (4) with methyl 5-oxo-4-(triphenylphosphoranylidene)hex-2-enoate (3), which was obtained from the reaction of methyl propynate (2) with acetylmethylenetriphenylphosphorane (1) at -5-0℃. Intramolecular elimination of Ph3PO took place when compound 5 was heated in aqueous methanol at 115-120℃ in sealed tube, yielding dimethyl 2-trifluoromethyl-4-methylisophthalate (6a) from 5a and methyl 5-acetyl-4-hydroxy-2-heptafluoropropanylbenzoate (6b) from 5b, respectively. The structures of compounds 5, 6a and 6b were confirmed by IR, MS, 1H NMR, 19F NMR and 13C NMR spectroscopy and elemental analyses. Rection mechanisms for the formation of compounds 5, 6a and 6b were proposed.     

4,5,6-三取代-2H-吡喃-2-酮的简便合成法

2H-吡喃-2-酮及其衍生物是有机合成的蓬要中间体。对于它们的合成已有许多报道,例如利用烯醇醚或烯醇砖醚与丁酰氯反应;羰基化合物与甲氧亚甲螭丙二酸二甲酯反应;α-苯基丙醛酸酯与丙酮的成环缩合2,6-二氯-3-三氯甲基吡啶与亚甲基丁二酸酯的反应,邻氰基苯乙炔、二苯乙二酮和丙酮的反应。但上述方法往往原料较难得到,产率较低或操作麻烦。     

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.     

A Novel Approach to Synthesis of Tricyclic Diterpenoid

A novel approach has been found and the first total synthesis of (±)-Salvirecognine was accomplished by using it. In which intramolecular cyclization and Friedel-Crafts alkylation took place simultaneously to afford key intermediates for synthesis of aromatic tricyclic diterpenoids OMe PPA O O O OMe 1 2 Scheme 1 As shown in Scheme 1 intramolecular cyclization and Friedel-Crafts alkylation took place simultaneously when compound 1 was treated by PPA at 125 ℃. In which the i-pr…     

Synthesis and properties of 3-cyano-4-(4-cyanophenyl)-1,4-dihydropyridine-2(3H)-thiones

Piperidinium 3-cyano-4-(4-cyanophenyl)-1,4-dihydropyridine-2(3H)-thiolates were obtained by the condensation of 1,3-dicarbonyl compounds, 4-cyanobenzaldehyde, and cyanothioacetamide in the presence of an equimolar amount of piperidine. The acidification of these thiolates gave the corresponding 1,4-dihydropyridine-2(3H)-thiones and pyridine-2(1H)-thione. Alkylation of 1,4-dihydropyridine-2-thiolates or the reaction mixture of the three-carbon condensation using iodacetamide gave 2-carbamoylmethylthio-1,4,5,6-tetrahydro- or 1,4-dihydropyridines, which were characterized by their conversion to 4,7-dihydrothieno[2,3-b]pyridines.Latvian Institute of Organic Synthesis, LV-1006, Riga, LatviaTranslated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 794–798, June, 2000.     

Synthesis of 2-substituted 4,5-dihydro-4-oxo-3-furancarboxylates using acylative intramolecular cyclization of sulfonium salts

A simple and efficient synthesis of 4,5-dihydro-4-oxo-3-furancarboxylates using an acylative intramolecular cyclization of sulfonium salts is described. The reaction involved the efficient formation of a mixed anhydride between a linear carboxylic acid and trifluoroacetic anhydride in the presence of N-methylimidazole, followed by the sequential conversion into a highly reactive acylammonium species in situ. This procedure is easily handled, uses readily available inexpensive reagents, and provides a variety of 2-substituted 4,5-dihydro-4-oxo-3-furancarboxylates.