新型取代3-芳基-1,2,4-三唑并[3,4-b]苯并噻唑的合成及其杀菌活性

为了寻找新的含苯并噻唑稠杂环农药先导化合物,利用取代2-肼基苯并噻唑与取代苯甲酸在三氯氧磷中回流反应,合成了18个新型取代3-芳基-1,2,4-三唑并[3,4-b]苯并噻唑化合物,并利用1H NMR,EI-MS及元素分析对其结构进行了表征.初步生物活性试验结果表明,在50 mg/L浓度下,部分目标化合物对立枯丝核菌(Rhizoctonia solani)、西瓜壳二孢菌(Ascochyta citrullina)、香蕉枯萎病菌(Fusarium oxysporum f.sp.cubense)、烟草炭疽病菌(Colletotrichum nicotianae)具有中等杀菌活性.然而,部分化合物对灰葡萄孢菌(Botrytis cinerea)反而起到一定促进生长作用.     

NOVEL THREE COMPONENT SYNTHESIS OF 1,2,4-TRIAZOLO[3,4-b]THIAZOLES AND THEIR ANTIMICROBIAL ACTIVITY

1,2,4-Triazolo[3,4-b]thiazole derivatives 5a–j have been synthesized by novel multi-component reaction of 2,4-dichloro-5-fluorophenacyl bromide (1), thiosemicarbazide (2), and aromatic carboxylic acids (4) using phosphorous oxychloride as the cyclizing agent. This reaction protocol is simple, efficient, and requires shorter reaction times in comparison to the conventional multi-step synthesis. The products were identified to be same by an alternate synthesis. All the compounds were screened for their antimicrobial activity against some of bacterial and fungal strains.     

Microwave Assisted Synthesis of 6-Aryl-3-substituted-5H-[1,2,4]-triazolo[4,3-b][1,2,4]triazoles: A Case for a Comparative Study

A simple and fast synthesis of 6-aryl-3-substituted-5H-[1,2,4]-triazolo[4,3-b][1,2,4]triazoles 4 in high yields has been developed by microwave assisted heterocyclization of N-(3-methylthio-5-substituted-4H-1,2,4-triazol-4-yl)benzenecarboximidamides 3 . The effectiveness of the microwave irradiation and conventional heating for the formation of compounds 4 has been investigated.     

The Synthesis of Some New 7‐Methyl‐3‐substituted‐1,2,4‐triazolo[3,4‐b]benzothiazoles

New 7‐Methyl‐3‐substituted‐1,2,4‐triazolo[3,4‐b]benzothiazoles were synthesized from p‐methylaniline to 5 with various aromatic carbonic acids. The yielded product 6a‐j was investigated with Elemental analyses, NMR, MS and IR techniques.     

Facile synthesis of some novel triazolo[3,4-b]thiadiazines and triazolo[4,3-b]tetrazines

4-Amino-5-ethyl-4H-1,2,4-triazole-3-thiol was used as a key intermediate for the synthesis of triazolo[3,4-b][1,3,4]thiadiazines, triazolo[4,3-b][1,2,4,5]tetrazines and Schiff’s base via reactions with various hydrazonoyl halides and salicyaldehyde, respectively. Moreover triazolyl-N-N′-triazole derivatives were prepared from reaction of Schiff’s base with various hydrazonoyl halides. The structures of all the newly synthesized heterocyclic compounds were established by considering elemental analysis and spectral data.     

Synthesis of 8-tert-Butyl-9-oxo-1,2,4-triazolo[4,5-b]-1,2,4-triazolo[3,4-c]-1,2,4-triazine

8-tert-Butyl-9-oxo-1,2,4-triazolo[4,5-b]-1,2,4-triazolo[3,4-c]-1,2,4-triazine has been synthesized by the interaction of 6-tert-butyl-3-hydrazino-1,2,4-triazolo[3,4-c]-1,2,4-triazin-5-one with formic acid. The conditions of carrying out the reaction are discussed. Spectral characteristics are given.     

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,     

Synthesis,Characterization and Crystal Structure of 3-o-Fluorophenyl-6-（4-decarboxydehydroabietyl）-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazole

Three novel 1,2,4-triazolo[3,4-b]-1,3,4-thiadiazoles were designed,synthesized and characterized by IR,NMR and APCI-MS.3-o-Fluorophenyl-6-(4-decarboxydehydroabietyl)-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazole(6a,C28H31FN4S) was structurally determined by single-crystal X-ray diffraction.The crystal belongs to the orthorhombic system,space group P212121 with a=6.0153(14),b=12.2577(19),c=34.055(3),V=2511.0(7)3,Z=4,Mr=474.63,Dc=1.255Mg/m3,λ=0.71073 ,μ(MoKα)=0.160 mm-1,F(000)=1008,the final R=0.0555 and wR=0.1248 for 3094 observed reflections with I2σ(I).There are six rings in the crystal structure of the title compound.The dihedral angle between 1,2,4-triazole and 1,3,4-thiadiaole rings is 1.4o,and that between 1,2,4-triazole and benzene ring D 25.5o.     

10-氯-5-二乙氧基甲基-1,3-二甲基色烯并[4,3-d]吡唑并[3,4-b]吡啶-6(3H)-酮的合成和晶体结构

利用L-脯氨酸催化的5-氯水杨醛(1)与6-甲基-4-羟基吡喃酮(2)的缩合反应及硫酸铜催化下与1,3-二甲基-5-氨基吡唑(3)的串联反应,合成得到了10-氯-1,3-二甲基-5-(2-氧代丙基)色烯并[4,3-d]吡唑并[3,4-b]吡啶-6(3H)-酮(4)和10-氯-5-二乙氧基甲基-1,3-二甲基色烯并[4,3-d]吡唑并[3,4-b]吡啶-6(3H)-酮(5).化合物5的结构通过单晶X射线衍射法确定:晶体属于三斜晶系,空间群P-1;相对分子质量Mr=803.68;晶胞参数a=1.03160(10)nm,b=1.42900(13)nm,c=1.44268(15)nm;V=1.9448(3)nm~3;Z=2;晶胞密度Dc=1.372g/cm~3;吸收系数μ=0.228mm-1;单胞中电子的数目F(000)=840.晶体结构用直接法解出,经全矩阵最小二乘法对原子参数进行修正,最终的偏离因子为R=0.0681,w R=0.2051.在晶体结构中色烯环与吡啶环及吡唑环近似于共平面.     

Synthesis and Tautomeric Structure of 7-Arylhydrazono-7H-[1,2,4]Triazolo[3,4-b][1,3,4]Thiadiazines

Two synthetic approaches were developed for the title compounds 8a-g via coupling of diazotized anilines with 7-acetyl-6-methyl-3-phenyl-7H-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazine 7 , and reaction of N-aryl 2-oxopropanehydrazonoyl chlorides 9 with 4-amino-3-mercapto-5-phenyl-1,2,4-triazole 1 . The tautomeric structures of 8 were elucidated by their spectral analyses and correlation of their acid dissociation constants with Hammett equation.     

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.     

[1,2,4]三唑并[3,4-b][1,3,4]噻二嗪类衍生物的合成及生物活性研究进展

[1,2,4]三唑并[3,4-b][1,3,4]噻二嗪作为极具前景的活性基团,在抗菌、抗肿瘤等方面具有多种药理活性,在药物和化学领域受到了广泛的关注。本文以含三唑并噻二嗪结构化合物的合成及其在抗肿瘤、抗菌等方面的生物活性为依据,对近几年国内外关于[1,2,4]三唑并[3,4-b][1,3,4]噻二嗪类化合物的研究进行分析总结,以期为后续该类新型抗肿瘤化合物的设计合成提供参考。     

Synthesis of Some New Pyrazolo[3,4-b]Pyridlne and Pyrazolo[3,4-d]Pyrimidine Derivatives1

Several pyrazolo[3,4-b]pyridine (3,4) and pyrazolo-[3,4-d]pyrimidine (5-13) derivatives were prepared using 5-amino-l-(5-ethyl-5H-1,2,4-triazino[5,6-b]-indol-3-yl)-lH-pyrazole-4-carbonitrile (2) . The pyridine derivatives 3 and 4 were obtained by reaction of 2 with malononitrile and ethyl cyanoacetate, respectively, while pyrimidine analogs 5-13 were synthesized cither by a one-step or multi-step sequence.     

新型含氟1,2,4-三唑[3,4-b]-1,3,4-噻二唑衍生物的合成及其除草活性

以对氟苯甲酰肼为初始原料,经成盐、环化和一锅法反应制得中间体5-对氟苯基-2,4-二氢-1,2,4-三唑-3-硫酮磷亚胺(4);4与芳基异氰酸酯发生氮杂Wittig反应,后经成环反应合成了11个新型的含氟6-芳氨基-1,2,4-三唑[3,4-b]-1,3,4-噻二唑衍生物(6a~6k),其结构经~1H NMR,~(13)C NMR,IR和HR-MS表征。对单、双子叶植物的除草活性测试结果表明:浓度为100 mg·L~(-1)时,6c和6f对稗草和萝卜的茎和根的生长表现出优异的抑制活性,抑制率高达100%。     

含脱羧脱氢松香基的1,2,4-三唑并[3,4-b]-1,3,4-噻二唑衍生物的合成、表征及抑菌活性

用POCl3为催化剂和脱水剂,3-取代-4-氨基-5-巯基-1,2,4-三唑4和10分别与脱氢松香酸1反应制得14种未见文献报道的3-取代-6-(4′-脱羧脱氢松香基)-1,2,4-三唑并[3,4-b-]-1,3,4-噻二唑衍生物]5a~5e和11a~11i;所有化合物的结构均经IR、¹H NMR、¹³C NMR 和MS测试技术分析确认。 抑菌活性测试表明,目标化合物对白色念珠菌(C.Albicans)、大肠杆菌(E.Coli)、藤黄微球菌(M.Luteus)和痢疾志贺杆菌(S.Dysenteriae)均有一定的抑制作用。     

Conversion of novel palladacycles into oxopyrrolo[3,4-b]quinolines

The quinolinylcyclopalladated complexes 3a–b were synthesised in good yields (81% and 77%) by the insertion reaction of the prepared dinuclear palladium complexes [Pd(C,N-2-C₉H₄N-CHO-3-R-6)Cl(PPh₃)]₂ [(R = H (2a), R = OMe (2b)] with isonitrile XyNC (Xy = 2,6-Me₂C₆H₃). The cyclopalladated complexes 3a–b were also obtained in low yields (39% and 33.5%) via a one pot oxidative addition reaction of quinoline chloride 1a–b with isonitrile XyNC:Pd(dba)₂ (4:1). The reactions of 3a–b with Tl(TfO) (TfO = triflate, CF₃SO₃) in the presence of H₂O or EtOH causes depalladation reactions of the complexes to provide the corresponding organic compounds 4a–b, 5a–b and 6a–b in yields (41%, 27% and 18–19%). The products were characterized by satisfactory elemental analyses and spectral studies (IR, ¹H, ¹³C and ³¹P NMR). The crystal structures of 2a, 3a and 3b were determined by X-ray diffraction studies.     

含双-三唑并噻二唑环的庚烷类衍生物的合成及抗菌活性

The aroylhydrazides were prepared by esterification and hydrazinolysis of corresponding aromatic carboxylic acids.The reaction of aroylhydrazides with CS2/KOH in absolute ethanol gave potassium aroyldithiocarbazates and then hydrazinolysis of potassium aroyldithiocarbazates with hydrazine hydrate afforded 3-aryl-4-amino-5-mercapto-1,2,4-triazoles(1a～1g).New seven compounds of bis[(3-aryl)-s-triazolo[3,4-b]-[1,3,4]thiadiazole derivatives(2a～2g) were synthesized in high yields by cyclization of nonanedioic ac...     

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。     

Molecular and crystal structure of 5,7-diphenyl-7-methyl-4,7-dihydro-1,2,4-triazolo[1,5-a]pyrimidine

The molecular and crystal structures of 5,7-diphenyl-7-methyi-4,7-dihydro-1,2,4-triazolo[1,5-a]pyrimidine have been studied by X-ray structural methods. The crystal is monoclinic,a=16.112(3),b=13.489(3),c=14.480(3)Å, =101.62(2)°,Z=8, space groupC2/c,R=0.071. The presence of short intermolecular contacts indicates considerable steric strain in the molecule. The dihydropyrimidine ring exists in an unevenly planar boat conformation. Increasing the steric strain of the dihydrocycle leads to a twisted conformation.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1912–1914, November, 1993.