3-（5-H/CH3-苯并咪唑-2-亚甲硫基）-5-取代-[1,2,4]三唑-4-胺衍生物的合成、结构和生物活性

利用3-巯基-4-氨基-5-取代-1,2,4-三唑和2-氯甲基-5-取代-苯并咪唑在氢氧化钠溶液中反应,得到17个3-(5-H/CH3-苯并咪唑-2-亚甲硫基)-5-取代-[1,2,4]三唑-4-胺衍生物.所有目标化合物经元素分析、红外光谱、核磁共振氢谱确定结构;采用溶液法得到化合物3f与Co2+形成的配合物,通过X射线单晶衍射确定结构.初步的生物活性测试结果表明,所合成的化合物对小麦芽鞘和绿豆发芽有着较好的生长调节作用;化合物3d,3i对金黄色葡萄球菌具有一定的抑制作用.     

含1,2,4-三唑-5-硫酮席夫碱的新型1,2,4-三唑并[1,5-a]嘧啶衍生物的合成及生物活性研究

以2-苄硫基-5-甲基-7-羟基-1,2,4-三唑并[1,5-a]嘧啶为原料,经醚化、肼解、成盐、关环和席夫碱反应合成了20个新型的含1,2,4-三唑-5-硫酮席夫碱的1,2,4-三唑并[1,5-a]嘧啶类化合物,通过IR,1H NMR,MS和元素分析对所合成的化合物进行了结构表征.初步生物活性测试结果表明,部分化合物表现出一定的抑菌或较好的抗烟草花叶病毒(TMV)活性.在500μg/mL浓度下,化合物6b,6f和6p对TMV的抑制率分别为41%,43%和40%.     

3-(4-吡啶基)-4-(6-取代色酮-3-基-亚甲氨基)-5-芳氨基-1,2,4-三唑的合成

N-芳基-N'-[(4-吡啶基)羰基]氨基硫脲用85%的水合肼环化, 得到3-(4-吡啶基)-4-氨基-5-芳氨基-1,2,4-三唑(2a～2c). 然后再与3-甲酰基色酮(3a～3d)反应, 制备得到了一系列新化合物: 3-(4-吡啶基)-4-(6-取代色酮-3-基亚甲氨基)-5-芳氨基-1,2,4-三唑(4a～4c, 5a～5c, 6a～6c, 7a～7c). 化合物的结构经元素分析, IR, ¹H NMR和MS确证.     

4-取代苯次甲亚胺-5-(1-苯基-3-甲基-5-氯吡唑)-2H-1,2,4-三唑-3-硫酮的合成

以乙醇为溶剂,冰醋酸为催化剂,4-氨基-5-(1-苯基-3-甲基-5-氯吡唑)-1,2,4-三唑-3-硫酮(1)与芳醛经缩合反应合成了7个新型的4-取代苯次甲亚胺-5-(1-苯基-3-甲基-5-氯吡唑)-4H-1,2,4-三唑-3-硫酮(3a~3g),收率66%~74%,其结构经1H NMR,IR及元素分析表征。合成4-(苯次甲亚胺)-5-(1-苯基-3-甲基-5-氯吡唑)-2H-1,2,4-三唑-3-硫酮(3a)的最佳反应条件为:以乙醇为溶剂,乙酸为催化剂,1 10 mmol,n(苯甲醛)∶n(1)=1.2,于75℃反应3 h,产率74%。     

5-取代-4-氨基-1,2,4-三唑硫酮席夫碱合成、表征及生物活性

为了筛选出高活性的1,2,4-三唑席夫碱化合物,本文以二氨基硫脲与取代羧酸为原料,回流反应生成中间体5-取代-4-氨基-1,2,4-三唑硫酮,再与2-氯-6-氟苯甲醛在冰乙酸催化下合成了一系列三唑席夫碱类新化合物。目标化合物结构通过IR、元素分析、1H NMR、ESI-MS进行表征。采用室内平皿法初步测定了标题化合物对烟草赤星病、马铃薯干腐病、小麦赤霉病、西瓜枯萎病4种植物病原菌的生物活性,结果表明,合成的部分化合物具有较好的抑菌活性。     

超声辐射下合成4,5-二氢-1-取代胺亚甲基-3-(2-三氟甲基苯并[d]咪唑- 1-亚甲基)-4-芳基-1,2,4-三唑-5-硫酮

以1-肼羰亚甲基-2-三氟甲基苯并[d]咪唑(1)为原料, 与芳基异硫氰酸酯在无水乙醇中反应得酰氨基硫脲2a～2d, 继而在氢氧化钠水溶液中合环得4,5-二氢-3-(2-三氟甲基苯并[d]咪唑-1-亚甲基)-4-芳基-1,2,4-三唑-5-硫酮(3a～3d), 然后分别采用超声辐射法和常规加热法与四种胺反应合成了16个未见报道的Mannich碱4a～4d, 5a～5d, 6a～6d和7a～7d. 与常规加热法对比, 超声辐射法具有操作简单, 反应时间短, 条件温和, 产率高, 副反应少等优点, 为此类化合物的合成提供了一种有效的新方法. 目标化合物的结构经元素分析, IR和¹H NMR确证.     

2-[3-苯氧甲基-4-苯基-[1,2,4]三唑-5-硫基]乙酰胺的合成、晶体结构表征及生物活性

在微波辐射下, 由苯氧乙酰肼出发, 合成了一系列三唑类衍生物, 利用单晶X射线衍射法测定了化合物5f的单晶结构. 化合物5f通过分子间氢键及范德华力形成了三维网状结构的超分子. 这些化合物对植物根的生长具有比较明显的促进活性.     

2-(3-芳氧甲基-4-苯基-1,2,4-三唑-5-硫基)乙酸的微波合成及生物活性研究

在微波辐射条件下, 芳氧乙酰肼经两步反应制得4-苯基-3-芳氧甲基-1,2,4-三唑-5-硫酮衍生物, 再与氯乙酸反应得到6种尚未见文献报道的2-(3-芳氧甲基-4-苯基-1,2,4-三唑-5-硫基)乙酸衍生物. 目标化合物的结构经IR, ¹H NMR和元素分析进行了确证. 生物活性试验结果表明, 该类化合物对双子叶植物油菜具有良好的生物调节活性.     

5-苄基-4-氨基-3-巯基-1,2,4-三唑席夫碱合成与生物活性研究

为进一步研究三唑席夫碱化合物的合成与性质,以熔融法合成中间体5-苄基-4-氨基-3-巯基-1,2,4-三唑,再与取代醛在冰醋酸催化下回流反应合成了6个1,2,4-三唑席夫碱化合物,其结构通过元素分析,红外光谱,核磁共振氢谱进行了表征。生物测试结果表明,合成的三唑席夫碱化合物对烟草赤星病、马铃薯干腐病、小麦赤霉病、番茄早疫病、西瓜枯萎病5种植物病原菌具有较好的抑菌活性。     

微波促进下3-(2-苯并呋喃基)-4-氨基-5-巯基-1,2,4-三唑

微波辐射条件下, 首先由2-苯并呋喃甲酰肼依次与二硫化碳和水合肼反应合成3-(2-苯并呋喃基)-4-氨基-5-巯基- 1,2,4-三唑, 进一步在微波辐射条件下由4-氨基-5-巯基-1,2,4-三唑分别与芳甲酸/芳氧基乙酸、α-溴代苯乙酮及芳醛反应以较高产率制得了相应的1,2,4-三唑并[3,4-b]-1,3,4-噻二唑、1,2,4-三唑并[3,4-b]-1,3,4-噻二嗪及4-芳亚甲基亚胺基-5-巯基-1,2,4-三唑. 产物结构经IR, ¹H NMR, MS及元素分析进行了表征.     

Syntheses and Crystal Structures of 4-Amino-3- （3-hyd roxyp ropyl）- 1H-1,2,4-triazole-5（4H）-thione and 6-（4-Biphenylyl）-3-（3-hydroxypropyl）-7H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazine

1INTRODUCTION It has been reported that3,6-disubstituted-7H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazines have a broad spec-trum of bioactivities,such as antimicrobial[1],antibac-terial,antifungal[2],anti-inflammatory[3],diuretic[4],an-thelmintic and analgesic[5].They can also be used as plant-growth regulating agents[6],photographic coup-lers,dyes for improved preservability and absorption characteristics,and inhibitors of malignant cellularZOU K.H.et al.:Syntheses and Crystal Structures o…     

Synthesis, Crystal Structure, Antibacterial Activities and Theoretical Computation of 3-（2-Hydroxybenzly）-4-（4-isopropylbenzylideneamino）-（1H）-1,2,4-triazole-5-thione

1INTRODUCTION Recently,compounds containing pyrazole,imida-zole,triazole(including benzotriazole),pyridine,tetrazole and indole have attracted much interest because they exhibit some fungicidal activity,plant-growth regulating activity and antibacterial acti-vity[1～10].Schiff bases also constitute a good type of biologically active substructure[11～14],and the sulfur-containing Schiff bases are particularly effective.Studies of pyrazole Schiff base-type fungicides andtriazole compounds c…     

Synthesis and Crystal Structure of 5-（p-Toly1）-4- [2-（2,4-dichlorophenoxy）acetamido]-l,2,4- triazole-3-thione Ethyl Acetate Solvate

A novel compound 5-（p-tolyl）-4-[2-（2,4-dichlorophenoxy）acetamido]-1,2,4-tria zole- 3-thione 2a has been synthesized by the reaction of 5-（p-tolyl）-4-amino-1,2,4-triazole-3-thione 1 with 2-（2,4-dich/orophenoxy）acetyl ch/oride. Interestingly, the title compound 2 was obtained when 2a crystallizes from a mixed solution of petroleum ether and ethyl acetate, and it has been characterized by elemental analysis, IR, ^1H NMR spectra and single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group P1 with a = 9.780（5）, b = 10.876（6）, c = 11.615（6） /A, a = 104.822（7）, β= 94.105（6）, ）, = 94.305（6）°, V= 1185.7（11）/A3, Z = 2,μ = 0.397 mm^-1, Mr= 497.39, Dx= 1.393 g/cm^3, F（000） = 516, S = 1.097, the final R = 0.0730 and wR = 0.2133 for 4111 unique reflections （Rint = 0.0525） with 3212 observed ones. The dihedral angles made by the triazole ring with the methyl- and chloro-substituted benzene rings are 43.5（7） and 50.2（9）°, respectively. Some intra- and intermolecular hydrogen bonds together with C-H…π interactions existing in the lattice stabilize the crystal structure.     

Synthesis and Crystal Structure of 1-（4-Fluorophenyl）-2-hexylthiobenzo[4,5]-furo[3,2-d]-1,2,4-triazolo[1,5-a]pyrimidin-5（1H）-one

The crystal structure of the title compound 1-(4-fluorophenyl) -2-hexylthio-benzo [4,5]furo[3,2-d]-1,2,4-triazolo[1,5-a]pyrimidin-5(1H) -one(C23H21FN4O2S,Mr = 436.5) has been prepared and determined by single-crystal X-ray diffraction. The crystal is of monoclinic,space group P21/n with a = 13.9854(3) ,b = 17.2678(4) ,c = 18.1828(5) ,β = 99.364(2) °,V = 4332.58(18) 3,Z = 4,Dc = 1.338,F(000) =1824,μ = 0.185 mm-1,MoKa radiation(λ = 0.71073) ,R = 0.0538 and wR = 0.1162 for 4728 observed reflections with I > 2σ(I) . X-ray diffraction analysis reveals the fused rings of benzo[4,5]furo[3,2-d]-1,2,4-triazolo[1,5-a] pyrimidin-5(1H) -one system are nearly coplanar. The crystal packing is mainly stabilized by weak intermolecular C-H···O hydrogen bond and π-π interactions.     

Regioselectivity of the monohalogenation of 4-allyl-3-allylamino-1,2,4-triazole-5-thione

The monohalogenation of 4-allyl-3-allylamino-1,2,4-triazole-5-thione has been studied. It was established that the action of bromine and iodine on 4-allyl-3-allylamino-1,2,4-triazole-5-thione at low temperatures leads to selective closure of a thiazoline ring. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 922–926, June, 2007.     

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.     

Synthesis of 5-Hydroxymethyl-8-methyl-3-(3-aryl-[1,2,4]oxadiazol-5-yl)-2H-pyrano[2,3-c]pyridin-2-ones and Their Esters

New 5-hydroxymethyl-8-methyl-3-(3-aryl-[1,2,4]oxadiazol-5-yl)-2H-pyrano-[2,3-c]pyridin-2-ones and their esters were synthesized. The structure of obtained compounds was determined through a complete ¹H NMR analysis.     

2-芳基-5-(5-苯基-2H-四唑-2-亚甲基)-1,3,4-噁二唑类化合物的研究

作者曾研究2-芳基-5-(2-苯基-4-喹啉基)-1,3,4-噁二唑类衍生物,并发现它们具有促进小麦发芽生长的功效。Juby和Shan等报道某些四唑类化合物具有消炎性     

5-甲基-1,2,4-三唑-3-硫酮类糖苷化合物的合成及抗菌活性

在KOH/丙酮体系中, 以5-甲基-4-N-取代苯基亚胺/胺基-1,2,4-三唑-3-硫酮为原料, 与溴-α-D-四乙酰葡萄糖进行Kenigs-Knorr反应合成了10个新颖的化合物—5-甲基-4-N-取代苯基亚胺基/胺基-3-S-(2',3',4',6'-四-O-乙酰基-β-D-吡喃葡萄糖基)-1,2,4-三唑(2a~2e, 5a~5e); 并在二氯甲烷/甲醇/甲醇钠混合体系中水解脱除乙酰基, 得到10个新颖的化合物—5-甲基-4-N-取代苯基亚胺基-3-S-(β-D-吡喃葡萄糖基)-1,2,4-三唑(3a~3e)及5-甲基-4-N-取代苯基胺基-3-S-(β-D-吡喃葡萄糖基)-1,2,4-三唑(6a~6e). 化合物的结构均经核磁共振波谱(NMR)、 红外光谱(IR)和高分辨质谱(HRMS)分析确证. 生物活性测试结果表明, 目标化合物对大肠杆菌、 金黄色葡萄球菌、 枯草芽孢杆菌和白色念珠球菌普遍具有较好的抗菌活性. 化合物3d和3e对4种菌株的最小抑菌浓度相对较低, 表现出较强的广谱抗菌活性.     

Synthesis of 4-amino-5-(4,6-diphenyl-2-pyrimidinyl)-3,4-dihydro-2H-1,2,4-triazole-3-thione and its reactions with C-electrophiles

4-Amino-5-(4,6-diphenyl-2-pyrimidinyl)-3,4-dihydro-2H-1,2,4-trazole-3-thione is formed from the reaction of 4,6-diphenylpyrimidinecarboxylic acid or its ethyl ester with thiocarbonyl hydrazide. Alkylation of the product leads to S-alkyl derivaties or 6-substituted 3-(4,6-diphenyl-2-pyriimidinyl)-7H-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazine. Acetylation of 4-amino-5-(4,6-diphenyl-2-pyrimidinyl)-3,4-dihydro-2H-1,2,4-triazole-3-thione gave under different conditions monoacetyl-, diacetyl, and triacetyl derivatives at the amino group and the N₍₂₎ atom, whereas benzoylation gave a benzoyl group at the amino group and 3-(4,6-diphenyl-2-pyrimidinyl)-6-phenyl-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazole. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, 1088–1094, July, 2007.