3,5-二甲氧基苯乙烯环酮类化合物的合成及表征

研发环氧合酶(COSX)/5-脂氧酶(5-LOX)双重抑制剂是降低非甾体抗炎药胃肠道(GI)副作用的有效途径之一[1]。大多数二叔丁基苯酚类化合物具有较强的COX/5-LOX双重抑制作用,例如达布飞龙甲磺酸盐(darbufelone mesilate)用于治疗类风湿性关节炎和骨关节炎,GI不良反应小且长效,目前处     

腈亚胺的1,3-偶极环加成反应合成螺吡唑-吡咯里嗪类化合物

通过2-芳亚甲基-2,3-二氢-1H-吡里-1-酮与腈亚胺[经苯甲酰氯苯腙(2)与三乙胺反应生成]的1,3-偶极环加成反应,以较高收率合成了一系列的4-芳基-2,5-二苯基-2H,4H-二氢-螺[吡唑-3,2’-吡咯里嗪]-1’(3’H)-酮.采用NMR,IR,质谱和元素分析等多种谱学技术对产物进行了结构表征.     

3-芳基-2(5H)-呋喃酮-氟喹诺酮杂合体多靶点抗菌化合物的设计、合成及其作用机理研究

借助杂合体药物和多靶点药物的设计方法,将含有3-芳基-2(5H)-呋喃酮结构单元的酪氨酰t-RNA合成酶抑制剂与氟喹诺酮(DNA促旋酶抑制剂)相融合,设计合成了7个结构全新的3-芳基-2(5H)-呋喃酮-氟喹诺酮杂合体化合物.体外抗菌活性筛选发现,大多数化合物对革兰氏阳性菌、革兰氏阴性菌以及真菌均具有较好抑制作用.酶活性评价和分子模拟研究表明,该类化合物是通过干扰蛋白质合成和DNA复制来发挥抑菌作用的双重抑制剂.这些结果充分说明,3-芳基-2(5H)-呋喃酮-氟喹诺酮杂合体化合物作为抗菌化合物有进一步研究的价值.     

金属引导的发散型傅-克环化反应合成羰基稠合的吲哚/吡咯（英文）

报道了金属引导由N-(2-炔基芳基)内酰胺发散型合成羰基稠合的吲哚/吡咯的方法.该反应通过可调控的酰基正离子区域选择性傅-克环化反应进行,同时具有底物范围广,原子经济性和步骤经济性高等优势,有望用于含有相关结构的生物活性分子的合成.     

无催化剂条件下合成喹啉并吡咯并喹啉衍生物

以芳醛、5-氨基吲哚和4-羟基喹啉-2-酮为原料,在回流的乙醇中,无需加入任何催化剂,可高产率得到一系列13-芳基-6,13-二氢化-3H-喹啉并[4,3-b]吡咯并[3,2-f]喹啉-12(11H)-酮衍生物,并通过X射线单晶衍射分析确证了4b的结构.该方法简单,容易操作,为稠合五环含双喹啉杂环化合物提供了有效的合成方法.     

芳基吡唑氟尿嘧啶类化合物的设计、合成与杀虫活性研究

利用以γ-氨基丁酸(GABA)受体抑制剂芳基吡唑类杀虫剂的关键结构5-氨基-3-氰基-1-(取代苯基)吡唑为基本母核,设计、合成了26个创新结构芳基吡唑氟尿嘧啶化合物.目标化合物结构均采用1H NMR,FTIR和元素分析进行了结构确证,以小菜蛾和库蚊为靶标进行了杀虫活性测试.评价结果表明创制化合物具有优越的杀虫活性:在浓度为1000 mg·L-1时,化合物5a~5c,5e,5m及5u对库蚊具有100%的杀虫活性;在浓度为400 mg·L-1时,化合物5p对小菜蛾具有94.5%的杀虫活性.初步构效关系研究表明:苯环上取代基种类及位置等对化合物的生物活性有重要的影响.     

2,5-二甲基-3,4-二乙酰基-1-芳基吡咯的合成

多取代吡咯;二乙酰基己二酮;取代苯胺;2;5-二甲基-3;4-二乙酰基-1-芳基吡咯的合成     

5-芳基四氮唑衍生物的高效合成方法与酯基的伴生降解

以氯化铟为催化剂,通过芳基腈和叠氮化钠的[3+2]环加成反应合成了一系列5-芳基四氮唑,含各种官能团的底物都可以获得高产率.此合成方法还对酯的分解有催化效果,可以在合成四氮唑的同时对酯进行脱保护获得羧酸和醇.     

3-芳基-6-甲基-1,6-二氢-1,2,4,5-四嗪及其衍生物的合成和晶体结构

以乙腈和芳基腈为原料, 经过醚化、环化和还原三步方便且有效地合成了3-芳基-6-甲基-1,6-二氢-1,2,4,5-四嗪, 并在此基础上合成了一系列新的3-芳基-6-甲基-1,6-二氢-1,2,4,5-四嗪衍生物, 通过元素分析, ¹H NMR, IR和HRMS对这些化合物进行了表征. 对化合物N-邻甲基苯-3-苯基-6-甲基-1,6-二氢-1,2,4,5-四嗪-1-甲酰胺(5a)的X射线晶体衍射研究表明: 其属于单斜晶系, P2_{1 /c空间群, 晶胞参数a＝1.3941(6) nm, b＝0.5675(2) nm, c＝2.0614(8) nm; α＝γ＝90°, β＝102.055(6)°; V＝1.5949(11) nm³, 此类化合物的四嗪环采用不对称船式结构, 且具有同芳香性.}     

N-羟乙基-N-芳基丙炔酰胺的芳基磺酰化及螺-三环化反应

报道了一种在四丁基碘化铵(TBAI)和过氧硫酸氢钾复合盐(oxone)存在下,磺酰自由基诱导N-羟乙基-N-芳基丙炔酰胺的螺-三环化串联反应,并合成了系列1-芳基-2-对甲苯磺酰基-5,6-二氢苯并[b]吡咯并[2,1-c][1,4]噁嗪-3(7a H)-酮.螺-三环化串联包括磺酰自由基对炔烃的α-加成、ipso-环化和螺环中间体的邻位俘获.     

Five-Membered 2,3-Dioxo Heterocycles: XLV. Thermolysis of 5-Aryl-4-phenyl-2,3-dihydrofuran-2,3-diones in the Absence of Other Partners and in the Presence of Carbonyl Compounds

Aroyl(phenyl)ketenes generated by thermolysis of 5-aryl-4-phenyl-2,3-dihydrofuran-2,3-diones undergo [4+2]-cyclodimerization to 3-aroyl-6-aryl-3,5-diphenyl-3,4-dihydro-2H-pyran-2,4-diones. Heating of the latter leads to rearrangement with formation of 4-aroyloxy-6-aryl-3,5-diphenyl-2H-pyran-2-ones. Thermolysis of 5-aryl-4-phenyl-2,3-dihydrofuran-2,3-diones in the presence of carbonyl compounds yields 6-aryl-5-phenyl-4H-1,3-dioxin-4-ones.     

Five-membered 2.3-dioxo heterocycles: LXVIII. Three pathways in the reaction of methyl 3-aroyl-1-aryl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates with 3-amino-5,5-dimethylcyclohex-2-en-1-one

Methyl 3-aroyl-1-aryl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates reacted with 3-amino-5,5-dimethylcyclohex-2-en-1-one having no substituent on the nitrogen atom to give 3-aroyl-4-arylamino-6′,6′-dimethyl-6′,7′-dihydro-5H-spiro[furan-2,3′-indole]-2′,4′,5′(1′H,5′H)-triones or methyl 12-aroyl-11-aryl-9-hydroxy-5,5-dimethyl-3,10-dioxo-8,11-diazatricyclo[7.2.1.0^2,7]dodec-2(7)-ene-1-carboxylates. The latter underwent thermal recyclization to 3′-aroyl-1′-aryl-4′-hydroxy-6,6-dimethyl-6,7-dihydrospiro[indole-3,2′-pyrrole]-2,4,5′(1H,1′H,5H)-triones.     

Studies on the Syntheses and Biological Activities of 3-Aryl-6-(1,1'-biphenyl-4-yl)-7H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazines

IntroductionAmongst various heterocycles 3 ,6 -disubstituted- 7H- 1 ,2 ,4- triazolo[3 ,4- b][1 ,3 ,4]thiadiazines have received considerable attentionduring the lasttwo decades as potentially biologicalactive agents[1,2 ] . A literature survey indicated thatthis kind of N - bridged heterocycles displayed awide spectrum of biological properties,such asantimicrobial[3] ,antibacterial,antifungal[4 ] ,antiinflammatory[5] ,diuretic[6 ] ,anthelmintic,andanalgesic[7] . They can also be used as the p…     

2-Acyl(aroyl)-1,1,3,3-tetracyanopropenides: VI. Reaction with hydrogen halides

Reactions of 2-aroyl-1,1,3,3-tetracyanopropenides with hydrogen halides in solvents of low dielectric permittivity result in the formation of 6-amino-2-aroyl-2-halopyridine-3,5-dicarbonitriles. 2-Acyl-1,1,3,3-tetracyanopropenides under similar conditions afford 2-(2-alkylidene-5-amino-4-cyano-2,3-dihydrofuran-3-ylidene)propanedinitriles. In solvents of high dielectric permittivity the result of the reaction depends on the nature of the hydrogen halide and the acyl(aroyl) substituent: With HCl and HBr 2-aroyl-1,1,3,3-tetracyanopropenides form 2-(5-amino-2-aryl-2-halo-4-cyano-2,3-dihydrofuran-3-ylidene)-propanedinitriles, and 2-acyl-1,1,3,3-tetracyanopropenides give 2-(2-alkylidene-5-amino-4-cyano-2,3-dihydrofuran-3-ylidene)propanedinitriles; with HI depending on the reaction conditions and the structure of the acyl substituent 2-(5-amino-2-aryl-4-cyano-2,3-dihydrofuran-3-ylidene)propanedinitriles, 2-(5-amino-4-cyano-2,3-dihydrofuran-3-ylidene) propane-dinitrile, 2-amino-4-(dimethoxybenzyl)-6-iodo-5-cyanonicotinamide, 4-amino-6-iodo-3-oxo-2,3-dihydro-1H-pyrrolo[3,4-c]pyridine-7-carbonitrile, or 4-amino-6-iodo-3-oxo-1-ethylidene-1,3-dihydrofuro[3,4-c]pyridine-7-carbonitrile are obtained.     

Cyclopropanation of N-substituted 3-aryl-2-cyanoprop-2-enamides and derivatives of 5,5-Dimethyl-2-oxo-2,5-dihydrofuran-3-carboxylic acid and 2-oxochromene-3-carboxylic acid with bromine-containing zinc enolates

Zinc enolates derived from 1-aryl-2,2-dibromoalkanones react with N-substituted 3-aryl-2-cyanoprop-2-enamides and 5,5-dimethyl-2-oxo-2,5-dihydrofuran-3-carboxylic and 2-oxochromene-3-carboxylic acid derivatives to give, respectively, N-substituted 2-alkyl-3-aryl-2-aroyl-1-cyanocyclopropane-1-carboxamides, 6-(4-bromobenzoyl)-4,4,6-trimethyl-2-oxo-3-oxabicyclo[3.1.0]hexane-1-carboxylic acid ethyl ester and morpholide, and 1-alkyl-1-aroyl-2-oxo-1a,7b-dihydrocyclopropla[c]chromene-1a-carboxylic acids as a single geometric isomer. Treatment of 1-alkyl-1-aroyl-2-oxo-1a,7b-dihydrocyclopropa[c]chromene-1a-carboxylic acids with carboxylic acid anhydrides leads to the formation of the corresponding 9c-alkyl-1-aryl-3,4-dioxo-9b,9c-dihydro-2,5-dioxacyclopenta[2,3]cyclopropa[1,2-a]naphthalen-1-yl carboxylates.     

Reactions of 1-(4-aminosulfonylphenyl)-5-aryl-4-aroyl-3-hydroxy-3-pyrrolin-2-ones with arylamines and hydrazine hydrate

Depending on the reaction condition, 1-(4-aminosulfonylphenyl)-5-aryl-4-aroyl-3-hydroxy-3-pyrrolin-2-ones reacted with aromatic amines to yield 3-arylamino-3-pyrrolin-2-ones or 4-[aryl (arylamino) methylene]tetrahydropyrrole-2,3-diones. Reactions of 1-(4-aminosulfonylphenyl)-5-aryl-4-aroyl-3-hydroxy-3-pyrrolin-2-ones with hydrazine hydrate afforded pyrrolo[3,4-c]pyrazol-6-ones.     

Synthesis of annelated [a]aza-anthracenones and thieno[3,2-g]aza-naphthalenones through ring transformation of 2H-pyran-2-one followed by photocyclization

A concise synthesis of some new classes of heterocycles (4-aryl-11-oxo-1,2,3,11-tetrahydro-1,3a-diaza-cyclopenta[a]anthracen-6-carbonitriles and 5-aryl-12-oxo-1,3,4,12-tetrahydro-2H-1,4a-diazabenzo[a]anthracene-7-carbonitriles) has been developed by the ring transformation of suitably functionalized 2H-pyran-2-one with α-oxoketene cyclic aminals to intermediates (8-aroyl-5-aryl-2,3-dihydro-1H-imidazo[1,2-a]pyridine-7-ylidene)-acetonitriles and (9-aroyl-6-aryl-1,2,3,4-tetrahydropyrido[1,2-a]pyrimidin-8-ylidene)-acetonitriles) followed by their photocyclization either in CHCl₃ or acetonitrile. This reaction was further explored for the synthesis of methyl 4-aryl-11-oxo-1,2,3,11-tetrahydro-1,3a,9-triaza-cyclopenta[a]anthracene-6-carboxylate, 4-aryl-11-oxo-1,2,3,11-tetrahydro-1,3a,9-triaza-cyclopenta[a]anthracene-6-carbonitriles, 5-aryl-12-oxo-1,3,4,12-tetrahydro-2H-1,4a,10-triazabenzo[a]anthracene-7-carbonitriles, 4-aryl-10-oxo-1,2,3,10-tetrahydro-9-thia-1,3a-diazadicyclopenta[a,g]naphthalene-6-carbonitriles and 5-aryl-11-oxo-1,3,4,11-tetrahydro-2H-10-thia-1,4a-diazacyclopenta[b]phenanthrene-7-carbonitriles from the similar reactions.     

稠杂环化合物的研究(Ⅳ)——5-醛胺基-1-芳基-1,2,3-连三唑[2,3-d]嘧啶-4-酮类衍生物的合成及抗菌性能

我们已报道了1-芳基-4-乙氧羰基-5-氨基-1,2,3-连三唑类衍生物(1)的合成及抗菌活性,为研究药物构效关系,我们利用1的酰肼3同甲酸反应,制得了尚未报道的5-醛胺基-1-芳基-1,2,3-连三唑[2,3-d]嘧啶-4-酮(4_(a-c))及5-氨基-6-羟基-7H-1-(间硝基)苯基-1,2,3-连三唑[2,3-d]嘧啶-4-酮(5_d).并观察了它们对枯草杆菌,金黄色葡萄球菌等繁殖的抑制作用。     

Synthesis,stereochemistry, and isomeric transformations of cis- and trans-1,2-dimethyl-4-aryl-5-aroyl-2-imidazolines

The corresponding trans- and cis-1,2-dimethyl-4-aryl-5-aroyl-2-imidazolines were obtained from complexes of cis- and trans-1-methyl-2-aryl-3-aroylaziridines with BF₃ by heating with acetonitrile. The reaction proceeds with inversion of the configuration of the starting 3-aroylaziridines. In the presence of bases the complexes of cis-1,2-dimethyl-4-aryl-5-aroyl-2-imidazolines readily undergo isomerization to the corresponding trans analogs. The structures of the products were established on the basis of the IR, PMR, and mass spectra and the results of elementary analysis. The configurations of the compounds were determined by means of the Overhauser nuclear effect.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 952–957, July, 1981.     

Five-Membered 2,3-Dioxo Heterocycles: XLVII. Reaction of 5-Aryl-4-phenyl-2,3-dihydrofuran-2,3-diones with Compounds Containing C = N and C≡N Bonds

Thermal decarbonylation of 5-aryl-4-phenyl-2,3-dihydrofuran-2,3-diones gives rise to intermediate aroyl(phenyl)ketenes which react with nonactivated Schiff bases, N,N'-dicyclohexylcarbodiimide, and p-di-methylaminobenzonitrile according to the [4 + 2]-cycloaddition pattern with formation of 6-aryl-5-phenyl-4H-1,3-oxazin-4-ones. Reactions of 5-aryl-4-phenyl-2,3-dihydrofuran-2,3-diones with activated Schiff bases at a temperature below the thermolysis temperature lead to 4-aroyl-4-phenyltetrahydropyrrole-2,3-diones.