3-芳基-6-对甲苯甲酰氨基均三唑并[3,4-b]-1,3,4-噻二唑的合成及生物活性

利用3-芳基-4-氨基-5-巯基-1,2,4-均三唑和对甲苯甲酰异硫氰酸酯在乙腈中反应, 得到一系列3-芳基-6-对甲苯甲酰氨基均三唑并[3,4-b]-1,3,4-噻二唑, 用¹H NMR, IR, MS和元素分析确定了其结构, 并对其进行了抗菌活性测试.     

3-(3＇-芳基-5＇-硫酮-1＇,2＇,4＇-三唑-4＇-基)-氨甲酰基色酮类化合物的合成

报道3-甲酰基色酮经Jones试剂氧化后得到3-羧基色酮,再与3-芳基-4-氨基-5-硫酮-1,2,4-三唑在POl3作用下,得到一系列3-(3＇-芳基-5＇-硫酮-1＇,2＇,4＇-三唑-4-＇-基)-氨甲酰基色酮类化合物.所有化合物的结构均经IR,LCMS,1H NMR,元素分析确证.     

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.     

酰氨基硫脲及相关杂环衍生物研究（XXV）──1－［5′－氨基－1′－（4″－氯苯基）－1′，2′，3′－三唑－4′－甲酰基］－4－芳基氨基硫脲的合成和波谱研究

通过５－氨基－１－（４′－氯苯基）－４－甲酰肼基－１，２，３－三唑与芳基异硫氰酸酯的反应，合成了１３种新的１－［５′－氨基－１′－４″－氯苯基）－１′，２′，３′－三唑－４′－甲酰基］－４－芳基氨基硫脲类化合物３ａ－１，经元素分析、ＩＲ、１ＨＮＭＲ以及ＭＳ确证其结构。     

3-(3′-芳基-5′-硫酮-1′,2′,4′-三唑-4′-基)-氨甲酰基色酮类化合物的合成

报道 3 甲酰基色酮经Jones试剂氧化后得到 3 羧基色酮 ,再与 3 芳基 4 氨基 5 硫酮 1,2 ,4 三唑在POCl3 作用下 ,得到一系列 3 (3′ 芳基 5′ 硫酮 1′ ,2′,4′ 三唑 4′ 基 ) 氨甲酰基色酮类化合物 .所有化合物的结构均经IR ,LC MS ,1HNMR ,元素分析确证     

1-[3′-(4"-甲氧基苯基)-5′-甲基异噁唑-4′-甲酰基]-4-芳基氨基硫脲及其衍生物的合成

以3,5-二取代异噁唑-4-甲酰肼为基本原料制备关键中间体1-(3-对甲氧基苯基-5-甲基异噁唑-4-基)-4-芳基氨基硫脲(3a～3c);3在不同条件下经关环反应制得含有3,5-二取代异噁唑的2-芳氨基噻二唑(4a～4c),2-芳氨基噁二唑(5a～5c)和3-[3′-(4"-甲氧基苯基)-5′-甲基-异噁唑4′-基)-4-芳基-1,2,4-三唑-5-硫酮(6a～6c);6与碘甲(乙)烷反应合成了4-芳基-5-[3′-(4″-甲氧基苯基)-5′-甲基异噁唑-4′-基]-3-甲(乙)硫基-1,2,4-三唑(7a～8c),其结构经1H NMR,IR,MS和元素分析表征,其中4,5,7和8未见文献报道.     

1-[3’-(4″-甲氧基苯基)-5’-甲基异噁唑-4’-甲酰基]-4-芳基氨基硫脲及其衍生物的合成

以3,5-二取代异噁唑-4-甲酰肼为基本原料制备关键中间体1-(3-对甲氧基苯基-5-甲基异噁唑-4-基)-4-芳基氨基硫脲(3a～3c);3在不同条件下经关环反应制得含有3,5-二取代异噁唑的2-芳氨基噻二唑(4a～4c),2-芳氨基噁二唑(5a～5c)和3-[3’-(4″-甲氧基苯基)-5’-甲基-异噁唑-4’-基)-4-芳基-1,2,4-三唑-5-硫酮(6a～6c);6与碘甲(乙)烷反应合成了4-芳基-5-[3’-(4″-甲氧基苯基)-5’-甲基异噁唑-4’-基]-3-甲(乙)硫基-1,2,4-三唑(7a～8c),其结构经1H NMR,IR,MS和元素分析表征,其中4,5,7和8未见文献报道。     

N-5-(1H-1,2,4-三唑基)-N′-芳甲酰基脲的合成与生物活性

以5-氨基-1H-1,2,4-三唑-3-羧酸与酰基异氰酸酯反应,合成了15个新的N-5-(1H-1,2,4-三唑基)-N′-芳甲酰基脲,用核磁共振氢谱、红外光谱和元素分析确证了其结构,并进行了室内生物活性测试.生测试验证明部分酰基脲类化合物具有良好的植物生长调节活性,其中N-5-(3-羧基-1,2,4-三唑基)-N′-o-氯苯甲酰基脲、N-5-(3-羧基-1,2,4-三唑基)-N′-o-溴苯甲酰基脲和N-5-(3-羧基-1,2,4-三唑基)-N′-P(或m)-甲基苯甲酰基脲具有优良的生长素活性.     

酰氨基硫脲及相关杂环衍生物研究（XXV）

通过５－氨基－１－（４＇－氯苯基－４－甲酰肼基－１，２，３－三唑与芳基异硫氰酸酯的反应，合成了１３种新的１－［５＇－氨基－１＇－（４＇＇－氯苯基）－１＇，２＇，３＇－三唑－４＇－甲酰基］－４－芳基氨基硫脲类化全物３ａ－１，经元素分析，ＩＲ，ＨＮＭＲ以及ＭＳ确证其结构。     

2-芳胺基-5-[5′-氨基-1′-(4″-氯苯基)-1′,2′,3′-三唑-4′-基]-1,3,4-噻二唑的合成~≠

1-[5’-氨基-1’-(4”-氯苯基)-1,2,3-三唑-4’-甲酰基]-4-芳基-3-氨基硫脲在浓硫酸催化下环化得到2-芳胺基-5-[5’-氨基-1’-(4”-氯苯基)-1’,2’,3’,-三唑-4’-基]-1,3,4-噻二唑2a～i,依次法合成了九个标题化合物,收率为30～74％。化合物2i的结构用X-光衍射单晶分析确证。     

Reactions of 3-(4-Aryl-2-thiazolyl)- and 3-(2-Benzothiazolyl)-2-iminocoumarins with N-Nucleophiles

The reaction of 3-(4-aryl-2-thiazolyl)- and 3-(2-benzothiazolyl)-2-iminocoumarins with N-nucleophiles was studied. This reaction gives 2-N-substituted 3-(4-aryl-2-thiazolyl)- and 3-(2-benzothiazolyl)iminocourmarins. N-Nucleophiles such as arylamines, heterocyclic amines, and hydrazine derivatives undergo this reaction.     

DIASTEREOSELECTIVE SYNTHESIS AND STEREOCHEMISTRY OF (Z)-1-[3-ARYL-2-(PHENYLSULFANYL)-2-OXIRANYL]-1-ETHANONES

Diastereoselective synthesis of a series of (Z)-1-[3-aryl-2-(phenylsulfanyl)-2-oxiranyl]-1-ethanones was effected from the reaction of (Z)-4-aryl-3-(phenylsulfanyl)-3-buten-2-ones with alkaline hydrogen peroxide in tetrahydrofuran. The stereochemistry of the oxiranes has been deduced from two-dimensional NOESY spectrum.     

Reactivity of N-(omega-haloalkyl)-beta-lactams with regard to lithium aluminium hydride: novel synthesis of 1-(1-aryl-3-hydroxypropyl)aziridines and 3-aryl-3-(N-propylamino)propan-1-ols

The reactivity of 4-aryl-1-(2-chloroethyl)azetidin-2-ones and 4-aryl-1-(3-bromopropyl)azetidin-2-ones with regard to lithium aluminium hydride has been evaluated for the first time. 4-Aryl-1-(2-chloroethyl)azetidin-2-ones were transformed into novel 1-(1-aryl-3-hydroxypropyl)aziridines through an unprecedented conversion of beta-lactams into 2,3-unsubstituted aziridine derivatives. Unexpectedly, 4-aryl-1-(3-bromopropyl)azetidin-2-ones underwent dehalogenation towards 3-aryl-3-(N-propylamino)propan-1-ols upon treatment with LiAlH(4). 1-(1-Aryl-3-hydroxypropyl)aziridines were further elaborated by means of ring opening reactions using benzyl bromide in acetonitrile towards 3-aryl-3-[N-benzyl-N-(2-bromoethyl)amino]propan-1-ols and using aluminium(iii) chloride in diethyl ether, affording 3-aryl-3-[N-(2-chloroethyl)amino]propan-1-ols.     

The application of (Z)-3-aryl-3-haloenoic acids to the synthesis of (Z)-5-benzylidene-4-arylpyrrol-2(5H)-ones

Studies directed at the synthesis of (Z)-5-benzylidene-4-arylpyrrol-2(5H)-ones from (Z)-3-aryl-3-haloenoic acids are described. The successful strategy relies on the preparation of (Z)-3-aryl-3-haloenoic acids from acetophenones through the corresponding (Z)-3-aryl-3-haloenals and the conversion of the (Z)-3-aryl-3-haloenoic acids to (Z)-5-benzylidene-4-aryl-5H-furan-2-ones. The furanones were subsequently treated with primary amines and dehydrated to the corresponding (Z)-5-benzylidene-4-arylpyrrol-2(5H)-ones.     

Transformation of trans-4-aryl-3-chloro-1-(2-chloroethyl)azetidin-2-ones into 3-aryl-2-(ethylamino)propan-1-ols via intermediate 1-(1-aryl-2-chloro-3-hydroxypropyl)aziridines and trans-2-aryl-3-(hydroxymethyl)aziridines

trans-4-Aryl-3-chloro-1-(2-chloroethyl)azetidin-2-ones, prepared through cyclocondensation of chloroketene and the appropriate imines in a diastereoselective way, were unexpectedly transformed into 3-aryl-2-(ethylamino)propan-1-ols using LiAlH(4) in THF under reflux. A stepwise analysis showed that the initially formed 1-(1-aryl-2-chloro-3-hydroxypropyl)aziridines were converted into trans-2-aryl-3-(hydroxymethyl)aziridines, most probably via N-spiro bis-aziridinium intermediates, which were subsequently prone to undergo ring opening by LiAlH(4) to afford 3-aryl-2-(ethylamino)propan-1-ols.     

Nitrile oxide cycloaddition routes to 2-(isoxazolyl)-benzoates and 2-(1,2,4-oxadiazol-3-yl)benzoates

Cycloaddition of aromatic nitrile oxides to methyl o-vinylbenzoate produced methyl 2-(3-aryl-2-isoxazolin-5-yl)benzoates; the isoxazolines were converted to methyl 2-(3-arylisoxazol-5-yl)benzoates. Reaction of the nitrile oxide from o-methoxycarbonylbenzohydroximinoyl chloride ( 11 ) with phenylacetylene, styrenes, and aromatic nitriles resulted in methyl 2-(5-phenylisoxazol-3-yl)benzoate, methyl 2-(5-aryl-2-isoxazolin-3-yl)-benzoates ( 15 ), and methyl 2-(5-aryl-1,2,4-oxadiazol-3-yl)benzoates, respectively. The isoxazolines 15 were converted to the corresponding isoxazoles 16 .     

Total synthesis of (S)-(+)-curcudiol, and (S)-(+)- and (R)-(-)-curcuphenol.

A highly enantioselective synthesis of the versatile chiral synthons possessing one stereogenic center, (S)- and (R)-4-aryl-5-hydroxy-(2E)-pentenoate (3) was achieved based on the enzymatic reaction of (+/-)-3 with commercially available lipases MY-30 or OF-360 from Candida rugosa. Application of (S)-3 and (R)-3 to the total syntheses of(S)-curcuphenol (1), (S)-curcudiol (2), and (R)-curcuphenol (1), respectively, is described.     

Synthesis and spectral characteristics of 1-(3-pyridyl)-3-aryl-8-nitro(amino)benzo-[f]quinolines

1-(3-pyridyl)-3-aryl-8-aminobenzo[f]quinolines were synthesized by reduction with tin in acidic media of 1-(3-pyridyl)-3-aryl-8-nitrobenzo[f]quinolines obtained by catalytic condensation of arylidene(6-nitro)-2-naphthylamines with acetylpyridine. The structures of the compounds were proved by a set of data from elementary analysis and IR, UV, and mass spectroscopy. The change in the luminescence of 1-(3-pyridyl)-3-aryl-8-aminobenzo[f]quinoline as a function of the solvent was studied.Translated from Khimiya Geterotsiklicheskikh Soedtnenii, No. 12, pp. 1646–1649, December, 1978.     

Synthesis of aryl 2-(2-imidazolyl)ethyl ketones

The Claisen-Schmidt condensation of 1-(triphenylmethyl)-2-imidazolecarboxaldehyde with acetophenones yielded 1-aryl-3-[1-(triphenylmethyl)-2-imidazolyl]propen-1-ones 7 . Selective catalytic hydrogenation over platinum of 7 furnished 1-aryl-3-(2-imidazolyl)-1-propanones 8 . An alternate synthesis of 8 started with sodium borohydride reduction of 7 to give allylic alcohols, 1-aryl-3-[1-(triphenylmethyl)-2-imidazolyl]-2-propen-1-ols 10 , which were rearranged by hot aqueous sodium to 8 . Acid hydrolysis of 8 provided the title compounds and triphenylmethanol.     

Reaction of Methyl 1-(2-Bromoisobutyryl)cyclopentane-carboxylate and 3-(1-Bromocyclopentyl)-2,2-dimethyl-3-oxo-propionate with Zinc and Aromatic Aldehydes

Methyl 1-(2-bromoisobutyryl)cyclopentanecarboxylate and 3-(1-bromocyclopentyl)-2,2-dimethyl-3-oxopropionate react with zinc and aromatic aldehydes to afford 8-aryl-9,9-dimethyl-7-oxaspiro[4.5]decane-6,10-diones and 10-aryl-7,7-dimethyl-9-oxaspiro[4.5]decane-6,8-diones, respectively.