3-芳基-4-[4''-(2,2,6,6-四甲基哌啶-1-氧)]-1,2,4-三唑啉-5-硫酮类的合成

本文用芳酰肼和2,2,6,6-四甲基-4-异硫氰基-哌啶-1-氧以无水乙醇为溶剂,在氩气保护下反应,制得八种1-芳酰基-4-[4'(2,2,6,6-四甲基哌啶-1-氧)]氨基硫脲(1),继而研究1在几种碱催化下脱水的环化反应。试验结果表明,只有在1mol的K2CO3水溶液中,才能较满意地使1环化,得到预期的3-芳基-4-(4'-2,2, 6,6-四甲基哌啶-1-氧)-1,2,4-三唑啉-5 硫酮。     

1—苯乙酰基—4—芳酰基氨基硫脲的合成及其在碱催化下的环化反应

1-酰基-4-芳基氨基硫脲类化合物在碱性条件下环化为具有广泛生物活性的3-取代基-4-芳基-1,2,4-三唑啉-5-硫酮的反应报道甚多,但1,4-位都含羰基的酰氨基硫脲在碱性条件下环化反应迄今报道较少。我们曾研究了1-[5-(α-萘)-2H-四唑-2-乙酰基]-4-芳酰基氨基硫脲和1-(α-萘乙酰基)-4-芳酰基氨基硫脲在碱催化下环化为3-取代基-4-芳酰基-1,2,4-三唑啉-5-硫酮的反应,它们在低浓度下均有一定的生物活性。本文研究了1-苯乙酰基-4-芳酰基氨基硫脲1_(a～m)在1mol/L K_2CO_3溶液催化下的环化反应,得到环化产物3-苄基-4-芳酰基-1,2,     

双（1—乙酰基—4—取代苯甲酰基氨基硫脲）及其衍生物的合成

由丁二酰肼Ⅰ与取代苯甲酰基异硫氰酯在无水CaCl_2处理过的乙腈溶剂中亲核加成,制得一系列未知的双(1-乙酰基-4-取代苯甲酰基氨基硫脲)衍生物Ⅱ,Ⅱ在碱性条件下环化为未知的双(3-亚甲基-4-取代苯甲酰基-1,2,4-三唑啉-5-硫酮)Ⅲ ,所有化合物结构均经鉴定,部分化合物对枯草芽孢杆菌和大肠杆菌有抑制作用。     

酰氨基硫脲及有关的杂环衍生物的研究 I:1-氰乙酰基-4-芳基氨基硫脲及有关的杂环衍生物的合成

合成了九个1-氰乙酰基-4-芳基氨基硫脲类化合物和四个3-氰甲基-4-芳基-1,2,4-三唑啉与硫酮类化合物和四个2-苯基氨基-5-取代-1,3-噻二唑类化合物.并初步研究了这些化合物的抗结核菌活性和植物生长促进作用.     

2-[1-(1,2,4-三唑)甲基]-3-乙酰基-2,5-二取代芳基-1,3,4-噁二唑啉类化合物的合成

在冰醋酸存在下, 4-取代苯乙酮和溴素容易进行溴代反应, 得到α-溴-4-取代苯乙酮; 将其和1,2,4-三唑在丙酮中反应, 得到α-(1,2,4-三唑-1-基)-4-取代苯乙酮2; 在冰醋酸催化下, 2和4-取代苯甲酰肼1进行缩合, 得到相应酰腙衍生物3; 化合物3在乙酸酐的作用下环化生成一系列2-[1-(1,2,4-三唑)甲基]-3-乙酰基-2,5-二取代芳基-1,3,4-噁二唑啉4. 化合物4的结构经IR, 1H NMR, MS, 元素分析和单晶衍射确证.     

酰氨基硫脲及其相关杂环衍生物的研究(Ⅹ)——1-(4′-吡啶甲酰基)-4-芳酰胺基硫脲类化合物环化反应的研究

本文研究1-(4′-吡啶甲酰基)-4-芳酰胺基硫脲(Ⅰ)在碱催化条件下的环化反应。结果表明,当(Ⅰ)芳环连接吸电子基如硝基、卤素或推电子取代基如甲基和甲氧基等时,均环化为3-(4′-吡啶基)-4-芳酰基-1,2,4-三唑啉-5-硫酮(Ⅱ),通过质谱裂解碎片分析确定其结构,并初步评价部分化合物对结核菌的抑制作用。     

3-(N-取代苯基-2-乙酰胺基)硫基-4-N-取代邻羟苯基亚胺基-5-甲基-1,2,4-三唑类化合物的合成及生物活性研究

以对称二氨基硫脲为原料,与冰醋酸反应生成5-甲基-4-氨基-1,2,4-三唑-3-硫酮(1);在弱酸性条件下,1与取代水杨醛反应生成席夫碱中间体5-甲基-4-(N-取代邻羟苯基)亚胺基-1,2,4-三唑-3-硫酮(2a～2c);最后在碱性条件下分别与N-取代苯基-2-氯乙酰胺发生烷基化反应生成15种未见报道的目标化合物3-(N-取代苯基-2-乙酰胺基)硫基-4-(N-取代邻羟苯基)亚胺基-5-甲基-1,2,4-三唑(3a～3o),其结构经IR,1H NMR,13C NMR确证.初步生物测试表明,质量分数为0.01%时,3a～3o对白色念珠菌的抑菌率均达90%以上,具有很强的抑菌活性;对金黄色葡萄球菌、大肠杆菌的抑菌率达80%以上,具有较强的抑菌活性.     

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。     

3-甲基-4-氨基-1,2,4-三唑-5-硫酮席夫碱的合成及生物活性研究

用自制的二氨基硫脲与乙酸反应得到3-甲基-4-氨基-1,2,4-三唑-5-硫酮, 然后以醋酸为反应溶剂和催化剂, 使之与取代芳香醛反应, 合成了8个三唑类席夫碱化合物. 通过¹H NMR, IR和元素分析对所有化合物进行了结构表征. 并对这些化合物进行了初步生物活性测试, 结果表明大部分化合物具有较好的抑菌活性, 并对席夫碱结构与活性的关系进行了探讨.     

3-取代苯氧甲基-4-氨基-1,2,4-三唑-5-硫酮席夫碱的合成、结构表征和生物活性研究

以醋酸为反应溶剂和催化剂,用自制的4-氨基-4,5-二氢-3-取代苯氧甲基-1,2,4-三唑-5-硫酮与4-氟苯甲醛反应合成了5个4-氨基-4,5-二氢-3-取代苯氧甲基-1,2,4-三唑-5-硫酮席夫碱化合物,通过1HNMR、IR和元素分析对所有化合物进行了结构表征.初步生物活性测试结果表明所有化合物具有优良的杀菌活性,并对席夫碱结构与活性的关系进行了探讨.     

Synthesis and Transformations of 4-(4-Ethoxycarbonylphenylamino)- and 4-(2-Carboxyphenylamino)quinolines

Synthesis was performed of 4-(4-ethoxycarbonylphenylamino)- and 4-(2-carboxyphenylamino)-2-methylquinolines by reaction of 2-methyl-4-chloroquinoline with anesthesin and anthranilic acid. In concentrated sulfuric acid 4-(2-carboxyphenylamino)-2-methylquinoline underwent cyclization into 6-hydroxy-7-methylquinolino[3,2-c]quinoline, and the alkaline hydrolysis of 4-(4-ethoxycarbonylphenyl-amino)quinoline afforded 2-methyl-4-(4-carboxyphenylamino)quinoline.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 5, 2005, pp. 786–787.Original Russian Text Copyright © 2005 by Avetisyan, Aleksanyan, Ambartsumyan.     

One-Pot Three-Component Synthesis of a Series of 2-Amino-4-(4-oxo-4H-chromen-3-yl)-5-(2,2,2-trifluoroacetyl)-6-(trifluoromethyl)-4H-pyrans and 2-Amino-4-(4-oxo-4H-chromen-3-yl)-5-(thiophene-2-carbonyl)-6-(trifluoromethyl)-4H-pyrans as Promising Anticancer Agents

Russian Journal of Organic Chemistry - Novel functionalized 2-amino-4-(4-oxo-4H-chromen-3-yl)-5-(2,2,2-trifluoroacetyl)-6-(trifluoro­methyl)-4H-pyrans and...     

1-(4-氯苯胺基)-4-(4-吡啶甲基)-2,3-二氮杂萘琥珀酸盐的合成与抑制肿瘤活性

研究了1-(4-氯苯胺基)-4-(4-吡啶甲基)-2,3-二氮杂萘琥珀酸盐的合成工艺,采用苯酞和吡啶甲醛为起始原料,经加成、重排、取代和成盐4步反应得到目标化合物。 中间体及目标化合物通过1H NMR、MS和HPLC进行了表征。 重结晶纯化后的目标化合物纯度为98.1%。 对荷瘤（人大肠癌HT 29细胞）裸鼠的抑癌活性测定表明,该化合物具有明显的抑制肿瘤生长作用。     

Synthesis of substituted 2-ethyl-3-(4-hydrazinocarbonylphenyl)-4-quinazo-lones and 2-ethyl-3-(4-hydrazinocarbonylmethylphenyl)-4-quinazolones

Some substituted 2-ethyl-3-(4-hydrazinocarbonylphenyl)-4-quinazolones and 2-ethyl-3-(4-hydrazinocarbonylmethylphenyl)-4-quinazolones were synthesized and characterized by their sharp melting points, elemental analyses and spectral data.     

1- and 2-(4-Hydroxycarbonylphenyl)-4-oxo-4,5,6,7-tetrahydroindazoles

Reactions of 4-hydrazinobenzoic acid with 2-formyl- and 2-acetyldimedones were utilized to synthesize 6,6-dimethyl- and 3,6,6-trimethyl-1-(4-hydroxycarbonylphenyl)-4-oxo-4,5,6,7-tetrahydroindazoles corre-spondingly, and the reaction with 2-cyano-3-ethoxy-5,5-dimethylcyclohex-2-en-1-one gave 2-(4-hydroxy-carbonylphenyl)-3-amino-4-oxo-6,6-dimethyl-4,5,6,7-tetrahydroindazole. Riga Technical University, Riga LV-1658. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 516–519, April, 1997.     

Synthesis of 4-(4-phenyl-3-pyrazolyl)-4H-1,2,4-triazoles

4-(4-PhenyI-3-pyrazolyl)-4H-1,2,4-triazoles and 4-phenyl-5-(4H-1,2,4-triazol4-yl)-3-pyrazolols were prepared by the reaction of formylhydrazine on α-phenyl-α-cyanoacetaldehydes and ethyl α-phenyl-α-cyanoacetates.     

Dielectric Properties of 4-(2,3-Epoxypropoxy)- and 4-Propoxy-4'-alkoxyazoxybenzenes

The temperature dependences of the dielectric permittivity of 4-(2,3-epoxypropoxy)-4'-alkoxyazoxybenzenes (n = 1-10) and 4-propoxy-4'-alkoxyazoxybenzenes (n = 1-10) with mesomorphic properties were measured by dielectrometry. The introductrion of the terminal epoxy group increases the dielectric permittivity and its anisotropy. The dipole moments of molecules of 4-(2,3-epoxypropoxy)-4'-alkoxyazoxybenzenes (n = 1-10) and 4-propoxy-4'-alkoxyazoxybenzenes (n = 1-10) were determined by the second Debye method. The epoxy-substituted azoxybenzenes have higher dipole moments than their structural analogs.     

On the aromaticity of square planar Ga4(2-) and In4(2-) in gaseous NaGa4- and NaIn4- clusters

We investigated the electronic structure and chemical bonding of two bimetallic clusters NaGa4- and NaIn4-. Photoelectron spectra of the anions were obtained and compared with ab initio calculations. We found that the ground state of the two anions contains a square planar dianion interacting with a Na+ cation. The Ga4(2-) and In4(2-) dianions both possess two delocalized pi electrons and are considered to be aromatic, similar to that recently found in Al4(2-). Using calculations for a model compound, we showed that a recently synthesized Ga4-organometallic compound also contains an aromatic -Ga4(2-)- unit, analogous to the gaseous clusters.     

Synthesis of 1-(3',4'-dihydroxyphenyl)-7-(4"-hydroxyphenyl)- 4hepten-3-one

Natural diarylheptanoids have significant bioactivities. Some of them are potent inhibitors against prostaglandin biosynthesizing enzyme (PG synthetase) and 5-lipoxygenase (LT synthetase)1-2. Compound 1 was firstly isolated from Alnus rubra bark3. So far its synthesis has not been reported yet. Herein, we report the synthesis of compound 1. Meantime, compound 24 was also obtianed as an intermediate. Compound 7 and 16 were converted to compound 10 and 18 respectively, because compound 1…     

Selenium heterocycles. XXXVII . Synthesis of 4-(thiazol-4-yl)-1,2,3-selenadiazoles and 4-(selenazol-4-yl)-1,2,3-selenadiazoles

Starting from readily available 2-substituted-4-formylthiazoles and selenazoles, a series of 4-(2-aryl-4-selenazolyl)-1,2,3-selenadiazoles I and 4-(2-substituted-4-thiazolyl)-1,2,3-selenadiazoles II were prepared. Pyrolysis of compound II afforded (2-substituted-4-thiazolyl) acetylenes VII. Addition of potassium hydroxide pellets to an alcoholic solution of II gave 2-substituted-1,4-diselenafulvenes VIII. Decomposition of compound II with base followed by the addition of carbon disulfide gave 5-substituted 2-thioxo-1,3-thiaselenoles XI.