Synthesis of 1-[2-Methyl-6(8)-R-quinolin-4-yl]thiosemicarbazides

1-(2-Methylquinolin-4-yl)thiocemicarbazides and S-(2-methylquinolin-4-yl)thiosemicarbazide hydrochlorides were synthesized by reaction of 6(8)-substituted 4-chloro-2-methylquinolines with thiosemicarbazide under different conditions. Alkaline hydrolysis of the hydrochlorides afforded substituted 1-(2-methylquinolin-4-yl)thiosemicarbazides.     

Synthesis of N-Substituted Derivatives of 2-(4-Amino-2-methyl-1H-indol-3-yl)- and 2-(6-Amino-2-methyl-1H-indol-3-yl)acetic Acids

A method was developed for the production of indole compounds containing an amino group at positions 4 and 6 of the benzene ring on the basis of the indolization of the 3-acetylaminophenylhydrazone of ethyl levulinate. A series of derivatives of 2-(4-amino-2-methyl-1H-indol-3-yl)- and 2-(6-amino-2-methyl-1H-indol-3-yl)acetic acids at the 4- and 6-amino group were synthesized.     

Synthesis of 3-(6-R-Benzothiazol-2-yl)-4-methyl-1,2,5-oxadiazoles

The nitrosation of N-aryl-3-oxobutanethioamides afforded 1-(6-R-benzothiasol-2-yl)-1-hydroxyimino-2-propanones that at oximation with hydroxylamine were converted into 1-(6-R-benzothiazol-2-yl)-1,2-dihydroxyiminopropanes. The latter were dehydrated by heating with succinic anhydride at 140°C yielding therewith 3-(6-R-benzothiazol-2-yl)-4-methyl-1,2,5-oxadiazoles.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 5, 2005, pp. 759–761.Original Russian Text Copyright © 2005 by Britsun, Borisevich, Samoilenko, Lozinskii.     

Synthesis of 4'-(2,6,6-trimethyl -2-cyclohexen-1-yl) -3'-buten-2'-ketoxime-N-O-alkyl ethers

4'-(2,6,6-Trimethyl-2-cyclohexen-1-yl)-3'-buten-2'-ketoxime-N-O-alkyl ethers have been synthesized starting from alpha-ionone, separated into their E and Z isomers and characterized on the basis of (1)H-NMR and mass spectra.     

New 4-quinaldinol derivatives XVII. 2-Methyl-3-(3-chloro-2-buten-1-yl)-4-hydroxyquinoline-6-carboxylic acid and some of its transformations

1-(2-Methyl-4-hydroxy-6-carboxy-3-quinolinyl)-3-butanone and 1-(2-methyl-4-chloro-6-carboxy-3-quinolinyl)-3-butanone were obtained by the acid hydrolysis of 2-methyl-3-(3-chloro-2-buten-1-yl)-4-hydroxy(chloro)quinoline-6-carboxylic acids and their esters.See [6] for communication XVI.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1681–1682, December, 1971.     

Syntheses of substituted 1-methyl-2-(1,3,4-thiadiazol-2-yl)-4-nitropyrroles and 1-methyl-2-(1,3,4-oxadiazol-2-yl)-4-nitropyrroles

Starting from readily available ethyl-4-nitropyrrole-2-carboxylate ( 1 ), substituted 1-methyl-2-(1,3,4-thiadiazol-2-yl)-4-nitropyrroles and 1-methyl-2-(1,3,4-oxadiazol-2-yl)-4-nitropyrroles were prepared. The reaction of 1 with diazomethane gave ethyl 1-methyl-4-nitropyrrole-2-carboxylate ( 2 ). Reaction of compound 2 with hydrazine hydrate afforded the corresponding hydrazide 3 . The reaction of 3 with formic acid yielded 1-(1-methyl-4-nitropyrrole-2-carboxyl)-2-(formyl)hydrazine ( 7 ). Refluxing of the latter with phosphorus pentasulfide in xylene yielded compound 6 in 40% yield. Reaction of compound 7 with phosphorus pentoxide afforded compound 9 . Reaction of compound 3 with 1,1′-carboxyldiimidazole in the presence of triethylamine yielded 2-(1-methyl-4-nitro-2-pyrrolyl)-1,3,4-oxadiazoline-4(H)-5-one ( 11 ). Refluxing compound 3 with cyanogen bromide in methanol gave compound 12 . Compound 13 could be obtained through the reaction of compound 3 with carbon disulfide in basic medium. Alkylation of compound 13 afforded the correspanding alkylthio derivative 14 . Reaction of 1-methyl-4-nitropyrrole-2-carboxylic acid ( 15 ) with thiosemicarbazide and phosphorus oxychloride gave 2-amino-5-(1-methyl-4-nitro-2-pyrrolyl)-1,3,4-thiadiazole ( 16 ). Sandmeyer reaction of compound 16 yielded 2-chloro-5-(1-methyl-4-nitro-2-pyrrolyl)-1,3,4-thiadiazole ( 17 ). Refluxing of the latter with thiourea afforded 2-(1-methyl-4-nitro-2-pyrrolyl)-1,3,4-thiadiazoline-4(H)-5-thione ( 18 ). Alkylation of compound 18 gave the corresponding alkylthio derivative 19 . Oxidation of the latter with hydrogen peroxide in acetic acid yielded 2-(1-methyl-4-nitro-2-pyrrolyl)-5-methylsulfonyl-1,3,4-thiadiazole ( 20 ).     

Synthesis of 6-(5-sulfanyl-1H-tetrazol-1-yl)-2H-chromen-2-one and 5-methyl-1-(2-oxo-2H-chromen-6-yl)-1H-1,2,3-triazole-4-carboxylic acid

Russian Journal of Organic Chemistry -     

Facile and Simple Synthesis of Novel 1-Methyl-2-(2-substituted-oxazol-4-yl)-1H-benzimidazole Derivatives

Novel 1-methyl-2-(2-substituted-oxazol-4-yl)-1H-benzimidazole derivatives were obtained in good yields and purity by treating corresponding 2-benzimidazolyl esters with acetamide in the presence of BF₃-etherate, a Lewis acid.     

2-甲基-1-(4-芳基噻唑-2-基)-苯并咪唑-6-甲酸乙酯的合成、表征及生物活性

以4-乙酰氨基苯甲酸乙酯为原料设计合成了14 种2-甲基-1-(4-芳基噻唑-2-基)-苯并咪唑-6-甲酸乙酯新化合物. 化合物结构经质谱、1H NMR、红外光谱和元素分析等确证, 并用单晶X射线衍射仪测定了化合物5a的晶体结构. 生物活性实验结果表明, 化合物5c(500 mg/L)对小麦白粉病菌抑制率达到95%; 化合物5e对辣椒疫霉病菌(25 mg/L)的抑制率为61.9%, 对油菜菌核病菌(500 mg/L) 抑制率高达97.2%; 化合物5k(25 mg/L) 对小麦赤霉病菌抑制率为55.1%.     

Synthesis and Biological Activity of New 2-{[6-Methyl-2-(pyrrolidin-1-yl)pyrimidin-4-yl]oxy}acetohydrazide Derivatives

Russian Journal of General Chemistry - The reaction of 6-methyl-2-(pyrrolidin-1-yl)pyrimidin-4(3H)-one with methyl chloroacetate, followed by hydrazinolysis, gave...     

1-(2, 6, 6-三甲基-1-环己烯基-)-3-甲基-2-丁烯-4-醛合成新工艺

1-(2; 6; 6-三甲基-1-环己烯基-)-3-甲基-2-丁烯-4-醛合成新工艺;(三甲基环己烯基)甲基丁烯醛;卡宾反应; β-紫罗兰酮;三甲基溴化硫     

新型1-(1,3,5-三嗪-6-基)-3-甲基-4-(5-苯基-1,3,4-噁二唑-2-基)吡唑的合成及活性评价

设计合成了18个以吡唑桥连1,3,4-噁二唑和1,3,5-三嗪的新型多杂环分子[7A(a~f),7B(a~f)和7C(a~f)];通过红外光谱(IR)、核磁共振波谱(NMR)和高分辨质谱(HRMS)等对目标分子进行了结构表征;评价了目标分子对蛋白酪氨酸磷酸酯酶1B(PTP1B)和细胞分裂周期25磷酸酯酶B(Cdc25B)的抑制活性.结果表明,所有目标分子对PTP1B和Cdc25B均有较好的抑制活性,其中,9个目标分子表现出优异的PTP1B和Cdc25B抑制效果,IC50值低于齐墩果酸(PTP1B抑制活性测试参照物)和正钒酸钠(Cdc25B抑制活性测试阳性参照物),有望成为潜在的PTP1B和Cdc25B抑制剂.     

Synthesis and tautomerism of 2-(3,5-diaryl-1H-pyrazol-4-yl)-1-methyl-1H-benzimidazoles

The cyclocondensation of 1-methyl-2-phenacyl-1H-benzimidazole with aroylhydrazines yields 2-(3,5-diaryl-1H-pyrazol-4-yl)-1-methyl-1H-benzimidazoles. The ¹H NMR spectra indicate that these products display tautomerism. The more stable tautomers have structures containing electron-donor aryl substituents at C-5 and electron-withdrawing aryl substituents at C-3 of the pyrazole ring.     

1-(Pyrimidin-4-yl)pyrazol-5(4H)-one derivatives: I. Synthesis of 3-methyl-1-(6-methyl-2-methylsulfanylpyrimidin-4-yl)-pyrazol-5-ol and specificity of its Knoevenagel reaction

3-Methyl-1-(6-methyl-2-methylsulfanylpyrimidin-4-yl)-1H-pyrazol-5-ol available via cyclocondensation of 6-methyl-2-methylsulfanylpyrimidin-4-ylhydrazine with ethyl acetoacetate reacted with aromatic aldehydes to give two kinds of products, 4-arylmethylidene-5-oxo-4,5-dihydropyrazole and arylbis(5-hydroxypyrazol-4-yl)methane derivatives, depending on the substituent in the aromatic aldehyde.     

2-甲基-6-对甲苯基-1,6-庚二烯的合成

以对甲苯乙酮(1)为原料,经烯醇硅醚化,Lewis酸催化Michael加成反应和Wittig反应,合成了新倍半萜烯化合物2-甲基-6-对甲苯基-1,6-庚二烯。