On the choice of optimal conformation in linear free-energy relationships. Reactivity of 2-[(carboxymethyl)sulfanyl]-4-oxo-4-arylbutanoic acids with diphenyldiazomethane

Rate constants for the esterification of eleven 2-[(carboxymethyl)sulfanyl]-4-oxo-4-arylbutanoic acids with diphenyldiazomethane in ethanol at 30 °C were determined, and correlated with substituent constants using classical Hammett and related methods. Statistically valid results for the para-substituted compounds were obtained by the Swain–Lupton approach. The compounds studied had significant conformational mobility due to seven rotatable bonds in their backbone. Going beyond the classical Hammett approach, we established a relatively fast procedure to find the optimal conformations that can be used in linear free-energy relationships, combining molecular dynamics with semiempirical calculations, and calculations using a higher level of theory (DFT and MP2). Fair correlations were observed with frontier orbitals, allowing inclusion of ortho-substituted derivatives and clarifying artifact-like data, as perceived by the Hammett-type approach.     

Mass Spectra of New Heterocycles: XXIII. Electron Impact and Chemical Ionization Study of 5-[(Cyanomethyl)sulfanyl]- and 5-[(1,3-Dioxolan-2-ylmethyl)sulfanyl]-1H-pyrrol-2-amines

Russian Journal of Organic Chemistry - The fragmentation of 5-[(cyanomethyl)sulfanyl]- and 5-[(1,3-dioxolan-2-ylmethyl)sulfanyl]-1H-pyrrol-2-amines under electron impact (70 eV) and chemical...     

Synthesis of hetarylquinolines proceeding from 2-[(2-methylquinolin-4-yl)sulfanyl]acetohydrazide substituted in the benzene ring

At intramolecular cyclization of phenylhydrazinocarbothioamide in alkaline and acidic media quinolyl-substituted triazoles and thiadiazoles are obtained. Quinolyl-substituted thiazolidines and thiazolidinones were obtained at interaction of phenylhydrazinocarbothioamides with bromoacetophenone and ethyl bromoacetate.     

Synthesis of 2-[(Pyrrol-2-yl)sulfanyl]acetic Acids by Reaction of Pyrrolo[2,1-c][1,4]oxazinetriones with 2-Sulfanylacetic Acid

Russian Journal of Organic Chemistry - 8-Aroyl-3,4-dihydro-1H-pyrrolo[2,1-c][1,4]oxazine-1,6,7-triones reacted with 2-sulfanylacetic acid to give...     

Synthesis of substituted in benzene ring 4-[(2-aminophenyl)thio]-, 4-[(2-mercaptophenyl)amino]-2-methylquinolines and (4E)-4-[(2-mercaptophenyl)imino]-2-methyl-1,4-dihydroquinolines

By a reaction of 2-methyl-4-chloroquinolines with o-mercaptoaniline under various conditions synteses were performed of substituted in the benzene ring 4-[(2-aminophenyl)thio]-2-methylquinolines and (4E)-4-[(2-mercaptophenyl)imino]-2-methyl-1,4-dihydroquinolines that were respectively by isomerization or rearrangement converted into 4-[(2-mercaptophenyl)amino]-2-methylquinolines.     

1-取代-7-3-[(乙氨基)甲基]-1-吡咯基喹诺酮N1位定量构效关系

喹诺酮类抗菌药物因其具有广谱、低毒以及口服吸收良好等特点而受到越来越多的关注.对N1位的构效关系曾有研究报道,但其建立的定量构效关系式相关性较差.为了对N1位的构效关系有更深入的认识,本文以取代基的表面积和分子体积为参数.     

Synthesis of methyl 4-aryl-4-oxo-2-[(4-sulfamoylphenyl)amino]but-2-enoates and their reaction with ninhydrin

The reaction of methyl 4-aryl-2,4-dioxobut-2-enoates with 4-aminobenzenesulfonamide in acetic acid–ethanol (1: 1) afforded methyl (2Z)-4-aryl-4-oxo-2-(4-sulfamoylanilino)but-2-enoates which reacted with ninhydrin in glacial acetic acid to give 3-aroyl-4-(4-sulfamoylanilino]-5H-spiro[furan-2,2′-indene]-1′,3′,5-triones.     

Aryl ethers of 4-[(2-hydroxyethyl)sulfanyl]pyrimidine derivatives: Pathways of synthesis and fungicidal activity of their salt forms

2-Amino-4-[(2-aryloxyethyl)sulfanyl]-6-methylpyrimidines were obtained by S-alkylation of 2-amino-6-methylpyrimidin-4(3H)-thione with 2-aryloxyethyl chlorides. Since 2-amino-4-[(2-chloroethyl)sulfanyl]-6-methylpyrimidine is prone to in situ intramolecular cyclization it cannot be used in Claisen reaction. The bromination of the target compounds provided 5-bromo derivatives; some of their hydrochlorides exhibited fungicidal activity.     

Synthesis of 4-[(3,3-Dimethyl-3,4-dihydroisoquinolin-1-yl)sulfanyl]anilines by the Ritter Reaction

Russian Journal of Organic Chemistry - The Ritter cyclocondensation of 2-methyl-3-phenylpropan-2-ol with 4-isocyanatoaniline, 2-methyl-4-thiocyanatoaniline, and ethyl 4-amino-3-thiocyanatobenzoate...     

Synthesis and Antinociceptive Activity of N -Substituted 4-Aryl-4-oxo-2-[(3-thiophen-2-yl)amino]but-2-enamides

2-{[5-Aryl-2-oxofuran-3(2H)-ylidene]amino}thiophene-3-carboxylic acid derivatives reacted with substituted amines to give new N-substituted 4-aryl-4-oxo-2-[(3-thiophen-2-yl)amino]but-2-enamides. Antinociceptive activity of the synthesized compounds was studied.     

新型1-(4-取代苯基)-3-[4-(4-氧香豆素基)苯基]硫脲衍生物的合成及其抑菌活性

以4-羟基香豆素为原料,经氯化、醚化和异硫氰酸化3步反应制得中间体——4-(4-异硫氰酸酯苯氧基)香豆素(3);3与取代芳香胺经加成反应合成了9个新型的1-(4-取代苯基)-3-[4-(4-氧香豆素基)苯基]硫脲衍生物(4a~4i),其结构经1H NMR,13C NMR,IR和MS(ESI)表征。采用浑浊度法测试了4的抑菌活性。结果表明:4a、4b、4e和4f抑制烟草青枯菌活性EC50值分别为112.02、121.39、88.72和86.90μg·mL~(-1),优于噻菌铜(130.25μg·mL~(-1));4a、4b、4e和4f抑制番茄青枯菌活性EC50值分别为107.89、110.69、82.43和82.48μg·mL~(-1),优于噻菌铜(123.94μg·mL~(-1))。     

Synthesis of 3-{3-[(4-methylcyclohex-3-enyl-carbonyl)amino]-4-oxo-3,4-dihydroquinazolin-2-yl}propanoic acid anilides

With the aim of discovering potential diuretic agents amongst quinazoline anilides we have prepared anilides of 3-{3-[(4-methylcyclohex-3-enylcarbonyl)amino]-4-oxo-3,4-dihydroquinazolin-2-yl}propanoic acid. Optimal conditions for obtaining of the starting acid have been established, and anilides have been synthesized by the mixed anhydrides method.     

Synthesis of Methyl 4-Aryl-4-oxo-2-{4-[(1,3-thiazol-2-yl)-sulfamoyl]phenylamino}but-2-enoates and Their Reactions with Ninhydrin

Russian Journal of Organic Chemistry - The reaction of methyl aroylpyruvates with 2-(4-aminobenzenesulfonamido)thiazole (norsulfazole) in acetic acid-ethanol (1: 1) afforded methyl...     

2-[(4-氯苯基亚氨基)甲基]-8-羟基喹啉质子转移的理论研究

研究了2-[(4-氯苯基亚氨基)甲基]-8-羟基喹啉的三种质子转移途径: 分子内质子转移、水分子辅助质子转移和甲醇分子辅助质子转移. 以该席夫碱化合物的晶体结构作为模型, 在B3LYP/6-31＋G(d)水平上, 优化得到稳定态和过渡态的几何构型. 对三类质子转移前后的结构、能量、红外光谱、化学位移进行研究, 结果表明水分子辅助质子转移和甲醇分子辅助质子转移中, 水和甲醇分子利用氢键作用参与质子转移过程, 形成七元环状过渡态, 大大降低了反应的能垒, 有利于质子的转移, 氢键在降低活化能方面起着重要作用.     

4-卤-5-(4-甲基-2H-1-苯并-2-吡喃酮-7-氧基)-2-取代-3(2H)-哒嗪酮衍生物的合成和生物活性研究

通过4,5-二氯(溴)-3(2H)-哒嗪酮与7-羟基-4-甲基香豆素在CH3CN/K2CO3体系下的缩合反应,将具有生物活性的哒嗪酮环引入到苯并吡喃酮结构中,设计、合成了9个含哒嗪酮环的香豆素类化合物,其中8个为新化合物.所有化合物的结构均经NMR,MS和元素分析确证.初步生物活性测试结果表明:化合物4-氯-5-(4-甲基-2H-1-苯并吡喃-2-酮-7-氧基)-2-(4-硝基苯基)-3(2H)-哒嗪酮对黄瓜根部具有一定的抑制作用.     

Asymmetric azomethine ligands based on 2-[(2-aminophenyl)aminomethylidene]-3-oxo-3-polyfluoroalkylpropionates and aldehydes

The condensation of ethyl 2-[(2-aminophenyl)aminomethylidene]-3-oxo-3-polyfluoroalkyl-propionates with aldehydes (salicylaldehyde, furfural, and benzaldehyde) affords the corresponding azomethine derivatives exhibiting the complexing ability toward copper and nickel ions.