Synthesis and structure of 2-hydroxy-3-formylbenzo[b]thiophene azomethines

A number of 2-hydroxy-3-formylbenzo[b]thiophene azomethines and their derivatives, which model the individual tautomeric forms, were synthesized. As a result of a study of the electronic, vibrational, and PMR spectra, a ketone-amine structure, the stability of which is confirmed by quantum-mechanical calculations of the atomization energies of the individual tautomeric forms calculated by the Pariser-Parr-Pople (PPP) method within the Dewar , parametrization, was assigned to these azomethines.Communication XVIII from the series Benzoid—Quinoid Tautomerism of Azomethines and Their Structural Analogs. See [1] for communication XVII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 635–642, May, 1975.     

Synthesis and structure of azomethines based onN-vinyl derivatives of 2-amino- and 2-formylimidazoles

New Schiff's bases of theN-vinylimidazole andN-vinylbenzimidazole series were synthesized.¹H NMR data suggest that the azomethines exist in theE-form with respect to the CH=N bond and that the vinyl groups havetrans-orientation relative to each other. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 10, pp. 1857–1859, October, 1997.     

Synthesis of cis-1-methyl-2-aryl-3-aroylaziridines

trans-1-Methyl-2-aryl-3-aroylaziridines readily undergo epimerization to give the corresponding cis isomers in high yields in the presence of catalytic amounts of quaternary ammonium bases (trimethylbenzylammonium or triethylmethylammonium hydroxide). The structures of the compounds obtained were established on the basis of the IR and PMR spectra and the results of elementary analysis.Translated from Khimiya Geterotsilicheskikh Soedinenii, No. 10, pp. 1353–1355, October, 1980.     

Synthesis and properties of azomethines based on 1-nitrophenyl-2-formylpyrroles

Schiff bases were obtained by the reaction of 1-nitrophenyl-2-formylpyrroles with aromatic amines, and their spectral characteristics were studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 53–56, January, 1989.     

2-甲基-1-苯基丙胺的合成、拆分与结构表征

手性氨基醇由于原料来源广泛、便于合成,现已作为手性配体和手性助剂被广泛应用于不对称合成中。手性氨基烷基酚是许多抗生素和生物活性物质的主要成分,且在不对称催化和不对称诱导反应中取得了令人满意的效果。但自然界中氨基烷基酚贫乏,其合成和拆分也较困难。     

1-甲基-3,4-二苯基喹啉-2(1H)-酮的合成和结构表征

以N-甲基苯胺和苯丙炔酸为原料,经过缩合、亲电环化、偶联反应合成了1-甲基-3,4-二苯基喹啉-2(1H)-酮;利用核磁共振谱和气相色谱-质谱表征了产物的结构.结果表明,所用合成方法具有产率高、反应条件温和、操作简单等优点,目标产物的总产率达62.7%.     

Synthesis and reactions of 1-methyl-3-formylindazole

It is shown that oxidation of 1-methyl-3-hydroxymethylenediazole with a solution of potassium dichromate in dilute sulfuric acid gives a 30% yield of 1-methyl-3-formylindazole. Condensation products of the latter with malonic acid, nitromethane acetophenone, hippuric acid, hydantoin, thiohydantoin, and rhodanine are obtained. An oxime and a semicarbazone are prepared.     

Synthesis and crystal structure of ethyl 1-benzyl-2-hydroxy-5-methyl-3-oxo-2-phenacyl-2,3-dihydropyrrole-4-carboxylate

Reaction of 5-phenyl-2,3-dihydro-2,3-furandione with ethyl 3-benzylamino-2-butenoate, resulting in ethyl 1-benzyl-2-hydroxy-5-methyl-3-oxo-2-phenacyl-2,3-dihydropyrrole-4-carboxylate and benzylamide ofN-benzoylpyruvic acid, was studied. The structure of the pyrrole derivative was confirmed by X-ray analysis.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1552–1555, August, 1995.     

Synthesis and structure elucidation of 3-methoxy-1-methyl-1H-1,2,4,-triazol-5-amine and 5-methoxy-1-methyl-1H-1,2,4,-triazol-3-amine

Previously it was shown that condensation of dimethyl N-cyanodithioimidocarbonate ( 1a ) with methylhydrazine gave predominantly 1-methyl-5-methylthio-1H-,2,4-triazol-3-amine ( 2 ), which was initially identified erroneously as the regioisomer l-methyl-3-methylthio-1H-1,2,4-triazol-5-amine ( 3 ). We have found that reaction of dimethyl N-cyanoimidocarbonate ( 1b ) with methyl hydrazine affords a high yield of 3-methoxy-1-methyl-1H-1,2,4-triazol-5-amine ( 4 ) rather than the regioisomer 5-methoxy-1-methyl-1H-1,2,4-triazol-3-amine ( 5 ). The structure assignment of 4 was confirmed by X-ray crystallographic analysis of the benzenesulfonyl isocyanate adduct 7 . Triazole 5 was obtained after reacting dimethyl N-cyanothioimidocarbonate ( 1c ) with methylhydrazine.     

Synthesis and structure of 1-methyl-4-(3-thiocarbamoyl-3-cyanopropenylidene)-1,4-dihydroquinoline

1,4-Dimethylquinolinium iodide reacts with (2-nitrophenyl)aminomethylenecyano-thioacetamide in the presence of triethylamine to give 1-methyl-4-(3-thiocarbamoyl-3-cyanopropylidene)-1,4-dihydroquinoline, the structure of which has been established by x-ray crystallography. The molecule is virtually planar, the dihedral angle between the dihydroquinoline nucleus and the 3-thiocarbamoyl-3-cyanopropylidene group being 3.39°. The bond lengths found indicate considerable transfer of charge between the dihydroquinoline ring and the cyanothioacetamide group. The crystal contains stacks of molecules with an interplanar spacing of 3.351 Å, which could also facilitate charge transfer.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 896–902, April, 1991.     

1-羟基-1-甲基-3-氧-异吲哚类衍生物的合成

邻苯二甲酸酐与丙二酸反应合成邻乙酰基苯甲酸(1);1经酰氯化反应得邻乙酰基苯甲酰氯(2);2与伯胺反应合成了3个1-羟基-1-甲基-3-氧-异吲哚化合物,总收率65.0%～76.8%,其结构经1H NMR, 13C NMR, IR和MS表征.     

Synthesis and heterocyclization of 3-aryl-2-methyl-2-thiocyanatopropanamides

Reactions of arenediazonium tetrafluoroborates with methacrylamide in the presence of potassium thiocyanate in aqueous acetone (1: 2.5) or aqueous dimethyl sulfoxide (1: 4) gave the corresponding 3-aryl-2-methyl-2-thiocyanatopropanamides which underwent heterocyclization in boiling acetic anhydride to produce difficultly accessible 2-(acetyl)amino-5-benzylthiazol-4(5H)-ones.     

4-甲基-3-硝基苯甲腈和2-甲基-5-硝基苯甲腈的合成与表征

4-甲基-3-硝基苯甲腈和2-甲基-5-硝基苯甲腈是重要的有机合成中间体[1,2],因其芳环上具有硝基和氰基两个第二类取代基,同时又有一个可参与反应的甲基而使得这两个化合物在有机合成领域有着广泛的应用前景.芳环上的甲基可以氧化为酸,也可进一步反应形成酰氯、酯等功能基;芳环上的氰基可水解成羧基,也可以与叠氮钠在Lewis酸催化下形成具有生物活性的四唑衍生物;芳环上的硝基经还原可形成氨基,如4-甲基-3-硝基苯甲腈通过化学反应可环合形成药物中间体6-氰基吲哚[2～4].     

1-甲基-5,6,7,8-四氢异喹啉酮-4-甲胺的合成研究

以环己酮为起始原料,经缩合、酰化及酸性水解反应制得2 乙酰基环己酮（1）;在三乙烯二胺催化下,1与氰基乙酰胺环化得四氢异喹啉酮（2）和四氢喹啉酮（3）混合物,在乙醇中回流并趁热过滤进行分离纯化得2和3; 2经催化加氢反应合成1-甲基-5,6,7,8-四氢异喹啉酮-4-甲胺,3步总收率39.8%,其结构经¹H NMR、¹³C NMR、 ¹H-¹⁵N HMBC和MS确证。