Synthesis of substituted β-(2-selenienyl)-ethylamines

Substituted -(2-selenienyl)ethylamines were synthesized by the reduction of the corresponding ,-unsaturated nitro compounds. 2-(-Nitrovinyl)selenophene was alkoxylated and aminated.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 184–186, February, 1971     

Efficient Synthesis of 1-(2-Propynyl)pyrrole

Russian Journal of Organic Chemistry -     

Synthesis of 3-(2-Aminoethyl)pyrrole Derivatives

3-(2-Di-n-propylaminoethyl)pyrrole (1a) was prepared in good yield by reduction of pyrrole-3-(N,N-di-n-propylglyoxamide) (9) with lithium aluminum hydride. 3-(2-Di-n-propylaminoethyl)-5-acetylpyrrole (1b) was prepared by first acetylation of 1-p-toluenesulfonyl-3-(2-di-n-propylaminoethyl)pyrrole (6) followed by hydrolysis of the p-toluenesulfonyl substituent. The starting material 6 was prepared by homologation of 1-(p-toluenesulfonyl)pyrrole-3-carboxaldehyde (3) to the corresponding acetaldehyde followed by reductive amination of the latter.     

双-[2-吡咯(乙氧基)]乙烷的合成及其电化学聚合

以吡咯和二缩三乙二醇为原料合成了N取代吡咯衍生物单体--双-[2-吡咯(乙氧基)]乙烷,并用循环扫描伏安技术研究了该单体的电化学聚合过程.结果表明:在乙腈/高氯酸锂溶液中,双-[2-吡咯(乙氧基)]乙烷在铟锡氧化物导电玻璃(ITO)、Pt、Au、玻璃碳、石墨电极上均能顺利发生反应,形成一定厚度的聚合物膜.但聚合速率、膜的结构、膜的颜色有差异.溶剂水对聚合有明显影响.形成的聚合膜具有良好的电化学稳定性.     

Synthesis of 2-(methoxycarbonyl)methyl-7-phenylacetamido-3-thiacepham-4-carboxylates

Representatives of the title compounds have been prepared from a benzyl-penicillin-derived intermediate.     

Synthesis of functionalized pyrrolidin-2-ones and (S)-Vigabatrin from pyrrole

Starting from pyrrole, the novel 3,4-didehydropyrohomoglutamate 8 or (ent)-8 can be efficiently synthesized in up to 91% ee, which can be utilized as a versatile building block toward functionalized pyrrolidin-2-ones. Moreover, (ent)-8 can be readily converted to (S)-Vigabatrin, being an irreversible inhibitor for GABA-T, which is used as adjunctive therapy in patients that suffer from epilepsy.     

Synthesis and IR spectra of 5-phenyl-2-(1-phenyl-2-trichloroacetylethenyl)pyrrole

5-Phenyl-2-(1-phenyl-2-trichloroacetylethenyl)pyrrole was synthesized by the reaction of 2-phenylpyrrole with 1-phenyl-2-trichloroacetylacetylene on silicon oxide. The structure of an intramolecular proton-transfer H-complex was assigned to the title compound based on analysis of its IR spectra in solutions in the temperature range of 165–298 K. Published inIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 1945–1947, November, 2000.     

3-(2-氰基乙氧基)甲基-和3-[甲氧基(三乙氧基)]甲基-3'-甲基氧杂环丁烷的合成及其共聚体研究

以三羟甲基乙烷为原料, 通过脱水反应首先制得3-羟甲基-3'-甲基氧杂环丁烷(HMO). HMO再分别与丙烯腈和二缩三乙二醇单甲醚反应得到两个取代氧杂环丁烷单体3-(2-氰基乙氧基)甲基-和3-[甲氧基(三乙氧基)]甲基-3'-甲基氧杂环丁烷(HMOAN和HMOPEO). 再用阳离子开环聚合方法, 以BF 3\5乙醚作催化剂, 丁二醇为引发剂, 将两类单体共聚即可得到一系列不同组成的共聚物(PAP). 利用 1H NMR谱图计算了该共聚物中两种不同结构单元的比, 结果表明, 其与投料比基本吻合. GPC测得该共聚物的数均分子量范围为2 756～5 342, 分子量分布为1.26～1.83. DSC测试结果发现, 除在225～246 K之间有一个玻璃化转变温度之外, 在305～348 K之间还存在一个热转变温度. TGA测得共聚物的分解温度为573 K, 远高于目前广泛使用的液体电解质. 电导率测试结果表明, AN20的室温电导率可达到1.07×10 -5 S/cm, 353 K时电导率可达到2.79×10 -4 S/cm, 接近实用要求.     

Chemistry of 2-hetarylbenzimidazoles. 8. Synthesis and properties of 1-methyl-2-(5′-methyl-2′-selenienyl)benzimidazole

1-Methyl-2-(5-methyl-2-selenienyl)benzimidazole was synthesized and subjected to electrophilic-substitution reactions: nitration, bromination, sulfonation, chloromethylation, formylation, and acylation. The substituent usually enters the 4 position of the selenophene ring, but nitration with acetyl nitrate leads to a mixture of 5-nitro and 4-nitro derivatives. Oxidation of 2-selenienylbenzimidazole with potassium permanganate leads to the 5-carboxy derivative, while oxidation with selenium dioxide leads to the 5-hydroxymethyl and 5-formyl derivatives.See [1] for Communication 7.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1636–1639, December, 1987.     

Synthesis of tri- and tetramethylene[b]pyrrole derivatives from 2-(1-ethoxy-2-bromoethyl)cycloalkanones

Tri- and tetramethylene[b]pyrrole derivatives were synthesized by treatment of the corresponding 2-(1-ethoxy-2-bromoethyl)cycloalkanones with an aqueous solution of sodium hydroxide and a methanol solution of a primary amine. The transformation proceeds through a step involving 1,3-dehydrobromination and opening of the three-membered ring in the intermediately formed spirocyclic ketones.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 37–39, January, 1992.     

Synthesis of some 4-(hetaryl)methyl-γ-lactones

The reaction of alkylglycidylmalonate and alkylglycidylacetoacetate esters with pyrrolidine, piperidine, and morpholine has given butanolides in which these heterocycles are attached to the 4-position of the lactone ring.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 20–22, January, 1988.     

Synthesis of 3-hydroxy-1-methyl-2-(methylthio) pyrrole from methyl isothiocyanate and prop-2-yn-1-ol

A methylated adduct of lithiated 1-(1-ethoxyethoxy)allene and methyl isothiocyanate undergoes intramolecular cyclization in the presence of CuBr to give 3-(1-ethoxyethoxy)-1-methyl-2-(methylthio)pyrrole. The methanolysis of the latter affords 3-hydroxy-1-methyl-2-(methylthio)pyrrole. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1645–1647, September, 2000.     

2-(5-取代苯氧甲基-1,3,4-噻二唑-2-亚胺基)-5-(取代苯基亚甲基)-4- 噻唑啉酮的合成

以2-氨基-5-取代苯氧甲基-1,3,4-噻二唑(1)为起始原料, 合成了中间体2-氯乙酰氨基-5-取代苯氧甲基-1,3,4-噻二唑)-2-乙酰亚胺(2)和2-(5-取代苯氧甲基-1,3,4-噻二唑-2-亚胺基)-4-噻唑啉酮(3), 化合物3进一步与取代苯甲醛发生类Knoevenagle缩合反应, 得到了一系列2-(5-取代苯氧甲基-1,3,4-噻二唑-2-亚胺基)-5-(取代苯基亚甲基)-4-噻唑啉酮类化合物4a～4p. 目标化合物4a～4p的结构经IR, ¹H NMR和元素分析确证.     

2-苯氧(硫)甲基-6,7-亚甲二氧-3-喹啉酸乙酯及其衍生物的合成

6-氨基胡椒醛与乙酰乙酸乙酯在碱的催化下, 缩合产物与NBS发生溴代反应, 生成2-溴甲基-6,7-亚甲二氧基-3-喹啉酸乙酯,产物与苯酚,取代苯酚, 苯硫酚, 取代苯硫酚发生Williamson取代反应, 高分辨地得到一系列喹啉吩醚衍生物, 苯酚和硫酚上的吸电子基团有利于增强亲核能力,有利于Williamson反应.     

Synthesis and herbicidal activities of methyl-1-(2,4-dichlorophenoxyacetoxy)alkylphosphonate monosalts

A series of 1-(2,4-dichlorophenoxyacetoxy)alkylphosphonic acid dimethyl esters 5 and its corresponding phosphonate monosalts 6 were synthesized as potential herbicide. The phosphonate monosalts can be prepared from 1-(2,4-dichlorophenoxyacetoxy)alkylphosphonic acid dimethyl esters 5, which were synthesized by the condensation of O,O-dimethyl-1-hydroxyalkylphosphonates with dichlorophenoxyacetic chloride. This method provides a simple and efficient procedure for the synthesis of phosphonate derivatives containing sensitive groups to acid, base or water such as carboxylate ester bond; and the herbicidal activity of title compounds was evaluated in a set of experiments in greenhouse. Most of the compounds exhibited notable herbicidal activity.     

Synthesis and Some Chemical Conversions of 2-([2,2]-5-Paracyclophanyl)pyrrole

2-([2,2]-5-Paracyclophanyl)pyrrole has been synthesized and nitration and formylation of it have been effected. The 1--cyanoethyl derivative and 2-formyl-5-paracyclophanyl-3H-pyrrolizine have been obtained from 5-formyl-2-([2,2]-5-paracyclophanyl)pyrrole by the action of acrylonitrile and acrolein respectively under Michael reaction conditions.     

Investigations in the field of the chemistry of 2-hetarylbenzimidazoles. 6. Synthesis and properties of 1-methyl-2-(2′-selenienyl)benzimidazole

2-(2-Selenienyl)benzimidazole has been synthesized by a Weidenhagen reaction and converted into the N-methylated derivative. Electrophilic-substitution reactions (nitration, sulfonation, bromination, chloromethylation, and acylation) in the selenophene ring have been studied. It has been shown that the substituent enters the position of the selenophene ring in most cases. The bromination of 1-methyl-2-(2-selenienyl)benzimidazole in acetic acid produces the 3,5-dibromo derivative, whereas 1-methyl-5(or 6)-bromo-2-(3,5-dibromo-2-selenienyl)benzimidazole is obtained in polyphosphoric acid.For Report 5, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1531–1534, November, 1983.     

Diastereoselective Michael additions of N-Boc-2-(tert-butyldimethylsiloxy)pyrrole to 2-(Arylsulfinyl)-1,4-benzoquinones

Reactions of 2-(arylsulfinyl)-1,4-benzoquinones 1a-c with N-(tert-butoxycarbonyl)-2-(tert-butyldimethylsiloxy)pyrrole 2 have been studied under different catalytic conditions. Under BF(3).OEt(2) catalysis, reactions were completely stereoselective leading to the Michael-type adducts 3, whereas in the presence of SnCl(4) diastereomeric mixtures of the pyrrolo[3,2-b]benzofuranes 5 and 6 were obtained. The latter products result from a tandem process involving the Michael reaction followed by an intramolecular cyclization of the intermediates 3 and 4, the first step being hardly stereoselective. Reactions catalyzed by Eu(fod)(3) evolved in a highly stereoselective manner yielding the products 3 or 5 depending on the electronic density of the arylsulfinyl group.