quantum chemical and experimental studies on the mechanism of alkylation of β-dicarbonyl compounds. the synthesis of five and six membered heterocyclic spiro derivatives量子化学和实验研究β-dicarbonyl化合物的烷基化的机制。.pdfVIP

Molecules 2004, 9, 922-938 molecules ISSN 1420-3049 Quantum Chemical and Experimental Studies on the Mechanism of Alkylation of β-Dicarbonyl Compounds. The Synthesis of Five and Six Membered Heterocyclic Spiro Derivatives Nurettin Sadikov 1, Şahin Nasibov 1, Cemil Öğretir 2,*, Halil Berber 3 and Ali Hüseyinli 4 1 Baku St. University, Faculty of Chemistry, Department of Organic Chemistry, Baku, Azerbayijan 2 Osmangazi University, Faculty of Arts and Sciences, Chemistry Department, 26040 Eskişehir, Turkey 3 Anadolu University, Faculty of Sciences, Chemistry Department, 26470 Eskişehir, Turkey 4 Baku St. University, Faculty of Chemistry, Department of Analytical Chemistry, Baku, Azerbayijan * Author to whom correspondence may be addressed; e-mail: cogretir@.tr; Tel.: (+90) 222 229 04 33, ext. 2352; Fax: (+90) 222 239 35 78 Received: 5 March 2004 / Accepted: 24 June 2004 / Published: 30 November 2004 Abstract: The alkylation of β-dicarbonyl compounds in a K CO /DMSO system was 2 3 found to afford O- and C-alkylated derivatives, depending on the type of the β-dicarbonyl compound involved. The alkyl derivatives obtained were used in the synthesis of some new spiro barbituric acid derivatives. Quantum chemical calculations were carried out to elucidate the reaction mechanisms for some typical synthesis. Keywords: Alkylation of β-dicarbonyl compounds; spiro derivatives of barbituric acid, 2-chloro-1-(2- chloroethoxy)ethane; theoretical studies. Introduction The alkylation reactions of β-dicarbonyl derivative