8-氮杂-5,7-二甲基-2-三氟甲基色酮与烷基巯基乙酸酯之间的新型氧化还原反应。含CF3的2-吡啶酮衍生物的简便合成。

A novel redox reaction between 8-Aza-5,7-dimethyl-2-trifluoromethylchromone and alkyl mercaptoacetates. Facile synthesis of CF3-containing 2-pyridone derivatives.

作者信息

Sosnovskikh Vyacheslav Ya, Barabanov Mikhail A, Usachev Boris I

机构信息

Department of Chemistry, Ural State University, Lenina 51, 620083 Ekaterinburg, Russia.

出版信息

J Org Chem. 2004 Nov 26;69(24):8297-304. doi: 10.1021/jo049117m.

DOI:10.1021/jo049117m

PMID:15549800

Abstract

8-Aza-5,7-dimethyl-2-trifluoromethylchromone reacts with alkyl mercaptoacetates in the presence of triethylamine to give pyrido derivatives of 2-oxa-7-thiabicyclo[3.2.1]octane, which undergo the reductive ring opening to alkyl 2-[[3-(4,6-dimethyl-2-oxo-1,2-dihydropyridin-3-yl)-3-oxo-1-(trifluoromethyl)propyl]sulfanyl]acetates. The latter can be also obtained directly from 8-aza-5,7-dimethyl-2-trifluoromethylchromone and behave as the masked alpha,beta-unsaturated ketone, 4,6-dimethyl-3-(4,4,4-trifluorobut-2-enoyl)pyridin-2(1H)-one. This compound was independently synthesized from 3-acetyl-4,6-dimethyl-2-pyridone, and its synthetic potential was studied. A wide variety of 2-pyridone derivatives containing the CF(3) group have been prepared in good to moderate yields.

摘要

8-氮杂-5,7-二甲基-2-三氟甲基色酮在三乙胺存在下与烷基巯基乙酸酯反应，生成2-氧杂-7-硫杂双环[3.2.1]辛烷的吡啶衍生物，这些衍生物经还原开环生成烷基2-[[3-(4,6-二甲基-2-氧代-1,2-二氢吡啶-3-基)-3-氧代-1-(三氟甲基)丙基]硫基]乙酸酯。后者也可直接由8-氮杂-5,7-二甲基-2-三氟甲基色酮制得，且表现为掩蔽的α,β-不饱和酮，即4,6-二甲基-3-(4,4,4-三氟丁-2-烯酰基)吡啶-2(1H)-酮。该化合物由3-乙酰基-4,6-二甲基-2-吡啶酮独立合成，并对其合成潜力进行了研究。已制备出多种含CF(3)基团的2-吡啶酮衍生物，产率良好至中等。