Synthesis of Perfluoroalkyl-1H-benzo[c]quinolizin-l-one Derivatives from 2-Methylquinolines
-
- KONAKAHARA Takeo
- Department of Industrial Chemistry, Faculty of Science and Technology, Science University of Tokyo
-
- KUBOTA Shin
- Department of Industrial Chemistry, Faculty of Science and Technology, Science University of Tokyo
-
- SANO Kazuya
- Department of Industrial Chemistry, Faculty of Science and Technology, Science University of Tokyo
-
- MURAYAMA Takashi
- Department of Industrial Chemistry, Faculty of Science and Technology, Science University of Tokyo
Bibliographic Information
- Other Title
-
- 2-メチルキノリン誘導体を用いるペルフルオロアルキル置換1H-ベンゾ[c]キノリジン-1-オン誘導体の合成
- Synthesis of Perfluoroalkyl-1H-benzo(c)quinolizin-1-one Derivatives from 2-Methylquinolines.
Abstract
As an extension of our synthetic investigation on heterocycles using silicon reagents, preparation of perfluoroalkyl-1 H-benzo[ c ]quinolizin-1-onesw as studied. An addition-cyclization reaction of perfluoro(2-methyl-2-pentene) [ 2 ] with a 2-quinolylmethyl carbanion generated from 2-(trimethylsilylmethyl)quinoline [3 a] in the presence of a catalytic amount of tetrabutylammonium fluoride (TBAF) afforded 3-pentafluoroethyl-2-trifluoromethyl-1 Hbenzo[c ]quinolizin-1-one [6 a] in 36% yield, accompanied with the corresponding adduct [4 a] and E/Z alkenes [5 a] (1, 29 and 11% yields, respectively). These intermediate compounds [4 a] and E/Z-[5 a] were effectively transformed into the final product [6 a] on heating in wet xylene. An equilibrium constant KE-Z for E-Z isomerization of [5 a] was 2.44 in refluxing dry tetrahydrofuran (THF) and the calculated ΔGE→Z was 2.5 x 103 J⋅ K-1mol-1. Under the optimized conditions ([3]:[2]: [KF] =1: 3: 1; at -5°C for 3 h in THF, then refluxed for 6 h in xylene after quenching with water and replacement of the solvent), the reaction of [3a] or the methyl- or chloro-substituted analogs gave the corresponding 1 Hbenzo[c ]quinolizin-1-one derivatives [6a]-[6e] in 93 (substituent R =H), 92 (R =6-CH, ), 83(R = 8 -CH3), 90(R =8-Cl), 86%, (R =10-Cl) yields, respectively, and 5-methyl-3-pen tafluoroethyl2-trifluoromethyl-1 H-benzo[ c ]quinoxalizin-1-one [6 f] in 35% yield.
Journal
-
- NIPPON KAGAKU KAISHI
-
NIPPON KAGAKU KAISHI 1992 (12), 1455-1462, 1992-12-10
The Chemical Society of Japan
- Tweet
Keywords
Details 詳細情報について
-
- CRID
- 1390282679365982208
-
- NII Article ID
- 130004159815
-
- ISSN
- 21850925
- 03694577
-
- Data Source
-
- JaLC
- Crossref
- CiNii Articles
-
- Abstract License Flag
- Disallowed