由N-苯基[1,3]苯并噁嗪正离子与烯烃[4+2]反应合成喹啉并[1,2-c][1,3]苯并噁嗪-6-酮衍生物  

Synthesis of Quino[1,2-c][1,3]benzoxazin-6-ones by [4+2] Reaction of [1,3]Benzoxazin-2-onium Ions with Olefins

作　　者：王俊蒲[1] 张炜[1] 黄利敏[1] 

机构地区：[1]兰州大学功能有机分子化学国家重点实验室,兰州730000

出　　处：《高等学校化学学报》2007年第10期1881-1884,共4页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:20472027)资助.

摘　　要：以BF3.OEt2为催化剂,在室温下通过4-羟基-N-苯基[1,3]苯并噁嗪-2-酮的脱羟基产生N-苯基[1,3]苯并噁嗪正离子,然后与富电子烯烃发生Diels-Alder反应,合成出了一系列喹啉并[1,2-c1,3]苯并噁嗪-6-酮和喹啉并[1,2-c1,3]萘并噁嗪-6-酮衍生物.The N-acyliminium cations are powerful intermediates in the construction of nitrogen-containing heterocycles. They are much more reactive than iminium cations in both intramolecular cyclizations and intermolecular cycloadditions. In this paper, a new and efficient route for the synthesis of quino [ 1,2-c ] [ 1,3 ] benzoxazin-6-ones （3a-3h） and quino [ 1,2-c ] [ 1,3 ] naphthoxazin-6-ones （3i-3j） was developed via Diels- Alder reaction of N-acyliminium cations with olefins （2a-2d） in moderate and good yields at an ambient temperature. The N-acyliminium cations, N-phenyl [ 1,3 ] benzoxazin-2-onium ion and N-phenyl [ 1,3 ] naphthoxazin-2-onium ion, are easily prepared by BF3 ·OEt2 catalyzed dehydroxylation of 4-hydroxy-3-phenyl [ 1,3 ] benzoxazin-2-ones （ 1 a-1 c ） and 4-hydroxy-3-phenyl [ 1,3 ] naphthoxazin-2-one （ 1 d ）.

关 键 词：喹啉并[1 2-c][1 3]苯并噁嗪-6-酮 4-羟基-N-苯基[1 3]苯并噁嗪-2-酮 N-酰基亚铵离子 

分 类 号：O624.6[理学—有机化学]