重氮萘酮在环醚中热解反应研究  

Thermolysis of 1,4-Diazonaphthones in Cyclic Ethers

作　　者：张炜[1] 牟宗宏[1] 杨立[1] 刘中立[1] 

机构地区：[1]兰州大学

出　　处：《有机化学》2001年第2期155-159,共5页Chinese Journal of Organic Chemistry

摘　　要：三种带有不同取代基的重氮萘酮(1a～1c)在THF和二氧六环中加热分解给出不同的产物.1-重氮-4-萘酮(1a)的热解产物主要是重氮萘酮热解后产生的烯酮卡宾(2a)与环醚开环后形成的聚合物;3-甲基-1-重氮-4-萘酮(1b)的热解产物比较复杂,除冠醚类产物之外,还有烯酮卡宾对四氢呋喃和二氧六环的C-H键的插入反应产物、螺环化合物、2-甲基萘酚以及难以分离的聚合物;3-硝基-1-重氮-4-萘酮(lc)的热解产物主要是聚合物,此外还有少量C-H键的插入反应产物和2-硝基萘酚.对重氮萘酮热解反应的机理作了讨论.1,4-Diazonaphthone, 3-methyl-1,4-diazonaphthone and 3-nitro-1,4-diazonaphthone were pyrolyzed in THF and dioxane to give different products. Spiro[naphthalene-1(4H),2'-pyran]-4-one-3',4',5',6'-tetrhydro (5), 2-methyl-4-(2'-tetrahydrofuranyl)naphthol (6), 2-methyl-naphthol (7) and 1:1 polymer were produced in pyrolysis of 3-methyl-1, 4-diazonaphthone in THF; Bis[( 2-methyl-1,4-naphthylene)-22-crown-6] (8), spiro[1', 4'-dioxepane-7', 1 (4H)-naphthalene-4-one] (9), 2-methyl-4-(2' -dioxanyl) naphthol (10), 2-methyl-naphthol (7) and 1:1 polymer were produced in pyrolysis of 3-methyl-1,4-diazonaphthone in dioxane. Only 1:1 polymers were obtained in pyrolysis of 1,4-diazonaphthone in both THF and dioxane. 3-Nitro-1, 4-diazonaphthone gave 2-nitro-4-(2'-tetrahydrofuranyl) naphthol (11), 2-nitro-naphthol (12) besides 1:1 polyme in THF. The reaction mechanism is discussed.

关 键 词：热解反应 重氮萘酮 烯酮卡宾 环醚 反应机理 

分 类 号：O625.64[理学—有机化学]