摘要
酮的烯醇硅醚的富电子碳碳双键易被亲电子基团进攻,生成取代酮类化合物。例如,在TiCl_4等Lewis酸的存在下,卤代烷与酮的烯醇三甲硅醚反应生成2-烷基取代酮。迄今为止,还没有卤代氟烷与酮的烯醇非醚反应研究的报道。我们将3,3-二甲基-2-丁酮的烯醇三甲硅醚与等摩尔的1,1,1-三氟-2,2,2-三溴乙烷及催化量的过氧化月桂酰进行光照3h后,б_F-10 ppm处出现一新峰,与CF_3CBr_3(2)的δ_F0 ppm处峰的面积比为2:3。继续光照,δ_F-
UV irradiation of CH_2=C(OSiMe_3)CMe_3 (1) with equal mole of CF_3CBr_3 (2) gave a mixture of Me_3SiBr (3), CF_3CBr_2CH_2COCMe_3 (4), CF_3CBr=CHCOCMe_3 (5) and pinacolone (6). 1 also reacted with Cl(CF_2), I (7, n=2:8, n=4:9, n=6) under simitar condition to give the fluorinated ketone, CI(CF_2)_nCH_2COCMe_3 (10, n=2:11, n=4:12, n=6) and Me_3Sil respectively. Treatment of compounds 4, 10, 11 and 12 with aqueous NaHCO_3 or NaOH furnished the corresponding α,β-enone 5 and (CI(CF_2)_(n-1)CF=CHCOCMe_3 (13, n=2:14, n=4:15, n=6) in good yield.
出处
《有机化学》
SCIE
CAS
CSCD
北大核心
1989年第1期38-40,共3页
Chinese Journal of Organic Chemistry
关键词
片呐酮
氟烷基化
烯醇
三甲基硅醚
pinacolone
trimethylsilyl enol ether
fluoroalkylation
ultraviolet irradiation
