【摘要】 四种代表性的酰基过氧化物,苯甲酰过氧化物(1),环丙基甲酰过氧化物(2),月桂酰过氧化物(3)和三氟乙酰过氧化物(4),在HMPA(溶剂)中分解,生成高产率的相应羧酸(6),同时,又检测到HMPA的羧基化产物(8),烷基化产物(9)及脱氢二聚体(10)。各过氧化物的分解速度和产物鉴定表明,HMPA能作为电子给予体与上述酰基过氧化物发生单电子转移反应。更多还原

【Abstract】 In hexamethylphosphoric triamide (HMPA), four representative diacyl peroxides, namely, benzoyl peroxide (1), cyclopropylformyl peroxide (2), lauroyl peroxide (3) and trifluoroacetyl peroxide (4), all decompose at rates much higher than those expected from their unimolecular thermal decomposition, and the corresponding carboxylic acids are formed in high yields (74～97％). Furthermore, several radical colligation products formed from HMPA molecules can be identified. Evidently, the initial step in the reaction between a diacyl peroxide and the "solvent" HMPA involves an electron transfer with the latter acting as the donor.更多还原