一些过氧化酰热分解反应的CIDNP研究

A CIDNP Study on the Decomposition of Diacyl Peroxides

用核磁共振研究过氧化癸酰,过氧化壬酰,过氧化5-甲基己酰和过氧化3-甲基丁酰分别在邻二氯苯的饱和碘溶液或四氯化碳中的热分解反应.观察到烷基自由基的笼反应产物烯烃(R_(-H))和扩散产物 RX(R=烷基,X=Cl,I)的 CIDNP 多重效应.对过氧化酰热分解反应及自由基对的形成和反应机理作了讨论.

The thermal decomposition of decanoyl peroxide(1),nonanoyl peroxide(2),5-methylhexanoyl peroxide(3),and 3-methylbutyryl peroxide(4)in botho-dichlorobenzene(ODCB)and carbon tetrachloride was carried out at 80-85℃,andmonitored by NMR.The E/A multiplet effect of α-CH_2 protons of alkenes and A/Emultiplet effect of α-CH_2 protons of alkyl halides were observed.The relative intensitiesof CIDNP lines and relative concentrations of polarized and normal products changedwith the reaction time.The reaction mechanism was discussed.