The Law And Mechanism Of The Substitutional Reaction Of 5-chloromethyl-8-hydroxyquinoline With Aromatic Amines

N alkylation and C alkylation of aromatic amines have been widely used in the preparation of organic intermediates and organic synthesis. Generally, in the process of the alkylation of aromatic amines, N alkylation and C alkylation reaction occur simultaneously. Usually, N alkylation is easier access than C alkylation due to the fact that the activity energy of C alkylation of aromatic amines is higher than that of N alkylation of aromatic amines. Therefore, it is significant that if N alkylation products and C alkylation products can be obtained selectively by controlling the conditions. The alkylation between 5-chloromethyl-8-hydroxyquinoline and aromatic amines has been paid much attention to in the alkylation of aromatic amines. We found in the reaction between 5-chloromethyl-8-hydroxyquinoline and diphenylamine that the substituted products of aromatic amines in the 5-sited of 8-hydroxyquinoline connected through C-N bond was obtained when acetonitrile was used as solvent, NaHCO3 as base, and the temperature was 70-80℃; And the substituted products of aromatic amines in the 5-sited of 8-hydroxyquinoline connected through C-C bond was obtained when DMF was used as solvent, K2CO3 as base, and the temperature was 120℃. At present, the substitution reaction through C-C bond has not been reported yet. The phenomenon that different substitued products were produced under different conditions arised my great interest.Therefore, this work studied the reaction between 5-chloromethyl-8- hydroxyquinoline and aromatic amines, the effects of amine'structure and reaction conditions on the selectivity of N substitued products and C substitued products. Also we studied the mechanism of the reaction. The main points of this paper are as follows:1. We studied the law of amine'structure on the substitutued products mainly by exploring the reaction between 5-chloromethyl-8-hydroxyquinoline and different amines and reaction between different benzyl chlorides and amine.2. We studied the factors that affect the reaction between 5-chloromethyl -8-hydroxyquinoline and aromatic amines. We mainly investigated the effects of base, solvent and temperature on the selectivity of N alkylation products and C alkylation products, and also studied how the products change with the reaction time.3. We explored the mechanism of the C alkylation between 5-chloromethyl -8-hydroxyquinoline and aromatic amines. Through studying the influence factors of the reaction and related experiment designs, we suggested that what the elementary steps of the reaction can be and the intermediate can be carbocation. Above all, we proposed the mechanism of the C alkylation between 5-chloromethyl-8- hydroxyquinoline and aromatic amines.