Study on Synthetic Technology of p-Aminodiphenylamine
|School||Nanjing University of Technology and Engineering|
|Keywords||4 - Aminodiphenylamine Nitrobenzene Aniline Hydrogenation|
This paper studies the aniline and nitrobenzene two synthesis Synthesis of 4 - amino- diphenylamine . With IR, MS and HNMR of intermediates, products and by- products were characterized . Method is the use of chloro aniline nitrobenzene and aniline in CuO and PEG-2000 catalyst, to form 4 - Nitrodiphenylamine intermediates, and then by catalytic hydrogenation Synthesis of 4 - amino- diphenylamine . Under nitrogen was added acid binding agent K 2 CO 3 , Synthesis of 4 - Nitrodiphenylamine by factors of influence on the reaction , to obtain the optimum conditions as follows: feed ratio n ( aniline ): n (K 2 CO 3 ): n ( p-chloronitrobenzene ) = 1.5:0.6:1 amount of catalyst m (CuO): m (PEG-2000): m ( p-chloronitrobenzene ) = 5:10:100 , the reaction temperature is 185 ~ 190 ℃, the reaction time was 7.0h, 94.5% yield of the intermediate . Of 5% Pd / C as catalyst Recovery 4 - Nitrodiphenylamine , experimental analysis , optimal conditions : m (Pd / C): m (4 - Nitrodiphenylamine ) = 1:100 , reaction pressure 1.0MPa, stirring speed of 1000r/min, the reaction temperature is 80 ℃, reaction time was 90min, the yield was 97.2% . Nitrobenzene method is the use of aniline and nitrobenzene in TMA (OH) · 5H 2 O catalyzed synthesis of 4 - nitroso diphenylamine and 4 - Nitrodiphenylamine intermediates, and then use \Using cyclohexane as water azeotropic dehydration synthesis intermediates, by controlling the feed ratio of effective control of the generation of azobenzene , aniline and nitrobenzene optimal conditions were as follows: feed ratio is n ( aniline ) : n ( nitrobenzene ): n (TMA (OH) · 5H 2 O) = 5:1:1, reaction temperature is 70 ℃, reaction time 2.0h, the yield was 93.7 intermediates % . With 5% Pd / C as catalyst , without isolation of the intermediate product was directly Synthesis of 4 - aminodiphenylamine , the optimum conditions of : m (Pd / C): m ( mixture ) = 1:100 , and the reaction pressure was 1.0MPa , the reaction temperature is 80 ℃, reaction time was 180min, the yield was 98.8% .