Highly selective preparation of valuable dinitronaphthalene from catalytic nitration of 1‐nitronaphthalene with NO₂ over HY zeolite

Abstract

In this work, a simple method for the highly selective preparation of valuable dinitronaphthalene from 1-nitronaphthalene employing NO 2 as a nitrating agent has been developed. The results demonstrated that HY zeolite as an eco-friendly and stable catalyst exhibits good catalytic performances. The total selectivity to valuable dinitronaphthalene compounds including 1,5-, 1,4-, and 1,3-dinitronaphthalene can reach 87.6 % in our present nitration reaction. Meanwhile, the physico-chemical properties of catalysts were characterized by XRD, FTIR, TG/DTG, BET, and NH 3 -TPD, and the probable nitration reaction mechanism was also suggested in this paper. The present nitration process seems to be a mild, eco-friendly, and economical route for the preparation of valuable dinitronaphthalene compounds.

Synthetic Protocols for Aromatic Nitration: A Review

“…complex attack on aryl ring via electrophilic reaction and give nitrated product. [41] Efficient green aromatic nitration developed by Guo et al using Bi(NO 3 ) 3 .5H 2 O/MgSO 4 by ball milling (Scheme 33). This mechanochemical reaction was performed under specific rotating speed (400 rpm) and final product was extract by using dichloromethane.…”

“…This H‐Complex intermediate generate NO 2 + complex by releasing HNO 2 . This NO 2 + complex attack on aryl ring via electrophilic reaction and give nitrated product [41] …”

Acid‐free and highly efficient one‐step nitration of naphthalene with NO2 promoted by O2‐Ac2O in Fe‐ and Cu‐modified S2O82−/ZrO2 catalyst to 1,5‐dinitronaphthalene under mild conditions

“…[11] As a result, the highly selective preparation of 1,5-DNN by NT nitration in a single step under mild conditions is of great significance. Most processes, except for the nitration routes, concentrate on using solid catalysts to substitute sulphuric acid, such as solid superacid, [12] modified montmorillonite clay, [13] zeolite, [14,15] and inorganic ionic solid. [16] Among them, [17,18] Al-modified ZrO 2 as the support and (NH 4 ) 2 S 2 O 8 as the sulphur source showed the best activity for n-pentane isomerization.…”

“…Most processes, except for the nitration routes, concentrate on using solid catalysts to substitute sulphuric acid, such as solid superacid, [ 12 ] modified montmorillonite clay, [ 13 ] zeolite, [ 14,15 ] and inorganic ionic solid. [ 16 ] Among them, [ 17,18 ] solid superacid (SO 4 2− /ZrO 2 ) exhibited excellent activity for esterification, nitration, isomerization, dehydration, alkylation, and other reactions.…”