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41.3.2.1.1 Method 1: Nitration of Anilines

DOI: 10.1055/sos-SD-041-00393

Jahn, U.Science of Synthesis, (201041388.

The N-nitration of anilines is one of the most frequently used methods for the synthesis of N-aryl-N-nitroamines. The yield and selectivity are, however, highly dependent on the substitution pattern of the starting aniline and the reagent used for nitration. Generally, aniline itself and donor-substituted anilines are nitrated on the ring, and N-aryl-N-nitroamines are rarely, if ever, observed. One can suspect that N-aryl-N-nitroamines are formed during nitration as fleeting intermediates, but undergo the N-nitroamine rearrangement under the reaction conditions. Acceptor-substituted anilines, in which the ring electron density is diminished, are nitrated at the amino group in moderate to good yields (Table 1). The most common nitrating agents are 90100% nitric acid alone or in acetic acid, fuming nitric acid in acetic acid and acetic anhydride, or fuming nitric acid in sulfuric acid. However, nitronium tetrafluoroborate or dinitrogen pentoxide have also been used occasionally for this purpose. Using nitric acid, nitric acid in acetic acid, or nitric acid in acetic anhydride, N-nitroamines with unchanged substitution patterns can be isolated (entries 1, 2, 1335, and 37).[‌165‌‌178‌] Several functional groups in the starting anilines such as ortho- and para-sulfonate, para-carboxylate, para-formyl, and para-acyl groups are subject to exchange by a nitro group during nitration, giving nitro(nitroamino)benzenes (entries 312).[‌166‌,‌167‌] Other ring nitrations occur only rarely (entries 36 and 38).[‌177‌,‌178‌] Ring nitration in addition to N-nitration to nitro(nitroamino)benzenes is more favored when the nitric acid/sulfuric acid reagent is applied (entries 4044 and 4851).[‌168‌‌170‌,‌179‌‌184‌] The facile introduction of additional nitro groups may be due to the presence of sulfuric acid, which is commonly used to promote the N-nitroamine rearrangement. Sulfonate groups are concomitantly exchanged during the nitration process (entries 46 and 47).[‌181‌] Polynitrated N-nitroamines tend to transform into diazonium phenolates (diazophenols) under the reaction conditions {see Science of Synthesis, Vol. 28 [Quinones and Heteroatom Analogues (Section 28.1128.11)]}. There is great interest in N-nitroamines as agricultural products and explosives, and a large number of N-nitroanilines and their salts have appeared in the patent literature.[‌185‌‌192‌]

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References