Infrared Spectra of the Nitration Products of Diphenylamine

Abstract

The infrared spectra of the 19 nitration products of diphenylamine were established. A comparison was made of the spectra obtained and assignments were made to the principle bands. The compounds considered were diphenylamine, N-nitrosodiphenylamine, 4-nitrosodiphenylamine, 2-nitrodiphenylamine, 4-nitrodiphenylamine, N-nitroso-2-nitrodiphenylamine, N-nitroso-4-nitrodiphenylamine, 2,2′-dinitrodiphenylamine, 2,4-dinitrodiphenylamine, 2,4′-dinitrodiphenylamine, 4,4′-dinitrodiphenylamine, N-nitroso-2,4′-dinitrodiphenylamine, N-nitroso-4,4′-dinitrodiphenylamine, 2,2′,4-trinitrodiphenylamine, 2,4,4′-trinitrodiphenylamine, 2,4,6-trinitrodiphenylamine, 2,2′,4,4′-tetranitrodiphenylamine, 2,2′,4,4′,6-pentanitrodiphenylamine, 2,2′,4,4′,6,6′-hexanitrodiphenylamine, and picric acid (2,4,6-trinitrophenol).

Synthetic Procedures Yielding Targeted Nitro and Nitroso Derivatives of the Propellant Stabilisers Diphenylamine, N-Methyl-4-nitroaniline, and N,N′-Diethyl-N,N′-diphenylurea

“…The resulting precipitate was collected and recrystallised from glacial acetic acid to afford the title compound (l.15 g, 88.7%) as red crystals, mp 156±157 C (lit. mp 157 C (6±8) );n max (KBr) (9) (2) The title compound was synthesised using a similar procedure to that outlined above for the dinitro-diphenylamine, except 1-chloro-2,4,6-trinitrobenzene (picryl chloride (10) ) was used in place of l-chloro-2,4-dinitrobenzene. The resulting precipitate was collected and recrystallised from glacial acetic acid to afford the desired product (1.21 g, 79%), mp 179 C (lit.…”

“…The resulting precipitate was collected and recrystallised from glacial acetic acid to afford the desired product (1.21 g, 79%), mp 179 C (lit. mp 178±179 C (6±8) ); n max (KBr) (9) acm À1 3330 (NH), 3090, 1610, 1335 (CÀN), 1270 (NO 2 ); d H (CD 3 COCD 3 ) 7.35 (m, 5H, C 6 H 5 ), 9.08 (s,2H, ArÀH), 10.24 (br s, 1 H, NÀH, exchangeable).…”

“…On cooling the solution yielded the 2,2 H ,4-trinitrodiphenylamine as orange crystals (2.60 g, 86%), mp 182 C (lit. mp 183±184 C (11) ); n max (KBr) (9) acm À1 3270 (NH), 3100, 1610 (NH), 1300 (NO 2 ); d H (deutero-DMSO) 7.11±8.39 (m, 6H, ArÀH), 8.91 (d,1H, ArÀH) 11.50 (br s, lH, NÀH, exchangeable).…”

“…After drying (Na 2 SO 4 ) the organic layer was concentrated to yield a yellow oil, which gave product as yellow crystals on recrystallisation from ethanol (75 cm 3 ) and water (150 cm 3 ) (1.85 g, 61%), mp 186 C (lit. mp l83±l84 C (11) ); n max (KBr) (9) (5) To a solution of 1-chloro-2,4-dinitrobenzene (2.02 g, 0.01 moles) in dimethlyformamide (20 cm 3 ) was added 2,4dinitroaniline (1.83 g, 0.01 moles). The resulting solution was applied to a column of basic alumina (50 g) and the column eluted with dimethylformamide (200 cm 3 ).…”

“…Recrystallisation from glacial acetic acid (80 cm 3 ) furnished the title compound as yellow needles (2.41 g, 69%); mp 198 C (lit. mp 199 C (11) ); n max (KBr) (9) N-Methyl-2,4-dinitroaniline (6) (a) Methylamine (1.5 cm 3 of a 40% waw aqueous solution), and pyridine (5 cm 3 ) were added to a solution of 1chloro-2,4-dinitrobenzene (4.05 g, 0.02 moles) in methanol and the mixture heated under re¯ux for 4 hours. The methanol was removed under reduced pressure, and the residue triturated with cold water.…”