2.4- Dinitroaniline Dinitrobenzene

Dimethyl sulfate, 57 Dimethyl sulfide, 57 Dimethyl sulfoxide, 57 Dimethyl terephthalate, 57 Dimetilan, 57 Dinitroanilines, 57 Dinitrobenzenes, 58 Dinitrolmide, 58 Dinitronaphthalenes, 58 Dinitro-o-Cresol, 58 Dinitrophenols, 58... 

Van der Schalie, W.H. The Acute and ChronicToxicity of 3,5-Dinitroaniline, 1,3-Dinitrobenzene, and 1,3,5-Trichlorobenzene to Freshwater Aquatic Organisms, U.S. Army Medical Bioengineering Research and Development Laboratory, Fort Detrick, MD, Technical Report 8305 (1983), 53 p. 

Hydrogen displacement from unsymmetrical substrates like 1,3-dinitrobenzene can produce a mixture of products. Reaction of 1,3-dinitrobenzene with hydroxylamine produces a mixture of 2,4-dinitroaniline and 2,6-dinitroaniline l,3-diamino-2,4-dinitrobenzene is formed if two equivalents of hydroxylamine are employed. °... 

Edwards and Meacock189, following amide hydrolyses in strong acid solution, used a uv spectrophotometric method. Bunton et al.224 followed the hydrolysis of NN-dimethylbenzamide by adding an alcoholic solution of l-fluoro-2-4-dinitrobenzene and alkali to aliquots of reaction mixture and determining the N,N-dimethyl-2,4-dinitroaniline spectrophotometrically at 381 m/tt. 

N-Cyclohexyl-2,4-dinitroaniline or 2,4-Dinitro -1-cyclohexyl ami nobenzene, C6H3(N02)2.NH.C6H, mw 265.26, N 15.84% yel crysts, mp 155 readily sol in benz acet si sol in light petroleum ale insol in w was prepd by heating for 3 hrs on a w bath a soln of 1-chloro-2,4-dinitrobenzene 45% aq cyclohexylamine. Nitration yields an expl compd... 

The presence of electron-withdrawing groups (notably the nitro group) sited in the ortho or para positions of an aryl halide facilitates the halogen replacement. Here the mechanism proceeds by an addition-elimination sequence and it is discussed and illustrated in the formation of 2,4-dinitroaniline and 2,4-dinitrophenylhydrazine (Section 6.8.2, p. 959), and in the use of 1-fluoro-2,4-dinitrobenzene in the derivatisation of an amino group in an amino acid (Section 9.6.23, p. 1279). 

This method cannot be applied to polynitro amines, since these are so weakly basic that they can be diazotised only under special conditions in strongly acidic media (Section 6.7.1, p. 922). In such cases use may be made of the susceptibility to nucleophilic displacement of halogen when activated by ortho and para nitro groups. Thus the valuable reagent 2,4-dinitrophenylhydrazine (Expt 6.93) is readily prepared by reacting l-chloro-2,4-dinitrobenzene with hydrazine. Reaction with ammonia similarly gives 2,4-dinitroaniline (cognate preparation in Expt 6.93). 

Dinitration of p-chloro(trifluoromethyl)benzene will take place at the ring positions ortho to the chlorine. Compound A is 2-chloro-5-(trifluoromethyl)-l,3-dinitrobenzene. Trifluralin is formed by nucleophilic aromatic substitution of chlorine by dipropylamine. Trifluralin is N, A-dipropyl-4-(trifluoromethyl)-2,6-dinitroaniline. 

This property of nitro compounds was first observed by Foord [78] with regard to o- nitrophenol, 2,4-dinitrophenol, picric acid, m- dinitrobenzene, 2,4-dinitro-toluene, 1,3,8-trinitronaphthalene, 2,4-dinitroaniline and other higher nitrated aromatic compounds. 

Trinitrobenzene cannot be obtained by the nitration of o- dinitrobenzene. Kamer and Contardi have prepared this isomer from 2,6-dinitroaniline ... 

Nowadays 2,4-dinitroaniline is prepared on a large scale by treating chloro-dinitrobenzene with ammonia. The method was first reported by Engelhardt and Lachinov [9] in 1870. Heating 2,4-dinitrophenol with an excess of urea at 208°C... 

Dinitroaniline has weak explosive properties of the order of m- dinitrobenzene. However, its sensitivity to impact, according to Wohler and Wenzelberg [10] is considerably higher than that of dinitrobenzene and similar to that of TNT. 

Pd-C in both ethanol and DMF, little, if any, selectivity was obtained product ratios were 50 50 in ethanol and 60 40 in DMF. Palladium black in ethanol, which afforded 4-amino-5-nitroveratrole in 70-75% yield from 4,5-dinitroveratrole, provided no selectivity with 2,4-dinitroaniline, as well as with o- and m-dinitrobenzenes both nitro groups were hydrogenated.140 Reduction by sodium borohydride and Pd-C in methanol also does not appear to be selective, as 1,2,4-triaminobenzene is formed.141 It is of interest that over Pt-C in acidic alcohol 2,4-dinitroaniline is selectively hydrogenated at the 4-nitro group to give 4-amino-2-nitroaniline in 70% yield.142... 

Measured concentrations of 2-ADNT and 2,4-DANT in spiked sediments at the end of a short mixing period (up to 4 h) were also substantially lower than nominal concentrations [8,9,13], as expected based on the description of the fate of those compounds in sediment [7], Spiking of TNB to sediment resulted in the formation of l-amino-3,5-dinitrobenzene, also called 3,5-dinitroaniline [13]. Similar to TNT, reduced transformation products of TNB can form covalent bonds with the sediment and resist solvent extraction, thus explaining the substantial difference between the analytically determined concentrations of extractable compounds and the expected concentrations. Similar to TNT, air-drying of sediment spiked with TNB or 2,4-DANT prior to solvent extraction appears to promote a decrease of the extraction efficiency of parent and transformation products, as lower extraction efficiencies were observed with air-drying [8] than without air-drying [13] for those compounds in separate studies. A direct comparison of the extraction efficiency of spiked sediment extracted wet and air-dried, conducted for 2,6-DNT [12], should be performed for other major explosives for validation of the recommendation of wet extraction [12] of sediments contaminated with explosive compounds. 

A-(2-Hydroxyethyl)-2,4-dinitroaniline 548 Ethanolamine (0.5 g) is shaken at room temperature for 3 h with sodium hydrogen carbonate (1 g), water (10 g), and a solution of 1-fluoro-2,4-dinitrobenzene (0.8 g) in ethanol (20 ml). Then, to remove the excess of fluorodinitro-benzene, glycine (0.2 g) is added, shaking is continued for a further 2 h, the alcohol is removed in a vacuum, and the residue is treated with water. Extraction with ether, evaporation of the ether extract, and recrystallization of the residue from ethanol give reddish-yellow needles (1.62 g, 86.4%), m.p. 92°. 

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