Picramide

A mixture of 229 g. (1.0 mole) of picric acid (m.p. 120-121°) and 180 g. (3.0 moles) of urea is heated in a bath held at 173° for 36 hours. The cooled reaction mixture is extracted with 1.5 1. of water at 40°, 

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In general the method is not as useful for the preparation of arylamines as for aliphatic amines. But the method becomes of preparative interest when the nuclear halogenated compound contains in addition some electron withdrawing substituents e.g., -N02, -CN etc. in ortho and para positions. Thus, 2, 4, 6 trinitroaniline (picramide) is readily prepared by the action of aqueous ammonia on... 

Substituted Phenyl 2,4,6-trinitrophenyl sulphides. By UV-VIS measurements of the reactions of 4 -substituted phenyl 2,4,6-trinitrophenyl sulphides with amines in DMSO, Crampton s group131 showed the presence of two well-separated processes which were interpreted by Scheme 7129. In each case a rapid reversible equilibrium was established leading to the 3-adduct (10). They also observed a second, much slower process resulting in formation of the N-substituted picramide derivatives, 13. The final spectra were identical to those of the independently prepared products, 13. Chamberlain and Crampton133 showed that the reaction products are in rapid equilibrium with anions derived from them by amine addition at the 3-position and/or loss of a side-chain proton, but they did not find evidence for the accumulation of spectroscopically observable concentrations of intermediates such as 12. 

Solutions of sodium or potassium nitrates in concentrated sulfuric acid can be used as a substitute for anhydrous mixed acid." 2,4,6-Trinitroaniline (picramide) has been synthesized via the addition of a solution of potassium nitrate in concentrated sulfuric acid to a solution of either o- or p-acetanilide in oleum. ... 

The presence of three nitro groups on the aromatic ring of picryl chloride makes the chloro group extremely reactive towards nucleophiles. Picryl chloride (87) is hydrolyzed to picric acid (4) in the presence of hot water or aqueous sodium hydroxide. Aminolysis of picryl chloride in the presence of primary and secondary amines is complete in minutes at room temperature. Picryl chloride is therefore a very useful starting material for the synthesis of a range of other picryl derivatives. The reaction of picryl chloride (87) with ammonia can be used to synthesize 2,4,6-trinitroaniline (53) (picramide). Treatment of picryl chloride with alcohols under reflux forms picric acid and the alkyl chloride of the corresponding alcohol, whereas the same reaction in the presence of alkali metal hydroxides, or the alkoxide anion of... 

Picryl chloride (87) reacts with hydroxylamine hydrochloride to yield 2,4,6-trinitroaniline (53) (picramide) and not the expected At-hydroxy-2,4,6-trinitroaniline. In contrast, the same reaction in the presence of sodium ethoxide is reported to yield 4,6-dinitrobenzofuroxan (94) via substitution of the halogen by hydroxylamine, followed by an internal redox reaction between the hydroxyamino group and one of the adjacent o-nitro groups. ... 

Other explosives, such as 2,4,6-trinitroanisole (7),33b.226 2,4,6-trinitroaniline (picramide), and tetryl (101), ° are conveniently prepared from the nitration of the corresponding 2,4-dinitro derivatives, which in turn, are prepared from the reaction of 2,4-dinitrochlorobenzene with the appropriate nucleophile. 

Recently, TATB (14) has been synthesized by treating TNB and picramide (53) with VNS aminating agents like 4-amino-1,2,4-triazole (ATA) and 1,1,1-trimethylhydrazinium iodide (TMHI) in the presence of sodium methoxide in Hydroxylamine has been used... 

The reaction of nitronium salts with primary amines is not usually a feasible route to primary nitramines, except in the case of some electron-deficient arylamines . Picramide... 

Tire present paper describes a simple and convenient procedure for the identification of explosives viz Picramide Hexyl 2,4-Dinitrophenetole (DNP) Tetryl s-TNT s-TNB 2,4,6-Trinitroanisole (TNA) 2,4-Dinitroanisole (DNA) 2,4,6-Trinitro-phenetole (TNP) DNCB m-DNB and Picryl Chloride (PC) in ordnance stores as charge-transfer complexes with amines utilizing TLC... 

It was seen that irrigating solvent had pronounced effect on the relative mobilities of the n complexes eg the Rf values of Tetryl and Picramide. were reversed with petroleium ether—ethyl acetate (9 1) compared to MCB-EDC system ... 

F. Pisani prepd 2,4,6TTrinitroaniline, also known as Picramide (Vol 1 of Encycl, pp A409-R A410-L)... 

Trinitroanilina o Picramide (TNA) is an explosive equal in power to PA (Picric Acid). Its props are described in Belgrano (Ref 31, pp 270—71) but uses are not indicated... 

As a rule explosives were listed and described under their parent compounds arranged in alphabetical order, as for example 2,4,6-Trinitroaniline or Picramide is described under ANILINE in Vol I of Encycl. Most of the metallic salts are described under the names of their anions as, for example, Lead Azide (LA) is described under AZIDES, Mercuric Fulminate (MF), under FULMINATES, whereas some salts are described under the names of their cations- as for example Ammonium Nitrate (AN) is described under AMMONIUM in Vol 1... 

Dinitro-p-cresol 2,4,6-rTrinitroaniline (Picramide) sym-Trinitromesytylene (1,3,5-Triraethyl-2,4,6-trinitrobenzene) 2,4,6-Trinitroresorcinol (Styphnic Acid) 2-Amino-... 

On heating with alcoholic ammonia a picramide is formed [3] ... 

ProcChemSoc (London) 1964, 232-33 CA 61, 14050(1964)(UV absorption spectra of Dipicramide other ring-substituted picramides in dioxane)... 

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