Trinitrophenols

If phenol is heated with more concentrated nitric add (in the presence of sulphuric acid), nitration occurs ultimately at the para and at both the ortho positions, giving picric acid or 2,4,6-trinitrophenol. To prepare picric acid, however, it is more convenient first to heat the phenol with sulphuric acid, whereby a mixture of 0- and p-phenol sulphonic acids is readily obtained. If this mixture is now heated with concentrated nitric acid, nitration occurs at the... 

Picric Acid and Ammonium Picrate. Picric acid (PA) (2,4,6,-trinitrophenol) was the first modem high explosive to be used extensively as a burster ia gun projectiles. It was first obtained by nitration of iadigo, and used primarily as a fast dye for silk and wool. It offered many advantages when compressed, it was used as a booster for other explosives, and when cast (melting poiat 122.5°C) served as a burster ia shell it was stable, iasensitive, nonhygroscopic, relatively nontoxic, and of high density when cast, and could be made economically by simple nitration. 

Because the highest possible interfacial area is desired for the heterogeneous reaction mixture, advances have also been made in the techniques used for mixing the two reaction phases. Several jet impingement reactors have been developed that are especially suited for nitration reactions (14). The process boosts reaction rates and yields. It also reduces the formation of by-products such as mono-, di-, and trinitrophenol by 50%. First Chemical (Pascagoula, Mississippi) uses this process at its plant. Another technique is to atomize the reactant layers by pressure injection through an orifice nozzle into a reaction chamber (15). The technique uses pressures of typically 0.21—0.93 MPa (30—135 psi) and consistendy produces droplets less than 1 p.m in size. The process is economical to build and operate, is safe, and leads to a substantially pure product. 

The compound can be prepared from 2,4,6-trinitrophenol (picric acid [88-89-1]) by reduction with sodium hydrosulfide (163), with ammonia —hydrogen sulfide followed by acetic acid neutralization of the ammonium salt (164), with ethanolic hydrazine and copper (165), or electrolyticaHy with vanadium sulfate in alcoholic sulfuric acid (159). Heating 4,6-dinitro-2-benzamidophenol in concentrated HQ. at 140°C also yields picramic acid (166). 

Reaction with cold nitric acid results primarily ia the formation of 5-nitrosahcyhc acid [96-97-9]. However, reaction with fuming nitric acid results ia decarboxylation as well as the formation of 2,4,6-trinitrophenol [88-89-1] (picric acid). Sulfonation with chlorosulfonic acid at 160°C yields 5-sulfosahcyhc acid [56507-30-3]. At higher temperatures (180°C) and with an excess of chlorosulfonic acid, 3,5-disulfosahcyhc acid forms. Sulfonation with hquid sulfur trioxide ia tetrachloroethylene leads to a nearly quantitative yield of 5-sulfosahcylc acid (1). 

During certain substitution reactions, the carboxyl group is often replaced by the entering group. An example is fuming nitric acid, which results in the formation of trinitrophenol. Another is the bromination of saUcyhc acid in aqueous solution to yield 2,4,6-tribromophenol [25376-38-9] (eq. 6). 

The procedure of simultaneous extracting-spectrophotometric determination of nitrophenols in wastewater is proposed on the example of the analysis of mixtures of mono-, di-, and trinitrophenols. The procedure consists of extraction concentrating in an acid medium, and sequential back-extractions under various pH. Such procedures give possibility for isolation o-, m-, p-nitrophenols, a-, P-, y-dinitrophenols and trinitrophenol in separate groups. Simultaneous determination is carried out by summary light-absorption of nitrophenol-ions. The error of determination concentrations on maximum contaminant level in natural waters doesn t exceed 10%. The peculiarities of application of the sequential extractions under fixed pH were studied on the example of mixture of simplest phenols (phenol, o-, m-, />-cresols). The procedure of their determination is based on the extraction to carbon tetrachloride, subsequent back-extraction and spectrophotometric measurement of interaction products with diazo-p-nitroaniline. 

Trimethyl benzene 2.4.6- Trinitrophenol, see Picric acid 2.4.6- Trinitrophenyl-methylnitramine, see Tetryl CT... 

Dipping solution Dissolve 100 mg picric acid (2,4,6-trinitrophenol) in 36 ml acetic acid (96%) and carefully add 6 ml perchloric acid (70%). 

Multiple substitution by strongly electron-withdrawing groups greatly increases the acidity of phenols, as the pK values for 2,4-dinitrophenol (4.0) and 2,4,6-trinitrophenol (0.4) in Table 24.2 attest. 

As we ve seen, aromatic substitution reactions usually occur by an electrophilic mechanism. Aryl halides that have electron-withdrawing substituents, however, can also undergo nucleophilic aromatic substitution. For example. 2,4,6-trinitrochlorobenzene reacts with aqueous NaOH at room temperature to give 2,4,6-trinitrophenol. The nucleophile OH- has substituted for Cl-. 

Historically, the outbreak of the first World War provided a stimulus for the industrial preparation of large amounts of synthetic phenol, which was needed as a raw material to manufacture the explosive picric acid (2,4,6-trinitrophenol). Today, more than 2 million tons of phenol is manufactured each year in the United States for use in such products as Bakelite resin and adhesives for binding plywood. 

Details have been collected for the determination of some 50 elements by this technique21,22 and it is possible to effect many difficult separations, such as Cu and Bi, Cd and Zn, Ni and Co it has been widely used in the nuclear energy industry. A number of organic compounds can also be determined by this procedure, e.g. trichloroacetic acid and 2,4,6-trinitrophenol are reduced at a mercury cathode in accordance with the equations... 

Trinitrophenol and Picric Acid (PA). Although the prepn of PA from phenol is no longer practiced in the USA, it was used as late as WWII in Engl, Fr, Ger, Italy, Japan and the USSR... 

---