Acid picric

Picric acid [(trinitrophenol) (C6H3N307)] was found to be a suitable replacement for blackpowder in 1885 by Turpin, and in 1888 black-powder was replaced by picric acid in British munitions under the name Liddite. Picric acid is probably the earliest known nitrophenol it is mentioned in the alchemical writings of Glauber as early as 1742. In the second half of the 19th century, picric acid was widely used as a fast dye for silk and wool. It was not until 1830 that the possibility of using picric acid as an explosive was explored by Welter. 

Designolle and Brugere suggested that picrate salts could be used as a propellant, while in 1871, Abel proposed the use of ammonium picrate as an explosive. In 1873, Sprengel showed that picric acid could be detonated to an explosion and Turpin, utilizing these results, replaced blackpowder with picric acid for the filling of munition shells. In Russia, Panpushko prepared picric acid in 1894 and soon realized its potential as an explosive. Eventually, picric acid (1,2) was accepted all over the world as the basic explosive for military uses. 

Picric acid did have its problems in the presence of water it caused corrosion of the shells, its salts were quite sensitive and prone to acci- 

Picric acid (2,4,6-trinitrophenol, melting point 122°C) is manufactured by the nitration of mixed phenolsulfonates with mixed acid. Mixed acid increases the yield of desired products. 

The heavy metal salts of picric acid are dangerously sensitive, and its major use is for the manufacture of ammonium picrate (Explosive D). 

Picric Acid (Picronitric Acid, 2,4,6-Trinitrophenol, Trinitrophenol) 

Uses Picric acid is a white to yellowish, highly flammable crystalline substance. It is used in the manufacture of fireworks, matches, electric batteries, colored glass, explosives, and disinfectants. Pharmaceutical, textile, and leather industries also make use of picric acid. 

Toxicity Picric acid causes adverse effects on the skin of animals and humans like allergies, dermatitis, irritation, and sensitization. Absorption of picric acid by the system causes headache, fever, nausea, diarrhea, and coma. In high concentrations, picric acid is known to cause damage to erythrocytes, kidney, and liver.68 69 

Other Names Picric acid l-Hydroxy-2,4,6-trinitrobenzene 2,4,6-Trinitrophenol C.I. 10305 Carbazotic acid Melinite NSC 36947 NSC 56147 Nitroxanthic acid PA Picral Picronitric acid Trinitrophenol 

CA Index Name Phenol, 2,4,6-trinitro-CAS Registry Number 88-89-1 Merck Index Number 7410 Chemical Structure 

Chemical/Dye Class Nitro Molecular Formula C6H3N3O7 Molecular Weight 229.10 pH Range 0.0-1.3 

Physical Form Pale yellow glittering crystals 

Solubility Soluble in water, ethanol, benzene, chloroform insoluble in toluene UV-Visible 354 nm 

DEVELOPMENT OF MILITARY EXPLOSIVES Development of Picric Acid 

Pro/iL-y/nw. -Yellow, prism.itic crystals m. p. 122 5° sublimes on gently heating explodes on detonation o.isily soluble in alcohol and ether with diffiailly in cold, iiioie readily in hot u.itei the solution has i hitter taste. 

Reaction. -- i. To in ac ueous solution of juicric acid add a little polassiiiin cyanide solution, and warm. A brown ciystal-line precipitate of isopui puric acid separates. 

Add picric, acid ind i few drops of caustic soda to a dilute solution of grape suga c, md warm. I he liquid turns deep brown. 

Dissolve naphthalene in a little spirit, and add an equal quantity of a solution of picric acid in spirit. On cooling, yellow needles of naphthalene picrate separate, C,oHg.CQH20H(NO,)3. Benzene forms colourless crystals, anthracene, scarlet needles, having a similar composition. Sec Appendix, p. 295. 

RISK OF EXPLOSION BY SHOCK, FRICTION, FIRE, OR OTHER SOURCE OF IGNITION FORMS VERY SENSITIVE EXPLOSIVE METALLIC COMPOUNDS 

NOTE Picric acid should be kept moist with not less than half its own weight of water. In the laboratory, it is commonly used in alcoholic solutions. 

Pale yellow, odorless, intensely bitter crystals mp, 122-123°C. Explodes above 300oC.  

Explosive flash point, 150°C ignition temperature, less than 300°C oxidizing agent. Extinguish fire with water do not use carbon dioxide.2 

Explosive solid, which is usually stored as water-wet paste.3 

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Some nitro-compounds are themselves coloured and can be used as dyestuffs, e.g. picric acid. In this case the nitro-group can be considered to be the chromophore. For aliphatic nitro-compounds see nitroparaffins. 

CfiHsNjOs. Red needles m.p. 168-169°C. Soluble in dilute acids and alkalis. Prepared by reduction of picric acid with sodium hydrogen sulphide, ft is used for the preparation of azodyes, which can be after-chromed by treatment with metallic salts owing to the presence of a hydroxyl group ortho to the amino-group. 

It is prepared by the direct nitration of toluene with a mixture of nitric and sulphuric acids. TNT is a very stable, violent and powerful high explosive, but less sensitive to shock and friction than picric acid. It is widely used as a filling for shells, bombs, etc. often mixed with ammonium nitrate and other high explosives. The lower grades of TNT may contain isomers which under hot storage conditions may give rise to exudation. 

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 if stored in bulk should, for safety, first be damped. Smaller quantities may be safely kept whilst dry, but should be stored in bottles having cork or rubber stoppers glass stoppers should never be used for potentially explosive substances, because on replacing the stopper some of the material may be ground between the neck of the flask and the stopper, and so caused to explode. 

Reactions of Picric Acid, (i) The presence of the three nitro groups in picric acid considerably increases the acidic properties of the phenolic group and therefore picric acid, unlike most phenols, will evolve carbon dioxide from sodium carbonate solution. Show this by boiling picric acid with sodium carbonate solution, using the method described in Section 5, p. 330. The reaction is not readily shown by a cold saturated aqueous solution of picric acid, because the latter is so dilute that the sodium carbonate is largely converted into sodium bicarbonate without loss of carbon dioxide. 

To a cold aqueous solution of picric acid, add about an equal volume of dilute potassium cyanide solution. An orange coloration develops and rapidly darkens to a deep red. 

Uses of Picric Acid. The following further reactions of picric acid are used for analytical purposes in the laboratory. 

Identification of Aromatic Hydrocarbons. Picric acid combines with many aromatic hydrocarbons, giving addition products of definite m.p. Thus with naphthalene it gives yellow naphthalene picrate, C oHg,(N08)jCeHiOH, m.p. 152°, and with anthracene it gives red anthracene picrate, C 4Hio,(NOj)jCeHjOH, m.p. 138 . For practical details, see p. 394. 

Identification of Amines. Picric acid combines with many amines to give crystalline picrates, of general formula B,(NO )aCeHjOH, where B is a molecule of a monacidic base. These picrates have usually sharp melting- or decomposition-points, and serve to characterise the amines concerned. They may be formed either by (a) direct union of the acid and the base in a suitable solvent, or (6) by the interaction of sodium picrate and a salt of the amine in aqueous solution. 

If an ethanolic solution of picric acid is similarly added to one of aniline, no precipitation occurs, owing to the high solubility of aniline picrate in ethanol. If, however, a cold aqueous solution of aniline hydrochloride is added to a similar solution of sodium picrate and the mixture shaken, yellow crystals of aniline picrate, m.p. 165 , soon separate. 

Picric acid is used on a large scale as a high explosive, but for this purpose requires a detonator. If a few small crystals of the pure acid are heated on a crucible lid, they first melt, and ultimately burn harmlessly with a smoky flame. Metallic salts of picric acid are much less stable than the free acid,... 

If cold saturated ethanolic solutions of the recrystallised tetrahydrocarbazole and of picric acid are mixed and stirred, the chocolate-brown picrate of the carbazole slowly crystallises. After it has been filtered off at the pump, washed with a small quantity of ethanol, and dried, it has m.p. 145-146°. 

I or examples of other similar methopicriitcs uniting tvith picric acid or sodium picrate to livc "double piciatcs" ot larioiis stiibilifics, see b. (i. M inii... 

A) Picrates. Attempt precipitation of picrates by (a) mixing cold ethanolic solutions of the amine and of picric acid (saturated) or... 

Some less reactive tertiary amines can be mixed with an excess of methyl toluene-/)-sulphonate, m.p. 28 , and the mixture (without a solvent) heated to a much higher temperature. The mixture is allowed to cool, but before solidification occurs, it is thoroughly stirred with ether to extract unused sulphonate, and the insoluble quaternary metho-toluene-/)-sulphonate may then crystallise. If ciystallisation does not occur, dissolve this residue in ethanol and treat one portion with ethanolic picric acid (to precipitate the methopicrate) and another portion with cold concentrated ethanolic sodium iodide (to precipitate the methiodide). (M.ps. of the siilphon.ates, pp. 553 -554.)... 

Make a concentrated solution of anthracene in hot acetone. To about 2 ml. of this solution add a cold concentrated acetone solution of picric acid drop by drop, and note the formation of a red coloration which becomes deeper on further addition of the acid. If excess of picric acid is added, however, the solution becomes paler in colour, and this is to be avoided if possible. Boil to ensure that both components are in solution and then transfer to a small porcelain basin or watch-glass ruby-red crystals of anthracene picrate separate out on cooling. The product, however, is often contaminated with an excess of either anthracene or of picric acid, which appear as yellowish crystals. 

Picric acid is usually stored damp for safety, and acetone is therefore a better solvent than benzene or this test the solutions musi be almost saturated, however. 

Place a mixture of 0-5 g. of finely powdered thiourea, 0-5 g. of the alkyl halide and 5 ml. of alcohol in a test-tube or small flask equipped with a reflux condenser. Reflux the mixture for a j)eriod depending upon the nature of the halide primary alkyl bromides and iodides, 10-20 minutes (according to the molecular weight) secondary alkyl bromides or iodides, 2-3 hours alkyl chlorides, 3-5 hours polymethy lene dibromides or di-iodides, 20-50 minutes. Then add 0 5 g. of picric acid, boil until a clear solution is obtained, and cool. If no precipitate is obtained, add a few drops of water. RecrystaUise the resulting S-alkyl-iso-thiuronium picrate from alcohol. 

Picrates of p-naphthyl alkyl ethers. Alkyl halides react with the sodium or potassium derivative of p-naphthol in alcoholic solution to yield the corresponding alkyl p-naphthyl ethers (which are usually low m.p. solids) and the latter are converted by alcoholic picric acid into the crystalline picrates ... 

Mix together 1 0 g. of pure p-naphthol and the theoretical quantity of 50 per cent, potassium hydroxide solution, add 0-5 g. of the halide, followed by sufficient rectified spirit to produce a clear solution. For alkyl chlorides, the addition of a little potassium iodide is recommended. Heat the mixture under reflux for 15 minutes, and dissolve any potassium halide by the addition of a few drops of water. The p-naphthyl ether usually crystallises out on cooling if it does not, dilute the solution with 10 per cent, sodium hydroxide solution untU precipitation occurs. Dissolve the p-naphthyl ether in the minimum volume of hot alcohol and add the calculated quantity of picric acid dissolved in hot alcohol. The picrate separates out on cooling. Recrystallise it from rectified spirit. 

Picrates, Picric acid combines with amines to yield molecular compounds (picrates), which usually possess characteristic melting points. Most picrates have the composition 1 mol amine 1 mol picric acid. The picrates of the amines, particularly of the more basic ones, are generally more stable than the molecular complexes formed between picric acid and the hydrocarbons (compare Section IV,9,1). 

If the amine is soluble in water, mix it with a slight excess (about 25 per cent.) of a saturated solution of picric acid in water (the solubility in cold water is about 1 per cent.). If the amine is insoluble in water, dissolve it by the addition of 2-3 drops of dilute hydrochloric acid (1 1) for each 2-3 ml. of water, then add a sUght excess of the reagent. If a heavy precipitate does not form immediately after the addition of the picric acid solution, allow the mixture to stand for some time and then shake vigorously. Filter off the precipitated picrate and recrystaUise it from boiling water, alcohol or dilute alcohol, boiUng 10 per cent, acetic acid, chloroform or, best, benzene. 

The following alternative procedure may sometimes be employed. Dissolve 0-5 g. of the amine in 5 ml. of rectified spirit and add 5 ml, of a cold saturated solution of picric acid in alcohol. Warm on a water bath... 

Unlike aliphatic hydrocarbons, aromatic hydrocarbons can be sul-phonated and nitrated they also form characteristic molecular compounds with picric acid, styphnic acid and 1 3 5-trinitrobenzene. Many of the reactions of aromatic hydrocarbons will be evident from the following discussion of crystalline derivatives suitable for their characterisation. 

Picrates, Many aromatic hydrocarbons (and other classes of organic compounds) form molecular compounds with picric acid, for example, naphthalene picrate CioHg.CgH2(N02)30H. Some picrates, e.g., anthracene picrate, are so unstable as to be decomposed by many, particularly hydroxylic, solvents they therefore cannot be easily recrystaUised. Their preparation may be accomplished in such non-hydroxylic solvents as chloroform, benzene or ether. The picrates of hydrocarbons can be readily separated into their constituents by warming with dilute ammonia solution and filtering (if the hydrocarbon is a solid) through a moist filter paper. The filtrate contains the picric acid as the ammonium salt, and the hydrocarbon is left on the filter paper. 

The foUowing are typical experimental details for the preparation of naphthalene picrate. Dissolve 0 -1 g. of naphthalene and 0-2 g. of picric acid separately in the minimum volume of hot rectified spirit (about 2 ml.), mix the solutions and allow to cool. FUter and wash with 2 ml. of alcohol. RecrystaUise from hot alcohol, ethyl acetate or ether. 

Picric acid, the 2 4 6-trinitro derivative of phenol, cannot be prepared in good yield by the action of nitric acid upon phenol since much of the latter is destroyed by oxidation and resinous products are also formed. It is more convenient to heat the phenol with concentrated sulphuric acid whereby a mixture of o- and p-phenolsulphonic acids is obtained upon treatment of the mixture with concentrated nitric acid, nitration occurs at the two positicsis mela to the —SOjH group in each compound, and finally, since sulphonation is reversible, the acid groups are replaced by a third iiitro group yielding picric acid in both cases ... 

Picrates of aromatic ethers. Most phenohc ethers react with picric acid in chloroform or alcoholic solution to yield crystalUne picrates (compare At oTnatic Hydrocarbons, Section IV,9,1). 

Dissolve 0 01 mol of the phenohc ether in 10 ml. of warm chloroform, and also (separately) 0 01 mol of picric acid plus 5 per cent, excess (0 -241 g.) in 10 ml. of chloroform. Stir the picric acid solution and pour in the solution of the phenohc ether. Set the mixture aside in a 100 mb beaker and ahow it to crystallise. Recrystahise the picrate from the minimum volume of chloroform. In most cases equahy satisfactory results may be obtained by conducting the preparation in rectified spirit (95 per cent. CjHgOH). The m.p. should be determined immediately after recrystallisation. It must be pointed out, however, that the picrates of aromatic ethers suflFer from the disadvantage of being comparatively unstable and may undergo decomposition during recrystaUisation. 

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