Trinitro derivatives

It is also to he noted that ortho and para substitution often occur together in the same molecule, so that the group R enters the para and also both the ortho positions thus both aniline and phenol on bromination readily give symmetric (2,4,6) tribromo-compounds (p. 165), while both toluene and phenol on nitration readily give the symmetric trinitro-derivatives (p. 170). 

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 ... 

Urbanski et al (Ref 7) found that the addition of mono-, di- and trinitro derivatives of benz or toluene to PETN lowers its thermal stability as detd by heating the mixt in the temp range 120—132°. The extent of thermal decompn of PETN, heated alone or in mixts, can be estimated by the decreasing pH which indicates formation of acidic decompn products. Fig 3 shows how the addition of TNT enhances PETN decompn... 

Triketone (57), a key intermediate in the synthesis of 4,4,7,7,11,11-hexanitropentacyclo [6.3.0.0 .0 °.0 ]undecane (61) (Zlj-hexanitrotrishomocubane), has been synthesized independently by both Marchand and co-workers, and Fessner and Prinzach. Marchand and co-workers prepared the trioxime (58) from the corresponding triketone (57). Oxidation of (58) with peroxytrifluoroacetic acid in acetonitrile provides a direct route to the trinitro derivative (59) in 35 % yield, this yield reflecting an efficiency of 70 % for the oxidation of each oxime group. Subsequent oxidative nitration of (59) with sodium nitrite and potassium ferricyanide in aqueous sodium hydroxide yields the target T>3-hexanitrotrishomocubane (61). 

Paquette and co-workers synthesized the 5,11-dinitro isomer of 1,3-bishomopentaprismane (95) by treating the dioxime (94) with a buffered solution of m-CPBA in refluxing acetonitrile. A significant amount of lactone by-product (96) is formed during this step and may account for the low isolated yield of (95). Oxidative nitration of (95) with sodium nitrite and potassium ferricyanide in alkaline solution yields a mixture of isomeric trinitro derivatives, (97) and (98), in addition to the expected 5,5,11,11-tetranitro derivative (99), albeit in low yield. Incomplete reactant to product conversion in this reaction may result from the low solubility of either (97) or (98) in the reaction medium, and hence, incomplete formation of the intermediate nitronate anions. 

Some substrates like benzoic acid, benzaldehyde etc. are so deactivated that direct nitration to their trinitro derivatives is not possible. Direct nitration of benzoic acid with excess fuming nitric and concentrated sulfuric acids at a temperature of 145 °C for several hours results in the formation of 3,5-dinitrobenzoic acid (54-58 %). The use of oleum in such reactions can significantly reduce the rate of nitration due to carbonyl protonation (see Section 4.3.3). Consequently, indirect routes are used for the synthesis of polynitroarylenes like 2,4,6-trinitrobenzoic acid and 2,4,6-trinitrobenzaldehyde (Section 4.9). 

Other pyrimidine substrates to be converted to A, A -dinitro derivatives by loss of N-substituents include the diacyl compounds 503 and 504, and the di-(/ftt-butyl) compound 505 <2000JOC1200>. In the case of the disulfamic acid derivative 506, O-nitration also occurred, to give the trinitro derivative 507 <2000RCB1082>. 

Many nitro derivs of hydroxybenzaldehyde are known (See Beil 8, 56-7, 62-3, 83 [63]) but none of these is explosive, even the trinitro derivative, (N02)3C6H(0H)eH0, although it melts (161°) with decomposition. However reacting the latter with hydrazine sulfate produces the explosive ... 

N 16.7%, OB -91.7% pale yellow cryst (from ale), darkens 250°, mp 284° (with decomp) insol in most solvs except hot ale. Prepd by heating 5,7-Dinitro-indol-dicarboxylic acid in water. Its Et ester-Trinitro derivative melts at 202-205° and is stable (Ref 2)... 

Ksilil (Russ, Xylitej in Fr, Ksylit in Polish, TNX). A term given to commercial Trinitro-xylene (TNX) which consists chiefly of the trinitro derivatives, of meta-, with some ortho-and para-xylenes. It is a greyish-yellow substance prepd by the nitration of commercial xylene by mixed nitric-sulfuric acid. It is insol in w. Ksilil is slightly more, sensitive to initiation, and about as sensitive to impact and bullet test as TNT. It was used in composite expls as a partial substitute for TNT Refs 1) PATR 2145 (1955), p Rus 10-L 2) Gorst (1957), 100 3) Urbanski 1 (1964),... 

Lead Trinitroresorcinates. See under Trinitro-derivatives of Dihydroxybenzene in Vol 5 of Encycl, pp D1277-Lff... 

This compd was prepd by adding dropwise the above trinitro deriv in acetic anhydride to 100% nitric acid cooled to 5°. The soln was stirred for 20 mins at 5° and poured onto ice (Ref 2). Heat of combustion 1806cal/g (Ref 2) Other props reported are crystal d 1.79, hot bar ignition temp 219°, sensitivity — same as Pencolite (Ref 3)... 

Ethylester (Trinitro Deriv) of N.N - Dini-tromethylonedicarbamic Acid,... 

Dinitro-4metbyl-l -metbyl-benzenet CHsC H3CaHs(N02)2 mw 210,20, N13-33% mp 62.5°. Prepd from the 2,3,6-trinitro derivative (see below) by reaction with ammonia to give the 3 ammo, mp 143° which was reacted in ale with HNO to remove the amino -group... 

The key representative of aromatic nitramines is the trinitro derivative of phenyl-methylnitramine—tetryl. This is 2,4,6-trinitrophenyhnethylnitramineorpicrylmethyl-nitramine or N-2,4,6-tetranitro-N-methylaniline. 

The more recent work of Garkson, Holden and Malkin [4] shows, however, that the reaction proceeds somewhat differently. In fact, the dinitroderivative (II) which undergoes demethylation to the substance (IV) is formed first, and then the nitramine (VI) is isomerized (p. 5) to the trinitro derivative (V), before the latter is nitrated to tetryl ... 

As a starting material for the preparation of sym-trinitrotriazidobenzene, 1,3,5-trichlorobenzene is used. It is obtained by the chlorination of aniline and the removal of the amino group. Nitration to the trinitro derivative is described in Vol. I. The final reaction is simple powdered 1,3,5,-trichloro-2,4,6-trinitrobenzene is added to an aqueous alcohol solution of sodium azide. The precipitated product is washed with alcohol and water and dried at a moderate temperature. The product so obtained may be purified by crystallization from chloroform. 

With mineral acids, including nitric acid produced by the decomposition of powder, the N-nitroso compound undergoes rearrangement to form p-nitrosodiphenylamine (IV). This substance is readily oxidized to p-nitrodiphenylamine (V). Furthermore, the higher nitrated products, i.e. dinitro derivatives (VI) and (VII) and trinitro derivatives (VIII) may be formed in powder. Davis and Ashdown isolated 2,4,4 -tri-nitrodiphenylamine from American pyrocollodion powder by heating a sample in a closed vessel for 240 days at a temperature of 65°C. At the end of the heating period brown nitric oxides were given off by the powder. 

Dinitra-2, 6-diaminoanisole, gm-red ndls (from ethyl acet), mp 237° diffc sol in most org solvs was prepd, as above, using the 3, 4, 6-trinitro deriv (Ref 2)... 

Its trinitro deriv, 1,1 -Dinitramino-N-nitro dimetbylamine,, CH2NH.N02... 

Trinitro-4,4 -dicbloroazoxybenzene, yel crysts (from glac acet ac), mp 186-87°(Ref 3) 189° (dec rapidly at 193°)(Ref 2). Trinitro derivs are prepd by nitrating the dichloro deriv. Their expl props were not reported... 

Diethoxyazoxybenzene and Its Trinitro- Derivative. See under Azoxyphenetole in Vol 1, p A670-R... 

May be Considered as the parent compd of its trinitro deriv, although not used to prep it ... 

Tetranitrodietbylphenylenediamine, Cj H NgOg, not found in Beil or in CA N,N, 2,4,6-Pentamtro-N,N -diethyl-1,3-pheny-lenedfamine, (C N CgHtNWC ) mw 389.24, N 25.19% col crysts, mp 165° was obtd by nitrating the above trinitro deriv (Refs 1 2). Its expl props were not reported... 

Dinitro-, mp 166-67° and 2,4,6-Trinitro- derivs were prepd by Jadhov Merchant (Ref 2)... 

Uses Besides its uses as a reagent in analytical chemistry, as substitute for camphor in celluloid, it serves as a parent material for manuf of mono, di- and trinitro derivs used in the form of lead salts in priming expls... 

The Trinitro deriv, C9H7N3Og, was not found in the literature thru 1966 Refs 1) Beil 8, 242 2) Beil 8, 255... 

Di met hoxy picric Acid or 2,4,6-Trinitro-3,5-dimethoxyphenol, (H3CO)2C6H(NO 3OH, mw 289-16, N 14.53% crysts mp 76.5° was prepd by the following reactions 3,5 diuitromethoxy-benzene with AlCl3 at 130° yielded (Q2N)5C6OH which by Blanskma method fot the introduction of MeO groups yield the trinitro deriv (Ref 3) Refs 1) Beil 6, 1081 16305 2) Beil -... 

I.J. Schaffner, USRubber Co Quarterly Rept No 4(1948), pi2 (Trinitro deriv)... 

Blanksma Fohr (Ref 2) reported. prepn of the 2,4,6-trinitro deriv, mp 104°, bitter taste, by nitrating the dinitro compd with anhyd nitric acid sulfuric acid at 0°for... 

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