Trinitro nitrate

In the oily product, the ratio of dinitro nitrate and trinitro nitrate is about 70 30. The product is diluted by water for the waste acids. After separation, the precipitate includes more nitrate ester, which contains about 90 % glycerine dinitrate. 

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 ... 

The operation of the nitronium ion in these media was later proved conclusively. "- The rates of nitration of 2-phenylethanesulphonate anion ([Aromatic] < c. 0-5 mol l i), toluene-(U-sulphonate anion, p-nitrophenol, A(-methyl-2,4-dinitroaniline and A(-methyl-iV,2,4-trinitro-aniline in aqueous solutions of nitric acid depend on the first power of the concentration of the aromatic. The dependence on acidity of the rate of 0-exchange between nitric acid and water was measured, " and formal first-order rate constants for oxygen exchange were defined by dividing the rates of exchange by the concentration of water. Comparison of these constants with the corresponding results for the reactions of the aromatic compounds yielded the scale of relative reactivities sho-wn in table 2.1. 

Electrophilic substitution reactions of diarylamines are easily accompHshed since the amino group activates the aromatic ring. Thus, DPA reacts with bromine or chlorine to form the 2,2H,4 tetrahalo derivative nitration usually produces the trinitro compound. 

N 16.47%, OB to C02 —103.4%, triclinic needles (from ale). prisms (from acet), mp 238.2°, bp expl at 415°, d 1.48g/cc. Insol in w, si sol in hot ale eth, misc in hot acet benz. Can be prepd by treating mesitylene with a mixt of. nitric sulfuric acids in the cold (Refs 2 3). Blanksma (Ref 4) prepd it by dissolving mesitylene in sulfuric acid, partial sulfonation taking place, and then adding the soln to nitric acid, with the pptn of trinitio-mesitylene. Kholevo (Ref 6) nitrated mesitylene with nitric acid 27, sulfuric acid 69, water 4% to yield white crysts. The expl power of trinitro-mesitylene is less than PA (Ref 9), and it develops a bomb press 84% that of TNT (Ref 8), Its impact sensitivity is 52% that of TNT (Ref 7), and it expls at 415° (Ref 5)... 

Registry No 19092-03-6. It has been shown to be an intermediate in the prepn of Tetryl from N,N-dimethylaniline as it can be prepd from N,N-dimethylariiline or 2,4-dinitro-N-methylaniline by the action of 70% nitric acid in 90% yield (Refs 13 14) and can be nitrated to Tetryl with a mixt of 64% sulfuric acid, 15% nitric. acid, and-21%-w yield 91.9% (Ref 14). It can be isolated from commercial Tetryl and identified by thin layer chromatography (Ref 21) N,2,6-Trinitro-N-methylaniline (2,6-dinitrophenyl-methylnitramine), mp 110.8 874.9kcal/... 

N, 2,3,4-Tetranitro-N-methylaniline (2,3,4-trinitrophenyl-N-methylnitramine), mp 122.5° prepd by the nitration of 2,3,5-trinitro-N-niethyl-aniline with nitric acid (concn unspecified)... 

N,2,4,5-Tetranitro-N-methylaniline (2,4,5-trinitrophenyl-N-m ethylnitramine), needles from nitric acid mp 143.5° prepd by nitration of 2,4,5-trimtro-N-methylaniline, or by the action of 90% nitric acid on 2,4,5-trinitro-N.N-dimethylaniline (Refs 1 3) 2,3,4,6-Tetranitro-N-methylaniline, mp 127° prepd by the action of sulfuric acid on N,2,4,5-tetranitro-N-methylaniline (Refs 2 3)... 

X,X-Trinitro-1-Methyl naphthalene, mp 180-81°, straw-yellow needles from CC14. V si sol in ale, appreciably sol in CCI4, chlf AcOH. Prepn from 4-nit ro-1-me thy lnaphthalene by nitration with mixed nitric-sulfuric acids Refs 1) Beil 5, (266) 2) R. Lesser A. 

X,X,X-Trinitro-2-Methylnaphthalene, mp 182°, cryst from benz. Prepn from 2-methylnaph-thalene in glac AcOH by nitration at 0° with fuming nitric acid Ref Beil 5, 1635 ... 

Mortier and Sandon. Patented in 1897 the following cannon powd K nitrate 65, trinitro-cresol 25, charcoal 9 stearic acid 1%... 

Nitrated Solvent Naphtha (N.S.N.). As nitration of crude solvent naphtha by the usual one-stage method results in yields that are too low, because of oxidation, E. Blecher et al (Ref 3) proposed nitrating only the refined material, and in two stages. The two-stage method is described in Colver, pp 255 686—87 (Ref 4). The product consists chiefly of 2,4,6-Trinitro-mesitylene (see under Mesitylene and Deriva- tives in this Vol), and 3,5,6-trinitropseudocumene, with small quantities of the nitrated products of xylene, ethylbenzene, etc... 

Trinitro-1-Naphthol (2,4,5-Trinitro-1-hydroxy naphthalene). Yellow leaflets or prisms mp 189—90° bp, explds. Sol in hot AcOH, si sol in hot w, ale, benz, eth acetate, xylene cold AcOH. Prepn from 2,4-dinitro-naphthol by nitration, or from 4-chlor-1,3,8-trinitronaphthalene by heating with 0.1 N NaOH in w or ale... 

Tri nitro-1 -N aphthol (2,4,7 -Trinitro-1 -oxy-naphthalene). Yellow prisms from AcOH or benz, mp 145° (decompn). Sol in AcOH glac AcOH. Prepn from 2,4-dinitro-l-naphthol by mixed acid (nitric-sulfuric-acetic) nitration. The compound is extracted as the Na salt from... 

X,4,6-Trinitro-2-Naphthol (X, 4,6-Trinitro- 2-oxy-naphthalene). Yellow needles from ale, mp 150° (decompn). Prepn from 4,6-dibromo-2-naphthol by nitration with nitrous-nitric acid. Rapid decompn occurs above 159°... 

Oxybenzoic Acid, Nitrated Leed Salt (Lead 2,4,6-Trinitro-3-Oxybenzoate, Trinitrometa-oxybenzoate in Fr). H. Ficheroulle and A. Kovache (Ref) prepd and characterized this material... 

The crude product contains isomers other than that required and also nitrated phenolic compounds resulting from side reactions. The usual method of purification is to treat the crude product with sodium sulphite, which converts asymmetric trinitro compounds to sulphonic acid derivatives, and to wash out the resulting soluble products with alkaline water. The purity of the product is determined by the melting point, the minimum value for Grade I TNT commonly being 80-2°C. Unless adequate purity is achieved, slow exudation of impurities can occur during storage and the TNT then becomes insensitive. 

Nitration of a series of mesomeric betaines was extensively studied in connection with their potential use as explosives (Scheme 3). Nitration of l,2,3-triazolo[2,l- ]benzotriazole 74 can be achieved selectively, occurring first at the 7-position which is followed by nitration at the 3- and 5-positions. Thus, nitration with 45% nitric acid gives a mixture of 7-nitro derivative 75 (39%) and dinitro derivative 76 (58%), while 70% nitric acid yields a mixture of 3,7- (52%), 5,7- (23%), and 3,5-dinitro (5%) isomers 76-78. Clean trinitration to 3,5,7-trinitro-l,2,3-triazolo[2,l- ]benzotriazole 79... 

When l,3r5-triazine is allowed to react with dinitrogen pentoxide and quenched with methanol the cis and trans isomers of 13 3-trinitro-2,4,6-trimethoxy-hexahy drotriazine are obtained. Nitration of the triazine in deuterated nitromethane at -10 °C affords the mixture of cis and trans 2,4,6-trinitrato-l,3,5-trinitro-hexahydro-13,5-triazines which are decomposed at room temperature . Hexahydro-13,5-triaryl-133-triazines cyclorevert upon exposure to HC1 gas to give solid arylmethylene iminium chlorides as new versatile reagents... 

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). 

Trinitrobenzene is present in crude TNT manufactured by mixed acid nitration and results from methyl group oxidation followed by decarboxylation." In fact, a convenient method for the synthesis of 1,3,5-trinitrobenzene involves oxidation of 2,4,6-trinitrotoluene with a solution of sodium dichromate in sulfuric acid, followed by decarboxylation of the resulting 2,4,6-trinitrobenzoic acid in boiling water." 1,3,5-Trinitrobenzene is prepared from 2,4,6-trinitro-m-xylene by a similar route." 2,4,6-Trinitroanisole can be prepared from the... 

Chapman studied the nitrolysis of symmetrical methylenediamines. The nitrolysis of N, N, N, M-tetramethylmethylenediamine with nitric acid-acetic anhydride-ammonium nitrate mixtures gives both dimethylnitramine and RDX the latter probably arises from the nitroT ysis of hexamine formed from the reaction of ammonium nitrate and formaldehyde released from the hydrolysis of the methylenediamine. The same reaction with some morpholine-based methylenediamines (105) allows the synthesis of l,3,5-trinitro-l,3,5-triazacycloalkanes (106). 

Treatment of DPT (239) with dinitrogen pentoxide in pure nitric acid leads to the isolation of the nitrate ester (249), an unstable explosive which is highly sensitive to impact and readily undergoes hydrolysis. A low nitration temperature favours the formation of (249) and its presence during the nitrolysis of hexamine is clearly undesirable. The nitrolysis of DPT (239) with one equivalent of pure nitric acid in an excess of acetic anhydride yields 1-acetomethyl-3,5,7-trinitro-l,3,5,7-tetraazacyclooctane (251), a useful starting material for the synthesis of other explosives. ... 

The Mannich condensation between nitromethane, formaldehyde and t-butylamine, followed by nitrolysis of the resulting product (101), has been used to synthesize 1,3,5-trinitro-hexahydropyrimidine (102) (TNHP) treatment of the latter with formaldehyde in a Henry type methylolation, followed by 0-nitration with nitric acid, yields the nitrate ester (103). ... 

Li and co-workers recognised the potential of cyclic IV-nitroureas as energetic materials and reported the synthesis of 2,4,6,8-tetranitro-2,4,6,8-tetraazabicyclo[3.3.0]octane-3-one (109) (K-55) from the nitration of 2,4,6,8-tetraazabicyclo[3.3.0]octane-3-one dihydrochloride (108) with absolute nitric acid in acetic anhydride at room temperature the latter obtained from the condensation of lV,lVL(iiformyl-4,5-dihydroxyimidazolidine (107) with urea in aqueous hydrochloric acid. Pagoria and co-workers " " reported the synthesis of 2,4,6-trinitro-2,4,6,8-tetraazabicyclo[3.3.0]octane-3-one (110) (HK-55) in 72% yield from the nitration of (108) with 90 % nitric acid in acetic anhydride at subambient temperature (Table 5.3). HK-55 has a relatively high density (1.905 g/cm ) coupled with a low sensitivity to shock. 

The nitrolysis of hexamine is a direct route to the military high explosives 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX) and l,3,5,7-tetranitro-13,5,7-tetraazacyclooctane (HMX). " The direct nitrolysis of hexamine with dinitrogen pentoxide in absolute ifitric acid provides RDX in 57 % yield. RDX prepared by this process is exceptionally pure, but other reagents, like ammonium nitrate-nitric acid-acetic anhydride, give much higher yields, partly because they use ammonium nitrate to supplement for ammonium nitrogen deficiency in the reaction. 

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