2,4,6-Tetryl

Tetryl, also called tetranitromethylaniline, has a melting point of about 130°C with some decomposition. It is nonhygroscopic and practically insoluble in water but highly soluble in acetone and benzene. It can be stored for over 20 years at ambient temperatures with no noticeable change in properties. 

Tetryl is prepared by the nitration of dimethyl aniline followed by the oxidation of one of the n-methyl groups to CO2 and more nitration. 

Tetryl is used as a booster where it is mixed with TNT (called tetrytol) and some graphite to help pressing the mixture. 

Ammonium nitrate is easily made by reacting nitric acid with ammonium hydroxide  

The reaction is exothermic and can be carried out in a borehole prior to its detonation. The thermal decomposition of NH4NO3 yields nitrous oxide, N2O  

In the U SA, tetryl has not been considered for use in new explosive trains since 1973, however, it is still manufactured and used in Germany and India. On the contrary, it is no longer synthesized in the UK as both the material itself and its manufacture are considered to pose health hazards. 

An explosive called tetryl was also being developed at the same time as picric acid. Tetryl was first prepared in 1877 by Mertens and its structure established by Romburgh in 1883. Tetryl (1.3) was used as an explosive in 1906, and in the early part of this century it was frequently used as the base charge of blasting caps. 

Around 1902 the Germans and British had experimented with trinitrotoluene [(TNT) (C7H5N306)], first prepared by Wilbrand in 1863. The first detailed study of the preparation of 2,4,6-trinitrotoluene was by Beilstein and Kuhlberh in 1870, when they discovered the isomer 2,4,5-trinitrotoluene. Pure 2,4,6-trinitrotoluene was prepared in 1880 by Hepp and its structure established in 1883 by Claus and Becker. The manufacture of TNT began in Germany in 1891 and in 1899 aluminium was mixed with TNT to produce an explosive composition. In 1902, TNT was adopted for use by the German Army replacing picric acid, and in 1912 the US Army also started to use TNT. By 1914, TNT (1.4) became the standard explosive for all armies during World War I. 

Production of TNT was limited by the availability of toluene from coal tar and it failed to meet demand for the filling of munitions. Use of a mixture of TNT and ammonium nitrate, called amatol, became wide- 

Other Names Aniline, A-methyl-A,2,4,6-tetranitro- 2,4,6,N-Tetramtro-Af-methylaniline 2,4,6-Tetryl 2,4,6-Trinitro-A-methyl-A-nitroaniline 2,4,6-Trinitrophenyl-A-methyInitramine 2,4,6-Trinitrophenylmethylnitroamine CE A-Methyl-Af,2,4,6-tetranitroamline N-Methyl-N-picrylnit-ramine A-Picryl-A-methylnitramine NSC 2166 Nitramine Nitramine (indicator) Picrylmethyl-nitramine Picrylnitromethylamine TetraUt Tetralite Tetril Tetryl CA Index Name Benzenamine, A-methyl-iV,2,4,6-tetranitro-CAS Registry Number 479-45-8 Merck Index Number 6573 Chemical Structure 

Chemical/Dye Class Nitro Molecular Formula C7H5N5O8 Molecular Weight 287.14 pH Range 10.8-13.0 

Solubility Insoluble in water soluble in ethanol, ether, benzene, acetic add Melting Point 130-132°C 

Boiling Point (Calcd.) 503.7+ 50.0°C Pressure 760 Torr Synthesis Synthetic methodsi n 

Major Applications Explosives,2.3.9-iv paints, 1 food storage  

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Tetryl Tetrytols Teuber reaction Teutsch route Tevdek II... 

Tetiyl. 2,4,6-Trinitrophenylmethylm tramine (tetryl) was used ia pressed form, mostly as a booster explosive and as a base charge ia detonators and blasting caps because of its sensitivity to initiation by primary explosives and its relatively high energy content. Properties are presented ia Table 11 (173). Batch and continuous processes for the production of tetryl have been developed. Tetryl is no longer used ia the United States and has been replaced by RDX (174-178). 

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

Effect of Compaction on Predetonation Coiumn Length of Tetryl. p... 

Uses It can be used as a secondary charge in detonators replacing Tetryl. Mixts with Diaz onitrophenol (Encycl 2, B59) or Tetrazene... 

Measurement of Acidity or Alkalinity of Explosives. (Measurement of pH value). These tests consist essentially of extrg the sample of expl with w (either cold in the case of liquids such as NG, or hot for solids such as TNT, Tetryl, PA, etc), and detg the acidity of the resulting extr either by titration, colorimetric methods or by means of a pH meter. These tests are described under the individual compds... 

Heat of fusion. The Qfusi0n °f mixts of MEDINA with PETN, HMX, TNT, RDX, BTNEU, EDNA, Styphnic Acid, PA, Tetryl are given in Ref 13, p 9 ... 

Toxicity. MEDINA is apparently non-toxic to rabbit penile mucosa its cumulative effect on abraded and intact rabbit skin is slightly greater than Tetryl no damage was observed to rabbit cornea and there was no evidence of sensitization by subcutaneous injection in guinea pigs. It was concluded that its toxicity is similar to that of Tetryl (Ref 11, p 138)... 

Exposure of moist expls (0.5% moisture) with common metals at 50° for two years (two months at 71° and 100% relative humidity for phosphate coated steel) resulted in from very slight to very heavy corrosion for practically all of the metals shown in the above table. Stainless steel was unaffected by any expl, acid proof black painted steel was not affected by 75/25 Tetrytol and 50/50 Pentolite, and Mg-Al alloy (Jl) was unaffected by BkPdr. Phosphate coated steel exhibited considerable corrosion with BkPdr, but was unaffected by TNT, RDX, Comp B, Tetryl or 50/50 Pentolite (Ref 3)... 

Azide Powder Styphnate B PETN RDX Tetryl TNT Amatol H alette Tetrytol Ednatol Pentolite... 

Pure samples are best prepd by the methylation of acetanilide or benzanilide to the N-methyl compds followed by acid hyd. It has been prepd commercially by the action of methyl ale on aniline in an autoclave under press and by the action of methyl amine on halobenzenes. For a summary of prepns see Refs 6 9. It may be separated from aniline and dime thy laniline by treatment of the mixt with benzenesulfonyl chloride. Dimethylamline fails to react and is extd out with dil acid. Aniline forms benzenesulfonanilide which is acidic and is removed by washing with dil base, leaving the N-methylbenzenesulfonanilide. Purified N-methylaniline is obtd by acid hyd (Ref 8). N-Methylaniline is used as an additive to raise the octane no of motor fuels (Ref 6), as a dyestuff intermediate (Ref 3), in the prepn of Tetryl (see below), and in the prepn of Methylcentralite (Encycl, Vol 2, C137-R)... 

It is prepd by the action of methylamine on 4-chloro-l-nitrobenzene (Ref 5) by the action of methyl iodide (Ref 6), or methyl sulfate on 4-nit roaniline (Ref 7) or by the hydrolysis of 4-nitro-N-methylformanilide with hot coned aq HC1 (Ref 8). In a study of the effect of nitric acid concn on the prods of the nitration of N,N-dimethylaniline to form Tetryl, it was isolated in low yield by the action of nitric acid, d 1.046g/cc, plus Na nitrite on N,N-dimethylaniline (Ref 10). A eutectic mixt with N-ethyl-4-nitroaniline has been patented as a stabilizer for NC (Ref 12). Studies at NPF indicate that 4-nitro-N-methyl-aniline is superior to Centralite, 2-nitrodiphenyl-amine, or Acardite in stabilizing. NC Refs 1) Beil 12, 586, (295) 1125 ... 

Dinitro-N-methylaniline, orange needles, mp 106-07° (Ref 5). Q 895.35kcal/mole, Qf 2.45kcaJ/mole, 6.55kcal/mole (Ref 15). It has been found as a by-prod in the prepn of the 2,4-isomer (Ref 15). It has been sepd from other compds related to Tetryl by thin layer chromatography (Ref 19)... 

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/... 

Trinitro-N-methylaniline (N-methyl picra-mide), yellow needles from EtOH contg acid, mp /l4.8° (Refs 4 7) the UV spectrum has a peak at 340 and a shoulder at 410—20m (Ref 19) CA Registry No 1022-07-7. It is prepd by the hydrolysis of the N nitroso compd (see below) at 70—80° (Ref 5) by the action of coned sulfuric acid (Ref 8) or UV light (Ref 12) on Tetryl by the action of methyl amine on Ethyl Picrate (Ref 18) or Tetryl (Ref 7) or by the action of nitric acid (d 1.42g/cc) at 0° on N,N-dimethylaniline (Ref 10). It is present in crude Tetryl and is the active der-matitic agent in the latter (Ref 12). It can be isolated from crude Tetryl and identified by thin layer chromatography (Ref 21)... 

Tetranitro-N-methylani lines (except Tetryl), C7H5N5O8, mw 287.15, N 24.39%, OB to CO2 —47.4%. The following isomers have been reported in the literature, but theu expl props have not been examined... 

AC4 r-Hexanitro-N-methylaniline N-Methyl-N-pen tanitrophenylnitramine, 2,5-Dinitro tetryl). 

Tetryl (Refs 2 3) thermal stability at 90°, evolves oxides of nitrogen in hrs (Refs 2 3) Refs 1) Beil 13, 425 2) Van Duin Van... 

It is an expl, more powerful than TNT (about 133% by Ballistic Mortar), and comparable to Tetryl in sensitivity. Its Vel of Deton is 7420 m/sec at d 1.5g/cc, and 5490m/sec at d l.Og/cc. Qc is about 380kcal/mole. It is practically non-hygroscopic and its thermal stability is satisfactory. Has been used by DuPont Co as a base charge for some detonators Refs I) Beil — not found 2) H. Biltz et al, JPraktChem 142, 193-200 (1935) CA 29, 3652 (1935) 3) Anon, Report on Nitro-... 

Nitroisobutylglycol dinitrate). CH3.C.N02(CH20N02)2, mw 225.14, N 18.67%, OB to C02 —24.87%, mp 38°, ignites above 240°. Prepd from the glycol by nitration with mixed acid, with 90% yield. Brisance, crushes 53g sand, equivalent to Tetryl. Qc is 531.4cal/mole. Impact sensitivity, FI 86% relative to PA, with Bruceton No 5 machine,... 

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