Tetryl reaction

Tetryl Tetrytols Teuber reaction Teutsch route Tevdek II... 

Tetryl. In the manufacture of Tetryl, it is usual not to nitrate dime thy laniline directly, but to dissolve it first in coned sulfuric acid and then to nitrate the dimethylaniline sulfate so obtained. Direct nitration of dimethylaniline proceeds so violently that it can be carried out only under specialized conditions. Many years experience of Tetryl manufacture has shown that the ratio of sulfuric acid to dimethylaniline should not be lower than 3 1, since a smaller amount of sulfuric acid may be detrimental to the nitration process. However, the ratio of sulfuric acid to dimethylaniline must not be too high, otherwise Tetryl yield is decreased. Temp must be maintained between 20-45° to avoid sulfonation of the benzene ring. Care must be exercised not to leave any unreacted dimethylaniline prior to introduction of nitric acid, because of the potential violence of the dimethyl-aniline-nitric acid reaction. Consequently, continuous methods of prepn are to be preferred as they inherently minimize accumulation of unreacted dimethylaniline... 

The two studies, taken together, suggest that tetryl, not TNT, leads to the formation of picrate, since neither the LANL results nor the Holston results showed the formation of picrate in the absence of tetryl. If this is correct, the formation of lead picrate cannot occur when Composition B and M28 propellant are coprocessed, provided no tetryl contamination is present. The solubility of lead picrate in the reaction medium under consideration is not known. Because lead in solution at high pH is predominantly in the form of plumbite ion (HPb02), the concentration of free Pb2+ ions should be very low, and the solubility product of lead picrate would have to be exceedingly small for... 

The steel burster tubes from projectiles are unaffected by the caustic in the COINS. To enhance reaction rates, burster tubes are sheared into three pieces by the burster size-reduction machine to provide more surface area for the reaction of tetryl with caustic. The... 

Other explosives, such as 2,4,6-trinitroanisole (7),33b.226 2,4,6-trinitroaniline (picramide), and tetryl (101), ° are conveniently prepared from the nitration of the corresponding 2,4-dinitro derivatives, which in turn, are prepared from the reaction of 2,4-dinitrochlorobenzene with the appropriate nucleophile. 

Tetryl (8) can be synthesized in two steps from 2,4-dinitrochlorobenzene (231). Thus, reaction of the latter with methylamine under aqueous conditions yields 2,4-dinitro-lV-methylaniline (228), which readily undergoes nitration to tetryl (8) on treatment with mixed... 

Tetryl has been synthesized by treating picryl chloride with the potassium salt of methyl-nitramine but the reaction is of theoretical interest only. ... 

Amino-1,2,4-triazole is a useful starting material for the synthesis of many 1,2,4-triazole-based explosives. Jackson and Coburn synthesized a number of picryl- and picrylamino-substituted 1,2,4-triazoles. PATO (99) is synthesized from the reaction of 3-amino-1,2,4-triazole (98) with picryl chloride (67). ° PATO has also been synthesized from the reaction of 3-amino-l,2,4-triazole with A,2,4,6-tetranitromethylaniline (tetryl). PATO has a low sensitivity to impact and is thermally stable up to 310 °C. PATO (VOD 7469 m/s) exhibits lower performance to TATB (VOD 8000 m/s) which is the common benchmark standard for thermal stability and insensitivity in explosives. 

The addition of certain nitroaromatic explosives to basic nonaqueous solutions results in the formation of a strongly colored reaction product, as shown in Figure 13.10. When comparing a set of 13 different explosives, only TNT, TNB, and tetryl formed these visibly colored products at a concentration of 10 mg/L... 

Figure 13.10 Visible absorption spectra for 1 mg/L TNT, TNB, and tetryl in acetoni-trile/methanol [87.5/12.5 (v/v)] containing 2.5 mM NaOH and 1.0 mM SDS. Inlaid are the chemical reactions of TNT, TNB, and tetryl in basic acetonitrile/methanol. (Reprinted from [38] with permission from Elsevier.)...

Cook (Ref 1), in describing thermal decomposition of some HE s conducted in the quartz spring apparatus (described in Ref 1, p 175 and shown there in Figs 8.1a 8.1b), stated that PETN, RDX, Tetryl and to a small extent TNT decomposed autocatalyti-cally. EDNA followed the first-order decomposition law only until about 5% of the explosive had decomposed and then the reaction stabilized. The term autostabilization was applied here on the supposition that one of the condensed decomposition products of EDNA which accumulated in the explosive apparently tended to stabilize the bulk of expl and thus slow down the decomposition. After about 10% of the expl had decompd, however, the "autocatalysis developed. 

Dremin Shvedov (Ref 3) measured by an electromagnet method the CJ pressure time of reaction in detonation waves of RDX, TNT, PETN, Tetryl, DINA, and of some of their mixts. The results obtd were significantly different from previous data. An attempt was made to explain this difference Refs 1) W.E. Deal, "Measurement of Chapman-Jouguet Pressure for Explosives", JChemPhys 27, 796-800(1957) 2) N.L. 

The reactions are based on the reduction of aromatic nitrocompds such as PA, TNT, Tetryl, etc into amines which give rise to several super-imposed reactions, such as formation of diazocompds or endothermic expls... 

At the bottom of the vessel are placed 2 to 4 g of Tetryl (which can be replaced with MF or LA). In the middle of the vessel is a 5-mm canal, c, filled with porous silica gel. When the top part, A, of the device forces the water stored in the container, B to flow thru the capillary, e, in the canal, c, and to the vessel contg D, the reactions described above would take place. The needle, L, sliding along dial indicates the delay. 

M.A. Cook et al, JACS 79, 32(1957) (Velocity-diameter curves, velocity transients and reaction rates in PETN, RDX, EDNA Tetryl)... 

The majority of aromatic-aliphatic nitramines undergo denitration on heating with phenol, especially in the presence of sulphuric acid. Tetryl, for example, undergoes the following reaction ... 

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 ... 

The reaction can also be carried out by dissolving dimethylaniline first in an excess of nitric add, s.g. 1.40 (e.g. in the weight ratio of nitric acid to dimethylaniline of approximately 15 1) then adding excess nitric add, s.g. 1.50 to this solution, until the final weight ratio is approximately 25 1, finally proceeding as above. In tfrit way tetryl, m,p, 129.S°C i obtained in approximately 83% yield. 

In technical operations dimethylaniline is employed as a starting material chiefly because it is obtainable more easily and is much cheaper than methylaniline. Moreover, tetryl prepared from dimethylaniline is purer than that from methylaniline. Hence the preparation of tetryl from dimethylaniline is more economic, in spite of the greater consumption of nitric acid by dimethylaniline which uses up nitric acid to oxidize one of the N-methyl groups. The yield is not higher than 80%, due to the side-reactions. 

Tetryl combines with an excess of sodium sulphide to form a 13% solution. Even at room temperature the nitro groups are reduced with the formation of a non-explosive substance. This reaction is exploited for the destruction of waste tetryl. 

Roginskii and Lukin [43] found that tetryl is not liable to explode when heated at 150°C in a sealed ampoule, though at temperatures above 150°C, e.g. between 150 and 170°C, explosion may ensue as result of chain reactions occurring during decomposition on long-continued heating. 

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