Trinitroanisole complex

Trinitroanisole Complex, CHj O-CgHjtNOjJj -[ 3CHAcNaCOaC1Hs, red amor ppt, expl on j heating sol in ale or acet. It was obtained on I treating a benzolic soln of TNAns with a ben2olic soln of ethyl sodium acetate. Another expl complex was obtained on treating TNAns with ethyl sodium malonate Ref C.L. Jackson Si F.H.Gazzolo, Amer Chem-J 23, 376(1900) JCS 78, I, 433-4(1900)... 

Activation energies have also been measured for the formation of adducts from 2,4-dinitroanisole and methoxide, 16 8 kcal mole-1 (Fendler, 1966), and 2,4-dinitro-l-methoxynaphthalene and methoxide, 13-8 kcal mole-1 (Fendler et al., 1968). For the latter compound the activation energy for reversal to reactants was 16-5 kcal mole-1, while the entropies of activation for the forward and reverse reactions were — 17 and —18 e.u. respectively. Fendler has also calculated that the corresponding entropies of activation for the 2,4,6-trinitroanisole complex are —14 and —11 e.u., and as a result has suggested that the... 

A careful study of the reaction of 2 4 6 trinitroanisole with sodium methoxide revealed that two different Meisenheimer complexes were present Suggest reasonable structures for these two complexes... 

Tire present paper describes a simple and convenient procedure for the identification of explosives viz Picramide Hexyl 2,4-Dinitrophenetole (DNP) Tetryl s-TNT s-TNB 2,4,6-Trinitroanisole (TNA) 2,4-Dinitroanisole (DNA) 2,4,6-Trinitro-phenetole (TNP) DNCB m-DNB and Picryl Chloride (PC) in ordnance stores as charge-transfer complexes with amines utilizing TLC... 

The two Meisenheimer complexes are the sodium salts of the anions shown. It was observed that compound A was the more stable of the two. Compound B was present immediately after adding sodium methoxide to 2,4,6-trinitroanisole but underwent relatively rapid isomerization to compound A. 

Recently crystal structure determinations of the complexes derived from 2,4,6-trinitroanisole and methoxide (Ueda et al., 1967) and 2,4,6-trinitrophenetole and ethoxide (Destro et al., 1967) have shown that the two alkoxy groups are indeed identical in the complex and that the plane defined by their oxygen atoms and Cl is orthogonal to the ring. The C6-C1-C2 bond angle is 109°, very close to the tetrahedral angle required for an sp3-hybridized carbon. 

Azide ions react with 2,4,6-trinitroanisole at temperatures below —10° in aprotic solvents to give an addition complex (Caveng and Zollinger, 1967). The NMR spectrum indicates addition at Cl. Similarly it has been found from NMR evidence (Servis, 1967) that diethyl-amine and triethylamine give adducts at Cl with 2,4,6-trinitroanisole in dimethyl sulphoxide. The latter adduct is unusual in that it is apparently the zwitterion 11. However, addition of triethylamine to... 

The values of the equilibrium constants (Kx) for complex formation from 2,4-dinitroanisole and 2,6-dinitroanisole are much smaller than that from 2,4,6-trinitroanisole, as expected. However, the values for the dinitroanisoles are much greater than for 1,3-dinitrobenzene itself, presumably because of similar steric and electronic factors to those which enhance the complex formation of 2,4,6-trinitroanisole relative... 

It is of interest that the equilibrium constant for sulphite addition to 2,4,6-trinitroanisole is similar in this case to the value for 1,3,6-trinitrobenzene, addition occurring in each case at a ring carbon carrying hydrogen. This indicates that the electronic effects of the substituents at Cl do not appear to affect the stabilities of the adducts greatly. The increased stability of the picramide complex may result from some... 

As previously discussed in section III.A.l, azide ion undergoes addition-elimination Ar reactions with bond-formation being rate-limiting or sufficiently close to it to have equivalent results. At low temperatures the intermediate addition complex from the interaction of azide ion with 2,4,6-trinitroanisole has been detected by Caveng and Zollinger . These workers observed characteristic p.m.r. resonances arising from the sigma complex (147) at —40° in acetonitrile and... 

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