The Chemistry of Powder and Explosives - Sciencemadness Dot Org

136 AROMATIC XiTRO COMPOUNDS
with aniline is bright red; that with naphthalene, yellow. The
compounds with amines are beautifully crystalline substances,
procurable by warming the components together in alcohol, and
are formed generally in the molecular proportions 1 to 1, although
diphenylamine and quinoline form compounds in which two
molecules of TNB are combined with one of the base.
Trinitrobenzene gives red colors with ammonia and with aqueous
alkalies. On standing in the cold with methyl alcoholic
sodium methylate, it yields 3,5-dinitroanisol by a metathetical
reaction. 9
OCH3
+ CH3ONa > + NaNO,
NO2 NO.4 J-NO,
On boiling with alcoholic soda solution it undergoes a partial
reduction to form 3,3',5,5'-tetranitroazoxybenzene. 10
NO2
NO2
>—N=N-
O
NO*
NO2
The first product, however, of the reaction of methyl alcoholic
caustic alkali on TNB is a red crystalline addition product having
the empirical composition TNB CH3ONa £H2O, isolated by
Lobry de Bruyn and van Leent 11 in 1895. The structure of this
substance has been discussed by Victor Meyer, 12 by Angeli, 13 by
Meisenheimer, 14 and by Schlenck, 15 and is probably best represented
by the formula which Meisenheimer suggested. It is thus
Vecchiotti, AM accad. Lincei, 20, II, 377 (1911); 21, II, 161 (1912);
Sastry, /. Chem. Sec, 109, 270 (1916); Hainmick and Sixsmith, J. Chem.
Sec, 972 (1939).
9 Lobry de Bruyn, Rec trav. chim., 9, 208 (1890).
10 Lobry de Bruyn and van Leent, ibid., 13, 148 (1894).
11 Ibid., 14, 150 (1895).
12 her., 29, 848 (1896).
13 Gazz. chim. ital, 27, II, 366 (1897). Compare also Hantzsch and Kissel,
Ber., 32, 3137 (1899).
14 Ann., 323,214,241 (1902).
15 .Ber., 47, 473 (1914).