The Chemistry of Powder and Explosives - Sciencemadness Dot Org

DIAZODINITROPHENOL 443
Preparation of m-Nitrobenzenediazonium Perchlorate. Half a gram
of m-nitroaniline is suspended in 5 cc. of water in a wide test tube, and
0.5 cc. of concentrated hydrochloric acid and 2.2 cc. of 20% perchloric
acid solution are added. After the nitraniline has dissolved, 15 cc. of
water is added and the solution is cooled by immersing the test tube
in a beaker filled with a slurry of cracked ice. One-quarter of a gram
of sodium nitrite dissolved in 1 or 2 cc. of water is added in 3 or 4
portions, the mixture being shaken after each addition or stirred with
a stirring rod the end of which is covered with a short piece of rubber
tubing. After standing in the cold for 5 minutes, the material is transferred
to a filter, and the feltlike mass of pale yellow needles is washed
with cold water, with alcohol, and with ether. The product is dried in
several small portions on pieces of filter paper.
Diazodinitrophenol (DDNP, Dinol)
4,6-Dinitrobenzene-2-diazo-l-oxide, or diazodinitrophenol as it
is more commonly called, occupies a place of some importance in
the history of chemistry, for its discovery by Griess 5e led him
to undertake his classic researches on the diazonium compounds
and the diazo reaction. He prepared it by passing nitrous gas
into an alcoholic solution of picramic acid, but it is more conveniently
prepared by carrying out the diazotization in aqueous
solution with sodium nitrite and hydrochloric acid.
OH OH 0—N
-NH2 diazotize
NO2 NO2 NO2
Picric acid Picramic acid Diazodinitrophenol
Picramic acid, red needles, m. p. 169°, may be prepared by evaporating
ammonium picratc in alcohol solution with ammonium
sulfide.
Preparation of Diazodinitrophenol. Ten grams of picramic acid is
suspended in 120 cc. of 5% hydrochloric acid in a beaker which stands
in a basin of ice water, and the mixture is stirred rapidly with a
mechanical stirrer. Sodium nitrite (3.6 grams) dissolved in 10 cc. of
water is added all at once, and the stirring is continued for 20 minutes.
The product is collected on a filter and washed thoroughly with ice
56 Ann., 106, 123 (1858), 113, 205 (1860).