The Chemistry of Powder and Explosives - Sciencemadness Dot Org

236 NITRIC ESTERS
by dissolving erythrite in strong nitric acid with cooling, and then
precipitating by the addition of concentrated sulfuric acid. 64 It
crystallizes from alcohol in colorless plates, m.p. 61°. Its use as
an addition to smokeless powder has been suggested, 65 but it is
as powerful as nitroglycerin, and has the advantage over it that
it is a solid, and it would be suitable, if it were cheaper, for the
same uses as nitromannite.
Nitromannite (Mannitol hexanitrate)
NO2—O—CHj—(CH—ONO2)4—CH,!—ONO2
d-Mannitol occurs fairly widely distributed in nature, particularly
in the Fraxinus ornus, the sap of which is manna. It may
also be procured by the reduction of d-mannose either electrolytically
or by means of sodium amalgam, or along with d-sorbite
by the reduction of d-fructose. It may be nitrated satisfactorily
with the same mixed acid as is used for the nitration of glycerin,
or more conveniently, because the mass of crystals is so voluminous,
by dissolving in strong nitric acid and precipitating by the
addition of concentrated sulfuric acid.
Preparation of Nitromannite. Fifty grams of nitric acid (specific
gravity 1.51) is cooled thoroughly in a 300-cc. Erlenmeyer pyrex flask
immersed in a freezing mixture of ice and salt. Ten grams of mannite
is then introduced in small portions at a time while the flask is tilted
from side to side and the contents is stirred gently with a thermometer,
care being taken that the temperature does not rise above 0°. After
all is dissolved, 100 grams of sulfuric acid (specific gravity 1.84) is
added slowly from a dropping funnel while the liquid is stirred and the
temperature is maintained below 0°. The porridge-like mass is filtered
on a sinter-glass filter, or on a Biichner funnel with a hardened filter
paper, washed with water, then with dilute sodium bicarbonate solution,
then finally again with water. The crude product is dissolved in
boiling alcohol; the solution is filtered if need be, and on cooling deposits
white needle crystals of nitromannite, m.p. 112-113°. A second
crop of crystals may be obtained by warming the alcoholic mother
liquors to boiling, adding water while still boiling until a turbidity
appears, and allowing to cool. Total yield about 23 grams.
Nitromannite is readily soluble in ether and in hot alcohol,
only slightly soluble in cold alcohol, and insoluble in water.
64 Stenhouse, Ann., 70, 226 (1849); 130, 302 (1864).
«S5Ger. Pat. 110,289 (1898); Brit. Pat. 27,397 (1898).