Monoses.—The aldoses are fully esterified, in the pentoses 4 OH, in the hexoses 5 OH groups reacting. The pentose nitrates are comparatively stable at 50°; the hexose nitrates on the other hand are extremely unstable, showing a loss of weight of 30-40 p.ct. when kept 24 hours at this temperature.
Xylose is differentiated by tending to pass into an anhydride form (C5H10O5-H2O) under this esterification. When treated in fact with the mixed acids, instead of by the process usually adopted by the authors of solution in nitric acid and subsequent addition of the sulphuric acid, it is converted into the dinitrate C5H6O2.(NO3)2.
Ketoses (C6).—These are sharply differentiated from the corresponding aldoses by giving trinitrates C6H7O2(NO3)3 instead of pentanitrates, the remaining OH groups probably undergoing internal condensation. The products are, moreover, extremely stable. It is also noteworthy that levulose gave this same product, the trinitrate of the anhydride (levulosan) by both methods of nitration (supra).
The bisaccharides or bioses all give the octonitrates. The degree of instability is variable. Cane-sugar gives a very unstable nitrate. The lactose nitrate is more stable. Thus at 50° it loses only 0.7 p.ct. in weight in eight days; at 75° it loses 1 p.ct. in twenty-four hours, but with a rapid increase to 23 p.ct. in fifty-four hours. The maltose octonitrate melts (with decomposition) at a relatively high temperature, 163°-164°. At 50°-75° it behaves much like the lactose nitrate.
Trisaccharide.—Raffinose yielded the product
C18H21O5.(NO3)11.
Starch yields the hexanitrate (C12) by both methods of nitration. The product has a high melting and decomposing point, viz. 184°, and when thoroughly purified is quite stable. It is noted that a yield of 157 p.ct. of this nitrate was obtained, and under identical conditions cellulose yielded 170 p.ct.
Wood gum, from beech wood, gave a tetranitrate (C10 formula) insoluble in all the usual solvents for this group of esters.
The authors point out in conclusion that the conditions of instability and decomposition of the nitrates of the monose-triose series are exactly those noted with the cellulose nitrates as directly prepared and freed from residues of the nitrating acids. They also lay stress upon the superior stability of the nitrates of the anhydrides, especially of the ketoses.