THE ACTION OF HYDROXYLAMINE ON METHYL ALPHA- AND BETA- D -GLUCOPYRANOSIDE TETRANITRATE IN PYRIDINE

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A pyridine solution of dulcitol hexanitrate evolved gas and becamc highly colored when warmed to 50°C.; dilution with water caused the precipitation of 67y0 of the theoretical amount of a dulcitol pentanitratc. The product was characterized a s D,L-galactitol-1,2,4,5,6-pentanitrate by methylation to a monomethyl dulcitol pentanitrate, denitration of the latter, and periodate oxidation of the monomethyl dulcitol obtained. The hesitol derivatives were all obtained in a pure crystalline form. The signiticnnce of the data now available on the selective partial denitration by pyridine of hesitol hexanitrates is briefly discussed. INTRODUCTIONIn a previous research (5) it was shown t h a t excess pyridine a t 35°C. selectively removed the third (or equivalent fourth) nitrate group from D-mannit01 hexailitrate t o give ~-mannitol-1,2,3,5,6-pentanitrate in 73% yield. This reaction was first described in 1903 by \Vigner (14) who also reported a good yield of a mannitol pentanitrate from the action of alcoholic pyridine on mannitol hexanitrate. Wigner also nitrated dulcitol (I) t o obtain a hexanitrate melting a t "about 95"" ( 3 , 4 , 13) and found t h a t alcoholic pyridine had almost 110 effect on this product even a t the boiling point. Warming a solution of the dulcitol hexanitrate in pure pyridine, however, caused a reaction accompanied by evolution of a gas, and, on pouring the reaction mixture into water, Wigner obtained a crystalline product which "sintered a t 71" and melted a t about 75"" after three recrystallizations from aqueous alcohol. Analysis iiidicated this product t o be a dulcitol pentanitrate.In the present research Wigner's results were confirmed and the dulcitol pentanitrate was characterized a s the racemic D-and L-galactitol-1,2,4,5,Gpentanitrate (111) by a series of reactions parallel t o t h a t previously described (5) for the characterizatioii of ~-mannitol-1,2,3,5,6-pentanitrate.Dulcitol hexanitrate (D-or L-galactitol-1,2,3,4,5,6-hexanitrate) (11) was prepared in 92% yield by direct nitration of dulcitol (galactitol) (I) with nitric-sulphuric acid mixture, and the pure, crystalline, optically inactive compoulld melted a t 98-99°C. and had the correct nitrate nitrogen content. Hydrogellolysis of a sample of the hexanitrate produced dulcitol quantitativelj. ( 5 , 6). T h e hexanitrate dissolved readily in pure pyridine a t 30°C. t o give a n initially colorless solution which became orange-colored in five minutes. No gas evolution xilas observed until the solutioil was warmed t o 50°C., whereupon an exothermic reaction commenced, brown fumes were observed in the open vessel, and fine, colorless, needle-like crystals appeared on the inner ~valls of the flask above the solution. T h e vigorous reaction subsided within a few minutes and after 24 hr. the dark-red solutioll was poured into

“…The analytical procedures for nitrate nitrogen, methoxyl, and periodate oxidation products were previously described (5,6,10).…”

Section: Methodsmentioning

confidence: 99%

The Action of Pyridine on Dulcitol Hexanitrate

McKeown¹,

Hayward²

1955

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“…Similar curves were obtained a t concentrations of and 10-a M. These spectra were distinctly different from those of open-chain, secondary aliphatic nitrate esters, which showed a characteristic inflection a t 270 m p (25), but agreed well with those of other polynitrate esters (31). T h e other nitratr ssters employed have been described else~vhere (26)(27)(28)(29)34).…”

Section: Chromatograplrymentioning

confidence: 99%

Photolysis of Nitrate Esters: Part I. Photonitration of Diphenylamine

Hayward¹,

Kitchen²,

Livingstone³

1962

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The photolysis of nitrate esters dissolved in benzene or ethanol or absorbed on hlter paper occurred readily under illumination in the 265 mp t o 334 mp spectral region. Equimolar amounts of 1,4;3,6-dianhydro-D-glucitol-2,5-dinitrate and diphenylamine dissolved in absolute ethanol or benzene did not react in the dark a t 25'. Irradiation of the nitrogen-purged solutions for 2 hours a t 15' with a mercury arc followed by chromatographic separation yielded 2-nitro-, 4-nitro-, N-nitroso-, and 4-nitroso-diphenylamine together with about 4% unreacted diphenylamine and an unidentified mixture of more polar compounds. In a partial fractionation of the aromatic photoproducts approximately 80% of the original diphenylamine was recovered in the form of the monosubstituted derivatives which contained about 37% of the original ester nitrogen as C-nitro groups and 2 to 3% as C-and iV-nitroso groups.

“…Mathews, and Williams (8) and was assumed to be nitrogen (19,28); any carbon monoxide present in the evolved gas would have bee11 oxidized a t room temperature to the dioxide by the nitrogen dioxide. I n the ailalysis of the oxygen-and-mercury-treated gas a repass through the ethanol pipette established that the loss in volume of the gas (<1.5%) on passage through the potassium hydroxide solution was probably due t o absorptioil of ethanol vapor and not t o acid gases.…”

Section: Gas Evolved From D-mannitol Eltexanitrate and Pyridinementioning

confidence: 99%

“…After removal of the nitric oxide the remaining gas was analyzed for nitrous oxide, carbon dioxide, and the ltnotvn excess of oxygen in an Orsat apparatus (28) and for nitrogen by gas-density measurements on the ilonabsorbable residual gas (19,28). Appropriate corrections were made for the pyridine vapor and its coabsorption with the nitrous oxide.…”

mentioning

confidence: 99%

THE ACTION OF PYRIDINE ON D-MANNITOL HEXANITRATE

Brown¹,

Hayward²

1955

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From a 0.368Msolution of D-mannitol hexanitrate in pyricline a t 3 0 f 5'C. a gas consisting of nitric oxide, nitrous oxide, and nitrogen was evolved and D-mannitol-1,2,4,5,6-pentanitrate and pyridinium nitrate were recovered after d i l~~t i o n with water. The amount and composition of the gas mixture were sensitive to traces of moisture in the pyridine. Establishment of a material balance for the reaction indicated that approximately two moles of pyridine s~~ffered ring cleavage while 0.25 11lole of hexanitrate was completely denitrated and 0.75 mole of pentanitrate was formed. Some features of the tnechanism of the denitration reaction are discussed.