Pentanitrate esters

Friederich and Flick " ° synthesized the tetranitrate ester (67) by condensing cyclopentanone with four equivalents of formaldehyde followed by nitration of the condensation product (66) with mixed acid. Reduction of the ketone group of (66), followed by nitration, yields the pentanitrate ester (69). A similar route was used to synthesize analogous nitrate esters from cyclohexanone. ... 

Dihydroxylation of the allyl groups of (70) with hydrogen peroxide and catalytic osmium tetroxide, followed by 0-nitration of the product (72), yields the hexanitrate ester (73). Similar treatment of the mono-allyl ether (74) affords the pentanitrate ester (76). Evans and Callaghan also 0-nitrated the hydroxy groups of (70) and (74) to yield the dinitrate and trinitrate esters, (71) and (75), respectively. The dinitrate ester (71) may find use as a monomer for the synthesis of energetic binders. 

Interest has focused on derivatives of mannitol hexanitrate (14) as potential explosives because although this nitrate ester is a powerful explosive it has some property characteristics of a primary explosive. Treatment of mannitol hexanitrate (14) with pyridine or ammonium carbonate " in aqueous acetone leads to a very selective denitration with the formation of mannitol-1,2,3,5,6-pentanitrate (77). Marans and co-workers synthesized the acetate (78), the propionate (79), and the phenylacetate (80) derivatives of mannitol-1,2,3,5,6-pentanitrate and all have significantly lower melting points than mannitol hexanitrate. The incorporation of such groups can also help to increase the solubility of an explosive in the melt of another explosive. 

Mannitol hexanitrate is obtained by nitration of mannitol with mixed nitric and sulfuric acids. Similarly, nitration of sorbitol using mixed acid produces the hexanitrate when the reaction is conducted at 0—3°C and at —10 to —75°C, the main product is sorbitol pentanitrate (117). Xylitol, ribitol, and L-arabinitol are converted to the pentanitrates by fuming nitric acid and acetic anhydride (118). Phosphate esters of sugar alcohols are obtained by the action of phosphorus oxychloride (119) and by alcoholysis of organic phosphates (120). The 1,6-dibenzene sulfonate of D-mannitol is obtained by the action of benzene sulfonyl chloride in pyridine at 0°C (121). To obtain 1,6-dimethanesulfonyl-D-mannitol free from anhydrides and other by-products, after similar sulfonation with methane sulfonyl chloride and pyridine the remaining hydroxyl groups are acetylated with acetic anhydride and the insoluble acetyl derivative is separated, followed by deacetylation with hydrogen chloride in methanol (122). Alkyl sulfate esters of polyhydric alcohols result from the action of sulfur trioxide—trialkyl phosphates as in the reaction of sorbitol at 34—40°C with sulfur trioxide—triethyl phosphate to form sorbitol hexa(ethylsulfate) (123). 

Both esters, and specially hexanitroinositol, were suggested by Crater [71] for use in explosives practice instead of tetryl for filling detonators and boosters. In explosive strength, sensitiveness to mechanical shock, and stability both esters are similar to nitromannite. References to quebrachitol pentanitrate can be found in the patents of Burke and McGill [72]. 

A number of such compds were prepd and then converted to the corresponding nitric esters by Wolfram et al of Ohio State Univ while working under a US Ordnance Corps contract(Ref 5 6). They found that all the pentanitrates prepd by them could be detonated by gentle heat or by a hammer blow on steel. Thermal stability tests have shown that the aldonamide pentanitrates are more stable than aldonic acid pentanitrates or their methyl esters and that the esters were less stable than the corresponding acids. All of their purified nitrates underwent rapid decompn at their mp s, accompanied by violent bubbling and evolution of nitrogen oxides. No residue was visible after decompn... 

Some of the pentanittates were suggested for use in propellants. To determine the suitability of these nitrates for this puipose, compatibility tests were made with NC (12.6%N). The aldonamide pentanitrate and the metliyl ester of aldonie acid pentanitrate were found to be compatible with NC in film formation(employing ethyl acetate as the solvent) and the stability of the film was comparable to that of the free pentanitrate ... 

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