Process for the 2-stage synthesis of hexanitrohexaazaisowurtzitane starting from a primary amine
View Patent ↗A subject-matter of the present invention is a novel process for the synthesis of hexanitrohexaazaisowurtzitane (HNIW), a compound of use as energetic filler in powders, propellants and explosives. This process comprises a first stage of reaction of an α,β-dicarbonyl derivative with a primary amine which makes it possible to form a hexasubstituted hexaazaisowurtzitane derivative. The HNIW is subsequently obtained directly, in a single reaction stage, by nitration of the hexasubstituted hexaazaisowurtzitane derivative. This process, in only 2 stages starting from a primary amine, is particularly simple and inexpensive.
1. A process for the synthesis of hexanitrohexaazaisowurtzitane, consisting of:
a) reacting an α,β-dicarbonyl compound with a primary amine to form a hexasubstituted hexaazaisowurtzitane compound, and
b) nitrating the hexasubstituted hexaazaisowurtzitane compound obtained in step (a) to directly obtain the hexanitrohexaazaisowurtzitane.
2. The process according to claim 1 , wherein the α,β-dicarbonyl compound is glyoxal.
3. The process according to claim 1 , wherein the primary amine is chosen from the group consisting of heteroarylmethylamines and allylamines; propargylamine; parachlorobenzenesulphenamide and 1-napthylmethylamine.
4. The process according to claim 3 , wherein the primary amine is allylamine or 2-aminomethylfuran.
5. The process according to claim 1 , wherein the first stage of reaction of an α,β-dicarbonyl compound with a primary amine is carried out in a mixture of a polar organic solvent and water, in the presence of an acid catalyst.
6. The process according to claim 5 , wherein the acid catalyst/α,β-dicarbonyl compound molar ratio is between 0.25 and 0.6.
7. The process according to claim 1 , wherein the primary amine/α,β-dicarbonyl compound molar ratio is between 2.5 and 3.5.
8. The process according to claim 1 , wherein the temperature of the reaction of the primary amine with the α,β-dicarbonyl compound is between 0° C. and 25° C.
9. The process according to claim 1 , wherein the hexasubstituted hexaazaisowurtzitane compound formed is isolated from the reaction medium before nitration.
10. The process according to claim 1 , wherein the nitration of the hexasubstituted hexaazaisowurtzitane compound is carried out using a sulphuric acid/nitric acid mixture.
11. The process according to claim 1 , wherein the nitration of the hexasubstituted hexaazaisowurtzitane compound is carried out in the presence of an organic solvent.
12. The process according to claim 11 , wherein during the stage of nitration of the hexasubstituted hexaazaisowurtzitane compound, the reactants are mixed in the presence of the organic solvent at a temperature of between −10° C. and 25° C., all or part of the organic solvent is subsequently removed and then the nitration reaction is continued at a temperature of between 45° C. and 85° C.
13. 2,4,6,8,10,12-hexa R-2,4,6,8,10,12-hexaazatetracylco(5.5.0.05 5,9 .0 3,11 ) dodecane compounds, wherein R is chosen from the group consisting of heteroarylmethyl groups, allyl groups, propargyl groups, trimethylsilyethyl groups, naphthylmethyl groups and sulphenyl groups.