Process for the synthesis and recovery of nitramines

1. A method for preparing an N-heterocyclomethyl polynitrazaalkane, selected from the group consisting of 1,9-bis-(3′,5′-dinitro-1′,2′,4′-triazolo)-2,5,8-trinitrazanonane and 1,6-bis-(3′,5′-dinitro-1′,2′,4′-triazolo)-2,5-dinitrahexane, the method comprising:

halomethylating a polynitrazaalkane in at least one solvent with a halogenating agent to form an N-halomethyl polynitrazaalkane, wherein the polynitrazaalkane has at least one terminal nitraza moiety and wherein the N-halomethyl polynitrazaalkane comprises an N-halomethyl moiety having a halogen atom;

substituting a heterocyclic nucleophile for the halogen atom of the N-halomethyl polynitrazaalkane to form a clathrate comprising an N-heterocyclomethyl polynitrazaalkane, wherein the heterocyclic nucleophile comprises a triazole; and

recovering the N-heterocyclomethyl polynitrazaalkane from the clathrate by precipitation in a nonsolvent.

2. The method of claim 1 , wherein halomethylating the polynitrazaalkane in the at least one solvent with the halogenating agent to form the N-halomethyl polynitrazaalkane comprises forming the N-halomethyl polynitrazaalkane having a halogen atom comprising a member selected from the group consisting of chlorine, bromine, and iodine.

3. The method of claim 1 , wherein substituting the heterocyclic nucleophile for the halogen atom of the N-halomethyl polynitrazaalkane comprises substituting a triazole for the halogen atom.

4. The method of claim 1 , wherein substituting the heterocyclic nucleophile for the halogen atom of the N-halomethyl polynitrazaalkane comprises substituting a triazole having at least one nitro substituent for the halogen atom.

5. The method of claim 1 , wherein substituting the heterocyclic nucleophile for the halogen atom of the N-halomethyl polynitrazaalkane comprises substituting a triazole having two nitro substituents for the halogen atom.

6. The method of claim 1 , wherein substituting the heterocyclic nucleophile for the halogen atom of the N-halomethyl polynitrazaalkane to form the clathrate comprising the N-heterocyclomethyl polynitrazaalkane comprises forming the clathrate comprising at least one pair of methylene-spaced nitramine moieties.

7. The method of claim 1 , wherein substituting the heterocyclic nucleophile for the halogen atom of the N-halomethyl polynitrazaalkane to form the clathrate comprising the N-heterocyclomethyl polynitrazaalkane comprises forming the clathrate comprising at least two pairs of methylene-spaced nitramine moieties.

8. The method of claim 1 , wherein substituting the heterocyclic nucleophile for the halogen atom of the N-halomethyl polynitrazaalkane to form the clathrate comprising the N-heterocyclomethyl polynitrazaalkane comprises forming the clathrate comprising two heterocyclomethyl groups.

9. The method of claim 1 , wherein substituting the heterocyclic nucleophile for the halogen atom of the N-halomethyl polynitrazaalkane to form the clathrate comprising the N-heterocyclomethyl polynitrazaalkane comprises forming the clathrate comprising 1,9-bis-(3′,5′-dinitro-1′,2′,4′-triazolo)-2,5,8-trinitrazanonane.

10. The method of claim 1 , wherein substituting the heterocyclic nucleophile for the halogen atom of the N-halomethyl polynitrazaalkane to form the clathrate comprising the N-heterocyclomethyl polynitrazaalkane comprises forming the clathrate comprising 1,6-bis-(3′,5′-dinitro-1′,2′,4′-triazolo)-2,5-dinitrahexane.

11. The method of claim 1 , wherein recovering the N-heterocyclomethyl polynitrazaalkane from the clathrate by precipitation in the nonsolvent comprises selecting the nonsolvent to comprise a member selected from the group consisting of methanol and methylene chloride.

12. The method of claim 1 , wherein halomethylating the polynitrazaalkane in the at least one solvent with the halogenating agent to form the N-halomethyl polynitrazaalkane and substituting the heterocyclic nucleophile for the halogen atom of the N-halomethyl polynitrazaalkane to form the clathrate comprising the N-heterocyclomethyl polynitrazaalkane comprises:

hydroxymethylating the at least one terminal nitraza moiety of the polynitrazaalkane to form at least one N-hydroxymethyl nitraza moiety;

esterifying the at least one N-hydroxymethyl nitraza moiety of the polynitrazaalkane with a leaving group; and

substituting the heterocyclic nucleophile for the leaving group of the polynitrazaalkane to form the N-heterocyclomethyl polynitrazaalkane, the substituting taking place in the at least one solvent.

13. The method of claim 1 , wherein the polynitrazaalkane to be halomethylated is prepared by a method comprising:

providing a polyamine comprising at least one primary amine moiety and at least one secondary amine moiety;

perchlorinating the polyamine to convert the at least one primary amine moiety into an N-perchlorinated amine moiety having two chlorine atoms and to convert the at least one secondary amine moiety into an N-chlorinated amine moiety having one chlorine atom;

nitrating the polyamine to substitute respective nitro moieties for one of the chlorine atoms of the N-perchlorinated amine moiety and for the chlorine atom of the N-chlorinated amine moiety; and

dechlorinating the polyamine.

14. The method of claim 1 , wherein the polynitrazaalkane to be halomethylated is prepared by a method comprising:

providing a polyamine comprising at least two primary amine moieties;

perchlorinating the polyamine to convert the at least two primary amine moieties into respective N-perchlorinated amine moieties each having two respective chlorine atoms;

nitrating the polyamine to substitute respective nitro moieties for one of the chlorine atoms of each of the N-perchlorinated amine moieties; and

dechlorinating the polyamine.

15. The method of claim 1 , wherein the polynitrazaalkane to be halomethylated is prepared by a method comprising:

providing a polyamine comprising at least one primary amine moiety and at least one secondary amine moiety;

acylating the polyamine to convert the at least one primary amine moiety into an acylated amine moiety while leaving the at least one secondary amine moiety non-acylated;

nitrating the acylated polyamine to substitute respective nitro moieties for hydrogen atoms of the acylated amine moiety and the at least one non-acylated secondary amine moiety; and

deacylating the acylated amine moiety.

16. The method of claim 1 , wherein the polynitrazaalkane to be halomethylated is prepared by a method comprising:

providing a polyamine comprising at least two primary amine moieties;

acylating the polyamine to convert the at least two primary amine moieties into respective acylated secondary amine moieties of an N-acylated polyamine;

nitrating the acylated polyamine to substitute respective nitro moieties for hydrogen atoms of the acylated secondary amine moieties; and

deacylating the acylated secondary amine moieties.

17. The method of claim 1 , wherein substituting the heterocyclic nucleophile for the halogen atom of the N-halomethyl polynitrazaalkane to form the clathrate comprising the N-heterocyclomethyl polynitrazaalkane comprises heterocyclomethylating 1,2-dinitrazaethylene.