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United States Patent (19) 11 Patent Number: 5,739,325 Wardle Et Al

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United States Patent (19) 11 Patent Number: 5,739,325 Wardle Et Al US005739325A United States Patent (19) 11 Patent Number: 5,739,325 Wardle et al. 45 Date of Patent: Apr. 14, 1998 54 HYDROGENOLYSIS OF 24,68,10,12 Chemical Abstracts, 120: 248721w, Propellants and Explo HEXABENZYL-2,4,6,8,10,12 HEXAAZATETRACYCLO5.5.0.0.0) sives, "The thermal stability of the polymorphs of hexani DODECANE trohexaazaisowurtzitane. Part I”, vol. 120, (1994). Chemical Abstracts, 120: 221778h, Propellants and Explo 75) Inventors: Robert B. Wardle, Logan; W. Wayne sives, "Diagnostic scheme for polynitrocage compounds', Edwards, Tremonton, both of Utah vol. 120 (1994). 73) Assignee: Thiokol Corporation, Ogden, Utah Arnold T. Nielsen et al., Polyazapolycyclics by Condensa tion of Aldehydes with Amines. 2. Formation of 2,4,6,8.10, 12-Hexabenzyl-24.8.10, 12-hexaazatetracyclo (21) Appl. No.: 568,451 (5.5.0.0.0') dodecanes from Glyoxal and 22 Filed: Dec. 7, 1995 Benzylamines', Journal of Organic Chemistry, vol. 55, pp. (51 Int. Cl. ... CO7D 255/04 1459-1466(1990). 52 U.S.C. ............................................. 540/554; 149/92 58 Field of Search ............................... 149/92; 540/554, Primary Examiner-Richard D. Lovering 540/556; 54.6/1; 564/107, 141, 144 Attorney, Agent, or Firm-Cushman Darby & Cushman IP Group of Pillsbury Madison & Sutro, LLP; Ronald L. (56) References Cited Lyons, Esq. U.S. PATENT DOCUMENTS 57 ABSTRACT 2,459,002 1/1949 Parker et al. ....................... 56.4/144 X 2,485.855 10/1949 Blomquist et al. ... 149/92 X A process for the hydrogenolysis of 2.4.6.8, 10.12 3.228,929 1/1966 Frankel ................................... 540/554 hexabenzyl-2,4,6,8.10.12-hexaazatetracyclo[5.5.0.0. 3,535,390 10/1970 Driscoll ......... ... 149/88 X O'") dodecane ("HBIW") is disclosed. In the process, a 4,432,902 2/1984 McGuire et al ... 149/92 X quantity of HBIW, a cosolvent, and a bromine source are 4,485,237 11/1984 Willer ............... ... 149/92 X placed into a reaction vessel, Acetic anhydride and a palla 4,487,938 12/1984 Boileau et al. ......................... 548/304 dium hydrogenolysis catalyst are rapidly added to the reac 5,124,493 6/1992 Lukasavage et al. ..... ... 149/92 X tion vessel. The hydrogenolysis catalyst should be substan 5,409,617 4/1995 Ross et al. .............................. 210,762 tially free of water. The reaction vessel is purged of an atmosphere capable of reacting with hydrogen, and hydro OTHER PUBLICATIONS gen is quickly introduced into the reaction vessel to convert Anthony J. Bellamy, "Reductive Debenzylation of Hexa the HBIW to tetraacetyldibenzylhexaazaisowurtzitane benzyl-hexaazaisowurtizitane.” Tetrahedron, vol. 51, No. ("TADB"). The acetic anhydride is added immediately prior 16, pp. 4711-4722 (1995). to hydrogen introduction so that the acetic anhydride does Chemical Abstracts, 120: 221757a, Propellants and Explo not have time to react with the HBIW to form an acetylated sives, "Synthesis and explosive performance characteristics derivative prior to commencement of the desired hydroge of polynitro polycyclic cage explosives", vol. 120, p. 232 nation reaction. The process requires very little palladium (1994). catalyst, preferably less than 10% wit/wt based on the HBIW Chemical Abstracts, 121: 38726w, Propellants and Explo substrate. The TADB, precipitated on the palladium hydro sives, "The thermal stability of the polymorphs of hexani genolysis catalyst, is subjected to a second hydrogenation trohexaazaisowurtzitane'', vol. 121, p. 186 (1994). step using a formic acid solvent in the presence of hydrogen Chemical Abstracts, 120: 32623e, Propellants and Explo to form tetraacetyldiformylhexaazaisowurtzitane ("TADF"). sives, "Thermal stability of hexanitrohexaazaisowurtzitane in an Estane formulation”, vol. 120, (1994). 27 Claims, No Drawings 5,739,325 1. 2 HYDROGENOLYSIS OF 2,468,10,12 find conditions which would effect partial or complete HEXABENZYL-2,4,6,8,10,12 debenzylation of HBI.W. The yield of toluene was used as an HEXAAZATETRACYCLO15.5.0.0.0. indicator of the extent of reductive debenzylation. When the DODECANE toluene yield was low, the recovery of starting material was usually high, whereas in those experiments where reason GOVERNMENT RIGHTS able yields of the tetrabenzylated product were obtained, the The U.S. Government has a certain rights in this invention toluene yield was at or slightly below 4 mmol per mmol of as provided for by the terms of contract No. N00014-91-C- starting material. 0254 awarded by the Office of Naval Research. Bellamy's experiments used 1 mmol HBIW (708 mg) in 1O combination with various solvents, acetylating agents, and FIELD OF THE INVENTION hydrogenation catalysts. The following different hydroge nation catalysts were tested by Bellamy: dried Degussa type The present invention relates to the hydrogenolysis of E101 NE/W 10% Pd on activated carbon, dried Pearlman's 2.4.6.8,10,12-hexabenzyl-2,4,6,8,10.12-hexaazatetracyclo catalyst (palladium hydroxide on carbon, 20% Pd), and (5.5.0.0.0'ldodecane, sometimes referred to as "hexa 15 moist Pearlman's catalyst. The catalysts were used at quan benzylhexaazaisowurtzitane” and hereinafter referred to as tities from 70 mg to 710 mg (10% wt?wt to 100% wit/wt “HBIW. based on HBIW substrate). According to Bellamy, at least 50% wit/wt and preferably 100% wt?wt catalyst, based on BACKGROUND OF INVENTION HBIW substrate, was necessary to achieve acceptable An important step in the synthesis of 2.4.6.8,10,12 debenzylation of the HBI.W. hexanitro-2,4,6,8,10,12-hexaazatetracyclo[5.5.0.0.0." The palladium-based catalyst used in the hydrogenolysis dodecane, sometimes referred to as "HINTW" or "CL-20," is step represent a major expense in the overall cost to syn the hydrogenolysis of the chemical intermediate HBIW. thesize CL-20. Arnold T. Nielsen has reported that the HBIW can be synthesized according to the procedure catalyst cost is over $200 per pound of CL-20 ultimately described by Nielsen et al., “Polyazapolycyclics by Con 25 produced. See, copending application Ser. No. 07/292,028, densation of Aldehydes with Amines. 2. Formation of 24, filed Dec. 21, 1988 and Ser. No. 07/989,369, filed Dec. 8, 6,8.10.12-Hexabenzyl-2.4.6.8,10,12-hexaazatetracyclo 1992, and the references cited therein, which applications (5.5.0.0.0') dodecanes from Glyoxal and and references are incorporated herein by reference. Benzylamines,” Journal of Organic Chemistry, Vol. 55, pp. In the original synthesis of CL-20 reported by Arnold T. 1459-66, (1990). An improvement to the hydrogenolysis of 30 Nielsen, "Synthesis of Polynitropolyaza Caged Nitramines.” HBIW would represent an improvement in the overall Chemical Propulsion Information Agency (CPIA), publica synthesis of CL-20. tion number 473, December 1987, the TADB is converted to CL-20 is a polycyclic caged nitramine oxidizer. For most CL-20 via a dinitro so intermediate, existing weapons systems, the most critical ingredient in teraacetylidinitrosohexaazaisowurtzitane, as shown below: both propellant and explosive applications is the oxidizer. 35 CL-20, with its substantial increase in performance output, Ac Ac represents a major breakthrough in energy capabilities for AN 1 N1A. future propellant and explosive systems. It may be possible N N1 to replace existing weapons system energetic fills with CL-20 to increase shaped charge anti-armor penetration, increase missile payload velocity and standoff, increase underwater torpedo effectiveness and lethality, and improve gun propellant impetus. The current open literature techniques of HBIW hydro genolysis are reported by Anthony J. Bellamy, "Reductive 45 Debenzylation of Hexabenzylhexaazaisowurtzitane." Tetrahedron, Vol. 51, No. 16, pp. 4711-22 (1995). A repre sentation of the current hydrogenolysis step is set forth below: 50 Although effective, this route uses large amounts of Pd(OH) ?carbon and the expensive BF-based nitrating agents. 55 / N An improvement to the Nielsen route for the cleavage of Bn NB the final benzyl groups is depicted below: ANAc 1 N1A.Ac ANAc 1 N1A.Ac N3–8 N1 Nos N N1 N N Bn1 YBn ON1 NNo The product is tetraacetyldibenzylhexaazaisowurtzitane 65 (“TADB"). Bellamy reports the catalytic hydrogenation of HBIW under a variety of conditions with the objective to 5,739,325 3 -continued ON NO2 Bn. Bn ONN N1,No. SNN 1) N35N1 H2, Ac2O N, 1NN2 Pd) Cosolvent 3-k N N Bromine N oN1 YNO, Bn1 NBn Ac Ac As explained in greater detail in copending application ANN 1 N1N1A. Ser. Nos. 07/292,028 and 07/989,369, it would be an 10 advancement in the art to avoid the formation of the dini x & troso intermediate and the need for expensive BF-based 1. N N NB reagents and to provide a simpler route for the formation of Bll CL-20. It would be a further significant advancement in the art to 15 According to the process, a quantity of HBTW and a provide a process for the hydrogenolysis of 2,4,6,8,10,12 cosolvent are introduced into a reaction vessel. Currently hexabenzyl-2,4,6,8.10.12-hexaazatetracyclo[5.5.0.0.0. preferred cosolvents which have been shown to provide 11ldodecane which requires less catalyst than currently significant improvement are N,N-dimethylformamide known processes, thereby reducing the overall manufactur (“DMF"), N-methylpyrollidone ("NMP"), and 1,2- ing cost of CL-20. It would also be an advancement in the dimethoxyethane. Of course, other known and novel cosol art to provide a process for the hydrogenolysis of 2.4.6.8, vents can be used, but they may not provide the same 10, 12-hexabenzyl-2.4.6.8.10.12-hexaazatetracyclo[5.5.0.0. improvement in reproducibility and in reducing the catalyst 9.0"dodecane which produces high yields of the desired loading as with the cosolvents mentioned above.
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