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Benzylamine-Free, Heavy-Metal-Free Synthesis of CL-20

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Benzylamine-Free, Heavy-Metal-Free Synthesis of CL-20 Benzylamine-Free, Heavy-Metal-Free Synthesis of CL-20 SERDP SEED Project WP-1518 Naval Air Warfare Center Weapons Division China Lake Naval Air Systems Command Principal Investigator: Dr. Robert D. Chapman Chemistry Branch (Code 498200D) Research Division Research & Engineering Sciences Department Naval Air Warfare Center Weapons Division 1900 N. Knox Rd. Stop 6303 China Lake, CA 93555-6106 Contributors: Dr. Richard A. Hollins Dr. Thomas J. Groshens David A. Nissan December 28, 2006 Approved for public release; distribution is unlimited Form Approved REPORT DOCUMENTATION PAGE OMB No. 0704-0188 The public reporting burden for this collection of information is estimated to average 1 hour per response, including the time for reviewing instructions, searching existing data sources, gathering and maintaining the data needed, and completing and reviewing the collection of information. Send comments regarding this burden estimate or any other aspect of this collection of information, including suggestions for reducing the burden, to the Department of Defense, Executive Services and Communications Directorate (0704-0188). Respondents should be aware that notwithstanding any other provision of law, no person shall be subject to any penalty for failing to comply with a collection of information if it does not display a currently valid OMB control number. PLEASE DO NOT RETURN YOUR FORM TO THE ABOVE ORGANIZATION. 1. REPORT DATE (DD-MM-YYYY) 2. REPORT TYPE 3. DATES COVERED (From - To) 4. TITLE AND SUBTITLE 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) 5d. PROJECT NUMBER 5e. TASK NUMBER 5f. WORK UNIT NUMBER 7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) 8. PERFORMING ORGANIZATION REPORT NUMBER 9. SPONSORING/MONITORING AGENCY NAME(S) AND ADDRESS(ES) 10. SPONSOR/MONITOR'S ACRONYM(S) 11. SPONSOR/MONITOR'S REPORT NUMBER(S) 12. DISTRIBUTION/AVAILABILITY STATEMENT 13. SUPPLEMENTARY NOTES 14. ABSTRACT 15. SUBJECT TERMS 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF 18. NUMBER 19a. NAME OF RESPONSIBLE PERSON a. REPORT b. ABSTRACT c. THIS PAGE ABSTRACT OF PAGES 19b. TELEPHONE NUMBER (Include area code) Standard Form 298 (Rev. 8/98) Prescribed by ANSI Std. Z39.18 This report was prepared under contract to the Department of Defense Strategic Environmental Research and Development Program (SERDP). The publication of this report does not indicate endorsement by the Department of Defense, nor should the contents be construed as reflecting the official policy or position of the Department of Defense. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise, does not necessarily constitute or imply its endorsement, recommendation, or favoring by the Department of Defense. Table of Contents List of Acronyms.............................................................................................................................ii List of Figures .................................................................................................................................ii Acknowledgements .........................................................................................................................ii Executive Summary ........................................................................................................................ 1 Objective ......................................................................................................................................... 2 Background ..................................................................................................................................... 2 Materials and Methods.................................................................................................................... 4 Results and Accomplishments ........................................................................................................ 7 Conclusions ................................................................................................................................... 20 Appendix. Experimental Section (Supporting Data)..................................................................... 23 Appendix. List of Technical Publications..................................................................................... 27 i List of Acronyms BINAP 2,2′-Bis(diphenylphosphino)-1,1′-binaphthalene CL-20 Hexanitrohexaazaisowurtzitane COD Cyclooctadiene DMAC Dimethylacetamide DMSO Dimethyl sulfoxide HAIW Hexaacetylhexaazaisowurtzitane HAllylIW Hexaallylhexaazaisowurtzitane HBIW Hexabenzylhexaazaisowurtzitane HHTDD 2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazatricyclododecane-5,11-dione HMX Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine HNW Hexanitrohexaazawurtzitane HPIW Hexa(1-propenyl)hexaazaisowurtzitane MsOH Methanesulfonic acid NMR Nuclear magnetic resonance RDX Hexahydro-1,3,5-trinitro-1,3,5-triazine TADA Tetraacetylhexaazaisowurtzitane TADF Tetraacetyldiformylhexaazaisowurtzitane TADH Tetraacetylhexaazaisowurtzitane TAIW Tetraacetylhexaazaisowurtzitane TEX 4,10-Dinitro-2,6,8,12-tetraoxa-4,10-diaza-tetracyclododecane THF Tetrahydrofuran TsOH p-Toluenesulfonic acid List of Figures Figure 1. Current production process for CL-20............................................................................. 3 Figure 2. Proposed benzylamine-free preparation of CL-20 precursor .......................................... 5 Figure 3. 1H NMR spectrum of crude reaction sample: photooxygenation of HPIW .................. 15 Figure 4. 1H NMR spectrum of crude reaction sample: nitrolysis of oxidation product 6 to CL-20............................................................ 17 Figure 5. Benzylamine-free, heavy-metal-free route to CL-20..................................................... 21 Figure A-1. 1H NMR spectrum of crude reaction sample: preparation of HPIW......................... 23 Figure A-2. 13C NMR spectrum of crude reaction sample: preparation of HPIW........................ 24 Figure A-3. 1H NMR spectrum of crude reaction sample: nitrolysis of HPIW ............................ 26 Acknowledgements In addition to the Principal Investigator, Dr. Richard A. Hollins and Dr. Thomas J. Groshens (Chemistry Branch, Research Division, Research & Engineering Sciences Department, NAWCWD) and Mr. David A. Nissan (Naval Research Enterprise Intern Program, Summer 2006) carried out the work described in this report. ii Executive Summary SERDP Statement of Need PPSON-06-03 called for new “green chemistry” approaches to the preparation of precursors to important energetic ingredients, such as nitrogenous poly- cycles. One of the most important new ingredients for DoD applications is CL-20, but its produc- tion process suffers from several economic and environmental disadvantages, mostly related to requirements for benzylamine starting material and for heavy metal (typically, palladium) cata- lysts used in debenzylation steps. Besides its high material cost, benzylamine is an environ- mentally undesirable starting material. The main objective of this SEED project was to demon- strate the feasibility of preparing the hexaazaisowurtzitane cage in a form that is directly nitrolyzable to CL-20 without a requirement for expensive benzylamine starting material or heavy metal catalysts, thereby introducing a new, preferably lower-cost, less wasteful, and environmentally cleaner process to produce CL-20. Ultimately, this project was fully successful in demonstrating a new route to CL-20 that met these requirements, but many unsuccessful reaction runs were carried out along the way. Many attempts were made to achieve the transformation originally proposed for this project: the condensation of 1,4-diformyl-2,3,5,6-tetrahydroxypiperazine (1) with any 1,1,2,2- tetraamidoethane (2) to form a hexaacylhexaazaisowurtzitane suitable as a precursor to CL-20. All of our attempts at this condensation, under many different conditions, were unsuccessful. We next performed degradation chemistry on a known nitramine, HHTDD, in attempts to reorganize its degradation intermediates into a hexaazaisowurtzitane cage, but initial attempts were unsuc- cessful. The recent publication by French researchers of a new hexaazaisowurtzitane derivative, hexaallylhexaazaisowurtzitane (HAllylIW), presented a new opportunity to prepare a superior precursor to CL-20 without a requirement for benzylamine or heavy metal catalysts. We applied a known transformation—base-catalyzed isomerization of allylamines into 1-propenylamines— to HAllylIW to prepare a new derivative, hexa(1-propenyl)hexaazaisowurtzitane (HPIW). We next performed photooxygenation of this intermediate by singlet oxygen—using oxygen gas photolyzed by a quartz halogen headlamp in the presence of a tetraphenylporphine sensitizer—in order to oxidize the 1-propenyl substituents to formyl substituents. The resulting hexa- or poly- formylhexaazaisowurtzitane was expected to be a new suitable precursor to CL-20. Although the oxidation reaction did not go to completion to produce hexaformylhexaazaisowurtzitane, the partially oxidized product formed did indeed undergo nitrolysis to form CL-20 in a clean reaction. Furthermore, we demonstrated that the new intermediate, HPIW, underwent direct nitrolysis to form CL-20, though initial conditions did not do so as cleanly as with its oxidation product as a precursor for nitrolysis. This reactivity of the enamine HPIW is explained to be a mechanistically reasonable transformation. This SEED project constituted only a feasibility
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