DISSERTATION ZUR ERLANGUNG DES DOKTORGRADES DER FAKULTÄT FÜR CHEMIE UND PHARMAZIE DER LUDWIG-MAXIMILIANS-UNIVERSITÄT MÜNCHEN SYNTHESIS, CHARACTERIZATION AND TESTING OF POTENTIAL ENERGETIC MATERIALS TOMASZ GRZEGORZ WITKOWSKI aus Zawiercie, POLEN 2017 Gedruckt mit Unterstützung des Deutschen Akademischen Austauschdienstes. Erklärung: Diese Dissertation wurde im Sinne von § 7 der Promotionsordnung vom 28. November 2011 von Herrn Professor Dr. Thomas M. Klapötke betreut. Eidesstattliche Versicherung: Diese Dissertation wurde eigenständig und ohne unerlaubte Hilfe erarbeitet. München, den 09. Januar 2017 Witkowski Tomasz Dissertation eingereicht am: 09. Januar 2017 1. Gutachter: Prof. Dr. Thomas M. Klapötke 2. Gutachter: Prof. Dr. Konstantin Karaghiosoff Mündliche Prüfung am: 24.04.2017 Acknowledgement First of all, I am indebted to and I would like to thank Prof. Dr. Thomas M. Klapötke for giving me the opportunity to undertake my Ph.D. research under his supervision and for giving me the freedom to investigate the topics of my choice. Prof. Dr. Thomas M. Klapötke has been an excellent mentor, who has supported me throughout, took care of my every request, and gave me the benefit of his wide knowledge. I would like also to thank him for the opportunity to attend several conferences to present my research results. Secondly, I would like to thank Prof. Dr. Konstantin Karaghiosoff for crystal structure and NMR spectra measurements, as well as for solving X-ray structures even on the weekend and late at night. Finally, I would like to thank him for agreeing to be the second referee of my doctoral thesis and the second examiner during my thesis defense. I would like to thank Prof. Dr. Jürgen Evers, Prof. Dr. Manfred Heuschmann, Prof. Dr. Andreas Kornath, and Prof. Dr. Ingo-Peter Lorenz for agreeing to be members in the Ph.D. defense committee. I would like to express my sincere appreciation to Prof Dr. Andreas Kornath for giving me the opportunity to work in his research group, as well as for providing much guidance and advice concerning fluorine chemistry. I am deeply indebted to and I would like to gratefully thank Dr. Eng. Mirosław Gibas and Dr. Eng. Anna Korytkowska-Wałach for all the support they have given me. The research results presented in this thesis would not have been possible without your help. Special thanks also go to the German Academic Exchange Service (DAAD) for funding my Ph.D. studies within the framework of a Ph.D. fellowship. I would like to thank Dr. Jörg Stierstorfer for all the support he has provided me and for his professional advice. Dr. Burkhard Krumm is thanked for safety advice and for multinuclear NMR measurements. Ms. Irene Scheckenbach is gratefully thanked for her indispensable help in handling the formalities and bureaucracies of different institutions and for helping me to get settled when I moved to Munich. Ms. Gabriele Schmeißer is gratefully thanked for her helpfulness and for her very friendly attitude. I am deeply grateful to Dr. Dennis Fischer, above all, for his great interest and outstanding knowledge in every aspect of energetic materials, and for being an extremely honest person. I I am extremely grateful to Martin Härtel for his immeasurable help when I moved to Munich, as well as for long discussions in the evenings about chemistry – and not only of energetic materials. I would like to thank Dr. Magdalena Rusan for her endless help in both writing a scholarship proposal and settling in Munich, as well as for being a good friend. I would like to thank all of the people in the Institute of Industrial Organic Chemistry in Poland, especially Dr. Eng. Zenon Wilk, Justyna Hadzik Ms. Sc., Daniel Hadzik, Piotr Koślik Ms. Sc., Ms. Klaudia Kroczek, and Mr. Henryk Zuń Eng. for the long-time cooperation and the fruitful joint research on jet penetration capability and the underwater explosion tests of selected explosives. I would like to thank Dr. Jennifer Gottfried for the great collaboration on the estimation of the detonation velocities of selected energetic materials using the laser-induced air shock from energetic materials method. I would like to thank all of my labmates, including Marc Bölter, Dr. Dennis Fischer, Rafał Lewczuk, Judyta Rećko, Dr. Philipp Schmid, and Maurus Völkl for creating a pleasant and supportive atmosphere. The entire research groups of Prof. Dr. Thomas M. Klapötke and Prof. Dr. Andreas Kornath, are thanked and in particular Dr. Michael Feller, Ivan Gospodinov, Dr. Alexander Kaufmann, Dr. Marcos Kettner, Dr. Norbert Mayr, Yvonne Morgenstern, Dr. Carolin Pflüger, Dr. Sebastian Rest, and Dr. Benedikt Stiasny who helped me in many aspects during my Ph.D. studies. My Bachelor, “F-praktikum” and Masters students are acknowledged for their contributions to my research; Johannes Fessler, Harald Zikeli, Dominik Dosch, and Andreas Drechsel. I am also highly indebted to Stefan Huber not only for the many impact sensitivity, friction and electrostatic discharge tests of the energetic materials described in this thesis, but also for his serious and honest advice at the beginning of my research at LMU. The X-ray and the analytical teams are thanked for measuring single crystals, NMR, MS, and elemental analysis of the compounds described in this thesis. I would like to thank everyone else who has helped me during my research at LMU. Finally, and most importantly, I would like express my genuine appreciation to my wife for her immense support, encouragement, boundless patience, and also for her forgiving approach to my spontaneous personality and unpredictable ideas. II Contents 1. Introduction ....................................................................................................................... 1 2. Summary and Conclusion ................................................................................................. 5 3. Synthesis, Characterization and Crystal Structures of Two Bi-oxadiazole Derivatives Featuring the Trifluoromethyl Group ............................................................................. 13 4. Determination of the Initiating Capability of Detonators Containing TKX-50, MAD-X1, PETNC, DAAF, RDX, HMX or PETN as a Base Charge, by Underwater Explosion Test .................................................................................................................................. 23 5. 5,5′-Bis(2,4,6-trinitrophenyl)-2,2′-bi(1,3,4-oxadiazole) (TKX-55): A Thermally Stable Explosive with Outstanding Properties........................................................................... 45 6. Experimental Study on the Heat Resistant Explosive 5,5′-Bis(2,4,6-trinitrophe- nyl)-2,2′-bi(1,3,4-oxadiazole) (TKX-55): the Jet Penetration Capability and Underwater Explosion Performance ................................................................................................... 55 7. Synthesis and Investigation of Advanced Energetic Materials Based on Bispyrazolylmethanes ................................................................................................ 71 8. Estimated Detonation Velocities for TKX-50, MAD-X1, BDNAPM, BTNPM, TKX-55 and DAAF using the Laser-induced Air Shock from Energetic Materials Technique ... 89 9. Synthesis and Characterization of 5-Methyl-2,4,6-trinitrobenzene-1,3-diol and Its Energetic Cesium Salt ................................................................................................... 107 10. Nitrogen-Rich Energetic 1,2,5-Oxadiazole-Tetrazole – Based Energetic Materials .... 121 11. Covalent and Ionic Insensitive High-Explosives .......................................................... 137 12. Appendix: Underwater Test Results ............................................................................. 163 13. Appendix: General Information .................................................................................... 169 List of publications ................................................................................................................. 175 III Chapter 1 1. Introduction 1.1 Definition and Classification Research into new energetic materials (EMs) with improved properties is an ongoing project in many research groups. Depending on the purpose the EMs should fulfill, research is focused on improving different key characteristics of the materials. EMs are usually subdivided into following classes:[1] Primary explosives (“primers”) are substances which are principally used to detonate secondary explosives.[1a, 1b, 1d-f] Primary explosives undergo very rapid combustion (or deflagration) to detonation transfer and are significantly more sensitive towards external stimuli (e.g.: heat, impact, friction, electrostatic discharge) than secondary explosives.[1a, 1b, 1d- f] More details on primary explosives are given in the introduction to chapter nine. Secondary explosives (“high explosives”) are less sensitive to external stimuli but higher performing than primary explosives.[1a, 1b, 1e, 1f] Modern trends in the research of high explosives can be divided into following key areas: high performance explosives, heat resistant explosives, and low sensitivity explosives.[1e, 1f] Tertiary explosives (“blasting agents”) – are highly insensitive to external stimuli (e.g.: impact, friction, heat, shock) and consequently must be initiated using an intermediate charge of a secondary explosive (“booster”).[1a, 1c, 1d, 1f] Moreover these explosives posses a relatively large critical diameter and are therefore not used in small charges.[1a] Tertiary explosives are predominantly used in large-scale