III International Conference

PP-I-27STUDY OF ONE-POT REDUCTIVE DEBENZYLATION-ACYLATION OFSUBSTITUTED HEXABENZILHEXAAZAIZOWURTZITANES OVERPALLADIUM-BASED CATALYSTSKoskin A.P., Simakova I.L.Boreskov Institute of Catalysis SB RAS, Novosibirsk, RussiaE-mail: simakova@catalysis.ruHexanitrohexaazaisowurtzitane (HNIW) has been suggested earlier as a new generationof perspective highly energetic material. However its application is restricted because of highcost of a product synthesis. Different precursors could be used forhexaarylhexaazaisowurtzitane (HAIW) preparation which differ strongly in reactioncapability. In present work we have studied of one-pot process reductive dearylation-acylationof substituted HAIW over palladium-based catalysts. The general kinetic peculiarities andPd/C catalyst resistance to deactivation during the process are investigated.Polycyclic nitramines is known to be high-dense and energy-rich explosives. One of themis hexanitrohexaazaisowurtzitane (HNIW) also referred to as CL-20 that has been developedas a new generation of perspective explosives. The propellants or explosives composed ofHNIW are expected to increase the performance in specific impulse, burn rate, and detonationvelocity [1]. A great number of studies and calculations have been published on the physicalproperties of HNIW and for potential military applications [2], but the published informationon the synthesis of CL-20 is rather limited.OH2OHPhCH 2 NH 2CH 3 CN, H +80%CHArH 2 C2 Ar4N 32N CH 2 Ar6N1511 N 1279 8NCHN2 Ar10CH 2 ArArH 2 C3, HAIWPd/C, H 2Ac 2 OArH 2 CNNArH 2 CAcN AcNNN AcAc4, TADAIWPd/C, H 2HCOOHOHCNNOHCAcN AcNNN AcAcHNO 3NH 4 NO 3O 2 NNNO2 NNO 2N NO 2NNN NO 2NO 25, TADFIW 1, HNIWSynthesis of polycyclic nitramines usually includes three stages: formation of apolycyclic cage of hexaarylhexaazaisowurtzitane (HAIW) by condensation of benzylamineswith glyoxal, cage transformation to obtain HNIW precursor (in two stages) and its nitrolysis[3]. Second two-step stage of synthesis CL-20 proceeds as one-pot reductive debenzylationacylationover palladium-based catalyst. The latter is the most important stage in the CL-20synthesis. At the same time Pd/C catalyst was found to be deactivated during 3→4→5 thatdoes not permit to use it in recycles.56