154010-97-6Relevant academic research and scientific papers
Thermal decomposition of 1,3,3-trinitroazetidine in the gas phase, solution, and melt
Nedel'Ko,Korsunskii,Makhova,Chukanov,Larikova,Ovchinnikov,Tartakovsky
, p. 2028 - 2034 (2009)
1,3,3-Trinitroazetidine (TNAZ) was synthesized using the alternative approach based on the transformation of 3-oximino-1-(p-toluenesulfonyl)azetidine in the reaction with nitric acid through intermediate pseudonitrol. The thermal decomposition of TNAZ in the gas phase, melt and m-dinitrobenzene solution in a wide concentration range (5-80%) was studied by manometry, volumetry, thermogravimetry, IR spectroscopy, and mass spectrometry. In the gas phase in the temperature range from 170 to 220°C the thermal decomposition proceeds according to the first-order kinetic law with the activation energy 40.5 kcal mol-1 and pre-exponential factor 1015.0 s-1. The major gaseous reaction products are N2, NO, NO2, CO2, H2O, and nitroacetaldehyde, and trace amounts of CO and HCN are formed. The rate-determining step of the process is the homolytic cleavage of the N-NO2 bond in the TNAZ molecule. In melt at 170-210 °C the thermal decomposition proceeds with the pronounced self-acceleration and the maximum reaction rates are observed at conversions 53.9-67.4%. The solid decomposition products accelerate the reaction. It is most likely that the autocatalysis of TNAZ decomposition in the liquid phase is due to the autocatalytic decomposition of 1-nitroso-3,3-dinitroazetidine, which is formed by the thermal decomposition of TNAZ. In m-dinitrobenzene TNAZ also decomposes with self-acceleration. The higher the concentration in the solution, the more pronounced the self-acceleration. Additives of picric acid moderately accelerate the thermal decomposition of TNAZ, whereas hexamethylenetetraamine additives exert a strong acceleration.
Improved synthesis of an energetic material, 1,3,3-trinitroazetidine (TNAZ) exploiting 2-iodoxy benzoic acid (IBX) as an oxidising agent
Singh, Alok,Sikder, Nirmala,Sikder, Arun K.
, p. 2560 - 2563 (2007/10/03)
Tetrahydropyranyl protected 1,3-dihalo-2-propanol reacts with p-toluene sulfonamide in the presence of K2CO3 to give corresponding N-p-tosyl-3-azetidinol. Deprotection and oxidation with iodoxy benzoic acid followed by oximation of N-p-tosyl-3-azetidinone readily affords the corresponding azetidine oxime in almost quantitative yield. The subsequent oxidative nitrolysis of oxime gives 1,3,3-trinitroazetidine (TNAZ) through a new sequence of reactions with excellent purity (> 99%) and moderate yield (40%).
Synthesis of 1,3,3-Trinitroazetidine via the Oxidative Nitrolysis of N-p-Tosyl-3-azetidinone Oxime
Axenrod, T.,Watnick, C.,Yazdekhasti, H.,Dave, P. R.
, p. 1959 - 1964 (2007/10/02)
The tert-butyldimethylsilyl ether of 1,3-dibromo-2-propanol reacted with p-toluenesulfonamide in the presence of K2CO3 to give the corresponding N-p-tosyl-3-azetidinol.The same azetidinol was obtained when the similarly silyl-protected 3-(p-toluenesulfonamido)propan-2-ol 1(p-toluenesulfonate) was treated with LiH.Desilylation and oxidation of the N-p-tosyl-3-azetidinol followed by oximation readily afforded N-p-tosyl-3-azetidinone oxime.Oxidative nitrolysis of the latter intermediate delivered 1,3,3-trinitroazetidine through a new sequence of reactions.
Novel Syntheses of 1,3,3-Trinitroazetidine
Katritzky, Alan R.,Cundy, Darren J.,Chen, Jie
, p. 271 - 276 (2007/10/02)
Alternative methods for the synthesis of 1,3,3-trinitroazetidine (TNAZ) from epichlorohydrin, and benzhydrylamine have been developed.These approaches employ N-sulfonyl-3-(hydroxyimino)azetidines as penultimate intermediates and represent an improvement over previously published methods which require either diazo containing intermediates or involve low yielding procedures.Parallel methods employing N-benzhydryl- and N-benzyl-3-(hydroxyimino)azetidine were also investigated as alternate routes to TNAZ
Synthesis of 1,3,3-Trinitroazetidine
Axenrod, Theodore,Watnick, Clara,Yazdekhasti, Hamid,Dave, Paritosh R.
, p. 6677 - 6680 (2007/10/02)
The t-butyldimethylsilyl ether of 3-(p-toluenesulfonamido)propane-2-ol-1-(p-toluenesulfonate) on treatment with LiH undergoes ring closure to the corresponding azetidine which is readily converted to N-tosyl-3-azetidinone oxime.By oxidative nitrolysis the latter affords 1,3,3-trinitroazetidine.
