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InChI:InChI=1/C3H4N4O6/c8-5(9)3(6(10)11)1-4(2-3)7(12)13/h1-2H2

Upstream product

• 154010-97-6 3-oximino-1-(p-toluenesulfonyl) azetidine 
• 125735-38-8 N-tert-butyl-3,3-dinitroazetidine 

Relevant academic research and scientific papers

Thermal decomposition of 1,3,3-trinitroazetidine in the gas phase, solution, and melt

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.

Synthesis of heterocyclic geminal nitro azides

The oxidative azidation reactions of C-nitro-substituted saturated heterocyclic compounds, viz., the nitro derivatives of oxetane, azetidine, 1,3-dioxane, tetrahydro-1,3-oxazine, and hexahydropyrimidine, were investigated. A novel representatives of the geminal nitro azides were prepared and their physicochemical properties were studied. The process of the formation of the geminal dinitro compounds upon oxidative azidation was analyzed.

Improved synthesis of an energetic material, 1,3,3-trinitroazetidine (TNAZ) exploiting 2-iodoxy benzoic acid (IBX) as an oxidising agent

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%).

Improved synthesis of an energetic material, 1,3,3-trinitroazetidine exploiting 1-azabicyclo [1.1.0]Butane

Expeditious synthesis of 1-nitroso-3-nitroazetidine (6), a useful key intermediate for the synthesis of 1,3,3-trinitroazetidine (4), was investigated by using 1-azabicyclo[1.1.0]butane (3) and NaNO2 in the presence of some acids. The most efficient method was achieved in 26% yield by treatment of 3 with NaNO2 in the presence of H2SO4. Conversion of 6 into 4 was also carried out.

Thermal decomposition pathways of 1,3,3-trinitroazetidine (TNAZ), related 3,3-dinitroazetidium salts, and 15N, 13C, and 2H isotopomers

The thermal decomposition of 1,3,3-trinitroazetidine (TNAZ) and related 3,3-dinitroazetidium (DNAZ+) salts was examined neat and in solution. TNAZ kinetics were found (160-250 °C) to be first-order and nearly identical neat and in benzene, with an activation energy of 46.6 kcal/mol (195 kJ/mol). The DNAZ+ salts were less thermally stable than TNAZ, and neat did not decompose in a first-order fashion. However, in aqueous solution the DNAZ+ salts did decompose following first-order kinetics; their rates were similar with minor differences apparently related to the strength of the anion as a conjugate base. Like simple nitramines such as dimethylnitramine, TNAZ tended to form N2O rather than N2, but unlike other nitramines it formed about as much NO as N2O. TNAZ isotopomers labeled with 13C and with 15N were prepared and used to identify the origin of the decomposition gases and the identity of the condensed-phase products. Early in the decomposition of TNAZ, most of the NO came from the nitro group attached to the azetidium ring nitrogen. Most of the N2O was the result of the nitro groups interacting with each other, while the majority of the N2 contained one nitrogen from the ring. Many condensed products have been identified, but five stand out because they are formed in the thermolysis of TNAZ and the three DNAZ+ salts [NO3-, Cl-, N(NO2)2-]. These are 3,5-dinitropyridine (M, always a minor product), 1-formyl-3,3-dinitroazetidine (L), 1,3-dinitroazetidine (K), 1-nitroso-3,3-dinitroazetidine (E), and 1-nitroso-3-nitroazetidine (G); the identity of the first four has been confirmed by use of authentic samples. Of these five, the last four have been shown to interconvert with TNAZ and each other under the conditions of these experiments. This study confirms the presence of two competitive TNAZ decomposition pathways. Under the conditions of this study, N-NO2 homolysis is slightly favored, but products, such as K, resulting from C-NO2 scission, are also well represented.

Synthesis of trinitroazetidine compounds

Method of synthesizing a 1,3,3 trinitroazetidine compound (TNAZ) comprising the steps of: selecting a compound of the formula I: STR1 wherein R' is one of hydrogen and an organic group and R is selected from the group consisting of electron withdrawing and electron donating groups; and, reacting the selected compound with a nitrolyzing agent such that a TNAZ compound is formed from the reaction.

Synthesis of 1,3,3-Trinitroazetidine via the Oxidative Nitrolysis of N-p-Tosyl-3-azetidinone Oxime

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.

Synthesis of 3,3-dinitroazetidine

The compound, 3,3-dinitroazetidine, and a process of preparing 3,3-dinitroazetidine including reacting a mixture of 1-tertiary-butyl-3,3-dinitroazetidine and benzyl chloroformate to form 1-(benzyloxycarbonyl)-3,3-dinitroazetidine, reacting the 1-(benzyloxycarbonyl)-3,3-dinitroazetidine and trifluoromethanesulfonic acid to form 3,3-dinitroazetidinium trifluoromethanesulfonate, and neutralizing the 3,3-dinitroazetidinium trifluoromethanesulfonate with a base to form 3,3-dinitroazetidine are provided. Salts of the 3,3-dinitroazetidine and preparation of such salts are also disclosed.

Novel Syntheses of 1,3,3-Trinitroazetidine

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