We report the synthesis and characterization of several bicyclic mono- and dinitrourea compounds as energetic materials and discuss their use as precursors to other energetic compounds. The new nitrolyzing reagent, trifluoromethanesulfonic acid anhydride/20% N2O5/nitric acid, will also be described. 相似文献
A number of highly efficient methods for the preparation of novel derivatives of 9-selenabicyclo[3.3.1]nonane in high yields based on selenium dibromide and cis,cis-1,5-cyclooctadiene are reported. The one-pot syntheses of 2,6-diorganyloxy-9-selenabicyclo[3.3.1]nonanes using various O-nucleophiles including alkanols, phenols, benzyl, allyl, and propargyl alcohols were developed. New 2,6-bis(1,2,3-triazol-1-yl)-9-selenabicyclo[3.3.1]nonanes were obtained by the copper-catalyzed 1,3-dipolar cycloaddition of 2,6-diazido-9-selenabicyclo[3.3.1]nonane with unsubstituted gaseous acetylene and propargyl alcohol. The synthesis of 2,6-bis(vinylsulfanyl)-9-selenabicyclo[3.3.1]nonane, based on the generation of corresponding dithiolate anion from bis[amino(iminio)methylsulfanyl]-9-selenabicyclo[3.3.1]nonane dibromide, followed by the nucleophilic addition of the dithiolate anion to unsubstituted acetylene, was developed. The glutathione peroxidase-like activity of the obtained water-soluble products was estimated and compounds with high activity were found. Overall, 2,6-Diazido-9-selenabicyclo[3.3.1]nonane exhibits the highest activity among the obtained compounds. 相似文献
Summary 1-Aza-3-oxabicyclo[3.3.1]nonan-2-one, an N-bridgehead bicyclic urethane, polymerized in bulk under the influence of dibutyltin oxide and p-toluenesulfonic acid. In solution the monomer polymerizes in the presence of phosphoric acid. This is only the second example of ring opening polymerization of a bicyclo[3.3.1]nonane. The driving force in the present case is thought to be the relief of strain energy in the monomer conferred by its chair-boat conformation. 相似文献
Transannular Reactions of Cycloalkenes, Cycloalkadienes and Cycloalkatrienes. VIII. The Electrophilic Addition of Pseudohalogenes to Cycloocta-1(Z), 5(Z)-diene The reaction of cycloocta-1(Z), 5(Z)-diene 5 with chlorothiocyanate is described. The main process is the normal anti-addition to produce trans-5-chloro-6-thiocyanato-(Z)-cyclooctene 6 . In addition 2,6-dichloro-9-thiabicyclo [3.3.1] nonane 7 and 2,6-dithiocyanato-9-thiabicyclo[3.3.1] nonane 8 are obtained as products of a transannular reaction. 相似文献
The regioselectivity of transannular O-heterocyclization of cycloocta-1,5-diene ( 1 ) with phenylsulfenyl chloride and methanol or water, respectively, is determined by the oxy-component which acts as nucleophilic partner in the electrophilic three component reaction. The thermodynamically more stable endo, endo-2,6-bis(phenylsulfenyl)-9-oxabicyclo[3.3.1]nonane ( 2 ) is formed almost exclusively in methanol while the isomeric 9-oxabicyclo[4.2.1]nonane ( 3 ) is favored under kinetic control in the presence of water. The oxidation of 2 or 3 yields the bissulfones 4 and 5 , respectively. 相似文献
A formal amide insertion reaction for the synthesis of nitrogen‐bridged polycyclic frameworks with diverse functionalities was developed using a sustainable copper catalyst as an advantageous alternative to precious rhodium catalysts. The remarkable feature of this methodology is the amount of catalyst loading (0.05 mol%). The optimized reaction conditions enable access to aromatic ring‐fused 8‐azabicyclo[3.2.1]octane, 9‐azabicyclo[3.3.1]nonane, and 6‐azabicyclo[3.2.2]nonane derivatives in moderate to excellent yields.
The aliphatic energetic plasticizers with three and four –CH2 between nitrate ester and nitramine were synthesized to obtain a plasticizer that is more stable than N-butyl-N-nitratoethyl nitramine (BuNENA) with two –CH2. First, amino alcohol compounds such as propylamino propanol (PAP) and ethylamino butanol (EAB) as a precursor of energetic plasticizer were synthesized. However, unlike in BuNENA synthesis, various side reactions occurred in the nitration of amino alcohols. Fortunately, it was possible to considerably suppress the formation of side products in the nitration of PAP by using a solvent and an appropriate concentration of nitric acid. In addition, an energetic plasticizer with higher oxygen content was obtained through the nitration of intermediate, amide alcohol, which was formed in the synthesis of EAB. 相似文献
2,4,6,8 ‐ Tetranitro – 2,4,6,8 ‐ tetraazabicyclo[3.3.1]nonane‐3,7‐dione (TNPDU) has been synthesized from propane diurea by nitration with nitric acid‐acetic anhydride with a yield of 85 %. The molecular structure of the compound has been determined by elemental analysis, IR and 1H‐NMR spectroscopy. Some of the properties including thermal and explosion delay behaviour of the compound and its mixtures with high explosives, are reported. An analogous compound 2,5,7,9‐tetranitro‐2,5,7,9‐tetraazabicyclo[4.3.0]nonane–8–one (TNABN) has also been evaluated for some of the explosive properties considering its good stability and insensitiveness as compared to other nitrodiurea derivatives. 相似文献