Synthesis of 2-monofunctionalized 2,4,6,8-tetraazabicyclo[3.3.0]octane-3,7-diones

New (1R*,5S*)-2-R-2,4,6,8-tetraazabicyclo[3.3.0]octane-3,7-diones containing the terminal carboxy or hydroxy group in the substituent R were synthesized by cyclocondensation of 4,5-dihydroxyimidazolidin-2-one with 1-R-ureas. Single-crystal X-ray diffraction analysis showed that 2-carboxyethyl-2,4,6,8-tetraazabicyclo[3.3.0]octane-3,7-dione crystallizes as a racemate.     

N-Silylation of 2,4,6-Trialkyl-2,4,6,8-tetraazabicyclo[3.3.0]octane-3,7-diones

N-Trimethylsilyl derivatives of 2,4,6,8-tetraazabicyclo[3.3.0]octane-3,7-diones have been prepared for the first time and the electrophilic substitution reaction of the trimethylsilyl group has been studied.     

Reaction of 1,3,5-tri-tert-butylbenzene with 2,4,6,8-tetraiodo-2,4,6,8-tetraazabicyclo[3.3.0]octane-3,7-dione

Reactions of 1,3,5-tri-tert-butylbenzene with 2,4,6,8-tetraiodo-2,4,6,8-tetraazabicyclo[3.3.0]octane-3,7-dione in acetic and trifluoroacetic acids involve substitution of one or two tert-butyl groups in the aromatic ring with formation of mono-, di-, and triiodo-substituted derivatives. No iodo derivatives are formed in acetonitrile.     

Successful synthesis of 2,4,6,8-tetraiodo-2,4,6,8tetraazabicyclo[3.3.0]octane-3,7-dione

Tomsk Polytechnical University. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1695–1696, December, 1995. Original article submitted November 27, 1995.     

2,4,6,8-Tetraiodo-2,4,6,8-tetraazabicyclo[3.3.0]octane-3,7-dione as a mild and convenient reagent for iodination of aromatic compounds

2,4,6,8-Tetraiodo-2,4,6,8-tetraazabicyclo[3.3.0]octane-3,7-dione (tetraiodoglycoluril) is a convenient reagent for preparative iodination of benzene, alkylbenzenes, polycyclic hydrocarbons, aromatic amines, and phenol ethers in organic solvents under mild conditions.     

Synthesis and structure of 2,4,6,8-tetramethyl-3,7-dithia-2,4,6,8-tetraazabicyclo[3.3.0]octane 3,3,7,7-tetraoxide

Condensation of N,N′-dimethylsulfamide with glyoxal gave 2,4,6,8-tetramethyl-3,7-dithia-2,4,6,8-tetraazabicyclo[3.3.0]octane 3,3,7,7-tetraoxide, a sulfur-containing analog of 2,4,6,8-tetramethyl-2,4,6,8-tetraazabicyclo[3.3.0]octane-3,7-dione (Mebicar). The product structure was studied by X-ray analysis.     

3,7-二硝亚胺基-2,4,6,8-四硝基-2,4,6,8-四氮杂双环[3.3.0]辛烷结构与性能的量子化学研究

设计了一种新型高能量密度化合物--3,7-二硝亚胺基-2,4,6,8-四硝基-2,4,6,8-四氮杂双环[3.3.0]辛烷, 应用密度泛函理论(DFT)的B3LYP 方法在6-31G(d,p)基组水平上对该化合物进行了结构全优化, 并计算得到其红外(IR)光谱; 通过键级分析获得热解引发键的位置为N7-N22, 同时求得校正后的键离解能为91.47 kJ/mol. 采用Monte-Carlo方法预测该化合物的理论密度为2.16 g/cm³; 基于理论密度并结合等键反应及Kamlet-Jacobs公式预测了生成焓、爆速、爆压和爆热值分别为1219.94 kJ/mol, 10.43 km/s, 53.44 GPa和7407.84 J/g. 以上性能参数显示, 该目标化合物达到了高能量密度化合物的基本要求, 是一种潜在的含能材料. 同时给出了该化合物的逆合成路线.     

Preparation of Bicyclo[3.3.0]octane-2,8-dione- and Declain-1,8-dione-Derivatives

Alkylation of bicyclo[3.3.0]octane-2,8-dione ( 1 ), which is prepared by a modification of the procedure described in the literature, gives the methyl- and propynyl-derivatives 6 and 7 (Scheme 1). In addition to the method described previously (Scheme 2), 9-methyl-cis-decalin-1,8-dione 9 is obtainable stereoselectively either by cyclization of keto-acid 16 , or by aldol cyclization of keto-aldehyde 26 and oxydation of the resulting alcohols 24 and 25 (Scheme 4). The β-keto-alcohols 24 and 25 undergo a base-catalyzed isomerization; the trans-decalin isomers 27 and 28 are not detected in this equilibrium mixture (Schemes 4 and 5)l. Monoreduction of cis-dione 9 gives the endo-alcohol 25 , while 27 is the favored product of the reductin of trans-dione 10 (Scheme 4). Optically pure (+)- 25 can be prepared from (9S,10R)-monoacetal 29 (Scheme 5).     

Kinetic Study on the Exothermic Decomposition Reaction of 2,4,6,8-Tetranitro-2,4,6,8-tetraazabicyclo[3,3,1]onan-3,7-dione

Introduction 2,4,6,8-Tetranitro-2,4,6,8-tetraazabicyclo[3,3,1]nonan- 3,7-dione (1) is a novel energetic cyclourea nitramine containing four —NO2 groups (Figure 1). The detona-tion velocity corresponding to =1.93 gcm-3 is 9034 ms-1. It is the potential high explosive. Its preparation,1 properties1 and hydrolytic behavior2 have been reported. Thermal behavior is one of the most important aspects of the compound in practical application. However, its kinetic parameters of thermal decomposition…