Mannich condensations 1,5-diazocines

Adolph and Cichra synthesized a number of polynitroperhydro-1,5-diazocines and compared their properties with the powerful military explosive HMX. A type of Mannich condensation was used to form the 1,5-diazocine rings the condensation of ammonia and methylamine with formaldehyde and bis(2,2-dinitroethyl)nitramine (46) forming diazocines (47) and (48) respectively. 1,3,3,7,7-Pentanitrooctahydro-1,5-diazocine (47) is A-nitrated to 1,3,3,5,7,7-hexanitrooctahydro-l,5-diazocine (52) in near quantitative yield using mixed acid. 

Adolph and Cichra prepared some A-nitroso-l,5-diazocines from the condensation of bis(2,2-dinitroethyl)nitrosoamine (49) with formaldehyde and various amines. 3,3,7,7-Tetranitro-1 -nitrosooctahydro-1,5-diazocine (50), the product obtained from the Mannich condensation of (49), formaldehyde and ammonia, was used to prepare nitro- and nitroso- 1,5-diazocines (52), (53), and (54). 

In a novel 1,4-diazocine synthesis, diacetylene was condensed with ED and 1,2-propylenediamine to afford diazocines 123 (63DOK1353). Nakamura and Kamila ran a Mannich condensation with benzoylpyrrole 124 and... 

Other Mannich and Mannich-type condensations (also see Section II, C, 1) have been used to synthesize 1,5-diazocines. Two groups reported reacting the tetranitro-A-nitroso compound 152 (R = NO) with alkylam-ines and formaldehyde, affording tetranitro-A-nitrosodiazocines 153 (R = NO, R1 = Me) (81IZV1676 83S830) and 153 (R = NO R1 = H, i-Pr)... 

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