Synthesis of New Nitroamino-Containing 1,2,4-Triazines by Reaction of 1-Amino-2-nitroguanidine with α-Diketones

A Review on the Reactivity of 1-Amino-2-Nitroguanidine (ANQ)

“…Under the catalysis of acid, a linear monohydrazone ( 64 ) was prepared by an equimolar ratio of ANQ and butane-2,3-dione. A 2-fold excess of ANQ was used to generate a 5:8 ratio of a mixture of monohydrazone ( 64 ) and dihydrazone ( 65 ) [71], as seen in Scheme 20. Similarly, ANQ reacted with acetylacetone to generate acetylacetonenitroguanylosazone [72].…”

“…As long as the reaction temperature and reaction time were properly adjusted, 3,5-dimethyl- N -nitro-1 H -pyrazole-1-carboxamidine (75) was formed by reaction of ANQ and pentane-2,4-dione, no matter in acidic or basic conditions [85,86], as seen in Scheme 23. However, ANQ reacted with butane-2,3-dione and 1,2-diphenylethanedione in acid or base conditions leading to different nitroamino products containing 1,2,4-triazine [71]. In water-alkaline solution, ANQ reacted with 2,3-butanedione to form 3-nitroamino-5,6-dimethyl-1,2,4-triazine ( 76 ) by heterocyclization at room temperature.…”

“…When using an acid catalyst, 5-ethoxy-4,5-dihydro-(2 H )-1,2,4-triazine ( 79 ) was separated, and the synthesis of 79 could be regarded as the result of the alkoxylation of the initially formed intermediate. Compound 79 was unstable and it could be converted to compound 78 by eliminating ethanol in DMSO- d 6 solution, as seen in Scheme 25 [71].…”