Mononitroso derivatives

Zhao J-S, A Halasz, L Paquet, C Beaulieu, J Hawari (2002) Biodegradation of hexahydro-l,3,5-trinitro-l,3,5-triazine and its mononitroso derivative hexahydro-l-nitroso-3,5-dinitro-l,3,5-triazine by Klebsiella pneumoniae strain SCZ-1 isolated from an anaerobic slndge. Appl Environ Microbiol 68 5336-5341. 

Acidity. Hector s bases are mono-acid bases34-80,40,41>50,51 the presence of only one imino group in the preferred formulation 35 accounts well for the observed exclusive formation of monoalkyl, monoacyl, and mononitroso derivatives. The A-ethyl derivative30 is reducible to s-diphenylguanidine and ethylamine and is therefore regarded54 as 37, and the nitroso derivative as 38. 

Urbanski and co-workers prepared a number of 1,5-diazocines (see Section II,C,1) and investigated their conformations. In one study, molecular refractions were determined for compounds 101 (cis and trans, R = Me, Et, n- Pr R1 = H). Infrared spectra of these compounds showed both bonded NH2 and NOz groups the compounds formed only monohydrochlorides and mononitroso derivatives. These facts suggested intramolecular hydrogen bonding between the two ring nitrogen atoms. The experimental dipole moment of trans-101 (R = Et, R1 = H) was consistent with that calculated for a crown conformation (184), with the two... 

The formation of a monobenzoyl derivative and a mononitroso derivative, b.p. 176°/4 mm., [a]u — 155° (no solvent) shows that anabasine is a secondary-tertiary diacidic base. This conclusion is substantiated by the formation of an A-methylanabasine, b.p. 268°, when the base is heated with formaldehyde and formic acid (420). With potassium permanganate anabasine is oxidized to nicotinic acid whereas dehydrogenation either with silver acetate or with zinc dust causes the loss of six hydrogen atoms and the formation of 3, 2-dipyridyl, b.p. 293-294° (picrate, m.p. 151-152°)(423). These experiments support structure CLXXIV previously applied to anabasine (399), a formulation that is confirmed by the following experiments. When A-benzoylanabasine methiodide is oxidized with potassium ferricyanide, the 7V-benzoyl derivative of the corresponding pyridone,... 

The TOF velocity spectra show that the molecular weight of the CH3NHCHO product is -118, suggesting that this product leaves the reaction cell as a dimer. However, it is possible that this product has a structure that is somewhat different from N-methylformamide (e.g. acetamide). The two unique sets of products each have a mononitroso derivative of the parent compound. Experiments conducted under conditions in which RDX and HMX only evaporate and do not decompose show no evidence of the nitroso derivative, thus, this product is formed during the decomposition and is not a contaminant in the starting material. The other products that are unique to the RDX decomposition are NO2 and hydroxy-s-triazine (HST). These two products indicate that rupture of the N-N bond is an important reaction path way in RDX. The products that are unique to the decomposition of HMX are CO, C2H 20, and a nonvolatile residue (NVR). 

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