Oxidative N-nitration of secondary amines

Reaction of secondary amines with the nitrite anion assisted by diacetoxyiodobenzene results in respective N-nitroamines. It is the first example of oxidative nitration of the amino group. N-Nitrosoamines are by-products. The yields and the ratio of the nitration and nitrosation products depend on the nature of the starting amine, cation of the salt used, and the solvent.     

Acylation of 1-methoxy-3-methyl-1-triazene 2-oxide

Chlorides and anhydrides of carboxylic (including dicarboxylic) acids react with salts of 1-methoxy-3-methyl-1-triazene 2-oxides to give the corresponding 3-acyl-1-methoxy-3-methyl-1-triazene 2-oxides.     

Trinitroethyl ethers of substituted alcohols

The influence of the trinitromethane salt cations and the substituents in the alkyl moiety of chloromethyl ethers of alcohols on the yields of trinitroethyl ethers of the substituted alcohols formed from them was established. On this basis a representative series of previously unavailable trinitroethanol ethers was synthesized.     

<Emphasis Type="Italic">N</Emphasis>-(2-Azidoethyl) derivatives of methylenebis(1-oxytriaz-1-ene 2-oxides)

A method for synthesizing new compounds capable of releasing NO within living organisms, namely, 2-azidoethyl derivatives of methylenebis(1-oxytriaz-1-ene 2-oxides) bearing one or few 2-azidoethyl moieties, was developed. The synthesis involves nucleophilic substitution of the bromine atoms of the parent 2-bromoethyl derivatives of methylenebis(1-oxytriaz-1-ene 2-oxides) with the azide group. Some of the synthesized compounds are of interest as promising energetic materials.     

<Emphasis Type="Italic">N</Emphasis>-β-Nitroxyethyl derivatives of 1,1’-[methylenebis(oxy)]bis(triaz-1-ene 2-oxides)

Synthetic procedures towards new N-β-hydroxyethyl- and N-β-bromoethylated 1,1’-[methyl enebis(oxy)]bis(triaz-1-ene 2-oxides) were developed. N-β-Nitroxyethyl[methylenebis(oxy)]- bis(triaz-1-ene 2-oxides) were first synthesized by nitration of N-β-hydroxyethyl derivatives and nucleophilic substitution of the bromine atom of N-β-bromoethyl derivatives. The first representative of a new class of energetic compounds, namely, (1-nitroxymethoxy)triaz-1-ene 2-oxide, was synthesized.     

Synthesis of 1-alkoxy-3-(2-hydroxyethyl)-1-triazene 2-oxides

Synthetic procedure to access the first representatives of a new series of 3-monosubstitued functional derivatives of 1-alkoxy-1-triazene 2-oxides, i.e., 1-alkoxy-3-(2-hydroxyethyl)- and 1-alkoxy-3-(2-acetoxyethyl)-1-triazene 2-oxides, were elaborated. 1-Alkoxy-3,3-bis(2-hydroxyethyl)-1-triazene 2-oxides were used to derive 3-(2-acetoxyethyl)-, 3-(2-bromoethyl)- and 3-(2-cyanoethyl)substituted 1-alkoxy-3-(2-acetoxyethyl)-1-triazene 2-oxides.     

Synthesis of 3,3-bis(2-hydroxyethyl) and 3,3,3’-tris(2-hydroxyethyl) derivatives of 1,1’-[methylenebis(oxy)]bis(triaz-1-ene 2-oxides)

Synthetic procedures to access new potential NO donors that can generate NO in living systems, 3,3-bis(2-hydroxyethyl) and 3,3,3’-tris(2-hydroxyethyl) derivatives of 1,1’-[methylenebis(oxy)]bis(3,3-dialkyltriaz-1-ene 2-oxides), were elaborated. 3,3-Bis(2-acetoxyethyl)-1(chloromethoxy)triaz-1-ene 2-oxide reacts with 1-hydroxytriaz-1-ene 2-oxide sodium salts to give a series of alkylated 3,3-bis(2-acetoxyethyl) derivatives. Deacetylation of the latter produces 3-(2-hydroxyethyl)-11,11-dialkyl-6,8-dioxa-3,4,5,9,10,11-hexaazaundeca-4,9-dien-1-ol 4,10-dioxides and 11-alkyl-3-(2-hydroxyethyl)-6,8-dioxa-3,4,5,9,10,11-hexaazatrideca-4,9-diene-1,13-diol 4,10-dioxides.     

3,4-Bis(α-nitroalkyl-ONN-azoxy)furazans and some of their derivatives

Reaction of pseudonitroles and their derivatives with diaminofurazan in the presence of dibromoisocyanuric acid (DBI) resulted in symmetrical 3,4-bis(-nitroalkyl-ONN-azoxy)-furazans or their derivatives. For the synthesis of bis(nitroalkyl-ONN-azoxy)furazans bearing various a-nitroalkyl-ONN-azoxy groups, the method based on the reaction of ??-nitronitroso compounds with 3-amino-4-(nitroalkyl)-ONN-azoxy)furazans (in the presence of DBI) was developed. Synthetic procedures towards aforementioned compounds with nitromethyl-, dibromonitromethyl-, trinitromethyl-ONN-azoxy and other groups were described.     

New method for the synthesis of 2-substitutedN, N′-diacylimidazolidines

A method for the synthesis of 2-substitutedN, N′-diacylimidazolidines was developed. The method is based on the reactions of acylating reagents (carboxylic acid chlorides and anhydrides, sulfonic acid chlorides, a carbamic acid chloride, and ethyl chlorocarbonate) with Schiff's bases prepared by the reaction ofN-acylethylenediamines with aldehydes. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya. No. 5, pp. 896–900, May, 2000.