The 1-alkoxy-6-nitro-1,2,3-benzotriazole system

The 1-alkoxy-6-nitro-1,2,3-benzotriazole system has been synthesized and characterized via its physical and chemical properties. INDO/molecular orbital calculations provide a good account of the major bands in its ultraviolet absorption spectrum.     

Synthesizing isomeric methoxy derivatives of 6-nitro-9-chlordacridine and 6-nitroacridone

Condensation of 2-chloro-4-nitrobenzoic acid with o, m, and p-anisidines under the conditions of the Ullmann reaction gives the corresponding 2-, 3-, or 4-methoxy derivatives of 5-nitrodiphenylamine-2-carboxylic acid. Phosphorus oxychloride cyclizes the latter to the corresponding methoxy-substituted 6-nitro-9-chloroacridines, and the latter, when treated with dilute hydrochloric acid, give good yields of methoxy derivatives of 6-nitroacridones.     

Asymmetric oxidation of 4-nitro-6-trifluoromethyl-1,2,3-benzotrithiole

Both enantiomers of 4-nitro-6-trifluoromethyl-1,2,3-benzotrithiole 1-oxide as analogs of Varacins B and C were synthesized for the first time. The use of the Modena method ensures higher optical purity but lower yields of the chiral sulfoxides, as compared to the Kagan procedure.     

Crystal Structure of 6-Chloro-4-nitro-2-phenylpyrimidine

The crystal structures of 6-chloro-4-nitro-2-phenylpyrimidine and 6-chloro-2-phenylpyrimidine have been determined using X-ray diffraction. The effect of the nitro group and the endocyclic nitrogen atoms on the geometric parameters of the 2- and 4-nitropyrimidine molecules, and also related -nitroazines are compared.     

Synthesis of enantiomers of 6-nitro- and 6-amino-2-methyl-1,2,3,4-tetrahydroquinolines

Enantiomers of 2-methyl-6-nitro-1,2,3,4-tetrahydroquinoline have been obtained by kinetic resolution of racemic 2-methyl-1,2,3,4-tetrahydroquinoline in acylation with acyl chlorides of N-protected amino acids followed by regioselective nitration of the diastereoisomeric amides and acidic hydrolysis. The introduction of a trifluoroacetyl protecting group into the position 1 of the enantio pure nitro compound followed by the reduction led to (S)-6-amino-2-methyl-1-trifluoroacetyl-1,2,3,4-tetra-hydroquinoline in a high yield.     

Synthesis of 5-amino-6-nitro-1,2,3,4-tetrazine 1,3-dioxide

5-Amino-(tert-butyl-NNO-azoxy)-1,2,3,4-tetrazine 1,3-dioxide reacts with nitronium tetra-fluoroborate to give 5-amino-6-nitro-1,2,3,4-tetrazine 1,3-dioxide. This compound is of interest as a new energetic material. A plausible reaction mechanism involves electrophilic substitution of the tert-butyl-NNO-azoxy group by the nitro group.

     

Isomeric methoxy derivatives of 6-nitro-9-(p-anisylamino)acridine

1-, 2-, 3-, and 4-methoxy derivatives of 6-nitro-9-(p-anisylamino) acridine ate synthesized.     

3-Arylidene-6-nitro-1,8-naphthaledes and phenalene-1,3-diones based on them

Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1288–1289, September, 1993.     

Reactions of 4-Aryl-2-hydrazino-3-nitro-6-R-quinolines with HNO2

The reaction of 4-aryl-2-hydrazino-3-nitro-6-R-quinolines with NaNO₂ in AcOH gives the corresponding tetrazolo[1,5-a]quinolines. In contrast to tetrazolo[1,5-c]pyrimidines they cannot be converted to 6-R-4-phenyl[1,2,5]oxadiazolo[3,4-b]quinoline-3-oxides by heating in THF, toluene, or AcOH. Total energy quantum-chemical calculations using the MINDO/3 and MNDO methods show that [1,2,5]oxadiazolo[3,4-b]quinoline-3-oxides are significantly higher in energy (230-280 kcal/mol) than the mentioned tetrazolo[1,5-a]quinolines and hence their formation is unlikely.