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.

     

Synthesis and structure of 6- and 7-nitro-1-oxoisochroman-4-spirooxiranes

The reaction of diazomethane with 4-nitrophthalic acid anhydride gave 4- and 5-nitro-2-carbomethoxy--diazoacetophenones and 6- and 7-nitro-1-oxoisochroman-4-spirooxiranes. The structure of 7-nitro-1-oxoisochroman-4-spirooxirane was investigated by x-ray diffraction analysis.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1322–1325, October, 1989.     

Synthesis and constants of 6-nitro-2,3-dihydroquinolin-4(1h)-one

In the literature, there has appeared a communication [1] on the synthesis of 6-nitro-2, 3-dihydroquinolin-4(1H)-one (I) with mp 125–126C (2,4-dinitrophenylhydrazone, mp 269–270C) by the reaction of p-nitroaniline with acrylic acid. Quinolinone I with mp 232–234C (2,4-dinitrophenylhydrazone, mp 327–329C) was obtained by us by decarboxycyclization of N-(2-carboxy-4-nitrophenyl)--alanine in acetic anhydride in the presence of potassium acetate [2].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1390–1392, October, 1979.     

Synthesis of 6-nitro-4-sulfanyl-1H-indole derivatives from 2,4,6-trinitrotoluene

The synthesis of 6-nitro-4-sulfanyl-1H-indoles from 2,4,6-trinitrotoluene (TNT) is described. The first step is the nucleophilic substitution of an ortho-nitro group with a thiol to give the corresponding sulfide. The latter were transformed into the corresponding enamines upon treatment with dimethylformamide dimethyl acetal (DMF DMA). The enamines were converted into the indoles applying the Batcho–Leimgruber synthetic protocol.     

Synthesis of 6-nitro-8-chloro-2,3-dieydro-4(1H)-quinolone

6-Nitro-8-chloro-2,3-dihydro-4(1H)-quinolone and its dehydrogenation product-6-nitro-8-chloro-4-hydroxyquinoline — were isolated in the cyclization of N-(2-chloro-4-nitrophenyl--alanine in polyphosphoric acid.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 954–956, July, 1978.     

Synthesis and reduction of esters of N-(4-amino-5-nitro-6-pyrimidyl)amino acids

The reaction of esters of amino acids with 4-amino-6-chloro-5-nitropyrimidine has yielded esters of (4-amino-5-nitro-6-pyrimidyl)amino acids. The reduction of the esters of -(4-amino-5-nitro-6-pyrimidylamino) acids has yielded 4-amino-6-hydroxy-7,8-dihydropteridines. -(4-Amino-5-nitro-6-pyrimidylamino) acids and the ester of N-(4-amino-5-nitro-6-pyrimidyl)--alanine do not cyclize and on reduction give the corresponding diaminopyrimidine derivatives.     

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.     

Synthesis and characterization of energetic 3-nitro-1,2,4-oxadiazoles

All new: 3-Nitro-5-guanidino-1,2,4-oxadiazole (NOG) was synthesized from diaminoglycoluril with in situ generated dimethyldioxirane (DMDO). The impact sensitivity of NOG is more than 40?J with a decomposition temperature of 290?°C. Some other energetic derivatives have been prepared and characterized.     

Synthesis of 3-nitro-4-amino- and 3,4-diaminothiocoumarins

Nitration of 4-hydroxythiocoumarin gave 3-nitro-4-hydroxythiocoumarin, which was converted to 3-nitro-4-chlorothiocoumarin by the action of phosphorus oxychloride in dimethylformamide. The corresponding 3-nitro-4-aminothiocoumarins were synthesized by reaction of 3-nitro-4-chlorothiocoumarin with ammonia or amines. The 3-nitro-4-aminothiocoumarins were hydrogenated in alcohol over Raney nickel to give 3,4-diaminothiocoumarins. The-aminovinylcarbonyl form of the 4-substituted 3-aminothiocoumarins was established on the basis of the UV, IR, and PMR spectra.See [1] for our preliminary communication.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 43–47, January, 1978.     

Synthesis and some conversions of 6-methyl- and 1,6-dimethyl-5-nitro-4-phenyl-2-oxo-1,2,3,4-tetrahydropyrimidines

Using a modification of the Biginelli reaction, we have synthesized 6-methyl- and 1,6-dimethyl-5-nitro-4-phenyl-2-oxo-1,2,3,4-tetrahydropyrimidines. We have studied some of their chemical conversions involving the methyl group on the C₍₆₎ atom, the nitrogen atoms of the pyrimidine ring, and the phenyl substituent.Translated from Khimiya Geterosiklicheskikh Soedinenii, No. 3, pp. 388–392, March, 1993.     

Synthesis of 5(and 6)-nitro-4-methyl-2,3-dihydro-1h-1,5-benzo-2-diazepinones

The reaction of 4-nitro-o-phenylenediamine (I) with acetoacetic ester at room temperature under acid catalysis gives ethyl 3-(2-amino-5-nitrophenylamino)crotonate (II), which is readily cyclized to 7-nitro-4-methyl-2,3-dihydro-1H-1,5-benzo-2-diazepinone (III) on heating with alkaline agents. The reaction of I with acetoacetic ester in refluxing xylene gives isomeric 8-nitro-4-methyl-2,5-dihydro-1H-1,5-benzo-2-diazepinone (IVa) or 8-nitro-4-methyl-2,3-dihydro-1H-1,5-benzo-2-diazepinone (IVb), which are readily interconverted. The synthesis of IV is complicated by the side formation of 5-nitro-2-methylbenzimidazole (V) and thermal rearrangement of IVa and IVb to 5-nitro-1-isopropenylbenzimidazolone (VI). 6-Nitro-1-isopropenylbenzimidazolone (VII) is similarly obtained on heating III.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 696–699, May, 1972.