Reactions ofN-nitramines and their trimethylsilyl derivatives withN,N-bis(trimethylsilyloxy)enamines

Trimethylsilyl derivatives of methyl- and ethylnitramine react asN-centered nucleophiles with 2-N,N-bis(trimethylsilyloxy)aminopropene to give trimethylsilyl derivatives of hitherto unknown α-(N-nitro)alkylamino-substituted acetone oximes. As an ambident nucleophile, nonsubstituted methylnitramine reacts with the same enamine to give both a product of N,C-corss-coupling and a product of O,C-cross-coupling,viz., N′-methyl-N-[(2-trimethylsilyloxyimino)propoxy]diazeneN-oxide. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2045–2047, October, 1998.     

Chemistry of N,N-bis(silyloxy)enamines. 4. Study of the reactions of N,N-bis(silyloxy)enamines with 1,3-diones

Smooth C,C-cross-coupling of N,N-bis(silyloxy)enamines with methyl malonates gives the corresponding methyl -hydroxyiminoalkylmalonates.     

Reaction ofN,N-bis(chloromethyl)amides withN,N′-diacylated alkene(arylene)diamines

Reactions ofN,N-bis(chloromethyl)amides withN,N′-diacyl derivatives of ethylenediamine (oro-phenylenediamine) result in formation of the corresponding 1,3,5-triacylated perhydro-1,3,5-triazepines (or their benzoanalogs) or 1,3-diacylated imidazolidines (or their benzoanalogs). Reactions ofN,N-bis(chloromethyl)amides withN,N′-ditosylated trimethylenediamine occur in a similar way. The direction of the reactions depends on the type of the acyl substituents and the strength of the bases. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2270–2273, November, 1998.     

Chemistry of <Emphasis Type="Italic">N,N</Emphasis>-bis(silyloxy)enamines 7. Quaternization of tertiary amines and nitrogen-containing heterocycles by <Emphasis Type="Italic">N,N</Emphasis>-bis(silyloxy)enamines

Coupling of N,N-bis(silyloxy)enamines with tertiary amines and nitrogen-containing heterocycles affording the corresponding functionalized ammonium or iminium salts was studied. The area of its application was determined, and optimal procedures for the synthesis of the target products were proposed. The mechanism including the formation of conjugated nitroso alkene or a silylnitrosonium cation as key intermediates is discussed.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2137–2143, October, 2004.     

Synthesis ofN,N′-dialkylmethylenebis(nitramines) fromN-alkylsulfamates

Symmetrical and unsymmetricalN,N′-dialkylmethylenebis(nitramines) were obtained fromN-alkylsulfamates by condensation with formaldehyde and subsequent nitration. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1085–1087, June, 2000.     

A new method for the synthesis ofN,N′-thiobisamines

Reaction of secondary amines (morpholine and piperidine) with sulfur and iodine affordedN,N′-thiobisamines in good yields. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1891–1892, October, 1997.     

Reactions ofN,N-dibromo-tert-butylamine with ketoximes

Reactions of acetone, cyclohexanone, and adamantanone oximes withN,N-dibromo-tert-butylamine result in the correspondingC-bromo-diazene-N-oxides. In the case of benzophenone oxime,O, O'-(diphenylmethylene)-bis-benzophenone oxime has been obtained.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 176–177, January, 1994.     

Novel synthesis of α-nitroalkenes from nitroalkanes via halogenation of intermediate N,N-bis(silyloxy)enamines

An approach to conjugated nitroalkenes via oxidation of N,N-bis(silyloxy)enamines with bromine or iodine in the presence of tetra-n-butylammonium acetate is described. The acetate ion plays a key role by acting as a mild desilylating reagent. This new strategy allows the synthesis of α-nitroalkenes from the corresponding nitroalkanes.     

Synthesis and chemical transformations of silicon-containing derivatives ofN,N-dimethylhydrazine

Reactions of carbofunctional organosilicon compounds withN,N-dimethyl-N′-trimethylsilylhydrazine andN,N-dimethyl-N′,N′-bis(trimethylsilyl)hydrazine were studied. The composition and structure of the reaction products were found to be dependent on the reagent nature and the reaction conditions. 1,4-Dimethylamino-2,2,5,5-tetramethyl-1,4-diaza-2,5-disilacyclohexane, a first representative of a new type of 2,5-disilapiperazines, was synthesized. A scheme of its formation was proposed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 169–173, January, 1999.     

Synthesis of high-molecular-weight polyamine by radical polymerization ofN,N-diallyl-N-methylamine

The first synthesis of high-molecular-weight poly(N,N-diallyl-N-methylamine) by thermal (at 30 and 50°C) and photoinduced (at 21 °C) radical polymerization ofN,N-diallyl-N-methylamine (DAMA) in aqueous solution in the presence of an equimolar amount of trifluoroacetic acid (TFA) and by polymerization of the newly synthesized equimolar DAMA·TFA salt is reported. Data of¹H NMR spectroscopy indicate that the molecules of the monomer under chosen conditions are in the protonated form. This leads to a decrease in the contribution of the reaction of degradative chain transfer to the monomer and its transformation into effective chain transfer to the monomer. A bimolecular chain termination mechanism was estabilished and the possibility of controlling the polymerization rate and the molecular weight of the polymer was demonstrated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 430–436, March. 2000.     

Vibrational spectra and structure ofN,N-dinitromethylamine

The vibrational (IR and Raman) spectra ofN,N-dinitromethylamine were studied. The assignments of the bands were carried out using a comparison of spectra obtained in different aggregate states, invoking the results of normal coordinate analysis. The most probable symmetry of the molecule was shown to beC _s with a planar configuration of the N(NO₂)₂ moiety.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1503–1507, August, 1995.     

Synthesis of α,α′-bis(R-benzylidene)cycloalkanones catalyzed by potassium hydrogen sulfate under solvent-free conditions

Cyclopentanone or cyclohexanone were condensed with aromatic aldehydes to give corresponding α,α′-bis(R-benzylidene)cyclopentanones or α,α′-bis(R-benzylidene)cyclohexanones. The reaction was catalyzed by potassium hydrogen sulfate with a yield of 84–95% under solvent-free conditions.     

Photoinduced electron transfer in N,N-bis(pyridylmethyl)naphthalenediimides: study of their potential as pH chemosensors

The change in fluorescent properties of a series of N,N-bis(pyridylmethyl)naphthalenediimides (BIPy-NDIs) as function of pH were investigated. The naphthalenediimide dyes displayed OFF–ON pH sensing properties owing to photoinduced electron transfer in the pH range from 1.7 to 4.1. The fluorescence enhancement of the chemosensors studied is based on the hindering of photoinduced energy-electron transfer (PET) from pyridine ring to the naphthalene fluorophore by protonation. Moreover, using density functional theory theoretical calculations of molecular orbitals, it was verified that protonation nitrogen atom in pyridine ring inhibits the PET process. The best selective response for monitoring pH in the presence of different metal ions, was exhibited by BIPy-NDI 1B. In addition, 1B was applied for determination of pH in real samples of commercial vinegars. The results were consistent with those obtained by glass electrode method, indicating that the new probe could be a practical pH indicator in strongly acidic conditions.     

Synthesis of 6-(N-azolyl)cyclohex-2-enones fromN-acetonylazoles

N-Acetonylazoles react with chalcones in the presence of a base to givetrans-3,5-disubstituted 6-(N-azolyl)cyclohex-2-enones. Usually, the reactions are fast and high-yielding. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 557–561, March, 1999.     

A convenient method for the preparation ofN-unsubstituted hydrazones of aromatic ketones and aldehydes

A general and useful method for the synthesis ofN-unsubstituted hydrazones of aromatic ketones and aldehydes in good yields was elaborated. The use of a large excess of hydrazine hydrate and catalytic amounts ofp-toluenesulfonic acid makes it possible to prepare the hydrazones without an admixture of the corresponding azine. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2197–2199, November, 1999.     

Synthesis and structures of complexes ofN-2-nitroxyethylpicolinamide and 2-(2-pyridyl)-2-oxazoline with PdCl2

The reaction ofN,N′-bis(2-nitroxyethyl)pyridine-2,6-dicarboxamide with PdCl₂ afforded previously unknowncis-(N-2-nitroxyethylpicolinamide-N,N′)dichloropalladium(II) andcis-[2-(2-pyridyl)-2-oxazoline-N,N′]dichloropalladium(II), which were isolated as a cocrystallizate of the molecular compounds. Its structure was established by X-ray diffraction analysis. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1604–1606, August, 1999.     

Syntheses based on (N,N-difluoroamino)dinitroacetonitrile

High reactivity of the nitrite group in (NN-difluoroamino)dinitroacetonitrile was demonstrated. Based on its reaction with HN₃, a new preparative method for the synthesis of 5-[(N,N-difluoroamino)dinitromethylltetrazole was developed; some derivatives of the latter compound have been obtained.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8. pp. 2056–2058, August, 1996.     

N-methyI-N-(triethoxysilylmethyl) andN-methyl-N-(silatran-1-ylmethyl) substituted glycine and alanine

Organosilicon derivatives of glycine, - and -alanine, and -methylalanine were prepared by the reaction of methyl esters of - and -halocarboxylic acids withN-methylaminomethyltriethoxysilane in the presence of triethylamine. The compounds synthesized were converted into the correspondingN-silatran-l-ylmethyl derivatives. Trimethylsilyliodoacetate reacts withN-methylaminomethyltrietoxysilane to give 2,2-diethoxy4-methyl-1-oxa-4-aza-2-silacyclohexane-6-one. Its reaction with triethanolamine leads toN-methyl-N-(silatran-l-ylmethyl)glycine.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 341–343, February, 1995.     

The reaction of salts ofN-(β-hydroxyalkyl)-N′-hydroxydiazeneN-oxides with dihalomethanes

Methylene-bis[N′-oxydiazene-N-(β-hydroxyalkyl)N-oxides] were synthesized by the reaction of salts ofN-(β-hydroxyalkyl)-N′-hydroxydiazeneN-oxides with diahalomethanes. The effect of the nature of the starting reagents and the reaction condtions on the yields of the target compounds was studied. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2266–2269, November, 1998.     

Reaction of 2-chloro-3-(4-N,N-dimethylaminoanilino)-1,4-naphthoquinone with cyclic amines (piperidine,morpholine, and pyrrolidine)

It was shown that the reaction of 2-chloro-3-(4-N,N-dimethylaminoanilino)-1,4-naphthoquinone with piperidine in the absence of a solvent gives not only a product of replacement of the chlorine atom by a piperidino group, 3-(4-N,N-dimethylaminoanilino)-2-piperidino-1,4-naphthoquinone, but also 2-(4-N,N-dimethylaminoanilino)-1,4-naphthoquinone and 2-(4-N,N-dimethylaminoanilino-2-piperidino)-1,4-naphthoquinone. The latter compounds are the only reaction products formed in dimethyl sulfoxide. The reaction with morpholine occurs in a similar way, whereas that with pyrrolidine gives only a product of replacement of the chlorine atom by hydrogen.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2451–2454, December, 1995.