Preparation ofN-nitrohydroxylamines by substitutive nitration

Interaction of Na- or K-salts ofN-acetyl-N-methylhydroxylamines with aryl or aryl halides results in correspondingO-substitutedN-acetyl-N-methylhydroxylamines. Nitration of these compounds by nitronium salts or dinitrogen pentoxide results inO-substitutedN-methyl-N-nitrohydroxylamines.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 239–241, January, 1996.     

Catalytic silylotropy inN-trimethylsilylpyrazole derivatives

Silylotropy in 4-substitutedN-trimethylsilypyrazoles is studied by dynamic¹H,¹³C, and²⁹Si NMR spectroscopy. The catalytic 1,2-migration of a trimethylsilyl group in 4-halo-N-trimethylsilylpyrazoles was detected. Silylotropy inN-trimethylsilylpyrazoles in the presence of halogens of trimethylhalosilanes is believed to proceed through formation ofN,N-bis(trimethylsilyl)pyrazolium salts, the barrier of silylotropy in pyrazoles being markedly reduced.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 3011–3013, December, 1996.     

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.     

Thermal decomposition ofC-iodotetrazoles

Thermal decomposition of 1-substitutedC-iodotetrazoles in melt and solutions has been investigated. Thermal stabilities, kinetic and activation parameters, and compositions of products of thermolysis ofC-iodotetrazolcs depend on the substituent nature. The scheme of thermolysis ofC-iodotetrazoles has been suggested.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 68–71, January, 1996.     

Formation and thermal decomposition of adducts of phthalimidonitrene with spiro(1-pyrazolinecyclopropanes)

Oxidation ofN-aminophthalimide with lead tetraacetate in the presence of spiro(1-pyrazolinecyclopropanes) at temperature from −20°C to −30°C resulted in the formal generation of phthalimidonitrene followed by its addition at the N=N bond of the pyrazoline ring to form 5(3)-substitutedN-{spiro[1-pyrazolinio-3(5),1′-cyclopropane]}-N-phthalimidoamides (azimines), whose regioisomeric compositions were determined to a large extent by the nature of the substituents in the pyrazoline ring. The structures of phthalimidoazimines were established based on the NMR spectra and X-ray diffraction data. Thermal conversions of the resulting adducts, which proceeded either with retention or with opening of the spiro-fused cyclopropane ring, were studied. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1328–1333, July, 1999.     

Alkylation of salts ofN-nitrohydroxylamines with chloromethylnitramines

The reactions of Ag-salts ofN-nitmhydroxyumines withN-methyl-N-chloromethylnitramine afford mainly products ofO-alkylation, whereas the reactions of the corresponding Li-, Na-, K-, Mg-, and NH₄-sals in the presence of tetrabutylammonium (TBAB) give mainly products ofN-alkylation. The reactions of the corresponding. NH₄-salts with bis-(chloromethyl)nitramine in the presence of TBAB lead solely to products ofO-alkylation. Increasing in the amount of TBAB results in the appearance of theN-isomer.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1740–1744, July, 1996.     

Phosphorylation ofN-trimethylsilyllactams

Treatment ofN-trimethylsilyllactams with phosphoryl chlorides results in mixtures of products, whose formation can be explained by competition betweenN- andO-phosphorylation.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1644–1648, September, 1994.     

N-Phosphorylated lactams

The phosphorylation ofN-trimethylsilyllactams by phosphorus(III) acid chlorides results in correspondingN-phosphinolactams in high yields. The derivatives thus obtained have been used in the synthesis ofN-phosphoryl- andN-thiophosphoryllactams. The reversibility of the reaction of phosphinolactams has been established.For communication 1 see Ref. 1.Translated fromIzyestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2250–2255, November, 1995.     

Über Darstellung und Reaktivität von 2,4-Diazabicyclo[3.3.1]nonan-3-onen

The 2-cyclohexenones1 a andd resp. react with urea in HCl/EtOH to give 1-hydroxy-4-methyl-7-phenyl- and 1-hydroxy-2,4-diazabicyclo[3.3.1]nonane-3-ones3a and3d resp., whereas the 2-cyclohexenones1b andc resp. transformed by urea to 1,7-dimethyl- and 1-methyl-4-ureido-2,4-diazabicyclo[3.3.1]nonan-3-ones9b andc resp. In the condensation of isophorone1e with urea a product C₁₃H₂₈N₈O₄ of indisdinct structure was formed, whereas the bicyclus3e could not be isolated.Reaction ofAcOAc with3a yielded the 5-methyl-3-oxo-7-phenyl-2,4-diazabicyclo[3.3.1]non-1-ylacetate (15); on heating of3a with acids decomposition to1a and urea took place. NoWagner-Meerwein-rearrangement was observed. The MS-spectra of3a andd are discussed; NMR- and IR-data are reported.No significant herbicidal, fungicidal or insecticidal activity was found in screening-tests on3a.

     

Strukturelle Abwandlungen anN-Acetylneuraminsäure, 4. Mitt. Transformationen am Diethyl-dithioketal desN-Acetylneuraminsäure-γ-lactons

Partial protection of diethyldithioketal ofN-acetylneuraminic acid--lactone using one or two equivalents oft-butyldimethylchlorosilane leads to the 9-O-silyletherderivative7 and the 8,9-bis-O-silylderivative5, resp. The reaction of1 as well as7 with 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane (TIPSiCl₂) yields selectively the protected products4 and9. The 9,8,7,6-tetra-O-acetyl-N-acetylneuraminic acid--lactone derivative3 is formed by the oxidative desulfurazation of the peracteylated form of1 (i. e.2) by means ofNBS. By reaction of5 withTPPDEAD the 6,7-carbonato compound6 arises instead of the expected 6,7-epoxyderivative. The analogous carbonate8 is formed by treating7 with bisimidazolylcarbonate.

     

13C and1H NMR study of 3-R-substitutedtrans-2-oxadecalins and 1-R-substitutedcis- andtrans-2-oxahydrindans

Previously synthesized 3-substitutedcis- andtrans-2-oxadecalins and 1-substitutedcis- andtrans-2-oxahydrindans were studied by ¹³ C and ¹ H NMR. The structure and configuration of these compounds were established.A. V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 117912 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 861–865, April, 1992.     

Strukturelle Abwandlungen anN-Acetylneuraminsäure, 3

From methyl-5-acetylamino-7,8-anhydro-4,9-O-bis-(t-butyldimethylsilyl)-3,5-dideoxy--D-glycero-D-galacto-2-nonulopyranosidonic acid methylester (1) the derivatives1 a and1 b were obtained by removing the 9-O-(t-butyldimethylsilyl)group withBu ₄NF, followed by acetylation. Treatment of1 b with 80% acetic acid and acetanhydride/pyridine yields the 8-epi-N-acetylneuraminic acid derivative2 a and the 7-epi-N-acetylneuraminic acid derivative3 a in a ratio of 3:1 (Scheme 1). The structure elucidation of2 b was achieved by converting2 b via the 4,9-bis-O-(tBDMSi)-8-O-tosyl-derivative2 d into the epoxide1 (Scheme 2). Using the same sequence the epoxides4 and5 were transformed into theN-acetylneuraminic acid derivative6 a and the 7,8-bis-epi-N-acetylneuraminic acid derivative7 a (Scheme 3). After treatment with sodium hydroxide and 0.025m HCl and Dowex 50 H⁺ the 8-epi-, 7-epi- and 7,8-bis-epi-N-acetylneuraminic acids2,3, and7 were obtained. These three compounds were tested withCMP-N-acetylneuraminic acid synthetase.

Herrn KollegenK. Schlögl mit den besten Wünschen zum 60. Geburtstag.     

Synthesis and studies of organic nitrates of the heterofunctional series

N-Nicotinoyltris(hydroxymethy)aminomethane trinitrate hydronitrate, an analog ofN-nicotinoylethanolamine nitrate (the active principle of the antianginal drug nicorandil), was prepared byO-nitration of the corresponding triol with concentrated HNO₃. The structure of the reaction product was established by X-ray structural analysis. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2224–2227, December, 1997.     

Reaction of sulfenamides withN,N-dimethylaniline in the presence of phosphorus(v) oxochloride

Reaction of arylsulfenamides withN,N-dimethylaniline in the presence of POCl₃ at room temperature affords unsymmetrical diaryl sulfide, onlypara-substitutedN,N-dimethylanilines being formed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 178–179, January, 2000.     

Reaction of sulfenamides withN,N-dimethylaniline in the presence of phosphorus(v) oxochloride

Reaction of arylsulfenamides withN,N-dimethylaniline in the presence of POCl₃ at room temperature affords unsymmetrical diaryl sulfide, onlypara-substitutedN,N-dimethylanilines being formed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 178–179, January, 2000.     

Interaction of hydrosilanes with carbon dioxide and secondary amines or silylamines

The reaction of hydrosilanes with carbon dioxide and secondary amines or silylamines was studied for the first time. The dependence of the composition and the structure of the products obtained on the nature of the reagents and on the reaction conditions was found. The hydrosilane-carbon dioxide system, unknown previously, can be used as anN-siloxycarbonylating reagent in the synthesis ofO-silylurethanes. A scheme for the formation ofO-silylurethanes was proposed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2309–2312, September, 1996.     

Darstellung von Organoquecksilber—Stickstoffverbindungen durch Synproportionierung

The exchange reaction ofR ₂Hg and >N–Hg–N< compounds yielding organomercury—nitrogen compounds may be widely applied, as shown here in the synthesis ofN-phenylmercury-amides,-imides,-heterocycles and-triazenes.

     

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.     

The Claisen rearrangement in the aminophenol series

Novel compounds, dihydropyranylaminophenols, were synthesized by condensation of 3,4-dibromo-4-methyltetrahydropyran with aminophenols followed by the Claisen rearrangement ofO-andN-substituted products. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 517–520, March, 1999.     

Synthesis and some transformation ofN-allyl-N′-methoxy-andN-allyl-N′-tosyloxydiazeneN-oxides

The first representatives ofN-2-alkenyl-N′-alkoxydiazeneN-oxides andN-2-alkenyl-N′-sulphonyloxydiazeneN-oxides have been synthesized. Some reactions of the double bond in these compounds have been studied. The possibility of isomerization ofN-2-alkenyl-N′-alkoxydiazeneN-oxides toN-alk-1-enyl derivatives has been discovered. See Ref. 1 and the references therein. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 2262–2265, November, 1998.