Synthesis ofN-(3-azido-2-nitroxypropyl)-,N-(2,3-diazidopropyl)-, andN-(2-azido-3-methoxypropyl)-N-alkylnitramines

N-(3-Azido-2-nitroxypropyl)-N-alkylnitramines andN-(2,3-diazidopropyl)-N-alkylnitramines were prepared by nitration and azidation ofN-alkyl-N-(2-hydroxy-3-chloropropyl)sulfamates andN-(3-azido-2-hydroxypropyl)-N-alkylsulfamates. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 206–208, January, 1999.     

Synthesis of O-[4,6-Di-O-Acetyl-4-O-(2,3,4,6-Tetra-O-Acetyl-β-D-Galactopyranosyl)-2-Deoxy-2-Hydroxyimino-D-Arabino-Hexopyranosyl]-N-Benzyloxycarbonyl-L-Serine Methyl Esters And Their Transformations

ABSTRACT

3,6-Di-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-2-deoxy-2-hydroxyimino-α- and -β-D-arabino-hexopyranosides of N-benzyloxycarbonyl-L-serine methyl ester as well as of ethanol have been synthesised from D-lactal hexaacetate via nitrosyl chloride, followed by condensation with L-serine derivatives and ethanol, respectively. The compounds of L-serine thus obtained were modified at C-2 and C-3 to afford L-serine derivatives attached to disaccharides containing terminal α-D-gluco-, 2-acetamido-α-D-gluco-, β-D-manno, 2-acetamido-β-D-manno-pyranosyl, 3-azido-2-hydroxyimino-α-D-arabino-, and α-D-ribo-hexopyranosyl residues.     

Synthesis ofN-methacryloyl- andN-allyl-substituted derivatives of ethyl 5-oxo-2-pyrrolidinecarboxylate

A method for the preparation of previously unknownN-methacryloyl- andN-allyl-derivatives of ethyl 5-oxo-2-pyrrolidinecarboxylate has been developed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 767–769, March, 1996.     

Functional polymers. XII: Synthesis and polymerization of 2(2-vinyl-4-hydroxyphenyl)2H-benzotriazole and 2(3-vinyl-4-hydroxyphenyl)2H-benzotriazole

Condensation of diazotizedo-nitroaniline with 3-ethylphenol or with 2-ethylphenol followed by reduction of the resulting azo compound with zinc dust in sodium hydroxide solution gave 2-(2-ethyl-4-hydroxyphenyl)2H-benzotriazole and 2(3-ethyl-4-hydroxyphenyl)2H-benzotriazole, respectively. The individual compounds were acetylated, brominated withN-bromosuccinimide to the corresponding 1-bromoethyl compounds which were then dehydrobrominated with triethyl amine in acetonitrile and hydrolyzed to 2(2-vinyl-4-hydroxyphenyl)2H-benzotriazole or 2(3-vinyl-4-hydroxyphenyl)2H-benzotriazole. The two monomers could be polymerized and copolymerized with styrene and methyl methacrylate. The ethyl as well as the vinyl compounds and the corresponding polymers, when tested, are ineffective as ultraviolet absorbers as they have structures of 4-hydroxyphenyl rather than 2-hydroxyphenyl compounds with respect to the benzotriazole ring. A careful NMR analysis for the correct structural assignment is also described.Part XI:S. Yoshida andO. Vogl, Makromol. Chem., in press.     

Acid-catalyzed attack of the dinitrogen ligand in thecis-(Me2PhP)4Mo(N2)2 andtrans-(Ph2PCH2CH2PPh2W(N2)2 complexes by nitronium and nitrosonium cations with the formation of nitrogen oxides

The interaction of labeled dinitrogen complexescis-(Me₂PhP)₄Mo(¹⁵N₂)₂ andtrans-(dppe)₂W(¹⁵N₂)₂ with non-labeled nitronium and nitrosonium fluoroborates,¹⁴NO₂BF₄ and¹⁴NOBF₄, in sulfolane at room temperature in the presence of H₂SO₄ results in rapid formation of labeled nitrous and nitric oxides (¹⁵N¹⁴NO,¹⁵NO), as well as¹⁵N¹⁴N. The yield of the products depends on the reagent ratio and reaches 10–20 mol. % per mole of a complex under optimum conditions. The mechanism of the reactions found is proposed. It involves the step of protonation of the dinitrogen ligand to form the corresponding hydrazido(2–) derivatives, which are then attacked by nitronium or nitrosonium cations. In accordance with the mechanism proposed, it was established that the hydrazido(2–) complexes, (Me₂PhP)₃Mo(¹⁵N₂H₂)Cl₂ and (dppe)₂W(¹⁵N₂H₂)Cl₂, are capable of forming¹⁵N¹⁴NO,¹⁵NO, and¹⁵N¹⁴N under the action of¹⁴NO₂BF₄ and¹⁴NOBF₄ in the absence of an acid.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 13–13, July, 1995.     

Synthesis of 1,3,4-thiaza- and 1,3,4-oxazaphosphol-2-lines based onN-phosphorylated (thio)ureas

The reactions ofO-phenyl chloromethylisothiocyanatothioxophosphonate andO-phenyl chloromethylisocyanatophosphonate with trimethylsilyldiethylamine lead to the formation of 1,3,4-thiazaphosphol-2-ine and 1,3,4-oxazaphosphol-2-ine, respectively. Phosphorylation ofN-methyl-N-phenyl-N,N-bis(trimethylsilyl)urea withO-phenyl chloromethylchlorophos phonate gives 1,3,4-diazaphospholidin-2-one.Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 7, pp. 1857–1859, July, 1996.     

Synthesis and structure of 2-amino- 5-azolyl-3-cyano-4H-pyrans

Previously unknown 5-azolylpyrans were obtained by reactions ofN-acetonyl- andN-phenacylimidazoles, -triazoles, and -tetrazoles with arylmethylenemalononitriles. The structure of 2-amino-3-cyano-6-methyl-5-(5-nitrotetrazol-2-yl)-4-phenyl-4H-pyran was established by X-ray structural analysis.Deceased.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 2050–2055, August, 1996.     

Reaction of vinyloxyalkylamines with mercaptoacetic acid

N-[2(3)-Hydroxyalkylj-4-thiazolidinones have been synthesized by the reaction of 2(3)-vinyloxyalkylamines with mercaptoacetic acid in 24–69 % yield. The structure of the compounds obtained was supported by (R and¹H NMR spectroscopic data.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 677–679, March, 1996.     

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.     

Synthesis and Chemical Transformation of 2 -Acetoxyimino-3,4, 6-tri-O-acetyl-2-deoxy-β-D-arabino-hexopyranosyl Azide

Abstract

The title compound 3 has been synthesized from 3,4,6-tri-O-acetyl-2-deoxy-2-nitroso-α-D-glucopyranosyl chloride (1) via compound 2. Azide reduction of 3 is accompanied by O→N-acetyl migration to afford N-acetyl-N-(3,4,6-tri-O-acetyl-2-deoxy-2-hydroxyimino-β-D-arabino-hexopyranosyl) amine (4), also characterized as its Z and E peracetates. On the basis of IR, ¹H NMR and X-ray structural data from compound 4, its β-NHAc configuration, (Z) 2-hydroxyimino, and °S₂ conformation, were established.     

Reaction ofN-(3,3,3-trifluoro-2-trifluoromethylprop-1-enyl)dimethylamine with MgSO4·7H2O. Synthesis of 4,4-difluoro-5-trifluoromethyl-2-(2,2,2-trifluoro-1-trifluoromethylethyl)-4H-1,3-dioxine andcis/trans-3-dimethylamino-2-trifluoromethacryloyl fluoride

4,4-Difluoro-5-trifluoromethyl-2-(2,2,2-trifluoro-1-trifluoromethylethyl)-4H-1,3-dioxine andcis/trans-3-dimethylamino-2-trifluoromethacryloyl fluoride were obtained by reaction ofN-(3,3,3-trifluoro-2-trifluoromethylprop-1-enyl)dimethylamine with MgSO₄·7H₂O. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1069–1071, May, 1997.     

Synthesis of 3-(6-R-Benzothiazol-2-yl)-4-methyl-1,2,5-oxadiazoles

The nitrosation of N-aryl-3-oxobutanethioamides afforded 1-(6-R-benzothiasol-2-yl)-1-hydroxyimino-2-propanones that at oximation with hydroxylamine were converted into 1-(6-R-benzothiazol-2-yl)-1,2-dihydroxyiminopropanes. The latter were dehydrated by heating with succinic anhydride at 140°C yielding therewith 3-(6-R-benzothiazol-2-yl)-4-methyl-1,2,5-oxadiazoles.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 5, 2005, pp. 759–761.Original Russian Text Copyright © 2005 by Britsun, Borisevich, Samoilenko, Lozinskii.     

Various approaches to the use of 3-acetyl-2-amino-4-hydroxy-1,3-pentadienecarbonitrile in heterocyclic synthesis

Two approaches to the use of 3-acetyl-2-amino-4-hydroxy-1,3-pentadienecarbonitrile (1) in heterocyclic synthesis are considered. A method for preparing 3-acetyl-4-amino-5-cyano-2-methylpyridine directly from1 andN,N-dimethylformamide dimethylacetal (DMF DMA) was proposed, together with a synthetic route to 2-(2-amino-3-cyano-6-hydroxy-phenyl)-8-cyano-5-hydroxy-4-methylquinoline based on the transformation of hydroxyvinyl ketone1 into its diphenylboron chelate and condensation of the latter with DMF DMA. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 127–130, January, 1997.     

Reactions with pyrrolidine-2,4-diones,II: New approaches to the synthesis of substituted 5,6-dihydropyrrolo[3,4-d][1,2,3]triazol-4(2H,4H)ones

Summary Approaches leading to 5,6-dihydro-5,6-diphenyl-2-substituted-pyrrolo[3,4-d][1,2,3]-triazol-4(2H,4H)-ones (10) are described. The first approach consists of cyclodehydrating 3(or 4)-hydroxyimino-1,5-diphenyl-4(or 3)-(4-substituted phenylhydrazono)pyrrolidin-2-ones (4,7) with boiling acetic anhydride. The second approach involves cyclization of 3(or 4)-acetoxyimino-1,5-diphenyl-4(or 3)-(4-substituted phenylhydrazono)pyrrolidin-2-ones (8,9) with elimination of acetic acid upon treatment with sodium hydroxide.Part of the work has been presented at the 8^th International Congress of Heterocyclic Chemistry (August 1981), Graz, Austria     

Synthesis and biological activity of novel mitomycin C analogs derived from mitomycin A

A variety of mitomycin C analogs were synthesized from mitomycin A and their biological activities were studied. Mitomycin A ( 1 ) underwent nucleophilic displacement reactions involving intramolecular hydrogen migrations upon treatment with nitrogen nucleophiles bearing mobile hydrogens, but the mode of hydrogen migration depended on the nature of the nucleophiles. The reaction with alkoxyamines gave compounds 6 and 7 which have the 5H-6-alkoxyimino-4,7-dione structure in ring A of 1 . However, the reaction with hydroxylamine and benzoylhydrazine afforded compounds 11 and 13 which have the 4-hydroxy-6-hydroxyimino-7-one structure and the 4-hydroxy-6-hydrazono-7-one structure, respectively, in ring A of 1 . These products were converted into various types of mitomycin C derivatives by methylation with methyl iodide or dimethyl sulfate. The mechanistic features of these reactions are discussed. The in vitro and in vivo biological activities were tested by using P388 leukemia and Sarcoma 180 tumor cells. Several of the synthesized compounds exhibited better activity than that of mitomycin C.     

Synthesis and conversions of 3-(4-amino-5-methyl-4H-1,2,4-triazol-3-ylmethylene)-2-oxo-1,2,3,4-tetrahydroquinoxaline

The reaction of the hydrazone 3a with hydrazine hydrate in DBU/ethanol conveniently gave 3-(4-amino-5-methyl-4H-1,2,4-triazol-3-ylmethylene)-2-oxo-1,2,3,4-tetrahydroquinoxaline 6 . The reactions of 6 with an equimolar and 2-fold molar amount of nitrous acid afforded 3-(α-hydroxyimino-4-amino-5-methyl-4H-1,2,4-triazol-3-ylmethyl)-2-oxo-1,2-dihydroquinoxaline 9 and 3-(α-hydroxyimino-5-methyl-2H-1,2,4-triazol-3-ylmethyl)-2-oxo-1,2-dihydroquinoxaline 10 , respectively, which were converted into the 3-heteroarylisoxazolo[4,5-b]quin-oxalines 13a,b and 11 , respectively. Compound 9 was also cyclized into the 8-quinoxalinyl-1,2,4-triazolo-[3,4-f][1,2,4]triazines 14a,b .     

Synthese von 1-Ary1-4-methylthio-2-azetidinonen

TheN-arylthioformimidates4 a-e, which may be obtained byS-alkylation of the thioformanilides3 a-e, react with chloroacetylchloride/triethylamine to yield the (3R,4S/3S,4R)-1-aryl-3-chloro-4-methylthio-2-azetidinones5 a-e and the formanilides6 a-e. Dehalogenation of5 b-e with tri-n-butyltinhydride yield the title compounds7 b-e. Hydrogenolysis of7 b and7 c yields7 f and7 g.

     

Formation of 3-pyrrolin-2-one or imidazolidine derivatives by slow dimerization of N-substituted aziridine-2-carboxylates

Prolonged storage (45–60 days) of N-methyl- or N-cyclopropylaziridine-2-carboxylates leads to their dimerization through the N—C(3) bond cleavage to form 1,3-disubstituted 2-methylimidazolidine-2,4-dicarboxylates in high yields. Prolonged storage of 1-benzyl-aziridine-2-carboxylate (like the reactions of alkyl pyruvates with primary amines) results in cyclocondensation to yield 3-pyrrolin-2-one derivative. Dedicated to Corresponding Member of the Russian Academy of Sciences E. P. Serebryakov on the occasion of his 70th birthday. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 1025–1029, April, 2005.     

Über N1- und N2-substituierte 2-Amino-5,6-dihydro-4(1H)-pyrimidinone

The reactions of the monosubstituted guanidines2 b-h with methyl acrylate in dimethylformamide or ethanol as solvent preferentially afford 1-substituted 2-amino-5,6-dihydro-4(1H)-pyrimidinones6 b-h. The structures of 1-hexyl- and 1-benzyl-4-pyrimidinones6 c, e and of the picrate of 1-phenylpyrimidinone6 g were proved by comparison with authentic samples, which were prepared from N-substituted ethyl 3-amino-propionates14 c, e andg and cyanamide. Accordingly,6 g is not identical with authentic 2-phenylaminopyrimidinone7 g (prepared from 2-methylthio-4-pyrimidinone10 and 2-thioxo-4-pyrimidinone12 respectively, compare¹⁰).N,N-Disubstituted guanidines2 i-m react with methyl acrylate in dimethylformamide as solvent to afford N²,N²-disubstituted 2-amino-5,6-dihydro-4-(1H)-pyrimidinones7 i-m. Action of morpholine-4-carboxamidine (21) on methyl acrylate in ethanol yields 2-morpholinopyrimidinone71 as byproduct and 3-ethoxy-N-[morpholino(amino)methylene]propionamide (91) as mainproduct.

Herrn Prof. Dr.Robert Ott mit den besten Wünschen zum 60. Geburtstag gewidmet.     

Synthesis of 1,2,4-substituted hexahydropyridazines and X-ray structural investigation of 4-hydroxyimino-2-methyl-1-phenethylhexahydropyridazine

A series of new 1,2,4-substituted hexahydropyridazines was prepared in order to evaluate qualitatively and quantitatively the role and influence of substituents on the biological activity of this system. An X-ray structural investigation of 4-hydroxyimino-2-methyl-1-phenethylhexahydropyridazine was performed. The compounds considered exhibit moderate local anesthetic, antihistaminic, and anticonvulsive activity.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 539–541, March, 1993.