Synthesis of 3-alkoxy-2-nitroxypropyl-N-alkylnitramines

It was shown that 3-alkoxy-2-nitroxypropyl-N-alkylnitramines can be prepared by nitration of the corresponding 3-alkoxy-2-hydroxypropyl-N-alkylsulfamates. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1987–1989, November, 1997.     

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 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 of 3-nitro-3-azalk-2-yl ethers

PrimaryN-nitramines react with vinyl ethers to give 3-nitro-3-azalk-2-yl ethers. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 621–623, March, 1999.     

Synthesis and structures of complexes ofN-(2-aminoethyl)diaziridines with transition metal salts

A series of complexes ofN-(2-aminoethyl)diaziridines with transition metal salts (Zn²⁺, Cd²⁺, Ni²⁺, Co²⁺, Mn²⁺, or Fe²⁺) were synthesized. Their structures were established by IR and NMR spectroscopy. The structure of bis[1,2-bis(2-aminoethyl)diaziridine]cadmium(II) diperehlorate was confirmed by X-ray diffraction analysis. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1910–1914, November, 2000.     

系列单取代烷氧基-2-羟丙基-β-环糊精的合成与表征

以环氧氯丙烷和脂肪醇为原料, 通过相转移催化法合成了乙基、正丙基、正丁基和正戊基缩水甘油醚(1～4), 并利用所合成的缩水甘油醚和β-环糊精为原料, 分别在弱碱水溶液(1.5%)和强碱水溶液(30%)中制备并用硅胶柱分离出单2位取代的乙氧基、丙氧基、丁氧基和戊氧基-2-羟丙基-β-环糊精(1a～4a)和单6位取代的丙氧基、丁氧基和戊氧基-2-羟丙基-β-环糊精(2b～4b), 利用薄层色谱、红外光谱、差热扫描量热分析、质谱和核磁共振等手段对所合成的产品进行了表征.     

Chemical properties ofN-(amidomethy)- andN-(imidomethyl)glycine derivatives 2. Reactions at alkoxycarbonyl and carboxyl groups

N-(Aroylarnmomethylfglycine amides were synthesized by reactions ofN-(aroyllminomethyl) glycine esters with ammonia. Alkaline hydrolysis ofN-(amidomethyl)glycine,N-(irnidornethyl)glycine, andN-(amidomethyl)pheriylalariiiie esters afforded the correspondingN-(amidowthyVa-amirio acids- Reactions of the Last-mentioned compounds with ethyl esters of glycine, alanine, and phenylalanine in the presence of dicyclohexylcarbodiimide yielded dipeptides containingNh-amidomethyl substituents.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1770–1771, July, 1996.     

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.     

Synthesis and properties ofN-[1-hydroxyimino-2-methyl-1-(2-pyridyl)prop-2-yl]hydroxylamine and heterocyclic derivatives based on it

N-[1-Hydroxyimino-2-methyl-1-(2-pyridyl)prop-2-yl]hydroxylamine, a new representative of the series of α-hydroxylamino oximes, was synthesized. Based on this compounds, 3-imidazoline 3-oxide and 2-imidazoline 3-oxide derivatives, were obtained, and some of their chemical properties were investigated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 131–136, January, 1997.     

Synthesis,structures and properties ofN-(trihalogermylmethyl)-substituted amides,lactams and imides,the derivatives of the five-coordinate germanium

The formation of trichlorogermyl-substituted amides, lactams, and imides occurs when 2Et₂O·HGeCl₃ is condensed with compounds possessing the -NCH₂Cl fragment and equally well when HGeCl₃ interacts with compounds containing -NCH₂OH and-NCH₂OSiMe₃ groups. In some cases, the use of the latter is more advantageous from the preparative point of view. In compounds thus obtained, the germanium is five-coordinate due to the coordination . Deceased August 13, 1993. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1793–1799, October, 1993.     

Quantum chemical study of the transformation of 2-(N-alkylamino)-3-(indol-1-yl)-and 2-(N-alkylamino)-3-(indol-3-yl)maleimides by protic acids: Tandem hydride transfer/cyclization mechanism

The geometric parameters, the charge distribution, and the energetics of N-methyl-2-(N-ethylanilino)-3-(indol-1-yl)-and N-methyl-2-(N-ethylanilino)-3-(indol-3-yl)maleimides and their conjugated acids were studied by density functional theory calculations at the B3LYP/6-31G(d) level. The mechanism of the tandem hydride transfer/cyclization sequence, which occurs after protonation of N-methyl-2-(N-ethylanilino)-3-(indol-1-yl)-and N-methyl-2-(N-ethylanilino)-3-(indol-3-yl)maleimides, was analyzed. The investigation of the potential energy surface for the tandem hydride transfer/cyclization of the iminium cation that formed upon protonation revealed that the hydride transfer followed by intramolecular cyclization at position 7 of the indole fragment in N-methyl-2-(N-ethylanilino)-3-(indol-1-yl)maleimide is the preferable process, unlike alternative intramolecular cyclization involving the cationic center at the C(2) atom of the indole fragment and the benzene ring of the N-ethylaniline fragment of the indoleninium cation in N-methyl-2-(N-ethylanilino)-3-(indol-3-yl)maleimide. A study of the key intermediates of the assumed reaction mechanism demonstrated that these intermediates are actually stationary points on the potential energy surface (minima and transition states). Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2069–2073, December, 2006.     

Synthesis of N-nitrooxazolidines and N-nitrotetrahydro-1,3-oxazines from N-(2-hydroxyalkyl)- and N-(3-hydroxyalkyl)sulfamates

A method was developed for the preparation of functionally substituted N-nitrooxazolidines and N-nitrotetrahydro-1,3-oxazines by nitration of the products obtained in the reactions of N-(2-hydroxyalkyl)- and N-(3-hydroxyalkyl)sulfamates with formaldehyde.     

Reaction of 2-(2-oxoethylidene)furan-3(2H)-ones with isopropylidenehydrazides of aromatic carboxylic acids: Synthesis of 3-hydroxy-3-(2-oxoethyl)-2,3-dihydropyridazin-4(1H)-ones

3-Hydroxy-3-(2-oxoethyl)-6-phenyl-2,3-dihydropyridazin-4(1H)-ones were obtained by the reaction of methyl 3-oxo-5-phenylfuran-2(3H)-ylideneacetate or 2-[2-(4-chlorophenyl)-2-oxoethylidene]-5-phenylfuran-3(2H)-one with benzoic or p-nitrobenzoic isopropylidenehydrazides. Equilibrium C₍₅₎H and C₍₅₎H₂ tautomeric forms were detected in solutions of the 4-chlorophenyl derivatives in DMSO-d₆. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1156–1158, August, 2007.     

Alkylation of salts ofN-(β-hydroxyalkyl)-N′-hydroxydiazeneN-oxides with alkyl halides and dimethyl sulfate

Salts ofN-(β-hydroxyalkyl)-N′-hydroxydiazeneN-oxides, RCH(OH)CH₂N(O)=NO⁻ M⁺ (R=Me, Prⁱ, or Bu^t; and M=Li, Na, K, Ag, NH₄, or Me₄N), were prepared. Their alkylation with alkyl halides R′X (X=Cl, Br, or I) and dimethyl sulfate was studied. Generally, alkylation afforded mixtures ofN-(β-hydroxyalkyl)-N′-alkoxydiazeneN-oxides RCH(OH)CH₂N(O)=NOR′ andO-alkyl-N-(β-hydroxyalkyl)-N-nitrosohydroxylamines RCH(OH)CH₂N(NO)OR′. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1996–2001, October, 1998.     

Synthesis of 1-(N-alkylnitraminomethyl)-3-nitroureas usingN-alkylsulfamates

1-(N-alkylnitraminomethyl)-3-nitroureas were prepared by nitration of condensation products of urea with formaldehyde andN-alkylsulfamate.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2041–2042, November, 1994.     

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.     

Synthesis ofN-substituted 2-(5,6,7,8-tetrafluoro-4-oxo-1,4-dihydroquinolin-3-yl)glyoxylic acids

Methods for the synthesis of the earlier unknownN-substituted 2-(5,6,7,8-tetrafluoro-4-oxo-1,4-dihydroquinolin-3-yl)glycoxylic acids their esters from copper chelate of ethyl pentafluorobenzoylpyruvate were developed. The structure of intermediate ethyl 4-(R-amino)-2-oxo-3-pentafluorobenzoylbut-3-enoates is discussed. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1234–1239, July, 2000.     

Synthesis of 4-aminoisoxazole-3-carboxamides using base-promoted nitrosation of N-substituted cyanoacetamides

The reactions of N-substituted cyanoacetamides with EtONO in the presence of an equimolar amount of EtONa afforded the corresponding sodium salts of hydroxyimino derivatives in 70—95% yields. The latter were transformed into 4-amino-5-(4-bromobenzoyl)isoxazole-3-carboxamides in 30—57% yields using the known method.     

Synthesis and structure of the complex of 2-(2-pyridyl)-2-oxazoline with PdCl2

The reaction ofN-2-nitroxyethylpicolinamide with PdCl₂ afforded the new complexcis-[2-(2-pyridyl)-2-oxazoline-N,N′]dichloropalladium(u). The structure of this complex was established by X-ray diffraction analysis. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 561–563, March, 2000.     

Synthese und Reaktionsverhalten von 3-(Bis(alkylthio)methylen)-3H-isobenzofuran-1-on-und 2-(Bis(alkylthio)methylen)-3(2H)-benzofuranon-Derivaten

Summary 3(Bis(alkylthio)methylene)-3H-isobenzofuran-1-ones2a–e and 2-(bis(alkylthio)methylene)-3(2H)-benzofuranone derivatives4a–c are obtained by reaction of phthalides1a–d or 3(2H)-benzofuranone (coumaranone3), respectively, with carbon disulfide under basic conditions followed by alkylation. The reaction behaviour of the new compounds2 and4 is investigated. 2-((2-Dimethylthio-1-oxo)ethyl)benzoic acid N,N-dimethylamide (7a) and 2-((2-dimethylthio-1-oxo)ethyl)-benzoic acid 2-methylpiperidide (7b) are surprisingly formed instead of the methylthio substitution products by treatment of2a with the corresponding amine in the presence of aluminum chloride.

Herrn Professor Dr. Dr. h. c.Waldemar Adam zum 60. Geburtstag gewidmet