Reaction of γ-benzylideneaminopropanol with dialkyl phosphorochloridites

Reactions of dialkyl phosphorochloridites with 3-(N-benzylideneamino)propan-1-ol follow two pathways giving rise to linear dialkyl 1-(3-chloropropylamino)benzylphosphonates and diastereomeric cyclic 2-alkoxy-2-oxo-3-phenyl-1,4,2-oxazaphosphepanes. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1453–1455, June, 2005.     

Reaction of ethylN,N-(p-methoxybenzal)-p-aminobenzoate with dialkyl phosphonates

Abstact Interaction of ethylN,N-(p-methoxybenzal)-p-aminobenzoate with dialkyl phosphonates results in dialkyl (N-p-ethoxycarbonylphenylamino)-p-methoxybenzal phosphonates. In the resulting compounds hydrogen bonds are observed by IR spectroscopy.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1301–1303, May, 1996.     

Synthesis of new dialkyl α-aminophosphonates and dialkyl α-aminothiophosphonates

New dialkyl α-aminophosphonates and α-aminothiophosphonates were synthesized by reactions of dialkyl phosphites orO,O-dialkyl thiophosphites withN-benzylidene 2-(vinyloxy)ethylamine orN-(4-fluorobenzylidene)-2-(vinyloxy)ethylamine. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1815–1817, September, 1999.     

New reaction pathway of dialkyl phosphorochloridites with salts of α-benzylideneaminocarboxylic acids. Direct synthesis of α-aminophosphonates from isostructural α-benzylideneaminocarboxylic acids

The reaction of sodium N-benzylidenevalinate with dialkyl phosphorochloridites is accompanied by decarboxylation and yields diastereomeric N-(1-dialkoxyphosphoryl-2-methylpropyl)-N-(1-dialkoxyphosphorylbenzyl)amines. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1449–1452, June, 2005.     

Regioselective Reaction of <Emphasis Type="Italic">N</Emphasis><Superscript>1</Superscript>-Benzyl-<Emphasis Type="Italic">N</Emphasis><Superscript>2</Superscript>-(4-nitrophenyl)ethanediamide and Acetylenic Esters

Summary. The regioselective reaction of N¹-benzyl-N²-(4-nitrophenyl)ethanediamide with dialkyl acetylenedicarboxylates or alkyl propiolates in the presence of triphenylphosphine leads to dialkyl 4-benzylamino-1-(4-nitrophenyl)-5-oxo-2,5-dihydro-1H-pyrrole-2,3-dicarboxylates or alkyl 4-benzylamino-1-(4-nitrophenyl)-2-oxo-5-pyrrolidinecarboxylates in good yields.     

Two-fragment α-adrenolytics

Dialkyl β-(2-aroxyethylamino)ethylphosphonates,N-[β-(2-methoxyphenoxy)ethyl]-N′-[β-(diethoxyphosphoryl)ethyl]-α,ω-diaminoalkanes, and diethyl β-(N-arylpiperazino)ethyl-phosphonates were synthesized by the reactions of dialkyl vinylphosphonates with β-aroxyethylamines,N-[β-(2-methoxyphenoxy)ethyl]-α,ω-diaminoalkanes, andN-aryl-piperazines, respectively. The compounds synthesized exhibit hypotensive and α-adrenolytic activities. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 987–991, May 1999.     

The reaction of (N-isocyanimino)triphenylphosphorane with dialkyl acetylenedicarboxylates in the presence of 1,3-diphenyl-1,3-propanedione: a novel three-component reaction for the stereoselective synthesis of dialkyl (Z)-2-(5,7-diphenyl-1,3,4-oxadiazepin-2-yl)-2-butenedioates

Reactions of dialkyl acetylenedicarboxylates with (N-isocyanimino)triphenylphosphorane in the presence of 1,3-diphenyl-1,3-propanedione proceed smoothly at room temperature to afford dialkyl (Z)-2-(5,7-diphenyl-1,3,4-oxadiazepin-2-yl)-2-butenedioates in high yields. The stereochemistry of the final products were confirmed by single crystal X-ray structure determination. The reaction is completely stereoselective.     

Michael reaction. V. Stereochemistry of the NaNH2 catalyzed two-step reaction between phenylacetic acid dialkyl amides and methyl cinnamate or cinnamic acid dialkyl amides

The reaction is investigated between sodium-metallated (NaNH₂) phenylacetic acid dialkyl amides and methyl cinnamate or cinnamic acid dialkyl amides. The thermodynamic equilibrium between the diastereomeric 2,3-diphenylglutaric acid amidoesters or diamides is 5/95 in favour of thethreo-isomer. Under kinetic conditions the stereochemistry of the reaction depends on the nature of the donor and the solvent.

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Michael Reaktion. V. Stereochemie der durch NaNH₂ katalysierten zweistufigen Reaktion zwischen Dialkylamiden der Phenylessigsäure und Methylestern oder Dialkylamiden der Zimtsäure

Zusammenfassung Die Umsetzung zwischen der mit festem NaNH₂ gewonnenen Natriumderivaten der Dialkylamiden der Phenylessigsäure und Methylestern oder Dialkylamiden der Zimtsäure wurde untersucht. Das thermodynamischeE/T-Verhältnis zwischen den gewonnenen diastereomeren Amidestern und Diamiden der 2,3-Diphenylglutarsäure beträgt in allen Fällen 5/95. Das stereochemische Ergebnis unter kinetischen Bedingungen hängt von der Natur des Donators und von den Lösungsmitteln ab.

     

Syntheses based on anabasine. Preparation and transformations of N-oxides

The oxidation of N-acetyl-and N-benzoylanabasine with the tert-butyl hydroperoxide (TBHP)— MoCl₅ system or MCPBA proceeds selectively at the nitrogen atom of the pyridine ring. The oxidation of N-methylanabasine under similar conditions gives a mixture of stereo-isomeric N-oxides at the piperidine nitrogen atom, their ratio depending on the reagent used. The oxidation of anabasine by TBHP— MoCl₅ or MCPBA is accompanied by dehydrogenation and results in anabaseine N-oxide. The reactions of anabasine and anabaseine pyridine N-oxides with acetic anhydride were investigated. The substituted 1H-3-pyridin-2-ones were prepared. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 322—328, February, 2006.     

Reactions of dialkyl phosphonates and phosphonates with bis(benzylideneimino)toluene

Dialkyl phosphonates bind to the C=N bond of bis(benzylideneimino)toluene, with formation of dialkyl (benzylideneimino)benzylaminobenzyl phosphonates. The complicated character of IR spectra of these compounds is connected with the possibility of formation of dimeric cyclic associates and intramolecular hydrogen bonding. Phosphinic acid reacts with bis(benzylidenimino)toluene in a 2: 1 ratio to affordN,N-benzylidenebis(-amino-benzytphosphonic) acid.Translated fromIzvestiya Akademii Nouk. Seriya Khimicheskaya, No. 5, pp. 1303–1305, May, 1996.     

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.     

One-pot, three-component reaction of isocyanides, dialkyl acetylenedicarboxylates, and non-cyclic anhydrides: synthesis of 2,5-diaminofuran derivatives and dialkyl (E)-2-[(N-acyl-N-alkylamino)carbonyl]-2-butenedioates

Abstract  

Isocyanides, dialkyl acetylenedicarboxylates, and non-cyclic anhydrides, for example acetic anhydride or benzoic anhydride, react in one-pot to afford 2,5-diaminofuran derivatives and dialkyl (E)-2-[(N-acyl-N-alkylamino)carbonyl]-2-butenedioates in fairly good yields at room temperature.     

Reaction of N-Heterocycles with Acetylenedicarboxylates in the Presence of N-Alkylisatins or Ninhydrin. Efficient Synthesis of Spiro Compounds

Summary. The 1,3-dipolar intermediates generated by addition of isoquinoline, to dialkyl acetylenedicaboxylates are trapped by N-alkylisatins to produce dialkyl 1,2-dihydro-2-oxo-1-alkylspiro[3H-indol-3,2′-[2H,11bH][1,3]oxazino[2,3-a]isoquinoline]-3′,4′-dicarboxylates in excellent yields. The reaction of isoquinoline, quinoline, or pyridine with dimethyl acetylenedicarboxylate in the presence of ninhydrin led to dimethyl 1,2-dihydro-1,3-dioxospiro[3H-indene-3,2′-[2H,11bH][1,3]oxazino[2,3-a]isoquinoline]-3′,4′-dicarboxylate, dimethyl 1,2-dihydro-1,3-dioxospiro[3H-indene-3,3′[3H,4aH][1,3]oxazino[3,2-a]quinoline]-1,2-dicarboxylate, or dimethyl 1,2-dihydro-1,3-dioxospiro[3H-indene-3,2′-[2H,9aH]pyrido[2,1-b][1,3]oxazino]-3,4-dicarboxylate.     

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.     

Reductivetrans-2,6-diallylation of pyridines with allylboranes. Synthesis oftrans- andcis-2,6-diallyl-1,2,5,6-tetrahydropyridines and their deuterated derivatives

The reductivetrans-2,6-diallylation of pyridines with triallyl- and allyl(dialkyl)boranes has been discovered. Heating (40–100 °C) of pyridine, deuteropyridine, or 3-bromopyridine complexes with triallylborane in the presence of alcohols (ROH or CH₃OD), water, or Et₂NH results in the respectivetrans-2,6-diaIlyl-1,2,5,6-tetrahydropyridines (2,3,22, or25) in 20–97 % yields. A preparative method for the isomerization oftrans-2,6-diallyl compounds2 and25 into the respectivecis-isomers4 and28 by heating them with triallyl- or allyl(dialkyl)boranes (125–150 °C) has been suggested. The hydrogenation oftrans- orcis-2,6-diallyl-1,2,5,6-tetrahydropyridines gavetrans- orcis-2,6-dipropylpiperidines, respectively. Thecis- andtrans-configurations of compounds2 and4 were established by analyzing the NMR spectra ofN-benzyl (7 and13) andN,N-dimethyl (6 and 14) derivatives of piperidine derivatives5 and8. A possible mechanism for the reductive diallylation of pyridines has been discussed.Translated fromIzyestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 693–704, April, 1994.This study was financially supported by the Russian Foundation for Basic Research (Project 93-03-18193).     

Efficient and Simple Route for the Synthesis of N-(2-Pyridyl)-4-ethoxy-5-oxo-2,5-dihydro-1H-pyrrole-2,3-dicarboxylates

Three-component reaction of 2-aminopyridines, dialkyl acetylenedicarboxylates, triphenylphosphine, and ethyl chlorooxoacetate in the presence of triethylamine provides a sufficient route for the synthesis of dialkyl N-(2-pyridyl)-4-ethoxy-5-oxo-2,5-dihydro-1H-pyrrole-2,3-dicarboxylates in good yields.     

(N-methyl-N-alkoxymethylaminomethyl)dialkoxysilanes and bis[N-methyl-N-(dialkoxysilylmethyl)amino]methanes

(N-methyl-N-alkoxymethylaminomethyl)-dialkoxysilanes and bis[N-methyl-N-(dialkoxymethyl)amino]methanes were first obtained by the interaction of (N-methylaminomethyl) dialkoxy-R-silanes with chloromethyl alkyl ethers in yields of 40–67% and 10–25 %, respectively.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 382–383, February, 1995.     

Synthesis of new functionally substituted fullerenopyrrolidines

New fullerenopyrrolidines were synthesized by the three-component reactions of fullerene C₆₀, N-methylglycine, and aromatic aldehydes, viz., N,N-bis(2-chloroethyl)-4-aminobenzaldehyde, N-(2-chloroethyl)-N-methyl-4-aminobenzaldehyde, indole-3-carbaldehyde, 4-phenylbenzaldehyde, and anthracene-9-carbaldehyde. The structures of the resulting compounds were established by spectroscopic methods.     

Preferential Reactivity of Pyridylmagnesiumchloride with N,N-Dialkyl Arylamides over Carbonitriles: Synthesis of 2-(Aroyl) Pyridines

Reaction of 2-pyridylmagnesium chlorides with N,N-dialkyl arylamides afford exclusively 2-(aroyl) pyridines in high yields and purity without the formation of any tertiary alcohol. This method employs easily available raw materials and avoids the use of hazardous lithium reagents and cryogenic conditions. Further, preferential reactivity of this Grignard reagent with N,N-dialkyl arylamides over its carbonitrile counterparts offers a variety of 2-(aroyl) pyridines including the ones containing carbonitrile groups on the aryl ring.     

Microwave-assisted catalyst-free synthesis of tetrasubstituted pyrroles using dialkyl acetylenedicarboxylates and monophenacylanilines

An efficient catalyst-free microwave-assisted synthesis of tetrasubstituted pyrroles using dialkyl acetylenedicarboxylates and substituted monophenacylanilines has been developed. Axial chirality has been noticed in some N-(α-naphthyl/2-isopropylphenyl)-2,3-dicarbethoxy-4-arylpyrroles, but not with N-aryl-2,3-dicarbethoxy-4-(α-naphthyl)pyrrole.