Cyanoethylation of some n-substituted 2,5-dimethyl-4-piperidones

1,2,5-Trimetnyl- and 1-(-chlorocrotyl)-2,5-dimethyl-5-(-cyanoethyl)-4-piperidones were synthesized and separated into individual isomers. The corresponding isomeric 5-(-carboxyethyl)-4-piperidones were obtained by hydrolysis. The isomeric 1,2,5-trimethyl-3,5-bis(-cyanoethyl)- and 1,2,5-trimethyl-3,3,5-tris(-cyanoethyl)-4-piperidones were synthesized by subsequent cyanoethylation of the individual 1,2,5-trimethyl-5-(-cyanoethyl)-4-piperidone isomers.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 479–481, April, 1971.     

Esters of (1,2, 5-trimethyl-4-hydroxy-4-piperedyl)- and phenyl-(1,2, 5-trimethyl-4-hydroxy-4-piperidyl) acetic acids

The methyl ester of a new hydroxy acid of the piperidine series (-phenyl--(1,2, 5-trimethyl-4-hydroxy 4-piperidyl)acetic acid) has been prepared. Ethyl -(1,2, 5-trimethyl-4-hydroxy-4-piperidyl)acetate has been converted into the substituted pyridine, 1,1-diphenyl-2-(2-5-dimethyl-4-pyridyl)ethylene.     

Condensation of 1,2,5-trimethyl-4-piperidone with ethyl- and naphthylacetylenes and synthesis of substituted pyridines

The Favorskii reaction with 1,2,5-trimethyl-4-piperidone and ethyl- and naphthylacetylenes gave the corresponding piperidols, the hydrogenation of which gave 1,2,5-trimethyl-4-nbutyl(or 2-naphthylethyl)-4-piperidols. 4-Phenyl- and 4-butyl-2,5-dimethylpyridine were condensed with formaldehyde, and some of the transformations of the resulting-hydroxyethyl derivatives were studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 349–352, March, 1973.     

Synthesis of stereoisomeric 1,3-dimethyl- and 1,2,5-trimethyl-4-acyl(benzoyl)-4-piperidinols

In order to synthesize stereoisometric 4-acyl(benzoyl)-1, 3-dimethyl and-1, 2, 5-trimethyl-4-piperidinols, the reaction of the geometrical isomers of 4-cyano-1, 3-dimethyl- and -1, 2, 5-trimethyl-4-piperidinols and the amines and imidic esters corresponding to them with some alkyl- and arylmagnesium halides, leading to the corresponding isomeric piperidinic -ketols, has been studied. The dependence of the reactivity of the geometrical isomers of the compounds studied on the spatial orientation of their functional groups has been shown.     

Indole derivatives

The Fischer cyclization of arylhydrazones of 1,3-dimethyl-, 1, 3, 5-trimethyl-, and 1, 3, 6-trimethyl-4-piperidones is examined. An unusual duration of the reaction is found, resulting in rearrangement products (1, 2, 3, 4-tetrahydropyrimido[3,4-a]indoles). It is shown that hydrogenation of the latter gives 2-(-dimethylaminoalkyl)-3-methylindoles.For Part XXX, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1219–1224, September, 1970.     

Synthesis and stereoisomerism of N-oxides of the decahydroquinoline series

The stereochemistry of the oxidation of epimeric (with respect to the 2 and 4 positions) 1-ethyl (n-propyl, n-butyl)-2-methyl-4-ethynyl-, 1,2,9-trimethyl-4-ethynyl(vinyl, ethyl, acetyl)-, and 1,2,2-trimethyl-4-ethynyl-trans-decahydro-4-quinolols was investigated. A preferred axial orientation of the NO bond was established on the basis of a comparison of the chemical shifts of the 3-H _a and 3-H_e protons of the bases and N-oxides.See [1] for communication IV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1378–1382, October, 1976.     

Substituted pyridines. Dehydrogenation,desamination, and n-desmethylation of 4-amino-1, 2, 5-trimethylpiperidine and (1, 2, 5-trimethyl-4-piperidyl)benzylideneamine

4-Amino-1, 2, 5-trimethylpiperidine and (1, 2, 5-trimethyl-4-piperidyl)benzylideneamine are partially converted into, -lutidine as a result of dehydrogenation, desamination, and N-desalkylation over a type K-12 dehydrogenating catalyst.     

N-substituted 2, 5-dimethyl-4-ethynyl(vinyl)piperid-4-ols

They -isomers of 1-(3-chlorobuten-2-yl)- and 1-benzyl-2,5-dimethyl-4-ethynylpiperid-4-ols (I, II) and of 1-(3-chlorobuten-2-yl)-2,5-diemethyl-4-vinylpiperid-4-ol (III) and the quaternary salts of compounds I–III and of the -isomers of the 1,2,5-trimethyl-4-ethynyl-(vinyl)piperid-4-ols [1] have been synthesized.     

Syntheses of di-and tetrahydropyrroles

The cyclization of -nitro carbonyl compounds containing all the required substituents has been used to obtain polysubstituted 1-pyirolines. Ethyl -acetyl-,-dimethyl--nitrobutyrate and methyl 4-acetyl-4-ethoxycarbonyl-5, 5-dimethyl-6-nitrocaproate have given respectively, 3-ethoxycarbonyl-2, 4, 4-trimethyl- and 3-ethoxycarbonyl-3-methoxycarbonylethyl-2, 4, 4- trimethyl-1-pyrrolines.     

Basicities and structures of 4,4,6-trimethyl-2-arylamino-5,6-dihydro-4H-1,3-thiazines and 4,4,6-trimethyl-2-arylamino-5,6-dihydro-4H-1,3-oxazines

The relative basicities of 4,4,6-trimethyl-2-arylamino-5,6-dihydro-4H-1,3-thiazines and 4,4,6-trimethyl-2-arylamino-5, 6-dihydro-4H-1,3-oxazines, which are capable of amine-imine tautomerism, and of model compounds with fixed amine and imine structures were determined by potentiometric titration in methanol. Good correlation of the pK _a values with the Hammett constants in the investigated reaction series was found. The inapplicability of the use of the pK _a values of model compounds for the determination of the tautomeric equilibrium constants in the case of some N-heterocyclic amines of nonaromatic character with an aryl substituent attached to the exocyclic nitrogen atom of the amidine fragment of the molecule is demonstrated.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1621–1624, December, 1976.     

Di- and trimethyl-substituted 2-azafluorenes and dibasic acids of 2-azafluorenone

Dehydrocyclization of the corresponding 2,5-dimethyl-4-arylpyridines gave 3,5- and 3,8-dimethyl- and 3,5,7- and 3,5,8-trimethyl-2-azafluorenones. Dibasic acids of 2-azafluorenone were obtained from -carboxyarylcinchomeronic acid.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1664–1667, December, 1972.     

Reaction of 2-arylidene-5-methylcyclopentane-1,3,4-trione with β-aminovinylcarbonyl compounds

A simple method is proposed for the synthesis of the previously unknown 2,6,6-trimethyl-9-phenyl-4,5,6,7,8,9-hexahydrobenz[f]-4-azaindane-1,3,8-triones, 2,5-dimethyl-6-R-7-phenyl-4,7-dihydro-4-azaindane-1,3-diones, and their derivatives from 2-arylidene-5-methylcyclopentane-1,3,4-trione and-aminovinylcarbonyl compounds.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 632–636, May, 1971.     

Syntheses,structures, and reactions of di- and tetrahydropyrroles

PMR spectroscopy showed that 2,4,4-trimethyl-, 2,4,4-trimethyl-3-carbethoxy-, and 2,4,4-trimethyl-3-acetyl-¹-pyrrolines usually exist in solutions exclusively in the imine form, regardless of the polarity of the solvents.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 475–478, April, 1971.     

Reaction of dimedone with aldehydes and β-aminovinyl carbonyl compounds

The unsymmetrical condensation of dimedone, an aldehyde, and various -aminovinyl carbonyl compounds, and also bisacetonitrile, has given 3, 4-disubstituted derivatives of 2, 7, 7-trimethyl-5-oxo-1, 4, 5, 6, 7, 8-hexahydroquinoline (Va-f). Compounds Va, d, f have been oxidized with H₂CrO₄ to the corresponding 3, 4-disubstituted 2, 7, 7-trimethyl-5-oxo-5, 6, 7, 8-tetrahydroquinolines (VIa-c). The IR spectra of compounds Va-c, f and VIa and the UV spectra of compounds Va, c, f, and VIa, c have been recorded.     

Transformations of epoxyketones of the carane series using bases

Conclusions -3,4-Epoxycarane-2,5-dione when treated with alcoholates and alkali in alcohol forms 3,6,6-trimethyl-2-oxobicyclo[3. 1. 0]-3-hexen-4-yl-formic acid and-3,4-epoxycaran-2-on-5-ol, whereas in dioxane the first product is formed exclusively.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 677–679, March, 1984.     

Schiff bases in syntheses of substituted naphthylamines,naphthyridines, azaphenanthrenes,and benzocarbazole

9-Methylnaphtho[2,1-b][1,6]naphthyrldine and 2,3-dimethyl-1-azaphenanthrene were obtained on a K-16 dehydrogenating catalyst from N-(1,2,5-trimethyl-4-piperidylidene)--naphthylamine, while N-cyclohexylidene--naphthylamine yielded N-phenyl--naphthylamine and benzo[a]carbazole.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1400–1403, October, 1972.     

Stereochemistry of heterocyclic compounds

Summary On the basis of a number of chemical reactions, views are expressed on the possible steric structure of 1, 2, 5-trimethyl-4-ethyl-4-piperidinol isomers (I,, ), the corresponding acetylenic alcohols (II, ,), and certain piperidine derivatives obtained from them.     

Silyl Modification of Biologically Active Compounds. 9. Synthesis and Biological Activity of Novel 1,3-Disilabenzo[5,6]cyclohexene Derivatives

We have synthesized a series of 1,3-disilabenzo[5,6]cyclohexene derivatives starting from (o-bromomethylphenyl)dimethylchlorosilane. Based on NMR data, we have concluded that there is a transannular N Si interaction in the 3',3'-5-trimethyl-2,8-dioxa-5-aza-1-silacyclooctane-1-spiro-1'-(1',3'-disilabenzo[4',5']cyclohexene) obtained. We have studied the psychotropic activity of this compound and its iodomethylate and also 3-(3-chloropropyl)-1,1,3-trimethyl-1,3-disilabenzo[5,6]cyclohexene, and we have shown that they have a sedative effect.     

1,4-bis(4′-hydroxy-1′,2′,5′-trimethyl-4-piperidyl)-1,3-butadiyne and its derivatives

1.4-Bis(4-hydroxy-1,2,5-trimethyl-4-piperidyl)-1.3-butadiyne has been synthesized from the individual isomers of 4-ethynyl-1,2,5-trimethyl-4-piperidol. Hydrogenation, bromination, and cleavage have given, respectively, 1,4-bis(4-hydroxy-1,2,5-trimethyl-4-piperidyl)butane, 1,4-bis(4-nydroxy-1,2,5-trimethyl-4-piperidyl)-1,2,3,4-tetrabromo-1, 3-butadiene, and 4-(1,3-butadiynyl)-1,2,5-trimethyl-4-piperidol.     

Sensitized photochemical reactions of some silyl-1,3-butadienes: Synthesis of 2,2,4-trimethyl-3-methylene-2-silabicyclo [2.1.1]Hexane

The photolysis of 2,4,4-trimethyl-4-sila-3-methylene-l,5-hexadiene

yielded 2,2,4-trimethyl-3-methylene-2-silabicyclo[2.1.1]hexane as the only volatile photoproduct in high yield. However, 2,4,4-trimethyl-4-sila-3-methylene-1,6-heptadiene

was found to be photochemically non-reactive under identical reaction conditions, and the 1-substituted butadienes (VI) and (VIII)

underwent cis-trans isomerism on photolysis.