Reaction of dimethylamines with epimeric (at the 2 and 4 positions) trans-2-methyl- and trans-1,2-dimethyl-4-vinylethynyldecahydro-4-quinolols

A mixture of the corresponding 4-(4-dimethylamino-1,2-butadienyl)- and 4-(4-dimethylamino-1-butynyl)decahydro-4-quinolols, with predominance of the allene components, is formed from each vinylacetylenic alcohol as a result of the addition of diethylamine to epimeric (at the 2 and 4 positions) trans-2-methyl- and trans-1,2-dimethyl-4-vinylethynyldecahydro-4-quinolols. On the basis of the PMR spectra and data on the stabilities of allenic and acetylenic diamino alcohols under the conditions of their formation, it was concluded that the addition of dimethylamine to 4-vinylethynyldecahydro-4-quinolols proceeds simultaneously via two pathways — at the 1,4 and 3,4 positions of the vinylethynyl substituent.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 940–945, July, 1976.The authors thank A. S. Fridman and T. E. Prokof'ev for their participation in the discussion of the PMR spectra.     

Reaction of alkali-metal hypohalites with stereoisomeric 2-methyl-1-alkyl-2-methyl-4-ethynyldecahydro-4-quinolols

Isomeric 1-alkyl-2-methyl-4- (haloethynyl) decahydro-4-quinolols were synthesized by reaction of the individual stereoisomers of 1-alkyl-2-methyl-4-ethynyl-decahydro-4-quinolols with alkali solutions of potassium hypochlorite and hypobromite. 1-Chloro-2-methyl-4-ethynyl decahydro-4-quinolols are formed by the action of an alkaline solution of potassium hypochlorite on isomeric 2-methyl-4-ethynyldecahydro-4-quinolols. Hydrogenolysis of the carbon-halogen bond accompanied by hydrogenation of the CC bond was observed under conditions of catalytic hydrogenation of 1,2-dimethy1-4-(haloethynyl) decahydro-4-quinolols. Primarily hydrogenolysis of the nitrogen-halogen bond and subsequent reduction of the acetylenic bond occur in the hydrogenation of 1-chloro-2-methyl-4-ethynyldecahydro-4-quinolols. Replacement of chlorine by hydrogen and subsequent alkylation of the resulting secondary amine and formation of the hydrochlorides of the corresponding N-methyl-substituted acetylenic alcohols occur in the reaction of the chloramines with a mixture of formaldehyde and formic acid.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 98–103, January, 1976.     

Synthesis and stereoisomerism of N-oxides of the decahydroquinoline series

The results of the oxidation of a number of 4-substituted 1,2-dimethyldecahydro-4-quinolones with hydrogen peroxide in methanol are in conformity with the results obtained by us earlier and confirm that the stereochemistry of the oxidation of nitrogen depends on the configuration of the methyl substituent in the 2 position of the decahydroquinoline ring. Under these conditions, the epimeric 1,2-dimethyl-trans-decahydro-4-quinolones undergo partial interisomerization at the 2 position to give a mixture of three N-oxides that correspond to both amino ketones. The oxidation of the corresponding ketals proceeds like the oxidation of amino alcohols without epimerization. It is thereby shown that the epimerization of the C₂ center during the formation of the N-oxides from epimeric 1,2-dimethyl-trans-decahydro-4-quinolones occurs with the participation of the carbonyl group.     

Synthesis and stereoisomerism of the decahydroquinoline series N-oxides 6. X-ray diffraction study of 1,2e-dimethyl-4a-ethynyl-4e-hydroxy-trans-decahydroquinoline N-oxide hydrobromide

The results of x-ray diffraction analysis on 1,2e-dimethyl-4a-ethynyl-4e-hydroxy-trans-decahydroquinoline N-oxide hydrobromide corroborated the orientation of the substituents at the nitrogen atom that was determined previously from PMR data.For Communication 5, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 82–85, January, 1993.     

Diaza crown ethers based on sym-triazine derivatives

The reaction of 2-dialkylamino-4,6-dichloro-1,3,5-triazines with the disodium derivatives of di- and triethyleneglycols, has given four new diaza crown ethers. The structures of the compounds synthesized have been established by IR and PMR spectroscopy and elementary analysis.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1277–1279, September, 1984.     

Synthesis of macroheterocycles on the basis of 2,2-dimethyl-4-oxotetrahydropyran

Macrocyclic compounds of a new type were synthesized by the reaction of 2,2-dimethyl-4-oxos-5,5-bis (-succiminidooxycarbonylethyl)tetrahydropyran with diamines under conditions that do not require high dilution of the reagents. It was established that 1,9-diazo-12,15-dioxa-2,8-dioxocycloheptadecane-5-spiro-3-(6,6-dimethyl-4-oxo)tetrahydropyran forms a complex that includes water molecules.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1458–1461, November, 1984.     

Investigation of the spatial orientation of the hydroxy group and the intramolecular hydrogen bond in stereoisomeric 2,9-dimethyl- and 1,2,9-trimethyldecahydro-4-quinolols and their 4-ethynyl-substituted derivatives by IR spectroscopy

The spatial orientation of the hydroxy group in stereoisomeric 2,9-dimethyl- and 1,2,9-trimethyldecahydro-4-quinolols and their 4-ethynyl-substituted derivatives was established by IR spectroscopy. The formation of an intramolecular hydrogen bond in the equatorial isomers of trans- and cis-2,9-dimethyl- and 1,2,9-trimethyldecahydro-4-quinolols and cis-2,9-dimethyl- and 1,2,9-trimethyl-4-ethynyldecahydro-4-quinolols, which leads to a small degree of distortion of the chair conformation of the heteroring, was demonstrated. The enthalpy of formation of the hydrogen bond was calculated. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 796–800, June, 1980.