Heteroadamantanes and their derivatives. 6. Synthesis and mass-spectrometric investigation of 5-mono- and 5,6-disubtituted 6-oxo-1,3-diazaadamantanes

The corresponding 5-mono- and 5,7-disubstituted 6-oxo-1,3-diazaadamantanes were obtained with high yields by the condensation of mono- and ,'-disubstituted acetones with hexamethylenetetramine in the presence of glacial acetic acid, and their structures were confirmed by IR and PMR spectra. The behavior of the compounds under electron impact was studied, and the main fragmentation paths of their molecules were determined.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1679–1685, December, 1985.     

Heteroadamantanes and their derivatives. 9. Synthesis of 1,5-dinitro-3,7-diazabicyclo[3.3.1]nonane and derived 2,2-disubstituted 5,7-dinitro-1,3-diazaadamantanes

Heating 1,5-dinitro-3,7-di(tert-butyl)-3,7-diazabicyclo[3.3.1]-nonane with concentrated hydrobromic acid gives 1,5-dinitro-3,7-diazabicyclo[3.3.1]nonane. Cyclization of the latter with various aldehydes and ketones gave a series of 2,2-disubstituted 5,7-dinitro-1,3-diazaadamantanes. The behavior of the synthesized compounds under electron impact has been studied.For Communication 8 see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 538–542, April, 1990.     

Heteroadamantanes and their derivatives 26. Synthesis of derivatives of hydroxybenzyldiazahomoadamantane

Summary 1-(4-Hydroxy-3-nitrobenzyl)-3,6-diazahomoadamantan-9-one was obtained by the nitration of hydroxybenzyldiazahomoadamantanone. The behavior of the carbonyl group of this ketone and of its nitro derivative has been studied. The structures of the functional derivatives obtained were confirmed by data of IR, PMR, and mass spectra.For part 25 see [1].M. V. Lomonosov Moscow State Academy of Fine Chemical Technology, Moscow 117571. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 391–394, March, 1995.Original article submitted December 29, 1994.     

Heteroadamantanes and their derivatives. 3. The synthesis of 6-hydroxy-5-methoxycarbonyl-1,3-diazaadamantane

The interaction of methyl 3-oxo-4-(phenylthio)butyrate with formaldehyde and ammonium acetate yielded 5-methoxycarbonyl-6-oxo-7-phenylthio-1,3-diazaadamantane, which, on being heated with skeletal nickel in isopropanol was converted into 6-hydroxy-5-methoxycarbonyl-1,3-diazaadamantane. The structures of the compounds have been confirmed by IR and PMR spectroscopy.For Communication 2, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 661–663, May, 1985.     

Heteroadamantanes and their derivatives. 4. Synthesis of 1,3,5-triazaadamantane

Reduction of 7-nitro-1,3,5-triazaadamantane with hydrazine hydrate in the presence of Raney nickel gave 7-hydroxyamino- and 7-amino-1,3,5-triazaadamantane, from which 7-chloro-, 7-bromo-, and 7-thiocyanato-1,3,5-triazaadamantanes were synthesized by substitutive deamination. Desulfurization of 7-thiocyanato-1,3,5-triazaadamantane in the presence of Raney nickel gave 1,3,5-triazaadamantane.For Communication 3, see [1].Translated from Khitniya Geterotsiklicheskikh Soedinenii, No. 6, pp. 837–840, June, 1985.     

Heteroadamantanes and their derivatives

5,7,-Dinitro-6,6-dimethyl-1,3-diazaadamantane was synthesized by condensation of 1,3-dinitro-2,2-dimethyl-propane with hexamethylenetetramine. Like the previously prepared 5,7-dinitro-1,3-diazaadamantane, it is converted into the corresponding diamino derivative with hydrazine hydrate in the presence of a nickel catalyst, and the diamino compounds gave the 5,7-dibromo derivatives on treatment with sodium nitrite in conc. HBr. The latter were converted to 6,6-dimethyl-1,3-diazaadamantane and 1,3-diazaadamantane on treatment with hydrazine hydrate in the presence of nickel catalyst in ethanol.For Communication 18 see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 230–233, February, 1993.     

Synthesis of 1,3-disubstituted-5-oxo-7a-methyl-5,7a-dihydroindoles

Cycloaddition and addition reactions of ethyl propiolate with a series of 1,3,5-substituted-2-amino-4-methylpyrroles to form, 1,3-disubstituted-5-oxo-7a-methyl-5,7a-dihydroindoles are described. High resolution mass spectral and pmr data are presented.     

Heteroadamantanes and their derivatives. 10. Hydrolysis of 7-bromo-1,3,5-triazaadamantane

Potentiometric titration was used to determine the rate constants of hydrolysis of 7-bromo-1,3,5-triazaadamantane at 50 and 80C. It was shown that the rate of this reaction is significantly lower than the rate of hydrolysis of 1-bromoadamantane.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 543–545, April, 1990.     

Heteroadamantanes and their derivatives. 14. Synthesis of 3,6-diazahomoadamantan-9-ols and their acetates

The reduction of 3,6-diazahomoadamantan-9-ones with metal hydrides gave 3,6-diazahomoadamantan-9-ols, which were convened to acetates by the action of acetic anhydride. The effect of the substituents in the nodal positions on the rates of reduction and acylation is demonstrated.See [1] for Communication 13.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 804–809, June, 1991.     

Heteroadamantanes and their derivatives. 13. Synthesis of 1-azaadamantane and some derivatives of it

3,5,7-Tribromo-1-azaadamantane is made by the action of sodium nitrite on 3,5,7-triamino-1-azaadamantane in concentrated hydrobromic acid. The reduction of this compound with hydrazine hydrate in the presence of a nickel catalyst gives 1-azaadamantane.For Communication 12, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1083–1085, August, 1990.     

Synthesis and mass spectra of 4-mono- and 4,4-disubstituted 5,6-tetramethylenetetrahydro-1,3-oxazine-2-thiones

The syntheses and mass spectra of 5,6-tetramethylenetetrahydro-1,3-oxazine-2-thione and its 4-mono- and 4,4-disubstituted analogs are reported. The primary decay processes under electron impact are loss of the 1,3-oxazine ring, formation of hydrocarbon ions, and rearrangement of the [M–C₆H₉]⁺ ion.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1668–1672, December, 1989.     

Heteroadamantanes and their derivatives. 21. Synthesis of thioureas of the 3,6-diazahomoadamantane series

Unsubstituted and phenyl-substituted thioureas were obtained by the action of benzoyl isothiocyanate and phenyl isothiocyanate on amino-substituted diazahomoadamantanes.For Communication 20 see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 814–817, June, 1993.     

Stereoselective synthesis of 3-mono- and 1,3-disubstituted 4-phenyl-1,2,3,4-tetrahydroisoquinolines

(1S,2S)-(+)-Thiomicamine was transformed in high yield and with high diastereoselectivity into (3R,4R)-4-phenyl-1,2,3,4-tetrahydroisoquinoline-3-carboxylic acid and enantiomerically pure (3R,4R)-3-hydroxymethyl-4-phenyl- and (1R,3R,4R)-3-hydroxymethyl-1-methyl-4-phenyl-1,2,3,4-tetrahydroisoquinoline derivatives.     

Synthesis and conversions of polyhedral compounds. 28. Synthesis of 2-(naphthyl-1′) and 2-(2′-hydroxynaphthyl-1′) derivatives of 5,7-dialkyl-1,3-diazaadamantanes

2-Naphthyl and 2-(2′-hydroxynaphthyl) derivatives of 5,7-dialkyl-1,3-diazaadamantanes were synthesized by the reaction of the corresponding 5,7-dialkyl-3,7-diazabicyclo[3.3.1]nonanes with naphthaldehyde or 2-hydroxynaphthaldehyde. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, 1548–1555, October, 2007.     

Heteroadamantanes and their derivatives. 12. Synthesis of 1,3,6-triazahomoadamantane — A new heterocyclic system

8-Nitro-1,3,6-triazahomoadamantane was obtained by the condensation of nitromethane with an equimolar mixture of 1,4,6,9-tetraazatricyclo[4.4.1.1^4.9]dodecane and hexamethylenetetramine. By reducing it with hydrazine hydrate in the presence of Raney nickel, 8-amino-1,3,6-triazahomoadamantane was synthesized. This was converted to 8-bromo-1,3,6-triazahomoadamantane by the action of sodium nitrite in hydrobromic acid. The 1,3,6-triazahomoadamantane was obtained by reduction of the bromo derivative with hydrazine hydrate in the presence of Raney nickel. The structures of the compounds synthesized were confirmed by PMR and mass spectroscopy.See [1] for Communication 11.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 681–684, May, 1990.     

Synthesis of 6-mono- and 5,6-disubstituted 1,2,3-triazolo[4,5-d]pyrimidin-7-ones

The reactions of N-substituted 4-amino-3-benzyl-1,2,3-triazole-5-carboxamides with phosphorus oxochloride and dimethylformamide at 80 °C or with triethyl orthoacetate and acetic anhydride at 160 °C afforded 6-mono- or 5,6-disubstituted 1,2,3-triazolo[4.5-d]pyrimidin-7-ones in 30—85% and 65—90% yields, respectively.     

Heteroadamantanes and their derivatives. 23. Reduction of nitroaryl derivatives of 3,6-diazahomoadamantane

It has been found that nitroaryl derivatives of diazahomoadamantane can be reduced selectively by hydrazine. New data are presented on the noncatalytic reduction of p-nitrophenyldiazahomoadamantane by hydrazine hydrate.For Communication 22 see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1405–1408, October, 1993.