T. M. Serova

Synthesis of fragrant 1,3-diazaadamantan-6-ones

Abstract5-Benzyl-1,3-diazaadamantan-6-one and its derivatives at the benzene ring were synthesized by the condensation of hexamethylenetetramine with 4-phenylbutan-2-one (jasmarol) and its derivatives, viz., 4-(4-hydroxyphenyl)butan-2-one (raspberry ketone), 4-(4-methoxyphenyl)butan-2-one (anisylacetone), and 4-(4-hydroxy-3-methoxyphenyl)butan-2-one (vanillylacetone, zingerone).

Synthesis of 1-(pyridin-4-yl)-3,6-diazahomoadamantane and its derivatives

Condensation of 1-(pyridin-4-yl)propan-2-one with 1,3,6,8-tetraazatricyclo[4.4.1.13,8]dodecane gave 1-( pyridin-4-yl)-3,6-diazahomoadamantan-9-one as intermediate product in the synthesis of 1-(pyridin-4-yl)-3,6-diazahomoadamantane and its derivatives having functional substituents at the bridging carbon atom in the homoadamantane skeleton.

Synthesis of fragrant substances. Diazaadamantanones

By condensation of hexamethylenetetramine and tetramethylenediethylenetetramine with 1-(4-methoxyphenyl)propan-2-one and 1-(3,4-dimethoxyphenyl)propan-2-one new fragrant substances, diazaadamantanones, were synthesized. By heating of 5-(4-methoxyphenyl)-1,3-diazaadamantan-6-one and 1-(4-methoxyphenyl)-3,6-diazahomoadamantan-9-one with hydrobromic acid 5-(4-hydroxyphenyl)-1,3-diazaadamantan-6-one and 1-(4-hydroxyphenyl)-3,6-diazahomoadamantan-9-one were obtained.

Synthesis of fragrant 3,6-diazahomoadamantan-9-ones

A condensation of tetramethylenediethylenetetramine with 4-phenylbutan-2-one and its derivatives such as 4-(4-hydroxyphenyl)butan-2-one, 4-(4-methoxyphenyl)butan-2-one, and 4-(4-hydroxy-3-methoxyphenyl)butan-2-one led to fragrant compounds: 1-benzyl-3,6-diazahomoadamantan-9-one and its derivatives at the benzene ring.

Formation of 1,3-diazaadamantane derivatives by the reaction of bispidine derivatives with dialdehydes

Heating of 3,7-di(tert-butyl)-1,5-dimethyl-3,7-diazabicyclo[3.3.1]nonan-9-one with hydro-bromic acid gave 1,5-dimethyl-3,7-diazabicyclo[3.3.1]nonan-9-one (1,5-dimethylbispidin-9-one). Condensation of this compound or 1,5-dimethylbispidin-9-ol with dialdehydes afforded new compounds containing two 1,3-diazaadamantane moieties in one molecule, which are connected either directly or through spacers.

Synthesis of 1-benzyl-3,6-diazahomoadamantane

By condensation of 4-phenylbutan-2-one with tetramethylenediethylenetetramine 1-benzyl-3,6-diazahomoadamantan-9-one was synthesized. Further nitration of 1-benzyl-3,6-diazahomoadamantan-9-one yielded 1-(4-nitrobenzyl)-3,6-diaɛahomoadamantan-9-one. The modification of the nitro and carbonyl groups resulted in the formation of 1-benzyl-3,6-diazahomoadamantane and its derivatives with functional groups in the benzene ring and at the bridge carbon atom C9.

Heteroadamantanes and Their Derivatives: XXV. Synthesis of 3,6-Diazahomoadamantane-9-spirothiiranes

By treating 3,6-diazahomoadamantane-9-spirooxiranes with potassium thiocyanate 3,6-diazahomoadamantane-9-spirothiiranes were obtained which further by reductive desulfuration were converted into 3-methyl- and 9-methylene-3,6-diazahomoadamantanes.

Synthesis of 3,6-diazahomoadamantane

Condensation of 1-phenylsulfanylpropan-2-one with 1,3,6,8-tetraazatricyclo[4.4.1.13,8]dodecane gave 1-phenylsulfanyl-3,6-diazahomoadamantan-9-one which was reduced to 1-phenylsulfanyl-3,6-diazahomoadamantane, and the latter was subjected to desulfurization over Raney nickel to obtain previously unknown 3,6-diazahomoadamantane. Heating of 9-phenyl-3,6-diazahomoadamantan-9-ols with Raney nickel resulted in reduction of the hydroxy group with formation of 9-phenyl-3,6-diazahomoadamantanes.

Synthesis of N,N′-di(1-adamantyl)bispidin-9-ones

The condensation product of adamantan-1-amine with formaldehyde, 1,3,5-tri(1-adamantyl)-1,3,5-triazacyclohexane, was treated with three different types of ketones: symmetric (RCH2)2CO, nonsymmetric RCH2COCH3, and acetone to obtain 1,5-R-N,N′-di(1-adamantyl) bispidin-9-ones, N,N′-di(1-adamantyl)-1-[(1-adamantylamino)methyl]-5-methylbispidin-9-one, and N,N′-di(1-adamantyl)-1,5-bis[(1-adamantylamino)methyl]bispidin-9-one. 1,5-R-N,N′-Di(1-adamantyl)bispidin-9-ones were reduced with sodium borohydride to 1,5-R-N,N′-di(1-adamantyl)bispidin-9-ols.

Synthesis of a new type of 1,3-diazaadamantan-6-ones

A new type of 1,3-diazaadanamtan-6-ones was synthesized by heating the 3,7-di(tert-butyl)-1-[(tert-butylamino)methyl]bispidin-9-one derivatives with concentrated hydrobromic acid followed by condensation with formaldehyde.