T. Kiriyama

Studies on hetero-cage compounds—VI : Transannular cyclizations in pentacyclo[6.2.1.0.2,70.4,1005,9]undecan-3,6-dione system

Abstract Several 4-oxa- and -aza-bird-cage compounds were prepared by transannular cyclizations of pentacyclo[6.2.1.0. 2,7 0. 4,10 0 5,9 ]undecan-3,6-dione ( 3 ). Diol derivatives of 3 cyclized to afford the corresponding 4-oxa-bird-cage derivatives such as 9 , 16a and 16b . The corresponding 3-keto-6-ol derivatives ( 6 , 10a and 10b ) did not cyclize transannularly, while 3-imino-6-ol, 3-keto-6-amino, and 3- imino-6-amino type derivatives cyclized to afford 3-substituted 4-oxa- and -aza-bidr-cage compounds such as 12 , 14 and 18 . The transannular cyclization reactivity in the 3 system has been compared with that in the bicyclo[3.3.1]nona-3,7-dione system ( 1 ).

Synthesis of adamantane derivatives—XIII : Synthesis of 9-methyl-9-azatricyclo[3.3.1.03,7]nonane (9-methyl-9-azanoradamantane) and its derivatives☆

Pyrolytic decomposition of the sodium salt of pseudopelletierine tosylhydrazone in diglyme gave 80% yield of 9-methyl-9-azatricyclo[3.3.1.03,7]nonane (IIIa), while the decomposition in ethylene glycol afforded IIIa (11%) and 9-methyl-9-azabicyclo-[3.3.1]nonene-2 (IV) (35%) and the pyrolysis without solvent gave IIIa (53%) and IV (19%). The photolytic decomposition in ether gave also IIIa (30·3%) and IV (33·3%), but in this case, together with 1-azatricyclo[4.3.0.13,9]nonane (V) (6·1%) and 9-methyl-9-azatricyclo[3.3.1.01,3]nonane (VI) (4·3%). The Hofmann degradation of the methiodide (VIIa) of IIIa afforded 7-dimethylaminobicyclo[3.3.0]octene-2 (VIII) which was further converted to bicyclo[3.3.0] octene-2 (XII) by repeated Hofmann degradation after the hydrogenation. IIIa was converted to 9-azatricyclo[3.3.1.03,7]nonane (IIIc) via an N-oxide (XIII), followed by an N-acetyl derivative (IIIb), and also by direct oxidation of IIIa with mercuric acetate. Bromination of IIIa and VIIa afforded the corresponding perbromides VIIb and VIIc respectively.

Synthesis of Adamantane Derivatives. XIX. Aluminum Chloride-Catalyzed Reactions of N-Chloro-1-Adamantylamine Derivatives

Abstract The chemical behavior of 1-adamantylnitrenium ion seems to be not known much compared to 1-adamantylcarbinyl cation,2 though one example of the rearrangement of 1-adamantylnitrenium ion to 4-azahomoacamantyl ion has been reported recently by Kovacic et al in the reaction of 1-M,N-dichloroaminoadamantane with aluminum chloride.3 From our interest in the reactivity and rearrangement aptitude of 1-adamantylnitrenium ion, we investigated the reactions of various N-substituted N-chloro-1-adamantylamine derivatives with aluminum chloride. This communication deals with the preliminary results which indicated that the reactions of 1-adamantylnitrenium ion are much affected by the N-substituents and also by the solvents used.