Adamantanone → Tricyclo[3.3.1.1(3,7)-]decanone, oxime

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Reaction Steps

To 30 g of 2-adamantanone (Aldrich Chem. Co.) in 100 mL of methanol was added 50 g of hydroxylamine hydrochloride and 92 g of sodium acetate trihydrate and the mixture was refluxed for 2 hours. The mixture was concentrated in vacuo, the residue was distributed between 250 mL of dichloromethane and 50 mL of water. The organic layer was separated, dried with magnesium sulfate and concentrated in vacuo to give 30 g of crude 2-adamantanone oxime. This was dissolved in 100 mL of chloroform and 135 g of PPE (polyphosphate ester, prepared by refluxing phosphorus pentoxide with diethyl ether in chloroform, as described by G. Schramm, H. Groetsch, and W. Pollmann, Angew. Chem., Internat. Ed., 1,1 (1962)) was added carefully. When the exothermic reaction ceased, the mixture was refluxed for 5 minute. Then it was cooled in ice, diluted with 500 mL of water and stirred overnight. The organic layer was separated, dried with magnesium sulfate and concentrated in vacuo to give 16.6 g of the crude lactam product. This was dissolved in 250 mL of chloroform and 11 mL of phosphorus oxychloride was added dropwise in 30 minutes. After stirring for additional 1 hour at room temperature, to this stirred mixture was added 25 mL of triethylamine and a solution of 16 g of 4,6-dichloro-2-aminobenzonitrile (4,6-dichloroanthranilonitrile) which was prepared by the methodology shown in Example 11.

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