反应详情

To a solution of 100 ml of 2-hydroxyadamantane dissolved in 250 ml pyridine is added 137.9 g of trifluoroacetic anhydride dropwise, and the reaction mixture is stirred overnight. The reaction mixture is poured over ice then diluted to 1.0 liter with water and extracted three times with 500 ml of diethyl ether. The combined diethyl ether extracts are washed with 5% hydrochloric acid until the wash is acidic then washed once with 5% sodium bicarbonate solution and dried over magnesium sulfate. The solvent is removed under reduced pressure to give 2-adamantyl trifluoroacetate as an oil. 50 Grams of 2-adamantyl trifluoroacetate are dissoled in 500 ml of hexane and photolyzed (254 nm) for 4 days. The solvent is removed under reduced pressure and the oily residue is placed in a low pressure column and eluted with dichloroethane. The starting material is the first major component eluted. The second major component is the product, 1-trifluoroacetyl-2-hydroxyadamantane which is crystallized from pentane. To 100 ml of 10% sodium hydroxide solution is added 13.0 g of 1-trifluoroacetyl-2-hydroxyadamantane. The reaction mixture is heated for 15 minutes on a steam bath then diluted to 200 ml with water and washed two times with 150 ml of diethyl ether. The aqueous solution is acidified with concentrated hydrochloric acid. The precipitate is collected by filtration, washed with water and dried in a steam cabinet to give 2-hydroxy-1-adamantanecarboxylic acid. 6.7 Grams of 2-hydroxy-1-adamantanecarboxylic acid are dissolved in 50 ml of acetone and enough 8 N Jones Reagent (chromic anhydride in dilute sulfuric acid) is added to retain a red color for 1 minute. Isopropyl alconhol is added to destroy any excess Jones reagent and the solvent is removed under reduced pressure. The residue is diluted with water, collected by filtration and washed with water then suction dried to give 2-keto-1-adamantanecarboxylic acid. 4.7 Grams of 2-keto-1-adamantanecarboxylic acid is dissolved in 75 ml of ethanol and hydrogenated over platinum oxide in the presence of ammonia gas under 60 psi of pressure at room temperature. The solvent is removed under reduced pressure. 15 ml of water is added to the residue and removed under reduced pressure. This step is repeated with another 15 ml of water then the residue is dried at 100° C. under reduced pressure for 1 hour to give 2-amino-1-adamantanecarboxylic acid which is represented by the following structure ##STR45##

1. customfor 1 minute
2. additionIsopropyl alconhol is added
3. customto destroy any excess Jones reagent
4. customthe solvent is removed under reduced pressure
5. additionThe residue is diluted with water
6. filtrationcollected by filtration
7. washwashed with water
8. customthen suction dried