反应详情

温度

20 °C

A sodium naphthalene solution in 1,2-dimethoxy ethane (3 L) was prepared from sodium (39 g) and naphthalene (236 g) at 25°-35° C. during 2 hours. Solid d-2-methyl-3-toluene-p-sulfonyl-1,2,4,5-tetrahydro-3H,3-benzazepinne (90 g) was added during 20 minutes at 22°-26° C. with a cooling bath in place. The reaction was stirred for 2.5 hours at room temperature (about 20° C.). The reaction mixture was decomposed by adding water (50 ml) at 15°-20° C. and evaporating the solvent. The residue was dissolved in ether/water and the ether layer was separated. The ether was washed with dilute HCl and the acid layer was separated. Aqueous sodium hydroxide was added and the amine isolated in ether afforded an oil. The oil was converted to the hydrochloride which was gummy. Trituration with hot acetone (200 ml) afforded a brown solid which later turned blue, melting point 184°-187° C. Ether was added to the acetone and further 8.4 g was obtained, melting point 178°-182° C. The dark green filtrates were evaporated and the residue dissolved in water. Basification with aqueous NaOH and extraction with ether afforded an oil. The oil was converted to the hydrochloride in ether and the gummy salt was treated with warm acetone and the resulting solid was filtered, melting point less than 140° C. The solid was dissolved in acetone (50 ml)/isopropanol (17.5 ml) at reflux and cooled in a refrigerator at about 4° C. The first crop of crystals was filtered, melting point 178°-182° C. The filtrate was evaporated and the gummy residue was triturated with acetone and the solid filtered, melting point 120°-130° C. The salts so prepared were combined and made basic with NaOH and the free amine was isolated in ether. The oil was distilled to give a colorless amine which afforded a solid hydrochloride from ether. The salt was dissolved in hot isopropanol (125 ml), filtered and diluted with ether (125 ml). Immediate crystallization began and the suspension was stirred for 16 hours at room temperature. The salt was filtered to give a solid melting at 183°-187° C. [α]57825 =-32.39° (C=1.05 in CH3OH).

1. additionSolid d-2-methyl-3-toluene-p-sulfonyl-1,2,4,5-tetrahydro-3H,3-benzazepinne (90 g) was added during 20 minutes at 22°-26° C. with a cooling bath in place
2. customevaporating the solvent
3. dissolutionThe residue was dissolved in ether/water
4. customthe ether layer was separated
5. washThe ether was washed with dilute HCl
6. customthe acid layer was separated
7. additionAqueous sodium hydroxide was added