反应详情

A solution consisting of 4.52 gm. (0.0136 mole) of 4-[[(ethoxycarbonyl)methyl]methylamino]-4-phenylcyclohexanone, ethylene ketal, p-toluenesulfonate (prepared in Example 35, above), and 100 ml. tetrahydrofuran is added to a suspension of 0.52 gm. lithium aluminum hydride in 10 ml. tetrahydrofuran. This reaction is heated at the reaction mixture is heated at the reflux temperature for four (4) hours, after which heating it is allowed to cool and then chilled in an ice bath. To the chilled solution is added 0.52 ml. water followed by 0.52 ml. of 14% aqueous sodium hydroxide, and finally followed by another 1.56 ml. water. A gel forms and the gelatinous liquid is poured through a filter. The filtrate is collected and the liquids removed by evaporation under reduced pressure. The residue thus obtained is chromatographed on a 400 ml. column of silica gel and the chromatogram is developed by elution with a 3% solutin of methanol in methylene chloride which has been saturated with ammonia. The fractions containing the prospective product, as determined by thin layer chromatography, are combined and the solvents removed by evaporation under reduced pressure. The residue thus obtained is dissolved in diethyl ether and then hydrogen chloride saturated diethyl ether is added. A precipitate forms which is collected on a filter and recrystallized from a mixture of methylene chloride and ethyl acetate. There is thus obtained 2.56 gm. (58% yield) of 4-[(2-hydroxyethyl)methylamino]-4-phenylcyclohexanone ethylene ketal hydrochloride having a melting range from 184° to 186° C. A second crop of crystals obtained by removing some of the solvent mixture from the mother liquors by evaporation under reduced pressure weighs 0.56 gm. and has a melting range from 176° to 182° C.

1. temperatureThis reaction is heated at the reaction mixture
2. temperatureafter which heating it
3. temperatureto cool
4. temperaturechilled in an ice bath
5. additionTo the chilled solution is added 0.52 ml
6. additionA gel forms and the gelatinous liquid is poured through a filter
7. customThe filtrate is collected
8. customthe liquids removed by evaporation under reduced pressure
9. customThe residue thus obtained
10. customis chromatographed on a 400 ml
11. washcolumn of silica gel and the chromatogram is developed by elution with a 3% solutin of methanol in methylene chloride which
12. additionThe fractions containing the prospective product
13. customthe solvents removed by evaporation under reduced pressure
14. customThe residue thus obtained
15. customA precipitate forms which is collected on
16. filtrationa filter
17. customrecrystallized from a mixture of methylene chloride and ethyl acetate