反应详情

To a 2-phase mixture of 25.1 g (0.106 mol) of 1-(3-methoxyphenyl)-3,4-dihydronaphthalene, 20 g (0.238 mol) of sodium bicarbonate, 200 ml of water, and 400 ml of methylene chloride at 5° C. was added 24.4 g of 80-85% m-chloroperbenzoic acid portion-wise over 15 minutes. The internal temperature rose to 10° C. After the addition was complete, the mixture was stirred at 0°-5° C. for 2 hr. The layers were separated and the aqueous layer was extracted with 100 ml of methylene chloride. The combined organic layers were extracted with 200 ml of 10% sodium carbonate and then with 100 ml of water, dried over MgSO4 and evaporated to an oil. IR, NMR, and thin layer chromatography indicated the presence of a mixture of epoxide and 1,2-diol monoester. The crude mixture was stirred 3 hours at room temperature in 1M solution of sodium hydroxide in 5:1 ethanol-water. After adjusting the pH to 8 with HCl, the bulk of the solvent was evaporated. The residue was taken up in 500 ml of ether, which was then washed with 50 ml of water, dried over MgSO4, and evaporated. The oily residue was dissolved in 300 ml of dry toluene containing 0.050 g of p-toluenesulfonic acid and refluxed 3 hour in a Dean-Stark apparatus. The solution was washed with 50 ml of 5% sodium bicarbonate and with 50 ml of water, dried over MgSO4 and evaporated to give 25.1 g of the title compound, which was characterized as its 2,4-dinitrophenyl hydrazone derivative, m.p. 161°-161.5° C. (ethanol).

1. customrose to 10° C
2. additionAfter the addition
3. customThe layers were separated
4. extractionthe aqueous layer was extracted with 100 ml of methylene chloride
5. extractionThe combined organic layers were extracted with 200 ml of 10% sodium carbonate
6. dry with materialwith 100 ml of water, dried over MgSO4
7. customevaporated to an oil
8. additionthe presence of a mixture of epoxide and 1,2-diol monoester
9. stirringThe crude mixture was stirred 3 hours at room temperature in 1M solution of sodium hydroxide in 5:1 ethanol-water
10. customthe bulk of the solvent was evaporated
11. washwhich was then washed with 50 ml of water
12. dry with materialdried over MgSO4
13. customevaporated
14. dissolutionThe oily residue was dissolved in 300 ml of dry toluene containing 0.050 g of p-toluenesulfonic acid
15. temperaturerefluxed 3 hour in a Dean-Stark apparatus
16. washThe solution was washed with 50 ml of 5% sodium bicarbonate and with 50 ml of water
17. dry with materialdried over MgSO4
18. customevaporated