反应详情

A 3.1 ml (5.0 mmole) of n-butyllithium.hexane solution was added dropwise to 1.51 g (5.0 mmole) of 1-benzyl-2,3,4,5-tetramethoxy-6-methylbenzene and 0.83 ml (5×1.1 mmole) of 1,1,2,2-tetramethylethylenediamine dissolved in anhydrous tetrahydrofuran (15 ml), under an atmosphere of argon at -5° C. over the period of 5 minutes, followed by stirring at -5° to 0° C. for 25 minutes. Then, a solution of 0.96 g (5.0 mmole) of 4-chlorobutanol.tetrahydropyranyl ether in tetrahydrofuran (5 ml) was added to the mixed solution over the period of 5 minutes, followed by stirring for further 15 minutes under ice-cooling. Subsequently, the cooling bath was removed, and stirring was effected at room temperature for 20 minutes. The reaction solution was cooled with ice, and made acid by adding a 10% aqueous phosphoric acid solution, and the product was extracted with isopropyl ether. The organic layer was separated out, washed with aqueous sodium chloride solution, dried (magnesium sulfate). The solvent was distilled off and the residue was dissolved in methanol (15 ml), followed by addition of 48 mg (5×1/20 mmole) of p-toluenesulfonic acid and stirring at 70° C. for 15 minutes. After cooling by standing at room temperature, the mixed solution was neutralized by adding an aqueous sodium hydrogen-carbonate solution, and the solvent was distilled off. Isopropyl ether and water were added to the residue to effect extraction. The isopropyl ether layer was washed with aqueous sodium chloride solution, dried (magnesium sulfate) and evaporated. The residual solution was chromatographed on a silica gel column to perform purification (elution with isopropyl ether) to thereby give 1.29 g (69%) of 5-(2,3,4,5-tetramethoxy-6-methylphenyl)-5-phenylpentane-1-ol. Its typical physical properties and nuclear magnetic resonance spectrum data are shown in Table 14.

1. stirringby stirring for further 15 minutes under ice-
2. temperaturecooling
3. customSubsequently, the cooling bath was removed
4. stirringstirring
5. waitwas effected at room temperature for 20 minutes
6. temperatureThe reaction solution was cooled with ice
7. additionby adding a 10% aqueous phosphoric acid solution
8. extractionthe product was extracted with isopropyl ether
9. customThe organic layer was separated out
10. washwashed with aqueous sodium chloride solution
11. dry with materialdried (magnesium sulfate)
12. distillationThe solvent was distilled off
13. dissolutionthe residue was dissolved in methanol (15 ml)
14. stirringstirring at 70° C. for 15 minutes
15. temperatureAfter cooling
16. customby standing at room temperature
17. distillationthe solvent was distilled off
18. additionIsopropyl ether and water were added to the residue
19. extractionextraction
20. washThe isopropyl ether layer was washed with aqueous sodium chloride solution
21. dry with materialdried (magnesium sulfate)
22. customevaporated
23. customThe residual solution was chromatographed on a silica gel column
24. custompurification (elution with isopropyl ether)