| 摘要 |
<p>Improved method for (I) R = MeO or Me2N (a) II (R=MeO; 0.1 equiv.) in dioxan (100 ml.) was added (30 mins.) to EtNO2 (0.1 equiv.) in dioxan (100 ml.) and 40% PhCH2.Me3NOH Aq. (2 ml.), at >0 deg., heated 6 hrs. at 100 deg., cooled, acidified (HCl), extd. (Et2O), and evapd., giving III. (b) This (4.3 g.) in EtOH (50 ml.) was mixed with NaOH (10 g.) in EtOH (60 ml.), acidified after 10 mins., by dropwise (30 mins.), addition of 2N-H2SO4 (400 ml.), NaOH added to pH 4, filtered, washed, and dried, giving IV. (c) This (0.01 mol. as Na salt) was dissolved in H2O (100 ml.), NaBH4 (0.1 mol.) in H2O (20 ml.) added, stirred 4 hrs. at 20 deg., and acidified, giving V. (d) V (0.1 mol.) in MeOH (100 ml.), was hydrog. over Pd-C (100 ml.) until 0.3 mol. H2 was adsorbed. The soln. was filtered and evapd., giving VI. (e) This (0.1 mol.) and p-chlorobenzoic anhydride (0.1 mol.), were refluxed 2 h. in PhH (100 ml.), washed with H2O, dried, and chromat. on Florisil, giving VII. (f) This (0.1 equiv.) in C6H5N (250 ml.) at 0 deg., was treated with MeSO2Cl (0.1 equiv.), stirred 3 h. at 0 deg., concd. to 50 ml., poured into ice-water (300 ml), and extd. (CHCl3). The extract was dried, evapd., and the residue chromat. on Florisil, giving VIII. (g) VIII (from f) was heated with CF3CO2H (5 ml) in dioxan (100 ml.), evapd. in vac., neutralised to pH 3, extd. with Et2O, washed, and evapd. giving IX. (h) This (1 pt.) in cyclohexene (20 pts.) and t-BuOH (50 pts.), was refluxed with Pd-C (1 pt.) for 5 hrs., filtered, concd., filtered, and recryst. from t-BuOH, giving I (R=MeO).</p> |
