Methanol → HCID 90412642, compound

Participants

Reaction Conditions

Reaction Steps

Into a 500 L reactor was charged 100 L of methanol, followed by addition of 6 (9.7 kg) and CeCl3-7H2O (7.2 kg) in 1 kg portions over 0.5 hour. Temperature of the reaction mixture rose ˜5° C. during the addition. The reaction mixture was cooled down to −10° C., and NaBH4 (0.77 kg) was added in portions (˜150 g) over 1 hour resulting in strong H2 evolution with elevation of the reaction temperature. The transparent reaction mixture was then stirred for 2 hours at 0° C. until HPLC indicated complete conversion. Then 150 L of brine were added to result in white precipitates. The suspension was concentrated under vacuum to remove most of methanol and ethyl acetate (100 L) was added to the resulting residue and the mixture was stirred for 30 minutes. Then the organic layer was separated washed with brine (20 L) and dried over sodium sulfate, filtered and concentrated to dryness, and the residue was used directly in the next step. Sample from the reaction mixture and standard samples for compounds 6 and 7 were applied to a commercial silica gel TLC plate, with petroleum ether/ethyl acetate=4:1 as the mobile phase. 6 and 7 can be detected under UV254 or visualized using iodine treatment. The Rf for 6 was ˜0.55 while the Rf for compound 7 was ˜0.57; 1H-NMR (300 MHz, CDCl3) δ 7.21-7.48 (m, 15H), 5.20 (d, J=5.7 Hz, 1H), 4.77 (t, J=5.7 Hz, 1H), 4.39 (dd, J=5.4, 11.2 Hz, 1H), 3.90 (d, J=12.0 Hz, 1H), 3.79 (d, J=12.0 Hz, 1H), 2.81 (d, J=11.2 Hz, 1H), 1.43 (s, 3H), 1.32 (s, 3H); 13C-NMR DEPT-135 (75 MHz, CDCl3) δ 128.79, 127.89, 127.11, 82.91, 78.14, 76.48, 62.58 (OCH2—), 27.54, 27.11.

Provenance & Evidence