Sodium Hydroxide → Adriamycin aglycone

Participants

Reaction Steps

Daunomycinone (IX) (10 mg, 0.025 mmole) was placed in CHCl3 (1 ml). Br2 (13.5 mg) in CHCl3 (0.25 ml) was added and the solution stirred at 23° for 16 hrs. The solvent was removed and the residue was dissolved in 80% aq acetone (5 ml). NaOH (1.1 mg. 0.028 mmole) was added and the blue solution was refluxed for 5 min when the red color returned. The solution was concentrated to approximately 2 ml, diluted with water (10 ml) and extracted with 50% CHCl3 /MeOH (3 × 10 ml). The extracts were combined, dried and evaporated. The residue was crystallized from CHCl3 -MeOH/pet. ether (30°-60°) to afford 9.0 mg (87%) of (XI): irnujol 2.85 (OH), 5.75 (C = O), 615, 628 μ (chelated quinone); pmr 100 MHz CDCl3 δ 2.0-2.5 (m, 2H, 8-H2), 2.8-3.2 (m, 2H, 10-H2), 3.43 (m, 1H, 9-OH), 4.09 (s, 3H, OMe), 4.70 (d, 2H, J = 16Hz, 14-H2), 5.34 (m, 1H, ∥1/2 = 8Hz, 7-H), 7.38 (dd, 1H, J = 8Hz and J = 1Hz, 3-H), 7.76 (t, 1H, J = 8Hz, 2-H), 8.00 (dd, 1H, J = 8Hz and J = 1Hz, 1-H), 13.24 (s, 1H, 6-OH), 13.99 (s, 1H, 11-OH).

Provenance & Evidence