ACETYLATION AND FORMYLATION OF ALCOHOLS
185
1H NMR (CDCl3), δ (ppm): 3.29 (4H, s), 7.26 (2H, m), 7.55 (4H, m), 7.85 (4H, m);
EIMS: (m/z) = 495 (M+); CHN Anal. Calcd for C14H14Br2N2O4S2: C 33.75, H 2.83, N
5.62, S 12.87. Found: C 33.80, H 2.86, N 5.68, S 12.81.
General Procedure for Acetylation of Alcohols and Phenols
Using Ac2O Catalyzed with BNBBS Under Solvent-Free Conditions
To a solution of alcohol or phenol (1 mmol) and acetic anhydride (1.5 mL), BNBBS
(0.1 mmol, 50 mg) was added, and the mixture was stirred at room temperature for the
specified time (Table I). After completion of the reaction, the reaction was quenched with
saturated NaHCO3 (10 mL). The product was extracted with CH2Cl2 (3 × 10 mL), and the
organic layer was dried over anhydrous Na2SO4. CH2Cl2 was evaporated under reduced
pressure to afford almost pure products. For further purification, the resulting mixture was
applied on a silica gel pad and was washed with a mixture of n-hexane:acetone (10:1).
General Procedure for Formylation of Alcohols Using Formic Acid
Catalyzed with BNBBS Under Solvent-Free Conditions
To a solution of alcohol (1 mmol) and formic acid (2 mL), BNBBS (0.1 mmol, 50 mg)
was added, and the mixture was stirred at room temperature for the specified time (Table II).
After completion of the reaction (TLC), the reaction was quenched with saturated NaHCO3
(
10 mL). The product was extracted with CH2Cl2 (3 × 10 mL), and the organic layer was
dried over anhydrous Na2SO4. The CH2Cl2 was evaporated under reduced pressure to give
almost pure products. In the some cases, the reaction mixture was passed through a short
column of silica gel using n-hexane:acetone (10:1) as an eluent.
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