ORDER
REPRINTS
1936
SEPULVEDA-BOZA ET AL.
2,4-Dihydroxy-3-methylphenyl-30-ethoxycarbonylbenzylketone (3b) –
2,6-Dihydroxytoluene and ethyl 3-(cyanomethyl)benzoate gave a mixture
of ketone (3b) and its carboxylic acid. This mixture was washed with a
5% NaHCO3 solution and the insoluble residue filtered to give product
(3b) with 61% yield, recrystallized from dichloromethane, mp 157ꢀC. H
1
NMR (DMSO-d6) d 1.30 (3 H, t, J ¼ 6.5 Hz, CH3CH2O), 1.96 (3 H, s, 3-
Me), 4.29 (2 H, q, J ¼ 6.5 Hz, CH3CH2O), 4.42 (2 H, s, benzyl CH2), 6.50 (1
H, d, J ¼ 9.0 Hz, 5-H), 7.45 (1 H, t, J ¼ 8.0 Hz, 50-H), 7.55 (1 H, m, 60-H),
7.80–7.90 (3 H, m, 6-H, 40-H and 20-H), 10.62 (1H, s, 4-OH), 12.85 (1 H, s, 2-
OH). UV (MeOH) ꢀmax 233 and 297 nm.
2,4-Dihydroxy-3-methylphenyl-30-trifluoromethylbenzylketone (3c) –
2,6-Dihydroxytoluene and 3-trifluoromethylphenylacetonitrile gave product
(3c) in 79% yield, crystallized from dichloromethane, mp 167ꢀC. H N MR
1
(DMSO-d6) d 2.96 (3 H, s, 3-Me), 4.47 (2 H, s, benzyl CH2), 6.41 (1 H, d,
J ¼ 9.0 Hz, 5-H), 7.54 (1 H, t, J ¼ 8.0 Hz, 50-H), 7.57 (1 H, d, J ¼ 7 Hz, 40-H),
7.61 (1 H, d, J ¼ 7 Hz, 60-H), 7.67 (1H, s, 20-H), 7.85 (1 H, d, J ¼ 9 Hz, 6-H),
10.60 (1H, s, 4-OH), 12.80 (1 H, s, 2-OH). UV (MeOH) ꢀmax 218 and 287 nm.
2,4-Dihydroxy-3-methylphenyl-40-methoxybenzylketone (3d) – 2,6-
Dihydroxytoluene and 4-methoxyphenylacetonitrile gave (3d) with 58%
yield, mp 172–173ꢀC. H NMR (DMSO-d6) d 1.96 (3 H, s, 3-CH3), 3.71
1
(3 H, s, OCH3), 4.20 (2 H, s, benzyl CH2), 6.48 (1 H, d, J ¼ 8.8 Hz, 5-H), 6.89
(2 H, d, J ¼ 8.6 Hz, 30-H and 50-H), 7.21 (2H, d, J ¼ 8.6 Hz, 20-H, and 60-H),
7.84 (1 H, d, J ¼ 8.8 Hz, 6-H), 10.60 (1H, s, 4-OH), 13.01 (1 H, s, 2-OH). 13
C
NMR (DMSO-d6) d 7.38, 42.87, 54.94, 107.17, 110.31, 111.48, 113.81,
127.05, 130.10, 130.30, 157.99, 162.48, 162.70, 202.79.
2,4-Dihydroxy-30-trifluoromethylbenzylketone (3e) – 1,3-Dihydroxy-
benzene and 3-trifluoromethylphenylacetonitrile gave (3e) with 60% yield,
mp 165ꢀC. H NMR (DMSO-d6) d 4.44 (2 H, s, benzyl CH2), 6.33 (1 H, d,
1
J ¼ 2.0 Hz, 3-H), 6.44 (1 H, dd, J ¼ 9.0 Hz, J0 ¼ 2.0 Hz, 5-H), 7.55–7.71 (4H,
m, 20-H, 40-H, 50-H and 60-H), 7.95 (1 H, d, J ¼ 9.0 Hz, 6-H), 10.74 (1H, s,
4-OH), 12.40 (1 H, s, 2-OH). UV (MeOH) ꢀmax 232, 277 and 315 nm.
2,4,5-Trihydroxy-30-trifluoromethylbenzylketone(3f) – 1,2,4-Trihydroxy-
benzene and 3-trifluoromethylphenylacetonitrile gave compound (3f) with
45% yield, mp 170ꢀC. H NMR (DMSO-d6) d 4.42 (2 H, s, benzyl CH2),
1
6.34 (1 H, s, 3-H), 7.35 (1 H, s, 6-H), 7.52–7.61 (3H, m, 40-H, 50-H and 60-H),
7.65 (1 H, s, 20-H), 8.88 (1 H, s, 5-OH), 10.50 (1H, s, 4-OH), 11.96 (1 H, s,
2-OH).
2,3,4-Trihydroxyphenyl-30,40-methylenedioxybenzylketone (3g) – 1,2,3-
Trihydroxybenzene and 3,4-methylenedioxyphenylacetonitrile gave com-
pound (3g) in 49% yield, mp 125–126ꢀC (ethanol/water). 1H N MR
(DMSO-d6) d 4.20 (2 H, s, benzyl CH2), 6.00 (2 H, s, OCH2O), 6.46 (1 H,
d, J ¼ 8.2 Hz, 5-H), 6.78–6.88 (3 H, m, 20-H, 50-H and 60-H), 7.52 (1 H, d,