PAPER
Direct Acylation of Phenol and Naphthol Derivatives
2051
2-Hydroxy-3¢,4-dimethylbenzophenone (3c)
1-(2-Hydroxy-4-methylphenyl)ethanone (3j)21
IR (neat): 3280–2900, 1635, 1610 cm–1.
1H NMR (CDCl3, 250 MHz): d = 2.28 (s, 3 H, CH3), 2.58 (s, 3 H,
CH3), 6.45 (d, J = 8.4 Hz, 1 H, Ph), 6.68 (s, 1 H, Ph), 7.50 (d, J =
8.1 Hz, 1 H, Ph), 12.27 (s, 1 H, OH).
1H NMR (CDCl3, 250 MHz): d = 2.32 (s, 3 H, CH3), 2.45 (s, 3 H,
CH3), 6.69–7.51 (m, 7 H, Ph), 12.17 (s, OH).
13C NMR (CDCl3, 62.9 MHz): d = 21.77, 22.38, 118.81, 119.05,
122.71, 126.65, 127.04, 128.48, 128.83, 129.85, 131.04, 132.85,
133.95, 134.96, 163.80.
13C NMR (CDCl3, 62.9 MHz): d = 22.32, 26.85, 117.94, 118.77,
120.60, 130.99, 148.47, 162.86, 204.29.
1-(2-Hydroxy-4-methylphenyl)hexan-1-one (3k)
IR (neat): 3550–3250, 1641, 1605 cm–1.
3¢-Bromo-2-hydroxy-4-methylbenzophenone (3d)18e
1H NMR (CDCl3, 250 MHz): d = 2.41 (s, 3 H, CH3), 6.67–7.71 (m,
7 H, Ph), 11.85 (s, 1 H, OH).
13C NMR (CDCl3, 62.9 MHz): d = 22.45, 119.01, 120.66, 127.93,
129.67, 132.19, 133.47, 133.59, 136.87, 140.27, 163.87, 199.71.
1H NMR (CDCl3, 250 MHz): d = 0.93 [t, J = 2.0 Hz, 3 H,
(CH2)4CH3], 1.38 (m, 4 H, CH3CH2CH2), 1.75 (m, 2 H,
CH2CH2CH2), 2.36 (s, 3 H, CH3), 2.92 (t, J = 5.7 Hz, 2 H, COCH2),
6.69 (d, J = 8.1 Hz, 1 H, Ph), 6.73 (s, 1 H, Ph), 7.63 (d, J = 8.1 Hz,
1 H, Ph), 12.49 (s, 1 H, OH).
2-Hydroxy-4¢-Chloro-4-methylbenzophenone (3e)
13C NMR (CDCl3, 62.9 MHz): d = 14.33, 22.28, 22.89, 24.74,
31.66, 38.54, 117.53, 118.88, 120.49, 129.47, 148.10, 163.03,
206.78.
White crystals; mp 81 °C.
IR (KBr): 3280–2900, 1635, 1605 cm–1.
1H NMR (CDCl3, 250 MHz): d = 2.37 (s, 3 H, CH3), 5.90–7.52 (m,
2-(11-Bromo-1-undecanoyl)-5-methylphenol (3l)18e
1H NMR (CDCl3, 250 MHz): d = 1.32–1.85 (m, 16 H, CH2), 2.35 (s,
3 H, CH3), 2.94 (t, J = 5.5 Hz, 2 H, COCH2), 3.40 (t, J = 5.8 Hz, 2
H, CH2Br), 6.71 (d, J = 8.1 Hz, 1 H, Ph), 7.25 (s, 1 H, Ph), 7.62 (d,
J = 8.1 Hz, 1 H, Ph), 12.43 (s, 1 H, OH).
7 H, Ph), 12.01 (s, 1 H, OH).
13C NMR (CDCl3, 62.9 MHz): d = 22.42, 117.06, 119.00, 120.52,
129.04, 130.92, 131.91, 133.51, 136.76, 138.53, 148.81, 163.81,
200.07.
13C NMR (CDCl3, 62.9 MHz): d = 22.30, 25.03, 28.53, 29.11,
29.74, 33.19, 34.43, 38.56, 117.54, 118.90, 120.49, 130.27, 148.12,
163.04, 206.75.
2-Hydroxy-4,4¢-dimethylbenzophenone (3f)
White crystals; mp 72 °C.
IR (KBr): 3300–2900, 1645, 1610 cm–1.
1H NMR (CDCl3, 250 MHz): d = 2.35 (s, 3 H, CH3), 2.42 (s, 3 H,
CH3), 6.65–7.40 (m, 7 H, Ph), 12.14 (s, OH).
13C NMR (CDCl3, 62.9 MHz): d = 21.65, 22.03, 118.48, 119.95,
122.42, 126.66, 129.23, 129.34, 130.25, 133.51, 142.54, 147.87,
163.40, 200.92.
1-(2-Hydroxy-4-methylphenyl)octadecan-1-one (3m)
IR (KBr): 3000–2800, 1645, 1471 cm–1.
1H NMR (CDCl3, 250 MHz): d = 0.87 [t, J = 6.8 Hz, 3 H,
(CH2)16CH3], 1.28–1.78 (m, 30 H, 15 × CH2), 2.37 (s, 3 H, CH3),
2.93 (t, J = 7.6 Hz, 2 H, COCH2), 6.71 (d, J = 8.2 Hz, 1 H, Ph), 7.28
(s, 1 H, Ph), 7.64 (d, J = 8.2 Hz, 1 H, Ph), 12.46 (s, 1 H, OH).
13C NMR (CDCl3, 62.9 MHz): d = 14.52, 22.31, 25.10, 29.75,
29.83, 29.87, 30.09, 32.32, 38.63, 118.91, 120.48, 130.29, 144.20,
160.60, 200.10.
2-Hydroxy-4¢-methoxy-4-methylbenzophenone (3g)
White crystals; mp 97 °C.
IR (KBr): 3300–2800, 1640, 1605 cm–1.
1H NMR (CDCl3, 250 MHz): d = 2.36 (s, 3 H, OCH3), 3.85 (s, 3 H,
CH3), 6.69 (d, J = 8.1 Hz, 1 H, Ph), 6.86 (s, 1 H, Ph), 6.92 (m, 2 H,
Ph), 7.49 (d, J = 8.1 Hz, 1 H, Ph), 7.52 (m, 2 H, Ph), 12.10 (s, 1 H,
OH).
13C NMR (CDCl3, 62.9 MHz): d = 22.34, 55.88, 114.00, 117.47,
120.20, 122.79, 126.92, 130.96, 132.05, 132.65, 133.61, 147.88,
163.12, 163.54, 200.03.
1-(4-Fluoro-2-hydroxyphenyl)ethanone (3n)
IR (neat): 3000–2900, 1620, 1600 cm–1.
1H NMR (CDCl3, 250 MHz): d = 2.60 (s, 3 H, CH3), 6.63 (d, J = 2.8
Hz, 1 H, Ph), 7.25 (s, 1 H, Ph), 7.72 (d, J = 2.9 Hz, 1 H, Ph), 12.59
(s, 1 H, OH).
13C NMR (CDCl3, 62.9 MHz): d = 27.01, 105.53, 107.71, 117.32,
133.30, 161.96, 166.70, 201.12.
Cyclohexyl(2-hydroxy-4-methylphenyl)methanone (3h)
1-(4-Ethyl-2-hydroxyphenyl)ethanone (3o)
IR (KBr): 3000–2800, 1640, 1580, 1242 cm–1.
IR (neat): 3500–3300, 1645, 1580 cm–1.
1H NMR (CDCl3, 250 MHz): d = 1.26–1.91 (m, 10 H, CH2), 2.31 (s,
3 H, CH3), 3.28 (m, 1 H, COCH), 6.73 (d, J = 8.2 Hz, 1 H, Ph), 6.81
(s, 1 H, Ph), 7.56 (d, J = 8.2 Hz, 1 H, Ph), 13.65 (s, 1 H, OH).
13C NMR (CDCl3, 62.9 MHz): d = 22.28, 25.76, 26.18, 26.25,
29.36, 29.98, 45.48, 116.40, 119.12, 120.42, 122.55, 130.07,
148.07, 163.67, 209.91.
1H NMR (CDCl3, 250 MHz): d = 1.21 (t, J = 5.2 Hz, 3 H, CH2CH3),
2.52–2.65 (m, 5 H, CH2CH3, COCH3), 6.73–6.83 (m, 2 H, Ph), 7.26
(d, J = 2.4 Hz, 1 H, Ph), 12.30 (s, 1 H, OH).
13C NMR (CDCl3, 62.9 MHz): d = 15.12, 26.87, 29.52, 113.30,
117.54, 119.54, 117.45, 131.09, 145.30, 160.01, 199.89.
1-(2,4-Dihydroxyphenyl)ethanone (3p)21
1H NMR (DMSO, 250 MHz): d = 2.49 (s, 3 H, COCH3), 5.71 (s, 1
H, OH), 6.30 (m, 2 H, Ph), 7.46 (d, J = 8.2 Hz, 1 H, Ph), 12.61 (s, 1
H, OH).
13C NMR (DMSO, 62.9 MHz): d = 26.62, 103.86, 108.10, 114.20,
133.46, 164.10, 200.00.
1-(2-Hydroxy-4-methylphenyl)-2-phenylethanone (3i)
IR (KBr): 3100–2900, 1641, 1583 cm–1.
1H NMR (CDCl3, 250 MHz): d = 2.32 (s, 3 H, CH3), 4.25 (s, 2 H,
COCH2), 6.46–7.74 (m, 8 H, Ph), 12.25 (s, 1 H, OH)
13C NMR (CDCl3, 62.9 MHz): d = 45.42, 119.04, 120.73, 127.53,
129.16, 129.81, 130.72, 134.58, 148.65, 163.45, 203.66.
Synthesis 2006, No. 12, 2047–2052 © Thieme Stuttgart · New York