Arch. Pharm. Pharm. Med. Chem. 2002, 335, 94–98
Synthesis and Antimicrobial Activity 97
( )-1-(4-Benzyloxyphenyl)-3,4-dihydroxybutan-1-one (4b)
( )-1-(4-Hydroxyphenyl)propanol (3a)
From 150 mg (0.6 mmol) of 2b and 2.0 g α-AD mix.Yield: 100
From 150 mg (0.6 mmol) of 2a.Yield: 70 mg (77%) as a colour-
less oil.
mg (58%) as a white solid mp: 90.0°C.
1H-NMR (d4-methanol) δ (ppm) = 3.10 (d, J = 5.9 Hz, 2H, CH2),
3.55 (d, J = 5.9 Hz, 2H, CH2O), 4.22 (tt, J = 5.9 Hz, J = 5.9 Hz,
1H, CH), 5.15 (s, 2H, CH2O), 7.06 (d, J = 8.8 Hz, 2H, aromat.
CH), 7.24–7.25 (m, 5H, aromat. CH), 7.97 (d, J = 8.8 Hz, 2H,
aromat. CH). 13C-NMR (d4-methanol) δ (ppm) = 41.63 (CH2),
65.59 (CH2O), 69.84 (CH2O), 68.97 (CH), 114.41 (2 aromat.
CH), 127.48 (2 aromat. CH), 127.77 (aromat. CH), 127.98
(quart. C), 128.26 (2 aromat. CH), 130.74 (2 aromat. CH),
138.01 (quart. C), 164.37 (quart. C), 199.59 (CO). MS (CI) m/z
= 287 (M+ + 1, 20), 269 (40), 227 (100).IR (KBr) ν (cm–1) = 3376,
2925, 1676, 1602, 1509, 1254, 1174, 1016, 821. Calcd.: C:
71.31 H: 6.34 Found: C: 70.97 H: 6.38 C17H18O4 (286.3).
1H-NMR (d6-acetone) δ (ppm) = 0.77 (t, J = 7.4 Hz, CH3), 1.61
(m, 1H, CH2), 1.71 (m, 1H, CH2), 4.40 (t, J = 6.8 Hz, 1H, CH),
6.70 (d, J = 8.5 Hz, 2H, aromat.CH), 7.05 (d, J = 8.5 Hz, 2H, ar-
omat.CH).13C-NMR (d6-acetone) δ (ppm) = 10.21 (CH3), 31.83
(CH2), 75.44 (CH), 115.13 (2 aromat. CH), 127.05 (2 aromat.
CH), 136.09 (quart. C), 156.12 (quart. C). All data were in full
accordance with the values given in [8]. C9H12O2 (152.19).
( )-1-(4-Hydroxyphenyl)pentanol (3b)
From 150 mg (0.5 mmol) of 2c.Yield: 65 mg (72%) as a colour-
less oil.
1H-NMR (CDCl3) δ (ppm) = 0.87 (t, J = 7.0 Hz, 3H, CH3), 1.33
(m, 4H, CH2), 1.70 (m, 1H, CH2), 1.82 (m, 1H, CH2), 4.60 (t, J =
6.7 Hz, 1H, CH), 6.77 (d, J = 8.6 Hz, 2H, aromat. CH), 7.18 (d,
J = 8.6 Hz, 2H, aromat.CH).13C-NMR (CDCl3) δ (ppm) = 13.99
(CH3), 22.54 (CH2), 28.01 (CH2), 38.43 (CH2), 74.55 (CH),
115.45 (2 aromat. CH), 127.41 (2 aromat. CH), 136.55 (quart.
C), 155.19 (quart. C). MS (EI) m/z = 180 (M+, 5), 123 (100).
Calcd.: C: 73.30 H: 8.95 Found: C: 72.95 H: 8.91. C11H16O2
(180.25).All data were in full accordance with those given in [6].
( )-1-(4-Benzyloxyphenyl)-4,5-dihydroxypentan-1-one (4c)
From 200 mg (0.8 mmol) of 2c and 2.0 g α-AD mix.Yield: 135
mg (57%) as a white solid, mp: 80.1°C.
1H-NMR (CDCl3) δ (ppm) = 1.20 (m, 2H, CH2), 1.81 (m, 2H,
CH2), 3.06 (dd, 1H, CH), 3.42 (dd, 1H, CH), 3.59 (dd, 1H, CH),
3.61 (m, 1H, CH), 5.06 (s, 2H, CH2), 6.93 (d, J = 8.8 Hz, 2H, ar-
omat. CH), 7.19–7.35 (m, 5H, aromat. CH), 7.89 (d, J = 8.8 Hz,
2H, aromat. CH). 13C-NMR (CDCl3) δ (ppm) = 27.17 (CH2),
34.44 (CH2), 66.81 (CH2O), 70.15 (CH2O), 71.73 (CH), 73.89
(CH), 74.38 (CH), 114.33 (2 aromat. CH), 127.01 (2 aromat.
CH), 127.47 (2 aromat.CH), 128.26 (2 aromat.CH), 128.70 (ar-
omat. CH), 131.99 (quart. C), 136.20 (quart. C), 162.99 (quart.
C), 199.59 (CO). MS (CI) m/z (%) = 301 (M+ + 1, 10), 283 (20),
91 (100). IR (KBr) ν (cm–1) = 3364, 2925, 1676, 1601, 1509,
1454, 1379, 1302, 1254, 1168, 1016, 916, 862.Calcd.:C:71.98
H: 7.71 Found: C: 71.88 H: 7.53. C18H20O4 (300.4)
( )-1-(4-Hydroxyphenyl)hexanol (3c)
From 760 mg (2.7 mmol) of 2d.Yield: 510 mg (96%) as a col-
ourless oil.
1H-NMR (CDCl3) δ (ppm) = 0.88 (t, J = 8.2 Hz, 3H, CH3), 1.15–
1.79 (m, 6 , CH2), 4.53 (dd, J = 7.5 Hz, J = 13.5 Hz, 1H, CH),
6.79 (d, J = 8.9 Hz, 2H, aromat.CH), 7.18 (d, J = 8.9 Hz, 2H, ar-
omat. CH). 13C-NMR (CDCl3) δ (ppm) = 14.32 (CH3), 23.18
(CH2), 39.66 (CH2), 74.26 (CH), 115.71 (2 aromat. CH), 128.11
(2 aromat. CH), 137.54 (quart. C), 156.83 (quart. C). MS (EI)
m/z = 176 (M+ – 18, 15), 137 (40), 107 (100).IR (KBr) ν (cm–1) =
3333, 3024, 2956, 2931, 1614, 1598, 1454, 1240, 1171, 1109,
1005, 949, 895. C12H18O2 (194.28).
( )-1-(4-Benzyloxyphenyl)-5,6-dihydroxyhexan-1-one (4d)
From 250 mg (1.3 mmol) of 2d and 2.0 g α-AD mix. Yield:
175 mg (42%) as a white solid: mp: 120.6°C.
1H-NMR (CDCl3) δ (ppm) = 1.18 (m, 2H, CH2), 1.44 (m, 2H,
CH2), 1.80 (m, 2H, CH2), 3.40 (dd, J = 11.2, Hz, J = 8.1 Hz, 1H,
CH), 3.59 (dd, J = 3.4 Hz, J = 11.2 Hz, 1H, CH), 3.64 (m, 1H,
CH), 5.07 (s, 2H, CH2), 6.94 (d, J = 10.0 Hz, 2H, aromat. CH),
7.23–7.38 (m, 5H, aromat. CH), 7.88 (d, J = 10.0 Hz, 2H, aro-
mat. CH). 13C-NMR (CDCl3) δ (ppm) = 19.81 (CH2), 32.71
(CH2), 37.76 (CH2), 66.71 (CH2O), 70.14 (CH2O), 71.65 (CH),
114.61 (aromat. CH), 127.46 (aromat. CH), 128.25 (aromat.
CH), 128.70 (aromat.CH), 130.35 (aromat.CH), 136.15 (quart.
C), 162.67 (quart. C), 199.41 (CO). MS (CI): m/z (%) = 315
(M+ + 1, 100), 297 (50), 249 (55). IR (NaCl film) ν (cm–1) =
3289, 2923, 1675, 1602, 1508, 1455, 1413, 1377, 1303, 1253,
1172, 1109, 1051, 1009, 916. Calcd.: C: 72.59 H: 7.05 Found:
C: 72.47 H: 7.52. C19H22O4 (314.4).
( )-4-Benzyloxyphenyldihydroxyalkanones 4a–e
1.0 mol of the alkene 2a–e was dissolved in 20 mL of a mixture
of tert-butanol and water (1:1) and 2.0 g α-AD mix were added.
The suspension was cooled to 0°C and stirred for 12 hours.
Then it was quenched with 20 mL 10% Na2SO3 solution and ex-
tracted with ethyl acetate (3 × 50 mL). The combined organic
layers were evaporated.The residue was purified by FCC (ethyl
acetate).
( )-1-(4-Benzyloxyphenyl)-2,3-dihydroxypropan-1-one (4a)
From 200 mg (0.8 mmol) of 2a and 2.0 g α-AD mix. Yield:
140 mg (65%) as a white solid, mp: 140.1°C.
( )-1-(4-Benzyloxyphenyl)-6,7-dihydroxyheptan-1-one (4e)
1H-NMR (CDCl3) δ (ppm) = 3.82 (dd, J = 5.1 Hz, J = 11.3 Hz,
1H, CH), 3.96 (dd, J = 3.8 Hz, J = 11.3 Hz, 1H, CH), 5.19 (m,
1H, CH), 5.26 (m, 2H, CH2O), 7.09 (d, J = 8.9 Hz, 2 H, aromat.
CH), 7.24–7.60 (m, 5H, aromat. CH), 7.99 (d, J = 8.9 Hz, 2H,
aromat. CH). 13C-NMR (CDCl3) δ (ppm) = 65.95 (CH2O), 71.16
(CH2O), 75.57 (CH), 115.88 (2 aromat. CH), 128.60 (2 aromat.
CH), 129.09 (2 aromat. CH), 129.56 (aromat. CH), 132.06
(2 aromat. CH), 133.20 (quart. C), 164.60 (quart. C), 210.31
(CO). MS (CI) m/z = 273 (100), 243 (70), 211 (75). IR (KBr)
ν (cm–1) = 3376, 2925, 1672, 1605, 1575, 1509, 1453, 1381,
1244, 1176, 1122, 1056, 1019, 974. Calcd.: C: 70.58 H: 5.92
Found: C: 70.70 H: 6.17. C16H16O4 (274.3).
From 500 mg (1.7 mmol) of 2e and 2.0 g α AD mix. Yield:
510 mg (90%) as a white solid mp: 145°C.
1H-NMR (CDCl3) δ (ppm) = 1.24–1.75 (m, 6H, CH2), 2.88 (t, J =
7.1 Hz, 2H, CH2), 3.36 (m, 2H, CH), 3.54 (m, 1H, CH), 5.08 (s,
2H, CH2), 6.96 (d, J = 8.8 Hz, 2H, aromat. CH), 7.36 (m, 5H,
aromat. CH), 7.89 (d, J = 8.8 Hz), 2 H, aromat. CH). 13C-NMR
(CDCl3) δ (ppm) = 29.12 (CH2), 30.23 (CH2), 37.80 (CH2), 43.78
(CH2), 69.75 (CH2O), 73.02 (CH2O), 75.08 (CH), 117.74 (2
aromat. CH), 130.12 (2 aromat. CH), 130.46 (2 aromat. CH),
130.96 (aromat.CH), 131.57 (2 aromat.CH), 139.94 (quart.C),
140.20 (quart.C), 167.56 (quart.C), 204 (CO).MS (CI):m/z (%)