H-3@), 6.92 (dd, J 8.1 and 1.1 Hz, 1 H, H-5@), 7.33 (dd, J 8.4 and
2.1 Hz, 1 H, H-5A), 7.46 (dd, J 8.4 and 8.1 Hz, 1 H, H-4@), 7.50
(d, J 2.1 Hz, 1 H, H-3A), 7.66 (d, J 8.4 Hz, 1 H, H-6@), 8.28 (d, J
16.0 Hz, 1 H, H-b), 12.74 (s, 1 H, 6@-OH). 13C NMR: d \ 32.5
(C-2), 113.9 (C-3@), 114.5 (C-1@), 116.5 (C-5@), 119.4 (C-a), 127.8
(C-5A), 128.6 (C-3A), 130.3 (C-6A), 130.5 (C-1A), 135.5 (C-4@),
136.2 (C-2A), 137.4 (C-4A), 142.6 (C-b), 151.2 (C-2@), 164.0 (C-6@),
164.2 (C2O), 203.2 (C-1). EI-MS: m/z (rel. int.) 350 (M~`, 20),
199 (54), 171 (56), 164 (12), 152 (21), 137 (100), 136 (52), 135
(45), 123 (13), 109 (14), 108 (23), 101 (16), 100 (16), 99 (33), 77
(16), 75 (23), 74 (19), 51 (21).
2º,6º-Di(2-methoxycinnamoyloxy)acetophenone 3c. Yield
83%, mp 100È101 ¡C. 1H NMR: d \ 2.52 (s, 3 H, H-2), 3.92 (s,
6 H, 2 ] OCH ), 6.71 (d, J 16.1 Hz, 2 H, 2 ] H-a), 6.95 (d, J
3
7.8 Hz, 2 H, 2 ] H-3A), 7.00 (t, J 7.8 Hz, 2 H, 2 ] H-5A), 7.15
(d, J 8.2 Hz, 2 H, H-3@,5@), 7.40 (dt, J 7.8 and 1.6 Hz, 2 H,
2 ] H-4A), 7.48 (t, J 8.2 Hz, 1 H, H-4@), 7.56 (dd, J 7.8 and 1.6
Hz, 2 H, 2 ] H-6A), 8.17 (d, J 16.1 Hz, 2 H, 2 ] H-b). 13C
NMR: d \ 31.3 (C-2), 55.5 (2 ] OCH ), 111.2 (2 ] C-3A),
3
116.8 (2 ] C-a), 120.3 (C-3@,5@), 120.8 (2 ] C-5A), 122.9 (2 ] C-
1A), 128.5 (C-1@), 129.6 (2 ] C-6A), 130.7 (C-4@), 132.3 (2 ] C-4A),
143.3 (2 ] C-b), 147.9 (C-2@,6@), 158.7 (2 ] C-2A), 165.3
(2 ] C2O), 199.0 (C-1). EI-MS m/z (rel. int.) 472 (M~`, 2), 161
(100), 146 (6), 118 (12), 105 (15), 77 (8).
2º(3,4-Dibenzyloxycinnamoyloxy)-6º-hydroxyacetophenone
1i. Yield 77%, mp 122È124 ¡C. 1H NMR: d \ 2.61 (s, 3 H,
H-2), 5.21 and 5.22 (s, 4 H, 3A,4A-OCH C H ), 6.44 (d, J 15.9
2º,6º-Di(4-chlorocinnamoyloxy)acetophenone 3d. Yield 76%,
mp 165È166 ¡C. 1H NMR: d \ 2.50 (s, 3 H, H-2), 6.57 (d, J
16.1 Hz, 2 H, 2 ] H-a), 7.15 (d, J 8.2 Hz, 2 H, H-3@,5@) 7.40 (d,
J 8.3 Hz, 4 H, 2 ] H-3A,5A), 7.50 (t, J 8.2 Hz, 1 H, H-4@), 7.52
(d, J 8.3 Hz, 4 H, 2 ] H-2A,6A), 7.82 (d, J 16.1 Hz, 2 H,
2 ] H-b). 13C NMR: d \ 31.3 (C-2), 116.8 (2 ] C-a), 120.4 (C-
3@,5@), 128.2 (C-1@), 129.4 (2 ] C-3A,5A), 129.6 (2 ] C-2A,6A),
130.9 (C-4@), 132.3 (2 ] C-1A), 137.0 (2 ] C-4A), 146.3 (2 ] C-b),
147.8 (C-2@,6@), 164.5 (2 ] C2O), 198.6 (C-1). EI-MS: m/z (rel.
int.) 480 (M~`, 1), 462 (13), 165 (100), 137 (26), 102 (19), 101
2 6
5
Hz, 1 H, H-a), 6.64 (dd, J 8.0 and 1.1 Hz, 1 H, H-3@), 6.89 (dd,
J 8.5 and 1.1 Hz, 1 H, H-5@), 6.95 (d, J 8.3 Hz, 1 H, H-5A), 7.15
(dd, J 8.3 and 2.0 Hz, 1 H, H-6A), 7.18 (d, J 2.0 Hz, 1 H, H-2A),
7.30È7.48 (m, 11 H, H-4@ and H-2,3,4,5,6 of 3A,4A-OCH C H ),
2 6
5
7.80 (d, J 15.9 Hz, 1 H, H-b), 12.73 (s, 1 H, 6@-OH). 13C NMR:
d \ 32.4 (C-2), 70.8 and 71.4 (3A,4A-OCH C H ), 113.9 (C-3@),
2 6
5
114.0 (C-5A,6A), 114.6 (C-1@), 116.2 (C-5@), 123.7 (C-a), 127.0 (C-
2A), 127.1, 127.2, 127.3, 127.4, 128.0, 128.4 and 128.6 (C-1A and
C-2,3,4,5,6 of 3A,4A-OCH C H ), 135.4 (C-4@), 136.4 and 136.7
2 6
5
(19), 75 (7). Anal. calcd. for C
found: C 64.86, H, 3.76%.
H
Cl O : C 64.88, H 3.77;
(C-1 of 3A,4A-OCH C H ), 148.0 (C-b), 149.0 (C-3A), 151.5 (C-2@),
26 18
2 5
2 6
5
151.8 (C-4A), 163.9 (C-6@), 165.1 (C2O), 203.4 (C-1). EI-MS: m/z
(rel. int.) 494 (M~`, 1), 343 (66), 91 (100).
2º,6º-Di(4-methylcinnamoyloxy)acetophenone 3e. Yield 92%,
mp 154È156 ¡C. 1H NMR: d \ 2.40 (s, 6 H, 2 ] 4A-CH ), 2.51
3
(s, 3 H, H-2), 6.55 (d, J 15.9 Hz, 2 H, 2 ] H-a), 7.15 (d, J 8.2
Synthesis of 2º,6º-dicinnamoyloxyacetophenones 3a–i
Hz, 2 H, H-3@,5@), 7.23 (d, J 8.1 Hz, 4 H, 2 ] H-3A,5A), 7.48 (t, J
8.2 Hz, 1 H, H-4@), 7.48 (d, J 8.1 Hz, 4 H, 2 ] H-2A,6A), 7.85 (d,
To a suspension of 2@,6@-dihydroxyacetophenone (0.76 g, 5.0
mmol) in dichloromethane (30 ml), the appropriate cinnamic
acid (10 mmol), 4-pyrrolidinopyridine (148 mg, 1 mmol) and
N,N-dicyclohexylcarbodiimide (2.1 g, 10 mmol) were added.
The reaction mixture was stirred at room temperature for 30
min. The obtained dicyclohexylurea was Ðltered o† and
washed with dichloromethane (2 ] 20 ml). The Ðltrate was
evaporated to dryness and the residue puriÐed by silica gel
column chromatography (using an 8 : 2 mixture of
dichloromethaneÈlight petroleum). After evaporation of the
solvents, the obtained residue was recrystallized in ethanol to
provide 3a–i.
J 15.9 Hz, 2 H, 2 ] H-b). 13C NMR: d \ 21.6 (2 ] 4A-CH ),
3
31.3 (C-2), 115.1 (2 ] C-a), 120.4 (C-3@,5@), 128.4 (C-1@), 128.5
(2 ] C-2A,6A), 129.8 (2 ] C-3A,5A), 130.7 (C-4@), 131.2 (2 ] C-1A),
141.6 (2 ] C-4A), 147.8 (2 ] C-b and C-2@,6@), 164.9 (2 ] C2O),
198.8 (C-1). EI-MS: m/z (rel. int.) 440 (M~`, 4), 422 (17), 145
(100), 117 (34), 116 (10), 115 (32), 91 (19), 65 (6). Anal. calcd. for
C
H
O : C 76.35, H 5.49; found: C 76.50, H, 5.66%.
28 24
5
2º,6º-Di(4-methoxycinnamoyloxy)acetophenone 3f. Yield
82%, mp 157È158 ¡C. 1H NMR: d \ 2.51 (s, 3 H, H-2), 3.86 (s,
6 H, 2 ] OCH ), 6.46 (d, J 15.9 Hz, 2 H, 2 ] H-a), 6.93 (d, J
3
8.7 Hz, 4 H, 2 ] H-3A,5A), 7.14 (d, J 8.2 Hz, 2 H, H-3@,5@), 7.47
(t, J 8.2 Hz, 1 H, H-4@), 7.54 (d, J 8.7 Hz, 4 H, 2 ] H-2A,6A),
7.83 (d, J 15.9 Hz, 2 H, 2 ] H-b). 13C NMR: d \ 31.3 (C-2),
2º,6º-Dicinnamoyloxyacetophenone 3a. Yield 77%, mp 140È
142 ¡C. 1H NMR: d \ 2.51 (s, 3 H, H-2), 6.61 (d, J 16.0 Hz, 2
H, 2 ] H-a), 7.16 (d, J 8.2 Hz, 2 H, H-3@,5@), 7.40È7.46 (m, 6 H,
2 ] H-3A,4A,5A), 7.50 (t, J 8.2 Hz, 1 H, H-4@), 7.57È7.61 (m, 4 H,
2 ] H-2A,6A), 7.88 (d, J 16.0 Hz, 2 H, 2 ] H-b). 13C NMR:
d \ 31.3 (C-2), 116.2 (2 ] C-a), 120.4 (C-3@,5@), 128.3 (C-1@),
128.5 (2 ] C-2A,6A), 129.0 (2 ] C-3A,5A), 130.8 (C-4@), 131.0
(2 ] C-4A), 133.8 (2 ] C-1A), 147.8 (2 ] C-b and C-2@,6@), 164.7
(2 ] C2O), 198.7 (C-1). EI-MS: m/z (rel. int.) 412 (M~`, 16),
131 (100), 103 (72), 102 (20), 77 (50), 51 (17). Anal. calcd. for
55.4 (2 ] OCH ), 113.6 (2 ] C-a), 114.5 (2 ] C-3A,5A), 120.3
3
(C-3@,5@), 126.6 (2 ] C-1A), 128.4 (C-1@), 130.3 (2 ] C-2A,6A),
130.7 (C-4@), 147.5 (2 ] C-b), 147.9 (C-2@,6@), 162.0 (2 ] C-4A),
165.0 (2 ] C2O), 198.9 (C-1). EI-MS: m/z (rel int.) 472 (M~`,
4), 384 (40), 302 (12), 259 (16), 203 (21), 176 (22), 161 (100), 134
(23), 133 (23), 121 (28), 98 (13), 77 (9), 55 (10).
2º,6º-Di(4-benzyloxycinnamoyloxy)acetophenone 3g. Yield
80%, mp 172È173 ¡C.1H NMR d \ 2.50 (s, 3 H, H-2), 5.12 (s, 4
H, 2 ] OCH C H ), 6.46 (d, J 15.9 Hz, 2 H, 2 ] H-a), 7.01 (d,
C
H
O : C 75.72, H 4.89; found: C 75.52, H 4.79%.
26 20
5
2 6
5
J 8.8 Hz, 4 H, 2 ] H-3A,5A), 7.14 (d, J 8.2 Hz, 2 H, H-3@,5@),
7.34È7.51 (m, 11 H, H-4@ and 10 H of 2 ] OCH C H ), 7.53
2º,6º-Di(2-chlorocinnamoyloxy)acetophenone 3b. Yield 81%,
2 6
5
mp 102È104 ¡C.1H NMR: d \ 2.54 (s, 3 H, H-2), 6.61 (d, J
16.1 Hz, 2 H, 2 ] H-a), 7.19 (dd, J \ 8.2 Hz, 2 H, H-3@,5@), 7.32
(dt, J 7.4 and 1.6 Hz, 2 H, 2 ] H-4A), 7.37 (dt, J 7.4 and 2.0
Hz, 2 H, 2 ] H-5A), 7.46 (dd, J 7.4 and 1.6 Hz, 2 H, 2 ] H-6A),
7.51 (t, J 8.2 Hz, 1 H, H-4@), 7.70 (dd, J \ 7.4 and 2.0 Hz, 2 H,
2 ] H-3A), 8.30 (d, J 16.1 Hz, 2 H, 2 ] H-b). 13C NMR:
d \ 31.4 (C-2), 118.9 (2 ] C-a), 120.5 (C-3@,5@), 127.2 (2 ] C-5A),
127.9 (2 ] C-3A), 128.6 (C-1@), 130.3 (2 ] C-6A), 130.8 (C-4@),
131.8 (2 ] C-4A), 132.1 (2 ] C-1A), 135.4 (2 ] C-2A), 143.4
(2 ] C-b), 147.7 (C-2@,6@), 164.2 (2 ] C2O), 198.6 (C-1). EI-MS:
m/z (rel. int.) 480 (M~`, 2), 445 (8), 316 (2), 301 (2), 273 (2), 165
(100), 137 (32), 102 (18), 101 (27), 75 (8). Anal. calcd. for
(d, J 8.8 Hz, 4 H, 2 ] H-2A,6A), 7.82 (d, J 15.9 Hz, 2 H,
2 ] H-b). 13C NMR: d \ 31.3 (C-2), 70.1 (2 ] OCH C H ),
2 6
5
113.7 (2 ] C-a), 115.3 (2 ] C-3A,5A), 120.3 (C-3@,5@), 126.9
(2 ] C-1A), 127.5 (2 ] C-2,6 of OCH C H ), 128.2 (2 ] C-4 of
2 6
5
OCH C H ), 128.4 (C-1@), 128.7 (2 ] C-3,5 of OCH C H ),
2 6
5
2 6 5
130.3 (2 ] C-2A,6A), 130.6 (C-4@), 136.3 (2 ] C-1 of
OCH C H ), 147.4 (2 ] C-b), 147.9 (C-2@,6@), 161.1 (2 ] C-4A),
165.0 (2 ] C2O), 198.8 (C-1). EI-MS: m/z (rel. int.) 624 (M~`,
1), 335 (2), 282 (2), 237 (61), 146 (6), 137 (5), 118 (6), 91 (100), 83
(10), 65 (10).
2 6
5
2º,6º-Di(2,4-dichlorocinnamoyloxy)acetophenone 3h. Yield
90%, mp 138È140 ¡C. 1H NMR: d \ 2.53 (s, 3 H, H-2), 6.59
C
H
Cl O : C 64.88, H 3.77; found: C 64.86, H, 3.76%.
26 18
2 5
90
New J. Chem., 2000, 24, 85È92