May-Jun 2003 Reactions of o-Quinones with α-Methyl- (or Methylene) Substituted Phosphorus Ylides
403
5,7-Di(tert-butyl)-2-phenyl-1-benzofuran (6b).
128.8, 130.6, 131.1, 131.6, 138.6, 143.1, 146.4; ms (EI): m/z 297
(40, M + H), 296 (87, M ), 295 (100), 279 (41), 265 (49), 252
(36), 219 (29), 218 (53), 189 (73), 165 (35), 91 (55), 77(35).
+
+
This compound was obtained (Table 1) as white crystalls, mp
-1 1
90-92 °C (hexane); ir: 3050, 1600, 1165 cm ; H nmr: δ 1.39 (s,
Anal. Calcd. for C H O: C 89.1, H 5.4. Found: C 88.7, H 5.3.
22 16
9H), 1.58 (s, 9H), 6.97 (s, 1H), 7.25 (s, 1H), 7.28-7.35 (m, 1H),
13
7.40-7.46 (m, 3H), 7.86 (d, 2H, J=6.4); C nmr: δ 30.0, 31.9,
3-Phenylphenanthro[9,10-b]furan (19a).
34.5, 34.8, 101.4, 114.9, 119.1, 124.7, 128.1, 128.7, 129.3, 130.9,
133.7, 145.7, 151.2, 155.1; ms (EI): m/z 306 (85, M ), 291 (100),
This compound was obtained (Table 1) as yellow crystalls, mp
+
-1
1
47-49 °C (n-hexane); ir: 3050, 1600, 1510 cm ; H nmr: δ 7.38-
7.73 (m, 9H), 7.74 (s, 1H), 8.00 (d, 1H, J=8.1), 8.40 (d, 1H,
275 (10), 244 (14), 105 (33), 77 (22), 57 (87); For C H O hrms
22 26
Calcd. 306.1978; Found: 306.1975.
13
J=7.8), 8.73 (d, 2H, J=8.3); C nmr: δ 117.9, 120.7, 122.0,
Anal. Calcd. for C H O: C 86.2, H 8.55. Found: C 86.1, H 8.8.
22 26
122.4, 123.3, 123.6, 124.0, 125.0, 125.1, 126.0, 126.5, 127.0,
127.8, 128.4, 128.6, 129.2, 129.9, 133.1, 141.4, 149.7; ms (EI):
6-(2-Phenylethenyl)-1,3-benzodioxol-5-ol (4c).
+
+
+
m/z 295 (54, M + H), 294 (42, M ), 293 (61, M - H), 265 (100),
263 (51), 131(34), 119 (42), 105 (45).
This compound was obtained (Table 1) as yellow crystalls, mp
109-111 °C (ether/hexane); ir (KBr): 3478, 1618, 1594, 1158
Anal. Calcd. for C H O: C 89.8, H 4.8. Found: C 89.8, H 4.8.
22 14
-1 1
cm ; H nmr: δ 5.03 (s, 1H, -OH), 5.91 (s, 2H), 6.40 (s, 1H), 6.90
(d, 1H, J=16.1), 7.00 (s, 1H), 7.20-7.43 (m, 4H), 7.49 (d, 2H,
J=7.6); C nmr: δ 98.4, 101.3, 105.3, 117.6, 122.6, 125.2, 126.3,
2-Methyl-2-phenylphenanthro[9,10-d][1,3]dioxole (20a).
13
This compound was obtained (Table 1) as yellow crystalls, mp
85-87 °C (ether/hexane) (lit.[18] mp 90 °C).
127.4, 128.1, 128.6, 143.8, 146.2, 148.2; ms (ESI): m/z 240
+
(M+H) ; For C H O hrms Calcd. 240.0781; Found: 240.0782.
15 12
3
6-(1-Phenylvinyl)-1,3-benzodioxol-5-ol (18b).
Phenanthro[9,10-b]furan (9).
This compound was obtained (Table 1) as yellow oil; ir: 3500,
3040, 1620,1495, 1220, 1170, 1120, 1080 cm ; H nmr: δ 5.13
This compound was obtained (Table 1) as white crystalls, mp
118-120 °C (ether/hexane) (lit.[22] mp 118-119 °C).
-1
1
(s, 1H), 5.35 (s, 1H), 5.79 (s, 1H, -OH, exchangeable with D O),
2
13
10-Phenanthro[9,10-b]furan-3-yl-9-phenanthrenol (12).
5.89 (s, 2H), 6.50 (s, 1H), 6.55 (s, 1H), 7.42-7.26 (m, 5H);
C
nmr: δ 97.9, 101.1, 109.1, 116.4, 118.9, 127.1, 128.5, 128.6, 139.6,
141.2, 145.3, 148.1, 148.3; ms (EI): m/z 240 (57, M ), 239 (100),
225 (22), 181 (7), 152 (17), 139 (9), 128 (12), 115 (9).
This compound was obtained (Table 1) as light yellow crystalls,
+
mp 273-276 °C (dichloromethane/hexane); ir: 3478, 3050, 1615,
-1 1
1595 cm ; H nmr: δ 5.87 (s, 1H, -OH, exchangeable with D O),
2
Anal. Calcd. for C H O : C 75.0, H 5.0. Found: C 74.6,
15 12
3
7.14 (t, 1H, J=7.6), 7.36 (t, 1H, J=7.6), 7.42-7.61 (m, 4H), 7.67-
7.87 (m, 4H), 7.97 (s, 1H), 8.46 (d, 1H, J=9.5), 8.50 (t, 1H, J=9.7),
H 5.1.
13
8.65-8.86 (m, 4H); C nmr: δ 105.4, 107.0, 111.1, 111.2, 113.2,
7-Phenylfuro[2,3-f][1,3]benzodioxole (19b) [16].
114.6, 120.7, 120.9, 122.7, 123.3, 123.5, 123.7, 124.1, 124.3,
124.4, 124.7, 125.4, 125.6, 125.7, 126.6, 126.7, 126.9, 127.1,
127.3, 127.6, 127.8, 141.3, 143.4, 143.7, 148.2; ms (EI): m/z 411
(17, M +H), 410 (100, M ), 409 (32), 392 (9), 391 (9), 381 (92),
351 (60), 349 (56), 218 (7), 196 (48), 182 (38), 175 (66).
This compound was obtained (Table 1) as yellow crystallls, mp
109-110 °C (ether); ir (dichloromethane): 3040, 1585, 1275,
-1
1
1225, 1140 cm ; H nmr: δ 5.99 (s, 2H), 6.56 (s, 1H), 6.95 (s,
+
+
13
1H), 7.48-7.57 (m, 4H), 7.62 (d, 2H, J=6.4); C nmr: δ 98.9,
101.9, 106.4, 110.0, 119.8, 123.8, 128.2, 128.4, 128.6, 131.4,
Anal. Calcd. for C H O : C 87.8, H 4.4. Found: C 87.8, H
30 18
2
+
136.5, 145.3, 146.6; ms (EI): m/z 238 (50, M ), 210 (10), 181
4.3.
(14), 161 (11), 133 (13), 131 (12), 105 (100), 77 (82).
10-Hydroxy-10-vinyl-9(10H)-phenanthrenone (16).
2-Methyl-2-phenyl[1,3]dioxole[4,5-f][1,3]benzodioxole (20b).
This compound was obtained (Table 1) as light brown crys-
This compound was obtained (Table 1) as white crystalls, mp
105-107 °C (ether/hexane); ir: 3480, 3050, 1680, 1595 cm ; H
-1
1
-1
1
talls, mp 45-47 °C (ether/hexane); ir: 3050, 1595, 1080 cm ; H
nmr: δ 4.30 (s, 1H, -OH, exchangeable with D O), 5.05 (d, 1H,
2
nmr: δ 1.95 (s, 3H), 5.79 (s, 1H), 5.83 (s, 1H), 6.46 (s, 2H), 7.41-
J=10.4), 5.30 (d, 1H, J=16.9), 5.84 (dd, 1H, J=10.4 and 16.9),
7.40- 7.45 (m, 3H), 7.68-7.73 (m, 2H), 7.85-7.88 (m, 1H), 7.92-
13
7.31 (m, 3H), 7.61-7.54 (m, 2H); C nmr: δ 26.8, 93.0, 98.5,
100.9, 101.3, 117.3, 124.9, 128.1, 128.3, 128.6, 128.8, 141.0,
13
7.98 (m, 2H); C nmr: δ 80.4, 115.5, 123.3, 124.0, 126.4, 127.7,
+
141.3; ms (EI): m/z 256 (38, M ), 239 (10), 154 (100), 103 (50).
128.2, 128.4, 129.3, 129.6, 135.3, 137.7, 138.6, 138.8, 139.9,
Anal. Calcd. for C H O : C 70.3, H 4.7. Found: C 69.9, H 4.9.
+
15 12 4
200.9; ms (EI): m/z 236 (14, M ), 209 (12), 208 (13), 207 (18),
194 (98), 189 (11), 181 (100), 165 (32), 152 (62), 126 (8).
Cyclization of Alkenylphenols 4b, 18a and 18b to Corresponding
Anal. Calcd. for C H O : C 81.3, H 5.1.Found: C 81.3, H
Furans.
16 12
2
5.0.
Cyclization of 4b.
10-(1-Phenylvinyl)-9-phenanthrenol (18a).
A solution of 4b (52 mg, 0.168 mmole) and DDQ (75 mg, 0.33
mmole) in dry benzene (2 ml) was heated under reflux for 1 h.
The reaction mixture was concentrated and the residue was
extracted with chloroform (15 ml). The organic layer was washed
This compound was obtained (Table 1) as yellow crystalls, mp
-1
1
124-126 °C (ether/hexane); ir: 3460, 3060, 1585 cm ; H nmr: δ
5.62 (s, 1H, =CH ), 6.09 (s, 1H, -OH, exchangeable with D O),
2
2
with 5% NaHCO solution (10 ml), then with water (10 ml),
6.41 (s, 1H, =CH ), 7.24-7.35 (m, 2H), 7.36-7.51 (m, 4H), 7.54 (d,
3
2
dried (Na SO ) and concentrated. The residue was separated by
column chromatography (hexane/ethyl acetate 50:1) to give
1H, J=7.8), 7.64-7.82 (m, 2H), 8.42 (d, 1H, J=7.3), 8.64 (d, 1H,
J=8.0), 8.70 (d, 2H, J=7.8); C nmr: δ 99.1, 119.2, 122.5, 123.3,
2
4
13
124.0, 124.9, 125.7, 126.1, 126.4, 126.6, 126.9, 127.3, 128.6,
dihydrofuran 5 (22 mg, 42%) and furan 6b (13 mg, 25%).