March 2009
Synthesis of Pyrone Carbaldehydes, Pyrone Sulfonium Ylides, and Related Epoxides
271
130.39, 132.07, 132.38, 132.91, 139.70, 161.74, 162.24,
178.99 ppm; ms: m/z (%): 416 (Mþ, 3), 387 (8), 155 (21), 40
(68), 139 (100), 105 (55), 102 (38), 91 (79), 77 (52), 69 (8).
Anal. Calcd. for C29H20O3: C, 83.69; H, 4.80. Found: C,
83.30; H, 4.90.
2-{4-[3-(2-Chlorophenyl)oxiranyl]phenyl}-6-phenyl-4H-pyran-
4-one (6b2). White solid, 0.039 g (78%), mp 195–196ꢁC, FT-
IR (KBr): 3039, 2987, 1646 (pyrone C¼¼O), 1604, 1391, 1032,
764 cmꢂ1
;
1H NMR (CDCl3): d 3.83 (d, 1H, J ¼ 1.2 Hz,
epoxide-H), 4.23 (d, 1H, J ¼ 1.2 Hz, epoxide-H), 6.85 (s, 2H,
vinyl-H), 7.26-7.40 (m, 4H, Ar-H), 7.54-7.56 (m, 5H, Ar-H),
7.86-7.91 (m, 4H, Ar-H) ppm; 13C NMR (CDCl3): d 59.35,
60.52, 110.43, 110.48, 124.78, 124.97, 125.27, 125.39, 126.16,
128.19, 128.30, 130.38, 130.51, 132.20, 133.61, 139.43,
161.99, 162.49, 179.15 ppm; ms: m/z (%): 402 and 400 (Mþ,
5 and 14), 371 (7), 105 (73), 102 (100), 89 (97), 77 (39).
Anal. Calcd. for C25H17ClO3: C, 74.95; H, 4.24. Found: C,
74.70; H, 4.30.
2-{4-[3-(4-Methoxyphenyl)oxiranyl]phenyl-6-phenyl-4H-py-
ran-4-one (6b7). White solid, 0.06g (62%), mp 170–171ꢁC,
FT-IR (KBr): 3055, 2955, 1644 (pyrone C¼¼O), 1605, 1511,
1388, 1249, 829 cmꢂ1 1H NMR (CDCl3): d 3.82 (s, 3H,
;
OCH3), 3.83 (d, 1H, J ¼ 1.6 Hz, epoxide-H), 3.92 (d, 1H, J
¼ 1.6 Hz, epoxide-H), 6.81 (s, 2H, vinyl-H), 6.92 (d, 2H, J
¼ 8 Hz, Ar-H), 7.26-7.29 (m, 2H, Ar-H), 7.48-7.55 (m, 5H,
Ar-H), 7.84-7.87 (m, 4H, Ar-H) ppm; 13C NMR (CDCl3): d
54.30, 60.99, 62.02, 110.40, 110.42, 113.07, 124.89, 125.11,
125.15, 125.80, 127.47, 128.13, 130.22, 130.37, 130.42,
139.93, 158.93, 161.85, 162.29, 179.07 ppm; ms: m/z (%):
396 (Mþ, 31), 368 (52), 367 (100), 275 (21), 121 (68), 120
(58), 105 (66), 102 (38), 91 (79), 77 (52), 69 (8). Anal.
Calcd. for C26H20O4: C, 78.84; H, 5.04. Found: C, 78.45; H,
5.20.
2-{4-[3-(4-Nitrophenyl)oxiranyl]phenyl}-6-phenyl-4H-pyran-
4-one (6b3). White solid, 0.09 g (89%), mp 228–230ꢁC, FT-IR
(KBr): 3060, 2985, 1645 (pyrone C¼¼O), 1597, 1514 (N¼¼O),
1442, 1393, 1339 (N¼¼O), 846 cmꢂ1
;
1H NMR (CDCl3): d
3.94 (d, 1H, J ¼ 1.2 Hz, epoxide-H), 4.00 (d, 1H, J ¼ 1.2 Hz,
epoxide-H), 6.82 (s, 2H, vinyl-H), 7.50-7.55 (m, 7H, Ar-H),
7.85-7.91 (m, 4H, Ar-H), 8.26 (d, 2H, J ¼ 8 Hz, Ar-H) ppm;
13C NMR (CDCl3): 60.87, 61.62, 110.49, 110.63, 122.96,
124.95, 125.31, 128.20, 130.34, 130.55, 130.86, 138.65,
142.75, 147.02, 161.69, 162.49, 179.03 ppm. Anal. Calcd. for
C25H17NO5: C, 73.05; H, 4.16; N, 3.40. Found: C, 72.80; H,
4.00; N, 3.40.
2-Phenyl-6-[4-(3-styryloxiranyl)phenyl]-4H-pyran-4-one
(6b8). Yellow solid, 0.069g (71%), mp 97–99ꢁC, FT-IR
(KBr): 3057, 2858, 1650 (pyrone C¼¼O), 1600, 1497, 1447,
1
1395, 884 cmꢂ1; H NMR (CDCl3): d 3.54 (dd, 1H, J ¼ 1.6,
8 Hz, epoxide-H), 3.96 (d, 1H, J ¼ 1.6 Hz, epoxide-H), 6.08
(dd, 1H, J ¼ 8, 16 Hz, vinyl-H), 6.82 (s, 2H, C3- and C5-H),
6.85 (d, 1H, J ¼ 16 Hz, vinyl-H), 7.28-7.56 (m, 10H, Ar-H),
7.85-7.88 (m, 4H, Ar-H) ppm; 13C NMR (CDCl3): d 59.12,
62.44, 110.43, 110.46, 124.52, 124.93, 125.14, 125.20, 125.52,
127.32, 127.70, 128.16, 130.28, 130.40, 130.46, 134.00,
134.79, 139.82, 161.89, 162.37, 179.15 ppm; ms: m/z (%):
392 (Mþ, 4), 364 (6), 363 (100), 276 (12), 275 (33), 248 (23),
147 (30), 133 (34), 130 (33), 116 (53), 115 (100), 105 (57),
102 (39), 77 (30), 69 (21). Anal. Calcd. for C27H20O3: C,
82.67; H, 5.09. Found: C, 82.43; H, 4.14.
2-{4-[3-(2-Nitrophenyl)oxiranyl]phenyl}-6-phenyl-4H-pyran-
4-one (6b4). White solid, 0.094 g (93%), mp 240–241ꢁC, FT-
IR (KBr): 3068, 2855, 1643 (pyrone C¼¼O), 1591, 1520
(N¼¼O), 1399, 1340 (N¼¼O), 852 cmꢂ1
;
1H NMR (CDCl3): d
3.87 (d, 1H, J ¼ 2 Hz, epoxide-H), 4.49 (d, 1H, J ¼ 2 Hz,
epoxide-H), 6.81-6.82 (m, 2H, vinyl-H), 7.51-7.57 (m, 6H, Ar-
H), 7.73-7.74 (m, 2H, Ar-H), 7.84-7.90 (m, 4H, Ar-H), 8.19
(d, 1H, J ¼ 8 Hz, Ar-H) ppm; 13C NMR (CDCl3): d 59.40,
60.37, 110.44, 110.55, 123.77, 124.92, 125.25, 125.53, 126.04,
127.92, 128.14, 130.38, 130.43, 130.66, 132.42, 133.44,
138.87, 146.47, 161.86, 162.35, 179.10 ppm. Anal. Calcd. for
C25H17NO5: C, 73.05; H, 4.13; N, 3.40. Found: C, 72.65; H,
4.00; N 3.40.
2-Phenyl-6-[4-(3-p-tolyloxiranyl)phenyl]-4H-pyran-4-one
(6b9). White solid, 0.075g (80%), mp 203–205ꢁC, FT-IR
(KBr): 3058, 2992, 1641 (pyrone C¼¼O), 1614, 1391, 1021,
2-{4-[3-(4-Fluorophenyl)oxiranyl]-phenyl}-6-phenyl-4H-
pyran-4-one(6b5). White solid, 0.083g (88%), mp 186–
187ꢁC, FT-IR (KBr): 3058, 2984, 1645 (pyrone C¼¼O), 1601,
813 cmꢂ1 1H NMR (CDCl3): d 2.37 (s, 3H, CH3), 3.85 (d,
;
1H, J ¼ 1.6 Hz, epoxide-H), 3.93 (d, 1H, J ¼ 1.6 Hz, epox-
ide-H), 6.82 (s, 2H, vinyl-H), 7.19-7.26 (m, 4H, Ar-H), 7.49-
7.55 (m, 5H, Ar-H), 7.85-7.88 (m, 4H, Ar-H) ppm; 13C NMR
(CDCl3): d 20.22, 61.11, 62.16, 110.47, 110.48, 124.46,
124.93, 125.16, 125.20, 128.16, 128.33, 130.31, 130.43,
130.45, 132.52, 137.50, 139.94, 161.89, 162.35, 179.1 ppm;
ms: m/z (%): 380 (Mþ, 46), 351 (59), 275 (33), 133 (25), 114
(53), 105 (100), 102 (88), 89 (27), 77 (55). Anal. Calcd. for
C26H20O3: C, 82.14; H, 5.26. Found: C, 82.00; H, 5.58.
1
1507, 1447, 1392, 1230, 831 cmꢂ1; H NMR (CDCl3): d 3.87
(d, 1H, J ¼ 1.6 Hz, epoxide-H), 3.91 (d, 1H, J ¼ 1.6 Hz,
epoxide-H), 6.83 (s, 2H, vinyl-H), 7.07-7.11 (m, 2H, Ar-H),
7.32-7.35 (m, 2H, Ar-H), 7.49-7.55 (m, 5H, Ph-H), 7.85-7.89
(m, 4H, Ar-H) ppm; 13C NMR (CDCl3): d 61.18, 61.53,
110.54, 114.59, 114.80, 124.96, 125.23, 126.19, 126.27,
128.19, 130.43, 130.50, 131.28, 131.31, 139.52, 160.69,
161.84, 162.40, 163.15, 179.13 ppm; ms: m/z (%): 384 (Mþ,
16), 355 (17), 147 (13), 108 (85), 105 (67), 102 (100), 77
(36), 69 (18). Anal. Calcd. for C25H17FO3: C, 78.16; H, 4.42.
Found: C, 77.77; H, 4.40.
2-Phenyl-6-[4-(3-phenyloxiranyl)phenyl]-4H-pyran-4-one
(6b10). White solid, 0.075g (83%), mp 197–199ꢁC, FT-IR
(KBr): 3059, 2986, 1645 (pyrone C¼¼O), 1603, 1393,
1
879cmꢂ1; H NMR (CDCl3): d 3.88 (d, 1H, J ¼ 1.6 Hz, epox-
2-[4-(3-Naphthalen-2-yl-oxiranyl)-phenyl]-6-phenyl-4H-4-
one (6b6). White solid, 0.086g (84%), mp 187–189ꢁC, FT-IR
(KBr): 3051, 2976, 1642 (pyrone C¼¼O), 1600, 1503, 1390,
ide-H), 3.93 (d, 1H, J ¼ 1.6 Hz, epoxide-H), 6.81 (s, 2H,
vinyl-H), 7.35-7.39 (m, 5H, Ar-H), 7.49-7.54 (m, 5H, Ar-H),
7.84-7.87 (m, 4H, Ar-H) ppm; 13C NMR (CDCl3): d 61.12,
62.05, 110.65, 110.79, 124.45, 124.87, 125.11, 125.18, 127.53,
127.59, 128.11, 130.31, 130.35, 130.41, 135.47, 139.73,
161.80, 162.29, 179.14 ppm; ms: m/z (%): 366 (Mþ, 75), 337
(5), 195 (16), 191 (32), 133 (22), 130 (31) 105 (100), 102
(100), 89 (81), 77 (56), 69 (15). Anal. Calcd. for C25H18O3: C,
82.01; H, 4.91. Found: C, 81.66; H, 5.00.
1
824 cmꢂ1; H NMR (CDCl3): d 4.05 (d, 1H, J ¼ 1.6, epoxide-
H), 4.06 (d, 1H, J ¼ 1.6, epoxide-H), 6.83 (s, 2H, vinyl-H),
7.42-7.57 (m, 8H, Ar-H), 7.48-7.57 (m, 7H, Ar-H), 7.84-7.90
(m, 8H, Ar-H) ppm; 13C NMR (CDCl3): d 61.21, 62.30,
110.41, 110.42, 121.56, 124.15, 124.86, 125.12, 125.20,
125.26, 125.48, 126.75, 126.77, 127.51, 128.10, 130.35,
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet