Job/Unit: O20180
/KAP1
Date: 11-04-12 17:22:51
Pages: 10
trans-2,3-Dihydrofurans with Trifluoromethyl and Sulfonyl Substituents
[3-(4-Methoxyphenyl)-4-tosyl-5-trifluoromethyl-trans-2,3-dihydro-
furan-2-yl](phenyl)methanone (7Da): Light yellow solid. Yield
442 mg, 88%. M.p. 157.9–158.4 °C. H NMR (500 MHz, CDCl3):
δ = 2.35 (s, 3 H, CH3), 3.83 (s, 3 H, OCH3), 4.74 (d, J = 5.0 Hz, 1
H, furan-H), 5.77 (d, J = 5.0 Hz, 1 H, furan-H), 6.79 (d, J = 8.0 Hz,
H, CH3), 2.94 [s, 6 H, N(CH3)2], 4.76 (d, J = 5.0 Hz, 1 H, furan-
H), 5.11 (d, J = 5.0 Hz, 1 H, furan-H), 6.51 (d, J = 8.5 Hz, 2 H,
Ar-H), 6.84 (d, J = 8.5 Hz, 2 H, Ar-H), 7.03 (d, J = 7.0 Hz, 2 H,
Ar-H), 7.23 (d, J = 7.0 Hz, 2 H, Ar-H) ppm. 13C NMR (125 MHz,
CDCl3): δ = 21.6, 30.9, 40.3, 56.2, 75.6, 112.6, 115.2, 117.2 (q, 1JC,F
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2 H, Ar-H), 7.04–7.05 (m, 4 H, Ar-H), 7.21–7.23 (m, 2 H, Ar-H), = 273.5 Hz), 120.4, 124.8, 128.0, 128.5, 129.4, 137.1, 144.6, 147.7
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7.46–7.48 (m, 2 H, Ar-H), 7.62–7.65 (m, 1 H, Ar-H), 7.80 (d, J = (q, JC,F = 41.3 Hz), 151.1 ppm. 19F NMR (470 MHz, CDCl3): δ
7.5 Hz, 2 H, Ar-H) ppm. 13C NMR (125 MHz, CDCl3): δ = 21.5,
30.9, 53.1, 55.4, 89.90 114.6,117.4 (q, JC,F = 272.5 Hz), 120.7,
= –63.11 (s, CF ) ppm. IR (KBr): ν = 2922, 2814, 2245, 1649, 1597,
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1527, 1349, 1329, 1203, 1163, 1133, 1076, 1013, 810 cm–1. MS (EI):
m/ z ( %) = 4 37 (2 ) [ M + H]+ , 43 6 ( 9) [M ]+ , 183 (100).
C21H19F3N2O3S (436.45): calcd. C 57.79, H 4.39, N 6.42; found C
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127.8, 129.0, 129.2, 129.3, 129.3, 132.6, 133.9, 134.5, 137.8, 144.3,
149.8 (q, 2JC,F = 40.0 Hz), 159.9, 190.6 ppm. 19F NMR (470 MHz,
CDCl ): δ = –63.25 (s, CF ) ppm. IR (KBr): ν = 2975, 2941, 1696, 57.80, H 4.46, N 6.45.
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1649, 1596, 1331, 1251, 1210, 1181, 1163, 1145, 1106, 1074, 812,
694 cm–1. MS (EI): m/z (%) = 502 (1) [M]+, 105 (100). C26H21F3O5S
(502.50): calcd. C 62.14, H 4.21; found C 62.24, H 4.30.
Methyl 3-[4-(Dimethylamino)phenyl]-4-tosyl-5-trifluoromethyl-
trans-2,3-dihydrofuran-2-carboxylate (7Ec): Brown solid. Yield
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394 mg, 84%. M.p. 124.5–125.3 °C. H NMR (500 MHz, CDCl3):
3-(4-Methoxyphenyl)-4-tosyl-5-trifluoromethyl-trans-2,3-dihydro- δ = 2.32 (s, 3 H, CH3), 2.93 [s, 6 H, N(CH3)2], 3.82 (s, 3 H,
furan-2-carbonitrile (7Db): Light yellow solid. Yield 364 mg, 86%. CO2CH3), 4.63 (d, J = 5.0 Hz, 1 H, furan-H), 4.94 (d, J = 5.0 Hz,
M.p. 83.1–84.2 °C. H NMR (500 MHz, CDCl3): δ = 2.37 (s, 3 H, 1 H, furan-H), 6.51 (d, J = 9.0 Hz, 2 H, Ar-H), 6.89 (d, J = 9.0 Hz,
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CH3), 3.81 (s, 3 H, OCH3), 4.83 (d, J = 5.0 Hz, 1 H, furan-H), 5.14
(d, J = 5.0 Hz, 1 H, furan-H), 6.78 (d, J = 8.5 Hz, 2 H, Ar-H),
6.97 (d, J = 8.5 Hz, 2 H, Ar-H), 7.08 (d, J = 8.0 Hz, 2 H, Ar-H),
2 H, Ar-H), 7.00 (d, J = 8.0 Hz, 2 H, Ar-H), 7.20 (d, J = 8.0 Hz,
2 H, Ar-H) ppm. 13C NMR (125 MHz, CDCl3): δ = 21.5, 30.9,
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40.5, 53.1, 54.4, 86.5, 112.7, 117.4 (q, JC,F = 272.5 Hz), 120.7,
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7.22 (d, J = 8.0 Hz, 2 H, Ar-H) ppm. 13C NMR (125 MHz,
124.8, 127.9, 128.5, 129.2, 137.8, 144.0, 149.1 (q, JC,F = 41.3 Hz),
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CDCl3): δ = 21.6, 31.0, 53.3, 55.5, 90.0, 114.8, 117.6 (q, JC,F
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150.6, 168.4 ppm. 19F NMR (470 MHz, CDCl3): δ = –63.41 (s,
272.5 Hz), 120.8, 127.9, 129.2, 129.5, 134.6, 137.9, 144.5, 149.9 (q,
CF ) ppm. IR (KBr): ν = 2965, 2895, 1761, 1641, 1524, 1337, 1323,
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2JC,F = 41.25 Hz), 160.0 ppm. 19F NMR (470 MHz, CDCl3): δ = 1206, 1180, 1160, 1141, 1109, 1048, 812 cm–1. MS (EI): m/z (%) =
–63.15 (s, CF ) ppm. IR (KBr): ν = 2961, 2925, 2249, 1652, 1598,
470 (28) [M + H]+, 469 (100) [M]+. C22H22F3NO5S (469.47): calcd.
C 56.28, H 4.72, N 2.98; found C 56.38, H 4.79, N 3.02.
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1515, 1334, 1259, 1198, 1162, 1140, 1079, 1033, 809 cm–1. MS (EI):
m/z (%) = 423 (12) [M]+, 91 (100). C20H16F3NO4S (423.40): calcd.
C 56.73, H 3.81, N 3.31; found C 56.80, H 3.88, N 3.36.
[3-(3-Chlorophenyl)-4-tosyl-5-trifluoromethyl-trans-2,3-dihydro-
furan-2-yl](phenyl)methanone (7Fa): Light yellow solid. Yield
436 mg, 86%. M.p. 99.5–100.3 °C. 1H NMR (500 MHz, CDCl3): δ
= 2.39 (s, 3 H, CH3), 4.79 (d, J = 5.0 Hz, 1 H, furan-H), 5.74 (d,
Methyl 3-(4-Methoxyphenyl)-4-tosyl-5-trifluoromethyl-trans-2,3-di-
hydrofuran-2-carboxylate (7Dc): Light yellow oil. Yield 379 mg,
83%. 1H NMR (500 MHz, CDCl3): δ = 2.32 (s, 3 H, CH3), 3.77 (s, J = 5.0 Hz, 1 H, furan-H), 6.97 (d, J = 8.0 Hz, 2 H, Ar-H), 7.07
3 H, CO2CH3), 3.81 (s, 3 H, OCH3), 4.73 (d, J = 5.0 Hz, 1 H,
furan-H), 4.93 (d, J = 5.0 Hz, 1 H, furan-H), 6.71 (d, J = 8.5 Hz,
2 H, Ar-H), 6.96 (d, J = 8.5 Hz, 2 H, Ar-H), 7.01 (d, J = 8.0 Hz,
2 H, Ar-H), 7.19 (d, J = 8.0 Hz, 2 H, Ar-H) ppm. 13C NMR
(125 MHz, CDCl3): δ = 21.5, 30.9, 53.2, 54.3, 55.4, 86.4, 114.5,
117.4 (q, 1JC,F = 272.5 Hz), 127.8, 129.0, 129.3, 129.6, 133.7, 137.6,
(d, J = 8.0 Hz, 2 H, Ar-H), 7.24–7.26 (m, 2 H, Ar-H), 7.36–7.37
(m, 2 H, Ar-H), 7.46–7.49 (m, 2 H, Ar-H), 7.63–7.66 (m, 1 H, Ar-
H), 7.79–7.81 (m, 2 H, Ar-H) ppm. 13C NMR (125 MHz, CDCl3):
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δ = 21.7, 31.1, 53.0, 89.6, 117.4 (q, JC,F = 272.5 Hz), 127.8, 128.7,
128.7, 128.8, 129.2, 129.2, 129.6, 129.9, 132.5, 132.6, 134.8, 136.8,
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137.6, 145.0, 150.3 (q, JC,F = 41.3 Hz), 190.4 ppm. 19F NMR
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144.5, 149.5 (q, JC,F = 40.0 Hz), 159.8, 168.2 ppm. 19F NMR
(470 MHz, CDCl ): δ = –63.00 (s, CF ) ppm. IR (KBr): ν = 2925,
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(470 MHz, CDCl ): δ = –63.41 (s, CF ) ppm. IR (KBr): ν = 2957, 1699, 1597, 1645, 1597, 1334, 1199, 1161, 1109, 1079, 693 cm–1.
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1762, 1646, 1597, 1513, 1331, 1254, 1198, 1160, 1077, 1032, MS (EI): m/z (%) = 506 (1) [M]+, 105 (100). HRMS (EI): calcd.
813 cm–1. MS (EI): m/z (%) = 456 (19) [M]+, 301 (100). HRMS for C25H18ClF3O4S [M]+ 506.0566; found 506.0564.
(EI): calcd. for C21H19F3O6S [M]+ 456.0854; found 456.0851.
Methyl 3-(3-Chlorophenyl)-4-tosyl-5-trifluoromethyl-trans-2,3-dihy-
{3-[4-(Dimethylamino)phenyl]-4-tosyl-5-trifluoromethyl-trans-2,3-di-
hydrofuran-2-yl}(phenyl)methanone (7Ea): Brown solid. Yield
443 mg, 86%. M.p. 129.8–130.1 °C. H NMR (500 MHz, CDCl3):
drofuran-2-carboxylate (7Fc): Light yellow oil. Yield 387 mg, 84%.
1H NMR (500 MHz, CDCl3): δ = 2.36 (s, 3 H, CH3), 3.86 (s, 3 H,
CO2CH3), 4.72 (d, J = 5.0 Hz, 1 H, furan-H), 4.92 (d, J = 5.0 Hz,
1 H, furan-H), 6.87–6.88 (m, 1 H, Ar-H), 7.01–7.06 (m, 3 H, Ar-
H), 7.16–7.28 (m, 4 H, Ar-H) ppm. 13C NMR (125 MHz, CDCl3):
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δ = 2.33 (s, 3 H, CH3), 2.98 [s, 6 H, N(CH3)2], 4.66 (d, J = 5.0 Hz,
1 H, furan-H), 5.79 (d, J = 5.0 Hz, 1 H, furan-H), 6.58 (d, J =
8.5 Hz, 2 H, Ar-H), 6.98 (d, J = 8.5 Hz, 2 H, Ar-H), 7.00 (d, J =
8.0 Hz, 2 H, Ar-H), 7.21 (d, J = 8.0 Hz, 2 H, Ar-H), 7.45–7.48 (m,
2 H, Ar-H), 7.61–7.64 (m, 1 H, Ar-H), 7.80–7.82 (m, 2 H, Ar-H)
ppm. 13C NMR (125 MHz, CDCl3): δ = 21.5, 30.9, 40.4, 53.4, 90.0,
112.8, 117.5 (q, 1JC,F = 272.5 Hz), 124.7, 127.8, 128.9, 129.0, 129.2,
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δ = 21.5, 30.9, 53.4, 54.5, 86.0, 117.2 (q, JC,F = 272.5 Hz), 126.2,
127.7, 127.8, 128.6, 129.5, 130.4, 135.1, 137.1, 139.3, 145.0, 150.4
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(q, JC,F = 41.3 Hz), 167.8 ppm. 19F NMR (470 MHz, CDCl3): δ
= –63.17 (s, CF ) ppm. IR (KBr): ν = 2954, 2928, 1759, 1645, 1596,
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1336, 1198, 1168, 1143, 1080, 811, 797 cm–1. MS (EI): m/z (%) =
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131.5, 132.5, 134.4, 138.0, 143.8, 149.4 (q, JC,F = 40.0 Hz), 150.7,
461 (1) [M + H]+, 460 (5) [M]+, 305 (100). C20H16ClF3O5S (460.85):
190.8 ppm. 19F NMR (470 MHz, CDCl3): δ = –63.26 (s, CF3) ppm. calcd. C 52.12, H 3.50; found C 52.22, H 3.58.
IR (KBr): ν = 2924, 2896, 1698, 1647, 1611, 1524, 1329, 1199, 1150,
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[3-(4-Bromophenyl)-4-tosyl-5-trifluoromethyl-trans-2,3-dihydro-
furan-2-yl](phenyl)methanone (7Ga): Light yellow solid. Yield
447 mg, 81%. M.p. 166.3–167.2 °C. H NMR (500 MHz, CDCl3):
δ = 2.39 (s, 3 H, CH3), 4.80 (d, J = 5.0 Hz, 1 H, furan-H), 5.74 (d,
J = 5.0 Hz, 1 H, furan-H), 6.98 (d, J = 8.0 Hz, 2 H, Ar-H), 7.08
(d, J = 8.0 Hz, 2 H, Ar-H), 7.25–7.27 (m, 2 H, Ar-H), 7.37 (d, J =
8.0 Hz, 2 H, Ar-H), 7.47–7.50 (m, 2 H, Ar-H), 7.63–7.66 (m, 1 H,
1109, 1076, 809, 693 cm–1. MS (EI): m/z (%) = 516 (8) [M + H]+,
515 (28) [M]+, 105 (100). HRMS (EI): calcd. for C27H24F3NO4S
[M]+ 515.1378; found 515.1380.
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3-[4-(Dimethylamino)phenyl]-4-tosyl-5-trifluoromethyl-trans-2,3-di-
hydrofuran-2-carbonitrile (7Eb): Brown solid. Yield 367 mg, 84%.
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M.p. 143.4–143.7 °C. H NMR (500 MHz, CDCl3): δ = 2.15 (s, 3
Eur. J. Org. Chem. 0000, 0–0
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