786
V.A. Petrov, W. Marshall / Journal of Fluorine Chemistry 132 (2011) 783–791
Table 2
NMR data for new compoundsa.
Compound no.
1H NMR (
d
, ppm, J, Hz)
19F NMR (
d
, ppm, J, Hz)
13C NMR (
d, ppm, J, Hz)
3a
2.21(1H, d, 15.4), 2.96(1H, dd, 15.4, 8.1),
3.86(1H, d, 6.6), 4.06(1H, s), 4.12(1H, d, 6.1),
5.92(1H, d, 7.8), 6.33(1H, t, 6.4), 6.58(1H, t, 7.7)
À64.95(3F, q, 11.7), À66.99(3F,
qd, 11.7, 2.4), À69.67(3F, q, 10.1),
À71.36(3F, q, 10.1)
26.12, 38.42, 40.71, 43.07,
62.32(sept, 26.0), 63.76(sept, 25.0),
121.15, 123.53(q, 286.0),
123.92(q, 286.0), 123.98(q, 284.0),
124.26(q, 282.0), 128.92,
132.23, 137.67
3b
1.30(2H, m), 1.78(1H, d, 13.6), 1.86(2H, m), 1.96(1H, d, 13.6),
2.17(1H, t, 12.1), 2.27(1H, d, 15.8), 3.00(1H, dd, 15.8, 8.2),
3.81(1H, s), 4.10(1H, s), 4.15(1H, d, 7.3), 5.90(2H, m)
À64.72(3F, q, 11.2), À66.62(3F,
qd, 11.2, 2.5), À69.53(3F, q, 10.2),
À71.18(3F, q, 10.2)
25.76, 25.98, 26.03, 26.13, 30.56,
31.29, 41.04, 41.61, 42.84, 42.85,
61.56(sept, 26.0), 64.56(sept, 25.5),
119.47, 119.63, 123.73(q, 288.0),
123.99(q, 284.0), 124.00(q, 288.0),
124.40(q, 282.0), 138.55,
149.86(q, 2.5)
3c
1.95(3H, s), 2.18(1H, d, 15.6), 2.94(1H, dd, 15.6, 8.2),
3.54(1H, m), 4.03(2H), 5.87(2H, t, 8.2)
À64.95(3F, q, 11.5), À67.12(3F,
qd, 11.5, 2.5), À69.62(3F, q, 10.4),
À71.27(3F, q, 10.4)
20.48, 25.64, 41.54, 42.79, 43.04,
61.49(sept, 28.0), 64.54(sept, 26.0),
119.80, 121.79 123.63(q, 285.0),
123.95(q, 286.0), 124.32(q, 282.0),
138.59, 141.57(q, 2.0)
3d
1.13(9H, s), 2.18(1H, d, 15.9), 2.73(1H, dd, 15.9, 8.0),
3.94(1H, m), 4.05(1H, m), 4.09(1H, d, 7.3) 5.84(1H, dm, 7.9),
5.91(1H, dm, 8.1),
À64.68(3F, q, 11.9), À66.71(3F,
qd, 11.9, 2.6), À69.81(3F, q, 10.1),
À71.34(3F, q, 10.1)
25.58, 28.29, 34.69, 49.22, 41.98,
42.64, 61.29(sept, 26.7),
64.39(sept, 25.4),
119.18, 119.50, 123.78(q, 284.0),
124.00(q, 283.0), 124.43(q, 281.0),
138.34, 152.46(q, 2.0)
3e
2.19(1H, d, 15.4), 2.97(1H, dd, 15.4, 8.0), 3.80(1H, s),
À64.76(3F, q, 10.1), À67.36(3F,
qd, 10.1, 2.2), À69.61(3F, q, 10.1),
À71.70(3F, q, 10.1)
4.02(1H, s), 4.18(1H, d, 7.0), 5.94(1H, m), 6.18(1H, dm, 7.4)
3f
2.22(1H, d, 15.4), 2.92(1H, dd, 15.4, 8.0), 3.76(1H, d, 11.2),
3.99(1H, s), 4.23(1H, dd, 7.9, 2.5), 5.57(1H, m), 5.95(1H, m)
À64.53(3F, q, 11.5), À67.00(3F,
qt, 11.5, 2.1), À69.57(3F, q, 10.0),
À71.13(3F, q, 10.0), À101.34(1F, m)
À64.76(3F, q, 11.2), À66.51(3F,
qd, 11.2, 2.0), À69.57(3F, q, 9.9),
À71.17(3F, q, 9.9)
3gb,c
3hd,e
2.13(1H, d, 15.5), 2.88(1H, dd, 15.5, 8.0), 3.76(3H, s), 3.89(1H, s),
4.07(1H, dd, 7.8), 4.86(1H, dm, 7.6) 5.76(1H, dm, 7.6)
1.25(3H, t, 7.1), 2.12(1H, d, 15.0), 2.86(1H, dd, 15.0, 8.0),
3.51(1H, m), 3.73(2H, q, 7.1), 3.89(1H, m), 4.05(1H, dd, 7.8),
4.80(1H, dm, 7.6) 5.70(1H, dm, 7.4)
À64.78(3F, q, 11.6), À66.55(3F,
qd, 11.6, 2.1), À69.59(3F, q, 10.2),
À71.18(3F, q, 10.2)
4ae
4be
3.35(2H, AB quart.), 4.86(1H, t, 8.4) 7.20–7.40(5H)
1.30–3.0(10H), 3.31(2H, AB quart.), 4.82(1H, t, 8.4)
7.20–7.40(4H)
À73.18(3F, q, 9.7), À74.39(3F, q, 9.7)
À73.14(3F, q, 9.9), À74.36(3F, q, 9.9)
4ce
4d
1.95(3H, s), 3.32(2H, AB quart.), 4.83(1H, t, 8.4)
7.19(2H, d, 7.3), 7.31(2H, d, 7.3)
À73.16(3F, q, 9.7), À74.37(3F, q, 9.7)
À73.15(3F, q, 9.8), À74.36(3F, q, 9.8)
1.31(9H, s), 3.33(2H, A:B quart.), 4.84(1H, t, 8.3), 7.41(2H, d),
7.48(2H, d)
4e
4f
3.84(2H, A:B quart.), 4.84(1H, t, 8.4), 7.32(2H), 7.44(2H)
3.32(2H, A:B quart.), 4.84(1H, t, 8.4), 7.07(2H), 7.51(2H)
73.23(3F, q, 9.6), À74.42(3F, q, 9.6)
À73.20(3F, q, 9.6), À74.39(3F, q, 9.6)
À112.74(1F, m)
4g
4h
4if
4j
3.25(2H, A:B quart.), 3.74(3H, s), 4.75(1H, t, 8.7), 6.84(2H, d),
7.38(2H, d)
À73.11(3F, q, 9.7), À74.34(3F, q, 9.7)
1.35(3H, t, 7.0), 3.25(2H, A:B quart.), 3.96(2H, q, 7.0),
4.74(1H, t, 8.1), 6.82(2H, d), 7.36(2H, d)
À73.10(3F, q, 9.6), À74.33(3F, q, 9.6)
À73.12(3F, q, 9.9), À74.33(3F, q, 9.9)
1.28(9H, s), 3.26(2H, A:B quart.), 3.96(2H, q, 7.0), 4.75(1H, t, 8.1),
6.92(2H, d), 7.34(2H, d)
3.32(2H, A:B quart.), 3.88(3H, s), 3.92(3H, s), 4.80(1H, t, 8.0),
6.83(1H, d), 7.01(1Hdd) 7.15(1H, d)
À73.20(3F, q, 10.2),
À74.36(3F, q, 10.2)
36.95, 36.56, 46.88(sept, 31.9),
55.15, 114.26, 123.74(q, 280),
125.34(q, 278),
128.96, 132.62, 159.96
5
2.21(1H, d, 15.6), 3.31(1H, dd, 15.6, 8.0), 5.01(1H, s), 4.06(1H, s),
6.03(1H, t, 6.0), 6.40(1H, d), 6.46(1H, d), 7.18(1H, d)
7.27(2H, m), 7.56(1H, d)
À69.53(3F, q, 9.8), À70.58
(3F, q, 9.8)
5a
2.38(2H, t, 6.1), 3.04(2H, t, 6.1), 7.31(1H, d), 7.51(1H, t),
7.57(1H, t), 7.71(1Hd), 7.84(1H, d), 8.24(1H, d)
À71.12(s)
27.13, 40.31, 57.36(sept, 27.2),
121.76, 123.81(q, 283), 123.94,
126.95, 127.87, 128.28, 128.76,
129.41, 130.40, 133.01, 141.37
6
2.30(2H, t, 6.3), 2.94(2H, t, 6.3), 7.36(1H, m), 7.77(1H, m), 7.88(1H, m)
2.27(2H, t, 5.6), 2.84(2H, t, 5.6), 7.13(1H, m), 7.27(1H, m), 7.33(1H, m)
2.28(2H, m), 2.84(2H, t, 6.10, 6.91(1H, m), 7.07(1H, m), 7.16(1H, m)
3.00(2H, t, 5.8), 3.27(2H, t, 5.8), 7.38(1H), 7.62(1H), 8.04(1H)
À63.14(3F, s), À70.09(6F, s)
À71.28(s)
6a
6b
7
À72.29(s), À114.13(m)
À62.89(3F, s), À67.28(6F, s)
23.88, 32.12, 58.74(sept, 26.8),
122.40, 124.10(q, 284), 124.55,
124.77, 126.36(m), 131.72, 142.45
24.15, 32.60, 56.77(sept, 28.1),
124.12(q, 286), 125.29,
7a
2.96(2H, t, 5.8), 3.17(2H, t, 5.8), 7.18(1H), 7.25(1H), 7.76(1H)
À67.25(s)
129.35(sept, 3.2), 129.92, 132.15,
132.78, 136.83
a
In CDCl3 solvent.
b
Reported values: À3.97(3F, q, 10), À2.66(3F, q, 10), À0.966(3F, q, 11), À0.98; (3F, q, 11) ppm (FCCl2CCl2F, external standard).
c
In the product isolated from the reaction carried out in the presence of Bu4N+FꢁÀÁH2O, a second set of signals corresponding to isomer of 3g was present:
d
= À63.51(q,
10.2 Hz), À64.71(q, 11.7 Hz), À66.41(qd, 11.7, 2.3 Hz), À67.14(q, 10.3 Hz) ppm.
In the product isolated in the reaction carried out in the presence of Bu4N+FꢁÀÁH2O, a second set of signals corresponding to isomer of 3h was present:
d
= À63.39(3F, q,
d
10.8 Hz), À64.75(3F, q, 11.7 Hz), À66.44(3F, qd, 11.7, 2.8 Hz), À67.16(3F, q, 10.8 Hz) ppm.
e
Characterized by NMR in the crude reaction mixture.
2:1 Diels–Alder adduct 1H NMR: 1.31(9H, s), 2.12(1H, d, 15.2), 2.86(1H, dd, 15.2, 8.0), 3.37(1H, s) 3.87(1H, s), 3.99(1H, d, 8.0), 4.88(1H, dm, 8.0), 5.73(1H, s) ppm; 19F NMR:
f
À64.78(3F, q, 11.6), À66.55(3F, qt, 11.5, 1.8), À69.59(3F, q, 10.5), À71.80(3F, q, 10.5) ppm.