C.-Y. Wang et al. / Journal of Fluorine Chemistry 126 (2005) 996–1001
999
(6 mL) under nitrogen atmosphere. Then the mixture was
3.5.4. 2-Styryl-4-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,
stirred at 70 8C for about 15 h. The solvent was removed
under vacuum to afford a white solid, then ethanol (1.5 mL)
was added. The mixture was shaken vigorously and filtered.
Then the filtration cake was dissolved in dichloromethane
at elevated temperature, cooled to ꢀ10 8C and fluorous
boronates 5 were obtained by rapid filtration.
11,11-henicosaflu-orodecyl)-[1,3,2] dioxaborolane(5d)
Yield: 196 mg (94%) 1H NMR (300 MHz, CDCl3) d 7.5–
7.50 (m, 2H), 7.44 (d, J = 18.3 Hz, 1H), 7.40–7.33 (m, 3H),
6.18 (d, J = 18.3 Hz, 1H), 4.95–4.86 (m, 1H), 4.54–4.48 (t,
J = 9.0 Hz, 1H), 4.04–3.98 (t, J = 9.0 Hz, 1H), 2.70–2.57
(m, 1H), 2.48–2.34 (m, 1H); 19F NMR (282 MHz, CDCl3) d
ꢀ80.97 (s, 3F), ꢀ112.81 (s, 2F), ꢀ122.07 (s, 10F), ꢀ122.98
(s, 2F), ꢀ123.80 (s, 2F), ꢀ126.40 (s, 2F); IR(KBr) 2965,
2923, 1625, 1577, 1450, 1351, 1212, 1151, 1113, 1025, 881,
752, 695, 649, 558, 529 cmꢀ1; MS (EI, 70 ev, m/z) 707 (M+,
20), 706 (M+ ꢀ 1,100), 173 (71), 143 (15), 117 (25), 116
(55), 69 (16); Anal. Calcd. for C21H12F21BO2: C 35.69,
H 1.71; Found: C 35.55, H 2.01.
3.5.1. 2-Phenyl-4-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,
11,11,11-henicosafluorodecyl-[1,3,2] dioxaborolane (5a)
1
Yield: 191 mg (94%), H NMR (400 MHz, CDCl3) d
7.82–7.80 (m, 2H), 7.52–7.48 (m, 1H), 7.41–7.34 (m, 2H),
4.58 (dd, J1 = 8.0 Hz, J2 = 8.0 Hz, 1H), 4.09 (dd,
J1 = 8.0 Hz, J2 = 8.0 Hz, 1H), 2.73–2.65 (m, 1H), 2.45–
2.38 (m, 1H); 19F NMR (376 MHz, CDCl3) d ꢀ80.67 (s, 3F),
ꢀ112.40 (s, 2F), ꢀ121.72 (s, 10F), ꢀ122.65 (s, 2F),
ꢀ123.47 (s, 2F), ꢀ126.06 (s, 2F); IR (KBr) 2963, 2921,
1603, 1500, 1485, 1441, 1406, 1386, 1355, 1218, 1151,
1095, 1027, 884, 802, 760, 700, 648, 556, 529 cmꢀ1; MS
(EI, 70 ev, m/z) 680 (M+, 29), 148 (10), 147 (100), 118 (28),
117 (12), 91 (32), 77 (5), 69 (9). Anal. Calcd. for
C19H10F21BO2: C 33.56, H 1.48; Found: C 33.86, H
1.70.
3.5.5. 2-Thienyl-4-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,
11,11-henicosafluorodecyl)-[1,3,2] dioxaborolane(5e)
Yield: 190 mg (94%) 1H NMR (400 MHz, CDCl3) d 7.69
(d, J = 4.0 Hz, 2H), 7.22(t, J = 4.0 Hz 1H), 5.02–4.95 (m,
1H), 4.60–4.56 (dd, J1 = 8.0 Hz, J2 = 8.0 Hz, 1H), 4.12–4.08
(dd, J1 = 8.0 Hz, J2 = 8.0 Hz, 1H), 2.76–2.71 (m, 1H), 2.45–
2.39 (m, 1H); 19F NMR (376 MHz) d ꢀ80.69 (s, 3F), ꢀ112.37
(s, 2F), ꢀ121.71 (s, 10F), ꢀ122.65 (s, 2F), ꢀ123.48 (s, 2F),
ꢀ126.06 (s, 2F); IR(KBr) 2997, 2926, 1524, 1438, 1428,
1360, 1303, 1208, 1151, 1062, 1020, 885, 657, 556,
529 cmꢀ1; MS (EI, 70 ev, m/z) 687 (M+ + 1, 12), 686
(M+, 54), 153 (100), 124 (24), 97 (35), 69 (20); Anal. Calcd.
for C17H8F21BO2S: C 29.76, H 1.17; Found: C 29.83,
H 1.13.
3.5.2. 2-p-Tolyl-4-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,
10,11,11,11-henicosafluorodecyl)-[1,3,2]
dioxaborolane(5b)
1
Yield: 195 mg (94%), H NMR (400 MHz, CDCl3) d
7.70(d, J = 8.0 Hz, 2H), 7.21(d, J = 8 Hz, 2H), 5.00–4.95
(m, 1H), 4.57 (dd, J1 = 7.2 Hz, J2 = 9.2 Hz, 1H), 4.08 (dd,
J1 = 7.2 Hz, J2 = 9.2 Hz, 1H), 2.73–2.69 (m, 1H), 2.44–2.38
(m, 1H), 2.38 (s, 3H); 19F NMR (376 MHz, CDCl3) d
ꢀ80.68 (s, 3F), ꢀ112.39 (s, 2F), ꢀ121.71 (s, 10F), ꢀ122.64
(s, 2F), ꢀ123.47 (s, 2F), ꢀ126.05 (s, 2F); IR(KBr) 2989,
2921, 1614, 1519, 1486, 1438, 1409, 1386, 1354, 1322,
1217, 1152, 1092, 1022, 884, 816, 647, 556, 529 cmꢀ1; MS
(EI, 70 ev, m/z) 695 (M+ + 1,17), 694 (M+, 80), 161 (100),
132 (44), 105 (48), 91 (28), 69 (15). Anal. Calcd for
C20H12F21BO2: C 34.60, H 1.74; Found: C 34.38, H
2.15.
3.5.6. 2-(4-Methylthiophenyl)-4-(2,2,3,3,4,4,5,5,6,6,
7,7,8,8,9,9,10,10,11,11,11-henicosafluorodecyl)-
[1,3,2]dioxaborolane(5f)
Yield: 206 mg (94%) 1H NMR (400 MHz, CDCl3) d
7.68(s, 1H), 7.56(d, J = 8.0 Hz 1H), 7.48–7.38 (m, 1H), 7.32
(d, J = 8.0 Hz 1H), 5.00–4.97 (m, 1H), 4.58 (dd, J1 = 8.0 Hz,
J2 = 8.0 Hz, 1H), 4.09 (dd, J1 = 8.0 Hz, J2 = 8.0 Hz, 1H),
2.79–2.64 (m, 1H), 2.50 (s, 3H), 2.53–2.30 (m, 1H); 19F
NMR (376 MHz) d ꢀ80.67 (s, 3F), ꢀ112.34 (s, 2F),
ꢀ121.68 (s, 10F), ꢀ122.62 (s, 2F), ꢀ123.44 (s, 2F),
ꢀ126.03 (s, 2F); IR(KBr) 2983, 2920, 1631, 1592, 1440,
1353, 1209, 1152, 1017, 998, 881, 791, 701, 650, 556,
530 cmꢀ1; MS (EI, 70 ev, m/z) 728 (M+ + 2, 7), 727 (M+ + 1,
23), 726 (M+, 100), 193 (23), 164 (7), 137 (27), 69 (14);
Anal. Calcd. for C20H12F21BO2S: C 33.08, H 1.67; Found: C
33.05, H 2.15.
3.5.3. 2-(4-Methoxyphenyl)-4-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,
9,9,10,10,11,11,11-henicosafluorodecyl)-[1,3,2]
dioxaborolane (5c)
Yield: 195 mg (94%) 1H NMR (400 MHz, CDCl3) d 7.75
(d, J = 8.0 Hz, 2H), 6.92 (d, J = 8.0 Hz, 2H), 4.99–4.93 (m,
1H), 4.56 (dd, J1 = 8.0 Hz, J2 = 8.0 Hz, 1H), 4.06 (dd,
J1 = 8.0 Hz, J2 = 8.0 Hz, 1H), 3.84 (s, 3 H), 2.72–2.68 (m,
1H), 2.43–2.36 (m, 1H); 19F NMR (376 MHz, CDCl3) d
ꢀ80.68 (s, 3 F), ꢀ112.37 (s, 2F), ꢀ121.70 (s, 10F), ꢀ122.63
(s, 2F), ꢀ123.46 (s, 2F), ꢀ126.04 (s, 2F); IR (KBr) 2962,
2934, 2839, 1608, 1569, 1486, 1454, 1439, 1413, 1386,
1355, 1296, 1215, 1151, 1095, 1031, 885, 831, 797, 646,
556, 529 cmꢀ1; MS (EI, 70 ev, m/z) 711 (M+ + 1, 23), 710
(M+, 100), 177 (41), 148 (26), 121 (39), 69 (16); Anal. Calcd.
for C20H12F21BO3: C 33.83, H 1.70; Found: C 33.79, H 1.70.
3.5.7. 2-(4-Chlorophenyl)-4-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,
9,9,10,10,11,11,11-henicosafluorodecyl)-[1,3,2]
dioxaborolane (5g)
Yield: 196 mg (94%) 1H NMR (400 MHz, CDCl3) d 7.73
(d, J = 8.0 Hz, 2H), 7.39 (d, J = 8.0 Hz, 2H), 5.02–4.95 (m,
1H), 4.58 (dd, J1 = 8.0 Hz, J2 = 8.0 Hz, 1H), 4.09 (dd,
J1 = 8.0 Hz, J2 = 8.0 Hz, 1H), 2.74–2.67 (m, 1H), 2.45–2.38
(m, 1H); 19F NMR (376 MHz, CDCl3) d ꢀ80.67 (s, 3F),
ꢀ112.37 (s, 2F), ꢀ121.69 (s, 10F), ꢀ122.62 (s, 2F),