The Journal of Organic Chemistry
Page 8 of 11
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Hz, 3H), 3.12 (s, 3H), 6.86 (t, J = 8.3 Hz, 1H), 7.32–7.38 (m,
5.7 Hz), 159.1, 163.3 (dd, JFC = 245.2, 15.8 Hz), 166.0 (dd, JFC
=
243.8, 15.8 Hz); LRMS (EI) m/z: 292 (M+); HRMS (EIꢀTOF) m/z:
(M+) Calcd. for C16H18F2OSi: 292.1095, found: 292.1099; IR
(neat): 772, 809, 837, 980, 1031, 1178, 1196, 1239, 1287, 1381,
1456, 1516, 1602, 2837, 2957 cmꢀ1.
1H); 13C{1H} NMR (150 MHz, CDCl3/TMS) δ (ppm): 0.1 (t, JFC
= 2.9 Hz), 35.0, 38.3 (d, JFC = 2.9 Hz), 111.7 (dd, JFC = 27.5, 4.3
Hz), 114.2 (t, JFC = 35.4 Hz), 120.5 (dd, JFC = 23.1, 4.3 Hz),
131.2–131.3 (m), 162.2 (dd, JFC = 244.9, 16.6 Hz), 166.7, 167.4
(dd, JFC = 246.4, 15.2 Hz); LRMS (EI) m/z: 257 (M+); HRMS (EIꢀ
TOF) m/z: (M+) Calcd. for C12H17F2NOSi: 257.1047, found:
257.1078; IR (neat): 778, 842, 991, 1089, 1189, 1247, 1398, 1606,
1639, 2957 cmꢀ1.
2,4-Difluoro-4’-cyano-3-trimethylsilylbiphenyl (6p). Recrystalꢀ
lized from acetone/hexane, pale yellow needless, mp 55 °C. 68.9
1
mg (81%). H NMR (400 MHz, CDCl3/TMS) δ (ppm): 0.40 (t, J
= 1.4 Hz, 9H), 6.92 (t, J = 7.8 Hz, 1H), 7.35–7.41 (m, 1H), 7.59
2,4-Difluoro-4’-methyl-3-trimethylsilylbiphenyl (6k). Colorless oil.
(dd, J = 8.5, 1.7 Hz, 2H), 7.72 (d, J = 8.3 Hz, 2H); 13C{1H} NMR
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55.2 mg (66%). H NMR (400 MHz, CDCl3/TMS) δ (ppm): 0.39
(100 MHz, CDCl3/TMS) δ (ppm): 0.2, 111.2, 111.8 (dd, JFC
27.3, 3.3 Hz), 114.6 (t, JFC = 35.2 Hz), 118.7, 123.1 (dd, JFC
18.2, 4.1 Hz), 129.7 (d, JFC = 3.3 Hz), 132.1, 132.6 (dd, JFC = 10.8,
=
=
(s, 9H), 2.39 (s, 3H), 6.86 (td, J = 8.8, 1.0 Hz, 1H), 7.23–7.25 (m,
2H), 7.33–7.39 (m, 3H); 13C{1H} NMR (100 MHz, CDCl3/TMS)
δ (ppm): 0.29 (t, JFC = 3.3 Hz), 21.2, 111.2 (dd, JFC = 27.0, 4.1
Hz), 113.8 (dd, JFC = 36.0, 33.6 Hz), 124.9 (dd, JFC = 18.8, 3.3
Hz), 128.9 (d, JFC = 2.5 Hz), 129.1, 132.6–132.8 (m, 2C), 137.3,
163.3 (dd, JFC = 245.0, 15.6 Hz), 166.1 (dd, JFC = 244.4, 15.6 Hz);
LRMS (EI) m/z: 276 (M+); HRMS (EIꢀTOF) m/z: (M+) Calcd. for
C16H18F2Si: 276.1146, found: 276.1152; IR (neat): 718, 741, 771,
806, 842, 980, 1020, 1053, 1112, 1127, 1196, 1242, 1380, 1413,
1456, 1605, 1896, 2363, 2949, 2957 cmꢀ1.
5.0 Hz), 140.3, 163.3 (dd, JFC = 246.6, 15.7 Hz), 167.0 (dd, JFC
=
246.6, 16.6 Hz); LRMS (EI) m/z: 287 (M+); HRMS (EIꢀEB) m/z:
(M+) Calcd. for C16H15F2NSi: 287.0942, found: 287.0937; IR
(neat): 744, 764, 772, 815, 841, 983, 1050, 1132, 1196, 1241,
1250, 1378, 1460, 1607, 1734, 2225, 2367, 2861, 2962 cmꢀ1.
2,4-Difluoro-4’-nitro-3-trimethylsilylbiphenyl (6q). Recrystallized
from acetone/hexane, pale yellow needless, mp 67–70 °C. 58.7
1
mg (64%). H NMR (400 MHz, CDCl3/TMS) δ (ppm): 0.41 (s,
2,4-Difluoro-3’-methyl-3-trimethylsilylbiphenyl (6l). Colorless oil.
9H), 6.94 (t, J = 8.3 Hz, 1H), 7.38–7.44 (m, 1H), 7.65 (dd, J = 8.8,
2.0 Hz, 2H), 8.29 (d, J = 8.8 Hz, 2H); 13C{1H} NMR (150 MHz,
CDCl3/TMS) δ (ppm): 0.16–0.22 (m), 111.9 (td, JFC = 22.9, 2.9
Hz), 114.7 (t, JFC = 35.1 Hz), 122.8 (dd, JFC = 18.6, 4.3 Hz) 123.6
(d, JFC = 17.2 Hz), 129.9 (d, JFC = 8.6 Hz), 132.5–132.8 (m),
1
71.5 mg (86%). H NMR (400 MHz, CDCl3/TMS) δ (ppm): 0.39
(t, J = 1.4 Hz, 9H), 2.40 (s, 3H), 6.86 (t, J = 8.3 Hz, 1H), 7.16 (d,
J = 7.3 Hz, 1H), 7.23–7.39 (m, 4H); 13C{1H} NMR (100 MHz,
CDCl3/TMS) δ (ppm): 0.3 (t, JFC = 2.9 Hz), 21.5, 111.2 (dd, JFC
26.9, 3.7 Hz), 113.8 (dd, JFC = 35.6, 33.1 Hz), 125.1 (dd, JFC
=
=
142.3, 147.1, 163.3 (dd, JFC = 246.7, 15.8 Hz), 167.2 (dd, JFC
=
18.6, 3.7 Hz), 126.2 (d, JFC = 2.5 Hz), 128.3 (d, JFC = 2.5 Hz),
129.8 (d, JFC = 2.5 Hz), 132.8–132.9 (m, 2C), 135.6 (d, JFC = 1.7
246.0, 16.5 Hz); LRMS (EI) m/z: 307 (M+); HRMS (EIꢀTOF) m/z:
(M+) Calcd. for C15H15F2NO2Si: 307.0840, found: 307.0827; IR
(neat): 731, 773, 816, 842, 984, 1012, 1097, 1110, 1129, 1243,
1346, 1456, 1509, 1598, 2356, 2452, 2958, 3079 cmꢀ1.
Hz), 138.0, 163.3 (dd, JFC = 245.8, 15.7 Hz), 166.2 (dd, JFC
=
244.1, 15.7 Hz); LRMS (EI) m/z: 276 (M+); HRMS (EIꢀTOF) m/z:
(M+) Calcd. for C16H18F2Si: 276.1146, found: 276.1127; IR
(neat): 700, 786, 842, 877, 1126, 1241, 1377, 1458, 1606, 2957
cmꢀ1.
3-Fluoro-2-trimethylsilylnitrobenzene (6r). Yellow oil. 41.1 mg
1
(64%). H NMR (400 MHz, CDCl3/TMS) δ (ppm): 0.38 (d, J =
2.4 Hz, 9H), 7.21–7.26 (m, 1H), 7.44–7.49 (m, 1H), 7.63 (d, J =
7.8 Hz, 1H); 13C{1H} NMR (100 MHz, CDCl3/TMS) δ (ppm): 0.2
(d, JFC = 4.9 Hz), 119.4 (d, JFC = 3.3 Hz), 119.7, 120.0, 121.8 (d,
JFC = 34.4 Hz), 131.4 (d, JFC = 9.8 Hz), 167.0 (d, JFC = 246.6 Hz);
LRMS (EI) m/z: 198 (M–CH3)+; HRMS (EIꢀTOF) m/z: (M–CH3)+
Calcd. for C8H9FNO2Si: 198.0387, found: 198.0367; IR (neat):
707, 741, 805, 842, 934, 1107, 1234, 1356, 1441, 1529, 2902,
2957 cmꢀ1.
2,4-Difluoro-3-triethylsilylbiphenyl (7a). Yellow oil. 68.3 mg
(76%). 1H NMR (400 MHz, CDCl3/TMS) δ (ppm): 0.92–0.99 (m,
15H), 6.88 (t, J = 8.3 Hz, 1H), 7.35–7.49 (m, 6H); 13C{1H} NMR
(150 MHz, CDCl3/TMS) δ (ppm): 4.4, 7.4, 111.3 (dd, JFC = 27.2,
2.9 Hz), 111.6 (d, JFC = 37.3 Hz), 125.0 (dd, JFC = 18.6, 4.3 Hz),
127.5, 128.4, 129.1 (d, JFC = 2.9 Hz), 132.9 (dd, JFC = 10.5, 5.0
2,4-Difluoro-2’-methyl-3-trimethylsilylbiphenyl (6m). Colorless
1
oil. 56.2 mg (68%). H NMR (400 MHz, CDCl3/TMS) δ (ppm):
0.38 (t, J = 1.5 Hz, 9H), 2.18 (s, 3H), 6.86 (t, J = 8.3 Hz, 1H),
7.17–7.31 (m, 5H); 13C{1H} NMR (100 MHz, CDCl3/TMS) δ
(ppm): 0.2 (t, JFC = 2.5 Hz), 19.9 (d, JFC = 2.5 Hz), 110.9 (dd, JFC
= 26.5, 4.1 Hz), 113.5 (t, JFC = 34.8 Hz), 124.8 (dd, JFC = 21.9,
3.7 Hz), 125.7, 127.9, 130.0, 130.1 133.2–133.4 (m), 135.5, 136.7,
163.3 (dd, JFC = 243.3, 15.7 Hz), 166.3 (dd, JFC = 244.1, 15.7 Hz);
LRMS (EI) m/z: 276 (M+); HRMS (EIꢀTOF) m/z: (M+) Calcd. for
C16H18F2Si: 276.1146, found: 276.1142; IR (neat): 726, 759, 842,
980, 1036, 1120, 1194, 1241, 1386, 1458, 1608, 2957 cmꢀ1.
2,4-Difluoro-4’-tert-butyl-3-trimethylsilylbiphenyl (6n). Recrysꢀ
tallized from hexane, colorless crystals, mp 62–65 °C. 73.2 mg
1
(77%). H NMR (400 MHz, CDCl3/TMS) δ (ppm): 0.39 (s, 9H),
Hz), 135.8, 163.7 (dd, JFC = 245.2, 15.8 Hz), 166.7 (dd, JFC =
1.35 (s, 9H), 6.86 (t, J = 8.3 Hz, 1H), 7.34–7.47 (m, 5H); 13C{1H}
NMR (100 MHz, CDCl3/TMS) δ (ppm): 0.3 (t, JFC = 2.9 Hz), 31.3,
34.6, 111.3 (dd, JFC = 27.0, 4.1 Hz), 113.7 (d, JFC = 34.4 Hz),
125.0, 125.4, 128.7 (d, JFC = 3.3 Hz), 132.7–132.8 (m, 2C), 150.5,
163.4 (dd, JFC = 244.1, 15.6 Hz), 166.1 (dd, JFC = 244.1, 15.6 Hz);
LRMS (EI) m/z: 318 (M+); HRMS (EIꢀTOF) m/z: (M+) Calcd. for
C19H24F2Si: 318.1615, found: 318.1598; IR (neat): 771, 814, 840,
980, 1015, 1112, 1127, 1194, 1240, 1248, 1380, 1454, 1602, 2861,
2919, 2957 cmꢀ1.
243.8, 15.8 Hz); LRMS (EI) m/z: 304 (M+); HRMS (EIꢀTOF) m/z:
(M+) Calcd. for C18H22F2Si: 304.1459, found: 304.1470; IR
(neat): 718, 733, 767, 796, 818, 981, 1003, 1022, 1058, 1126,
1196, 1243, 1381, 1452, 1605, 2875, 2955, 3034 cmꢀ1.
2,4-Difluoro-3-triphenylsilylbiphenyl (8a). Recrystallized from
acetone/hexane, colorless prisms, mp 119–121 °C. 36.3 mg (81%,
1
0.10 mmol scale). H NMR (400 MHz, CDCl3/TMS) δ (ppm):
6.93 (t, J = 8.3 Hz, 1H), 7.30–7.44 (m, 14H), 7.52 (q, J = 8.3 Hz,
1H), 7.62 (d, J = 7.3 Hz, 6H); 13C{1H} NMR (100 MHz,
CDCl3/TMS) δ (ppm): 109.9 (dd, JFC = 33.6, 31.1 Hz), 111.9 (dd,
JFC = 26.2, 4.1 Hz), 125.5 (dd, JFC = 18.0, 4.1 Hz), 127.6, 127.8,
128.4, 129.1 (d, JFC = 2.5 Hz), 129.6, 133.8 (d, JFC = 1.6 Hz),
134.4 (dd, JFC = 10.2, 5.3 Hz), 135.3 (d, JFC = 1.6 Hz), 136.0,
163.4 (dd, JFC = 250.3, 13.5 Hz), 166.4 (dd, JFC = 248.2, 13.9 Hz);
LRMS (EI) m/z: 448 (M+); HRMS (EIꢀEB) m/z: (M+) Calcd. for
C30H22F2Si: 448.1459, found: 448.1454; IR (neat): 706, 765, 813,
2,4-Difluoro-4’-methoxy-3-trimethylsilylbiphenyl (6o). Brown oil.
1
72.0 mg (82%). H NMR (400 MHz, CDCl3/TMS) δ (ppm): 0.39
(d, J = 1.5 Hz, 9H), 3.85 (s, 3H), 6.85 (t, J = 8.3 Hz, 1H), 6.95–
6.98 (m, 2H), 7.31–7.42 (m, 3H); 13C{1H} NMR (150 MHz,
CDCl3/TMS) δ (ppm): 0.3 (t, JFC = 2.9 Hz), 55.3, 111.2 (dd, JFC
26.5, 3.6 Hz), 113.8 (t, JFC = 35.1 Hz), 113.9, 124.6 (dd, JFC
=
=
18.6, 2.9 Hz), 128.0, 130.2 (d, JFC = 2.9 Hz), 132.6 (dd, JFC = 10.0,
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