760 J . Org. Chem., Vol. 62, No. 3, 1997
845 cm-1 1H NMR (200 MHz, acetone-d6) δ 8.08 (dt, J ) 8.9,
5.8 Hz, 1H), 6.93 (ddd, J ) 7.87, 6.41, 1.46 Hz, 1H), 0.42 (t, J )
0.15 Hz, 9H); 13C NMR (75 MHz, CDCl3) δ 169.3 (dd, J ) 253,
15.5 Hz), 159.7 (dd, J ) 259, 17 Hz), 134.3 (d, J ) 9.0 Hz), 129.0
(d, J ) 11.7 Hz), 117.3 (t, J ) 35.4 Hz), 111.9 (dd, J ) 29, 3.6
Hz), -0.1(s); MS (CI, CH4) m/ z 232, 215, 97, 79. Anal. Calcd
for C9H11F2NO2Si: C, 46.74; H, 4.79; N, 6.06. Found: C, 46.69;
H, 4.80; N, 6.12.
Notes
;
6.78 (dt, J ) 9.1, 4.9 Hz, 1H), 0.39 (d, J ) 2.1 Hz, 9H); 13C NMR
(75 MHz, CDCl3) δ 169.5 (d, J ) 252.0 Hz), 158.2 (dd, J ) 245.1,
10.0 Hz), 152.6 (dd, J ) 252.3, 12.2 Hz), 141.8 (dd, J ) 252.3,
12.2 Hz), 138.5, 129.5 (d, J ) 12.4 Hz), 123.9 (d, J ) 33.6 Hz),
115.3 (d, J ) 9.4 Hz), 113.2 (d, J ) 29.6 Hz), 110.8 (dd, J )
23.1, 3.7 Hz) 105.7 (dd, J ) 27.2, 21.9 Hz), 104.8 (d, J ) 25.2
Hz), 0.2; MS (CI, CH4) m/ z 342, 326, 212, 199. Anal. Calcd for
C15H14F3NO3Si: C, 52.78; H, 4.13; N, 4.10. Found: C, 52.71;
H, 4.22; N, 4.07.
Using the same general procedure, the following compounds
were prepared in the yields indicated in Table 2 and gave the
following analytical data.
2-(2,4-Dich lor op h en oxy)-4-flu or o-3-(t r im et h ylsilyl)n i-
tr oben zen e (Ta ble 2, en tr y 14): IR (film) 3083, 2958, 1595,
3,5-Diflu or o-4-(tr im eth ylsilyl)n itr oben zen e (Ta ble 2, en -
tr y 8): IR (film) 3100, 2960, 1605, 1532, 1405, 1350, 1250,1168,
1090, 845 cm-1; 1H NMR (200 MHz, acetone-d6) δ 7.78 (dt, J )
7.0, 2.1 Hz, 2H), 0.42 (t, J ) 3.5 Hz, 9H); 13C NMR (75 MHz,
CDCl3) δ 166.2 (dd, J ) 246, 15.8 Hz), 150.0 (t, J ) 12.0 Hz),
122.2 (t, J ) 35.0 Hz), 106.9 (dd, J ) 35.0, 3.1 Hz), -0.3 (t, J )
2.5 Hz); MS (CI, CH4) m/ z 232, 216, 202. Anal. Calcd for
C9H11F2NO2Si: C, 46.74; H, 4.79; N, 6.06. Found: C, 46.65; H,
4.92; N, 5.99.
1547,1505, 1345, 1250, 1205, 845 cm-1 1H NMR (200 MHz,
;
acetone-d6) δ 8.24 (dd, J ) 9.0, 5.8 Hz, 1H), 7.62 (d, J ) 2.5 Hz,
1H), 7.33 (dd, J ) 9.0, 8.0 Hz, 1H), 7.24 (dd, J ) 8.9, 2.6 Hz,
1H), 6.72 (d, J ) 8.9 Hz 1H), 0.33 (d, J ) 1.9 Hz, 9H); 13C NMR
(75 MHz, CDCl3) δ 169.4 (d, J ) 252.2 Hz), 152.5, 152.3 (d, J )
6.3 Hz), 138.4 (d, J ) 3.5 Hz), 130.9, 129.7 (d, J ) 12.3 Hz),
128.1, 127.6, 124.4, 123.7 (d, J ) 20.0 Hz) 113.8 (d, J ) 7.2 Hz),
113.3, 0.27 (d, J ) 3.3 Hz); MS (CI, CH4) m/ z 374, 358, 344,
249, 232, 212. Anal. Calcd for C15H14Cl2FNO3Si: C, 48.14; H,
3.77; N, 3.76. Found: C, 48.26; H, 3.50; N, 3.85.
2,3,4-Tr iflu or o-5-(tr im eth ylsilyl)n itr oben zen e (Ta ble 2,
en tr y 9): IR (film) 2860, 1612, 1540, 1440, 1250, 1056, 846 cm-1
;
2-P h en oxy-4-flu or o-3-(tr im eth ylsilyl)n itr oben zen e (Table,
en tr y 15): IR (film) 3090, 2980, 1596, 1570,1527, 1489, 1440,
1395, 1345, 1255, 1213, 1110, 875, 845 cm-1; 1H NMR (200 MHz,
acetone-d6) δ 8.15 (dd, J ) 9.0, 5.8 Hz, 1H), 7.33 (m, 1H), 7.26
(dd, J ) 5.8, 4.9 Hz, 1H), 7.10 (t, J ) 7.4 Hz, 1H), 6.84 (m, 2H),
0.30 (d, J ) 1.9 Hz, 9H); 13C NMR (75 MHz, CDCl3) δ 169.3 (d,
J ) 253.1 Hz), 157.5, 153.1 (d, J ) 17.3 Hz), 139.3, 130.2, 129.6,
129.0 (d, J ) 12.1 Hz), 122.8, 114.8, 112.5 (d, J ) 29.7 Hz), 0.2
(d, J ) 3.5 Hz); MS (CI, CH4) m/ z 306, 290, 249, 232. Anal.
Calcd for C15H16FNO3Si: C, 58.99; H, 5.28; N, 4.61. Found: C,
59.18; H, 5.11; N, 4.56.
1H NMR (200 MHz, acetone-d6) δ 8.00 (ddd, J ) 8.1, 4.8, 2.6
Hz, 2H), 0.42 (t, J ) 1.0 Hz, 9H); 13C NMR (75 MHz, CDCl3) δ
157.8 (ddd, J ) 251.8, J ) 6.2, 2.4 Hz), 146.9 (ddd, J ) 268.7,
7.6, 5.1 Hz), 140.0 (ddd, J ) 257.6, 14.2, 5.6 Hz), 134.3, 124.8
(dt, J ) 13.7, 3.6 Hz), -1.7. Anal. Calcd for C9H10F3NO2Si: C,
43.38; H, 4.04; N, 5.62. Found: C, 43.32; H, 4.09; N, 5.55.
3,4-Diflu or o-2-(tr im eth ylsilyl)n itr oben zen e (Ta ble 2, en -
tr y 10): IR (film) 3100, 2950, 1535, 1530, 1455, 1298, 1270, 1251,
1
835 cm-1; H NMR (200 MHz, acetone-d6) δ 7.89 (ddd, J ) 8.9,
5.8, 1.6 Hz, 1H), 7.60 (dt, J ) 9.1, 8.9 Hz, 1H), 0.39 (d, J ) 2.4
Hz, 9H); 13C NMR (75 MHz, CDCl3) δ 154.4 (dd, J ) 246.5, 12.3
Hz), 153.3 (dd, J ) 258.5, 17.9 Hz), 150.6 (d, J ) 8.9 Hz), 125.6
(d, J ) 29.9 Hz), 120.9 (dd, J ) 7.4, 6.5 Hz), 117.9 (d, J ) 18.8
Hz), -0.2 (d, J ) 7.7 Hz); MS (CI, CH4) m/ z 232, 216, 160. Anal.
Calcd for C9H11F2NO2Si: C, 46.74; H, 4.79; N, 6.06. Found: C,
46.47; H, 4.48; N, 5.95.
3-F lu or o-2-(tr im eth ylsilyl)n itr oben zen e (Ta ble 2, en tr y
11): IR (film) 3100, 2980, 2953, 1607, 1535, 1441, 1358, 1235,
1109, 850 cm-1; 1H NMR (200 MHz, acetone-d6) δ 7.65 (dd, J )
8.0, 1.0 Hz, 1H), 7.48 (dt, J ) 8.2, 5.5 Hz, 1H), 7.50 (dt, J ) 8.6,
1.1 Hz, 1H), 0.39 (d, J ) 2.3 Hz, 9H); 13C NMR (75 MHz, CDCl3)
δ 167.0 (d, J ) 245.6 Hz), 156.4, 131.3 (d, J ) 9.5 Hz), 122.3 (d,
J ) 34.3 Hz), 119.8 (d, J ) 28.3 Hz), 119.4 (d, J ) 3.1 Hz), 0.2
(d, J ) 4.4 Hz); MS (CI, CH4) m/ z 214, 198. Anal. Calcd for
C9H12FNO2Si: C, 50.68; H, 5.67; N, 6.67. Found: C, 50.90; H,
5.69; N, 6.52.
2,4-Diflu or o-3-(tr im eth ylsta n n yl)n itr oben zen e (3). To a
-78 °C solution of 0.83 mL (3.46 mmol) of (tert-butyldimethyl-
silyl)-tert-butylamine in THF (5 mL) was added 2.14 mL (3.29
mmol) of n-BuLi (1.54 M in hexane), and the solution was
allowed to warm to 0 °C to provide a solution of LiBSBA. In a
separate flask, a solution of 0.3 mL (2.74 mmol) of 2,4-difluoro-
1-nitrobenzene in THF (10 mL) was cooled to -78 °C, and 1.64
mL (4.11 mmol) of Me3SnCl (2.5 M in THF) was added. The
LiBSBA solution was then added dropwise to maintain an
internal temperature below -74 °C. The resulting mixture was
stirred for 30 min at -78 °C and then partitioned between 1 M
HCl and Et2O. The aqueous phase was separated and extracted
with ether. The combined organic phases were washed with 1
M HCl (3×) and brine, dried over MgSO4, and concentrated.
Purification by flash chromatography (10% acetone/hexane)
provided 636 mg (75%) of the title compound: IR (film) 3090,
2990, 1600, 1580, 1525, 1445, 1345, 995, 745 cm-1; 1H NMR (200
MHz, acetone-d6) δ 8.17 (dt, J ) 8.8, 5.9 Hz, 1H), 7.16 (dd, J )
8.97, 5.8 Hz, 1H), 0.50 (m, 9H); 13C NMR (75 MHz, CDCl3) δ
169.7 (dd, J ) 321.8, 19.2 Hz), 159.7 (dd, J ) 252.9, 21.1 Hz),
133.8 (d, J ) 10.1 Hz), 128.8 (dd, J ) 10.7, 2.1 Hz), 118.1 (dd, J
) 51.2, 48.9 Hz), 111.4 (dd, J ) 26.8, 3.6 Hz), -7.7 (s, with tin
satellites at 185 Hz); MS (CI, CH4) m/ z 324, 322, 320, 160. Anal.
Calcd for C9H11F2NO2Sn: C, 33.59; H, 3.44; N, 4.37. Found:
C, 33.48; H, 3.43; N, 4.40.
2-(Tr im et h ylsilyl)-1,3-d in it r ob en zen e (Ta b le 2, en t r y
12): mp 94-95 °C; IR (film) 3090, 2970, 1538, 1355, 1287, 1256,
1047, 905, 840, 713 cm-1; 1H NMR (200 MHz, acetone-d6) δ 8.03
(d, J ) 7.7 Hz, 2H), 7.62 (t, J ) 7.7 Hz, 1H), 0.38 (s, 9H); 13C
NMR (100 MHz, CDCl3) δ 157.2, 131.7, 130.4, 126.8, -0.63; MS
(CI, CH4) m/ z 241, 225. Anal. Calcd for C9H12N2O4Si: C, 44.97;
H, 5.03; N, 11.70. Found: C, 45.30; H, 4.66; N, 11.54.
2-(2,4-Diflu or op h en oxy)-4-flu or o-3-(t r im et h ylsilyl)n i-
tr oben zen e (Ta ble 2, en tr y 13): IR (film) 3083, 2958, 1595,
1547,1505, 1345, 1250, 1205, 845 cm-1 1H NMR (200 MHz,
;
acetone-d6) δ 8.20 (dd, J ) 9.0, 6.0 Hz, 1H), 7.30 (dd, J ) 9.0,
8.0 Hz, 1H), 7.23 (ddd, J ) 11.1, 7.9, 3.2 Hz, 1H), 6.86 (m, 1H),
J O961839T