W.-t. Xiong et al. / Tetrahedron 67 (2011) 5235e5243
5241
Yellow oil. 1H NMR (CDCl3, 300 MHz):
d
8.12 (1H, br s, NH), 7.87 (1H,
75 MHz):
d
155.2 (C]O, t, J¼34 Hz), 135.6, 131.9 (q, J¼32 Hz), 130.0,
s), 7.80 (1H, d, J¼6.6 Hz), 7.57e7.52 (2H, m). 19F NMR (CDCl3,
123.9, 123.4 (CF3, q, J¼271 Hz), 123.2 (q, 3J¼4.0 Hz), 117.7 (q,
3J¼4.0 Hz). IR (KBr) cmꢀ1: 3316, 1712, 1558, 1455, 1334, 1227, 1171,
1137, 1073. MS (EI) m/z: 357 (Mþ, 27), 188 (ArNHCOþ, 78), 160
282 MHz):
d
ꢀ63.1 (3F, s, ArCF3), ꢀ64.9 (2F, s, ICF2), ꢀ78.4 (2F, t,
J¼12 Hz, CF2O), ꢀ85.6 (2F, t, J¼12.4 Hz, OCF2). 13C NMR (CDCl3,
2
2
100 MHz):
d
155.2 (t, JCeF¼34 Hz), 135.7, 132.0 (q, JCeF¼33 Hz),
(ArNHþ, 100), 145 (CF3C6H4
þ, 94), 69 (CF3þ, 99). HRMS (EI) m/z calcd
for C11H5F10NO: 357.0211; found: 357.0207.
130.1, 123.6, 123.5 (q, J¼271 Hz), 123.0 (q, J¼4.0 Hz), 117.4 (q,
3JCeF¼4.0 Hz), 114.8 (t-t, J¼285,31 Hz), 113.9 (t, J¼285 Hz), 89.5 (t-
t, J¼318, 42 Hz). IR (KBr) cmꢀ1: 3314, 2929, 1720, 1560, 1456, 1332,
4.1.11. 30-Trifluoromethyl-isopropoxyoxalanilide 3eb.
1148. MS (EI) m/z: 481 (Mþ, 21), 226 (ICF2CF2
þ
ꢀ1, 25), 187
(ArNHCOþꢀ1, 100), 160 (ArNHþ, 84), 145 (CF3C6H4
þ
, 67), 100
F3C
(HCF2CF2
found: 480.9222.
þ
ꢀ1, 59). HRMS (EI) m/z calcd for C11H5F9INO2: 480.9221;
O O
N C C O
H
4.1.8. 30-Trifluoromethyl-2,2-difluoro-2-(1,1,2,2-tetrafluoroethoxy)
acetanilide 3bb.
Yellow oil. 1H NMR (CDCl3, 300 MHz):
d 9.10 (1H, br s, NH), 7.94
(1H, s), 7.89 (1H, d, J¼7.8 Hz), 7.48 (2H, quint, J¼7.8 Hz), 5.21 (1H,
F3C
sept, J¼6.3 Hz, OCH), 1.40 (6H, d, J¼6.0 Hz, 2CH3). 19F NMR (CDCl3,
O
282 MHz):
d
ꢀ62.8 (3F, s, ArCF3). 13C NMR (CDCl3, 75 MHz):
d 160.2,
N C CF2OCF2CF2H
H
154.6, 137.0, 131.6 (q, J¼33 Hz), 129.8, 123.7 (q, J¼270 Hz), 123.0,
122.0 (q, J¼4.0 Hz), 116.7 (d, J¼3.0 Hz), 72.5, 21.5. IR (KBr) cmꢀ1
:
3292, 2987, 1698, 1552, 1452, 1333, 1168, 1128, 1073. MS (EI) m/z:
Yellow oil. 1H NMR (CDCl3, 300 MHz):
d 8.15 (1H, br s, NH), 7.86
275 (Mþ, 10), 188 (ArNHCOþ, 17), 160 (ArNHþ, 14), 145 (CF3C6H4
10), 43 (C3H7 , 100). HRMS (EI) m/z calcd for C12H12F3NO3:
275.0769; found: 275.0765.
þ,
(1H, s), 7. 79 (1H, d, J¼6.9 Hz), 7.56e7.49 (2H, m), 5.90 (1H, t-t,
þ
J¼3.0, 53 Hz, HCF2). 19F NMR (CDCl3, 282 MHz):
d
ꢀ63.3 (3F, s,
ArCF3), ꢀ78.2 (2F, t, J¼12 Hz, CF2O), ꢀ88.5 (2F, s, OCF2), ꢀ137.5 (2F,
d, J¼53.3 Hz, CF2H). 13C NMR (CDCl3, 100 MHz):
d 156.2 (C]O, t,
4.1.12. 20-Chloro-50-trifluoromethyl-2,2-difluoro-2-(1,1,2,2-
tetrafluoroethoxy)acetanilide 3bd.
J¼35 Hz), 135.7, 131.8 (q, J¼33 Hz), 129.9, 124.0, 123.5 (CF3, q,
J¼271 Hz), 123.0 (q, 2J¼4.0 Hz), 117.7 (q, J¼4.0 Hz), 116.3 (t-t, J¼252,
40 Hz), 114.0 (OCF2, t, J¼284 Hz), 106.9 (HCF2, t-t, J¼252, 39 Hz). IR
(KBr) cmꢀ1: 3435, 3311, 1722, 1610, 1563, 1497, 1456, 1333, 1131. MS
(EI) m/z: 355 (Mþ, 28), 188 (ArNHCOþ, 100), 160 (ArNHþ, 79), 145
F3C
O
N C CF2OCF2CF2H
H
(CF3C6H4þ, 66), 101 (HCF2CF2þ, 63), 51 (HCF2þ, 55). HRMS (EI) m/z
calcd for C11H6F9NO2: 355.0255; found: 355.0257.
Cl
4.1.9. 30-Trifluoromethyl-2,2-difluoro-2-(2-chloro-1,1,2,2-
tetrafluoroethoxy)acetanilide 3cb.
Yellow oil. 1H NMR (CDCl3, 300 MHz):
d 8.68 (1H, s), 8.58 (1H, br
s, NH), 7.59 (1H, d, J¼8.7 Hz), 7.45 (1H, dd, J¼2.1, 8.7 Hz), 5.92 (1H, tt,
J¼2.7, 52.8 Hz, HCF2). 19F NMR (CDCl3, 282 MHz):
d
ꢀ62.9 (3F, s,
F3C
ArCF3), ꢀ77.8 (2F, t, J¼11.8 Hz, CF2O), ꢀ88.0 (2F, m, OCF2), ꢀ137.1
O
(2F, td, J¼4.5, 55.5 Hz, CF2H). 13C NMR (CDCl3, 75 MHz):
d 155.5 (t,
N C CF2OCF2CF2Cl
H
J¼35.0 Hz), 132.8, 130.6 (q, J¼33 Hz), 129.9, 127.3, 123.3 (q,
J¼3.0 Hz), 123.2 (q, J¼271 Hz), 118.6 (q, J¼5.0 Hz), 116.3 (t-t, J¼280,
30 Hz), 113.7 (t, J¼284 Hz), 106.9 (t-t, J¼252, 40 Hz). IR (KBr) cmꢀ1
:
Yellow oil. 1H NMR (CDCl3, 300 MHz):
d 8.11 (1H, br s, NH), 7.87
3402, 1745, 1596, 1547, 1435, 1333, 1133, 1083. MS (EI) m/z: 391/389
(1H, s), 7. 80 (1H, d, J¼6.0 Hz), 7.57e7.52 (2H, m). 19F NMR (CDCl3,
(Mþ, 3/10), 354 (MþꢀCl, 40), 222 (ArNHCOþ, 33), 194 (ArNHþ, 54),
282 MHz):
d
ꢀ62.9 (3F, s, ArCF3), ꢀ73.6 (2F, s, ClCF2), ꢀ78.2 (2F, t,
101 (HCF2CF2þ, 100), 51 (HCF2þ, 51). HRMS (EI) m/z calcd for
J¼12.1 Hz, CF2O), ꢀ86.7 (2F, t, J¼12.1 Hz, OCF2). 13C NMR (CDCl3,
C11H5ClF9NO2: 388.9865; found: 388.9849.
75 MHz):
d
155.3 (t, J¼34 Hz), 135.7, 131.9 (q, J¼33 Hz), 130.0, 123.7,
4.1.13. 2-Chloro-50-trifluoromethyl-isopropoxyoxalanilide 3fd.
123.5 (q, J¼271 Hz), 123.1 (q, J¼4 Hz), 117.5 (q, J¼4 Hz). IR (KBr)
cmꢀ1: 3313, 1718, 1561, 1456, 1333, 1180, 1137. MS (EI) m/z: 388
(Mþꢀ1, 12), 188 (ArNHCOþ, 100), 160 (ArNHþ, 63), 145 (CF3C6H4
þ,
F3C
O O
43), 135 (ClCF2CF2þ, 30), 85 (ClCF2þ, 29). HRMS (EI) m/z calcd for
C11H5F9ClNO2: 388.9865; found: 388.9865.
N C C O
H
4.1.10. 30-Trifluoromethyl-2,2,3,3,4,4,4-heptafluorobutyranilide 3db.
Cl
F3C
Orange solid, mp 58e60 ꢁC. 1H NMR (CDCl3, 300 MHz):
d 9.58
O
(1H, br s, NH), 8.81 (1H, s), 7.55 (1H, d, J¼8.1 Hz), 7.39 (1H, d,
N C
H
CF2CF2CF3
J¼8.1 Hz), 5.24 (1H, sept, J¼6.3 Hz, OCH), 1.43 (6H, d, J¼6.6 Hz,
2CH3). 19F NMR (CDCl3, 282 MHz):
d
ꢀ62.8 (3F, s ArCF3). 13C NMR
(CDCl3, 75 MHz):
d
159.5, 154.3, 133.9, 130.3 (q, J¼33 Hz), 129.7,
Yellow oil. 1H NMR (CDCl3, 300 MHz):
d 8.10 (1H, br s, NH), 7.86
126.6 (m), 123.2 (q, J¼271 Hz), 122.2 (q, J¼4.0 Hz), 117.8 (q,
(1H, s), 7. 79 (1H, d, J¼6.9 Hz), 7.55e7.52 (2H, m). 19F NMR (CDCl3,
J¼4.0 Hz), 72.6, 21.4. IR (KBr) cmꢀ1: 3365, 2987, 1722, 1534, 1330,
1129, 1102, 1082. MS (EI) m/z: 311/309 (Mþ, 1/3), 43 (C3H7
þ, 100).
282 MHz):
d
ꢀ62.9 (3F, s, ArCF3), ꢀ80.5 (3F, t, J¼8.7 Hz, CF3), ꢀ120.3
(2F, quart, J¼8.5 Hz, CF2), ꢀ126.7 (2F, s, CF2). 13C NMR (CDCl3,
HRMS (EI) m/z calcd for C12H11ClF3NO3: 309.0380; found: 309.0384.