R. Csuk et al. / Tetrahedron 60 (2004) 5737–5750
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1H, NH). 13C NMR (100 MHz, CDCl3): d¼52.0, 111.2 (dd,
J¼18.4, 4.6 Hz), 112.7, 113.7, 118.0, 118.1, 126.3 (dd, J¼
9.2, 3.1 Hz), 131.6, 134.1, 140.7 (ddd, J¼250.9, 16.1,
16.1 Hz), 145.7 (ddd, J¼247.1, 10.7, 2.3 Hz), 147.0, 147.4
(ddd, J¼247.1, 10.7, 2.3 Hz), 145.7 (ddd, J¼247.1, 10.7,
2.3 Hz), 168.6. 19F NMR (188 MHz, CDCl3): d¼2140.0
(m, F), 2143.7 (d, J¼20.1 Hz, F), 2158.6 (ddd, J¼23.1,
23.1, 8.4 Hz, F). IR (KBr): n¼3304m, 2997w, 2955m,
1682s, 1615s, 1589s, 1536s, 1514s, 1491s, 1455m, 1436s,
1330m, 1315m, 1293m, 1255s, 1221s, 1191m, 1168m,
1141m, 1090s, 1060m, 1042m cm21. UV–vis (methanol):
168.2. 19F NMR (188 MHz, CDCl3): d¼258.7 (s, OCF3).IR
(KBr): n¼3321m, 2957m, 1697s, 1599s, 1576s, 1516s,
1439m, 1425s, 1406m, 1321m, 1257s, 1226s, 1200s, 1153s,
1100s, 1080w, 1014w cm21. UV–vis (methanol): lmax
(log 1)¼243 nm (4.40). MS (ESI, MeOH): m/z¼344.2
(100%, (M2H)2). HRMS for C15H11ClF3NO3: calcd:
345.0380; found: 345.0381.
3.5.33. Methyl 4-chloro-2-(2,4-difluoroanilino)benzoate
(7s). Compound 7s (1.7 g, 86%) was obtained from methyl
4-chloro-2-iodobenzoate (2.0 g, 6.8 mmol) and 2,4-difluoro-
aniline (1.1 g, 8.5 mmol) following GP2. Mp 89–91 8C. 1H
NMR (400 MHz, CDCl3): d¼3.89 (s, 3H, OCH3), 6.69 (dd,
1H, J¼8.7, 2.1 Hz, Harom), 6.78 (t, 1H, J¼1.7 Hz, Harom),
6.86–6.96 (m, 2H, Harom), 7.28–7.34 (m, 1H, Harom), 7.87
(d, 1H, J¼8.7 Hz, Harom), 9.30 (s, 1H, NH). 13C NMR
(100 MHz, CDCl3): d¼52.0, 105.0 (dd, J¼23.8, 23.8 Hz),
110.3, 111.4 (dd, J¼21.5, 3.8 Hz), 112.8, 117.6, 123.7 (dd,
J¼12.3, 3.1 Hz), 126.9 (dd, J¼10.0, 2.3 Hz), 132.7, 140.6,
149.0, 156.9 (dd, J¼247.1, 10.7 Hz), 159.9 (dd, J¼250.1,
12.3 Hz), 168.1. 19F NMR (188 MHz, CDCl3): d¼2113.6
(m, F), 2118.5 (m, F). IR (KBr): n¼3294w, 3070w,
2959w, 1693s, 1603m, 1579s, 1518s, 1435m, 1328m,
1287m, 1261s, 1245s, 1206m, 1186m, 1144m, 1101s,
1085m cm21. UV–vis (methanol): lmax (log 1)¼242 nm
(4.50). MS (ESI, MeOH): m/z¼296.3 (100%, (M2H)2).
HRMS for C14H10ClF2NO2: calcd: 297.0368; found:
297.0366.
l
max (log 1)¼233 nm (4.47). MS (ESI, MeOH): m/z¼282.0
(100%, (MþH)þ). HRMS for C14H10F3NO2: 281.0664;
found: 281.0664.
3.5.30. Methyl 2-(2,4-dimethoxyanilino)benzoate (7p).
Compound 7p (2.1 g, 97%) was obtained from methyl
2-iodobenzoate (2.0 g, 7.6 mmol) and 2,4-dimethoxyaniline
(1.4 g, 9.1 mmol) following GP2. 1H NMR (500 MHz,
CDCl3): d¼3.80 (s, 3H, OCH3), 3.81 (s, 3H, OCH3), 3.88 (s,
3H, OCH3), 6.46 (dd, 1H, J¼8.5, 3.1 Hz, Harom), 6.54 (d,
1H, J¼3.1 Hz, Harom), 6.64 (ddd, 1H, J¼7.9, 6.7, 1.2 Hz,
Harom), 6.95 (d, 1H, J¼8.5 Hz, Harom), 7.21–7.26 (m, 2H,
Harom), 7.92 (dd, 1H, J¼8.5, 1.2 Hz, Harom), 9.13 (s, 1H,
NH). 13C NMR (125 MHz, CDCl3): d¼51.6, 55.5, 55.7,
99.6, 103.9, 111.3, 113.4, 116.1, 122.7, 124.8, 131.5, 134.0,
149.1, 154.2, 157.4, 168.9. IR (kap.): n¼3333m, 3001w,
2950m, 2836w, 1686s, 1604s, 1578m, 1519s, 1454s, 1437s,
1415m, 1249s, 1209s, 1188m, 1159s, 1129m, 1084s,
1035m cm21. UV–vis (methanol): lmax (log 1)¼233 nm
(4.46). MS (ESI, MeOH): m/z¼288.4 (100%, (MþH)þ).
HRMS for C16H17NO4: calcd: 287.1158; found: 287.1155.
3.5.34. Methyl 4-chloro-2-(2,3,4-trifluoroanilino)benzo-
ate (7t). Compound 7t (1.2 g, 54%) was prepared from
methyl 4-chloro-2-iodobenzoate (2.0 g, 6.8 mmol) and
2,3,4-trifluoroaniline (1.2 g, 8.1 mmol) following GP2. Mp
122–124 8C. 1H NMR (400 MHz, CDCl3): 3.90 (s, 3H,
OCH3), 6.74 (dd, 1H, J¼8.7, 2.1 Hz, Harom), 6.83 (t, 1H,
J¼1.6 Hz, Harom), 6.94–7.02 (m, 1H, Harom), 7.04–7.12 (m,
1H, Harom), 7.89 (d, 1H, J¼8.7 Hz, Harom), 9.39 (s, 1H, NH).
13C NMR (100 MHz, CDCl3): d¼52.1, 110.7, 111.6 (dd,
J¼17.6, 3.8 Hz), 113.1, 118.2, 119.1 (dd, J¼7.7, 3.8 Hz),
125.3 (dd, J¼9.2, 3.1 Hz), 132.8, 140.6 (ddd, J¼252.4,
14.6, 14.6 Hz), 140.6, 146.1 (ddd, J¼249.4, 12.3, 3.8 Hz),
148.3 (ddd, J¼247.8, 10.0, 2.3 Hz), 148.3, 168.1. 19F NMR
(188 MHz, CDCl3): d¼2138.1 (m, F), 2142.3 (m, F),
2157.8 (ddd, J¼23.1, 23.1, 8.4 Hz, F). IR (KBr): n¼
3244m, 2969w, 1696s, 1617s, 1594s, 1534s, 1515s, 1491s,
1441m, 1419m, 1328m, 1293m, 1257s, 1217m, 1190w,
1168w, 1151w, 1105m, 1082w, 1049s cm21. UV–vis
(methanol): lmax (log 1)¼241 nm (4.42). MS (ESI,
MeOH): m/z¼300.3 (90%, (M2H)2), 623.3 (100%
[(M2H)2Na]2). HRMS for C14H9ClF3NO2: calcd:
315.0274; found: 315.0274.
3.5.31. Methyl 2-(2,5-dimethoxyanilino)benzoate (7q).78
Compound 7q (1.6 g, 73%) was obtained as an oil from
methyl 2-iodobenzoate (2.0 g, 7.6 mmol) and 2,5-dimethoxy-
aniline (1.4 g, 9.1 mmol) following GP2. 1H NMR
(400 MHz, CDCl3): d¼3.75 (s, 3H, OCH3), 3.84 (s, 3H,
OCH3), 3.89 (s, 3H, OCH3), 6.51 (dd, 1H, J¼9.1, 2.9 Hz,
Harom), 6.74 (ddd, 1H, J¼7.1, 7.1, 1.3 Hz, Harom), 6.83 (d,
1H, J¼8.7 Hz, Harom), 7.03 (d, 1H, J¼2.9 Hz, Harom), 7.32
(ddd, 1H, J¼7.1, 6.6, 1.7 Hz, Harom), 7.38 (dd, 1H, J¼8.7,
1.3 Hz, Harom), 7.95 (dd, 1H, J¼7.9, 1.7 Hz, Harom), 9.45 (s,
1H, NH). 13C NMR (100 MHz, CDCl3): d¼51.8, 55.8, 56.5,
106.5, 106.7, 112.0, 113.2, 114.7, 117.4, 131.1, 131.5,
133.8, 145.5, 146.5, 153.6, 168.4. IR (film): n¼3328m,
3078w, 2999m, 2950m, 2834m, 1732m, 1690s, 1597s,
1579s, 1526s, 1455s, 1436s, 1314s, 1288s, 1260s, 1217s,
1200s, 1180s, 1164m, 1132s, 1085s, 1046s, 1026m cm21
.
UV–vis (methanol): lmax (log 1)¼233 nm (4.50). MS (ESI,
MeOH): m/z¼288.1 (100%, (MþH)þ). HRMS for
C16H17NO4: calcd: 287.1158; found: 287.1159.
3.5.35. Methyl 5-nitro-2-[4-(trifluoromethoxy)anilino]-
benzoate (7u). Compound 7u (2.0 g, 87%) was prepared
from methyl 2-iodo-5-nitrobenzoate (2.0 g, 6.5 mmol) and
4-trifluoromethoxyaniline (1.4 g, 7.9 mmol) following GP2.
Mp 49–52 8C. 1H NMR (400 MHz, CDCl3): d¼3.96 (s, 3H,
OCH3), 7.03 (d, 1H, J¼9.5 Hz, Harom), 7.24–7.30 (m, 4H,
Harom), 8.13 (dd, 1H, J¼9.5, 2.5 Hz, Harom), 8.95 (d, 1H,
J¼2.5 Hz, Harom), 10.13 (s, 1H, NH). 13C NMR (100 MHz,
CDCl3): d¼52.5, 110.5, 112.9, 120.4 (q, J¼275.4 Hz),
122.4, 125.8, 128.8, 129.4, 137.0, 137.8, 146.8, 152.4,
167.6. 19F NMR (188 MHz, CDCl3): d¼258.7 (s, OCF3).
3.5.32. Methyl 4-chloro-2-[4-(trifluoromethoxy)anilino]-
benzoate (7r). Compound 7r (2.1 g, 90%) was obtained
from methyl 4-chloro-2-iodobenzoate (2.0 g, 6.8 mmol) and
4-trifluoromethoxyaniline (1.5 g, 8.5 mmol) following GP2.
1
Mp 104–105 8C. H NMR (400 MHz, CDCl3): d¼3.89 (s,
3H, OCH3), 6.70 (dd, 1H, J¼8.3, 1.7 Hz, Harom), 7.1 (d, 1H,
J¼2.1 Hz, Harom), 7.16–7.24 (m, 4H, Harom), 7.88 (d, 1H,
J¼8.3 Hz, Harom), 9.53 (s, 1H, NH). 13C NMR (100 MHz,
CDCl3): d¼52.0, 110.4, 113.2, 117.8, 120.5 (q, J¼
256.6 Hz), 122.3, 124.1, 132.9, 138.6, 140.6, 145.5, 148.6,