ꢀ
P. Acs et al. / Tetrahedron 62 (2006) 12051–12056
12055
5.94; N, 11.00. Found: C, 56.41; H, 5.73; N, 10.81. Yield:
80%. Isolated as pale brown crystalline material. Mp 169–
171 ꢀC.
6.34 (br s, 2H, NH2); 4.50 (dd, 8.2 Hz, 5.2 Hz, 1H,
NHCH); 3.68 (s, 3H, OCH3); 2.20 (m, 1H, CH(CH3)2);
0.87 (d, 6.8 Hz, 3H, CH3); 0.84 (d, 6.8 Hz; 3H, CH3). MS
(m/z/rel int.): 278 (M+)/10; 120/100; 92/21. Anal. Calcd
for C14H18N2O4 (278.31): C, 60.42; H, 6.52; N, 10.07.
Found: C, 60.32; H, 6.76; N, 10.02. Yield: 48%. Isolated
as brown powder-like crystalline material. Mp 121–123 ꢀC.
4.4.10. N-tert-Butyl-(2-amino-5-bromo-phenyl)-glyoxyl-
amide (5d). H NMR (CDCl3) d: 8.62 (s, 1H, Ar-H); 7.33
1
(d, 8 Hz, 1H, Ar-H); 6.70 (br s, 1H, CONH); 6.52 (d, 8 Hz,
1H, Ar-H); 6.25 (br s, 2H, NH2); 1.40 (s, 9H, C(CH3)3).
13C NMR (CDCl3) d: 188.8; 162.6; 150.9; 135.9; 133.1;
120.5; 118.3; 114.9; 51.8; 28.4. IR (KBr, cmꢁ1): 3490,
3350 (br, diffuse), 1690, 1650, 1611. MS (m/z/rel int.):
300(298) (M+)/27(26); 200(198)/96(95); 57/100. Anal.
Calcd for C12H15N2O2Br (299.17): C, 48.18; H, 5.05; N,
9.36. Found: C, 48.05; H, 5.22; N, 9.17. Yield: 83%. Isolated
as brown crystalline material. Mp 187–189 ꢀC.
4.4.16. Methyl N-{(20-amino-phenyl)glyoxyloyl}-proli-
nate (9a). H NMR (CDCl3) d: 7.70 (d, 8 Hz, 1H, Ar-H);
1
7.23 (t, 8 Hz, 1H, Ar-H); 6.58–6.70 (m, 2H, Ar-H); 6.35
(br s, 2H, NH2); 4.60 (m, 1H, CHCOOCH3); 3.76 (s, 3H,
OCH3); 3.40–3.50 (m, 2H, NCH2); 1.9–2.3 (m, 4H,
CH2CH2). 13C NMR (CDCl3) d: 193.2; 172.0; 165.3;
152.0; 136.0; 133.8; 132.0; 116.9; 116.2; 58.0; 52.4; 47.3;
19.3; 14.5. IR (KBr, cmꢁ1): 3480, 3340 (br, diffuse), 1726,
1656. MS (m/z/rel int.): 276 (M+)/10; 120/100; 92/20.
Anal. Calcd for C14H16N2O4 (276.29): C, 60.86; H, 5.84;
N, 10.14. Found: C, 60.77; H, 5.98; N, 10.02. Yield: 68%.
Isolated as yellow powder-like crystalline material. Mp
143 ꢀC.
4.4.11. N-tert-Butyl-(2-amino-5-cyano-phenyl)-glyoxyl-
amide (5e). H NMR (CDCl3) d: 8.95 (s, 1H, Ar-H); 7.42
1
(d, 8 Hz, 1H, Ar-H); 7.22 (s, 1H, CONH); 6.70 (br s, 2H,
NH2); 6.62 (d, 8 Hz, 1H, Ar-H); 1.43 (s, 9H, C(CH3)3).
13C NMR (CDCl3) d: 188.6; 161.8; 154.4; 140.5; 137.3;
119.0; 117.6; 114.1; 51.9; 28.4. IR (KBr, cmꢁ1): 3480,
3340 (br, diffuse), 2240, 1700, 1652, 1605. MS (m/z/rel
int.): 245 (M+)/20; 145/65; 118/94; 57/100. Anal. Calcd
for C13H15N3O2 (245.28): C, 63.66; H, 6.16; N, 17.13.
Found: C, 63.55; H, 6.37; N, 16.97. Yield: 68%. Isolated
as pale brown crystalline material. Mp 170–171 ꢀC.
4.4.17. Methyl N-{(20-amino-50-methyl-phenyl)glyoxyl-
oyl}-prolinate (9b). 1H NMR (CDCl3) d: 7.50 (s, 1H,
Ar-H); 7.13 (d, 8 Hz, 1H, Ar-H); 6.58 (d, 8 Hz, 1H, Ar-H);
6.15 (br s, 2H, NH2); 4.63 (m, 1H, CHCOOCH3); 3.80 (s,
3H, OCH3); 3.40–3.50 (m, 2H, NCH2); 2.24 (s, 3H,
ArCH3); 1.9–2.3 (m, 4H, CH2CH2). 13C NMR (CDCl3) d:
193.3; 171.9; 165.8; 149.8; 137.4; 133.0; 125.5; 116.8;
113.4; 58.0; 52.3; 47.0; 24.6; 20.2. IR (KBr, cmꢁ1): 3490,
3370 (br, diffuse), 1776, 1676. MS (m/z/rel int.): 290 (M+)/
13; 134/100; 106/22. Anal. Calcd for C15H18N2O4
(290.32): C, 62.06; H, 6.25; N, 9.65. Found: C, 62.01; H,
6.38; N, 9.47. Yield: 71%. Isolated as yellow crystalline
material. Mp 155–157 ꢀC.
4.4.12. N-tert-Butyl-(2-amino-5-nitro-phenyl)-glyoxyl-
amide (5f). H NMR (CDCl3) d: 9.60 (s, 1H, Ar-H); 8.13
1
(d, 8 Hz, 1H, Ar-H); 7.05 (br s, 2H, NH2); 6.80 (br s, 1H,
CONH); 6.70 (d, 8 Hz, 1H, Ar-H); 1.41 (s, 9H, C(CH3)3).
13C NMR (CDCl3) d: 188.9; 161.7; 156.1; 137.1; 132.3;
130.2; 117.0; 112.5; 52.0; 28.4. IR (KBr, cmꢁ1): 3440 (br,
diffuse), 1690, 1653. Anal. Calcd for C12H15N3O4
(265.27): C, 54.33; H, 5.70; N, 15.84. Found: C, 54.20; H,
5.88; N, 15.67. Yield: 86%. Isolated as orange crystalline
material. Mp 219 ꢀC.
4.4.18. Methyl N-{(20-amino-50-chloro-phenyl)glyoxyl-
oyl}-prolinate (9c). 1H NMR (CDCl3) d: 7.70 (s, 1H,
Ar-H); 7.23 (d, 8 Hz, 1H, Ar-H); 6.62 (d, 8 Hz, 1H, Ar-H);
6.35 (br s, 2H, NH2); 4.63 (m, 1H, CHCOOCH3); 3.82 (s,
3H, OCH3); 3.40–3.50 (m, 2H, NCH2); 1.9–2.3 (m, 4H,
CH2CH2). 13C NMR (CDCl3) d: 192.5; 171.9; 165.0;
150.3; 136.0; 132.4; 128.4; 120.8; 118.4; 58.3; 52.2; 47.0;
29.1; 24.4. IR (KBr, cmꢁ1): 3480, 3355 (br, diffuse), 1772,
1674. MS (m/z/rel int.): 312(310) (M+)/3(1); 128/100.
Anal. Calcd for C14H15N2O4Cl (310.74): C, 54.11; H,
4.87; N, 9.02. Found: C, 54.23; H, 4.98; N, 9.17. Yield:
65%. Isolated as yellow crystalline material. Mp 155–
156 ꢀC.
4.4.13. Methyl N-{(20-amino-phenyl)glyoxyloyl}-glyci-
nate (7a). H NMR (CDCl3) d: 8.20 (d, 8 Hz, 1H, Ar-H);
1
7.40 (t, 8 Hz, 1H, Ar-H); 6.62–6.74 (m, 3H, Ar-H+CONH);
6.35 (br s, 2H, NH2); 4.18 (d, 5.6 Hz, 2H); 3.71 (s, 3H,
OCH3). MS (m/z/rel int.): 236 (M+)/21; 208/6; 120/100;
92/28. Anal. Calcd for C11H12N2O4 (236.23): C, 55.93; H,
5.12; N, 11.86. Found: C, 55.80; H, 5.31; N, 11.69. Yield:
46%. Isolated as waxy yellow material.
4.4.14. Methyl N-{(20-amino-phenyl)glyoxyloyl}-alani-
1
nate (7a0). H NMR (CDCl3) d: 8.30 (d, 8 Hz, 1H, Ar-H);
7.43 (t, 8 Hz, 1H, Ar-H); 6.60–6.72 (m, 3H, Ar-H+CONH);
6.23 (br s, 2H, NH2); 4.60 (qi, 7.5 Hz, 1H, CHCH3); 3.71
(s, 3H, OCH3); 1.45 (d, 7.5 Hz, 3H, CHCH3). 13C NMR
(CDCl3) d: 188.5; 172.5; 163.3; 151.7; 136.0; 134.1; 132.0;
116.7; 116.0; 52.5; 48.0; 18.0. IR (KBr, cmꢁ1): 3480, 3370
(br, diffuse), 1745, 1688, 1632. MS (m/z/rel int.): 250 (M+)/
17; 120/100; 92/20. Anal. Calcd for C12H14N2O4 (250.25):
C, 57.59; H, 5.64; N, 11.19. Found: C, 57.30; H, 5.81; N,
10.95. Yield: 48%. Isolated as waxy yellow material.
4.4.19. Methyl N-{(20-amino-50-nitro-phenyl)glyoxyloyl}-
prolinate (9f). 1H NMR (CDCl3) d: 8.60 (d, 1.4 Hz, 1H, Ar-
H); 8.03 (dd, 1.4 Hz, 8 Hz, 1H, Ar-H); 7.3 (br s, 2H, NH2);
6.73 (d, 8 Hz, 1H, Ar-H); 4.61 (m, 1H, CHCOOCH3); 3.82
(s, 3H, OCH3); 3.40–3.50 (m, 2H, NCH2); 1.9–2.3 (m, 4H,
CH2CH2). 13C NMR (CDCl3) d: 192.1; 171.7; 164.2;
156.0; 137.1; 131.4; 131.0; 117.5; 112.0; 58.8; 52.6;
47.0; 29.1; 24.1. IR (KBr, cmꢁ1): 3430, 3300 (br, diffuse),
1722, 1654. MS (m/z/rel int.): 321 (M+)/2; 253/9; 128/100.
Anal. Calcd for C14H15N3O6 (321.29): C, 52.34; H, 4.71;
N, 13.08. Found: C, 52.22; H, 4.78; N, 13.19. Yield: 58%.
Isolated as red-brown powder-like crystalline material. Mp
188–190 ꢀC.
4.4.15. Methyl N-{(20-amino-phenyl)glyoxyloyl}-valinate
1
(7a00). H NMR (CDCl3) d: 8.25 (d, 8 Hz, 1H, Ar-H); 7.42
(t, 8 Hz, 1H, Ar-H); 6.65–6.75 (m, 3H, Ar-H+CONH);