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A. Takaꢀcs et al. / Tetrahedron 63 (2007) 10372–10378
(34), 135 (98), 106 (81), 78 (100). Analysis calculated for
C9H10N2O3 (194.19): C, 55.67; H, 5.19; N, 14.43. Found:
C, 55.62; H, 5.33; N, 14.28. Yield: 61%.
57 (100). Analysis calculated for C11H14N2O3 (206.24): C,
64.06; H, 6.84; N, 13.58. Found: C, 64.01; H, 6.97; N,
13.38. Yield: 44%.
4.4.8. 2-(N-(10-Methoxycarbonyl-ethyl)-carboxamido)-
pyridine (1f). H NMR (CDCl3) d: 8.55 (d, 4.4 Hz, 1H,
4.4.13. 3-(N-Phenyl-carboxamido)-pyridine (2b). 1H
NMR (CDCl3) d: 9.05 (d, 1.8 Hz, 1H, Py); 8.69 (dd,
3.6 Hz, 1.8 Hz, 1H, Py); 8.50 (br s, 1H, NH); 8.16 (d,
8.0 Hz, 1.8 Hz, 1H, Py); 7.62 (d, 7.6 Hz, 2H, Ph); 7.30–
7.40 (m, 3H, Ph+Py); 7.16 (t, 7.2 Hz, 1H, Ph). 13C NMR
(CDCl3) d: 164.1; 152.2; 148.0; 137.6; 135.4; 130.9;
129.1; 125.0; 123.6; 120.6. IR (KBr (cmꢁ1)): 3351 (NH);
1655 (CON). MS m/z (rel int. %): 198 (68), 106 (100), 78
(63). Analysis calculated for C12H10N2O (198.22): C,
72.71; H, 5.08; N, 14.13. Found: C, 72.64; H, 5.21; N,
14.01. Yield: 7%.
1
Py); 8.46 (br s, 1H, NH); 8.16 (d, 7.6 Hz, 1H, Py); 7.82
(dt, 7.6 Hz, 1.4 Hz, 1H, Py); 7.40 (dt, 4.4 Hz, 1.4 Hz, 1H,
Py); 4.78 (qi, 7.0 Hz, 1H, CH(CH3)); 3.85 (s, 3H, OCH3);
1.51 (d, 7.0 Hz, 3H, CH(CH3)). 13C NMR (CDCl3) d:
173.1; 163.9; 149.4; 148.2; 137.2; 126.3; 122.2; 52.4;
48.1; 18.4. IR (KBr (cmꢁ1)): 3382 (NH); 1744 (COO);
1674 (CON). MS m/z (rel int. %): 208 (3), 149 (100), 106
(54), 78 (80). Analysis calculated for C10H12N2O3
(208.22): C, 57.69; H, 5.81; N, 13.45. Found: C, 57.85; H,
5.94; N, 13.26. Yield: 12%.
4.4.14. 3-(N,N-Penta-1,5-diyl-carboxamido)-pyridine
(2c). 1H NMR (CDCl3) d: 8.50 (m, 2H, Py); 7.60 (d,
7.4 Hz, 1H, Py); 7.22 (dt, 7.4 Hz, 1.6 Hz, 1H, Py); 3.60 (br
s, 2H, NCH2); 3.24 (br s, 2H, NCH2); 1.60 (br s, 4H,
2ꢂCH2); 1.48 (br s, 2H, CH2). 13C NMR (CDCl3) d:
164.3; 154.7; 151.3; 136.7; 134.8; 123.9; 47.1; 42.4; 26.3;
25.4; 24.3. IR (KBr (cmꢁ1)): 1635 (CON). MS m/z (rel int.
%): 190 (100), 106 (72), 78 (49). Analysis calculated for
C11H14N2O (190.24): C, 69.45; H, 7.42; N, 14.72. Found:
C, 69.60; H, 7.52; N, 14.49. Yield: 60%.
4.4.9. 2-(N-(10-Methoxycarbonyl-butan-1,4-diyl)-carbox-
amido)-pyridine (1g). H NMR (CDCl3) d: 8.58; 8.40 (d,
1
4.4 Hz, 1H, Py); 8.00; 7.86 (d, 7.6 Hz, 1H, Py); 7.70–7.76
(m, 1H, Py); 7.25–7.32 (m, 1H, Py); 5.12; 4.65 (m, 1H,
NCH); 3.7–4.00 (m, 2H, NCH2); 3.70; 3.59 (s, 3H,
OCH3); 1.9–2.3 (m, 4H, CH2CH2). 13C NMR (CDCl3) d:
173.4; 172.6; 166.2; 165.5; 153.4; 152.8; 147.8; 147.1;
136.8; 136.7; 125.0; 124.5; 61.6; 60.1; 52.1; 51.9; 49.7;
48.2; 31.8; 28.8; 25.4; 22.0. IR (KBr (cmꢁ1)): 1744
(COO); 1631 (CON). MS m/z (rel int. %): 234 (11), 175
(38), 128 (100), 106 (51), 78 (84). Analysis calculated for
C12H14N2O3 (234.25): C, 61.53; H, 6.02; N, 11.96. Found:
C, 61.63; H, 6.14; N, 11.80. Yield: 20%.
4.4.15. 3-(N,N-Penta-1,5-diyl-glyoxylamido)-pyridine
1
(2c0). H NMR (CDCl3) d: 9.10 (br s, 1H, Py); 8.80 (br s,
1H, Py); 8.22 (d, 7.6 Hz, 1H, Py); 7.42 (dt, 7.6 Hz, 1.6 Hz,
1H, Py); 3.65 (br s, 2H, NCH2); 3.30 (br s, 2H, NCH2);
1.65 (br s, 4H, 2ꢂCH2); 1.60 (br s, 2H, CH2). 13C NMR
(CDCl3) d: 190.3; 167.5; 150.4; 147.6; 134.7; 132.1;
123.3; 47.0; 42.3; 26.2; 25.4; 24.3. IR (KBr (cmꢁ1)): 1672
(br, CO, CON). MS m/z (rel int. %): 218 (3), 190 (42), 112
(100), 69 (70). Analysis calculated for C12H14N2O2
(206.24): C, 64.06; H, 6.84; N, 13.58. Found: C, 64.22; H,
6.99; N, 13.29. Yield: 22%.
4.4.10. 2-(N-(10-Benzyloxycarbonyl-butan-1,4-diyl)-carb-
oxamido)-pyridine (1h). H NMR (CDCl3) d: 8.58; 8.18
1
(d, 4.4 Hz, 1H, Py); 7.97; 7.88 (d, 7.6 Hz, 1H, Py); 7.70
(m, 1H, Py); 7.20–7.45 (m, 6H, Py+Ph); 5.0–5.25 (m, 2H,
CH2Ph); 5.15; 4.72 (m, 1H, NCH); 3.75–4.05 (m, 2H,
NCH2); 1.85–2.3 (m, 4H, CH2CH2). 13C NMR (CDCl3) d:
172.7; 172.0; 166.3; 165.5; 153.5; 152.7; 147.9; 147.0;
136.7; 135.8; 135.7; 128.5; 128.3; 128.2; 124.9; 124.5;
124.3; 66.7; 66.5; 61.7; 60.2; 49.6; 48.3; 31.8; 28.8; 25.4;
21.9. IR (KBr (cmꢁ1)): 1743 (COO); 1632 (CON). MS m/z
(rel int. %): 310 (8), 219 (20), 204 (81), 175 (76), 106
(80), 91 (83), 78 (100). Analysis calculated for
C18H18N2O3 (310.35): C, 69.66; H, 5.85; N, 9.03. Found:
C, 69.82; H, 5.97; N, 8.90. Yield: 23%.
4.4.16. 3-(N,N-Penta-3-oxa-1,5-diyl-carboxamido)-pyri-
dine (2d). H NMR (CDCl3) d: 8.45 (m, 2H, Py); 7.58 (d,
1
7.2 Hz, 1H, Py); 7.20 (dt, 7.4 Hz, 1.6 Hz, 1H, Py); 3.60 (br
s, 4H, 2ꢂCH2); 3.45 (t, 2H, CH2); 3.22 (t, 2H, CH2). 13C
NMR (CDCl3) d: 167.4; 151.4; 148.0; 135.1; 132.3; 123.4;
66.7; 66.6; 46.3; 41.8. MS m/z (rel int. %): 192 (20), 191
(63), 177 (28), 106 (100), 86 (30), 78 (79). Analysis calcu-
lated for C10H12N2O2 (192.22): C, 62.49; H, 6.29; N,
14.57. Found: C, 62.56; H, 6.11; N, 14.45. Yield: 32%.
4.4.11. 3-(N-tert-Butyl-carboxamido)-pyridine (2a). 1H
NMR (CDCl3) d: 8.9 (br s, 1H, Py); 8.7 (br s, 1H, Py);
8.06 (d, 4.8 Hz, 1H, Py); 7.42 (m, 1H, Py); 5.95 (br s, 1H,
NH); 1.42 (s, 9H, C(CH3)3). 13C NMR (CDCl3) d: 165.0;
151.8; 147.7; 134.9; 132.1; 123.3; 51.8; 28.8. IR (KBr
(cmꢁ1)): 3370 (NH); 1673 (CON). MS m/z (rel int. %):
178 (12), 163 (30), 123 (28), 106 (100), 78 (45). Analysis
calculated for C10H14N2O (178.23): C, 67.39; H, 7.92; N,
15.72. Found: C, 67.27; H, 8.08; N, 15.50. Yield: 34%.
4.4.17. 3-(N,N-Penta-3-oxa-1,5-diyl-glyoxylamido)-pyri-
1
dine (2d0). H NMR (CDCl3) d: 9.08 (br s, 1H, Py); 8.78
(d, 4.2 Hz, 1H, Py); 8.20 (d, 7.4 Hz, 1H, Py); 7.40 (dt,
7.4 Hz, 4.2 Hz, 1H, Py); 3.70 (br s, 4H, 2ꢂCH2); 3.60 (t,
2H, CH2); 3.33 (t, 2H, CH2). 13C NMR (CDCl3) d: 189.4;
164.2; 154.8; 151.2; 148.0; 136.7; 128.8; 123.8; 66.7;
66.5; 46.3; 41.8. IR (KBr (cmꢁ1)): 1684 (CO); 1646
(CON). MS m/z (rel int. %): 220 (4), 192 (61), 114 (94),
106 (52), 78 (51), 70 (100). Analysis calculated for
C11H12N2O3 (220.23): C, 59.99; H, 5.49; N, 12.72. Found:
C, 59.82; H, 5.60; N, 12.51. Yield: 43%.
1
4.4.12. 3-(N-tert-Butyl-glyoxylamido)-pyridine (2a0). H
NMR (CDCl3) d: 9.45 (s, 1H, Py); 8.78 (d, 3.6 Hz, 1H,
Py); 8.62 (d, 8.0 Hz, 1H, Py); 7.40 (m, 1H, Py); 7.00 (br s,
1H, NH); 1.46 (s, 9H, C(CH3)3). 13C NMR (CDCl3) d:
187.4; 160.2; 153.8; 152.1; 138.5; 129.2; 123.2; 51.8;
28.3. IR (KBr (cmꢁ1)): 3357 (NH); 1655 (br, CO, CON).
MS m/z (rel int. %): 206 (2), 107 (40), 106 (42), 78 (76),
4.4.18. 3-(N-(Methoxycarbonylmethyl)-carboxamido)-
pyridine (2e). H NMR (CDCl3) d: 9.00 (s, 1H, Py); 8.70
1