684
I. E. Głowacka et al.
Arch. Pharm. Chem. Life Sci. 2013, 346, 677–687
Diethyl [4-(carbamoyl)-1,2,3-triazol-1-yl]-
Diethyl 1-hydroxy-2-[4-(carbamoyl)-1,2,3-triazol-1-yl]-
methylphosphonate 14a
ethylphosphonate 14e
From 13a (0.090 g, 0.325 mmol) the phosphonate 14a (0.082 g,
96%) was obtained as a white powder. m.p.: 112–113°C; IR (KBr):
n ¼ 3379, 3189, 2987, 2900, 1667, 1193, 1078, 1042 cmꢁ1; 1H NMR
(300 MHz, CD3OD): d ¼ 7.84 (s, 1H, HC50); 4.07 (d, J ¼ 12.5 Hz, 2H,
From 13e (0.060 g, 0.196 mmol) the phosphonate 14e (0.054 g,
98%) was obtained as a white powder. m.p.: 95–97°C; IR (KBr):
n ¼ 3416, 3206, 2984, 2931, 1636, 1217, 1048 cmꢁ1
;
1H NMR
(300 MHz, CD3OD): d ¼ 8.43 (s, 1H, HC50); 4.80 (ddd, J ¼ 14.4 Hz,
J ¼ 6.3 Hz, J ¼ 3.3 Hz, 1H, PCCHaHb); 4.62 (ddd, J ¼ 14.4 Hz, J ¼ 9.6
Hz, J ¼ 7.2 Hz, 1H, PCCHaHb); 4.26–4.14 (m, 4H, 2 ꢂ POCH2CH3),
PCH2); 3.58–3.26 (m, 4H, 2 ꢂ POCH2CH3), 0.61 (t, J ¼ 7.2 Hz, 6H,
13
–
2 ꢂ POCH2CH3); C NMR (75.5 MHz, CD OD): d ¼ 164.7 (s, C O);
–
3
–
–
–
143.5 (s, HC C); 128.0 (s, HC C); 62.3 (d, J ¼ 6.3 Hz, POC); 48.5 (d,
4.36 (dt, J ¼ 9.6 Hz, J ¼ 3.3 Hz, 1H, PCH(OH)); 1.35 (t, J ¼ 7.2 Hz, 6H,
–
J ¼ 147.2 Hz, PC); 17.2 (d, J ¼ 6.4 Hz, POCC); 31P NMR (121.5 MHz,
CD3OD): d ¼ 9.29 ppm. Anal. calcd. for C8H15N4O4P: C, 36.65; H,
5.77; N, 21.37. Found: C, 36.44; H, 5.62; N, 21.12.
2 ꢂ POCH2CH3); C NMR (75.5 MHz, CD OD): d ¼ 164.7 (s, C O);
13
–
–
3
–
–
–
140.3 (s, HC C); 129.0 (s, HC C); 67.7 (d, J ¼ 167.7 Hz, PC); 64.9 (d,
–
J ¼ 7.4 Hz, POC); 64.7 (d, J ¼ 7.4 Hz, POC); 53.1 (d, J ¼ 10.0 Hz, C-2);
17.0 (d, J ¼ 5.1 Hz, POCC); 31P NMR (121.5 MHz, CD3OD): d ¼ 21.80
ppm. Anal. calcd. for C9H17N4O5P: C, 36.99; H, 5.86; N, 19.17.
Found: C, 37.12; H, 5.69; N, 19.20.
Diethyl 2-[4-(carbamoyl)-1,2,3-triazol-1-yl]-
ethylphosphonate 14b
From 13b (0.070 g, 0.240 mmol) the phosphonate 14b (0.065 g,
99%) was obtained as a white powder. m.p.: 115–117°C; IR (KBr):
Diethyl 2-hydroxy-3-[4-(carbamoyl)-1,2,3-triazol-1-yl]-
propylphosphonate 14f
n ¼ 3398, 2984, 2909, 2878, 1677, 1238, 1028 cmꢁ1
;
1H NMR
(300 MHz, CDCl3): d ¼ 8.36 (s, 1H, HC50); 7.02 (brs, 1H, NH); 5.80
(brs, 1H, NH); 4.68 (dt, J ¼ 12.7 Hz, J ¼ 7.4 Hz, 2H, PCCH2); 4.16–4.06
(m, 4H, 2 ꢂ POCH2CH3), 2.46 (dt, J ¼ 18.6 Hz, J ¼ 7.4 Hz, 2H, PCH2);
1.31 (t, J ¼ 7.0 Hz, 6H, 2 ꢂ POCH2CH3); 13C NMR (75.5 MHz, CDCl3):
From 13f (0.076 g, 0.248 mmol) the phosphonate 14f (0.061 g, 85%)
was obtained as an amorphous solid. m.p.: 186–188°C; IR
(KBr): n ¼ 3410, 3300, 2986, 2900, 1650, 1221, 1034 cmꢁ1; 1H NMR
(300 MHz, CD3OD): d ¼ 8.37 (s, 1H, HC50); 4.66 (dd, J ¼ 13.8 Hz,
J ¼ 3.6 Hz, 1H, PCCCHaHb); 4.44 (dd, J ¼ 13.8 Hz, J ¼ 7.5 Hz,
1H, PCCCHaHb); 4.20–4.06 (m, 4H, 2 ꢂ POCH2CH3), 2.22–1.97
(m, 2H, PCHaHb); 1.34 (t, J ¼ 7.2 Hz, 3H, POCH2CH3); 1.33
(t, J ¼ 7.2 Hz, 3H, POCH2CH3); 13C NMR (75.5 MHz, CD3OD):
–
–
–
–
d ¼ 162.2 (s, C O); 142.9 (s, HC C); 126.6 (s, HC C); 62.4 (d,
–
–
J ¼ 6.3 Hz, POC); 45.2 (s, PCC); 27.3 (d, J ¼ 141.0 Hz, PC); 16.6 (d,
J ¼ 5.7 Hz, POCC); 31P NMR (121.5 MHz, CDCl3): d ¼ 26.05 ppm.
Anal. calcd. for C9H17N4O4P: C, 39.13; H, 6.20; N, 20.28. Found: C,
39.29; H, 6.33; N, 20.23.
–
–
–
–
–
d ¼ 158.9 (s, C O); 140.9 (s, HC C); 126.8 (s, HC C); 67.6;
–
63.6 (d, J ¼ 6.8 Hz, POC); 63.3 (d, J ¼ 6.8 Hz, POC); 57.8 (d,
J ¼ 14.2 Hz, PCCC); 32.0 (d, J ¼ 141.4 Hz, PC); 16.6 (d, J ¼ 6.5 Hz,
POCC); 31P NMR (121.5 MHz, CD3OD): d ¼ 29.68 ppm. Anal. calcd.
for C10H19N4O5P: C, 39.22; H, 6.25; N, 18.29. Found: C, 39.01; H,
6.13; N, 18.39.
Diethyl 3-[4-(carbamoyl)-1,2,3-triazol-1-yl]-
propylphosphonate 14c
From 13c (0.090 g, 0.310 mmol) the phosphonate 14c (0.083 g,
96%) was obtained as a white powder. m.p.: 110–112°C; IR (KBr):
n ¼ 3417, 3186, 2980, 2907, 1648, 1238, 1038 cmꢁ1
;
1H NMR
(300 MHz, CDCl3): d ¼ 8.25 (s, 1H, HC50); 7.24 (brs, 1H, NH); 6.52
(brs, 1H, NH); 4.54 (t, J ¼ 6.9 Hz, 2H, PCCCH2); 4.18–4.05 (m, 4H,
2 ꢂ POCH2CH3), 2.28 (dqu, J ¼ 15.3 Hz, J ¼ 6.9 Hz, 2H, PCCH2); 1.76
(ddd, J ¼ 15.3 Hz, J ¼ 8.0 Hz, J ¼ 6.9 Hz, 2H, PCH2); 1.33 (t, J ¼ 7.1 Hz,
6H, 2 ꢂ POCH2CH3); 13C NMR (75.5 MHz, CD3OD): d ¼ 164.6 (s,
Diethyl 2-{[4-(carbamoyl)-1,2,3-triazol-1-yl]ethoxy}-
methylphosphonate 14g
From 13g (0.100 g, 0.311 mmol) the phosphonate 14g (0.095 g,
98%) was obtained as an amorphous solid. m.p.: 65–67°C; IR (KBr):
n ¼ 3413, 3193, 2987, 2902, 1651, 1262, 1038 cmꢁ1
;
1H NMR
C O); 143.8 (s, HC C); 127.8 (s, HC C); 63.5 (d, J ¼ 6.6 Hz, POC);
(300 MHz, CDCl3): d ¼ 8.27 (s, 1H, HC50); 7.28 (brs, 1H, NH); 5.85
(brs, 1H, NH); 4.63 (t, J ¼ 4.8 Hz, 2H, OCH2CH2N); 4.18–3.98 (m, 4H,
2 ꢂ POCH2CH3), 4.01 (t, J ¼ 4.8 Hz, 2H, OCH2CH2N); 3.79 (d,
–
–
–
–
–
–
51.4 (d, J ¼ 17.4 Hz, PCCC), 24.8 (d, J ¼ 4.6 Hz, PCC); 23.2 (d,
J ¼ 142.6 Hz, PC); 16.9 (d, J ¼ 5.7 Hz, POCC); 31P NMR (121.5 MHz,
CDCl3): d ¼ 30.90 ppm. Anal. calcd. for C10H19N4O4P: C, 41.38; H,
6.60; N, 19.30. Found: C, 41.50; H, 6.41; N, 19.33.
J ¼ 8.1 Hz, 2H, PCH2O); 1.33 (t, J ¼ 7.0 Hz, 6H, 2 ꢂ POCH2CH3);
13
–
–
–
–
C NMR (75.5 MHz, CDCl ): d ¼ 162.2 (s, C O); 142.8 (s, HC C);
3
–
–
127.0 (s, HC C); 70.8 (d, J ¼ 10.3 Hz, OCH2CH2N); 65.3 (d,
J ¼ 166.1 Hz, PC); 62.6 (d, J ¼ 6.5 Hz, POC); 50.4 (s, OCH2CH2N);
16.5 (d, J ¼ 5.6 Hz, POCC); 31P NMR (121.5 MHz, CDCl3): d ¼ 21.26
ppm. Anal. calcd. for C10H19N4O5P: C, 39.22; H, 6.25; N, 18.29.
Found: C, 39.39; H, 6.12; N, 18.14.
Diethyl 4-[4-(carbamoyl)-1,2,3-triazol-1-yl]-
butylphosphonate 14d
From 13d (0.068 g, 0.224 mmol) the phosphonate 14d (0.064 g,
98%) was obtained as a white powder. m.p.: 87–89°C; IR (KBr):
n ¼ 3418, 3180, 3039, 2983, 2934, 1656, 1242, 1031 cmꢁ1; 1H NMR
(300 MHz, CDCl3): d ¼ 8.16 (s, 1H, HC50); 7.17 (brs, 1H, NH);
6.20 (brs, 1H, NH); 4.44 (t, J ¼ 6.9 Hz, 2H, PCCCCH2); 4.18–4.02
(m, 4H, 2 ꢂ POCH2CH3), 2.19–2.05 (m, 2H, CH2); 1.85–1.60
(m, 4H, 2 ꢂ CH2); 1.34 (t, J ¼ 7.2 Hz, 3H, POCH2CH3); 1.32
(t, J ¼ 7.2 Hz, 3H, POCH2CH3); 13C NMR (75.5 MHz, CD3OD):
Diethyl 2-{[4-(carbamoyl)-1,2,3-triazol-1-yl]ethoxy}-
ethylphosphonate 14h
From 13h (0.092 g, 0.274 mmol) the phosphonate 14h (0.085 g,
98%) was obtained as a colorless oil. IR (film): n ¼ 3403, 3176, 2983,
2930, 1660, 1231, 1032 cmꢁ1; 1H NMR (300 MHz, CDCl3): d ¼ 8.32
(s, 1H, HC50); 7.19 (brs, 1H, NH); 5.96 (brs, 1H, NH); 4.60 (t,
J ¼ 4.7 Hz, 2H, OCH2CH2N); 4.14–4.04 (m, 4H, 2 ꢂ POCH2CH3), 3.84
(t, J ¼ 4.7 Hz, 2H, OCH2CH2N); 3.79 (dt, J ¼ 13.1 Hz, J ¼ 7.3 Hz, 2H,
PCH2CH2O); 2.08 (dt, J ¼ 18.6 Hz, J ¼ 7.3 Hz, 2H, PCH2CH2O); 1.31 (t,
J ¼ 7.0 Hz, 6H, 2 ꢂ POCH2CH3); 13C NMR (75.5 MHz, CDCl3):
–
–
–
–
–
d ¼ 164.6 (s, C O); 143.8 (s, HC C); 127.6 (s, HC C); 63.4 (d,
–
J ¼ 6.2 Hz, POC); 51.0 (s, PCCCC); 31.7 (d, J ¼ 15.7 Hz, PCCC), 25.3 (d,
J ¼ 140.9 Hz, PC); 20.4 (d, J ¼ 5.1 Hz, PCC); 16.9 (d, J ¼ 6.1 Hz, POCC);
31P NMR (121.5 MHz, CDCl3): d ¼ 31.90 ppm. Anal. calcd. for
C11H21N4O4P: C, 43.42; H, 6.96; N, 18.41. Found: C, 43.32; H, 7.09;
N, 18.49.
–
–
–
–
–
d ¼ 162.4 (s, C O); 142.7 (s, HC C); 127.0 (s, HC C); 68.7
–
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