Issue in Honor of Prof. Pawe. Kafarski ARKIVOC 2012 (iv) 252-263
7.1 Hz, CH3), 1.76-1.87 (2H, m, PCH2CH2), 2.24-2.34 (2H, m, PCH2), 4.03 (3H, s, OCH3), 4.06 (3H, s, OCH3), 4.12-4.18 (4H, m, OCH2), 4.75 (2H, t, 3JHH = 7.1 Hz, NCH2). 13C NMR (75.5 MHz, CDCl3): .C 16.14 (d, 3JPC = 6.0 Hz, CH3), 22.27 (d, 1JPC = 139.7 Hz, PCH2), 23.25 (PCH2CH2), 50.20 (d, 3JPC = 17.0, NCH2), 52.37 (OCH3), 53.22 (OCH3), 61.46 (OCH2), 61.54 (OCH2), 129.67 (C=), 139.70 (C=), 158.50 (C=O), 160.18 (C=O). Anal. Calcd for C13H22N3O7P: C, 42.98; H, 6.10; N, 11.57; P, 8.53%. Found: C, 43.00; H, 6.17; N, 11.43; P, 8.61%. Tetramethyl {1-[2-(diethoxyphosphoryl)ethyl]-1H-1,2,3-triazole-4,5-diyl}bis(phosphonate) (3c) was prepared by the same procedure from azidophosphonate 1a and tetramethyl acetylenediphosphonate 2b at 60 °C for 2 h. Brown oil, yield 95%; IR (thin layer, .max, cm-1): 1032 (br, P-O-C), 1266 (br, P=O). 31P NMR (121.5 MHz, CDCl3): .P 3.67, 7.45, 24.62. 1H NMR
(300.1 MHz, CDCl3): .H 1.39 (6H, t, 3JHH = 7.1 Hz, CH3), 2.16-2.25 (2H, m, PCH2), 3.95 (6H, s, OCH3), 3.99 (6H, s, OCH3), 4.17-4.22 (4H, m, OCH2), 5.00-5.08 (2H, m, NCH2). 13C NMR (75.5 MHz, CDCl3): .C 15.45 (CH3), 26.57 (d, 1JPC = 139.9 Hz, PCH2), 44.82 (NCH2), 52.89 (OCH3), 52.97 (OCH3), 53.36 (OCH3), 53.43 (OCH3), 61.17 (OCH2), 61.20 (OCH2), 129.35 (dd, 1JPC = 216.4 Hz, 2JPC = 34.1 Hz, PC=), 141.56 (dd, 1JPC = 236.8 Hz, 2JPC =20.3 Hz, PC=). Anal. Calcd for C12H26N3O9P3: C, 32.08; H, 5.83; N, 9.35%. Found: C, 32.00; H, 5.91; P, 9.30%. Tetramethyl 2H-1,2,3-triazole-4,5-diylbis(phosphonate) (5). Tetramethyl acetylenediphosphonate 2b (400 mg, 1.65 mmol). was slowly dropped to the solution of sodium azide (113 mg, 1.73 mmol) in water (5 ml) at room temperature. The reaction mixture was stirred for 0.5 h, followed by the acidification to pH=3 by aq.HCl. Then water was removed under reduced pressure, the residue was dissolved in acetonitrile (6 ml), NaCl precipitated was filtered off, and filtrate was concentrated in vacuo and dried over P2O5 to give the final white solid, yield 81%, 380 mg, mp 100 °.; IR (KBr, .max, cm-1): 1029 (P-O-C), 1246 (P=O). 31P NMR (121.5 MHz, CDCl3): .P 8.49. 1H NMR (300.1 MHz, CDCl3): .H 3.90 (12H, s, OCH3), 13.87 (1H, br. s, NH). 13C NMR (75.5 MHz, CDCl3): .C 54.05 (OCH3), 54.12 (OCH3), 128.59 (dd, 1JPC = 237.0 Hz, 3JPC = 27.0 Hz, C-C). Anal. Calcd for C6H13N3O6P2•0.25 NaCl: C, 24.28; H, 4.41; N, 14.16%. Found: C, 24.19; H, 4.50; N, 14.36%. Diethyl [2-[4,5-bis(amino)carbonyl]-1H-1,2,3-triazol-1-yl]alkyl]phosphonates (6a-c,7) (general procedure). The solution of the corresponding triazole 3a,b (2.0 mmol) and amine (4.0 mmol) in methanol (5 ml) was vigorously stirred at room temperature until the completion of the reaction according 31P NMR and TLC monitoring of the reaction course (namely, 12, 14 and 24 h for 6b, 6c, and 6a, respectively). Then solvent was removed under reduced pressure to give products with high purity.
Diethyl [3-[4,5-bis[(butylamino)carbonyl]-1H-1,2,3-triazol-1-yl]propyl]phosphonate (6a).
Brown oil, 91%; IR (thin layer, .max, cm-1): 1030, 1058 (P-O-C), 1245 (P=O), 1676 (C=O). 31P NMR (121.5 MHz, CDCl3): .P 30.37. 1H NMR (300.1 MHz, CDCl3): .H 0.88-0.94 (6H, m, CH3 in nBu), 1.26 (6H, t, 3JHH = 7.1 Hz, CH3), 1.34-1.42 (4H, m, CH2CH3), 1.56-1.61 (4H, m, CH2CH2CH3), 1.67-1.79 (2H, m, PCH2CH2), 2.11-2.23 (2H, m, PCH2), 3.32-3.46 (4H, m, NHCH2), 4.02-4.07 (4H, m, OCH2), 4.95 (2H, t, 3JHH = 6.9 Hz, NCH2), 7.78 (1H, br. s, NH),
11.13 (1H, br. s, NH). 13C NMR (75.5 MHz, CDCl3): .C 15.24 (CH3 in Bu), 16.74 (d, 3JPC = 6.0 Page 259 ©ARKAT-USA, Inc.
