Complete crystallographic data for the structural analysis have been deposited with the Cambridge Crystallographic Data Centre; CCDC reference number 2145469(4b) and 2145470(4c). and These data are provided free of charge by the joint Cambridge Crystallographic Data Centre via: http://www.ccdc.cam.ac.uk/datarequest/cif
2.2.1. Typical procedure for compounds 4(a-n)
In a 10 mL round-bottom flask, a mixture of benzaldehyde (1 mmol, 100 µL) and sulfamide (1 mmol,) and then diethylphosphite (1 mmol) was taken at room temperature. The reaction mixture was subjected to ultrasonication/Microwave irradiation for appropriate time (60-90min). After completion of the reaction, as indicated by TLC, a mixture of diethyl ether/n-hexane (4:1) was added and left to cool at 6°C overnight. Finally, the desired product was obtained with good yields after a simple filtration and drying. This procedure was followed for the preparation of all the sulfamidophosphonat listed in Table 4.
White powder. m.p = 124–126°C. Rf (EtOAc-Petet: 50/50) = 0.13. IR (KBr/cm-1) νmax= 3277.22 and 3218.05(NH2), 3100.68(NH), 1335.62 and 1163.55 (SO2), 1209.17(P = O), 1050.80 (P-O). 31P NMR (120 MHz, DMSO d6) δ = 20.82; 1H NMR (400 MHz, DMSO) δ = 1.07 (t, 3JH-H 6.8 Hz, 3H, H3C-CH2-), 1.20 (t, 3JH-H 7.2 Hz, 3H, H3C-CH2-) 3.72–3.92 (m, 2H, -H2C-CH3), 3.99–4.07 (m, 2H, -H2C-CH3) 4.65 (dd, J1(H-H) 9.6, J2(Hc-p) 24 Hz, 1H, *CH), 6.5 (s, 2H, NH2), 7.24–7.33 (m, 3H, H-Ar), 7.46–7.48 (m, 2H, H-Ar), 7.7 (d, J 12 Hz ,1H, NH). 13C NMR (100 MHz, DMSO) δ = 16.1(d, 3JC-p 5.4Hz, CH3), 16.3(d, 3JC-p 5.5 Hz, -CH3), 53,54-55.09(d, 1JC-P 155 Hz, *CH), 62.4(d, 2JC-p 6.6 Hz, -CH2-), 62.86(d, 2JC-p 6.9 Hz, -CH2-), 127.45 (d, JC-p 3 Hz, CH-Ar), 127.86 (d, JC-p 2 Hz, 2CH-Ar), 128.52 (d, JC-p 5 Hz, CH-Ar), 136.08 (C-Ar) ppm.
White powder. m.p = 153–155°C. Rf (EtOAc- Petet: 50/50) = 0.15. IR (KBr/cm-1) νmax= 3261.24 and 3230.50 (NH2), 3092.25(NH), 1335.16, 1143.55(SO2), 1235.13(P = O), 1015.71 (P-O). 31P NMR (120 MHz, DMSO): δ = 20.22; 1H NMR (400 MHz, DMSOd6) δ = 1.1 (t, 3JH-H 8 Hz, 3H, H3C-CH2-), δ = 1.2 (t, 3JH-H 8 Hz, 3H, H3C-CH2-) 3.79–3.97 (m, 2H, -H2C-CH3), 4.01–4.08 (m, 2H, -H2C-CH3) 4.71 (dd, J1(H-H) 12, J2(Hc-p) 24Hz, 1H, *CH), 6.56 (s, 2H, NH2), 7.38–7.41 (m, 2H, H-Ar), 7.48–7.51 (m, 2H, H-Ar) 7.74 (dd, J 4 Hz ,1H, NH). 13C NMR (100 MHz, DMSO): 16.04 (d, 3JC-p 5 Hz, H3C-CH2-), 16.21 (d, 3JC-p 6 Hz, H3C-CH2-), 52,82-54.37 (d, 1JC-P 155Hz *CH), 62.37(d, 2JC-p 7Hz, H3C-CH2-), 62.88(d, 2JC-p 7Hz, H3C-CH2-), 127.74(d, JC-p 2Hz, 2CH-Ar), 130.28(d, JC-p 5 Hz, 2CH-Ar), 132.08(d, JC-p 3 Hz, (Cl-C-Ar), 135.25(C-Ar) ppm.
White powder. m.p = 162–164°C. Rf (EtOAc- Petet: 50/50) = 0.19. IR (KBr/cm-1) νmax= 3268.75, 3216.57 (NH2), 3100.00(NH), 1334.19, 1144.86(SO2), 1233.51(P = O), 1016.09 (P-O). 31P NMR (120 MHz, DMSO) δ = 22.19; 1H NMR (400 MHz, DMSO): δ = 1.08 (t, 3JH-H 4.6 Hz, 3H, H3C-CH2-), δ = 1.22 (t, 3JH-H 7 Hz, 3H, H3C-CH2-), 3.67–3.99(m, 2H, H3C-CH2-), 4.01–4.10(m, 2H, -H2C-CH3), 4.70 (dd, J1(H-H) 6.6, J2(Hc-p) 16.2 Hz 1H,*CH), 6.58 (s, 2H, NH2), 7.38–7.39 (d, 2H, J(H-H) 5.6 Hz, H-Ar), 7.48–7.50 (m, 2H, H-Ar), 7.77 (d, J 7.2 Hz, 1H, NH ); 13C NMR (100 MHz, DMSO) 16.53 (d, H3C-CH2-), 16.75 (d, H3C-CH2-), 53,54-54.57 (d, 1JC-P 103.3Hz *CH), 62.86(d, 2JC-p 4.7Hz, H3C-CH2-), 63.38 (d, 2JC-p 4.7Hz, H3C-CH2-), 128.25(2CH-Ar), 130.78(d, JC-p 4 Hz, 2CH-Ar), 132.57(d, JC-p 2.5 Hz, C-Ar), 135.75(F-C-Ar) ppm.
White powder. m.p = 218–220°C. Rf (EtOAc- Petet: 50/50) = 0.25. IR (KBr/cm-1) νmax= 3275.25 and 3215.12 (NH2), 3096.61(NH), 1335.10 and 1143.94(SO2), 1236.78(P = O), 1049.55(P-O). 31P NMR (120 MHz, DMSO) δ = 19.82 (d, JP-H 5.76 Hz, P-CH); 1H NMR (400 MHz, DMSOd6) δ = 1.07 (t, 3JH-H 7.2 Hz, 3H, H3C-CH2-), δ = 1.95 (t, 3JH-H 7.2 Hz, 3H, H3C-CH2-) 3.727–3.793 (m, 1H, -H2C-CH3), 3.833–3.895 (m, 1H, -H2C-CH3) 4.95–4.018 (m, 2H, -H2C-CH3), 4.60 (d, J(Hc-p) 24Hz 1H, *CH), 7.16 (d, J 2 Hz, 2H, H-Ar), 7.35 (d, J 8.4 Hz, 2H, H-Ar), 8.11 (sbr, 1H, NH); 13C NMR (100 MHz, DMSO) δ = 16.04 (d, 3JC-p 5.5 Hz, H3C-CH2-), 16.24 (d, 3JC-p 5.4 Hz, H3C-CH2-), 53.65 (d, 1JC-P 154.6Hz *CH), 62.42 (d, 2JC-p 6.9 Hz, H3C-CH2-), 62.89 (d, 2JC-p 7Hz, H3C-CH2-), 120.89 (d, JC-p 7 Hz, Br-C-Ar), 130.29 (d, JC-p 5 Hz, 2CH-Ar), 130.51 (d, JC-p 5 Hz 2CH-Ar), 134.65 (C-Ar) ppm.
White powder. m.p = 137–139°C. Rf (EtOAc- Petet: 50/50) = 0.17. IR (KBr/cm-1) νmax= 3268.93 and 3251.12 (NH2), 3102.28(NH), 1334.75 and 1145.00(SO2), 1233.93(P = O), 1016.67(P-O).1H NMR (400 MHz, DMSOd6) δ = 1.08 (t, 3JH-H 7.2 Hz, 3H, H3C-CH2-), δ = 1.21 (t, 3JH-H 7.2 Hz, 3H, H3C-CH2-), 2.29 (S, 3H, -CH3), 3.70–4.07 (m, 4H, -H2C-CH3), 4.64 (dd, J1(H-H) 7, J2(Hc-p) 20.6 Hz 1H,*CH), 6.51 (s, 2H, NH2), 7.03–7.18 (m, 2H, H-Ar), 7.20–7.28 (m, 2H, H-Ar), 7.60 (dd, J1 2.8 Hz, J2 10 Hz ,1H, NH). 13C NMR (100 MHz, DMSO) 16.03 (d, 3JC-p 5.5 Hz, H3C-CH2-), 16.25 (d, 3JC-p 5.4 Hz, H3C-CH2-), 21.03(S, CH3), 54.22 (d, 1JC-P 154.2Hz *CH), 62.28(d, 2JC-p 13.4Hz, H3C-CH2-), 62.78(d, 2JC-p 6.9Hz, H3C-CH2-), 125.55 (d, JC-p5.5 Hz, CH-Ar), 127.63 (d, JC-p12.1 Hz, CH-Ar), 128.81 (d, JC-p5.4 Hz, CH-Ar), 129.05(d, JC-p5.8 Hz, CH-Ar), 135.64(d, JC-p54.3 Hz, C-Ar),136.68 (d, JC-p10.6 Hz, CH3-C-Ar) ppm.
White powder. m.p = 133–135°C. Rf (EtOAc- Petet: 50/50) = 0.15. IR (KBr/cm-1) νmax= 3342.05 and 3296.17(NH2), 3160.71(NH), 1319.94 and 1149.70 (SO2), 1227.04(P = O), 1080.56(P-O). 1H NMR (400 MHz, DMSOd6) δ = 1.06 (t, 3JH-H 4.6 Hz 3H, H3C-CH2-), δ = 1.20 (t, 3JH-H 4.8 Hz 3H, H3C-CH2-), 3.73 (s, 3H, OCH3), 3.74–3.88 (m, 1H, -H2C-CH3), 3.89–3.91 (m, 1H, -H2C-CH3), 4.00-4.06 (m, 2H, -H2C-CH3), 4.68 (dd, J1(H-H) 4.8, J2(Hc-p) 16 Hz 1H,*CH), 6.55 (s, 2H, NH2), 7.31 (t, JH-H 5.4 Hz 2H, H-Ar), 4.46–4.48 (dd, 2H, H-Ar), 6.69 (d, J 6.8 Hz ,1H, NH); 13C NMR (100 MHz, DMSO) 16.05 (d, 3JC-p 3.6 Hz, H3C-CH2-), 16.27 (d, 3JC-p 3.6 Hz, H3C-CH2-), 54.25 (d, 2JC-P 102.9 Hz *CH), 58.49 (OCH3), 62.29 (H3C-CH2), 62.77 (H3C-CH2-), 127.37 (d, JC-p 2.1 Hz, 2Car) 127.79 (2 Car) 128.47 (d, JC-p 4 Hz, CAr), 136.06 (Cq-OCH3) ppm.
White powder. m.p = 172–174°C. Rf (EtOAc- Petet: 50/50) = 0.25. 3294.12 and 3243.10 (NH2), 3122.34(NH), 1334.76 and 1156.23(SO2), 1231.37(P = O), 1021.43(P-O). 31P NMR (120 MHz, DMSO) δ20.63; 1H NMR (400 MHz, DMSO) δ = 1.22ppm (t, 3JH-H 7 Hz, 3H, CH3), δ = 1.06 (t, 3JH-H 5.2 Hz, 3H, CH3), 3.76–3.98 (m, 2H, CH2), 4.00-4.10 (m, 2H, -H2C-CH3), 4.88 (dd, J1(H-H) 8.4, J2(Hc-p)24.2 Hz 1H,*CH), 6.55 (s, 2H, NH2), 7.42–7.90 (m, 7H, H-Ar), 8.00 (s,1H, NH). 13C NMR (100 MHz, DMSO) 15.53 (d, 3JC-p 5.5 Hz, H3C-CH2-), 16.74 (d, 3JC-p 5.5 Hz, H3C-CH2-), 54.98 (d, 2JC-P 154.2Hz *CH), 62.85 (d, 2JC-p 6.9Hz, H3C-CH2-), 63.34(d, 2JC-p 6.9Hz, H3C-CH2-), 126.35-134.25 (CH-Ar) ppm.
White powder. m.p = 154–156°C. Rf (EtOAc- Petet: 50/50) = 0.26. IR (KBr/cm-1) νmax= 3288.57(NH2), 3174.66(NH), 1344.13-1152.91(SO2), 1289.76(P = O), 1152.91(P-O); 1H NMR (400 MHz, DMSO) δ = 1.09ppm (t, J 4.6 Hz, 3H, CH3,), δ = 1.20ppm (t, J 4.6 Hz, 3H, CH3,) 3.80–3.94 ppm (m, 2H, CH2), 4.01–4.06 (m, 2H, CH2) 4.70 (dd, J 6.6 Hz, 1H, CH,), 6.57ppm (s, 2H, NH2), 7.38 (d, 2H, H-Ar), 7.48–7.50 (m, 2H, Har), 7.77ppm (d, J 7.2 Hz ,1H, NH). 13C NMR (100 MHz, DMSO) 16.15 (d, 3JC-p 5.5 Hz, H3C-CH2-), 16.35 (d, 3JC-p 5.1 Hz, H3C-CH2-), 52.87 (d, 2JC-P 151.3Hz *CH), 62.59 (d, 2JC-p 9.6 Hz, H3C-CH2-), 62.85(d, 2JC-p 6.9Hz, H3C-CH2-), 127.09 (s, Car), 128.19 (d, JC-p 2.5 Hz, Car)131.80 (s, Car), 130.14 (d, JC-p 5.5 Hz, Car), 135.54 (C-Ar) ppm.
White powder. m.p = 160–162°C. Rf (EtOAc- Petet: 50/50) = 0.20. IR (KBr/cm-1) νmax= 3286.65 (NH2), 3194.04(NH), 1304.54 and 1148.98(SO2), 1282.64(P = O), 1051.56(P-O). 1H NMR (400 MHz, DMSO) δ = 1.06 (t, 3JH-H 7 Hz, 3H, H3C-CH2-), δ = 1.17 (t, 3JH-H 7 Hz, 3H, H3C-CH2-), 3.72–3.94(m, 2H, H3C-CH2-), 4.00-4.09(m, 2H, -H2C-CH3), 4.70 (dd, J1(H-H) 6.9, J2(Hc-p) 24.4 Hz 1H,*CH), 6.55 (s, 2H, NH2), 7.05–7.56 (m, 4H, H-Ar), 7.67 (d, J 2 Hz). 13C NMR (100 MHz, DMSO) 16.09 (d, 3JC-p 5.1 Hz, H3C-CH2-), 16.31 (d, 3JC-p 4.1 Hz, H3C-CH2-), 52.81 (d, 1JC-P 153.1Hz *CH), 61.17(d, 2JC-p 5.5Hz, H3C-CH2-), 62.30(d, 2JC-p 13.4Hz, H3C-CH2-), 126.91 (d, 2CH-Ar), 129.42 (d, JC-p5.8Hz, CH-Ar), 132.32 (s, CH-Ar), 150.21(d, JC-p13.5Hz, Cq-Ar), 156.84 (d, JC-p2.6Hz, Cl-C-Ar) ppm.
White powder. m.p = 165–167°C. Rf (EtOAc- Petet: 50/50) = 0.20 IR (KBr/cm-1) νmax= 3336.30 and 3270.40(NH2), 3102.25(NH), 1315.53-1149.46(SO2), 1208.35(P = O), 1027.13(P-O). 1H NMR (400 MHz, DMSO) δ = 1.05ppm (t, J 4.6 Hz, 3H, CH3,), δ = 1.22ppm (t, J 4.6 Hz, 3H, CH3,), 3.77–3.93 (m, 2H, -H2C-CH3), 4.04–4.09 (m, 2H, -H2C-CH3), 5.01 (dd, J1(H-H) 6.6, J2(Hc-p) 16.2 Hz 1H,*CH), 6.63 (s, 2H, NH2), 7.13–7.20 (m, 2H, H-Ar), 7.30–7.33 (m, 1H, H-Ar), 7.71 (t, Jc-p 5 Hz,1H, H-Ar), 7.80 (d, Jc-p 6.4 Hz,1H, NH). 13C NMR (100 MHz, DMSO) 15.99 (d, 3JC-p 3.6 Hz, H3C-CH2-), 16.26 (d, 3JC-p 3.6 Hz, H3C-CH2-), 46.88 (d, 1JC-P 5.8Hz *CH), 62.46 (d, 2JC-p 2.5Hz, H3C-CH2-), 62.99(d, 2JC-p 4.7Hz, H3C-CH2-), 114.72 (d, JC-p 14.8 Hz, CH-Ar), 123.83 (d, JC-p 9.8 Hz, CH-Ar), 129.71(d, JC-p62.8Hz, CH-Ar), 158.58(C-Ar),160.25 (F-C-Ar) ppm.
White powder. m.p = 180–182°C. Rf (EtOAc- Petet: 50/50) = 0.17. IR (KBr/cm-1) νmax= 3343.79(NH2), 3097.92(NH), 1323.66-1147.64 (SO2), 1219.42(P = O), 1016.02(P-O).
1H NMR (400 MHz, DMSO) δ = 1.08 (t, J 7.2 Hz, 3H, CH3,), δ = 1.17ppm (t, J 7 Hz, 3H, CH3,) 3.75–3.99 (m, 2H, CH2), 4.00-4.09 (m, 2H, CH2) 5.21 (dd, J1(H-H) 9.6, J2(Hc-p) 24.8 Hz 1H,*CH), 6.86 (s, 2H, NH2), 7.05–7.55 (m, 4H, H-Ar), 6.61 (d, Jc-p 1.6 Hz,1H, NH). 13C NMR (100 MHz, DMSO) 16.16 (d, 3JC-p 5.5 Hz, H3C-CH2-), 16.37 (d, 3JC-p 5.1 Hz, H3C-CH2-), 52.75 (d, 1JC-P 152 Hz *CH), 62.57 (d, 2JC-p 6.9Hz, H3C-CH2-), 62.79(d, 2JC-p 6.6 Hz, H3C-CH2-), 115.16 (d, JC-p 2.5 Hz, CH-Ar), 127.10 (CH-Ar), 130.25-130.38(2CH-Ar), 131.74(C-Ar),132.58 (OH-C-Ar) ppm.
White powder. m.p = 150–152°C. Rf (EtOAc- Petet: 50/50) = 0.18 IR (KBr/cm-1) νmax= 3335.00 and 3257.22(NH2), 3167.08(NH), 1343.22-1162.93 (SO2), 1271.23(P = O), 1037.28(P-O). 1H NMR (400 MHz, DMSO) δ = 1.08 (t, J 4.8 Hz, 3H, CH3,), δ = 1.13ppm (t, J 4.8 Hz, 3H, CH3,), 3.74 (s, 2 OCH3), 3.85–3.98 (m, 2H, CH2), 4.01–4.06 (m, 2H, CH2) 4.59 (dd, J1(H-H) 6.6, J2(Hc-p) 15.4 Hz 1H,*CH), 6.56 (s, 2H, NH2), 6.86–7.03 (m, 3H, H-Ar), 7.61 (d, Jc-p 1.6 Hz,1H, NH). 13C NMR (100 MHz, DMSO) 16.28 (d, 3JC-p 3.2 Hz, H3C-CH2-), 16.34 (d, 3JC-p 2.1 Hz, H3C-CH2-), 55.44 (d, 1JC-P 2.5 Hz, 2JC-P 4.9 Hz *CH),61.75 (s, 2OCH3) 62.06 (d, 2JC-p 4.3Hz, H3C-CH2-), 62.24 (d, 2JC-p 4.3 Hz, H3C-CH2-), 111.22 (d, JC-p 3.6 Hz, CH-Ar), 112.38(d, JC-p 3.2 Hz, CH-Ar), 119.80(d, JC-p 4.3 Hz, CH-Ar), 121.00(d, JC-p 4.7 Hz, C-Ar), 128.17 (MeO-C-Ar), 130.69 (MeO-C-Ar) ppm.
White powder. m.p = 158–160°C. Rf (EtOAc- Petet: 50/50) = 0.26,31P NMR (120 MHz, DMSO) δ20.63, 1H NMR (400 MHz, DMSOd6) δ = 1.03 (t, 3JH-H 7.2Hz, 3H, H3C-CH2-), δ = 1.34 (t, 3JH-H 7 Hz, 3H, H3C-CH2-), 3.60–3.70 (m, 1H, -H2C-CH3), 3.85–3.95 (m, 1H, -H2C-CH3), 4.19–4.56 (m, 2H, -H2C-CH3), 4.84 (d, J(H-H) 5.6 Hz,1H,*CH), 6.28 (s, 1H, NH), 7.06–7.55 (m, 10H, H-Ar), 8.54 (s, 1H, HC = N), 13C NMR (100 MHz, DMSO) 16.18 (d, 3JC-p 5.8 Hz, H3C-CH2-), 16.56 (d, 3JC-p 5.8 Hz, H3C-CH2-), 55.88 (d, 1JC-P 154.2Hz *CH), 63.89 (d, 2JC-p 6.9Hz, H3C-CH2-), 64.11(d, 2JC-p 7.3Hz, H3C-CH2-), 128.31-134.52 (C-Ar), 169.21 (HC = N) ppm.
White powder. m.p = 160–162°C. Rf (EtOAc- Petet: 50/50) = 0.24, 1H NMR (400 MHz, DMSOd6) δ = 1.01 (t, 3JH-H 4.8Hz, 3H, H3C-CH2-), δ = 1.23 (t, 3JH-H 4.8 Hz, 3H, H3C-CH2-), 3.66–3.70 (m, 1H, -H2C-CH3), 3.71–3.87 (m, 1H, -H2C-CH3), 4.03–4.08 (m, 2H, -H2C-CH3), 5.25 (d, J(H-H) 15.2 Hz,1H,*CH), 6.61 (d, J(H-H) 6.4Hz, 1H, H-Ar), 6.67 (t, J(H-H)4.4Hz 1H, H-Ar), 6.76 (t, J(H-H) 5.2 Hz ,1H, H-Ar), 6.89 (d, J(H-H) 5.2 Hz,1H, H-Ar), 6. 93 (t, J(H-H) 5.2 Hz,1H,H-Ar), 7.20 (dd, J(H-H) 1.2 Hz, J(H-p) 5.2 Hz 1H,H-Ar), 7.40–7.42 (m,1H,H-Ar), 7.45 (d, J(H-H) 3.6 Hz, 1H, H-Ar), 8.59 (s, 1H, NH), 8.91 (s, 1H, HC = N), 9.65 (b, 1H, -OH), 10.59 (b, 1H, -OH); 13C NMR (100 MHz, DMSO) 15.96 (d, 3JC-p 5.5 Hz, H3C-CH2-), 16.25 (d, 3JC-p 3.6 Hz, H3C-CH2-), 55.47 (d, 1JC-P 102.5Hz *CH), 62.43(d, 2JC-p 4.4Hz, H3C-CH2-), 62.62(d, 2JC-p 4.7Hz, H3C-CH2), 114.68 (C-Ar), 165.22 (HC = N) ppm.