Molecules 2010, 15
5119
(d, 18H, J = 6.3 Hz, 6CH3), 1.42-1.59 (m, 2H, CH2), 1.76-1.89 (m, H, CH), 4.26-4.48 (m, 2H, NCH2),
4.69-4.78 (m, 2H, 2OCH), 5.09 (d, 1H, J = 5.75 Hz, CH), 6.27 (s, 1H, PCH), 7.06-7.46 (m, 10H, ArH),
7.81 (s, 1H, NH), 8.73 (br s, 1H, NH); 13C-NMR (CDC13): δ 183.9, 172.0, 138.2, 135.5, 128.7, 128.5,
127.6, 127.2, 73.2, 56.4, 55.9, 43.5, 40.2, 38.7, 24.3, 23.1; 31P-NMR (CDCl3): δ 22.8; IR (KBr, cm-1): v
3285, 3063, 2929, 1674, 1558, 1215, 1014; Anal. Calcd for C27H40N3O4PS: C 60.77, H 7.55, N 7.87;
Found: C 60.63, H 7.24, N 7.66.
Dibutyl (3-(
L-1-benzylamino-4-methyl-1-oxopentan-2-yl)thioureido)(phenyl)methylphosphonate (3d).
1
Colorless viscous liquid, yield 86%; [
α
]20 -16.4º (c 0.1, acetone); H-NMR (CDC13): δ 0.80-0.95 (m,
D
12H, 4CH3), 1.20-1.43 (m, 10H, 5CH2), 1.55-1.72 (m, 1H, CH), 3.66-4.05 (m, 2H, NCH2), 4.11-4.55
(m, 4H, 2OCH2), 5.04 (d, 1H, J = 6.3 Hz, CH), 6.27 (s, 1H, PCH), 6.43(s, 1H, NH), 6.92-7.44 (m,
13
10H, ArH), 7.83 (s, 1H, NH), 8.70 (br s, 1H, NH); C-NMR (CDC13): δ 184.5, 170.6, 138.2, 135.6,
31
128.9, 128.6, 127.8, 67.7, 65.8, 55.5, 43.4, 34.8, 32.2, 26.9, 18.8, 13.7; P-NMR (CDCl3): δ 22.1; IR
(KBr, cm-1): v 3269, 3082, 2953, 1670, 1550, 1220, 1024; Anal. Calcd for C29H44N3O4PS: C, 62.01; H,
7.90; N, 7.48; Found: C 62.28, H 7.67, N 7.72.
Diethyl (3-(
L-1-benzylamino-3,3-dimethyl-1-oxobutan-2-yl)thioureido)(phenyl)methylphosphonate (3e).
1
White crystals, yield 98%; m.p. 157-159 ºC; [
α
]20 +15.5º (c 0.1, acetone); H-NMR (CDC13): δ 0.98
D
(s, 9H, C(CH3)3), 1.07 (t, 6H, J = 6.9 Hz, 2CH3), 3.75-4.06 (m, 2H, NCH2), 4.10-4.46 (m, 4H, 2OCH2),
4.93 (d, 1H, J = 8.6 Hz, CH(t-Bu)), 6.26 (s, 1H, PCH), 6.47 (s, 1H, NH), 7.15-7.47 (m, 10H, ArH),
13
7.92 (s, 1H, NH), 9.03 (br s, 1H, NH); C-NMR (CDCl3): δ 184.3, 170.7, 138.2, 135.4, 128.7, 128.0,
31
127.4, 66.3, 64.1, 55.4, 43.4, 34.8, 26.9; 16.5; P-NMR (CDCl3): δ 21.7; IR (KBr, cm-1): v 3292,
3068, 2965, 2867, 1669, 1562, 1221, 1013; Anal. Calcd for C25H36N3O4PS: C 59.39, H 7.18, N 8.31;
Found: C 59.52, H 7.34, N 8.12.
Dipropyl
(3-(L-1-benzylamino-3,3-dimethyl-1-oxobutan-2-yl)thioureido)(phenyl)methylphosphonate
1
(3f). White crystals, yield 93%; m.p. 171-172 ºC; [
α
]20 +9.6º (c 0.1, acetone); H-NMR (CDC13): δ
D
0.76 (t, 6H, J = 6.85 Hz, 2CH3), 1.03 (s, 9H, 3CH3), 1.42-1.74 (m, 4H, 2CH2), 3.70-3.95 (m, 2H,
NCH2), 4.09-4.47 (m, 4H, 2OCH2), 4.94 (d, 1H, J = 8.6 Hz, CH(t-Bu)), 6.25 (s, 1H, PCH), 6.53 (s, 1H,
13
NH), 7.12-7.47 (m, 10H, ArH), 7.94 (s, 1H, NH), 9.11 (br s, 1H, NH); C-NMR (CDC13): δ 184.4,
170.6, 138.0, 135.2, 128.7, 128.4, 127.5, 69.4, 65.8, 55.3, 43.3, 34.7, 26.8, 24.0, 9.9; 31P-NMR
(CDCl3): δ 21.5; IR (KBr, cm-1): v 3288, 3056, 2952, 2873, 1677, 1543, 1218, 1012; Anal. Calcd for
C27H40N3O4PS: C 60.77, H 7.55, N 7.87; Found: C 60.52, H 7.71, N 7.59.
Diisopropyl
(3-(L-1-benzylamino-3,3-dimethyl-1-oxobutan-2-yl)thioureido)(phenyl)methylphos-
1
phonate (3g). White crystals, yield 96%; m.p. 176-177 ºC; [
α
]2D0 +7.2º (c 0.1, acetone); H-NMR
(CDC13, 500 MHz): δ 1.01 (s, 9H, 3CH3), 1.19 (d, 12H, J = 6.3 Hz, 4CH3), 4.22-4.46 (m, 2H, NCH2),
4.63-4.84 (m, 2H, 2OCH), 4.96 (d, 1H, J = 7.45 Hz, CH(t-Bu)), 6.32 (s, 1H, PCH), 6.38 (s, 1H, NH),
13
7.11-7.52 (m, 10H, ArH), 7.80 (s, 1H, NH), 9.05 (br s, 1H, NH); C-NMR (CDC13, 125 MHz): δ
184.6, 170.7, 138.3, 135.8, 128.9, 128.6, 127.4, 73.1, 66.4, 55.9, 43.2, 34.6, 27.0, 24.3; 31P-
NMR(CDCl3, 200 MHz): δ 19.7; IR (KBr, cm-1): v 3286, 3057, 2963, 2861, 1672, 1548, 1224, 1011;
Anal. Calcd for C27H40N3O4PS: C 60.77, H 7.55, N 7.87; Found: C 60.91, H 7.34, N 7.48.