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31P NMR dP (202 MHz, DMSO) 9.35. Anal. calcd for: C14H16NO5P:
C, 54.37; H, 5.21; N, 4.53. Found: C, 54.22; H, 5.10; N, 4.31.
6-Oxo-6,7,8,9,10,11-hexahydro-cyclohepta[c]chromen-3-yl
methyl phosphoroamidate (9l). Yield 34%, mp 181–184 ꢂC; vmax
(KBr)/cmꢀ1 3301, 1689, 1606, 1506, 1379, 1248, 1161, 1043, 947,
891, 777, 681; 1H NMR dH (500 MHz, DMSO) 1.40–1.65 (4H, m,
CH2), 1.75–1.90 (2H, m, CH2), 2.70–2.80 (2H, m, CH2), 2.85–3.00
(2H, m, CH2), 3.68 (3H, d, J 11.7, CH3), 5.22 (2H, d, JP–N 7.3,
NH2), 7.10–7.20 (2H, m, Ar–H), 7.89 (1H, d, J 8.8, Ar–H); 13C
NMR dC (125 MHz, DMSO) 161.6, 154.3, 153.6 (d, JP–C 6.1), 153.4,
127.1, 126.7, 117.4 (d, JP–C 5.3), 116.6, 108.5 (d, JP–C 5.3), 53.7 (d,
JP–C 5.7), 32.0, 28.1, 26.7, 25.9, 25.3; 31P NMR dP (202 MHz,
DMSO) 9.35. Anal. calcd for: C15H18NO5P: C, 55.73; H, 5.61; N,
4.33. Found: C, 55.61; H, 5.54; N, 4.15.
4-Oxo-1,2,3,4-tetrahydro-cyclopenta[c]chromen-7-yl
ethyl
phosphoroamidate (9g). Yield 34%, mp 187–189 ꢂC; vmax (KBr)/
cmꢀ1 3340, 1710, 1610, 1566, 1508, 1392, 1261, 1151, 1030, 940,
1
883, 714, 667; H NMR dH (500 MHz, DMSO) 1.25 (3H, t, J 7.1,
CH3), 2.10 (2H, quin, J 7.6, CH2), 2.74 (2H, t, J 7.3, CH2), 3.06
(2H, t, J 7.8, CH2), 4.06 (2H, m, CH2), 5.19 (2H, d, JP–N 7.3, NH2),
7.17–7.25 (2H, m, Ar–H), 7.59 (1H, d, Ar–H); 13C NMR dC (125
MHz, DMSO) 158.9, 156.1, 154.2, 153.2 (d, JP–C 6.2), 126.4, 125.4,
116.8 (d, JP–C 4.8), 114.7, 107.8 (d, JP–C 5.3), 62.2 (d, JP–C 5.7),
31.7, 21.9, 16.0 (d, JP–C 6.6); 31P NMR dP (202 MHz, DMSO) 8.02.
Anal. calcd for: C14H16NO5P: C, 54.37; H, 5.21; N, 4.53. Found: C,
54.22; H, 5.09; N, 4.69.
6-Oxo-7,8,9,10-tetrahydro-6H-benzo[c]chromen-3-yl
ethyl
phosphoroamidate (9h). Yield 36%, mp 167–170 ꢂC; vmax (KBr)/
cmꢀ1 3354, 1695, 1609, 1558, 1506, 1387, 1257, 1161, 1034, 930,
1
891, 725, 683; H NMR dH (500 MHz, DMSO) 1.24 (3H, t, J 7.1,
General method for the synthesis of phosphorodiamidate
derivatives
CH3), 1.70–1.77 (4H, m, CH2), 2.40–2.49 (2H, m, CH2), 2.76–2.78
(2H, m, CH2), 4.02–4.07 (2H, m, CH2) 5.18 (2H, d, JP–N 7.3, NH2),
7.16–7.18 (2H, m, Ar–H), 7.70 (1H, d, J 8.0, Ar–H); 13C NMR dC
(125 MHz, DMSO) 160.5, 152.7 (d, JP–C 6.1), 152.0, 147.2, 125.1,
121.3, 116.6 (d, JP–C 4.8), 116.1, 107.6 (d, JP–C 4.8), 62.1 (d, JP–C
5.3), 24.7, 23.6, 21.1, 20.7, 16.0 (d, JP–C 7.0); 31P NMR dP (202
MHz, DMSO) 8.03. Anal. calcd for: C15H18NO5P: C, 55.73; H,
5.61; N, 4.33. Found: C, 55.86; H, 5.69; N, 4.18.
To an ice-cooled solution of phosphorus oxychloride (0.354 g,
2.3 mmol) in dry THF (7 mL) was added a solution of the
tricyclic coumarin (2.3 mmol) in THF dropwise, followed by
triethylamine (0.233 g, 2.3 mmol). The reaction mixture was
stirred under a nitrogen atmosphere for 1 h. The precipitate of
triethylamine hydrochloride was removed by ltration, and a
solution of NH3 in methanol (5 mL) was added. Aer concen-
tration under vacuum, the crude product was crystallized from
methanol to give the desired product.
6-Oxo-6,7,8,9,10,11-hexahydro-cyclohepta[c]chromen-3-yl ethyl
phosphoroamidate (9i). Yield 32%, mp 163–165 ꢂC; vmax (KBr)/
cmꢀ1 3316, 1687, 1608, 1566, 1508, 1382, 1246, 1169, 1039, 951,
1
4-Oxo-1,2,3,4-tetrahydro-cyclopenta[c]chromꢂen-7-yl phos-
phorodiamidate (9m). Yield 33%, mp 188–190 C; vmax (KBr)/
cmꢀ1 3340, 1691, 1610, 1558, 1504, 1391, 1216, 1130, 972, 895,
889, 733, 681; H NMR dH (500 MHz, DMSO) 1.25 (3H, t, J 7.1,
CH3), 1.40–1.60 (4H, m, CH2), 1.75–1.90 (2H, m, CH2), 2.70–2.80
(2H, m, CH2), 2.85–3.00 (2H, m, CH2), 4.00–4.10 (2H, m, CH2),
5.19 (2H, d, JP–N 6.8, NH2), 7.10–7.20 (2H, m, Ar–H), 7.88 (1H, d, J
8.8, Ar–H); 13C NMR dC (125 MHz, DMSO) 161.6, 154.3, 153.8 (d,
JP–C 6.2), 153.4, 127.0, 126.6, 117.4 (d, JP–C 5.3), 116.5, 108.5 (d, JP–C
5.3), 62.9 (d, JP–C 5.7), 32.0, 28.1, 26.7, 25.9, 25.3, 16.7 (d, JP–C 7.0);
31P NMR dP (202 MHz, DMSO) 8.03. Anal. calcd for: C16H20NO5P:
C, 56.97; H, 5.98; N, 4.15. Found: C, 57.13; H, 6.07; N, 4.32.
4-Oxo-1,2,3,4-tetrahydro-cyclopenta[c]chromen-7-yl methyl
phosphoroamidate (9j). Yield 36%, mp 164–166 ꢂC; vmax (KBr)/
cmꢀ1 3323, 1707, 1610, 1510, 1394, 1263, 1155, 1049, 964, 887,
793, 664; 1H NMR dH (500 MHz, DMSO) 2.1 (2H, quin, J 7.6,
CH2), 2.73 (2H, t, J 7.3, CH2), 3.04 (2H, t, J 7.6, CH2), 3.68 (3H, d, J
11.2, CH3), 5.24 (2H, d, JP–N 7.3, NH2), 7.17–7.24 (2H, m, Ar–H),
7.58 (1H, d, J 8.3, Ar–H); 13C NMR dC (125 MHz, DMSO) 159.6,
156.7, 154.9, 153.8 (d, JP–C 5.7), 127.1, 126.2, 117.5 (d, JP–C 5.3),
115.5, 108.5 (d, JP–C 5.3), 53.7 (d, JP–C 5.7), 32.4, 30.9, 22.6; 31P
NMR dP (202 MHz, DMSO) 14.09. Anal. calcd for: C13H14NO5P:
C, 52.89; H, 4.78; N, 4.74. Found: C, 52.75; H, 4.69; N, 4.55.
6-Oxo-7,8,9,10-tetrahydro-6H-benzo[c]chromen-3-yl methyl
phosphoroamidate (9k). Yield 28%, mp 183–187 ꢂC; vmax (KBr)/
cmꢀ1 3311, 1699, 1608, 1508, 1386, 1258, 1159, 1055, 960, 885,
789, 680; 1H NMR dH (500 MHz, DMSO) 1.65–1.80 (4H, m, CH2),
2.37–2.43 (2H, m, CH2), 2.70–2.80 (2H, m, CH2), 3.68 (3H, d, J
11.2, CH3), 5.22 (2H, d, JP–N 7.3, NH2), 7.14–7.20 (2H, m, Ar–H),
7.69 (1H, d, J 8.3, Ar–H); 13C NMR dC (125 MHz, DMSO) 160.5,
152.6 (d, JP–C 6.1), 152.0, 147.1, 125.1, 121.4, 116.6 (d, JP–C 4.8),
116.2, 107.6 (d, JP–C 5.3), 53.0 (d, JP–C 5.7), 24.7, 23.6, 21.1, 20.7;
1
729; H NMR dH (500 MHz, DMSO) 2.10 (2H, quin, J 7.3, CH2),
2.74 (2H, t, J 7.3, CH2), 3.05 (2H, t, J 7.6, CH2), 4.53 (4H, d, JP–N
4.4, NH2), 7.10–7.30 (2H, m, Ar–H), 7.54 (1H, d, J 8.0, Ar–H); 13
C
NMR dC (125 MHz, DMSO) 159.8, 157.0, 155.1 (d, JP–C 6.6), 154.9,
126.7, 125.5, 118.1 (d, JP–C 5.3), 114.7, 108.8 (d, JP–C 4.8), 32.4,
30.8, 22.7; 31P NMR dP (202 MHz, DMSO) 16.01. Anal. calcd for:
C
12H13N2O4P: C, 51.43; H, 4.68; N, 10.00. Found: C, 51.57; H,
4.59; N, 10.18.
6-Oxo-7,8,9,10-tetrahydro-6H-benzo[c]chromen-3-yl phos-
ꢂ
phorodiamidate (9n). Yield 46%, mp 188–191 C; vmax (KBr)/
cmꢀ1 3364, 1683, 1610, 1562, 1504, 1386, 1217, 1140, 962, 893,
725; 1H NMR dH (500 MHz, DMSO) 1.68–1.75 (4H, m, CH2),
2.37–2.48 (2H, m, CH2), 2.71–2.74 (2H, m, CH2), 4.52 (4H, d, JP–
N 4.4, NH2), 7.11–7.20 (2H, m, Ar–H), 7.61 (1H, d, J 8.8, Ar–H);
13C NMR dC (125 MHz, DMSO) 161.4, 154.6 (d, JP–C 6.6), 152.7,
148.0, 125.3, 121.4, 117.9 (d, JP–C 5.3), 116.0, 108.5 (d, JP–C 4.8),
25.3, 24.3, 21.8, 21.5; 31P NMR dP (202 MHz, DMSO) 15.99.
Anal. calcd for: C13H15N2O4P: C, 53.06; H, 5.14; N, 9.52. Found:
C, 53.23; H, 5.26; N, 9.72.
6-Oxo-6,7,8,9,10,11-hexahydro-cyclohepta[c]chromen-3-yl phos-
ꢂ
phorodiamidate (9o). Yield 41%, mp 187–189 C (with decom-
position); vmax (KBr)/cmꢀ1 3232, 1703, 1605, 1564, 1504, 1381,
1
1203, 1142, 949, 908, 729; H NMR dH (500 MHz, DMSO) 1.46–
1.49 (2H, m, CH2), 1.55–1.58 (2H, m, CH2), 1.79–1.82 (2H, m,
CH2), 2.73–2.78 (2H, m, CH2), 2.90–2.97 (2H, m, CH2), 4.53 (4H,
d, JP–N 3.9, NH2), 7.12–7.22 (2H, m, Ar–H), 7.83 (1H, d, J 8.8, Ar–
H); 13C NMR dC (125 MHz, DMSO) 161.8, 154.9 (d, JP–C 6.6),
This journal is © The Royal Society of Chemistry 2014
RSC Adv., 2014, 4, 44350–44358 | 44355