SYNTHESIS OF PHOSPHONATED 3-(BENZYLAMINOMETHYL)COUMARINS
3689
=
(1658) and 1244 (P O); (400 MHz; CDCl3) 1.31 (6H, overlapping triplets,
2 ꢂ OCH2CH3), 3.10 (2H, d, JP,H ¼ 22 Hz, CH2P), 4.09 (2H, overlapping signals,
2 ꢂ CH2OP), 4.51 and 4.85 (4H, 2 ꢂ s, 2 ꢂ CH2N), 7.22–7.67 (9H, overlapping multi-
plets, Ar-H) and 7.98 (1H, s, 4-H); dC (100 MHz; CDCl3)15 16.3 (d, JP,C ¼ 6.3 Hz,
2 ꢂ OCH2CH3), 33.6 (d, JP,C ¼ 130 Hz, CH2P), 45.8 and 52.7 (2 ꢂ CH2N), 62.9 (d,
JP,C ¼ 6.6 Hz, 2 ꢂ CH2OP), 116.3, 119.3, 123.5 124.4, 126.2, 128.0, 128.7, 129.1,
=
131.2, 135.9, 139.6 and 153.1 (Ar-C), 161.3 and 166.1 (C O); m=z 443 (M þ 1,
10%) and 106 (100%).
Diethyl N-Benzyl-N-[(8-ethoxy-2-oxo-2H-chromen-3-yl)-
methyl]carbamoylmethylphosphonate 10b
The procedure described for the synthesis of compound 10d was followed
using N-benzyl-2-chloro-N-[(8-ethoxy-2-oxo-2H-chromen-3-yl)methyl]acetamide 9b
(0.30 g, 0.8 mmol) and triethyl phosphite (0.26 ml, 2 mmol). Chromatography
afforded diethyl N-benzyl-N-[(8-ethoxy-2-oxo-2H-chromen-3-yl)methyl]carbamoyl-
methylphosphonate 10b as a brown oil (0.19 g, 77%) (Found Mþ: 487.174816.
C25H30NO7P requires M, 487.175991); nmax (nujol)=cmꢁ1 OꢁC O (1721), NꢁC O
=
=
=
(1658) and 1244 (P O); (400 MHz; CDCl3) 1.28 (6H, overlapping triplets,
2 ꢂ OCH2CH3), 1.46 (3H, t, J ¼ 7 Hz, Ar-OCH2CH3), 3.1 (2H, d, JP,H ¼ 22 Hz,
CH2P), 4.17 (6H, overlapping multiplets, 2 ꢂ CH2OP and Ar-OCH2CH3), 4.50
and 4.82 (4H, 2 ꢂ s, 2 ꢂ CH2N), 7.10–7.43 (8H, overlapping multiplets, Ar-H),
7.92 (1H, s, 4-H); dC (100 MHz; CDCl3)15 14.7 (Ar-OCH2CH3), 16.3 (d,
JP,C ¼ 4.2 Hz, 2 ꢂ OCH2CH3), 27.4 (d, JP,C ¼ 298 Hz, CH2P), 45.8 and 52.7
(2 ꢂ CH2N), 62.8 (d, JP,C ¼ 4.3 Hz, 2 ꢂ CH2OP), 65.0 (Ar-OCH2CH3), 119.5,
120.1, 124.2, 124.6, 126.3; 127.9, 128.0, 128.7, 129.1, 136.0, 139.8 and 146.3
=
(Ar-C), 160.9 and 166.1 (C O); m=z 487 (M þ 1, 24%) and 106 (100%).
Diethyl N-Benzyl-N-[(6-chloro-2-oxo-2H-chromen-3-yl)-
methyl]carbamoylmethylphosphonate 10c
The procedure described for the synthesis of compound 10d was followed
using N-benzyl-2-chloro-N-[(6-chloro-2-oxo-2H-chromen-3-yl)methyl]acetamide 9c
(0.46 g, 1.2 mmol) and triethyl phosphite (0.40 ml, 2 mmol). Chromatography afforded
diethyl N-benzyl-N-[(6-chloro-2-oxo-2H-chromen-3-yl)methyl]carbamoylmethylphoþs-
phonate 10c as a yellow solid (0.455 g, 77%), m.p. 165–167 ꢀC (Found M :
477.111852. C23H25ClNO6P requires M: 477.110804); nmax (nujol)=cmꢁ1 OꢁC O
=
=
=
(1721), NꢁC O (1658) and 1244 (P O); (400 MHz; CDCl3) 1.35 (6H, overlapping
triplets, 2 ꢂ OCH2CH3), 3.14 (2H, d, JP,H ¼ 22 Hz, CH2P), 4.09 (4H, overlapping mul-
tiplets, 2 ꢂ CH2OP), 4.55 and 4.87 (4H, 2 ꢂ s, 2 ꢂ CH2N), 7.27–7.49 (7H, m, Ar-H),
7.56 (1H, s, 5-H) and 7.93 (1H, s, 4-H); dC (100 MHz; CDCl3)15 16.3 (d, JP,C ¼ 6.2 Hz,
2 ꢂ OCH2CH3), 33.6 (d, JP,C ¼ 130 Hz, CH2P), 45.9 and 52.8 (2 ꢂ CH2N), 62.9 (d,
JP,C ¼ 6.5 Hz, 2 ꢂ CH2OP) 117.8, 120.4, 124.9, 127.2, 127.9, 128.7, 129.1, 129.7,
=
131.1, 135.8, 138.1 and 151.4 (Ar-C), 160.6 and 166.2 (C O); m=z 477 (M þ 1, 10%)
and 106 (100%).