Phosphoryl Amino Acids
605
Compound P1. C24H28NO8P
0.5404 g chrysin and 0.5398 g N-phosphoryl L-Alanine were added to a
solution of 40 ml THF. The mixture was stirred until chrysin was dis-
solved and then a solution of DCC and DMAP (0.5936 g DCC + 0.0530 g
DMAP) was added with vigorous stirring in ice-water bath. The reaction
proceeded for 12 h at 5–10◦C. The solution was removed by distillation.
The product was further purified by column chromatography (ethyl ac-
etate:petroleum ether:ethanol = 50:40:1). The yield of yellow product
1
is 62%. m.p. 155–156◦C. H NMR (400 MHz, DMSO) δ: 8.10 (d, 2H,
J = 7.40, 2ꢀ-H, 6ꢀ-H), 7.62 (m, 3H, 3ꢀ-H, 4ꢀ-H, 5ꢀ-H), 7.13 (s, 1H, 3-H),
7.09 (d, 1H, J = 1.1, 6-H), 6.60 (s, 1H, J = 1.2, 8-H), 4.51 (m, 2H, 2ꢀꢀꢀ-H),
4.05 (m, 1H, 2ꢀꢀ-H), 2.53 (1H, N-H), 1.47 (m, 3H, 1ꢀꢀ-H), 1.28 (m, 12H,
1ꢀꢀꢀ-H). 13C NMR δ: 182.82 (s, 1C, 4-C), 172.21 (s, 1C, 3ꢀꢀ-C), 164.57 (s, 1C,
5-C), 160.88 (s, 1C, 2-C), 156.69 (s, 1C, 9-C), 156.22 (s, 1C, 7-C), 132.80
(s, 1C, 1ꢀ-C), 130.63 (s, 2C, 3ꢀ-C, 5ꢀ-C), 129.57 (s, 1C, 4ꢀ-C), 126.83 (d, 2C,
J = 98,2ꢀ-C, 6ꢀ-C), 108.66 (s, 1C, 10-C), 106.11 (s, 1C, 6-C), 105.31 (s, 1C,
3-C), 101.84 (s, 1C, 8-C), 70.34 (m, 1C, 2ꢀꢀꢀ-C), 50.68 (s, C, 2ꢀꢀ-C), 23.89 (d,
1C, J = 17.6, 1ꢀꢀꢀ-C), 19.67 (d, 1C, J = 26.4, 1ꢀꢀ-C). 31P NMR (400 MHz,
D2O): δ: 6.243. ESI-MS/MS: m/z: 490[M + H]+, 978 [2M], 1001 [2M
+ Na]+. IR 1265 (PO). A molecular formula of C24H28NO8P was de-
termined from the molecular ion peak at 490.1639.1130 m/z [M+H]+
(calcd. 490.1631 for C24H28NO8P ) obtained by ESIQ-TOF.
Compound P2. C26H32NO8P
0.4678 g chrysin and 0.5895 g phosphoryl L-valine was added to a solu-
tion of 40 ml THF. The mixture was stirred until chrysin was dissolved
and then a solution of DCC and DMAP (0.5216 g DCC + 0.0568 g DMAP)
was added dropwise with vigorous stirring in ice-water bath. The reac-
tion proceeded for 12 h at 5–10◦C. The solution was removed by distilla-
tion. The product was further purified by column chromatography (ethyl
acetate:petroleum ester:ethanol = 50:40:1). The yield of yellow prod-
1
uct is 60%. m.p. 176–178. H NMR (400 MHz, DMSO): δ: 8.14 (d, 2H,
J = 7.20, 2ꢀ-H, 6ꢀ-H), 7.62 (m, 3H, 3ꢀ-H, 4ꢀ-H, 5ꢀ-H), 7.16 (s, 1H, 3-H),
7.09 (d, 1H, J = 0.8, 6-H), 6.60 (s, 1H, 8-H), 4.49 (m, 2H, 2ꢀꢀꢀ-H), 3.67 (m,
1H, 3ꢀꢀ-H), 2.52 (1H, N-H), 2.13 (m, 1H, 2ꢀꢀ-H), 1.24 (m, 12H, 1ꢀꢀꢀ-H),
1.03 (m, 6H, 1ꢀꢀ-H). 13C NMR δ:182.84 (s, 1C, 4-C), 171.30 (s, 1C, 4ꢀꢀ-C),
164.57 (s, 1C, 5-C), 160.87 (s, 1C, 2-C), 156.73 (s, 1C, 9-C), 155.93 (s,
1C, 7-C), 132.82 (s, 1C, 1ꢀ-C), 130.63 (s, 2C, 3ꢀ-C, 5ꢀ-C), 129.55 (s, 1C,
4ꢀ-C), 126.99 (d, 2C, J = 98, 2ꢀ-C, 6ꢀ-C), 108.72 (s, 1C, 10-C), 106.13 (s,
1C, 6-C), 105.12 (s, 1C, 3-C), 101.82 (s, 1C, 8-C), 70.45 (d, 1C, J = 55.6,
2ꢀꢀꢀ-C), 60.91 (s, 1C, 3ꢀꢀ-C), 31.53 (s, 1C, 2ꢀꢀ-C), 19.05 (d, 1C, J = 27,