PAPER
Phosphonylation of Flavones and Coumarins
1049
13C NMR (75 MHz, CDCl3): d = 178.1, 161.0 (d, JP-C = 11.6 Hz),
156.8, 150.7, 150.6, 134.2, 133.7 (d, JP-C = 20.0 Hz), 130.8, 130.1,
129.0, 126.0, 125.7, 124.2, 121.7, 118.3, 113.4, 63.1 (d, JP-C = 5.3
Hz), 16.6 (d, JP-C = 6.1 Hz).
Hz), 117.9 (d, JP-C = 197.1 Hz), 116.9, 63.5 (d, JP-C = 5.7 Hz), 16.5
(d, JP-C = 6.1 Hz).
HRMS (EI): m/z [M]+ calcd for C13H15O5P: 282.0657; found:
282.0657.
HRMS (EI): m/z [M]+ calcd for C19H18ClO5P: 392.0580; found:
392.0580.
Diethyl (7-Methyl-2-oxo-2H-chromen-3-yl)phosphonate (5b)
Yellow powder; yield: 0.19 g (65%); mp 62–64 °C.
Diethyl (2-Methyl-4-oxo-4H-chromen-3-yl)phosphonate (3i)
Yellow liquid; yield: 0.018 g (6%).
1H NMR (400 MHz, CDCl3): d = 8.15 (d, J = 7.0 Hz, 1 H, ArH),
7.66 (t, J = 7.8 Hz, 1 H, ArH), 7.40 (d, J = 7.9 Hz, 2 H, ArH), 4.29–
4.15 (m, 4 H, 2 CH2), 2.87 (s, 3 H, CH3), 1.36 (t, J = 7.0 Hz, 6 H, 2
CH3).
1H NMR (400 MHz, CDCl3): d = 8.40 (s, 1 H, C4-H), 7.39 (d,
J = 7.5 Hz, 1 H, ArH), 7.06 (d, J = 7.4 Hz, 2 H, ArH), 4.19 (m, 4 H,
2 CH2), 2.40 (s, 3 H, 7-CH3), 1.30 (s, 6 H, 2 CH3).
13C NMR (100 MHz, CDCl3): d = 158.9, 155.6, 153.7, 146.4, 129.3,
126.4, 117.1, 115.8, 106.6 (d, JP-C = 200.7 Hz), 63.5, 22.3, 16.6.
HRMS (EI): m/z [M]+ calcd for C14H17O5P: 296.0814; found:
296.0815.
HRMS (EI): m/z [M]+ calcd for C14H17O5P: 296.0814; found:
296.0813.
Diethyl (6-Methyl-2-oxo-2H-chromen-3-yl)phosphonate (5c)
Yellow powder; yield: 0.22 g (74%); mp 74–76 °C.
Diethyl (4-Oxo-4H-chromen-3-yl)phosphonate (3j)
Yellow liquid; yield: 0.014 g (5%).
1H NMR (400 MHz, CDCl3): d = 8.51 (d, J = 7.9 Hz, 1 H, 2-H), 8.22
(d, J = 9.6 Hz, 1 H, ArH), 7.72 (t, J = 7.8 Hz, 1 H, ArH), 7.51–7.44
(m, 2 H, ArH), 4.32–4.19 (m, 4 H, 2 CH2), 1.37 (t, J = 7.1 Hz, 6 H,
2 CH3).
1H NMR (400 MHz, CDCl3): d = 8.40 (d, J = 17.1 Hz, 1 H, 4-H),
7.38 (d, J = 8.5 Hz, 1 H, ArH), 7.30 (s, 1 H, ArH), 7.17 (d, J = 8.5
Hz, 1 H, ArH), 4.23–4.17 (m, 4 H, 2 CH2), 2.35 (s, 3 H, 6-CH3), 1.31
(t, J = 7.0 Hz, 6 H, 2 CH3).
13C NMR (100 MHz, CDCl3): d = 159.0 (2 peaks), 158.9 (2 peaks),
153.7, 153.6, 135.6, 135.0, 129.2, 117.9 (2 peaks), 117.8 (2 peaks),
116.8, 63.6, 20.9, 16.6.
HRMS (EI): m/z [M]+ calcd for C13H15O5P: 282.0657; found:
282.0658.
HRMS (EI): m/z [M]+ calcd for C14H17O5P: 296.0814; found:
296.0814.
Diethyl (E)-(4-Oxo-2-styryl-4H-chromen-3-yl)phosphonate
(3k)
Yellow liquid; yield: 0.10 g (27%).
Diethyl (7-Methoxy-2-oxo-2H-chromen-3-yl)phosphonate (5d)
Yellow oil; yield: 0.24 g (78%).
1H NMR (400 MHz, CDCl3): d = 8.72 (d, J = 15.9 Hz, 1 H, a-H),
8.19 (dd, J = 1.5, 7.9 Hz, 1 H, ArH), 7.80 (d, J = 15.9 Hz, 1 H, b-
H), 7.71–7.70 (m, 3 H, ArH), 7.54 (d, J = 8.3 Hz, 1 H, ArH), 7.44–
7.40 (m, 4 H, ArH), 4.33–4.17 (m, 4 H, 2 CH2), 1.38 (t, J = 7.1 Hz,
6 H, 2 CH3).
13C NMR (75 MHz, CDCl3): d = 177.1, 167.8 (d, JP-C = 24.8 Hz),
155.0, 140.5, 135.4, 134.4, 130.4, 129.1, 128.6, 126.2, 125.7, 123.4
(d, JP-C = 7.7 Hz), 120.0, 117.6, 109.4 (d, JP-C = 187.6 Hz), 62.9 (d,
JP-C = 5.8 Hz), 16.6 (d, JP-C = 6.4 Hz).
1H NMR (400 MHz, CDCl3): d = 8.60–8.20 (m, 1 H, ArH), 7.47 (d,
J = 8.6 Hz, 1 H, ArH), 6.84 (dd, J = 1.6, 34.0 Hz, 1 H, ArH), 6.79
(d, J = 2.0 Hz, 1 H, ArH), 4.23–4.22 (m, 4 H, 2 CH2), 3.88 (s, 3 H,
7-OCH3), 1.37–1.34 (t, J = 5.7 Hz, 6 H, 2 CH3).
13C NMR (100 MHz, CDCl3): d = 165.3, 157.9, 154.0 (d, JP-C = 17.6
Hz), 130.9, 113.8, 112.1 (d, JP-C = 12.4 Hz), 108.7 (d, JP-C = 189.7
Hz), 101.0, 63.6 (d, JP-C = 3.1 Hz), 56.4, 16.8 (d, JP-C = 4.9 Hz).
HRMS (EI): m/z [M]+ calcd for C14H17O6P: 312.0763; found:
312.0762.
HRMS (EI): m/z [M]+ calcd for C21H21O5P: 384.1127; found:
384.1126.
Diethyl (4-Methoxy-2-oxo-2H-chromen-3-yl)phosphonate (5e)
Yellow oil; yield: 0.20 g (63%).
Diethyl (E)-[1-(4-Oxo-4H-chromen-2-yl)-2-phenylvinyl]phos-
phonate (3k¢)
1H NMR (400 MHz, CDCl3): d = 7.78 (d, J = 8.1 Hz, 1 H, ArH),
7.57 (t, J = 7.8 Hz, 1 H, ArH), 7.26 (d, J = 7.0 Hz, 2 H, ArH), 4.26
(s, 3 H, 3-OCH3), 4.23–4.19 (m, 4 H, 2 CH2), 1.32 (t, J = 7.0 Hz, 6
H, 2 CH3).
13C NMR (100 MHz, CDCl3): d = 175.3, 160.9 (d, JP-C = 10.3 Hz),
154.3, 134.6, 125.0, 124.6, 117.1, 103.4 (d, JP-C = 195.6 Hz), 65.5,
63.5 (d, JP-C = 6.2 Hz), 16.6 (d, JP-C = 6.7 Hz).
Yellow liquid; yield: 0.16 g (42%).
1H NMR (400 MHz, CDCl3): d = 8.23 (dd, J = 1.5, 8.0 Hz, 1 H,
ArH), 7.89 (d, J = 23.5 Hz, 1 H, b-H), 7.66–7.62 (m, 1 H, ArH),
7.42 (t, J = 7.5 Hz, 2 H, ArH), 7.32–7.30 (m, 3 H, ArH), 7.28–7.25
(m, 2 H, ArH), 6.47 (d, J = 2.3 Hz, 1 H, C3-H), 4.23–4.16 (m, 4 H,
2 CH2), 1.34 (t, J = 7.1 Hz, 6 H, 2 CH3).
13C NMR (75 MHz, CDCl3): d = 176.5, 171.5 (d, JP-C = 19.6 Hz),
154.0, 134.7, 133.7, 131.9, 131.5, 129.5, 128.1, 126.5, 125.4, 124.2
(d, JP-C = 7.5 Hz), 119.8, 112.5 (d, JP-C = 195.6 Hz), 107.9, 62.8 (d,
JP-C = 5.8 Hz), 16.1 (d, JP-C = 6.4 Hz).
HRMS (EI): m/z [M]+ calcd for C14H17O6P: 312.0763; found
312.0762.
HRMS (EI): m/z [M]+ calcd for C21H21O5P: 384.1127; found:
384.1127.
Diethyl (4,6-Dimethyl-2-oxo-2H-chromen-3-yl)phosphonate
(5f)
Yellow powder; yield: 0.23 g (75%); mp 30–32 °C.
1H NMR (400 MHz, CDCl3): d = 7.55 (s, 1 H, ArH), 7.39 (d, J = 8.4
Hz, 1 H, ArH), 7.18 (d, J = 8.4 Hz, 1 H, ArH), 4.28–4.17 (m, 4 H, 2
CH2), 2.95 (d, J = 2.4 Hz, 3 H, 4-CH3), 2.41 (s, 3 H, 7-CH3), 1.34 (t,
J = 7.1 Hz, 6 H, 2 CH3).
13C NMR (75 MHz, CDCl3): d = 163.4 (d, JP-C = 9.8 Hz), 158.8 (d,
JP-C = 14.9 Hz), 151.8, 135.0, 134.3, 125.9, 119.7 (d, JP-C = 15.5
Hz), 116.8, 115.0 (d, JP-C = 194.5 Hz), 63.1 (d, JP-C = 5.9 Hz), 21.2,
17.3 (d, JP-C = 4.0 Hz), 16.5 (d, JP-C = 6.3 Hz).
Diethyl (2-Oxo-2H-chromen-3-yl)phosphonate (5a)
White powder; yield: 0.18 g (65%); mp.65–66 °C.
1H NMR (400 MHz, CDCl3): d = 8.51 (d, 3JPH = 17.2 Hz, 1 H, C4-
H), 7.63–7.58 (m, 2 H, ArH), 7.36–7.31 (m, 2 H, ArH), 4.32–4.20
(m, 4 H, 2 CH2), 1.37 (t, J = 7.1 Hz, 6 H, 2 CH3).
13C NMR (75 MHz, CDCl3): d = 158.3 (d, JP-C = 14.6 Hz), 155.3,
153.5 (d, JP-C = 6.4 Hz), 134.4, 129.5, 125.1, 118.0 (d, JP-C = 14.1
© Thieme Stuttgart · New York
Synthesis 2012, 44, 1043–1050