Green Chemistry
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(1.2 mmol), and palladacycle II (1 mol%) was dissolved in H2O Hz, 1H), 7.75–7.69 (m, 1H), 7.53 (d, J = 5.6 Hz, 1H), 7.42 (d, J =
(2 mL) in a 10 mL vial under nitrogen atmosphere. The 5.2 Hz, 1H), 4.75–4.66 (m, 2H), 1.40 (d, J = 6.4 Hz, 6H), 1.22 (d,
mixture then refluxed for 16 h. After the reaction was com- J = 6.0 Hz, 6H); 13C NMR (CDCl3, 100 MHz) δ 143.3 (d, J = 3.3
plete, the mixture was filtered through a pad of Celite, and Hz), 139.1 (d, J = 17.0 Hz), 128.1 (d, J = 10.9 Hz), 127.6, 126.3
washed with dichloromethane. And the mixture was added (d, J = 11.0 Hz), 125.5 (d, J = 188.5 Hz), 124.2 (d, J = 1.3 Hz),
into H2O (25 mL) and extracted with dichloromethane (10 mL) 122.6 (d, J = 15.8 Hz), 70.7 (d, J = 5.3 Hz), 24.1 (d, J = 3.9 Hz),
for three times. The combined organic layer was dried over 23.9 (d, J = 4.8 Hz); 31P NMR (CDCl3, 163 MHz) δ 18.1; HRMS:
anhydrous Na2SO4 and filtered. After removal of the solvent m/z 299.0871 ([M + H]+, C14H20O3PS+ calcd 299.0871).
in vacuum, the residue was purified by flash chromatography
on silica gel (dichloromethane/methanol) to give the pure 65%; 1H NMR (400 MHz, CDCl3) δ 7.71 (dd, J = 13.2 Hz and 8.0
product. Hz, 2H), 7.26 (dd, J = 8.0 Hz and 4.0 Hz, 2H), 4.71–4.62 (m,
Diisopropyl (4-butylphenyl)phosphonate (3n). Oil, yield:
Diisopropyl (2-acetamidophenyl)phosphonate (3e). Oil, 2H), 2.65 (t, J = 7.6 Hz, 2H), 1.65–1.57 (m, 2H), 1.41–1.32 (m,
yield: 62%; 1H NMR (400 MHz, CDCl3) δ 10.69 (s, 1H), 8.58 8H), 1.22 (d, J = 6.4 Hz, 6H), 0.93 (t, J = 7.4 Hz, 3H); 13C NMR
(t, J = 7.2 Hz, 1H), 7.61–7.48 (m, 2H), 7.11 (t, J = 5.6 Hz, 1H), (CDCl3, 100 MHz) δ 147.3 (d, J = 3.0 Hz), 131.7 (d, J = 10.2 Hz),
4.69–4.61 (m, 2H), 2.21 (s, 3H), 1.39 (d, J = 6.0 Hz, 6H), 128.3 (d, J = 15.2 Hz), 126.6 (d, J = 189.6 Hz), 70.4 (d, J = 5.4
1.23 (d, J = 6.0 Hz, 6H); 13C NMR (CDCl3, 100 MHz) Hz), 35.6, 33.1, 24.0 (d, J = 3.8 Hz), 23.7 (d, J = 4.8 Hz), 22.2,
δ 169.0, 142.4 (d, J = 7.5 Hz), 133.7 (d, J = 2.2 Hz), 132.6 13.8; 31P NMR (CDCl3, 163 MHz) δ 17.9; HRMS: m/z 299.1771
(d, J = 5.7 Hz), 122.8 (d, J = 13.6 Hz), 120.6 (d, J = 11.4 Hz), ([M + H]+, C16H28O3P+ calcd 299.1775).
115.1 (d, J = 179.1 Hz), 71.6 (d, J = 5.4 Hz), 25.2, 24.0 (d, J =
Diisopropyl
(4-methoxy-3-methylphenyl)phosphonate
3.8 Hz), 23.7 (d, J = 5.0 Hz); 31P NMR (CDCl3, 163 MHz) (3o). Oil, yield: 90%; 1H NMR (400 MHz, CDCl3) δ 7.64 (dd, J =
δ 17.9; HRMS: m/z 300.1365 ([M + H]+, C14H23NO4P+ calcd 12.4 Hz and 9.0 Hz, 1H), 7.57 (d, J = 12.4 Hz, 1H), 6.87 (dd, J =
300.1365).
8.2 Hz and 3.4 Hz, 1H), 4.69–4.60 (m, 2H), 3.86 (s, 3H), 3.09 (s,
Diisopropyl (3-methoxyphenyl)phosphonate (3g). Oil, yield: 3H), 1.37 (d, J = 6.4 Hz, 6H), 1.22 (d, J = 6.4 Hz, 6H); 13C NMR
86%; 1H NMR (400 MHz, CDCl3) δ 7.42–7.32 (m, 3H), (CDCl3, 100 MHz) δ 160.7 (d, J = 3.4 Hz), 133.8 (d, J = 11.1 Hz),
7.08–7.05 (m, 1H), 4.73–4.64 (m, 2H), 3.85 (s, 3H), 1.38 131.4 (d, J = 10.9 Hz), 126.6 (d, J = 15.4 Hz), 120.3 (d, J = 207.3
(d, J = 6.4 Hz, 6H), 1.23 (d, J = 6.0 Hz, 6H); 13C NMR Hz), 109.3 (d, J = 16.8 Hz), 70.2 (d, J = 5.3 Hz), 55.2, 23.9 (d, J =
(CDCl3, 100 MHz) δ 159.1 (d, J = 18.7 Hz), 131.0 (d, J = 3.8 Hz), 23.7 (d, J = 4.8 Hz); 31P NMR (CDCl3, 163 MHz) δ 18.6;
186.1 Hz), 129.5 (d, J = 17.4 Hz), 123.9 (d, J = 9.1 Hz), 118.3 HRMS: m/z 287.1407 ([M + H]+, C14H24O4P+ calcd 287.1409).
(d, J = 2.6 Hz), 116.2 (d, J = 10.2 Hz), 70.7 (d, J = 5.3 Hz), 55.3,
Diisopropyl
[3-(dimethylamino)phenyl]phosphonate
24.0 (d, J = 3.6 Hz), 23.8 (d, J = 4.7 Hz); 31P NMR (CDCl3, (3p). Oil, yield: 90%; 1H NMR (400 MHz, CDCl3) δ 7.33–7.28
163 MHz) δ 17.0; HRMS: m/z 273.1254 ([M + H]+, C13H22O4P+ (m, 2H), 7.19–7.07 (m, 2H), 6.85 (dd, J = 8.4 Hz and 2.0 Hz,
calcd 273.125).
1H), 4.71–4.62 (m, 2H), 2.98 (s, 6H), 1.37 (d, J = 6.4 Hz, 6H),
Diisopropyl (4-vinylphenyl)phosphonate (3i). Oil, yield: 1.23 (d, J = 6.4 Hz, 6H); 13C NMR (CDCl3, 100 MHz) δ 150.0 (d,
1
58%; H NMR (400 MHz, CDCl3): δ 7.78 (dd, J = 13.2 Hz and J = 16.8 Hz), 130.0 (d, J = 184.3 Hz), 129.0 (d, J = 17.2 Hz), 119.2
8.0 Hz, 2H), 7.48 (dd, J = 7.6 Hz and 3.6 Hz, 2H), 6.73 (dd, J = (d, J = 9.0 Hz), 115.6 (d, J = 3.0 Hz), 115.2 (d, J = 12.5 Hz), 70.4
17.6 Hz and 10.8 Hz, 1H), 5.85 (d, J = 17.6 Hz, 1H), 5.37 (d, J = (d, J = 5.2 Hz), 40.3, 24.0 (d, J = 3.7 Hz), 23.7 (d, J = 4.9 Hz); 31
P
10.8 Hz, 1H), 4.73–4.64 (m, 2H), 1.37 (d, J = 6.4 Hz, 6H), 1.22 NMR (CDCl3, 163 MHz) δ 18.7; HRMS: m/z 286.1567 ([M + H]+,
(d, J = 6.4 Hz, 6H); 13C NMR (CDCl3, 100 MHz) δ 141.1 (d, J = C14H25NO3P+ calcd 286.1570).
3.3 Hz), 136.0 (d, J = 1.3 Hz), 132.0 (d, J = 10.0 Hz), 128.8 (d, J =
Diisopropyl (2-chlorophenyl)phosphonate (3s). Oil, yield:
189.0 Hz), 126.0 (d, J = 15.3 Hz), 116.3, 70.7 (d, J = 5.4 Hz), 24.0 69%; 1H NMR (400 MHz, CDCl3) δ 8.05 (dd, J = 14.4 Hz and
(d, J = 3.9 Hz), 23.8 (d, J = 4.8 Hz); 31P NMR (CDCl3, 163 MHz) 7.2 Hz, 1H), 7.47–7.44 (m, 2H), 7.38–7.27 (m, 1H), 4.78–4.69
δ 17.1; HRMS: m/z 269.1310 ([M + H]+, C14H22O3P+ calcd (m, 2H), 1.40 (d, J = 6.0 Hz, 6H), 1.26 (d, J = 6.4 Hz, 6H);
269.1307).
13C NMR (CDCl3, 100 MHz) δ 136.8 (d, J = 2.8 Hz), 136.0 (d,
Diisopropyl (4-methoxycarbonylphenyl)phosphonate (3j). J = 8.0 Hz), 133.3 (d, J = 2.5 Hz), 130.7 (d, J = 10.1 Hz), 128.5 (d,
Oil, yield: 85%; 1H NMR (400 MHz, CDCl3) δ 8.11 (dd, J = J = 189.1 Hz), 126.3 (d, J = 13.7 Hz), 71.4 (d, J = 5.6 Hz), 24.1
7.8 Hz and 3.8 Hz, 2H), 7.90 (dd, J = 12.8 and 8.0 Hz, (d, J = 4.1 Hz), 23.7 (d, J = 4.8 Hz); 31P NMR (CDCl3, 163 MHz)
2H), 4.76–4.67 (m, 2H), 3.95 (s, 3H), 1.38 (d, J = 6.0 Hz, δ 12.5; HRMS: m/z 277.0762 ([M + H]+, C12H19ClO3P+ calcd
6H), 1.23 (d, J = 6.4 Hz, 6H); 13C NMR (CDCl3, 100 MHz) 277.0760).
δ 166.4, 134.9 (d, J = 185.9 Hz), 133.2 (d, J = 3.3 Hz), 131.8 (d,
J = 9.9 Hz), 129.3 (d, J = 14.9 Hz), 71.2 (d, J = 5.6 Hz), 52.5, 24.1
(d, J = 3.9 Hz), 23.8 (d, J = 4.7 Hz); 31P NMR (CDCl3, 163 MHz)
Acknowledgements
δ 15.3; HRMS: m/z 301.1206 ([M + H]+, C14H22O5P+ calcd
301.1199).
We are grateful to the National Natural Science Foundation of
Diisopropyl (benzo[b]thiophen-5-yl)phosphonate (3k). Pale China (No. 21172200, 21102134) and the Innovation Fund for
1
yellow solid, mp 104–105 °C; yield: 73%; H NMR (400 MHz, Outstanding Scholar of Henan Province (No. 621001100) for
CDCl3) δ 8.36 (d, J = 14.4 Hz, 1H), 7.96 (dd, J = 8.4 Hz and 3.6 financial support to this research.
This journal is © The Royal Society of Chemistry 2013
Green Chem., 2013, 15, 1055–1060 | 1059