3
3
4
NMR (CDCl3): d 16.06 (d, 3J = 6.6 Hz, CH3), 62.57 (d, 2J = 5.2 Hz,
6.54 (dd, J = 3.4, 1.7 Hz, 1 H, H-4¢), 7.16 (tdd, J = 7.6, JPH
=
1
4
3
4
OCH2), 114.24 (d, J = 179.3 Hz, Cq-1), 119.68 (s, Cq-2¢), 120.98
3.1, J = 1.0 Hz, 1 H, H-5), 7.27 (dd, J = 3.4, J = 0.7 Hz, 1 H,
(d, 3J = 11.4 Hz, CH-3), 123.48 (d, 3J = 13.5 Hz, CH-5), 127.52 (s,
CH-5¢), 128.57 (s, CH-6¢), 131.27 (s, CH-3¢), 132.44 (d, 2J = 5.9 Hz,
CH-6), 133.62 (s, CH-4¢), 133.99 (d, 4J = 2.2 Hz, CH-4), 138.06 (s,
H-3¢), 7.58 (partly superimp. t br, J = ca. 8, 7 Hz, 1 H, H-4),
3
7.61 (superimp. dd, 3J = 1.7, 4J = 0.7 Hz, 1 H, 5¢-H), 7.63 (partly
superimp. ddd, 3JPH = 14.8, 3J = 7.7, 4J = 1.5 Hz, 1 H, H-6), 8.76 (t
Cq-1¢), 142.23 (d, 2J = 7.4 Hz, Cq-2), 166.08 ppm (s, CO). 31P{ H}
br, 3J ª JPH = 7–8 Hz, 1 H, H-3), 11.39 ppm (br s, NH). 13C{ H}
NMR (CDCl3): d 16.17 (d, 3J = 6.5 Hz, CH3), 62.67 (d, 2J = 5.2 Hz,
OCH2), 112.07 (s, CH-4¢), 113.60 (d, 1J = 179.1 Hz, Cq-1), 115.13
(s, CH-3¢), 121.00 (d, 3J = 11.8 Hz, CH-3), 123.16 (d, 3J = 14.3 Hz,
1
4
1
NMR (CDCl3): d 19.59 ppm. MS (EI, 70 eV, 100 ◦C): m/z (%) =
413 (10) [M+], 411 (9) [M+], 275 (46), 273 (48), 184 (100), 182 (97).
Anal. calcd. for C17H19BrNO4P (412.21): H 4.65, N 3.40; found:
H 4.90, N 3.50.
2
4
CH-5), 132.56 (d, J = 5.4 Hz, CH-6), 134.05 (d, J = 2.5 Hz,
CH-4), 142.36 (d, 2J = 6.6 Hz, Cq-2), 145.09 (s, CH-5¢), 148.03 (s,
1i. 1H NMR (CDCl3): d 1.30 (t, 3J = 7.0 Hz, 6 H, CH3), 4.07–
4.19 (m, 4 H, OCH2), 7.03 (td, 3J = 8.1, 7.5, 4J = 1.6 Hz, 1 H, H-4),
7.38 (td, 3J = 8.0, 4J = 1.3 Hz, 1 H, H-5), 7.57 (dd, 3J = 8.1, 4J =
Cq-2¢), 156.66 ppm (s, CO). 31P{ H} NMR (CDCl3): d 19.81 ppm.
1
◦
MS (EI, 70 eV, 345 C): m/z (%) = 324 (14), 323 (85) [M+], 250
(10), 214 (11), 200 (11), 186 (67), 183 (15), 156 (13), 155 (22), 95
(100). Anal. calcd. for C15H18NO5P (323.28): C 55.73, H 5.61, N
4.33; found: C 56.12, H 5.80, N 4.44.
3
4
4
1.2 Hz, 1 H, H-3), 7.59 (superimp. m, J = 7.5, JPH = 3.3, J =
1.5 Hz, 1 H, H-4¢), 7.66 (tt, 3J = 7.8, 7.2, JPH + 4J = 3.2 Hz, 1 H,
H-5¢), 7.73 (t br, 3J = 7.5, 4JPH = 5.1, 4J = 1.2 Hz, 1 H, H-6¢), 8.02
(ddd, 3JPH = 14.1, 3J = 7.5, 4J = 1.2 Hz, 1 H, H-3¢), 8.37 (brs, NH),
{2-[(Thiophene-2-carbonyl)amino]phenyl}phosphonic acid di-
ethyl ester (2g). A mixture of compound 1g (500 mg, 1.77 mmol),
palladium acetate (15 mg, 3.8 mol%) and triethyl phosphite
(0.45 mL, 2.62 mmol) was heated at 180 ◦C for 15 min. At
room temperature the mixture was diluted with ethyl acetate
and filtered through celite. The filtrate was concentrated, and the
crude product was purified by column chromatography on silica
eluting with hexane–ethyl acetate (75 : 25) to give a pale brown oil,
which formed 552 mg (92%) of colorless crystals in few hours at
room temperature, m.p. 94–95 ◦C. Crystal data are compiled in
Table 1 (for selected bond lengths and angles see Fig. 1). 1H NMR
(CDCl3): d 1.34 (td, 3J = 7.0, 4JPH = 0.3 Hz, 6 H, CH3), 4.09 (m, 4
H, OCH2), 7.13 (partly superimp. dd, 3J = 5.0, 3.8 Hz, 1 H, H-4¢),
7.15 (partly superimp. tdd, 3J = 7.6, 4JPH = 3.1, 4J = 1.0 Hz, 1 H,
H-5), 7.54 (dd, 3J = 5.0, 4J = 1.1 Hz, 1 H, H-3¢), 7.60 (superimp.
1
8.45 ppm (d br, 3J = 8.1 Hz, 1 H, H-6). 13C{ H} NMR (CDCl3): d
16.25 (d, 3J = 6.2 Hz, CH3), 62.91 (d, 2J = 6.0 Hz, OCH2), 114.13 (s,
Cq-2), 122.56 (s, CH-6), 125.68 (s, CH-4), 125.79 (d, 1J = 187.1 Hz,
3
Cq-2¢), 128.31 (s, CH-5), 128.88 (d, J = 12.7 Hz, CH-6¢), 130.04
(d, 3J = 14.1 Hz, CH-4¢), 132.43 (s, CH-3), 132.71 (d, 4J = 2.9 Hz,
2
CH-5¢), 133.51 (d, J = 8.9 Hz, CH-3¢), 135.79 (s, Cq-1), 140.06
1
(d, 2J = 9.8 Hz, Cq-1¢), 166.85 ppm (d, 3J = 4.4 Hz, CO). 31P{ H}
NMR (CDCl3): d 17.29 ppm. MS (EI, 70 eV, 185 ◦C): m/z (%) =
413 (1.1) [M+], 411 (1) [M+], 242 (12), 241 (97), 185 (100), 167 (22).
Anal. calcd. for C17H19BrNO4P (412.21): C 49.53, N 3.40; found:
C 49.60, N 3.41.
2i. 1H NMR (CDCl3): d 1.26 (t, 3J = 7.1 Hz, 6 H, CH3), 1.30
(t, 3J = 7.1 Hz, 6 H, CH3), 4.00–4.23 (m, 8 H, OCH2), 7.18 (tdd,
4
4
3
3J = 7.6, JPH = 3.1, J = 0.9 Hz, 1 H, H-5), 7.53 (tdd, J = 7.5,
3
3
4
3
ddd and br t, JPH = 14.3, J = 7.7, J = 1.5 Hz, 1 H, H-6; J =
4JPH = 3.5, 4J = 1.7 Hz, 1 H, H-4¢), 7.57–7.70 (m, 4 H, H-4, H-6,
H-5¢, H-6¢), 8.02 (ddd, JPH = 14.0, J = 7.6, J = 1.1 Hz, 1 H,
7–8 Hz, 1 H, H-4), 7.88 (dd, 3J = 3.8, 4J = 1.1 Hz, 1 H, H-5¢), 8.77
3
3
4
3
4
4
(t, J = 8.3, JPH ca. 6, J = 1.1 Hz, 1 H, H-3), 11.57 ppm (br s,
3
4
1
NH). 13C{ H} NMR (CDCl3): d 16.17 (d, 3J = 6.6 Hz, CH3), 62.72
H-3¢), 8.71 (t br, J = 8.0, JPH = 6.9 Hz, 1 H, H-3), 10.72 ppm
(br s, NH). 13C{ H} NMR (CDCl3): d 16.21, 16.30 (2d, each 3J =
1
2
1
(d, J = 5.2 Hz, OCH2), 113.35 (d, J = 179.3 Hz, Cq-1), 120.60
6.7 Hz, CH3), 62.56, 62.63 (2d, 2J = 5.1, 4.7 Hz, OCH2), 114.72 (d,
3
3
(d, J = 11.7 Hz, CH-3), 122.98 (d, J = 13.4 Hz, CH-5), 128.01
(s, CH-4¢), 128.69 (s, CH-5¢), 131.20 (s, CH-3¢), 132.44 (d, J =
1J = 179.9 Hz, Cq-1), 121.71 (d, J = 11.4 Hz, CH-3), 123.53 (d,
3
2
3J = 13.5 Hz, CH-5), 126.71 (d, 1J = 186.7 Hz, Cq-2¢), 127.20 (d,
3J = 13.1 Hz, CH-6¢), 129.67 (d, 3J = 14.2 Hz, CH-4¢), 132.49 (d,
2J = 4.0 Hz, CH-6), 132.55 (br s, CH-4), 134.08 (s, CH-5¢), 134.15
(d, 2J = 6.7 Hz, CH-3¢), 141.06 (d, 2J = 9.6 Hz, Cq-1¢), 142.42 (d,
4
5.3 Hz, CH-6), 134.19 (d, J = 2.5 Hz, CH-4), 140.33 (s, Cq-2¢),
142.90 (d, 2J = 7.9 Hz, Cq-2), 160.30 ppm (s, CO). 31P{ H} NMR
1
(CDCl3): d 20.43 ppm. MS (EI, 70 eV, 300 ◦C): m/z (%) = 340 (7),
339 (44) [M+], 228 (6), 202 (25), 110 (100), 83 (5). Anal. calcd. for
C15H18NO4PS (339.35): C 53.09, H 5.35, N 4.13; found: C 53.28,
H 5.71, N 4.20.
2J = 7.2 Hz, Cq-2), 167.33 ppm (d, 3J = 4.5 Hz, CO). 31P{ H} NMR
1
(CDCl3): d 19.51 (s), 16.96 (s) ppm. MS (EI, 70 eV, 210 ◦C): m/z
(%) = 470 (1), 469 (9) [M+], 242 (13), 241 (100), 213 (25), 185 (60),
167 (12). Anal. Calcd for C21H29NO7P2 (469.40): C, 53.73; H, 6.23,
N, 2.98. Found: C, 53.88; H, 6.62; N, 3.14.
2-(Pyridine-2-carbonylamido)phenylphosphonic acid diethyl es-
ter (2h). A mixture of compound 1h (4.6 g, 16.6 mmol),
palladium acetate (140 mg, 4.0 mol%)◦ and triethyl phosphite
(4.3 mL, 25.1 mmol) was heated at 210 C for 30 min. At room
temperature the reaction mixture was diluted with ethyl acetate
and filtered through celite. The filtrate was concentrated and the
crude product was purified by column chromatography on silica,
eluting with hexane–ethyl acetate (70 : 30) yielding 4.0 g (72%) pale
yellow oil. H NMR (CDCl3): d 1.34 (t, J = 7.1 Hz, 6 H, CH3),
4.09–4.28 (m, 4 H, OCH2), 7.21 (td, 3J = 7.6, 4JPH = 3.2 Hz, 1 H,
H-5), 7.47 (ddd, 3J = 7.6, 4.8, 4J = 1.0 Hz, 1 H, H-5¢), 7.61 (br t,
3J = 8.1, 7.6 Hz, 1 H, H-4), 7.81 (ddd, 3JPH = 14.8, 3J = 7.7, 4J =
1.6 Hz, 1 H, H-6), 7.89 (td, 3J = 7.7, 4J = 1.6 Hz, 1 H, H-4¢), 8.29
(br d, 3J = 7.8 Hz, 1 H, H-3¢), 8.72 (br d, 3J = 4.0 Hz, 1 H, H-6¢),
2-(Furan-2-carbonylamido)phenylphosphonic acid diethyl ester
(2f). A mixture of compound 1f (3.3 g, 12.4 mmol), palladium
acetate (111 mg, 4.0 mol%) and triethyl phosphite (3.2 mL,
18.7 mmol) was heated at 180 ◦C for 1 h. Then the reaction mixture
was allowed to warm to room temperature, diluted with ethyl
acetate and filtered through Celite. The filtrate was concentrated
and the crude product was purified by column chromatography
on silica, eluting with hexane/ethyl acetate (75 : 25) to give a pale
yellow oil, which formed 3.24 g (81%) colorless crystals within
few hours at room temperature, m.p. 97–98 ◦C. 1H NMR (CDCl3):
d 1.33 (td, 3J = 7.1, 4JPH = 0.4 Hz, 6 H, CH3), 4.13 (m, 4 H, OCH2),
1
3
This journal is
The Royal Society of Chemistry 2011
Dalton Trans., 2011, 40, 211–224 | 219
©