ORDER
REPRINTS
a-Ketophosphonates Preparation by Oxidation
1467
2JHH ¼ 7.1 Hz, 2-OCH2CH3), 7.28–7.6 (m, 3H), 8.03–8.25 (m, 2H) ppm; 13
C
3
NMR (CDCl3, TMS): 16.64 (d, JCP ¼ 5.7 Hz, 2-OCH2CH3), 64.31
2
(d, JCP ¼ 7.5 Hz, 2-OCH2CH3), 129.15, 130.06, 135.03, 136.29 (–C6H5),
1
199.12 (d, JCP ¼ 177.5 Hz, C55O) ppm; IR (neat): n 1650 (C55O), 1267
(P55O) cm21; MS: Mþ (242), M–P(O)(OEt)2 (105); Elemental analysis for
C11H15O4P requires C 54.5%, H 6.2%; found: C 54.2%, H 6.0%.
Diethyl 4-methyl-benzoyl phosphonate (2b). B.p. 130–1318C/
1
0.05 mmHg (lit.[2a] b.p. 116–1178C/0.03 mmHg); H NMR (CDCl3, TMS):
2
d 1.29–1.42 (t, 6H, JHH ¼ 7.1 Hz, 2-OCH2CH3), 2.35 (s, 3H, –CH3),
2
2
4.11–4.16 (dq, 4H, JPH ¼ 7.1 Hz, JHH ¼ 7.1 Hz, 2-OCH2CH3), 7.12–7.21
(m, 2H), 8.04–8.07 (m, 2H) ppm; 13C NMR (CDCl3, TMS): 16.67
3
2
(d, JCP ¼ 5.7 Hz, 2-OCH2CH3), 22.18 (–CH3), 64.24 (d, JCP ¼ 7.5 Hz,
2-OCH2CH3), 127.35, 129.89, 130.31, 146.41 (–C6H4), 198.46
1
(d, JCP ¼ 176.6 Hz, C55O) ppm; IR (neat): n 1650 (C55O), 1261 (P55O)
cm21; MS: Mþ (256), M–P(O)(OEt)2 (119); Elemental analysis for
C12H17O4P requires C 56.2%, H 6.6%; found: C 56.0%, H 6.1%.
Diethyl 4-methoxy-benzoyl phosphonate (2c). B.p. 166–1678C/
0.05 mmHg (lit.[2a] b.p. 175–1798C/1.5 mmHg); H NMR (CDCl3, TMS): d
1
2
1.11–1.29 (t, 6H, JHH ¼ 7.1 Hz, 2-OCH2CH3), 3.80 (s, 3H, –CH3), 3.90–
2
2
4.10 (dq, 4H, JPH ¼ 7.1 Hz, JHH ¼ 7.1 Hz, 2-OCH2CH3), 6.84–6.90
(m, 2H), 7.42–7.50 (m, 2H) ppm; 13C NMR (CDCl3, TMS): 16.75
3
2
(d, JCP ¼ 5.7 Hz, 2-OCH2CH3), 55.59 (–CH3), 63.46 (d, JCP ¼ 7.5 Hz,
2-OCH2CH3), 114.03, 128.82, 129.21, 159.78 (–C6H4), 198.01
1
(d, JCP ¼ 176.2 Hz, C55O) ppm; IR (neat): n 1655 (C55O), 1265 (P55O)
cm21; MS: Mþ (272), M–P(O)(OEt)2 (135); Elemental analysis for
C12H17O5P requires C 52.9%, H 6.2%; found: C 52.2%, H 5.9%.
Diethyl 2,4,6-trimethyl-benzoyl phosphonate (2d). B.p. 108–1098C/
0.07 mmHg (lit.[2a] b.p. 131–1328C/0.3 mmHg);1H NMR (CDCl3, TMS): d
2
1.25–1.32 (t, 6H, JHH ¼ 7.1 Hz, 2-OCH2CH3), 2.23 (s, 6H, 2,6-diCH3),
2
2
2.27 (s, 3H, 4-CH3), 4.06–4.17 (dq, 4H, JPH ¼ 7.1 Hz, JHH ¼ 7.1 Hz,
2-OCH2CH3), 6.83 (s, 2H) ppm; 13C NMR (CDCl3, TMS): 16.81
3
(d, JCP ¼ 5.7 Hz, 2-OCH2CH3), 21.17 (2,6-diCH3), 21.38 (4-CH3), 63.12
2
(d, JCP ¼ 7.5 Hz, 2-OCH2CH3), 129.74, 130.3, 137.69, 137.75 (–C6H2),
1
199.01 (d, JCP ¼ 177.0 Hz, C55O) ppm; IR (neat): n 1665 (C55O), 1250
(P55O) cm21; MS: Mþ (284), M–P(O)(OEt)2 (142); Elemental analysis for
C14H21O4P requires C 59.1%, H 7.4%; found: C 59.3%, H 7.6%.
Diethyl 2-chloro-benzoyl phosphonate (2e). B.p. 105–1068C/
1
0.05 mmHg (lit.[18] b.p. 158–1608C, 2.3 mmHg); H NMR (CDCl3, TMS):
2
d
1.58 (t, 6H, JHH ¼ 7.1 Hz, 2-OCH2CH3), 4.17–4.30 (m, 4H,
2-OCH2CH3), 7.24–7.44 (m, 3H), 8.14–8.20 (m, 1H) ppm; 13C NMR (CDCl3,
3
2
TMS): 16.65 (d, JCP ¼ 5.7 Hz, 2-OCH2CH3), 64.82 (d, JCP ¼ 7.4
Hz, 2-OCH2CH3), 126.84, 127.10, 130.64–132.07, 132.68–133.85,