PAPER
Preparation of a-Acetoxyphosphonates
1773
2f
1JP,H = 14.2 Hz, CH), 7.95 (t, 1 H, JH,H = 8.0 Hz, C6H4), 7.85 (d, 1
H, JH,H = 7.5 Hz, C6H4), 8.20 (d, 1 H, JH,H = 8.1 Hz, C6H4), 8.34 (s,
1 H, C6H4).
IR (neat): 1755 cm–1 (C=O).
1H NMR (CCl4/TMS): d = 1.20–1.28 (m, 6 H, 2 OCH2CH3), 2.15 [s,
3 H, OC(O)CH3], 3.94–4.00 (m, 4 H, 2 OCH2CH3), 5.97 (d, 1 H,
1JP,H = 13.82 Hz, CH), 7.27–7.41 (m, 4 H, C6H4).
13C NMR (CDCl3, TMS): d = 16.10–16.26 (m, 2 OCH2CH3), 20.55
1
[OC(O)CH3], 63.56–63.80 (2 OCH2CH3), 69.30 (d, JC,P = 169.8
Hz, CH), 122.34–123.43, 129.45, 135.79, 148.13 (C6H4), 168.99 [d,
13C NMR (CCl4/TMS): d = 17.89 (d, 3JC,P = 5.8 Hz, 2 OCH2CH3),
3JC,P = 8.7 Hz, OC(O)CH3].
17.98 (d, 3JC,P = 5.8 Hz, 2 OCH2CH3), 22.01 [OC(O)CH3], 64.14 (d,
2JC,P = 6.3 Hz, 2 OCH2CH3), 70.84 (d, JC,P = 168.4 Hz, CH),
MS (70 eV): m/z = 331 (M+).
1
3
127.62–130.86, 135.78, 137.46 (C6H4), 169.13 [d, JC,P = 7.9 Hz,
Anal. Calcd for C13H18NO7P: C, 47.13; H, 5.44. Found: C, 47.15; H,
5.45.
OC(O)CH3].
MS (70 eV): m/z = 320 (M+), 322 (M + 2).
2k
Anal. Calcd for C13H18ClO5P: C, 48.75; H, 5.62. Found: C, 48.71;
H, 5.61.
IR (neat): 1759 cm–1 (C=O).
1H NMR (CDCl3/TMS): d = 1.25–1.30 (m, 6 H, 2 OCH2CH3), 2.23
[s, 3 H, OC(O)CH3], 4.10–4.12 (m, 4 H, 2 OCH2CH3), 6.22 (d, 1 H,
1JP,H = 14.9 Hz, CH), 7.67 (m, 2 H, JH,H = 7.1 Hz, C6H4), 8.23 (d, 2
H, JH,H = 7.5 Hz, C6H4), 8.40 (d, 1 H, JH,H = 8.2 Hz, C6H4).
2g
IR (neat): 1756 cm–1 (C=O).
1H NMR (CDCl3/TMS): d = 1.16–1.28 (m, 6 H, 2 OCH2CH3), 2.15
[s, 3 H, OC(O)CH3], 3.89–4.10 (m, 4 H, 2 OCH2CH3), 6.16 (d, 1 H,
1JP,H = 13.6 Hz, CH), 7.33–7.48 (m, 4 H, C6H4).
3
13C NMR (CDCl3/TMS): d = 16.62 (d, JC,P = 16.6 Hz, 2
1
OCH2CH3), 63.87–64.13 [OC(O)CH3], 70.1 (d, JC,P = 168 Hz,
CH), 123.89, 128.73–128.81, 141.30, 148.19 (C6H4), 169.38 [d,
13C NMR (CDCl3/TMS): d = 16.53–16.75 (2 OCH2CH3), 21.15
3JC,P = 8.6 Hz, OC(O)CH3].
1
[OC(O)CH3], 63.61–63.89 (2 OCH2CH3), 70.85 (d, JC,P = 165.7
Hz, CH), 127.42–130.21, 133.74, 133.78 (C6H4), 169.56 [d,
MS (70 eV): m/z = 331 (M+).
3JC,P = 9.0 Hz, OC(O)CH3].
Anal. Calcd for C13H18NO7P: C, 47.13; H, 5.44. Found: C, 47.16; H,
5.47.
MS (70 eV): m/z = 320 (M+), 322 (M + 2).
Anal. Calcd for C13H18ClO5P: C, 48.75; H, 5.62. Found: C, 48.69;
H, 5.63.
2l
IR (neat): 1749 cm–1 (C=O).
2h
1H NMR (CDCl3/TMS): d = 1.16–1.34 (m, 6 H, 2 OCH2CH3), 2.19
[s, 3 H, OC(O)CH3], 3.89–4.14 (m, 4 H, 2 OCH2CH3), 6.32 (d, 1 H,
1JPH, = 13.7 Hz, CH), 7.44–7.48 (m, 2 H, C10H7), 7.61 (d, 1 H,
JH,H = 8.5 Hz, C10H7), 7.78–7.86 (m, 3 H, C10H7), 7.96 (s, 1 H,
C10H7).
IR (neat): 1749 cm–1 (C=O).
1H NMR (CDCl3/TMS): d = 1.22–1.35 (m, 6 H, 2 OCH2CH3), 2.17
[s, 3 H, OC(O)CH3], 4.01–4.26 (m, 4 H, 2 OCH2CH3), 6.85 (d, 1 H,
1JP,H = 17.9 Hz, CH), 7.17–7.23 (m, 1 H, C6H3), 7.32–7.35 (m, 2 H,
C6H3).
3
13C NMR (CDCl3/TMS): d = 16.29 (d, JC,P = 5.85 Hz, 2
3
OCH2CH3), 16.42 (d, JC,P = 5.7 Hz, 2 OCH2CH3), 20.88
13C NMR (CDCl3/TMS): d = 16.43 (d, 3JC,P = 5.8 Hz, 2 OCH2CH3),
2
[OC(O)CH3], 63.42 (d, JC,P = 6.5 Hz, 2 OCH2CH3), 70.63 (d,
16.57 (d, 3JC,P = 5.8 Hz, 2 OCH2CH3), 22.24 [OC(O)CH3], 63.66 (d,
1JC,P = 170.3 Hz, CH), 125.33–128.27, 130.88, 130.92–133.31
(C10H7), 169.31 [d, 3JC,P = 9.2 Hz, OC(O)CH3].
2JC,P = 6.8 Hz, 2 OCH2CH3), 69.45 (d, JC,P = 174.1 Hz, CH),
1
128.96, 129.67, 129.69, 130.32, 130.36, 135.94 (C6H3), 169.51 [d,
3JC,P = 10.4 Hz, OC(O)CH3].
MS (70 eV): m/z = 336 (M+).
MS (70 eV): m/z = 355 (M+), 357 (M + 2), 359 (M + 4).
Anal. Calcd for C17H21O5P: C, 60.71; H, 6.25. Found: C, 60.70; H,
6.25.
Anal. Calcd for C13H17Cl2O5P: C, 43.9; H, 4.8. Found: C, 43.92; H,
4.83.
2m
IR (neat): 1759 cm–1 (C=O).
2i
IR (neat): 1748 cm–1 (C=O).
1H NMR (CDCl3/TMS): d = 1.03–1.32 (m, 6 H, 2 OCH2CH3), 2.20
8s, 3 H, OC(O)CH3], 3.99–4.20 (m, 4 H, 2 OCH2CH3), 6.19 (d, 1 H,
1JP,H = 14.1 Hz, CH), 7.36–7.41 (m, 1 H, C5H4N), 7.91 (d, 1 H,
JH,H = 7.7 Hz, C5H4N), 8.61–8.71 (m, 2 H, C5H4N).
1H NMR (CDCl3/TMS): d = 1.19–1.38 (m, 6 H, 2 OCH2CH3), 2.24
[s, 3 H, OC(O)CH3], 4.05–4.25 (m, 4 H, 2 OCH2CH3), 6.25 (d, 1 H,
1JP,H = 14.2 Hz, CH), 7.59 (t, 1 H, JH,H = 7.9 Hz, C6H4), 7.85 (d,
JH,H = 7.5 Hz, 1 H, C6H4), 8.20 (d, JH,H = 8.1 Hz, 1 H, C6H4), 8.34
(s, 1 H, C6H4).
13C NMR (CDCl3/TMS): d = 16.54 (d, 3JC,P = 5.5 Hz, 2 OCH2CH3),
16.63 (d, 3JCP, = 5.5 Hz, 2 OCH2CH3), 20.94 [OC(O)CH3], 63.99–
1
64.16 (2 OCH2CH3), 68.46 (d, JC,P = 171.4 Hz, CH), 124.05,
3
13C NMR (CDCl3/TMS): d = 16.18 (d, JC,P = 5.85 Hz, 2
3
136.67, 148.32–149.28 (C5H4N), 169.36 [d, JC,P = 8.9 Hz,
3
OCH2CH3), 16.24 (d, JC,P = 5.7 Hz, 2 OCH2CH3), 20.55
OC(O)CH3].
MS (70 eV): m/z = 287 (M+).
2
[OC(O)CH3], 63.67 (d, JC,P = 6.5 Hz, 2 OCH2CH3), 69.30 (d,
1JC,P = 169.8 Hz, CH), 122.34–123.42, 128.67, 135.79 (C6H4),
168.99 [d, 3JCP = 8.68 Hz, OC(O)CH3].
Anal. Calcd for C12H18NO5P: C, 50.2; H, 6.3. Found: C, 50.0; H,
6.0.
MS (70 eV): m/z = 331 (M+).
Anal. Calcd for C13H18NO7P: C, 47.13; H, 5.44. Found: C, 47.11; H,
5.43.
2n
IR (neat): 1746 cm–1 (C=O).
2j
1H NMR (CDCl3/TMS): d = 1.30–1.36 (m, 6 H, 2 OCH2CH3), 2.17
[s, 3 H, OC(O)CH3], 4.17–4.22 (m, 4 H, 2 OCH2CH3), 5.81–5.90
1H NMR (CDCl3/TMS): d = 1.19–1.37 (m, 6 H, 2 OCH2CH3), 2.24
[s, 3 H, OC(O)CH3], 4.06–4.25 (m, 4 H, 2 OCH2CH3), 6.25 (d, 1 H,
Synthesis 2004, No. 11, 1771–1774 © Thieme Stuttgart · New York