B. Quiclet-Sire et al. / Journal of Organometallic Chemistry 643–644 (2002) 404–408
407
then AcOEt); IR (neat, w cm−1): 3435 (NH, broad);
1668 (CꢁO); 1240 (PꢁO); 1028 (PꢀOꢀC); 1H-NMR
(CDCl3, 200 MHz, l ppm): 7.24 (5H, m, Ph); 6.95 (1H,
bs, HH), 6.64 (1H, two triplets, J=6 Hz, ꢁCH); 3.73
128.9; 122.1; 121.4; 115.6; 114.7; 114.1 and 114.0 (Ph,
2
CꢁCH); 55.2 (OCH3); 53.2 (d, JPC=5.3 Hz) 52.9 (d,
2JPC=4.8 Hz) (2OCH3); 24.9; 23.3 (CH3); m/z (CI,
NH3): 300 [MH+]; 268 [MH+−MeOH]; 257 [MH+−
COCH3]. Anal. Calc. for C13H18NO5P·1/2H2O: C,
50.65; H, 6.17. Found: C, 50.74; H, 6.09%.
3
(6H, d, JPH=11.1 Hz, 2OCH3); 3.47 (2H, m, CH2);
2.13 (3H, s, CH3); 13C-NMR (CDCl3, 50 MHz, l ppm):
168.4 (CꢁO); 144.5; 144.1; 138.4; 128.7; 126.6 (Ph,
CꢁCH); 53.1 (d, 2JPC=6.0 Hz, 2OCH3); 35.3 (d, 3JPC
=
2.2.6. Dimethyl (1-acetylamino-2-naphthalen-1-yl-
6inyl)-phosphonate (8f)
15.1 Hz, CH2); 23.3 (CH3); m/z (CI, NH3): 284 [MH+];
252 [MH+−MeOH]. Anal. Calc. for C13H18NO4P: C,
55.12; H, 6.41. Found: C, 55.21; H, 6.58%.
This compound (Z–E cal/l) was obtained as a yel-
lowish oil in 81% yield (eluent: AcOEt–pentane=1/1,
then AcOEt); IR (neat, w cm−1): 3437 and 3237 (NH,
1
2.2.3. Dimethyl [1-acetylamino-2-(4-fluoro-phenyl)-
6inyl]-phosphonate (8c)
broad); 1673 (CꢁO); 1241 (PꢁO); 1030 (PꢀOꢀC); H-
NMR(CDCl3, 250 MHz, l ppm): 8.0–7.38 (8H, m, Ar,
3
This compound (Z–E cal/l) was obtained as colour-
less oil in 71% yield (eluent: AcOEt, then MeOH); IR
(neat, w cm−1): 3436 and 3233 (NH); 1671 (CꢁO); 1234
CꢁCH); 3.84; 3.35 (6H, 4d, JPH=11.2 Hz, 2OCH3);
2.18; 1.87 (3H, 2s, CH3); 13C-NMR (CDCl3, 62.5 MHz,
l ppm): 169.6 and 168.9 (CꢁO); 133.5; 132.9; 132.2 and
131.4 (4C, Arq, CqꢁCH); 130.9; 130.8; 129.5; 128.6;
128.5; 128.3; 126.8; 126.6; 126.2; 125.9; 125.2; 125.0;
124.9 and 124.0 (8C Ar, CꢁCH); 53.3; 52.8 (2C, 2d,
2JPC=5.4 Hz, 2CH3); 24.8 and 22.9 (CH3); m/z (IC,
NH3): 320 [MH+]; 288 [MH+−MeOH]. Anal. Calc.
for C16H18NO4P·H2O: C, 56.97; H, 5.93. Found: C,
56.94; H, 5.81%.
1
(PꢁO); 1031 (PꢀOꢀC); H-NMR (CDCl3, 200 MHz, l
ppm): 7.89 (1H, s, NH); 7.53–6.97 (5H, m, Ph and
3
ꢁCH); 3.77; 3.58 (6H, 2d, JPH=11.2 Hz, 2OCH3, Z
and E); 2.15 and 2.10 (3H, 2s, CH3); 13C-NMR
(CDCl3, 50 MHz, l ppm): 168.7 (CꢁO); 160.7; 139.7;
139.3; 131.7; 131.5; 130.8; 130.7; 115.9; 115.5; 115.2 and
114.7 (Ph, CꢁCH); 53.2 (d, 2JPC=5.5 Hz); 52.9 (d,
2JPC=4.5 Hz) (2OCH3, Z and E); 24.9; 23.4 (CH3);
m/z (CI, NH3): 288 [MH+]; 256 [MH+−MeOH]; 245
[MH+−COCH3]. Anal. Calc. for C12H15FNO4P·1/
2H2O: C, 48.65; H, 5.41. Found: C, 48.43; H, 5.31%.
2.2.7. Dimethyl (1-acetylamino-3-methyl-but-1-
enyl)-phosphonate (8g)
This compound (Z–E cal/l) was obtained as a
colourless oil in 77% yield (eluent: AcOEt, then
MeOH–CH2Cl2=1/4); IR (neat, w cm−1): 3449 and
3237 (NH, broad); 1670 (CꢁO); 1241 (PꢁO); 1031
2.2.4. Dimethyl [1-acetylamino-2-(4-bromo-phenyl)-
6inyl]-phosphonate (8d)
1
This compound (Z–E cal/l) was obtained as colour-
less oil in 75% yield (eluent: AcOEt–pentane=1/1,
then AcOEt); IR (neat, w cm−1): 3437 and 3234 (NH);
1673 (CꢁO); 1240 (PꢁO); 1030 (PꢀOꢀC); 1H-NMR
(CDCl3, 250 MHz, l ppm): 7.72 (1H, s large, NH);
7.48–7.15 (5H, m, Ph and ꢁNH); 3.78; 3.59 (6H, 2d,
3JPH=11.3 Hz, 2OCH3, Z and E); 2.14; 2.09 (3H, 2s,
CH3); 13C-NMR (CDCl3, 62.5 MHz, l ppm): 168.6
(CꢁO); 139.2; 138.8; 131.8; 131.0; 130.9; 130.5 (Ph,
(PꢀOꢀC); H-NMR (CDCl3, 200 MHz, l ppm): 7.75
(1H, broad s, NH); 6.42 and 6.33 (1H, two doublets,
3
J=12 Hz, CHꢁ); 3.73 (6H, d, JPH=11.1 Hz, 2OCH3);
2.62 (1H, m, CH); 2.09 (3H, s, CH3CO); 1.05 (3H, s,
CH3); 1.02 (3H, s, CH3); 13C-NMR (CDCl3, 62.5 MHz,
l ppm): 169.0 (CꢁO); 154.2 and 153.9 (CHꢁ); 121.8;
118.4 (Cq); 52.6; 52.5 (OCH3); 27.8; 27.6 (CH3CO); 22.6
(CH); 21.1 (2CH3); m/z (CI, NH3): 236 [MH+]; 204
[MH+−MeOH]. Anal. Calc. for C9H18NO4P·1/2H2O:
C, 44.26; H, 7.79. Found: C, 43.85; H, 7.73%.
2
CꢁCH); 53.2 and 52.9 (2d, JPC=5.3 Hz, 2OCH3, Z
and E); 24.8 and 23.3 (CH3). Anal. Calc. for
C12H15BrNO4P·12H2O: C, 40.34; H, 4.48. Found: C,
40.41; H, 4.59%.
2.2.8. Dimethyl (1-acetylamino-hex-1-enyl)-
phosphonate (8h)
This compound (Z–E cal/l) was obtained as a
colourless oil in 89% yield (eluent: AcOEt–pentane=1/
1, then AcOEt); IR (neat, w cm−1): 3460 and 3239 (NH,
2.2.5. Dimethyl [1-acetylamino-2-(3-methoxy-
phenyl)-6inyl]-phosphonate (8e)
1
This compound (Z–E=1/1) was obtained as colour-
less oil in 72% yield (eluent: AcOEt, then MeOH); IR
(neat, w cm−1): 3437 and 3232 (NH); 1670 (CꢁO); 1239
broad); 1670 (CꢁO); 1241 (PꢁO); 1029 (PꢀOꢀC); H-
NMR (CDCl3, 200 MHz, l ppm): 7.63 (1H, broad d,
NH); 6.54 (1H, apparent quintet, CHꢁ); 3.74 (6H,
1
3
(PꢁO); 1029 (PꢀOꢀC); H-NMR (CDCl3, 300 MHz, l
d+d, JPH=41.1 Hz, 2OCH3); 2.11 (3H, bs, CH3CO);
ppm): 7.63 (1H, broad s, NH); 7.30–6.82 (5H, m, Ph,
ꢁCH); 3.80 (3H, s, OCH3); 3.81 and 3.60 (6H, 2d,
3JPH=11.7 Hz, 2OCH3, Z and E); 2.15 and 2.10 (3H,
2s, CH3); 13C-NMR (CDCl3, 62.5 MHz, l ppm): 168.8
(CꢁO); 159.6; 159.1; 140.9; 140.6; 134.9; 134.7; 129.6;
2.09; 1.38 (6H, m, 3CH2); 0.90 (3H, bt, J=7.5 Hz,
CH3); 13C-NMR (CDCl3, 75 MHz, l ppm): 168.3
(CꢁO); 147.1 (CHꢁ, d, 2JPC=20.6 Hz); 121.6; 52.8; 52.7
(2C, 2OCH3); 30.0 (CH2); 28.6 and 28.4 (CH2); 23.0
(CH3CO); 22.4 (CH2); 13.7 (CH3); m/z (IC, NH3): 250