J.-O. Durand, D. Massiot et al.
FULL PAPER
1
AcOEt). The product was isolated as a pale yellow oil (39 g, 94%).
supra) leaving to two different H signals. Following Harris×
work[2c] in which the isotropic shielding of acidic protons were
correlated to the oxygen oxygen bond distance for hydrogen
bonds of phosphonic acids, the shift of 10.5(Æ0.5) ppm for H3
corresponds to 2.62 < r(O1 ¥¥¥ O3) < 2.67 ä. The shift of
12(Æ0.5) ppm for H2 corresponds to 2.55 < r(O1 ¥¥¥ O2) <
2.59 ä. Crystallographic measurements gave r(O1 ¥¥¥ O3)
2.60 ä and r(O1 ¥¥¥ O2) 2.55 ä. Thus, correlation results
are in agreement with crystallographic measurements with
less than 5% error. The single broadened PO3H2 signal for
phase B indicated different contributions, with a higher
mobility of the phosphonic proton environment. If this bond
3
3
3
1H NMR (CDCl3): d 7.33 (d, J 8.2 Hz, 2H), 7.21 (dd, J 8.2 Hz, J
3
3
3
2.2 Hz, 2H), 6.66 (dd, J 16.7 Hz, J 10.9 Hz, 1H), 5.7 (d, J 16.7 Hz,
1H), 5.2 (d, 3J 10.9 Hz, 1H), 4.22-3.98 (m, 4H), 3.11 (d, 2J 21.8 Hz, 2H),
1.26 ppm (t, 3J 7.1 Hz, 6 H) ; 13C NMR (CDCl3): d 136.74 (dd, 6J
5
2
2.1 Hz, 1C), 136.52 (d, J 3.9 Hz, 1C), 131.51 (d, J 9.3Hz, 1H), 130.24
(dd, 3J 6.7 Hz, 2C), 126.65 (dd, 4J 3.2 Hz, 2C), 113.95 (td, 7J 1.5 Hz,
1C), 62.38 (td, 2J 6.7 Hz, 2C), 33.82 (td, 1J 173.1 Hz, 1C), 16.69 pp, (qd,
3J 5.9 Hz, 2C); 31P NMR (CDCl3): d 27.4 ppm; IR: nÄ 3100, 2981, 2840,
1630, 1513, 1408, 1248, 1163, 1028, 980 860 cmÀ1
.
P-Vinylbenzylphosphonic acid: Diethylparavinylbenzylphosphonate (10 g,
39.4 mmol) was dissolved in CH2Cl2 (50 mL). TMSBr (18.08 g, 0.19 mol)
was added, and the reaction was stirred overnight. The mixture was
concentrated in vacuo and the oily residue was hydrolyzed with H2O
(11.7 mL, 0.65 mol). The white precipitate was filtered and recrystallized
from H2O or CH3CN and dried in air. The product was isolated as white
needles (5.2 g, 67%). M.p. 164 1678C; 1H NMR ([D6]DMSO): d 8.79 (s,
2H), 7.39 (d, 3J 8 Hz, 2H), 7.23(d, 3J 8 Hz, 2H), 6.71 (dd, 3J 10.9 Hz,
3J 17.7 Hz, 1H), 5.79 (d, 3J 17.7 Hz, 1H), 5.22 (d, 3J 10.9 Hz, 1H),
consists on one P O group linked to one hydroxyl group, or
one hydroxyl group linked to another one, its length can be
calculated following Harris× correlation.[2c]. Considering a
chemical shift of d 12.5 ppm, we obtained an average
distance r(O ¥¥¥ O) 2.53ä, which is close to the O ¥¥¥ O
distances calculated in phase A.
2
2.96 ppm (d, J 21.6 Hz, 2H); 13C NMR ([D6]DMSO): d 137.4 (d, 1C),
135.8 (dd, 4J 3.7 Hz, 2C), 135. 0 (d, 2J 9.0 Hz, 1C), 130.8 (dd, 3J 6.3Hz,
2C), 126.6 (d, 5J 3Hz, 1C), 114.4 (t, 1C), 36.1 ppm (td, 1J 131.7 Hz, 1C);
31P NMR ([D6]DMSO): d 22.2 ppm; HR MAS (FAB , GT): calcd:
199.0589; found: 199.0524.
Phase A: IR (KBr): 3558, 2750, 2317, , 1629, 1511, 1407, 1267, 1233, 1098,
Conclusion
998, 910, 846, 803cm À1
.
Phase B: IR (KBr): 3560, 3273, 3086, 3043, 3006, 2952, 2722, 2340, 1693,
1511, 1407, 1261, 1224, 1145, 1098, 1010, 953, 910, 846, 803 cmÀ1
We have revisited the synthesis of styrenyl phosphonic acid 2.
Its crystals were studied by X-ray crystalography and NMR
experiments; this allowed us to differentiate two crystalline
phases, one anhydrous phase A and one hydrated phase B,
with different hydrogen bonding features. Description of the
proton environments in these two phases was performed by
.
X-ray powder calculation for phase B (TREOR): a 9.065(2), b 6.313(1),
c 19.993(3) ä; b 107.25(1)8; M(20) 49, F(20) 107.(0.003903, 48).
CCDC-200070 contains the supplementary crystallographic data for this
conts/retrieving.html (or from the Cambridge Crystallographic Data Centre,
12 Union Road, Cambridge CB2 1EZ, UK; fax: (44)1223-336033; or
deposit@ccdc.cam.uk). Data collection parameters are available as Sup-
porting Information.
1
using recent high-resolution H NMR experiments. Informa-
tion brought by these studies will be useful for the modifica-
tion of surface metal oxides by reaction with acid 2 in which
one, two, or three P-O-metal bonds are involved.
Acknowledgement
We thank Professor G. Bodenhausen (ENS, Paris) for the access to the
Bruker 600 spectrometer. We thank the referees for important adivce. We
Experimental Section
¬
acknowledge financial support from CNRS, Region Centre and European
Community contracts HPRI-CT-1999-00042 and HPMT-CT-2000-00169.
All reactions were carried out under an argon atmosphere. Solvents were
1
dried by standard methods and were distilled prior to use. H, 13C, and 31
P
NMR liquid-state spectra were obtained on a Bruker AC200 spectrometer.
IR spectra were recorded on a Perkin Elmer 1600 FT spectrometer. Mass
spectra were recorded on a Jeol JMS-DX300 instrument using FAB mode
with a glycerol-thioglycerol (GT) matrix. Powder diffraction diagrams were
registered on a X×Pert Philips diffactometer with a copper anticathode
(Ka1). Simulation of powders diffraction diagrams were performed with
Poudrix software (J. Langier and B. Bochu) and indexations were
performed with TREOR program. Single-crystal X-ray structure was
performed with an Enraf-Nonius CAD4 (four circle) diffractometer.
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spectrometer (7 T), except the 1H high magnetic field spectra, which were
recorded at 14 T. Spectra were referenced relative to TMS and H3PO4 at
0 ppm for 1H and 31P, respectively. Radio-frequency fields between 50 to
60 kHz were employed. A ramp for polarization transfer[10] was used in
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Hartmann Hahn match condition and improve signal-to-noise ratio.
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0.163mol) was suspended in THF (170 mL) at 0 8C. Diethylphosphite
(25.3mL, 0.196 mol) was added drop wise. The mixture was allowed to
come to RT, then transferred by cannula to a solution of 1-chloromethyl-4-
vinylbenzene (25g, 0.163mol) and NaI (2.44 g, 16.3mmol) in THF
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AcOEt, and the mixture was filtered through celite. Volatiles were
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