Phosphorylating Power of Red Phosphorus towards Aldehydes in Basic and in Acidic Media
FULL PAPER
Tetrahedron Lett. 1990, 31, 5463Ϫ5466. Ϫ [1d] Ya. A. Dorfman,
M. M. Aleshkova, A. S. Karinskaya, A. K. Borangazieva, M.
M. Kebekbaeva, J. Gen. Chem. USSR 1991, 61, 999Ϫ1008;
Chem. Abstr. 1992, 116, 21132y.
Bis(α-hydroxybenzyl)phosphinic Acid (5a): This compound was ob-
tained by reactions A (from 3a), E and H (purified from reaction
H). Solvents were removed under vacuum. To the resulting residue
was added toluene and the crude product was precipitated. The
precipitate was separated from the supernatant and recrystallized
from chloroform at low temperature in 15% yield as a white solid.
Ϫ M.p. 192Ϫ193°C (from CHCl3). Ϫ 31P NMR (32.44 MHz,
[2]
[2a] L. Maier, Top. Curr. Chem. 1971, 19, 1Ϫ59. Ϫ [2b] C. Brown,
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1
[3]
[4]
[5]
[6]
[7]
[8]
[D6]DMSO): δ ϭ 38.4 (m). Ϫ H NMR (80.13 MHz, [D6]DMSO):
D. Semenzin, G. Etemad-Moghadam, D. Albouy, M. Koenig,
Tetrahedron Lett. 1994, 35, 3297Ϫ3300.
2
δ ϭ 7.40Ϫ7.30 (m, 10 H), 5.15 (d, JHP ϭ 7.4 Hz, 2 H). Ϫ 13C
D. Albouy, G. Etemad-Moghadam, M. Vinatoru, M. Koenig,
J. Organomet. Chem. 1997, 529, 295Ϫ299.
NMR (62.90 MHz, [D6]DMSO): δ ϭ 138.7 (s), 128.9 (m), 70.6 (d,
1JCP ϭ 108.8 Hz). Ϫ IR (KBr, cmϪ1): ν˜ ϭ 3500Ϫ3000 (OH), 1162
(PϭO). Ϫ MS (DCI/NH3); m/z: 279 [M ϩ 1]ϩ, 124 [PhCHOH ϩ
NH3]ϩ. Ϫ C14H15O4P·0.5 H2O (287.237): calcd. C 58.54, H 5.61;
found C 58.57, H 5.40.
M. Pourbaix, N. de Zoubov, J. Van Muylder, Atlas dЈEquilibres
Electrochimiques, Gauthier-Villars, Paris, 1963.
D. Semenzin, G. Etemad-Moghadam, D. Albouy, O. Diallo, M.
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1990, 31, 5587Ϫ5590.
Bis[α-hydroxy-α-(4-tolyl)methyl]phosphinic Acid (5b): This com-
pound was obtained by Reaction H in 10% yield from the reaction
mixture and could not be purified.
J. A. Sikorski,M. J. Miller, D. S. Braccolino, D. G. Cleary, S. D.
Corey, J. L. Font, K. J. Gruys, C. Y. Han, K. C. Lin, P. D.
Pansegrau, J. E. Ream, D. Schnur,A. Shah, M. C. Walker, Phos-
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E. K. Baylis, Eur. Pat. Appl. EP 614900, 1994.
Bis(α-hydroxycinnamyl)phosphinic Acid (5c): This compound was
obtained by reaction H. Solvents were removed under vacuum.
After addition of distilled H2O, products were extracted with di-
ethyl ether. The organic layer was concentrated to dryness. Ad-
dition of n-hexane to the residue caused the formation of a precipi-
tate which was separated from the supernatant and recrystallized
from acetic acid at low temperature to obtain 5c as a white solid
in 16% yield. Ϫ M.p. 155Ϫ157°C (from CH3COOH). Ϫ 31P NMR
(32.44 MHz, [D6]DMSO): δ ϭ 40.1 (m, 33%), 38.8 (m, 67%). Ϫ
1H NMR (250.13 MHz, [D6]DMSO): δ ϭ 7.40Ϫ7.20 (m, 10 H),
6.70Ϫ6.40 (m, 4 H), 4.75Ϫ4.68 (m, 32%) ϩ 4.65Ϫ4.58 (m, 68%) (2
H). Ϫ 13C NMR (62.90 MHz, [D6]DMSO): δ ϭ 136.6 (s), 129.97
(s), 129.81 (s), 128.53 (s), 127.28 (s), 126.83 (s), 126.49 (s), 126.12
[9]
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20112m. Ϫ
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516346, 1992. Ϫ
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[13e]
119Ϫ122. Ϫ
497Ϫ502. Ϫ
E. Öhler, S. Kotzinger, Synthesis 1993,
1
1
(s), 69.18 (d, JCP ϭ 104.4 Hz), 68.13 (d, JCP ϭ 105.6 Hz). Ϫ IR
(KBr, cmϪ1): ν˜ ϭ 3083Ϫ3000 (OH), 2836.5 (PϪOH), 1069 (PϭO).
Ϫ HRMS (glycerol; FAB < 0) for C18H19O4P; m/z: calcd. 329.0942,
found 329.0937 [M Ϫ 1]ϩ. Ϫ C18H19O4P (330.302): calcd. C 65.45,
H 5.76; found C 65.20, H 5.50.
[13f]
J. Holz, M. Quirmbach, A. Börner, Synthesis
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1997, 983Ϫ1006. Ϫ
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A. N. Pudovik, I. V. Konovalova, Synthesis 1979, 81Ϫ96.
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Ϫ
[14c] P. Majewski, Synthesis 1987, 555Ϫ557. Ϫ [14d] H. Wynberg,
Ab A. Smaardijk, Tetrahedron Lett. 1983, 24, 5899Ϫ5900.
Bis[hydroxy(2-pyridyl)methyl]phosphinic Acid Hydrochloride (5d):
This compound was obtained by reaction H. Solvents were re-
moved under vacuum. The residue was taken up in distilled H2O
and extracted with diethyl ether. The aqueous layer was concen-
trated to dryness. The residue was purified by successive recrystalli-
zation from ethanol at low temperature giving 5d as a white solid
in 35% yield. Ϫ M.p. 148Ϫ150°C (from EtOH). Ϫ 31P NMR (32.44
MHz, D2O): δ ϭ 28.2 (67%), 26.8 (33%). Ϫ 1H NMR (80.13 MHz,
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N. J.Gordon, S. A. Jr. Evans, J. Org. Chem. 1993, 58,
[15b]
5293Ϫ5294. Ϫ
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T. Imamoto, T. Oshiki, T. Onozawa, T. Kusumoto, K.
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I. Petnehazy, Z. M. Jaszay, G. Keglevich, P. Tenenyi, L.
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[16b]
2
259Ϫ262. Ϫ
C. Yuan, S. Li, C. Li, S. Chen, W. Huang, G.
D2O): δ ϭ 8.77Ϫ7.89 (m, 8 H), 5.64 (d, JHP ϭ 12 Hz, 61%) ϩ
Wang, C. Pan, Y. Zhang, Heteroatom Chem. 1997, 8, 103Ϫ122.
2
5.55 (d, JHP ϭ 13 Hz, 39%) (2 H). Ϫ 13C NMR (62.90 MHz,
[17] [17a]
F. Texier-Boullet, A. Foucaud, Synthesis 1982, 165Ϫ166
[17b]
D2O): δ ϭ 155.8 (s), 148.6 (s), 143.2 (s), 128.2 (s), 127.9 (s), 71.6
(d, 1JCP ϭ 104.6 Hz), 71.1 (d, 1JCP ϭ 105.4 Hz). Ϫ IR (KBr, cmϪ1):
ν˜ ϭ 3751.5 (OH), 3080.5 (PϪOH), 1159.5 (PϭO), 1030.0 (CϪN).
Ϫ MS (MNBA; FAB > 0); m/z: 281 [M ϩ 1]ϩ. Ϫ C12H15Cl2N2O4P
(353.13): calcd. C 40.81, H 4.28, N 7.93; found C 41.10, H 4.07,
N 7.85.
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[19]
[20]
[21]
[22]
[23]
Bis(α-hydroxybenzyl)phosphane (6a): This compound was obtained
by reaction I. It was stable in acidic solution but it decomposed
during simple evaporation of the solvent. It could not be isolated
but it was identified by 31P-NMR and mass spectra. Ϫ 31P NMR
(32.44 MHz, dioxane/HCl): δ ϭ Ϫ41.4 (td, 1JPH ϭ 208 Hz, 2JPH ϭ
18 Hz). Ϫ MS (glycerol; FAB > 0); m/z: 247 [M ϩ 1]ϩ.
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867