S. Chikkali, D. Gudat
FULL PAPER
less precipitate formed was isolated by filtration, washed twice with
5 mL of DME, and dried in vacuo for 4 h.
ether (10 mL). This mixture was stirred for five minutes at room
temperature and an excess of conc. hydrochloric acid (2 mL,
24 mmol) was added. A colorless precipitate formed immediately.
The reaction mixture was then stirred for further 60 min, the pre-
cipitate filtered off, washed twice with diethyl ether (5 mL), and
dried for 1 h in vacuo. Yield: 1.86 g (90%); m.p. 104 °C; elemental
analysis: C19H18ClO2P (344.78): calcd. C 66.19 H 5.26 Cl 10.28;
found C 66.76 H 5.38 Cl 8.54. 31P{1H}NMR (solid, 162 MHz, CP/
MAS): δiso = –0.8.
2-[(Diphenylphosphinoyl)methyl]phenol (5a): Yield 2.59 g (70%);
m.p. 177 °C; elemental analysis: C19H17O2P (308.32): calcd. C 74.02
H 5.56, found C 73.90 H 5.37. Spectroscopic data are identical with
the values reported in the literature.[7]
3-[(Diphenylphosphinoyl)methyl]benzene-1,2-diol (5b): Yield 3.31 g
(85%); m.p. 194 °C; elemental analysis: C19H17O3P (324.32): calcd.
C 70.37 H 5.28; found C 70.44 H 5.35. 1H NMR (400 MHz,
CDCl3): δ = 8.2 (br., 2 H, OH), 7.74 (m, 4 H, o-H), 7.58 (m, 2 H,
p-H), 7.50 (m, 4 H, m-H), 6.81 (ddd, 3JHH = 8.0 Hz, 4JHH = 1.7 Hz,
4-[(Diphenylphosphanyl)hydroxymethyl]phenol (4c): A solution of
diphenylphosphane (2) (1.43 mL, 8.2 mmol) and 4-hydroxybenzal-
dehyde (3c) (1.00 g, 8.2 mmol) in methanol (10 mL) was stirred for
5 min at room temperature and conc. hydrochloric acid (0.25 mL,
3 mmol) was added. A colorless precipitate formed immediately.
The reaction mixture was stirred for further 60 min, the precipitate
filtered off and dried for 1 h in vacuo. Yield: 2.27 g (90%); m.p.
168 °C; elemental analysis: C19H17O2P (308.32): calcd. C 74.02 H
5.92; found 74.29 H 5.92. 31P NMR (101 MHz, THF): δ = –2.3 (s)
ppm. 31P{1H}NMR (solid, 162 MHz, CP/MAS): δiso = –7.2 ppm.
3
5
6JPH = 1.7 Hz, 1 H, H-6), 6.63 (dt, JHH = 8.0 Hz, JPH = 0.9 Hz,
3
4
4
1 H, H-5), 6.34 (dddm, JHH = 7.7 Hz, JHH = 1.7 Hz, JPH
=
2
1.7 Hz, 1 H, H-4), 3.73 (d, JPH = 12.8 Hz, 2 H, CH2) ppm.
13C{1H} NMR (100 MHz, CDCl3): δ = 148.2 (d, JPC = 2.7 Hz),
143.9 (d, JPC = 4.2 Hz), 133.2 (d, JPC = 2.7 Hz, p-C), 131.6 (d, JPC
= 9.6 Hz, o-C), 130.9 (d, JPC = 100.4 Hz, i-C), 129.4 (d, JPC
=
12.1 Hz, m-C), 122.9 (d, JPC = 6.3 Hz), 121.7 (d, JPC = 1.9 Hz),
119.9 (d, JPC = 8.4 Hz), 114.6 (d, JPC = 2.5 Hz), 35.6 (d, JPC
=
67.1 Hz, CH2) ppm. 31P NMR (101 MHz, CDCl3): δ = 40.4 (s)
ppm. MS (EI = 70 eV): m/z (%) = 324.1 (100) [M+]; 202.1 (38)
[Ph2POH+], 201 (54) [Ph2PO+].
Bis[hydroxy(3-hydroxyphenyl)methyl]diphenylphosphonium Toluene-
sulfonate (7e/7eЈ): A solution of diphenylphosphane (2) (1.43 mL,
8.2 mmol) and 3-hydroxy benzaldehyde (3e) (1.00 g, 8.2 mmol) in
DME (5 mL) was stirred for 5 min at room temperature and p-
toluenesulfonic acid (0.60 g, 3.2 mmol) was added. A colorless pre-
cipitate began to form after 10 min. The reaction mixture was
stirred for 12 h, the precipitate filtered off, washed twice with
DME, and dried for 4 h in vacuo. Yield: 1.73 g (90%); m.p. 121 °C;
elemental analysis: C33H31O7PS (602.64): calcd. C 65.77 H 5.19;
found 65.39 H 5.30. 31P{1H}NMR (solid, 162 MHz, CP/MAS): δiso
= 30.5, 29.9 ppm.
4-[(Diphenylphosphinoyl)methyl]phenol (5c): Yield 2.22 g (60%);
m.p. 223 °C; elemental analysis: C19H17O2P (308.32): calcd. C 74.02
1
H 5.56; found 74.19 H 5.82. H NMR (400 MHz, CDCl3): δ = 8.2
(br., 1 H, OH), 7.76 (m, 4 H, o-H), 7.57 (m, 2 H, p-H), 7.49 (m, 4
2
H, m-H), 6.82 (m, 2 H, C6H4), 6.56 (m, 2 H, C6H4), 3.62 (d, JPH
= 12.2 Hz, 2 H, CH2) ppm. 13C{1H} NMR (100 MHz, CDCl3): δ
2
= 156.9 (d, JPC = 1.7 Hz), 132.7 (s), 131.8 (d, JPC = 9.2 Hz, o-C),
3
131.6 (d, JPC = 4.8 Hz), 129.3 (d, JPC = 11.7 Hz, m-C), 128.6 (d,
General Procedure for the Synthesis of Phenol-Functionalized Phos-
phanes: The appropriate phosphane oxide 5a–d (10 mmol) was dis-
solved in dry THF (100 mL). Methyl iodide (0.69 mL, 11 mmol)
was added via a syringe and the solution stirred for 2 h at room
temperature. The mixture was then cooled to 0 °C and solid LiAlH4
(1.7 g, 45 mmol) added in several small portions. The reaction mix-
ture was warmed to ambient temperature, and stirring was contin-
ued for another 5–6 h. The progress of the reaction was monitored
by TLC. The reaction flask was again cooled to 0 °C, and 50 mL
of 1 hydrochloric acid were added in several portions (the first
few drops had to be added very carefully until the exothermic reac-
tion became less violent). The organic layer was separated and the
aqueous layer washed with ethyl acetate (3×50 mL). The combined
organic phases were dried overnight with Na2SO4 and all volatiles
evaporated in vacuo. The crude products were purified by column
chromatography (silica, petroleum ether:ethyl acetate = 7:3).
JPC = 99.6 Hz), 120.7 (d, JPC = 7.5 Hz), 117.0 (d, JPC = 2.1 Hz),
37.4 (d, JPC = 72.1 Hz, CH2) ppm. 31P NMR (162 MHz, CDCl3):
δ = 32.2 (s) ppm.
4-[(Diphenylphosphinoyl)methyl]benzene-1,2-diol (5d): Yield 3.50 g
(90%); m.p. 192 °C; elemental analysis: C19H17O3P (324.32): calcd.
C 70.37 H 5.28; found C 69.98 H 5.17. 1H NMR (250 MHz,
CDCl3): δ = 7.47 to 7.23 (m, 10 H, C6H5), 6.53 (s, 1 H, C6H3), 6.31
3
3
(d, JHH = 8.1 Hz, 1 H, C6H3), 6.12 (d, JHH = 8.1, 1 H, C6H3),
3.42 (d, 2JPH = 12.9 Hz, 2 H, CH2) ppm. 13C{1H} NMR (62 MHz,
CD3CN/CDCl3): δ = 143.8 (d, JPC = 2.3 Hz), 143.2 (d, JPC
=
3.1 Hz), 131.7 (d, JPC = 1.8 Hz, p-C), 130.3 (d, JPC = 9.4 Hz, o-C),
128.1 (d, JPC = 11.7 Hz, m-C), 126.9 (d, JPC = 101.8 Hz, i-C), 121.2
(d, JPC = 6.1 Hz), 120.9 (d, JPC = 8.4 Hz), 116.6 (d, JPC = 4.8 Hz),
114.4 (d, JPC = 2.3 Hz), 35.1 (d, JPC = 68.2 Hz) ppm. 31P NMR
(101 MHz, CDCl3): δ = 40.4 (s) ppm.
3-[(Diphenylphosphinoyl)methyl]phenol (5e): Yield 2.22 g (60%);
m.p. 198 °C; elemental analysis: C19H17O2P (308.32): calcd. C 74.02
H 5.56; found C 74.10 H 5.60. 1H NMR (250 MHz, CD3CN/
CDCl3): δ = 7.55 (m, 4 H, o-H), 7.40 to 7.25 (m, 6 H, m/p-H), 6.80
2-[(Diphenylphosphanyl)methyl]phenol (8a): Yield 1.81 g (62%); col-
orless oil, elemental analysis: C19H17OP (292.32): calcd. C 78.07 H
5.86; found C 74.33 H 5.91. 1H NMR (250 MHz, [D8]toluene): δ
= 6.8 to 7.5 (m, 10 H, C6H5), 6.80 (t, 1 H, 3JHH = 7.7 Hz), 6.74 (d,
1 H, JHH = 7.7 Hz), 6.61 (d, 1 H, JHH = 7.8 Hz), 6.50 (t, 1 H,
3JHH = 7.5 Hz), 3.32 (s, 2 H, CH2) ppm. 31P{1H} NMR (101 MHz,
[D8]toluene): δ = –15.0 ppm. The 1H NMR spectroscopic data
match those published earlier.[11]
3
3
3
3
(t, JHH = 8.0 Hz, 1 H, H-5), 6.59 (s, 1 H, H-2), 6.44 (d, JHH
=
3
8.0 Hz, 1 H, H-4/6), 6.41 (d, JHH = 8.0 Hz, 1 H, H-4/6), 3.50 (d,
2JPH = 13.4 Hz, 2 H, CH2) ppm. 13C{1H} NMR (62 MHz,
CD3CN/CDCl3): δ = 157.1 (d, JPC = 2.6 Hz), 132.4 (d, JPC
=
2.9 Hz, p-C), 131.2 (d, JPC = 9.5 Hz, o-C), 131.0 (s), 130.9 (d, JPC
= 102.3 Hz, i-C), 129.5 (d, JPC = 2.1 Hz), 128.9 (d, JPC = 11.8 Hz,
m-C), 121.8 (d, JPC = 5.8 Hz), 117.5 (d, JPC = 5.0 Hz), 114.2 (d, JPC
= 2.9 Hz), 37.1 (d, JPC = 67.1 Hz) ppm. 31P{1H}NMR (101 MHz,
CDCl3): δ = 31.4 ppm.
3-[(Diphenylphosphanyl)methyl]benzene-1,2-diol (8b): Yield 1.85 g
(60%); m.p. 82 °C; elemental analysis: C19H17O2P (308.32): calcd.
C 74.02 H 5.56; found C 73.91 H 5.73. 1H NMR (400 MHz,
CDCl3): δ = 7.52 to 7.30 (m, 10 H, C6H5), 6.78 (dm, 3JHH = 7.9 Hz,
1 H, C6H3), 6.64 (tm, JHH = 7.9 Hz, 1 H, C6H3), 6.43 (dm, JHH
= 7.9 Hz, 1 H, C6H3), 6.02 (br., 1 H, OH), 5.86 (br., 1 H, OH),
3.52 (d, 2JPH = 1.7 Hz, 2 H, CH2) ppm. 13C{1H} NMR (100 MHz,
CDCl3): δ = 145.0 (d, JPC = 1.6 Hz), 141.7 (d, JPC = 3.7 Hz), 132.8
3
3
2-[(Diphenylphosphanyl)hydroxymethyl]phenol Hydrochloride (6a):
2-Hydroxybenzaldehyde (3a) (0.64 mL, 6 mmol) was added to a
solution of diphenylphosphane 2 (1.05 mL, 6 mmol) in diethyl
3008
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Eur. J. Inorg. Chem. 2006, 3005–3009