60
SHAIKHUTDINOVA et al.
phosphorus, 3.1 g of 4-methoxybenzyl chloride, and
0.5 g of benzyltriethylammonium chloride in 40 ml
of dioxane, we added dropwise a solution of 35 g of
KOH in 15 ml of H2O. The reaction mixture was
heated for 3 h at 85 90 C and cooled, the organic
layer was separated, the solvent was distilled off, and
the residue was diluted with 40 ml of chloroform.
The resulting suspension was filtered, the chloroform
filtrate was washed with water and dried over po-
tassium carbonate, the solvent was distilled off, and
the residue was washed with ether. We obtained 1.5 g
of a white crystalline product which, according to
3JHH 3.4 Hz). 31P NMR spectrum (CDCl3), P, ppm:
36.7 (1JPH 469 Hz). Found, %: C 66.27; H 6.44;
P 10.89. C16H19O3P. Calculated, %: C 66.21; H 6.55;
P 10.69.
4-Methoxybenzylphosphonous acid (V). A solu-
tion of 0.18 g of 4-methoxybenzylphosphine in 5 ml
of chloroform was kept for 1 h at room temperature
with continuous bubbling of air. A reaction mixture
was obtained whose 31P NMR spectrum contained
signals of the initial phosphine III, 4-methoxybenzyl-
1
phosphine oxide (VI) ( 12.3 ppm, JPH 476.5 Hz),
P
and phosphonous acid V, in the percent ratio of
16 : 64 : 20, respectively. Bubbling of air was contin-
ued for an additional 1 h, after which the solvent was
distilled off, and the residue was washed with ether.
Yield of phosphonous acid V 0.18 g (82%); white
1
the H and 31P NMR spectra, contained 60% phos-
phine oxide I (yield 32%) and 40% phosphine oxide
II (yield 22%).
b. Similarly, but at 70 C from 3.1 g of white phos-
phorus and 3.1 g of 4-methoxybenzyl chloride, we
obtained 1.5 g of a white crystalline product which,
1
crystals, mp 78 80 C. IR spectrum, , cm : 2350
(P H), 1180 (P=O). 1H NMR spectrum, , ppm: 3.06 d
(2H, CH2P), 3.75 s (3H, CH3O), 6.88, 7.10 m (4H,
C6H4), 10.03 m (1H, OH) (1JPH 18.2 Hz). 31P NMR
spectrum, P, ppm: 35.1 (1JPH 557 Hz). Found, %:
C 50.28; H 6.10; P 15.64. C8H11O3P. Calculated, %:
C 51.61; H 5.91; P 16.67.
1
according to the H and 31P NMR spectra, contained
28% phosphine oxide I (yield 15%), 58% phosphine
oxide II (yield 30%), and 14% compound with
34.1 ppm, JPH 558 Hz.
P
1
Reaction of 4-methoxybenzyl chloride with phos-
phine. To a stirred suspension of 10 g of KOH in
50 ml of DMSO and 6.3 ml of H2O, purged with
argon and saturated with phosphine at 40 45 C,
we added dropwise, with continuous phosphine bub-
bling, a solution of 4.7 g of 4-methoxybenzyl chlo-
ride in 5 ml of DMSO over a period of 3 h. The re-
action mixture was heated at 40 45 C for an addi-
tional 1 h in the flow of phosphine, after which
the phosphine flow was stopped, and the mixture
was purged with argon, cooled, diluted with water,
and extracted with ether. The ether extract was
washed with water and dried over potassium car-
bonate, and the solvent was distilled off. The prod-
uct, which, according to the 31P NMR spectrum,
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1
85% phosphine IV (
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1
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3
2JPH 2.9, JHH 7.4 Hz). The bottom residue was
exposed to air for 1 h and washed with ether;
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1
1
cm : 2320 (P H), 1170 (P=O). H NMR spectrum
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(6H, CH3O), 6.84, 7.10 m (8H, C6H4) (2JPH 14.4,
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 1 2001