Synthesis of quaternary phosphonium salts from phosphorylated sterically hindered phenols

Full text of DOI:10.1134/S1070428012120159

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 12, pp. 1574–1575. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © V.V. Andriyashin, Yu.V. Bakhtiyarova, R.A. Cherkasov, V.I. Galkin, I.V. Galkina, 2012, published in Zhurnal Organicheskoi
Khimii, 2012, Vol. 48, No. 12, pp. 1603–1604.
SHORT
COMMUNICATIONS
Synthesis of Quaternary Phosphonium Salts
from Phosphorylated Sterically Hindered Phenols
V. V. Andriyashin, Yu. V. Bakhtiyarova, R. A. Cherkasov, V. I. Galkin, and I. V. Galkina
Kazan (Volga Region) Federal University, ul. Kremlevskaya 18, Kazan, 420008 Tatarstan, Russia
e-mail: vig54@mail.ru
Received May 21, 2012
DOI: 10.1134/S1070428012120159
Phosphorus-containing derivatives of sterically hin-
dered phenols exhibit diverse biological activity [1–3].
In the present communication we describe a procedure
for the synthesis of new 2,6-di-tert-butylphenol deriv-
atives possessing simultaneously phosphonium and
phosphonate fragments.
In the first step, fusion of Mannich base I with
dimethyl or diphenyl phosphonate gave phosphonates
II and III, respectively [4]. Their bromination with
N-bromosuccinimide according to the procedure de-
scribed in [5] and subsequent quaternization of tertiary
phosphines with bromobenzylphosphonates IV and V
afforded phosphonium salts VI–IX which were isolat-
ed as high-melting colorless crystalline substances.
The structure of IX was confirmed by the X-ray dif-
fraction data; the results will be reported elsewhere.
1.5 g (8 mmol), was added to a solution of 2.7 g
(8 mmol) of compound II in 20 ml of carbon tetra-
chloride, and the mixture was irradiated with a 300-W
tungsten filament lamp over a period of 3 h. After
cooling, the precipitate of succinimide was filtered off.
Oily product IV separated from the solution in 30 min
and crystallized after addition of 10 ml of heptane.
Yield 2.4 g (71%), mp 105°C (from heptane). 1H NMR
spectrum (CH3OD), δ, ppm: 2.79 s [18H, C(CH3)3],
7.12 s (1H, OH), 5.12 d (1H, CHBr, JPH = 11.27 Hz),
5.17 s (3H, CH3O), 5.19 s (3H, CH3O), 8.82 d (2H,
C6H2, JPH = 1.47 Hz). 31P NMR spectrum (CH3OD):
δP 21.0 ppm. Found, %: C 50.45; H 7.02; P 7.75.
C17H28BrO4P. Calculated, %: C 50.13; H 6.93; P 7.60.
Diphenyl bromo(3,5-di-tert-butyl-4-hydroxy-
phenyl)methylphosphonate (V) was synthesized in
a similar way. Yield 2 g (76%), mp 85°C (from
Dimethyl bromo(3,5-di-tert-butyl-4-hydroxyphe-
nyl)methylphosphonate (IV). N-Bromosuccinimide,
1
heptane). H NMR spectrum (CH3OD), δ, ppm: 2.75 s
Br
t-Bu
t-Bu
O
t-Bu
O
NMe2
P
P
(RO)2P(O)H
–Me2NH
NBS
OR
OR
RO
RO
HO
HO
HO
Bu-t
Bu-t
II, III
Bu-t
I
IV, V
'
PR3
t-Bu
O
P
'
R3P
Br–
OR
RO
HO
Bu-t
VI–IX
NBS is N-bromosuccinimide; II, IV, R = Me; III, V, R = Ph; VI, R = Me, R′ = Ph; VII, R = Me, R′ = Bu;
VIII, R = R′ = Ph; IX, R = Ph, R′ = Bu.
1574

SYNTHESIS OF QUATERNARY PHOSPHONIUM SALTS
1575
[18H, C(CH3)3], 7.02 s (1H, OH), 4.88 d (1H, CHBr,
Found, %: C 68.34; H 6.04; P 7.82. C45H47BrO4P2.
Calculated, %: C 68.10; H 5.97; P 7.80.
J
PH = 21.02 Hz), 8.13–8.83 m (10H, C6H5), 8.87 d (2H,
C6H2, JPH = 1.65 Hz). 31P NMR spectrum (CH3OD):
δP 11.8 ppm. Found, %: C 61.15; H 6.14; P 5.84.
C27H32BrO4P. Calculated, %: C 61.02; H 6.07; P 5.83.
Tributyl[(3,5-di-tert-butyl-4-hydroxyphenyl)(di-
phenoxyphosphoryl)methyl]phosphonium bromide
(IX). Yield 0.322 g (88%), mp 229°C (decomp).
31P NMR spectrum (CH3OD), δP, ppm: 9.8, 34.4.
Found, %: C 64.01; H 8.21; P 8.53. C39H59BrO4P2.
Calculated, %: 63.84; H 8.10; P 8.44.
Phosphonium salts VI–IX (general procedure).
Triphenylphosphine or tributylphosphine, 0.5 mol, was
added to a solution of 0.5 mmol of phosphonate IV or
V in 10 ml of diethyl ether. After 30 min, the crystal-
line product was filtered off, washed with diethyl ether,
and dried in air.
1
The H and 31P NMR spectra were measured on
a Bruker Avance-400 spectrometer; the chemical shifts
were determined relative to the residual proton signal
of the solvent (1H) or 85% H3PO4 (31P, external
reference).
[(3,5-Di-tert-butyl-4-hydroxyphenyl)(dimethoxy-
phosphoryl)methyl]triphenylphosphonium bromide
(VI). Yield 0.268 g (80%), mp 145°C (decomp.).
31P NMR spectrum (CH3OD), δP, ppm: 17.9, 23.5.
Found, %: C 63.01; H 6.67; P 9.31. C35H43BrO4P2.
Calculated, %: C 62.78; H 6.47; P 9.25.
REFERENCES
1. Ovchinnikova, L.P., Rotskaya, U.N., Vasyunina, E.A.,
Sinitsina, O.I., Kandalintseva, N.V., Prosenko, A.E., and
Nevinskii, G.A., Bioorg. Khim., 2009, vol. 35, p. 417.
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3. Andriyashin, V.V., Bakhtiyarova, Yu.V., Galkina, I.V., and
Galkin, V.I., Abstracts of The Butlerov International Con-
gress on Organic Chemistry, Kazan, Russia, 2011, p. 363.
Tributyl[(3,5-di-tert-butyl-4-hydroxyphenyl)(di-
methoxyphosphoryl)methyl]phosphonium bromide
(VII). Yield 0.264 g (87%), mp 240°C (decomp).
31P NMR spectrum (CH3OD), δP, ppm: 19.9, 34.1.
Found, %: C 57.43; H 9.67; P 10.23. C29H55BrO4P2.
Calculated, %: C 57.14; H 9.09; P 10.16.
[(3,5-Di-tert-butyl-4-hydroxyphenyl)(diphenoxy-
phosphoryl)methyl]triphenylphosphonium bromide
(VIII). Yield 0.367 g (78%), mp 238°C (decomp.).
31P NMR spectrum (CH3OD), δP, ppm: 8.2, 23.4.
4. Mukmeneva, N.A., Kadyrova, V.Kh., and Zharko-
va, V.M., Zh. Obshch. Khim., 1992, vol. 62, p. 1670.
5. Gross, H., Keitel, I., and Costisella, B., Phosphorus,
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 12 2012