Synthesis of quaternary phosphonium salts on the basis of 2,6-di-tert-butyl-4-methylphenol

Full text of DOI:10.1134/S1070428012120160

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 12, pp. 1576–1577. © 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. 1605–1606.
SHORT
COMMUNICATIONS
Synthesis of Quaternary Phosphonium Salts on the Basis
of 2,6-Di-tert-butyl-4-methylphenol
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/S1070428012120160
Phosphorus-containing 2,6-di-tert-butyl-4-methyl-
phenol derivatives exhibit a broad spectrum of antibac-
terial and antimycotic activity and are widely used as
antioxidants [1, 2]. Depending on the substituents on
the phosphorus atom, these compounds are active
against pathogenic microorganisms in humans and
animals, in particular against Staphylococcus aureus,
Escherichia coli, Salmonella paratyphi B, Pseudo-
monas aeruginosa, and Candida albicans. We previ-
ously described a procedure for the synthesis of quater-
nary phosphonium derivatives of 2,6-di-tert-butyl-4-
methylphenol (I) by quaternization of tertiary phos-
phines with 3,5-di-tert-butyl-4-hydroxybenzyl bromide
(II) which was prepared by bromination of phenol I
with N-bromosuccinimide [3]. The reactions of benzyl
bromide II with triphenylphosphine (III), methyldi-
phenylphosphine (IV), and tributylphosphine (V), as
well as with 1,2-bis(diphenylphosphino)ethane (VI),
1,3-bis(diphenylphosphino)propane (VII), and 1,6-bis-
(diphenylphosphino)hexane (VIII), in diethyl ether at
room temperature gave the corresponding crystalline
phosphonium salts IX–XIV.
The
31P NMR spectra of IX–XIV contained only
one signal in the region δP 23.2–33.4 ppm, which cor-
1
responds to the phosphonium group. In the H NMR
spectra of these compounds, a singlet at δ 2.5 ppm
from protons in the tert-butyl groups, a doublet at
δ ~6 ppm from the methylene protons, a singlet at
δ 7 ppm from the OH proton, and a doublet at δ 8.0–
8.5 ppm from protons in the meta positions of the
phenol ring were observed. The structure of phospho-
nium salt XII was confirmed by X-ray analysis; the
results will be reported elsewhere. All newly synthe-
sized phosphonium salts showed a high antimicrobial
activity.
4-Bromomethyl-2,6-di-tert-butylphenol (II) was
1
synthesized as described in [3]. mp 56°C. H NMR
spectrum (CH3OD), δ, ppm: 2.80 s [18H, C(CH3)3],
5.97 s (1H, CH2Br), 7.00 s (1H, OH), 8.62 s (2H,
C6H2). Found, %: C 60.54; H 8.01. C15H23BrO4. Cal-
culated, %: C 60.21; H 7.75.
Phosphonium salts IX–XIV (general procedure).
Equimolar amounts (0.001 mol) of bromide II in 5 ml
R'
t-Bu
t-Bu
Br
P
R2R'P (III–V)
Br–
R
R
HO
Br
HO
Bu-t
Bu-t
II
IX–XI
Bu-t
Bu-t
t-Bu
Ph2P(CH2)nPPh2 (VI–VIII)
HO
OH
2Br–
Ph Ph
Ph
Ph
HO
P
P
( )n
Bu-t
t-Bu
Bu-t
II
XII–XIV
III, IX, R = R′ = Ph; IV, X, R = Ph, R′ = Me; V, XI, R = R′ = Bu; VI, XII, n = 2; VII, XIII, n = 3; VIII, XIV, n = 6.
1576

SYNTHESIS OF QUATERNARY PHOSPHONIUM SALTS
1577
of diethyl ether and the corresponding tertiary phos-
phine or bis-phosphine in 5 ml of diethyl ether were
mixed together at room temperature, and the mixture
was kept for 10–20 min. The precipitate was filtered
off and washed with diethyl ether.
Ethane-1,2-diylbis[(3,5-di-tert-butyl-4-hydroxy-
benzyl)diphenylphosphonium] dibromide (XII).
31
Yield 0.463 g (93%), mp 195°C (decomp.). P NMR
spectrum (CH3OD): δP 29.2 ppm. Found, %: C 67.53;
H 7.14; P 6.20. C56H70Br2O2P2. Calculated, %:
C 67.47; H 7.08; P 6.21.
(3,5-Di-tert-butyl-4-hydroxybenzyl)triphenyl-
phosphonium bromide (IX). Yield 0.533 g (95%),
Propane-1,3-diylbis[(3,5-di-tert-butyl-4-hydroxy-
1
benzyl)diphenylphosphonium] dibromide (XIII).
mp 225°C (decomp.). H NMR spectrum (CH3OD), δ,
31
Yield 0.454 g (90%), mp 215°C (decomp.). P NMR
ppm: 2.58 s [18H, C(CH3)3], 5.92 d (2H, CH2, JPH
13.87 Hz), 7.00 s (1H, OH), 8.09 d (2H, C6H2, JPH
=
=
spectrum (CH3OD): δP 24.9 ppm. Found, %: C 67.74;
H 7.25; P 6.20. C57H72Br2O2P2. Calculated, %:
C 67.72; H 7.18; P 6.13.
2.69 Hz), 8.87–9.28 m (15H, C6H5). 31P NMR spec-
trum (CH3OD): δP 23.4 ppm. Found, %: C 70.70;
H 7.00; P 5.62. C33H38BrOP. Calculated, %: C 70.58;
H 6.82; P 5.52.
Hexane-1,6-diylbis[(3,5-di-tert-butyl-4-hydroxy-
benzyl)diphenylphosphonium] dibromide (XIV).
Yield 0.481 (92%), mp 162°C (decomp.). 31P NMR
spectrum (C2D5OD): δP 25.4 ppm. Found, %: C 68.65;
H 7.51; P 5.94. C60H78Br2O2P2. Calculated, %:
C 68.44; H 7.47; P 5.88.
(3,5-Di-tert-butyl-4-hydroxybenzyl)methyl(di-
phenyl)phosphonium bromide (X). Yield 0.489 g
1
(98%), mp 242°C (decomp.). H NMR spectrum
(CH3OD), δ, ppm: 2.65 s [18H, C(CH3)3], 3.70 d (3H,
1
The H and 31P NMR spectra were recorded on
CH3, JPH = 13.68 Hz), 5.63 d (2H, CH2, JPH
14.41 Hz), 7.02 s (1H, OH), 8.17 d (2H, C6H2, JPH
=
=
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).
2.78 Hz), 9.04–9.25 m (10H, C6H5). 31P NMR spec-
trum (CH3OD): δP 23.2 ppm. Found, %: C 67.40;
H 7.29; P 6.17 C28H36BrOP. Calculated, %: C 67.33;
H 7.26; P 6.20.
REFERENCES
Tributyl(3,5-di-tert-butyl-4-hydroxybenzyl)-
phosphonium bromide (XI). Yield 0.476 g (95%),
colorless crystals, mp 188°C (decomp.). H NMR
1. Zenkov, N.K., Kandalintseva, N.V., Lankin, V.Z.,
Menytsikova, E.B., and Prosenko, A.E., Fenol’nye bio-
antioksidanty (Phenolic Bioantioxidants). Novosibirsk:
Sib. Otd. Ross. Akad. Med. Nauk, 2003.
2. 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.
1
spectrum (CH3OD), δ, ppm: 2.27–3.47 m (27H, C4H9),
2.80 s [18H, C(CH3)3], 4.90 d (2H, CH2, JPH
=
=
14.09 Hz), 7.11 s (1H, OH), 8.45 d (2H, C6H2, JPH
31
2.52 Hz). P NMR spectrum (CH3OD): δP 33.4 ppm.
Found, %: C 64.82; H 10.19; P 6.17. C27H50BrOP.
Calculated, %: C 64.66; H 10.05; P 6.18.
3. Kim, D.H. and Kummerow, F.A., J. Am. Chem. Soc.,
1961, vol. 39, p. 150.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 12 2012