Synthesis and oxidation of (4-hydroxy-3,5-di-tert-butylphenyl)- methanebis[diethyl(diphenyl)phosphine oxides]

Full text of DOI:10.1134/S1070363210030278

ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 3, pp. 533–535. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © M.B. Gazizov, R.K. Ismagilov, L.P. Shamsutdinova, R.Z. Musin, R.F. Karimova, A.A. Bashkirtsev, O.G. Sinyashin, 2010, published
in Zhurnal Obshchei Khimii, 2010, Vol. 80, No. 3, pp. 505–507.
LETTERS
TO THE EDITOR
Synthesis and Oxidation of (4-Hydroxy-3,5-di-tert-butylphenyl)-
methanebis[diethyl(diphenyl)phosphine Oxides]
M. B. Gazizova, R. K. Ismagilova, L. P. Shamsutdinovaa, R. Z. Musinb,
R. F. Karimovaa, A. A. Bashkirtseva, and O. G. Sinyashinb
aKazan State Technological University, ul. K. Marksa 68, Kazan, 420015 Tatarstan, Russia
e-mail: mukattisg@mail.ru
b Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center, Russian Academy of Sciences,
ul. Arbuzova 8, Kazan, 420088 Tatarstan, Russia
Received July 2, 2009
DOI: 10.1134/S1070363210030278
The phosphorylated sterically hindered phenols and
methylenequinones are potential inhibitors of oxida-
tion of organic materials like polymers, petrochemical
products, and biological systems [1–2]. In extension of
studying the reaction of geminal polyhalides with
aprotic nucleophilic reagents [3–5] we studied the
reaction of 4-hydroxy-3,5-di-tert-butylbenzal chloride
I with diethyl and diphenyl chlorophosphines.
temperature for 24 h. The reaction of dichloride I with
diphenyl chlorophosphine requires the heating of the
reagents mixture at 100–110°С for 3 h. Adducts III
form in high yields as colorless hygroscopic viscous
products, weakly fuming in the air. According to the
31Р NMR spectra, compounds IIIa (δP 69.36 ppm) and
IIIb (δP 71.02 ppm) have phosphonium structure in
keeping with the literature data [6, 7]. The treatment of
adducts IIIa and IIIb with anhydrous ethanol followed
by evaporating of the solvents in a vacuum gives the
corresponding bisphosphine oxides IV.
The reaction of dichloride I with diethyl chloro-
phosphine was found to proceed at keeping the hexane
solution of reagents taken in the ratio 1:2 at room
t-Bu
t-Bu
HO
t-Bu
CH[(P+R2Cl)Cl_]2
HO
t-Bu
CHCl2
+
2 R2PCl
III
I
II
t-Bu
t-Bu
HO
t-Bu
[O]
2 EtOH
_2 (EtCl + HCl)
O
C[P(O)R2]2
CH[P(O)R2]2
t-Bu
V
IV
R = Et (a), Ph (b).
Several minutes after dissolving the crude pro-
duct IVa in a large excess of benzene (~1:10) pre-
cipitates the crystalline solvate complex A, 4-hydroxy-
3,5-di-tert-butylphenyl)methanebis(diethylphosphine
oxide) with benzene. The complex was separated by
filtration.
The solvate complex A melts with decomposing at
the temperature close to the boiling temperature of
benzene (78–83°С). On the following gradual heating
for 30–60 min to 145–150°С, the abundant liberation
of benzene bubbles was observed, and crystals of
individual bisphosphine oxide IVa form in the melt
533

534
GAZIZOV et al.
mass. The process completes by the total mass
crystallization. Benzene mass loss corresponds to the
components ratio in the solvate complex A which is
approximately equal to 1:2.
sium ferrocyanide over 3–6 h yields the corresponding
bisphosphorylated methylenequinones V.
(4-Hydroxy-3,5-di-tert-butylphenyl)methanebis-
(diethylphosphine oxide) (IVa). To a solution of
3.44 g of diethyl chlorophosphine in 10 ml of hexane
was added a solution of 3.99 g of dichloride I in 25 ml
of hexane. The mixture was kept for 24 h at room
temperature. The formed viscous mass was twice
washed with hexane and dissolved in 15 ml of ethanol.
This solution was stirred at room temperature for 3 h.
Then the solvent was removed and the residue was
dissolved in 40 ml of cold benzene. The product
precipitates from this solution after 5–10 min as
solvate complex with benzene. Yield 0.63 g, mp 78–
83°С (decomp.). Mass spectrum (1) for sample A (40°С),
m/z (%): 79(6.7), 78(100.0) [М+2], 77(22.6), 52(9,7), 51
(8.7), 50(7.3), 39(7.8); mass spectrum (2) for sample А
(CH3)3C
P(O)(CH2CH3)2
2 C6H6
HO
CH
P(O)(CH2CH3)2
(CH3)3C
A
In the mass spectrum (EI) of the complex A the ion
peak with m/z 428 belongs to the molecular ion (М+) of
the molecule of IVa structure. The presence of two
compounds in A is based on a comparison of the mass
spectra (1) and (2) recorded at the various temperature
of the sample admission into the ions source. The
intensity peaks ratio of ions m/z 78 and 428 originating
from М+-ions of the molecule of benzene and IVa is
1.0:0.0 and 0.2:1.0 at the admission system tempera-
ture 40°С (1) and 90°С (2) respectively. The mass
spectrum (1) coincided virtually with the mass
spectrum of benzene from the instrument computer
database. The mass spectra changes attest that on the
mass spectral studying benzene fractionation occurs
from the sample and the residue is enriched with the
low-volatile compound IVa.
(90°С): 429(4.7), 428(49.7), [М+ ], 413(2.3) [М1 – СН3]+,
1
399(3.1) [М1 – С2Н5]+, 372(17.6) [М1 – С4Н8]+, 371
(69.5) [М1 – С4Н9]+, 324 (79.0), 323(44.6), 278(56.5),
247(37.8), 219 (100.0), 78(10.9) [С6Н6]+, 77(16.5)
[С6Н5]+, 57 (69.0) [С4Н9]+.
Benzene solution was concentrated in a vacuum.
The product crystallizes gradually on slow heating of
viscous residue to 150°С. Yield 2.81 g (47%), mp
168–173°С (isooctane–benzene, 10:1) (174–175°С
[2]). 1Н NMR spectrum (CDCI3), δ, ppm: 0.75–1.30 m
(12H, СН2СН3), 1.40 s [18H, C(CH3)3], 1.60–2.38 m
The main processes of the molecule IVa decay at
the electron impact, mass spectrum (2), are due to the
hydrocarbon particles ejection from ethyl and tert-
butyl groups. As a result of these processes the ions
[М – CН3]+, [М – C2Н5]+, [М – C4Н8]+, [М – C4Н9]+
form.
2
(8H, CH2СН3), 3.28 t (1Н, РСНР, JPH 15 Hz), 5.38 s
(1H, OH), 7.38 br. s (2H, C6H2). Found, %: Р 14.30,
14.65. С23Н42О3Р2. Calculated, %: Р 14.49.
(4-Hydroxy-3,5-di-tert-butylphenyl)methanebis-
(diphenylphosphine oxide) (IVb). A mixture of 0.73 g
of dichloride I and 1.11 g of diphenyl chlorophosphine
was heated in a sealed ampule at 100–110°С for 3 h.
The formed adduct was dissolved in 10 ml of ethanol.
Then the volatile substances were evaporated. Yield
0.81 g (71%), mp 263.5–266°С (toluene) (262–264°С
[2]). 1Н NMR spectrum (CDCI3), δ, ppm: 1.10 s [18Н,
The presence of ion peak m/z 324 owes to Р–С
bond cleavage and diethylphosphinyl group Р(О)
(C2Н5 )2 release with the migration of the one hydrogen
atom to the charged fragment. In the mass spectrum (2)
of compound IVa the ion peak m/z 219, formed
probably from the ion m/z 324 after release of one
more diethylphosphinyl group, is maximal by in-
tensity. The presence of other firagment ions with low
values of m/z in the mass spectrum (2) is evidently
determined by sequential decay of the mentioned ions
at the electron impact.
2
C(CH3)], 4.63 t (1H, PCHP, JРН 16 Hz), 4.98 s (1H,
OH), 6.88 s (2H, C6H2), 7.07–8.13 m (20 H, C6H5).
Found, %: P 10.35, 10.41. С39Н42О3Р2. Calculated, %:
Р 10.00.
4-Bis(diethylphosphinyl)methylene-2,6-di-tert-
butylcyclohexadien-2,5-one (Va). To a solution of
2.14 g of bisphosphine oxide IVa in 20 ml of benzene
was added a solution of 9.87 g of potassium
ferricyanide in 90 ml of 2N КОН under stirring for 3 h.
The colored benzene solution was separated, washed
After the mother liquor concentrating the viscous
noncrystallizable mass remains. The heating of it to
150°С leads to bisphosphine oxide IVa.
The oxidation of benzene solution of bisphosphine
oxides IVa and IVb with alkaline solution of potas-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 3 2010

SYNTHESIS AND OXIDATION OF (4-HYDROXY-3,5-DI-tert-BUTYLPHENYL)-...
with water to neutral reaction, and dried with sodium
REFERENCES
535
sulfate. Then benzene was evaporated in a vacuum.
Yield 1.32 g (62%), orange crystalline substance, mp
183–185°С (heptane). 1Н NMR spectrum (ССl4 +
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