Synthesis and Properties of [(4-Hydroxy-3,5-di-tert-butylphenyl)- chloromethanediphenylphosphine Oxide

Full text of DOI:10.1134/S1070363212090241

ISSN 1070-3632, Russian Journal of General Chemistry, 2012, Vol. 82, No. 9, pp. 1587–1589. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © M.B. Gazizov, R.K. Ismagilov, L.P. Shamsutdinova, R.F. Karimova, R.Z. Musin, K.A. Nikitina, A.A. Bashkirtsev, O.G. Sinyashin,
2012, published in Zhurnal Obshchei Khimii, 2012, Vol. 82, No. 9, pp. 1553–1555.
LETTERS
TO THE EDITOR
Synthesis and Properties of [(4-Hydroxy-3,5-di-tert-butylphenyl)-
chloromethanediphenylphosphine Oxide
M. B. Gazizova, R. K. Ismagilova, L. P. Shamsutdinovaa, R. F. Karimovaa, R. Z. Musinb,
K. A. Nikitinab, A. A. Bashkirtseva, and O. G. Sinyashinb
a Kazan State Technological University, ul. Marksa 68, Kazan, Tatarstan, 420015 Russia
e-mail: mukattisg@mail.ru
b Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy of Sciences,
Kazan, Tatarstan, Russia
Received March 23, 2012
DOI: 10.1134/S1070363212090241
Previously, 4-hydroxy-3,5-di-tert-butylbenzylidene-
chloride (gem-dichloride) I has been found to react
with esters of P(III)-acids in molar ratios of 1:2 and 1:1
and secondary chlorophosphines in the ratio of 1:2 by
the scheme of the exhaustive dechlorophosphorylation
to form (4-hydroxy-3,5-di-tert-butylphenyl)methanedi-
phosphonates and -diphosphine oxides [1, 2].
chlorophosphine II in a 1:1 ratio occurs at room
temperature over 24–48 h to give adduct III of the
equimolar amounts of the reactants. Adduct III is a
colorless crystalline solid. The 31P NMR spectral data
(δP 36.31 ppm) confirm the phosphonium structure.
At treating with sulfur dioxide adduct III trans-
forms into [(4-hydroxy-3,5-di-tert-butylphenyl)chloro-
methanediphenylphosphine oxide IV.
The reaction of gem-dichloride I with diphenyl-
t-Bu
t-Bu
−
+
HO
t-Bu
CHCl2 + Ph2PCl
HO
t-Bu
CHClPPh2Cl Cl
III
I
II
t-Bu
HO
t-Bu
III + SO2
CHClP(O)Ph2 + SOCl2
IV
Adduct III also decomposes when exposed to
moisture in air over 10–15 days. The process takes
place with the release of hydrogen chloride and the
formation of phosphine oxide IV.
spectra of both products IV synthesized are identical.
The structure of IV was confirmed by the EI mass
spectrometry. The main decay processes of compound
IV are associated with the primary release of hydrogen
chloride, and then of diphenylphosphinyl groups and
hydrocarbon radicals. In the mass spectrum (EI) of IV
the most intensive peak with m/z 418 belongs to the
ion formed by the release of hydrogen chloride from
Compound IV was also obtained via the reaction
of hydrogen chloride with 4-(diphenylphosphinyl-
methylene)-2,6-di-tert-butylcyclo-hexadien-2,5-one V.
1
The melting points and the H, 31P NMR and IR
1587

1588
GAZIZOV et al.
the molecular ion. The ion peak with m/z 217 is the
result of releasing diphenylphosphinyl group from the
ion with m/z 418. Also in the spectra the following
peaks, m/z, were observed: 403 [418 – Me]+, 361
[418 – t-Bu]+, 201 [Ph2P=O]+.
The reactions of compound IV with anhydrous
ethanol, triethylamine, and esters of P(III)-acids
proceed in high yields.
[(4-Hydroxy-3,5-di-tert-butyl)chloromethane-
diphenylchlorophosphonium chloride (III).
A
The reaction of adduct III with an excess of
anhydrous ethanol results in hydrochloric salt VI.
Treating salt VI with triethylamine provides phosphine
oxide VI .
t-Bu
mixture of a solution of 2.89 g (0.01 mol) of gem-
dichloride I in 30 ml of hexane and 2.20 g (0.01 mol)
of diphenylchlorophosphine II in 10 ml of hexane was
kept for 48 h at room temperature. After removing of
the solvent the solid residue was ground to a fine
powder. A sample of the product (0.25 g) was washed
with a small amount of cold benzene to yield 0.18 g of
a colorless crystalline adduct III, mp 175–180°C. 31P
NMR spectrum: δP 36.31 ppm. Found P, %: 5.95, 5.80.
С27Н32ОРCl3. Calculated P, %: 6.08.
2EtOH
III
HO
HCl
CHP(O)Ph2
OEt
−EtCl
−HCl
t-Bu
t-Bu
VI
[(4-Hydroxy-3,5-di-tert-butyl)chloromethane-
Et3N
diphenylphosphine oxide (IV). а. Through
a
HO
t-Bu
CHP(O)Ph2
OEt
VII
suspension of 4.89 g of the adduct III in 60 ml of
benzene was passed dry sulfur dioxide for 1 h until
complete disappearance of the solid phase. Volatile
components were removed in vacuo, the residue was
triturated with hexane to complete solidification. Yield
−Et3N HCl
1
2.46 g (57%), mp 183–187°C (toluene). H NMR
[(4-Hydroxy-3,5-di-tert-butylphenyl)chloromethane-
diphenylphosphine oxide IV corresponds to the poorly
studied class of the phosphorylated halogen derivatives
of the sterically hindered phenols. We showed the high
reactivity of this compound with respect to the rea-
gents of basic and nucleophilic character.
spectrum (CCl4 + CDCl3), δ, ppm: 1.48 s [18H, C
2
(CH3)33], 5.45 d (1H, CHP, JPH 6.5 Hz), 7.12 d (2H,
C6H2, JHH 2 Hz), 7.40–8.2 m (10H, C6H5). 31P NMR
spectrum: δP 26.55 ppm. Found, %: Cl 7.60; P 7.18.
С27Н32О2РCl. Calculated, %: Cl 7.81; P 6.82.
t-Bu
EtOH
HO
CH(OEt)P(O)Ph2 + HCl
t-Bu
VII
t-Bu
O
t-Bu
Et3N
HCl
HO
t-Bu
CHP(O)Ph2 + Et3N
CH P(O)Ph2
Cl
t-Bu
V
IV
t-Bu
R2POEt
HO
CH[P(O)R2]P(O)Ph2 + EtCl
t-Bu
R=OEt (а), Et (b).
VIIIа, VIIIb
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 9 2012

SYNTHESIS AND PROPERTIES OF [(4-HYDROXY-3,5-DI-tert-BUTYLPHENYL)-...
1589
1
b. Through a solution of 2.9 g (0.005 mol) of the
phosphorylated methylenequinone V in 30 ml of
benzene was passed dry hydrogen chloride for 15–20 min.
After removing of the volatile components in vacuo
the residue was treated with hexane to yield 2.18 g
(96%) of compound IV, mp 185–187°C (toluene).
(toluene) (160°C [5]). H NMR spectrum (СCl4 +
3
СDCl3), δ, ppm: 1.12 t (3Н, СН3, JHH 6 Hz), 1.20 t
(3Н, СН3, JHH 6 Hz), 1.42 s [18Н, С(СН3)3], 3.85–
3
4.25 m (5H, ОСН2, PCHP), 5.18 s (ОH), 7.10 br.s (2Н,
С6Н2), 7.20–8.20 m (10Н, С6Н5). 31Р NMR spectrum,
δP, ppm: 19.32 (phosphine oxide), 26.12 (phos-
phonate). Found Р, %: 10.50, 10.55. С31Н42О5Р2. Cal-
culated Р, %: 11.13.
[(4-Hydroxy-3,5-di-tert-butyl)ethoxymethane-
diphenylphosphine oxide (VII). а. Adduct III,
prepared from 1.45 g (0.005 mol) of gem-dichloride I
and 1.10 g (0.005 mol) of diphenylchlorophosphine,
was boiled with 15 ml of anhydrous ethanol for 1 h.
After removing of the volatile components in vacuo
the residue was dissolved in 30 ml of toluene and
treated with 0.50 g of triethylamine. The resulting
triethylamine hydrochloride was filtered off. The
residue was concentrated. Yield 1.40 g (60%), mp
170–173°C (heptane–toluene) (170–172°C [3]). IR
spectrum, ν, cm–1: 3350 br. (OH, as), 1595 (С6H5),
[(4-Hydroxy-3,5-di-tert-butylphenyl)(diethylphos-
phinyl)methanediphenylphosphine oxide (VIIIb).
To 1.59 g (0.0035 mol) of compound IV was added
dropwise 0.47 g (0.0035 mol) of ethyldiethylphos-
phinite. The mixture self-heated to 70°C. Ethyl chlo-
ride release and the crystal mixture restructuring occur.
After 3 h the reaction mixture was treated with toluene.
Yield 1.53 (84%), mp 222–224°C (toluene). H NMR
spectrum (СDCl3), δ, ppm: 0.95–1.40 m (6Н, СН3),
1.45 s [18Н, С(СН3)3], 1.70–2.40 m (4H, СН2), 4.04 t
1
2
1
(1H, PСНP, JPH 16 Hz), 5.25 s (1H, ОH), 7.10 br. s
(2Н, С6Н2), 7.35–8.05 m (10Н, С6Н5). Found Р, %:
11.45, 11.65. С31Н42О3Р. Calculated Р, %: 11.83.
1150 (P=O). Н NMR spectrum(СCl4 + d-acetone), δ,
ppm: 1.15 t (3Н, СН3, 3JHH 6 Hz), 1.35 s [18Н, С(СН3)3],
2
3.35–3.70 m (2H, ОCH2), 5.00 d (1Н, PСН, JPH
4
10 Hz), 5.60 br.s (1H, OH), 6.75 d (2H, C6H2, JHH
The 1H NMR spectra were recorded on a Tesla BS-
567A (100 MHz) spectrometer relative to internal
TMS. The 31P NMR spectra were registered on a CXP-
100 instrument (36.5 MHz) relative to external 85%
H3PO4. The mass spectra were obtained by electron
impact on a TRACE MS Finnigan MAT instrument
(70 eV, 200°C) at a direct input of the substance into
the ion source. The processing of mass spectral data
was performed using a Xcalibur software. The peaks
of the ions containing the most common isotopes are
given.
2 Hz), 7.30–8.10 m (10H, С6Н5). Found P, %: 6.35,
6.43. С29Н37О3Р. Calculated P, %: 6.68.
b. A solution of 0.91 g (0.002 mol) of compound
IV in 5 ml of anhydrous ethanol was refluxed for
30 min. After distilling off the volatile components in a
vacuum the residue was treated with hexane to yield
0.60 g (65%) of the product VII, mp 170–172°C
(heptane–toluene).
4-(Diphenylphosphinylmethylene)-2,6-di-tert-
butylcyclohexadien-2,5-one (V). Adding a solution of
0.11 g (0.001 mol) of triethylamine in 3 ml of benzene
to a solution of 0.45 g (0.001 mol) of compound IV in
20 ml of benzene at stirring resulted in a colorless
precipitate. The reaction mixture was kept for 6 h at
room temperature. Then triethylamine hydrochloride
(0.11 g, 80.3%) was filtered off. The residue was
concentrated in a vacuum. Yield 0.37 g (88%), mp
216–219°C (toluene) (219–221°C [4]).
REFERENCES
1. Gazizov, M.B., Ismagilov, R.K., Shamsutdinova, L.P.,
Karimova, R.F., and Sinyashin, O.G., Russ. J. Gen.
Chem., 2005, vol. 75, no. 12, p. 1971.
2. Gazizov, M.B., Ismagilov, R.K., Shamsutdinova, L.P.,
Musin, R.Z., Karimova, R.F., Bashkirtsev, A.A., and
Sinyashin, O.G., Russ. J. Gen. Chem., 2010, vol. 80,
no. 3, p. 533.
3. Gazizov, M.B., Ismagilov, R.K., Karimova, R.F.,
Shamsutdinova, L.P., and Sinyashin, O.G., Dokl.
Chem., 2005, vol. 400, no. 1–3, p. 1.
4. Ismagilov, R.K., Moskva, V.V., Arkhipov, V.V., and
Ivantsov, A.B., Zh. Obshch. Khim., 1991, vol. 61,
no. 2, p. 387.
[(4-Hydroxy-3,5-di-tert-butylphenyl)(diethoxy-
phosphoryl)methanediphenylphosphine oxide (VIIIа).
A mixture of 0.91 g (0.002 mol) of compound IV and
0.37 g (0.0022 mol) of triethyl phosphite was kept at
120–130°C for 40 min to complete the active release
of ethyl chloride. The crystallized reaction mixture was
treated with hexane. Yield 1.10 g (98%), mp 162–163°C
5. Gross, H., Keitel, J., and Costisella, B., Phosph., Sulf.,
Silicon, Relat. Elem., 1991, vol. 62, p. 35.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 9 2012