Low-temperature oxidation of 3,6-di-tert-butyl-o-benzoquinone and 3,6-di-tert-butylpyrocatechol with tert-butyl hydroperoxide in the presence of aluminum, titanium, and zirconium tert-butylates

Article abstract of DOI:10.1134/S1070363206080202

Systems consisting of metal (Al, Ti, Zr) tert-butylate and tert-butyl hydroperoxide oxidize 3,6-di-tert-butyl-o-benzoquinone under mild conditions (room temperature, benzene). With (t-BuO)₃Al and (t-BuO) ₄Zr, the major reaction products are 5-hydroxy-3,6-di-tert-butyl-2,3- epoxy-p-benzoquinone, and with (t-BuO)₄Ti, 2-hydroxy-3,6-di-tert- butyl-p-benzoquinone. Under the conditions of this reaction, 3,6-di-tert-butylpyrocatechol initially transforms into 3,6-di-tert-butyl-o- benzoquinone. The reactions involve metalcontaining peroxides. Nauka/Interperiodica 2006.

Full text of DOI:10.1134/S1070363206080202

ISSN 1070-3632, Russian Journal of General Chemistry, 2006, Vol. 76, No. 8, pp. 1275 1281.
Pleiades Publishing, Inc., 2006.
Original Russian Text
pp. 1329 1336.
L.P. Stepovik, M.V. Gulenova, A.S. Shavyrin, G.K. Fukin, 2006, published in Zhurnal Obshchei Khimii, 2006, Vol. 76, No. 8,
Low-Temperature Oxidation of 3,6-Di-tert-butyl-o-benzoquinone
and 3,6-Di-tert-butylpyrocatechol with tert-Butyl Hydroperoxide
in the Presence of Aluminum, Titanium,
and Zirconium tert-Butylates
L. P. Stepovika, M. V. Gulenovaa, A. S. Shavyrinb, and G. K. Fukinb
a Lobachevsky Nizhni Novgorod State University,
pr. Gagarina 23, Nizhni Novgorod, 603950 Russia
e-mail: gulmv@rambler.ru
b Razuvaev Institute of Organometallic Chemistry,
Russian Academy of Sciences, Nizhni Novgorod, Russia
Received January 24, 2006
Abstract Systems consisting of metal (Al, Ti, Zr) tert-butylate and tert-butyl hydroperoxide oxidize 3,6-di-
tert-butyl-o-benzoquinone under mild conditions (room temperature, benzene). With (t-BuO)3Al and
(t-BuO)4Zr, the major reaction products are 5-hydroxy-3,6-di-tert-butyl-2,3-epoxy-p-benzoquinone, and with
(t-BuO)4Ti, 2-hydroxy-3,6-di-tert-butyl-p-benzoquinone. Under the conditions of this reaction, 3,6-di-tert-
butylpyrocatechol initially transforms into 3,6-di-tert-butyl-o-benzoquinone. The reactions involve metal-
containing peroxides.
DOI: 10.1134/S1070363206080202
The reactions of sterically hindered o-benzoqui-
nones and the corresponding pyrocatechols with per-
oxy derivatives (H2O2, peroxy acids, hydroperoxides)
yield various products depending on the nature of the
oxidant and reaction conditions. 3,5-Di-tert-butylpyro-
catechol and 4-tert-butylpyrocatechol are quantitative-
ly oxidized with tert-butyl hydroperoxide I in the
presence of catalytic amounts of RuCl2(PPh3)2 [1] to
the corresponding o-benzoquinones (20 C). 3,5-Di-
tert-butyl-o-benzoquinone is oxidized with an alkaline
solution of H2O2 in methanol to form products of
intradiol cleavage and ring opening [2]. The reaction
of this quinone with I in the presence of Triton B
catalyst gives 3,5-di-tert-butyl-5,6-epoxycyclohexene-
1,2-dione in 42% yield [3]. It should be noted that
epoxy quinones are of particular interest because of
their biological activity. They are widely used in
biology, pharmacology, and as key intermediates in
the synthesis of various organic compounds [4].
and III with I involves predominantly radical steps
resulting in the intermediate formation of o-semiqui-
none and tert-butylperoxy radical; their further reac-
tion yields the above products.
In this study we examined the reactions of quinone
II and pyrocatechol III with the oxidizing systems
t-BuOOH metal tert-butylate (metal: Al, IV; Ti, V;
Zr, VI). We showed previously that the reactions of
the components of the oxidizing systems consisting
of metal alcoholate IV [6], V [7], or VI [8] and
t-BuOOH (1 : 2, C6H6, 20 C) involve the formation
of metal-containing peroxides (t-BuO)n 1MOOBu-t
and trioxides (t-BuO)n 1MOOOBu-t. Decomposition
of the latter species is accompanied by the release of
oxygen and by homolysis with the generation of al-
koxy and peroxy radicals identified by ESR [6 8].
Systems consisting of I and IV VI are effective oxi-
dants of various classes of organic compounds (al-
kanes, alkylarenes, alkenes, alcohols, saturated and
unsaturated ethers and esters) [6 13]. Depending on
the structure of the substrate, the oxidizing species
can be oxygen generated by the systems, peroxides
(t-BuO)n 1MOOBu-t, or trioxides.
Glushakova et al. [5] reported that 3,6-di-tert-butyl-
o-benzoquinone II and 3,6-di-tert-butylpyrocatechol
III react with I at 70 and 90 C. They isolated a num-
ber of products; the major products were 3,6-di-tert-
butyl-1-oxacyclohepta-3,5-diene-2,7-dione (15 30%)
and 2-hydroxy-3,6-di-tert-butyl-p-benzoquinone (10
60%). Glushakova et al. believe that oxidation of II
The reactions of II and III with systems consisting
of I and IV VI were performed in benzene at 20 C
and component ratio of 1 : 2 : 1. Under these condi-
1275

1276
STEPOVIK et al.
Table 1. Products of the reaction of 3,6-di-tert-butyl-o-benzoquinone with the system M(OBu-t)n t-BuOOH, 1 : 1 : 2
(M = Al, n = 3; M = Ti, Zr, n = 4) in C6H6 at 20 C (moles per mole of the starting quinone)
Ti(OBu-t)4
Al(OBu-t)3
Zr(OBu-t)4
Reaction productsa
0 C
20 C
3.43
20 C
20 C
Volatile reaction products
3.59
t-BuOH
3.45
3.93
Products of hydrolysis of nonvolatile residueb
t-BuOH
2.27
0.65
Traces
2.44
0.74
Traces
0.20
1.59
0.05
0.95
2.10
0.15
0.63
0.13
2-Hydroxy-3,6-di-tert-butyl-p-benzoquinone
5-Hydroxy-3,6-di-tert-butyl-2,3-epoxy-p-benzoquinone
Unchanged 3,6-di-tert-butyl-p-benzoquinone
Not determined
a
b
Averaged results.
Metal amount 1 mol in all cases.
tions, compounds II and III react neither with perox-
ide I nor with metal alcoholates IV VI, taken sepa-
rately. Quinone II reacts with the oxidizing system
consisting of I and IV VI to form 2-hydroxy-3,6-di-
tert-butyl-p-benzoquinone VII and 5-hydroxy-3,6-di-
tert-butyl-2,3-epoxy-p-benzoquinone VIII (Table 1).
The yield of hydroxy quinone VII is maximal with
titanium alcoholate V, and epoxy quinone VIII is the
major product of the reactions involving zirconium
and especially aluminum alcoholates.
We believe that the first step of the reactions of
quinone II with the oxidizing systems consisting of I
and IV VI is the nucleophilic 1,4-addition of a metal-
containing peroxide or tert-butyl hydroperoxide to
the conjugated system involving one of the carbonyl
groups, followed by the reaction of the hydroxy group
with the metal alcoholate [scheme (1)].
(t-BuO)n 1MOOBu-t
O
OH
O
OM(OBu-t)n 1
O
t-BuOO
a
OM(OBu-t)n 1
H2O
O
O
(1)
H
or
t-BuOH
O
O
t-BuOOH, M(OBu-t)n
b
A
VII
M = Al, n = 3; M = Ti, Zr, n = 4.
Scheme (1) fully describeds the oxidation of II
with the system I V. However, with aluminum and
zirconium tert-butylates, alkoxy compounds A under-
go further oxidation, yielding previously unknown
5-hydroxy-3,6-di-tert-butyl-2,3-epoxy-p-benzoquinone
VIII. A single crystal X-ray diffraction study of VIII
(see figure) showed that the t-Bu groups are arranged
in the eclipsed conformation relative to each other.
The carbon ring C1 6 has a boat conformation. The
C3 and C6 atoms deviate from the C1C2C4C5 plane
by 0.172 and 0.355 , respecively. The dihedral angle
between the C1C2O1 and C1C2C4C5 planes is 89.2
(Table 2). The known related compounds have a simi-
lar conformation [14]. The C O and C C distances in
VIII are typical for compounds of this kind.
epoxidized with hydroperoxides in the presence of
aluminum and titanium alcoholates; this reaction is
a route to epoxy alcohols [15 17]. The process occurs
by the intramolecular mechanism via formation of
metal-containing peroxides. Zirconium complexes
containing the methyl and allyloxy ligands take up
oxygen with its insertion into the Zr CH3 bond and
formation of the peroxymethyl group, also capable of
intramolecular epoxidation [18].
It is well known that hydroxy-p-quinones and some
of their derivatives exist in solutions in a thermody-
namic equilibrium with the corresponding isomers of
o-quinones [19 21]. Similar transformations can be
suggested for compounds of type A. One of isomeri-
zation pathways is shown in scheme (2).
It is known that allyl-type alcohols are readily
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 8 2006

LOW-TEMPERATURE OXIDATION OF 3,6-DI-tert-BUTYL-o-BENZOQUINONE
1277
(2)
O
O
O
O
O
(t-BuO)nM
t-BuOH
O
t-BuOH
(t-BuO)nM
OM(OBu-t)n 1
OH
OH
O
OM(OBu-t)n 1
O
A
B
The subsequent reaction of compounds B with I
yields metal-containing peroxides whose decomposi-
tion is accompanied by epoxidation of the allylic
double bond [scheme (3)].
O
t-Bu
O
O
O
O
O
t-BuOOH
t-BuOH
B
(t-BuO)n 2MO
(t-BuO)n 2MO
O
(3)
C
O
O
H2O
O
O
O
M(OH)n, t-BuOH
OH
HO
O
VIII
M = Al, n = 3; M = Zr, n = 4.
The presence of quinones VII and VIII in the reac-
tion mixture in the form of alcoholates is confirmed
by the pH-chromism [20]. The red-brown color of the
solutions changes to yellow as a result of hydrolysis
with a 10% solution of sulfuric acid.
C9
C10
C8
Transformations described by schemes (2) and (3)
were actually observed in the reaction of VII with the
system I IV (1 : 1 : 1, C6H6, 20 C): epoxy quinone
VIII was isolated in a yield of 0.90 0.95 mol per
mole of VII. However, with titanium alcoholate V this
transformation was not observed. We assumed that
titanium derivative A does not isomerize [scheme (2)].
Indeed, the reaction of VII with Ti(OBu-t)4 yields
compound A with the release of 1 mol of t-BuOH.
However, the subsequent treatment of A (M = Ti)
with 1 mol of peroxide I resulted in the recovery of
0.85 mol of VII, and only 0.07 mol of VIII was ob-
tained.
C7
C2
O2
C3
C1
C6 O4
O1
O3
C4
C12
C5
C11
To prove the participation of metal-containing per-
oxides in the formation of compounds VII and VIII
[schemes (1), (3)], we performed model reactions of
an aluminum-containing peroxide (t-BuO)2AlOOBu-t
[22, 23] with quinones I and VII at an equimolar ratio
of the reactants (benzene, 20 C). The reaction of
(t-BuO)2AlOOBu-t with I yielded 0.26 mol of VIII
and 0.60 mol of VII, which confirms the initial forma-
C14
C13
Molecular structure of VIII.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 8 2006

1278
STEPOVIK et al.
Table 2. Selected geometric parameters of VIII: bond
lengths (d, ) and bond angles ( , deg)
dominantly the nucleophilic 1,4-addition of the metal-
containing peroxide to the conjugated system. With
the aluminum- and zirconium-containing peroxides,
this is followed by the epoxidation with the formation
of the hydroxy(epoxy) quinone.
Bond
d
Bond
d
O1 C1
O1 C2
C1 C6
C1 C2
O2 C3
C2 C3
1.424(7)
1.440(6)
1.479(8)
1.480(8)
1.216(6)
1.524(8)
O3 C4
C3 C4
O4 C6
C4 C5
C5 C6
1.355(6)
1.472(8)
1.228(6)
1.356(7)
1.472(8)
Oxidation of pyrocatechol III was studied with the
systems I IV and I V as examples (C6H6, 20 C). The
ratio pyrocatechol : metal alcoholate : hydroperoxide
was 1 : 1 : 2. In both cases quinone II was detected,
but its yield did not exceed 0.20 mol (here and herein-
after, per mole of III). The major fraction of II under-
goes further oxidation [schemes (1) (3)]; from the re-
actions, we isolated 0.76 mol of quinone VII with
Ti(OBu-t)4 and 0.55 mol of VII + 0.20 mol of epoxy
quinone VIII with Al(OBu-t)3.
Angle
Angle
C1O1C2
O1C1C2
62.2(4)
59.4(4)
O1C2C1
58.4(3)
Since the reactions of components of oxidizing sys-
tems are accompanied by the generation of alkoxy and
peroxy radicals [6, 8], the homolytic pathway of for-
mation of II seems also possible. However, we believe
that the direct reaction of the metal-containing per-
oxides with pyrocatechol III, yielding quinone II
[scheme (4)], is more probable.
tion of compound VII. Hydroxy quinone VII is epoxi-
dized with di-tert-butoxy-tert-butylperoxyaluminum.
The yield of VIII reaches 0.90 mol.
Thus, the first step of the reaction of quinone II
with the systems consisting of I and IV VI is pre-
(OBu-t)n 2
M
O
O
O
OH
+ (t-BuO)n 1MOOBu-t
t-BuOH
OH
H
O
O
+ t-BuOH + [(t-(BuO)n 2MO]n
(4)
O
Indeed, as major product of the reaction of III with
(t-BuO)2AlOOBu-t (1 : 1, 20 C) we isolated qui-
none II (0.74 mol). Also we detected quinone VII
(0.07 mol). The scheme involving a metal monoal-
koxy compound was suggested previously for the oxi-
dation of pyrocatechols to quinones with hydroperox-
ide I in the presence of ruthenium salts [1].
The GLC analysis of reaction products in the liquid
phase was performed with a Tsvet-2-65 chromato-
graph equipped with a flame-ionization detector; the
carrier gas was argon. Low-boiling components (tert-
butyl alcohol, tert-butyl hydroperoxide) were analyzed
on a 1200 3-mm column, stationary phase 15%
dinonyl phthalate on Chromaton N-AW-DMCS. The
column temperature was varied within 60 120 C. The
chromatographic analysis of 2-hydroxy-3,6-di-tert-
butyl-p-benzoquinone and 5-hydroxy-3,6-di-tert-butyl-
2,3-epoxy-p-benzoquinone was performed on a 1200
3-mm column, stationary phase 10% Reoplex-400 on
Inerton AW-HMDC, column temperature 130 150 C.
EXPERIMENTAL
The reaction products were analyzed by GLC,
1
TLC, H and 13C NMR, and IR spectroscopy. The IR
spectra were recorded on Specord-1000 and Bruker FS
IR-120 devices (liquid films between KBr windows).
The NMR spectra were measured in CDCl3 on a
Bruker Avance DPX-200 spectrometer.
The chromatograms were treated using authentic
samples as external references. All manipulations with
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 8 2006

LOW-TEMPERATURE OXIDATION OF 3,6-DI-tert-BUTYL-o-BENZOQUINONE
1279
metal-containing compounds were performed under
dry oxygen-free argon.
in the anisotropic approximation for all nonhydrogen
atoms. The hydrogen atoms were placed in idealized
positions and refined in the rider model. The correc-
tions for absorption were made using the SADABS
program [33].
The qualitative identification of the quinones and
their derivatives was performed by thin-layer chroma-
tography on Silufol UVC-254 plates in the system
petroleum ether ethyl acetate (22 : 1) or THF ethyl
acetate (5 : 1).
The structure was deposited at the Cambridge
Crystallographic Database, no. 263223.
In aqueous acid solutions from the hydrolysis, we
determined the content of t-BuOH [24] and of the
metal (precipitation of hydroxide followed by calcina-
tion to oxide).
Oxidation of 3,6-di-tert-butyl-o-benzoquinone
with the Al(OBu-t)3 t-BuOOH system (1 : 1 : 2).
To a dark green solution of 0.90 g of 3,6-di-tert-butyl-
o-benzoquinone in 15 ml of benzene, we added in
succession 1.02 g of (t-BuO)3Al and 0.75 g of
t-BuOOH. After mixing the components, the solution
became claret-colored. The solvent and low-boiling
components were condensed in a trap cooled with
liquid nitrogen. This fraction contained 1.05 g of tert-
butyl alcohol. The residue was a dark cherry-red
mobile mass; it was dissolved in diethyl ether and
treated with 10% H2SO4. The ether extract, according
to the chromatographic analysis, contained 0.48 g of
tert-butyl alcohol, 0.97 g of 5-hydroxy-3,6-di-tert-
butyl-2,3-epoxy-p-benzoquinone, and 0.05 g of 2-hy-
droxy-3,6-di-tert-butyl-p-benzoquinone. The presence
of epoxy compound VIII was confirmed by qualitative
reactions for oxirane ring: formation of a silver iodate
precipitate [34] and a color reaction with pyridine on
heating [35].
Aluminum tri-tert-butylate was prepared by the
reaction of Al with 2-methyl-2-propanol [25] and was
sublimed at 160 170 C (1 mm Hg). Found Al, %:
11.08. C12H27AlO3. Calculated Al, %: 10.98. Titani-
um tetra-tert-butylate was prepared by treatment of
TiCl4 with tert-butyl alcohol in the presence of NH3
[26], bp 82 83 C (2 mm Hg), n2D0 1.4420 [27]. Zirco-
nium tetra-tert-butylate was synthesized by the Sinor
company (Nizhni Novgorod); main substance content
99.9% {bp 70 C (2 mm Hg) [28]}.
Di-tert-butoxy-tert-butylperoxyaluminum was pre-
pared from di-tert-butoxyaluminum chloride and
t-BuOOH in the presence of diethylamine [22, 23].
The activity of the peroxide was no less than 96%.
The concentration of tert-butyl hydroperoxide used in
this study was no less than 99.6 99.8%.
To isolate compound VIII, the ether extract was
evaporated. The dry residue was dissolved in 3 ml of
ethanol, and the solution was diluted with 150 ml of
water. Within 5 6 h, lustrous pale yellow crystals
precipitated from the solution; mp 81 C. IR spectrum
2-Hydroxy-3,6-di-tert-butyl-p-benzoquinone was
prepared by treatment of 3,6-di-tert-butyl-4-methoxy-
o-benzoquinone with a 40% solution of HBr [29]; mp
84 C [5]. Compounds II and III were prepared by the
previously described procedures; their melting points
agree with published data [30, 31].
1
(perfluorinated oil), , cm : 3370, 3295, 3015, 2991,
2962, 2868, 1690, 1660, 1607, 1474, 1459, 1397,
1365, 1327, 1261, 1189, 1071, 1055, 946, 917, 799,
1
X-ray diffraction study of VIII. Single crystals of
C14H20O4 were prepared by crystallization from iso-
octane; the solvent was evaporated over a period of
several weeks. The experimental sets of intensities
were obtained with a Smart-APEX automatic diffrac-
tometer (graphite monochromator, MoK radiation,
scanning). Crystal data for VIII (C14H20O4) at
780, 728, 639, 617. H NMR spectrum (CDCl3), ,
ppm: 1.15, 1.32 s [9H, C(CH3)3], 3.79 s (1H, CH),
7.26 s (1H, OH). 13C NMR spectrum, DEPT (CDCl3),
C, ppm: 25.8, 29.2 [C(CH3)3], 32.0, 34.7 [C(CH3)3],
57.1 (C2H), 65.3 (C3), 128.5 (C6), 151.0 (C5), 190.4,
193.2 (C=O). Found, %: C 66.71; H 7.96. C14H20O4.
Calculated, %: C 66.64; H 7.99.
20 C: monoclinic system, a 9.655(6), b 7.134(5), c
3
Reaction of 3,6-di-tert-butyl-o-benzoquinone
with the Zr(OBu-t)4 t-BuOOH system, 1 : 1 : 2.
A mixture of 0.17 g of 3,6-di-tert-butyl-o-benzoqui-
none and 0.30 g of Zr(OBu-t)4 in 15 ml of benzene
was treated with 0.14 g of t-BuOOH. The reaction is
exothermic. The reaction solution was red-brown. The
condensate of low-boiling products contained 0.22 g
of t-BuOH. The residue, a dark cherry-red viscous
mass, was hydrolyzed in ether with 10% H2SO4 and
extracted with ether. The ether extract was yellow.
The presence of hydroxy quinones VII and VIII in
20.497(13)
;
100.725(11) , V 1387.2(15)
,
space group P21/c, Z 4, F(000) 544, 2.02
3
1
19.99 , dcalc 1.208 g cm , 0.088 mm . A total of
6057 unique reflections were measured, of which
1292 (Rint 0.12) were observed; the final divergence
factors were as follows: R1 0.0829 [I > 2 (I)], RW2
0.1562 (whole data set).
The structure was solved by the direct method
using the SHELXTL program package [32] and re-
fined by the least-squares method with respect to Fh2kl
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 8 2006

1280
STEPOVIK et al.
the ether extract was confirmed by the pH-chromism
[20]. On adding several drops of 0.5 N NaOH to an
aliquot of the ether solution, its color changed from
yellow to crimson-red, and on acidification with 0.5 N
H2SO4 it became yellow again.
ether extract revealed the presence of 0.37 g of 5-hy-
droxy-3,6-di-tert-butyl-2,3-epoxy-o-benzoquinone and
0.01 g of unchanged hydroxy quinone VII. The aque-
ous acid solution contained 0.08 g of t-BuOH.
Reaction of 3,6-di-tert-butylpyrocatechol with
the Ti(OBu-t)4 t-BuOOH system, 1 : 1 : 2. To a
mixture of 0.33 g of 3,6-di-tert-butylpyrocatechol and
0.51 g of Ti(OBu-t)4 in 10 ml of benzene, we added
0.27 g of t-BuOOH. On adding I, the emerald-green
solution became claret-colored. The reaction mixture
was allowed to stand at room temperature for 5 h. The
solvent and low-boiling substances were condensed
in a trap cooled with liquid nitrogen. The condensate
contained 0.50 g of t-BuOH.
The ether extract, according to the GLC analysis,
contained 0.03 g of 2-hydroxy-3,5-di-tert-butyl-p-ben-
zoquinone, 0.12 g of 5-hydroxy-3,6-di-tert-butyl-2,3-
epoxy-p-benzoquinone, and 0.10 g of t-BuOH. Qui-
nones II, VII, and VIII were separated by column
chromatography (adsorbent Silicagel 60, 0.060
0.020 mm, eluent petroleum ether diethyl ether, 22 :
1). The reaction progress was monitored by TLC. The
initial quinone was washed out from the adsorbent
successively with benzene and ethyl acetate; 0.022 g
of 3,6-di-tert-butyl-o-benzoquinone was recovered.
The samples of the isolated products, when mixed
with the authentic samples, show no depression of the
The residue was a dry claret-brown mass; it was
hydrolyzed as described above. Chromatographic
analysis of the ether extract revealed the presence of
0.08 g of t-BuOH and 0.26 g of 2-hydroxy-3,6-di-tert-
butyl-o-benzoquinone. By TLC we identified 3,6-di-
tert-butyl-o-benzoquinone and unchanged pyrocate-
chol (THF ethyl acetate, 9 : 1). To isolate pure VII,
the ether extract was evaporated. The dry residue was
dissolved in 3 ml of ethanol. On adding 100 ml of
water, bright yellow crystals of the hydroxy quinone
precipitated (0.20 g, 75%); mp 84 C [5]. No depres-
sion of the melting point was observed on mixing
with an authentic sample.
1
melting point. The H NMR spectrum of VII is iden-
tical to that given in [29].
The aqueous acid phase contained 0.02 g of t-BuO
groups, as determined by the Denigés method.
The reaction of II with the system I V and the
analysis of the reaction products were performed
similarly.
Reaction of 3,6-di-tert-butyl-o-benzoquinone
with (t-BuO)2AlOOBu-t, 1 : 1. To 1.21 g of di-tert-
butyl-tert-butylperoxyaluminum in 17 ml of benzene,
we added 0.91 g of 3.6-di-tert-butyl-o-benzoquinone.
The solution instantaneously turned wine-red, with
slight warming up. The low-boiling fraction contained
0.30 g of tert-butyl alcohol.
ACKNOWLEDGMENTS
The authors are grateful to N.O. Druzhkova for the
kindly submitted sample of 3,6-di-tert-butyl-o-benzo-
quinone.
The residue was a dark brown solid. The ether
extract after its hydrolysis contained 0.50 g of tert-
butyl alcohol, 0.65 g of 2-hydroxy-3,6-di-tert-butyl-
o-benzoquinone, and 0.30 g of 5-hydroxy-3,6-di-tert-
butyl-2,3-epoxy-o-benzoquinone. By TLC we identi-
fied unchanged 3,6-di-tert-butyl-o-benzoquinone. The
aqueous acid solution contained 0.20 g of t-BuOH
(determined as described previously).
The study was performed within the framework of
the Russian Federation President’s program for sup-
port of leading scientific schools (project no. NSh-
1652.2003.3).
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