Alkoxylation of 3,6-Di-tert-butyl-1,2-benzoquinone. New Bis-1,2-benzoquinones

Article abstract of DOI:10.1134/S1070428011040038

Alkoxylation of 3,6-di-tert-butyl-1,2-benzoquinone with a number of diols, including propane-1,3- diol, butane-1,4-diol, di-, and triethylene glycols, and cyclohexane-1,4-diyldimethanol, was studied. Nine new 4-alkoxy-3,6-di-tert- butyl-1,2-benzoquinones were synthesized, four of which were bis-1,2-benzoquinones with different tethers (6-13 atoms) between the quinone fragments. Depending on the length of the chain between the hydroxy groups in glycols, bicyclic 4,5-disubstituted 3,6-di-tert-butyl-1,2-benzoquinones were formed or their stepwise alkoxylation occurred. The newly synthesized o-benzoquinone derivatives can be reduced with alkali metals to give radical anions and converted into semiquinone chelates with manganese carbonyl. Pleiades Publishing, Ltd., 2011.

Full text of DOI:10.1134/S1070428011040038

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 4, pp. 486–495. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © M.P. Shurygina, N.O. Druzhkov, M.V. Arsen’ev, M.P. Bubnov, G.K. Fukin, S.A. Chesnokov, V.K. Cherkasov, 2011, published in
Zhurnal Organicheskoi Khimii, 2011, Vol. 47, No. 4, pp. 490–498.
Alkoxylation of 3,6-Di-tert-butyl-1,2-benzoquinone.
New Bis-1,2-benzoquinones
M. P. Shurygina, N. O. Druzhkov, M. V. Arsen’ev, M. P. Bubnov, G. K. Fukin,
S. A. Chesnokov, and V. K. Cherkasov
Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences,
ul. Tropinina 49, Nizhnii Novgorod, 603950 Russia
e-mail: sch@iomc.ras.ru
Received July 13, 2010
Abstract—Alkoxylation of 3,6-di-tert-butyl-1,2-benzoquinone with a number of diols, including propane-1,3-
diol, butane-1,4-diol, di-, and triethylene glycols, and cyclohexane-1,4-diyldimethanol, was studied. Nine new
4-alkoxy-3,6-di-tert-butyl-1,2-benzoquinones were synthesized, four of which were bis-1,2-benzoquinones
with different tethers (6–13 atoms) between the quinone fragments. Depending on the length of the chain
between the hydroxy groups in glycols, bicyclic 4,5-disubstituted 3,6-di-tert-butyl-1,2-benzoquinones were
formed or their stepwise alkoxylation occurred. The newly synthesized o-benzoquinone derivatives can be
reduced with alkali metals to give radical anions and converted into semiquinone chelates with manganese
carbonyl.
DOI: 10.1134/S1070428011040038
Interest in sterically hindered o-benzoquinones is
determined by their wide application as precursors in
the synthesis of organometallic compounds [1]. 3,6-Di-
tert-butyl-1,2-benzoquinone (I) and its derivatives are
capable of undergoing one- and two-electron reduction
with formation of o-semiquinone radical anion and
pyrocatechol dianion [2]. These species are observed
in coordination compounds with metals, depending on
the ratio of the redox parameters of o-quinone and
metal. Functionalization of o-benzoquinone with a view
to vary their redox properties can be performed in
several ways. Like most conjugated unsaturated
ketones, the most typical reaction of 3,6-di-tert-butyl-
1,2-benzoquinone is nucleophilic 1,4-addition [3].
Various reagents may be used as nucleophiles: organo-
metallic compounds [4], alcohols [5], primary and
secondary amines [6, 7], CH acids [8, 9]. New steri-
cally hindered o-benzoquinones can be synthesized via
nucleophilic replacement from 4-substituted 3,6-di-
tert-butyl-1,2-benzoquinones. For example, fluoro
[10], sulfur-containing [11], and alkoxy derivatives [5]
of 3,6-di-tert-butyl-1,2-benzoquinone were obtained in
such a way. In the recent time, polyfunctional o-benzo-
quinones, including bis-o-benzoquinones, attract spe-
cific interest. Up to now, only a few examples of
sterically hindered bis-o-benzoquinones have been
reported; the quinone fragments therein were linked
either directly [12] or through an ethylene [4], ethene
[13], piperidine [7], and m-phenylene bridges [14]. The
goal of the present work was to synthesize new
alkoxy-substituted bis-o-benzoquinones with different
lengths of the bridge between the quinone fragments.
3,6-Di-tert-butyl-1,2-benzoquinone reacted with
primary alcohols according to the nucleophilic 1,4-ad-
Scheme 1.
Bu-t
Bu-t
Bu-t
Bu-t
Bu-t
O
O
OH
OH
O
O
OH
OH
I
KOH, MeCN
+
ROH
+
RO
RO
Bu-t
Bu-t
Bu-t
I
II
486

ALKOXYLATION OF 3,6-DI-tert-BUTYL-1,2-BENZOQUINONE.
487
Scheme 2.
Bu-t
Bu-t
Bu-t
Bu-t
Bu-t
Bu-t
O
O
O
O
O
O
O
O
I or III
KOH, MeCN
+
HO
Z
OH
Z
Z
X
HO
O
O
O
Bu-t
Bu-t
I, III
IVa–VIIIa
Vb–VIIIb
I, X = H; III, X = MeO; IV, Z = (CH2)3; V, Z = (CH2)4; VI, Z = CH2CH2OCH2CH2; VII, Z = CH2(CH2OCH2)2CH2;
VIII, Z =
.
Scheme 3.
OH
Bu-t
Bu-t
Bu-t
O
O
O
O
O
O
OH
OH
O
O
KOH, MeCN
[O]
O
Bu-t
Bu-t
Bu-t
IVa
IX
dition pattern with participation of the carbonyl group
(Scheme 1) [5]. As in reactions of 3,6-di-tert-butyl-1,2-
benzoquinone with other nucleophiles described previ-
ously [7], in all cases 3,6-di-tert-butylbenzene-1,2-diol
(II) was formed in ~50% yield calculated on the initial
compound I. Presumably, the primary addition prod-
uct, the corresponding 4-alkoxy-3,6-di-tert-butylben-
zene-1,2-diol, is oxidized with the initial quinone.
Alkoxylation of o-benzoquinones can also follow nu-
cleophilic replacement mechanism, as in the reaction
with 3,6-di-tert-butyl-4-methoxy-1,2-benzoquinone
(III). This reaction seems to be more advantageous
than nucleophilic 1,4-addition due to high rate, eco-
nomic consumption of o-benzoquinone, and the
absence of additional pyrocatechol oxidation step
(correspondingly, no pyrocatechol II is formed as by-
product).
butyl-4-(4-hydroxybutoxy)-1,2-benzoquinone (Va),
3,6-di-tert-butyl-4-hydroxy-5-[2-(2-hydroxyethoxy)-
ethoxy]-1,2-benzoquinone (VIa), 3,6-di-tert-butyl-4-
hydroxy-5-{2-[2-(2-hydroxyethoxy)ethoxy]ethoxy}-
1,2-benzoquinone (VIIa), and 3,6-di-tert-butyl-4-{[4-
(hydroxymethyl)cyclohexyl]methoxy}-1,2-benzoqui-
O2
O3
C3
C4
C2
C1
In this work we used as nucleophiles a number of
glycols: propane-1,3-diol, butane-1,4-diol, diethylene
and triethylene glycols, and cyclohexane-1,4-diyldi-
methanol. Taking into account that these diols possess
two independent reaction centers, their reaction with
3,6-di-tert-butyl-1,2-benzoquinone was expected to
produce mono- and bis-o-benzoquinones IVa–VIIIa
and Vb–VIIIb, depending on the reactant ratio
(Scheme 2). In the first step the reaction of o-benzo-
quinone with glycols gives 4-alkoxy-3,6-di-tert-butyl-
1,2-benzoquinones, namely 3,6-di-tert-butyl-4-(3-hy-
droxypropoxy)-1,2-benzoquinone (IVa), 3,6-di-tert-
O1
C5
O4
C6
Fig. 1. Structure of the molecule of 6,9-di-tert-butyl-3,4-di-
hydro-2H-1,5-benzodioxepine-7,8-dione (IX) according to
the X-ray diffraction data.
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SHURYGINA et al.
488
Table 1. Selected bond lengths in the molecules of
4,4′-[2,2′-oxybis(ethane-2,1-diyl)bis(oxy)]bis(3,6-di-tert-
butylcyclohexa-3,5-diene-1,2-dione) (VIb), 4,4′-{2,2′-
[ethane-1,2-diylbis(oxy)]bis(ethane-2,1-diyl)bis(oxy)}bis-
(3,6-di-tert-butylcyclohexa-3,5-diene-1,2-dione) (VIIb), and
6,9-di-tert-butyl-3,4-dihydro-2H-1,5-benzodioxepine-7,8-
dione (IX)
(Scheme 3). The structure of quinone IX was proved
by X-ray analysis (Fig. 1, Table 1). According to the
X-ray diffraction data, the O(CH2)3O fragment in
molecules IX in crystal is disordered. The principal
geometric parameters of molecule IX are typical of
such compounds, but the C=O bond lengths differ
from each other [1.207(2) and 1.216(2) Å]. The
O1C1C2O2 fragment is not planar, and the correspond-
ing torsion angle is equal to 30.6°.
Bond
d, Å
Bond
d, Å
Compound VIb
Prokof’eva at al. [15] previously studied the reac-
tion of 3,6-di-tert-butyl-1,2-benzoquinone with ethyl-
ene glycol and observed formation of only bicyclic
4,5-disubstituted product, 5,8-di-tert-butyl-2,3-dihy-
dro-1,4-benzodioxine-6,7-dione. Increase of the length
of the hydrocarbon chain in glycol to four carbon
atoms and more hampers intramolecular ring closure.
O1A–C1A
O2A–C2A
O1–C1
O1–C4A
O1B–C1B
O2B–C2B
O2–C2
O2–C3
O3–C4
O3–C4B
C1B–C6B
1.214(2)
1.220(2)
1.450(2)
1.355(2)
1.211(2)
1.224(2)
1.423(2)
1.417(3)
1.494(3)
1.351(2)
1.478(3)
C1A–C2A
C2A–C3A
C3A–C4A
C4A–C5A
C5A–C6A
C1A–C6A
C1B–C2B
C2B–C3B
C3B–C4B
C4B–C5B
C5B–C6B
1.548(2)
1.457(2)
1.353(2)
1.510(3)
1.342(3)
1.459(3)
1.548(3)
1.457(3)
1.360(3)
1.476(3)
1.342(3)
4-Substituted 3,6-di-tert-butyl-1,2-benzoquinones
Va–VIIIa possess a side-chain hydroxy group which
can be involved in further transformations. Therefore,
quinones Va–VIIIa were used as substrates in the
second functionalization step to obtain bis-o-benzo-
quinones (Scheme 2). By carrying out alkoxylation
with two- (nucleophilic substitution in III) or fourfold
(nucleophilic 1,4-addition to compound I) excess of
initial o-quinone I or III with respect to glycol we
isolated four new bis-o-benzoquinones: 4,4′-[butane-
1,4-diylbis(oxy)]bis(3,6-di-tert-butyl-1,2-benzoqui-
none) (Vb), 4,4′-[2,2′-oxybis(ethane-2,1-diyl)bis(oxy)]-
bis(3,6-di-tert-butyl-1,2-benzoquinone) (VIb),
4,4′-{2,2′-[ethane-1,2-diylbis(oxy)]bis(ethane-2,1-di-
yl)bis(oxy)}bis(3,6-di-tert-butyl-1,2-benzoquinone)
(VIIb), and 4-{[4-(2,5-di-tert-butyl-3,4-dioxocyclo-
hexa-1,5-dien-1-yloxy)cyclohexyl]methoxy}-3,6-di-
tert-butyl-1,2-benzoquinone (VIIIb). All new o-qui-
nones were characterized by elemental analyses and IR
Compound VIIba
O1A–C1A
O2A–C2A
O1–C1
O1–C4A
O2–C2
O2–C3
1.213(2)
1.224(2)
1.444(2)
1.352(2)
1.417(2)
1.416(2)
C1A–C2A
C2A–C3A
C3A–C4A
C4A–C5A
C5A–C6A
C1A–C6A
1.552(3)
1.454(3)
1.360(3)
1.473(3)
1.338(3)
1.475(3)
Compound IX
O1–C1
O2–C2
O3–C4
O3–C15
O4–C5
O4–C17
1.207(2)
1.216(2)
1.397(2)
1.433(3)
1.382(3)
1.407(3)
C1–C2
C2–C3
C3–C4
C4–C5
C5–C6
C1–C6
1.548(2)
1.457(2)
1.353(2)
1.510(3)
1.342(3)
1.459(3)
1
and H and 13C NMR spectra. The IR spectra of all
compounds contained a number of characteristic ab-
sorption bands [16], in particular a strong narrow band
typical of carbonyl group (1680 cm–1) and a band
belonging to ether C–O–C bond (1250 cm–1). Com-
pounds Va–VIIIa displayed a broadened band at
3300 cm–1 due to stretching vibrations of the hydroxy
group. The 1H NMR spectra of the isolated compounds
were very similar: protons in the tert-butyl groups
resonated as two singlets at δ 1.2–1.4 ppm, the OCH2
groups gave multiplet signals in the region δ 3.80–
4.20 ppm, and the 5-H signal appeared as a singlet at
δ 6.82–6.85 ppm. The structure of compounds VIb and
VIIb was proved by X-ray analysis (Figs. 2, 3;
Table 1). The OCCO fragments in molecules VIb and
VIIb are nonplanar with the torsion angles equal to
a
Molecule occupies the inversion center.
none (VIIIa). 4-Alkoxy-o-benzoquinones IVa–VIIIa
were formed in high yield (~80%) when the reaction
was carried out in excess diol. Compounds Va–VIIIa
were isolated as individual substances and character-
ized by spectral methods (see Experimental). In the
reaction of o-benzoquinone I with propan-1,3-diol
compound IVa was detected only by TLC. Presum-
ably, it rapidly underwent intramolecular cyclization to
6,9-di-tert-butyl-3,4-dihydro-2H-1,5-benzodioxepine-
7,8-dione (IX) which was isolated as the only product
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 4 2011

ALKOXYLATION OF 3,6-DI-tert-BUTYL-1,2-BENZOQUINONE.
489
Scheme 4.
Bu-t
Bu-t
Bu-t
Bu-t
O
O
O
O
O
HO–
(1)
–RO–
RO
HO
O
OH
Bu-t
Bu-t
Bu-t
Bu-t
Bu-t
Bu-t
6
12
O
OH
11
1
O
O
KOH, MeCN, Δ
5
4
+
7
10
O
(2)
(3)
2
9
O
OH
OH
8
3
t-Bu
OH
Bu-t
Bu-t
Bu-t
X
Bu-t
Bu-t
O
O
O
O
O
KOH
HO
O
O
m
Bu-t
Bu-t
VIa, VIIa
m = 2, 3.
30.8° (34.0°) and 6.7° (6.7°), respectively. The tethers
connecting the quinone fragments are packed differ-
ently. The OCH2CH2OCH2CH2O fragment in molecule
VIb is bent in such a way that the quinone fragments
are arranged one above the other with a distance of
5.864 Å between them. The triethylene glycol frag-
ment OCH2CH2OCH2CH2OCH2CH2O in compound
VIIb is almost linear. Obviously, different conforma-
tions of the polyether fragments VIb and VIIb are
related to specificity of their crystal packing.
analysis. o-Benzoquinones VIa and VIIa underwent
one more transformation [Scheme 4, reaction (3)].
Their alkaline hydrolysis leads to the formation of not
O1
C2A
O1A
C1
O2A
C2
C1A
The yields of bis-o-benzoquinones did not exceed
30%. It was found previously [17] that 3,6-di-tert-
butyl-4-methoxy-1,2-benzoquinone undergoes hydrol-
ysis with formation of 3,6-di-tert-butyl-2-hydroxy-1,4-
benzoquinone. Probably, 4-alkoxy-1,2-benzoquinones
are also hydrolyzed during the process. We have
revealed several side reactions which impair the yield
of the target products (Scheme 4). Alkoxylation in al-
kaline medium is accompanied by hydrolysis of o-ben-
zoquinones Va–VIIIa to hydroxy-p-benzoquinone in
up to 50% yield [Scheme 4, reaction (1)]. 3,6-Di-tert-
butyl-2-hydroxy-1,4-benzoquinone reacts with 3,6-di-
tert-butylbenzene-1,2-diol to give 2′,4,5′,7-tetra-tert-
butyl-3′-hydroxyspiro[1,3-benzodioxole-2,1′-cyclo-
hexa[2,5]dien]-4′-one (X); we specially synthesized
the latter by reaction (2) (Scheme 4). Compound X
was isolated as individual substance, and its structure
was confirmed by NMR and IR spectra and elemental
O3
C4
C5
O6
C2B
O2B
O1B
C1B
Fig. 2. Structure of the molecule of 4,4′-[2,2′-oxybis(ethane-
2,1-diyl)bis(oxy)]bis(3,6-di-tert-butylcyclohexa-3,5-diene-
1,2-dione) (VIb) according to the X-ray diffraction data.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 4 2011

SHURYGINA et al.
490
O2AA
initially, and then blue color due to o-semiquinone ap-
O1AA
C1AA
C2AA
peared. The ESR spectra of potassium complexes with
radical anions derived from Vb–VIIb, VIIIa, and
VIIIb were similar; they displayed doublets of triplets
due to hyperfine coupling of the unpaired electron with
proton in position 5 of the pseudoaromatic o-semi-
quinone ring (hyperfine coupling constant 0.35–
0.37 mT) and two protons in the α-CH2 group (HCC
0.02–0.03 mT (Scheme 5, Fig. 4). Both HCC values
are typical of such compounds [5]. The ESR spectral
parameters are given in Table 2.
O1B
C1B
O2B
C3
C2
O1
C2B
C1
C3B
O2
Scheme 5.
Bu-t
Bu-t
C2A
O
O
O
C1A
O1A
K, THF
K+
·
–
O2A
R'
O
R'
O
O
Fig. 3. Structure of the molecule of 4,4′-{2,2′-[ethane-1,2-
diylbis(oxy)]bis(ethane-2,1-diyl)bis(oxy)}bis(3,6-di-tert-
butylcyclohexa-3,5-diene-1,2-dione) (VIIb) according to the
X-ray diffraction data.
Bu-t
Bu-t
Irradiation of toluene solutions of o-quinones Vb,
VIb, VIIIa, and VIIIb with visible light in the pres-
ence of Mn2(CO)10 resulted in the formation of para-
magnetic manganese chelate complexes (Scheme 6,
Fig. 5). The ESR spectra of o-semiquinone tetracar-
bonyl manganese chelates are sextets of doublets of
triplets due to hyperfine coupling of the unpaired
electron with magnetically active manganese isotope
(55Mn, I = 5/2, 100%), proton in position 5 of the
semiquinone ring, and two protons in the side-chain
α-methylene group. As follows from the data in
Tables 2 and 3, the g-factors and HCCs for the ex-
amined radical anion adducts of o-quinones are similar
to each other and are comparable to those reported for
structurally related compounds [5].
only monohydroxy-p-benzoquinone but also bicyclic
product described previously [15] in up to 30% yield.
The contribution of reactions (1)–(3) becomes appre-
ciable due to considerably increased reaction time
(equimolar amounts of the reactants) as compared to
the first functionalization step.
o-Quinones can be reduced to radical anions via
addition of one electron. With a view to determine spin
density distribution in radical anions derived from
the newly synthesized o-quinones, the corresponding
potassium and tetracarbonylmanganese complexes
were obtained and their ESR spectra were recorded.
These metals were selected taking into account speci-
ficity of their coordination properties. It is known that
potassium usually gives rise to solvent-separated ion
pair [18] and that manganese typically forms chelate
structures [19]. In the reaction of compound VIIIa
with potassium evolution of hydrogen was observed
The ESR spectra of complexes formed by radical
anion of IX showed a different pattern. The spectrum
of the potassium complex at room temperature is satis-
factorily simulated as a triplet of triplets with HCCs of
0.046 and 0.022 mT (due to interactions with pairwise
equivalent protons in the α-CH2 groups). However,
both reduction and rise in temperature changed the
spectral pattern, depending on the solvent (Fig. 6).
This may be the result of two independent processes:
association on cooling which is related to transforma-
tion of solvent-separated ion pairs into contact and
“defrosting” of hindered molecular motions on heat-
ing. The formation of contact ion pairs follows from
the appearance of additional hyperfine structure on
cooling to 230–250 K in diethyl ether. Furthermore, in
this solvent we observed monotonic increase of the
g-factor from 2.0051 at 290 K to 2.0054 at 230 K,
1
2
2.0106
2.0083
2.0059
2.0036
2.0013
g-Factor
Fig. 4. (1) Experimental and (2) simulated ESR spectra of
radical anion derived from bis-o-benzoquinone Vb.
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ALKOXYLATION OF 3,6-DI-tert-BUTYL-1,2-BENZOQUINONE.
491
Scheme 6.
Bu-t
Bu-t
O
O
O
·
–
Mn2(CO)10, PhMe, hν
Mn(CO)4
O
R'
O
R'
O
Bu-t
Bu-t
which corresponds to increase of the contribution of
heteroatom (oxygen) orbitals to the unpaired electron
orbital due to approach of positively charged species
(K+). No analogous pattern was observed in tetrahy-
drofuran which is characterized by stronger solvating
power.
were recorded on FSM-1201 (Russia) and Specord
M-40 spectrometers. The solvents used were purified
and dehydrated by standard methods [20]. 3,6-Di-tert-
butyl-1,2-benzoquinone and 3,6-di-tert-butyl-4-me-
thoxy-1,2-benzoquinone were synthesized according to
the procedures described in [5, 21]. Propane-1,3-diol,
butane-1,4-diol, diethylene and triethylene glycols,
and cyclohexane-1,4-diyldimethanol were commercial
products (Fluka).
The presence of a seven-membered ring in mole-
cule IX implies the existence of different conformers
and their interconversions. Figure 7 shows three pos-
sible conformers of IX together with the corresponding
enantiomers. The most energetically favorable con-
former is A, next follows conformer B, and structure C
is the least stable. Molecular modeling (HyperChem
7.01) gave the following energies (arbitrary units):
26.59 (A), 29.77 (B), and 31.21 (C). Variation of tem-
perature should change the relative contributions of
these conformers. In addition, variation of temperature
is accompanied by change of the rate of their intercon-
versions; therefore, it is difficult to unambiguously
interpret the observed variations in the ESR spectra.
1
2
2.0190
2.0131
2.0072
2.0014
1.9956
g-Factor
Fig. 5. (1) Experimental and (2) simulated ESR spectra of
tetracarbonylmanganese chelate with radical anion derived
from o-benzoquinone VIIIa.
To conclude, we have synthesized nine new 4-alk-
oxy-3,6-di-tert-butyl-1,2-benzoquinone derivatives.
Among these, four compounds are bis-o-benzoqui-
nones with different lengths of the tether (6–13 atoms)
connecting the quinone fragments. Depending on the
length of the chain between the hydroxy groups in
glycols, their reactions with 3,6-di-tert-butyl-1,2-ben-
zoquinones lead to the formation of bicyclic 4,5-disub-
stituted 3,6-di-tert-butyl-1,2-benzoquinones or involve
stepwise alkoxylation. The newly synthesized o-benzo-
quinone derivatives are capable of being converted
into radical anions via reduction with alkali metals and
forming o-semiquinone chelates with transition metals.
1
2
3
EXPERIMENTAL
1
The H and 13C NMR spectra were recorded on
a Bruker Avance DPX-200 spectrometer at 200 and
50 MHz, respectively, using CDCl3 as solvent and
tetramethylsilane as internal reference. The ESR spec-
tra were measured on a Bruker ER 200D-SRC spec-
trometer equipped with an ER 4105 DR double reso-
nator (operating frequency 9.5 GHz). The IR spectra
2.0063
2.0057
2.0051
g-Factor
2.0045
2.0039
Fig. 6. ESR spectra of potassium complex with radical anion
IX at (1) 290 K (THF), (2) 210 K (Et2O), and (3) 350 K
(2-methyltetrahydrofuran).
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SHURYGINA et al.
492
Table 2. Parameters of the ESR spectra of radical anions
derived from quinones Vb–VIIb, VIIIa, and VIIIb (THF,
290 K)
acetate (20:1 to 1:1) as eluent; a dark red fraction was
collected.
3,6-Di-tert-butyl-4-(4-hydroxybutoxy)cyclohexa-
3,5-diene-1,2-dione (Va). Yield 2.50 g (81%), dark red
oily substance. IR spectrum (mineral oil), ν, cm–1:
3450, 1685, 1640, 1625, 1550, 1485, 1460, 1395,
1380, 1360, 1300, 1240, 1200, 1080, 945, 890, 830,
Parameter
gi
Vb
VIb
VIIb VIIIb VIIIa
02.0056 02.0052 02.0055 02.0055 02.0057
0.362 0.359 0.367 0.367 0.366
0.024 0.025 0.026 0.026 0.029
ai(1H), mT
ai(2H), mT
1
735, 682, 640, 600. H NMR spectrum, δ, ppm: 1.24 s
and 1.32 s (9H each, t-Bu), 1.71–1.81 m (2H, CH2),
1.85–1.96 m (2H, CH2), 3.71–3.79 m (2H, CH2O),
4.13 t (2H, CH2O, J = 6.2 Hz), 6.85 s (1H, 5-H).
13C NMR spectrum, δC, ppm: 28.96 and 30.54 (CH3),
35.09 and 35.16 (CMe3), 62.32 and 69.46 (CH2O),
129.74 (C3), 130.05 (C5), 149.53 (C6), 162.71 (C4),
181.62 and 182.23 (C=O). Found, %: C 70.02; H 9.07.
C18H28O4. Calculated, %: C 70.13; H 9.09.
Table 3. Parameters of the ESR spectra of the complexes
formed by quinones Vb, VIb, VIIIa, and VIIIb with do-
decacarbonyldimanganese in toluene at 290 K
Parameter
gi
Vb
VIb
VIIIa
VIIIb
02.0034 02.0033 02.0034 02.0035
ai(1H), mT
ai(2H), mT
ai(Mn), mT
0.363
0.054
0.644
0.363
0.051
0.646
0.362
0.058
0.622
0.361
0.058
0.623
3,6-Di-tert-butyl-4-hydroxy-5-[2-(2-hydroxy-
ethoxy)ethoxy]cyclohexa-3,5-diene-1,2-dione (VIa).
Yield 2.49 g (77%), dark red oily substance. IR spec-
trum (mineral oil), ν, cm–1: 3450, 1750, 1690, 1650,
1635, 1560, 1490, 1465, 1400, 1390, 1360, 1300,
1250, 1200, 1160, 1140, 1075, 1030, 1000, 970, 920,
o-Quinones Va–VIIIa and IX (general procedure).
A mixture of 50 ml of acetonitrile, 2.2 g (10 mmol) of
compound I or 1 g (4 mmol) of III, 5 ml (50 mmol) of
the corresponding diol, and solid potassium hydroxide
was slightly heated for 5–15 h under stirring using
a magnetic stirrer. The progress of the reaction was
monitored by TLC. As compound I was consumed,
PbO2 was added to the mixture. When the reaction was
complete, the mixture was filtered, washed with
an aqueous solution of sodium carbonate and water,
and extracted with diethyl ether. The extract was evap-
orated, and the products were isolated by chromatog-
raphy on silica gel (0.2–0.5 mm) using benzene–ethyl
1
890, 855, 740. H NMR spectrum, δ, ppm: 1.24 s and
1.32 s (9H each, t-Bu), 1.71–1.81 m (2H, CH2), 1.85–
1.96 m (2H, CH2), 3.71–3.79 m (2H, CH2O), 4.09–
13
4.16 m (2H, CH2O), 6.91 s (1H, 5-H). C NMR spec-
trum, δC, ppm: 28.95 and 30.48 (CH3), 35.17 (CMe3);
61.81, 68.64, 69.59, and 72.62 (CH2O); 129.74,
130.05, 149.53, and 162.71 (C3, C5, C6, C4); 181.62
and 182.23 (C=O). Found, %: C 66.60; H 8.62.
C18H28O5. Calculated, %: C 66.67; H 8.64.
3,6-Di-tert-butyl-4-hydroxy-5-{2-[2-(2-hydroxy-
ethoxy)ethoxy]ethoxy}cyclohexa-3,5-diene-1,2-di-
one (VIIa). Yield 2.58 g (70%), dark red oily sub-
stance. IR spectrum (mineral oil), ν, cm–1: 3450, 1690,
1650, 1635, 1555, 1490, 1470, 1405, 1390, 1365,
1310, 1250, 1205, 1135, 1085, 1040, 1005, 940, 925,
A
B
1
895, 860, 840, 740. H NMR spectrum, δ, ppm: 1.24 s
and 1.32 s (9H each, t-Bu), 1.71–1.81 m (2H, CH2),
1.85–1.96 m (2H, CH2), 3.71–3.79 m (2H, CH2O),
13
4.09–4.16 m (2H, CH2O), 6.92 s (1H, 5-H). C NMR
spectrum, δC, ppm: 28.95 and 30.48 (CH3), 35.16
(CMe3); 61.81, 68.64, 69.46, and 72.62 (CH2O);
130.50, 130.93, 149.54, and 162.55 (C3, C5, C6, C4);
181.48 and 182.38 (C=O). Found, %: C 65.23; H 8.70.
C20H32O6. Calculated, %: C 65.21; H 8.69.
3,6-Di-tert-butyl-4-{[4-(hydroxymethyl)cyclo-
hexyl]methoxy}cyclohexa-3,5-diene-1,2-dione
(VIIIa). Yield 2.49 g (68%), dark red powder,
mp 141–143°C. IR spectrum (mineral oil), ν, cm–1:
C
Fig. 7. Enantiomer pairs of radical anion IX (tert-butyl
groups are not shown for the sake of simplicity).
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ALKOXYLATION OF 3,6-DI-tert-BUTYL-1,2-BENZOQUINONE.
493
3315, 1682, 1640, 1638, 1550, 1460, 1400, 1390,
1370, 1302, 1240, 1200, 1084, 1037, 954, 897, 884,
826. H NMR spectrum, δ, ppm: 0.98–1.16 m (4H,
1250, 1235, 1200, 1160, 1140, 1130, 1090, 1075, 1040,
1010, 940, 920, 905, 860, 835, 740. H NMR spec-
1
1
trum, δ, ppm: 1.21 s and 1.32 s (18H each, t-Bu), 3.83–
3.90 m (4H, CH2), 4.18–4.25 m (4H, CH2O), 6.87 s
(2H, 5-H). 13C NMR spectrum, δC, ppm: 28.97 and
30.53 (CH3), 35.19 (CMe3), 68.53 and 69.88 (CH2O);
130.59, 130.72, 149.66, and 162.29 (C3, C5, C6, C4);
181.41 and 182.37 (C=O). Found, %: C 70.79; H 8.48.
C32H46O7. Calculated, %: C 70.84; H 8.49.
CH2), 1.24 s and 1.31 s (9H each, t-Bu), 1.50–1.80 m
(2H, CH), 1.84–2.00 m (4H, CH2), 3.50 d (2H,
CH2OH, J = 6.1 Hz), 3.88 d (2H, CH2O, J = 6.2 Hz),
6.83 s (1H, 5-H). 13C NMR spectrum, δC, ppm: 29.1
and 30.7 (CH3), 28.8 and 29.3 (CH2), 35.2 and 35.3
(CMe3), 38.4 and 40.4 (CH), 68.5 and 75.1 (CH2O);
129.7, 130.4, and 149.5 (C3, C5, C6); 163.1 (C4), 181.7
and 182.3 (C=O). Found, %: C 72.90; H 9.38.
C22H34O4. Calculated, %: C 72.93; H 9.39.
4,4′-{2,2′-[Ethane-1,2-diylbis(oxy)]bis(ethane-
2,1-diyl)bis(oxy)}bis(3,6-di-tert-butylcyclohexa-3,5-
diene-1,2-dione (VIIb). Yield 0.59 g (20%), dark red
crystals, mp 113–115°C. IR spectrum (mineral oil), ν,
cm–1: 1690, 1645, 1630, 1550, 1490, 1460, 1425, 1405,
1385, 1360, 1330, 1310, 1255, 1245, 1200, 1150, 1115,
1090, 1050, 1040, 1010, 925, 905, 875, 860, 740, 725.
1H NMR spectrum, δ, ppm: 1.21 s and 1.32 s (18H
each, t-Bu), 3.67 s (4H, CH2), 3.76–3.82 m (4H,
CH2O), 4.17–4.24 m (4H, CH2O), 6.87 s (2H, 5-H).
13C NMR spectrum, δC, ppm: 28.98 and 30.53 (CH3),
35.16 (CMe3); 68.62, 69.81, and 70.86 (CH2O);
130.32, 131.06, 149.40, and 162.62 (C3, C5, C6, C4);
181.53 and 182.38 (C=O). Found, %: C 69.60; H 8.50.
C34H50O8. Calculated, %: C 69.62; H 8.53.
6,9-Di-tert-butyl-3,4-dihydro-2H-1,5-benzodiox-
epine-7,8-dione (IX). Yield 2 g (68%), red crystals,
mp 148–150°C. IR spectrum (mineral oil), ν, cm–1:
1660, 1645, 1585, 1540, 1460, 1395, 1375, 1365,
1320, 1295, 1255, 1240, 1200, 1165, 1115, 1070, 1020,
995, 950, 930, 883, 870, 855, 825, 815, 781, 720, 660,
1
650, 630. H NMR spectrum, δ, ppm: 1.30 s (18H,
t-Bu), 2.22 quint (2H, CH2, J = 5.77 Hz), 4.25 t (4H,
CH2O, J = 5.77 Hz). 13C NMR spectrum, δC, ppm:
29.52 (CH3), 30.52 (CH2), 35.55 (CMe3), 70.07
(CH2O), 132.47 (C3, C6), 161.07 (C5, C4), 186.40
(C=O). Found, %: C 69.84; H 8.21. C17H24O4. Calcu-
lated, %: C 69.86; H 8.22.
3,6-Di-tert-butyl-4-{[4-(2,5-di-tert-butyl-3,4-dioxo-
cyclohexa-1,5-dien-1-yloxy)cyclohexyl]methoxy}-
cyclohexa-3,5-diene-1,2-dione (VIIIb). Yield 0.67 g
(23%), dark red powder, mp 263–265°C. IR spectrum
(mineral oil), ν, cm–1: 1680, 1660, 1635, 1540, 1460,
1405, 1395, 1380, 1295, 1250, 1230, 1195, 1095,
Bis-o-quinones Vb–VIIIb (general procedure).
The reactions were carried out as described above, the
reactant ratio quinone I–glycol being 4:1 (III–glycol
2:1); reaction time 100 h. When 4-alkoxy-3,6-di-tert-
butyl-1,2-benzoquinones Va–VIIIa were used as start-
ing compounds, the ratio quinone–glycol was 1:1.
1
1075, 1020, 945, 895, 736, 722, 680, 595. H NMR
spectrum, δ, ppm: 1.12–1.20 m (4H, CH2), 1.25 s and
1.32 s (18H each, t-Bu), 1.75–1.90 m (2H, CH), 1.95–
2.05 m (4H, CH2), 3.89 d (4H, CH2O, J = 6.2 Hz),
4,4′-[Butane-1,4-diylbis(oxy)]bis(3,6-di-tert-butyl-
cyclohexa-3,5-diene-1,2-dione) (Vb). Yield 0.8 g
(31%), dark red crystals, mp 182–185°C. IR spectrum
(mineral oil), ν, cm–1: 1690, 1650, 1625, 1585, 1490,
1470, 1410, 1400, 1390, 1370, 1335, 1310, 1255,
1240, 1230, 1200, 1175, 1080, 1040, 950, 930, 905,
13
6.82 s (2H, 5-H). C NMR spectrum, δC, ppm: 29.09
and 30.7 (CH3), 29.11 (CH2), 35.2 (CMe3), 38.2 (CH),
74.9 (CH2O); 130.0, 130.4, and 149.6 (C3, C5, C6);
162.9 (C4O), 181.7 and 182.3 (C=O). Found, %:
C 74.40; H 8.95. C36H52O6. Calculated, %: C 74.48;
H 8.97.
1
890, 830, 740. H NMR spectrum, δ, ppm: 1.25 s and
1.32 s (18H each, t-Bu), 1.97–2.06 m (4H, CH2), 4.12–
13
4.20 m (4H, CH2O), 6.84 s (2H, 5-H). C NMR spec-
trum, δC, ppm: 26.54 (CH2), 28.96 and 30.57 (CH3),
35.14 (CMe3), 69.05 (CH2O), 129.79 and 149.75
(C5, C6), 162.32 (C4), 181.48 and 182.27 (C=O).
Found, %: C 73.12; H 8.76. C32H46O6. Calculated, %:
C 73.00; H 8.74.
2′,4,5′,7-Tetra-tert-butyl-3′-hydroxy-4′H-spiro-
[1,3-benzodioxole-2,1′-cyclohexa[2,5]dien]-4′-one
(X). A solution of 0.094 g (0.4 mmol) of 2-hydroxy-
3,6-di-tert-butyl-1,4-benzoquinone (II) and 0.089 g
(0.4 mmol) of compound II in acetonitrile in the pres-
ence of potassium hydroxide was heated for 1 h under
reflux. The mixture was extracted with toluene, and the
extract was evaporated. Light yellow powder separated
from hexane. Yield 0.093 g (53%), mp 236–238°C. IR
spectrum (mineral oil), ν, cm–1: 3790, 1655, 1635,
4,4′-[2,2′-Oxybis(ethane-2,1-diyl)bis(oxy)]bis-
(3,6-di-tert-butylcyclohexa-3,5-diene-1,2-dione)
(VIb). Yield 0.65 g (24%), dark red crystals, mp 73–
75°C. IR spectrum (mineral oil), ν, cm–1: 1690, 1650,
1625, 1550, 1490, 1470, 1400, 1385, 1360, 1305,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 4 2011

SHURYGINA et al.
494
1625, 1490, 1470, 1410, 1400, 1390, 1370, 1350,
1340, 1290, 1260, 1240, 1205, 1140, 1090, 1045,
1035, 995, 980, 950, 935, 875, 810, 795, 670, 645,
The structures were solved by the direct method
and were refined by the least-squares procedure with
respect to F2hkl in anisotropic approximation for all non-
hydrogen atoms. Hydrogen atoms were placed into
ideal positions (from the viewpoint of geometry con-
siderations) and were refined in isotropic approxima-
tion according to the riding model. All calculations
were performed using SHELXTL software package
[24]. Corrections for absorption by crystals of VIb,
VIIb, and IX were introduced using SADABS2x
program. The complete sets of crystallographic data
for compounds VIb, VIIb, and IX were deposited to
the Cambridge Crystallographic Data Centre [entry
nos. CCDC 728527 (VIb), CCDC 728528 (VIIb), and
CCDC 728526 (IX)]. The principal bond lengths in
molecules VIb, VIIb, and IX are collected in Table 1.
1
615. H NMR spectrum, δ, ppm: 1.18 s (9H, t-Bu),
1.33 s (18H, t-Bu), 1.34 s (9H, t-Bu), 6.50 s (1H, 12-H),
6.78 s (2H, 4-H, 5-H). 13C NMR spectrum, δC, ppm:
28.85, 29.05, and 29.32 (CH3); 33.75, 34.02, and 35.53
(CMe3); 118.63 and 138.54 (C4, C5, C12); 109.86,
125.30, 132.29, 140.76, 144.70, and 146.28 (C1, C2,
C3, C6, C8, C9, C11); 181.66 (C=O). Found, %: C 76.30;
H 9.05. C28H40O4. Calculated, %: C 76.36; H 9.09.
Potassium and manganese o-semiquinone com-
plexes were obtained according to standard procedures
[22, 23]. An ESR ampule was charged with the corre-
sponding o-quinone and metallic potassium, degassed
tetrahydrofuran was recondensed thereto, the ampule
was shaken until the mixture changed its color, and its
ESR spectrum was recorded. A degassed toluene solu-
tion containing dodecacarbonyldimanganese and
o-quinone was irradiated in an ESR ampule with
a KGM-24-150 lamp until change of color.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
nos. 09-03-00668-a, 09-02-01118-a, 10-03-00788-a,
11-03-97040-r_povolzh’e_a) and by the President of
the Russian Federation (project no. NSh-7065.2010.3).
X-Ray analysis of single crystals of VIb, VIIb,
and IX was performed on a Smart Apex diffractometer
(MoKα irradiation, graphite monochromator, λ =
0.71073 Å). Compound VIb: crystal dimensions 1.02×
0.22×0.20 mm at 100(2) K; C35H53O7; monoclinic
crystal system; unit cell parameters: a = 24.942(2), b =
18.318(2), c = 15.006(1) Å; β = 93.004(2)°; V =
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