Catalytic alkylation of pyrocatechol with camphene

Article abstract of DOI:10.1134/S1070363212060163

Regularities of the pyrocatechol alkylation with camphene in the presence of aluminum-containing homogeneous catalysts and heterogeneous acid catalysts were studied. The effect of the catalyst type on the reaction selectivity and the product composition was established. The most selective heterogeneous catalyst for the C-alkylation of pyrocatechol is montmorillonite KSF, which leads to a rearrangement of the terpene fragment to isocamphyl structure. Homogeneous organoalyuminum compounds are found to be nonselective catalysts for the alkylation of pyrocatechol at the benzene ring. Original Russian Text. V.M. Fomin, A.E. Shirokov, 2012.

Full text of DOI:10.1134/S1070363212060163

ISSN 1070-3632, Russian Journal of General Chemistry, 2012, Vol. 82, No. 6, pp. 1130–1134. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © I.Yu. Chukicheva, I.V. Fedorova, Yu.S. Matveev, A.V. Kutchin, 2012, published in Zhurnal Obshchei Khimii, 2012, Vol. 82, No. 6,
pp. 973–977.
Catalytic Alkylation of Pyrocatechol with Camphene
I. Yu. Chukicheva, I. V. Fedorova, Yu. S. Matveev, and A. V. Kutchin
Institute of Chemistry, Komi Scientific Center, Ural Branch of the Russian Academy of Sciences,
ul. Pervomaiskaya 48, Syktyvkar, 167982, Russia
e-mail: chukicheva-iy@chemi.komisc.ru
Received March 22, 2011
Abstract—Regularities of the pyrocatechol alkylation with camphene in the presence of aluminum-containing
homogeneous catalysts and heterogeneous acid catalysts were studied. The effect of the catalyst type on the
reaction selectivity and the product composition was established. The most selective heterogeneous catalyst for
the C-alkylation of pyrocatechol is montmorillonite KSF, which leads to a rearrangement of the terpene
fragment to isocamphyl structure. Homogeneous organoalyuminum compounds are found to be nonselective
catalysts for the alkylation of pyrocatechol at the benzene ring.
DOI: 10.1134/S1070363212060163
Alkylation of phenols, including dihydric, with
terpenes (camphene, β-pinene) with the use of zeolites
as catalysts to create an organized reaction medium has
been described. However, the conversion of initial
reagents and the selectivity of these processes were
insignificant [1–3]. The regio- and stereoselectivity of
the alkylation of phenols with camphene in the
presence of aluminum alkoxides is ascribed to the
proceeding of the intramolecular alkylation in the
aluminum coordination sphere [4].
presence of aluminum-containing homogeneous
catalysts and heterogeneous acid catalysts aimed at the
selective synthesis of the C-alkylated pyrocatechol.
The alkylation conditions as well as the composition of
the reaction products were determined by the structure
of the initial phenols and olefins, as well as by the
features of the used catalyst. The composition of the
products of alkylation of phenols with camphene is
complicated by the opportunity of skeletal rearrange-
ments of the intermediate carbocation arising from
camphene, the initial bicyclic monoterpene [7, 8].
Previously, we studied the alkylation of dihyd-
roxybenzenes with camphene in the presence of alu-
minum phenolate and aluminum isopropoxide [5, 6].
The aluminum phenoxide as one of the most active
organo-aluminum catalysts was used as the catalyst for
preparation in situ of mixed aluminum phenoxides. It
was shown that the reaction of pyrocatechol with
camphene at 160–170°C in the presence of aluminum
phenoxide proceeded with the yield of up to 75.5% to
afford the product of O-alkylation IIIa, the monoether
with isobornyl structure of the terpene substituent.
We found that the use of aluminum pyrocatecholate
at 120°C for the alkylation of pyrocatechol I with camphene
II leads to the formation of the isobornyl catechol
ether IIIa (78%) as the main product (see the table),
like in the case of catalysis with aluminum phenoxide.
Raising the temperature of the reaction mixture to 160°C
leads to a decrease in the process selectivity: a mixture
of the products of O- and C-alkylation is formed with
different terpene substituents. Using (acac)2AlCl leads
to the formation of almost equal amounts of products
of O- and C-alkylation containing isobornyl and iso-
campenyl terpene substituents. The interaction of pyro-
catechol I with camphene II catalyzed by the sulfonic
acid cation exchanger FIBAN K-1 was carried out
using different solvents (see the table). At boiling in
methylene chloride (40°C) the alkylation proceeds
with high selectivity and the formed product is the
pyrocatechol monoester with isobornyl structure of
terpene substituent IIIa in up to 99% yield.
It was found that C-alkylation of pyrocatechol
occurred only at a sufficiently high temperature (200°C).
Probably, in this case, the reaction conditions cor-
respond to thermodynamic control of the reaction that
results in the rearrangement of the ether of pyro-
catechol to the product of the C-alkylation.
In this research we continued the study on the
alkylation of pyrocatechol I with camphene II in the
1130

1131
CATALYTIC ALKYLATION OF PYROCATECHOL WITH CAMPHENE
OR
11
OH
OH
HO
R
O
R
O
16
15
12
13
R
R'
OH
14
HO
IIIa_IIIc
IV
V
catalyst
+
OH
OH
OH
O
R
OH
R
OH
OH
R
O
R
I
II
R
R
VIa_VId
VIIa_VIId
VIIIa, VIIIb, VIIId
IХa, IXb
IV, R = 2-(1,7,7-trimethylbicyclo[2.2.1]heptan-2-yl); V, R = 1,7,7-trimethylbicyclo[2.2.1]heptan-2-yl, R' = 2,2,3-
9
7
8
7
10
2
10
trimethylbicyclo[2.2.1]heptan-5-yl); III, VI_IХ,
(b);
R =
(a);
4
1
5
3
9
6
1
4
2
6
H
5
3
9
H
8
7
7
10
10
(c);
(d).
4
1
5
3
2
6
9
1
4
2
5
6
H
3
H
8
8
catalyst is one of the following substances: FIBAN K-1, FIBAN K-2, FIBAN K-3, aluminum pyrocatecholate, (acac)2AlCl .
It was noted that raising the temperature of the
reaction mixture by performing the reaction in hexane
(70°C) or heptane (about 100°C) leads to a decrease in
selectivity and the formation of a complex mixture of
products of O- and C-alkylation with a different struc-
ture of terpene substituent. Dihydric phenols are easily
oxidized, which may explain the appearance in these
conditions of the oxidation products (18%), including
dialkylated quinones IXa and IXb (see the table).
is the predominant formation of products with iso-
camphyl terpene substituent. In addition, the main
product of the alkylation of pyrocatechol I with cam-
phene II is the para-alkylated pyrocatechol with iso-
camphyl terpene substituent (VIIIb, 38–57%) regard-
less of the temperature and the ratio of initial reagents
(see the table). The interaction of pyrocatechol with an
excess of camphene leads to the formation of a
complex mixture of dialkylated phenols with the
terpene substituents in ortho- and para-positions. In
this case the products with isobornyl substituent also
were not detected. Carrying out the reaction by re-
fluxing in CH2Cl2 contributes to the selective forma-
tion of ether IIIa as in the case of FIBAN K-1.
Use of FIBAN K-4 and FIBAN X-1 as catalysts in
the same solvents does not lead to the pyrocatechol
alkylation. This difference in efficiency between
FIBANS K-1, X-1, and K-4 is due to the difference
between their functional groups. FIBAN K-1 is a fibrous
strong acidic cation exchanger (functional group is
SO3H). Its polymeric base is polypropylene fiber with
the grafted copolymer of styrene and divinylbenzene.
FIBAN K-4 is a weak acid cation exchanger
(functional group is COOH). FIBAN X-1 is a fibrous
chelating ion ex-changer containing functional groups
N(CH2COO)2 and COOH.
Thus, the studied heterogeneous catalysts promote
selective formation of desired products. Using KSF
and FIBAN K-1 in a low-temperature regime contributes
to the O-alkylation and the formation of ethers with
isobornyl structure of the terpene fragment. The most
selective heterogeneous catalyst for the C-alkylated
pyrocatechol is montmorillonite KSF, which leads to
the terpene fragment rearrangement into isocamphyl
structure. Homogeneous organoaluminum compounds
are nonselective catalysts for the alkylation of the
An interesting feature of the alkylation of
pyrocatechol I with camphene II in the presence of
KSF clay (the clay from the group of layered silicates)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 6 2012

1132
CHUKICHEVA et al.
Conditions of alkylation of pyrocatechol with camphene and the products obtained
Ratio of reaction products, %
Ratio
I:II:
(mol)
Reaction Conversi
III
b
VI
VII
VIII
conditions
on, %
IVa Va
IX
a
c
b
а
c
d
b
а
c
d
b
а
c
d
FIBAN K-1
3
1:1
100°С,
С7Н16, 2 h
85
99
90
1
–
8
–
–
3
–
–
7
–
–
5
–
3
20
8
12
5
–
26
8
7
–
–
–
–
–
8
2
–
70°С,
С6Н14, 4 h
24
99
8
6
–
–
7
40°С,
СН2Сl2, 2 h
–
–
–
–
–
–
–
–
–
–
–
–
–
KSF
1:1
1:2
40°С,
СН2Сl2, 3 h
99
87 13
–
–
–
–
–
–
–
8
–
–
–
–
–
–
–
–
100°С,
С7Н16, 2 h
100°С, 3 h
98
91
–
–
4
–
–
–
4
–
17
–
–
–
9
–
4
–
8
16
7
51
57
–
–
11
3
3
–
3
–
–
–
–
–
–
3
160°С, 2 h
100°С, 4 h
98
98
1
–
–
1
9
14
–
12
6
15 40
8
–
7
–
–
10
21
–
–
4
–
38
5
–
160°С, 3 h
98
–
–
–
31
12
50
–
7
–
Aluminum pyrocatecholate
1:1
1:1
120°С, 10 h
160°С, 3 h
50
80
78
37 14
6
1
4
–
3
–
–
–
–
–
5
–
–
–
–
4
5
11
–
–
–
–
–
5
10
16
–
–
–
–
–
–
(acac)2AlCl
–
160°С, 4 h
90
38 13
–
–
–
–
–
2
22
–
–
3
13
–
–
pyrocatechol ring. The alkylation products are mainly
the compounds with isobornyl terpene substituent.
H2SO4, 100 ml of 95% ethanol) followed by heating to
100–150°C.
EXPERIMENTAL
For column chromatography Silica gel 60 (70–
230 μm) was used. In the syntheses the following catalysts
were used: montmorillonite KSF from Acros Organics,
cation exchangers FIBAN K-1, K-4, and X-1 provided
by the Institute of Physical Organic Chemistry of the
National Academy of Sciences of Belarus.
1H and 13C NMR spectra were recorded on a Bruker
Avance II 300 instrument (operating frequency 300 MHz
and 75 MHz respectively), solvent deuterochloroform.
As the internal reference the signals of chloroform (δH
7.26 ppm, δC 76.90 ppm) were used. The purity of
starting materials was checked and the analysis of reac-
tion products was carried out by GLC on a Shimadzu
GC-2010AF chromatograph using a capillary column
HP-1 (60 m×0.25 mm×0.25 μ, temperature 100–240°C,
heating rate 6°C per minute). Flame ionization
detector, carrier gas helium. Melting point was deter-
mined on a Koeffler heating block.
Alkylation of pyrocatechol with camphene in the
presence of aluminum-containing catalysts. In a
two-neck 100 ml flask equipped with a thermometer
and reflux condenser was heated a mixture of 0.80 g
(7 mmol) of pyrocatechol, 1 g (7 mmol) of camphene,
and 10 wt % of aluminum pyrocatecholate or
(acac)2AlCl with respect to the initial pyrocatechol.
During the reaction the temperature was maintained at
120°C and 160°C to complete conversion of camphene
(control by GLC and TLC). After the reaction comple-
tion the reaction mixture was cooled, diluted with
diethyl ether, 50% hydrochloric acid was poured to it
to decompose the catalyst, then the mixture was
washed with saturated NaHCO3 and water until neutral
The reaction progress was monitored by TLC on
Sorbfil plates using the solvent system petroleum
ether–diethyl ether with increasing fraction of the
latter. For the detection of substances the plate was
treated with a solution of KMnO4 (25 g of KMnO4,
300 ml of H2O, 0.5 ml of conc. H2SO4), as well as with
a solution of vanillin (1 g of vanillin, 5 ml of conc.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 6 2012

1133
CATALYTIC ALKYLATION OF PYROCATECHOL WITH CAMPHENE
reaction. The organic layer was dried over anhydrous
Na2SO4 and the solvent was evaporated. The pyro-
catechol alkylation products were isolated using
column chromatography.
H2), 5.81 s (1H, OH), 6.73 d (1H, H16, J 9 Hz), 6.82 d
(1H, H15, J 9 Hz), 7.00 d (1H, H14, J 9 Hz). 13C NMR
spectrum (CDCl3, 75 MHz), δ, ppm: 12.03 (C10), 16.01
(C10'), 20.38 (C8), 20.79 (C9), 24.49 (C8'), 27.73 (C9'),
30.36 (C5), 32.04 (C7'), 32.68 (C4'), 33.67 (C6'), 34.27
(C6), 39.57 (C3), 39.83 (C5'), 40.66 (C4), 45.88 (C1),
47.21 (C2', C3'), 49.65 (C7), 49.81 (C1'), 85.78 (C2),
109.33 (C16), 118.17 (C14), 118.81 (C15), 133.56 (C13),
143.72 (C11), 144.46 (C12).
Alkylation of pyrocatechol with camphene in the
presence of acid catalysts. In the case of sulfonic acid
cation exchangers, FIBAN K-1, K-4, and X-1, catalyst
was taken in amount 10 wt % with respect to the initial
pyrocatechol; montmorillonite KSF was taken in a
weight ratio 1:1 to the pyrocatechol. The mixture of
pyrocatechol, camphene, and the catalyst taken in the
calculated amounts was heated at a desired tempera-
ture in a two-neck flask equipped with a thermometer
and a reflux condenser. The reaction was carried out
either in an organic solvent, or in melt. The reaction
conditions are shown in the table.
3,6-Di-(1,7,7-Trimethylbicyclo[2.2.1]hept-exo-2-
yl)benzo-1,2-diol (VIа). Yellow oil. 1Н NMR
spectrum (300 МHz, CDCl3), δ, ppm (J, Hz): 0.84 s
9
9'
(6Н, СН3810, СН310'), 0.90 s (6Н, СН3 , СН3 ), 1.26 s
8'
(3Н, СН3 , СН3 ), 3.04 t (2Н, Н2, Н2', J 6 Гц), 4.65 s
(2ОН), 1.39–1.48 m (6Н, Н4, Н4', Н5, Н5', Н6, Н6'),
1.55–1.68 m (3Н, Н3, Н3', Н5, Н5', Н6, Н6'), 1.84-1.85 m
(1Н, Н3), 6.71-6.95 m (2Н, Н15, Н16). 13С NMR
spectrum (CDCl3, 75 МHz), δ, ppm: 12.43 (С10, C10'),
20.61 (С9, C9'), 21.45 (С8, C8'), 27.59 (С5, C5'), 34.38
(С6, C6'), 40.11 (С3, C3'), 45.53 (С2, C2'), 46.13 (С4,
C4'), 48.84 (С1, C1'), 49.93 (С7, C7'), 125 (С15, C16),
142.4 (С11, C14), 145.18 (С12, C13).
Upon the reaction completion the mixture was
dissolved in diethyl ether, filtered from the catalyst,
and the reaction products was separated by column
chromatography. The structure of these compounds
was evaluated using the spectral methods (NMR).
Spectral and chromatographic characteristics of
compounds IIIa–IIIc, VIIa, VIIb, and VIIIa are
identical to those described earlier [5].
3,6-Di-(2,2,3-Trimethylbicyclo[2.2.1]hept-exo-2-
1
yl)benzo-1,2-diol (VIb). Yellow oil. заменить на: Н
NMR spectrum (300 МHz, CDCl3), δ, ppm (J, Hz):
2-(1,7,7-Trimethylbicyclo[2.2.1]heptan-2-yl)-6-
(1,7,7-trimethylbicyclophenol[2.2.1]heptan-2-yloxy)
phenol (IV). Colorless powder, mp 136°C. H NMR
9
0.92 d (6Н, СН310, СН310', J 6 Hz), 0.94 s (6Н, СН3 ,
9'
8
8'
СН3 ), 1.08 s (3Н, СН3 , СН3 ), 2.91 t (2Н, Н5, Н5', J
6 Hz), 5.24, 5.18 s (1Н each, 2ОН), 1.35-1.49 m (4Н,
Н6, Н6', Н7, Н7'), 1.63–1.88 m (6Н, Н7, Н7', Н1, Н1', Н4,
Н4'), 2.17–2.34 m (2Н, Н3, Н3'), 6.71–6.95 m (2Н, Н15,
Н16). 13С NMR spectrum (CDCl3, 75 МHz), δ, ppm:
16.2 (С10, С10'), 27.6 (С9, С9'), 24.8 (С8, С8'), 33.5 (С7,
С7'), 40.7 (С6, С6'), 32.6 (С5, С5'), 50.9 (С4, С4'), 39.6
(С3, С3'), 48.8 (С2, С2'), 49.7 (С1, С1'), 116.61 (С15,
С16), 130.80 (С11, С14), 141.45 (С12, С13).
1
spectrum (300 MHz, CDCl3), δ, ppm (J, Hz): 0.83 s
9'
8'
(3Н, СH310'), 0.88 s (3Н, СH3 ), 0.94 s (3Н, СH3 ),
10
9
8
0.95 s (3Н, СH3 ), 1.03 s (3Н, СH3 ), 1.07 s (3Н, СH3 ,
1.03–1.14 m (4H, H6, H5, H6', H5'), 1.31–1.45 m (4H,
H4, H6', H6, H4') , 1.64–1.67 m (4H, H3, H5, H3', H5') ,
1.85–1.91 m (2H, H3, H3'), 3.32 t (1H, H2', J 6 Hz),
4.10–4.19 m (1H, H2), 5.86 s (1H, OH), 6.70 d (1H,
H16, J 9 Hz), 6.79 t (1H, H15, J 9 Hz), 6.96 d (1H, H14,
J 9 Hz). 13C NMR spectrum (CDCl3, 75 MHz), δ, ppm:
12.31 (C10, C10'), 20.36 (C8, C8'), 21.43 (C9, C9'), 27.55
(C5, C5'), 34.24 (C6, C6'), 39.80 (C3, C3'), 45.29 (C4),
47.00 (C2', C4'), 47.82 (C1'), 49.32 (C7), 48.08 (C1),
50.00 (C7'), 85.71 (C2), 109.54 (C16), 118.26 (C14),
120.15 (C15), 129.73 (C13), 145.32 (C11), 147.11 (C12).
3,6-Di-(2,2,4-Trimethylbicyclo[2.2.1]hept-exo-5-
1
yl)benzo-1,2-diol (VIc). Yellow oil. H NMR spec-
trum (300 MHz, CDCl3), δ, ppm (J, Hz): 1.03 s (6H,
9
9'
8
8'
CH3 , CH3 ), 1.06 s (6H, CH3 , CH3 ), 1.26 s (6H,
CCH310, CCH310'), 1.25–1.43 m (4H, H3, H3', H7, H7'),
1.50–1.71 m (4H, H6, H6', H1, H1'), 1.75–1.85 m (6H,
H1, H1', H3, H3', H7, H7'), 2.15–2.4 m (2H, H6, H6'), 2,7 t
(2H, H5, H5'), 5.00 s (2OH), 6.65 s (2H, H15, H16). 13C
NMR spectrum (CDCl3, 75 MHz), δ, ppm: 17.00 (C10,
C10'), 26.78 (C9, C9'), 28.98 (C8, C8'), 33.00 (C6, C6'),
33.49 (C7, C7'), 39.64 (C2, C2'), 40.76 (C5, C5'), 45.29
(C3, C3'), 39.64 (C2, C2'), 49.77 (C1, C1'), 51.04 (C4,
C4'), 143.00 (C12, C13), 132 (C11, C14), 110.99 (C15, C16).
2-(2,2,3-Trimethylbicyclo[2.2.1]heptan-2-yl)-6-
(1,7,7-trimethylbicyclophenol[2.2.1]heptan-2-yloxy)
phenol (V). Colorless oil. 1H NMR spectrum
(300 MHz, CDCl3), δ, ppm (J, Hz): 0.87 d (3H,
8'
9'
CCH310', J 6 Hz), 1.06 d (6H, CH3 , CH3 , J 6 Hz),
8
9
1.09 s (6H, CH3 , CH3 ), 1.16 s (3H, CH10), 1.18–1.22
m (3H, H6, H5, H7'), 1.46–1.49 m (7H, H6, H6', H5, H1', H7',
H3', H4), 1.67–1.69 m (1H, H3), 1.70–1.94 m (3H, H3,
H6', H4'), 3.11 t (1H, H5', J 6 Hz), 4.10–4.21 m (1H,
3,6-Di-(1,4,7-anti-trimethylbicyclo[2.2.1]hept-
1
exo-2-yl)benzo-1,2-diol (VId). Yellow oil. H NMR
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 6 2012

1134
CHUKICHEVA et al.
8'
spectrum (300 MHz, CDCl3), δ, ppm (J, Hz): 0.6 s
CH3 ), 1.16–1.37 m (6H, 2H6, 2H6', H7, H7'), 1.40–1.95
m (4H, H7, H7', H1, H1'), 2.99 t (2H, H2, H2', J 6 Hz),
6.78–6.85 m (2H, H15, H16). 13C NMR spectrum
(CDCl3, 75 MHz), δ, ppm: 16.19 (C10, C10'), 25.00 (C9,
C9'), 27.31 (C8, C8'), 29.70 (C5, C5'), 33.38 (C6, C6'),
39.32 (C3, C3'), 44.89 (C4, C4'), 45.39 (C2, C2'), 48.39
(C7, C7'), 50.7 (C1, C1'), 134.14 (C15, C16),145.02 (C11,
C14), 180.01 (C12, C13).
9
9'
8
8'
(6H, CH3 , CH3 ), 0.80 s (6H, CH3 , CH3 ), 1.05 s
(6H, CCH310, CCH310'), 1.35–1.75 m (8H, 2H5, 2H5',
2H6, 2H6'), 1.8–1.95 m (2H, 2H3, 2H3'), 2.00 m (2H,
H7, H7'), 2.15–2.48 m (2H, H2, H2'), 5.13, 5.29 s (1Н
each, 2ОН), 6.7–6.85 m (2H, H14, H16). 13C NMR
spectrum (CDCl3, 75 MHz), δ, ppm: 8.36 (C8, C8'),
17.16 (C9, C9'), 19.02 (C10, C10'), 34.45 (C5, C5'), 37.73
(C6, C6'), 45.12 (C4, C4'), 46.55 (C3, C3'), 49.04 (C7,
C7'), 50.00 (C1, C1'), 51.06 (C2, C2'), 139.43(C11, C14),
140.63 (C12, C13), 112.59 (C15, C16).
3,6-Di-(exo-2,2,3-Trimethylbicyclo[2.2.1]hept-2-
1
yl)-benzo-1,2-quinone (IXb). Yellow oil. H NMR
spectrum (300 MHz, CDCl3), δ, ppm (J, Hz): 0.84–
8
0.98 m (6H, CCH310, CCH310'), 1.11 s (12H, CH3 ,
3-(exo-2,2,4-Trimethylbicyclo[2.2.1]hept-5-yl)-
1
8'
9
9'
CH3 , CH3 , CH3 ), 1.15–1.35 m (6H, 2H6, 2H6', H7,
H7'), 1.40–1.95 m (4H, H7, H7', H1, H1'), 2.05–2.20 m
(4H, H4, H4', H3, H3'), 2.70 m (2H, H5, H5'), 6.65–6.75
m (2H, H15, H16). 13C NMR spectrum (CDCl3, 75
MHz), δ, ppm: 14.00 (C10, C10'), 24.75 (C8, C8'), 27.5
(C9, C9'), 32.89 (C5, C5'), 33.65 (C7, C7'), 40.67 (C6,
C6'), 41.20 (C3, C3'), 50.70 (C4, C4'), 49.55 (C1, C1'),
49,63 (C2, C2'), 124.60 (C15, C16), 145.00 (C14, C11),
182.00 (C12, C13).
benzo-1,2-diol (VIIc). Yellow oil. H NMR spectrum
9
(300 MHz, CDCl3), δ, ppm (J, Hz): 0,84 s (3H, CH3 ),
8
0.9 s (3H, CH3 ), 1.13 s (3H, CCH310), 1.35–1.50 m
(2H, H3, H7), 1.61–1.75 m (3H, H1, H3, H7), 1.79–1.98
(1H, H6), 2.15–2.38 m (1H, H6), 2.7 t (1H, H5), 5.2 s
(2OH), 6.6–6.7 m (3H, H13, H14, H16). 13C NMR
spectrum (CDCl3, 75 MHz), δ, ppm: 11.09 (C10), 14.09
(C9), 24.34 (C8), 30.30 (C6), 34.11 (C7), 39.21 (C2),
40.93 (C5), 45.68 (C3), 39.60 (C2), 48.87 (C1), 51.00
(C4), 143.21 (С13), 142.8 (С12), 130.00 (С11), 118.23
(С14), 116.51 (С15), 111.05 С16).
ACKNOWLEDGMENTS
This work was supported by the Program of the
Presidium of the Russian Academy “Development of
methods for preparation of chemical substances and
creation of new materials,” (project no. 09-P3-1010).
3-(exo-1,4,7-Trimethylbicyclo[2.2.1]hept-2-yl)-
1
benzo-1,2-diol (VIId). Yellow oil. H NMR spectrum
9
(300 MHz, CDCl3), δ, ppm (J, Hz): 0,73 s (3H, CH3 ),
8
0.74 d (3H, CH3 , J 6Hz), 1.06 s (3H, CCH310), 1.35–
1.50 m (2H, H3, H7), 1.61–1.75 m (3H, H1, H3, H7),
1.79–1.98 m (1H, H6), 2.15–2.38 m (1H, H6), 2.7 t
(1H, H5), 5.2 s (2OH), 6.6–6.7 m (3H, H13, H14, H16).
13C NMR spectrum (CDCl3, 75 MHz), δ, ppm: 8.30
(C10), 17.16 (C9), 19.02 (C8), 30.296 (C6), 34.114 (C7),
39.215 (C2), 40.93 (C5), 45.68 (C3), 39.60 (C2), 48.87
(C1), 51.00 (C4), 142.58 (С13), 141.31 (С12), 129.96
(С11), 118.74 (С14), 116.65 (С15), 111.23 С16).
REFERENCES
1. Fomenko, V.V., Korchagina, D.V., Salakhutdinov, N.F.,
and Barkhash, V.A., Helvetica Chimica Acta, 2002,
vol. 85, p. 2358.
2. Salakhutdinov, N.F., Volcho, K.P., Korchagina, D.V.,
Tatarova, L.E., and Barkhash, V.A., Tetrahedron, 1998,
vol. 54, p. 15619.
3. Fomenko, V.V., Korchagina, D.V., Salakhutdinov, N.F.,
Ione, K.T., and Barkhash, V.A., Zh. Org. Khim., 2000,
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4. Chukicheva, I.Yu., Spirikhin, L.V., and Kuchin, A.V.,
Zh. Org. Khim., 2008, vol. 44, no. 1, p. 69.
4-(exo-2,2,3-Trimethylbicyclo[2.2.1]hept-5-yl)-
benzo-1,2-diol (VIIIb). Yellow oil. 1H NMR spectrum
(300 MHz, CDCl3), δ, ppm (J, Hz): 0.90 d (3H,
9
8
CCH310, J 6 Hz), 1.05 s (6H, CH3 , CH3 ), 1.32–1.39 m
(2H, H6, H7), 1.69–1.90 m (3H, H7, H1, H4), 2.16–2.24
m (2H, H3, H6'), 2.7 t (1H, H5), 5.65 s (2OH), 6.68–
6.93 m (3H, H12, H15, H16). 13C NMR spectrum
(CDCl3, 75 MHz), δ, ppm: 16.28 (C10), 24.84 (C8),
27.56 (C9), 32.00 (C5), 33.42 (C7), 39.46 (C3), 40.54
(C6), 49.03 (C1), 49.73 (C4), 49.50 (C2), 114.38 (C15),
115.25 (C16), 119.41 (C12), 140.98 (C11), 141.28 (C13),
143.27 (C14).
5. Chukicheva, I.Yu., Timusheva, I.V., Spirikhin, L.V.,
and Kutchin, A.V., Chemistry of Natural Compounds,
2007, vol. 43, no. 3, p. 245.
6. Chukicheva, I.Yu., Kuchin, A.V., Spirikhin, L.V., and
Ipatova, E.U., Khimiya i Komp’yuternoe Modelirovanie.
Butlerovskie Soobshcheniya, 2003, no. 1, p. 16.
7. Kheifits, L.A. and Aul’chenko, I.S., Khimiya i tekh-
nologiya dushistykh veshchestv i masel (Chemistry and
Technology of Perfumed Substances and Oils), Moscow:
Pishchevaya Promyshlennost’, 1968, Proceedings, no. 8,
p. 142.
3,6-Di-(exo-1,7,7-Trimethylbicyclo[2.2.1]hept-2-
1
yl)-benzo-1,2-quinone (IXa). Yellow oil. H NMR
8. Koptyug, V.A., Shubin, V.G., and Barkhash, V.A.,
Sovremennye problemy karbonievykh ionov (Modern
Problems of Carbonium Ions), Novo- sibirsk, 1975.
spectrum (300 MHz, CDCl3), δ, ppm (J, Hz): 0.80–
9
9'
8
1.10 m (18H, CCH310, CCH310', CH3 , CH3 , CH3 ,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 6 2012