Alkylation of aluminum phenolate with unsaturated monoterpenes

Full text of DOI:10.1134/S0012500811040124

ISSN 0012ꢀ5008, Doklady Chemistry, 2011, Vol. 437, Part 2, pp. 127–128. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © A.V. Kutchin, I.Yu. Chukicheva, I.V. Fedorova, O.A. Shumova, 2011, published in Doklady Akademii Nauk, 2011, Vol. 437, No. 6, pp. 776–777.
CHEMISTRY
Alkylation of Aluminum Phenolate
with Unsaturated Monoterpenes
Corresponding Member of the RAS A. V. Kutchin, I. Yu. Chukicheva,
I. V. Fedorova, and O. A. Shumova
Received July 6, 2010
DOI: 10.1134/S0012500811040124
Useful properties of natural phenolic compounds ether (
with terpene substituents (their physiological and yield of
antioxidant activity) promote the development of terpene substituent (IIa) was 23%. When temperature
strategies for the synthesis of their analogues and novel was increased to 160 C, the reaction lasted for 2 h to
I) (77%, Scheme 1) as a main product. The
oꢀalkylated phenol with isobornyl structure of
°
derivatives.
form mainly Cꢀalkylation products (95%) with preꢀ
dominance of phenol IIa (73%). The yield of Oꢀalkyꢀ
Terpenoids are prone to different skeleton rearꢀ
lation product
A specific feature of alkylation of aluminum pheꢀ
noxide with ꢀpinene under the same conditions
(160 C, 2 h) is a high yield of chromanꢀlike products
III and IV (37%). Moreover, the reaction also leads to
ꢀisobornylphenol IIa (34%) and ꢀisocamphylpheꢀ
nol IIb (10%). ꢀAlkylated phenol (16%), which is not
I was only 5%.
rangements; therefore, the selectivity of alkylation of
aromatic compounds with terpenes is the main condiꢀ
tion of the process [1–4].
β
°
The use of aluminum alkoxides as catalysts is
known to ensure the selective alkylation of phenols. In
particular, the alkylation of different phenols with
o
o
p
camphene leads to oꢀisobornylphenols in 85% and
typical for the reactions of (PhO)3Al, was also isolated
from the mixture of products. The composition of the
alkylation product mixture did not change when the
reaction time increased to 6 h. In the reaction of aluꢀ
higher yields [5, 6]. Regioꢀ and stereoselectivity of this
process is explained by the fact that the alkylation proꢀ
ceeds intramolecularly within coordination sphere of
aluminum [7].
minum phenoxide with
products is determined by carbocations
resulting from ꢀpinene by the Wagner–Meerwein
rearrangement and carbocation of the pꢀmenthane
structure resulting from the opening of the strained
fourꢀmembered ring of ꢀpinene. Initially formed carꢀ
bocations , and have identical sterical possibiliꢀ
ties for addition to aluminum phenoxide [13].
β
ꢀpinene, the structure of the
The methods of preparation of aluminum acylates
and alkoxides derived from higher fatty acids and aluꢀ
minum alkoxides of terpene alcohols by the reaction
of corresponding acids or alcohols with aluminum or
aluminum isopropoxide are known [8–10].
A,
B, and
C
β
D
β
We have found recently that the high reactivity of
aluminum phenoxide favors its alkylation with terpene
alcohols with high selectivity to give terpenophenols of
different structural types [11].
A,
B
C
In this work, we have studied the alkylation of aluꢀ
minum phenoxide with bicyclic unsaturated terpenes
(camphene,
ꢀpinene) as a development of concept of
reaction realization in organized medium.
β
;
;
+
+
+
We found that the reaction of aluminum phenoxide
+
with camphene at 100 C leads to phenyl isobornyl
°
A
B
C
D
Institute of Chemistry, Komi Research Center, Ural Branch,
Russian Academy of Sciences, Pervomaiskaya ul. 48,
Syktyvkar, 167982 Russia
All products were isolated by preparative column
chromatography on silica gel (70/230 , petroleum
μ
127

128
KUTCHIN et al.
Al
O
3
100, 160°С
160°С
OH
OH
+ IIa +
+
+
O
O
H
H
O
H
I
IIa
III
IV
IIb
Scheme 1.
5. Chukicheva, I.Yu. and Kutchin, A.V., Ross. Khim. Zh.
2004, vol. 47, no. 3, pp. 21–37.
6. Chukicheva, I.Yu., Timusheva, I.V., Spirikhin, L.V.,
and Kutchin, A.V., Chem. Nat. Comp., 2007, vol. 43,
no. 3, pp. 245–249.
,
ether–Et2O as an eluent). The structures of obtained
compounds were established on the basis of 1H and 13C
NMR data. Physicochemical constants and spectral
characteristics of compounds
those described earlier [7, 14].
I–IV agree well with
7. Chukicheva, I.Yu., Spirikhin, L.V., and Kutchin, A.V.,
Zh. Org. Khim., 2008, vol. 44, no. 1, pp. 69–73.
8. Vyshinskaya, L.I., Vasil’eva, G.A., and Vishꢀ
nyakova, T.A., Zh. Org. Khim., 1997, vol. 67, no. 3,
pp. 367–369.
ACKNOWLEDGMENTS
This work was supported by the Russian Academy
of Sciences (the program of the Presidium of the RAS
no. 18 “Development of Methods for Preparation of
Chemical Compounds and Design of New Materiꢀ
als,” project no. 09ꢀPꢀ3ꢀ1010).
9. Shmerkovich, M.E., Matveev, Yu.S., and Kutchin, A.V.,
Khim. Rast. Syr’ya, 1999, no. 1, pp. 5–12.
10. Matveev, Yu.S., Kataeva, N.A., Kozhemyakina, T.I.,
and Kutchin, A.V., Koord. Khim., 1999, vol. 25, no. 12,
pp. 900–907.
11. Kutchin, A.V., Fedorova, I.V., Koroleva, A.A., and
Chukicheva, I.Yu., Dokl. Chem., 2010, vol. 434, part 2,
pp. 266–268 [Dokl. Akad. Nauk, 2010, vol. 434, no. 6,
pp. 768–770].
12. Chukicheva, I.Yu., Koroleva, A.A., Timusheva, I.V.,
and Kutchin, A.V., Izv. Vyssh. Uchebn. Zaved., Khim.
Khim. Tekhnol., 2009, no. 1, pp. 27–33
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DOKLADY CHEMISTRY Vol. 437
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2011