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ChemComm
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DOI: 10.1039/C5CC08747C
COMMUNICATION
Journal Name
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the synthetic point of view. Although trifluoromethylbenzene
can be in general hydrolyzed to benzoic acid by the action of
concentrated sulfuric acid at 100oC or by using of superacids,26
these conditions cannot be applied for extended PAHs,
because of the polymerization and numerous side reactions.
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Fig. 5 a) Hydrolysis of 19; b) HPLC profile of the reaction products after
reaction of 19 with sulphuric acid at 100oC; c) HPLC profile of the reaction
mixture as obtained after reaction of 11 on alumina at 150oC for 120 min
(MeOH/AcOH extract). HPLC conditions: 5PYE column, eluent
MeOH:toluene 4:1, 30oC, flow rate 1 mL/min, detection 300 nm.
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To demonstrate the efficiency of our approach the relative large
trifluoromethylated benzophenanthrene 19 was used as a model
compound.27 Hydrolysis experiments with sulfuric acid and triflic 17.
acid gave complex mixtures in both cases. In contrast the hydrolysis
of 19 on non-activated alumina at 150oC for 120 min resulted in
18.
clean CF3 to COOH conversion with 96% yield (Fig. 5).
19.
Summing up we have demonstrated that the C-F bond in CF3
group can be effectively activated at mild conditions. The presented
20.
K. Y. Amsharov, M. A. Kabdulov and M. Jansen, Angew.
Chem. Int. Edit., 2012, 51, 4594.
approach is practical, because it can be scaled up and does not
require expensive reagents. Because of the high tolerance of the
21.
K. Y. Amsharov and P. Merz, J. Org. Chem., 2012, 77, 5445.
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CF3 group to many organic reactions this functionality can be easily
22.
introduced into the PAH system. Direct intramolecular cyclization in
ortho trifluoromethylarenes on activated alumina allows facile
synthesis of cyclic ketones. As a result of unprecedentedly high
selectivity respective products can be obtained in highly pure form
by simple extraction. The high selectivity of the reaction is a
consequence of an effective encapsulation of the reagent in to the
alumina nanopore environment. Further, taking into account the
possibility to perform effective hydrolysis of the CF3 group, the
presented approach opens a way for simple access to various
carboxylated large PAHs molecules. In general our finding
demonstrates that the CF3 functionality can be reconsidered as
synthetically useful functionality and an effective synthon for
carboxyl groups. Further applications of alumina assisted C-F bond
activation are under investigation in our laboratory.
23.
24.
25.
26.
27.
Authors are grateful to the Deutsche Forschungsgemeinschaft
for financial support.
Notes and references
1
T. Hiyama, Organofluorine Compounds Chemistry and
Applications, Springer, New York, 2000
2.
H. Amii and K. Uneyama, Chem. Rev., 2009, 109, 2119.
4 | J. Name., 2012, 00, 1-3
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