Process for the catalytic oxidation of...

Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing

Reexamination Certificate

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C568S367000, C568S361000

Reexamination Certificate

active

06191312

ABSTRACT:

The present invention relates to a catalytic process for the selective oxidation of a bicyclooctanol to give a bicyclooctanone using an active-carbon-supported heteropolymetallate anion catalyst. In particular, the invention relates to oxidizing 1,5-dimethylbicyclo[3.2.1]octan-8-ol to the ketone using oxygen, oxygen-containing gases or air.
BACKGROUND OF INVENTION
Various processes are known for oxidizing secondary alcohols to give ketones. However, these conventional oxidation processes are associated with numerous disadvantages, e.g.
the use of relatively expensive oxidizing agents in stoichiometric quantities or even in excess,
the separation and disposal of used and unused oxidizing agent,
the production of salts, creating disposal costs and making isolation of the product more difficult,
high pressures,
low selectivity, and
lack of complete conversion.
Examples of known established processes are the Oppenauer oxidation using Al systems and the H
2
O
2
oxidation using Ti, Mo and V systems, and transfer (de)hydrogenations.
The conventional processes are therefore frequently expensive and energy-intensive and burdened by considerable material separation problems in the isolation of the product from a complex reaction mixture. It is often difficult to dispose of oxidizing agents and auxiliary chemicals without harming the environment.
An object of the present invention was to provide a process for the selective oxidation of bicyclooctanols to the ketones which avoids the disadvantages of conventional oxidations, has low costs and is environmentally acceptable.
An oxidation process has now been found which uses an active-carbon-supported catalyst comprising a heteropolymetallate anion and which, under mild reaction conditions and even at atmospheric pressure, can use inexpensive oxidizing agents, such as oxygen-containing gases and even air,
and can achieve high conversions and even complete conversion with high selectivities
and without producing salts.
SUMMARY OF THE INVENTION
The present invention therefore provides a process for preparing a bicyclooctanone, in particular 1,5-dialkylbicyclo[3.2.1]octan-8-one, by reacting a bicyclooctanol, in particular 1,5-dialkylbicyclo[3.2.1]octan-8-ol, with
a. a catalyst applied to an active-carbon support and comprising heteropolyoxometallate anions of vanadium, molybdenum and phosphorus, and also a corresponding alkali-metal, alkaline-earth-metal and/or ammonium counter ion, and
b. a gaseous, oxygen-containing oxidizing agent.


REFERENCES:
patent: 3860635 (1975-01-01), Kitchens
patent: 3928246 (1975-12-01), Stadler et al.
patent: 4100197 (1978-07-01), Jaedicke et al.
patent: 4146574 (1979-03-01), Onoada et al.
patent: 5091354 (1992-02-01), Ellis, Jr. et al.
patent: 2 441 604 (1980-06-01), None
Fujibayashi et al. An Efficient Aerobic Oxidation of Various Organic Compounds Catalyzed by Mixed Addenda Heteropolyoxometalates Containing Molybdenum and Vanadium (1996).
Neumann et al. Selective Aerobic Oxidative Dehydrogenation of Alcohols and Amines Catalyzed by a Supported Molybdenum-Vanadium Heteropolyanion Salt Na5PMo2v2040. (1991).
CA:77:87478 abs of Bull Soc Chim Fr by Brun (5) pp. 1825-1834, 1972.
CA:97:72234 abs of Tetrahedron Lett. by Becker 23(18) pp. 1883-1886, 1982.
CA:84:42911 abs of J Am Chem Soc by Mueller 97(23) pp. 6862-6863, 1975.
CA: 86:90097 abs of Arzneim.-Forsch. by Scheiber 26(10) pp. 1797-800, 1976.
CA:101:210915 abs of J Pharm Sci by De la Cuesta et al 73(9) pp. 1307-1309, 1984.

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