Electrolysis: processes – compositions used therein – and methods – Electrolytic synthesis – Preparing organic compound
Reexamination Certificate
1998-10-16
2001-05-29
Wong, Edna (Department: 1741)
Electrolysis: processes, compositions used therein, and methods
Electrolytic synthesis
Preparing organic compound
C205S440000
Reexamination Certificate
active
06238543
ABSTRACT:
FIELD OF THE INVENTION
This invention concerns a process for the electrolytic coupling of carboxylic acids, the process carried out in a polymer electrolyte membrane reactor.
TECHNICAL BACKGROUND OF THE INVENTION
The electrolytic coupling of carboxylic acids, i.e. the Kolbe reaction, is usually carried out in a parallel plate reactor, in the presence of aqueous solvents, organic cosolvents and added salt electrolytes. Furthermore, it is common for the platinum anode electrode material to be consumed during the course of the reaction. Another disadvantage is the potential evolution of hydrogen gas at the cathode with concomitant safety concerns. The following disclosures may be relevant to various aspects of the present invention and may be briefly summarized as follows:
Organic Syntheses, Collective Volume 7, John Wiley and Sons, N.Y., N.Y., 1990, pages 181-185, describes a classical method for the synthesis of dimethyl decanedioate from methyl hydrogen hexanedioate (adipic acid, monomethyl ester).
Z. Ogumi et al., Electrochimica Acta, Vol. 28, No. 11, pp 1687-1693, 1983 discloses the use of platinum catalyst supported on solid polymer electrolyte material as electrodes in the electrolytic coupling of carboxylic acids where cosolvents were added to maintain the polymer electrolytes conductivity. Ogumi discloses the use of a solid polymer electrolyte material coated with catalyst on one side which functioned as an electrode and separator, but not as an electrolyte, in a two chamber electrolytic cell. Ogumi also discloses the use of a solid polymer electrolyte material coated with catalyst on both sides which functioned as an electrode, but not as a separator, in an electrolytic cell.
SUMMARY OF THE INVENTION
Briefly stated, and in accordance with one aspect of the present invention, there is provided an improved process for the preparation of organic compounds of the structure (II) from one or more carboxylic acids of the structures (I) and (I′) according to the equation
where R and R′ are independently selected from the group consisting of hydrogen, alkyl containing from about one to about six carbon atoms, substituted alkyl, phenyl, substituted phenyl, aralkyl and ring-substituted aralkyl, the process comprising the steps of:
a) introducing (I) and (I′) in the vapor state or as neat organic liquids in the absence of an organic solvent to the anode side of a polymer electrode membrane reactor;
b) supplying, concurrently, an oxygen carrying gas to the cathode side of the reactor;
c) passing at least one equivalent of electrical current through the polymer electrode membrane reactor resulting in the formation of the compound (II) on the anode side of the reactor and the formation of water on the cathode side of the reactor; and
d) isolating the compound (II) from the anode side effluent from the polymer electrode membrane reactor. In the above process the polymer electrode membrane reactor may comprise a gas manifold, flow channels, a membrane electrode assembly, and a current collector.
Pursuant to another aspect of the present invention, there is provided a process for the preparation of organic compounds of the structure (II) from one or more carboxylic acids of the structures (I) and (I′) according to the equation
where R and R′ are independently selected from the group consisting of hydrogen, alkyl containing from about one to about six carbon atoms, substituted alkyl, phenyl, substituted phenyl, aralkyl and ring-substituted aralkyl, said process comprising the steps of:
a) introducing (I) and (I′) in the vapor state or as neat organic liquids in the absence of an organic solvent to the anode side of a polymer electrode membrane reactor;
b) passing at least one equivalent of electrical current through the polymer electrode membrane reactor resulting in the formation of the compound (II) on the anode side of said reactor and the formation of hydrogen on the cathode side of said reactor; and
c) isolating the compound (II) from the anode side effluent from the polymer electrode membrane reactor. In this second process the polymer electrode membrane reactor may comprise a gas manifold, flow channels, a membrane electrode assembly, and a current collector.
REFERENCES:
Ogumi et al., “Application of the Solid Polymer Electrolyte (SPE) Method to Organic Electrochemistry—III. Kolbe Type Reactions on Pt-SPE”, Electrochimica Acta, vol. 28, No. 11, pp. 1687-1693, 1983 no month available.*
Yan et al., “A Model for the Kolbe Reaction of Acetate in a Parallel-Plate Reactor”, J. Appl. Electrochem., vol. 26, No. 2, pp. 175-185. abstract only, 1996 no month available.*
D. A. White,Organic Syntheses, Collective vol. 7, 181-185, 1990 no month available.
Z. Ogumi et al.,Electrochimica Acta, 28, No. 11, 1687-1693, 1983 no month available.
Fedkiw Peter S.
Hicks Michael T.
Law, Jr. Clarence Garland
E. I. Du Pont de Nemours and Company
Wong Edna
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