Electrolysis: processes – compositions used therein – and methods – Electrolytic synthesis – Preparing organic compound
Reexamination Certificate
2002-03-20
2004-05-11
Wong, Edna (Department: 1753)
Electrolysis: processes, compositions used therein, and methods
Electrolytic synthesis
Preparing organic compound
C205S427000
Reexamination Certificate
active
06733652
ABSTRACT:
The present invention relates to a process for the electrolytic transformation of organic compounds, in which one electrode simultaneously serves to transfer both oxidation and reduction equivalents.
An objective of preparative organic electrochemistry is to utilize the processes occurring in an electrochemical process at both electrodes in parallel.
An example of such a process is the oxidative dimerization of 2,6-dimethylphenol which is coupled with the dimerization of maleic esters (M. M. Baizer, in: H. Lund, M. M. Baizer (editors), Organic Electrochemistry, Marcel Dekker, New York, 1991, pages 142 ff.).
A further example is the coupled synthesis of phthalide and t-butylbenzaldehyde, as described in DE 196 18 854.
However, it is also possible to utilize the cathode process and the anode process to prepare a single product or to destroy one starting material. Examples of such electrochemical processes are the production of butyric acid (Y. Chen, T. Chou, J. Chin. Inst. Chem. Eng. 27 (1996) pages 337-345), the anodic dissolution of iron which is coupled with the cathodic formation of ferrocene (T. Iwasaki et al., J. Org. Chem. 47 (1982) pages 3799 ff.) or the decomposition of phenol (A. P. Tomilov et al., Elektrokhimiya 10 (1982) page 239).
A new opportunity opens up when oxidation and reduction take place at one and the same electrode. This means that a substrate receives both oxidation and reduction equivalents either simultaneously or successively.
A successive transfer of oxidation and reduction equivalents at one electrode is possible, for example, in cyclic voltametry in which the potential of the electrode switches between positive and negative values at a predetermined rate within a period of time (cf., for example, D. Sawyer, A. Sobkowiak, J. Roberts Jr., Electrochemistry for Chemists, Second Ed., pages 68-78, John Wiley & Sons, Inc. New York 1995).
In the context of the present invention, it has now been found that an anode is able to transfer reduction equivalents to a substrate which has already taken up anodic redox equivalents.
The process is not restricted to the anode, but can likewise be carried out at the cathode under suitable conditions.
It is an object of the present invention to provide an electrochemical process in which an organic compound is oxidized in one electrode process and the oxidation product is reduced at the same electrode.
We have found that this object is achieved by the process of the present invention for the electrolytic transformation of at least one organic compound in an electrolysis cell, wherein the organic compound is both oxidized and reduced at one electrode.
In a preferred embodiment of the invention, the process of the present invention occurs in an undivided cell.
In a further preferred embodiment of the invention, the organic compound is both oxidized and reduced, preferably hydrogenated, at the anode.
In one preferred embodiment of the invention, the organic compound is hydrogenated by means of hydrogen at the one electrode, with hydrogen being formed as product at the other electrode or being supplied from outside to the electrolysis circuit.
In another preferred embodiment of the invention, the organic compound is both reduced and oxidized, preferably oxygenated, at the cathode. In the following, the invention will be illustrated by the example of anodes which simultaneously oxidize and hydrogenate.
Organic compounds which can be used as starting materials in the process of the present invention are in principle all organic compounds which have reducible groups, preferably a furan or a substituted furan.
The process is not restricted to furan or substituted furans, but extends to all compounds and classes of compounds which are oxidizable or reducible or both by methods of organic electrochemistry. An overview of the classes of compounds is given by H. Lund, M. M. Baizer, (editors) “Organic Electrochemistry”, 3rd edition, Marcel Dekker, New York 1991.
Suitable compounds of the stated classes are, for example, compounds containing double bonds, e.g.
1) Olefins
where R
1
to R
4
are each an alkyl, aryl or alkoxy group, a hydrogen atom, a (substituted) amino group, a halogen atom or a cyano group and the substituents R
1
to R
4
may be identical or different.
The double bonds can be part of open-chain or cyclic compounds, and can be part of the ring or of the chain or of both.
For the purposes of the present invention, cyclic systems containing double bonds can be, in particular, aromatic systems.
In the compounds having a cyclic structure, one or more element(s) of the cyclic structure can be an unsubstituted or substituted heteroatom such as N, S, O, P.
The cyclic compounds may bear one or more functional substituents of the following types:
carboxyl groups, carbonyl groups (and N analogues), carboxymethyl groups, nitrile groups, isonitrile groups, azo (azoxy) groups, nitro groups, amino groups, substituted amino groups, halogens.
2) Alkynes
where R
5
and R
6
are each a hydrogen atom or an aryl, alkyl, carboxyl or alkoxycarbonyl group, and the substituents R
5
and R
6
may be identical or different.
3) Carbonyl Compounds
R
7
—CO—R
8
where R
7
and R
8
are each an aryl, alkyl, alkoxy or aryloxy group or a substituted amino group or a halogen atom, and the substituents R
7
and R
8
may be identical or different.
In a preferred embodiment of the process of the present invention, furan is used. Apart from furan, substituted furans such as the following compounds are also preferred:
furfural (furan 2-aldehyde), alkyl-substituted furans, furans bearing —CHO, —COOH, —COOR groups, where R is an alkyl, benzyl, aryl or, in particular, a C
1
-C
4
alkyl group, —CH(OR
1
)(OR
2
) groups, where R
1
and R
2
may be identical or different and R
1
and R
2
are each an alkyl, benzyl, aryl or, in particular, C
1
-C
4
-alkyl group, and —CN groups in the 2, 3, 4 or 5 positions.
In the reaction of organic compounds according to the present invention, it is possible to use solvents and electrolyte salts as are described in H. Lund, M. M. Baizer, (editors) “Organic Electrochemistry”, 3rd edition, Marcel Dekker, New York 1991.
According to the present invention, the oxidation of furans is preferably carried out in the presence of methanol or in the presence of ethanol or a mixture thereof, but more preferably in the presence of methanol. These substrates can simultaneously be a reactant and solvent.
As solvents in the reaction of furans, it is generally possible to use all suitable alcohols in addition to the organic compound and the compound used for oxidation.
As electrolyte salts in the reaction of furans in the process of the present invention, it is possible to use not only NaBr but also, for example, alkali metal halides and/or alkaline earth metal halides, with bromides, chlorides and iodides being conceivable as halides. Ammonium halides can likewise be used.
Pressure and temperature can be matched to the conditions which are customary in catalytic hydrogenations.
In a preferred embodiment of the process of the present invention, the reaction temperature T is <50° C., preferably <25° C., the pressure p is <3 bar and the pH is in the neutral region.
In a preferred embodiment of the process of the present invention, intermediates are introduced in addition to the starting materials which are introduced into the preferably undivided electrolysis cell. The term intermediate refers to the product or products which is/are obtained by the electrolytic oxidation according to the present invention of the organic compound or compounds, in particular a furan or a substituted furan or a mixture of two or more thereof, and is therefore present in the electrolysis circuit. The concentration of additional intermediates is set by means of customary electrochemical and electrocatalytic parameters, for example current density and type and amount of catalyst, or the intermediate is added to the circuit.
In respect of the specific choice of the material of the electrodes, there is no restriction in the process of the present invention, as
Gutenberger Guido
Pütter Hermann
BASF - Aktiengesellschaft
Oblon & Spivak, McClelland, Maier & Neustadt P.C.
Wong Edna
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