EP0808920B1 - Process for the electrochemical reduction of organic compounds - Google Patents

Description

The present invention relates to a method for electrochemical Reduction of organic compounds.

So far, the electrochemical reduction of organic compounds industrially only in exceptional cases, e.g. for cathodic dimerization of Acrylonitrile. The industrial use of electrochemical reduction up to now is on cathodes due to economically insufficient current densities and thus too small space-time yields (STA), too low current yields, the formation of hydrogen, too low selectivities in view to several possible reduction steps, lack of availability of the special catalytically active cathodes on an industrial scale and / or short service lives of the catalytically active cathodes were not possible.

A computer-based simulation for the electrochemical hydrogenation of glucose is described by V. Anantharaman et al. in J. Electrochem. Soc., 141 , pp. 2742-2752 (1994), the results of this simulation being based on experimental data from K. Park et al. Described in J. Electrochem. Soc., 132, pp. 1850 ff. (1985) or in J. Appl. Electrochem., 16 , p. 941 ff. (1986). As is apparent from this publication, hydrogen is also formed in this reaction, which is carried out using a flow reactor with a glass frit and powdered Raney nickel embedded therein as the electrically conductive substance as the cathode.

It is also known from publications on preparative organic electrochemistry (for example Electrochimica Acta, 39 , pp. 2109-2115 (1994)) that anodes and cathodes which are used in preparative electrochemistry must have special electrochemical properties. Such electrodes are often produced by coating metallic or carbon-like carrier electrodes using appropriately adapted coating methods such as plasma spraying, soaking and baking, hot pressing, etc. (see instead of many EP-B 0 435 434).

A disadvantage of these established manufacturing processes is that the electrodes after inactivation of the catalytically active layer often from the Electrolysis apparatus removed and fed to an external regeneration must be, so that short catalyst life is an economical Exclude use of the electrochemical synthesis system. Another The disadvantage is the complex production of the catalytically active Layer as such and the difficulty in achieving sufficient Connection to the carrier electrode. The development effort for a classic electrode coating process is economically justified often only for larger technical processes, such as chlor-alkali electrolysis or the cathodic dimerization of acrylonitrile. The use of commercial heterogeneous catalysts are often prohibited because one thermal change in thermal coating processes or a Coverage of the active areas during cold gluing processes is not excluded can be.

A catalytically active electrode that consists of a filter layer with a flow through it Suspension of finely dispersed catalyst material on a porous body is carried out according to EP-B 0 479 052 in one process used to separate metal ions from process and waste water.

In view of the prior art set out above, the invention lies in the The task is based on a method for reducing organic compounds to provide, which on the one hand provides high space-time yields, a high Selectivity with multiply reducible compounds enables the Avoid formation of hydrogen during the reduction and in industrial Scale is applicable.

This object is achieved by means of a method for electrochemical reduction of an organic compound by contact bring the organic compound with a cathode, the cathode a carrier made of a conductive material and one on top of it through Pre-formed, electrically conductive, cathodically polarized layer includes.

It is in the operating state within the scope of the method according to the invention the catalytically active electrode due to the pressure drop across the Pre-formed, electrically conductive, cathodically polarized Layer stabilized. The catalytically active electrode can be used for regeneration suspended again by reversing the flow and, for example, by filtration or suction. This makes the reduction more organic Connections carried out on a system that is suitable for a to form and disassemble catalytically active electrode in the process, whereby only interventions that are necessary in the operational practice of a chemical operation, such as switching pumps and Actuators.

As a carrier for the electrically conductive, cathodically polarized layer electrically conductive materials are used. Here are for example Materials such as stainless steel, steel, nickel, nickel alloys, tantalum, platinum-plated Tantalum, titanium, platinized titanium, graphite, electrode carbon and the like To name materials and their mixtures.

Preferably the supports are in the form of permeable porous material, i.e. the carrier has pores. These can be in the form of commercially available filter fabrics be woven from metal wires or carbon fibers. For example, Filter fabric according to the type of linen weave, twill weave, twill weave, the lace weave and the satin weave. Can also also perforated metal foils, metal felts, graphite felts, edge filters, sieves or porous sintered bodies as large supports in the form of plates or Candles are used. The pore size of the support is generally 5 to 300 µm, preferably 50 to 200 µm. When executing the The wearer must always ensure that this is as large as possible free Has area, so when performing the method according to the invention only small pressure drops can be overcome. Usually possess those which can be used well in the context of the present method Carrier preferably at least about 30%, more preferably at least about 20% and especially about 50% free space, the free The maximum area is approximately 70%.

As an electrically conductive material for the electrically conductive, cathodic Polarized layer can use all electrically conductive materials as long as it is possible, by floating on the carrier defined above to form a layer.

The cathodically polarized layer preferably contains a metal conductive metal oxide or carbon-like material such as e.g. Coal, in particular Activated carbon, carbon black or graphite, or a mixture of two or more of it.

All classic hydrogenation metals, in particular, are preferred as metals the metals of subgroups I, II and VIII of the periodic table, especially Co, Ni, Fe, Ru, Rh, Re, Pd, Pt, Os, Ir, Ag, Cu, Zn, Pb and Cd. Ni, Co, Ag and Fe are preferably used as Raney-Ni, Raney-Co, Raney-Ag and Raney-Fe, which may be caused by foreign metals like Mo, Cr, Au, Mn, Hg, Sn or other elements of the periodic table, in particular S, Se, Te, Ge, Ga, P, Pb, As, Bi and Sb can be doped, used.

The metals used according to the invention are preferably finely divided and / or activated form.

Furthermore, conductive metal oxides, e.g. Magnetite become.

In addition, the cathodically polarized layer can also by itself Alluvial formation of the carbonaceous material defined above can be formed.

In addition, the cathode can be constructed in situ by the above metals and conductive oxides each on carbonaceous Materials, especially activated carbon, are washed onto the support.

Thus, the present invention also relates to a method of the here in The type in question, the cathodically polarized layer being a metal or a conductive metal oxide or a mixture of two or more of which, each applied to activated carbon, contains.

In particular, layers containing Pd / C, Pt / C, Ag / C, Ru / C, Re / C, Rh / C, Ir / C, Os / C and Cu / C included, these in turn by foreign metals or other elements of the periodic table, preferably S, Se, Te, Ge, Ga, P, Pb, As, Bi and Sb can be doped.

In addition, the above metals can be in the form of nanoclusters, their manufacture e.g. is described in DE-A-44 08 512, on surfaces, such as. Metals and carbonaceous materials, to the carrier be washed ashore.

In addition, the cathodically polarized layer can be an electrically conductive one Auxiliary material containing the liability of the metals defined above, Metal oxides or nanoclusters on the support improves or the surface the cathode enlarged, with electrically conductive oxides such as magnetite and Coal, especially activated carbon, carbon black, carbon fiber and graphite are.

In a further embodiment of the present method, a Cathode used, which is obtained by first electrically conductive auxiliary material is washed onto the carrier and then this auxiliary material in situ by reduction of salts of metals of the I., II. And / or VIII. Subgroup on the coated electrode with these Metals is doped. As salts of the above Metals are preferred Metal halides, phosphates, sulfates, chlorides, carbonates, nitrates and the metal salts of organic acids, preferably formates, acetates, propionates and benzoates, particularly preferably acetates.

The cathode used according to the invention is constructed in situ by that the above Metals or metal oxides directly or after application of the electrically conductive auxiliary material washed onto the carrier become.

The average particle size of the particles forming the layer defined above and the thickness of the layer is always chosen so that an optimal Relationship between filter pressure loss and hydraulic throughput guaranteed and an optimal mass transfer is possible. In general, the average particle size about 1 to about 400 microns, preferably about 30 to about 150 microns, the thickness of the layer is generally about 0.05 mm to about 20 mm, preferably about 0.1 to about 5 mm.

It should be noted that in the process according to the invention in general the pore size of the support the average diameter of the layer forming particles, so that two or more particles during the Forming the layer on the carrier across the spaces Form bridges, which has the advantage that due to the formation of the layer the carrier no significant flow obstruction for the to be reduced solution containing organic compound is formed. Preferably the pore size of the support is about two to about four times as large like the average particle size of the particles forming the layer. Of course can also be used in the context of the present invention Pore sizes are used that are smaller than the average particle size of the particles forming the layer, but then very precisely the flow obstruction emanating from the layer being formed pay attention.

As already indicated above, the cathode used according to the invention in situ by floating the components forming the layer on the electrically conductive carrier formed, the forming the layer Particle-containing solution flows through the carrier until the entire Solids content of this solution is washed up or held.

After completion of the reduction or when the catalytically active ones have been consumed This can be done by simply switching the flow direction from the layer Carrier separated and disposed of or regenerated regardless of the reduction become. After the used shift is completely out of the system has been removed, it is then possible again with the carrier to coat the particles forming the layer and, after more complete Alluviation of these particles, the reduction of the organic compound to continue.

The current densities within the process according to the invention are generally about 100 to about 10,000 A / m ² , preferably about 1,000 to about 4,000 A / m ² .

The throughput of the solution containing the organic compounds to be reduced is generally about 1 to about 4,000 m ³ / (m ² xh), preferably about 50 to about 1,000 m ³ / (m ² xh). At a system pressure of generally approximately 1 × 10 ⁴ Pa (absolute) to approximately 4 × 10 ⁶ Pa, preferably approximately 4 × 10 ⁴ Pa to approximately 1 × 10 ⁶ Pa, the pressure loss in the layer is approximately 1 at the flow rates used according to the invention x 10 ⁴ Pa to about 2 x 10 ⁵ Pa, preferably about 2.5 x 10 ⁴ Pa to about 7.5 x 10 ⁴ Pa.

The process according to the invention is generally carried out at temperatures between approximately -10 ° C to the boiling point of the solvent or Solvent mixture carried out, but temperatures between about 20 ° C and about 50 ° C, especially near room temperature, are preferred.

The method according to the invention can be dependent on the one to be reduced Compound in acid, i.e. at a pH below 7, preferably is -2 to 5, more preferably 0 to 3, in neutral, i.e. at pH about 7, and in basic, i.e. at a pH, the over 7, preferably 9 to 14 and especially 12 to 14 medium is carried out.

The reaction at normal pressure and at room temperature is particularly preferred carried out.

In the context of the method according to the invention, the type of used Cell type, the shape and arrangement of the electrodes are not decisive Influence, so that in principle all cell types common in electrochemistry can be used.

a) ungeteilte Zellen Ungeteilte Zellen mit planparalleler Elektrodenanordnung oder kerzenförmigen Elektroden kommen bevorzugt dann zum Einsatz, wenn weder Edukte noch Produkte in störender Weise durch den Anodenprozeß verändert werden oder miteinander reagieren. Vorzugsweise werden die Elektroden planparallel angeordnet, weil bei dieser Ausführungsform bei kleinem Elektrodenspalt (1 mm bis 10 mm, vorzugsweise 3 mm) eine homogene Stromverteilung gegeben ist.

b) geteilte Zellen Geteilte Zellen mit planparalleler Elektrodenanordnung oder kerzenförmigen Elektroden kommen vorzugweise dann zum Einsatz, wenn der Katholyt vom Anolyten getrennt sein muß, um z.B. chemische Nebenreaktionen auszuschließen oder um die nachfolgende Stofftrennung zu vereinfachen. Als Trennmedium können Ionenaustauschermembranen, mikroporöse Membranen, Diaphragmen, Filtergewebe aus nichtelektronenleitenden Materialien, Glasfritten sowie poröse Keramiken eingesetzt werden. Vorzugsweise werden Ionenaustauschermembranen, insbesondere Kationenaustauschermembranen, verwendet, wobei darunter wiederum solche Membranen vorzugsweise verwendet werden, die aus einem Copolymer aus Tetrafluorethylen und einem perfluorierten Monomer, das Sulfogruppen enthält, bestehen. Vorzugsweise werden auch bei geteilten Zellen die Elektroden planparallel angeordnet, da bei dieser Ausführungsform bei kleinen Elektrodenspalten (zwei Spalte zu je 0 mm bis 10 mm, bevorzugt anodisch 0 mm, kathodisch 3 mm) eine homogene Stromverteilung gegeben ist. Vorzugsweise liegt das Trennmedium direkt auf der Anode.

The following two types of apparatus are mentioned as examples:

a) Undivided cells Undivided cells with a plane-parallel electrode arrangement or candle-shaped electrodes are preferably used when neither starting materials nor products are changed in a disruptive manner by the anode process or react with one another. The electrodes are preferably arranged plane-parallel, because in this embodiment a homogeneous current distribution is given with a small electrode gap (1 mm to 10 mm, preferably 3 mm).

b) Divided cells Divided cells with a plane-parallel electrode arrangement or candle-shaped electrodes are preferably used when the catholyte has to be separated from the anolyte, for example to rule out chemical side reactions or to simplify the subsequent material separation. Ion exchange membranes, microporous membranes, diaphragms, filter fabrics made of non-electron-conducting materials, glass frits and porous ceramics can be used as the separation medium. Ion exchange membranes, in particular cation exchange membranes, are preferably used, with those membranes which consist of a copolymer of tetrafluoroethylene and a perfluorinated monomer which contains sulfo groups being preferably used. The electrodes are preferably also arranged plane-parallel in divided cells, since in this embodiment a homogeneous current distribution is given in the case of small electrode gaps (two gaps each with 0 mm to 10 mm, preferably anodically 0 mm, cathodically 3 mm). The separation medium is preferably located directly on the anode.

The design of the anode is common to both types of apparatus. As Electrode materials can generally be perforated materials such as Nets, expanded metal sheets, lamellas, profile webs, grids and smooth sheets use. With the plane-parallel electrode arrangement, this is done in Shape of flat surfaces, in the embodiment with candle-shaped electrodes in the form of a cylindrical arrangement.

The choice of anode material or its coating depends on Anolyte solvent. So are preferred in organic systems Graphite electrodes used, while in aqueous systems preferably Materials or coatings with low oxygen overvoltage be used. Examples of acidic anolytes are titanium or Tantalum carrier with electrically conductive intermediate layers, on which electrically conductive mixed oxides of IV. to VI. Subgroup to be applied are doped with metals or metal oxides of the platinum group.

In the case of basic anolytes, iron or nickel anodes are preferred Commitment.

In principle, all protic solvents, i.e. Solvent, which contain or release protons and / or hydrogen bonds can train, e.g. Water, alcohols, amines, Carboxylic acids etc., if necessary. in a mixture with aprotic polar solvents, such as. THF to use in the inventive method. Preferably are reduced because of the conductivity to be maintained Alcohols, e.g. Methanol, ethanol, 1-propanol, isopropanol, 1-butanol, sec-butanol or tert-butanol, ethers, e.g. Diethyl ether, 1,2-dimethoxyethane, Furan, tetrahydrofuran and dimethylformamide are used. Further water is preferred, optionally as a mixture with one or more of the above. Alcohols, ethers and DMF are used, with a mixture of water Methanol, THF or DMF is particularly preferred.

As an alternative to the alcohols mentioned above, the corresponding alcohols can also be used Acids or amines can be used.

Fatty acids are preferably used as carboxylic acids. The following should be mentioned:
Formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, oenanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, isovaleric acid.

If organic compounds are used which are not soluble in the abovementioned solvents, these can, however, also be brought into solution without problems by surface-active substances, in particular higher alcohols as solvents or solvent addition, fatty alcohols in particular being mentioned. Fatty alcohols are understood to mean the following alcohols:
1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 10-undecen-1-ol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-pentadecanol, 1- Hexadecanol, 1-heptadecanol, 1-octadecanol.

Of course, the corresponding alcohols are also included Contain hydroxyl group on other carbon atoms, according to the invention applicable.

When using higher alcohols or higher carboxylic acids or Higher amines should be noted that the reaction at relatively high Temperatures must be carried out to maintain the viscosity of the product Solutions in a tolerable range for the implementation Keep area.

In general, the reduction according to the invention is carried out in the presence of a Auxiliary electrolytes made. The addition of the same serves for adjustment the conductivity of the electrolysis solution and / or to control the selectivity the reaction. The content of the electrolyte is usually one Concentration from about 0.1 to about 10, preferably about 1 up to about 5% by weight, based in each case on the reaction mixture. As Auxiliary electrolyte come protonic acids, such as organic acids, whereby Methanesulfonic acid, benzenesulfonic acid or toluenesulfonic acid can be called and mineral acids, e.g. Sulfuric acid and phosphoric acid, into consideration. Neutral salts can also be used as auxiliary electrolytes be used. Metal cations of lithium come as cations, Sodium, potassium, but also tetraalkylammonium cations, e.g. Tetramethylammonium, Tetraethylammonium, tetrabutylammonium and dibutyldimethylammonium in question. The following are to be mentioned as anions: fluoride, tetrafluoroborate, Sulfonates, e.g. Methanesulfonate, benzenesulfonate, toluenesulfonate, Sulfates, e.g. Sulfate, methyl sulfate, ethyl sulfate, phosphates such as e.g. Methyl phosphate, ethyl phosphate, dimethyl phosphate, diphenyl phosphate, hexafluorophosphate, Phosphonates, e.g. Methylphosphonate methyl ester and Phenylphosphonate methyl ester.

Basic compounds, such as e.g. Alkali or alkaline earth metal hydroxides, carbonates, bicarbonates and alcoholates can be used, where the alcoholate anions are methylate, ethylate, butylate and isopropylate are preferably used.

The cations in these basic compounds come again as above cations mentioned in question.

As can be seen directly from what has been said above, the invention can Process not only using a homogeneous solution of the organic compound to be reduced in a suitable solvent be carried out, but also consisting of a two-phase system from a phase containing at least one organic solvent such as defined above and the organic compound to be reduced, and one second, water-containing phase.

The electrochemical reduction according to the invention can either be continuous or be carried out discontinuously. With both reactions the cathode is first produced in situ by placing on the Support a catalytically active layer is formed by floating. To do this, the carrier is left as long as a suspension of the finely divided Metal and / or the conductive metal oxide and / or the nanocluster and / or the carbonaceous material, that is, the material that is washed up should be flowed through until essentially the entire amount of material contained in the suspension on the carrier. If this the case can be visually recognized, for example, that the to At the beginning of the precoat, cloudy suspension becomes clear.

If an intermediate layer is also to be washed up, the Carrier through a suspension of the material forming the intermediate layer flows through until essentially the entire amount used located on the carrier. Subsequently, mm floating of the cathodically Proceed polarized layer forming material as described above.

When using an intermediate layer, it is also possible to the carrier provided with an intermediate layer with a solution or a suspension of a metal salt of a metal with which the carrier layer to be doped, to flow through, and by applying a suitable Voltage to the cell is present in this solution or suspension To reduce metal cations in situ at the cathode.

After completion of the production of the cathode, the reducing organic compound fed into the system and introduced a previously precisely defined amount of electricity into the system. Thanks to the precise control of the amount of electricity supplied, it is within limits of the method according to the invention possible, also partially reduced compounds isolate.

In the complete reduction of the organic used as starting materials Compounds the selectivities are at least 70%, in general over 80% and with particularly smooth reductions with larger ones 95%.

During the isolation of the manufactured product, possibly used Catalyst can be replaced by changing the flow direction in the electrolysis cell is reversed, whereby the stranded layer Loses contact with the support and the catalyst e.g. by suction or filtration of the suspension containing them can be removed.

Then the layer can be built up again as described above and then new educt can be added and implemented.

Furthermore, the steps implementation (reduction), renewal of the catalyst and renewed implementation (reduction) also carried out alternately by first floating the cathode as described above is produced in situ, then the organic to be reduced Connection supplied and this is implemented after the completion of the implementation the flow direction within the electrolytic cell is changed and the spent catalyst, e.g. by filtering, is then removed the cathode in turn with fresh the cathodically polarized layer educational material is built up and then further reduced.

Of course, this change between implementation, removal of the used layer and renewal of the cathode repeated as often as required be, which leads to the fact that the inventive method not only discontinuously, but can also be carried out continuously, what especially at extremely low downtimes during regeneration or leads when changing the catalyst.

In a further preferred embodiment of the invention The process is the electrolysis unit, consisting of at least one Cathode with a common catholyte circuit, stationary as homogeneous continuous reactor operated. That means that after one time Flooding the catalyst with a defined concentration level of starting materials and products. For this, the reaction solution is constantly pumped in a circuit via the electrochemically active cathode and the circuit continuously fed educt, from this circuit constantly Product is removed so that the reactor content is constant over time remains.

The advantage of this process control compared to discontinuous Reaction control consists in the simpler process control with less Apparatus expenditure.

The reaction disadvantage that either unfavorable concentration ratios (i.e. low educt concentrations and high product concentrations at the end point of the reaction) or a higher separation effort at the Refurbishment must be accepted with the following equipment Arrangement that is particularly preferred can be met:

At least two electrolysis units are connected in series, whereby the starting material is fed to the first unit and the product to the last unit is removed. This way of driving ensures that in the first electrolysis unit (s) with significantly cheaper concentration profiles is worked as in the last unit (s). So on average across all electrolysis units compared to a reaction procedure, in which the electrolysis units are operated in parallel, higher space-time yields reached.

This cascade connection of the electrolysis units is then particularly of Advantage if the required production capacity anyway the installation requires multiple electrolysis units.

In principle, organic compounds are in the process according to the invention all organic compounds with reducible groups as starting materials applicable. It can be used as products, depending on the total amount of charge added, both partially reduced compounds as completely reduced compounds can also be obtained. For example starting from an alkyne, the corresponding alkene as well are obtained as the corresponding fully hydrogenated or reduced Alkane.

Organic compounds which have at least one are preferably reduced of the following reducible groups or bonds: C-C double bonds, C-C triple bonds, aromatic C-C linkages, Carbonyl groups, thiocarbonyl groups, carboxyl groups, ester groups, C-N triple bonds, C-N double bonds, aromatic C-N bonds, Nitro groups, nitroso groups, C-halogen single bonds, with further preferably an organic compound is selected from one selected Group containing: nitriles, dinitriles, nitro, dinitro compounds, saturated and unsaturated ketones, aminocarboxylic acids.

In particular, by the method according to the invention the following classes of organic compounds are reduced.

Organic compounds that have the following structural unit: C = C

wobei R¹, R², R³ und R⁴ jeweils unabhängig voneinander Wasserstoff, eine Alkylgruppe, eine Arylgruppe, eine Aralkylgruppe, eine Alkylarylgruppe, eine Alkoxyalkylgruppe, eine Alkoxygruppe oder eine Acylgruppe sind.The above definition includes all organic compounds which have at least one CC double bond, such as, for example, unsaturated carboxylic acids, aromatic compounds which are substituted by one or more alkenyl groups, and compounds of the general formula (A)

wherein R ¹ , R ² , R ³ and R ^{4 are} each independently hydrogen, an alkyl group, an aryl group, an aralkyl group, an alkylaryl group, an alkoxyalkyl group, an alkoxy group or an acyl group.

Organic compounds which have the structural unit (II): C ≡ C

The above definition includes all organic compounds which have at least one CC triple bond, such as, for example, the compounds of the general formula (B), R ¹ - ≡ - R ² where R ¹ and R ^{2 are} as defined above.

Organic compounds which have the structural unit (III):

wobei

R¹

wie oben definiert ist und

X¹

ein Halogenatom, eine Alkoxygruppe, eine NR'R"-Gruppe, eine SR'-Gruppe und eine P(R')₂-Gruppe sein kann, wobei R' und R'' gleich oder verschieden sein können und wie oben für R¹ bis R⁴ definiert sind.

The above definition includes all organic compounds which have at least one aromatic ring of the above formula, such as, for example, all aromatic monocyclic or polycyclic hydrocarbons and monocyclic substituted aromatic compounds of the general formula (C)

in which

R ¹

is as defined above and

X ¹

may be a halogen atom, an alkoxy group, an NR'R "group, an SR 'group and a P (R') ₂ group, where R 'and R"' may be the same or different and as above for R ¹ until R ^{4 are} defined.

wobei

Y

eine NR'-, P(R')₃-Gruppe, Sauerstoff und/oder Schwefel ist und R' wie oben definiert ist,

R⁵

wie oben für R¹ bis R⁴ definiert sein kann und darüber hinaus Halogen sein kann, und

n

eine ganze Zahl von 1 bis 6, m eine ganze Zahl von 1 bis 4 und o und p eine ganze Zahl von 1 bis 3 sind, wobei die maximale Anzahl der Ringatome 12 beträgt.

Organic compounds that have the structural unit (IV)

in which

Y

is an NR'-, P (R ') ₃ group, oxygen and / or sulfur and R' is as defined above,

R ⁵

as defined above for R ¹ to R ⁴ and can also be halogen, and

n

is an integer from 1 to 6, m is an integer from 1 to 4 and o and p are an integer from 1 to 3, the maximum number of ring atoms being 12.

wobei Y, X¹ und R¹ wie oben definiert sind.The above definition includes all organic compounds which have at least one heterocyclic ring, such as 5-, 6- or higher-membered, unsaturated heterocycles which contain 1 to 3 nitrogen atoms and / or an oxygen or sulfur atom, for example compounds of the general formula (D. )

where Y, X ¹ and R ^{1 are} as defined above.

wobei X eine NR"'-Gruppe, Sauerstoff und/oder Schwefel sein kann, wobei R''' eine Alkylgruppe, eine Arylgruppe, eine Alkoxygruppe, Wasserstoff oder eine Hydroxylgruppe sein kann.Organic compounds that have the structural unit (V)

where X can be an NR "'group, oxygen and / or sulfur, where R"''can be an alkyl group, an aryl group, an alkoxy group, hydrogen or a hydroxyl group.

wobei X, R¹ und R² wie oben definiert sind und darüber hinaus auch aliphatische oder aromatische, gesättigte oder ungesättigte Carbonsäurederivate, die dann die Struktur R¹COOR² besitzen, wobei R¹ und R² wieder wie oben definiert sind. The above definition includes all organic compounds which have at least one carbon-heteroatom double bond, such as aldehydes, ketones and the corresponding thio compounds and imines, which can be represented by the following general formula (E)

where X, R ¹ and R ^{2 are} as defined above and also aliphatic or aromatic, saturated or unsaturated carboxylic acid derivatives, which then have the structure R ¹ COOR ² , where R ¹ and R ^{2 are} again as defined above.

Organic compounds that have the structural unit (VI): C ≡ N

The above definition includes all organic compounds which have at least one CN triple bond, such as dinitriles and mononitriles, the latter being represented by the following general formula (F) R ¹ - C ≡ N where R ^{1 is} as defined above.

Organic compounds which have the structural unit (VII): C - X ² - O _x R ² _y

R¹ und R²

wie oben definiert sind,

X²

Stickstoff, Phosphor oder Schwefel ist,

x

eine ganze Zahl von 1 bis 3 ist und y 0 oder 1 ist.

The above definition encompasses all organic compounds which have at least one bond of the above type, ie all heterocarbonyl-analogous compounds of the above type, with particular mention being made of nitro and nitroso compounds, these heterocarbonyl-analogous compounds being represented by the general formula (G) can be displayed R ¹ - X ² -O _x R ² _y in which

R ¹ and R ²

are as defined above,

X ²

Is nitrogen, phosphorus or sulfur,

x

is an integer from 1 to 3 and y is 0 or 1.

Organic compounds which have the structural unit (VIII) C - Z where Z is fluorine, chlorine, bromine, iodine and / or an alkoxy group.

worin

R¹ bis R³ und Z

wie oben definiert sind, und

R⁶

wie oben für R¹ bis R⁴ definiert ist und darüber hinaus eine Formiat-, Trifluoracetat-, Mesylat- und Tosylatgruppe sein kann.

The above definition includes all organic compounds which have halogen atoms as defined above or have an oxyalkyl group, such as saturated hydrocarbons or aromatic hydrocarbons, which are substituted by at least one of the above-mentioned groups and, for example, by the following two general formulas (H) and (I ) can be displayed

wherein

R ¹ to R ³ and Z

are as defined above, and

R ⁶

as defined above for R ¹ to R ⁴ and can also be a formate, trifluoroacetate, mesylate and tosylate group.

The following connection classes or connections can be used in detail are implemented:

1. Zu nennen sind dabei insbesondere Alkene mit 2 bis 20, vorzugsweise 2 bis 10 und insbesondere 2 bis 6 C-Atomen, wie z.B. Ethen, Propen, 1-Buten, 2-Buten, Isobuten, 1-Penten, 2-Penten, 3-Penten, 2-Methyl-1-buten, 3-Methyl-1-buten, 2-Methyl-2-buten, 1-Hexen, 2-Hexen, 3-Hexen, 1-Hepten, 2-Hepten, 3-Hepten, 1-Octen, 2-Octen, 3-Octen, 4-Octen, 1-Nonen, 2-Nonen, 3-Nonen, 4-Nonen, 1-Decen, 2-Decen, 3-Decen, 4-Decen, 5-Decen, 1-Undecen, 5-Undecen, 1-Dodecen, 6-Dodecen, 1-Tridecen, 1-Tetradecen, 1-Pentadecen, 1-Hexadecen, 1-Heptadecen und Tetrahydrogeranylaceton. Alkine mit 2 bis 20, vorzugsweise 2 bis 10 und insbesondere 2 bis 6 C-Atome, wie zum Beispiel Acetylen, Propin, Butin, Pentin, 3-Methyl-1-butin, Hexin, Heptin, Octin, Nonin, Decin, Undecin, Dodecin, Tridecin, Tetradecin, Pentadecin, Hexadecin, Heptadecin, Methylbutinol, Dehydrolinalool, Hydrodehydrolinalool und 1,4-Butindiol.Polyene und Polyine mit 4 bis 20, vorzugsweise 4 bis 10 C-Atomen, wie zum Beispiel Butadien, Butadiin, 1,3-, 1,4-Pentadien, Pentadiin, 1,3-, 1,4-, 1,5-, 2,4-Hexadien, Hexadiin, 1,3,5-Hexatrien, 1,3-, 2,4-, 1,6-Heptadien und 1,3-, 1,7-, 2,4-, 3,5-Octadien.

2. Ungesättigte monocyclische Kohlenwasserstoffe mit mindestens einer Doppel- und/oder Dreifachbindung. Zu nennen sind dabei insbesondere Cycloalkene mit 5 bis 20, vorzugsweise 5 bis 10 C-Atomen, wie zum Beispiel Cyclopenten, Cyclohexen, Cyclohepten, Cyclopentadien, Cyclohexadien, Cycloheptatrien, Cyclooctatetraen und 4-Vinylcyclohexen.Cycloalkine mit 6 bis 20 C-Atomen, wie z.B. Cycloheptin und Cyclooctadiin;monocyclische Aromaten mit 6 bis 12 C-Atomen, wie zum Beispiel Benzol, Toluol, 1,2-, 1,3-, 1,4-Xylol, 1,2,4-, 1,3,5-, 1,2,3-Trimethylbenzol, Ethylbenzol, 1-Ethyl-3-methylbenzol, Cumol, Styrol, Stilben sowie Divinylbenzol.

3. Ungesättigte polycyclische Kohlenwasserstoffe mit 8 bis 20 C-Atomen, wie zum Beispiel Pentalen, Inden, Naphthalin, Azulen, Heptalen, Biphenylen, as-Indacen, s-Indacen, Acenaphthylen, Fluoren, Phenalen, Phenanthren, Anthracen, Fluoranthen, Acephenantrylen, Aceanthrylen, Triphenylen, Pyren, Chrysen, Naphthacen, Pleiaden, Picen, Perylen und Pentaphen;

4. ungesättigte polycyclische Kohlenwasserstoffe mit 8 bis 20 C-Atomen, die über Einfach- oder Doppelbindungen miteinander verknüpft sind, wie zum Beispiel Biphenyl, 1,2'-Binaphthyl, sowie o- und p-Terphenyl.

5. Ungesättigte heterocyclische Systeme mit Einheiten gemäß obiger Struktur (IV) mit 5 bis 12 Gliedern, die 1 bis 3 Stickstoffatome und/oder Sauerstoff- oder Schwefelatome und mindestens eine C-C-Doppelbindung im Ring aufweisen, die zu den entsprechenden heterocyclischen Verbindungen, die mindestens eine C-C-Doppelbindung weniger als das Edukt aufweisen, und ggf. zu den entsprechenden gesättigten heterocyclischen Verbindungen umgesetzt werden können, wie zum Beispiel Thiophen, Benzo[b]thiophen, Dibenzo[b,d]thiophen, Thianthren, Pyrane, wie z.B. 2H-Pyran oder 4H-Pyran, Furan, 1,4- und 1,3-Dihydrofuran, Benzofuran und Isobenzofuran, 4aH-Isochromen, Xanthen, 1H-Xanthen, Phenoxathiin, Pyrrol, 2H-Pyrrol, Imidazol, 4H-Imidazol, Pyrazol, 4H-Pyrazol, Pyridin, Pyrazin, Pyrimidin, Pyridazin, Indolizin, Isoindol, 3aH-Isoindol, Indol, 3aH-Indol, Indazol, 5H-Indazol, Purin, 4H-Chinolizin, Chinolin, Isochinolin, Phthalazin, 1,8-Naphthyridin, Chinoxalin, Chinazolin, Cinnolin, Pteridin, Carbazol, 8aH-Carbazol, β-Carbolin, Phenanthridin, Acridin, Perimidin, 1,7-Phenanthrolin, Phenazin, Phenarsazin, Phenothiazin, Phenoxazin, Oxazol, Isoxazol, Phosphindol, Thiazol, Isothiazol, Furazan, Phosphinolin, Chroman, Isochroman, 2-, 3-Pyrrolin, 2-, 4-Imidazolin, 2-, 3-Pyrazolin, Indolin, Isoindolin, Phosphindolin, 1,2,3-, 1,2,4-, 1,3,4-, 1,2,5-Oxadiazol, 1,2,3-, 1,2,4-, 1,3,4-, 1,2,5-Thiadiazol und 1,2,3-, 1,2,4-, und 1,3,5-Triazin.

6. Organische Verbindungen mit mindestens einer Doppelbindung zwischen einem Kohlenstoffatom und einem von Kohlenstoff verschiedenen Atom, das ausgewählt wird unter Stickstoff, Phosphor, Sauerstoff und Schwefel, wie oben als Struktur (V) definiert, wobei N und P wie oben definiert selbst wiederum substituiert sein können, die zu den entsprechenden hydrierten Verbindungen umgesetzt werden können, wobei insbesondere Carbonylverbindungen mit 2 bis 20 C-Atomen, vorzugsweise 2 bis 10 C-Atomen und insbesondere 2 bis 6 C-Atomen wie z.B. aliphatische und aromatische Aldehyde, wie z.B. Acetaldehyd, Propionaldehyd, n-Butyraldehyd, Valeraldehyd, Caproaldehyd, Heptaldehyd, Phenylacetaldehyd, Acrolein, Crotonaldehyd, Benzaldehyd, o-, m-, p-Tolualdehyd, Salicylaldehyd, Zimtaldehyd, o-, m-, p-Anisaldehyd, Nicotinaldehyd, Furfural, Glyceraldehyd, Glycolaldehyd, Citral, Vanillin, Piperonal, Glyoxal, Malonaldehyd, Succinaldehyd, Glutaraldehyd, Adipaldehyd, Phthalaldehyd, Isophthalaldehyd und Terephthalaldehyd;
Ketone, wie z.B. Aceton, Methylethylketon, 2-Pentanon, 3-Pentanon, 2-Hexanon, 3-Hexanon, Methylisobutylketon, Cyclohexenon, Acetophenon, Propiophenon, Benzophenon, Benzalaceton, Dibenzalaceton, Benzalacetophenon, 2,3-Butandion, 2,4-Pentandion, 2,5-Hexandion, Desoxybenzoin, Chalkon, Benzil, 2,2'-Furil, 2,2'-Furoin, Acetoin, Benzoin, Anthron und Phenanthron; gesättigte und ungesättigte aliphatische und aromatische Mono- und Dicarbonsäuren mit 1 bis 20, vorzugsweise 2 bis 10, weiter bevorzugt 2 bis 6 Kohlenstoffatomen, wie zum Beispiel Ameisensäure, Essigsäure, Propionsäure, Buttersäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, Acrylsäure, Propiolsäure, Methacrylsäure, Crotonsäure, Isocrotonsäure und Ölsäure,
Cyclohexancarbonsäure, Benzoesäure, Phenylessigsäure, o-, m-, p-Toluoylsäure, o-, p-Chlorbenzoesäure, o-, p-Nitrobenzoesäure, Salicylsäure, Phthalsäure, Naphthoesäure, Zimtsäure, Nicotinsäure,
sowie substituierte acyclische und cyclische Carbonsäuren, wie z.B. Milchsäure, Äpfelsäure, Mandelsäure, Salicylsäure, Anissäure, Vanillinsäure, Veratrumsäure,
Oxocarbonsäuren, wie z.B. Glyoxylsäure, Brenztraubensäure, Acetessigsäure, Lävulinsäure;
α-Aminocarbonsäuren, d.h. alle α-Aminocarbonsäuren, wie z.B. Alanin, Arginin, Cystein, Prolin, Tryptophan, Tyrosin und Glutamin,
aber auch andere Aminocarbonsäuren, wie z.B. Hippursäure, Anthranilsäure, Carbaminsäure, Carbazinsäure, Hydantoinsäure, Aminohexansäure, und 3- und 4-Aminobenzoesäure;
gesättigte und ungesättigte Dicarbonsäuren, mit 2 bis 20 Kohlenstoffatomen, wie z.B. Oxalsäure, Malonsäure, Bernsteinsäure, Glutarsäure, Adipinsäure, Pimelinsäure, Korksäure, Azelainsäure, Sebacinsäure, Maleinsäure, Fumarsäure, Phthalsäure, Isophthalsäure, Terephthalsäure, und Sorbinsäure,sowie Ester der oben genannten Carbonsäuren zu nennen sind, wobei insbesondere die Methyl-, Ethyl- und Ethylhexylester zu nennen sind.

7. Organische Verbindungen mit Einheiten gemäß Struktur (VI), also Mono- und Dinitrile mit 2 bis 20, vorzugsweise 2 bis 10, weiter bevorzugt 2 bis 6 Kohlenstoffatomen, die zu den entsprechenden Iminen, Aminen bzw. Aminonitrilen und Diaminen umgesetzt werden können. Dabei sind insbesondere die folgenden Nitrile zu nennen:
   Acetonitril, Propionitril, Butyronitril, Stearinsäurenitril, Acrylnitril, Methacrylnitril, Isocrotonsäurenitril, 3-Butennitril, Propinnitril, 3-Butinnitril, 2,3-Butadiennitril, Glutarsäuredinitril, Maleinsäuredinitril, Fumarsäuredinitril, Adipodinitril, 2-Hexen-1,6-dinitril, 3-Hexen-1,6-dinitril, Methantricarbonitril, Phthalodinitril, Terephthalsäuredinitril, 1,6-Dicyanohexan und 1,8-Dicyanooctan.

8. Heterocarbonylanaloge Verbindungen mit mindestens einer Einheit der oben stehend definierten Struktur (VII), wobei insbesondere Nitro- und Nitrosoverbindungen zu nennen sind, die jeweils zu den entsprechenden reduzierten Verbindungen, wie z.B. Aminen umgesetzt werden können. Insbesondere sind dabei aliphatische oder aromatische, gesättigte oder ungesättigte, acyclische oder cyclische Nitro- und Nitrosoverbindungen mit 1 bis 20, vorzugsweise 2 bis 10, insbesondere 2 bis 6 Kohlenstoffatomen, wie z.B. Nitrosomethan, Nitrosobenzol, 4-Nitrosophenol, 4-Nitroso-N,N-dimethylanilin und 1-Nitrosonaphthalin,
Nitromethan, Nitroethan, 1-Nitropropan, 2-Nitropropan, 1-Nitrobutan, 2-Nitrobutan, 1-Nitro-2-methylpropan, 2-Nitro-2-methylpropan, Nitrobenzol, m-, o- und p-Dinitrobenzol, 2,4- und 2,6-Dinitrotoluol, o-, m- und p-Nitrotoluol, 1- und 2- Nitronaphthalin, 1,5- und 1,8-Dinitronaphthalin, 1,2-Dimethyl-4-nitrobenzol, 1,3-Dimethyl-2-nitrobenzol, 2,4-Dimethyl-1-nitrobenzol, 1,3-Dimethyl-4-nitrobenzol, 1,4-Dimethyl-2,3-dinitrobenzol, 1,4-Dimethyl-2,5-dinitrobenzol und 2,5-Dimethyl-1,3-dinitrobenzol, o-, mund p-Chlornitrobenzol, 1,2-Dichlor-4-nitrobenzol, 1,4-Dichlor-2-nitrobenzol, 2,4-Dichlor-1-nitrobenzol und 1,2-Dichlor-3-nitrobenzol, 2-Chlor-1,3-dinitrobenzol, 1-Chlor-2,4-dinitrobenzol, 2,4,5-Trichlor-1-nitrobenzol, 1,2,4-Trichlor-3,5-dinitrobenzol, Pentachlornitrobenzol, 2-Chlor-4-nitrotoluol, 4-Chlor-2-nitrotoluol, 2-Chlor-6-nitrotoluol, 3-Chlor-4-nitrotoluol, 4-Chlor-3-nitrotoluol, Nitrostyrol, 1-(2'-Furyl)-2-nitroethanol und Dinitropolyisobuten,
o-, m-, p-Nitroanilin, 2,4-, 2,6-Dinitroanilin, 2-Methyl-3-nitroanilin, 2-Methyl-4-nitroanilin, 2-Methyl-5-nitroanilin, 2-Methyl-6-nitroanilin, 3-Methyl-4-nitroanilin, 3-Methyl-5-nitroanilin, 3-Methyl-6-nitroanilin, 4-Methyl-2-nitroanilin, 4-Methyl-3-nitroanilin, 3-Chlor-2-nitroanilin, 4-Chlor-2-nitroanilin, 5-Chlor-2-nitroanilin, 2-Chlor-6-nitroanilin, 2-Chlor-3-nitroanilin, 4-Chlor-3-nitroanilin, 3-Chlor-5-nitroanilin, 2-Chlor-5-nitroanilin, 2-Chlor-4-nitroanilin, 3-Chlor-4-nitroanilin, o-, p- und m-Nitrophenol, 5-Nitro-o-cresol, 4-Nitro-m-cresol, 2-Nitro-p-cresol, 3-Nitro-p-cresol, 4,6-Dinitro-o-cresol und 2,6-Dinitro-p-cresol zu nennen.

9. Halogenhaltige aromatische oder aliphatische Kohlenwasserstoffe oder Verbindungen, die durch eine Alkoxygruppe substituiert sind, (wie oben definiert als Struktur VIII, bzw. Formeln G und H), die zu den entsprechenden Kohlenwasserstoffen reduziert werden können. Als Edukte sind dabei insbesondere Verbindungen mit 2 bis 20 C-Atomen und 1 bis 6, vorzugsweise 1 bis 3 Halogenatomen, vorzugsweise Chlor, Fluor, Brom oder Iod, weiter bevorzugt Chlor, Fluor, Brom und insbesondere Chlor und Brom, wie z.B. Brombenzol und Trichlorethylen, aber selbstverständlich auch alle mit einem oder mehreren der o.g. Halogenatomen oder einer Alkoxygruppe substituierten, unter den Punkten 1. bis 7. genannten Verbindungen zu nennen.

10. Weiterhin können natürliche und synthetische Farbstoffe, wie sie z.B. in "Ullmanns Enzyklopädie der technischen Chemie", 4. Aufl. (1976), Bd 11, S. 99-144 ausführlich beschrieben sind, wobei insbesondere Carotinoide, wie z.B. Astaxanthin, Carotin, Chinon-Farbstoffe, wie z.B. Dianthronyl, Alkannin, Carminsäure, 1,8-Dihydroxy-3-methyl-anthrachinon, Krapp-Farbstoffe, wie z.B. 1,2-, 1,3- und 1,4-Dihydroxyanthrachinon, 1,2,4-Trihydroxyanthrachinon, 1,3-Dihydroxy-2-methyl-anthrachinon und 1,2-Dihydroxy-1-methoxy-anthrachinon, indigoide Farbstoffe, wie z.B. synthetischer oder natürlicher Indigo, Indigotin, Anil und 6,6'-Dibrom-Indigo, Pyron-Farbstoffe, wie z.B. Flavon, Isoflavon und Flavanon zu nennen sind verwendet werden.

Unsaturated acyclic hydrocarbons with at least one double and / or triple bond corresponding to structures (I) and (II) above, which form the corresponding saturated compounds or, if the starting materials have more than one CC double bond and / or at least one CC triple bond , can also be converted to the corresponding compounds which have at least one double bond less than the starting materials or have a double bond instead of a triple bond.

1. Mention should be made in particular of alkenes with 2 to 20, preferably 2 to 10 and in particular 2 to 6, carbon atoms, such as, for example, ethene, propene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, 3-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 1-hexene, 2-hexene, 3-hexene, 1-heptene, 2-heptene, 3- Hepten, 1-octene, 2-octene, 3-octene, 4-octene, 1-non, 2-non, 3-non, 4-non, 1-decene, 2-decene, 3-decene, 4-decene, 5-decene, 1-undecene, 5-undecene, 1-dodecene, 6-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene and tetrahydrogeranylacetone. Alkynes with 2 to 20, preferably 2 to 10 and in particular 2 to 6 C atoms, such as, for example, acetylene, propyne, butyne, pentine, 3-methyl-1-butyne, hexyne, heptine, octyne, nonyne, decyne, undecine, Dodecin, tridecin, tetradecin, pentadecin, hexadecin, heptadecin, methylbutinol, dehydrolinalool, hydrodehydrolinalool and 1,4-butynediol. Polyenes and polyynes with 4 to 20, preferably 4 to 10 carbon atoms, such as butadiene, butadiene, 1.3 -, 1,4-pentadiene, pentadiine, 1,3-, 1,4-, 1,5-, 2,4-hexadiene, hexadiine, 1,3,5-hexatriene, 1,3-, 2,4- , 1,6-heptadiene and 1,3-, 1,7-, 2,4-, 3,5-octadiene.

2. Unsaturated monocyclic hydrocarbons with at least one double and / or triple bond. Particularly noteworthy are cycloalkenes with 5 to 20, preferably 5 to 10, carbon atoms, such as, for example, cyclopentene, cyclohexene, cycloheptene, cyclopentadiene, cyclohexadiene, cycloheptatriene, cyclooctatetraene and 4-vinylcyclohexene e.g. cycloheptin and cyclooctadiin; monocyclic aromatics with 6 to 12 carbon atoms, such as, for example, benzene, toluene, 1,2-, 1,3-, 1,4-xylene, 1,2,4-, 1,3,5 -, 1,2,3-trimethylbenzene, ethylbenzene, 1-ethyl-3-methylbenzene, cumene, styrene, stilbene and divinylbenzene.

3. Unsaturated polycyclic hydrocarbons with 8 to 20 carbon atoms, such as, for example, pentals, indenes, naphthalene, azulene, heptals, biphenyls, as-indacene, s-indacene, acenaphthylene, fluorene, phenals, phenanthrene, anthracene, fluoranthene, acephenane tylene, Aceanthrylene, triphenylene, pyrene, chrysene, naphthacene, pleiades, picene, perylene and pentaphen;

4. unsaturated polycyclic hydrocarbons with 8 to 20 carbon atoms, which are linked to one another via single or double bonds, such as biphenyl, 1,2'-binaphthyl, and o- and p-terphenyl.

5. Unsaturated heterocyclic systems with units according to structure (IV) with 5 to 12 members, which have 1 to 3 nitrogen atoms and / or oxygen or sulfur atoms and at least one CC double bond in the ring, to the corresponding heterocyclic compounds which have at least have a CC double bond less than the starting material, and can optionally be converted to the corresponding saturated heterocyclic compounds, such as, for example, thiophene, benzo [b] thiophene, dibenzo [b, d] thiophene, thianthrene, pyrans, such as, for example, 2H- Pyran or 4H-pyran, furan, 1,4- and 1,3-dihydrofuran, benzofuran and isobenzofuran, 4aH isochromes, xanthene, 1H-xanthene, phenoxathiine, pyrrole, 2H-pyrrole, imidazole, 4H-imidazole, pyrazole, 4H -Pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine, isoindole, 3aH-isoindole, indole, 3aH-indole, indazole, 5H-indazole, purine, 4H-quinolizine, quinoline, isoquinoline, phthalazine, 1,8-naphthyridine, quinoxaline , Quinazoline, cinnoline, pteridine, carbazole, 8aH -Carbazole, β-carboline, phenanthridine, acridine, perimidine, 1,7-phenanthroline, phenazine, phenarsazine, phenothiazine, phenoxazine, oxazole, isoxazole, phosphindole, thiazole, isothiazole, furazane, phosphinoline, chroman, isochroman, 2-, 3- Pyrroline, 2-, 4-imidazoline, 2-, 3-pyrazoline, indoline, isoindoline, phosphindoline, 1,2,3-, 1,2,4-, 1,3,4-, 1,2,5-oxadiazole , 1,2,3-, 1,2,4-, 1,3,4-, 1,2,5-thiadiazole and 1,2,3-, 1,2,4- and 1,3,5 -Triazine.

6. Organic compounds with at least one double bond between a carbon atom and an atom other than carbon, which is selected from nitrogen, phosphorus, oxygen and sulfur, as defined above as structure (V), where N and P are themselves substituted as defined above can, which can be converted to the corresponding hydrogenated compounds, in particular carbonyl compounds having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms and in particular 2 to 6 carbon atoms, such as, for example, aliphatic and aromatic aldehydes, such as, for example, acetaldehyde and propionaldehyde , n-butyraldehyde, valeraldehyde, caproaldehyde, heptaldehyde, phenylacetaldehyde, acrolein, crotonaldehyde, benzaldehyde, o-, m-, p-tolualdehyde, salicylaldehyde, cinnamaldehyde, o-, m-, p-anisaldehyde, nicotinaldehyde, furfural, glyceraldehyde , Citral, Vanillin, Piperonal, Glyoxal, Malonaldehyde, Succinaldehyde, Glutaraldehyde, Adipaldehyde, Phthalaldehyde, Isophthalaldehyde and Terephthalal dehyd;
Ketones such as acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, methyl isobutyl ketone, cyclohexenone, acetophenone, propiophenone, benzophenone, benzalacetone, dibenzalacetone, benzalacetophenone, 2,3-butanedione, 2,4- Pentanedione, 2,5-hexanedione, deoxybenzoin, chalcone, benzil, 2,2'-furil, 2,2'-furoin, acetoin, benzoin, anthrone and phenanthrone; saturated and unsaturated aliphatic and aromatic mono- and dicarboxylic acids with 1 to 20, preferably 2 to 10, more preferably 2 to 6 carbon atoms, such as, for example, formic acid, acetic acid, propionic acid, butyric acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, Acrylic acid, propiolic acid, methacrylic acid, crotonic acid, isocrotonic acid and oleic acid,
Cyclohexane carboxylic acid, benzoic acid, phenylacetic acid, o-, m-, p-toluoyl acid, o-, p-chlorobenzoic acid, o-, p-nitrobenzoic acid, salicylic acid, phthalic acid, naphthoic acid, cinnamic acid, nicotinic acid,
as well as substituted acyclic and cyclic carboxylic acids, such as lactic acid, malic acid, mandelic acid, salicylic acid, anisic acid, vanillic acid, veratrum acid,
Oxocarboxylic acids such as glyoxylic acid, pyruvic acid, acetoacetic acid, levulinic acid;
α-aminocarboxylic acids, ie all α-aminocarboxylic acids, such as alanine, arginine, cysteine, proline, tryptophan, tyrosine and glutamine,
but also other aminocarboxylic acids, such as, for example, hippuric acid, anthranilic acid, carbamic acid, carbazinic acid, hydantoic acid, aminohexanoic acid, and 3- and 4-aminobenzoic acid;
saturated and unsaturated dicarboxylic acids with 2 to 20 carbon atoms, such as, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid and the sorbic acid mentioned above, and also sorbic acid, and ester are to be mentioned, in particular the methyl, ethyl and ethylhexyl esters.

7. Organic compounds with units according to structure (VI), ie mono- and dinitriles with 2 to 20, preferably 2 to 10, more preferably 2 to 6 carbon atoms, which can be converted to the corresponding imines, amines or aminonitriles and diamines. The following nitriles should be mentioned in particular:
Acetonitrile, propionitrile, butyronitrile, stearonitrile, acrylonitrile, methacrylonitrile, isocrotonitrile, 3-butenenitrile, propynitrile, 3-butynitrile, 2,3-butadiene nitrile, glutaronitrile, maleic dinitrile, fumaric acid hexinitrile, 3-butynitrinitrile, adipinitrile, 3-butynitrile Hexen-1,6-dinitrile, methane tricarbonitrile, phthalonitrile, terephthalic acid dinitrile, 1,6-dicyanohexane and 1,8-dicyanooctane.

8. Heterocarbonyl-analogous compounds having at least one unit of the structure (VII) defined above, in particular mentioning nitro and nitroso compounds, which can each be converted into the corresponding reduced compounds, such as, for example, amines. In particular, aliphatic or aromatic, saturated or unsaturated, acyclic or cyclic nitro and nitroso compounds with 1 to 20, preferably 2 to 10, in particular 2 to 6 carbon atoms, such as, for example, nitrosomethane, nitrosobenzene, 4-nitrosophenol, 4-nitroso-N, N-dimethylaniline and 1-nitrosonaphthalene,
Nitromethane, nitroethane, 1-nitropropane, 2-nitropropane, 1-nitrobutane, 2-nitrobutane, 1-nitro-2-methylpropane, 2-nitro-2-methylpropane, nitrobenzene, m-, o- and p-dinitrobenzene, 2, 4- and 2,6-dinitrotoluene, o-, m- and p-nitrotoluene, 1- and 2-nitronaphthalene, 1,5- and 1,8-dinitronaphthalene, 1,2-dimethyl-4-nitrobenzene, 1,3 -Dimethyl-2-nitrobenzene, 2,4-dimethyl-1-nitrobenzene, 1,3-dimethyl-4-nitrobenzene, 1,4-dimethyl-2,3-dinitrobenzene, 1,4-dimethyl-2,5-dinitrobenzene and 2,5-dimethyl-1,3-dinitrobenzene, o-, and p-chloronitrobenzene, 1,2-dichloro-4-nitrobenzene, 1,4-dichloro-2-nitrobenzene, 2,4-dichloro-1-nitrobenzene and 1,2-dichloro-3-nitrobenzene, 2-chloro-1,3-dinitrobenzene, 1-chloro-2,4-dinitrobenzene, 2,4,5-trichloro-1-nitrobenzene, 1,2,4-trichloro -3,5-dinitrobenzene, pentachloronitrobenzene, 2-chloro-4-nitrotoluene, 4-chloro-2-nitrotoluene, 2-chloro-6-nitrotoluene, 3-chloro-4-nitrotoluene, 4-chloro-3-nitrotoluene, nitrostyrene , 1- (2'-furyl) -2-nitroethanol and dinitropolyisobutene,
o-, m-, p-nitroaniline, 2,4-, 2,6-dinitroaniline, 2-methyl-3-nitroaniline, 2-methyl-4-nitroaniline, 2-methyl-5-nitroaniline, 2-methyl-6 -nitroaniline, 3-methyl-4-nitroaniline, 3-methyl-5-nitroaniline, 3-methyl-6-nitroaniline, 4-methyl-2-nitroaniline, 4-methyl-3-nitroaniline, 3-chloro-2-nitroaniline , 4-chloro-2-nitroaniline, 5-chloro-2-nitroaniline, 2-chloro-6-nitroaniline, 2-chloro-3-nitroaniline, 4-chloro-3-nitroaniline, 3-chloro-5-nitroaniline, 2 -Chlor-5-nitroaniline, 2-chloro-4-nitroaniline, 3-chloro-4-nitroaniline, o-, p- and m-nitrophenol, 5-nitro-o-cresol, 4-nitro-m-cresol, 2 -Nitro-p-cresol, 3-nitro-p-cresol, 4,6-dinitro-o-cresol and 2,6-dinitro-p-cresol.

9. Halogen-containing aromatic or aliphatic hydrocarbons or compounds which are substituted by an alkoxy group (as defined above as structure VIII or formulas G and H) which can be reduced to the corresponding hydrocarbons. The starting materials here are in particular compounds having 2 to 20 carbon atoms and 1 to 6, preferably 1 to 3 halogen atoms, preferably chlorine, fluorine, bromine or iodine, more preferably chlorine, fluorine, bromine and in particular chlorine and bromine, such as, for example, bromobenzene and Trichlorethylene, but of course also all of the compounds mentioned under points 1 to 7, which are substituted by one or more of the above-mentioned halogen atoms or an alkoxy group.

10. Natural and synthetic dyes, as described in detail in, for example, "Ullmann's Encyclopedia of Industrial Chemistry", 4th edition (1976), vol. 11, pp. 99-144, in particular carotenoids, such as, for example, astaxanthin, carotene Quinone dyes such as dianthronyl, alkannin, carminic acid, 1,8-dihydroxy-3-methylanthraquinone, madder dyes such as 1,2-, 1,3- and 1,4-dihydroxyanthraquinone, 1,2 , 4-trihydroxyanthraquinone, 1,3-dihydroxy-2-methylanthraquinone and 1,2-dihydroxy-1-methoxyanthraquinone, indigo dyes, such as synthetic or natural indigo, indigotine, anil and 6,6'-dibromo Indigo, pyrone dyes, such as flavone, isoflavone and flavanone should be mentioned.

1. Umsetzung von Dinitrilen gesättigter aliphatischer Dicarbonsäuren zum entsprechenden Aminonitril, wie z.B. die selektive Umsetzung von Adipodinitril zum Aminocapronitril unter weitgehender Vermeidung der vollständigen Reduktion zum Hexamethylendiamin. Für diese Art der Umsetzungen eignen sich insbesondere folgende die kathodisch polarisierte Schicht bildende Materialien:Raney-Ni, Raney-Co und Pd/C, wobei im neutralen bis basischen Medium gearbeitet wird (pH-Wert 7 bis 14).

2. Ferner können auch Dinitrile aromatischer Carbonsäuren zu den entsprechenden Aminonitrilen umgesetzt werden, wie z.B. Phtalodinitril zu 2-Aminobenznitril, wobei hier insbesondere folgende die kathodisch polarisierte Schicht bildende Materialien zur Anwendung kommen:
Raney-Ni, Raney-Co, wobei ebenfalls im neutralen bis basischen Medium gearbeitet wird.

3. Umsetzung von aliphatischen oder aromatischen Carbonsäuredinitrilen zu den entsprechenden Diaminen, wie z.B. die Umsetzung von Adipodinitril zum Hexamethylendiamin Diese Umsetzung wird vorzugsweise mit den unter 1. definierten die kathodisch polarisierte Schicht bildende Materialien (Dinitrile aliphatischer Carbonsäuren) bzw. den unter 2. definierten die kathodisch polarisierte Schicht bildende Materialien (Dinitrile aromatischer Carbonsäuren) durchgeführt, wobei jeweils unter den in 1. bzw. 2. angegebenen Bedingungen umgesetzt wird.

4. Umsetzung von Imino-Isophoronnitril zum Isophorondiamin Hier wird mit den gleichen die kathodisch polarisierte Schicht bildenden Materialien und unter den gleichen Bedingungen, wie unter 1. definiert, gearbeitet.

5. Umsetzung von aromatischen Dinitroverbindungen zu den entsprechenden Diaminoverbindungen, wie z.B. die Umsetzung von Dinitrotoluol zu Diaminotoluol Hierzu werden bevorzugt folgende die kathodisch polarisierte Schicht bildende Materialien verwendet:
Raney-Ni und Pd/C, wobei in ungefähr neutralem Medium (pH-Wert 5 bis 7) gearbeitet wird.

6. Umsetzung von aromatischen Aminocarbonsäuren zu den entsprechenden Aminohydroxyderivaten, wie z.B. die Umsetzung von 2-Aminobenzoesäure zu 2-Aminobenzylalkohol, wobei bei dieser Art von Umsetzung insbesondere die folgenden die kathodisch polarisierte Schicht bildenden Materialien zur Anwendung kommen: Cu-Katalysatoren, wie z.B. Cu/C, wobei im sauren Medium (pH-Wert 0 bis 7) gearbeitet wird.

7. Umsetzung von natürlichen und synthetischen Farbstoffen zu Verbindungen, die an einer oder mehreren C-C-Doppelbindungen hydriert werden, wie z.B. die Umsetzung von Indigo zu Leukoindigo und 1,4-Dihydroxyanthrachinon zu 1,4-Dihydroxy-2,3-dihydroanthrachinon, wobei insbesondere die folgenden die kathodisch polarisierte Schicht bildenden Materialien zum Einsatz kommen: Pd/C, Pt/C, Rh/C und Ru/C, wobei im sauren Medium gearbeitet wird.

The process according to the invention is particularly preferably used for the following reactions:

1. Conversion of dinitriles of saturated aliphatic dicarboxylic acids to the corresponding aminonitrile, such as, for example, the selective conversion of adiponitrile to aminocapronitrile while largely avoiding complete reduction to hexamethylenediamine. The following materials, which form the cathodically polarized layer, are particularly suitable for this type of reaction: Raney-Ni, Raney-Co and Pd / C, the process being carried out in a neutral to basic medium (pH 7 to 14).

2. Furthermore, dinitriles of aromatic carboxylic acids can also be converted to the corresponding aminonitriles, such as, for example, phthalodinitrile to 2-aminobenzonitrile, the following materials in particular forming the cathodically polarized layer being used here:
Raney-Ni, Raney-Co, which also works in a neutral to basic medium.

3. Conversion of aliphatic or aromatic carboxylic acid dinitriles to the corresponding diamines, such as, for example, the conversion of adiponitrile to hexamethylene diamine. This reaction is preferably carried out with the materials forming the cathodically polarized layer (dinitriles of aliphatic carboxylic acids) or those defined under 2 cathodically polarized layer-forming materials (dinitriles of aromatic carboxylic acids) carried out, in each case under the conditions specified in 1 and 2, respectively.

4. Conversion of imino-isophoronenitrile to the isophoronediamine. The same materials that form the cathodically polarized layer and under the same conditions as defined under 1. are used here.

5. Conversion of aromatic dinitro compounds to the corresponding diamino compounds, such as, for example, the conversion of dinitrotoluene to diaminotoluene. The following materials which form the cathodically polarized layer are preferably used for this purpose:
Raney-Ni and Pd / C, working in an approximately neutral medium (pH 5 to 7).

6. Conversion of aromatic aminocarboxylic acids to the corresponding aminohydroxy derivatives, such as, for example, the conversion of 2-aminobenzoic acid to 2-aminobenzyl alcohol, the following materials in particular forming the cathodically polarized layer being used in this type of reaction: Cu catalysts, such as Cu / C, working in an acidic medium (pH 0 to 7).

7. Conversion of natural and synthetic dyes to compounds which are hydrogenated on one or more CC double bonds, such as the conversion of indigo to leucoindigo and 1,4-dihydroxyanthraquinone to 1,4-dihydroxy-2,3-dihydroanthraquinone, where In particular, the following materials forming the cathodically polarized layer are used: Pd / C, Pt / C, Rh / C and Ru / C, the process being carried out in an acid medium.

EXAMPLES example 1

In a divided cell with an anode and cathode area of 100 cm ² each, a filter plate was covered with a 50 µm twill weave made of stainless steel material no. 1.4571 installed as cathode. The filtrate can be removed from a cavity under the filter fabric via a separate filtrate line.

A titanium anode coated with Ta / Ir mixed oxide was used as the anode Development of oxygen used. A Nafion 324 cation exchange membrane was used as the separation medium (Commercial product from Du Pont). The shared Cell was placed in a two-circuit electrolysis apparatus with pump circuits built-in.

The reaction was carried out batchwise in the following order:

1100 g of 5% aqueous sulfuric acid were used as the anolyte.

The catholyte was prepared by adding 5 g of vinclozolin [(RS) -3- (3,5-dichlorophenyl) -5-methyl-5-vinyl-oxazoline-2,4-dione] in a mixture consisting of 500 g water, 375 g methanol, 375 g isobutanol and 65 g acetic acid were solved. 1200 g of the catholyte batch were added to the cathode circuit filled.

After titrimetric determination, the catholyte preparation is before the reaction chloride-free.

With the filtrate drain closed, 15 g of graphite powder was added to the circulating catholyte circuit and dispersed in the circulation. The floating was done by closing the catholyte circulation and opening the filtrate drain. The pressure in the cathode chamber rose to 4 × 10 ⁵ Pa and the filtrate throughput was 12 l / h. In the same way, 5 g of catalyst (Degussa type E101N / D, 10% Pd on carbon) were then additionally washed in. A direct current of 20 A was then applied for 30 minutes, which required a cell voltage of initially 35 V to 7.5 V at the end of the test.

After titrimetric determination, 850 ppm of chloride were discharged into the reaction proven, this corresponds to a turnover of 90%.

A gas chromatographic evaluation of the product obtained confirmed the following implementation:

Example 2

The following example, which relates to the reduction of adiponitrile (ADN) to hexamethylenediamine (HDA), and the subsequent examples were carried out in the following apparatus. Electrolytic cell divided flow type electrolytic cell membrane Nafion-324 anode DeNora DSA (anode area: 100 cm ² ) cathode Armored braid made of stainless steel material no. 1.4571 (cathode area: 100 cm ² , pore size: 50 µm) Flow about 20 l / h through the cathode.

1200 g of 2% sulfuric acid were used as the anolyte.

The catholyte consisted of a mixture of 693 g of methanol, 330 g of H ₂ O, 22 g of NaOH, 55 g of adiponitrile (0.509 mol) and 7.5 g of Raney nickel (BASF H ₁ -50).

The implementation was carried out as follows:
First, the two cell compartments were filled and then the Raney nickel was washed to the above cathode within 10 minutes.

The electrolysis was then carried out at a temperature between 30 and 40 ° C. with a current density of 1000 A / m ² at normal pressure. The electrolysis was stopped after 8.5 F / mol ADN. After the NaOH had been separated off by electrolysis, the product was isolated by distillation. 56 g (95% based on the amount of ADN used) of hexamethylene diamine were obtained.

Example 3

Using the same reaction apparatus, the same anolyte and the same catholyte as in Example 2, adiponitrile became 6-aminocapronitrile (ACN) implemented, the manufacture of the cathode and the Electrolysis was carried out in the same manner as in Example 2 however, the electrolysis is terminated after 4 F / mol ADN has been. After separation of the NaOH and subsequent distillation 38.7 g (0.34 mol, 68% based on ADN) aminocapronitrile, 16% hexamethylene diamine and 14% ADN isolated. The selectivities were 79% for Aminocapronitrile and 18.6% for hexamethylenediamine.

Example 4

The following implementation was carried out using the same device and using the same anolyte as in Example 2 carried out. A mixture of 110 g (0.92 mol) acetophenone, 638 g of methanol, 330 g of water, 22 g of NaOH and 7.5 g of Raney nickel used.

The manufacture of the cathode and the implementation were the same Performed as in Example 2, but with the electrolysis after 2.3 F / mol acetophenone was stopped.

After dilution with water (1 1), the product was extracted with 5 x 200 ml MTBE (tert-butyl methyl ether), evaporation and distillation isolated, and 101.3 g (yield: 90% based on acetophenone) Obtain 1-phenylethanol.

Example 5

The reduction from 2-cyclohexanone to cyclohexanol was used the same device and the same anolyte as in example 2 performed. A mixture of 737 g of methanol, 330 g water, 11 g NaOH, 22 g 2-cyclohexanone and 7.5 g Raney nickel used. The reaction was carried out as in Example 2, with however, the electrolysis was stopped after 6 F / mol of 2-cyclohexanone. The discharge obtained was concentrated by distillation to 270 g, with 500 ml Diluted water and extracted with 5 x 200 ml MTBE. Then was the organic phase was distilled and 21.7 g of cyclohexanol were obtained, which corresponds to a yield of 95% based on 2-cyclohexanone.

Example 6

This example was carried out in the same apparatus as Example 2. 1100 g of 1% sulfuric acid were used as the anolyte. The Catholyte consisted of a mixture of 418 g of methanol, 318 g of dist. Water, 297 g of sodium methyl sulfate solution 7.4% in methanol, 55 g Cyclohexanone oxime (0.487 mol) and 8 g copper powder.

The implementation was carried out as follows:
First, the cell compartments were filled and then the copper powder washes onto the above cathode within 10 minutes. Thereafter, the electrolysis was carried out at a temperature between 30 and 50 ° C with a current density of 1000 A / m ² under normal pressure. A charge of 12 F / mol based on the oxime used was applied.

For working up, the catholyte was adjusted to pH with sodium hydroxide solution from 13, the copper powder filtered off, the filtrate concentrated to 639 g and extracted five times with 100 g MTBE each. After drying and removal the crude product of the solvent was distilled. As a reaction product 35.2 g of cyclohexylamine (73% based on the oxime used) be isolated.

Example 7

This example was carried out in the same apparatus as Example 2. 1100 g of 1% sulfuric acid were used as the anolyte. The Catholyte consisted of a mixture of 418 g of methanol, 330 g of dist. Water, 297 g sodium methyl sulfate solution, 7.4% in methanol, 55 g 2-butyne-1,4-diol (0.64 mol) and 15 g Raney nickel (BASF H1-50).

The reaction was carried out analogously to Example 6:
A charge of 4.5 F / mol based on the diol used was applied.

For working up, the catholyte was filtered and the filtrate was largely concentrated and distilled the crude product. 23 g 1,4-butanediol and 12.4 g of 2-butene-1,4-diol can be isolated.

Example 8

This example was carried out in the same apparatus as Example 2. 1100 g of 1% sulfuric acid were used as the anolyte. The Catholyte consisted of a mixture of 704 g of methanol, 330 g of dist. Water, 11 g sulfuric acid, 55 g nitrobenzene (0.447 mol) and 8 g copper powder.

The reaction was carried out analogously to Example 6:
A charge of 6.45 F / mol based on the substrate was applied.

For working up, the catholyte was adjusted to pH with sodium hydroxide solution from 13, the copper powder filtered off, the filtrate concentrated to 597 g and extracted five times with 100 g MTBE each. After drying and removal the crude product of the solvent was distilled. As a reaction product 26.2 g of aniline could be isolated.

Example 9

This example was carried out in the same apparatus as example 2, in a modification, an edge filter (pore size 100 µm) was made Stainless steel used as the cathode. There were 1100 g of 1% sulfuric acid Anolyte used. The catholyte consisted of a mixture of 806 g Methanol, 377 g dist. Water, 52 g sodium hydroxide, 48 g 2-thienylacetonitrile (0.391 mol) and 30 g Raney nickel (BASF H1-50).

The reaction was carried out at 21 ° C. and a current density of 1000 A / m ² . The starting material was added in 14 portions. A charge of 6.45 F / mol based on the substrate was applied.

For working up, the nickel powder was filtered off, the catholyte with Neutralized sulfuric acid and removed the methanol by distillation. To Adjusting the pH to 13 was extracted with MTBE. After drying and removing the solvent, the crude product was distilled. As 37 g of thienylethylamine could be isolated from the reaction product.

Example 10

This example was carried out in the same apparatus as example 2, in a modification, an edge filter (pore size 100 µm) was made platinized titanium used as cathode. There were 1200 g of 1% sulfuric acid used as an anolyte. The catholyte consisted of a mixture 651 g ethylene glycol dimethyl ether, 651 g, dist. Water, 28 g sodium hydroxide, 70 g 2-thienylacetonitrile (0.569 mol) and 50 g Raney nickel (BASF H1-50).

The reaction was carried out at 23 ° C. and a current density of 1000 A / m ² . A charge of 5.5 F / mol based on the substrate was applied.

For working up, the nickel powder was filtered off, the filtrate was mixed with 4% sodium hydroxide added and saturated with NaCl. After separation of the Phases were distilled. 45 g of thienylethylamine could be used as the reaction product be isolated.

Example 11

This example was carried out in the same apparatus as example 2, in a modification, an edge filter (pore size 100 µm) was made platinized titanium used as cathode. There were 1200 g of 1% sulfuric acid used as an anolyte. The catholyte consisted of a mixture 882 g methanol, 420 g dist. Water, 28 g sodium hydroxide, 70 g veratryl cyanide (0.395 mol) and 50 g Raney nickel (BASF H1-50).

The reaction was carried out at 21 ° C. and a current density of 1000 A / m ² . A charge of 4 F / mol based on the substrate was applied.

For working up, the nickel powder was filtered off, the methanol from the Filtrate removed by distillation and the remaining aqueous crude solution with 5x each 100 g MTBE extracted. After drying and removing the solvent the crude product was distilled. 54.5 g Homoveratrylamine can be isolated.

Claims (8)

1. A process for the electrochemical reduction of an organic compound by bringing the organic compound into contact with a cathode, wherein the cathode comprises a support made of an electrically conductive material and an electrically conductive, cathodically polarized layer formed thereon in situ by alluviation.
2. The process as claimed in claim 1, wherein the cathodically polarized layer contains a metal, a conductive metal oxide or a carbonaceous material or mixtures of two or more thereof.
3. The process as claimed in claim 1 or 2, wherein the cathodically polarized layer contains a metal of the Ist, IInd or VIIIth subgroup of the Periodic Table of the Elements, in each case as the free metal or conductive metal oxide, or a mixture of two or more thereof.
4. The process as claimed in at least one of claims 1 to 3, wherein the cathodically polarized layer contains a metal or a conductive metal oxide or a mixture of two or more thereof, applied to activated carbon in each case.
5. The process as claimed in at least one of claims 1 to 3, wherein the cathodically polarized layer contains Raney nickel, Raney cobalt, Raney silver or Raney iron.
6. The process as claimed in at least one of claims 1 to 5, wherein the support made of electrically conductive material has pores.
7. The process as claimed in at least one of claims 1 to 6, wherein an organic compound is reduced which has at least one of the following reducible groups or bonds: C-C double bonds, C-C triple bonds, aromatic C-C linkages, carbonyl groups, thiocarbonyl groups, carboxyl groups, ester groups, C-N triple bonds, C-N double bonds, aromatic C-N linkages, nitro groups, nitroso groups, C-halogen single bonds.
8. The process as claimed in at least one of claims 1 to 7, wherein an organic compound is reduced which is selected from a group comprising:
   nitriles, dinitriles, nitro compounds, dinitro compounds, saturated and unsaturated ketones, aminocarboxylic acids.