EP0808920A1 - Process for the electrochemical reduction of organic compounds - Google Patents

Abstract

A process for the electrochemical reduction of an organic compound by bringing the organic compound into contact with a cathode, the cathode comprising a carrier made of an electrically conductive material and an electrically conductive, cathodically polarized layer formed thereon by precoating.

Description

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

So far, the electrochemical reduction of organic compounds has been used industrially only in exceptional cases, e.g. for cathodic dimerization of acrylonitrile. The industrial use of electrochemical reduction on cathodes has so far been due to economically inadequate current densities and thus too small space-time yields (STA), too low current yields, the formation of hydrogen, and too low selectivities with regard to several possible reduction steps, lack of availability special catalytically active cathodes on an industrial scale and / or short service lives of the catalytically active cathodes have not been 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, this reaction too, which is carried out using a flow reactor with a glass frit and a powdery embedded therein Raney nickel is carried out as an electrically conductive substance as a cathode, hydrogen is formed.

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, after the catalytically active layer has been inactivated, the electrodes frequently have to be removed from the electrolysis apparatus and fed to an external regeneration, so that short catalyst service lives preclude economic use of the electrochemical synthesis system. Another disadvantage is the complex production of the catalytically active layer as such and the difficulties in achieving a sufficient connection with the carrier electrode. The development effort for a classic electrode coating process is economically justified only for larger technical processes, such as chlor-alkali electrolysis or the cathodic dimerization of acrylonitrile. The use of commercially available heterogeneous catalysts is often forbidden because a thermal change in thermal coating processes or a covering of the active areas in cold adhesive processes cannot be ruled out.

A catalytically active electrode, which flows through a filter layer consisting of a suspension of finely dispersed catalyst material on a porous body is used according to EP-B 0 479 052 in a process for the separation of metal ions from process and waste water.

In view of the prior art set out above, the object of the invention is to provide a process for reducing organic compounds which, on the one hand, delivers high space-time yields, enables high selectivity for compounds which can be reduced several times, and which avoids the formation of hydrogen during the reduction and is applicable on an industrial scale.

This object is achieved according to the invention by means of a method for the electrochemical reduction of an organic compound by bringing the organic compound into contact with a cathode, the cathode comprising a carrier made of a conductive material and an electrically conductive, cathodically polarized layer formed thereon by precoating .

In the context of the method according to the invention, the catalytically active electrode is stabilized in the operating state by the pressure loss at the electrically conductive, cathodically polarized layer formed by precoating. For regeneration, the catalytically active electrode can be suspended again by reversing the flow and removed, for example, by filtration or suction. The reduction of organic compounds is thus carried out on a system which is suitable for forming and dismantling a catalytically active electrode in the process, only interventions being necessary which are already established in the operational practice of a chemical operation, such as switching pumps and actuators.

Electrically conductive materials are used as carriers for the electrically conductive, cathodically polarized layer. For example, materials such as stainless steel, steel, nickel, nickel alloys, tantalum, platinum-coated tantalum, titanium, platinum-coated titanium, graphite, electrode carbon and similar materials and their mixtures are to be mentioned.

Preferably the supports are in the form of permeable porous material, i.e. the carrier has pores. These can be woven in the form of commercially available filter fabrics made of metal wires or carbon fibers. For example, Filter fabric according to the type of linen weave, twill weave, twill braid weave, braid weave and satin weave. In addition, perforated metal foils, metal felts, graphite felts, edge filters, sieves or porous sintered bodies can also be used as large-area supports in the form of plates or candles. The pore size of the support is generally 5 to 300 microns, preferably 50 to 200 microns. When executing the carrier, care must always be taken to ensure that it has as large a free area as possible, so that only slight pressure losses can be overcome when carrying out the method according to the invention. Usually, the supports which can be used well in the context of the present method preferably have at least approximately 30%, more preferably at least approximately 20% and in particular approximately 50% free area, the free area being a maximum of approximately 70%.

All electrically conductive materials can be used as the electrically conductive material for the electrically conductive, cathodically polarized layer, as long as it is possible to form a layer from these by floating onto the carrier defined above.

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

All classic hydrogenation metals, in particular the metals of subgroups I, II and VIII of the Periodic Table, in particular Co, Ni, Fe, Ru, Rh, Re, Pd, Pt, Os, Ir, Ag, Cu, Zn, are preferably used as metals , 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 such as 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 used.

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

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

In addition, the cathodically polarized layer can also be formed by simply floating the carbon-like material defined above.

In addition, the cathode can be built up in situ in that the abovementioned metals and conductive oxides are washed onto the support in each case on carbon-like materials, in particular activated carbon.

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

In particular, layers which contain Pd / C, Pt / C, Ag / C, Ru / C, Re / C, Rh / C, Ir / C, Os / C and Cu / C should be mentioned, 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-mentioned metals can be in the form of nanoclusters, the production of which e.g. in DE-A-44 08 512, on surfaces such as e.g. Metals and carbonaceous materials that are washed onto the carrier.

In addition, the cathodically polarized layer can contain an electrically conductive auxiliary material which improves the adhesion of the above-defined metals, metal oxides or nanoclusters to the support or increases the surface of the cathode, with electrically conductive oxides such as magnetites and carbon, in particular activated carbon, carbon black, carbon fiber and graphite are to be mentioned.

In a further embodiment of the present method, a cathode is used, which is obtained by first washing the electrically conductive auxiliary material onto the support and then this auxiliary material in situ by reducing salts of metals of I., II. And / or VIII Subgroup is doped with these metals on the coated electrode. As salts of the above Metals are preferably 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 built up in situ by the fact that the above-mentioned metals or metal oxides are applied directly or after application of the electrically conductive auxiliary material are washed onto the carrier.

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 ratio of filter pressure loss and hydraulic throughput is guaranteed and an optimal mass transfer is possible. Generally the average particle size is about 1 to about 400 µm, preferably about 30 to about 150 µm, 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, the pore size of the support generally exceeds the average diameter of the particles forming the layer, so that two or more particles form bridges over the interspaces during the formation of the layer on the support, which has the advantage that the formation of the layer on the support results in no appreciable flow obstruction for the solution containing the organic compound to be reduced. Preferably the pore size of the support is about two to about four times the average particle size of the particles forming the layer. Of course, supports with pore sizes which are smaller than the average particle size of the particles forming the layer can also be used in the context of the present invention, but attention must then be paid very precisely to the flow obstruction emanating from the layer which forms.

As already indicated above, the cathode used according to the invention is formed in situ by floating the constituents forming the layer onto the electrically conductive support, the constituents forming the layer Particle-containing solution flows through the carrier until the entire solids content of this solution is suspended or held.

After the reduction has ended or when the catalytically active layer has been used up, it can be separated from the support by simply switching the flow direction and disposed of or regenerated independently of the reduction. After the used layer has been completely removed from the system, it is then possible again to coat the support again with the particles forming the layer and, after these particles have been completely suspended, continue to reduce the organic compound.

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, but temperatures between approximately 20 ° C. and approximately 50 ° C., in particular in the vicinity of room temperature, are preferred.

Depending on the compound to be reduced, the process according to the invention can be carried out in acid, i.e. at a pH below 7, preferably -2 to 5, more preferably 0 to 3, in neutral, i.e. at a pH of about 7, and in basic, i.e. medium is carried out at a pH which is above 7, preferably from 9 to 14 and in particular from 12 to 14.

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

In the context of the method according to the invention, the type of cell type used, the shape and the arrangement of the electrodes have no decisive influence, so that in principle all cell types customary 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 disruptively changed 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 avoid chemical side reactions to exclude 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 the case of 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. Perforated materials such as nets, expanded metal sheets, lamellae, profile webs, grids and smooth sheets can generally be used as electrode materials. In the case of the plane-parallel electrode arrangement, this takes place in the form 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 the solvent of the anolyte. For example, graphite electrodes are preferably used in organic systems, while materials or coatings with a low oxygen overvoltage are preferably used in aqueous systems. Examples of acidic anolytes are titanium or tantalum carriers with electrically conductive intermediate layers on which electrically conductive mixed oxides of IV. To VI. Subgroup are applied, which are doped with metals or metal oxides of the platinum group to name.

In the case of basic anolytes, iron or nickel anodes are preferably used.

In principle, all protic solvents, i.e. Solvents that contain or release protons and / or can form hydrogen bonds, e.g. Water, alcohols, amines, carboxylic acids etc., if necessary. in a mixture with aprotic polar solvents, e.g. THF to use in the inventive method. It is preferred to use lower alcohols, e.g. Methanol, ethanol, 1-propanol, isopropanol, 1-butanol, sec-butanol or tert-butanol, ether, such as e.g. Diethyl ether, 1,2-dimethoxyethane, furan, tetrahydrofuran and dimethylformamide are used. Water is further preferred, optionally as a mixture with one or more of the above. Alcohols, ethers and DMF are used, a mixture of water with methanol, THF or DMF being particularly preferred.

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

• Ameisensäure, Essigsäure, Propionsäure, Buttersäure, Valeriansäure, Capronsäure, Önanthsäure, Caprylsäure, Pelargonsäure, Caprinsäure, Undecansäure, Laurinsäure, Tridecansäure, Myristinsäure, Pentadecansäure, Palmitinsäure, Margarinsäure, Stearinsäure, Nonadecansäure, Isobuttersäure, Isovaleriansäure.

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.

• 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.

If organic compounds are used which are not soluble in the abovementioned solvents, these can, however, also be problem-free by means of surface-active substances, in particular higher alcohols as solvents or solvent additive are brought into solution, with 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.

The corresponding alcohols which contain the hydroxyl group on other carbon atoms can of course also be used according to the invention.

When using higher alcohols or higher carboxylic acids or higher amines, it should be noted that the reaction must then be carried out at relatively high temperatures in order to keep the viscosity of the solutions obtained within a range tolerable for carrying out the reaction.

In general, the reduction according to the invention is carried out in the presence of an auxiliary electrolyte. The addition of the same serves to adjust the conductivity of the electrolysis solution and / or to control the selectivity of the reaction. The content of the electrolyte is usually at a concentration of approximately 0.1 to approximately 10, preferably approximately 1 to approximately 5% by weight, based in each case on the reaction mixture. Protonic acids, such as, for example, organic acids, where methanesulfonic acid, benzenesulfonic acid or toluenesulfonic acid can be mentioned, and mineral acids, such as, for example, sulfuric acid and phosphoric acid, are suitable as the auxiliary electrolyte. Neutral salts can also be used as auxiliary electrolytes. Metal cations of lithium, sodium, potassium, but also tetraalkylammonium cations, such as, for example, tetramethylammonium, come as cations. Tetraethylammonium, Tetrabutylammonium and Dibutyldimethylammonium in question. The following are to be mentioned as anions: fluoride, tetrafluoroborate, sulfonates, such as, for example, methanesulfonate, benzenesulfonate, toluenesulfonate, sulfates, such as, for example, sulfate, methylsulfate, ethylsulfate, phosphates, such as, for example, methylphosphate, ethylphosphate, dimethylphosphate, diphenylphosphate, such as methylafluorophosphate, hexafluorophosphate, such as hexafluorophosphate Phenylphosphonate methyl ester.

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

The cations mentioned above can again be used as cations in these basic compounds.

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

The electrochemical reduction according to the invention can be carried out either continuously or batchwise. In both reaction procedures, the cathode is first produced in situ by forming a catalytically active layer on the support by precoating. For this purpose, the carrier is left in 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 to be washed up, until essentially all of the material contained in the suspension is on the support. Whether this is the case can be visually recognized, for example, by the fact that the suspension, which is cloudy at the start of the precoat, becomes clear.

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

When using an intermediate layer, it is also possible to flow through 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 is to be doped, and by applying a suitable voltage to the cell in it To reduce the solution or suspension of existing metal cations in situ at the cathode.

After completion of the production of the cathode, the organic compound to be reduced is then fed into the system and reduced by introducing a precisely defined amount of current into the system. By precisely controlling the amount of electricity supplied, it is possible within the scope of the method according to the invention to isolate even partially reduced connections.

When the organic compounds used as starting materials are completely reduced, the selectivities are at least 70%, in general over 80% and with particularly smooth reductions at greater than 95%.

During the isolation of the manufactured product, any used catalyst can be replaced by reversing the direction of flow in the electrolysis cell, as a result of which the washed-on layer loses contact with the support and the catalyst e.g. can be removed by suction or filtration of the suspension containing them.

The layer can then be built up again as described above and new feed can then be added and reacted.

Furthermore, the steps of conversion (reduction), renewal of the catalyst and renewed conversion (reduction) can also be carried out alternately, by first producing the cathode in situ as described above, then adding the organic compound to be reduced and converting it, after completion of the implementation, the flow direction within the electrolysis cell is changed and the used catalyst, for example is removed by filtering, then the cathode is again built up with fresh material forming the cathodically polarized layer and is then further reduced.

Of course, this change between conversion, removal of the used layer and renewal of the cathode can be repeated as often as desired, which means that the process according to the invention can be carried out not only batchwise, but also continuously, which in particular leads to extremely short downtimes during regeneration or during Changing the catalyst leads.

In a further preferred embodiment of the method according to the invention, the electrolysis unit, consisting of at least one cathode with a common catholyte circuit, is operated stationary as a homogeneously continuous reactor. This means that after the catalyst has been washed once, a defined concentration level of starting materials and products is maintained. For this purpose, the reaction solution is continuously pumped in a circuit via the electrochemically active cathode and educt is continuously fed to the circuit, product being continuously removed from this circuit so that the reactor content remains constant over time.

The advantage of this process control in comparison to the discontinuous reaction control consists in the simpler process control with less equipment.

The reaction-technical disadvantage that either unfavorable concentration ratios (i.e. low reactant concentrations and high product concentrations at the end point of the reaction) or a higher separation effort during work-up must be accepted with the following apparatus arrangement, which is particularly preferred:

At least two electrolysis units are connected in series, the starting material being fed to the first unit and the product being removed from the last unit. This procedure ensures that the concentration in the first electrolysis unit (s) is significantly lower than that in the last unit (s). This means that, on average, higher space-time yields are achieved across all electrolysis units compared to a reaction procedure in which the electrolysis units are operated in parallel.

This cascade connection of the electrolysis units is particularly advantageous when the required production capacity requires the installation of several electrolysis units.

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

Organic compounds which have at least one of the following reducible groups or bonds are preferably reduced: CC double bonds, CC triple bonds, aromatic CC linkages, carbonyl groups, thiocarbonyl groups, carboxyl groups, ester groups, CN triple bonds, CN double bonds, aromatic CN linkages , Nitro groups, nitroso groups, C-halogen single bonds, further preferably reducing an organic compound selected from a group comprising: nitriles, dinitriles, nitro, dinitro compounds, saturated and unsaturated ketones, aminocarboxylic acids.

The following classes of organic compounds in particular can be reduced by the method according to the invention.

Organic compounds that have the following structural unit:

C = C (I)

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 C mindestensC 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 (II)

The above definition includes all organic compounds which have at least one C ― C triple bond, such as, for example, the compounds of the general formula (B),

R ¹ -≡-R ² (B)

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 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 to 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 encompasses all organic compounds which have at least one heterocyclic ring, such as, for example, 5-, 6- or higher-membered, unsaturated heterocycles which contain 1 to 3 nitrogen atoms and / or an oxygen atom. or contain 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 (VI)

The above definition encompasses all organic compounds which have at least one C ― N triple bond, such as dinitriles and mononitriles, the latter being represented by the following general formula (F)

R ¹ - C ≡ N (F)

where R ^{1 is} as defined above.

Organic compounds which have the structural unit (VII):

C - X ² - O _x R ² _y (VII)

R¹ und R²

wie oben definiert sind,

X²

Stickstoff, Phosphor oder Schwefel ist,

x

eine ganze Zähl 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 (G)

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 (VIII)

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 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 gemaß 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, Maloraldehyd, 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-, m-und 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 polyines having 4 to 20, preferably 4 to 10, carbon atoms, such as, for example, butadiene, butadiene, 1,3-, 1,4-pentadiene, pentadiene, 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 having 5 to 20, preferably 5 to 10, carbon atoms, such as, for example, cyclopentene, cyclohexene, cycloheptene, cyclopentadiene, cyclohexadiene, cycloheptatriene, cyclooctatetraene and 4-vinylcyclohexene.
  Cycloalkynes with 6 to 20 C atoms, such as 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 the above structure (IV) with 5 to 12 members, the 1 to 3 nitrogen atoms and / or oxygen or sulfur atoms and at least one CC double bond have in the ring, which can be converted to the corresponding heterocyclic compounds which have at least one CC double bond less than the starting material and, if appropriate, to the corresponding saturated heterocyclic compounds, such as, for example, thiophene, benzo [b] thiophene, dibenzo [b , d] thiophene, thianthrene, pyrans, such as 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, I. sochroman, 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 into the corresponding hydrogenated compounds, in particular
  Carbonyl compounds with 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, propionaldehyde, n-butyraldehyde, valeraldehyde, caproaldehyde, heptaldehyde, Phenylacetaldehyde, acrolein, crotonaldehyde, benzaldehyde, o-, m-, p-tolualdehyde, salicylaldehyde, cinnamaldehyde, o-, m-, p-anisaldehyde, nicotinaldehyde, furfural, glyceraldehyde, glycolaldehyde, citral, vanillin, piperonal, glyoxal, maloraldehyde Succinaldehyde, glutaraldehyde, adipaldehyde, phthalaldehyde, isophthalaldehyde and terephthalaldehyde;
  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 amino carboxylic acids, such as. B. 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 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 sorbic acid,
  and esters of the above-mentioned carboxylic acids 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-butonitrinitrile, adiponitrile, 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-, m- 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 -Trichlor-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-chloro-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, "Ullmanns 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 the selective conversion of Adiponitrile to aminocapronitrile, 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, working in 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-aminobenzitrile, the following materials in particular forming the cathodically polarized layer being used here: Raney-Ni, Raney-Co, likewise likewise in the neutral to basic medium is worked.
• 3. Conversion of aliphatic or aromatic carboxylic acid dinitriles to the corresponding diamines, such as 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) defined under 1. or the materials forming the cathodically polarized layer (dinitriles of aromatic carboxylic acids) defined under 2., in each case under the 2. specified conditions is implemented.
• 4. Conversion of imino-isophoronenitrile to isophoronediamine
  Here, the same materials forming the cathodically polarized layer and under the same conditions as defined under 1. are used.
• 5. Conversion of aromatic dinitro compounds to the corresponding diamino compounds, such as the conversion of dinitrotoluene to diaminotoluene
  The following materials forming 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, working 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 for oxygen development was used as the anode. A Nafion 324 cation exchange membrane (commercial product from Du Pont) served as the separation medium. The divided cell was installed in a two-circuit electrolysis apparatus with pump circuits.

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 of water, 375 g of methanol, 375 g of isobutanol and 65 g of acetic acid were dissolved. 1200 g of the catholyte batch were filled into the cathode circuit.

According to titrimetric determination, the catholyte preparation is free of chloride before the reaction.

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 detected in the reaction discharge, which corresponds to a conversion 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 was converted to 6-aminocapronitrile (ACN), the preparation of the cathode and the electrolysis being carried out in the same manner as in Example 2, but with the electrolysis was already stopped after 4 F / mol ADN. After separation of the NaOH and subsequent distillation 38.7 g (0.34 mol, 68% based on ADN) aminocapronitrile, 16% hexamethylenediamine and 14% ADN isolated. The selectivities were 79% for aminocapronitrile and 18.6% for hexamethylenediamine.

Example 4

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

The preparation of the cathode and the reaction were carried out in the same manner as in Example 2, but the electrolysis was stopped after 2.3 F / mol of acetophenone.

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

Example 5

The reduction of 2-cyclohexanone to cyclohexanol was carried out using the same device and the same anolyte as in Example 2. A mixture of 737 g of methanol, 330 g of water, 11 g of NaOH, 22 g of 2-cyclohexanone and 7.5 g of Raney nickel was used as the catholyte. 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 to 270 g by distillation, diluted with 500 ml of water and extracted with 5 × 200 ml of MTBE. The organic phase was then 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 of cyclohexanone oxime (0.487 mol) and 8 g of 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 a pH of 13 with sodium hydroxide solution, the copper powder was filtered off, the filtrate was concentrated to 639 g and extracted five times with 100 g each of MTBE. After drying and removing the solvent, the crude product was distilled. 35.2 g of cyclohexylamine (73% based on the oxime used) could be isolated as the reaction product.

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, the filtrate was largely concentrated and the crude product was distilled. 23 g of 1,4-butanediol and 12.4 g of 2-butene-1,4-diol were isolated as the reaction product.

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

Example 9

This example was carried out in the same apparatus as example 2, in a modification an edge filter (pore size 100 μm) made of stainless steel was used as the cathode. 1100 g of 1% sulfuric acid were used as the anolyte. The catholyte consisted of a mixture of 806 g of methanol, 377 g of 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 was neutralized with sulfuric acid and the methanol was removed by distillation. After adjusting the pH to 13, extraction was carried out with MTBE. After drying and removing the solvent, the crude product was distilled. 37 g of thienylethylamine could be isolated as 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) made of platinized titanium was used as the cathode. 1200 g of 1% sulfuric acid were used as the anolyte. The catholyte consisted of a mixture of 651 g of 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 and saturated with NaCl. After the phases had been separated, the mixture was distilled. 45 g of thienylethylamine could be isolated as the reaction product.

Example 11

This example was carried out in the same apparatus as Example 2, in a modification an edge filter (pore size 100 μm) made of platinized titanium was used as the cathode. 1200 g of 1% sulfuric acid were used as the anolyte. The catholyte consisted of a mixture of 882 g of methanol, 420 g of 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 was removed from the filtrate by distillation and the remaining crude aqueous solution was extracted with 5 × 100 g of MTBE. After drying and removing the solvent, the crude product was distilled. 54.5 g of homoveratrylamine could be isolated as the reaction product.

Claims (8)

A process for the electrochemical reduction of an organic compound by bringing the organic compound into contact with a cathode, the cathode comprising a carrier made of an electrically conductive material and an electrically conductive, cathodically polarized layer formed thereon by precoating. The method of claim 1, wherein the cathodically polarized layer contains a metal, a conductive metal oxide or a carbon-like material, or mixtures of two or more thereof. A method according to claim 1 or 2, wherein the cathodically polarized layer contains a metal of subgroup I, II or VIII of the periodic table, in each case as free metal or conductive metal oxide, or a mixture of two or more thereof. Method according to 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, each applied to activated carbon. Method according to at least one of claims 1 to 3, wherein the cathodically polarized layer contains Raney nickel, Raney cobalt, Raney silver or Raney iron. Method according to at least one of claims 1 to 5, wherein the carrier made of electrically conductive material has pores. Method according to 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: CC double bonds, CC triple bonds, aromatic CC linkages, carbonyl groups, thiocarbonyl groups, carboxyl groups, ester groups, CN triple bonds, CN double bonds, aromatic CN linkages, nitro groups, nitroso groups, C-halogen single bonds. Method according to at least one of claims 1 to 7, wherein an organic compound is reduced, selected from a group comprising: Nitriles, dinitriles, nitro, dinitro compounds, saturated and unsaturated ketones, aminocarboxylic acids.