KR20010023671A - Electrochemical Reduction Of Organic Compounds - Google Patents

Abstract

The present invention relates to a method for electrochemically reducing an organic compound by contacting an organic compound with a negative electrode comprising a support comprising an electrically conductive material and a cathodic electroconductive layer formed thereon.

Description

Electrochemical Reduction Of Organic Compounds

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

To date, electrochemical reduction of organic compounds has been used only on an industrial scale, in exceptional cases such as, for example, negative dimerization of acrylonitrile. Current densities are inadequate for economics, which have very small space-time yields (STY), very low current yields, hydrogen formation, very low selectivity in terms of many reducible steps, and special catalytic activity Electrochemical reduction on the cathode has not been industrially available until now, since the cathode is not sufficient to be available on a technical scale and / or it means that the activity start time of the catalytically active cathode is very short.

Computer-assisted simulations of the electrochemical hydrogenation of glucose are described by V. Anantharaman et al. Electrochem, Soc., 141, (1994) pp. 2742-2752, the results of this simulation compared to experimental data of K. Park et al. Electrochem. Soc., 132 (1985) pp. 1850 and below] and [J. Appl. Electrochem., 16, (1986) pp. 941 and below.

It can be seen from the literature that this reaction carried out using a continuous reactor comprising a calcined-glass disc as negative electrode and powder Raney nickel embedded as an electrically conductive material likewise generates hydrogen.

It is also known in the literature on manufacturing organic electrochemistry (e.g., Electrochimica Acta, 39, (1994) pp. 2109-2115) that the anode and cathode used in manufacturing electrochemistry must have special electrochemical properties. have. Such electrodes are often manufactured by coated metal or carbon support electrodes through suitably adopted coating methods such as plasma spraying, impregnation and heating, hot pressing (see EP-B 0 435 434 instead of many), and the like.

A disadvantage of this established manufacturing method is that the short catalyst activity initiation time precludes economical use of the electrochemical synthesis system, since the electrode is often removed from the electrolysis device and regenerated externally after deactivation of the catalytically active layer. A further disadvantage is that it is difficult to produce such a catalytically active layer and to make a suitable bond with the supporting electrode. Development efforts for typical electrode coating methods can in many cases be economical only in major industrial processes such as chlor-alkali electrolysis or cathodic dimerization of acrylonitrile. The use of commercially available heterogeneous catalysts is often not a practical option, since in the case of heat coating methods it is not possible to exclude the shielding of the active area in the case of heat transfer or cold-bonding methods.

A catalytically active electrode configured as a sparged filter layer comprising a suspension of catalyst material finely dispersed on a porous substrate is used for the process of separating metal ions from process water and effluent according to EP-B 0 479 052.

In the aspects of the prior art indicated above, the object of the present invention is to obtain high space-time yields on the one hand, and to allow high selectivity to avoid the formation of hydrogen during reduction in the case of multiple reducible compounds, which can be used on an industrial scale. It is to provide a method for reducing an organic compound.

This object is achieved through a method of electrochemically reducing an organic compound by contacting an organic compound with a negative electrode comprising a support comprising a conductive material according to the invention and a cathodic electroconductive layer formed by charging during reaction thereon. .

Within the scope of the novel process during operation, this involves a catalytically active electrode which is stabilized by the pressure drop in the cathodic electroconductive layer formed by the charging. For regeneration purposes, the catalytically active electrode can be resuspended by reversal of flow and released, for example by filtration or removal by suction. Thus, the reduction of organic compounds is carried out on a system suitable for forming and removing catalytically active electrodes in the process and only requiring adjustments already made within the operating performance of the chemical plant, such as the exchange of pumps and the final control of the components. do.

Electrically conductive layers, such as alloy steel, steel, nickel, nickel alloys, tantalum, platinum alloyed tantalum, titanium, platinum alloyed titanium, graphite, electrode carbon and similar materials, and mixtures thereof. It is used as a support for the.

The support is preferably present as a permeable porous material, ie a support having pores. They are woven from metal wires or carbon fibers in the form of commercially available filter fabrics. Common examples include filter fabrics of plain, twill, twill, chain and runners. In addition, a perforated metal foil, a metal felt, a graphite felt, an edge filter, a screen or a porous calcined body may be used as a support having a large surface area in the form of a plate or a candle. The pore size of the support is generally 5 to 300 μm, preferably 50 to 200 μm. The support should be designed to provide the largest openable surface area so that the pressure drop to be overcome in carrying out the method according to the invention is small. In general, a support readily usable within the scope of the method preferably has an open surface area of at least about 30%, more preferably at least about 20% and especially about 50%, with an open surface area of about 70%. It is as follows.

The electroconductive material used as the cathodic electroconductive layer can be any electroconductive material as long as they can form a layer by charging with respect to the support as defined above.

The cathodic layer preferably contains a carbon material such as a metal, a conductive metal oxide or, for example, carbon, in particular activated carbon, carbon black or graphite or a mixture of two or more thereof.

The metals used are preferably all typical hydrogenated metals, in particular metals of subgroups I, II and VIII of the periodic table, in particular Co, Ni, Fe, Ru, Rh, Re, Pd, Pt, Os, Ag, Cu, Zn, Pb And Cd, of which Ni, Co, Ag and Fe are preferably used as Raney Ni, Co, Raney Ag and Raney Fe, any of which are 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.

The metals used according to the invention are preferably present in finely dispersed (or) active form.

It is also possible to use conductive metal oxides such as magnetite.

Also, the cathodic layer may be formed only by the filling of the carbon material as defined above.

In addition, the negative electrode may be constituted by a carbon material deposited on a support during the reaction, in particular the aforementioned metals and conductive oxides on activated carbon.

The invention therefore also relates to a process of the type referred to herein as a cathodic layer containing in each case a metal or conductive metal oxide or a mixture of two or more thereof applied to activated carbon.

In particular impurity metal or other elements of the periodic table, preferably Pd / C, Pt / C, Ag / C, Ru / C, optionally doped with S, Se, Te, Ge, Ga, P, Pb, As, Bi and Sb Preference is given to layers containing, Re / C, Rh / C, Ir / C, Os / C and Cu / C.

In addition, the above-mentioned metals that are loaded onto the support may be in the form of nanoclusters on the surface, such as, for example, metals and carbon materials, for example described in DE-A-44 08 512.

In addition, the cathodic layer improves the adhesion of the nanoclusters on the above-mentioned metals, metal oxides or supports or improves the surface area of the cathode, magnetite and carbon, in particular the electrically conductive oxides such as activated carbon, carbon black, carbon fiber and graphite. It may contain an electrically conductive adjuvant.

In another embodiment of the process, first obtained by means of an electroconductive aid which is deposited on a support and subsequently doped with a metal via reduction of metal salts of subgroups I, II, VIII on the electrode coated during the reaction. Use a cathode. Salts of the above-mentioned metals which are preferably used are metal halides, metal phosphates, metal sulfates, metal chlorides, metal carbonates, metal nitrates and organic acids, preferably formate, acetate, propionate and benzoate, Especially preferred are metal salts of acetate.

In doing so, the negative electrode used according to the invention is constituted during the reaction by the above-mentioned metal or metal oxide which is either directly charged to the support or after application of the electroconductive aid.

The average particle size of the particles forming the layer defined above and the thickness of the layer are always selected to ensure the optimum ratio of filter drop and hydraulic throughput and to allow for optimal mass transfer. The average particle size is generally about 1 to about 400 μm, preferably about 30 to about 150 μm, and the thickness of the layer is generally about 0.05 mm to about 20 mm, preferably about 0.1 to about 5 mm.

Herein in the method according to the invention the pore size of the support generally exceeds the average diameter of the particles forming the layer so that at least two particles form bridges in the gap while a layer is formed on the support, which is a layer on the support. It should be noted that there is an advantage that the formation of does not cause any significant disturbance of flow for the solution containing the organic compound to be reduced. Preferably the pore size of the support is about 2 to 4 times the particles forming the layer. Of course, it is also possible to use a support having a pore size smaller than the average particle size of the particles forming the layer within the scope of the present invention, in which case very close observation should be maintained of the extent to which flow is impeded by the layers formed. .

As already mentioned above, the cathode used in accordance with the invention is characterized by the fact that the total proportion of solids in the solution is reduced by the filling of a solution containing the layer forming particles and the layer forming particles with respect to the electrically conductive support during the reaction. It is formed by spreading the support until it is filled or kept on.

After the reduction is complete or when the catalytically active layer is consumed, they can be separated from the support by simple switching of the flow direction and can be treated or regenerated independently of the reduction, in which the spent layer is completely removed from the system. Thereafter, the support may be recoated one or more times using the particles forming the layer, and after the particles have been completely loaded, the redox of the organic compound may be continued.

In the process according to the invention the current density is generally from about 100 to about 10000 A / m ² , preferably from about 1000 to about 4000 A / m ² .

The throughput of the solution containing the organic compound to be reduced is generally about 1 to about 4000 m ³ / (m ² xh), preferably about 50 to about 1000 m ³ / (m ² xh). Generally the pressure in the system is from about 1 x 10 ⁴ Pa (absolute) to 4 x 10 ⁶ Pa, preferably from about 4 x 10 ⁴ Pa to about 1 x 10 ⁶ Pa, and the layer pressure at the throughput used according to the invention. The drop is about 1 × 10 ⁴ Pa to about 2 × 10 ⁵ Pa, preferably about 2.5 × 10 ⁴ Pa to about 7.5 × 10 ⁴ Pa.

The process according to the invention is generally carried out at a boiling point of from about −10 ° C. to the solvent or solvent mixture, from about 20 ° C. to about 50 ° C., but particularly close to room temperature.

The process according to the invention depends on the compound to be reduced in an acidic medium, ie at a pH of 7 or less, preferably at -2 to 5, more preferably at 0 to 3, in a neutral medium, ie at a pH of about 7, and In a basic medium, ie at a pH of at least 7, preferably at 9-14, in particular 12-14.

Especially preferably the reaction is carried out at standard pressure and room temperature.

Since the type, shape and arrangement of electrodes used within the scope of the method according to the invention do not exhibit any deterministic effect, it is essentially possible to use any cell form common in electrochemistry.

By way of example, the following two devices may be mentioned.

a) undivided cell

Non-dividing cells with planar-parallel electrode arrangements or candles in the form of candles are preferably used when the starting materials as well as the products are not adversely affected by the anode method or do not react with each other. Since this embodiment combines a narrow electrode gap (1 mm to 10 mm, preferably 3 mm) with a uniform current distribution, the electrodes are preferably arranged in plane-parallel.

b) split cell

A non-dividing cell having a planar-parallel electrode arrangement or a candle-type electrode is preferably used when the catholyte is separated from the anolyte, for example to exclude chemical side reactions or to simplify subsequent separation of the material. The separation medium used may be in the form of ion exchange membranes, microporous membranes, diaphragms, filter fabrics made of a material that does not conduct electrons, calcined-glass discs and porous ceramics. Preference is given to using ion exchange membranes, in particular cation exchange membranes, and alternatively to the use of membranes consisting of copolymers of tetrafluoroethylene and perfluorinated monomers containing sulfo groups. Since the present embodiment combines a narrow electrode gap (0 mm to 10 mm, preferably anode 0 mm, cathode 3 mm) with a uniform current distribution, the electrodes are preferably arranged in plane-parallel. Preferably the separation medium is located directly on the anode.

What the two devices have in common is the design of the anode. Suitable electrode materials used are generally perforated materials such as nets, metal mesh, lamellae, forming webs, grids and smooth metal sheets. In the case of a planar-parallel electrode arrangement, this is carried out in embodiments comprising candle-shaped electrode arrangements in the form of flat sheets and in the form of cylinders.

The choice of anode material and its coating depends on the anolyte solvent. That is, it is preferable to use graphite electrodes in organic systems, while it is preferable to use materials or coatings with low oxygen overpotentials in aqueous systems. Examples of acidic anolyte referred to herein are titanium or tantalum supports having an electroconductive mixed oxide of subgroups IV to VI and having an electroconductive intermediate layer doped thereon with a metal or metal oxide of platinum group.

Iron anodes or nickel anodes are preferably used with basic anolyte.

Solvents that can be used in the process according to the invention are essentially all protic solvents, ie those which contain or release protons and / or can form hydrogen bonds, for example water, alcohols, amines, carboxylic acids, etc. Solvents that can be mixed with aprotic polar solvents such as, for example, THF. Because of their ability to maintain conductivity, lower specification alcohols such as, for example, diethyl ether, for example methanol, ethanol, 1-propanol, isopropanol, 1-butanol, secondary-butanol or tert-butanol, Preference is given to ethers such as 1,2-dimethoxyethane, furan, tetrahydrofuran and dimethylformamide. Also preferred are water which can be mixed with one or more of the abovementioned alcohols, ethers and DMF, with methanol, THF or a mixture of DMF and water being particularly preferred.

As an alternative to the abovementioned alcohols, it is also possible to use the corresponding acids or amines.

The carboxylic acid used is preferably formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelagonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid. Fatty acids such as pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, isobutyric acid and isovaleric acid.

In the case of using organic compounds which are insoluble in the above-mentioned solvents, they can alternatively be solutiond without difficulty through higher alcohols, in particular fatty alcohols, as surfactants, in particular as solvents or solvent additives. As used herein, the term fatty alcohol refers to 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 10-undecen-1-ol, 1-dodecanol And alcohols such as 1-tridecanol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, and 1-octadecanol.

Of course, corresponding alcohols which simultaneously carry hydroxy groups on different carbon atoms can likewise be used according to the invention.

Keep in mind that when higher alcohols or higher carboxylic acids or higher amines are used, the conversion is carried out at a relatively high temperature so that the viscosity of the solution obtained is within the acceptable range for carrying out the conversion. Should be.

Reduction according to the invention is generally carried out in the presence of a supporting electrolyte. A supporting electrolyte is added to control the conductivity of the electrolysis solution and / or to control the selectivity of the reaction. Generally the content of electrolyte is in each case from about 0.1 to about 10, preferably from about 1 to about 5 weight percent, based on the reaction mixture. Possible supporting electrolytes include, for example, organic acids such as methanesulfonic acid, benzenesulfonic acid or toluenesulfonic acid, and protic acids such as inorganic acids such as sulfuric acid and phosphoric acid. In addition, the supporting electrolyte used may also be a neutral salt. Suitable cations herein are not only metal cations of lithium, sodium, potassium, but also tetraalkylammonium cations such as, for example, tetramethylammonium, tetraethylammonium, tetrabutylammonium and dibutyldimethylammonium. The anions mentioned are fluorides, tetrafluoroborates, for example sulfonates such as methanesulfonate, benzenesulfonate, toluenesulfonate, sulfates such as sulfate, methyl sulfate, ethyl sulfate, for example methyl phosphate , Phosphates such as ethyl phosphate, dimethyl phosphate, diphenyl phosphate, hexafluorophosphate, for example phosphonates such as methyl methylphosphonate and methyl phenylphosphonate.

In addition, basic compounds such as, for example, hydroxides, carbonates, carbonates and alcoholates of alkali metals or alkaline earth metals are suitable for use and are suitable for the use of methylates, ethylates, butylates and isopropylates in alcoholic anions. Use is preferred.

Suitable cations for such basic compounds include those mentioned above.

Directly from the foregoing, the process according to the invention not only uses a homogeneous solution of the organic compound to be reduced in a suitable solvent, but also contains a phase and water containing at least one organic solvent as defined above and the organic compound to be reduced. It can be carried out in a two phase system consisting of a containing phase.

The electrochemical reduction according to the invention can be carried out continuously or discontinuously. In both reaction forms, the cathode is first prepared by a catalytically active layer formed on the support by charging during the reaction. Due to this, the spraying of the support with a suspension of finely dispersed metal and / or conductive metal oxides and / or nanoclusters and / or carbon materials, i.e. the material to be filled, essentially results in the total amount of material contained in the suspension Until it is held on a support. This is the case, for example, when it can be observed visually through the suspension which becomes cloudy and clear at the beginning of an alluvial.

In addition, when the interlayer is deposited, the support is sparged with a suspension of the material forming the interlayer until essentially the entire amount used is maintained on the support. This is done by the method described above for filling the material forming the cathodic layer.

If an intermediate layer is used, the metal cations present in the solution or suspension are reduced during the reaction at the cathode by sparging the support provided in the intermediate layer with a solution or suspension of the metal salt of the metal doped into the support layer and applying a suitable voltage to the cell. There is an additional option.

After the preparation of the negative electrode is completed, the organic compound to be reduced is fed to the system and the system is supplied with the exact amount of electricity previously defined. By precisely controlling the amount of electricity supplied, it is possible to isolate partially reduced compounds within the scope of the process according to the invention.

In the case of complete reduction of the organic compound used as starting material, the selectivity is at least 70%, in general at least 80% and at least 95%, especially for reductions that proceed smoothly.

In the process of isolating the product produced, reversal of the flow direction in the electrolysis cell as a result of the fact that the packed bed loses contact with the support and the catalyst can be removed, for example, by suction or filtration of the suspension containing the catalyst. There is an option for the spent catalyst to be substituted.

After one or more layers have been configured as described above, fresh starting materials can be fed and converted.

In addition, the stage of the conversion (reduction), the regeneration of the catalyst and the regenerated conversion (reduction) according to the alternative, firstly the negative electrode is prepared during the reaction by charging as described above, then the organic compound to be reduced is used and converted, After the conversion is completed, the spent catalyst is removed, for example by filtration removal, after which the direction of flow in the electrolysis cell changes, and then the cathode is reconstituted with a new material that forms a cathodic layer, followed by reduction. Is performed.

Of course, this shift between conversion, removal of the spent layer and regeneration of the cathode is carried out not only discontinuously but also continuously in accordance with the process according to the invention, which results in extremely short downtimes, particularly during regeneration or replacement of the catalyst. Can be repeated any number of times.

In another preferred embodiment of the process according to the invention, the electrolysis unit comprising one or more cathodes having a common catholyte circuit is operated in standard condition as a uniformly continuous reactor. This means that after the catalyst has been charged once, the starting materials and products maintain the defined concentration levels. This allows for continuous recycling by ejecting the reaction solution through an electrochemically active cathode, the circuit being fed continuously with starting material and withdrawing the product continuously from this circuit, so that the reactor content remains constant over the operating time .

The advantage of the control method of this process compared to discontinuously operated reactions lies in simplified process control involving less complex equipment.

Disadvantages associated with adverse concentration conditions (ie low starting material concentration and high product concentration at the end of the conversion) or conversion that must withstand more difficult separations during processing are offset by the particularly preferred following device arrangement.

Two or more electrolysis units are connected in series, the starting material is fed in the first unit and the product exits in the final unit. This mode of operation ensures that the initial electrolysis unit (s) operate in a concentration profile that is significantly more advantageous than the final unit (s). This means that the space-time yield averaged over all electrolysis units is achieved higher than adjusting the reaction to run the electrolysis units in parallel.

This series arrangement of electrolysis units is particularly advantageous when the production capacity required in any case requires the installation of multiple electrolysis units.

Organic compounds suitable for use in the process according to the invention include essentially any organic compound which contains a reducible group as starting material. Products obtainable in the process include both partially reduced compounds and fully reduced compounds depending on the total charge introduced. For example, when starting from alkyne, both the corresponding alkenes and the corresponding fully hydrogenated or reduced alkanes can be obtained.

Preferably, the organic compound is a CC double bond, CC triple bond, aromatic CC bond, carbonyl group, thiocarbonyl group, carboxyl group, ester group, CN triple bond, CN double bond, aromatic CN bond, nitro group, nitroso group, C-halogen It is a reduced organic compound having at least one reducing group or bond in a single bond, more preferably selected from the group comprising nitrile, dinitrile, nitro compound, dinitro compound, saturated and unsaturated ketones, aminocarboxyl.

The process according to the invention in particular reduces essentially the following classes of organic compounds.

Organic compound containing the following structural unit

<Structure I>

The definition includes all organic compounds containing one or more C-C double bonds, such as, for example, unsaturated carboxylic acids, aromatic compounds substituted with one or more alkenyl groups, and compounds of formula (A).

In the above formula,

R ¹ , R ² , R ³ and R ⁴ are each independently of each other hydrogen, alkyl, aryl, aralkyl, alkylaryl, alkoxyalkyl, alkoxy or acyl.

Organic compound containing structural unit (II).

<Structure II>

The definition includes all organic compounds containing one or more C-C triple bonds, such as, for example, compounds of formula (B).

In the above formula,

R ¹ and R ² are as defined above.

Organic compound containing structural unit (III).

<Structure III>

The definition includes all organic compounds containing 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 formula (C).

In the above formula,

R ¹ is as defined above,

X ¹ may be halogen, alkoxy, NR′R ″, SR ′ and P (R ′) ₂ , wherein R ′ and R ″ may be the same or different and as defined above for R ¹ to R ⁴ ).

Organic compound containing structural unit (IV).

<Structure IV>

In the above formula,

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

R ⁵ may be as defined above for R ¹ to R ⁴ , further may be halogen,

n is an integer of 1-6, m is an integer of 1-4, o and p are an integer of 1-3, and a maximum ring atom is 12.

The above definitions include, for example, unsaturated heterocyclic compounds, for example 5-, 6- or higher, containing 1 to 3 nitrogen atoms and / or oxygen or sulfur atoms, such as for example compounds of formula (D). All organic compounds containing at least one heterocyclic ring are included.

In the above formula,

Y, X ¹ and X ² are as defined above.

Organic compound containing a structural unit (V).

<Structure V>

In the above formula,

X may be NR ′ ″, oxygen and / or sulfur, wherein R ′ ″ is alkyl, aryl, alkoxy, hydrogen or hydroxyl.

The definition includes all organic compounds containing one or more carbon-heteroatom double bonds, such as aldehydes, ketones and the corresponding thio compounds and imines, which can be represented by the formula (E) below.

Wherein X, R ¹ and R ² are as defined above and are further aliphatic or aromatic saturated or unsaturated carboxylic acids having a R ¹ COOR ² structure, wherein R ¹ and R ² are as defined above. Derivatives.

Organic compound containing structural unit (VI).

<Structure VI>

The definition includes all organic compounds containing at least one C-N triple bond such as, for example, dinitrile and mononitrile represented by the formula:

In the above formula,

R ¹ is as defined above.

Organic compound containing structural unit (VII).

<Structure VII>

The definition includes all organic compounds containing at least one of the above types of bonds, in particular those of any heterocarbonyl homologue of the above form in nitro and nitroso compounds, wherein the heterocarbonyl homologs are of formula (G) Is displayed.

In the above formula,

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 compound containing structural unit (VIII).

<Structure VIII>

In the above formula,

Z is fluorine, chlorine, bromine, iodine and / or alkoxy.

The definition includes, for example, a halogen atom or an oxyalkyl group as defined above, such as a saturated hydrocarbon or an aromatic hydrocarbon substituted with one or more of the aforementioned groups, for example represented by the following two formulas (H) and (I) It includes all organic compounds that can be.

In the above formula,

R ¹ to R ³ and Z are as defined above,

R ⁶ is as defined above for R ¹ to R ⁴ and may further be formate, trifluoroacetate, mesylate and tosylate.

In essence, the following compounds or classes of compounds can be converted.

When converted to obtain a corresponding saturated compound, or if the starting material contains one or more CC double bonds and / or one or more CC triple bonds, alternatively having double bonds instead of double bonds or triple bonds smaller than the starting material Unsaturated bicyclic hydrocarbons having at least one double bond and / or triple bond corresponding to the above structures (I) and (II) to obtain the corresponding compounds.

1. Particularly mentioned herein are those having 2 to 20, preferably 2 to 10 and especially 2 to 6 carbon atoms, 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-heptene, 1-octene, 2-octene, 3-octene, 4-octene, 1-nonene, 2-nonene, 3-nonene, 4-nonene, 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 Alkenes such as -heptadecene and tetrahydrogeranylacetone.

2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, especially 2 to 6 carbon atoms, for example, acetylene, propylene, butyne, pentine, 3-methyl-1-butyne, hexyne, heptin, octin, nonnin, desine, undecine , Alkynes such as dodecine, tridecine, tetradecine, pentadecine, hexadecine, heptadecin, methylbutynol, dihydrolinalol, hydrodihydrolinalol and 1,4-butyndiol.

4 to 20 carbon atoms, preferably 4 to 10 carbon atoms, for example butadiene, butadiene, 1,3-, 1,4-pentadiene, pentadiene, 1,3-, 1,4-, 1 , 5-, 2,4-hexadiene, hexadiyne, 1,3,5-hexatriene, 1,3-, 2,4-, 1,6-heptadiene and 1,3-, 1,7 -Polyenes such as 2,4-, 3,5-octadiene and polyyne.

2. Unsaturated monocyclic hydrocarbons having one or more double and / or triple bonds.

Particularly mentioned among them are those having 5 to 20 carbon atoms, preferably 5 to 10 carbon atoms, for example cyclopentene, cyclohexene, cycloheptene, cyclopentadiene, cyclohexadiene, cycloheptatriene, cyclooctatetraene and Cycloalkenes such as 4-vinylcyclohexene.

Cycloalkynes such as cycloheptin and cyclooctadiyne having 6 to 20 carbon atoms.

6 to 12 carbon atoms, for example benzene, toluene, 1,2-, 1,3-, 1,4-xylene, 1,2,4-, 1,3,5-, 1,2,3- Monocyclic aromatic compounds such as trimethylbenzene, ethylbenzene, 1-ethyl-3-methylbenzene, cumin, styrene, stilbene and divinylbenzene.

3. 8 to 20 carbon atoms, for example pentylene, indene, naphthalene, azulene, heptylene, biphenylene, as-indacene, s-indacene, acenaphthylene, fluorene, phenylene, phenane Unsaturated polycyclic hydrocarbons such as tren, anthracene, fluoranthene, acefenanthryl, aceanthryl, triphenylene, pyrene, chrysene, naphthacene, pleadene, pisene, perylene and pentaphene.

4. Unsaturated polycyclic hydrocarbons such as biphenyl, 1,2'-binafthyl and o- and p-terphenyl having 8 to 20 carbon atoms bonded to each other via single or double bonds.

5. Containing from 1 to 3 nitrogen atoms and / or oxygen or sulfur atoms and at least one CC double bond in the ring and converted to obtain a corresponding heterocyclic compound having at least one CC double bond less than the starting material, If necessary it can be converted to give the corresponding saturated heterocyclic compound, for example thiophene, benzo [b] -thiophene, dibenzo [b, d] thiophene, thianthrene, pyran (eg 2H -Pyran or 4H-pyran), furan, 1,4- and 1,3-dihydrofuran, benzofuran and isobenzofuran, 4aH-isochromen, xanthene, 1H-xanthene, phenoxanthine, pyrrole, 2H-pyrrole, imidazole, 4H-imidazole, pyrazole, 4-H-pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine, isoindole, 3aH-isoindole, indole, 3aH-indole, indah Sol, 5H-indazole, purine, 4H-quinolizine, quinoline, isoquinoline, phthalazine, 1,8-naphthyridine, quinoxaline, quinazoline, cinnoline, fr Lidine, carbazole, 8aH-carbazole, β-carboline, phenanthridine, acridine, perimidine, 1,7-phenanthroline, phenazine, phenarazine, phenothiazine, phenoxazine, oxazole , Isoxazole, phosphindole, thiazole, isothiazole, furazane, phosphinoline, chromman, isochroman, 2-, 3-pyrroline, 2-, 4-imidazoline, 2-, 3- Pyrazoline, indolin, isoindolin, phosphindolin, 1,2,3-, 1,2,4-, 1,3,4-, 1,2,5-oxadiazole, 1,2,3 -5, such as 1,2,4-, 1,3,4-, 1,2,5-thiadiazole and 1,2,3-, 1,2,4- and 1,3,5-triazine Unsaturated heterocyclic system containing units consistent with structure (IV) having from 12 to 12 components.

6. The carbon atom and selected from nitrogen, phosphorus, oxygen and sulfur as defined above as structures (V), N and P, optionally substituted by themselves and converted to the corresponding hydrogenated compound, in particular having from 2 to 20, preferably 2 to 10 and in particular 2 to 6 carbonyl compounds, for example acetaldehyde, propionaldehyde, n-butyraldehyde, valeraldehyde, caproaldehyde, heptaaldehyde, phenylacetaldehyde, Acroline, crotonaldehyde, benzaldehyde, o-, m-, p-tolualdehyde, salicyaldehyde, cinnamic aldehyde, o-, m-, p-anisaldehyde, nicotinaldehyde, perfural, glyceraldehyde, glycolaldehyde, Such as citral, vanillin, piperonal, glyoxal, malonaldehyde, succinic aldehyde, glutaraldehyde, adialdehyde, phthalaldehyde, isophthalaldehyde and terephthalaldehyde Bangjok and an aromatic aldehyde; Acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, methyl isobutyl ketone, cyclohexenone, acetophenone, propiophenone, benzophenone, benzalacetone, dibenzal Acetone, benzalacetophenone, 2,3-butanedione, 2,4-pentanedione, 2,5-hexanedione, dioxybenzoin, chalcone, benzyl, 2,2'-furyl, 2,2 ' Organic compounds having at least one double bond between carbon and atoms other than carbon, such as ketones such as puroin, acetoin, benzoin, anthrone and phenanthrone.

1 to 20, preferably 2 to 10, more preferably 2 to 6 carbon atoms, for example formic acid, acetic acid, propionic acid, butyric acid, caprylic acid, capric acid, lauric acid, myristic acid, pal Mittic acid, stearic acid, acrylic acid, propiolic acid, methacrylic acid, crotonic acid, isocrotonic acid and oleic acid, cyclohexanecarboxylic acid, benzoic acid, phenylacetic acid, o-, m-, p-toluic acid, o-, p Saturated and unsaturated aliphatic and aromatic mono- and dicarboxylic acids such as -chlorobenzoic acid, o-, p-nitrobenzoic acid, salicylic acid, phthalic acid, naphthoic acid, cinnamic acid, nicotinic acid, and for example lactic acid, malic acid, mandelic acid, Substituted bicyclic and cyclic carboxylic acids such as salicylic acid, aniseic acid, vanyl acid, veratroic acid, such as glyoxylic acid, pyruvic acid, acetoacetic acid, levulinic acid, such as alanine Arginine, Cysteine, Proline, Tryptophan Α-aminocarboxylic acids such as tyrosine and glutamine, ie all α-aminocarboxylic acids, as well as, for example, hypuric acid, anthranilic acid, carbamic acid, carbamic acid, hydantoic acid, aminohexanoic acid, and Saturated and unsaturated aliphatic and aromatic mono- and dicarboxylic acids such as other aminocarboxylic acids such as 3- and 4-aminobenzoic acids.

2-20 carbon atoms, for example oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suveric acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid And saturated and unsaturated dicarboxylic acids such as sorbic acid, and esters of the aforementioned carboxylic acids, in particular methyl, ethyl and ethylhexyl esters.

7. Organic compounds containing units consistent with structure (VI), ie 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, converted to the corresponding imines, amines or aminonitriles, respectively And mono- and dinitriles from which diamines can be obtained. Particularly mentioned among these are the following nitriles.

Acetonitrile, propionitrile, butyronitrile, stearonitrile, acrylonitrile, methacrylonitrile, isocrotononitrile, 3-butenecarbonitrile, propynecarbonitrile, 3-butynecarbonitrile, 2,3- Butadienecarbonitrile, glutarodinitrile, maleodinitrile, fumarodinitrile, adipodinitrile, 2-hexene-1,6-dicarbonitrile, 3-hexene-1,6-dicarbonitrile, methanetricarbonitrile, Phthalodinitrile, terephthalodinitrile, 1,6-dicyanohexane and 1,8-dicyanooctane.

8. References are made to heterocarbonyl homologs, in particular nitro and nitroso compounds, which contain at least one unit of structure (VII) as defined above which can be converted in each case to obtain a corresponding reduced compound such as, for example, an amine. do.

Particularly mentioned among these are those having 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms, especially 2 to 6 carbon atoms, 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-nitrobenzene, 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-chloro-3-nitrobenzene, 2-chloro-1,3-dinitrobenzene, 1-chloro-2,4-dinitrobenzene, 2,4,5-trichloro Rho-1-nitrobenzene, 1,2,4-trichloro-3,5-dinitrobenzene, pentachloronitrobenzene, 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-nitro Aniline, 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-nitro Aniline, 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 Aliphatic or aromatic, saturated or unsaturated, bicyclic, such as 2-nitro-p-cresol, 3-nitro-p-cresol, 4,6-dinitro-o-cresol and 2,6-dinitro-p-cresol Or cyclic nitro and nitroso compounds

9. A compound substituted by an alkoxy group (as defined above in structures VIII and in formulas G and H) which may be reduced to a halogen containing aromatic or aliphatic hydrocarbon or a corresponding hydrocarbon.

Particularly mentioned as starting materials are 2 to 20 carbon atoms, 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, preferably chlorine, fluorine, bromine or iodine, more preferably chlorine, fluorine, bromine and In particular chlorine and bromine, for example compounds such as bromobenzene and trichloroethylene, but any compounds mentioned in items 1 to 7 are of course substituted with one or more of the aforementioned halogen atoms or alkoxy groups.

10. Further, see, eg, Ullmanns Enzyklopaedie der technischen Chemie, 4th Edition (1976), Vol. 11, pp. 99-144, natural and synthetic dyes described in detail, among them carotenoids such as, for example, astaxanthin, carotene, for example dianthronyl, alkanine, carminic acid, 1,8-dihydroxy Quinone dyes such as 3-methylanthraquinone, for example 1,2-, 1,3- and 1,4-dihydroxyanthraquinone, 1,2,4-trihydroxyanthraquinone, 1,3- Alizarin dyes such as dihydroxy-2-methylanthraquinone and 1,2-dihydroxy-1-methoxyanthraquinone, for example synthetic or natural indigo, indigotin, anil and 6,6'-dibromo Indigo dyes such as indigo are mentioned, for example pylon dyes such as flavones, isoflavones and flavanones.

Especially preferably, the process according to the invention is used for the following conversion.

1. Conversion of the dinitrile to the corresponding aminonitrile of saturated aliphatic dicarboxylic acids, such as selective reduction of adipodinitrile to aminocapronitrile, for example, while avoiding full reduction to hexamethylenediamine.

Particularly suitable for this type of conversion are the following materials which form a layer which is polarized with a cathode.

Raney Ni, Raney Co and Pd / C, conversion is carried out in neutral to basic medium (pH 7-14).

2. Conversion of the dinitriles of aromatic carboxylic acids to the corresponding aminonitriles, for example from phthalodinitriles to 2-aminobenzonitriles, in which case the following materials form especially cathodic layers Is used.

Raney Ni, Raney Co, conversion is carried out in neutral to basic media.

3. Conversion of aliphatic or aromatic carboxylic acid dinitriles to the corresponding diamines, eg, adipodinitrile to hexamethylenediamine.

This conversion is preferably a material forming an anodized layer as defined in item 1 (dinitrile of aliphatic carboxylic acid) or a material forming an anodized layer as defined in item 2 (aromatic carboxyl Dinitrile of acid), and the conversion is carried out in each case under the conditions specified in 1 and 2, respectively.

4. Conversion of imino-isophorononitrile to isophoronediamine.

The same conditions and materials used to form the same cathodic layer as defined in item 1 are used.

5. Conversion of aromatic dinitro compounds to the corresponding diamino compounds, for example dinitrotoluene to diaminotoluene.

For this purpose, it is preferable to use the following materials for forming the cathodic layer.

Raney Ni and Pd / C, conversion is carried out in approximately neutral medium (pH 5-7).

6. Conversion of aromatic aminocarboxylic acids to the corresponding aminohydroxy derivatives, for example from 2-aminobenzoic acid to 2-aminobenzyl alcohols, the conversion of which forms in particular the following materials forming the cathodic layer Use

For example, a Cu catalyst, such as Cu / C, conversion is carried out in acidic medium (pH 0-7).

7. Conversion of natural and synthetic dyes to compounds that are hydrogenated on one or more CC double bonds, eg indigo to leucoindigo and 1,4-dihydroxyanthraquinone to 1,4-dihydroxy- The following materials are used which form a layer which is converted to 2,3-dihydroanthraquinone, in particular polarized to the cathode.

Pd / C, Pt / C, Rh / C and Ru / C, conversion is carried out in acidic medium.

<Example 1>

In a divided cell each having a positive electrode surface area and a negative electrode surface area of 100 cm ² , a filter plate was coated with 50 μm of the hard cloth of alloy steel material 1.4571 as the negative electrode. The filtrate was withdrawn from the cavity at the bottom of the filter fabric through a separation filtrate line.

Used for the anode is titanium oxide, designed to release oxygen and coated with Ta / Ir mixed oxides. The separation medium used is Nafion-324 cation exchange membrane (commercially available from Du Pont). The divided cells were mounted in a dual-circuit electrolysis device equipped with a pump circuit.

The conversion was carried out discontinuously in the following order.

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

5 g of vinclozoline [(RS) -3- (3,5-dichlorophenyl) -5-methyl-5-vinyl-oxazoline-2,4-dione] was added 500 g of water, 375 g of methanol, A catholyte was prepared by dissolving in a mixture of 375 g isobutanol and 65 g acetic acid. The cathode circuit was filled with 1200 g of catholyte batch.

According to the titration analysis, the catholyte before the reaction was free of chloride.

The filtrate outlet was closed and 15 g of graphite powder was added to the circulating catholyte and dispersed in the circulating fluid. The circulation of the catholyte was interrupted and the filtrate outlet opened to fill. The pressure in the cathode compartment increased to 4 x 10 ⁵ Pa and the throughput of the filtrate was 12 l / h. Subsequently additional charge was carried out in the same way with 5 g of catalyst (Degussa Type E101N / D, 10% palladium on carbon). Over 30 minutes, a DC current of 20 A was initially applied which required a voltage of 35 V and later required a cell voltage of 7.5 V.

According to the titration analysis, 850 ppm of chloride corresponding to 90% conversion was measured in the emissions from the reaction.

The following conversion was confirmed by analyzing the product obtained via gas chromatography.

<Scheme>

<Example 2>

The following and subsequent examples relating to the reduction of adipodinitrile (ADN) to hexamethylenediamine (HDA) were carried out in the following apparatus.

Electrolysis Cell: Split Electrolysis Cell in Flow-Cell Form

Membrane: Nafion-324

Anode: DeNora DSA (Anode surface area: 100 cm ² )

Cathode: armor chain of alloy steel material 1.4571 (cathode surface area: 100 cm ² , pore size: 50 μm)

Throughput: about 20 l / h through cathode

1200 g of 2% strength sulfuric acid was used as anolyte.

Catholyte consisted of a mixture of 693 g of methanol, 330 g of H ₂ O, 22 g of NaOH, 55 g of adipic Fordyce nitrile (0.509 mol) and 7.5 g Raney nickel (BASF H ₁ -50) of the.

The conversion was carried out as follows.

First the two cell compartments were filled and the cathode was washed with Raney nickel over 10 minutes.

Then, electrolysis was performed under standard pressure at a current density of 1000 A / m ² at 30 to 40 ° C. After 8.5 F / mol of ADN, electrolysis was stopped. After NaOH was isolated via electrolysis, the product was isolated by distillation. 56 g (95% based on the amount of ADN used) of hexamethylenediamine were obtained.

<Example 3>

Using the same reaction apparatus, anolyte and catholyte as in Example 2, the adiponnitrile was converted to 6-aminocapronitrile (ACN), and the preparation and electrolysis of the negative electrode was carried out after electrolysis of only 4 F / mol ADN It was carried out in the same manner as in Example 2 except that it was stopped. NaOH was isolated and then distilled to isolate 38.7 g (0.34 mol, 68% ADN) of aminocapronitrile, 16% hexamethylenediamine and 14% ADN. Selectivity was 79% for aminocapronitrile and 18.6% for hexamethylenediamine.

<Example 4>

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

Preparation and conversion of the negative electrode was carried out in the same manner as in Example 2 except that the electrolysis was stopped at only 2.3 F / mol of acetophenone.

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

<Example 5>

Reduction of 2-cyclohexanone to cyclohexanol was carried out using the same apparatus and anolyte as in Example 2. The catholyte used was a mixture of 737 g methanol, 330 g water, 11 g NaOH, 22 g 2-cyclohexanone and 7.5 g Raney nickel. The conversion was carried out in the same manner as in Example 2 except that the electrolysis was stopped after 6 F / mol of 2-cyclohexanone. The resulting product was distilled to 270 g, concentrated, diluted with 500 ml of water and extracted with 5 x 200 ml of MTBE. The organic phase was distilled off and 21.7 g of cyclohexanol was obtained, corresponding to 95% yield based on 2-cyclohexanone.

<Example 6>

This example was carried out in the same apparatus as Example 2. 1100 g of 1% sulfuric acid anolyte was used. The catholyte was a mixture of 418 g methanol, 318 g distilled water, 297 g sodium methyl sulfate solution, 55 g cyclohexanone oxime (0.487 mol) and 8 g copper powder at a concentration of 7.4% in methanol.

The conversion was carried out as follows.

After filling the cell compartments first, the negative electrode was washed with copper powder for 10 minutes. The electrolysis was then carried out under standard pressure at a current density of 1000 A / m ² at a temperature of 30 to 50 ° C. A charge of 12 F / mol was applied based on the oxime used.

To treat the product, the catholyte was adjusted to pH 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 MTBE each. After drying and removing the solvent, the crude product was distilled off. 35.2 g of cyclohexylamine (73% based on the oxime used) were isolated as reaction product.

<Example 7>

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

The conversion was carried out in a similar manner to Example 6.

Based on the diol used, a charge of 4.5 F / mol was applied.

To treat the product, the catholyte was filtered, the majority of the filtrate was evaporated and the crude product was distilled off. 23 g butanediol-1,4 and 12.4 g 2-butene-1,4-diol were isolated as reaction product.

<Example 8>

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

The conversion was carried out in a similar manner to Example 6.

Based on the substrate, a charge of 6.45 F / mol was applied.

To treat the product, the catholyte was adjusted to pH 13 with sodium hydroxide solution, the copper powder was filtered off, the filtrate was concentrated to 597 g and washed five times with 100 g MTBE each. The crude product was distilled off after drying and removal of the solvent. 26.2 g of aniline was isolated as reaction product.

<Example 9>

This example was carried out in the same apparatus as Example 2 in which an edge filter (pore size 100 μm) made of alloy steel was adapted to be used as the cathode. 1100 g of 1% sulfuric acid was used as the anolyte. The catholyte consisted of a mixture of 806 g methanol, 377 g distilled water, 52 g sodium hydroxide solution, 48 g 2-thienylacetonitrile (0.391 mol) and 30 g Raney nickel (BASF H1-50). .

The conversion was carried out at a current density of 1000 A / m ² at 21 ° C. Starting material was added to 14 batches. Based on the substrate, a charge of 6.45 F / mol was applied.

To process the product, the nickel powder was filtered off, the catholyte was neutralized with sulfuric acid and methanol was distilled off. The pH was adjusted to 13 and then extracted with MTBE. After drying and removing the solvent, the crude product was distilled off. 37 g of thienylethylamine were isolated as reaction product.

<Example 10>

This example was carried out in the same apparatus as Example 2 in which an edge filter (pore size 100 μm) made of platinum alloyed titanium was adapted to be used as the cathode. 1200 g of 1% sulfuric acid was used as the anolyte. The catholyte is a mixture of 651 g ethylene glycol dimethyl ether, 651 g distilled water, 28 g sodium hydroxide solution, 70 g 2-thienylacetonitrile (0.569 mol) and 50 g Raney nickel (BASF H1-50) Was done.

The conversion was carried out at 23 ° C. with a current density of 1000 A / m ² . Based on the substrate, a charge of 5.5 F / mol was applied.

To process the product, the nickel powder was filtered off and the filtrate was mixed with 4% sodium hydroxide and saturated with NaCl. Distillation after phase separation. 45 g of thienylethylamine were isolated as reaction product.

<Example 11>

This example was carried out in the same apparatus as Example 2 in which an edge filter (pore size 100 μm) made of platinum alloyed titanium was adapted to be used as the cathode. 1200 g of 1% sulfuric acid was used as the anolyte. The catholyte consisted of a mixture of 882 g methanol, 420 g distilled water, 28 g sodium hydroxide solution, 70 g veratryl cyanide (0.395 mol) and 50 g Raney nickel (BASF H1-50).

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

To treat the product, the nickel powder was filtered off, methanol was distilled off from the filtrate, and the remaining aqueous crude solution was extracted five times with 100 g of MTBE each. After drying and removing the solvent, the crude product was distilled off. 54.5 g of homoveratrilamine was isolated as reaction product.

Claims (8)

A method for electrochemically reducing an organic compound by contacting an organic compound with a negative electrode comprising a support comprising an electrically conductive material and a cathodic electroconductive layer formed by charging over the reaction thereon. The method of claim 1, wherein the cathodic layer contains a metal, conductive metal oxide or carbon material or a mixture of two or more thereof. 3. The method according to claim 1, wherein the cathodic layer contains in each case a metal of subgroup I, II or VIII of the periodic table as a free metal or a conductive metal oxide or a mixture of two or more thereof. The process according to claim 1, wherein the cathodic layer contains in each case a metal or conductive metal oxide or mixture of two or more thereof applied to the activated carbon. The method of claim 1, wherein the cathodic layer contains Raney Nickel, Raney Cobalt, Raney Silver, or Raney Iron. The method according to claim 1, wherein the support composed of the electrically conductive material has pores. The CC double bond, CC triple bond, aromatic CC bond, carbonyl group, thiocarbonyl group, carboxyl group, ester group, CN triple bond, CN double bond, aromatic CN bond, nitro group according to any one of claims 1 to 6 , A method of reducing an organic compound having at least one reducible group or bond of a nitroso group, a C-halogen single bond. The method of claim 1, wherein the organic compound is selected from the group consisting of nitriles, dinitriles, nitro compounds, dinitro compounds, saturated and unsaturated ketones, aminocarboxylic acids.