EP1206590B1 - Method for producing carbonyl compounds which are oxidized in position alpha - Google Patents

Method for producing carbonyl compounds which are oxidized in position alpha Download PDF

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EP1206590B1
EP1206590B1 EP00956251A EP00956251A EP1206590B1 EP 1206590 B1 EP1206590 B1 EP 1206590B1 EP 00956251 A EP00956251 A EP 00956251A EP 00956251 A EP00956251 A EP 00956251A EP 1206590 B1 EP1206590 B1 EP 1206590B1
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compound
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formula
phenyl
alkyl
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French (fr)
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EP1206590A1 (en
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Hermann Pütter
Kerstin Schierle-Arndt
Jörg Botzem
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds

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  • EP-A-460 451 describes a process for the production of ⁇ -hydroxymethyl ketals by electrochemical oxidation of Aldehydes or ketones in the presence of alcohols and halogen compounds known as auxiliary electrolytes. Reworking the Examples shows that under the described process conditions more highly oxidized carbonyl compounds are also formed, when the carbonyl group is in the ⁇ position to an aromatic Rest stands. For example, a methylene group in the ⁇ position be oxidized to the carbonyl group up to the carbonyl function and in addition, the carbonyl bond originally present can be oxidized in the aldehyde or keto function to the carboxyl group.
  • the unpublished German patent application 19904929 relates to a process for the preparation of 2,2,3,3-tetramethoxypropanol by electrochemical oxidation of methylglyoxaldimethylacetal using a mixture containing methanol, Water and an auxiliary electrolyte as an electrolysis medium and a cathode made of iron, steel, platinum or zinc.
  • the object of the present invention was therefore a To provide an electrochemical process from which Carbonyl compounds in keto or aldehyde function in high yields ⁇ -hydroxy ketals, ⁇ -ketal aldehydes, ⁇ -ketoacetals, ⁇ -ketal carboxylic acid esters and can produce ⁇ -keto orthoesters. Accordingly, the method defined above was invented.
  • the process according to the invention is particularly suitable for the preparation of compounds of the general formula I III or IV in which the radical R 4 in the acetalized carbonyl group is derived from methanol or ethanol.
  • n, V, W and R 5 have the same meaning as in formula Ia or III or the general formula IVa in which n, V, W, R 4 and R 5 have the same meaning as in formula Ia or IIIa.
  • the process is also particularly suitable for the preparation of compounds of the general formula Ib H 2m C m -CHOH-CH 2 (OR 4 ) 2 in which m is a number from 1 to 10 and R 4 has the same meaning as in formula II and for the preparation of which a compound of the general formula Vb H 2m C m -CH 2 -CHO starts.
  • auxiliary electrolyte contained in the electrolysis solution it is generally a halogen-containing auxiliary electrolyte such as elemental halogen, alkyl halides or halogen halides.
  • Halogen-containing salts in particular can also be preferred Iodides or bromides can be used.
  • Ammonium halides such as ammonium bromide, ammonium iodide or tetrabutylammonium iodide.
  • Metal halides are particularly preferred furthermore alkali halides such as sodium bromide, sodium iodide, potassium iodide or potassium bromide.
  • the metal salts (S) are preferably those which are derived from mineral acids.
  • the anions of the metal salt is it, for example, phosphate, sulfate, nitrate, Perchlorate or halide.
  • the cations of the metal salt (S) are preferred around iron, nickel, platinum, palladium, cobalt, zinc, silver or Copper ions.
  • the metal salt (S) becomes the electrolysis solution added in such amounts that the metal ions therein in amounts from 1 to 1000, preferably 5 to 500, preferably 5 to 300 Ppm, based on the total amount of the electrolysis liquid are included.
  • the usual cosolvents are used for the electrolysis liquid to. These are those in the organic Chemically common inert solvents with a high Oxidation potential. Dimethyl carbonate may be mentioned as an example or propylene carbonate.
  • the Electrolysis liquid can also be added to water, the Water content, however, 5 wt .-%, based on the total amount of Electrolysis liquid should not exceed.
  • the ratio of the products of general formulas I and V as well of the other by-products to the starting compounds in the Electrolysis liquid and the ratio of the individual products with different degrees of oxidation to each other is natural depending on the progress of the reaction.
  • the ratio of the products of general formulas I, III, IV and V and the other by-products to the starting compounds in the electrolysis liquid and the ratio of individual products with different degrees of oxidation to each other is naturally dependent on the progress of the reaction.
  • the amount of charge used for the reaction is 1 to 7 F per mole of starting compound of the general formula V.
  • 3.5 to 4 F are preferably used if mixtures are desired be the main components of the formula I and III should contain and 4.5 to 5.5 F if mixtures are desired be the main components of the formula I and IV should contain.
  • the method according to the invention can be used in all customary electrolysis cell types be performed. preferably one works with undivided flow cells.
  • the current densities at which the process is carried out are generally 0.5 to 25 A / dm 2 .
  • the temperatures are usually -20 to 60 ° C, preferably 0 to 60 ° C. In general, normal pressure is used. Higher pressures are preferably used when working at higher temperatures in order to avoid boiling of the starting compounds or cosolvents.
  • noble metals such as platinum or metal oxides such as ruthenium or chromium oxide or mixed oxides of the Ruo x TiO x type are suitable as anode materials.
  • Graphite or carbon electrodes are preferred.
  • Iron, steel, nickel are usually used as cathode materials or precious metals such as platinum as well as graphite or carbon materials into consideration.
  • the electrolysis liquid becomes worked up general separation methods.
  • the electrolysis liquid generally distilled first and the individual Compounds are in the form of different fractions won separately. Further cleaning can, for example by crystallization or by chromatography.

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  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A method for producing compounds which are oxidized in an alpha position by electrochemical reaction with alcohol in the presence of an auxiliary electrolyte and catalytic amounts of a metal salt.

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von einer Verbindung der allgemeinen Formel I

Figure 00010001
in der R1, R2, R3 Wasserstoff, C1- bis C20-Alkyl, C2- bis C20-Alkenyl, C2- bis C20-Alkinyl, C3- bis C12-Cycloalkyl, C4- bis C20-Cycloalkyl-alkyl, C1- bis C20-Hydroxyalkyl, gegebenenfalls durch C1- bis C8-Alkyl, C1- bis C8-Alkoxy, Halogen, C1- bis C4-Halogenalkyl, C1- bis C4-Halogenalkoxy, Phenyl, Phenoxy, Halogenphenyl, Halogenphenoxy, Carboxy, C2- bis C8-Alkoxycarbonyl oder Cyano substituiertes Aryl oder C7- bis C20-Arylalkyl, oder R1 und R2 oder R3 gemeinsam eine gegebenenfalls durch C1- bis C8-Alkyl, C1- bis C8-Alkoxy und/oder Halogen ein- bis zweifach substituierte C2- bis C9-Alkandiyleinheit, in der 1 oder 2 Methylgruppen auch durch eine Einheit (CH=CH) ersetzt sein können, bedeutet und R3 zusätzlich eine acetalisierte Carbonylgruppe, in der sich die Alkoxygruppen von einem Alkohol der allgemeinen Formel II R4-OH ableiten, in der R4 für C1- bis C6-Alkyl steht, bedeutet und
U eine acetalisierte Carbonylgruppe, in der sich die Alkoxygruppen von einem Alkohol der allgemeinen Formel II ableiten oder einer Verbindung der allgemeinen Formel III R3-V-W-R1 in der R1 die gleiche Bedeutung wie in Formel I hat und R3 ausschließlich gegebenenfalls C1- bis C8-Alkyl, C1- bis C8-Alkoxy, Halogen, C1- bis C4-Halogenalkyl, C1- bis C4-Halogenalkoxy, Phenyl, Phenoxy, Halogenphenyl, Halogenphenoxy, Carboxy, C2- bis C8-Alkoxycarbonyl oder Cyano substituiertes Aryl ist

V
eine Carbonylgruppe bedeutet oder die gleiche Bedeutung wie U in Formel I hat und
W
die gleiche Bedeutung wie V hat, mit der Maßgabe, daß eine der Gruppen V oder W eine Carbonylgruppe und die andere Gruppe eine acetalisierte Carbonylgruppe bedeutet
oder
einer Verbindung der allgemeinen Formel IV R3-V-W-O-R4 in der R4 die gleiche Bedeutung wie in Formel II hat, V und W die gleiche Bedeutung wie in Formel II haben und R3 die gleiche Bedeutung wie in Formel III hat,
indem man eine Verbindung der allgemeinen Formel V
Figure 00020001
in der V, R1, R2 und R3 die gleiche Bedeutung wie in Formel I bzw. III haben, mit der Maßgabe, daß
  • für den Fall, daß eine Verbindung der Formel III gewünscht wird, nur eine solche Verbindung Va eingesetzt wird, in der
    R1
    ausschließlich Wasserstoff bedeutet und
    R3
    ausschließlich gegebenenfalls durch C1- bis C8-Alkyl, C1- bis C8-Alkoxy, Halogen, C1- bis C4-Halogenalkyl, C1- bis C4-Halogenalkoxy, Phenyl, Phenoxy, Halogenphenyl, Halogenphenoxy, Carboxy, C2- bis C8-Alkoxycarbonyl oder Cyano substituiertes Aryl und
  • für den Fall, daß Verbindungen der Formel IV gewünscht werden, nur eine solche Verbindung Vb eingesetzt wird, in der
    R1 und R2
    ausschließlich Wasserstoff bedeuten,
    R3
    ausschließlich gegebenenfalls durch C1- bis C8-Alkyl, C1- bis C8-Alkoxy, Halogen, C1- bis C4-Halogenalkyl, C1- bis C4-Halogenalkoxy, Phenyl, Phenoxy, Halogenphenyl, Halogenphenoxy, Carboxy, C2- bis C8-Alkoxycarbonyl oder Cyano substituiertes Aryl
mit einem Alkohol der allgemeinen Formel II in Gegenwart eines Hilfselektrolyten und 1 bis 1000 Gew.-ppm Metallionen, bezogen auf die Gesamtmenge der Elektrolyseflüssigkeit eines Metallsalzes (S), abgeleitet von einem Metall der 1., 2., 6. oder 8. Nebengruppe oder von Blei, Zinn oder Rhenium, elektrochemisch umsetzt.The present invention relates to a process for the preparation of a compound of the general formula I.
Figure 00010001
in which R 1 , R 2 , R 3 are hydrogen, C 1 to C 20 alkyl, C 2 to C 20 alkenyl, C 2 to C 20 alkynyl, C 3 to C 12 cycloalkyl, C 4 - to C 20 -cycloalkyl-alkyl, C 1 - to C 20 -hydroxyalkyl, optionally by C 1 - to C 8 -alkyl, C 1 - to C 8 -alkoxy, halogen, C 1 - to C 4 -haloalkyl, C 1 - to C 4 -haloalkoxy, phenyl, phenoxy, halophenyl, halophenoxy, carboxy, C 2 - to C 8 -alkoxycarbonyl or cyano-substituted aryl or C 7 - to C 20 -arylalkyl, or R 1 and R 2 or R 3 together an optionally C 1 - to C 8 alkyl, C 1 - to C 8 -alkoxy and / or halogen-substituted one to two C 2 - to C 9 -Alkandiyleinheit, wherein 1 or 2 methylene groups by a unit (CH = CH) can be replaced, and R 3 additionally represents an acetalized carbonyl group in which the alkoxy groups are derived from an alcohol of the general formula II R 4 -OH derive, in which R 4 is C 1 - to C 6 alkyl, means and
U is an acetalized carbonyl group in which the alkoxy groups are derived from an alcohol of the general formula II or a compound of the general formula III R 3 -VWR 1 in which R 1 has the same meaning as in formula I and R 3 exclusively optionally C 1 - to C 8 -alkyl, C 1 - to C 8 -alkoxy, halogen, C 1 - to C 4 -haloalkyl, C 1 - bis C 4 -haloalkoxy, phenyl, phenoxy, halophenyl, halophenoxy, carboxy, C 2 - to C 8 -alkoxycarbonyl or cyano substituted aryl
V
represents a carbonyl group or has the same meaning as U in formula I and
W
has the same meaning as V, with the proviso that one of the groups V or W is a carbonyl group and the other group is an acetalized carbonyl group
or
a compound of the general formula IV R 3 -VWOR 4 in which R 4 has the same meaning as in formula II, V and W have the same meaning as in formula II and R 3 has the same meaning as in formula III,
by using a compound of the general formula V
Figure 00020001
in which V, R 1 , R 2 and R 3 have the same meaning as in formula I or III, with the proviso that
  • in the event that a compound of formula III is desired, only such a compound Va is used in which
    R 1
    means only hydrogen and
    R 3
    exclusively optionally by C 1 - to C 8 -alkyl, C 1 - to C 8 -alkoxy, halogen, C 1 - to C 4 -haloalkyl, C 1 - to C 4 -haloalkoxy, phenyl, phenoxy, halophenyl, halophenoxy, carboxy , C 2 - to C 8 alkoxycarbonyl or cyano substituted aryl and
  • in the event that compounds of the formula IV are desired, only one compound Vb is used in which
    R 1 and R 2
    only mean hydrogen,
    R 3
    exclusively optionally by C 1 - to C 8 -alkyl, C 1 - to C 8 -alkoxy, halogen, C 1 - to C 4 -haloalkyl, C 1 - to C 4 -haloalkoxy, phenyl, phenoxy, halophenyl, halophenoxy, carboxy , C 2 - to C 8 alkoxycarbonyl or cyano substituted aryl
with an alcohol of the general formula II in the presence of an auxiliary electrolyte and 1 to 1000 ppm by weight of metal ions, based on the total amount of the electrolysis liquid of a metal salt (S), derived from a metal of subgroup 1, 2, 6 or 8 or of lead, tin or rhenium, electrochemically converted.

Aus der EP-A-460 451 ist ein Verfahren zur Herstellung von α-Hydroxymethylketalen durch elektrochemische Oxidation von Aldehyden bzw. Ketonen in Gegenwart von Alkoholen und Halogenverbindungen als Hilfselektrolyten bekannt. Die Nacharbeitung der Beispiele zeigt, daß unter den beschriebenen Verfahrensbedingungen auch höher oxydierte Carbonylverbindungen gebildet werden, wenn die Carbonylgruppe in α-Stellung zu einem aromatischen Rest steht. So kann zum Beispiel eine Methylengruppe in α-Position zur Carbonylgruppe bis zur Carbonylfunktion oxydiert werden und zusätzlich kann die ursprünglich vorhandene Carbonylbindung in Aldehyd oder Ketofunktion bis zur Carboxylgruppe oxydiert werden. Es entstehen also nicht nur α-Hydroxyketale sondern auch α-Ketaldehyde, α-Ketoacetale, α-Ketalcarbonsäureester und α-Ketoorthoester. Dieses Verfahren vermag jedoch noch nicht vollständig zu befriedigen, da die Gesamtausbeute der genannten Wertprodukte relativ gering ist und zusätzlich große Mengen an sonstigen weitgehend unbrauchbaren Produkten gebildet werden.EP-A-460 451 describes a process for the production of α-hydroxymethyl ketals by electrochemical oxidation of Aldehydes or ketones in the presence of alcohols and halogen compounds known as auxiliary electrolytes. Reworking the Examples shows that under the described process conditions more highly oxidized carbonyl compounds are also formed, when the carbonyl group is in the α position to an aromatic Rest stands. For example, a methylene group in the α position be oxidized to the carbonyl group up to the carbonyl function and in addition, the carbonyl bond originally present can be oxidized in the aldehyde or keto function to the carboxyl group. Not only do α-hydroxyketals arise, but also α-ketaldehydes, α-ketoacetals, α-ketalcarboxylic esters and α-ketoorthoesters. However, this procedure is not yet able fully satisfied, since the total yield of the above Value products is relatively low and also large amounts of other largely unusable products.

Die nicht vorveröffentlichte Deutsche Patentanmeldung 19904929 betrifft ein Verfahren zur Herstellung von 2,2,3,3-Tetramethoxypropanol durch elektrochemische Oxydation von Methylglyoxaldimethylacetal unter Verwendung einer Mischung enthaltend Methanol, Wasser und einen Hilfselektrolyten als Elektrolysemedium und einer Kathode aus Eisen, Stahl, Platin oder Zink.The unpublished German patent application 19904929 relates to a process for the preparation of 2,2,3,3-tetramethoxypropanol by electrochemical oxidation of methylglyoxaldimethylacetal using a mixture containing methanol, Water and an auxiliary electrolyte as an electrolysis medium and a cathode made of iron, steel, platinum or zinc.

Die Aufgabe der vorliegenden Erfindung bestand also darin, ein elektrochemisches Verfahren bereitzustellen, mit dem man aus Carbonylverbindungen in Keto- oder Aldehydfunktion in hohen Ausbeuten α-Hydroxyketale, α-Ketalaldehyde, α-Ketoacetale, α-Ketalcarbonsäureester und α-Ketoorthoester herstellen kann. Demgemäß wurde das vorstehend definierte Verfahren erfunden. The object of the present invention was therefore a To provide an electrochemical process from which Carbonyl compounds in keto or aldehyde function in high yields α-hydroxy ketals, α-ketal aldehydes, α-ketoacetals, α-ketal carboxylic acid esters and can produce α-keto orthoesters. Accordingly, the method defined above was invented.

Das erfindungsgemäße Verfahren eignet sich besonders zur Herstellung von Verbindungen der allgemeinen Formel I III oder IV, in der sich der Rest R4 in der acetalysierten Carbonylgruppe von Methanol oder Ethanol ableitet.The process according to the invention is particularly suitable for the preparation of compounds of the general formula I III or IV in which the radical R 4 in the acetalized carbonyl group is derived from methanol or ethanol.

Unter den Verbindungen der Formel I sind solche der Formel Ia

Figure 00040001
in der U die gleiche Bedeutung wie in Formel I hat,

n
0, 1, 2 oder 3 bedeutet und
R5
C1- bis C8-Alkyl, C1- bis C8-Alkoxy, Halogen, C1- bis C4-Halogenalkyl, C1- bis C4-Halogenalkoxy, Phenyl, Phenoxy, Halogenphenyl, Halogenphenoxy, Carboxy, C2- bis C8-Alkoxycarbonyl oder Cyano bedeutet, bevorzugt.
Among the compounds of formula I are those of formula Ia
Figure 00040001
in which U has the same meaning as in formula I,
n
0, 1, 2 or 3 means and
R 5
C 1 to C 8 alkyl, C 1 to C 8 alkoxy, halogen, C 1 to C 4 haloalkyl, C 1 to C 4 haloalkoxy, phenyl, phenoxy, halophenyl, halophenoxy, carboxy, C 2 - to C 8 -alkoxycarbonyl or cyano means preferred.

Gleichfalls bevorzugt sind Verbindungen der allgemeinen Formel IIIa

Figure 00040002
in der n, V, W und R5 die gleiche Bedeutung wie in Formel Ia bzw. III haben
Figure 00040003
oder der allgemeinen Formel IVa
in der n, V, W, R4 und R5 die gleiche Bedeutung wie in Formel Ia bzw. IIIa haben. Likewise preferred are compounds of the general formula IIIa
Figure 00040002
in which n, V, W and R 5 have the same meaning as in formula Ia or III
Figure 00040003
or the general formula IVa
in which n, V, W, R 4 and R 5 have the same meaning as in formula Ia or IIIa.

Diese Verbindungen werden hergestellt, indem man als Ausgangsverbindung der allgemeinen Formel V eine solche der allgemeinen Formel Va

Figure 00050001
einsetzt, in der n und R5 die gleiche Bedeutung wie in Formel Ia haben.These compounds are prepared by starting from the general formula V with one of the general formula Va
Figure 00050001
uses, in which n and R 5 have the same meaning as in formula Ia.

Weiterhin eignet sich das Verfahren besonders zur Herstellung von Verbindungen der allgemeinen Formel Ib H2mCm-CHOH-CH2(OR4)2 in der m eine Zahl von 1 bis 10 bedeutet und R4 die gleiche Bedeutung wie bei Formel II hat und zu deren Herstellung man eine Verbindung der allgemeinen Formel Vb H2mCm-CH2-CHO einsetzt.The process is also particularly suitable for the preparation of compounds of the general formula Ib H 2m C m -CHOH-CH 2 (OR 4 ) 2 in which m is a number from 1 to 10 and R 4 has the same meaning as in formula II and for the preparation of which a compound of the general formula Vb H 2m C m -CH 2 -CHO starts.

Ganz besonders eignet sich das Verfahren zur Herstellung von

  • 2-Phenyl-2,2-dimethoxyethanol, 2-Phenyl-2,2-dimethoxyacetaldehyd und 2-Phenyl-glyoxaldimethylacetal aus Methanol und Acetophenon
  • α-Hydroxyocatanaldimethylacetal aus Octanal und
  • 2,2,3,3-Tetramethoxypropanol aus Methylglyocaldimethylacetal.
The process is particularly suitable for the production of
  • 2-phenyl-2,2-dimethoxyethanol, 2-phenyl-2,2-dimethoxyacetaldehyde and 2-phenyl-glyoxaldimethylacetal from methanol and acetophenone
  • α-Hydroxyocatanaldimethylacetal from octanal and
  • 2,2,3,3-tetramethoxypropanol from methylglyocaldimethyl acetal.

Als Hilfselektrolyt, der in der Elektrolyselösung enthalten ist, handelt es sich im Allgemeinen um einen halogenhaltigen Hilfselektrolyten wie elementares Halogen, Alkylhalogenide oder Halogenwaserstoffe. Bevorzugt können auch halogenhaltige Salze insbesondere Jodide oder Bromide eingesetzt werden. Beispiele sind Ammoniumhalogenide wie Ammoniumbromid, Ammoniumjodid oder Tetrabutylammoniumjodid. Besonders bevorzugte Metallhalogenide sind weiterhin Alkalihalogenide wie Natriumbromid, Natriumjodid, Kaliumjodid oder Kaliumbromid. As an auxiliary electrolyte contained in the electrolysis solution, it is generally a halogen-containing auxiliary electrolyte such as elemental halogen, alkyl halides or halogen halides. Halogen-containing salts in particular can also be preferred Iodides or bromides can be used. examples are Ammonium halides such as ammonium bromide, ammonium iodide or tetrabutylammonium iodide. Metal halides are particularly preferred furthermore alkali halides such as sodium bromide, sodium iodide, potassium iodide or potassium bromide.

Bei den Metallsalzen (S) handelt es sich bevorzugt um solche, die sich von Mineralsäuren ableiten. Bei den Anionen des Metallsalzes handelt es sich also beispielsweise um Phosphat, Sulfat, Nitrat, Perchlorat oder Halogenid.The metal salts (S) are preferably those which are derived from mineral acids. For the anions of the metal salt is it, for example, phosphate, sulfate, nitrate, Perchlorate or halide.

Bei den Kationen des Metallsalzes (S) handelt es sich bevorzugt um Eisen-, Nickel-, Platin-, Palladium-, Cobalt-, Zink-, Silberoder Kupferionen. Das Metallsalz (S) wird der Elektrolyselösung in solchen Mengen zugesetzt, daß dessen Metallionen darin in Mengen von 1 bis 1000, bevorzugt 5 bis 500, bevorzugt 5 bis 300 Gew.ppm, bezogen auf die Gesamtmenge der Elektrolyseflüssigkeit enthalten sind.The cations of the metal salt (S) are preferred around iron, nickel, platinum, palladium, cobalt, zinc, silver or Copper ions. The metal salt (S) becomes the electrolysis solution added in such amounts that the metal ions therein in amounts from 1 to 1000, preferably 5 to 500, preferably 5 to 300 Ppm, based on the total amount of the electrolysis liquid are included.

Gegebenenfalls setzt man der Elektrolyseflüssigkeit übliche Cosolvenzien zu. Dabei handelt es sich um die in der organischen Chemie allgemein üblichen inerten Lösungsmittel mit einem hohen Oxidationspotential. Beispielhaft genannt seien Dimethylcarbonat oder Propylencarbonat. Neben den genannten Cosolvenzien kann der Elektrolyseflüssigkeit auch Wasser zugesetzt werden, wobei der Wassergehalt allerdings 5 Gew.-%, bezogen auf die Gesamtmenge der Elektrolyseflüssigkeit, nicht überschreiten sollte.If necessary, the usual cosolvents are used for the electrolysis liquid to. These are those in the organic Chemically common inert solvents with a high Oxidation potential. Dimethyl carbonate may be mentioned as an example or propylene carbonate. In addition to the above-mentioned cosolvents, the Electrolysis liquid can also be added to water, the Water content, however, 5 wt .-%, based on the total amount of Electrolysis liquid should not exceed.

Im allgemeinen ist die Elektrolyseflüssigkeit wie folgt zusammengesetzt:

  • einer Ausgangsverbindung der allgemeinen Formel V
  • einem Alkohol der allgemeinen Formel II
  • einem halogenhaltigen Hilfselektrolyten
  • katalytischen Mengen des Metallsalzes (S)
  • gegebenenfalls den gewünschten Produkten der allgemeinen Formeln I, III und IV
  • gegebenenfalls sonstigen Nebenprodukten der Elektrolyse die von den Verbindungen der allgemeinen Formeln I, II, III, IV und V abgeleitet sind
  • gegebenenfalls sonstigen üblichen Cosolventien
In general, the electrolysis liquid is composed as follows:
  • a starting compound of the general formula V
  • an alcohol of the general formula II
  • a halogen-containing auxiliary electrolyte
  • catalytic amounts of metal salt (S)
  • optionally the desired products of the general formulas I, III and IV
  • optionally other by-products of electrolysis which are derived from the compounds of the general formulas I, II, III, IV and V.
  • optionally other usual cosolvents

Das Verhältnis der Produkte der allgemeine Formeln I und V sowie der sonstigen Nebenprodukte zu den Ausgangsverbindungen in der Elektrolyseflüssigkeit und das Verhältnis der einzelnen Produkte mit unterschiedlichem Oxidationsgrad zueinander ist naturgemäß abhängig vom Reaktionsfortschritt.The ratio of the products of general formulas I and V as well of the other by-products to the starting compounds in the Electrolysis liquid and the ratio of the individual products with different degrees of oxidation to each other is natural depending on the progress of the reaction.

Das Verhältnis der Produkte der allgemeinen Formeln I, III, IV und V sowie der sonstigen Nebenprodukte zu den Ausgangsverbindungen in der Elektrolyseflüssigkeit und das Verhältnis der einzelenen Produkte mit unterschiedlichem Oxidationsgrad zueinander ist naturgemäß abhängig vom Reaktionsfortschritt.The ratio of the products of general formulas I, III, IV and V and the other by-products to the starting compounds in the electrolysis liquid and the ratio of individual products with different degrees of oxidation to each other is naturally dependent on the progress of the reaction.

Im allgemeinen beträgt die zur Umsetzung aufgewendete Ladungsmenge 1 bis 7 F pro Mol Ausgangsverbindung der allgemeinen Formel V. Bevorzugt werden 3,5 bis 4 F eingesetzt, wenn Mischungen gewünscht werden, die als Hauptkomponenten Verbindungen der Formel I und III enthalten sollen und 4,5 bis 5,5 F, wenn Mischungen gewünscht werden, die als Hauptkomponenten Verbindungen der Formel I und IV enthalten sollen.In general, the amount of charge used for the reaction is 1 to 7 F per mole of starting compound of the general formula V. 3.5 to 4 F are preferably used if mixtures are desired be the main components of the formula I and III should contain and 4.5 to 5.5 F if mixtures are desired be the main components of the formula I and IV should contain.

Das erfindungsgemäße Verfahren kann in allen üblichen Elektrolysezellentypen durchgeführt werden. vorzugsweise arbeitet man mit ungeteilten Durchflusszellen.The method according to the invention can be used in all customary electrolysis cell types be performed. preferably one works with undivided flow cells.

Die Stromdichten, bei denen man das Verfahren durchführt, betragen im allgemeinen 0,5 bis 25 A/dm2. Die Temperaturen betragen üblicherweise -20 bis 60°C, bevorzugt 0 bis 60°C. Im allgemeinen wird bei Normaldruck gearbeitet. Höhere Drücke werden bevorzugt dann angewandt, wenn bei höheren Temperaturen gearbeitet werden soll, um eine Sieden der Ausgangsverbindungen bzw. Cosolventien zu vermeiden.The current densities at which the process is carried out are generally 0.5 to 25 A / dm 2 . The temperatures are usually -20 to 60 ° C, preferably 0 to 60 ° C. In general, normal pressure is used. Higher pressures are preferably used when working at higher temperatures in order to avoid boiling of the starting compounds or cosolvents.

Als Anodenmaterialien eignen sich beispielsweise Edelmetalle wie Platin oder Metalloxide wie Ruthenium oder Chromoxid oder Mischoxide des Typs RuoxTiOx. Bevorzugt sind Graphit oder Kohleelektroden.For example, noble metals such as platinum or metal oxides such as ruthenium or chromium oxide or mixed oxides of the Ruo x TiO x type are suitable as anode materials. Graphite or carbon electrodes are preferred.

Als Kathodenmaterialien kommen in der Regel Eisen, Stahl, Nickel oder Edelmetalle wie Platin sowie Graphit oder Kohlematerialien in Betracht.Iron, steel, nickel are usually used as cathode materials or precious metals such as platinum as well as graphite or carbon materials into consideration.

Nach Beendigung der Reaktion wird die Elektrolyseflüssigkeit nach allgemeinen Trennmethoden aufgearbeitet. Hierzu wird die Elektrolyseflüssigkeit im allgemeinen zunächst destilliert und die einzelnen Verbindungen werden in Form von unterschiedlichen Fraktionen getrennt gewonnen. Eine weitere Reinigung kann beispielsweise durch Kristallisation oder chromatographisch erfolgen. After the reaction has ended, the electrolysis liquid becomes worked up general separation methods. For this, the electrolysis liquid generally distilled first and the individual Compounds are in the form of different fractions won separately. Further cleaning can, for example by crystallization or by chromatography.

Experimenteller TeilExperimental part

Alle Versuche wurden in einer ungeteilten Zelle mit 11 bipolaren Elektroden (10 Spalte, Spaltabstand 1,5 mm) durchgeführt.All experiments were carried out in an undivided cell with 11 bipolar ones Electrodes (10 columns, gap distance 1.5 mm) performed.

Stromdichte: 3,4 A/dm2 Current density: 3.4 A / dm 2

Durchfluß: 400 l/hFlow: 400 l / h

Beispiel 1:Example 1:

Ansatz 450 g Acetophenon 30 g Kaliumiodid 2460 g Methanol Fe(III): 5 ppm Kathode Stahl 1.4301 Anode Graphit Dauer 7,03 h Temperatur 36 °C Ladungsmenge 3,5 F Stromstärke 5 A Umsatz >99 % Ausbeuten der Wertprodukte: 2-Phenyl-2.2-dimethoxy-ethanol 24 % 5 2-Phenyl-2.2-dimethoxy-acetaldehyd 42 % 2-Phenylglyoxaldimethylacetal 0 % Phenylglyoxylsäuremethylorthoester und 2-Phenyl-2.2-dimethoxyessigsäuremethylester 0 % Gesamt 66 % approach 450 g acetophenone 30 g potassium iodide 2460 g of methanol Fe (III): 5 ppm cathode Steel 1.4301 anode graphite duration 7.03 h temperature 36 ° C amount of charge 3.5 F amperage 5 A sales > 99% Yields of the valuable products: 2-phenyl-2.2-dimethoxy-ethanol 24% 5 2-phenyl-2,2-dimethoxy acetaldehyde 42% 2-Phenylglyoxaldimethylacetal 0% Phenylglyoxylsäuremethylorthoester and 2-phenyl-2,2-dimethoxyacetic acid methyl ester 0% total 66%

Beispiel 2:Example 2:

Ansatz 450 g Acetophenon 30 g Kaliumiodid 2460 g Methanol Fe(III): 5 ppm Kathode Graphit Anode Graphit Dauer 7,03 h Temperatur 36°C Ladungsmenge 3,5 F Stromstärke 5 A Umsatz 84 % Ausbeuten der Wertprodukte: 2-Phenyl-2.2-dimethoxy-ethanol 15 % 2-Phenyl-2.2-dimethoxy-acetaldehyd 24 % 2-Phenylglyoxaldimethylacetal 8 % Phenylglyoxylsäuremethylorthoester und 2-Phenyl-2.2-dimethoxyessigsäuremethylester 3 % Gesamt 50 % approach 450 g acetophenone 30 g potassium iodide 2460 g of methanol Fe (III): 5 ppm cathode graphite anode graphite duration 7.03 h temperature 36 ° C amount of charge 3.5 F amperage 5 A sales 84% Yields of the valuable products: 2-phenyl-2.2-dimethoxy-ethanol 15% 2-phenyl-2.2-dimethoxy-acetaldehyde 24% 2-Phenylglyoxaldimethylacetal 8th % Phenylglyoxylsäuremethylorthoester and 2-phenyl-2,2-dimethoxyacetic acid methyl ester 3% total 50%

Beispiel 3 (4118/98-176):Example 3 (4118 / 98-176):

Ansatz 450 g Acetophenon 90 g Kaliumiodid 2460 g Methanol Fe(III) : 5 ppm Kathode Stahl 1.4301 Anode Graphit Dauer 7,03 h Temperatur 55-58°C Ladungsmenge 3,5 F Stromstärke 5 A Umsatz 88 % Ausbeuten der Wertprodukte: 2-Phenyl-2.2-dimethoxy-ethanol 38 % 2-Phenyl-2.2-dimethoxy-acetaldehyd 19% 2-Phenylglyoxaldimethylacetal 12% Phenylglyoxylsäuremethylorthoester und 2-Phenyl-2.2-dimethoxyessigsäuremethylester 1% Gesamt 70 % approach 450 g acetophenone 90 g potassium iodide 2460 g of methanol Fe (III): 5 ppm cathode Steel 1.4301 anode graphite duration 7.03 h temperature 55-58 ° C amount of charge 3.5 F amperage 5 A sales 88% Yields of the valuable products: 2-phenyl-2.2-dimethoxy-ethanol 38% 2-phenyl-2.2-dimethoxy-acetaldehyde 19% 2-Phenylglyoxaldimethylacetal 12% Phenylglyoxylsäuremethylorthoester and 2-phenyl-2,2-dimethoxyacetic acid methyl ester 1% total 70%

Beispiel 4:Example 4:

Ansatz 450 g Acetophenon 90 g Kaliumiodid 2460 g Methanol Fe(III): 5 ppm Kathode Stahl 1.4301 Anode Graphit Dauer 10,47 h Temperatur 55-58°C Strommenge 5,5 F Stromstärke 5 A Umsatz >99 % Ausbeuten der Wertprodukte: 2-Phenyl-2.2-dimethoxy-ethanol 39 % 2-Phenyl-2.2-dimethoxy-acetaldehyd 0 % 2-Phenylglyoxaldimethylacetal 3 % Phenylglyoxylsäuremethylorthoester und 2-Phenyl-2.2-dimethoxyessigsäuremethylester 39 % approach 450 g acetophenone 90 g potassium iodide 2460 g of methanol Fe (III): 5 ppm cathode Steel 1.4301 anode graphite duration 10.47 h temperature 55-58 ° C electricity 5.5 F amperage 5 A sales > 99% Yields of the valuable products: 2-phenyl-2.2-dimethoxy-ethanol 39% 2-phenyl-2.2-dimethoxy-acetaldehyde 0% 2-Phenylglyoxaldimethylacetal 3% Phenylglyoxylsäuremethylorthoester and 2-phenyl-2,2-dimethoxyacetic acid methyl ester 39%

Beispiel 5:Example 5:

Ansatzapproach 450 g Octanal450 g octanal 90 g Kaliumiodid90 g potassium iodide 2460 g Methanol2460 g of methanol Fe (III): 5 ppmFe (III): 5 ppm Kathodecathode MKUS-F04 (SGL)MKUS-F04 (SGL) Anodeanode Graphitfilz RVG 2003, 6 mm (Deutsche Carbon)Graphite felt RVG 2003, 6 mm (German carbon) Dauerduration 3,76 h3.76 h Temperaturtemperature 55-58°C55-58 ° C Strommengeelectricity 2 F2 F Stromstärkeamperage 5 A5 A Umsatzsales >99 %> 99% Ausbeuteyield 37 % α-Hydroxyoctanaldimethylacetal37% α-hydroxyoctanal dimethylacetal

Beispiel 6:Example 6:

Ansatzapproach 450 g Octanal450 g octanal 90 g Kaliumiodid90 g potassium iodide 2460 g Methanol2460 g of methanol Fe (III): 5 ppmFe (III): 5 ppm Kathodecathode MKUS-F04 (SGL)MKUS-F04 (SGL) Anode
(Deutsche Carbon)anode
(German carbon) Graphitfilz RVG 2003, 6 mmGraphite felt RVG 2003, 6 mm Dauerduration 3,76 h3.76 h Temperaturtemperature 26-28°C26-28 ° C Strommengeelectricity 2 F2 F Stromstärkeamperage 5 A5 A Umsatzsales 97 %97% Ausbeuteyield 45 % α-Hydroxyoctanaldimethylacetal45% α-hydroxyoctanal dimethyl acetal

Beispiel 7:Example 7:

Ansatzapproach 450 g Methylglyoxaldimethylacetal450 g of methylglyoxal dimethyl acetal 45 g Kaliumiodid45 g of potassium iodide 2505 g Methanol2505 g of methanol 0,11 g NiSO4 0.11 g NiSO 4 Kathodecathode Graphitgraphite Anodeanode Graphitgraphite Dauerduration 5 h5 h Temperaturtemperature 30 °C30 ° C Stromstärkeamperage 5 A5 A Umsatzsales 52% 52% Selektivitätselectivity 59,4%59.4% Ausbeute an 2,2,3,3-TetramethoxypropanolYield of 2,2,3,3-tetramethoxypropanol 31 %31%

Vergleichsbeispiel 1:Comparative Example 1:

Ansatz 450 g Acetophenon 30 g Kaliumiodid 2460 g Methanol Kathode Stahl 1.4301 Anode Graphit Dauer 7,03 h Temperatur 36°C Ladungsmenge 3,5 F Stromstärke 5 A Umsatz 98 % Ausbeuten der Wertprodukte: 2-Phenyl-2.2-dimethoxy-ethanol 19 % 2-Phenyl-2.2-dimethoxy-acetaldehyd 12 % 2-Phenylglyoxaldimethylacetal 5 % Phenylglyoxylsäuremethylorthoester und 2-Phenyl-2.2-dimethoxyessigsäuremethylester 9 % Gesamt 45 % approach 450 g acetophenone 30 g potassium iodide 2460 g of methanol cathode Steel 1.4301 anode graphite duration 7.03 h temperature 36 ° C amount of charge 3.5 F amperage 5 A sales 98% Yields of the valuable products: 2-phenyl-2.2-dimethoxy-ethanol 19% 2-phenyl-2.2-dimethoxy-acetaldehyde 12% 2-Phenylglyoxaldimethylacetal 5% Phenylglyoxylsäuremethylorthoester and 2-phenyl-2,2-dimethoxyacetic acid methyl ester 9% total 45%

Vergleichsbeispiel 2:Comparative Example 2:

Ansatz 450 g Acetophenon 30 g Kaliumiodid 2460 g Methanol Kathode Graphit Anode Graphit Dauer 7,03 h Temperatur 36 °C Ladungsmenge 3,5 F Stromstärke 5 A Umsatz 95% Ausbeuten der Wertprodukte: 2-Phenyl-2.2-dimethoxy-ethanol 7 % 2-Phenyl-2.2-dimethoxy-acetaldehyd 25 % 2-Phenylglyoxaldimethylacetal 3 % Phenylglyoxylsäuremethylorthoester und 2-Phenyl-2.2-dimethoxyessigsäuremethylester 1 % Gesamt 36% approach 450 g acetophenone 30 g potassium iodide 2460 g of methanol cathode graphite anode graphite duration 7.03 h temperature 36 ° C amount of charge 3.5 F amperage 5 A sales 95% Yields of the valuable products: 2-phenyl-2.2-dimethoxy-ethanol 7% 2-phenyl-2.2-dimethoxy-acetaldehyde 25% 2-Phenylglyoxaldimethylacetal 3% Phenylglyoxylsäuremethylorthoester and 2-phenyl-2,2-dimethoxyacetic acid methyl ester 1 % total 36%

Vergleichsbeispiel 3:Comparative Example 3:

Ansatzapproach 450 g Octanal 90 g Kaliumiodid450 g octanal 90 g potassium iodide 2460 g Methanol 2460 g of methanol Kathodecathode Graphitgraphite Anodeanode Graphitgraphite Dauerduration 3,76 h3.76 h Temperaturtemperature 55-58°C55-58 ° C Strommengeelectricity 2 F2 F Stromstärkeamperage 5 A5 A Umsatzsales >99 %> 99% Ausbeuteyield 30 %30%

Vergleichsbeispiel 4:Comparative Example 4:

Ansatzapproach 450 g Octanal450 g octanal 90 g Kaliumiodid90 g potassium iodide 2460 g Methanol2460 g of methanol Kathodecathode Graphitgraphite Anodeanode Graphitgraphite Dauerduration 3,76 h3.76 h Temperaturtemperature 26-28°C26-28 ° C Strommengeelectricity 2 F2 F Stromstärkeamperage 5 A5 A Umsatzsales >99 %> 99% Ausbeuteyield 40 %40%

Vergleichbeispiel 5:Comparative example 5:

Ansatzapproach 450 g Methylglyoxaldimethylacetal450 g of methylglyoxal dimethyl acetal 45 g Kaliumiodid45 g of potassium iodide 2505 g Methanol2505 g of methanol Kathodecathode Graphitgraphite Anodeanode Graphitgraphite Dauerduration 5 h5 h Temperaturtemperature 30 °C30 ° C Stromstärkeamperage 5 A5 A Umsatzsales >99%> 99% Selektivitätselectivity 24,6%24.6% Ausbeuteyield 2,2,3,3-Tetramethoxypropanol2,2,3,3-tetramethoxypropanol 24,6%24.6%

Claims (12)

  1. A process for the preparation of a compound of the general formula I
    Figure 00180001
    where R1, R2, R3 are hydrogen, C1- to C20-alkyl, C2- to C20-alkenyl, C2- to C20-alkynyl, C3- to C12-cycloalkyl, C4- to C20-cycloalkyl-alkyl, C1- to C20-hydroxyalkyl, or aryl or C7- to C20-arylalkyl which is unsubstituted or substituted by C1- to C8-alkyl, C1- to C8-alkoxy, halogen, C1- to C4-haloalkyl, C1- to C4-haloalkoxy, phenyl, phenoxy, halophenyl, halophenoxy, carboxyl, C2- to C8-alkoxycarbonyl or cyano, or R1 and R2 or R3 together are a C2- to C9-alkanediyl unit which is unsubstituted, monosubstituted or disubstituted by C1- to C8-alkyl, C1- to C8-alkoxy and/or halogen and in which one or two methyl groups may also be replaced by a (CH=CH) unit and R3 is additionally an acetylated carbonyl group in which the alkoxy groups are derived from an alcohol of the general formula II R4-OH where R4 is C1- to C6-alkyl, and
    U is an acetylated carbonyl group in which the alkoxy groups are derived from an alcohol of the general formula II, or is a compound of the general formula III R3-V-W-R1 where R1 is as defined under the formula I, and R3 is exclusively aryl which is unsubstituted or substituted by C1- to C8-alkyl, C1- to C8-alkoxy, halogen, C1- to C4-haloalkyl, C1- to C4-haloalkoxy, phenyl, phenoxy, halophenyl, halophenoxy, carboxyl, C2- to C8-alkoxycarbonyl or cyano,
    V
    is a carbonyl group or is as defined for U under the formula I, and
    W
    is as defined for V, with the proviso that one of the groups V and W is a carbonyl group and the other is an acetylated carbonyl group,
    or
    a compound of the general formula IV R3 -V-W-O-R4 where R4 is as defined under the formula II, V, W and R3 are as defined under the formula III,
    by subjecting a compound of the general formula V
    Figure 00190001
    where V, R1, R2 and R3 are as defined under the formula I or III, with the proviso that
    in the case where a compound of the formula III is desired, use is only made of a compound Va in which
    R1
    is exclusively hydrogen and
    R3
    is exclusively aryl which is unsubstituted or substituted by C1- to C8-alkyl, C1- to C8-alkoxy, halogen, C1- to C4-haloalkyl, C1- to C4-haloalkoxy, phenyl, phenoxy, halophenyl, halophenoxy, carboxyl, C2- to C8-alkoxycarbonyl or cyano, and
    in the case where a compound of the formula IV is desired, use is only made of a compound Vb in which
    R1 and R2
    are exclusively hydrogen,
    R3
    is exclusively aryl which is unsubstituted or substituted by C1- to C8-alkyl, C1- to C8-alkoxy, halogen, C1- to C4-haloalkyl, C1- to C4-haloalkoxy, phenyl, phenoxy, halophenyl, halophenoxy, carboxyl, C2- to C8-alkoxycarbonyl or cyano,
    to an electrochemical reaction with an alcohol of the general formula II in the presence of an auxiliary electrolyte and from 1 to 1000 ppm by weight of metal ions, based on the total amount of electrolysis liquid, of a metal salt (S) derived from a metal from the 1st, 2nd, 6th or 8th sub-group or from lead, tin or rhenium.
  2. A process as claimed in claim 1 for the preparation of a compound of the general formula Ia
    Figure 00200001
    where U is as defined under the formula I,
    n
    is 0, 1, 2 or 3, and
    R5
    is C1- to C8-alkyl, C1- to C8-alkoxy, halogen, C1- to C4-haloalkyl, C1- to C4-haloalkoxy, phenyl, phenoxy, halophenyl, halophenoxy, carboxyl, C2- to C8-alkoxycarbonyl or cyano,
    or of the general formula IIIa
    Figure 00200002
    where n, V, W and R5 are as defined under the formula Ia or III,
    or of the general formula IVa
    Figure 00210001
    where n, V, W, R4 and R5 are as defined under the formula Ia or IIIa, by employing, as starting compound of the general formula V, a compound of the general formula Va
    Figure 00210002
    where n and R5 are as defined under the formula Ia.
  3. A process as claimed in claim 2, where the compound of the general formula Ia is 2-phenyl-2,2-dimethoxyethanol, the compound of the general formula IIIa is 2-phenyl-2,2-dimethoxyacetaldehyde or 2-phenylglyoxal dimethyl acetal, the compound of the general formula IVa is phenylglyoxylic acid methyl orthoester, and the compound of the general formula Va is acetophenone.
  4. A process as claimed in claim 1, where the compound of the general formula I is a compound of the general formula Ib H2mCm-CHOH-CH2(OR4)2 where m is a number from 1 to 10, and R4 is as defined under the formula II, and the compound of the general formula V is a compound of the general formula Vb H2mCm-CH2-CHO
  5. A process as claimed in any one of claims 1 to 4, where the compound of the formula I is 2,2,3,3-tetramethoxypropanol, and the starting compound employed is methylglyoxal dimethyl acetal.
  6. A process as claimed in any one of claims 1 to 5, where the anions of the metal salt (S) are derived from mineral acids.
  7. A process as claimed in any one of claims 1 to 6, where the anions of the metal salt (S) are phosphate, sulfate, nitrate, perchlorate or halide.
  8. A process as claimed in any one of claims 1 to 7, where the cations of the metal salt (S) are iron, nickel, platinum, palladium, cobalt, zinc, silver or copper.
  9. A process as claimed in any one of claims 1 to 8, where the electrolysis liquid contains a halogen-containing auxiliary electrolyte.
  10. A process as claimed in any one of claims 1 to 9, where
    the proportion of the starting compounds and products of the general formulae I, III, IV and V and of the other by-products of electrolysis from the abovementioned compounds is from 1 to 70% by weight,
    the proportion of the alcohol of the general formula II is from 14.9 to 94.9% by weight,
    the proportion of auxiliary electrolyte is from 0.1 to 5% by weight, and
    the proportion of any co-solvents present is from 0 to 70% by weight,
    based on the electrolysis liquid.
  11. A process as claimed in any one of claims 1 to 10, where the electrolysis is carried out in an undivided electrolysis cell.
  12. A process as claimed in any one of claims 1 to 11, where the anodes employed are made of noble metals, noble-metal oxides, graphite or carbon materials, and the cathodes employed are made of iron, steel, nickel, zinc, noble metals, graphite or carbon materials.
EP00956251A 1999-08-06 2000-07-21 Method for producing carbonyl compounds which are oxidized in position alpha Expired - Lifetime EP1206590B1 (en)

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