EP0283807A1 - Process for the preparation of methoxyacetaldehyde dialkyl acetals - Google Patents

Process for the preparation of methoxyacetaldehyde dialkyl acetals Download PDF

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EP0283807A1
EP0283807A1 EP88103423A EP88103423A EP0283807A1 EP 0283807 A1 EP0283807 A1 EP 0283807A1 EP 88103423 A EP88103423 A EP 88103423A EP 88103423 A EP88103423 A EP 88103423A EP 0283807 A1 EP0283807 A1 EP 0283807A1
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formula
radical
alkanol
amine
compound
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EP0283807B1 (en
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Dieter Dr. Degner
Eberhard Prof.Dr. Steckhan
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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
    • C25B3/20—Processes
    • C25B3/23—Oxidation

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  • the invention relates to a new electrochemical process for the preparation of methoxy acetaldehyde dialkyl acetals.
  • alkylbenzenes such as toluene or p-xylene
  • benzoic acid esters in the presence of alkanols and triarylamines of the formula III.
  • the advantageous result of the process of this invention is surprising, because here the acetals are formed in high selectivities and are not further oxidized to the corresponding esters.
  • R represents an alkyl group having 1 to 4 carbon atoms
  • R is e.g. one of the residues: -CH3, -C2H5, -C3H7 or -C4H9.
  • the preferred starting material is 1,2-dimethoxyethane.
  • alkanols of the formula ROH examples include Ethanol, propanol, isopropanol, butanol, isobutanol and preferably methanol.
  • Triarylamine compounds of the formula III are compounds of the following structure They contain, for example, F, Cl or Br atoms as halogen atoms.
  • Compounds of the formula III are, for example, tris (4-bromophenyl) amine, bis (4-bromophenyl) - (2,4-dibromophenyl) amine, bis (2,4-dibromophenyl) -4-bromophenylamine, tris (2,4-dibromophenyl) amine, tris- (4-chlorophenyl) amine, bis- (4-chlorophenyl) - (2,4-dichlorophenyl) amine, bis- (2,4-dichlorophenyl) - (4th -chlorophenyl) amine and tris (2,4-dichlorophenyl) amine, of which tris (2,4-dibromophenyl) amine and tris (2,4-dich
  • the electrolyte is supplemented with the conductive salts commonly used in organic electrochemistry, such as salts of tetrafluoroboric acid, salts of alkyl or arylsulfonic acids or salts of alkylsulfuric acids and salts of perchloric acid.
  • conductive salts commonly used in organic electrochemistry, such as salts of tetrafluoroboric acid, salts of alkyl or arylsulfonic acids or salts of alkylsulfuric acids and salts of perchloric acid.
  • alcoholates such as NaOCH3 and KOCH3 come into consideration.
  • cosolvents can be added to the electrolyte.
  • co-solvents come e.g. B. halogenated hydrocarbons, such as methylene chloride, dichloroethane, 1,2-dichloropropane or nitriles, such as acetonitrile.
  • the cosolvents are the alcohol z. B. in amounts up to 60 parts by weight per 100 parts by weight of alkanol.
  • the method according to the invention does not require a special electrolysis cell; an undivided flow cell is preferably used.
  • All anode materials which are customary per se and which are stable under the electrolysis conditions such as noble metals, e.g. B. gold or platinum.
  • Graphite is preferably used.
  • cathode material u. a. Graphite, iron, steel, nickel or even noble metals such as platinum.
  • the electrolyte used in electrooxidation has the following composition, for example: 1 to 70% by weight of starting compound of the formula II 30 to 96% by weight alkanol with or without cosolvent 0.3 to 5% by weight of triarylamine compounds of the formula III 0.3 to 4% by weight of conductive salt
  • Electrolysis is carried out at current densities of 0.25 to 10 A / dm2, advantageously from 0.5 to 5 A / dm2, preferably at 1.0 to 4 A / dm2.
  • the amount of charge is 1 to 10, preferably 2 to 8 F per mole of starting material.
  • the upper limit of the electrolysis temperatures is the boiling point of the alkanol or the cosolvent. Expediently, electrolysis is carried out at temperatures up to 5 ° C. below the boiling point of the electrolyte. When using methanol e.g. at temperatures up to 60 ° C, preferably at 20 to 60 ° C, electrolyzed. The process can be carried out batchwise or continuously.
  • the electrolysis discharges are worked up using methods known per se.
  • the electrolysis discharge is expediently worked up by distillation. Excess alkanol and any cosolvent used are first distilled off, conductive salt and triarylamino compound are filtered off and the methoxiacetaldehyde dialkyl acetals become cleaned, e.g. B. by distillation. Alkanol, cosolvent, conductive salt and triarylamino compound and unreacted compounds of the formula II can be recycled to the electrolysis.
  • the methoxy acetaldehyde dialkyl acetals obtainable by the process according to the invention are valuable intermediates for the synthesis of medicaments, in particular sulfonamides.
  • Apparatus undivided cell with 6 electrodes, bipolar electrode arrangement, electrode spacing: 0.5 mm, anodes and cathodes: graphite.
  • Composition of the electrolyte 1225 g (13.61 mol) of 1,2-dimethoxyethane 12.3 g sodium benzenesulfonate 12.3 g sodium methylate 12.3 g tris (2,4-dibromophenyl) amine 1188 g of methanol Current density: 3.3 A / dm2 Temperature: 27 to 28 ° C Electrolysis with 2.2 F / mol 1,2-dimethoxyethane
  • the electrolyte is pumped through the cell at 200 l / h via a heat exchanger.
  • the electrolysis discharge is examined by gas chromatography. Thereafter, in addition to 938 g of unreacted 1,2-dimethoxyethane, 269 g of CH3O-CH2CH (OCH3) 2 and 61 g of CH3O-CH2-CH2-O-CH2-OCH3.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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  • Metallurgy (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

Process for the preparation of methoxyacetaldehyde dialkyl acetals by electrooxidation of 1-methoxy-2-alkoxyethane in the presence of alkanols and certain triarylamine compounds.

Description

Die Erfindung betrifft ein neues elektrochemisches Verfahren zur Herstellung von Methoxiacetaldehyddialkylacetalen.The invention relates to a new electrochemical process for the preparation of methoxy acetaldehyde dialkyl acetals.

Die Elektrooxidation von 1,2-Dimethoxiethan ist z.B. aus der DE-OS 30 00 243 bekannt. Bei diesem Verfahren entstehen entsprechend nachfolgendem Reaktionsschema eine Reihe von Nebenprodukten

Figure imgb0001
Es bestand daher die Aufgabe, ein Verfahren zu finden, das es ermöglicht, Methoxiacetaldehyddialkylacetale mit größerer Selektivität herzustellen.The electrooxidation of 1,2-dimethoxyethane is known, for example, from DE-OS 30 00 243. This process produces a number of by-products according to the reaction scheme below
Figure imgb0001
 The object was therefore to find a process which makes it possible to prepare methoxiacetaldehyde dialkyl acetals with greater selectivity.

Es wurde nun gefunden, daß man Methoxiacetaldehyddialkylacetale der allgemeinen Formel
    CH₃O-CH₂-CH(OR)₂      I
durch Elektrooxidation von Verbindungen der Formel
    CH₃O-CH₂-CH₂OR      II
in Gegenwart eines Alkanols der Formel ROH, wobei R einen Alkylrest mit 1 bis 4 C-Atomen bedeutet, mit erheblich höherer Selektivität erhält, wenn man die Elektrooxidation in Gegenwart einer Triarylaminverbindung der Formel

Figure imgb0002
in der beide A entweder Wasserstoffatome oder zusammen eine Einfach­bindung, X ein Halogenatom oder einen H₃COC-, NO₂- oder NC-Rest, Y ein Wasserstoffatom, einen NO₂- oder CH₃COC-Rest oder ein Halogenatom und Z ein Wasserstoffatom, einen NO₂-Rest oder ein Halogenatom bedeuten, durchführt.It has now been found that methoxiacetaldehyde dialkyl acetals of the general formula
CH₃O-CH₂-CH (OR) ₂ I
by electrooxidation of compounds of the formula
CH₃O-CH₂-CH₂OR II
in the presence of an alkanol of the formula ROH, where R is an alkyl radical having 1 to 4 carbon atoms, with considerably higher selectivity if the electrooxidation is carried out in the presence of a triarylamine compound of the formula
Figure imgb0002
 in which both A are either hydrogen atoms or together a single bond, X is a halogen atom or an H₃COC, NO₂ or NC radical, Y is a hydrogen atom, a NO₂ or CH₃COC radical or a halogen atom and Z is a hydrogen atom, a NO₂ radical or is a halogen atom.

Es ist zwar aus der US-PS 4 612 092 bekannt, daß man Alkylbenzole, wie Toluol oder p-Xylol, in Gegenwart von Alkanolen und Triarylaminen der Formel III zu Benzoesäureestern elektrolysieren kann. Demgegenüber ist das vorteilhafte Ergebnis des Verfahrens dieser Erfindung aber überraschend, weil hier die Acetale in hohen Selektivitäten entstehen und nicht zu den entsprechenden Estern weiter oxidiert werden.It is known from US Pat. No. 4,612,092 that alkylbenzenes, such as toluene or p-xylene, can be electrolyzed to benzoic acid esters in the presence of alkanols and triarylamines of the formula III. In contrast, the advantageous result of the process of this invention is surprising, because here the acetals are formed in high selectivities and are not further oxidized to the corresponding esters.

In der Ausgangsverbindung II steht R für eine Alkylgruppe mit 1 bis 4 C-Atomen, R ist z.B. einer der Reste: -CH₃, -C₂H₅, -C₃H₇ oder -C₄H₉. Bevorzugtes Ausgangsmaterial ist 1,2-Dimethoxiethan.In the starting compound II, R represents an alkyl group having 1 to 4 carbon atoms, R is e.g. one of the residues: -CH₃, -C₂H₅, -C₃H₇ or -C₄H₉. The preferred starting material is 1,2-dimethoxyethane.

Als Alkanole der Formel ROH kommen z.B. Ethanol, Propanol, Isopropanol, Butanol, Isobutanol und vorzugsweise Methanol in Betracht.Examples of alkanols of the formula ROH include Ethanol, propanol, isopropanol, butanol, isobutanol and preferably methanol.

Triarylaminverbindungen der Formel III sind Verbindungen folgender Struktur

Figure imgb0003
Sie enthalten als Halogenatome z.B. F-, Cl- oder Br-Atome. Verbindungen der Formel III sind z.B. Tris-(4-bromphenyl)-amin, Bis-(4-bromphenyl)-­(2,4-dibromphenyl)-amin, Bis-(2,4-dibromphenyl)-4-bromphenylamin, Tris-(2,4-dibromphenyl)-amin, Tris-(4-chlorphenyl)-amin, Bis-(4-chlor­phenyl)-(2,4-dichlorphenyl)-amin, Bis-(2,4-dichlorphenyl)-(4-chlor­phenyl)-amin und Tris-(2,4-dichlorphenyl)-amin, von denen Tris-(2,4-di­bromphenyl)-amin und Tris-(2,4-dichlorphenyl)-amin bevorzugt sind.Triarylamine compounds of the formula III are compounds of the following structure
Figure imgb0003
 They contain, for example, F, Cl or Br atoms as halogen atoms. Compounds of the formula III are, for example, tris (4-bromophenyl) amine, bis (4-bromophenyl) - (2,4-dibromophenyl) amine, bis (2,4-dibromophenyl) -4-bromophenylamine, tris (2,4-dibromophenyl) amine, tris- (4-chlorophenyl) amine, bis- (4-chlorophenyl) - (2,4-dichlorophenyl) amine, bis- (2,4-dichlorophenyl) - (4th -chlorophenyl) amine and tris (2,4-dichlorophenyl) amine, of which tris (2,4-dibromophenyl) amine and tris (2,4-dichlorophenyl) amine are preferred.

Dem Elektrolyten werden die in der organischen Elektrochemie üblichen Leitsalze, wie Salze der Tetrafluorborsäure, Salze von Alkyl- oder Arylsulfonsäuren oder Salze von Alkylschwefelsäuren sowie Salze der Perchlorsäure zugesetzt. Weiterhin kommen Alkoholate, wie NaOCH₃ und KOCH₃ in Betracht.The electrolyte is supplemented with the conductive salts commonly used in organic electrochemistry, such as salts of tetrafluoroboric acid, salts of alkyl or arylsulfonic acids or salts of alkylsulfuric acids and salts of perchloric acid. Furthermore, alcoholates such as NaOCH₃ and KOCH₃ come into consideration.

Zur Erhöhung der Löslichkeit des Elektronenüberträgers können dem Elektrolyten Kolösungsmittel zugesetzt werden. Als Kolösungsmittel kommen z. B. Halogenkohlenwasserstoffe, wie Methylenchlorid, Dichlorethan, 1,2-Dichlorpropan oder Nitrile, wie Acetonitril in Betracht. Die Kolösungsmittel werden dem Alkohol z. B. in Mengen bis zu 60 Gew.-Teilen pro 100 Gew.-Teile Alkanol zugegeben.To increase the solubility of the electron carrier, cosolvents can be added to the electrolyte. As co-solvents come e.g. B. halogenated hydrocarbons, such as methylene chloride, dichloroethane, 1,2-dichloropropane or nitriles, such as acetonitrile. The cosolvents are the alcohol z. B. in amounts up to 60 parts by weight per 100 parts by weight of alkanol.

Das erfindungsgemäße Verfahren benötigt keine besonderen Elektrolysezelle, bevorzugt wird eine ungeteilte Durchflußzelle eingesetzt. Als Anoden können alle an sich üblichen Anodenmaterialien verwendet werden, die unter den Elektrolysebedingungen stabil sind, wie Edelmetalle, z. B. Gold oder Platin. Bevorzugt verwendet man Graphit. Als Kathodenmaterial kommen u. a. Graphit, Eisen, Stahl, Nickel oder auch Edelmetalle, wie Platin, in Betracht.The method according to the invention does not require a special electrolysis cell; an undivided flow cell is preferably used. All anode materials which are customary per se and which are stable under the electrolysis conditions, such as noble metals, e.g. B. gold or platinum. Graphite is preferably used. As cathode material u. a. Graphite, iron, steel, nickel or even noble metals such as platinum.

Der bei der Elektrooxidation eingesetzte Elektrolyt hat beispielsweise folgende Zusammensetzung:

1 bis 70 Gew.% Ausgangsverbindung der Formel II
30 bis 96 Gew.% Alkanol mit oder ohne Kolösungsmittel
0,3 bis 5 Gew.% Triarylaminverbindungen der Formel III
0,3 bis 4 Gew.% Leitsalz
The electrolyte used in electrooxidation has the following composition, for example:

1 to 70% by weight of starting compound of the formula II
30 to 96% by weight alkanol with or without cosolvent
0.3 to 5% by weight of triarylamine compounds of the formula III
0.3 to 4% by weight of conductive salt

Man elektrolysiert bei Stromdichten von 0,25 bis 10 A/dm², vorteilhaft von 0,5 bis 5 A/dm², bevorzugt bei 1,0 bis 4 A/dm². Die Ladungsmenge beträgt 1 bis 10, vorzugsweise 2 bis 8 F pro Mol Ausgangsstoff.Electrolysis is carried out at current densities of 0.25 to 10 A / dm², advantageously from 0.5 to 5 A / dm², preferably at 1.0 to 4 A / dm². The amount of charge is 1 to 10, preferably 2 to 8 F per mole of starting material.

Die Elektrolysetemperaturen sind nach oben hin durch den Siedepunkt des Alkanols bzw. des Kolösungsmittels begrenzt. Zweckmäßigerweise elektrolysiert man bei Temperaturen bis 5°C unterhalb des Siedepunktes des Elektrolyten. Bei Verwendung von Methanol wird z.B. bei Temperaturen bis 60°C, vorzugsweise bei 20 bis 60°C, elektrolysiert. Das Verfahren kann sowohl diskontinuierlich als auch kontinuierlich durchgeführt werden.The upper limit of the electrolysis temperatures is the boiling point of the alkanol or the cosolvent. Expediently, electrolysis is carried out at temperatures up to 5 ° C. below the boiling point of the electrolyte. When using methanol e.g. at temperatures up to 60 ° C, preferably at 20 to 60 ° C, electrolyzed. The process can be carried out batchwise or continuously.

Die Aufarbeitung der Elektrolyseausträge nimmt man nach an sich bekannten Methoden vor. Zweckmäßigerweise wird der Elektrolyseaustrag destillativ aufgearbeitet. Überschüssiges Alkanol und evtl. eingesetztes Kolösungs­mittel werden zunächst abdestilliert, Leitsalz und Triarylaminoverbindung werden abfiltriert und die Methoxiacetaldehyddialkylacetale werden gereinigt, z. B. durch Destillation. Alkanol, Kolösungsmittel, Leitsalz und Triarylaminoverbindung sowie nicht umgesetzte Verbindungen der Formel II können zur Elektrolyse zurückgeführt werden.The electrolysis discharges are worked up using methods known per se. The electrolysis discharge is expediently worked up by distillation. Excess alkanol and any cosolvent used are first distilled off, conductive salt and triarylamino compound are filtered off and the methoxiacetaldehyde dialkyl acetals become cleaned, e.g. B. by distillation. Alkanol, cosolvent, conductive salt and triarylamino compound and unreacted compounds of the formula II can be recycled to the electrolysis.

Die nach dem erfindungsgemäßen Verfahren erhältlichen Methoxiacetaldehyd­dialkylacetale sind wertvolle Zwischenprodukte für die Synthese von Arzneimitteln insbesondere von Sulfonamiden.The methoxy acetaldehyde dialkyl acetals obtainable by the process according to the invention are valuable intermediates for the synthesis of medicaments, in particular sulfonamides.

Beispiel 1example 1 Elektrosynthese von MethoxiacetaldehyddimethylacetalElectrosynthesis of methoxy acetaldehyde dimethyl acetal

Apparatur: Ungeteilte Zelle mit 6 Elektroden, bipolare Elektroden­anordnung, Elektrodenabstände: 0,5 mm, Anoden und Kathoden: Graphit.

Zusammensetzung des Elektrolyten:
1225 g (13,61 Mol) 1,2-Dimethoxiethan
12,3 g Natriumbenzolsulfonat
12,3 g Natriummethylat
12,3 g Tris(2,4-dibromphenyl)amin
1188 g Methanol

Stromdichte: 3,3 A/dm²

Temperatur: 27 bis 28°C

Elektrolyse mit 2,2 F/Mol 1,2-Dimethoxiethan
Apparatus: undivided cell with 6 electrodes, bipolar electrode arrangement, electrode spacing: 0.5 mm, anodes and cathodes: graphite.

Composition of the electrolyte:
1225 g (13.61 mol) of 1,2-dimethoxyethane
12.3 g sodium benzenesulfonate
12.3 g sodium methylate
12.3 g tris (2,4-dibromophenyl) amine
1188 g of methanol

Current density: 3.3 A / dm²

Temperature: 27 to 28 ° C

Electrolysis with 2.2 F / mol 1,2-dimethoxyethane

Der Elektrolyt wird während der Elektrolyse mit 200 l/h über einen Wärmetauscher durch die Zelle gepumpt. Der Elektrolyseaustrag wird gaschromatographisch untersucht. Hiernach erhält man neben 938 g unumgesetzten 1,2-Dimethoxiethan 269 g CH₃O-CH₂CH(OCH₃)₂ und 61 g CH₃O-CH₂-CH₂-O-CH₂-OCH₃.During the electrolysis, the electrolyte is pumped through the cell at 200 l / h via a heat exchanger. The electrolysis discharge is examined by gas chromatography. Thereafter, in addition to 938 g of unreacted 1,2-dimethoxyethane, 269 g of CH₃O-CH₂CH (OCH₃) ₂ and 61 g of CH₃O-CH₂-CH₂-O-CH₂-OCH₃.

Hieraus errechnen sich:
Umsatz 1,2-Dimethoxiethan: 23,4 %
Selektivität CH₃O-CH₂-CH(OCH₃)₂: 70,3 %
Selektivität CH₃O-CH₂-CH₂O-CH₂-OCH₃: 15,9 %From this can be calculated:
Turnover 1,2-dimethoxyethane: 23.4%
Selectivity CH₃O-CH₂-CH (OCH₃) ₂: 70.3%
Selectivity CH₃O-CH₂-CH₂O-CH₂-OCH₃: 15.9%

Beispiel 2 (Vergleichsversuch)Example 2

Man verfährt wie im Beispiel 1 beschrieben, wobei man jedoch ohne Zusatz von Tris-(2,4-dibromphenyl-)-amin arbeitet. Dabei werden folgende Ergebnisse erhalten:
Umsatz 1,2-Dimethoxiethan: 28,4 %
Selektivität CH₃O-CH₂-CH(OCH₃)₂: 43,8 %
Selektivität CH₃O-CH₂-CH₂-O-CH₂OCH₃: 42,2 %The procedure is as described in Example 1, but the process is carried out without the addition of tris (2,4-dibromophenyl) amine. The following results are obtained:
Turnover 1,2-dimethoxyethane: 28.4%
Selectivity CH₃O-CH₂-CH (OCH₃) ₂: 43.8%
Selectivity CH₃O-CH₂-CH₂-O-CH₂OCH₃: 42.2%

Claims (6)

1. Verfahren zur Herstellung von Methoxiacetaldehyddialkylacetalen der Formel
      CH₃O-CH₂-CH(OR)₂      I
durch Elektrooxidation von Verbindungen der Formel
      CH₃O-CH₂-CH₂OR      II,
in Gegenwart eines Alkanols der Formel ROH, wobei R einen Alkylrest mit 1 bis 4 C-Atomen bedeutet, dadurch gekennzeichnet, daß man die Elektrooxidation in Gegenwart einer Triarylaminverbindung der Formel
Figure imgb0004
 in der beide A entweder Wasserstoffatome oder zusammen eine Einfachbindung, X ein Halogenatom oder einen H₃COC-, NO₂- oder NC-Rest, Y ein Wasserstoffatom, einen NO₂- oder CH₃COC-Rest oder ein Halogenatom und Z ein Wasserstoffatom, einen NO₂-Rest oder ein Halogenatom bedeuten, durchführt.1. Process for the preparation of methoxy acetaldehyde dialkyl acetals of the formula
CH₃O-CH₂-CH (OR) ₂ I
by electrooxidation of compounds of the formula
CH₃O-CH₂-CH₂OR II,
in the presence of an alkanol of the formula ROH, where R is an alkyl radical having 1 to 4 carbon atoms, characterized in that the electrooxidation in the presence of a triarylamine compound of the formula
Figure imgb0004
 in which both A are either hydrogen atoms or together a single bond, X is a halogen atom or an H₃COC, NO₂ or NC radical, Y is a hydrogen atom, a NO₂ or CH₃COC radical or a halogen atom and Z is a hydrogen atom, a NO₂ radical or is a halogen atom. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man als Verbindung II 1,2-Dimethoxiethan verwendet.2. The method according to claim 1, characterized in that 1,2-dimethoxyethane is used as the compound II. 3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man als Alkanol Methanol verwendet.3. The method according to claim 1, characterized in that methanol is used as the alkanol. 4. Verfahren nach den Ansprüchen 1 und 2, dadurch gekennzeichnet, daß man als Triarylaminverbindung Tris-(2,4-dibromphenyl)-amin oder Tris-(2,4-­dichlorphenyl)-amin verwendet.4. Process according to claims 1 and 2, characterized in that tris (2,4-dibromophenyl) amine or tris (2,4-dichlorophenyl) amine is used as the triarylamine compound. 5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man einen Elektrolyten verwendet, der einen Gehalt an Ausgangsverbindung der Formel II von 1 bis 70 Gew.%, an Alkanol, mit oder ohne Kolösungs­mittel, von 30 bis 96 Gew.%, an Triarylamin der Formel III von 0,3 bis 5 Gew.% und an Leitsalz von 0,3 bis 4 Gew.% aufweist.5. The method according to claim 1, characterized in that an electrolyte is used which has a content of starting compound of formula II from 1 to 70 wt.%, Of alkanol, with or without cosolvent, from 30 to 96 wt.%, Of triarylamine of the formula III from 0.3 to 5% by weight and of conducting salt from 0.3 to 4% by weight. 6. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man bei Stromdichten von 0,25 bis 10 A/dm² und mit einer Ladungsmenge von 1 bis 10 F pro Mol Ausgangsstoff der Formel II elektrolysiert.6. The method according to claim 1, characterized in that electrolysed at current densities of 0.25 to 10 A / dm² and with a charge of 1 to 10 F per mole of starting material of the formula II.
EP88103423A 1987-03-14 1988-03-05 Process for the preparation of methoxyacetaldehyde dialkyl acetals Expired - Lifetime EP0283807B1 (en)

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DE19873708337 DE3708337A1 (en) 1987-03-14 1987-03-14 METHOD FOR PRODUCING METHOXIACETALDEHYDDIALKYLACETALS
DE3708337 1987-03-14

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004085710A2 (en) * 2003-03-25 2004-10-07 Degussa Ag Method for the anodic alkoxylation of organic substrates

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3000243A1 (en) * 1980-01-05 1981-07-09 Hoechst Ag, 6230 Frankfurt Electrochemical alkoxylation of aliphatic ether(s) - using vitreous carbon or platinum anode(s)
EP0152801A2 (en) * 1984-02-03 1985-08-28 BASF Aktiengesellschaft Process for manufacturing benzaldehyde dialkylacetals
US4612092A (en) * 1984-09-27 1986-09-16 Basf Aktiengesellschaft Preparation of aromatic carboxylates

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3000243A1 (en) * 1980-01-05 1981-07-09 Hoechst Ag, 6230 Frankfurt Electrochemical alkoxylation of aliphatic ether(s) - using vitreous carbon or platinum anode(s)
EP0152801A2 (en) * 1984-02-03 1985-08-28 BASF Aktiengesellschaft Process for manufacturing benzaldehyde dialkylacetals
US4612092A (en) * 1984-09-27 1986-09-16 Basf Aktiengesellschaft Preparation of aromatic carboxylates

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004085710A2 (en) * 2003-03-25 2004-10-07 Degussa Ag Method for the anodic alkoxylation of organic substrates
WO2004085710A3 (en) * 2003-03-25 2005-04-21 Degussa Method for the anodic alkoxylation of organic substrates

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EP0283807B1 (en) 1991-04-10
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