EP0030588B1 - Process for the preparation of p-tert.-butylbenzaldehyde - Google Patents
Process for the preparation of p-tert.-butylbenzaldehyde Download PDFInfo
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- EP0030588B1 EP0030588B1 EP80105721A EP80105721A EP0030588B1 EP 0030588 B1 EP0030588 B1 EP 0030588B1 EP 80105721 A EP80105721 A EP 80105721A EP 80105721 A EP80105721 A EP 80105721A EP 0030588 B1 EP0030588 B1 EP 0030588B1
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- tert
- anode
- butylbenzaldehyde
- butyltoluene
- metal oxide
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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
Definitions
- the present invention relates to a process for producing an aldehyde, namely p-tert. Butylbenzaldehyde.
- butylbenzaldehyde has been obtained by oxidation of p-tert. Butyltoluene with chemical oxidizing agents, especially with manganese dioxide. This procedure has serious disadvantages, in particular with regard to the manganese salts which are obtained in large quantities. Furthermore, the manganese dioxide used here is not supplied in the same quality, but rather in very different quality, which of course does not allow a uniform procedure.
- the inventive method for the production of p-tert. Butylbenzaldehyde by anodic oxidation of p-tert. Butyl toluene is that the oxidation in a p-tert. Carries out medium containing butyltoluene, which consists of a non-oxidative aqueous mineral acid and optionally an organic solvent, if desired in the presence of a metal salt.
- Metal anode anodes for example lead dioxide or manganese dioxide anodes, are expediently used as anodes in the process according to the invention.
- a particularly preferred embodiment of the method according to the invention consists in using a metal oxide-titanium composite anode.
- Such composite anodes consist of a carrier made of titanium, which is provided with a metal oxide coating, an intermediate layer of a carbide or boride of the elements of the IV. And V. subgroup being applied to the titanium surface before the metal oxide coating is applied.
- Such a composite anode namely a lead dioxide-titanium composite anode, and its production is described in German Patent 2,344,645.
- An improved method for producing such an anode is described in German Offenlegungsschrift No. 2,722,840. According to the invention, such a lead dioxide-titanium composite anode is preferably used.
- manganese dioxide is used as the anode material, this can be applied either to graphite or to lead or to lead dioxide.
- graphite anodes can advantageously be used in the invention.
- anode materials that can be used are precious metals, e.g. B. platinum or platinized titanium.
- the cathode materials used in the method according to the invention are not critical. Steel, nickel and copper, for example, are suitable as cathode materials.
- the electrodes both the anode and the cathode, can have customary shapes.
- the electrodes can be designed in the form of plates or grids or as expanded metal.
- the electrolysis can be carried out in undivided or in divided cells, in which case the latter can be divided with membranes or diaphragms made of conventional membrane or diaphragm materials.
- the voltages and currents used depend on the solvent used, the size of the cell and the current density used. A voltage of between approximately 3 and approximately 20 V is generally used.
- the current density can vary within wide limits, the current densities generally between approximately 0.01 and approximately 100 mA per cm 2 , in particular between approximately 0.4 and approximately 50 may be mA per cm 2 .
- the electrolysis according to the invention can be carried out directly in a mixture of an electrolyte and the p-tert used as the starting material. Butyltoluene are carried out using no other solvent.
- aqueous acids in particular non-oxidative mineral acids, can be used as electrolytes.
- Sulfuric acid has proven to be particularly suitable. It is advisable to work with a 5-50%, especially with a 7.5-15%, aqueous sulfuric acid.
- a mixture which consists of the abovementioned aqueous acid and an inert organic solvent, for example a hydrocarbon such as hexane, a chlorinated hydrocarbon such as dichloroethane or methylene chloride, a tertiary lower alkanol, for example tert. Butanol, or acetone.
- an inert organic solvent for example a hydrocarbon such as hexane, a chlorinated hydrocarbon such as dichloroethane or methylene chloride, a tertiary lower alkanol, for example tert. Butanol, or acetone.
- the proportion of the organic solvent in the mixture is expediently from about 10 to about 60%.
- phase transfer catalyst for example a tetraalkylammonium salt, such as tetrabutylammonium hydrogen sulfate.
- a phase transfer catalyst is the dodecyl hydrogen sulfate sodium salt.
- metal oxide anodes in particular metal oxide composite anodes
- dichloroethane as the solvent
- graphite anodes acetone has proven to be particularly advantageous as solvent.
- Butylbenzaldehyde in particular when graphite anodes are used, in addition to the desired p-tert. Butylbenzaldehyde in smaller amounts the corresponding alcohol. This can be separated by distillation and returned to the process, i. H. the starting material, p-tert. Butyltoluene, can be added.
- the concentration of the starting material in the electrolyte mixture used can generally vary between about 1 and 80%, in particular between about 10 and 50%, preferably between about 10 and 20%.
- the temperature used in carrying out the method according to the invention is not critical. However, there is an upper limit on the boiling point of the solvent. Generally one works between room temperature and about 80 ° C, in particular between room temperature and about 60 ° C.
- Metal salts for example manganese-II salts, such as manganese-II sulfate or cerium III salts, such as cerium-III sulfate, can be added to the electrolyte in a manner known per se, in only small amounts, for example in an amount of about 10% based on the amount of the batch.
- an undivided electrolysis cell provided with a graphite foil with a surface area of 25 cm 2 as the anode and a nickel wire as the cathode, a solution of 2.5 ml of p-tert. Butyltoluene in 40 ml of 3N aqueous sulfuric acid and 80 ml of acetone at room temperature, 0.75 A current and 7.8-8.5 V voltage electrolyzed with stirring. After the electrolysis has ended (after 2 hours), a sample is taken and extracted with chloroform. The products are determined by gas chromatography. With a conversion of 79%, the yield of p-tert. Butylbenzaldehyde (based on converted p-tert. Butyltoluene) 60 mol%, the yield of p-tert. Butylbenzyl alcohol 10 mol%.
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
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- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung eines Aldehyds, nämlich von p-tert. Butylbenzaldehyd.The present invention relates to a process for producing an aldehyde, namely p-tert. Butylbenzaldehyde.
Der p-tert. Butylbenzaldehyd wurde bisher durch Oxydation von p-tert. Butyltoluol mit chemischen Oxydationsmitteln, insbesondere mit Mangandioxyd, hergestellt. Diese Verfahrensweise hat schwerwiegende Nachteile, insbesondere im Hinblick auf die hierbei in großen Mengen anfallenden Mangansalze. Weiterhin wird das hierbei verwendete Mangandioxyd nicht in gleichbleibender, sondern vielmehr in sehr unterschiedlicher Qualität geliefert, was naturgemäß eine einheitliche Verfahrensführung nicht ermöglicht.The p-tert. So far, butylbenzaldehyde has been obtained by oxidation of p-tert. Butyltoluene with chemical oxidizing agents, especially with manganese dioxide. This procedure has serious disadvantages, in particular with regard to the manganese salts which are obtained in large quantities. Furthermore, the manganese dioxide used here is not supplied in the same quality, but rather in very different quality, which of course does not allow a uniform procedure.
In Helv. Chem. Acta 9, 1097 (1926) ist die Elektrosynthese von in 4-Stellung substituierten Benzaldehyden durch anodische Oxydation der entsprechenden Alkylbenzole beschrieben. Bei diesem bekannten Verfahren, bei dem man die Alkylbenzole in schwefelsaurer Lösung elektrolysiert, werden die Benzaldehyde nur in geringer Ausbeute erhalten und es bereitet außerdem die Isolierung der Aldehyde aus dem bei der Elektrolyse entstehenden Vielkomponentengemisch so große Schwierigkeiten, daß sich diese Synthese in der Technik nicht realisieren ließ.Helv. Chem. Acta 9, 1097 (1926) describes the electrosynthesis of benzaldehydes substituted in the 4-position by anodic oxidation of the corresponding alkylbenzenes. In this known process, in which the alkylbenzenes are electrolyzed in sulfuric acid solution, the benzaldehydes are obtained only in low yield and it also causes the isolation of the aldehydes from the multicomponent mixture resulting from the electrolysis so great difficulties that this synthesis is not technically feasible realized.
Abweichend von diesem in Helv. Chem. Acta beschriebenen Stand der Technik werden gemäß US-A-4 148 696 alkylsubstituierte aromatische Verbindungen wie beispielsweise p-tert. Butyltoluol, nicht in schwefelsaurer Lösung oxidiert, sondern vielmehr in einer wäßrigen Alkancarbonsäure, wie beispielsweise Essigsäure, Isovaleriansäure oder dgl. Man war offenbar der Meinung, daß die schlechten Ausbeuten, wie sie nach dem Verfahren gemäß der genannten Literaturstelle aus Helv. Chem. Acta erhalten werden, darauf beruhen, daß man dort in Gegenwart einer Mineralsäure, wie Schwefelsäure, gearbeitet hat, und daß man daher davon abgehen müsse, eine Mineralsäure, wie Schwefelsäure, zu verwenden. So wird denn auch gemäß US-A-4148696 (Beispiel 111) bei der anodischen Oxydation von p-tert. Butyltoluol wäßrige Essigsäure verwendet. Nach wie vor erhält man aber bei dieser Verfahrensweise den gewünschten p-tert. Butylbenzaldehyd nur in verhältnismäßig geringen Ausbeuten, wobei der Umsatz sehr gering ist und verhältnismäßig große Mengen an unerwünschtem p-tert. Butylbenzylacetat anfallen. Den gewünschten p-tert. Butylbenzaldehyd erhält man in einer Ausbeute von nur etwa 48%.Deviating from this prior art described in Helv. Chem. Acta, according to US Pat. No. 4,148,696, alkyl-substituted aromatic compounds such as p-tert. Butyltoluene, not oxidized in sulfuric acid solution, but rather in an aqueous alkane carboxylic acid, such as, for example, acetic acid, isovaleric acid or the like. Apparently, it was believed that the poor yields obtained by the process according to the above-mentioned literature from Helv. Chem. Acta will be based on the fact that one has worked there in the presence of a mineral acid, such as sulfuric acid, and that one must therefore proceed from using a mineral acid, such as sulfuric acid. Thus, according to US-A-4148696 (Example 111) in the anodic oxidation of p-tert. Butyltoluene aqueous acetic acid used. However, the desired p-tert is still obtained with this procedure. Butylbenzaldehyde only in relatively low yields, the conversion being very low and relatively large amounts of undesirable p-tert. Butylbenzyl acetate arise. The desired p-tert. Butylbenzaldehyde is obtained in a yield of only about 48%.
Es wurde nun ein Verfahren gefunden, welches nicht mit den obigen Nachteilen und Schwierigkeiten verbunden ist und welches es dennoch ermöglicht, das gewünschte Produkt in hoherAusbeute zu erhalten.A process has now been found which is not associated with the above disadvantages and difficulties and which nevertheless makes it possible to obtain the desired product in high yield.
Das erfindungsgemäße Verfahren zur Herstellung von p-tert. Butylbenzaldehyd durch anodische Oxydation von p-tert. Butyltoluol besteht darin, daß man die Oxydation in einem das p-tert. Butyltoluol enthaltenden Medium durchführt, welches aus einer nicht-oxidativen wäßrigen Mineralsäure und gegebenenfalls einem organischen Lösungsmittel besteht, gewünschtenfalls in Gegenwart eines Metallsalzes.The inventive method for the production of p-tert. Butylbenzaldehyde by anodic oxidation of p-tert. Butyl toluene is that the oxidation in a p-tert. Carries out medium containing butyltoluene, which consists of a non-oxidative aqueous mineral acid and optionally an organic solvent, if desired in the presence of a metal salt.
Als Anoden werden beim erfindungsgemäßen Verfahren zweckmäßig Metalloxydanoden, beispielsweise Bleidioxyd- oder Mangandioxyd-Anoden verwendet.Metal anode anodes, for example lead dioxide or manganese dioxide anodes, are expediently used as anodes in the process according to the invention.
Eine besonders bevorzugte Ausführungsform des erfindungsgemäßen Verfahrens besteht darin, daß man eine Metalloxyd-Titan-Verbundanode verwendet. Solche Verbundanoden bestehen aus einem Träger aus Titan, welcher mit einer Metalloxydauflage versehen ist, wobei auf der Titanoberfläche vor der Aufbringung des Metalloxydüberzuges eine Zwischenschicht aus einem Carbid oder Borid der Elemente der IV. und V. Nebengruppe aufgebracht wird. Eine derartige Verbundanode, nämlich eine Bleidioxyd-Titan-Verbundanode, sowie deren Herstellung ist in der deutschen Patentschrift 2 344 645 beschrieben. Ein verbessertes Verfahren zur Herstellung einer derartigen Anode ist in der deutschen Offenlegungsschrift 2 722 840 beschrieben. Erfindungsgemäß wird bevorzugt eine derartige Bleidioxyd-Titan-Verbundanode verwendet.A particularly preferred embodiment of the method according to the invention consists in using a metal oxide-titanium composite anode. Such composite anodes consist of a carrier made of titanium, which is provided with a metal oxide coating, an intermediate layer of a carbide or boride of the elements of the IV. And V. subgroup being applied to the titanium surface before the metal oxide coating is applied. Such a composite anode, namely a lead dioxide-titanium composite anode, and its production is described in German Patent 2,344,645. An improved method for producing such an anode is described in German Offenlegungsschrift No. 2,722,840. According to the invention, such a lead dioxide-titanium composite anode is preferably used.
Bei Verwendung von Mangandioxyd als Anodenmaterial kann dieses entweder auf Graphit oder auf Blei oder auch auf Bleidioxyd aufgebracht sein.If manganese dioxide is used as the anode material, this can be applied either to graphite or to lead or to lead dioxide.
Ferner können beim erfindungsgemäßen mit Vorteil Graphitanoden verwendet werden.Furthermore, graphite anodes can advantageously be used in the invention.
Weitere verwendbare Anodenmaterialien sind Edelmetalle, z. B. Platin oder platiniertes Titan.Other anode materials that can be used are precious metals, e.g. B. platinum or platinized titanium.
Die beim erfindungsgemäßen Verfahren verwendeten Kathodenmaterialien sind nicht kritisch. Als Kathodenmaterialien sind beispielsweise Stahl, Nickel und Kupfer geeignet.The cathode materials used in the method according to the invention are not critical. Steel, nickel and copper, for example, are suitable as cathode materials.
Die Elektroden, und zwar sowohl die Anode wie auch die Kathode, können übliche Formen aufweisen. Beispielsweise können die Elektroden in Form von Platten oder Gittern oder als Streckmetall ausgebildet sein.The electrodes, both the anode and the cathode, can have customary shapes. For example, the electrodes can be designed in the form of plates or grids or as expanded metal.
Die Elektrolyse kann in ungeteilten oder in unterteilten Zellen durchgeführt werden, wobei im letzteren Falle die Unterteilung mit Membranen oder Diaphragmen aus üblichen Membran- bzw. Diaphragmen-Materialien erfolgen kann.The electrolysis can be carried out in undivided or in divided cells, in which case the latter can be divided with membranes or diaphragms made of conventional membrane or diaphragm materials.
Die angewandten Spannungen und Stromstärken richten sich nach dem verwendeten Lösungsmittel, nach der Größe der Zelle und nach der angewandten Stromdichte. Im allgemeinen arbeitet man mit einer Spannung zwischen etwa 3 und etwa 20 V. Die Stromdichte kann innerhalb weiter Grenzen schwanken, wobei die Stromdichten im allgemeinen zwischen etwa 0,01 und etwa 100 mA pro cm2, insbesondere zwischen etwa 0,4 und etwa 50 mA pro cm2 betragen können.The voltages and currents used depend on the solvent used, the size of the cell and the current density used. A voltage of between approximately 3 and approximately 20 V is generally used. The current density can vary within wide limits, the current densities generally between approximately 0.01 and approximately 100 mA per cm 2 , in particular between approximately 0.4 and approximately 50 may be mA per cm 2 .
Die erfindungsgemäße Elektrolyse kann direkt in einem Gemisch eines Elektrolyten und des als Ausgangsmaterial verwendeten p-tert. Butyltoluol durchgeführt werden, wobei kein weiteres Lösungsmittel verwendet wird. Als Elektrolyten können beispielsweise wäßrige Säuren, insbesondere nicht-oxidative Mineralsäuren verwendet werden. Als besonders geeignet hat sich hierbei die Schwefelsäure erwiesen. Zweckmäßig arbeitet man hierbei mit einer 5-50%igen, insbesondere mit einer 7,5-15%igen wäßrigen Schwefelsäure.The electrolysis according to the invention can be carried out directly in a mixture of an electrolyte and the p-tert used as the starting material. Butyltoluene are carried out using no other solvent. For example, aqueous acids, in particular non-oxidative mineral acids, can be used as electrolytes. Sulfuric acid has proven to be particularly suitable. It is advisable to work with a 5-50%, especially with a 7.5-15%, aqueous sulfuric acid.
Besonders bevorzugt ist die Verwendung eines Gemisches, welches aus der obengenannten wäßrigen Säure und einem inerten organischen Lösungsmittel besteht, beispielsweise einem Kohlenwasserstoff, wie Hexan, einem chlorierten Kohlenwasserstoff, wie Dichloräthan oder Methylenchlorid, einem tertiären niederen Alkanol, beispielsweise tert. Butanol, oder Aceton. Zweckmäßig beträgt der Anteil des organischen Lösungsmittels im Gemisch etwa 10 bis etwa 60%. Wenn ein derartiges Gemisch als organische Komponente ein mit Wasser nicht mischbares organisches Lösungsmittel enthält oder wenn man überhaupt ohne Verwendung eines zusätzlichen Lösungsmittels arbeitet (Verwendung des Ausgangsmaterials als Lösungsmittel) wird zweckmäßigerweise ein Phasentransferkatalysator verwendet, beispielsweise ein Tetraalkylammoniumsalz, wie Tetrabutylammoniumhydrogensulfat. Ein weiteres Beispiel eines solchen Phasentransfer-Katalysators ist das Dodecylhydrogensulfat-Natriumsalz.It is particularly preferred to use a mixture which consists of the abovementioned aqueous acid and an inert organic solvent, for example a hydrocarbon such as hexane, a chlorinated hydrocarbon such as dichloroethane or methylene chloride, a tertiary lower alkanol, for example tert. Butanol, or acetone. The proportion of the organic solvent in the mixture is expediently from about 10 to about 60%. If such a mixture contains as an organic component a water-immiscible organic solvent or if one works at all without the use of an additional solvent (use of the starting material as solvent), a phase transfer catalyst is advantageously used, for example a tetraalkylammonium salt, such as tetrabutylammonium hydrogen sulfate. Another example of such a phase transfer catalyst is the dodecyl hydrogen sulfate sodium salt.
Bei Verwendung von Metalloxydanoden, insbesondere von Metalloxyd-Verbundanoden hat es sich als besonders zweckmäßig erwiesen, als Lösungsmittel Dichloräthan zu verwenden, während sich bei Verwendung von Graphitanoden Aceton als Lösungsmittel als besonders vorteilhaft erwiesen hat.When using metal oxide anodes, in particular metal oxide composite anodes, it has proven to be particularly expedient to use dichloroethane as the solvent, while when using graphite anodes, acetone has proven to be particularly advantageous as solvent.
Insbesondere bei Verwendung von Graphitanoden bildet sich neben dem gewünschten p-tert. Butylbenzaldehyd in geringeren Mengen der entsprechende Alkohol. Dieser kann durch Destillation abgetrennt und in das Verfahren zurückgeführt, d. h. dem Ausgangsmaterial, p-tert. Butyltoluol, zugemischt werden.In particular when graphite anodes are used, in addition to the desired p-tert. Butylbenzaldehyde in smaller amounts the corresponding alcohol. This can be separated by distillation and returned to the process, i. H. the starting material, p-tert. Butyltoluene, can be added.
Die Konzentration des Ausgangsmaterials im verwendeten Elektrolytgemisch kann im allgemeinen zwischen etwa 1 und 80% schwanken, insbesondere zwischen etwa 10 und 50%, vorzugsweise zwischen etwa 10 und 20%.The concentration of the starting material in the electrolyte mixture used can generally vary between about 1 and 80%, in particular between about 10 and 50%, preferably between about 10 and 20%.
Die bei der Ausführung des erfindungsgemäßen Verfahrens angewandte Temperatur ist nicht kritisch. Sie wird jedoch nach oben hin durch den Siedepunkt des Lösungsmittels begrenzt. Im allgemeinen arbeitet man zwischen Raumtemperatur und etwa 80°C, insbesondere zwischen Raumtemperatur und etwa 60° C.The temperature used in carrying out the method according to the invention is not critical. However, there is an upper limit on the boiling point of the solvent. Generally one works between room temperature and about 80 ° C, in particular between room temperature and about 60 ° C.
Dem Elektrolyten können in an sich bekannterWeise Metallsalze, beispielsweise Mangan-II-Salze, wie Mangan-II-Sulfat oder Cer-III-Salze, wie Cer-III-Sulfat zugesetzt werden, und zwar in nur geringen Mengen, beispielsweise in einer Menge von etwa 10% bezogen auf die Menge des Ansatzes.Metal salts, for example manganese-II salts, such as manganese-II sulfate or cerium III salts, such as cerium-III sulfate, can be added to the electrolyte in a manner known per se, in only small amounts, for example in an amount of about 10% based on the amount of the batch.
Während der Elektrolyse ist für kräftiges Durchmischen des Ansatzes zu sorgen.Ensure that the batch is thoroughly mixed during the electrolysis.
In ein Glasgefäß mit Deckel werden 2,5 ml p-tert. Butyltoluol, 10 ml Dichloräthan und 110 ml 10N Schwefelsäure gegeben und unter Magnetrührung emulgiert. Als Anode wird Titanstreckmetall (5x5 cm), beschichtet mit Bleidioxyd, verwendet [Bleidioxyd-Titan-Verbundelektrode, beschrieben in Zeitschrift für Naturforschung »316, 39-50 (1976)], als Kathode dient ein Nickeldraht im Abstand von 3 cm von der Anode. Zwischen den Elektroden wird eine Spannung von 3,4 Volt angelegt, worauf sich ein Strom von 50 mA einstellt. Die Temperatur wird durch extreme Kühlung auf 25°C gehalten. Nach dem Durchgang von 1,55 Ah, was 100% des theoretisch benötigten Stromes entspricht, wird die Elektrolyse abgebrochen. Die Reaktionslösung wird dreimal mit je 60 ml Chloroform extrahiert und der kombinierte Extrakt im Gaschromatogramm quantitativ analysiert. Bei einem Umsatz von 83% resultiert eine Ausbeute an p-tert. Butylbenzaldehyd von 77% der Theorie.2.5 ml of p-tert are placed in a glass vessel with a lid. Butyltoluene, 10 ml dichloroethane and 110 ml 10N sulfuric acid and emulsified with magnetic stirring. Expanded titanium (5x5 cm) coated with lead dioxide is used as the anode [lead dioxide-titanium composite electrode, described in Zeitschrift für Naturforschung »316, 39-50 (1976)], a nickel wire at a distance of 3 cm from the anode is used as the cathode . A voltage of 3.4 volts is applied between the electrodes, whereupon a current of 50 mA is established. The temperature is kept at 25 ° C by extreme cooling. After the passage of 1.55 Ah, which corresponds to 100% of the theoretically required current, the electrolysis is stopped. The reaction solution is extracted three times with 60 ml of chloroform and the combined extract is analyzed quantitatively in the gas chromatogram. With a conversion of 83%, a yield of p-tert results. Butylbenzaldehyde of 77% of theory.
In einer ungeteilten Elektrolysezelle, versehen mit einer Graphitfolie von 25 cm2 Oberfläche als Anode und einem Nickeldraht als Kathode, wird eine Lösung von 2,5 ml p-tert. Butyltoluol in 40 ml 3N wäßriger Schwefelsäure und 80 ml Aceton bei Raumtemperatur, 0,75 A Stromstärke und 7,8-8,5 V Spannung unter Rühren elektrolysiert. Nach Beendigung der Elektrolyse (nach 2 Stunden) wird eine Probe entnommen und mit Chloroform extrahiert. Die Produkte werden gaschromatographisch bestimmt. Bei einem Umsatz von 79% beträgt die Ausbeute an p-tert. Butylbenzaldehyd (bezogen auf umgesetztes p-tert. Butyltoluol) 60 Mol-%, die Ausbeute an p-tert. Butylbenzylalkohol 10 Mol-%.In an undivided electrolysis cell, provided with a graphite foil with a surface area of 25 cm 2 as the anode and a nickel wire as the cathode, a solution of 2.5 ml of p-tert. Butyltoluene in 40 ml of 3N aqueous sulfuric acid and 80 ml of acetone at room temperature, 0.75 A current and 7.8-8.5 V voltage electrolyzed with stirring. After the electrolysis has ended (after 2 hours), a sample is taken and extracted with chloroform. The products are determined by gas chromatography. With a conversion of 79%, the yield of p-tert. Butylbenzaldehyde (based on converted p-tert. Butyltoluene) 60 mol%, the yield of p-tert. Butylbenzyl alcohol 10 mol%.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT80105721T ATE7235T1 (en) | 1979-11-16 | 1980-09-24 | PROCESS FOR THE PRODUCTION OF P-TERT. BUTYLBENZALDEHYDE. |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH10254/79 | 1979-11-16 | ||
| CH1025479 | 1979-11-16 | ||
| CH603480 | 1980-08-08 | ||
| CH6034/80 | 1980-08-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0030588A1 EP0030588A1 (en) | 1981-06-24 |
| EP0030588B1 true EP0030588B1 (en) | 1984-04-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP80105721A Expired EP0030588B1 (en) | 1979-11-16 | 1980-09-24 | Process for the preparation of p-tert.-butylbenzaldehyde |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP0030588B1 (en) |
| DE (1) | DE3067628D1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3322399A1 (en) * | 1983-06-22 | 1985-01-10 | Basf Ag, 6700 Ludwigshafen | METHOD FOR THE PRODUCTION OF BENZ ALDEHYDDIALKYLACETALEN |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0012942A2 (en) * | 1978-12-22 | 1980-07-09 | BASF Aktiengesellschaft | Electrolytic process for producing benzaldehydes |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2351932A1 (en) * | 1976-05-21 | 1977-12-16 | Rhone Poulenc Ind | METHYLBENZENES ANODIC OXIDATION PROCESS |
| US4148696A (en) * | 1978-03-20 | 1979-04-10 | Uop Inc. | Electrochemical oxidation of activated alkyl aromatic compounds |
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1980
- 1980-09-24 DE DE8080105721T patent/DE3067628D1/en not_active Expired
- 1980-09-24 EP EP80105721A patent/EP0030588B1/en not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0012942A2 (en) * | 1978-12-22 | 1980-07-09 | BASF Aktiengesellschaft | Electrolytic process for producing benzaldehydes |
Non-Patent Citations (1)
| Title |
|---|
| Helv. Chem. Acta. 9, 1097 (1926) * |
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| Publication number | Publication date |
|---|---|
| EP0030588A1 (en) | 1981-06-24 |
| DE3067628D1 (en) | 1984-05-30 |
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