EP0029995B1 - Process for the preparation of 4-tert.-butylbenzaldehyde - Google Patents
Process for the preparation of 4-tert.-butylbenzaldehyde Download PDFInfo
- Publication number
- EP0029995B1 EP0029995B1 EP80107345A EP80107345A EP0029995B1 EP 0029995 B1 EP0029995 B1 EP 0029995B1 EP 80107345 A EP80107345 A EP 80107345A EP 80107345 A EP80107345 A EP 80107345A EP 0029995 B1 EP0029995 B1 EP 0029995B1
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- EP
- European Patent Office
- Prior art keywords
- tert
- acid
- electrolysis
- butylbenzaldehyde
- butyltoluene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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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 the electrochemical production of 4-tert. Butylbenzaldehyde.
- the nucleic and side chain-substituted fatty acid esters also form as by-products in this process. Furthermore, the processing of the electrolysis discharges requires a number of separation operations. When the synthesis is carried out industrially, the fatty acids and fatty acid salts must be separated from the benzaldehydes and recycled, and then the benzaldehydes must be separated from the fatty acid esters.
- 4-tert-butylbenzaldehyde is obtained by electrochemical oxidation of 4-tert. Butyltoluene in the presence of mineral acids can be produced considerably more advantageously if the electrochemical oxidation is carried out in the presence of additional alkyl, alkenyl or arylsulfonic acids. 4-tert. Butylbenzaldehyde in high yield.
- Another major advantage of the method according to the invention is the simple processing of the electrolysis discharges. Thus, after the electrolysis has ended, the 4-tert can be obtained from the organic phase obtained by phase separation. Isolate butylbenzaldehyde directly by distillation.
- the new process can be carried out batchwise or continuously. Electrolysis does not require a special electrolysis cell. You can e.g. B. in the technically frequently used plate and frame cell.
- the electrolyte consists of 4-tert. Butyltoluene and an aqueous solution of a mineral acid to which small amounts of an alkyl, alkenyl or arylsulfonic acid are added.
- a mineral acid to which small amounts of an alkyl, alkenyl or arylsulfonic acid are added.
- sulfuric acid is used as the mineral acid.
- Long-chain alkyl sulfonic acids, alkenyl sulfonic acids or aryl sulfonic acids which additionally carry alkyl groups in the aryl radical are preferably used as sulfonic acid.
- Long-chain alkyl sulfonic acids or alkenyl sulfonic acids are understood to mean those with at least 6 carbon atoms.
- suitable sulfonic acids are: aliphatic sulfonic acids, such as the acids of the formulas C 14 H 29 SO 3 H, C 16 H 33 SO 3 H and C 17 H 35 SO 3 H, or aliphatic-aromatic sulfonic acids, such as benzenesulfonic acids, on the benzene ring still carry alkyl radicals of the formulas C 10-14 H 21-29 , or butylnaphthalenesulfonic acid. Mixtures of sulfonic acids can also be used.
- Suitable anode materials are e.g. B. lead dioxide or titanium coated with lead dioxide.
- lead, iron, steel or graphite electrodes are used as cathodes.
- the electrolysis itself is carried out at current densities of 1 to 10 A / dm 2 and temperatures between 10 and 90 ° C.
- the 4-tert. Butyltoluene conversion is preferably 10 to 50%.
- the electrolysis discharges are preferably worked up by distillation. After phase separation, the organic phase is distilled in vacuo.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Description
Die vorliegende Erfindung betrifft ein Verfahren zur elektrochemischen Herstellung von 4-tert. Butylbenzaldehyd.The present invention relates to a process for the electrochemical production of 4-tert. Butylbenzaldehyde.
Die Elektrosynthese von substituierten Benzaldehyden durch anodische Oxidation der entsprechenden Alkylbenzole wird z. B. in Helv. Chim. Acta 9, 1097 (1926) beschrieben. Die Elektrolyse wird bei diesem Verfahren in schwefelsaurer Lösung durchgeführt. Die Benzaldehyde entstehen dabei jedoch nur in geringen Ausbeuten, und die Isolierung der Aldehyde aus den entstehenden Vielkomponentengemischen bereitet Schwierigkeiten. Aus der US-A 4 148 696 ist bekannt, daß man Benzaldehyde durch elektrochemische Oxidation der entsprechenden Alkylaromaten herstellen kann, wenn man die Elektrolyse in Gegenwart von Fettsäuren, deren Alkali- oder Erdalkalisalzen sowie von Tetraalkyl-ammoniumsalzen durchführt. Bei diesem Verfahren entstehen jedoch neben den Benzaldehyden auch die kern- und seitenkettensubstituierten Fettsäureester als Nebenprodukte. Weiterhin erfordert die Aufarbeitung der Elektrolyseausträge eine Reihe von Trennoperationen. So müssen bei einer technischen Durchführung der Synthese die Fettsäuren und Fettsäuresalze von den Benzaldehyden abgetrennt sowie rückgeführt und danach die Benzaldehyde von den Fettsäureestern abgetrennt werden.The electrosynthesis of substituted benzaldehydes by anodic oxidation of the corresponding alkylbenzenes is, for. B. in Helv. Chim. Acta 9, 1097 (1926). In this process, the electrolysis is carried out in sulfuric acid solution. However, the benzaldehydes are formed only in low yields, and the isolation of the aldehydes from the resulting multicomponent mixtures is difficult. From US-A 4 148 696 it is known that benzaldehydes can be prepared by electrochemical oxidation of the corresponding alkyl aromatics if the electrolysis is carried out in the presence of fatty acids, their alkali metal or alkaline earth metal salts and tetraalkylammonium salts. In addition to the benzaldehydes, the nucleic and side chain-substituted fatty acid esters also form as by-products in this process. Furthermore, the processing of the electrolysis discharges requires a number of separation operations. When the synthesis is carried out industrially, the fatty acids and fatty acid salts must be separated from the benzaldehydes and recycled, and then the benzaldehydes must be separated from the fatty acid esters.
Es wurde nun gefunden, daß man 4-tert.-Butylbenzaldehyd durch elektrochemische Oxidation von 4-tert. Butyltoluol in Gegenwart von Mineralsäuren erheblich vorteilhafter herstellen kann, wenn man die elektrochemische Oxidation in Gegenwart von zusätzlichen Alkyl-, Alkenyl- oder Arylsulfonsäuren durchführt. Nach dem erfindungsgemäßen Verfahren erhält man 4-tert. Butylbenzaldehyd in hoher Ausbeute. Ein weiterer wesentlicher Vorteil des erfindungsgemäßen Verfahrens besteht in der einfachen Aufarbeitung der Elektrolyseausträge. So kann man nach Beendigung der Elektrolyse aus der durch Phasentrennung erhaltenen organische Phase den 4-tert. Butylbenzaldehyd direkt durch Destillation isolieren.It has now been found that 4-tert-butylbenzaldehyde is obtained by electrochemical oxidation of 4-tert. Butyltoluene in the presence of mineral acids can be produced considerably more advantageously if the electrochemical oxidation is carried out in the presence of additional alkyl, alkenyl or arylsulfonic acids. 4-tert. Butylbenzaldehyde in high yield. Another major advantage of the method according to the invention is the simple processing of the electrolysis discharges. Thus, after the electrolysis has ended, the 4-tert can be obtained from the organic phase obtained by phase separation. Isolate butylbenzaldehyde directly by distillation.
Das neue Verfahren kann sowohl diskontinuierlich als auch kontinuierlich durchgeführt werden. Die Elektrolyse erfordert keine spezielle Elektrolysezelle. Sie kann z. B. in der technisch häufig eingesetzten Platten- und Rahmenzelle durchgeführt werden. Der Elektrolyt besteht aus 4-tert. Butyltoluol und einer wäßrigen Lösung einer Mineralsäure, der geringe Mengen einer Alkyl-, Alkenyl- oder Arylsulfonsäure zugesetzt werden. Als Mineralsäure wird beispielsweise Schwefelsäure eingesetzt. Als Sulfonsäure dienen vorzugsweise langkettige Alkylsulfonsäuren, Alkenylsulfonsäuren oder Arylsulfonsäuren, die im Arylrest zusätzlich Alkylgruppen tragen. Unter langkettigen Alkylsulfonsäuren bzw. Alkenylsulfonsäuren versteht man solche mit mindestens 6 C-Atomen. Als geeignete Sulfonsäuren seien beispielsweise genannt : aliphatische Sulfonsäuren, wie die Säuren der Formeln C14H29SO3H, C16H33SO3H und C17H35SO3H oder aliphatisch-aromatische Sulfonsäuren, wie Benzolsulfonsäuren, die am Benzolring noch Alkylreste der Formeln C10-14H21-29 tragen, oder Butylnaphthalinsulfonsäure. Man kann auch Gemische der Sulfonsäuren einsetzen.The new process can be carried out batchwise or continuously. Electrolysis does not require a special electrolysis cell. You can e.g. B. in the technically frequently used plate and frame cell. The electrolyte consists of 4-tert. Butyltoluene and an aqueous solution of a mineral acid to which small amounts of an alkyl, alkenyl or arylsulfonic acid are added. For example, sulfuric acid is used as the mineral acid. Long-chain alkyl sulfonic acids, alkenyl sulfonic acids or aryl sulfonic acids which additionally carry alkyl groups in the aryl radical are preferably used as sulfonic acid. Long-chain alkyl sulfonic acids or alkenyl sulfonic acids are understood to mean those with at least 6 carbon atoms. Examples of suitable sulfonic acids are: aliphatic sulfonic acids, such as the acids of the formulas C 14 H 29 SO 3 H, C 16 H 33 SO 3 H and C 17 H 35 SO 3 H, or aliphatic-aromatic sulfonic acids, such as benzenesulfonic acids, on the benzene ring still carry alkyl radicals of the formulas C 10-14 H 21-29 , or butylnaphthalenesulfonic acid. Mixtures of sulfonic acids can also be used.
Die in den Elektrolyse eingesetzten Elektrolyte haben beispielsweise folgende Zusammensetzung : 5 bis 50 Gew.% 4-tert. Butyltoluol, 0,5 bis 10 Gew.% Schwefelsäure, 40 bis 90 Gew.% Wasser und 0,05 bis 5 Gew.% Sulfonsäure.The electrolytes used in the electrolysis have, for example, the following composition: 5 to 50% by weight 4-tert. Butyltoluene, 0.5 to 10% by weight sulfuric acid, 40 to 90% by weight water and 0.05 to 5% by weight sulfonic acid.
Geeignete Anodenmaterialien sind z. B. Bleidioxid oder mit Bleidioxid beschichtetes Titan. Als Kathoden werden beispielsweise Blei-, Eisen-, Stahl oder Graphitelektroden eingesetzt. Die Elektrolyse selbst wird bei Stromdichten von 1 bis 10 A/dm2 und Temperaturen zwischen 10 und 90 °C durchgeführt. Der 4-tert. Butyltoluolumsatz beträgt vorzugsweise 10 bis 50 %. Die Aufarbeitung der Elektrolyseausträge erfolgt vorzugsweise destillativ. Nach Phasentrennung wird die organische Phase im Vakuum destilliert.Suitable anode materials are e.g. B. lead dioxide or titanium coated with lead dioxide. For example, lead, iron, steel or graphite electrodes are used as cathodes. The electrolysis itself is carried out at current densities of 1 to 10 A / dm 2 and temperatures between 10 and 90 ° C. The 4-tert. Butyltoluene conversion is preferably 10 to 50%. The electrolysis discharges are preferably worked up by distillation. After phase separation, the organic phase is distilled in vacuo.
Unumgesetztes 4-tert. Butyltoluol wird zur Elektrolyse zurückgeführt.Unreacted 4-tert. Butyltoluene is returned to the electrolysis.
4-tert. Butylbenzaldehyd ist ein wertvolles Zwischenprodukt für Fungizide sowie für Riechstoffe (Lilial).4-tert. Butylbenzaldehyde is a valuable intermediate for fungicides and for fragrances (Lilial).
Apparatur : geteilte Zelle mit Kationenaustauschermembran
- Anode : Pb02
- Anolyt : 300 g 4-tert. Butyltoluol
- 1 200 g 5 % ige wäßrige Schwefelsäure
- 15 g 30 %ige wäßrige Lösung von C1sH31S03H
- Katholyt : 5 %ige wäßrige Schwefelsäure
- Kathode : Pb
- Stromdichte : 5 A/dm2
- Temperatur: 30 bis 32 °C
- Elektrolyse mit 3,3 F/Mol 4-tert. Butyltoluol
- Anode: Pb0 2
- Anolyte: 300 g 4-tert. Butyltoluene
- 1,200 g of 5% aqueous sulfuric acid
- 15 g 30% aqueous solution of C 1 sH 31 S0 3 H
- Catholyte: 5% aqueous sulfuric acid
- Cathode: Pb
- Current density: 5 A / dm 2
- Temperature: 30 to 32 ° C
- Electrolysis with 3.3 F / mol 4-tert. Butyltoluene
Der Elektrolyt wird während der Elektrolyse über einen Wärmeaustauscher gepumpt. Nach Beendigung der Elektrolyse wird eine Phasentrennung durchgeführt und die organische Phase bei zwei Torr und 60 bis 120 °C fraktioniert abdestilliert. Hierbei erhält man neben 180 g unumgesetzten 4-tert. Butyltoluol 92,4 g 4-tert.-Butylbenzaldehyd. Dies entspricht einer Ausbeute von 70,4 %.The electrolyte is pumped through a heat exchanger during the electrolysis. After the end of the electrolysis, the phases are separated and the organic phase is distilled off at two torr and 60 to 120 ° C. In addition to 180 g of unreacted 4-tert. Butyltoluene 92.4 g 4-tert-butylbenzaldehyde. This corresponds to a yield of 70.4%.
Claims (4)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2948455 | 1979-12-01 | ||
DE19792948455 DE2948455A1 (en) | 1979-12-01 | 1979-12-01 | METHOD FOR PRODUCING 4-TERT. BUTYLBENZALDEHYDE. |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0029995A1 EP0029995A1 (en) | 1981-06-10 |
EP0029995B1 true EP0029995B1 (en) | 1983-05-11 |
Family
ID=6087391
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP80107345A Expired EP0029995B1 (en) | 1979-12-01 | 1980-11-25 | Process for the preparation of 4-tert.-butylbenzaldehyde |
Country Status (5)
Country | Link |
---|---|
US (1) | US4298438A (en) |
EP (1) | EP0029995B1 (en) |
JP (1) | JPS5693882A (en) |
CA (1) | CA1152936A (en) |
DE (2) | DE2948455A1 (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58502027A (en) * | 1981-11-23 | 1983-11-24 | バロ−ス・コ−ポレ−ション | Peripherals adapted to monitor low data rate serial input/output interfaces |
US4402804A (en) * | 1982-05-17 | 1983-09-06 | Ppg Industries, Inc. | Electrolytic synthesis of aryl alcohols, aryl aldehydes, and aryl acids |
DE3322399A1 (en) * | 1983-06-22 | 1985-01-10 | Basf Ag, 6700 Ludwigshafen | METHOD FOR THE PRODUCTION OF BENZ ALDEHYDDIALKYLACETALEN |
DE3913166A1 (en) * | 1989-04-21 | 1990-10-25 | Basf Ag | METHOD FOR PRODUCING BENZALDEHYDDIALKYLACETALS AND NEW BENZALDEHYDDIALKYLACETALS AND BENZYL ESTERS |
ES2522545T3 (en) | 2010-02-11 | 2014-11-17 | Basf Se | Process for obtaining m-substituted alkyl toluenes by isomerization with ionic liquids as catalysts |
US8367875B2 (en) | 2010-02-11 | 2013-02-05 | Basf Se | Process for the preparation of m-substituted alkyltoluenes by isomerization with ionic liquids as catalysts |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2351932A1 (en) * | 1976-05-21 | 1977-12-16 | Rhone Poulenc Ind | Anodic oxidn. of toluene and xylene(s) - to produce methyl benzyl ether(s) and methoxy benzaldehyde(s) |
DE2855508A1 (en) * | 1978-12-22 | 1980-07-10 | Basf Ag | METHOD FOR PRODUCING BENZALDEHYDES |
-
1979
- 1979-12-01 DE DE19792948455 patent/DE2948455A1/en not_active Withdrawn
-
1980
- 1980-10-29 CA CA000363483A patent/CA1152936A/en not_active Expired
- 1980-11-03 US US06/203,597 patent/US4298438A/en not_active Expired - Lifetime
- 1980-11-25 DE DE8080107345T patent/DE3063185D1/en not_active Expired
- 1980-11-25 EP EP80107345A patent/EP0029995B1/en not_active Expired
- 1980-12-01 JP JP16816280A patent/JPS5693882A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
DE3063185D1 (en) | 1983-06-16 |
JPS6330992B2 (en) | 1988-06-21 |
CA1152936A (en) | 1983-08-30 |
EP0029995A1 (en) | 1981-06-10 |
DE2948455A1 (en) | 1981-06-11 |
JPS5693882A (en) | 1981-07-29 |
US4298438A (en) | 1981-11-03 |
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