EP0030588A1 - Procédé de préparation de p-tert.-butylbenzaldéhyde - Google Patents

Procédé de préparation de p-tert.-butylbenzaldéhyde Download PDF

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Publication number
EP0030588A1
EP0030588A1 EP80105721A EP80105721A EP0030588A1 EP 0030588 A1 EP0030588 A1 EP 0030588A1 EP 80105721 A EP80105721 A EP 80105721A EP 80105721 A EP80105721 A EP 80105721A EP 0030588 A1 EP0030588 A1 EP 0030588A1
Authority
EP
European Patent Office
Prior art keywords
tert
anode
butylbenzaldehyde
butyltoluene
solvent
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.)
Granted
Application number
EP80105721A
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German (de)
English (en)
Other versions
EP0030588B1 (fr
Inventor
Peter Dr. Seiler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
F Hoffmann La Roche AG
Original Assignee
F Hoffmann La Roche AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by F Hoffmann La Roche AG filed Critical F Hoffmann La Roche AG
Priority to AT80105721T priority Critical patent/ATE7235T1/de
Publication of EP0030588A1 publication Critical patent/EP0030588A1/fr
Application granted granted Critical
Publication of EP0030588B1 publication Critical patent/EP0030588B1/fr
Expired legal-status Critical Current

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Classifications

    • 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 that occur 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.
  • Butylbenzaldehyde consists in that p-tert. Butyltoluene electrochemically oxidized. Such anodic oxidation avoids using Disadvantages associated with manganese dioxide as a chemical oxidizing agent and allows p-tert. Obtaining butylbenzaldehyde in a simple manner and in high yields, and moreover as a usable by-product on the! Cathode still produces hydrogen.
  • Metal anode anodes for example lead dioxide or manganese dioxide anodes, are expediently used as anodes in the electrochemical 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 case of the invention.
  • anode materials that can be used are precious metals, e.g. Platinum or platinum-plated titanium.
  • Athodenmaterialien K used in the inventive process 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. In general, a voltage of between approximately 3 and approximately 20 V is used.
  • the current density can vary within wide limits, the current densities generally between approximately 0.01 and approximately 100 mA per cm, in particular between approximately 0.4 and approximately 50 mA can be 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 expedient to work with a 5-50%, especially with a 7.5-15% aqueous sulfuric acid.
  • a mixture which consists of the above-mentioned 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.e. 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, and only in small amounts, for example in an amount of about 1% 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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  • 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)
EP80105721A 1979-11-16 1980-09-24 Procédé de préparation de p-tert.-butylbenzaldéhyde Expired EP0030588B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80105721T ATE7235T1 (de) 1979-11-16 1980-09-24 Verfahren zur herstellung von p-tert. butylbenzaldehyd.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CH10254/79 1979-11-16
CH1025479 1979-11-16
CH6034/80 1980-08-08
CH603480 1980-08-08

Publications (2)

Publication Number Publication Date
EP0030588A1 true EP0030588A1 (fr) 1981-06-24
EP0030588B1 EP0030588B1 (fr) 1984-04-25

Family

ID=25698867

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80105721A Expired EP0030588B1 (fr) 1979-11-16 1980-09-24 Procédé de préparation de p-tert.-butylbenzaldéhyde

Country Status (2)

Country Link
EP (1) EP0030588B1 (fr)
DE (1) DE3067628D1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4539081A (en) * 1983-06-22 1985-09-03 Basf Aktiengesellschaft Preparation of benzaldehyde dialkyl acetals

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2351932A1 (fr) * 1976-05-21 1977-12-16 Rhone Poulenc Ind Procede d'oxydation anodique de methylbenzenes
US4148696A (en) * 1978-03-20 1979-04-10 Uop Inc. Electrochemical oxidation of activated alkyl aromatic compounds

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2855508A1 (de) * 1978-12-22 1980-07-10 Basf Ag Verfahren zur herstellung von benzaldehyden

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2351932A1 (fr) * 1976-05-21 1977-12-16 Rhone Poulenc Ind Procede d'oxydation anodique de methylbenzenes
US4148696A (en) * 1978-03-20 1979-04-10 Uop Inc. Electrochemical oxidation of activated alkyl aromatic compounds

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4539081A (en) * 1983-06-22 1985-09-03 Basf Aktiengesellschaft Preparation of benzaldehyde dialkyl acetals

Also Published As

Publication number Publication date
EP0030588B1 (fr) 1984-04-25
DE3067628D1 (en) 1984-05-30

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