EP0012942A2 - Procédé de préparation électrolytique de benzaldéhydes - Google Patents

Procédé de préparation électrolytique de benzaldéhydes Download PDF

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Publication number
EP0012942A2
EP0012942A2 EP79105128A EP79105128A EP0012942A2 EP 0012942 A2 EP0012942 A2 EP 0012942A2 EP 79105128 A EP79105128 A EP 79105128A EP 79105128 A EP79105128 A EP 79105128A EP 0012942 A2 EP0012942 A2 EP 0012942A2
Authority
EP
European Patent Office
Prior art keywords
tert
electrolysis
formula
hydrogen atom
acetate
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
EP79105128A
Other languages
German (de)
English (en)
Other versions
EP0012942B1 (fr
EP0012942A3 (en
Inventor
Dieter Dr. Dipl.-Chem. Degner
Hardo Dr. Dipl.-Chem. Siegel
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of EP0012942A2 publication Critical patent/EP0012942A2/fr
Publication of EP0012942A3 publication Critical patent/EP0012942A3/xx
Application granted granted Critical
Publication of EP0012942B1 publication Critical patent/EP0012942B1/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 invention relates to a method for the electrochemical production of benzaldehydes.
  • R 1 represents a hydrogen atom, an alkyl radical or an aryl radical
  • R 2 represents a hydrogen atom or an.alkyl group with 1 to 6 C atoms
  • R 3 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • Suitable alkyl radicals R 1 , R 2 and R 3 are those having 1 to 6, preferably 1 to 4, carbon atoms. Phenyl radicals which can be substituted by alkyl, halogen, alkoxy and / or acyloxy groups may be mentioned as aryl radicals R 1 .
  • Starting materials of formula II are thus methylbenzenes, benzyl alcohols or the alkanoic acid esters of benzyl alcohols which are not substituted in the 4-position or contain the radical R 1 mentioned , such as toluene, p-xylene, p-tert-butyl-toluene, p-phenyltoluene , Benzyl alcohol, p-methylbenzyl alcohol, p-tert-butylbenzyl alcohol, benzyl acetate, p-methylbenzyl acetate and p-tert-butylbenzyl acetate.
  • Preferred alkanoic acids of formula III are formic acid, acetic acid and propionic acid.
  • a mixture of the benzene derivative of the formula II, water and the alkanoic acid of the formula III is used as the electrolyte, which may additionally contain a conductive salt to improve the conductivity.
  • the usual salts in organic electrochemistry can be used as the conductive salts, which are soluble in the solution to be electrolyzed and largely stable under the test conditions.
  • Fluoride such as NaF and KF, tetrafluoroborate such as NaBF 4 and Et 4 NBF 4 , perchlorate such as NaClO 4 and Et 4 ClO 4 and sulfate such as Et 4 NSO 4 Et are particularly advantageous as conductive salts.
  • the composition of the electrolyte can be chosen within wide limits.
  • the solutions used in electrolysis have the following composition, for example:
  • the electrode materials used in the process according to the invention will be those which are stable under the conditions of the electrolysis.
  • Suitable anode materials are, for example, graphite, noble metals such as platinum and noble metal coated titanium electrodes.
  • graphite, iron, steel, lead or precious metal electrodes are used as cathodes.
  • Current density and turnover can also be selected within wide limits. The current density is, for example, 1 to 10 A / dm 2 .
  • the electrolysis itself is, for example. with 2 to 12, preferably 4 to 12 F / mol of starting compound and at temperatures below 100 ° C, advantageously between 10 and 90 ° C.
  • the method according to the invention can be carried out both in divided and in undivided electrolysis cells.
  • the electrolysis discharges are generally worked up by distillation. Alkanoic acid, water and any starting materials still present are separated from the benzaldehydes by distillation and can be returned to the electrolysis.
  • the conductive salts used can then be separated from the aldehydes, for example by filtration, and can also be used again in the electrolysis.
  • the benzaldehydes can be further purified, for example, by rectification.
  • the carboxylic acid esters of the corresponding benzyl alcohols obtained as by-products in the process according to the invention can be returned to the electrolysis. However, they can also be isolated before this recycling and saponified to the corresponding benzyl alcohols by processes known per se, for example by acidic transesterification with CH 3 OH / H 2 SO 4 .
  • benzaldehydes obtainable by the process according to the invention are valuable intermediates for active substances and fragrances.
  • 4-tert-butylbenzaldehyde finds e.g. Use as a preliminary product for fungicides and serves as a starting material for the fragrance Lilial.
  • the electrolyte is pumped through a heat exchanger during the electrolysis.
  • the electrolyte is pumped through a heat exchanger during the electrolysis.
  • the electrolyte is pumped through a heat exchanger during the electrolysis.
  • the electrolyte is pumped through a heat exchanger during the electrolysis.
  • the electrolyte is pumped through a heat exchanger during the electrolysis.
  • the electrolyte is pumped through a heat exchanger during the electrolysis.
  • the electrolyte is pumped through a heat exchanger during the electrolysis.
  • the electrolyte is pumped through a heat exchanger during the electrolysis.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP79105128A 1978-12-22 1979-12-13 Procédé de préparation électrolytique de benzaldéhydes Expired EP0012942B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2855508 1978-12-22
DE19782855508 DE2855508A1 (de) 1978-12-22 1978-12-22 Verfahren zur herstellung von benzaldehyden

Publications (3)

Publication Number Publication Date
EP0012942A2 true EP0012942A2 (fr) 1980-07-09
EP0012942A3 EP0012942A3 (en) 1980-07-23
EP0012942B1 EP0012942B1 (fr) 1982-01-27

Family

ID=6058012

Family Applications (1)

Application Number Title Priority Date Filing Date
EP79105128A Expired EP0012942B1 (fr) 1978-12-22 1979-12-13 Procédé de préparation électrolytique de benzaldéhydes

Country Status (5)

Country Link
US (1) US4235683A (fr)
EP (1) EP0012942B1 (fr)
JP (1) JPS5589487A (fr)
DE (2) DE2855508A1 (fr)
DK (1) DK149618C (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0072914A1 (fr) * 1981-08-19 1983-03-02 BASF Aktiengesellschaft Procédé de préparation de benzaldéhydes alcoxy-substitués
EP0030588B1 (fr) * 1979-11-16 1984-04-25 F. HOFFMANN-LA ROCHE & CO. Aktiengesellschaft Procédé de préparation de p-tert.-butylbenzaldéhyde
EP0231053A1 (fr) * 1986-01-06 1987-08-05 The Dow Chemical Company Procédé électrocatalytique pour la préparation de méthides de quinone et de dihydroxybenzophénones

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4164233A (en) * 1978-03-07 1979-08-14 Mcandrew James R Vehicle covering apparatus
DE2948455A1 (de) * 1979-12-01 1981-06-11 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von 4-tert. butylbenzaldehyd.
US4387007A (en) * 1980-11-17 1983-06-07 Hoffmann-La Roche Inc. Process for the manufacture of an aldehyde
GB8309571D0 (en) * 1983-04-08 1983-05-11 Albright & Wilson Accelerated sealing of anodised aluminium
DE3913166A1 (de) * 1989-04-21 1990-10-25 Basf Ag Verfahren zur herstellung von benzaldehyddialkylacetalen und neue benzaldehyddialkylacetale und benzylester
KR102307579B1 (ko) * 2019-09-18 2021-10-05 한국과학기술연구원 벤즈알데하이드 제조방법

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
JPS583035B2 (ja) * 1976-04-12 1983-01-19 株式会社クラレ パラフェノキシトルエンの酸化方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4148696A (en) * 1978-03-20 1979-04-10 Uop Inc. Electrochemical oxidation of activated alkyl aromatic compounds

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Band 19 (1925), Seite 783, C.A. MANN et al.: "Electrochemical oxidation of toluene to benzaldehyde", & Trans.Am.Electrochem.Soc. 47 (preprint), 1925. *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0030588B1 (fr) * 1979-11-16 1984-04-25 F. HOFFMANN-LA ROCHE & CO. Aktiengesellschaft Procédé de préparation de p-tert.-butylbenzaldéhyde
EP0072914A1 (fr) * 1981-08-19 1983-03-02 BASF Aktiengesellschaft Procédé de préparation de benzaldéhydes alcoxy-substitués
EP0231053A1 (fr) * 1986-01-06 1987-08-05 The Dow Chemical Company Procédé électrocatalytique pour la préparation de méthides de quinone et de dihydroxybenzophénones

Also Published As

Publication number Publication date
DK149618B (da) 1986-08-11
DE2962005D1 (en) 1982-03-11
JPS5589487A (en) 1980-07-07
EP0012942B1 (fr) 1982-01-27
EP0012942A3 (en) 1980-07-23
DK149618C (da) 1987-02-02
DE2855508A1 (de) 1980-07-10
DK543079A (da) 1980-06-23
US4235683A (en) 1980-11-25
JPS6350434B2 (fr) 1988-10-07

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