EP0072914B1 - Procédé de préparation de benzaldéhydes alcoxy-substitués - Google Patents

Procédé de préparation de benzaldéhydes alcoxy-substitués Download PDF

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Publication number
EP0072914B1
EP0072914B1 EP82106344A EP82106344A EP0072914B1 EP 0072914 B1 EP0072914 B1 EP 0072914B1 EP 82106344 A EP82106344 A EP 82106344A EP 82106344 A EP82106344 A EP 82106344A EP 0072914 B1 EP0072914 B1 EP 0072914B1
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EP
European Patent Office
Prior art keywords
alkyl
oxide
hydrogen
substituted benzaldehydes
production
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Expired
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EP82106344A
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German (de)
English (en)
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EP0072914A1 (fr
Inventor
Dieter Dr. Degner
Hans Dr. Roos
Heinz Hannebaum
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BASF SE
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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
    • 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
    • C25B3/01—Products
    • C25B3/07—Oxygen containing compounds

Definitions

  • the present invention relates to a process for the electrochemical production of alkyl-substituted benzaldehydes.
  • DE-OS 2 855 508 describes a process in which the electrooxidation of the alkylbenzenes in water and alkanoic acids is carried out.
  • the alkyl-substituted benzaldehydes are obtained in good yields.
  • the disadvantage of this method is the decrease in the current yields at very high conversions.
  • the graphite anodes show a graphite removal in the long-term test.
  • the object was therefore to find a process which makes it possible to obtain the benzaldehydes in the electrooxidation of alkylbenzenes for the preparation of the corresponding benzaldehydes, even at high conversions, in good current yields and with improved electrode stability.
  • graphite anodes which are treated with metal oxides such as ruthenium oxide, titanium dioxide, iron oxide, chromium oxide, cobalt oxide, manganese dioxide, nickel oxide or with carbides such as Tungsten carbide, are coated.
  • metal oxides such as ruthenium oxide, titanium dioxide, iron oxide, chromium oxide, cobalt oxide, manganese dioxide, nickel oxide or with carbides such as Tungsten carbide.
  • Mixtures of the coating materials mentioned can also be used, such as a mixture of iron oxide and cobalt oxide.
  • alkyl radicals R 'and R 2 in the starting materials of formula II are, for. B. those with 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.
  • Starting materials of formula II are thus methylbenzenes, benzyl alcohols or the alkanoic acid esters of benzyl alcohols which are not substituted or contain the radical R 'mentioned, such as toluene, p-xylene, p-tert-butyltoluene, p-phenyltoluene, benzyl alcohol, p-methylbenzyl alcohol , p-tert-butylbenzyl alcohol, benzyl acetate, p-methylbenzyl acetate and p-tert-butylbenzyl acetate.
  • R 'mentioned such as toluene, p-xylene, p-tert-butyltoluene, p-phenyltoluene, benzyl alcohol, p-methylbenzyl alcohol , p-tert-butylbenzyl alcohol, benzyl acetate, p-methylbenz
  • Formic acid acetic acid and propionic acid are preferred as alkanoic acids.
  • a mixture of the benzene derivative of the formula II, water and the alkanoic acid 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.
  • Examples of conductive salts are tetrafluorobarates, fluorides, hexafluorophosphates, sulfates or sulfonates. The method is preferably carried out in undivided cells.
  • the alkylbenzene compound of the formula II is preferably converted to over 80%.
  • the current density in the method is, for. B. between 1 and 15 A / dm 2.
  • the electrolysis can be carried out batchwise as well as be carried out continuously.
  • the electrolysis discharges are preferably worked up by distillation.
  • the electrolyte from water-alkanoic acid conducting salt is expediently returned to the electrolysis.
  • the graphite anodes to be used according to the invention may e.g. B. by coating the electrode base with the help of thermal spraying or by thermal decomposition of suitable compounds.
  • the oxides or carbides are fed directly in powder form to a spraying system, preferably a plasma spraying system, and are applied to the graphite body with the aid thereof.
  • the compound is applied to the graphite body in dissolved form and the active layer is produced by baking at elevated temperature.
  • So z. B. a titanium oxide layer by spraying or brushing the electrode with butyl titanate in butanol and then heating to 500 to 600 ° C.
  • the coated anodes mentioned surprisingly result in an improvement in the selectivity and an increase in the current yields even at high conversions. This considerably simplifies the processing of the electrolysis discharges. Furthermore, the coated graphite electrodes allow longer running times due to the lower removal.
  • the process according to the invention is intended to be based on the electrosynthesis of 4-tert. Butylbenzaldehyde are explained in more detail.
  • the electrolyte is pumped through a heat exchanger during the electrolysis. After the electrolysis has ended, water and acetic acid are distilled off at atmospheric pressure, NaBF 4 is filtered off and the crude 4-tert. Butylbenzaldehyde (TBA) pure distilled at 2 to 20 torr and 40 to 125 ° C.

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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)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)

Claims (2)

1. Procédé de préparation de benzaldéhydes alcoylsubstitués de la formule générale
Figure imgb0011
dans laquelle R' désigne un atome d'hydrogène, un radical alcoyle ou un groupe aryle, par électro-oxydation de dérivés d'alcoyl-benzènes de la formule générale
Figure imgb0012
dans laquelle X désigne un atome d'hydrogène, un groupe oxhydryle ou un groupe R2-COO-, dans lequel R peut désigner un atome d'hydrogène ou un radical alcoyle, dans de l'eau ou dans un acide alca- noïque, caractérisé en ce que l'on emploie des anodes en graphite, revêtues d'oxydes de métaux ou de carbures.
2. Procédé suivant la renvendication 1, caractérisé en ce que l'on emploie des anodes en graphite, revêtues d'oxyde de rethénium, de bioxyde de titane, d'oxyde de fer, d'oxyde de chrome, d'oxyde de cobalt, de bioxyde de manganèse, d'oxyde de nickel ou de carbure de tungstène.
EP82106344A 1981-08-19 1982-07-15 Procédé de préparation de benzaldéhydes alcoxy-substitués Expired EP0072914B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3132726 1981-08-19
DE19813132726 DE3132726A1 (de) 1981-08-19 1981-08-19 Verfarhen zur herstellung von alkylsubstituierten benzaldehyden

Publications (2)

Publication Number Publication Date
EP0072914A1 EP0072914A1 (fr) 1983-03-02
EP0072914B1 true EP0072914B1 (fr) 1984-10-31

Family

ID=6139614

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82106344A Expired EP0072914B1 (fr) 1981-08-19 1982-07-15 Procédé de préparation de benzaldéhydes alcoxy-substitués

Country Status (4)

Country Link
US (1) US4411746A (fr)
EP (1) EP0072914B1 (fr)
JP (1) JPS5845387A (fr)
DE (2) DE3132726A1 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58502027A (ja) * 1981-11-23 1983-11-24 バロ−ス・コ−ポレ−ション 低デ−タ転送率の直列入出力インタ−フェイスをモニタするようにされた周辺装置
US4643807A (en) * 1985-12-13 1987-02-17 The Dow Chemical Company Process for electrochemically forming an aromatic compound containing one or more alpha-acyloxylated aliphatic substitutent(s)
AU6672286A (en) * 1986-01-06 1987-07-09 Dow Chemical Company, The Electrocatalytic method for producing quinone methides and dihydroxybenzophenones
US4808494A (en) * 1986-03-12 1989-02-28 Combustion Engineering, Inc. Thermally actuated hydrogen secondary battery
NL8601826A (nl) * 1986-07-12 1988-02-01 Stamicarbon Werkwijze voor de elektrochemische oxidatie van organische produkten.
US4871430A (en) * 1987-02-19 1989-10-03 The Dow Chemical Company Novel multifunctional compounds and electrolytic oxidative coupling process
IT1221775B (it) * 1988-01-08 1990-07-12 Giuseppe Bianchi Processo di sintesi di sostanze organiche per via elettrochimica indiretta con sistema redox allo stato solido
DE3913166A1 (de) * 1989-04-21 1990-10-25 Basf Ag Verfahren zur herstellung von benzaldehyddialkylacetalen und neue benzaldehyddialkylacetale und benzylester
ATE113582T1 (de) * 1991-09-19 1994-11-15 Hoechst Ag Verfahren zur oxidation von hydroxymethylpyridinderivaten zu pyridincarbonsäurederivaten.
US10156841B2 (en) 2015-12-31 2018-12-18 General Electric Company Identity management and device enrollment in a cloud service
CN120041877B (zh) * 2025-03-18 2026-04-21 浙江工业大学 一种氧化镍掺杂二氧化锰催化剂及其制备方法和应用

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3775284A (en) * 1970-03-23 1973-11-27 J Bennett Non-passivating barrier layer electrodes
US3977959A (en) * 1973-09-13 1976-08-31 Basf Aktiengesellschaft Anodes for electrolysis
DE2600631A1 (de) * 1976-01-09 1977-07-14 Bitzer Diethelm Verfahren zum beschichten von anorganischen substraten mit carbiden, nitriden und/oder carbonitriden
US4148696A (en) * 1978-03-20 1979-04-10 Uop Inc. Electrochemical oxidation of activated alkyl aromatic compounds
EP0004386B1 (fr) * 1978-03-28 1982-11-24 Diamond Shamrock Technologies S.A. Electrodes pour procédés électrochimiques, en particulier pour l'électrométallurgie
DE2855508A1 (de) 1978-12-22 1980-07-10 Basf Ag Verfahren zur herstellung von benzaldehyden

Also Published As

Publication number Publication date
EP0072914A1 (fr) 1983-03-02
DE3132726A1 (de) 1983-03-03
DE3261133D1 (en) 1984-12-06
JPS5845387A (ja) 1983-03-16
US4411746A (en) 1983-10-25

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