EP0129795B1 - Procédé de production de dialkylacétals de benzaldéhyde - Google Patents

Procédé de production de dialkylacétals de benzaldéhyde Download PDF

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Publication number
EP0129795B1
EP0129795B1 EP84106858A EP84106858A EP0129795B1 EP 0129795 B1 EP0129795 B1 EP 0129795B1 EP 84106858 A EP84106858 A EP 84106858A EP 84106858 A EP84106858 A EP 84106858A EP 0129795 B1 EP0129795 B1 EP 0129795B1
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EP
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weight
tert
electrolysis
acid
electrolyte
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German (de)
English (en)
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EP0129795A3 (en
EP0129795A2 (fr
Inventor
Dieter Dr. Degner
Heinz Hannebaum
Hardo Dr. Siegel
Walter Dr Gramlich
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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

Definitions

  • This invention relates to a new process for the preparation of alkyl substituted benzaldehyde dialkyl acetals by electrooxidation of alkyl toluenes.
  • EP-PS 12 240 describes a process for the preparation of benzaldehyde dialkyl acetals, in which the electrooxidation of the toluenes is carried out in alcoholic solution and in the presence of tetraalkylammonium sulfonates and phosphates as conductive salts.
  • z. B collidine as an auxiliary base for the electrolyte.
  • yields of only 64 and 55% are achieved using this method. Better yields can only be achieved if the low-boiling by-products are first hydrogenated on Pd catalysts and then returned to the electrolysis.
  • FR-PS 2 351 932 describes a process in which toluenes are anodically oxidized on Pt electrodes.
  • electrolytes consist of toluene, an inert organic solvent such as methylene chloride, methanol and a H0 3 S group Acid exist.
  • the electrooxidation of P-xylene gives a mixture by this process which, in addition to ether and ester compounds, also contains 4-methylbenzaldehyde but no 4-methylbenzaldehyde dimethyl acetal.
  • the benzaldehyde dialkyl acetals are obtained by avoiding the disadvantages described in a particularly economical manner and in good yields by the process according to the invention.
  • Alkyl radicals with 1 to 8 carbon atoms are, for example, methyl, ethyl, isopropyl, n-, iso- and tert-butyl groups.
  • Preferred alkyltoluenes are xylenes and butyltoluenes, such as p-xylene and 4-tert-butyltoluene. Of the two alkanols, methanol is of particular technical interest.
  • Acids containing H0 3 S groups come e.g. B .. Acids of the formula R 3- SO 3 H in which -R3 represents an alkyl, aryl, hydroxy or alkoxy group.
  • Preferred acids are methanesulfonic acid, benzenesulfonic acid and methylsulfuric acid, especially sulfuric acid.
  • the method according to the invention does not require a special electrolysis cell; it is preferably carried out in undivided electrolysis cells.
  • Preferred electrolytes are those which have an alkanol content of 70 to 90% by weight, an alkyl toluene content of 8.5 to 30% by weight and an acid content of 0.05 to 1.5% by weight.
  • All anode materials which are customary per se and are stable under the electrolysis conditions can be used as anodes, graphite anodes are preferably used.
  • steel, nickel, precious metals or graphite can be used as cathode materials.
  • the current densities are, for example, 2 to 20 A / dm 2
  • electrolysis is preferably carried out at current densities of 2 to 12 A / dm 2 .
  • the electrolysis temperature is limited by the boiling point of the alkanol. When using methanol, electrolysis is carried out, for example, at temperatures up to 60 ° C., preferably at 20 to 60 ° C.
  • the process according to the invention offers the possibility of largely converting the alkyltoluenes and the alkylbenzylalkyl ethers which have passed through as intermediates without the selectivities of the electrooxidation being significantly impaired.
  • the electrolysis is carried out with 2.8 to 7, preferably 4 to 6.5 F per mole of alkyl toluene.
  • the process can be carried out batchwise or continuously.
  • the electrolysis discharges can be worked up in a very simple manner.
  • the alkanol and any alkyltoluenes and alkylbenzylalkyl ethers which may still be present are then distilled off and, if appropriate, returned to the electrolysis.
  • the alkylbenzaldehyde dialkyl acetals can then be further purified by vacuum distillation.
  • the benzaldehyde dialkyl acetals obtainable by the new process are valuable precursors for fragrances and fungicides.
  • the electrolyte is pumped through a heat exchanger at 200 l / h during the electrolysis.
  • Example 2 It is electrolyzed and worked up as indicated in Example 1. This gives 51.6 g of p-xylene, 34.4 g of 4-methylbenzyl ether and 366.9 g of 4-methylbenzaldehyde dimethyl acetal. This corresponds to a yield of 67.6% .
  • the electrolyte is pumped through a heat exchanger at 200 l / h during the electrolysis.
  • Example 4 It is electrolyzed and worked up as described in Example 4. There are 11.8 g of 4-tert-butylbenzyl methyl ether and 353.6 g of 4-tert-butyl-benzaldehyde dimethyl acetal. This corresponds to a yield of 74.3%.

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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)

Claims (4)

1.- Procédé de préparation de dialkylacétals de benzaldéhyde de formule générale
Figure imgb0007
dans laquelle R1 représente un radical alkyle à 1-8 atomes de C et R2 un radical méthyle ou éthyle, par électro- oxydation d'alkyltoluènes de formule générale
Figure imgb0008
dans un alcanol de formule R20H et en présence d'un acide contenant le groupe H03S, caractérisé en ce qu'on mène l'électro-oxydation avec un électrolyte dont la teneur en alcanol s'élève à 60-90 % en poids, la teneur en alkyltoluène à 8,5-40 % en poids et la teneur en acide à 0,01-1,5 % en poids.
2.- Procédé selon la revendication 1, caractérisé en ce qu'on utilise un électrolyte dont la teneur en alcanol s'élève à 70-90 % en poids, la teneur en alkyltoluène à 8,5-30 % en poids et la teneur en acide à 0,05-1,5 % en poids.
3.- Procédé selon la revendication 1, caractérisé en ce que l'électrolyte contient, en tant qu'acide, de l'acide benzènesulfonique, de l'acide méthanesulfonique, de l'acide méthylsulfurique ou de l'acide sulfurique.
4.- Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce qu'on utilise, comme alkyltoluène, le 4-tert.-butyltoluène et en ce que le produit de l'électrolyse est neutralisé avec une lessive.
EP84106858A 1983-06-22 1984-06-15 Procédé de production de dialkylacétals de benzaldéhyde Expired EP0129795B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3322399 1983-06-22
DE19833322399 DE3322399A1 (de) 1983-06-22 1983-06-22 Verfahren zur herstellung von benz aldehyddialkylacetalen

Publications (3)

Publication Number Publication Date
EP0129795A2 EP0129795A2 (fr) 1985-01-02
EP0129795A3 EP0129795A3 (en) 1985-09-25
EP0129795B1 true EP0129795B1 (fr) 1988-02-24

Family

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Family Applications (1)

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EP84106858A Expired EP0129795B1 (fr) 1983-06-22 1984-06-15 Procédé de production de dialkylacétals de benzaldéhyde

Country Status (4)

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US (1) US4539081A (fr)
EP (1) EP0129795B1 (fr)
JP (1) JPH0641638B2 (fr)
DE (2) DE3322399A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3529074A1 (de) * 1985-08-14 1987-02-19 Basf Ag Verfahren zur herstellung von benzoesaeureorthoestern sowie verbindungen dieser klasse
US5030276A (en) * 1986-10-20 1991-07-09 Norton Company Low pressure bonding of PCD bodies and method
DE3713732A1 (de) * 1987-04-24 1988-11-17 Basf Ag Neue benzaldehyddialkylacetale, ihre herstellung und verwendung
DE3814180A1 (de) * 1988-04-27 1989-11-09 Basf Ag Verfahren zur herstellung von tetralinderivaten und neue tetralinderivate
DE4201544A1 (de) * 1992-01-22 1993-07-29 Basf Ag Verfahren zur herstellung von benzaldehydacetalen
DE10063195A1 (de) 2000-12-19 2002-06-20 Basf Ag Bipolare quasigeteilte Elektrolysezellen
JP5553884B2 (ja) 2009-03-27 2014-07-16 ビーエーエスエフ ソシエタス・ヨーロピア ３−第三ブチルベンズアルデヒドジメチルアセタールを製造するための電気化学的方法
US8889920B2 (en) 2010-02-12 2014-11-18 Basf Se Process for preparing 4-isopropylcyclohexylmethanol
ES2719585T3 (es) * 2010-02-12 2019-07-11 Basf Se Procedimiento para la preparación de 4-isopropilciclohexilmetanol

Family Cites Families (8)

* 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
DE2851732A1 (de) * 1978-11-30 1980-06-12 Bayer Ag Verfahren zur herstellung von substituierten benzaldehyd-dialkylacetalen
US4318783A (en) * 1978-11-30 1982-03-09 Bayer Aktiengesellschaft Process for the preparation of optionally substituted benzaldehyde dialkyl acetals
DE2912058A1 (de) * 1979-03-27 1980-10-09 Bayer Ag Verfahren zur herstellung von gegebenenfalls substituierten benzaldehyd- dialkylacetalen
JPS5620174A (en) * 1979-07-27 1981-02-25 Fuso Kagaku Kogyo Kk Preparation of p-t-butylbenzaldehyde and its acetal
EP0030588B1 (fr) * 1979-11-16 1984-04-25 F. HOFFMANN-LA ROCHE & CO. Aktiengesellschaft Procédé de préparation de p-tert.-butylbenzaldéhyde
DE2948455A1 (de) * 1979-12-01 1981-06-11 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von 4-tert. butylbenzaldehyd.
JPS5687683A (en) * 1979-12-17 1981-07-16 Fuso Kagaku Kogyo Kk Manufacture of p-acetoxybenzaldehyde or its acetal

Also Published As

Publication number Publication date
EP0129795A3 (en) 1985-09-25
EP0129795A2 (fr) 1985-01-02
JPS6052586A (ja) 1985-03-25
DE3469444D1 (en) 1988-03-31
US4539081A (en) 1985-09-03
DE3322399A1 (de) 1985-01-10
JPH0641638B2 (ja) 1994-06-01

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