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EP0164705B1 - Procédé de production de phtalaldéhydacétals - Google Patents

Procédé de production de phtalaldéhydacétals Download PDF

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Publication number
EP0164705B1
EP0164705B1 EP85107063A EP85107063A EP0164705B1 EP 0164705 B1 EP0164705 B1 EP 0164705B1 EP 85107063 A EP85107063 A EP 85107063A EP 85107063 A EP85107063 A EP 85107063A EP 0164705 B1 EP0164705 B1 EP 0164705B1
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EP
European Patent Office
Prior art keywords
bis
benzene
electrolysis
alkanol
phthalaldehyde
Prior art date
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Expired
Application number
EP85107063A
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German (de)
English (en)
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EP0164705A3 (en
EP0164705A2 (fr
Inventor
Dieter Dr. Degner
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
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BASF SE
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Publication date
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Publication of EP0164705A3 publication Critical patent/EP0164705A3/de
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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 electrochemical process for the production of phthalaldehyde acetals.
  • Phthalaldehyde acetals can e.g. B. by reacting phthalaldehydes with o-esters (J. Chem. Soc. Perkin II, 1975, 1656).
  • the phthalaldehydes required as starting materials are provided, for. B. by the Sommelet process from bis (chloromethyl) benzenes and hexamethylenetetramine. This z. B. in J. Chem. Soe.
  • the process described in 1950, 2141 to 2145 provides only moderate yields and is not very environmentally friendly.
  • phthalaldehyde acetals of the general formula in which R is an alkyl radical having 1 to 4 carbon atoms can advantageously be prepared by alkoxymethylbenzenes of the general formula
  • alkoxymethylbenzenes of formula II such.
  • B called: 1,2-, 1,3- or 1,4-bis (methoximethyl) benzene, 1,2-, 1,3- or 1,4-bis (ethoximethyl) benzene, 1, 2-, 1,3- or 1,4-bis (propoximethyl) benzene, 1,2-, 1,3- or 1,4-bis (isopropoximethyl) benzene and 1,2-, 1,3 - or 1,4-bis (tert. butoxmethyl) benzene.
  • Alcohols of the formula ROH are e.g. B. methanol, ethanol, propamol and butanol.
  • the electrochemical oxidation according to the invention can be carried out in technically customary electrolysis cells. Undivided flow cells are particularly suitable.
  • a solution of the bis- (alkoxymethyl) benzene of the formula II in the alkanol is expediently used as the electrolyte, which solution may contain an auxiliary electrolyte to improve the conductivity.
  • auxiliary electrolytes z.
  • B. bases such as alkali metal alcoholates, neutral salts such as fluorides, tetrafluoroborates, sulfonates and sulfates and acids such as alkyl sulfonic acids, alkanesulfonic acids and sulfuric acid.
  • Neutral auxiliary electrolytes such as KF and KSO 3 C 6 H 5 or acidic auxiliary electrolytes such as H Z S0 4 , CH 3 S0 3 H or C 6 H 5 S0 3 H are preferably used.
  • anodes in the electrolysis according to the invention for. B. precious metals, metal oxides such as Ru0 2 and Pb0 2 or graphite.
  • the preferred anode material is graphite.
  • the current densities are 0.1 to 20 A / dm 3 , current densities between 2 and 8 A / dm 2 are preferred.
  • the temperatures are advantageously at least 5'C below the boiling point of the alkanol used, provided the electrolysis is carried out without pressure. For example, electrolysis is carried out at -5 to 55 ° C, preferably 10 to 50 ° C.
  • the electrolysis is carried out with 4 to 12 F / mol of bis (alkoxymethyl) benzene. It is preferably electrolyzed with 7 to 10 F / mol of bis (alkoxymethyl) benzene, so that the bis (alkoxymethyl) benzene is largely reacted.
  • the electrolysis can be carried out batchwise or continuously.
  • the electrolysis discharges are preferably worked up by distillation. Unreacted alkanol can be returned to the electrolysis without purification. Electrode inactivations or electrode corrosion are not observed even when the electrolyte is reused many times.
  • the phthalaldehyde acetals obtainable by the process of the invention are intermediates e.g. B. for the production of dyes and optical brighteners and also serve for the synthesis of special polymers.
  • the electrolyte was pumped through the cell at a flow rate of 200 l / h via a heat exchanger. After the electrolysis had ended, the electrolysis discharge was neutralized with sodium methylate. Then methanol was distilled off at normal pressure and 65 to 75 ° C. and the precipitated salt was separated off at 60 to 70 ° C. using a pressure filter. The residue was pure distilled at 100 to 120 ° C and 3 mbar. This gave 3.5 g of 1,4-bis (methoxymethyl) benzene and 222.2 g of terephthalaldialdehyde tetramethyl acetal.
  • the electrolyte was pumped through the cell at a flow rate of 200 l / h via a heat exchanger.
  • the electrolysis discharge was carried out as described in Example 1, but without adding sodium methylate.
  • Working up gave 0.4 g of 1,4-bis (methoxymethyl) benzene and 158.2 g of terephthalaldehyde tetramethyl acetal. From this, a conversion of 1,4-bis (methoxymethyl) benzene of 99.7%, a yield of terephthalaldehyde tetramethyl acetal of 80.1% and a selectivity for terephthalaldehyde tetramethyl acetal of 80.4% are calculated.
  • the recovered methanol and potassium benzene sulfonate could be used again for electrolysis.
  • the electrolyte was pumped through the cell at a flow rate of 200 l / h via a heat exchanger. After the electrolysis had ended, methanol was distilled off from the electrolysis discharge at atmospheric pressure and 65 to 80 ° C. The precipitated potassium benzene sulfonate was separated off on a pressure filter and the filtrate was fractionally distilled at 100 to 120 ° C. and 5 mbar. This gave 3.8 g of 1,2-bis (methoxymethyl) benzene and 230.3 g of o-phthalaldehyde tetramethyl acetal.

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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 d'acétals d'aldéhydes phtaliques de la formule générale
Figure imgb0010
dans laquelle R désigne un radical alkyle en C1 à C4, caractérisé en ce que l'on soumet des alcoxy-méthyl- benzènes de la formule générale
Figure imgb0011
en présence d'un alcanol de la formule RoH, où R possède la signification définie, à des températures pouvant aller-jusqu'à 5°C en-dessous de la température d'ébullition de l'alcanol, à une électrolyse avec une densité de courant comprise entre 0,1 et 20 A/dm2.
2. Procédé suivant la revendication 1, caractérisé en ce que l'électrolyse est réalisée dans une cellule non subdivisée à écoulement continu.
3. Procédé suivant la revendication 1, caractérisé en ce que l'électrolyte est composé de 65 à 98 % en poids d'alcanol, de 2 à 30 % en poids de bis-(alcoxy-méthyl)benzène et de 0,1 à 5 % en poids d'un électrolyte auxiliaire.
4. Procédé suivant la revendication 3, caractérisé en ce que l'électrolyte auxiliaire est choisi parmi KF, KSO3C6H5, HZSO4, CH3S03H et C6H5SO3H.
EP85107063A 1984-06-14 1985-06-07 Procédé de production de phtalaldéhydacétals Expired EP0164705B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3421976 1984-06-14
DE19843421976 DE3421976A1 (de) 1984-06-14 1984-06-14 Verfahren zur herstellung von phthalaldehydacetalen

Publications (3)

Publication Number Publication Date
EP0164705A2 EP0164705A2 (fr) 1985-12-18
EP0164705A3 EP0164705A3 (en) 1986-04-23
EP0164705B1 true EP0164705B1 (fr) 1987-09-02

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP85107063A Expired EP0164705B1 (fr) 1984-06-14 1985-06-07 Procédé de production de phtalaldéhydacétals

Country Status (3)

Country Link
EP (1) EP0164705B1 (fr)
JP (1) JPH0647746B2 (fr)
DE (2) DE3421976A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3913166A1 (de) * 1989-04-21 1990-10-25 Basf Ag Verfahren zur herstellung von benzaldehyddialkylacetalen und neue benzaldehyddialkylacetale und benzylester
DE4122314A1 (de) * 1991-07-05 1993-01-07 Basf Ag O-phthaldialdehydtetraalkylacetale, ihre herstellung und ihre verwendung als depotverbindung
DE4201544A1 (de) * 1992-01-22 1993-07-29 Basf Ag Verfahren zur herstellung von benzaldehydacetalen
DE4308846A1 (de) * 1993-03-19 1994-09-22 Basf Ag Verfahren zur Herstellung von Terephthalaldehydtetraalkylacetalen

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4318783A (en) * 1978-11-30 1982-03-09 Bayer Aktiengesellschaft Process for the preparation of optionally substituted benzaldehyde dialkyl acetals
DE3048992A1 (de) * 1980-12-24 1982-07-15 Hoechst Ag, 6000 Frankfurt 4,4'-diphenylether-dialdehyd-bis-dimethylacetal und ein verfahren zu seiner herstellung
DE3108790A1 (de) * 1981-03-07 1982-09-16 Dynamit Nobel Ag, 5210 Troisdorf Verfahren zur herstellung von bis(dialkoximethyl)benzolen

Also Published As

Publication number Publication date
EP0164705A3 (en) 1986-04-23
JPS6112886A (ja) 1986-01-21
DE3421976A1 (de) 1985-12-19
DE3560532D1 (en) 1987-10-08
EP0164705A2 (fr) 1985-12-18
JPH0647746B2 (ja) 1994-06-22

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