EP0460451B1 - Process for the preparation of alpha-hydroxymethyl-ketals - Google Patents
Process for the preparation of alpha-hydroxymethyl-ketals Download PDFInfo
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- EP0460451B1 EP0460451B1 EP91108248A EP91108248A EP0460451B1 EP 0460451 B1 EP0460451 B1 EP 0460451B1 EP 91108248 A EP91108248 A EP 91108248A EP 91108248 A EP91108248 A EP 91108248A EP 0460451 B1 EP0460451 B1 EP 0460451B1
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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
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- the present invention relates to a process for the preparation of ⁇ -hydroxymethylketals by electrochemical oxidation of carbonyl compounds with alkanols in the presence of an auxiliary electrolyte and optionally water.
- JP-A-57/188 686 describes the ⁇ -hydroxylation of aliphatic aldehydes and ketones in neutral solution in the presence of large amounts of water directly to the ⁇ -hydroxyaldehydes and ⁇ -hydroxyketones. According to these methods, however, numerous ⁇ -hydroxy compounds are not or only with difficulty accessible.
- the object of the invention was therefore to remedy the disadvantages mentioned above.
- All radicals R 5 ' to R 9' can be not equal to hydrogen, 0 to 3 are preferably not hydrogen, 0 to 2 are particularly preferably not hydrogen.
- One to three times substituted means one, two or three times substituted.
- auxiliary electrolytes iodides or bromides are used, such as ammonium halides, e.g. Ammonium bromide, ammonium iodide and tetrabutylammonium iodide and particularly preferably metal halides such as sodium bromide, sodium iodide, potassium iodide and potassium bromide.
- ammonium halides e.g. Ammonium bromide, ammonium iodide and tetrabutylammonium iodide and particularly preferably metal halides such as sodium bromide, sodium iodide, potassium iodide and potassium bromide.
- the composition of the electrolyte can be chosen within wide limits.
- the electrolyte generally contains 0.1 to 5% by weight of water.
- the electrolytes can have the following compositions, for example: 1 to 49, preferably 5 to 30% by weight of ketone of the formula II 50 to 98.9, preferably 70 to 95% by weight of alkanol of the formula III 0.1 to 5, preferably 0.5 to 3% by weight of auxiliary electrolyte and 0.1 to 5, preferably 0.5 to 3 wt .-% water.
- the electrochemical oxidation is preferably carried out at current densities of 0.5 to 25 A / dm 2 and at temperatures of (-20) to 60 ° C., in particular 0 to 40 ° C. Higher temperatures are possible, but generally have no advantages.
- the reaction can be carried out at reduced or elevated, but preferably at normal pressure (atmospheric pressure) and in electrolysis cells which are conventional per se. One preferably works with undivided flow cells.
- Suitable anode materials are, for example, noble metals such as platinum or oxides such as ruthenium and chromium oxide or RuO x TiO x mixed oxides and preferably graphite.
- Iron, steel, nickel and noble metals such as platinum and preferably graphite are generally considered as cathode materials.
- Preferred compounds I are listed in the table below: R1 R2 R3 R4 methyl 4-methoxyphenyl H methyl methyl 2-methoxyphenyl H methyl 2-methoxyphenyl methyl H methyl Phenyl Propyl H methyl methyl 2-fluorophenyl H methyl methyl 2-methyl-buten-2-yl H methyl 2,5-dimethyl-hexen-2-yl H H methyl Dimethoxymethyl H H methyl tert-butyl H H methyl tert-butyl 4-fluorophenyl H methyl methyl 4-fluorophenyl H methyl methyl 4-fluorophenyl H methyl
- hydroxymethyl ketals I and the formula I ' are important precursors for hydroxyphenones and can be converted into crop protection agents, photoinitiators, fragrances and pharmaceutical products.
- the starting compounds II were subjected to electrolysis in an undivided cell with 11 bipolar electrodes in an electrolyte which contained 45 g of potassium iodide as auxiliary electrolyte.
- Anode and cathode were made of graphite.
- the current density was 3.3 A / dm2 and the electrolysis temperature was 25 ° C.
- the electrolyte was pumped through the cell at a flow rate of 200 l / h.
- Table A The exact composition of the electrolyte as well as further details of Examples 1 to 3 and Experiments 4 to 6, which were carried out for comparison without the addition of water, are summarized in Table A.
- the starting compounds II ' were subjected to electrolysis in an undivided cell with 11 bipolar electrodes in an electrolyte which contained 45 g of potassium iodide as auxiliary electrolyte.
- Anode and cathode were made of graphite.
- the current density was 3.3 A / dm2 and the electrolysis temperature was 25 ° C.
- the electrolyte was pumped through the cell at a flow rate of 200 l / h.
- Table B The exact composition of the electrolyte as well as further details of the examples are summarized in Table B:
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von α-Hydroxymethylketalen durch elektrochemische Oxidation von Carbonylverbindungen mit Alkanolen in Gegenwart eines Hilfselektrolyten und gegebenenfalls Wasser.The present invention relates to a process for the preparation of α-hydroxymethylketals by electrochemical oxidation of carbonyl compounds with alkanols in the presence of an auxiliary electrolyte and optionally water.
Aus Z. Naturforsch. B 31 (1976) 175 ist die elektrochemische Synthese von Hydroxyisobutyraldehyddimethylacetal aus Isobutyraldehyd und Methanol in Gegenwart von Wasser und eines Elektrolyten bekannt.From Z. Naturforsch. B 31 (1976) 175 discloses the electrochemical synthesis of hydroxyisobutyraldehyde dimethyl acetal from isobutyraldehyde and methanol in the presence of water and an electrolyte.
Aus J.Chem.Soc. Perkin I, 73-77, (1986) ist die elektrochemische Oxidation von aliphatischen Aldehyden und Ketonen unter basischen Bedingungen zu α-Hydroxyacetalen und -ketalen bekannt. Die Oxidation unter neutralen Bedingungen führt nur zu geringen Ausbeuten (JP-A 57/188 684).From J.Chem.Soc. Perkin I, 73-77, (1986) discloses the electrochemical oxidation of aliphatic aldehydes and ketones under basic conditions to α-hydroxyacetals and ketals. Oxidation under neutral conditions leads to low yields (JP-A 57/188 684).
In der JP-A-57/188 686 wird die α-Hydroxylierung von aliphatischen Aldehyden und Ketonen in neutraler Lösung in Gegenwart größerer Mengen Wasser direkt zu den α-Hydroxyaldehyden und α-Hydroxyketonen beschrieben. Nach diesen Methoden sind jedoch zahlreiche α-Hydroxyverbindungen nicht oder nur schwer zugänglich.JP-A-57/188 686 describes the α-hydroxylation of aliphatic aldehydes and ketones in neutral solution in the presence of large amounts of water directly to the α-hydroxyaldehydes and α-hydroxyketones. According to these methods, however, numerous α-hydroxy compounds are not or only with difficulty accessible.
Aus Tetrahedron Letters 25, 691-694 (1984) und aus J. Org. Chem., 51, 130-135 (1986) ist die Herstellung von α-Hydroxymethylarylketalen aus schwer zugänglichen Ausgangsverbindungen unter basischen Bedingungen in mehrstufigen Reaktionen mit langen Reaktionszeiten bekannt.Tetrahedron Letters 25, 691-694 (1984) and J. Org. Chem., 51, 130-135 (1986) disclose the preparation of α-hydroxymethylaryl ketals from starting compounds which are difficult to access under basic conditions in multi-stage reactions with long reaction times.
Die elektrochemische Oxidation von aliphatischen Aldehyden und Ketonen mit anodisch erzeugtem "J⁺" in Gegenwart eines Alkohols unter basischen Bedingungen zu den entsprechenden α-Hydroxyacetalen und -ketalen ist in J. Chem. Soc., Perk. I, 73-77 (1986) beschrieben. Die Oxidation unter neutralen Bedingungen liefert nur geringe Ausbeuten (JP-A-57/188 684). Die Bildung von α-Hydroxyverbindungen aus aromatischen Ketonen ist nicht beschrieben. Vielmehr ist aus Tetrahedron Letters 30, 371-374 (1989) bekannt, daß Arylketone unter ähnlichen Bedingungen, d.h. in alkoholischer Lösung, aber mit Jod/Lithiumperchlorat als Hilfselektrolyt entweder gar nicht oxidiert werden oder nur zu den Ketalen reagieren. In Gegenwart von Orthoestern unter ansonsten unveränderten Bedingungen findet keine 2-Hydroxylierung sondern eine 1,2-Umlagerung des Arylrestes zu 2-Alkyl-2-arylessigsäureestern statt.The electrochemical oxidation of aliphatic aldehydes and ketones with anodically generated “J⁺” in the presence of an alcohol under basic conditions to give the corresponding α-hydroxyacetals and ketals is described in J. Chem. Soc., Perk. I, 73-77 (1986). Oxidation under neutral conditions gives only low yields (JP-A-57/188 684). The formation of α-hydroxy compounds from aromatic ketones is not described. Rather, it is known from Tetrahedron Letters 30, 371-374 (1989) that aryl ketones under similar conditions, i.e. in alcoholic solution, but with iodine / lithium perchlorate as auxiliary electrolyte either not be oxidized at all or only react to the ketals. In the presence of orthoesters under otherwise unchanged conditions there is no 2-hydroxylation but a 1,2-rearrangement of the aryl radical to 2-alkyl-2-arylacetic acid esters.
Der Erfindung lag daher die Aufgabe zugrunde, den zuvor genannten Nachteilen abzuhelfen.The object of the invention was therefore to remedy the disadvantages mentioned above.
Demgemäß wurde ein neues und verbessertes Verfahren zur Herstellung von α-Hydroxymethylketalen der allgemeinen Formel I
in der die Substituenten
- R¹
- C₁- bis C₂₀-Alkyl, C₂- bis C₂₀-Alkenyl, C₂- bis C₂₀-Alkinyl, C₃- bis C₁₂-Cycloalkyl, C₄- bis C₂₀-Cycloalkyl-alkyl, C₁- bis C₂₀-Hydroxyalkyl, gegebenenfalls durch C₁- bis C₈-Alkyl, C₁- bis C₈-Alkoxy, Halogen, C₁- bis C₄-Halogenalkyl, C₁- bis C₄-Halogenalkoxy, Phenyl, Phenoxy, Halogenphenyl, Halogenphenoxy, Carboxy, C₂- bis C₈- Alkoxycarbonyl oder Cyano substituiertes Aryl oder C₇- bis C₂₀-Arylalkyl, oder R¹ und R² oder R² und R³ gemeinsam eine gegebenenfalls durch C₁- bis C₈-Alkyl, C₁- bis C₈-Alkoxy und/oder Halogen ein- bis zweifach substituierte (CH₂)n- oder (CH=CH)m-Gruppe, in der n für 1 bis 10 und m für 1 bis 3 steht,
- R², R³
- Wasserstoff oder einen Rest R¹ und
- R⁴
- C₁- bis C₈-Alkyl
in der R¹, R² und R³ die obengenannte Bedeutung haben, mit einem Alkanol der allgemeinen Formel III
R⁴-OH (III),
in der R⁴ die obengenannte Bedeutung hat, in Gegenwart von 0,1 bis 5 Gew.% Wasser elektrochemisch oxidiert, wobei als Hilfselektrolyt ein Bromid oder Jodid dient, ein Verfahren zur Herstellung von α-Hydroxymethylarylketalen der allgemeinen Formel I'
in der die Substituenten
- R3'
- Wasserstoff, C₁- bis C₂₀-Alkyl, C₂- bis C₂₀-Alkenyl, C₂- bis C₂₀-Alkinyl, C₂- bis C₂₀-Alkoxyalkyl, C₄- bis C₂₀-Alkenyloxyalkyl, C₃- bis C₁₂-Cycloalkyl oder C₄- bis C₂₀-Cycloalkyl-alkyl,
- R4'
- C₁- bis C₈-Alkyl und
- R5',R6',R7',R8',R9'
- unabhängig voneinander Wasserstoff, C₁- bis C₈-Alkyl, C₁- bis C₈-Alkoxy, C₂- bis C₈-Alkenyl, C₃- bis C₈-Alkenyloxy, C₂- bis C₈-Alkinyl, C₃- bis C₈-Alkinyloxy, Halogen, Cyano, Phenyl, Phenoxy, Halogenphenyl, Halogenphenoxy, Carboxy, C₂- bis C₈-Alkoxycarbonyl, C₃- bis C₈-Alkenyloxycarbonyl, C₃- bis C₈-Alkinyloxycarbonyl oder R5' und R6' oder R6' und R7' gemeinsam eine gegebenenfalls durch C₁- bis C₈-Alkyl, C₁- bis C₈-Alkoxy und/ oder Halogen ein- bis zweifach substituierte (CH₂)n'- oder (CH=CH)m'-Gruppe, in der n' für 1 bis 10 und m' für 1 bis 3 steht,
in der R3' die oben genannten Bedeutungen haben, mit einem Alkanol der allgemeinen Formel III'
R4'-OH (III'),
in der R4' die oben genannten Bedeutungen hat, in Gegenwart von 0,1 bis 5 Gew.-% Wasser elektrochemisch oxidiert, wobei als Hilfselektrolyt ein Bromid oder Jodid dient. Als Ausgangsverbindungen zur Herstellung der erfindungsgemäßen α-Hydroxymethylketale I bzw. Arylmethylketone I' kommen prinzipiell alle Ketone der allgemeinen Formeln II und II' in Betracht, die unter den Elektrolysebedingungen inerte Substituenten tragen.Accordingly, a new and improved process for the preparation of α-hydroxymethyl ketals of the general formula I
in which the substituents
- R¹
- C₁ to C₂₀ alkyl, C₂ to C₂₀ alkenyl, C₂ to C₂₀ alkynyl, C₃ to C₁₂ cycloalkyl, C₄ to C₂₀ cycloalkyl alkyl, C₁ to C₂₀ hydroxyalkyl, optionally by C₁ to C₈ -Alkyl, C₁- to C₈-alkoxy, halogen, C₁- to C₄-haloalkyl, C₁- to C₄-haloalkoxy, phenyl, phenoxy, halophenyl, halophenoxy, carboxy, C₂- to C₈- alkoxycarbonyl or cyano-substituted aryl or C₇- bis C₂₀-arylalkyl, or R¹ and R² or R² and R³ together together a (CH₂) n - or (CH = CH) m optionally substituted by C₁- to C₈-alkyl, C₁- to C₈-alkoxy and / or halogen Group in which n is 1 to 10 and m is 1 to 3,
- R², R³
- Hydrogen or a radical R¹ and
- R⁴
- C₁ to C₈ alkyl
in which R¹, R² and R³ have the meaning given above, with an alkanol of the general formula III
R⁴-OH (III),
in which R⁴ has the abovementioned meaning, electrochemically oxidized in the presence of 0.1 to 5% by weight of water, a bromide or iodide serving as the auxiliary electrolyte, a process for the preparation of α-hydroxymethylaryl ketals of the general formula I '
in which the substituents
- R 3 '
- Hydrogen, C₁ to C₂₀ alkyl, C₂ to C₂₀ alkenyl, C₂ to C₂₀ alkynyl, C₂ to C₂₀ alkoxyalkyl, C₄ to C₂₀ alkenyloxyalkyl, C₃ to C₁₂ cycloalkyl or C₄ to C₂₀ cycloalkyl -alkyl,
- R 4 '
- C₁ to C₈ alkyl and
- R 5 ' , R 6' , R 7 ' , R 8' , R 9 '
- independently of one another hydrogen, C₁ to C₈ alkyl, C₁ to C₈ alkoxy, C₂ to C₈ alkenyl, C₃ to C₈ alkenyloxy, C₂ to C₈ alkynyl, C₃ to C₈ alkynyloxy, halogen, cyano, Phenyl, phenoxy, halophenyl, halophenoxy, carboxy, C₂- to C₈-alkoxycarbonyl, C₃- to C₈-alkenyloxycarbonyl, C₃- to C₈-alkynyloxycarbonyl or R 5 ' and R 6' or R 6 ' and R 7' together, optionally by one C₁ to C₈ alkyl, C₁ to C₈ alkoxy and / or halogen mono- to disubstituted (CH₂) n 'or (CH = CH) m ' group, in which n 'is 1 to 10 and m' represents 1 to 3,
in which R 3 'have the meanings given above, with an alkanol of the general formula III'
R 4 ' -OH (III'),
in which R 4 'has the meanings given above, is electrochemically oxidized in the presence of 0.1 to 5% by weight of water, a bromide or iodide serving as the auxiliary electrolyte. In principle, all ketones of the general formulas II and II 'which carry substituents which are inert under the electrolysis conditions are suitable as starting compounds for the preparation of the α-hydroxymethyl ketals I or aryl methyl ketones I' according to the invention.
Als Substituenten R¹ bis R⁴, R3' bis R9' und Indices n, n', m und m' in den Formeln I bis III und I' bis III' kommen unabhängig voneinander für das Verfahren folgende Bedeutungen in Betracht:
- R¹
-
- unverzweigtes oder verzweigtes C₁- bis C₂₀-Alkyl, vorzugsweise unverzweigtes oder verzweigtes C₁- bis C₁₂-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, tert.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, iso-Heptyl, n-Octyl, iso-Octyl, n-Nonyl, iso-Nonyl, n-Decyl, iso-Decyl, n-Undecyl, iso-Undecyl, n-Dodecyl und iso-Dodecyl,
- unverzweigtes oder verzweigtes C₂- bis C₂₀-Alkenyl, vorzugsweise unverzweigtes oder verzweigtes C₂- bis C₈-Alkenyl, wie Allyl, 2-Buten-1-yl, 3-Buten-2-yl, 4-Buten-1-yl, 2-Penten-1-yl und 2,2-Dimethylpenten-1-yl,
- unverzweigtes oder verzweigtes C₂- bis C₂₀-Alkinyl, vorzugsweise unverzweigtes oder verzweigtes C₂- bis C₈-Alkinyl, wie Propinyl, 1,1-Dimethyl-2-propinyl, 1-Methyl-2-propinyl, 1-Butinyl, 2-Butinyl und 4,4-Dimethylbut-2-in-1-yl,
- C₃- bis C₁₂-Cycloalkyl, bevorzugt C₃- bis C₈-Cycloalkyl, wie Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl, Cycloheptyl und Cyclooctyl,
- C₄- bis C₂₀-Cycloalkyl-alkyl, bevorzugt C₄- bis C₈-Cycloalkylalkyl, wie Cyclopentyl-methyl, 2-Cyclopentyl-ethyl, 1-Cyclopentyl-ethyl, Cyclohexyl-methyl, 1-Cyclohexylethyl und 2-Cyclohexyl-ethyl,
- unverzweigtes oder verzweigtes C₁- bis C₂₀-Hydroxyalkyl, bevorzugt unverzweigtes oder verzweigtes C₁- bis C₈-Hydroxyalkyl, wie Hydroxymethyl, 1-Hydroxyethyl, 2-Hydroxyethyl, 1-Hydroxypropyl, 2-Hydroxypropyl und 3-Hydroxypropyl,
- Aryl, wie Phenyl, 1-Naphthyl und 2-Naphthyl, bevorzugt Phenyl,
- ein- bis dreifach durch C₁- bis C₈-Alkyl substituiertes Aryl, bevorzugt ein- bis dreifach durch C₁- bis C₄-Alkyl substituiertes Phenyl, wie 2-Methylphenyl, 4-Methylphenyl, 2-Ethylphenyl, 4-Ethylphenyl, 3-Methylphenyl, 2,4-Dimethylphenyl, 3,4-Dimethylphenyl und 3,4,5-Trimethylphenyl,
- ein- bis dreifach durch C₁- bis C₈-Alkoxy substituiertes Aryl, bevorzugt ein- bis dreifach durch C₁- bis C₄-Alkoxy substituiertes Phenyl, wie 2-Methoxyphenyl, 2-Ethoxyphenyl, 3-Methoxyphenyl, 4-Methoxyphenyl, 3-Ethoxyphenyl, 4-Ethoxyphenyl, 3,4-Dimethoxyphenyl und 3,4,5-Trimethoxyphenyl,
- ein- bis dreifach durch C₁- bis C₄-Halogenalkyl substituiertes Aryl, bevorzugt ein- bis dreifach durch C₁- bis C₂-Fluor- und Chloralkyl Phenyl, besonders bevorzugt ein- bis dreifach durch Trifluormethyl und Trichlormethyl, substituiertes Phenyl, wie 4-Trifluormethylphenyl und 4-Trichlormethylphenyl,
- ein- bis dreifach durch C₁- bis C₄-Halogenalkoxy substituiertes Aryl, bevorzugt ein- bis dreifach durch C₁- bis C₂-Fluor- und Chloralkoxy Phenyl, besonders bevorzugt ein- bis dreifach durch Trifluormethoxy und Trichlormethoxy substituiertes Phenyl, wie Trifluormethoxyphenyl,
- ein- bis dreifach durch Halogen substituiertes Aryl, bevorzugt ein- bis dreifach durch Fluor oder Chlor substituiertes Phenyl, wie 4-Chlorphenyl, 3,4-Dichlorphenyl, 4-Bromphenyl, 4-Fluorphenyl und 4-Fluor-3-chlorphenyl,
- ein- bis dreifach durch Halogenphenyl substituiertes Aryl, bevorzugt ein- bis dreifach durch Fluor- und/oder Chlorphenyl substituiertes Phenyl wie (4-Chlorphenyl)-phenyl,
- ein- bis dreifach durch Halogenphenoxy substituiertes Aryl, bevorzugt ein- bis dreifach durch Fluor- und/oder Chlorphenoxy substituiertes Phenyl, wie (4-Fluorphenoxy)-phenyl,
- ein- bis dreifach durch Carboxy substituiertes Aryl, bevorzugt ein- bis dreifach durch Carboxy substituiertes Phenyl, wie 2-Carboxyphenyl, 3-Carboxyphenyl und 4-Carboxyphenyl,
- ein- bis dreifach durch C₂- bis C₈-Alkoxycarbonyl substituiertes Aryl, bevorzugt ein- bis dreifach durch C₂- bis C₄-Alkoxycarbonyl substituiertes Phenyl, wie 4-Methoxycarbonylphenyl, 4-Ethoxycarbonylphenyl, 2-Methoxycarbonylphenyl, 2-Ethoxycarbonylphenyl und 3-Methoxycarbonylphenyl,
- ein- bis dreifach durch Cyano substituiertes Aryl, bevorzugt ein- bis dreifach durch Cyano substituiertes Phenyl, wie 2-Cyanophenyl, 3-Cyanophenyl und 4-Cyanophenyl,
- C₇- bis C₂₀-Arylalkyl, bevorzugt C₇- bis C₁₂-Arylalkyl wie Benzyl, Phenylethyl, Phenylpropyl und Phenylisopropyl,
- im Arylteil ein- bis dreifach durch Halogen substituiertes C₇- bis C₂₀-Aryl-alkyl, bevorzugt im Phenylteil ein- bis dreifach durch Fluor oder Chlor C₇- bis C₁₀-Phenyl-alkyl, wie 4-Fluorbenzyl, 4-Chlorbenzyl, 2,4-Dichlorbenzyl und 3,4-Dichlorbenzyl,
- im Arylteil ein- bis dreifach durch C₁- bis C₈-Alkyl substituiertes C₇- bis C₂₀-Aryl-alkyl, bevorzugt im Phenylteil ein- bis dreifach durch C₁- bis C₄-Alkyl substituiertes C₇- bis C₁₀-Phenyl-alkyl, besonders bevorzugt im Phenylteil ein- bis dreifach durch C₁- bis C₂-Alkyl substituiertes C₇- bis C₁₀-Phenylalkyl, wie 4-Methylbenzyl, 4-Ethylbenzyl und 4-Methylphenethyl,
- im Arylteil ein- bis dreifach durch C₁- bis C₈-Alkoxy substituiertes C₇- bis C₂₀-Aryl-alkyl, bevorzugt im Phenylteil ein- bis dreifach durch C₁- bis C₄-Alkoxy substituiertes C₇- bis C₁₀-Phenylalkyl, besonders bevorzugt im Phenylteil ein- bis dreifach durch C₁- bis C₂-Alkoxy substituiertes C₇- bis C₁₀-Phenylalkyl, wie 4-Methoxybenzyl, 4-Ethoxybenzyl und 4-Methoxyphenethyl,
- im Arylteil ein- bis dreifach durch C₁- bis C₄-Halogenalkyl, substituiertes C₇- bis C₂₀-Arylalkyl, bevorzugt im Phenylteil ein- bis dreifach durch C₁- bis C₂-Fluor- und Chloralkyl substituiertes C₇- bis C₁₀-Phenylalkyl, besonders bevorzugt im Phenylteil ein- bis dreifach durch Trifluormethyl und Trichlormethyl substituiertes C₇-C₁₀-Phenylalkyl, wie 4-Trifluormethylbenzyl und 4-Trichlormethylbenzyl,
- im Arylteil ein- bis dreifach durch C₁- bis C₄-Halogenalkoxy substituiertes C₇- bis C₂₀-Arylalkyl, bevorzugt im Phenylteil ein- bis dreifach durch C₁- bis C₂-Halogenalkoxy substituiertes C₇- bis C₁₀-Phenylalkyl, besonders bevorzugt ein- bis dreifach durch Trifluormethoxy und Trichlormethoxy substituiertes C₇- bis C₁₀-Phenylalkyl, wie 4-Trifluormethoxybenzyl und 4-Trichlormethoxybenzyl,
- ein- bis dreifach durch Halogenphenyl substituiertes C₇- C₂₀-Arylalkyl, bevorzugt ein- bis dreifach durch Fluor- und/oder Chlorphenyl substituiertes C₇- bis C₁₂-Phenylalkyl, wie 4-Chlorphenethyl und 4-Fluorphenethyl,
- ein- bis dreifach durch Halogenphenoxy substituiertes C₇- C₂₀-Arylalkyl, bevorzugt ein- bis dreifach durch Fluor- und/oder Chlorphenoxy substituiertes C₇- bis C₁₂-Phenylalkyl, wie 2-Chlorphenoxymethyl und 4-Chlorphenoxymethyl,
- ein- bis dreifach durch Carboxy substituiertes C₇- C₂₀-Arylalkyl, bevorzugt ein- bis dreifach durch Carboxy substituiertes C₇- bis C₁₂-Phenylalkyl, wie 4-Carboxybenzyl, 4-Carboxyphenethyl, 2-Carboxybenzyl und 2-Carboxyphenylethyl,
- ein- bis dreifach durch C₂- bis C₈-Alkoxycarbonyl substituiertes C₇- C₂₀-Arylalkyl, bevorzugt ein- bis dreifach durch C₂- bis C₄-Alkoxycarbonyl substituiertes C₇- bis C₁₂-Phenylalkyl, wie 4-Methoxycarbonylbenzyl, 2-Methoxycarbonylbenzyl, 4-Ethoxycarbonylbenzyl und 2-Ethoxycarbonylbenzyl,
- ein- bis dreifach durch Cyano substituiertes C₇- C₂₀-Arylalkyl, bevorzugt ein- bis dreifach durch Cyano substituiertes C₇- bis C₁₂-Phenylalkyl, wie 2-Cyanobenzyl, 4-Cyanobenzyl, 2-Cyanophenethyl und 4-Cyanophenethyl,
- durch ein, zwei oder drei Phenylgruppen substituiertes Phenyl, wie 2-(Phenyl)phenyl, 3-(Phenyl)-phenyl, 4-(Phenyl)-phenyl und 3,4-(Diphenyl)-phenyl,
- durch ein, zwei oder drei Phenoxygruppen substituiertes Phenyl, wie 4-Phenoxyphenyl und 2-Phenoxyphenyl,
- durch Halogen und C₁- bis C₄-Alkyl zwei- oder dreifach substituiertes Phenyl, wie 2-Methyl-4-chlorphenyl und 3-Methyl-4-fluorphenyl,
- durch Halogen und C₁- bis C₄-Alkoxy zwei- oder dreifach substituiertes Phenyl, wie 3-Chlor-4-methoxyphenyl,
- durch Halogen und C₁- bis C₄-Halogenalkyl zwei- oder dreifach substituiertes Phenyl, wie 2-Chlor-4-trifluormethylphenyl,
- durch Halogen und Phenoxy zwei- oder dreifach substituiertes Phenyl, wie 3-Chlor-4-phenoxyphenyl,
- durch C₁- bis C₄-Alkyl und C₁- bis C₄-Alkoxy zwei- oder dreifach substituiertes Phenyl, wie 2-Methyl-4-methoxyphenyl,
- durch C₁- bis C₄-Alkyl und C₁- bis C₄-Halogenalkyl zwei- oder dreifach substituiertes Phenyl, wie 3-Methyl-4-trichlormethylphenyl,
- durch C₁- bis C₄-Alkyl und Phenoxy zwei- oder dreifach substituiertes Phenyl, wie 2-Methyl-4-phenoxyphenyl,
- durch C₁- bis C₄-Alkoxy und C₁- bis C₄-Halogenalkyl zwei- oder dreifach substituiertes Phenyl, wie 3-Trifluormethyl-4-methoxyphenyl,
- durch C₁- bis C₄-Alkoxy und Phenoxy zwei- oder dreifach substituiertes Phenyl, wie 3-Methoxy-4-phenoxyphenyl,
- durch C₁- bis C₄-Halogenalkyl und Phenoxy zwei- oder dreifach substituiertes Phenyl, wie 3-Trifluormethyl-4-phenoxyphenyl,
- durch Halogen, C₁- bis C₄-Alkyl und C₁- bis C₄-Alkoxy dreifach substituiertes Phenyl, wie 2-Chlor-3-tert.-butyl-4-methoxyphenyl,
- durch Halogen, C₁- bis C₄-Alkyl und C₁- bis C₄-Halogenalkyl dreifach substituiertes Phenyl, wie 2-Methyl-3-chlor-4-trifluormethylphenyl,
- durch Halogen, C₁- bis C₄-Alkyl und Phenoxy dreifach substituiertes Phenyl, wie 4-Chlor-2-ethyl-3-phenoxyphenyl,
- durch Halogen, C₁- bis C₄-Alkoxy und C₁- bis C₄-Halogenalkyl dreifach substituiertes Phenyl, wie 3-Chlor-4-methoxy-3-trifluormethylphenyl,
- durch Halogen, C₁- bis C₄-Alkoxy und Phenoxy dreifach substituiertes Phenyl, wie 2-Fluor-4-ethoxy-3-phenoxyphenyl,
- durch Halogen, C₁- bis C₄-Halogenalkyl und Phenoxy dreifach substituiertes Phenyl, wie 4-Fluor-3-trifluormethyl-2-phenoxyphenyl,
- durch C₁- bis C₄-Alkyl, C₁- bis C₄-Alkoxy und C₁- bis C₄-Halogenalkyl dreifach substituiertes Phenyl, wie 4-Methyl-3-methoxy-2-trichlormethylphenyl,
- durch C₁- bis C₄-Alkyl, C₁- bis C₄-Alkoxy und Phenoxy dreifach substituiertes Phenyl, wie 4-Methyl-3-ethoxy-2-phenoxyphenyl,
- durch C₁- bis C₄-Alkyl, C₁- bis C₄-Halogenalkyl und Phenoxy dreifach substituiertes Phenyl, wie 2-Methyl-4-trifluormethyl-3-phenoxyphenyl,
- durch C₁- bis C₄-Alkoxy, C₁- bis C₄-Halogenalkyl und Phenoxy dreifach substituiertes Phenyl, wie 4-Methoxy-2-trichlormethyl-3-phenoxyphenyl,
- R², R³
-
- Wasserstoff oder einen Rest R¹,
- R¹ und R² oder R² und R³ gemeinsam
-
- (CH₂)n, wie CH₂, (CH₂)₂, (CH₂)₃, (CH₂)₄, (CH₂)₅ und (CH₂)₆, bevorzugt (CH₂)₃, (CH₂)₄, (CH₂)₅, (CH₂)₆, besonders bevorzugt (CH₂)₃ und (CH₂)₄,
- (CH=CH)m, wie (CH=CH), (CH=CH)₂, (CH=CH)₃, bevorzugt (CH=CH)₂, (CH=CH)₃ besonders bevorzugt (CH=CH)₂,
- n
-
- 1 bis 6, vorzugsweise 3 bis 6, besonders bevorzugt 3 und 4,
- m
-
- 1 bis 3, vorzugsweise 2 und 3, besonders bevorzugt 2.
- R3'
-
- Wasserstoff
- unverzweigtes oder verzweigtes C₁- bis C₂₀-Alkyl, vorzugsweise C₁- bis C₁₂-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, tert.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, iso-Heptyl, n-Octyl, n-Nonyl, iso-Nonyl, n-Decyl, iso-Decyl, n-Undecyl, iso-Undecyl, n-Dodecyl und iso-Dodecyl, besonders bevorzugt unverzweigtes oder verzweigtes C₁- bis C₈-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, tert.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, iso-Heptyl, n-Octyl,
- unverzweigtes oder verzweigtes C₂- bis C₂₀-Alkenyl, vorzugsweise unverzweigtes oder verzweigtes C₂- bis C₈-Alkenyl, wie Vinyl, Allyl, Buten-1-yl, Buten-2-yl, Buten-3-yl, Penten-1-yl, Penten-2-yl, Penten-3-yl, Penten-4-yl, Hexen-1-yl, Hexen-2-yl, Hexen-3-yl und Hexen-4-yl,
- unverzweigtes oder verzweigtes C₂- bis C₂₀-Alkinyl, vorzugsweise unverzweigtes oder verzweigtes C₂- bis C₈-Alkinyl, wie Ethinyl, 1-Propin-3-yl, 1-Butin-3-yl, 1-Pentin-3-yl, 1-Hexin-5-yl, 1-Heptin-6-yl und 1-Octin-7-yl,
- unverzweigtes oder verzweigtes C₂- bis C₂₀-Alkoxyalkyl, bevorzugt unverzweigtes oder verzweigtes C₂- bis C₈-Alkoxyalkyl, wie Methoxymethyl, Ethoxymethyl, n-Propoxymethyl, iso-Propoxymethyl, n-Butoxymethyl, iso-Butoxymethyl, sec.-Butoxymethyl, tert.-Butoxymethyl, n-Pentoxymethyl, iso-Pentoxymethyl, sec.-Pentoxymethyl, tert.-Pentoxymethyl, neo-Pentoxymethyl, 1,2-Dimethylpropoxymethyl, n-Hexoxymethyl, iso-Hexoxymethyl, sec.-Hexoxymethyl, n-Heptoxymethyl, iso-Heptoxymethyl, Methoxy-1-ethyl, Ethoxy-1-ethyl, n-Propoxy-1-ethyl, iso-Propoxy-1-ethyl, n-Butoxy-1-ethyl, iso-Butoxy-1-ethyl, sec.-Butoxy-1-ethyl, tert.-Butoxy-1-ethyl, n-Pentoxy-1-ethyl, iso-Pentoxy-1-ethyl, sec.-Pentoxy1-ethyl, tert.-Pentoxy-1-ethyl, neo-Pentoxy-1-ethyl, 1,2-Dimethylpropoxy-1-ethyl, n-Hexoxy-1-ethyl, iso-Hexoxyl-ethyl, sec.-Hexoxy-1-ethyl, Methoxy-2-ethyl, Ethoxy-2-ethyl, n-Propoxy-2-ethyl, iso-Propoxy-2-ethyl, n-Butoxy-2-ethyl, iso-Butoxy-2-ethyl, sec.-Butoxy-2-ethyl, tert.-Butoxy-2-ethyl, n-Pentoxy-2-ethyl, iso-Pentoxy-2-ethyl, sec.-Pentoxy-2-ethyl, tert.-Pentoxy-2-ethyl, neo-Pentoxy-2-ethyl, 1,2-Dimethyl-propoxy-2-ethyl, n-Hexoxy-2-ethyl, iso-Hexoxy-2-ethyl und sec.-Hexoxy-2-ethyl,
- unverzweigtes oder verzweigtes C₄- bis C₂₀-Alkenyloxyalkyl, bevorzugt unverzweigtes oder verzweigtes C₄- bis C₈-Alkenyloxyalkyl, wie Allyloxymethyl, Allyloxy-1-ethyl, Allyloxy-2-ethyl, Allyloxy-1-propyl und Allyloxy-2-propyl,
- C₃- bis C₁₂-Cycloalkyl, bevorzugt C₃- bis C₈-Cycloalkyl, wie Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl, Cycloheptyl und Cyclooctyl,
- C₄- bis C₂₀-Cycloalkyl-alkyl, bevorzugt C₄- bis C₈-Cycloalkylalkyl, wie Cyclopentyl-methyl, 2-Cyclopentyl-ethyl, 1-Cyclopentyl-ethyl, Cyclohexyl-methyl, 1-Cyclohexylethyl und 2-Cyclohexylethyl,
- R4'
-
- C₁- bis C₈-Alkyl, vorzugsweise unverzweigtes C₁- bis C₈-Alkyl wie Methyl, Ethyl, Propyl, Butyl, n-Pentyl, n-Hexyl, n-Heptyl oder n-Octyl, besonders bevorzugt unverzweigtes C₁- bis C₄-Alkyl wie Methyl, Ethyl, n-Propyl oder n-Butyl,
- R5',R6',R7',R8',R9'
-
- unabhängig voneinander
- Wasserstoff
- C₁- bis C₈-Alkyl, bevorzugt C₁- bis C₄-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl oder tert.-Butyl, besonders bevorzugt Methyl oder Ethyl,
- C₁- bis C₈-Alkoxy, bevorzugt C₁- bis C₄-Alkoxy wie Methoxy, Ethoxy, n-Propoxy, iso-Propoxy, n-Butoxy, iso-Butoxy, sec.-Butoxy oder tert.-Butoxy, besonders bevorzugt Methoxy oder Ethoxy,
- C₂- bis C₈-Alkenyl, bevorzugt C₂- bis C₄-Alkenyl wie Vinyl, Allyl, 3-Buten-1-yl, 2-Buten-1-yl und 1-Buten-1-yl,
- C₃- bis C₈-Alkenyloxy, bevorzugt C₃- bis C₆-Alkenyloxy wie Allyloxy, Buten-1-yloxy, Buten-2-yloxy, Buten-3-yloxy, Penten-1-yloxy, Penten-2-yloxy, Penten-3-yloxy, Penten-4-yloxy, Hexen-1-yloxy und Hexen-2-yloxy,
- C₂- bis C₈-Alkinyl, bevorzugt C₂- bis C₄-Alkinyl wie Ethinyl, 2-Propin-1-yl und 3-Butin-1-yl,
- C₃- bis C₈-Alkinyloxy, bevorzugt C₃- bis C₄-Alkinyloxy wie Propinyloxy und Butinyloxy,
- Halogen wie Fluor, Chlor, Brom oder Iod, bevorzugt Fluor, Chlor und Brom,
- Cyano,
- Phenyl,
- Phenoxy,
- Halogenphenyl, bevorzugt Chlorphenyl wie 2-Chlorphenyl und 4-Chlorphenyl,
- Halogenphenoxy, bevorzugt Chlorphenoxy wie 2-Chlorphenoxy und 4-Chlorphenoxy,
- Carboxy,
- C₂- bis C₈-Alkoxycarbonyl, bevorzugt C₂- bis C₄-Alkoxycarbonyl wie Methoxycarbonyl, Ethoxycarbonyl, Propoxycarbonyl, Isopropoxycarbonyl, n-Butoxycarbonyl, Isobutoxycarbonyl und tert.-Butoxycarbonyl,
- C₃- bis C₈-Alkenyloxycarbonyl, bevorzugt C₃- bis C₆-Alkenyloxycarbonyl wie Allyloxycarbonyl, Buten-1-yloxycarbonyl, Penten-1-yloxycarbonyl und Hexen-1-yloxycarbonyl,
- C₃- bis C₈-Alkinyloxycarbonyl, bevorzugt C₃- bis C₅-Alkinyloxycarbonyl wie Propinyloxycarbonyl und Butinyloxycarbonyl,
- R5' und R6' oder R6' und R7'
- gemeinsam
- (CH₂)n, wie CH₂, (CH₂)₂, (CH₂)₃, (CH₂)₄, (CH₂)₅ und (CH₂)₆, bevorzugt (CH₂)₃, (CH₂)₄, (CH₂)₅, (CH₂)₆, besonders bevorzugt (CH₂)₃ und (CH₂)₄,
- (CH=CH)m, wie (CH=CH), (CH=CH)₂, (CH=CH)₃, bevorzugt (CH=CH)₂, (CH=CH)₃ besonders bevorzugt (CH=CH)₂,
- n
-
- 1 bis 10, vorzugsweise 3 bis 6, besonders bevorzugt 3 und 4,
- m
-
- 1 bis 3, vorzugsweise 2 und 3, besonders bevorzugt 2.
- R¹
-
- unbranched or branched C₁ to C₂₀ alkyl, preferably unbranched or branched C₁ to C₁₂ alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec.-butyl, tert.- Butyl, n-pentyl, iso-pentyl, sec.-pentyl, tert.-pentyl, neo-pentyl, 1,2-dimethylpropyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl , n-octyl, iso-octyl, n-nonyl, iso-nonyl, n-decyl, iso-decyl, n-undecyl, iso-undecyl, n-dodecyl and iso-dodecyl,
- unbranched or branched C₂ to C₂₀ alkenyl, preferably unbranched or branched C₂ to C₈ alkenyl, such as allyl, 2-buten-1-yl, 3-buten-2-yl, 4-buten-1-yl, 2- Penten-1-yl and 2,2-dimethylpenten-1-yl,
- unbranched or branched C₂ to C₂₀ alkynyl, preferably unbranched or branched C₂ to C₈ alkynyl, such as propynyl, 1,1-dimethyl-2-propynyl, 1-methyl-2-propynyl, 1-butynyl, 2-butynyl and 4,4-dimethylbut-2-in-1-yl,
- C₃- to C₁₂-cycloalkyl, preferably C₃- to C₈-cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl,
- C₄- to C₂₀-cycloalkyl-alkyl, preferably C₈- to C₈-cycloalkylalkyl, such as cyclopentyl-methyl, 2-cyclopentyl-ethyl, 1-cyclopentyl-ethyl, cyclohexyl-methyl, 1-cyclohexylethyl and 2-cyclohexyl-ethyl,
- unbranched or branched C₁ to C₂₀ hydroxyalkyl, preferably unbranched or branched C₁ to C₈ hydroxyalkyl such as hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl and 3-hydroxypropyl,
- Aryl, such as phenyl, 1-naphthyl and 2-naphthyl, preferably phenyl,
- aryl monosubstituted to trisubstituted by C₁ to C₈ alkyl, preferably phenyl monosubstituted to trisubstituted by C₁ to C₄ alkyl, such as 2-methylphenyl, 4-methylphenyl, 2-ethylphenyl, 4-ethylphenyl, 3-methylphenyl, 2,4-dimethylphenyl, 3,4-dimethylphenyl and 3,4,5-trimethylphenyl,
- aryl mono- to trisubstituted by C₁- to C₈-alkoxy, preferably phenyl mono- to trisubstituted by C₁- to C₄-alkoxy, such as 2-methoxyphenyl, 2-ethoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 3-ethoxyphenyl, 4-ethoxyphenyl, 3,4-dimethoxyphenyl and 3,4,5-trimethoxyphenyl,
- aryl substituted one to three times by C₁- to C₄-haloalkyl, preferably phenyl mono- to triple by C₁- to C₂-fluoro- and chloroalkyl, particularly preferably phenyl substituted by trifluoromethyl and trichloromethyl, such as 4-trifluoromethylphenyl and 4-trichloromethylphenyl,
- aryl monosubstituted to trisubstituted by C₁- to C₄-halooxy, preferably phenyl mono- to trisubstituted by C₁- to C₂-fluoro and chloroalkoxy, particularly preferably phenyl monosubstituted to trisubstituted by trifluoromethoxy and trichloromethoxy, such as trifluoromethoxyphenyl,
- aryl which is mono- to trisubstituted by halogen, preferably phenyl mono- or trisubstituted by fluorine or chlorine, such as 4-chlorophenyl, 3,4-dichlorophenyl, 4-bromophenyl, 4-fluorophenyl and 4-fluoro-3-chlorophenyl,
- aryl monosubstituted to trisubstituted by halophenyl, preferably phenyl monosubstituted to trisubstituted by fluorophenyl and / or chlorophenyl such as (4-chlorophenyl) phenyl
- aryl monosubstituted to trisubstituted by halophenoxy, preferably phenyl monosubstituted to trisubstituted by fluorine and / or chlorophenoxy, such as (4-fluorophenoxy) phenyl,
- aryl monosubstituted to trisubstituted by carboxy, preferably phenyl monosubstituted to trisubstituted by carboxy, such as 2-carboxyphenyl, 3-carboxyphenyl and 4-carboxyphenyl,
- aryl monosubstituted to trisubstituted by C₂ to C₈alkoxycarbonyl, preferably phenyl monosubstituted to trisubstituted by C₂- to C₄alkoxycarbonyl, such as 4-methoxycarbonylphenyl, 4-ethoxycarbonylphenyl, 2-methoxycarbonylphenyl, 2-ethoxycarbonylphenyl and 3-methoxycarbonylphenyl,
- aryl monosubstituted to trisubstituted by cyano, preferably phenyl monosubstituted to trisubstituted by cyano, such as 2-cyanophenyl, 3-cyanophenyl and 4-cyanophenyl,
- C₇ to C₂₀ arylalkyl, preferably C₇ to C₁₂ arylalkyl such as benzyl, phenylethyl, phenylpropyl and phenylisopropyl,
- in the aryl part mono- to trisubstituted by halogen C₇- to C₂₀-aryl-alkyl, preferably in the phenyl part mono- to triple by fluorine or chlorine C₇- to C₁yl-phenyl-alkyl, such as 4-fluorobenzyl, 4-chlorobenzyl, 2.4 -Dichlorobenzyl and 3,4-dichlorobenzyl,
- in the aryl part monosubstituted to trisubstituted by C₁ to C₈-alkyl, C₇ to C₂₀ arylalkyl, preferably in the phenyl part monosubstituted to trisubstituted by C₁- to C Alkyl-alkyl, C₀- to C₁₀-phenyl-alkyl, particularly preferably in Phenyl part mono- to trisubstituted by C₁- to C₂-alkyl C₇- to C₁₀-phenylalkyl, such as 4-methylbenzyl, 4-ethylbenzyl and 4-methylphenethyl,
- in the aryl part monosubstituted to trisubstituted by C₁ to C₈alkoxy, C₇ to C₂₀ arylalkyl, preferably in the phenyl part monosubstituted to trisubstituted by C₁ to C₄alkoxy, C₇ to C₁₀phenylalkyl, particularly preferably in the phenyl part - C dre- to C₁ Phen-substituted by C₁- to C₂-alkoxy-C₁- phenylalkyl, such as 4-methoxybenzyl, 4-ethoxybenzyl and 4-methoxyphenethyl,
- in the aryl part mono- to trisubstituted by C₁- to C₄-haloalkyl, substituted C₇- to C₂₀-arylalkyl, preferably in the phenyl part mono- to trisubstituted by C₁- to C₂-fluoro and chloroalkyl, C₇ to C₁₀-phenylalkyl, particularly preferably Phenyl part mono- to trisubstituted by trifluoromethyl and trichloromethyl C₇-C₁₀-phenylalkyl, such as 4-trifluoromethylbenzyl and 4-trichloromethylbenzyl,
- in the aryl part monosubstituted to trisubstituted by C₁ to C₄-haloalkoxy, C₇ to C₂₀ arylalkyl, preferably in the phenyl part monosubstituted to trisubstituted by C₁ to C₂-haloalkoxy, C₇ to C₁₀ phenylalkyl, particularly preferably monosubstituted to triple by Trifluoromethoxy and trichloromethoxy substituted C₇ to C₁₀ phenylalkyl, such as 4-trifluoromethoxybenzyl and 4-trichloromethoxybenzyl,
- C₇- C₂₀-arylalkyl mono- to trisubstituted by halophenyl, preferably C₇ to C₁₂-phenylalkyl monosubstituted to trisubstituted by fluorine and / or chlorophenyl, such as 4-chlorophenethyl and 4-fluorophenethyl
- C₇- C₂₀ arylalkyl mono- to trisubstituted by halophenoxy, preferably C₇ to C₁₂ phenylalkyl monosubstituted to trisubstituted by fluorine and / or chlorophenoxy, such as 2-chlorophenoxymethyl and 4-chlorophenoxymethyl,
- C bis to C₂₀ arylalkyl which is mono- to trisubstituted by carboxy, preferably C₇ to C₁₂ phenylalkyl which is mono- to trisubstituted by carboxy, such as 4-carboxybenzyl, 4-carboxyphenethyl, 2-carboxybenzyl and 2-carboxyphenylethyl,
- mono- to trisubstituted by C₂- to C₈-alkoxycarbonyl, C₇- C₂₀-arylalkyl, preferably mono- to trisubstituted by C₂- to C₄-alkoxycarbonyl, preferably C₇- to C₁₂-phenylalkyl, such as 4-methoxycarbonylbenzyl, 2-methoxycarbonylbenzyl, 4-ethoxycarbonylbenzyl and 2-ethoxycarbonylbenzyl,
- mono- to trisubstituted by cyano-substituted C₇- C₂₀-arylalkyl, preferably mono- to trisubstituted by cyano-substituted C₇- to C₁₂-phenylalkyl, such as 2-cyanobenzyl, 4-cyanobenzyl, 2-cyanophenethyl and 4-cyanophenethyl,
- phenyl substituted by one, two or three phenyl groups, such as 2- (phenyl) phenyl, 3- (phenyl) phenyl, 4- (phenyl) phenyl and 3,4- (diphenyl) phenyl,
- phenyl substituted by one, two or three phenoxy groups, such as 4-phenoxyphenyl and 2-phenoxyphenyl,
- phenyl which is disubstituted or trisubstituted by halogen and C₁- to C₄-alkyl, such as 2-methyl-4-chlorophenyl and 3-methyl-4-fluorophenyl,
- phenyl which is disubstituted or trisubstituted by halogen and C₁- to C₄-alkoxy, such as 3-chloro-4-methoxyphenyl,
- phenyl which is disubstituted or trisubstituted by halogen and C₁- to C₄-haloalkyl, such as 2-chloro-4-trifluoromethylphenyl,
- phenyl which is disubstituted or trisubstituted by halogen and phenoxy, such as 3-chloro-4-phenoxyphenyl,
- phenyl which is disubstituted or trisubstituted by C₁- to C₄-alkyl and C₁- to C₄-alkoxy, such as 2-methyl-4-methoxyphenyl,
- phenyl which is disubstituted or trisubstituted by C₁- to C₄-alkyl and C₁- to C₄-haloalkyl, such as 3-methyl-4-trichloromethylphenyl,
- phenyl which is disubstituted or trisubstituted by C₁- to C₄-alkyl and phenoxy, such as 2-methyl-4-phenoxyphenyl,
- phenyl which is disubstituted or trisubstituted by C₁- to C₄-alkoxy and C₁- to C₄-haloalkyl, such as 3-trifluoromethyl-4-methoxyphenyl,
- phenyl which is disubstituted or trisubstituted by C₁- to C₄alkoxy and phenoxy, such as 3-methoxy-4-phenoxyphenyl,
- phenyl which is disubstituted or trisubstituted by C₁- to C₄-haloalkyl and phenoxy, such as 3-trifluoromethyl-4-phenoxyphenyl,
- phenyl trisubstituted by halogen, C₁- to C₄-alkyl and C₁- to C₄-alkoxy, such as 2-chloro-3-tert-butyl-4-methoxyphenyl,
- phenyl trisubstituted by halogen, C₁- to C₄-alkyl and C₁- to C₄-haloalkyl, such as 2-methyl-3-chloro-4-trifluoromethylphenyl,
- phenyl trisubstituted by halogen, C₁- to C₄-alkyl and phenoxy, such as 4-chloro-2-ethyl-3-phenoxyphenyl,
- phenyl trisubstituted by halogen, C₁- to C₄-alkoxy and C₁- to C₄-haloalkyl, such as 3-chloro-4-methoxy-3-trifluoromethylphenyl,
- phenyl trisubstituted by halogen, C₁- to C₄-alkoxy and phenoxy, such as 2-fluoro-4-ethoxy-3-phenoxyphenyl,
- phenyl trisubstituted by halogen, C₁- to C₄-haloalkyl and phenoxy, such as 4-fluoro-3-trifluoromethyl-2-phenoxyphenyl,
- phenyl trisubstituted by C₁- to C₄-alkyl, C₁- to C₄-alkoxy and C₁- to C₄-haloalkyl, such as 4-methyl-3-methoxy-2-trichloromethylphenyl,
- phenyl which is triply substituted by C₁- to C₄-alkyl, C₁- to C₄-alkoxy and phenoxy, such as 4-methyl-3-ethoxy-2-phenoxyphenyl,
- phenyl trisubstituted by C₁- to C₄-alkyl, C₁- to C₄-haloalkyl and phenoxy, such as 2-methyl-4-trifluoromethyl-3-phenoxyphenyl,
- phenyl which is triply substituted by C₁- to C₄-alkoxy, C₁- to C₄-haloalkyl and phenoxy, such as 4-methoxy-2-trichloromethyl-3-phenoxyphenyl,
- R², R³
-
- Hydrogen or a radical R¹,
- R¹ and R² or R² and R³ together
-
- (CH₂) n , such as CH₂, (CH₂) ₂, (CH₂) ₃, (CH₂) ₄, (CH₂) ₅ and (CH₂) ₆, preferably (CH₂) ₃, (CH₂) ₄, (CH₂) ₅, ( CH₂) ₆, particularly preferably (CH₂) ₃ and (CH₂) ₄,
- (CH = CH) m , such as (CH = CH), (CH = CH) ₂, (CH = CH) ₃, preferably (CH = CH) ₂, (CH = CH) ₃ particularly preferably (CH = CH) ₂ ,
- n
-
- 1 to 6, preferably 3 to 6, particularly preferably 3 and 4,
- m
-
- 1 to 3, preferably 2 and 3, particularly preferably 2.
- R 3 '
-
- hydrogen
- unbranched or branched C₁ to C₂₀ alkyl, preferably C₁ to C₁₂ alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n -Pentyl, iso-pentyl, sec.-pentyl, tert.-pentyl, neo-pentyl, 1,2-dimethylpropyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl, n- Octyl, n-nonyl, iso-nonyl, n-decyl, iso-decyl, n-undecyl, iso-undecyl, n-dodecyl and iso-dodecyl, particularly preferably unbranched or branched C₁- to C₈-alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec.-butyl, tert.-butyl, n-pentyl, iso-pentyl, sec.-pentyl, tert.-pentyl, neo-pentyl, 1, 2-dimethylpropyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl, n-octyl,
- unbranched or branched C₂ to C₂₀ alkenyl, preferably unbranched or branched C₂ to C₈ alkenyl, such as vinyl, allyl, buten-1-yl, buten-2-yl, buten-3-yl, penten-1-yl, Penten-2-yl, penten-3-yl, penten-4-yl, hexen-1-yl, hexen-2-yl, hexen-3-yl and hexen-4-yl,
- unbranched or branched C₂ to C₂₀ alkynyl, preferably unbranched or branched C₂ to C₈ alkynyl, such as ethynyl, 1-propin-3-yl, 1-butyn-3-yl, 1-pentyn-3-yl, 1- Hexin-5-yl, 1-heptin-6-yl and 1-octin-7-yl,
- unbranched or branched C₂ to C₂₀ alkoxyalkyl, preferably unbranched or branched C₂ to C₈ alkoxyalkyl, such as methoxymethyl, ethoxymethyl, n-propoxymethyl, iso-propoxymethyl, n-butoxymethyl, iso-butoxymethyl, sec.-butoxymethyl, tert.- Butoxymethyl, n-pentoxymethyl, iso-pentoxymethyl, sec.-pentoxymethyl, tert.-pentoxymethyl, neo-pentoxymethyl, 1,2-dimethylpropoxymethyl, n-hexoxymethyl, iso-hexoxymethyl, sec.-hexoxymethyl, n-heptoxymethyl, iso-heptoxymethyl , Methoxy-1-ethyl, ethoxy-1-ethyl, n-propoxy-1-ethyl, iso-propoxy-1-ethyl, n-butoxy-1-ethyl, iso-butoxy-1-ethyl, sec.-butoxy- 1-ethyl, tert-butoxy-1-ethyl, n-pentoxy-1-ethyl, iso-pentoxy-1-ethyl, sec.-pentoxy1-ethyl, tert.-pentoxy-1-ethyl, neo-pentoxy-1 -ethyl, 1,2-dimethylpropoxy-1-ethyl, n-hexoxy-1-ethyl, iso-hexoxyl-ethyl, sec.-hexoxy-1-ethyl, methoxy-2-ethyl, ethoxy-2-ethyl, n- Propoxy-2-ethyl, iso-propoxy-2-ethyl, n-butoxy-2-ethyl, iso-butoxy-2-ethyl, sec.-butoxy-2-ethyl, tert.-butoxy-2-ethyl, n- Pentoxy-2-eth yl, iso-pentoxy-2-ethyl, sec.-pentoxy-2-ethyl, tert.-pentoxy-2-ethyl, neo-pentoxy-2-ethyl, 1,2-dimethyl-propoxy-2-ethyl, n- Hexoxy-2-ethyl, iso-hexoxy-2-ethyl and sec.-hexoxy-2-ethyl,
- unbranched or branched C₄ to C₂₀ alkenyloxyalkyl, preferably unbranched or branched C₄ to C₈ alkenyloxyalkyl, such as allyloxymethyl, allyloxy-1-ethyl, allyloxy-2-ethyl, allyloxy-1-propyl and allyloxy-2-propyl,
- C₃- to C₁₂-cycloalkyl, preferably C₃- to C₈-cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl,
- C₄- to C₂₀-cycloalkyl-alkyl, preferably C₄- to C₈-cycloalkylalkyl, such as cyclopentyl-methyl, 2-cyclopentyl-ethyl, 1-cyclopentyl-ethyl, cyclohexyl-methyl, 1-cyclohexylethyl and 2-cyclohexylethyl,
- R 4 '
-
- C₁ to C₈ alkyl, preferably unbranched C₁ to C₈ alkyl such as methyl, ethyl, propyl, butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl, particularly preferably unbranched C₁ to C₄ alkyl such as Methyl, ethyl, n-propyl or n-butyl,
- R 5 ' , R 6' , R 7 ' , R 8' , R 9 '
-
- independently of each other
- hydrogen
- C₁ to C₈ alkyl, preferably C₁ to C₄ alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl or tert-butyl, particularly preferably methyl or Ethyl,
- C₁ to C₈ alkoxy, preferably C₁ to C₄ alkoxy such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy or tert-butoxy, particularly preferably methoxy or ethoxy ,
- C₂- to C₈-alkenyl, preferably C₂- to C₄-alkenyl such as vinyl, allyl, 3-buten-1-yl, 2-buten-1-yl and 1-buten-1-yl,
- C₃- to C₈-alkenyloxy, preferably C₃- to C₆-alkenyloxy such as allyloxy, buten-1-yloxy, buten-2-yloxy, buten-3-yloxy, penten-1-yloxy, penten-2-yloxy, penten-3 -yloxy, penten-4-yloxy, hexen-1-yloxy and hexen-2-yloxy,
- C₂ to C₈ alkynyl, preferably C₂ to C₄ alkynyl such as ethynyl, 2-propin-1-yl and 3-butyn-1-yl,
- C₃- to C₈-alkynyloxy, preferably C₃- to C₄-alkynyloxy such as propynyloxy and butynyloxy,
- Halogen such as fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine and bromine,
- Cyano,
- Phenyl,
- Phenoxy,
- Halophenyl, preferably chlorophenyl such as 2-chlorophenyl and 4-chlorophenyl,
- Halophenoxy, preferably chlorophenoxy such as 2-chlorophenoxy and 4-chlorophenoxy,
- Carboxy,
- C₂ to C₈ alkoxycarbonyl, preferably C₂ to C₄ alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl and tert-butoxycarbonyl,
- C₃- to C₈-alkenyloxycarbonyl, preferably C₃- to C₆-alkenyloxycarbonyl such as allyloxycarbonyl, buten-1-yloxycarbonyl, penten-1-yloxycarbonyl and hexen-1-yloxycarbonyl,
- C₃- to C₈-alkynyloxycarbonyl, preferably C₃- to C₅-alkynyloxycarbonyl such as propynyloxycarbonyl and butynyloxycarbonyl,
- R 5 ' and R 6' or R 6 ' and R 7'
- together
- (CH₂) n , such as CH₂, (CH₂) ₂, (CH₂) ₃, (CH₂) ₄, (CH₂) ₅ and (CH₂) ₆, preferably (CH₂) ₃, (CH₂) ₄, (CH₂) ₅, ( CH₂) ₆, particularly preferably (CH₂) ₃ and (CH₂) ₄,
- (CH = CH) m , such as (CH = CH), (CH = CH) ₂, (CH = CH) ₃, preferably (CH = CH) ₂, (CH = CH) ₃ particularly preferably (CH = CH) ₂ ,
- n
-
- 1 to 10, preferably 3 to 6, particularly preferably 3 and 4,
- m
-
- 1 to 3, preferably 2 and 3, particularly preferably 2.
Alle Reste R5' bis R9' können ungleich Wasserstoff sein, bevorzugt sind 0 bis 3 ungleich Wasserstoff, besonders bevorzugt sind 0 bis 2 ungleich Wasserstoff.All radicals R 5 ' to R 9' can be not equal to hydrogen, 0 to 3 are preferably not hydrogen, 0 to 2 are particularly preferably not hydrogen.
Ein- bis dreifach substituiert bedeutet ein-, zwei- oder dreifach substituiert.One to three times substituted means one, two or three times substituted.
Um eine für die Elektrolyse ausreichende Leitfähigkeit des Elektrolyten zu gewährleisten, wird der Elektrolysemischung ein halogenhaltiger Hilfselektrolyt zugefügt. Als Hilfselektrolyte werden Jodide oder Bromide eingesetzt, wie Ammoniumhalogenide, z.B. Ammoniumbromid, Ammoniumiodid und Tetrabutylammoniumiodid und besonders bevorzugt Metallhalogenide wie Natriumbromid, Natriumiodid, Kaliumiodid und Kaliumbromid.In order to ensure sufficient conductivity of the electrolyte for the electrolysis, a halogen-containing auxiliary electrolyte is added to the electrolysis mixture. As auxiliary electrolytes iodides or bromides are used, such as ammonium halides, e.g. Ammonium bromide, ammonium iodide and tetrabutylammonium iodide and particularly preferably metal halides such as sodium bromide, sodium iodide, potassium iodide and potassium bromide.
Die Zusammensetzung des Elektrolyten kann in weiten Grenzen gewählt werden. Der Elektrolyt enthält im allgemeinen 0,1 bis 5 Gew.-% Wasser. Die Elektrolyten können beispielsweise folgende Zusammensetzungen haben:
1 bis 49, vorzugsweise 5 bis 30 Gew.-% Keton der Formel II
50 bis 98,9, vorzugsweise 70 bis 95 Gew.-% Alkanol der Formel III
0,1 bis 5, vorzugsweise 0,5 bis 3 Gew.-% Hilfselektrolyt und
0,1 bis 5, vorzugsweise 0,5 bis 3 Gew.-% Wasser.The composition of the electrolyte can be chosen within wide limits. The electrolyte generally contains 0.1 to 5% by weight of water. The electrolytes can have the following compositions, for example:
1 to 49, preferably 5 to 30% by weight of ketone of the formula II
50 to 98.9, preferably 70 to 95% by weight of alkanol of the formula III
0.1 to 5, preferably 0.5 to 3% by weight of auxiliary electrolyte and
0.1 to 5, preferably 0.5 to 3 wt .-% water.
Vorzugsweise nimmt man die elektrochemische Oxidation bei Stromdichten von 0,5 bis 25 A/dm² und bei Temperaturen von (-20) bis 60°C, insbesondere 0 bis 40°C vor. Höhere Temperaturen sind möglich, bringen aber im allgemeinen keine Vorteile. Die Reaktion kann bei vermindertem oder erhöhtem, vorzugsweise jedoch bei Normaldruck (Atmosphärendruck) und in an sich üblichen Elektrolysezellen durchgeführt werden. Vorzugsweise arbeitet man mit ungeteilten Durchflußzellen.The electrochemical oxidation is preferably carried out at current densities of 0.5 to 25 A / dm 2 and at temperatures of (-20) to 60 ° C., in particular 0 to 40 ° C. Higher temperatures are possible, but generally have no advantages. The reaction can be carried out at reduced or elevated, but preferably at normal pressure (atmospheric pressure) and in electrolysis cells which are conventional per se. One preferably works with undivided flow cells.
Als Anodenmaterialien eignen sich beispielsweise Edelmetalle wie Platin oder Oxide wie Ruthenium- und Chromoxid oder RuOxTiOx-Mischoxide und bevorzugt Graphit.Suitable anode materials are, for example, noble metals such as platinum or oxides such as ruthenium and chromium oxide or RuO x TiO x mixed oxides and preferably graphite.
Als Kathodenmaterialien kommen in der Regel Eisen, Stahl, Nickel und Edelmetalle wie Platin und bevorzugt Graphit in Betracht.Iron, steel, nickel and noble metals such as platinum and preferably graphite are generally considered as cathode materials.
Die Aufarbeitung erfolgt in an sich bekannter Weise, vorzugsweise werden die erfindungsgemäßen Verbindungen I destillativ aufgearbeitet.Working up is carried out in a manner known per se; the compounds I according to the invention are preferably worked up by distillation.
Bevorzugte Verbindungen I sind nachfolgend tabellarisch aufgeführt:
Die Hydroxymethylketale I und der Formel I' stellen wichtige Vorprodukte für Hydroxyphenone dar und können zu Pflanzenschutzmitteln, Photoinitiatoren, Riechstoffen und pharmazeutischen Produkten umgesetzt werden.The hydroxymethyl ketals I and the formula I 'are important precursors for hydroxyphenones and can be converted into crop protection agents, photoinitiators, fragrances and pharmaceutical products.
Die Ausgangsverbindungen II wurden in einer ungeteilen Zelle mit 11 bipolaren Elektroden in einem Elektrolyten, der 45 g Kaliumjodid als Hilfselektrolyt enthielt, einer Elektrolyse unterworfen. Anode wie Kathode bestanden aus Graphit. Die Stromdichte betrug 3,3 A/dm² und die Elektrolysetemperatur 25°C. Der Elektrolyt wurde mit einem Durchfluß von 200 l/h durch die Zelle gepumpt. Die genaue Zusammensetzung des Elektrolyten wie auch weitere Einzelheiten der Beispiele 1 bis 3 und der Versuche 4 bis 6, die zum Vergleich ohne Zusatz von Wasser durchgeführt wurden, sind in Tabelle A zusammengestellt.
Die Ausgangsverbindungen II' wurden in einer ungeteilten Zelle mit 11 bipolaren Elektroden in einem Elektrolyten, der 45 g Kaliumiodid als Hilfselektrolyten enthielt, einer Elektrolyse unterworfen. Anode wie auch Kathode bestanden aus Graphit. Die Stromdichte betrug 3,3 A/dm² und die Elektrolysetemperatur 25°C. Der Elektrolyt wurde mit einem Durchfluß von 200 l/h durch die Zelle gepumpt. Die genaue Zusammensetzung des Elektrolyten wie auch weitere Einzelheiten der Beispiele sind in Tabelle B zusammengestellt:
Claims (5)
- A process for preparing α-hydroxymethyl ketals of the general formula IR¹ is C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl, C₂-C₂₀-alkynyl, C₃-C₁₂-cycloalkyl, C₄-C₂₀-cycloalkylalkyl, C₁-C₂₀-hydroxyalkyl, unsubstituted or C₁-C₈-alkyl, C₁-C₈-alkoxy, halogen, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, phenyl, phenoxy, halophenyl, halophenoxy, carboxyl, C₂-C₈-alkoxycarbonyl or cyanosubstituted aryl or C₇-C₂₀-arylalkyl, or R¹ and R² or R² and R³ together are (CH₂)n or (CH=CH)m which is unsubstituted or mono- or disubstituted by C₁-C₈-alkyl, C₁-C₈-alkoxy and/or halogen and in which n is 1 to 10 and m is 1 to 3;R² and R³ are hydrogen or a radical R¹ andR⁴ is C₁-C₈-alkyl,by electrochemical means in the presence of water and of an auxiliary electrolyte, which comprises electrochemical oxidation of a carbonyl compound of the general formula II
R⁴-OH (III)
in the presence of from 0.1 to 5 % by weight of water, using a bromide or iodide as auxiliary electrolyte. - A process for preparing α-hydroxymethyl aryl ketals of the general formula I'R3' is hydrogen, C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl, C₂-C₂₀-alkynyl, C₂-C₂₀-alkoxyalkyl, C₄-C₂₀-alkenyloxyalkyl, C₃-C₁₂-cycloalkyl or C₄-C₂₀-cycloalkylalkyl,R4' is C₁-C₈-alkyl andR5', R6', R7', R8' and R9' are hydrogen, C₁-C₈-alkyl, C₁-C₈-alkoxy, C₂-C₈-alkenyl, C₃-C₈-alkenyloxy, C₂-C₈-alkynyl, C₃-C₈-alkynyloxy, halogen, cyano, phenyl, phenoxy, halophenyl, halophenoxy, carboxyl, C₂-C₈-alkoxycarbonyl, C₃-C₈-alkenyloxycarbonyl, C₃-C₈-alkynyloxycarbonyl, or R5' and R6' or R6' and R7' together are (CH₂)n' or (CH=CH)m' which is unsubstituted or mono- or disubstituted by C₁-C₈-alkyl, C₁-C₈-alkoxy and/or halogen and in which n' is 1 to 10 and m' is 1 to 3,by electrochemical means, which comprises electrochemical oxidation of an aryl methyl ketone of the general formula II'
R4'-OH (III')
in the presence of from 0.1 to 5 % by weight of water, using a bromide or iodide as auxiliary electrolyte. - A process as claimed in claim 1, wherein an electrolyte of the composition
1 to 49 % by weight of carbonyl compound of the formula II,
50 to 98.9 % by weight of an alkanol of the formula III,
0.1 to 5 % by weight of an auxiliary electrolyte and
0.1 to 5 % by weight of water
is used for the electrochemical oxidation. - A process as claimed in claim 1, wherein the electrochemical oxidation is carried out on graphite electrodes.
- A process as claimed in claim 1, wherein the electrochemical oxidation is carried out at from -20 to 60°C and at current densities of 0.5 to 25 A/dm².
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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DE4017576A DE4017576A1 (en) | 1990-05-31 | 1990-05-31 | Alpha-hydroxy-methyl-ketal(s) and acetal(s) prepn. - by electrochemical oxidn. of carbonyl cpd. with an alkanol in presence of small amt. of water |
DE4017576 | 1990-05-31 | ||
DE4017575 | 1990-05-31 | ||
DE4017575A DE4017575A1 (en) | 1990-05-31 | 1990-05-31 | Prepn. of alpha-hydroxy-methyl-aryl-ketal(s) - by electrochemical oxidation of an aryl-methyl ketone with an alkanol in the presence of a small amt. of water |
Publications (2)
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EP0460451A1 EP0460451A1 (en) | 1991-12-11 |
EP0460451B1 true EP0460451B1 (en) | 1995-05-10 |
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EP91108248A Expired - Lifetime EP0460451B1 (en) | 1990-05-31 | 1991-05-22 | Process for the preparation of alpha-hydroxymethyl-ketals |
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US (1) | US5266171A (en) |
EP (1) | EP0460451B1 (en) |
DE (1) | DE59105416D1 (en) |
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US5500099A (en) * | 1995-05-09 | 1996-03-19 | Hoechst Celanese Corporation | Process for the electrochemical oxidation of arylketones |
DE19730308A1 (en) * | 1997-07-15 | 1999-01-21 | Basf Ag | Process for the preparation of catechol monoethers and catechols |
DE19805778A1 (en) * | 1998-02-12 | 1999-08-19 | Basf Ag | Process for the preparation of 2-cycloalkenones |
DE19838046A1 (en) | 1998-08-21 | 2000-02-24 | Basf Ag | Process for the preparation of alpha-diketones from ketols or ketals of ketols |
DE19904929A1 (en) * | 1999-02-06 | 2000-08-10 | Basf Ag | Process for the preparation of 2,2,3,3-tetramethoxypropanol |
DE19937108A1 (en) * | 1999-08-06 | 2001-02-08 | Basf Ag | Process for the preparation of alpha-oxidized carbonyl compounds |
DE10063195A1 (en) | 2000-12-19 | 2002-06-20 | Basf Ag | Electrolysis cell, useful for production of organic and inorganic products, has electrochemically active counter electrode area that is smaller than that of working electrode |
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DE2848397C2 (en) * | 1978-11-08 | 1982-09-23 | Basf Ag, 6700 Ludwigshafen | Electrochemical production of benzaldehyde dialkyl acetals substituted in the 4-position |
US4318783A (en) * | 1978-11-30 | 1982-03-09 | Bayer Aktiengesellschaft | Process for the preparation of optionally substituted benzaldehyde dialkyl acetals |
JPS57188686A (en) * | 1981-05-16 | 1982-11-19 | Toyo Soda Mfg Co Ltd | Production of alpha-hydroxy carbonyl compound |
JPS57188684A (en) * | 1981-05-16 | 1982-11-19 | Toyo Soda Mfg Co Ltd | Production of alpha-hydroxy acetal and alpha-hydroxy ketal or the like |
DE3913166A1 (en) * | 1989-04-21 | 1990-10-25 | Basf Ag | METHOD FOR PRODUCING BENZALDEHYDDIALKYLACETALS AND NEW BENZALDEHYDDIALKYLACETALS AND BENZYL ESTERS |
-
1991
- 1991-05-22 EP EP91108248A patent/EP0460451B1/en not_active Expired - Lifetime
- 1991-05-22 DE DE59105416T patent/DE59105416D1/en not_active Expired - Fee Related
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