DE4017575A1 - 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 - Google Patents
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 waterInfo
- Publication number
- DE4017575A1 DE4017575A1 DE4017575A DE4017575A DE4017575A1 DE 4017575 A1 DE4017575 A1 DE 4017575A1 DE 4017575 A DE4017575 A DE 4017575A DE 4017575 A DE4017575 A DE 4017575A DE 4017575 A1 DE4017575 A1 DE 4017575A1
- Authority
- DE
- Germany
- Prior art keywords
- alkyl
- ethyl
- aryl
- prepn
- electrochemical oxidation
- 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.)
- Withdrawn
Links
- 238000006056 electrooxidation reaction Methods 0.000 title claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 125000005002 aryl methyl group Chemical group 0.000 title claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 9
- 150000002367 halogens Chemical class 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 5
- 125000005059 halophenyl group Chemical group 0.000 claims abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 3
- -1 cyano, phenyl Chemical group 0.000 claims description 85
- 239000003792 electrolyte Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims 1
- 125000003342 alkenyl group Chemical group 0.000 abstract description 5
- 125000000217 alkyl group Chemical group 0.000 abstract description 5
- 125000000304 alkynyl group Chemical group 0.000 abstract description 5
- 125000003302 alkenyloxy group Chemical group 0.000 abstract description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 abstract description 2
- 238000003541 multi-stage reaction Methods 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 125000005092 alkenyloxycarbonyl group Chemical group 0.000 abstract 1
- 125000005133 alkynyloxy group Chemical group 0.000 abstract 1
- 125000005225 alkynyloxycarbonyl group Chemical group 0.000 abstract 1
- 239000003814 drug Substances 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 abstract 1
- 239000003223 protective agent Substances 0.000 abstract 1
- 230000008707 rearrangement Effects 0.000 abstract 1
- 238000006467 substitution reaction Methods 0.000 abstract 1
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 150000002431 hydrogen Chemical group 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 125000006665 (C2 to C4) alkoxycarbonyl group Chemical group 0.000 description 1
- 238000007148 1,2 rearrangement reaction Methods 0.000 description 1
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 1
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019899 RuO Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000005452 alkenyloxyalkyl group Chemical group 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 125000005336 allyloxy group Chemical group 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004981 cycloalkylmethyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000005929 isobutyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])OC(*)=O 0.000 description 1
- 125000005928 isopropyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 125000005484 neopentoxy group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002905 orthoesters Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000002409 penten-3-yl group Chemical group C=CC(CC)* 0.000 description 1
- 125000002262 penten-4-yl group Chemical group C=CCC(C)* 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004742 propyloxycarbonyl group Chemical group 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
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
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)
Abstract
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von α-Hydroxymethylarylketalen durch elektrochemische Oxidation von Arylmethylketonen mit Alkanolen in Gegenwart eines Hilfselektrolyten und 0 bis 5 Gew.-% Wasser.The present invention relates to a method for producing α-Hydroxymethylaryl ketals by electrochemical oxidation of aryl methyl ketones with alkanols in the presence of an auxiliary electrolyte and 0 to 5% by weight water.
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.From Tetrahedron Letters 25, 691-694 (1984) and from J. Org. Chem., 51, 130-135 (1986) is the preparation of α-hydroxymethylaryl ketals from difficult to access starting compounds under basic conditions in known 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 Bedindungen 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 for the corresponding α-hydroxyacetals and ketals is in J. Chem. Soc., Perk. I, 73-77 (1986). The oxidation under neutral conditions only give low yields (JP-A-57/188 684). The 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. H. in alcoholic Solution, but either with iodine / lithium perchlorate as auxiliary electrolyte not be oxidized or only react to the ketals. In the presence of Orthoesters under otherwise unchanged conditions will not find any 2-hydroxylation but a 1,2-rearrangement of the aryl radical to 2-alkyl-2- arylacetic acid esters instead.
Der Erfindung lag daher die Aufgabe zugrunde, ein Verfahren zur Herstellung von α-Hydroxymethylarylketalen zur Verfügung zu stellen und den zuvor genannten Nachteilen abzuhelfen.The invention was therefore based on the object of a method for the production of α-hydroxymethylaryl ketals and the previously available remedied disadvantages.
Demgemäß wurde ein Verfahren zur Herstellung von α-Hydroxymethylarylketalen der allgemeinen Formel IAccordingly, there has been a process for producing α-hydroxymethylaryl ketals of the general formula I
in der die Substituenten
R¹ 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,
R² C₁- bis C₈-Alkyl und
R³, R⁴, R⁵, R⁶, R⁷ 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 R³ und R⁴ oder R⁴ und R⁵ 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,
gefunden, welches dadurch gekennzeichnet ist, daß man ein Arylmethylketon
der allgemeinen Formel IIin which the substituents
R¹ is 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,
R² is C₁ to C₈ alkyl and
R³, R⁴, R⁵, R⁶, R⁷ 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 R³ and R⁴ or R⁴ and R⁵ together an optionally by C₁ to C₈ alkyl, C₁ to C₈ alkoxy and / or halogen monosubstituted or disubstituted (CH 2 ) n - or (CH = CH) m group, in which n for 1 to 10 and m for 1 up to 3,
found, which is characterized in that an aryl methyl ketone of the general formula II
in der Ar und R¹ die oben genannten Bedeutungen haben, mit einem Alkanol der allgemeinen Formel IIIin which Ar and R¹ have the meanings given above, with an alkanol of the general formula III
R²-OH (III)R²-OH (III)
in der R² die oben genannten Bedeutungen hat, in Gegenwart eines Hilfselektrolyten und 0 bis 5 Gew.% Wasser elektrochemisch oxidiert.in which R² has the meanings given above, in the presence of an auxiliary electrolyte and 0 to 5% by weight of water electrochemically oxidized.
Als Ausgangsverbindungen kommen prinzipiell alle Arylmethylketone der Formel II in Betracht, die unter den Elektrolysebedingungen inerte Substituenten tragen. In principle, all aryl methyl ketones come as starting compounds Formula II which is inert under the electrolysis conditions Bear substituents.
Dabei haben die Substituenten in den Formeln I, II und III im einzelnen
folgende Bedeutungen:
R¹ 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.-Heyl, n-Heptyl,
iso-Heptyl, n-Octyl, n-Nonyl, iso-Nonyl, n-Decyl,
iso-Decyl, n-Undecyl, iso-Undecyl, n-Dodecyl und
iso-Dodecyl, besonders bevorzugtes 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-2-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.-Pentoxy-1-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-Alkenylolxyalkyl, 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-alkyl,
2-Cyclopentyl-ethyl, 1-Cyclopentyl-ethyl, Cycloalkyl-
methyl, 1-Cyclohexylethyl und 2-Cyclohexylethyl,
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,
R³, R⁴, R⁵, R⁶, R⁷ 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-1-yloxy,
Penten-1-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-Propn-1-yl und 3-Butin-1-yl,
C₃- bis C₈-Alkinyloxy, bevorzugt C₃- bis C₄-
Alkinyloxy wie Propinoxy und Butinoxy,
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,
R³ und R⁴ oder R⁴ und R⁵ 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,
1 bis 10, vorzugsweise 3 bis 6, besonders
bevorzugt 3 und 4,
1 bis 3, vorzugsweise 2 und 3, besonders bevorzugt
2.The substituents in the formulas I, II and III have the following meanings:
R¹ is hydrogen,
unbranched or branched C₁ to C₂₀ alkyl, preferably 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.-Heyl, n-heptyl, iso-heptyl, n- Octyl, n-nonyl, iso-nonyl, n-decyl, iso-decyl, n-undecyl, iso-undecyl, n-dodecyl and iso-dodecyl, particularly preferred 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-2-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-pentoxy-1-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-pentox y-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 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-alkyl, 2-cyclopentyl-ethyl, 1-cyclopentyl-ethyl, cycloalkyl-methyl, 1-cyclohexylethyl and 2-cyclohexylethyl,
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,
R³, R⁴, R⁵, R⁶, R⁷ independently of one another
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-1-yloxy, penten-1-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-propn-1-yl and 3-butyn-1-yl,
C₃- to C₈-alkynyloxy, preferably C₃- to C₄-alkynyloxy such as propynoxy and butynoxy,
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,
R³ and R⁴ or R⁴ and R⁵ together
(CH 2 ) n , such as CH 2 , (CH 2 ) 2 , (CH 2 ) 3 , (CH 2 ) 4 , (CH 2 ) 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,
1 to 10, preferably 3 to 6, particularly preferably 3 and 4,
1 to 3, preferably 2 and 3, particularly preferably 2.
Alle Reste R³ bis R⁷ können ungleich Wasserstoff sein, bevorzugt sind 0 bis 3 ungleich Wasserstoff, besonders bevorzugt sind 0 bis 2 bis ungleich Wasserstoff.All radicals R³ to R⁷ may not be hydrogen, 0 are preferred to 3 not equal to hydrogen, 0 to 2 to not equal are particularly preferred Hydrogen.
Um eine für die Elektrolyse ausreichende Leitfähigkeit des Elektrolyten zu gewährleisten, wird der Elektrolysemischung ein vorzugsweise halogenhaltiger Hilfselektrolyt zugefügt. Als Hilfselektrolyte kommen beispielsweise elementares Halogen, Alkylhalogenid und Halogenwasserstoff, bevorzugt werden Jodide oder Bromide eingesetzt, wie Ammoniumhalogenide, z. B. Ammoniumbromid, Ammmoniumiodid und Tetrabutylammoniumiodid und besonders bevorzugt Metallhalogenide wie Natriumbromid, Natriumiodid, Kaliumiodid und Kaliumbromid, in Betracht.To ensure sufficient conductivity of the electrolyte for the electrolysis ensure, the electrolysis mixture is preferably a halogen-containing Auxiliary electrolyte added. Examples of auxiliary electrolytes are: elemental halogen, alkyl halide and hydrogen halide, preferred iodides or bromides are used, such as ammonium halides, e.g. B. Ammonium bromide, ammonium iodide and tetrabutylammonium iodide and especially 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 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 R²-OH,
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 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 alkanol R²-OH,
0.1 to 5, preferably 0.5 to 3 wt .-% 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 taken at current densities of 0.5 to 25 A / dm² and at temperatures from (-20) to 60 ° C, especially 0 up to 40 ° C. Higher temperatures are possible, but generally bring no advantages. The reaction can be reduced or increased, but preferably at normal pressure (atmospheric pressure) and in itself usual electrolysis cells are carried out. 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 Precious metals such as platinum and preferably graphite.
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, preferably the compounds I according to the invention worked up by distillation.
Die Hydroxymethylarylketale I stellen wichtige Vorprodukte für Hydroxyphenone dar und können zu Pflanzenschutzmitteln, Photoinitiatoren und pharmazeutischen Produkten umgesetzt werden.The hydroxymethylaryl ketals I are important precursors for Hydroxyphenones are and can be used as pesticides, photoinitiators and pharmaceutical products.
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 der Tabelle zusammengestellt: The starting compounds II were in an undivided cell with 11 bipolar electrodes in an electrolyte containing 45 g of potassium iodide Contained auxiliary electrolytes, subjected to electrolysis. Anode as well The cathode consisted of graphite. The current density was 3.3 A / dm² and the Electrolysis temperature 25 ° C. The electrolyte was flowed through 200 l / h pumped through the cell. The exact composition of the electrolyte as well as further details of the examples are in the table compiled:
Claims (5)
R¹ 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,
R² C₁- bis C₈-Alkyl und
R³, R⁴, R⁵, R⁶, R⁷ 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 R³ und R⁴ oder R⁴ und R⁵ 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,
dadurch gekennzeichnet, daß man ein Arylmethylketon der allgemeinen Formel II in der Ar und R¹ die oben genannten Bedeutungen haben, mit einem Alkanol der allgemeinen Formel IIIR²-OH (III),in der R² die oben genannten Bedeutungen hat, in Gegenwart eines Hilfselektrolyten und 0 bis 5 Gew.-% Wasser elektrochemisch oxidiert.1. Process for the preparation of α-hydroxymethylaryl ketals of the general formula I in which the substituents
R¹ is 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,
R² is C₁ to C₈ alkyl and
R³, R⁴, R⁵, R⁶, R⁷ 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 R³ and R⁴ or R⁴ and R⁵ together an optionally by C₁ to C₈ alkyl, C₁ to C₈ alkoxy and / or halogen monosubstituted or disubstituted (CH 2 ) n - or (CH = CH) m group, in which n for 1 to 10 and m for 1 up to 3,
characterized in that an aryl methyl ketone of the general formula II in which Ar and R¹ have the meanings given above, with an alkanol of the general formula IIIR²-OH (III) in which R² has the meanings mentioned above, in the presence of an auxiliary electrolyte and 0 to 5% by weight of water, electrochemically oxidized.
1 bis 49 Gew.-% Keton der Formel II,
50 bis 98,8 Gew.-% Alkanol R²-OH,
0,1 bis 5 Gew.-% Hilfselektrolyt und
0,1 bis 5 Gew.-% Wasser
verwendet.2. The method according to claim 1, characterized in that for the electrochemical oxidation an electrolyte of the composition
1 to 49% by weight of ketone of the formula II,
50 to 98.8% by weight of alkanol R²-OH,
0.1 to 5 wt .-% auxiliary electrolyte and
0.1 to 5% by weight of water
used.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
| DE59105416T DE59105416D1 (en) | 1990-05-31 | 1991-05-22 | Process for the preparation of alpha-hydroxymethyl-ketals. |
| EP91108248A EP0460451B1 (en) | 1990-05-31 | 1991-05-22 | Process for the preparation of alpha-hydroxymethyl-ketals |
| US07/705,786 US5266171A (en) | 1990-05-31 | 1991-05-28 | Preparation of α-hydroxymethal acetals |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 (1)
| Publication Number | Publication Date |
|---|---|
| DE4017575A1 true DE4017575A1 (en) | 1991-12-05 |
Family
ID=6407572
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE4017575A Withdrawn 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 |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE4017575A1 (en) |
-
1990
- 1990-05-31 DE DE4017575A patent/DE4017575A1/en not_active Withdrawn
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