EP0460451B1 - Procédé de production d'alpha-hydroxyméthyl-kétals - Google Patents
Procédé de production d'alpha-hydroxyméthyl-kétals Download PDFInfo
- Publication number
- 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
- Authority
- EP
- European Patent Office
- Prior art keywords
- bis
- alkyl
- phenyl
- und
- ethyl
- 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.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 9
- 238000002360 preparation method Methods 0.000 title description 6
- -1 C3-C8-alkenyloxy Chemical group 0.000 claims description 371
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 86
- 229910052736 halogen Inorganic materials 0.000 claims description 38
- 150000002367 halogens Chemical class 0.000 claims description 38
- 125000003118 aryl group Chemical group 0.000 claims description 29
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 29
- 239000003792 electrolyte Substances 0.000 claims description 26
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 238000006056 electrooxidation reaction Methods 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000005059 halophenyl group Chemical group 0.000 claims description 7
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 4
- 125000005002 aryl methyl group Chemical group 0.000 claims description 3
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims 6
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims 2
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 125000004767 (C1-C4) haloalkoxy group Chemical group 0.000 claims 1
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 claims 1
- 125000006734 (C2-C20) alkoxyalkyl group Chemical group 0.000 claims 1
- 125000004648 C2-C8 alkenyl group Chemical group 0.000 claims 1
- 125000004649 C2-C8 alkynyl group Chemical group 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 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 description 23
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 15
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 14
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 10
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 10
- 125000004093 cyano group Chemical group *C#N 0.000 description 9
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 9
- 238000005868 electrolysis reaction Methods 0.000 description 8
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 8
- 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 8
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 7
- 229910052731 fluorine Inorganic materials 0.000 description 7
- 239000011737 fluorine Substances 0.000 description 7
- 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 7
- 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 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 6
- 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 6
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 6
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 6
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- 125000000304 alkynyl group Chemical group 0.000 description 5
- 150000002576 ketones Chemical class 0.000 description 5
- 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 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 4
- 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 4
- 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 4
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 4
- 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 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 4
- 125000004851 cyclopentylmethyl group Chemical group C1(CCCC1)C* 0.000 description 4
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 4
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 125000006665 (C2 to C4) alkoxycarbonyl group Chemical group 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000000068 chlorophenyl group Chemical group 0.000 description 3
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 125000004066 1-hydroxyethyl group Chemical group [H]OC([H])([*])C([H])([H])[H] 0.000 description 2
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 description 2
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 2
- 125000005809 3,4,5-trimethoxyphenyl group Chemical group [H]C1=C(OC([H])([H])[H])C(OC([H])([H])[H])=C(OC([H])([H])[H])C([H])=C1* 0.000 description 2
- 125000003762 3,4-dimethoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C(OC([H])([H])[H])C([H])=C1* 0.000 description 2
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 2
- 125000004207 3-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(OC([H])([H])[H])=C1[H] 0.000 description 2
- 125000004801 4-cyanophenyl group Chemical group [H]C1=C([H])C(C#N)=C([H])C([H])=C1* 0.000 description 2
- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004217 4-methoxybenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1OC([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 2
- 125000006181 4-methyl benzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])C([H])([H])* 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 125000005336 allyloxy group Chemical group 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 230000015572 biosynthetic process Effects 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004965 chloroalkyl group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 2
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 2
- 238000005805 hydroxylation reaction Methods 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 125000005929 isobutyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])OC(*)=O 0.000 description 2
- 125000005928 isopropyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 2
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 2
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 125000006504 o-cyanobenzyl group Chemical group [H]C1=C([H])C(C#N)=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 2
- 125000006505 p-cyanobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C#N)C([H])([H])* 0.000 description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- 125000002409 penten-3-yl group Chemical group C=CC(CC)* 0.000 description 2
- 125000002262 penten-4-yl group Chemical group C=CCC(C)* 0.000 description 2
- 125000003884 phenylalkyl group Chemical group 0.000 description 2
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004344 phenylpropyl group Chemical group 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
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004742 propyloxycarbonyl group Chemical group 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000004784 trichloromethoxy group Chemical group ClC(O*)(Cl)Cl 0.000 description 2
- ALOQXNPKUXJYQG-UHFFFAOYSA-N 1,1-dimethoxy-2-methylpropan-2-ol Chemical compound COC(OC)C(C)(C)O ALOQXNPKUXJYQG-UHFFFAOYSA-N 0.000 description 1
- 238000007148 1,2 rearrangement reaction Methods 0.000 description 1
- 125000004972 1-butynyl group Chemical group [H]C([H])([H])C([H])([H])C#C* 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
- 125000000069 2-butynyl group Chemical group [H]C([H])([H])C#CC([H])([H])* 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
- 125000006512 3,4-dichlorobenzyl group Chemical group [H]C1=C(Cl)C(Cl)=C([H])C(=C1[H])C([H])([H])* 0.000 description 1
- 125000004189 3,4-dichlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(Cl)C([H])=C1* 0.000 description 1
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 1
- 125000006283 4-chlorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1Cl)C([H])([H])* 0.000 description 1
- 125000004176 4-fluorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1F)C([H])([H])* 0.000 description 1
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 1
- 125000000173 4-trifluoromethoxy benzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1OC(F)(F)F)C([H])([H])* 0.000 description 1
- 125000001318 4-trifluoromethylbenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])*)C(F)(F)F 0.000 description 1
- 125000004199 4-trifluoromethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C(F)(F)F 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241001136792 Alle Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 125000003302 alkenyloxy group Chemical group 0.000 description 1
- 125000005452 alkenyloxyalkyl group Chemical group 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000005133 alkynyloxy 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
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000004490 chloroalkoxy group Chemical group 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000001207 fluorophenyl group Chemical group 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 150000004694 iodide salts Chemical class 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
- 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
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002905 orthoesters Chemical class 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- TURAMGVWNUTQKH-UHFFFAOYSA-N propa-1,2-dien-1-one Chemical group C=C=C=O TURAMGVWNUTQKH-UHFFFAOYSA-N 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(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
Definitions
- 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:
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Materials For Photolithography (AREA)
Claims (5)
- Procédé de préparation d'α-hydroxyméthylcétals de la formule générale I
R¹ représente un radical alkyle en C₁ à C₂₀, alcényle en C₂ à C₂₀, alcynyle en C₂ à C₂₀, cycloalkyle en C₃ à C₁₂, cycloalkyl(C₄-C₂₀)alkyle, hydroxyalkyle en C₁ à C₂₀, aryl(C₇-C₂₀)alkyle ou aryle, éventuellement substitué par des radicaux alkyle en C₁ à C₈, alcoxy en C₁ à C₈, des atomes d'halogènes, des radicaux halogénoalkyle en C₁ à C₄, halogénoalcoxy en C₁ à C₄, phényle, phénoxy, halogénophényle, halogénophénoxy, carboxyle, alcoxy(C₂-C₈)carbonyle ou cyano, ou bien R¹ et R², ou R² et R³, en commun, représentent un radical (CH₂)n ou (CH=CH)m où n a une valeur qui varie de 1 à 10 et m a une valeur qui varie de 1 à 3, éventuellement une ou deux fois substitué par des radicaux alkyle en C₁ à C₈, alcoxy en C₁ à C₈ et/ou des atomes d'halogènes,R² et R³ représentent chacun un atome d'hydrogène ou un reste R¹ etR⁴ représente un radical alkyle en C₁ à C₈,par voie électrochimique, en présence d'eau comme aussi d'un électrolyte adjuvant, caractérisé en ce que l'on oxyde électrochimiquement et en présence de 0,1 à 5% en poids d'eau un composé de la formule générale II
R⁴―OH (III),
où on se sert, à titre d'électrolyte adjuvant, d'un bromure ou d'un iodure. - Procédé de préparation d'α-hydroxyméthylarylcétals de la formule générale I'
R3' représente un atome d'hydrogène, un radical alkyle en C₁ à C₂₀, alcényle en C₂ à C₂₀, alcynyle en C₂ à C₂₀, alcoxy(C₂-C₂₀)alkyle, alcényl(C₄-C₂₀)oxyalkyle, cycloalkyle en C₃ à C₁₂ ou cyloalkyl(C₄-C₂₀)alkyle,R4' représente un radical alkyle en C₁ à C₈ etR5' R6', R7', R8' et R9' représentent chacun un atome d'hydrogène, un radical alkyle en C₁ à C₈, alcoxy en C₁ à C₈, alcényle en C₂ à C₈, alcényloxy en C₃ à C₈, alcynyle en C₂ à C₈, alcynyloxy en C₃ à C₈, un atome d'halogène, un radical cyano, phényle, phénoxy, halogénophényle, halogénophénoxy, carboxyle, alcoxy(C₂-C₈)carbonyle, alcényl(C₃-C₈)oxycarbonyle, alcynyl(C₃-C₈)oxycarbonyle, ou bien R5' et R6', ou R6' et R7', en commun, forment un radical (CH₂)n' ou (CH=CH)m' éventuellement une ou deux fois substitué par des radicaux alkyle en C₁ à C₈, alcoxy en C₁ à C₈ et/ou des atomes d'halogènes, n' ayant une valeur qui varie de 1 à 10 et m' ayant une valeur qui varie de 1 à 3,par voie électrochimique, caractérisé en ce que l'on oxyde électrochimiquement et en présence de 0,1 à 5% en poids d'eau, une arylméthylcétone de la formule générale II'
R⁴'―OH (III'),
où l'on se sert, à titre d'électrolyte adjuvant, d'un bromure ou d'un iodure. - Procédé suivant la revendication 1, caractérisé en ce qu'en vue de l'oxydation électrochimique, on utilise un électrolyte de la composition suivante :
1 à 49% en poids d'un composé carbonylé de la formule II,
50 à 98,9% en poids d'un alcanol de la formule III,
0,1 à 5% en poids d'un électrolyte adjuvant et
0,1 à 5% en poids d'eau. - Procédé suivant la revendication 1, caractérisé en ce que l'on entreprend l'oxydation électrochimique sur des électrodes en graphite.
- Procédé suivant la revendication 1, caractérisé en ce que l'on entreprend l'oxydation électrochimique à des températures qui varient de -20°C à +60°C et à des densités de courant de 0,5 à 25 A/dm².
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4017576A DE4017576A1 (de) | 1990-05-31 | 1990-05-31 | Verfahren zur herstellung von (alpha)-hydroxymethylacetalen und (alpha)-hydroxymethylketalen |
| DE4017575A DE4017575A1 (de) | 1990-05-31 | 1990-05-31 | Verfahren zur herstellung von (alpha)-hydroxymethylarylketalen |
| DE4017576 | 1990-05-31 | ||
| DE4017575 | 1990-05-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0460451A1 EP0460451A1 (fr) | 1991-12-11 |
| EP0460451B1 true EP0460451B1 (fr) | 1995-05-10 |
Family
ID=25893726
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP91108248A Expired - Lifetime EP0460451B1 (fr) | 1990-05-31 | 1991-05-22 | Procédé de production d'alpha-hydroxyméthyl-kétals |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US5266171A (fr) |
| EP (1) | EP0460451B1 (fr) |
| DE (1) | DE59105416D1 (fr) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5500099A (en) * | 1995-05-09 | 1996-03-19 | Hoechst Celanese Corporation | Process for the electrochemical oxidation of arylketones |
| DE19730308A1 (de) * | 1997-07-15 | 1999-01-21 | Basf Ag | Verfahren zur Herstellung von Brenzcatechinmonoethern und Brenzcatechinen |
| DE19805778A1 (de) * | 1998-02-12 | 1999-08-19 | Basf Ag | Verfahren zur Herstellung von 2-Cycloalkenonen |
| DE19838046A1 (de) | 1998-08-21 | 2000-02-24 | Basf Ag | Verfahren zur Herstellung von alpha-Diketonen aus Ketolen oder Ketalen von Ketolen |
| DE19904929A1 (de) * | 1999-02-06 | 2000-08-10 | Basf Ag | Verfahren zur Herstellung von 2,2,3,3-Tetramethoxypropanol |
| DE19937108A1 (de) * | 1999-08-06 | 2001-02-08 | Basf Ag | Verfahren zur Herstellung von in alpha-Stellung oxidierten Carbonylverbindungen |
| DE10063195A1 (de) | 2000-12-19 | 2002-06-20 | Basf Ag | Bipolare quasigeteilte Elektrolysezellen |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2848397C2 (de) * | 1978-11-08 | 1982-09-23 | Basf Ag, 6700 Ludwigshafen | Elektrochemische Herstellung von in 4-Stellung substituierten Benzaldehyddialkylacetalen |
| 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 (de) * | 1989-04-21 | 1990-10-25 | Basf Ag | Verfahren zur herstellung von benzaldehyddialkylacetalen und neue benzaldehyddialkylacetale und benzylester |
-
1991
- 1991-05-22 DE DE59105416T patent/DE59105416D1/de not_active Expired - Fee Related
- 1991-05-22 EP EP91108248A patent/EP0460451B1/fr not_active Expired - Lifetime
- 1991-05-28 US US07/705,786 patent/US5266171A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP0460451A1 (fr) | 1991-12-11 |
| DE59105416D1 (de) | 1995-06-14 |
| US5266171A (en) | 1993-11-30 |
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