WO1999065853A1 - Procede de preparation de composes p-hydroxymandeliques eventuellement substitues - Google Patents
Procede de preparation de composes p-hydroxymandeliques eventuellement substitues Download PDFInfo
- Publication number
- WO1999065853A1 WO1999065853A1 PCT/FR1999/001442 FR9901442W WO9965853A1 WO 1999065853 A1 WO1999065853 A1 WO 1999065853A1 FR 9901442 W FR9901442 W FR 9901442W WO 9965853 A1 WO9965853 A1 WO 9965853A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- formula
- carbon atoms
- radical
- catalyst
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 56
- 150000001875 compounds Chemical class 0.000 title claims abstract description 37
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims abstract description 92
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 12
- 150000001491 aromatic compounds Chemical group 0.000 claims abstract description 10
- YHXHKYRQLYQUIH-UHFFFAOYSA-N 4-hydroxymandelic acid Chemical compound OC(=O)C(O)C1=CC=C(O)C=C1 YHXHKYRQLYQUIH-UHFFFAOYSA-N 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 3
- -1 hydroxyl aromatic compound Chemical class 0.000 claims description 66
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 57
- 239000002253 acid Substances 0.000 claims description 36
- 125000004432 carbon atom Chemical group C* 0.000 claims description 36
- 239000003054 catalyst Substances 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 24
- 235000006408 oxalic acid Nutrition 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 17
- 150000003254 radicals Chemical class 0.000 claims description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 15
- 150000007513 acids Chemical class 0.000 claims description 15
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 229920006395 saturated elastomer Polymers 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- HMNKTRSOROOSPP-UHFFFAOYSA-N 3-Ethylphenol Chemical compound CCC1=CC=CC(O)=C1 HMNKTRSOROOSPP-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 6
- 229960001867 guaiacol Drugs 0.000 claims description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 6
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 6
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012429 reaction media Substances 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 125000002950 monocyclic group Chemical group 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 4
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000002837 carbocyclic group Chemical group 0.000 claims description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- 235000012141 vanillin Nutrition 0.000 claims description 3
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims description 3
- ZUUNZDIGHGJBAR-UHFFFAOYSA-N 1h-imidazole-2,5-dicarboxylic acid Chemical class OC(=O)C1=CNC(C(O)=O)=N1 ZUUNZDIGHGJBAR-UHFFFAOYSA-N 0.000 claims description 2
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 claims description 2
- ZNCUUYCDKVNVJH-UHFFFAOYSA-N 2-isopropoxyphenol Chemical compound CC(C)OC1=CC=CC=C1O ZNCUUYCDKVNVJH-UHFFFAOYSA-N 0.000 claims description 2
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical compound [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 3
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- RMLFFXFBUSQFJY-UHFFFAOYSA-N OC(=O)C(O)=O.OC(=O)CC(O)=O.OC(=O)CCC(O)=O Chemical compound OC(=O)C(O)=O.OC(=O)CC(O)=O.OC(=O)CCC(O)=O RMLFFXFBUSQFJY-UHFFFAOYSA-N 0.000 claims 1
- 125000002015 acyclic group Chemical group 0.000 claims 1
- 239000000543 intermediate Substances 0.000 claims 1
- DFFZOPXDTCDZDP-UHFFFAOYSA-N naphthalene-1,5-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1C(O)=O DFFZOPXDTCDZDP-UHFFFAOYSA-N 0.000 claims 1
- VAWFFNJAPKXVPH-UHFFFAOYSA-N naphthalene-1,6-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC2=CC(C(=O)O)=CC=C21 VAWFFNJAPKXVPH-UHFFFAOYSA-N 0.000 claims 1
- 125000003367 polycyclic group Chemical group 0.000 claims 1
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical class OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 229940015043 glyoxal Drugs 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 2
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N 2-Ethylphenol Chemical compound CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- ASHGTJPOSUFTGB-UHFFFAOYSA-N 3-methoxyphenol Chemical compound COC1=CC=CC(O)=C1 ASHGTJPOSUFTGB-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- CGQCWMIAEPEHNQ-UHFFFAOYSA-N DL-Vanillylmandelic acid Natural products COC1=CC(C(O)C(O)=O)=CC=C1O CGQCWMIAEPEHNQ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229960002510 mandelic acid Drugs 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 2
- XWMLFCHJBNDGFN-UHFFFAOYSA-N n-(3-formyl-4-hydroxyphenyl)acetamide Chemical compound CC(=O)NC1=CC=C(O)C(C=O)=C1 XWMLFCHJBNDGFN-UHFFFAOYSA-N 0.000 description 2
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 125000006353 oxyethylene group Chemical group 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-dioxonaphthalene Natural products C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 1
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- WWGQHTJIFOQAOC-UHFFFAOYSA-N 2,3,5-trichlorophenol Chemical compound OC1=CC(Cl)=CC(Cl)=C1Cl WWGQHTJIFOQAOC-UHFFFAOYSA-N 0.000 description 1
- UMPSXRYVXUPCOS-UHFFFAOYSA-N 2,3-dichlorophenol Chemical compound OC1=CC=CC(Cl)=C1Cl UMPSXRYVXUPCOS-UHFFFAOYSA-N 0.000 description 1
- OEEUPULXQBRPEO-UHFFFAOYSA-N 2,4-Dimethyladipic acid Chemical compound OC(=O)CC(C)CC(C)C(O)=O OEEUPULXQBRPEO-UHFFFAOYSA-N 0.000 description 1
- RANCECPPZPIPNO-UHFFFAOYSA-N 2,5-dichlorophenol Chemical compound OC1=CC(Cl)=CC=C1Cl RANCECPPZPIPNO-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- MOEFFSWKSMRFRQ-UHFFFAOYSA-N 2-ethoxyphenol Chemical compound CCOC1=CC=CC=C1O MOEFFSWKSMRFRQ-UHFFFAOYSA-N 0.000 description 1
- TWLSOWAQVSIFIF-UHFFFAOYSA-N 2-hydroxy-2-(2-hydroxyphenyl)acetic acid Chemical class OC(=O)C(O)C1=CC=CC=C1O TWLSOWAQVSIFIF-UHFFFAOYSA-N 0.000 description 1
- KDTZBYPBMTXCSO-UHFFFAOYSA-N 2-phenoxyphenol Chemical compound OC1=CC=CC=C1OC1=CC=CC=C1 KDTZBYPBMTXCSO-UHFFFAOYSA-N 0.000 description 1
- LCHYEKKJCUJAKN-UHFFFAOYSA-N 2-propylphenol Chemical compound CCCC1=CC=CC=C1O LCHYEKKJCUJAKN-UHFFFAOYSA-N 0.000 description 1
- VPOMSPZBQMDLTM-UHFFFAOYSA-N 3,5-dichlorophenol Chemical compound OC1=CC(Cl)=CC(Cl)=C1 VPOMSPZBQMDLTM-UHFFFAOYSA-N 0.000 description 1
- HORNXRXVQWOLPJ-UHFFFAOYSA-N 3-chlorophenol Chemical compound OC1=CC=CC(Cl)=C1 HORNXRXVQWOLPJ-UHFFFAOYSA-N 0.000 description 1
- RTZZCYNQPHTPPL-UHFFFAOYSA-N 3-nitrophenol Chemical compound OC1=CC=CC([N+]([O-])=O)=C1 RTZZCYNQPHTPPL-UHFFFAOYSA-N 0.000 description 1
- HBUCPZGYBSEEHF-UHFFFAOYSA-N 3-phenoxyphenol Chemical compound OC1=CC=CC(OC=2C=CC=CC=2)=C1 HBUCPZGYBSEEHF-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 125000001204 arachidyl 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])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])[H] 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 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
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl 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])* 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical compound C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000005817 fluorobutyl group Chemical group [H]C([H])(F)C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003784 fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 125000005816 fluoropropyl group Chemical group [H]C([H])(F)C([H])([H])C([H])([H])* 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 125000005027 hydroxyaryl group Chemical group 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 1
- 229960001047 methyl salicylate Drugs 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- JRNGUTKWMSBIBF-UHFFFAOYSA-N naphthalene-2,3-diol Chemical compound C1=CC=C2C=C(O)C(O)=CC2=C1 JRNGUTKWMSBIBF-UHFFFAOYSA-N 0.000 description 1
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002897 organic nitrogen compounds Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 150000002907 osmium Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- KHUXNRRPPZOJPT-UHFFFAOYSA-N phenoxy radical Chemical compound O=C1C=C[CH]C=C1 KHUXNRRPPZOJPT-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 1
- 239000000523 sample Substances 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
- 238000007086 side reaction Methods 0.000 description 1
- 125000004079 stearyl 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])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])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
Definitions
- the present invention relates to a process for the preparation of optionally substituted and derived p-hydroxymandelic compounds.
- optionally substituted p-hydroxymandelic compounds means an aromatic compound at least carrying a -CHOH-COOH group in the para position of a hydroxyl group.
- the present invention relates more particularly to the preparation of p-hydroxymandelic acid and 3-methoxy p-hydroxymandelic acid.
- One of the conventional synthesis routes for p-hydroxymandelic acids consists in carrying out the condensation in an alkaline medium, of glyoxylic acid on phenol and / or its corresponding derivatives.
- the yield is limited by the fact that the condensation reaction is not selective and also leads to o-hydroxymandelic acids and to dimandelic acids.
- the reaction yield is reduced due to a parasitic side reaction. Indeed, glyoxyliqu ⁇ acid in an aqueous alkaline medium, is transformed according to the Cannizaro reaction, into oxalic and glycolic acids.
- glyoxylic acid Given the difficulty of obtaining satisfactory reaction yields, it is important to control the various process parameters and, in particular, the quality of the glyoxylic acid used.
- the most important process from an industrial point of view for the preparation of glyoxylic acid consists in oxidizing glyoxal with nitric acid. This gives aqueous solutions of glyoxylic acid, which, in addition to the unreacted glyoxal, also contain oxalic acid, organic acids, such as formic acid, acetic acid, glycolic acid. and nitric acid. Until now, we have not stopped looking for new methods of separation and purification of glyoxylic acid.
- DE-A 2 501 743 discloses a process according to which glyoxylic acid is separated from these impurities by extraction using aliphatic or cycloaliphatic alcohols or esters of aliphatic alcohols with low carbon condensation.
- a process for obtaining aqueous solutions of glyoxylic acid free of other acids which consists in treating the starting solution with an organic nitrogen compound, preferably a tertiary amine at a temperature at most equal to 50 ° C. and then to extract glyoxylic acid by exhausting the organic phase with water, at a higher temperature.
- an organic nitrogen compound preferably a tertiary amine
- the present invention relates specifically to a process for the preparation of optionally substituted p-hydroxymandelic compounds and derivatives which consists in carrying out the condensation in water, in the presence of an alkaline agent, of an aromatic compound carrying at least one hydroxyl group and whose position in para is free, with glyoxylic acid, said process being characterized in that the reaction is carried out in the presence of an effective amount of a compound carrying at least two carboxylic functions.
- the use of the catalyst of the invention makes it possible to increase the reaction yield.
- Another advantage of the process of the invention is that it can use a more technical glyoxylic acid and containing inter alia oxalic acid.
- the process of the invention applies very particularly to phenol but also to substituted phenols having at least one position in para-unsubstituted.
- the aromatic ring carries at least one hydroxyl group but it can also carry one or more other substituents. Usually, by several substituents, less than four substituents are defined per aromatic ring.
- a hydrocarbon group having from 1 to 20 carbon atoms chosen from alkyl, alkoxy, hydroxyalkyl, cycloalkyl, aryl, phenoxy, alkoxyalkyl, fluoroalkyl, hydroxyalkoxyalkylene groups,
- R groups placed on two vicinal carbon atoms can form together and with the carbon atoms which carry them a benzene ring.
- R radicals capable of being carried by the aromatic ring are given below:
- alkyl radicals such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, n-octyl, 2-ethylhexyl, decyl, octadecyl, eicosyl,
- - alkoxy radicals such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, hexyloxy, decyloxy, hexadecyloxy, octadecyloxy or a phenoxy radical,
- hydroxyalkyl radicals such as hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxyhexyl, hydroxydecyl,
- cycloalkyl radicals such as cyclopentyl, cyclohexyl, cycloheptyl, fluoroalkyl radicals such as fluoromethyl, difluoromethyl, trifluoromethyl, fluoroethyl, trifluoro- 1, 1, 1 ethyl, pentafluoroethyl, fluoropropyl, fluorobutyl, trifluoroamyl,
- hydroxyalkyoxyalkylene radicals such as hydroxymethyloxyethylene, hydroxyethyl di- (oxyethylene), hydroxyethyl tri- (oxyethylene), hydroxy-ethyloxypropylene-1, 2, hydroxyethyloxybutylene, hydroxypropyloxypropylene, hydroxybutyloxybutylene, hydroxybutyl di- (oxybutylene),
- halogen atoms such as fluorine, chlorine, bromine or iodine.
- - x is equal to 0, 1, 2 or 3,
- - R represents one of the following groups or functions:. a hydrogen atom,. an alkyl radical, linear or branched, having from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms,
- a linear or branched alkoxy radical having from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms,. a group - OH,. a group - CHO,
- the compounds of formula (I) are chosen in which the identical or different radicals R are a hydrogen atom, an linear or branched alkyl radical having from 1 to 4 carbon atoms such as methyl and ethyl radicals , n-propyl, isopropyl, n-butyl or isobutyl, a linear or branched alkoxy radical having from 1 to 4 carbon atoms such as methoxy or ethoxy radicals, a group - CHO or a chlorine atom and x is preferably equal to 0 or 1.
- R are a hydrogen atom, an linear or branched alkyl radical having from 1 to 4 carbon atoms such as methyl and ethyl radicals , n-propyl, isopropyl, n-butyl or isobutyl, a linear or branched alkoxy radical having from 1 to 4 carbon atoms such as methoxy or ethoxy radicals, a group - CHO or a
- bromo-6 naphthol-2 those corresponding to formula (I) having a chain of benzene nuclei:
- the aromatic compounds carrying at least one hydroxyl group preferably used are: phenol, o-cresol, m-cresol, 3-ethyl phenol, tert-butyl-2 phenol, guaiacol, guetol.
- R-j represents a valence bond or an optionally substituted hydrocarbon radical containing from 1 to 40 carbon atoms.
- R- symbolizes a hydrocarbon radical, substituted or not, which can be an acyclic aliphatic radical, saturated or unsaturated, linear or branched; a carbocyclic, saturated, unsaturated or aromatic, monocyclic or polycyclic radical; a heterocyclic, saturated, unsaturated or aromatic, monocyclic or polycyclic radical.
- R1 represents an acyclic aliphatic residue, saturated or unsaturated, linear or branched. More precisely, R-
- the hydrocarbon chain can optionally be: (1) - interrupted by one of the following groups called Y: - 0 -; - CO -; - COO -; - NOT - ; - CO - N -; - S -; - SO--.
- R2 R2 in these formulas represents hydrogen or a linear or branched alkyl radical having from 1 to 4 carbon atoms, preferably a methyl or ethyl radical or a radical of type - (CH2) p - COOH in which p is a number between 1 and 5,
- represents a monocyclic or polycyclic aromatic hydrocarbon residue are also suitable for carrying out the process of the invention.
- R- preferably represents an aromatic hydrocarbon residue, and in particular a benzene residue corresponding to the general formula (III):
- - n is an integer from 0 to 4, preferably from 0 to 3,
- - R3 represents one of the following groups or functions:
- a hydrogen atom a linear or branched alkyl radical having from 1 to 4 carbon atoms,
- the compounds of formula (II) are chosen in which the radical R-
- the compounds carrying at least two carboxylic functions can correspond to the general formula (II) in which the radical R-
- R- may also represent a saturated carbocyclic residue or comprising 1 or 2 unsaturations in the ring, generally having from 3 to 7 carbon atoms, preferably 6 carbon atoms in the ring; said ring being able to be substituted by 1 to 5 radicals Rg preferably 1 to 3, R “having the meanings stated previously for the substituents of the aromatic hydrocarbon residue of general formula (III).
- R- radicals As preferred examples of R- radicals
- the compounds carrying at least two carboxylic functions can also correspond to formula (II) in which R-
- Rj represents a divalent radical constituted by a chain of two to four residues as defined above, aliphatic residue, aromatic or cycloaliphatic residue.
- catalysts suitable for the present invention mention may be made very particularly of the compounds carrying at least two following carboxylic functions: - aliphatic dicarboxylic acids such as : . oxalic acid. malonic acid. succinic acid. glutaric acid. adipic acid
- the compounds preferably used are: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid , isophthalic acid, terephthalic acid.
- Aminopolycarboxylic acids are also perfectly suitable for implementing the process of the invention.
- aminopolycarboxylic acids capable of being used in the process of the invention there may be mentioned, among others:
- EDTA ethylenediaminotetracetic acid
- DTPA diethylenetriaminopentacetic acid
- N.T.A. nitrilotriacetic acid
- ethylenediaminotetracetic acid is preferably chosen.
- the reaction is carried out in the presence of an alkali metal hydroxide which can be sodium or potassium hydroxide.
- sodium hydroxide is preferably chosen.
- concentrations and the quantities of reagents to be used the preferred conditions are defined below.
- a glyoxylic acid solution in accordance with the process of the invention, use is made of a glyoxylic acid solution.
- concentration of said solution is not critical and can vary widely, for example, between 15 and 70% by weight. Commercial solutions are used, the concentration of which is approximately
- glyoxylic acid is reacted with the excess aromatic hydroxy compound of formula (I).
- the molar ratio between the aromatic hydroxyl compound of formula (I) and the glyoxylic acid varies between 1.5 and 4.0 and is preferably chosen between 2.0 and 3.0.
- the alkali metal hydroxide solution used has a concentration generally between 10 and 50% by weight.
- concentration of the starting solution is not critical. However, as the concentration of the hydroxylated aromatic compound of formula (I) is advantageously low in the reaction medium, a dilute solution of alkali metal is used to dilute the reaction medium.
- the amount of alkali metal hydroxide introduced into the reaction medium takes account of the amount necessary to salify the hydroxyl function of the hydroxyl aromatic compound of formula (I) and of the amount necessary to salify the carboxylic function of glyoxylic acid.
- the aromatic hydroxy compound of formula (I) has salifiable functions other than the hydroxyl group, the quantity of alkali metal hydroxide necessary to salify all the salifiable functions which may be hydroxyl groups and / or carboxylic functions is therefore introduced. COOH.
- the amount of alkali metal hydroxide can vary widely and be equal to, near, or in excess of stoichiometry. Generally, the amount of alkali metal hydroxide varies between 80 and 120% of the stoichiometric amount.
- the concentration of the hydroxylated aromatic compound of formula (I) is preferably between 0.5 and 1.5 moles / liter, and more particularly around 1 mole / liter.
- the amount of catalyst used is determined so that the molar ratio between the catalyst and the hydroxylated aromatic compound of formula (I) is between 0.005 and 0.025 and preferably between 0.01 and 0.02.
- the amount of catalyst used expressed by the ratio between the number of moles of catalyst and the number of moles of glyoxylic acid is advantageously chosen between 0.5 and 2.5% preferably, between 1 and 2%.
- the preferred catalyst is oxalic acid.
- glyoxylic acid solutions may contain very small amounts of oxalic acid.
- the oxalic acid from the reaction can therefore be supplied in part by the starting solution.
- the amount of oxalic acid should be supplemented by adding oxalic acid or any other dicarboxylic acid so that the abovementioned ratios are observed.
- a solution of glyoxylic acid comprising from 0.6 to 3%, preferably from 1.2 to 2.6% by weight of oxalic acid expressed based on the weight of glyoxylic acid.
- the reaction temperature is advantageously chosen between 20 ° C and 60 ° C, and preferably between 30 ° C and 40 ° C.
- the process of the invention is carried out at atmospheric pressure but under a controlled atmosphere of inert gases, preferably nitrogen or rare gases, in particular nitrogen.
- reaction medium comprising the aromatic hydroxyl compound of formula (I), water and alkali metal hydroxide in an amount necessary to salify the hydroxyl group and other possible salifiable functions of the compound of formula (I), the glyoxylic acid solution and the catalyst are introduced and, in parallel, the alkali metal hydroxide solution used in an amount necessary to salify the COOH function.
- the reaction medium is kept under stirring and at the temperature chosen in the above-mentioned range for a variable duration ranging from 1 to 10 hours.
- Another variant embodiment of the invention consists in adding the reaction catalyst not to the aqueous glyoxylic acid solution, but simultaneously with the aromatic hydroxyl compound of formula (I).
- the optionally substituted p-hydroxymandelic acid obtained is separated in salified form according to conventional separation techniques, in particular by crystallization.
- the process of the invention applies very particularly well when an aqueous solution of glyoxylic acid is used comprising monofunctional acids such as acetic, formic and glycolic acid and in particular when there is presence of acetic acid whose concentration varies between 0.1 and
- a preferred application of the invention is the preparation of hydroxyaromatic aldehydes, by oxidation of the compounds of formula (IV) obtained according to the invention.
- the oxidation of the compounds of formula (IV) can be carried out according to the techniques described in the literature. So, we can refer to P. HEBERT
- Oxidation is generally carried out by oxygen or air under pressure, in the presence of a suitable catalyst such as, for example, chromium, cobalt, copper, vanadium or osmium derivatives.
- a suitable catalyst such as, for example, chromium, cobalt, copper, vanadium or osmium derivatives.
- the invention provides easy access to 4-hydroxy benzaldehyde and vanillin and its analogs, for example 3-ethyl, 3-isopropyl vanillin, by oxidation of p-hydroxymandelic acid and 3-methoxy-3-p-hydroxymandelic, 3-ethoxy-3-p-hydroxy-mandelic or isopropoxy-3 p-hydroxymandelic, respectively.
- Example 1 is reproduced with the difference that no oxalic acid is charged. The results obtained are as follows:
- Example 1 is reproduced but using a 50% glyoxylic acid solution containing 0.4% by weight of oxalic acid.
- the results obtained are as follows:
- example 1 is reproduced, but other types of dicarboxylic acids are used, such as malonic acid, succinic acid as well as E.D.T.A.
- the glyoxylic acid solution used contains oxalic acid at 0.09%, lower carboxylic acids such as acetic acid at 1%, formic and glycolic acid in a respective amount less than 0.3%.
- dicarboxylic acid expressed in mole% relative to glyoxylic acid.
- the amount of oxalic acid used in the glyoxylic acid solution is increased.
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Abstract
Description
Claims
Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE69915061T DE69915061T2 (de) | 1998-06-16 | 1999-06-16 | Verfahren zur herstellung von gegebenenfalls substituierten p-hydroxymandelsäuren |
KR1020007014223A KR20010072614A (ko) | 1998-06-16 | 1999-06-16 | 임의 치환된 p-히드록시만델 화합물의 제조방법 |
AU41508/99A AU4150899A (en) | 1998-06-16 | 1999-06-16 | Method for preparing p-hydroxymandelic compounds optionally substituted |
US09/719,839 US6753441B1 (en) | 1998-06-16 | 1999-06-16 | Method for preparing p-hydroxymandelic compounds optionally substituted |
CA002334848A CA2334848A1 (fr) | 1998-06-16 | 1999-06-16 | Procede de preparation de composes p-hydroxymandeliques eventuellement substitues |
EP99925110A EP1087924B1 (fr) | 1998-06-16 | 1999-06-16 | Procede de preparation de composes p-hydroxymandeliques eventuellement substitues |
JP2000554680A JP2002518358A (ja) | 1998-06-16 | 1999-06-16 | 任意に置換されたp−ヒドロキシマンデル酸化合物の製造方法 |
BR9911247-7A BR9911247A (pt) | 1998-06-16 | 1999-06-16 | Processo para preparação de compostos p-hidroximandélicos opcionalmente substituìdos e derivados e usos de compostos p-hidroximandélicos e do ácido p-hidroximandélico e dos ácidos metóxi-3 p-hidroximandélico, etóxi-3 p-hidroximandélico ou isopropóxi-3 p-hidroximandélico |
AT99925110T ATE260234T1 (de) | 1998-06-16 | 1999-06-16 | Verfahren zur herstellung von gegebenenfalls substituierten p-hydroxymandelsäuren |
NO20006443A NO20006443L (no) | 1998-06-16 | 2000-12-15 | Fremgangsmåte for fremstilling av eventuelt substituerte p- hydroksymandelforbindelser |
HK02101745.4A HK1040390B (zh) | 1998-06-16 | 2002-03-07 | 可被取代的對羥基扁桃酸類化合物的製備方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR98/07586 | 1998-06-16 | ||
FR9807586A FR2779718B1 (fr) | 1998-06-16 | 1998-06-16 | Procede de preparation de composes p-hydroxymandeliques eventuellement substitues et derives |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1999065853A1 true WO1999065853A1 (fr) | 1999-12-23 |
Family
ID=9527456
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR1999/001442 WO1999065853A1 (fr) | 1998-06-16 | 1999-06-16 | Procede de preparation de composes p-hydroxymandeliques eventuellement substitues |
Country Status (17)
Country | Link |
---|---|
US (1) | US6753441B1 (fr) |
EP (1) | EP1087924B1 (fr) |
JP (1) | JP2002518358A (fr) |
KR (1) | KR20010072614A (fr) |
CN (1) | CN1217907C (fr) |
AT (1) | ATE260234T1 (fr) |
AU (1) | AU4150899A (fr) |
BR (1) | BR9911247A (fr) |
CA (1) | CA2334848A1 (fr) |
DE (1) | DE69915061T2 (fr) |
ES (1) | ES2217757T3 (fr) |
FR (1) | FR2779718B1 (fr) |
HK (1) | HK1040390B (fr) |
NO (1) | NO20006443L (fr) |
RU (1) | RU2232746C2 (fr) |
WO (1) | WO1999065853A1 (fr) |
ZA (1) | ZA200007016B (fr) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101811947A (zh) * | 2010-03-12 | 2010-08-25 | 重庆欣欣向荣精细化工有限公司 | 乙基香兰素生产工艺中减少邻位乙基香兰素生成的方法 |
WO2011039331A1 (fr) | 2009-10-02 | 2011-04-07 | Rhodia Operations | Procede de separation de composes phenoliques sous forme salifiee |
US20110230674A1 (en) * | 2008-05-22 | 2011-09-22 | Rhodia Operations | Method of separating phenolic compounds in salified form |
WO2014016146A1 (fr) | 2012-07-26 | 2014-01-30 | Rhodia Operations | Procede de preparation d'alkoxyphenol et d'alkoxyhydroxybenzaldehyde |
WO2014016145A1 (fr) | 2012-07-26 | 2014-01-30 | Rhodia Operations | Procédé de préparation d'alkoxyhydroxybenzaldéhyde sensiblement exempte d'alkyl-alkoxyhydroxybenzaldéhyde |
EP2796441A2 (fr) | 2014-05-26 | 2014-10-29 | Rhodia Opérations | Procédé de préparation de composés p-hydroxymandéliques en réacteurs agités |
WO2015091328A1 (fr) | 2013-12-18 | 2015-06-25 | Rhodia Operations | Procede de separation de composes mandeliques sous forme salifiee et son utilisation pour la preparation d'aldehyde aromatique |
US9650322B2 (en) | 2012-07-26 | 2017-05-16 | Rhodia Operations | Method for producing alkoxyhydroxybenzaldehyde |
WO2019020773A1 (fr) | 2017-07-28 | 2019-01-31 | Rhodia Operations | Nouvelle vanilline et/ou éthylvanilline, son procédé de préparation et son utilisation |
FR3116819A1 (fr) | 2020-12-01 | 2022-06-03 | Rhodia Operations | Procédé de préparation de frambinone |
Families Citing this family (5)
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FR2917085B1 (fr) * | 2007-06-06 | 2009-07-17 | Rhodia Recherches & Tech | Procede de preparation d'un aldehyde hydroxyaromatique. |
CN101417942B (zh) * | 2007-10-26 | 2011-09-21 | 宝山钢铁股份有限公司 | 一种制备对羟基扁桃酸的方法 |
FR2925047B1 (fr) * | 2007-12-18 | 2010-01-01 | Rhodia Operations | Procede de preparation de composes p-hydroxymandeliques eventuellement substitues et derives. |
US11484052B2 (en) | 2017-07-28 | 2022-11-01 | Rhodia Operations | Vanillin and/or ethylvanillin, process for their preparations and use thereof |
CN109956858B (zh) * | 2017-12-26 | 2022-02-15 | 万华化学集团股份有限公司 | 一种制备3-甲氧基-4-羟基扁桃酸的方法 |
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US4165341A (en) * | 1977-02-04 | 1979-08-21 | Ube Industries, Ltd. | Process for preparing protocatechualdehyde and its derivatives |
FR2462415A1 (fr) * | 1979-07-25 | 1981-02-13 | Hoechst France | Procede de preparation d'acides hydroxyarylglycoliques racemiques et produits nouveaux en resultant |
NL9202248A (nl) * | 1992-12-23 | 1994-07-18 | Univ Delft Tech | Werkwijze voor het scheiden van de ortho- en para-isomeer van hydroxyamandelzuur of een zout daarvan, de volgens deze werkwijze verkregen ortho- en para-isomeer van hydroxyamandelzuur, alsmede de toepassing van de ortho-isomeer in de bereiding van EDDHA. |
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- 1998-06-16 FR FR9807586A patent/FR2779718B1/fr not_active Expired - Fee Related
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- 1999-06-16 RU RU2001101531/04A patent/RU2232746C2/ru not_active IP Right Cessation
- 1999-06-16 EP EP99925110A patent/EP1087924B1/fr not_active Expired - Lifetime
- 1999-06-16 BR BR9911247-7A patent/BR9911247A/pt not_active Application Discontinuation
- 1999-06-16 CN CN998087335A patent/CN1217907C/zh not_active Expired - Fee Related
- 1999-06-16 DE DE69915061T patent/DE69915061T2/de not_active Expired - Fee Related
- 1999-06-16 JP JP2000554680A patent/JP2002518358A/ja not_active Withdrawn
- 1999-06-16 AU AU41508/99A patent/AU4150899A/en not_active Abandoned
- 1999-06-16 ES ES99925110T patent/ES2217757T3/es not_active Expired - Lifetime
- 1999-06-16 WO PCT/FR1999/001442 patent/WO1999065853A1/fr not_active Application Discontinuation
- 1999-06-16 AT AT99925110T patent/ATE260234T1/de not_active IP Right Cessation
- 1999-06-16 US US09/719,839 patent/US6753441B1/en not_active Expired - Fee Related
- 1999-06-16 KR KR1020007014223A patent/KR20010072614A/ko not_active Application Discontinuation
- 1999-06-16 CA CA002334848A patent/CA2334848A1/fr not_active Abandoned
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2000
- 2000-11-29 ZA ZA200007016A patent/ZA200007016B/xx unknown
- 2000-12-15 NO NO20006443A patent/NO20006443L/no not_active Application Discontinuation
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2002
- 2002-03-07 HK HK02101745.4A patent/HK1040390B/zh not_active IP Right Cessation
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US4401830A (en) * | 1980-01-11 | 1983-08-30 | Ube Industries, Ltd. | Process for preparation of 3-alkoxy-4-hydroxyphenylacetic acid |
US4337355A (en) * | 1980-06-20 | 1982-06-29 | Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha | Process for preparing 4-hydroxyphenylacetic acid |
US5248816A (en) * | 1991-10-11 | 1993-09-28 | Imperial Chemical Industries Plc | Process for making 2-hydroxymandelic acid and 2-hydroxybenzaldehydes |
EP0578550A1 (fr) * | 1992-07-10 | 1994-01-12 | Rhone-Poulenc Chimie | Procédé de para-hydroxyalkylation de composés aromatiques hydroxylés |
Cited By (22)
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US9006496B2 (en) | 2008-05-22 | 2015-04-14 | Rhodia Operations | Method of separating phenolic compounds in salified form |
US20110230674A1 (en) * | 2008-05-22 | 2011-09-22 | Rhodia Operations | Method of separating phenolic compounds in salified form |
WO2011039331A1 (fr) | 2009-10-02 | 2011-04-07 | Rhodia Operations | Procede de separation de composes phenoliques sous forme salifiee |
US20120264982A1 (en) * | 2009-10-02 | 2012-10-18 | Rhodia Operations | Method for separating salified phenolic compounds |
US9403745B2 (en) | 2009-10-02 | 2016-08-02 | Rhodia Operations | Method for separating salified phenolic compounds |
US9079842B2 (en) * | 2009-10-02 | 2015-07-14 | Rhodia Operations | Method for separating salified phenolic compounds |
CN101811947A (zh) * | 2010-03-12 | 2010-08-25 | 重庆欣欣向荣精细化工有限公司 | 乙基香兰素生产工艺中减少邻位乙基香兰素生成的方法 |
US9334216B2 (en) | 2012-07-26 | 2016-05-10 | Rhodia Operations | Method for producing alkoxyphenol and alkoxy-hydroxybenzaldehyde |
US9284247B2 (en) | 2012-07-26 | 2016-03-15 | Rhodia Operations | Method for producing alkoxy-hydroxybenzaldehyde that is substantially free of alkyl-alkoxy-hydroxybenzaldehyde |
EP2799421A1 (fr) | 2012-07-26 | 2014-11-05 | Rhodia Operations | Procede de preparation d'alkoxyphenol et d'alkoxyhydroxybenzaldehyde |
US9650322B2 (en) | 2012-07-26 | 2017-05-16 | Rhodia Operations | Method for producing alkoxyhydroxybenzaldehyde |
WO2014016146A1 (fr) | 2012-07-26 | 2014-01-30 | Rhodia Operations | Procede de preparation d'alkoxyphenol et d'alkoxyhydroxybenzaldehyde |
WO2014016145A1 (fr) | 2012-07-26 | 2014-01-30 | Rhodia Operations | Procédé de préparation d'alkoxyhydroxybenzaldéhyde sensiblement exempte d'alkyl-alkoxyhydroxybenzaldéhyde |
US9567283B2 (en) | 2013-12-18 | 2017-02-14 | Rhodia Operations | Method for separating mandelic compounds in salified form and use of same for preparing aromatic aldehyde |
WO2015091328A1 (fr) | 2013-12-18 | 2015-06-25 | Rhodia Operations | Procede de separation de composes mandeliques sous forme salifiee et son utilisation pour la preparation d'aldehyde aromatique |
WO2015181023A1 (fr) | 2014-05-26 | 2015-12-03 | Rhodia Operations | Procede de preparation de composes p-hydroxymandeliques en reacteurs agites |
FR3021314A1 (fr) * | 2014-05-26 | 2015-11-27 | Rhodia Operations | Procede de preparation de composes p-hydroxymandeliques en reacteurs agites |
EP2796441A2 (fr) | 2014-05-26 | 2014-10-29 | Rhodia Opérations | Procédé de préparation de composés p-hydroxymandéliques en réacteurs agités |
EP2796441A3 (fr) * | 2014-05-26 | 2015-02-25 | Rhodia Opérations | Procédé de préparation de composés p-hydroxymandéliques en réacteurs agités |
WO2019020773A1 (fr) | 2017-07-28 | 2019-01-31 | Rhodia Operations | Nouvelle vanilline et/ou éthylvanilline, son procédé de préparation et son utilisation |
FR3116819A1 (fr) | 2020-12-01 | 2022-06-03 | Rhodia Operations | Procédé de préparation de frambinone |
WO2022117670A1 (fr) | 2020-12-01 | 2022-06-09 | Rhodia Operations | Procédé de préparation de frambinone |
Also Published As
Publication number | Publication date |
---|---|
KR20010072614A (ko) | 2001-07-31 |
ZA200007016B (en) | 2001-06-14 |
CN1217907C (zh) | 2005-09-07 |
US6753441B1 (en) | 2004-06-22 |
NO20006443L (no) | 2001-02-16 |
HK1040390B (zh) | 2006-04-28 |
JP2002518358A (ja) | 2002-06-25 |
HK1040390A1 (en) | 2002-06-07 |
FR2779718B1 (fr) | 2000-12-29 |
NO20006443D0 (no) | 2000-12-15 |
DE69915061T2 (de) | 2005-02-03 |
DE69915061D1 (de) | 2004-04-01 |
ES2217757T3 (es) | 2004-11-01 |
RU2232746C2 (ru) | 2004-07-20 |
EP1087924B1 (fr) | 2004-02-25 |
CN1320111A (zh) | 2001-10-31 |
EP1087924A1 (fr) | 2001-04-04 |
CA2334848A1 (fr) | 1999-12-23 |
ATE260234T1 (de) | 2004-03-15 |
FR2779718A1 (fr) | 1999-12-17 |
AU4150899A (en) | 2000-01-05 |
BR9911247A (pt) | 2001-10-09 |
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