EP3969434A1 - Verfahren zur reinigung von eugenol und neuartige zusammensetzungen mit eugenol - Google Patents
Verfahren zur reinigung von eugenol und neuartige zusammensetzungen mit eugenolInfo
- Publication number
- EP3969434A1 EP3969434A1 EP20724855.0A EP20724855A EP3969434A1 EP 3969434 A1 EP3969434 A1 EP 3969434A1 EP 20724855 A EP20724855 A EP 20724855A EP 3969434 A1 EP3969434 A1 EP 3969434A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- eugenol
- weight
- equal
- stabilizing compound
- compound
- 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.)
- Pending
Links
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 title claims abstract description 256
- 239000005770 Eugenol Substances 0.000 title claims abstract description 130
- 229960002217 eugenol Drugs 0.000 title claims abstract description 130
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 title claims abstract description 128
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 239000000203 mixture Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000000746 purification Methods 0.000 title claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 98
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 65
- LREHGXOCZVBABG-UHFFFAOYSA-N 2-methoxy-6-prop-2-enylphenol Chemical compound COC1=CC=CC(CC=C)=C1O LREHGXOCZVBABG-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000004821 distillation Methods 0.000 claims abstract description 28
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 claims description 31
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 28
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 claims description 27
- 239000004250 tert-Butylhydroquinone Substances 0.000 claims description 27
- 235000019281 tert-butylhydroquinone Nutrition 0.000 claims description 27
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 24
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 claims description 18
- 229930003427 Vitamin E Natural products 0.000 claims description 15
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 claims description 15
- 239000011709 vitamin E Substances 0.000 claims description 15
- 235000019165 vitamin E Nutrition 0.000 claims description 15
- 229940046009 vitamin E Drugs 0.000 claims description 15
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 14
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 13
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 claims description 12
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Chemical class CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 11
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 108010024636 Glutathione Proteins 0.000 claims description 9
- 229960003180 glutathione Drugs 0.000 claims description 9
- 235000003969 glutathione Nutrition 0.000 claims description 9
- 150000002989 phenols Chemical class 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 8
- 235000010378 sodium ascorbate Nutrition 0.000 claims description 8
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims description 8
- 229960005055 sodium ascorbate Drugs 0.000 claims description 8
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 7
- 229920001174 Diethylhydroxylamine Polymers 0.000 claims description 7
- 239000004260 Potassium ascorbate Substances 0.000 claims description 7
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 claims description 7
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 7
- 235000019275 potassium ascorbate Nutrition 0.000 claims description 7
- 229940017794 potassium ascorbate Drugs 0.000 claims description 7
- CONVKSGEGAVTMB-RXSVEWSESA-M potassium-L-ascorbate Chemical compound [K+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] CONVKSGEGAVTMB-RXSVEWSESA-M 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- IXPUJMULXNNEHS-UHFFFAOYSA-L copper;n,n-dibutylcarbamodithioate Chemical compound [Cu+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC IXPUJMULXNNEHS-UHFFFAOYSA-L 0.000 claims description 6
- 235000010288 sodium nitrite Nutrition 0.000 claims description 6
- 229960000819 sodium nitrite Drugs 0.000 claims description 6
- 229940066767 systemic antihistamines phenothiazine derivative Drugs 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000000018 nitroso group Chemical group N(=O)* 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000001484 phenothiazinyl group Chemical class C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 claims 3
- 238000000926 separation method Methods 0.000 abstract description 5
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 42
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 28
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 25
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 21
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical class C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 19
- 229950000688 phenothiazine Drugs 0.000 description 19
- 229960001867 guaiacol Drugs 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 description 8
- -1 methoxy, ethoxy, propoxy, iso-propoxy Chemical group 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000000113 differential scanning calorimetry Methods 0.000 description 7
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000005937 allylation reaction Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- OWZPCEFYPSAJFR-UHFFFAOYSA-N 2-(butan-2-yl)-4,6-dinitrophenol Chemical compound CCC(C)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O OWZPCEFYPSAJFR-UHFFFAOYSA-N 0.000 description 4
- KDQPMQNHVQVVMR-UHFFFAOYSA-N 2-methyl-4-nitrophenol Chemical compound CC1=CC([N+]([O-])=O)=CC=C1O KDQPMQNHVQVVMR-UHFFFAOYSA-N 0.000 description 4
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical compound CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 description 4
- JSTCPNFNKICNNO-UHFFFAOYSA-N 4-nitrosophenol Chemical compound OC1=CC=C(N=O)C=C1 JSTCPNFNKICNNO-UHFFFAOYSA-N 0.000 description 4
- BJIOGJUNALELMI-ONEGZZNKSA-N Isoeugenol Natural products COC1=CC(\C=C\C)=CC=C1O BJIOGJUNALELMI-ONEGZZNKSA-N 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- BJIOGJUNALELMI-ARJAWSKDSA-N cis-isoeugenol Chemical compound COC1=CC(\C=C/C)=CC=C1O BJIOGJUNALELMI-ARJAWSKDSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 150000002990 phenothiazines Chemical class 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- BJIOGJUNALELMI-UHFFFAOYSA-N trans-isoeugenol Natural products COC1=CC(C=CC)=CC=C1O BJIOGJUNALELMI-UHFFFAOYSA-N 0.000 description 4
- WGVKWNUPNGFDFJ-DQCZWYHMSA-N β-tocopherol Chemical compound OC1=CC(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C WGVKWNUPNGFDFJ-DQCZWYHMSA-N 0.000 description 4
- LPQTVHUEAIDBBY-UHFFFAOYSA-N 2,3-ditert-butyl-6-methoxyphenol Chemical compound COC1=CC=C(C(C)(C)C)C(C(C)(C)C)=C1O LPQTVHUEAIDBBY-UHFFFAOYSA-N 0.000 description 3
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 3
- 238000010934 O-alkylation reaction Methods 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical class OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000202 analgesic effect Effects 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 235000006708 antioxidants Nutrition 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001311 chemical methods and process Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 3
- XUXUHDYTLNCYQQ-UHFFFAOYSA-N 4-amino-TEMPO Chemical group CC1(C)CC(N)CC(C)(C)N1[O] XUXUHDYTLNCYQQ-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical compound NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229940066595 beta tocopherol Drugs 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- UBQKCCHYAOITMY-UHFFFAOYSA-N pyridin-2-ol Chemical compound OC1=CC=CC=N1 UBQKCCHYAOITMY-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 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
- 239000011732 tocopherol Substances 0.000 description 2
- 229960001295 tocopherol Drugs 0.000 description 2
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 235000007680 β-tocopherol Nutrition 0.000 description 2
- 239000011590 β-tocopherol Substances 0.000 description 2
- OILXMJHPFNGGTO-UHFFFAOYSA-N (22E)-(24xi)-24-methylcholesta-5,22-dien-3beta-ol Natural products C1C=C2CC(O)CCC2(C)C2C1C1CCC(C(C)C=CC(C)C(C)C)C1(C)CC2 OILXMJHPFNGGTO-UHFFFAOYSA-N 0.000 description 1
- RQOCXCFLRBRBCS-UHFFFAOYSA-N (22E)-cholesta-5,7,22-trien-3beta-ol Natural products C1C(O)CCC2(C)C(CCC3(C(C(C)C=CCC(C)C)CCC33)C)C3=CC=C21 RQOCXCFLRBRBCS-UHFFFAOYSA-N 0.000 description 1
- WBHAUHHMPXBZCQ-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound COC1=CC=CC(C)=C1O WBHAUHHMPXBZCQ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- WSGDRFHJFJRSFY-UHFFFAOYSA-N 4-oxo-TEMPO Chemical compound CC1(C)CC(=O)CC(C)(C)N1[O] WSGDRFHJFJRSFY-UHFFFAOYSA-N 0.000 description 1
- HROZLGRKFUCIJJ-UHFFFAOYSA-N 6-methyleugenol Chemical compound COC1=CC(CC=C)=CC(C)=C1O HROZLGRKFUCIJJ-UHFFFAOYSA-N 0.000 description 1
- OQMZNAMGEHIHNN-UHFFFAOYSA-N 7-Dehydrostigmasterol Natural products C1C(O)CCC2(C)C(CCC3(C(C(C)C=CC(CC)C(C)C)CCC33)C)C3=CC=C21 OQMZNAMGEHIHNN-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- DNVPQKQSNYMLRS-NXVQYWJNSA-N Ergosterol Natural products CC(C)[C@@H](C)C=C[C@H](C)[C@H]1CC[C@H]2C3=CC=C4C[C@@H](O)CC[C@]4(C)[C@@H]3CC[C@]12C DNVPQKQSNYMLRS-NXVQYWJNSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-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
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- QYSXJUFSXHHAJI-XFEUOLMDSA-N Vitamin D3 Natural products C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)CCCC(C)C)=C/C=C1\C[C@@H](O)CCC1=C QYSXJUFSXHHAJI-XFEUOLMDSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229940087168 alpha tocopherol Drugs 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229940072107 ascorbate Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000010634 clove oil Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- DNVPQKQSNYMLRS-SOWFXMKYSA-N ergosterol Chemical compound C1[C@@H](O)CC[C@]2(C)[C@H](CC[C@]3([C@H]([C@H](C)/C=C/[C@@H](C)C(C)C)CC[C@H]33)C)C3=CC=C21 DNVPQKQSNYMLRS-SOWFXMKYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 229960003966 nicotinamide Drugs 0.000 description 1
- 235000005152 nicotinamide Nutrition 0.000 description 1
- 239000011570 nicotinamide Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229960000984 tocofersolan Drugs 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
- 235000010384 tocopherol Nutrition 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- QYSXJUFSXHHAJI-YRZJJWOYSA-N vitamin D3 Chemical compound C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)CCCC(C)C)=C\C=C1\C[C@@H](O)CCC1=C QYSXJUFSXHHAJI-YRZJJWOYSA-N 0.000 description 1
- 235000005282 vitamin D3 Nutrition 0.000 description 1
- 239000011647 vitamin D3 Substances 0.000 description 1
- 229940021056 vitamin d3 Drugs 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 235000004835 α-tocopherol Nutrition 0.000 description 1
- 239000002076 α-tocopherol Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
- C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/46—Use of additives, e.g. for stabilisation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Definitions
- the present invention relates to a process for the purification of eugenol and to novel compositions comprising Teugenol.
- Document CN 105294409 indicates a purification process in which eugenol is purified using n-octane and K 2 CO 3 , the mixture is filtered, then washing with water of the K 2 CO 3 is carried out and finally l purified eugenol is distilled from the aqueous phase.
- the present invention relates to the efficient and selective manufacture of eugenol, in particular a process allowing the separation of eugenol and orthoeugenol, on an industrial scale, efficiently and under good safety conditions.
- a first object of the present invention relates to a novel process for the purification of eugenol in which a crude eugenol is distilled in the presence of at least one stabilizing compound.
- the present invention also relates to a process for separating G eugenol and orthoeugenol by distillation in the presence of at least one stabilizing compound.
- phenol derivative represents a compound comprising a unit corresponding to formula (III):
- R represents a hydroxyl, a linear or branched alkyl, preferably comprising between 1 and 6 carbon atoms, alkenyl, an alkoxy group, preferably comprising between 1 and 6 carbon atoms, a nitro group, or a nitroso group
- R2 represents an alkyl linear or branched, preferably comprising between 1 and 6 carbon atoms and n is between 0 and 5, preferably n is equal to 0, 1, 2 or 3.
- the group R is chosen from the group consisting of hydroxyl , methyl, ethyl, propyl, n-butyl, t-butyl, methoxy, ethoxy, propoxy, iso-propoxy, nitro, nitroso.
- the group R2 is chosen from methyl, ethyl, propyl, n-butyl, t-butyl.
- a phenol derivative can be chosen from compounds of the tocopherol family, in particular ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, d-tocopherol.
- phenothiazine derivative refers to compounds comprising the unit according to formula (V):
- TEMPO (2,2,6,6-tetramethylpiperidin-l-yl) oxy
- TEMPO-OH (4-hydroxy-2,2,6,6-tetramethylpiperidin-l-yl) oxy
- au (4-Oxo-2,2,6,6-tetramethyl-1 -piperidin-1-yl) oxy
- 4-Amino-2,2,6, 6-tetramethylpiperidine-1-oxyl (4-amino-TEMPO)
- Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (Bishydroxy TEMPO sebacate).
- stabilizer refers to a compound capable of maintaining the qualities of a product without affecting said product, such as coloring, chemical or thermal stability, in particular during manufacture, storage or. handling of the product.
- the crude eugenol according to the present invention may contain impurities, in particular linked to the process for synthesizing T eugenol, such as o-eugenol, or product of O-alkylation of guaiacol or of G eugenol, the impurities may also from the starting compounds used in the reaction.
- the content by weight of each impurity present in the composition relative to the weight of the composition is less than the content of eugenol in the composition.
- purified eugenol refers to a composition comprising essentially of G eugenol, in particular comprising at least 80% of eugenol, preferably at least 90% by weight of eugenol, even more preferably. at least 95% by weight and even more preferably at least 99% by weight relative to the weight of the composition.
- eugenol is obtained from guaiacol and allyl halide, preferably allyl chloride as described in document FR 2302991.
- the alkylation reaction is carried out. in the presence of an aqueous solution of an alkali metal, or of an alkaline earth metal hydroxide, such as NaOH or KOH.
- the reaction can be carried out in the presence of a catalyst, in particular a copper-based catalyst such as CuCl, CuCl 2 .2I3 ⁇ 4C), Cu (N03) 2, Cu (OAc) 2 .2I3 ⁇ 4C).
- the reaction can also be carried out in the presence of a composite catalyst as described in patent application CN 105294409.
- the amount of catalyst is greater than or equal to 0.01% by weight, preferably greater than or equal to 0.02% by weight, more preferably greater than or equal to 0.05% by weight, and very preferably greater than or equal to 0.1% by weight relative to the amount of guaiacol.
- the amount of catalyst is less than or equal to 10% by weight, preferably less than or equal to 5% by weight, more preferably less than or equal to 2% by weight, and very preferably greater than or equal to 1% by weight relative to to the amount of guaiacol.
- the reaction is generally carried out in the presence of an ammonium or ammonia salt as described in document FR 2302991.
- the ammonia can form with the catalyst a copper-amine type complex.
- a first object of the present invention relates to a process for purifying a crude eugenol by distillation in the presence of at least one stabilizing compound.
- the present invention relates to a process for purifying a crude eugenol by distillation in the presence of at least one stabilizing compound and / or an auxiliary compound.
- the object of the present invention is in particular to:
- At least one stabilizing compound is chosen from the group consisting of phenol derivatives, phenothiazine derivatives, TEMPO derivatives, CB (copper dibutyl dithiocarbamate), para-benzoquinone, para-phenylenediamine, diethylhydroxylamine, manganese (II) acetate, sodium nitrite, sodium or potassium ascorbate or glutathione.
- the at least one stabilizing compound is selected from the group consisting above further comprising bis (2, 2,6,6-tetramethyl-4-piperidyl) sebacate.
- the at least one stabilizing compound is chosen from a group according to the first aspect or according to the second aspect or according to the third aspect or a group according to the fourth aspect, said group further comprising bis (2,2 , 6,6-tetramethyl-4-piperidyl) sebacate.
- At least one stabilizing compound is chosen from the group consisting of vitamin E, butyl-hydroxyanisole (BHA), tert-butylcatechol (TBC), bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate , sodium ascorbate, tert-butylhydroquinone (TBHQ), para-methoxyphenol (PMP) or glutathione.
- the purification process is carried out in the presence of a stabilizer.
- the inventors have surprisingly discovered that the addition of at least one stabilizing compound during the distillation of crude eugenol makes it possible to move the temperature zone towards which the thermal decomposition takes place. initiates to prevent the distillation process from being unstable or even explosive.
- the method according to the present invention can be operated under appropriate safety conditions.
- the purification process is carried out in the presence of at least one stabilizing compound chosen from the group consisting of phenol derivatives, phenothiazine derivatives, TEMPO, CB (copper dibutyl dithiocarbamate) derivatives, para-benzoquinone, para-phenylenediamine, diethylhydroxylamine, manganese (II) acetate, sodium nitrite, sodium or potassium ascorbate or glutathione and optionally in the presence of at least one auxiliary compound chosen from the group consisting of vitamin E, butyl-hydroxyanisole (BHA), dibutylhydroxytoluene (BHT), tert-butylhydroquinone (TBHQ).
- at least one stabilizing compound chosen from the group consisting of phenol derivatives, phenothiazine derivatives, TEMPO, CB (copper dibutyl dithiocarbamate) derivatives, para-benzoquinone, para-phenylenediamine, diethyl
- the at least one stabilizing compound is chosen from the above group further comprising bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate.
- the total amount of stabilizing compound is greater than or equal to 50 ppm, preferably greater than or equal to 100 ppm, more preferably greater than or equal to 500 ppm, and more preferably greater than or equal to 1000 ppm relative to the amount of eugenol.
- the at least one stabilizing compound is added to the distillation boiler.
- the at least one stabilizing compound is chosen from stabilizing compounds having a boiling point higher than that of eugenol, preferably the boiling point of the stabilizing compound is greater than or equal to T eu + 1 ° C, preferably greater than or equal to T eu + 5 ° C, more preferably greater than or equal to T eu + 10 ° C.
- the at least one stabilizing compound is added to the distillation column.
- the at least one stabilizing compound can be chosen from stabilizing compounds having a boiling point higher than that of eugenol.
- the at least one stabilizing compound can be chosen from stabilizing compounds having a boiling point less than or equal to that of G eugenol, preferably the boiling point of the stabilizing compound is less than or equal to T eu ⁇ 1 ° C. , preferably less than or equal to T eu -5 ° C, more preferably less than or equal to T eu -10 ° C.
- the distillation is carried out using TBC and PMP.
- the TBC is added to the still boiler and the PMP to the still column.
- TBC and PMP are added to the still boiler.
- the distillation is carried out at a temperature greater than or equal to 90 ° C, preferably greater than or equal to 100 ° C and very preferably greater than or equal to 110 ° C, and even more preferably greater than or equal to 120 ° C.
- the distillation is carried out at a temperature less than or equal to 200 ° C, preferably less than or equal to 190 ° C and very preferably less than or equal to 180 ° C, and even more preferably less than or equal to 150 ° vs.
- the distillation also makes it possible to separate the excess of guaiacol, the products of O-alkylation of eugenol and / or of guaiacol and of ortho-eugenol.
- the guaiacol used in the preparation of eugenol can also contain certain impurities such as veratrole or 6-methyl guaiacol, the reaction mixture obtained at the end of the allylation reaction can also contain allylation products of said impurities, in particular allyl-veratrole or 4-allyl-6-methylguaiacol.
- the reaction mixture obtained at the end of the allylation reaction can also contain isomerization products of the allyl group, in particular isoeugenol or meta-eugenol (also known under the name of 2-methoxy-5 - (prop-2-en-1-yl) phenol).
- the eugenol obtained at the end of the distillation contains an amount greater than or equal to 0.01% by weight, preferably greater than or equal to 0.05% by weight, and even more preferably greater than or equal to 0.1% by weight of ortho-eugenol relative to the total weight of the composition
- the process according to the present invention allows in particular the separation of G eugenol and guaiacol.
- the process according to the present invention allows the preparation of eugenol having satisfactory organoleptic properties.
- eugenol obtained according to the process of the invention exhibits organoleptic properties similar to those of eugenol obtained by extraction of a natural product.
- the present invention relates to a process for the preparation of eugenol which comprises a purification process as defined above.
- the process for preparing eugenol generally includes a step of preparing a crude eugenol. This step can in particular be carried out as described in document LR 2302991, in particular by allylation of guaiacol.
- the process for preparing eugenol comprises a second step in which the crude eugenol is purified by a method of purification by distillation in the presence of at least one stabilizing compound.
- the present invention relates to the use of a stabilizer compound to stabilize a eugenol purification process.
- the present invention relates to a composition
- a composition comprising eugenol and between 0.1 and 10,000 ppm of at least one stabilizing compound or at least one stabilizing compound and at least one auxiliary compound, in which the stabilizing compound is selected from the group consisting of phenol derivatives, phenothiazine derivatives, TEMPO, CB (copper dibutyl dithiocarbamate), para-benzoquinone, para-phenylenediamine, diethylhydroxylamine, manganese acetate (II ), sodium nitrite, sodium or potassium ascorbate or glutathione and the auxiliary compound is selected from the group consisting of vitamin E, butyl-hydroxyanisole (BHA), dibutylhydroxytoluene (BHT), tert-butylhydroquinone (TBHQ).
- the above composition further comprises bis (2, 2,6,6-tetramethyl-4-piperidyl) sebacate.
- the total amount of stabilizing compound in the composition is greater than or equal to 0.1 ppm, preferably greater than or equal to 1 ppm, more preferably greater than or equal to 10 ppm, and more preferably greater than or equal to 100 ppm relative to the amount of eugenol.
- the total amount of stabilizing compound is less than or equal to 10,000 ppm, preferably less than or equal to 5000 ppm, more preferably less than or equal to 2000 ppm, more preferably less than or equal to 1000 ppm, and even more preferably less than or equal to 500 ppm relative to the amount of eugenol.
- the total amount of auxiliary compound is greater than or equal to 0 ppm, preferably greater than or equal to 0.1 ppm, more preferably greater than or equal to 1 ppm, and more preferably greater than or equal to 10 ppm relative to to the amount of eugenol.
- the total amount of auxiliary compound is less than or equal to 5000 ppm, preferably less than or equal to 2500 ppm, more preferably less than or equal to 2000 ppm, and more preferably less than or equal to 1000 ppm relative to the amount of eugenol.
- At least one stabilizing compound is a compound of formula (IV) or phenothiazine (PTZ) in particular chosen from the group as constituted above additionally comprising bis (2,2,6,6-tetramethyl- 4-piperidyl) sebacate.
- the composition according to the invention comprises a stabilizing compound. According to another particular aspect, the composition according to the invention comprises two stabilizing compounds.
- the composition according to the invention comprises at least one stabilizing compound chosen from the group consisting of T hydroquinone (HQ), para-methoxyphenol (PMP), tert-butylcatechol (TBC), phenothiazine (PTZ ) and at least one auxiliary compound, selected from the group consisting of vitamin E, butyl-hydroxyanisole (BHA), dibutylhydroxytoluene (BHT), tert-butylhydroquinone (TBHQ).
- HQ T hydroquinone
- PMP para-methoxyphenol
- TBC tert-butylcatechol
- PTZ phenothiazine
- at least one auxiliary compound selected from the group consisting of vitamin E, butyl-hydroxyanisole (BHA), dibutylhydroxytoluene (BHT), tert-butylhydroquinone (TBHQ).
- the composition according to the invention comprises at least one stabilizing compound chosen from the group consisting of 2,4-dimethyl-6-tert-butylphenol (Topanol A), 2,4-dinitro-6-sec- butylphenol, 2-methyl-4,6-dinitrophenol, para-nitrosophenol, 2-methyl-4-nitrophenol and at least one auxiliary compound, selected from the group consisting of vitamin E, butyl-hydroxyanisole (BHA), dibutylhydroxytoluene (BHT) , tert-butylhydroquinone (TBHQ).
- BHA butyl-hydroxyanisole
- BHT dibutylhydroxytoluene
- TBHQ tert-butylhydroquinone
- the composition according to the present invention comprises at least 90% by weight of eugenol, preferably at least 95% by weight of eugenol, more preferably at least 99% by weight, even more preferably at least 99.5 % and even more preferably at least 99.95% by weight of eugenol relative to the total weight of the composition.
- the content of ortho-eugenol in the composition is less than or equal to 10% by weight, preferably less than or equal to 8% by weight, very preferably less than or equal to 5% by weight and even more preferably less than or equal to 1% by weight relative to the weight of the composition.
- the iso-eugenol content in the composition is less than or equal to 5% by weight, preferably less than or equal to 2% by weight, very preferably less than or equal to 1% by weight and even more preferably less than or equal to 0.5% by weight relative to the weight of the composition.
- the present invention finally relates to a composition
- a composition comprising at least 90% by weight of eugenol and up to 10% by weight of ortho-eugenol relative to the total weight of the composition.
- the composition comprises at least at least 95% by weight of eugenol, more preferably at least 99% by weight and even more preferably at least 99.5% by weight of eugenol relative to the total weight of the composition.
- the orthoeugenol content in the composition is less than or equal to 10% by weight, preferably less than or equal to 8% by weight, very preferably less than or equal to 5% by weight and even more preferably less than or equal to 1% by weight relative to the weight of the composition.
- the inventors have discovered that the compositions according to the present invention exhibit satisfactory organoleptic properties.
- the compositions according to present invention have organoleptic properties similar or at least equivalent to those of eugenol obtained by extraction of a natural product.
- compositions according to the present invention can be used in perfumery or in aromatic, analgesic, antibacterial or antioxidant compositions.
- the compositions according to the present invention exhibit properties suitable for their use in perfumery or in aromatic, analgesic, antibacterial or antioxidant compositions, in particular in terms of organoleptic properties.
- Table 2 indicates that in the absence of a stabilizing compound, the thermal decomposition of eugenol begins at 275 ° C releasing 398J / g.
- Examples 2 to 9 indicate that in the presence of a stabilizing compound, the thermal decomposition of eugenol is initiated above 285 ° C and releases a significantly lower amount of energy, thus making it possible to operate. distillation process under suitable safety conditions.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (3)
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FR1905219A FR3096050B1 (fr) | 2019-05-17 | 2019-05-17 | Procede de purification d’eugenol et nouvelles compositions comprenant de l’eugenol |
EP19200216 | 2019-09-27 | ||
PCT/EP2020/063521 WO2020234123A1 (fr) | 2019-05-17 | 2020-05-14 | Procede de purification d'eugenol et nouvelles compositions comprenant de l'eugenol |
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EP3969434A1 true EP3969434A1 (de) | 2022-03-23 |
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EP20724855.0A Pending EP3969434A1 (de) | 2019-05-17 | 2020-05-14 | Verfahren zur reinigung von eugenol und neuartige zusammensetzungen mit eugenol |
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US (1) | US20220234979A1 (de) |
EP (1) | EP3969434A1 (de) |
JP (1) | JP2022532779A (de) |
CN (1) | CN113840819A (de) |
WO (1) | WO2020234123A1 (de) |
Family Cites Families (9)
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CA1030558A (en) * | 1974-08-16 | 1978-05-02 | Robert S. Desimone | Process for the selective allylation of ortho alkoxy phenols |
FR2302991A1 (fr) | 1975-03-07 | 1976-10-01 | Ube Industries | Procede pour la preparation d'ortho-alcoxy-para-allylphenols |
WO2007015260A2 (en) * | 2005-04-19 | 2007-02-08 | Camlin Fine Chemicals Ltd. | Improvement in synthesis of butylated hydroxyanisole from tertiary butyl hydroquinone |
US9439416B2 (en) * | 2005-11-30 | 2016-09-13 | Eden Research Plc | Compositions and methods comprising terpenes or terpene mixtures selected from thymol, eugenol, geraniol, citral, and l-carvone |
KR101701548B1 (ko) * | 2009-10-06 | 2017-02-01 | 바스프 에스이 | 벤조트로폴론을 함유하는 식물 추출물 및/또는 관련 벤조트로폴론 유도체의 사용에 의한 가정용 제품, 바디-관리 제품 및 식품의 안정화 |
CN104326885A (zh) * | 2014-10-09 | 2015-02-04 | 广西壮族自治区林业科学研究院 | 一种从丁香罗勒油中提取高纯丁香酚的方法 |
CN105294409B (zh) | 2015-09-15 | 2019-11-05 | 重庆欣欣向荣精细化工有限公司 | 一种丁香酚合成方法 |
CN105709140A (zh) * | 2016-01-20 | 2016-06-29 | 吕红风 | 一种治疗过敏性肺炎的药物组合物及其制备方法 |
CN108383695B (zh) * | 2018-06-01 | 2021-03-05 | 重庆欣欣向荣精细化工有限公司 | 丁香酚的制备方法及其应用和制备得到的丁香酚 |
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2020
- 2020-05-14 EP EP20724855.0A patent/EP3969434A1/de active Pending
- 2020-05-14 CN CN202080036785.1A patent/CN113840819A/zh active Pending
- 2020-05-14 JP JP2021568586A patent/JP2022532779A/ja active Pending
- 2020-05-14 WO PCT/EP2020/063521 patent/WO2020234123A1/fr active Application Filing
- 2020-05-14 US US17/610,754 patent/US20220234979A1/en active Pending
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WO2020234123A1 (fr) | 2020-11-26 |
JP2022532779A (ja) | 2022-07-19 |
CN113840819A (zh) | 2021-12-24 |
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