CN112110807A - Method for synthesizing vanillin by oxidizing eugenol with ozone - Google Patents
Method for synthesizing vanillin by oxidizing eugenol with ozone Download PDFInfo
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- CN112110807A CN112110807A CN201910531239.4A CN201910531239A CN112110807A CN 112110807 A CN112110807 A CN 112110807A CN 201910531239 A CN201910531239 A CN 201910531239A CN 112110807 A CN112110807 A CN 112110807A
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- Prior art keywords
- vanillin
- carrying
- isoeugenol
- reaction
- eugenol
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- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 title claims abstract description 122
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 title claims abstract description 108
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 235000012141 vanillin Nutrition 0.000 title claims abstract description 107
- 238000000034 method Methods 0.000 title claims abstract description 88
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000005770 Eugenol Substances 0.000 title claims abstract description 61
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229960002217 eugenol Drugs 0.000 title claims abstract description 61
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 25
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 21
- PZSJOBKRSVRODF-UHFFFAOYSA-N vanillin acetate Chemical compound COC1=CC(C=O)=CC=C1OC(C)=O PZSJOBKRSVRODF-UHFFFAOYSA-N 0.000 claims abstract description 69
- 238000005886 esterification reaction Methods 0.000 claims abstract description 45
- BJIOGJUNALELMI-ONEGZZNKSA-N Isoeugenol Natural products COC1=CC(\C=C\C)=CC=C1O BJIOGJUNALELMI-ONEGZZNKSA-N 0.000 claims abstract description 40
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 40
- BJIOGJUNALELMI-ARJAWSKDSA-N cis-isoeugenol Chemical compound COC1=CC(\C=C/C)=CC=C1O BJIOGJUNALELMI-ARJAWSKDSA-N 0.000 claims abstract description 40
- BJIOGJUNALELMI-UHFFFAOYSA-N trans-isoeugenol Natural products COC1=CC(C=CC)=CC=C1O BJIOGJUNALELMI-UHFFFAOYSA-N 0.000 claims abstract description 40
- 230000008569 process Effects 0.000 claims abstract description 39
- IUSBVFZKQJGVEP-SNAWJCMRSA-N isoeugenol acetate Chemical compound COC1=CC(\C=C\C)=CC=C1OC(C)=O IUSBVFZKQJGVEP-SNAWJCMRSA-N 0.000 claims abstract description 37
- IUSBVFZKQJGVEP-UHFFFAOYSA-N trans-isoeugenol acetate Natural products COC1=CC(C=CC)=CC=C1OC(C)=O IUSBVFZKQJGVEP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 27
- 230000003647 oxidation Effects 0.000 claims abstract description 26
- CMTKJYPJPSONIT-UHFFFAOYSA-K trichlororuthenium;triphenylphosphane Chemical compound Cl[Ru](Cl)Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 CMTKJYPJPSONIT-UHFFFAOYSA-K 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims description 66
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 47
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 39
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 238000004821 distillation Methods 0.000 claims description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- 230000002829 reductive effect Effects 0.000 claims description 27
- 230000032050 esterification Effects 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 23
- 238000010992 reflux Methods 0.000 claims description 20
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 18
- WURFKUQACINBSI-UHFFFAOYSA-M ozonide Chemical compound [O]O[O-] WURFKUQACINBSI-UHFFFAOYSA-M 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 238000005815 base catalysis Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 230000009471 action Effects 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000008213 purified water Substances 0.000 claims description 6
- 238000006722 reduction reaction Methods 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims description 4
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 claims description 4
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 4
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 4
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 4
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical class [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- 229940007550 benzyl acetate Drugs 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical group O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 239000007800 oxidant agent Substances 0.000 abstract description 6
- 238000011161 development Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- 238000007670 refining Methods 0.000 abstract 1
- 238000004065 wastewater treatment Methods 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 19
- 239000003921 oil Substances 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 244000290333 Vanilla fragrans Species 0.000 description 8
- 235000009499 Vanilla fragrans Nutrition 0.000 description 8
- 235000012036 Vanilla tahitensis Nutrition 0.000 description 8
- 239000003513 alkali Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 6
- ZMQAAUBTXCXRIC-UHFFFAOYSA-N safrole Chemical compound C=CCC1=CC=C2OCOC2=C1 ZMQAAUBTXCXRIC-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000796 flavoring agent Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 231100000331 toxic Toxicity 0.000 description 5
- 230000002588 toxic effect Effects 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 235000019634 flavors Nutrition 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 229960001867 guaiacol Drugs 0.000 description 3
- 229920005610 lignin Polymers 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006385 ozonation reaction Methods 0.000 description 3
- 239000012286 potassium permanganate Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- IBGBGRVKPALMCQ-UHFFFAOYSA-N 3,4-dihydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1O IBGBGRVKPALMCQ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 108010005214 Vanillyl-alcohol oxidase Proteins 0.000 description 2
- CGQCWMIAEPEHNQ-UHFFFAOYSA-N Vanillylmandelic acid Chemical compound COC1=CC(C(O)C(O)=O)=CC=C1O CGQCWMIAEPEHNQ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000013373 food additive Nutrition 0.000 description 2
- 239000002778 food additive Substances 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000010805 inorganic waste Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- IPBVNPXQWQGGJP-UHFFFAOYSA-N phenyl acetate Chemical compound CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 2
- SATCULPHIDQDRE-UHFFFAOYSA-N piperonal Chemical compound O=CC1=CC=C2OCOC2=C1 SATCULPHIDQDRE-UHFFFAOYSA-N 0.000 description 2
- 238000007867 post-reaction treatment Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- SKPCFEKMDDAMPN-BJILWQEISA-M sodium;2-methoxy-4-[(e)-prop-1-enyl]phenolate Chemical compound [Na+].COC1=CC(\C=C\C)=CC=C1[O-] SKPCFEKMDDAMPN-BJILWQEISA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229940034610 toothpaste Drugs 0.000 description 2
- 239000000606 toothpaste Substances 0.000 description 2
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- 206010020649 Hyperkeratosis Diseases 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 244000299461 Theobroma cacao Species 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 235000015895 biscuits Nutrition 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 235000012970 cakes Nutrition 0.000 description 1
- 229940025250 camphora Drugs 0.000 description 1
- 239000010238 camphora Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000019219 chocolate Nutrition 0.000 description 1
- 235000020965 cold beverage Nutrition 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- LJQKCYFTNDAAPC-UHFFFAOYSA-N ethanol;ethyl acetate Chemical compound CCO.CCOC(C)=O LJQKCYFTNDAAPC-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 235000019264 food flavour enhancer Nutrition 0.000 description 1
- 229930182478 glucoside Natural products 0.000 description 1
- 150000008131 glucosides Chemical class 0.000 description 1
- 239000007952 growth promoter Substances 0.000 description 1
- 235000015243 ice cream Nutrition 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 235000008446 instant noodles Nutrition 0.000 description 1
- 229930013686 lignan Natural products 0.000 description 1
- 150000005692 lignans Chemical class 0.000 description 1
- 235000009408 lignans Nutrition 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229940126601 medicinal product Drugs 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000013048 microbiological method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229940081310 piperonal Drugs 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229960003371 protocatechualdehyde Drugs 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000004114 suspension culture Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000002916 wood waste Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
-
- 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
- C07C41/32—Preparation of ethers by isomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
Abstract
The invention relates to the technical field of organic chemical synthesis, in particular to a method for synthesizing vanillin by oxidizing eugenol with ozone, which comprises the following steps: adding triphenylphosphine ruthenium chloride as a catalyst into eugenol for isomerization reaction to obtain isoeugenol for esterification reaction to obtain isoeugenol acetate, carrying out ozone oxidation and reduction on the isoeugenol acetate, carrying out acetovanillin alcoholysis, and refining to obtain a pure product. The invention solves the problems of low production yield, use of metal oxidant and difficult wastewater treatment of a eugenol method in the prior art, the eugenol adopts triphenylphosphine ruthenium chloride as a catalyst, no wastewater is generated in the process, and isoeugenol acetate adopts ozone oxidation, so that the use of a heavy metal oxidant is avoided, the process conforms to the green development trend, and the process has the advantages of environmental protection and high yield.
Description
Technical Field
The invention relates to the technical field of organic chemical synthesis, in particular to a method for synthesizing vanillin by oxidizing eugenol with ozone.
Background
Vanillin is one of important edible spices, is an edible flavor enhancer, has vanilla bean flavor and strong milk flavor, is an indispensable important raw material in the food additive industry, is widely applied to various flavor-enhancing foods needing milk flavor enhancement, such as cakes, cold drinks, chocolates, candies, biscuits, instant noodles, bread, tobaccos, flavor-enhancing wine, toothpaste, soap, perfume, cosmetics, ice cream, beverages and daily cosmetics, and plays roles in enhancing and fixing flavor. It can also be used for soap, toothpaste, rubber, plastics, and medicinal products. Meets the FCC IV standard.
Vanillin has wide application field in foreign countries, and is widely used for producing medical intermediates, plant growth promoters, bactericides, lubricating oil antifoaming agents, electroplating brightening agents, printed circuit board production conductive agents and the like. The domestic vanillin is mainly used as a food additive, and the application of the domestic vanillin in the field of medicines is continuously widened in recent years, so that the domestic vanillin becomes the most potential field for applying vanillin. At present, domestic vanillin consumption is as follows: 55% in the food industry, 30% in the medical intermediate, 10% in the feed flavoring agent, 5% in the cosmetics industry, etc.
At present, the synthesis of vanillin mainly comprises: chemical synthesis, natural extraction and biological synthesis. The literature reports that many methods for preparing vanillin by chemical synthesis methods mainly include lignin method, safrole method, eugenol method, guaiacol method and the like. Lignin is widely present in wood waste, straw, peat, pulp waste and distillers' grains, and the lignin contained in these wastes can be utilized to prepare vanillin. The yield of vanillin generated by sulfonating waste liquid of paper making in Li Guangzhou of Anhui university of Engineers and oxidizing the waste liquid can reach 10.8 percent at most. The safrole method comprises isomerizing safrole (derived from oleum Camphora) under alkaline condition, oxidizing to piperonal, and then adding PCl5Preparing protocatechualdehyde under the action of the above-mentioned raw materials, finally making methylation reaction by using dimethyl sulfate so as to obtain vanillin. At the end of the 19 th century, Reimer and TieTnann began to synthesize vanillin using the eugenol process. At present, the most common method is to isomerize eugenol into sodium isoeugenol in the presence of alkali, then oxidize the sodium isoeugenol into vanillin sodium salt by using an oxidizing agent, and then neutralize and crystallize to obtain vanillin. Chinese patent CN107188791A discloses a method for synthesizing vanillin from eugenol raw material by isomerization, esterification, oxidation and hydrolysis processes. The process for synthesizing vanillin by using the guaiacol method is mature, and is a mainstream method adopted in the vanillin synthesis industry at present. From the 80 s in the 20 th century, most foreign manufacturers have condensed guaiacol with glyoxylic acid under alkaline conditions to produce 3-methoxy-4-hydroxymandelic acid, and the condensation reaction liquid is used for recovering unreacted guaiacolAfter the lignan is oxidized by catalysis, the corresponding ketonate is generated, and the ketonate is decarboxylated under the acidic condition to generate vanillin.
Vanillin is widely present in nature in free form and in the form of glucosides, especially in Vanilla, in amounts of about 20g/kg (dry weight). A deep-processed vanilla product is mainly an infusion of vanilla, and is prepared by cutting vanilla into pieces, placing into an extractor, extracting with 95% ethanol at 50-60 deg.C, and filtering. This process is costly, time consuming, and solvent remains.
In 1991, Knuth et al suggested that vanilla callus cell suspension culture secreted a complex vanilla-flavored substance, and that 0.099g/L vanillin could be obtained after continuous extraction with activated carbon for 14 days without precursor. Van den Heuvel et al found that vanillin could be produced using Vanillyl Alcohol Oxidase (VAO).
Eugenol is used as a raw material, a direct oxidation method is generally adopted for industrially producing vanillin, namely, eugenol and strong alkali are heated together to isomerize into isoeugenol, and then the isoeugenol is directly oxidized. The vanillin produced by the process has good fragrance, but the production cost is high, the production yield is about 60%, only a few manufacturers adopt the process at present, and the total yield is very small. Patent CN107188791A discloses a method for obtaining vanillin by using eugenol as raw material through isomerization, esterification and potassium permanganate oxidation, but the method has the following disadvantages: the isomerization reaction temperature is high and the time is long; toxic solvents of dichloromethane and triethylamine are used in the phenolic hydroxyl protection process, so that the fragrance and the quality of the vanillin product are influenced; the oxidation reaction uses a metal oxidant KMnSO4The waste liquid generated by the reaction is difficult to treat, has serious pollution to the environment and is gradually eliminated.
The plant extraction method has its own advantages, and vanillin extracted from the plant vanilla is natural, but because the planting area of the vanilla is limited, the yield is greatly influenced by climate, the labor intensity of crop planting and processing is too high, and the produced natural vanillin can not meet the market demand.
The microbial vanillin production method overcomes the influence of chemically synthesized vanillin on human body in the food field, has no toxic or side effect, and has the advantages of short period, no influence of seasons and natural environment, low cost, batch production and the like. At present, the world only has france Rodiya companies to produce vanillin by a microbiological method, but the enterprises are still in the beginning stage, and the supply of the vanillin is limited.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a method for synthesizing vanillin by oxidizing eugenol with ozone, which is used for solving the problems that the production yield of a eugenol method is low, a metal oxidant is used, and waste water is difficult to treat in the prior art.
In order to attain the above and other related objects,
in a first aspect of the present invention, a method for synthesizing vanillin by ozone oxidation of eugenol is provided, which comprises the following steps:
isomerization of S1 eugenol: adding triphenylphosphine ruthenium chloride as a catalyst into eugenol for isomerization reaction, and carrying out reduced pressure distillation to collect isoeugenol;
esterification of S2 isoeugenol: adding an esterification catalyst and acetic anhydride into isoeugenol for esterification reaction to obtain isoeugenol acetate;
s3 redox of isoeugenol acetate: mixing isoeugenol acetate with a solvent, putting the mixture into an ozone oxidation tower, introducing ozone for oxidation reaction to form an ozonide, and reacting the ozonide under the action of a reducing agent to generate an acetyl vanillin solution;
alcoholysis of S4 acetyl vanillin: adding an alkaline alcoholysis catalyst into an acetyl vanillin solution, carrying out base catalysis alcoholysis under reflux to obtain vanillin, adjusting the pH to 6-7 after the alcoholysis is finished, carrying out reduced pressure distillation to recover the solvent, and washing the residual oil phase to obtain a crude vanillin product;
s5 refined vanillin: crystallizing the crude vanillin to obtain a pure vanillin product.
The vanillin process is environment-friendly, the reaction conditions are mild and easy to control, the reaction conversion rate and the selectivity are obviously improved, and the process quality is stable.
The isomerization of the eugenol adopts triphenylphosphine ruthenium chloride as a catalyst, no solvent is needed, no waste water is generated, and the catalyst can be repeatedly used. The process is simple and easy to control, the pollution is less, the yield reaches 99 percent, the purification effect is good, and the industrial production is easy to realize. The traditional isomerization process uses potassium hydroxide solution, which produces a large amount of alkaline wastewater. Adopting carbonyl iron to catalyze and obtain isoeugenol. But the production process uses a large amount of acid and alkali, generates a large amount of waste water and can cause serious pollution to the environment. And the carbonyl iron catalyst is easy to be poisoned, so that the catalytic effect is reduced.
The oxidation of the isoeugenol acetate takes ozone as an oxygen source, and has the advantages of high reaction rate, mild conditions and high reaction selectivity. The post-reaction treatment is very simple, has no pollution to the environment, and meets the development requirements and trends of the current green chemistry and clean processes; the traditional synthesis method is to prepare the isoeugenol acetate by oxidizing potassium permanganate or potassium dichromate, has high relative yield, but generates a large amount of inorganic wastes such as manganese dioxide, chromium and the like, and has great influence on the environment.
In an embodiment of the present invention, the method includes the following steps:
isomerization of S1 eugenol: the method comprises the following steps of (1) mixing triphenylphosphine ruthenium chloride and eugenol according to a mass ratio of (0.0001-0.05): 1, carrying out isomerization reaction for 3-8 h at the temperature of 0-150 ℃, and then carrying out reduced pressure distillation to collect isoeugenol;
esterification of S2 isoeugenol: the esterification catalyst, acetic anhydride and isoeugenol are mixed according to the molar ratio of (0.01-1): (1-5): 1, carrying out esterification reaction at the temperature of 50-200 ℃ after mixing, and continuously fractionating acetic acid generated in a reaction system in the esterification reaction process until the reaction is complete to obtain isoeugenol acetate;
s3 redox of isoeugenol acetate: mixing isoeugenol acetate and a solvent according to a mass ratio of 1: (1-20), introducing the mixture into an ozone oxidation tower, and carrying out oxidation reaction at-30-100 ℃ until the raw materials are completely oxidized into ozonides, wherein the molar ratio of the ozonides to the reducing agent is 1: (0.1-10), carrying out reduction reaction on ozonide at the temperature of-10-100 ℃ to generate an acetyl vanillin solution;
alcoholysis of S4 acetyl vanillin: adding potassium carbonate into the acetyl vanillin solution, wherein the molar ratio of the acetyl vanillin to the potassium carbonate is 1: (0.01-2), carrying out base catalysis alcoholysis under reflux to obtain vanillin, adjusting the pH to 6-7 after the alcoholysis is finished, carrying out reduced pressure distillation to recover the solvent, carrying out oil-water separation, washing the residual oil phase with a supersaturated sodium bicarbonate water solution and purified water in sequence to be neutral, and obtaining crude vanillin when the oil phase accounts for 20-80% of the whole volume of the solution in the alcoholysis process;
s5 refined vanillin: and (3) rectifying the crude vanillin, then carrying out dynamic crystallization by using ethanol as a solvent, carrying out centrifugal separation, and drying to obtain a pure vanillin product.
In an embodiment of the present invention, the method includes the following steps:
isomerization of S1 eugenol: the method comprises the following steps of (1) mixing triphenylphosphine ruthenium chloride and eugenol according to the mass ratio of (0.002-0.05): 1, carrying out isomerization reaction for 3-8 h at the temperature of 20-140 ℃ after mixing, and then carrying out reduced pressure distillation to collect isoeugenol;
esterification of S2 isoeugenol: the esterification catalyst, acetic anhydride and isoeugenol are mixed according to the molar ratio of (0.02-0.5): (1-3): 1, performing esterification reaction at the temperature of 80-170 ℃, and continuously fractionating acetic acid generated in a reaction system in the esterification reaction process until the reaction is complete to obtain isoeugenol acetate;
s3 redox of isoeugenol acetate: mixing isoeugenol acetate and a solvent according to a mass ratio of 1: (1-10), introducing the mixture into an ozone oxidation tower, and carrying out oxidation reaction at the temperature of-20-70 ℃ until the raw materials are completely oxidized into ozonides, wherein the molar ratio of the ozonides to the reducing agent is 1: (0.3-3), carrying out reduction reaction on ozonide at the temperature of 0-80 ℃ to generate an acetyl vanillin solution;
alcoholysis of S4 acetyl vanillin: adding potassium carbonate into the acetyl vanillin solution, wherein the molar ratio of the acetyl vanillin to the potassium carbonate is 1: (0.1-1.5) carrying out base catalysis alcoholysis under reflux to obtain vanillin, adjusting the pH to 6-7 after the alcoholysis is finished, carrying out reduced pressure distillation to recover the solvent, carrying out oil-water separation, washing the residual oil phase to be neutral by a supersaturated sodium bicarbonate aqueous solution and purified water in sequence, and obtaining crude vanillin, wherein the oil phase accounts for 50-80% of the whole volume of the solution in the alcoholysis process;
s5 refined vanillin: and (3) rectifying the crude vanillin, then carrying out dynamic crystallization by using ethanol as a solvent, carrying out centrifugal separation, and drying to obtain a pure vanillin product.
In an embodiment of the present invention, the method includes the following steps:
isomerization of S1 eugenol: the method comprises the following steps of (1) mixing triphenylphosphine ruthenium chloride and eugenol according to the mass ratio of (0.004-0.04): 1, carrying out isomerization reaction for 3-8 h at the temperature of 50-80 ℃, and then carrying out reduced pressure distillation to collect isoeugenol;
esterification of S2 isoeugenol: the esterification catalyst, acetic anhydride and isoeugenol are mixed according to the molar ratio of (0.05-0.2): (1-2): 1, carrying out esterification reaction at the temperature of 100-150 ℃ after mixing, and continuously fractionating acetic acid generated in a reaction system in the esterification reaction process until the reaction is complete to obtain isoeugenol acetate;
s3 redox of isoeugenol acetate: mixing isoeugenol acetate and a solvent according to a mass ratio of 1: (2-6), introducing the mixture into an ozone oxidation tower, and carrying out oxidation reaction at the temperature of-10-50 ℃ until the raw materials are completely oxidized into ozonides, wherein the molar ratio of the ozonides to the reducing agent is 1: (0.5-2), carrying out reduction reaction on ozonide at the temperature of 40-70 ℃ to generate an acetyl vanillin solution;
alcoholysis of S4 acetyl vanillin: adding potassium carbonate into the acetyl vanillin solution, wherein the molar ratio of the acetyl vanillin to the potassium carbonate is 1: (0.5-1), carrying out base catalysis alcoholysis under reflux to obtain vanillin, adjusting the pH to 6-7 after the alcoholysis is finished, carrying out reduced pressure distillation to recover the solvent, carrying out oil-water separation, washing the residual oil phase with a supersaturated sodium bicarbonate water solution and purified water in sequence to be neutral, and obtaining crude vanillin when the oil phase accounts for 70-80% of the whole volume of the solution in the hydrolysis process;
s5 refined vanillin: and (3) rectifying the crude vanillin, then carrying out dynamic crystallization by using ethanol as a solvent, carrying out centrifugal separation, and drying to obtain a pure vanillin product.
In an embodiment of the present invention, the esterification catalyst is at least one of anhydrous sodium carbonate, anhydrous sodium acetate and/or anhydrous potassium carbonate, which avoids the use of toxic solvent dichloromethane and strong-odor triethylamine.
In one embodiment of the present invention, the esterification catalyst is anhydrous sodium carbonate. The esterification reaction of the isoeugenol and the acetic anhydride is catalyzed by anhydrous sodium carbonate without a solvent; the use of a toxic solvent dichloromethane and triethylamine with strong smell is avoided.
In an embodiment of the invention, the solvent is at least one of ethanol, methanol, benzyl acetate, water and/or toluene. And (3) carrying out alcoholysis on the acetyl vanillin under the action of ethanol and potassium carbonate to obtain vanillin, wherein the front distillation fraction distilled after alcoholysis is recycled. The traditional process is that acetyl vanillin is hydrolyzed under the action of dilute hydrochloric acid to separate out vanillin, and the water phase is neutralized to be neutral by liquid alkali for treatment, so that a large amount of waste water is produced, and the environmental impact is large.
In an embodiment of the invention, the solvent is an ethanol aqueous solution.
In an embodiment of the present invention, the reducing agent is zinc powder and/or sodium metabisulfite.
As mentioned above, the method for synthesizing vanillin by oxidizing eugenol with ozone has the following beneficial effects:
1. the vanillin process is environment-friendly, the reaction conditions are mild and easy to control, the reaction conversion rate and selectivity are obviously improved, and the process quality is relatively stable;
2. the isomerization of the eugenol adopts triphenylphosphine ruthenium chloride as a catalyst, no solvent is needed, no waste water is generated, and the catalyst can be repeatedly used. The process is simple and easy to control, the pollution is less, the yield reaches 99 percent, the purification effect is good, and the industrial production is easy to realize. The traditional isomerization process uses potassium hydroxide solution, which produces a large amount of alkaline wastewater. Adopting carbonyl iron to catalyze and obtain isoeugenol. But the production process uses a large amount of acid and alkali, generates a large amount of waste water and can cause serious pollution to the environment. The carbonyl iron catalyst is easy to be poisoned, so that the catalytic effect is reduced;
3. the esterification reaction of isoeugenol and acetic anhydride adopts anhydrous Na2CO3Catalysis, no solvent is needed; the use of a toxic solvent dichloromethane and triethylamine with strong smell is avoided;
4. the oxidation of the isoeugenol acetate takes ozone as an oxygen source, and has the advantages of high reaction rate, mild conditions and high reaction selectivity. The post-reaction treatment is very simple, has no pollution to the environment, and meets the development requirements and trends of the current green chemistry and clean processes; the traditional synthetic method is prepared by oxidizing isoeugenol acetate by potassium permanganate or potassium dichromate, has high relative yield, but generates a large amount of inorganic wastes such as manganese dioxide, chromium and the like, and has great influence on the environment;
5. and (3) carrying out alcoholysis on the acetyl vanillin under the action of ethanol and potassium carbonate to obtain vanillin, wherein the front distillation fraction distilled after alcoholysis is recycled. The traditional process is that acetyl vanillin is hydrolyzed under the action of dilute hydrochloric acid to separate out vanillin, and the water phase is neutralized to be neutral by liquid alkali for treatment, so that a large amount of waste water is produced, and the environmental impact is large.
Drawings
FIG. 1 is a process flow diagram of example 1;
FIG. 2 is a process flow diagram of example 2.
Detailed Description
The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure.
Example 1
The method for synthesizing vanillin by oxidizing eugenol with ozone comprises the following steps:
1. and (3) isomerization reaction:
adding 500g of eugenol and 4.0g of catalyst triphenylphosphine ruthenium chloride into a reaction kettle, uniformly mixing, heating to 50-60 ℃, and keeping the temperature for reaction for 4 hours until the content of eugenol is lower than 1%. Then directly carrying out reduced pressure distillation to obtain 495g of isoeugenol with the content of 98.5 percent and the mass yield of 99 percent.
And (3) adding 500g of eugenol and 1g of new catalyst into the catalyst and part of organic matters in the rest kettle in the previous example, still heating to 50-60 ℃, and keeping the temperature for reacting for 4-5 hours. When the content of eugenol is lower than 1 percent, reduced pressure distillation is directly carried out to obtain 496g of isoeugenol with the content of 98.4 percent, and the mass yield is 99 percent.
2. Esterification reaction:
adding 10g of anhydrous sodium carbonate and 390g of acetic anhydride into a 1000ml three-neck flask with a thermometer and a reflux condenser, and stirring and heating; when the temperature of the system rises to 100 ℃, 400g of isoeugenol is dripped; continuously heating to 120 ℃ after dripping; at the moment, reflux occurs in the reaction bottle, and the acetic acid generated by the reaction is continuously distilled out by normal pressure distillation, so that the reaction temperature is maintained between 130 and 150 ℃ for continuous reaction for 3 hours. After the reaction was completed, 250g of water was added to quench the reaction and the esterification product was washed. After cooling, 500g of isoeugenol acetate with the content of 98.5 percent is obtained, and the mass yield is 99 percent.
3. Ozone oxidation:
120g of isoeugenol acetate was dissolved in 300g of 40% aqueous ethanol. The solution was put into a 1000ml jacketed reaction flask, the gas flow was adjusted, and O was introduced3The gas is subjected to ozonization reaction, and the reaction temperature is controlled to be-20-0 ℃. The ozone oxidation time is 1-2 h, and sampling detection is carried out until the oxidation is complete.
100g of a 20% sodium metabisulfite solution was charged into a flask equipped with a stirrer, a thermometer, a reflux and dropping device, and then ozonide was dropped to carry out a reaction. And after the dropwise addition, cooling in a water bath to control the reaction temperature to be 60-70 ℃.
4. Alcoholysis reaction:
adding 40g of anhydrous potassium carbonate into the reductive decomposition system of the ozonide, starting stirring, heating to 85 ℃, and carrying out reflux reaction for about 4 hours to complete the reaction. Then adding dilute sulphuric acid to adjust the pH value to be subacidity, distilling off ethanol and ethyl acetate at normal pressure, and carrying out oil-water phase separation on the residual materials in the kettle. The main component of the oil phase is vanillin, the oil phase is separated, and the oil phase is washed by 30g of water for 2 times. Finally, the vanillin is put into an alcohol water solution for recrystallization, and finished product vanillin 73g with the content of more than 99% is obtained.
Taking 200g of ethyl acetate-ethanol mixed solution, wherein the ethyl acetate content is 30%, the ethanol content is 70%, adding 32g of solid sodium hydroxide and 15g of water, heating to 50 ℃, reacting for 4h, and reacting completely. The filtered solid is 37g of hydrated sodium acetate and a small amount of unreacted sodium hydroxide, and the residual filtrate is ethanol with the content of 99 percent and the weight of 198 g. The recovered ethanol returns to the alcoholysis step, and the reaction effect is good.
Example 2
The method for synthesizing vanillin by oxidizing eugenol with ozone comprises the following steps:
1. and (3) isomerization reaction:
adding 500g of eugenol and 3.0g of catalyst triphenylphosphine ruthenium chloride into a reaction kettle, uniformly mixing, heating to 60-80 ℃, and keeping the temperature for reaction for 4 hours until the content of eugenol is lower than 1%. Then directly carrying out reduced pressure distillation to obtain 495g of isoeugenol with the content of 98.5 percent and the mass yield of 99 percent.
And (3) adding 500g of eugenol and 2g of new catalyst into the catalyst and part of organic matters in the rest kettle in the previous example, still heating to 60-80 ℃, and keeping the temperature for reaction for 5.0 h. When the content of eugenol is lower than 1 percent, directly carrying out reduced pressure distillation to obtain 495g of isoeugenol with the content of 98.6 percent, wherein the mass yield is 99 percent.
2. Esterification reaction:
adding 20g of anhydrous sodium acetate and 360g of acetic anhydride into a 1000ml three-neck flask with a thermometer and a reflux condenser, and stirring and heating; when the temperature of the system rises to 100 ℃, 400g of isoeugenol is dripped; continuously heating to 120 ℃ after dripping; at the moment, reflux occurs in the reaction bottle, and the acetic acid generated by the reaction is continuously distilled out by normal pressure distillation, so that the reaction temperature is maintained between 130 and 150 ℃ for continuous reaction for 3 hours. After the reaction was completed, 250g of water was added to quench the reaction and the esterification product was washed. After cooling, 490g of white crystal isoeugenol acetate with the content of 98.9 percent is obtained, and the mass yield is 98 percent.
3. Ozone oxidation:
herba Lysimachiae Foenumgraeci120g of phenol acetate is dissolved in 300g of water-ethanol solution, and the volume ratio of water to ethanol is 1: 1. The solution was put into a 1000ml jacketed reaction flask, the gas flow was adjusted, and O was introduced3The gas is subjected to ozonization reaction, and the reaction temperature is controlled to be 50-70 ℃. The ozone oxidation time is 1-2 h, and sampling detection is carried out until the oxidation is complete.
In a flask equipped with a stirrer, a thermometer, a reflux and dropping device, 40g of zinc powder was charged, and then ozonide was dropped to carry out a reaction. And after the dropwise addition, cooling in a water bath to control the reaction temperature to be 40-60 ℃.
4. Alcoholysis reaction:
adding 40g of anhydrous potassium carbonate into the reductive decomposition system of the ozonide, starting stirring, heating to 90 ℃, and carrying out reflux reaction for about 4 hours to complete the reaction. Then after the pH value is adjusted to be weakly acidic by dilute sulfuric acid, ethanol and ethyl acetate are distilled out by atmospheric pressure distillation, and the oil and water phases of the residual materials in the kettle are separated. The main component of the oil phase is vanillin, the oil phase is separated, and the oil phase is washed by 30g of water for 2 times. The lower organic phase was separated and subjected to fast distillation to yield 75.0g of crude vanillin with a content of > 95%. Finally, the vanillin is put into an alcohol water solution for recrystallization, and finished vanillin 71g with the content of more than 99% is obtained.
Example 3
The method for synthesizing vanillin by oxidizing eugenol with ozone comprises the following steps:
1. and (3) isomerization reaction:
adding 500g of eugenol and 0.1g of catalyst triphenylphosphine ruthenium chloride into a reaction kettle, uniformly mixing, heating to 120-150 ℃, and keeping the temperature for reaction for 6 hours until the content of eugenol is lower than 1%. Then, 491g of isoeugenol with the content of 98.8 percent is obtained by directly carrying out reduced pressure distillation, and the mass yield is 98 percent.
And adding 500g of eugenol and 0.03g of new catalyst into the catalyst and part of organic matters in the rest kettle in the previous example, still heating to 120-150 ℃, and keeping the temperature for reacting for 4-5 h. When the content of eugenol is lower than 1 percent, directly carrying out reduced pressure distillation to obtain 495g of isoeugenol with the content of 98.4 percent, wherein the mass yield is 99 percent.
2. Esterification reaction:
adding 25g of anhydrous sodium carbonate and 400g of acetic anhydride into a 1000ml three-neck flask with a thermometer and a reflux condenser, and stirring and heating; when the temperature of the system rises to 120 ℃, 400g of isoeugenol is dripped; and (3) refluxing occurs in the reaction bottle after dripping, and the acetic acid generated by the reaction is continuously distilled out by normal pressure distillation, so that the reaction temperature is maintained between 150 ℃ and 180 ℃ for continuous reaction for 2 hours. After the reaction was completed, 250g of water was added to quench the reaction and the esterification product was washed. 485g of white crystal isoeugenol acetate with the content of 98.9 percent is obtained after cooling, and the mass yield is 98 percent.
3. Ozone oxidation:
120g of isoeugenol acetate was dissolved in 400g of 40% aqueous ethanol. The solution was put into a 1000ml jacketed reaction flask, the gas flow was adjusted, and O was introduced3The gas is subjected to ozonization reaction, and the reaction temperature is controlled to be 0-10 ℃. The ozone oxidation time is 1-2 h, and sampling detection is carried out until the oxidation is complete.
200g of a 20% sodium metabisulfite solution was placed in a flask equipped with a stirrer, a thermometer, a reflux and dropping device, and then an ozonide was dropped to carry out a reaction. And after the dropwise addition, cooling in a water bath to control the reaction temperature to be 50-70 ℃.
4. Alcoholysis reaction:
adding 40g of anhydrous sodium acetate into the reductive decomposition system of the ozonide, starting stirring, heating to 85 ℃, and carrying out reflux reaction for about 4 hours to complete the reaction. Then adding dilute sodium hydroxide to adjust the pH value to be weakly acidic, distilling off ethanol and ethyl acetate at normal pressure, and carrying out oil-water phase separation on the residual materials in the kettle. The main component of the oil phase is vanillin, the oil phase is separated, and the oil phase is washed by 30g of water for 2 times. The lower organic phase was separated and subjected to fast distillation to yield 75.9g of crude vanillin with a content of > 95%. Finally, the vanillin is put into an alcohol water solution for recrystallization, and 72g of finished vanillin with the content of more than 99% is obtained.
In conclusion, the eugenol in the invention adopts triphenylphosphine ruthenium chloride as a catalyst, no waste water is generated in the process, and the isoeugenol acetate is oxidized by ozone, so that the use of heavy metal oxidants is avoided, the process conforms to the green development trend, and the process has the advantages of environmental protection and high yield. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (9)
1. A method for synthesizing vanillin by oxidizing eugenol with ozone is characterized by comprising the following steps:
isomerization of S1 eugenol: adding triphenylphosphine ruthenium chloride as a catalyst into eugenol for isomerization reaction, and carrying out reduced pressure distillation to collect isoeugenol;
esterification of S2 isoeugenol: adding an esterification catalyst and acetic anhydride into isoeugenol for esterification reaction to obtain isoeugenol acetate;
s3 redox of isoeugenol acetate: mixing isoeugenol acetate with a solvent, putting the mixture into an ozone oxidation tower, introducing ozone for oxidation reaction to form an ozonide, and reacting the ozonide under the action of a reducing agent to generate an acetyl vanillin solution;
alcoholysis of S4 acetyl vanillin: adding an alkaline alcoholysis catalyst into an acetyl vanillin solution, carrying out base catalysis alcoholysis under reflux to obtain vanillin, adjusting the pH to 6-7 after the alcoholysis is finished, carrying out reduced pressure distillation to recover the solvent, and washing the residual oil phase to obtain a crude vanillin product;
s5 refined vanillin: crystallizing the crude vanillin to obtain a pure vanillin product.
2. The method for synthesizing vanillin by oxidizing eugenol with ozone as claimed in claim 1, comprising the steps of:
isomerization of S1 eugenol: the method comprises the following steps of (1) mixing triphenylphosphine ruthenium chloride and eugenol according to a mass ratio of (0.0001-0.05): 1, carrying out isomerization reaction for 3-8 h at the temperature of 0-150 ℃, and then carrying out reduced pressure distillation to collect isoeugenol;
esterification of S2 isoeugenol: the esterification catalyst, acetic anhydride and isoeugenol are mixed according to the molar ratio of (0.01-1): (1-5): 1, carrying out esterification reaction at the temperature of 50-200 ℃ after mixing, and continuously fractionating acetic acid generated in a reaction system in the esterification reaction process until the reaction is complete to obtain isoeugenol acetate;
s3 redox of isoeugenol acetate: mixing isoeugenol acetate and a solvent according to a mass ratio of 1: (1-20), introducing the mixture into an ozone oxidation tower, and carrying out oxidation reaction at-30-100 ℃ until the raw materials are completely oxidized into ozonides, wherein the molar ratio of the ozonides to the reducing agent is 1: (0.1-10), carrying out reduction reaction on ozonide at the temperature of-10-100 ℃ to generate an acetyl vanillin solution;
alcoholysis of S4 acetyl vanillin: adding potassium carbonate into the acetyl vanillin solution, wherein the molar ratio of the acetyl vanillin to the potassium carbonate is 1: (0.01-2), carrying out base catalysis alcoholysis under reflux to obtain vanillin, adjusting the pH to 6-7 after the alcoholysis is finished, carrying out reduced pressure distillation to recover the solvent, carrying out oil-water separation, washing the residual oil phase with a supersaturated sodium bicarbonate water solution and purified water in sequence to be neutral, and obtaining crude vanillin when the oil phase accounts for 20-80% of the whole volume of the solution in the alcoholysis process;
s5 refined vanillin: and (3) rectifying the crude vanillin, then carrying out dynamic crystallization by using ethanol as a solvent, carrying out centrifugal separation, and drying to obtain a pure vanillin product.
3. The method for synthesizing vanillin by oxidizing eugenol with ozone as claimed in claim 1 or 2, comprising the steps of:
isomerization of S1 eugenol: the method comprises the following steps of (1) mixing triphenylphosphine ruthenium chloride and eugenol according to the mass ratio of (0.002-0.05): 1, carrying out isomerization reaction for 3-8 h at the temperature of 20-140 ℃ after mixing, and then carrying out reduced pressure distillation to collect isoeugenol;
esterification of S2 isoeugenol: the esterification catalyst, acetic anhydride and isoeugenol are mixed according to the molar ratio of (0.02-0.5): (1-3): 1, performing esterification reaction at the temperature of 80-170 ℃, and continuously fractionating acetic acid generated in a reaction system in the esterification reaction process until the reaction is complete to obtain isoeugenol acetate;
s3 redox of isoeugenol acetate: mixing isoeugenol acetate and a solvent according to a mass ratio of 1: (1-10), introducing the mixture into an ozone oxidation tower, and carrying out oxidation reaction at the temperature of-20-70 ℃ until the raw materials are completely oxidized into ozonides, wherein the molar ratio of the ozonides to the reducing agent is 1: (0.3-3), carrying out reduction reaction on ozonide at the temperature of 0-80 ℃ to generate an acetyl vanillin solution;
alcoholysis of S4 acetyl vanillin: adding potassium carbonate into the acetyl vanillin solution, wherein the molar ratio of the acetyl vanillin to the potassium carbonate is 1: (0.1-1.5) carrying out base catalysis alcoholysis under reflux to obtain vanillin, adjusting the pH to 6-7 after the alcoholysis is finished, carrying out reduced pressure distillation to recover the solvent, carrying out oil-water separation, washing the residual oil phase to be neutral by a supersaturated sodium bicarbonate aqueous solution and purified water in sequence, and obtaining crude vanillin, wherein the oil phase accounts for 50-80% of the whole volume of the solution in the alcoholysis process;
s5 refined vanillin: and (3) rectifying the crude vanillin, then carrying out dynamic crystallization by using ethanol as a solvent, carrying out centrifugal separation, and drying to obtain a pure vanillin product.
4. The method for synthesizing vanillin through ozone oxidation of eugenol according to any one of claims 1 to 3, comprising the following steps:
isomerization of S1 eugenol: the method comprises the following steps of (1) mixing triphenylphosphine ruthenium chloride and eugenol according to the mass ratio of (0.004-0.04): 1, carrying out isomerization reaction for 3-8 h at the temperature of 50-80 ℃, and then carrying out reduced pressure distillation to collect isoeugenol;
esterification of S2 isoeugenol: the esterification catalyst, acetic anhydride and isoeugenol are mixed according to the molar ratio of (0.05-0.2): (1-2): 1, carrying out esterification reaction at the temperature of 100-150 ℃ after mixing, and continuously fractionating acetic acid generated in a reaction system in the esterification reaction process until the reaction is complete to obtain isoeugenol acetate;
s3 redox of isoeugenol acetate: mixing isoeugenol acetate and a solvent according to a mass ratio of 1: (2-6), introducing the mixture into an ozone oxidation tower, and carrying out oxidation reaction at the temperature of-10-50 ℃ until the raw materials are completely oxidized into ozonides, wherein the molar ratio of the ozonides to the reducing agent is 1: (0.5-2), carrying out reduction reaction on ozonide at the temperature of 40-70 ℃ to generate an acetyl vanillin solution;
alcoholysis of S4 acetyl vanillin: adding potassium carbonate into the acetyl vanillin solution, wherein the molar ratio of the acetyl vanillin to the potassium carbonate is 1: (0.5-1), carrying out base catalysis alcoholysis under reflux to obtain vanillin, adjusting the pH to 6-7 after the alcoholysis is finished, carrying out reduced pressure distillation to recover the solvent, carrying out oil-water separation, washing the residual oil phase with a supersaturated sodium bicarbonate water solution and purified water in sequence to be neutral, and obtaining crude vanillin when the oil phase accounts for 70-80% of the whole volume of the solution in the alcoholysis process;
s5 refined vanillin: and (3) rectifying the crude vanillin, then carrying out dynamic crystallization by using ethanol as a solvent, carrying out centrifugal separation, and drying to obtain a pure vanillin product.
5. The method for synthesizing vanillin by oxidizing eugenol with ozone according to any one of claims 1 to 4, wherein the method comprises the following steps: the esterification catalyst is at least one of anhydrous sodium carbonate, anhydrous sodium acetate and/or anhydrous potassium carbonate.
6. The method for synthesizing vanillin by oxidizing eugenol with ozone as claimed in any one of claim 5, wherein the method comprises the following steps: the esterification catalyst is anhydrous sodium carbonate.
7. The method for synthesizing vanillin by oxidizing eugenol with ozone according to any one of claims 1 to 4, wherein the method comprises the following steps: the solvent is at least one of ethanol, methanol, benzyl acetate, water and/or toluene.
8. The method for synthesizing vanillin by oxidizing eugenol with ozone according to any one of claim 7, wherein the method comprises the following steps: the solvent is ethanol water solution.
9. The method for synthesizing vanillin by oxidizing eugenol with ozone according to any one of claims 1 to 4, wherein the method comprises the following steps: the reducing agent is zinc powder and/or sodium metabisulfite.
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