CN106520898A - Refining method of novel menthol - Google Patents
Refining method of novel menthol Download PDFInfo
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- CN106520898A CN106520898A CN201610934955.3A CN201610934955A CN106520898A CN 106520898 A CN106520898 A CN 106520898A CN 201610934955 A CN201610934955 A CN 201610934955A CN 106520898 A CN106520898 A CN 106520898A
- Authority
- CN
- China
- Prior art keywords
- menthol
- lipase
- purification
- sodium alginate
- dissolved
- Prior art date
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- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229940041616 menthol Drugs 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 25
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 title claims 5
- 238000007670 refining Methods 0.000 title abstract description 5
- NOOLISFMXDJSKH-KXUCPTDWSA-N (-)-Menthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@H]1O NOOLISFMXDJSKH-KXUCPTDWSA-N 0.000 claims abstract description 39
- 239000004367 Lipase Substances 0.000 claims abstract description 28
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical class [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 claims abstract description 22
- 235000010410 calcium alginate Nutrition 0.000 claims abstract description 19
- 239000000648 calcium alginate Substances 0.000 claims abstract description 19
- 229960002681 calcium alginate Drugs 0.000 claims abstract description 19
- 102000004882 Lipase Human genes 0.000 claims abstract description 15
- 108090001060 Lipase Proteins 0.000 claims abstract description 15
- 235000019421 lipase Nutrition 0.000 claims abstract description 15
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 37
- 235000010413 sodium alginate Nutrition 0.000 claims description 37
- 239000000661 sodium alginate Substances 0.000 claims description 37
- 229940005550 sodium alginate Drugs 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 20
- 102000004190 Enzymes Human genes 0.000 claims description 18
- 108090000790 Enzymes Proteins 0.000 claims description 18
- 239000004005 microsphere Substances 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 16
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 15
- -1 menthol ester Chemical class 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- 238000000746 purification Methods 0.000 claims description 12
- 235000006679 Mentha X verticillata Nutrition 0.000 claims description 11
- 235000002899 Mentha suaveolens Nutrition 0.000 claims description 11
- 235000001636 Mentha x rotundifolia Nutrition 0.000 claims description 11
- 210000004556 brain Anatomy 0.000 claims description 11
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 claims description 10
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 239000007853 buffer solution Substances 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000000502 dialysis Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 238000010828 elution Methods 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 2
- 239000001110 calcium chloride Substances 0.000 claims 1
- 229910001628 calcium chloride Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 235000019504 cigarettes Nutrition 0.000 abstract description 7
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 230000003287 optical effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- XJBRSZAYOKVFRH-UHFFFAOYSA-N (5-methyl-2-propan-2-ylcyclohexyl) prop-2-enoate Chemical compound CC(C)C1CCC(C)CC1OC(=O)C=C XJBRSZAYOKVFRH-UHFFFAOYSA-N 0.000 abstract 1
- 238000005886 esterification reaction Methods 0.000 abstract 1
- 235000013599 spices Nutrition 0.000 description 14
- 239000003205 fragrance Substances 0.000 description 8
- 108010093096 Immobilized Enzymes Proteins 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 6
- 235000013305 food Nutrition 0.000 description 6
- 230000002159 abnormal effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 230000035943 smell Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 4
- 108010091086 Recombinases Proteins 0.000 description 4
- 102000018120 Recombinases Human genes 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 235000018102 proteins Nutrition 0.000 description 4
- 102000004169 proteins and genes Human genes 0.000 description 4
- 108090000623 proteins and genes Proteins 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- NALMPLUMOWIVJC-UHFFFAOYSA-N n,n,4-trimethylbenzeneamine oxide Chemical compound CC1=CC=C([N+](C)(C)[O-])C=C1 NALMPLUMOWIVJC-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011697 sodium iodate Substances 0.000 description 3
- 235000015281 sodium iodate Nutrition 0.000 description 3
- 229940032753 sodium iodate Drugs 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 241000208125 Nicotiana Species 0.000 description 2
- 244000061176 Nicotiana tabacum Species 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 235000010443 alginic acid Nutrition 0.000 description 2
- 229920000615 alginic acid Polymers 0.000 description 2
- 238000011914 asymmetric synthesis Methods 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- NEHNMFOYXAPHSD-UHFFFAOYSA-N citronellal Chemical compound O=CCC(C)CCC=C(C)C NEHNMFOYXAPHSD-UHFFFAOYSA-N 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000001727 in vivo Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 230000003252 repetitive effect Effects 0.000 description 2
- 210000000697 sensory organ Anatomy 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019505 tobacco product Nutrition 0.000 description 2
- QMVPMAAFGQKVCJ-SNVBAGLBSA-N (+)-β-citronellol Chemical compound OCC[C@H](C)CCC=C(C)C QMVPMAAFGQKVCJ-SNVBAGLBSA-N 0.000 description 1
- 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
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 1
- 241001474374 Blennius Species 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 241000985905 Candidatus Phytoplasma solani Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-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
- 206010020772 Hypertension Diseases 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
- 235000014435 Mentha Nutrition 0.000 description 1
- 241001072983 Mentha Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- 208000008589 Obesity Diseases 0.000 description 1
- FRYDSOYOHWGSMD-UHFFFAOYSA-N [C].O Chemical compound [C].O FRYDSOYOHWGSMD-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229940025250 camphora Drugs 0.000 description 1
- 239000010238 camphora Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000019522 cellular metabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940099352 cholate Drugs 0.000 description 1
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 1
- BHQCQFFYRZLCQQ-OELDTZBJSA-N cholic acid Chemical compound C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)[C@@H](O)C1 BHQCQFFYRZLCQQ-OELDTZBJSA-N 0.000 description 1
- 229930003633 citronellal Natural products 0.000 description 1
- 235000000983 citronellal Nutrition 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 230000037213 diet Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000000968 intestinal effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 235000020824 obesity Nutrition 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- GOPBSKKOGHDCEH-UHFFFAOYSA-N periodic acid;sodium Chemical compound [Na].OI(=O)(=O)=O GOPBSKKOGHDCEH-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000011321 prophylaxis Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000000391 smoking effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P41/00—Processes using enzymes or microorganisms to separate optical isomers from a racemic mixture
- C12P41/003—Processes using enzymes or microorganisms to separate optical isomers from a racemic mixture by ester formation, lactone formation or the inverse reactions
- C12P41/004—Processes using enzymes or microorganisms to separate optical isomers from a racemic mixture by ester formation, lactone formation or the inverse reactions by esterification of alcohol- or thiol groups in the enantiomers or the inverse reaction
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
- C12N11/10—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a carbohydrate
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
- C12N9/14—Hydrolases (3)
- C12N9/16—Hydrolases (3) acting on ester bonds (3.1)
- C12N9/18—Carboxylic ester hydrolases (3.1.1)
- C12N9/20—Triglyceride splitting, e.g. by means of lipase
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
- C12P7/22—Preparation of oxygen-containing organic compounds containing a hydroxy group aromatic
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12Y—ENZYMES
- C12Y301/00—Hydrolases acting on ester bonds (3.1)
- C12Y301/01—Carboxylic ester hydrolases (3.1.1)
- C12Y301/01003—Triacylglycerol lipase (3.1.1.3)
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- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Zoology (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Genetics & Genomics (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Microbiology (AREA)
- Biotechnology (AREA)
- Biomedical Technology (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
Abstract
The invention provides a refining method of novel menthol. The refining method comprises the following steps: (1) carrying out esterification reaction on menthol, thus synthesizing menthyl acrylate; (2) synthesizing a modified calcium alginate gel carrier, and fixing lipase through the calcium alginate gel carrier; and (3) carrying out chiral resolution on menthol by adopting the fixed lipase, thus obtaining L-menthol. According to the refining method provided by the invention, the used raw materials are safe, the resolution selectivity is high, and the prepared L-menthol is high in optical purity and good in effect when used for cigarettes; the technological conditions are mild, the product can be recycled for a plurality of times, and the application prospect is wide.
Description
Technical field
The invention belongs to spice preparation field, specifically a kind of process for purification of mint brain.
Background technology
Organism perceives spice, the fragrance of essence to be completed by the acceptor molecule of biological internal enzyme or cell surface
, and the acceptor molecule of biological internal enzyme or cell surface is all with chiral molecule, their elementary cell such as carbon
Hydrate, aminoacid etc. are also all chiral, so resulted in the compound with identical chemical constitution, due to them
Chirality it is different and there are different fragrance.1961, Ohloff delivered the perfume (or spice) of first chiral spice (+)-β-citronellol 1
Taste attribute.(+) -1 has citronellal fragrance, and (-) -1 has Oleum Pelargonii Graveolentiss fragrance.Subsequently, it has been found that different enantiomers
The degree that can behave as different fragrance or fragrance is different.The chiral spice of different optical purities can also show different smelling
Threshold.As the chiral spice of enantiomer-pure has many advantages, with more preferable flavouring essence quality compared with racemic mixture, therefore
The chiral importance in spice is increasingly subject to pay attention to.It is quick with technologies such as asymmetric synthesis, bioconversion, separating-purifyings
Development, increasing chirality spice are lifted the veil of mystery, and the application of the chiral spice of enantiomer-pure has become spice
One trend of fragrance industry development, so far, the chiral spice for having document report has reached about 500 kinds.But due to right
The preparation cost for reflecting the pure chiral spice of body is generally higher, and the application of the chiral spice of enantiomer-pure is also very limited.It is chiral fragrant
The research of material is receiving more universal concern in recent years, but the preparation method of many chirality spice also lacks practicality, away from
It is far away from commercial Application.The method of asymmetric synthesis of inexpensive practical is also urgently further to be researched and developed.
For Mentholum, due to there are 3 chiral centres in menthol molecule, there are 8 isomers in theory, 4
To, in racemic compound, D- and MENTHOL are the compounds at present with most important industrial value.But, D- and L- Herba Menthaes
There is huge difference in the abnormal smells from the patient of alcohol.MENTHOL has fresh, brisk, diffusible abnormal smells from the patient, and with sweet pungent stimulation
Property abnormal smells from the patient；Its feature is similar to the key odor of Fructus Piperiss, and D- isomers have pungent penetrating odor, and referred to as wooden sample is thin
Lotus abnormal smells from the patient, micro-strip Camphora abnormal smells from the patient.MENTHOL has very strong cooling effect, and this property is hardly deposited in D- menthols
.The difference of exactly this property causes MENTHOL more much bigger than the value of D- menthol.
Existing MENTHOL has plenty of synthesis, and such as Japanese STOL company passes through isomerisation of olefin technology dissymmetric synthesis
Production, and muguet compound etc. is produced up to over thousands of ton, become the largest example of current chiral catalysis commercial Application.But the L- for synthesizing
The fragrance of menthol does not have the naturally pure and fresh of natural l-menthol, and this is a critical defect for essence and flavoring agent industry；
And the raw material for synthesizing inevitably has the residual of some solvents, chemical reagent, this is for Nicotiana tabacum L. this food service industry
It is a potential safety hazard；And this method separating step is more and yield is not high.Using crystallization process simultaneously more than natural l-menthol
Split, be opposite-handed crystal seed to be separately added in two regions of supersaturated solution, while obtaining two kinds of enantiomer crystallizations.It is this
The fractionation of direct crystallization method is more convenient, economical, but which is of limited application, because only existing with mixture in whole racemic modification
Account for 10%.Therefore carry out fractionation to the racemic menthol (D, MENTHOL) in natural Oleum menthae to have very important significance.
Enzyme is conventional biocatalyzer, can be catalyzed all reactions for constituting cellular metabolism, with general chemical catalysis
Agent is compared enzyme and is had the advantage that：High catalytic efficiency, specificity are strong, and reaction condition is gentle, active controllable, wide material sources.At present,
Enzyme has been widely used for brewageing, detection, medicine, the field such as biochemical industry.Although enzyme can be catalyzed manyization in vivo
Reaction is learned, but it is still defective as industrial catalyst.Because the chemical nature of enzyme is protein, its catalysis characteristics is strictly
Depend on accurate functional localization between the three-D space structure of protein, and substrate and protein active group.Resolvase is deposited
Temperature living, pH value range are narrower, and heat, strong acid, highly basic, organic solvent etc. are not sufficiently stable, and easily inactivation and degeneration, are urging
Also have the shortcomings that other are difficult to overcome in changing reaction, resolvase is not a kind of preferably catalysis for modern industry
Agent.In order to overcome the shortcoming of resolvase, people to start exploration and combine water-soluble enzyme with insoluble carrier, make not
It is dissolved in the derivant of the enzyme of water.Meanwhile, the major part activity of enzyme can be kept again, and is not easily runed off in catalytic reaction, here it is
So-called " immobilized enzyme ".Compared with resolvase, immobilized enzyme is keeping its efficient, single-minded and gentle enzymic catalytic reaction characteristic
While, also with lot of advantages：The stability of enzyme is high；Can repeat or continuous use；From product, segregation ratio relatively holds
Easily；Operation is continuous and controllable；Process is simple；With the effect for adjusting catalytic property；The poisoning of protein is prevented, and prevents micro-
It is biological contaminated.Developed rapidly in ambits such as chemistry, biology, biological engineering, medical science and life sciences, and,
Because with save resources and the energy, reduce or the Impacts on ecology and environment prevented and remedied pollution and the strategy that meets sustainable development will
Ask.
One of major obstacle of immobilized enzyme application is carrier problem.Because carrier must be cheap, it is easy to activates, and prepares
Activity of the immobilized enzyme and stability it is high.The selection of carrier is considered as in terms of two：One is its physics, mechanical performance and chemistry, life
Thing stability；Two is the chemical-bond type that the reactivity of its surface group and enzyme are combined.The immobilized enzyme of function admirable needs root
According to application purpose and enzyme viability, suitable fixation support and process for fixation are selected.
Sodium alginate also known as sodium alginate, seaweed gel, Algin, alginate, are by the natural polysaccharide carbon extracted in Thallus Laminariae (Thallus Eckloniae)
Hydrate.It is widely used in the products such as food, medicine, weaving, printing and dyeing, papermaking, daily-use chemical industry.Sodium alginate is not only one kind
The food additive of safety, and can be as bionic foods or the base material of remedy diet, as it is actually a kind of natural fibre
Dimension element, can slow down the absorption of fatty sugar and cholate, and the effect with triglyceride and blood glucose in reduce serum cholesterol, blood can
The modern diseasies such as prophylaxis of hypertension, diabetes, obesity.It can suppress poisonous metal such as strontium, cadmium, lead etc. in vivo in intestinal
Accumulation, exactly because sodium alginate these important function, are at home and abroad increasingly valued by the people.Japanese's handle is rich in brown
The food of sodium alginate is referred to as " life prolonging food ", and American is then called " marvellous food addition
Agent ".
The content of the invention
For above-mentioned the deficiencies in the prior art, the present invention provides a kind of process for purification of mint brain, and the method material is pacified
Entirely, selectivity height is split, the MENTHOL optical purity of preparation is high, and cigarette is good with effect.
The technical scheme that the present invention is provided：A kind of process for purification of mint brain, comprises the steps：
(1) mol ratio is taken for 1:1～2:1 ethyl acetate and menthol, are dissolved in dehydrated alcohol, are heated to reflux anti-
10h is answered, etoh solvent after stopped reaction, is rotated out, crude product is obtained, with distillation water elution 3 times, menthol ester is obtained；
(2) take sodium alginate, add the distilled water of its 50 times of weight, vibration dissolving, add its weight 1.1%～
10.8% sodium metaperiodate, the lucifuge reaction 24h at 4 DEG C, obtains the sodium alginate for aoxidizing；
Shown in the following reaction equation of chemical reaction process：
(3) by the sodium alginate after oxidation, it is added dropwise in calcium chloride solution, soaks 30-60min, distillation washing 3 times is simultaneously oozed
Analysis, is filtrated to get calcium alginate microsphere；
(4) lipase is taken, the calcium alginate microsphere obtained by step (3) is added, is dissolved in the buffer solution of pH4～6, under room temperature
Stirring 1-3h, with strainer filtering, separates calcium alginate microsphere carrier and filtrate, being fixed lipase；
(5) menthol ester of synthesis in step (1) is weighed, is dissolved in dehydrated alcohol, and is added a certain amount of step (4) institute
The immobilized-lipase for obtaining, in 30-40 DEG C, 150-200r/min stirring 1h-8h, then separates immobilized-lipase and enzymolysis bottom
Thing, that is, the MENTHOL after being split.
The ethyl acetate added in the step (1) and the total amount of menthol and the mass ratio of dehydrated alcohol are 20:90.
Further, in the step (2), the oxidizability of the sodium alginate of gained oxidation is 0.5%～10%.
Further, in the step (3) calcium chloride solution mass fraction be 2%～5%, the sodium alginate of oxidation with
The mass ratio of calcium chloride solution is 1:10-1:50.
Further, in the step (4), the enzyme concentration ratio of lipase is 10-30mg/0.1g calcium alginate microspheres.
Further, in the step (5) menthol ester be dissolved in the ratio that 1mmol is dissolved in 3mL dehydrated alcohol it is anhydrous
In ethanol.
Further, in the step (5) menthol ester and immobilized-lipase reaction ratio 100mL:1g～
100mL:3g。
Beneficial effects of the present invention：The modified calcium alginate of autonomous synthesis is used for the present invention carrier of fixed fat enzyme,
It is prepared for the material with chiral separation performance.The present invention is using the ortho position dihydroxy on repetitives in sodium alginate linear structure
Base, interrupts the C-C keys of connection vicinal hydroxyl groups with oxidants such as sodium metaperiodates, obtains sodium alginate of the surface rich in aldehyde radical, i.e. oxygen
The sodium alginate of change, the sodium alginate of oxidation run into calcium ion can be formed uniqueness gelling performance it is micro- to obtain calcium alginate
Ball, using the aldehyde radical on modified calcium alginate gel surface, is used as the binding site with amino residue on lipase, so as to fixed lipid
Fat enzyme, for the purification of MENTHOL.Gained immobilized-lipase safety, fractionation selectivity are high, the MENTHOL optics of preparation
Purity is high, and cigarette is good with effect；And process conditions are gentle, product can be recycled for multiple times, with wide application prospect.
Specific embodiment
With reference to specific embodiment, the present invention is described further.
Embodiment 1
(1) mol ratio is taken for 1:1 ethyl acetate and menthol, are dissolved in 4.5 times of ethyl acetate and the total matter of menthol
In the dehydrated alcohol of amount, heating reflux reaction 10h rotates out etoh solvent, obtains crude product after stopped reaction, with distillation washing
It is de- 3 times, obtain menthol ester；
(2) sodium alginate is taken, adds the distilled water of its 50 times of weight, vibration dissolving to add the 1.2% of its weight height
Sodium iodate, the lucifuge reaction 24h at 4 DEG C obtain the sodium alginate for aoxidizing, and the oxidizability of the sodium alginate of gained oxidation is
0.9%；
(3) by the sodium alginate after oxidation, it is added dropwise in 2% calcium chloride solution of its 10 times of quality, soaks 35min,
Distillation washing 3 times dialysis, are filtrated to get calcium alginate microsphere；
(4) 10mg lipases are taken, the calcium alginate microsphere obtained by addition/0.1g steps (3) is dissolved in the buffer solution of pH4,
1h is stirred under room temperature, with strainer filtering, calcium alginate microsphere carrier and filtrate, being fixed lipase is separated；
(5) the menthol ester 100mL of synthesis in step (1) is weighed, is dissolved in dehydrated alcohol, and is added a certain amount of step
(4) the immobilized-lipase 1g obtained by, in 32 DEG C, 150r/min stirring 7h, then separates immobilized-lipase and enzymolysis substrate, i.e.,
MENTHOL after being split.
Embodiment 2
(1) mol ratio is taken for 1.4:1 ethyl acetate and menthol, are dissolved in 4.5 times of ethyl acetate and menthol is total
In the dehydrated alcohol of quality, heating reflux reaction 10h rotates out etoh solvent, obtains crude product, uses distilled water after stopped reaction
Eluting 3 times, obtains menthol ester；
(2) sodium alginate is taken, adds the distilled water of its 50 times of weight, vibration dissolving to add the 5.4% of its weight height
Sodium iodate, the lucifuge reaction 24h at 4 DEG C obtain the sodium alginate for aoxidizing, and the oxidizability of the sodium alginate of gained oxidation is
4.7%；
(3) by the sodium alginate after oxidation, it is added dropwise in 3% calcium chloride solution of its 20 times of quality, soaks 50min,
Distillation washing 3 times dialysis, are filtrated to get calcium alginate microsphere；
(4) lipase 16mg is taken, the calcium alginate microsphere obtained by 0.1g steps (3) is added, is dissolved in the buffer solution of pH5,
2.5h is stirred under room temperature, with strainer filtering, calcium alginate microsphere carrier and filtrate, being fixed lipase is separated；
(5) the menthol ester 100mL of synthesis in step (1) is weighed, is dissolved in dehydrated alcohol, and is added a certain amount of step
(4) the immobilized-lipase 2g obtained by, in 35 DEG C, 175r/min stirring 4h, then separates immobilized-lipase and enzymolysis substrate, i.e.,
MENTHOL after being split.
Embodiment 3
(1) mol ratio is taken for 2:1 ethyl acetate and menthol, are dissolved in 4.5 times of ethyl acetate and the total matter of menthol
In the dehydrated alcohol of amount, heating reflux reaction 10h rotates out etoh solvent, obtains crude product after stopped reaction, with distillation washing
It is de- 3 times, obtain menthol ester；
(2) sodium alginate is taken, adds the distilled water of its 50 times of weight, vibration dissolving to add the 10% of its weight height
Sodium iodate, the lucifuge reaction 24h at 4 DEG C obtain the sodium alginate for aoxidizing, and the oxidizability of the sodium alginate of gained oxidation is
9.5%；
(3) by the sodium alginate after oxidation, it is added dropwise in 4% calcium chloride solution of its 50 times of quality, soaks 55min,
Distillation washing 3 times dialysis, are filtrated to get calcium alginate microsphere；
(4) 26mg lipases are taken, the calcium alginate microsphere obtained by 0.1g steps (3) are added, is dissolved in the buffer solution of pH6,
3h is stirred under room temperature, with strainer filtering, calcium alginate microsphere carrier and filtrate, being fixed lipase is separated；
(5) the menthol ester 100mL of synthesis in step (1) is weighed, is dissolved in dehydrated alcohol, and is added a certain amount of step
(4) the immobilized-lipase 3g obtained by, in 40 DEG C, 200r/min stirring 2h, then separates immobilized-lipase and enzymolysis substrate, i.e.,
MENTHOL after being split.
Oxidizability is defined as the mole percent that oxidized uronic acid unit accounts for total sodium alginate uronic acid unit.Oxidation
The measuring method of degree：By the starch indicator of 0.5mL and the sodium alginate soln reaction for just being aoxidized, in sodium alginate soln
There is oxidation-reduction reaction in the sodium metaperiodate that do not consume and sodium iodide, the iodine for discharging and starch generation chromogenic reaction and be in red
Brown, determines its absorbance at 480nm.The amount of remaining sodium metaperiodate is determined by standard curve, minusing obtains periodic acid
Sodium waste amount, so as to obtain the oxidizability of sodium alginate, specific formula for calculation is as follows：
Consumptions of the wherein N for sodium metaperiodate, m0For the quality of sodium alginate before modified, M is sodium alginate repetitives
Relative molecular mass.
The MENTHOL being refining to obtain by unpurified menthol and by the inventive method carries out evaluation of smokeing panel test.From yellow crane
The soft blue not aromatic tobacco in building, menthol is dissolved with 95% ethanol, is sprayed on tobacco shred and is rolled by hand according to 1ppm and smoke panel test
Cigarette.Cigarette sample moisture content, committee are adjusted by (GB/T16447-1996 Nicotiana tabacum L.s and tobacco product adjust the atmospheric environment with test)
Cigarette committee member is commented in support tobacco product quality monitoring testing station tissue Hubei Province, by (GB5606.4-1996 Medicated cigarette sense organ technical requirements)
Regulation, smoked panel test.Smoking result is shown in Table 1.As a result show, immobilized enzyme process after refined MENTHOL perfume quantity,
There is in terms of mouthfeel and smoke transportation obvious advantage, clean level, zest, miscellaneous QI, aroma quality etc. is mainly shown as
The improvement of aspect.Although and immobilized enzyme consumption is big, by enzyme and the covalent bond of carrier, preventing pheron pair well
" pollution " of substrate, while the increase of its consumption compensate for its defect kinetically, can preferably promote MENTHOL
Split, obtain the superior MENTHOL of effect.
The sense organ evaluating meter of 1 menthol of table
The detailed description of specific embodiments of the present invention is the foregoing is only, the present invention is not limited with this, it is all at this
Any modification, equivalent and improvement for being made in the mentality of designing of invention etc., should be included in protection scope of the present invention it
It is interior.
Claims (7)
1. a kind of process for purification of mint brain, it is characterised in that comprise the steps：
(1) mol ratio is taken for 1:1～2:1 ethyl acetate and menthol, are dissolved in dehydrated alcohol, and heating reflux reaction 10h stops
Etoh solvent is rotated out after only reacting, crude product is obtained, with distillation water elution 3 times, menthol ester is obtained；
(2) sodium alginate is taken, adds the distilled water of its 50 times of weight, vibration dissolving to add the 1.1%～10.8% of its weight
Sodium metaperiodate, at 4 DEG C lucifuge reaction 24h, obtain aoxidize sodium alginate；
(3) by the sodium alginate of the oxidation obtained by step (2), it is added dropwise in calcium chloride solution, soaks 30-60min, distillation washing
3 times and dialysis, are filtrated to get calcium alginate microsphere；
(4) lipase is taken, the calcium alginate microsphere obtained by step (3) is added, is dissolved in the buffer solution of pH4～6, stirred under room temperature
1-3h, with strainer filtering, separates calcium alginate microsphere carrier and filtrate, being fixed lipase；
(5) menthol ester of synthesis in step (1) is weighed, is dissolved in dehydrated alcohol, and is added obtained by a certain amount of step (4)
Immobilized-lipase, in 30-40 DEG C, 150-200r/min stirring 1h-8h, then separates immobilized-lipase and enzymolysis substrate, i.e.,
MENTHOL after being split.
2. the process for purification of mint brain according to claim 1, it is characterised in that：Add in the step (1)
The total amount of ethyl acetate and menthol is 20 with the mass ratio of dehydrated alcohol:90.
3. the process for purification of mint brain according to claim 1, it is characterised in that：Gained oxygen in the step (2)
The oxidizability of the sodium alginate of change is 0.5%～10%.
4. the process for purification of mint brain according to claim 1, it is characterised in that：Calcium chloride in the step (3)
The mass fraction of solution is 2～5%, and the sodium alginate of oxidation and the mass ratio of calcium chloride solution are 1:10-1:50.
5. the process for purification of mint brain according to claim 1, it is characterised in that：Lipase in the step (4)
Enzyme concentration ratio be 10-30mg/0.1g calcium alginate microspheres.
6. the process for purification of mint brain according to claim 1, it is characterised in that：Menthol in the step (5)
Ester is dissolved in dehydrated alcohol with the ratio that 1mmol is dissolved in 3mL dehydrated alcohol.
7. the process for purification of mint brain according to claim 1, it is characterised in that：Menthol in the step (5)
Ester is 100mL with the reaction ratio of immobilized-lipase:1g～100mL:3g.
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| WO2020119280A1 (en) * | 2018-12-10 | 2020-06-18 | 华南理工大学 | Method for enzymatic resolution of chiral substance |
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| CN103468779A (en) * | 2013-09-24 | 2013-12-25 | 阜阳市百富安香料有限公司 | Preparation method of L-menthol |
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| CN103468779A (en) * | 2013-09-24 | 2013-12-25 | 阜阳市百富安香料有限公司 | Preparation method of L-menthol |
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