CN115073340B - Synthesis method of canthaxanthin - Google Patents
Synthesis method of canthaxanthin Download PDFInfo
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- CN115073340B CN115073340B CN202210748643.9A CN202210748643A CN115073340B CN 115073340 B CN115073340 B CN 115073340B CN 202210748643 A CN202210748643 A CN 202210748643A CN 115073340 B CN115073340 B CN 115073340B
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- FDSDTBUPSURDBL-LOFNIBRQSA-N canthaxanthin Chemical compound CC=1C(=O)CCC(C)(C)C=1/C=C/C(/C)=C/C=C/C(/C)=C/C=C/C=C(C)C=CC=C(C)C=CC1=C(C)C(=O)CCC1(C)C FDSDTBUPSURDBL-LOFNIBRQSA-N 0.000 title claims abstract description 72
- OOUTWVMJGMVRQF-DOYZGLONSA-N Phoenicoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)C(=O)C(O)CC1(C)C)C=CC=C(/C)C=CC2=C(C)C(=O)CCC2(C)C OOUTWVMJGMVRQF-DOYZGLONSA-N 0.000 title claims abstract description 36
- 235000012682 canthaxanthin Nutrition 0.000 title claims abstract description 36
- 239000001659 canthaxanthin Substances 0.000 title claims abstract description 36
- 229940008033 canthaxanthin Drugs 0.000 title claims abstract description 36
- 238000001308 synthesis method Methods 0.000 title claims abstract description 14
- OENHQHLEOONYIE-UKMVMLAPSA-N all-trans beta-carotene Natural products CC=1CCCC(C)(C)C=1/C=C/C(/C)=C/C=C/C(/C)=C/C=C/C=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C OENHQHLEOONYIE-UKMVMLAPSA-N 0.000 claims abstract description 46
- 235000013734 beta-carotene Nutrition 0.000 claims abstract description 46
- 239000011648 beta-carotene Substances 0.000 claims abstract description 46
- OENHQHLEOONYIE-JLTXGRSLSA-N β-Carotene Chemical compound CC=1CCCC(C)(C)C=1\C=C\C(\C)=C\C=C\C(\C)=C\C=C\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C OENHQHLEOONYIE-JLTXGRSLSA-N 0.000 claims abstract description 46
- TUPZEYHYWIEDIH-WAIFQNFQSA-N beta-carotene Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CCCC1(C)C)C=CC=C(/C)C=CC2=CCCCC2(C)C TUPZEYHYWIEDIH-WAIFQNFQSA-N 0.000 claims abstract description 45
- 229960002747 betacarotene Drugs 0.000 claims abstract description 45
- 239000007800 oxidant agent Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 37
- 230000001590 oxidative effect Effects 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000013078 crystal Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 81
- 239000000243 solution Substances 0.000 claims description 44
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 41
- 239000000047 product Substances 0.000 claims description 24
- 229910001463 metal phosphate Inorganic materials 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 17
- 229910052723 transition metal Inorganic materials 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- 239000006227 byproduct Substances 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- -1 transition metal salt Chemical class 0.000 claims description 11
- 239000011575 calcium Substances 0.000 claims description 8
- 150000007522 mineralic acids Chemical class 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 10
- 238000010189 synthetic method Methods 0.000 claims 10
- 229910052742 iron Inorganic materials 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 abstract description 11
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000006317 isomerization reaction Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000010791 quenching Methods 0.000 abstract description 2
- 230000000171 quenching effect Effects 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 238000004458 analytical method Methods 0.000 description 28
- 238000005070 sampling Methods 0.000 description 12
- 239000007791 liquid phase Substances 0.000 description 9
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000004321 preservation Methods 0.000 description 5
- 235000005074 zinc chloride Nutrition 0.000 description 4
- 239000011592 zinc chloride Substances 0.000 description 4
- KKAJSJJFBSOMGS-UHFFFAOYSA-N 3,6-diamino-10-methylacridinium chloride Chemical compound [Cl-].C1=C(N)C=C2[N+](C)=C(C=C(N)C=C3)C3=CC2=C1 KKAJSJJFBSOMGS-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- AUNGANRZJHBGPY-SCRDCRAPSA-N Riboflavin Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-SCRDCRAPSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 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
- 241000322338 Loeseliastrum Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- ANVAOWXLWRTKGA-XHGAXZNDSA-N all-trans-alpha-carotene Natural products CC=1CCCC(C)(C)C=1/C=C/C(/C)=C/C=C/C(/C)=C/C=C/C=C(C)C=CC=C(C)C=CC1C(C)=CCCC1(C)C ANVAOWXLWRTKGA-XHGAXZNDSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000013793 astaxanthin Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- FDSDTBUPSURDBL-DKLMTRRASA-N canthaxanthin Chemical compound CC=1C(=O)CCC(C)(C)C=1\C=C\C(\C)=C\C=C\C(\C)=C\C=C\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)C(=O)CCC1(C)C FDSDTBUPSURDBL-DKLMTRRASA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000021466 carotenoid Nutrition 0.000 description 1
- 150000001747 carotenoids Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 235000007144 ferric diphosphate Nutrition 0.000 description 1
- 239000011706 ferric diphosphate Substances 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- CADNYOZXMIKYPR-UHFFFAOYSA-B ferric pyrophosphate Chemical compound [Fe+3].[Fe+3].[Fe+3].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O CADNYOZXMIKYPR-UHFFFAOYSA-B 0.000 description 1
- 229940036404 ferric pyrophosphate Drugs 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- LUWAXJZIBNMNDC-UHFFFAOYSA-H tricalcium diphosphate hydrochloride Chemical compound Cl.[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LUWAXJZIBNMNDC-UHFFFAOYSA-H 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
- C07C403/24—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by six-membered non-aromatic rings, e.g. beta-carotene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
Abstract
The invention discloses a synthesis method of canthaxanthin, which takes beta carotene as a raw material and generates canthaxanthin through oxidation reaction under the action of an oxidant. The selectivity of canthaxanthin prepared by the process is up to 90 percent, and the content of unilateral oxidation products can be effectively controlled to be 0-1wt percent, preferably 0.01-0.8wt percent, more preferably 0.1-0.5wt percent based on the raw material beta carotene. The method does not need further isomerization post-treatment, can obtain crystals with higher purity, has high all-trans content, greatly reduces the solvent consumption, avoids complex operations such as quenching oxidant, washing and the like in the traditional process, and greatly reduces the production cost.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a synthesis method of canthaxanthin.
Background
Canthaxanthin, also known as canthaxanthin, beta-carotene-4, 4' -dione, calico red, is an important carotenoid. The canthaxanthin is widely applied to the aspects of nutrition fortification, coloring and the like of foods and feeds due to the oxidation resistance and the coloring performance of the canthaxanthin.
At present, canthaxanthin is mainly prepared by a chemical method. The chemical synthesis has low cost, high content and stable production, thereby obtaining market acceptance. The patents EP1253131A1 and CN1417207A, CN110372555A report that the method for preparing canthaxanthin by using beta-carotene as raw material is a one-step oxidation method, so that the method has the characteristics of easy operation, simple equipment and the like.
But the solubility of beta-carotene and canthaxanthin in a solvent is smaller in the reaction process, and the mass transfer influence in the reaction process is larger, so that a large amount of impurities are generated in the oxidation process, the selectivity is only 70-80%, the trans content of Huang Suquan at the end of the reaction is only 60% due to the existence of the impurities in the reaction liquid, further isomerization reaction treatment is needed, and the low selectivity of the oxidation reaction and the low all-trans content of the product are main factors for restricting the economical efficiency of the oxidation reaction.
Therefore, how to create a synthesis method of canthaxanthin with little solvent consumption, few byproducts, high selectivity and high all-trans content is extremely critical.
Disclosure of Invention
In order to solve the problems, the invention provides a method for synthesizing canthaxanthin, which controls the selectivity and trans-content of canthaxanthin by controlling the content of a single-side product in the reaction process, and has the advantages of high trans-content of the obtained canthaxanthin Huang Suquan, high purity, reduced process flow and reduced production cost.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
a synthesis method of canthaxanthin comprises the steps of dissolving raw material beta-carotene in a solvent, and reacting in the presence of an oxidant to prepare canthaxanthin, wherein the mass content of a unilateral product A is controlled to be 0-1wt%, preferably 0.01-0.8wt%, more preferably 0.1-0.5wt% in the reaction process according to the mass of the added beta-carotene;
the structural formula of the unilateral product A is as follows:
preferably, the oxidizing agent is a transition metal oxide supported metal phosphate.
The transition metal oxide is one or more of oxides of transition metals A titanium, vanadium, manganese, copper and zinc, preferably ZnO.
The metal phosphate is one or more of sodium, potassium, magnesium, calcium, cobalt, titanium and iron phosphate, preferably Ca 3 P 2 O 8 。
Preferably, the mass content of phosphate in the oxidant is 1.0wt% to 50wt%.
Preferably, the preparation method of the oxidant comprises the following steps:
adding inorganic acid solution of metal phosphate into transition metal salt solution, adding ammonia water, collecting the obtained precipitate, and drying to obtain oxidant.
Preferably, the mixing temperature of the transition metal salt and the metal phosphate is 10-90 ℃, preferably 30-80 ℃, and the mass ratio of the metal phosphate to the transition metal salt is 0.05:1-5:1, preferably 0.1:1-1:1. The preferred inorganic acid is one or more of nitric acid, hydrochloric acid and sulfuric acid, preferably hydrochloric acid, and the mass percentage of the metal phosphate in the inorganic acid solution of the metal phosphate is 1-70wt%, preferably 10-50wt%.
The transition metal salt is one or more of transition metal titanium, vanadium, manganese, copper and zinc.
Preferably, the molar ratio of ammonia to transition metal salt in the aqueous ammonia is from 1:1 to 100:1, preferably from 10:1 to 50:1. The mass fraction of the transition metal salt solution is 1 to 80wt%, preferably 10 to 50wt%. After adding ammonia water, stirring and reacting for a period of time, stirring and reacting for 1-12h, preferably 3-8h. .
Further, the synthesis method of canthaxanthin comprises the following steps:
(1) The raw material beta-carotene is dissolved in a solvent, and is added into a reaction kettle for bottom paving in one step under the stirring state. The oxidant is added into the mixture to react for a period of time at a certain temperature, wherein the mass content of the unilateral product A is controlled to be 0-1wt%, preferably 0-0.5wt%, and more preferably 0.01-0.5 wt% in the reaction process.
(2) After the reaction is finished, the reaction solution is rapidly cooled and filtered to separate out crystals, and the content of canthaxanthin and all-trans thereof in the solid is measured.
In the invention, the solvent is one or more of chloroform, dichloromethane, dichloroethane, ethyl acetate, acetone and carbon tetrachloride, preferably dichloromethane. The addition amount of the solvent is 1 to 50 times, preferably 5 to 10 times, the mass of the beta-carotene.
In the invention, the mass ratio of the oxidant to the raw material beta-carotene is 0.01:1-1:0.5, preferably 0.05:1-1:1.
In the present invention, the reaction time is 0.5 to 10 hours, preferably 1 to 5 hours.
The reaction temperature is 10 to 100℃and preferably 50 to 80 ℃.
The reaction speed is 50-800 rpm, preferably 100-500 rpm, and the reaction pressure is 0.01-10.0 MPa, preferably 0.1-5.0 MPa.
In the present invention, the low-temperature crystallization temperature is-30 to 50 ℃, preferably-10 to 20 ℃.
The invention has the beneficial effects that:
(1) The method comprises the steps of preparing canthaxanthin by oxidizing all-trans beta-carotene, firstly generating an all-trans 1 canthaxanthin product (the all-trans structure has the lowest potential energy and is more stable than cis-form), isomerizing the all-trans form under the reaction condition (on metal ions of the active center of a catalyst) to generate cis-form, and finally obtaining a cis/trans-form mixture. The molecular chain of the unilaterally-produced oxidation product with the two end groups containing oxygen groups is more angular Huang Suduan, so that a metal complex can be formed on the surface of the catalyst, and the occurrence rate of isomerization reaction is slowed down. The unilateral product with similar and more polar molecular structure can be adsorbed around the product macromolecule (canthaxanthin), so that the possibility of converting all-trans into cis-form is reduced. By adopting the preparation method, the content of the unilateral oxidation product can be effectively controlled to be 1000-10000ppm.
(2) The method does not need further isomerization post-treatment, so that the crystal with higher purity can be obtained with the total purity of more than 96 percent, the total trans-form content is higher than 90 percent, the canthaxanthin selectivity is up to 90 percent, the solvent consumption is greatly reduced, the complicated operations of quenching oxidants, washing and the like in the traditional process are avoided, and the production cost is greatly reduced.
Drawings
FIG. 1 shows the nuclear magnetic resonance hydrogen spectrum of the single-sided product A.
FIG. 2 shows the nuclear magnetic resonance spectrum of the single-sided product A.
The specific embodiment is as follows:
the reagents of dichloromethane, ethanol, inorganic salt and ammonia water used in the invention are purchased from Shanghai Taitan technology Co., ltd, and beta-carotene is purchased from New and adult Co., ltd, and the purity is 96%.
In the following examples of the present invention, the content and purity of each component were measured and calculated by an external standard method of a high performance liquid chromatograph, and the conversion rate was calculated based on the content of the product; the liquid chromatography conditions were as follows: chromatographic column: waters XSelect HSS T3,4.6 μm×250mm; sample injection amount: 2-10 mu L, and performing fine adjustment according to the condition of the sample; column temperature: 40 ℃; flow rate: 1mL/min; a detector: an ultraviolet detector (UV) with a detection wavelength of 254-400 nm; mobile phase: acetonitrile/0.1% phosphoric acid in water; when in sample measurement, a liquid phase external standard curve is established by a pure product, and the mass fraction (content) of each detection substance is calculated by the linear relation of the concentration and the liquid phase peak area. The analysis of each component in the oxidant is carried out by adopting ion chromatography, and the conditions of the ion chromatography are consistent with those of liquid chromatography.
Single side product ACharacterization: the nuclear magnetic resonance hydrogen spectrum and the carbon spectrum of the molecular structure are respectively shown in figures 1 and 2.
Example 1:
preparation of an oxidant: 100g of 10wt% calcium phosphate hydrochloric acid solution was added to 1000g of 10wt% zinc chloride (0.735 mol) aqueous solution at 30℃and 1030g of 25wt% ammonia (7.35 mol) was added thereto, followed by stirring and mixing for 3 hours, and the obtained precipitate was collected, dried and used as an oxidizing agent, which was designated as ZnO/Ca 3 P 2 O 8 Ca in oxidant 3 P 2 O 8 The mass content of (2) was 14.85%.
Preparing a methylene dichloride solution of beta-carotene with the mass fraction of 16.6wt% (the content of the beta-carotene is 1.0 mol), adding the solution into a reaction kettle at the stirring rotation speed of 100rpm for bottom paving, adding 26.8g of oxidant into the solution, raising the temperature of the reaction kettle to 50 ℃, increasing the pressure to 0.144Mpa, and after 5 hours of heat preservation, ending the reaction.
The mass content of the single side product in the reaction solution (based on the mass of the beta-carotene added at the beginning) is respectively 0.11 percent (1 h of reaction), 0.13 percent, 0.15 percent, 0.18 percent and 0.20 percent (5 h of reaction) in the sampling analysis reaction solution at 1h intervals in the reaction process. After the reaction is finished for 5 hours, sampling analysis shows that the conversion rate of beta-carotene is 97.9%, the selectivity of canthaxanthin is 99.9%, and the actual content of unilateral products in the reaction mixed solution is 333ppm.
After analysis, the materials are rapidly cooled to minus 10 ℃, filtered and dried, the purity of the crystals obtained by solid-liquid phase analysis is 98.9 percent, wherein the mass content of all-trans-angle flavine is 91.5 percent, and analysis shows that trace raw materials of beta carotene and unilateral products are dissolved in the filtrate, thus simply and conveniently realizing the separation of the products, impurities and raw materials
In addition, the total solvent consumption in the oxidation reaction process is calculated to be 6 times of beta-carotene and is far smaller than 20-60 times of that in CN113735753A and 40-60 times of that in CN111825588A, so that the oxidation reaction process is more energy-saving and efficient.
Example 2:
adding 5.0g of 20wt% ferric phosphate hydrochloric acid solution into 100g of 20wt% zinc chloride (0.147 mol) water solution at 40 ℃, adding 412g of 25wt% ammonia water (2.94 mol) into the water solution, stirring and mixing for 4 hours, collecting the obtained precipitate, drying the precipitate to serve as an oxidant, and marking as ZnO/FePO 4 FePO in oxidant 4 The mass content of (2) was 10.25%.
Preparing a dichloromethane solution of beta-carotene with the mass fraction of 14.3wt% (the content of the beta-carotene is 1.0 mol), adding the dichloromethane solution into a reaction kettle at the stirring rotation speed of 200rpm for bottom paving, adding 268g of oxidant into the dichloromethane solution, raising the temperature of the reaction kettle to 60 ℃, increasing the pressure to 0.197Mpa, and after 5h of heat preservation, ending the reaction.
The mass content of the single side product in the reaction solution is respectively (based on the mass of the beta carotene added at the beginning), 0.25%, 0.33%, 0.44%, 0.49% and 0.53% in the sampling analysis at 1 hour interval in the reaction process. After the reaction is finished for 5 hours, the conversion rate of the sampling analysis beta-carotene is 98.2%, the selectivity of canthaxanthin is 97.22%, and the actual content of the unilateral product in the reaction mixed solution is 757ppm.
After analysis, the material was rapidly cooled to-5 ℃ and then filtered and dried, and the purity of the crystals obtained by solid-liquid phase analysis was 98.2%, wherein the mass content of all-trans-angular flavin was 90.3%.
Example 3:
preparation of an oxidant: 100g of hydrochloric acid solution of 50wt% calcium phosphate is added into 100g of copper chloride (0.3875 mol) water with the mass fraction of 50wt% at 50 ℃, 2712.5g of ammonia water (19.375 mol) with the mass fraction of 25wt% is added into the solution, and then the solution is stirred and mixed for 5 hours, the obtained precipitate is collected, dried and used as an oxidant, and the oxidant is named as CuO/Ca 3 P 2 O 8 Ca in oxidant 3 P 2 O 8 The mass content of (2) was 20.5%.
Preparing a dichloromethane solution of beta-carotene with the mass fraction of 9.1wt% (the content of the beta-carotene is 1.0 mol), adding the dichloromethane solution into a reaction kettle at the stirring rotation speed of 500rpm for bottom paving, adding 536.4g of oxidant into the dichloromethane solution, increasing the temperature of the reaction kettle to 80 ℃, increasing the pressure to 0.347Mpa, and preserving the heat for 1h to finish the reaction.
The mass content of the single side product in the reaction solution is respectively (based on the mass of the beta carotene added at the beginning), 0.32%, 0.52%, 0.76%, 0.88% and 0.94% in the sampling analysis at 10min intervals in the reaction process. After the reaction is finished for 1 hour, sampling analysis shows that the conversion rate of beta-carotene is 95.6%, the selectivity of canthaxanthin is 99.06%, and the actual content of unilateral products in the reaction mixed solution is 854.5ppm.
After analysis, the material was rapidly cooled to 20 ℃ and then filtered and dried, and the purity of the crystals obtained by solid-liquid phase analysis was 97.5%, wherein the mass content of all-trans-angular flavine was 90.3%.
Example 4:
preparation of an oxidant: 500g of a sulfuric acid solution of 10wt% magnesium phosphate was added to 1000g of a 10wt% aqueous solution of titanium tetrachloride (0.537 mol) at 50℃and 1030g of 25wt% aqueous ammonia (7.35 mol) was added thereto, followed by stirring and mixing for 6 hours, and the obtained precipitate was collected, dried and used as an oxidizing agent, which was designated as TiO 2 /Mg 3 P 2 O 8 Mg in oxidant 3 P 2 O 8 The mass content of (2) is 20.4%
Preparing a methylene dichloride solution of beta-carotene with the mass fraction of 16.6wt% (the content of the beta-carotene is 1.0 mol), adding the solution into a reaction kettle at the stirring rotation speed of 100rpm for bottom paving, adding 53.6g of oxidant into the solution, raising the temperature of the reaction kettle to 50 ℃, increasing the pressure to 0.144Mpa, and after 5 hours of heat preservation, ending the reaction.
The mass content of the single side product in the reaction solution (based on the mass of the beta-carotene added at the beginning) is respectively 0.03%, 0.17%, 0.25%, 0.046% and 0.845% in the sampling analysis at 1h interval in the reaction process. After the reaction is finished for 5 hours, the conversion rate of the sampling analysis beta-carotene is 98.9%, the selectivity of canthaxanthin is 99.15%, and the actual content of the unilateral product in the reaction mixed solution is 5070ppm.
After analysis, the material was rapidly cooled to-10 ℃ and then filtered and dried, and the purity of the crystals obtained by solid-liquid phase analysis was 98.2%, wherein the mass content of all-trans-angular flavine was 90.1%.
Example 5:
preparation of an oxidant: 200g of hydrochloric acid solution of 50wt% ferric pyrophosphate is added into 1000g of zinc chloride water solution with the mass fraction of 10wt% at 50 ℃, 1030g of ammonia water with the mass fraction of 25wt% is added into the zinc chloride water solution, the mixture is stirred and mixed for 8 hours, the obtained precipitate is collected, dried and used as an oxidant, and the ZnO/Fe is marked as ZnO/Fe 4 (P 2 O 7 ) 3 Mg in oxidant 3 P 2 O 8 The mass content of (2) was 30.6%.
Preparing a methylene dichloride solution of beta-carotene with the mass fraction of 16.6wt% (the content of the beta-carotene is 1.0 mol), adding the solution into a reaction kettle at the stirring rotation speed of 100rpm for bottom paving, adding 26.8g of oxidant into the solution, raising the temperature of the reaction kettle to 50 ℃, increasing the pressure to 0.144Mpa, and after 5 hours of heat preservation, ending the reaction.
The mass content of the single side product in the reaction solution is respectively 0.123%, 0.336%, 0.441%, 0.516% and 0.994% by mass of the beta-carotene added in the process of sampling analysis at 1 hour interval. After the reaction is finished for 5 hours, sampling analysis shows that the conversion rate of beta-carotene is 97.8%, the selectivity of canthaxanthin is 99.0%, and the actual content of unilateral products in the reaction mixed solution is 5964ppm.
After analysis, the material was rapidly cooled to-10 ℃ and then filtered and dried, and the purity of the crystals obtained by solid-liquid phase analysis was 97.6%, wherein the mass content of all-trans-angular flavin was 90.6%
Comparative example 1:
preparing a methylene dichloride solution of beta-carotene with the mass fraction of 16.6wt% (the content of the beta-carotene is 1.0 mol), adding the solution into a reaction kettle at the stirring rotation speed of 100rpm for bottom paving, adding 26.8g of oxidant sodium chlorate solid particles into the solution, raising the temperature of the reaction kettle to 50 ℃, raising the pressure to 0.144Mpa, and finishing the reaction after the heat preservation is carried out for 5 hours. .
After analysis, the material was rapidly cooled to-10 ℃ and then filtered and dried, and the purity of the crystals obtained by solid-liquid phase analysis was 75.0%.
The mass content of the single side product in the reaction solution (based on the mass of the beta-carotene added at the beginning) in the sampling analysis reaction solution at 1 hour interval in the reaction process is respectively 0.65%, 0.78%, 0.94%, 1.24% and 7.51%. After the reaction is finished for 5 hours, sampling analysis is carried out, the conversion rate of beta carotene is 99.9%, the selectivity of canthaxanthin is 75.6%, and the actual mass content of a unilateral product in the reaction mixed solution is 1.073%.
After analysis, the material was rapidly cooled to-10 ℃ and then filtered and dried, and the purity of the crystals obtained by solid-liquid phase analysis was 92.7%, wherein the mass content of all-trans-angular flavin was 79.8%.
As is clear from comparative example 1, when the oxidizing agent contains only the transition metal oxide, the rate of the tandem side reaction is greatly increased, and the content of the single-side product A is increased, which eventually results in the canthaxanthin crystals not reaching the standard.
Claims (36)
1. A synthesis method of canthaxanthin is characterized in that raw material beta-carotene is dissolved in a solvent, and the raw material beta-carotene reacts in the presence of an oxidant to prepare canthaxanthin, wherein the mass content of unilateral product A is controlled to be 0-1wt% in the reaction process according to the mass of the added beta-carotene;
the structural formula of the unilateral product A is as follows:
the oxidant is transition metal oxide loaded metal phosphate;
the transition metal oxide is one or more of transition metal oxides of titanium, copper and zinc; the metal phosphate is one or a mixture of more of metal magnesium, calcium and iron.
2. The method of synthesis according to claim 1, wherein the transition metal oxide is ZnO;
the metal phosphate is Ca 3 P 2 O 8 。
3. The synthetic method according to claim 1, wherein the mass content of the single-side product A is controlled to be 0.01-0.8wt% in the reaction process.
4. The synthetic method according to claim 3, wherein the mass content of the single-side product A is controlled to be 0.1-0.5wt% in the reaction process.
5. The synthetic method according to claim 1, wherein the mass content of phosphate in the oxidizing agent is 1.0wt% to 50wt%.
6. The synthetic method of claim 1 wherein the method of preparing the oxidizing agent comprises the steps of:
adding inorganic acid solution of metal phosphate into transition metal salt solution, adding ammonia water, collecting the obtained precipitate, and drying to obtain oxidant.
7. The method according to claim 6, wherein the mixing temperature of the transition metal salt and the metal phosphate is 10-90 ℃, and the mass ratio of the metal phosphate to the transition metal salt is 0.05:1-5:1.
8. The method according to claim 7, wherein the mixing temperature of the transition metal salt and the metal phosphate is 30-80 ℃, and the mass ratio of the metal phosphate to the transition metal salt is 0.1:1-1:1.
9. The method of synthesis according to claim 6, wherein the inorganic acid is one or more of nitric acid, hydrochloric acid and sulfuric acid.
10. The method of synthesis according to claim 9, wherein the inorganic acid is hydrochloric acid.
11. The synthesis method according to claim 6, wherein the mass percentage of the metal phosphate in the inorganic acid solution of the metal phosphate is 1-70wt%.
12. The synthesis method according to claim 11, wherein the mass percentage of the metal phosphate in the inorganic acid solution of the metal phosphate is 10-50wt%.
13. The method of synthesis according to claim 6, wherein the transition metal salt is one or more of the salts of transition metals titanium, copper and zinc.
14. The method according to claim 6, wherein the molar ratio of ammonia to transition metal salt in the aqueous ammonia is 1:1 to 100:1.
15. The method of claim 14, wherein the molar ratio of ammonia to transition metal salt in the aqueous ammonia is from 10:1 to 50:1.
16. The method according to claim 6, wherein the ammonia is added and then stirred for a period of time, and the stirring is carried out for 1 to 12 hours.
17. The method of synthesis according to claim 16, wherein the reaction is carried out for 3 to 8 hours with stirring after adding ammonia.
18. The synthesis method according to claim 1, wherein the synthesis method of canthaxanthin comprises the steps of:
(1) Dissolving raw material beta-carotene in a solvent, adding the raw material beta-carotene into a reaction kettle for paving the bottom in one step under a stirring state, adding an oxidant into the reaction kettle, and reacting for a period of time at a certain temperature, wherein the mass content of a unilateral product A is controlled to be 0-1wt% in the reaction process;
(2) After the reaction is finished, the reaction solution is rapidly cooled and filtered to separate out crystals, and the content of canthaxanthin and all-trans thereof in the solid is measured.
19. The synthetic method of claim 18 wherein the mass content of the single-side product a is controlled to be 0.01-0.8wt% during the reaction in step (1).
20. The synthesis method according to claim 19, wherein the mass content of the single-side product a is controlled to be 0.1wt% to 0.5wt% in the reaction process of step (1).
21. The method of synthesis according to claim 18, wherein the solvent is one or more of chloroform, dichloromethane, dichloroethane, ethyl acetate, acetone and carbon tetrachloride.
22. The method of synthesis according to claim 21, wherein the solvent is dichloromethane.
23. The synthetic method of claim 18 wherein the solvent is added in an amount of 1 to 50 times the mass of the β -carotene.
24. The synthetic method of claim 23 wherein the solvent is added in an amount of 5 to 10 times the mass of the β -carotene.
25. The synthesis method according to claim 1, wherein the mass ratio of the oxidizing agent to the raw material beta-carotene is 0.01:1-1:0.5.
26. The synthesis process according to claim 25, wherein the mass ratio of the oxidizing agent to the raw material β -carotene is 0.05:1 to 1:1.
27. The synthetic method according to claim 1, wherein the reaction time is 0.5 to 10 hours.
28. The method of claim 27, wherein the reaction time is 1 to 5 hours.
29. The synthetic method according to claim 1, wherein the reaction temperature is 10 to 100 ℃.
30. The method of claim 29, wherein the reaction temperature is 50 to 80 ℃.
31. The method of synthesis according to claim 18, wherein the reaction stirring speed is 50 to 800rpm.
32. The method of claim 31, wherein the reaction stirring speed is 100 to 500rpm.
33. The synthetic method according to claim 1, wherein the reaction pressure is 0.01 to 10.0MPa.
34. The method of synthesis according to claim 33, wherein the reaction pressure is 0.1 to 5.0MPa.
35. The method according to claim 18, wherein the low-temperature crystallization temperature is-30 to 50 ℃.
36. The method according to claim 35, wherein the low-temperature crystallization temperature is-10 to 20 ℃.
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