CN106565659B - 一种制备维生素e乙酸酯的方法 - Google Patents
一种制备维生素e乙酸酯的方法 Download PDFInfo
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- CN106565659B CN106565659B CN201610934587.2A CN201610934587A CN106565659B CN 106565659 B CN106565659 B CN 106565659B CN 201610934587 A CN201610934587 A CN 201610934587A CN 106565659 B CN106565659 B CN 106565659B
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- Prior art keywords
- catalyst
- chloride
- bromide
- carboxylic acid
- mcm
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- 238000000034 method Methods 0.000 title claims abstract description 66
- ZAKOWWREFLAJOT-CEFNRUSXSA-N D-alpha-tocopherylacetate Chemical compound CC(=O)OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C ZAKOWWREFLAJOT-CEFNRUSXSA-N 0.000 title claims abstract description 37
- ZAKOWWREFLAJOT-UHFFFAOYSA-N d-alpha-Tocopheryl acetate Natural products CC(=O)OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C ZAKOWWREFLAJOT-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229940042585 tocopherol acetate Drugs 0.000 title claims abstract description 37
- 239000003426 co-catalyst Substances 0.000 claims abstract description 38
- 239000002808 molecular sieve Substances 0.000 claims abstract description 30
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 229910001507 metal halide Inorganic materials 0.000 claims abstract description 20
- 150000005309 metal halides Chemical class 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 20
- -1 2,3,5- trimethylhydroquinone diester Chemical class 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000013311 vegetables Nutrition 0.000 claims abstract description 13
- 229910000039 hydrogen halide Inorganic materials 0.000 claims abstract description 6
- 239000012433 hydrogen halide Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000002360 preparation method Methods 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 13
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 12
- JXLWCZWBHZGUEE-UHFFFAOYSA-N (4-acetyloxy-2,3,5-trimethylphenyl) acetate Chemical compound CC(=O)OC1=CC(C)=C(OC(C)=O)C(C)=C1C JXLWCZWBHZGUEE-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 6
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 4
- 229910000043 hydrogen iodide Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 4
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 4
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 238000005660 chlorination reaction Methods 0.000 claims description 3
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910021612 Silver iodide Inorganic materials 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 229910021550 Vanadium Chloride Inorganic materials 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 2
- NKQIMNKPSDEDMO-UHFFFAOYSA-L barium bromide Chemical compound [Br-].[Br-].[Ba+2] NKQIMNKPSDEDMO-UHFFFAOYSA-L 0.000 claims description 2
- 229910001620 barium bromide Inorganic materials 0.000 claims description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 2
- 229910001626 barium chloride Inorganic materials 0.000 claims description 2
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- LSACYLWPPQLVSM-UHFFFAOYSA-N isobutyric acid anhydride Chemical compound CC(C)C(=O)OC(=O)C(C)C LSACYLWPPQLVSM-UHFFFAOYSA-N 0.000 claims description 2
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 claims description 2
- 229910001623 magnesium bromide Inorganic materials 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- NGYIMTKLQULBOO-UHFFFAOYSA-L mercury dibromide Chemical compound Br[Hg]Br NGYIMTKLQULBOO-UHFFFAOYSA-L 0.000 claims description 2
- 239000002923 metal particle Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 claims description 2
- 229940045105 silver iodide Drugs 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- PGAPATLGJSQQBU-UHFFFAOYSA-M thallium(i) bromide Chemical compound [Tl]Br PGAPATLGJSQQBU-UHFFFAOYSA-M 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 229940102001 zinc bromide Drugs 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 1
- 239000000908 ammonium hydroxide Substances 0.000 claims 1
- 229910052790 beryllium Inorganic materials 0.000 claims 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 238000000967 suction filtration Methods 0.000 claims 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims 1
- 150000003624 transition metals Chemical class 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 3
- 239000003381 stabilizer Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000003321 amplification Effects 0.000 abstract 1
- 238000003199 nucleic acid amplification method Methods 0.000 abstract 1
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 21
- 229930003427 Vitamin E Natural products 0.000 description 12
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 12
- 229940046009 vitamin E Drugs 0.000 description 12
- 239000011709 vitamin E Substances 0.000 description 12
- 235000019165 vitamin E Nutrition 0.000 description 12
- 230000008569 process Effects 0.000 description 7
- 239000007848 Bronsted acid Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- AUFZRCJENRSRLY-UHFFFAOYSA-N 2,3,5-trimethylhydroquinone Chemical compound CC1=CC(O)=C(C)C(C)=C1O AUFZRCJENRSRLY-UHFFFAOYSA-N 0.000 description 4
- 239000002841 Lewis acid Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 150000007517 lewis acids Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OXEURVFAJQZVRZ-UHFFFAOYSA-N CC1C(C)=C(O)C=C(C)C1(O)CC(O)=O Chemical class CC1C(C)=C(O)C=C(C)C1(O)CC(O)=O OXEURVFAJQZVRZ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 108090000371 Esterases Proteins 0.000 description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- LWBPNIJBHRISSS-UHFFFAOYSA-L beryllium dichloride Chemical compound Cl[Be]Cl LWBPNIJBHRISSS-UHFFFAOYSA-L 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 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
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
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- 238000003541 multi-stage reaction Methods 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
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- 229960001295 tocopherol Drugs 0.000 description 2
- 206010000234 Abortion spontaneous Diseases 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 208000001034 Frostbite Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010021929 Infertility male Diseases 0.000 description 1
- 208000007466 Male Infertility Diseases 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- TUCNEACPLKLKNU-UHFFFAOYSA-N acetyl Chemical compound C[C]=O TUCNEACPLKLKNU-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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- OVBPIULPVIDEAO-LBPRGKRZSA-N folic acid Chemical compound C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-LBPRGKRZSA-N 0.000 description 1
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Abstract
本发明提供一种制备维生素E乙酸酯的方法,通入卤化氢气体作为催化剂,金属卤化物与金属单质负载在分子筛上作为助催化剂与稳定剂,通过2,3,5‑三甲基氢醌二酯(TMHQ‑DA)与异植物醇(IPL)反应制备维生素E乙酸酯(VEA)。该工艺具有催化剂活性高,对设备腐蚀小,原料可一步直接生成维生素E乙酸酯,产物稳定性好,易实现工业化放大生产。
Description
技术领域
本发明涉及维生素E乙酸酯的制备方法,属于精细化工合成领域。
背景技术
维生素E(Vitamin E)是一种脂溶性维生素,其水解产物为生育酚,是最主要的抗氧化剂之一。生育酚能促进性激素分泌,使男子精子活力和数量增加;使女子雌性激素浓度增高,提高生育能力,预防流产,还可用于防治男性不育症、烧伤、冻伤、毛细血管出血、更年期综合症、美容等方面。维生素E乙酸酯在医药、食品、化妆品、饲料等领域具有广泛的应用前景与市场价值。
德国公开专利文献DE2000111402公开了一种使用卤化锌(Lewis酸)和含水质子酸(Bronsted酸)作为催化剂,通过三甲基氢醌二酯与异植物醇在极性溶剂与水混合物中进行缩合来生产维生素E乙酸酯。这种方法充分的利用了极性溶剂去溶解催化剂便于后期回收套用,然而,其中的含卤化锌废水后期难以处理,且含水质子酸会造成容易造成部分维生素E乙酸酯分解为维生素E及其它杂质,甚至还需通过后续再酯化的方式得到维生素E乙酸酯,流程较为复杂。
欧洲公开专利文献EP1583753(A1)提供了一种使用2,3,6-三甲基氢醌-1-乙酸酯与植物醇或异植物醇或(异)植物醇衍生物在式Mn+(Rl SO3 -)n催化剂存在下,在非质子有机溶剂中反应生成α-生育酚乙酸酯。但是反应产物是含有维生素E乙酸酯、维生素E等的混合物,只有在一种原料大量过量时才能够得到不含维生素E的维生素E乙酸酯产品,这样造成原料的浪费,增加了后处理过程,同时该工艺中使用的催化剂制备工艺非常复杂。
中国公开专利文献CN103396392A提供了一种使用2,3,5-三甲基氢醌与异植物醇在氧化镁负载二氧化硅作为催化剂的条件下,通过反应可以制得维生素E。然而,其所得产品维生素E需要转化为更加稳定的维生素E乙酸酯才更加便于储存。另外,其制备工艺中两种原料2,3,5-三甲基氢醌与异植物醇同时一次投入反应体系,使异植物醇转化为其他杂质的风险增高。
欧洲公开专利文献EP603695提供了在液态或超临界二氧化碳体系中,以酸性催化剂盐酸、氯化锌与离子交换剂为催化剂,通过三甲基氢醌和异植物醇通过缩合反应合成维生素E。该工艺操作过程较为复杂,催化剂回收套用困难,存在设备腐蚀严重与废液处理麻烦的问题。
欧洲公开专利文献EP01104141.5中使用生物酯酶将三甲基氢醌二乙酯先转化为三甲基氢醌-4-乙酸酯,随后进行提纯后通过缩合得到维生素E乙酸酯。然而众所周知,生物酯酶在精细化工生产中实现大规模工业化生产难度较大,而且酶解工艺要求苛刻,因此使得工艺路线更加复杂,经济性降低。
综上可以看出,目前制备维生素E乙酸酯的方法存在催化剂对设备腐蚀或难以回收问题,且工艺路线复杂,需多步反应才能获得最终产品维生素E乙酸酯,部分工艺废液难以处理,环保压力大等问题。因此,需要寻求一种新的维生素E乙酸酯的制备方法解决上述技术问题。
发明内容
本发明的目的是提供一种制备维生素E乙酸酯的方法,以卤化氢气体作为催化剂,金属卤化物与金属单质负载在分子筛上作为助催化剂与稳定剂,2,3,5-三甲基氢醌二酯(TMHQ-DA)与异植物醇(IPL)反应制备维生素E乙酸酯(VEA)。该工艺具有催化剂活性高,对设备腐蚀小,产物稳定性好。
为达到以上发明目的,本发明的技术方案如下:
一种维生素E乙酸酯的制备方法,包括如下步骤:
卤化氢气体作为催化剂,以羧酸酐与羧酸作为混合溶剂的条件下,原料2,3,5-三甲基氢醌二酯(TMHQ-DA)与异植物醇(IPL)进行反应制备得到维生素E乙酸酯(VEA)。
本发明方法中,所述原料2,3,5-三甲基氢醌二酯(TMHQ-DA)与异植物醇(IPL)结构如式(1)与(2)所示:
产物维生素E乙酸酯的结构如式(3)所示:
其中Ac代表CH3CO。
本发明方法中,催化剂卤化氢气体是持续通入反应体系的,所述的催化剂卤化氢气体包含但不限于氯化氢、溴化氢、碘化氢和氟化氢气体中的一种或多种,优选氯化氢、溴化氢和碘化氢中的一种或多种,更优选氯化氢;所述催化剂的总用量为基于2,3,5-三甲基氢醌二酯摩尔量的1-200%,优选为5-100%,更优选为10-30%。
本发明方法中,还包括使用金属卤化物与金属单质负载在分子筛上作为助催化剂,所述助催化剂可表示为A1Xa/A2/分子筛,其中A1Xa为金属卤化物,A2为金属单质。优选地,所述分子筛为MCM-48,优选的助催化剂可将其表示为A1Xa/A2/MCM-48。
本发明中,以所述助催化剂的总重量计,载体分子筛的含量为75-99.8%,金属卤化物A1Xa的含量为0.1-17%,金属单质A2的含量为0.01-10%。
作为一种优选的助催化剂A1Xa/A2/MCM-48,以A1Xa/A2/MCM-48总重量计,MCM-48分子筛载体的含量为92-99.3%,金属卤化物A1Xa的含量为0.5-7%,金属单质A2的含量为0.2-2%。
本发明方法中,所述助催化剂中的金属卤化物选自碱土金属卤化物、过渡金属卤化物和第IIIA族~第VA族金属卤化物中的一种或多种;优选氯化铍、氯化镁、氯化钙、氯化钛、氯化钒、氯化钡、氯化亚铁、氯化铁、氯化亚铜、氯化铜、氯化锰、氯化锌、氯化银、氯化铝、溴化钠、溴化锰、溴化钡、溴化铜、溴化镁、溴化锌、溴化铝、溴化铊、溴化汞、碘化银和碘化锌等中的一种或多种,更优选的是氯化亚铁、氯化铁、氯化铜、氯化锌、氯化铝、溴化铜和溴化铝等中的一种或多种。
本发明方法中,所述的金属单质作为助催化剂中的稳定剂,选自Ti、Fe、Ni、Zn、Ga、Ge、Zr、Mo、Ru、Rh和Pd中的一种或多种,优选Fe、Ni、Zn和Rh中的一种或多种,更优选Fe和/或Zn。
本发明所述助催化剂具有以下特征:以分子筛为助催化剂的载体,以金属卤化物为助催化剂活性组分起助催化作用,金属单质起稳定作用。助催化剂金属卤化物作为一种较弱的Lewis酸,一方面对反应具有协同催化的作用,有助于提高目标产物的转化率与选择性;同时能够对反应中可能存在的少量水进行吸附。金属单质的加入一方面能起到防止产物维生素E乙酸酯发生分解的作用,起稳定作用,另一方面对原料及产物具有还原作用防止原料发生氧化变质。
作为优选的方案,本发明方法中,所述助催化剂A1Xa/A2/MCM-48的制备方法包括以下步骤:
(1)MCM-48分子筛的制备:
将十六烷基三甲基溴化铵(CTAB)加入水中,然后分别加入无水甲醇和浓氨水,常温超声30min后,逐滴加入正硅酸乙酯(TEOS),室温下超声30min后,经抽滤并水洗至pH=7,在90~200℃,优选120℃下干燥1-2.5h,优选2h,并研磨成粉,之后置于马弗炉中450~950℃,优选800℃焙烧4~10h,优选4h,即可得MCM-48分子筛;
(2)A1Xa/A2/MCM-48分子筛的制备:
在惰性气体保护条件下,将金属卤化物A1Xa与纳米级金属颗粒A2加入水中,在常温下充分混合,将上述制备的MCM-48分子筛加入其中,50℃充分混合,然后在100-150℃,优选120℃条件下干燥4-12h,优选6h即可得到A1Xa/A2/MCM-48分子筛。
本发明中,助催化剂A1Xa/A2/MCM-48的制备方法步骤(1)中,浓氨水的浓度为25wt%,各物质的质量用量比为CTAB:水:甲醇:浓氨水:TEOS=10:10-500:10-1000:1-200:1-200。
本发明中,助催化剂A1Xa/A2/MCM-48的制备方法步骤(2)中,各物质的质量用量比为A1Xa:A2:MCM-48:水=1-20:100-600:0.4-10:1000-2000。
采用本发明的方法制备的助催化剂A1Xa/A2/MCM-48属于介孔分子筛,具有约2~10nm左右的均一孔径及两套相互独立的三维螺旋孔道网络结构,其作为助催化剂的热稳定性较好;同时,MCM-48分子筛作为一种孔径大的吸附剂,可很好的吸附反应液中微量的汞、铬、镉、铅、锰、锡、银等离子半径大、不易被微孔分子筛所吸附的重金属离子,从而降低产品中重金属含量,保证维生素E乙酸酯的重金属指标。
本发明可以很好的解决Lewis酸和Bronsted酸对设备的腐蚀问题,催化剂与助催化剂协同作用下使反应活性和产物选择性大大提高,可降低产物水解,提高反应的抗氧化性能,助催化剂中分子筛的引入,使得反应液中重金属含量有所降低。羧酸酐与羧酸作为混合溶剂的应用,可以实现不稳定中间体维生素E完全转化为更加稳定的维生素E乙酸酯。
所述中间体维生素E的结构如下式(4)所示:
本发明方法中,助催化剂在反应体系中是以浆料的形式使用,用量为相对于底物TMHQ-DA用量的0.05-50wt%,优选为0.1-30wt%,更优选为2-15wt%。
本发明方法中,所述的羧酸酐与羧酸混合溶剂中羧酸酐和羧酸的结构如式(5)和式(6)所示:
其中,R和R’分别独立地表示脂肪烃基、脂环烃基或芳香烃基团,优选为C1-6的脂肪烃基团,更优选为C1-4的脂肪烃基团。
所述羧酸酐优选为乙酸酐、丙酸酐、丁酸酐和异丁酸酐中的一种或多种,更优选乙酸酐。
所述羧酸优选为乙酸、丙酸和丁酸中的一种或多种。
本发明方法中,所述的羧酸酐与原料TMHQ-DA的摩尔比在0.05:1-10:1均是合适的,优选摩尔比为0.1:1-5:1,更优选摩尔比为0.2:1-2:1。
本发明方法中,所述的羧酸与原料TMHQ-DA的摩尔比在0.1:1-10:1均是合适的,优选摩尔比为0.5:1-9:1,更优选摩尔比为2:1-8:1。
本发明方法中,所述TMHQ-DA与IPL的摩尔比为1:0.8-2;优选1:0.9-1.1。
本发明方法中,是在反应温度20℃-150℃下进行的,并优选在30℃-100℃,更优选在50℃-90℃。作为优选的方案,若反应温度过低,则反应速率较慢,原料IPL有变质的风险,时间成本增大;若反应温度过高,但产物选择性有所下降。然而在优选的温度范围内,反应可在2~10h内原料TMHQ-DA的转化率高于99%。
本发明所述方法制备得到主产物维生素E乙酸酯选择性可高达98%以上,产品总收率可高达96%以上。
本发明的有益效果在于:
1、首次采用卤化氢气体作为TMHQ-DA与IPL反应制备维生素E乙酸酯的催化剂,能够降低产物维生素E乙酸酯的分解,提高催化效率。与传统的Lewis酸与Bronsted酸作为催化剂相比避免了水的引入,解决对设备的腐蚀问题,从而使产物品质得到提升,产品维生素E乙酸酯更加稳定。
2、助催化剂中将金属卤化物与金属单质负载于分子筛上,可很好的吸附反应液中微量的汞、铬、镉、铅、锰、锡、银等离子半径大、不易被微孔分子筛所吸附的重金属离子,从而降低产品中重金属含量,保证维生素E乙酸酯的重金属指标;同时,使反应废水中的金属离子含量大大降低,使原料及溶剂单耗大大降低。
3、催化剂与助催化剂协同作用下使反应活性和产物选择性大大提高,可降低产物水解,提高反应的抗氧化性能。
4、羧酸酐与羧酸作为混合溶剂的应用,可以实现不稳定中间体维生素E完全转化为更加稳定的维生素E乙酸酯。
5、实现了多步反应到一步反应的高效合并,降低了设备投资和时间成本。
具体实施方法
下面的实施例将对本发明所提供的方法予以进一步的说明,但本发明不限于所列出的实施例,还应包括在本发明所要求的权利范围内其它任何公知的改变。
气相色谱分析条件:安捷伦气相色谱,色谱柱HP-5进行在线测定,二阶程序升温,初始温度100℃,保持2分钟后以5℃/min的速率升至130℃;再以15℃/min的速率升至280℃,保持17分钟。载气高纯N2,分流比100:1。进样温度280℃,检测器为FID,检测器温度300℃。
实施例1
助催化剂1制备方法如下:
MCM-48分子筛制备:取10g十六烷基三甲基溴化铵(CTAB)加入100g纯水中,然后分别加入110g甲醇和20g浓氨水,常温超声30min后,逐滴加入15g正硅酸乙酯(TEOS),室温下超声30min后,经抽滤并用纯水洗至pH=7,在120℃下干燥2h并研磨成粉,之后置于马弗炉中800℃焙烧4h,即可得MCM-48分子筛。
A1Xa/A2/MCM-48分子筛制备:在氮气保护条件下,将2.5g FeCl2与1.0g纳米级Fe颗粒加入400g纯水中,在常温下充分搅拌混合,将制备的MCM-48分子筛60g加入其中,50℃充分搅拌2h,搅拌完毕在120℃条件下干燥6h即可得到FeCl2/Fe/MCM-48分子筛,将此催化剂记为助催化剂1(简写助1,下同)。
实施例2-7
助催化剂2-7制备方法与助催化剂1类似,物料配比与详细物质组成如下表1所示:
表1助催化剂2-7制备原料配方表
实施例8
将70.0gTMHQ-DA、30.2g乙酸酐与142.3g冰醋酸加入500mL三口烧瓶中,加热至70℃使TMHQ-DA全溶,开启搅拌,加入1.40g助催化剂1,以7.4mL/min的速度通入氯化氢气体,随后开始滴加IPL(87.9g),滴加120min,滴加完毕继续反应60min,反应完毕,停止通氯化氢气体,取样分析,原料TMHQ-DA转化率99.6%,产物维生素E乙酸酯选择性98.3%。停止搅拌,静置3min后反应液分两层,上层为维生素E乙酸酯产品相,下层为助催化剂和溶剂相。
实施例9~14
操作方法与实施例8基本相同,物质、配比变化与结果分析如表2所示。
表2实施例9-14物料配比与结果分析
Claims (34)
1.一种维生素E乙酸酯的制备方法,包括如下步骤:
卤化氢气体作为催化剂,金属卤化物与金属单质负载在分子筛上作为助催化剂,以羧酸酐与羧酸作为混合溶剂的条件下,原料2,3,5-三甲基氢醌二酯与异植物醇进行反应制备得到维生素E乙酸酯。
2.根据权利要求1所述的方法,其特征在于,所述催化剂是持续通入反应体系的,所述的催化剂包含氯化氢、溴化氢、碘化氢和氟化氢气体中的一种或多种。
3.根据权利要求2所述的方法,其特征在于,所述的催化剂为氯化氢、溴化氢和碘化氢中的一种或多种。
4.根据权利要求3所述的方法,其特征在于,所述的催化剂为氯化氢。
5.根据权利要求1所述的方法,其特征在于,所述助催化剂表示为A1Xa/A2/分子筛,其中A1Xa为金属卤化物,A2为金属单质;
以所述助催化剂的总重量计,载体分子筛的含量为75-99.8%,金属卤化物A1Xa的含量为0.1-17%,金属单质A2的含量为0.01-10%。
6.根据权利要求5所述的方法,其特征在于,所述分子筛为MCM-48;助催化剂为A1Xa/A2/MCM-48。
7.根据权利要求5所述的方法,其特征在于,以所述助催化剂的总重量计,载体分子筛的含量为92-99.3%,金属卤化物A1Xa的含量为0.5-7%,金属单质A2的含量为0.2-2%。
8.根据权利要求1所述的方法,其特征在于,所述助催化剂中的金属卤化物选自碱土金属卤化物、过渡金属卤化物和第IIIA族~第VA族金属卤化物中的一种或多种;
所述金属单质选自Ti、Fe、Ni、Zn、Ga、Ge、Zr、Mo、Ru、Rh和Pd中的一种或多种。
9.根据权利要求8所述的方法,其特征在于,所述助催化剂中的金属卤化物选自氯化铍、氯化镁、氯化钙、氯化钛、氯化钒、氯化钡、氯化亚铁、氯化铁、氯化亚铜、氯化铜、氯化锰、氯化锌、氯化银、氯化铝、溴化钠、溴化锰、溴化钡、溴化铜、溴化镁、溴化锌、溴化铝、溴化铊、溴化汞、碘化银和碘化锌中的一种或多种。
10.根据权利要求9所述的方法,其特征在于,所述助催化剂中的金属卤化物选自氯化亚铁、氯化铁、氯化铜、氯化锌、氯化铝、溴化铜和溴化铝中的一种或多种。
11.根据权利要求8所述的方法,其特征在于,所述金属单质选自Fe、Ni、Zn和Rh中的一种或多种。
12.根据权利要求11所述的方法,其特征在于,所述金属单质选自Fe和/或Zn。
13.根据权利要求1所述的方法,其特征在于,所述助催化剂的用量为相对于2,3,5-三甲基氢醌二酯用量的0.05-50wt%。
14.根据权利要求13所述的方法,其特征在于,所述助催化剂的用量为相对于2,3,5-三甲基氢醌二酯用量的0.1-30wt%。
15.根据权利要求14所述的方法,其特征在于,所述助催化剂的用量为相对于2,3,5-三甲基氢醌二酯用量的2-15wt%。
16.根据权利要求1所述的方法,其特征在于,所述催化剂的总用量为基于2,3,5-三甲基氢醌二酯摩尔量的1-200%。
17.根据权利要求16所述的方法,其特征在于,所述催化剂的总用量为基于2,3,5-三甲基氢醌二酯摩尔量的5-100%。
18.根据权利要求17所述的方法,其特征在于,所述催化剂的总用量为基于2,3,5-三甲基氢醌二酯摩尔量的10-30%。
19.根据权利要求6所述的方法,其特征在于,制备所述A1Xa/A2/MCM-48,包括以下步骤:
(1)MCM-48分子筛制备:
取一定量十六烷基三甲基溴化铵加入纯水中,然后分别加入无水甲醇和浓氨水,常温超声,逐滴加入一定量正硅酸乙酯,室温下超声后,经抽滤、水洗、干燥焙烧后,可得MCM-48分子筛;
(2)A1Xa/A2/MCM-48分子筛的制备:
在惰性气体保护条件下,将金属卤化物A1Xa与纳米级金属颗粒A2加入一定量的纯水中,在常温下充分搅拌混合,将制备的MCM-48分子筛加入其中,50℃充分混合,干燥后即可得到A1Xa/A2/MCM-48分子筛;
十六烷基三甲基溴化铵:水:甲醇:氨水:正硅酸乙酯=10:10-500:10-1000:1-200:1-200,A1Xa:A2:MCM-48:水=1-20:100-600:0.4-10:1000-2000,以上为质量比。
20.根据权利要求1所述的方法,其特征在于,所述羧酸酐和羧酸分别如式(5)和式(6)所示:
其中,R和R’分别独立地表示脂肪烃基、脂环烃基或芳香烃基团。
21.根据权利要求20所述的方法,其特征在于,R和R’分别独立地表示C1-6的脂肪烃基团。
22.根据权利要求21所述的方法,其特征在于,R和R’分别独立地表示C1-4的脂肪烃基团。
23.根据权利要求20所述的方法,其特征在于,所述羧酸酐为乙酸酐、丙酸酐、丁酸酐和异丁酸酐中的一种或多种。
24.根据权利要求23所述的方法,其特征在于,所述羧酸酐为乙酸酐。
25.根据权利要求20所述的方法,其特征在于,所述羧酸为乙酸、丙酸和丁酸中的一种或多种。
26.根据权利要求1所述的方法,其特征在于,所述羧酸酐与2,3,5-三甲基氢醌二酯的摩尔比为0.05:1-10:1;所述羧酸与2,3,5-三甲基氢醌二酯的摩尔比为0.1:1-10:1。
27.根据权利要求26所述的方法,其特征在于,所述羧酸酐与2,3,5-三甲基氢醌二酯的摩尔比为0.1:1-5:1。
28.根据权利要求27所述的方法,其特征在于,所述羧酸酐与2,3,5-三甲基氢醌二酯的摩尔比为0.2:1-2:1。
29.根据权利要求26所述的方法,其特征在于,所述羧酸与2,3,5-三甲基氢醌二酯的摩尔比为0.5:1-9:1。
30.根据权利要求29所述的方法,其特征在于,所述羧酸与2,3,5-三甲基氢醌二酯的摩尔比为2:1-8:1。
31.根据权利要求1所述的方法,其特征在于,所述2,3,5-三甲基氢醌二酯与异植物醇的摩尔比为1:0.8-2;反应温度为20℃-150℃。
32.根据权利要求31所述的方法,其特征在于,所述2,3,5-三甲基氢醌二酯与异植物醇的摩尔比为1:0.9-1.1。
33.根据权利要求31所述的方法,其特征在于,所述反应温度为30℃-100℃。
34.根据权利要求33所述的方法,其特征在于,所述反应温度为50℃-90℃。
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