CN107787313B - 由c6和c5糖制备2,5,6-三羟基-3-己烯酸和2,5-二羟基-3-戊烯酸及其酯 - Google Patents
由c6和c5糖制备2,5,6-三羟基-3-己烯酸和2,5-二羟基-3-戊烯酸及其酯 Download PDFInfo
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- CN107787313B CN107787313B CN201680035463.9A CN201680035463A CN107787313B CN 107787313 B CN107787313 B CN 107787313B CN 201680035463 A CN201680035463 A CN 201680035463A CN 107787313 B CN107787313 B CN 107787313B
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- Prior art keywords
- acid
- dihydroxy
- trihydroxy
- sugar
- lewis acid
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- 235000000346 sugar Nutrition 0.000 title claims abstract description 53
- 150000002148 esters Chemical class 0.000 title claims abstract description 29
- GJPSTUKDZFMWBP-UHFFFAOYSA-N 2,5-dihydroxypent-3-enoic acid Chemical compound OCC=CC(O)C(O)=O GJPSTUKDZFMWBP-UHFFFAOYSA-N 0.000 title claims abstract description 23
- PEPJGLGUVINFJT-UHFFFAOYSA-N OC(C(=O)O)C=CC(CO)O Chemical compound OC(C(=O)O)C=CC(CO)O PEPJGLGUVINFJT-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 150000008163 sugars Chemical class 0.000 title abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 32
- 239000002841 Lewis acid Substances 0.000 claims abstract description 23
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims description 66
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 37
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims description 33
- 239000003054 catalyst Substances 0.000 claims description 32
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 21
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 21
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 150000001720 carbohydrates Chemical class 0.000 claims description 17
- MZKTXBADKDWHNA-UHFFFAOYSA-N COC(C(C=CCO)O)=O Chemical compound COC(C(C=CCO)O)=O MZKTXBADKDWHNA-UHFFFAOYSA-N 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 13
- CTZSOSYDLAWAME-UHFFFAOYSA-N COC(C(C=CC(CO)O)O)=O Chemical compound COC(C(C=CC(CO)O)O)=O CTZSOSYDLAWAME-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 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 claims description 9
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 9
- 239000008103 glucose Substances 0.000 claims description 9
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical group Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 9
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 8
- 229930091371 Fructose Natural products 0.000 claims description 6
- 239000005715 Fructose Substances 0.000 claims description 6
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- SERHXTVXHNVDKA-UHFFFAOYSA-N pantolactone Chemical compound CC1(C)COC(=O)C1O SERHXTVXHNVDKA-UHFFFAOYSA-N 0.000 claims description 6
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- QPBYLOWPSRZOFX-UHFFFAOYSA-J tin(iv) iodide Chemical compound I[Sn](I)(I)I QPBYLOWPSRZOFX-UHFFFAOYSA-J 0.000 claims description 5
- -1 1, 2-dihydroxyethyl Chemical group 0.000 claims description 4
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- JYJIGFIDKWBXDU-MNNPPOADSA-N inulin Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@]1(OC[C@]2(OC[C@]3(OC[C@]4(OC[C@]5(OC[C@]6(OC[C@]7(OC[C@]8(OC[C@]9(OC[C@]%10(OC[C@]%11(OC[C@]%12(OC[C@]%13(OC[C@]%14(OC[C@]%15(OC[C@]%16(OC[C@]%17(OC[C@]%18(OC[C@]%19(OC[C@]%20(OC[C@]%21(OC[C@]%22(OC[C@]%23(OC[C@]%24(OC[C@]%25(OC[C@]%26(OC[C@]%27(OC[C@]%28(OC[C@]%29(OC[C@]%30(OC[C@]%31(OC[C@]%32(OC[C@]%33(OC[C@]%34(OC[C@]%35(OC[C@]%36(O[C@@H]%37[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O%37)O)[C@H]([C@H](O)[C@@H](CO)O%36)O)[C@H]([C@H](O)[C@@H](CO)O%35)O)[C@H]([C@H](O)[C@@H](CO)O%34)O)[C@H]([C@H](O)[C@@H](CO)O%33)O)[C@H]([C@H](O)[C@@H](CO)O%32)O)[C@H]([C@H](O)[C@@H](CO)O%31)O)[C@H]([C@H](O)[C@@H](CO)O%30)O)[C@H]([C@H](O)[C@@H](CO)O%29)O)[C@H]([C@H](O)[C@@H](CO)O%28)O)[C@H]([C@H](O)[C@@H](CO)O%27)O)[C@H]([C@H](O)[C@@H](CO)O%26)O)[C@H]([C@H](O)[C@@H](CO)O%25)O)[C@H]([C@H](O)[C@@H](CO)O%24)O)[C@H]([C@H](O)[C@@H](CO)O%23)O)[C@H]([C@H](O)[C@@H](CO)O%22)O)[C@H]([C@H](O)[C@@H](CO)O%21)O)[C@H]([C@H](O)[C@@H](CO)O%20)O)[C@H]([C@H](O)[C@@H](CO)O%19)O)[C@H]([C@H](O)[C@@H](CO)O%18)O)[C@H]([C@H](O)[C@@H](CO)O%17)O)[C@H]([C@H](O)[C@@H](CO)O%16)O)[C@H]([C@H](O)[C@@H](CO)O%15)O)[C@H]([C@H](O)[C@@H](CO)O%14)O)[C@H]([C@H](O)[C@@H](CO)O%13)O)[C@H]([C@H](O)[C@@H](CO)O%12)O)[C@H]([C@H](O)[C@@H](CO)O%11)O)[C@H]([C@H](O)[C@@H](CO)O%10)O)[C@H]([C@H](O)[C@@H](CO)O9)O)[C@H]([C@H](O)[C@@H](CO)O8)O)[C@H]([C@H](O)[C@@H](CO)O7)O)[C@H]([C@H](O)[C@@H](CO)O6)O)[C@H]([C@H](O)[C@@H](CO)O5)O)[C@H]([C@H](O)[C@@H](CO)O4)O)[C@H]([C@H](O)[C@@H](CO)O3)O)[C@H]([C@H](O)[C@@H](CO)O2)O)[C@@H](O)[C@H](O)[C@@H](CO)O1 JYJIGFIDKWBXDU-MNNPPOADSA-N 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 229920000945 Amylopectin Polymers 0.000 claims description 3
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 claims description 3
- 229920001202 Inulin Polymers 0.000 claims description 3
- 229930182830 galactose Natural products 0.000 claims description 3
- 229940029339 inulin Drugs 0.000 claims description 3
- BJHIKXHVCXFQLS-PQLUHFTBSA-N keto-D-tagatose Chemical compound OC[C@@H](O)[C@H](O)[C@H](O)C(=O)CO BJHIKXHVCXFQLS-PQLUHFTBSA-N 0.000 claims description 3
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 3
- LTSUHJWLSNQKIP-UHFFFAOYSA-J tin(iv) bromide Chemical compound Br[Sn](Br)(Br)Br LTSUHJWLSNQKIP-UHFFFAOYSA-J 0.000 claims description 3
- 229910021623 Tin(IV) bromide Inorganic materials 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims description 2
- 239000006188 syrup Substances 0.000 claims description 2
- 235000020357 syrup Nutrition 0.000 claims description 2
- ZSUXOVNWDZTCFN-UHFFFAOYSA-L tin(ii) bromide Chemical compound Br[Sn]Br ZSUXOVNWDZTCFN-UHFFFAOYSA-L 0.000 claims 2
- JTDNNCYXCFHBGG-UHFFFAOYSA-L tin(ii) iodide Chemical compound I[Sn]I JTDNNCYXCFHBGG-UHFFFAOYSA-L 0.000 claims 2
- 230000010933 acylation Effects 0.000 claims 1
- 238000005917 acylation reaction Methods 0.000 claims 1
- 230000029936 alkylation Effects 0.000 claims 1
- 238000005804 alkylation reaction Methods 0.000 claims 1
- 230000009435 amidation Effects 0.000 claims 1
- 238000007112 amidation reaction Methods 0.000 claims 1
- 238000004440 column chromatography Methods 0.000 claims 1
- 238000002425 crystallisation Methods 0.000 claims 1
- 230000008025 crystallization Effects 0.000 claims 1
- 238000001212 derivatisation Methods 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 claims 1
- 238000006884 silylation reaction Methods 0.000 claims 1
- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 14
- 239000000758 substrate Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 10
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 10
- 229940057867 methyl lactate Drugs 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 10
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 235000014633 carbohydrates Nutrition 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 238000005112 continuous flow technique Methods 0.000 description 3
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- PHZLMBHDXVLRIX-UHFFFAOYSA-M potassium lactate Chemical compound [K+].CC(O)C([O-])=O PHZLMBHDXVLRIX-UHFFFAOYSA-M 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 2
- IWHLYPDWHHPVAA-UHFFFAOYSA-N 6-hydroxyhexanoic acid Chemical compound OCCCCCC(O)=O IWHLYPDWHHPVAA-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001722 carbon compounds Chemical class 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 2
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- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
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- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
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- NGCDGPPKVSZGRR-UHFFFAOYSA-J 1,4,6,9-tetraoxa-5-stannaspiro[4.4]nonane-2,3,7,8-tetrone Chemical compound [Sn+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O NGCDGPPKVSZGRR-UHFFFAOYSA-J 0.000 description 1
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
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- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
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- LKDRXBCSQODPBY-AMVSKUEXSA-N L-(-)-Sorbose Chemical compound OCC1(O)OC[C@H](O)[C@@H](O)[C@@H]1O LKDRXBCSQODPBY-AMVSKUEXSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920000057 Mannan Polymers 0.000 description 1
- 238000012565 NMR experiment Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PYMYPHUHKUWMLA-LMVFSUKVSA-N Ribose Natural products OC[C@@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-LMVFSUKVSA-N 0.000 description 1
- 229910008449 SnF 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- HMFHBZSHGGEWLO-UHFFFAOYSA-N alpha-D-Furanose-Ribose Natural products OCC1OC(O)C(O)C1O HMFHBZSHGGEWLO-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
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- 150000001649 bromium compounds Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
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- 230000003197 catalytic effect Effects 0.000 description 1
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- 229920002678 cellulose Polymers 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
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- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000003818 flash chromatography Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002663 humin Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000012613 in situ experiment Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003893 lactate salts Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 150000002739 metals Chemical group 0.000 description 1
- JBKTVPSFVUFSAO-UHFFFAOYSA-N methyl 2-hydroxybut-3-enoate Chemical compound COC(=O)C(O)C=C JBKTVPSFVUFSAO-UHFFFAOYSA-N 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000001521 potassium lactate Substances 0.000 description 1
- 235000011085 potassium lactate Nutrition 0.000 description 1
- 229960001304 potassium lactate Drugs 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 description 1
- HIAIVILTZQDDNY-UHFFFAOYSA-J tin(4+);trifluoromethanesulfonate Chemical compound [Sn+4].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F HIAIVILTZQDDNY-UHFFFAOYSA-J 0.000 description 1
- YUOWTJMRMWQJDA-UHFFFAOYSA-J tin(iv) fluoride Chemical class [F-].[F-].[F-].[F-].[Sn+4] YUOWTJMRMWQJDA-UHFFFAOYSA-J 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 229920001221 xylan Polymers 0.000 description 1
- 150000004823 xylans Chemical class 0.000 description 1
- 125000000969 xylosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)CO1)* 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
-
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/40—Unsaturated compounds
- C07C59/42—Unsaturated compounds containing hydroxy or O-metal groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B01J29/00—Catalysts comprising molecular sieves
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- B01J29/7057—Zeolite Beta
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Abstract
本发明涉及在路易斯酸材料的存在下由C6和C5糖制备2,5,6‑三羟基‑3‑己烯酸和2,5‑二羟基‑3‑戊烯酸或其酯,其中2,5,6‑三羟基‑3‑己烯酸和2,5‑二羟基‑3‑戊烯酸或其酯的收率超过15%。
Description
描述:
本发明涉及在路易斯酸催化剂存在下由C6和C5糖制备和回收2,5,6-三羟基-3-己烯酸和2,5-二羟基-3-戊烯酸及其酯。
背景:
碳水化合物代表了生物质的最大部分,并且正在建立其有效用作制备商业化学品的原料的各种策略。生物质由于其作为补充物的潜力,并最终取代石油作为用于此目的的原料而具有特别受关注的。由生物质获得的碳水化合物包含C6和C5糖,并且由于它们是高度官能化的短链碳化合物的潜在来源而在工业上受到特别的关注。这对于市售不可得的高度官能化的短链碳化合物例如2,5,6-三羟基-3-己烯酸和2,5-二羟基-3-戊烯酸及其酯是特别重要的。命名这些化合物的一般方法是α-羟基-β-烯-酸及其酯。这种化合物的一般分子结构是
R'-HC=CH-CHOH-COOR (I)
其中R'和R表示-H、-烷基或羟烷基。目前,2,5,6-三羟基-3-己烯酸和2,5-二羟基-3-戊烯酸是通过纤维素的碱性降解制备的:Svensk Papperstidning(1974)16,p 593-602和J.Appl.Polymer Sci.(1978)22,pp 615-623;以及mannan:Acta Chem Scan.(1980)40,pp 9-14。然而,这些反应的产物组成包含许多化合物,因此所得产物收率低(5mg/g产物)。另外,由于在该工艺中产生多种反应产物,所提出的方法在工业上是不可行的。
已知包含C6和/或C5糖的糖组合物可以是在Sn-BEA存在下制备乳酸甲酯中的底物。EP 2 184 270 B1和Science(2010)328,pp 602–605分别报导了在160℃下在甲醇中来自蔗糖、葡萄糖和果糖的乳酸甲酯的收率分别为64%、43%和44%。然而,观察到与此反应有关的大量副产物,报道的主要副产物是乙烯基乙醇酸甲酯(3-11%)。
已经提出,在所公开的反应过程中可能会产生少量类似于糖精酸的化合物,包括显著量的高极性产物。已经推测这些高极性的产物是C6糖精酸的甲酯。这样的C6糖精酸描述于Carbohydrate Res.(1996)280,pp 47-57。然而,这个参考文献没有提到该化合物的本身、产量百分比和数量,而这些化合物是高极性产物的组分。
Green Chem.(2012)14,pp 702-706公开了与Science(2010)328,pp 602–605相似的反应条件,其中反应温度是变化的。已测定的产品和未转化的糖的总收率为至少51%。
ChemSusChem(2015)8,pp 613-617公开了当在反应过程中加入碱离子时,在非均相硅酸锡催化剂存在下从糖获得的乳酸甲酯收率的增加(从20-25%增加到66-71%)。
因此,希望提供用于制备高官能化的C6和C5化合物的基于路易斯酸的催化方法。另外,希望通过工业上可行的直接选择性方法以高收率提供高官能化的C6和C5化合物。
发明概述
根据本发明,已经发现,通过选择特定的反应条件,例如糖组合物中的糖的浓度、催化剂的量、溶剂和介质的碱度,可以选择性且高收率地由包含一种或多种选自C6和C5糖组成的组中的糖的糖组合物获得α-羟基-β-烯酸如2,5,6-三羟基-3-己烯酸和2,5-二羟基-3-戊烯酸及其酯。
根据本发明,提供了制备下式的α-羟基-β-烯-酸或其酯的方法:
R’-HC=CH-CHOH-COOR (I)
其中R选自-H和C1-C8-烷基组成的组;和
R'是羟甲基或1,2-二羟乙基;
该方法包括以下步骤:
a.使包含一个或多个C6和/或C5糖单元的糖组合物与路易斯酸材料接触;和
b.回收2,5,6-三羟基-3-己烯酸和/或2,5-二羟基-3-戊烯酸或其酯。
该方法的优点是可以高于15%的收率回收2,5,6-三羟基-3-己烯酸或2,5-二羟基-3-戊烯酸及其酯。优选地,酯的收率高于20%、25%、30%。
根据本发明的一个实施方案,C1-C8烷基选自甲基、乙基、丙基、异丙基、丁基、异丁基、戊基、己基、庚基、辛基组成的组。
这种α-羟基-β-烯-酸或其酯是高度官能化的,并且作为平台分子(或基础化学品/中间体),它们提供对化学工业有利的特性,例如用于生产聚酯。它们可以与其它单体例如乳酸或ε-己内酯聚合或共聚。
式(I)化合物是结构上令人感兴趣的分子,可以设想其用于许多应用。该化合物的结构类似于6-羟基己酸的结构,因此式I的化合物可用于类似的应用。然而,与6-羟基己酸不同,式(I)的化合物允许其它官能团,例如作为双键和仲醇,这引入了将其用作官能化聚酯单体的可能性。
2,5-,6-三羟基-3-己烯酸或2,5-二羟基-3-戊烯酸的酯优选为甲酯。2,5,6-三羟基-3-己烯酸甲酯和2,5-二羟基-3-戊烯酸甲酯也可以被称为“THM”和“DPM”。
在没有任何其它说明的情况下,2,5,6-三羟基-3-己烯酸或2,5-二羟基-3-戊烯酸及其酯的收率以基于糖原料的摩尔计算。
糖组合物也可以被称为“糖组合物”或“底物”。在本文中,糖组合物是指溶于溶剂中的糖。类似地,在本文中,术语“糖(saccharide)”、“糖(sugar)”和“底物”可互换使用。糖组合物优选包含一种或多种选自蔗糖、木糖、***糖、甘露糖、塔格糖、半乳糖、葡萄糖、果糖、菊粉、支链淀粉(淀粉)和糖浆组成的组中的C6和/或C5糖单元。表6中可以找到各种糖组合物的使用实例。
根据本发明的一个实施方案,糖组合物(糖组合物)中C6和/或C5化合物(糖单元)的浓度为高于10g/L,优选高于50g/L。在本文中,“C6和/或C5化合物的浓度”是指糖组合物中糖单体的总浓度或组合浓度。
路易斯酸材料作为电子对受体来增加底物的反应性。在本文中,路易斯酸材料催化糖单元(糖)转化为例如2,5,6-三羟基-3-己烯酸和2,5-二羟基-3-戊烯酸及其酯。路易斯酸材料包括锡盐,例如锡氯化物(SnCl4和SnCl2);锡氟化物(SnF4和SnF2);锡溴化物(SnBr4和SnBr2);锡碘化物(SnI4和SnI2);乙酰丙酮锡(SnC10H14O4);焦磷酸锡(Sn2P2O7);乙酸锡(Sn(CH3CO2)4和Sn(CH3CO2)2);草酸锡(Sn(C2O4)2和SnC2O4);三氟甲磺酸锡((CF3SO3)2Sn和(CF3SO3)4Sn)以及以多孔结构存在的材料,如固体路易斯酸。在本文中,路易斯酸材料也可以称为“催化剂”。
固体路易斯酸材料可以是结晶的或非结晶的。非结晶固体路易斯酸材料包括有序介孔无定形材料,例如Sn-MCM-41和Sn-SBA-15;或其他介孔无定形形式。结晶微孔材料包括沸石材料和类沸石(zeotype)材料。有时通过在高于400℃的温度下煅烧材料来再生路易斯酸材料是有利的,以保持2,5,6-三羟基-3-己烯酸和2,5-二羟基-3-戊烯酸和其酯的高选择性和/或收率。
沸石材料是微孔晶体结构的结晶铝硅酸盐。
类沸石材料是其中沸石材料的铝原子部分或全部被金属(金属原子)如锆(Zr)、钛(Ti)和锡(Sn)代替的材料。
本发明涉及一种方法,其中路易斯酸材料骨架结构选自由BEA、MFI、FAU、MOR、FER、MWW、MCM-41和SBA-15或其混合物组成的组。
本发明涉及一种方法,其中路易斯酸材料包含活性金属,其选自由Sn、Ti、Pb、Zr、Ge和Hf或其混合物组成的组中的一种或多种。
本发明涉及一种方法,其中路易斯酸材料选自Sn-BEA、Sn-MFI、Sn-FAU、Sn-MOR、Sn-MWW、Sn-MCM-41和Sn-SBA-15、SnCl4、SnCl2或其混合物。优选地,材料是Sn-BEA或Sn-MCM-41或SnCl4。
根据本发明的另一个实施方案,Sn-BEA通过使用氟化氢的直接合成方法或通过表2和表7中收集的后处理方法来制备。EP 1 010 667 B1中描述了直接合成方法的实例。Sn-BEA通过氟化物直接合成法或后处理法制备,以避免在Sn-BEA中存在碱性组分。这样的碱性组分是例如在WO2015/024875 A1中说明的钾离子。优选地,存在于反应溶液中的任何碱性物质以小于0.13mM的浓度或以小于催化剂组合物的0.5重量%的量存在。
在WO2015/024875A1(催化剂A)中说明了用于制备Sn-BEA的后处理方法的实例。氟化氢路线(也称为直接合成工艺)描述于EP 1 010 667 B1中。
根据本发明的方法可以连续流动方法或分批方法进行。在本文中,连续流动方法应理解为长时间地发生的反应或过程,且反应物在溶剂中通过反应室进料。适合大规模生产是连续流方法的一个优点。
根据本发明的另一个实施方案,该方法是连续方法,其中重时空速为0.005至10h-1,如0.01至5h-1或0.05至1h-1。
根据本发明的另一个实施方案,催化剂与底物的比例针对如表4所示的每种糖浓度进行优化,以获得高于15%、20%、25%、30%、35%或甚至高达50%的2,5,6-三羟基-3-己烯酸或2,5-二羟基-3-戊烯酸及其酯的收率。例如,当糖为木糖时,催化剂与底物的质量比(Rm)优选为Rm>0.1,例如0.2;更优选0.1<Rm<0.8,例如0.25<Rm<0.75。
根据本发明的另一方面,所述方法在110℃至200℃,110℃至190℃,110至180℃的温度下,优选140至170℃的温度下进行,如表1所示。
根据本发明的另一方面,溶剂是极性溶剂。极性溶剂是指介电常数超过15的组合物,例如DMSO、二甲基甲酰胺、乙腈、甲醇、乙醇、水或其混合物。使用极性或弱极性溶剂的优点是2,5,6-三羟基-3-己烯酸或2,5-二羟基-3-戊烯酸酯及其酯的收率可以高于20%。优选地,基于初始糖的摩尔数,酯的收率高于25%、30%、35%、40%、45%或甚至高达50%。
根据本发明的一个实施方案,溶剂包含DMSO。令人惊奇的是,2,5,6-三羟基-3-己烯酸(THA)和/或2,5-二羟基-3-戊烯酸(DPA)的收率高于20%,例如高于25、30、35、40或45%,如表8所示。优选地,溶剂包含DMSO和水,其中水的浓度为2至50wt%,如5至30wt%。优选地,溶剂是DMSO和水的混合物。
根据本发明,存在于反应溶液中或路易斯酸材料环境中的碱金属离子浓度保持在小于0.13mM的浓度或保持在小于催化剂组合物的0.5重量%的量。
保持离子浓度低的优点在于,可以得到高于15%的2,5,6-三羟基-3-己烯酸或2,5-二羟基-3-戊烯酸及其酯的收率,如表5所示。酯的收率优选高于20%、25%、30%、35%、40%、45%或甚至高达50%。当存在的碱金属离子的浓度小于0.13mM时,乳酸甲酯的收率保持低于30%,更优选低于20%或15%,结果是糖转化为期望的式I产物的转化率提高。
如本文所用,碱金属离子应理解为源自碱金属元素本身或碱金属的盐的金属离子。更具体地说,碱金属的盐包含至少一种金属离子和至少一种阴离子。金属离子的实例是钾、钠、锂、铷和铯。碱金属盐的实例是碳酸盐、硝酸盐、乙酸盐、乳酸盐、氯化物、溴化物和氢氧化物。盐的实例是K2CO3、KNO3、KCl、乙酸钾(CH3CO2K)、乳酸钾(CH3CH(OH)CO2K)、Na2CO3、Li2CO3、Rb2CO3
此外,根据本发明,式I的化合物,例如2,5,6-三羟基-3-己烯酸或2,5-二羟基-3-戊烯酸和/或其酯在反应介质中的浓度高于10g/L,收率大于15%、20%、25%、30%、35或甚至高达50%。此外,根据本发明,反应组合物中糖的浓度高于5重量%,如表3所示。
实施例:
Sn-BEA的制备:
A.通过直接合成方法(HF路线)制备Sn-BEA的方法
Sn-β沸石是通过修改Valencia等人描述的路线[US6306364 B1]合成的。在典型的合成步骤中,在小心搅拌下将30.6g f原硅酸四乙酯(TEOS,Aldrich,98%)加入到33.1g氢氧化四乙基铵(TEAOH,Sigma-Aldrich,35%水溶液),形成两相溶液。在搅拌~60分钟后,获得一相;滴加溶于2.0mL的去离子水中的五水合氯化锡(IV)(SnCl4·5H2O,Aldrich,98%)。保持搅拌几个小时以使由TEOS水解形成的乙醇蒸发。最后,将在1.6g去离子水中的3.1g氢氟酸(HF,Fluka,47-51%)加入到凝胶中,得到具有以下摩尔组成的固体:1.0Si:0.005Sn:0.02Cl-:0.55TEA+:0.55F-:7.5H2O。然后均质化所有样品并转移到置于不锈钢高压釜中的聚四氟乙烯容器中,随后在140℃放置14天。过滤回收固体,用去离子水洗涤,然后在空气中于80℃下干燥过夜。通过在静态空气中以2℃/min将样品加热至550℃来除去材料中包含的有机模板,并在该温度下保持6小时。
B.通过后处理方法制备Sn-BEA的方法。
根据ChemSusChem 2015,8,613-617中描述的方法制备Sn/β(Si/Sn=125)。将商业沸石β,即(Zeolyst,Si/Al 12.5,NH4+形式)在550℃下煅烧6小时以获得H+形式并在80℃下用10g浓硝酸(HNO3,Sigma-Aldrich,≥65%)/克沸石β粉末处理12小时。过滤得到的固体,用足量的水洗涤,并以2℃/min的斜率在550℃下煅烧6小时以获得脱铝的β。该固体通过初始润湿法浸渍,Si/Sn比为125。为此,将氯化锡(II)(0.128g,Sigma-Aldrich,98%)溶于5.75mL水中并加入到脱铝的5gβ中。浸渍过程后,将样品在110℃下干燥12小时,再在550℃下煅烧6小时。
C.制备Sn-MCM-41的方法
根据Green Chemistry,2011,13,1175-1181中描述的路线制备有序介孔硅酸锡Sn-MCM-41。在典型的合成中,将26.4g硅酸四乙基铵(TMAS,Aldrich,水中15-20wt%,≥99.99%)缓慢加入到13.0g十六烷基三甲基溴化铵(CTABr,Sigma,≥99.0%)溶于38.0g水的溶液中,并将混合物搅拌约1小时。此时,将SnCl4·5H2O和在2.1g水中的盐酸(HCl,Sigma-Aldrich,min.37%)滴加到该溶液中并搅拌1.5小时。向此溶液中加入12.2g TEOS并搅拌3小时,得到一种凝胶组合物:1.0Si:0.005Sn:0.44CTABr:0.27TMA:0.08Cl-:46H2O。然后将样品转移至置于不锈钢高压釜中的特氟隆衬里容器中并置于140℃的预热炉中15小时。过滤回收固体,用充足的水洗涤,然后在80℃下干燥过夜。最后煅烧该材料,其中样品在静态空气中以2℃/min加热至550℃并在该温度下保持6小时。
实施例1:
a.在典型的反应中,将0.150g无碱的Sn-β沸石(Si/Sn=150)、0.45g糖和15.0g无水甲醇(15.0g,Sigma-Aldrich,>99.8%)加入不锈钢的压力容器中(40cc,Swagelok)。将反应器关闭并置于在160℃下的预热油浴中,在700rpm搅拌,使其反应20小时。反应后,通过将反应器浸没在冷水中使容器迅速冷却。通过GC-MS(Agilent 6890,配备有Agilent 5973质量选择检测器的Phenomenex Zebron ZB-5柱)鉴别糖衍生物。
b.或者,将4.0g无水甲醇(Sigma-Aldrich,>99.8%)、0.36g糖(Sigma-Aldrich,>99%)和期望量的无碱的Sn-β加入到5mL玻璃微波瓶(Biotage)中。将反应容器加热至160℃,同时在Biotage引发剂+微波合成仪中以600rpm搅拌2小时。冷却后,过滤样品并随后分析。在相关反应中,通过用1mM K2CO3(Sigma-Aldrich,>99.0%)在甲醇中的标准溶液替换适当部分的甲醇溶剂来添加碱盐,以获得所需浓度。
将无水氯化锡(IV)(Sigma Aldrich,St.Louis,MO,USA)溶解于d6-DMSO(SigmaAldrich)至终浓度为10%(w/v)。将碳水化合物(包括葡萄糖、果糖、核糖、***糖、菊粉、木聚糖和支链淀粉(淀粉))(均来自Sigma Aldrich,Megazymes(Bray,Ireland)Carbosynth(Compton,UK))在1.5ml Eppendorf safelock管中以对应于0.3-1M的糖单体的浓度(30-100mg/500μl终体积)溶解于d6-DMSO中。加入水(D2O)至终体积比(v/v)为0、5、10、15或20%。从储备溶液中加入无水氯化锡(IV),通常至最终的碳水化合物:催化剂摩尔比为10:1。将含有在d6-DMSO中的碳水化合物、10体积%催化剂和特定水部分的反应混合物孵育,同时在Eppendorf热混合器中以600rpm在99℃下振荡20小时。反应后将样品转移到5mm NMR样品管中,并立即在30℃下通过1H和13C NMR光谱分析。由于形成了腐黑物,样品有一些变色,但是其在整个实验中保持透明(尽管稍微着色),且具有最好的THA收率。通过比较底物溶液的13C NMR信号积分和产物混合物的信号积分(均归一化至d6-DMSO信号),并且通过将不与1H NMR谱的羟基区域重叠的信号(该信号包括乳酸酯和乳酸酯低聚物甲基,3-脱氧化合物亚甲基和THA烯烃以及HMF呋喃氢信号)积分来估计收率。当从C6糖获得以%molC计的收率时,乳酸酯的摩尔分数除以因子2。通过将反应混合物从1.5ml Eppendorf safelock管直接转移到NMR管,然后将分光计中的NMR管加热到所需温度来进行原位实验。然后在反应进程后进行含有一系列1H或13C核磁共振光谱的伪2D谱。为了信号识别,记录葡萄糖和木糖衍生的反应混合物的同-和异-核分配谱(homo-and heteronuclear assignment spectra)。所有光谱都记录在配备有TCI Z-梯度低温探头和18.7T磁体(Oxford Magnet Technology,Oxford,UK)的Bruker(Switzerland)Avance II 800MHz光谱仪上,或者记录在配备有室温智能探头的Bruker Avance III 600MHz光谱仪上。用Bruker Topspin 2.1或Bruker Topspin 3.0记录、处理和分析NMR光谱。
实施例2-3:按照实施例1b,其中过程的温度分别升高到170℃和降低到14℃。根据方法A使用的催化剂是Sn-β(Si/Sn=150)。
表1:在不同工艺温度下来自C6糖(葡萄糖)的2,5,6-三羟基-3-己烯酸甲酯(THM)的收率。
实施例 | 温度(℃) | 收率(%) |
1 | 140 | 12 |
2 | 160 | 14.5 |
3 | 170 | 17.3 |
如表1所示,提高温度可以提高收率。
实施例4-6:按照实施例1a,其中在160℃下的原料是木糖,而不是葡萄糖,并使用不同的催化剂。
表2:使用不同催化剂的来自C5糖(木糖)的2,5-二羟基-3-戊烯酸甲酯(PPM)的收率。
实施例 | 催化剂 | 收率(%) |
4 | 方法A(Si/Sn=200) | 27.5 |
5 | 方法A(Si/Sn=150) | 24.5 |
6 | 方法B(Si/Sn=125) | 18.1 |
如表2所示,用于制备催化剂的方法A在给定的条件下提供了增加的收率。
实施例7-10:按照实施例1b,其中在160℃下原料是木糖,并且反应组合物中木糖具有不同的初始浓度wt%。
表3:在160℃下的2,5-二羟基-3-戊烯酸甲酯(PPM)的收率。根据方法A使用的催化剂是Sn-β(Si/Sn=150)。
实施例 | 木糖浓度wt% | DPM收率(%) |
7 | 4.3 | 26 |
8 | 8.3 | 32 |
9 | 15 | 30 |
10 | 23 | 30 |
如表3中所观察到的,似乎较高的木糖浓度导致增加的DPM收率,直到在约7wt%的木糖浓度达到DPM的阈值收率,并且可能在8-9wt%左右具有较小的峰值。这个事实是令人惊讶的,因为糖实验通常以低于5g/L的浓度进行。尤其值得注意的是,高达30g/L的浓度产生与较低浓度相当的DPM收率。当使用高浓度的糖时,获得高收率产物是不常见的。
实施例11-16:按照实施例1b,其中在160℃下原料是木糖,并且使用不同量的催化剂导致不同的催化剂与底物的比例。
表4:2,5-二羟基-3-戊烯酸甲酯(DPM)和乳酸甲酯(ML)的收率,木糖浓度为9wt%。根据方法A使用的催化剂是Sn-β(Si/Sn=150)。
实施例 | 催化剂/底物质量比 | DPM收率(%) | ML收率(%) |
11 | 0 | 0 | 1 |
12 | 0.125 | 15 | 25 |
13 | 0.25 | 23 | 24 |
14 | 0.5 | 32 | 15 |
15 | 0.75 | 30 | 15 |
16 | 1 | 30 | 14 |
如表4所示,当催化剂/底物的比例为0.5时,获得DPM的最高收率。相应地,可以通过调节催化剂/底物的比例来优化DPM的收率。非常值得注意的是,ML的收率随着DPM的增加而同时下降。当使用不同量的催化剂时,这种催化剂选择性的变化非常惊人,并且之前没有报道过。为了获得高收率的DPM,催化剂/底物的比例应当高于0.25。
实施例17-24:按照实施例1b,其中在160℃下原料是木糖,并使用不同浓度的在甲醇中的碱金属离子(K2CO3)。
表5:2,5-二羟基-3-戊烯酸甲酯(DPM)和乳酸甲酯(ML)的收率,木糖浓度为9wt%。根据方法A使用的催化剂是Sn-β(Si/Sn=150)。
如表5所示,碱金属离子的浓度对DPM的收率有影响。如本文所示例的,对于K2CO3,低于0.1mM的碱金属离子浓度导致DPM收率高于20%。ML收率必须保持低于30%。因此,DPM是在反应混合物中发现的主要产物。
实施例25-30:按照实施例1a,其中在160℃下原料是其他糖(而不是葡萄糖)。根据方法B,使用的催化剂是Sn-β(Si/Sn=125)
表6:来自不同糖的2,5,6-三羟基-3-己烯酸甲酯(THM)的收率。根据方法B,使用的催化剂是Sn-β(Si/Sn=125)。
实施例 | 糖 | 收率(%) |
25 | 果糖 | 17.8 |
26 | 甘露糖 | 14.7 |
27 | 山梨糖 | 17.3 |
28 | 半乳糖 | 11.5 |
29 | 塔格糖 | 9.0 |
30 | 蔗糖 | 15.3 |
如表6所示,所有测试的C6单糖和二糖都产生THM。
实施例31-33:按照实施例1在160℃下并且使用不同的催化剂,所述催化剂根据实施例B和C制备。
表7:来自不同催化剂的2,5,6-三羟基-3-己烯酸甲酯(THM)的收率
实施例 | 催化剂 | 收率(%) |
31 | 方法A(Si/Sn=125) | 16.1 |
32 | 方法B(Si/Sn=125) | 13.8 |
33 | 方法C(Si/Sn=125) | 17.7 |
如表7中所见,用于制备催化剂的方法C是优选的。
实施例34-38:在90℃下按照实施例1c进行,并且在DMSO中加入不同量的水。
表8:具有不同量的水的2,5,6-三羟基-3-己烯酸(THA)的收率
实施例 | 水(wt%) | THA收率(%) | HMF收率(%) |
34 | 0 | 20 | 42 |
35 | 5 | 47 | 32 |
36 | 10 | 49 | 25 |
37 | 15 | 48 | 22 |
38 | 20 | 43 | 20 |
如表8所示,溶剂混合物中存在5-15wt%的水是优选的。
实施例39-44:在90℃下按照实施例1c进行,并且在DMSO中来自不同糖的2,5-二羟基-3-戊烯酸。
表9:来自不同糖的2,5,6-三羟基-3-己烯酸(THA)和2,5-二羟基-3-戊烯酸(DPA)的收率
实施例 | 糖 | THA收率(%) | DPA收率(%) |
39 | 葡萄糖 | 49 | - |
40 | 蔗糖 | 44 | - |
41 | 果糖 | 44 | - |
42 | 木糖 | - | 49 |
43 | ***糖 | - | 48 |
44 | 菊粉 | 42 | - |
实施例45:2,5,6-三羟基-3-己烯酸甲酯(THM)和2,5-二羟基-3-戊烯酸甲酯(DPM)的制备、纯化和鉴别:
2,5,6-三羟基-3-己烯酸甲酯(THM)的制备和纯化
将后处理的Sn-β(3g)、葡萄糖(12g,Sigma-Aldrich,>99.0%)和甲醇(200g,Sigma-Aldrich,>99.8%)加入到特氟龙衬里的1L高压釜反应器(Autoclave Engineers)。将反应器密封并加热至160℃,同时在450rpm下搅拌16小时。然后将反应混合物冷却并过滤,得到粗的反应混合物。粗的反应混合物在40℃下减压浓缩。将2.1g浓缩物溶于甲醇中,在硅藻土上蒸发,通过快速柱色谱(硅胶15 40目,CH2Cl2->20:1CH2Cl2:MeOH)纯化,得到0.30g纯的THM。
2,5-二羟基-3-戊烯酸甲酯(PPM)的制备和纯化
将后处理的Sn-β(7.5g)、木糖(30g,Sigma-Aldrich,>99%)、去离子水(3g)和甲醇(300g,Sigmada Aldrich,>99.8%)加入到特氟龙衬里的1L高压釜反应器(AutoclaveEngineers)。将反应器密封并加热至160℃,同时在450rpm下搅拌16小时。然后将反应混合物冷却并过滤,得到包含15-20%DPM的粗反应混合物。粗反应混合物在减压下浓缩。将浓缩物溶于甲醇中,在硅藻土上蒸发,通过干柱真空色谱法(硅胶60(15-40μm),庚烷→乙酸乙酯)纯化,得到纯度>94%的DPM(GC-MS)。
分析与鉴别
在Bruker Ascend 400光谱仪上记录NMR实验,在400MHz记录1H-NMR且在100MHz记录13C-NMR。化学位移以相对于残余溶剂信号的ppm给出,并且以相对于TMS而言低场的形式报告化学位移。在LC-TOF(ES)上记录HRMS。
2,5,6-三羟基-3-己烯酸甲酯(THM)
1H-NMR(400MHz,CD3OD):δ(ppm)5.93(dd,J=15.3,4.3Hz,1H),5.88(dd,J=15.3,4.1Hz,1H),4.69(d,J=4.1Hz,1H),4.14(ddd,J=6.7,4.7,4.1Hz,1H),3.73(s,3H),3.51(dd,J=10.9,4.7Hz,1H)3.45(dd,J=10.9,6,7Hz,1H).13C-NMR(100MHz,CD3OD):δ(ppm)174.6,133.8,129.4,73.4,72.2,67.0,52.6.HRMS(ESI+)m/z,对于C7H12O5[M+Na]+计算为:199.0577;实测为:199.0572。
2,5-二羟基-3-戊烯酸甲酯(DPM)
1H NMR(400MHz,CD3OD)δ5.89(dtd,J=15.5,5.0,1.4Hz,1H),5.72(ddt,J=15.5,5.7,1.7 Hz,1H),4.76(s,4H),4.58(ddt,J=5.7,1.4,1.4 Hz,1H),3.99(ddd,J=5.0,1.6,1.4 Hz,2H),3.63(s,3H),3.21(p,J=3.3,1.6 Hz,1H).13C NMR(101 MHz,CD3OD)δ173.2,132.2,126.8,70.9,61.3,51.2
Claims (24)
1.一种用于制备下式的α-羟基-β-烯-酸或其酯的方法,
R’-HC=CH-CHOH-COOR (I)
其中
R选自-H和C1-C8-烷基;和
R'是羟甲基或1,2-二羟乙基;
所述方法包括以下步骤:
a.使包含一个或多个C6和/或C5糖单元的糖组合物与路易斯酸材料接触;和
b.回收2,5,6-三羟基-3-己烯酸和/或2,5-二羟基-3-戊烯酸或其酯,
其中存在于路易斯酸材料环境中的碱金属离子浓度保持在小于0.13mM的浓度或保持在小于催化剂组合物的0.5重量%的量。
2.根据权利要求1所述的方法,其中2,5,6-三羟基-3-己烯酸或2,5-二羟基-3-戊烯酸的酯是2,5,6-三羟基-3-己烯酸甲酯和2,5-二羟基-3-戊烯酸甲酯。
3.根据权利要求1或2所述的方法,其中所述糖组合物包含一种或多种选自蔗糖、木糖、甘露糖、塔格糖、半乳糖、葡萄糖、果糖、***糖、菊粉、支链淀粉和糖浆组成的组中的C6和/或C5糖单元。
4.根据权利要求1或2所述的方法,其中所述糖组合物含有至少10重量%的糖单元。
5.根据权利要求1或2所述的方法,其中所述糖组合物包含极性溶剂。
6.根据权利要求5所述的方法,其中所述糖组合物包含一种或多种选自甲醇、乙醇、DMSO和水组成的组中的溶剂。
7.根据权利要求1或2所述的方法,其中所述糖组合物中存在的任何碱金属离子以小于0.3mM的浓度存在。
8.根据权利要求1或2所述的方法,其中所述糖组合物中的碱金属离子浓度为小于0.3mM。
9.根据权利要求1或2所述的方法,其中所述路易斯酸材料含有小于0.5重量%的碱金属离子。
10.根据权利要求1或2所述的方法,其中所述路易斯酸材料是Sn-BEA。
11.根据权利要求1或2所述的方法,其中所述路易斯酸材料是Sn-MCM-41。
12.根据权利要求1或2所述的方法,其中所述路易斯酸材料为锡盐。
13.根据权利要求12所述的方法,其中所述锡盐选自SnCl4、SnCl2、SnF4、SnF2、SnBr4、SnBr2、SnI4、SnI2、SnC10H14O4、Sn2P2O7、Sn(CH3CO2)4、Sn(CH3CO2)2、Sn(C2O4)2、SnC2O4、(CF3SO3)2Sn和(CF3SO3)4Sn。
14.根据权利要求1或2所述的方法,其中所述糖组合物在30-190℃的温度下与路易斯酸材料接触。
15.根据权利要求14所述的方法,其中所述温度为80-170℃。
16.根据权利要求1或2所述的方法,其中所述糖组合物与所述路易斯酸材料接触至少10秒的时间。
17.根据权利要求1或2所述的方法,其中所述方法在连续条件下进行。
18.根据权利要求17所述的方法,其中重时空速为0.005至10h-1。
19.根据权利要求1或2所述的方法,其中所述α-羟基-β-烯-酸或其酯经历选自酰化、甲硅烷基化、烷基化、水解、氢化、酰胺化的衍生化。
20.根据权利要求1所述的方法,其中步骤b)包括α-羟基-β-烯-酸或其酯或其衍生物的纯化。
21.根据权利要求20所述的方法,其中所述纯化包括在减压下蒸发所述溶剂。
22.根据权利要求20或21所述的方法,其中所述纯化包括通过柱色谱纯化所述α-羟基-β-烯-酸或其酯或其衍生物。
23.根据权利要求20或21所述的方法,其中所述纯化包括通过蒸馏纯化α-羟基-β-烯-酸或其酯或其衍生物。
24.根据权利要求20或21所述的方法,其中所述纯化包括通过结晶纯化所述α-羟基-β-烯-酸或其酯或其衍生物。
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