CN109705070A - 一种5,5’-二烷氧酰基-[2,2’]联呋喃类化合物的制备方法 - Google Patents
一种5,5’-二烷氧酰基-[2,2’]联呋喃类化合物的制备方法 Download PDFInfo
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- CN109705070A CN109705070A CN201910120276.6A CN201910120276A CN109705070A CN 109705070 A CN109705070 A CN 109705070A CN 201910120276 A CN201910120276 A CN 201910120276A CN 109705070 A CN109705070 A CN 109705070A
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- Prior art keywords
- dialkoxy
- preparation
- acyl groups
- furfuran compound
- join
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Links
- -1 furfuran compound Chemical class 0.000 title claims abstract description 28
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 125000002252 acyl group Chemical group 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 239000003381 stabilizer Substances 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 3
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 3
- 125000003884 phenylalkyl group Chemical group 0.000 claims abstract description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 57
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 21
- 235000011056 potassium acetate Nutrition 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 4
- YNHIGQDRGKUECZ-UHFFFAOYSA-L PdCl2(PPh3)2 Substances [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- LFKXWKGYHQXRQA-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;iron Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LFKXWKGYHQXRQA-FDGPNNRMSA-N 0.000 claims description 2
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 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 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 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 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 2
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical compound [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 125000004802 cyanophenyl group Chemical group 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- OSHOQERNFGVVRH-UHFFFAOYSA-K iron(3+);trifluoromethanesulfonate Chemical compound [Fe+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F OSHOQERNFGVVRH-UHFFFAOYSA-K 0.000 claims description 2
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 claims description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims 2
- MJEMIOXXNCZZFK-UHFFFAOYSA-N ethylone Chemical compound CCNC(C)C(=O)C1=CC=C2OCOC2=C1 MJEMIOXXNCZZFK-UHFFFAOYSA-N 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- 229910001948 sodium oxide Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052725 zinc Inorganic materials 0.000 abstract description 3
- 239000011701 zinc Substances 0.000 abstract description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 68
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 36
- 239000000047 product Substances 0.000 description 35
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 17
- 238000005160 1H NMR spectroscopy Methods 0.000 description 17
- 101150003085 Pdcl gene Proteins 0.000 description 17
- 238000004440 column chromatography Methods 0.000 description 17
- 239000012043 crude product Substances 0.000 description 17
- 229910001873 dinitrogen Inorganic materials 0.000 description 17
- 239000002904 solvent Substances 0.000 description 17
- 238000012512 characterization method Methods 0.000 description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000002240 furans Chemical class 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- QGXJTDHPWUQRFT-UHFFFAOYSA-N 2-methyl-3H-furan-2-carboxylic acid Chemical compound CC1(OC=CC1)C(=O)O QGXJTDHPWUQRFT-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000000052 vinegar Substances 0.000 description 2
- NOOLISFMXDJSKH-KXUCPTDWSA-N (-)-Menthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@H]1O NOOLISFMXDJSKH-KXUCPTDWSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- SBCORMQLNNLHSM-UHFFFAOYSA-N C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.O1C=CC=C1 Chemical compound C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.O1C=CC=C1 SBCORMQLNNLHSM-UHFFFAOYSA-N 0.000 description 1
- KDCYGRMQCBWOSQ-UHFFFAOYSA-N CC1(C(C=CO1)Br)C(=O)O Chemical compound CC1(C(C=CO1)Br)C(=O)O KDCYGRMQCBWOSQ-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropanol Chemical compound CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
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- 238000005859 coupling reaction Methods 0.000 description 1
- KTHXBEHDVMTNOH-UHFFFAOYSA-N cyclobutanol Chemical compound OC1CCC1 KTHXBEHDVMTNOH-UHFFFAOYSA-N 0.000 description 1
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- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
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- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical group O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
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- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 229950009195 phenylpropanol Drugs 0.000 description 1
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- 238000007670 refining Methods 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Landscapes
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种5,5’‑二烷氧酰基‑[2,2’]联呋喃类化合物的制备方法,属于联呋喃类化合物的制备领域。本发明的制备方法将
Description
技术领域
本发明属于高性能聚醋、环氧树脂、聚酞胺和聚氨醋等聚合物单体制备领域,具体涉及一种5,5’-二烷氧酰基-[2,2’]联呋喃类化合物制备方法。
背景技术
随着人们对化石资源的过渡开采,有限的化石资源日益变得枯竭,另外,化石资源炼制过程中带来大量的环境污染和温室效应,因此利用具有生物质来源的平台化合物制备各种官能材料受到各国政府以及学术界的高度重视并投入大量人力物力进行研究。比如呋喃二甲酸因含有刚性的呋喃环和对位的二甲酸基结构,可直接用于聚醋、环氧树脂、聚酞胺、聚氨醋等高性能工程塑料。比如现在利用聚呋喃二甲酸替代传统的对苯二甲酸酯类(PET),其在模量、抗蠕变等方面具有优良的力学性能,同时具有更高的玻璃化转变温度和热变形温度。但是聚呋喃二甲酸再热稳定性上尚有欠缺。最近芬兰科学家JuhaP.Heiskanen(Macromolecules 2018,51,1822-1829)报道联5,5’-二烷氧酰基-[2,2’]联呋喃聚酯的热稳定性较聚呋喃二甲酸具有明显提高。
目前对于联5,5’-二烷氧酰基-[2,2’]联呋喃聚酯单体的合成主要包括以下三种方法,方法一是基于钯催化条件下由2-糠酸甲酯氧化偶联得到,该方法是高压气相反应,温度高,产物中等(Jpn.Kokai Tokkyo Koho,2018150415;Organic Letters,16(10),2732-2735;2014)。方法二是基于钯催化下2-糠酸甲酯和5-溴-2-糠酸甲酯发生中性偶联反应得到,该反应需要在强碱性条件下进行,产率比较低(Macromolecules,51(5),1822-1829;2018)。第三种方法是基于5-溴-2-呋喃糠酸甲酯在NiCl2(PPh3)2催化剂下还原偶联得到,但是该方法需要一当量的金属单质如锌,铟等作为还原剂,不原子经济,成本高(TetrahedronLetters,49(27),4302-4305;2008;Jpn.Kokai Tokkyo Koho,2018150415)。另外使用的Ni催化剂具有环境危害性。以上三种方法的合成路线如下所示:
发明内容
为了克服现有的联5,5’-二烷氧酰基-[2,2’]联呋喃酯合成技术中的缺点与不足,本发明的目的在于提供一种联5,5’-二烷氧酰基-[2,2’]联呋喃酯化合物的制备方法。该方法不需要严格无水条件,不需要使用强碱,不需要高压条件,用廉价的还原剂替代金属锌单质作为还原剂,具有操作简便成本低廉等优势。
本发明的目的通过下述技术方案实现。
一种5,5’-二烷氧酰基-[2,2’]联呋喃类化合物的制备方法,其特征在于,包括如下步骤:
将还原剂、碱、催化剂和稳定剂加入有机溶剂中,氮气或者氩气条件下,回流反应得到5,5’-二烷氧酰基-[2,2’]联呋喃类化合物,结构通式为
其中X=Cl,Br或I;R为C1~C17的饱和脂肪烃、脂环烃、苯基烷基。
优选的,所述5,5’-二烷氧酰基-[2,2’]联呋喃类化合物的结构如下所示:
优选的,所述回流反应的温度为0~160℃。
优选的,所述回流反应的时间为1~60小时。
优选的,所述有机溶剂为苯、甲苯、二甲苯、均三甲苯、氯苯、邻二氯苯、间二氯苯、对二氯苯、氟苯、五氟苯、六氟苯、乙酸乙酯、乙酸叔丁酯、乙酸丙酯、乙腈、苯腈、四氢呋喃、乙醚和1,4-二氧六环中的一种或几种的混合物。
优选的,所述的还原剂为甲醇、乙醇、异丙醇、丁醇,乙二醇,1,3-丙二醇,1,2-丙二醇,丙三醇,1,4丁二醇,葡萄糖和甘露糖中的一种或几种的混合物。
优选的,所述的催化剂为Fe(OAc)2、Cu(OAc)2、Co(OAc)2、Mn(OAc)2、Pd(OAc)2、Pd(PPh3)4、PdCl2、PdCl2(PPh3)2、PdCl2(PPh3)2、Pd2(dba)3、Ni(acac)2、Fe(acac)2、Fe(OTf)2、FeCl2、Fe(acac)3、Fe(OTf)3、FeCl3和FeCl2中的一种或几种的混合物。
优选的,所述稳定剂为聚乙烯吡咯烷酮(缩写PVP,分子量为1~6万)。
优选的,所述的碱为醋酸钾、醋酸钠、醋酸铯、碳酸钾、碳酸钠、碳酸氢钾、碳酸氢钠、氢氧化钠、氢氧化钾、磷酸钠、磷酸钾、磷酸氢钠、磷酸氢钾,三乙胺、吡啶、二异丙基乙基胺和N-甲基吗啡啉的一种或者几种的混合物。
优选的,所述和还原剂的摩尔比为100:1~1:100;所述和碱的摩尔比为100:1~1:1;所述和催化剂的摩尔比为100:1~1:100;所述和稳定剂的摩尔比为100:1~1:1。
优选的,所述和还原剂的摩尔比为100:1~1:1。
本发明相对于现有技术,具有如下的优点与效果:
(1)本发明所用的还原剂是廉价可再生的醇类物质,不需要金属单质;
(2)本发明不需要严格的无水条件和高温高压操作,操作简单,成本低廉。
具体实施方式
下面结合实施例对本发明作进一步详细的描述,但本发明的实施方式不限于此。
实施例1
在25mL schlenk反应管中加入0.015mmol PdCl2(PPh3)2,55.9mgPVP(K30),0.75mmol乙酸钾,氮气条件下,加入2.5ml甲苯,再加入1mmol的乙醇和0.5mmol的110℃下回流反应30小时,减压脱除溶剂得粗产品,然后用快速柱层析分离得产物51mg(74%)。产物的结构表征物理常数:1H NMR(400MHz,CDCl3)δ7.25(d,J=3.6Hz,1H),6.91(d,J=3.6Hz,1H),4.40(q,J=7.1Hz,2H),1.41(t,J=7.1Hz,3H).13C NMR(100MHz,CDCl3)δ158.5,148.2,144.7,119.4,109.3,61.2,14.3.
实施例2
在100mL schlenk反应管中加入0.06mmol PdCl2(PPh3)2,224mgPVP(K30),3mmol乙酸钾,氮气条件下,加入10ml甲苯,再加入4mmol的异丙醇和2mmol的110℃下回流反应30小时,减压脱除溶剂得粗产品,然后用快速柱层析分离得产物220mg(71%)。产物的结构表征物理常数:1H NMR(400MHz,CDCl3)δ7.21(s,2H),6.88(s,2H),5.30–5.17(m,2H),1.37(d,J=5.8Hz,12H).13C NMR(100MHz,CDCl3)δ158.1,148.2,144.9,119.2,109.2,69.0,21.9.
实施例3
在50mL schlenk反应管中加入0.03mmol PdCl2(PPh3)2,112mgPVP(K30),1.5mmol乙酸钾,氮气条件下,加入5ml甲苯,再加入2mmol的正丁醇和1mmol的110℃下回流反应30小时,减压脱除溶剂得粗产品,然后用快速柱层析分离得产物102mg(61%)。产物的结构表征物理常数:1H NMR(400MHz,CDCl3)δ7.25(d,J=3.5Hz,1H),6.91(d,J=3.5Hz,1H),4.35(t,J=6.7Hz,2H),1.81–1.72(m,2H),1.49(d,J=7.5Hz,2H),1.00(t,J=7.5Hz,3H).13C NMR(100MHz,CDCl3)δ158.5,148.2,144.7,119.3,109.3,65.0,30.7,19.1,13.7.
实施例4
在25mL schlenk反应管中加入0.015mmol PdCl2(PPh3)2,55.9mgPVP(K30),0.75mmol乙酸钾,氮气条件下,加入2.5ml甲苯,再加入1mmol的异丁醇和0.5mmol的90℃下回流反应30小时,减压脱除溶剂得粗产品,然后用快速柱层析分离得产物104mg(62%)。产物的结构表征物理常数:1H NMR(400MHz,CDCl3)δ7.24(d,J=2.8Hz,2H),6.89(d,J=2.8Hz,2H),4.11(d,J=6.6Hz,4H),2.12–2.01(m,2H),1.01(d,J=6.7Hz,12H).13C NMR(100MHz,CDCl3)δ158.5,148.3,144.6,119.4,109.3,71.1,27.9,19.1.
实施例5
在25mL schlenk反应管中加入0.015mmol PdCl2(PPh3)2,55.9mgPVP(K30),0.75mmol乙酸钾,氮气条件下,加入2.5ml甲苯,再加入1mmol的乙醇和0.5mmol的60℃下回流反应30小时,减压脱除溶剂得粗产品,然后用快速柱层析分离得产物60mg(36%)。产物的结构表征物理常数:1H NMR(400MHz,CDCl3)δ7.12(d,J=3.5Hz,2H),6.83(d,J=3.5Hz,2H),1.59(s,18H).13C NMR(100MHz,CDCl3)δ157.8,148.0,145.6,118.7,108.9,82.3,28.2.
实施例6
在50mL schlenk反应管中加入0.03mmol PdCl2(PPh3)2,112mgPVP(K30),1.5mmol乙酸钾,氮气条件下,加入5ml甲苯,再加入2mmol的环丁醇和1mmol的25℃下回流反应30小时,减压脱除溶剂得粗产品,然后用快速柱层析分离得产物86mg(52%)。产物的结构表征物理常数:1H NMR(400MHz,CDCl3)δ7.23(d,J=3.5Hz,2H),6.88(d,J=3.5Hz,2H),5.29–5.13(m,2H),2.45(dt,J=15.0,7.5Hz,4H),2.22(dd,J=14.1,6.0Hz,4H),1.93–1.63(m,4H).13C NMR(100MHz,CDCl3)δ157.8,148.2,144.6,119.4,109.3,69.6,30.4,13.5.
实施例7
在100mL schlenk反应管中加入0.06mmol PdCl2(PPh3)2,224mgPVP(K30),3mmol乙酸钾,氮气条件下,加入10ml甲苯,再加入4mmol的环戊醇和2mmol的80℃下回流反应30小时,减压脱除溶剂得粗产品,然后用快速柱层析分离得产物228mg(64%)。产物的结构表征物理常数:1H NMR(400MHz,CDCl3)δ7.19(s,2H),6.87(s,2H),5.40(s,2H),1.96(s,4H),1.83(d,J=12.6Hz,8H),1.65(s,4H).13C NMR(100MHz,CDCl3)δ158.3,148.2,144.9,119.2,109.2,78.1,32.7,23.8.
实施例8
在100mL schlenk反应管中加入0.06mmol PdCl2(PPh3)2,224mgPVP(K30),1.5mmol乙酸钾,氮气条件下,加入10ml甲苯,再加入4mmol的正己醇和2mmol的120℃下反应30小时,减压脱除溶剂得粗产品,然后用快速柱层析分离得产物256mg(66%)。产物的结构表征物理常数:1H NMR(400MHz,CDCl3)δ7.23(d,J=3.6Hz,1H),6.89(d,J=3.6Hz,1H),4.32(t,J=6.8Hz,2H),1.80–1.71(m,2H),1.47–1.31(m,6H),0.91(t,J=7.0Hz,3H).13C NMR(100MHz,CDCl3)δ158.5,148.2,144.6,119.3,109.2,65.3,31.4,28.6,25.5,22.5,13.9.
实施例9
在25mL schlenk反应管中加入0.015mmol PdCl2(PPh3)2,55.9mgPVP(K30),50mmol乙酸钾,氮气条件下,加入2.5ml甲苯,再加入1mmol的环己醇和0.5mmol的110℃下回流反应30小时,减压脱除溶剂得粗产品,然后用快速柱层析分离得产物67mg(68%)。产物的结构表征物理常数:1H NMR(400MHz,CDCl3)δ7.21(d,J=2.2Hz,2H),6.88(d,J=2.5Hz,2H),5.01(dd,J=10.7,7.0Hz,2H),1.95(d,J=10.5Hz,4H),1.78(s,4H),1.63–1.25(m,12H).13C NMR(100MHz,CDCl3)δ158.0,148.2,145.0,119.1,109.2,73.7,31.6,25.4,23.7.
实施例10
在25mL schlenk反应管中加入0.015mmol PdCl2(PPh3)2,55.9mgPVP(K30),12.5mmol乙酸钾,氮气条件下,加入2.5ml甲苯,再加入1mmol的环庚醇和0.5mmol的110℃下回流反应30小时,减压脱除溶剂得粗产品,然后用快速柱层析分离得产物67mg(57%)。产物的结构表征物理常数:1H NMR(400MHz,CDCl3)δ7.20(d,J=3.6Hz,2H),6.88(d,J=3.6Hz,2H),5.23–5.13(m,2H),2.05–1.96(m,4H),1.86–1.67(m,8H),1.63–1.47(m,13H).13C NMR(100MHz,CDCl3)δ158.0,148.2,145.0,119.1,109.2,76.2,33.8,28.3,22.9.
实施例11
在100mL schlenk反应管中加入0.06mmol PdCl2(PPh3)2,224mgPVP(K30),100mmol乙酸钾,氮气条件下,加入2.5ml甲苯,再加入4mmol的正辛醇和2mmol的160℃下回流反应30小时,减压脱除溶剂得粗产品,然后用快速柱层析分离得产物74mg(66%)。产物的结构表征物理常数:1H NMR(400MHz,CDCl3)δ7.24(s,2H),6.91(s,2H),4.33(s,4H),1.77(s,4H),1.36(d,J=48.5Hz,21H),0.90(s,6H).13C NMR(101MHz,CDCl3)δ158.5,148.2,144.6,119.4,109.3,65.4,31.8,29.2,28.7,25.9,22.6,14.1.
实施例12
在100mL schlenk反应管中加入0.06mmol PdCl2(PPh3)2,224mgPVP(K30),2mmol乙酸钾,氮气条件下,加入2.5ml甲苯,再加入4mmol的异辛醇和2mmol的100℃下回流反应30小时,减压脱除溶剂得粗产品,然后用快速柱层析分离得产物77mg(70%)。产物的结构表征物理常数:1H NMR(400MHz,CDCl3)δ7.22(d,J=3.5Hz,2H),6.89(d,J=3.5Hz,2H),4.24(d,J=5.6Hz,4H),1.71(dd,J=11.6,5.7Hz,2H),1.48–1.28(m,16H),0.94(m,12H).13C NMR(100MHz,CDCl3)δ158.6,148.2,144.6,119.2,109.2,67.5,38.9,30.5,28.9,23.9,22.9,14.0,11.0.
实施例13
在25mL schlenk反应管中加入0.015mmol PdCl2(PPh3)2,55.9mgPVP(K30),0.75mmol乙酸钾,氮气条件下,加入2.5ml甲苯,再加入1mmol的仲辛醇和0.5mmol的110℃下回流反应30小时,减压脱除溶剂得粗产品,然后用快速柱层析分离得产物73mg(65%)。产物的结构表征物理常数:1H NMR(400MHz,CDCl3)δ7.20(d,J=3.6Hz,2H),6.88(d,J=3.6Hz,2H),5.14(dd,J=12.8,6.3Hz,2H),1.72(m,2H),1.65–1.54(m,2H),1.38–1.26(m,23H),0.88(t,J=6.7Hz,6H).13C NMR(100MHz,CDCl3)δ158.2,148.2,144.9,119.1,109.2,72.3,36.0,31.7,29.1,25.3,22.6,20.0,14.0.
实施例14
在25mL schlenk反应管中加入0.015mmol PdCl2(PPh3)2,55.9mgPVP(K30),0.75mmol乙酸钾,氮气条件下,加入2.5ml甲苯,再加入1mmol的环乙烷乙醇和0.5mmol的110℃下回流反应30小时,减压脱除溶剂得粗产品,然后用快速柱层析分离得产物78mg(70%)。产物的结构表征物理常数:1H NMR(400MHz,CDCl3)δ7.22(d,J=3.6Hz,2H),6.88(d,J=3.6Hz,2H),4.36(t,J=6.9Hz,4H),1.78(s,2H),1.77–1.69(m,6H),1.64(dd,J=13.5,6.6Hz,6H),1.43(dtd,J=14.3,7.3,3.6Hz,2H),1.29–1.13(m,6H),0.99(m,4H).13C NMR(101MHz,CDCl3)δ158.53,148.23,144.69,119.33,109.27,63.58,36.02,34.68,33.19,26.46,26.19.
实施例15
在25mL schlenk反应管中加入0.015mmol PdCl2(PPh3)2,55.9mgPVP(K30),1.6mmol乙酸钾,氮气条件下,加入2.5ml甲苯,再加入1mmol的L-薄荷醇和0.5mmol的110℃下回流反应30小时,减压脱除溶剂得粗产品,然后用快速柱层析分离得产物67mg(53%)。产物的结构表征物理常数:1H NMR(400MHz,CDCl3)δ7.21(d,J=3.4Hz,2H),6.89(d,J=3.4Hz,2H),4.93(td,J=10.8,4.1Hz,2H),2.11(d,J=11.9Hz,2H),1.98–1.88(m,2H),1.72(d,J=11.4Hz,4H),1.53(t,J=11.2Hz,4H),1.27(d,J=9.9Hz,2H),1.13(q,J=11.9Hz,4H),0.95–0.90(m,12H),0.82(d,J=6.9Hz,6H)13CNMR(100MHz,CDCl3)δ158.1,148.2,144.8,119.1,109.2,75.3,47.1,40.9,34.2,31.4,26.5,23.7,22.0,20.6,16.6.
实施例17
在25mL schlenk反应管中加入0.015mmol PdCl2(PPh3)2,55.9mgPVP(K30),0.75mmol乙酸钾,氮气条件下,加入2.5ml甲苯,再加入1mmol的苄醇和0.5mmol的100℃下回流反应30小时,减压脱除溶剂得粗产品,然后用快速柱层析分离得产物75mg(75%)。产物的结构表征物理常数:1H NMR(400MHz,CDCl3)δ7.38(dt,J=17.0,7.8Hz,10H),7.24(d,J=2.6Hz,2H),6.86(d,J=2.6Hz,2H),5.34(s,4H).13C NMR(100MHz,CDCl3)δ158.2,148.4,144.4,135.6,128.7,128.5,128.4,119.9,109.5,66.8.
实施例18
在50mL schlenk反应管中加入0.03mmol PdCl2(PPh3)2,112mgPVP(K30),30mmol乙酸钾,氮气条件下,加入5ml甲苯,再加入2mmol的苯基丙醇和1mmol的110℃下回流反应30小时,减压脱除溶剂得粗产品,然后用快速柱层析分离得产物61mg(54%)。产物的结构表征物理常数:1H NMR(400MHz,CDCl3)δ7.29(t,J=7.6Hz,4H),7.24–7.17(m,8H),6.90(d,J=3.6Hz,2H),4.35(t,J=6.5Hz,4H),2.77(t,J=7.6Hz,4H),2.16–1.99(m,5H).13C NMR(101MHz,CDCl3)δ158.4,148.3,144.5,141.0,128.5,128.4,126.1,119.5,109.4,64.5,32.2,30.2.
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (10)
1.一种5,5’-二烷氧酰基-[2,2’]联呋喃类化合物的制备方法,其特征在于,包括如下步骤:
将还原剂、碱、催化剂和稳定剂加入有机溶剂中,在氮气或者氩气条件下,回流反应得到5,5’-二烷氧酰基-[2,2’]联呋喃类化合物,结构通式为
其中X=Cl,Br或I;R为C1~C17的饱和脂肪烃、脂环烃、苯基烷基;
所述还原剂为醇类化合物。
2.根据权利要求1所述的一种5,5’-二烷氧酰基-[2,2’]联呋喃类化合物的制备方法,其特征在于,所述5,5’-二烷氧酰基-[2,2’]联呋喃类化合物的结构如下所示:
3.根据权利要求1所述的一种5,5’-二烷氧酰基-[2,2’]联呋喃类化合物的制备方法,其特征在于,所述回流反应的温度为0~160℃。
4.根据权利要求1所述的一种5,5’-二烷氧酰基-[2,2’]联呋喃类化合物的制备方法,其特征在于,所述回流反应的时间为1~60小时。
5.根据权利要求1所述的一种5,5’-二烷氧酰基-[2,2’]联呋喃类化合物的制备方法,其特征在于,所述有机溶剂为苯、甲苯、二甲苯、均三甲苯、氯苯、邻二氯苯、间二氯苯、对二氯苯、氟苯、五氟苯、六氟苯、乙酸乙酯、乙酸叔丁酯、乙酸丙酯、乙腈、苯腈、四氢呋喃、乙醚和1,4-二氧六环中的一种或几种的混合物。
6.根据权利要求1所述的一种5,5’-二烷氧酰基-[2,2’]联呋喃类化合物的制备方法,其特征在于,所述的还原剂为甲醇、乙醇、异丙醇、丁醇,乙二醇,1,3-丙二醇,1,2-丙二醇,丙三醇,1,4丁二醇,葡萄糖和甘露糖中的一种或几种的混合物。
7.根据权利要求1所述的一种5,5’-二烷氧酰基-[2,2’]联呋喃类化合物的制备方法,其特征在于,所述的催化剂为Fe(OAc)2、Cu(OAc)2、Co(OAc)2、Mn(OAc)2、Pd(OAc)2、Pd(PPh3)4、PdCl2、PdCl2(PPh3)2、PdCl2(PPh3)2、Pd2(dba)3、Ni(acac)2、Fe(acac)2、Fe(OTf)2、FeCl2、Fe(acac)3、Fe(OTf)3、FeCl3和FeCl2中的一种或几种的混合物。
8.根据权利要求1所述的一种5,5’-二烷氧酰基-[2,2’]联呋喃类化合物的制备方法,其特征在于,所述稳定剂为聚乙烯吡咯烷酮,分子量为1~10万。
9.根据权利要求1所述的一种5,5’-二烷氧酰基-[2,2’]联呋喃类化合物的制备方法,其特征在于,所述的碱为醋酸钾、醋酸钠、醋酸铯、碳酸钾、碳酸钠、碳酸氢钾、碳酸氢钠、氢氧化钠、氢氧化钾、磷酸钠、磷酸钾、磷酸氢钠、磷酸氢钾、三乙胺、吡啶、二异丙基乙基胺和N-甲基吗啡啉的一种或者几种的混合物。
10.根据权利要求1所述的一种5,5’-二烷氧酰基-[2,2’]联呋喃类化合物的制备方法,其特征在于,所述和还原剂的摩尔比为100:1~1:100;所述和碱的摩尔比为100:1~1:1;所述和催化剂的摩尔比为100:1~1:100;所述和稳定剂的摩尔比为100:1~1:1。
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