CN113979974B - 一种2,5-呋喃二甲酸的合成工艺 - Google Patents
一种2,5-呋喃二甲酸的合成工艺 Download PDFInfo
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- CN113979974B CN113979974B CN202111405433.1A CN202111405433A CN113979974B CN 113979974 B CN113979974 B CN 113979974B CN 202111405433 A CN202111405433 A CN 202111405433A CN 113979974 B CN113979974 B CN 113979974B
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- catalyst
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- drying
- ethanol
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- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 100
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 99
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims abstract description 64
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 30
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- -1 2, 5-furan dicarboxylic acid ester Chemical class 0.000 claims abstract description 6
- UKRYIKCRRFOEOD-UHFFFAOYSA-N 5-iodofuran-2-carboxylic acid Chemical compound OC(=O)C1=CC=C(I)O1 UKRYIKCRRFOEOD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims abstract 3
- 239000000243 solution Substances 0.000 claims description 50
- 238000006243 chemical reaction Methods 0.000 claims description 49
- 239000004005 microsphere Substances 0.000 claims description 48
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 42
- 239000012876 carrier material Substances 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 17
- 239000002608 ionic liquid Substances 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 239000005457 ice water Substances 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000004440 column chromatography Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 8
- MYAJTCUQMQREFZ-UHFFFAOYSA-K tppts Chemical compound [Na+].[Na+].[Na+].[O-]S(=O)(=O)C1=CC=CC(P(C=2C=C(C=CC=2)S([O-])(=O)=O)C=2C=C(C=CC=2)S([O-])(=O)=O)=C1 MYAJTCUQMQREFZ-UHFFFAOYSA-K 0.000 claims description 8
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 7
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 238000010790 dilution Methods 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 229920001400 block copolymer Polymers 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims 10
- 238000010438 heat treatment Methods 0.000 claims 7
- 239000003960 organic solvent Substances 0.000 claims 3
- 238000007872 degassing Methods 0.000 claims 2
- 238000001704 evaporation Methods 0.000 claims 2
- 230000007717 exclusion Effects 0.000 claims 2
- 238000001354 calcination Methods 0.000 claims 1
- 230000003113 alkalizing effect Effects 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 39
- 150000001875 compounds Chemical class 0.000 description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000005810 carbonylation reaction Methods 0.000 description 12
- 238000006192 iodination reaction Methods 0.000 description 12
- 230000026045 iodination Effects 0.000 description 11
- 229910052763 palladium Inorganic materials 0.000 description 9
- 239000003208 petroleum Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 230000006315 carbonylation Effects 0.000 description 7
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 7
- 238000004809 thin layer chromatography Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 5
- 238000000605 extraction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- ZOUWOGOTHLRRLS-UHFFFAOYSA-N palladium;phosphane Chemical compound P.[Pd] ZOUWOGOTHLRRLS-UHFFFAOYSA-N 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004042 decolorization Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- ZPUCINDJVBIVPJ-LJISPDSOSA-N cocaine Chemical compound O([C@H]1C[C@@H]2CC[C@@H](N2C)[C@H]1C(=O)OC)C(=O)C1=CC=CC=C1 ZPUCINDJVBIVPJ-LJISPDSOSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- LAULFZIZDHINAX-UHFFFAOYSA-N furan-2-carboxylic acid Chemical compound OC(=O)C1=CC=CO1.OC(=O)C1=CC=CO1 LAULFZIZDHINAX-UHFFFAOYSA-N 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002402 hexoses Chemical class 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229920003987 resole Polymers 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- YVTQHZDUDUCGRD-UHFFFAOYSA-N 5-bromofuran-2-carboxylic acid Chemical compound OC(=O)C1=CC=C(Br)O1 YVTQHZDUDUCGRD-UHFFFAOYSA-N 0.000 description 1
- 241000194107 Bacillus megaterium Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- QZRGKCOWNLSUDK-UHFFFAOYSA-N Iodochlorine Chemical compound ICl QZRGKCOWNLSUDK-UHFFFAOYSA-N 0.000 description 1
- 208000000913 Kidney Calculi Diseases 0.000 description 1
- 206010029148 Nephrolithiasis Diseases 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000003444 anaesthetic effect Effects 0.000 description 1
- 150000003931 anilides Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- FISPNUUIQAWGFU-UHFFFAOYSA-L calcium furan-2,5-dicarboxylate Chemical compound [Ca++].[O-]C(=O)c1ccc(o1)C([O-])=O FISPNUUIQAWGFU-UHFFFAOYSA-L 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 229960003920 cocaine Drugs 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- PHGMGTWRSNXLDV-UHFFFAOYSA-N diethyl furan-2,5-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)O1 PHGMGTWRSNXLDV-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012336 iodinating agent Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007721 medicinal effect Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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Abstract
本发明公开了一种2,5‑呋喃二甲酸的合成工艺,以呋喃‑2‑甲酸和碘化钾催化剂,制备2‑碘‑5‑呋喃甲酸;再制得2‑碘‑5‑呋喃甲酸酯;并以Pd催化剂与三乙胺和乙醇制得2,5‑呋喃二甲酸酯;加碱并中和后得到产物2,5‑呋喃二甲酸。
Description
技术领域
本发明涉及精细化工合成技术领域,具体涉及一种2,5-呋喃二甲酸的合成工艺。
背景技术
2,5-呋喃二甲酸(FDCA)是2004年美国能源部列出的12种高附加值生物基化学物质之一,由于具有巨大的市场潜力而被称为“沉睡的巨人”。研究表明,FDCA具有一定的医药作用。其中,2,5-呋喃二甲酸二乙酯具有与可卡因类似的麻醉作用,2,5-呋喃二甲酸钙盐能够抑制巨大芽孢杆菌的生长,FDCA的衍生酰苯胺具有抗菌作用。同时,FDCA作为一种强络合剂,可用于去除肾结石,其四氢呋喃稀释液还可用于制备人造移植静脉。另外,FDCA作为多元羧酸是消防泡沫的重要成分,可以应用于消防领域。最重要的是,FDCA的结构与石油化学衍生物对苯二甲酸相似,可作为替代品用于聚合物的合成。近年来,其因广泛应用于众多领域而备受关注。
FDCA合成工艺一般分为生物合成法和化学合成法,其中,化学合成法的应用较为普遍,通常以5-羟甲基糠醛(HMF)、糠酸糠醛、己糖二酸、二甘醇酸等为起始原料,通过催化剂选择性氧化或脱水环化制备而成。HMF虽为主流方法,但过程选择性低,有副产物生成,且HMF化学性质不稳定,易发生进一步分解或聚合,不易储存;沈志明等和PAN等以糠酸糠醛为原料经过歧化反应生成FDCA,这一方法会生成副产物呋喃,分离困难,同时歧化反应需要的强碱性环境,会生成大量盐类物质,对环境污染较大;己糖二酸法脱水环化过程碳化现象严重,产率较低;二甘醇酸法原料较难制备、成本高昂,同时制备过程中需要使用许多其他试剂,因此较难用于工业化制备中。尹国川等以呋喃-2-甲酸(糠酸)为原料,依次经过溴代、酯化、羰化和水解4步反应制备FDCA,取得了较好的效果,但第三步羰化反应的时间较长,且产率还有待提升。
发明内容
针对上述尹国川等以呋喃-2-甲酸(糠酸)为原料的四步反应合成方法,为解决现有技术缺陷,本发明公开了一种高羰化反应产率的2,5-呋喃二甲酸合成工艺。第一步采用了双氧水氧化直接碘化法,使用高溶解性的碘化钾为碘化剂,生成化合物a的碘代过程迅速,且氧化产物为水,绿色环保。在第三步羰化反应中,由于碘代芳烃的高反应活性,反应过程迅速,同时利用高分散性的负载离子液体钯催化剂,大大提高了由化合物b到化合物c的转化产率。
为了达到上述目的,本发明提供如下技术方案:
一种2,5-呋喃二甲酸的合成工艺,其特征在于,包括以下步骤:
(1)搅拌条件下,在乙醇和水的混合溶液中缓慢滴加浓硫酸,再加入呋喃-2-甲酸和负载于催化剂载体材料(MC)(优选为微球,即催化剂载体材料微球)(以下如无特别说明,MC均指催化剂载体材料微球)上的碘化钾,在冰水浴条件下缓慢滴加30%H2O2溶液。滴加完毕,升温至70℃反应6h,薄层色谱(TLC)跟踪反应,原料点消失,冷却至室温,加入亚硫酸氢钠溶液脱色,直至颜色不再变化。再用二氯甲烷萃取,有机相用饱和NaHCO3溶液洗涤,水层用二氯甲烷萃取,合并有机相以无水硫酸钠干燥,蒸除溶剂,硅胶柱层析(纯石油醚),真空干燥得到化合物a(2-碘-5-呋喃甲酸)。
(2)将化合物a溶于甲醇中,加入一定质量浓度的浓硫酸,保温在100℃回流反应24h。TCL点板检查,减压浓缩去除溶剂,向剩余反应混合物中加入冰水,并用饱和碳酸钠溶液调节pH,经乙酸乙酯萃取后,再用饱和盐水洗涤,干燥浓缩后得化合物b(2-碘-5-呋喃甲酸酯)。
(3)将化合物b溶解于DMF中,加入三乙胺和乙醇,再加入催化剂载体材料微球(MC)或活性炭(AC)负载离子液体钯催化剂(水溶性钯膦络合物,Pd-TPPTS-IL/MC或Pd-TPPTS-IL/AC),将反应瓶里的气体置换为一氧化碳。保温在140℃,在一定的一氧化碳气体压力下搅拌反应24h。经TCL点板检查反应结束后,加入水稀释并用乙酸乙酯萃取,再用饱和盐水洗涤,进行干燥浓缩后,通过简单的柱层析,得到化合物c(2,5-呋喃二甲酸酯)。
(4)将化合物c置于甲醇和水中混合搅拌溶解,再加入氢氧化钠,保温在100℃,搅拌反应24h,TCL点板检查。冷却后调节pH,静置过滤,冰水洗涤,干燥后得到产物2,5-呋喃二甲酸。
进一步地,所述步骤(1)中催化剂载体材料微球(MC)的制备方法如下:
催化剂载体以嵌段共聚物EO106PO70EO106(其中EO表示乙氧基,PO表示丙氧基)作为模板剂合成。
(1)常温下将模板剂溶解在乙醇中。然后在搅拌下加入可溶性酚醛树脂前驱体(含有苯酚和甲醛的乙醇溶液)。溶液中模板剂:苯酚:甲醛:乙醇的摩尔比约为0.012:1:2:80。
(2)将均匀溶液倒入盘中以在室温下蒸发乙醇12h,然后在100℃下加热24h。
(3)将制备的产物在管式炉中以150cm3/min的气体流速在900℃下煅烧3h,该气体含有体积百分比约为2.5%氧气的氩气气氛。
(4)所得材料进一步在纯二氧化碳气氛中以150cm3/min的流速在750℃下反应3h后得到催化剂载体材料。
将上述催化剂载体材料进行制粒形成微球待用即催化剂载体材料微球(MC),所述催化剂载体材料微球粒径为20-2000微米,优选为20-500微米,进一步优选为20-200微米,最优选为30-100微米;若使用筛网对微球进行分筛,优选筛网为50-400目,进一步优选为100-400目。
进一步地,所述步骤(1)中碘化钾催化剂(KI/MC)的制备方法如下:
(1)将KI在搅拌下溶解于无水乙醇中。该催化剂溶液在40℃下保持约30min。
(2)将催化剂载体材料微球用无水乙醇浸渍1h,除去乙醇并烘干倒入KI乙醇溶液中。KI与催化剂载体材料微球质量比为1:5。
(3)在40℃下经过30min后,使催化剂载体材料微球充分吸收KI乙醇溶液后干燥备用。
进一步地,所述步骤(1)中呋喃-2-甲酸与碘化钾与H2O2的摩尔比为1:1:2。
进一步地,所述步骤(1)中乙醇与水的体积比为1:3。
进一步地,所述步骤(2)中浓硫酸的质量百分浓度为98%。
进一步地,所述步骤(2)中调节pH值为7~8。
进一步地,所述步骤(3)中Pd催化剂(Pd-TPPTS-IL/MC)制备方法如下:
(1)在严格排除氧气的条件下进行。在典型的制备实验中,将Pd(OAc)2和TPPTS在搅拌下溶解在离子液体[bmim][p-CH3C6H4SO3]中。该催化剂溶液在40℃下保持约30min。其中Pd(OAc)2与TPPTS的投料摩尔比为1:6。
(2)将催化剂载体材料微球在真空下脱气并在氩气下储存。然后,将它们用无水乙醇浸渍1h,除去乙醇并烘干后倒入该催化剂溶液中。
(3)在40℃下经过30min后,使催化剂载体材料微球充分吸收催化剂溶液后,干燥备用(优选为在超临界二氧化碳条件下进行干燥)。
进一步地,所述步骤(3)中钯与化合物b与三乙胺与乙醇的投料摩尔比为1:50:60:60。
进一步地,所述步骤(3)中钯催化剂离子液体的负载量为10%。
进一步地,所述步骤(3)中一氧化碳气体压力为4MPa。
进一步地,所述步骤(3)中柱层析填料乙酸乙酯与石油醚体积比为1:10。
进一步地,所述步骤(4)中甲醇与水的体积比为1:5。
进一步地,所述步骤(4)中调节pH值为1~2。
进一步地,所述步骤(1)(2)(3)(4)中TLC展开剂石油醚与乙酸乙酯体积比为3:1。
与现有的以呋喃-2-甲酸为原料的四步反应合成方法技术相比,本发明具有如下优点和有益效果:
本发明提供的2,5-呋喃二甲酸合成工艺,以呋喃-2-甲酸为起始原料,在碘代过程采用了双氧水氧化直接碘化法。一氯化碘碘化也是一种直接碘化法,反应步骤简单,产率较高,但一氯化碘具有强腐蚀性且易分解,不便于使用和储存。双氧水氧化直接碘化法的原料和活化剂廉价易得,产率也较高,因为在卤素单质中碘单质的溶解度是最小的,故使用高溶解性的碘化钾为碘化剂,加速了碘代过程,且过氧化氢氧化后的产物为水,绿色环保。在第三步羰化反应中,C-H键断裂需要很高的能量,对底物的结构和催化剂的类型要求苛刻。在卤代芳烃羰化过程中,卤素原子作为离去基团时,碘原子的离去倾向最大,其稳定性远低于溴原子,因此利用碘化钾替代溴素得到的碘代芳烃具有高羰化活性,反应过程迅速。同时,本方法合成了负载离子液体钯催化剂,该催化剂是将溶有水溶性钯膦络合物的离子液体负载于载体上,在载体表面形成离子液体液膜,而钯膦络合物可在液膜中自由移动,具有高分散性,有利于钯膦络合物催化活性的发挥。通过反应底物的重选和催化剂的改进,碘取代基能够更高效的转化为酯基,使得第三步羰化反应产率大大提高。本方法具有高度的创新性,反应条件温和,产率高,具有很高的经济价值和社会效益,更适于工业化生产。
具体实施方式
以下将结合具体实施例对本发明提供的技术方案进行详细说明,应理解下述具体实施方式仅用于说明本发明而不用于限制本发明的范围。
实施例1
催化剂载体材料微球(MC)制备:催化剂载体以嵌段共聚物EO106PO70EO106作为模板剂合成。常温下将3.0g模板剂溶解在60.0g乙醇中。然后在搅拌下加入15.0g可溶性酚醛树脂前驱体(含有1.80g苯酚和1.15g甲醛的乙醇溶液)。将均匀溶液倒入盘中以在室温下蒸发乙醇12h,然后在100℃下加热24h。将制备的产物在管式炉中以150cm3/min的气体流速在900℃下煅烧3h,该气体含有体积百分比约为2.5%氧气的氩气气氛。所得材料进一步在纯二氧化碳气氛中以150cm3/min的流速在750℃下反应3h后得到催化剂载体材料。将上述催化剂载体材料进行制粒形成微球并使用400目筛网处理后制得催化剂载体材料微球(MC)待用。
实施例2-1
碘化钾催化剂(KI/MC)制备:将1.0g KI在搅拌下溶解10ml无水乙醇中。
该催化剂溶液在40℃下保持约30min。总共5.0g的催化剂载体材料微球用无水乙醇浸渍1h,除去乙醇并烘干倒入KI乙醇溶液中。在40℃下经过30min后,使催化剂载体材料微球充分吸收KI乙醇溶液后干燥备用。
实施例2-2
碘单质催化剂(I2/MC)制备:将1.0g I2在搅拌下溶解10ml无水乙醇中。该催化剂溶液在40℃下保持约30min。总共5.0g的催化剂载体材料微球用无水乙醇浸渍1h,除去乙醇并烘干倒入I2乙醇溶液中。在40℃下经过30min后,使催化剂载体材料微球充分吸收I2乙醇溶液后干燥备用。
实施例3-1
Pd催化剂(Pd-TPPTS-IL/MC)制备:在严格排除氧气的条件下进行。在典型的制备实验中,将Pd(OAc)2(16.0mg,0.07mmol)和TPPTS(240.5mg,0.42mmol)在搅拌下溶解在离子液体[bmim][p-CH3C6H4SO3](5.9ml)中。该催化剂溶液在40℃下保持约30min。总共5.0g的催化剂载体材料微球在真空下脱气并在氩气下储存。然后,将它们用无水乙醇浸渍1h,除去乙醇并烘干后倒入该催化剂溶液中。在40℃下经过30min后,使催化剂载体材料微球充分吸收催化剂溶液后,在超临界二氧化碳条件下干燥备用。
实施例3-2
Pd催化剂(Pd-TPPTS-IL/AC)制备:在严格排除氧气的条件下进行。在典型的制备实验中,将Pd(OAc)2(16.0mg,0.07mmol)和TPPTS(240.5mg,0.42mmol)在搅拌下溶解在离子液体[bmim][p-CH3C6H4SO3](5.9ml)中。该催化剂溶液在40℃下保持约30min。总共5.0g的活性炭在真空下脱气并在氩气下储存。然后,将它们用无水乙醇浸渍1h,除去乙醇并烘干后倒入该催化剂溶液中。在40℃下经过30min后,使活性炭充分吸收催化剂溶液后,在超临界二氧化碳条件下干燥备用。
实施例4
碘代反应:搅拌条件下,在40ml溶剂(乙醇:水=1:3,v:v)中缓慢滴加2.5g浓硫酸,再加入2.8g(25mmol)呋喃-2-甲酸和24.9g(含25mmol KI)KI/MC催化剂,在冰水浴条件下缓慢滴加30%H2O2溶液5.2ml(50mmol)。滴加完毕,升温至70℃反应6h,薄层色谱(TLC)跟踪反应,原料点消失,冷却至室温,加入0.1mol/L亚硫酸氢钠溶液脱色,直至颜色不再变化。再用二氯甲烷萃取,有机相用饱和NaHCO3溶液洗涤,水层用二氯甲烷萃取,合并有机相以无水硫酸钠干燥,蒸除溶剂,硅胶柱层析(纯石油醚),真空干燥得到化合物a 5.24g(22mmol),收率88.1%。
比较例1
碘代反应(碘单质为碘化剂):搅拌条件下,在40ml溶剂(乙醇:水=1:3,v:v)中缓慢滴加2.5g浓硫酸,再加入2.8g(25mmol)呋喃-2-甲酸和19.05g(理论含25mmol I2)I2/MC,在冰水浴条件下缓慢滴加30%H2O2溶液5.2ml(50mmol)。滴加完毕,升温至70℃反应10h,薄层色谱(TLC)跟踪反应,原料点消失,冷却至室温,加入0.1mol/L亚硫酸氢钠溶液脱色,直至颜色不再变化。再用二氯甲烷萃取,有机相用饱和NaHCO3溶液洗涤,水层用二氯甲烷萃取,合并有机相以无水硫酸钠干燥,蒸除溶剂,硅胶柱层析(纯石油醚),真空干燥得到化合物a4.23g(17mmol),收率71.2%。
实施例5
酯化反应:将5.95g(25mmol)化合物a溶于200ml甲醇中,加入6ml质量浓度为98%的浓硫酸,保温在100℃回流反应24h。TCL点板检查,减压浓缩去除溶剂,向剩余反应混合物中加入200ml冰水,并用饱和碳酸钠溶液调节pH为7~8,经乙酸乙酯萃取后,再用饱和盐水洗涤,干燥浓缩后得化合物b 5.78g(23mmol),收率92%。
实施例6
羰化反应:将6.30g(25mmol)化合物b溶解于60ml DMF中,加入3.04g(30mmol)三乙胺和1.38g(30mmol)乙醇,再加入35.07g(含0.5mmol Pd(OAc)2)负载离子液体钯催化剂(Pd-TPPTS-IL/MC,离子液体为[bmim][p-CH3C6H4SO3],负载量为10%,无机载体为催化剂载体材料MC)。反应体系置于不锈钢高压反应釜中,保温在140℃,通入一氧化碳,压力4MPa,搅拌反应24h。经TCL点板检查反应结束后,加入120ml水稀释并用乙酸乙酯萃取,再用饱和盐水洗涤,进行干燥浓缩后,通过简单的柱层析(乙酸乙酯:石油醚=1:10,v:v),得到化合物c4.92g(24.8mmol),收率99.3%。
实施例7
羰化反应(活性炭为催化剂载体):将6.30g(25mmol)化合物b溶解于60ml DMF中,加入3.04g(30mmol)三乙胺和1.38g(30mmol)乙醇,再加入35.07g(含0.5mmol Pd(OAc)2)负载离子液体钯催化剂(Pd-TPPTS-IL/AC,离子液体为[bmim][p-CH3C6H4SO3],负载量为10%,无机载体为活性炭AC)。反应体系置于不锈钢高压反应釜中,保温在140℃,通入一氧化碳,压力4MPa,搅拌反应36h。经TCL点板检查反应结束后,加入120ml水稀释并用乙酸乙酯萃取,再用饱和盐水洗涤,进行干燥浓缩后,通过简单的柱层析(乙酸乙酯:石油醚=1:10,v:v),得到化合物c 4.24g(21.4mmol),收率85.7%。
比较例2
羰化反应(溴代芳烃为反应底物,普通钯催化剂):将5.13g(25mmol)5-溴-呋喃-2-甲酸酯溶解于60ml DMF中,加入3.04g(30mmol)三乙胺和1.38g(30mmol)乙醇,再加入0.35g(0.5mmol)二(三苯基膦)二氯化钯催化剂。反应体系置于不锈钢高压反应釜中,保温在140℃,通入一氧化碳,压力4MPa,搅拌反应48h。经TCL点板检查反应结束后,加入120ml水稀释并用乙酸乙酯萃取,再用饱和盐水洗涤,进行干燥浓缩后,通过简单的柱层析(乙酸乙酯:石油醚=1:10,v:v),得到化合物c 3.18g(16.0mmol),收率64.3%。
比较例3
羰化反应(普通钯催化剂):将6.30g(25mmol)化合物b溶解于60ml DMF中,加入3.04g(30mmol)三乙胺和1.38g(30mmol)乙醇,再加入0.35g(0.5mmol)二(三苯基膦)二氯化钯催化剂。反应体系置于不锈钢高压反应釜中,保温在140℃,通入一氧化碳,压力4MPa,搅拌反应36h。经TCL点板检查反应结束后,加入120ml水稀释并用乙酸乙酯萃取,再用饱和盐水洗涤,进行干燥浓缩后,通过简单的柱层析(乙酸乙酯:石油醚=1:10,v:v),得到化合物c3.79g(19.1mmol),收率76.5%。
实施例8
水解反应:将4.95g(25mmol)化合物c搅拌溶解于30ml甲醇与150ml水的混合溶剂中,再加入2.5g(62.5mmol)氢氧化钠,保温在100℃,搅拌反应24h,TCL点板检查。冷却后用稀盐酸调节pH为1~2,静置过滤,冰水洗涤,干燥后得到产物2,5-呋喃二甲酸3.55g(22.8mmol),收率91%。
实施例4、5、6、8总收率73.2%。
以上实施例仅为本发明较佳的具体实施方式,不能理解为对本发明专利范围的限制。任何熟悉本技术领域的技术人员在不脱离本发明原理的前提下,根据本发明的技术方案做出的若干改进或等同替换,都应涵盖在本发明的保护范围之内。
Claims (9)
1.一种2,5-呋喃二甲酸的合成工艺,其特征在于,包括以下步骤:
(1)搅拌条件下,在乙醇和水的混合溶液中缓慢滴加浓硫酸,再加入呋喃-2-甲酸和碘化钾催化剂,在冰水浴条件下添加H2O2溶液后升温至70℃反应后冷却并萃取有机相,蒸除溶剂并干燥得到2-碘-5-呋喃甲酸;
(2)将2-碘-5-呋喃甲酸溶于溶剂中,加入浓硫酸,保温在100℃回流反应,去除溶剂调节pH,萃取并洗涤干燥浓缩得2-碘-5-呋喃甲酸酯;
(3)将2-碘-5-呋喃甲酸酯溶解于溶剂中,加入三乙胺和乙醇,再加入Pd催化剂,将反应气氛置换为一氧化碳,加热并搅拌反应后,加水稀释并萃取、洗涤,干燥浓缩并经柱层析后得到2,5-呋喃二甲酸酯;
(4)将2,5-呋喃二甲酸酯置于溶剂中搅拌溶解,加热并加入碱搅拌反应,冷却后调节pH,静置过滤,冰水洗涤,干燥后得到产物2,5-呋喃二甲酸;
所述Pd催化剂进一步包含催化剂载体材料微球,所述催化剂载体材料微球的制备步骤为:
(a)常温下将嵌段共聚物EO106PO70EO106溶解在乙醇中,加入含有苯酚和甲醛的乙醇溶液后形成均匀溶液;所述嵌段共聚物EO106PO70EO106:苯酚:甲醛:乙醇的摩尔比为(0.01-0.02):1:(1.5-3):(60-100);
(b)将所述均匀溶液蒸发,并在100℃下加热得到初产物;
(c)将所述初产物在含有体积百分比1-10%氧气的氩气气氛中在500-1000℃下煅烧次产物;
(d)将所述次产物进一步在纯二氧化碳气氛中在500-1000℃下反应后并进行制粒形成微球后得到所述催化剂载体材料微球;
所述Pd催化剂的制备方法为:
(i)在严格排除氧气的条件下,将Pd(OAc)2和TPPTS在搅拌下溶解在离子液体[bmim][p-CH3C6H4SO3]中形成Pd催化剂溶液;Pd(OAc)2与TPPTS的投料摩尔比为1:6;
(ii)将所述催化剂载体材料在真空下脱气并在氩气下用无水乙醇浸渍,除去乙醇并烘干后倒入所述Pd催化剂溶液中;
(iii)所述催化剂载体材料微球充分吸收所述Pd催化剂溶液后干燥,制得所述Pd催化剂。
2.根据权利要求1所述的一种2,5-呋喃二甲酸的合成工艺,其特征在于,所述碘化钾催化剂进一步包含催化剂载体材料微球。
3.根据权利要求2所述的一种2,5-呋喃二甲酸的合成工艺,其特征在于,所述碘化钾催化剂为负载于所述催化剂载体材料微球上的碘化钾。
4.根据权利要求3所述的一种2,5-呋喃二甲酸的合成工艺,其特征在于,所述碘化钾催化剂的制备方法为:
(1)将KI在搅拌下溶解于有机溶剂中形成KI溶液;
(2)将所述催化剂载体材料用所述有机溶剂浸渍后,除去所述有机溶剂并烘干后倒入所述KI溶液中;KI与所述催化剂载体材料质量比为1:5;
(3)在加热条件下使所述催化剂载体材料充分吸收KI溶液后干燥制得所述碘化钾催化剂。
5.一种2,5-呋喃二甲酸的合成工艺,其特征在于,包括以下步骤:
(1)搅拌条件下,在乙醇和水的混合溶液中缓慢滴加浓硫酸,再加入呋喃-2-甲酸和碘化钾催化剂,在冰水浴条件下添加H2O2溶液后升温至70℃反应后冷却并萃取有机相,蒸除溶剂并干燥得到2-碘-5-呋喃甲酸;
(2)将2-碘-5-呋喃甲酸溶于溶剂中,加入浓硫酸,保温在100℃回流反应,去除溶剂调节pH,萃取并洗涤干燥浓缩得2-碘-5-呋喃甲酸酯;
(3)将2-碘-5-呋喃甲酸酯溶解于溶剂中,加入三乙胺和乙醇,再加入Pd催化剂,将反应气氛置换为一氧化碳,加热并搅拌反应后,加水稀释并萃取、洗涤,干燥浓缩并经柱层析后得到2,5-呋喃二甲酸酯;
(4)将2,5-呋喃二甲酸酯置于溶剂中搅拌溶解,加热并加入碱搅拌反应,冷却后调节pH,静置过滤,冰水洗涤,干燥后得到产物2,5-呋喃二甲酸;
所述Pd催化剂的制备方法为:
(i)在严格排除氧气的条件下,将Pd(OAc)2和TPPTS在搅拌下溶解在离子液体[bmim][p-CH3C6H4SO3]中形成Pd催化剂溶液;Pd(OAc)2与TPPTS的投料摩尔比为1:6;
(ii)将活性炭在真空下脱气并在氩气下用无水乙醇浸渍,除去乙醇并烘干后倒入所述Pd催化剂溶液中;
(iii)所述活性炭充分吸收所述Pd催化剂溶液后干燥,制得所述Pd催化剂。
6.根据权利要求1-5任意一项所述的一种2,5-呋喃二甲酸的合成工艺,其特征在于,所述呋喃-2-甲酸与碘化钾与H2O2的摩尔比为1:1:2。
7.根据权利要求1-5任意一项所述的一种2,5-呋喃二甲酸的合成工艺,其特征在于,所述Pd催化剂中的钯元素与2-碘-5-呋喃甲酸酯与三乙胺与乙醇的投料摩尔比为1:50:60:60。
8.根据权利要求1或5所述的一种2,5-呋喃二甲酸的合成工艺,其特征在于,所述Pd催化剂中离子液体的重量百分比负载量为10%。
9.根据权利要求1-5任意一项所述的一种2,5-呋喃二甲酸的合成工艺,其特征在于,所述一氧化碳的气体压力为4MPa。
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