CN107881201A - A kind of method of m-hydroxybenzoic acid synthesis resorcinol - Google Patents
A kind of method of m-hydroxybenzoic acid synthesis resorcinol Download PDFInfo
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- CN107881201A CN107881201A CN201711085880.7A CN201711085880A CN107881201A CN 107881201 A CN107881201 A CN 107881201A CN 201711085880 A CN201711085880 A CN 201711085880A CN 107881201 A CN107881201 A CN 107881201A
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- Prior art keywords
- hydroxybenzoic acid
- resorcinol
- synthesis
- reaction
- solvent
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- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 30
- DNUYOWCKBJFOGS-UHFFFAOYSA-N 2-[[10-(2,2-dicarboxyethyl)anthracen-9-yl]methyl]propanedioic acid Chemical compound C1=CC=C2C(CC(C(=O)O)C(O)=O)=C(C=CC=C3)C3=C(CC(C(O)=O)C(O)=O)C2=C1 DNUYOWCKBJFOGS-UHFFFAOYSA-N 0.000 title claims abstract description 22
- IJFXRHURBJZNAO-UHFFFAOYSA-N meta--hydroxybenzoic acid Natural products OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 21
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 108010090785 inulinase Proteins 0.000 claims abstract description 18
- XXRCUYVCPSWGCC-UHFFFAOYSA-N Ethyl pyruvate Chemical compound CCOC(=O)C(C)=O XXRCUYVCPSWGCC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229940117360 ethyl pyruvate Drugs 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- 150000007529 inorganic bases Chemical class 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 150000005167 3-hydroxybenzoic acids Chemical class 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 6
- 229940100630 metacresol Drugs 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical group 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 239000002351 wastewater Substances 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 238000000605 extraction Methods 0.000 abstract description 3
- 238000012805 post-processing Methods 0.000 abstract description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 239000000975 dye Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 239000003814 drug Substances 0.000 description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 229930091371 Fructose Natural products 0.000 description 2
- 239000005715 Fructose Substances 0.000 description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 2
- 229920001202 Inulin Polymers 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 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 description 2
- 229940029339 inulin Drugs 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- UNEATYXSUBPPKP-UHFFFAOYSA-N 1,3-Diisopropylbenzene Chemical compound CC(C)C1=CC=CC(C(C)C)=C1 UNEATYXSUBPPKP-UHFFFAOYSA-N 0.000 description 1
- 229940018563 3-aminophenol Drugs 0.000 description 1
- ZGXJTSGNIOSYLO-UHFFFAOYSA-N 88755TAZ87 Chemical compound NCC(=O)CCC(O)=O ZGXJTSGNIOSYLO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 108090000604 Hydrolases Proteins 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 230000003255 anti-acne Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- JTBSVTOJNRIGJF-UHFFFAOYSA-N benzoic acid 3-hydroxybenzoic acid Chemical compound OC=1C=C(C(=O)O)C=CC1.C(C1=CC=CC=C1)(=O)O JTBSVTOJNRIGJF-UHFFFAOYSA-N 0.000 description 1
- BBSRDVDCIHLOTJ-UHFFFAOYSA-N benzoic acid phenol Chemical compound C1(=CC=CC=C1)O.C1(=CC=CC=C1)O.C1(=CC=CC=C1)C(=O)O BBSRDVDCIHLOTJ-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229940118199 levulan Drugs 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 230000001256 tonic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
- C12P7/22—Preparation of oxygen-containing organic compounds containing a hydroxy group aromatic
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- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Zoology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Microbiology (AREA)
- General Chemical & Material Sciences (AREA)
- Biotechnology (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of method of m-hydroxybenzoic acid synthesis resorcinol, reacted using one-step synthesis, by by raw material m-hydroxybenzoic acid, solvent in molar ratio 18:Dissolved in 10 30 addition autoclaves, add catalyst and be catalyzed, catalyst is the mixture of ethyl pyruvate and inulinase, and resorcinol is obtained through extraction, distilation steps；This reaction reduce it is conventionally produced during soda acid pollution and reduce the uses of a large amount of organic solvents, belong to environmentally friendly chemical reaction；Post processing generation waste water is few, reduces environmental pollution.
Description
Technical field
The present invention relates to the method for m-hydroxybenzoic acid synthesis resorcinol.
Background technology
Resorcinol (chemical formula：C6H4 (OH) 2), also referred to as resorcinol, resorcinol are that two hydrogen of benzene meta are optionally substituted by a hydroxyl group
The compound formed afterwards.Resorcinol white, needle-shaped crystals, there is offending smell, be placed in air and gradually redden, it is water-soluble
By force, there is stronger toxicity.Soluble in water, ethanol, ether, are slightly soluble in chloroform.
The preparation method of resorcinol is more, such as benzene sulfonated alkali fusion method, resorcinol and phenol co-production method, m-phenylene diamine (MPD)
Method, m-Diisopropylbenzene method, m-aminophenol Hydrolyze method etc..
The application of resorcinol is than wide.It is mainly used in rubber adhesive, synthetic resin, dyestuff, preservative, doctor
Medicine and analytical reagent etc.；Measure for nitrite and nitrate；Accelerator and synthetic resin as epoxy resin cure,
Adhesive, dyestuff, the ultra-violet absorber of medicine (PAS)；Manufacture as a variety of organic chemicals and dyestuff, it is
The intermediate of fur dyes；For medicine, dyestuff, rubber, plastics, photosensitive material, chemical fibre, explosive industry etc., also it is used to prepare
Cord dipping, the foaming agent solution of foam urea formaldehyde resin of tire, and make the medicated premix of anti-acne cosmetics, hair tonic
Bactericide in agent etc.；For system dye, plastics, medicine, synthetic fibers etc..
M-hydroxybenzoic acid benzoic acid is important medicine and Dyestuff synthesis intermediate.It is mainly using resorcinol as raw material
Prepared.Resorcinol is prepared using it to be rarely reported.There is document report to cross and isophthalic is prepared with potassium carbonate and benzoic acid
Diphenol, the substantial amounts of alkali of its course of reaction, processing procedure acid is caused to measure excessive, not only consumption of raw materials is more, also creates
More waste water.Also document report prepares resorcinol with carbonate ion liquid and benzoic acid, it is former used in its process
Expect that (referring to carbonate ion liquid) price is higher, be not suitable for industrialized production.Carbon dioxide is carried out instead at ambient pressure with benzoic acid
The report answered, but need to add substantial amounts of saleratus in the method reaction, it is more that post processing produces waste water, and react normal pressure,
Carried out in the aqueous solution, it is therefore desirable to flowed back, not only utilization rate of carbon dioxide is low, and accessory substance is also more, therefore yield is relatively low
(highest 60%)；If use carbon dioxide recovery gas (for industrial waste gas, the volume content of carbon dioxide is 65~75%)
Reacted, then yield is lower.
Inulinase (inulinase) is a kind of hydrolase that can hydrolyze levulan fructose glycosidic bond.Secrete the micro- of inulinase
Biology is distributed very extensively in nature, and the multiple-microorganism in soil, water and animal alimentary canal can be secreted.Inulinase can be
Hydrolytic inulin is into fructose or FOS under certain temperature conditionss.Its price is cheap, and due to its special construction, in organic conjunction
Also there is the effect of promoting some reactions to carry out into reaction.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of m-hydroxybenzoic acid synthesis resorcinol
Method.
A kind of method of m-hydroxybenzoic acid synthesis resorcinol, specific steps include：By raw material m-hydroxybenzoic acid, molten
Mole volume ratio (mol/mL) 1-8 is pressed in agent:10-30, which is added in autoclave, to be dissolved, and is added catalyst and is catalyzed, institute
Catalyst is stated as ethyl pyruvate and the mixture of inulinase；After reaction solution obtained by said process is cooled into room temperature, filtering,
Solvent is filtered out, gained filtrate is extracted using organic solvent, after the extract layer removing organic solvent of gained, obtains solid,
With distilled water dissolved solid, inorganic base regulation pH value of solution is added, distillation, obtains resorcinol.
Wherein filtering, extraction step when catalyst is reclaimed.
Synthetic reaction is carried out in the autoclave with Teflon liner and stainless steel outer lining.Reaction is entered within the liner
OK, Teflon liner can exclude the interference of the metallic atom on metal pipe-wall as a kind of high polymer material.Utilized before reaction
Hyperthermal distilled water discharges distilled water after being preheated to reactor.In reaction, porous ceramics can be added in a kettle or is divided
The carriers such as son sieve, to be formed on loading, promote the contact area of reactant, improve reaction rate.Carrier used is silicon
Glue, metal oxide molecular sieve, aluminum oxide, zeolite, diatomite, activated carbon, sepiolite, porous ceramics etc..
Described solvent is a kind of and mixture of ethanol in ethyl acetate, methyl tertiary butyl ether(MTBE).
The mass ratio of mixed catalyst ethyl pyruvate and inulinase is 2:1.During using mixed catalyst, first weigh certain
The ethyl pyruvate of quality is dissolved in ethanol, then ethyl acetate, the methyl tertiary butyl ether(MTBE) of proper volume are added into mixed solution
In a kind of solvent, make mixed catalyst repeat merge, add reactor in.
Described organic solvent is one kind in polyethylene glycol, dimethylformamide, hexamethylene.
Described inorganic base is alkali metal base compound or alkaline-earth metal alkali cpd.
Add inorganic base and adjust pH value of solution to 9-12.
The reaction uses the amount of solvent as 2-6.5L/mol m-hydroxybenzoic acids.
The reaction uses the amount of mixed catalyst as 0.1~12mol%/mol m-hydroxybenzoic acids.
Synthetic reaction pressure is 0.5~4.0MPa.
Synthesis reaction temperature is 100-150 DEG C.
Found through Shen many experiments, the present invention is using m-hydroxybenzoic acid as initiation material, in ethyl pyruvate and inulinase
Form carboxyl restructuring under mixed catalytic, the intermediate in general intermediate product that compares is more stable, and phenol is produced after hydrolysis.This
When the reason for kind intermediate is stable is carboxyl probably as catalyst, enzyme serves stable work to lone pair electrons part
With.
The method of the metacresol catalysis oxidation synthesis m-hydroxybenzoic acid of the present invention, it is possible to achieve：
(1) using m-hydroxybenzoic acid under the conditions of existing for high pressure, oxygen, under mixed catalytic effect, a step directly obtains
To resorcinol.Reduce it is conventionally produced during soda acid pollution and reduce the uses of a large amount of organic solvents, category
In environmentally friendly chemical reaction.
(2) composite catalyst used, can shorten the reaction time, improve the conversion ratio of product, reach 95%.It is therein
Dextrase catalyst raw material is easy to get, and price is cheap, and has catalytic action, reduces reaction temperature and pressure, when shortening reaction
Between, promote one step of reaction to carry out.
(3) catalyst compensate for the reaction of inulinase using the mixture of ethyl pyruvate and inulinase as catalyst
Time slightly long deficiency, promotes reaction forward progress, and it is few that post processing produces waste water, reduces environmental pollution.
(4) reacted filtering, extraction, distilation steps can improve product purity.
Embodiment
The following detailed description of the specific implementation of the present invention, it is necessary to it is pointed out here that, implement to be only intended to this hair below
Bright further explanation, it is impossible to be interpreted as limiting the scope of the invention, art skilled person is according to above-mentioned
Some nonessential modifications and adaptations that the content of the invention is made to the present invention, still fall within protection scope of the present invention.
Embodiment 1：
The mixture of raw material 5mol m-hydroxybenzoic acids, 100mL ethyl acetate and ethanol is added in autoclave
Row dissolving, the mixture catalyzer for adding ethyl pyruvate and inulinase are catalyzed, reaction pressure 4.0MPa, reaction temperature
For 100 degrees Celsius, react 1 hour；After decomposition reaction liquid obtained by said process is cooled into room temperature, filtering, solvent is filtered out,
Gained filtrate is extracted using polyethylene glycol, after the extract layer removing polyethylene glycol of gained, is obtained solid, is dissolved with distilled water
Solid, it is 9 to add inorganic base regulation pH value of solution, distillation, obtains resorcinol.The matter of mixed catalyst ethyl pyruvate and inulinase
Amount is than being 2:1.Reaction conversion ratio is 95%.
Embodiment 2：
The mixture of raw material 10mol m-hydroxybenzoic acids, 200mL ethyl acetate and ethanol is added in autoclave
Row dissolving, the mixture catalyzer for adding ethyl pyruvate and inulinase are catalyzed, reaction pressure 3.5MPa, reaction temperature
For 150 degrees Celsius, react 1.5 hours；After decomposition reaction liquid obtained by said process is cooled into room temperature, filtering, filter out molten
Agent, gained filtrate are extracted using polyethylene glycol, after the extract layer removing polyethylene glycol of gained, are obtained solid, are used distilled water
Dissolved solid, it is 9.5 to add inorganic base regulation pH value of solution, distillation, obtains resorcinol.Mixed catalyst ethyl pyruvate and inulin
The mass ratio of enzyme is 2:1.Reaction yield is 94%.
Embodiment 3：
The mixture of raw material 6mol m-hydroxybenzoic acids, 120mL ethyl acetate and ethanol is added in autoclave
Row dissolving, the mixture catalyzer for adding ethyl pyruvate and inulinase are catalyzed, reaction pressure 4MPa, and reaction temperature is
100 degrees Celsius, react 2 hours；After reaction solution obtained by said process is cooled into room temperature, filtering, solvent, gained filter are filtered out
Liquid is extracted using polyethylene glycol, after the extract layer of gained removing polyethylene glycol, obtains solid, with distilled water dissolved solid,
It is 11 to add inorganic base regulation pH value of solution, distillation, obtains resorcinol.The quality of mixed catalyst ethyl pyruvate and inulinase
Than for 2:1.Reaction yield is 91.5%.
Comparative example 1：
The mixture of raw material 10mol m-hydroxybenzoic acids, 200mL ethyl acetate and ethanol is added in autoclave
Row dissolving, add conventional catalyst and be catalyzed, through two reactions, the reaction time is 6 hours；By the reaction obtained by said process
After liquid is cooled to room temperature, filtering, solvent is filtered out, gained filtrate is extracted using polyethylene glycol, the extract layer removing of gained
After polyethylene glycol, solid is obtained, with distilled water dissolved solid, it is 9.5 to add inorganic base regulation pH value of solution, distillation, obtains isophthalic two
Phenol.Reaction yield is 80.5%.
Comparative example 2：
The mixture of raw material 6mol m-hydroxybenzoic acids, 120mL ethyl acetate and ethanol is added in autoclave
Row dissolving, the catalyst for adding inulinase are catalyzed, reaction pressure 4MPa, and reaction temperature is 100 degrees Celsius；By above-mentioned mistake
After reaction solution obtained by journey is cooled to room temperature, filtering, solvent is filtered out, gained filtrate is extracted using polyethylene glycol, gained
Extract layer removing polyethylene glycol after, obtain solid, with distilled water dissolved solid, it is 11 to add inorganic base regulation pH value of solution, is steamed
Evaporate, obtain resorcinol.Reaction yield is 86.5%, and the reaction time is 4 hours.
Although for illustrative purposes, it has been described that illustrative embodiments of the invention, those skilled in the art
Member it will be understood that, can be in form and details in the case of the scope and spirit for not departing from invention disclosed in appended claims
The upper change for carrying out various modifications, addition and replacement etc., and all these changes should all belong to appended claims of the present invention
Protection domain, and each step in each department of claimed product and method, can be in any combination
Form is combined.Therefore, to disclosed in this invention embodiment description be not intended to limit the scope of the present invention,
But for describing the present invention.Correspondingly, the scope of the present invention is not limited by embodiment of above, but by claim or
Its equivalent is defined.
Claims (10)
- A kind of 1. method of m-hydroxybenzoic acid synthesis resorcinol, it is characterised in that：Raw material m-hydroxybenzoic acid, solvent are pressed Molal volume ratio (mol/mL) 1-8:100-300, which is added in autoclave, to be dissolved, and is added catalyst and is catalyzed, described Catalyst is the mixture of ethyl pyruvate and inulinase, reacts 1-2 hours；Reaction solution obtained by said process is cooled to room Wen Hou, filtering, filters out solvent, and gained filtrate is extracted using organic solvent, after the extract layer removing organic solvent of gained, Solid is obtained, with distilled water dissolved solid, inorganic base regulation pH value of solution is added, distillation, obtains resorcinol.
- A kind of 2. method of m-hydroxybenzoic acid synthesis resorcinol according to claim 1, it is characterised in that：Mixing is urged The mass ratio of agent ethyl pyruvate and inulinase is 2:1.
- A kind of 3. method of m-hydroxybenzoic acid synthesis resorcinol according to claim 1, it is characterised in that：Described Solvent is a kind of and mixture of ethanol in ethyl acetate, methyl tertiary butyl ether(MTBE).
- A kind of 4. method of m-hydroxybenzoic acid synthesis resorcinol according to claim 1, it is characterised in that：Described Organic solvent is one kind in polyethylene glycol, dimethylformamide, hexamethylene.
- A kind of 5. method of m-hydroxybenzoic acid synthesis resorcinol according to claim 1, it is characterised in that：Described Inorganic base is alkali metal base compound or alkaline-earth metal alkali cpd.
- A kind of 6. method of metacresol catalysis oxidation synthesis m-hydroxybenzoic acid according to claim 1, it is characterised in that： Add inorganic base and adjust pH value of solution to 9-12.
- A kind of 7. method of metacresol catalysis oxidation synthesis m-hydroxybenzoic acid according to claim 1, it is characterised in that： The reaction uses the amount of solvent as 2-6.5L/mol m-hydroxybenzoic acids.
- A kind of 8. method of metacresol catalysis oxidation synthesis m-hydroxybenzoic acid according to claim 1, it is characterised in that： The reaction uses the amount of mixed catalyst as 0.1~12mol%/mol m-hydroxybenzoic acids.
- A kind of 9. method of metacresol catalysis oxidation synthesis m-hydroxybenzoic acid according to claim 1, it is characterised in that： Synthetic reaction pressure is 0.5~4.0MPa.
- 10. a kind of method of metacresol catalysis oxidation synthesis m-hydroxybenzoic acid according to claim 1, its feature exist In：Synthesis reaction temperature is 100-150 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112645799A (en) * | 2020-12-09 | 2021-04-13 | 山东兴强化工产业技术研究院有限公司 | Resorcinol post-treatment process |
| CN112645800A (en) * | 2020-12-09 | 2021-04-13 | 山东兴强化工产业技术研究院有限公司 | Resorcinol synthesis process |
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| EP0429077A2 (en) * | 1989-11-24 | 1991-05-29 | MITSUI TOATSU CHEMICALS, Inc. | Process for producing inulooligosaccharides |
| WO2001090370A2 (en) * | 2000-05-19 | 2001-11-29 | Nordzucker Ag | Method for microbial production of difructose anhydride iii, micro-organism used therefor and enzyme with inulase ii activity and dna sequences coding therefor |
| CN101624611A (en) * | 2009-08-13 | 2010-01-13 | 浙江大学 | Preparation method of inulase zymolyte for promoting clostridium butyricum to grow |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP0429077A2 (en) * | 1989-11-24 | 1991-05-29 | MITSUI TOATSU CHEMICALS, Inc. | Process for producing inulooligosaccharides |
| WO2001090370A2 (en) * | 2000-05-19 | 2001-11-29 | Nordzucker Ag | Method for microbial production of difructose anhydride iii, micro-organism used therefor and enzyme with inulase ii activity and dna sequences coding therefor |
| CN101624611A (en) * | 2009-08-13 | 2010-01-13 | 浙江大学 | Preparation method of inulase zymolyte for promoting clostridium butyricum to grow |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112645799A (en) * | 2020-12-09 | 2021-04-13 | 山东兴强化工产业技术研究院有限公司 | Resorcinol post-treatment process |
| CN112645800A (en) * | 2020-12-09 | 2021-04-13 | 山东兴强化工产业技术研究院有限公司 | Resorcinol synthesis process |
| CN112645800B (en) * | 2020-12-09 | 2023-02-03 | 山东兴强化工产业技术研究院有限公司 | A kind of Resorcinol synthesis technique |
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