CN112321426B - Catalytic oxidation process for preparing 4-acyloxy-2-methyl-2-butenal - Google Patents
Catalytic oxidation process for preparing 4-acyloxy-2-methyl-2-butenal Download PDFInfo
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- CN112321426B CN112321426B CN202011052341.5A CN202011052341A CN112321426B CN 112321426 B CN112321426 B CN 112321426B CN 202011052341 A CN202011052341 A CN 202011052341A CN 112321426 B CN112321426 B CN 112321426B
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- 230000003197 catalytic effect Effects 0.000 title abstract description 13
- 230000003647 oxidation Effects 0.000 title description 7
- 238000007254 oxidation reaction Methods 0.000 title description 7
- 238000004519 manufacturing process Methods 0.000 title description 2
- 239000003054 catalyst Substances 0.000 claims abstract description 61
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 238000002360 preparation method Methods 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 51
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 238000000605 extraction Methods 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical compound O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 claims description 2
- URVYVINLDPIJEH-ZZXKWVIFSA-N [(e)-4-chloro-3-methylbut-2-enyl] acetate Chemical group CC(=O)OC\C=C(/C)CCl URVYVINLDPIJEH-ZZXKWVIFSA-N 0.000 claims 1
- 238000012805 post-processing Methods 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 7
- 239000002351 wastewater Substances 0.000 abstract description 7
- 150000003839 salts Chemical class 0.000 abstract description 6
- 230000003321 amplification Effects 0.000 abstract description 3
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 28
- 239000000047 product Substances 0.000 description 17
- -1 etc.) Substances 0.000 description 16
- 239000012074 organic phase Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 229910052742 iron Inorganic materials 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- FOCAUTSVDIKZOP-UHFFFAOYSA-M chloroacetate Chemical compound [O-]C(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-M 0.000 description 5
- 229940089960 chloroacetate Drugs 0.000 description 5
- 230000006837 decompression Effects 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 3
- 235000018660 ammonium molybdate Nutrition 0.000 description 3
- 239000011609 ammonium molybdate Substances 0.000 description 3
- 229940010552 ammonium molybdate Drugs 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- RMVRCOSGEKBHPQ-UHFFFAOYSA-N chloro hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OCl RMVRCOSGEKBHPQ-UHFFFAOYSA-N 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000013460 polyoxometalate Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- QSGCJQBBHYWZHS-UHFFFAOYSA-N 2-methylpropyl 2-chloroacetate Chemical compound CC(C)COC(=O)CCl QSGCJQBBHYWZHS-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- HSJKGGMUJITCBW-UHFFFAOYSA-N beta-hydroxybutyraldehyde Natural products CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 2
- VIRPUNZTLGQDDV-UHFFFAOYSA-N chloro propanoate Chemical compound CCC(=O)OCl VIRPUNZTLGQDDV-UHFFFAOYSA-N 0.000 description 2
- NEHNMFOYXAPHSD-UHFFFAOYSA-N citronellal Chemical compound O=CCC(C)CCC=C(C)C NEHNMFOYXAPHSD-UHFFFAOYSA-N 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 235000015393 sodium molybdate Nutrition 0.000 description 2
- 239000011684 sodium molybdate Substances 0.000 description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 2
- KUYMVWXKHQSIAS-UHFFFAOYSA-N tert-butyl 2-chloroacetate Chemical compound CC(C)(C)OC(=O)CCl KUYMVWXKHQSIAS-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- PWANZHNQNGHLSF-UHFFFAOYSA-N (1-chloro-3-methylbut-3-enyl) acetate Chemical compound CC(=C)CC(Cl)OC(C)=O PWANZHNQNGHLSF-UHFFFAOYSA-N 0.000 description 1
- FAGZYUKVQKTQDU-UHFFFAOYSA-N 2-chloro-2-fluoropropanoic acid Chemical compound CC(F)(Cl)C(O)=O FAGZYUKVQKTQDU-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241000167854 Bourreria succulenta Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910016525 CuMo Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- XXIKYCPRDXIMQM-UHFFFAOYSA-N Isopentenyl acetate Chemical compound CC(C)=CCOC(C)=O XXIKYCPRDXIMQM-UHFFFAOYSA-N 0.000 description 1
- 238000005718 Kornblum oxidation reaction Methods 0.000 description 1
- 244000178870 Lavandula angustifolia Species 0.000 description 1
- 235000010663 Lavandula angustifolia Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 238000006007 Sommelet synthesis reaction Methods 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- WJGAPUXHSQQWQF-UHFFFAOYSA-N acetic acid;hydrochloride Chemical compound Cl.CC(O)=O WJGAPUXHSQQWQF-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YJRGMUWRPCPLNH-UHFFFAOYSA-N butyl 2-chloroacetate Chemical compound CCCCOC(=O)CCl YJRGMUWRPCPLNH-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000019693 cherries Nutrition 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229930003633 citronellal Natural products 0.000 description 1
- 235000000983 citronellal Nutrition 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- SJMLNDPIJZBEKY-UHFFFAOYSA-N ethyl 2,2,2-trichloroacetate Chemical compound CCOC(=O)C(Cl)(Cl)Cl SJMLNDPIJZBEKY-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-M hexadecanoate Chemical compound CCCCCCCCCCCCCCCC([O-])=O IPCSVZSSVZVIGE-UHFFFAOYSA-M 0.000 description 1
- NGLNCTNUNFMLBM-UHFFFAOYSA-N hexadecanoic acid;hydrochloride Chemical compound Cl.CCCCCCCCCCCCCCCC(O)=O NGLNCTNUNFMLBM-UHFFFAOYSA-N 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000000055 hyoplipidemic effect Effects 0.000 description 1
- 230000002218 hypoglycaemic effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 239000001102 lavandula vera Substances 0.000 description 1
- 235000018219 lavender Nutrition 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- IVRIRQXJSNCSPQ-UHFFFAOYSA-N propan-2-yl carbonochloridate Chemical compound CC(C)OC(Cl)=O IVRIRQXJSNCSPQ-UHFFFAOYSA-N 0.000 description 1
- YYFIGOPUHPDIBO-UHFFFAOYSA-N propanoic acid;hydrochloride Chemical compound Cl.CCC(O)=O YYFIGOPUHPDIBO-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000037351 starvation Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 150000004370 vitamin A ester derivatives Chemical class 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 229940045997 vitamin a Drugs 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/881—Molybdenum and iron
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a preparation method of 4-acyloxy-2-methyl-2-butenal, which comprises the following steps: firstly, preparing raw materials, then reacting the materials prepared in the step 1, and finally, preparing the 4-acyloxy-2-methyl-2-butenal through post-treatment. The preparation method of 4-acyloxy-2-methyl-2-butenal has simple process and mild reaction conditions, is carried out in the presence of a catalyst, has good catalytic activity and excellent stability and durability, can obtain a product with higher yield by using the catalyst as the catalyst, has low preparation cost, and simultaneously has less waste salt and waste water generated in the preparation process, accords with the green chemistry concept and has high industrial amplification feasibility.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a catalytic oxidation method for preparing 4-acyloxy-2-methyl-2-butenal.
Background
Chloro (halo) isopentenyl acetate is an important intermediate for products such as synthetic medicines (hypolipidemic, hypoglycemic, vitamin a, vitamin E, etc.), fragrances (citronellal, lavender alcohol, etc.), pigments (cherry red, orange red, deep blue, orange, etc.), etc.
The oxidation product of chloroisopentenyl acetate, 4-acyloxy-2-methyl-2-butenal (hereinafter referred to as C5 aldol ester), is an important intermediate for preparing vitamin A ester (acetate, propionate, palmitate) and other compounds, and in the prior art, there are mainly two oxidation methods:
DMSO Oxidation (Kornblum Oxidation)
The method has low yield of 40-50%, needs to recover dimethyl sulfide, has pungent smell and poor reaction repeatability, and the used reagent DMSO has certain toxicity, and generates a large amount of wastewater in the post-treatment process, thus being unfavorable for environmental protection.
2. Urotropine oxidation (Sommelet reaction)
The method is suitable for oxidizing the benzyl halide compound into aldehyde, the yield is 70-80%, and the yield of the aliphatic halogenated hydrocarbon compound is only 20%, so that the method has low synthesis yield, and the industrial three wastes are larger, which is not beneficial to environmental protection.
Therefore, a method for preparing 4-acyloxy-2-methyl-2-butenal with less waste water and waste salt, environmental protection and high yield is needed to be provided.
Disclosure of Invention
Based on the technical background, the inventor makes a keen approach, and found that: the preparation method comprises the steps of preparing raw materials, and preparing a catalyst, wherein the catalyst is Anderson type polyoxometallate taking Fe as a center, and then, the catalyst is used as a catalyst, and the C5 aldehyde ester is prepared by taking chloroester as a raw material. The preparation method of 4-acyloxy-2-methyl-2-butenal has the advantages of simple process, mild reaction conditions, good catalytic activity of the catalyst taking Fe as a center, low cost, excellent stability and durability, high yield of products can be obtained by using the catalyst as the catalyst, the preparation cost is low, and meanwhile, waste salt and waste water generated in the preparation process are less, so that the preparation method accords with the green chemistry concept, and the industrial amplification feasibility is high.
The first aspect of the present invention is to provide a method for preparing 4-acyloxy-2-methyl-2-butenal, comprising the steps of:
step 1, preparing raw materials;
step 2, reacting the substances prepared in the step 1;
and step 3, performing post-treatment to obtain a final product.
In a second aspect, the present invention provides 4-acyloxy-2-methyl-2-butenal produced by the process for producing 4-acyloxy-2-methyl-2-butenal according to the first aspect of the present invention.
The preparation method of 4-acyloxy-2-methyl-2-butenal provided by the invention has the following advantages that:
(1) The preparation method of the 4-acyloxy-2-methyl-2-butenal has lower preparation cost, less waste water and waste salt generated in the preparation process, and accords with the green chemical concept;
(2) The preparation method of 4-acyloxy-2-methyl-2-butenal has mild reaction conditions;
(3) The preparation method of 4-acyloxy-2-methyl-2-butenal adopts the oxometalate taking iron as the center as a catalyst, has good catalytic activity and excellent stability and durability;
(4) The preparation method of 4-acyloxy-2-methyl-2-butenal has high product yield and industrial amplifying value.
Detailed Description
The features and advantages of the present invention will become more apparent and evident from the following detailed description of the invention.
In a first aspect, the present invention provides a process for the preparation of 4-acyloxy-2-methyl-2-butenal, the process comprising the steps of:
step 1, preparing raw materials;
step 2, reacting the substances prepared in the step 1;
and step 3, performing post-treatment to obtain a final product.
This step is specifically described and illustrated below.
Step 1, preparing raw materials.
The raw materials comprise acetonitrile aqueous solution and C5 chloroester, in the invention, the acetonitrile aqueous solution is used as a solvent, the inventor discovers that a single solvent reaction system is heterogeneous and has poor catalytic effect, and the catalyst has poor solubility and lower reaction conversion rate probably due to the heterogeneous solvent, and the acetonitrile aqueous solution is used as the solvent to make the reaction system homogeneous, so that the catalyst has good solubility therein, the catalytic effect is obviously improved, and the product yield is further improved.
When the mass ratio of acetonitrile to water is 1: (0.5-2), preferably 1:1. The catalyst has better solubility in the solvent and better catalytic effect.
In the invention, the C5 chloro ester is selected from one or more of chloro acetate, chloro propionate, chloro palmitate, tert-butyl chloroacetate, isopropyl chloroformate, ethyl trichloroacetate, n-butyl chloroacetate and isobutyl chloroacetate; preferably, the C5 chloro ester is selected from one or more of chloro acetate, chloro propionate, chloro palmitate, tert-butyl chloroacetate and isobutyl chloroacetate; more preferably, the C5 chloride is selected from one or more of chloride acetate, chloride propionate and chloride palmitate.
According to a preferred embodiment of the present invention, the preparation of the catalyst is also included in step 1. According to the invention, the catalyst is preferably an Anderson type polyoxometalate, which is a condensed acid formed by condensing an inorganic oxy acid. It is mainly an inorganic metal-oxygen cluster compound with special structure and property formed by oxygen connection of pre-transition metal elements. Anderson type polyoxometallate has the advantages of mild catalytic condition, high yield and selectivity and the like. The inventor discovers that the catalyst used as the catalyst in the invention avoids the defects of pollution, difficult recovery and complicated post-treatment of the traditional acid-base catalysis. And the catalyst is used for preparing the aldehyde ester, so that the preparation efficiency and the yield of the aldehyde ester can be effectively improved.
According to a further preferred embodiment of the present invention, the catalyst is prepared by the steps of:
step 1-1, adding an A element-containing compound into inorganic oxyacid for reaction;
and step 1-2, after the reaction is finished, performing post-treatment to obtain the catalyst.
In the present invention, the a element is a metal element, preferably selected from copper, iron, cobalt, nickel or zinc, more preferably an Fe element.
The present inventors found that when the element a is Fe, the catalyst is an Anderson-type polyoxometalate centered on Fe, fe is cheaper, the catalyst prepared centered on it is cheaper, and at the same time, the present inventors found that an Anderson-type polyoxometalate centered on iron as the catalyst of the present invention can effectively increase the yield of the product, and waste water and waste salts generated in the preparation process of 4-acyloxy-2-methyl-2-butenal are fewer.
In step 1-1, the a-element-containing compound is selected from one of an a-element-containing oxide, an inorganic salt, and a hydroxide, preferably, the a-element-containing compound is selected from one of ferric oxide, ferric sulfate, ferrous sulfate, and ferric hydroxide, and more preferably, the a-element-containing compound is selected from ferric sulfate or ferrous sulfate.
The inorganic oxy acid is selected from ammonium molybdate, sodium molybdate, potassium molybdate, ammonium tungstate or sodium tungstate, preferably the inorganic oxy acid is selected from ammonium molybdate, sodium molybdate or sodium tungstate, more preferably the inorganic oxy acid is selected from ammonium molybdate.
The mass ratio of the A-element-containing compound to the inorganic oxygen acid is 1: (2-6), preferably, the mass ratio of the a element-containing compound to the inorganic oxy acid is 1: (2.5 to 5), more preferably, the mass ratio of the compound containing an element A to the inorganic oxy acid is 1: (3-4.5). It is found by experiment that when the mass ratio of the compound containing the A element to the inorganic oxy acid is 1: (2-6), the catalyst obtained has a higher yield.
The amount of the solvent to be added in the present invention is not particularly limited as long as the inorganic oxy acid is completely dissolved. The mass ratio of the solvent to the inorganic oxygen acid is preferably (15-20): 1, more preferably 16:1.
Before adding the A-containing compound, the inorganic oxy acid dissolved in the solvent is heated to 80 to 120 ℃, preferably 90 to 110 ℃, more preferably 100 ℃. The purpose of the heating is to dissolve the inorganic oxy acid dissolved in the solvent.
The a-containing compound is dissolved in a solvent, preferably water, and the amount of the solvent to be added is not particularly limited as long as the iron-containing compound can be completely dissolved. The mass ratio of the solvent to the A-element-containing compound is preferably (2-6): 1, more preferably (3 to 5): 1.
the addition mode of the compound containing the element A is preferably dropwise addition, and the dropwise addition can ensure that reactants are always in a starvation state, thereby being more beneficial to the forward reaction and the improvement of the product yield.
The reaction is preferably carried out while stirring, more preferably after the addition of the element-A-containing compound is completed, and stirring is more advantageous for the progress of the reaction and further for the improvement of the product yield. The reaction temperature is 80 to 120 ℃, preferably 90 to 110 ℃, more preferably 100 ℃. The stirring time is 0.5 to 5 hours, preferably 1 to 3 hours, more preferably 1 to 2 hours. Experiments show that the reaction temperature is 80-120 ℃, the stirring time is 0.5-5 h, the reaction is more facilitated, and the catalyst yield is higher.
In step 1-2, the post-treatment includes filtration, precipitation and drying. After the reaction is completed, filtration is carried out for the purpose of removing insoluble matters.
The precipitation mode is preferably standing or low-temperature stirring, the standing is carried out at room temperature, and the standing time is 1-5 days; the stirring at low temperature is carried out at 1-10 ℃, preferably 5-10 ℃, and the stirring can accelerate the precipitation of the solid, and the stirring time is 2-5 hours, preferably 4 hours. More preferably, the precipitation mode is standing, and experiments show that the catalyst prepared by the standing mode has higher yield.
After standing or stirring, filtering, collecting precipitated solid, and recrystallizing the collected solid in deionized water at 70-90deg.C, preferably 80deg.C. The recrystallization is carried out for 1 to 3 times, and the purpose of the recrystallization is to purify the prepared product.
Drying is performed after recrystallization, preferably vacuum drying.
The prepared catalyst, C5 chloroester and acetonitrile aqueous solution are weighed and placed in a container, and the mass ratio of the catalyst to the chloroester to the acetonitrile is 1: (5-50): (5-30), preferably, the mass ratio of the catalyst, the chloroester and the acetonitrile is 1: (5-40): (5-28), more preferably, the mass ratio of the catalyst, the C5 chloroester and the acetonitrile is 1: (9-33): (7-26). The inventors found that the amount of catalyst added affects the yield of the final product produced when the mass ratio of catalyst, C5 chloroester and acetonitrile is 1: (5-50): (5-30) the highest yield of 4-acyloxy-2-methyl-2-butenal.
And 2, reacting the substances prepared in the step 1.
The weighed catalyst, chloroester and acetonitrile water solution prepared in the step 1 are placed in a container, and the temperature is raised to carry out reaction, wherein the container is preferably a four-mouth bottle.
The reaction also incorporates an oxidising agent, which in the present invention is selected from oxygen, hydrogen peroxide, t-butyl peroxide or air, preferably oxygen or air, more preferably oxygen. Experiments show that when the oxidant is oxygen, the yield of the prepared product is highest.
The reaction temperature is 50 to 90 ℃, preferably 60 to 80 ℃, more preferably 70 to 80 ℃, for example 75 ℃. The reaction time is 3 to 10 hours, preferably 5 to 8 hours, more preferably 6 to 7 hours.
The reaction temperature affects the reaction rate and the product yield, and the inventor discovers that the catalyst has the highest catalytic activity when the reaction temperature is 50-90 ℃, and can obtain the product with higher yield on the premise of higher preparation efficiency, especially when the reaction temperature is 75 ℃. The reaction time is adapted to the reaction temperature, and when the reaction time is 3-10 h, the reaction is more complete and the product yield is higher.
According to the invention, the reaction is preferably carried out under stirring, and the stirring mode is preferably mechanical stirring, so that the stirring can further accelerate the reaction progress, improve the preparation efficiency, fully mix the reaction raw materials and improve the yield.
And step 3, performing post-treatment to obtain a final product.
The post-treatment of the invention comprises filtration, extraction, drying and desolventizing. After the reaction is finished, filtering, extracting, drying and desolventizing are sequentially carried out.
The filtration is preferably performed after the completion of the reaction and the temperature is reduced, more preferably after the temperature is reduced to 15 to 25 ℃, for example, after the temperature is reduced to 20 ℃.
In the invention, the filtered filter residue is used for recycling the catalyst, and the recycled catalyst can be used for next preparation, thereby not only reducing the cost, but also conforming to the green chemical industry concept. The filtrate was collected and extracted.
The collected filtrate is added with an extractant for extraction, wherein the extractant is preferably ethyl acetate, and the inventor discovers that the ethyl acetate is used as the extractant of the invention, so that the extraction efficiency can be effectively improved, and meanwhile, a product with higher yield can be prepared.
The extraction is preferably 1 to 5 times, more preferably 3 times. When the extraction is carried out for 3 times, the yield of the product prepared by the preparation method is highest, and the preparation process is simplified.
After the extraction is completed, all organic phases are combined and dried, preferably by adding anhydrous sodium sulfate. The organic phase is dried, which is more favorable for the subsequent desolventizing.
According to the invention, the desolventizing is preferably performed under reduced pressure, and the C5 aldol ester is obtained after desolventizing. The yield of the C5 aldehyde ester prepared by the preparation method can reach 80-90%.
In a second aspect, the present invention provides 4-acyloxy-2-methyl-2-butenal produced by the process for producing 4-acyloxy-2-methyl-2-butenal according to the first aspect of the present invention.
The invention has the beneficial effects that:
(1) The preparation method of 4-acyloxy-2-methyl-2-butenal adopts the Anderson type polyoxometallate taking Fe as a center as a catalyst, and has the advantages of low cost, good catalytic activity, high catalytic condition temperature, excellent stability and durability and the like;
(2) The preparation method of the 4-acyloxy-2-methyl-2-butenal has less waste water and waste salt generated in the preparation process, and the catalyst can be recycled, so that the method accords with the concept of green chemical industry;
(3) The preparation method of the 4-acyloxy-2-methyl-2-butenal has low preparation cost, simple preparation process and high industrial amplification feasibility;
(4) The preparation method of the 4-acyloxy-2-methyl-2-butenal has higher product yield which can reach 80-90%.
Examples
The invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not intended to limit the scope of the invention.
Example 1 catalyst preparation
500mL four-necked flask was charged with 18.73g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O (15 mmol) and 299.60g deionized water were heated to 100deg.C to dissolve. Simultaneously weighing Fe 2 (SO 4 ) 3 (11.5 mmol) was dissolved in 23.30g deionized water and slowly added dropwise to boiling (NH) 4 ) 6 Mo 7 O 24 And (3) in the solution, stirring thoroughly for 1h after the dripping. After the reaction, insoluble matters were filtered, the filtrate was allowed to stand at room temperature for two days, a yellowish white solid was precipitated, the solid was collected by filtration, recrystallized twice in deionized water at 80℃and dried under vacuum to give 13.69g of a white solid (11.4 mmol, hereinafter referred to as iron catalyst) in a yield of 98.7%. (NH) 4 ) 3 [FeMo 6 O 18 (OH) 6 ]·7H 2 O。IR:3165(νas NH,m),1640.57(δOH m),1400.95(δNH,s),946.05(νMo=O,vs),845.10(νMo=O,vs),649.37(νMo-O-Mo,vs),574.83(νMo-O-Mo,w)cm -1 。
Example 2 catalyst preparation
Into a 2000mL four-necked flask was charged 62.42g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O (50 mmol) and 998.67g deionized water were heated to 100deg.C to dissolve. 18.36g of Fe is weighed again 2 (SO 4 ) 3 (45.5 mmol) was dissolved in 55.08g deionized water and slowly added dropwise to boiling (NH) 4 ) 6 Mo 7 O 24 And (3) in the solution, stirring thoroughly for 1.5h after the dripping. Filtering insoluble substances after the reaction is finished, stirring the filtrate for 4 hours at the temperature of 5 ℃,the yellowish white solid precipitated, the solid was collected by filtration, recrystallized twice in deionized water at 80℃and dried under vacuum to give 54.08g of a white solid iron catalyst (45 mmol) in 99.0% yield.
Example 3
500mL four-necked flask was charged with 6.01g of the iron catalyst (5 mmol) obtained in example 1, 87.42g of chloro acetate (0.5 mol), 78.68g of acetonitrile and 78.68g of water, and the mixture was stirred under an oxygen atmosphere at a temperature of 70℃for 6 hours. And after the reaction is finished, the temperature is reduced to 20 ℃, the catalyst is recovered from filter residues, an organic phase is collected by separating filtrate, and 39.34g of ethyl acetate is added into a water phase for extraction three times. All organic phases are combined and dried over anhydrous sodium sulfate, and 61.27g of crude C5 aldehyde acetate is obtained after decompression and desolventization, and the yield is 86.2%.
Example 4
1000mL four-necked flask was charged with 27.04g of the iron catalyst (23 mmol) obtained in example 1, 262.27g of chloro acetate (1.5 mol), 209.82g of acetonitrile and 209.82g of water, and the mixture was stirred under an oxygen atmosphere at a temperature of 75℃for 7 hours. And after the reaction is finished, the temperature is reduced to 25 ℃, the catalyst is recovered from filter residues, an organic phase is collected by separating filtrate, and 104.91g of ethyl acetate is added into a water phase for extraction three times. All organic phases are combined and dried over anhydrous sodium sulfate, and 189.77g of crude C5 aldehyde acetate is obtained after decompression and desolventization, and the yield is 89.0%.
Example 5
500mL four-necked flask was charged with 4.81g of the iron catalyst (4 mmol) obtained in example 2, 75.97g of chlorofluoro-propionate (0.4 mol), 53.18g of acetonitrile and 53.18g of water, and the mixture was stirred under an oxygen atmosphere at a temperature of 70℃for 7 hours. And after the reaction is finished, the temperature is reduced to 20 ℃, the catalyst is recovered from filter residues, an organic phase is collected by separating filtrate, and 26.59g of ethyl acetate is added into a water phase for extraction three times. All organic phases are combined and dried over anhydrous sodium sulfate, and the crude product of 52.66g of C5 aldehyde propionate can be obtained after decompression and desolventization, and the yield is 84.3%.
Example 6
1000mL four-necked flask was charged with 8.41g of the iron catalyst (7 mmol) obtained in example 2, 270.21g of chloro palmitate (0.7 mol), 216.17g of acetonitrile and 216.17g of water, and the mixture was stirred under an oxygen atmosphere at 75℃for 6 hours. And after the reaction is finished, the temperature is reduced to 20 ℃, the catalyst is recovered from filter residues, an organic phase is collected by separating filtrate, and 108.08g of ethyl acetate is added into a water phase for extraction three times. All organic phases are combined and dried over anhydrous sodium sulfate, and then the crude product of 203.80g of C5 aldehyde palmitate is obtained after decompression and desolventization, and the yield is 86.0%.
Comparative example
Comparative example 1 copper catalyst preparation
1000mL four-necked flask was charged with 37.45g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O (30 mmol) and 561.75g deionized water were heated to 100deg.C to dissolve. Simultaneously weighing CuSO 4 (43.4 mmol) was dissolved in 139.91g deionized water and slowly added dropwise to boiling (NH) 4 ) 6 Mo 7 O 24 In the solution, the reaction was stopped after the completion of the dropwise addition by stirring for 1 hour, insoluble matters were filtered, the filtrate was allowed to stand still at room temperature for two days, a blue solid was precipitated, the solid was collected by filtration, and dried in vacuo to give 51.70g of the product (26.4 mmol, hereinafter referred to as copper catalyst) in a yield of 60.8%.
(NH 4 ) 4 [CuMo 6 O 18 (OH) 6 ]·5H 2 O。IR:1631.65(δOH m),1400.56(δNH,s),931.62(νMo=O,vs),897.66(νMo=O,vs),640.18(νMo-O-Mo,vs),577.68(νMo-O-Mo,w)cm -1 。
Comparative example 2
A1000 mL four-necked flask was charged with 27.04g of the copper catalyst prepared in comparative example 1, 262.27g of chloroacetate (1.5 mol), 209.82g of acetonitrile and 209.82g of water, and the mixture was stirred at 75℃for 7 hours under an oxygen atmosphere. And after the reaction is finished, the temperature is reduced to 25 ℃, the catalyst is recovered from filter residues, an organic phase is collected by separating filtrate, and 104.91g of ethyl acetate is added into a water phase for extraction three times. All organic phases are combined and dried over anhydrous sodium sulfate, and the crude product of 149.26g C5 aldehyde acetate can be obtained after decompression and desolventization, and the yield is 75%.
The invention has been described in detail in connection with the specific embodiments and exemplary examples thereof, but such description is not to be construed as limiting the invention. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, and these fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (2)
1. A process for the preparation of 4-acyloxy-2-methyl-2-butenal, comprising the steps of:
step 1, preparing raw materials, wherein the raw materials comprise acetonitrile aqueous solution and C5 chloroester;
the C5 chloroester is 1-acetoxy-4-chloro-3-methyl-2-butene;
the preparation raw materials also comprise the preparation of a catalyst;
the catalyst is (NH) 4 ) 3 [FeMo 6 O 18 (OH) 6 ]·7H 2 O;
The catalyst is prepared by the following steps:
step 1-1, adding an A element-containing compound into inorganic oxyacid for reaction;
step 1-2, after the reaction is finished, post-treating to prepare a catalyst;
in the step (1-1),
the compound containing the element A is Fe 2 (SO 4 ) 3 ;
The inorganic oxy acid is (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O;
The mass ratio of the compound containing the element A to the inorganic oxygen acid is 1: (2-6);
the reaction temperature is 80-120 ℃, the reaction is carried out under stirring, and the stirring time is 0.5-5 h;
step 2, reacting the substances prepared in the step 1, wherein an oxidant is added in the reaction, the oxidant is oxygen, the reaction temperature is 60-80 ℃, and the reaction time is 5-8 hours;
step 3, post-processing to obtain a final product; the post-treatment comprises filtration, extraction, drying and desolventizing;
extracting the filtrate with an extractant, wherein the extractant is ethyl acetate;
in the step 1, the catalyst, C5 chloroester and acetonitrile water solution which are weighed and prepared are placed in a container;
the mass ratio of the catalyst to the C5 chloroester to the acetonitrile is 1: (5-50): (5-30);
the mass ratio of acetonitrile to water is 1: (0.5-2).
2. The method according to claim 1, wherein in step 3,
anhydrous sodium sulfate was added to dry.
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Publication number | Priority date | Publication date | Assignee | Title |
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Non-Patent Citations (1)
Title |
---|
Investigation of catalytic activity of cobalt–Schiff base complex covalently linked to the polyoxometalate in the alkene and benzyl halide oxidation with hydrogen peroxide;Valiollah Mirkhani等;《Catalysis Communications》;20081231;第9卷;第219-223页 * |
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