CN117414873A - Catalyst for alcohol transesterification reaction, application of catalyst and synthetic method of asymmetric dialkyl carbonate - Google Patents
Catalyst for alcohol transesterification reaction, application of catalyst and synthetic method of asymmetric dialkyl carbonate Download PDFInfo
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- CN117414873A CN117414873A CN202311355263.XA CN202311355263A CN117414873A CN 117414873 A CN117414873 A CN 117414873A CN 202311355263 A CN202311355263 A CN 202311355263A CN 117414873 A CN117414873 A CN 117414873A
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 30
- 238000005809 transesterification reaction Methods 0.000 title claims abstract description 30
- 238000010189 synthetic method Methods 0.000 title abstract description 6
- 150000003752 zinc compounds Chemical class 0.000 claims abstract description 14
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 12
- 150000001412 amines Chemical class 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- -1 beta-oxo propyl Chemical group 0.000 claims description 18
- OQBXZODAWFALJO-UHFFFAOYSA-N 2-oxopropyl hydrogen carbonate Chemical compound CC(=O)COC(O)=O OQBXZODAWFALJO-UHFFFAOYSA-N 0.000 claims description 15
- 238000005580 one pot reaction Methods 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 12
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000003495 polar organic solvent Substances 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 229940100890 silver compound Drugs 0.000 claims description 5
- 150000003379 silver compounds Chemical class 0.000 claims description 5
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 3
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 238000001308 synthesis method Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 6
- 239000001569 carbon dioxide Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000012039 electrophile Substances 0.000 abstract description 4
- 230000000269 nucleophilic effect Effects 0.000 abstract description 4
- 229920005862 polyol Polymers 0.000 abstract description 3
- 150000003077 polyols Chemical class 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- FJLGSLSITVQVRJ-UHFFFAOYSA-N benzyl ethyl carbonate Chemical compound CCOC(=O)OCC1=CC=CC=C1 FJLGSLSITVQVRJ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 2
- 229910001958 silver carbonate Inorganic materials 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JABYJIQOLGWMQW-UHFFFAOYSA-N undec-4-ene Chemical compound CCCCCCC=CCCC JABYJIQOLGWMQW-UHFFFAOYSA-N 0.000 description 2
- 229960000314 zinc acetate Drugs 0.000 description 2
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229940057499 anhydrous zinc acetate Drugs 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 150000005678 chain carbonates Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000005677 organic carbonates Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 description 1
- 229940019931 silver phosphate Drugs 0.000 description 1
- 229910000161 silver phosphate Inorganic materials 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 1
Classifications
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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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- 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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
-
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1808—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with zinc, cadmium or mercury
-
- 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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
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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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0237—Amines
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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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
- B01J31/0251—Guanidides (R2N-C(=NR)-NR2)
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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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
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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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
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- 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
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a catalyst for alcohol transesterification and application thereof, and a synthetic method of asymmetric dialkyl carbonate, and relates to the technical field of synthesis of dialkyl carbonate. The catalyst for alcohol transesterification of the invention comprises a metallic zinc compound and an auxiliary agent; the auxiliary agent is organic amine strong alkali. The catalyst provided by the invention can activate the ester carbonyl and can activate the alcohol hydroxyl, so that the nucleophilic attack capability of the alcohol raw material is enhanced, and the ester carbonyl is more efficient in receiving electrophiles. The catalyst of the invention is used for alcohol transesterification, improves the reaction efficiency, and solves the difficult problems of limited thermodynamic and extremely low efficiency of the technical route for directly preparing asymmetric dialkyl carbonate by reacting two different polyols with carbon dioxide.
Description
Technical Field
The invention relates to the technical field of synthesis of dialkyl carbonate, in particular to a catalyst for alcohol transesterification and application thereof, and a method for synthesizing asymmetric dialkyl carbonate.
Background
The dialkyl carbonate can be classified into symmetrical carbonate and asymmetrical carbonate, wherein the asymmetrical carbonate has the characteristics of medium boiling point, low melting point, low viscosity, good low-temperature performance, no corrosion, self cleaning, strong dissolving capacity and the like, and can be used as lithium ion battery electrolyte, lubricating oil base oil, special paint solvent, special spice solvent and the like. Lithium secondary batteries using asymmetric carbonates as electrolytes have superior performance, including increased energy density, increased discharge capacitance, longer life cycle, and higher safety performance, compared to symmetric organic carbonates, and are more important lithium ion battery electrolyte components than symmetric carbonates. In addition, as an important organic synthesis intermediate, an asymmetric carbonate can be used as a protecting group for an alcoholic hydroxyl group or a phenolic hydroxyl group.
Using different polyols and CO 2 Asymmetric carbonates can be prepared by reaction, but the reaction is thermodynamically limited and very inefficient. Methanol, ethanol and CO 2 The three-component one-pot reaction is used for preparing methyl ethyl carbonate as an example, a mixed product system is adopted after the reaction, the components comprise dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and the like, the reaction is an equilibrium reaction, and the yield and the content of all the components are very low. The improvement of the reaction efficiency and the chemical selectivity are required to be carried out simultaneously, namely, the problems of thermodynamic limitation are overcome and the development of a chemical specific catalyst is the most critical. However, this problem is very challenging and no effective solution has been available to date.
Disclosure of Invention
The invention aims to provide a catalyst for alcohol transesterification, application thereof and a synthetic method of asymmetric dialkyl carbonate, which solve the problems of limited thermodynamic and extremely low efficiency of a technical route for directly preparing the asymmetric dialkyl carbonate by reacting two different polyols with carbon dioxide.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a catalyst for alcohol transesterification, which comprises a metallic zinc compound and an auxiliary agent; the auxiliary agent is organic amine strong alkali.
Preferably, the metallic zinc compound comprises zinc acetate, zinc chloride, zinc phosphate or zinc oxide.
Preferably, the strong organic amine base comprises 1, 8-diazabicyclo [5.4.0] undec-7-ene, 1, 5-diazabicyclo [4.3.0] -5-nonene, 1, 3-tetramethylguanidine, or triethylamine.
Preferably, the molar ratio of the metallic zinc compound to the auxiliary agent is 1:1-20.
The invention provides application of the catalyst in the preparation of dialkyl carbonate by catalyzing monohydric alcohol and beta-oxo propyl carbonate to carry out alcohol transesterification.
The invention provides a synthetic method of asymmetric dialkyl carbonate, which comprises the following steps: mixing monohydric alcohol with a structure shown in a formula 1, beta-oxo propyl carbonate with a structure shown in a formula 2, a catalyst in the scheme and a polar organic solvent, and performing alcohol transesterification reaction to obtain asymmetric dialkyl carbonate with a structure shown in a formula 3;
the beta-oxo-propyl carbonate is prepared from monohydric alcohol R 3 OH, propargyl alcohol having the structure shown in formula 4, and CO 2 Is prepared by one-pot reaction;
R 4 OH formula 1;
in the formulas 1 to 4, R 4 Is alkyl, R 3 Is alkyl or aromatic ring-containing benzyl, and R 3 And R is R 4 Different; r is R 1 And R is 2 Independently H, alkyl or aryl, and R 1 And R is 2 At least one of them being an alkyl group.
Preferably, the amount of the metallic zinc compound in the catalyst is 0.5 to 30mol% of the beta-oxo-propyl carbonate.
Preferably, the molar ratio of the beta-oxo-propyl carbonate to the monohydric alcohol having the structure shown in formula 1 is 1:1-50.
Preferably, the temperature of the alcohol transesterification reaction is 30-150 ℃ and the time is 2-24 hours.
Preferably, the preparation method of the beta-oxo propyl carbonate comprises the following steps: to monohydric alcohol R 3 Mixing OH, triphenylphosphine, basic silver compound, propargyl alcohol with a structure shown in formula 4 and organic solvent, and introducing CO into the obtained mixture under airtight condition 2 And carrying out one-pot reaction to obtain the beta-oxo propyl carbonate.
The invention provides a catalyst for alcohol transesterification, which comprises a metallic zinc compound and an auxiliary agent; the auxiliary agent is organic amine strong alkali. The beta-oxo propyl carbonate is an asymmetric chain carbonate, but the alkyl substituents at two ends are more, so that a certain steric hindrance effect is brought to an active ester carbonyl group, the alcohol transesterification reaction space effect is obvious, and the conversion efficiency is low. Aiming at the structural characteristics of the reaction molecules and the catalytic reaction principle, the catalyst provided by the invention has the multi-functional characteristic, not only can activate the ester carbonyl, but also can activate the alcohol hydroxyl, so that the nucleophilic attack capability of the alcohol raw material is enhanced, and the ester carbonyl is more efficient in receiving electrophiles. The catalyst of the invention is used for alcohol transesterification reaction, thereby improving the reaction efficiency.
The invention provides an intermittent step-by-step catalytic synthesis method for preparing asymmetric dialkyl carbonate by utilizing beta-oxo propyl carbonate and another monohydric alcohol through alcohol transesterification, which solves the problem of extremely low technical route efficiency of preparing the asymmetric dialkyl carbonate by directly reacting monohydric alcohol with carbon dioxide through developing a high-efficiency catalyst.
Detailed Description
In the present invention, the raw materials used are commercially available products well known in the art, unless specifically described otherwise.
The invention provides a catalyst for alcohol transesterification, which comprises a metallic zinc compound and an auxiliary agent; the auxiliary agent is organic amine strong alkali.
In the present invention, the metallic zinc compound preferably includes zinc acetate, zinc chloride, zinc phosphate or zinc oxide; the strong organic amine base preferably comprises 1, 8-diazabicyclo [5.4.0]]Undec-7-ene (DBU), 1, 5-diazabicyclo [4.3.0]-5-nonene (DBN), 1, 3-Tetramethylguanidine (TMG) or triethylamine (Et) 3 N); the molar ratio of the metallic zinc compound to the auxiliary agent is preferably 1:1 to 20, more preferably 1:5 to 15, and even more preferably 1:8 to 12.
The catalyst provided by the invention has the characteristics of multifunction, not only can activate the ester carbonyl, but also can activate the alcohol hydroxyl, so that the nucleophilic attack capability of the alcohol raw material is enhanced, and the ester carbonyl is more efficient in receiving electrophiles. The catalyst of the invention is used for alcohol transesterification reaction, thereby improving the reaction efficiency.
The invention provides an application of the catalyst in the preparation of dialkyl carbonate by catalyzing monohydric alcohol and beta-oxo propyl carbonate through alcohol transesterification.
In the present invention, the dialkyl carbonate is preferably a symmetrical dialkyl carbonate or an asymmetrical dialkyl carbonate.
The invention provides a synthetic method of asymmetric dialkyl carbonate, which comprises the following steps: mixing monohydric alcohol with a structure shown in a formula 1, beta-oxo propyl carbonate with a structure shown in a formula 2, a catalyst in the scheme and a polar organic solvent, and performing alcohol transesterification reaction to obtain asymmetric dialkyl carbonate with a structure shown in a formula 3;
the beta-oxo-propyl carbonate is prepared from monohydric alcohol R 3 OH, propargyl alcohol having the structure shown in formula 4, and CO 2 Is prepared by one-pot reaction;
R 4 OH formula 1;
in the formulas 1 to 4, R 4 Is alkyl, R 3 Is alkyl or aromatic ring-containing benzyl, and R 3 And R is R 4 Different; r is R 1 And R is 2 Independently H, alkyl or aryl, and R 1 And R is 2 At least one of them being an alkyl group.
In the present invention, the preparation method of the beta-oxo-propyl carbonate preferably comprises the following steps: to monohydric alcohol R 3 Mixing OH, triphenylphosphine, basic silver compound, propargyl alcohol with a structure shown in formula 4 and organic solvent, and introducing CO into the obtained mixture under airtight condition 2 And carrying out one-pot reaction to obtain the beta-oxo propyl carbonate.
In the present invention, the monohydric alcohol R 3 R in OH 3 Is alkyl or aromatic ring-containing benzyl, when R 3 In the case of an alkyl group, the alkyl group is preferably a linear alkyl group, more preferably a linear alkyl group having 1 to 25 carbon atoms, and still more preferably a linear alkyl group having 1 to 5 carbon atoms; when R is 3 In the case of an aromatic ring-containing benzyl group, the aromatic ring-containing benzyl group is preferably benzyl. In the present invention, the basic silver compound is preferably silver carbonate, silver phosphate or silver oxide; r in said 4 1 And R is 2 Independently H, alkyl or aryl, and R 1 And R is 2 At least one of the alkyl groups is an alkyl group, preferably a linear alkyl group, more preferably a linear alkyl group having 1 to 5 carbon atoms; in an embodiment of the invention, the R 1 And R is 2 Is methyl, n-propyl or n-butyl. In the present invention, when R is 1 Or R is 2 When aromatic, the aromatic group preferably includes phenyl, p-methylphenyl or p-ethylphenyl. In the present invention, the organic solvent is preferably acetonitrile or N, N-Dimethylformamide (DMF).
In the present invention, the basic silver compound is preferably used in an amount of monohydric alcohol R 3 5 to 20mmol of OH; the triphenylphosphine is preferably used in an amount of monohydric alcohol R 3 5 to 40mol% of OH; said monohydric alcohol R 3 The molar ratio of OH to propargyl alcohol having the structure represented by formula 4 is 1:1 to 10, more preferably 1:3 to 8, still more preferably 1:5 to 6. The invention has no special requirement on the dosage of the organic solvent, and can prepare monohydric alcohol R 3 The OH and propargyl alcohol are completely dissolved.
In the present invention, the one-pot reaction is preferably carried out in a reaction vessel. In the present invention, the CO 2 The filling amount of (2) is preferably such that the pressure in the closed environment reaches 0.5 to 5.0MPa, more preferably 1 to 4MPa, and still more preferably 2 to 3MPa. In the present invention, the temperature of the one-pot reaction is preferably 40 to 100 ℃, more preferably 60 to 80 ℃; the one-pot reaction time is preferably 5 to 24 hours, more preferably 10 to 20 hours, and still more preferably 14 to 16 hours. In the present invention, the one-pot reaction is preferably carried out under stirring.
In the present invention, the one-pot reaction is as follows:
after the one-pot reaction is completed, the invention preferably reduces the reaction kettle to room temperature, slowly discharges unreacted carbon dioxide, opens the reaction kettle, takes out the mixed material, removes the organic solvent, and obtains the product beta-oxo propyl carbonate by column chromatography separation.
After the beta-oxo-propyl carbonate is obtained, the invention mixes the monohydric alcohol with the structure shown in the formula 1, the beta-oxo-propyl carbonate, the catalyst described in the scheme and the polar organic solvent to carry out alcohol transesterification reaction to obtain the asymmetric dialkyl carbonate with the structure shown in the formula 3.
In the present invention, in the formula 1, R 4 The alkyl group is preferably a linear alkyl group, more preferably a linear alkyl group having 1 to 25 carbon atoms. In embodiments of the invention, R 4 Is ethyl or n-propyl.
In the present invention, the amount of the metallic zinc compound used in the catalyst is preferably 0.5 to 30mol%, more preferably 5 to 25mol%, still more preferably 10 to 20mol% of the β -oxopropyl carbonate.
In the present invention, the polar organic solvent is preferably acetonitrile or N, N-Dimethylformamide (DMF). The invention has no special requirement on the dosage of the polar organic solvent, and can completely dissolve monohydric alcohol with the structure shown in the formula 1 and beta-oxo propyl carbonate.
In the present invention, the molar ratio of the β -oxopropyl carbonate to the monohydric alcohol having the structure represented by formula 1 is preferably 1:1 to 50, more preferably 1:5 to 45, still more preferably 1:10 to 40, still more preferably 1:20 to 30.
In the present invention, the temperature of the transesterification reaction of alcohols is preferably 30 to 150 ℃, more preferably 50 to 130 ℃, still more preferably 80 to 100 ℃; the time is preferably 2 to 24 hours, more preferably 5 to 20 hours, and still more preferably 10 to 15 hours. The products of the transesterification reaction of alcohols described in the present invention are asymmetric dialkyl carbonates and alpha-hydroxy ketones.
In the present invention, the equation of the transesterification reaction of alcohols is as follows:
after the alcohol transesterification reaction is completed, the present invention preferably further comprises subjecting the obtained reaction product to column chromatography to obtain ethylbenzyl carbonate. In the present invention, the eluting agent used for the column chromatography is preferably ethyl acetate and n-hexane, and the volume ratio of the ethyl acetate to the n-hexane is preferably 1:5 to 50, more preferably 1:10 to 40, and even more preferably 1:20 to 30.
The catalyst for transesterification of alcohols, the use thereof, and the method for synthesizing asymmetric dialkyl carbonate according to the present invention will be described in detail with reference to examples, but they should not be construed as limiting the scope of the present invention.
The following examples and comparative examples were prepared using beta-oxopropyl carbonate as follows:
to a 50mL autoclave was added 5mol% of silver carbonate (relative toMonohydric alcohol), triphenylphosphine 10mol% (relative to monohydric alcohol), monohydric alcohol (benzyl alcohol, R 3 ＝PhCH 2 ) 0.01mol, propargyl alcohol (R) 1 ＝R 2 =me), the reaction vessel was closed and CO was charged 2 The pressure is 1.0MPa, the reaction temperature is 80 ℃, the reaction time is 16 hours, and the acetonitrile accounts for 30 percent of the volume of the reaction kettle. After the reaction is completed, the temperature is reduced to room temperature, unreacted carbon dioxide is slowly discharged, a reaction kettle is opened, the mixed material is taken out, and the gas chromatograph detects the product beta-oxo propyl carbonate with the yield of 85 percent. The product beta-oxo propyl carbonate is obtained by column chromatography separation, and the leaching agent uses ethyl acetate and n-hexane (v) Second step :v Positive direction ＝1:3～1:20)。
Example 1
2mol% of anhydrous zinc acetate (relative to ethanol) and 4mol% of 1, 8-diazabicyclo [5.4.0 were weighed out separately]Undec-7-ene (relative to ethanol) was added to a tetrafluoro liner in a 50mL autoclave, placed in a magnetic rod, and then beta-oxopropyl carbonate (R) 1 ＝R 2 =me) 0.01mol, ethanol 0.1mol, and N, N-Dimethylformamide (DMF) 15mL, the liquid content was 30% of the effective volume in the reactor, and the reaction was stirred at 80 ℃ for 8h. After the reaction is finished, the mother liquor composition is analyzed and quantified. The conversion rate of the beta-oxo propyl carbonate is 80.5%, the yield of the ethyl benzyl carbonate is 78.6%, and the yield of the alpha-hydroxy ketone is 79.2%.
Examples 2 to 7
The procedure is as in example 1, and the specific reaction conditions are shown in Table 1.
Comparative examples 1 to 3
The differences from example 1 are shown in Table 1.
TABLE 1 reaction conditions and reaction results for examples and comparative examples
From the results in table 1, it can be seen that the catalyst provided by the invention not only can activate the ester carbonyl group, but also can activate the alcohol hydroxyl group, so that the nucleophilic attack ability of the alcohol raw material is enhanced, and the ester carbonyl group is more efficient in receiving electrophiles. The catalyst provided by the invention is used for alcohol transesterification, so that the reaction efficiency is improved, the problem of extremely low technical route efficiency of preparing asymmetric dialkyl carbonate by directly reacting monohydric alcohol and carbon dioxide is solved, and the catalyst has a good technical application prospect.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A catalyst for transesterification of alcohols, comprising a metallic zinc compound and an auxiliary agent; the auxiliary agent is organic amine strong alkali.
2. The catalyst of claim 1, wherein the metallic zinc compound comprises zinc acetate, zinc chloride, zinc phosphate, or zinc oxide.
3. The catalyst of claim 1 wherein the strong organic amine base comprises 1, 8-diazabicyclo [5.4.0] undec-7-ene, 1, 5-diazabicyclo [4.3.0] -5-nonene, 1, 3-tetramethylguanidine, or triethylamine.
4. A catalyst according to any one of claims 1 to 3, wherein the molar ratio of the metallic zinc compound to the promoter is from 1:1 to 20.
5. Use of the catalyst according to any one of claims 1 to 4 for catalyzing the transesterification of monohydric alcohols with beta-oxopropyl carbonate to prepare dialkyl carbonates.
6. A method for synthesizing asymmetric dialkyl carbonate, which is characterized by comprising the following steps: mixing monohydric alcohol with a structure shown in a formula 1, beta-oxo propyl carbonate with a structure shown in a formula 2, the catalyst of any one of claims 1-4 and a polar organic solvent, and performing alcohol transesterification reaction to obtain asymmetric dialkyl carbonate with a structure shown in a formula 3;
the beta-oxo-propyl carbonate is prepared from monohydric alcohol R 3 OH, propargyl alcohol having the structure shown in formula 4, and CO 2 Is prepared by one-pot reaction;
R 4 OH formula 1;
in the formulas 1 to 4, R 4 Is alkyl, R 3 Is alkyl or aromatic ring-containing benzyl, and R 3 And R is R 4 Different; r is R 1 And R is 2 Independently H, alkyl or aryl, and R 1 And R is 2 At least one of them being an alkyl group.
7. The method according to claim 6, wherein the amount of the metal zinc compound in the catalyst is 0.5 to 30mol% based on the beta-oxopropyl carbonate.
8. The method according to claim 6, wherein the molar ratio of the beta-oxopropyl carbonate to the monohydric alcohol having the structure represented by formula 1 is 1:1 to 50.
9. The method according to any one of claims 6 to 8, wherein the alcohol transesterification reaction is carried out at a temperature of 30 to 150 ℃ for a time of 2 to 24 hours.
10. The synthesis method according to claim 6, wherein,the preparation method of the beta-oxo propyl carbonate comprises the following steps: to monohydric alcohol R 3 Mixing OH, triphenylphosphine, basic silver compound, propargyl alcohol with a structure shown in formula 4 and organic solvent, and introducing CO into the obtained mixture under airtight condition 2 And carrying out one-pot reaction to obtain the beta-oxo propyl carbonate.
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