CN117069687A - Method for catalyzing and fixing carbon dioxide by halogen-free organic ion to catalyst - Google Patents
Method for catalyzing and fixing carbon dioxide by halogen-free organic ion to catalyst Download PDFInfo
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- CN117069687A CN117069687A CN202310945420.6A CN202310945420A CN117069687A CN 117069687 A CN117069687 A CN 117069687A CN 202310945420 A CN202310945420 A CN 202310945420A CN 117069687 A CN117069687 A CN 117069687A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 35
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 150000005676 cyclic carbonates Chemical class 0.000 claims abstract description 9
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 142
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 99
- 239000001257 hydrogen Substances 0.000 claims description 43
- 229910052739 hydrogen Inorganic materials 0.000 claims description 43
- 150000002118 epoxides Chemical class 0.000 claims description 35
- 150000002500 ions Chemical class 0.000 claims description 22
- 230000035484 reaction time Effects 0.000 claims description 21
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- 150000007530 organic bases Chemical class 0.000 claims description 13
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 12
- UBQKCCHYAOITMY-UHFFFAOYSA-N pyridin-2-ol Chemical group OC1=CC=CC=N1 UBQKCCHYAOITMY-UHFFFAOYSA-N 0.000 claims description 12
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 10
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 10
- -1 N-atom organic bases Chemical class 0.000 claims description 8
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 238000001308 synthesis method Methods 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 6
- 150000002357 guanidines Chemical class 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical group CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 4
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 3
- SFJRUJUEMVAZLM-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxymethyl]oxirane Chemical compound CC(C)(C)OCC1CO1 SFJRUJUEMVAZLM-UHFFFAOYSA-N 0.000 claims description 3
- WHNBDXQTMPYBAT-UHFFFAOYSA-N 2-butyloxirane Chemical compound CCCCC1CO1 WHNBDXQTMPYBAT-UHFFFAOYSA-N 0.000 claims description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 3
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 3
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- UURSXESKOOOTOV-UHFFFAOYSA-N dec-5-ene Chemical compound CCCCC=CCCCC UURSXESKOOOTOV-UHFFFAOYSA-N 0.000 claims description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 3
- WPUNBCKVQVACJB-UHFFFAOYSA-N 2-(4-chlorophenyl)-3-[[3-(4-chlorophenyl)oxiran-2-yl]methoxymethyl]oxirane Chemical compound C1=CC(Cl)=CC=C1C1C(COCC2C(O2)C=2C=CC(Cl)=CC=2)O1 WPUNBCKVQVACJB-UHFFFAOYSA-N 0.000 claims description 2
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 claims description 2
- QNYBOILAKBSWFG-UHFFFAOYSA-N 2-(phenylmethoxymethyl)oxirane Chemical compound C1OC1COCC1=CC=CC=C1 QNYBOILAKBSWFG-UHFFFAOYSA-N 0.000 claims description 2
- FDZMLNCJBYFJBH-UHFFFAOYSA-N 2-[(2,3-dibromophenoxy)methyl]oxirane Chemical compound BrC1=CC=CC(OCC2OC2)=C1Br FDZMLNCJBYFJBH-UHFFFAOYSA-N 0.000 claims description 2
- GAMYYCRTACQSBR-UHFFFAOYSA-N 4-azabenzimidazole Chemical compound C1=CC=C2NC=NC2=N1 GAMYYCRTACQSBR-UHFFFAOYSA-N 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims description 2
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 claims description 2
- 125000004970 halomethyl group Chemical group 0.000 claims description 2
- 150000005232 imidazopyridines Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- OEBXWWBYZJNKRK-UHFFFAOYSA-N 1-methyl-2,3,4,6,7,8-hexahydropyrimido[1,2-a]pyrimidine Chemical compound C1CCN=C2N(C)CCCN21 OEBXWWBYZJNKRK-UHFFFAOYSA-N 0.000 claims 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims 1
- 238000010189 synthetic method Methods 0.000 claims 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims 1
- JABYJIQOLGWMQW-UHFFFAOYSA-N undec-4-ene Chemical compound CCCCCCC=CCCC JABYJIQOLGWMQW-UHFFFAOYSA-N 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000004593 Epoxy Substances 0.000 abstract description 5
- 150000002367 halogens Chemical class 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 229910001220 stainless steel Inorganic materials 0.000 description 73
- 239000010935 stainless steel Substances 0.000 description 73
- 238000001228 spectrum Methods 0.000 description 56
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 54
- 238000005481 NMR spectroscopy Methods 0.000 description 44
- 239000000243 solution Substances 0.000 description 42
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 36
- 239000000203 mixture Substances 0.000 description 21
- 238000004440 column chromatography Methods 0.000 description 19
- 239000007789 gas Substances 0.000 description 18
- 239000005457 ice water Substances 0.000 description 18
- 239000011259 mixed solution Substances 0.000 description 18
- 239000003208 petroleum Substances 0.000 description 18
- 238000007789 sealing Methods 0.000 description 18
- 239000007787 solid Substances 0.000 description 18
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 15
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- GCNTZFIIOFTKIY-UHFFFAOYSA-N 4-hydroxypyridine Chemical compound OC1=CC=NC=C1 GCNTZFIIOFTKIY-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 5
- GRFNBEZIAWKNCO-UHFFFAOYSA-N 3-pyridinol Chemical compound OC1=CC=CN=C1 GRFNBEZIAWKNCO-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 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 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- LKMJVFRMDSNFRT-SCSAIBSYSA-N (2s)-2-(methoxymethyl)oxirane Chemical compound COC[C@@H]1CO1 LKMJVFRMDSNFRT-SCSAIBSYSA-N 0.000 description 1
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 1
- MUUOUUYKIVSIAR-UHFFFAOYSA-N 2-but-3-enyloxirane Chemical compound C=CCCC1CO1 MUUOUUYKIVSIAR-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005059 halophenyl group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910021654 trace metal Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
-
- 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
-
- 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
-
- 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
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- 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)
-
- 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
- B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for catalyzing and fixing carbon dioxide by using a halogen-free organic ion pair catalyst, which is used for synthesizing cyclic carbonate by using an epoxy substrate shown in a formula II and carbon dioxide in the presence of a catalyst shown in a formula I at a temperature of between 100 and 120 ℃. Compared with other existing catalytic systems, the catalyst has the obvious advantages of no solvent, less catalyst consumption, mildness, high efficiency, low cost, easy preparation, no metal, no halogen and the like, and the catalyst is easy to prepare and has wide applicability.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a method for catalyzing and fixing carbon dioxide by using a halogen-free organic ion pair catalyst.
Background
Fossil fuel combustion has been the basis for almost all power generation in the past 140 years; still providing the fuel needed for heating for almost all sea, land, air transportation and providing the thermal energy needed to drive other businesses. The carbon dioxide level in the atmosphere has risen from about 280ppm at the beginning of the industrial revolution to 316ppm to 417ppm in 2020. Carbon dioxide is a major component of greenhouse gases, and the concentration of carbon dioxide in the atmosphere increases dramatically, causing many environmental problems such as global warming, sea level elevation, and frequent extreme weather. Chemical fixation of carbon dioxide into chemicals with high added value is the most popular, as carbon dioxide can be a renewable and inexpensive carbon source in the chemical industry. However, only 1% of the carbon dioxide emitted each year is chemically synthesized in industry, which has a negligible share in the huge amount of artificial carbon dioxide emissions. Among many methods for fixing carbon dioxide, the method of combining carbon dioxide with epoxide to form cyclic carbonate (CCE reaction) is one of the most promising routes for utilizing carbon dioxide, because cyclic carbonate has a wide range of applications, such as aprotic polar solvents, electrolyte microelectronics of lithium ion batteries, and the like.
Because carbon dioxide has thermodynamic stability and chemical inertness, designing a catalyst that can efficiently activate carbon dioxide is critical to the industrialization of the reaction. In past studies, metal catalysis and organic catalysis were the two most common forms of catalyzing CCE reactions. Metal catalysts are widely and intensively studied. Among them, metal catalysts are metal complexes (angel. Chem. Int. Ed.2011,50,8510), alkali metal salts (catalyst. Sci. Technology. 2019,9,4393), and metal oxides (Chemical Engineering journal.2021,405, 126907), and the like. However, metal catalysis can cause trace metal residues in cyclic carbonate products, which may pollute the environment and cannot be directly applied to fields such as biomedicine and microelectronics, which have strict limits on the metal residues. In recent years, organic catalysts have been widely used for CCE reactions due to their excellent catalytic activity and thermodynamic stability. Most organic catalysts contain halogen, have the advantages of high halogen activity, high selectivity and the like, but the organic catalysts can cause irreversible corrosion and damage to a reaction container, and can cause serious damage to the environment, so that the practical application of the reaction in industrial scenes is limited.
Non-halogen organic catalysts are of industrial interest and practical applicability. The catalyst is free of metal residue and halogen-free, and can avoid halide-induced reactionReactor corrosion risk. Simultaneously has high activity and high selectivity, and can rapidly catalyze CCE reaction to realize CO 2 Is fixed chemically. In this respect, the ionic liquid has better thermal stability, wider adjustable range of liquid and better adsorption effect on carbon dioxide. However, these catalysts or raw materials are expensive, or the purification process is complicated, or the synthetic steps are excessive, so that the yield is lowered, thereby limiting the wide production applications thereof.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a method for catalyzing and fixing carbon dioxide by using a halogen-free organic ion pair catalyst. The invention develops a halogen-free pyridine anion-containing organic ion pair catalyst for preparing five-membered cyclic carbonate by catalyzing and fixing carbon dioxide and epoxide. The catalyst has the advantages of low cost and easy obtainment of raw materials, no treatment for one-step synthesis, good thermal stability, and realization of high-efficiency conversion of cycloaddition reaction of epoxide and carbon dioxide under extremely low load. The five-membered cyclic carbonate obtained by the method has no metal and halogen residues, and has great industrialized application potential from the aspects of environmental protection and economy.
The invention provides a method for preparing cyclic carbonate by catalyzing epoxy immobilized carbon dioxide by using a halogen-free organic ion pair catalyst consisting of hydroxypyridine and common organic base for the first time. The target product is directly obtained by reacting the hydroxypyridine with 3 different substitution sites with common commercially available organic base in solvent, and can be directly used after drying, the synthesis steps are simple, and the yield is high.
In order to expand the application of the carbonic ester in industrial production industrialization, the method finds out the problem from the actual demand and solves the problem, and utilizes a halogen-free organic ion pair catalyst consisting of hydroxypyridine and common organic base, wherein conjugate acid of the common commercial organic base is used as a hydrogen bond acceptor (HBD) to activate epoxy, oxo-anions of pyridine anions are used to activate carbon dioxide, so that various substituted cyclic carbonic esters are synthesized.
The technical scheme for achieving the purpose is as follows:
a method for catalyzing and fixing carbon dioxide by using a halogen-free organic ion pair catalyst comprises the steps of adopting epoxide shown in a formula (II) and carbon dioxide to generate a cyclic carbonate compound under the catalysis of the halogen-free ion pair catalyst shown in a formula (I) under the condition of no solvent:
wherein the Hydrogen Bond Donor (HBD) is selected from the conjugate acids of common commercial organic bases; wherein the organic base may be selected from C 1 ～C 4 Alkyl substituted quaternary ammonium base compound, C 1 ～C 4 Alkyl substituted or unsubstituted guanidine, imidazopyridine compounds,
the structure of the epoxide is shown as a formula (II):
said R is 1 And R is 2 Selected from hydrogen, n-butyl, halogen-substituted alkyl, phenyl, benzyl or R 3 -O-CH 2 -, said R 3 Selected from phenyl, phenyl substituted with alkyl of 1 to 3 carbon atoms, halogen substituted phenyl, allyl or straight or branched alkyl of 1 to 4 carbon atoms, said R 1 And R is 2 Are of the same or different construction.
The preparation method of the halogen-free ion pair catalyst shown in the formula (I) comprises the steps of adopting any one combination of the organic base and hydroxypyridine substituted by three different positions of ortho position, meta position and para position, carrying out acid-base neutralization at 0-25 ℃, and reacting at room temperature for 6-24 hours, wherein the molar ratio of hydroxypyridine to organic base is 0.5-2:1.
Preferably said R 1 And R is 2 When the same is used, the R is selected from phenyl 1 And R is 2 At different times, selected from hydrogen, n-butyl, halomethyl, phenyl, halophenyl, R 3 -O-CH 2 -, said R 3 Selected from phenyl, tolyl, allyl, t-butyl, or methyl.
Preferably said C 1 ～C 4 The alkyl substituted quaternary ammonium base compound is selected from tetrabutylammonium hydroxide, tetrapropylammonium hydroxide and tetraethyl hydroxideAmmonium; the imidazopyridine-containing organic base is selected from 1,5, 7-triazidine bicyclo (4.4.0) dec-5-ene (TBD), 7-methyl-1, 5, 7-triazabicyclo [4.4.0]]Dec-5-ene (MTBD), 1, 8-diazabicyclo [5.4.0]Undec-7-ene (DBU), 4-Dimethylaminopyridine (DMAP);
the C is 1 ～C 4 The alkyl substituted or unsubstituted guanidine is selected from Tetramethylguanidine (TMG), guanidine, 1-dimethylguanidine. Preferably, the catalyst of formula I is selected from the following structures:
structure and numbering
More preferably, the halogen-free catalyst of formula (I) is selected from the group consisting of the structures:
structure and numbering
Preferably, the epoxide of formula II is selected from the group consisting of styrene oxide, bromopropane oxide, epichlorohydrin, t-butyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, butyl oxirane, methoxymethyl oxirane, 2-toluene glycidyl ether, 1, 2-epoxy-5-hexene.
The structure of the epoxide is shown below:
structure and numbering
More preferably the epoxide is selected from the group consisting of epichlorohydrin, epibromohydrin, allyl glycidyl ether, t-butyl glycidyl ether, benzyl glycidyl ether, 4-chlorobenzeneglycidyl ether, dibromophenylglycidyl ether, phenylglycidyl ether, 2-toluene glycidyl ether, styrene oxide, (methoxymethyl) ethylene oxide, butyl ethylene oxide.
The reaction temperature is 80-120 ℃, the reaction time is 1-24h, the initial pressure of carbon dioxide is 0.05-10MPa, and the molar ratio of epoxide shown as formula (II) to halogen-free catalyst shown as formula (I) is 100:0.1-100:5
The preferable reaction temperature is 100-120 ℃, the preferable reaction time is 6-24h, the initial pressure of carbon dioxide is 1-2MPa, and the molar ratio of epoxide shown in formula (II) to halogen-free catalyst shown in formula (I) is 100:0.5 to 100:1
Preferably, the specific method for fixing carbon dioxide comprises the following steps: adding a catalyst shown in a formula I and an epoxy compound shown in a formula II into a stainless steel pressure reaction tube under the protection of inert gas or nitrogen, then filling 1-2Mpa carbon dioxide into the reactor, heating to 100-120 ℃ under the atmosphere of carbon dioxide, and reacting for 6-24 hours to obtain a solution containing a product.
Preferably, the reacted solution is cooled and subjected to column chromatography, and then is spin-dried to obtain the product.
Preferably, the synthesis method of the catalyst shown in the formula I is as follows: slowly dripping an organic alkali organic solution into an organic solution of hydroxypyridine under the condition of stirring, reacting at 0-25 ℃ after the addition, spin-drying, and vacuum drying to obtain the product.
Preferably, the solvent in the commercial organic base organic solution is methanol, and the solvent in the organic solution of the pyridine compound is methanol.
Advantageous effects
The technical scheme of the invention can at least achieve one of the following beneficial effects:
(1) Compared with the prior art that a metal catalyst (magnesium-aluminum mixed oxide) is utilized, the cyclic carbonate synthesized by the halogen catalyst has the characteristics of high yield, no metal residue, no halogen residue, wide application and the like.
(2) The reaction process does not need to use a solvent, avoids the toxicity of an organic solvent, is easy to separate in a later period, and achieves a green chemical process.
(3) The catalytic system uses an ion pair bifunctional catalyst, activates an epoxy substrate through the hydrogen bond action of HBD, fixes carbon dioxide by using oxygen anions of pyridine anions, and is relatively simple.
(4) The invention has the advantages of simple catalytic reaction of the catalytic system, simple process, simple and convenient required equipment and suitability for industrialized amplification.
(5) The catalyst system used in the invention is cheap and easy to prepare, and the catalyst dosage is small, thus the invention has the characteristic of high-efficiency quantitative conversion.
In conclusion, compared with other existing catalytic systems, the catalyst has the obvious advantages of no solvent, less catalyst consumption, high efficiency, low-cost and easy preparation of the catalyst, no metal, no halogen and the like.
Drawings
Embodiments of the present invention will be described in detail with reference to the accompanying drawings, in which
Fig. 1: the hydrogen-carbon spectrum of the carbonate product of example 1;
fig. 2 to 20: the hydrogen-carbon spectra of the carbonate products of examples 2 to 19, respectively;
fig. 21 to 27: the hydrogen-carbon spectra of the catalysts obtained in examples 1 to 6.
Detailed Description
The invention will be further illustrated by the following examples, which are intended to illustrate, but not to limit, the invention. It will be understood by those of ordinary skill in the art that these examples are not limiting of the invention in any way and that appropriate modifications and data changes may be made thereto without departing from the spirit and scope of the invention.
The nuclear magnetic resonance hydrogen spectrum involved in the examples was measured by Bruker Assend TM-400 nuclear magnetic resonance hydrogen spectrometer (Bruker), the deuterated reagent was deuterated chloroform (CDCl) 3 ) Or deuterated DMSO (DMSO-d 6).
The starting materials used in the examples below were all purchased from Alfa Aesar.
The catalytic system used in the examples had the following structure:
structure and numbering
The epoxide used in the examples had the following structure:
structure and numbering
Example 1:
epoxide (A) (1.6 ml,10mmol,1.0 equiv), ion-pair catalyst 1 (0.0117 g,0.05mmol,0.05 equiv) were charged into a stainless steel pressure reaction tube. Sealing stainless steel pressure reaction tube with CO 2 Air in the stainless steel pressure reaction tube is replaced for 3 times, and then CO is filled into the reaction kettle 2 The initial pressure is 1MPa, the temperature is raised to 120 ℃, and the reaction time is 24 hours. After the reaction was completed, the stainless steel pressure reaction tube was cooled by an ice-water mixture at 0 ℃ to release a residual gas, and after column chromatography (petroleum ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, and the solution was spin-dried on a spin-evaporator to obtain a yellow solid, which was dried to a constant weight with a conversion of 90% and a selectivity of 92%. The hydrogen spectrum of the product is shown in figure 1, (nuclear magnetic resonance hydrogen spectrum, 400Hz, CDCl) 3 ). The spectrogram data are: 1 h NMR (400 mhz, chloroform-d) delta 7.44-7.37 (m, 3H), 7.36-7.30 (m, 2H), 5.65 (t, j=8.0 hz, 1H), 4.77 (t, j=8.4 hz, 1H), 4.29 (dd, j=8.6, 7.8hz, 1H). The carbon spectrum of the product is shown in figure 2, (nuclear magnetic resonance hydrogen spectrum, 101Hz, CDCl) 3 ). The spectrogram data are: 13 C NMR(101MHz,Chloroform-d)δ154.11,134.98,128.77,128.28,125.07,77.16,70.31。
the preparation method of the catalyst 1 comprises the following steps: 4-hydroxypyridine (3 mmol,0.2853g,1.0 equiv) was dissolved in 15ml methanol and stirred well. TBD (3 mmol,0.4176g,1 equiv) was dissolved in 10ml of methanol (10 ml). The methanol solution of TBD was added dropwise to the methanol solution of 4-hydroxypyridine at 0deg.C with stirring. After the TBD solution was added dropwise, the mixture was stirred at room temperature for 12 hours. After the reaction, the methanol solvent is removed under reduced pressure, and the reaction is trueAfter several days of air drying, the catalyst 1 was obtained as a yellow oil. The hydrogen spectrum is shown in FIG. 21, (nuclear magnetic resonance hydrogen spectrum, 400Hz, DMSO-d 6). The spectrogram data are: 1 h NMR (400 mhz, dmso-d 6) delta 7.72 (d, j=5.7 hz, 2H), 6.69 (s, 2H), 6.10 (d, j=5.7 hz, 2H), 3.19 (d, j=13.8 hz, 8H), 1.85 (p, j=5.9 hz, 4H). The carbon spectrum of the product is shown in FIG. 22, (nuclear magnetic resonance hydrogen spectrum, 101Hz, DMSO-d 6). The spectrogram data are: 13 C NMR(101MHz,DMSO-d6)δ173.84,151.04,148.63,115.59,46.24,37.57,20.57。
example 2:
epoxide (A) (1.6 ml,10mmol,1.0 equiv), ion pair catalyst 2 (0.0117 g,0.05mmol,0.05 equiv) were charged into a stainless steel pressure reaction tube. Sealing stainless steel pressure reaction tube with CO 2 Air in the stainless steel pressure reaction tube is replaced for 3 times, and then CO is filled into the reaction kettle 2 The initial pressure is 1MPa, the temperature is raised to 120 ℃, and the reaction time is 24 hours. After the reaction was completed, the stainless steel pressure reaction tube was cooled by an ice-water mixture at 0 ℃ to release a residual gas, and after column chromatography (petroleum ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, and the solution was spin-dried on a spin-evaporator to obtain a yellow solid, which was dried to a constant weight with a conversion of 75% and a selectivity of 80%.
The preparation method of the catalyst 2 comprises the following steps: 3-hydroxypyridine (3 mmol,0.2853g,1.0 equiv) was dissolved in 15ml methanol and stirred well. TBD (3 mmol,0.4176g,1 equiv) was dissolved in 10ml of methanol (10 ml). The methanol solution of TBD was added dropwise to the methanol solution of 3-hydroxypyridine at 0deg.C with stirring. After the TBD solution was added dropwise, the mixture was stirred at room temperature for 12 hours. After the reaction was completed, the methanol solvent was removed under reduced pressure, and dried in vacuo for several days to give catalyst 2 as a yellow oil. The hydrogen spectrum is shown in FIG. 23, (nuclear magnetic resonance hydrogen spectrum, 400MHz, DMSO-d 6). The spectrogram data are: 1 H NMR(400MHz,DMSO-d6)δ8.04(s,2H),7.76(d,J＝2.9Hz,1H),7.48(dd,J＝4.5,1.4Hz,1H),6.87(dd,J＝8.2,4.4Hz,1H),6.66(ddd,J＝8.3,3.0,1.5Hz,1H),3.25–3.13(m,8H),1.83(p,J＝5.9Hz,4H)。
example 3:
epoxide (A) (1.6 ml,10mmol,1.0 equiv), ion-pair catalyst 3(0.0117 g,0.05mmol,0.05 equiv) was added to a stainless steel pressure reaction tube. Sealing stainless steel pressure reaction tube with CO 2 Air in the stainless steel pressure reaction tube is replaced for 3 times, and then CO is filled into the reaction kettle 2 The initial pressure is 1MPa, the temperature is raised to 120 ℃, and the reaction time is 24 hours. After the reaction was completed, the stainless steel pressure reaction tube was cooled by an ice-water mixture at 0 ℃ to release a residual gas, and after column chromatography (petroleum ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, and the solution was spin-dried on a spin-evaporator to obtain a yellow solid, which was dried to a constant weight with a conversion of 70% and a selectivity of 78%.
The preparation method of the catalyst 3 comprises the following steps: 2-hydroxypyridine (3 mmol,0.2853g,1.0 equiv) was dissolved in 15ml methanol and stirred well. TBD (3 mmol,0.4176g,1 equiv) was dissolved in 10ml of methanol (10 ml). The methanol solution of TBD was added dropwise to the methanol solution of 2-hydroxypyridine at 0deg.C with stirring. After the TBD solution was added dropwise, the mixture was stirred at room temperature for 12 hours. After the reaction was completed, the methanol solvent was removed under reduced pressure, and dried in vacuo for several days to give catalyst 3 as a yellow oil. The hydrogen spectrum is shown in FIG. 24, (nuclear magnetic resonance hydrogen spectrum, 400Hz, DMSO-d 6). The spectrogram data are: 1 H NMR(400MHz,DMSO-d6)δ8.81(s,2H),7.61–7.53(m,1H),7.18(ddd,J＝8.9,6.9,2.4Hz,1H),6.08–5.99(m,2H),3.26–3.17(m,8H),1.85(p,J＝5.9Hz,4H)。
example 4:
epoxide (A) (1.6 ml,10mmol,1.0 equiv), ion-pair catalyst 4 (0.0124 g,0.05mmol,0.05 equiv) were charged into a stainless steel pressure reaction tube. Sealing stainless steel pressure reaction tube with CO 2 Air in the stainless steel pressure reaction tube is replaced for 3 times, and then CO is filled into the reaction kettle 2 The initial pressure is 1MPa, the temperature is raised to 120 ℃, and the reaction time is 24 hours. After the reaction was completed, the stainless steel pressure reaction tube was cooled by an ice-water mixture at 0 ℃ to release a residual gas, and after column chromatography (petroleum ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, and the solution was spin-dried on a spin-evaporator to obtain a yellow solid, which was dried to a constant weight with a conversion of 78% and a selectivity of 80%.
The preparation method of the catalyst 4 comprises the following steps of: 4-hydroxypyridine (3 mmol,0.2853g,1.0 equiv) was dissolved in 15ml methanol and stirred well. MTBD (3 mmol,0.4597g,1 equiv) was dissolved in 10ml methanol (10 ml). The methanol solution of MTBD was added dropwise to the methanol solution of 4-hydroxypyridine at 0deg.C with stirring. After the MTBD solution was added dropwise, it was stirred at room temperature for 12 hours. After the reaction was completed, the methanol solvent was removed under reduced pressure, and dried in vacuo for several days to give catalyst 4 as a yellow oil. The hydrogen spectrum is shown in FIG. 25, (nuclear magnetic resonance hydrogen spectrum, 400Hz, DMSO-d 6). The spectrogram data are: 1 H NMR(400MHz,DMSO-d6)δ7.83–7.72(m,2H),6.28–6.19(m,2H),6.06(s,2H),3.23–3.12(m,8H),2.85(s,3H),1.89(p,J＝6.0Hz,2H),1.79(p,J＝5.9Hz,2H)。
example 5:
epoxide (A) (1.6 ml,10mmol,1.0 equiv), ion pair catalyst 5 (0.0124 g,0.05mmol,0.05 equiv) was charged to a stainless steel pressure reactor tube. Sealing stainless steel pressure reaction tube with CO 2 Air in the stainless steel pressure reaction tube is replaced for 3 times, and then CO is filled into the reaction kettle 2 The initial pressure is 1MPa, the temperature is raised to 120 ℃, and the reaction time is 24 hours. After the reaction was completed, the stainless steel pressure reaction tube was cooled by an ice-water mixture at 0 ℃ to release a residual gas, and after column chromatography (petroleum ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, and the solution was spin-dried on a spin-evaporator to obtain a yellow solid, which was dried to a constant weight with a conversion of 77% and a selectivity of 83%.
The preparation method of the catalyst 5 comprises the following steps: 4-hydroxypyridine (3 mmol,0.2853g,1.0 equiv) was dissolved in 15ml methanol and stirred well. DBU (3 mmol,0.4586g,1 equiv) was dissolved in 10ml methanol (10 ml). The methanol solution of DBU was added dropwise to the methanol solution of 4-hydroxypyridine at 0deg.C with stirring. After the DBU solution was added dropwise, it was stirred at room temperature for 12 hours. After the reaction was completed, the methanol solvent was removed under reduced pressure, and dried in vacuo for several days to give catalyst 5 as a yellow oil. The hydrogen spectrum is shown in FIG. 26, (nuclear magnetic resonance hydrogen spectrum, 400Hz, DMSO-d 6). The spectrogram data are: 1 H NMR(400MHz,DMSO-d6)δ8.24(s,2H),7.86–7.73(m,2H),6.27–6.13(m,2H),3.37–3.27(m,4H),3.15(d,J＝5.8Hz,4H),1.79(p,J＝5.8Hz,2H),1.62–1.51(m,6H)。
example 6:
epoxide (A) (1.6 ml,10mmol,1.0 equiv), ion-pair catalyst 6 (0.0109 g,0.05mmol,0.05 equiv) were charged into a stainless steel pressure reaction tube. Sealing stainless steel pressure reaction tube with CO 2 Air in the stainless steel pressure reaction tube is replaced for 3 times, and then CO is filled into the reaction kettle 2 The initial pressure is 1MPa, the temperature is raised to 120 ℃, and the reaction time is 24 hours. After the reaction was completed, the stainless steel pressure reaction tube was cooled by an ice-water mixture at 0 ℃ to release a residual gas, and after column chromatography (petroleum ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, and the solution was spin-dried on a spin-evaporator to obtain a yellow solid, which was dried to a constant weight with a conversion of 66% and a selectivity of 71%.
The preparation method of the catalyst 6 comprises the following steps: 4-hydroxypyridine (3 mmol,0.2853g,1.0 equiv) was dissolved in 15ml methanol and stirred well. DMAP (3 mmol,0.3365g,1 equiv) was dissolved in 10ml of methanol (10 ml). The methanol solution of DMAP was added dropwise to the methanol solution of 4-hydroxypyridine at 0 ℃ with stirring. After the DMAP solution was added dropwise, it was stirred at room temperature for 12 hours. After the reaction was completed, the methanol solvent was removed under reduced pressure, and dried in vacuo for several days to give catalyst 6 as a yellow oil. The hydrogen spectrum is shown in FIG. 27, (nuclear magnetic resonance hydrogen spectrum, 400Hz, DMSO-d 6). The spectrogram data are: 1 H NMR(400MHz,DMSO-d6)δ8.16–8.03(m,2H),7.70(d,J＝6.9Hz,2H),6.66–6.53(m,2H),6.17(d,J＝6.8Hz,2H),3.51–3.25(m,2H),2.94(s,6H).
example 7:
epoxide (A) (1.6 ml,10mmol,1.0 equiv), ion pair catalyst 1 (0.0234 g,0.1mmol,0.1 equiv) was charged to a stainless steel pressure reaction tube. Sealing stainless steel pressure reaction tube with CO 2 Air in the stainless steel pressure reaction tube is replaced for 3 times, and then CO is filled into the reaction kettle 2 The initial pressure is 1MPa, the temperature is raised to 120 ℃, and the reaction time is 24 hours. After the reaction was completed, the stainless steel pressure reaction tube was cooled by an ice-water mixture at 0℃to release residual gas, and after column chromatography (petroleum ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, and the solution was purified by spin-dryingSpin-drying on a steamer gave a yellow solid which was dried to constant weight with a conversion of 94% and a selectivity of 96%.
Example 8:
epoxide (A) (1.6 ml,10mmol,1.0 equiv), ion-pair catalyst 1 (0.0117 g,0.05mmol,0.05 equiv) were charged into a stainless steel pressure reaction tube. Sealing stainless steel pressure reaction tube with CO 2 Air in the stainless steel pressure reaction tube is replaced for 3 times, and then CO is filled into the reaction kettle 2 The initial pressure is 1MPa, the temperature is raised to 100 ℃, and the reaction time is 24 hours. After the reaction was completed, the stainless steel pressure reaction tube was cooled by an ice-water mixture at 0 ℃, the residual gas was released, and after column chromatography (petroleum ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, and the solution was spin-dried on a spin-evaporator to obtain a yellow solid, which was dried to constant weight with a conversion of 86% and a selectivity of 88%.
Example 9:
epoxide (A) (1.6 ml,10mmol,1.0 equiv), ion-pair catalyst 1 (0.0117 g,0.05mmol,0.05 equiv) were charged into a stainless steel pressure reaction tube. Sealing stainless steel pressure reaction tube with CO 2 Air in the stainless steel pressure reaction tube is replaced for 3 times, and then CO is filled into the reaction kettle 2 The initial pressure is 2MPa, the temperature is raised to 120 ℃, and the reaction time is 24 hours. After the reaction was completed, the stainless steel pressure reaction tube was cooled by an ice-water mixture at 0 ℃, the residual gas was released, and after column chromatography (petroleum ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, and the solution was spin-dried on a spin-evaporator to obtain a yellow solid, which was dried to a constant weight with a conversion of 95% and a selectivity of 96%.
Example 10:
epoxide (B) (0.8 ml,10mmol,1.0 equiv), ion-pair catalyst 1 0.0117g,0.05mmol,0.05equiv) was added to a stainless steel pressure reaction tube. Sealing stainless steel pressure reaction tube with CO 2 Air in the stainless steel pressure reaction tube is replaced for 3 times, and then CO is filled into the reaction kettle 2 The initial pressure is 1MPa, the temperature is raised to 120 ℃, and the reaction time is 6 hours. After the reaction is completed, the stainless steel pressure reaction tube is cooled by an ice-water mixture to 0 ℃ to release residual gas, and column chromatography is carried outAfter (petroleum ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, and the solution was spin-dried on a spin-evaporator to obtain a yellow solid, which was dried to constant weight with a conversion of 98% and a selectivity of 97%. The hydrogen spectrum of the product is shown in FIG. 3, (nuclear magnetic resonance hydrogen spectrum, 400Hz, CDCl) 3 ). The spectrogram data are: 1 h NMR (400 mhz, chloroform-d) delta 4.95 (dq, j=8.2, 5.3hz, 1H), 4.59 (dd, j=8.9, 8.2hz, 1H), 4.35 (dd, j=8.9, 5.9hz, 1H), 3.58 (d, j=5.2 hz, 2H). The carbon spectrum is shown in fig. 4, and the spectrum data are: 13 C NMR(101MHz,Chloroform-d)δ154.23,74.09,68.23,31.42。
example 11:
epoxide (C) (0.8 ml,10mmol,1.0 equiv), ion pair catalyst 1 (0.0117 g,0.05mmol,0.05 equiv) was charged to a stainless steel pressure reactor tube. Sealing stainless steel pressure reaction tube with CO 2 Air in the stainless steel pressure reaction tube is replaced for 3 times, and then CO is filled into the reaction kettle 2 The initial pressure is 1MPa, the temperature is raised to 120 ℃, and the reaction time is 6 hours. After the reaction was completed, the stainless steel pressure reaction tube was cooled by an ice-water mixture at 0 ℃, the residual gas was released, and after column chromatography (petroleum ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, and the solution was spin-dried on a spin-evaporator to obtain a yellow solid, which was dried to a constant weight with a conversion of 98% and a selectivity of 98%. The hydrogen spectrum of the product is shown in FIG. 5, (nuclear magnetic resonance hydrogen spectrum, 400Hz, CDCl) 3 ). The spectrogram data are: 1 h NMR (400 mhz, chloro-d) delta 4.99 (ddt, j=8.3, 5.7,3.9hz, 1H), 4.55 (t, j=8.7 hz, 1H), 4.33 (dd, j=8.9, 5.7hz, 1H), 3.80 (dd, j=12.5, 4.3hz, 1H), 3.69 (dd, j=12.5, 3.7hz, 1H). The carbon spectrum is shown in fig. 6, and the spectrum data are: 13 CNMR(101MHz,Chloroform-d)δ154.50,74.48,66.86,44.19。
example 12:
epoxide (D) (1.5 ml,10mmol,1.0 equiv), ion-pair catalyst 1 (0.0234 g,0.1mmol,0.1 equiv) was charged to a stainless steel pressure reactor tube. Sealing stainless steel pressure reaction tube with CO 2 Air in the stainless steel pressure reaction tube is replaced for 3 times, and then CO is filled into the reaction kettle 2 Heating to 120 deg.C under 1MPa24h. After the reaction was completed, the stainless steel pressure reaction tube was cooled by an ice-water mixture at 0 ℃, the residual gas was released, and after column chromatography (petroleum ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, and the solution was spin-dried on a spin-evaporator to obtain a yellow solid, which was dried to a constant weight with a conversion of 66% and a selectivity of 99%. The hydrogen spectrum of the product is shown in FIG. 7, (nuclear magnetic resonance hydrogen spectrum, 400Hz, CDCl) 3 ). The spectrogram data are: 1 h NMR (400 mhz, chloroform-d) delta 4.82-4.69 (m, 1H), 4.47 (t, j=8.2 hz, 1H), 4.38 (dd, j=8.3, 5.8hz, 1H), 3.61 (dd, j=10.3, 4.6hz, 1H), 3.53 (dd, j=10.3, 3.6hz, 1H), 1.19 (s, 9H). The carbon spectrum is shown in fig. 8, and the spectrum data are: 13 C NMR(101MHz,Chloroform-d)δ155.27,75.26,74.06,66.73,61.43,27.44,24.87,1.16.
example 13:
epoxide (E) (1.2 ml,10mmol,1.0 equiv), ion-pair catalyst 1 (0.0117 g,0.05mmol,0.05 equiv) were charged to a stainless steel pressure reaction tube. Sealing stainless steel pressure reaction tube with CO 2 Air in the stainless steel pressure reaction tube is replaced for 3 times, and then CO is filled into the reaction kettle 2 The initial pressure is 1MPa, the temperature is raised to 120 ℃, and the reaction time is 18h. After the reaction was completed, the stainless steel pressure reaction tube was cooled by an ice-water mixture at 0 ℃, the residual gas was released, and after column chromatography (petroleum ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, and the solution was spin-dried on a spin-evaporator to obtain a yellow solid, which was dried to constant weight with a conversion of 69% and a selectivity of 99%. The hydrogen spectrum of the product is shown in FIG. 9, (nuclear magnetic resonance hydrogen spectrum, 400Hz, CDCl) 3 ). The spectrogram data are: 1 h NMR (400 mhz, chloro form-d) delta 5.89-5.75 (m, 1H), 5.25-5.11 (m, 2H), 4.79 (ddt, j=9.1, 6.5,3.5hz, 1H), 4.46 (t, j=8.3 hz, 1H), 4.33 (ddt, j=7.1, 6.0,1.3hz, 1H), 3.99 (dq, j=5.9, 1.4hz, 2H), 3.65 (dd, j=11.2, 3.5hz, 1H), 3.60-3.52 (m, 1H). The carbon spectrum is shown in fig. 10, and the spectrum data are: 13 CNMR(101MHz,Chloroform-d)δ155.06,133.71,117.65,75.19,72.41,68.83,66.21。
example 14:
epoxide (F) (1.4 ml,10mmol,1.0 equiv), ion pair catalyst 1 (0.011)7g,0.05mmol,0.05 equiv) was added to a stainless steel pressure reaction tube. Sealing stainless steel pressure reaction tube with CO 2 Air in the stainless steel pressure reaction tube is replaced for 3 times, and then CO is filled into the reaction kettle 2 The initial pressure is 1MPa, the temperature is raised to 120 ℃, and the reaction time is 12h. After the reaction was completed, the stainless steel pressure reaction tube was cooled by an ice-water mixture at 0 ℃, the residual gas was released, and after column chromatography (petroleum ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, and the solution was spin-dried on a spin-evaporator to obtain a yellow solid, which was dried to a constant weight with a conversion of 99% and a selectivity of 99%. The hydrogen spectrum of the product is shown in FIG. 11, (nuclear magnetic resonance hydrogen spectrum, 400Hz, CDCl) 3 ). The spectrogram data are: 1 h NMR (400 mhz, chloro-d) delta 7.35-7.27 (m, 2H), 7.02 (tt, j=7.4, 1.1hz, 1H), 6.94-6.87 (m, 2H), 5.03 (dddd, j=8.1, 5.9,4.4,3.6hz, 1H), 4.62 (t, j=8.4 hz, 1H), 4.54 (dd, j=8.5, 5.9hz, 1H), 4.24 (dd, j=10.5, 4.4hz, 1H), 4.16 (dd, j=10.6, 3.6hz, 1H). The carbon spectrum is shown in fig. 12, and the spectrum data are: 13 C NMR(101MHz,Chloroform-d)δ157.88,129.85,122.18,114.75,74.18,67.01,66.41。
example 15:
epoxide (G) (1.3 ml,10mmol,1.0 equiv), ion pair catalyst 1 (0.0117G, 0.05mmol,0.05 equiv) was charged to a stainless steel pressure reactor tube. Sealing stainless steel pressure reaction tube with CO 2 Air in the stainless steel pressure reaction tube is replaced for 3 times, and then CO is filled into the reaction kettle 2 The initial pressure is 1MPa, the temperature is raised to 120 ℃, and the reaction time is 24 hours. After the reaction was completed, the stainless steel pressure reaction tube was cooled by an ice-water mixture at 0 ℃ to release a residual gas, and after column chromatography (petroleum ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, and the solution was spin-dried on a spin-evaporator to obtain a yellow solid, which was dried to a constant weight with a conversion of 68% and a selectivity of 99%. The hydrogen spectrum of the product is shown in FIG. 13, (nuclear magnetic resonance hydrogen spectrum, 400Hz, CDCl) 3 ). The spectrogram data are: 1 h NMR (400 mhz, chloroform-d) delta 4.69 (qd, j=7.5, 5.4hz, 1H), 4.55-4.49 (m, 1H), 4.05 (dd, j=8.4, 7.2hz, 1H), 1.82-1.74 (m, 1H), 1.71-1.62 (m, 1H), 1.45-1.29 (m, 4H), 0.90 (t, j=7.0 hz, 3H). Carbon spectrumAs shown in fig. 14, the spectrogram data are: 13 C NMR(101MHz,Chloroform-d)δ155.21,77.34,77.16,69.48,33.59,26.47,22.29,13.85。
example 16:
epoxide (H) (1.1 ml,10mmol,1.0 equiv), ion pair catalyst 1 (0.0117 g,0.05mmol,0.05 equiv) was charged to a stainless steel pressure reactor tube. Sealing stainless steel pressure reaction tube with CO 2 Air in the stainless steel pressure reaction tube is replaced for 3 times, and then CO is filled into the reaction kettle 2 The initial pressure is 1MPa, the temperature is raised to 120 ℃, and the reaction time is 12h. After the reaction was completed, the stainless steel pressure reaction tube was cooled by an ice-water mixture at 0 ℃, the residual gas was released, and after column chromatography (petroleum ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, and the solution was spin-dried on a spin-evaporator to obtain a yellow solid, which was dried to a constant weight with a conversion of 98% and a selectivity of 99%. The hydrogen spectrum of the product is shown in FIG. 15, (nuclear magnetic resonance hydrogen spectrum, 400Hz, CDCl) 3 ). The spectrogram data are: 1 h NMR (400 mhz, chloro-d) delta 4.79 (ddt, j=8.4, 6.1,3.7hz, 1H), 4.47 (t, j=8.4 hz, 1H), 4.34 (dd, j=8.4, 6.1hz, 1H), 3.62 (dd, j=11.1, 3.6hz, 1H), 3.53 (dd, j=11.1, 3.8hz, 1H), 3.39 (s, 3H). The carbon spectrum is shown in fig. 16, and the spectrum data are: 13 C NMR(101MHz,Chloroform-d)δ155.06,75.13,71.52,68.64,66.24,59.68,1.07。
example 17
Epoxide (I) (1.7 ml,10mmol,1.0 equiv), ion pair catalyst 1 (0.0117 g,0.05mmol,0.05 equiv) was charged to a stainless steel pressure reactor tube. Sealing stainless steel pressure reaction tube with CO 2 Air in the stainless steel pressure reaction tube is replaced for 3 times, and then CO is filled into the reaction kettle 2 The initial pressure is 1MPa, the temperature is raised to 120 ℃, and the reaction time is 12h. After the reaction was completed, the stainless steel pressure reaction tube was cooled by an ice-water mixture at 0 ℃, the residual gas was released, and after column chromatography (petroleum ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, and the solution was spin-dried on a spin-evaporator to obtain a yellow solid, which was dried to constant weight with a conversion of 90% and a selectivity of 99%. The hydrogen spectrum of the product is shown in FIG. 17, (nuclear magnetic resonance hydrogen spectrum, 400Hz, CDCl) 3 ). The spectrogram data are: 1 h NMR (400 mhz, chloro form-d) delta 7.16 (tt, j=5.9, 4.6,2.1hz, 2H), 6.93 (td, j=7.4, 1.0hz, 1H), 6.81-6.75 (m, 1H), 5.05 (ddt, j=8.6, 5.5,3.3hz, 1H), 4.65-4.56 (m, 2H), 4.26 (dd, j=10.6, 3.5hz, 1H), 4.13 (dd, j=10.6, 3.1hz, 1H), 2.22 (s, 3H). The carbon spectrum is shown in fig. 18, and the spectrum data is: 13 CNMR(101MHz,Chloroform-d)δ155.86,154.90,131.21,127.21,127.00,121.78,110.92,74.33,67.11,66.36,16.10。
example 18:
epoxide (J) (1.2 ml,10mmol,1.0 equiv), ion-pair catalyst 1 (0.0117 g,0.05mmol,0.05 equiv) was charged to a stainless steel pressure reaction tube. Sealing stainless steel pressure reaction tube with CO 2 Air in the stainless steel pressure reaction tube is replaced for 3 times, and then CO is filled into the reaction kettle 2 The initial pressure is 1MPa, the temperature is raised to 120 ℃, and the reaction time is 24 hours. After the reaction was completed, the stainless steel pressure reaction tube was cooled by an ice-water mixture at 0 ℃, the residual gas was released, and after column chromatography (petroleum ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, and the solution was spin-dried on a spin-evaporator to obtain a yellow solid, which was dried to constant weight with a conversion of 90% and a selectivity of 98%. The hydrogen spectrum of the product is shown in FIG. 19, (nuclear magnetic resonance hydrogen spectrum, 400Hz, CDCl) 3 ). The spectrogram data are: 1 h NMR (400 mhz, chloro form-d) delta 5.78 (ddt, j=16.9, 10.1,6.6hz, 1H), 5.11-4.99 (m, 2H), 4.72 (qd, j=7.6, 5.1hz, 1H), 4.53 (t, j=8.1 hz, 1H), 4.08 (dd, j=8.4, 7.2hz, 1H), 2.28-2.13 (m, 2H), 1.96-1.87 (m, 1H), 1.79-1.70 (m, 1H). The carbon spectrum is shown in fig. 20, and the spectrum data are: 13 C NMR(101MHz,Chloroform-d)δ155.07,136.17,116.56,76.43,69.44,63.81,33.18,28.77,1.12。
Claims (10)
1. a method for catalyzing and fixing carbon dioxide by using a halogen-free organic ion pair catalyst is characterized by comprising the following steps of: the cyclic carbonate is obtained by adopting a halogen-free ion pair catalyst shown in a formula (I), epoxide and carbon dioxide under the condition of no solvent
Wherein the HBD is selected from the group consisting of conjugated acids containing N-atom organic bases; wherein the organic base is C 1 ～C 4 Alkyl substituted quaternary ammonium base compound, C 1 ～C 4 Alkyl substituted guanidine or unsubstituted guanidine, containing imidazopyridine compounds,
the structure of the epoxide is shown as a formula (II):
said R is 1 And R is 2 Selected from hydrogen, n-butyl, halogen substituted alkyl, phenyl, benzyl, R 3 -O-CH 2 -, said R 3 Selected from phenyl, phenyl substituted by alkyl of 1 to 3 carbon atoms, halogen substituted phenyl, allyl or straight or branched alkyl of 1 to 4 carbon atoms, or R 1 And R is 2 The R is connected to form cyclohexane 1 And R is 2 Are of the same or different construction.
2. The synthesis method according to claim 1, wherein: the preparation method of the halogen-free ion pair catalyst shown in the formula (I) comprises the steps of adopting any one combination of organic alkali and hydroxypyridine substituted by three different positions of ortho position, meta position and para position, carrying out acid-base neutralization at 0-25 ℃, and reacting at room temperature for 6-24 hours, wherein the molar ratio of hydroxypyridine to the organic alkali is 0.5-2:1.
3. The synthesis method according to claim 2, characterized in that: the organic base is methanol.
4. The synthesis method according to claim 1, wherein: said R is 1 And R is 2 When the same is used, the R is selected from phenyl 1 And R is 2 At different times, is selected from hydrogen, n-butyl, halomethyl, phenyl,Halogenated phenyl, R 3 -O-CH 2 -, said R 3 Selected from phenyl, tolyl, allyl, t-butyl, or methyl.
5. The synthesis method according to claim 1, wherein: the C is 1 ～C 4 The alkyl substituted quaternary ammonium base compound is selected from tetrabutylammonium hydroxide, tetrapropylammonium hydroxide and tetraethylammonium hydroxide;
the imidazopyridine-containing organic base is selected from 1,5, 7-triazobicyclo (4.4.0) dec-5-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, 1, 8-diazo bisspiro [5.4.0] undec-7-ene and 4-dimethylaminopyridine;
the C is 1 ～C 4 The alkyl substituted guanidine or unsubstituted guanidine is selected from Tetramethylguanidine (TMG), guanidine, and 1, 1-dimethylguanidine.
6. The method according to claim 1, characterized in that: the structure of the halogen-free ion pair catalyst shown in the formula (I) is as follows
7. The synthesis method according to claim 1, wherein: the structure of the epoxide represented by the formula (II) is shown as follows
8. The synthetic method according to claim 1, wherein the epoxide of formula (II) is selected from epichlorohydrin, epibromohydrin, allyl glycidyl ether, t-butyl glycidyl ether, benzyl glycidyl ether, 4-chlorobenzeneglycidyl ether, dibromophenylglycidyl ether, phenylglycidyl ether, 2-toluene glycidyl ether, styrene oxide, (methoxymethyl) ethylene oxide, butyl ethylene oxide.
9. The synthesis method according to claim 1, wherein: the molar ratio of the epoxide shown in the formula (II) to the halogen-free catalyst shown in the formula (I) is 100:0.5 to 100:1, the reaction temperature is 80-120 ℃, the reaction time is 1-24h, and the initial pressure of carbon dioxide is 0.05-10MPa.
10. The method of synthesis according to claim 9, wherein: the molar ratio of the epoxide shown in the formula (II) to the halogen-free catalyst shown in the formula (I) is 100:0.5 to 100:1, the reaction temperature is 100-120 ℃, the reaction time is 6-24h, and the initial pressure of carbon dioxide is 1-2Mpa.
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