CN108554456A - A kind of application of rare earth imidazole salt compound as catalyst - Google Patents
A kind of application of rare earth imidazole salt compound as catalyst Download PDFInfo
- Publication number
- CN108554456A CN108554456A CN201810515924.3A CN201810515924A CN108554456A CN 108554456 A CN108554456 A CN 108554456A CN 201810515924 A CN201810515924 A CN 201810515924A CN 108554456 A CN108554456 A CN 108554456A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- reaction
- salt compound
- catalyst
- imidazole salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 rare earth imidazole salt compound Chemical class 0.000 title claims abstract description 61
- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 47
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 110
- 238000006243 chemical reaction Methods 0.000 claims abstract description 102
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 61
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 55
- 150000001541 aziridines Chemical class 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 150000002910 rare earth metals Chemical group 0.000 claims abstract description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 120
- 239000002904 solvent Substances 0.000 claims description 34
- 239000011261 inert gas Substances 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- PCPYTNCQOSFKGG-UHFFFAOYSA-N 1-chlorobuta-1,3-diene Chemical class ClC=CC=C PCPYTNCQOSFKGG-UHFFFAOYSA-N 0.000 claims description 13
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- NJLYZISHBSABMZ-UHFFFAOYSA-N 1,3-bis[2,6-di(propan-2-yl)phenyl]-2h-imidazole Chemical class CC(C)C1=CC=CC(C(C)C)=C1N1C=CN(C=2C(=CC=CC=2C(C)C)C(C)C)C1 NJLYZISHBSABMZ-UHFFFAOYSA-N 0.000 claims description 6
- 229940015043 glyoxal Drugs 0.000 claims description 6
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 6
- 150000002602 lanthanoids Chemical class 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 5
- 229920002866 paraformaldehyde Polymers 0.000 claims description 5
- 150000002460 imidazoles Chemical class 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- KQOQKTQVYKCWPN-UHFFFAOYSA-N C(C)(C)C1=C(C(=CC=C1)C(C)C)C1=C(N=CN1)C1=C(C=CC=C1C(C)C)C(C)C Chemical class C(C)(C)C1=C(C(=CC=C1)C(C)C)C1=C(N=CN1)C1=C(C=CC=C1C(C)C)C(C)C KQOQKTQVYKCWPN-UHFFFAOYSA-N 0.000 claims 1
- 239000011260 aqueous acid Substances 0.000 claims 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 claims 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 229910052772 Samarium Inorganic materials 0.000 abstract description 4
- 229910052769 Ytterbium Inorganic materials 0.000 abstract description 4
- 229910052727 yttrium Inorganic materials 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000006978 adaptation Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 31
- UUJCYIMTWZWQFW-UHFFFAOYSA-N 1-ethyl-2-phenylaziridine Chemical compound CCN1CC1C1=CC=CC=C1 UUJCYIMTWZWQFW-UHFFFAOYSA-N 0.000 description 25
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- 239000007787 solid Substances 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 description 5
- FLIPVKQYNWMJSJ-UHFFFAOYSA-N 2-phenyl-1-propylaziridine Chemical compound CCCN1CC1C1=CC=CC=C1 FLIPVKQYNWMJSJ-UHFFFAOYSA-N 0.000 description 5
- WDGCBNTXZHJTHJ-UHFFFAOYSA-N 2h-1,3-oxazol-2-id-4-one Chemical class O=C1CO[C-]=N1 WDGCBNTXZHJTHJ-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000007306 functionalization reaction Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- WDZMBYZWOSXOIZ-UHFFFAOYSA-N 1-butyl-2-phenylaziridine Chemical compound CCCCN1CC1C1=CC=CC=C1 WDZMBYZWOSXOIZ-UHFFFAOYSA-N 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910002249 LaCl3 Inorganic materials 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- UUFQTNFCRMXOAE-UHFFFAOYSA-N 1-methylmethylene Chemical compound C[CH] UUFQTNFCRMXOAE-UHFFFAOYSA-N 0.000 description 1
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical class CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 description 1
- PBHROHRYFHKKSY-UHFFFAOYSA-N 2-[2,6-di(propan-2-yl)phenyl]-1h-imidazole Chemical class CC(C)C1=CC=CC(C(C)C)=C1C1=NC=CN1 PBHROHRYFHKKSY-UHFFFAOYSA-N 0.000 description 1
- GMXHYZUAGZTPMT-UHFFFAOYSA-N C(CC)N1C(C1)C1=CC=C(C=C1)C Chemical compound C(CC)N1C(C1)C1=CC=C(C=C1)C GMXHYZUAGZTPMT-UHFFFAOYSA-N 0.000 description 1
- 101100165177 Caenorhabditis elegans bath-15 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- QQUNOUMTXXCEBH-UHFFFAOYSA-N O1[CH-]C(C=C1)=O Chemical class O1[CH-]C(C=C1)=O QQUNOUMTXXCEBH-UHFFFAOYSA-N 0.000 description 1
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 description 1
- 101100438134 Rattus norvegicus Cabs1 gene Proteins 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910009523 YCl3 Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- CKLHRQNQYIJFFX-UHFFFAOYSA-K ytterbium(III) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Yb+3] CKLHRQNQYIJFFX-UHFFFAOYSA-K 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
- C07D263/18—Oxygen atoms
- C07D263/20—Oxygen atoms attached in position 2
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
- C07D263/18—Oxygen atoms
- C07D263/20—Oxygen atoms attached in position 2
- C07D263/22—Oxygen atoms attached in position 2 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to other ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
-
- 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
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
-
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- 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
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/38—Lanthanides other than lanthanum
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
A kind of application the invention discloses rare earth imidazole salt compound as catalyst.The general formula of rare earth imidazole salt compound is [RECl4(THF)2] (HIPr), wherein RE is rare earth metal, one kind in La, Sm, Yb, Y；HIPr is 1,3 2 (2,6 diisopropyl phenyl) glyoxaline cations；The rare earth imidazole salt compound synthesis of the present invention is simple, and structure is clear, and high income.Application process invention also provides the preparation method of above compound and as catalyst aziridine derivative and carbon dioxide reaction, application process mild condition, activity is high, good, the substrate wide adaptation range of selectivity.
Description
The present invention be entitled a kind of rare earth imidazole salt compound and preparation method thereof with as catalyst application,
The applying date is September in 2016 20, application No. is the divisional applications of 201610834147X patent applications, belongs to the application of product
Technology segment.
Technical field
The present invention relates to the preparing technical fields of catalyst, and in particular to a kind of rare earth imidazole salt compound is as catalyst
Application, aziridine derivative and carbon dioxide reaction can be catalyzed.
Background technology
5- substitution oxazolidones are important heterocyclic compound, are not only common synthetic intermediate and chiral auxiliary,
And it is the important skeleton structure of active medicine.Replace Evil as Material synthesis 5- using the derivative of aziridine and carbon dioxide
The advantage that oxazolidone has its exclusive, one：The reaction belongs to the reaction of atom economy type, and no coupling product generates；Secondly：Carbon dioxide
It is a kind of abundant, renewable and cheap C1 raw materials, it is activated and using the concern that attract numerous researchers always；Its
Three：The derivative species of aziridine are more, and synthesis is simple, are conducive to the oxazolidine for synthesizing substituent group variation Feng Fu according to demand
Ketone product.At present, it has been found that some catalyst have preferable catalytic effect to such reaction, include mainly：One, amino-functionalization is urged
Agent；Two, Jie Kong Jin Shu Phosphonium hydrochlorates；Three, metal Al, Cr catalyst；Four, ionic-liquid catalyst etc..
Report about amino-functionalization catalyst：
2010, Liu seminars reported deacidite D301R, have successfully been catalyzed azacyclo- in a mild condition
The reaction of propane and carbon dioxide, being formed has excellent regioselective 5- aryl -2- oxazolidones；2014, Nale classes
Topic group studies CO with amino-functionalization mesostructured material catalyst2With aziridine derivative He Cheng oxazolidones,
Utilize the amino-functionalization MCM-41 of 25 wt%（The amine addition of 14.6wt%）, 5 MPa it is lower 40 DEG C react 8 hours, obtained target
Molecule.（Referring to：A. H. Liu; L. N. He; S. Y. Peng; Z. D. Pan; J. L. Wang; J. GaoSci. China Chem. 2010, 53(7), 1578. ;B. N. Deepak；R. Surjyakanta; P.
Kulamani; M. B. Bhalchandra Applied Catalysis A: General2014, 469, 340）.
Report about mesoporous metal phosphate catalyst system and catalyzing：
2014, Ma seminars delivered with the biradical mesoporous metal titanium phosphate activation aziridine of soda acid and CO2Ring add
At reaction, for biradical synergistic effect so that high conversion rate, yield is high, and selectivity is good, easy to operate；2015, Lin seminars were also sent out
Mesoporous zirconium phosphate catalyst is showed, for catalysis aziridine and CO2Heterogeneous cycloaddition reaction has very high efficiency, and
There is no solvent and co-catalyst in its system, has been proved good activity, selectivity is also higher, and recoverable.
But reaction temperature reaches 100 DEG C.（Referring to：T. Y. Ma; S. Z. QiaoCatalysis 2014, 4, 3847. ;X.
Lin; Z. Yang; L. He; Z. Yuan Green Chem. 2015, 17, 795）.
Report about metal Al, Cr catalyst system and catalyzing
2014, Ren seminars proposed difunctional Al catalysts.This Salen-Al does catalyst, intramolecular quaternary ammonium salt
The catalyst system and catalyzing for doing co-catalyst is used for aziridine and CO2Ring-opening reaction on, show good selectivity, it
The complete configuration on methine carbon can be retained；2015, Adhikari seminars were found that Salen-Cr catalyst system and catalyzings are catalyzed
CO2It is reacted Yu oxazolidone with highly selective, and does not need the participation of co-catalyst.（Referring to：W. M. Ren; Y. Liu;
X. B. Lu Org. Chem. 2014,79,9771.;Debashis; W. M. Aaron; B. Mu-Hyun; T. N.
Son Binh Chem. Sci.2015, 6, 1293.）.
Report about alkaline ionic liquid catalyst
2010, Yang seminars were found that a series of alkali ionic liquids easily prepared, can under solvent-free conditions, efficiently
Rate, highly selective catalysis aziridine and CO2Reaction prepares 5- aryl -2- oxazolidones.（Referring to： Z. Z. Yang; L.
N. He; S. Y. Peng; A. H. Liu Green Chem.2010, 12, 1850.）.
Although existing catalyst system and catalyzing can be catalyzed aziridine derivative and carbon dioxide reaction, get Dao oxazolidinone
Compound, but there is problems in these systems, such as：The regioselectivity of catalyst is poor, catalyst dosage is big,
Catalyst metals type is limited, severe reaction conditions, substrate universality difference etc..Therefore, find a kind of raw material sources it is simple,
The preparation method that reaction condition is mild, universality is good is meaningful with high effects ground He Cheng oxazolidinone compounds.
Invention content
It is an object of the present invention to provide a kind of rare earth imidazole salt compounds and preparation method thereof, can be used as catalyst nitrogen
Heterocycle propane and CO2Reaction prepares 5- substituted oxaolidones compounds, and catalytic activity is high, and regioselectivity is good, and substrate is suitable
It answers range wide, can overcome the shortcomings of existing synthetic method well.
The present invention is to realize the technical solution of above-mentioned technical purpose：
A kind of rare earth imidazole salt compound, chemical structure of general formula are as follows：
Wherein, RE is rare earth metal.
The chemical formula of the rare earth imidazole salt compound of the present invention is [RECl4(THF)2] (HIPr), RE is rare earth metal, choosing
From one kind in La, Sm, Yb, Y；HIPr is 1,3- bis- (2,6- diisopropyl phenyls) glyoxaline cation.
Present invention simultaneously provides a kind of preparation method of the rare earth imidazole salt compound, easy to operate, separating-purifyings
Conveniently, cost of material is low, reaction condition is mild, gained compound structure is clear；Specifically include following steps：
（1）Using 2,6-DIPA and glyoxal as raw material, using acid solution as catalyst, two (2,6- diisopropyls are prepared
Phenyl) two Chlorobutadienes；
（2）With two (2,6- diisopropyl phenyl) two Chlorobutadienes, paraformaldehyde for raw material, in presence of hydrochloric acid, 1,3- is prepared
Two (2,6- diisopropyl phenyls) imidazoles villaumites；
（3）With 1,3- bis- (2,6- diisopropyl phenyl) imidazoles villaumite, lanthanide terchlorides compound for raw material, in tetrahydrofuran,
Prepare rare earth imidazole salt compound.
In above-mentioned technical proposal, two (2,6- diisopropyl phenyl) two Chlorobutadienes are prepared specifically, by 2,6- diisopropyls
Base aniline is added to reaction bulb with glyoxal and appropriate absolute ethyl alcohol；Make catalyst with appropriate aqueous formic acid again；Reaction solution
Become yellow from colourless rapidly, after 1h, there are a large amount of yellow solids to generate；It is filtered after stirring 48h at room temperature, obtains yellow
Solid is washed 3 times with cold absolute methanol, obtains pure products two (2,6- diisopropyl phenyl) two Chlorobutadienes；Its reaction side
Formula is as follows：
Above-mentioned two (2,6- diisopropyl phenyl) two Chlorobutadienes are dissolved in toluene, the paraformaldehyde pulverized in advance is added,
It is stirred at reflux 1h at 50 DEG C, until most of paraformaldehyde solid dissolves；40 DEG C are cooled to, Isosorbide-5-Nitrae-dioxy of hydrochloric acid is added dropwise
Six ring solution, the reaction was continued 40 h；Reaction is finished, and decompression filters, and filter cake is washed 3 times with THF, obtains the target product 1,3- of pale pink
Two (2,6- diisopropyl phenyl) imidazoles villaumites, abbreviation HIPrCl；Its reaction equation is as follows：
In above-mentioned technical proposal, rare earth imidazole salt compound is prepared specifically, according to 1:(2,6- bis- is different by 1,3- bis- for 1 molar ratio
Propyl phenyl) imidazoles villaumite and lanthanide terchlorides compound（RECl3）Mixing, reacts 24 under conditions of 50 DEG C, in THF solvents
H, centrifugation, takes supernatant concentration, concentrate to be crystallized in pure THF and obtain colourless bulk crystals, is rare earth imidazole salt compound；Its
Reaction equation is as follows：
In above-mentioned technical proposal, step（1）In, be added 88% aqueous formic acid 0.5-1.5 mol% it is anti-as catalyst
It should carry out at room temperature；Easily controllable reaction rate, easy to operate, yield is high；It is preferred that 2,6- diisopropyl anilines and glyoxal
It is 2:1 molar ratio.
In above-mentioned technical proposal, step（2）In, by two (2,6- diisopropyl phenyl) two Chlorobutadienes, poly at 50 DEG C
Formaldehyde is stirred at reflux, and is conducive to solid formaldehyde and the contact of two (2,6- diisopropyl phenyl) two Chlorobutadienes is uniform, ensure interface
Stable reaction efficiently carries out completely, improves raw material availability；At 40 DEG C, Isosorbide-5-Nitrae-dioxane solution of hydrochloric acid is added dropwise, makes reaction
Excessively acutely, and the yield of 1,3- bis- (2,6- diisopropyl phenyl) imidazoles villaumite can will not be improved.
In above-mentioned technical proposal, step（3）In, reaction temperature is 50 DEG C, is easily obtained, and controllability is good, is conducive to solid
Body formaldehyde and the contact of two (2,6- diisopropyl phenyl) two Chlorobutadienes are uniform, ensure that interfacial reaction stability and high efficiency carries out completely,
Improve raw material availability.
In above-mentioned technical proposal, step（3）In, lanthanide terchlorides compound by tetrahydrofuran activation again with 1,3- bis-
(2,6- diisopropyl phenyl) imidazoles villaumite mixes so that reaction is easy to carry out and the reaction was complete, and by-product is few.It is preferred that 1,3- bis-
The molar ratio of (2,6- diisopropyl phenyls) imidazoles villaumite and lanthanide terchlorides compound is 1:1.
Rare earth imidazole salt compound structure prepared by the present invention is clear, is brand new, the catalytic effect of catalyst is notable
Better than similar catalyst, excellent catalytic effect can realize the multiple cycle profit of catalyst under the premise of not reducing catalytic effect
With.This structure also makes that the dosage of catalyst is small, regioselectivity is good, reaction condition is mild, the universality of substrate is good, to difference
The reaction of aziridine derivative and carbon dioxide have preferable catalytic action.The invention also discloses above-mentioned rare earth miaows
Azoles salt compound is in catalysis aziridine derivative and the application in carbon dioxide reaction.
In above-mentioned technical proposal, the chemical structural formula of aziridine derivative is as follows：
Wherein, R1 、R2It is independent to be selected from H, C2H5、CH3CH2CH2、CH3CH2CH2CH2、(CH3)C、CH3CH(CH3)CH2、Ph、
PhCH2-、CH3Ph、CH3CH2Ph、ClPh、C6H11Deng.
In the present invention, the molar ratio of aziridine derivative and rare earth imidazole salt compound is 100:（0.5~1）, excellent
0.75% is selected, reaction temperature is 40 DEG C~70 DEG C, and the reaction time is 10h~15h, preferably 50 DEG C reaction 12h；It is disclosed by the invention
For rare earth imidazole salt compound as catalyst, regioselectivity is good, catalyst dosage is small, catalyst lean soil species class is more, anti-
It answers mild condition, the universality of substrate good, has preferably to the reaction of different aziridine derivative and carbon dioxide
Catalytic action.
The invention also discloses a kind of 5- replace oxazolidones preparation method, include the following steps, anhydrous and oxygen-free,
Under inert gas shielding, rare earth imidazole salt compound is added in reaction bulb, inert gas is drained, connects carbon dioxide airbag,
It is added under solvent or condition of no solvent, reinjects aziridine substrate, reacted, obtain 5- substitution oxazolidones.
The chemical structure of general formula of the rare earth imidazole salt compound is as follows：
Wherein, RE is rare earth metal.
Reaction process can indicate as follows：
Further, after reaction, if reaction adds solvent, reaction solution is extracted three times with ether, is spin-dried for solvent, obtains
Product 5- replaces oxazolidones；If reaction is solvent-free, it is not necessarily to extraction processing, simplifies preparation process, while saving preparation
Cost.
In above-mentioned technical proposal, reaction temperature is 40 DEG C~70 DEG C, preferably 50 DEG C.
In above-mentioned technical proposal, the molar ratio of aziridine derivative and rare earth imidazole salt compound is 100:（0.5~
1）, preferably 100:0.75.
In above-mentioned technical proposal, the reaction time is 10h~15h, preferably 12h.
In above-mentioned technical proposal, the solvent is hydrocarbon solvent such as n-hexane, toluene, dimethyl sulfoxide (DMSO), N, N '-dimethyl
Formamide etc..
In above-mentioned technical proposal, catalyst can be added in reaction vessel in solid form, solve the prior art and need elder generation
The defect of catalyst-solvent, increasing simplify operation, save organic reagent, reduce environmental pollution；Simultaneous reactions condition
Mildly, product yield high；Achieve unexpected technique effect.
Due to the application of the above technical scheme, the present invention has following advantages compared with prior art:
1. rare earth imidazole salt compound structure disclosed by the invention is clear, synthetic method is simple, and yield is high, isolates and purifies simply,
For being catalyzed, reaction time zone field selectivity is good, catalyst dosage is small, catalyst lean soil species class is more, reaction condition is mild, substrate
Universality it is good.
2. rare earth imidazole salt compound disclosed by the invention derives as catalyst activity height for being catalyzed aziridine
When object is with carbon dioxide reaction, the dosage of catalyst is 0.5~1 mol% of reactant aziridine derivative, product yield
Higher, selectivity is good, and less catalyst amount is also beneficial to the purification of product.
3. raw material is easy to get in rare earth imidazole salt compound preparation method disclosed by the invention, reaction condition is mild, reaction bottom
Object universality is wide, and the catalyst energy efficient catalytic aziridine derivative and carbon dioxide reaction of preparation, the reaction time is short, mesh
The high income of product is marked, selectivity is good, and operation process is simple.
Specific implementation mode
Below in conjunction with embodiment, next the present invention will be described in detail.
Embodiment one：Prepare [RECl4(THF)2](HIPr) (RE = La、Sm、Yb、Y)
1）Before preparing rare earth imidazole salts, HIPrCl is first prepared, preparation method is as follows：
By 53.1g（300mmol）2,6-DIPA, the glyoxal water solution of 16.95mL (150mmol, 40%),
150 mL absolute ethyl alcohols are added in 500 mL eggplant-shape bottles.Catalyst is made into 88wt% aqueous formic acid 0.5-1.5 mol% additions.
Reaction solution becomes yellow from colourless rapidly, after 1h, has a large amount of yellow solids to generate.It filters, obtains after stirring 48h at room temperature
It to yellow solid, is washed 3 times with cold absolute methanol, obtains 44.62 g of pure products (yield 79.1%).
By 37.6 g（100mmol）Two (2,6- diisopropyl phenyl) two Chlorobutadienes, 1.68g（100 mmol）Formaldehyde is solid
Body, 160mL toluene are added in 500 mL three neck round bottom.1 h is stirred at reflux at 50 DEG C, until formaldehyde is largely molten
Solution.Reaction solution is slightly cooled to 40 DEG C, and the dioxane solution 58mL of HCl is added with syringe（100mmol, 1.723mol/L）, instead
Liquid color is answered to be changed into red by yellow
Until brown, and with the generation of white solid.After reactant is stirred at reflux 40h at 40 DEG C, filters, washed with THF
It washs 3 times, obtains pink colour blocks of solid.The dissolving of about 40mL absolute ethyl alcohols is added, is spin-dried for solvent, so that solid is become powder, then use THF
Washing 3 times, obtains 21.94g off-white powders HIPrCl（Yield 51.7%）.
2）Prepare [RECl4(THF)2](HIPr)
Weigh anhydrous RECl3It is added in the peace a word used in place name bottle of water removal deoxygenation, argon gas protection, seals bottle after adding appropriate tetrahydrofuran, at room temperature
Stir-activating.It weighs and anhydrous LaCl3The anhydrous HIPrCl of equivalent is added in the peace a word used in place name bottle of another water removal deoxygenation, argon gas protection,
Suitable tetrahydrofuran is added, is stirred.Then in above-mentioned RECl3Tetrahydrofuran suspension in be added HIPrCl tetrahydrochysene furan
It mutters suspension, system moment becomes micro- muddy, seals bottle, is reacted under 50 DEG C of stirring conditions.After 40-48 h, stop reaction, stands and divide
Layer.It is centrifuged off the white solid of lower layer, clear liquid has been concentrated into a large amount of clear crystals and has been precipitated, and to clear, slow cooling obtains thermosol
Colourless bulk crystals, as prepared catalyst rare earth imidazole salt compound.
By LaCl3It is changed to SmCl3、YbCl3、YCl3Different rare earth imidazole salt compounds can be prepared.
[LaCl4(THF)] (HIPr) data：Nuclear magnetic resonance spectroscopy：1H NMR (400 MHz, DMSO-d 6) δ1.16
(d, J=8.0 Hz, 12H, 4CH3), 1.26 (d, J = 8.0 Hz, 12H, 4CH3), 1.74-1.77 (m, 4H,
2CH2), 2.32 (m, 4H, 4CH), 3.35 (s, 2H), 3.58-3.62 (m, 4H, 2CH2), 7.53 (d, J =
8.0 Hz, 4H, ArH), 7.69 (t, J = 8.0 Hz, 2H, ArH), 8.59 (s, 2H, 2NCH), 10.26(s,
1H, HCl)。
[SmCl4(THF)2] (HIPr) data：Mp.：221-222℃(dec.).
[YbCl4(THF)2] (HIPr) data：Mp.：150-151℃.
[YCl4(THF)2] (HIPr) data：Nuclear magnetic resonance spectroscopy：1H NMR (400 MHz, DMSO-d 6) δ1.15
(d, J = 6.8 Hz, 12H, 4CH3), 1.24 (d,J = 6.7 Hz, 12H, 4CH3), 1.77-1.69 (m, 8H,
4CH2), 2.34 (m, 4H, 4CH), 3.57 (m, 8H, 4CH2), 7.51 (d,J =7.8 Hz, 4H, ArH), 7.67
(t, J=7.8 Hz, 2H, ArH), 8.59 (s, 2H, 2NCH), 10.34 (s, 1H, HCl).Data above proves mesh
Mark compound is successfully prepared.
Embodiment two：Under condition of no solvent, [the LaCl of 0.75 mol%4(THF)] (HIPr) is catalyzed under 50 DEG C, normal pressure
The reaction of N- ethyl -2- phenyl aziridine and carbon dioxide：
Under anhydrous and oxygen-free, inert gas shielding, [LaCl is added in reaction bulb4(THF)] (HIPr) is protected in carbon dioxide airbag
Under shield, N- ethyl -2- phenyl aziridine is added, is stirred to react in 50 DEG C of constant temperature bath 12 hours and obtains product, calculates
Yield is 86%, selective A:B is 8:92.
Embodiment three：Under condition of no solvent, [the YbCl of 0.75 mol%4(THF)2] (HIPr) be catalyzed under 50 DEG C, normal pressure
The reaction of N- ethyl -2- phenyl aziridine and carbon dioxide：
Under anhydrous and oxygen-free, inert gas shielding, [YbCl is added in reaction bulb4(THF)2] (HIPr), in carbon dioxide airbag
Under protection, N- ethyl -2- phenyl aziridine is added, is stirred to react in 50 DEG C of constant temperature bath 12 hours and obtains product, counts
It is 56% to calculate yield, selective A:B is 3:97.
Example IV：Under condition of no solvent, [the SmCl of 0.75 mol%4(THF)2] (HIPr) be catalyzed under 50 DEG C, normal pressure
The reaction of N- ethyl -2- phenyl aziridine and carbon dioxide：
Under anhydrous and oxygen-free, inert gas shielding, [SmCl is added in reaction bulb4(THF)2] (HIPr), in carbon dioxide airbag
Under protection, N- ethyl -2- phenyl aziridine is added, is stirred to react in 50 DEG C of constant temperature bath 12 hours and obtains product, counts
It is 75% to calculate yield, selective A:B is 9:91.
Embodiment five：Under condition of no solvent, [the YCl of 0.75 mol%4(THF)2] (HIPr) be catalyzed N- under 50 DEG C, normal pressure
The reaction of ethyl -2- phenyl aziridine and carbon dioxide：
Under anhydrous and oxygen-free, inert gas shielding, [YCl is added in reaction bulb4(THF)2] (HIPr), it is protected in carbon dioxide airbag
Under shield, N- ethyl -2- phenyl aziridine is added, is stirred to react in 50 DEG C of constant temperature bath 12 hours and obtains product, calculates
Yield is 55%, selective A:B is 9:91.
Embodiment six：Under condition of no solvent, [the LaCl of 0.75mol%4(THF)] (HIPr) is catalyzed N- under 40 DEG C, normal pressure
The reaction of ethyl -2- phenyl aziridine and carbon dioxide：
Under anhydrous and oxygen-free, inert gas shielding, [LaCl is added in reaction bulb4(THF)] (HIPr) is protected in carbon dioxide airbag
Under shield, N- ethyl -2- phenyl aziridine is added, is stirred to react in 40 DEG C of constant temperature bath 10 hours and obtains product, calculates
Yield is 55%, selective A:B is 9:91.
Embodiment seven：Under condition of no solvent, [the LaCl of 1 mol%4(THF)] (HIPr) is catalyzed N- second at 50 DEG C under normal pressure
The reaction of base -2- phenyl aziridine and carbon dioxide：
Under anhydrous and oxygen-free, inert gas shielding, [LaCl is added in reaction bulb4(THF)] (HIPr) is protected in carbon dioxide airbag
Under shield, N- ethyl -2- phenyl aziridine is added, is stirred to react in 50 DEG C of constant temperature bath 12 hours and obtains product, calculates
Yield is 92%, selective A:B is 8:92.
Embodiment eight：Under condition of no solvent, [the SmCl of 0.75 mol%4(THF)] (HIPr) is catalyzed under 50 DEG C, normal pressure
The reaction of N- ethyl -2- phenyl aziridine and carbon dioxide：
Under anhydrous and oxygen-free, inert gas shielding, [SmCl is added in reaction bulb4(THF)] (HIPr) is protected in carbon dioxide airbag
Under shield, N- ethyl -2- phenyl aziridine is added, is stirred to react in 50 DEG C of constant temperature bath 15 hours and obtains product, calculates
Yield is 71%, selective A:B is 9:91.
Embodiment nine：Under condition of no solvent, [the LaCl of 0.5 mol%4(THF)] (HIPr) is catalyzed N- under 50 DEG C, normal pressure
The reaction of ethyl -2- phenyl aziridine and carbon dioxide：
Under anhydrous and oxygen-free, inert gas shielding, [LaCl is added in reaction bulb4(THF)] (HIPr) is protected in carbon dioxide airbag
Under shield, N- ethyl -2- phenyl aziridine is added, is stirred to react in 50 DEG C of constant temperature bath 12 hours and obtains product, calculates
Yield is 42%, selective A:B is 10:90.
Embodiment ten：Under condition of no solvent, [the LaCl of 0.75 mol%4(THF)] (HIPr) is catalyzed under 40 DEG C, normal pressure
The reaction of N- ethyl -2- phenyl aziridine and carbon dioxide：
Under anhydrous and oxygen-free, inert gas shielding, [LaCl is added in reaction bulb4(THF)] (HIPr) is protected in carbon dioxide airbag
Under shield, N- ethyl -2- phenyl aziridine is added, is stirred to react in 40 DEG C of constant temperature bath 12 hours and obtains product, calculates
Yield is 85%, selective A:B is 8:92.
Embodiment 11：Under condition of no solvent, [the LaCl of 0.75 mol%4(THF)] (HIPr) is urged under 70 DEG C, normal pressure
Change the reaction of N- ethyl -2- phenyl aziridine and carbon dioxide：
Under anhydrous and oxygen-free, inert gas shielding, [LaCl is added in reaction bulb4(THF)] (HIPr) is protected in carbon dioxide airbag
Under shield, N- ethyl -2- phenyl aziridine is added, is stirred to react in 70 DEG C of constant temperature bath 12 hours and obtains product, calculates
Yield is 47%, selective A:B is 9:91.
Embodiment 12：Using dimethyl sulfoxide as solvent, [the LaCl of 0.75 mol%4(THF)] (HIPr) at 50 DEG C, normal pressure
The reaction of lower catalysis N- ethyl -2- phenyl aziridine and carbon dioxide：
Under anhydrous and oxygen-free, inert gas shielding, [LaCl is added in reaction bulb4(THF)] (HIPr) is protected in carbon dioxide airbag
Under shield, N- ethyl -2- phenyl aziridine is added, is stirred to react in 50 DEG C of constant temperature bath 12 hours and obtains product, calculates
Yield is 99%, selective A:B is 3:97.
Embodiment 13：Using toluene as solvent, [the LaCl of 0.75 mol%4(THF)] (HIPr) is urged under 40 DEG C, normal pressure
Change the reaction of N- ethyl -2- phenyl aziridine and carbon dioxide：
Under anhydrous and oxygen-free, inert gas shielding, [LaCl is added in reaction bulb4(THF)] (HIPr) is protected in carbon dioxide airbag
Under shield, N- ethyl -2- phenyl aziridine is added, is stirred to react in 40 DEG C of constant temperature bath 12 hours and obtains product, calculates
Yield is 37%, selective A:B is 4:96.
Embodiment 14：Under condition of no solvent, [the LaCl of 1 mol%4(THF)] (HIPr) is catalyzed N- under 50 DEG C, normal pressure
The reaction of propyl -2- phenyl aziridine and carbon dioxide：
Under anhydrous and oxygen-free, inert gas shielding, [LaCl is added in reaction bulb4(THF)] (HIPr) is protected in carbon dioxide airbag
Under shield, N- propyl -2- phenyl aziridine is added, is stirred to react in 50 DEG C of constant temperature bath 12 hours and obtains product, calculates
Yield is 95%, selective A:B is 13: 87.
Embodiment 15：Under condition of no solvent, [the LaCl of 1mol%4(THF)] (HIPr) is catalyzed N- under 50 DEG C, normal pressure
The reaction of butyl -2- phenyl aziridine and carbon dioxide：
Under anhydrous and oxygen-free, inert gas shielding, [LaCl is added in reaction bulb4(THF)] (HIPr) is protected in carbon dioxide airbag
Under shield, N- propyl -2- phenyl aziridine is added, is stirred to react in 50 DEG C of constant temperature bath 12 hours and obtains product, calculates
Yield is 99%, selective A:B is 28: 72.
Embodiment 16：Under condition of no solvent, [the YCl of 1 mol%4(THF)] (HIPr) is catalyzed N- under 50 DEG C, normal pressure
The reaction of butyl -2- phenyl aziridine and carbon dioxide：
Under anhydrous and oxygen-free, inert gas shielding, [YCl is added in reaction bulb4(THF)] (HIPr) is protected in carbon dioxide airbag
Under shield, N- butyl -2- phenyl aziridine is added, is stirred to react in 50 DEG C of constant temperature bath 10 hours and obtains product, calculates
Yield is 47%, selective A:B is 7: 93.
Embodiment 17：Under condition of no solvent, [the LaCl of 0.75 mol%4(THF)] (HIPr) is urged under 50 DEG C, normal pressure
Change the reaction of N- propyl -2- phenyl aziridine and carbon dioxide：
Under anhydrous and oxygen-free, inert gas shielding, [LaCl is added in reaction bulb4(THF)] (HIPr) is protected in carbon dioxide airbag
Under shield, N- propyl -2- phenyl aziridine is added, is stirred to react in 50 DEG C of constant temperature bath 12 hours and obtains product, calculates
Yield is 83%, selective A:B is 4: 96.
Embodiment 18：Under condition of no solvent, [the LaCl of 0.5mol%4(THF)] (HIPr) is catalyzed under 50 DEG C, normal pressure
The reaction of N- propyl -2- rubigan aziridine and carbon dioxide：
Under anhydrous and oxygen-free, inert gas shielding, [LaCl is added in reaction bulb4(THF)] (HIPr) is protected in carbon dioxide airbag
Under shield, N- propyl -2- rubigan aziridine is added, is stirred to react in 50 DEG C of constant temperature bath 12 hours and obtains product,
It is 46% to calculate yield, selective A:B is 12: 88.
Embodiment 19：Under condition of no solvent, [the LaCl of 1 mol%4(THF)] (HIPr) is catalyzed N- under 50 DEG C, normal pressure
The reaction of propyl -2- p-methylphenyls aziridine and carbon dioxide：
Under anhydrous and oxygen-free, inert gas shielding, [LaCl is added in reaction bulb4(THF)] (HIPr) is protected in carbon dioxide airbag
Under shield, N- propyl -2- p-methylphenyl aziridine is added, is stirred to react 15 hours and is produced in 50 DEG C of constant temperature bath
Object, it is 94% to calculate yield, selective A:B is 7: 93.
Embodiment 20：Using dimethyl sulfoxide as solvent, [the YbCl of 0.75 mol%4(THF)] (HIPr) at 50 DEG C, normal pressure
The reaction of lower catalysis N- ethyl -2- phenyl aziridine and carbon dioxide：
Under anhydrous and oxygen-free, inert gas shielding, [YbCl is added in reaction bulb4(THF)] (HIPr) is protected in carbon dioxide airbag
Under shield, -2 phenyl aziridine of N- ethyls is added, is stirred to react in 50 DEG C of constant temperature bath and obtains within 12 hours product, calculates production
Rate is 88%, selective A:B is 5:95.
Embodiment 21：Under condition of no solvent, [the LaCl of 1 mol%4(THF)] (HIPr) is catalyzed under 50 DEG C, normal pressure
The reaction of N- ethyl -2- phenyl aziridine and carbon dioxide：
Under anhydrous and oxygen-free, inert gas shielding, [LaCl is added in reaction bulb4(THF)] (HIPr) is protected in carbon dioxide airbag
Under shield, -2 phenyl aziridine of N- ethyls is added, is stirred to react in 50 DEG C of constant temperature bath and obtains within 10 hours product, calculates production
Rate is 76%, selective A:B is 10:90.
Bu Fen oxazolidone nuclear magnetic datas manufactured in the present embodiment are as follows：
1H NMR（400MHz, CDCl3）δ1.17（t,J = 7.24 Hz, 3H）,3.27-3.44(m, 3H), 3.91(t,J = 8.72 Hz, 1H), 5.47(t, J = 7.92 Hz, 1H), 7.33-7.42(m, 5H)。
1H NMR（400MHz, CDCl3）δ1.17 (t,J = 7.24 Hz, 3H), 3.29-3.45(m, 3H),
3.93(t, J = 8.72 Hz, 1H), 5.46(t, J = 8.2, 1H), 7.29-7.38(m, 4H)。
1H NMR（400MHz, CDCl3）δ1.17(t,J = 7.76 Hz, 3H), 2.35(s, 3H), 3.29-3.43
(m, 3H), 3.89(t, J = 8.68 Hz, 1H), 5.43(t, J = 7.96, 1H), 7.18-7.28 (m, 4H)。
The present invention is prepared using a kind of rare earth imidazole salt compound catalysis aziridine derivative and carbon dioxide reaction
The chemical formula of oxazolidinone compounds, rare earth imidazole salts is：[RECl4(THF)2] (HIPr), in formula RE indicate rare earth metal from
Son, one kind in La, Sm, Yb, Y, HIPr 1,3- bis- (2,6- diisopropyl phenyl) glyoxaline cation.The catalyst system and catalyzing
In rare-earth metal catalyst structure it is clear, be readily synthesized, catalytic activity is high, and catalyst amount is few.Preparation disclosed by the invention
Raw material is easy to get in method, and reaction condition is mild, and substrate universality is wide, the high income of target product, operation and post-processes
Journey is simple.The application of this catalyst be it is completely new, currently without about with the approximate catalyst of this catalyst structure in the present invention
Application in reaction.Certain above-described embodiment is to be enumerated made by technical concepts and features to illustrate the invention rather than thoroughly
It lifts, its object is to allow person skilled in the art to can understand the content of the present invention and implement it accordingly, can not be limited with this
Protection scope of the present invention.The modification that all Spirit Essences according to main technical schemes of the present invention are done, should all cover in this hair
Within bright protection domain.
Claims (9)
1. application of the rare earth imidazole salt compound as catalyst aziridine derivative and carbon dioxide reaction, special
Sign is that the chemical structure of general formula of the rare earth imidazole salt compound is as follows：
Wherein, RE is rare earth metal.
2. application described in claim 1, which is characterized in that the preparation method of the rare earth imidazole salt compound includes following step
Suddenly：
（1）Using 2,6-DIPA and glyoxal as raw material, using acid solution as catalyst, two (2,6- diisopropyls are prepared
Phenyl) two Chlorobutadienes；
（2）With two (2,6- diisopropyl phenyl) two Chlorobutadienes, paraformaldehyde for raw material, in presence of hydrochloric acid, 1,3- is prepared
Two (2,6- diisopropyl phenyls) imidazoles villaumites；
（3）With 1,3- bis- (2,6- diisopropyl phenyl) imidazoles villaumite, lanthanide terchlorides compound for raw material, in tetrahydrofuran,
Prepare rare earth imidazole salt compound.
3. application according to claim 2, it is characterised in that：Step（1）In, prepare two (2,6- diisopropyl phenyls) two
Chlorobutadiene adds first specifically, 2,6-DIPA and glyoxal and absolute ethyl alcohol are added in reaction bulb
Aqueous acid filters after stirring 48h at room temperature, obtains two (2,6- diisopropyl phenyl) two Chlorobutadienes；Step（2）In, system
Standby 1,3-, bis- (2,6- diisopropyl phenyl) imidazoles villaumites are specifically, two (2,6- diisopropyl phenyl) two Chlorobutadienes are dissolved in
Toluene is added powdery paraformaldehyde, is stirred at 50 DEG C；Then 40 DEG C are cooled to, Isosorbide-5-Nitrae-dioxane solution of hydrochloric acid is added dropwise,
The reaction was continued 40 h, obtain 1,3- bis- (2,6- diisopropyl phenyl) imidazoles villaumite；Step（3）In, prepare rare earth imidazoles salinization
Object is closed specifically, by 1,3- bis- (2,6- diisopropyl phenyl) imidazoles villaumite is mixed with lanthanide terchlorides compound, in 50 DEG C of conditions
Under, in THF solvents react 24 h, centrifugal treating, takes supernatant concentration, concentrate to crystallize and obtain in pure THF after reaction
Rare earth imidazole salt compound.
4. application according to claim 1, it is characterised in that：The reaction is carried out in the case where having solvent or condition of no solvent.
5. application according to claim 1, it is characterised in that：The reaction temperature is 40 DEG C~70 DEG C；Reaction time is
10h~15h.
6. application according to claim 1, it is characterised in that：The molar ratio of the aziridine derivative and catalyst
It is 100:（0.5~1）.
7. application of the rare earth imidazole salt compound as catalyst in preparing 5- substituted oxazolidinones described in claim 1.
It, will under anhydrous and oxygen-free, inert gas shielding 8. a kind of preparation method of 5- substituted oxazolidinones, includes the following steps
Rare earth imidazole salt compound is added in reaction bulb；Then inert gas is drained, carbon dioxide is passed through, reinjects aziridine bottom
Object is reacted, and 5- substituted oxazolidinones are obtained；
The chemical structure of general formula of the rare earth imidazole salt compound is as follows：
Wherein, RE is rare earth metal.
9. the preparation method of 5- substituted oxazolidinones according to claim 8, it is characterised in that：There are solvent or solvent-free item
Under part, aziridine substrate is injected；The dosage of the rare earth imidazole salt compound is aziridine substrate mole
（0.5~1）%；Reaction temperature is 40 DEG C~70 DEG C；Reaction time is 10h~15h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810515924.3A CN108554456B (en) | 2016-09-20 | 2016-09-20 | Application of rare earth imidazolium salt compound as catalyst |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610834147.XA CN106432307B (en) | 2016-09-20 | 2016-09-20 | A kind of rare earth imidazole salt compound and preparation method thereof and the application as catalyst |
| CN201810515924.3A CN108554456B (en) | 2016-09-20 | 2016-09-20 | Application of rare earth imidazolium salt compound as catalyst |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610834147.XA Division CN106432307B (en) | 2016-09-20 | 2016-09-20 | A kind of rare earth imidazole salt compound and preparation method thereof and the application as catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108554456A true CN108554456A (en) | 2018-09-21 |
| CN108554456B CN108554456B (en) | 2021-02-12 |
Family
ID=58166928
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810515924.3A Active CN108554456B (en) | 2016-09-20 | 2016-09-20 | Application of rare earth imidazolium salt compound as catalyst |
| CN201610834147.XA Active CN106432307B (en) | 2016-09-20 | 2016-09-20 | A kind of rare earth imidazole salt compound and preparation method thereof and the application as catalyst |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610834147.XA Active CN106432307B (en) | 2016-09-20 | 2016-09-20 | A kind of rare earth imidazole salt compound and preparation method thereof and the application as catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN108554456B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108101721A (en) * | 2017-12-20 | 2018-06-01 | 西安近代化学研究所 | A kind of preparation method of metal salt combustion catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4324669B2 (en) * | 2004-01-21 | 2009-09-02 | 独立行政法人産業技術総合研究所 | Method for producing cyclic urethane |
| CN102548640A (en) * | 2009-09-24 | 2012-07-04 | 株式会社东芝 | Carbon dioxide absorbent solution |
| CN104583172A (en) * | 2012-07-04 | 2015-04-29 | 株式会社可乐丽 | Metal complex, and absorbent, occlusion material and separation material produced therefrom |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103641811B (en) * | 2013-12-20 | 2015-05-20 | 苏州大学张家港工业技术研究院 | Method for preparing cyclic carbonate |
| CN105153059B (en) * | 2015-09-11 | 2018-03-06 | 苏州大学 | The preparation method of Yi Zhong oxazolidinone compounds |
-
2016
- 2016-09-20 CN CN201810515924.3A patent/CN108554456B/en active Active
- 2016-09-20 CN CN201610834147.XA patent/CN106432307B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4324669B2 (en) * | 2004-01-21 | 2009-09-02 | 独立行政法人産業技術総合研究所 | Method for producing cyclic urethane |
| CN102548640A (en) * | 2009-09-24 | 2012-07-04 | 株式会社东芝 | Carbon dioxide absorbent solution |
| CN104583172A (en) * | 2012-07-04 | 2015-04-29 | 株式会社可乐丽 | Metal complex, and absorbent, occlusion material and separation material produced therefrom |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106432307A (en) | 2017-02-22 |
| CN106432307B (en) | 2018-07-31 |
| CN108554456B (en) | 2021-02-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Guo et al. | Cu (i)-catalyzed chemical fixation of CO 2 with 2-alkynylaniline into 4-hydroxyquinolin-2 (1 H)-one | |
| CN106432307B (en) | A kind of rare earth imidazole salt compound and preparation method thereof and the application as catalyst | |
| CN101664699B (en) | Catalyzer used for preparing acidamide compound and application thereof | |
| CN109879813A (en) | A kind of new process synthetic method of 2- sulfydryl -5- methoxybenzimidazol | |
| CN111747926B (en) | Improved synthetic process method of topiramate free base | |
| CN110218192B (en) | Preparation method of 2-amino-4, 6-dimethoxypyrimidine | |
| CN109265403B (en) | Synthesis method of benzimidazole and derivatives thereof | |
| CN112062705A (en) | Synthesis method of 7-methyltryptophan | |
| CN115340475B (en) | Preparation method of 1-diphenyl diazene oxide or derivative thereof | |
| CN101279929B (en) | Preparation of optically active 3-amino-N-cyclopropyl-2-hydroxyl hexanamide | |
| CN101088999A (en) | Process of synthesizing 3-amino quinine dihydrochloride | |
| CN115340474B (en) | Application of zirconium hydroxide as catalyst in catalyzing aniline or derivative thereof to prepare 1-diphenyl diazene oxide or derivative thereof | |
| CN114671781B (en) | Method for converting arylbenzylamine into arylnitrile compound | |
| CN114436803B (en) | Preparation method of 3- (4-chlorophenyl) -1, 5-diphenylpentane-1, 5-dione compound | |
| CN111925341B (en) | Preparation method of piperazine | |
| CN113441135B (en) | Preparation method of 2-amino-3H-phenoxazin-3-one or derivative thereof | |
| CN110292948B (en) | Application of imines-functionalized imidazole chloride salt as catalyst in preparation of aromatic heterocyclic formate compounds | |
| CN112521289B (en) | Oxaallylamine compound and preparation method and application thereof | |
| CN101343213B (en) | Allyl ether series compound and preparation thereof | |
| CN104370807B (en) | The synthetic method of a kind of 6-hydroxyl-5-nitronicotinic acid and process for separation and purification thereof | |
| CN117964553A (en) | Method for selectively synthesizing 2-amido quinoline-N-oxide compound from quinoline-N-oxide compound | |
| CN115124452A (en) | Preparation method of 2- (4-amino-2-ethoxyphenyl) isoindole-1, 3-dione | |
| CN115504891A (en) | Preparation method of 2-methoxy ethylamine | |
| CN114082442A (en) | Succinimidyl ionic liquid and method for catalytically synthesizing quinazoline-2, 4(1H,3H) -diketone by using same | |
| CN115925501A (en) | Preparation method of cyclopropane compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |