CN106311330B - Ion pair type rare-earth metal catalyst and its preparation method and application - Google Patents
Ion pair type rare-earth metal catalyst and its preparation method and application Download PDFInfo
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- CN106311330B CN106311330B CN201610711320.7A CN201610711320A CN106311330B CN 106311330 B CN106311330 B CN 106311330B CN 201610711320 A CN201610711320 A CN 201610711320A CN 106311330 B CN106311330 B CN 106311330B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 42
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- -1 oxyl Chemical group 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 18
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 16
- 238000005935 nucleophilic addition reaction Methods 0.000 claims abstract description 15
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 12
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 12
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 11
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical group [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims abstract description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 49
- 150000002500 ions Chemical class 0.000 claims description 37
- 229910006400 μ-Cl Inorganic materials 0.000 claims description 22
- 239000003960 organic solvent Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 15
- 239000003446 ligand Substances 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 238000010668 complexation reaction Methods 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- BAYUSCHCCGXLAY-UHFFFAOYSA-N 1-(3-methoxyphenyl)ethanone Chemical compound COC1=CC=CC(C(C)=O)=C1 BAYUSCHCCGXLAY-UHFFFAOYSA-N 0.000 claims description 2
- ARKIFHPFTHVKDT-UHFFFAOYSA-N 1-(3-nitrophenyl)ethanone Chemical compound CC(=O)C1=CC=CC([N+]([O-])=O)=C1 ARKIFHPFTHVKDT-UHFFFAOYSA-N 0.000 claims description 2
- WYECURVXVYPVAT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Br)C=C1 WYECURVXVYPVAT-UHFFFAOYSA-N 0.000 claims description 2
- AJKVQEKCUACUMD-UHFFFAOYSA-N 2-Acetylpyridine Chemical compound CC(=O)C1=CC=CC=N1 AJKVQEKCUACUMD-UHFFFAOYSA-N 0.000 claims description 2
- XSAYZAUNJMRRIR-UHFFFAOYSA-N 2-acetylnaphthalene Chemical compound C1=CC=CC2=CC(C(=O)C)=CC=C21 XSAYZAUNJMRRIR-UHFFFAOYSA-N 0.000 claims description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 claims description 2
- GNKZMNRKLCTJAY-UHFFFAOYSA-N 4'-Methylacetophenone Chemical compound CC(=O)C1=CC=C(C)C=C1 GNKZMNRKLCTJAY-UHFFFAOYSA-N 0.000 claims description 2
- YQYGPGKTNQNXMH-UHFFFAOYSA-N 4-nitroacetophenone Chemical compound CC(=O)C1=CC=C([N+]([O-])=O)C=C1 YQYGPGKTNQNXMH-UHFFFAOYSA-N 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- NRNHJIRMWBDTJE-UHFFFAOYSA-N pentan-3-one;toluene Chemical compound CCC(=O)CC.CC1=CC=CC=C1 NRNHJIRMWBDTJE-UHFFFAOYSA-N 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- NAGBNJKFFFSVGU-UHFFFAOYSA-N [Cl].C(C)(=O)C1=CC=CC=C1 Chemical group [Cl].C(C)(=O)C1=CC=CC=C1 NAGBNJKFFFSVGU-UHFFFAOYSA-N 0.000 claims 1
- 230000006315 carbonylation Effects 0.000 claims 1
- 238000005810 carbonylation reaction Methods 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 claims 1
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 17
- 125000000217 alkyl group Chemical group 0.000 abstract description 9
- 230000001681 protective effect Effects 0.000 abstract description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 22
- 239000000047 product Substances 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-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
- 239000008188 pellet Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229960000935 dehydrated alcohol Drugs 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- LEIMLDGFXIOXMT-UHFFFAOYSA-N trimethylsilyl cyanide Chemical compound C[Si](C)(C)C#N LEIMLDGFXIOXMT-UHFFFAOYSA-N 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000007344 nucleophilic reaction Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- ZSKGQVFRTSEPJT-UHFFFAOYSA-N pyrrole-2-carboxaldehyde Chemical compound O=CC1=CC=CN1 ZSKGQVFRTSEPJT-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 231100000004 severe toxicity Toxicity 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- PONXTPCRRASWKW-ZIAGYGMSSA-N (1r,2r)-1,2-diphenylethane-1,2-diamine Chemical compound C1([C@@H](N)[C@H](N)C=2C=CC=CC=2)=CC=CC=C1 PONXTPCRRASWKW-ZIAGYGMSSA-N 0.000 description 1
- PONXTPCRRASWKW-UHFFFAOYSA-N 1,2-diphenylethane-1,2-diamine Chemical compound C=1C=CC=CC=1C(N)C(N)C1=CC=CC=C1 PONXTPCRRASWKW-UHFFFAOYSA-N 0.000 description 1
- ZDOYHCIRUPHUHN-UHFFFAOYSA-N 1-(2-chlorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC=C1Cl ZDOYHCIRUPHUHN-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- DANBQHLZCHUINA-UHFFFAOYSA-N [SiH4].N#CC#N Chemical compound [SiH4].N#CC#N DANBQHLZCHUINA-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000004896 high resolution mass spectrometry Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- 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
-
- 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
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
- B01J2231/342—Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones
- B01J2231/343—Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones to prepare cyanhydrines, e.g. by adding HCN or TMSCN
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of ion pair type rare-earth metal catalysts and its preparation method and application, the structure such as formula (I) of the ion pair type rare-earth metal catalyst or (II) are shown, wherein, in above formula, R is selected from the alkyl of H, C1-C6 or the oxyl of C1-C6, and RE is selected from scandium, yttrium or lanthanide element.The ion pair type rare-earth metal catalyst as made from this method can be catalyzed trimethyl silicane nitrile to the nucleophilic addition of carbonyls under mild conditions, and reaction efficiency height and environmentally protective；In addition, the method for preparation ion pair type rare-earth metal catalyst has the characteristics that the yield of simple step, mild condition, reaction rate and product is higher,
Description
Technical field
The present invention relates to rare-earth metal catalysts, and in particular, to ion pair type rare-earth metal catalyst and its preparation side
Method and application.
Background technique
α-cyanalcohol is a kind of organic synthesis intermediate for having and value being widely applied, is passed through due to its polyfunctional group structure
Further reaction can synthesize the compounds such as a-amino acid or 'alpha '-hydroxy acids.Industrial production cyanalcohol mainly uses hydrogen cyanide to carbonyl
It is prepared by the nucleophilic addition of compound.This method uses the hydrogen cyanide of severe toxicity as nucleopilic reagent.It compares, passes through trimethyl
The nucleophilic addition of cyanogen silane (TMSCN) and aldehydes or ketones obtains cyanalcohol using hydrolysis can be to avoid the cyaniding for using severe toxicity
Hydrogen industrially has significant application value.But the nucleophilic addition of existing trimethylsilyl cyanide (TMSCN) and aldehydes or ketones
There is the disadvantages of needing catalytic amount big, catalytic efficiency is not high and needs using organic solvent in reaction.
Summary of the invention
The object of the present invention is to provide a kind of ion pair type rare-earth metal catalysts and its preparation method and application, by this
Ion pair type rare-earth metal catalyst made from method can be catalyzed trimethyl silicane nitrile to carbonyls under mild conditions
Nucleophilic addition, and reaction efficiency height and environmentally protective；In addition, the method for preparation ion pair type rare-earth metal catalyst
Have the characteristics that the yield of simple step, mild condition, reaction rate and product is higher.
To achieve the goals above, the present invention provides a kind of ion pair type rare-earth metal catalyst, the ion pair type is dilute
The structure of earth metal catalyst such as formula (I) or (II) are shown,
Wherein, in above formula, R is selected from the alkyl of H, C1-C6 or the oxyl of C1-C6, and RE is selected from scandium, yttrium or lanthanide series metal member
Element.
The present invention also provides a kind of preparation method of above-mentioned ion pair type rare-earth metal catalyst, the preparation methods
Are as follows: it, will be the ligand one of the structure as shown in formula (III), the structure as shown in formula (V) in the presence of organic solvent and protection gas
[(Me3Si)2N]3RE(μ-Cl)Li(THF)3Complexation reaction is carried out so that the ion pair type rare earth gold of the structure as shown in formula (I) is made
Metal catalyst；
Alternatively, organic solvent and protection gas in the presence of, will the structure as shown in formula (IV) ligand two, such as formula (V) institute
Show the [(Me of structure3Si)2N]3RE(μ-Cl)Li(THF)3Complexation reaction is carried out so that the ion pair of the structure as shown in formula (II) is made
Type rare-earth metal catalyst；
Wherein, R is selected from the alkyl of H, C1-C6 or the oxyl of C1-C6, and RE is selected from scandium, yttrium or lanthanide element.
Invention further provides a kind of above-mentioned ion pair type rare-earth metal catalysts in catalysis trimethyl silicane nitrile pair
Application in the nucleophilic addition of carbonyls.
Through the above technical solutions, one aspect of the present invention passes through [(Me3Si)2N]3RE(μ-Cl)Li(THF)3With ligand one
Or ligand two carries out the ion pair type rare-earth metal catalyst that the structure as shown in formula (I) or (II) is made in complexation reaction；It is another
Aspect is catalyzed trimethyl silicane nitrile to the nucleophilic addition of carbonyls using ion pair type rare-earth metal catalyst, and then
To preparing α-cyanalcohol intermediate.In addition, the nucleophilic addition has the advantages that reaction efficiency height and environmentally protective；Meanwhile
The method for preparing ion pair type rare-earth metal catalyst has the yield of simple step, mild condition, reaction rate and product equal
Higher feature.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the single crystal diffraction figure of catalyst II-2 in embodiment 2.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of ion pair type rare-earth metal catalyst, the structures of the ion pair type rare-earth metal catalyst
As shown in formula (I) or (II),
Wherein, in above formula, R is selected from the alkyl of H, C1-C6 or the oxyl of C1-C6, and RE is selected from scandium, yttrium or lanthanide series metal member
Element.
In the present invention, the selection within the above range of R and RE, but consider from the yield of preparation, it is preferable that R choosing
From the alkyl of H, C1-C3 or the oxyl of C1-C3, RE is selected from scandium, yttrium or lanthanide element；It is highly preferred that R is selected from H, C1-
The alkyl of C3 or the oxyl of C1-C3, RE are selected from scandium, yttrium or lanthanide element；It is further preferred that R be H, RE be selected from Er,
Sm, Dy or Y.
The present invention also provides a kind of preparation method of above-mentioned ion pair type rare-earth metal catalyst, the preparation methods
Are as follows: it, will be the ligand one of the structure as shown in formula (III), the structure as shown in formula (V) in the presence of organic solvent and protection gas
[(Me3Si)2N]3RE(μ-Cl)Li(THF)3Complexation reaction is carried out so that the ion pair type rare earth gold of the structure as shown in formula (I) is made
Metal catalyst；
Alternatively, organic solvent and protection gas in the presence of, will the structure as shown in formula (IV) ligand two, such as formula (V) institute
Show the [(Me of structure3Si)2N]3RE(μ-Cl)Li(THF)3Complexation reaction is carried out so that the ion pair of the structure as shown in formula (II) is made
Type rare-earth metal catalyst；
Wherein, R is selected from the alkyl of H, C1-C6 or the oxyl of C1-C6, and RE is selected from scandium, yttrium or lanthanide element.
In this preparation method, the selection within the above range of R and RE, but consider from the yield of product, it is preferable that
R is selected from the alkyl of H, C1-C3 or the oxyl of C1-C3, and RE is selected from scandium, yttrium or lanthanide element；It is highly preferred that R be selected from H,
The alkyl of C1-C3 or the oxyl of C1-C3, RE are selected from scandium, yttrium or lanthanide element；It is further preferred that R is H, RE is selected from
Er, Sm, Dy or Y.
In the present invention, the dosage of each material can select in a wide range, but in order to further increase yield, it is excellent
Selection of land, relative to 1mmol [(Me3Si)2N]3RE(μ-Cl)Li(THF)3, the dosage of ligand one or ligand two is 2-
2.5mmol；It is highly preferred that relative to 1mmol [(Me3Si)2N]3RE(μ-Cl)Li(THF)3, the dosage of organic solvent is 15-
25mL。
In the above preparation method, the actual conditions of complexation reaction can select in a wide range, but in order into one
Step improves yield, it is preferable that complexation reaction at least meets the following conditions: reaction temperature is 45-55 DEG C, reaction time 12-
24h。
Meanwhile in the present invention, the specific type of organic solvent and protection gas can select in a wide range, but be
Further increase yield and reaction rate, it is preferable that organic solvent be selected from n-hexane, tetrahydrofuran and toluene one kind or
It is a variety of；It is highly preferred that protection gas is selected from one of helium, nitrogen and argon gas or a variety of.
Invention further provides a kind of above-mentioned ion pair type rare-earth metal catalysts in catalysis trimethyl silicane nitrile pair
Application in the nucleophilic addition of carbonyls.
In above-mentioned application, the dosage of ion pair type rare-earth metal catalyst can select in a wide range, but be
It further increases catalytic effect and reduces cost, it is preferable that relative to the carbonyls of 1mmol, ion pair type rare earth
The dosage of metallic catalyst is 0.0001-0.01mmol, more preferably 0.002-0.01mmol.
In above-mentioned application, the dosage of raw material can select in a wide range, but in order to further increase yield, it is excellent
Selection of land, relative to the carbonyls of 1mmol, the dosage of trimethyl silicane nitrile is 1-1.5mmol.
In addition, the specific reflection condition of nucleophilic addition can select in a wide range, but in order to improve reaction
Yield, it is preferable that nucleophilic addition at least meets the following conditions: reaction temperature be 20-30 DEG C, reaction time 2-6h.
In addition, the specific type of carbonyls can select in a wide range in above-mentioned application, but in order into
One step improves the yield of reaction, it is preferable that carbonyls is selected from ketone compounds or aldehyde compound；It is highly preferred that carbonyl
Based compound is selected from alkanones compound, alicyclic ring ketone compounds, aromatic ketone compounds or heterocyclic ketones；Into one
Step preferably, carbonyls be 3- methyl -2- butanone, cyclohexanone, cyclopentanone, acetophenone, melilotal, to chlorobenzene second
Ketone, parabromoacetophenone, p-nitroacetophenone, o-methyl-benzene ethyl ketone, o-chloroacetophenone, ortho-nitroacetophenone, m-nitroacetophenone,
Meta-methoxy acetophenone, 2- acetonaphthone, 2- acetylpyridine.
On the basis of above-mentioned content, the specific type of organic solvent and protection gas can select in a wide range,
But in order to further increase the yield of nucleophilic addition and reaction rate, it is preferable that in the system of nucleophilic addition
In further include organic solvent；It is highly preferred that organic solvent is selected from one of n-hexane, tetrahydrofuran and ether or a variety of.Its
In, the dosage of organic solvent can select in a wide range, but in order to further control cost and environmental protection, more preferably instead
It can should carry out under solvent-free conditions.
Finally, in the present invention, all THF refer to tetrahydrofuran.
The structure for catalyzed by rare-earth complex agent that the present invention will be described in detail by way of examples below is in SMART
Diffraction data is collected on CCD diffractometer.Using the MoK alpha ray of graphite monochromatic, T=293 (2) K, ω are swept
Technology is retouched, whole intensity datas are through Lp factor calibration, and using 5.03 program of SHELXTL, crystal structure uses heavy-atom method solution
Out, whole non-hydrogen atom coordinate parameters are obtained after being taken turns Fourier transformation more, theoretical hydrogenation method obtains all hydrogen atom coordinates,
Anisotropic temperature factor is corrected through complete matrix least square method (SHELXS-97) to all non-hydrogen atoms；Elemental analysis passes through
Perkin-Elmer Model 2400Series II elemental analyzer is measured.
Intermediate [(Me used in embodiment3Si)2N]3RE(μ-Cl)Li(THF)3(RE is yttrium and lanthanide series metal) is ginseng
Examine document that Wang Shaowu et al. publishes (E.H.Sheng, S.W.Wang, G.S.Yang, S.L.Zhou, L.Cheng,
K.H.Zhang, Z.X.Huang.Organometallics 2003,22,684) in method be prepared.
Preparation example 1
The preparation of the ligand one of the structure as shown in formula (III):
At 25 DEG C, 1,2- diphenyl ethylene diamine (5.31g, 25.0mmol) is dissolved in 30mL dehydrated alcohol, then plus
Enter 2- pyrrole aldehyde (5.46g, 50mmol), stirring makes it completely dissolved, and the p-methyl benzenesulfonic acid of catalytic amount is then added, 4 is small
When after a large amount of light yellow solids are precipitated in reaction solution, crude product is obtained by filtration, is finally recrystallized to give with dehydrated alcohol light yellow
Solid (7.32g, yield 80%).
The characterization result of product are as follows:1H NMR(500MHz,CDCl3):δ7.84(s,2H),7.13-7.03(m,10H),
7.76(s,2H),7.28-7.27(m,2H),6.28-6.27(m,2H),6.09-6.07(m,2H),4.56(s,2H).13C NMR
(125MHz,CDCl3):δ152.9,142.2,130.7,128.4,127.2,122.1,114.9,110.0,80.7.HR-MS
(ESI)Calcd.For C24H22N4[M+H+]:367.1917,found:367.1913.
Preparation example 2
The preparation of the ligand one of the structure as shown in formula (IV):
At 25 DEG C, by (1R, 2R) -1,2- diphenyl ethylene diamine (5.31g, 25.0mmol) is dissolved in 30mL dehydrated alcohol
In, then be added 2- pyrrole aldehyde (5.46g, 50mmol), stirring makes it completely dissolved, then be added catalytic amount to methylbenzene
A little floccule is precipitated in sulfonic acid in reaction solution after 4 hours, which is spin-dried on a rotary evaporator, again with methylene chloride
Secondary dissolution is eventually adding saturated sodium carbonate extraction and removes a small amount of p-methyl benzenesulfonic acid, solvent finally is drained in organic phase concentration
Obtain light yellow powder solid (7.78g, yield 85%).
The characterization result of product are as follows: 1H NMR (500MHz, CDCl3): δ 7.84 (s, 2H), 7.13-7.03 (m, 10H),
7.76(s,2H),7.28-7.27(m,2H),6.28-6.27(m,2H),6.09-6.07(m,2H),4.56(s,2H).
Embodiment 1
The preparation of ion pair type rare-earth metal catalyst I-1:
Under protection of argon gas, by [(Me3Si)2N]3Er(μ-Cl)Li(THF)3Two neck bottles are added in (0.95g, 1.05mmol)
In, compound III-1 (0.77g, 2.10mmol) then is added, adds the THF (tetrahydrofuran) of 20mL, it is anti-under the conditions of 50 DEG C
It answers solution after 12h to become light brown, then drains the mixed solution, n-hexane washing, export n-hexane and vacuum pumping is added
It does to powdered, is eventually adding 10mL toluene and extracts recrystallization, stand 2 days under the conditions of -5 DEG C, obtain light brown rhombohedral crystal
(0.81g, yield 65%).
The characterize data of product are as follows: IR (KBr pellets, cm-1):ν3458(s),1631(s),1597(m),1392
(w),1311(m),1267(m),1031(s),974(m),740(w),700(m).Anal.Calcd for ErC64H72N8O4Li:
C,64.51；H,6.09；N,9.40；Found:C,63.63；H,5.69；N,9.53.
Embodiment 2
The preparation of ion pair type rare-earth metal catalyst I-2:
It carries out that light brown rhomboidan (0.93g, yield 69%) is made according to the method for embodiment 1, except that will
[(Me3Si)2N]3Er(μ-Cl)Li(THF)3(0.95g, 1.05mmol) is changed to [(Me3Si)2N]3Sm(μ-Cl)Li(THF)3
The dosage of compound III-1 is changed to 2.30mmol by (1.02g, 1.15mmol).
The characterize data of product are as follows: IR (KBr pellets, cm-1):ν3421(s),1629(s),1593(s),1421
(m),1311(m),1031(m),738(w),700(m).Anal.Calcd for SmC64H72N8O4Li:C,65.44；H,6.18；
N,9.54；Found:C,64.98；H,5.48；N,9.85.
Embodiment 3
The preparation of ion pair type rare-earth metal catalyst I-3:
It carries out that light brown rhomboidan (0.69g, yield 58%) is made according to the method for embodiment 1, except that will
[(Me3Si)2N]3Er(μ-Cl)Li(THF)3(0.95g, 1.05mmol) is changed to [(Me3Si)2N]3Dy(μ-Cl)Li(THF)3
The dosage of compound III-1 is changed to 2.00mmol by (0.90g, 1.00mmol).
The characterize data of product are as follows: IR (KBr pellets, cm-1):ν3481(s),2360(s),1629(s),1597
(m),1390(w),1311(m),1031(m),974(m),738(w),700(m).Anal.Calcd for SmC64H72N8O4Li:
C,64.77；H,6.12；N,9.44；Found:C,64.72；H,5.72；N,9.43.
Embodiment 4
The preparation of ion pair type rare-earth metal catalyst II-1:
It carries out that light brown rhomboidan (0.55g, yield 46%) is made according to the method for embodiment 1, except that will
[(Me3Si)2N]3Er(μ-Cl)Li(THF)3(0.95g, 1.05mmol) is changed to [(Me3Si)2N]3Y(μ-Cl)Li(THF)3
Compound III-1 is changed to compound IV-1 (0.88g, 2.40mmol) by (0.99g, 1.20mmol).
The characterize data of product are as follows:1H NMR(500MHz,C4D8O):δ8.00(s,4H),7.32-7.00(m,20H),
6.89(s,4H),6.35(s,4H),6.05(m,4H),4.78(s,4H).13C NMR(75MHz,C4D8O):δ140.4,127.3,
126.3,126.1,125.7,124.5,120.6,113.5,106.9,77.6,65.3,65.1,64.8,64.5,64.2,63.9,
23.5,23.0,22.7,22.4,22.2,21.9,0.16.IR(KBr pellets,cm-1):ν3473(s),2360(s),1616
(s),1595(m),1431(w),1388(w),1031(m),972(m),700(s),609(s).
Embodiment 5
The preparation of ion pair type rare-earth metal catalyst II-2:
It carries out that light brown rhomboidan (0.60g, yield 50%) is made according to the method for embodiment 1, except that will
[(Me3Si)2N]3Er(μ-Cl)Li(THF)3(0.95g, 1.05mmol) is changed to [(Me3Si)2N]3Sm(μ-Cl)Li(THF)3
Compound III-1 is changed to compound IV-1 (0.85g, 2.32mmol) by (1.03g, 1.16mmol).
The characterize data of product are as follows: IR (KBr pellets, cm-1):ν3415(s),2364(s),1624(s),1595
(m),1388(w),1033(m),1029(m),698(s),609(s).
Embodiment 6
The preparation of ion pair type rare-earth metal catalyst II-3:
It carries out that light brown rhomboidan (0.42g, yield 42%) is made according to the method for embodiment 1, except that will
[(Me3Si)2N]3Er(μ-Cl)Li(THF)3Dosage be changed to 1.08mmol, compound III-1 is changed to compound IV-1
(0.79g,2.16mmol)。
The characterize data of product are as follows: IR (KBr pellets, cm-1):ν3473(s),2360(s),1620(s),1598
(m),1390(w),1311(m),1029(m),700(s),609(s).Anal.Calcd for ErC50H46N8Li:C,64.52；
H,5.41；N,11.15；Found:C,64.20；H,5.48；N,10.72.
Application examples 1
At argon gas protection and 25 DEG C, rare earth metal complex and acetophenone compound are added in the reaction flask of 50mL
(1.0mmol) stirs 2-3 minutes, adds trimethyl silicane nitrile (1.2mmol), after reaction, filters, and yield is 99 weights
The product for measuring % can be directly obtained by being concentrated in vacuo liquid phase, remaining product obtains purified product by column chromatography for separation, stream
Dynamic is mutually ethyl acetate: petroleum ether=1:10；It specifically the results are shown in Table 1.
Table 1
Application examples 2
At argon gas protection and 25 DEG C, it is added in the reaction flask of 50mL catalyst I-1 (0.0001mmol) and various
Ketone compound (1.0mmol) is stirred 2-3 minutes, is added trimethyl silicane nitrile (1.2mmol), after reacting 4h, filtering, and yield
It can be directly obtained by being concentrated in vacuo liquid phase for the product of 99 weight %, remaining product obtains purifying by column chromatography for separation and produces
Object, mobile phase are ethyl acetate: petroleum ether=1:10, concrete outcome are shown in Table 2.
Table 2
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (17)
1. a kind of ion pair type rare-earth metal catalyst, which is characterized in that the structure of the ion pair type rare-earth metal catalyst
As shown in formula (I) or (II),
Wherein, in above formula, R H, RE are selected from scandium, yttrium or lanthanide element.
2. ion pair type rare-earth metal catalyst according to claim 1, wherein the R be H, the RE be selected from Er,
Sm, Dy or Y.
3. a kind of preparation method of ion pair type rare-earth metal catalyst as described in claim 1, which is characterized in that the system
Preparation Method are as follows: organic solvent and protection gas in the presence of, will the structure as shown in formula (III) ligand one, as shown in formula (V) knot
[(the Me of structure3Si)2N]3RE(μ-Cl)Li(THF)3The ion pair type that complexation reaction is carried out so that the structure as shown in formula (I) is made is dilute
Earth metal catalyst；
Alternatively, organic solvent and protection gas in the presence of, will the structure as shown in formula (IV) ligand two, as shown in formula (V) knot
[(the Me of structure3Si)2N]3RE(μ-Cl)Li(THF)3The ion pair type that complexation reaction is carried out so that the structure as shown in formula (II) is made is dilute
Earth metal catalyst；
Wherein, R H, RE are selected from scandium, yttrium or lanthanide element.
4. preparation method according to claim 3, wherein the R is H, and the RE is selected from Er, Sm, Dy or Y.
5. preparation method according to claim 3, wherein relative to [(Me described in 1mmol3Si)2N]3RE(μ-Cl)Li
(THF)3, the dosage of the ligand one or ligand two is 2-2.5mmol.
6. preparation method according to claim 3, wherein relative to [(Me described in 1mmol3Si)2N]3RE(μ-Cl)Li
(THF)3, the dosage of the organic solvent is 15-25mL.
7. preparation method according to claim 3, wherein the complexation reaction at least meets the following conditions: reaction temperature
It is 45-55 DEG C, reaction time 12-24h.
8. the preparation method according to any one of claim 3-7, wherein the organic solvent is selected from n-hexane, four
Hydrogen furans and toluene it is one or more.
9. the preparation method according to any one of claim 3-7, wherein the protection gas be selected from helium, nitrogen and
One of argon gas is a variety of.
10. a kind of ion pair type rare-earth metal catalyst as claimed in claim 1 or 2 is in catalysis trimethyl silicane nitrile to carbonylation
Close the application in the nucleophilic addition of object.
11. application according to claim 10, wherein relative to the carbonyls of 1mmol, the ion pair type
The dosage of rare-earth metal catalyst is 0.0001-0.01mmol.
12. application according to claim 11, wherein relative to the carbonyls of 1mmol, the ion pair type
The dosage of rare-earth metal catalyst is 0.002-0.01mmol.
13. application according to claim 10, wherein relative to the carbonyls of 1mmol, the trimethyl silicane
The dosage of nitrile is 1-1.5mmol.
14. application according to claim 10, wherein the nucleophilic addition at least meets the following conditions: reaction temperature
Degree is 20-30 DEG C, reaction time 2-6h.
15. application described in any one of 0-14 according to claim 1, wherein the carbonyls is selected from ketone chemical combination
Object or aldehyde compound.
16. application according to claim 14, wherein the carbonyls is selected from alkanones compound, alicyclic ketone
Class compound, aromatic ketone compounds or heterocyclic ketones.
17. application according to claim 15, wherein the carbonyls is 3- methyl -2- butanone, cyclohexanone, ring
Pentanone, acetophenone, melilotal, parachloroacetophenone, parabromoacetophenone, p-nitroacetophenone, o-methyl-benzene ethyl ketone, adjacent chlorine
Acetophenone, ortho-nitroacetophenone, m-nitroacetophenone, meta-methoxy acetophenone, 2- acetonaphthone, 2- acetylpyridine.
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