CN108906124A - Application of the triscyclopentadienyl rare earth metal complex as catalyst in catalysis ketone and pinacol borine synthetic reaction - Google Patents
Application of the triscyclopentadienyl rare earth metal complex as catalyst in catalysis ketone and pinacol borine synthetic reaction Download PDFInfo
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- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 62
- 229910000085 borane Inorganic materials 0.000 title claims abstract description 56
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 33
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 30
- 150000002576 ketones Chemical class 0.000 title claims abstract description 21
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 7
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 4
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 3
- -1 cyclopentadienyl rare-earth metal Chemical class 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 150000003997 cyclic ketones Chemical class 0.000 claims description 6
- 150000008365 aromatic ketones Chemical group 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims 1
- 230000035484 reaction time Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 4
- 238000012805 post-processing Methods 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 229910052779 Neodymium Inorganic materials 0.000 abstract description 2
- 229910052772 Samarium Inorganic materials 0.000 abstract description 2
- 229910052769 Ytterbium Inorganic materials 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 abstract description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 abstract description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 abstract description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 36
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 26
- 230000005291 magnetic effect Effects 0.000 description 21
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 20
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 18
- 239000012298 atmosphere Substances 0.000 description 17
- 230000018044 dehydration Effects 0.000 description 17
- 238000006297 dehydration reaction Methods 0.000 description 17
- 239000011261 inert gas Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- 230000005311 nuclear magnetism Effects 0.000 description 14
- 238000005160 1H NMR spectroscopy Methods 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 235000010338 boric acid Nutrition 0.000 description 7
- 239000004327 boric acid Substances 0.000 description 7
- 229960002645 boric acid Drugs 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical group CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- SXVPOSFURRDKBO-UHFFFAOYSA-N Cyclododecanone Chemical compound O=C1CCCCCCCCCCC1 SXVPOSFURRDKBO-UHFFFAOYSA-N 0.000 description 4
- 238000006197 hydroboration reaction Methods 0.000 description 4
- BSMGLVDZZMBWQB-UHFFFAOYSA-N 2-methyl-1-phenylpropan-1-one Chemical compound CC(C)C(=O)C1=CC=CC=C1 BSMGLVDZZMBWQB-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910052693 Europium Inorganic materials 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- YFKBXYGUSOXJGS-UHFFFAOYSA-N 1,3-Diphenyl-2-propanone Chemical compound C=1C=CC=CC=1CC(=O)CC1=CC=CC=C1 YFKBXYGUSOXJGS-UHFFFAOYSA-N 0.000 description 2
- WYECURVXVYPVAT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Br)C=C1 WYECURVXVYPVAT-UHFFFAOYSA-N 0.000 description 2
- XHLHPRDBBAGVEG-UHFFFAOYSA-N 1-tetralone Chemical compound C1=CC=C2C(=O)CCCC2=C1 XHLHPRDBBAGVEG-UHFFFAOYSA-N 0.000 description 2
- WXCMHFPAUCOJIG-UHFFFAOYSA-N 4'-tert-Butyl-2',6'-dimethyl-3',5'-dinitroacetophenone Chemical compound CC(=O)C1=C(C)C([N+]([O-])=O)=C(C(C)(C)C)C([N+]([O-])=O)=C1C WXCMHFPAUCOJIG-UHFFFAOYSA-N 0.000 description 2
- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 description 2
- YQYGPGKTNQNXMH-UHFFFAOYSA-N 4-nitroacetophenone Chemical compound CC(=O)C1=CC=C([N+]([O-])=O)C=C1 YQYGPGKTNQNXMH-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N dimethylacetone Natural products CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- XWCIICLTKWRWCI-UHFFFAOYSA-N 1-(2,4,6-trimethylphenyl)ethanone Chemical compound CC(=O)C1=C(C)C=C(C)C=C1C XWCIICLTKWRWCI-UHFFFAOYSA-N 0.000 description 1
- YOMBUJAFGMOIGS-UHFFFAOYSA-N 2-fluoro-1-phenylethanone Chemical compound FCC(=O)C1=CC=CC=C1 YOMBUJAFGMOIGS-UHFFFAOYSA-N 0.000 description 1
- GNKZMNRKLCTJAY-UHFFFAOYSA-N 4'-Methylacetophenone Chemical compound CC(=O)C1=CC=C(C)C=C1 GNKZMNRKLCTJAY-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 229940124158 Protease/peptidase inhibitor Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 201000006491 bone marrow cancer Diseases 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- GXJABQQUPOEUTA-RDJZCZTQSA-N bortezomib Chemical compound C([C@@H](C(=O)N[C@@H](CC(C)C)B(O)O)NC(=O)C=1N=CC=NC=1)C1=CC=CC=C1 GXJABQQUPOEUTA-RDJZCZTQSA-N 0.000 description 1
- 229960001467 bortezomib Drugs 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 210000002751 lymph Anatomy 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000137 peptide hydrolase inhibitor Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 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
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
-
- 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
- C07F5/02—Boron compounds
- C07F5/04—Esters of boric acids
-
- 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
- B01J2531/0225—Complexes comprising pentahapto-cyclopentadienyl analogues
-
- 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
- B01J2531/36—Yttrium
-
- 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
- B01J2531/37—Lanthanum
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
Application the invention discloses triscyclopentadienyl rare earth metal complex as catalyst in catalysis ketone and pinacol borine synthetic reaction, includes the following steps, catalyst, borine and ketone is uniformly mixed, reaction prepares borate；The molecular formula of triscyclopentadienyl rare earth metal complex is represented by：Ln(Cp)3, Ln expression rare earth metal, one of lanthanum, yttrium, neodymium, ytterbium, samarium in lanthanide series.The preparation method has higher catalytic activity, simultaneous reactions mild condition, and product postprocessing is easy, and the reaction time is short, and catalyst amount is low, and has the good substrate scope of application, and can carry out industrialized production.
Description
The invention belongs to a kind of entitled method for preparing borate using triscyclopentadienyl rare earth metal complex, application numbers
It is 201710162331.9, the applying date is the divisional application of the March in 2017 of patent application on the 17th, belongs to application method technology department
Point.
Technical field
The invention belongs to organic synthesis fields, and in particular to a kind of triscyclopentadienyl rare earth metal complex is being catalyzed as catalyst
Application in ketone and pinacol borine synthetic reaction.
Background technique
The application range of boric acid ester compound is very extensive, not only can be used as polymeric additive, gasoline additive,
Bactericidal agent, fire retardant use, and may be used as lube oil additive and motor vehicle brake fluid.Meanwhile boric acid or borate can be with
Other a variety of functional groups are converted to, it is a kind of important reagent in organic synthesis, and the research as chiral drug is also just gradually
In deeply, chiral boric acid is used to synthesize bortezomib as medicines structure unit now, it is the treatment of first approval
The Protease Inhibitor drugs of multiple bone marrow cancer and lymph cancer, so the application prospect of chiral boric acid or borate is very wide
Greatly.Rare earth ion, which is formed by complex, has unique physiochemical properties and under certain condition more significant magnetics
Property.Importantly, the irregular variation with the variation of radius of the stability of rare earth compounding, and influence complexes stability
Factor deionization radius outside, the change of metal ligancy in complex, the steric effect of ligand, hydration levels and valence link at
Divide and also generates important influence to complexes stability.Therefore researcher passes through phase interaction of the rare earth ion with different ligands
With largely changing, modify and enhance its characteristic.For example be entrained in conducting polymer CN-PPP in europium complex,
The energy transfer efficiency of symmetrical and asymmetric luxuriant and rich with fragrance beta-diketon europium complex is only 0.053%, far below the beta-diketon of symmetrical biphenyl
The 1.1% of europium complex.
Addition reaction using carbonyls and borine be synthesize the borate containing different substituents most directly, it is most former
The method of subeconomy.But research shows that in the case where no catalyst, some borines（Such as pinacol borine）It is difficult to occur
Hydroboration, it may be possible to which the lewis acidity of this kind of borine is too low to be caused.The synthesis of borate has several different methods, the
A kind of method that method namely uses earliest is directly reacted with boron chloride with alcohol or phenol, borate made from this method
There are the unobtainable drawbacks of raw material.Second method is reacted by the direct polycondensation of boric acid and alcohol or phenol, and such method is used
The advantages of be that raw material is easy to get, yield is high, and preparation process is simple to operation, becomes existing frequently-used method.The third method is benefit
With reacting for borax and alcohol or phenol, the advantages of this method is that borax is lower than boric acid price and be easily made, but there are products to be difficult to
The shortcomings that separation.In addition to this there are also some other methods to synthesize borate, such as the ester friendship of borate and alcohol or phenol
Change the direct reaction of reaction, boron oxide and alcohol or phenol.But these methods are more or less all to be had some drawbacks or is
The high requirements on the equipment, it is difficult to which industrialized production does not meet economic benefit or is that post-reaction treatment is more complicated, it is difficult to obtain
Higher yield or raw material are difficult to obtain, and price is more expensive.In existing catalyst system, catalyst amount is larger, when reaction
Between it is partially long, substrate universality is lower.Rare earth catalyst hydroboration reports less, and triscyclopentadienyl rare earth catalyst hydroboration at present
It does not have been reported that.
Summary of the invention
Goal of the invention of the invention is to provide a kind of method for preparing borate using triscyclopentadienyl rare earth metal complex, passes through
The application of triscyclopentadienyl rare earth metal complex, catalyzing ketone compound and pinacol borine prepare borate, which has
Higher catalytic activity, simultaneous reactions mild condition, product postprocessing are easy, and the reaction time is short, and catalyst amount is low, and has very
The good substrate scope of application, and industrialized production can be carried out.
In order to achieve the above objectives, the technical solution adopted by the present invention is that：It is a kind of to be prepared using triscyclopentadienyl rare earth metal complex
The method of borate, includes the following steps, catalyst, borine and ketone is uniformly mixed, reaction prepares borate；It is described to urge
Agent is triscyclopentadienyl rare earth metal complex；The chemical structural formula of the triscyclopentadienyl rare earth metal complex is as follows：
。
In above-mentioned technical proposal, the borine is pinacol borine；The ketone is aromatic ketone or fatty cyclic ketones；The virtue
One of for example following structural formula of the chemical structural formula of ketone musk：
、、, wherein R is phenyl, substituted-phenyl or heterocycle virtue
Base, such as thienyl；One of for example following structural formula of chemical structural formula of the fat cyclic ketones：
、, wherein n is 3~15.
In above-mentioned technical proposal, the dosage of the triscyclopentadienyl rare earth metal complex is the 0.01~1% of the mole of ketone；Institute
The molar ratio of the dosage and ketone of stating borine is 1~1.2: 1；Reaction time is 30min~1h；Reaction temperature is room temperature.
In above-mentioned technical proposal, the reaction carries out in organic solvent, carries out preferably in tetrahydrofuran.
In above-mentioned technical proposal, after reaction, solvent is removed under reduced pressure in reaction solution, obtains different substituted boracic acid esters.
It is anti-in catalysis ketone and the synthesis of pinacol borine as catalyst that the invention also discloses triscyclopentadienyl rare earth metal complexs
Application in answering；The chemical structural formula of the triscyclopentadienyl rare earth metal complex is as follows：
The molecular formula of above-mentioned triscyclopentadienyl rare earth metal complex is represented by：Ln(Cp)3, Ln indicates rare earth metal, selected from group of the lanthanides member
One of lanthanum, yttrium, neodymium, ytterbium, samarium in element.
In above-mentioned technical proposal, the borine is pinacol borine；The ketone is aromatic ketone or fatty cyclic ketones；The virtue
One of for example following structural formula of the chemical structural formula of ketone musk：
、、, wherein R is phenyl, substituted-phenyl or heterocycle virtue
Base；One of for example following structural formula of chemical structural formula of the fat cyclic ketones：
、, wherein n is 3~15.
In above-mentioned technical proposal, the dosage of the triscyclopentadienyl rare earth metal complex is the 0.01~1% of the mole of ketone；Institute
The molar ratio of the dosage and ketone of stating borine is 1~1.2: 1；Reaction time is 30min~1h.
Above-mentioned triscyclopentadienyl rare earth metal complex, which can be catalyzed ketone and react with the Borohydride reduction of pinacol borine, prepares boric acid
Ester, therefore application of the above-mentioned triscyclopentadienyl rare earth metal complex as catalyst in synthesis borate is claimed in the present invention.
In above-mentioned technical proposal, the reaction temperature is room temperature.
Since above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：
1. triscyclopentadienyl Lanthanide complex catalyst amount disclosed by the invention only needs the 0.01 ~ 1% of ketone mole；Reaction speed quickly, instead
Answering temperature is room temperature, and reaction can reach 99% or more yield for 60 minutes；It is catalyzed the reaction using triscyclopentadienyl lanthanum catalyst, was both dropped
Low catalyst amount, and yield is improved, the required reaction time is short, and reaction condition is mild, and product is easy to handle, and height accords with
Close the requirement of atom economy synthesis and green chemical reaction;
2. the present invention is for the first time with the hydroboration of triscyclopentadienyl rare earth metal complex catalysis ketone, the structure of catalyst is simple, is easy
Preparation, can efficiently be catalyzed such reaction;
3. triscyclopentadienyl rare earth metal complex disclosed by the invention is wide to the scope of application of substrate, suitable for different spaces steric hindrance, no
With the ketone of electronic effect, and reaction process is simply controllable, high income, and product postprocessing is easy, and is suitble to industrialized production, is boron
The industry of acid esters is combined to provide more more options.
Specific embodiment
Embodiment one:Y(Cp)3It is catalyzed acetophenone and pinacol borine synthesizes borate
Under atmosphere of inert gases, catalyst Y (Cp) is added in by dehydration and deoxidation treated reaction flask3 5.2 mg, add
Enter 3 ml of tetrahydrofuran, then takes 20.6 μ L with liquid-transfering gun（0.01mol%）It is added in another reaction flask, then be added with liquid-transfering gun
Pinacol borine (174 μ L, 1.2 mmol), then acetophenone (116.7 μ L, 1mmol) is added with liquid-transfering gun, it is reacting at room temperature
After 1h, a drop is drawn in nuclear magnetic tube with dropper, CDCl is added3Wiring solution-forming.It is computed1It is 98% that H, which composes yield,.The nuclear-magnetism of product
Data:1H NMR (400 MHz, CDCl3) δ 7.40 – 7.22 (m, 5H), 1.51 – 1.47 (d, J=6.5Hz,
3H), 1.24 (s, 6H), 1.21 (s, 6H)。
Embodiment two:Nd(Cp)3It is catalyzed acetophenone and pinacol borine synthesizes borate
Under atmosphere of inert gases, catalyst n d (Cp) is added in by dehydration and deoxidation treated reaction flask35.3 mg,
3 ml of tetrahydrofuran is added, then takes 23.3 μ L with liquid-transfering gun（0.01mol%）It is added in another reaction flask, then added with liquid-transfering gun
Enter pinacol borine (174 μ L, 1.2 mmol), then acetophenone (116.7 μ L, 1mmol) is added with liquid-transfering gun, it is anti-in room temperature
After answering 1h, a drop is drawn in nuclear magnetic tube with dropper, CDCl is added3Wiring solution-forming.It is computed1H composes yield and is greater than 99%.Product
Nuclear magnetic data is the same as embodiment one.
Embodiment three:Sm(Cp)3It is catalyzed acetophenone and pinacol borine synthesizes borate
Under atmosphere of inert gases, catalyst Sm (Cp) is added in by dehydration and deoxidation treated reaction flask32.1 mg,
2 ml of tetrahydrofuran is added, then takes 39.8 μ L with liquid-transfering gun（0.01mol%）It is added in another reaction flask, then added with liquid-transfering gun
Enter pinacol borine (174 μ L, 1.2 mmol), then acetophenone (116.7 μ L, 1mmol) is added with liquid-transfering gun, it is anti-in room temperature
After answering 1h, a drop is drawn in nuclear magnetic tube with dropper, CDCl is added3Wiring solution-forming.It is computed1It is 99% that H, which composes yield,.The core of product
Magnetic data is the same as embodiment one.
Example IV:La(Cp)3It is catalyzed acetophenone and pinacol borine synthesizes borate
Under atmosphere of inert gases, catalyst La (Cp) is added in by dehydration and deoxidation treated reaction flask32.8mg adds
Enter 2 ml of tetrahydrofuran, then takes 29 μ L with liquid-transfering gun（0.01mol%）It is added in another reaction flask, then frequency is added with liquid-transfering gun
Any alcohol borine (174 μ L, 1.2 mmol), then acetophenone (116.7 μ L, 1mmol) is added with liquid-transfering gun, in room temperature reaction 1h
Afterwards, a drop is drawn in nuclear magnetic tube with dropper, CDCl is added3Wiring solution-forming.It is computed1H composes yield and is greater than 99%.The nuclear-magnetism of product
Data consistent with Example one.
Embodiment five:Yb(Cp)3It is catalyzed acetophenone and pinacol borine synthesizes borate
Under atmosphere of inert gases, catalyst Yb (Cp) is added in by dehydration and deoxidation treated reaction flask34.3mg adds
Enter 3 ml of tetrahydrofuran, then takes 30.7 μ L with liquid-transfering gun（0.01mol%）It is added in another reaction flask, then be added with liquid-transfering gun
Pinacol borine (174 μ L, 1.2 mmol), then acetophenone (116.7 μ L, 1mmol) is added with liquid-transfering gun, it is reacting at room temperature
After 1h, a drop is drawn in nuclear magnetic tube with dropper, CDCl is added3Wiring solution-forming.It is computed1It is 97% that H, which composes yield,.The nuclear-magnetism of product
Data consistent with Example one.
Embodiment six: La(Cp)3Catalyzing iso-butane acyl benzene and pinacol borine synthesize borate
Under atmosphere of inert gases, catalyst La (Cp) is added in by dehydration and deoxidation treated reaction flask34.8mg adds
Enter 4 ml of tetrahydrofuran, then takes 33.8 μ L with liquid-transfering gun（0.01mol%）It is added in another reaction flask, then be added with liquid-transfering gun
Pinacol borine (174 μ L, 1.2 mmol), then isobutyrophenone (150 μ L, 1mmol) is added with liquid-transfering gun, it is reacting at room temperature
After 1h, a drop is drawn in nuclear magnetic tube with dropper, CDCl is added3Wiring solution-forming.It is computed1It is 99% that H, which composes yield,.The nuclear-magnetism of product
Number:1H NMR (400 MHz, CDCl3) δ 7.34 – 7.26 (m, 4H), 7.25 – 7.19 (m, 1H), 4.81
(d, J = 6.2 Hz, 1H), 1.96 (dq, J = 13.4, 6.7 Hz, 1H), 1.21 (s, 6H), 1.17 (s,
6H), 0.90 (d, J = 6.7 Hz, 3H), 0.83 (d, J = 6.8 Hz, 3H)。
Embodiment seven: La(Cp)3It is catalyzed acetanisole and pinacol borine synthesizes borate
Under atmosphere of inert gases, catalyst La (Cp) is added in by dehydration and deoxidation treated reaction flask34.8mg adds
Enter 4 ml of tetrahydrofuran, then takes 37.1 μ L with liquid-transfering gun（0.01mol%）It is added in another reaction flask, then be added with liquid-transfering gun
Pinacol borine (190.8 μ L, 1.3 mmol), then acetanisole (164.6mg, 1.1mmol) is weighed, in room temperature
After reacting 1h, a drop is drawn in nuclear magnetic tube with dropper, CDCl is added3Wiring solution-forming.It is computed1It is 99% that H, which composes yield,.Product
Nuclear-magnetism number:1H NMR (400 MHz, CDCl3) δ 7.38 – 7.17 (m, 2H), 6.94 – 6.68 (m, 2H),
5.20 (q, J = 6.4 Hz, 1H), 3.79 (s, 3H), 1.47 (d, J = 6.4 Hz, 3H), 1.24 (s,
6H), 1.22 (s, 6H)。
Embodiment eight: La(Cp)3Catalysis synthesizes borate to fluoro acetophenone and pinacol borine
Under atmosphere of inert gases, catalyst La (Cp) is added in by dehydration and deoxidation treated reaction flask37mg is added
Then 5 ml of tetrahydrofuran takes 29 μ L with liquid-transfering gun（0.01mol%）It is added in another reaction flask, then frequency is added where with liquid-transfering gun
Alcohol borine (174 μ L, 1.2 mmol), then isobutyrophenone (120.9 μ L, 1mmol) is added with liquid-transfering gun, in room temperature reaction 1h
Afterwards, a drop is drawn in nuclear magnetic tube with dropper, CDCl is added3Wiring solution-forming.It is computed1It is 99% that H, which composes yield,.The nuclear-magnetism of product
Number:1H NMR (400 MHz, CDCl3) δ 7.38 – 7.29 (m, 2H), 7.05 – 6.94 (m, 2H), 5.21
(q, J = 6.4 Hz, 1H), 1.47 (d, J = 6.4 Hz, 3H), 1.24 (s, 6H), 1.21 (s, 6H)。
Embodiment nine: La(Cp)3It is catalyzed melilotal and pinacol borine synthesizes borate
Under atmosphere of inert gases, catalyst La (Cp) is added in by dehydration and deoxidation treated reaction flask37mg is added
Then 5 ml of tetrahydrofuran takes 29 μ L with liquid-transfering gun（0.01mol%）It is added in another reaction flask, then frequency is added where with liquid-transfering gun
Alcohol borine (174 μ L, 1.2 mmol), then isobutyrophenone (133.5 μ L, 1mmol) is added with liquid-transfering gun, in room temperature reaction 1h
Afterwards, a drop is drawn in nuclear magnetic tube with dropper, CDCl is added3Wiring solution-forming.It is computed1H composes yield and is greater than 99%.The nuclear-magnetism of product
Number:1H NMR (400 MHz, CDCl3) δ 7.31 – 7.25 (m, 2H), 7.16 (t, J = 7.4 Hz, 2H),
5.24 (q, J = 6.4 Hz, 1H), 2.35 (s, 3H), 1.27 (s, 6H), 1.24 (s, 6H)。
Embodiment ten: La(Cp)3It is catalyzed 1-tetralone and pinacol borine synthesizes borate
Under atmosphere of inert gases, catalyst La (Cp) is added in by dehydration and deoxidation treated reaction flask37mg is added
Then 5 ml of tetrahydrofuran takes 29 μ L with liquid-transfering gun（0.01mol%）It is added in another reaction flask, then frequency is added where with liquid-transfering gun
Alcohol borine (174 μ L, 1.2 mmol), then 1-tetralone (132.8 μ L, 1mmol) is added with liquid-transfering gun, it is reacting at room temperature
After 1h, a drop is drawn in nuclear magnetic tube with dropper, CDCl is added3Wiring solution-forming.It is computed1H composes yield and is greater than 99%.The core of product
Magnetic number:1H NMR (400 MHz, CDCl3) δ 7.43 – 7.35 (m, 1H), 7.19 – 7.13 (m, 2H),
7.08 (m, 4.9 Hz, 1H), 2.94 – 2.58 (m, 2H), 2.14 – 1.99 (m, 1H), 2.00 – 1.90
(m, 2H), 1.82 – 1.67 (m, 1H), 1.31 (s, 6H), 1.29 (s, 6H)。
Embodiment 11: La(Cp)3It is catalyzed adjacent methyl ethyl ketone and pinacol borine synthesizes borate
Under atmosphere of inert gases, catalyst La (Cp) is added in by dehydration and deoxidation treated reaction flask33.9mg adds
Enter 3 ml of tetrahydrofuran, then takes 31.3 μ L with liquid-transfering gun（0.01mol%）It is added in another reaction flask, then be added with liquid-transfering gun
Pinacol borine (174 μ L, 1.2 mmol), then adjacent methyl ethyl ketone (130.8 μ L, 1mmol) is added with liquid-transfering gun, in room temperature
After reacting 1h, a drop is drawn in nuclear magnetic tube with dropper, CDCl is added3Wiring solution-forming.It is computed1It is 99% that H, which composes yield,.Product
Nuclear-magnetism number:1H NMR (400 MHz, CDCl3) δ 7.55 (m,1H), 7.33 – 7.08 (m, 3H), 5.45 (q,
J = 6.4 Hz, 1H), 1.48 (d, J = 6.4 Hz, 3H), 1.26 (s, 6H), 1.22 (s, 6H)。
Embodiment 12: La(Cp)3It is catalyzed 2,4,6- trimethylacetophenone and pinacol borine synthesizes borate
Under atmosphere of inert gases, catalyst La (Cp) is added in by dehydration and deoxidation treated reaction flask33.9mg adds
Enter 3 ml of tetrahydrofuran, then takes 31.3 μ L with liquid-transfering gun（0.01mol%）It is added in another reaction flask, then be added with liquid-transfering gun
Pinacol borine (174 μ L, 1.2 mmol), then with liquid-transfering gun be added 2,4,6- trimethylacetophenones (166.4 μ L,
1mmol), after reacting at room temperature 1h, a drop is drawn in nuclear magnetic tube with dropper, CDCl is added3Wiring solution-forming.It is computed1H spectrum produces
Rate is 99%.The nuclear-magnetism number of product:1H NMR (400 MHz, CDCl3) δ 6.79 (s, 2H), 5.65 (q, J = 6.8
Hz, 1H), 2.41 (s, 6H), 2.24 (s, 3H), 1.52 (d, J = 6.8 Hz, 3H), 1.21 (s, 6H),
1.17 (s, 6H)。
Embodiment 13: La(Cp)3It is catalyzed parabromoacetophenone and pinacol borine synthesizes borate
Under atmosphere of inert gases, catalyst La (Cp) is added in by dehydration and deoxidation treated reaction flask33.9mg adds
Enter 3 ml of tetrahydrofuran, then takes 38 μ L with liquid-transfering gun（0.01mol%）It is added in another reaction flask, then frequency is added with liquid-transfering gun
Any alcohol borine (211.5 μ L, 1.4 mmol), then parabromoacetophenone (241.8mg, 1.2mmol) is weighed, in room temperature reaction 1h
Afterwards, a drop is drawn in nuclear magnetic tube with dropper, CDCl is added3Wiring solution-forming.It is computed1It is 98% that H, which composes yield,.The nuclear-magnetism of product
Number:1H NMR (400 MHz, CDCl3) δ 7.41 (m, 2H), 7.21 (m, 2H), 5.16 (q, J = 6.4
Hz, 1H), 1.42 (d, J = 6.5 Hz, 3H), 1.20 (s, 6H), 1.18 (s, 6H)。
Embodiment 14: La(Cp)3It is catalyzed p-nitroacetophenone and pinacol borine synthesizes borate
Under atmosphere of inert gases, catalyst La (Cp) is added in by dehydration and deoxidation treated reaction flask33.9mg adds
Enter 3 ml of tetrahydrofuran, then takes 31.8 μ L with liquid-transfering gun（0.01mol%）It is added in another reaction flask, then be added with liquid-transfering gun
Pinacol borine (177 μ L, 1.2 mmol), then p-nitroacetophenone (167.9mg, 1mmol) is weighed, in room temperature reaction 2h
Afterwards, a drop is drawn in nuclear magnetic tube with dropper, CDCl is added3Wiring solution-forming.It is computed1It is 98% that H, which composes yield,.The nuclear-magnetism of product
Number:1H NMR (400 MHz, CDCl3) δ 8.16 – 8.08 (m, 2H), 7.47 (m, 2H), 5.26 (q, J =
6.5 Hz, 1H), 1.44 (d, J = 6.5 Hz, 3H), 1.19 (s, 6H), 1.16 (s, 6H)。
Embodiment 15: La(Cp)3It is catalyzed 1- (2- thienyl) ethyl ketone and pinacol borine synthesizes borate
Under atmosphere of inert gases, catalyst La (Cp) is added in by dehydration and deoxidation treated reaction flask318.5mg,
1.6 ml of tetrahydrofuran is added, then takes 353 μ L (1mol%) to be added in another reaction flask with liquid-transfering gun, then be added with liquid-transfering gun
Pinacol borine (174.1 μ L, 1.2 mmol), then with liquid-transfering gun be added 1- (2- thienyl) ethyl ketone (108 μ L, 1
Mmol), after reacting at room temperature 1h, a drop is drawn in nuclear magnetic tube with dropper, CDCl is added3Wiring solution-forming.It is computed1H composes yield
It is 99%.The nuclear-magnetism number of product:1H NMR (400 MHz, CDCl3) δ 7.21 – 7.19 (m, 1H), 6.97 –
6.92 (m, 2H), 5.48 (q, J = 6.4 Hz, 1H), 1.60 (d, J = 6.4 Hz, 3H), 1.25 (d, J
= 4.9 Hz, 12H)。
Embodiment 16: La(Cp)3It is catalyzed cyclododecanone and pinacol borine synthesizes borate
Under atmosphere of inert gases, catalyst La (Cp) is added in by dehydration and deoxidation treated reaction flask318.5mg,
1.6 ml of tetrahydrofuran is added, then takes 340.8 μ L (1mol%) to be added in another reaction flask with liquid-transfering gun, then added with liquid-transfering gun
Enter pinacol borine (168.8 μ L, 1.16 mmol), then weighs cyclododecanone (168.8 mg, 0.97mmol), it is anti-in room temperature
After answering 1h, a drop is drawn in nuclear magnetic tube with dropper, CDCl is added3Wiring solution-forming.It is computed1It is 100% that H, which composes yield,；Catalyst
It is 99% for 0.01 mol % yield.The nuclear-magnetism number of product:1H NMR (400 MHz, CDCl3) δ 4.11 (dt, J =
31.5, 15.5 Hz, 1H), 1.66 – 1.53 (m, 2H), 1.32 (m, 22H), 1.17 (s, 12H)。
Embodiment 17: La(Cp)3It is catalyzed dibenzyl ketone and pinacol borine synthesizes borate
Under atmosphere of inert gases, catalyst La (Cp) is added in by dehydration and deoxidation treated reaction flask318.5mg,
1.6 ml of tetrahydrofuran is added, then takes 286 μ L (1mol%) to be added in another reaction flask with liquid-transfering gun, then be added with liquid-transfering gun
Pinacol borine (142.2 μ L, 0.98 mmol), then dibenzyl ketone (171.7 mg, 0.82mmol) are weighed, it is reacting at room temperature
After 1h, a drop is drawn in nuclear magnetic tube with dropper, CDCl is added3Wiring solution-forming.It is computed1It is 100% that H, which composes yield,；Catalyst is
0.01 mol % yield is 99%.The nuclear-magnetism number of product:1H NMR (400 MHz, CDCl3) δ 7.26 – 7.12 (m,
10H), 4.42 (dt, J = 8.7, 4.5 Hz, 1H), 2.78 (m, 4H), 0.90 (s, 12H)。
Claims (4)
1. application of the triscyclopentadienyl rare earth metal complex as catalyst in catalysis ketone and pinacol borine synthetic reaction；Described three
The chemical structural formula of cyclopentadienyl rare-earth metal complex is as follows：
。
2. application according to claim 1, which is characterized in that the Ln indicates rare earth metal, in lanthanide series
One of lanthanum, yttrium；The borine is pinacol borine；The ketone is aromatic ketone or fatty cyclic ketones；The change of the aromatic ketone
Learn one of for example following structural formula of structural formula：
、、, wherein R is phenyl, substituted-phenyl or heterocycle virtue
Base；One of for example following structural formula of chemical structural formula of the fat cyclic ketones：
、, wherein n is 3~15.
3. application according to claim 1, which is characterized in that the dosage of the triscyclopentadienyl rare earth metal complex is rubbing for ketone
The 0.01~1% of that amount；The dosage of the borine and the molar ratio of ketone are 1~1.2: 1；The synthesising reacting time be 30min~
1h, temperature are room temperature.
4. application of the triscyclopentadienyl rare earth metal complex as catalyst in synthesis borate；The triscyclopentadienyl rare earth metal complex
Chemical structural formula it is as follows：
。
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