CN110256474A - Application of the three silicon amine rare earth compoundings in catalysis carbonic ester and borine reaction - Google Patents
Application of the three silicon amine rare earth compoundings in catalysis carbonic ester and borine reaction Download PDFInfo
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- borine
- ester
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- carbonic
- carbonic ester
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- 229910000085 borane Inorganic materials 0.000 title claims abstract description 53
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 44
- -1 silicon amine rare earth Chemical class 0.000 title claims abstract description 42
- 150000002148 esters Chemical class 0.000 title claims abstract description 34
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 28
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 24
- 239000010703 silicon Substances 0.000 title claims abstract description 24
- 238000013329 compounding Methods 0.000 title claims abstract description 21
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 9
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims abstract description 60
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 9
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 8
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 6
- QUWGNYVHIGWIKU-UHFFFAOYSA-N carbonic acid;styrene Chemical class OC(O)=O.C=CC1=CC=CC=C1 QUWGNYVHIGWIKU-UHFFFAOYSA-N 0.000 claims description 5
- 125000006182 dimethyl benzyl group Chemical group 0.000 claims description 5
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 4
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 3
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- HMWVNKJRYWXJGS-UHFFFAOYSA-N C(C)(=O)OC=C.[C] Chemical group C(C)(=O)OC=C.[C] HMWVNKJRYWXJGS-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 27
- 238000006197 hydroboration reaction Methods 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 18
- 230000018044 dehydration Effects 0.000 description 14
- 238000006297 dehydration reaction Methods 0.000 description 14
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- 229960002645 boric acid Drugs 0.000 description 4
- 235000010338 boric acid Nutrition 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 230000005311 nuclear magnetism Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000007866 anti-wear additive Substances 0.000 description 1
- 239000013556 antirust agent Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 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
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
-
- 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)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses application of the three silicon amine rare earth compoundings in catalysis carbonic ester and borine reaction, include the following steps, under nitrogen atmosphere, in the presence of three silicon amine rare earth compoundings, by borine and carbonate reaction, obtain borate.The present invention is for the first time with the hydroboration of catalyzed by rare-earth complex carbonic ester and pinacol borine, to develop the catalyst of a kind of new and effective catalysis hydroboration, its structure is simple, synthesis is easy, the application of three silicon amine rare earth compoundings is not only expanded, the method for the synthetic reaction of richer carbonic ester and pinacol borine.
Description
Technical field
The present invention relates to a kind of application fields of organolanthanide complexes, and in particular to three silicon amine rare earth compoundings exist
The application being catalyzed in the hydroboration of carbonic ester and borine.
Background technique
Organic boric acid ester is considered as orthoboric acid B (OH)3In hydrogen replaced by organic group after derivative, in addition there are
Metaboric acid ester (ROBO)3.The application range of boric acid ester compound is very extensive, it is a kind of main of synthesis boron-containing compound
Raw material, this is one of its important use.Furthermore boric acid ester compound acts not only as the antirust agent of cleaning agent, anti-corrosion
Agent, polymeric additive, antiwear additive, motor vehicle brake fluid, gasoline additive, fire retardant use, and may be used as lubricating
Oil additive etc..
Since initiative research has been carried out to borine from Stock in 1912 et al., the short of electricity sub-feature of borine and right
The probing into of its Nature of bonding attracts people's note that research of borine has become an important research of chemistry subject always
Field.Boron alkyl acid esters becomes the hot research field of organoboron compound in recent years, as hydrogen storage material and organic anti-
Go back original reagent is used as in answering, the reverse side such as chiral catalysis reagent have obtained extensive research and application.Existing catalyst system used
Crossing manganic complexes is catalyst, NaOtBu is co-catalyst, and higher temperature is needed just to realize the efficient progress of reaction.
Summary of the invention
Goal of the invention of the invention is to provide the application of three silicon amine rare earth compoundings, can be catalyzed carbonic ester and pinacol
Borine prepares borate, while having high catalytic activity, low catalyst amount, has good substrate to try out range.
In order to achieve the above objectives, the technical solution adopted by the present invention is that: three silicon amine rare earth compoundings catalysis carbonic ester and
Application in borine reaction；The chemical structural formula of the three silicon amine rare earth compounding is as follows:
A method of borate is prepared, is included the following steps, it, will in the presence of three silicon amine rare earth compoundings under nitrogen atmosphere
Borine and carbonate reaction, obtain borate.
The molecular formula of above-mentioned three silicon amine rare earth compounding may be expressed as: RE [N (SiMe3)2]3, RE expression rare earth metal, choosing
From lanthanum, yttrium, neodymium, ytterbium, one of the samarium in lanthanide series.
In above-mentioned technical proposal, the borine is pinacol borine；The carbonic ester is ethylene carbonate, propylene carbonate
Ester, carbonic acid styrene esters, carbonic acid chlorostyrene ester, carbonic acid t-butyl styrene ester, dimethyl carbonate, dimethyl benzyl, Sanya
Methyl carbonic etc.；Or the chemical structural formula of carbonic ester is as follows:
In above-mentioned technical proposal, the dosage of the three silicon amine rare earth compounding is 0.5 % of carbonic ester mole；The borine,
The molar ratio of carbonic ester is 3.3:1.
In above-mentioned technical proposal, the temperature of the reaction is room temperature.
Specific steps of the three silicon amine rare earth compounding disclosed by the invention as catalyst preparation borate are as follows:
All raw materials pass through the processing of anhydrous and oxygen-free, and under nitrogen atmosphere, catalyst, borine and carbonic ester are mixed；Then room temperature
6h is reacted, then ingress of air terminates reaction, obtains different substituted borates.
Above-mentioned technical proposal can be expressed as follows:
Due to the above technical solutions, the present invention has the following advantages over the prior art:
1. the present invention is for the first time with the hydroboration of catalyzed by rare-earth complex carbonic ester and pinacol borine, to develop one kind
The catalyst of new and effective catalysis hydroboration, structure is simple, and synthesis is easy, and has not only expanded the cooperation of three silicon amine rare earths
The method of the synthetic reaction of the application of object, richer carbonic ester and pinacol borine.
2. three silicon amine rare earth compounding disclosed by the invention can high activity at room temperature catalysis carbonic ester and boron
The hydroboration of alkane, catalyst amount are only 0.5 % of carbonic ester mole, and reaction can reach 99% or more yield, and
Some catalyst systems are compared, and both reduce catalyst amount, and improve yield.
Three silicon amine rare earth compounding disclosed by the invention is wide to the scope of application of substrate, be suitable for different substituents position,
The carbonic ester of different electronic effects is combined to provide more more options for the industry of borate；And reaction process is simply controllable,
High income, product postprocessing are easy, and are suitble to industrialized production.
Specific embodiment
The present invention will be further described below with reference to examples:
[N (the SiMe of embodiment one: La3)2]3It is catalyzed ethylene carbonate and pinacol borine synthesizes borate
Under nitrogen atmosphere, catalyst La [N (SiMe is added in by dehydration and deoxidation treated reaction flask3)2]3 ( 3.1
Mg, 0.005mmol), ethylene carbonate (66.6 μ L., 1 mmol) is added with liquid-transfering gun, then frequency is added where with liquid-transfering gun again
Alcohol borine (435.9 μ L, 3 mmol), after reacting at room temperature 6h, ingress of air terminates reaction, draws a drop in core with dropper
In magnetic tube, CDCl is added3Wiring solution-forming.It is computed1It is 70 % that H, which composes yield,.The nuclear magnetic data of product:1H NMR (400 MHz,
CDCl3) δ 3.94 (s, 4H, CH2), 3.60 (s, 3H, CH3OBpin), 1.25 (d, 40H, CH3)。
[N (the SiMe of embodiment two: Yb3)2]3It is catalyzed ethylene carbonate and pinacol borine synthesizes borate
Under nitrogen atmosphere, catalyst Yb [N (SiMe is added in by dehydration and deoxidation treated reaction flask3)2]3 (3.3
Mg, 0.005mmol), ethylene carbonate (66.6 μ L, 1mmol) is added with liquid-transfering gun, pinacol then is added with liquid-transfering gun again
Borine (478.8 μ L, 3.3 mmol), after reacting at room temperature 6h, ingress of air terminates reaction, draws a drop in core with dropper
In magnetic tube, CDCl is added3Wiring solution-forming.It is computed1It is 30 % that H, which composes yield,.The nuclear magnetic data of product is the same as embodiment one.
[N (the SiMe of embodiment three: Nd3)2]3It is catalyzed ethylene carbonate and pinacol borine synthesizes borate
Under nitrogen atmosphere, catalyst n d [N (SiMe is added in by dehydration and deoxidation treated reaction flask3)2]3 (3.2
Mg, 0.005mmol), ethylene carbonate (66.6 μ L, 1mmol) is added with liquid-transfering gun, pinacol then is added with liquid-transfering gun again
Borine (478.8 μ L, 3.3 mmol), after reacting at room temperature 6h, ingress of air terminates reaction, draws a drop in nuclear-magnetism with dropper
CDCl is added in Guan Zhong3Wiring solution-forming.It is computed1It is 94 % that H, which composes yield,.The nuclear magnetic data of product is the same as embodiment one.
Example IV: La [N (SiMe3)2]3It is catalyzed ethylene carbonate and pinacol borine synthesizes borate
Under nitrogen atmosphere, catalyst La [N (SiMe is added in by dehydration and deoxidation treated reaction flask3)2]3 ( 3.1
Mg, 0.005mmol), ethylene carbonate (66.6 μ L, 1mmol) is added with liquid-transfering gun, then frequency is added where with liquid-transfering gun again
Alcohol borine (478.8 μ L, 3.3 mmol), after reacting at room temperature 6h, ingress of air terminate reaction, with dropper draw one drop in
In nuclear magnetic tube, CDCl is added3Wiring solution-forming.It is computed1It is 99 % that H, which composes yield,.The nuclear magnetic data of product is the same as embodiment one.
[N (the SiMe of embodiment five: La3)2]3It is catalyzed propene carbonate and pinacol borine synthesizes borate
Under nitrogen atmosphere, catalyst La [N (SiMe is added in by dehydration and deoxidation treated reaction flask3)2]3 ( 3.1
Mg, 0.005mmol), propene carbonate (84.8 μ L, 1mmol) is added with liquid-transfering gun, then frequency is added where with liquid-transfering gun again
Alcohol borine (478.8 μ L, 3.3 mmol), after reacting at room temperature 6h, ingress of air terminate reaction, with dropper draw one drop in
In nuclear magnetic tube, CDCl is added3Wiring solution-forming.It is computed1It is 97 % that H, which composes yield,.The nuclear magnetic data of product:1H NMR (400
MHz, CDCl3) δ4.30-4.26 (m, 1H, CH), 3.75 (d, 2H, CH2), 3.60 (s, 3H, CH3OBpin),
1.24 (s, 40H, OBpin), 1.17 (d, 3H, CH3)。
[N (the SiMe of embodiment six: La3)2]3It is catalyzed carbonic acid styrene esters and pinacol borine synthesizes borate
Under nitrogen atmosphere, catalyst La [N (SiMe is added in by dehydration and deoxidation treated reaction flask3)2]3 ( 3.1
Mg, 0.005mmol), it is added carbonic acid styrene esters (164.2 mg, 1mmol), pinacol boron then is added with liquid-transfering gun again
Alkane (478.8 μ L, 3.3 mmol), after reacting at room temperature 6h, ingress of air terminates reaction, draws a drop in nuclear-magnetism with dropper
CDCl is added in Guan Zhong3Wiring solution-forming.It is computed1It is 99 % that H, which composes yield,.The nuclear magnetic data of product:1H NMR (400 MHz,
CDCl3) δ 7.31-7.16 (m, 5H, ArCH), 5.17-5.14 (m, 1H, CH), 3.90-3.80 (m, 2H,
CH2), 3.51 (s, 3H, CH3OBpin), 1.15 (d, 40H, OBpin)。
[N (the SiMe of embodiment seven: La3)2]3It is catalyzed carbonic acid chlorostyrene ester and pinacol borine synthesizes borate
The chemical structural formula of carbonic acid chlorostyrene ester is as follows:
Under nitrogen atmosphere, catalyst La [N (SiMe is added in by dehydration and deoxidation treated reaction flask3)2]3 ( 3.1
Mg, 0.005mmol), it is added carbonic acid chlorostyrene ester (198.6 mg, 1mmol), pinacol then is added with liquid-transfering gun again
Borine (478.8 μ L, 3.3 mmol), after reacting at room temperature 6h, ingress of air terminates reaction, draws a drop in core with dropper
In magnetic tube, CDCl is added3Wiring solution-forming.It is computed1It is 94 % that H, which composes yield,.The nuclear magnetic data of product:1H NMR (400 MHz,
CDCl3) δ 7.28-7.20 (m, 4H, ArCH), 5.12-5.09 (m, 1H, CH), 3.87-3.80 (m, 2H,
CH2), 3.55 (s, 3H, CH3OBpin), 1.21-1.15 (m, 40H, OBpin)。
[N (the SiMe of embodiment eight: La3)2]3It is catalyzed carbonic acid t-butyl styrene ester and pinacol borine synthesizes borate
The chemical structural formula of carbonic acid t-butyl styrene ester is as follows:
Under nitrogen atmosphere, catalyst La [N (SiMe is added in by dehydration and deoxidation treated reaction flask3)2]3 ( 3.1
Mg, 0.005mmol), it is added carbonic acid t-butyl styrene ester (220.27 mg, 1mmol), frequency then is added with liquid-transfering gun again
Which alcohol borine (478.8 μ L, 3.3 mmol), after reacting at room temperature 6h, ingress of air terminates reaction, draws a drop with dropper
In nuclear magnetic tube, CDCl is added3Wiring solution-forming.It is computed1It is 99 % that H, which composes yield,.The nuclear magnetic data of product:1H NMR (400
MHz, CDCl3) δ 7.28-7.23 (m, 4H, ArCH), 5.16-5.12 (m, 1H, CH), 3.90-3.80 (m,
2H, CH2), 3.52 (s, 3H, CH3OBpin), 1.23 (s, 9H, C(CH3)3), 1.18-1.13 (m, 40H,
OBpin)。
[N (the SiMe of embodiment nine: La3)2]3It is catalyzed trimethylene carbonate and pinacol borine synthesizes borate
Under nitrogen atmosphere, catalyst La [N (SiMe is added in by dehydration and deoxidation treated reaction flask3)2]3 ( 3.1
Mg, 0.005mmol), it is added trimethylene carbonate (102.09 mg, 1mmol), pinacol then is added with liquid-transfering gun again
Borine (478.8 μ L, 3.3 mmol) draws a drop in nuclear magnetic tube with dropper, CDCl is added after reacting at room temperature 6h3Match
At solution.It is computed1It is 99 % that H, which composes yield,.The nuclear magnetic data of product:1H NMR (400 MHz, CDCl3) δ 3.95-
3.92 (m, 4H, CH2), 3.60 (s, 3H, CH3OBpin), 1.87-1.80 (q, 4H, CH2), 1.26-1.24
(m, 40H, OBpin)。
[N (the SiMe of embodiment ten: La3)2]3It is catalyzed carbonic ester and pinacol borine synthesizes borate
The chemical structural formula of carbonic ester is as follows:
Under nitrogen atmosphere, catalyst La [N (SiMe is added in by dehydration and deoxidation treated reaction flask3)2]3 ( 3.1
Mg, 0.005mmol), carbonic ester (157.6 μ L, 1mmol) is added with liquid-transfering gun, pinacol then is added with liquid-transfering gun again
Borine (478.8 μ L, 3.3 mmol) draws a drop in nuclear magnetic tube with dropper, CDCl is added after reacting at room temperature 6h3Match
At solution.It is computed1It is 95 % that H, which composes yield,.The nuclear magnetic data of product:1H NMR (400 MHz, CDCl3) δ 3.61 (d,
4H, CH2), 3.55 (s, 3H, CH3OBpin), 1.21-1.19 (m, 44H, OBpin & (CH2)2), 0.85-
0.78 (m, 6H, CH3)。
[N (the SiMe of embodiment 11: La3)2]3It is catalyzed dimethyl benzyl and pinacol borine synthesizes borate
Under nitrogen atmosphere, catalyst La [N (SiMe is added in by dehydration and deoxidation treated reaction flask3)2]3 ( 3.1
Mg, 0.005mmol), dimethyl benzyl (210.4 μ L, 1mmol) is added with liquid-transfering gun, then frequency is added where with liquid-transfering gun again
Alcohol borine (478.8 μ L, 3.3 mmol), after reacting at room temperature 6h, ingress of air terminate reaction, with dropper draw one drop in
In nuclear magnetic tube, CDCl is added3Wiring solution-forming.It is computed1It is 99 % that H, which composes yield,.The nuclear magnetic data of product:1H NMR (400
MHz, CDCl3) δ7.35-7.23 (m, 10H, ArCH), 4.92 (s, 4H, CH2), 3.60 (s, 3H,
CH3OBpin), 1.25 (d, 40H, OBpin)。
12 Cp of embodiment3Nd is catalyzed dimethyl carbonate and pinacol borine synthesizes borate
Under nitrogen atmosphere, catalyst Cp is added in by dehydration and deoxidation treated reaction flask3Nd (1.7 mg,
0.005mmol), dimethyl carbonate (84.2 μ L, 1mmol) is added with liquid-transfering gun, pinacol borine then is added with liquid-transfering gun again
(478.8 μ L, 3.3 mmol), after reacting at room temperature 6h, ingress of air terminates reaction, draws a drop in nuclear magnetic tube with dropper
In, CDCl is added3Wiring solution-forming.It is computed, raw material does not react.
13 Cp of embodiment3Nd is catalyzed ethylene carbonate and pinacol borine synthesizes borate
Under nitrogen atmosphere, catalyst Cp is added in by dehydration and deoxidation treated reaction flask3Nd (1.7 mg,
0.005mmol), ethylene carbonate (66.6 μ L, 1mmol) is added with liquid-transfering gun, pinacol boron then is added with liquid-transfering gun again
Alkane (478.8 μ L, 3.3 mmol), after reacting at room temperature 6h, ingress of air terminates reaction, draws a drop in nuclear-magnetism with dropper
CDCl is added in Guan Zhong3Wiring solution-forming.It is computed, raw material does not react.
The hydroboration of carbonic ester cannot be catalyzed by illustrating the triscyclopentadienyl rare earth catalyst under present circumstances.
[N (the SiMe of embodiment 14: La3)2]3It is catalyzed dimethyl carbonate and pinacol borine synthesizes borate
Under nitrogen atmosphere, catalyst La [N (SiMe is added in by dehydration and deoxidation treated reaction flask3)2]3 ( 3.1
Mg, 0.005mmol), dimethyl carbonate (84.2 μ L, 1mmol) is added with liquid-transfering gun, then frequency is added where with liquid-transfering gun again
Alcohol borine (478.8 μ L, 3.3 mmol), after reacting at room temperature 6h, ingress of air terminate reaction, with dropper draw one drop in
In nuclear magnetic tube, CDCl is added3Wiring solution-forming.It is computed1It is 99 % that H, which composes yield,.The nuclear magnetic data of product:1H NMR (400
MHz, CDCl3) δ 3.53 (s, 9H, CH3OBpin), 1.18 (s, 40H, OBpin)。
Three silicon amine organolanthanide complexes of the invention, have many advantages, such as to be easily-synthesized, at low cost, the cooperation of silicon amine rare earth
There are Ln-N keys for object, use lower catalyst amount, mild reaction condition, under conditions of being not necessarily to solvent as catalyst
The hydroboration that carbonic ester can be efficiently catalyzed should generate boron alkyl acid esters.
Claims (10)
1. application of the three silicon amine rare earth compoundings in catalysis carbonic ester and borine reaction；The change of the three silicon amine rare earth compounding
It is as follows to learn structural formula:
Wherein, RE indicates rare earth metal.
2. application according to claim 1, which is characterized in that RE is selected from one of lanthanum, yttrium, neodymium, ytterbium, samarium.
3. application according to claim 1, which is characterized in that the borine is pinacol borine；The carbonic ester is carbon
Vinyl acetate, propene carbonate, carbonic acid styrene esters, carbonic acid chlorostyrene ester, carbonic acid t-butyl styrene ester, carbonic acid diformazan
Ester, dimethyl benzyl, trimethylene carbonate；Or the chemical structural formula of carbonic ester is as follows:
。
4. application according to claim 1, which is characterized in that the dosage of the three silicon amine rare earth compounding is rubbed for carbonic ester
0.5 % of your amount；The borine, carbonic ester molar ratio be 3.3:1.
5. application according to claim 1, which is characterized in that the temperature of the reaction is room temperature, and the time is 6 hours.
6. a kind of method for preparing borate, includes the following steps, under nitrogen atmosphere, in the presence of three silicon amine rare earth compoundings,
By borine and carbonate reaction, borate is obtained；The chemical structural formula of the three silicon amine rare earth compounding is as follows:
Wherein, RE indicates rare earth metal.
7. preparing the method for borate according to claim 6, which is characterized in that RE in lanthanum, yttrium, neodymium, ytterbium, samarium one
Kind.
8. preparing the method for borate according to claim 6, which is characterized in that the borine is pinacol borine；It is described
Carbonic ester be ethylene carbonate, propene carbonate, carbonic acid styrene esters, carbonic acid chlorostyrene ester, carbonic acid t-butyl styrene ester,
Dimethyl carbonate, dimethyl benzyl, trimethylene carbonate；Or the chemical structural formula of carbonic ester is as follows:
。
9. preparing the method for borate according to claim 6, which is characterized in that the use of the three silicon amine rare earth compounding
Amount is 0.5 % of carbonic ester mole；The borine, carbonic ester molar ratio be 3.3:1.
10. preparing the method for borate according to claim 6, which is characterized in that the temperature of the reaction is room temperature, time
It is 6 hours.
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| CN106188118A (en) * | 2016-06-30 | 2016-12-07 | 苏州大学 | The application in the hydroboration of catalysis ketone and borine of the three silicon amine rare earth compoundings |
| CN110003261A (en) * | 2019-04-15 | 2019-07-12 | 南京林业大学 | A kind of Hydroboronation process of organic carbon hydrochlorate |
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| CN110003261A (en) * | 2019-04-15 | 2019-07-12 | 南京林业大学 | A kind of Hydroboronation process of organic carbon hydrochlorate |
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| WO2021253868A1 (en) * | 2020-06-16 | 2021-12-23 | 苏州大学 | Method for hydroboration of carbonate |
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