CN108948058B - Application of rare earth metal complexes of tricyclocene as catalyst in catalyzing aldehyde and pinacol borane synthesis reaction - Google Patents
Application of rare earth metal complexes of tricyclocene as catalyst in catalyzing aldehyde and pinacol borane synthesis reaction Download PDFInfo
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- 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 System
- C07F5/02—Boron compounds
- C07F5/04—Esters of boric acids
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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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Abstract
The invention discloses an application of a rare earth metallocene complex as a catalyst in catalyzing aldehyde and pinacol borane synthesis reaction, which comprises the following steps of stirring and mixing the catalyst, borane and aldehyde uniformly to prepare boric acid ester through reaction, wherein the molecular formula of the rare earth metallocene complex can be represented as L n (Cp)3L n represents rare earth metal selected from one of lanthanide, the preparation method has higher catalytic activity, mild reaction condition, easy product post-treatment, short reaction time, low catalyst consumption, good substrate application range and industrial production.
Description
The invention belongs to a method for preparing boric acid ester based on a rare earth metal metallocene complex, which is a divisional application with the application number of 201710162142.1 and the application date of 2017, 3, month and 17, and belongs to the technical part of an application method.
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to application of a rare earth metal metallocene serving as a catalyst in catalyzing aldehyde and pinacol borane synthesis reaction.
Background
The borate compounds have wide application range, can be used as polymer additives, gasoline additives, sterilizing agents and flame retardants, and can also be used as lubricating oil additives and automobile brake fluid. Meanwhile, boric acid or boric acid ester can be converted into other multiple functional groups, which is an important reagent in organic synthesis, and is gradually and deeply researched as a chiral medicament, and the chiral boric acid is used as a medicinal structural unit to synthesize bortezomib which is the first approved protease inhibitor medicament for treating multiple myeloma and lymphoma, so that the application prospect of the chiral boric acid or boric acid ester is very wide. The addition reaction of carbonyl compounds and boranes is the most direct and most atom-economical method for synthesizing borate esters containing different substituents. However, studies have shown that without a catalyst, some boranes (such as pinacolborane) are difficult to hydroborate, possibly due to too low a lewis acidity of such boranes. In the existing catalytic system, the catalyst consumption is large, the reaction time is long, and the substrate universality is low.
For example, in the case of doping europium complexes in a conductive polymer CN-PPP, the energy transfer efficiency of β -diketone europium complexes of symmetric and asymmetric phenanthrene is only 0.053%, which is far lower than that of β -diketone europium complexes of symmetric biphenyl by 1.1%.
Disclosure of Invention
The invention aims to provide a method for preparing borate based on a rare earth metallocene complex, which is used for catalyzing aldehyde compounds and pinacol borane to prepare borate through the application of the rare earth metallocene complex.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for preparing boric acid ester based on a rare earth metal cyclopentadienyl complex comprises the following steps of uniformly stirring and mixing a catalyst, borane and aldehyde, and reacting to prepare boric acid ester; the catalyst is a rare earth metal metallocene complex; the chemical structural formula of the rare earth metal tricyclene complex is as follows:
in the technical scheme, the borane is pinacol borane; the chemical structural formula of the aldehyde is
、
、
、
Wherein R is selected from: hydrogen, halogen, methyl or methoxy.
In the technical scheme, the dosage of the metallocene rare earth metal complex is 0.01-1% of the molar weight of aldehyde; the molar ratio of the used amount of the borane to the aldehyde is 1-1.2: 1; the reaction time is 30 min-1 h; the reaction temperature was room temperature.
In the above technical scheme, the reaction is carried out in an organic solvent, preferably tetrahydrofuran.
In the technical scheme, after the reaction is finished, the solvent is removed from the reaction liquid under reduced pressure, and n-hexane is added into the residual liquid to obtain different substituted boric acid esters.
The invention also discloses the application of the rare earth metal complexes of the metallocene as a catalyst in catalyzing the synthesis reaction of aldehyde and pinacol borane; the chemical structural formula of the rare earth metal tricyclene complex is as follows:
the molecular formula of the above-mentioned metallocene rare earth metal complex can be represented by L n (Cp)3L n represents a rare earth metal selected fromLanthanum, yttrium, neodymium, ytterbium and samarium in lanthanide series elements.
In the technical scheme, the borane is pinacol borane; the chemical structural formula of the aldehyde is
、
、
、
Wherein R is selected from: hydrogen, halogen, methyl or methoxy.
In the technical scheme, the dosage of the metallocene rare earth metal complex is 0.01-1% of the molar weight of aldehyde; the molar ratio of the used amount of the borane to the aldehyde is 1-1.2: 1; the reaction time is 30 min-1 h.
The rare earth metallocene complex can catalyze hydroboration reduction reaction of aldehyde and pinacol borane to prepare boric acid ester, so the invention requests to protect the application of the rare earth metallocene complex as a catalyst in synthesizing boric acid ester.
In the technical scheme, the reaction temperature is room temperature.
The above technical solution can be expressed as follows:
R1are substituents obtained according to the above.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. the dosage of the lanthanum trimaran complex catalyst disclosed by the invention only needs 0.01-1% of the molar weight of aldehyde; the reaction speed is high, the reaction temperature is room temperature, and the yield of the reaction can reach more than 95 percent after 30 minutes of reaction; the lanthanum chloride catalyst is used for catalyzing the reaction, so that the using amount of the catalyst is reduced, the yield is improved, the required reaction time is short, the reaction condition is mild, the product is easy to treat, and the requirements of atom economic synthesis and green chemical reaction are highly met;
2. the invention uses the rare earth metal complexes of the metallocene to catalyze the hydroboration reaction of aldehyde for the first time, and the catalyst has simple structure, is easy to prepare and can catalyze the reaction with high efficiency;
3. the rare earth metal tricyclene complex disclosed by the invention has a wide application range on a substrate, is suitable for aldehydes with different steric hindrance and different electronic effects, is simple and controllable in reaction process, high in yield, easy in product post-treatment, and suitable for industrial production, and provides more choices for industrial synthesis of boric acid ester.
Detailed Description
Example one Y (Cp)3Synthesis of boric acid ester by catalyzing benzaldehyde and pinacol borane
Adding catalyst Y (Cp) into a reaction bottle subjected to dehydration and deoxidation treatment under an inert gas atmosphere3(1mol%) tetrahydrofuran solution, then pinacolborane (145.1. mu. L, 1mmol) was added using a pipette, benzaldehyde (101.1. mu. L, 1mmol) was added using a pipette, and after reaction at room temperature for 30min, CDCl was added3Preparing a solution. Is calculated by1The yield of the H spectrum is 98%. Nuclear magnetic data for the product 1H NMR (400 MHz, CDCl3) 7.37-7.31 (m, 4H), 7.27(dt, J = 6.1, 3.3 Hz, 1H), 4.94 (s, 2H), 1.27 (s, 12H).
Example two Y (Cp)3Synthesis of boric acid ester by catalyzing benzaldehyde and pinacol borane
Adding catalyst Y (Cp) into a reaction bottle subjected to dehydration and deoxidation treatment under an inert gas atmosphere3(0.2mol%) tetrahydrofuran solution, then pinacolborane (145.1. mu. L, 1mmol) was added with a pipette, benzaldehyde (101.1. mu. L, 1mmol) was added with a pipette, and after reaction at room temperature for 30min, CDCl was added3Preparing a solution. Is calculated by1The yield of H spectrum is 97%, and the nuclear magnetic data of the product is the same as that of the first example.
EXAMPLE III Y (Cp)3Synthesis of boric acid ester by catalyzing benzaldehyde and pinacol borane
Adding catalyst Y (Cp) into a reaction bottle subjected to dehydration and deoxidation treatment under an inert gas atmosphere3(0.1mol%) tetrahydrofuran solution, then pinacolborane (145.1. mu. L, 1mmol) was added with a pipette, benzaldehyde (101.1. mu. L, 1mmol) was added with a pipette, and after reaction at room temperature for 30min, CDCl was added3Preparing a solution. Is calculated by1The yield of the H spectrum is 96%. The nuclear magnetic data of the product are the same as in example one.
Example four Y (Cp)3Synthesis of boric acid ester by catalyzing benzaldehyde and pinacol borane
Adding catalyst Y (Cp) into a reaction bottle subjected to dehydration and deoxidation treatment under an inert gas atmosphere3(1mol%) tetrahydrofuran solution, then pinacolborane (145.1. mu. L, 1mmol) was added using a pipette, benzaldehyde (101.1. mu. L, 1mmol) was added using a pipette, and after 1h reaction at room temperature, CDCl was added3Preparing a solution. Is calculated by1The yield of the H spectrum is 99%. The nuclear magnetic data of the product are the same as in example one.
Nd, Sm and Yb are used to replace Y, and the yield is respectively more than 99%, 99% and 99%.
EXAMPLE V L a (Cp)3Synthesis of boric acid ester by catalyzing benzaldehyde and pinacol borane
Adding catalyst L a (Cp) into the reaction flask after dehydration and deoxidation treatment under inert gas atmosphere33.7mg, 2 ml of tetrahydrofuran was added, 22. mu. L (0.01mol%) was taken by a pipette and added to another reaction flask, pinacolborane (174. mu. L, 1.2 mmol) was added by a pipette, benzaldehyde (101.6. mu. L, 1mmol) was added by a pipette after 1 hour of reaction at room temperature, one drop was pipetted into a nuclear magnetic tube, and CDCl was added3Preparing a solution. Is calculated by1The yield of the H spectrum is 100%. The nuclear magnetic data of the product are the same as in example one.
Example six L a (Cp)3Synthesis of boric acid ester by catalyzing benzaldehyde and pinacol borane
Adding catalyst L a (Cp) into the reaction flask after dehydration and deoxidation treatment under inert gas atmosphere33.7mg, 2 ml of tetrahydrofuran was added, 22. mu. L (0.01mol%) was taken with a pipette and added to another reaction flask, and pinacolborane was added with a pipetteAlkane (174 μ L, 1.2 mmol), benzaldehyde (101.6 μ L, 1mmol) was added with a pipette, reacted at room temperature for 30min, one drop was pipetted into a nuclear magnetic tube, and CDCl was added3Preparing a solution. Is calculated by1The yield of the H spectrum is more than 99 percent. The nuclear magnetic data of the product are the same as in example one.
EXAMPLE seventhly L a (Cp)3Synthesis of boric acid ester by catalyzing benzaldehyde and pinacol borane
Adding catalyst L a (Cp) into the reaction flask after dehydration and deoxidation treatment under inert gas atmosphere35mg, adding tetrahydrofuran 3 ml, adding 24.4 mu L (0.01mol%) into another reaction bottle by using a pipette, adding pinacolborane (145.1 mu L, 1mmol) by using the pipette, adding benzaldehyde (101.6 mu L, 1mmol) by using the pipette, reacting at room temperature for 30min, sucking one drop by using a dropper into a nuclear magnetic tube, adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is more than 99 percent. The nuclear magnetic data of the product are the same as in example one.
EXAMPLE eighthly L a (Cp)3Method for synthesizing boric acid ester by catalyzing p-tolualdehyde and pinacol borane
Adding catalyst L a (Cp) into the reaction flask after dehydration and deoxidation treatment under inert gas atmosphere33.7mg, 2 ml of tetrahydrofuran was added, 22. mu. L (0.01mol%) was taken by a pipette and added to another reaction flask, pinacolborane (174. mu. L, 1.2 mmol) was added by a pipette, p-tolualdehyde (117.9. mu. L, 1mmol) was added by a pipette after 1 hour of reaction at room temperature, one drop was pipetted into a nuclear magnetic tube, and CDCl was added3Preparing a solution. The calculated 1H spectral yield was 100%. Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3) 7.37 – 7.31 (m, 4H), 7.27(dt, J = 6.1, 3.3 Hz, 1H), 4.94 (s, 2H), 1.27 (s, 12H)。
EXAMPLE nine L a (Cp)3Method for synthesizing boric acid ester by catalyzing o-methylbenzaldehyde and pinacol borane
Adding catalyst L a (Cp) into the reaction flask after dehydration and deoxidation treatment under inert gas atmosphere33.7mg, 2 ml tetrahydrofuran was added, then 22. mu. L (0.01mol%) was taken with a pipette and added to another reaction flask, followed by addition of pinacolborane with a pipette(174. mu. L, 1.2 mmol), o-methylbenzaldehyde (115.6. mu. L, 1mmol) was added with a pipette, and after 1 hour of reaction at room temperature, one drop was pipetted into a nuclear magnetic tube, and CDCl was added3Preparing a solution. The calculated 1H spectral yield was 100%. Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3) 7.37 – 7.31 (m, 4H), 7.27(dt, J = 6.1, 3.3 Hz, 1H), 4.94 (s, 2H), 1.27 (s, 12H)。
EXAMPLE ten L a (Cp)3Catalysis of 2,4, 6-trimethyl benzaldehyde and pinacol borane to synthesize borate
Adding catalyst L a (Cp) into the reaction flask after dehydration and deoxidation treatment under inert gas atmosphere33.7mg, 2 ml tetrahydrofuran, 22 μ L (0.01mol%) in another flask with pipette, pinacolborane (174 μ L, 1.2 mmol) in another flask with pipette, 2,4, 6-trimethylbenzaldehyde (147.5 μ L, 1mmol) in another flask, reacting at room temperature for 1h, pipette one drop of NMR tube, adding CDCl3Preparing a solution. The calculated 1H spectral yield was 100%. Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3) 7.37 – 7.31 (m, 4H), 7.27(dt, J = 6.1, 3.3 Hz, 1H), 4.94 (s, 2H), 1.27 (s, 12H)。
EXAMPLE eleventh L a (Cp)3Synthesis of boric acid ester by catalyzing o-methoxybenzaldehyde and pinacol borane
Adding catalyst L a (Cp) into the reaction flask after dehydration and deoxidation treatment under inert gas atmosphere33.7mg, 2 ml tetrahydrofuran, 22 μ L (0.01mol%) in another flask with pipette, pinacolborane (174 μ L, 1.2 mmol) in another flask with pipette, o-methoxybenzaldehyde (120.8 μ L, 1mmol) in another flask, reaction at room temperature for 1h, one drop by pipette in nuclear magnetic tube, CDCl in another flask3Preparing a solution. The calculated 1H spectral yield was 100%. Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3) 7.41 (dd, J = 7.5, 0.7 Hz,1H), 7.23 (dd, J = 7.8, 1.4 Hz, 1H), 6.95 (t, J = 7.5 Hz, 1H), 6.84 (d, J =8.1 Hz, 1H), 4.98 (s, 2H), 3.81 (s, 3H), 1.34 – 1.21 (m, 12H)。
example twelve L a (Cp)3Catalytic p-chlorobenzaldehydeAnd pinacolborane Synthesis of Borate esters
Adding catalyst L a (Cp) into the reaction flask after dehydration and deoxidation treatment under inert gas atmosphere33.5mg, adding tetrahydrofuran 3 ml, then adding 24.4 μ L (0.01mol%) into another reaction flask by using a pipette, adding pinacolborane (174 μ L, 1.2 mmol) by using the pipette, adding p-chlorobenzaldehyde (117.5 μ L, 1mmol) by using the pipette, reacting for 1h at room temperature, sucking one drop by using a dropper into a nuclear magnetic tube, adding CDCl3Preparing a solution. The calculated 1H spectral yield was 100%. Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3) 7.36 (s, 1H), 7.26 – 7.18(m, 3H), 4.89 (s, 2H), 1.27 (s, 12H)。
EXAMPLE thirteen L a (Cp)3Method for synthesizing boric acid ester by catalyzing p-bromobenzaldehyde and pinacol borane
Adding catalyst L a (Cp) into the reaction flask after dehydration and deoxidation treatment under inert gas atmosphere33.5mg, adding tetrahydrofuran 3 ml, then adding 18.5 mu L (0.01mol%) into another reaction bottle by using a pipette, adding pinacolborane (132 mu L, 0.91 mmol) by using the pipette, weighing p-bromobenzaldehyde (140.3mg, 0.76mmol), reacting for 1h at room temperature, sucking one drop by using a dropper into a nuclear magnetic tube, adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 99%. Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3) 7.36 (s, 1H), 7.26 – 7.18 (m, 3H),4.89 (s, 2H), 1.27 (s, 12H)。
example fourteen L a (Cp)3Method for synthesizing boric acid ester by catalyzing o-chlorobenzaldehyde and pinacol borane
Adding catalyst L a (Cp) into the reaction flask after dehydration and deoxidation treatment under inert gas atmosphere33.5mg, adding tetrahydrofuran 3 ml, then adding 18.5 mu L (0.01mol%) into another reaction bottle by using a pipette, adding pinacol borane (174 mu L, 1.2 mmol) by using the pipette, weighing o-chlorobenzaldehyde (117.5 mu L, 1mmol), reacting for 1h at room temperature, sucking one drop by using a dropper into a nuclear magnetic tube, adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 100%.
Example fifteen L a (Cp)3Synthesis of boric acid ester by catalyzing isovaleraldehyde and pinacol borane
Adding catalyst L a (Cp) into the reaction flask after dehydration and deoxidation treatment under inert gas atmosphere33.5mg, adding tetrahydrofuran 3 ml, then adding 18.5 mu L (0.01mol%) into another reaction bottle by using a pipette, adding pinacolborane (174 mu L, 1.2 mmol) by using the pipette, weighing isovaleraldehyde (1mmol), reacting for 1h at room temperature, sucking one drop by using a dropper into a nuclear magnetic tube, adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is more than 99 percent.
Example sixteen L a (Cp)3Synthesis of boric acid ester by catalyzing 3-pyridylaldehyde and pinacol borane
Adding catalyst L a (Cp) into the reaction flask after dehydration and deoxidation treatment under inert gas atmosphere33.5mg, adding tetrahydrofuran 3 ml, then adding 18.5 mu L (0.01mol%) into another reaction bottle by using a pipette, adding pinacolborane (174 mu L, 1.2 mmol) by using the pipette, weighing 3-pyridylaldehyde (1mmol), reacting for 1h at room temperature, sucking one drop by using a dropper into a nuclear magnetic tube, adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is more than 99 percent.
Claims (1)
1. The application of the rare earth metal complexes of the tricyclocene as a catalyst in catalyzing the synthesis reaction of aldehyde and pinacol borane; the chemical structural formula of the rare earth metal tricyclene complex is as follows:
l n is selected from one of lanthanum, yttrium, neodymium, ytterbium and samarium in lanthanide elements, the aldehyde is benzaldehyde, p-tolualdehyde, o-tolualdehyde, 2,4, 6-trimethylbenzaldehyde, p-chlorobenzaldehyde, p-bromobenzaldehyde, o-chlorobenzaldehyde, isovaleraldehyde or 3-pyridylaldehyde, the dosage of the metallocene rare earth metal complex is 0.01-1% of the molar weight of the aldehyde, the molar ratio of the dosage of the pinacol borane to the aldehyde is 1-1.2: 1, the synthesis reaction time is 30 min-1 h, and the temperature is room temperature.
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| CN107474063B (en) * | 2017-08-14 | 2019-11-22 | 苏州大学 | A method of preparing borate |
| CN107556334B (en) * | 2017-09-15 | 2019-06-21 | 苏州大学 | The method for preparing borate based on three fragrant oxygen rare earth compoundings |
| WO2019056280A1 (en) * | 2017-09-21 | 2019-03-28 | 南通纺织丝绸产业技术研究院 | Method for preparing borate |
| CN107930696B (en) * | 2017-11-10 | 2020-02-11 | 苏州大学 | Application of rare earth trimethyl cyclopentadienyl complex in catalyzing hydroboration reaction of imine and borane |
| CN108187746B (en) * | 2017-12-25 | 2020-08-14 | 苏州大学 | Application of trisilamide rare earth metal complex in catalyzing reaction of aldehyde and allyl boric acid |
| CN108083981B (en) * | 2017-12-25 | 2020-10-09 | 苏州大学 | Application of rare earth metal complexes of metallocene in catalyzing reaction of aldehyde and allyl boric acid |
| CN111763226A (en) * | 2020-06-16 | 2020-10-13 | 苏州大学 | Hydroboration reaction method of carbonic ester |
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| CN106046036A (en) * | 2016-06-30 | 2016-10-26 | 苏州大学张家港工业技术研究院 | Application of trisilazane-rare earth complex in catalysis of hydroboration reaction between aldehyde and borane |
| CN106040304A (en) * | 2016-06-30 | 2016-10-26 | 苏州大学 | Application of beta-diimine divalent rare earth boron hydrogen complex to hydroboration of catalytic aldehyde and borane |
| 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 |
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| CN106883255B (en) | 2018-12-21 |
| CN106883255A (en) | 2017-06-23 |
| CN108948058A (en) | 2018-12-07 |
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