CN108906124B - Application of rare earth metal tricyclocene complex as catalyst in catalysis of synthesis reaction of ketone and pinacol borane - Google Patents

Application of rare earth metal tricyclocene complex as catalyst in catalysis of synthesis reaction of ketone and pinacol borane Download PDF

Info

Publication number
CN108906124B
CN108906124B CN201810893002.6A CN201810893002A CN108906124B CN 108906124 B CN108906124 B CN 108906124B CN 201810893002 A CN201810893002 A CN 201810893002A CN 108906124 B CN108906124 B CN 108906124B
Authority
CN
China
Prior art keywords
rare earth
ketone
catalyst
earth metal
pipette
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201810893002.6A
Other languages
Chinese (zh)
Other versions
CN108906124A (en
Inventor
薛明强
陈素芳
颜丹丹
沈琪
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suzhou University
Original Assignee
Suzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Suzhou University filed Critical Suzhou University
Priority to CN201810893002.6A priority Critical patent/CN108906124B/en
Publication of CN108906124A publication Critical patent/CN108906124A/en
Application granted granted Critical
Publication of CN108906124B publication Critical patent/CN108906124B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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 System
    • 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

Abstract

The present invention discloses a rare earth metal metallocene complex asThe application of the catalyst in catalyzing the synthesis reaction of ketone and pinacol borane comprises the following steps of uniformly stirring and mixing the catalyst, borane and ketone, and reacting to prepare boric acid ester; the molecular formula of the rare earth metallocene complex can be represented as follows: ln (Cp)3And Ln represents rare earth metal selected from one of lanthanum, yttrium, neodymium, ytterbium and samarium in lanthanide series. The preparation method has higher catalytic activity, mild reaction conditions, easy product post-treatment, short reaction time, low catalyst consumption, good substrate application range and industrial production.

Description

Application of rare earth metal tricyclocene complex as catalyst in catalysis of synthesis reaction of ketone and pinacol borane
The invention belongs to a method for preparing boric acid ester by utilizing a rare earth metal metallocene complex, which is a divisional application with the application number of 201710162331.9 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 cyclopentadienyl complex as a catalyst in catalyzing synthesis reaction of ketone and pinacol borane.
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 complex formed by the rare earth ions has unique physiochemical properties and more remarkable magnetic properties under certain conditions. Importantly, the stability of the rare earth complex changes irregularly along with the change of the radius, and factors influencing the stability of the complex, such as the change of the coordination number of metal in the complex, the steric effect of a ligand, the hydration degree and the valence bond component, have important influence on the stability of the complex besides the ionic radius. Therefore, researchers can change, modify and enhance the characteristics of the rare earth ions to a great extent through the interaction of the rare earth ions and different ligands. For example, when europium complexes are doped in a conductive polymer CN-PPP, the energy transfer efficiency of the beta-europium diketone complexes of symmetrical phenanthrene and asymmetrical phenanthrene is only 0.053 percent and is far lower than 1.1 percent of the beta-europium diketone complexes of symmetrical biphenyl.
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. There are several different methods for synthesizing borate, the first method, i.e. the method used at the earliest, is to use boron trichloride to directly react with alcohol or phenol, and the borate prepared by the method has the defect that raw materials are difficult to obtain. The second method is a direct condensation reaction of boric acid and alcohol or phenol, and the method has the advantages of easily available raw materials, high yield, simple preparation process and easy operation, and becomes a common method at present. The third method is to use the reaction of borax with alcohol or phenol, which has the advantages of lower price than boric acid and easy preparation, but has the disadvantage of difficult product separation. In addition, there are other methods for synthesizing borate esters, such as transesterification of borate esters with alcohols or phenols, and direct reaction of boron oxide with alcohols or phenols. However, these methods have disadvantages, such as high equipment requirements, difficulty in industrial production, and non-economic efficiency, or complicated post-reaction treatment, difficulty in obtaining high yield, or difficulty in obtaining raw materials and high cost. In the existing catalytic system, the catalyst consumption is large, the reaction time is long, and the substrate universality is low. Rare earth catalyzed hydroboration reactions are reported less at present, but the rare earth catalyzed hydroboration reaction of the metallocene is not reported.
Disclosure of Invention
The invention aims to provide a method for preparing boric acid ester by utilizing a metallocene rare earth metal complex, which is used for catalyzing ketone compounds and pinacol borane to prepare boric acid ester by applying the metallocene rare earth metal complex.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for preparing boric acid ester by utilizing a rare earth metal cyclopentadienyl complex comprises the following steps of uniformly stirring and mixing a catalyst, borane and ketone, and reacting to prepare the 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:
Figure 376204DEST_PATH_IMAGE001
。
in the technical scheme, the borane is pinacol borane; the ketone is aromatic ketone or aliphatic cyclic ketone; the chemical structural formula of the aromatic ketone is shown as one of the following structural formulas:
Figure 978349DEST_PATH_IMAGE002
、
Figure 50210DEST_PATH_IMAGE003
、
Figure 850938DEST_PATH_IMAGE004
wherein R is phenyl, substituted phenyl or a heterocyclic aryl group, such as thienyl; the chemical structural formula of the aliphatic cyclic ketone is shown as one of the following structural formulas:
Figure 841897DEST_PATH_IMAGE005
、
Figure 642321DEST_PATH_IMAGE006
wherein n is 3-15.
In the technical scheme, the dosage of the metallocene rare earth metal complex is 0.01-1% of the molar weight of the ketone; the molar ratio of the borane to the ketone 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 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 ketone and pinacol borane; the chemical structural formula of the rare earth metal tricyclene complex is as follows:
Figure 376928DEST_PATH_IMAGE001
the molecular formula of the above-mentioned metallocene rare earth metal complex can be expressed as follows: ln (Cp)3And Ln represents rare earth metal selected from one of lanthanum, yttrium, neodymium, ytterbium and samarium in lanthanide series.
In the technical scheme, the borane is pinacol borane; the ketone is aromatic ketone or aliphatic cyclic ketone; the chemical structural formula of the aromatic ketone is shown as one of the following structural formulas:
Figure 235424DEST_PATH_IMAGE002
、
Figure 803809DEST_PATH_IMAGE003
、
Figure 911705DEST_PATH_IMAGE004
wherein R is benzeneA group, a substituted phenyl group or a heterocyclic aryl group; the chemical structural formula of the aliphatic cyclic ketone is shown as one of the following structural formulas:
Figure 653265DEST_PATH_IMAGE005
、
Figure 897426DEST_PATH_IMAGE006
wherein n is 3-15.
In the technical scheme, the dosage of the metallocene rare earth metal complex is 0.01-1% of the molar weight of the ketone; the molar ratio of the borane to the ketone is 1-1.2: 1; the reaction time is 30 min-1 h.
The rare earth metallocene complex can catalyze the hydroboration reduction reaction of ketone and pinacol borane to prepare borate, so the invention requests to protect the application of the rare earth metallocene complex as a catalyst in synthesizing borate.
In the technical scheme, the reaction temperature is room temperature.
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 ketone; the reaction speed is high, the reaction temperature is room temperature, and the yield can reach more than 99 percent after the reaction is carried out for 60 minutes; 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 the ketone for the first time, and the catalyst has simple structure, is easy to prepare and can efficiently catalyze the reaction;
3. the rare earth metal tricyclene complex disclosed by the invention has a wide application range on a substrate, is suitable for ketones 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 acetophenone and pinacol borane
Adding catalyst Y (Cp) into the reaction bottle which is subjected to dehydration and deoxidation treatment under the inert gas atmosphere3 5.2 mg, adding tetrahydrofuran 3 ml, then adding 20.6 μ L (0.01 mol%) into another reaction flask by using a pipette, adding pinacolborane (174 μ L, 1.2mmol) by using the pipette, adding acetophenone (116.7 μ L, 1mmol) by using the pipette, reacting for 1h at room temperature, absorbing one drop by using a dropper into a nuclear magnetic tube, adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 98%. Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3) 7.40 – 7.22 (m, 5H), 1.51 – 1.47 (d, J=6.5Hz, 3H), 1.24 (s, 6H), 1.21 (s, 6H)。
EXAMPLE two Nd (Cp)3Synthesis of boric acid ester by catalyzing acetophenone and pinacol borane
Adding a catalyst Nd (Cp) into a reaction bottle subjected to dehydration and deoxidation treatment under an inert gas atmosphere35.3 mg, adding tetrahydrofuran 3 ml, then adding 23.3. mu.L (0.01 mol%) into another reaction flask by using a pipette, adding pinacolborane (174. mu.L, 1.2mmol) by using the pipette, adding acetophenone (116.7. mu.L, 1mmol) by using the pipette, reacting for 1h at room temperature, absorbing 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 III Sm (Cp)3Synthesis of boric acid ester by catalyzing acetophenone and pinacol borane
Adding a catalyst Sm (Cp) into a reaction bottle subjected to dehydration and deoxidation treatment under an inert gas atmosphere32.1 mg, 2 ml tetrahydrofuran, 39.8. mu.L (0.01 mol%) with pipette into another reaction flask, pinacolborane (174. mu.L, 1.2mmol) with pipette, acetophenone (116.7. mu.L, 1mmol) with pipette after 1h reaction at room temperature, one drop with dropper into nuclear magnetic tube, CDCl3Preparing 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.
EXAMPLE four La (Cp)3Synthesis of boric acid ester by catalyzing acetophenone and pinacol borane
Adding catalyst La (Cp) into a reaction bottle which is subjected to dehydration and deoxidation treatment under an inert gas atmosphere32.8mg, 2 ml of tetrahydrofuran was added, then 29. mu.L (0.01 mol%) was taken by a pipette and added to another reaction flask, then pinacolborane (174. mu.L, 1.2mmol) was added by the pipette and acetophenone (116.7. mu.L, 1mmol) was added by the 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 more than 99 percent. The nuclear magnetic data of the product are the same as in example one.
Figure 699029DEST_PATH_IMAGE007
EXAMPLE V Yb (Cp)3Synthesis of boric acid ester by catalyzing acetophenone and pinacol borane
Adding catalyst Yb (Cp) into a reaction bottle after dehydration and deoxidation treatment under an inert gas atmosphere34.3mg, adding tetrahydrofuran 3 ml, then adding 30.7 μ L (0.01 mol%) into another reaction flask by using a pipette, adding pinacolborane (174 μ L, 1.2mmol) by using the pipette, adding acetophenone (116.7 μ L, 1mmol) by using the pipette, reacting for 1h at room temperature, absorbing one drop by using a dropper into a nuclear magnetic tube, adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 97%. The nuclear magnetic data of the product are the same as in example one.
EXAMPLE six La (Cp)3Synthesis of boric acid ester by catalyzing isobutyrophenone and pinacol borane
Adding catalyst La (Cp) into a reaction bottle which is subjected to dehydration and deoxidation treatment under an inert gas atmosphere34.8mg, 4 ml of tetrahydrofuran was added, 33.8. mu.L (0.01 mol%) was taken out with a pipette and added to another reaction flask, pinacolborane (174. mu.L, 1.2mmol) was added with a pipette, isobutyrophenone (150. mu.L, 1mmol) was added with a pipette, and after 1 hour of reaction at room temperature, the mixture was droppedSucking one drop of the tube into a nuclear magnetic tube, and adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 99%. Nuclear magnetic number of the product:1H NMR (400 MHz, CDCl3) 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)。
EXAMPLE seventhly La (Cp)3Method for synthesizing boric acid ester by catalyzing p-methoxyacetophenone and pinacol borane
Adding catalyst La (Cp) into a reaction bottle which is subjected to dehydration and deoxidation treatment under an inert gas atmosphere34.8mg, adding tetrahydrofuran 4 ml, adding 37.1 μ L (0.01 mol%) with a pipette into another reaction flask, adding pinacolborane (190.8 μ L, 1.3 mmol) with the pipette, weighing p-methoxyacetophenone (164.6mg, 1.1mmol), reacting at room temperature for 1h, sucking one drop with a dropper into a nuclear magnetic tube, adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 99%. Nuclear magnetic number of the product:1H NMR (400 MHz, CDCl3) 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)。
EXAMPLE eighthly La (Cp)3Method for catalyzing p-fluoro acetophenone and pinacol borane to synthesize boric acid ester
Adding catalyst La (Cp) into a reaction bottle which is subjected to dehydration and deoxidation treatment under an inert gas atmosphere37mg, adding tetrahydrofuran 5 ml, adding 29 μ L (0.01 mol%) with pipette into another reaction flask, adding pinacolborane (174 μ L, 1.2mmol) with pipette, adding isobutyrophenone (120.9 μ L, 1mmol) with pipette, reacting at room temperature for 1h, sucking one drop with dropper into nuclear magnetic tube, adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 99%. Nuclear magnetic number of the product:1H NMR (400 MHz, CDCl3) 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)。
EXAMPLE nine La (Cp)3Catalytic p-methylbenzeneSynthesis of boronic esters from ethanone and pinacol borane
Adding catalyst La (Cp) into a reaction bottle which is subjected to dehydration and deoxidation treatment under an inert gas atmosphere37mg, adding tetrahydrofuran 5 ml, taking 29 μ L (0.01 mol%) by using a pipette, adding into another reaction flask, adding pinacolborane (174 μ L, 1.2mmol) by using the pipette, adding isobutyrophenone (133.5 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. Is calculated by1The yield of the H spectrum is more than 99 percent. Nuclear magnetic number of the product:1H NMR (400 MHz, CDCl3) 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)。
EXAMPLE ten La (Cp)3Synthesis of boric acid ester by catalyzing 1-tetralone and pinacol borane
Adding catalyst La (Cp) into a reaction bottle which is subjected to dehydration and deoxidation treatment under an inert gas atmosphere37mg, tetrahydrofuran 5 ml, then 29. mu.L (0.01 mol%) by pipette into another reaction flask, then pinacolborane (174. mu.L, 1.2mmol) by pipette, then 1-tetralone (132.8. mu.L, 1mmol) by pipette after 1h reaction at room temperature, one drop by pipette into nuclear magnetic tube, and CDCl was added3Preparing a solution. Is calculated by1The yield of the H spectrum is more than 99 percent. Nuclear magnetic number of the product:1H NMR (400 MHz, CDCl3) 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)。
EXAMPLE eleven La (Cp)3Synthesis of boric acid ester by catalyzing o-methyl ethyl ketone and pinacol borane
Adding catalyst La (Cp) into a reaction bottle which is subjected to dehydration and deoxidation treatment under an inert gas atmosphere33.9mg, 3 ml of tetrahydrofuran was added, then 31.3. mu.L (0.01 mol%) was taken with a pipette and added to another reaction flask, then pinacolborane (174. mu.L, 1.2mmol) was added with a pipette and o-methylethylketone (130.8. mu.L, 1mmol) was added with a pipette,after reacting at room temperature for 1h, pipette one drop into a nuclear magnetic tube, add CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 99%. Nuclear magnetic number of the product:1H NMR (400 MHz, CDCl3) 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)。
EXAMPLE twelve La (Cp)3Catalysis of 2, 4, 6-trimethyl acetophenone and pinacol borane synthesis boric acid ester
Adding catalyst La (Cp) into a reaction bottle which is subjected to dehydration and deoxidation treatment under an inert gas atmosphere33.9mg, adding tetrahydrofuran 3 ml, adding 31.3 μ L (0.01 mol%) into another reaction flask by using a liquid-transferring gun, adding pinacolborane (174 μ L, 1.2mmol) by using the liquid-transferring gun, adding 2, 4, 6-trimethylacetophenone (166.4 μ L, 1mmol) by using the liquid-transferring gun, reacting for 1h at room temperature, sucking one drop of nuclear magnetic tube by using a dropper, adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 99%. Nuclear magnetic number of the product:1H NMR (400 MHz, CDCl3) 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)。
EXAMPLE thirteen La (Cp)3Catalytic synthesis of boric acid ester from p-bromoacetophenone and pinacol borane
Adding catalyst La (Cp) into a reaction bottle which is subjected to dehydration and deoxidation treatment under an inert gas atmosphere33.9mg, adding tetrahydrofuran 3 ml, then adding 38 μ L (0.01 mol%) into another reaction flask by using a liquid transfer gun, adding pinacolborane (211.5 μ L, 1.4 mmol) by using the liquid transfer gun, weighing p-bromoacetophenone (241.8mg, 1.2mmol), reacting for 1h at room temperature, absorbing one drop by using a dropper into a nuclear magnetic tube, adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 98%. Nuclear magnetic number of the product:1H NMR (400 MHz, CDCl3) 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)。
example fourteen La (Cp)3Method for synthesizing boric acid ester by catalyzing p-nitroacetophenone and pinacol borane
Adding catalyst La (Cp) into a reaction bottle which is subjected to dehydration and deoxidation treatment under an inert gas atmosphere33.9mg, adding tetrahydrofuran 3 ml, then adding 31.8 μ L (0.01 mol%) into another reaction bottle by using a pipette, adding pinacolborane (177 μ L, 1.2mmol) by using the pipette, weighing p-nitroacetophenone (167.9mg, 1mmol), reacting for 2h 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 98%. Nuclear magnetic number of the product:1H NMR (400 MHz, CDCl3) 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)。
EXAMPLE fifteen La (Cp)3Catalysis of 1- (2-thienyl) ethanone and pinacol borane synthesis of boric acid ester
Adding catalyst La (Cp) into a reaction bottle which is subjected to dehydration and deoxidation treatment under an inert gas atmosphere318.5mg, adding 1.6 ml tetrahydrofuran, then adding 353 uL (1mol%) into another reaction bottle by using a pipette, adding pinacolborane (174.1 uL, 1.2mmol) by using the pipette, adding 1- (2-thienyl) ethanone (108 uL, 1mmol) by using the pipette, reacting for 1h at room temperature, absorbing 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 number of the product:1H NMR (400 MHz, CDCl3) 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)。
example sixteen La (Cp)3Synthesis of boric acid ester by catalyzing cyclododecanone and pinacol borane
Adding catalyst La (Cp) into a reaction bottle which is subjected to dehydration and deoxidation treatment under an inert gas atmosphere318.5mg, adding 1.6 ml of tetrahydrofuran, then adding 340.8 mu L (1mol%) into another reaction bottle by using a pipette, adding pinacolborane (168.8 mu L, 1.16 mmol) by using the pipette, weighing cyclododecanone (168.8 mg, 0.97mmol), 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 percent; the yield of the catalyst was 99% at 0.01 mol%. Nuclear magnetic number of the product:1H NMR (400 MHz, CDCl3) 4.11 (dt, J = 31.5, 15.5 Hz, 1H), 1.66 – 1.53 (m, 2H), 1.32 (m, 22H), 1.17 (s, 12H)。
example seventeen La (Cp)3Synthesis of boric acid ester by catalyzing dibenzyl ketone and pinacol borane
Adding catalyst La (Cp) into a reaction bottle which is subjected to dehydration and deoxidation treatment under an inert gas atmosphere318.5mg, adding 1.6 ml tetrahydrofuran, then adding 286 uL (1mol%) with a pipette into another reaction flask, adding pinacolborane (142.2 uL, 0.98 mmol) with a pipette, weighing dibenzyl ketone (171.7 mg, 0.82mmol), reacting for 1h at room temperature, sucking one drop with a dropper into a nuclear magnetic tube, adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 100 percent; the yield of the catalyst was 99% at 0.01 mol%. Nuclear magnetic number of the product:1H NMR (400 MHz, CDCl3) 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 (2)

1. the application of the rare earth metal complexes of the tricyclocene as a catalyst in catalyzing the synthesis reaction of ketone and pinacol borane; the chemical structural formula of the rare earth metal tricyclene complex is as follows:
Figure DEST_PATH_IMAGE002
ln represents rare earth metal and is selected from one of lanthanum and yttrium in lanthanide series; the borane is pinacol borane; the ketone is acetophenone, isobutyrophenone, p-methoxyacetophenone, p-fluoroacetophenone, p-methylacetophenone, 1-tetralone, o-methylacetophenone, 2, 4, 6-trimethylacetophenone, p-bromoacetophenone, p-nitroacetophenone, 1- (2-thienyl) acetophenone, cyclododecanone or dibenzylketone.
2. The use according to claim 1, wherein the amount of the rare earth metallocene complex is 0.01 to 1 percent of the molar amount of the ketone; the molar ratio of the borane to the ketone is 1-1.2: 1; the synthesis reaction time is 30 min-1 h, and the temperature is room temperature.
CN201810893002.6A 2017-03-17 2017-03-17 Application of rare earth metal tricyclocene complex as catalyst in catalysis of synthesis reaction of ketone and pinacol borane Active CN108906124B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810893002.6A CN108906124B (en) 2017-03-17 2017-03-17 Application of rare earth metal tricyclocene complex as catalyst in catalysis of synthesis reaction of ketone and pinacol borane

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201810893002.6A CN108906124B (en) 2017-03-17 2017-03-17 Application of rare earth metal tricyclocene complex as catalyst in catalysis of synthesis reaction of ketone and pinacol borane
CN201710162331.9A CN106883256B (en) 2017-03-17 2017-03-17 A method of borate is prepared using triscyclopentadienyl rare earth metal complex

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CN201710162331.9A Division CN106883256B (en) 2017-03-17 2017-03-17 A method of borate is prepared using triscyclopentadienyl rare earth metal complex

Publications (2)

Publication Number Publication Date
CN108906124A CN108906124A (en) 2018-11-30
CN108906124B true CN108906124B (en) 2020-11-17

Family

ID=59181729

Family Applications (2)

Application Number Title Priority Date Filing Date
CN201710162331.9A Active CN106883256B (en) 2017-03-17 2017-03-17 A method of borate is prepared using triscyclopentadienyl rare earth metal complex
CN201810893002.6A Active CN108906124B (en) 2017-03-17 2017-03-17 Application of rare earth metal tricyclocene complex as catalyst in catalysis of synthesis reaction of ketone and pinacol borane

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CN201710162331.9A Active CN106883256B (en) 2017-03-17 2017-03-17 A method of borate is prepared using triscyclopentadienyl rare earth metal complex

Country Status (1)

Country Link
CN (2) CN106883256B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11440924B2 (en) 2017-04-15 2022-09-13 Soochow University Method for preparing borate ester on basis of tricyclopentadienyl rare earth metal complex
CN107540700B (en) * 2017-09-15 2019-06-25 苏州大学 The method for preparing borate using 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
CN108707162B (en) * 2018-05-14 2020-09-01 南京林业大学 Keto hydroboration reaction method under catalyst-free and solvent-free conditions
CN111763226A (en) * 2020-06-16 2020-10-13 苏州大学 Hydroboration reaction method of carbonic ester

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005014509A1 (en) * 2003-07-15 2005-02-17 Dsm Ip Assets B.V. Process for the preparation of enantiomerically enriched esters and alcohols
CN103159791A (en) * 2013-04-02 2013-06-19 苏州大学 Rare-earth metal organic compound, as well as preparation method and application thereof
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

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106046036B (en) * 2016-06-30 2018-05-29 苏州大学张家港工业技术研究院 Application of the three silicon amine rare earth compoundings in the hydroboration of catalysis aldehyde and borine

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005014509A1 (en) * 2003-07-15 2005-02-17 Dsm Ip Assets B.V. Process for the preparation of enantiomerically enriched esters and alcohols
CN103159791A (en) * 2013-04-02 2013-06-19 苏州大学 Rare-earth metal organic compound, as well as preparation method and application thereof
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

Also Published As

Publication number Publication date
CN108906124A (en) 2018-11-30
CN106883256B (en) 2018-12-21
CN106883256A (en) 2017-06-23

Similar Documents

Publication Publication Date Title
CN108906124B (en) Application of rare earth metal tricyclocene complex as catalyst in catalysis of synthesis reaction of ketone and pinacol borane
CN108948058B (en) Application of rare earth metal complexes of tricyclocene as catalyst in catalyzing aldehyde and pinacol borane synthesis reaction
CN108570065B (en) Method for synthesizing boric acid ester based on β -diimine divalent rare earth boron hydrogen complex
CN108164555B (en) Synthesis method of boric acid ester
CN106188118B (en) Application of the three silicon amine rare earth compoundings in the hydroboration of catalysis ketone and borine
CN106749372A (en) A kind of preparation method of organic boronic ester compounds
CN107930696B (en) Application of rare earth trimethyl cyclopentadienyl complex in catalyzing hydroboration reaction of imine and borane
WO2021253847A1 (en) Use of deprotonated phenyl bridged β-ketimine lithium compound in hydroboration reaction
CN112500428B (en) Application of anilino lithium compound in catalyzing reaction of carboxylic acid compound and borane hydroboration
Laye et al. The Trityl‐Cation Mediated Phosphine Oxides Reduction
CN111995497A (en) Preparation method of allyl alcohol
CN110818733B (en) Method for preparing boric acid ester by using disilylamine rare earth complex to catalyze hydroboration reaction of imine and borane
CN110357914B (en) Application of trisilamine rare earth complex in preparation of boric acid ester by catalyzing reaction of ester and borane
CN108031492B (en) Preparation method of boric acid ester
CN108440590A (en) The method for preparing borate using fatty aldehyde
CN107474063B (en) A method of preparing borate
CN110256474B (en) Application of trisilamine rare earth complex in catalyzing reaction of carbonate and borane
Pospiech et al. Diborylated Magnesium Anthracene as Precursor for B2H5−‐Bridged 9, 10‐Dihydroanthracene
CN107540700A (en) The method for preparing borate using three fragrant oxygen rare earth compoundings
CN109438493B (en) Method for preparing borate based on n-butyl lithium
WO2018188104A1 (en) Method for preparing borate ester on basis of tricyclopentadienyl rare earth metal complex
CN109485668A (en) The method that room temperature prepares borate
CN109438491B (en) Method for preparing boric acid ester by non-catalytic hydroboration reaction of aromatic carboxylic acid
WO2019056280A1 (en) Method for preparing borate
CN109651082B (en) Method for preparing aliphatic alcohol at room temperature

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant