CN108570065B - Method for synthesizing boric acid ester based on β -diimine divalent rare earth boron hydrogen complex - Google Patents
Method for synthesizing boric acid ester based on β -diimine divalent rare earth boron hydrogen complex Download PDFInfo
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
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- B01J31/22—Organic complexes
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
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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
Abstract
The invention discloses a method for synthesizing boric acid ester based on β -diimine divalent rare earth boron hydrogen complex, which utilizes β -diimine rare earth dichloride and NaBH4Reacting in tetrahydrofuran solvent, and obtaining β -diimine divalent rare earth boron hydrogen complex through in-situ Na/K reductionipr2‑(C6H3)‑NC(Me)CHC(Me)N‑(C6H3)‑2,6‑ipr2]Ln‑BH4 .The β -diimine divalent rare earth hydroboron complex disclosed by the invention can catalyze the hydroboration reaction of borane and ketone with high activity under mild conditions, and has the advantages of short reaction time, mild reaction conditions and simple and convenient post-treatment method.
Description
The invention relates to application of β -diimine divalent rare earth boron hydrogen complex in catalyzing hydroboration reaction of ketone and borane, which is filed for divisional application of invention patents with 2016, 6, 30 and 201610501609.6, and belongs to the part of a preparation method of a compound.
Technical Field
The invention relates to a rare earth metal complex catalytic reaction, in particular to an application of β -diimine divalent rare earth boron hydrogen complex in catalyzing hydroboration reaction of borane and ketone.
Background
The application of borate ester is rapidly developed, such as trimethyl borate is largely used for preparing high-energy fuel; in addition, it is also used as an antifriction and anti-friction additive for lubricating oils, a rubber-metal adhesion promoter, a stabilizer in polymers, etc.; therefore, the synthesis of organoborates has been a focus of research. The reduction of boranes with carbonyl compounds, such as ketones, is the most straightforward and most atom-efficient method for synthesizing boronic esters containing different substituents. But the reaction conditions are severe in the absence of a catalyst. Therefore, the need to explore new catalytic systems to enable the mild, efficient synthesis of organic boronic acid esters has become more urgent. At present, the literature reports that the catalytic system for hydroboration reaction of carbonyl compound and borane is relatively few, and borane (diborane), metal oxide, metal organic compound and the like are mainly used; as a class of catalytic systems, metal organic compounds are widely used to form a class of catalysts with functionality through self-assembly. Metallo-organic compounds that have been reported to catalyze this reaction are: main group metal complexes, secondary group metal zinc complexes, transition metal molybdenum, titanium and ruthenium complexes. In modern rare earth metal organic chemistry, the self-assembled rare earth metal complex becomes a high-activity catalytic system due to the ligand with a unique structure and the high-efficiency controllable initiating group, so far, no report about the catalysis of the boron hydrogenation reaction of borane and carbonyl compounds by the rare earth complex is found, and in view of the high-activity catalytic effect of the complex, the expansion of the application of the complex has important application value and also has important theoretical significance for the research of organic boron chemistry.
Disclosure of Invention
The invention aims to provide an application of β -diimine divalent rare earth boron hydrogen complex in catalyzing hydroboration reaction of borane and ketone.
In order to achieve the purpose, the technical scheme adopted by the invention is that β -diimine divalent rare earth boron hydrogen complex is applied to catalyzing the hydroboration reaction of borane and ketone, wherein the molecular structural formula of the β -diimine divalent rare earth boron hydrogen complex is as follows:
wherein Ln is rare earth metal ytterbium or samarium.
The molecular formula of the β -diimine divalent rare earth boron hydrogen complex can be expressed as [2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Ln-BH4 .2THF, Ln represents rare earth metal, and is selected from one of ytterbium and samarium in lanthanide, and THF is tetrahydrofuran.
The β -diimine divalent rare earth boron hydrogen complex can catalyze the hydroboration reaction of borane and ketone, wherein the borane is pinacol borane, and the ketone is acetophenone or o-methylacetophenone, p-methylacetophenone, o-chloroacetophenone, p-chloroacetophenone, 2-acetylfuran, 2-acetylthiophene and 2-naphthylethanone.
In the technical scheme, the β -diimine divalent rare earth boron hydrogen complex, ketone and borane are mixed according to the molar ratio of 0.1-0.5 percent to 1: 1.
In the technical scheme, the temperature of the hydroboration reaction is room temperature, and the reaction time is 5-15 minutes.
The invention also discloses a method for catalyzing the hydroboration reaction of borane and ketone by using the β -diimine divalent rare earth hydroboron complex, which comprises the following steps:
under the anhydrous and oxygen-free conditions, in an inert gas atmosphere, uniformly mixing a catalyst, borane and ketone in sequence; reacting for 5-15 minutes; with CDCl3Terminating the reaction, decompressing the reaction liquid to remove the solvent, adding n-hexane (3X 2 mL) into the residual liquid to take away the high-boiling point solvent to obtain products which are different substituted boric acid esters, wherein the catalyst is β -diimine divalent rare earth boron hydrogen complex.
In the technical scheme, the borane is pinacol borane; the ketone is acetophenone or o-methylacetophenone, p-methylacetophenone, o-chloroacetophenone, p-chloroacetophenone, 2-acetylfuran, 2-acetylthiophene and 2-naphthylethanone; the amount of the catalyst is 0.1-0.5% of the mole number of the ketone; the molar ratio of the used amount of borane to the used amount of ketone is 1: 1; the temperature of the reaction was room temperature.
The invention further discloses a method for synthesizing boric acid ester, which comprises the steps of sequentially and uniformly mixing a catalyst, borane and ketone in an inert gas atmosphere under the anhydrous and oxygen-free conditions; reacting for 5-15 minutes; with CDCl3Terminating the reaction, decompressing the reaction liquid to remove the solvent, adding n-hexane (3X 2 mL) into the residual liquid to take away the high-boiling point solvent to obtain products which are different substituted boric acid esters, wherein the catalyst is β -diimine divalent rare earth boron hydrogen complex.
In the technical scheme, the borane is pinacol borane; the ketone is acetophenone or o-methylacetophenone, p-methylacetophenone, o-chloroacetophenone, p-chloroacetophenone, 2-acetylfuran, 2-acetylthiophene and 2-naphthylethanone; the amount of the catalyst is 0.1-0.5% of the mole number of the ketone; the molar ratio of the used amount of borane to the used amount of ketone is 1: 1; the temperature of the reaction was room temperature.
The above technical solution can be expressed as follows:
R1、R2from the starting ketone.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. the invention firstly uses the rare earth complex to catalyze the hydroboration reaction of borane and ketone, thereby developing a novel high-efficiency rare earth metal catalyst- β -diimine divalent rare earth hydroboration complex for catalyzing the hydroboration reaction, not only expanding the application of the rare earth complex, but also enriching the hydroboration reaction method of borane and ketone.
2. The β -diimine divalent rare earth boron hydrogen complex disclosed by the invention can catalyze ketone and borane to synthesize borate with high activity under mild conditions (room temperature), compared with a plurality of catalysts reported in literature, the dosage of the catalyst only needs 0.1-0.5% of the molar weight of the ketone under the condition of achieving the same yield, the reaction time is very short, the yield of more than 90% can be obtained in 5 minutes of reaction, and the reaction efficiency is extremely high.
3. The β -diimine divalent rare earth boron hydrogen complex disclosed by the invention has a wide application range on substrates, is suitable for ketones with different substituent positions and different electronic effects, and is simple and controllable in reaction process, high in yield, easy in product post-treatment and suitable for industrial production.
Detailed Description
The invention is further described below with reference to the following examples:
the first embodiment is as follows: [2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Yb-BH4 .2THF (tetrahydrofuran) is used for catalyzing hydroboration reaction of acetophenone and pinacol borane
In the reaction flask after dehydration and deoxidation treatment, 0.1 mL of catalyst [2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Yb-BH4 .2THF in toluene (0.01M), then pinacolborane (0.145 mL, 1mmol) was added by syringe, followed by acetophenone (0.117 mL, 1 mmol). After 5min of reaction, 0.5mL CDCl was added3To obtain the corresponding pinacol borate with the nuclear magnetic yield of 90 percent, C6H5CH(CH3)OB(OC(CH3)2C(CH3)2O). Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3): 7.36 (d, 2H, ArH),7.16-7.11 (m, 3H, ArH), 5.25 (q, 1H, ArCH), 1.49 (d, 3H, CH 3CH), 1.21 (d,12H, C(CH 3)2) ppm.11B NMR (128 MHz, CDCl3): 25.8 ppm。
example two: [2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Sm-BH4 .2THF (tetrahydrofuran) is used for catalyzing hydroboration reaction of acetophenone and pinacol borane
In the reaction flask after dehydration and deoxidation treatment, 0.1 mL of catalyst [2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Sm-BH4 .2THF in toluene (0.01M), then pinacolborane (0.145 mL, 1mmol) was added by syringe, acetophenone (0.117 mL, 1mmol) was added by syringe, after 10min of reaction, 0.5mL CDCl was added3To obtain the corresponding pinacol borate with the nuclear magnetic yield of 92 percent, C6H5CH(CH3)OB(OC(CH3)2C(CH3)2O). The nuclear magnetic data of the product are the same as in example one.
Example three: [2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Sm-BH4 .2THF is used for catalyzing hydroboration reaction of o-methylacetophenone and pinacol borane
In the reaction flask after dehydration and deoxidation treatment, 0.1 mL of catalyst [2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Sm-BH4 .2THF in toluene (0.01M), then pinacolborane (0.145 mL, 1mmol) was added by syringe, followed by o-methylacetophenone (0.131 mL, 1 mmol). After 10min of reaction, 0.5mL CDCl was added3To obtain the corresponding pinacol borate with nuclear magnetic yield of 91 percent, C6H5CH(CH3)OB(OC(CH3)2C(CH3)2O). Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3): 7.53 (d, 1H,ArH), 7.16 (td, 1H, ArH), 7.13 (td, 1H, ArH), 7.10 (t, 1H, ArH), 5.43 (q, 1H,ArCH), 2.34 (s, 1H, ArCH 3 ), 1.45 (d, 3H, CH 3CH), 1.21 (d, 12H, C(CH 3)2) ppm.11B NMR (128 MHz, CDCl3): 25.6 ppm。
example four: [2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Sm-BH4 .2THF is used for catalyzing hydroboration reaction of o-chloroacetophenone and pinacol borane
In the reaction flask after dehydration and deoxidation treatment, 0.1 mL of catalyst [2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Sm-BH4 .2THF in toluene (0.01M) was added followed by pinacolborane (0.145 mL, 1mmol) by syringe and o-chloroacetophenone (0.130 mL, 1mmol) by syringe. After 10min of reaction, 0.5mL CDCl was added3To obtain the corresponding pinacol borate with the nuclear magnetic yield of 99 percent, C6H5CH(CH3)OB(OC(CH3)2C(CH3)2O). Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3): 7.65 (dd, 1H,ArH), 7.28-7.21 (m, 3H, ArH), 5.63 (q, 1H, ArCH),1.50 (d, 3H, CH 3CH), 1.22(d, 12H, C(CH 3)2) ppm.11B NMR (128 MHz, CDCl3): 25.8 ppm。
example five: [2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Sm-BH4 .2THF (tetrahydrofuran) catalyzes hydroboration reaction of p-methylacetophenone and pinacol borane
In the reaction flask after dehydration and deoxidation treatment, 0.1 mL of catalyst [2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Sm-BH4 .2THF in toluene (0.01M), then pinacolborane (0.145 mL, 1mmol) was added by syringe, followed by p-methylacetophenone (0.135 mL, 1 mmol). After 10min of reaction, 0.5mL CDCl was added3To obtain the corresponding pinacol borate with the nuclear magnetic yield of 92 percent, C6H5CH(CH3)OB(OC(CH3)2C(CH3)2O). Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3): 7.25 (d, 2H,ArH), 7.12 (d, 2H, ArH), 5.21 (q, 1H, ArCH), 2.32 (s, 1H, ArCH 3 ), 1.47 (d,3H, CH 3CH), 1.22 (d, 12H, C(CH 3)2) ppm.11B NMR (128 MHz, CDCl3): 26.1 ppm。
example six: [2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Sm-BH4 .2THF (tetrahydrofuran) is used for catalyzing hydroboration reaction of p-chloroacetophenone and pinacol borane
In the reaction flask after dehydration and deoxidation treatment, 0.1 mL of catalyst [2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Sm-BH4 .2THF in toluene (0.01M) was added followed by pinacolborane (0.145 mL, 1mmol) by syringe and p-chloroacetophenone (0.130 mL, 1mmol) by syringe. After 10min of reaction, 0.5mL CDCl was added3To obtain the corresponding pinacol borate with the nuclear magnetic yield of 97 percent, C6H5CH(CH3)OB(OC(CH3)2C(CH3)2O). Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3): 7.29 (d, 4H,ArH), 5.22 (q, 1H, ArCH), 1.46 (d, 3H, CH 3CH), 1.23 (d, 12H, C(CH 3)2) ppm.11BNMR (128 MHz, CDCl3): 25.6 ppm。
example seven: [2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Yb-BH4 .2THF (tetrahydrofuran) is used for catalyzing hydroboration reaction of p-chloroacetophenone and pinacol borane
In the reaction flask after dehydration and deoxidation treatment, 0.3 mL of catalyst [2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Yb-BH4 .2THF in toluene (0.01M) was added followed by pinacolborane (0.145 mL, 1mmol) by syringe and p-chloroacetophenone (0.130 mL, 1mmol) by syringe. After 10min of reaction, 0.5mL CDCl was added3To obtain the corresponding pinacol borate with the nuclear magnetic yield of 97 percent, C6H5CH(CH3)OB(OC(CH3)2C(CH3)2O). The nuclear magnetic data of the product are the same as example six.
Example eight: [2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Sm-BH4 .2THF (tetrahydrofuran) is used for catalyzing hydroboration reaction of p-chloroacetophenone and pinacol borane
In the reaction flask after dehydration and deoxidation treatment, 0.5mL of catalyst [2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Sm-BH4 .2THF in toluene (0.01M) was added followed by pinacolborane (0.145 mL, 1mmol) by syringe and p-chloroacetophenone (0.130 mL, 1mmol) by syringe. After 10min of reaction, 0.5mL CDCl was added3To obtain the corresponding pinacol borate with the nuclear magnetic yield of 98 percent, C6H5CH(CH3)OB(OC(CH3)2C(CH3)2O). The nuclear magnetic data of the product are the same as example six.
Example nine: [2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Yb-BH4 .2THF (tetrahydrofuran) catalyzed hydroboration reaction of 2-acetylfuran and pinacol borane
In the reaction flask after dehydration and deoxidation treatment, 0.1 mL of catalyst [2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Yb-BH4 .2THF in toluene (0.01M) was added followed by pinacolborane (0.145 mL, 1mmol) by syringe and 2-acetylfuran (1 mmol) by syringe. After 5min of reaction, 0.5mL CDCl was added3The product was obtained in 91% nuclear magnetic yield. Nuclear magnetic data of the product:1H NMR (400 MHz,CDCl3): 7.33 (s, 1H), 6.28(m, 1H), 6.23(m, 1H, C4H3O), 5.24 (q,J=6.4Hz, 1H,CH), 1.54 (d,J=6.4, 3H, CH3), 1.25(s, 12H, CH3).11B NMR (128 MHz, CDCl3):22.21 ppm。
example ten: [2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Sm-BH4 .2THF (tetrahydrofuran) catalyzed hydroboration reaction of 2-acetylfuran and pinacol borane
In the reaction flask after dehydration and deoxidation treatment, 0.3 mL of catalyst [2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Sm-BH4 .2THF in toluene (0.01M), then pinacolborane (0.145 mL, 1mmol) was added by syringe, 2-acetylfuran (1 mmol) was added by syringe, after 10min of reaction, 0.5mL CDCl was added3The product was obtained with a nuclear magnetic yield of 95%. The nuclear magnetic data of the product are the same as in example nine.
Example eleven: [2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Yb-BH4 .2THF (tetrahydrofuran) is used for catalyzing hydroboration reaction of 2-acetylthiophene and pinacol borane
In the reaction flask after dehydration and deoxidation treatment, 0.1 mL of catalyst [2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Yb-BH4 .2THF in toluene (0.01M), then pinacolborane (0.145 mL, 1mmol) was added by syringe, followed by 2-ethaneAcylthiophene (1 mmol). After 10min of reaction, 0.5mL CDCl was added3The product was obtained in a nuclear magnetic yield of 94%. Nuclear magnetic data of the product:1H NMR (CDCl3,400 MHz): 7.18 (m, 1H), 6.95(m, 1H), 6.91(m, 1H, C4H3S), 5.48 (q,J=6.4Hz, 1H,CH), 1.59 (d,J=6.4, 3H, CH3), 1.24 + 1.23(two s, 6H each).11B NMR (128 MHz,CDCl3):: 22.19 ppm。
example twelve: [2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Sm-BH4 .2THF (tetrahydrofuran) is used for catalyzing hydroboration reaction of 2-naphthyl ethyl ketone and pinacol borane
In the reaction flask after dehydration and deoxidation treatment, 0.5mL of catalyst [2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Sm-BH4 .2THF in toluene (0.01M), then pinacolborane (0.145 mL, 1mmol) was added with syringe and 2-naphthaleneacetone 1mmol was added with syringe, after 10min reaction, 0.5mL CDCl was added3The product was obtained in a nuclear magnetic yield of 93%.
The reactions of the invention are all carried out at room temperature, and according to the results of the examples, the β -diimine divalent rare earth borohydride complex disclosed by the invention has the advantages of high efficiency in catalyzing the hydroboration reaction of borane and ketone, little catalyst dosage, mild reaction and wide substrate application range, and is an efficient, simple and mild method for preparing borate.
Claims (1)
1. A method for synthesizing boric acid ester comprises the following steps of adding a toluene solution of a catalyst into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon, adding pinacolborane into an injector, adding ketone into the reaction bottle by using the injector, reacting at room temperature for 10min, and adding CDCl3Terminating the reaction, decompressing the reaction liquid to remove the solvent, and adding the residual liquid into n-hexane to obtain boric acid ester; the molecular structural formula of the catalyst is as followsShown in the figure:
the Ln is selected from one of ytterbium and samarium; the ketone R1OCR2Is acetophenone or o-methylacetophenone, p-methylacetophenone, o-chloroacetophenone, p-chloroacetophenone, 2-acetylfuran, 2-acetylthiophene, 2-naphthylethanone; the amount of the catalyst is 0.1-0.5% of the mole number of the ketone; the molar ratio of the used amount of borane to the used amount of ketone is 1: 1; the temperature of the reaction is room temperature; the method is represented as follows:
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| CN107540700B (en) * | 2017-09-15 | 2019-06-25 | 苏州大学 | The method for preparing borate using three fragrant oxygen rare earth compoundings |
| CN107602594B (en) * | 2017-09-27 | 2019-09-03 | 南京林业大学 | A kind of asymmetry beta-diimine monovalence magnesium complex and preparation method thereof and the application in the hydroboration of nitrile |
| CN107602595B (en) * | 2017-09-27 | 2019-09-03 | 南京林业大学 | A kind of beta-diimine monovalence magnesium compound and preparation method thereof and the application in aldehyde ketone hydroboration |
| CN107840857B (en) * | 2017-10-19 | 2020-05-29 | 杭州师范大学 | Silicon cyanation reaction method for catalyzing ketone by borohydride |
| CN108191891B (en) * | 2018-01-09 | 2019-11-05 | 南京林业大学 | Asymmetric beta-diimine monovalence magnesium compound and its preparation method and application |
| 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 |
| CN111747972A (en) * | 2020-06-16 | 2020-10-09 | 苏州大学 | Deprotonated beta-ketimine lithium compound and preparation method thereof |
| CN111807998B (en) * | 2020-07-31 | 2022-07-26 | 苏州大学 | Chiral ligand and application thereof in catalytic preparation of optically active secondary alcohol |
| CN113680389B (en) * | 2021-08-20 | 2023-09-05 | 安徽师范大学 | Multidentate beta-diimine ligand rare earth metal catalyst and preparation method and application thereof |
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