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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- 238000000034 method Methods 0.000 title claims abstract description 11
- -1 boric acid ester Chemical class 0.000 title claims abstract description 8
- 239000004327 boric acid Substances 0.000 title claims abstract description 6
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 6
- 229910052761 rare earth metal Inorganic materials 0.000 title abstract description 30
- 150000002910 rare earth metals Chemical class 0.000 title abstract description 29
- 229910000071 diazene Inorganic materials 0.000 title abstract description 21
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title abstract description 18
- 229910052796 boron Inorganic materials 0.000 title abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title abstract description 16
- 239000001257 hydrogen Substances 0.000 title abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 title abstract description 16
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 150000002576 ketones Chemical class 0.000 claims abstract description 29
- 229910000085 borane Inorganic materials 0.000 claims abstract description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 claims description 29
- LZPWAYBEOJRFAX-UHFFFAOYSA-N 4,4,5,5-tetramethyl-1,3,2$l^{2}-dioxaborolane Chemical compound CC1(C)O[B]OC1(C)C LZPWAYBEOJRFAX-UHFFFAOYSA-N 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 26
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 16
- 230000018044 dehydration Effects 0.000 claims description 13
- 238000006297 dehydration reaction Methods 0.000 claims description 13
- YXWWHNCQZBVZPV-UHFFFAOYSA-N 2'-methylacetophenone Chemical compound CC(=O)C1=CC=CC=C1C YXWWHNCQZBVZPV-UHFFFAOYSA-N 0.000 claims description 12
- GNKZMNRKLCTJAY-UHFFFAOYSA-N 4'-Methylacetophenone Chemical compound CC(=O)C1=CC=C(C)C=C1 GNKZMNRKLCTJAY-UHFFFAOYSA-N 0.000 claims description 12
- BUZYGTVTZYSBCU-UHFFFAOYSA-N 1-(4-chlorophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Cl)C=C1 BUZYGTVTZYSBCU-UHFFFAOYSA-N 0.000 claims description 10
- WYJOVVXUZNRJQY-UHFFFAOYSA-N 2-Acetylthiophene Chemical compound CC(=O)C1=CC=CS1 WYJOVVXUZNRJQY-UHFFFAOYSA-N 0.000 claims description 10
- IEMMBWWQXVXBEU-UHFFFAOYSA-N 2-acetylfuran Chemical compound CC(=O)C1=CC=CO1 IEMMBWWQXVXBEU-UHFFFAOYSA-N 0.000 claims description 8
- ZDOYHCIRUPHUHN-UHFFFAOYSA-N 1-(2-chlorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC=C1Cl ZDOYHCIRUPHUHN-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- XSAYZAUNJMRRIR-UHFFFAOYSA-N 2-acetylnaphthalene Chemical compound C1=CC=CC2=CC(C(=O)C)=CC=C21 XSAYZAUNJMRRIR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 239000007788 liquid Substances 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
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- 229910052786 argon Inorganic materials 0.000 claims 1
- 238000006197 hydroboration reaction Methods 0.000 abstract description 26
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract description 25
- 230000000694 effects Effects 0.000 abstract description 5
- 230000035484 reaction time Effects 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 239000012279 sodium borohydride Substances 0.000 abstract 1
- 229910000033 sodium borohydride Inorganic materials 0.000 abstract 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 11
- BMQDAIUNAGXSKR-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid Chemical compound CC(C)(O)C(C)(C)OB(O)O BMQDAIUNAGXSKR-UHFFFAOYSA-N 0.000 description 8
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 238000004607 11B NMR spectroscopy Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 150000001728 carbonyl compounds Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QLYPHTMKMPIJNG-UHFFFAOYSA-N 1-naphthalen-2-ylpropan-1-one Chemical compound C1=CC=CC2=CC(C(=O)CC)=CC=C21 QLYPHTMKMPIJNG-UHFFFAOYSA-N 0.000 description 1
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
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- 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
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
-
- 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
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/04—Esters of boric acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- 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
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
-
- 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)
- Catalysts (AREA)
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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