CN108570065A - The method for synthesizing borate based on β-di-imidogen bivalent rare earth boron hydrogen complex - Google Patents
The method for synthesizing borate based on β-di-imidogen bivalent rare earth boron hydrogen complex Download PDFInfo
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- CN108570065A CN108570065A CN201810532922.5A CN201810532922A CN108570065A CN 108570065 A CN108570065 A CN 108570065A CN 201810532922 A CN201810532922 A CN 201810532922A CN 108570065 A CN108570065 A CN 108570065A
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- borine
- ketone
- rare earth
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- imidogen
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- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims abstract description 10
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 5
- 229910052761 rare earth metal Inorganic materials 0.000 title abstract description 28
- 150000002910 rare earth metals Chemical class 0.000 title abstract description 28
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title abstract description 22
- 229910052796 boron Inorganic materials 0.000 title abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title abstract description 20
- 239000001257 hydrogen Substances 0.000 title abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 title abstract description 20
- 229910000085 borane Inorganic materials 0.000 claims abstract description 53
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 150000002576 ketones Chemical class 0.000 claims abstract description 30
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical group CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims description 56
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 claims description 31
- 239000003054 catalyst Substances 0.000 claims description 28
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical group CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 14
- IEMMBWWQXVXBEU-UHFFFAOYSA-N 2-acetylfuran Chemical class 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
- WYJOVVXUZNRJQY-UHFFFAOYSA-N 2-Acetylthiophene Chemical class CC(=O)C1=CC=CS1 WYJOVVXUZNRJQY-UHFFFAOYSA-N 0.000 claims description 6
- NRNHJIRMWBDTJE-UHFFFAOYSA-N pentan-3-one;toluene Chemical compound CCC(=O)CC.CC1=CC=CC=C1 NRNHJIRMWBDTJE-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
- GNKZMNRKLCTJAY-UHFFFAOYSA-N 4'-Methylacetophenone Chemical compound CC(=O)C1=CC=C(C)C=C1 GNKZMNRKLCTJAY-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000011261 inert gas 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
- 238000000605 extraction Methods 0.000 claims 1
- IMACFCSSMIZSPP-UHFFFAOYSA-N phenacyl chloride Chemical compound ClCC(=O)C1=CC=CC=C1 IMACFCSSMIZSPP-UHFFFAOYSA-N 0.000 claims 1
- 238000006197 hydroboration reaction Methods 0.000 abstract description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 3
- 229910052747 lanthanoid Inorganic materials 0.000 abstract description 2
- 238000012805 post-processing Methods 0.000 abstract description 2
- 229910000071 diazene Inorganic materials 0.000 abstract 1
- 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 15
- 229910052786 argon Inorganic materials 0.000 description 12
- 230000018044 dehydration Effects 0.000 description 12
- 238000006297 dehydration reaction Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 238000002347 injection Methods 0.000 description 12
- 239000007924 injection Substances 0.000 description 12
- 230000005311 nuclear magnetism Effects 0.000 description 12
- 230000008859 change Effects 0.000 description 9
- 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
- 238000004607 11B NMR spectroscopy Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 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
- 239000012327 Ruthenium complex Substances 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
- GJSJZQZEDAUFBH-UHFFFAOYSA-N benzene;pentan-3-one Chemical compound CCC(=O)CC.C1=CC=CC=C1 GJSJZQZEDAUFBH-UHFFFAOYSA-N 0.000 description 1
- 229960002645 boric acid Drugs 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- -1 boric acid ester Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 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
- 238000004519 manufacturing process Methods 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
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
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
- B01J31/2204—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
Landscapes
- 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 kind of methods synthesizing borate based on β-di-imidogen bivalent rare earth boron hydrogen complex, utilize β-diimine lanthanide dichloride and NaBH4It is reacted in tetrahydrofuran solvent, and restores by Na/K in situ to obtain β-di-imidogen bivalent rare earth boron hydrogen complex：[2,6‑ipr2‑(C6H3)‑NC(Me)CHC(Me)N‑(C6H3)‑2,6‑ipr2]Ln‑BH4 .2THF.β disclosed by the invention-di-imidogen bivalent rare earth boron hydrogen complex can be catalyzed to high activity the hydroboration of borine and ketone under mild conditions, have the reaction time short, and reaction condition is mild, and post-processing approach is simply, conveniently.
Description
The present invention is that entitled β-di-imidogen bivalent rare earth boron hydrogen complex is anti-in catalysis ketone and borine hydroboration
Application, the applying date in answering are on June 30th, 2016, application No. is the divisional applications of 201610501609.6 patents of invention, are belonged to
In the preparation method part of compound.
Technical field
The present invention relates to a kind of catalysis of rare earth metal complex to react, and in particular to a kind of β-di-imidogen bivalent rare earth boron
Application of the hydrogen complex in the hydroboration of catalysis borine and ketone.
Background technology
The application of borate has obtained quick development, as trimethylborate is largely used to prepare high-energy fuel；In addition,
It also serves as the stabilizer etc. in the antifriction anti-friction additive, rubber-metal bonding accelerating agent, polymer of lubricating oil；Therefore, have
The synthesis of machine borate is always research hotspot.Borine and carbonyls（Such as ketone）Reduction reaction, be synthesis containing not
With most direct, most atom economy the method for the borate of substituent group.But the reaction is reacted in the absence of a catalyst
Condition is harsher.Therefore, new catalyst system and catalyzing is explored, can be mild, efficiently synthesizing the demand of organic boric acid ester becomes more
Urgently.Document report is less about the catalyst system and catalyzing of the hydroboration of carbonyls and borine at present, mainly there is monoborane
（Diborane）, metal oxide and metallo-organic compound etc.；As one kind of catalyst system and catalyzing, metallo-organic compound passes through
Being self-assembly of one kind, there is functional catalyst to have obtained extensive utilization.The metal for being catalyzed the reaction reported is organic
Compound has：Main group metal complexes, the second B metal Zn complex, transition metal molybdenum, titanium and ruthenium complex.In the modern times
In Organolanthanide Chemistry, the rare earth metal complex of self assembly because with unique texture ligand and efficiently controllable draw
Hair group becomes the catalyst system and catalyzing of a kind of high activity, up to the present also finds no about catalyzed by rare-earth complex borine
With the report of the hydroboration of carbonyls this one kind cooperation is expanded in view of the catalytic effect of such complex high activity
The application of object not only has significant application value, while also having important theory significance to the research of organic boron chemistry.
Invention content
The object of the present invention is to provide a kind of β-di-imidogen bivalent rare earth boron hydrogen complexs in the boron for being catalyzed borine and ketone
Application in hydrogenation.
In order to achieve the above objectives, the technical solution adopted by the present invention is：β-di-imidogen bivalent rare earth boron hydrogen complex exists
The application being catalyzed in the hydroboration of borine and ketone；The molecular structural formula of the β-di-imidogen bivalent rare earth boron hydrogen complex
As follows:
Wherein Ln is rare earth metal ytterbium or samarium.
The molecular formula of above-mentioned β-di-imidogen bivalent rare earth boron hydrogen complex is represented by： [2,6-ipr2-(C6H3)-NC
(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Ln-BH4 .2THF, Ln indicate rare earth metal, in the ytterbium, samarium in lanthanide series
One kind, THF is tetrahydrofuran.
Above-mentioned β-di-imidogen bivalent rare earth boron hydrogen complex can be catalyzed the hydroboration of borine and ketone, the borine
For pinacol borine；The ketone be acetophenone or o-methyl-benzene ethyl ketone, melilotal, o-chloroacetophenone, to chlorobenzene second
Ketone, 2- acetyl furans, 2- acetyl thiophenes, 2- acetonaphthones.
In above-mentioned technical proposal, in molar ratio, β-di-imidogen bivalent rare earth boron hydrogen complex: ketone: borine is（0.1~
0.5%）∶1∶1.
In above-mentioned technical proposal, the temperature of the hydroboration is room temperature, and the reaction time is 5~15 minutes.
The invention also discloses the hydroborations of β-di-imidogen bivalent rare earth boron hydrogen complex catalysis borine and ketone
Method includes the following steps：
Under the conditions of anhydrous and oxygen-free, in an inert gas atmosphere, catalyst, borine are uniformly mixed with ketone successively；5~15 points of reaction
Clock；Use CDCl3Reaction is terminated, solvent is removed under reduced pressure in reaction solution, and n-hexane is added in raffinate（3×2 mL）It is molten to take away higher boiling
Agent obtains product, is different substituted boracic acid esters；The catalyst is β-di-imidogen bivalent rare earth boron hydrogen complex.
In above-mentioned technical proposal, the borine is pinacol borine；The ketone is acetophenone or o-methyl-benzene ethyl ketone, right
Methyl acetophenone, o-chloroacetophenone, parachloroacetophenone, 2- acetyl furans, 2- acetyl thiophenes, 2- acetonaphthones；The catalysis
The amount of agent is the 0.1~0.5% of ketone molal quantity；The dosage of borine and the molar ratio of ketone dosage are 1:1；The temperature of the reaction is
Room temperature.
The present invention further discloses a kind of methods of synthesis borate, under the conditions of anhydrous and oxygen-free, in inert gas atmosphere
In, catalyst, borine are uniformly mixed with ketone successively；Reaction 5~15 minutes；Use CDCl3Reaction is terminated, reaction solution is removed under reduced pressure
N-hexane is added in solvent, raffinate（3×2 mL）To take away high boiling solvent, product is obtained, is different substituted boracic acid esters；It is described
Catalyst is β-di-imidogen bivalent rare earth boron hydrogen complex.
In above-mentioned technical proposal, the borine is pinacol borine；The ketone is acetophenone or o-methyl-benzene ethyl ketone, right
Methyl acetophenone, o-chloroacetophenone, parachloroacetophenone, 2- acetyl furans, 2- acetyl thiophenes, 2- acetonaphthones；The catalysis
The amount of agent is the 0.1~0.5% of ketone molal quantity；The dosage of borine and the molar ratio of ketone dosage are 1:1；The temperature of the reaction is
Room temperature.
Above-mentioned technical proposal can indicate as follows：
R1、R2Come from raw ketone.
Since above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：
1. the present invention is for the first time with the hydroboration of catalyzed by rare-earth complex borine and ketone, a kind of new and effective to develop
It is catalyzed rare-earth metal catalyst-β-di-imidogen bivalent rare earth boron hydrogen complex of hydroboration；Rare earth has not only been expanded to match
Close the application of object, and the method for enriching the hydroboration of borine and ketone.
2. β disclosed by the invention-di-imidogen bivalent rare earth boron hydrogen complex can be in a mild condition（Room temperature）Height is living
Property catalysis ketone and borine synthesize borate, compared with several catalyst of document report, in the case where reaching identical yield,
Catalyst amount only needs the 0.1~0.5% of ketone mole；Reaction time is very short, and it can must be more than 90% receipts to react 5 minutes highests
Rate, reaction efficiency are high.
3. β disclosed by the invention-di-imidogen bivalent rare earth boron hydrogen complex is wide to the scope of application of substrate, it is suitable for
Different substituents position, different electronic effect ketone；And reaction process is simply controllable, high income, and product postprocessing is easy, and fits
Close industrialized production.
Specific implementation mode
With reference to embodiment, the invention will be further described：
Embodiment one：[2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Yb-BH4 .2THF is catalyzed benzene
Ethyl ketone and pinacol borine hydroboration
In by the processed reaction bulb of dehydration and deoxidation, 0.1 mL catalyst [2,6- is added under protection of argon gasipr2-
(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Yb-BH4 .The toluene solution (0.01 M) of 2THF, then with injection
Pinacol borine (0.145 mL, 1 mmol) is added in device, then acetophenone (0.117 mL, 1 mmol) is added with syringe.Instead
After answering 5 min, 0.5 mL CDCl are added3, it is 90% corresponding pinacol borate, C to obtain nuclear-magnetism yield6H5CH(CH3)OB(OC
(CH3)2C(CH3)2O).The nuclear magnetic data of 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。
Embodiment two：[2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Sm-BH4 .2THF is urged
Change acetophenone and pinacol borine hydroboration
In by the processed reaction bulb of dehydration and deoxidation, 0.1 mL catalyst [2,6- is added under protection of argon gasipr2-
(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Sm-BH4 .The toluene solution (0.01 M) of 2THF, then with injection
Pinacol borine (0.145 mL, 1 mmol) is added in device, then acetophenone (0.117 mL, 1 mmol) is added with syringe, instead
After answering 10 min, 0.5 mL CDCl are added3, it is 92% corresponding pinacol borate, C to obtain nuclear-magnetism yield6H5CH(CH3)OB(OC
(CH3)2C(CH3)2O).The nuclear magnetic data of product is the same as embodiment one.
Embodiment three：[2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Sm-BH4 .2THF is urged
Change o-methyl-benzene ethyl ketone and pinacol borine hydroboration
In by the processed reaction bulb of dehydration and deoxidation, 0.1 mL catalyst [2,6- is added under protection of argon gasipr2-
(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Sm-BH4 .The toluene solution (0.01 M) of 2THF, then with injection
Device is added pinacol borine (0.145 mL, 1 mmol), then with syringe be added o-methyl-benzene ethyl ketone (0.131 mL, 1
mmol).After reacting 10 min, 0.5 mL CDCl are added3, it is 91% corresponding pinacol borate, C to obtain nuclear-magnetism yield6H5CH
(CH3)OB(OC(CH3)2C(CH3)2O).The nuclear magnetic data of 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 IV：[2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Sm-BH4 .2THF is urged
Change o-chloroacetophenone and pinacol borine hydroboration
In by the processed reaction bulb of dehydration and deoxidation, 0.1 mL catalyst [2,6- is added under protection of argon gasipr2-
(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Sm-BH4 .The toluene solution (0.01 M) of 2THF, then with injection
Device be added pinacol borine (0.145 mL, 1 mmol), then with syringe be added o-chloroacetophenone (0.130 mL, 1
mmol).After reacting 10 min, 0.5 mL CDCl are added3, it is 99% corresponding pinacol borate, C to obtain nuclear-magnetism yield6H5CH
(CH3)OB(OC(CH3)2C(CH3)2O).The nuclear magnetic data of 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。
Embodiment five：[2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2] Sm-BH4 .2THF is urged
Change melilotal and pinacol borine hydroboration
In by the processed reaction bulb of dehydration and deoxidation, 0.1 mL catalyst [2,6- is added under protection of argon gasipr2-
(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Sm-BH4 .The toluene solution (0.01 M) of 2THF, then with injection
Device be added pinacol borine (0.145 mL, 1 mmol), then with syringe be added melilotal (0.135 mL, 1
mmol).After reacting 10 min, 0.5 mL CDCl are added3, it is 92% corresponding pinacol borate, C to obtain nuclear-magnetism yield6H5CH
(CH3)OB(OC(CH3)2C(CH3)2O).The nuclear magnetic data of 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。
Embodiment six：[2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Sm-BH4 .2THF is urged
Change parachloroacetophenone and pinacol borine hydroboration
In by the processed reaction bulb of dehydration and deoxidation, 0.1 mL catalyst [2,6- is added under protection of argon gasipr2-
(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Sm-BH4 .The toluene solution (0.01 M) of 2THF, then with injection
Device be added pinacol borine (0.145 mL, 1 mmol), then with syringe be added parachloroacetophenone (0.130 mL, 1
mmol).After reacting 10 min, 0.5 mL CDCl are added3, it is 97% corresponding pinacol borate, C to obtain nuclear-magnetism yield6H5CH
(CH3)OB(OC(CH3)2C(CH3)2O).The nuclear magnetic data of 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. 11B
NMR (128 MHz, CDCl3): 25.6 ppm。
Embodiment seven：[2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Yb-BH4 .2THF is urged
Change parachloroacetophenone and pinacol borine hydroboration
In by the processed reaction bulb of dehydration and deoxidation, 0.3 mL catalyst [2,6- is added under protection of argon gasipr2-
(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Yb-BH4 .The toluene solution (0.01 M) of 2THF, then with injection
Device be added pinacol borine (0.145 mL, 1 mmol), then with syringe be added parachloroacetophenone (0.130 mL, 1
mmol).After reacting 10 min, 0.5 mL CDCl are added3, it is 97% corresponding pinacol borate, C to obtain nuclear-magnetism yield6H5CH
(CH3)OB(OC(CH3)2C(CH3)2O).The nuclear magnetic data of product is the same as embodiment six.
Embodiment eight：[2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2] Sm-BH4 .2THF is urged
Change parachloroacetophenone and pinacol borine hydroboration
In by the processed reaction bulb of dehydration and deoxidation, 0.5 mL catalyst [2,6- is added under protection of argon gasipr2-
(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Sm-BH4 .The toluene solution (0.01 M) of 2THF, then with injection
Device be added pinacol borine (0.145 mL, 1 mmol), then with syringe be added parachloroacetophenone (0.130 mL, 1
mmol).After reacting 10 min, 0.5 mL CDCl are added3, it is 98% corresponding pinacol borate, C to obtain nuclear-magnetism yield6H5CH
(CH3)OB(OC(CH3)2C(CH3)2O).The nuclear magnetic data of product is the same as embodiment six.
Embodiment nine：[2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Yb-BH4 .2THF is urged
Change 2- acetyl furans and pinacol borine hydroboration
In by the processed reaction bulb of dehydration and deoxidation, 0.1 mL catalyst [2,6- is added under protection of argon gasipr2-
(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Yb-BH4 .The toluene solution (0.01 M) of 2THF, then with injection
Pinacol borine (0.145 mL, 1 mmol) is added in device, then 2- acetyl furans (1 mmol) are added with syringe.Reaction 5
After min, 0.5 mL CDCl are added3, obtain the product that nuclear-magnetism yield is 91%.The nuclear magnetic data of 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。
Embodiment ten：[2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Sm-BH4 .2THF is urged
Change 2- acetyl furans and pinacol borine hydroboration
In by the processed reaction bulb of dehydration and deoxidation, 0.3 mL catalyst [2,6- is added under protection of argon gasipr2-
(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Sm-BH4 .The toluene solution (0.01 M) of 2THF, then with injection
Pinacol borine (0.145 mL, 1 mmol) is added in device, then 2- acetyl furans (1 mmol), reaction is added with syringe
After 10min, 0.5 mL CDCl are added3, obtain the product that nuclear-magnetism yield is 95%.The nuclear magnetic data of product is the same as embodiment nine.
Embodiment 11：[2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Yb-BH4 .2THF
It is catalyzed 2- acetyl thiophenes and pinacol borine hydroboration
In by the processed reaction bulb of dehydration and deoxidation, 0.1 mL catalyst [2,6- is added under protection of argon gasipr2-
(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Yb-BH4 .The toluene solution (0.01 M) of 2THF, then with injection
Pinacol borine (0.145 mL, 1 mmol) is added in device, then 2- acetyl thiophenes (1 mmol) are added with syringe.Reaction
After 10min, 0.5 mL CDCl are added3, obtain the product that nuclear-magnetism yield is 94%.The nuclear magnetic data of 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。
Embodiment 12：[2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Sm-BH4 .2THF
It is catalyzed 2- acetonaphthones and pinacol borine hydroboration
In by the processed reaction bulb of dehydration and deoxidation, 0.5mL catalyst [2,6- is added under protection of argon gasipr2-
(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Sm-BH4 .The toluene solution (0.01 M) of 2THF, then with injection
Pinacol borine (0.145 mL, 1 mmol) is added in device, then 1 mmol of 2- acetonaphthones is added with syringe), react 10 min
Afterwards, 0.5 mL CDCl are added3, obtain the product that nuclear-magnetism yield is 93%.
The reaction of the present invention all carries out at room temperature, result according to the embodiment, it can be verified that β-two disclosed by the invention
The hydroboration efficiency that imido grpup bivalent rare earth boron hydrogen complex is catalyzed borine and ketone is very high, and catalyst amount it is few,
Reaction is mild, wide application range of substrates, is a kind of method for preparing borate efficiently, simple, mild.
Claims (2)
1. a kind of method of synthesis borate, includes the following steps, under the conditions of anhydrous and oxygen-free, in an inert gas atmosphere, successively
Catalyst, borine are uniformly mixed with ketone；Reaction 5~15 minutes；Use CDCl3Reaction is terminated, solvent is removed under reduced pressure in reaction solution, remains
Extraction raffinate is added in n-hexane, obtains borate；The molecular structural formula of the catalyst is as follows:
。
2. the method for synthesizing borate according to claim 1, it is characterised in that：The one kind of the Ln in ytterbium, samarium；Institute
It is pinacol borine to state borine；The ketone is acetophenone or o-methyl-benzene ethyl ketone, melilotal, o-chloroacetophenone, right
Chloro-acetophenone, 2- acetyl furans, 2- acetyl thiophenes, 2- acetonaphthones；The amount of the catalyst be ketone molal quantity 0.1~
0.5%；The dosage of borine and the molar ratio of ketone dosage are 1:1；The temperature of the reaction is room temperature.
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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 |
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