CN108329338A - A method of preparing borate - Google Patents

A method of preparing borate Download PDF

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CN108329338A
CN108329338A CN201810085946.0A CN201810085946A CN108329338A CN 108329338 A CN108329338 A CN 108329338A CN 201810085946 A CN201810085946 A CN 201810085946A CN 108329338 A CN108329338 A CN 108329338A
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aldehyde
borine
catalyst
syringe
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CN108329338B (en
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薛明强
朱章野
洪玉标
沈琪
郑煜
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Suzhou University
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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
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
    • B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
    • B01J2231/342—Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones
    • B01J2231/344—Boronation, e.g. by adding R-B(OR)2
    • 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
    • B01J2531/30—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)

Abstract

The invention discloses a kind of method preparing borate, specially two (beta diimine base) ytterbiums are the hydroboration of catalyst aldehyde and borine, and the molecular formula of catalyst is [2 Me C6H4‑NC(Me)CHC(Me)N‑C6H4‑2‑Me]2Ln‑N(SiMe3)2, Ln indicates rare earth metal, is selected from Nd, and one kind in Pr is used as catalyst in borine and aldehyde reaction generate borate, can be under mild conditions（Room temperature）, with the extremely short time（5 10 minutes）, with aldehyde hydroboration occurs for high yield catalysis borine, to be the first using such reaction of catalysis of rare-earth compound.

Description

A method of preparing borate
The present invention is entitled two (beta-diimine base) ytterbiums in catalysis aldehyde and borine hydroboration Application, the applying date be on June 30th, 2016, application No. is the divisional application of 201610502173.2 patent applications, belonging to Close the technology of preparing part of object.
Technical field
A kind of application of two (beta-diimine base) ytterbium of the present invention, and in particular to side preparing borate Method.
Technical background
Since Ebelman and Bouquet in 1846 has synthesized organoboron compound first, organic boron chemistry has one More than hundred years developing history, especially nearest decades, organoboron compound has obtained rapid development.Organic boric acid ester has The features such as nontoxic, environmental-friendly, performance is stablized.Organic boric acid ester can be used not only as fluxing in plasticizer, welding process A kind of important raw material in agent, flame retardant for textile, coupling agent, lube oil additive etc. and organic synthesis.For example, utilizing Carbonyls generates borate with borine equivalent reaction, and then hydrolysis obtains alcohol, is a kind of method efficiently synthesizing alcohol (Abdulafeez A. Oluyadi; Shuhua Ma; and Clare N. Muhoro, Organometallics2013,32, 70-78).Therefore, it is still the hot spot of chemist research for the synthesis of borate.
Borine and carbonyls 1:Hydroboration occurs for 1 equivalent, is a kind of method of direct synthesis borate, and With Atom economy.But research shows that in the case of no catalyst, some borines（Such as pinacol borine）It is difficult to occur Hydroboration, that is reported on document at present reacts the catalytic body owner of synthesis borate about catalysis borine with carbonyls If about Main group metal complexes and transient metal complex（Referring to：Zhi Yang; Mingdong Zhong; Xiaoli Ma; Susmita De; Chakkittakandiyil Anusha; Pattiyil Parameswaran; Herbert W. Roesky, Angew. Chem. Int. Ed. 2015, 54 ；Terrance J. Hadlington; Markus Hermann; Gernot Frenking; Cameron Jones, J. Am. Chem. Soc. 2014, 136, 3028−3031).So far, as catalyst, such reaction yet there are no report to rare earth metal complex, also have no To related two（Beta-diimine base）The report of hydroboration occurs for ytterbium catalysis of carbonyl chemical combination object and borine.
Invention content
The goal of the invention of the present invention is to provide a kind of application of two (beta-diimine base) rare earth silicon aminates, i.e., with two (β- Di-imidogen) ytterbium be effective catalyst catalysis of carbonyl chemical combination object（Aldehyde）Hydroboration occurs with borine.Utilize appearance Catalyst easily obtained, two (beta-diimine base) rare earth silicon aminates reduce catalyst sheet while providing high catalytic activity Body prepares difficulty, reduces post processing cost.
To achieve the above object of the invention, the technical solution adopted by the present invention is：Two (beta-diimine base) rare earth silicon aminates In catalysis aldehyde and the application in borine hydroboration；The chemical structural formula of described two (beta-diimine base) rare earth silicon aminate For：
The molecular formula of above-mentioned two (beta-diimine base) rare earth silicon aminate is represented by [2-Me-C6H4-NC(Me)CHC(Me)N- C6H4-2-Me]2Ln-N(SiMe3)2, Ln indicates the rare earth ion of positive trivalent, one kind in praseodymium or neodymium in formula.
The invention also discloses the sides of two (beta-diimine base) ytterbiums catalysis aldehyde and borine generation hydroboration Method includes the following steps：
Under anhydrous and oxygen-free environment, in atmosphere of inert gases, catalyst [2- is added in the reaction bulb by dehydration and deoxidation processing Me-C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Ln-N(SiMe3)2, aldehyde is then added, is uniformly mixed, adds borine, 5 ~ 10 min are reacted, CDCl is used3Reaction is terminated, solvent is removed under reduced pressure in reaction solution, and raffinate adds hexane（3×5 ml）It washes It washs, obtains product.
The invention also discloses two (beta-diimine base) rare earth silicon aminates as catalyst answering in preparing borate With.
The present invention further discloses a kind of preparation method of borate, includes the following steps：
Under anhydrous and oxygen-free environment, in atmosphere of inert gases, catalyst [2- is added in the reaction bulb by dehydration and deoxidation processing Me-C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Ln-N(SiMe3)2, aldehyde is then added, is uniformly mixed, adds borine, 5 ~ 10 min are reacted, CDCl is used3Reaction is terminated, solvent is removed under reduced pressure in reaction solution, and raffinate adds hexane（3×5 ml）It washes It washs, obtains corresponding different substituted boracic acid esters.
In above-mentioned technical proposal, the aldehyde is selected from aromatic aldehyde, and the chemical constitution of one kind in fatty aldehyde, the aromatic aldehyde is logical Formula is；Wherein R is one kind in electron-withdrawing group or electron donating group, can be selected from halogen, nitro, Dimethylamino, methyl, methoxyl group；The fatty aldehyde is selected from, acetaldehyde, isopentyl aldehyde, valeraldehyde, n-hexyl aldehyde；Borine is selected from pinacol Borine.The catalyst amount can be the 0.1~0.5% of aldehyde molal quantity, and the molar ratio of pinacol borine and aldehyde is 1: 1, react and be Temperature is room temperature, and the reaction time is that 5~10 min are differed.
Above-mentioned technical proposal can indicate as follows：
R1Come from reaction raw materials aldehyde.
Due to the application of the above technical scheme, the present invention has the following advantages compared with prior art：
1. the present invention uses catalyzing of rare-earth metal system catalysis aldehyde that hydroboration occurs with borine for the first time, to use carbonyl compound Object prepares borate with borine generation hydroboration and provides new scheme, has expanded two (beta-diimine base) ytterbiums Application.
2. with borine urging for hydroboration occurs for two (beta-diimine base) ytterbiums catalysis aldehyde disclosed by the invention It is high (catalyst amount only needs the 0.1 ~ 0.5% of aldehyde mole) to change activity, reaction condition is mild (room temperature), the reaction time it is short (5 ~ 10 min), and reaction efficiency is high, reaction is simple controllable, and post-processing is simple, reduces the pollution to environment.
3. catalyst disclosed by the invention is for the aromatic aldehyde of different the position of substitution, different electronic effects and to fatty aldehyde There is preferable universality, the boric acid ester compound to obtain different substituents structure provides more selections.
Specific implementation mode
The present invention is described further with reference to embodiment：
Embodiment one： [2-Me-C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Pr-N(SiMe3)2It is catalyzed benzaldehyde and frequently which Alcohol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, argon gas protection is lower to be added 0.0037 g catalyst) [2-Me-C6H4-NC (Me)CHC(Me)N-C6H4-2-Me]2Pr-N(SiMe3)2 (0.5% mole dosage, similarly hereinafter) is then added 0.081 with syringe ML benzaldehydes, catalyst dissolving, are uniformly mixed, then 0.116 mL pinacol borines are added with syringe, and mixture is at room temperature After reacting 10 min, 0.5 mLCDCl is added in stirring3, nuclear-magnetism yield is 99%, and CDCl is removed under reduced pressure later3And toluene, Yi Jiwei The aldehyde of reaction is added n-hexane (3 × 5 mL) and washs, drains, obtain corresponding pinacol borate C6H5CH2OB(OC(CH3)2C (CH3)2O).The nuclear magnetic data of product:1H NMR (CDCl3, 400 MHz): δ 7.33-7.20 (m, 5H, ArH), 4.91 (s, 2H, CH2), 1.23 (s, 12H, CH3). 11B{1H} NMR (CDCl3, 128 MHz): δ 22.50 (s, B-O)。
Embodiment two：[2-Me-C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Pr-N(SiMe3)2Be catalyzed benzaldehyde with Pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, under argon gas protection, 0.02 mL catalyst [2-Me- is added with syringe C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Pr-N(SiMe3)2 The toluene solution (0.02 M) of (0.1% dosage), is then used 0.040 mL benzaldehydes are added in syringe, stir evenly, then 0.058 mL pinacol borines are added with syringe, and mixture is in room The lower stirring of temperature, after reacting 10 min, is added 0.5 mLCDCl3, nuclear-magnetism yield is 97%, and CDCl is removed under reduced pressure later3And toluene, with And unreacted aldehyde, n-hexane (3 × 5 mL) is added and washs, drains, obtains corresponding pinacol borate C6H5CH2OB(OC (CH3)2C(CH3)2O).The nuclear magnetic data of product is the same as embodiment one.
Embodiment three：[2-Me-C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Nd-N(SiMe3)2Be catalyzed benzaldehyde with Pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, under argon gas protection, 0.02 mL catalyst [2-Me- is added with syringe C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Nd-N(SiMe3)2 The toluene solution (0.02 M) of (0.1% dosage), is then used 0.040 mL benzaldehydes are added in syringe, stir evenly, then 0.058 mL pinacol borines are added with syringe, and mixture is in room The lower stirring of temperature, after reacting 5 min, is added 0.5 mLCDCl3, nuclear-magnetism yield is 95%, and CDCl is removed under reduced pressure later3And toluene, with And unreacted aldehyde, n-hexane (3 × 5 mL) is added and washs, drains, obtains corresponding pinacol borate C6H5CH2OB(OC (CH3)2C(CH3)2O).The nuclear magnetic data of product is the same as embodiment one..
Example IV：[2-Me-C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Pr-N(SiMe3)2Catalysis is to fluorobenzene first Aldehyde and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, under argon gas protection, 0.02 mL catalyst [2-Me- is added with syringe C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]Pr-N(SiMe3)2 The toluene solution (0.02 M) of (0.1% dosage), is then used 0.043 mL 4-Fluorobenzaldehydes are added in syringe, stir evenly, then 0.058 mL pinacol borines, mixture is added with syringe It is stirred at room temperature, after reacting 10min, 0.5 mLCDCl is added3, nuclear-magnetism yield is 93%, and CDCl is removed under reduced pressure later3And first Benzene and unreacted aldehyde are added n-hexane (3 × 5mL) and wash, drains, obtain corresponding pinacol boratep-F- C6H4CH2OB(OC(CH3)2C(CH3)2O).The nuclear magnetic data of product:1H NMR (CDCl3, 400 MHz): δ 7.33-7.29 (m, 2H, ArH), 7.03-6.97 (m, 2H, ArH), 4.87 (s, 2H, CH2), 1.25(s, 12H, CH3).11B{1H} NMR (CDCl3, 128 MHz): δ 22.42 (s, B-O)。
Embodiment five： [2-Me-C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Nd-N(SiMe3)2Catalysis is to fluorobenzene first Aldehyde and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, under argon gas protection, 0.02 mL catalyst [2-Me- is added with syringe C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Nd-N(SiMe3)2 The toluene solution (0.02 M) of (0.1% dosage), is then used 0.043 mL 4-Fluorobenzaldehydes are added in syringe, stir evenly, then 0.058 mL pinacol borines, mixture is added with syringe It is stirred at room temperature, after reacting 10 min, 0.5 mLCDCl is added3, nuclear-magnetism yield is 90%, and CDCl is removed under reduced pressure later3And first Benzene and unreacted aldehyde are added n-hexane (3 × 5 mL) and wash, drains, obtain corresponding pinacol boratep-F- C6H4CH2OB(OC(CH3)2C(CH3)2O).The same example IV of nuclear magnetic data of product.
Embodiment six： [2-Me-C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Pr-N(SiMe3)2Chlorobenzene first between catalysis Aldehyde and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, under argon gas protection, 0.02 mL catalyst [2-Me- is added with syringe C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Pr-N(SiMe3)2 The toluene solution (0.02 M) of (0.1% dosage), is then used 0.045 mL m chlorobenzaldehydes are added in syringe, stir evenly, then 0.058 mL pinacol borines, mixture is added with syringe It is stirred at room temperature, after reacting 10 min, 0.5 mLCDCl is added3, nuclear-magnetism yield is 99%, and CDCl is removed under reduced pressure later3And first Benzene and unreacted aldehyde are added n-hexane (3 × 5 mL) and wash, drains, obtain corresponding pinacol boratem-Cl- C6H4CH2OB(OC(CH3)2C(CH3)2O)。
Embodiment seven： [2-Me-C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Nd-N(SiMe3)2Chlorobenzene first between catalysis Aldehyde and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, under argon gas protection, 0.02 mL catalyst [2-Me- is added with syringe C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Nd-N(SiMe3)2 The toluene solution (0.02 M) of (0.1% dosage), is then used 0.045 mL m chlorobenzaldehydes are added in syringe, stir evenly, then 0.058 mL pinacol borines, mixture is added with syringe It is stirred at room temperature, after reacting 10 min, 0.5 mLCDCl is added3, nuclear-magnetism yield is 93%, and CDCl is removed under reduced pressure later3And first Benzene and unreacted aldehyde are added n-hexane (3 × 5 mL) and wash, drains, obtain corresponding pinacol boratem-Cl- C6H4CH2OB(OC(CH3)2C(CH3)2O)。
Embodiment eight： [2-Me-C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Pr-N(SiMe3)2The adjacent chlorobenzene first of catalysis Aldehyde and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, under argon gas protection, 0.02 mL catalyst [2-Me- is added with syringe C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Pr-N(SiMe3)2 The toluene solution (0.02 M) of (0.1% dosage), is then used 0.045 mL o-chlorobenzaldehydes are added in syringe, stir evenly, then 0.058 mL pinacol borines, mixture is added with syringe It is stirred at room temperature, after reacting 10 min, 0.5 mLCDCl is added3, nuclear-magnetism yield is 99%, and CDCl is removed under reduced pressure later3And first Benzene and unreacted aldehyde are added n-hexane (3 × 5 mL) and wash, drains, obtain corresponding pinacol borateo-Cl- C6H4CH2OB(OC(CH3)2C(CH3)2O).The nuclear magnetic data of product:1H NMR (CDCl3, 400MHz): δ 7.51 (d, 1H, ArH), 7.34-7.17 (m, 3H, ArH), 5.02 (s, 2H, CH2), 1.27(s, 12H, CH3). 11B{1H} NMR (CDCl3, 128 MHz): δ 22.48 (s, B-O)。
Embodiment nine： [2-Me-C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Pr-N(SiMe3)2Catalysis is to chlorobenzene first Aldehyde and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, under argon gas protection, 0.02 mL catalyst [2-Me- is added with syringe C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Pr-N(SiMe3)2 The toluene solution (0.02 M) of (0.1% dosage), is then used 0.0647 g o-chlorobenzaldehydes are added in syringe, stir evenly, then 0.058 mL pinacol borines, mixture is added with syringe It is stirred at room temperature, after reacting 10 min, 0.5 mLCDCl is added3, nuclear-magnetism yield is 99%, and CDCl is removed under reduced pressure later3And first Benzene and unreacted aldehyde are added n-hexane (3 × 5 mL) and wash, drains, obtain corresponding pinacol boratep-Cl- C6H4CH2OB(OC(CH3)2C(CH3)2O)。
Embodiment ten： [2-Me-C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Pr-N(SiMe3)2Catalysis is to bromobenzene first Aldehyde and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, under argon gas protection, 0.02 mL catalyst [2-Me- is added with syringe C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]Pr-N(SiMe3)2 The toluene solution (0.02 M) of (0.1% dosage), is then used 0.040 g p-bromobenzaldehydes are added in syringe, stir evenly, then 0.058 mL pinacol borines, mixture is added with syringe It is stirred at room temperature, after reacting 10 min, 0.5 mLCDCl is added3, nuclear-magnetism yield is 99%, and CDCl is removed under reduced pressure later3And first Benzene and unreacted aldehyde are added n-hexane (3 × 5 mL) and wash, drains, obtain corresponding pinacol boratep-Br- C6H4CH2OB(OC(CH3)2C(CH3)2O)。
Embodiment 11： [2-Me-C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Pr-N(SiMe3)2Catalysis is to nitro Benzaldehyde and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, under argon gas protection, 0.02 mL catalyst [2-Me- is added with syringe C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Pr-N(SiMe3)2 The toluene solution (0.02 M) of (0.1% dosage), is then used 0.0604 g paranitrobenzaldehydes are added in syringe, stir evenly, then 0.058 mL pinacol borines, mixing is added with syringe Object is stirred at room temperature, and after reacting 10 min, 0.5 mLCDCl is added3, nuclear-magnetism yield is 99%, and CDCl is removed under reduced pressure later3With Toluene and unreacted aldehyde are added n-hexane (3 × 5 mL) and wash, drains, obtain corresponding pinacol boratep-NO2- C6H4CH2OB(OC(CH3)2C(CH3)2O)。
Embodiment 12：[2-Me-C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Pr-N(SiMe3)2It is catalyzed 4- diformazans Aminobenzaldehyde and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, under argon gas protection, 0.02 mL catalyst [2-Me- is added with syringe C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Pr-N(SiMe3)2 The toluene solution (0.02 M) of (0.1% dosage), is then used 0.0597 g 4- dimethylaminobenzaldehydes are added in syringe, stir evenly, then 0.058 mL pinacol boron is added with syringe Alkane, mixture are stirred at room temperature, and after reacting 10 min, 0.5 mLCDCl is added3, nuclear-magnetism yield is 99%, is removed under reduced pressure later CDCl3And toluene and unreacted aldehyde, addition n-hexane (3 × 5 mL) wash, drain, obtain corresponding pinacol boric acid Ester 4-Me2N-C6H4CH2OB(OC(CH3)2C(CH3)2O)。
Embodiment 13：[2-Me-C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Pr-N(SiMe3)2The adjacent methyl of catalysis Benzaldehyde and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, under argon gas protection, 0.02 mL catalyst [2-Me- is added with syringe C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Pr-N(SiMe3)2 The toluene solution (0.02 M) of (0.1% dosage), then again 0.046 mL o-tolualdehydes are added with syringe, stir evenly, then 0.058 mL pinacol borines are added with syringe, mix It closes object to be stirred at room temperature, after reacting 10min, 0.5 mLCDCl is added3, nuclear-magnetism yield is 99%, and CDCl is removed under reduced pressure later3With Toluene and unreacted aldehyde are added n-hexane (3 × 5 mL) and wash, drains, obtain corresponding pinacol borateo-Me- C6H4CH2OB(OC(CH3)2C(CH3)2O).The nuclear magnetic data of product:1H NMR (CDCl3, 400MHz): δ 7.41-7.38 (m, 1H, ArH), 7.19-7.13 (m, 3H, ArH), 4.93 (s, 2H, CH2), 2.31(s, 3H, CH3), 1.26(s, 12H, CH3). 11B{1H} NMR (CDCl3, 128 MHz): δ 22.48 (s, B-O)。
Embodiment 14：[2-Me-C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Pr-N(SiMe3)2Catalysis is to methyl Benzaldehyde and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, under argon gas protection, 0.02 mL catalyst [2-Me- is added with syringe C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Pr-N(SiMe3)2 The toluene solution (0.02 M) of (0.1% dosage), then again 0.047 mL p-tolyl aldehydes are added with syringe, stir evenly, then 0.058 mL pinacol borines are added with syringe, mix It closes object to be stirred at room temperature, after reacting 10 min, 0.5 mLCDCl is added3, nuclear-magnetism yield is 95%, and CDCl is removed under reduced pressure later3 And toluene and unreacted aldehyde, addition n-hexane (3 × 5 mL) wash, drain, obtain corresponding pinacol boratep- Me-C6H4CH2OB(OC(CH3)2C(CH3)2O).The nuclear magnetic data of product:1H NMR (CDCl3, 400MHz): δ 7.23 (d, 2H, ArH), 7.13 (d, 2H, ArH), 4.88 (s, 2H, CH2), 2.32(s, 3H, CH3), 1.25(s, 12H, CH3). 11B{1H} NMR (CDCl3, 128 MHz): δ 22.47 (s, B-O)。
Embodiment 15：[2-Me-C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Pr-N(SiMe3)2It is catalyzed 2,4,6- Trimethylbenzaldehyde and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, under argon gas protection, 0.02 mL catalyst [2-Me- is added with syringe C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Pr-N(SiMe3)2 The toluene solution (0.02 M) of (0.1% dosage), is then used 0.059 mL, 2,4,6- trimethylbenzaldehydes are added in syringe, stir evenly, then 0.058 mL pinacol boron is added with syringe Alkane, mixture are stirred at room temperature, and after reacting 10 min, 0.5 mLCDCl is added3, nuclear-magnetism yield is 99%, is removed under reduced pressure later CDCl3And toluene, n-hexane (3 × 5 mL) is then added and washs, drains, obtains corresponding pinacol borate 2,4,6-Me3- C6H4CH2OB(OC(CH3)2C(CH3)2O).The nuclear magnetic data of product:1H NMR (CDCl3, 400MHz): δ 6.81 (s, 2H, ArH), 4.94 (s, 2H, CH2), 2.37(s, 6H, CH3), 2.23(s, 3H, CH3), 1.24(s, 12H, CH3). 11B{1H} NMR (CDCl3, 128 MHz): δ 22.33 (s,B-O)。
Embodiment 16：[2-Me-C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Pr-N(SiMe3)2Catalysis is to methoxy Benzaldehyde and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, under argon gas protection, 0.02 mL catalyst [2-Me- is added with syringe C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Pr-N(SiMe3)2 The toluene solution (0.02 M) of (0.1% dosage), is then used 0.048 mL P-methoxybenzal-dehyde is added in syringe, stirs evenly, then 0.058 mL pinacol borines are added with syringe, mixes It closes object to be stirred at room temperature, after reacting 10 min, 0.5 mLCDCl is added3, nuclear-magnetism yield is 94%, and CDCl is removed under reduced pressure later3 And toluene, n-hexane (3 × 5 mL) is then added and washs, drains, obtains corresponding pinacol boratep-MeO-C6H4CH2OB (OC(CH3)2C(CH3)2O)。
Embodiment 17：[2-Me-C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Pr-N(SiMe3)2The adjacent methoxy of catalysis Benzaldehyde and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, under argon gas protection, 0.02 mL catalyst [2-Me- is added with syringe C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Pr-N(SiMe3)2 The toluene solution (0.02 M) of (0.1% dosage), is then used 0.048 mL o-methoxybenzaldehydes are added in syringe, stir evenly, then 0.058 mL pinacol borines are added with syringe, mix It closes object to be stirred at room temperature, after reacting 10min, 0.5 mLCDCl is added3, nuclear-magnetism yield is 94%, and CDCl is removed under reduced pressure later3With Then toluene is added n-hexane (3 × 5 mL) and washs, drains, obtain corresponding pinacol borateo-MeO-C6H4CH2OB(OC (CH3)2C(CH3)2O).The nuclear magnetic data of product:1H NMR (CDCl3, 400MHz): δ 7.41 (d, 1H, ArH), 7.29-7.21 (m, 1H, ArH), 6.95 (t, 1H, ArH), 6.83 (d, 1H, ArH), 4.99 (s, 2H, CH2), 3.80 (s, 3H, CH3), 1.27(s, 12H, CH3). 11B{1H} NMR (CDCl3, 128 MHz): δ 22.50 (s,B-O)。
Embodiment 18：[2-Me-C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Pr-N(SiMe3)2Be catalyzed acetaldehyde and Pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, under argon gas protection, 0.02 mL catalyst [2-Me- is added with syringe C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Pr-N(SiMe3)2 The toluene solution (0.02 M) of (0.1% dosage), is then used 0.016 mL acetaldehyde is added in syringe, stirs evenly, then 0.058 mL pinacol borines are added with syringe, and mixture is in room temperature After reacting 10 min, 0.5 mLCDCl is added in lower stirring3, nuclear-magnetism yield is 99%, and CDCl is removed under reduced pressure later3And toluene, then N-hexane (3 × 5 mL) is added to wash, drains, obtains corresponding pinacol borate CH3CH2OB(OC(CH3)2C(CH3)2O)。
Embodiment 19：[2-Me-C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Pr-N(SiMe3)2It is catalyzed n-hexyl aldehyde With pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, under argon gas protection, 0.02 mL catalyst [2-Me- is added with syringe C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Pr-N(SiMe3)2 The toluene solution (0.02 M) of (0.1% dosage), is then used 0.049 mL n-hexyl aldehydes are added in syringe, stir evenly, then 0.058 mL pinacol borines are added with syringe, and mixture is in room The lower stirring of temperature, after reacting 10 min, is added 0.5 mLCDCl3, nuclear-magnetism yield is 99%, and CDCl is removed under reduced pressure later3And toluene, so N-hexane (3 × 5 mL) is added afterwards to wash, drains, obtains corresponding pinacol borate CH3(CH2)4CH2OB(OC(CH3)2C (CH3)2O).The nuclear magnetic data of product:1H NMR (CDCl3, 400MHz): δ 3.83 (t, 2H, CH2), 1.59-1.52 (m, 2H, CH2), 1.37-1.26 (m, 8H, CH2), 6.83 (d, 1H, ArH) 1.25 (s, 12H, CH3), 0.88(t, 3H, CH3). 11B{1H} NMR (CDCl3, 128 MHz): δ 22.09 (s,B-O)。
Embodiment 20：[2-Me-C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Pr-N(SiMe3)2It is catalyzed valeraldehyde With pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, under argon gas protection, 0.02 mL catalyst [2-Me- is added with syringe C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Pr-N(SiMe3)2 The toluene solution (0.02 M) of (0.1% dosage), is then used 0.042 mL valeraldehydes are added in syringe, stir evenly, then 0.058 mL pinacol borines are added with syringe, and mixture is in room The lower stirring of temperature, after reacting 10min, is added 0.5 mLCDCl3, nuclear-magnetism yield is 93%, and CDCl is removed under reduced pressure later3And toluene, so N-hexane (3 × 5 mL) is added afterwards to wash, drains, obtains corresponding pinacol borate CH3(CH2)3CH2OB(OC(CH3)2C (CH3)2O)。
Embodiment 21: [2-Me-C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Pr-N(SiMe3)2It is catalyzed isoamyl Aldehyde and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, under argon gas protection, 0.02 mL catalyst [2-Me- is added with syringe C6H4-NC(Me)CHC(Me)N-C6H4-2-Me]2Pr-N(SiMe3)2 The toluene solution (0.02 M) of (0.1% dosage), is then used 0.043 mL isopentyl aldehydes are added in syringe, stir evenly, then 0.058 mL pinacol borines are added with syringe, and mixture is in room The lower stirring of temperature, after reacting 10min, is added 0.5 mLCDCl3, nuclear-magnetism yield is 94%, and CDCl is removed under reduced pressure later3And toluene, so N-hexane (3 × 5 mL) is added afterwards to wash, drains, obtains corresponding pinacol borate (CH3)2CHCH2CH2OB(OC(CH3)2C (CH3)2O).The nuclear magnetic data of product:1H NMR (CDCl3, 400 MHz): δ 3.85 (t, 2H, CH2), 1.76- 1.66 (m, 1H, CH), 1.48-1.43 (m, 2H, CH2), 1.24 (s, 12H, CH3), 0.90(d, 6H, CH3). 11B{1H} NMR (CDCl3, 128 MHz): δ 22.25(s, B-O)。

Claims (2)

1. a kind of method preparing borate, includes the following steps：
Under anhydrous and oxygen-free environment, under atmosphere of inert gases, catalyst is added in the reaction bulb by dehydration and deoxidation processing, then Aldehyde is added, is uniformly mixed, adds borine, reacts 5~10 min, uses CDCl3Reaction is terminated, solvent is removed under reduced pressure in reaction solution, Raffinate adds hexane washing, obtains corresponding different substituted boracic acid esters；The chemical structural formula of the catalyst is：
。
2. the method for preparing borate according to claim 1, it is characterised in that：The Ln is selected from praseodymium or neodymium；The aldehyde choosing From one kind in aromatic aldehyde, fatty aldehyde；The borine is pinacol borine；The dosage of the catalyst is the 0.1 of aldehyde molal quantity ~0.5%；The molar ratio of the borine and aldehyde is 1: 1；The reaction temperature is room temperature.
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