CN106478717A - Rare earth metal containing three tooth NNP parts is obstructed the synthesis of Lewis Acids and Bases pair and its application - Google Patents

Rare earth metal containing three tooth NNP parts is obstructed the synthesis of Lewis Acids and Bases pair and its application Download PDF

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CN106478717A
CN106478717A CN201610855047.5A CN201610855047A CN106478717A CN 106478717 A CN106478717 A CN 106478717A CN 201610855047 A CN201610855047 A CN 201610855047A CN 106478717 A CN106478717 A CN 106478717A
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rare earth
alkyl
obstructed
lewis acids
earth metal
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CN106478717B (en
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徐信
许鹏飞
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Suzhou University
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
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    • 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
    • B01J31/1845—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 phosphorus
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
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    • C07F9/02—Phosphorus compounds
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
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    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/52—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from boron, aluminium, gallium, indium, thallium or rare earths
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
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    • 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
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds

Abstract

The present invention relates to catalytic field, specifically disclose a kind of rare earth metal and be obstructed Lewis Acids and Bases pair, its formula is that wherein RE represents rare earth element；N=1 or 2；R' is C1‑C4Alkyl；R1For C1‑C4Alkyl；R2For C1‑C4Chain-like alkyl, C3‑C6Cycloalkyl or aryl；R " is C1‑C4Alkyl.Above-mentioned rare earth metal is obstructed Lewis Acids and Bases pair, can effectively realize activation of small molecule and catalytic reaction, and can be with highly active catalytic unsaturation esters monomer polymerization.Invention additionally discloses its preparation method and the three tooth NNP parts and its derivant and its preparation method that synthesize it.The invention also discloses the application in activation of small molecule and polyisocyanate polyaddition of itself and its derivant.

Description

Rare earth metal containing three tooth NNP parts be obstructed Lewis Acids and Bases pair synthesis and its Application
Technical field
The present invention relates to catalytic field, more particularly to a kind of rare earth metal containing three tooth NNP parts is obstructed lewis acid The synthesis of alkali pair and its application.
Background technology
Be obstructed Lewis Acids and Bases to (frustrated Lewis pair, FLP), be that there is Louis's electron donor simultaneously With the system of receptor, due to its sterically hindered presence, Louis's bronsted lowry acids and bases bronsted lowry will not occur self-quenching (can not be formed traditional Lewis acid alkali adduct), therefore, the Louis's bronsted lowry acids and bases bronsted lowry site in system can react, thus showing with other molecules Go out some special properties and reactivity.The concept of Lewis Acids and Bases pair of being obstructed was proposed by Stephan etc. first in 2006, Attract wide attention.
In recent years, larger progress is achieved to the research of the Lewis Acids and Bases pair that are obstructed, find to be obstructed in research Louis Acid-base pair can make imines, enamine, enol ether etc. that hydrogenation to occur under conditions of no metal catalytic.Additionally, Stephan Also the Lewis Acids and Bases that are obstructed have been reported with Erker et al. to having activated olefins, alkynes, the function such as fixing carbon dioxide.
At present, it is obstructed Lewis Acids and Bases to mostly major element compound, because major element compound is in catalytic reaction Aspect application example is less and active relatively low, therefore needs a kind of Lewis Acids and Bases pair that are obstructed based on rare earth metal of synthesis badly.
Content of the invention
Based on this it is necessary to provide a kind of synthesis based on rare earth metal be obstructed Lewis Acids and Bases to three tooth NNP join Body.
A kind of three tooth NNP parts, the general structure of described three tooth NNP parts is as follows：
Wherein, n=1 or 2；R' is C1-C4Alkyl；R1For C1-C4Alkyl；R2For C1-C4Chain-like alkyl, C3-C6Cycloalkyl, Or aryl.
Above-mentioned three tooth NNP parts, can be used for synthesizing the Lewis Acids and Bases pair that are obstructed based on rare earth metal；Containing rare earth metal Be obstructed Lewis Acids and Bases to can effectively realize activation of small molecule and catalytic reaction, and can be with highly active catalytic unsaturation esters Monomer is polymerized.Above-mentioned three tooth NNP parts, also help Development of Novel rare-earth metal catalyst, promote rare earth metal organic simultaneously The development of chemistry.
Wherein in an embodiment, the structural formula of described three tooth NNP parts is:
Or,
The Lewis Acids and Bases pair present invention also offers a kind of rare earth metal is obstructed.
A kind of rare earth metal is obstructed Lewis Acids and Bases pair, and described rare earth metal is obstructed the general structure of Lewis Acids and Bases pair For：
Wherein, RE represents rare earth element；N=1 or 2；R' is C1-C4Alkyl；R1For C1-C4Alkyl；R2For C1-C4Chain alkane Base, C3-C6Cycloalkyl or aryl；R " is C1-C4Alkyl.
Above-mentioned rare earth metal is obstructed Lewis Acids and Bases pair, can effectively realize activation of small molecule and catalytic reaction, and can With highly active catalytic unsaturation esters monomer polymerization.Above-mentioned rare earth metal is obstructed Lewis Acids and Bases pair, also helps Development of Novel Rare-earth metal catalyst, promotes the development of Organolanthanide Chemistry simultaneously.
Wherein in an embodiment, the be obstructed structural formula of Lewis Acids and Bases pair of described rare earth metal is：
Or,
Wherein, DIPP represents 2,6- diisopropyl phenyl；Ar is 2,6- di-tert-butyl-phenyl.
The preparation method of Lewis Acids and Bases pair present invention also offers a kind of above-mentioned rare earth metal is obstructed.
A kind of rare earth metal is obstructed the preparation method of Lewis Acids and Bases pair, comprises the steps：
Three tooth NNP parts and the first rare earth compound are reacted in organic solvent and obtain the second rare earth compound；Described Three tooth NNP parts are three tooth NNP parts described in claim 1；Described first rare earth compound is trialkyl rare earth compound Or three amido rare earth compounds；Described second rare earth compound is dialkyl group rare earth compounding or two amido rare earth compoundings；
Described second rare earth compound and phenolic compounds are reacted in organic solvent and obtains the 3rd rare earth compound；Described Phenolic compounds are C1-C4The phenol that alkyl replaces；Described 3rd rare earth compound is monoalkyl rare earth compounding or monoamine base rare earth Coordination compound；
Described 3rd rare earth compound is reacted with cationic reagent and obtains rare earth metal and be obstructed Lewis Acids and Bases pair；Institute State cationic reagent and contain B (C6F5)4Functional group.
Above-mentioned preparation method, can simply and easily synthesizing rare-earth metal be obstructed Lewis Acids and Bases pair, and technique simplifies, permissible Effectively reduce the manufacturing cost of the Lewis Acids and Bases pair that are obstructed.Also help Development of Novel rare-earth metal catalyst simultaneously, push away simultaneously The development of dynamic Organolanthanide Chemistry.
Present invention also offers a kind of derivant of the Lewis Acids and Bases pair that are obstructed.
A kind of above-mentioned rare earth metal is obstructed the derivant of Lewis Acids and Bases pair, and the general structure of described derivant is：
Wherein, RE represents rare earth element；N=1 or 2；R' is C1-C4Alkyl；R1For C1-C4Alkyl；R2For C1-C4Chain alkane Base, C3-C6Cycloalkyl or aryl；R " is C1-C4Alkyl；R3For H, C1-C4Chain-like alkyl, C3-C6Cycloalkyl or aryl；R4For Alkoxyl, N, N- dialkyl group, H, C1-C4Chain-like alkyl, C3-C6Cycloalkyl or aryl；R5For H, C1-C4Chain-like alkyl, C3-C6Ring Alkyl or aryl；
Or,
Wherein, RE represents rare earth element；N=1 or 2；R' is C1-C4Alkyl；R1For C1-C4Alkyl；R2For C1-C4Chain alkane Base, C3-C6Cycloalkyl or aryl；R " is C1-C4Alkyl；R7For H, C1-C4Chain-like alkyl, C3-C6Cycloalkyl or aryl；R8For H、C1-C4Chain-like alkyl, C3-C6Cycloalkyl or aryl.
Said derivative is it is also possible to be catalyzed esters polyreaction.
Wherein in an embodiment, the structural formula of described derivant is：
Or,
Or,
Wherein, DIPP represents 2,6- diisopropyl phenyl；Ar is 2,6- di-tert-butyl-phenyl.
Present invention also offers a kind of preparation method of said derivative.
A kind of preparation method of said derivative, comprises the steps：
The rare earth metal Lewis Acids and Bases pair that are obstructed are reacted in organic solvent with carbonyl compound and obtain；
The described rare earth metal Lewis Acids and Bases that are obstructed are obstructed Lewis Acids and Bases to for the rare earth metal described in claim 3 Right；
The formula of described carbonyl compound is R4-CO-R3C=CH-R5Or
Wherein, R3For H, C1-C4Chain-like alkyl, C3-C6Cycloalkyl or aryl；R4For alkoxyl, N, N- dialkyl group, H, C1- C4Chain-like alkyl, C3-C6Cycloalkyl or aryl；R5For H, C1-C4Chain-like alkyl, C3-C6Cycloalkyl or aryl；R7For H, C1-C4 Chain-like alkyl, C3-C6Cycloalkyl or aryl；R8For H, C1-C4Chain-like alkyl, C3-C6Cycloalkyl or aryl.
The preparation method of said derivative, process is simple.
Present invention also offers above-mentioned rare earth metal is obstructed, Lewis Acids and Bases are to the application in activation of small molecule.
Present invention also offers above-mentioned rare earth metal is obstructed Lewis Acids and Bases to and its application in polyisocyanate polyaddition for the derivant.
Brief description
Fig. 1 is the mono-crystalline structures figure of the M1 in embodiment 3.
Fig. 2 is the mono-crystalline structures figure of the B1 in embodiment 5.
Fig. 3 is the mono-crystalline structures figure of the B2 in embodiment 6.
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, below in conjunction with specific embodiment, right The present invention is further elaborated.It should be appreciated that specific embodiment described herein is only in order to explain the present invention, It is not intended to limit the present invention.
A kind of three tooth NNP parts, the general structure of this three teeth NNP part is as follows：
Wherein, n=1 or 2；R' is C1-C4Alkyl；R1For C1-C4Alkyl；R2For C1-C4Chain-like alkyl, C3-C6Cycloalkyl, Or aryl.
Preferably, R' is isopropyl.
Preferably, R1For methyl.
Preferably, R2For phenyl.
It is highly preferred that the structural formula of this three teeth NNP part is:
Or,
Of course, it should be understood that the three tooth NNP parts of the present invention are not limited to represented by above-mentioned two structural formula Compound, can also be that other meets the compound of formula.
Above-mentioned three tooth NNP parts, can be used for synthesizing the Lewis Acids and Bases pair that are obstructed based on rare earth metal；Containing rare earth metal Be obstructed Lewis Acids and Bases to can effectively realize activation of small molecule and catalytic reaction, and can be with highly active catalytic unsaturation esters Monomer is polymerized.
Above-mentioned three tooth NNP parts can be obtained by the following method.
The structural formula of each raw material is as follows：
The structural formula of beta-diketon isWherein, R1For C1-C4Alkyl.
The structural formula of arylamine isWherein, R' is C1-C4Alkyl.
Phosphorous amine structure formula isWherein, n=1 or 2；R2For C1-C4Chain-like alkyl, C3-C6Ring Alkyl or aryl.
By above-mentioned beta-diketon with above-mentioned arylamine with mol ratio for 0.2～3, in organic solvent at 0～110 DEG C, React 1-100h in the presence of 0.1-0.3% molar equivalent p-methyl benzenesulfonic acid, obtain monolateral substituted imines.
The general structure of monolateral substituted imines is：
Then in the above-mentioned phosphorous amine of monolateral substituted imines and 0.2～3 equivalent, in 0.1～20% molar equivalent pair In the presence of toluenesulfonic acid, in organic solvent, at 0 DEG C～110 DEG C, reaction 1h～100h is obtained three tooth NNP parts.
The Lewis Acids and Bases pair present invention also offers a kind of rare earth metal is obstructed.
A kind of rare earth metal is obstructed Lewis Acids and Bases pair, and the be obstructed general structure of Lewis Acids and Bases pair of this rare earth metal is：
Wherein, RE represents rare earth element；N=1 or 2；R' is C1-C4Alkyl；R1For C1-C4Alkyl；R2For C1-C4Chain alkane Base, C3-C6Cycloalkyl or aryl；R " is C1-C4Alkyl.Represent conjugated structure,Represent coordinate bond.
Preferably, rare earth element is selected from Sc or Y.
Preferably, R' is isopropyl.
Preferably, R1For methyl.
Preferably, R2For phenyl.
Preferably, R " is di-t-butyl.
It is highly preferred that this rare earth metal is obstructed, the structural formula of Lewis Acids and Bases pair is：
Or,
Wherein, DIPP represents 2,6- diisopropyl phenyl；Ar is 2,6- di-tert-butyl-phenyl.
Of course, it should be understood that the rare earth metal of the present invention is obstructed, Lewis Acids and Bases are tied to being not limited to above-mentioned two Compound represented by structure formula, can also be that other meets the compound of formula.
Above-mentioned rare earth metal is obstructed Lewis Acids and Bases pair, can effectively realize activation of small molecule and catalytic reaction, and can With highly active catalytic unsaturation esters monomer polymerization.
The preparation method of Lewis Acids and Bases pair present invention also offers a kind of above-mentioned rare earth metal is obstructed.
A kind of rare earth metal is obstructed the preparation method of Lewis Acids and Bases pair, comprises the steps：
Step S1：Three tooth NNP parts and the first rare earth compound are reacted in organic solvent and obtains the second rare earth chemical combination Thing.
Wherein, three tooth NNP parts are three tooth NNP parts provided by the present invention；First rare earth compound is that trialkyl is dilute Earth compounds or three amido rare earth compounds.For example, the first rare earth compound is RE (CH2SiMe3)3Or RE (CH2SiMe3)3 (THF)2.
Wherein, the effect of organic solvent is to provide medium basis for reaction.Organic solvent can be selected from toluene, chlorobenzene etc.. Of course, it should be understood that organic solvent is not limited thereto, can also be that those skilled in the art think that suitably other has Machine solvent.
In step sl, one of the first rare earth compound alkyl or an amido are replaced by three tooth NNP parts, corresponding Ground, the second rare earth compound of formation is dialkyl group rare earth compounding or two amido rare earth compoundings；Namely three tooth NNP part with The reaction of trialkyl rare earth compound generates dialkyl group rare earth compound；Three tooth NNP parts and three amido rare earth compounds react life Become two amido rare earth compounds.
Preferably, the concrete operations of step S1 are：RE (CH by three tooth NNP parts and 0.2～3 equivalent2SiMe3)3, React 0.1～20h at -30 DEG C～100 DEG C in organic solvent.
With following reaction equation, the reaction of step S1 is intuitively illustrated, other reactions can refer to following reaction equation reason Solution.
Step S2：Above-mentioned second rare earth compound and phenolic compounds are reacted in organic solvent and obtains the 3rd rare earth chemical combination Thing；
Wherein, phenolic compounds are C1-C4The phenol that alkyl replaces.
In step s 2, one of the second rare earth compound alkyl or an amido are replaced by phenolic compounds, accordingly, The 3rd rare earth compound being formed is monoalkyl rare earth compounding or monoamine base rare earth compounding；Namely phenolic compounds and dialkyl group Rare earth compound reaction generates monoalkyl rare earth compound；It is dilute that phenolic compounds and two amido rare earth compounds react generation monoamine base Earth compounds.
Preferably, the concrete operations of step S2 are：The above-mentioned phenolate conjunction obtaining the second rare earth compound and 0.1～1 equivalent Thing, reacts 0.1～2h in organic solvent at -30 DEG C～100 DEG C.
With following reaction equation, the reaction of step S2 is intuitively illustrated, other reactions can refer to following reaction equation reason Solution.
Step S3：Above-mentioned 3rd rare earth compound is reacted with cationic reagent and obtains rare earth metal and be obstructed lewis acid Alkali pair.
Wherein, cationic reagent contains B (C6F5)4Functional group.Such as N, N- dimethyl puratized agricultural spray four (pentafluorophenyl group) boric acid Salt or [Ph3C][B(C6F5)4] etc..
In step s3, cationic reagent is by last alkyl in the 3rd rare earth compound or last amido Replace.
Preferably, the concrete operations of step S3 are：Above-mentioned monoalkyl rare earth compounding and the N of 0.2～3 equivalent, N- diformazan Base puratized agricultural spray four (pentafluorophenyl group) borate, reacts 5min～30min at -30 DEG C～100 DEG C.
With following two reaction equations, the reaction of step S3 is intuitively illustrated, other reactions can refer to following two instead Formula is answered to understand.
Above-mentioned preparation method, can simply and easily synthesizing rare-earth metal be obstructed Lewis Acids and Bases pair, technique simplifies, permissible Effectively reduce the manufacturing cost of the Lewis Acids and Bases pair that are obstructed.
Present invention also offers a kind of derivant of the Lewis Acids and Bases pair that are obstructed.
A kind of above-mentioned rare earth metal is obstructed the derivant of Lewis Acids and Bases pair, and the general structure of described derivant is：
Wherein, RE represents rare earth element；N=1 or 2；R' is C1-C4Alkyl；R1For C1-C4Alkyl；R2For C1-C4Chain alkane Base, C3-C6Cycloalkyl or aryl；R " is C1-C4Alkyl；R3For H, C1-C4Chain-like alkyl, C3-C6Cycloalkyl or aryl；R4For Alkoxyl, N, N- dialkyl group, H, C1-C4Chain-like alkyl, C3-C6Cycloalkyl or aryl；R5For H, C1-C4Chain-like alkyl, C3-C6Ring Alkyl or aryl；
Or,
Wherein, RE represents rare earth element；N=1 or 2；R' is C1-C4Alkyl；R1For C1-C4Alkyl；R2For C1-C4Chain alkane Base, C3-C6Cycloalkyl or aryl；R " is C1-C4Alkyl；R7For H, C1-C4Chain-like alkyl, C3-C6Cycloalkyl or aryl；R8For H、C1-C4Chain-like alkyl, C3-C6Cycloalkyl or aryl.
Preferably, R' is isopropyl.
Preferably, R1For methyl.
Preferably, R2For phenyl.
Preferably, R " is di-t-butyl.
Preferably, R3For H or methyl.
Preferably, R4For phenyl or methoxyl group.
Preferably, R5For phenyl or H.
It is highly preferred that the structural formula of described derivant is：
Or,
Or,
Wherein, DIPP represents 2,6- diisopropyl phenyl；Ar is 2,6- di-tert-butyl-phenyl.
Said derivative is it is also possible to be catalyzed esters polyreaction.
Present invention also offers a kind of preparation method of said derivative.
A kind of preparation method of said derivative, comprises the steps：
The rare earth metal Lewis Acids and Bases pair that are obstructed are reacted in organic solvent with carbonyl compound and obtain.
Wherein, the rare earth metal Lewis Acids and Bases that are obstructed are obstructed Lewis Acids and Bases to for rare earth metal provided by the present invention Right.
Wherein, the formula of described carbonyl compound is R4-CO-R3C=CH-R5Or
Wherein, R3For H, C1-C4Chain-like alkyl, C3-C6Cycloalkyl or aryl；R4For alkoxyl, N, N- dialkyl group, H, C1- C4Chain-like alkyl, C3-C6Cycloalkyl or aryl；R5For H, C1-C4Chain-like alkyl, C3-C6Cycloalkyl or aryl；R7For H, C1-C4 Chain-like alkyl, C3-C6Cycloalkyl or aryl；R8For H, C1-C4Chain-like alkyl, C3-C6Cycloalkyl or aryl.
Preferably, carbonyl compound is methyl methacrylate or chalcone.
Preferably, the response time is 0.1～20h.
The preparation method of the derivant of the present invention is it is not limited to be former with the rare earth metal of the purification Lewis Acids and Bases that are obstructed Material, can also be and be directly added into carbonyl compound and carry out reacting preparing rare earth metal and be obstructed in the system of Lewis Acids and Bases Arrive.
The preparation method of said derivative, process is simple.
Present invention also offers above-mentioned rare earth metal is obstructed Lewis Acids and Bases to and its derivant in activation of small molecule Application.
Preferably, above-mentioned rare earth metal is obstructed Lewis Acids and Bases in organic solvent to Isosorbide-5-Nitrae-unsaturation small molecule substrates Activated, thus Isosorbide-5-Nitrae additive reaction occurring and obtaining corresponding product.
For example, carry out addition with the methyl methacrylate of equivalent or chalcone at -20 DEG C～160 DEG C in toluene Reaction.
Present invention also offers above-mentioned rare earth metal is obstructed Lewis Acids and Bases to and its application in polyisocyanate polyaddition for the derivant.
Preferably, above-mentioned rare earth metal be obstructed Lewis Acids and Bases to and its derivant efficient catalytic esters in organic solvent The polymerization of substrate.For example in toluene or chlorobenzene at -20 DEG C～160 DEG C Methyl Methacrylate Catalyzed, methacrylic acid uncle Butyl ester, 2- methene butyrolactone, alpha-methylene-γ-methene valerolactone, caprolactone polymerization.
Below in conjunction with specific embodiment, the present invention is further elaborated.
Embodiment 1
2- ((2,6- diisopropyl phenyl) amido -3- amylene -2- ketone preparation method：
By acetylacetone,2,4-pentanedione (14.7ml, 0.143mol), 2,6-DIPA (28ml, 0.143mol) and catalytic amount P-methyl benzenesulfonic acid (0.247g, 1.43mmol) (150mL) in toluene is heated to the 12h that flows back.The water producing in reaction passes through to divide Hydrophone removes.Reactant liquor is removed solvent after terminating under vacuum by reaction, obtains yellow oily liquid 35g, and yield is 94%.
By 2- ((2,6- diisopropyl phenyl) amido -3- amylene -2- ketone (1.70g, 6.5mmol), 2- (diphenylphosphino) The p-methyl benzenesulfonic acid (0.112g, 0.65mmol) of ethamine (1.50g, 6.5mmol) and catalytic amount (60mL) in toluene is heated to Backflow 72h.The water producing in reaction is removed by water knockout drum.React and after terminating, reactant liquor is removed under vacuum solvent, Xiang Qi Freezing at middle addition about 5mL methanol is placed in -30 DEG C separates out yellow crystalline solid in 5 days.Sucking filtration, hexane (3 × 3mL) washs, very Empty dry.
Obtain three tooth NNP parts, be denoted as HL1.
HL1 is buff powder, and quality is 1.27g, and yield is 42%.
Three tooth NNP part HL1 are made respectively with high resolution mass spectrum, nucleus magnetic hydrogen spectrum, carbon is composed, phosphorus is composed to characterize its structure.Data As follows：
HRMS (ESI) m/z value of calculation：C31H40N2P[M+H]+:471.2924；Measured value：471.2938.
1H NMR(400MHz,C6D6,299K):δ=11.24 (br s, 1H, NH), 7.29 (m, 4H, o-Ph2P),7.19 (m,2H,m-NAr),7.11(m,1H,p-NAr),6.98(m,4H,m-Ph2P,2H,p-Ph2P),4.65(s,1H,MeC(N)CH), 3.16(sp,3JHH=6.9Hz, 2H, ArCHMe2),3.11(m,2H,NCH2),2.14(m,2H,PCH2),1.64(s,3H,MeC (NAr)),1.49(s,3H,MeC(NCH2CH2PPh2)),1.21(d,3JHH=7.3Hz, 6H, ArCHMe2),1.18(d,3JHH= 7.3Hz,6H,ArCHMe2).
13C{1H}NMR(101MHz,C6D6,299K):δ=166.5 (MeC (NAr)), 155.1 (MeC (NCH2CH2PPh2), 147.4(i-NAr),138.8(d,1JPC=14.1Hz, i-Ph2P),138.3(o-NAr),133.0(d,2JPC=19.1Hz, o- Ph2P),128.8(m-Ph2P),128.7(p-Ph2P),123.4(p-NAr),123.3(o-NAr),94.3(MeC(N)CH), 40.5(d,2JPC=24.1Hz, NHCH2),31.1(d,1JPC=15.0Hz, PCH2),28.6(ArCHMe2),24.3 (ArCHMe2),23.1(ArCHMe2),21.8(MeC(NAr)),19.0(MeC(NCH2CH2PPh2)).
31P{1H}NMR(162MHz,C6D6,299K):δ=- 21.5 (ν1/2～5Hz).
Embodiment 2
By 2- ((2,6- diisopropyl phenyl) amido -3- amylene -2- ketone (2.13g, 8.2mmol), 2- (diphenylphosphino) The p-methyl benzenesulfonic acid (0.141g, 0.82mmol) of propylamine (2.00g, 8.2mmol) and catalytic amount (80mL) in toluene is heated to Backflow 72h.The water producing in reaction is removed by water knockout drum.React and after terminating, reactant liquor is removed under vacuum solvent, Xiang Qi Freezing at middle addition about 5mL methanol is placed in -30 DEG C separates out yellow solid in 1 day.Sucking filtration, hexane (3 × 3mL) washs, and vacuum is done Dry.
Obtain three tooth NNP parts, be denoted as HL2.
HL2 is buff powder, and quality is 2.38g, and yield is 60%.
Three tooth NNP part HL1 are made respectively with high resolution mass spectrum, nucleus magnetic hydrogen spectrum, carbon is composed, phosphorus is composed to characterize its structure.Data As follows：
HRMS (ESI) m/z value of calculation：C31H40N2P[M+H]+:485.3080；Measured value：485.3102.
1H NMR(400MHz,C6D6,299K):δ=11.13 (br s, 1H, NH), 7.35 (m, 4H, o-Ph2P),7.20 (m,2H,m-NAr),7.14(m,1H,p-NAr),7.03(m,4H,m-Ph2P,2H,p-Ph2P),4.69(s,1H,MeC(N)CH), 3.14(sp,3JHH=6.9Hz, 2H, ArCHMe2),3.11(m,2H,NHCH2),2.00(m,2H,PCH2),1.66(s,3H,MeC (NAr)),1.64(s,3H,MeC(NCH2CH2PPh2)),1.56(m,2H,NCH2CH2),1.20(d,3JHH=6.9Hz, 6H, ArCHMe2),1.16(d,3JHH=6.9Hz, 6H, ArCHMe2).
13C{1H}NMR(101MHz,C6D6,299K):δ=166.7 (MeC (NHAr)), 155.6 (MeC (NCH2CH2PPh2), 147.5(i-NAr),139.2(d,1JPC=14.3Hz, i-Ph2P),138.3(o-NAr),133.0(d,2JPC=18.6Hz, o- Ph2P),128.8(d,3JPC=6.5Hz, m-Ph2P),128.7(p-Ph2P),123.4(p-NAr),123.3(o-NAr),93.8 (MeC(N)CH),43.9(d,3JPC=13.9Hz, NHCH2),28.5(ArCHMe2),27.5(d,2JPC=16.8Hz, NCH2CH2),25.8(d,1JPC=13.2Hz, PCH2),24.2(ArCHMe2),23.1(ArCHMe2),21.8(MeC(NAr)), 19.1(MeC(NCH2CH2PPh2)).
31P{1H}NMR(162MHz,C6D6,299K):δ=- 16.5 (ν1/2～5Hz).
Embodiment 3
To Sc (CH under room temperature2SiMe3)3(THF)2Toluene solution (225mg, 0.5mmol, 1.5mL) Deca HL1 first Benzole soln (235mg, 0.5mmol, 1.5mL).Standing and reacting 12h.Reactant liquor removes solvent under vacuo and obtains yellow solid.Warp Hexane (3 × 1mL) washs, vacuum drying.Obtain the first intermediate product, be denoted as M1.
M1 is light yellow solid, and quality is 290mg, and yield is 84%.
It is added dropwise over 2,6 di t butyl phenol in the toluene solution (345mg, 0.5mmol, 1.5mL) of M1 under room temperature Toluene solution (103mg, 0.5mmol, 1.5mL).1h is stirred under room temperature.Reactant liquor removes solvent under vacuo and obtains yellow admittedly Body.Through hexane (3 × 1mL) washing, vacuum drying, obtain the second intermediate product, be denoted as M2.
M2 is light yellow solid, and quality is 317mg, and yield is 79%.
By M2 (60.0mg, 0.074mmol) and N under room temperature, N- dimethyl puratized agricultural spray four (pentafluorophenyl group) borate (59.6mg, 0.074mmol) mixing in toluene (1mL).It is added thereto to 2mL hexane after 5min, obtain yellow oily precipitation, This grease washs through hexane (2 × 1mL), vacuum drying.Obtain rare earth metal to be obstructed Lewis Acids and Bases pair, be denoted as A1.
A1 is light yellow solid powder, and quality is 94.2mg, and yield is 91%.
M1, M2 and A1 are made respectively with elementary analysiss, nucleus magnetic hydrogen spectrum, carbon is composed, phosphorus is composed to characterize its structure.And list is done to M1 Brilliant diffraction.
The data of compound M1 is as follows：
Elementary analysiss:Value of calculation：C39H60N2PScSi2:C,67.98；H,8.78；N, 4.07. measured value：C,68.05；H, 8.35；N,4.47.
1H NMR(400MHz,C6D6,299K):δ=7.51 (m, 4H, o-Ph2P),7.17(m,2H,m-NAr),7.15(m, 1H,p-NAr),7.09(m,4H,m-Ph2P),7.05(m,2H,p-Ph2P),4.97(s,1H,MeC(N)CH),3.40(m,2H, NCH2),3.33(sp,3JHH=6.8Hz, 2H, ArCHMe2),2.38(m,2H,PCH2),1.67(s,3H,MeC(NAr)),1.66 (s,3H,MeC(NCH2CH2PPh2)),1.48(d,3JHH=6.8Hz, 6H, ArCHMe2),1.17(d,3JHH=6.8Hz, 6H, ArCHMe2),0.19(m,4H,CH2SiMe3),0.06(s,18H,Sc(CH2SiMe3)2).
13C{1H}NMR(101MHz,C6D6,299K):δ=166.1 (MeC (NAr)), 165.3 (MeC (NCH2CH2PPh2), 144.1(i-NAr),142.5(o-NAr),135.1(d,1JPC=4.5Hz, i-Ph2P),133.4(d,2JPC=15.1Hz, o- Ph2P),129.9(p-Ph2P),129.0(d,3JPC=7.7Hz, m-Ph2P),126.5(p-NAr),124.4(m-NAr),98.1 (MeC(N)CH),47.1(d,2JPC=14.4Hz, NCH2),44.9(m,CH2SiMe3),28.5(overlapped with ArCHMe2,PCH2),28.4(ArCHMe2),25.3(ArCHMe2),24.6(ArCHMe2),23.7(MeC(NAr)),22.5(MeC (NCH2CH2PPh2)),3.9(Sc(CH2SiMe3)2).
31P{1H}NMR(162MHz,C6D6,299K):δ=- 21.0 (ν1/2～20Hz).
The single crystal diffraction data of M1 is shown in Fig. 1.
The data of compound M2 is as follows：
Elementary analysiss:Value of calculation：C49H70N2OPScSi:C,72.92；H,8.74；N, 3.47. measured value：C,72.87；H, 8.56；N,3.53.
1H NMR(400MHz,C6D6,299K):δ=7.34 (m, 4H, o-Ph2P),7.30(m,2H,m-OAr),7.06(m, 1H,p-NAr,m,2H,m-NAr),7.03(m,4H,m-Ph2P,m,2H,p-Ph2P),6.87(m,1H,p-OAr),5.09(s,1H, MeC(N)CH),3.67(m,2H,NCH2),3.34(sp,3JHH=6.7Hz, 1H, ArCHMe2),2.85(sp,3JHH=6.7Hz, 1H,ArCHMe2),2.46(m,2H,PCH2),1.69(s,6H,MeC(NAr),MeC(NCH2CH2PPh2)),1.44(s,18H,C (CH3)3),1.35(d,3JHH=6.7Hz, 3H, ArCHMe2),1.14(d,3JHH=6.7Hz, 6H, ArCHMe2),1.02(d,3JHH =6.7Hz, 3H, ArCHMe2),0.35(d,2JHH=11.1Hz, 1H, CH2SiMe3),0.16(s,18H,CH2SiMe3),0.13 (d,2JHH=11.1Hz, 1H, CH2SiMe3).
13C{1H}NMR(101MHz,C6D6,299K):δ=166.8 (MeC (NCH2CH2PPh2),165.9(MeC(NAr)), 162.4(i-OAr),144.4(i-NAr),142.5(o-NAr),142.4(o-NAr),138.6(o-OAr),138.0(d,1JPC =11.2Hz, i-Ph2P),137.6(d,1JPC=11.1Hz, i-Ph2P),133.3(d,2JPC=18.8Hz, o-Ph2P),133.0 (d,2JPC=18.3Hz, o-Ph2P),129.2(p-Ph2P),129.0(p-Ph2P),128.9(d,3JPC=2.1Hz, m-Ph2P), 128.8(d,3JPC=1.8Hz, m-Ph2P),126.5(p-NAr),125.3(m-OAr),124.5(m-NAr),124.4(m- NAr),118.4(p-OAr),98.3(MeC(N)CH),47.8(d,2JPC=26.4Hz, NCH2),40.7(m,CH2SiMe3), 35.0(C(CH3)3),31.5(C(CH3)3),30.8(d,1JPC=13.5Hz, PCH2),29.5(ArCHMe2),28.3 (ArCHMe2),25.2(ArCHMe2),24.9(ArCHMe2),24.8(MeC(NAr)),24.6(ArCHMe2),24.5 (ArCHMe2),22.0(MeC(NCH2CH2PPh2)),4.2(CH2SiMe3).
31P{1H}NMR(162MHz,C6D6,299K):δ=- 19.3 (ν1/2～7Hz).
The data of compound A1 is as follows：
Elementary analysiss:Value of calculation：C69H59BF20N2OPSc:C,59.24；H,4.25；N, 2.00. measured value:C,60.04； H,4.67；N,1.80.
1H NMR(600MHz,C6D6/C6D5Br(5:1),299K):δ=7.10 (4H, m, o-Ph2P,4H,m,m-Ph2P, 2H,m,p-Ph2P,)7.07(1H,p),6.93(2H,m)(each m,NAr),6.96(2H,m),6.71(1H,p)(each m, OAr),5.00(s,1H,MeC(N)CH),3.35(br,NCH2),2.60(2H,sp,3JHH=6.6Hz, ArCHMe2),2.37(br, PCH2),1.78(s,3H,MeC(N)CH),1.43(s,3H,MeC(N)CH),1.00(s,18H,C(CH3)3),0.90(d,3JHH= 6.6Hz),0.62(br)(each 6H,ArCHMe2).
13C{1H}NMR(151MHz,C6D6/C6D5Br(5:1),299K):δ=170.8 (MeC (N) CH), 168.8 (MeC (N)CH),159.6(i),136.7(o),125.9(m),121.5(p)(OAr),133.4(i),n.o.(o),130.0(p), 128.3(m)(NAr),n.o.(i),132.6(m),130.2(d,3JPC=9.9Hz, o), 132.5 (p) (PPh2),102.5(MeC (N)CH),46.1(d,2JPC=3.8Hz, NCH2),34.5(ArCHMe2),31.5(C(CH3)3),24.9(d,1JPC=24.9Hz, PCH2),24.1,23.8(br)(ArCHMe2),23.2,22.6(MeC(N)CH)[C6F5not listed].
31P{1H}NMR(243MHz,C6D6/C6D5Br(5:1),299K):δ=- 8.2 (ν1/2～65Hz).
Embodiment 4
To Y (CH under room temperature2SiMe3)3(THF)2Toluene solution (247mg, 0.5mmol, 1.5mL) Deca HL1 toluene Solution (235mg, 0.5mmol, 1.5mL).Standing and reacting 12h.Reactant liquor removes solvent under vacuo and obtains yellow solid.Through oneself Alkane (3 × 1mL) washs, vacuum drying.Obtain the first intermediate product, be denoted as MY1.
It is added dropwise over 2,6 di t butyl phenol in the toluene solution (366mg, 0.5mmol, 1.5mL) of MY1 under room temperature Toluene solution (103mg, 0.5mmol, 1.5mL).1h is stirred under room temperature.Reactant liquor removes solvent under vacuo and obtains yellow admittedly Body.Through hexane (3 × 1mL) washing, vacuum drying, obtain the second intermediate product, be denoted as MY2.
By MY2 (63.0mg, 0.074mmol) and N under room temperature, N- dimethyl puratized agricultural spray four (pentafluorophenyl group) borate (59.6mg, 0.074mmol) mixing in toluene (1mL).It is added thereto to 2mL hexane after 5min, obtain pale yellowish oil and sink Form sediment, this grease washs through hexane (2 × 1mL), vacuum drying.Obtain rare earth metal and be obstructed Lewis Acids and Bases to A2.
A2 is light yellow solid powder, and quality is 95.1mg, and yield is 89%.
Lewis Acids and Bases that rare earth metal is obstructed make elementary analysiss to A2, single crystal diffraction, nucleus magnetic hydrogen spectrum, and carbon is composed, phosphorus spectrum with Characterize its structure.Data is as follows：
Elementary analysiss:Value of calculation：C69H59BF20N2OPY·C6H14:C,58.91；H,4.81；N, 1.83. measured value：C, 58.82；H,4.66；N,1.92.
1H NMR(600MHz,C6D6,299K):δ=7.17 (2H, m), 6.82 (1H, p) (each m, OAr), 7.06 (4H, o),7.05(2H,p),6.97(4H,m)(each m,PPh2),7.07(1H,p),6.93(2H,m)(each m,NAr),4.98 (s,1H,MeC(N)CH),3.22(td,2H,3JPH=21.1Hz,3JHH=6.0Hz, NCH2),2.50(sp,2H,3JHH= 6.8Hz,ArCHMe2),2.24(m,2H,PCH2),1.71(s,3H,MeC(NCH2CH2PPh2)),1.60(s,3H,MeC(NAr)), 1.28(s,18H,C(CH3)3),0.98(d,3JHH=6.8Hz), 0.89 (d,3JHH=7.1Hz) (each 6H, ArCHMe2).
13C{1H}NMR(151MHz,C6D6,299K):δ=167.2 (MeC (NAr)), 166.9 (MeC (NCH2CH2PPh2)), 160.3(i),137.0(o),125.9(m),119.7(p)(OAr),141.4(o),138.9(i),127.9(p),125.5(m) (NAr),132.5(d,2JPC=13.5Hz, o), 131.9 (p), 129.9 (d,3JPC=9.4Hz, m), 128.1 (overlapped with solvent,i)(PPh2),94.5(MeC(N)CH),46.8(d,2JPC=6.8Hz, NCH2),34.7(C(CH3)3), 31.4(C(CH3)3),29.7(ArCHMe2),28.8(d,1JPC=14.9Hz, PCH2),24.4(MeC(NAr)),24.3,23.6 (ArCHMe2),23.2(MeC(NCH2CH2PPh2)),[C6F5not listed].
31P{1H}NMR(243MHz,C6D6,299K):δ=- 6.8 (d,1JYP=94.8Hz).
Embodiment 5
By intermediate product M2 (50.0mg, 0.062mmol) and N under room temperature, N- dimethyl puratized agricultural spray four (pentafluorophenyl group) boric acid Salt (49.6mg, 0.062mmol) mixing in toluene (1mL).The toluene being added thereto to methyl methacrylate after 5min is molten Liquid (6.2mg, 0.062mmol, 0.5mL).Add 2mL hexane in reactant liquor after stirring reaction 1h under room temperature, obtain shallow in a large number Yellow solid, removes mother solution, and solid washs through hexane (2 × 1mL), vacuum drying.
Obtain rare earth metal to be obstructed the derivant of Lewis Acids and Bases pair, be denoted as B1.
B1 is light yellow solid powder, and quality is 80.4mg, and yield is 87%.
B1 is made with elementary analysiss, single crystal diffraction, nucleus magnetic hydrogen spectrum, carbon is composed, phosphorus is composed to characterize its structure.Data is as follows：
Elementary analysiss:Value of calculation：C74H67BF20N2O3PSc·C6H14:C,60.61；H,5.15；N, 1.77. measured value：C, 60.00；H,5.16；N,1.92.
1H NMR(400MHz,C6D6/C6D5Br(3:1),299K):δ=7.26 (1H, p), 7.17 (2H, m), 7.05 (2H, o)(each m,PPh),7.25(1H,p),7.09(2H,m),7.03(2H,o)(each m,PPh’),7.21(2H,m),6.81 (1H,)(each m,OAr),7.06(1H,p),6.9(1H,m)(each m,NAr),5.04(s,1H,MeC(N)CH),3.88, 2.49(each m,each 1H,PCH2),3.79,3.43(each m,each 1H,NCH2),3.00(sp,3JHH=6.6Hz, 1H,ArCHMe2),2.67(s,3H,CH3), C=2.66 (overlapped with CH3C=, 1H, ArCHMe2),2.65 (overlapped with CH3C=, 2H, CH2), C=1.57 (s, 3H, MeC (NCH2CH2PPh2)),1.55(s,3H,MeC (NAr)),1.36(s,18H,C(CH3)3),1.29(d,3JHH=6.8Hz), 1.14 (d,3JHH=6.8Hz), 0.86 (d,3JHH= 6.8Hz),0.82(d,3JHH=6.8Hz) (each 3H, ArCHMe2),0.88(s,3H,OMe).
13C{1H}NMR(101MHz,C6D6/C6D5Br(3:1),299K):δ=170.1 (MeC (NAr)), 166.8 (MeC (NCH2CH2PPh2)),161.5(i),138.1(o),125.4(m),119.6(p)(OAr),160.6(d,3JPC=9.1Hz, OC =), 143.6 (o), 143.5 (o), 139.4 (i), 128.1 (p), 124.5 (m) (NAr), 135.6 (d,4JPC=2.5Hz, p), 132.2(d,2JPC=9.3Hz, o), 130.8 (d,3JPC=11.1Hz, m), 118.1 (d,1JPC=53.2Hz, i) (PhP), 135.4(d,4JPC=2.6Hz, p), 131.7 (d,2JPC=8.5Hz, o), 130.1 (d,3JPC=12.1Hz, m), 117.3 (d,1JPC=40.5Hz, i) (Ph ' P), 101.8 (MeC (N) CH), 67.3 (d,2JPC=9.7Hz, CH2C=), 52.7 (d,3JPC= 1.4Hz,CH3), C=40.0 (NCH2),34.7(C(CH3)3),30.7(C(CH3)3),29.7,28.2(ArCHMe2),24.9, 24.6,24.023.6(ArCHMe2),24.8(d,1JPC=40.5Hz, PCH2),23.7(MeC(NAr)),21.8(d,1JPC= 49.9Hz,CH2), C=20.8 (MeC (NCH2CH2PPh2)),16.3(d,5JPC=0.8Hz, OMe) [C6F5not listed].
31P{1H}NMR(162MHz,C6D6/C6D5Br(3:1),299K):δ=11.5 (ν1/2～16Hz).
The single crystal diffraction data of B1 is shown in Fig. 2.
Embodiment 6
By intermediate product M2 (50.0mg, 0.062mmol) and N under room temperature, N- dimethyl puratized agricultural spray four (pentafluorophenyl group) boric acid Salt (49.6mg, 0.062mmol) mixing in toluene (1mL).It is added thereto to the toluene solution of chalcone after 5min (12.9mg,0.062mmol,0.5mL).Add 2mL hexane in reactant liquor after stirring reaction 1h under room temperature, obtain pale yellow in a large number Color solid, removes mother solution, and solid washs through hexane (2 × 1mL), vacuum drying.
Obtain rare earth metal to be obstructed the derivant of Lewis Acids and Bases pair, be denoted as B2.
B2 is light yellow solid powder, and quality is 74.6mg, and yield is 75%.
B2 is made with elementary analysiss, single crystal diffraction, nucleus magnetic hydrogen spectrum, carbon is composed, phosphorus is composed to characterize its structure.Data is as follows：
Elementary analysiss:Value of calculation：C84H71BF20N2O2PSc·C7H8:C,64.32；H,4.69；N, 1.65. measured value:C, 63.98；H,4.78；N,1.80.
1H NMR(400MHz,C6D6/C6D5Br(5:1),299K):δ=7.29 (1H, p), 7.21 (2H, o), 7.08 (2H, m)(each m,PhP),7.24(2H,m),6.83(1H,p)(each m,OAr),7.14(1H,p),7.05(2H,m),6.92 (2H,o)(each m,Ph’P),7.19(1H,p),6.94(2H,m),6.69(2H,o)(each m,CHPh),7.10(1H,p), 7.07(2H,m)(each m,NAr),6.91(m,2H,o),6.88(m,2H,m),n.o.(1H,p)(CPh),5.54(dd,2JPH =11.4Hz,3JHH=8.9Hz, 1H, CHPh), 5.10 (s, 1H, MeC (N) CH), 4.64 (dd,3JPH=25.6Hz,3JHH= 13.6Hz, 1H, CH=), 4.24,3.71 (each m, each 1H, NCH2),3.16,2.54(each m,each 1H,PCH2), 3.14(sp,3JHH=6.7Hz), 2.53 (sp,3JHH=6.7Hz) (each 1H, ArCHMe2),1.74(s,3H,MeC(NAr)), 1.54(s,3H,MeC(NCH2CH2PPh2)),1.39(s,18H,C(CH3)3),1.05(d,3JHH=6.8Hz), 0.97 (d,3JHH= 6.7Hz),0.91(d,3JHH=6.5Hz), 0.78 (d,3JHH=6.8Hz) (each 3H, ArCHMe2).
13C{1H}NMR(101MHz,C6D6/C6D5Br(5:1),299K):δ=170.3 (MeC (NAr)), 167.5 (MeC (NCH2CH2PPh2)),162.1(d,3JPC=10.9Hz, OC=), 161.7 (i), 138.3 (o), 125.4 (m), 119.5 (p) (OAr),143.3(o),143.2(o),139.7(i),128.1(p),124.4(m)(NAr),137.6(d,4JPC=4.0Hz, i),129.8(m),125.1(d,5JPC=2.1Hz, o), n.o. (p) (CPh), 135.7 (d,4JPC=2.5Hz, p), 133.9 (d ,2JPC=7.8Hz, o), 129.7 (d,3JPC=11.7Hz, m), 117.1 (d,1JPC=82.3Hz, i) (PhP), 135.4 (d,4JPC =2.2Hz, p), 133.0 (d,2JPC=8.1Hz, o), 130.4 (d,3JPC=11.2Hz, m), 116.1 (d,1JPC=68.7Hz, i)(Ph’P),133.3(d,2JPC=4.3Hz, i), 130.0 (overlapped with C6D5Br,m),129.6(d,4JPC= 2.3Hz,p),129.2(d,3JPC=6.5Hz, o) (CHPh), 101.8 (MeC (N) CH), 93.6 (d,2JPC=25.6Hz, CH =), 41.5 (NCH2),39.3(d,1JPC=40.9Hz, CHPh), 34.8 (C (CH3)3),30.8(C(CH3)3),30.1,27.9 (ArCHMe2),25.1,24.3,23.9,23.1(ArCHMe2),24.4(d,1JPC=46.1Hz, PCH2),23.8(MeC (NCH2CH2PPh2)),20.9(MeC(NAr)),[C6F5not listed].
31P{1H}NMR(162MHz,C6D6/C6D5Br(5:1),299K):δ=15.4 (ν1/2～6Hz).
The single crystal diffraction data of B2 is shown in Fig. 3.
Embodiment 7
By intermediate product M2 (60.0mg, 0.074mmol) and N under room temperature, N- dimethyl puratized agricultural spray four (pentafluorophenyl group) boric acid Salt (59.6mg, 0.074mmol) mixing in toluene (1mL).It is added thereto to after 5min in alpha-methylene-γ-methene penta The toluene solution (8.3mg, 0.074mmol, 0.5mL) of ester.2mL hexane is added in reactant liquor after stirring reaction 1h under room temperature, Obtain a large amount of light yellow solids, remove mother solution, solid washs through hexane (2 × 1mL), vacuum drying.
Obtain rare earth metal to be obstructed the derivant of Lewis Acids and Bases pair, be denoted as B3.
B3 is light yellow solid powder, and quality is 96.5mg, and yield is 86%.
B3 is made with elementary analysiss, nucleus magnetic hydrogen spectrum, carbon is composed, (display B3 is non-by two kinds for nmr analysis to characterize its structure for phosphorus spectrum Enantiomer is constituted).Data is as follows：
Elementary analysiss:Value of calculation：C75H67BF20N2O3PSc·C6H14:C,60.91；H,5.11；N, 1.75. measured value：C, 60.83；H,5.22；N,2.13.
1H NMR(400MHz,Tol-d8,283K)for two isomers:δ=7.28 (2H, p), 7.23 (2H, p), 7.10(8H,m),6.93(4H,o),6.87(2H,o),6.78(2H,o)(each m,PPh2),7.11(4H,m),6.75(2H, p)(each m,OAr),7.07(4H,m),7.03(2H,m)(each m,NAr),4.87(2H,S,MeC(N)CH),4.23(2H, m,OCH),4.00,3.35(each m,each 2H,NCH2),3.63,2.44(each m,each 2H,PCH2),3.20 (sept,3JHH=6.7Hz), 3.15 (sept,3JHH=6.7Hz), 2.80 (sept,3JHH=6.7Hz), 2.78 (sept,3JHH= 6.7Hz)(each 1H,ArCHMe2),2.76,2.49(each m,each 1H,PCH2CH2),2.12,1.60,1.40,0.86 (each m,each 1H,OCHCH2),1.70(s,3H,MeC(NCH2CH2PPh2)),1.67(s,3H,MeC (NCH2CH2PPh2)),1.54(6H,d,3JHH=5.8Hz, ArCHMe2),1.47(s,3H,MeC(NAr)),1.46(s,3H,MeC (NAr)),1.25(s,18H,C(CH3)3),1.23(s,18H,C(CH3)3),1.10(3H,d,3JHH=6.0Hz, OCHMe), 1.01(6H,d,3JHH=6.7Hz, ArCHMe2),0.99(3H,d,3JHH=6.3Hz, OCHMe), 0.90 (overlapped with hexane,ArCHMe2),0.49(3H,d,3JHH=6.7Hz, ArCHMe2),0.47(3H,d,3JHH=6.7Hz, ArCHMe2).
13C{1H}NMR(101MHz,Tol-d8,283K)for two isomers:δ=170.2 (MeC (NAr)), 170.1 (MeC(NAr)),167.9(MeC(NCH2CH2PPh2)),167.8(MeC(NCH2CH2PPh2)),163.5(d,3JPC=7.0Hz, OC=), 163.5 (d,3JPC=7.6Hz, OC=), 161.2 (i), 137.4 (o), 125.2 (m), 119.6 (p) (OAr), 144.9 (o),143.4(o),137.4(i),125.6(m),125.0(p)(NAr),135.5(d,4JPC=1.4Hz, p), 135.4 (d,4JPC=2.6Hz, p), 132.3 (d,2JPC=10.6Hz, o), 132.2 (d,2JPC=10.5Hz, o), 131.7 (d,2JPC= 8.3Hz,o),131.6(d,2JPC=8.3Hz, o), 130.6 (d,3JPC=11.4Hz, m), 130.1 (d,3JPC=12.1Hz, m), 130.0(d,3JPC=12.4Hz, m), 118.1 (d,1JPC=68.1Hz, i), 118.0 (d,1JPC=66.3Hz, i), 117.9 (d ,1JPC=72.0Hz, i), 117.8 (d,1JPC=67.0Hz, i) (Ph2P),100.4(MeC(N)CH),100.3(MeC(N)CH), 74.1(OCH2),74.0(OCH2),58.5(d,2JPC=8.4Hz, CH2C=), 58.4 (d,2JPC=8.8Hz, CH2), C=40.0 (NCH2),38.9(OCHCH2),34.2(C(CH3)3),30.6(C(CH3)3),30.5(C(CH3)3),29.1,29.0,28.2, 28.1(ArCHMe2),25.0,24.9,24.6,24.5,24.4,24.3,23.4,23.3(ArCHMe2),23.5(MeC(NAr)), 22.1,22.0(OCHCH3),20.7(overlapped with solvent,PCH2CH2),20.3(overlapped with solvent,MeC(NCH2CH2PPh2)),19.8(overlapped with solvent,PCH2),[C6F5not listed].
31P{1H}NMR(162MHz,Tol-d8,283K)for two isomers:δ=11.2 (ν1/2～20Hz).
Embodiment 8
In glove box, the rare earth metal Lewis Acids and Bases that are obstructed weighing 56.0mg to A1 and are dissolved in 0.4mL toluene, will 200.2mg methyl methacrylate adds in this solution.
Take out one after 24h to be added dropwise in deuterochloroform through nuclear-magnetism mensure monomer conversion ratio, be subsequently added thereto to 5ml The methanol solution of 5% hydrochloric acid goes out, and adds 20ml methanol stirring 1h, filters, be dried under vacuum to constant weight.
Survey number-average molecular weight and the molecular weight distribution of polymer.Data is shown in Table 1.
Embodiment 9
In glove box, the rare earth metal Lewis Acids and Bases that are obstructed weighing 57.7mg to A2 and are dissolved in 0.4mL toluene, will 200.2mg methyl methacrylate adds in this solution.
Take out one after 4h to be added dropwise in deuterochloroform through nuclear-magnetism mensure monomer conversion ratio, be subsequently added thereto to 5ml The methanol solution of 5% hydrochloric acid goes out, and adds 20ml methanol stirring 1h, filters, be dried under vacuum to constant weight.
Survey number-average molecular weight and the molecular weight distribution of polymer.Data is shown in Table 1.
Embodiment 10
In glove box, the rare earth metal Lewis Acids and Bases that are obstructed weighing 28.0mg to A1 and are dissolved in 1mL chlorobenzene, will The 2- methene butyrolactone of 196.2mg adds in this solution.
The methanol solution being added thereto to the hydrochloric acid of 5ml 5% after 6h goes out, and adds 20ml methanol stirring 1h, filters, very Sky is dried to constant weight.
Survey the yield of polymer, survey number-average molecular weight and the molecular weight distribution of polymer.Data is shown in Table 1.
Embodiment 11
In glove box, the rare earth metal Lewis Acids and Bases that are obstructed weighing 28.9mg to A2 and are dissolved in 1mL chlorobenzene, will The 2- methene butyrolactone of 196.2mg adds in this solution.
The methanol solution being added thereto to the hydrochloric acid of 5ml 5% after 1.5h goes out, and adds 20ml methanol stirring 1h, filters, It is dried under vacuum to constant weight.
Survey the yield of polymer, survey number-average molecular weight and the molecular weight distribution of polymer.Data is shown in Table 1.
Embodiment 12
In glove box, the rare earth metal Lewis Acids and Bases that are obstructed weighing 28.0mg to A1 and are dissolved in 1mL chlorobenzene, will Alpha-methylene-the γ of 224.3mg-methene valerolactone adds in this solution.
Take out one after 1h to be added dropwise in deuterochloroform through nuclear-magnetism mensure monomer conversion ratio, be subsequently added thereto to 5ml The methanol solution of 5% hydrochloric acid goes out, and adds 20ml methanol stirring 1h, filters, be dried under vacuum to constant weight.
Survey number-average molecular weight and the molecular weight distribution of polymer.Data is shown in Table 1.
Embodiment 13
In glove box, the rare earth metal Lewis Acids and Bases that are obstructed weighing 28.9mg to A2 and are dissolved in 1mL chlorobenzene, will Alpha-methylene-the γ of 224.3mg-methene valerolactone adds in this solution.
Take out one after 3min to be added dropwise in deuterochloroform through nuclear-magnetism mensure monomer conversion ratio, be subsequently added thereto to 5ml The methanol solution of 5% hydrochloric acid goes out, and adds 20ml methanol stirring 1h, filters, be dried under vacuum to constant weight.
Survey number-average molecular weight and the molecular weight distribution of polymer.Data is shown in Table 1.
Embodiment 14
In glove box, the rare earth metal Lewis Acids and Bases that are obstructed weighing 28.9mg to A2 and are dissolved in 8mL chlorobenzene, will 1794.1mg alpha-methylene-γ-methene valerolactone adds in this solution.
Take out one after 5min to be added dropwise in deuterochloroform through nuclear-magnetism mensure monomer conversion ratio, be subsequently added thereto to 5ml The methanol solution of 5% hydrochloric acid goes out, and adds 20ml methanol stirring 1h, filters, be dried under vacuum to constant weight.
Survey number-average molecular weight and the molecular weight distribution of polymer.Data is shown in Table 1.
Table 1
Wherein, monomer conversion is recorded by nuclear-magnetism, data representation polymer yield in bracket, and polymer yield passes through to claim Weight method records.Number-average molecular weight and molecular weight distribution are recorded by GPC.
Rare earth metal provided by the present invention be can be seen that by the data in table 1 and be obstructed Lewis Acids and Bases to poly- to ester Conjunction has preferable catalytic effect.

Claims (10)

1. a kind of three tooth NNP parts are it is characterised in that the general structure of described three tooth NNP parts is as follows：
Wherein, n=1 or 2；R' is C1-C4Alkyl；R1For C1-C4Alkyl；R2For C1-C4Chain-like alkyl, C3-C6Cycloalkyl or virtue Base.
2. three tooth NNP parts according to claim 1 are it is characterised in that the structural formula of described three tooth NNP parts is：
3. a kind of rare earth metal is obstructed Lewis Acids and Bases to the Lewis Acids and Bases pair it is characterised in that described rare earth metal is obstructed General structure is：
Wherein, RE represents rare earth element；N=1 or 2；R' is C1-C4Alkyl；R1For C1-C4Alkyl；R2For C1-C4Chain-like alkyl, C3-C6Cycloalkyl or aryl；R " is C1-C4Alkyl.
4. rare earth metal according to claim 3 is obstructed Lewis Acids and Bases to it is characterised in that described rare earth metal is obstructed The structural formula of Lewis Acids and Bases pair is：
Wherein, DIPP represents 2,6- diisopropyl phenyl；Ar is 2,6- di-tert-butyl-phenyl.
5. the rare earth metal described in a kind of claim 3 be obstructed Lewis Acids and Bases pair preparation method it is characterised in that include as Lower step：
Three tooth NNP parts and the first rare earth compound are reacted in organic solvent and obtain the second rare earth compound；Described three teeth NNP part is three tooth NNP parts described in claim 1；Described first rare earth compound is trialkyl rare earth compound or three Amido rare earth compound；Described second rare earth compound is dialkyl group rare earth compounding or two amido rare earth compoundings；
Described second rare earth compound and phenolic compounds are reacted in organic solvent and obtains the 3rd rare earth compound；Described phenolate Compound is C1-C4The phenol that alkyl replaces；Described 3rd rare earth compound is monoalkyl rare earth compounding or the cooperation of monoamine base rare earth Thing；
Described 3rd rare earth compound is reacted with cationic reagent and obtains rare earth metal and be obstructed Lewis Acids and Bases pair；Described sun Ionization reagent contains B (C6F5)4Functional group.
6. the rare earth metal described in a kind of claim 3 be obstructed Lewis Acids and Bases pair derivant it is characterised in that described derivative The general structure of thing is：
Wherein, RE represents rare earth element；N=1 or 2；R' is C1-C4Alkyl；R1For C1-C4Alkyl；R2For C1-C4Chain-like alkyl, C3-C6Cycloalkyl or aryl；R " is C1-C4Alkyl；R3For H, C1-C4Chain-like alkyl, C3-C6Cycloalkyl or aryl；R4For alcoxyl Base, N, N- dialkyl group, H, C1-C4Chain-like alkyl, C3-C6Cycloalkyl or aryl；R5For H, C1-C4Chain-like alkyl, C3-C6Cycloalkanes Base or aryl；
Or,
Wherein, RE represents rare earth element；N=1 or 2；R' is C1-C4Alkyl；R1For C1-C4Alkyl；R2For C1-C4Chain-like alkyl, C3-C6Cycloalkyl or aryl；R " is C1-C4Alkyl；R7For H, C1-C4Chain-like alkyl, C3-C6Cycloalkyl or aryl；R8For H, C1- C4Chain-like alkyl, C3-C6Cycloalkyl or aryl.
7. derivant according to claim 6 is it is characterised in that the structural formula of described derivant is：
Or,
Or,
Wherein, DIPP represents 2,6- diisopropyl phenyl；Ar is 2,6- di-tert-butyl-phenyl.
8. a kind of preparation method of the derivant described in claim 6 is it is characterised in that comprise the steps：
The rare earth metal Lewis Acids and Bases pair that are obstructed are reacted in organic solvent with carbonyl compound and obtain；
The described rare earth metal Lewis Acids and Bases that are obstructed are obstructed Lewis Acids and Bases pair to for the rare earth metal described in claim 3；
The formula of described carbonyl compound is R4-CO-R3C=CH-R5Or
Wherein, R3For H, C1-C4Chain-like alkyl, C3-C6Cycloalkyl or aryl；R4For alkoxyl, N, N- dialkyl group, H, C1-C4Chain Shape alkyl, C3-C6Cycloalkyl or aryl；R5For H, C1-C4Chain-like alkyl, C3-C6Cycloalkyl or aryl；R7For H, C1-C4Chain Alkyl, C3-C6Cycloalkyl or aryl；R8For H, C1-C4Chain-like alkyl, C3-C6Cycloalkyl or aryl.
9. the rare earth metal described in any one of claim 3-4 is obstructed Lewis Acids and Bases to the application in activation of small molecule.
10. the rare earth metal described in any one of claim 3-4 be obstructed Lewis Acids and Bases to or any one of claim 6-7 described in Application in polyisocyanate polyaddition for the derivant.
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