CN106478717B - Rare earth metal containing three tooth NNP ligands is obstructed the synthesis and its application of Lewis Acids and Bases pair - Google Patents
Rare earth metal containing three tooth NNP ligands is obstructed the synthesis and its application of Lewis Acids and Bases pair Download PDFInfo
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- 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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- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
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- 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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- 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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- 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 general formula isWherein, 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 ligands and its derivative and its preparation method that synthesize it.The invention also discloses the application of itself and its derivative in activation of small molecule and polyisocyanate polyaddition.
Description
Technical field
The present invention relates to catalytic field, it is obstructed lewis acid more particularly to a kind of rare earth metal for containing three tooth NNP ligands
The synthesis and its application of alkali pair.
Background technology
Lewis Acids and Bases be obstructed to (frustrated Lewis pair, FLP), is that there is Louis's electron donor at the same time
With the system of acceptor, due to the presence of its steric hindrance, self-quenching, which will not occur, for Louis's bronsted lowry acids and bases bronsted lowry (cannot form traditional
Lewis acid alkali adduct), therefore, Louis's bronsted lowry acids and bases bronsted lowry site in system can react with other molecules, so as to show
Go out some special properties and reactivity.The concept of Lewis Acids and Bases pair of being obstructed proposed by Stephan etc. first in 2006,
Attract wide attention.
In recent years, the research to the Lewis Acids and Bases pair that are obstructed achieves larger progress, and the Louis that is obstructed is found in research
Acid-base pair can make imines, enamine, enol ether etc. that hydrogenation occur under conditions of no metal catalytic.In addition, Stephan
The Lewis Acids and Bases that are obstructed also have been reported with Erker et al. to the function such as activated olefins, alkynes, fixed carbon dioxide.
At present, Lewis Acids and Bases are obstructed to being mostly major element compound, since major element compound is in catalytic reaction
Aspect application example is less and active relatively low, therefore there is an urgent need for synthesize a kind of Lewis Acids and Bases pair that are obstructed based on rare earth metal.
The content of the invention
Based on this, it is necessary to provide it is a kind of synthesize based on rare earth metal be obstructed Lewis Acids and Bases to three tooth NNP match somebody with somebody
Body.
A kind of three tooth NNP ligands, the general structure of the three teeth NNP ligands are 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 teeth NNP ligands, available for be obstructed Lewis Acids and Bases pair of the synthesis based on rare earth metal;Containing rare earth metal
The Lewis Acids and Bases pair that are obstructed can effectively realize activation of small molecule and catalytic reaction, and can be with highly active catalytic unsaturation esters
Monomer polymerization.Above-mentioned three teeth NNP ligands, also help Development of Novel rare-earth metal catalyst, while promote rare earth metal organic
The development of chemistry.
In one of the embodiments, the structural formula of the three teeth NNP ligands is:
Or,
It is obstructed Lewis Acids and Bases pair present invention also offers a kind of rare earth metal.
A kind of rare earth metal is obstructed Lewis Acids and Bases pair, and the rare earth metal is obstructed the general structures 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, while promote the development of Organolanthanide Chemistry.
In one of the embodiments, the be obstructed structural formula of Lewis Acids and Bases pair of the rare earth metal is:
Or,
Wherein, DIPP represents 2,6- diisopropyl phenyls;Ar is 2,6- di-tert-butyl-phenyls.
It is obstructed present invention also offers a kind of above-mentioned rare earth metal the preparation methods of Lewis Acids and Bases pair.
A kind of rare earth metal is obstructed the preparation methods of Lewis Acids and Bases pair, includes the following steps:
Three tooth NNP ligands and the first rare earth compound are reacted to obtain the second rare earth compound in organic solvent;It is described
Three tooth NNP ligands are three tooth NNP ligands described in claim 1;First rare earth compound is trialkyl rare earth compound
Or three amido rare earth compound;Second rare earth compound is dialkyl group rare earth compounding or two amido rare earth compoundings;
Second rare earth compound and phenolic compounds are reacted to obtain the 3rd rare earth compound in organic solvent;It is described
Phenolic compounds is C1-C4Alkyl-substituted phenol;3rd rare earth compound is monoalkyl rare earth compounding or monoamine base rare earth
Complex;
React to obtain rare earth metal by the 3rd rare earth compound and cationic reagent to 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 is simplified, can be with
Effectively reduce the manufacture cost for the Lewis Acids and Bases pair that are obstructed.Development of Novel rare-earth metal catalyst is also helped at the same time, is pushed away at the same time
The development of dynamic Organolanthanide Chemistry.
Present invention also offers a kind of derivative for the Lewis Acids and Bases pair that are obstructed.
A kind of above-mentioned rare earth metal is obstructed the derivatives of Lewis Acids and Bases pair, and the general structure of the derivative 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
Alkoxy, 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, can also be catalyzed esters polymerisation.
In one of the embodiments, the structural formula of the derivative is:
Or,
Or,
Wherein, DIPP represents 2,6- diisopropyl phenyls;Ar is 2,6- di-tert-butyl-phenyls.
Present invention also offers a kind of preparation method of said derivative.
A kind of preparation method of said derivative, includes the following steps:
The rare earth metal Lewis Acids and Bases pair that are obstructed are reacted to obtain in organic solvent with carbonyls;
The rare earth metal is obstructed Lewis Acids and Bases to being obstructed Lewis Acids and Bases for the rare earth metal described in claim 3
It is right;
The general formula of the carbonyls is R4-CO-R3C=CH-R5Or
Wherein, R3For H, C1-C4Chain-like alkyl, C3-C6Cycloalkyl or aryl;R4For alkoxy, 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, technique are simple.
Present invention also offers above-mentioned rare earth metal to be obstructed Lewis Acids and Bases to the application in activation of small molecule.
It is obstructed the application of Lewis Acids and Bases pair and its derivative in polyisocyanate polyaddition present invention also offers above-mentioned rare earth metal.
Brief description of the drawings
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.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with embodiment
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are only to explain the present invention,
It is not intended to limit the present invention.
A kind of three tooth NNP ligands, the general structure of the three teeth NNP ligands are 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 the three teeth NNP ligands is:
Or,
Of course, it should be understood that the three tooth NNP ligands of the present invention are not limited to represented by above-mentioned two structural formula
Compound, can also be other compounds for meeting general formula.
Above-mentioned three teeth NNP ligands, available for be obstructed Lewis Acids and Bases pair of the synthesis based on rare earth metal;Containing rare earth metal
The Lewis Acids and Bases pair that are obstructed can effectively realize activation of small molecule and catalytic reaction, and can be with highly active catalytic unsaturation esters
Monomer polymerization.
Above-mentioned three teeth NNP ligands can be made 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' 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 and above-mentioned arylamine using molar ratio as 0.2~3, in organic solvent at 0~110 DEG C,
1-100h is reacted in the presence of 0.1-0.3% molar equivalent p-methyl benzenesulfonic acid, obtains unilateral substituted imines.
The general structure of unilateral substituted imines is:
Then in unilateral substituted imines and the above-mentioned phosphorous amine of 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, three tooth NNP ligands are made in reaction 1h~100h.
It is obstructed Lewis Acids and Bases pair present invention also offers a kind of rare earth metal.
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 the 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 the rare earth metal is obstructed, the structural formula of Lewis Acids and Bases pair is:
Or,
Wherein, DIPP represents 2,6- diisopropyl phenyls;Ar is 2,6- di-tert-butyl-phenyls.
Of course, it should be understood that the rare earth metal of the present invention is obstructed Lewis Acids and Bases to being not limited to above-mentioned two knot
Compound represented by structure formula, can also be other compounds for meeting general 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.
It is obstructed present invention also offers a kind of above-mentioned rare earth metal the preparation methods of Lewis Acids and Bases pair.
A kind of rare earth metal is obstructed the preparation methods of Lewis Acids and Bases pair, includes the following steps:
Step S1:Three tooth NNP ligands and the first rare earth compound are reacted in organic solvent to obtain the second rare earth chemical combination
Thing.
Wherein, three tooth NNP ligands are three teeth NNP ligands provided by the present invention;First rare earth compound is dilute for trialkyl
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, it can also be that those skilled in the art think suitably other and have
Solvent.
In step sl, three tooth NNP ligands substitute an alkyl in the first rare earth compound or an amido, 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 ligands with
Trialkyl rare earth compound reaction generation dialkyl group rare earth compound;Three tooth NNP ligands and the reaction of three amido rare earth compounds are given birth to
Into two amido rare earth compounds.
Preferably, the concrete operations of step S1 are:By three tooth NNP ligands and the RE (CH of 0.2~3 equivalent2SiMe3)3,
0.1~20h is reacted in organic solvent at -30 DEG C~100 DEG C.
Intuitively illustrated with reaction of the following reaction equation to step S1, other reactions can refer to following reaction equation reason
Solution.
Step S2:Above-mentioned second rare earth compound and phenolic compounds are reacted to obtain the 3rd rare earth chemical combination in organic solvent
Thing;
Wherein, phenolic compounds C1-C4Alkyl-substituted phenol.
In step s 2, phenolic compounds substitutes an alkyl in the second rare earth compound or an amido, accordingly,
The 3rd rare earth compound formed is monoalkyl rare earth compounding or monoamine base rare earth compounding;Namely phenolic compounds and dialkyl group
Rare earth compound reaction generation monoalkyl rare earth compound;Phenolic compounds and two amido rare earth compounds reaction generation monoamine base are dilute
Earth compounds.
Preferably, the concrete operations of step S2 are:It is above-mentioned to obtain the phenolate conjunction of the second rare earth compound and 0.1~1 equivalent
Thing, reacts 0.1~2h at -30 DEG C~100 DEG C in organic solvent.
Intuitively illustrated with reaction of the following reaction equation to step S2, other reactions can refer to following reaction equation reason
Solution.
Step S3:React to obtain rare earth metal by above-mentioned 3rd rare earth compound and cationic reagent to 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 or last amido in the 3rd rare earth compound
Substitution.
Preferably, the concrete operations of step S3 are:The N of above-mentioned monoalkyl rare earth compounding and 0.2~3 equivalent, N- diformazans
Base puratized agricultural spray four (pentafluorophenyl group) borate, reacts 5min~30min at -30 DEG C~100 DEG C.
Intuitively illustrated with reaction of following two reaction equations to step S3, 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, and technique simplifies, can be with
Effectively reduce the manufacture cost for the Lewis Acids and Bases pair that are obstructed.
Present invention also offers a kind of derivative for the Lewis Acids and Bases pair that are obstructed.
A kind of above-mentioned rare earth metal is obstructed the derivatives of Lewis Acids and Bases pair, and the general structure of the derivative 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
Alkoxy, 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 the derivative is:
Or,
Or,
Wherein, DIPP represents 2,6- diisopropyl phenyls;Ar is 2,6- di-tert-butyl-phenyls.
Said derivative, can also be catalyzed esters polymerisation.
Present invention also offers a kind of preparation method of said derivative.
A kind of preparation method of said derivative, includes the following steps:
The rare earth metal Lewis Acids and Bases pair that are obstructed are reacted to obtain in organic solvent with carbonyls.
Wherein, rare earth metal is obstructed Lewis Acids and Bases to being obstructed Lewis Acids and Bases for rare earth metal provided by the present invention
It is right.
Wherein, the general formula of the carbonyls is R4-CO-R3C=CH-R5Or
Wherein, R3For H, C1-C4Chain-like alkyl, C3-C6Cycloalkyl or aryl;R4For alkoxy, 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, carbonyls is methyl methacrylate or chalcone.
Preferably, the reaction time is 0.1~20h.
The preparation method of the derivative of the present invention, it is not limited to which Lewis Acids and Bases are obstructed as original using the rare earth metal of purifying
Material, can also be and be directly added into carbonyls and react preparing rare earth metal and be obstructed in the system of Lewis Acids and Bases
Arrive.
The preparation method of said derivative, technique are simple.
Present invention also offers above-mentioned rare earth metal to be obstructed Lewis Acids and Bases pair and its derivative in activation of small molecule
Using.
Preferably, above-mentioned rare earth metal is obstructed Lewis Acids and Bases in organic solvent to Isosorbide-5-Nitrae-unsaturation small molecule substrates
Activated, so that Isosorbide-5-Nitrae addition reaction occur and obtain corresponding product.
For example, the methyl methacrylate or chalcone with equivalent at -20 DEG C~160 DEG C in toluene carry out addition
Reaction.
It is obstructed the application of Lewis Acids and Bases pair and its derivative in polyisocyanate polyaddition present invention also offers above-mentioned rare earth metal.
Preferably, above-mentioned rare earth metal is obstructed Lewis Acids and Bases pair and its derivative efficient catalytic esters in organic solvent
The polymerization of substrate.Such as in toluene or chlorobenzene at -20 DEG C~160 DEG C Methyl Methacrylate Catalyzed, methacrylic acid uncle
Butyl ester, 2- methenes 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 phenyls) amido -3- amylene -2- ketone preparation methods:
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 reflux 12h.The water produced in reaction is by dividing
Hydrophone removes.Reaction solution is removed into solvent under vacuum after reaction, obtains yellow oily liquid 35g, yield 94%.
By 2- ((2,6- diisopropyl phenyls) 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
Flow back 72h.The water produced in reaction is removed by water knockout drum.Reaction solution is removed into solvent, Xiang Qi under vacuum after reaction
Middle addition about 5mL methanol, which is placed in freezing at -30 DEG C 5 days, separates out yellow crystalline solid.Filter, hexane (3 × 3mL) washing, very
Sky is dry.
Three tooth NNP ligands are obtained, are denoted as HL1.
HL1 is buff powder, quality 1.27g, yield 42%.
Three tooth NNP ligands HL1 are made with high resolution mass spectrum, nucleus magnetic hydrogen spectrum respectively, carbon is composed, and phosphorus is composed to characterize its structure.Data
It is as follows:
HRMS (ESI) m/z calculated values: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):(the ν of δ=- 21.51/2~5Hz)
Embodiment 2
By 2- ((2,6- diisopropyl phenyls) 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
Flow back 72h.The water produced in reaction is removed by water knockout drum.Reaction solution is removed into solvent, Xiang Qi under vacuum after reaction
Middle addition about 5mL methanol, which is placed in freezing at -30 DEG C 1 day, separates out yellow solid.Filter, hexane (3 × 3mL) washing, vacuum is done
It is dry.
Three tooth NNP ligands are obtained, are denoted as HL2.
HL2 is buff powder, quality 2.38g, yield 60%.
Three tooth NNP ligands HL1 are made with high resolution mass spectrum, nucleus magnetic hydrogen spectrum respectively, carbon is composed, and phosphorus is composed to characterize its structure.Data
It is as follows:
HRMS (ESI) m/z calculated values: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):(the ν of δ=- 16.51/2~5Hz)
Embodiment 3
At room temperature to Sc (CH2SiMe3)3(THF)2Toluene solution (225mg, 0.5mmol, 1.5mL) be added dropwise HL1 first
Benzole soln (235mg, 0.5mmol, 1.5mL).Stand reaction 12h.Reaction solution removes solvent and obtains yellow solid under vacuo.Through
Hexane (3 × 1mL) washs, vacuum drying.The first intermediate product is obtained, is denoted as M1.
M1 is light yellow solid, quality 290mg, yield 84%.
2,6 di t butyl phenol is added dropwise into the toluene solution (345mg, 0.5mmol, 1.5mL) of M1 at room temperature
Toluene solution (103mg, 0.5mmol, 1.5mL).1h is stirred at room temperature.Reaction solution removes solvent and obtains yellow under vacuo to be consolidated
Body.Washed through hexane (3 × 1mL), vacuum drying, obtains the second intermediate product, be denoted as M2.
M2 is light yellow solid, quality 317mg, yield 79%.
At room temperature by M2 (60.0mg, 0.074mmol) and N, N- dimethyl puratized agricultural spray four (pentafluorophenyl group) borate
(59.6mg, 0.074mmol) mixing in toluene (1mL).2mL hexanes are added after 5min thereto, obtain yellow oily precipitation,
The grease is washed 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, quality 94.2mg, yield 91%.
Make elemental analysis, nucleus magnetic hydrogen spectrum respectively to M1, M2 and A1, carbon is composed, and phosphorus is composed to characterize its structure.And list is done to M1
Brilliant diffraction.
The data of compound M1 are as follows:
Elemental analysis:Calculated value: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):(the ν of δ=- 21.01/2~20Hz)
The single crystal diffraction data of M1 are shown in Fig. 1.
The data of compound M2 are as follows:
Elemental analysis:Calculated value: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):(the ν of δ=- 19.31/2~7Hz)
The data of compound A1 are as follows:
Elemental analysis:Calculated value: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):(the ν of δ=- 8.21/2~65Hz)
Embodiment 4
At room temperature to Y (CH2SiMe3)3(THF)2Toluene solution (247mg, 0.5mmol, 1.5mL) be added dropwise HL1 toluene
Solution (235mg, 0.5mmol, 1.5mL).Stand reaction 12h.Reaction solution removes solvent and obtains yellow solid under vacuo.Through oneself
Alkane (3 × 1mL) washs, vacuum drying.The first intermediate product is obtained, is denoted as MY1.
2,6 di t butyl phenol is added dropwise into the toluene solution (366mg, 0.5mmol, 1.5mL) of MY1 at room temperature
Toluene solution (103mg, 0.5mmol, 1.5mL).1h is stirred at room temperature.Reaction solution removes solvent and obtains yellow under vacuo to be consolidated
Body.Washed through hexane (3 × 1mL), vacuum drying, obtains the second intermediate product, be denoted as MY2.
At room temperature by MY2 (63.0mg, 0.074mmol) and N, N- dimethyl puratized agricultural spray four (pentafluorophenyl group) borate
(59.6mg, 0.074mmol) mixing in toluene (1mL).2mL hexanes are added after 5min thereto, pale yellowish oil is obtained and sinks
Form sediment, which 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, quality 95.1mg, yield 89%.
The Lewis Acids and Bases that are obstructed to rare earth metal make A2 elemental analysis, single crystal diffraction, nucleus magnetic hydrogen spectrum, carbon spectrum, phosphorus spectrum with
Characterize its structure.Data are as follows:
Elemental analysis:Calculated value: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
At room temperature by intermediate product M2 (50.0mg, 0.062mmol) and N, N- dimethyl puratized agricultural spray four (pentafluorophenyl group) boric acid
Salt (49.6mg, 0.062mmol) mixing in toluene (1mL).The toluene for adding methyl methacrylate after 5min thereto is molten
Liquid (6.2mg, 0.062mmol, 0.5mL).2mL hexanes are added into reaction solution after stirring reaction 1h at room temperature, are obtained a large amount of shallow
Yellow solid, removes mother liquor, and solid is washed through hexane (2 × 1mL), vacuum drying.
Obtain rare earth metal to be obstructed the derivatives of Lewis Acids and Bases pair, be denoted as B1.
B1 is light yellow solid powder, quality 80.4mg, yield 87%.
Make elemental analysis, single crystal diffraction, nucleus magnetic hydrogen spectrum to B1, carbon is composed, and phosphorus is composed to characterize its structure.Data are as follows:
Elemental analysis:Calculated value: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 are shown in Fig. 2.
Embodiment 6
At room temperature by intermediate product M2 (50.0mg, 0.062mmol) and N, N- dimethyl puratized agricultural spray four (pentafluorophenyl group) boric acid
Salt (49.6mg, 0.062mmol) mixing in toluene (1mL).The toluene solution of chalcone is added after 5min thereto
(12.9mg,0.062mmol,0.5mL).2mL hexanes are added into reaction solution after stirring reaction 1h at room temperature, are obtained a large amount of pale yellow
Color solid, removes mother liquor, and solid is washed through hexane (2 × 1mL), vacuum drying.
Obtain rare earth metal to be obstructed the derivatives of Lewis Acids and Bases pair, be denoted as B2.
B2 is light yellow solid powder, quality 74.6mg, yield 75%.
Make elemental analysis, single crystal diffraction, nucleus magnetic hydrogen spectrum to B2, carbon is composed, and phosphorus is composed to characterize its structure.Data are as follows:
Elemental analysis:Calculated value: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 are shown in Fig. 3.
Embodiment 7
At room temperature by intermediate product M2 (60.0mg, 0.074mmol) and N, N- dimethyl puratized agricultural spray four (pentafluorophenyl group) boric acid
Salt (59.6mg, 0.074mmol) mixing in toluene (1mL).Added thereto in alpha-methylene-γ-methene penta after 5min
The toluene solution (8.3mg, 0.074mmol, 0.5mL) of ester.2mL hexanes are added into reaction solution after stirring reaction 1h at room temperature,
A large amount of light yellow solids are obtained, remove mother liquor, solid is washed through hexane (2 × 1mL), vacuum drying.
Obtain rare earth metal to be obstructed the derivatives of Lewis Acids and Bases pair, be denoted as B3.
B3 is light yellow solid powder, quality 96.5mg, yield 86%.
Make elemental analysis to B3, nucleus magnetic hydrogen spectrum, carbon spectrum, (nmr analysis show that B3 is non-by two kinds to phosphorus spectrum to characterize its structure
Enantiomter is formed).Data are as follows:
Elemental analysis:Calculated value: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 for weighing 56.0mg is obstructed Lewis Acids and Bases to A1 and is dissolved in 0.4mL toluene, will
200.2mg methyl methacrylates are added in the solution.
One is taken out after 24h to be added dropwise in deuterochloroform through nuclear-magnetism measure monomer conversion ratio, then adds 5ml thereto
The Jia Chun Rong Ye temper of 5% hydrochloric acid goes out, and adds 20ml methanol stirring 1h, filtering, is dried under vacuum to constant weight.
Survey the number-average molecular weight and molecular weight distribution of polymer.Data are shown in Table 1.
Embodiment 9
In glove box, the rare earth metal for weighing 57.7mg is obstructed Lewis Acids and Bases to A2 and is dissolved in 0.4mL toluene, will
200.2mg methyl methacrylates are added in the solution.
One is taken out after 4h to be added dropwise in deuterochloroform through nuclear-magnetism measure monomer conversion ratio, then adds 5ml thereto
The Jia Chun Rong Ye temper of 5% hydrochloric acid goes out, and adds 20ml methanol stirring 1h, filtering, is dried under vacuum to constant weight.
Survey the number-average molecular weight and molecular weight distribution of polymer.Data are shown in Table 1.
Embodiment 10
In glove box, the rare earth metal for weighing 28.0mg is obstructed Lewis Acids and Bases to A1 and is dissolved in 1mL chlorobenzenes, will
The 2- methene butyrolactone of 196.2mg is added in the solution.
The molten liquid temper of first alcohol for adding the hydrochloric acid of 5ml 5% after 6h thereto goes out, and adds 20ml methanol stirring 1h, filters, very
Sky is dry to constant weight.
The yield of polymer is surveyed, surveys the number-average molecular weight and molecular weight distribution of polymer.Data are shown in Table 1.
Embodiment 11
In glove box, the rare earth metal for weighing 28.9mg is obstructed Lewis Acids and Bases to A2 and is dissolved in 1mL chlorobenzenes, will
The 2- methene butyrolactone of 196.2mg is added in the solution.
The molten liquid temper of first alcohol for adding the hydrochloric acid of 5ml 5% after 1.5h thereto goes out, and adds 20ml methanol stirring 1h, filters,
It is dried under vacuum to constant weight.
The yield of polymer is surveyed, surveys the number-average molecular weight and molecular weight distribution of polymer.Data are shown in Table 1.
Embodiment 12
In glove box, the rare earth metal for weighing 28.0mg is obstructed Lewis Acids and Bases to A1 and is dissolved in 1mL chlorobenzenes, will
Alpha-methylene-the γ of 224.3mg-methene valerolactone is added in the solution.
One is taken out after 1h to be added dropwise in deuterochloroform through nuclear-magnetism measure monomer conversion ratio, then adds 5ml thereto
The Jia Chun Rong Ye temper of 5% hydrochloric acid goes out, and adds 20ml methanol stirring 1h, filtering, is dried under vacuum to constant weight.
Survey the number-average molecular weight and molecular weight distribution of polymer.Data are shown in Table 1.
Embodiment 13
In glove box, the rare earth metal for weighing 28.9mg is obstructed Lewis Acids and Bases to A2 and is dissolved in 1mL chlorobenzenes, will
Alpha-methylene-the γ of 224.3mg-methene valerolactone is added in the solution.
One is taken out after 3min to be added dropwise in deuterochloroform through nuclear-magnetism measure monomer conversion ratio, then adds 5ml thereto
The Jia Chun Rong Ye temper of 5% hydrochloric acid goes out, and adds 20ml methanol stirring 1h, filtering, is dried under vacuum to constant weight.
Survey the number-average molecular weight and molecular weight distribution of polymer.Data are shown in Table 1.
Embodiment 14
In glove box, the rare earth metal for weighing 28.9mg is obstructed Lewis Acids and Bases to A2 and is dissolved in 8mL chlorobenzenes, will
1794.1mg alpha-methylenes-γ-methene valerolactone is added in the solution.
One is taken out after 5min to be added dropwise in deuterochloroform through nuclear-magnetism measure monomer conversion ratio, then adds 5ml thereto
The Jia Chun Rong Ye temper of 5% hydrochloric acid goes out, and adds 20ml methanol stirring 1h, filtering, is dried under vacuum to constant weight.
Survey the number-average molecular weight and molecular weight distribution of polymer.Data are shown in Table 1.
Table 1
Wherein, monomer conversion is measured by nuclear-magnetism, and data representation polymer yield in bracket, polymer yield passes through title
Weight method measures.Number-average molecular weight and molecular weight distribution are measured by GPC.
Rare earth metal provided by the present invention, which is can be seen that, by the data in table 1 is obstructed Lewis Acids and Bases to gathering to ester
Conjunction has preferable catalytic effect.
Claims (9)
1. a kind of three tooth NNP ligands, it is characterised in that the general structure of the three teeth NNP ligands 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 teeth NNP ligands according to claim 1, it is characterised in that the structural formula of the three teeth NNP ligands is:
Or,
The Lewis Acids and Bases pair 3. a kind of rare earth metal is obstructed, it is characterised in that the rare earth metal is obstructed Lewis Acids and Bases pair
General structure is:
Wherein, RE represents Y or Sc;N=1 or 2;R' is C1-C4Alkyl;R1For C1-C4Alkyl;R2For C1-C4Chain-like alkyl, C3-C6
Cycloalkyl or aryl;R " is C1-C4Alkyl.
The Lewis Acids and Bases pair 4. rare earth metal according to claim 3 is obstructed, it is characterised in that the rare earth metal is obstructed
The structural formula of Lewis Acids and Bases pair is:
Or,
Wherein, DIPP represents 2,6- diisopropyl phenyls;Ar is 2,6- di-tert-butyl-phenyls.
The preparation method of Lewis Acids and Bases pair 5. the rare earth metal described in a kind of claim 3 is obstructed, it is characterised in that including such as
Lower step:
Three tooth NNP ligands and the first rare earth compound are reacted to obtain the second rare earth compound in organic solvent;Three tooth
NNP ligands are three tooth NNP ligands described in claim 1;First rare earth compound is trialkyl rare earth compound or three
Amido rare earth compound;Second rare earth compound is dialkyl group rare earth compounding or two amido rare earth compoundings;
Second rare earth compound and phenolic compounds are reacted to obtain the 3rd rare earth compound in organic solvent;The phenolate
Compound is C1-C4Alkyl-substituted phenol;3rd rare earth compound coordinates for monoalkyl rare earth compounding or monoamine base rare earth
Thing;
React to obtain rare earth metal by the 3rd rare earth compound and cationic reagent to be obstructed Lewis Acids and Bases pair;The sun
Ionization reagent contains B (C6F5)4Functional group.
The derivative of Lewis Acids and Bases pair 6. the rare earth metal described in a kind of claim 3 is obstructed, it is characterised in that the derivative
The general structure of thing is:
Wherein, RE represents Y or Sc;N=1 or 2;R' is C1-C4Alkyl;R1For C1-C4Alkyl;R2For C1-C4Chain-like alkyl, C3-C6
Cycloalkyl or aryl;R " is C1-C4Alkyl;R3For H, C1-C4Chain-like alkyl, C3-C6Cycloalkyl or aryl;R4For alkoxy, N,
N- dialkyl group, H, C1-C4Chain-like alkyl, C3-C6Cycloalkyl or aryl;R5For H, C1-C4Chain-like alkyl, C3-C6Cycloalkyl or virtue
Base;
Or,
Wherein, RE represents Y or Sc;N=1 or 2;R' is C1-C4Alkyl;R1For C1-C4Alkyl;R2For C1-C4Chain-like alkyl, C3-C6
Cycloalkyl or aryl;R " is C1-C4Alkyl;R7For H, C1-C4Chain-like alkyl, C3-C6Cycloalkyl or aryl;R8For H, C1-C4Chain
Shape alkyl, C3-C6Cycloalkyl or aryl.
7. derivative according to claim 6, it is characterised in that the structural formula of the derivative is:
Or,
Or,
Wherein, DIPP represents 2,6- diisopropyl phenyls;Ar is 2,6- di-tert-butyl-phenyls.
8. the preparation method of the derivative described in a kind of claim 6, it is characterised in that include the following steps:
The rare earth metal Lewis Acids and Bases pair that are obstructed are reacted to obtain in organic solvent with carbonyls;
The rare earth metal is obstructed Lewis Acids and Bases to being obstructed Lewis Acids and Bases pair for the rare earth metal described in claim 3;
The general formula of the carbonyls is R4-CO-R3C=CH-R5Or
Wherein, R3For H, C1-C4Chain-like alkyl, C3-C6Cycloalkyl or aryl;R4For alkoxy, 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. claim 3-4 any one of them rare earth metals are obstructed described in Lewis Acids and Bases pair or claim any one of 6-7
Application of the derivative in polyisocyanate polyaddition.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103071533A (en) * | 2013-02-04 | 2013-05-01 | 中国科学院上海有机化学研究所 | Pb(Ni1/3Nb2/3)O3 (PNN) ligand-iron complex catalyst and preparation method and application thereof |
CN103889992A (en) * | 2011-08-02 | 2014-06-25 | 罗克伍德锂有限责任公司 | Homoleptic rare earth triaryl complexes |
CN104203966A (en) * | 2011-08-02 | 2014-12-10 | 罗克伍德锂有限责任公司 | [eta]5:[eta]1-cyclopentadienylidene-phosphorane constrained geometry complexes of rare earth metals |
CN104725420A (en) * | 2013-12-23 | 2015-06-24 | 中国科学院上海有机化学研究所 | PNN ligand, PNN ligand iron or cobalt complex, and preparation method and application thereof |
-
2016
- 2016-09-27 CN CN201610855047.5A patent/CN106478717B/en not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103889992A (en) * | 2011-08-02 | 2014-06-25 | 罗克伍德锂有限责任公司 | Homoleptic rare earth triaryl complexes |
CN104203966A (en) * | 2011-08-02 | 2014-12-10 | 罗克伍德锂有限责任公司 | [eta]5:[eta]1-cyclopentadienylidene-phosphorane constrained geometry complexes of rare earth metals |
CN103071533A (en) * | 2013-02-04 | 2013-05-01 | 中国科学院上海有机化学研究所 | Pb(Ni1/3Nb2/3)O3 (PNN) ligand-iron complex catalyst and preparation method and application thereof |
CN103962183A (en) * | 2013-02-04 | 2014-08-06 | 中国科学院上海有机化学研究所 | PNN ligand-metal complex catalyst as well as preparation method and application thereof |
CN104725420A (en) * | 2013-12-23 | 2015-06-24 | 中国科学院上海有机化学研究所 | PNN ligand, PNN ligand iron or cobalt complex, and preparation method and application thereof |
Non-Patent Citations (3)
Title |
---|
Activation of carbon dioxide and carbon disulfide by a scandium N-heterocyclic carbene complex;Polly L. Arnold et al.,;《Dalton Trans.》;20131028;第43卷;第34-37页 * |
Andy M. Chapman et al.,.Frustrated Lewis Pairs beyond the Main Group: Synthesis,Reactivity, and Small Molecule Activation with Cationic Zirconocene Phosphinoaryloxide Complexes.《J. Am. Chem. Soc.》.2011,第133卷(第45期),第18463-18478页. * |
Frustrated Lewis Pair Behavior of [Cp2ZrOCR2CH2PPh2]+ Cations;Xin Xu et al.,;《Organometallics》;20150205;第34卷(第11期);第2655-2661页 * |
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