CN102503966A - Schiff-base ligand-based rare-earth metal complex, preparation method and applications - Google Patents

Abstract

The invention relates to a rare earth metal complex based on a Schiff base ligand, a preparation method and an application. The complex is prepared by reacting a Schiff base ligand with a rare earth metal amine compound. The complex is used as a catalyst without the assistance of any activator or co-catalyst, can directly and efficiently catalyze the hydroalkoxylation reaction and the hydroamination reaction, and can be recycled in the catalytic reaction. The general structural formula of this type of rare earth supported catalyst is as follows:

Description

Rare earth metal complex based on Schiff base ligand, preparation method and use

technical field

The invention relates to a class of rare earth metal complexes based on Schiff base ligands, which form self-supporting catalysts through coordination between Schiff base ligands and rare earth metal ions, wherein rare earth metal ions provide catalytic centers and nodes of the skeleton, and coordinate The body constitutes the framework of the entire self-supporting catalyst. The advantage is that these self-supported catalysts are heterogeneous in commonly used organic solvents and exhibit unique performance in catalyzing hydroalkoxidation and hydroamination reactions. The rare earth self-supporting catalyst can be recycled, and the rare earth metal will not remain in the product, which is in line with the concept of green chemistry. the

technical background

Heterocyclic compounds are an important class of organic compounds, which exist as core units in many natural products and synthetic drugs. In the route of synthesizing nitrogen-containing heterocycles and oxygen-containing heterocycles, intramolecular hydroamination and hydroalkoxylation of double bonds (or triple bonds) with amino groups (or hydroxyl groups) is the most atom-economical synthesis method. the

In 1989, the Marks group first reported that rare earth metal compounds could catalyze the intramolecular hydroamination of alkenes. They gave a possible reaction mechanism (Gagne, M.R.; Marks, T.J.J.Am.Chem.Soc.1989, 111, 4108.):

In 2007, the Marks research group reported that the rare earth metal amine compound La[N(SiMe ₃ ) ₂ ] ₃ can realize intramolecular hydroalkoxylation of allenes containing hydroxyl groups, and then obtain oxygen-containing heterocyclic products. This is the first report on the rare earth compound-catalyzed hydroalkoxylation of olefins. The reaction mechanism is different from that catalyzed by transition metal compounds.

Ln catalyzes intramolecular hydroalkoxylation of allenols;

La[N(SiMe ₃ ) ₂ ] ₃ catalyzes the hydroalkoxylation reaction mechanism of unsaturated hydrocarbons containing hydroxyl groups.

In 2005, the Livinghouse research group reported the intramolecular hydroamination of olefins catalyzed by rare earth metal yttrium complexes. Their research group used a sulfur-containing phenolic yttrium complex as a catalyst. The catalyst has high catalytic efficiency for the intramolecular hydroamination of olefins (Kim, Y.K., Livinghouse, T.Org.Lett.2005, 7, 1737.):

Yttrium complexes catalyze intramolecular hydroamination reactions. the

In 2007, the Marks research group reported that a rare earth complex supported by an organophosphorus oxide ligand containing o-naphthol was used as a catalyst. This catalyst can catalyze the hydroamination reaction of olefins at room temperature with a high yield (98%), but The ee value is low (26%) (Yu, X.H., Marks, T.J.Organometallics.2007, 26, 365.):

Samarium complexes catalyze the hydroamination of alkenes. the

With the increasing awareness of global environmental protection and the concept of sustainable development, the development of highly efficient, economical, recyclable and reusable catalysts has become one of the goals pursued by many researchers. Many catalysts (including ligands and metals) that have been developed so far are not only costly, but it is difficult to realize recycling under homogeneous catalytic conditions, and the loss of harmful substances such as heavy metals into the product also restricts its application, especially in pharmaceuticals. Not acceptable in the preparation and manufacture of intermediates. Therefore, many types of heterogeneous catalysts have been developed successively. the

The most popular porous materials are metal-organic frameworks (Metal-Organic Frameworks, MOFs), which are composed of bidentate or multidentate organic ligand molecules and metal ions or atomic clusters under mild conditions by solution chemistry. It is assembled by the principle of automatic identification, so it can also be called self-supporting material. . Such metal-organic framework materials have shown promising applications in catalysis, separation, gas storage, host-guest chemistry, sensing, multifunctional materials, etc. When they are used for catalysis, we call them self-supported catalysts. the

Since self-supported catalysts have the characteristics of porosity and adsorption of small molecules of inorganic molecular sieves, and they often have extremely low solubility in many organic solvents, such catalysts provide a new way for heterogeneous catalytic reactions. The self-supporting catalyst model is as follows:

In 1982, Efraty et al. reported the heterogeneous hydrogenation of 1-hexene catalyzed by self-supporting catalyst [RhCl(CO)(1,4-(CN) ₂ C ₆ H ₄ )] _n . This self-supported catalyst can be prepared from [Rh(CO) ₂ Cl] ₂ with two equivalents of 1,4-diisocyanobenzene in dichloromethane. The specific structure of this catalyst is not clear, the author believes that there may be three forms of linear polymers, non-linear polymers and tetragonal oligomers (Efraty, A.; Frinstein, I.Inorg.Chem.1982, 21, 3115.):

In 1994, Fuiita et al. reported the first silicocyanation reaction of aromatic aldehydes catalyzed by crystalline self-supported catalysts with well-defined structures. The author used 4,4'-bipyridine (4,4'-bpy) to react with Cd(NO ₃ ) ₂ in ethanol-water system to form a colorless and transparent crystalline self-supporting catalyst {[Cd(4, 4'-bpy) ₂ (H ₂ O) ₂ ](NO ₃ ) ₂ ·H ₂ O} _n (1),. The catalyst has a two-dimensional planar square network structure, in which the metal ion Cd(II) can act as a Lewis acid to electrophilicly activate aromatic aldehydes and catalyze the nucleophilic addition reaction of trimethylsilonitrile to them. In the subsequent report, the author used this catalyst to catalyze the nucleophilic addition reaction of trimethylsilylnitrile to imine, and most of the substrates could react rapidly, with the yield ranging from 70% to 99%. Although the author verified that the whole reaction process is carried out in a heterogeneous phase, the recycling results of the catalyst are not given (Ohmori O., Fujita M. Chem. Commun. 2004, 1586-1587; Kato CN, Ono M., Hino T. , et al. Catal. Commun. 2006, 7: 673-677.). Self-Supported Catalyst {[Cd(4,4'-bpy) ₂ (H ₂ O) ₂ ](NO ₃ ) ₂ ·H ₂ O} _n (1) Catalyzed Heterogeneous Silicocyanation of Aromatic Aldehydes and Imines The heterogeneous silicocyanation reaction is as follows:

Lin Wenbin's research group catalyzed the hydrogenation reaction of aromatic ketones with chiral self-supporting catalysts L5-Ru-Zr and L6-Ru-Zr, and the ee value can reach 99.2%. And the catalyst can be recycled for more than 10 times without decay (Ma, L.; Abney, C.; Lin, W. Chemical Society Reviews, 2009, 38: 1248-1256.). Chiral self-supporting catalysts catalyze the hydrogenation of heterogeneous aromatic ketones as follows:

Ding Kuiling's group used 0.1mol.% chiral self-supporting catalyst to catalyze the hydrogenation reaction of aromatic ketones, and the reaction conversion rate and ee value can reach 99% (Ding, K.; Wang, Z.; Wang, X.; Liang, Y.; Wang, X. Chemistry-A European Journal, 2006, 12: 5188-5197.):

Contents of the invention

The object of the invention is to provide a rare earth metal complex containing Schiff base ligands, which is a rare earth supported catalyst. the

The purpose of the present invention is also to provide a method for preparing the above-mentioned rare earth metal complex containing Schiff base ligands and the ligands in the supported catalyst. the

Another object of the present invention is to provide the use of the above-mentioned rare earth metal complexes containing Schiff base ligands. It is used to catalyze intramolecular hydroalkoxylation or intramolecular hydroamination. Under heating at 75°C, the catalyst can efficiently catalyze intramolecular hydroalkoxylation or intramolecular hydroamination. the

The structural formula of the rare earth metal complex containing Schiff base ligand provided by the invention is as follows:

In the above structural formula, linker represents a single bond, a C _1-8 alkyl group, a phenyl group, a phenyl group substituted by a single or double C6-C20 aryl group;

R ¹ is phenyl, phenyl substituted by single or double C _1-4 alkyl or C _1-4 alkyl;

X is tri(C ₁ ~C ₅ alkyl) silicon-substituted amine group; M is Y, Sc or rare earth metal ion of lanthanide ion; ----→ is a coordination bond or no bond;

n is a natural number in the range of 2-500, more preferably 2-100, more preferably 10-50. the

Wherein, the Schiff base ligand can be a compound of the following configuration:

The present invention also provides the synthetic method of above-mentioned Schiff base ligand, and this synthetic method is as follows:

Compound 1 or 7 and (linker)(B(OH) ₂ ) undergo Suzuki coupling reaction under the catalysis of Pd(PPh ₃ ) ₄ and base to obtain compound 5 or 8, respectively;

In an organic solvent, under the action of BBr ₃ , the methyl protecting group is removed to obtain compound 6 or 9;

Compound 6 or 9 reacted with H ₂ NR ¹ under reflux in an organic solvent to obtain Schiff base ligands L1-L6 respectively;

The reaction of the present invention is recommended to be carried out under inert gas. the

Wherein R1 is phenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl or n-butyl;

The structural formulas of compounds 1, 5, 6, 7, 8 and 9 are as follows:

The linker and Schiff base ligands L1-L6 are the same as those described above. the

The above-mentioned Schiff base ligand preparation process, taking the Schiff base ligand L1 as an example, can be simply expressed by the following reaction formula:

In the formula, Me represents methyl, EtOH represents ethanol, n-Bu represents n-butyl, DME represents ethylene glycol dimethyl ether, DMF represents N,N-dimethylformamide, and DCM represents dichloromethane. the

Compound 1 and potassium iodide are reacted at room temperature in an organic solvent such as DMF under the catalysis of a base. After a few hours, quench with saturated ammonium chloride solution, extract with a solvent such as dichloromethane, combine the organic phases, and evaporate the solvent under reduced pressure , recrystallized with a solvent such as n-hexane, and compound 2 was obtained after the above treatment. the

Under a nitrogen atmosphere, dissolve compound 2 in a solvent such as absolute ethanol, add a catalytic amount of concentrated hydrochloric acid dropwise, then add triethyl orthoformate, heat and reflux for several hours, distill off the solvent under reduced pressure, and use saturated sodium bicarbonate solution Quench, extract with a solvent such as dichloromethane, combine the organic phases, evaporate the solvent under reduced pressure, and obtain compound 3 after the above treatment. the

Under nitrogen atmosphere, at -78°C, add the n-hexane solution of butyllithium to the organic solvent of compound 3, such as tetrahydrofuran, drop by drop. After reacting for 2 hours, add trimethyl borate dropwise, return to room temperature and react overnight , and then adjust the pH to 1 with dilute hydrochloric acid, extract with an organic solvent such as ethyl acetate, combine the organic phases, evaporate the organic solvent under reduced pressure, recrystallize with ethyl acetate, and obtain compound 4 after the above treatment. the

Under nitrogen atmosphere, heat compound 4 and compound 1 under the action of Pd(PPh ₃ ) ₄ and a base in an organic solvent such as a mixed solvent of DME and water, heat to reflux for 2 days, quench with dilute hydrochloric acid, and use an organic solvent such as Extract with dichloromethane, combine the organic phases, distill off the solvent under reduced pressure, perform column purification, and obtain compound 5 after the above treatment.

Under a nitrogen atmosphere, add BBr ₃ dropwise to an organic solvent of compound 5 such as dichloromethane at -78°C. After several hours of reaction, add ice water to quench, extract with an organic solvent such as dichloromethane, and combine the organic phases , the solvent was distilled off under reduced pressure, recrystallized from dichloromethane, and compound 6 was obtained after the above treatment.

Compound 6 and 2,6-dimethylaniline were refluxed in an organic solvent such as absolute ethanol. After several hours, the solvent was evaporated under reduced pressure, recrystallized with absolute ethanol, and ligand L1 was obtained through the above treatment. the

In the above method of the present invention, the organic solvent used recommends DMF, dehydrated alcohol, tetrahydrofuran, DME, methylene chloride, toluene; The base used is recommended to be sodium carbonate, potassium carbonate, cesium carbonate; The acid used is recommended to be hydrochloric acid. the

The present invention provides a class of above-mentioned rare earth metal complexes containing Schiff base ligands, the structural formula of which is as follows:

Among them, linker represents a single bond, C _1-8 alkyl, phenyl, single or double C6 ~ C20 aryl substituted phenyl, and is further recommended as a single bond, 1,3-bis(4-hydroxy-5-( 2,6-diisopropylbenzimine)methyl)phenyl or 1,3-bis(4-hydroxy-5-(2,6-dimethylbenzimine)methyl)phenyl;

R ¹ is phenyl, phenyl substituted by mono or double C _1-4 alkyl or C _1-4 alkyl, further recommended is phenyl, 2,6-dimethylphenyl, 2,6-diiso Propylmethyl or n-butyl;

X is an amino group substituted with a tri(C ₁ ~C ₅ alkyl) silicon group, further recommended as N(SiMe ₃ ) ₂ ; M is a rare earth metal ion of Y, Sc or lanthanide ion, further recommended as La, Y, Nd or Sm; ----→ is a coordination bond or no bond;

n is a natural number in the range of 2-500, more preferably 2-100, more preferably 10-50. the

The present invention also provides the synthetic method of above-mentioned rare earth metal complex, and this synthetic method is as follows:

Ligands L1-L6 and rare earth metal amine compound MX ₃ are obtained by stirring and reacting for 0.1-12 hours in an organic solvent at 25-50°C.

Wherein, the molar ratio of ligand L1, L2, L5 or L6 to rare earth metal amine compound _MX3 is 1:0.8～1:1.5; the molar ratio of ligand L3 or L4 to rare earth metal amine compound _MX3 is 1: 0.5～1:0.8; the rare earth metal amine compound MX ₃ is recommended to be Ln(N(SiMe ₃ ) ₂ ) ₃ (Ln=La, Y, Nd, Sm); the organic solvent is recommended to be toluene or n-hexane.

R1, M, X, linker, and n are as described above. the

In the method of the present invention, the preparation process of the above-mentioned rare earth metal complexes containing Schiff base ligands takes the preparation of C1 by the reaction of ligand L1 and La(N(SiMe ₃ ) ₂ ) ₃ as an example, which can be simply represented by the following reaction formula :

The reaction conditions recommended to the synthetic method of above-mentioned reaction are specifically as follows:

Add the toluene solution of the ligand L1 dropwise to the La(N(SiMe ₃ ) ₂ ) ₃ toluene (Toluene) solution, and an orange-red precipitate is precipitated. The system is stirred at room temperature for 1 hour, and the supernatant is removed after centrifugation. The residual solid After repeated washing with toluene for several times, the obtained red solid was dried under vacuum for 3 hours and used for hydroalkoxylation.

Among them, the ligands L1-L6, R ¹ , M, and X are as described above, and n=35.

A class of rare earth metal supported catalysts containing Schiff base ligands synthesized by the present invention does not require any activators, the coexistence of activators and co-catalysts, or any organic or inorganic supports, and can catalyze hydroalkoxylation and hydroamination reactions , which is further recommended for intramolecular hydroalkoxylation and hydroamination reactions. the

Detailed ways

The following implementation examples will help to further understand the present invention, but can not limit the content of the present invention. the

Example 1

In a 50mL single-necked bottle, add 4,4'-dihydroxy-3,3'-dialdehyde biphenyl (127g, 52mmol), 2,6-dimethylaniline (0.23mL, 1.05mmol) and 10mL absolute ethanol , heated to reflux for 2 hours. The solvent was removed, and the residual solid was recrystallized from absolute ethanol to obtain 3,3'-bis-(2,6-dimethylbenimine)methyl)biphenyl-4,4'-diol L1 (140mg, 60 % yield (yield)). ¹ H NMR (400MHz, CDCl ₃ ): δ(ppm) 13.14 (s, 2H, OH)), 8.42 (s, 2H, N=CH), 7.58 (dd, J=2.4, 3.6Hz, 2H, ArH) , 7.52 (d, J=2.4Hz, 2H, ArH), 7.11-7.15 (m, 6H, ArH), 7.01-7.06 (m, 2H, ArH), 2.22 (s, 24H ^, CH ₃ ); (100MHz, CDCl ₃ ): δ(ppm) 116.4, 110.4, 97.9, 81.0, 80.8, 79.6, 77.8, 77.7, 77.5, 74.5, 68.5, 67.5. HRMS (MALDI): C ₃₀ H ₂₉ N ₂ O ₂ (M ⁺ ) Calculated value: 449.2223; Measured value: 449.2224.

Example 2

In a 50mL single-necked bottle, add 4,4'-dihydroxy-3,3'-dialdehyde biphenyl (127mg, 0.52mmol), 2,6-diisopropylaniline (0.26mL, 1.05mmol) and 10mL without water and ethanol, heated to reflux for 2 hours. The solvent was removed, and the residual solid was recrystallized from absolute ethanol to obtain 3,3'-bis-(2,6-diisopropylphenylimine)methyl)biphenyl-4,4'-diol L2 (150mg, 63% yield). ¹ H NMR (400MHz, CDCl ₃ ): δ(ppm) 13.15 (s, 2H, OH)), 8.39 (s, 2H, CH=N), 7.64 (dd, J=2, 2Hz, 2H, ArH), 7.53(d, J=2Hz, 2H, ArH), 7.20(s, 6H, ArH), 7.16(d, J=8.8Hz, 2H, ArH), 2.98-3.05(m, 4H, CH(CH ₃ ) ₂ ), 1.19 (d, J=7.2Hz, 24H, CH(CH ₃ ) ₂ ); ¹³ C NMR (100MHz, CDCl ₃ ): δ(ppm) 166.7, 160.6, 146.2, 138.8, 131.7, 131.6, 130.2, 125.7 , 123.4, 118.9, 28.3, 23.7. HRMS (MALDI): Calcd. for C ₃₈ H ₄₅ N ₂ O ₂ (M ⁺ ): 561.3482; Found: 561.3476.

Example 3

In a 50mL single-necked bottle, add 1,3,5-tris(4-hydroxy-5-formylphenyl)benzene (1g, 2.3mmol), 2,6-dimethylaniline (1.5mL, 6.8mmol), without A mixed solvent of water, ethanol and toluene (v/v=2/1), heated under reflux for 2 hours to complete the reaction. The solvent was removed, and the residual solid was recrystallized from absolute ethanol to obtain 1,3,5-tris-(4-hydroxy-5-(2,6-dimethylbenimine)methyl)benzene L3 (1.4g, 65 %yield). ¹ H NMR (400MHz, CDCl ₃ ): δ(ppm) 13.22 (s, 3H, OH), 8.45 (s, 3H, CH=N), 7.76 (dd, J=2.0, 2.4Hz, 3H, ArH), 7.69(s, 3H, ArH), 7.65(d, J=2.4Hz, 3H, ArH), 7.18(m, 3H, ArH), 7.11(m, 6H, ArH), 7.04(m, 3H, ArH), 2.23 (s, 18H, CH ₃ ); ¹³ C NMR (100MHz, CDCl ₃ ): δ (ppm) 166.8, 161.2, 148.1, 141.7, 132.3, 132.2, 130.8, 128.5, 128.4, 125.2, 123.9, 119.1, 118.1, 18.6. HRMS (MALDI): Calcd. for C ₅₁ H ₄₆ N ₃ O ₃ (M ⁺ ): 748.3547; Found: 748.3533.

Example 4

In a 50mL single-necked bottle, add 1,3,5-tris(4-hydroxy-5-formylphenyl)benzene (1g, 2.3mmol), 2,6-diisopropylaniline (1.7mL, 6.8mmol), A mixed solvent of absolute ethanol and toluene (v/v=2/1), heated under reflux for 2 hours to complete the reaction. The solvent was removed, and the residual solid was recrystallized from absolute ethanol to obtain 1,3,5-tris-(4-hydroxy-5-(2,6-diisopropylphenylimine)methyl)benzene L4 (1.2 g, 65% yield). ¹ H NMR (400MHz, CDCl ₃ ): δ(ppm) 13.24 (s, 3H, OH), 8.40 (s, 3H, CH=N), 7.76 (dd, J=2.0, 2.4Hz, 3H, ArH), 7.70(s, 3H, ArH), 7.65(d, J=2.4Hz, 3H, ArH), 7.20(m, 12H, ArH), 3.02(m, 6H, CH(CH ₃ ) ₂ ), 1.20(d, J=6.8Hz, 36H, CH(CH ₃ ) ₂ ); ¹³ C NMR (100MHz, CDCl ₃ ): δ(ppm) 166.6, 161.2, 146.1, 141.8, 138.8, 132.4, 130.9, 125.8, 124.1, 123.5, 119.0 , 118.2, 28.3, 23.7. HRMS (MALDI): Calcd. for C ₆₃ H ₇₀ N ₃ O ₃ (M ⁺ ): 916.5409; Found: 916.5412.

Example 5

Add 4,4'-dihydroxy-3,3'-dialdehyde biphenyl (127mg, 0.52mmol), aniline (0.18mL, 1.05mmol) and 10mL absolute ethanol into a 50mL single-necked bottle, and heat to reflux for 2 hours. The solvent was removed, and the residual solid was recrystallized from absolute ethanol to obtain 3,3'-bis-phenyliminomethylbiphenyl-4,4'-diol L5 (120 mg, 83% yield). ¹ H NMR (400MHz, CDCl ₃ ): δ(ppm) 13.12 (s, 2H, OH)), 8.87 (s, 2H, CH=N), 7.79 (dd, J=2, 2Hz, 2H, ArH), 7.67 (d, J=2Hz, 2H, ArH), 7.48 (s, 4H, ArH), 7.17 (m, 4H, ArH); ¹³ C NMR (100MHz, CDCl ₃ ): δ (ppm) 166.0, 160.1, 152.2 , 152.0, 134.3, 134.1, 128.5, 123.4, 119.2, 119.0, 118.9. HRMS (MALDI): Calcd. for C ₂₆ H ₂₀ N ₂ O ₂ (M ⁺ ): 392.1582; Found: 392.2576.

Example 6

In a 50mL single-necked bottle, add 4,4'-dihydroxy-3,3'-dialdehyde biphenyl (127mg, 0.52mmol), n-butylamine (0.28mL, 1.05mmol) and 10mL of absolute ethanol, and heat to reflux for 2 Hour. The solvent was removed, and the residual solid was recrystallized from absolute ethanol to obtain 3,3'-bis-n-butylaminomethylbiphenyl-4,4'-diol L6 (95 mg, 85% yield). ¹ H NMR (400MHz, CDCl ₃ ): δ(ppm) 13.22 (s, 2H, OH)), 8.56 (s, 2H, CH=N), 7.89 (dd, J=2, 2Hz, 2H, ArH), 7.77(d, J=2Hz, 2H, _ArH ), 7.07(d, _J =2Hz, 2H, ArH), 3.71(t, J=3Hz, 2H, _{CH3CH2CH2CH2 )} , 1.65(m, 2H, _{CH3CH2CH2CH2 ) ,} 1.31 ₍ m, _{2H , CH3CH2CH2CH2 )} , 0.90 ( _t , J=4Hz, _{3H , CH3CH2CH2CH2} ); ^13C NMR (100MHz, CDCl ₃ ): δ (ppm) 160.0, 157.5, 134.3, 132.8, 131.4, 125.1, 120.9, 61.5, 33.8, 20.3, 13.8. HRMS (MALDI): C ₂₂ H ₂₈ N ₂ O ₂ (M ⁺ ) calculated value: 352.2252; measured value: 352.2356.

Example 7

A 2 mL toluene solution of La(N(SiMe ₃ ) ₂ ) ₃ (60 mg, 0.097 mmol) was slowly dropped into a 10 mL toluene solution of L1 (44 mg, 0.097 mmol), and a precipitate formed immediately. After stirring overnight at room temperature, centrifuge, remove the supernatant, and wash the precipitate with 5×3 mL toluene to obtain the rare earth self-supported catalyst C1 (70 mg, 97% yield), n=35.

Example 8

A 2 mL toluene solution of L1 (44 mg, 0.097 mmol) was slowly dropped into a 10 mL toluene solution of La(N(SiMe ₃ ) ₂ ) ₃ (60 mg, 0.097 mmol), and a precipitate formed immediately. After stirring at room temperature overnight, centrifuge, remove the supernatant, and wash the precipitate with 5×3 mL toluene to obtain the rare earth self-supporting catalyst C2 (70 mg, 96% yield), n=30.

Example 9

A 2 mL toluene solution of La(N(SiMe ₃ ) ₂ ) ₃ (60 mg, 0.097 mmol) was slowly dropped into a 10 mL toluene solution of L2 (47 mg, 0.097 mmol), and a precipitate formed immediately. After stirring overnight at room temperature, centrifuge, remove the supernatant, and wash the precipitate with 5×3 mL toluene to obtain the rare earth self-supported catalyst C3 (80 mg, 96% yield), n=50.

Example 10

A 2 mL toluene solution of L2 (47 mg, 0.097 mmol) was slowly dropped into a 10 mL toluene solution of La(N(SiMe ₃ ) ₂ ) ₃ (60 mg, 0.097 mmol), and a precipitate formed immediately. After stirring overnight at room temperature, centrifuge, remove the supernatant, and wash the precipitate with 5×3 mL toluene to obtain the rare earth self-supported catalyst C4 (83 mg, 99% yield) n=45.

Example 11

A 2 mL toluene solution of La(N(SiMe ₃ ) ₂ ) ₃ (60 mg, 0.097 mmol) was slowly dropped into a 10 mL toluene solution of L3 (49 mg, 0.065 mmol), and a precipitate formed immediately. After stirring overnight at room temperature, centrifuge, remove the supernatant, and wash the precipitate with 5×3 mL toluene to obtain the rare earth self-supporting catalyst C5 (65 mg, 95% yield), n=10.

Example 12

A solution of L3 (49 mg, 0.065 mmol) in 2 mL of toluene was slowly dropped into a solution of La(N(SiMe ₃ ) ₂ ) ₃ (60 mg, 0.097 mmol) in 10 mL of toluene, and a precipitate formed immediately. After stirring overnight at room temperature, centrifuge, remove the supernatant, and wash the precipitate with 5×3 mL toluene to obtain the rare earth self-supporting catalyst C6 (66 mg, 97% yield), n=20.

Example 13

A 2 mL toluene solution of La(N(SiMe ₃ ) ₂ ) ₃ (60 mg, 0.097 mmol) was slowly dropped into a 10 mL toluene solution of L4 (54 mg, 0.065 mmol), and a precipitate formed immediately. After stirring overnight at room temperature, centrifuge, remove the supernatant, and wash the precipitate with 5×3 mL toluene to obtain the rare earth self-supported catalyst C7 (76 mg, 96% yield), n=20.

Example 14

A 2 mL toluene solution of L4 (54 mg, 0.065 mmol) was slowly dropped into a 10 mL toluene solution of La(N(SiMe ₃ ) ₂ ) ₃ (60 mg, 0.097 mmol), and a precipitate formed immediately. After stirring overnight at room temperature, centrifuge, remove the supernatant, and wash the precipitate with 5×3 mL toluene to obtain the rare earth self-supported catalyst C8 (78 mg, 99% yield), n=30.

Example 15

A 2 mL toluene solution of Y(N(SiMe ₃ ) ₂ ) ₃ (55 mg, 0.097 mmol) was slowly dropped into a 10 mL toluene solution of L1 (44 mg, 0.097 mmol), and a precipitate formed immediately. After stirring at room temperature overnight, centrifuge, remove the supernatant, and wash the precipitate with 5×3 mL toluene to obtain rare earth self-supported catalyst C9 (71 mg, 97% yield), n=30.

Example 16

A 2 mL toluene solution of L1 (44 mg, 0.097 mmol) was slowly dropped into a 10 mL toluene solution of Y(N(SiMe ₃ ) ₂ ) ₃ (55 mg, 0.097 mmol), and a precipitate formed immediately. After stirring overnight at room temperature, centrifuge, remove the supernatant, and wash the precipitate with 5×3 mL toluene to obtain the rare earth self-supported catalyst C10 (72 mg, 99% yield), n=30.

Example 17

A 2 mL toluene solution of Y(N(SiMe ₃ ) ₂ ) ₃ (55 mg, 0.097 mmol) was slowly dropped into a 10 mL toluene solution of L2 (47 mg, 0.097 mmol), and a precipitate formed immediately. After stirring overnight at room temperature, centrifuge, remove the supernatant, and wash the precipitate with 5×3 mL toluene to obtain the rare earth self-supported catalyst C11 (82 mg, 96% yield), n=35.

Example 18

A 2 mL toluene solution of L2 (47 mg, 0.097 mmol) was slowly dropped into a 10 mL toluene solution of Y(N(SiMe ₃ ) ₂ ) ₃ (55 mg, 0.097 mmol), and a precipitate formed immediately. After stirring overnight at room temperature, centrifuge, remove the supernatant, and wash the precipitate with 5×3 mL toluene to obtain the rare earth self-supported catalyst C12 (84 mg, 98% yield), n=35.

Example 19

A 2 mL toluene solution of Nd(N(SiMe ₃ ) ₂ ) ₃ (61 mg, 0.097 mmol) was slowly dropped into a 10 mL toluene solution of L1 (44 mg, 0.097 mmol), and a precipitate formed immediately. After stirring overnight at room temperature, centrifuge, remove the supernatant, and wash the precipitate with 5×3 mL toluene to obtain the rare earth self-supported catalyst C13 (69 mg, 95% yield), n=30.

Example 20

A 2 mL toluene solution of L1 (44 mg, 0.097 mmol) was slowly dropped into a 10 mL toluene solution of Nd(N(SiMe ₃ ) ₂ ) ₃ (61 mg, 0.097 mmol), and a precipitate formed immediately. After stirring overnight at room temperature, centrifuge, remove the supernatant, and wash the precipitate with 5×3 mL toluene to obtain the rare earth self-supporting catalyst C14 (71 mg, 98% yield), n=30.

Example 21

A 2 mL toluene solution of Nd(N(SiMe ₃ ) ₂ ) ₃ (61 mg, 0.097 mmol) was slowly dropped into a 10 mL toluene solution of L2 (47 mg, 0.097 mmol), and a precipitate formed immediately. After stirring at room temperature overnight, centrifuge, remove the supernatant, and wash the precipitate with 5×3 mL toluene to obtain the rare earth self-supported catalyst C15 (80 mg, 96% yield), n=30.

Example 22

A solution of L2 (47 mg, 0.097 mmol) in 2 mL of toluene was slowly dropped into a solution of Nd(N(SiMe ₃ ) ₂ ) ₃ (61 mg, 0.097 mmol) in 10 mL of toluene, and a precipitate formed immediately. After stirring overnight at room temperature, centrifuge, remove the supernatant, and wash the precipitate with 5×3 mL toluene to obtain rare earth self-supported catalyst C16 (82 mg, 99% yield), n=30.

Example 23

A 2 mL toluene solution of Sm(N(SiMe ₃ ) ₂ ) ₃ (61 mg, 0.097 mmol) was slowly dropped into a 10 mL toluene solution of L1 (44 mg, 0.097 mmol), and a precipitate formed immediately. After stirring overnight at room temperature, centrifuge, remove the supernatant, and wash the precipitate with 5×3 mL toluene to obtain the rare earth self-supported catalyst C17 (68 mg, 95% yield), n=20.

Example 24

A 2 mL toluene solution of L1 (44 mg, 0.097 mmol) was slowly dropped into a 10 mL toluene solution of Nd(N(SiMe ₃ ) ₂ ) ₃ (61 mg, 0.097 mmol), and a precipitate formed immediately. After stirring at room temperature overnight, centrifuge, remove the supernatant, and wash the precipitate with 5×3 mL toluene to obtain rare earth self-supported catalyst C18 (69 mg, 96% yield), n=20.

Example 25

A 2 mL toluene solution of Nd(N(SiMe ₃ ) ₂ ) ₃ (61 mg, 0.097 mmol) was slowly dropped into a 10 mL toluene solution of L2 (47 mg, 0.097 mmol), and a precipitate formed immediately. After stirring overnight at room temperature, centrifuge, remove the supernatant, and wash the precipitate with 5×3 mL toluene to obtain the rare earth self-supported catalyst C19 (79 mg, 95% yield), n=20.

Example 26

A solution of L2 (47 mg, 0.097 mmol) in 2 mL of toluene was slowly dropped into a solution of Nd(N(SiMe ₃ ) ₂ ) ₃ (61 mg, 0.097 mmol) in 10 mL of toluene, and a precipitate formed immediately. After stirring overnight at room temperature, centrifuge, remove the supernatant, and wash the precipitate with 5×3 mL toluene to obtain the rare earth self-supporting catalyst C20 (81 mg, 97% yield), n=20.

Example 27

A 2 mL toluene solution of L2 (47 mg, 0.097 mmol) was slowly dropped into a 10 mL toluene solution of La(N(SiMe ₃ ) ₂ ) ₃ (60 mg, 0.097 mmol), and a precipitate formed immediately. After heating and stirring at 50°C for 12 hours, it was centrifuged, the supernatant was removed, and the precipitate was washed with 5×3 mL toluene to obtain the rare earth self-supporting catalyst C4a (83 mg, 99% yield), n=35.

Example 28

A 2 mL toluene solution of L2 (47 mg, 0.097 mmol) was slowly dropped into a 10 mL toluene solution of Y(N(SiMe ₃ ) ₂ ) ₃ (55 mg, 0.097 mmol), and a precipitate formed immediately. After heating and stirring at 50°C for 12 hours, it was centrifuged, the supernatant was removed, and the precipitate was washed with 5×3 mL toluene to obtain the rare earth self-supported catalyst C12 (84 mg, 98% yield), n=30.

Example 29

A solution of L2 (47 mg, 0.097 mmol) in 2 mL of toluene was slowly dropped into a solution of Nd(N(SiMe ₃ ) ₂ ) ₃ (61 mg, 0.097 mmol) in 10 mL of toluene, and a precipitate formed immediately. After heating and stirring at 50° C. for 12 hours, centrifuge, remove the supernatant, and wash the precipitate with 5×3 mL toluene to obtain the rare earth self-supporting catalyst C16a (82 mg, 99% yield), n=30.

Example 30

A solution of L2 (47 mg, 0.097 mmol) in 2 mL of n-hexane was slowly dropped into a solution of La(N(SiMe ₃ ) ₂ ) ₃ (60 mg, 0.097 mmol) in 10 mL of THF, and a precipitate formed immediately. After stirring overnight at room temperature, centrifuge, remove the supernatant, and wash the precipitate with 5×3 mL toluene to obtain the rare earth self-supported catalyst C4b (83 mg, 99% yield), n=30.

Example 31

A solution of L4 (54 mg, 0.065 mmol) in 2 mL of n-hexane was slowly dropped into a solution of La(N(SiMe ₃ ) ₂ ) ₃ (60 mg, 0.097 mmol) in 10 mL of tetrahydrofuran, and a precipitate formed immediately. After stirring overnight at room temperature, centrifuge, remove the supernatant, and wash the precipitate with 5×3 mL toluene to obtain the rare earth self-supported catalyst C6a (66 mg, 97% yield), n=15.

Example 32

A 2 mL toluene solution of La(N(SiMe ₃ ) ₂ ) ₃ (60 mg, 0.097 mmol) was slowly dropped into a 10 mL toluene solution of L5 (41 mg, 0.087 mmol), and a precipitate formed immediately. After stirring overnight at room temperature, centrifuge, remove the supernatant, and wash the precipitate with 5×3 mL toluene to obtain the rare earth self-supported catalyst C21 (67 mg, 95% yield), n=15.

Example 33

A 2 mL toluene solution of L5 (41 mg, 0.087 mmol) was slowly dropped into a 10 mL toluene solution of La(N(SiMe ₃ ) ₂ ) ₃ (60 mg, 0.097 mmol), and a precipitate formed immediately. After stirring overnight at room temperature, centrifuge, remove the supernatant, and wash the precipitate with 5×3 mL toluene to obtain the rare earth self-supporting catalyst C22 (71 mg, 97% yield), n=15.

Example 34

A 2 mL toluene solution of La(N(SiMe ₃ ) ₂ ) ₃ (60 mg, 0.097 mmol) was slowly dropped into a 10 mL toluene solution of L6 (43 mg, 0.088 mmol), and a precipitate formed immediately. After stirring overnight at room temperature, centrifuge, remove the supernatant, and wash the precipitate with 5×3 mL toluene to obtain the rare earth self-supported catalyst C23 (66 mg, 96% yield), n=15.

Example 35

A 2 mL toluene solution of L6 (43 mg, 0.088 mmol) was slowly dropped into a 10 mL toluene solution of La(N(SiMe ₃ ) ₂ ) ₃ (60 mg, 0.097 mmol), and a precipitate formed immediately. After stirring at room temperature overnight, centrifuge, remove the supernatant, and wash the precipitate with 5×3 mL toluene to obtain the rare earth self-supporting catalyst C24 (66 mg, 96% yield), n=15.

Example 36

The hydroalkoxylated substrate 2,2-dimethyl-4-pentyn-1-ol (14.9 mg, 0.164 mmol) was formulated into a 420 mg C ₆ D ₆ solution, and 12% molar equivalent of a rare earth supported catalyst was added (self-supported cat.) (C1-C24), heating at 75°C, monitoring the reaction in situ. The effects of these catalysts are shown in Table 1:

Table 1. Intramolecular hydroalkoxylation of 2,2-dimethyl-4-pentyn-1-ol catalyzed by rare earth supported catalysts C1～C24

Example 37

The substrate 2,2-dimethyl-4-pentyn-1-ol (14.9mg, 0.164mmol) of the hydroalkoxylation reaction was formulated into a 420mg C ₆ D ₆ solution, and 12% molar equivalent of catalyst C4 was added, Heating at 75°C and monitoring the reaction in situ, the conversion was 97% after heating for 5 hours. Under a nitrogen atmosphere, pour out the supernatant in the in-situ NMR tube, rinse the catalyst solid with 2×0.5mL LC ₆ D ₆ solution, and then add 420mg of 2,2-dimethyl-4-pentyn-1-ol C ₆ D ₆ solution, heated at 75°C. That is, the catalyst is recycled. Repeated 6 times, we found that the catalytic effect of catalyst C4 after recycling is shown in Table 2:

Table 2. Recycling and Utilization of C4 Catalysts Supported by Rare Earth Metals

Example 38

The hydroalkoxylated substrate 2,2-dimethyl-4-pentyn-1-ol (14.9 mg, 0.164 mmol) was formulated into a 420 mg C ₆ D ₆ solution, and 12% molar equivalent of a rare earth supported catalyst was added (C4, C4a or C4b), heating at 75°C, and monitoring the reaction in situ. The effects of these catalysts are shown in Table 3:

Table 3. Intramolecular hydroalkoxylation of 2,2-dimethyl-4-pentyn-1-ol catalyzed by rare earth metal supported catalysts C4, C4a and C4b synthesized under different conditions

Example 39

The hydroalkoxylated substrate 2,2-dimethyl-4-pentyn-1-ol (14.9 mg, 0.164 mmol) was formulated into a 420 mg C ₆ D ₆ solution, and 12% molar equivalent of a rare earth supported catalyst was added (C12 or C12a), heated at 75°C, and monitored the reaction in situ. The effects of these catalysts are shown in Table 4:

Table 4. Intramolecular hydroalkoxylation of 2,2-dimethyl-4-pentyn-1-ol catalyzed by rare earth metal supported catalysts C12 and C12a synthesized under different conditions

Example 40

Hydroalkoxylated substrate 2,2-dimethyl-4-pentyn-1-ol (14.9mg, 0.164mmol) was made into 420mg of C6D6 solution, and 12% molar equivalent of rare earth supported catalyst (C16 or C16a), heating at 75°C, monitoring the reaction in situ. The effects of these catalysts are shown in Table 5:

Table 5. Intramolecular hydroalkoxylation of 2,2-dimethyl-4-pentyn-1-ol catalyzed by rare earth metal supported catalysts C16 and C16a synthesized under different conditions

Example 41

The hydroalkoxylated substrate 2,2-dimethyl-4-pentyn-1-ol (14.9 mg, 0.164 mmol) was formulated into a 420 mg C ₆ D ₆ solution, and 12% molar equivalent of a rare earth supported catalyst was added (C8 or C8a), heating at 75°C, monitoring the reaction in situ. The effects of these catalysts are shown in the table below:

Table 10. Intramolecular oxyhydrogenation of 2,2-dimethyl-4-pentyn-1-ol catalyzed by rare earth metal supported catalysts C8 and C8a synthesized under different conditions

Example 42

The hydroaminated substrate 4,4-dimethyl-5-amino-1-pentene (19.7 mg, 0.174 mmol) was formulated into a 420 mg C ₆ D ₆ solution, and 12% molar equivalent of rare earth supported Catalysts (C1-C4), heated at 75°C, reaction monitored in situ. The effects of these catalysts are shown in Table 11:

Table 11. Intramolecular hydroamination of 4,4-dimethyl-5-amino-1-pentene catalyzed by rare earth supported catalysts C1～C20

Example 43

The substrate 2,2-dimethyl-4-pentyn-1-ol (44.7mg, 0.492mmol) of the hydroalkoxylation reaction was formulated into a 1.5g toluene solution, put into a stopcock bottle, and 12% molar equivalent Catalyst C4 was heated at 75° C. for 3 hours, and 0.25 mL of the solution was sampled with a needle tube under a nitrogen atmosphere, and the conversion rate was measured to be 98% by ¹ H NMR. Under a nitrogen atmosphere, remove the supernatant, rinse the catalyst solid with 2×0.5mL toluene solution, add 1.5g 2,2-dimethyl-4-pentyn-1-ol in toluene solution, heat at 75°C . That is to recycle the catalyst. Repeated 6 times, we found that the catalytic effect of catalyst C4 after recycling is shown in Table 12:

Table 12. Recycling and Utilization of C4 Catalysts Supported by Rare Earth Metals

The structure of ligand L1-L6 described in the embodiment is as follows:

L1: R ¹ =2,6-dimethylphenyl

L2: R ¹ =2,6-diisopropylphenyl

L5: R ¹ =phenyl

L6: R ¹ = n-butyl

L3: R ¹ =2,6-dimethylphenyl

L4: R ¹ =2,6-diisopropylphenyl

The structure of catalyst C1-C24 is as follows:

1,2: R ¹ =2,6-dimethylphenyl, Ln=La

3,4: R ¹ =2,6-diisopropylphenyl, Ln=La

5,6: R ¹ =2,6-dimethylphenyl, Ln=La

7,8: R ¹ =2,6-diisopropylphenyl, Ln=La

9,10: R ¹ =2,6-dimethylphenyl, Ln=Y

11,12: R ¹ =2,6-diisopropylphenyl, Ln=Y

13, 14: R ¹ =2,6-dimethylphenyl, Ln=Nd

15, 16: R ¹ =2,6-diisopropylphenyl, Ln=Nd

17, 18: R ¹ =2,6-dimethylphenyl, Ln=Sm

19, 20: R ¹ =2,6-diisopropylphenyl, Ln=Sm

21, 22: R ¹ =phenyl, Ln=La

23, 24: R ¹ = n-butyl, Ln = La.

Claims (11)

1. A class of rare earth metal complexes based on Schiff base ligands, characterized in that they have the following structural formula:

In the above structural formula, linker represents a single bond, a C _1-8 alkyl group, a phenyl group, a phenyl group substituted by a single or double C6-C20 aryl group; R ¹ is phenyl, phenyl substituted by single or double C _1-4 alkyl or C _1-4 alkyl; X is tri(C ₁ ~C ₅ alkyl) silicon-substituted amine group; M is Y, Sc or rare earth metal ion of lanthanide ion; ----→ is a coordination bond or no bond; n is a natural number from 2 to 500. 2. A class of rare earth metal complexes based on Schiff base ligands as claimed in claim 1, characterized in that said n is a natural number ranging from 2 to 100. 3. A class of rare earth metal complexes based on Schiff base ligands as claimed in claim 1, characterized in that the Schiff base ligands have a structural formula as follows:

Wherein, R ¹ is as described in claim 1. 4. A class of rare earth metal complexes based on Schiff base ligands as claimed in claim 1, characterized in that said linker represents a single bond, 1,3-bis(4-hydroxyl-5-(2,6 -diisopropylphenylimine) methyl) phenyl or 1,3-bis(4-hydroxyl-5-(2,6-dimethylphenylimine) methyl) phenyl; the X is N(SiMe ₃ ) ₂ ; said M is La, Y, Nd or Sm; said C _1-4 alkyl substituted phenyl is 2,6-dimethylphenyl or 2,6-diiso Propylphenyl; the C _1-4 alkyl group is n-butyl or tert-butyl. 5. a kind of preparation method based on the rare earth metal complex of Schiff base ligand as described in claim 1, it is characterized in that Schiff base ligand and rare earth metal amine group as described in claim 3 Compound MX ₃ is obtained by reacting in an organic solvent at 25-50°C for 0.1-12 hours; the molar ratio of the Schiff base ligand to the rare earth metal amine compound is 1:0.5-1:1.5; wherein R ¹ , M, X, linker as claimed in claim 1. 6. a kind of preparation method based on the rare earth metal complex of Schiff base ligand as claimed in claim 5 is characterized in that described Schiff base ligand has following structural formula:

7. a kind of preparation method based on the rare earth metal complex of Schiff base ligand as claimed in claim 5 is characterized in that described Schiff base ligand obtains by following method respectively: Compound 1 or 7 and (linker)(B(OH) ₂ ) undergo Suzuki coupling reaction under the catalysis of Pd(PPh ₃ ) ₄ and base to obtain compound 5 or 8, respectively; In an organic solvent, under the action of BBr ₃ , the methyl protecting group is removed to obtain compound 6 or 9; Compound 6 or 9 reacts with H ₂ NR ¹ in an organic solvent under reflux to obtain ligands L1-L6 respectively; Wherein R1 is phenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl or n-butyl; The structural formulas of compounds 1, 5, 6, 7, 8 and 9 are as follows:

The Schiff base ligands L1-L6 are the same as those described in claim 6. 8. a kind of preparation method based on the rare earth metal complex of Schiff base ligand as claimed in claim 5 is characterized in that described Schiff base ligand L1, L2, L5 or L6 and rare earth metal amido compound The molar ratio of the Schiff base ligand L3 or L4 to the rare earth metal amine compound is 1:0.8～1:1.5; the molar ratio of the Schiff base ligand L3 or L4 is 1:0.5～1:0.8; the Schiff base ligand L1～L6 is as The description of claim 6; the organic solvent is toluene or C5-C10 alkane. 9. The use of a class of rare earth metal complexes based on Schiff base ligands as claimed in claim 1, characterized in that it is used as a catalyst for heterogeneous hydroalkoxylation or hydroamination. 10. The use according to claim 9, characterized in that it does not require any activator, coexistence of activator and co-catalyst, or any organic or inorganic carrier when used to catalyze hydroalkoxylation or hydroamination. 11. The use according to claim 9, characterized in that the catalytic hydroalkoxylation or hydroamination reaction is carried out in an organic solvent or in a solvent-free state at a temperature of 25°C to 75°C.