CN102503966A - Schiff-base ligand-based rare-earth metal complex, preparation method and applications - Google Patents
Schiff-base ligand-based rare-earth metal complex, preparation method and applications Download PDFInfo
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Abstract
The invention relates to a Schiff-base ligand-based rare-earth metal complex, a preparation method and applications. The complex is prepared by reacting a Schiff-base ligand with a rare-earth metal amino compound. When the complex is used as a catalyst, hydrogen-alkane oxidation reaction and hydroamination can be directly and efficiently catalyzed without the assistance of any activating agents or cocatalysts, and moreover, the complex can be recycled in catalytic reaction. The structural general formula of the rare-earth supported catalyst is shown as follows in the specification.
Description
Technical field
The present invention relates to one type of rare earth metal complex based on schiff base ligand; System forms self-supported catalyst by schiff base ligand and rare earth ion through coordination; Wherein rare earth ion provides the node of catalytic center and skeleton, and part constitutes the framework of whole self-supported catalyst.Its advantage is that these self-supported catalysts are non-homogeneous in organic solvent commonly used, in reaction of catalysis hydrogen alkoxide and hydroamination reaction, shows particular performances.The rare earth self-supported catalyst can be recycled, and rare earth metal can not remain in the product, meets the Green Chemistry theory.
Technical background
Heterogeneous ring compound is one type of important organic cpds, and it is present in many natural products and the synthetic drugs as core cell.In the route of synthetic nitrogen heterocyclic ring, Oxygenic heterocyclic compounds, the amination of intramolecularly hydrogen, the reaction of hydrogen alkoxide of two keys (or triple bond) and amino (or hydroxyl) is the compound method of Atom economy.
1989, but Marks group at first reports the intramolecularly hydroamination reaction of rare earth compound catalyzed alkene.They have provided possible reaction mechanism (Gagne, M.R.; Marks, T.J.J.Am.Chem.Soc.1989,111,4108.):
2007, the report rare earth metal amino-complex La [N (SiMe of Marks seminar
3)
2]
3Can realize containing the couplet alkene generation intramolecularly hydrogen alkoxide reaction of hydroxyl, and then obtain the oxygen heterocyclic ring product.This is the reported first about the reaction of catalysis of rare-earth compound alkene hydrogen alkoxide.Its reaction mechanism is different with the catalytic reaction mechanism of transistion metal compound.
Ln catalysis joins enol intramolecularly hydrogen alkoxylation;
La [N (SiMe
3)
2]
3Catalysis contains the hydrogen alkoxylation mechanism of the unsaturated hydrocarbons of hydroxyl.
2005, hydrogenating amination in the catalytic olefin hydrocarbon molecules of Livinghouse seminar report rare earth metal yttrium complex, what their seminar used is that a kind of yttrium complex that contains thiophenol is as catalyzer.This catalyzer has higher catalytic efficiency (Kim, Y.K., Livinghouse, T.Org.Lett.2005,7,1737.) to the intramolecularly hydrogen amination of alkene:
The complex catalysis intramolecularly hydroamination reaction of yttrium.
2007, Marks seminar reported that again the rare earth compounding of the organophosphorus monoxide ligand support that contains adjacent naphthols makees catalyzer, and this catalyzer is the hydroamination reaction of high productivity (98%) catalyzed alkene at room temperature; But ee value lower (26%) (Yu; X.H., Marks, T.J.Organometallics.2007; 26,365.):
The hydroamination reaction of samarium complex catalyzed alkene.
Along with the enhancing of global environmental consciousness with adhere to the theory of Sustainable development, exploitation is efficient, economical, recyclable to have become one of target that numerous investigators pursue with the catalyzer of recycling.A lot of catalyzer (comprising part and metal) of having developed at present not only cost are high; Under the homogeneous catalysis condition, being difficult to realize reclaiming recycling uses; And be lost to the application that objectionable impurities such as heavy metal in the product have also restricted it, especially in the preparation of pharmaceutical intermediate be unacceptable in producing.Therefore, people have developed a lot of types of heterogeneous catalyst successively.
The most popular porous material surely belongs to metal-organic framework material (Metal-Organic Frameworks; MOFs); This type material is assembled with solution chemical processes principle through automatic identification under mild conditions by bidentate or multiple tooth organic ligand molecule and metals ion or cluster, thereby also can be referred to as from support materials.。This metalloid-organic framework materials has shown good application prospects at aspects such as catalysis, separation, atmosphere storage, host-guest chemistry, sensing, multifunctional materials, and when they were used for catalysis, we were referred to as self-supported catalyst.
Because self-supported catalyst has the porousness of inorganic molecule sieve and to small molecules absorption, and they often have extremely low solvability in many organic solvents, thereby this type of catalyzer is that heterogeneous catalytic reaction provides a new approach.The self-supported catalyst model is following:
Nineteen eighty-two, Efraty etc. reported with self-supported catalyst [RhCl (CO) (and 1,4-(CN)
2C
6H
4)]
nThe heterogeneous hydrogenation of catalytic 1-hexene.This self-supported catalyst can pass through [Rh (CO)
2Cl]
2With two normal 1,4-two isonitrile base benzene prepare in methylene dichloride.The concrete structure of this catalyzer is also unclear, and the author thinks might exist line polymer, non-line polymer and tetragonal oligomer three kinds of forms (Efraty, A.; Frinstein, I.Inorg.Chem.1982,21,3115.):
1994, Fuiita etc. reported the catalytic aromatic aldehyde silicon of the crystalline state self-supported catalyst cyanogenation that the first structure is clear and definite.The author is with 4,4 '-dipyridyl (4,4 '-bpy) with Cd (NO
3)
2Reaction has generated a kind of water white crystalline state self-supported catalyst { [Cd (4,4 '-bpy) in ethanol-water system
2(H
2O)
2] (NO
3)
2H
2O}
n(1).This catalyzer has two dimensional surface square mesh structure, and wherein Metal Ions Cd (II) can be used as the close electric activation aromatic aldehyde of Lewis acid, and catalysis trimethyl silicane nitrile is to its nucleophilic addition.In report subsequently, the author is with the nucleophilic addition of this catalyst trimethyl silicane nitrile to imines, but most substrate rapid reaction, and yield is 70%～99%.Although it is heterogeneous carrying out that the author has verified entire reaction course, what do not provide catalyzer recycles result (OhmoriO., Fujita M.Chem.Commun.2004,1586-1587; Kato C.N., Ono M., Hino T., et al.Catal.Commun.2006,7:673-677.).{ [Cd (4,4 '-bpy) for self-supported catalyst
2(H
2O)
2] (NO
3)
2H
2O}
n(1) the heterogeneous silicon cyanogenation of the heterogeneous silicon cyanogenation of catalysis aromatic aldehyde and imines is following:
The refined seminar of Lin Wen with chirality self-supported catalyst L5-Ru-Zr and L6-Ru-Zr catalysis the hydrogenation of aromatic ketone, the ee value can reach 99.2%.And this catalyzer can recycle unattenuated more than 10 times (Ma, L.; Abney, C.; Lin, W.Chemical Society Reviews, 2009,38:1248-1256.).The hydrogenation of the heterogeneous aromatic ketone of chirality self-supported catalyst catalysis is following:
Fourth Kui Ling group is with the hydrogenation of 0.1mol.% chirality self-supported catalyst catalysis aromatic ketone, and reaction conversion ratio and ee value can reach 99% (Ding, K.; Wang, Z.; Wang, X.; Liang, Y.; Wang, X.Chemistry-A European Journal, 2006,12:5188-5197.):
Summary of the invention
The object of the invention provides a kind of rare earth metal complex that contains schiff base ligand, is a kind of rare earth loaded type catalyzer.
The object of the invention also provides a kind of above-mentioned preparation method who contains the rare earth metal complex and the part in the loaded catalyst thereof of schiff base ligand.
Another purpose of the present invention has provided the above-mentioned purposes that contains the rare earth metal complex of schiff base ligand.Be used for reaction of hydrogen alkoxide or intramolecularly hydroamination reaction in the catalytic molecular.Under 75 ℃ of heating, interior hydrogen alkoxide reaction of catalytic molecular efficiently of this catalyzer or intramolecularly hydroamination reaction.
The structural formula of the rare earth metal complex that contains schiff base ligand provided by the invention is following:
In the said structure formula, linker representes singly-bound, C
1-8Alkyl, phenyl, list or two C6～substituted phenyl of C20 aryl;
R
1Be phenyl, list or two C
1-4Substituted phenyl of alkyl or C
1-4Alkyl;
X is three (C
1～C
5Alkyl) silica-based substituted amido; M is the rare earth ion of Y, Sc or lanthanide ion;----→ be co-ordination bond or do not have key;
N is the natural number in 2～500, further is recommended as 2～100, more preferably 10～50.
Wherein, schiff base ligand can be the compound of following configuration:
The present invention also provides the compound method of above-mentioned schiff base ligand, and this compound method is following:
Compound 1 or 7 with (linker) (B (OH)
2) at Pd (PPh
3)
4Get compound 5 or 8 respectively with the following Suzuki of generation of the catalysis linked reaction of alkali;
In organic solvent, BBr
3Deviate from the basic compound 6 or 9 that gets of methyl protection under the effect;
Compound 6 or 9 and H
2NR
1Back flow reaction obtains schiff base ligand L1～L6 respectively in organic solvent;
Reaction of the present invention is recommended under the rare gas element to be carried out.
Wherein R1 is a phenyl, 2, and 6-3,5-dimethylphenyl, 2,6-diisopropyl phenyl or normal-butyl;
Compound 1,5,6,7,8 and 9 structural formulas are following:
Wherein linker, schiff base ligand L1～L6 are ditto said.
Above-mentioned schiff base ligand prepares process, is example with schiff base ligand L1, can simply represent with following reaction formula:
Me represent methylidene in the formula, EtOH represents ethanol, and n-Bu represents normal-butyl, and DME represents glycol dimethyl ether, and DMF represents N, dinethylformamide, DCM represents methylene dichloride.
Compound 1 and potassiumiodide are under the catalysis of alkali, and among organic solvent such as the DMF, room temperature reaction is after several hours; Use the saturated ammonium chloride solution cancellation,, merge organic phase with solvent dichloromethane extraction for example; Decompression down boils off solvent, with solvent such as normal hexane recrystallization, pass through above-mentioned handle compound 2.
Under the nitrogen atmosphere, compound 2 is dissolved in solvent such as absolute absolute ethyl alcohol, drips the concentrated hydrochloric acid of catalytic amount; Add triethyl orthoformate again, behind the reflux number hour, the pressure reducing and steaming solvent; Use the saturated sodium bicarbonate solution cancellation,, merge organic phase with solvent dichloromethane extraction for example; Decompression down boils off solvent, pass through above-mentioned handle compound 3.
Under the nitrogen atmosphere, under-78 ℃, the hexane solution of butyllithium is dropwise joined in the organic solvent such as THF of compound 3; React after 2 hours, drip trimethyl borate again, drip the recovery room temperature reaction and spend the night; Transfer pH to 1 with Hydrogen chloride again,, merge organic phase with organic solvent such as ethyl acetate extraction; The pressure reducing and steaming organic solvent is used re-crystallizing in ethyl acetate, through above-mentioned handle compound 4.
Under the nitrogen atmosphere, with compound 4 and compound 1 at Pd (PPh
3)
4Under the effect of alkali, in the mixed solvent of organic solvent such as DME and water, reflux 2 days is used the Hydrogen chloride cancellation, with organic solvent such as dichloromethane extraction, merges organic phase, and decompression boils off solvent down, column purification, pass through above-mentioned handle compound 5.
Under the nitrogen atmosphere, under-78 ℃, with BBr
3Be added drop-wise in the organic solvent such as methylene dichloride of compound 5, behind the stoichiometric number hour, add the frozen water cancellation, with organic solvent such as dichloromethane extraction,, merge organic phase, boil off solvent under the decompression, use the methylene dichloride recrystallization, pass through above-mentioned handle compound 6.
With compound 6 and 2, the 6-xylidine refluxes in organic solvent such as absolute ethyl alcohol, and after several hours, the pressure reducing and steaming solvent is used the absolute ethyl alcohol recrystallization, obtains ligand L 1 through above-mentioned processing.
In aforesaid method of the present invention, the organic solvent of use is recommended DMF, absolute ethyl alcohol, THF, DME, methylene dichloride, toluene; The alkali that uses is recommended as yellow soda ash, salt of wormwood, cesium carbonate; Used acid is recommended as hydrochloric acid.
The invention provides one type of above-mentioned rare earth metal complex that contains schiff base ligand, its structural formula is following:
Wherein, linker representes singly-bound, C
1-8Alkyl, phenyl, list or two C6～substituted phenyl of C20 aryl, further be recommended as singly-bound, 1,3-two (4-hydroxyl-5-(2,6-diisopropyl benzene imines) methyl) phenyl or 1,3-two (4-hydroxyl-5-(2,6-dimethyl benzene imines) methyl) phenyl;
R
1Be phenyl, list or two C
1-4Substituted phenyl of alkyl or C
1-4Alkyl, further be recommended as phenyl, 2,6-3,5-dimethylphenyl, 2,6-di-isopropyl methyl or normal-butyl;
X is three (C
1～C
5Alkyl) silica-based substituted amido further is recommended as N (SiMe
3)
2M is the rare earth ion of Y, Sc or lanthanide ion, further is recommended as La, Y, Nd or Sm;----→ be co-ordination bond or do not have key;
N is the natural number in 2～500, further is recommended as 2～100, more preferably 10～50.
The present invention also provides the compound method of above-mentioned rare earth metal complex, and this compound method is following:
Ligand L 1～L6 and rare earth metal amino-complex MX
3Under organic solvent and 25～50 ℃, stirring reaction 0.1～12h obtains.
Wherein, ligand L 1, L2, L5 or L6 and rare earth metal amino-complex MX
3Mol ratio be 1: 0.8～1: 1.5; Ligand L 3 or L4 and rare earth metal amino-complex MX
3Mol ratio be 1: 0.5～1: 0.8; Rare earth metal amino-complex MX
3Be recommended as Ln (N (SiMe
3)
2)
3(Ln=La, Y, Nd, Sm); Organic solvent is recommended as toluene or normal hexane.
R1, M, X, linker, n are as previously mentioned.
In the inventive method, the preparation process of the above-mentioned rare earth metal complex that contains schiff base ligand is with ligand L 1 and La (N (SiMe
3)
2)
3Prepared in reaction C1 is an example, can simply represent with following reaction formula:
Reaction conditions to the compound method of above-mentioned reaction is recommended is specific as follows:
The toluene solution of ligand L 1 is dropwise joined La (N (SiMe
3)
2)
3Toluene (Toluene) solution in, separate out orange deposition, stirred 1 hour under the system room temperature, remove supernatant after centrifugal, residual solid with the toluene repetitive scrubbing repeatedly after dry 3 hours, is used for the reaction of hydrogen alkoxide under the gained red solid vacuum.
Wherein, ligand L 1～L6, R
1, M, X as previously mentioned, n=35.
The rare earth metal loaded catalyst that one type of synthetic of the present invention contains schiff base ligand without any need for acvator, acvator and promotor exist jointly, or any organic or inorganic carrier; Can catalysis hydrogen alkoxide react and hydroamination reaction, further recommend to be used for reaction of intramolecularly hydrogen alkoxide and hydroamination reaction.
Embodiment
The present invention will be helped further to understand through following embodiment, but content of the present invention can not be limited.
Embodiment 1
In the 50mL single port bottle, adding 4,4 '-dihydroxyl-3,3 '-dialdehyde-based biphenyl (127g, 52mmol), 2, the 6-xylidine (0.23mL, 1.05mmol) with the 10mL absolute ethyl alcohol, reflux (reflux) 2 hours.Remove and to desolvate, residual solids is used the absolute ethyl alcohol recrystallization, obtain 3,3 '-two-(2,6-dimethyl benzene imines) methyl) biphenyl-4,4 '-glycol L1 (140mg, 60% productive rate (yield)).
1H 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);
13C NMR (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
30H
29N
2O
2(M
+) calculated value: 449.2223; Measured value: 449.2224.
Embodiment 2
In the 50mL single port bottle, adding 4,4 '-dihydroxyl-3,3 '-dialdehyde-based biphenyl (127mg, 0.52mmol), 2, the 6-diisopropyl aniline (0.26mL, 1.05mmol) with the 10mL absolute ethyl alcohol, reflux 2 hours.Remove and to desolvate, residual solids is used the absolute ethyl alcohol recrystallization, obtain 3,3 '-two-(2,6-diisopropyl benzene imines) methyl) biphenyl-4,4 '-glycol L2 (150mg, 63%yield).
1H 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);
13C 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): C
38H
45N
2O
2(M
+) calculated value: 561.3482; Measured value: 561.3476.
Embodiment 3
In the 50mL single port bottle, add 1,3, and 5-three (4-hydroxyl-5-aldehyde radical phenyl) benzene (1g, 2.3mmol), 2, the 6-xylidine (1.5mL, 6.8mmol), the mixed solvent of absolute ethyl alcohol and toluene (v/v=2/1), reflux reacted completely in 2 hours.Remove and desolvate, residual solids is used the absolute ethyl alcohol recrystallization, obtains 1,3, and 5-three-(4-hydroxyl-5-(2,6-dimethyl benzene imines) methyl) benzene L3 (1.4g, 65%yield).
1H 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);
13C 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): C
51H
46N
3O
3(M
+) calculated value: 748.3547; Measured value: 748.3533.
Embodiment 4
In the 50mL single port bottle, add 1,3, and 5-three (4-hydroxyl-5-aldehyde radical phenyl) benzene (1g, 2.3mmol), 2, the 6-diisopropyl aniline (1.7mL, 6.8mmol), the mixed solvent of absolute ethyl alcohol and toluene (v/v=2/1), reflux reacted completely in 2 hours.Remove and desolvate, residual solids is used the absolute ethyl alcohol recrystallization, obtains 1,3, and 5-three-(4-hydroxyl-5-(2,6-diisopropyl benzene imines) methyl) benzene L4 (1.2g, 65%yield).
1H 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);
13C 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): C
63H
70N
3O
3(M
+) calculated value: 916.5409; Measured value: 916.5412.
Embodiment 5
In the 50mL single port bottle, adding 4,4 '-dihydroxyl-3,3 '-dialdehyde-based biphenyl (127mg, 0.52mmol), aniline (0.18mL, 1.05mmol) with the 10mL absolute ethyl alcohol, reflux 2 hours.Remove and to desolvate, residual solids is used the absolute ethyl alcohol recrystallization, obtain 3,3 '-two-benzene formimino biphenyl-4,4 '-glycol L5 (120mg, 83%yield).
1H 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);
13C 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): C
26H
20N
2O
2(M
+) calculated value: 392.1582; Measured value: 392.2576.
Embodiment 6
In the 50mL single port bottle, adding 4,4 '-dihydroxyl-3,3 '-dialdehyde-based biphenyl (127mg, 0.52mmol), n-Butyl Amine 99 (0.28mL, 1.05mmol) with the 10mL absolute ethyl alcohol, reflux 2 hours.Remove and to desolvate, residual solids is used the absolute ethyl alcohol recrystallization, obtain 3,3 '-two-n-Butyl Amine 99 methyl diphenyl-4,4 '-glycol L6 (95mg, 85%yield).
1H 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, CH
3CH
2CH
2CH
2), 1.65 (m, 2H, CH
3CH
2CH
2CH
2), 1.31 (m, 2H, CH
3CH
2CH
2CH
2), 0.90 (t, J=4Hz, 3H, CH
3CH
2CH
2CH
2);
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
22H
28N
2O
2(M
+) calculated value: 352.2252; Measured value: 352.2356.
Embodiment 7
With La (N (SiMe
3)
2)
3(60mg, 2mL toluene solution 0.097mmol) slowly splash into L1, and (44mg in 10mL toluene solution 0.097mmol), generates deposition immediately.Centrifugal after the stirred overnight at room temperature, remove supernatant, will precipitate toluene wash with 5 * 3mL, obtain rare earth self-supported catalyst C1 (70mg, 97%yield), n=35.
Embodiment 8
(44mg, 2mL toluene solution 0.097mmol) slowly splashes into La (N (SiMe with L1
3)
2)
3(60mg in 10mL toluene solution 0.097mmol), generates deposition immediately.Centrifugal after the stirred overnight at room temperature, remove supernatant, will precipitate toluene wash with 5 * 3mL, obtain rare earth self-supported catalyst C2 (70mg, 96%yield), n=30.
Embodiment 9
With La (N (SiMe
3)
2)
3(60mg, 2mL toluene solution 0.097mmol) slowly splash into L2, and (47mg in 10mL toluene solution 0.097mmol), generates deposition immediately.Centrifugal after the stirred overnight at room temperature, remove supernatant, will precipitate toluene wash with 5 * 3mL, obtain rare earth self-supported catalyst C3 (80mg, 96%yield), n=50.
Embodiment 10
(47mg, 2mL toluene solution 0.097mmol) slowly splashes into La (N (SiMe with L2
3)
2)
3(60mg in 10mL toluene solution 0.097mmol), generates deposition immediately.Centrifugal after the stirred overnight at room temperature, remove supernatant, will precipitate toluene wash with 5 * 3mL, obtain rare earth self-supported catalyst C4 (83mg, 99%yield) n=45.
Embodiment 11
With La (N (SiMe
3)
2)
3(60mg, 2mL toluene solution 0.097mmol) slowly splash into L3, and (49mg in 10mL toluene solution 0.065mmol), generates deposition immediately.Centrifugal after the stirred overnight at room temperature, remove supernatant, will precipitate toluene wash with 5 * 3mL, obtain rare earth self-supported catalyst C5 (65mg, 95%yield), n=10.
Embodiment 12
(49mg, 2mL toluene solution 0.065mmol) slowly splashes into La (N (SiMe with L3
3)
2)
3(60mg in 10mL toluene solution 0.097mmol), generates deposition immediately.Centrifugal after the stirred overnight at room temperature, remove supernatant, will precipitate toluene wash with 5 * 3mL, obtain rare earth self-supported catalyst C6 (66mg, 97%yield), n=20.
Embodiment 13
With La (N (SiMe
3)
2)
3(60mg, 2mL toluene solution 0.097mmol) slowly splash into L4, and (54mg in 10mL toluene solution 0.065mmol), generates deposition immediately.Centrifugal after the stirred overnight at room temperature, remove supernatant, will precipitate toluene wash with 5 * 3mL, obtain rare earth self-supported catalyst C7 (76mg, 96%yield), n=20.
Embodiment 14
(54mg, 2mL toluene solution 0.065mmol) slowly splashes into La (N (SiMe with L4
3)
2)
3(60mg in 10mL toluene solution 0.097mmol), generates deposition immediately.Centrifugal after the stirred overnight at room temperature, remove supernatant, will precipitate toluene wash with 5 * 3mL, obtain rare earth self-supported catalyst C8 (78mg, 99%yield), n=30.
Embodiment 15
With Y (N (SiMe
3)
2)
3(55mg, 2mL toluene solution 0.097mmol) slowly splash into L1, and (44mg in 10mL toluene solution 0.097mmol), generates deposition immediately.Centrifugal after the stirred overnight at room temperature, remove supernatant, will precipitate toluene wash with 5 * 3mL, obtain rare earth self-supported catalyst C9 (71mg, 97%yield), n=30.
Embodiment 16
(44mg, 2mL toluene solution 0.097mmol) slowly splashes into Y (N (SiMe with L1
3)
2)
3(55mg in 10mL toluene solution 0.097mmol), generates deposition immediately.Centrifugal after the stirred overnight at room temperature, remove supernatant, will precipitate toluene wash with 5 * 3mL, obtain rare earth self-supported catalyst C10 (72mg, 99%yield), n=30.
Embodiment 17
With Y (N (SiMe
3)
2)
3(55mg, 2mL toluene solution 0.097mmol) slowly splash into L2, and (47mg in 10mL toluene solution 0.097mmol), generates deposition immediately.Centrifugal after the stirred overnight at room temperature, remove supernatant, will precipitate toluene wash with 5 * 3mL, obtain rare earth self-supported catalyst C11 (82mg, 96%yield), n=35.
Embodiment 18
(47mg, 2mL toluene solution 0.097mmol) slowly splashes into Y (N (SiMe with L2
3)
2)
3(55mg in 10mL toluene solution 0.097mmol), generates deposition immediately.Centrifugal after the stirred overnight at room temperature, remove supernatant, will precipitate toluene wash with 5 * 3mL, obtain rare earth self-supported catalyst C12 (84mg, 98%yield), n=35.
Embodiment 19
With Nd (N (SiMe
3)
2)
3(61mg, 2mL toluene solution 0.097mmol) slowly splash into L1, and (44mg in 10mL toluene solution 0.097mmol), generates deposition immediately.Centrifugal after the stirred overnight at room temperature, remove supernatant, will precipitate toluene wash with 5 * 3mL, obtain rare earth self-supported catalyst C13 (69mg, 95%yield), n=30.
Embodiment 20
(44mg, 2mL toluene solution 0.097mmol) slowly splashes into Nd (N (SiMe with L1
3)
2)
3(61mg in 10mL toluene solution 0.097mmol), generates deposition immediately.Centrifugal after the stirred overnight at room temperature, remove supernatant, will precipitate toluene wash with 5 * 3mL, obtain rare earth self-supported catalyst C14 (71mg, 98%yield), n=30.
Embodiment 21
With Nd (N (SiMe
3)
2)
3(61mg, 2mL toluene solution 0.097mmol) slowly splash into L2, and (47mg in 10mL toluene solution 0.097mmol), generates deposition immediately.Centrifugal after the stirred overnight at room temperature, remove supernatant, will precipitate toluene wash with 5 * 3mL, obtain rare earth self-supported catalyst C15 (80mg, 96%yield), n=30.
Embodiment 22
(47mg, 2mL toluene solution 0.097mmol) slowly splashes into Nd (N (SiMe with L2
3)
2)
3(61mg in 10mL toluene solution 0.097mmol), generates deposition immediately.Centrifugal after the stirred overnight at room temperature, remove supernatant, will precipitate toluene wash with 5 * 3mL, obtain rare earth self-supported catalyst C16 (82mg, 99%yield), n=30.
Embodiment 23
With Sm (N (SiMe
3)
2)
3(61mg, 2mL toluene solution 0.097mmol) slowly splash into L1, and (44mg in 10mL toluene solution 0.097mmol), generates deposition immediately.Centrifugal after the stirred overnight at room temperature, remove supernatant, will precipitate toluene wash with 5 * 3mL, obtain rare earth self-supported catalyst C17 (68mg, 95%yield), n=20.
Embodiment 24
(44mg, 2mL toluene solution 0.097mmol) slowly splashes into Nd (N (SiMe with L1
3)
2)
3(61mg in 10mL toluene solution 0.097mmol), generates deposition immediately.Centrifugal after the stirred overnight at room temperature, remove supernatant, will precipitate toluene wash with 5 * 3mL, obtain rare earth self-supported catalyst C18 (69mg, 96%yield), n=20.
Embodiment 25
With Nd (N (SiMe
3)
2)
3(61mg, 2mL toluene solution 0.097mmol) slowly splash into L2, and (47mg in 10mL toluene solution 0.097mmol), generates deposition immediately.Centrifugal after the stirred overnight at room temperature, remove supernatant, will precipitate toluene wash with 5 * 3mL, obtain rare earth self-supported catalyst C19 (79mg, 95%yield), n=20.
Embodiment 26
(47mg, 2mL toluene solution 0.097mmol) slowly splashes into Nd (N (SiMe with L2
3)
2)
3(61mg in 10mL toluene solution 0.097mmol), generates deposition immediately.Centrifugal after the stirred overnight at room temperature, remove supernatant, will precipitate toluene wash with 5 * 3mL, obtain rare earth self-supported catalyst C20 (81mg, 97%yield), n=20.
Embodiment 27
(47mg, 2mL toluene solution 0.097mmol) slowly splashes into La (N (SiMe with L2
3)
2)
3(60mg in 10mL toluene solution 0.097mmol), generates deposition immediately.50 ℃ of heated and stirred are centrifugal after 12 hours, remove supernatant, will precipitate the toluene wash with 5 * 3mL, obtain rare earth self-supported catalyst C4a (83mg, 99%yield), n=35.
Embodiment 28
(47mg, 2mL toluene solution 0.097mmol) slowly splashes into Y (N (SiMe with L2
3)
2)
3(55mg in 10mL toluene solution 0.097mmol), generates deposition immediately.50 ℃ of heated and stirred are centrifugal after 12 hours, remove supernatant, will precipitate the toluene wash with 5 * 3mL, obtain rare earth self-supported catalyst C12 (84mg, 98%yield), n=30.
Embodiment 29
(47mg, 2mL toluene solution 0.097mmol) slowly splashes into Nd (N (SiMe with L2
3)
2)
3(61mg in 10mL toluene solution 0.097mmol), generates deposition immediately.50 ℃ of heated and stirred are centrifugal after 12 hours, remove supernatant, will precipitate the toluene wash with 5 * 3mL, obtain rare earth self-supported catalyst C16a (82mg, 99%yield), n=30.
Embodiment 30
(47mg, 2mL hexane solution 0.097mmol) slowly splashes into La (N (SiMe with L2
3)
2)
3(60mg in 10mL tetrahydrofuran solution 0.097mmol), generates deposition immediately.Stirring at normal temperature spend the night the back centrifugal, remove supernatant, will precipitate toluene wash with 5 * 3mL, obtain rare earth self-supported catalyst C4b (83mg, 99%yield), n=30.
Embodiment 31
(54mg, 2mL hexane solution 0.065mmol) slowly splashes into La (N (SiMe with L4
3)
2)
3(60mg in 10mL tetrahydrofuran solution 0.097mmol), generates deposition immediately.Stirring at normal temperature spend the night the back centrifugal, remove supernatant, will precipitate toluene wash with 5 * 3mL, obtain rare earth self-supported catalyst C6a (66mg, 97%yield), n=15.
Embodiment 32
With La (N (SiMe
3)
2)
3(60mg, 2mL toluene solution 0.097mmol) slowly splash into L5, and (41mg in 10mL toluene solution 0.087mmol), generates deposition immediately.Centrifugal after the stirred overnight at room temperature, remove supernatant, will precipitate toluene wash with 5 * 3mL, obtain rare earth self-supported catalyst C21 (67mg, 95%yield), n=15.
Embodiment 33
(41mg, 2mL toluene solution 0.087mmol) slowly splashes into La (N (SiMe with L5
3)
2)
3(60mg in 10mL toluene solution 0.097mmol), generates deposition immediately.Centrifugal after the stirred overnight at room temperature, remove supernatant, will precipitate toluene wash with 5 * 3mL, obtain rare earth self-supported catalyst C22 (71mg, 97%yield), n=15.
Embodiment 34
With La (N (SiMe
3)
2)
3(60mg, 2mL toluene solution 0.097mmol) slowly splash into L6, and (43mg in 10mL toluene solution 0.088mmol), generates deposition immediately.Centrifugal after the stirred overnight at room temperature, remove supernatant, will precipitate toluene wash with 5 * 3mL, obtain rare earth self-supported catalyst C23 (66mg, 96%yield), n=15.
Embodiment 35
(43mg, 2mL toluene solution 0.088mmol) slowly splashes into La (N (SiMe with L6
3)
2)
3(60mg in 10mL toluene solution 0.097mmol), generates deposition immediately.Centrifugal after the stirred overnight at room temperature, remove supernatant, will precipitate toluene wash with 5 * 3mL, obtain rare earth self-supported catalyst C24 (66mg, 96%yield), n=15.
Embodiment 36
With the substrate 2 of hydrogen alkoxide, (14.9mg 0.164mmol) is made into the C of 420mg to 2-dimethyl--4-pentyne-1-alcohol
6D
6Solution, the rare earth loaded type catalyzer (self-supportedcat.) that adds 12% molar equivalent (C1-C24), 75 ℃ of heating, in-situ monitoring reaction.The effect of these catalyzer is as shown in table 1:
The rare earth loaded catalyzer C1～C24 of table 1. is catalytic 2,2-dimethyl--4-pentyne-1-alcohol intramolecularly hydrogen alkoxide reaction
Embodiment 37
With the substrate 2 of hydrogen alkoxide reaction, (14.9mg 0.164mmol) is made into the C of 420mg to 2-dimethyl--4-pentyne-1-alcohol
6D
6Solution adds the catalyzer C4 of 12% molar equivalent, 75 ℃ of heating, and the in-situ monitoring reaction was heated after 5 hours, and transformation efficiency is 97%.Under nitrogen atmosphere, the upper strata stillness of night in the original position nuclear-magnetism pipe is toppled over, with 2 * 0.5mLC
6D
6Behind the solution rinse catalyst solid, add 420mg 2, the C of 2-dimethyl--4-pentyne-1-alcohol
6D
6Solution, 75 ℃ of heating.Promptly carry out the recycling of catalyzer.6 times repeatedly, catalytic effect was as shown in table 2 after we found the recycling of catalyzer C4:
The recycling of table 2. rare earth metal supported catalyst C4 catalyzer
Embodiment 38
With the substrate 2 of hydrogen alkoxide, (14.9mg 0.164mmol) is made into the C of 420mg to 2-dimethyl--4-pentyne-1-alcohol
6D
6Solution adds the rare earth loaded type catalyzer (C4, C4a or C4b) of 12% molar equivalent, 75 ℃ of heating, in-situ monitoring reaction.The effect of these catalyzer is as shown in table 3:
Synthetic rare earth metal supported catalyst C4 under table 3. different condition, C4a and C4b are catalytic 2,2-dimethyl--4-pentyne-1-alcohol intramolecularly hydrogen alkoxide reaction
Embodiment 39
With the substrate 2 of hydrogen alkoxide, (14.9mg 0.164mmol) is made into the C of 420mg to 2-dimethyl--4-pentyne-1-alcohol
6D
6Solution adds the rare earth loaded type catalyzer (C12 or C12a) of 12% molar equivalent, 75 ℃ of heating, in-situ monitoring reaction.The effect of these catalyzer is as shown in table 4:
Synthetic rare earth metal supported catalyst C12 and C12a are catalytic 2 under table 4. different condition, 2-dimethyl--4-pentyne-1-alcohol intramolecularly hydrogen alkoxide reaction
Embodiment 40
With the substrate 2 of hydrogen alkoxide, (14.9mg 0.164mmol) is made into the C6D6 solution of 420mg to 2-dimethyl--4-pentyne-1-alcohol, adds the rare earth loaded type catalyzer (C16 or C16a) of 12% molar equivalent, 75 ℃ of heating, in-situ monitoring reaction.The effect of these catalyzer is as shown in table 5:
Synthetic rare earth metal supported catalyst C16 and C16a are catalytic 2 under table 5. different condition, 2-dimethyl--4-pentyne-1-alcohol intramolecularly hydrogen alkoxide reaction
Embodiment 41
With the substrate 2 of hydrogen alkoxide, (14.9mg 0.164mmol) is made into the C of 420mg to 2-dimethyl--4-pentyne-1-alcohol
6D
6Solution adds the rare earth loaded type catalyzer (C8 or C8a) of 12% molar equivalent, 75 ℃ of heating, in-situ monitoring reaction.The effect of these catalyzer is as shown in the table:
Synthetic rare earth metal supported catalyst C8 and C8a are catalytic 2 under table 10. different condition, 2-dimethyl--4-pentyne-1-alcohol intramolecularly oxygen hydrogenation
Embodiment 42
With the aminating substrate 4 of hydrogen, (19.7mg 0.174mmol) is made into the C of 420mg to 4-dimethyl--5-amido-1-amylene
6D
6Solution adds the rare earth loaded type catalyzer (C1-C4) of 12% molar equivalent, 75 ℃ of heating, in-situ monitoring reaction.The effect of these catalyzer is as shown in table 11:
The rare earth loaded catalyzer C1～C20 of table 11. is catalytic 4,4-dimethyl--5-amido-1-amylene intramolecularly hydroamination reaction
Embodiment 43
With the substrate 2 of hydrogen alkoxide reaction, (44.7mg 0.492mmol) is made into the toluene solution of 1.5g to 2-dimethyl--4-pentyne-1-alcohol; Pack in the cock bottle, add the catalyzer C4 of 12% molar equivalent, 75 ℃ of heating are after 3 hours; Under nitrogen atmosphere, with needle tubing sampling 0.25mL solution, through
1It is 98% that H NMR records transformation efficiency.Under nitrogen atmosphere, with removing supernatant, behind 2 * 0.5mL toluene solution rinse catalyst solid, add 1.5g 2, the toluene solution of 2-dimethyl--4-pentyne-1-alcohol, 75 ℃ of heating.Promptly carry out the recycling of catalyzer.6 times repeatedly, catalytic effect was as shown in table 12 after we found the recycling of catalyzer C4:
The recycling of table 12. rare earth metal supported catalyst C4 catalyzer
The structure of ligand L 1-L6 described in the embodiment is following:
L1:R
1=2, the 6-3,5-dimethylphenyl
L2:R
1=2, the 6-diisopropyl phenyl
L5:R
1=phenyl
L6:R
1=normal-butyl
L3:R
1=2, the 6-3,5-dimethylphenyl
L4:R
1=2, the 6-diisopropyl phenyl
The structure of catalyzer C1-C24 is following:
1,2:R
1=2,6-3,5-dimethylphenyl, Ln=La
3,4:R
1=2,6-diisopropyl phenyl, Ln=La
5,6:R
1=2,6-3,5-dimethylphenyl, Ln=La
7,8:R
1=2,6-diisopropyl phenyl, Ln=La
9,10:R
1=2,6-3,5-dimethylphenyl, Ln=Y
11,12:R
1=2,6-diisopropyl phenyl, Ln=Y
13,14:R
1=2,6-3,5-dimethylphenyl, Ln=Nd
15,16:R
1=2,6-diisopropyl phenyl, Ln=Nd
17,18:R
1=2,6-3,5-dimethylphenyl, Ln=Sm
19,20:R
1=2,6-diisopropyl phenyl, Ln=Sm
21,22:R
1=phenyl, Ln=La
23,24:R
1=normal-butyl, Ln=La.
Claims (11)
1. one type of rare earth metal complex based on schiff base ligand is characterized in that having following structural formula:
In the said structure formula, linker representes singly-bound, C
1-8Alkyl, phenyl, list or two C6～substituted phenyl of C20 aryl;
R
1Be phenyl, list or two C
1-4Substituted phenyl of alkyl or C
1-4Alkyl;
X is three (C
1～C
5Alkyl) silica-based substituted amido; M is the rare earth ion of Y, Sc or lanthanide ion;----→ be co-ordination bond or do not have key;
N is the natural number in 2～500.
2. one type of rare earth metal complex based on schiff base ligand described in claim 1 is characterized in that described n is 2～100 natural number.
3. one type of rare earth metal complex based on schiff base ligand described in claim 1 is characterized in that described schiff base ligand, and structural formula is following:
Wherein, R
1According to claim 1.
4. one type of rare earth metal complex as claimed in claim 1 based on schiff base ligand; It is characterized in that described linker representes singly-bound, 1,3-two (4-hydroxyl-5-(2,6-diisopropyl benzene imines) methyl) phenyl or 1; 3-two (4-hydroxyl-5-(2,6-dimethyl benzene imines) methyl) phenyl; Described X is N (SiMe
3)
2Described M is La, Y, Nd or Sm; Described C
1-4The substituted phenyl of alkyl is 2,6-3,5-dimethylphenyl or 2,6-diisopropyl phenyl; Described C
1-4Alkyl be the normal-butyl or the tertiary butyl.
5. one type of preparation method based on the rare earth metal complex of schiff base ligand described in claim 1 is characterized in that schiff base ligand and rare earth metal amino-complex MX described in claim 3
3In organic solvent and 25～50 ℃ of reaction 0.1～12h acquisitions down; The mol ratio of described schiff base ligand and rare earth metal amino-complex is 1: 0.5～1: 1.5; R wherein
1, M, X, linker according to claim 1.
6. one type 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. one type 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 is obtained by following method respectively:
Compound 1 or 7 with (linker) (B (OH)
2) at Pd (PPh
3)
4Get compound 5 or 8 respectively with the following Suzuki of generation of the catalysis linked reaction of alkali;
In organic solvent, BBr
3Deviate from the basic compound 6 or 9 that gets of methyl protection under the effect;
Compound 6 or 9 and H
2NR
1Back flow reaction obtains ligand L 1～L6 respectively in organic solvent;
Wherein R1 is a phenyl, 2, and 6-3,5-dimethylphenyl, 2,6-diisopropyl phenyl or normal-butyl;
Compound 1,5,6,7,8 and 9 structural formulas are following:
Described schiff base ligand L1～L6 is said with claim 6.
8. one type of preparation method as claimed in claim 5 based on the rare earth metal complex of schiff base ligand, the mol ratio that it is characterized in that described schiff base ligand L1, L2, L5 or L6 and rare earth metal amino-complex is 1: 0.8～1: 1.5; The mol ratio of described schiff base ligand L3 or L4 and rare earth metal amino-complex is 1: 0.5～1: 0.8; Schiff base ligand L1～L6 such as claim 6 are said; Described organic solvent is the alkane of toluene or C5～C10.
9. one type of purposes based on the rare earth metal complex of schiff base ligand described in the claim 1 is characterized in that the catalyzer as heterogeneous hydrogen alkoxide reaction or hydroamination reaction.
10. purposes as claimed in claim 9, when it is characterized in that being used for catalysis hydrogen alkoxide reaction or hydroamination reaction, without any need for acvator, acvator and promotor exist jointly, perhaps any organic or inorganic carrier.
11. like right 9 described purposes, it is characterized in that in organic solvent or solvent-free state under, under 25 ℃～75 ℃ conditions, carry out reaction of catalysis hydrogen alkoxide or hydroamination reaction.
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