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

A technology of rare earth metals and Schiff bases, applied in the direction of organic compound/hydride/coordination complex catalysts, compounds containing elements of group 3/13 of the periodic table, chemical instruments and methods, etc. Problems such as recycling results, low ee value, etc.

Inactive Publication Date: 2012-06-20
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI +1
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0013] 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.):
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 C.N., Ono M., Hino T. , et al. Catal. Commun. 2006, 7: 673-677.)

Method used

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  • Schiff-base ligand-based rare-earth metal complex, preparation method and applications
  • Schiff-base ligand-based rare-earth metal complex, preparation method and applications
  • Schiff-base ligand-based rare-earth metal complex, preparation method and applications

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0078]

[0079] 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=2.4 Hz, 2H, ArH), 7.11-7.15(m, 6H, ArH), 7.01-7.06(m, 2H, ArH), 2.22(s, 24H, CH 3 ); 13 C 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 30 h 29 N 2 o 2 (M + ) calculated value: 449.2223; measured value: 449.2224.

Embodiment 2

[0081]

[0082] 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 ); 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 38 h 45 N 2 o 2 (M + ) calculated value: 561.3482; measured value: 561.3476.

Embodiment 3

[0084]

[0085] 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): C 51 h 46 N 3 o 3 (M + ) calculated value: 748.3547; measured value: 748.3533.

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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 [0001] 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. technical background [0002] 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 ...

Claims

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Application Information

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IPC IPC(8): C07F5/00B01J31/22C07D307/28C07D207/06
CPCY02P20/55
Inventor 陈耀峰孙逸琳王利民
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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