Cobalt complex, preparation method thereof, and application thereof in selective catalysis of transfer hydrogenation reaction of cyano group

A transfer hydrogenation and complex technology, which is applied in catalytic reaction, amino compound preparation, organic compound preparation, etc., achieves high research value and application prospect, simple preparation and high catalytic activity

Active Publication Date: 2018-04-27
TSINGHUA UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Among them, the reduction of cyano group usually faces the problem of chemoselective reduction. For example, how to obtain primary amine and secondary amine compounds through chemoselective reduction will be a big challenge.

Method used

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  • Cobalt complex, preparation method thereof, and application thereof in selective catalysis of transfer hydrogenation reaction of cyano group
  • Cobalt complex, preparation method thereof, and application thereof in selective catalysis of transfer hydrogenation reaction of cyano group
  • Cobalt complex, preparation method thereof, and application thereof in selective catalysis of transfer hydrogenation reaction of cyano group

Examples

Experimental program
Comparison scheme
Effect test

preparation example Construction

[0074] 2. Preparation of N-Me-Py-NNP ligand

[0075] 1. Synthesis of di-tert-butylphosphine borane complex

[0076]

[0077] Under the protection of argon, add BH 3 • THF solution (24 mL of 1M solution in THF, 24 mmol). After the reaction was stirred at room temperature for 4 h, the solvent was drained to obtain a white solid (2.74 g, 90%). 1 H NMR (400MHz, CDCl 3 )δ3.84( 1 J H-P =345Hz, 3 J H-H =6.5Hz, 1H), 1.25(d, J=13.6Hz, 18H), 0.57(m brw, 3H). 13 C NMR (101MHz, CDCl 3 )δ30.5(d,J C-P =27.5Hz), 28.9. 31P NMR (162MHz, CDCl 3 )δ48.00(q).

[0078] 2. Synthesis of 2-di-tert-butylphosphinoethylamine borane complex

[0079]

[0080] Under argon, add di-tert-butylphosphine borane complex (1.52g, 10mmol) and n-hexane (20ml) to a 100mL Shrek bottle, cool the mixture to -78°C, Add n-butyllithium (2.5M, 8.8mL, 22mmoL) dropwise to the system. After the addition, the reaction was raised to room temperature, and stirring was continued for 1 h to obtain tBu 2 PLi·BH ...

Embodiment 1

[0094] Embodiment 1, synthetic pyridine NNP-CoCl 2 Complex compound (shown in formula 2)

[0095] The reaction equation is as follows:

[0096]

[0097] A solution of degassed THF (5ml) in which pyridine NNP ligand (0.28g, 1.0mmol) was dissolved was added to THF (5ml) of cobalt dichloride (0.115g, 0.90mmol). After the ligand was added, the reaction was suspended The color of the liquid changed from blue to pink, stirred at room temperature (25°C) for 12 hours, then concentrated the solution to 2ml, added 15ml of degassed n-hexane, stirred for 1 hour, filtered with argon, and dried the obtained filter cake to obtain a pink solid (0.339 g, 83%).

[0098] Elemental analysis: theoretical value (%): C, 46.84; H, 7.13; N, 6.83; measured: C, 46.82; H, 7.34; N, 6.62.

[0099] NMR 1 H NMR (400MHz, CD 2 Cl 2 )δ=50.72(br),44.82(br),41.24(br),34.48(br),3.27(br),2.57(br),2.32(br),1.37(br),-2.88(br).

[0100] Magnetic distance: 4.3μ B.

[0101] Infrared (KBr): 3430, 2951, 1607, ...

Embodiment 2

[0103] Embodiment 2, synthesis Py-imine-NNP-CoCl 2 Complex compound (shown in formula 3)

[0104] The reaction equation is as follows:

[0105]

[0106] A solution of degassed THF (5 mL) in which the Py-imine-NNP ligand (0.278 g, 1.0 mmol) was dissolved was added in THF (5 mL) of cobalt dichloride (0.115 g, 0.90 mmoL). After the ligand was added, The reaction was stirred at room temperature (25° C.) for 8 h, then the solution was concentrated to 2 mL, 15 mL of degassed n-hexane was added, stirred for 1 hour, filtered with argon, and the obtained filter cake was dried to obtain a brown solid (0.330 g, 91%).

[0107] Elemental analysis: theoretical value (%): C, 47.08; H, 6.67; N, 6.86; measured: C, 46.60; H, 6.37; N, 7.12.

[0108] NMR: 1 H NMR (400MHz, CD 2 Cl 2 )δ=60.94(br),51.19(br),48.81(br),3.48(br),1.94(br),0.90(br),-0.59(br).

[0109] Magnetic distance: 4.2μ B.

[0110] Infrared: (KBr): 3433, 3060, 2944, 2867, 1653, 1600, 1567, 1470, 1445, 1394, 1372, 1299, 11...

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Abstract

The invention discloses a cobalt complex, a preparation method thereof, and an application thereof in the selective catalysis of a transfer hydrogenation reaction of a cyano group. The structural formula of the cobalt complex is represented by formula I. The cobalt complex is prepared through a reaction of a cobalt salt and an NNP ligand or a PNP ligand under the protection of an inert atmosphere;and the chemical formula of the cobalt salt is CoX12, wherein X1 represents halogen, a sulfate radical, a perchlorate radical, a hexafluorophosphate radical, a hexafluoroantimonate radical, a tetrafluoroborate radical, a trifluoromethanesulfonate radical or a tetra(pentafluorophenyl)borate radical. The cobalt complex can be used in the selective catalysis of the transfer hydrogenation reaction ofthe cyano group to obtain a primary amine compound, a secondary amine compound and a tertiary amine compound, the primary amine compound, the secondary amine compound and the tertiary amine compoundare important intermediates in a series of subsequent functionalizing reactions, and the cobalt complex has a very high catalysis activity, and has great research values and a great application prospect.

Description

technical field [0001] The invention relates to a cobalt complex, a preparation method thereof and an application in selective catalytic cyano group transfer hydrogenation reaction, belonging to the technical field of metal complexes. Background technique [0002] Catalytic hydrogenation of unsaturated compounds is a very important class of reactions in the chemical industry. Currently, such hydrogenation reactions typically use noble metal catalysts such as iridium, ruthenium, rhodium, palladium and platinum. However, these noble metals are not only expensive but also highly toxic, which will undoubtedly limit the wide application of the above reactions. Therefore, the development of cheap and low-toxic transition metal catalysts will be of great significance. [0003] Cobalt, as an element rich in the earth, is cheap and easy to get, and it is a vitamin B 12 It is an important constituent element, widely exists in the living body, and has little biological toxicity. Pr...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F15/06B01J31/24C07C211/27C07C211/29C07C211/30C07C211/07C07C211/12C07C209/48C07C213/02C07C217/58C07C227/04C07C229/38C07D213/38C07D213/803C07D213/80C07D213/73C07D215/06C07D333/20C07D295/03C07D295/15C07D267/20C07C319/20C07C323/32C07C211/45C07C211/52C07C213/00C07C227/18C07C229/36C07C215/28C07C211/35C07C211/38
CPCB01J31/24B01J2231/643B01J2531/0213B01J2531/0244B01J2531/845C07C209/48C07C213/00C07C213/02C07C227/04C07C227/18C07C319/20C07D213/38C07D213/73C07D213/80C07D213/803C07D215/06C07D267/20C07D295/03C07D295/15C07D333/20C07F15/065C07C211/27C07C211/29C07C217/58C07C229/38C07C211/30C07C323/32C07C211/07C07C211/12C07C211/45C07C211/52C07C229/14C07C229/36C07C215/28C07C211/35C07C211/38
Inventor 刘强付绍敏
Owner TSINGHUA UNIV
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