Binuclear rhodium complex containing ortho-carborane structure and preparation and application thereof

A rhodium complex and carborane technology, applied in the field of binuclear semi-sandwich trivalent rhodium complexes, can solve the problems of high requirements for reaction equipment, harsh reaction conditions, cumbersome operation, etc., and achieve low requirements for reaction equipment and mild reaction conditions , good universal effect

Active Publication Date: 2019-09-17
SHANGHAI INST OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Among them, the method of halogenated hydrocarbons as alkylating reagents is that the nitrogen negative ion intermediate formed by the substrate and strong base (sodium tert-butoxide or butyllithium, etc. air-sensitive reagents) at low temperature carries out nucleophilic attack on halogenated hydrocarbons. , to generate alkane-substituted products, but this method has hars

Method used

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  • Binuclear rhodium complex containing ortho-carborane structure and preparation and application thereof
  • Binuclear rhodium complex containing ortho-carborane structure and preparation and application thereof
  • Binuclear rhodium complex containing ortho-carborane structure and preparation and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] Synthesis of the binuclear semi-sandwich rhodium complex Rh containing ortho-carborane:

[0032]

[0033] At -78°C, n-BuLi (1.6M) in n-hexane (1.00 mL, 1.6 mmol) was slowly added dropwise to the o-C 2 B 10 h 10 (92.0mg, 0.64mmol) in tetrahydrofuran solution, stirred at this temperature for 30 minutes, slowly rose to room temperature and continued to react for 30 minutes, then added Se (50.5mg, 0.64mmol), and continued to react at room temperature for 1 hour. Then the binuclear rhodium compound [Cp*RhCl 2 ] 2 (256.0 mg, 0.32 mmol) was added to the reaction system for an additional 3 hours. After the reaction, stand and filter, and dry the solvent under reduced pressure. The obtained crude product is separated by column chromatography (petroleum ether / dichloromethane=6:1) to obtain the dark red target product rhodium complex Rh (257.1 mg, produced rate 81%).

[0034] 1 H NMR (400MHz, CDCl 3 ,25℃): δ=4.23(s,2H),1.69(s,30H,Cp*).Theoretical value of elemental anal...

Embodiment 2

[0036] Rh catalyzed N-methylation of arylamines:

[0037]

[0038] The rhodium complex Rh prepared in Example 1 was used as a catalyst to catalyze the N-methylation reaction of arylamines: to aniline (10mmol, 0.93g) and CH 3 Add the toluene solution of the binuclear semi-sandwich rhodium complex (0.01mmol, 9.9mg) containing ortho-carborane in I (10mmol, 1.42g), the reaction temperature is room temperature, and the reaction time is 100 minutes, after finishing, the concentrated reaction solution is directly Separation by silica gel column chromatography, drying to constant mass, to obtain the corresponding N-methylated product C 7 h 9 N (93% yield), 1 H NMR (400MHz, CDCl 3 , 25°C): δ=7.48 (d, J=7.0Hz, 2H), 7.36-7.27 (m, 3H), 5.23 (brs, 1H), 2.56 (s, 3H). Elemental analysis: C 78.46, H 8.47, N 13.07 (theoretical); C 78.50, H 8.51, N 13.03 (actual).

Embodiment 3

[0040] Rh catalyzed N-methylation of arylamines:

[0041]

[0042] The rhodium complex Rh prepared in Example 1 was used as a catalyst to catalyze the N-methylation reaction of arylamines: to 4-methylaniline (10mmol, 1.07g) and CH 3 Add the toluene solution of the binuclear semi-sandwich rhodium complex (0.01mmol, 9.9mg) containing ortho-carborane in I (10mmol, 1.42g), the reaction temperature is room temperature, and the reaction time is 60 minutes. After finishing, the concentrated reaction solution is directly Separation by silica gel column chromatography, drying to constant mass, to obtain the corresponding N-methylated product C 8 h 11 N (yield 90%), 1 H NMR (400MHz, CDCl 3,25℃):δ=7.45(d,J=7.0Hz,2H),7.38(d,J=7.2Hz,2H),5.25(brs,1H),2.57(s,3H),2.23(s,3H ). Elemental analysis: Elemental analysis: C 79.29, H 9.15, N 11.56 (theoretical); C 79.32, H 9.22, N 11.53 (actual).

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Abstract

The invention relates to a binuclear rhodium complex containing an ortho-carborane structure and preparation and application thereof. The preparation method of the rhodium complex comprises the following steps: 1) adding an n-BuLi solution into an ortho-carborane solution, and then reacting for 30-60 min at room temperature; 2) adding selenium and reacting for 1-2h at room temperature; 3) adding [Cp*RhCl2]2, reacting at room temperature for 3-6h, and performing post-treating to obtain the rhodium complex; and the rhodium complex is used to catalyze arylamine N-methylation reaction to prepare arylamine N-methylated derivatives. Compared with the prior art, the preparation method of the binuclear semi-sandwich rhodium complex containing the ortho-carborane structure is simple and green, has excellent selectivity and higher yield, and the prepared rhodium complex has higher catalytic activity at room temperature, can be used for catalyzing aromatic amine N-methylation reaction to prepare the aromatic amine N-methylation derivatives, has high catalytic reaction yield, and has wide industrial application prospect.

Description

technical field [0001] The invention belongs to the technical field of synthetic chemistry and relates to a binuclear semi-sandwich trivalent rhodium complex containing an ortho carborane structure and its preparation and application. Background technique [0002] Nitrogen-containing compounds are very important intermediates in organic synthesis, and the alkylation reaction of nitrogen atoms in N-H-containing compounds is an important way to synthesize such compounds. The most commonly used alkylating reagents for the alkylation reaction of nitrogen atoms in N-H-containing compounds are halogenated hydrocarbons and sulfuric acid esters. Among them, the method of using halogenated hydrocarbons as alkylating reagents is to carry out nucleophilic attack on halogenated hydrocarbons by the nitrogen negative ion intermediate formed by the substrate and strong base (sodium tert-butoxide or butyllithium, etc. to air-sensitive reagents) at low temperature. , to generate alkane-subs...

Claims

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Application Information

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IPC IPC(8): C07F15/00B01J31/22C07C209/60C07C211/48C07C211/52
CPCB01J31/2295B01J2231/4277B01J2531/0225B01J2531/822C07C209/60C07F15/0073C07C211/48C07C211/52
Inventor 姚子健吕文瑞李荣建高永红邓维
Owner SHANGHAI INST OF TECH
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