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A kind of binuclear rhodium complex containing ortho carborane structure and its preparation and application

A rhodium complex and carborane technology, applied in the field of binuclear semi-sandwich trivalent rhodium complexes, can solve problems such as carcinogenicity, high requirements for reaction equipment, and harsh reaction conditions

Active Publication Date: 2021-05-11
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 harsh reaction conditions, complex operations, and high requirements for reaction equipment; sulfuric acid esters (such as dimethyl sulfate, diethyl sulfate, etc.) are a class of active alkyl groups. Alkylation reagent can carry out alkylation reaction under milder conditions, but its toxicity is relatively high, and it is carcinogenic, thus limiting its application in industry

Method used

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  • A kind of binuclear rhodium complex containing ortho carborane structure and its preparation and application
  • A kind of binuclear rhodium complex containing ortho carborane structure and its preparation and application
  • A kind of binuclear rhodium complex containing ortho carborane structure and its preparation and application

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 (92.0 mg, 0.64 mmol) 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 (50.5 mg, 0.64 mmol), 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 was finished, stand and filter, and dry the solvent under reduced pressure. The crude product obtained was 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...

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, and the concentrated reaction solution after finishing 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 its preparation and application. The preparation method of the rhodium complex comprises the following steps: 1) adding n-BuLi solution to the ortho-carborane solution, Then react at room temperature for 30-60min; 2) add selenium, and react at room temperature for 1-2h; 3) add [Cp*RhCl 2 ] 2 , and react at room temperature for 3‑6h, and obtain the rhodium complex after post-treatment; the rhodium complex is used to catalyze the N-methylation reaction of arylamine 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 in the present invention is simple and green, has excellent selectivity and higher yield, and the prepared rhodium complex is stable at room temperature It has high catalytic activity, can be used to catalyze the N-methylation reaction of arylamines to prepare N-methylated derivatives of arylamines, has high catalytic reaction yield, and has wide industrial application prospects.

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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Patent Type & Authority Patents(China)
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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