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Ruthenium complex containing carboranyl benzimidazole structure as well as preparation method and application of ruthenium complex

A technology containing carboryl benzimidazole and carboryl benzimidazole, which is applied in the field of semi-sandwich ruthenium complexes and its preparation, and can solve problems such as environmental impact, expensive iridium complexes, and large toxic selenium compounds , achieving high stability, high catalytic activity and yield, and simple synthesis process

Active Publication Date: 2019-07-16
SHANGHAI INST OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although the catalytic yield of the trivalent iridium complex to primary amines is high, the price of the iridium complex is expensive, and the more toxic selenium compound is used in the synthesis process, which has a greater impact on the environment.

Method used

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  • Ruthenium complex containing carboranyl benzimidazole structure as well as preparation method and application of ruthenium complex
  • Ruthenium complex containing carboranyl benzimidazole structure as well as preparation method and application of ruthenium complex
  • Ruthenium complex containing carboranyl benzimidazole structure as well as preparation method and application of ruthenium complex

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] Synthesis of half-sandwich ruthenium complexes containing ortho-carboryl benzimidazole structures:

[0032]

[0033] Among them, "·" represents the boron-hydrogen bond B-H.

[0034] 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 1 hour, then added bromobenzimidazole (126.7mg, 0.64mmol), and continued to react at room temperature for 6 Hour. Then the binuclear ruthenium compound [(p-cymene)RuCl 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 crude product obtained is separated by column chromatography (petroleum ether / tetrahydrofuran=6:1) to obtain the orange-red target product ruthenium (II) complex Ru (254.4 mg, Yield 75%).

[00...

Embodiment 2

[0038] Ruthenium(II) complexes catalyze the autoxidative coupling reaction of primary amines:

[0039]

[0040] The ruthenium complex prepared in Example 1 was used as a catalyst to catalyze the autoxidative coupling reaction of primary amines: in benzylamine (1mmol, 107mg), add a compound containing ortho carborane o-C 2 B 10 h 10 The divalent ruthenium complex (0.001mmol, 1.3mg) in toluene (toluene) solution, and pass into air as an oxidant to react, the reaction temperature is 60°C, and the reaction time is 180 minutes. After the end, the concentrated reaction solution is directly passed through the silica gel column Chromatographic separation, drying to constant mass, to obtain the corresponding imine compound C 14 h 13 N (yield 87%), 1 H NMR (400MHz, CDCl 3):δ=8.32(s,1H),7.72-7.69(m,2H),7.35-7.33(d,J=1.8Hz,3H),7.27-7.26(d,J=4.4Hz,4H),7.20- 7.17 (m, 1H), 4.75 (s, 2H), elemental analysis: C 86.12, H 6.71, N 7.17 (theoretical); C 86.06, H 6.68, N 7.12 (actual).

Embodiment 3

[0042] Ruthenium(II) complexes catalyze the autoxidative coupling reaction of primary amines:

[0043]

[0044] The ruthenium complex prepared in Example 1 was used as a catalyst to catalyze the autoxidative coupling reaction of primary amines: in 4-methylbenzylamine (1mmol, 137mg), add an ortho carborane o-C 2 B 10 h 10 Divalent ruthenium complex (0.001mmol, 1.3mg) in toluene solution, and air was introduced as an oxidant to react, the reaction temperature was 80°C, and the reaction time was 60 minutes. After the end, the concentrated reaction solution was directly separated by silica gel column chromatography , dried until the mass remains unchanged, and the corresponding imine compound C 16 h 17 N (yield 96%), 1 H NMR (400MHz, CDCl 3 ):δ=8.38(s,1H),7.70-7.64(d,J=6.8Hz,2H),7.39-7.36(d,J=4.0Hz,2H),7.30-7.18(m,4H),4.75( s, 2H), 2.41 (s, 3H), 2.35 (s, 3H), elemental analysis: C86.05, H 7.67, N 6.27 (theoretical); C 86.14, H 7.65, N 6.32 (actual).

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Abstract

The invention relates to a ruthenium complex containing a carboranyl benzimidazole structure as well as a preparation method and application of the ruthenium complex. The preparation method of the ruthenium complex comprises the following steps: 1) adding a n-BuLi solution into a carborane solution, and performing a reaction at room temperature for 30-60 min; 2) adding bromobenzimidazole, and performing a reaction at room temperature for 6-8 h; and 3) adding [(p-cymene)RuCl2]2, performing a reaction at room temperature for 3-5 h, and performing post treatment to obtain the ruthenium complex. The ruthenium complex is used to catalyze self-oxidative coupling of primary amines to prepare imine compounds. Compared with the prior art, the method provided by the invention uses the dinuclear ruthenium compound [(p-cymene)RuCl2]2 as a raw material, and the [(p-cymene)RuCl2]2 is reacted with the n-BuLi and o-carbonboryl benzimidazole to obtain the bivalent half-sandwich ruthenium complex containing the o-carbonboryl benzimidazole structure; and the ruthenium complex provided by the invention has stable physicochemical properties and thermal stability, is still stable at high temperature of300 DEG C, has a simple and green synthetic process, and exhibits excellent activity in the reaction of catalyzing the self-oxidative coupling of primary amines to prepare the imine compounds.

Description

technical field [0001] The invention belongs to the technical field of synthetic chemistry, and relates to a semi-sandwich ruthenium complex containing an ortho-carboryl benzimidazole structure and a preparation method and application thereof. Background technique [0002] Since imine compounds can participate in a series of organic reactions such as addition reactions, epoxidation reactions, and condensation reactions, they have been widely used in the fields of medicine, pesticides, functional materials, organic intermediates, and corrosion mitigation. Imine compounds can be used as intermediates to prepare different important compounds such as amines and aldehydes and ketones. Therefore, the synthesis of imine compounds has always been one of the focuses of research in the field of chemistry. In recent years, in order to meet the requirements of green synthesis, researchers have developed a variety of methods for the synthesis of imines. Compared with other methods, the ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F17/02B01J31/22C07C251/24C07C249/02
CPCB01J31/2295B01J2531/0225B01J2531/0241B01J2531/821C07C249/02C07F17/02C07C251/24
Inventor 姚子健樊晓楠高永红邓维
Owner SHANGHAI INST OF TECH
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