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Ruthenium Complex Containing Ortho-Carboryl Benzoxazole Structure and Its Preparation and Application

A technology of carboryl benzoxazole and ruthenium complexes, which is applied in the field of semi-sandwich ruthenium complexes and its preparation, can solve the problems of high toxic selenium compounds, iridium complexes, high prices, and environmental impact, and achieve stable physical Chemical properties, preparation methods are simple and green, and the effect of stable thermal stability

Active Publication Date: 2021-02-26
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 Ortho-Carboryl Benzoxazole Structure and Its Preparation and Application
  • Ruthenium Complex Containing Ortho-Carboryl Benzoxazole Structure and Its Preparation and Application
  • Ruthenium Complex Containing Ortho-Carboryl Benzoxazole Structure and Its Preparation and Application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] Synthesis of semi-sandwich ruthenium complexes Ru with ortho carboryl benzoxazole structure:

[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 bromobenzoxazole (126.7mg, 0.64mmol), continued to react at room temperature 6 hours. 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 obtained crude product is separated by column chromatography (petroleum ether / tetrahydrofuran=6:1) to obtain the orange-red target product ruthenium (II) complex Ru (241.2 mg, Yield 71%).

[0035] 1 H NMR (4...

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: to benzylamine (10mmol, 1.07g) was added an ortho carborane o-C 2 B 10 h 10 Divalent ruthenium complex (0.002mmol, 2.6mg) in toluene solution, and air was introduced as an oxidant to react, the reaction temperature was 30°C, and the reaction time was 180 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 14 h 13 N (yield 86%), 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: C86.12, H 6.71, N 7.17 (theoretical); C 86.03, H 6.69, 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 (10mmol, 1.37g), add an ortho carborane o-C 2 B 10 h 10 Divalent ruthenium complex (0.002mmol, 2.6mg) in toluene solution, and air was introduced as an oxidant to react, the reaction temperature was 30°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 (93% yield), 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 86.10, H 7.69, N 6.30 (actual).

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Abstract

The invention relates to a ruthenium complex containing an ortho-carboryl benzoxazole structure and its preparation and application. The preparation method of the ruthenium complex comprises the following steps: 1) adding n-BuLi solution to an ortho-carborane solution , then react at room temperature for 30‑60min; 2) add bromobenzoxazole, and react at room temperature for 6‑8h; 3) add [(p‑cymene)RuCl 2 ] 2 , and reacted at room temperature for 3‑5h, after post-treatment to obtain the ruthenium complex; the ruthenium complex is used to catalyze the autoxidative coupling of primary amines to prepare imine compounds. Compared with the prior art, the bivalent half-sandwich ruthenium complex containing the ortho-carboryl benzoxazole structure prepared by the present invention has stable physical and chemical properties and thermal stability, and the ruthenium complex can The product is still stable, and the preparation method is simple and green, and it shows excellent catalytic activity and yield in the reaction of catalyzing the autoxidative coupling of primary amines to synthesize 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 benzoxazole 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 us...

Claims

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Application Information

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