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Ruthenium complex containing ortho-carbonboryl benzoxazole structure and preparation and application thereof

A technology of carboryl benzoxazole and ruthenium complexes, which is applied in the field of semi-sandwich ruthenium complexes and their preparation, can solve problems such as environmental impact, expensive iridium complexes, and highly toxic selenium compounds, and achieve stable thermal Stability, the preparation method is simple and green, and the effect of stabilizing physical and chemical properties

Active Publication Date: 2019-08-09
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-carbonboryl benzoxazole structure and preparation and application thereof
  • Ruthenium complex containing ortho-carbonboryl benzoxazole structure and preparation and application thereof
  • Ruthenium complex containing ortho-carbonboryl benzoxazole structure and preparation and application thereof

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-carbonboryl benzoxazole structure and preparation and application thereof. A preparation method of the ruthenium complex comprises thefollowing steps that 1, an n-BuLi solution is added into an ortho-carborane solution for a reaction at the room temperature for 30-60 minutes; 2, bromobenzoxazole is added for a reaction at the room temperature for 6-8 hours; 3, [(p-cymene)RuCl2]2 is added for a reaction at the room temperature for 3-5 hours, and post-treatment is carried out to obtain the ruthenium complex; the ruthenium complexis used for catalyzing auto-oxidation coupling of primary amines to prepare imine compounds. Compared with the prior art, the prepared bivalent semi-sandwich ruthenium complex containing the ortho-carbonboryl benzoxazole structure has the advantages that the ruthenium complex has stable physical and chemical properties and thermal stability and is still stable at the high temperature of 300 DEG C;moreover, the preparation method is simple and environmentally friendly, and the ruthenium complex achieves excellent catalytic activity and a high yield in the reaction of catalyzing auto-oxidationcoupling of primary amines to prepare 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 Applications(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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