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Half-sandwich ruthenium complex containing ortho-carborane benzothiazole as well as preparation and application

A technology of carboryl benzene and complexes, which is applied in the field of semi-sandwich ruthenium complexes containing ortho-carboryl benzothiazoles, can solve the problems of harsh reaction conditions, poor catalyst stability, sensitivity, etc., and achieve The effect of short reaction time, simple and green preparation method, and high yield

Active Publication Date: 2020-11-20
SHANGHAI INST OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Matsuzaka reported that a ruthenium catalyst can catalyze this reaction (J.Am.Chem.Soc.2016,138,14836), but the catalyst is not stable, sensitive to air and water, and the reaction conditions are relatively harsh, requiring high temperature (150 degrees) and longer reaction time (24 hours)

Method used

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  • Half-sandwich ruthenium complex containing ortho-carborane benzothiazole as well as preparation and application
  • Half-sandwich ruthenium complex containing ortho-carborane benzothiazole as well as preparation and application
  • Half-sandwich ruthenium complex containing ortho-carborane benzothiazole as well as preparation and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0037] Synthesis of Semi-Sandwich Ruthenium Complexes Containing Ortho-Carboryl Benzothiazole Structure

[0038]

[0039] At –78°C, n-BuLi (1.6 mmol) in n-hexane was slowly added dropwise to the ortho-carborane o-C 2 B 10 h 10 (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 bromobenzothiazole (0.64mmol), and continued to react at room temperature for 6 hours. Then the binuclear ruthenium compound [CpRuCl 2 ] 2(0.32 mmol) was added to the reaction system and reacted for another 3 hours. After the reaction was finished, stand and filter, and dry the solvent under reduced pressure, and the crude product obtained was separated by column chromatography (petroleum ether / tetrahydrofuran=5:1) to obtain the red target product ruthenium (II) complex Ru (yield 76% ).

[0040] 1 H NMR (400MHz, CDCl 3 ,25℃): δ=7.89(d, J=7.2Hz, 1H), 7.73(t, J=7.5Hz, 1H), 7.50(d, J=7.0...

Embodiment 2

[0042] catalytic condensation reaction

[0043]

[0044] The catalyst prepared in Example 1 is used to catalyze the synthesis of stilbene derivatives: toluene (1.2mmol), benzaldehyde (1.0mmol), t BuOK (1.5mmol) and ruthenium complex Ru (0.02mmol) were dissolved in 3mL of toluene, and reacted at 60°C for 8 hours. After the end, the concentrated reaction solution was directly separated by silica gel column chromatography, dried until the mass remained constant, and the corresponding Product C 14 h 12 (yield 93%), 1 H NMR (400MHz, CDCl 3 ,25°C): δ7.52-7.47(m,4H),7.36-7.30(m,4H),7.25-7.19(m,2H),7.11(s,2H). Elemental Analysis Theoretical Value C 14 h 12 : C 93.29, H 6.71; Found: C 93.33, H 6.65. The specific results are shown in Table 1.

Embodiment 3

[0046] catalytic condensation reaction

[0047]

[0048] Catalysts prepared in Example 1 were used to catalyze the synthesis of stilbene derivatives: toluene (1.1mmol), 4-methylbenzaldehyde (1.0mmol), t BuOK (1.2mmol) and ruthenium complex Ru (0.03mmol) were dissolved in 3mL of toluene, and reacted at 50°C for 10 hours. After the completion, the reaction solution was concentrated and directly separated by silica gel column chromatography, and dried until the mass remained constant to obtain the corresponding product C 15 h 14 (yield 95%), 1 H NMR (400MHz, CDCl 3 ,25℃):δ7.47(d,2H,J=7.5Hz),7.38(d,2H,J=8.0Hz),7.31(t,2H,J=7.5Hz),7.21(t,1H,J = 7.5Hz), 7.13 (d, 2H, J = 8.0Hz), 7.06 (d, 1H, J = 16.0Hz), 7.02 (d, 1H, J = 16.0Hz), 2.33 (s, 3H). Elemental Analysis Theoretical Value C 15 h 14 : C 92.74, H7.26; Experimental value: C 92.80, H7.31. The specific results are shown in Table 1.

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Abstract

The invention relates to a half-sandwich ruthenium complex containing ortho-carborane alkyl benzothiazole as well as preparation and application thereof. The preparation method specifically comprisesthe following steps: i) adding an organic mixed solution of n-butyl lithium into an organic mixed solution of ortho-carborane at the temperature of -70 DEG C to-80 DEG C, then heating to the room temperature, and continuously reacting for 30-60 minutes; ii) adding bromo-benzothiazole, and carrying out a reaction for 6-8 hours at a room temperature; and iii) adding a binuclear ruthenium compound, reacting at the room temperature for 3-5 hours, and separating to obtain the half-sandwich ruthenium complex. The catalyst is applied to preparation of stilbene derivatives by catalyzing condensation reaction of methylbenzene and aromatic aldehyde. Compared with the prior art, the disclosed complex is insensitive to air and water and stable in property, and shows efficient catalytic activity in catalyzing the condensation reaction of methylbenzene and aromatic aldehyde, and the preparation method is simple, green, high in yield, mild in reaction conditions and good in universality.

Description

technical field [0001] The invention belongs to the technical field of synthetic chemistry, and in particular relates to a semi-sandwich ruthenium complex containing an ortho-carboryl benzothiazole and its preparation and application. Background technique [0002] Carborane-based metal complexes are widely used as catalysts in the chemical industry, and the semi-sandwich structure organometallic complexes have more novel structures in this kind of compounds. Therefore, it is of great significance to explore the metal-organic compounds with semi-sandwich structure and their synthesis methods based on carboranes as ligands. [0003] On the other hand, the stilbene skeleton is a structural unit of many important drug molecules and optical molecules. Exploring efficient synthetic methods of such compounds is one of the important research fields of organic chemistry. Both the traditional Wittig reaction and Heck reaction are important methods for preparing this compound; howeve...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F15/00B01J31/22C07C1/207C07C15/18C07C41/30C07C43/215C07C201/12C07C205/06C07C17/263C07C25/24C07C22/04
CPCC07F15/0046B01J31/1815C07C1/2072C07C41/30C07C201/12C07C17/263B01J2531/821C07C15/18C07C43/215C07C205/06C07C25/24C07C22/04
Inventor 姚子健卞明
Owner SHANGHAI INST OF TECH
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