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Dipyridyl tetradentate ligand ruthenium complex as well as preparation method and application thereof

The technology of a tetradentate ligand and a ruthenium complex is applied to the bipyridine tetradentate ligand ruthenium complex and the fields of preparation and application thereof, and can solve the problems of large amount of catalyst, increased production cost, unfavorable industrialized production and the like

Active Publication Date: 2014-08-13
NANKAI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] Generally speaking, the homogeneous catalytic hydrogenation of esters can be carried out under relatively mild conditions, but most of the reported reaction temperatures still require 100 °C and above, and the amount of catalyst used is large, which increases the production cost and is not conducive to Industrial production

Method used

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  • Dipyridyl tetradentate ligand ruthenium complex as well as preparation method and application thereof
  • Dipyridyl tetradentate ligand ruthenium complex as well as preparation method and application thereof
  • Dipyridyl tetradentate ligand ruthenium complex as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0044] Preparation of Ligand 1

[0045]

[0046] 2-methyl-6-(tri-n-butyltin base)pyridine (8): add 2-methyl- 6-bromopyridine (20.0 g, 116 mmol), the system was replaced by an argon atmosphere, and anhydrous tetrahydrofuran (200 mL) was added. The temperature of the system was controlled to -78°C with a liquid nitrogen-acetone cooling bath, and a solution of n-butyllithium in n-hexane (2.4M, 56.0 mL, 134 mmol) was added dropwise for 30 minutes. After dropping, continue to stir at -78°C for 2 hours. Tri-n-butyltin chloride (45.4 g, 140 mmol) was added dropwise into the system with a syringe, and the dropping time was 30 minutes. After dropping, continue to stir at -78°C for 30 minutes, then return to room temperature and react overnight (14 hours). The system was desolvated with a rotary evaporator, the residue was diluted with ether (300 mL), washed with water (200 mL) and saturated brine (200 mL) successively, the organic phase was dried over anhydrous sodium sulfate, an...

Embodiment 2

[0053] Preparation of Ligand 2

[0054]

[0055] 2-[(tert-butyldimethylsilyl)methyl]-6-bromopyridine (12): Add 2-hydroxymethyl- 6-bromopyridine (10.6g, 56.4mmol) and imidazole (15.4g, 226mmol), the system was replaced by an argon atmosphere, anhydrous DMF (50mL) was added, and tert-butyldimethyl Chlorosilane (10.2 g, 67.7 mmol). After the addition was complete, the reaction was stirred at room temperature for 1 hour. TLC monitored the reaction to be complete. Water (50 mL) was added to quench the reaction, and the product was extracted with diethyl ether (3×100 mL). The organic phase was washed with water (100 mL) and saturated brine (100 mL) successively. Dry over anhydrous sodium sulfate and let stand. The desiccant was removed by suction filtration, the filtrate was desolvated by a rotary evaporator, the residue was distilled under reduced pressure, and the 92°C / 0.1mmHg fraction was collected to obtain 15.3 g of a colorless oily liquid product, yield: 90%. 1 H NMR (40...

Embodiment 3

[0061] Preparation of Ligand 3

[0062]

[0063] 6,6'-dimethylol-2,2'-bipyridine (16): Add 12 (8.49g, 28.1mmol), 13( 16.9g, 33.0mmol), tetrakis(triphenylphosphine) palladium (1.14g, 0.99mmol) and anhydrous lithium chloride (3.60g, 84.9mmol), the system was degassed three times by freezing and thawing with liquid nitrogen, and finally replaced with Argon atmosphere. The system was heated to 120° C. with an oil bath, and the reaction was stirred for 12 hours until a large amount of palladium black was produced in the system. At this time, GC showed that 12 had been completely converted. The system was cooled to room temperature, diluted with ethyl acetate (100 mL), filtered through celite to remove insoluble matter, and 6N hydrochloric acid was added to make the system acidic (pH=3), and the layers were separated. The aqueous phase was adjusted to alkaline (pH=13) with 6N aqueous sodium hydroxide solution, extracted with diethyl ether (3×100 mL), the organic phase was washe...

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Abstract

The invention relates to a dipyridyl tetradentate ligand ruthenium complex as well as a preparation method of the complex and application of the complex to a reaction for hydrogenating ester compounds into alcohol compounds. A method for catalytically hydrogenating the ester compounds into the alcohol compounds by using the dipyridyl tetradentate ligand ruthenium complex is characterized by comprising the following steps: by taking 0.001mol% to 0.3mol% of the dipyridyl tetradentate ligand ruthenium complex based on the ester compounds, as a catalyst, adding 1mol%-10mol% of alkali based on the ester compounds, and catalytically hydrogenating the ester compounds into the corresponding alcohol compounds under the conditions that the temperature is 25-100 DEG C and the hydrogen pressure is 1-10MPa. The dipyridyl tetradentate ligand ruthenium complex is convenient to prepare, stable in structure and excellent in catalytic activity in hydrogenation reaction of the ester compounds. According to the preparation method, the shortcomings of requirements on high-temperature high-pressure reaction conditions and high catalyst consumption in an existing homogeneous or non-homogeneous catalytic hydrogenation system of the ester compounds are overcome, the catalyst consumption is low, the reaction conditions are mild, the reaction selectivity is good, and the economy and the safety of a production system are improved.

Description

technical field [0001] The invention relates to a novel bipyridine tetradentate ligand ruthenium complex, a preparation method thereof and an application in the hydrogenation reaction of ester compounds into alcohol compounds. Background technique [0002] The reduction of ester compounds to prepare alcohols is an important reaction in organic synthesis, which is of great significance both in basic scientific research and in industrial production. The reduction of ester compounds to alcohol compounds is commonly used in laboratories such as lithium aluminum hydride and other negative hydrogen reagents, and these negative hydrogen reagents will produce a large amount of inorganic waste during post-treatment, and these active negative hydrogen reagents will It will bring potential safety hazards and limit its application in industrial production. The reduction of esters to alcohols by catalytic hydrogenation is a highly atom-economical method, so the development of catalysts ...

Claims

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Application Information

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IPC IPC(8): C07F9/6558C07F9/58C07D213/38C07F15/00B01J31/24B01J31/22C07B41/02C07C29/149C07C31/20C07C41/26C07C43/13C07C31/125C07C33/26C07C67/31C07C69/675C07C33/22C07C31/08
Inventor 周其林李威谢建华王立新
Owner NANKAI UNIV
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