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Novel process for preparing (C6Me6)2Ru organic metal complex

A technology of organometallic complexes, which is applied in the field of synthesis process development of organometallic complexes, can solve the problems of low overall yield and low safety factor in the preparation process, achieve high yield, reduce production cost and operation difficulty, The effect of reagent stabilization

Inactive Publication Date: 2011-11-09
BEIJING UNIV OF CHEM TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Fischer Synthesis [C 6 Me 6 ] 2 There are four steps in the Ru process, three of which need to be carried out under anhydrous and oxygen-free conditions. The reactants and reagents need to be dehydrated and deoxygenated. The safety factor of the preparation process is low, and the total yield is relatively low, only 19% (based on RuCl 3 )

Method used

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  • Novel process for preparing (C6Me6)2Ru organic metal complex

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Effect test

Embodiment 1

[0022] 1) Take 0.300 g of RuCl 3 ·3H 2 O, 1.8mL phellandrene, and 18mL absolute ethanol were placed in a 50mL single-necked flask, reacted at reflux temperature for 4 hours, then stopped the reaction, naturally cooled to room temperature, and then stood still for 10 hours at -22°C, with reddish-brown Crystals were formed, filtered, and the filter cake was washed with absolute ethanol at 4°C to obtain a reddish-brown crystal product. The filtrate was concentrated by vacuum distillation, and the concentrated solution was repeated to recover the product in the filtrate, combined and dried in a vacuum oven at 80°C for 1 hour to obtain [RuCl 2 (C 10 h 14 )] 2 The product is 0.300 g, and the product yield is 67.7%.

[0023] 2) Take 3.800 g of hexamethylbenzene raw material and place it in a reactor at 165° C. until the hexamethylbenzene is completely melted, and raise the temperature of the reactor to 178° C. Get the [RuCl of step 1) preparation 2 (C 10 h 14 )] 2 Product 0...

Embodiment 2

[0027] 1) Take 0.222 grams of RuCl 3 ·3H 2 O, 1.1mL phellandrene, and 10mL absolute ethanol were placed in a 25mL single-necked flask, reacted at reflux temperature for 4 hours, then stopped the reaction, naturally cooled to room temperature, and then stood still for 10 hours at -22°C, with reddish-brown Crystals were formed, filtered, and the filter cake was washed with absolute ethanol at 4°C to obtain a reddish-brown crystal product. The filtrate is concentrated by vacuum distillation, and the concentrated solution repeats the above operations to reclaim the product in the filtrate, merges and dries the product to obtain [RuCl 2 (C 10 h 14 )] 2 The product is 0.199g, and the product yield is 77%.

[0028] 2) Take 3.000 g of hexamethylbenzene raw material and place it in a reactor at 165° C. until the hexamethylbenzene is completely melted, and raise the temperature of the reactor to 175° C. Get the [RuCl of step 1) preparation 2 (C 10 h 14 )] 2 Product 0.300 gram,...

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Abstract

Ruthenium is a transition metal element, has multiple valence states and complicated coordination states and can form various organic complexes. The bivalent ruthenium organic compound is the most common, and researches on the trivalent and the nulvalent ruthenium organic complexes are fewer. [C6Me6]2Ru is similar to ferrocene in shape and has a bread sandwich structure. E.O.Fischer firstly reports the synthesis of the compound [C6Me6]2Ru; aluminum powder and diethyl aluminum chloride used in the reaction have active chemical properties and can be oxidized and even burn and explode in air; and aluminum trichloride and aluminum tribromide are very sensitive to water. A Fischer [C6Me6]2Ru synthesis technology comprises four steps, wherein three steps need to be performed in an anhydrous and oxygen-free condition, reactants and reagents need to be dehydrated and deoxidized, the safety coefficient of a preparation process is low and the total yield is lower and is 19% only (in terms of RuCl3). The invention develops a brand new synthesis design way, in which RuCl3 hydrate is adopted as a raw material, four steps are performed for synthesis and reaction to prepare the [C6Me6]2Ru; the yield of the novel process reaches 39%, which is improved by 20% compared with that of the E.O.Fischer synthesis technology, and the reagents used in the synthesis process are stable and readily available; except for the last step of sodium ammonia reduction, dehydration and deoxidization are not needed in the other three steps, therefore, the operation technology process is simplified, the safety coefficient is raised, and the novel process is suitable for the industrialized production. The organic metal Ru(O) complex which is wide in application range is a potential homogeneous catalyst, can be applied to catalysis of aromatic hydrogenation and asymmetrical catalysis, and can also be applied to the field of clinical medicaments to serve as a novel anti-cancer medicament.

Description

technical field [0001] The invention belongs to the field of synthesis process development of organometallic complexes, in particular to an organometallic complex C 6 Me 6 Ru(O)C 6 Me 6 new preparation process. Background technique [0002] Organometallic complexes are widely used, mainly in organic synthesis, coordination catalysis and new anticancer drugs. After the middle of the twentieth century, more and more metal-organic complexes have been developed and produced huge economic value. [C 6 Me 6 ] 2 Ru is a transition metal organic complex, which has the ability to catalyze the selective hydrogenation of arenes, and it is also a potential anticancer drug with great development prospects. In 1970, E.O.Fischer first synthesized [C 6 Me 6 ] 2 Ru, which uses aluminum powder to reduce ruthenium trichloride to relatively active ruthenium dichloride, and then reacts with hexamethylbenzene under the action of diethylaluminum chloride to synthesize a divalent rutheniu...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F15/00
Inventor 王艳辉张远洋刘俊红王乾龙汤城
Owner BEIJING UNIV OF CHEM TECH
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