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Cyclo-octadiene complex containing dinitrogen ligand low-valent metal rhodium (I) and preparation method thereof

A technology of cyclooctadiene and nitrogen ligands, which is applied in the field of potential coupling and hydrogenation reaction catalysts and its synthesis, and can solve the problems of metal center oxidation, low yield, and cumbersome steps

Inactive Publication Date: 2016-08-03
PETROCHINA CO LTD
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  • Abstract
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Problems solved by technology

However, the metal rhodium complexes reported so far have low yields, cumbersome steps, complex post-treatment methods, and the tendency to multi-ligand coordination in the synthesis process.
[0003] The object of the present invention is to solve the problems (metal center oxidation, low yield, complex handling and multi-ligand coordination) in the process of synthesizing low-valent metal rhodium complexes, and to use two (trimethylsilyl) amino strong bases In the presence of the organic dinitrogen ligand 2-(pyrrole-2-methyleneamino)anisole with methoxy and pyrrole groups and (1,5-cyclooctadiene)rhodium chloride (I ) dimer compound reaction, efficiently synthesized low-valent metal rhodium (I) complexes

Method used

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  • Cyclo-octadiene complex containing dinitrogen ligand low-valent metal rhodium (I) and preparation method thereof

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preparation example Construction

[0020] A cyclooctadiene complex containing dinitrogen ligand low-valent metal rhodium (I) and its preparation method, the reaction schematic diagram is as attached figure 1 As shown, the specific steps are as follows:

[0021] (1) React a certain proportion of o-methoxyaniline and pyrrole-2-carboxaldehyde in anhydrous alcoholic solvent, acetic acid is used as a catalyst, the reaction temperature is 70-90°C, and the reaction is stirred for 8-12 hours to obtain diazepam Phosphine ligand 2-(pyrrole-2-methyleneamino) anisole;

[0022] (2) Under the protection of an inert gas, 2-(pyrrole-2-methyleneamino) anisole and bis(trimethylsilyl)amino strong base are stirred in anhydrous solvent at room temperature for deprotonation reaction, and the reaction time for 20-40 minutes, and then reacted with (1,5-cyclooctadiene) rhodium (I) dimer compound in situ for 3-6 hours to obtain a mixture that was easily evaporated to dryness, and its solvent was evaporated After drying, use an organic...

Embodiment 1

[0030] Synthesis of the cyclooctadiene complex of dinitrogen ligand metal rhodium (I), the anhydrous solvent used in the step (2) is anhydrous tetrahydrofuran, the base used is two (trimethylsilyl) amide lithium, deprotonation reaction The reaction temperature between the product and (1,5-cyclooctadiene)rhodium(I) chloride dimer is 45° C., and the reaction time is 6 hours.

[0031] (1) Weigh 950mg (10mmol) of pyrrole-2-carbaldehyde and add it to a 100ml round-bottomed flask with a magnetic stirrer, measure 20ml of anhydrous methanol with a syringe and add it to the reaction flask, add a drop of acetic acid, and keep stirring in batches 1.23 g (10 mmol) of o-methoxyaniline was added, and the reaction system was kept under reflux for 8 hours, and the resulting mixture was cooled to obtain the solid product 2-(pyrrole-2-methyleneamino)anisole.

[0032] (2) The reaction is carried out under nitrogen protection conditions by utilizing a double row tube device. Weigh 190 mg of 2-(p...

Embodiment 2

[0034] The synthesis of the cyclooctadiene complex of dinitrogen ligand metal rhodium (I), the anhydrous solvent anhydrous tetrahydrofuran used in the step (2), the alkali used is two (trimethylsilyl) sodium amide, and the deprotonation reaction product The temperature of the reaction with (1,5-cyclooctadiene)rhodium(I) chloride dimer is 45° C., and the reaction time is 4 hours.

[0035] (1) For the preparation of 2-(pyrrole-2-methyleneamino)anisole, see step 1 of Example 1.

[0036] (2) The reaction is carried out under nitrogen protection conditions by utilizing a double row tube device. Weigh 190 mg of 2-(pyrrole-2-methyleneamino) anisole (0.95 mmol, dissolved in 8 ml of anhydrous tetrahydrofuran solvent), then pour it into a 25 ml round-bottomed flask with a magnetic stirring bar, add 1 ml of bis(tri A tetrahydrofuran solution of methylsilyl) sodium amide (1.0mmol), reacted for 40 minutes to obtain a yellow solution; weigh (1,5-cyclooctadiene) rhodium chloride (I) dimer c...

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Abstract

The invention discloses a cyclo-octadiene complex containing a dinitrogen ligand low-valent metal rhodium (I) and a preparation method thereof. The method comprise the following steps: 1) anhydrous alcohol is taken as a solvent and acetic acid is taken as a catalyst, o-anisidine and pyrrole-2-formaldehyde are reacted to prepare a dinitrogen schiff base ligand 2-(pyrrole-2-methylene amino)anisole; and 2) under condition that inert gas protection and existence of dis(trimethylsilyl)amino strong base, the 2-(pyrrole-2-methylene amino)anisole ligand and a (1,5-cyclo-octadiene) rhodium chloride (I) dimer are subjected to a reaction in an organic solvent to prepare the cyclo-octadiene complex containing the dinitrogen ligand low-valent metal rhodium (I). The method has the advantages that the reaction yield is high, reaction steps and post treatment are simple, a structure of the obtained compound is unique, the complex contains low-valent rhodium metal ions and easily left cyclo-octadiene organic ligand, and is a latent catalyst for coupling and hydrogenation reactions.

Description

technical field [0001] The invention relates to a low-valent metal rhodium complex and a synthesis method thereof, and in more detail relates to a potential coupling and hydrogenation reaction catalyst and a synthesis method thereof. Background technique [0002] The transition metal rhodium complex catalyst is a kind of metal complex with low-valent metal rhodium as the active center and nitrogen-containing or phosphorus-containing coordination atoms as ligands. Such metal complexes have the advantages of high activity, high stability and low reaction temperature in catalytic hydrogenation, hydroformylation and coupling reactions of nitro, carbonyl and aromatic compounds. However, the synthesis process of metal rhodium complexes reported so far has low yield, cumbersome steps, complex post-treatment methods, and multi-ligand coordination. [0003] The object of the present invention is to solve the problems (metal center oxidation, low yield, complex handling and multi-lig...

Claims

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Application Information

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IPC IPC(8): C07F15/00B01J31/22
Inventor 葛汉青白正帅刘肖飞张峰黄荣禄南洋李燕王雨光何崇慧翁志强赵素英胡晓丽景志刚王书峰高冬梅
Owner PETROCHINA CO LTD
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