A biomimetic aqueous heterogeneous catalytic system catalyzes the condensation reaction between aromatic aldehydes and malonate diesters
A malonate diester, heterogeneous catalysis technology, applied in the field of fine chemicals of chemical engineering, can solve the problems of useless value by-products, reduced reaction selectivity, loss of raw materials and products, etc., to achieve saving and full utilization, Improve selectivity and yield, reduce the effect of oxidation
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Embodiment 1
[0044] Embodiment 1 A kind of method that adopts clean technology to synthesize benzoylidene dimethylmalonate comprises the following steps:
[0045] (1) At room temperature, put 50% of the total amount of dimethyl malonate, soluble amino-containing substances, protonic acid, metal salt, and aqueous mixed solvent into the reactor, adjust the pH to 5-6, and , after heating to 30° C., gradually add benzaldehyde or its mixture with the remaining 50% dimethyl malonate. Continue to react at this temperature until the product phase no longer continues to increase;
[0046] (2) From the reaction mixture obtained in step (1), separate out the product-rich phase and the catalyst-containing solvent phase by means of the difference in specific gravity, wherein the solvent phase is recycled;
[0047] (3) The product-rich phase obtained in step (2) is washed with a 1:1 methanol-water solution to remove a small amount of unreacted raw materials to obtain the condensation product dimethyl p...
Embodiment 2
[0048] Embodiment 2 A kind of method that adopts clean technique to synthesize diethyl phenylidene malonate comprises the following steps:
[0049] (1) Put diethyl malonate accounting for 50% of the total amount, amine-containing substances insoluble in solvents, protonic acids, metal salts, and water-containing mixed solvents into the reactor, adjust pH 7 to 8, and simulate sunlight irradiation After heating up to 50°C, gradually add the mixture of benzaldehyde and the remaining 50% diethyl malonate. Continue the reaction at this temperature until the product phase does not continue to increase;
[0050] (2) From the reaction mixture obtained in step (1), use the difference in specific gravity to separate the product-rich phase, solvent phase and solvent-insoluble solid phase containing amine-based substances, and the latter two can be recycled;
[0051] (3) adopt underpressure distillation to the rich product phase that step (2) obtains, to slough a small amount of unreacte...
Embodiment 3
[0052] Embodiment 3 A kind of method that adopts clean technology to synthesize dimethyl benzomalonate comprises the following steps:
[0053] (1) Put all insoluble amine-containing substances, protonic acids, metal salts, aqueous mixed solvents, aromatic aldehydes and dimethyl malonate into the reactor, adjust the pH to 6-7, and heat up to 25 After ℃, maintain this temperature and continue the reaction until the product phase does not continue to increase;
[0054] (2) From the reaction mixture obtained in step (1), use the difference in specific gravity to separate the product-rich phase, the solvent phase and the solid phase amine-containing substance insoluble in the solvent phase, and the latter two can be recycled;
[0055] (3) The product-rich phase obtained in step (2) is washed with 1:1 (volume ratio) methanol-water solution to remove a small amount of unreacted raw materials to obtain the condensation product dimethyl phenylidene malonate or substituted phenylidene ...
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