A kind of phthalazinone derivative, preparation method of the derivative and catalyst for preparation thereof

A derivative, the technology of phthalazinone, which is applied in the field of ionic liquid catalysis, can solve the problems of large amount of ionic liquid catalyst used, complex product purification process, and less cycle times, so as to improve synthesis purity, quality and performance assurance, and improve The effect of utilization

Active Publication Date: 2018-12-18
东港智科产业园有限公司
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0007] The purpose of the present invention is to overcome the low utilization rate of raw materials, long reaction time, complex product purification process, large amount of ionic liquid catalyst used, and catalyst phthalazinone derivatives in the prior art when using acidic ionic liquid to catalyze the four-component reaction to prepare phthalazinone derivatives The loss in the circulation process is large, which leads to the disadvantages of less recycling times and the need for a series of treatments before the catalyst is recycled. A phthalazinone derivative, a preparation method of the derivative and a catalyst for its preparation are provided.

Method used

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  • A kind of phthalazinone derivative, preparation method of the derivative and catalyst for preparation thereof
  • A kind of phthalazinone derivative, preparation method of the derivative and catalyst for preparation thereof
  • A kind of phthalazinone derivative, preparation method of the derivative and catalyst for preparation thereof

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preparation example Construction

[0034] A kind of preparation method of phthalazinone derivative of the present invention, this method is to be reaction raw material with aromatic aldehyde, succinic anhydride, 5,5-dimethyl-1,3-cyclohexanedione and hydrazine hydrate, in acidic The catalysis of the ionic liquid catalyst prepares the phthalazinone derivative, and its chemical reaction formula is:

[0035]

[0036] In the above formula, substance I is aromatic aldehyde, substance II is succinic anhydride, substance III is 5,5-dimethyl-1,3-cyclohexanedione, substance IV is hydrazine hydrate, and substance V is prepared by the present invention 3,4,7,8-tetrahydro-3,3-dimethyl-11-aryl-2H-phthalazin[1,2-α]indole-1,6,9(11H)-trione , the structural formula of the acidic ionic liquid catalyst is:

[0037]

[0038] Aromatic aldehydes in the present invention are benzaldehyde, p-chlorobenzaldehyde, p-nitrobenzaldehyde, m-nitrobenzaldehyde, p-tolualdehyde, p-methoxybenzaldehyde, p-bromobenzaldehyde, 2,4-di Any one of...

Embodiment 1

[0047] Add 1mmol succinic anhydride, 1mmol 5,5-dimethyl-1,3-cyclohexanedione, 1mmol benzaldehyde, 1.2mmol hydrazine hydrate and 0.12mmol acidic ionic liquid to the belt filled with 5ml 98% ethanol aqueous solution In a 50ml single-necked bottle with a stir bar and a condenser. Heat to reflux for 35 minutes, TLC (thin plate chromatography) detection, the raw material point disappears, cool to room temperature, crush the precipitated solid, let stand, filter with suction, wash the filter residue with 98% ethanol aqueous solution, and vacuum dry to obtain 3, 4, 7 , 8-tetrahydro-3,3-dimethyl-11-phenyl-2H-phthalazin[1,2-α]indole-1,6,9(11H)-trione, the yield is 94% , directly add succinic anhydride, 5,5-dimethyl-1,3-cyclohexanedione, benzaldehyde and hydrazine hydrate to the collected filtrate for repeated use.

[0048] 3,4,7,8-tetrahydro-3,3-dimethyl-11-phenyl-2H-phthalazine[1,2-α]indole-1,6,9(11H) obtained in this example - The performance parameters of triketone are as follows:...

Embodiment 2

[0050] Add 1mmol succinic anhydride, 1mmol 5,5-dimethyl-1,3-cyclohexanedione, 1mmol p-chlorobenzaldehyde, 1.1mmol hydrazine hydrate and 0.10mmol acidic ionic liquid to 7ml 98% ethanol aqueous solution in a 50ml single-necked bottle with a stirrer bar and a condenser. Heated to reflux for 28 minutes, TLC (thin plate chromatography) detection, the raw material point disappeared, cooled to room temperature, crushed the precipitated solid, let stand, suction filtered, the filter residue was washed with 98% ethanol aqueous solution, and vacuum dried to obtain 11-(4- Chlorophenyl)-3,4,7,8-tetrahydro-3,3-dimethyl-2H-phthalazin[1,2-α]indole-1,6,9(11H)-trione, The yield is 93%. Succinic anhydride, 5,5-dimethyl-1,3-cyclohexanedione, p-chlorobenzaldehyde and hydrazine hydrate are directly added to the collected filtrate for repeated use.

[0051] The 11-(4-chlorophenyl)-3,4,7,8-tetrahydro-3,3-dimethyl-2H-phthalazine[1,2-α]indole-1,6 obtained in this example , The performance parameters...

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Abstract

The invention discloses a phthalazinone derivative and a preparation method thereof, and a catalyst used for preparation of the phthalazinone derivative, belonging to the technical field of ionic liquid catalysis. According to the invention, a mol ratio of aromatic aldehyde to succinic anhydride to 5,5-dimethyl-1,3-cyclohexanedione to hydrazine hydrate is 1: 1: 1: (1.0-1.2); the molar weight of an ionic liquid catalyst is 8 to 15% of the molar weight of aromatic aldehyde; the volume dose of a reaction solvent aqueous ethanol solution in terms of milliliter is 5 to 8 times of the molar weight of aromatic aldehyde in terms of millimole; reflux time is 21 to 53 min; after completion of the reaction, cooling to room temperature and pumping filtration are successively carried out; and a filter residue is subjected to washing and vacuum drying so as to obtain 3,4,7,8-tetrahydro-3,3-dimethyl-11-aryl-2H-phthalizine[1,2-alpha]-indolo-1,6,9(11H)-trione. The invention has the characteristics that the catalyst is high in activity; reaction time is short; the prepared derivative is simple to purify; the raw materials are high in utilization rate; the whole preparation process is simple and convenient in operation; etc.; so the preparation method is suitable for industrial large-scale application.

Description

technical field [0001] The invention belongs to the technical field of ionic liquid catalysis, and more specifically relates to a phthalazinone derivative, a preparation method of the derivative and a catalyst for preparation thereof. Background technique [0002] Phthalazinone compounds are a class of six-membered nitrogen-containing heterocyclic rings with good biological activity, which occupy an important position in the research and development of medicine and pesticides. In terms of pesticides, pesticides related to phthalazinone compounds are widely used, such as insecticides, herbicides, plant growth regulators, fungicides, etc.; in terms of medicine, phthalazinone compounds can be used as cyclooxygenase inhibitors , calcium sensitizers and phosphodiesterase inhibitors, etc., and can be used for the treatment of related diseases. [0003] Among them, the multi-component synthesis method is the most important method for the synthesis of phthalazinone derivatives. It ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D487/04B01J31/02
CPCB01J31/0271B01J31/0285C07D487/04
Inventor 沈智培卢华沈建忠
Owner 东港智科产业园有限公司
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