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One-pot synthesis method for 4-aryl methylene-2,6-disubstituted-2,5-cyclohexadiene-1-one

A technology of aryl methylene and cyclohexadiene, which is applied in the fields of chemical instruments and methods, preparation of organic compounds, carbon-based compounds, etc., can solve the difficult operation of the format reaction, is difficult to obtain, and cannot meet the needs of the pharmaceutical field Questions such as requirements

Inactive Publication Date: 2016-03-23
PTG ADVANCED CATALYST CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] US3660505 mentions the use of Grignard reaction to reduce methyl quinone, and then oxidizes the product by potassium ferricyanide, but the Grignard reaction operation is difficult, the yield is low, and it is difficult to industrialize
US4032547 mentions the preparation of this product by the mixed oxidation method of persulfate and potassium ferricyanide, but the amount of waste water is relatively large
US4216158 mentions the preparation of this product with two-(3,5-disubstituent-4-hydroxyphenyl) sulfide and lead oxide as raw materials, but the raw materials are expensive and difficult to obtain
EP0744392 mentioned the method of synthesizing the product with benzaldehyde and substituted phenol, but the post-treatment is extremely cumbersome, and the content after column chromatography can only reach 90%, and the content can only reach 96% after finishing with extremely high vacuum. Meet the requirements of the pharmaceutical field

Method used

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  • One-pot synthesis method for 4-aryl methylene-2,6-disubstituted-2,5-cyclohexadiene-1-one
  • One-pot synthesis method for 4-aryl methylene-2,6-disubstituted-2,5-cyclohexadiene-1-one
  • One-pot synthesis method for 4-aryl methylene-2,6-disubstituted-2,5-cyclohexadiene-1-one

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0056] Add 242.8g (1.1768mol) of 2,6-di-tert-butylphenol, 128.4g (1.2099mol) of benzaldehyde, 29.2g of hexahydropyridine (84.0g will be added dropwise later, totaling 113.2g, 1.3294mol), toluene into a 1000ml three-necked flask 35ml, heat up and reflux to divide the water, add dropwise 84.0g of hexahydropyridine, after the addition is complete, then reflux to divide the water for 3h;

[0057] Then add acetic anhydride (1.43mol), 110-125 ℃ insulation reaction for 30min, add toluene, wash with water, wash with saturated saline, dry over anhydrous sodium sulfate, filter, desolvate under reduced pressure, mixed solvent (ethyl acetate: n-hexane volume ratio =3:1) recrystallized to obtain 314.2g of wet product, and dried to obtain 274.2g (yield: 79.1%).

[0058] This embodiment makes the product 1 HNMR picture as shown figure 2 As shown, the displacement values ​​(ppm) in the upper part of the figure are from left to right: 7.531, 7.526, 7.466, 7.455, 7.416, 7.405, 7.401, 7.395, ...

Embodiment 2

[0064] Add 60.7g (0.2942mol) of 2,6-di-tert-butylphenol, 32.1g (0.3025mol) of benzaldehyde, 7.3g of hexahydropyridine (21.0g will be added dropwise later, totaling 28.3g, 0.3324mol), toluene into a 250ml three-necked flask 9ml, heat up and reflux to divide the water, add dropwise 21.0g of hexahydropyridine, after the addition is complete, then reflux to divide the water for 3h;

[0065] Then add propionic anhydride (0.3573mol), keep the reaction at 110-125°C for 30min, add toluene, wash with water, wash with saturated brine, dry over anhydrous sodium sulfate, filter, precipitate under reduced pressure, ethyl acetate / n-hexane (3:1) The mixed solvent was recrystallized to obtain 80.8g of wet product, and dried to obtain 57.1g (yield: 65.9%). of the resulting product 1 HNMR chart and GC chart are similar to Example 1.

Embodiment 3

[0067] Add 20.8g (0.1008mol) of 2,6-di-tert-butylphenol into a 100ml three-necked flask, 11.0g (0.1036mol) of benzaldehyde, 2.5g of di-n-propylamine (9.0g will be added dropwise later, totaling 11.5g, 0.1138mol), toluene 3ml, heat up and reflux to divide the water, add 9.0g of di-n-propylamine dropwise, after the addition is completed, then reflux and divide the water for 3h;

[0068] Then add butyric anhydride (0.12mol), keep warm at 110-125°C for 30 minutes, add toluene, wash with water, wash with saturated brine, dry over anhydrous sodium sulfate, filter, and precipitate under reduced pressure, ethyl acetate / n-hexane (3:1) The mixed solvent was recrystallized to obtain 23.6g of wet product, and dried to obtain 20.8g (yield: 70.0%). of the resulting product 1 HNMR chart and GC chart are similar to Example 1.

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Abstract

The invention discloses a one-pot synthesis process for 4-aryl methylene-2,6-disubstituted-2,5-cyclohexadiene-1-one. The process comprises the following steps: using 2,6-disubstituted phenol and benzaldehyde as initial raw materials; in the presence of a solvent, adding secondary amine and carrying out reaction to generate Mannich base; and then adding anhydride to obtain the product 4-aryl methylene-2,6-disubstituted-2,5-cyclohexadiene-1-one. By adopting the method disclosed by the invention, the 4-aryl methylene-2,6-disubstituted-2,5-cyclohexadiene-1-one can be prepared under normal conditions, intermediates do not need to be separated and purified, the operation is safe, the energy resources are saved, and the process is suitable for large-scale production.

Description

technical field [0001] The present invention relates to a synthesis method of organic compounds, in particular to a novel method for one-pot synthesis of 4-aryl methylene-2,6-disubstituent-2,5-cyclohexadien-1-one method. Background technique [0002] 4-Arylmethylene-2,6-disubstituent-2,5-cyclohexadien-1-one acts as an enzyme inhibitor of cyclooxygenase and 5-lipoxygenase, which is widely used in cold, fever, It is mainly used in the treatment of various diseases such as inflammation, and it is mainly used in medicine and pesticides. [0003] US3660505 mentions the use of Grignard reaction to reduce methyl quinone and then oxidize it with potassium ferricyanide to obtain the product. However, the Grignard reaction is difficult to operate, the yield is low, and it is difficult to industrialize. US4032547 mentions that this product is prepared by the mixed oxidation method of persulfate and potassium ferricyanide, but the amount of waste water is relatively large. US4216158 ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C45/51C07C49/683
CPCC07C45/512C07C49/683C07C213/02C07C215/50C07D295/096
Inventor 王碧波高建勋
Owner PTG ADVANCED CATALYST CO LTD
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