Synthesis method of 2-(1-hydroxy-4-keto-2,5-cyclohexadiene)-pyran-4-ketone

A technology of cyclohexadiene and a synthesis method, which is applied in the field of pharmaceutical synthesis, can solve the problems of high price of 4-ethynyl anisole, difficult operation and danger, many side reactions of cyclization, etc., and achieves cheap raw materials, equipment and reaction. Low-condition, low-cost effect

Active Publication Date: 2016-11-09
WUCHANG UNIV OF TECH
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  • Abstract
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Problems solved by technology

But this synthesis method has the following disadvantages: 1) the 4-ethynyl anisole used in the synthesis is expensive and difficult to buy; 2) the ring closure and ring opening of the isoxazole ring are difficult to operate, and the yield is low, such as isoxazole The ring opening of oxazole compounds with Mo(CO)6 requires the use of toxic and volatile Mo(CO)6. The experiment is not easy to operate and has certain risks, and has little production value; 3) Butene-1-one compounds are There are many cyclization side reactions under the conditions, and it is difficult to purify

Method used

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  • Synthesis method of 2-(1-hydroxy-4-keto-2,5-cyclohexadiene)-pyran-4-ketone
  • Synthesis method of 2-(1-hydroxy-4-keto-2,5-cyclohexadiene)-pyran-4-ketone
  • Synthesis method of 2-(1-hydroxy-4-keto-2,5-cyclohexadiene)-pyran-4-ketone

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Embodiment 1

[0028] A kind of synthetic method of 2-(1-hydroxyl-4-ketone-2,5-cyclohexadiene)-pyran-4-one, its step is:

[0029] 1) Synthesis of 1-(4-methoxyphenyl)-1-trimethylsiloxyethylene:

[0030] in N 2 Under protection, 10g (69.59mmol) of p-methoxyacetophenone and 16.85g (146.5mmol) of triethylamine were dissolved in 200ml of acetonitrile, and slowly added dropwise to the above mixed solution (dropping was completed within 15min) 15.92g ( 146.5mmol) trimethylchlorosilane, stirring and reacting at room temperature for 3h, after the completion of the reaction, stop N 2 protection, slowly add 150mL saturated NH 4 The Cl solution was extracted three times with 50 ml of n-hexane. After the extraction was completed, the obtained organic phase was dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated and dried to obtain 12.7 g of a brown oily liquid with a yield of 86.0%. TLC: Rf=0.6 (petroleum ether / ethyl acetate=10 / 1). The crude product obtained by this treatm...

Embodiment 2

[0049] A kind of synthetic method of 2-(1-hydroxyl-4-ketone-2,5-cyclohexadiene)-pyran-4-one, its step is:

[0050] 1) Synthesis of 1-(4-methoxyphenyl)-1-trimethylsiloxyethylene:

[0051] in N 2 Under protection, 17.7g (175mmol) of diisopropylamine was dissolved in anhydrous tetrahydrofuran, and the temperature was lowered to -45~-40°C, and then 76ml of 2.2M n-butyllithium was slowly added dropwise, and the reaction was carried out at this temperature for 20~30min. Then naturally raise the temperature to room temperature and react for 1.5~2h. After the reaction is completed, cool down to -45~-40°C, slowly add 10g (66.59mmol) p-methoxyacetophenone, stir for 10min, then slowly add 14.5g (133.2 mmol) trimethylchlorosilane, stirring reaction at room temperature for 3h, after the completion of the reaction, stop N 2 protection, slowly add 220mL saturated NH 4 The Cl solution was extracted three times with 60 ml of n-hexane. After the extraction was completed, the obtained organic...

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Abstract

The invention discloses a synthesis method of 2-(1-hydroxy-4-keto-2,5-cyclohexadiene)-pyran-4-ketone. The method comprises the steps that 1, on the condition of nitrogen protection and alkali existence, methoxy acetophenone is subjected to siloxane protection under the room temperature, and 1-(4-methoxy phenyl)-1-trimethyl siloxyethylene is obtained; 2, on the condition of nitrogen protection and mild acidity, 1-(4-methoxy phenyl)-1-trimethyl siloxyethylene and oxalyl chloride are subjected to a condensation reaction under the temperature of 0-5 DEG C, and 5-(4-methoxyl phenyl)-2, 3-dihydrofuran-2, 3-diketone is obtained; 3, 5-(4-methoxyl phenyl)-2, 3-dihydrofuran-2, 3-diketone and vinyl ethyl ether are subjected to reflux conditions to obtain 2-(4-methoxyl phenyl)-4H-pyrane-4-ketone; 4, under the nitrogen protection, demethylating is performed on the 2-(4-methoxyl phenyl)-4H-pyrane-4-ketone to obtain 2-(4-hydroxyl phenyl)-4H-pyrane-4-ketone; 5, under the room temperature, the 2-(4-hydroxyl phenyl)-4H-pyrane-4-ketone is subjected to a reaction under the effect of an oxidizing agent to obtain 2-(1-hydroxy-4-keto-2,5-cyclohexadiene)-pyran-4-ketone. The method is easy to implement, raw materials are easy to obtain, and the yield is high.

Description

technical field [0001] The invention relates to the technical field of medicine synthesis, in particular to a synthesis method of 2-(1-hydroxy-4-ketone-2,5-cyclohexadiene)-pyran-4-one. Background technique [0002] 2-(1-Hydroxy-4-keto-2,5-cyclohexadiene)-pyran-4-one has α, β-unsaturated ketone structure, the compound is effective for human gynecological tumors, prostate tumors, digestive system tumors And blood system tumors have a significant inhibitory effect without affecting the normal hematopoietic system and immune system. In addition, the compound can effectively inhibit tumor growth in H22 tumor-bearing mice, but has no effect on peripheral blood leukocytes, the ratio of peripheral blood granulocytes to lymphocytes, thymus index, and spleen index. [See also: Nguyen Kim Lan, et al. An anti-tumor compound and its preparation method and application, CN201110081818.7, 2011.04.01] [0003] The existing method for synthesizing 2-(1-hydroxyl-4-ketone-2,5-cyclohexadiene)-...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D309/38
CPCC07D309/38
Inventor 王小华阮金兰刘阳
Owner WUCHANG UNIV OF TECH
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