2-(2-hydroxy - substituted phenethyl sulfenyl]-3h-pyrimidin-4-ketone compounds and synthesis method and application thereof
A technology of ketone compounds and phenethyl, which is applied in the field of 2--3H-pyrimidin-4-one compounds and their synthesis, can solve the problems of unsatisfactory bioavailability and poor water solubility, and achieve convenient synthesis and obvious inhibition The effect of action
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Embodiment 1
[0029] The preparation of embodiment one β-keto ester (3)
[0030] Put 0.1 mol of substituted diethyl malonate (2) (diethyl methyl malonate, diethyl ethyl malonate) in 150 mL of absolute ethanol, add 0.1 mol of KOH in ethanol, Stir at room temperature for 12 hours, evaporate the solvent under reduced pressure, wash twice with ether or ethyl acetate, and evaporate the solvent again under reduced pressure to obtain monopotassium substituted diethyl malonate, which is directly used in the next reaction.
[0031] Put 0.1 mol of monopotassium substituted diethyl malonate in 150 mL of anhydrous acetonitrile, and add 0.18 mol of anhydrous MgCl in sequence 2 , 0.15mol Et 3 N, stirred at room temperature for 2 hours; 0.048mol of substituted phenylacetic acid / cyclohexylacetic acid (1) was placed in 100mL of anhydrous acetonitrile, and 0.05mol of N,N-carbonyldiimidazole was added batch by batch, reacted for one hour, and then Add the reaction mixture to substituted diethyl malonate mon...
Embodiment 2
[0032] Example 2 Preparation of 5-alkyl-6-(substituted benzyl / cyclohexylmethyl)-2-thio-3H-pyrimidin-4-one (4)
[0033]In a dry reaction flask, add 10 g (0.43 mol) of sodium metal in 300 mL of absolute ethanol in batches, and after the sodium is dissolved and cooled, add 24 g (0.315 mol) of thiourea at one time, and then dropwise add β-keto ester ( 3) 20 mL of ethanol solution, the mixture was heated to reflux for 5-7 hours, TLC traced to the β-keto ester raw material point disappeared, then stopped heating, cooled, evaporated the solvent under reduced pressure, dissolved the residue in 300 mL of water, and used concentrated Adjust the pH value to about 6 with hydrochloric acid, a large amount of white precipitates are produced, filter with suction, wash the filter cake with water, and dry to obtain 5-alkyl-6-(substituted benzyl / cyclohexylmethyl)-2-sulfanyl-3H- Pyrimidin-4-one (4) can be directly used in the next step of target compound synthesis without purification.
Embodiment 3
[0034] Example 3 Preparation of 2-[(substituted phenyl)carbonylmethylthio]-6-substituted benzyl / cyclohexylmethyl-5-alkyl-3H-pyrimidin-4-one compound (5)
[0035] 2mmol of 6-(substituted benzyl / cyclohexylmethyl)-5-alkyl-2-sulfanyl-3H-pyrimidin-4-one (4) and 2mmol of K 2 CO 3 Place in a reaction bottle, add 15 mL of anhydrous N, N-dimethylformamide (DMF), stir at room temperature for 30 min, add 2.2 mmol of each α-bromoacetophenone, stir at room temperature for 12-16 hours, TLC Track until the raw material point disappears, stop the reaction, add 100mL of ice water, a white precipitate is formed, filter with suction, recrystallize with ethanol, part of it needs to be purified by column chromatography to obtain pure product.
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