Substituted dihydrobenzofuran-piperidine-methanone derivatives, their preparation and use
A technology of substituents and drugs, applied in the field of dihydrobenzofuran-piperidine-methanone derivatives, can solve the problems of few Tankyrase small molecule inhibitors and the like
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Embodiment 1
[0080] 2-[[3-[4-(2,3-dihydrobenzofuran-5-carbonyl)-1-piperidinyl]-2-oxo-pyrrolidin-1-yl]methyl]-3, 5,7,8-Tetrahydropyrano[4,3-d]pyrimidin-4-one (Compound 1)
[0081] 2-[[3-[4-(2,3-dihydrobenzofuran-5-carbonyl)-1-piperidyl]-2-oxo-pyrrolidin-1-yl]methyl]-3,5,7,8-tetrahydropyrano[4 ,3-d]pyrimidin-4-one
[0082]
[0083] The first step: tert-butyl 4-methoxy(methyl)carbamoyl)piperidine-1-carboxylate (1B)
[0084] tert-butyl 4-(methoxy(methyl)carbamoyl)piperidine-1-carboxylate
[0085]
[0086] Dissolve N,N'-carbonyldiimidazole (21.0g, 0.13mol) in anhydrous dichloromethane (200mL), add dropwise 1-tert-butoxycarbonylpiperidine-4-carboxylic acid (1A) (23.0g, 0.10 mmol) in anhydrous dichloromethane (100 mL), stirred for 30 minutes after dropping, added dimethylhydroxylamine hydrochloride (12.7 g, 0.13 mol) in batches, and reacted at room temperature for 3 hours. Add citric acid solution (wt=10%, 250mL) to the reaction solution, separate the layers, wash the organic phase with...
Embodiment 2
[0119] 2-[[3-[4-(2,3-dihydrobenzofuran-5-carbonyl)-1-piperidinyl]-2-oxo-pyrrolidin-1-yl]methyl]-3H- Cyclohepta[d]imidazol-4-one (Compound 2)
[0120] 2-[[3-[4-(2,3-dihydrobenzofuran-5-carbonyl)-1-piperidyl]-2-oxo-pyrrolidin-1-yl]meth yl]-3H-cyclohepta[d]imidazol-4- one
[0121]
[0122]
[0123] first step:
[0124] 2-[3-[4-(2,3-Dihydrobenzofuran-5-carbonyl)-1-piperidinyl]-2-oxo-pyrrolidin-1-yl]acetonitrile (2B)
[0125] 2-[3-[4-(2,3-dihydrobenzofuran-5-carbonyl)-1-piperidyl]-2-oxo-pyrrolidin-1-yl]acetonit rile
[0126]
[0127] 3-4-(2,3-Dihydrobenzofuran-5-carbonyl)piperidin-1-yl)pyrrolidin-2-one (1G) (0.53 g, 1.68 mmol) was dissolved in dry THF (10 mL) 2-bromoacetonitrile (0.61g, 5.04mmol) was added, cooled to 0°C under nitrogen protection, sodium hydride (0.12g, 5.04mol) was added to the reaction solution, and reacted at 0°C for 30 minutes. Add water (10 mL) dropwise to quench the reaction, extract with dichloromethane (20 mL×2), combine the organic layers, wa...
Embodiment 3
[0145] 2-[[3-[4-(6-fluoro-2,3-dihydrobenzofuran-7-carbonyl)-1-piperidinyl]-2-oxo-pyrrolidin-1-yl]methyl ]-3,5,7,8-tetrahydropyrano[4,3-d]pyrimidin-4-one (Compound 3)
[0146] 2-[[3-[4-(6-fluoro-2,3-dihydrobenzofuran-7-carbonyl)-1-piperidyl]-2-oxo-pyrrolidin-1-yl]methyl]-3,5,7,8 -tetrahydropyrano[4,3-d]pyrimidin-4-one
[0147]
[0148] The first step: 5-bromo-6-fluoro-2,3-dihydrobenzofuran (3B)
[0149] 5-bromo-6-fluoro-2,3-dihydrobenzofuran
[0150]
[0151] Add 48% hydrobromic acid solution (160 mL) to 6-fluoro-2,3-dihydrobenzofuran-5-amine (3A) (10.0 g, 65.30 mmol) at room temperature, and stir to dissolve. After cooling to 0° C., an aqueous solution (160 mL) of sodium nitrite (9.79 g, 142 mmol) was slowly added dropwise over 1 hour. Raise the temperature to room temperature and stir for 30 minutes, then cool to 0°C again, add cuprous bromide (14.20 g, 98.99 mmol) in batches, react at room temperature for 40 minutes after the addition, and heat to 140°C for 1.5 hours...
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