A kind of environment-friendly preparation method of istradefylline
A technology of istradefylline and cyclization reaction, applied in the field of medicinal chemistry, can solve the problems of unenvironmental protection in production process, unstable use, large amount of waste water, etc., and achieve the effects of low cost, few raw materials and few side reactions
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Embodiment 1
[0071] Embodiment 1: The preparation of istradefylline (I) is prepared according to route 1
[0072] Step (a): Methyl 2-(N-methyl-N-(E)-3,4-dimethoxyphenylacryloyl)aminocyanoacetate (IV 1 ) preparation
[0073] In a 500 ml four-necked flask, add 250 g of dichloromethane, 25.5 g (0.2 moles) of methyl 2-methylaminocyanoacetate (II 1 ), 30 grams of triethylamine, cooling, cooling to 5-10 ° C, dropwise adding 45.5 grams (0.2 moles) of (E)-3,4-dimethoxyphenylacryloyl chloride (Ⅲ) and 100 grams of dichloromethane The mixed solution was dropped, reacted at 30-35°C for 5 hours, cooled to room temperature, filtered, the filter cake was washed once with 30 g of dichloromethane, the dichloromethane phase was combined, the solvent was recovered by distillation, and dried to obtain 60.7 g of light yellow solid 2 -Methyl (N-methyl-N-(E)-3,4-dimethoxyphenylacryloyl)aminocyanoacetate, liquid phase purity 99.9%, yield 95.5%.
[0074] Preparation of istradefylline (Ⅰ)
[0075] In a 500 ml f...
Embodiment 2
[0078] Embodiment 2: The preparation of istradefylline (I) is prepared according to route 1
[0079] Step (a): ethyl 2-(N-methyl-N-(E)-3,4-dimethoxyphenylacryloyl)aminocyanoacetate (IV 2 ) preparation
[0080] In a 500 ml four-neck flask, add 250 g of 1,2-dichloroethane, 28.5 g (0.2 moles) of ethyl 2-methylaminocyanoacetate (II 2 ), 30 grams of triethylamine, cooled, cooled to 15-20 ° C, dropwise added 45.5 grams (0.2 moles) of (E)-3,4-dimethoxyphenylacryloyl chloride (Ⅲ) and 100 grams of 1,2- The mixed solution of dichloroethane, dropwise, react at 50-55°C for 3 hours, cool down to room temperature, filter, wash the filter cake once with 30 grams of 1,2-dichloroethane, combine the organic phases, recover the solvent by distillation, and dry , to obtain 62.2 grams of light yellow solid 2-(N-methyl-N-(E)-3,4-dimethoxyphenylacryloyl) ethyl aminocyanoacetate, liquid phase purity 99.9%, yield 93.2% .
[0081] Preparation of istradefylline (Ⅰ)
[0082] In a 500 ml four-necked ...
Embodiment 3
[0083] Embodiment 3: The preparation of istradefylline (I) is prepared according to route 2
[0084] Step (a): Preparation of 1,3-diethyl-5-methylamino-6-aminouracil (Ⅵ)
[0085] In a 500 ml four-neck flask equipped with a distillation system, add 200 g of 1,4-dioxane, 12.8 g (0.1 mole) of methyl 2-methylaminocyanoacetate (Ⅱ 1 ), 14.0 grams (0.12 moles) of 1,3-diethylurea, reacted at 100-105 ° C for 4 hours, and distilled off the methanol produced at the same time. React at 95°C for 3 hours, recover 1,4-dioxane by distillation under reduced pressure, add 50 g of isopropanol to the residue, heat to reflux for 1 hour, filter while hot, cool the filtrate to room temperature, crystallize, filter, and dry. 20.3 g of off-white solid 1,3-diethyl-5-methylamino-6-aminouracil was obtained, the liquid phase purity was 99.97%, and the yield was 95.8%.
[0086] Step (b): 1,3-diethyl-5-(N-methyl-N-(E)-3,4-dimethoxyphenylacryloyl)amino-6-aminouracil (V) preparation
[0087] Into a 500 ml...
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