Potassium Acetate → (7-Oxo-1-phenyl-1,7-dihydropyrazolo[1,5-a]pyrimidin-5-yl)methyl acetate

HRID 1154535ノート

反応式

HRID 1154535 の反応式
Cl[CH2:2][C:3]1[N:4]=[C:5]2[CH:12]=[CH:11][N:10]([C:13]3[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=3)[N:6]2[C:7](=[O:9])[CH:8]=1.[C:19]([O-:22])(=[O:21])[CH3:20].[K+]>CN(C)C=O>[C:19]([O:22][CH2:2][C:3]1[N:4]=[C:5]2[CH:12]=[CH:11][N:10]([C:13]3[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=3)[N:6]2[C:7](=[O:9])[CH:8]=1)(=[O:21])[CH3:20]

参加物

4

反応物 2

HCID 517044Potassium AcetateHCID 132320785-(Chloromethyl)-1-phenylpyrazolo[1,5-a]pyrimidin-7(1H)-one

生成物 1

HCID 13232097(7-Oxo-1-phenyl-1,7-dihydropyrazolo[1,5-a]pyrimidin-5-yl)methyl acetate

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

実験手順

5-chloromethyl-1-phenyl-1H,7H-pyrazolo[1,5-a]pyrimidine-7-one (5.2 g), prepared according to Example 1, was dissolved in dimethylformamide (30 ml) and reacted with anhydrous potassium acetate (4 g) under stirring at room temperature for 20 hours. After dilution with ice water the precipitate was filtered and washed with water to give 5-acetoxymethyl-1-phenyl-1H,7H-pyrazolo[1,5-a]pyrimidine-7-one, m.p. 172°-175° C., (4.9 g) which was hydrolized by treatment with 8% HCl (50 ml) under stirring at 90° C. for 30 minutes. The reaction mixture was neutralized with 35% NaOH and the precipitate was filtered and washed with water to give 5-hydroxymethyl-1-phenyl-1H,7H-pyrazolo[1,5-a]pyrimidine-7-one, m.p. 241°-242° C., (4.1 g), which was reacted with dicyclohexylcarbodiimide (8 g) in benzene (60 ml) and dimethylsulphoxide (15 ml) in the presence of trifluoroacetic acid (0.6 ml) and pyridine (1 ml) under stirring at room temperature for 20 hours. After treatment with oxalic acid bihydrate (1.8 g) at room temperature, the precipitate of dicyclohexylurea was filtered off and the organic solution was evaporated in vacuo to dryness: the residue was purified over a SiO2 column using chloroform: ethyl acetate=95:5 as eluent. The 7-formyl-1-phenyl-1H,7H-pyrazolo[1,5-a]pyrimidine-7-one so obtained (2.5 g) was reacted with the ylide obtained by treatment of (3-pyridyl)-methyl-triphenylphosphonium chloride (4.2 g) with potassium tert-butoxide (1.25 g) in dimethylsulphoxide (20 ml) at room temperature for 30 minutes. After dilution with ice water the precipitate was filtered and washed with water: crystallization from isopropyl alcohol gave 2.05 g of 1-phenyl-5-trans-[2-(3-pyridyl)ethenyl]-1H,7H-pyrazolo[1,5-a]pyrimidine-7-one, m.p. 221°-224° C.

後処理

  1. filtrationAfter dilution with ice water the precipitate was filtered
  2. washwashed with water

出典と根拠

ORDレコード
ord-9cbf763db3154e56b04436edaa953ddf
出典データセット
uspto-grants-1984_12
特許番号
US04490376

反応ノート

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