Water → 4-Chloro-5-[[1-(2,4-dichlorophenyl)-2-(1H-imidazol-1-yl)ethoxy]methyl]-1-ethyl-3-methyl-1H-pyrazolo[3,4-b]pyridine, hydrochloride

HRID 237112

反応式

HRID 237112 の反応式
[OH-].[Na+].O.[Cl:4][C:5]1[CH:10]=[C:9]([Cl:11])[CH:8]=[CH:7][C:6]=1[CH:12]([OH:19])[CH2:13][N:14]1[CH:18]=[CH:17][N:16]=[CH:15]1.[Cl:20][C:21]1[C:26]([CH2:27]Cl)=[CH:25][N:24]=[C:23]2[N:29]([CH2:33][CH3:34])[N:30]=[C:31]([CH3:32])[C:22]=12>[Cl-].C([N+](C)(C)C)C1C=CC=CC=1.O1CCCC1>[ClH:4].[Cl:20][C:21]1[C:26]([CH2:27][O:19][CH:12]([C:6]2[CH:7]=[CH:8][C:9]([Cl:11])=[CH:10][C:5]=2[Cl:4])[CH2:13][N:14]2[CH:18]=[CH:17][N:16]=[CH:15]2)=[CH:25][N:24]=[C:23]2[N:29]([CH2:33][CH3:34])[N:30]=[C:31]([CH3:32])[C:22]=12

参加物

7

反応物 4

HCID 962WaterHCID 14798Sodium HydroxideHCID 32238(+-)-alpha-(2,4-Dichlorophenyl)-1H-imidazole-1-ethanolHCID 21315234HCID 21315234、化合物

生成物 1

HCID 1317115234-Chloro-5-[[1-(2,4-dichlorophenyl)-2-(1H-imidazol-1-yl)ethoxy]methyl]-1-ethyl-3-methyl-1H-pyrazolo[3,4-b]pyridine, hydrochloride

試薬・触媒・溶媒 2

HCID 5963Benzyltrimethylammonium chloride触媒HCID 8028Tetrahydrofuran溶媒2 回

実験手順

In a three necked flask (250 ml.), fitted with a stirrer, reflux condenser and gas inlet tube are introduced 24.4 g. of sodium hydroxide (0.61 mol.) and 23 ml. of water. While passing nitrogen through the flask, the solution is cooled to 45° and then are added 6.43 g. of 1-(2,4-dichlorophenyl)-2-(1H-imidazol-1-yl)ethanol (0.025 mol.), [prepared according to J. Med. Chem., Vol. 12, 784 (1969)], 0.43 g. of benzyltrimethylammonium chloride and 25 ml. of tetrahydrofuran. To the mixture, which is warmed to 50°, a solution of 6.1 g. of 4-chloro-5-chloromethyl-1-ethyl-3-methyl-1H-pyrazolo[3,4-b]-pyridine (0.025 mol.) in 10 ml. of tetrahydrofuran is added from a prewarmed dropping funnel within 3 minutes. The mixture is stirred vigorously for 3 hours at 60° using a water bath. Then the warm mixture is transferred into a separating funnel, the lower aqueous sodium hydroxide is extracted with 10 ml. of tetrahydrofuran. The combined tetrahydrofuran layers are dried by means of sodium sulfate and after the solvent has been removed the residual oil is extracted with ether, treated with charcoal and filtered. To the solution of free base are added dropwise 5.9 ml. of ethereal hydrochloric acid (30.9%). The precipitated 4-chloro-5[[1-(2,4-dichlorophenyl)-2-(1H-imidazol-1-yl)ethoxy]methyl]- 1-ethyl-3-methyl-1H-pyrazolo[3,4-b]pyridine, hydrochloride is filtered off, dried in the vacuum desiccator and recrystallized from acetonitrile, m.p. 200°-201°; yield 5.67 g. (45%).

後処理

  1. customIn a three necked flask (250 ml.), fitted with a stirrer
  2. temperaturereflux condenser and gas inlet tube
  3. additionare introduced 24.4 g
  4. temperaturethe solution is cooled to 45°
  5. additionare added 6.43 g
  6. temperatureTo the mixture, which is warmed to 50°
  7. customwithin 3 minutes
  8. customThen the warm mixture is transferred into a separating funnel
  9. extractionthe lower aqueous sodium hydroxide is extracted with 10 ml
  10. dry with materialThe combined tetrahydrofuran layers are dried by means of sodium sulfate
  11. customafter the solvent has been removed the residual oil
  12. extractionis extracted with ether
  13. additiontreated with charcoal
  14. filtrationfiltered
  15. additionTo the solution of free base are added dropwise 5.9 ml
  16. filtrationThe precipitated 4-chloro-5[[1-(2,4-dichlorophenyl)-2-(1H-imidazol-1-yl)ethoxy]methyl]- 1-ethyl-3-methyl-1H-pyrazolo[3,4-b]pyridine, hydrochloride is filtered off
  17. customdried in the vacuum desiccator
  18. customrecrystallized from acetonitrile, m.p. 200°-201°

出典と根拠

ORDレコード
ord-2d8f9ce8f7e74557a5a675132fb1c625
出典データセット
uspto-grants-1979_06
特許番号
US04159380

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