2-Fluoroethyl bromide → 2-[2,4-dichloro-5-(1-methylethoxy)phenyl]-4-(2-fluoroethyl)-1,2,4-triazine-3,5(2H,4H)-dione

HRID 35426

反応式

HRID 35426 の反応式
[H-].[Na+].[Cl:3][C:4]1[CH:9]=[C:8]([Cl:10])[C:7]([O:11][CH:12]([CH3:14])[CH3:13])=[CH:6][C:5]=1[N:15]1[C:20](=[O:21])[NH:19][C:18](=[O:22])[CH:17]=[N:16]1.[OH-].[K+].Br[CH2:26][CH2:27][F:28]>O1CCCC1.[Br-].C([N+](CCCC)(CCCC)CCCC)CCC>[Cl:3][C:4]1[CH:9]=[C:8]([Cl:10])[C:7]([O:11][CH:12]([CH3:14])[CH3:13])=[CH:6][C:5]=1[N:15]1[C:20](=[O:21])[N:19]([CH2:26][CH2:27][F:28])[C:18](=[O:22])[CH:17]=[N:16]1

参加物

7

反応物 4

HCID 129822-Fluoroethyl bromideHCID 14797Potassium HydroxideHCID 24758Sodium hydrideHCID 142769712-[2,4-dichloro-5-(1-methylethoxy)phenyl]-1,2,4-triazine-3,5(2H,4H)-dione2 回

生成物 1

HCID 147478322-[2,4-dichloro-5-(1-methylethoxy)phenyl]-4-(2-fluoroethyl)-1,2,4-triazine-3,5(2H,4H)-dione収率 36.8%

試薬・触媒・溶媒 2

HCID 74236Tetrabutylammonium Bromide触媒HCID 8028Tetrahydrofuran溶媒3 回

実験手順

To a stirred mixture of 0.084 g (0.0035 mole) of sodium hydride in 20 mL of tetrahydrofuran was added a solution of 1.0 g (0.003 mole) of 2-[2,4-dichloro-5-(1-methylethoxy)phenyl]-1,2,4-triazine-3,5(2H,4H)-dione (Compound 51, Example III, Step F) in 5 mL of tetrahydrofuran. The resulting mixture was stirred at room temperature for one hour. Tetrabutylammonium bromide (0.5 g, 0.002 mole) and potassium hydroxide (0.5 g, 0.009 mole) were added, and the mixture was heated at 60°-70° C. for approximately 1.5 hours. While maintaining the temperature at 60° C., a solution of 0.5 g (0.004 mole) of 1-bromo-2-fluoroethane in 5 mL of tetrahydrofuran was added. After complete addition, the mixture was allowed to cool to room temperature and was stirred for approximately 18 hours. The mixture was partitioned between dilute aqueous hydrochloric acid and ethyl acetate. The organic phase was dried over anhydrous magnesium sulfate and filtered. Evaporation of the filtrate under reduced pressure produced an oil. The oil was subjected to column chromatography on silica gel, eluting with ethyl acetate:n-heptane (1:1). Evaporation of the appropriate fractions provided a solid which was recrystallized from ethyl acetate:n-heptane to give 0.4 g of 2-[2,4-dichloro-5-(1-methylethoxy)phenyl]-4-(2-fluoroethyl)-1,2,4-triazine-3,5(2H,4H)-dione, Compound 26 in the tables.

後処理

  1. temperaturethe mixture was heated at 60°-70° C. for approximately 1.5 hours
  2. temperatureWhile maintaining the temperature at 60° C.
  3. additionAfter complete addition
  4. temperatureto cool to room temperature
  5. stirringwas stirred for approximately 18 hours
  6. customThe mixture was partitioned between dilute aqueous hydrochloric acid and ethyl acetate
  7. dry with materialThe organic phase was dried over anhydrous magnesium sulfate
  8. filtrationfiltered
  9. customEvaporation of the filtrate under reduced pressure
  10. customproduced an oil
  11. washeluting with ethyl acetate:n-heptane (1:1)
  12. customEvaporation of the appropriate fractions
  13. customprovided a solid which
  14. customwas recrystallized from ethyl acetate

出典と根拠

ORDレコード
ord-b65ea52150e7489fb2c37050e4be883a
出典データセット
uspto-grants-1988_08
特許番号
US04766233

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