Benzene → 4-Bromo-2-fluoro-1,1'-biphenyl

HRID 326027

反応式

HRID 326027 の反応式
N(OCCC(C)C)=O.[Br:9][C:10]1[CH:16]=[CH:15][C:13](N)=[C:12]([F:17])[CH:11]=1.[CH:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1>Cl.O.[Zn].[Fe]>[Br:9][C:10]1[CH:16]=[CH:15][C:13]([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)=[C:12]([F:17])[CH:11]=1

参加物

8

反応物 3

HCID 241Benzene2 回HCID 8053Isoamyl NitriteHCID 1230504-Bromo-2-fluoroaniline

生成物 1

HCID 5210634-Bromo-2-fluoro-1,1'-biphenyl

試薬・触媒・溶媒 4

HCID 23925Iron触媒HCID 23994Zinc触媒HCID 313Hydrochloric Acid溶媒HCID 962Water溶媒

実験手順

Solutions of 375 ml (325 g, 2.8 moles) of isoamyl nitrite, and of 378 grams (2.0 moles) of crude 4-bromo-2-fluoroaniline in 250 ml benzene are added separately and simultaneously dropwise over about 20 hours to 3500 ml of benzene vigorously stirred under a nitrogen atmosphere, and kept in a water bath at 65° C. The mixture is kept overnight at 65° C., then cooled, washed twice with 250 ml of water and evaporated. The dark oily residue is dissolved in 750 ml methanol and 450 ml concentrated hydrochloric acid, and treated with 138 grams (2.1 moles) of granular zinc, added in small portions over about 6 hours. In order to complete this "reductive upgrading", the solution is treated with 54 grams (1.0 mole) of fine iron filings over 0.5 hours. Within one hour the color of the mixture is visibly lighter. The solution is diluted with one liter of water and one liter of Skellysolve B hexanes, and the liquids are decanted from the remaining metals. The aqueous phase is extracted twice with one liter of Skellysolve B hexanes and the one liter of water, one liter of 1 N NaOH, and one liter of water. The solution is then passed through anhydrous sodium sulfate and evaporated to provide 389 grams of 4-bromo-2-fluoro-biphenyl.

後処理

  1. customkept in a water bath at 65° C
  2. temperaturecooled
  3. washwashed twice with 250 ml of water
  4. customevaporated
  5. dissolutionThe dark oily residue is dissolved in 750 ml methanol
  6. additionadded in small portions over about 6 hours
  7. waitWithin one hour the color of the mixture is visibly lighter
  8. customthe liquids are decanted from the remaining metals
  9. extractionThe aqueous phase is extracted twice with one liter of Skellysolve B hexanes
  10. customevaporated

出典と根拠

ORDレコード
ord-601a58a21c684548beb39da1256352bc
出典データセット
uspto-grants-1984_04
特許番号
US04443631

関連ノート

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