Acetic Acid → 4-Bromo-2-fluoro-1,1'-biphenyl

HRID 326026

反応式

HRID 326026 の反応式
[Br:1][C:2]1[CH:8]=[CH:7][C:5](N)=[C:4]([F:9])[CH:3]=1.[C:10](O)(=O)[CH3:11].N([O-])=O.[Na+].Cl>C1C=CC=CC=1.[Fe].CO.O>[Br:1][C:2]1[CH:8]=[CH:7][C:5]([C:11]2[CH:10]=[CH:4][CH:3]=[CH:2][CH:8]=2)=[C:4]([F:9])[CH:3]=1

参加物

9

反応物 4

HCID 176Acetic AcidHCID 313Hydrochloric AcidHCID 1230504-Bromo-2-fluoroanilineHCID 23668193Sodium Nitrite

生成物 1

HCID 5210634-Bromo-2-fluoro-1,1'-biphenyl収率 102.9%

試薬・触媒・溶媒 4

HCID 23925Iron触媒HCID 241Benzene溶媒2 回HCID 887Methanol溶媒HCID 962Water溶媒

反応条件

温度
65 °C

実験手順

A solution of 96 grams (0.50 mole) of crude 4-bromo-2-fluoroaniline and 60.0 grams (1.0 mole) of glacial acetic acid in 100 ml of benzene is added dropwise over 7 hours to a mixture of 69.0 grams (1.0 mole) of sodium nitrite, 69 ml water, and 700 ml of benzene kept at 65° C. The mixture is then allowed to stir at 65° C. overnight (12 hours) under a nitrogen atmosphere. The cooled mixture is washed twice with 400 ml of 1 N hydrochloric acid, then heated under reflux overnight (13 hours) with 20 grams (0.36 mole) of iron powder, 250 ml of methanol, and 150 ml (1.8 moles) of concentrated hydrochloric acid. The resultant solution is cooled and the benzene layer is washed with 490 ml of water, and evaporated at 40° C./40 mm Hg. The resultant dark oil is distilled at 10 mm Hg pressure to obtain 64.6 grams (51.5%) of 4-bromo-2-fluorobiphenyl as the entire distillate of boiling point mostly ~132~141° C./8 mm. The product crystalizes on seeding.

後処理

  1. customkept at 65° C
  2. washThe cooled mixture is washed twice with 400 ml of 1 N hydrochloric acid
  3. temperatureheated
  4. washthe benzene layer is washed with 490 ml of water
  5. customevaporated at 40° C./40 mm Hg
  6. distillationThe resultant dark oil is distilled at 10 mm Hg pressure

出典と根拠

ORDレコード
ord-83cff94e6f00477887f5b620ade91594
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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