Triethylamine → 2-Fluoro-4-(trifluoromethyl)aniline

HRID 919166ノート

反応式

HRID 919166 の反応式
[F:1][C:2]1[CH:10]=[C:9]([C:11]([F:14])([F:13])[F:12])[CH:8]=[CH:7][C:3]=1C(O)=O.C([N:17](CC)CC)C.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=O)C=CC=CC=1>CC(O)(C)C.Cl[Cu]>[F:1][C:2]1[CH:10]=[C:9]([C:11]([F:14])([F:13])[F:12])[CH:8]=[CH:7][C:3]=1[NH2:17]

参加物

6

反応物 3

HCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 5180032-Fluoro-4-(trifluoromethyl)benzoic acid

生成物 1

HCID 27376742-Fluoro-4-(trifluoromethyl)aniline収率 58%

試薬・触媒・溶媒 2

HCID 62652Cuprous chloride触媒HCID 6386tert-Butanol溶媒

反応条件

温度
50 °C

実験手順

To the solution of 2-fluoro-4-(trifluoromethyl)benzoic acid (1 kg, 4.805 mol, 1.00 equivalent “eq.”) and CuCl (14.26 g, 0.144 mol, 0.03 eq.) in t-BuOH (11.7 L) was added triethylamine (TEA, 533.8 g, 5.286 mol, 1.10 eq.) dropwise at room temperature (rt). Then the solution was heated to 50° C. and diphenylphosphoryl azide (DPPA, 1393 g, 5.045 mol, 1.05 eq.) was added dropwise to the solution at 50-60° C. After heating at 80˜85° C. overnight the solution was concentrated under vacuum. The residual was dissolved in H2O and filtered. The filtrate was extracted with ethyl acetate. The organic layers was dried with Na2SO4, filtered and concentrated under vacuum. The residual was dissolved in tert-Butyl methyl ether (TBME) and HCl (gas) was bubbled in for 2 hours. The filtrate was collected and dissolved in water and basified with 2 M NaOH. The solution was extracted with TBME. The organic layers were dried and concentrated under vacuum to give 2-fluoro-4-(trifluoromethyl) aniline (498 g, 58%) as a red oil.

後処理

  1. temperatureAfter heating at 80˜85° C. overnight the solution
  2. concentrationwas concentrated under vacuum
  3. dissolutionThe residual was dissolved in H2O
  4. filtrationfiltered
  5. extractionThe filtrate was extracted with ethyl acetate
  6. dry with materialThe organic layers was dried with Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated under vacuum
  9. dissolutionThe residual was dissolved in tert-Butyl methyl ether (TBME)
  10. customHCl (gas) was bubbled in for 2 hours
  11. customThe filtrate was collected
  12. dissolutiondissolved in water and basified with 2 M NaOH
  13. extractionThe solution was extracted with TBME
  14. customThe organic layers were dried
  15. concentrationconcentrated under vacuum

出典と根拠

ORDレコード
ord-d935a6917e6944fb8540c86ba1aaf421
出典データセット
uspto-grants-2016_03
特許番号
US09273007B2

反応ノート

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