Ammonium Chloride → 5-Bromo-4-(2,4-difluorophenoxy)-2-methylbenzenamine

HRID 909187ノート

反応式

HRID 909187 の反応式
[Br:1][C:2]1[CH:7]=[C:6]([N+:8]([O-])=O)[C:5]([CH3:11])=[CH:4][C:3]=1[O:12][C:13]1[CH:18]=[CH:17][C:16]([F:19])=[CH:15][C:14]=1[F:20].[NH4+].[Cl-]>C1COCC1.CO.[Zn]>[Br:1][C:2]1[C:3]([O:12][C:13]2[CH:18]=[CH:17][C:16]([F:19])=[CH:15][C:14]=2[F:20])=[CH:4][C:5]([CH3:11])=[C:6]([NH2:8])[CH:7]=1

参加物

6

反応物 2

HCID 25517Ammonium ChlorideHCID 574187591-Bromo-2-(2,4-difluorophenoxy)-4-methyl-5-nitrobenzene

生成物 1

HCID 574187605-Bromo-4-(2,4-difluorophenoxy)-2-methylbenzenamine収率 81%

試薬・触媒・溶媒 3

HCID 23994Zinc触媒HCID 887Methanol溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

1-Bromo-2-(2,4-difluoro-phenoxy)-4-methyl-5-nitro-benzene (87.0 g, 253 mmol) was dissolved in THF (300 mL) and diluted with MeOH (900 mL). Zinc dust (82.7 g, 1.26 mol) was added and 1 L of saturated NH4Cl was added slowly so that the reaction temperature never exceeded 42° C. The reaction was mechanically stirred vigorously for 16 hours. The reaction was filtered through Celite and the filter cake was washed with ethyl acetate. The filtrate was then concentrated with 1.2 L of saturated NH4OAc. When the THF/MeOH was removed, the solids were collected and washed with water. The solids were then stirred in 1 L water for 30 min, then collected via filtration and rinsed with water (1 L) in three portions. The resulting solid was dried under high vacuum for 48 hours to produce 64 g of the desired product (81% yield). MS (ESI+) m/z 314, 316 (M+1, Br pattern) detected; 1H NMR (400 mHz, CDCl3) δ 6.92 (m, 1H), 6.91 (s, 1H), 6.75 (m, 2H), 6.70 (s, 1H), 3.57 (br. s, 2H), 2.08 (s, 3H).

後処理

  1. filtrationThe reaction was filtered through Celite
  2. washthe filter cake was washed with ethyl acetate
  3. concentrationThe filtrate was then concentrated with 1.2 L of saturated NH4OAc
  4. customWhen the THF/MeOH was removed
  5. customthe solids were collected
  6. washwashed with water
  7. stirringThe solids were then stirred in 1 L water for 30 min
  8. filtrationcollected via filtration
  9. washrinsed with water (1 L) in three portions
  10. customThe resulting solid was dried under high vacuum for 48 hours

出典と根拠

ORDレコード
ord-61418bec99474a4a8ba866753998954a
出典データセット
uspto-grants-2011_09
特許番号
US08017641B2

反応ノート

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