Tert-Butylamine → N-tert-butyl-4-(difluoromethyl)pyridin-2-amine

HRID 1057035ノート

反応式

HRID 1057035 の反応式
[F:1][CH:2]([F:10])[C:3]1[CH:8]=[CH:7][N+:6]([O-])=[CH:5][CH:4]=1.F[P-](F)(F)(F)(F)F.Br[P+](N1CCCC1)(N1CCCC1)N1CCCC1.C(N(CC)CC)C.[C:42]([NH2:46])([CH3:45])([CH3:44])[CH3:43]>ClCCCl.C(Cl)Cl>[C:42]([NH:46][C:7]1[CH:8]=[C:3]([CH:2]([F:10])[F:1])[CH:4]=[CH:5][N:6]=1)([CH3:45])([CH3:44])[CH3:43]

参加物

7

反応物 4

HCID 6385Tert-ButylamineHCID 8471TriethylamineHCID 2733179PyBroPHCID 90015270Pyridine, 4-(difluoromethyl)-, 1-oxide

生成物 1

HCID 90015299N-tert-butyl-4-(difluoromethyl)pyridin-2-amine収率 65%

試薬・触媒・溶媒 2

HCID 111,2-Dichloroethane溶媒HCID 6344Dichloromethane溶媒

反応条件

温度
100 °C

実験手順

A suspension of 4-difluoromethyl-pyridine-N-oxide (4.95 g, 34.1 mmol), bromo-tris-pyrrolidino-phosphonium hexafluorophosphate (20.7 g, 44.3 mmol), triethylamine (15.6 mL, 111 mmol), and anhydrous tert-butylamine (4.6 mL, 43 mmol) in DCE (100 mL, 0.33 M) was sealed in pressure tube and stirred at 100° C. for 3.5 hr. After cooling to rt, the mixture was diluted with CH2Cl2 and washed with sat. aq. NaHCO3. The organics were dried over MgSO4 and following concentration, the reaction residue was purified by flash column chromatography (100:0-80:20 heptanes/EtOAc) to afford N-tert-butyl-4-(difluoromethyl)pyridin-2-amine as a yellow liquid (4.43 g, 65%); 1H NMR (400 MHz, CDCl3) δ 8.15 (d, J=5.2 Hz, 1H), 6.65-6.28 (m, 3H), 4.62 (br s, 1H), 1.44 (s, 9H).

後処理

  1. customwas sealed in pressure tube
  2. temperatureAfter cooling to rt
  3. washwashed with sat. aq. NaHCO3
  4. dry with materialThe organics were dried over MgSO4
  5. concentrationconcentration
  6. customthe reaction residue was purified by flash column chromatography (100:0-80:20 heptanes/EtOAc)

出典と根拠

ORDレコード
ord-a2a0f222d2ad4652b9f30c5e94e21303
出典データセット
uspto-grants-2016_07
特許番号
US09399636B2

反応ノート

読み込み中…