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

HRID 1057035노트

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HRID 1057035 반응식
[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]

참가 물질

7

반응물 4

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

생성물 1

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

시약·촉매·용매 2

HCID 111,2-Dichloroethane용매HCID 6344Dichloromethane용매

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온도
100 °C

실험 절차

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).

후처리

  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)

출처 및 근거

ORD 기록
ord-a2a0f222d2ad4652b9f30c5e94e21303
출처 데이터셋
uspto-grants-2016_07
특허 번호
US09399636B2

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