Hydrogen Peroxide → 3-Bromo-2-ethyl-6-nitropyridine

HRID 1049245노트

반응식

HRID 1049245 반응식
OO.[Br:3][C:4]1[CH:5]=[CH:6][C:7]([NH2:12])=[N:8][C:9]=1[CH2:10][CH3:11].C(Cl)Cl.[OH-:16].[Na+].[OH:18]S(O)(=O)=O>>[Br:3][C:4]1[C:9]([CH2:10][CH3:11])=[N:8][C:7]([N+:12]([O-:18])=[O:16])=[CH:6][CH:5]=1

참가 물질

6

반응물 5

HCID 784Hydrogen PeroxideHCID 1118Sulfuric Acid2회HCID 6344DichloromethaneHCID 14798Sodium HydroxideHCID 217103385-Bromo-6-ethylpyridin-2-amine

생성물 1

HCID 904030533-Bromo-2-ethyl-6-nitropyridine수율 52%

실험 절차

A 0° C. solution of H2SO4 (11 mL, 10.83 mmol) was treated slowly with 30% hydrogen peroxide (5.5 mL, 9.42 mmol) in an open flask, stirred for 5 minutes, treated drop-wise with a solution of 5-bromo-6-ethylpyridin-2-amine (3.83 g, 19.05 mmol) in H2SO4 (11 mL) and stirred overnight as the cooling bath expired. The solution was poured into ice water, treated with DCM, cooled in an ice bath and treated slowly with 50% NaOH until pH˜9. The layers were separated, the aqueous layer extracted with DCM (1×) and the combined organics were washed with brine, dried over Na2SO4, concentrated to dryness and purified via silica gel chromatography (EtOAc/Hex) to afford 3-bromo-2-ethyl-6-nitropyridine (2.31 g, 52%) as a yellow oil. 1H NMR (400 MHz, DMSO-d6): δ 8.43 (d, J=8.5 Hz, 1H), 8.04-8.03 (m, 1H), 2.96 (q, J=7.5 Hz, 2H), 1.24 (t, J=7.5 Hz, 3H); MS (ESI) m/z: 233.0 (M+H+).

후처리

  1. stirringstirred overnight as the cooling bath
  2. temperaturecooled in an ice bath
  3. customThe layers were separated
  4. extractionthe aqueous layer extracted with DCM (1×)
  5. washthe combined organics were washed with brine
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated to dryness
  8. custompurified via silica gel chromatography (EtOAc/Hex)

출처 및 근거

ORD 기록
ord-fbd30c202723479ca5fcdc0997e5b2df
출처 데이터셋
uspto-grants-2016_07
특허 번호
US09382228B2

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