Hydrazinium, 1,1,1-trimethyl-, iodide (1:1) → 3-(3-Bromo-5-chlorophenoxy)-4-chloro-2-nitroaniline

HRID 505520

반응식

HRID 505520 반응식
CC(C)([O-])C.[K+].[I-].C[N+:9](C)(C)N.[Br:13][C:14]1[CH:15]=[C:16]([CH:28]=[C:29]([Cl:31])[CH:30]=1)[O:17][C:18]1[C:23]([N+:24]([O-:26])=[O:25])=[CH:22][CH:21]=[CH:20][C:19]=1[Cl:27]>CN(C=O)C.[Cu]Cl>[Br:13][C:14]1[CH:15]=[C:16]([CH:28]=[C:29]([Cl:31])[CH:30]=1)[O:17][C:18]1[C:23]([N+:24]([O-:26])=[O:25])=[C:22]([CH:21]=[CH:20][C:19]=1[Cl:27])[NH2:9]

참가 물질

6

반응물 3

HCID 18683Hydrazinium, 1,1,1-trimethyl-, iodide (1:1)HCID 23665647Potassium tert-butoxideHCID 56833647HCID 56833647, 화합물

생성물 1

HCID 568336493-(3-Bromo-5-chlorophenoxy)-4-chloro-2-nitroaniline

시약·촉매·용매 2

HCID 62652Cuprous chloride촉매HCID 6228Dimethylformamide용매2회

반응 조건

온도
-40 °C

실험 절차

To copper (I) chloride (5.45 mg, 0.055 mmol) and potassium tert-butoxide (247 mg, 2.204 mmol) suspended in DMF (3 mL) at 0° C. was added 1,1,1-trimethylhydrazinium iodide (139 mg, 0.689 mmol). This mixture was allowed to stir for several minutes at which point the mixture was cooled to −40° C. and 2-(3-bromo-5-chlorophenoxy)-1-chloro-3-nitrobenzene (200 mg, 0.551 mmol) as a solution in DMF (1 mL) was added dropwise. The reaction was maintained at −40° C. for 15 minutes and was then quenched at −40° C. with saturated aqueous ammonium chloride (10 mL). Water (10 mL) was added and the mixture was allowed to warm to room temperature. The mixture was extracted with ethyl acetate (2×50 mL). The combined organic fractions were washed with water (3×50 mL), dried (MgSO4), filtered and the solvent was evaporated under reduced pressure. The resulting residue was purified by automated column chromatography on silica gel (40 g) eluting with 0-25% EtOAc/hexanes to give the title product. LRMS (M+1)=378.7.

후처리

  1. temperatureThe reaction was maintained at −40° C. for 15 minutes
  2. customwas then quenched at −40° C. with saturated aqueous ammonium chloride (10 mL)
  3. additionWater (10 mL) was added
  4. temperatureto warm to room temperature
  5. extractionThe mixture was extracted with ethyl acetate (2×50 mL)
  6. washThe combined organic fractions were washed with water (3×50 mL)
  7. dry with materialdried (MgSO4)
  8. filtrationfiltered
  9. customthe solvent was evaporated under reduced pressure
  10. customThe resulting residue was purified by automated column chromatography on silica gel (40 g)
  11. washeluting with 0-25% EtOAc/hexanes

출처 및 근거

ORD 기록
ord-ccf239251028453396b0c06c02f3fadb
출처 데이터셋
uspto-grants-2010_08
특허 번호
US07781454B2

연결된 노트

불러오는 중…