1,2-Dichlorobenzene → 3-Fluoro-5-nitrobenzoic acid

HRID 266858

반응식

HRID 266858 반응식
[F:1][B-](F)(F)F.N#[O+].N[C:9]1[CH:10]=[C:11]([CH:15]=[C:16]([N+:18]([O-:20])=[O:19])[CH:17]=1)[C:12]([OH:14])=[O:13].ClC1C=CC=CC=1Cl>C(#N)C>[F:1][C:9]1[CH:10]=[C:11]([CH:15]=[C:16]([N+:18]([O-:20])=[O:19])[CH:17]=1)[C:12]([OH:14])=[O:13]

참가 물질

5

반응물 3

HCID 72391,2-DichlorobenzeneHCID 2393423-Amino-5-nitrobenzoic acidHCID 11137142Nitrilooxonium tetrafluoroborate

생성물 1

HCID 27590473-Fluoro-5-nitrobenzoic acid수율 64.2%

시약·촉매·용매 1

HCID 6342Acetonitrile용매

실험 절차

A vigorously stirred slurry of nitrosonium tetrafluoroborate (3.53 g, 30.2 mM) in acetonitrile (50 ml) under an atmosphere of argon was cooled in an ice bath, and 3-amino-5-nitrobenzoic acid (5.0 g, 27.5 mM) was added in three portions. The temperature was then allowed to rise to ambient, and the mixture was stirred for 48 hours. 1,2-Dichlorobenzene (50 ml) was added, and acetonitrile distilled from the mixture at reduced pressure. The mixture was then heated to 170° for 30 minutes, when gas evolution had ended. After cooling, the mix was poured into dichloromethane (200 ml), and extracted with NaHCO3 solution. After back washing the aqueous phase with dichloromethane, it was acidified (2M hydrochloric acid), and organics extracted with ethyl acetate (2×100 ml). The combined organic layers were washed with brine, and dried over MgSO4. Crude product was purified by chromatography on silica, eluting with a gradient from dichloromethane/acetic acid (99:1) to dichloromethane/isopropanol/acetic acid (80:20:1), to give 3-fluoro-5-nitrobenzoic acid (3.26 g, 64%). Nmr (DHSO-d6): δ 8.14 (dm, 1H); 8.37 (dt, 1H); 8.46 (m, 1H).

후처리

  1. distillationacetonitrile distilled from the mixture at reduced pressure
  2. temperatureThe mixture was then heated to 170° for 30 minutes
  3. temperatureAfter cooling
  4. additionthe mix was poured into dichloromethane (200 ml)
  5. extractionextracted with NaHCO3 solution
  6. washAfter back washing the aqueous phase with dichloromethane, it
  7. extractionorganics extracted with ethyl acetate (2×100 ml)
  8. washThe combined organic layers were washed with brine
  9. dry with materialdried over MgSO4
  10. customCrude product was purified by chromatography on silica
  11. washeluting with a gradient from dichloromethane/acetic acid (99:1) to dichloromethane/isopropanol/acetic acid (80:20:1)

출처 및 근거

ORD 기록
ord-bcdfcb9bf16d4b70a4a26a0aab1bf326
출처 데이터셋
uspto-grants-1997_07
특허 번호
US05652233

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