Methyl chlorodifluoroacetate → 6-Methoxy-3-nitro-2-(trifluoromethyl)pyridine

HRID 1297286노트

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HRID 1297286 반응식
Cl[C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][CH:5]=[C:4]([O:11][CH3:12])[N:3]=1.[F-:13].[K+].Cl[C:16]([F:22])([F:21])C(OC)=O.[NH4+].[OH-].[NH4+].[Cl-]>CN(C=O)C>[CH3:12][O:11][C:4]1[N:3]=[C:2]([C:16]([F:22])([F:13])[F:21])[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][CH:5]=1

참가 물질

6

반응물 4

HCID 73935Methyl chlorodifluoroacetateHCID 522689Potassium FluorideHCID 27950292-Chloro-6-methoxy-3-nitropyridineHCID 21863491Ammonium chloride ammonium hydroxide

생성물 1

HCID 282423586-Methoxy-3-nitro-2-(trifluoromethyl)pyridine

시약·촉매·용매 1

HCID 6228Dimethylformamide용매

실험 절차

2-Chloro-6-methoxy-3-nitropyridine (5 g) was heated with Cul (6.05 g), KF(anhydrous, 3.0 g), methyl 2-chloro-2,2-difluoroacetate(6.8 ml) in DMF (28 ml) at 130° C. for 8 hrs. After cooling, it was poured into 1:9 mixture of NH4OH/NH4Cl(100 ml), stirred until homogeneous and extracted with Ethyl acetate. The organic layer were combined, washed with brine and dried (MgSO4), The flash column chromatography (SiO2, 1˜3% EtOAc in heptane) yielded 3.90 g (65%). 1H NMR (CDCl3) δ 4.02, 6.96, 8.10; IR (liq.) 2389 (w), 2254 (w), 2196 (w), 2163 (w), 2017 (w), 1605 (s), 1586 (s), 1538 (s), 1482 (s), 1340 (s), 1290 (s), 1261 (s), 1205 (s), 1180 (s), 1155 (s) cm−1 Anal. Calcd for C7H5F3N2O3: C, 37.85; H, 2.27; N, 12.61; F, 25.66. Found: C, 37.68; H, 2.29; N, 12.30.

후처리

  1. temperatureAfter cooling
  2. extractionextracted with Ethyl acetate
  3. washwashed with brine
  4. dry with materialdried (MgSO4)
  5. customThe flash column chromatography (SiO2, 1˜3% EtOAc in heptane) yielded 3.90 g (65%)

출처 및 근거

ORD 기록
ord-1b7d9a390d2241da95e621f9b5b54104
출처 데이터셋
uspto-grants-2007_07
특허 번호
US07250418B2

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