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

HRID 1297286ノート

反応式

HRID 1297286 の反応式
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

参加物

6

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

実験手順

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.

後処理

  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%)

出典と根拠

ORDレコード
ord-1b7d9a390d2241da95e621f9b5b54104
出典データセット
uspto-grants-2007_07
特許番号
US07250418B2

反応ノート

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