Phosphorus oxychloride → Methyl 4-chloroquinoline-6-carboxylate

HRID 509340ノート

反応式

HRID 509340 の反応式
[CH3:1][O:2][C:3]([C:5]1[CH:6]=[C:7]2[C:12](=[CH:13][CH:14]=1)[N+:11]([O-])=[CH:10][CH:9]=[CH:8]2)=[O:4].P(Cl)(Cl)([Cl:18])=O>>[Cl:18][C:8]1[C:7]2[C:12](=[CH:13][CH:14]=[C:5]([C:3]([O:2][CH3:1])=[O:4])[CH:6]=2)[N:11]=[CH:10][CH:9]=1

参加物

3

反応物 2

HCID 24813Phosphorus oxychlorideHCID 21707072Methyl quinoline-6-carboxylate 1-oxide

生成物 1

HCID 58441390Methyl 4-chloroquinoline-6-carboxylate収率 25.8%

実験手順

To 6-(methoxycarbonyl)quinoline-N-oxide from the above step was added phosphoryl trichloride (5 mL, 54.6 mmol). The resulting mixture was then stirred at rt under N2 for 2 h. The reaction was then slowly quenched by addition to an ice cold solution of saturated aqueous NaHCO3 (50 mL) in an ice bath with rapid stirring. The aqueous solution was extracted with EtOAc (3×50 mL). The organic layers were combined, washed with saturated aqueous NaHCO3 (25 mL), H2O (25 mL), dried (MgSO4), and concentrated. Purification by ISCO (40 g SiO2, 0-50% EtOAc/hexanes) gave as the major product, methyl 4-chloroquinoline-6-carboxylate (330 mg, 1.489 mmol, 25.8% yield over 3 steps) (m/z=221.9) as a white solid. Also isolated was the more polar, methyl 2-chloroquinoline-6-carboxylate with same mass (m/z=221.9).

後処理

  1. customThe reaction was then slowly quenched by addition to an ice cold solution of saturated aqueous NaHCO3 (50 mL) in an ice bath with rapid stirring
  2. extractionThe aqueous solution was extracted with EtOAc (3×50 mL)
  3. washwashed with saturated aqueous NaHCO3 (25 mL), H2O (25 mL)
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated
  6. customPurification by ISCO (40 g SiO2, 0-50% EtOAc/hexanes)

出典と根拠

ORDレコード
ord-1ca5e032d79546caa9f8284bfe725e8c
出典データセット
uspto-grants-2015_08
特許番号
US09096527B2

反応ノート

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