Trifluoromethanesulfonic anhydride → Methyl 3-(trifluoromethylsulfonyloxy)-pyridine-2-carboxylate

HRID 389824ノート

反応式

HRID 389824 の反応式
[S:1]([O:8]S(C(F)(F)F)(=O)=O)([C:4]([F:7])([F:6])[F:5])(=[O:3])=[O:2].O[C:17]1[C:18]([C:23]([O:25][CH3:26])=[O:24])=[N:19][CH:20]=[CH:21][CH:22]=1>C(Cl)Cl>[F:5][C:4]([F:7])([F:6])[S:1]([O:8][C:17]1[C:18]([C:23]([O:25][CH3:26])=[O:24])=[N:19][CH:20]=[CH:21][CH:22]=1)(=[O:3])=[O:2]

参加物

4

反応物 2

HCID 67749Trifluoromethanesulfonic anhydrideHCID 819341Methyl 3-Hydroxy-2-pyridinecarboxylate

生成物 1

HCID 11066008Methyl 3-(trifluoromethylsulfonyloxy)-pyridine-2-carboxylate

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

反応条件

温度
0 °C

実験手順

Triflic anhydride (5.0 g, 18.0 mmol) was added dropwise to a cold (0° C.) solution of methyl 3-hydroxypicolinate (2.5 g, 16.3 mmol) and TEA (2.5 mL, 18.0 mmol) in CH2Cl2 (80 mL). The mixture was stirred at 0° C. for 1 h before it was allowed to warm up to room temperature where it stirred for an additional 1 h. The mixture was then quenched with saturated NaHCO3 solution (40 mL) and the organic layer was separated, washed with brine, dried over MgSO4 and concentrated to give methyl 3-(trifluoromethylsulfonyloxy)picolinate (i.e. Cap-174, step a) (3.38 g, 73%) as a dark brown oil (>95% pure) which was used directly without further purification. 1H NMR (300 MHz, CDCl3) δ ppm 8.72-8.79 (1H, m), 7.71 (1H, d, J=1.5 Hz), 7.58-7.65 (1H, m), 4.04 (3H, s). Rt=1.93 min (Cond.-MD1); LC/MS: Anal. Calcd. for [M+H]+ C8H7F3NO5S: 286.00. found: 286.08.

後処理

  1. temperatureto warm up to room temperature where it
  2. stirringstirred for an additional 1 h
  3. customThe mixture was then quenched with saturated NaHCO3 solution (40 mL)
  4. customthe organic layer was separated
  5. washwashed with brine
  6. dry with materialdried over MgSO4
  7. concentrationconcentrated

出典と根拠

ORDレコード
ord-54010a8be28d4f499ebeeba3166e28b3
出典データセット
uspto-grants-2013_02
特許番号
US08383094B2

反応ノート

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