Dimethyl Sulfoxide → 1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carbaldehyde

HRID 220453ノート

反応式

HRID 220453 の反応式
[CH3:1][N:2]1[CH:6]=[C:5]([CH2:7][OH:8])[C:4]([C:9]([F:12])([F:11])[F:10])=[N:3]1.CS(C)=O.C(Cl)(=O)C(Cl)=O.C(N(CC)CC)C>C(Cl)Cl>[CH3:1][N:2]1[CH:6]=[C:5]([CH:7]=[O:8])[C:4]([C:9]([F:10])([F:11])[F:12])=[N:3]1

参加物

6

反応物 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 21039553(1-Methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl)methanol

生成物 1

HCID 533020711-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carbaldehyde

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

反応条件

温度
-78 °C

実験手順

Dissolve (1-methyl-3-trifluoromethyl-1H-pyrazol-4-yl)-methanol (1.41 g, 7.83 mmol) in DCM (25 mL) and dimethylsulfoxide (2.22 mL, 31.3 mmol) and cool to −78° C. Add oxalyl chloride (1.91 mL, 21.9 mmol) dropwise over 15 min. and stir at −78° C. for an additional 1 hr. Add triethylamine (6.55 mL, 47.0 mmol) dropwise and stir another 1 hr. Quench with water (20 mL) and dilute with DCM (50 mL) and warm to room temperature for 1 hr. Separate the organic layer; dry (sodium sulfate), filter, concentrate and purify (silica gel chromatography, eluting with 80:20 hexanes:ethyl acetate), to give the title preparation (0.98 g, 71%). 1H-NMR (400 MHz, CDCl3) δ 9.94 (s, 1H), 7.97 (s, 1H), 3.99 (s, 3H).

後処理

  1. customQuench with water (20 mL)
  2. additiondilute with DCM (50 mL)
  3. temperaturewarm to room temperature for 1 hr
  4. customSeparate the organic layer
  5. dry with materialdry (sodium sulfate)
  6. filtrationfilter
  7. concentrationconcentrate
  8. custompurify
  9. wash(silica gel chromatography, eluting with 80:20 hexanes:ethyl acetate)
  10. customto give the title
  11. custompreparation (0.98 g, 71%)

出典と根拠

ORDレコード
ord-2925f8cc3ef44929bb764946bc2bebc4
出典データセット
uspto-grants-2012_06
特許番号
US08202873B2

反応ノート

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