Acetic Acid → 2-bromo-1-[3-methyl-1-(propan-2-yl)-1H-1,2,4-triazol-5-yl]ethan-1-one

HRID 1498158ノート

反応式

HRID 1498158 の反応式
C([O:3][C:4]([C:6]1[N:7]([CH:12]([CH3:14])[CH3:13])[N:8]=[C:9]([CH3:11])[N:10]=1)=O)C.[Br:15][CH2:16]Br.C[Li].C(O)(=O)C>C1COCC1.O>[Br:15][CH2:16][C:4]([C:6]1[N:7]([CH:12]([CH3:14])[CH3:13])[N:8]=[C:9]([CH3:11])[N:10]=1)=[O:3]

参加物

7

反応物 4

HCID 176Acetic AcidHCID 3024DibromomethaneHCID 582047541H-1,2,4-Triazole-5-carboxylic acid, 3-methyl-1-(1-methylethyl)-, ethyl esterHCID 178418348HCID 178418348、化合物

生成物 1

HCID 582048242-bromo-1-[3-methyl-1-(propan-2-yl)-1H-1,2,4-triazol-5-yl]ethan-1-one

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
-78 °C

実験手順

To a solution of 2-isopropyl-5-methyl-2H-[1,2,4]triazole-3-carboxylic acid ethyl ester (12.09 g, 61.3 mmol) and dibromomethane (8.63 mL, 122.6 mmol) in THF (500 mL) at −78° C. was added methyllithium (40.9 mL, 122.6 mmol, 3M solution in diethoxymethane) dropwise. The reaction mixture was stirred at −78° C. for 15 min. Acetic acid (3 mL) was added and the reaction mixture allowed to warm to RT. The reaction mixture was diluted with water and extracted with ethyl acetate (3×30 mL). The combined organic extracts were washed with brine, dried (MgSO4) and concentrated in vacuo. The resultant residue was subjected to flash chromatography (SiO2, gradient 0-100% ethyl acetate in cyclohexane) to give 2-Bromo-1-(2-isopropyl-5-methyl-2H-[1,2,4]triazol-3-yl)-ethanone as a colourless oil which crystallised on standing (11.26 g, 75%). 1H NMR 400 MHz (CDCl3) δ: 5.41 (1H, sept, J=6.6 Hz), 4.67 (2H, s), 2.44 (3H, s), 1.49 (6H, d, J=6.6 Hz)

後処理

  1. temperatureto warm to RT
  2. extractionextracted with ethyl acetate (3×30 mL)
  3. washThe combined organic extracts were washed with brine
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated in vacuo

出典と根拠

ORDレコード
ord-70b3215411d34bacba46ab0655e0b076
出典データセット
uspto-grants-2015_12
特許番号
US09198918B2

反応ノート

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