Formamide → methyl[4-(5-bromo-1-methyl-1H-pyrazol-4-yl)-1H-imidazol-1-yl]carbamate

HRID 1907214ノート

反応式

HRID 1907214 の反応式
[Br:1][C:2]1[N:6]([CH3:7])[N:5]=[CH:4][C:3]=1[C:8](=O)[CH2:9][N:10]([CH:16]=O)[NH:11][C:12]([O:14][CH3:15])=[O:13].C([O-])(=O)C.[NH4+].C([NH2:26])=O.C(#N)C>O>[Br:1][C:2]1[N:6]([CH3:7])[N:5]=[CH:4][C:3]=1[C:8]1[N:26]=[CH:16][N:10]([NH:11][C:12](=[O:13])[O:14][CH3:15])[CH:9]=1

参加物

6

反応物 4

HCID 713FormamideHCID 6342Acetonitrile2 回HCID 517165Ammonium AcetateHCID 86669721methyl 2-[2-(5-bromo-1-methyl-1H-pyrazol-4-yl)-2-oxoethyl]-2-formylhydrazinecarboxylate

生成物 1

HCID 86669722methyl[4-(5-bromo-1-methyl-1H-pyrazol-4-yl)-1H-imidazol-1-yl]carbamate

試薬・触媒・溶媒 1

HCID 962Water溶媒

反応条件

温度
130 °C

実験手順

Methyl 2-[2-(5-bromo-1-methyl-1H-pyrazol-4-yl)-2-oxoethyl]-2-formylhydrazine carboxylate (1.20 g, 3.76 mmol) was mixed with ammonium acetate (1.16 g, 15.0 mmol), formamide (4 mL) and acetonitrile (5 mL). The reaction was heated to 130° C., and the acetonitrile was allowed to boil off for 10 minutes. Heating was continued for an additional 4 hours. After addition of water, the crude mixture was extracted eight times with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo; purification via silica gel chromatography (Gradient: 0% to 100% [10% methanol in ethyl acetate] in heptane) afforded the product as a pinkish solid. Yield: 800 mg, 2.67 mmol, 19% over two steps. LCMS m/z 299.8 (M+1). 1H NMR (400 MHz, CD3OD) δ 3.80 (br s, 3H), 3.90 (s, 3H), 7.52 (d, J=1.3 Hz, 1H), 7.77 (d, J=1.3 Hz, 1H), 7.85 (s, 1H).

後処理

  1. temperatureHeating
  2. waitwas continued for an additional 4 hours
  3. extractionthe crude mixture was extracted eight times with ethyl acetate
  4. dry with materialThe combined organic layers were dried over sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. custompurification via silica gel chromatography (Gradient: 0% to 100% [10% methanol in ethyl acetate] in heptane)

出典と根拠

ORDレコード
ord-41302aa17ebc47b0a320eeb7ee5845f3
出典データセット
uspto-grants-2013_12
特許番号
US08598155B2

反応ノート

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