Pyrazole → 2-Methoxy-4-(1H-pyrazol-1-yl)aniline

HRID 32797

反応式

HRID 32797 の反応式
Br[C:2]1[CH:8]=[CH:7][C:5]([NH2:6])=[C:4]([O:9][CH3:10])[CH:3]=1.[NH:11]1[CH:15]=[CH:14][CH:13]=[N:12]1.C([O-])([O-])=O.[K+].[K+].CN[C@H]1[C@H](NC)CCCC1.[Na+].[Cl-]>CN1C(=O)CCC1.[Cu]I.CCOC(C)=O>[CH3:10][O:9][C:4]1[CH:3]=[C:2]([N:11]2[CH:15]=[CH:14][CH:13]=[N:12]2)[CH:8]=[CH:7][C:5]=1[NH2:6]

参加物

9

反応物 5

HCID 1048PyrazoleHCID 5234Sodium ChlorideHCID 11430Potassium CarbonateHCID 4592574-Bromo-2-methoxyanilineHCID 2733821trans-N,N'-dimethyl-1,2-cyclohexanediamine

生成物 1

HCID 597943592-Methoxy-4-(1H-pyrazol-1-yl)aniline収率 90%

試薬・触媒・溶媒 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 8857Ethyl Acetate溶媒HCID 13387N-methyl-2-pyrrolidone溶媒

反応条件

温度
150 °C

実験手順

To a solution of 4-bromo-2-(methyloxy)aniline (400 mg, 1.979 mmol) in anh. NMP (4 mL), at r.t., under N2, were added pyrazole (269 mg, 2 eq), K2CO3 (819 mg, 3 eq), CuI (377 mg, 1 eq) and (1R,2R)-diaminomethylcyclohexane (281 mg, 1 eq). The reaction mixture was stirred at 150° C. for 3 hr. It was cooled down to r.t. and poured into EtOAc/sat.aq. NaCl. The phases were separated and the organic layer was washed with sat.aq. NH4Cl (20 mL) and sat.aq. NaCl (20 mL). The combined aqueous layers were extracted back with EtOAc (20 mL) and the combined organic extracts were dried over anh. Na2SO4. The solids were filtered and the solvent evaporated. The crude product was purified by flash chromatography (silica gel, cHex/EtOAc 7:3) to give the title compound as a brown oil (336 mg, 90%)

後処理

  1. temperatureIt was cooled down to r.t.
  2. customThe phases were separated
  3. washthe organic layer was washed with sat.aq
  4. extractionThe combined aqueous layers were extracted back with EtOAc (20 mL)
  5. dry with materialthe combined organic extracts were dried over anh. Na2SO4
  6. filtrationThe solids were filtered
  7. customthe solvent evaporated
  8. customThe crude product was purified by flash chromatography (silica gel, cHex/EtOAc 7:3)

出典と根拠

ORDレコード
ord-9dae480e5d5e4f97b07f3895141283dc
出典データセット
uspto-grants-2008_09
特許番号
US07427630B2

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