Diethyl Ether → 5-(2-Methoxy-5-nitrophenyl)-1-methyl-1H-pyrazole

HRID 1362953

反応式

HRID 1362953 の反応式
[CH3:1][N:2]1[CH:6]=[CH:5][CH:4]=[N:3]1.C([Li])CCC.CCCCCC.C(OCC)C.I[C:24]1[CH:29]=[C:28]([N+:30]([O-:32])=[O:31])[CH:27]=[CH:26][C:25]=1[O:33][CH3:34]>C1COCC1.[Cl-].[Zn+2].[Cl-].C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:34][O:33][C:25]1[CH:26]=[CH:27][C:28]([N+:30]([O-:32])=[O:31])=[CH:29][C:24]=1[C:6]1[N:2]([CH3:1])[N:3]=[CH:4][CH:5]=1

参加物

10

反応物 5

HCID 3283Diethyl EtherHCID 8058HexaneHCID 702551H-Pyrazole, 1-methyl-HCID 948062-Iodo-1-methoxy-4-nitrobenzeneHCID 178418339Butyllithium

生成物 1

HCID 231395315-(2-Methoxy-5-nitrophenyl)-1-methyl-1H-pyrazole収率 59.1%

試薬・触媒・溶媒 4

HCID 3007855Zincchloride触媒HCID 178418397HCID 178418397、化合物触媒HCID 8028Tetrahydrofuran溶媒2 回HCID 3007855Zincchloride溶媒

実験手順

A solution of N-methylpyrazole (5.12 g, 62.4 mmol) in THF (100 mL) was cooled to −78° C. and 2.5 M n-butyllithium in hexane (27.5 mL, 68.8 mmol) was added. After stirring for 30 minutes at the same temperature, 0.5 M zinc chloride in THF (107 mL, 53.5 mmol) and 1 M zinc chloride in diethyl ether (15.3 mL, 15.2 mmol) were added. The mixture was allowed to warm to room temperature and 2-iodo-4-nitroanisole (17.4 g, 62.4 mmol) followed by tetrakis(triphenylphosphine)palladium (3.6 g, 3.1 mmol) were added. After stirring at 60° C. for 20 hours, the black solution was concentrated on a rotary evaporator, and extracted with ethyl acetate and brine. Combined organic layers were dried over magnesium sulfate, filtered, and partly concentrated until a solid started to precipitate. Hexane was added, precipitate was filtered off, and washed with a cold 3:1 mixture of hexane/ethyl acetate to give 5-(2-methoxy-5-nitro-phenyl)-1-methyl-1H-pyrazole (8.6 g, 36.9 mmol, 59%) as a tan solid. LCMS m/z (%/o)=234 (M+H, 100). 1H NMR (400 MHz, CDCl3) δ: 8.34 (dd, J=2.8, 9.2 Hz, 1H), 8.19 (d, J=2.8 Hz, 1H), 7.56 (d, J=2.0 Hz, 1H), 7.08 (d, J=9.2 Hz, 1H), 6.31 (d, J=1.6 Hz, 1H), 3.96 (s, 3H), 3.74 (s, 3H).

後処理

  1. additionwere added
  2. additionwere added
  3. concentrationthe black solution was concentrated on a rotary evaporator
  4. extractionextracted with ethyl acetate and brine
  5. dry with materialCombined organic layers were dried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationpartly concentrated until a solid
  8. customto precipitate
  9. additionHexane was added
  10. filtrationprecipitate was filtered off
  11. washwashed with a cold 3:1 mixture of hexane/ethyl acetate

出典と根拠

ORDレコード
ord-993ce01f630f4c779856b18b3003c857
出典データセット
uspto-grants-2011_02
特許番号
US07884101B2

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