Hydrazine → 2-[4-(4-Amino-phenylethynyl)-1H-pyrazol-3-yl]-4-chloro-phenol

HRID 2075768

反応式

HRID 2075768 の反応式
[Cl:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[O:8][CH:7]=[C:6](I)[C:5]2=O.[C:14]([C:16]1[CH:22]=[CH:21][C:19]([NH2:20])=[CH:18][CH:17]=1)#[CH:15].C(N(C(C)C)CC)(C)C.[NH2:32][NH2:33]>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I.CC#N>[NH2:20][C:19]1[CH:21]=[CH:22][C:16]([C:14]#[C:15][C:6]2[C:5]([C:4]3[CH:3]=[C:2]([Cl:1])[CH:11]=[CH:10][C:9]=3[OH:8])=[N:32][NH:33][CH:7]=2)=[CH:17][CH:18]=1

参加物

8

反応物 4

HCID 9321HydrazineHCID 81531DiisopropylethylamineHCID 37600254-EthynylanilineHCID 116666776-Chloro-3-iodochromone2 回

生成物 1

HCID 1785075482-[4-(4-Amino-phenylethynyl)-1H-pyrazol-3-yl]-4-chloro-phenol収率 48.7%

試薬・触媒・溶媒 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 178418476HCID 178418476、化合物触媒HCID 6342Acetonitrile溶媒

実験手順

To a mixture of 6-chloro-3-iodo-chromone (1A, 6.12 g, 20 mmol) and 4-ethynylaniline (2.32 g, 24 mmol) and PdCl2(PPh3)2 (0.28 g, 0.4 mmol) and CuI (38 mg, 0.2 mmol) was added anhydrous CH3CN (200 mL). Upon stirring, diisopropylethylamine (DIPEA, 14 mL, 80 mmol) was added slowly to the above mixture. The reaction mixture was stirred at rt for 7 h. LCMS indicated all of 1A was consumed. Anhydrous hydrazine (5.3 mL, 80 mmol) was then added. The mixture was stirred at rt overnight. Solvent was removed. The residua was dissolved in dichloromethane and loaded onto a silica column eluting with dichloromethane/ethyl acetate (v/v 6/1, 2/1, 1/1, 1/2, 1/5) to afford the title compound 24A (3.02 g) as a yellowish solid in 48.7% yield. 1H NMR (CDCl3, 500 MHz) δ 10.05 (br s, 1H), 8.75 (d, 1H, J=2.0 Hz), 7.84 (s, 1H), 7.42 (d, 2H, J=8.5 Hz), 7.20 (dd, 1H, J=9.0, 2.0 Hz), 6.98 (d, 1H, J=8.5 Hz), 6.68 (d, 2H, J=8.0 Hz), 3.86 (s, 2H). LCMS (ESI) m/z 310.07 (MH+, 100); HPLC: tR=3.78 min.

後処理

  1. stirringThe reaction mixture was stirred at rt for 7 h
  2. customwas consumed
  3. stirringThe mixture was stirred at rt overnight
  4. customSolvent was removed
  5. dissolutionThe residua was dissolved in dichloromethane
  6. washeluting with dichloromethane/ethyl acetate (v/v 6/1, 2/1, 1/1, 1/2, 1/5)

出典と根拠

ORDレコード
ord-50644a70c6b9424a914ffc83f100fa34
出典データセット
uspto-grants-2011_04
特許番号
US07923004B2

関連ノート

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