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

HRID 2075768

반응식

HRID 2075768 반응식
[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

참가 물질

8

반응물 4

HCID 9321HydrazineHCID 81531DiisopropylethylamineHCID 37600254-EthynylanilineHCID 116666776-Chloro-3-iodochromone2회

생성물 1

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

시약·촉매·용매 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)촉매HCID 178418476HCID 178418476, 화합물촉매HCID 6342Acetonitrile용매

실험 절차

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.

후처리

  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)

출처 및 근거

ORD 기록
ord-50644a70c6b9424a914ffc83f100fa34
출처 데이터셋
uspto-grants-2011_04
특허 번호
US07923004B2

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