3,3-Dimethyl-1-butyne → 2-Amino-3-(3,3-dimethylbut-1-ynyl)-5-nitrobenzonitrile

HRID 1403920ノート

反応式

HRID 1403920 の反応式
[NH2:1][C:2]1[C:9](Br)=[CH:8][C:7]([N+:11]([O-:13])=[O:12])=[CH:6][C:3]=1[C:4]#[N:5].[CH3:14][C:15]([CH3:19])([CH3:18])[C:16]#[CH:17]>CCN(CC)CC.[Cu]I.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>[NH2:1][C:2]1[C:9]([C:17]#[C:16][C:15]([CH3:19])([CH3:18])[CH3:14])=[CH:8][C:7]([N+:11]([O-:13])=[O:12])=[CH:6][C:3]=1[C:4]#[N:5]

参加物

6

反応物 2

HCID 135123,3-Dimethyl-1-butyneHCID 871732-Amino-3-bromo-5-nitrobenzonitrile

生成物 1

HCID 591292522-Amino-3-(3,3-dimethylbut-1-ynyl)-5-nitrobenzonitrile収率 71%

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 8471Triethylamine溶媒

反応条件

温度
80 °C

実験手順

To a stirred solution of 2-amino-3-bromo-5-nitrobenzonitrile (2.4 g, 10 mmol) in dry Et3N (60 mL) was added CuI (380 mg, 5% mol) and Pd(PPh3)2Cl2 (470 mg, 5% mol) at room temperature. 3,3-dimethyl-but-1-yne (2.1 g, 25 mmol) was added dropwise to the mixture at room temperature. The reaction mixture was stirred at 80° C. for 10 h. The reaction mixture was filtered and the filtrate was poured into ice (60 g), extracted with ethyl acetate. The phases were separated and the organic phase was dried over Na2SO4. The solvent was removed under vacuum to obtain the crude product, which was purified by column chromatography (2-10% EtOAc in petroleum ether) to obtain 2-amino-3-(3,3-dimethylbut-1-ynyl)-5-nitrobenzonitrile (1.7 g, 71%). 1H NMR (300 MHz, CDCl3) δ 8.28 (d, J=2.7 Hz, 1H), 8.27 (d, J=2.7 Hz, 1H), 5.56 (br s, 2H), 1.37 (s, 9H).

後処理

  1. filtrationThe reaction mixture was filtered
  2. additionthe filtrate was poured into ice (60 g)
  3. extractionextracted with ethyl acetate
  4. customThe phases were separated
  5. dry with materialthe organic phase was dried over Na2SO4
  6. customThe solvent was removed under vacuum
  7. customto obtain the crude product, which
  8. customwas purified by column chromatography (2-10% EtOAc in petroleum ether)

出典と根拠

ORDレコード
ord-3cb8a8da41b64dbd8481c925eb4bff80
出典データセット
uspto-grants-2014_12
特許番号
US08912199B2

反応ノート

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