3,3-Dimethyl-1-butyne → 2-(3,3-Dimethyl-but-1-ynyl)-6-fluoro-4-nitro-phenylamine

HRID 503339ノート

反応式

HRID 503339 の反応式
Br[C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[C:4]([F:11])[C:3]=1[NH2:12].[CH3:13][C:14]([CH3:18])([CH3:17])[C:15]#[CH:16]>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>[CH3:13][C:14]([CH3:18])([CH3:17])[C:15]#[C:16][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[C:4]([F:11])[C:3]=1[NH2:12]

参加物

6

反応物 2

HCID 135123,3-Dimethyl-1-butyneHCID 143001412-Bromo-6-fluoro-4-nitroaniline

生成物 1

HCID 591292912-(3,3-Dimethyl-but-1-ynyl)-6-fluoro-4-nitro-phenylamine収率 36%

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 solution of 2-bromo-6-fluoro-4-nitro-phenylamine (11 g, 47 mmol) in dry Et3N (100 mL) was added CuI (445 mg, 5% mol), Pd(PPh3)2Cl2 (550 mg, 5% mol) and 3,3-dimethyl-but-1-yne (9.6 g, 120 mmol) under N2 protection. The mixture was stirred at 80° C. for 10 h. The reaction mixture was filtered, poured into ice (100 g), and extracted with EtOAc (50 mL×3). The combined organic extracts were dried over anhydrous Na2SO4 and evaporated under vacuum to give the crude product, which was purified by column chromatography on silica gel (petroleum ether/ethyl acetate 50:1) to give 2-(3,3-dimethyl-but-1-ynyl)-6-fluoro-4-nitro-phenylamine (4.0 g, 36%). 1H NMR (400 MHz, CDCl3) δ 8.02 (d, J=1.2 Hz, 1H), 7.84 (dd, J=2.4, 10.8 Hz, 1H), 4.85 (brs, 2H), 1.36 (s, 9H).

後処理

  1. filtrationThe reaction mixture was filtered
  2. additionpoured into ice (100 g)
  3. extractionextracted with EtOAc (50 mL×3)
  4. dry with materialThe combined organic extracts were dried over anhydrous Na2SO4
  5. customevaporated under vacuum
  6. customto give the crude product, which
  7. customwas purified by column chromatography on silica gel (petroleum ether/ethyl acetate 50:1)

出典と根拠

ORDレコード
ord-591a70e9a7664f73a1657c9a97761901
出典データセット
uspto-grants-2010_08
特許番号
US07776905B2

反応ノート

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