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

HRID 468344노트

반응식

HRID 468344 반응식
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]

참가 물질

6

반응물 2

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

생성물 1

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

시약·촉매·용매 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)촉매HCID 178418476HCID 178418476, 화합물촉매HCID 8471Triethylamine용매

반응 조건

온도
80 °C

실험 절차

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, =2.4, 10.8 Hz, 1H), 4.85 (brs, 2H), 1.36 (s, 9H).

후처리

  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)

출처 및 근거

ORD 기록
ord-c151f78058054ff391c11a41a12e91d9
출처 데이터셋
uspto-grants-2014_01
특허 번호
US08623905B2

반응 노트

불러오는 중…