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

HRID 468348노트

반응식

HRID 468348 반응식
[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]

참가 물질

6

반응물 2

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

생성물 1

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

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 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).

후처리

  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)

출처 및 근거

ORD 기록
ord-93e9f5f0fdd346a9bd8c63f7a91f6346
출처 데이터셋
uspto-grants-2014_01
특허 번호
US08623905B2

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