(1,1-Dimethylprop-2-ynyloxy)acetic acid methyl ester → [3-(4'-Chloro-4-methylbiphenyl-3-yl)-1,1-dimethylprop-2-ynyloxy]acetic acid methyl ester

HRID 468208노트

반응식

HRID 468208 반응식
Br[C:2]1[CH:3]=[C:4]([C:9]2[CH:14]=[CH:13][C:12]([Cl:15])=[CH:11][CH:10]=2)[CH:5]=[CH:6][C:7]=1[CH3:8].[CH3:16][O:17][C:18](=[O:26])[CH2:19][O:20][C:21]([CH3:25])([CH3:24])[C:22]#[CH:23]>C(N(CC)CC)C.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>[CH3:16][O:17][C:18](=[O:26])[CH2:19][O:20][C:21]([CH3:24])([CH3:25])[C:22]#[C:23][C:2]1[CH:3]=[C:4]([C:9]2[CH:14]=[CH:13][C:12]([Cl:15])=[CH:11][CH:10]=2)[CH:5]=[CH:6][C:7]=1[CH3:8]

참가 물질

6

반응물 2

HCID 13005744(1,1-Dimethylprop-2-ynyloxy)acetic acid methyl esterHCID 594459301-Bromo-5-(4-chlorophenyl)-2-methylbenzene

생성물 1

HCID 58312427[3-(4'-Chloro-4-methylbiphenyl-3-yl)-1,1-dimethylprop-2-ynyloxy]acetic acid methyl ester수율 42%

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 3-bromo-4′-chloro-4-methylbiphenyl (12.6 g, 44.7 mmol) and (1,1-dimethylprop-2-ynyloxy)acetic acid methyl ester (prepared according to WO2001/066544) (8.4 g, 53.8 mmol) in triethylamine (70 ml) is added bis(triphenylphosphine)palladium(II) dichloride (0.63 g, 0.9 mmol) and copper(I) iodide (0.34 g, 1.8 mmol). The reaction mixture is degassed and flushed with nitrogen (×3), then stirred under nitrogen at 80° C. for one hour. The cooled mixture is filtered through diatomaceous earth to remove the catalyst, and the filtrate evaporated in vacuo. The residue is resubjected to the same reaction conditions (8.4 g 1,1-dimethylprop-2-ynyloxy)acetic acid methyl ester, 0.63 g bis(triphenylphosphine)-palladium(II) dichloride, 0.34 g copper(I) iodide in 70 ml triethylamine under nitrogen) and stirred at 80° C. for one hour. The cooled mixture is filtered through diatomaceous earth, then concentrated in vacuo and purified by flash chromatography (hexane/ethyl acetate 3:1) to afford [3-(4′-chloro-4-methylbiphenyl-3-yl)-1,1-dimethylprop-2-ynyloxy]acetic acid methyl ester (6.70 g,) as an oil.

후처리

  1. customThe reaction mixture is degassed
  2. customflushed with nitrogen (×3)
  3. filtrationThe cooled mixture is filtered through diatomaceous earth
  4. customto remove the catalyst
  5. customthe filtrate evaporated in vacuo
  6. customThe residue is resubjected to the same reaction conditions (8.4 g 1,1-dimethylprop-2-ynyloxy)acetic acid methyl ester, 0.63 g bis(triphenylphosphine)-palladium(II) dichloride, 0.34 g copper(I) iodide in 70 ml triethylamine under nitrogen) and
  7. stirringstirred at 80° C. for one hour
  8. filtrationThe cooled mixture is filtered through diatomaceous earth
  9. concentrationconcentrated in vacuo
  10. custompurified by flash chromatography (hexane/ethyl acetate 3:1)

출처 및 근거

ORD 기록
ord-b6cf6fb0ca9341159255d1e5f2612b7a
출처 데이터셋
uspto-grants-2014_01
특허 번호
US08623907B2

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