Triethylamine → Ethyl 3-methyl-4-((triethylsilyl)ethynyl)benzoate

HRID 1259154ノート

反応式

HRID 1259154 の反応式
Br[C:2]1[CH:12]=[CH:11][C:5]([C:6]([O:8][CH2:9][CH3:10])=[O:7])=[CH:4][C:3]=1[CH3:13].[CH2:14]([Si:16]([CH2:21][CH3:22])([CH2:19][CH3:20])[C:17]#[CH:18])[CH3:15].C(N(CC)CC)C>CN(C=O)C.C(OCC)(=O)C.[OH-].[NH4+].[Cu]I>[CH3:13][C:3]1[CH:4]=[C:5]([CH:11]=[CH:12][C:2]=1[C:15]#[C:14][Si:16]([CH2:21][CH3:22])([CH2:19][CH3:20])[CH2:17][CH3:18])[C:6]([O:8][CH2:9][CH3:10])=[O:7]

参加物

8

反応物 3

HCID 8471TriethylamineHCID 637947(Triethylsilyl)acetyleneHCID 21729626Ethyl 4-bromo-3-methylbenzoate

生成物 1

HCID 66874679Ethyl 3-methyl-4-((triethylsilyl)ethynyl)benzoate

試薬・触媒・溶媒 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 6228Dimethylformamide溶媒HCID 8857Ethyl Acetate溶媒HCID 14923Ammonium Hydroxide溶媒

実験手順

A solution of ethyl 4-bromo-3-methylbenzoate (from the previous step) (1.0 eq.), triethyl(ethynyl)silane (1.1 eq.), trans-dichlororbis(triphenylphosphine)palladium (II) (10 mol %), copper (I) iodide (20 mol %), and triethylamine (5.0 eq.) in DMF (0.3 M) was stirred at 60° C. overnight. After cooling to ambient temperature, the reaction mixture was diluted with ethyl acetate and 10% aqueous ammonium hydroxide. The two phases were separated, and the aqueous layer was extracted twice with ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous MgSO4, and concentrated en vaccuo. The crude material was purified by flash chromatography on a COMBIFLASH® system (ISCO) using 0-5% ethyl acetate in hexane to give ethyl 3-methyl-4-((triethylsilyl)ethynyl)benzoate as a yellow oil.

後処理

  1. customThe two phases were separated
  2. extractionthe aqueous layer was extracted twice with ethyl acetate
  3. washThe combined organic layers were washed with brine
  4. dry with materialdried over anhydrous MgSO4
  5. concentrationconcentrated en vaccuo
  6. customThe crude material was purified by flash chromatography on a COMBIFLASH® system (ISCO)

出典と根拠

ORDレコード
ord-8ea53eea0c3346c7825311cfedae3842
出典データセット
uspto-grants-2013_06
特許番号
US08466167B2

反応ノート

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