Triethylamine → ethyl N-{2,4-difluoro-6-[2-(trimethylsilyl)ethynyl]phenyl}carbamate

HRID 1272233

反応式

HRID 1272233 の反応式
Br[C:2]1[CH:13]=[C:12]([F:14])[CH:11]=[C:10]([F:15])[C:3]=1[NH:4][C:5]([O:7][CH2:8][CH3:9])=[O:6].C(N(CC)CC)C.[CH3:23][Si:24]([C:27]#[CH:28])([CH3:26])[CH3:25]>CC#N.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>[CH3:23][Si:24]([C:27]#[C:28][C:2]1[CH:13]=[C:12]([F:14])[CH:11]=[C:10]([F:15])[C:3]=1[NH:4][C:5]([O:7][CH2:8][CH3:9])=[O:6])([CH3:26])[CH3:25]

参加物

7

反応物 3

HCID 8471TriethylamineHCID 66111TrimethylsilylacetyleneHCID 170685752-bromo-4,6-difluoro-N-carbethoxy aniline

生成物 1

HCID 22014809ethyl N-{2,4-difluoro-6-[2-(trimethylsilyl)ethynyl]phenyl}carbamate収率 71%

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 6342Acetonitrile溶媒

実験手順

In a 2L flask, 2-bromo-4,6-difluoro-N-carbethoxy aniline (42 g, 150 mmol) in CH3CN (500 mL) is degassed with vacuum and purged with N2. Dichlorobis(triphenylphosphine)palladium(II) (10.5 g, 15 mmol, 10 mol %), followed by CuI (710 mg, 4 mmol, 2.5 mol %) and triethyl amine (41 mL) are added and rinsed in with 100 mL of CH3CN. Trimethylsilyl acetylene (31.8 ml, 225 mmol) is added and reaction is refluxed under N2. Approximately 2 hours later, the starting material is consumed, indicated by TLC (20% ethyl acetate/hexane, UV). The reaction is cooled, filtered, concentrated, and the residue is dissolved in ethyl acetate, washed with H2O, brine, dried (Na2SO4), filtered, concentrated, and is purified by flash chromatography (SiO2, ethyl acetate/hexane gradient) to yield 30 g of 2-(trimethylsilylethynyl)-4,6-difluoro-N-carbethoxyaniline (71%).

後処理

  1. custompurged with N2
  2. additionare added
  3. washrinsed in with 100 mL of CH3CN
  4. customreaction
  5. temperatureis refluxed under N2
  6. customApproximately 2 hours later, the starting material is consumed
  7. temperatureThe reaction is cooled
  8. filtrationfiltered
  9. concentrationconcentrated
  10. dissolutionthe residue is dissolved in ethyl acetate
  11. washwashed with H2O, brine
  12. dry with materialdried (Na2SO4)
  13. filtrationfiltered
  14. concentrationconcentrated
  15. customis purified by flash chromatography (SiO2, ethyl acetate/hexane gradient)

出典と根拠

ORDレコード
ord-1e50c39617fa4b878a36aef60b266a14
出典データセット
uspto-grants-2007_04
特許番号
US07208505B2

関連ノート

読み込み中…