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

HRID 1272233

Reaktionsgleichung

Reaktionsgleichung von HRID 1272233
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]

Komponenten

7

Edukt 3

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

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 178418476HCID 178418476, VerbindungKatalysatorHCID 6342AcetonitrileLösungsmittel

Versuchsvorschrift

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%).

Aufarbeitung

  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)

Quellen und Nachweise

ORD-Eintrag
ord-1e50c39617fa4b878a36aef60b266a14
Quelldatensatz
uspto-grants-2007_04
Patentnummer
US07208505B2

Verknüpfte Notizen

Wird geladen…