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

HRID 1272233

반응식

HRID 1272233 반응식
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]

참가 물질

7

반응물 3

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

생성물 1

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

시약·촉매·용매 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)촉매HCID 178418476HCID 178418476, 화합물촉매HCID 6342Acetonitrile용매

실험 절차

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%).

후처리

  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)

출처 및 근거

ORD 기록
ord-1e50c39617fa4b878a36aef60b266a14
출처 데이터셋
uspto-grants-2007_04
특허 번호
US07208505B2

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