2-Methyl-3-butyn-2-ol → HCID 59392681, compound

HRID 216740Notes

Reaction equation

HRID 216740 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][CH:5]=[C:6]2[C:11]=1[N:10]=[C:9](Cl)[CH:8]=[N:7]2.[CH3:13][C:14]([OH:18])([C:16]#[CH:17])[CH3:15].CCN(CC)CC>[Cu]I.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>[Br:1][C:2]1[CH:3]=[CH:4][CH:5]=[C:6]2[C:11]=1[N:10]=[C:9]([C:17]#[C:16][C:14]([CH3:15])([OH:18])[CH3:13])[CH:8]=[N:7]2

Participants

6

Reactant 3

HCID 82582-Methyl-3-butyn-2-olHCID 8471TriethylamineHCID 593926708-Bromo-2-chloroquinoxaline

Product 1

HCID 59392681HCID 59392681, compound

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalyst

Procedure

A microwave tube is charged with 200 mg (0.821 mmol) of 8-Bromo-2-chloro-quinoxaline, 159 μl (1.64 mmol) of 2-Methyl-but-3-yn-2-ol, 231 μl (1.64 mmol) of Et3N, 6.26 mg (0.0329 mmol) of CuI and 11.8 mg (0.0164 mmol) of Pd(PPh3)2Cl2. After several cycles of vacuum/purge with argon, 5 ml of n-BuOH are added. The reaction mixture is then stirred at RT for 30 min. The reaction mixture is poured onto a solution of NaHCO3 and diluted with EtOAc and the phases are separated. The organic phase is washed several times with de-ionized water and the aqueous layer re-extracted with EtOAc. The combined organic layers are washed with brine, dried over Na2SO4, filtered and the filtrate is concentrated in vacuo. The residue is dissolved in CH2Cl2 and purified by chromatography (silicagel, hexane:EtOAc=1:1) to afford the title compound as a brown oil, Rt=1.026 min (Acquity HPLC BEH C18, 2.1×50 mm, 1.7 micron, detection 215 nM, 0.1 min 2% CH3CN in H2O, 2% to 100% CH3CN in H2O in 1.5 min, 0.4 min 100% CH3CN+0.1% TFA, flow rate 1.0 ml/min); MS: 291 (M+1, 79Br)+.

Workup

  1. customAfter several cycles of vacuum/purge with argon, 5 ml of n-BuOH
  2. additionare added
  3. additionThe reaction mixture is poured onto a solution of NaHCO3
  4. additiondiluted with EtOAc
  5. customthe phases are separated
  6. washThe organic phase is washed several times with de-ionized water
  7. extractionthe aqueous layer re-extracted with EtOAc
  8. washThe combined organic layers are washed with brine
  9. dry with materialdried over Na2SO4
  10. filtrationfiltered
  11. concentrationthe filtrate is concentrated in vacuo
  12. dissolutionThe residue is dissolved in CH2Cl2
  13. custompurified by chromatography (silicagel, hexane:EtOAc=1:1)

Sources & evidence

ORD record
ord-45169187c01b4f90b29cd06042c5b64a
Source dataset
uspto-grants-2012_06
Patent number
US08193189B2

Reaction notes

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