Sodium Carbonate → HCID 89782036, compound

HRID 1056265Notes

Reaction equation

HRID 1056265 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.C([O-])([O-])=O.[Na+].[Na+].[CH3:19][C:20]1[CH:25]=[CH:24][CH:23]=[C:22]([CH3:26])[C:21]=1B(O)O>C(#N)C.O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Br:1][C:2]1[CH:3]=[CH:4][CH:5]=[C:6]2[C:11]=1[N:10]=[C:9]([C:21]1[C:22]([CH3:26])=[CH:23][CH:24]=[CH:25][C:20]=1[CH3:19])[CH:8]=[N:7]2

Participants

7

Reactant 3

HCID 10340Sodium CarbonateHCID 5833222,6-Dimethylphenylboronic acidHCID 593926708-Bromo-2-chloroquinoxaline

Product 1

HCID 89782036HCID 89782036, compoundYield 12.2%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 6342AcetonitrileSolvent

Conditions

Temperature
80 °C

Procedure

Argon was bubbled into a mixture of 8-bromo-2-chloroquinoxaline (210e; 0.50 g, 2.05 mmol), Na2CO3 (1.09 g, 10.27 mmol), Pd(PPh3)4 (Strem; 0.119 g, 0.103 mmol), 2,6-dimethylbenzeneboronic acid (Aldrich; 0.31 g, 2.05 mmol) in 9 mL ACN and 3 mL water for 1 min. The reaction was sealed and heated to 80° C. overnight. The temperature was increased to 100° C. and the reaction was heated 8 h. The reaction was partitioned between water and DCM. The aqueous layer was extracted with DCM 3 times, and the combined organics were dried over anhydrous Na2SO4, filtered, and concentrated in vacuo. The material was treated with MeOH/DCM and adsorbed onto 2 g silica gel, dried, and purified by silica gel chromatography (40 g ISCO gold column) using 0-30% EtOAc/hexanes. The product-containing fractions were concentrated to afford 8-bromo-2-(2,6-dimethylphenyl)quinoxaline (0.08 g, 0.25 mmol, 12% yield) as an oil that solidifies very slowly to a white solid. 1H NMR (400 MHz, CDCl3) δ ppm 8.83 (1H, s), 8.09-8.19 (2H, m), 7.67 (1H, dd, J=8.2, 7.6 Hz), 7.27-7.33 (1H, m), 7.16-7.23 (2H, m), 2.18 (6H, s). m/z (ESI, +ve) 313.0/315.0 (M+H)+.

Workup

  1. customThe reaction was sealed
  2. temperatureThe temperature was increased to 100° C.
  3. temperaturethe reaction was heated 8 h
  4. customThe reaction was partitioned between water and DCM
  5. extractionThe aqueous layer was extracted with DCM 3 times
  6. dry with materialthe combined organics were dried over anhydrous Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. additionThe material was treated with MeOH/DCM
  10. customdried
  11. custompurified by silica gel chromatography (40 g ISCO gold column)
  12. concentrationThe product-containing fractions were concentrated

Sources & evidence

ORD record
ord-b5a879aa5e0c455e873ded3ea83c72bd
Source dataset
uspto-grants-2016_07
Patent number
US09394297B2

Reaction notes

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