Potassium Carbonate → HCID 90010077, compound

HRID 1056604Notes

Reaction equation

HRID 1056604 reaction equation
[CH2:1]([O:3][C:4](=[O:13])[C:5]1[CH:10]=[C:9]([Br:11])[C:8](Br)=[N:7][CH:6]=1)[CH3:2].[CH2:14](B(O)O)[CH3:15].C(=O)([O-])[O-].[K+].[K+]>O1CCOCC1.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:11][C:9]1[C:8]([CH2:14][CH3:15])=[N:7][CH:6]=[C:5]([CH:10]=1)[C:4]([O:3][CH2:1][CH3:2])=[O:13]

Participants

6

Reactant 3

HCID 11430Potassium CarbonateHCID 521157Ethylboronic acidHCID 46311326Ethyl 5,6-dibromopyridine-3-carboxylate

Product 1

HCID 90010077HCID 90010077, compoundYield 38%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
110 °C

Procedure

Method-2: A solution of ethyl-5,6-dibromonicotinate (6.0 g, 19.4 mmol, 1.0 eq; prepared by following the procedure described in WO2011024004), ethylboronic acid (1.72 g, 23.3 mmol, 1.2 eq) and potassium carbonate (8.0 g, 58.3 mmol, 3.0 eq) in 1,4-dioxane (10 mL) in a oven dried sealed tube was subjected to three cycles of evacuation-backfilling with argon, and then tetrakis(triphenylphosphine)palladium(0) (2.24 g, 1.94 mmol, 0.1 eq) was added. The sealed tube was sealed and the mixture was stirred and heated in an oil bath to 110° C. After three days of stirring at the same temperature, the reaction was cooled to RT and filtered through Celite®. The filtrate was evaporated and the resultant residue was purified by flash column chromatography (silica gel, ethyl acetate-hexane system as eluent) to afford 1.90 g (38%) of the desired product as a white solid. 1HNMR (400 MHz, CDCl3) δ 9.06 (d, J=1.5 Hz, 1H), 8.40 (d, J=1.5 Hz, 1H), 4.42 (q, J=7.0 Hz, 2H), 3.05 (q, J=7.0 Hz, 2H), 1.43 (t, J=7.0 Hz, 3H), 1.28 (t, J=7.0 Hz, 3H); GC-MS (m/z) 257, 259 [M+, Br79,81].

Workup

  1. customprepared
  2. customdried
  3. customsealed tube
  4. customThe sealed tube was sealed
  5. stirringAfter three days of stirring at the same temperature
  6. temperaturethe reaction was cooled to RT
  7. filtrationfiltered through Celite®
  8. customThe filtrate was evaporated
  9. customthe resultant residue was purified by flash column chromatography (silica gel, ethyl acetate-hexane system as eluent)

Sources & evidence

ORD record
ord-5ba0f0d2c77b48da9de0252540414f4f
Source dataset
uspto-grants-2016_07
Patent number
US09399638B2

Reaction notes

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