Potassium Carbonate → HCID 23436574, compound

HRID 2121258Notes

Reaction equation

HRID 2121258 reaction equation
[N+:1]([C:4]1[CH:13]=[CH:12][C:7]([C:8]([O:10][CH3:11])=[O:9])=[C:6](Br)[CH:5]=1)([O-:3])=[O:2].[C:15]1([CH3:24])[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=1B(O)O.C([O-])([O-])=O.[K+].[K+]>CN(C=O)C.CCOCC.O>[N+:1]([C:4]1[CH:13]=[CH:12][C:7]([C:8]([O:10][CH3:11])=[O:9])=[C:6]([C:16]2[CH:17]=[CH:18][CH:19]=[CH:20][C:15]=2[CH3:24])[CH:5]=1)([O-:3])=[O:2]

Participants

7

Reactant 3

HCID 11430Potassium CarbonateHCID 27332672-Methylphenyl boronic acidHCID 15833211Methyl 2-Bromo-4-nitrobenzoate

Product 1

HCID 23436574HCID 23436574, compoundYield 97%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
115 °C

Procedure

Methyl 4-nitro-2-bromobenzoate (11.40 g, 43.85 mmol) was dissolved in 100 mL of DMF. Air was removed and the system was flushed with nitrogen. To this solution was added Pd(PPh3)4 (1.63 g, 3.1% eq). The pale yellow solution was stirred for 15 min until the color changed to deep brown. 2-Tolylboronic acid (6.6 g, 48.5 mmol) was added followed by anhydrous K2CO3 (18.2 g, 3.0 eq). The mixture was heated at 115° C. for 18 hr and then cooled down. This mixture was diluted with 100 mL of ether and 50 mL of water. The aqueous solution was extracted with ether. The ether solution was washed with 1N hydrochloric acid and then dried and evaporated. The residue was purified by flash column chromatography (10:1=hexane/ethyl acetate) to give a pale yellow oil which slowly solidifies (11.53 g, 97% yield). 1H NMR (CDCl3) δ 8.28 (d, J=8.7 Hz, 1H), 8.06-8.13 (s and d, 2H), 7.22-7.34 (m, 3H), 7.07 (d, J=7.3 Hz, 1H), 3.66 (s, 3H), 2.10 (s, 3H), 13C NMR (CDCl3) δ 165.7, 148.6, 143.5, 138.5, 135.9, 134.7, 130.5, 129.3, 127.9, 127.7, 125.1, 121.5, 51.8, 19.3; HRMS (EI) calcd for Cl5H13O4N 271.0844, obsd 271.0842.

Workup

  1. customAir was removed
  2. customthe system was flushed with nitrogen
  3. additionTo this solution was added Pd(PPh3)4 (1.63 g, 3.1% eq)
  4. temperaturecooled down
  5. extractionThe aqueous solution was extracted with ether
  6. washThe ether solution was washed with 1N hydrochloric acid
  7. customdried
  8. customevaporated
  9. customThe residue was purified by flash column chromatography (10:1=hexane/ethyl acetate)
  10. customto give a pale yellow oil which

Sources & evidence

ORD record
ord-608c3f5013ee45bf8fb396b6d6ce9f1a
Source dataset
uspto-grants-2004_02
Patent number
US06693123B2

Reaction notes

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