Sodium Carbonate → HCID 86663047, compound

HRID 2410805Notes

Reaction equation

HRID 2410805 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][C:7](B(O)O)=[CH:6][CH:5]=1)([O-:3])=[O:2].C(=O)([O-])[O-].[Na+].[Na+].[NH2:19][C:20]1[C:29](Br)=[N:28][C:27]([Br:31])=[CH:26][C:21]=1[C:22]([O:24][CH3:25])=[O:23]>>[NH2:19][C:20]1[C:29]([C:7]2[CH:8]=[CH:9][C:4]([N+:1]([O-:3])=[O:2])=[CH:5][CH:6]=2)=[N:28][C:27]([Br:31])=[CH:26][C:21]=1[C:22]([O:24][CH3:25])=[O:23]

Participants

4

Reactant 3

HCID 10340Sodium CarbonateHCID 27735524-Nitrophenylboronic acidHCID 53419616Methyl 3-amino-2,6-dibromoisonicotinate

Product 1

HCID 86663047HCID 86663047, compoundYield 700%

Conditions

Temperature
110 °C

Procedure

A flask containing a mixture of 4-nitrophenylboronic acid (5.5 g, 32 9 mmol), sodium carbonate (10.3 g, 97 mmol), tetrakistriphenyphosphine palladium(0) (1.86 g, 1.61 mmol), and methyl 3-amino-2,6-dibromoisonicotinate (10 g, 32 3 mmol) was flushed with nitrogen, 1,4-dioxane (60.0 mL) followed by methanol (20 mL) were added, and the reaction heated at 110° C. for 16 h. The reaction mixture was partitioned between EtOAc and water. The organic phase was washed with sat. aq. Sodium bicarbonate solution and brine, dried with sodium sulfate, and the solvents removed. The residue was suspended and a mixture of EtOAc:hexane=1:4 and then filtered to give methyl 3-amino-6-bromo-2-(4-nitrophenyl)isonicotinate (9.3 g, 21 mmol, 66% yield). MS (ESI) m/z 354.04 (M+H). 1H NMR (500 MHz, chloroform-d) δ ppm 8.37 (2 H, d, J=8.85 Hz), 7.91 (1H, s), 7.88 (2H, d, J=8.85 Hz), 5.98 (2H, br. s.), 3.98 (3H, s).

Workup

  1. additionA flask containing
  2. customwas flushed with nitrogen, 1,4-dioxane (60.0 mL)
  3. additionwere added
  4. customThe reaction mixture was partitioned between EtOAc and water
  5. washThe organic phase was washed with sat. aq. Sodium bicarbonate solution and brine
  6. dry with materialdried with sodium sulfate
  7. customthe solvents removed
  8. additiona mixture of EtOAc
  9. filtrationhexane=1:4 and then filtered

Sources & evidence

ORD record
ord-b224ad0b64e24d82ab9028309b609e70
Source dataset
uspto-grants-2014_08
Patent number
US08815840B2

Reaction notes

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