Sodium Bicarbonate → HCID 58504760, compound

HRID 2367191Notes

Reaction equation

HRID 2367191 reaction equation
Cl[C:2]1[N:7]=[C:6]([NH2:8])[N:5]=[C:4]([NH:9][CH:10]2[CH2:15][CH2:14][CH2:13][CH2:12][CH2:11]2)[CH:3]=1.[C:16]([C:18]1[CH:23]=[CH:22][C:21](B(O)O)=[CH:20][C:19]=1[F:27])#[N:17].C([O-])(O)=O.[Na+]>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.O1CCOCC1>[NH2:8][C:6]1[N:7]=[C:2]([C:21]2[CH:22]=[CH:23][C:18]([C:16]#[N:17])=[C:19]([F:27])[CH:20]=2)[CH:3]=[C:4]([NH:9][CH:10]2[CH2:15][CH2:14][CH2:13][CH2:12][CH2:11]2)[N:5]=1

Participants

6

Reactant 3

HCID 516892Sodium BicarbonateHCID 2783130(4-Cyano-3-fluorophenyl)boronic acidHCID 21433275HCID 21433275, compound

Product 1

HCID 58504760HCID 58504760, compoundYield 37.6%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
95 °C

Procedure

In a 25 mL sealable tube under nitrogen were combined 6-chloro-N4-cyclohexyl-2,4-pyrimidinediamine (0.75 g, 3.31 mmol) and (4-cyano-3-fluorophenyl)boronic acid (0.546 g, 3.31 mmol) followed by 1,4-dioxane (13.2 mL) and saturated aqueous NaHCO3 (3.3 mL). The resulting mixture was degassed with nitrogen for 5 minutes. Pd(Ph3P)4 (0.19 g, 0.165 mmol) was added, the vial was sealed, and the reaction mixture was stirred for 16 hours at 95° C. The reaction was cooled to room temperature, decanted, and concentrated. The resulting orange oil was partitioned between EtOAc and water. The organic layer was separated, washed with brine, dried (MgSO4), filtered and concentrated. To the resulting yellow solid was added CH3CN (5 mL), and the mixture was sonicated. Filtration of the solid and washing with minimal CH3CN afforded the title compound (387 mg, 36%) as a light tan solid. LC-MS (ES) m/z=312 [M+H]+.

Workup

  1. customIn a 25 mL sealable tube under nitrogen were combined
  2. customThe resulting mixture was degassed with nitrogen for 5 minutes
  3. customthe vial was sealed
  4. temperatureThe reaction was cooled to room temperature
  5. customdecanted
  6. concentrationconcentrated
  7. customThe resulting orange oil was partitioned between EtOAc and water
  8. customThe organic layer was separated
  9. washwashed with brine
  10. dry with materialdried (MgSO4)
  11. filtrationfiltered
  12. concentrationconcentrated
  13. additionTo the resulting yellow solid was added CH3CN (5 mL)
  14. customthe mixture was sonicated
  15. filtrationFiltration of the solid
  16. washwashing with minimal CH3CN

Sources & evidence

ORD record
ord-50baa7b30e654050b4dfa71121770acb
Source dataset
uspto-grants-2014_04
Patent number
US08697685B2

Reaction notes

Loading…