Acetonitrile → HCID 90403870, compound

HRID 1468972Notes

Reaction equation

HRID 1468972 reaction equation
C(=O)([O-])[O-].[Na+].[Na+].CC1(C)C(C)(C)OB([C:15]2[CH:23]=[CH:22][C:18]3=[N:19][O:20][N:21]=[C:17]3[CH:16]=2)O1.[NH2:25][C:26]1[C:31]([F:32])=[C:30](Cl)[N:29]=[C:28]([C:34]([O:36][CH3:37])=[O:35])[C:27]=1[Cl:38].C(#N)C>O.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[NH2:25][C:26]1[C:31]([F:32])=[C:30]([C:15]2[CH:23]=[CH:22][C:18]3=[N:19][O:20][N:21]=[C:17]3[CH:16]=2)[N:29]=[C:28]([C:34]([O:36][CH3:37])=[O:35])[C:27]=1[Cl:38]

Participants

7

Reactant 4

HCID 6342AcetonitrileHCID 10340Sodium CarbonateHCID 22677265Methyl 4-amino-3,6-dichloro-5-fluoropicolinateHCID 467380042,1,3-Benzoxadiazole-5-boronic acid, pinacol ester

Product 1

HCID 90403870HCID 90403870, compoundYield 57.3%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 962WaterSolvent2×

Conditions

Temperature
85 °C

Procedure

Bis(triphenylphosphine)palladium(II) chloride (110 mg, 0.16 mmol) and sodium carbonate (210 mg, 2.0 mmol) were sequentially added to a stirred mixture of ˜60% 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzo[c][1,2,5]oxadiazole (900 mg, 2.2 mmol) and methyl 4-amino-3,6-dichloro-5-fluoropicolinate (480 mg, 2.0 mmol, 1.0 equiv) in a 1:1 mixture of water:acetonitrile (6.8 mL) at 23° C. The resulting brown mixture was heated to 85° C. and stirred for 4 h. The cooled reaction mixture was diluted with water (150 mL) and extracted with dichloromethane (3×80 mL). The combined organic layers were dried (magnesium sulfate), gravity filtered, and concentrated by rotary evaporation. The residue was purified by reverse phase column chromatography (5% acetonitrile to 100% acetonitrile gradient) to afford the title compound as a tan powder (370 mg, 57% yield).

Workup

  1. customat 23° C
  2. customThe cooled reaction mixture
  3. extractionextracted with dichloromethane (3×80 mL)
  4. dry with materialThe combined organic layers were dried (magnesium sulfate), gravity
  5. filtrationfiltered
  6. concentrationconcentrated by rotary evaporation
  7. customThe residue was purified by reverse phase column chromatography (5% acetonitrile to 100% acetonitrile gradient)

Sources & evidence

ORD record
ord-6d66d91456c542769ef773d9d530adae
Source dataset
uspto-grants-2015_04
Patent number
US09006250B2

Reaction notes

Loading…