Methanesulfonic Acid → 7-bromo-8-fluoro-3-(3-methoxy-3-methylbut-1-ynyl)-5'H-spiro[chromeno[2,3-b]pyridine-5,4'-oxazol]-2'-amine

HRID 335893Notes

Reaction equation

HRID 335893 reaction equation
[NH2:1][C:2]1[O:3][CH2:4][C:5]2([C:19]3[C:14](=[N:15][CH:16]=[C:17]([C:20]#[C:21][C:22]([CH3:25])([OH:24])[CH3:23])[CH:18]=3)[O:13][C:12]3[C:7]2=[CH:8][C:9]([Br:27])=[C:10]([F:26])[CH:11]=3)[N:6]=1.[CH3:28]S(O)(=O)=O.C([O-])(O)=O.[Na+]>CO>[Br:27][C:9]1[CH:8]=[C:7]2[C:5]3([CH2:4][O:3][C:2]([NH2:1])=[N:6]3)[C:19]3[C:14](=[N:15][CH:16]=[C:17]([C:20]#[C:21][C:22]([O:24][CH3:28])([CH3:23])[CH3:25])[CH:18]=3)[O:13][C:12]2=[CH:11][C:10]=1[F:26]

Participants

5

Reactant 3

HCID 6395Methanesulfonic AcidHCID 516892Sodium BicarbonateHCID 673829024-(2'-amino-7-bromo-8-fluoro-5'H-spiro[chromeno[2,3-b]pyridine-5,4'-oxazole]-3-yl)-2-methylbut-3-yn-2-ol

Product 1

HCID 673873667-bromo-8-fluoro-3-(3-methoxy-3-methylbut-1-ynyl)-5'H-spiro[chromeno[2,3-b]pyridine-5,4'-oxazol]-2'-amine

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

A solution of 4-(2′-amino-7-bromo-8-fluoro-5′H-spiro[chromeno[2,3-b]pyridine-5,4′-oxazole]-3-yl)-2-methylbut-3-yn-2-ol (0.580 g, 1.342 mmol) in 10 mL MeOH was treated with methanesulfonic acid (0.871 mL, 13.42 mmol). The resulting solution was allowed to stir at RT for 72 hours and was then heated at 85° C. for 3 hours. The reaction mixture was poured into saturated NaHCO3 (50 mL) and was extracted with EtOAc (3×25 mL). The organics were washed with brine, dried over MgSO4 and concentrated in vacuo. Purification of the crude residue by column chromatgraphy [0-100% (95:5 EtOAc/MeOH)/CH2Cl2] afforded 7-bromo-8-fluoro-3-(3-methoxy-3-methylbut-1-ynyl)-5′H-spiro[chromeno[2,3-b]pyridine-5,4′-oxazol]-2′-amine

Workup

  1. temperaturewas then heated at 85° C. for 3 hours
  2. extractionwas extracted with EtOAc (3×25 mL)
  3. washThe organics were washed with brine
  4. dry with materialdried over MgSO4
  5. concentrationconcentrated in vacuo
  6. customPurification of the crude residue by column chromatgraphy [0-100% (95:5 EtOAc/MeOH)/CH2Cl2]

Sources & evidence

ORD record
ord-1cf39d7711c4452eafa8b92bf93d7518
Source dataset
uspto-grants-2014_11
Patent number
US08883782B2

Reaction notes

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