Hydrochloric Acid → HCID 11845937, compound

HRID 424361Notes

Reaction equation

HRID 424361 reaction equation
Br[C:2]1[CH:3]=[N:4][CH:5]=[CH:6][CH:7]=1.C([Mg]Cl)(C)C.[F:13][C:14]1[CH:19]=[CH:18][C:17]([B:20]2[O:24][CH2:23]CO2)=[C:16](COCOC)[CH:15]=1.Cl>C1COCC1.O>[F:13][C:14]1[CH:15]=[CH:16][C:17]2[B:20]([C:2]3[CH:3]=[N:4][CH:5]=[CH:6][CH:7]=3)[O:24][CH2:23][C:18]=2[CH:19]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 122863-BromopyridineHCID 11845574HCID 11845574, compoundHCID 178418918HCID 178418918, compound

Product 1

HCID 11845937HCID 11845937, compoundYield 7.7%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of 3-bromopyridine (731 mg, 4.63 mmol) in THF (5 mL) was added isopropylmagnesium chloride (1 M in THF; 2.3 mL) at room temperature under nitrogen atmosphere, and the mixture was stirred for 1 h. To the mixture was added compound 6 (1.11 g, 4.63 mmol) in THF (4 mL), and the mixture was stirred at room temperature overnight. Water was added and the pH was adjusted to 7 with 1 N HCl. Then the mixture was extracted with ethyl acetate. The solvent was removed under reduced pressure, and the residue was dissolved in THF (30 mL). To the mixture was added 1 N HCl (10 mL), and the mixture was refluxed overnight. The pH was adjusted to 7 with aqueous NaHCO3 and the mixture was extracted with ethyl acetate. The organic layer was washed with brine and dried over anhydrous Na2SO4. The solvent was removed under reduced pressure and the residue was recrystallized from i-Pr2O to afford compound 15 (76 mg, 7.7%): mp 210-212° C.; 1H NMR (300 MHz, DMSO-d6) δ 4.94 (s, 2H), 6.9-7.1 (m, 2H), 7.36 (br s, 1H), 7.66 (dd, J=6.7, 5.3 Hz, 1H), 8.19 (d, J=6.7 Hz, 1H), 8.24 (br s, 1H), 8.64 (d, J=5.3 Hz, 1H): ESI-MS m/z 214 (M+H)+; Anal (C12H9BFNO.0.6H2O)C, H, N.

Workup

  1. stirringthe mixture was stirred at room temperature overnight
  2. extractionThen the mixture was extracted with ethyl acetate
  3. customThe solvent was removed under reduced pressure
  4. dissolutionthe residue was dissolved in THF (30 mL)
  5. additionTo the mixture was added 1 N HCl (10 mL)
  6. temperaturethe mixture was refluxed overnight
  7. extractionthe mixture was extracted with ethyl acetate
  8. washThe organic layer was washed with brine
  9. dry with materialdried over anhydrous Na2SO4
  10. customThe solvent was removed under reduced pressure
  11. customthe residue was recrystallized from i-Pr2O

Sources & evidence

ORD record
ord-fac23bcc60c14f7c999eb19bfb042314
Source dataset
uspto-grants-2012_01
Patent number
US08106031B2

Reaction notes

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