Hydrochloric Acid → HCID 67979568, compound

HRID 539293Notes

Reaction equation

HRID 539293 reaction equation
[Li]CCCC.Br[C:7]1[CH:8]=[N:9][CH:10]=[C:11]([C:13]#[C:14][CH2:15][CH3:16])[CH:12]=1.[B:17](OC(C)C)([O:22]C(C)C)[O:18]C(C)C.Cl.[OH-].[Na+]>CCOC(C)=O>[C:13]([C:11]1[CH:12]=[C:7]([B:17]([OH:22])[OH:18])[CH:8]=[N:9][CH:10]=1)#[C:14][CH2:15][CH3:16]

Participants

7

Reactant 5

HCID 313Hydrochloric AcidHCID 14798Sodium HydroxideHCID 21531Triisopropyl borateHCID 67979408HCID 67979408, compound2×HCID 178418339Butyllithium

Product 1

HCID 67979568HCID 67979568, compoundYield 76.3%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

n-BuLi (2.5 M in hexanes, 5.46 mL, 13.7 mmol) was added dropwise to a solution of 3-bromo-5-(but-1-ynyl)pyridine (Intermediate 48, 2.39 g, 11.4 mmol) and triisopropyl borate (3.15 mL, 13.65 mmol) in 2-Me THF (20 mL) at −50° C. The mixture was stirred for 1.5 h while the temperature was kept between −50 and −40° C. The mixture was lifted up from the cooling bath and 2 M aq. HCl (12 mL, 24 mmol) was added followed by stirring for 20 min. The mixture was diluted with EtOAc. Aq. NaOH (2 M) was added until pH about 12 was obtained in the aqueous phase. The phases were separated. The organic phase was extracted with dilute aq. NaOH and with water. The combined aqueous phases were washed with EtOAc, acidified to pH about 5 by the addition of conc. HCl and extracted with DCM. The organic phase was dried over Na2SO4 and concentrated to give 1.522 g (76% yield) of the title compound: 1H NMR (500 MHz, CDCl3) δ ppm 1.11-1.37 (m, 3 H), 2.26-2.58 (m, 2 H), 7.46-10.34 (m, 3 H); MS (ES+) m/z 176 [M+H]+.

Workup

  1. customwas kept between −50 and −40° C
  2. additionwas added
  3. stirringby stirring for 20 min
  4. customwas obtained in the aqueous phase
  5. customThe phases were separated
  6. extractionThe organic phase was extracted with dilute aq. NaOH and with water
  7. washThe combined aqueous phases were washed with EtOAc
  8. additionacidified to pH about 5 by the addition of conc. HCl
  9. extractionextracted with DCM
  10. dry with materialThe organic phase was dried over Na2SO4
  11. concentrationconcentrated

Sources & evidence

ORD record
ord-4b441e1023bd40018c84e7fb65fb5d06
Source dataset
uspto-grants-2014_10
Patent number
US08865911B2

Reaction notes

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