Pyridine → HCID 19430000, compound

HRID 1077678Notes

Reaction equation

HRID 1077678 reaction equation
[C:1]([C:3]([C:9]1[CH:14]=[CH:13][C:12]([CH:15]=[CH2:16])=[CH:11][CH:10]=1)([CH2:7][CH3:8])[C:4]([OH:6])=[O:5])#[N:2].C(Cl)(=O)C(Cl)=O.N1C=CC=CC=1.[C:29](O)([CH3:32])([CH3:31])[CH3:30]>C1C=CC=CC=1.CN(C=O)C.C(Cl)Cl>[C:1]([C:3]([C:9]1[CH:14]=[CH:13][C:12]([CH:15]=[CH2:16])=[CH:11][CH:10]=1)([CH2:7][CH3:8])[C:4]([O:6][C:29]([CH3:32])([CH3:31])[CH3:30])=[O:5])#[N:2]

Participants

8

Reactant 4

HCID 1049PyridineHCID 6386tert-ButanolHCID 65578Oxalyl chlorideHCID 19430001HCID 19430001, compound

Product 1

HCID 19430000HCID 19430000, compoundYield 70%

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideCatalystHCID 241BenzeneSolventHCID 6344DichloromethaneSolvent2×

Procedure

To an ice-cooled solution of 2-cyano-2(p-vinylphenyl)-butanoic acid (3 g, 0.014 mol) in benzene (100 mL) was added oxalyl chloride (5.3 g, 0.042 mol). The solution was cooled in an ice-bath and five drops of DMF was added to catalyze the acyl chloride formation. After being stirred at room-temperature for 4 h, all the solvent and excess oxalyl chloride was removed under reduced pressure. The crude acyl chloride was then taken up with small amount of benzene, filtered, concentrated, re-dissolved in CH2Cl2 (10 mL) and cooled in an ice-bath. To the solution, solutions of pyridine (3.2 g 0.042 mol) in CH2Cl2 and tert-butanol (5.2 g, 0.07 mol) in CH2Cl2 (5 mL) were added. After addition, the solution mixture was stirred at room-temperature for 6 h and quenched with diluted HCl (1%, 500-600 mL). The organic layer was separated, washed and saturated K2CO3 and NaCl solutions, dried over anhydrous Na2SO4, concentrated under reduced pressure and purified by liquid chromatography on silica gel with EtOAc-hexanes (1:9) as an eluent to provide an essentially pure product (2.6 g, 70%).

Workup

  1. temperatureThe solution was cooled in an ice-bath
  2. customall the solvent and excess oxalyl chloride was removed under reduced pressure
  3. filtrationfiltered
  4. concentrationconcentrated
  5. dissolutionre-dissolved in CH2Cl2 (10 mL)
  6. temperaturecooled in an ice-bath
  7. additionAfter addition
  8. stirringthe solution mixture was stirred at room-temperature for 6 h
  9. customquenched with diluted HCl (1%, 500-600 mL)
  10. customThe organic layer was separated
  11. washwashed
  12. dry with materialsaturated K2CO3 and NaCl solutions, dried over anhydrous Na2SO4
  13. concentrationconcentrated under reduced pressure
  14. custompurified by liquid chromatography on silica gel with EtOAc-hexanes (1:9) as an eluent

Sources & evidence

ORD record
ord-8f526ca4814f410a96ff19d3ecad43fb
Source dataset
uspto-grants-1996_08
Patent number
US05545509

Reaction notes

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