Pyridine → HCID 89713714, compound

HRID 1518978Notes

Reaction equation

HRID 1518978 reaction equation
[N:1]1[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[Cu](C#N)C#N.[Br-].[Li+].[C:14](Cl)(=[O:22])[O:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1.Br[Zn][CH:26]1[CH2:29][CH2:28][CH2:27]1.C([O-])(O)=O.[Na+]>C1COCC1.C(OCC)C>[CH:26]1([CH:4]2[CH:5]=[CH:6][N:1]([C:14]([O:15][C:16]3[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=3)=[O:22])[CH:2]=[CH:3]2)[CH2:29][CH2:28][CH2:27]1

Participants

9

Reactant 6

HCID 1049PyridineHCID 15891Phenyl chloroformateHCID 82050Lithium BromideHCID 516892Sodium BicarbonateHCID 178418260HCID 178418260, compoundHCID 178419767HCID 178419767, compound

Product 1

HCID 89713714HCID 89713714, compoundYield 87.7%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

Mix pyridine (3.0 mL, 37.5 mmol), copper cyanide (0.23 g, 2.50 mmol) and lithium bromide (0.44 g, 5.0 mmol) in THF (100 mL) at ambient temperature. Add phenyl carbonochloridate (3.91 g, 25.0 mmol) dropwise, and stir the mixture for 15 minutes. Add bromo(cyclobutyl)zinc (50 mL, 25.0 mmol) dropwise, and stir the mixture for 5 hours at ambient temperature. Add NaHCO3 (aq.) and 100 mL diethyl ether. Separate layers and extract the aqueous portion twice more with diethyl ether. Combine the organic portions and sequentially wash with 20% aqueous NH4Cl, [20% NH4Cl/20% NH4OH (1:1)] then brine; dry over sodium sulfate; filter; and collect the filtrate. Concentrate under reduced pressure to give the title compound (5.6 g, 85.5%). MS (m/z): 256 (M+1).

Workup

  1. extractionSeparate layers and extract the aqueous portion twice more with diethyl ether
  2. washsequentially wash with 20% aqueous NH4Cl, [20% NH4Cl/20% NH4OH (1:1)]
  3. dry with materialdry over sodium sulfate
  4. filtrationfilter
  5. customand collect the filtrate
  6. concentrationConcentrate under reduced pressure

Sources & evidence

ORD record
ord-4b43640d9cfe46449948e61268e44da7
Source dataset
uspto-grants-2015_07
Patent number
US09073856B2

Reaction notes

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