Diethyl Ether → Di-3-pyridinylmethanone

HRID 1780885Notes

Reaction equation

HRID 1780885 reaction equation
Br[C:2]1[CH:3]=[N:4][CH:5]=[CH:6][CH:7]=1.[CH2:8]([Li])[CH2:9][CH2:10][CH3:11].[CH3:13][N:14](OC)[C:15](OCC)=O.CC[O:24]CC>>[N:4]1[CH:5]=[CH:6][CH:7]=[C:2]([C:8]([C:9]2[CH:13]=[N:14][CH:15]=[CH:11][CH:10]=2)=[O:24])[CH:3]=1

Participants

5

Reactant 4

HCID 3283Diethyl Ether2×HCID 122863-BromopyridineHCID 533715Ethyl N-methoxy-N-methylcarbamateHCID 178418339Butyllithium

Product 1

HCID 298471Di-3-pyridinylmethanoneYield 33%

Procedure

To a solution of 3-bromopyridine (9.84 g, 0.062 mol) in 300 mL of ether cooled to -78° C. was added n-butyllithium (1.6M, 41 mL, 0.066 mol) and stirred for 30 min. N-Methyl,N-methoxy-urethane (3.76 g, 0.028 mol) in 20 mL of ether was added in 10 min, the mixture was stirred (-78° C.) for 1 h, allowed to warm to room temperature and stirred for 2 h. The reaction mixture was quenched with 6 N HCl (100 mL) and stirred. The aqueous layer was basified with 10% NaOH solution, extracted with ethyl acetate (2x) and methylene dichloride. The organic layer was dried over sodium sulfate, concentrated in vacuo, and the residue was purified by chromatography on silica (ethyl acetate, 10% methanol/ethyl acetate) to afford 1.7 g (33%) of di-(3-pyridyl)ketone.

Workup

  1. stirringthe mixture was stirred (-78° C.) for 1 h
  2. stirringstirred for 2 h
  3. customThe reaction mixture was quenched with 6 N HCl (100 mL)
  4. stirringstirred
  5. extractionextracted with ethyl acetate (2x) and methylene dichloride
  6. dry with materialThe organic layer was dried over sodium sulfate
  7. concentrationconcentrated in vacuo
  8. customthe residue was purified by chromatography on silica (ethyl acetate, 10% methanol/ethyl acetate)

Sources & evidence

ORD record
ord-4a2717cd7df54fff82247e99f00907ca
Source dataset
uspto-grants-1997_05
Patent number
US05631264

Reaction notes

Loading…