Ammonium Chloride → HCID 58360364, compound

HRID 2060743Notes

Reaction equation

HRID 2060743 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([Br:8])=[CH:4][N:3]=1.[Li]CCCC.[CH:14]([C:16]1[CH:17]=[C:18]([C:27]([O:29][CH2:30][CH3:31])=[O:28])[C:19](=[O:26])[N:20]2[C:25]=1[CH:24]=[CH:23][CH:22]=[CH:21]2)=[O:15].[Cl-].[NH4+]>C1(C)C=CC=CC=1>[Br:8][C:5]1[CH:6]=[CH:7][C:2]([CH:14]([OH:15])[C:16]2[CH:17]=[C:18]([C:27]([O:29][CH2:30][CH3:31])=[O:28])[C:19](=[O:26])[N:20]3[C:25]=2[CH:24]=[CH:23][CH:22]=[CH:21]3)=[N:3][CH:4]=1

Participants

6

Reactant 4

HCID 25517Ammonium ChlorideHCID 693532,5-DibromopyridineHCID 20634151Ethyl 1-formyl-4-oxo-4H-quinolizine-3-carboxylateHCID 178418339Butyllithium

Product 1

HCID 58360364HCID 58360364, compound

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
-78 °C

Procedure

To a solution of 2,5-dibromopyridine (1.00 g, 4.22 mmol) in 50 mL of toluene at −78° C. was added n-BuLi (2.0 mL, 5.0 mol, 2.5 M in THF) dropwise. After 2 h, ethyl 1-formyl-4-oxo-4H-quinolizine-3-carboxylate (1.35 g, 5.5 mmol) was added. The reaction was stirred at −78° C. for another 1 h, then transferred to a 0° C. ice water bath. After an additional 1 h at 0° C., saturated aqueous ammonium chloride (10 mL) was added. The mixture was warmed to rt and filtered to remove an insoluble brown solid. The filtrate was separated, and the organic layer was dried over sodium sulfate, filtered, and concentrated in vacuo. The resultant residue was subjected to purification via silica gel chromatography from 0-5% MeOH in CH2Cl2 to yield crude ethyl 1-[(5-bromopyridin-2-yl)(hydroxy)methyl]-4-oxo-4H-quinolizine-3-carboxylate that gave a mass ion (ES+) of 402.9 (79Br) for M+H+.

Workup

  1. customtransferred to a 0° C.
  2. waitAfter an additional 1 h at 0° C.
  3. temperatureThe mixture was warmed to rt
  4. filtrationfiltered
  5. customto remove an insoluble brown solid
  6. customThe filtrate was separated
  7. dry with materialthe organic layer was dried over sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customThe resultant residue was subjected to purification via silica gel chromatography from 0-5% MeOH in CH2Cl2

Sources & evidence

ORD record
ord-f62726cc7bb445c9b3d517d1f35fb70d
Source dataset
uspto-grants-2012_10
Patent number
US08278453B2

Reaction notes

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