Lithium Chloride → 3-Amino-5-fluoropyridine-2-carbaldehyde

HRID 473426Notes

Reaction equation

HRID 473426 reaction equation
[O:1]1CCO[CH:2]1[C:6]1[C:11]([NH2:12])=[CH:10][C:9]([F:13])=[CH:8][N:7]=1.[Cl-].[Li+]>CS(C)=O.O>[NH2:12][C:11]1[C:6]([CH:2]=[O:1])=[N:7][CH:8]=[C:9]([F:13])[CH:10]=1

Participants

4

Reactant 2

HCID 433294Lithium ChlorideHCID 583186212-(1,3-Dioxolan-2-yl)-5-fluoropyridin-3-amine

Product 1

HCID 583186473-Amino-5-fluoropyridine-2-carbaldehyde

Reagents, catalysts & solvents 1

HCID 23503278(Methanesulfinyl)methane--water (1/1)Solvent

Conditions

Temperature
90 °C

Procedure

To a solution of 2-(1,3-dioxolan-2-yl)-5-fluoropyridin-3-amine (5 g, 27.14 mmol) in DMSO: H2O (1:1) (162 mL) was added lithium chloride (6.9 g, 162.89 mmol). The reaction mixture was heated to 90° C. for 16 h and water was removed using dean-stark apparatus. Water was added to the reaction mass and extracted with EtOAc. Organic layer was washed with brine and dried over Na2SO4. The organic layer was concentrated in vacuo and purified by column chromatography on silica gel using 0-40% EtOAc in hexane to give 3-amino-5-fluoropicolinaldehyde: 1H NMR (400 MHz, DMSO-d6): δ 7.003-7.037 (m, 1H), 7.387 (br s, 2H), 7.944 (d, 1H, J=2.4 Hz), 9.853 (s, 1H); LC-MS (ESI) m/z 141.0 [M+H]+.

Workup

  1. customwater was removed
  2. additionWater was added to the reaction mass
  3. extractionextracted with EtOAc
  4. washOrganic layer was washed with brine
  5. dry with materialdried over Na2SO4
  6. concentrationThe organic layer was concentrated in vacuo
  7. custompurified by column chromatography on silica gel using 0-40% EtOAc in hexane

Sources & evidence

ORD record
ord-97d93b7e09de48a884b2c372325e862f
Source dataset
uspto-grants-2014_01
Patent number
US08633313B2

Reaction notes

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