Hydrochloric Acid → 4-Chloro-3,5-difluoropicolinaldehyde

HRID 1522565Notes

Reaction equation

HRID 1522565 reaction equation
[Cl:1][C:2]1[C:7]([F:8])=[CH:6][N:5]=[C:4]([C:9](OCC)=[O:10])[C:3]=1[F:14].CC(C[AlH]CC(C)C)C.Cl.C([O-])(O)=O.[Na+]>C1(C)C=CC=CC=1>[Cl:1][C:2]1[C:7]([F:8])=[CH:6][N:5]=[C:4]([CH:9]=[O:10])[C:3]=1[F:14]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 14487Diisobutylaluminum hydrideHCID 516892Sodium BicarbonateHCID 67469638Ethyl 4-chloro-3,5-difluoropicolinate

Product 1

HCID 848197844-Chloro-3,5-difluoropicolinaldehydeYield 96%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a solution of ethyl 4-chloro-3,5-difluoropicolinate (1.5 g, 6.77 mmol) in toluene (25 mL) at −78° C. was added DIBAL (6.77 mL, 6.77 mmol) and the mixture was stirred for 4 hours. Then 3N HCl solution (20 mL) was added slowly and the mixture was allowed to warm to room temperature. After 1 hour, a saturated solution of NaHCO3 was added and the mixture was extracted with Et2O (2×150 mL). The combined organics were dried over Na2SO4 and evaporated to give 4-chloro-3,5-difluoropicolinaldehyde (1.15 g, 6.48 mmol, 96% yield) as a yellow liquid which was used in next step without further purification. MS [M+H] found 178.0.

Workup

  1. waitAfter 1 hour
  2. extractionthe mixture was extracted with Et2O (2×150 mL)
  3. dry with materialThe combined organics were dried over Na2SO4
  4. customevaporated

Sources & evidence

ORD record
ord-a137d51109474907b73fc7455e47a9f7
Source dataset
uspto-grants-2015_07
Patent number
US09073918B2

Reaction notes

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