Sulfuric Acid → 5-Bromo-3-pyridinecarboxaldehyde

HRID 490969Notes

Reaction equation

HRID 490969 reaction equation
[H-].[Al+3].[Li+].[H-].[H-].[H-].C(OCC)(=O)C.N1(C(N)=O)CCOCC1.[Br:22][C:23]1[CH:24]=[C:25]([C:29](O)=[O:30])[CH:26]=[N:27][CH:28]=1.S(=O)(=O)(O)O>C1COCC1>[Br:22][C:23]1[CH:28]=[N:27][CH:26]=[C:25]([CH:24]=1)[CH:29]=[O:30]

Participants

6

Reactant 4

HCID 1118Sulfuric AcidHCID 8857Ethyl AcetateHCID 21226445Aluminium lithium hydrideHCID 695284275-Bromonicotinic acid morpholinamide

Product 1

HCID 27847345-Bromo-3-pyridinecarboxaldehydeYield 68.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

1.75 g of lithium aluminium hydride powder are suspended in 64 g of THF. A mixture of 5.9 g of ethyl acetate and 28 g of THF is subsequently added dropwise with cooling. After 30 minutes, this reaction mixture is added dropwise at 0° C. to 10° C. to a solution of 5.0 g of 5-bromopyridine-3-carboxylic acid morpholinamide from Example 3(a) in 30 g of THF (this corresponds to 150% excess of the reducing agent). After 1 hour, the reaction mixture is poured into 35 ml of 12% sulfuric acid, and the organic phase is evaporated to dryness. Recrystallisation from MTB ether and drying gives 1.91 g of product (=55.7% of theory). Melting point 95° C.

Workup

  1. additionis subsequently added dropwise
  2. temperaturewith cooling
  3. waitAfter 1 hour
  4. customthe organic phase is evaporated to dryness
  5. customRecrystallisation from MTB ether
  6. customdrying

Sources & evidence

ORD record
ord-a7c0dbcd863f4cd3bee8ed9a01153f4f
Source dataset
uspto-grants-2009_05
Patent number
US07528256B2

Reaction notes

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