Triethylamine → 6-Bromo-3-pyridinemethanol

HRID 1296002Notes

Reaction equation

HRID 1296002 reaction equation
[Br:1][C:2]1[CH:10]=[CH:9][C:5]([C:6](O)=[O:7])=[CH:4][N:3]=1.C(N(CC)CC)C.ClC(OCC)=O.[BH4-].[Na+]>O1CCCC1.O>[Br:1][C:2]1[N:3]=[CH:4][C:5]([CH2:6][OH:7])=[CH:9][CH:10]=1

Participants

7

Reactant 4

HCID 8471TriethylamineHCID 10928Ethyl chloroformateHCID 2389326-Bromonicotinic acidHCID 4311764Sodium borohydride

Product 1

HCID 64212496-Bromo-3-pyridinemethanolYield 74.5%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

After dissolving 6-bromonicotinic acid (65.7 g, 0.325 mol) in tetrahydrofuran (1600 ml), triethylamine (54 ml, 0.39 mol) and ethyl chloroformate (32.6 ml, 0.341 mol) were added while stirring on ice. The mixture was stirred for 20 minutes while cooling on ice, and the white crystals which precipitated upon filtration were removed and washed with tetrahydrofuran. The filtrate was stirred while cooling on ice, and an aqueous solution (211 ml) of sodium borohydride (18.4 g, 0.488 mol) was gradually added dropwise over a period of 30 minutes. After continued stirring for 1 hour and 20 minutes while cooling on ice, 800 ml of water was added and extraction was performed with ethyl acetate (600 ml×2), and then after washing the combined organic layers with brine (300 ml) and drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to yield the title compound (45.5 g, 74.5%). This was used without further purification for the following reaction.

Workup

  1. additionwere added
  2. stirringThe mixture was stirred for 20 minutes
  3. temperaturewhile cooling on ice
  4. customthe white crystals which precipitated upon filtration
  5. customwere removed
  6. washwashed with tetrahydrofuran
  7. stirringThe filtrate was stirred
  8. temperaturewhile cooling on ice
  9. stirringAfter continued stirring for 1 hour and 20 minutes
  10. additionwas added
  11. extractionextraction
  12. washafter washing the combined organic layers with brine (300 ml)
  13. dry with materialdrying over anhydrous magnesium sulfate
  14. distillationthe solvent was distilled off under reduced pressure

Sources & evidence

ORD record
ord-56e1eb8a5aeb40b48b32e8625909b484
Source dataset
uspto-grants-2007_07
Patent number
US07244730B2

Reaction notes

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