Ammonium Chloride → 4,4'-Bis(hydroxymethyl)-2,2'-bipyridine

HRID 2301250Notes

Reaction equation

HRID 2301250 reaction equation
C([O:3][C:4]([C:6]1[CH:11]=[CH:10][N:9]=[C:8]([C:12]2[CH:17]=[C:16]([C:18](OCC)=[O:19])[CH:15]=[CH:14][N:13]=2)[CH:7]=1)=O)C.[BH4-].[Na+].[Cl-].[NH4+].[BH4-]>C(O)C>[OH:19][CH2:18][C:16]1[CH:15]=[CH:14][N:13]=[C:12]([C:8]2[CH:7]=[C:6]([CH2:4][OH:3])[CH:11]=[CH:10][N:9]=2)[CH:17]=1

Participants

6

Reactant 4

HCID 25517Ammonium ChlorideHCID 28123BorohydrideHCID 4311764Sodium borohydrideHCID 12088573Diethyl [2,2'-bipyridine]-4,4'-dicarboxylate

Product 1

HCID 111602394,4'-Bis(hydroxymethyl)-2,2'-bipyridineYield 80%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

To a suspension of the diester (1) (3.0 g, 10.0 mmol) in 200 mL of absolute ethanol, 8.2 g of sodium borohydride was added in one portion. The mixture was refluxed for 3 hours, cooled to room temperature, then 200 mL of a saturated aqueous solution of ammonium chloride was added to decompose the excess borohydride. The ethanol was removed and the precipitated solid was dissolved with a minimum amount of water. The resulting solution was extracted with ethyl acetate (5×200 mL) then dried over sodium sulfate and rotary-evaporated. The 1.7 g (80% yield) of solid (2) thus obtained was used without further purification. 1H NMR (300 MHz, CD3OD) δ ppm: 4.75 (4H, s, 2CH2OH), 7.43 (2H, d, 3JHH=6 Hz, aryl H on C5 and C5′), 8.25 (2H, s, aryl H on C3 and C3′), 9.00 (2H, d, 3JHH=6 Hz, aryl H on C6 and C6′). Elemental analysis of C12H12N2O2: calcd. C 66.65, H 5.59, N 12.95%, found C 65.90, H 5.70, N 12.32%.

Workup

  1. additionwas added in one portion
  2. temperatureThe mixture was refluxed for 3 hours
  3. customThe ethanol was removed
  4. dissolutionthe precipitated solid was dissolved with a minimum amount of water
  5. extractionThe resulting solution was extracted with ethyl acetate (5×200 mL)
  6. dry with materialthen dried over sodium sulfate
  7. customrotary-evaporated

Sources & evidence

ORD record
ord-ea186fc40bc84a75bd5ae701905265fa
Source dataset
uspto-grants-2002_12
Patent number
US06500510B1

Reaction notes

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