Hydrochloric Acid → 2-Furyl-(3,4-dimethyl-2-pyridyl)-carbinol

HRID 46669Notes

Reaction equation

HRID 46669 reaction equation
C([Li])CCC.Br[C:7]1[C:12]([CH3:13])=[C:11]([CH3:14])[CH:10]=[CH:9][N:8]=1.[CH:15](=[O:21])[C:16]1[O:20][CH:19]=[CH:18][CH:17]=1.Cl.[OH-].[Na+]>CCOCC>[O:20]1[CH:19]=[CH:18][CH:17]=[C:16]1[CH:15]([C:7]1[C:12]([CH3:13])=[C:11]([CH3:14])[CH:10]=[CH:9][N:8]=1)[OH:21]

Participants

7

Reactant 5

HCID 313Hydrochloric AcidHCID 7362FurfuralHCID 14798Sodium HydroxideHCID 218222912-Bromo-3,4-dimethylpyridineHCID 178418339Butyllithium

Product 1

HCID 199854622-Furyl-(3,4-dimethyl-2-pyridyl)-carbinolYield 24%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent3×

Conditions

Temperature
-40 °C

Procedure

To 120 ml of a 0.74 M ether solution of butyl-lithium, there is slowly added under nitrogen atmosphere a solution of 10 g of 2-bromo-3,4-dimethylpyridine in 25 ml of anhydrous ether, the temperature being maintained at -40° C. Once the addition is concluded stirring is continued for one hour and 30 minutes, maintaining the same temperature. The temperature is increased to -25° C. and a solution of 5.3 ml of recently distilled furfural in 10 ml of anhydrous ether is added dropwise, following which the temperature is increased to -15° C. and the mixture is stirred for one hour. The reaction mixture is poured over 10% hydrochloric acid to acid pH, cooling from the exterior with ice. The aqueous layer is made alkaline with 10% sodium hydroxide, is cooled from the exterior and is extracted with ether. The ether layer is dried over anhydrous sodium sulphate, filtered and evaporated to dryness, the result being 4.9 g of an oil which is purified by filtration through a silica gel column. The fractions eluated with 95/5 and 70/30 proportions of benzene/chloroform, are collected to obtain 2.65 g (Yield 24%) of 2-furyl-(3,4-dimethyl-2-pyridyl)-carbinol (I). An analytical sample recrystallized from ethyl alcohol has a melting point of 61°-62° C. Calculated analysis for C12H13NO2 : C.70.91; H.6.45; N.6.89. Found: C.70.65; H.6.45; N. 6.88.

Workup

  1. additionOnce the addition
  2. temperaturemaintaining the same temperature
  3. temperatureThe temperature is increased to -25° C.
  4. temperatureis increased to -15° C.
  5. stirringthe mixture is stirred for one hour
  6. temperaturecooling from the exterior with ice
  7. temperatureis cooled from the exterior and
  8. extractionis extracted with ether
  9. dry with materialThe ether layer is dried over anhydrous sodium sulphate
  10. filtrationfiltered
  11. customevaporated to dryness
  12. filtrationis purified by filtration through a silica gel column
  13. customare collected

Sources & evidence

ORD record
ord-06f5586e829a4092998befb915d901b9
Source dataset
uspto-grants-1979_11
Patent number
US04174451

Reaction notes

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