Benzene → Alpha-tocopherol 5-n-butyl-2-pyridinecarboxylate

HRID 325932

Reaction equation

HRID 325932 reaction equation
C1C=CC=CC=1.[CH2:7]([C:11]1[CH:12]=[CH:13][C:14]([C:17]([OH:19])=[O:18])=[N:15][CH:16]=1)[CH2:8][CH2:9][CH3:10].S(Cl)(Cl)=O.[CH3:24][C:25]1[C:34]([CH3:35])=[C:33]2[C:28]([CH2:29][CH2:30][C:31]([CH2:37][CH2:38][CH2:39][CH:40]([CH2:42][CH2:43][CH2:44][CH:45]([CH2:47][CH2:48][CH2:49][CH:50]([CH3:52])[CH3:51])[CH3:46])[CH3:41])([CH3:36])[O:32]2)=[C:27]([CH3:53])[C:26]=1O>N1C=CC=CC=1>[CH3:10][CH2:9][CH2:8][CH2:7][C:11]1[CH:12]=[CH:13][C:14]([C:17]([O:19][C:26]2[C:27]([CH3:53])=[C:28]3[CH2:29][CH2:30][C:31]([CH2:37][CH2:38][CH2:39][CH:40]([CH2:42][CH2:43][CH2:44][CH:45]([CH2:47][CH2:48][CH2:49][CH:50]([CH3:52])[CH3:51])[CH3:46])[CH3:41])([CH3:36])[O:32][C:33]3=[C:34]([CH3:35])[C:25]=2[CH3:24])=[O:18])=[N:15][CH:16]=1

Participants

6

Reactant 4

HCID 241Benzene3×HCID 2116DL-alpha-TocopherolHCID 3442Fusaric AcidHCID 24386Thionyl Chloride2×

Product 1

HCID 134999Alpha-tocopherol 5-n-butyl-2-pyridinecarboxylateYield 46.6%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Conditions

Temperature
0 °C

Procedure

Ten milliliters of benzene was added to 4.51 g of 5-butylpicolinic acid, and 9 g of thionyl chloride was further added. The mixture was heated under reflux for 22 minutes. The excess of thionyl chloride and benzene were disiled off under reduced pressure, and 10 ml of benzene was added to the residue. The mixture was cooled to 0° C. and stirred. To the solution was added dropwise a solution of 5 g of dl-α-tocopherol in 4.25 ml of pyridine to perform the reaction for 1 hour and 40 minutes. The insoluble matter was removed by filtration from the reaction mixture, and the residue was washed with water, 1 N hydrochloric acid, water, a saturated aqueous solution of sodium bicarbonate and a saturated aqueous solution of sodium chloride in this order. Benzene was distilled off, and the residue was chromatographed on a silica gel column using benzene/ethyl acetate (4:1) as an eluent to give 3.2 g of dl-α-tocopheryl 5-butylpicolinate.

Workup

  1. additionwas further added
  2. temperatureThe mixture was heated
  3. temperatureunder reflux for 22 minutes
  4. additionwas added to the residue
  5. customthe reaction for 1 hour
  6. custom40 minutes
  7. customThe insoluble matter was removed by filtration from the reaction mixture
  8. washthe residue was washed with water, 1 N hydrochloric acid, water
  9. distillationBenzene was distilled off
  10. customthe residue was chromatographed on a silica gel column

Sources & evidence

ORD record
ord-e84cd651b4b24211a96cb2372b7b515a
Source dataset
uspto-grants-1984_04
Patent number
US04443459

Linked notes

Loading…