Sulfuric Acid → (S)-(+)-6-hydroxy-2,5,7,8-tetramethylchroman-2-methanol

HRID 262060Notes

Reaction equation

HRID 262060 reaction equation
O[CH:2]1[C:8]2=[C:9]([CH3:16])[C:10](=[O:15])[C:11]([CH3:14])=[C:12]([CH3:13])[C@:7]32[O:17][C@:4]([CH3:18])([CH2:5][O:6]3)[CH2:3]1.[H][H].S(=O)(=O)(O)O>Cl(O)(=O)(=O)=O.CO>[OH:15][C:10]1[C:9]([CH3:16])=[C:8]2[C:7](=[C:12]([CH3:13])[C:11]=1[CH3:14])[O:17][C@:4]([CH3:18])([CH2:5][OH:6])[CH2:3][CH2:2]2

Participants

6

Reactant 3

HCID 1118Sulfuric AcidHCID 57010753(3S,9aR)-(-)-2,3,4,5,7,9a-hexahydro-5-hydroxy-3,6,8,9-tetramethyl-3,9a-epoxy-1-benzoxepin-7-oneHCID 178418361HCID 178418361, compound2×

Product 1

HCID 9881178(S)-(+)-6-hydroxy-2,5,7,8-tetramethylchroman-2-methanolYield 111.3%

Reagents, catalysts & solvents 2

HCID 24247Perchloric AcidCatalystHCID 887MethanolSolvent

Procedure

A mixture of 0.59 g of (3S,9aR)-(-)-2,3,4,5,7,9a-hexahydro-5-hydroxy-3,6,8,9-tetramethyl-3,9a-epoxy-1-benzoxepin-7-one, 0.7 g of palladium-on-barium sulfate (5% by weight) and 3 drops of concentrated perchloric acid in 20 ml of methanol was hydrogenated with ca 120 ml of hydrogen under normal pressure. Subsequently, 2 ml of 2-N sulfuric acid were added and air was conducted into the mixture for 15 hours. The reaction mixture was again hydrogenated with ca 25 ml of hydrogen. After removal of the catalyst by filtration over Hyflo, the filtrate was treated with dilute sodium bicarbonate solution and extracted with ether. The combined organic phases were dried over magnesium sulfate. After distillation of the solvent on a rotary evaporator, there were obtained 0.62 g of brown crystals, which, for purification, was chromatographed on Kieselgel with acetic ester/toluene (1/1 parts by volume). The resulting (S)-(+)-6-hydroxy-hydroxy-2,5,7,8-tetramethylchroman-2-methanol crystallized from methylene chloride/hexane at a yield of 487 mg; melting point 126.5°- 128.5°.

Workup

  1. customAfter removal of the catalyst
  2. filtrationby filtration over Hyflo
  3. additionthe filtrate was treated with dilute sodium bicarbonate solution
  4. extractionextracted with ether
  5. dry with materialThe combined organic phases were dried over magnesium sulfate
  6. distillationAfter distillation of the solvent
  7. customon a rotary evaporator

Sources & evidence

ORD record
ord-37f964da04a243568c2bab9868639324
Source dataset
uspto-grants-1979_05
Patent number
US04153614

Reaction notes

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