Benzene → Tetrahydropyranyl ether

HRID 597326Notes

Reaction equation

HRID 597326 reaction equation
[H-].[Na+].CS(C)=O.[Br-].[C:8]([CH2:11][CH2:12][CH2:13][CH2:14][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)([OH:10])=[O:9].S(=O)(=O)(O)[O-:35].[K+].[CH:40]1C=[CH:44][CH:43]=[CH:42][CH:41]=1>>[O:35]1[CH2:44][CH2:43][CH2:42][CH2:41][CH:40]1[O:10][CH:8]1[CH2:11][CH2:12][CH2:13][CH2:14][O:9]1

Participants

6

Reactant 5

HCID 241BenzeneHCID 679Dimethyl Sulfoxide2×HCID 24758Sodium hydrideHCID 161236(4-Carboxybutyl)triphenylphosphonium bromideHCID 516920Potassium bisulfate

Product 1

HCID 263182Tetrahydropyranyl ether

Conditions

Temperature
20 °C

Procedure

Sodium hydride (0.57 g., 57 percent in mineral oil) in 25 ml. of dimethylsulfoxide, is added to 3 g. of 4-carboxybutyltriphenylphosphonium bromide. The reaction mixture is maintained at 20° C. with stirring for 30 min. A solution of 3α,5α-dihydroxy-2β-[(3R)-3-hydroxy-4-phenoxytrans-1-butenyl]-1α-cyclopentaneacetaldehyde γ-lactol bis(tetrahydropyranyl ether), 1.57 g., in 10 ml. of dimethylsulfoxide is added. The reaction mixture is stirred at ambient temperature for 2 hr. and diluted with 50 ml. of benzene. Potassium bisulfate (2.7 g. in 30 ml. of water) is slowly added, maintaining the reaction temperature at less than or equal to 10° C. The aqueous layer is extracted with 50 ml. of benzene and the organic extracts are washed successfully with 50 ml. of water and 50 ml. of brine before combining, drying, and evaporating. Evaporation yields an oil which is chromatographed on 100 g. of acid washed silica gel packed in 20 percent ethyl acetate and Skellysolve B. Elution with 20-75 percent ethyl acetate and Skellysolve B yields crude 16-phenoxy- 17,18,19,20-tetranor-PGF2α, bis-(tetrahydropyranyl ether).

Workup

  1. stirringThe reaction mixture is stirred at ambient temperature for 2 hr
  2. additionand diluted with 50 ml
  3. temperaturemaintaining the reaction temperature at less than or equal to 10° C
  4. extractionThe aqueous layer is extracted with 50 ml
  5. washof benzene and the organic extracts are washed successfully with 50 ml
  6. customdrying
  7. customevaporating
  8. customEvaporation
  9. customyields an oil which
  10. customis chromatographed on 100 g
  11. washof acid washed silica gel
  12. washElution with 20-75 percent ethyl acetate and Skellysolve B

Sources & evidence

ORD record
ord-5481f880f7ac42afa4378e53dbaad205
Source dataset
uspto-grants-1977_03
Patent number
US04013695

Reaction notes

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