Hydrochloric Acid → cis-5-Heptenamide

HRID 372567Notes

Reaction equation

HRID 372567 reaction equation
[Br-].CS([NH:6][C:7]([CH2:9][CH2:10][CH2:11][CH2:12][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)=[O:8])(=O)=O.[Na].[C:33](OCC)(=O)[CH3:34].Cl>CS(C)=O>[C:7]([NH2:6])(=[O:8])[CH2:9][CH2:10][CH2:11]/[CH:12]=[CH:33]\[CH3:34]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 8857Ethyl AcetateHCID 5360545SodiumHCID 19608840[4-(Methanesulfonylaminocarbonyl)butyl]triphenylphosphonium bromide

Product 1

HCID 86735722cis-5-Heptenamide

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent3×

Procedure

To a solution of 27.0 g. (52.0 mmoles) of (4-methanesulfonylaminocarbonyl-n-butyl)triphenylphosphonium bromide in 46 ml. of dimethyl sulfoxide is added dropwise 49.3 ml. (98.6 mmoles) of a 2.0M solution of sodium methylsulfonylmethide in dimethyl sulfoxide. To the resultant red solution is added over the course of 15 minutes a solution of 6.6 g. (20.8 mmoles) of the hemiacetal prepared in Example IV in 63 ml. of dimethyl sulfoxide. After being stirred for an additional 2.0 hours, the reaction is poured onto 600 ml. of ice-water. The cold aqueous layer is covered with ethyl acetate and acidified to pH~3 with 10% hydrochloric acid. The acidified aqueous layer is further extracted with ethyl acetate (2 × 200 ml.) and the combined organic extracts are washed with water followed by brine. Drying the organic layer over anhydrous sodium sulfate and concentration affords the crude product which is triturated with ether. Concentration of the ether provides N-methanesulfonyl 7-[2β-(1,3-oxathialan-2-yl)-3α -(tetrahydropyran-2-yloxy)-5α-hydroxycyclopent-1α-yl)]-cis-5-heptenamide (VI).

Workup

  1. additionTo the resultant red solution is added over the course of 15 minutes a solution of 6.6 g
  2. additionthe reaction is poured onto 600 ml
  3. extractionThe acidified aqueous layer is further extracted with ethyl acetate (2 × 200 ml.)
  4. washthe combined organic extracts are washed with water
  5. customDrying the organic layer
  6. concentrationover anhydrous sodium sulfate and concentration
  7. customaffords the crude product which
  8. customis triturated with ether

Sources & evidence

ORD record
ord-07decbeee9d2404785a25b40f23f137c
Source dataset
uspto-grants-1978_05
Patent number
US04091207

Reaction notes

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