Oxalic Acid → HCID 68132042, compound

HRID 1973496Notes

Reaction equation

HRID 1973496 reaction equation
[CH2:1]1[CH2:10][O:9][CH:8]2[CH:3]([C@:4]3([CH2:22][C@H:21]([OH:23])[C@H:20]4[C@@H:11]([CH2:12][CH2:13][C:14]5[CH:15]=[C:16]([O:24][CH3:25])[CH:17]=[CH:18][C:19]=54)[C@@H:6]3[CH2:7]2)[CH3:5])[O:2]1.N1C=CC=CC=1.ClC(Cl)C(O)=O.C(O)(=O)C(O)=O>CS(C)=O.C1C=CC=CC=1.CO.CCOCC>[CH2:1]1[CH2:10][O:9][CH:8]2[CH:3]([C@:4]3([CH2:22][C:21](=[O:23])[C@H:20]4[C@@H:11]([CH2:12][CH2:13][C:14]5[CH:15]=[C:16]([O:24][CH3:25])[CH:17]=[CH:18][C:19]=54)[C@@H:6]3[CH2:7]2)[CH3:5])[O:2]1

Participants

9

Reactant 4

HCID 971Oxalic AcidHCID 1049PyridineHCID 6597Dichloroacetic AcidHCID 86734259HCID 86734259, compound

Product 1

HCID 68132042HCID 68132042, compound

Reagents, catalysts & solvents 4

HCID 241BenzeneSolventHCID 679Dimethyl SulfoxideSolventHCID 887MethanolSolventHCID 3283Diethyl EtherSolvent

Procedure

To a stirred solution of 5.13 g of 17-ethylenedioxy-11β-hydroxy-3-methoxyestra-1,3,5(10)-triene in 25 ml of dimethylsulfoxide and 25 ml of benzene is added 3 ml of pyridine and 9.3 g of N,N-dicyclohexylcarbodiimide. This mixture is then cooled and 1.5 ml of dichloroacetic acid is added. The whole is next stirred at room temperature for 11/2 hours. It is diluted by the addition of 50 ml of ether and a solution of 4 g of oxalic acid in 10 ml of methanol is added dropwise. The resulting suspension is stirred for 40 minutes at room temperature and then filtered. The filtrate is concentrated to dryness and distributed between methylene chloride and a 10% aqueous solution of sodium bicarbonate. The organic phase is washed with water and dried (Na2SO4) before being evaporated to dryness under reduced pressure. The residue is placed on a column of silica-gel and eluted with chloroform containing various percentages of methanol. The fractions eluted with chloroform containing 5 % of methanol are combined and evaporated to yield a residue which is crystallized from hexane/ether (1:1). Thus is obtained 17-ethylenedioxy-3-methoxyestra-1,3,5(10)-trien-11-one, m.p. 122° - 123° C.

Workup

  1. temperatureThis mixture is then cooled
  2. stirringThe resulting suspension is stirred for 40 minutes at room temperature
  3. filtrationfiltered
  4. concentrationThe filtrate is concentrated to dryness
  5. washThe organic phase is washed with water
  6. dry with materialdried (Na2SO4)
  7. custombefore being evaporated to dryness under reduced pressure
  8. washeluted with chloroform containing various percentages of methanol
  9. washThe fractions eluted with chloroform containing 5 % of methanol
  10. customevaporated
  11. customto yield a residue which
  12. customis crystallized from hexane/ether (1:1)

Sources & evidence

ORD record
ord-d77a0f954ee242958e77e753bb2975f7
Source dataset
uspto-grants-1976_12
Patent number
US03997574

Reaction notes

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