Oxalic Acid → HCID 131710258, compound

HRID 1657366Notes

Reaction equation

HRID 1657366 reaction equation
[CH3:1][C@:2]12[CH2:18][CH2:17][C@H:16]3[C@@H:7]([CH2:8][CH2:9][C:10]4[CH:11]=[CH:12][CH:13]=[CH:14][C:15]=43)[C@@H:6]1[CH2:5][CH2:4][C:3]2=[O:19].C1C[O:23]CC1.[H-].C(O[Al](OC(C)(C)C)OC(C)(C)C)(C)(C)C.[Li+].[C:43](O)(=O)[C:44]([OH:46])=[O:45]>CCOCC.O.CO>[C:44]([O:46][C@H:1]1[CH2:4][CH2:5][C@H:6]2[C@H:7]3[C@H:16]([CH2:17][CH2:18][C@:2]12[CH2:3][OH:19])[C:15]1[CH:14]=[CH:13][C:12]([OH:23])=[CH:11][C:10]=1[CH2:9][CH2:8]3)(=[O:45])[CH3:43]

Participants

8

Reactant 4

HCID 971Oxalic AcidHCID 58823-Deoxy-estroneHCID 8028TetrahydrofuranHCID 16710494Lithium tri-tert-butoxyaluminohydride

Product 1

HCID 131710258HCID 131710258, compound

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 962WaterSolvent2×HCID 3283Diethyl EtherSolvent

Procedure

400 mg. of 3,18-bis)tetrahydropyranyloxy)-1,3,5(10)-estratrien-17-one is mixed, in 4 ml. of absolute THF, at 0° C. with 400 mg. of lithium tri-tert.-butoxyaluminum hydride and stirred for 30 minutes at room temperature. After the mixture has been poured into water, it is extracted with ether. The ether phase is washed neutral with water, dried, and evaporated. The residue of crude 3,18-bis(tetrahydropyranyloxy)-1,3,5(10)-estratrien-17β-ol is heated in 1 ml. of pyridine with 1 ml. of acetic anhydride for 30 minutes to 100° C. The mixture is then introduced into water, stirred for 45 minutes, extracted with ether, and washed neutral with water. After drying and evaporation, crude 3,18-bis(tetrahydropyranyloxy)-17β-acetoxy-1,3,5(10)-estratriene is obtained, which is heated to the boiling point in 4 ml. of methanol with 4 ml. of water and 0.4 g. of oxalic acid. After 1 hour, the mixture is taken up in ether, washed neutral with water, dried, and evaporated. After purification by chromatography over silica gel, 17β-acetoxy-1,3,5(10)-estratriene-3,18-diol is obtained.

Workup

  1. customat 0° C.
  2. extractionis extracted with ether
  3. washThe ether phase is washed neutral with water
  4. customdried
  5. customevaporated
  6. temperatureThe residue of crude 3,18-bis(tetrahydropyranyloxy)-1,3,5(10)-estratrien-17β-ol is heated in 1 ml
  7. additionThe mixture is then introduced into water
  8. extractionextracted with ether
  9. washwashed neutral with water
  10. customAfter drying
  11. customevaporation
  12. customcrude 3,18-bis(tetrahydropyranyloxy)-17β-acetoxy-1,3,5(10)-estratriene is obtained
  13. temperaturewhich is heated to the boiling point in 4 ml
  14. waitAfter 1 hour
  15. washwashed neutral with water
  16. customdried
  17. customevaporated
  18. customAfter purification by chromatography over silica gel

Sources & evidence

ORD record
ord-4dcc604246f344fc8cb0f19b65438f87
Source dataset
uspto-grants-1976_06
Patent number
US03960841

Reaction notes

Loading…