Trichlorofluoromethane → (+)-Estrone 3-methyl ether

HRID 1761821Notes

Reaction equation

HRID 1761821 reaction equation
FN(S(C(F)(F)F)(=O)=O)S(C(F)(F)F)(=O)=O.C(Cl)(Cl)(Cl)F.N(S(C(F)(F)F)(=O)=O)S(C(F)(F)F)(=O)=O.FF.C[C@]12CC[C@H]3C(=CCC4[C@@H]3CCCC4)C1=CC=C2.[CH3:57][O:58][C:59]1[C:76](F)=[CH:75][C:74]2[C@@H:73]3[C@H:64]([C@H:65]4[C@@:69]([CH2:71][CH2:72]3)([CH3:70])[C:68](=[O:78])[CH2:67][CH2:66]4)[CH2:63][CH2:62][C:61]=2[CH:60]=1.COC1C=CC2[C@@H]3[C@H]([C@H]4[C@@](CC3)(C)C(=O)CC4)CCC=2C=1F>>[CH3:57][O:58][C:59]1[CH:76]=[CH:75][C:74]2[C@@H:73]3[C@H:64]([C@H:65]4[C@@:69]([CH2:71][CH2:72]3)([CH3:70])[C:68](=[O:78])[CH2:67][CH2:66]4)[CH2:63][CH2:62][C:61]=2[CH:60]=1

Participants

8

Reactant 7

HCID 6389Trichlorofluoromethane3×HCID 24524FluorineHCID 157857Bis(trifluoromethane)sulfonimideHCID 9796313Methanesulfonamide, N,1,1,1-tetrafluoro-N-[(trifluoromethyl)sulfonyl]-HCID 125350834-Fluoro1,3,5(10)estratrien-3ol-17one methyl etherHCID 144744812-Fluoro1,3,5(10)estratrien-3ol-17one methyl etherHCID 69044490Estratrien

Product 1

HCID 92895(+)-Estrone 3-methyl ether

Procedure

The fluorination reaction was carried out in a 10 mm NMR tube. To 0.28 mmol of the estratrien methyl ether were added 2.5 ml of CDCl3 by vacuum transfer. The mixture was warmed to room temperature forming a colorless solution. This solution was cooled to -196° C. and 0.28 mmol each of FN(SO2CF3)2 and CFCl3 were added by vacuum transfer. The tube was sealed and warmed to -74° C. and then to 22° C. over a 2 hour period. Near -65° C., the colorless solution began to turn to a pale yellow color. After reaching 22° C., 19F NMR indicated a quantitative amount of (CF3SO2)2NH was formed. Two other fluorine resonances are observed in the ratio of 1:1 with a total area equal to the internal CFCl3 standard. These resonances at -140.2(m) and -168.6(m) ppm relative to CFCl3 are assignable to an equimolar mixture of the two monofluoro derivatives of the estratrien, 2-fluoro1,3,5(10)estratrien-3ol-17one methyl ether and 4-fluoro1,3,5(10)estratrien-3ol-17one methyl ether, respectively.

Workup

  1. customThe fluorination reaction
  2. customforming a colorless solution
  3. temperatureThis solution was cooled to -196° C.
  4. customThe tube was sealed
  5. temperaturewarmed to -74° C.
  6. customNear -65° C.
  7. customAfter reaching 22° C.
  8. customwas formed

Sources & evidence

ORD record
ord-42f15418f84b452ba3928532e15efef7
Source dataset
uspto-grants-1989_05
Patent number
US04828764

Reaction notes

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