Vinylidene fluoride → 8-(2,2,2-Trifluoroethylidene)-1,4-dioxaspiro[4.5]decane

HRID 1530796Notes

Reaction equation

HRID 1530796 reaction equation
[F:1][C:2]([F:4])=[CH2:3].[Li]C(CC)C.[O:10]1[C:14]2([CH2:19][CH2:18][CH2:17][CH2:16][CH2:15]2)[O:13][CH2:12][CH2:11]1.[Cl-].[NH4+].CCN(S(F)(F)[F:28])CC>C(Cl)Cl.C(OCC)C.O1CCCC1>[F:1][C:2]([F:28])([F:4])[CH:3]=[C:17]1[CH2:18][CH2:19][C:14]2([O:13][CH2:12][CH2:11][O:10]2)[CH2:15][CH2:16]1

Participants

9

Reactant 5

HCID 6369Vinylidene fluorideHCID 90931,4-Dioxaspiro(4.5)decaneHCID 25517Ammonium Chloride2×HCID 123472(Diethylamino)sulfur trifluorideHCID 178418400CID 53628100

Product 1

HCID 212526788-(2,2,2-Trifluoroethylidene)-1,4-dioxaspiro[4.5]decane

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-100 °C

Procedure

At −100° C., 22 g of 1,1-difluoroethylene were condensed into a solvent mixture of 400 ml of tetrahydrofuran and 100 ml of diethyl ether. Subsequently, 153 ml of a 1.3 molar solution of sec-BuLi were added dropwise to the reaction solution at a temperature between −90° C. and −100° C. Finally, 31.2 g of 1,4-dioxaspiro[4.5]decane were added, the solution was stirred at −100° C. for another 20 minutes and subsequently warmed to 0° C. with stirring. The reaction solution was poured into an aqueous ammonium chloride and extracted with methylene chloride and the combined organic phases were dried over magnesium sulfate and concentrated. The residue was taken up in 400 ml of methylene chloride and, at −70° C., reacted with 32 g (0.2 mol) of DAST, dissolved in 100 ml of methylene chloride. The mixture was then slowly warmed to 0° C. with stirring, and the reaction solution was subsequently poured into an aqueous ammonium chloride. The product was extracted with diethyl ether and the combined organic phases were dried over MgSO4 and concentrated. The residue was chromatographed over silica gel (petroleum ether/ethyl acetate 4:1), to give the title product as a colourless oil.

Workup

  1. customAt −100° C.
  2. customcondensed
  3. temperaturesubsequently warmed to 0° C.
  4. stirringwith stirring
  5. extractionextracted with methylene chloride
  6. dry with materialthe combined organic phases were dried over magnesium sulfate
  7. concentrationconcentrated
  8. customwas taken up in 400 ml of methylene chloride and, at −70° C.
  9. temperatureThe mixture was then slowly warmed to 0° C.
  10. stirringwith stirring
  11. extractionThe product was extracted with diethyl ether
  12. dry with materialthe combined organic phases were dried over MgSO4
  13. concentrationconcentrated
  14. customThe residue was chromatographed over silica gel (petroleum ether/ethyl acetate 4:1)

Sources & evidence

ORD record
ord-06c96a7b378a45e7b9a3621bb1afbcb6
Source dataset
uspto-grants-2001_03
Patent number
US06197729B1

Reaction notes

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