Chlorotrifluoroethylene → 8-(2-Chloro-1,2,2-trifluoroethylidene)-1,4-dioxaspiro[4.5]decane

HRID 1530792Notes

Reaction equation

HRID 1530792 reaction equation
Cl[C:2]([F:6])=[C:3]([F:5])[F:4].[Li]CCCC.[O:12]1[C:16]2([CH2:21][CH2:20][CH2:19][CH2:18][CH2:17]2)[O:15][CH2:14][CH2:13]1.[Cl-:22].[NH4+]>CCCCCC.C(OCC)C.O1CCCC1>[Cl:22][C:3]([F:5])([F:4])[C:2](=[C:19]1[CH2:20][CH2:21][C:16]2([O:15][CH2:14][CH2:13][O:12]2)[CH2:17][CH2:18]1)[F:6]

Participants

8

Conditions

Temperature
-60 °C

Procedure

At −100° C., 17.2 g of chlorotrifluoroethylene were condensed into 120 ml of tetrahydrofuran and 80 ml of diethyl ether. Over a period of 30 minutes, 84 ml of a 16 molar solution of n-BuLi in hexane were added dropwise at a temperature between −90° C. and −100° C. 18.8 g of 1,4-dioxaspiro[4.5]decane were added and the mixture was stirred at −60° C. for 1 h. The reaction solution was poured into aqueous ammonium chloride and extracted with diethyl ether and the combined organic phases were dried over magnesium sulfate and concentrated. The residue was taken up in 200 ml of pyrimidine and, at −30° C., mixed with 71 g of thionyl chloride. The reaction solution was slowly warmed to 0° C. and stirred for another 1.5 hours at this temperature. The reaction solution was poured onto ice and extracted with methylene chloride and the organic phase was dried over magnesium sulfate and concentrated. The residue was chromatographed over silica gel (petroleum ether:ethyl acetate 4:1), to give the title product as a yellow oil.

Workup

  1. customAt −100° C.
  2. extractionextracted with diethyl ether
  3. dry with materialthe combined organic phases were dried over magnesium sulfate
  4. concentrationconcentrated
  5. customwas taken up in 200 ml of pyrimidine and, at −30° C.
  6. additionmixed with 71 g of thionyl chloride
  7. temperatureThe reaction solution was slowly warmed to 0° C.
  8. stirringstirred for another 1.5 hours at this temperature
  9. additionThe reaction solution was poured onto ice
  10. extractionextracted with methylene chloride
  11. dry with materialthe organic phase was dried over magnesium sulfate
  12. concentrationconcentrated
  13. customThe residue was chromatographed over silica gel (petroleum ether:ethyl acetate 4:1)

Sources & evidence

ORD record
ord-f39592ed4e094ffda43c5d9d0a4f1600
Source dataset
uspto-grants-2001_03
Patent number
US06197729B1

Reaction notes

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