Dibromodifluoromethane → Methyl 12,12-difluoro-11-dodecenoate

HRID 1709640Notes

Reaction equation

HRID 1709640 reaction equation
O=[CH:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][C:12]([O:14][CH3:15])=[O:13].Br[C:17](Br)([F:19])[F:18].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>CC(N(C)C)=O.O.[Zn]>[F:18][C:17]([F:19])=[CH:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][C:12]([O:14][CH3:15])=[O:13]

Participants

7

Reactant 3

HCID 6382DibromodifluoromethaneHCID 11776TriphenylphosphineHCID 11020258Undecanoic acid, 11-oxo-, methyl ester

Product 1

HCID 11149322Methyl 12,12-difluoro-11-dodecenoateYield 49.5%

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 962WaterSolventHCID 31374DimethylacetamideSolvent

Procedure

A stirred mixture of 7.5 grams (0.035 mole) of methyl 11-oxoundecanoate and 14.7 grams (0.07 mole) of dibromodifluoromethane was cooled to 0°-10° C., and a solution of 18.4 grams (0.07 mole) of triphenylphosphine in 50 ml of dimethylacetamide was added dropwise. During the addition the temperature of the reaction mixture was maintained at 0°-10° C. Upon completion of addition the reaction mixture was allowed to warm to ambient temperature, and 4.6 grams (0.07 mole) of zinc dust was added in two portions. The addition caused an exothermic reaction which raised the temperature of the reaction mixture to 90° C. The reaction mixture was allowed to cool to ambient temperature where it stood without stirring for 60 hours. The reaction mixture was diluted with water and was subjected to a steam distillation with pentane. The appropriate fractions were combined and concentrated under reduced pressure yielding 4.3 grams of methyl 12,12-difluoro-11-dodecenoate. The nmr spectrum was consistent with the proposed structure.

Workup

  1. temperaturewas cooled to 0°-10° C.
  2. additionDuring the addition the temperature of the reaction mixture
  3. temperaturewas maintained at 0°-10° C
  4. additionUpon completion of addition the reaction mixture
  5. additionThe addition
  6. customan exothermic reaction which
  7. temperatureraised the temperature of the reaction mixture to 90° C
  8. temperatureto cool to ambient temperature where it
  9. distillationwas subjected to a steam distillation with pentane
  10. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-28f0ede115514d53928fe666fec9ecff
Source dataset
uspto-grants-1990_08
Patent number
US04950666

Reaction notes

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