Azobisisobutyronitrile → HCID 22261547, compound

HRID 1610535Notes

Reaction equation

HRID 1610535 reaction equation
[F:1][C:2]([F:14])([O:6][C:7]1[CH:8]=[C:9]([CH3:13])[CH:10]=[CH:11][CH:12]=1)[CH:3]([F:5])[F:4].BrN1C(=O)CCC1=O.N(C(C)(C)C#N)=NC(C)(C)C#N.[F:35][C:36]1[CH:37]=[C:38]([C:42](=[O:49])[CH2:43][C:44]([O:46][CH2:47][CH3:48])=[O:45])[CH:39]=[CH:40][CH:41]=1.[H-].[Na+].FC(F)(OC1C=C(CBr)C=CC=1)C(F)F>C(OCC)(=O)C.COCCOC.O>[F:35][C:36]1[CH:37]=[C:38]([C:42](=[O:49])[CH:43]([CH2:13][C:9]2[CH:10]=[CH:11][CH:12]=[C:7]([O:6][C:2]([F:14])([F:1])[CH:3]([F:4])[F:5])[CH:8]=2)[C:44]([O:46][CH2:47][CH3:48])=[O:45])[CH:39]=[CH:40][CH:41]=1

Participants

10

Reactant 6

HCID 6547AzobisisobutyronitrileHCID 24758Sodium hydrideHCID 67184N-bromobutanimideHCID 74438Benzene, 1-methyl-3-(1,1,2,2-tetrafluoroethoxy)-HCID 2063904Ethyl 3-(3-fluorophenyl)-3-oxopropanoateHCID 114603781-(Bromomethyl)-3-(1,1,2,2-tetrafluoroethoxy)benzene

Product 1

HCID 22261547HCID 22261547, compound

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 80711,2-DimethoxyethaneSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 3-(1,1,2,2-tetrafluoroethoxy)toluene (8.91 g, 42.8 mmol) in ethyl acetate (100 ml) were added N-bromosuccinimide (8.35 g, 46.9 mmol) and 2,2′-azobis(isobutyronitrile) (335 mg, 2.04 mmol), and the mixture was heated under reflux for 5 hrs. The reaction solution was concentrated and the crystals were filtered with hexane. The filtrate was concentrated to prepare 3-(1,1,2,2-tetrafluoroethoxy)-a-bromotoluene. To a solution of ethyl 3-(3-fluorophenyl)-3-oxopropanoate (8.57 g, 40.8 mmol) in 1,2-dimethoxyethane (80 ml) was added sodium hydride (60% in oil, 1.63 g, 40.8 mmol) under ice-cooling, and the mixture was stirred at room temperature for 30 min. To the reaction solution was dropwise added a solution of 3-(1,1,2,2-tetrafluoroethoxy)-α-bromotoluene prepared earlier in 1,2-dimethoxyethane (10 ml), and the mixture was stirred overnight at room temperature. The reaction solution was poured into water (100 ml), and the mixture was extracted with ethyl acetate (100 ml×2). The extract was washed with water and saturated brine, dried (anhydrous magnesium sulfate), and evaporated under reduced pressure. The residue was purified by silica gel column chromatography (hexane:ethyl acetate=10:1-6:1) and recrystallized from ethyl acetate-hexane to give the objective substance (8.86 g, 52%).

Workup

  1. temperaturethe mixture was heated
  2. temperatureunder reflux for 5 hrs
  3. concentrationThe reaction solution was concentrated
  4. filtrationthe crystals were filtered with hexane
  5. concentrationThe filtrate was concentrated
  6. customto prepare 3-(1,1,2,2-tetrafluoroethoxy)-a-bromotoluene
  7. temperaturecooling
  8. stirringthe mixture was stirred overnight at room temperature
  9. extractionthe mixture was extracted with ethyl acetate (100 ml×2)
  10. washThe extract was washed with water and saturated brine
  11. dry with materialdried (anhydrous magnesium sulfate)
  12. customevaporated under reduced pressure
  13. customThe residue was purified by silica gel column chromatography (hexane:ethyl acetate=10:1-6:1)
  14. customrecrystallized from ethyl acetate-hexane
  15. customto give the objective substance (8.86 g, 52%)

Sources & evidence

ORD record
ord-6925e4703b6648318079003a7298284e
Source dataset
uspto-grants-2006_01
Patent number
US06982348B2

Reaction notes

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