tert-Butanol → Ethyl 4,4,5,5,5-pentafluoro-3-(3-((methoxymethoxy)methyl)phenyl)pentanoate

HRID 1049573Notes

Reaction equation

HRID 1049573 reaction equation
CC(C)([O-])C.[Na+].C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1.[F:53][C:54]([F:77])([C:73]([F:76])([F:75])[F:74])[C:55]([C:62]1[CH:67]=[CH:66][CH:65]=[C:64]([CH2:68][O:69][CH2:70][O:71][CH3:72])[CH:63]=1)=[CH:56][C:57]([O:59][CH2:60][CH3:61])=[O:58].C(O)(C)(C)C>C1(C)C=CC=CC=1.[Cu]Cl.C(O)C>[F:53][C:54]([F:77])([C:73]([F:74])([F:75])[F:76])[CH:55]([C:62]1[CH:67]=[CH:66][CH:65]=[C:64]([CH2:68][O:69][CH2:70][O:71][CH3:72])[CH:63]=1)[CH2:56][C:57]([O:59][CH2:60][CH3:61])=[O:58]

Participants

8

Reactant 4

HCID 6386tert-ButanolHCID 634876Binap, (A+-)-HCID 23676156Sodium t-butoxideHCID 131736030HCID 131736030, compound

Product 1

HCID 117759918Ethyl 4,4,5,5,5-pentafluoro-3-(3-((methoxymethoxy)methyl)phenyl)pentanoateYield 26.6%

Reagents, catalysts & solvents 3

HCID 62652Cuprous chlorideCatalystHCID 702EthanolSolventHCID 1140TolueneSolvent

Procedure

Under a nitrogen atmosphere, copper (I) chloride (73.7 mg), sodium tert-butoxide (71.5 mg) and BINAP (463 mg) were stirred in toluene (12 mL) at room temperature for 10 min, and to the reaction mixture were successively added polymethylhydrosiloxane (1.67 mL), ethyl 4,4,5,5,5-pentafluoro-3-(3-((methoxymethoxy)methyl)phenyl)pent-2-enoate (1.37 g) and tert-butanol (854 μL) at room temperature. The reaction mixture was stirred at room temperature for 16 hr, ethanol (5 mL) was added at room temperature, and the mixture was filtered through celite. To the filtrate was added saturated aqueous ammonium chloride solution at room temperature, and the mixture was extracted with ethyl acetate. The extract was washed with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure and the residue was filtered through NH silica gel to give a crude product (366 mg) of the title compound as a colorless oil. This compound was used for the next step without further purification.

Workup

  1. customat room temperature
  2. filtrationthe mixture was filtered through celite
  3. additionTo the filtrate was added saturated aqueous ammonium chloride solution at room temperature
  4. extractionthe mixture was extracted with ethyl acetate
  5. washThe extract was washed with water and saturated brine
  6. dry with materialdried over anhydrous magnesium sulfate
  7. customThe solvent was evaporated under reduced pressure
  8. filtrationthe residue was filtered through NH silica gel

Sources & evidence

ORD record
ord-75e797f4a8c245e6a4097ff58e04dacc
Source dataset
uspto-grants-2016_07
Patent number
US09382188B2

Reaction notes

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