Hydrochloric Acid → 1-Fluoro-1-phenylsulfonyl-3-methyl-3-(4-chlorophenyl)-1-butene

HRID 1939687Notes

Reaction equation

HRID 1939687 reaction equation
[C:1]1([S:7]([CH2:10][F:11])(=[O:9])=[O:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.P(Cl)(OCC)(OCC)=O.C[Si]([N-][Si](C)(C)C)(C)C.[Li+].[Cl:31][C:32]1[CH:37]=[CH:36][C:35]([C:38]([CH3:43])([CH3:42])[CH2:39]C=O)=[CH:34][CH:33]=1.[Cl-].[NH4+].Cl>O1CCCC1.C(OCC)(=O)C>[F:11][C:10]([S:7]([C:1]1[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1)(=[O:9])=[O:8])=[CH:42][C:38]([CH3:43])([C:35]1[CH:36]=[CH:37][C:32]([Cl:31])=[CH:33][CH:34]=1)[CH3:39]

Participants

9

Reactant 6

HCID 313Hydrochloric AcidHCID 13139Diethyl chlorophosphateHCID 25517Ammonium ChlorideHCID 2733832Lithium HexamethyldisilazideHCID 2759036Fluoromethyl Phenyl SulfoneHCID 153325663-(4-Chlorophenyl)-3-methylbutyraldehyde

Product 1

HCID 538605131-Fluoro-1-phenylsulfonyl-3-methyl-3-(4-chlorophenyl)-1-butene

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent3×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-70 °C

Procedure

Under a nitrogen atmosphere, 25.0 grams (0.14 mole) of distilled fluoromethyl phenyl sulfone (prepared by the method of J. R McCarthy et al., Org. Syn. 1993, 72, 209), 24.8 grams (0.14 mole) of diethyl chlorophosphate, and 300 mL of anhydrous tetrahydrofuran are placed in a reaction vessel. The stirring mixture is cooled to about -70° C., and a solution of 310 mL (0.31 mole) of lithium bis(trimethylsilyl)amide (commercially available-1M in tetrahydrofuran) is added dropwise during a 15 minute period. Upon completion of addition, the reaction mixture is stirred at about -70° C. for one hour. After this time a solution of 19.7 grams (0.10 mole) of 3-(4-chlorophenyl)-3-methylbutyraldehyde in 65 mL of tetrahydrofuran is added via a syringe. Upon completion of addition, the reaction mixture is allowed to warm to ambient temperature where it is stirred for about two hours. The reaction mixture is then poured into an ice-cold mixture of 250 mL of ethyl acetate, 250 mL of saturated aqueous ammonium chloride, and 30 mL. of concentrated hydrochloric acid. The organic layer is separated, and the aqueous layer is extracted with ethyl acetate. The extract and the organic layer are combined, washed with 100 mL of saturated aqueous sodium chloride, and added with magnesium sulfate. The mixture is filtered, and the filtrate is concentrated under reduced pressure to a residue. The residue is subjected to column chromatography on silica gel. The product-containing fractions are combined and concentrated under reduced pressure, yielding 1-fluoro-1-phenylsulfonyl-3-methyl-3-(4-chlorophenyl)-1-butene.

Workup

  1. additionUpon completion of addition
  2. additionUpon completion of addition
  3. temperatureto warm to ambient temperature where it
  4. stirringis stirred for about two hours
  5. customThe organic layer is separated
  6. extractionthe aqueous layer is extracted with ethyl acetate
  7. extractionThe extract
  8. washwashed with 100 mL of saturated aqueous sodium chloride
  9. additionadded with magnesium sulfate
  10. filtrationThe mixture is filtered
  11. concentrationthe filtrate is concentrated under reduced pressure to a residue
  12. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-b7c3bd95a7be4797aefece35504182f7
Source dataset
uspto-grants-1997_12
Patent number
US05696259

Reaction notes

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