Methyl trifluoromethyl ketone → 1-(4-Phenylsulfonylphenyl)-3-hydroxy-3-methyl-4,4,4-trifluorobut-1-yne

HRID 35885

Reaction equation

HRID 35885 reaction equation
[C:1]1([S:7]([C:10]2[CH:15]=[CH:14][C:13]([C:16]#[CH:17])=[CH:12][CH:11]=2)(=[O:9])=[O:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[Li]CCCC.[F:23][C:24]([F:29])([F:28])[C:25]([CH3:27])=[O:26]>O1CCCC1>[F:23][C:24]([F:29])([F:28])[C:25]([OH:26])([CH3:27])[C:17]#[C:16][C:13]1[CH:12]=[CH:11][C:10]([S:7]([C:1]2[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=2)(=[O:9])=[O:8])=[CH:15][CH:14]=1

Participants

5

Reactant 3

HCID 9871Methyl trifluoromethyl ketoneHCID 199393204-PhenylsulfonylphenylethyneHCID 178418339Butyllithium

Product 1

HCID 199393031-(4-Phenylsulfonylphenyl)-3-hydroxy-3-methyl-4,4,4-trifluorobut-1-yneYield 75.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a cooled (-78° C.) solution of 4-phenylsulfonylphenylethyne (66 mg, 0.27 mmol) in freshly distilled tetrahydrofuran (2.5 mL) was added n-BuLi (109 mL, 2.5M solution in hexanes, 0.27 mmol). The solution was stirred for 10 minutes at -78° C. at which time 1,1,1-trifluoroacetone (272 mL, 1.0M solution in tetrahydrofuran, 0.27 mmol) was added. The reaction mixture was kept at -78° C. for five minutes before quenching with 2N HCl . Diethyl ether was added, and the aqueous layer extracted further with diethyl ether. The combined organic layers were dried, evaporated and the product purified by chromatography, with ethyl acetate:hexanes as eluent (1:4) to yield the title butyne as a white solid (72 mg, 75%); mp 94.8°-95.3° C.; 250 MHz NMR (CDCl3): 1.72 (s,3, CH3), 3.08 (s,1, OH), 7.48-7.60 (m,5, Ar), 7.87-7.94 (m,4, Ar); MS: m/z=355(M+ 1). Analysis for C17H13F3O3S: Calculated: C, 57.62; H, 3.70; Found: C, 57.46; H, 3.65.

Workup

  1. additionwas added
  2. custombefore quenching with 2N HCl
  3. additionDiethyl ether was added
  4. extractionthe aqueous layer extracted further with diethyl ether
  5. customThe combined organic layers were dried
  6. customevaporated
  7. customthe product purified by chromatography, with ethyl acetate

Sources & evidence

ORD record
ord-15e03f81b99f4241a3b39f8284c311e9
Source dataset
uspto-grants-1995_05
Patent number
US05411973

Linked notes

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