Trifluoroacetic acid → HCID 68182902, compound

HRID 1615544Notes

Reaction equation

HRID 1615544 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([C:9]2(O)[C:14]3[CH:15]=[CH:16][S:17][C:13]=3[CH2:12][CH2:11][CH2:10]2)[CH:5]=[CH:6][C:7]=1[Cl:8].C([SiH](CC)CC)C.FC(F)(F)C(O)=O>C(Cl)Cl>[Cl:1][C:2]1[CH:3]=[C:4]([CH:9]2[C:14]3[CH:15]=[CH:16][S:17][C:13]=3[CH2:12][CH2:11][CH2:10]2)[CH:5]=[CH:6][C:7]=1[Cl:8]

Participants

5

Reactant 3

HCID 6422Trifluoroacetic acidHCID 12052TriethylsilaneHCID 59143919HCID 59143919, compound

Product 1

HCID 68182902HCID 68182902, compoundYield 76.5%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a stirring solution of 4-(3,4-dichlorophenyl)-4,5,6,7-tetrahydro-1-benzothiophene-4-ol (4.50 g, 15.0 mmol) in methylene chloride (75 mL) were added triethylsilane (11 mL, 69 mmol) and trifluoroacetic acid (12.0 mL, 156 mmol). The solution became reddish orange but no exotherm was observed. The reaction was stirred for 2.5 hr at rt under an atmosphere of nitrogen. The resulting somewhat fluorescent reddish orange solution was concentrated on the rotovap. Ethyl acetate and water were added (˜100 ml each), the mixture was stirred, and a saturated solution of NaHCO3 was slowly added until the mixture became basic. The mixture was transferred to a separatory funnel, the organic layer was separated, and the aqueous layer was extracted again with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated to leave crude product as a light brown oil. The residue was purified using column chromatography on silica gel (80 g RediSep column, eluant 100% hexane) give the product (3.25 g, 76% yield) as a clear oil. LCMS: (FA) product did not give an ionization peak. 1H NMR (400 MHz, DMSO) δ 7.59-7.50 (d, J=8.3 Hz, 1H), 7.37-7.31 (d, J=2.1 Hz, 1H), 7.26-7.19 (d, J=5.2 Hz, 1H), 7.12-7.01 (dd, J=8.3, 2.1 Hz, 1H), 6.48-6.40 (d, J=5.2 Hz, 1H), 4.11-4.00 (t, J=6.2 Hz, 1H), 2.91-2.71 (m, 2H), 2.14-2.00 (m, 1H), 1.91-1.62 (m, 3H).

Workup

  1. concentrationThe resulting somewhat fluorescent reddish orange solution was concentrated on the rotovap
  2. additionEthyl acetate and water were added (˜100 ml each)
  3. stirringthe mixture was stirred
  4. additiona saturated solution of NaHCO3 was slowly added until the mixture
  5. customThe mixture was transferred to a separatory funnel
  6. customthe organic layer was separated
  7. extractionthe aqueous layer was extracted again with ethyl acetate
  8. washThe combined organic layers were washed with brine
  9. dry with materialdried over sodium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customto leave crude product as a light brown oil
  13. customThe residue was purified

Sources & evidence

ORD record
ord-304b475d6d0547afbc7f4833eb4eba8e
Source dataset
uspto-grants-2014_07
Patent number
US08765746B2

Reaction notes

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