p-Toluenesulfonic acid → HCID 67234731, compound

HRID 2367954Notes

Reaction equation

HRID 2367954 reaction equation
[C:1]1([CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][O:12][C:13]2[CH:20]=[CH:19][C:16]([CH:17]=[O:18])=[CH:15][C:14]=2[C:21]2[S:22][CH:23]=[CH:24][CH:25]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[OH:26][C:27]([C:30](O)([CH3:32])[CH3:31])([CH3:29])[CH3:28].C1(C)C=CC(S(O)(=O)=O)=CC=1.CCOC(C)=O>C1C=CC=CC=1.CCCCCC>[CH3:31][C:30]1([CH3:32])[C:27]([CH3:29])([CH3:28])[O:26][CH:17]([C:16]2[CH:19]=[CH:20][C:13]([O:12][CH2:11][CH2:10][CH2:9][CH2:8][CH2:7][C:1]3[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=3)=[C:14]([C:21]3[S:22][CH:23]=[CH:24][CH:25]=3)[CH:15]=2)[O:18]1

Participants

7

Reactant 4

HCID 6101p-Toluenesulfonic acidHCID 6425PinacolHCID 8857Ethyl AcetateHCID 86657224HCID 86657224, compound2×

Product 1

HCID 67234731HCID 67234731, compoundYield 808.4%

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 8058HexaneSolvent

Procedure

In a 500 mL 3-necked flask equipped with a stir-bar and condenser was placed 4-((5-phenylpentyl)oxy)-3-(thiophen-2-yl)benzaldehyde (Intermediate 7) (4.9 g, 1.4 mmol), pinacol (6.6 g, 5.6 mol) and p-toluenesulfonic acid (0.8 g, 4.2 mmol) in benzene (125 mL). The resulting mixture was refluxed for 1 h. TLC analysis (EtOAc:hexane; 1:1) showed the reaction was complete. The reaction was cooled to room temperature, washed with saturated NaHCO3 (2×75 mL), brine (1×75 mL), filtered through 1 PS filter paper and concentrated under reduced pressure to give a brown oil. The oil was flash chromatographed over silica gel (100 g) with anhydrous sodium sulfate (20 g) on top packed with hexane. The column was eluted with 12×50 mL of 15% EtOAc in hexane. The product was eluted to give 5.1 g (81%) 4,4,5,5-tetramethyl-2-(4-((5-phenylpentyl)oxy)-3-(thiophen-2-yl)phenyl)-1,3-dioxolane (Intermediate 8) as a yellow oil. HPLC analysis showed a purity of ˜97%. NMR (CDCl3) δ 7.8 (s, 1H), 7.55 (d, 1H), 7.1-7.4 (m, 8H), 6.95 (d, 1H), 6.0 (s, 1H), 4.1 (t, 2H), 2.7 (t, 2H), 1.95 (m, 2H), 1.7 (m, 2H), 1.6 (m, 2H), 1.35 (d, 12H).

Workup

  1. customIn a 500 mL 3-necked flask equipped with a stir-bar and condenser
  2. temperatureThe resulting mixture was refluxed for 1 h
  3. washwashed with saturated NaHCO3 (2×75 mL), brine (1×75 mL)
  4. filtrationfiltered through 1 PS
  5. filtrationfilter paper
  6. concentrationconcentrated under reduced pressure
  7. customto give a brown oil
  8. customchromatographed over silica gel (100 g) with anhydrous sodium sulfate (20 g) on top
  9. washThe column was eluted with 12×50 mL of 15% EtOAc in hexane
  10. washThe product was eluted

Sources & evidence

ORD record
ord-f4e91a422b634597b896eab0922f7ce7
Source dataset
uspto-grants-2014_04
Patent number
US08703745B1

Reaction notes

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