p-Toluenesulfonic acid → HCID 59799419, compound

HRID 1095434Notes

Reaction equation

HRID 1095434 reaction equation
[O:1]=[C:2]([C:20]1[CH:25]=[CH:24][C:23]([C:26]([F:29])([F:28])[F:27])=[CH:22][CH:21]=1)[CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][O:9][S:10]([C:13]1[CH:18]=[CH:17][C:16]([CH3:19])=[CH:15][CH:14]=1)(=[O:12])=[O:11].C1(C)C=CC(S(O)(=O)=O)=CC=1.[CH3:41][O:42]C(OC)OC.[C:48]([O-])(O)=O.[Na+]>CO.ClCCl>[CH3:48][O:1][C:2]([O:42][CH3:41])([C:20]1[CH:21]=[CH:22][C:23]([C:26]([F:29])([F:27])[F:28])=[CH:24][CH:25]=1)[CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][O:9][S:10]([C:13]1[CH:18]=[CH:17][C:16]([CH3:19])=[CH:15][CH:14]=1)(=[O:12])=[O:11]

Participants

7

Reactant 4

HCID 6101p-Toluenesulfonic acidHCID 9005Trimethyl orthoformateHCID 516892Sodium BicarbonateHCID 59799431HCID 59799431, compound

Product 1

HCID 59799419HCID 59799419, compoundYield 59%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6344DichloromethaneSolvent

Procedure

To a magnetically stirred solution of toluene-4-sulfonic acid 7-oxo-7-[4-(trifluoromethyl)phenyl]heptyl ester (2.77 g, 6.464 mmol) in methanol (75 ml), a catalytic amount of para-toluenesulfonic acid (0.097 g, 0.508 mmol) and excess trimethylorthoformate (16 ml, 142 mmol) were successively added. The resulting mixture was heated at reflux temperature for 20 hours. After allowing the reaction mixture to attain room temperature saturated aqueous NaHCO3 and dichloromethane were successively added. The separated organic layer was washed with saturated aqueous NaHCO3. The organic layer was subsequently dried over Na2SO4, filtered and concentrated in vacuo to give crude toluene-4-sulfonic acid 7,7-dimethoxy-7-[4-(trifluoromethyl)phenyl]heptyl ester which was purified by column chromatography (alumina, ethylacetate/heptane= 1/10 (v/v)) to give pure toluene-4-sulfonic acid 7,7-dimethoxy-7-[4-(trifluoromethyl)phenyl]heptyl ester (1.82 g, 59% yield). 1H-NMR (400 MHz, CDCl3) δ 0.84-0.93 (m, 2H), 1.06-1.26 (m, 4H), 1.51-1.57 (m, 2H), 1.80-1.86 (m, 2H), 2.44 (s, 3H), 3.13 (s, 6H), 3.94 (t, J=7, 2H), 7.32 (d, J˜8, 2H), 7.55 (d, J˜8, 2H), 7.60 (d, J˜8, 2H), 7.75 (d, J˜8, 2H).

Workup

  1. temperatureThe resulting mixture was heated
  2. temperatureat reflux temperature for 20 hours
  3. customto attain room temperature
  4. additionwere successively added
  5. washThe separated organic layer was washed with saturated aqueous NaHCO3
  6. dry with materialThe organic layer was subsequently dried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customto give crude toluene-4-sulfonic acid 7,7-dimethoxy-7-[4-(trifluoromethyl)phenyl]heptyl ester which
  10. customwas purified by column chromatography (alumina, ethylacetate/heptane= 1/10 (v/v))

Sources & evidence

ORD record
ord-bab984471618434ca7ae5345a9cae8d4
Source dataset
uspto-grants-2012_03
Patent number
US08138174B2

Reaction notes

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