p-Toluenesulfonic acid → HCID 19866533, compound

HRID 255968Notes

Reaction equation

HRID 255968 reaction equation
[H-].[Na+].[CH2:3](Br)[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.[CH2:11]([O:27][CH2:28][CH2:29][CH:30]([OH:52])[CH2:31][O:32]C(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH3:26].C1(C)C=CC(S(O)(=O)=O)=CC=1>CN(C)C=O.O>[CH2:11]([O:27][CH2:28][CH2:29][CH:30]([O:52][CH2:3][C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1)[CH2:31][OH:32])[CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH3:26]

Participants

7

Reactant 4

HCID 6101p-Toluenesulfonic acidHCID 7498Benzyl BromideHCID 24758Sodium hydrideHCID 19866545HCID 19866545, compound

Product 1

HCID 19866533HCID 19866533, compoundYield 55.3%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent2×

Conditions

Temperature
0 °C

Procedure

To a suspension of 6.17 g of 50% sodium hydride (washed with hexanes) in 245 ml of dry dimethylformamide was added 19.45 g of benzyl bromide at 0° C. A solution of 56.65 g of 4-(hexadecyloxy)-1-(triphenylmethoxy)-2-butanol in 60 ml of dimethylformamide was added dropwise with stirring at 0° C. under argon. The mixture was stirred overnight at room temperature, then poured into 1000 ml of iced water and extracted with petroleum ether. The organic phase was dried, the solvent removed and the residue dissolved in a mixture of 235 ml of methanol and 125 ml of tetrahydrofuran. A 500 mg portion of p-toluene sulfonic acid was added, the mixture was allowed to stand overnight and then the solvent was removed. The residue was dissolved in petroleum ether, washed with saturated aqueous sodium bicarbonate, dried and the solvent removed giving an oil. This oil was again subjected to treatment with p-toluenesulfonic acid in the solvent system described above, again giving an oil which was purified by HPLC, giving 23 g of the desired compound as an oil.

Workup

  1. stirringThe mixture was stirred overnight at room temperature
  2. extractionextracted with petroleum ether
  3. customThe organic phase was dried
  4. customthe solvent removed
  5. dissolutionthe residue dissolved in a mixture of 235 ml of methanol and 125 ml of tetrahydrofuran
  6. additionA 500 mg portion of p-toluene sulfonic acid was added
  7. customthe solvent was removed
  8. dissolutionThe residue was dissolved in petroleum ether
  9. washwashed with saturated aqueous sodium bicarbonate
  10. customdried
  11. customthe solvent removed
  12. customgiving an oil
  13. customagain giving an oil which
  14. customwas purified by HPLC

Sources & evidence

ORD record
ord-8c72b000488e4c989c9fca7da79b53ed
Source dataset
uspto-grants-1987_10
Patent number
US04699990

Reaction notes

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