Dimethyl Sulfoxide → 7-(p-Toluenesulfonyloxy)-2-heptenal

HRID 1598374Notes

Reaction equation

HRID 1598374 reaction equation
[C:1](Cl)(=[O:5])[C:2](Cl)=O.CS(C)=O.[C:11]1([CH3:27])[CH:16]=[CH:15][C:14]([S:17]([O:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25]O)(=[O:19])=[O:18])=[CH:13][CH:12]=1.C(N(CC)CC)C>ClCCl.C(Cl)(Cl)Cl>[C:11]1([CH3:27])[CH:12]=[CH:13][C:14]([S:17]([O:20][CH2:21][CH2:22][CH2:23][CH2:24][CH:25]=[CH:2][CH:1]=[O:5])(=[O:19])=[O:18])=[CH:15][CH:16]=1

Participants

7

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 114595781,5-Pentanediol monotosylate

Product 1

HCID 572535817-(p-Toluenesulfonyloxy)-2-heptenalYield 113.9%

Reagents, catalysts & solvents 2

HCID 6212ChloroformSolventHCID 6344DichloromethaneSolvent2×

Procedure

To a solution of oxalic chloride (19.9 ml, 0.229 mol) in dichloromethane (400 ml) was added dimethyl sulfoxide (32.4 ml, 0.457 mol) at -78° C. and the mixture was stirred for 15 minutes. To the reaction mixture was added dropwise over 30 minutes a solution of 5-hydroxypentyl p-toluenesulfonate (19.65 g, 76.16 mmol) in dichloromethane (50 ml) and the mixture was stirred for 15 minutes and then triethylamine (95.5 ml, 0.686 mol) was added dropwise over 10 minutes and allowed to rise to room temperature. After chloroform (200 ml) was added to the reaction mixture, it was washed successively with 5% aqueous hydrochloric acid (200 ml), saturated aqueous sodium hydrogen carbonate (200 ml) and saturated aqueous sodium chloride (200 ml), dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure to give 7-(p-toluenesulfonyloxy)-2-heptenal (24.5 g). This aldehyde was used for the subsequent reaction without purification.

Workup

  1. stirringthe mixture was stirred for 15 minutes
  2. customto rise to room temperature
  3. washwas washed successively with 5% aqueous hydrochloric acid (200 ml), saturated aqueous sodium hydrogen carbonate (200 ml) and saturated aqueous sodium chloride (200 ml)
  4. dry with materialdried over anhydrous magnesium sulfate
  5. distillationthe solvent was distilled off under reduced pressure

Sources & evidence

ORD record
ord-78df128b6e9f44328edbb4a78a9806c2
Source dataset
uspto-grants-1998_04
Patent number
US05736550

Reaction notes

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