Dimethyl Sulfoxide → 3-Trityloxypropanal

HRID 375726Notes

Reaction equation

HRID 375726 reaction equation
C(Cl)(=O)C(Cl)=O.CS(C)=O.[C:11]([O:30][CH2:31][CH2:32][CH2:33][OH:34])([C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)([C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.C(N(CC)CC)C>C(Cl)Cl.O>[C:11]([O:30][CH2:31][CH2:32][CH:33]=[O:34])([C:18]1[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=1)([C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1

Participants

7

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 3717013-(Trityloxy)-1-propanol

Product 1

HCID 5712233-TrityloxypropanalYield 81.5%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent3×

Conditions

Temperature
-70 °C

Procedure

To a solution of 91.4 g of oxalyl chloride in 1.12 1 of methylene chloride, pre-cooled to -70° C., a solution of 123.4 g of dimethylsulfoxide in 0.18 l of methylene chloride was added within 25 minutes. The solution was stirred for 10 minutes at -70° C. Then, a solution of 143.3 g of 3-trityloxy-1-propanol in 0.6 l of methylene chloride was added within 25 minutes, the temperature being maintained at -65° to -70° C. Stirring was continued for another 10 minutes, and then, 182 g of triethylamine were added within 5 minutes at -65° to -70° C. The mixture was stirred for 20 minutes at -70° C. and then allowed to warm up to 10° C. within 1 hour. After the addition of 1.2 1 of water, stirring was continued for 5 minutes. The layers were separated, and the aqueous phase was extracted with 1.2 l of methylene chloride. The organic phases were washed with 1.2 l of water, dried over sodium sulfate, and the solvent was evaporated in vacuo. The residue was crystallized from ethyl acetate/hexane to yield 116.0 g of 3-trityloxypropionaldehyde as white crystals of m.p. 97°-98° C.

Workup

  1. temperaturethe temperature being maintained at -65° to -70° C
  2. stirringStirring
  3. waitwas continued for another 10 minutes
  4. stirringThe mixture was stirred for 20 minutes at -70° C.
  5. temperatureto warm up to 10° C. within 1 hour
  6. stirringstirring
  7. waitwas continued for 5 minutes
  8. customThe layers were separated
  9. extractionthe aqueous phase was extracted with 1.2 l of methylene chloride
  10. washThe organic phases were washed with 1.2 l of water
  11. dry with materialdried over sodium sulfate
  12. customthe solvent was evaporated in vacuo
  13. customThe residue was crystallized from ethyl acetate/hexane

Sources & evidence

ORD record
ord-dd6efeb5ad874c8c95dedd3f417226f0
Source dataset
uspto-grants-1996_01
Patent number
US05486466

Reaction notes

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