Dimethyl Sulfoxide → HCID 13367859, compound

HRID 485504Notes

Reaction equation

HRID 485504 reaction equation
C(Cl)(=O)C(Cl)=O.CS(C)=O.[CH3:11][C:12]12[CH2:21][CH:16]([C:17]([CH3:20])([CH3:19])[O:18]1)[CH2:15][CH2:14][CH:13]2[OH:22].C(N(CC)CC)C>C(Cl)Cl>[CH3:11][C:12]12[CH2:21][CH:16]([C:17]([CH3:19])([CH3:20])[O:18]1)[CH2:15][CH2:14][C:13]2=[O:22]

Participants

6

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 13367858HCID 13367858, compound

Product 1

HCID 13367859HCID 13367859, compoundYield 122.4%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Conditions

Temperature
-60 °C

Procedure

To a solution of 6.72 g of oxalyl chloride in 150 ml of methylene chloride at -60° C. was added dropwise 8.24 g of dimethyl sulfoxide in 20 ml of methylene chloride. After stirring for 10 minutes at -60° C. under a nitrogen atmosphere, a solution of 7.50 g of 5,7,7-trimethyl-6-oxabicyclo[3.2.1]octan-4-ol in 40 ml of methylene chloride was added dropwise. A white precipitate formed. After stirring in the cold for 15 minutes, 22.22 g of triethylamine was added in a stream via syringe. The reaction mixture was allowed to rise to room temperature and after 15 minutes was poured into 200 ml of ice water. The resulting phases were separated and the aqueous phase was extracted with two 100 ml portions of methylene chloride. The combined organic phases were washed twice with 100 ml portions of saturated aqueous sodium chloride, dried (MgSO4) and concentrated in vacuo to leave 9.07 g of an orange liquid containing some beige solid. This crude mixture was diluted with hexane and filtered. The filtrate was dried (MgSO4) and concentrated in vacuo to leave 8.06 g of orange liquid. Vacuum distillation of the liquid gave two fractions of the desired product; 4.35 g, b.p. 78°-85° C. (4 mm) of 82% purity by GLC and 1.86 g, b.p. 85°-93° C. (4 mm) of 95% purity by GLC.

Workup

  1. customA white precipitate formed
  2. stirringAfter stirring in the cold for 15 minutes
  3. waitto rise to room temperature and after 15 minutes
  4. customThe resulting phases were separated
  5. extractionthe aqueous phase was extracted with two 100 ml portions of methylene chloride
  6. washThe combined organic phases were washed twice with 100 ml portions of saturated aqueous sodium chloride
  7. dry with materialdried (MgSO4)
  8. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-81f37cd23ba54349afa25ea9f3b58e75
Source dataset
uspto-grants-1985_08
Patent number
US04536586

Reaction notes

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