Oxalyl chloride → HCID 67624562, compound

HRID 1418805Notes

Reaction equation

HRID 1418805 reaction equation
[CH3:1][C:2]1[C:11]2[S:10][CH2:9][C:8]3[S:12][CH2:13][CH2:14][S:15][C:7]=3[C:6]=2[C:5]([CH3:16])=[C:4]([C:17]([OH:19])=[O:18])[CH:3]=1.[C:20](Cl)(=[O:24])[C:21](Cl)=O>C(Cl)Cl.CN(C)C=O>[CH3:1][C:2]1[C:11]2[S:10][CH2:9][C:8]3[S:12][CH2:13][CH2:14][S:15][C:7]=3[C:6]=2[C:5]([CH3:16])=[C:4]([C:17]([O:19][C:2]2[CH2:3][CH2:4][CH2:21][C:20](=[O:24])[CH:1]=2)=[O:18])[CH:3]=1

Participants

5

Reactant 2

HCID 65578Oxalyl chlorideHCID 67625499HCID 67625499, compound

Product 1

HCID 67624562HCID 67624562, compound

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideCatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

To a mixture of 0.78 g of the title compound of Step A in 35 mL of methylene chloride was added 0.66 mL of oxalyl chloride (purchased from Aldrich Chemical Co.) and 2 drops of N,N-dimethylformamide. The mixture was refluxed for 2 h and was then concentrated under reduced pressure to dryness. The resulting residue was redissolved in 30 mL of methylene chloride and the solution was evaporated to dryness again. Another 30 mL of methylene chloride was added to the residue and the solution was cooled to about 0° C. To this solution was added 0.31 g of 1,3-cyclohexanedione (purchased from Aldrich Chemical Co.) followed by addition of 1.0 mL of triethylamine. The mixture was stirred overnight while warming to room temperature. Saturated aqueous sodium bicarbonate was then added to the reaction mixture and the mixture was extracted with methylene chloride. The combined organic extracts were dried over MgSO4, filtered, and concentrated under reduced pressure to dryness. Chromatography of the crude product on silica gel eluting with a mixture of hexanes:ethyl acetate (8:1 and then 4:1) yielded 0.58 g of the title compound of Step B as a yellow solid melting at 120°-126° C. 1H NMR (CDCl3): δ 2.15 (m, 2H), 2.36 (s, 3H), 2.46 (t, 2H), 2.66 (t, 2H), 2.67 (s, 3H), 3.07 (m, 2H), 3.24 (br s, 2H), 3.41 (m, 2H), 6.00 (s, 1H), 7.60 (s, 1H).

Workup

  1. temperatureThe mixture was refluxed for 2 h
  2. concentrationwas then concentrated under reduced pressure to dryness
  3. dissolutionThe resulting residue was redissolved in 30 mL of methylene chloride
  4. customthe solution was evaporated to dryness again
  5. additionAnother 30 mL of methylene chloride was added to the residue
  6. additionTo this solution was added 0.31 g of 1,3-cyclohexanedione (purchased from Aldrich Chemical Co.)
  7. additionfollowed by addition of 1.0 mL of triethylamine
  8. temperaturewhile warming to room temperature
  9. additionSaturated aqueous sodium bicarbonate was then added to the reaction mixture
  10. extractionthe mixture was extracted with methylene chloride
  11. dry with materialThe combined organic extracts were dried over MgSO4
  12. filtrationfiltered
  13. concentrationconcentrated under reduced pressure to dryness
  14. additionChromatography of the crude product on silica gel eluting with a mixture of hexanes:ethyl acetate (8:1

Sources & evidence

ORD record
ord-24afb6967a1e4419ae3a543594cea2ad
Source dataset
uspto-grants-1999_03
Patent number
US05885936

Reaction notes

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