Oxalyl chloride → HCID 67574073, compound

HRID 1418812Notes

Reaction equation

HRID 1418812 reaction equation
[CH3:1][C:2]1[CH:15]=[C:14]([C:16]([OH:18])=[O:17])[C:13]([CH3:19])=[C:12]2[C:3]=1[CH:4]=[CH:5][C:6]1[S:11][CH2:10][CH2:9][S:8][C:7]=12.[C:20](Cl)(=[O:24])[C:21](Cl)=O>O1CCCC1.CN(C)C=O>[CH3:1][C:2]1[CH:15]=[C:14]([C:16]([O:18][C:2]2[CH2:3][CH2:4][CH2:21][C:20](=[O:24])[CH:1]=2)=[O:17])[C:13]([CH3:19])=[C:12]2[C:3]=1[CH:4]=[CH:5][C:6]1[S:11][CH2:10][CH2:9][S:8][C:7]=12

Participants

5

Reactant 2

HCID 65578Oxalyl chlorideHCID 67574013HCID 67574013, compound

Product 1

HCID 67574073HCID 67574073, compound

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

To a mixture of 0.40 g of the title compound of Step D in 25 mL of tetrahydrofuran was added 0.34 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. To the resulting residue was added 25 mL of tetrahydrofuran and evaporated to dryness again. Another 25 mL of tetrahydrofuran was added to the residue and the solution was cooled to about 0° C. To this mixture was added 0.16 g of 1,3-cyclohexanedione (purchased from Aldrich Chemical Co.) followed by addition of 0.52 mL of triethylamine. The mixture was stirred overnight at room temperature. To the reaction mixture was added saturated aqueous sodium bicarbonate 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 0.21 g of the title compound of Step E as a yellow solid melting at 126°-130° C. 1H NMR (CDCl3): δ 2.18 (m, 2H), 2.49 (t, 2H), 2.64 (s, 3H), 2.72 (t, 2H), 2.90 (t, 2H), 3.06 (s, 3H), 3.52 (t, 2H), 6.07 (s, 1H), 7.50 (d, 1H), 7.62 (s, 1H), 7.70 (d, 1H).

Workup

  1. temperatureThe mixture was refluxed for 2 h
  2. concentrationwas then concentrated under reduced pressure to dryness
  3. additionTo the resulting residue was added 25 mL of tetrahydrofuran
  4. customevaporated to dryness again
  5. additionAnother 25 mL of tetrahydrofuran was added to the residue
  6. additionTo this mixture was added 0.16 g of 1,3-cyclohexanedione (purchased from Aldrich Chemical Co.)
  7. additionfollowed by addition of 0.52 mL of triethylamine
  8. additionTo the reaction mixture was added saturated aqueous sodium bicarbonate
  9. extractionthe mixture was extracted with methylene chloride
  10. dry with materialThe combined organic extracts were dried over MgSO4
  11. filtrationfiltered
  12. concentrationconcentrated under reduced pressure to dryness
  13. additionChromatography of the crude product on silica gel eluting with a mixture of hexanes:ethyl acetate (8:1

Sources & evidence

ORD record
ord-b62ae0bc28e6464c87e0cd588bdbec7e
Source dataset
uspto-grants-1999_03
Patent number
US05885936

Reaction notes

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