Sodium Chloride → HCID 21849003, compound

HRID 617707Notes

Reaction equation

HRID 617707 reaction equation
[CH3:1][C:2]1[C:7]2[C:8]3([CH2:13][CH2:14][S:15][C:6]=2[C:5]([CH3:16])=[CH:4][C:3]=1[C:17]([OH:19])=[O:18])[S:12][CH2:11][CH2:10][S:9]3.C(Cl)(=O)C(Cl)=O.[C:26]1(=O)[CH2:31][CH2:30][CH2:29][C:28](=[O:32])[CH2:27]1.C(N(CC)CC)C.[Cl-].[Na+]>C(Cl)Cl.CN(C)C=O>[CH3:1][C:2]1[C:7]2[C:8]3([CH2:13][CH2:14][S:15][C:6]=2[C:5]([CH3:16])=[CH:4][C:3]=1[C:17]([O:19][C:26]1[CH2:31][CH2:30][CH2:29][C:28](=[O:32])[CH:27]=1)=[O:18])[S:12][CH2:11][CH2:10][S:9]3

Participants

8

Reactant 5

HCID 5234Sodium ChlorideHCID 8471TriethylamineHCID 104341,3-CyclohexanedioneHCID 65578Oxalyl chlorideHCID 10957942HCID 10957942, compound

Product 1

HCID 21849003HCID 21849003, compoundYield 70.7%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideCatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of the title compound of Step B (0.77 g, 2.4 mmol) in methylene chloride (25 mL) under a nitrogen atmosphere was added oxalyl chloride (Aldrich, 0.63 mL, 7.2 mmol) and 1 drop of N,N-dimethylformamide. The resulting mixture was refluxed for 1.5 h and was then evaporated to dryness. To the resulting residue was added methylene chloride (25 mL) and the resulting mixture was evaporated to dryness. Another 25 mL of methylene chloride was added to the residue, and the solution was cooled to about 0° C. To this mixture was added 1,3-cyclohexanedione (Aldrich, 0.30 g, 2.6 mmol) followed by addition of triethylamine (1.0 mL, 7.2 mmol). The mixture was stirred overnight while warming to room temperature. To the reaction mixture was added saturated aqueous sodium chloride and the resulting mixture was extracted three times with diethyl ether. The combined organic extracts were dried (MgSO4), filtered, and concentrated under reduced pressure to dryness. Chromatography of the crude product on silica gel with a mixture of hexanes:ethyl acetate (3:1) yielded the title compound of Step C (0.69 g) as a semi-solid. 1H NMR (CDCl3): δ2.13 (m,2H), 2.26 (s,3H), 2.45 (t,2H), 2.66 (m,2H), 2.76 (m,2H), 2.95 (s,3H), 3.18 (m,2H), 3.50-3.70 (4H), 6.00 (s,1H), 7.50 (s,1H).

Workup

  1. temperatureThe resulting mixture was refluxed for 1.5 h
  2. customwas then evaporated to dryness
  3. additionTo the resulting residue was added methylene chloride (25 mL)
  4. customthe resulting mixture was evaporated to dryness
  5. additionAnother 25 mL of methylene chloride was added to the residue
  6. temperaturewhile warming to room temperature
  7. extractionthe resulting mixture was extracted three times with diethyl ether
  8. dry with materialThe combined organic extracts were dried (MgSO4)
  9. filtrationfiltered
  10. concentrationconcentrated under reduced pressure to dryness
  11. additionChromatography of the crude product on silica gel with a mixture of hexanes:ethyl acetate (3:1)

Sources & evidence

ORD record
ord-4c58437d1e2b4655a622bda7df46181f
Source dataset
uspto-grants-1999_09
Patent number
US05952266

Reaction notes

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