Triethylamine → HCID 14851257, compound

HRID 1032241Notes

Reaction equation

HRID 1032241 reaction equation
[Br:1][C:2]1[C:10]([O:11][CH2:12][CH2:13][O:14][CH3:15])=[C:9]([S:16]([CH2:19][CH3:20])(=[O:18])=[O:17])[CH:8]=[CH:7][C:3]=1[C:4]([OH:6])=O.C(Cl)(=O)C(Cl)=O.[C:27]1(=[O:34])[CH2:32][CH2:31][CH2:30][C:29](=[O:33])[CH2:28]1.C(N(CC)CC)C>C(Cl)Cl.CN(C=O)C>[Br:1][C:2]1[C:10]([O:11][CH2:12][CH2:13][O:14][CH3:15])=[C:9]([S:16]([CH2:19][CH3:20])(=[O:18])=[O:17])[CH:8]=[CH:7][C:3]=1[C:4]([CH:28]1[C:29](=[O:33])[CH2:30][CH2:31][CH2:32][C:27]1=[O:34])=[O:6]

Participants

7

Reactant 4

HCID 8471TriethylamineHCID 104341,3-CyclohexanedioneHCID 65578Oxalyl chlorideHCID 14851228HCID 14851228, compound

Product 1

HCID 14851257HCID 14851257, compoundYield 47.7%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideCatalystHCID 6344DichloromethaneSolvent

Procedure

2-Bromo-3-(2-methoxyethoxy)-4-ethylsulfonyl benzoic acid (6.1 g, 0.018 mol) was diluted in 50 mL of methylene chloride and 2 drops of DMF were added, followed by the slow addition of oxalyl chloride (3.81 g, 0.03 mol). After the addition was complete, the solution was refluxed for 1 hour, cooled and concentrated under vacuum. The crude acid chloride was diluted in 25 mL of methylene chloride and 2.24 g (0.02 mol) of 1,3-cyclohexanedione was added, followed by an excess of triethylamine (4.0 g). After stirring overnight, the organic layer was washed three times with dilute (1 N) hydrochloric acid, dried and concentrated. The crude enol ester was dissolved in 25 mL of acetonitrile and ten drops of acetone cyanohydrin and 4 mL of triethylamine were added and this reaction mixture was stirred at room temperature for 48 hours. The organic phase was washed three times with 1 N hydrochloric acid and then extracted with base. The base extracts were combined and acidified and extracted three times with 50 mL of methylene chloride. The methylene chloride extracts were dried, concentrated and chromatographed on silica gel using ether/methylene chloride/acetic acid to give 3.96 g of pure 2-[2'-bromo-3'-(2-methoxyethoxy)-4'-ethylsulfonylbenzoyl]-1,3-cyclohexanedione.

Workup

  1. additionAfter the addition
  2. temperaturethe solution was refluxed for 1 hour
  3. temperaturecooled
  4. concentrationconcentrated under vacuum
  5. additionThe crude acid chloride was diluted in 25 mL of methylene chloride
  6. washthe organic layer was washed three times
  7. additionwith dilute (1 N) hydrochloric acid
  8. customdried
  9. concentrationconcentrated
  10. dissolutionThe crude enol ester was dissolved in 25 mL of acetonitrile
  11. additionten drops of acetone cyanohydrin and 4 mL of triethylamine were added
  12. stirringthis reaction mixture was stirred at room temperature for 48 hours
  13. washThe organic phase was washed three times with 1 N hydrochloric acid
  14. extractionextracted with base
  15. extractionextracted three times with 50 mL of methylene chloride
  16. dry with materialThe methylene chloride extracts were dried
  17. concentrationconcentrated
  18. customchromatographed on silica gel

Sources & evidence

ORD record
ord-000d1e9abaab4e92a387099538e6146f
Source dataset
uspto-grants-1990_09
Patent number
US04957538

Reaction notes

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