Oxalyl chloride → HCID 17816541, compound

HRID 2249661Notes

Reaction equation

HRID 2249661 reaction equation
[CH2:1]([O:3][C:4](=[O:21])[CH2:5][CH2:6][C:7]1[CH:8]=[C:9]([CH:13]=[CH:14][C:15]=1[O:16][CH2:17][CH:18]([CH3:20])[CH3:19])[C:10]([OH:12])=O)[CH3:2].C(Cl)(=O)C(Cl)=O.[Cl-].[Al+3].[Cl-].[Cl-].[CH2:32]([O:37][C:38]1[CH:43]=[CH:42][CH:41]=[C:40]([O:44]CCC(C)C)[CH:39]=1)[CH2:33][CH:34]([CH3:36])[CH3:35]>C(Cl)Cl.O.CN(C)C=O>[OH:44][C:40]1[CH:39]=[C:38]([O:37][CH2:32][CH2:33][CH:34]([CH3:36])[CH3:35])[CH:43]=[CH:42][C:41]=1[C:10]([C:9]1[CH:13]=[CH:14][C:15]([O:16][CH2:17][CH:18]([CH3:20])[CH3:19])=[C:7]([CH2:6][CH2:5][C:4]([O:3][CH2:1][CH3:2])=[O:21])[CH:8]=1)=[O:12]

Participants

8

Reactant 4

HCID 65578Oxalyl chlorideHCID 6451240Aluminum(III) Chloride2×HCID 17816522HCID 17816522, compoundHCID 22759692HCID 22759692, compound

Product 1

HCID 17816541HCID 17816541, compoundYield 40.6%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent2×

Procedure

In 10 ml of methylene chloride is dissolved 1.00 g of 3-(3-ethoxy-3-oxopropyl)-4-isobutoxybenzoic acid. After adding 0.36 ml of oxalyl chloride and 20 μl of N,N-dimethylformamide successively at ambient temperature, the mixture thus obtained is stirred at ambient temperature for one hour. Then, 0.95 g of aluminum chloride and 1.02 g of 1,3-diisopentyloxybenzene are successively added at 5-10° C., and stirred at the same temperature as above for 30 minutes and then at ambient temperature for 30 minutes. Then, 0.45 g of aluminum chloride is added at ambient temperature and stirred at the same temperature as above for 30 minutes. The reaction mixture is added to a mixture of methylene chloride and water, and the organic layer is separated. The organic layer thus obtained is washed with water and saturated aqueous solution of sodium chloride successively and dried over anhydrous magnesium sulfate, and the solvent is distilled off under reduced pressure. The residue thus obtained is purified by silica gel column chromatography (eluent; hexane:ethyl acetate=10:1) to obtain 0.63 g of ethyl 3-[5-(2-hydroxy-4-isopentyloxybenzoyl)-2-isobutoxyphenyl]propanoate as a light yellow oily product. A 0.60 g portion of the oily product obtained above is dissolved in 12 ml of ethanol, 1.3 ml of 5 mol/L sodium hydroxide solution is added, and the mixture thus obtained is stirred at ambient temperature for 2 hours. Chloroform and water are added to the reaction mixture, pH is adjusted to 2 with 6 mol/L hydrochloric acid, and the organic layer is separated. The organic layer thus obtained is washed with water and saturated aqueous solution of sodium chloride successively and dried over anhydrous magnesium sulfate, and then the solvent is distilled off under reduced pressure. Thus, 0.48 g of [5-(2-hydroxy-4-isopentyloxybenzoyl)-2-isobutoxyphenyl]-propanoic acid is obtained as a light yellow solid product.

Workup

  1. customthe mixture thus obtained
  2. stirringstirred at the same temperature as above for 30 minutes
  3. waitat ambient temperature for 30 minutes
  4. stirringstirred at the same temperature as above for 30 minutes
  5. customthe organic layer is separated
  6. customThe organic layer thus obtained
  7. washis washed with water and saturated aqueous solution of sodium chloride successively
  8. dry with materialdried over anhydrous magnesium sulfate
  9. distillationthe solvent is distilled off under reduced pressure
  10. customThe residue thus obtained
  11. customis purified by silica gel column chromatography (eluent; hexane:ethyl acetate=10:1)

Sources & evidence

ORD record
ord-daf87b26807245aa903f0f4af88ca34d
Source dataset
uspto-grants-2008_01
Patent number
US07314888B1

Reaction notes

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