Oxalyl chloride → HCID 20244299, compound

HRID 2164909Notes

Reaction equation

HRID 2164909 reaction equation
[C:1]([CH2:5][CH2:6][N:7]([CH3:14])[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)([O:3][CH3:4])=[O:2].[Cl-].[Al+3].[Cl-].[Cl-].[C:19](Cl)(=[O:23])[C:20](Cl)=[O:21]>O>[C:1]([CH2:5][CH2:6][N:7]([C:8]1[CH:13]=[CH:12][C:11]([C:20]([C:19]([C:11]2[CH:10]=[CH:9][C:8]([N:7]([CH3:14])[CH2:6][CH2:5][C:1]([O:3][CH3:4])=[O:2])=[CH:13][CH:12]=2)=[O:23])=[O:21])=[CH:10][CH:9]=1)[CH3:14])([O:3][CH3:4])=[O:2]

Participants

5

Reactant 3

HCID 65578Oxalyl chlorideHCID 337190methyl 3-(N-methylanilino)propanoateHCID 6451240Aluminum(III) Chloride

Product 1

HCID 20244299HCID 20244299, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

4,4'-bis(N-2-carbomethoxyethyl-N-methylamino)benzil was prepared according to the procedure of Tuzun, et al. (Org. Syn., 41, 1 (1961)). Charges were 86.4 g of N-2-carbomethoxyethyl-N-methylaniline (prepared according to the procedure in Example 1), 41.7 g of anhydrous aluminum chloride and 6.7 ml of oxalyl chloride. After the addition of 157 ml of water the reaction mixture was extracted three times with 100 ml portions of chloroform. The chloroform extract was washed with water, dried over anhydrous sodium sulfate and filtered. The solvent was removed on a steam bath and the dark brown residue was chromatographed on Activity I basic alumina (the most active and dried form, in terms of adsorbing power, of chromatographic grade alumina) using a 1:1 mixture of ethyl acetate and heptane. Fractions containing a new product which appeared to be free of starting material by TLC (thin layer chromatography) were combined and concentrated to a brown gum. The combined chromatography fractions were dissolved in 50 ml of 10 percent methanolic sodium hydroxide and refluxed overnight. A tan solid separated which was isolated by filtration, washed with methanol and dried. This material in water had λmax=382 nm and εmax=14,650. This is only one third the extinction coefficient reported for 4,4'-bis(dimethylamino)benzil. No further purification was attempted.

Workup

  1. customprepared
  2. extractionwas extracted three times with 100 ml portions of chloroform
  3. extractionThe chloroform extract
  4. washwas washed with water
  5. dry with materialdried over anhydrous sodium sulfate
  6. filtrationfiltered
  7. customThe solvent was removed on a steam bath
  8. customthe dark brown residue was chromatographed on Activity I basic alumina (the most active and
  9. customdried form
  10. additiona 1:1 mixture of ethyl acetate and heptane
  11. additionFractions containing a new product which
  12. concentrationconcentrated to a brown gum
  13. dissolutionThe combined chromatography fractions were dissolved in 50 ml of 10 percent methanolic sodium hydroxide
  14. temperaturerefluxed overnight
  15. customA tan solid separated which
  16. customwas isolated by filtration
  17. washwashed with methanol
  18. customdried
  19. customNo further purification

Sources & evidence

ORD record
ord-831c28e3287b40c79e4316bb9e6a9140
Source dataset
uspto-grants-1985_03
Patent number
US04507497

Reaction notes

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