Oxalyl chloride → HCID 20244299, compound

HRID 482955Notes

Reaction equation

HRID 482955 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 absorbing 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. customin terms of absorbing power
  11. additiona 1:1 mixture of ethyl acetate and heptane
  12. additionFractions containing a new product which
  13. concentrationconcentrated to a brown gum
  14. dissolutionThe combined chromatography fractions were dissolved in 50 ml of 10 percent methanolic sodium hydroxide
  15. temperaturerefluxed overnight
  16. customA tan solid separated which
  17. customwas isolated by filtration
  18. washwashed with methanol
  19. customdried
  20. customNo further purification

Sources & evidence

ORD record
ord-9264a7b7f7234e83bd3dc604bc25338e
Source dataset
uspto-grants-1986_03
Patent number
US04576975

Reaction notes

Loading…