Ethanolamine → Diethyl Oxalate

HRID 1376667Notes

Reaction equation

HRID 1376667 reaction equation
[C:1]([O:8][CH2:9][CH3:10])(=[O:7])[C:2]([O:4][CH2:5][CH3:6])=[O:3].[CH2:11]([CH2:13][NH2:14])[OH:12]>CC(C)=O>[C:1]([O:8][CH2:9][CH3:10])(=[O:7])[C:2]([O:4][CH2:5][CH3:6])=[O:3].[OH:12][CH2:11][CH2:13][NH:14][C:2](=[O:4])[C:1]([O:8][CH2:9][CH3:10])=[O:7]

Participants

5

Reactant 2

HCID 700EthanolamineHCID 7268Diethyl Oxalate

Product 2

HCID 7268Diethyl OxalateHCID 12253017HCID 12253017, compound

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent

Procedure

To 730.7 g (5 moles) of diethyl oxalate was added dropwise at room temperature a solution of 61.1 g (1 mole) of ethanolamine in 500 ml of acetone and, after the addition finished, treatment of the mixture by distillation under reduced pressure to remove the formed ethanol and the acetone and an excess amount of diethyl oxalate yielded ethyl 2-hydroxyethyloxamate. A mixture of 80.5 g (0.5 moles) of this ethyl 2-hydroxyethyloxamate, 50.6 g (0.5 moles) of triethylamine (hereinafter, referred to as TEA), 20.0 g of water, and 1000 ml of dioxane was warmed under reflux for 8 hours and treated with solvent removal followed by dehydration yielded a triethylamine salt of 2-hydroxyethyloxamic acid. A mixture of 11.7 g (0.05 moles) of this triethylamine salt of 2-hydroxyethyloxamic acid and 5.1 g (0.05 moles) of TEA was treated with dehydration by molecular sieve and then, dissolved with warming into 300 ml of THF. To this THF solution was added dropwise under a refluxing condition during 0.5 hours a solution of 5.2 g (0.05 moles) of methacrylic acid chloride in 30 ml of THF and, after the addition finished, the mixture was further stirred under the condition for 6 hours and treated with fractional extraction to get methacryloyloxyet hyloxamic acid of the following structure: ##STR17## Besides, identification of the methacrylolyloxyethyloxamic acid 1 was carried out with 13C-NMR spectra analysis (ppm, in CDCL3) and the results were 17.93 for (2), 38.86 for (6); 62.35 for (5), 120.59 for (1), 138.86 for (3), 158.01 for (7), 160.56 for (8), and 167.06 for (4).

Workup

  1. additionafter the addition
  2. distillationtreatment of the mixture by distillation under reduced pressure
  3. customto remove the formed ethanol

Sources & evidence

ORD record
ord-ca394168c7a84a779876eb516af474f2
Source dataset
uspto-grants-1997_09
Patent number
US05663262

Reaction notes

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