Triethylamine → HCID 55190932, compound

HRID 1686121Notes

Reaction equation

HRID 1686121 reaction equation
[CH3:1][O:2][C:3]1[CH:10]=[C:9]([O:11][CH3:12])[CH:8]=[CH:7][C:4]=1[CH2:5][NH2:6].C(N(CC)CC)C.Cl[C:21](=[O:27])[C:22]([O:24][CH2:25][CH3:26])=[O:23]>C1COCC1>[CH2:25]([O:24][C:22](=[O:23])[C:21]([NH:6][CH2:5][C:4]1[CH:7]=[CH:8][C:9]([O:11][CH3:12])=[CH:10][C:3]=1[O:2][CH3:1])=[O:27])[CH3:26]

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 20884Ethoxalyl chlorideHCID 5972502,4-Dimethoxybenzylamine

Product 1

HCID 55190932HCID 55190932, compoundYield 92.8%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
2.5 °C

Procedure

A clean and dry jacketed reactor was equipped with a condenser, a Claisen adapter, a temperature probe, and an addition funnel or head column. The reactor was flushed with nitrogen gas for at least 15 minutes. The reactor was then charged with 1,396 g (1 equiv., 8.3 mol) of 2,4-dimethoxybenzylamine, 1,693 g (2 equiv., 16.7 mol) of triethylamine, and 25,086 mL of THF. The mixture was cooled to from 0 to 5° C. Ethyl chlorooxoacetate (1140 g, 1 equiv., 8.3 mol) was added to an addition funnel or head column and charged to the batch at such a rate that the internal temperature did not exceed 10° C. Solids formed approximately ⅓ into the addition. After the addition was complete, the cooling was turned off and the slurry was allowed to stir for 30 minutes at from 5° C. to 15° C. When complete, the reaction was warmed to from 20° C. to 25° C. The organic phase was washed twice with 22,580 mL of 1 N HCl. The organic phase was then washed with 12,600 mL saturated sodium bicarbonate. Next, the organic phase was washed with 12,463 mL of brine and dried over magnesium sulfate. The mixture was filtered through a thin pad of celite and concentrated at from 40° C. to 45° C. to a yellow oil. A total of 2,052 g (7.7 mol, 92%) of the crude N-(2,4-dimethoxy-benzyl)-oxalamic acid ethyl ester was isolated.

Workup

  1. customA clean and dry jacketed reactor
  2. customwas equipped with a condenser
  3. customThe reactor was flushed with nitrogen gas for at least 15 minutes
  4. additionhead column and charged to the batch at such a rate that the internal temperature
  5. customdid not exceed 10° C
  6. customSolids formed approximately ⅓ into the addition
  7. additionAfter the addition
  8. temperatureWhen complete, the reaction was warmed to from 20° C. to 25° C
  9. washThe organic phase was washed twice with 22,580 mL of 1 N HCl
  10. washThe organic phase was then washed with 12,600 mL saturated sodium bicarbonate
  11. washNext, the organic phase was washed with 12,463 mL of brine
  12. dry with materialdried over magnesium sulfate
  13. filtrationThe mixture was filtered through a thin pad of celite
  14. concentrationconcentrated at from 40° C. to 45° C. to a yellow oil

Sources & evidence

ORD record
ord-a3a3c33496c44c97ae298ef6fc8a0dd1
Source dataset
uspto-grants-2012_04
Patent number
US08148536B2

Reaction notes

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