Diethyl Oxalate → HCID 178473089, compound

HRID 389925Notes

Reaction equation

HRID 389925 reaction equation
[Na].[CH2:2]([O:9][C:10]1[CH:15]=[C:14]([O:16][CH2:17][C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[C:13]([Cl:24])=[CH:12][C:11]=1[C:25](=[O:27])[CH3:26])[C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.[CH2:28]([O:30][C:31](=[O:37])[C:32](OCC)=[O:33])[CH3:29]>C(O)(=O)C>[CH2:2]([O:9][C:10]1[CH:15]=[C:14]([O:16][CH2:17][C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[C:13]([Cl:24])=[CH:12][C:11]=1[C:25](=[O:27])[CH:26]=[C:32]([OH:33])[C:31]([O:30][CH2:28][CH3:29])=[O:37])[C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1

Participants

5

Reactant 3

HCID 7268Diethyl OxalateHCID 5360545SodiumHCID 179636911-(2,4-Bis(benzyloxy)-5-chlorophenyl)ethanone

Product 1

HCID 178473089HCID 178473089, compoundYield 98%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

Sodium metal (1.35 g, 58 mmol) was cut into small pieces, rinsed with hexane to remove mineral oil, and added portion wise to anhydrous EtOH (100 ml) under a nitrogen atmosphere over a period of 20 min. The reaction mixture was stirred for a further 10 min until all sodium had reacted. 1-[2,4-bis(benzyloxy)-5-chlorophenyl]ethanone (10 g, 27.3 mmol) was added portion wise over 5 min, and the resulting suspension was then stirred for further 5 min at RT. Diethyloxalate (6 ml, 43 mmol) was added, resulting in a thick yellow coloured precipitate. The reaction mixture was heated to reflux for 4 h, affording a dark homogeneous solution, which, upon cooling, produced a solid mass to which acetic acid (6 ml) was added. The mixture was triturated to afford a yellow solid, which was filtered, washed sequentially with water, EtOH, and Et2O, and then dried under vacuo to afford the title compound ethyl 4-(2,4-bis(benzyloxy)-5-chlorophenyl)-2-hydroxy-4-oxobut-2-enoate (12.4 g, 98%) as a yellow solid.

Workup

  1. washrinsed with hexane
  2. customto remove mineral oil
  3. additionadded portion wise to anhydrous EtOH (100 ml) under a nitrogen atmosphere over a period of 20 min
  4. customhad reacted
  5. stirringthe resulting suspension was then stirred for further 5 min at RT
  6. customresulting in a thick yellow coloured precipitate
  7. temperatureThe reaction mixture was heated
  8. temperatureto reflux for 4 h
  9. customaffording a dark homogeneous solution, which
  10. temperatureupon cooling
  11. additionwas added
  12. customThe mixture was triturated
  13. customto afford a yellow solid, which
  14. filtrationwas filtered
  15. washwashed sequentially with water, EtOH, and Et2O
  16. customdried under vacuo

Sources & evidence

ORD record
ord-382bff0d3b7643f99893502da182d0ad
Source dataset
uspto-grants-2013_02
Patent number
US08383616B2

Reaction notes

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