Formaldehyde → Ethyl 2-benzylacrylate

HRID 1655360Notes

Reaction equation

HRID 1655360 reaction equation
C(NC(C)C)(C)C.[CH2:8]([O:10][C:11](=[O:23])[CH:12]([CH2:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)[C:13](C)=O)[CH3:9].C=O>O1CCCC1>[C:17]1([CH2:16][C:12]([C:11]([O:10][CH2:8][CH3:9])=[O:23])=[CH2:13])[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1

Participants

5

Reactant 3

HCID 712FormaldehydeHCID 7912DiisopropylamineHCID 246929Ethyl alpha-benzylacetoacetate

Product 1

HCID 11084648Ethyl 2-benzylacrylateYield 135.7%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

N-butyl lithium (201 ml of 1.6M) was added dropwise to diisopropyl amine (45 ml) in dry tetrahydrofuran (870 ml) at -78° C. After stirring at this temperature for 0.5 hours ethyl-2-benzylacetoacetate (39.6 g, 0.18M) in THF (250 ml) was added dropwise at 0° C. After stirring for 20 minutes, paraformaldehyde (35.42 g) was added at room temperature followed by stirring for one hour and refluxing for 4 hours. The reaction mixture was filtered and the liquid evaporated to dryness. The residue was dissolved in a mixture of KHCO3 /H2O and methylene chloride (1:1) and stirred for 0.5 hours. The layers were separated and the methylene chloride layer was dried over K2CO3 and then evaporated to dryness to yield 46.4 g of named product. This product was purified with a Prep-500 chromatograph eluting with hexane to 5% ethyl acetate/hexane gradient to yield 30 g of a clear liquid. ms (fd)= 190M+

Workup

  1. additionwas added dropwise at 0° C
  2. stirringby stirring for one hour
  3. temperaturerefluxing for 4 hours
  4. filtrationThe reaction mixture was filtered
  5. customthe liquid evaporated to dryness
  6. dissolutionThe residue was dissolved in a mixture of KHCO3 /H2O and methylene chloride (1:1)
  7. stirringstirred for 0.5 hours
  8. customThe layers were separated
  9. dry with materialthe methylene chloride layer was dried over K2CO3
  10. customevaporated to dryness

Sources & evidence

ORD record
ord-98b8aa1f25c14a998c4d2b4362bbe25b
Source dataset
uspto-grants-1993_10
Patent number
US05250542

Reaction notes

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