Water → 2-cyano-(E)-cinnamaldehyde

HRID 728030Notes

Reaction equation

HRID 728030 reaction equation
[Li].[C:2]([C:4]1[CH:11]=[CH:10][CH:9]=[CH:8][C:5]=1[CH:6]=O)#[N:3].[Br-].[O:13]1CCO[CH:14]1[CH2:18][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.O>CO.CN(C)C=O>[C:2]([C:4]1[CH:11]=[CH:10][CH:9]=[CH:8][C:5]=1/[CH:6]=[CH:18]/[CH:14]=[O:13])#[N:3]

Participants

7

Reactant 4

HCID 962WaterHCID 1012092-CyanobenzaldehydeHCID 2724194(1,3-Dioxolan-2-ylmethyl)triphenylphosphonium bromideHCID 3028194Lithium

Product 1

HCID 198233462-cyano-(E)-cinnamaldehydeYield 45%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
85 °C

Procedure

A solution of lithium (77 mg) in methanol (30 ml) was added during 2 hours to a stirred suspension of 2-cyanobenzaldehyde and (1,3-dioxolan-2-yl-methyl)-triphenyl phosphonium bromide (4.71 g) in dimethylformamide (34 ml) at 85° C. The mixture was stirred at 85° C. for 6 hours, allowed to cool and poured into water (450 ml). The reaction mixture was extracted with diethyl ether (3×120 ml) and the combined ether extracts washed with saturated brine, dried (MgSO4) and evaporated. The residue was dissolved and stirred in tetrahydrofuran (30 ml) and 3M hydrochloric acid (30 ml) for 2 hours. The mixture was diluted with water (100 ml) and extracted with diethyl ether (300 ml). The ether was washed with saturated sodium hydrogen carbonate solution (2×50 ml) and saturated brine, dried (MgSO4) and evaporated. The residue was purified by flash column chromatography on silica, eluting with n-hexane-ethyl acetate (80:20:, by volume) to give as a pale yellow solid 2-cyano-(E)-cinnamaldehyde (504 mg, 45%) m.p. 107°-110° C.; NMR: 6.82 (1H,q), 7.69 (5H,m) and 9.81 (1H,d); m/e 157 (M+).

Workup

  1. temperatureto cool
  2. extractionThe reaction mixture was extracted with diethyl ether (3×120 ml)
  3. washthe combined ether extracts washed with saturated brine
  4. dry with materialdried (MgSO4)
  5. customevaporated
  6. dissolutionThe residue was dissolved
  7. stirringstirred in tetrahydrofuran (30 ml)
  8. wait3M hydrochloric acid (30 ml) for 2 hours
  9. additionThe mixture was diluted with water (100 ml)
  10. extractionextracted with diethyl ether (300 ml)
  11. washThe ether was washed with saturated sodium hydrogen carbonate solution (2×50 ml) and saturated brine
  12. dry with materialdried (MgSO4)
  13. customevaporated
  14. customThe residue was purified by flash column chromatography on silica
  15. washeluting with n-hexane-ethyl acetate (80:20:, by volume)

Sources & evidence

ORD record
ord-df1c1978ad8b4a73855b7139a347daf6
Source dataset
uspto-grants-1991_09
Patent number
US05047412

Reaction notes

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