Sodium Iodide → Ethyl 3-phenylprop-2-enoate

HRID 1194570Notes

Reaction equation

HRID 1194570 reaction equation
Cl[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Na+].[I-].[C:10]([O:14][CH2:15][CH3:16])(=[O:13])[CH:11]=[CH2:12].C(N(CC)CC)C.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.[Pd].C(OCC)C>[C:10]([O:14][CH2:15][CH3:16])(=[O:13])[CH:11]=[CH:12][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

8

Reactant 5

HCID 5238Sodium IodideHCID 7964ChlorobenzeneHCID 8471TriethylamineHCID 8821Ethyl AcrylateHCID 80271Tri-o-tolylphosphine

Product 1

HCID 7649Ethyl 3-phenylprop-2-enoateYield 63.6%

Reagents, catalysts & solvents 2

HCID 72499888Dibenzalacetone palladiumCatalystHCID 3283Diethyl EtherSolvent

Procedure

Chlorobenzene (1130 mg, 10 mmoles, 1.090 ml) NiBr2 (438 mg, 2 mmoles) and NaI (1650 mg, 11 mmoles) were placed in a dry, degassed, airtight flask and were slurried in DMF (20 ml). The mixture was placed in a 140° C. oil bath for 4 to 5 h during which time it darkened to blue-green or deep red. The solution was cooled to room temperature and ethyl acrylate (1100 mg, 11 mmoles, 1.190 ml), triethylamine (Et3N) (1111 mg, 11 mmoles, 1.530 ml), tri-o-tolyl phosphine (P(otol)3) (1216 mg, 4 mmoles) and palladium dibenzylideneacetone (Pd(dba)2) (29 mg, 0.05 mmoles) were added. A cold finger condenser was affixed under a slow argon flow. The mixture was heated overnight in a 140° C. oil bath, typically 15 to 17 h. The mixture was cooled and mixed with about 100 ml diethyl ether (Et 2 O) to precipitate inorganic salts. If the mixture was to be analyzed by gas chromatography (GC) undecane (0.700 ml) was added as an internal standard. The coupling product was isolated by filtering the Et2O slurry through a 2"×2"(5.08 cm×5.08 cm) silica gel bed packed in a fritted funnel. The crude material was eluted with an additional 200 to 250 ml Et2O. The combined Et2O fractions were washed three times with 15 ml aqueous saturated NaCl solutions, dried over MgSO4, filtered and the solvent removed on the rotary evaporator. Radial chromatography (silica gel, 5:1 volume mixture of hexane and Et2O) afforded 1120 mg (65 mole % yield) of ethyl cinnamate as a yellow oil.

Workup

  1. customdegassed
  2. customairtight flask and were slurried in DMF (20 ml)
  3. customwas placed in a 140° C.
  4. customfor 4 to 5 h
  5. customA cold finger condenser was affixed under a slow argon
  6. temperatureThe mixture was heated overnight in a 140° C. oil bath
  7. customtypically 15 to 17 h
  8. temperatureThe mixture was cooled
  9. customto precipitate inorganic salts
  10. additionwas added as an internal standard
  11. customThe coupling product was isolated
  12. filtrationby filtering the Et2O slurry through a 2"×2"(5.08 cm×5.08 cm) silica gel bed
  13. custompacked in a fritted funnel
  14. washThe crude material was eluted with an additional 200 to 250 ml Et2O
  15. washThe combined Et2O fractions were washed three times with 15 ml aqueous saturated NaCl solutions
  16. dry with materialdried over MgSO4
  17. filtrationfiltered
  18. customthe solvent removed on the rotary evaporator
  19. additionRadial chromatography (silica gel, 5:1 volume mixture of hexane and Et2O)

Sources & evidence

ORD record
ord-607e7115639443d28d9480249229c044
Source dataset
uspto-grants-1989_03
Patent number
US04814489

Reaction notes

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