Methyl iodide → methyl (Z)-3-methoxy-2-(o-tolyl)prop-2-enoate

HRID 1721282Notes

Reaction equation

HRID 1721282 reaction equation
[C:1]1([CH3:12])[CH:6]=[CH:5][CH:4]=[CH:3][C:2]=1[CH2:7][C:8]([O:10][CH3:11])=[O:9].[H-].[Na+].[H][H].CI.[CH:19]([O:21][CH3:22])=O>CN(C)C=O.O1CCCC1.CO>[CH3:19][O:21]/[CH:22]=[C:7](/[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][C:1]=1[CH3:12])\[C:8]([O:10][CH3:11])=[O:9]

Participants

9

Reactant 5

HCID 6328Methyl iodideHCID 7865Methyl formateHCID 24758Sodium hydrideHCID 7021479Methyl 2-(2-methylphenyl)acetateHCID 178418361HCID 178418361, compound

Product 1

HCID 5478050methyl (Z)-3-methoxy-2-(o-tolyl)prop-2-enoate

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

Methyl o-tolylacetate (100 g) was dissolved in a mixture of methyl formate (450 ml) and dimethyl formamide (200 ml). The solution was added to a petrol washed suspension of sodium hydride (from 36.5 g of an 80% dispersion in oil) in dimethylformamide (100 ml) with cooling. The mixture was then stirred at room temperature overnight. Excess methyl formate and most of the dimethylformamide were evaporated and water (500 ml) was added. The mixture was treated with ether and the aqueous phase separated, acidified and extracted with ether. The extract was worked up in conventional manner to give a brown oil. This was dissolved in tetrahydrofuran and the solution added dropwise to sodium hydride (16.5 g of 80% dispersion in oil) in tetrahydrofuran (50 ml) with cooling. When hydrogen evolution had ceased, methyl iodide (35 ml) was added and the mixture heated to reflux for 5 hours. Methanol (5 ml) was added and the solvent evaporated. The resulting oil was partitioned between ether and water and the organic phase worked up in conventional manner to give to give methyl (Z)-3-methoxy-2-(o-tolyl)prop-2-enoate, m.p. 68°-70°. This product (185 g) was dissolved in carbon tetrachloride (1250 ml). N-Bromosuccinimide (159.3 g) was added and the mixture heated under reflux for 3 hours. The reaction mixture was then cooled and worked up to give a light brown oil. The crude product was triturated with a 10% solution of di-isopropyl ether in light petroleum to give methyl (E)-3-methoxy-2- 2-(bromomethyl)phenyl!prop-2-enoate, m.p. 87°-90° C., (Intermediate A).

Workup

  1. washwashed
  2. additionsuspension of sodium hydride (from 36.5 g of an 80% dispersion in oil) in dimethylformamide (100 ml)
  3. temperaturewith cooling
  4. customExcess methyl formate and most of the dimethylformamide were evaporated
  5. additionwater (500 ml) was added
  6. additionThe mixture was treated with ether
  7. customthe aqueous phase separated
  8. extractionextracted with ether
  9. customto give a brown oil
  10. temperaturewith cooling
  11. temperaturethe mixture heated
  12. temperatureto reflux for 5 hours
  13. customthe solvent evaporated
  14. customThe resulting oil was partitioned between ether and water
  15. customto give

Sources & evidence

ORD record
ord-8be5481bfb4d46f7a3c9579be0ddd9cf
Source dataset
uspto-grants-1996_04
Patent number
US05510344

Reaction notes

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