Iodine → HCID 21448619, compound

HRID 596866Notes

Reaction equation

HRID 596866 reaction equation
II.Br[C:4]([CH3:10])([CH3:9])[C:5]([O:7][CH3:8])=[O:6].[CH3:11][O:12][C:13]1[CH:18]=[CH:17][C:16]([CH2:19][C:20](OC)=[O:21])=[CH:15][CH:14]=1.S(=O)(=O)(O)O>O1CCCC1.[Zn]>[CH3:9][C:4]([CH3:10])([C:20]([CH2:19][C:16]1[CH:17]=[CH:18][C:13]([O:12][CH3:11])=[CH:14][CH:15]=1)=[O:21])[C:5]([O:7][CH3:8])=[O:6]

Participants

7

Reactant 4

HCID 807IodineHCID 1118Sulfuric AcidHCID 90097Methyl 2-bromo-2-methylpropionateHCID 90266Methyl 4-methoxyphenylacetate

Product 1

HCID 21448619HCID 21448619, compoundYield 60%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 8028TetrahydrofuranSolvent2×

Procedure

To a gently refluxing suspension of 227 g of granulated zinc, activated by the addition of 1 g of iodine, in 500 ml of dry tetrahydrofurane there is dropped with mechanical stirring and under exclusion of moisture, a solution of 700 g of methyl 2-bromoisobutyrate and 540 g of methyl p-methoxy-phenylacetate in 500 ml of tetrahydrofurane. As soon as the reaction has started, apparent from the formation of a turbidity and stronger reflux, the addition is continued at such a rate as to maintain gentle reflux with minimal application of external heating. After all of the solution has been added, stirring and refluxing is continued for 5 hours. Then the reaction mixture is cooled with ice and 1500 ml of 4 N sulphuric acid is added dropwise with vigorous stirring. The organic layer is separated, after the eventual removal of some solid material by filtration, and the aqueous solution extracted with ether. The combined organic solutions are washed with an aqueous solution of sodium bicarbonate. Evaporation of the solvent leaves the crude ester which is purified by distillation in vacuo. Yield 60 - 65%, boiling point 145° C (1 mm), nD20 1.5140.

Workup

  1. temperatureTo a gently refluxing
  2. additionis dropped
  3. temperaturestronger reflux
  4. additionthe addition
  5. temperatureto maintain gentle
  6. temperaturereflux with minimal application of external heating
  7. additionAfter all of the solution has been added
  8. stirringstirring
  9. temperaturerefluxing
  10. additionis added dropwise with vigorous stirring
  11. customThe organic layer is separated
  12. customafter the eventual removal of some solid material
  13. filtrationby filtration
  14. extractionthe aqueous solution extracted with ether
  15. washThe combined organic solutions are washed with an aqueous solution of sodium bicarbonate
  16. customEvaporation of the solvent

Sources & evidence

ORD record
ord-b01fee0c5d004726bfc89cfcba3066bf
Source dataset
uspto-grants-1977_03
Patent number
US04012392

Reaction notes

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