Methyl iodide → Methyl 4-(1-methoxy-1-oxopropan-2-yl)benzoate

HRID 1462386Notes

Reaction equation

HRID 1462386 reaction equation
[C:1]([O:14][CH3:15])(=[O:13])[CH2:2][C:3]1[CH:12]=[CH:11][C:6]([C:7]([O:9][CH3:10])=[O:8])=[CH:5][CH:4]=1.[H-].[K+].[CH3:18]I>O1CCCC1>[CH3:18][CH:2]([C:3]1[CH:12]=[CH:11][C:6]([C:7]([O:9][CH3:10])=[O:8])=[CH:5][CH:4]=1)[C:1]([O:14][CH3:15])=[O:13]

Participants

5

Reactant 3

HCID 6328Methyl iodideHCID 82127Potassium hydrideHCID 10536335Benzeneacetic acid, 4-(methoxycarbonyl)-, methyl ester

Product 1

HCID 157136Methyl 4-(1-methoxy-1-oxopropan-2-yl)benzoateYield 71%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of dimethyl homoterephthalate (7, R=H) (4.16 g, 20 mmole) in 15 ml of dry tetrahydrofuran was added dropwise over 15 minutes to a stirred mixture of potassium hydride (2.5 g of 35% oil suspension, 22 mmole) in 75 ml of dry tetrahydrofuran at 0° C. After 30 minutes a homogeneous yellow suspension had formed. Methyl iodide (2.79 g, 22 mmole) was then added over a 5 minute period and the resulting mixture stirred for 30 minutes. The mixture was quenched with 2 ml of 50% acetic acid, diluted with 500 ml of water and extracted with ether. The ether extract was washed with water, dried over magnesium sulfate and evaporated to leave an oil. The material was chromatographed on silica gel with elution by ether-hexane (1:9) to afford (71%) of a clear oil; m/e 222 (M+): NMR (CDCl3) 1.50 (3H, d, CH3), 3.65 (3H, s, OCH3), 3.93 (3H, s, OCH3 benzoate).

Workup

  1. customAfter 30 minutes a homogeneous yellow suspension had formed
  2. customThe mixture was quenched with 2 ml of 50% acetic acid
  3. additiondiluted with 500 ml of water
  4. extractionextracted with ether
  5. extractionThe ether extract
  6. washwas washed with water
  7. dry with materialdried over magnesium sulfate
  8. customevaporated
  9. customto leave an oil
  10. customThe material was chromatographed on silica gel with elution by ether-hexane (1:9)

Sources & evidence

ORD record
ord-0179b73c44294d0793a5922cd0485ea4
Source dataset
uspto-grants-1984_07
Patent number
US04460591

Reaction notes

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