Dimethyl Sulfate → HCID 15125732, compound

HRID 2108224Notes

Reaction equation

HRID 2108224 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[CH2:8][C:9]([O:11][CH3:12])=[O:10].[CH:13]([O:15][CH3:16])=O.[H-].[Na+].BrC1C=CC=CC=1C(=CO)C(OC)=O.C(=O)([O-])[O-].[K+].[K+].S(OC)(OC)(=O)=O>CN(C=O)C.O>[Br:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1/[C:8](=[CH:13]\[O:15][CH3:16])/[C:9]([O:11][CH3:12])=[O:10]

Participants

9

Reactant 6

HCID 6497Dimethyl SulfateHCID 7865Methyl formateHCID 11430Potassium CarbonateHCID 24758Sodium hydrideHCID 8063364Methyl 2-(2-bromophenyl)acetateHCID 67839179HCID 67839179, compound

Product 1

HCID 15125732HCID 15125732, compoundYield 88%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 6228DimethylformamideSolvent3×

Procedure

A mixture of methyl ortho-bromophenylacetate (5.23 g) and methyl formate (27.46 g) in DMF(6 ml) was added dropwise to a stirred suspension of sodium hydride (1.10 g) in DMF (45 ml) at 0° to 5° C. (frothing). When thin-layer chromatography showed that reaction was complete, the mixture was poured into water, acidified and extracted with ether. The extracts were dried and concentrated to give crude methyl 2-(2-bromophenyl)-3-hydroxypropenoate (5.95 g) as a yellow liquid which was used directly in the next step. The crude methyl 2-(2-bromophenyl)-3-hydroxypropenoate (5.95 g) was stirred with anhydrous potassium carbonate (6.38 g) and dimethyl sulphate (2.75 g) in DMF (40 ml). After 3 hours at room temperature, the reaction mixture was poured into water and extracted with ether (2×75 ml). The combined ether layers were washed with water and brine (×1) and dried. Filtration and evaporation gave a yellow oil which crystallised on standing to give (E)-methyl 2-(2-bromophenyl)-3-methoxypropenoate (5.20 g, 88% yield from methyl ortho-bromophenylacetate) as a crystalline solid, m.p. 68°-69° C., IR maxima 1712, 1638 cm-1 ; 1H n.m.r delta 3.73 (3H, s); 3.86 (3H, s); 7.56 (1H, s) p.p.m.

Workup

  1. customWhen thin-layer chromatography showed that reaction
  2. extractionextracted with ether
  3. customThe extracts were dried
  4. concentrationconcentrated
  5. customto give crude methyl 2-(2-bromophenyl)-3-hydroxypropenoate (5.95 g) as a yellow liquid which
  6. extractionextracted with ether (2×75 ml)
  7. washThe combined ether layers were washed with water and brine (×1)
  8. customdried
  9. filtrationFiltration and evaporation
  10. customgave a yellow oil which
  11. customcrystallised

Sources & evidence

ORD record
ord-3182d42ce6414a9f833aaa62fc2b78e5
Source dataset
uspto-grants-1990_06
Patent number
US04937374

Reaction notes

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