Dimethyl Sulfate → HCID 21803566, compound

HRID 1899793Notes

Reaction equation

HRID 1899793 reaction equation
[C:1](=O)([O-])[O-].[K+].[K+].[Br:7][C:8]1[CH:17]=[C:16]2[C:11]([CH:12]=[CH:13][CH:14]=[C:15]2[C:18]([CH2:20][C:21]([O:23][CH3:24])=[O:22])=[O:19])=[CH:10][CH:9]=1.S(OC)(OC)(=O)=O.[H-].[Na+]>O.CO.C(OC)(C)(C)C.CN1C(=O)N(C)CCC1>[CH3:1][O:19]/[C:18](/[C:15]1[C:16]2[C:11](=[CH:10][CH:9]=[C:8]([Br:7])[CH:17]=2)[CH:12]=[CH:13][CH:14]=1)=[CH:20]/[C:21]([O:23][CH3:24])=[O:22]

Participants

9

Reactant 4

HCID 6497Dimethyl SulfateHCID 11430Potassium CarbonateHCID 24758Sodium hydrideHCID 23371328HCID 23371328, compound

Product 1

HCID 21803566HCID 21803566, compoundYield 52.1%

Reagents, catalysts & solvents 4

HCID 887MethanolSolventHCID 962WaterSolvent2×HCID 15413tert-Butyl methyl etherSolventHCID 816462(1H)-Pyrimidinone, tetrahydro-1,3-dimethyl-Solvent2×

Conditions

Temperature
40 °C

Procedure

93 g (0.68 mol) of potassium carbonate are added to a stirred mixture of 189 g (0.61 mol) of methyl 7-bromo-1-naphthoylacetate and 500 ml of N,N'-dimethylpropyleneurea, and the mixture is stirred at 40° C. for 2 h. It is subsequently cooled to 0°-5° C., and a mixture of 85 g (0.68 mol) of dimethyl sulfate and 50 ml of N,N'-dimethylpropyleneurea is added dropwise. The mixture is then stirred at 40° C. for a further 2 h, and subsequently water and methyl tert-butyl ether are added. The aqueous phase is extracted once more with methyl tert-butyl ether, and the combined organic phases are dried over Na2SO4 and concentrated. The residue is taken up in 500 ml of N,N'-dimethylpropyleneurea, and 2.7 g (0.11 mol) of NaH are added. The mixture is stirred at room temperature for 15 h. Subsequently, 20 ml of methanol are added and the mixture is diluted with water and extracted with methyl tert-butyl ether. The organic phase is washed with water, dried over Na2SO4 and concentrated. The residue is recrystallized from methanol to give 102 g (52%) of methyl (E)-3-methoxy-3-(7-bromo-1-naphthyl)acrylate in the form of colorless crystals of melting point 111°-113° C.

Workup

  1. temperatureIt is subsequently cooled to 0°-5° C.
  2. additionis added dropwise
  3. stirringThe mixture is then stirred at 40° C. for a further 2 h
  4. extractionThe aqueous phase is extracted once more with methyl tert-butyl ether
  5. dry with materialthe combined organic phases are dried over Na2SO4
  6. concentrationconcentrated
  7. stirringThe mixture is stirred at room temperature for 15 h
  8. extractionextracted with methyl tert-butyl ether
  9. washThe organic phase is washed with water
  10. dry with materialdried over Na2SO4
  11. concentrationconcentrated
  12. customThe residue is recrystallized from methanol

Sources & evidence

ORD record
ord-d4fad2425d3340eb9a57feaa459e36af
Source dataset
uspto-grants-1996_11
Patent number
US05573999

Reaction notes

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