Carbon Dioxide → HCID 20040380, compound

HRID 1443324Notes

Reaction equation

HRID 1443324 reaction equation
[Br:1][C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=1[CH2:12]Br.C(=O)=O.[CH2:17]([Mg]Br)[CH3:18].[Cl-].[NH4+]>C(OCC)C.[Cu]I.C(#N)C.O1CCCC1>[Br:1][C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=1[CH2:12][CH2:17][CH3:18]

Participants

9

Reactant 4

HCID 280Carbon DioxideHCID 25517Ammonium ChlorideHCID 11460987Methyl 4-Bromo-3-(bromomethyl)benzoateHCID 178418443HCID 178418443, compound

Product 1

HCID 20040380HCID 20040380, compound

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 3283Diethyl EtherSolventHCID 6342AcetonitrileSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-40 °C

Procedure

In a 6-liter reactor equipped with a condenser, a central mechanical stirrer, a thermometer and a dropping funnel, introduce under nitrogen 141 g (0.46 mol) of methyl 4-bromo-3-bromomethylbenzoate, 4 liters of tetrahydrofuran and 8.9 g (0.045 mol) of copper (I) iodide. Cool the mixture to −40° C. using a bath of acetonitrile and dry ice. Add 168 cm3 of a 3M solution of ethylmagnesium bromide in diethyl ether and then allow the reaction temperature to increase to 0° C. After two hours of reaction hydrolyze the reaction mixture with 1 liter of 2.5M ammonium chloride solution. Separate the phases and extract the aqueous phase with 0.7 liter of methylene chloride. Combine the organic phases and evaporate the solvents. Pour heptane onto the product obtained and filter off the insoluble product which has formed. Evaporate the heptane and purify the resulting product by chromatography on silica gel (heptane/ethyl acetate=95/5). This gives 51 g of methyl 4-bromo-3-propylbenzoate in the form of colorless oil.

Workup

  1. customIn a 6-liter reactor equipped with a condenser, a central mechanical stirrer
  2. temperatureto increase to 0° C
  3. customAfter two hours of reaction
  4. customSeparate the phases
  5. extractionextract the aqueous phase with 0.7 liter of methylene chloride
  6. customevaporate the solvents
  7. customPour heptane onto the product obtained
  8. filtrationfilter off the insoluble product which
  9. customhas formed
  10. customEvaporate the heptane
  11. custompurify the resulting product by chromatography on silica gel (heptane/ethyl acetate=95/5)

Sources & evidence

ORD record
ord-ab5ddf5324fb49048bb1b4de813a0725
Source dataset
uspto-grants-2010_02
Patent number
US07659421B2

Reaction notes

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