Ethyl Bromide → HCID 13241451, compound

HRID 1388802Notes

Reaction equation

HRID 1388802 reaction equation
C(Br)C.[Mg].Cl[C:6]1[CH:11]=[CH:10][C:9]([CH:12]=[C:13]([CH3:15])[CH3:14])=[CH:8][CH:7]=1.Br[CH:17]([CH3:23])[C:18]([O:20][CH2:21][CH3:22])=[O:19].[Cl-].[NH4+]>[Ni](Cl)Cl.C1COCC1>[CH3:14][C:13]([CH3:15])=[CH:12][C:9]1[CH:10]=[CH:11][C:6]([CH:17]([CH3:23])[C:18]([O:20][CH2:21][CH3:22])=[O:19])=[CH:7][CH:8]=1

Participants

8

Reactant 5

HCID 6332Ethyl BromideHCID 25517Ammonium ChlorideHCID 79040Ethyl 2-bromopropionateHCID 209164Styrene, 4-chloro-beta,beta-dimethyl-HCID 5462224Magnesium

Product 1

HCID 13241451HCID 13241451, compoundYield 36.6%

Reagents, catalysts & solvents 2

HCID 24385Nickel DichlorideCatalystHCID 8028TetrahydrofuranSolvent4×

Conditions

Temperature
115 °C

Procedure

Under an atmosphere of nitrogen, 0.1 g of ethyl bromide was added to a solution composed of 0.27 g of magnesium turnings for Grignard reaction, 1.67 g of p-chloro-(2-methyl-1-propenyl)benzene and 1 ml of THF. After the starting of the reaction, the mixture was heated to 115° C. THF was added little by little so as to maintain the temperature in the range of 110° to 120° C., and the mixture was maintained at this temperature for 4 hours. After cooling, 5 ml of THF was added. The resulting Grignard reagent solution was added dropwise to a solution composed of 1.81 g of ethyl α-bromopropionate, 0.013 g of nickel chloride and 4 ml of THF. After the addition, the mixture was stirred for 1 hour, and an aqueous solution of ammonium chloride was added. The mixture was extracted with diethyl ether. The ethereal extract was washed with an aqueous solution of sodium chloride, dried, and concentrated. The concentrate was purified by silica gel column chromatography to give 0.85 g (yield 36.6%) of ethyl α-[p-(2-methyl-1-propenyl)phenyl]propionate having the following NMR spectrum.

Workup

  1. customAfter the starting of the reaction
  2. temperatureto maintain the temperature in the range of 110° to 120° C.
  3. temperaturethe mixture was maintained at this temperature for 4 hours
  4. temperatureAfter cooling
  5. additionAfter the addition
  6. extractionThe mixture was extracted with diethyl ether
  7. extractionThe ethereal extract
  8. washwas washed with an aqueous solution of sodium chloride
  9. customdried
  10. concentrationconcentrated
  11. customThe concentrate was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-7357aa223ac54dd49036972af57e662a
Source dataset
uspto-grants-1984_02
Patent number
US04433160

Reaction notes

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