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p-Bromochlorobenzene → 1-Methycyclopropyl 4-chlorophenyl ketone

HRID 847163
Notes
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Reaction equation

HRID 847163 reaction equation
[CH2:1]([Li])CCC.Br[C:7]1[CH:12]=[CH:11][C:10]([Cl:13])=[CH:9][CH:8]=1.CON(C)[C:17]([C:19]1(OC)[CH2:21][CH2:20]1)=[O:18].C(OCC)(=O)C>C(OCC)C>[Cl:13][C:10]1[CH:11]=[CH:12][C:7]([C:17]([C:19]2([CH3:1])[CH2:21][CH2:20]2)=[O:18])=[CH:8][CH:9]=1
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

6

Reactant 4

HCID 7806p-BromochlorobenzeneHCID 8857Ethyl AcetateHCID 19882457N,1-Dimethoxy-N-methylcyclopropane-1-carboxamideHCID 178418339Butyllithium

Product 1

HCID 678954001-Methycyclopropyl 4-chlorophenyl ketoneYield 97%

Reagents, catalysts & solvents 1

HCID 3283
Diethyl Ether
Solvent
2×

Conditions

Temperature
0 °C

Procedure

22 ml (0.036 mol) of a 1.6 molar n-butyl-lithium solution are added at -78° C. with stirring to a mixture of 6.9 g (0.036 mol) of 4-bromochlorobenzene and 70 ml of diethyl ether. The reaction mixture is warmed to 0° C. and stirred at this temperature for 15 minutes. After cooling to -78° C. again, a solution of 4.8 g (0.03 mol) of N-methoxy-N-methyl-1-methoxycyclopropane-carboxamide in 20 ml of diethyl ether is added rapidly. The mixture is then subsequently stirred at -78° C., at 0° C. and at room temperature, in each case for one hour. 20 ml of ethyl acetate are then added to the reaction mixture, which is stirred for 5 minutes and then poured into ice-water. The resulting mixture is extracted three times with ethyl acetate, and the combined organic phases are dried over sodium sulphate and then concentrated by stripping off the solvent under reduced pressure. 6.1 g (97% of theory) of 1-methycyclopropyl 4-chlorophenyl ketone are obtained in this manner and are reacted further without prior purification.

Workup

  1. temperatureAfter cooling to -78° C. again
  2. stirringThe mixture is then subsequently stirred at -78° C., at 0° C. and at room temperature, in each case for one hour
  3. stirringis stirred for 5 minutes
  4. extractionThe resulting mixture is extracted three times with ethyl acetate
  5. dry with materialthe combined organic phases are dried over sodium sulphate
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-b0a4f4e81c824cebbda9ae918154be97
Source dataset
uspto-grants-1992_08
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US05140035

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes