Hydrochloric Acid → Dimethyl 2-phenyl-3-cyano-6-bromohexane-3,4-dicarboxylate

HRID 1981283Notes

Reaction equation

HRID 1981283 reaction equation
[C:1]([CH:3]([CH:8]([C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)[CH3:9])[C:4]([O:6][CH3:7])=[O:5])#[N:2].Br[CH:17]([CH2:22][CH2:23][Br:24])[C:18]([O:20][CH3:21])=[O:19].C(=O)([O-])[O-].[K+].[K+].Cl>CS(C)=O>[C:10]1([CH:8]([C:3]([C:1]#[N:2])([C:4]([O:6][CH3:7])=[O:5])[CH:17]([C:18]([O:20][CH3:21])=[O:19])[CH2:22][CH2:23][Br:24])[CH3:9])[CH:11]=[CH:12][CH:13]=[CH:14][CH:15]=1

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 11430Potassium CarbonateHCID 296716Methyl 2,4-dibromobutanoateHCID 13276234Methyl 2-cyano-3-phenylbutyrate

Product 1

HCID 13292496Dimethyl 2-phenyl-3-cyano-6-bromohexane-3,4-dicarboxylate

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Procedure

A mixture of methyl 2-cyano-3-phenylbutyrate (78 g, 0.37 mole), methyl 2,4-dibromobutyrate (122 g, 0.47 mole), potassium carbonate (65 g, 0.47 mole) and DMSO (50 ml) was stirred on a ball mill apparatus. The reaction was completed in four hours. Ice water was added and the mixture was neutralized by adding cold hydrochloric acid. The aqueous solution was extracted several times with ether. The combined organic solution was washed sequentially with cold aqueous sodium bicarbonate and brine, then dried over magnesium sulfate. After removal of the solvent, the residue was purified by Kugelrohr distillation (100° C., 30 microns) to remove low boiling materials. The remaining oily residue (118 g., 84%) was found to be mainly the title bromide condensation product (ν<95% GC purity). MS m/e (% relative intensity) 383(M.+, 3) 381 (3), 202 (33), 182 (7), 180 (7), 105 (100).

Workup

  1. extractionThe aqueous solution was extracted several times with ether
  2. washThe combined organic solution was washed sequentially with cold aqueous sodium bicarbonate and brine
  3. dry with materialdried over magnesium sulfate
  4. customAfter removal of the solvent
  5. distillationthe residue was purified by Kugelrohr distillation (100° C., 30 microns)
  6. customto remove low boiling materials
  7. customthe title bromide condensation product (ν<95% GC purity)

Sources & evidence

ORD record
ord-a8d4949807ff49829e1f3a7c95ce7335
Source dataset
uspto-grants-1985_04
Patent number
US04514340

Reaction notes

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