Ethyl 3-(4-bromophenyl)-2-cyanoacrylate → Ethyl 3-(4-bromophenyl)-2-cyano-3-o-tolylpropanoate

HRID 1527961Notes

Reaction equation

HRID 1527961 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5](/[CH:8]=[C:9](\[C:15]#[N:16])/[C:10]([O:12][CH2:13][CH3:14])=[O:11])=[CH:4][CH:3]=1.[C:17]1([CH3:25])[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=1[Mg]Cl>C1(C)C=CC=CC=1>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([CH:8]([C:18]2[CH:19]=[CH:20][CH:21]=[CH:22][C:17]=2[CH3:25])[CH:9]([C:15]#[N:16])[C:10]([O:12][CH2:13][CH3:14])=[O:11])=[CH:6][CH:7]=1

Participants

4

Reactant 2

HCID 5378084Ethyl 3-(4-bromophenyl)-2-cyanoacrylateHCID 178424304HCID 178424304, compound

Product 1

HCID 67015643Ethyl 3-(4-bromophenyl)-2-cyano-3-o-tolylpropanoateYield 107.2%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
85 °C

Procedure

A solution of (E)-ethyl 3-(4-bromophenyl)-2-cyanoacrylate (59.4 g, 212 mmol) in toluene (420 mL) was added over 80 min at 0-5° C. to o-tolylmagnesium chloride solution (1 M in tetrahydrofuran, 276 mL, 276 mmol). The reaction mixture was heated at 85° C. for 1½ h, then poured upon ice water and partitioned between 1 M aq. hydrochloric acid solution and ethyl acetate. The organic layer was washed with brine, dried over magnesium sulfate, filtered, and evaporated to produce the title compound (84.6 g), which was directly used in the next step. Light yellow oil, MS: 370.0 [M−H]−.

Workup

  1. custompartitioned between 1 M aq. hydrochloric acid solution and ethyl acetate
  2. washThe organic layer was washed with brine
  3. dry with materialdried over magnesium sulfate
  4. filtrationfiltered
  5. customevaporated

Sources & evidence

ORD record
ord-ca07a5e479184607bd9a07b9fb093f19
Source dataset
uspto-grants-2015_07
Patent number
US09090565B2

Reaction notes

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