Ammonium Chloride → Dimethyl 4-cyano-1,3-benzenedicarboxylate

HRID 2246031Notes

Reaction equation

HRID 2246031 reaction equation
[CH3:1][O:2][C:3](=[O:15])[C:4]1[CH:13]=[CH:12][C:11](Br)=[C:6]([C:7]([O:9][CH3:10])=[O:8])[CH:5]=1.[Cu][C:17]#[N:18].[Cl-].[NH4+]>CN(C=O)C>[CH3:1][O:2][C:3](=[O:15])[C:4]1[CH:13]=[CH:12][C:11]([C:17]#[N:18])=[C:6]([C:7]([O:9][CH3:10])=[O:8])[CH:5]=1

Participants

5

Reactant 3

HCID 25517Ammonium ChlorideHCID 2824912Dimethyl 4-bromoisophthalateHCID 178418546HCID 178418546, compound

Product 1

HCID 10376118Dimethyl 4-cyano-1,3-benzenedicarboxylateYield 80%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of 4-bromoisophthalic acid dimethyl ester 202 (2.95 g, 10.8 mmol) in anhydrous DMF (50 ml), Copper(I) cyanide (1.20 g, 13.5 mmol) was added in one portion. The slurry solution was heated at reflux temperature for one hour. When the solution was cooled to ambient temperature, it was poured into 300 mL of ammonium chloride solution (10%) at 0° C. White precipitate was formed. The slurry solution was stirred at ambient temperature for 30 minutes. Then it was extracted with ethyl acetate. The combined extracts were dried over sodium sulfate. Removal of solvent gave white solid which was washed with cold methanol to give 1.89 g (80%) of 4-cyanoisophthalic acid dimethyl ester 203: 1H NMR (400 MHz, CDCl3) δ 3.95 (s, 3H), 4.05 (s, 3H), 7.91 (d, J=8 Hz, 1H), 8.30 (dd, J=1.7 Hz, J=8 Hz, 1H), 8.77 (d, J=1.7 Hz, 1H).

Workup

  1. temperatureThe slurry solution was heated
  2. temperatureat reflux temperature for one hour
  3. customWhite precipitate was formed
  4. extractionThen it was extracted with ethyl acetate
  5. dry with materialThe combined extracts were dried over sodium sulfate
  6. customRemoval of solvent
  7. customgave white solid which
  8. washwas washed with cold methanol

Sources & evidence

ORD record
ord-707d08f65374491588fb07a8e2b5065b
Source dataset
uspto-grants-2010_03
Patent number
US07687236B2

Reaction notes

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