Methyl chloroformate → Methyl 2-cyanobenzoate

HRID 1658458Notes

Reaction equation

HRID 1658458 reaction equation
[C:1]([OH:12])(=[O:11])[C:2]1[C:3](=[CH:7][CH:8]=[CH:9][CH:10]=1)[C:4]([NH2:6])=O.[CH2:13](N(CC)CC)C.ClC(OC)=O>C(Cl)Cl>[C:4]([C:3]1[CH:7]=[CH:8][CH:9]=[CH:10][C:2]=1[C:1]([O:12][CH3:13])=[O:11])#[N:6]

Participants

5

Reactant 3

HCID 6586Methyl chloroformateHCID 6957Phthalamic acidHCID 8471Triethylamine

Product 1

HCID 582554Methyl 2-cyanobenzoate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Phthalamic acid (240 g, 1.37 moles) in methylenechloride (1.7 l) was stirred and cooled to <5° in an ice bath. Triethylamine (244 ml, 176 g, 1.74 moles) was added and a clear solution was obtained. Methyl chloroformate (200 g, 163 ml, 2.1 moles) was added at such a rate that the temperature did not exceed 5°. As the addition continued, triethylamine hydrochloride precipitated and carbon dioxide was evolved. On completion of the addition, the ice bath was removed and stirring was continued for 12-20 hrs. at room temperature. Triethylamine hydrochloride was removed by filtration and the methylene chloride evaporated. The residue was dissolved in ether (2 l), and this ether solution washed with water, dried over anhydrous sodium sulfate and evaporated. Distillation under reduced pressure gave methyl 2-cyanobenzoate, b.p. 125° at 2.5 mm, 215 g (97%), a solid at room temperature, M.P. 45°-6°.

Workup

  1. temperaturecooled to <5° in an ice bath
  2. customa clear solution was obtained
  3. customdid not exceed 5°
  4. additionAs the addition
  5. customtriethylamine hydrochloride precipitated
  6. additionOn completion of the addition
  7. customthe ice bath was removed
  8. customat room temperature
  9. customTriethylamine hydrochloride was removed by filtration
  10. customthe methylene chloride evaporated
  11. dissolutionThe residue was dissolved in ether (2 l)
  12. washthis ether solution washed with water
  13. dry with materialdried over anhydrous sodium sulfate
  14. customevaporated
  15. distillationDistillation under reduced pressure

Sources & evidence

ORD record
ord-93126227cf7d4a7e8f7d3b784522cee2
Source dataset
uspto-grants-1976_06
Patent number
US03964896

Reaction notes

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