Hydrochloric Acid → Methyl 4-(cyanomethoxy)benzoate

HRID 1361021Notes

Reaction equation

HRID 1361021 reaction equation
[OH:1][C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][CH:3]=1.[I-].[Na+].C(=O)([O-])[O-].[K+].[K+].Cl[CH2:21][C:22]#[N:23].Cl>CC(C)=O.O>[C:22]([CH2:21][O:1][C:2]1[CH:3]=[CH:4][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:10][CH:11]=1)#[N:23]

Participants

8

Reactant 5

HCID 313Hydrochloric Acid2×HCID 5238Sodium Iodide2×HCID 7456MethylparabenHCID 7856Chloroacetonitrile3×HCID 11430Potassium Carbonate2×

Product 1

HCID 594916Methyl 4-(cyanomethoxy)benzoate

Reagents, catalysts & solvents 2

HCID 180AcetoneSolventHCID 962WaterSolvent2×

Procedure

To a mixture of methyl 4-hydroxybenzoate (30.0 g, 0.20 mol), sodium iodide (30.0 g, 0.20 mol) and potassium carbonate (27.6 g, 0.20 mol) in acetone (2000 mL) was added chloroacetonitrile (14.9 g, 0.20 mol). The mixture was stirred at RT for 3 days. Water was added and the mixture was acidified with 1N hydrochloric acid and the mixture was extracted with diethyl ether. The combined organic layers were dried over Na2SO4 and concentrated in vacuo. The residue was dissolved in acetone and chloroacetonitrile (6.04 g, 0.08 mol), sodium iodide (12.0 g, 0.08 mol) and potassium carbonate (11.1 g, 0.08 mol) were added and the mixture was stirred for 16 hours at RT and at 60° C. More chloroacetonitrile was added until the conversion was 97%. Water was added and the mixture was acidified with 1N hydrochloric acid and the mixture was extracted with diethyl ether. The combined organic layers were dried over Na2SO4 and concentrated in vacuo to afford methyl 4-cyanomethyloxybenzoate in quantitative yield. This compound was used without further purification in the following step.

Workup

  1. extractionthe mixture was extracted with diethyl ether
  2. dry with materialThe combined organic layers were dried over Na2SO4
  3. concentrationconcentrated in vacuo
  4. dissolutionThe residue was dissolved in acetone
  5. stirringthe mixture was stirred for 16 hours at RT and at 60° C
  6. extractionthe mixture was extracted with diethyl ether
  7. dry with materialThe combined organic layers were dried over Na2SO4
  8. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-a30bb249df2e425ea668342edb258337
Source dataset
uspto-grants-2011_02
Patent number
US07879893B2

Reaction notes

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