p-Toluenesulfonic acid → Methyl 3-phenoxypropionate

HRID 1761664Notes

Reaction equation

HRID 1761664 reaction equation
[O:1]([CH2:8][CH2:9][C:10]([OH:12])=[O:11])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:13]1(C)C=CC(S(O)(=O)=O)=CC=1>CO>[O:1]([CH2:8][CH2:9][C:10]([O:12][CH3:13])=[O:11])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

4

Reactant 2

HCID 6101p-Toluenesulfonic acidHCID 815963-Phenoxypropionic acid

Product 1

HCID 347927Methyl 3-phenoxypropionateYield 1,589.1%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To demonstrate the methyl ester, as well as the ethyl ester, may be used to make members of composition 7, we illustrate the preparation of the corresponding methyl ester of composition 7 in which the Et group is replaced by Me and X is O. A solution of 3-phenoxypropionic acid (10.0 g, 0.060 mol) and p-toluenesulfonic acid (0.6 g, 0.0033 mol) in methanol (250 mL) was heated at reflux through 3 Å molecular sieve for 36 hours under N2 in a flask equipped with a Soxhlet extractor and a condenser. The solution was allowed to cool to room temperature and then was concentrated to a volume of 50 mL, diluted with water (50 mL), and extracted with ether (2×75 mL). The combined organic layers were washed with 5% aqeuous NaHCO3 (75 mL), H2O (75 mL), and brine (75 mL). After drying (Na2SO4) the solution, the solvent was removed (vacuum). Vacuum distillation gave 9.45 grams (87.1%) of the title ester as a colorless liquid: by 85°-87° C./0.1 mm (literature reports 85° C./0.4 mm; see C. E. Rehberg and M. D. Dixon [J. Am. Chem. Soc. 72, 2205 [1972]): IR (neat) 1740-1750 cm-1 (C=O); 1H NMR (DCCl3) δ 2.78 [s, 2H, CH2CO2CH3 ], 3.70 [s, 3H, OCH3 ], 4.23 [2H, OCH], 6.84-7.02 and 7.18-7.35 [m, 5H, ArH]; 13C NMR (DCCl3) ppm 34.3 [H2CCO2 ], 51.7 [CH3 ], 63.2 [Ar--OCH2 ]; Ar--C [114.5, 120.8, 129.2, 158.3, 171.1].

Workup

  1. temperatureat reflux through 3 Å molecular sieve for 36 hours under N2 in a flask
  2. customequipped with a Soxhlet extractor and a condenser
  3. concentrationwas concentrated to a volume of 50 mL
  4. additiondiluted with water (50 mL)
  5. extractionextracted with ether (2×75 mL)
  6. washThe combined organic layers were washed with 5% aqeuous NaHCO3 (75 mL), H2O (75 mL), and brine (75 mL)
  7. dry with materialAfter drying (Na2SO4) the solution
  8. customthe solvent was removed (vacuum)
  9. distillationVacuum distillation

Sources & evidence

ORD record
ord-b672f7f0b649483ca78e91c68145014b
Source dataset
uspto-grants-1989_05
Patent number
US04826984

Reaction notes

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