Ethanol, 2-chloro-, 1-(4-methylbenzenesulfonate) → Methyl 5-chloro-2-(2-chloroethoxy)benzoate

HRID 78492

Reaction equation

HRID 78492 reaction equation
[CH3:1][O:2][C:3](=[O:12])[C:4]1[C:5](=[CH:7][CH:8]=[C:9]([Cl:11])[CH:10]=1)[OH:6].C1(C)C=CC(S(O[CH2:23][CH2:24][Cl:25])(=O)=O)=CC=1.C([O-])([O-])=O.[K+].[K+]>CN(C)C=O.C(OCC)(=O)C.O>[Cl:11][C:9]1[CH:8]=[CH:7][C:5]([O:6][CH2:23][CH2:24][Cl:25])=[C:4]([CH:10]=1)[C:3]([O:2][CH3:1])=[O:12]

Participants

7

Reactant 3

HCID 6639Ethanol, 2-chloro-, 1-(4-methylbenzenesulfonate)HCID 11430Potassium CarbonateHCID 77684Benzoic acid, 5-chloro-2-hydroxy-, methyl ester

Product 1

HCID 66846837Methyl 5-chloro-2-(2-chloroethoxy)benzoate

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
50 °C

Procedure

A mixture of methyl-5-chlorosalicylate (19.5 g, 105 mmol), 2-chloroethyl p-toluenesulfonate (19.3 mL, 107 mmol) and K2CO3 (28.9 g, 210 mmol) in 105 mL of N,N-dimethylformamide was warmed to 50° C. and allowed to stir for 18 hours. The mixture was cooled to ambient temperature, diluted with 25 mL of ethyl acetate and 25 mL of H2O. The layers were separated and the organic layer was dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. Purification via column chromatography (SiO2, 75% hexanes in ethyl acetate) afforded the title compound. MS (DCI/NH3) m/z 249 (M+H)+, 266 (M+NH4)+.

Workup

  1. temperatureThe mixture was cooled to ambient temperature
  2. customThe layers were separated
  3. dry with materialthe organic layer was dried over anhydrous Na2SO4
  4. filtrationfiltered
  5. concentrationconcentrated under reduced pressure
  6. customPurification via column chromatography (SiO2, 75% hexanes in ethyl acetate)

Sources & evidence

ORD record
ord-191942b1cd1f4610a6c345a57cd8f0b7
Source dataset
uspto-grants-2014_09
Patent number
US08841334B2

Linked notes

Loading…