Hydrochloric Acid → Methyl 2-methoxy-5-methylthiobenzoate

HRID 323391

Reaction equation

HRID 323391 reaction equation
[CH3:1][O:2][C:3]1[CH:12]=[CH:11][C:10](N)=[CH:9][C:4]=1C(OC)=O.Cl.N([O-])=O.[Na+].[CH2:19]([O:21][C:22]([SH:24])=S)C.[Na].[C:26](=O)([O-])[O-].[Na+].[Na+].[S-2].[Na+].[Na+].[OH-].[Na+].COS(OC)(=O)=O>O.C(OCC)(=O)C.CCCCCC>[CH3:1][O:2][C:3]1[CH:4]=[CH:9][C:10]([CH3:26])=[CH:11][C:12]=1[C:22]([O:21][CH3:19])=[S:24]

Participants

12

Reactant 9

HCID 313Hydrochloric Acid2×HCID 6497Dimethyl SulfateHCID 8823Ethyl xanthateHCID 10340Sodium CarbonateHCID 14798Sodium HydroxideHCID 14804Sodium SulfideHCID 89843Methyl 5-amino-o-anisateHCID 5360545SodiumHCID 23668193Sodium Nitrite

Product 1

HCID 53727199Methyl 2-methoxy-5-methylthiobenzoate

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 21226206Ethyl acetate hexaneSolvent

Procedure

Alternately, combine methyl 2-methoxy-5-aminobenzoate (1.0 g, 5.6 mmol) and 12 M aqueous hydrochloric acid solution (1.2 g and cool in an ice bath. Add a solution of sodium nitrite (0.37 g, 5.3 mmol) in water (3 mL). After 1.5 hours, add ethyl xanthic acid, sodium salt (0.76 g, 6.3 mmol) and sodium carbonate (0.67 g, 6.3 mmol). After 2 hours, evaporate in vacuo and add sodium sulfide (0.69 g, 2.7 mmol) and a 1 M aqueous sodium hydroxide solution (10 mL). After 4 hours, add dimethylsulfate and heat to reflux. After 24 hours, cool to ambient temperature, acidify with 12 M hydrochloric acid solution and extract with ethyl acetate. Separate the organic layer, extract with brine, dry over Na2SO4, filter, and evaporate in vacuo to give a residue. Chromatograph the residue on silica gel eluting with ethyl acetate/hexane 2/1 to give methyl 2-methoxy-5-methylthiobenzoate. Elemental Analysis calculated for C9H12O3S: C, 54.53; H, 5.08. Found: C, 54.64; H, 4.95.

Workup

  1. temperaturecool in an ice bath
  2. waitAfter 2 hours
  3. customevaporate in vacuo
  4. waitAfter 4 hours
  5. temperatureheat to reflux
  6. waitAfter 24 hours
  7. extractionextract with ethyl acetate
  8. customSeparate the organic layer
  9. extractionextract with brine
  10. dry with materialdry over Na2SO4
  11. filtrationfilter
  12. customevaporate in vacuo
  13. customto give a residue

Sources & evidence

ORD record
ord-92c476e1fc114bf59ed2b16fd3a42c1d
Source dataset
uspto-grants-2001_04
Patent number
US06211199B1

Linked notes

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