2-Methoxybenzoic acid → HCID 12357669, compound

HRID 560192Notes

Reaction equation

HRID 560192 reaction equation
C([Li])(CC)C.[CH3:6][O:7][C:8]1[CH:16]=[CH:15][CH:14]=[CH:13][C:9]=1[C:10]([OH:12])=[O:11].[CH3:17][S:18]SC>O1CCCC1>[CH3:6][O:7][C:8]1[CH:16]=[CH:15][CH:14]=[C:13]([S:18][CH3:17])[C:9]=1[C:10]([OH:12])=[O:11]

Participants

5

Reactant 3

HCID 113702-Methoxybenzoic acidHCID 12232Dimethyl DisulfideHCID 178418400CID 53628100

Product 1

HCID 12357669HCID 12357669, compoundYield 30%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

N,N,N′N′-Tetramethylethylendiamine (16 g, 138 mmol) was added drop-wise at −70° C. to a solution of sec-butyllithium (92 mL, 1.3 M in cyclohexane, 120 mmol) in 80 mL tetrahydrofuran. 2-Methoxybenzoic acid (7.0 g, 46 mmol) in 40 mL tetrahydrofuran was added drop-wise at −70° C. over 2 hours. After complete addition stirring was continued at −70° C. for another 2 hours. Dimethyl disulfide (15.2 g, 161 mmol) was added at −70° C. within 10 min. Stirring was continued at −70° C. for another hour and the reaction was allowed to slowly warm up over night. The reaction mixture was quenched with 40 mL water and extracted with 200 mL ethyl acetate. The aqueous phase was adjusted to pH1 by addition of 25% HCl and extracted twice with dichloromethane. The combined organic phases were dried on sodium sulfate, filtered and evaporated. The crude product was crystallized with cyclohexane and yielded the title compound as an off-white solid (2.7 g, 30%), MS: m/e=197.4 [(M−H)−].

Workup

  1. additionAfter complete addition
  2. stirringStirring
  3. waitwas continued at −70° C. for another hour
  4. temperatureto slowly warm up over night
  5. customThe reaction mixture was quenched with 40 mL water
  6. extractionextracted with 200 mL ethyl acetate
  7. additionThe aqueous phase was adjusted to pH1 by addition of 25% HCl
  8. extractionextracted twice with dichloromethane
  9. customThe combined organic phases were dried on sodium sulfate
  10. filtrationfiltered
  11. customevaporated
  12. customThe crude product was crystallized with cyclohexane

Sources & evidence

ORD record
ord-8e636e5011a5428f831a7a525256bf18
Source dataset
uspto-grants-2011_11
Patent number
US08063098B2

Reaction notes

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