Dimethyl Disulfide → 2-Methoxy-6-methylsulfanyl-4-trifluoromethyl-benzoic acid

HRID 659178

반응식

HRID 659178 반응식
C([Li])(CC)C.[CH3:6][O:7][C:8]1[CH:16]=[C:15]([C:17]([F:20])([F:19])[F:18])[CH:14]=[CH:13][C:9]=1[C:10]([OH:12])=[O:11].[CH3:21][S:22]SC>O1CCCC1>[CH3:6][O:7][C:8]1[CH:16]=[C:15]([C:17]([F:18])([F:19])[F:20])[CH:14]=[C:13]([S:22][CH3:21])[C:9]=1[C:10]([OH:12])=[O:11]

참가 물질

5

반응물 3

HCID 12232Dimethyl DisulfideHCID 36908732-Methoxy-4-(trifluoromethyl)benzoic acidHCID 178418400CID 53628100

생성물 1

HCID 591979212-Methoxy-6-methylsulfanyl-4-trifluoromethyl-benzoic acid수율 11.1%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매2회

실험 절차

N,N,N′N′-Tetramethylethylendiamine (21 g, 177 mmol) was added drop-wise at −70° C. to a solution of sec-butyllithium (110 mL, 1.4 M in cyclohexane, 154 mmol) in 180 mL tetrahydrofuran. 2-Methoxy-4-trifluoromethyl-benzoic acid (13 g, 59 mmol) in 60 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 (20 g, 207 mmol) was added at −70° C. within 10 min. Stirring was continued at −70° C. for another hour and the reaction was allowed to warm up. The reaction mixture was quenched with 150 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 heptane and yielded the title compound as a white solid (1.75 g, 11%), MS: m/e=265.1 [(M−H)−].

후처리

  1. additionAfter complete addition
  2. stirringStirring
  3. waitwas continued at −70° C. for another hour
  4. temperatureto warm up
  5. customThe reaction mixture was quenched with 150 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 heptane

출처 및 근거

ORD 기록
ord-906ff88d0934486fba5d4c181948c4bf
출처 데이터셋
uspto-grants-2011_12
특허 번호
US08080541B2

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