Hydrochloric Acid → 4-(Isopropylthio)-3-methylbenzoic acid

HRID 72931

반응식

HRID 72931 반응식
C([Li])CCC.Br[C:7]1[CH:15]=[CH:14][C:10]([C:11]([OH:13])=[O:12])=[CH:9][C:8]=1[CH3:16].[CH:17]([S:20]SCCC)([CH3:19])[CH3:18].Cl>C1COCC1.[OH-].[Na+]>[CH:17]([S:20][C:7]1[CH:15]=[CH:14][C:10]([C:11]([OH:13])=[O:12])=[CH:9][C:8]=1[CH3:16])([CH3:19])[CH3:18]

참가 물질

7

반응물 4

HCID 313Hydrochloric AcidHCID 821314-Bromo-3-methylbenzoic acidHCID 118529Isopropyl propyl disulfideHCID 178418339Butyllithium

생성물 1

HCID 585509264-(Isopropylthio)-3-methylbenzoic acid수율 35.8%

시약·촉매·용매 2

HCID 8028Tetrahydrofuran용매2회HCID 14798Sodium Hydroxide용매

반응 조건

온도
-78 °C

실험 절차

Butyllithium (16 mL of 1.6 M, 25.6 mmol) was added dropwise to a mixture of 4-bromo-3-methyl-benzoic acid (2.5 g, 11.6 mmol) and THF (63 mL) at −78° C. The reaction mixture was allowed to stir at −78° C. for 30 minutes before a solution of 2-isopropyldisulfanylpropane (1.7 g, 11.6 mmol) in THF (2 mL) was added dropwise. The mixture was allowed to stir at −78° C. for 30 minutes, then 30 minutes at room temperature. The reaction mixture was then diluted with 1M aqueous sodium hydroxide (100 mL). The organic layer was discarded and the aqueous layer was acidified with 4M aqueous hydrochloric acid. The aqueous layer was then extracted 3 times with ethyl acetate. The combined extracts were dried over sodium sulfate and concentrated in vacuo. The crude material was purified by silica gel column chromatography using a gradient of 0-5% MeOH in dichloromethane to give 4-(isopropylthio)-3-methylbenzoic acid (873 mg, 18%). MS m/z calc. 210.3. Found 211.2 (M+1)+. Retention time: 2.32 minutes (3 min run).

후처리

  1. additionwas added dropwise
  2. custom30 minutes
  3. customat room temperature
  4. extractionThe aqueous layer was then extracted 3 times with ethyl acetate
  5. dry with materialThe combined extracts were dried over sodium sulfate
  6. concentrationconcentrated in vacuo
  7. customThe crude material was purified by silica gel column chromatography

출처 및 근거

ORD 기록
ord-9afdff4de9624df2841f718aadf77f50
출처 데이터셋
uspto-grants-2014_09
특허 번호
US08828996B2

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