Carbon Dioxide → 4-Hydroxy[1,1'-biphenyl]-3-carboxylic acid

HRID 260090

반응식

HRID 260090 반응식
O1CCCCC1.[C:7]1([C:13]2[CH:18]=[CH:17][C:16]([OH:19])=[CH:15][CH:14]=2)[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1.C([Li])CCC.[C:25](=[O:27])=[O:26]>C1COCC1>[OH:19][C:16]1[CH:15]=[CH:14][C:13]([C:7]2[CH:8]=[CH:9][CH:10]=[CH:11][CH:12]=2)=[CH:18][C:17]=1[C:25]([OH:27])=[O:26]

참가 물질

6

반응물 4

HCID 280Carbon DioxideHCID 71034-HydroxybiphenylHCID 8894Tetrahydropyran2회HCID 178418339Butyllithium

생성물 1

HCID 675844-Hydroxy[1,1'-biphenyl]-3-carboxylic acid

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

실험 절차

2-hydroxy-5-phenylbenzoic acid was synthesized as follows. A solution of tetrahydropyran (THP)-protected 4-phenylphenol (474 mg. 2 mmol., prepared from 4-phenylphenol by standard methods described in Green and Wuts at pp. 31-34) in anhydrous THF (5 mL) was cooled to -78° C. and treated with n-Butyllithium (2 mL of 1.6M in hexanes). The reaction mixture was stirred and warmed to ambient temperature during which a tan suspension formed. After 2 hours, the reaction mixture was cooled to -78° C. and treated with excess anhydrous CO2 for several minutes. The reaction mixture was stirred and warmed to ambient temperature. After 2 hours, the reaction mixture was partitioned between ethyl ether and aqueous 1N NaOH. The aqueous layer was cooled to 0° C. with ice and acidified to pH 2 with aqueous 1N HCl. The aqueous solution was partitioned with methylene chloride. The organic layer was dried over magnesium sulfate. Concentration in vacuo yielded crude product as an off-white solid (258 mg, 2-hydroxy-5-phenylbenzoic acid). NMR spectroscopy of the crude material was consistent with the expected structure. 1H NMR (DMSO-d6) δ8.04 (d, J=3 Hz, 1H), 7.76 (dd, J=9, 3 Hz, 1H), 7.62 (d, J=7 Hz, 2H), 7.44 (t, J=7 Hz, 2H), 7.32 (t, J=7 Hz, 1H), 7.00 (d, J=9 Hz, 1H). Mass calculated: 466.5. Mass found 467.2. LC Gradient 25-45% acetonitrile over 13 minutes. LC retention time 3.5 minutes. The material was used without further purification.

후처리

  1. customformed
  2. temperaturethe reaction mixture was cooled to -78° C.
  3. stirringThe reaction mixture was stirred
  4. temperaturewarmed to ambient temperature
  5. waitAfter 2 hours
  6. customthe reaction mixture was partitioned between ethyl ether and aqueous 1N NaOH
  7. temperatureThe aqueous layer was cooled to 0° C. with ice
  8. customThe aqueous solution was partitioned with methylene chloride
  9. dry with materialThe organic layer was dried over magnesium sulfate
  10. concentrationConcentration in vacuo

출처 및 근거

ORD 기록
ord-f6018e568ad44c6fa9abe124fc4c890c
출처 데이터셋
uspto-grants-1996_06
특허 번호
US05525623

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