Ethylene Glycol → 2-(1-(3-Phenoxyphenyl)-2-oxabicyclo[2.2.2]octan-4-yl)acetic acid

HRID 1855037노트

반응식

HRID 1855037 반응식
CC1C=CC(S(OC[C:13]23[CH2:20][CH2:19][C:16]([C:21]4[CH:26]=[CH:25][CH:24]=[C:23]([O:27][C:28]5[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=5)[CH:22]=4)([CH2:17][CH2:18]2)[O:15][CH2:14]3)(=O)=O)=CC=1.[C-]#N.[Na+].[CH2:37]([OH:40])[CH2:38]O.[OH-:41].[K+]>[I-].C([N+](CCCC)(CCCC)CCCC)CCC.O>[O:27]([C:23]1[CH:22]=[C:21]([C:16]23[CH2:19][CH2:20][C:13]([CH2:38][C:37]([OH:40])=[O:41])([CH2:18][CH2:17]2)[CH2:14][O:15]3)[CH:26]=[CH:25][CH:24]=1)[C:28]1[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=1

참가 물질

7

반응물 4

HCID 174Ethylene GlycolHCID 8929Sodium CyanideHCID 14797Potassium HydroxideHCID 90408232(1-(3-Phenoxyphenyl)-2-oxabicyclo[2.2.2]octan-4-yl)methyl 4-methylbenzenesulfonate

생성물 1

HCID 904093542-(1-(3-Phenoxyphenyl)-2-oxabicyclo[2.2.2]octan-4-yl)acetic acid수율 91%

시약·촉매·용매 2

HCID 67553Tetrabutylammonium Iodide촉매HCID 962Water용매

반응 조건

온도
165 °C

실험 절차

A mixture of (1-(3-phenoxyphenyl)-2-oxabicyclo[2.2.2]octan-4-yl)methyl 4-methylbenzenesulfonate (400 mg, 0.861 mmol), NaCN (127 mg, 2.58 mmol), and tetrabutylammoniumiodide (31.8 mg, 0.086 mmol) was stirred at 165° C. overnight. The reaction mixture was then cooled to rt and extracted with EtOAc (10 mL). The organic extract was washed with water and concentrated in vacuo. The residue was taken up with ethylene glycol (5 mL) and water (1 mL), and 40% aqueous KOH (1208 mg, 8.61 mmol) was added. The reaction was heated at 165° C. for 18 h. The mixture was concentrated in vacuo and the remaining solution was diluted with water and adjusted to pH 3 with conc. HCl. The mixture was extracted with EtOAc (2×5 mL). The combined organic layers were washed with water, dried (MgSO4), filtered, and concentrated in vacuo to afford the title compound (280 mg, 91% yield) as a white solid. LCMS, [M−H]+=337.0. 1H NMR (500 MHz, CDCl3) δ 7.38-7.27 (m, 3H), 7.19-7.08 (m, 3H), 7.03-6.99 (m, 2H), 6.87 (ddd, J=8.1, 2.4, 0.9 Hz, 1H), 3.97 (s, 2H), 2.23 (s, 2H), 2.17-2.00 (m, 4H), 1.95-1.79 (m, 4H).

후처리

  1. temperatureThe reaction mixture was then cooled to rt
  2. extractionextracted with EtOAc (10 mL)
  3. extractionThe organic extract
  4. washwas washed with water
  5. concentrationconcentrated in vacuo
  6. additionwas added
  7. temperatureThe reaction was heated at 165° C. for 18 h
  8. concentrationThe mixture was concentrated in vacuo
  9. additionthe remaining solution was diluted with water
  10. extractionThe mixture was extracted with EtOAc (2×5 mL)
  11. washThe combined organic layers were washed with water
  12. dry with materialdried (MgSO4)
  13. filtrationfiltered
  14. concentrationconcentrated in vacuo

출처 및 근거

ORD 기록
ord-9f0c08f691f7482189c74afc1303bda4
출처 데이터셋
uspto-grants-2015_02
특허 번호
US08962660B2

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