Potassium Iodide → 3-(5-phenylthio-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamic acid

HRID 1648694노트

반응식

HRID 1648694 반응식
Cl[C:2]1[CH:27]=[CH:26][C:5]2=[N:6][N:7]([C:9]3[CH:10]=[C:11]([CH:18]=[C:19]([C:22]([CH3:25])([CH3:24])[CH3:23])[C:20]=3[OH:21])[CH2:12][CH2:13][C:14]([O:16]C)=[O:15])[N:8]=[C:4]2[CH:3]=1.[OH-].[Na+].[I-].[K+].[C:32]1([SH:38])[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1>CN(C)C=O>[C:32]1([S:38][C:2]2[CH:27]=[CH:26][C:5]3=[N:6][N:7]([C:9]4[CH:10]=[C:11]([CH:18]=[C:19]([C:22]([CH3:25])([CH3:24])[CH3:23])[C:20]=4[OH:21])[CH2:12][CH2:13][C:14]([OH:16])=[O:15])[N:8]=[C:4]3[CH:3]=2)[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1

참가 물질

6

반응물 4

HCID 4875Potassium IodideHCID 7969Thiophenol2회HCID 14798Sodium HydroxideHCID 30191402-(3'-tert-Butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole

생성물 1

HCID 212181283-(5-phenylthio-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamic acid수율 72.3%

시약·촉매·용매 1

HCID 6228Dimethylformamide용매2회

실험 절차

To a 1 liter, 4 necked, round-bottomed flask equipped with mechanical stirring and a nitrogen atmosphere is charged 100.0 g (0.258 mol) of methyl 3-(5-chloro-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate, 350 mL of N,N-dimethylformamide, and 61.9 g (0.773 tool) of 50% aqueous sodium hydroxide solution. The mixture is heated at 75°-80° C. for 3 hours at which point the ester hydrolysis is complete. A catalytic amount of potassium iodide (5.0 g) is added. Thiophenol (32.2 g, 0.258 mol) is then added over a 20 minute period while the temperature remains at 75°-80° C. An additional portion of N,N-dimethylformamide (200 mL) is added during the addition of thiophenol to facilitate stirring. A 25 mL fraction of water/methanol is removed and the solution is refluxed for 48 hours. The reaction mixture is cooled, then partitioned between 1.0 L of 1N hydrochloric acid and 1.0 L of ethyl acetate. The phases are separated and the organic phase is dried over anhydrous magnesium sulfate, and the solvent is then removed under reduced pressure until the total volume is 500 mL. To this is added 200 mL of heptane and the solution is allowed to sit overnight. The resultant crystals are collected by vacuum filtration, washed with 9:1 heptane:ethyl acetate, and dried to afford 83.5 g (72% yield) of the title compound; mp 154°-156° C.

후처리

  1. customTo a 1 liter, 4 necked, round-bottomed flask equipped
  2. temperatureThe mixture is heated at 75°-80° C. for 3 hours at which point
  3. customremains at 75°-80° C
  4. stirringto facilitate stirring
  5. customA 25 mL fraction of water/methanol is removed
  6. temperaturethe solution is refluxed for 48 hours
  7. temperatureThe reaction mixture is cooled
  8. custompartitioned between 1.0 L of 1N hydrochloric acid and 1.0 L of ethyl acetate
  9. customThe phases are separated
  10. dry with materialthe organic phase is dried over anhydrous magnesium sulfate
  11. customthe solvent is then removed under reduced pressure until the total volume is 500 mL
  12. additionTo this is added 200 mL of heptane
  13. filtrationThe resultant crystals are collected by vacuum filtration
  14. washwashed with 9:1 heptane
  15. dry with materialethyl acetate, and dried

출처 및 근거

ORD 기록
ord-0514119d10e84ce08e80c6b006325c97
출처 데이터셋
uspto-grants-1995_07
특허 번호
US05436349

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