p-Toluenesulfonic acid → 5-(2,3,4,5-Tetramethoxy-6-methylphenyl)-5-phenylpentane-1-ol

HRID 1646819

반응식

HRID 1646819 반응식
C([Li])CCC.[CH2:6]([C:13]1[C:18]([CH3:19])=[C:17]([O:20][CH3:21])[C:16]([O:22][CH3:23])=[C:15]([O:24][CH3:25])[C:14]=1[O:26][CH3:27])[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1.CC(C)(N)C(C)(C)N.Cl[CH2:37][CH2:38][CH2:39][CH2:40][OH:41].O1CCCCC1OC1CCCCO1.C1(C)C=CC(S(O)(=O)=O)=CC=1.C(=O)([O-])O.[Na+]>O1CCCC1.CCCCCC>[CH3:27][O:26][C:14]1[C:15]([O:24][CH3:25])=[C:16]([O:22][CH3:23])[C:17]([O:20][CH3:21])=[C:18]([CH3:19])[C:13]=1[CH:6]([C:7]1[CH:8]=[CH:9][CH:10]=[CH:11][CH:12]=1)[CH2:37][CH2:38][CH2:39][CH2:40][OH:41]

참가 물질

10

반응물 7

HCID 6101p-Toluenesulfonic acidHCID 135694-Chloro-1-butanolHCID 1233902,3-Butanediamione, 2,3-dimethyl-HCID 263182Tetrahydropyranyl etherHCID 516892Sodium BicarbonateHCID 190880281-Benzyl-2,3,4,5-tetramethoxy-6-methylbenzeneHCID 178418339Butyllithium

생성물 1

HCID 190880725-(2,3,4,5-Tetramethoxy-6-methylphenyl)-5-phenylpentane-1-ol수율 69%

시약·촉매·용매 2

HCID 8028Tetrahydrofuran용매2회HCID 8058Hexane용매

실험 절차

A 3.1 ml (5.0 mmole) of n-butyllithium.hexane solution was added dropwise to 1.51 g (5.0 mmole) of 1-benzyl-2,3,4,5-tetramethoxy-6-methylbenzene and 0.83 ml (5×1.1 mmole) of 1,1,2,2-tetramethylethylenediamine dissolved in anhydrous tetrahydrofuran (15 ml), under an atmosphere of argon at -5° C. over the period of 5 minutes, followed by stirring at -5° to 0° C. for 25 minutes. Then, a solution of 0.96 g (5.0 mmole) of 4-chlorobutanol.tetrahydropyranyl ether in tetrahydrofuran (5 ml) was added to the mixed solution over the period of 5 minutes, followed by stirring for further 15 minutes under ice-cooling. Subsequently, the cooling bath was removed, and stirring was effected at room temperature for 20 minutes. The reaction solution was cooled with ice, and made acid by adding a 10% aqueous phosphoric acid solution, and the product was extracted with isopropyl ether. The organic layer was separated out, washed with aqueous sodium chloride solution, dried (magnesium sulfate). The solvent was distilled off and the residue was dissolved in methanol (15 ml), followed by addition of 48 mg (5×1/20 mmole) of p-toluenesulfonic acid and stirring at 70° C. for 15 minutes. After cooling by standing at room temperature, the mixed solution was neutralized by adding an aqueous sodium hydrogen-carbonate solution, and the solvent was distilled off. Isopropyl ether and water were added to the residue to effect extraction. The isopropyl ether layer was washed with aqueous sodium chloride solution, dried (magnesium sulfate) and evaporated. The residual solution was chromatographed on a silica gel column to perform purification (elution with isopropyl ether) to thereby give 1.29 g (69%) of 5-(2,3,4,5-tetramethoxy-6-methylphenyl)-5-phenylpentane-1-ol. Its typical physical properties and nuclear magnetic resonance spectrum data are shown in Table 14.

후처리

  1. stirringby stirring for further 15 minutes under ice-
  2. temperaturecooling
  3. customSubsequently, the cooling bath was removed
  4. stirringstirring
  5. waitwas effected at room temperature for 20 minutes
  6. temperatureThe reaction solution was cooled with ice
  7. additionby adding a 10% aqueous phosphoric acid solution
  8. extractionthe product was extracted with isopropyl ether
  9. customThe organic layer was separated out
  10. washwashed with aqueous sodium chloride solution
  11. dry with materialdried (magnesium sulfate)
  12. distillationThe solvent was distilled off
  13. dissolutionthe residue was dissolved in methanol (15 ml)
  14. stirringstirring at 70° C. for 15 minutes
  15. temperatureAfter cooling
  16. customby standing at room temperature
  17. distillationthe solvent was distilled off
  18. additionIsopropyl ether and water were added to the residue
  19. extractionextraction
  20. washThe isopropyl ether layer was washed with aqueous sodium chloride solution
  21. dry with materialdried (magnesium sulfate)
  22. customevaporated
  23. customThe residual solution was chromatographed on a silica gel column
  24. custompurification (elution with isopropyl ether)

출처 및 근거

ORD 기록
ord-100b06159b0b45318be65e4a3241442e
출처 데이터셋
uspto-grants-1993_01
특허 번호
US05180742

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