Hydrochloric Acid → 6-(4-Benzyloxyphenyl)-2,4-hexanedione

HRID 16046

반응식

HRID 16046 반응식
[H-].[Na+].[C:3]([CH2:6][C:7](=[O:9])[CH3:8])(=[O:5])[CH3:4].CCCCCC.C([Li])CCC.[CH2:21]([O:28][C:29]1[CH:36]=[CH:35][C:32]([CH2:33]I)=[CH:31][CH:30]=1)[C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1.Cl>C1COCC1.CN(C)P(=O)(N(C)C)N(C)C>[CH2:21]([O:28][C:29]1[CH:30]=[CH:31][C:32]([CH2:33][CH2:8][C:7](=[O:9])[CH2:6][C:3](=[O:5])[CH3:4])=[CH:35][CH:36]=1)[C:22]1[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=1

참가 물질

9

반응물 6

HCID 313Hydrochloric AcidHCID 8058HexaneHCID 24758Sodium hydrideHCID 31261AcetylacetoneHCID 11723738p-Benzyloxybenzyl iodideHCID 178418339Butyllithium

생성물 1

HCID 597485826-(4-Benzyloxyphenyl)-2,4-hexanedione수율 63%

시약·촉매·용매 2

HCID 8028Tetrahydrofuran용매2회HCID 12679Hexamethylphosphoramide용매

반응 조건

온도
0 °C

실험 절차

That is, 0.30 g (60% in oil) (7.5 mmol) of sodium hydride was weighed in a nitrogen atmosphere and 20 ml of THF was added thereto and the mixture was cooled to 0° C. in an ice bath. To the suspension was dripped a mixed solution of 0.75 g (7.5 mmol) of acetylacetone and 0.5 ml of hexamethyl phosphoric triamide to produce colorless precipitate. After stirring the mixture at 0° C. for 10 minutes, 4.6 ml (7.5 mmol) of a hexane solution (1.6 M) of n-butyllithium was dripped therein to dissolve the precipitate and the mixture was further stirred at 0° C. for 20 minutes. To the obtained pale yellow transparent solution was dripped a solution of 2.28 g (7.0 mmol) of 4-benzyloxybenzyl iodide in 10 ml of THF. After stirring the reaction mixture at room temperature for 1 hour, it was cooled again to 0° C. Then, dilute hydrochloric acid was added thereto to neutralize it. After washing the organic layer with a saturated aqueous solution of sodium chloride, the solvent was distilled off by using a rotary evaporator. The residue was passed through a silica gel column (eluent: a mixed solvent of dichloromethane/hexane of 1:1 (by volume ratio)) to separate a main product. Separation of this and concentration to dryness under reduced pressure afforded 1.31 g (4.4 mmol) of the objective 6-(4-benzyloxyphenyl)-2,4-hexanedione as pale yellow solid. Yield: 63%. Identification was performed by elementary analysis of C and H, and 1H-NMR.

후처리

  1. additionwas added
  2. customto produce colorless precipitate
  3. dissolutionto dissolve the precipitate
  4. stirringthe mixture was further stirred at 0° C. for 20 minutes
  5. stirringAfter stirring the reaction mixture at room temperature for 1 hour
  6. temperatureit was cooled again to 0° C
  7. washAfter washing the organic layer with a saturated aqueous solution of sodium chloride
  8. distillationthe solvent was distilled off
  9. customa rotary evaporator
  10. customa mixed solvent of dichloromethane/hexane of 1:1 (by volume ratio)) to separate a main product
  11. customSeparation of this and
  12. concentrationconcentration to dryness under reduced pressure

출처 및 근거

ORD 기록
ord-7997ea332f144866b575a61adfbf1b53
출처 데이터셋
uspto-grants-2010_06
특허 번호
US07736757B2

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