Hydrochloric Acid → 1-Phenyl-cycloheptene

HRID 70725

반응식

HRID 70725 반응식
[C:1]1([CH3:11])[CH:6]=[C:5](C)[CH:4]=[C:3](C)[C:2]=1[Mg]Br.[C:12]1(=O)[CH2:18][CH2:17]C[CH2:15][CH2:14][CH2:13]1.P(Cl)(OC1C=CC=CC=1)(OC1C=CC=CC=1)=O.C1([Mg]Cl)C=CC=CC=1.Cl>C1COCC1.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.CCCCC>[C:1]1([C:11]2[CH2:15][CH2:14][CH2:13][CH2:12][CH2:18][CH:17]=2)[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1

참가 물질

9

반응물 5

HCID 313Hydrochloric AcidHCID 10400CycloheptanoneHCID 75654Diphenyl chlorophosphateHCID 178425415HCID 178425415, 화합물HCID 178478979HCID 178478979, 화합물

생성물 1

HCID 2781321-Phenyl-cycloheptene수율 43%

시약·촉매·용매 3

HCID 178418476HCID 178418476, 화합물촉매HCID 8003Pentane용매HCID 8028Tetrahydrofuran용매

반응 조건

온도
0 °C

실험 절차

Mesitylmagnesium bromide (18.0 mL, 18.0 mmol, 1.0 M in THF) was added over 15 minutes to a solution of cycloheptanone (2.0 g, 17.8 mmol) and diphenyl chlorophosphate (1.1 eq.) in THF (5 mL) at 0° C. The solution was stirred at 0° C. for 30 min, whereafter the solution was allowed to reach room temperature. After stirring the solution for 30 min, dichlorobis(triphenylphosphine)palladium (126 mg, 1 mol %) was added and the solution was warmed to 65° C. Phenylmagnesium chloride (10.8 mL, 1.2 equivalents in THF) was added over 10 minutes, resulting in a gentle reflux of the solvent. After stirring at 65° C. for 30 minutes, the mixture was cooled to rt and poured into a mixture of 3 N HCl (30 mL) and pentane (30 mL). The phases were separated, and the aqueous portion was extracted with pentane (30 mL). The combined organic phase was washed sequentially with 3 N HCl (20 mL), 3 M NaOH (2×20 mL), and brine (20 mL), and dried over MgSO4. Evaporation of the solvent followed by distillation using a Kugelrohr apparatus (oven temperature 100-140° C., 0.065 torr) yielded 1-phenylcycloheptene (1.29 g, 43%).

후처리

  1. customto reach room temperature
  2. stirringAfter stirring the solution for 30 min
  3. temperaturethe solution was warmed to 65° C
  4. customresulting in
  5. temperaturea gentle reflux of the solvent
  6. stirringAfter stirring at 65° C. for 30 minutes
  7. temperaturethe mixture was cooled to rt
  8. customThe phases were separated
  9. extractionthe aqueous portion was extracted with pentane (30 mL)
  10. washThe combined organic phase was washed sequentially with 3 N HCl (20 mL), 3 M NaOH (2×20 mL), and brine (20 mL)
  11. dry with materialdried over MgSO4
  12. customEvaporation of the solvent
  13. distillationfollowed by distillation
  14. customa Kugelrohr apparatus (oven temperature 100-140° C., 0.065 torr)

출처 및 근거

ORD 기록
ord-cf55e55e22074901a516bc2628059231
출처 데이터셋
uspto-grants-2014_09
특허 번호
US08822548B2

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