Hydrochloric Acid → 1-benzyl-6-methoxy-3,4-dihydro-1H-naphthalen-2-one

HRID 23362

Reaktionsgleichung

Reaktionsgleichung von HRID 23362
[CH3:1][O:2][C:3]1[CH:4]=[C:5]2[C:10](=[CH:11][CH:12]=1)[CH2:9][C:8](=[O:13])[CH2:7][CH2:6]2.N1CCCC1.[CH2:19](Br)[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1.Cl>C1(C)C=CC=CC=1.O>[CH2:19]([CH:9]1[C:10]2[C:5](=[CH:4][C:3]([O:2][CH3:1])=[CH:12][CH:11]=2)[CH2:6][CH2:7][C:8]1=[O:13])[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1

Komponenten

7

Edukt 4

HCID 313Hydrochloric AcidHCID 7498Benzyl BromideHCID 31268PyrrolidineHCID 755826-Methoxy-1,2,3,4-tetrahydronaphthalen-2-one

Produkt 1

HCID 107542391-benzyl-6-methoxy-3,4-dihydro-1H-naphthalen-2-oneAusbeute 84,7 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 962WaterLösungsmittelHCID 1140TolueneLösungsmittel

Versuchsvorschrift

A solution of 51 g (0.289 mol) of 6-methoxy-2-tetralone of formula A-1 wherein Rx is methoxy, and 24.2 mL (0.289 mol) of pyrrolidine in 1.5 L of toluene was heated to reflux, over a Dean-Stark trap, overnight. After removal of the azeotroped water, the reaction mixture was cooled to RT, concentrated to an oil, and dissolved in 725 mL of dioxane. To this solution was added 52 mL (0.434 mol) of benzyl bromide and the resulting solution was heated to reflux overnight. Water (100 mL) was added to the solution, and the resultant mixture was heated to reflux for an additional 2 h. The mixture was cooled to room temperature and poured into a solution of 1 N HCl and extracted 3 times with EtOAc. The organic layers were washed with H2O and saturated NaHCO3, then dried over Na2SO4, filtered, and evaporated to dryness. The crude product was purified by flash chromatography over SiO2 using 10% EtOAc to 15% EtOAc in hexanes as the gradient eluant to give 65.2 g of the title product of this preparation as a yellow oil (85%). IR (neat) 2937, 1712, 1500 cm−1; 1H NMR (400 MHz, CDCl3) δ 2.41-2.59 (m, 3H), 2.76 (dt, 1H, J=5.4, 15.5), 3.15-3.70 (m, 2H), 3.67 (t, 1H, J=6.3), 3.77 (s, 3H), 6.67-6.70 (m, 2H), 6.81 (d, 1H, J=8.1), 6.87-6.89 (m, 2H), 7.13-7.17 (m, 3H); 13C NMR (100 MHz, CDCl3) δ 27.44, 38.19, 39.19, 54.13, 55.14, 112.11, 112.96, 126.30, 128.07, 128.26, 129.35, 129.53, 138.05, 138.20, 158.30, 212.41; MS m/z 267 (M+H)+.

Aufarbeitung

  1. temperaturewas heated
  2. temperatureto reflux, over a Dean-Stark trap, overnight
  3. customAfter removal of the azeotroped water
  4. concentrationconcentrated to an oil
  5. dissolutiondissolved in 725 mL of dioxane
  6. temperaturethe resulting solution was heated
  7. temperatureto reflux overnight
  8. temperatureto reflux for an additional 2 h
  9. temperatureThe mixture was cooled to room temperature
  10. extractionextracted 3 times with EtOAc
  11. washThe organic layers were washed with H2O and saturated NaHCO3
  12. dry with materialdried over Na2SO4
  13. filtrationfiltered
  14. customevaporated to dryness
  15. customThe crude product was purified by flash chromatography over SiO2 using 10% EtOAc to 15% EtOAc in hexanes as the gradient eluant
  16. customto give

Quellen und Nachweise

ORD-Eintrag
ord-b6df93e6cdd94651a4d54b605673dd4d
Quelldatensatz
uspto-grants-2005_02
Patentnummer
US06852719B2

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