Benzaldehyde → 1-(1-Hydroxy-1,2,3,4-tetrahydro-1-naphthyl)-3-dimethylamino-1-phenyl-1-propene

HRID 1789114Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1789114
[C:1]([Li])(C)([CH3:3])[CH3:2].C(C1C=C(C(C)C)C=C(C(C)C)C=1S(NN=[C:26]([C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1)[CH:27](C)[CH2:28][N:29]([CH3:31])[CH3:30])(=O)=O)(C)C.[CH:39](=[O:46])[C:40]1[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=1.Cl>CCCCC.COCCOC.CC(C)=O.C(OCC)C.O>[OH:46][C:39]1([C:26]([C:33]2[CH:34]=[CH:35][CH:36]=[CH:37][CH:38]=2)=[CH:27][CH2:28][N:29]([CH3:30])[CH3:31])[C:40]2[C:45](=[CH:44][CH:43]=[CH:42][CH:41]=2)[CH2:3][CH2:1][CH2:2]1

Komponenten

10

Edukt 4

HCID 240BenzaldehydeHCID 313Hydrochloric Acid2×HCID 86741736beta-Dimethylamino-alpha-methylpropiophenone 2,4,6-triisopropylbenzenesulphonylhydrazoneHCID 178418306HCID 178418306, Verbindung

Produkt 1

HCID 544490061-(1-Hydroxy-1,2,3,4-tetrahydro-1-naphthyl)-3-dimethylamino-1-phenyl-1-propene

Reagenzien, Katalysatoren, Lösungsmittel 5

HCID 180AcetoneLösungsmittelHCID 962WaterLösungsmittelHCID 3283Diethyl EtherLösungsmittel2×HCID 8003PentaneLösungsmittelHCID 80711,2-DimethoxyethaneLösungsmittel

Reaktionsbedingungen

Temperatur
15 °C

Versuchsvorschrift

A 1.9M solution (30.4 cc) of tert-butyllithium in pentane is added to a solution of β-dimethylamino-α-methylpropiophenone 2,4,6-triisopropylbenzenesulphonylhydrazone (10.9 g) in 1,2-dimethoxyethane (109 cc), kept under nitrogen atmosphere at a temperature in the region of -75° C. Once the addition has been completed the reaction mixture is warmed slowly to 15° C. When gas evolution has stopped, the reaction mixture is cooled to a temperature in the region of -40° C. Benzaldehyde (4.2 g) is then added and stirring is continued for 20 minutes while the temperature is allowed to rise to approximately -5° C. Distilled water (50 cc), an aqueous solution (7cc) of concentrated hydrochloric acid, and then ethyl ether (200 cc) are added in succession. The organic phase is separated and then extracted with a 4N aqueous solution of hydrochloric acid (2×25 cc). The aqueous phases are combined, made alkaline to a pH in the region of 10 with a 10 N aqueous solution of sodium hydroxide and then extracted with ethyl acetate (3×150 cc). The organic phases are combined, dried over magnesium sulphate, filtered and then concentrated to dryness under reduced pressure (2.7 kPa) at 30° C. The orange oil obtained is dissolved in acetone (91 cc); a 5.6N solution (4.5 cc) of hydrochloric acid gas in ethyl ether is added to the solution obtained. The solid formed is separated off by filtration and then recrystallised from a mixture (48 cc) of isopropanol and isopropyl ether (80/20 by volume). In this way 4-dimethylamino-1,2-diphenyl-3-methyl-2-buten-1-ol (Z) hydrochloride (1.85 g) is obtained in the form of a white powder melting at 212° C.

Aufarbeitung

  1. customkept under nitrogen atmosphere at a temperature in the region of -75° C
  2. additionOnce the addition
  3. temperaturethe reaction mixture is cooled to a temperature in the region of -40° C
  4. customto rise to approximately -5° C
  5. customThe organic phase is separated
  6. extractionextracted with a 4N aqueous solution of hydrochloric acid (2×25 cc)
  7. extractionextracted with ethyl acetate (3×150 cc)
  8. dry with materialdried over magnesium sulphate
  9. filtrationfiltered
  10. concentrationconcentrated to dryness under reduced pressure (2.7 kPa) at 30° C
  11. customThe orange oil obtained
  12. customobtained
  13. customThe solid formed
  14. customis separated off by filtration
  15. customrecrystallised from a mixture (48 cc) of isopropanol and isopropyl ether (80/20 by volume)

Quellen und Nachweise

ORD-Eintrag
ord-e523d3bf6d6f4be7aaccce500d9e3658
Quelldatensatz
uspto-grants-1987_08
Patentnummer
US04686309

Notizen zur Reaktion

Wird geladen…