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

HRID 845167Notes

Reaction equation

HRID 845167 reaction equation
[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

Participants

10

Reactant 4

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

Product 1

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

Reagents, catalysts & solvents 5

HCID 180AcetoneSolventHCID 962WaterSolventHCID 3283Diethyl EtherSolvent2×HCID 8003PentaneSolventHCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
15 °C

Procedure

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 (7 cc) 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 10N 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.

Workup

  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)

Sources & evidence

ORD record
ord-4f8675e60a924d6b9e8298ce0d242203
Source dataset
uspto-grants-1988_07
Patent number
US04755599

Reaction notes

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