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

HRID 1789114ノート

反応式

HRID 1789114 の反応式
[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

参加物

10

反応物 4

HCID 240BenzaldehydeHCID 313Hydrochloric Acid2 回HCID 86741736beta-Dimethylamino-alpha-methylpropiophenone 2,4,6-triisopropylbenzenesulphonylhydrazoneHCID 178418306HCID 178418306、化合物

生成物 1

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

試薬・触媒・溶媒 5

HCID 180Acetone溶媒HCID 962Water溶媒HCID 3283Diethyl Ether溶媒2 回HCID 8003Pentane溶媒HCID 80711,2-Dimethoxyethane溶媒

反応条件

温度
15 °C

実験手順

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.

後処理

  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)

出典と根拠

ORDレコード
ord-e523d3bf6d6f4be7aaccce500d9e3658
出典データセット
uspto-grants-1987_08
特許番号
US04686309

反応ノート

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