Reaktion #82322

Reaktionsgleichung

epichlorohydrin

sodium amide

sodium hydrogencarbonate

ethyl acetate

KOH

phenylacetonitrile

hydrochloric acid

→

compound 25

Ausbeute 60.0%

(1S, 2R )-1-phenyl-2-hydroxymethylcyclopropane carboxylic anhydride

Ausbeute 60.0%

Lösungsmittel

benzene

benzene

ethanol

benzene

Reaktionsbedingungen

Aufarbeitung

1. 1
   Sonstigeto thereby obtain a suspension
2. 2
   Sonstigea reaction
3. 3
   Temperaturwhile cooling with ice
4. 4
   Sonstigea reaction
5. 5
   SonstigeAfter completion of the reaction
6. 6
   workup.DISTILLATIONthe reaction mixture was subjected to distillation under reduced pressure
7. 7
   Sonstigeto thereby remove the solvent
8. 8
   Sonstigeobtain a residue
9. 9
   Sonstigeto thereby obtain a mixture
10. 10
    TemperaturThe mixture was refluxed for 15 hours
11. 11
    Temperaturwhile cooling with ice
12. 12
    EinengenThe acidified mixture was concentrated under reduced pressure
13. 13
    Sonstigeto thereby obtain a residue
14. 14
    workup.ADDITIONwas further added for extraction
15. 15
    Sonstigeto obtain an organic layer
16. 16
    SonstigeThe organic layer was separated
17. 17
    Waschenwashed with saturated saline
18. 18
    Trocknendried over anhydrous sodium sulfate
19. 19
    workup.DISTILLATIONsubjected to distillation under reduced pressure
20. 20
    Sonstigeto thereby remove the solvent
21. 21
    Sonstigeobtain a residue
22. 22
    SonstigeThe obtained residue was purified by silica gel column chromatography (the composition of the developing solvent

Vorschrift

8.58 g (0.22 mol ) of sodium amide was suspended in 40 ml of anhydrous benzene, to thereby obtain a suspension. To the obtained suspension was dropwise added a solution of 11.5 ml (0.10 mol) of phenylacetonitrile in 20 ml of anhydrous benzene in a stream of argon gas at 0° C. Then, the resultant mixture was stirred at room temperature for 3 hours, to thereby effect a reaction. To the reaction mixture was dropwise added a solution of 6.8 ml (0.087 mol) of a racemic modification of epichlorohydrin in 20 ml of anhydrous benzene while cooling with ice. Then, the resultant mixture was stirred at room temperature for 2 hours to thereby effect a reaction. After completion of the reaction, the reaction mixture was subjected to distillation under reduced pressure to thereby remove the solvent and obtain a residue. To the obtained residue were added 20 ml of ethanol and 10 ml of an aqueous 1N-KOH solution to thereby obtain a mixture. The mixture was refluxed for 15 hours. After that period of time, 12N hydrochloric acid was added to the resultant mixture while cooling with ice to thereby acidify the mixture. The acidified mixture was concentrated under reduced pressure to thereby obtain a residue. A saturated aqueous sodium hydrogencarbonate solution was added to the obtained residue, and ethyl acetate was further added for extraction to obtain an organic layer. The organic layer was separated, washed with saturated saline, dried over anhydrous sodium sulfate, and subjected to distillation under reduced pressure to thereby remove the solvent and obtain a residue. The obtained residue was purified by silica gel column chromatography (the composition of the developing solvent was; ethyl acetate:hexane=1:3). As a result, compound 25 (yield: 60%) was obtained as an orange oily product.

Quelle