Reaktion #82319

Reaktionsgleichung

sodium amide

(R)-(-)-epichlorohydrin

phenylacetonitrile

hydrochloric acid

sodium hydrogencarbonate

ethyl acetate

KOH

→

compound 1

Ausbeute 58.0%

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

Ausbeute 58.0%

Lösungsmittel

benzene

benzene

benzene

ethanol

Reaktionsbedingungen

Aufarbeitung

1. 1
   workup.ADDITIONAfter completion of the addition
2. 2
   Sonstigea reaction
3. 3
   SonstigeTo the resultant reaction mixture
4. 4
   Temperaturwhile cooling with ice
5. 5
   workup.ADDITIONAfter completion of the addition
6. 6
   Sonstigea reaction
7. 7
   SonstigeAfter completion of the reaction
8. 8
   Sonstigethe resultant reaction mixture
9. 9
   workup.DISTILLATIONwas subjected to distillation under reduced pressure
10. 10
    Sonstigeto thereby remove the solvent
11. 11
    Sonstigeobtain a residue
12. 12
    Sonstigea reaction
13. 13
    workup.ADDITIONwas added to the mixture which
14. 14
    Temperaturcooling with ice
15. 15
    EinengenThe acidified mixture was concentrated under reduced pressure
16. 16
    Sonstigeto thereby obtain a residue
17. 17
    workup.ADDITIONwas further added for extraction
18. 18
    Sonstigeto obtain an organic layer
19. 19
    SonstigeThe organic layer was separated
20. 20
    Waschenwashed with saturated saline
21. 21
    Trocknendried over anhydrous sodium sulfate
22. 22
    workup.DISTILLATIONsubjected to distillation under reduced pressure
23. 23
    Sonstigeto thereby remove the solvent
24. 24
    Sonstigeobtain a residue
25. 25
    SonstigeThe obtained residue was purified by silica gel column chromatography (the composition of the developing solvent

Vorschrift

8.58 g (0.22 mmol) of sodium amide was suspended in 40 ml of anhydrous benzene. To the resultant 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. After completion of the addition, the resultant mixture was stirred at room temperature for 3 hours to effect a reaction. To the resultant reaction mixture was dropwise added a solution of 6.8 ml (0.087 mol) of (R)-(-)-epichlorohydrin in 20 ml of anhydrous benzene while cooling with ice. After completion of the addition, the resultant mixture was stirred at room temperature for 2 hours to effect a reaction. After completion of the reaction, the resultant reaction mixture was subjected to distillation under reduced pressure to thereby remove the solvent and obtain a residue. 20 ml of ethanol and 10 ml of an aqueous 1N-KOH solution were added to the obtained residue, and the resultant mixture was refluxed for 15 hours to effect a reaction. After completion of the reaction, 12N hydrochloric acid was added to the mixture which 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, 10.1 g (0.058 mol) of compound 1 (yield: 58%) was obtained as a yellow oily product.

Quelle