Reaktion #82320

Reaktionsgleichung

sodium amide

KOH

hydrochloric acid

phenylacetonitrile

(S)-(+)-epichlorohydrin

sodium hydrogencarbonate

ethyl acetate

→

compound 13

(1R, 2S)-1-phenyl-2-hydroxymethyl cyclopropane carboxylic anhydride

Lösungsmittel

ethanol

benzen

benzen

benzen

Reaktionsbedingungen

Aufarbeitung

1. 1
   workup.ADDITIONAfter the addition
2. 2
   Sonstigea reaction
3. 3
   Temperaturwhile cooling with ice
4. 4
   workup.ADDITIONAfter the addition
5. 5
   Sonstigea reaction
6. 6
   SonstigeAfter completion of the reaction
7. 7
   workup.DISTILLATIONthe resultant mixture was subjected to distillation under reduced pressure
8. 8
   Sonstigeto thereby remove the solvent
9. 9
   Sonstigeobtain a residue
10. 10
    Sonstigea reaction
11. 11
    workup.ADDITIONwas added to the resultant
12. 12
    Sonstigereaction mixture
13. 13
    Einengenthe acidified mixture was concentrated under reduced pressure
14. 14
    Sonstigeto thereby obtain a residue
15. 15
    workup.ADDITIONwas further added for extraction
16. 16
    Sonstigeto obtain an organic layer
17. 17
    SonstigeThe organic layer was separated
18. 18
    Waschenwashed with saturated saline
19. 19
    Trocknendried over anhydrous sodium sulfate
20. 20
    workup.DISTILLATIONsubjected to distillation under reduced pressure
21. 21
    Sonstigeto thereby remove the solvent
22. 22
    Sonstigeobtain a residue
23. 23
    SonstigeThe 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 benzen. To the resultant suspension was dropwise added a solution of 11.5 ml (0.10 mol) of phenylacetonitrile in 20 ml of anhydrous benzen in a stream of argon gas at 0° C. After the addition, the resultant mixture was stirred at room temperature for 3 hours to effect a reaction. To the resultant mixture was dropwise added a solution of 6.8 ml (0.087 mol) of (S)-(+)-epichlorohydrin in 20 ml of anhydrous benzen while cooling with ice. After the addition, the resultant mixture was stirred at room temperature for 2 hours to effect a reaction. After completion of the reaction, the resultant 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. The resultant mixture was refluxed for 15 hours to effect a reaction. After completion of the reaction, 12N hydrochloric acid was added to the resultant reaction mixture to thereby acidify the mixture, and 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 residue was purified by silica gel column chromatography (the composition of the developing solvent was; ethyl acetate:hexane=1:3). As a result, compound 13 (10.0 g) was obtained as an orange oily product.

Quelle