Direct evidence for the hydroxide extraction mechanism in the phase transfer catalyzed cyclopropanation of 4-halobutyronitrile in a solid-liquid system

Tetrahedron Letters

Volumn 39, Issue 52, 1998, Pages 9815-9818

  Cohen, Shlomo ^b   Zoran, Ami ^b   Sasson, Yoel ^a  

^a HEBREW UNIVERSITY OF JERUSALEM   (Israel)

^b NONE

Author keywords

[No Author keywords available]

Indexed keywords

4 BROMOBUTYRONITRILE; 4 CHLOROBUTYRONITRILE; BUTYRONITRILE; CYCLOPROPANE; HYDROXIDE; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; CHEMICAL REACTION; EXTRACTION; MOLECULAR STABILITY; PHASE TRANSITION;

EID: 0032564533     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(98)02240-0     Document Type: Article

References (18)

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4. 4. Makosza, M. in "Handbook of Phase Transfer Catalysis", Sasson, Y.; Neumann, R., Eds. Blackie Academic: London 1997, p. 135.
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7. 7. For other methods for assay of quaternary ammonium hydroxides see: Brandstrom, A.,"Preperative Ion-pair Extraction" Apotekarscocieteten Hassle Lakemedel, Stockholm. 1977. De la Zerda, J.; Sasson, Y., J. Chem. Soc., Perkin Trans. 2 1987, 1147.
8. 7. For other methods for assay of quaternary ammonium hydroxides see: Brandstrom, A.,"Preperative Ion-pair Extraction" Apotekarscocieteten Hassle Lakemedel, Stockholm. 1977. De la Zerda, J.; Sasson, Y., J. Chem. Soc., Perkin Trans. 2 1987, 1147.
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11. 10. It should be noted that synthetic procedures resulting with high yield and purity were developed in this study, both from 1 and from 2. These will be published elsewhere.
12. 11. Pure TBAOH was obtained by solvent evaporation (40 °C, 20 mmHg) of the commercial (Aldrich) 1M solution in MeOH. TBAOH (1.3 g, 5 mmol), 4-Br or Cl-butyronitrile (0.74 g , 5 mmol or 0.52 g, 5 mmol respectively) and 5 ml xylenes (h.p. 140°) as solvent were stirred at 40 °C. Reaction composition monitored by G.C. (30m, 5% diphenyl, 95% dimethylpolysiloxane Column and FID, Acenaphtene as internal standard). At least 8 samples were taken per run.
13. 12. 4-Br or Cl-Butyronitrile (0.88 g, 6 mmol or 0.62 g, 6 mmol respectively), TBABr or Cl (95 mg,0.6 mmol or 85 mg, 0.6 mmol respectively), freshly powdered solid NaOH (480 mg, 12 mmol), and 10 ml xylenes were stirred at 70 °C. Analysis were performed as above.
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