The first effective syntheses of cyanofluoromethylated amides, thioamides, and phosphorus compounds using 2-cyano-2-fluoro-2- phenylacetonitrile and Et3GeNa

Synthesis

Volumn , Issue 8, 1999, Pages 1319-1324

  Yokoyama, Yasuo ^a   Mochida, Kunio ^a  

^a GAKUSHUIN UNIVERSITY   (Japan)

Author keywords

Amides; Cyanfluoromethylation; Et3GeNa; Phosphorus compounds; Thioamides

Indexed keywords

AMIDE; BENZYL CYANIDE DERIVATIVE; PHOSPHORUS DERIVATIVE; THIOAMIDE;

ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; NONHUMAN; REACTION ANALYSIS; SYNTHESIS;

EID: 0032872304     PISSN: 00397881     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-1999-3543     Document Type: Article

References (21)

1. For selected reviews, see: a) Banks, R. E. Organofluorine Chemicals and Their Industrial Applications, Royal Soc. Chem. Ind.: London, 1979.
2. b) Filler, R.; Kobayashi, Y. Biomedical Aspects of Fluorine Chemistry, Kodansha Ltd.: Tokyo, 1982.
3. c) Liebman, J. K.; Greenberg, A.; Dolbier Jr., W. R. Fluorine-containing Molecules, Stru
4. d) Welch, J. T.; Eshwarakrishman, S. Fluorine Bioorganic Chemistry, Wiley: New York, 1991.
5. Takeuchi, Y. J. Synth. Org. Chem. Jpn. 1988, 46, 145 and Ref. 1.
6. a) Takeuchi, Y.; Takagi, K.; Yamada, T.; Nabetani, M.; Koizumi, T. J. Fluorine Chem. 1994, 68, 149.
7. b) Takeuchi, Y.; Kawahara, S.; Suzuki, S.; Koizumi, T. J. Org. Chem. 1996, 61, 301.
8. c) Takeuchi, Y. J. Syn. Org. Chem. Jpn. 1997, 55, 886.
9. a) Yokoyama, Y.; Mochida, K. J. Chem. Soc., Chem. Commun. 1998, 1093.
10. b) Yokoyama, Y.; Mochida, K. Synthesis 1998, in press.
11. Syntheses of cyanofluoromethylated compounds through the stepwise introduction of cyano and fluoro substituents have already reported. For example, the cyanoluoromethylated amide could be prepared by a stepwise technique, see: Takeuchi, Y.; Itoh, N.; Satoh, T.; Koizumi, T.; Yamaguchi, K. J. Org. Chem. 1993, 58, 1812, and references cited therein.
12. Syntheses of various organophosphorus compounds have been well investigated, but the synthetic method of this type of compound using the cyanofluoromethylation has not been reported at the present stage. For a selected review, see: Kosolapoff, G. M.; Maier, L. Organic Phosphorus Compounds, Wiley: New York, 1972-1976, and references cited therein.
13. When this preparative reaction was carried out at -60°C for 2 h, 2-fluoro-2-phenylacetonitrile was obtained as the major product, and the desired compound was synthesized in low yield.
14. a) Bulten, E. J.; Noltes, J. G. Tetrahedron Lett. 1966, 4389.
15. b) Bulten, E. J.; Noltes, J. G. Tetrahedron Lett. 1967, 1443.
16. a) 2-Fluoro-2-phenylthio-2-phenylacetonitrile: Ref. 4b.
17. b) Dipropyl chlorophosphate, diisopropyl chlorophosphate, dibutyl chlorophosphate, and diisobutyl chlorophosphate: Sosnovsky, G.; Zaret, E. H. J. Org. Chem. 1969, 34, 968.
18. c) Dipentyl chlorophosphate: Ramaswami, D.; Kirch, E. R. J. Am. Chem. Soc. 1953, 75, 1763.
19. d) Dihexyl chlorophosphate: Grosse-Ruyken, H.; Uhlig, K. J. Prakt. Chem. 1962, 18, 287.
20. e) Dipropylphosphinic chloride: Kosolapoff, G. M.; Watson, R. M. J. Am. Chem. Soc. 1951, 73, 4101.
21. f) Dibutylphosphinic chloride: Pollart, K. A.; Harwood, H. J. J. Org. Chem. 1962, 27, 4444.