Synthesis of 1,3-Selenazoles and Bis(selenazoles) from Primary Selenocarboxylic Amides and Selenourea

Abstract

The reaction of nitriles with P₂Se₅ in the presence of EtOH-H₂O afforded primary selenocarboxylic amides. The cyclization of these compounds with α-halo ketones afforded a variety of functionalized 1,3-selenazoles. The use of P₂Se₅ also allowed the convenient synthesis of selenocarboxylic diamides which were transformed into bis(selenazol-2-yl)alkanes (‘bis-selenazoles’). A practical method for the synthesis of selenourea was developed. This useful small building block was successfully applied to the synthesis of primary 2-amino-1,3-selenazoles.

cyclizations - heterocycles - nitriles - selenium - amides

References

1 Schwar K. Foltz CM. J. Am. Chem. Soc.  1957,  79:  3292 

2 Mills GC. J. Biol. Chem.  1957,  229:  189 

3 Rotruck JT. Pope AE. Ganther HE. Swanson AB. Hafemann DG. Hoekstra WG. Science  1973,  179:  588 

4 Goldstein BM. Kennedy SD. Hennen WJ. J. Am. Chem. Soc.  1990,  112:  8265 ; and references cited therein

5a Larsen R. 1,3-Selenazoles, In Comprehensive Heterocyclic Chemistry II   Vol. 3:  Katritzky A. Rees CW. Scriven EFV. Eds. Elsevier Science; Oxford: 1996.  Chap. 8.

5b Wirth T. Organoselenium Chemistry. Modern Developments in Organic Synthesis   Springer; Berlin: 2000. 

5c Koketsu M. Nada F. Ishihara H. Synthesis  2002,  195 ; and references cited therein

5d Geisler K. Pfeiffer W.-D. Müller C. Nobst E. Bulka E. Langer P. Synthesis  2003,  1215 

6a Lai L.-L. Reid DH. Synthesis  1993,  870 

6b Klayman DL. Griffins TS. J. Am. Chem. Soc.  1973,  95:  197 

6c For the use of LiAlH4/Se, see: Ishihara H. Koketsu M. Fukuta Y. Nada F. J. Am. Chem. Soc.  2001,  123:  8408 

6d See also: Koketsu M. Fukuta Y. Ishihara H. Tetrahedron Lett.  2001,  42:  6333 

7 Ogawa A. Miyaka J. Karasaki Y. Murai S. Sonoda N. J. Org. Chem.  1985,  50:  384 

8 Kaminski R. Glass RS. Skowronska A. Synthesis  2001,  1308 

9 Cohen VJ. Synthesis  1978,  668 

10 Brauer B. Handbuch der präparativen anorganischen Chemie   Ferd. Enke Verlag; Stuttgart: 1960.  p.732 

11 Geisler K. Jacobs A. Künstler A. Mattes M. Girrleit I. Zimmermann B. Bulka E. Pfeiffer W.-D. Langer P. Synlett  2002,  1983 ; and references cited therein

12 Bhattacharyya P. Woollins JD. Tetrahedron Lett.  2001,  5949 

13 Kudchadker MV. Zingaro RA. Irgolic KJ. Can. J. Chem.  1968,  46:  1415 

14 For the synthesis of thioamides from amides, see: Raucher S. Klein P. J. Org. Chem.  1981,  46:  3558 

For the synthesis of N,N-disubstituted selenocarboxylic amides, see:

15a Collhard-Charon C. Renson M. Bull. Soc. Chim. Belg.  1963,  72:  304 

15b Jensen KA. Nielsen PH. Acta Chim. Scand.  1966,  20:  597 

15c See also: Sukhai RS. de Jong R. Brandsma L. Synthesis  1977,  888 

16a For 4a, see: Hofmann G. Justus Liebigs Ann. Chem.  1889,  250:  294 ; and ref.⁶

16b For 4c and 4d, see: Zhang P.-P. Chen Z.-C. Synthesis  2000,  1219 

For 4o, see:

17a Metzger J. Bailly P. Compt. Rend. Acad. Sci.  1953,  237:  906 

17b Backer HJ. Bos H. Recl. Trav. Chim. Pays-Bas  1943,  62:  580 

18a Dunbar RE. Painter EP. J. Am. Chem. Soc.  1947,  69:  1833 

18b Hope H. Acta Chem. Scand.  1964,  18:  1800 

18c Badillo R. Breccia R. Ric. Sci.  1966,  36:  335 

18d For the reaction of thiourea with toxic NaHSe and methyl iodide, see: Liu B. Xu C. Zhou X. Huaxue Shiji  1993,  15:  334 ; Chem. Abstr. 1994, 457594

19 Zhou Y. Linden A. Heimgartner H. Helv. Chim. Acta  2000,  83:  1576 ; and references cited therein

20 Douglass IB. J. Am. Chem. Soc.  1937,  59:  740 

21 Flaig R. Hartmann H. Heterocycles  1997,  45:  875 

22 Huls R. Renson M. Bull. Soc. Chim. Belg.  1956,  65:  1956