An Efficient and General Synthesis of Se-Esters of Diselenophosphinic Acids via Reaction of Alkali Metal Diselenophosphinates with Organic Halides

Abstract

Alkali metal diselenophosphinates R^¹ ₂PSe₂M (R^¹ = aryl, arylalkyl, hetarylalkyl; M = Na, K, or Cs) readily react with organic halides R^²Hal (R^² = alkyl, allyl, propargyl, benzyl; Hal = Cl, Br, or I) under mild conditions (EtOH, 50-55 ˚C, 30 min) to afford the corresponding Se-esters of diselenophosphinic acids R^¹ ₂P(Se)SeR^² in high yields (77-95%).

Key words

diselenophosphinates - organic halides - esters - alkylation

References

• For reviews, see:
• 1a Fan D. Afzaal M. Mallik MA. Nguyen CQ. O’Brien P. Thomas PJ. Coord. Chem. Rev.  2007,  251:  1878 
• 1b Malik MA. Afzaal M. O’Brien P. Chem. Rev.  2010,  110:  4417 
• For examples of heavy-metal diselenophosphinates applies as single-source precursors of nanomaterials, see:
• 2a Nguyen CQ. Afzaal M. Malik MA. Helliwell M. Raftery J. O’Brien P. J. Organomet. Chem.  2007,  692:  2669 
• 2b Panneerselvam A. Nguyen CQ. Waters J. Malik MA. O’Brien P. Raftery J. Helliwell M. Dalton Trans.  2008,  4499 
• 2c Hasegawa Y. Adachi T. Tanaka A. Afzaal M. O’Brien P. Doi T. Hinatsu Y. Fujita K. Tanaka K. Kawai T. J. Am. Chem. Soc.  2008,  130:  5710 
• 2d Maneeprakorn W. Nguyen CQ. Malik MA. O’Brien P. Raftery J. Dalton Trans.  2009,  2103 
• 2e Panneerselvam A. Nguyen CQ. Malik MA. O’Brien P. Raftery J. J. Mater. Chem.  2009,  19:  419 
• 2f Tanaka A. Adachi T. Hasegawa Y. Kawai T. J. Alloys Compd.  2009,  488:  538 
• 2g Kawai T, Hasegawa Y, and Adachi T. inventors; US  20,090,015,919. 
• 2h Maneeprakorn W. Malik MA. O’Brien P. J. Mater. Chem.  2010,  20:  2329 
• 3 Lobana TS. Wang J.-C. Liu CW. Coord. Chem. Rev.  2007,  251:  91 
• 4 Egorova NS. Belova VV. Voshkin AA. Zhilov VI. Kholkin AI. Russ. J. Inorg. Chem. (Engl. Transl.)  2005,  50:  1902 
• 5a Moon J. Nam H. Kim S. Ryu J. Han C. Lee C. Lee S. Tetrahedron Lett.  2008,  49:  5137 
• 5b Song E. Jo Y. Bae G. Oh I.-K. Jung HM. Lee S. Bull. Korean Chem. Soc.  2009,  30:  2129 
• 6 Matolcsy G. Nadasy M. Andriska V. Pesticide Chemistry   Elsevier; Budapest: 1988. 
• 7a Kimura T. Murai T. J. Org. Chem.  2005,  70:  952 
• 7b Kimura T. Murai T. Mizuhata N. Heteroat. Chem.  2005,  16:  185 
• 7c Murai T. Kimura T. Curr. Org. Chem.  2006,  10:  1963 
• For reviews about the availability of secondary phosphines from red phosphorus, see:
• 8a Trofimov BA. Arbuzova SN. Gusarova NK. Russ. Chem. Rev. (Engl. Transl.)  1999,  68:  215 
• 8b Trofimov BA. Gusarova NK. Mendeleev Commun.  2009,  19:  295 
• 9 For examples of synthesis of alkali metal diselenophos-phinates from secondary phosphines, see: Artem’ev AV. Malysheva SF. Gusarova NK. Trofimov BA. Synthesis  2010,  2463 
• 10 For examples of synthesis of alkali metal diselenophos-phinates from secondary phosphine selenides, see: Trofimov BA. Artem’ev AV. Malysheva SF. Gusarova NK. J. Organomet. Chem.  2009,  694:  4116 
• 11a Duddeck H. Prog. Nucl. Magn. Reson. Spectrosc.  1995,  27:  1 
• 11b Duddeck H. In Encyclopedia of Nuclear Magnetic Resonance   Vol. 7:  Grant DM. Harris RK. Wiley; New York: 1996.  p.4623