Electrooxidation of Malonate and Acetylacetate Derivatives in the Presence of Halide Ions

Abstract

β-Dicarbonyl compounds, such as dimethyl malonate derivatives and methyl acetoacetate derivatives, were electrooxidized in methanol in the presence of halogen ions to afford the corresponding dimethyl α-halomalonates and methyl α-halocarboxylates. Electrooxidation of bis(β-dimethoxycarbonyl) derivatives similarly afforded cyclic compounds and dihalides.

Key words

cyclization - halogenation - electron transfer - halide - oxidation

References

• 1a Fichter F. Ruegg R. Helv. Chim. Acta  1937,  20:  1578 
• 1b Szper J. Bull. Soc. Chim. Fr.  1932,  51:  653 
• 2a Okubo T. Tsutusmi S. Bull. Chem. Soc. Jpn.  1964,  37:  1794 
• 2b Osa T. Ohkatsu Y. Tezuka M. 149th Electrochemical Society Meeting, Ext. Abst. P.764   American Chemical Society; Washington D.C.: 1976. 
• 2c White DA. J. Electrochem. Soc.  1977,  124:  1177 
• 2d Brettle R. Parkin JG. J. Chem. Soc. C  1967,  1352 
• 3 Shi X.-X. Dai L.-X. J. Org. Chem.  1993,  58:  4596 
• 4 Torii S. Uneyama K. Yamasaki N. Bull. Chem. Soc. Jpn.  1980,  53:  819 
• 5a Elinson MN. Fedukovich SK. Nikishin GI. Izv. Akad. Nauk., Ser. Khim.  1987,  228 ; Chem. Abstr. 1987, 107, 153951
• 5b Elinson MN. Fedukovich SK. Ugrak BI. Nikishin GI. Izv. Akad. Nauk., Ser. Khim.  1992,  2332 ; Chem. Abstr. 1993, 119, 49183
• 5c Elinson MN. Fedukovich SK. Nikishin GI. Izv. Akad. Nauk., Ser. Khim.  1990,  2783 ; Chem. Abstr. 1991,114, 184833
• 6a Adams R. Kann RM. Org. Synth., Coll. Vol. 1   Wiley; New York: 1941.  p.250 
• 6b Weiner N. Org. Synth. Coll. Vol. 2   Wiley; New York: 1943.  p.279 
• 7 Meerwein H. Liebigs Ann. Chem.  1908,  360:  344 
• 8 Boni M. Ghelfi F. Pagnoni UM. Pinetti A. Bull. Chem. Soc. Jpn.  1994,  67:  156 
• 9 Ikesu S, Kimura K, and Ohta K. inventors; Jpn. Kokai Tokkyo Koho  JP 11171876 A2.  ; Chem. Abstr. 1999, 131, 73644
• 10 Mor G. Ehret A. Cohen SG. Arch. Biochem. Biophys.  1976,  174:  158 
• 11 Beyler RE. Sarett LH. J. Am. Chem. Soc.  1952,  74:  1397 
• 12 Stohmann F. J. Prakt. Chem.  1892,  45:  475