New Protocol for the Synthesis of 2-Alkanoyl- and 2-Aryloyl-5,5-dimethylcyclohexane-1,3-diones by the Reaction of Dimedone with Various Aldehydes and Cyanogen Bromide in the Presence of Triethylamine

Abstract

A new route for the synthesis of 2-alkanoyl(aryloyl)-5,5-dimethylcyclohexane-1,3-diones as cyclic β-triketones is described. This synthesis was conducted by the reaction of dimedone with cyanogen bromide and triethylamine to form first the intermediate salt, followed by the addition of various aliphatic and aromatic aldehydes. The structures of the products were characterized by IR, ¹H, and ¹³C NMR spectroscopic techniques. A reaction mechanism is proposed.

Key words

2-alkanoyl(aryloyl)dimedone - dimedone - cyanogen bromide - aldehyde - cyclic β-triketone - acylation

• References

• 1 Hassall CH In Progress in Organic Chemistry . Vol. 4. Cook JW. New York; Academic Press: 1958: 115-139
• 2 Forsen S, Nilsson M. Acta Chem. Scand. 1959; 13: 1383
• 3 Akhrem AA, Lakhvich FA, Budai SI, Khelebnicova TS, Petrusevich II. Synthesis 1978; 925
• 4 Mudd A. J. Chem. Soc., Perkin Trans. 1 1981; 2357
• 5 Mudd A. J. Chem. Soc., Perkin Trans. 1 1983; 2161
• 6 Mudd A, Corbet SA. J. Chem. Ecol. 1982; 8: 843
• 7 Mudd A, Walters JH. H, Corbet SA. J. Chem. Ecol. 1984; 10: 1597
• 8 Mudd A. J. Chem. Ecol. 1985; 11: 51
• 9 Seitz T, Willms L, van Almsick A, Bieringer H, Auler T, Menne H. US Patent 6,774,086 B2, 2004
• 10 Seitz T, van Almsick A, Willms L, Schmitt MH, Auler T, Bieringer H, Menne H. US Patent 6,930,208 B2, 2005
• 11 van Almsick A, Willms L, Hacker E, Bieringer H. Patent 6,576,593 B2, 2003
• 12 Laszlo BZ, Arzie TJ. US Patent WO1998042648 A1, 1998
• 13 Tarun EI, Rubinov DB, Metelitza DI. Appl. Biochem. Microbiol. 2004; 40: 337
• 14a Fatiadi AJ. Synthesis 1974; 165
• 14b Fatiadi AJ. Synthesis 1974; 241
• 15 Crossley W, Renouf N. J. Chem. Soc. 1912; 101: 1524
• 16 Smith H. J. Chem. Soc. 1953; 803
• 17 Ablovatskaya MV, Gudriniece EY, Strakov AY. Latv. PSR Zinat. Akad. Vestis, Khim. Ser. 1989; 601 ; Chem. Abstr. 1990, 112, 178751q
• 18 Strakov AY, Gudriniece EY, Strakova IA. Khim. Heterocycl. Soed. 1988; 723 ; Chem. Abstr. 1989, 110, 154173k
• 19 Azevedo NR, Santos SC, De Miranda EG, Ferri PH. Phytochemistry 1997; 46: 1375
• 20 Mudd A. J. Chem. Soc., Chem. Commun. 1978; 1075
• 21 Akhrem AA, Lakhvich FA, Khripach VA, Klebanovich IB. Khim. Geterotsikl. Soedin. 1975; 4: 329
• 22 Nilsson M, Merényi F. Acta Chim. Scand. 1964; 18: 1368
• 23 Rubinov DB, Rubinova IL, Akhrem AA. Chem. Rev. 1999; 99: 1047
• 24 Noroozi Pesyan N, Shokr A, Behroozi M, Şahin E. J. Iran. Chem. Soc. 2013; 10: 565
• 25 Adamson J, Coe BJ, Grassam HL, Jeffery JC, Coles SJ, Hursthouse MB. J. Chem. Soc., Perkin Trans. 1 1999; 2483
• 26 http://www.chemicalbook.com/ChemicalProductProperty_EN_CB2415765.htm (accessed date: 12/27/2015).
• 27 Hartman WW, Dreger EE. Org. Synth. Coll. Vol. 2 . Wiley; New York: 1943: 150