Spontaneous organic reactions for energy-efficient synthesis

ORGN 708

Maghar S. Manhas, mmanhas@stevens.edu, Subhendu N Ganguly, gangulysn@yahoo.com, Ajay K. Bose, abose@stevens.edu, Arun Mandadi, arunmandadi@rediffmail.com, Amit K. Jain, jain_chinu2004@yahoo.com, and Deepu J. Varughese, dvarughe@stevens.edu. George Barasch Bioorganic Research Laboratory, Department of Chemistry and Chemical Biology, Stevens Institute of Technology, Castle Point on Hudson, Hoboken, NJ 07030
Traditional modes of synthetic reactions usually involve a solvent medium. It may be noted that solvents mask the intrinsic energy aspects of reactions. Therefore, only solvent-free reactions will be considered here. Some solvent-free organic reactions are endothermic, others are exothermic. Most exothermic reactions appear to need a short burst of external energy for initiation; some exothermic reactions, however, are spontaneous and proceed to completion on just mixing the reagents in the absence of a solvent. The variation in the exothermicity of a particular type of reaction depends on the components. The Knoevenagel condensation of benzaldehyde with malonic acid or malonic ester in the presence of a base for coumarin formation requires energy input. But when 4-nitrobenzaldehyde is mixed with malononitrile on a 2-3-gm scale, there is a spontaneous reaction and the temperature of the mixture reaches about 170 °C in about 1 min. A very different type of spontaneous reaction is self-assembly in high yield of a mixture of 6 moles of benzyl amine and 3 moles of glyoxal (catalyze by a few drops of formic acid). This cage compound is key intermediate for a high energy molecule.

 

Heterocycles and Aromatics
8:00 AM-12:00 PM, Thursday, 1 September 2005 Washington DC Convention Center -- Ballroom B, Oral

Division of Organic Chemistry

The 230th ACS National Meeting, in Washington, DC, Aug 28-Sept 1, 2005