Mills, Michael

Thanks to Clive Mabey, Michael Mills, and Richard Veryard for this example. 

Electron-poor alkenes are suitable starting points for Michael additions. For example, the arylidene malononitrile 363 adds quantitatively to solid dimedone (255) upon milling at 80 °C followed by heating of the yellow powder to 100 °C. The initial Michael adduct 364 is not isolated, as it cyclizes in the solid state to give the pyrone 365 with 100% yield [107] (Scheme 58). The potentials for waste-free solid-state chemistry are manifold indeed and deserve further exploration. 

The solid-state interaction of enamines (428, 333a) with trans-l,2-diben-zoylethene (87) provides quantitative yields of the pyrrole derivatives 445 or 446 [140]. These remarkable 5-cascades consist of initial vinylogous Michael addition, enol/keto tautomerism, imine/enamine tautomerism, cyclization, and elimination, all within the crystal without melting. A waste-free extraordinary atom economy is achieved that cannot nearly be obtained in solution. The milling times are unusually long here (3 h) but it s certainly worth the effort... 

S. Suzanne Nielsen (Chair 2001- ) Vice-Chair (1998-2000), Department of Food Science, Purdue University, West Lafayette, IN Grady W. Chism III (Vice-Chair 2001- ) Department of Food Science and Technology, Ohio State University, Columbus Michael H. Auerbach, Danisco USA, Inc., Ardsley, NY Jonathan DeVries, General Mills, Inc., Minneapolis, MN Mark Dreher, McNeil Nutritionals, New Brunswick, NJ Carl Frey, Pepsi Cola North America, Valhalla, NY David S. Frick, Sensient Colors, Inc., St. Louis, MO Glen Ishikawa, NutraSweet Company, Evanston, IL Richard W. Lane, Unilever Bestfoods NA, Englewood Cliffs, NJ John W. Salminen, Health Canada, Ottawa, Ontario, Canada... 

Michael H. Auerbach, Danisco Cultor America, Inc., Ardsley, New York Jonathan DeVries, General Mills, Inc., Minneapolis, Minnesota Mark Dreher, Mead Johnson Nutritionals, Evansville, Indiana... 

TERENCE V. ASHWORTH, MICHAEL J. CHETCUTI, LOUIS J. FARRUGIA, JUDITH A. K. HOWARD, JOHN C. JEFFERY, RONA MILLS, GEOFFREY N. PAIN, F. GORDON A. STONE, and PETER WOODWARD... 

It has also been demonstrated that ketimines may participate in reactions with nitrostyrenes providing fused pyrroles, as shown by the preparation of the system 311. The series of events leading to this outcome were suggested to involve a Michael-type addition of the enamine tautomer of the substrate 312 to the olefin, followed by annulation with concomitant elimination of the nitro functionality (Equation 92) <1999TL4177>. In addition, solid-state reactions of enamine esters or ketones with ( )-l,2-dibenzoylethene induced by milling gave excellent yields of pyrroles <1999AGE2896>. 

Submitted by WILLIAM S. REES, JR., MICHAEL D. HAMPTON, STEPHEN W. HALL, and JERRY L. MILLS ... 

Graham Mills University of Portsmouth, School of Pharmacy and Biomedical Sciences, St Michaels Building, White Swan Road, Portsmouth POl 2DT, UK... 

Keywords Michael reaction, azachalcone, high-speed vibration milling... 

This is the implication in many press accounts. Michael Pollen of the New York Times, for example, explored this tension in an article last year focusing on Cascadian Farms and its purchase by General Mills. Dr Jim Hanson has echoed his view at this workshop, stating that NOP standards have created commercialisation forces that favour larger farms. I respectfully disagree. 

As in any solid-liquid reaction, when the solid is sparingly soluble, reaction occurs within the solid by diffusion of the liquid-phase reactant into it across the liquid film surrounding the solid. Thus two diffusion parameters are operative, the solid-liquid mass transfer coefficient sl and the effective diffusivity D. of the reactant in the solid. A reaction in the solid can occur by any of several mechanisms. The simpler and more common of these were briefly explained in Chapter 15. For reactions following the sharp interface model, ultrasound can enhance either or both these constants. Indeed, in a typical solid-liquid reaction such as the synthesis of dibenzyl sulfide from benzyl chloride and sodium sulfide ultrasound enhances SL by a factor of 2 and by a factor of 3.3 (Hagenson and Doraiswamy, 1998). Similar enhancement in was found for a Michael addition reaction (Ratoarinoro et al., 1995) and for another mass transfer-limited reaction (Worsley and Mills, 1996). 

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