ABSTRACT:The chronology of 2-alkenyl azlactone research at 3M is discussed in terms of its origination; consideration of economics, overall safety, and opportunities for patent protection; elaboration of the chemistry; and, finally, applying lessons learned toward the development of commercial technologies. The chemistry is dominated by the presence of three electrophilic reaction centers and a readily polymerizable 2-alkenyl group.

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Active titanium metal, produced in a finely divided form by Feduction of Tic13 with either potassium or lithium, will reductively couple ketones and aldehydes to olefins. Although the intermolecular coupling works best when two identical carbonyls are coupled to a symmetrical product, unsymmetrical couplings can also be carried out in certain cases. The unsymmetrical coupling of a diaryl ketone with another partner is particularly efficient, and a mechanism to account for this is proposed. Intramolecular dicarbonyl coupling to form rings is also possible, and the combinaiion TiCls/Zn-Cu works best. Rings of size 4-16 and 22 are prepared in high yield. The nature of the active titanium metal is studied by scanning electron microscopy, and a mechanistic proposal accounting for all observed resulb is presented. It is believed that the coupling reaction occurs on the surface of the active titanium particle.

spectrum (70 eV) m/e (rei intensity) 260 (0.85), 214 (48), 213 (79), 182 (10), 118 (11), 117 (14), 110 (9), 109 (100), 105 (44), 104 (39), 103 (115), 93 (10), 91 (7), 77 (10).The residue after filtration was stripped of solvent and distilled to give a 3.48-g (16%) sample which was redistilled and a fraction of 1.27 g, bp 103-107 °C (0.07 mm), was taken: NMR (CDCf;) 5 3.66 (doublet, 6, POCH3), 5.75 and 6.26 (pair of doublets, 1.05, PC=CH2), 7.30 (m, 5, CgHg); mass spectrum (70 eV) m/e (rel intensity) 214 (5), 213 (53),