Alkoxides, Amides, and Other Bases

Franta, P. Lutz, and G. Beinert, Makromol. Chem., 1978, 179, 551. 

Beinert, E. Franta, J. Smid, and P. Rempp, Abstracts, 1st European Discussion Meeting on Polymer Science, Strasbourg, 1978, p. 140. 

The addition of ethereal solvents confers homogeneity on the system, although initiation is still rather slow. These donor molecules appear to function much as they do with Bu Li and break down the aggregated amide. 

More stable amides have been examined by Boileau and his collaborators. Generally, sodamide can generate carboanions only by abstraction of acidic hydrogen atoms however, when complexed with sodium alkoxide it is possible to generate strongly basic carboanions. Lithium and potassium amides suitably complexed are also effective, styrene being 

Boileau, P. Hemery, B. Kaempf, F. Schue, and M. Viguer, J. Polymer ScL, Part B, Polymer Letters, 1974, 12, 217. 

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Alkoxides, Amides, and other Bases. The use of alkoxides as initiators has recently received some attention because of their ease of handling relative to metal alkyls. In principle such species might be expected to be active only with monomers capable of yielding a more stable anion. Potassium methoxide in dimethylsulphoxide/methanol solution will oligomerize 4-vinylpyridine and here initiation seems to proceed via an acid/base equilibrium rather than by addition to the vinyl double bond (Scheme 15). With methyl methacrylate lithium t-butoxide is an initiator although an inefficient one. Furthermore, unused... 

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