Subject allyl monomers

The second intermediate, a 6 -<9-acroyl 6-0-allyl-dialkene was subjected to RCM (with Grubbs II catalyst) and afforded small amounts of the C2-sym-metrical derivative, accompanied by E- and Z-cyclic monomers.316... 

To pursue the idea of specific TCNE-allyl interactions, we suppose in Fig. 19 that each TCNE has a strong contact (J) with one MP and a weaker one (J < J) with the other. This results in a dimerized stack if J and J alternate precisely when the unit cell is doubled and there is no reason for an enlarged thermal ellipsoid. A more promising hypothesis is that J and J do not alternate precisely, so that sometimes two TCNE form strong contacts with the same MgP, to give trimers in Fig. 19. MgP sites with two weak (J ) contacts are monomers. There are equal numbers of J and J, but now the distribution is random, subject to the constraint that no more than two successive J or J can occur. 

Telomerization reactions, the formation of short oligomers from dienes, represent a very efficient organic transformation with an overall atom economy of 100%, and they have been the subject of intensive research in both academic and industrial laboratories. Complexes of palladium are known to catalyze the reaction of dienes with a variety of nucleophiles. Mechanistically, the reactions are thought to proceed by allyl coordination of two butadiene molecules to a palladium(O) center followed by the formation of a C-C bond. The eight-carbon chain is then attacked by a nucleophile at the terminal or at the 3 position. The reaction usnally leads to a mixture of cis/trans isomers and n- and iio-prodncts. When the nncleophile is methanol, l-methoxyocta-2,7-diene 1 (n-product) is generally the major prodnct, which is a nseful precnrsor for plasticizer alcohols (octanols), solvents, corrosion inhibitors, and monomers for polymerization. ... 

Included among the many types of vinyl monomers that have been subjected to photoinitiated cationic polymerization are styrene," substituted styrenes, a-methylstyrenes, N-vinylcarbazole, alkyl vinyl ethers, prop-l-en-l-yl ethers, ketene acetals, and alkoxyallenes. Most useful in the crosslinking photopolymerizations employed for UV curing applications are multifunctional vinyl ethers and multifunctional prop-l-en-l-yl ethers. A number of multifunctional vinyl ether monomers are available from commercial sources, while multifunctional prop-l-en-l-yl ethers can be readily prepared by catalytic isomerization from their corresponding allyl ether precursors. The photoinitiated cationic... 

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