Reaction of polystyryllithium and 2-polystyryl-1,1-diphenyl-ethyllithium with methyl acetate, methyl benzoate and the corresponding acyl chlorides

In the course of the reaction of polystyryllithium (PSL) and 2‐polystyryl‐1,1‐diphenylethyl‐lithium (PSDPEL) with methyl acetate (MA), methyl benzoate (MB) and acetyl (ACI) and benzoyl (BCI) chlorides as coupling agents (CA), the quantity of the product of combination P2Y, where P2 corresponds to do...

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Published in:Macromolecular chemistry and physics 1995-01, Vol.196 (1), p.85-98
Main Authors: Zgonnik, Vladimir, Melenevskaya, Elena, Kever, Jenö, Litvinova, Larisa, Khachaturov, Alexander, Terentieva, Irina
Format: Article
Language:eng ; rus
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Summary:In the course of the reaction of polystyryllithium (PSL) and 2‐polystyryl‐1,1‐diphenylethyl‐lithium (PSDPEL) with methyl acetate (MA), methyl benzoate (MB) and acetyl (ACI) and benzoyl (BCI) chlorides as coupling agents (CA), the quantity of the product of combination P2Y, where P2 corresponds to double molecular weight (MW) of the initial PS or PSDPE and the CA residue is referred to as Y, strongly depends on the nature of CA, and to a lower degree on the CA/PSL (PSDPEL) ratio and the nature of the solvent (benzene or THF). The maximum yield of P2Y from the reaction of MA and PSL did not exceed 80%, and 12% for MA and PSDPEL. It was shown using CD3COOCH3 and 500 MHz NMR that this incomplete conversion is due to a side reaction of PSL or PSDPEL with the D(H) atoms of the methyl group of MA, proceeding simultaneously with the main reaction and yielding PSD(H) or PSDPED(H). Using a special approach, the polymeric ketone corresponding to the first stage of this reaction can be obtained; its yield was in the case of PSL and MA higher than 50%. For the PSDPEL‐MA system, the product of the reaction, based on NMR data, consists of approximately equal portions of the polymeric ketone and the product resulting from the side reaction, i.e., PSDPE‐H. In the latter case the sterically hindered polymeric ketone did not react with excess PSL or PSDPEL. Products of the reaction of PSL or PSDPEL with MB dit not contain PSH or PSDPEH, respectively.
ISSN:1022-1352
1521-3935
DOI:10.1002/macp.1995.021960105