A Potential New RAFT–Click Reaction or a Cautionary Note on the Use of Diazomethane to Methylate RAFT‐synthesized Polymers†
Ming Chen A B , Graeme Moad A B and Ezio Rizzardo A
+ Author Affiliations
- Author Affiliations
A CSIRO Materials Science and Engineering, Bag 10, Clayton South, Vic. 3169, Australia.
B Corresponding authors. Email: ming.chen@csiro.au, graeme.moad@csiro.au
Australian Journal of Chemistry 64(4) 433-437 https://doi.org/10.1071/CH10471
Submitted: 21 December 2010 Accepted: 1 February 2011 Published: 18 April 2011
Abstract
It has been found that diazomethane undergoes a facile 1,3‐dipolar cycloaddition with both dithiobenzoate RAFT agents and the dithiobenzoate end‐groups of polymers formed by RAFT polymerization. Thus, 2‐cyanoprop‐2‐yl dithiobenzoate on treatment with diazomethane at room temperature provided a mixture of stereoisomeric 1,3‐dithiolanes in near quantitative (>95%) yield. A low‐molecular‐weight RAFT‐synthesized poly(methyl methacrylate) with dithiobenzoate end‐groups underwent similar reaction as indicated by immediate decolourization and a quantitative doubling of molecular weight. Higher‐molecular‐weight poly(methyl methacrylate)s were also rapidly decolourized by diazomethane and provided a product with a bimodal molecular weight distribution. Under similar conditions, the trithiocarbonate group does not react with diazomethane.
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