Effect of acid structure on deprotection of poly(2-trimethylsilyl-2-propyl methacrylate)

Deprotection of poly(2-trimethylsilyl-2-propyl methacrylate) was studied for various photogenerated acids. Deprotection of 2-trimethylsilyl-2-propyl (TMSP) ester did not occur in a catalytic manner when the photogenerated acid possessing a fluoride ion source such as SbF6- or AsF6- was used. Because the cleaved product, alpha-methyl-alpha-(trimethylsilyl)ethyl cation, undergoes rearrangement through methyl migration from silicon to carbon with nucleophilic attack on the silicon by the fluoride ion, the acid was consumed in the reaction. Fortunately, when the counterion of the acid does not provide a fluoride ion, e.g. sulfonate, the carbonium ion undergoes elimination to produce 2,2,3-trimethyl-2-silabut-3-ene, and regenerates another acid. The thermal stability of TMSP ester was very similar to t-butyl ester, and acid catalyzed cleavage of the TMSP begins at 80 degrees C. (C) 1999 Elsevier Science Ltd. All rights reserved.