Synthesis and evaluation of an ester-functional alkoxyamine for nitroxide-mediated polymerization

Authors

  • Anna C. Greene,

    1. Department of Chemistry, Dartmouth College, 6128 Burke Laboratory, Hanover, New Hampshire 03755
    Search for more papers by this author
  • Robert B. Grubbs

    Corresponding author
    1. Department of Chemistry, Dartmouth College, 6128 Burke Laboratory, Hanover, New Hampshire 03755
    2. Department of Chemistry, State University of New York, Stony Brook, New York 11794
    • Department of Chemistry, Dartmouth College, 6128 Burke Laboratory, Hanover, New Hampshire 03755
    Search for more papers by this author

Abstract

The ester-functional alkoxyamine 2,2-dimethyl-3-(1-(4-(methoxycarbonyl)phenyl)ethoxy)-4-(4-(methoxycarbonyl)phenyl)-3-azapentane (2) was efficiently synthesized for use as a functional initiator in nitroxide-mediated polymerization. Two equivalents of 1-(4-(methoxycarbonyl)phenyl)ethyl radical were added across the double bond of 2-methyl-2-nitrosopropane to form alkoxyamine 2, which was found to control the polymerization of styrene, isoprene, and n-butyl acrylate. The ester moieties were hydrolyzed for subsequent esterification with 1-pyrenebutanol to form a dipyrene-labeled initiator that was used to probe nitroxide end-group fidelity after styrene polymerization. High retention of nitroxide was confirmed by UV-vis studies over a range of monomer conversions. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6342–6352, 2009

Ancillary