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Chemical modification of halogenated polystyrene resins utilizing highly reactive copper and calcium and the chemistry of highly reactive copper contained in a polymer
Abstract
Highly reactive calcium was prepared by the lithium biphenylide reduction of calcium(II) halides, especially calcium(II) iodide in tetrahydrofuran at room temperature. This highly reactive calcium oxidatively adds to a variety of halogen-containing cross-linked polystyrene resins such as p-bromopolystyrene, p-chloropolystyrene, p-fluoropolystyrene, and chloromethylated polystyrene to prepare the corresponding polymeric organocalcium reagents. These organocalcium reagents react with a variety of electrophiles to yield functionalized polystyrene resins. Transmetallation with CuCN$\cdot$2LiBr yields calcium cuprate reagents which react with acid chlorides to form ketones, undergo cross-coupling reactions with halides containing functionality, and add via 1,4-conjugate addition to 2-cyclohexen-1-one. Bifunctionalization of the polymer can be achieved by the addition of highly reactive calcium to a functionalized polymer containing a halogen. Highly reactive copper was prepared by the lithium naphthalenide reductions of various copper(I) salt/ligand complexes in tetrahydrofuran. A majority of the research involved the reduction of a CuI$\cdot$PBu$\sb3$ complex to prepare the highly reactive copper and its subsequent addition to cross-linked p-bromopolystyrene of varying degrees of functionalization (DF = 0.31 and DF = 0.98). These insoluble, polymeric oragnocopper reagents reacted with a variety of electrophiles including substituted benzyl chlorides to prepare functionalized polymers. Bifunctionalization of the polymer can be achieved by the addition of highly reactive copper to a functionalized polymer containing a halogen. Other forms of highly reactive copper were reacted with p-bromopolystyrene as well as other halogenated polystyrene resins in an attempt to functionalize polystyrene resins. A polymer-supported triphenylphosphine copper(I) iodide complex was prepared and reduced with lithium naphthalenide in tetrahydrofuran to produce highly reactive copper contained in a polymer. This highly reactive copper contained in a polymer oxidatively adds to a variety of organic halides containing functionality to prepare polymer-supported organocopper reagents. These functionalized organocopper reagents can undergo cross-coupling reactions with acid chlorides to form ketones, react with other organic substrates, and intramolecularly open epoxides. In addition, the reaction pathway can be followed by solid-state $\sp{31}$P NMR of the phosphorus-containing polymers.
Subject Area
Polymers|Organic chemistry
Recommended Citation
O'Brien, Richard Alan, "Chemical modification of halogenated polystyrene resins utilizing highly reactive copper and calcium and the chemistry of highly reactive copper contained in a polymer" (1992). ETD collection for University of Nebraska-Lincoln. AAI9225489.
https://digitalcommons.unl.edu/dissertations/AAI9225489