Loading patent…
AssigneeBoard of Regents of the University of Nebraska
InventorReuben D. Rieke
Estimating the term…
Calcium-substituted polymeric reagents are provided. These reagents can be prepared via the oxidative addition of a soluble highly reactive calcium species to organic and inorganic polymers containing alkyl, aryl, or alkylaryl pendent groups substituted with halide atoms, cyanide molecules, 1,3-dienes, or any conjugated polyunsaturated system. Preferably, the polymer is a cross-linked p-bromopolystyrene, p-chloropolystyrene, p-fluoropolystyrene, or chloromethylated polystyrene. Preferably, the soluble highly reactive calcium species is prepared from the reduction of Ca(II) salts with an alkali metal arene, such as lithium biphenylide. These calcium-substituted polymeric reagents react with a variety of electrophiles to yield functionalized polymers. Reaction with Cu(I) salts yields calcium-substituted polymeric cuprate reagents, which can react, for example, with acid chlorides to form ketones, alkyl halides containing functionality, and undergo 1,4-conjugate addition with .alpha.,.beta.-unsaturated ketones, aldehydes, esters, and amides. Bifunctionalization of the polymer can be achieved by the addition of highly reactive calcium to a functionalized polymer containing a halogen. Polymers can be cross-coupled with dyes, UV stabilizers, biologically active substrates, molecules that impart specifically desired characteristics, among other desirable functional groups.
A calcium-substituted polymeric compound comprising a polymer substituted with calcium atoms in a covalent interaction, wherein the calcium atoms are derived from a soluble calcium species comprising formally zerovalent calcium metal atoms and a solubilizing agent in an ethereal, polyethereal, or hydrocarbon solvent.
A calcium-substituted polymeric compound comprising:
A calcium-substituted polymeric cuprate complex comprising a polymer complexed with calcium atoms and copper atoms, wherein the calcium atoms are derived from a soluble calcium species comprising formally zerovalent calcium metal atoms and a solubilizing agent.
A method of forming a calcium-substituted polymeric compound comprising combining a polymer containing reactive halogen, cyanide, 1,3-diene, or conjugated polyunsaturated groups with a soluble calcium species comprising formally zerovalent calcium metal atoms.
A method for preparation of functionalized polymers comprising reacting a calcium-substituted polymeric compound with an organic electrophile to replace the covalently bonded calcium in the calcium-substituted polymeric compound by the organic radical of the electrophile and form the functionalized polymer.
A method for preparation of functionalized polymers comprising:
A calcium-substituted polymer prepared by the reaction of a polymer containing at least one reactive site with a soluble calcium species comprising formally zerovalent calcium metal atoms.
A calcium-substituted polymeric cuprate prepared by the reaction of a calcium-substituted polymer with a soluble copper(I) salt;
Dependencies are inferred from the claim text.