Browsing by Subject "biphasic"
Now showing 1 - 2 of 2
Results Per Page
Sort Options
Item Phase selectively soluble polymer supports to facilitate homogeneous catalysis(2009-05-15) Ortiz-Acosta, DenisseSoluble polymers that have phase selective solubility are useful in synthesis because they simplify purification and separation. Such selectively soluble polymers simplify catalyst, reagent, and product recovery and enable the use of Green chemistry principles in homogeneous catalysis. However, while homopolymers have been reported that have excellent thermal and phase-dependent solubility, less is known about copolymers. Also, less is known about the phase selective solubility of polar aprotic N,N-dialkyl polyacrylamides. This work describes a library synthesis of dye-labeled poly(N-n-octadecylacrylamide-co-N-n-butylacrylamide) copolymers and study of the effects of polymer composition in phase selective solubility of these copolymers. To study the relative importance of n-octadecyl versus n-butyl groups, copolymers with different ratios of n-octadecylacrylamide and n-butylacrylamide but with similar degrees of polymerization and polydispersity were prepared by a split-pool synthesis using a highly soluble poly(N-acryloxy-2-dodecylsuccinimide) as the precursor. Polymer sequestrants were used to remove excess amines and the byproduct N-hydroxyl-2- dodecylsuccinimide without fractionation of the polyacrylamides. Results demonstrated that poly(N-n-octadecylacrylamide-co-N-n-butylacrylamide) copolymers? phase selective solubility is equally dependant of the polar n-butyl and nonpolar n-octadecyl groups on the copolymers. Dye-labeled poly(N,N-dialkylacrylamide)s prepared by the polymerization of N,N-dialkylacrylamides monomers with methyl, ethyl, propyl, butyl, hexyl, and dodecyl N-alkyl groups in a variety of thermomorphic or latent biphasic polar/nonpolar solvent mixtures were also prepared. Studies showed that poly(N,N-dialkylacrylamide)s have phase selective solubility that is highly dependent of the size of the N-alkyl group. Soluble polymers are known to be useful supports for catalysts. This thesis also describes approaches to immobilization of a variety of catalysts on polyisobutylene (PIB). The most effective of these catalysts were analogs of pyridyl N-oxides that have been used as organocatalysts for the catalytic allylation of a variety of aromatic aldehydes. PIB-supported N-oxide promoted the allylation of aldehydes in up to 99% isolated yield. The products were isolated in the polar phase of a thermomorphic system and the catalyst was recycled through five cycles.Item Syntheses and applications of soluble polyisobutylene (PIB)-supported transition metal catalysts(2009-05-15) Tian, JianhuaSoluble polymer supports facilitate the recovery and recycling of expensive transition metal complexes. Recently, polyisobutylene (PIB) oligomers have been found to be suitable polymer supports for the recovery of a variety of transition metal catalysts using liquid/liquid biphasic separations after a homogeneous reaction. Our work has shown that PIB-supported Ni(II) and Co(II) ?-diketonates prepared from commercially available vinyl terminated PIB oligomers possess catalytic activity like that of their low molecular weight analogs in Mukaiyama epoxidation of olefins. Carboxylic acid terminated PIB derivatives can act as carboxylate ligands for Rh(II) cyclopropanation catalysts. An achiral PIB-supported Rh(II) carboxylate catalyst showed good activity in cyclopropanation of styrene in hydrocarbon solvents, and could be easily recycled nine times by a post reaction extraction. Further application of PIB supports in asymmetric cyclopropanation reactions were investigated using PIBsupported arenesulfonyl Rh(II) prolinates derived from L-proline as examples. The PIBsupported chiral Rh carboxylates demonstrated moderate activity and were recovered and reused for four to five cycles. The prolinate catalyst prepared from PIB-anisole also showed encouraging enantioselectivity and about 8% ee and 13% ee were observed on trans- and cis-cyclopropanation product respectively. Finally, PIB oligomers can be modified in a multi step sequence to prepare PIBsupported chiral bisoxazolines that can in turn be used to prepare active, recyclable PIBsupported Cu(I) bisoxazoline complexes for olefin cyclopropanation. These chiral copper catalysts showed moderate catalytic activity and good stereoselectivity in cyclopropanation of styrene. A chiral ligand prepared from D-phenylglycinol provided the most effective stereo control and gave the trans- and cis-cyclopropanation product in 94% ee and 68% ee respectively. All three PIB-supported chiral bisoxazoline-Cu(I) catalysts could be reused five to six times.