CuCl/bipy

The direct synthesis of poly(3-sulfopropyl methacrylate)-fr-PMMA, PSP-MA-fr-PMMA (Scheme 27) without the use of protecting chemistry, by sequential monomer addition and ATRP techniques was achieved [77]. A water/DMF 40/60 mixture was used to ensure the homogeneous polymerization of both monomers. CuCl/bipy was the catalytic system used, leading to quantitative conversion and narrow molecular weight distribution. In another approach the PSPMA macroinitiator was isolated by stopping the polymerization at a conversion of 83%. Then using a 40/60 water/DMF mixture MMA was polymerized to give the desired block copolymer. In this case no residual SPMA monomer was present before the polymerization of MMA. The micellar properties of these amphiphilic copolymers were examined. 

A simple synthesis of 3-substituted and 23-disubstituted 4-chloiofuians was accomplished. It involves a CuCl/bipy-catalyzed regioselective cyclization of l-acetoxy-2.22-trichloroethyl allyl ether followed successively by dechloroacetoxylation with Zn dust and tandem dehydro-halogenation-aromatization with tBuOK/18-crown-6 <99CC2267>. 

HeterocycUzation. Captodative radicals are generated from a-heterosubstituted a-chloroacetic esters by treatment with CuCl bipy. Such a radical can be trapped in-tramolecularly by an alkene (e.g., a 3-butenyl group) attached to the a-heteroatom. Formation of five-membered ring heterocycles is a favorable process. Thus methyl 3-chloromethyltetrahydrofuran-2-carboxylate has been obtained in 75% yield as a mixture of cis and trans isomers (ratio 64 36). The glycine analog gives both pyrrolidine and piperidine derivatives. ... 

CuCl(bipy)2]Cl 2H2O P room g II =2.02 gl=2.19 probably trigonal bipyramidal 66E4... 

Diblock copolymers PEO-fo-PS have been prepared using PEO macroinitiator and ATRP techniques [125]. The macroinitiator was synthesized by the reaction of monohydroxy-functionalized PEO with 2-chloro-2-phenylacetyl-chloride. MALDI-TOF revealed the successful synthesis of the macroinitiators. The ATRP of styrene was conducted in bulk at 130 °C with CuCl as the catalyst and 2,2 bipyridine, bipy, as the ligand. Yields higher than 80% and rather narrow molecular weight distributions (Mw/Mn < 1.3) were obtained. The surface morphology of these samples was investigated by atomic force microscopy, AFM. 

Recently, atom transfer radical emulsion polymerization (ATRP) of styrene using chloro-terminated poly(ethylene glycol) (PEG-Cl) as maaoinitiator under microwave irradiation was successfully conducted and monodispersed nanoparticles were prepared. In the typical procedure used for ATRP in the presence of CuCl and 2,2 -bipyridine (bipy), styrene, PEG-Cl, and Tween-20 (5wt.%) were dispersed in deionized water, and the mixture was polymerized under microwave irradiation at 75 °C, while a stable dispersion was obtained after 1 h. It was found that the diameters of PEG-b-PS nanoparticles prepared under miaowave irradiation were smaller (<50nm) and more monodispersed than those prepared with conventional heating. 

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