Radical cyclopolymerization of allyl methacrylate (AMA) was investigated in detail, especially under the specified conditions; that is, above the ceiling temperature for a head‐to‐tail propagation (ΔGht ≥ 0) in the polymerization of methacrylate. Thus the structure of the polymer obtained was examined by 1H‐ and 13C‐NMR and infrared (IR) spectroscopy; no existence of unreacted pendant methacrylyl groups was observed, which suggests that, as a cyclopolymerization mechanism of AMA, intermolecular propagation of growing radicals, followed by intramolecular cyclization or intermolecular propagation of the resulting uncyclized methacrylyl radical, occurs exclusively with methacrylyl group. Temperature dependency of cyclization constant Kc was unusual; Kc increased rapidly at elevated temperatures and no linear relationship of ln Kc vs. 1/T was observed. Five‐membered ring formation was favored at an elevated temperature and diluted monomer concentration. These results are discussed thermodynamically in terms of controlled ring closure in cyclopolymerization.

α,β-Unsaturated esters bearing a chiral oxazolidine or perhydropyrrolo[1,2-c]imidazole auxiliary at the β-position have been prepared and applied to the cycloadditions with N-metalated azomethine ylides derived from α-(benzylideneamino) esters. These reactions are found to proceed with an exclusively high diastereofacial selectivity to give 2,4-pyrrolidinedicarboxylates with four consecutive chiral centers after the removal of chiral auxiliary. Detailed stereochemistry in the transition state is discussed.

Metal-4,4',4",4"'-tetracarboxyphthalocyanine [Metal = Fe(III), Co(II), Mt-taPc] were synthesized by the hydrolysis of metal-4,4 ',4 ",4 "'-tetracarboxamidephthalocyanine (Mt-tamPc). These metal-taPc are soluble in water and in aprotic polar solvents such as N.N '-dimethylformamide. Poly(styrene) bonded Mt-taPc was synthesized by Friedel-Crafts reaction of poly(styrene) with Mt-taPc tetraacid chloride. The polymers contain about 4 mole-% Mt-Pc rings which are covalently bonded to poly(styrene). The decomposition reaction of hydrogen peroxide by catalysis with polystyrene containing Mt-Pc rings was carried out in heterogeneous aqueous media at pH 7,O. The polymer catalysts show a catalase-like activity. The activation energies with the polymer bonded Mt-Pc were found to be about half of those with Mt-taPc.From continuous flow experiments in a column, the polymer attached catalyst was found to be very stable, compared with free Mt-taPc.

SynopsisRadical polymerization of diallyl maleate is kinetically discussed in terms of cyclopolymerization using 2,2'-azobisisobutyronitrile as an initiator and benzene as a solvent a t 60°C. Thus, the kinetic equations involving bicyclo-intramolecular cyclization are derived by assuming steady-state conditions for the different types of radicals, and various parameters involved in the equations are then estimated approximately from an extension of the corresponding model experimental results. The validity of these treatments is confirmed from the comparison with the experimental data including the relationships between the contents of the unreacted allylic and maleic double bonds and the monomer concentrations. In addition, the sequence distribution of the structural units of the polymer produced is discussed; for example, the content of the bicyclic structural units is estimated to be 47.2% a t a 10% dilution of the pure monomer. EXPERIMENTALDAM, a commercially available reagent, was distilled in vacuo under nitrogen. 2,2'-Azobisisobutyronitrile (AIBN) as an initiator and benzene as a solvent were purified by conventional methods. Polymerization procedure and analyses of polymers obtained were similar to the methods described in a previous article.'

The decomposition reaction of hydrogen peroxide was carried out by using Fe(II1)-3,4,3 ',4',3 ",4'~,3"',4"'-octacarboxyphthalocyanine (Fe(II1)-oaPc) as a catalyst, which has previously been reported by Boston et al. Fe(II1)-oaPc is a remarkably effective catalyst for the reaction, compared with hemin, other metal-phthalocyanine compounds, or other iron complexes such as [Fe(III)-(bipy),]X,. The kinetics of this reaction was also investigated in the pH range 5 3 -10,5 by measuring the initial velocity, V,, of the increasing concentration of 0, using a Warburg respirometer. The reaction proceeds according the catalase-like mechanism. On the basis of the results of Sigel et al., the reaction mechanism is discussed.