• Applied Chemistry for Engineering
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• v.21 no.3
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• pp.278-283
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• 2010

The cationic polymerization of oxolane high explosives which have pendant explosive groups such as azido, nitrato and hydrazino is investigated theoretically using the semiempirical MINDO/3, MNDO and AM1 methods. The nucleophilicity and basicity of oxolane high explosives can be explained by the negative charge on oxygen atom of oxolane. The reactivity of propagation in the polymerization of oxolane can be represented by the positive charge on carbon atom and the low LUMO energy of active species of oxolane. The reaction of the oxolane high explosives in oxonium ion form to the open chain carbenium ion form is expected by computational stability energy (17.950~30.197 kcal/mol) of the oxonium ion and carbenium ion favoring the carbenium ion. The relative equilibrium concentration of cyclic oxonium ion and carbenium ion is found to be a major determinant of mechanism, owing to the rapid equilibrium of these catoinic forms. Based on calculation, in the prepolymer propagation step, $S_N1$ mechanism will be at least as fast as that for $S_N2$ mechanism.

• Bulletin of the Korean Chemical Society
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• v.20 no.10
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• pp.1195-1199
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• 1999

2-(2,4,5-Trimethoxyphenyl)-4-methylene-1,3-dioxolane (1b), 2-(2,4,6-trimethoxyphenyl)-4-methylene-1,3-di-oxolane (2b), and 2-(3,4,5-trimethoxyphenyl)-4-methylene-1,3-dioxolane (3b) were prepared and polymerized with boron trifluoride. Boron trifluoride catalyzed reaction proceeded via mainly ring-opening polymerization and cyclization reaction to yield poly(keto ether) and 3(2H)-dihydrofuranone. The yields of polymer and cyclized product exhibited a dependency on the position of the methoxy substituents in the benzene ring of 2-phenyl-4-methylene-1,3-dioxolane derivatives. Electrophilic attack of methylene or oxygen atom on 4-meth-ylene-1,3-dioxolane ring were suggested for the polymerization and cyclization.

• Korean Journal of Crystallography
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• v.11 no.1
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• pp.22-27
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• 2000

The structure of cis-(malonato)[(4R,5R)-4,5-bis(aminomethyl)-2-isopropyl-1,3-dioxolane]platinum(II) with a potent anticancer activity has been determined by the X-ray crystallographic method. Crystal data are as follows: Pt(C/sub 11/H/sub 20/N₂O/sub 6/), M/sub 4/=471.38, monoclinic, P2₁, a=7.112(1), b=33.615(3), c=7.135(1)Å, β=116.80(1)°, V=1522.6(3)Å, and Z=4. The two independent molecules with very similar structures are approximately related by pseudo two-fold screw axis symmetry, which makes the monolinic cell look like the orthorhombic cell with one molecule in the asymmetric unit and space group C222₁. The crystal packing mode is similar to that of the analogue with the dimethyl substituents instead of the isopropyl group. The Pt atom is coordinate to two O and two N atoms in a square planar structure. The six-membered chelate ring in the leaving ligand assumes a conformation intermediate between the half chair and the boat forms. The seven-membered ring in the carrier ligand assumes a twist-chair conformation and the oxolane ring assumes an envelope conformation. Crystal packing consists of the extensive hydrogen-bonding network in the two-dimensional molecular layers and weak van der Waals interactions between these layers.