• Rapid Communication in Photoscience
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• v.3 no.4
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• pp.64-66
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• 2014

Synthesis of a deuterium-labeled derivative of nitrospirobenzopyran (NSP), one of representative photochromic compounds, has been described. Four deuteriums were successfully introduced on 1-methyl and ${\alpha}$-methyne relative to spiro-carbon in the title compound with more than 95atom%D purity. Main photodegraded products of NSP were two oxindoles in acetonitrile, and additional products were formed in poly(isobutyl-methacrylate) films possibly due to restricted molecular motion in polymer matrix. Quantitative HPLC analysis revealed that partial introduction of deuterium to NSP brought a noticeable isotope effect, recognizable enhancement in photo-resistivity of NSP, i.e.,8.3% in solutions and 29% in polymeric films.

• Bulletin of the Korean Chemical Society
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• v.13 no.1
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• pp.59-64
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• 1992

The contrasting behaviour of meso-and d,l-$D_3$-trishomocubylidene-$D_3$-trishomocubane (1 and 2) in the electrophilic addition reaction, the former giving rearranged spiro compound (1a and 1b) and the latter giving 1,2-adduct (2a and 2b), has been explained as arising from the secondary steric effects based on computational evidence. As the degree of out-of-plane deformation of the olefinic carbon atoms increases with reaction progress, the resulting internal congestion in the region behind the double bond becomes unbearably large in meso-1. The absence of symmetry plane across the double bond of d,l-2 helps for the closing fragments to adjust themselves.

• Bulletin of the Korean Chemical Society
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• v.35 no.9
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• pp.2717-2722
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• 2014

The reaction mechanism between azacyclopropenylidene and epoxypropane has been systematically investigated employing the second-order M${\o}$ller-Plesset perturbation theory (MP2) method to better understand the reactivity of azacyclopropenylidene with four-membered ring compound epoxypropane. Geometry optimization, vibrational analysis, and energy property for the involved stationary points on the potential energy surface have been calculated. It was found that for the first step of this reaction, azacyclopropenylidene can insert into epoxypropane at its C-O or C-C bond to form spiro intermediate IM. It is easier for the azacyclopropenylidene to insert into the C-O bond than the C-C bond. Through the ring-opened step at the C-C bond of azacyclopropenylidene fragment, IM can transfer to product P1, which is named as pathway (1). On the other hand, through the H-transferred step and subsequent ring-opened step at the C-N bond of azacyclopropenylidene fragment, IM can convert to product P2, which is named as pathway (2). From the thermodynamics viewpoint, the P2 characterized by an allene is the dominating product. From the kinetic viewpoint, the pathway (1) of formation to P1 is primary.