• Bulletin of the Korean Chemical Society
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• v.35 no.9
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• pp.2723-2725
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• 2014

Recently we have reported a novel class of anion receptors which are based on 2n-crown-n topology. Trioxane derivatives are capable of anion sensing through pure aliphatic C-H hydrogen bonding. In this work, we highlight another interesting property, i.e., they can also recognize cations as normal crown ethers (3n-crown-n topology). Since the same functional moiety can recognize anions and cations, these coronands are predicted to be amphi-ionophores. However, we could not detect cations even in the gas phase. Considering trioxane is analogous to [$1_6$]starand, this was rather counter-intuitive. The calculation results show that these coronands can detect alkali metals with very low affinity. The low affinity toward cations should be responsible for this failure of experimental detection. With careful theoretical study, we found that this low affinity toward cations could be explained by the unfavorable charge-dipolar moiety orientations as proposed by Cui et al. As in the case of [$1_6$]starand, this is an example that underscores the importance of charge-dipolar moiety orientation in supramolecular interactions.

• Journal of the Korean Chemical Society
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• v.22 no.6
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• pp.423-430
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• 1978

The initiation mechanism of trioxane polymerization catalyzed by Ti$Cl_4$ in nitrobenzene was investigated. The kinetic studies revealed that the rate of polymerization was drastically decreased by the addition of a minute amount of water or methanol. A third substance as cocatalyst was not required for the polymerization. Measurements of dielectric constants gave no evidence for the zwitterionic mechanism of the polymerization. The electric conductivity measurements of polymerization system and the initiator solution showed that the initiation was started by Ti$Cl_3^+$ cation, formed by a disproportionation of the initiator in nitrobenzene.

• Bulletin of the Korean Chemical Society
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• v.18 no.6
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• pp.644-648
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• 1997

Introduction of an alkyl substituent at the $C_{4\beta}$ position of antimalarial trioxanes has caused them to become more active in their antimalarial activity. We have designed a structurally simple 4β-phenyl substituted trioxane (3) as an active antimalarial since it can form a more stable carbon radical when reacting with ferrous bromide. The trioxane 3 has been prepared along with the corresponding isomer 4 according to the previously reported procedure. The synthesized trioxanes 3 and 4 were finally separated by using HPLC and assigned their stereochemistry by spectroscopy and X-ray crystallography. Their antimalarial activities were surprisingly low. The low activity was then rationalized based on the product distribution of the ferrous ion induced reaction of these trioxanes. These trioxanes with ferrous bromide did not produce any detectable amount of the corresponding $C_4$-hydroxylated product, consistent with the fact that neither $C_{4\beta}$-phenyl substituted nor $C_{4\alpha}$-phenyl substituted trioxane has any antimalarial activity. It implies that a $C_4$ substituent of antimalarial trioxanes has to stabilize an adjacent carbon-centered radical in a specific stability range in order to show a good antimalarial activity. This study, combined with related studies, could help develop more potent antimalarial trioxanes.

• Journal of the Korea Institute of Military Science and Technology
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• v.5 no.4
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• pp.49-56
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• 2002

For the purpose of the increase in the performance and thermal stability of PBX's, the mixed formal consisting of BDNPF, DNPBF and BDNBF were synthesized. In order to find out the optimal condition for the synthesis of energetic plasticizer, BDNPF, DNPBF and BDNBF, the synthetic procedures have been investigated. We synthesized DNP-OH and DNB-OH through oxidative nitration and controlled various composition of mixed formal by $H_{2}SO_{4}$ and s-trioxane to investigate optimal composition, and then characterized its thermo-physical properties.