• Bulletin of the Korean Chemical Society
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• v.33 no.6
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• pp.1939-1944
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• 2012

Benzoyloxy benzophenone derivatives were prepared in 3 steps including DCC coupling, Fries rearrangement and esterification from benzoic acids in 24-89% total yields. Among the prepared 12 benzophenone analogues 1a-1l, the compound 1b having three chloro groups at the para position showed maximum inhibitory effects of ICAM-1 expression but, 1a which have no substituents at all showed no inhibitory activity. This study provides the evidences that benzoyloxy benzophenone derivative, 1b may exert its anti-inflammatory activity by suppressing IFN-${\gamma}$-induced ICAM-1 expression.

• Bulletin of the Korean Chemical Society
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• v.26 no.10
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• pp.1520-1524
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• 2005

This paper describes the racemic and stereoselective synthetic route for a novel 4'$\alpha$-phenyl and 6'$\alpha$-methyl doubly branched carbocyclic nucleosides from an acyclic 2-hydroxy acetophenone. The installation of phenyl group at the 4'-position of carbocyclic nucleoside was successfully accomplished via a sequential [3,3]-sigmatropic rearrangement. The stereoselective introduction of a methyl group in the 6'$\alpha$-position was accomplished by Felkin-Anh controlled alkylation. Bis-vinyl 11 compound was successfully cyclized using a Grubbs’ catalyst II to desired carbocycles. The natural bases (adenine and cytosine) were efficiently coupled using a Pd(0) catalyst. Although all the synthesized compounds were examined for their activity against several viruses such as HIV-1, HSV-1, HSV-2 and HCMV, only cytosine analogues 17 exhibited weak antiviral activity against HCMV.

• Archives of Pharmacal Research
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• v.14 no.4
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• pp.319-324
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• 1991

2,6-Dimethyl-4-(3'-nitrophenyl)-3-methoxylaminocarbonyl-1,4-dihydropyridine-5-carboxylic acid methylester, 3b reacted with 2-cyanoethanol or benzylalcohol to give the corresponding cyanoethylurethane compound 6c in 40.6% yield and benzylurethane compound 6d in 32% yield. The cyanoethylurethane 6c was hydrolized in ethanolic NaOH to give 2,6-dimethyl-4-(3'-nitrophenyl)-1,4-dihydropyridine-3-amino-5-carboxylic acid 5-methyl ester. HCl 8 in 64.8% yield. Another acid hydrolysis of benzylurethane 6d gave 2,6-dimethyl-4-(3'-nitrophenyl)-1,4-dihydropyridine-3-amino-5-carboxylic acid 5-methylester. HBr 11 in 54.7% yield.

• Journal of the Korean Ceramic Society
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• v.32 no.5
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• pp.527-534
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• 1995

In this research, the emphasis was focused on the rearrangement and densification behavior of CaO particles when the aluminum was added to improve the hydration resistance. For the case of 0.5vol% Al added specimen, the rearrangement of CaO particles due to liquid aluminum was terminated near 140$0^{\circ}C$ where the theoretically calculated fractional volume of solid reached 0.74 under Ar atmosphere. The density of the specimen sintered at 155$0^{\circ}C$ for 5hrs reached 96% of relative theoretical density when the ambient was switched to O2 at intermediate and final stages of the sintering. The weight gain due to the hydration after 60 days under 72% of relative humidity at 26$^{\circ}C$ was less than 1%.

• Proceedings of the Korean Powder Metallurgy Institute Conference
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• 2006.09a
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• pp.68-69
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• 2006

When an alloy such as Ni-W is liquid phase sintered, heavy solid W particles sedimentate to the bottom of the container, provided that their volume fraction is less than a critical value. The sintering process evolves typically in two stages, diffusiondriven macrosegregation sedimentation followed by true sedimentation. During macrosegregation sedimentation, the overall solid volume fraction decreases concurrently with elimination of liquid concentration gradient. However, in the second stage of true sedimentation, the average solid volume fraction in the mushy zone increases with time. It is proposed that the true sedimentation results from particle rearrangement for higher packing efficiency.

• Mass Spectrometry Letters
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• v.9 no.1
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• pp.37-40
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• 2018

Farinomalein is a maleimide-bearing compound well known for its anti-fungal activity. In the present study, synthesis of farinomalein is achieved via Stobbe condensation followed by Haval-Argade contrathermodynamic rearrangement. Kinetically driven Stobbe condensation followed by condensation with beta-alanine reveals formation of two isomers of farinomalein. This article describes application of LC-MS/MS in structure elucidation of farinomalein 1 and its isomers 2 and 3 encountered in its synthesis. The proposed distinct fragmentation pathway is supported by rational organic reaction mechanism. These fragmentation pathways are significant for analytical method development of farinomalein in near future. The structures of farinomalein 1 and its isomers 2 and 3 have been assigned undisputedly.

• Bulletin of the Korean Chemical Society
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• v.13 no.6
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• pp.689-695
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• 1992

Methods for the selective functionalization of calix[4]arene at the upper rim are described. The diametrically substituted calix[4]arene dimethyl ether 2, obtained from the treatment of calix[4]arene 1 with methyl iodide in the presence of $K_2CO_3$, is converted to the two isomeric p-diacetylcalix[4]arene dimethyl ether 3 and 6 by direct substitution and by Fries rearrangement of corresponding diacetyloxycalix[4]arene dimethyl ether 5 respectively. Diametrically substituted p-diacetylcalix[4]arene 8 was also prepared by Fries rearrangement of calix[4]arene tetraacetate 7 using a limited amount of $AlCl_3$.

• Bulletin of the Korean Chemical Society
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• v.21 no.9
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• pp.860-866
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• 2000

Hydrocarbostyril, which is a key intermediate in our new synthetic route to 6-nitroquipazine, can be prepared from 1-indanone oxime by Beckmann rearrangement. We have optimized the reaction by using a Lewis acid, aluminum chloride,in the yield of 91% instead of common acids such as polyphosphoric acid,and sulfuric acid used in conventional Beckmann rearrangement (20% in the literature, 10% in our experiment).The optimized condition is established by usingthree equivalents of aluminum chloride in CH2Cl2 at -40 $^{\circ}C$ - room tempera-turefor 40 min. We have applied this condition to other 1-indanone derivatives, such as 4-methyl-, 4-methoxy-, 4-nitro and 6-nitro-1-indanones. The mechanism ofthis BR has been proposed on the basis of the effect of tem-perature and substituenton product ratio, with the aid of PM3 calculation for a model system.

• Bulletin of the Korean Chemical Society
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• v.18 no.4
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• pp.395-401
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• 1997

The substituent effects in the gas-phase rearrangement of carbenes to ketenes involved in the Wolff reaction have been investigated theoretically using the AM1 method. In the initial state, carbene, there is a relatively strong vicinal n-σ* interaction between the lone pair (n) and carbonyl group (σ*). In the bridged transition state (TS), electronic charge is transferred from the migrating ring (Z-ring) toward the nonmigrating ring (Y-ring). The carbenes are stabilized by an electron donor Y (δσY < 0) whereas the TS is stabilized by an electron acceptor Y (δσY > 0). Multiple regression analysis of log (kYZ/kHH)(=-δΔG≠/2.3RT) leads to a relatively large negative cross-interaction constant, ρYZ=-0.53, log (kYZ/kHH)=2.96 σY--1.40 σZ-0.53 σY-σZ reflecting an extensive structural change in the transition state due to the stabilization of the initial state by the vicinal n-σ* overlap. When the solvent (water) effects are accounted for by the SM2.1 model of the Cramer and Truhlar method, the magnitude of all the selectivity parameters, ρY-, ρZ and ρYZ (=-0.66) are increased.

• Bulletin of the Korean Chemical Society
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• v.18 no.6
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• pp.657-662
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• 1997

Gas-phase phenyl group migration within the protonated ketones has been studied MO theoretically using the AM1 method. The initial state structure shows relatively strong resonance delocalization of positive charge into the nonmigrating (Y) ring, while the ring migration (Z-ring) is nearly complete in the transition state. These results are reflected in the large $p^+_Z$ (<0) and $p^+_$Y (>0) values and in the predominant contribution of resonance (r) over inductive (field, f) effect, r/f ranging from 1.3 ($p^+_r$) to 1.5 ($p^+_z$). The cross-interaction constant $p_{YZ}$ is vanishingly small ($p_{YZ}$=0.03) which is in contrast to the larger magnitudes for benzilic ($p_{YZ}$=-0.48) and azibenzil ($p_{YZ}$=-0.53) rearrangement processes. The relationship found between the extent of resonance contribution in the initial state and the magnitude of $p_{YZ}$ provides strong support for the proportionality between the magnitude of $p_{YZ}$ and the change in the intensity of interaction, ${\Delta}I^{\cdot}_{YZ}$, in the activation process.