• Bulletin of the Korean Chemical Society
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• v.32 no.12
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• pp.4387-4391
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• 2011

The kinetic studies on the pyridinolysis of diisopropyl thiophosphinic chloride have been carried out in acetonitrile at $55.0^{\circ}C$. The free energy correlations for substituent X variations in the X-pyridines are biphasic concave upwards with a break point at X = 3-Ph. A concerted SN2 mechanism is proposed with a change of the attacking direction of the X-pyridine from a frontside attack for the strongly basic pyridines to a backside attack for the weakly basic pyridines. The factors to determine the rates and thio effects on the rates for the pyridinolyses of thiophophinic chloride, chlorothiophosphate, phosphinic chloride, phosphonochloridothioate, and chlorophosphate systems are briefly reviewed on the basis of the magnitude of the positive charge of the reaction center P atom and steric effects of the two ligands.

• Bulletin of the Korean Chemical Society
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• v.32 no.11
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• pp.3880-3886
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• 2011

The nucleophilic substitution reactions of diisopropyl thiophophinic chloride (3) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $65.0^{\circ}C$. The anilinolysis rate of 3 is rather slow to be rationalized by the conventional stereoelectronic effects. The obtained deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are secondary inverse ($k_H/k_D$ = 0.80-0.96). The anilinolyses of ten P=S systems in MeCN are reviewed on the basis of DKIEs and selectivity parameters to obtain systematic information on the DKIEs and mechanism for thiophosphoryl transfer reactions. The steric effects of the two ligands on reactivity, DKIEs, mechanism, and substituent effects of the nucleophile (X) on the DKIEs are discussed.

• Bulletin of the Korean Chemical Society
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• v.32 no.7
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• pp.2306-2310
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• 2011

The nucleophilic substitution reactions of diethyl thiophosphinic chloride with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at 55.0 $^{\circ}C$. The values of deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) invariably increase from secondary inverse ($k_H/k_D$ < 1) to primary normal (kH/kD > 1) as the nucleophiles change from the strongly basic to weakly basic anilines. The secondary inverse with the strongly basic anilines and primary normal DKIEs with the weakly basic anilines are rationalized by the gradual transition state (TS) variation from a predominant backside attack, via invariably increasing the fraction of a frontside attack, to a predominant frontside attack, in which the reaction mechanism is a concerted $S_N2$ pathway. A frontside attack involving a hydrogen bonded, four-center-type TS is substantiated by the primary normal DKIEs.

• Bulletin of the Korean Chemical Society
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• v.34 no.11
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• pp.3218-3222
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• 2013

The aminolyses, anilinolysis and pyridinolysis, of bis(2-oxo-3-oxazolidinyl) phosphinic chloride (1) have been kinetically investigated in acetonitrile at 55.0 and $35.0^{\circ}C$, respectively. For the reactions of 1 with substituted anilines and deuterated anilines, a concerted SN2 mechanism is proposed based on the selectivity parameters and activation parameters. The deuterium kinetic isotope effects ($k_H/k_D$) invariably increase from secondary inverse to primary normal as the aniline becomes more basic, rationalized by the transition state variation from a backside to a frontside attack. For the pyridinolysis of 1, the authors propose a stepwise mechanism with a rate-limiting step change from bond breaking for more basic pyridines to bond formation for less basic pyridines based on the selectivity parameters and activation parameters. Biphasic concave upward free energy relationship with X is ascribed to a change in the attacking direction of the nucleophile from a frontside attack with more basic pyridines to a backside attack with less basic pyridines.

• Bulletin of the Korean Chemical Society
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• v.23 no.3
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• pp.374-380
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• 2002

Several compounds of 3,9-dialkylxanthines were prepared from 1-methyl-6-chlorouracil via nucleophillic reactions with different aliphatic amines, followed by nitrosation, reduction, formaylation and finally dehydrocyclization. On the other hands, a series of 8-aryl-3,9-dimethylxanthines were synthesized by dehydrocyclization of 5-arylamido-1-methyl-6-methylaminouracils either by fussion or oxidation of 5-arylidine-amino-1-methyl-6-methylaminouracils using sodium periodate. Phosphoryl chloride was found to be uneffective reagent for dehydrocyclization that, gave another products from 1,3-oxazolo[5,4-d] pyrimidines.

• Bulletin of the Korean Chemical Society
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• v.32 no.6
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• pp.1997-2002
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• 2011

The nucleophilic substitution reactions of dicyclohexyl phosphinic chloride [3; $cHex_2$P(=O)Cl] with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at 60.0 $^{\circ}C$. The anilinolysis rate is too slow to be rationalized by the stereoelectronic effects. The rate is contrary to expectations for the electronic influence of the two ligands and exhibits exceptionally great negative deviation from the Taft's eq. The deuterium kinetic isotope effects (DKIEs) involving deuterated anilines invariably change from primary normal ($k_H/k_D$ > 1; max $k_H/k_D$ = 1.10 with X = 4-MeO) with the strongly basic anilines (X = 4-MeO, 4-Me, 3-Me) to secondary inverse ($k_H/k_D$ < 1; min $k_H/k_D$ = 0.673 with X = 3-Cl) with the weakly basic anilines (X = H, 4-F, 4-Cl, 3-Cl). A concerted $S_N2$ mechanism is proposed on the basis of both secondary inverse and primary normal DKIEs. The obtained DKIEs imply that the fraction of a frontside attack increases as the aniline becomes more basic. A hydrogen-bonded, four-center-type transition state is suggested for a frontside attack, while the trigonal bipyramidal pentacoordinate transition state is suggested for a backside attack.

• Carbon letters
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• v.17 no.1
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• pp.45-52
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• 2016

The attachment of 2-aminobenzamide to carboxylated multi-wall carbon nanotubes (MWCNTs)-COOH was achieved through the formation of amide bonds. Then, the functionalized MWCNTs, MWCNT-amide, were treated by phosphoryl chloride to produce MWCNT-quin. The products were characterized by Fourier transform infrared spectroscopy, Raman spectroscopy, scanning electron microscopy, thermogravimetric analysis, derivative thermogravimetric, steady-state fluorescence spectroscopy, and solubility testing. MWCNT-quin showed photo-electronic properties, which is due to the attachment of the 4-hydroxyquinazoline groups to them as proved by steady-state fluorescence spectroscopy. This suggests intramolecular interactions between the tubes and the attached 4-hydroxyquinazoline. The toxicity of the samples was evaluated in human embryonic kidney HEK293 and human breast cancer SKBR3 cell lines, and the viable cell numbers were measured by 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyltetrazolium bromide (MTT) after the cells were cultured for 24 h. Cellular investigations showed that the modified MWCNTs, particularly MWCNT-quin, have considerably significant toxic impact on SKBR3 as compared to HEK293 at the concentration of 5 µg/mL.