• Bulletin of the Korean Chemical Society
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• v.16 no.2
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• pp.153-157
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• 1995

Calix[6]arenes are selectively dialkylated at the lower rim and further functionalized by the aminomethylation and Claisen Rearrangement reactions. Dialkylation was conducted by the reaction of calix[6]arene and alkyl halides such as benzyl bromide, allyl bromide, ethyl bromoacetate, propyl bromide, and methyl iodide under the carefully controlled reaction conditions. Aminomethylation was carried out with the treatment of disubstituted calix[6]arene and secondary amine in the presence of formaldehyde. Claisen rearrangement reaction of the O-diallylcalix[6]arene produced the p-diallylcalix[6]arene.

• Journal of the Korean Chemical Society
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• v.13 no.2
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• pp.109-114
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• 1969

Halogen exchange reactions of benzyl halides have been studied in absolute acetone. Rate constants were calculated using an integrated rate expression derived for the reaction involving ion-pair association. The order of nucleophilicity of halide ions in acetone was found to be a reverse of the order in 90% aqueous enthanol solvent. This was interpreted by means of HSAB principle and solvation of halide ions. Net increase in rate of reaction in acetone compared with the rate in protic solvent resulted from large increase in ${\Delta}S^\neq$ rather than decrease in ${\Delta}H^\neq$. The solvation of the transition state also contribute to the net increase in rate.

• Journal of the Korean Chemical Society
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• v.16 no.5
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• pp.284-289
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• 1972

Rates of the reactions of m-and p-ring-substituted thiobenzamides with benzyl bromide in acetone have been determined by an electric conductivity method. The Hammett rule has been adopted for these reactions. It has been observed that an electron-attracting substituent accelerates the reaction while an electron-donating substituent retards the reaction, and a mechanism which accounts for the observed kinetics has been postulated. The activation energies and entropies of activation for these reactions have also been calculated.

• Bulletin of the Korean Chemical Society
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• v.17 no.4
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• pp.314-321
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• 1996

Isoxazolidine derivatives 7 and 8 were synthesized from N-benzyl-C-(2-benzyloxyethyl)nitrones by 1,3-dipolar cycloaddition with ethyl crotonate. The isoxazolidine derivatives were converted to β-amino acid esters 9a and 9b by reduction with zinc in acetic acid. The β-amino acid esters were reacted with methylmagnesium bromide to give the 2-azetidinones (13a, 13b). The benzyl group of 2-azetidinones were removed by Birch reduction. The products were oxidized with PDC to give 3-[1-(t-butyldimethylsilyloxy)ethyl]-4-carboxymethyl-2-azetidinone derivatives (2a, 2c).

• Bulletin of the Korean Chemical Society
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• v.29 no.7
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• pp.1332-1334
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• 2008

Stable crystalline 1-Benzyl-4-aza-1-azonia-bicyclo[2.2.2]octane tribromide (BABOT), can be readily synthesized from the reaction of the corresponding bromide with $HNO_3$ and aqueous KBr. Selective Oxidation of a variety of dialkyl and alkyl Aryl sulfides to the corresponding sulfoxides in high yield was achieved by this reagent in solution ($CH_3CN/H_2O$) and solvent free conditions. The reaction proceeds under neutral and mild conditions and can be carried out easily at room temperature with regeneration of BABOT. In this method purification of products is straightforward and no over oxidation to sulfone was noted.

• Journal of the Korean Chemical Society
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• v.39 no.8
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• pp.657-665
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• 1995

The oxidation of various benzyl ethers and benzyl alkyl ethers to benzoates has been studied in two-phase system of $CH_3CO_2Et$ and aqueous NaOCl (6.6 mol eq.). The oxidant N-oxo-4-methoxy-2,2,6,6-tetramethylpiperidium bromide (N-oxoammonium salt) was prepared in situ and recycled by addition of 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl (0.03 mol eq., 4-methoxy-TEMPO), co-catalyst KBr (0.03mol eq.) and second oxidant NaOCl. Thus the catalytic amount of 4-methoxy-TEMPO was used. An adjustment of the pH value of below 8.0 was also required for this reaction with 2.5 hr of reaction time at 0∼5$^{\circ}C$. Under these conditions benzyl ethers were oxidized to benzoates. The selectivity of oxidation of benzyl alkyl ethers is dependent on the acidity of hydrogen and steric effect of alkyl group.

• Journal of the Korean Chemical Society
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• v.13 no.2
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• pp.103-108
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• 1969

전보에 이어 90% 에탄올 용액에서의 염화 벤질 및 브롬화 벤질과 요오드화 이온 간의 교환반응을 연구하였다. HSAB이론을 도입하여 할로겐화 이온의 pb혼합 궤도가 서로 겹치는 전이 상태로서 실험 결과를 설명하였다.

• Bulletin of the Korean Chemical Society
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• v.20 no.10
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• pp.1172-1176
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• 1999

Nucleophilic substitution reaction of Y-benzyl bromide with X-pyridines are investigated in DMSO at 45.0℃. Biphasic rate dependence is observed on varying the substituents in the substrate (Y) as well as in the nucleophile (X). The two well-defined straight lines in the Hammett (ρy) and Bronsted ( βx) plots are interpreted to indicate the changes in transition-state structure, a decrease in bond cleavage as the substituent on the substrate is changed from electron-donors ( ρy < 0) to electron-acceptors ( ρy > 0), and an increase in the extent of bond formation with the corresponding changes of the substituent on the pyridine. A Jencks' type analysis of separate polar (ρ) and resonance (ρr) effects can also be accounted for by the change of the transition-state structure, not by the variable combination of polar and resonance effects.

• Bulletin of the Korean Chemical Society
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• v.7 no.4
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• pp.311-314
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• 1986

A series of tetramethyl 1-substituted benzyl-3a,7a-dihydro-1H-indole-2,3,3a,4-tetracarboxylates were prepared and their reactions with bromine were examined. The initial reaction seemed to be the formation of the intermediate N-bromo quaternary ammonium bromide. This intermediate underwent aromatization with loss of the 3a-methoxycarbonyl group. Bromine replaced the N-substituent of the p-methoxybenzyl compound and addition of bromine occurred across the $C_6-C_7$ double bond of the indole ring. Bromination of the benzyl ring and aromatization occurred for the m-methoxybenzyl compound.

• Journal of the Korean Chemical Society
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• v.23 no.6
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• pp.392-395
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• 1979

Some alkyl or aryl halides, such as ethyl bromide, butyl chloride, phenyl bromide and benzyl chloride, were reacted by Grignard's method with anhydrous tin tetrachloride in hydrocarbon media. When small amounts of ether were added into the Grignard reaction step, the reaction proceeded rather smoothly and gave good yields of corresponding organotin compounds.