• Korean Journal of Food Science and Technology
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• v.20 no.2
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• pp.176-187
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• 1988

Volatile flavor components in the Chinese quince fruits were trapped by simultaneous steam distillation-extraction method, and these were fractionated into the neutral, the basic, the phenolic and the acidic fraction. In the identification of carboxylic acids, the acidic fraction was methylated with diazomethane. Volatile flavor components in these fractions were analyzed by the high-resolution GC and GC-MS equipped with a fused silica capillary column. The total of one hundred and forty-five compounds from the steam volatile concentrate of the Chinese quince fruits were identified: they were 3 aliphatic hydrocarbons, 1 cyclic hydrocarbon, 4 aromatic hydrocarbons, 9 terpene hydrocarbons, 17 alcohols, 3 terpene alcohols, 6 phenols, 21 aldehydes, 7 ketones, 28 esters, 27 acids, 3 furans, 2 thiazoles, 2 acetals, 3 lactones and 9 miscellaneous ones. The greater part of the components except for carboxylic acids were identified from the neutral fraction. The neutral fraction gave a much higher yield than others and was assumed to be indispensable for the reproduction of the aroma of the Chinese quince fruits in a sensory evaluation. According to the results of the GC-sniff evaluation, 1-hexanal, cis-3-hexenal, trans-2-hexenal, 2-methyl-2-hepten-6-one, 1-hexanol, cis-3-hexenol, trans, trans-2, 4-hexadienal and trans-2-hexenol were considered to be the key compounds of grassy odor. On the other hand, esters seemed to be the main constituents of a fruity aroma in the Chinese quince fruits.

• Journal of the Korean Chemical Society
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• v.7 no.3
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• pp.189-196
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• 1963

Reactions between potassium fluoride with organic halogen-containing carboxylic acids in dimethyl formamide solvent gave a decarboxylation reaction for the case of fluoro carboxylic acids of the type of $CF_3\;COOH,\;C_3F_7COOH,\;and\;C_2F_5COOH,$ whereas an additional partial fluorination together with dimerization reaction occurred for the chlorine containing acids of the type of $CH_2ClCOOH,\;CH_3CHClCOOH, \;CHCl_2COOH\;and\;o-Cl-C_6H_4-COOH.$ The phenyl halides showed no reactivity, but the halides with two electron attracting substituents on the benzene ring gave mainly dimerization reaction. The esters and alcohols gave an usual fluorination reaction. The same reactions in absence of the solvent at the elevated temperature increase the yield of the dimerized product and gave the cyclized product, fluorenone, in case of ο-chlorobenzoic acid. It was found that the fluorination usually precede the decarboxylation reaction by checking the stiochemical sequence of reaction. Catalytic influence of potassium fluoride were discussed and the mechanism of the reaction was considered.

• Bulletin of the Korean Chemical Society
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• v.14 no.4
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• pp.469-475
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• 1993

The approximate rates and stoichiometry of the reaction of excess lithium tris(diethylamino)aluminum hydride (LTDEA) with selected organic compounds containing representative functional groups under standardized condition (tetrahydrofuran, 0$^{\circ}C$) were examined in order to define the characteristics of the reagent for selective reductions. The reducing ability of LTDEA was also compared with those of the parent lithium aluminum hydride (LAH) and lithium tris(dibutylamino)aluminum hydride (LTDBA). In general, the reactivity toward organic functionalities is in order of LAH${\gg}$LTDEA${\geq}$LTDBA. LTDEA shows a unique reducing characteristics. Thus, benzyl alcohol and phenol evolve hydrogen slowly. The rate of hydrogen evolution of primary, secondary, and tertiary alcohols is distinctive: 1-hexanol evolves hydrogen completely in 6 h, whereas 3-hexanol evolves hydrogen very slowly. However, 3-ethyl-3-pentanol does not evolve any hydrogen under these reaction conditions. Primary amine, such as n-hexylamine, evolves only 1 equivalent of hydrogen. On the other hand, thiols examined are absolutely inert to this reagent. LTDEA reduces aldehydes, ketones, esters, acid chlorides, and epoxides readily to the corresponding alcohols. Quinones, such as p-benzoquinone and anthraquinone, are reduced to the corresponding diols without hydrogen evolution. However, carboxylic acids, anhydrides, nitriles, and primary amides are reduced slowly, where as tertiary amides are readily reduced. Finally, sulfides and sulfoxides are reduced to thiols and sulfides, respectively, without evolution of hydrogen. In addition to that, the reagent appears to be an excellent partial reducing agent to convert esters, primary carboxamides, and aromatic nitriles into the corresponding aldehydes. Free carboxylic acids are also converted into aldehydes through treatment of acyloxy-9-BBN with this reagent in excellent yields.

• Journal of the Korean Chemical Society
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• v.33 no.1
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• pp.97-105
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• 1989

This study deals with micellar effects on hydrolyses of p-nitrophenyl carboxylic esters(p-NPCE) mediated by 2-alkylbenzimidazole(R-BI) and sodium 2-alkylbenzimidazole-5-sulfonate(R-BISO$_3$Na) in aqueous and CTABr solutions. The reactions mediated by R-BI and R-BISO$_3$Na in micellar solutions are obviously slower than those by benzimidazole(BI) and sodium benzimidazole-5-sulfonate(BISO$_3$Na) respectively, and the reaction rates were decreased with increase of lengths of alkyl groups. This prestents a striking contrast to the reactions in aqueous solutions without added CTABr, of which the reaction rates are on approximately same levels. It seems due to steric effect of alkyl groups for R-BI and R-BISO$_3$Na in the Stern layer of micelle, and it is supported by measured activation parameters(${\Delta}H^{\neq},\;{\Delta}G^{\neq}\;and\;{\Delta}S^{\neq}$) of the reactions in aqueous and micellar solutions. In addition to nucleophilic ability of benzimidazole(BI) moiety of R-BISO$_3$Na on the reactions, these compounds with long alkyl groups(nonyl to pentadecyl) which form a micelle of themselves increase the reaction rates due to their micellar catalyses in aqueous solutions, not including CTABr. We measured the isotope effects to elucidate the mechanism of hydrolyses of p-nitrophenyl carboxylic esters, and the relative first order rate constant($k'_{H_2O}/k'_{D_2O}$) are on range of 2.5∼3.2. This range is too high to conclude that the hydrolyses of p-NPA mediated by various R-BISO$_3$Na proceed by nucleophilic mechanism. In other words, the reactions are assumed to proceed in part by general basic one, as compared with the reaction catalyzed by imidazole(IM) in aqueous solution.

• Bulletin of the Korean Chemical Society
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• v.25 no.12
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• pp.1898-1906
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• 2004

Nonclassical quinazolinone analogs I, II, and III, in which the glutamic acid moiety of the classical antifolates is substituted by phenylglycine, phenylalanine or aminobenzoic acid and their methyl esters, were synthesized and evaluated as lipophilic inhibitors of thymidylate synthase (TS). The target compounds were generally potent inhibitors of L. casei and human TS with $IC_{50}$ values within the narrow range of 0.2-10 ${\mu}$M and 0.003-0.03 ${\mu}$M, respectively. Further, most of the target compounds showed cytotoxicity against tumor cell lines of murine and human origin with $IC_{50}$ values of as low as 0.050 ${\mu}$M. Substitution of another hydroxyl or carboxylic acid/ester group at the phenyl ring further increased the potency of TS inhibition and cell growth inhibition. Most effective were compounds If and Ic in which extra carboxylic acid/ester was present at the phenyl ring with nanomolar $IC_{50}$ values of 0.0044 and 0.0093 ${\mu}$M against human TS and submicromolar cytotoxic growth inhibition against all four tumor cell lines.

• Bulletin of the Korean Chemical Society
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• v.14 no.6
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• pp.743-749
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• 1993

The approximate rates and stoichiometry of the reaction of excess lithium tris(dihexylamino)aluminum hydride(LTDHA) with selected organic compounds containing representative functional groups under the standardized conditions (tetrahydrofuran, 0$^{\circ}$C) were studied in order to define the reducing characteristics of the reagent for selective reductions. The reducing ability of LTDHA was also compared with those of the parent lithium aluminum hydride(LAH), lithium tris(diethylamino)aluminum hydride(LTDEA), and lithium tris(dibutylamino)aluminum hydride(LTDBA). In general, the reactivity toward organic functionalities is in order of $LAH{\gg}LTDEA{\geq}LTDBA>LTDHA$. LTDHA shows a unique reducing characteristics. Thus, the reagent reduces aldehydes, ketones, esters, epoxides, and tertiary amides readily. Anthraquinone is cleanly reduced to 9,10-dihydro-9,10-anthracenediol without hydrogen evolution, whereas p-benzoquinone in inert to LTDHA. In addition to that, disulfides are also readily reduced to thiols without hydrogen evolution. However, carboxylic acids, anhydrides, nitriles, and primary amides are reduced slowly. Especially, this reagent reduces aromatic nitriles to the corresponding aldehydes in good yields.

• Bulletin of the Korean Chemical Society
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• v.12 no.6
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• pp.612-617
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• 1991

The approximate rates and stoichiometry of the reaction of excess 1,3,2-biphenyldioxaborepin [2,2'-biphenoxyborane (BPB)] with selected organic compounds containing representative functional groups under the standardized conditions (tetrahydrofuran, hydride to compound being 4 : 1, room temperature) was examined in order to define the characteristics of the reagent for selective reductions and compare its reducing power with those of other substituted boranes. The results indicate that BPB is unique and the reducing power is much stronger than that of other dialkoxyboranes, such as catecholborane and di-s-butoxyborane. BPB reduces aldehydes, ketones, quinones, lactones, tertiary amides, and sulfoxides readily. Carboxylic acids, anhydrides, esters, and nitriles are also reduced slowly. However, the reactions of acid chlorides, epoxides, primary amides, nitro compounds, and disulfides with this reagent proceed only sluggishly.

• Bulletin of the Korean Chemical Society
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• v.5 no.6
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• pp.240-244
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• 1984

8-Oxyquinoline dihydroboronite is prepared by mixing equimolar amounts of 8-hydroxyquinoline and borane-dimethyl sulfide complex in tetrahydrofuran at room temperature and its structure is determined by spectroscopic methods. The reagent is shown to be an extremely mild reducing agent and reduces aldehydes, cyclohexanones, and acid chlorides to some extent. The reagent in the presence of 0.1 equiv of boron trifluoride etherate in tetrahydrofuran at room temperature reduces selectively aldehydes in the presence of ketones, while the reagent in the presence of 1 equiv of boron trifluoride etherate rapidly reduces simple aldehydes and ketones but does not reduce carboxylic acids, esters, and amides.

• Journal of the Korean Chemical Society
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• v.23 no.3
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• pp.175-179
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• 1979

In acidic media such as aqueous acetic acid, phthalimide is reduced with zinc dust to give 3-hydroxyphthalimidine while the 2,2,2-trichloroethyl esters or glycosides are reductively cleaved. However, it has been discovered that, by employing a mixture of THF and pH 4.5 buffer solution as a solvent, 2,2,2-trichloroethyl group can be selectively removed with activated zinc dust in the presence of phthalimido function, provided that the reactant or the product does not have any free carboxylic acid function. By applying the above methods, reaction of $2,2,2-trichloroethyl 3,4,6-tri-O-acetyl-2-deoxy-2-phthalimido-{\beta}-D-glucopyranoside$ (1) with activated zinc dust gave a good yield of $3,4, 6-tri-O-acetyl-2-deoxy-2-phthalimido-{\beta}-D-glucopyranose$ (5) in THF-buffer solution, and $3,4,6-tri-O-acetyl-2-deoxy-2-(3-hydroxyphthalimidino)-{\beta}-D-glucopyranose$ (6) in aqueous acetic acid.

• Textile Coloration and Finishing
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• v.7 no.4
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• pp.61-73
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• 1995

Inorganic salts have negative or positive effects on the rates of many chemical reactions and also the rates of acidic and alkaline hydrolysis of carboxylic esters. The direction of salt effects on the hydrolysis of ester depends on the charge of esters. It is expected that the rate of the alkaline hydrolysis of Poly(ethylene terephthalte)(PET), polymeric solid carboxytic polyester with carboxyl end group at the polymer end, is also influenced by inorganic salts. In the present work, to clarify the effect of divalent cations on the alkaline hydrolysis of PET, many salts with divalent cations like $MgCl_{2},CaCl_{2},SrCl_{2},BaCl_{2},$ were added to the aqueous alkaline solutions. Then PET was hydrolyzed with aqueous NaOH solution having many salts under various conditions. Some conclusions obtained from the experimental results were summarized as follows. Many salts with various divalent cations increased or decreased the reaction rate of alkaline hydrolysis of PET depending on their electrophilicity, hydration property, ability of ion pair formation, solubility, and the degree of interactions between divalent cations and anions, etc. The hydrolysis was interrupted in the order of $Ca^{+2} and was generally accelerated in the order of $Ba^{+2}. It was inferred from the increase in ΔS$^*$and the decrease in the ΔG$^*$that the divalent cations $Sr^{+2}$ and $Ba^{+2}$attracted by PET increased the collision frequency between carbonyl carbon and $OH^{-}$ion and then accelerated the reaction rate. $Mg^{+2}$and $Ca^{+2}$decreased the reaction rate because of their strong interaction with $OH^{-}$.