• Bulletin of the Korean Chemical Society
• /
• 제13권5호
• /
• pp.531-537
• /
• 1992

The approximate rates and stoichiometry of the reaction of excess potassium 2-thexyl-1,3,2-dioxaborinane hydride(KTDBNH) with 55 selected compounds containing representative functional groups under standardized conditions (tetrahydrofuran, TEX>$0^{\circ}C$, reagent : compound=4 : 1) was examined in order to define the characteristics of the reagent for selective reductions. Benzyl alcohol and phenol evolve hydrogen immediately. However, primary, secondary and tertiary alcohols evolve hydrogen slowly, and the rate of hydrogen evolution is in order of $1^{\circ}$> $2^{\circ}$> $3^{\circ}$. n-Hexylamine is inert toward the reagent, whereas the thiols examined evolve hydrogen rapidly. Aldehydes and ketones are reduced rapidly and quantitatively to give the corresponding alcohols. Cinnamaldehyde is rapidly reduced to cinnamyl alcohol, and further reduction is slow under these conditions. The reaction with p-benzoquinone dose not show a clean reduction, but anthraquinone is cleanly reduced to 9,10-dihydro-9,10-anthracenediol. Carboxylic acids liberate hydrogen immediately, further reduction is very slow. Cyclic anhydrides slowly consume 2 equiv of hydride, corresponding to reduction to the caboxylic acid and alcohol stages. Acid chlorides, esters, and lactones are rapidly and quantitatively reduced to the corresponding carbinols. Epoxides consume 1 equiv hydride slowly. Primary amides evolve 1 equiv of hydrogen readily, but further reduction is slow. Tertiary amides are also reduced slowly. Both aliphatic and aromatic nitriles consume 1 equiv of hydride rapidly, but further hydride uptake is slow. Analysis of the reaction mixture with 2,4-dinitrophenylhydrazine yields 64% of caproaldehyde and 87% of benzaldehyde, respectively. 1-Nitropropane utilizes 2 equiv of hydride, one for hydrogen evolution and the other for reduction. Other nitrogen compounds examined are also reduced slowly. Cyclohexanone oxime undergoes slow reduction to N-cyclohexylhydroxyamine. Pyridine ring is slowly attacked. Disulfides examined are reduced readily to the correponding thiols with rapid evolution of 1 equiv hydrogen. Dimethyl sulfoxide is reduced slowly to dimethyl sulfide, whereas the reduction of diphenyl sulfone is very slow. Sulfonic acids only liberate hydrogen quantitatively without any reduction. Finally, cyclohexyl tosylate is inert to this reagent. Consequently, potassium 2-thexyl-1,3,2-dioxaborinane hydride, a monoalkyldialkoxyborohydride, shows a unique reducing characteristics. The reducing power of this reagent exists somewhere between trialkylborohydrides and trialkoxyborohydride. Therefore, the reagent should find a useful application in organic synthesis, especially in the field of selective reduction.

• 한국산업보건학회지
• /
• 제9권1호
• /
• pp.156-172
• /
• 1999

Potential chemical hazards encountered in painting operation of four shipyards and a ship-repair shop were investigated through the material safety data sheets (MSDS). Material safety data sheets (MSDS) for 307 paints, 50 thinners and 34 binders were collected and reviewed. It was shown that various organic solvents such as aromatic hydrocarbons, aliphatic hydrocarbons, ketones, alcohols, glycols, glycol ether acetates and esters were contained in painting materials. Of these solvents, xylene was found in the largest number of painting materials. sixty percent of the thinners contained xylene in the contents of 20-100%. Other most frequently found solvents were 1-methoxypropanol, 1-methoxypropyl acetate, n-butanol, methyl isobutyl ketone, toluene, isopropanol, and n-butyl acetate, etc. Glycol ethers such as 2-methoxyethanol (2-ME), 2-methoxyethyl acetate (2-MEA), 2-ethoxyethanol (2-EE), 2-ethoxyethyl acetate (2-EEA) and 2-butoxyethanol (2-BA) were regarded as having the potential to cause adverse reproductive effects, embryotoxic effect and hematotoxic effects, and were found in some epoxy panting materials. Coal tar pitch was included in some paints(13%) where polynuclear aromatic hydrocarbons (PAHs) could be contaminated. Inorganic pigments such as lead chromate and zinc potassium chromate were found in some paints (8%). The epoxy resin based paints, which may contain isocyanates such as toluene diisocyanates and hexamethylene diisocyanates causing potential sensitization and asthma to upper respiratory organ, were mostly used in the shipyards. The constituents in the MSDS were significantly different from the results analyzed using gas chromatography/mass detector: minor constituents or impurities were omitted in many MSDS. In conclusion, xylene was the most frequent organic solvent in painting materials, and glycol ethers, including 2-ME, 2-MEA, 2-EE, 2-EEA and 2-BA, were found some products. Also, painting workers may be exposed to PAHs, lead, chromate, isocyanates, organic tin and other various chemicals. The compositions of chemicals in painting materials were variable significantly, and the hazards were changed. These facts should be considered in environmental monitoring and control of the hazards.

• 한국식품과학회지
• /
• 제27권6호
• /
• pp.964-971
• /
• 1995

키조개 부산물로 부터 향미제로 응용하기 위하여 제조한 가수분해물의 유리아미노산 및 휘발성 향기성분을 분석한 결과, 유리아미노산의 경우 가수분해물이 생시료에 비해 3배 이상 증가하였으며 taurine의 함량이 가장 많았다. 그리고 생시료와 가수분해물의 휘발성 향기성분을 분석한 결과 총 109종의 화합물이 동정되었는데 이중에서 생시료는 88종, 가수분해물은 65종이 검출되었다. 그리고 이들은 주로 알데히드류(16종), 케톤류(17종), 알콜류(31종), 함질소화합물류(16종), 방향족화합물류(8종), 에스테르류(3종) 및 기타 화합물류(17종)으로 구성되어 있었다. 특히 생시료에서의 산화취 성분인 알데히드류 및 방향족화합물은 가수분해물에서 상당량 감소되었으며 반면에 고소한 향기성분인 heterocyclic 화합물이 상당량 검출되었다.

• 한국신재생에너지학회:학술대회논문집
• /
• 한국신재생에너지학회 2010년도 춘계학술대회 초록집
• /
• pp.251.2-251.2
• /
• 2010

Plant biomass has been proposed to be an alternative source for petroleum-based chemical compounds. Especially, phenolic chemical compounds can be obtained from lignin by chemical depolymerization processes because lignin consists of complex aromatic polymer such as trans-p-coumaryl, coniferyl and sinapyl alcohols, etc. Phenolic chemical compounds from lignin were usually produced in super critical water. However, we applied Near-critical water (NCW) system because NCW is known as a good solvent for lignin depolymerization. Organic matter like lignin can be solved in NCW system and the system has a unique acid-base property without conventional non-eco-friendly chemicals such as sulfuric acid and sodium hydroxide. In this work, we tried to optimize the NCW depolymerization system by adjusting the processing variables such as reaction time, temperature and pressure. Moreover, the amount of additional phenol was optimized by changing the molar ratio between water and phenol. Phenol was used as capping agent to prevent re-polymerization of active fragment such as formaldehyde. Alkali-lignin was used as a starting material and characterized by a Solid State 13C-NMR, FT-IR and EA (Elemental Analysis). GC-MS analysis confirmed that o-cresol, p-cresol, anisole and 4-hydroxyphathalic acid were the main product and they were quantitatively analyzed by HPLC.

• Bulletin of the Korean Chemical Society
• /
• 제25권4호
• /
• pp.501-505
• /
• 2004

Esterification of aliphatic or aromatic carboxylic acids with alcohols using 2-(4-nitrobenzenesulfonyl)-4,5-dichloropyridazin-3(2H)-one (3) in the presence of base in organic solvents gave the corresponding esters in excellent yields

• 한국수산과학회지
• /
• 제42권3호
• /
• pp.224-231
• /
• 2009

Volatile components in Olive Flounder fed diets containing 0, 2,5, 5.0, and 7.5% yuza (Citrus junas Sieb ex Tanaka) for 4 months were investigated. Samples were extracted by solid-phase micro extraction and analyzed by gas chromatography/mass spectrometry. Among 89 compounds detected, 82 were positively identified. Volatile compounds of Olive Flounder fed the unsupplemented diet comprised 12 acids, 10 alcohols, eight aldehydes, five aromatic compounds, nine esters, 12 hydrocarbons, four ketones, two monoterpenes, and one miscellaneous compound. Compounds identified in Olive Flounder fed the yuza-supplemented diets consisted of 10 esters, 11 monoterpenes, 13 sesquiterpenes, and two miscellaneous compounds, with the other compounds being the same as in the control. The most abundant class of compounds in flounders fed the yuza-supplemented diet was the monoterpenes, which included limonene, $\beta$-terpinene, $\beta$-trans-ocimene, and $\alpha$-terpinolene. Of the 13 sesquiterpenes identified in flounder fed the yuza-supplemented diet, bicyclogermacrene was the major volatile compound followed by allo-aromadendrene, trans-caryophyllene, and $\delta$-cadinene. Bicyclogermacrene and germacrene D content increased significantly as the yuza supplementation increased.

• 한국수산과학회지
• /
• 제41권6호
• /
• pp.414-418
• /
• 2008

Volatile compounds in Omangdungi (Styela plicata)-Doenjang (soybean paste) stew were analyzed using solvent-assisted flavor evaporation/gas chromatography/mass-selective detection/olfactometry (SAFE/GC/MSD/O) and aroma extract dilution analysis (AEDA). The GC/O analysis detected 37 volatile compounds, of which 32 were positively identified, and included 9 aldehydes, 5 alcohols, 4 aromatic hydrocarbons, 4 ketones, 3 esters, 3 N-containing compounds, 2 acids, 1 S-containing compound, and 1 furan. Nine aroma-active odorants ($\log_3FD{\geq}3.0$) in the sample included six compounds derived from Doenjang (3-methyl(thio)propanal, tetramethylpyrazine, 4-vinyl-2-methoxyphenol, 2-acetylpyrrole, butyric acid, and 2-methoxyphenol) and three compounds from Omangdungi (2-acetyl-2-thiazoline, 9-decanol, and 6-decenol). Three compounds derived from Omangdungi (9-decanol, 6-decenol, and 6-nonenol) were thought to enhance the seafood-like flavor of Omangdungi-Doenjang stew.

• 한국수산과학회지
• /
• 제43권6호
• /
• pp.606-613
• /
• 2010

In order to elucidate a mechanism responsible for the development of the odor characteristics of cooked, desirable-flavored shellfish, oysters were extracted using various solvents and the resulting extracts were evaluated organoleptically after cooking. The 80% aqueous methanol extract was found to produce a desirable cooked flavor. This oyster extract was fractionated using ion-exchange column chromatography and dialysis, and each of the fractions was subjected to cooking, followed by organoleptic evaluation. The outer dialysate fraction such as acidic and amphoteric water-soluble fractions produced a cooked oyster flavor. The volatile flavor compounds identified from cooked oyster included 29 hydrocarbons, 20 alcohols, 16 acids, 12 aldehydes, nine nitrogen-containing aromatic compounds, eight ketones, five furans, three esters, three phenols, and one benzene.

• 생약학회지
• /
• 제20권1호
• /
• pp.13-20
• /
• 1989

In continuation of our studies on essential oils of Angelica genus(Umbelliferae), We report on the components of essential oils obtained from the root of Angelica tenuissima Nakai(藁子). Oils were obtained from the dried roots by steam distillation and fractionated by column chromatography. Each isolate or fraction was identified by GC, GC-MS and spectral analysis. Essential oils of the root of A. tenuissima(Gaoben) were found to contain $\alpha-pinene,\;camphene,\;\beta-pinene,\;myrcene,\;\alpha-phellandrene,\;\Delta-3-carene,\;p-cymene,\;limonene,\;\gamma-terpinene,\;terpinolene,\;4-vinylguauacol,\;\gamma-elemene$, one aromatic compound, three unidentified sesquiterpene alcohols, butylidenephthalide, senkyunolide and Z-ligustilide which was the most abundant compound comprising 75% of the whole oil. Also butylphthalide and hydroxybutylidenephalide were tentatively identified.

• Mycobiology
• /
• 제42권4호
• /
• pp.353-360
• /
• 2014

Makgeolli is a traditional Korean alcoholic beverage. The flavor of makgeolli is primarily determined by metabolic products such as free sugars, amino acids, organic acids, and aromatic compounds, which are produced during the fermentation of raw materials by molds and yeasts present in nuruk, a Korean fermentation starter. In this study, makgeolli was brewed using the wild yeast strain Saccharomyces cerevisiae Y98-5, and temporal changes in the metabolites during fermentation were analyzed by ultra-high-performance liquid chromatography-quadrupole-time-of-flight mass spectrometry. The resultant data were analyzed by partial least squares-discriminant analysis (PLS-DA). Various metabolites, including amino acids, organic acids, sugar alcohols, small peptides, and nucleosides, were obviously altered by increasing the fermentation period. Changes in these metabolites allowed us to distinguish among makgeolli samples with different fermentation periods (1, 2, 3, 6, 7, and 8 days) on a PLS-DA score plot. In the makgeolli brewed in this study, the amounts of tyrosine ($463.13{\mu}g/mL$) and leucine ($362.77{\mu}g/mL$) were high. Therefore, our results indicate that monitoring the changes in metabolites during makgeolli fermentation might be important for brewing makgeolli with good nutritional quality.