• 자원환경지질
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• 제34권3호
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• pp.301-306
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• 2001

계면활성제를 이용한 오염복원에 있어서 제거효율에 영향을 주는 계면활성제 용액 pH의 최적범위를 조사하기 위하여 주상실험이 수행되었다. 톨루엔과 1,2,4-trichlorobenzene이 소수성 유기 화합물로서 선택되었다. 4%(v/v)의 sodium diphenyl oxide disulfonate(DOSL), trideceth-19-carboxylic acid(TDCA), octylphenoxypoly ethosye-thanol(OPEE)을 사용하여 두 종류의 아이오와 토양(Fruitfield sand, Webster clay loam)에 대한 용출실험을 수행하였다. 실험결과, 톨루엔과 1,2,4-trichlorobenzene의 제거효율은 계면활성제 용액 pH 10에서 나타났고, Furifield 사질토양에서 DOSL을 이용한 경우 최대 제거효율은 각각 94%, 97%였다. Fruitfield 사질토양에서 DOSL을 사용한 경우, pH 조절에 의하여 증가된 톨루엔과 1,2,4-trichlorobenzene의 제거효율은 각각 16%와 20%였다. Webster clay loam에서 DOSL을 이용한 경우 최대 제거효율은 각각 89%, 93%였다. Webster clay loam에서 DOSL을 사용한 경우, pH 조절에 의하여 증가된 톨루엔과 1,2,4-trichlorobenzene의 제거효율은 각각 26%와 19%였다. 이러한 실험결과는 NAPLs로 오염된 토양을 복원하는데 있어서 계면활성제 용액의 pH를 높게 유지하는 것이 바람직하다는 것을 의미한다.

• 대한화학회지
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• 제6권1호
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• pp.77-83
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• 1962

The solubilities of hydrogen bromide and methyl bromide in nitrobenzene and in 1,2,4-trichlorobenzene have been measured in the presence and absence of gallium bromide. When gallium bromide does not exist in the system, the solubilities of HBr and MeBr in nitrobenzene are greater than in 1,2,4-trichlorobenzene, indicating the greater basicity of nitrobenzene than 1,2,4-trichlorobenzene. When there exists gallium bromide in the system, the addition compounds, GaBr3·HBr and GaBr3·CH3Br, have been found to exist in solution. The addition compound of GaBr3·HBr is stable in nitrobenzene but unstable in 1,2,4-trichlorobenzene. On the other hand the addition compound of $GaBr_3{\cdot}CH_3Br$ is unstable in both solvents. All of these unstable addition compounds dissociate into components to large extents according to one of the following equilibria or both: $$GaBr_3{\cdot}RBr{\leftrightarrows}GaBr_3+RBr\;GaBr_3{\cdot}RBr{\leftrightarrows}1}2\;Ga_2Br_6+RBr$.$ where R denotes either hydrogen atom or methyl group.

• Toxicological Research
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• 제12권1호
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• pp.29-34
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• 1996

1,2,4-trichlorobenzene (1,2,4-TCB) is used as a dye carrier, an intermediate in the syn[hesis of herbicides, aflame retardant, and for other purpose. After a single oral administration of 1,2,4-TCB (200 mg/kg, 400 mg/kg) in rats, toxic effects were studied by means of serum biochemical and hematological analysis, and liver calcium concentration. Administration of 1,2,4-TCB resulted in dose-dependent manner liver and kidney damage being suggested by increased serum alanine aminbtransferase (ALT) activities, liver calcium concentration and blood urea nitrogen (BUN). Pretreatment with DL-buthionine sulfoximine (BSO, 2 mmol/kg, i.p.) considerably decreased liver glatathione concentration, which was accompanied by markedly elevated serum ALT activites. It is well-known that toxicity of halogenated benzene such as bromobenzene, 1,4-dichlorobenzene is increased by pretreatment of phenobarbital, and protected by pretreatment of cytochrorn P450 inhibitor including metyrapone. However, there were no obvious alterations in toxicity of 1,2,4-TCB by pretreatment of phenobarbital or metyrapone. In comparison with control group, treatment groups exhibited significant changes in some parameters of hematological analysis but all hematological values remained within normal ranges.

• 대한화학회지
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• 제7권1호
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• pp.65-68
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• 1963

The solubility of ethyl bromide in nitrobenzene and in 1,2,4-trichlorobenzene has been measured at $19^{\circ}$ in the presence and absence of gallium bromide. When gallium bromide does not exist in the system, the solubility of ethyl bromide in nitrobenzene is greater than in 1,2,4-trichlorobenzene, indicating the stronger interaction of ethyl bromide with nitrobenzene than with 1,2,4-trichlorobenzene. When there exists gallium bromide in the system, an unstable 1: 1 complex, C2H5Br·GaBr3, of gallium bromide with ethyl bromide is formed in the solution. The 1: 1 complex in solution dissociates into the components to a large extent according to one of the following equilibria or both: $C_2H_5Br{\cdot}GaBr_3{\rightleftarrows}C_2H_5Br+GaBr_3$C_2H_5Br{\cdot}GaBr_3{\rightleftarrows}C_2H_5Br+1}2GaBr_3$$ The stability of the 1: 1 complex of ethyl bromide with gallium bromide is compared with that of the corresponding complex of methyl bromide.

• Applied Biological Chemistry
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• 제22권2호
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• pp.109-122
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• 1979

잔류성(殘留性) 살충제(殺忠劑)인 BHC의 합리적(合理的) 사용방법(使用方法)을 찾기 위하여 용매추출법(溶媒抽出法)에 의한 ${\gamma}$-isomer를 분리(分離) 및 농축(濃縮)하였다. 그리고 불활성(不活性) 이성질체(異性質體)로 부터 1,2,4-trichlorobenzene, 2,4,5-trichloronitrobenzene, 2,4,5-trichloroaniline을 거쳐 3-(2,4,5-trichlorophenyl)-1-methyl urea를 합성(合成)하였으며 몇가지 작물(作物)에 대한 발아(發芽) 및 생육억제효과(生育抑制效果)를 조사하였다. 실험결과(實驗結果)를 요약(要約)하면 다음과 같다. 1. methanol-물 용매계(溶媒系)에서 BHC 원제(原劑)를 재결정(再結晶)하였고, ${\gamma}$-이성질체의 회수율(回收率) 95%에서 ${\gamma}$-이성질체의 조성(組成)이 49.5%로 강화(强化)된 BHC 결정(結晶)을 얻었다. 2. BHC 원제(原劑)를 85%의 methanol성(性) 수용액(水溶液)으로 추출(抽出)한 다음, chloroform이 분배(分配)시켜 재결정시켰을 때는 ${\gamma}$-이성질체의 회수율 90.5%에서 ${\gamma}$-이성질체의 조성(組成)이 89.6%로 농축된 BHC 결정을 얻을수 있었다. 3. BHC 원제로 부터 1,2,4-trichlorobenzene의 합성시(合成時), 합성수율(合成收率)은 alkali 농도(溫度)에 크게 좌우되며, 사용(使用)된 alkali의 종류에도 다소 영향을 받는다. 4. BHC 원제의 alkali 가수분해시(加水分解時) 계면활성제(界面活性劑)의 첨가(添加)는 1,2,4-trichlorobenzene의 수율(收率)을 높혔다. 특히 사급(四級)암모늄염은 1,2,4-trichlorobenzene의 수량(收量)을 크게 증가(增加)시켰다. 5. 1,2,4-trichlorobenzene으로 부터 2,4,5-trichloronitrobenzene의 합성시(合成時) nitro 화시약(化試藥)으로서 $HNO_3-H_2SO_4$를 사용하였을때 94.4%라는 높은 수율(收率)을 보였다. 6. 2,4,5-trichloronitrobenzene을 철(鐵)과 염산(鹽酸)으로 환원(還元)시켰을때, 생성(生成)된 2,4,5-trichloroaniline의 수율(收率)은 91.4%이였다. 7. BHC 원제(原劑)를 기준(基準)으로한 3-(2,4,5-trichlorophenyl)-1-methyl urea의 전수율(全收率)은 60.8%이었다. 8. 6종(種)의 작물에 대한 3-(2,4,5-trichlorophenot)-1-methyl urea의 발아(發芽) 및 생육억제효과(生育抑制效果)는 대조(對照)로 사용한 urea계(系) 제초제(除草劑)인 linuron, diuron 보다 강(强)하였으며, 또 본(本) 화합물(化合物)에 대한 감수성(感受性)은 작물의 종류(種類)와 부위(部位)에 따라 차이(差異)가 있었다.

• Bulletin of the Korean Chemical Society
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• 제2권4호
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• pp.138-141
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• 1981

The rate of the bromine-exchange reaction between gallium bromide and i-butyl bromide in 1,2,4-trichlorobenzene or nitrobenzene was measured at 19, 25 and $40^{\circ}C$, using i-butyl bromide labelled with Br-82. The results indicated that the exchange reaction was second order with respect to gallium bromide and first order with respect to i-butyl bromide. The third-order rate constant determined at $19{\circ}C$ was $3.28{\times}10^{-2}l^2{\cdot}mole^{-2}{\cdot}sec^{-1}$ in 1,2,4-trichlorobenzene and $9.25{\times}10^{-3}l^2{\cdot}mole^{-2}{\cdot}sec^{-1}$ in nitrobenzene. The activation energy, the enthalpy of activation and the entropy of activation for the exchange reaction were also determined.

• Bulletin of the Korean Chemical Society
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• 제2권3호
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• pp.86-89
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• 1981

The rate of the bromine-exchange reaction between gallium bromide and n-propyl bromide in 1,2,4-trichlorobenzene and in nitrobenzene was measured at 19, 25 and $40^{\circ}C$, using n-propyl bromide labelled with Br-82. The results indicated that the exchange reaction was second order with respect to gallium bromide and first order with respect to n-propyl bromide. The third-order rate constant determined at $19^{\circ}C$ is $2.9{\times} 10^{-2}l^2{\cdot}mole^{-2}{\cdot}sec^{-1}$ in 1,2,4-trichlorobenzene and $4.5{\times}10^{-3}l^2{\cdot}mole^{-2}{\cdot}sec^{-1}$. in nitrobenzene. The activation energy, the enthalpy of activation and the entropy of activation for the exchange reaction were also determined. Reaction mechanism for the bromine exchange of n-propyl bromide seemed to be similar to those observed in earlier studies with other alkyl bromides.

• 대한화학회지
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• 제15권5호
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• pp.228-235
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• 1971

니트로벤젠 및 1,2,4-트리클로로벤젠에서의 n-브롬화부틸의 溶解度를 $19^{\circ},\;25^{\circ},\;40^{\circ}C$에서 브롬화갈륨이 있을때와 없을때에 각각 測定하여 보았다. 브롬화갈륨이 存在하지 않을때에 니트로벤젠에서의 n-브롬화부틸의 溶解度가 1,2,4-트리클로로벤젠 보다 더 큰점은 n-브롬화부틸과 니트로벤젠과의 相互作用이 1,2,4-트리클로로벤젠 보다 더 강하다는 것을 나타낸다. 브롬화갈륨이 存在할 때에는 溶液內에서 n-브롬화부틸과 브롬화갈륨의 1:1 complex, $n-C_4H_9Br{\cdot}GaBr_3$가 형성된다. 이 complex의 instability constant K를 計算하였다. $n-C_4H_9Br{\cdot}GaBr_3{\\rightleftharpoons}n-C_4H_9Br+\frac{1}{2}Ga_2Br_6$ 또한 이 complex의 解離에 대한 엔탈피, 자유에너지 및 엔트로피도 산출하였다.

• 대한화학회지
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• 제24권4호
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• pp.302-309
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• 1980

니트로벤젠 및 1,2,4-트리클로로벤젠에서의 n-브롬화프로필의 溶解度를 19, 25, 40^{\circ}C$에서 브롬화갈륨이 있을 때와 없을 때에 각각 측정하여 보았다. 브롬화갈륨이 존재하지 않을때에 니트로벤젠에서의 n-브롬화프로필의 溶解度가 1,2,4-트리클로로벤젠에서보다 더 큰 점은 n-브롬화프로필과 니트로벤젠과의 상호작용이 1,2,4-트리클로로벤젠보다 더 강하다는 것을 나타낸다. 브롬화갈륨이 존재할 때에는 溶液內에서 n-브롬화프로필과 브롬화갈륨의 1:1 complex, $n-C_3H_7Br\cdotGaBr_3$가 형성된다. 이 complex의 instability constant K를 계산하였다. $$n-C_3H_7Br\cdotGaBr_3 \rightleftarrows n-C_3H_7Br ＋ \frac{1}{2Ga_2Br_6 }$$또한 이 complex의 解離에 대한 엔탈피, 자유에너지 및 엔트로피도 산출하였다. 브롬화갈륨과 브롬화알킨간의 complex의 안정도는 이들 알킬이온의 안정도와 상대적인 관계가 있다고 본다.

• Environmental Analysis Health and Toxicology
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• 제11권1_2호
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• pp.41-47
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• 1996

1, 2, 4-Trichlorobenzene (1, 2, 4-TCB) is used as a dye carrier, as an intermediate in the synthesis of herbicides, as a flame retardant, and for other purpose. After a single oral administration of 1, 2, 4-TCB (200 mg/kg, 400 mg/kg) in rats, toxic effects were studied by means of serum biochemical and heatological analysis, and liver calcium concentration. Administration of 1, 2, 4-TCB resulted in dose-dependent liver and kidney damage as estimated by increased serum alanine aminotransferase (ALT) activities, liver calcium concentration and blood urea nitrogen (BUN). Pretreatment with DL-buthionine sulfoximine (BSO, 2 mmol/kg, i.p. ) considerably decreased liver glutathione concentration, which was accompanied by markedly elevated serum ALT activites. It is well-known that toxicity of halogenated benzene such as bromobenzene, 1, 4-dichlorobenzene is increased by pretreatment of henobarbital (PB), and protected by pretreatment of cytochrome P450 inhibitor including metyrapone (MP). However, there was no obvious alterations in toxicity of 1, 2, 4-TCB by pretreatment of phenobarbital or metyrapone. In comparison with control group, treatment groups exhibited significant changes in some parameters of hematological analysis but all hematological values remined within normal ranges.