On the Utilization of Inactive BHC isomers -Synthesis of 3-(2,4,5-trichlorophenyl)-1-methyl urea as a herbicide-

BHC 이성질체(異性質體)의 활용(活用)에 관(關)한 연구(硏究) -제초제(除草劑)로서 3-(2,4,5-trichlorophenyl)-1- methyl urea의 합성(合成)-

Present study was carried out to reduce residual toxicity of BHC insecticides inherent in the organochlorine pesticides. For This end, r-isomer, the most potent insecticidal component among the BHC stereoisomers, was isolated and thus fortified by means of solvent precipitation. In parallel, 3-(2,4,5-trichlorophenyl)-1-methyl urea was prepared in good yield from technical BHC via 1,2,4-trichlorobenzene, 1,2,4,-trichloronitrobenzene, and 2,4,5-trichloroaniline. In addition, certain merit of the compound which make it possible to use as a herbicide is discussed. The results are summarized as follows; 1. Recrystallizing technical BHC from methanol-water binary solvent system, r-isomer was enriched to 49.7% at 95% recovery of r-isomer. 2. By partitioning technical BHC in 85% of methanolic solution into chloroform, r-isomer was fortified to 89.6% at 90.5% recovery of r-isomer. 3. Yield of 1,2,4-trichlorobenzene from technical BHC was greatly dependent upon concentration of alkalies and to less degree on the alkalies. 4. Surfactants, in particular cationic a quartenary ammonium salt, increased yield of 1,2,4-trichlorobenzene from technical BHC by alkaline hydrolysis. 5. Conversion of 1,2,4-trichlorobenzene to 2,4,5-trichloronitrobenzene was effected almost quantitatively utilizing $HNO_3-H_2SO_4$ nitrating agent at low temperature. 6. Yield of 91.4% was observed for the synthesis of 2,4,5-trichloroaniline by reducing 2,4,5-trichloronitrobenzene in the presence of iron turning and hydrochloric acid. 7. Overall yield based on BHC of 3-(2,4,5-trichlorophenyl)-1- methyl urea was 60.8%. 8. Inhibition effects, both germination and growth, 3-(2,4,5-trichlorophenyl)-1-methyl urea on several crops were found comparable to or more potent than those of $linuron{\circledR}\;and\;diuron{\circledR}$. In addition, it was also noted that susceptibility to the prepared compound depended upon the crops as well as specific part (shoots, roots) of the plant exposed to the chemicals.

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.