• 대한화학회지
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• 제34권1호
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• pp.19-28
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• 1990

니트로벤젠 용액 중에서 삼염화안티몬과 염화벤질, 염화-$\alpha$-페닐에틸, 염화디페닐메틸 등의 유기염소화합물 사이의 염소 교환반응에 관한 반응속도론적 연구를 수행하였다. 연구결과 이들 염소교환 반응속도는 삼염화안티몬에 관하여 2차이고 유기염화물에 관하여 1차인 반응속도식을 따르며, Rate = $k_3[SbCl_3]^2$ [Org-Cl] 삼염화안티몬과 유기염화물 사이의 염소 교환반응 속도상수는 유기염화물에 따라 다음과 같은 순서로 증가함을 알았다. 염화벤질 < 염화-$\alpha$-페닐에틸 < 염화디페닐메틸 그리고 이들 염소 교환반응에 관한 메카니즘도 제시하였다.

• Bulletin of the Korean Chemical Society
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• 제32권10호
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• pp.3692-3695
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• 2011

Poly(N,N'-Dichloro-N-ethyl-benzene-1,3-disulfonamide) (PCBS) and N,N,N',N'-Tetrachlorobenzene-1,3-disulfonamide (TCBDA) were found to be a mild and efficient reagent for the direct oxidative conversion of sulfur compounds to the corresponding arenesulfonyl chlorides in good to excellent yields through the oxidative chlorination. The overall process is simple, practical, and it provides convenient access to a variety of aryl or heteroarylsulfonyl chlorides. The mild reaction conditions and the broad substrate scope render this method attractive, and complementary to existing syntheses of aryl or heteroarylsulfonyl chlorides.

• 한국환경과학회지
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• 제5권5호
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• pp.561-567
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• 1996

31 종류의 유기 염소계 잔류 농약을 동시에 분석하는 기체 크로마토그래피 방법을 개발하기 위하여 본 연구를 수행하였다. 준비된 분석 시료를 ECD (electron capture detector)로 Ultra-2 column의 GC (gas chromatography)에 주입하였다. Column 충진 물질을 florisil과 alumina N으로 변화시키면서 잔류 용액을 column에 loading하고 용출 용매로는 ether . benzene(2 : 8) solution, hexane . benzene(1 . 1) solution, dichloromethane, acetone 및 methanol을 사용하였다. 분석 결과 column 충진 물질로 florisil을 사용하였을때 (첫째 조건) 6종류의 유기 염소(dichlorfluanid, captan, chlorofenvinfos, folpet, captafol과 dicofol)가 검출되지 않았다. 이 조건에서 dichloromethane과 methanol을 용출 용매로 첨가하였을때는 (둘째 조건) 첫째 분석 조건하에서 검출되지 않았던 6종류의 유기 염소가 검출되었고 thrin계 pesticides, 특히 captan과 captafol의 recovery가 증가하였다(첫째 조건에서와 마찬가지로 충진 물질로 florisil을 사용). 그러나 BHC(benzene hexachloride) 화합물의 recovery는 감 소하였다. 한편 alumina N을 column 충진 물질로 사용하였을 경우에는 dichlorfluanid, chlorofenvinfos, folpet 및 dicofol의 recovery가 증가하였으며 aldrin도 그러하였다. 하지만 captan과 captafol은 그렇지 못하였다. Thrin계 pesticides, captan 및 captafol을 동시에 검출하기 위하여 florisil과 alumina N을 충진 물질로 동시에 사용하고 n-hexane을 충진시켜 용출시킨 결과, captan과 captafol이 검출되지 않았는데 이는 column이 충분히 활성화되지 않았기 때문이라고 생각된다. Column(florisil과 alumina N을 충진 물질로 동시 사용)을 충분히 활성화시키고 여러가지 용출 용매를 사용하여 불순물을 제거하였을때 분석 결과가 가장 우수하였다(31 종류의 유기 염소계 잔류 농약이 sharp하게 검출되었고 높은 감도를 나타내었다).

• 농약과학회지
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• 제8권1호
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• pp.8-15
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• 2004

베타-케토아세트아닐라이드 염화물 유도체의 합성 및 이들 화합물의 대표적인 6종의 식물병원균에 대한 항균력을 조사하였다. Carousel Reaction Stations 장치를 이용하여 조합 합성 기법을 통하여 키틴 이합 체를 염소와 아닐린 유도체와 차례로 반응시켜 89종의 베타-케토아세트아닐라이드 클로라이드 유도체를 얻었다. 합성된 화합물 라이브러리의 항균력(in vivo)을 벼 도열병, 벼 잎집무늬마름병, 토마토 잿빛곰팡이병, 토마토 잎마름역병, 밀 붉은녹병, 보리 흰가루병 등의 주요 식물병에 대한 항균력 시험을 수행하였다. 일반적으로 페닐기의 4위치 (para) 치환체가 존재하는 화합물의 경우에 선택적으로 토마토 잎마름역병을 방제하였다.

• Bulletin of the Korean Chemical Society
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• 제11권1호
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• pp.60-64
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• 1990

The reactions of alkanesulfonyl chlorides with pyridines in the presence of various solvents have been studied by means of kinetic method. Alkanesulfonyl chlorides bearing ${\alpha}$-hydrogen with the normal attack of pyridine is found to be at the ${\alpha}$-hydrogen with elimination to form the sulfene intermediate evidently. From the mass spectra by the reaction of ethanesulfonyl chloride with 3-picoline in the presence of methanol-$d_1$, it has shown that the reaction has a witness favorable to the slulfene intermediate.

• Bulletin of the Korean Chemical Society
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• 제13권1호
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• pp.83-87
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• 1992

The ring expansion of 1,3-thiazolidines 4 derived from ${\beta}$-ketoacid derivatives to the corresponding dihydro-1,4-thiazines 1 by using the action of chlorine on 4 has been achieved. In the chlorinolysis unisolable sulfenyl chlorides 5 may be formed from chlorosulfonium ions 11 by ${\beta}$-elimination involving carbonyl activated methylene hydrogens. Addition of sulfenyl chloride to the internal double bond appears to form probable thiiranium ions 14, which in turn gave 1 with loss of acidic proton. Imminium ions 15 could be hydrolyzed easily to give enol 8. As a side reaction, dihydrothiazine that was formed was further chlorinated to produce dichlorides 16 which were rearranged readily to the chloromethyl compounds 10.

• Bulletin of the Korean Chemical Society
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• 제8권4호
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• pp.313-318
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• 1987

The approximate rate and stoichiometry of the reaction of excess Thexylbromoborane-methyl sulfide, $ThxBHBr{\cdot}SMe_2,$ with selected organic compounds containing representative functional groups under standardized conditions (methylene chloride, $0^{\circ}C)$ were studied in order to characterize the reducing characteristics of the reagent for selective reductions. The selectivity of the reagent was also compared to the selectivity of thexylchloroborane-methyl sulfide. Thexylbromoborane appears to be a much milder and hence more selective reducing agent than thexylchloroborane. The reagent tolerates many organic functionalities. Thus, the reagent shows very little reactivity or no reactivity toward acid chlorides, esters, epoxides, amides, nitro compounds including simple olefins. However, this reagent can reduce aldehydes, ketones, carboxylic acids, nitriles, and sulfoxides. Especially the reagent reduces carboxylic acids including ${\alpha},{\beta}$ -unsaturated ones and nitriles to the corresponding aldehydes. In addition to that, thexylbromoborane shows good stereoselectivity toward cyclic ketones, much better than the chloro-derivative.

• Bulletin of the Korean Chemical Society
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• 제13권2호
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• pp.199-207
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• 1992

The approximate rates and stoichiometry of the reaction of excess sodium diethyldihydroaluminate (SDDA) with 68 selected organic compounds containing representative functional groups were examined under standard conditions (THF-toluene, $0^{\circ}C$ in order to compare its reducing characteristics with lithium aluminum hydride (LAH), aluminum hydride, and diisobutylaluminum hydride (DIBAH) previously examined, and enlarge the scope of its applicability as a reducing agent. Alcohols, phenol, thiols and amines evolve hydrogen rapidly and quantitatively. Aldehydes and ketones of diverse structure are reduced rapidly to the corresponding alcohols. Reduction of norcamphor gives 11% exo-and 89% endo-norborneol. Conjugated aldehydes such as cinnamaldehyde are rapidly and cleanly reduced to the corresponding allylic alcohols. p-Benzoquinone is mainly reduced to hydroquinone. Hexanoic acid and benzoic acid liberate hydrogen rapidly and quantitatively, however reduction proceeds very slowly. Acid chlorides and esters tested are all reduced rapidly to the corresponding alcohols. However cyclic acid anhydrides such as succinic anhydride are reduced to the lactone stage rapidly, but very slowly thereafter. Although alkyl chlorides are reduced very slowly alkyl bromides, alkyl iodides and epoxides are reduced rapidly with an uptake of 1 equiv of hydride. Styrene oxide is reduced to give 1-phenylethanol quantitatively. Primary amides are reduced very slowly; however, tertiary amides take up 1 equiv of hydride rapidly. Tertiary amides could be reduced to the corresponding aldehydes in very good yield ( > 90%) by reacting with equimolar SDDA at room temperature. Hexanenitrile is reduced moderately accompanying 0.6 equiv of hydrogen evolution, however the reduction of benzonitrile proceeds rapidly to the imine stage and very slowly thereafter. Benzonitrile was reduced to give 90% yield of benzaldehyde by reaction with 1.1 equiv of hydride. Nitro compounds, azobenzene and azoxybenzene are reduced moderately at $0^{\circ}C$, but nitrobenzene is rapidly reduced to hydrazobenzene stage at room temperature. Cyclohexanone oxime is reduced to the hydroxylamine stage in 12 h and no further reaction is apparent. Pyridine is reduced sluggishly at $0^{\circ}C$, but moderately at room temperature to 1,2-dihydropyridine stage in 6 h; however further reaction is very slow. Disulfides and sulfoxides are reduced rapidly, whereas sulfide, sulfone, sulfonic acid and sulfonate are inert under these reaction conditions.

• Bulletin of the Korean Chemical Society
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• 제34권3호
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• pp.820-822
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• 2013

N,N,N',N'-Tetrabromobenzene-1,3-disulfonamide (TBBDA)/$PPh_3$ and N,N,N',N'-tetrachlorobenzene-1,3-disulfonamide (TCBDA)/$PPh_3$ are two highly reactive reagent systems for the conversion of alcohols corresponding into alkyl chlorides and bromides in moderate to excellent yields in dichloromethane at room temperature under mild and neutral conditions.

• Bulletin of the Korean Chemical Society
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• 제12권6호
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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.