Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
권호 표지

Nucleophilic Displacement at Sulfur Center (III). Kinetic Studies on Halide Exchange Reactions of Dimethylsulfamoyl Chloride in Dry Acetone

유황의 친핵 치환반응 (제3보). 아세톤 용매속에서의 Dimethylsulfamoyl Chloride의 할라이드 교환반응에 관한 속도론적 연구

  • Ikchoon Lee (Department of Chemistry, Inha University) ;
  • Shi Choon Kim (Department of Chemistry, College of General Studies Hanyang University)
  • Published : 1973.12.30
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Abstract

Kinetic study of halide exchange for dimethylsulfamoyl chloride in dry acetone by using radioisotopic halide ions has been carried out at two temperatures. The result of the order of nucleophilicity, as compared with benzenesulfonyl chloride, shows a similar tendency but reaction rate is slower, more than $10^{-2}$times, than benzenesulfonyl chloride. The activation parameter, ${\Delta}H^{\neq}\;and\;{\Delta}S^{\neq}$ decrease in sequence $Cl^-\;>\;Br^-\;>\;I^-$ in dimethylsulfamoyl chloride but it is the reverse order found for benzenesulfonyl chloride. The results are interpreted with bond-breaking, bond-formation, and electronic requirments, and in the light of HSAB Principle.

Dimethylsulfamoyl chloride의 할라이드 교환반응을 무수 아세톤 용매속에서 방사성 할라이드 이온을 사용하여 두 온도에서 속도론적으로 연구하였다. 그 결과를 benzensulfonyl chloride의 경우와 비교해 보면 친핵성에 있어서는 거의 비슷한 경향성을 나타내나, 반응속도는 dimethylsulfamoyl chloride 쪽이 $10^{-2}$배 이상이나 느린 경향을 나타낸다. 또한 활성화 파라미터, ${\Delta}H^{\neq}$나 ${\Delta}S^{\neq}$는 benzensulfonyl chloride의 경우와는 반대로 dimethylsulfamoyl chloride의 경우는 $Cl^-\;>\;Br^-\;>\;I^-$의 순서로 감소함을 나타낸다. 이 결과를 bond-breaking, bond formation, electronic requirment 및 HSAB 원리로 설명하였다.

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