The reactions of 2,4-dinitrobenzenesulfonyl chloride, and o-nitrobenzenesulfonyl chloride with potassium superoxide ($KO_2$) were carried out at -35˚-0℃ in various solvents such as dimethyl sulfoxide, tetrahydrofuran, and acetonitrile in order to study on the peroxy-intermediates such as peroxy-sulfenate and sulfonate which have been postulate to be unstable intermediate. The treatment of two arylsulfonyl chlorides with $KO_2$ gave only one product, i.e., the corresponding potassium sulfonate in good yields.
The reactions appear to be initiated by a nucleophilic attack of superoxide ion ($O_2^{\bar{\cdot}}$) on the sulfur atom to form peroxy-sulfonate intermediates, which convert to the corresponding sulfonates. When dimethyl sulfoxide was used as a trapping agent for the peroxy oxygen of peroxy-sulfonate intermediate, actually dimethyl sulfone of oxidation product along with the sulfonate was obtained in good yield. Thus, the reaction of arylsulfonyl chloride with $O_2^{\bar{\cdot}}$ undoubtedly is initiated by forming peroy-sulfonates, which are available as a new oxidizing reagent under mild condition in aprotic organic solvents.
While, the reactions of 2,4-dinitrobenzenesulfenyl chloride, and o-nitrobenzenesulfenyl chloride with $KO_2$ in THF or $CH_3CN$ gave the corresponding sulfonates and interestingly the corresponding disulfide were also obtained.
In the case of 2,4-dinitrobenzenesulfenyl chloride, only bis (2,4-dinitrophenyl) disylfide was obtained as main product. From the observation of these facts the reactions appear to be initiated by a nucleophilic attack of $O_2^{\bar{\cdot}}$ on the sulfenyl sulfur atom to form a peroxy-sulfenate intermediate, which may compete two pathways: one is proceeded via cleavage of peroxy-sulfenate intermediate to form thiyl radical yielding the disulfide, and the other is converted to peroxy-sulfenate intermediate yielding the sulfonate.
The reactions of 1,3-disubstituted thioureas with $O_2^{\bar{\cdot}}$ in DMSO or DMF gave the corresponding urea. In the case of using THF or $CH_3CN$ as solvent, the same reactions yielded the corresponding symmetrical guanidine derivatives through the mechanism is not clear yet.
아릴술포닐클로라이드, 아릴술페닐클로라이드와 티오우레아 유도체를 여러가지 용매하에서 반응시켜 불안정한 반응중간체인 과산화물에 대한 연구를 하였다.
아릴술포닐클로라이드와 아릴술페닐클로라이드의 경우에는 두가지 경우 모두가 유황원자에 슈퍼옥사이드의 친핵공격에 의해서 반응이 시작되어 퍼옥시술포네이트 (혹은 퍼옥시술페네이트) 중간체를 형성하여 생성물로 전환되는 것으로 생각된다.
그 이유는 트랩하기 위한 시약으로 디메틸술폭사이드나 칼콘유도체를 사용했을때, 생성물인 디메틸술폰과 칼콘 에폭사이드 유도체를 얻음으로써 설명된다.
한편, 티오우레아 유도체인 경우에는 슈퍼옥사이드와 반응하면 용매를 디메틸술폭사이드 (혹은 디메틸포름아미드)를 사용했을때 대응되는 우레아가 생성되고, 테트라히드로퓨란이나 아세트니트릴를 용매로 사용하면, 구아니딘 유도체가 생성되는데 그에 대한 반응기구는 아직 뚜렷이 밝혀지지 않았다.
