Abstract
The chemistry and applications of tert -butyl-N -chlorocyanamide in a variety of organic transformations is discussed in this account. The reagent was found to be highly versatile for chlorination and oxidation reactions in organic synthesis. tert -Butyl-N -chlorocyanamide is reactive and possesses a high active chlorine content; it is also safe, soluble in all organic solvents, and recyclable. The reagent is stable, in terms of its active chlorine content, under ambient conditions for a period of more than two years. tert -Butyl-N -chlorocyanamide is able to generate a high level of positive chlorine that is mainly responsible for its involvement in many useful organic transformations, including the conversion of sulfides into sulfoxides, ketoximes into gem -chloronitroso compounds, aldoximes into hydroximoyl chlorides and 2-isoxazolines, dialkyl and diaryl phosphites into dialkyl and diaryl chlorophosphates, and secondary alcohols into ketones, as well as the coupling of thiols to give disulfides and the oxidative decontamination of sulfur mustard (a chemical warfare agent) and its simulants. In addition, the reagent can undergo photolytic addition to various olefins.
1 Introduction
2 N -Chlorocyanamides
2.1 Basic Chemistry
2.2 Screening of N -Chlorocyanamides
2.3 Synthesis and Characterization of tert -Butyl-N -chlorocyanamide
2.4 General Properties of tert -Butyl-N -chlorocyanamide
2.5 Solubility
2.6 Safety Studies
2.7 Stability studies
3 Chemical Reactivity
3.1 Addition Reactions
3.1.1 Addition to Olefins
3.2 Chlorination Reactions
3.2.1 Conversion of Ketoximes into gem -Chloronitroso Compounds
3.2.2 Conversion of Aldoximes into Hydroximoyl Chlorides and 2-Isoxazolines
3.2.3 Conversion of Dialkyl and Diaryl Phosphites into Dialkyl and Diaryl Chlorophosphates
3.3 Oxidation Reactions
3.3.1 Conversion of Sulfides into Sulfoxides
3.3.2 Decontamination of Sulfur Mustard and Its Simulants
3.3.3 Coupling of Thiols To Give Disulfides
3.3.4 Conversion of Secondary Alcohols into Ketones
4 Conclusions and Perspectives
Key words
N -chloro compounds -
tert -butyl-N -chlorocyanamide - addition reactions - chlorinations - oxidations
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