Ethyl N-tert-butyl-4-nitrobenzenesulfonimidate and isopropyl N-(1-adamantyl)-4-nitrobenzenesulfonimidate have been shown to alkylate a variety of different phenols, along with thiophenol and selenophenol. It was shown that ethylation and isopropylation can be successfully carried out using these sulfonimidates with the help of an acid catalyst, tetrafluoroboric acid dimethyl ether complex. Their ability to alkylate selectively on functionally similar groups resulted in the formation of ethers, sulfides, and selenides. Competitive reactions with sterically hindered phenols formed the less sterically hindered ethers in greater amounts. Electronic substituent effects in para-substituted phenols favored alkylation on the more electron rich phenols. Hammett sigma para-substituent constants correlated with relative rates of phenol alkylations to give negative reaction constant (p) values for each alkyl sulfonimidate reagent. Thus, the major goal of this project was accomplished in finding general trends in functional groups, steric hindrance, and substituent effects to make reasonable predictions for sulfonimidate reactions in the future.
|Commitee:||Maricich, Tom J., Marinez, Eric, Schramm, Michael|
|School:||California State University, Long Beach|
|Department:||Chemistry and Biochemistry|
|School Location:||United States -- California|
|Source:||MAI 53/06M(E), Masters Abstracts International|
|Keywords:||Alkylation, Ethylation, Isopropylation, Phenols, Sulfonimidates|
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