Methylthiomethyl benzotriazole

Oxidative decarboxylation of cycloadducts of (1) affords access to -keto ester functionality. Treatment of the isoprene-(l) cycloadduct with methanol followed by TV chlorosuccinimide afforded the corresponding dimethyl acetal, which could be hydrolyzed to afford the -keto ester (eq 4).  

In bicyclic adducts (eq 1), thiol enol ethers are the direct products of oxidative decarboxylation reduction of the ester and subsequent hydrolysis of the thiol enol ethers affords a-methylene ketones (eq 5). Thus eqs (eq 4) and (eq 5) demonstrate the utility of (1) as a methoxycarbonylketene (2) or methyleneketene (3) synthon in [4 + 2] cycloaddition reactions. 

John C. Arthur Robert S. Coleman University of South Carolina, Columbia, SC, USA 

Solubility soluble in ether, THF, ethyl acetate, CH2CI2, CHCI3, and DMSO. 

Handling, Storage, and Precaution hygroscopic, shelf-stable, foul odor. 

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Introduction. All presently known organic synthesis applications of l-(methylthiomethyl)benzotriazole are based on the high acidity of the methylene group protons (and, thus, ready formation of a carbanion) and on the possibility of selective cleavage of benzotriazolyl or methylthio groups under a variety of conditions. 

Synthesis of Ketones from All l Halides or Carbonyl Compounds. l-(Methylthiomethyl)benzotriazole serves as a useful alternative to the well-known carbonyl group synthetic... 

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