- Aerobic Electrochemical Transformations of DDT to Oxygen-Incorporated Products Catalyzed by a B12 Derivative
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Electrochemical transformations of DDT into oxygen-incorporated products, amides and esters, catalyzed by a B12 derivative, heptamethyl cobyrinate perchlorate, have been developed under aerobic conditions. The dechlorinative oxygenation of DDT forms the acyl chloride as an intermediate for the synthesis of the amide and ester in the reaction with the amine and alcohol, respectively. This electrochemical method demonstrated with 20 oxygen-incorporated dechlorinated products up to 88% yields with 15 new compounds and was also successfully applied to the conversion of methoxychlor to an amide and ester.
- Hisaeda, Yoshio,Moniruzzaman, Mohammad,Ono, Toshikazu,Shimakoshi, Hisashi,Yano, Yoshio
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supporting information
p. 2784 - 2791
(2022/01/19)
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- Reactions of dimethoxycarbene with carbon-sulfur double bonds
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Unlike electrophilic carbenes, which react at sulfur to produce thiocarbonyl ylide intermediates, dimethoxycarbene (DMC), generated by thermolysis of an oxadiazoline at 110°C in benzene in a sealed tube, reacts at carbon, possibly to generate a zwitterionic intermediate, or at both carbon and sulfur in a concerted process that generates a thiirane. In case of the strained 2,2,4,4-tetramethylcyclobutane-1,3-dithione (2), an assumed zwitterion undergoes ring expansion. In analogous reactions, unstrained thiones afford thiiranes, possibly by ring closure of the postulated intermediates or by concerted addition. Desulfurization of thiiranes, which occurs spontaneously in some instances, results in the formation of ketene acetals, many of which hydrolyze during workup. O-Alkyl thioesters and xanthates react to afford products via insertion of the DMC into Csp2-O or Csp2-S bonds, respectively. Copyright
- Dawid, Malgorzata,Reid, Darren L.,Warkentin, John,Mloston, Grzegorz
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- Bis-trimethylsilylacetamide: A reagent for the control of Friedel-Crafts alkylation reactions using methyl chloromethoxyacetate
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The Friedel-Crafts alkylation reactions of electron rich aromatic compounds using methyl α-chloro-α-methoxyacetate and Lewis acids leads predominantly to the formation of diarylacetic acid derivatives in which the second stage of the sequence is favoured by the presence of hydrogen chloride generated in the first step; effective control can be achieved in a number of cases by the addition of bis-trimethylsilylacetamide.
- Earle, Martyn J.,Fairhurst, Robin A.,Heaney, Harry
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p. 6171 - 6174
(2007/10/02)
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