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The structure of thianthrenium biscarbethoxymethylide and the corresponding sulfoxide
Author(s) -
Ternay A. L.,
Baack J. C.,
Chu S. S. C.,
Napoleone V.,
Martin G.,
Alfaro C.
Publication year - 1982
Publication title -
journal of heterocyclic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.321
H-Index - 59
eISSN - 1943-5193
pISSN - 0022-152X
DOI - 10.1002/jhet.5570190425
Subject(s) - thianthrene , chemistry , sulfoxide , ylide , sulfur , aryl , oxide , crystal structure , crystallography , solvent , stereochemistry , medicinal chemistry , organic chemistry , alkyl
Thianthrene reacts with one equivalent of diethyl diazomalonate to form the monosulfonium ylide thianthrenium biscarbethoxymethylide. Single crystal X‐ray and 13 C‐nmr establish the conformation as pseudoequatorial (e') in both the solid state and solution. The angle of fold between aryl rings is 135.7°, the nearlyplanar malonylide fragment bisecting this angle. The carbonyl oxygen of the endo carbethoxy group is anti to the nonbonding electron pair on sulfur. The methylide carbon resonates at 50 ppm. The aromatic solvent induced shift (ASIS) technique indicates that thianthrene S oxide also is e'.