ヘテロ原子転位

抄録

New heteroatom rearrangements are described :
“S, N-, O, N-, and N, N-rearrangements” take place to afford the corresponding 1, 3-thiazines, 1, 3-oxazines, and pyrimidines when 3-alkyl-heteroatom group (MeS or MeSe) -3-heteroatom group (SH, OH, or NHPh) substituted acrylonitriles condense with carboxylic acids in the presence of dehydrating agents such as PPE, PPSE, phosphorus oxychloride, and 1-propanephosphonic acid cyclic anhydride. The key step of this reaction is considered to be the acylation of the cyano group of acrylonitriles followed by the 1, 3-transfer of the alkylheteroatom group.
In connection with this study, several new reagents and reactions are developed ; (1) Polyphosphate condensation reagent : PPSE (polyphosphoric acid trimethylsilyl ester); (2) O/S Exchange reagent : 2, 4-bis (phenylthio) - 1, 3-dithia-2, 4-diphosphetane 2, 4-disulfide ; (3) Decarboxyamidation reaction ; (4) Synthesis of S, Se-, S, Se'- and S, S'-dialkyl (di) thioselenocarbonates ; (5) Synthesis of 1, 3-selenazines.