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5‐Imino‐Δ 3 ‐1,2,4‐thiadiazoline derivatives with a linear N‐S…O grouping. Synthesis and crystal structures
Author(s) -
L'abbé Gerrit,
Vermeulen Guido,
Toppet Suzanne,
King Geoffrey S. D.,
Aerts Jozef,
Sengier Lieve
Publication year - 1981
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.5570180708
Subject(s) - chemistry , zwitterion , dimethyl acetylenedicarboxylate , reagent , crystal structure , chloride , medicinal chemistry , solvent , polar , organic chemistry , molecule , catalysis , cycloaddition , physics , astronomy
A series of carbonyl derivatives of 5‐imino‐Δ 3 ‐1,2,4‐thiadiazolines has been prepared and shown by X‐ray analysis of a selected example to have a trithiapentalene‐like structure. When diphenylketene was used as acylating reagent, the primary product ( 14 ), obtained at room temperature, rearranged on heating in a polar solvent into a Δ 2 ‐thiazolin‐4‐one ( 15 ). The structure of 15 has been confirmed by X‐ray analysis, and shown to be a zwitterion. Rearranged products ( i.e. , 16 and 20‐22 ) were also obtained when 3 was reacted with dimethyl acetylenedicarboxylate or methanesulfonyl chloride, whereas tosyl chloride gave normal tosylated derivatives ( 17‐19 ). The latter have also a nearly linear N‐S…O arrangement, but the interaction between S and O is weak.