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Toxic chlorinated methanoisobenzofuran derivatives
Author(s) -
Weil E. U.,
Colson J. G.,
Hoch P. E.,
Gruber R. H.
Publication year - 1969
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.5570060509
Subject(s) - chemistry , ketone , ether , yield (engineering) , alcohol , sulfuric acid , organic chemistry , medicinal chemistry , norbornene , materials science , monomer , metallurgy , polymer
Upon treatment with alcoholic base, 1,4,5,6,7,7‐hexachloro‐5‐norbornene‐ endo‐cis ‐2,3‐dimethanol (1) yields a tricyclic ether (111) which is converted by sulfuric acid to two epimeric 4,6,7,8,8‐pentachloro‐octahydro‐4,7‐methanoisobenzofuran‐5‐ones (111 A & B). These relatively nontoxic isomers, upon introduction of two chlorine atoms α and α′ to the ether oxygen, yield two epimeric products of high toxicity to insects and mammals. These 1,3,4,6,7,8,8‐heptachloro‐octahydro‐4,7‐methanoisobenzofuran‐5‐ones (IV A & B) upon transannular dehydrochlorination yield a toxic tetracyclic ketone (VI A). Reduction of this ketone by lithium aluminum hydride affords an alcohol (VII) of similarly high insecticidal toxicity. Nuclear magnetic resonance and infrared spectra are presented as evidence for the indicated structures. Results of this study are interpreted as indicative of the regions of the molecule which are critical in regard to toxicity.