Synthesis of new bicyclo[4.1.0]heptane-2,4-dione derivatives and their herbicidal activity

Abstract

Various triketone type 4-HPPD inhibitors were synthesized and their herbicidal activity and corn safety were evaluated. In the course of synthetic studies, we invented convenient methods to synthesize novel benzoyl-substituted bicyclo[4.1.0]heptanediones, and it was found that some showed excellent herbicidal activity against weeds in a corn field. Among these compounds, 3-(4-chloro-2-nitrobenzoyl)bicyclo[4.1.0]heptane-2,4-dione was found to be not only highly active against broadleaf weeds but also grass weeds, whereas it caused severe damage to corn. As a result of further efforts to modify benzoyl substituents, we found a compound, (1R*,6R*)-3-(2-chloro-4-methylsulfonylbenzoyl)bicyclo[4.1.0]heptane-2,4-dione, which provided a good combination of herbicidal activity and corn safety.

4-Hydroxyphenylpyruvate Dioxygenase Inhibitors: From Molecular Design to Synthesis

“…The bioactivity results showed high herbicidal activity against broad-leaved weeds and a good safety profile against corn (Scheme 9). 86 Benzofuran is a wide range of bioactive natural product. Therefore, benzofuran may be a promising aromatic moiety for integration into the 1,3-dicarbonyl pharmacophore.…”

Weed Control, 2. Individual Herbicides

“…The latter is rearranged to the desired product with potassium cyanide in the presence of triethylamine [392].…”

“…Sulcotrione is made according to the procedure given above for Mesotrione but with 3-methylmercaptochlorobenzene as starting material [392].…”

“…Tembotrione can be synthesized according to the above procedure for mesotrione but using 2-(2,2,2-trofluoromethoxymethyl)-3-mercaptomethylchlorobenzene [392,398].…”

Phosphine-catalyzed sequential annulation domino reaction: rapid construction of bicyclo[4.1.0]heptene skeletons

“…heptane ring systems are found in a variety of natural products and biologically active substances (Scheme 1). [1][2][3][4][5] They are also key building blocks in organic synthesis because of their latent reactivity inherent within their structure and may participate in a wide range of ring-opening reactions. 6 Among the various methods developed in the past decades for the synthesis of these useful architectures, the transitionmetal-catalyzed intramolecular cycloisomerization of heteroatom tethered 1,6-enynes is an important and commonly employed process that contributes to atom economy concepts (Scheme 2).…”