Synthesis and evaluation as biodegradable herbicides of halogenated analogs of L-meta-tyrosine

L-meta-tyrosine is an herbicidal nonprotein amino acid isolated some years ago from fine fescue grasses and characterized by its almost immediate microbial degradation in soil (half-life <24 h). Nine monohalogenated or dihalogenated analogs of this allelochemical have been obtained through a seven-step stereoselective synthesis from commercial halogenated phenols. Bioassays showed a large range of biological responses, from a growth root inhibition of lettuce seedling similar to that noted with m-tyrosine [2-amino-3-(2-chloro-5-hydroxyphenyl)propanoic acid or compound 8b] to an increase of the primary root growth concomitant with a delay of secondary root initiation [2-amino-3-[2-fluoro-5-hydroxy-3-(trifluoromethyl)phenyl]propanoic acid or compound 8h]. Compound 8b was slightly less degraded than m-tyrosine in the nonsterilized nutritive solution used for lettuce development, while the concentration of compound 8h remained unchanged for at least 2 weeks. These data indicate that it is possible to manipulate both biological properties and degradation of m-tyrosine by halogen addition.