Mode of action of herbicidal derivatives of aminomethylenebisphosphonic acid. I. Physiologic activity and inhibition of anthocyanin biosynthesis

N-Pyridylaminomethylenebisphosphonic acids constitute a class of promising herbicides. Since their mode of action at the cellular level is still poorly understood, we studied the influence of N-pyridylaminomethylenebisphosphonic acids on plant growth, at the whole plant and undifferentiated tissue levels, using seedlings and cell suspension cultures of mono- and dicotyledonous species. These compounds exhibited strong herbicidal properties, being equipotent with the popular herbicide glyphosate. Since they also depressed buckweed anthocyanin biosynthesis, the shikimate pathway could represent a site of action of N-pyridylaminomethylenebisphosphonic acids.

Stereoselective synthesis of 2-amino-1-hydroxy-3-phenylpropylphosphonic acid

Abstract A highly stereoselective synthesis of 2-amino-1-hydroxy-3-phenylpropylphosphonic acid was achieved by simple addition of diethyl phosphite to enantiomeric N-blocked phenylalaninals. These compouds exhibit significant herbicidal activity.

Herbicidal activity of derivatives of 9-aminofluoren-9-ylphosphonic acid

A series of derivatives of 9‐aminofluoren‐9‐ylphosphonic acid (phosphonic analogues of morphactins) were synthesized and screened for herbicidal activity against Lepidium sativum, Cucumis sativus and Lycopersicon esculentum. Ethyl 9‐(N‐alkylamino)fluoren‐9‐yl(phenyl)phosphinates appeared to be equipotent with glyphosate and thus may be recognized as new lead compounds for further structural modifications.

Plant-growth-regulating phosphono peptides

Phosphono peptides exhibited plant‐growth‐regulating activity when tested on Lepidium sativum and Cucumis sativus. The studies have provided evidence that the mechanism of action of these compounds may involve the uptake of the phosphono peptides into the plant, intracellular hydrolysis of the peptide bond and release of the P‐terminal aminoalkylphosphonic acid. This acid or its metabolite is then probably responsible for the observed physiological effect.

Transport of amino acids and their phosphonic acid analogues through supported liquid membranes containing macrocyclic carriers. Experimental parameters

Abstract Amino acid hydrochlorides are well transported through 1-decanol membranes containing Kryptofix 5 or 222 and supported in a porous polyacrylonitrile hollow fiber matrix. Factors which influence the transport of phenylalanine hydrochloride were studied in some detail using this sheet- as well as hollow fibre-supported liquid membranes. These studies show that the choice of the membrane phase, the kind of polymeric support and the mode of membrane preparation are of great importance for the efficiency of the process. The most vital step in the membrane preparation appears to be its activation by soaking in a solution of phenylalanine hydrochloride in a water-ethanol or water-propanol…

Crown-ether mediated transport of amino acids through an immobilized liquid membrane

The ability of soil-borne fungi to degrade organophosphonate carbon-to-phosphorus bonds

The ability of a wide variety of soil-borne fungal strains to degrade four structurally different compounds containing P-C bonds, namely the naturally occurring amino acid ciliatine, the popular herbicide glyphosate, phosphonoacetic acid and 2-amino-3-phosphonopropionic acid, was studied in order to show that soil fungi may play an important role in the biodegradation of organophosphonates. Most of the strains appeared to utilize ciliatine as the sole source of phosphorus for growth. Only a limited number of strains were able to grow on the other phosphonates used in this work. The strains of Trichoderma harzianum, Scopulariopsis sp. and Aspergillus niger chosen for more detailed study show…

Synthesis and herbicidal activity of isoxazole-substituted 1-aminoethylphosphonates and 1-hydroxyethylphosphonates

Isoxazole‐substituted 1‐aminoethyl‐ and 1‐hydroxyethyiphosphonates were synthesized by a multi‐step procedure and were screened for herbicidal activity against Lepidium sativum L. and Cucumis sativus L. All the synthesized compounds exhibited notable herbicidal activity.

ChemInform Abstract: Stereoselective Synthesis of 2-Amino-1-hydroxy-3- phenylpropylphosphonic Acid.

Abstract A highly stereoselective synthesis of 2-amino-1-hydroxy-3-phenylpropylphosphonic acid was achieved by simple addition of diethyl phosphite to enantiomeric N-blocked phenylalaninals. These compouds exhibit significant herbicidal activity.

Mode of action of herbicidal derivatives of aminomethylenebisphosphonic acid. Part II. Reversal of herbicidal action by aromatic amino acids

The herbicidal action of N-pyridylaminomethylenebisphosphonic acids is accompanied by an impairment of anthocyanin biosynthesis. This suggests that they might act as inhibitors of some steps in aromatic amino acid biosynthesis. Herbicidal effects were reversed by aromatic amino acids using both bacterial and plant models, a finding that strongly supports this hypothesis. Structural features of these compounds suggest the sixth enzyme in the shikimate pathway 5-enol-pyruvoylshikimate-3-phosphate (EPSP) synthase as a possible target, since a strong structural similarity exists between aminomethylenebisphosphonic acid and an inhibitor of EPSP synthase, the herbicide glyphosate. This is, howeve…

Effects of aminophosphates and their combinations with glyphosate on the growth ofLepidium sativumL. andCucumis sativusL.

Organophosphonate utilization by the wild‐type strain of cladosporium resinae

We studied the biodegradation of compounds containing phosphorus‐to‐carbon bond by using wild‐type strain of Cladosporium resinae. The substrate specificity of the strain was studied and we found that it is able to utilize a range of structurally diverse organophosphonates as a sole source of phosphorus. This ability is inducible as indicated by the presence of a lag phase of the growth. A popular herbicide glyphosate is also degraded by the fungi. This indicates that Cladosporium resinae may play an important role in biodegradation of this herbicide. The strain which we used, however, did not metabolise any phosphonates when they served as the sole carbon or nitrogen sources.

Plant-growth-regulatingN-(phosphonoacetyl)amines

A series of N‐(phosphonacetyl)amine derivatives were synthesized and screened for plant‐growth regulating activity on Lepidium sativum L. and Cucumis sativus L. Aromatic N‐(phosphonoacetyl)amines. which may be considered as possible analogues of N‐acylaniline herbicides obtained by replacement of their acyl group by the phosphonacetyl moiety, exhibited significant or moderate herbicidal activity. In contrast, N‐(phosphonoacetyl)amino acids and N‐(phosphonoacetyl)aminophosphonic acids promoted the growth of L. sativum and C. sativus roots.

Herbicidal derivatives of aminomethylenebisphosphonic acid. Part III. Structure-activity relationship.

Derivatives of aminomethylenebisphosphonic acids constitute a class of promising herbicides. More than 40 N-substituted aminomethylenephosphonic acids were synthesized and evaluated for their herbicidal activity on common cress (Lepidium sativum L.) and cucumber (Cucumis sativus L.). Some of the tested compounds were found to exhibit strong herbicidal properties being equal in activity with the popular herbicide glyphosate as well as parent N-pyridylaminomethylenephosphonic acids. N-Substituted iminodi(methylenephosphonic) acids, which may be considered as close analog of glyphosate, were inactive toward test plants.

Herbicidal activity of phosphonic and phosphinic acid analogues of glutamic and aspartic acids

Phosphonic and phosphinic acid analogues of glutamic and aspartic acids were synthesized and screened for herbicidal activity on Lepidium sativum L. Depending on the chemical structure, they exhibited significant or moderate herbicidal activity against L. sativum roots (with some representatives being equipotent with phosphinothricin), while their influence on shoot growth was negligible. Cucumis sativus L. appeared to be more tolerant to these analogues. The origin of this selectivity remains to be determined.

Herbicidally Active Derivatives of Aminomethylenebis-Phosphonic Acid-Mode of Action and Structure - Activity Relationship

Abstract: (N-pyridylamino)methylenebisphosphonates exhibit strong herbicidal activity which may be reversed by supplementation of the growth media with aromatic amino acids. They appeare to be the inhibitors of aromatic amino acids biosynthesis acting as inhibitors of DAHP synthase the first enzyme of shikimate pathway. Over 40 analogues of these acids were synthesized in order to determine the structure-activity relationship.

Recent advances in the research on herbicidally active aminomethylelebisphosphonic acids.

Influence of the mode of application of herbicidally active N-pyridylaminomethylenebi-sphosphonic acids on their uptake by plants was studied in some detail. The experimental evidence is given that accounts for a multiple mode of action of these herbicides.

Herbicidal activity of phosphonic, phosphinic, and phosphonous acid analogues of phenylglycine and phenylalanine

A series of phosphonic, phosphinic, and phosphonous acid analogues of phenylglycine and phenylalanine was synthesized and tested as herbicides against Lepidium sativum and Cucumis sativus. Aminobenzylphosphonic acids exhibited notable herbicidal activity and thus represent a group of the most active herbicides found among aminophosphonic acids.

Transport of dipeptides and phosphono dipeptides through an immobilized liquid membrane. Stereoselectivity of the process

Abstract Dipeptide and phosphono dipeptide hydrochlorides permeated well through a 1-decanol membrane supported in a porous polyethylene hollow fiber matrix. This transfer is easily accomplished either by passive or by carrier-facilitated (with Kryptofixes 222 or 5 present in the membrane phase) transport. The transport is stereoselective with l-l dipeptides being transported faster than their l-d isomers.