Structure-Activity Relationship Study of Xanthoxyline and Related Small Methyl Ketone Herbicides.

Xanthoxyline (1), a small natural methyl ketone, was previously reported as a plant growth inhibitor. In this research, related methyl ketones bearing electron-donating and electron-withdrawing groups, together with heteroaromatics, were investigated against seed germination and seedling growth of Chinese amaranth (Amaranthus tricolor L.) and barnyard grass [Echinochloa crus-galli (L.) Beauv]. The structure-activity relationships (SARs) of methyl ketone herbicides were clarified, and which types and positions of substituents were crucially important for activity were also clarified. Indole derivatives, namely, 3-acetylindole (43) and 3-acetyl-7-azaindole (44) were found to be the most active methyl ketones that highly suppressed plant growth at low concentrations. The molecular docking on the 4-hydroxyphenylpyruvate dioxygenase (HPPD) enzyme indicated that carbonyl, aromatic, and azaindole were key interactions of HPPD inhibitors. This finding would be useful for the development of small ketone herbicides.

The Allelopathic Activity of Extracts and Isolated from Spirulina platensis.

We determined the allelopathic effects of crude organic (hexane, ethyl acetate, and methanol) extracts of the cyanobacterial Spirulina platensis on barnyardgrass (Echinochloa crus-galli (L.) Beauv.) and Chinese amaranth (Amaranthus tricolor L.). The crude ethyl acetate extract showed the highest inhibitory activity and was subsequently fractionated by column chromatography into 23 fractions based on thin-layer chromatography band pattern similarities. Four concentrations (2000, 1000, 500, and 250 ppm) of each fraction were tested for their allelopathic activity. Fractions E6 and E13 exhibited the most significant inhibitory effects against Chinese amaranth. The constituents of the highly active E6F3-E6F5 fractions determined by GC-MS, chromatography, and spectroscopy included the fatty acids, γ-linolenic acid 15, oleic acid 12, and predominantly palmitic acid 7; minor constituents included 2-ethyl-3-methylmaleimide 9 and C11 norisoprenoids (dihydroactinidiolide 10 and 4-oxo-ß-ionone 13). Isolation of E13 fraction by column chromatography revealed four C13 norisoprenoids: 3-hydroxy-ß-ionone 17, 3-hydroxy-5α,6α-epoxy-ß-ionone 18, 3-hydroxy-5ß,6ß-epoxy-ß-ionone 19, and loliolide 20. Their structures were elucidated by NMR spectroscopy. All six isolated norisoprenoids inhibited seed germination and seedling growth of Chinese amaranth at concentrations of 250-1000 ppm. Allelochemicals from S. platensis could be utilized in the development of novel bioactive herbicides.

Enantioselective and Synergistic Herbicidal Activities of Common Amino Acids Against Amaranthus tricolor and Echinochloa crus-galli.

Amino acids have a wide range of biological activities, which usually rely on the stereoisomer presented. In this study, glycine and 21 common α-amino acids were investigated for their herbicidal property against Chinese amaranth (Amaranthus tricolor L.) and barnyard grass (Echinochloa crus-galli (L.) Beauv.). Both d- and l-isomers, as well as a racemic mixture, were tested and found that most compounds barely inhibited germination but moderately suppressed seedling growth. Various ratios of d:l-mixture were studied and synergy between enantiomers was found. For Chinese amaranth, the most toxic d:l-mixtures were at 3:7 (for glutamine), 8:2 (for methionine), and 5:5 (for tryptophan). For barnyard grass, rac-glutamine was more toxic than the pure forms; however, d-tryptophan exhibited greater activity than racemate and l-isomer, indicating the sign of enantioselective toxicity. The mode of action was unclear, but d-tryptophan caused bleaching of leaves, indicating pigment synthesis of the grass was inhibited. The results highlighted the enantioselective and synergistic toxicity of some amino acids, which relied upon plant species, chemical structures, and concentrations. Overall, our finding clarifies the effect of stereoisomers, and provides a chemical clue of amino acid herbicides, which may be useful in the development of herbicides from natural substances.

Herbicidal Activity of Flavokawains and Related trans-Chalcones against Amaranthus tricolor L. and Echinochloa crus-galli (L.) Beauv.

Flavokawains have a broad spectrum of biological activities; however, the herbicidal activity of these naturally occurring chalcones has been less investigated. Flavokawains and their analogues were prepared by the Claisen-Schmidt condensation reaction between xanthoxyline (or aromatic ketones) and a variety of aromatic and heteroaromatic aldehydes. These compounds were then evaluated for their inhibitory effect against representative dicot and monocot plants. Among 45 synthetic chalcones, derivatives containing phenoxyacetic acid, 4-(N,N-dimethylamino)phenyl, N-methylpyrrole, or thiophenyl groups inhibited the germination and growth of Chinese amaranth (Amaranthus tricolor L.) with moderate to high degrees compared to commercial butachlor. For barnyardgrass (Echinochloa crus-galli (L.) Beauv.), most of the thiophenyl chalcones interrupted shoot and root emergence. This finding highlighted the importance of functional groups on the herbicidal activity of chalcones. The level of inhibition also depended on the applied concentrations, plant species, and plant organs. (E)-2-(2-(3-Oxo-3-(thiophen-2-yl)prop-1-enyl)phenoxy)acetic acid (14f) was the most active compound among 45 derivatives. This chalcone could be a promising structure for controlling the germination and growth of weeds. The structure-activity relationship results provide useful information about the development of active chalconoids as novel natural product-like herbicides.

Inhibitory Effects of a Variety of Aldehydes on Amaranthus tricolor L. and Echinochloa crus-galli (L.) Beauv.

Thirty-seven commercial aldehydes containing aliphatic chains and aromatic rings as well as heteroaromatic rings were evaluated for their inhibitory activities against Chinese amaranth (Amaranthus tricolor L.) and barnyardgrass (Echinochloa crus-galli (L.) Beauv). Polysorbate 80 (Tween® 80) was used as a surfactant and the research was preliminarily conducted at 400 µM of all aldehydes. Among these aldehydes, (E)-cinnamaldehyde (7) showed the greatest inhibitory effect on seed germination, shoot and root growth of Chinese amaranth by 54.55%, 75.53%, and 85.13% respectively. Similarly, (E)-crotonaldehyde (5), a related α,ß-unsaturated aldehyde, inhibited the germination and seedling growth of the tested species at a high percentage. Apart from these two unsaturated aldehydes, no other aliphatic aldehydes had a harmful effect on Chinese amaranth. In terms of benzaldehyde (6), it had no effect on the tested plant; however, many of its derivatives displayed some inhibitory activity. Furthermore, for the ten common heteroaromatic aldehydes, picolinaldehyde (32) had a high inhibitory effect on Chinese amaranth which closely related to the effect of (E)-crotonaldehyde (5) and (E)-cinnamaldehyde (7), whereas, other heteroaromatic aldehydes showed lower effects. In the case of a monocot plant, barnyardgrass, no tested aldehydes reduced seed germination, however, (E)-cinnamaldehyde (7), 2,4,6-trimethoxybenzaldehyde (16) and 4-(dimethylamino)benzaldehyde (24) could inhibit the seedling growth of the plant with low to moderate levels. The herbicidal effects of the most active aldehydes were then further investigated in order to find the minimum concentration of these aldehydes suppressing the germination and growth of the tested plants. At concentrations as low as 50-100 µM some aldehydes could inhibit the seedling growth of the tested species. The structure-activity relationship (SAR) study reported here demonstrates the chemical clues governing the inhibitory activity of aldehydes which could be utilized in the development of highly effective herbicides in the near future.

Herbicidal Activities of Some Allelochemicals and Their Synergistic Behaviors toward Amaranthus tricolor L.

Seven allelochemicals, namely R-(+)-limonene (A), vanillin (B), xanthoxyline (C), vanillic acid (D), linoleic acid (E), methyl linoleate (F), and (±)-odorine (G), were investigated for their herbicidal activities on Chinese amaranth (Amaranthus tricolor L.). At 400 µM, xanthoxyline (C) showed the greatest inhibitory activity on seed germination and seedling growth of the tested plant. Both vanillic acid (D) and (±)-odorine (G) inhibited shoot growth, however, apart from xanthoxyline (C), only vanillic acid (D) could inhibit root growth. Interestingly, R-(+)-limonene (A) lightly promoted root length. Other substances had no allelopathic effect on seed germination and seedling growth of the tested plant. To better understand and optimize the inhibitory effects of these natural herbicides, 21 samples of binary mixtures of these seven compounds were tested at 400 µM using 0.25% (v/v) Tween® 80 as a control treatment. The results showed that binary mixtures of R-(+)-limonene:xanthoxyline (A:C), vanillin:xanthoxyline (B:C), and xanthoxyline:linoleic acid (C:E) exhibited strong allelopathic activities on germination and seedling growth of the tested plant, and the level of inhibition was close to the effect of xanthoxyline (C) at 400 µM and was better than the effect of xanthoxyline (C) at 200 µM. The inhibition was hypothesized to be from a synergistic interaction of each pair of alleochemicals. Mole ratios of each pair of allelochemicals ((A:C), (B:C), and (C:E)) were then evaluated, and the best ratios of the binary mixtures A:C, B:C and C:E were found to be 2:8, 2:8, and 4:6 respectively. These binary mixtures significantly inhibited germination and shoot and root growth of Chinese amaranth at low concentrations. The results reported here highlight a synergistic behavior of some allelochemicals which could be applied in the development of potential herbicides.

Evaluation of allelopathic, decomposition and cytogenetic activities of Jasminum officinale L. f. var. grandiflorum (L.) Kob. on bioassay plants.

Methanolic extracts prepared from dried leaves of Jasminum officinale f. var. grandiflorum (L.) Kob. (Spanish jasmine) inhibited seed germination and stunted both root and shoot length of the weeds Echinochloa crus-galli (L.) Beauv. and Phaseolus lathyroides L. The main active compound was isolated and determined by spectral data as a secoiridoid glucoside named oleuropein. In addition, a decrease in allelopathic efficacy appeared as the decomposition periods increased. The mitotic index in treated onion root tips decreased with increasing concentrations of the extracts and longer periods of treatment. Likewise, the mitotic phase index was altered in onion incubated with crude extract. Furthermore, crude extract produced mitotic abnormalities resulting from its action on chromatin organization and mitotic spindle.

Indole synthesis by controlled carbolithiation of o-aminostyrenes.

An effective synthesis of the functionalized indole ring system has been developed from substituted o-aminostyrene starting material. Our methodology involves a novel cascade reaction sequence of alkyllithium addition to the styrene double bond and subsequent trapping of the intermediate organolithium with a suitable electrophile, followed by an in situ ring closure and dehydration to generate the indole ring. This new reaction sequence allows for the introduction of molecular diversity at all positions on the indole scaffold. The procedure was shown to be successful with a range of both C and N substituents on the o-aminostyrenes. The reaction sequence was tolerant to the reactivity range of alkyllithiums such as tert-, sec-, and n-butyllithium. The electrophiles used were DMF, which generated indole products with C-2 unsubstituted, and nitriles, which incorporated the nitrile substituent at C-2. The o-aminostyrene starting materials were generated by a Pd-catalyzed cross-coupling reaction of a vinyl boronic acid equivalent with the readily available substituted o-bromoanilines.