Herbicidal activity and biochemical characteristics of the botanical drupacine against Amaranthus retroflexus L.

Botanical herbicide has been a hot topic in the research and development of novel pesticides. The herbicidal activity and biochemical characteristics of the botanical compound drupacine were studied by evaluating its effects on seed germination, seedling growth, morphological and physiological characteristics of Amaranthus retroflexus. Drupacine inhibited seed germination and seedling growth, and had a median inhibition concentration(IC50) value of 38.99 mg L-1against A. retroflexus root. The α-amylase activity and soluble sugar content in treated plants were significantly lower than that of the control. The expression of α-amylase gene was dosage-dependently inhibited compared to the untreated control. This suggested that inhibition of α-amylase activity was a mode of action on seed germination. The root hairs were significantly decreased and part of the root cap fell off after treatment with drupacine. The ultrastructure observation showed that cell damage of root tips increased with the treatment time. Drupacine also increased the relative conductivity and malondialdehyde(MDA) content. Peroxidase(POD), catalase(CAT), and superoxide dismutase(SOD) activities were significantly enhanced in the treatment compared to the control. These findings indicated that the physiological and biochemical reaction changes leading to morphological and membrane injuries were the main effects of drupacine on the inhibition of seedling growth. Drupacine can be developed as a botanical herbicide.

Antifungal,Insecticidal and Herbicidal Properties of Volatile Components from Paenibacillus polymyxa Strain BMP-11

The volatiles produced by Paenibacillus polymyxa strain BMP-11 which was isolated from the rhizosphere soil of cucumber in a greenhouse were analyzed by SPME-GC-MS.Based on the preliminary test,three kinds of purchased commercial products 1-octen-3-ol,benzothiazole and citronellol were chosen to give further assessment of their bioactivity.Antifungal bioassays in sealed dishes revealed that those three compounds strongly inhibited the mycelia growth of the eight pathogens at a low treatment dosage and induced the mycelial morphological abnormalities.During the experiment,we even found that citronellol completely prevented the pigment production of the tested fungus,Fusarium oxysporum,however,1-octen-3-ol and benzothiazole had slight effect.The germination was inhibited to different degrees when spores of Botrytis cinerea exposed to these compounds for 24 h in water agar plate.Furthermore,fumigation results showed that 1-octen-3-ol and benzothiazole had strong toxicity against Tribolium castaneum,LC50 was 16.76 and 3.50 mg L-1,respectively.The fumigation activity was also found similar to the positive control,1,3-dichloropropene （LC50 =10.13 mg L-1）.Results of herbicidal assays showed that tested compounds had inhibitory effects on the seed germination and seedling growth of Amaranthus retroflexus,Echinochloa crusgalli and Chenopodium album.Findings of the present study suggested that the antifungal,insecticidal and herbicidal properties of the components were contained in volatiles.These agents or even their derivatives may have a potential to be used as fungicide,insecticide as well as herbicide.

Isolation and Structural Indentification of Herbicidal Toxin Fractions Produced by Pythium aphanidermatum

In order to understand the compsition and structure of herbicidal component of Pythium aphanidermatum,the isolation and structural indentification were researched.The culture filtrate was extracted by ethyl acetate,petroleum,and chloroform with the same volume respectively and the activity of the crude toxin was bioassayed.The toxin was separated by using the method of thin layer chromatography（TLC）,then the main fraction was separated by HPLC,and the structure was analyzed by the sepctrum of IR,13C-NMR and 1HNMR.The results showed that the ethyl acetate extracts had the strongest herbicidal activity.Using the method of TLC,the bioassay results showed that the extracts with Rf 0.19 had the strongest effect on weeds and the inhibition to Digitaria sanguinalis and Amaranthus retroflexus reached five levels,and the component was proved to be dimethyl o-phthalate from the spectrum of IR,13C-NMR and 1HNMR,which was one of the components from the toxin,and it had herbicidal activity.

Synthesis and Herbicidal Activity of Novel Sulfonylureas Containing Thiadiazol Moiety

Thirteen novel sulfonylureas containing thiadiazole moiety were synthesized in a two-step reaction. Their structures were determined using IR, ^1H NMR, HRFTMS, and elemental analysis. Herbicidal activities of these compounds were determined in the green house bio-assay. The results show that four compounds among them exhibit some activity toward four tested herbs.

Synthesis and Herbicidal Activity of Novel 5-Substituted Benzenesulfonylureas

Sulfonylurea herbicides have been widely used because of their low application rates, good crop sdeetivities and low mammalian toxicities. However, some sulfonylureas might persist unfavourably in the environment with residual problems. In order to look for ecologically safer and environmentally benign sulfonylureas, and on keeping the pyrimidine ring being monosubstitated, 15 novd C5-monosubstituted benzenesulfonylurea compounds were synthesized. The structures of all the compounds synthesized were confirmed by demental analysis and ^1H NMR. Preliminary herbicidal activities of these new sulfonylurea compounds were determined by ALS screening （ in vitro） and pot bioassay experiments（ in vivo）. The herbicidal results show that some novel sulfonylureas are comparable to commercial Foramsulfuron and Monosulfuron.

Syntheses, Structures and Herbicidal Activity of Bis(5-R-2-hydroxybenzylidene) Thiocarbohydrazide Monobutyltin Complexes [R: H(T1), Me(T2)]

The 1,5-disubstituted thiocarbohydrazide ligands were prepared by the condensation of thiocarbohydrazide with salicylaldehyde and 5-methylsalicylaldehyde, respectively. The butyltin complexes,[(5-R-2-hydroxy)ArCH=NNH]2 CS(n-BuSnCl)2, R = H(T1);R = Me(T2), based on the1,5-disubstituted thiocarbohydrazide were obtained by microwave-assisted solvothermal reaction of n-butyltintrichloride precursor with the ligands in methanol environments, which have been structurally characterized by elemental analysis, IR and(1 H, 13 C) NMR spectra. The crystals belong to monoclinic system, space groups C2/c(T1) and Pc(T2), respectively. The Sn atom is six-coordinated with distorted octahedral geometry by O, N and S atoms from ligand, C atom of butyl and two Cl atoms. In the crystal, complex T1 forms three-dimensional supramolecular assembly mediated by noncovalent interactions such as C–H···Cl and π-stacking interactions.Similarly, T2 forms an interesting two-dimensional supramolecular structure by noncovalent interactions(e.g. C–H×××Cl and N–H×××Cl) of one-dimensional band-like chain. These ligands and its butyltin complexes have growth effect on the target plants, such as Portulaca oleracea L.,Amaranthus spinosus L., Cassia tora L., Brassica campestris L. ssp. chinensis var. utilis Tsen et Lee and Amaranthus tricolor L. The ligand L1 has a good inhibitory effect on the growth of Cassia tora L., and complex T2 has selective inhibition on the growth of Portulaca oleracea L. and Amaranthus tricolor L., which can be used as a candidate compound for Cassia tora L., Portulaca oleracea L.and Amaranthus tricolor L. herbicide.

Synthesis and Herbicidal Activities of 3-(Substituted phenyl)isoxazole Derivatives

Several novel 3-(substituted phenyl)isoxazole derivatives were prepared from phenyl butan-1,3-dione. Their structures were confirmed by 1H NMR, IR, and CIMS. Preliminary bioassay showed that some of them exhibited good activities toward various weeds.

Novel Synthesis,Crystal Structure and Herbicidal Activity of(3R,4R)-4,7,7-Trimethyl-6-oxabicyclo[3.2.1]octane-3,4-diol

The title compound, （3R,4R）-4,7,7-trimethyl-6-oxabicyclo[3.2.1]octane-3,4-diol （Cl0HlsO3）, has been synthesized by using one-step catalytic synthetic method from a-pinene and structurally characterized by means of IR, JH-NMR, J3C-NMR, HRMS and single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group P21/n with a = 7.277（4）, b = 18.177（11）, c = 7.939（5） A, β = 91.122（8）°, Z = 4, V = 1049.9（11） A, Dc = 1.178 g/cm3, Mr = 186.24, λ（MoKa） = 0.71073 A, μ = 0.09 mm^-1, F（000） = 408, R = 0.051 and wR = 0.144. The title complex molecules contained two hydroxyls and are connected through hydrogen bonds to generate a two-dimensional network. Especially, the preliminary herbicidal activity results show that the title compound exhibits herbicidal activity against rape （Brassica campestris） and barnyard grass （Echinochloa crusgalli）.

Synthesis and Herbicidal Activities of N'-(substituted pyrimidin-2-yl)-N-Substituted Phenoxyacetyl Thiourea Derivatives

Fifteen N'-(substituted pyrimidin-2-y1)-N-substituted phenoxyacetyl thioureas were synthesized and tested for biological activities. All of them are new compounds and their structures were confirmed by IR. IHNMR. MS and elemental analysis. Some of the target compounds showed excellent inhibitory activities against root and stalk of dicotyledon plant (such as radish). and selective on monoctyledon plant (such as rice).

Synthesis and Herbicidal Activity of Novel Sulfonylurea Derivatives

Sulfonylurea herbicides have been applied worldwide in agriculture. Some sulfonylurea residues might exist in soil longer than that people expected. However, flupyrsulfuron-methyl-sodium which was firstly reported as a new 5-substituted sulfonylurea herbicide has less than one month residual life. Therefore, 5-substituted benzenesulfonylureas are potential molecules to regulate its residual situation. In order to develop new sulfonylurea derivatives, the substituent on the critical 5-posotion of the benzene ring was optimized. On the basis of our former work on sulfonylureas which contains a characteristic mono-substituted pyrimidine moiety, twenty-six new sulfonylurea deriva- tives were synthesized and their structures were confirmed by 1H NMR, 31p NMR and elemental analysis. The greenhouse bioassay tests show that some title compounds exhibit potent herbicidal activity.

Synthesis,Crystal Structure and Herbicidal Activity of N-(4-Methylbenzyl)-4-(3-fluorophenyl)-4-piperidinol Hydrochloride

A novel compound N-（4-methylbenzyl）-4-（3-fluorophenyl）-4-piperidinol hydrochloride has been synthesized and its structure （C19H23ClFNO, Mr = 335.83） was characterized by elemental analysis, IR, ^1H NMR, MS and single-crystal X-ray diffraction analyses. The crystal belongs to the triclinic system, space group P1 with a = 7.2163（6）, b = 10.7905（9）, c = 12.2651（10） A, α = 109.576（2）,β = 98.407（2）,γ= 95.956（2）°, V= 878.14（13）A3, Z = 2, Dc = 1.270 g/cm^3,μ = 0.231 mm^-1, F（000） = 356, S = 1.100, the final R = 0.0525 and wR = 0.1425 for 3206 unique reflections （Rint = 0.0140） with 2736 observed ones （I 〉 2σ（I））. The piperidine ring exhibits a chair conformation. The dihedral angle made by the methyl- and fluoro-substituted benzene rings is 66.84（7）°. There are some intra- and intermolecular hydrogen bonding interactions among the molecules, which stabilize the whole crystal structure. The preliminary biological activity tests indicate good herbicidal activity for the title compound, in particular against the roots of some tested plants （such as Brassica campestris L. and Echinochloa crusgallis L.）.

Isolation and Structural Identification of Herbicidal Active Substance from Root of Flaveria bident(L.) Kuntze

In order to understand the composition and structure of herbicidal active substance from the root of Flaveria bidentis （L.） Kuntze, the isolation and structural identification were researched in this paper. The crude extract from the root ofF. bidentis （L.） Kuntze was extracted by petroleum ether, ethyl acetate, and water saturation of n-butyl alcohol, respectively, and the extraction fluid was separated by using the method of TLC, then the main fraction was separated by HPLC, and the structure of the herbicidal active substance was analyzed by LC-MS, elemental analysis and ~H-NMR. The results showed that the petroleum extraction had the strongest herbicidal activity, and the purple blue stripe separated by TLC had the strongest effect on Digitaria sanguinalis. The herbicidal active substance was identified as ct-terthienyl according to the data of LC-MS, elemental analysis and 1H-NMR.

Synthesis and herbicidal activities of pyridyl sulfonylureas:More convenient preparation process of phenyl pyrimidylcarbamates

Four 4-monosubstituted pyrimidine pyridyl sulfonylureas were synthesized from pyridinesulfonamide and phenyl pyrimidylcarbamate and screened for herbicidal activities. We also reported a convenient preparation process of phenyl pyrimidylcarbamates from pyrimidineamine and phenyl chloroformate.

Possible Mechanism Associated with Herbicidal Activity of Soybean Meal Hydrolysate (SMH)

Soybean meal hydrolyzate （SMH） has been proposed for use as a natural preemergence herbicide.However,the mechanism by which SMH exerts its herbicidal activity remains unclear.In this paper,the herbicidal activities of SMH against perennial ryegrass （Lolium perenne L.） under non-sterile and sterile conditions were evaluated and the relationship between the molecular weight of the ultrafiltration （UF） fractions of SMH and their herbicidal activities were investigated.Besides,the ammonia content changes of the media of SMH treatments 7 d after incubation were also analyzed.The results showed that SMH inhibited the radicle growth of germinating L.perenne seeds in a dose-dependent manner under non-sterile condition.However,SMH in the concentrations investigated increased the radicle length and shoot length by 14-17% and 11-15% respectively under sterile condition.The ammonia contents in the SMH media at all treatments increased greatly from less than 0.01 mg L-1 to up to 11.86-41.37 mg L-1 after 7 d incubation under non-sterile condition.However,ammonia content did not change under sterile condition,proposing that the herbicidal activity might be caused by the free ammonia released from SMH by microbial activity.There was no difference on the perennial ryegrass radicle inhibition among the UF fractions of SMH on an equivalent N basis.It could be concluded that SMH exerted its herbicidal activity through the free ammonia released under non-sterile condition instead of by specific peptide（s） in SMH.

Herbicidal Activities of Eupatorium adenophorum Extracts by 3 Extraction Methods

[ Objective ] The paper was to screen the better extraction method for herbicidal active substances of Eupatorium adenophorum. [ Method ] Three com- mon extraction methods, Soxhlet extraction, ultrasonic extraction and conventional extraction method, were used to prepare E. adenophorum extracts, and the herblcidal activity of E. adenophorum extracts extracted by 3 methods was studied by seed germination method. [ Result] The extraction rate of Soxhlet extraction was the highest of （22.54 ± 0.48 ）%, and the herbicidal activities of E. adenophorum extracted by Soxhlet extraction was relatively stronger. [ Conclusion] Soxhlet extraction was the better extraction method for herbicidal active substances of E. adenophorum.

Antimicrobial,herbicidal and antifeedant activities of mansonone E from the heartwoods of Mansonia gagei Drumm

In vitro biological activities including anti-phytopathogenic fungi, antibacterial, antifeedant and herbicidal activities of the extracts from the heartwoods of Mansonia gagei Drumm. were evaluated. The dichloromethane （DCM） extract displayed antifungal activity against four plant pathogenic fungi （Altemaria porri, Colletotrichum gloeosporioides, Fusarium oxysporum and Phytophthora parasitica） higher than the methanolic （MeOH） extract. The separation of the DCM extract using bioassay guided antifungal activity against P. parasiUca led to the isolation of mansorins A, B, and C, mansonones C, E, G and H. Among isolated compounds, mansonone E displayed the highest antifungal activity against P. parasitica, followed by mansonone C, mansorin B and mansonone G. This potent compound revealed the same minimum inhibitory concentrations （MIC） of 31 μg mL-1 against C. gloeosporioides and P. parasitica, and minimum fungicidal concentration （MFC） of 31 and 125 μg mL-1, respectively. Moreover, mansonone E exhibited highly significant antibacterial activity against both Xanthomonas oryzae pv. oryzae （Xoo） and X. oryzae pv. oryzicola （Xoc） with MIC and minimum bactericidal concentration （MBC） as 7.8 and 〉500μg mL-1, respectively. This compound furthermore could inhibit the feed of Spodoptera litura with 45.9% antifeedant and significantly herbicidal activity reduced the shoot and root growth of Brassica chinensis, Oryza sativa, Mimosa pigra and Echinochlooa crus-galli. Mansonone E has potential as a new natural pesticide for agricultural plant pathogen management.

Synthesis, Crystal Structure, and Herbicidal Activity of(3R,4R)-4,7,7-Trimethyl-6-oxabicyclo[3.2.1]octane-3,4-diol Mono-fatty Acid Esters

Four mono-fatty acid esters(Ia～d) were synthesized via the esterification of(3R,4R)-4,7,7-trimethyl-6-oxabicyclo[3.2.1]octane-3,4-diol(I) with fatty acid chlorides(CH_3(CH_2)_nCOCl, n = 0, 2, 4, 6) and structurally characterized by means of H RMS, IR, ~1 H-NMR, ^(13)C-NMR and X-ray diffraction. Compounds Ia～d all belong to monoclinic system, P2_1/c space group. Intermolecular O(2)–H(2)···O(1) hydrogen bonds, intramolecular O(2)–H(2)···O(3) hydrogen bonds and van der Waals' interaction between fatty acid ester groups link each of the mono-fatty acid ester molecules into a bilayer structure similar to liposome with the exposed hydrophobic moiety and the sandwiched lipophilic moiety. Especially, compounds Ia～d could be dissoluble or scattered in aqueous solution and showed hydrophilic/lipophilic property-dependent herbicidal activity against the dicotyledon plant rape(Brassica campestris) and the monocotyledon plant barnyard grass(Echinochloa crus galli). At the concentration of 10 mmol·L^(-1), the inhibition rates of compounds Ia～d against the root growth of rape are 31.9, 90.8, 99.5 and 100%, respectively and the inhibition rates against the shoot elongation of barnyard grass are 19.3, 50.0, 80.2 and 100%, respectively.

Synthesis, Crystal Structure and Herbicidal Activity of Methyl(E)-α-(Methoxyimino)-2-((4-(3-chloro-5-(trifluoromethyl)-pyridine-2-yl)phenoxy)methyl)benzeneacetate

The title compound methyl(E)-α-(methoxyimino)-2-((4-(3-chloro-5-(trifluoromethyl) pyridine-2-yl)phenoxy)methyl)benzeneacetate(C23 H18 ClF3 N2 O4) has been synthesized and structurally characterized by 1 H and 13 C NMR, and HRMS. Its absolute molecular configuration was investigated by X-ray crystallography. The crystal crystallizes in monoclinic system, space group P21/c with a = 15.0928(7), b = 19.6070(10), c = 7.5535(5) A,β= 98.176(5)°, V = 2212.6(2)A3, Z =4, Dc = 1.438 g/cm^3, F(000)= 984,μ(Mo Kα)= 0.231 mm-1, the final R = 0.0619 and wR = 0.1681 with 4034 observed reflections with I > 2σ(I). The title compound has significant inhibitory rate against broadleaf weeds. They are all 100% under the dose of 37.5 g.a.i/ha, which was better than mesotrione.

Synthesis and Herbicidal Activity of Novel Phenoxysulfonylureas Derivatives

Thirteen novel phenoxysulfonylureas derivatives were synthesized, and their structures were confirmed by MS, NMR and element analysis. The herbicidal activity and structure-activity relationship were also investigated. The results of preliminary active tests indicate that the compounds show moderate herbicidal activity.

Evaluation and Purification of Herbicidal Metabolites Produced by T.longibrachiatum

Laboratory tests were conducted to screen, purify and evaluate the potential herbicidal metabelites produced by five different Trichoderma species on preventing seed germination （ SGe） and shoot/root growth （ SGr/RGr ） of weeds. The results showed that the inhibiting rates （ IR, % ） on SGe and SGr/RGr of seedlings with 10% and 20% diluted culture filtrates produced by the strain of Tr673 were significantly higher （P ≤0.05） compared to those produced by the strains of Tr319, Tr347, Tr324 and Tr85. Purification of the metabolites of Tr673 culture filtrate was achieved by using silica gel column chromatography, preparative high- performance liquid chromatography and other methods. Ninhydrin reaction of the hydrolysate and the negative response of purified compound suggested that this compound could be a type of poptaibels. The bioassay with purified compound （62.5 mg/L） of Tr673 showed that SGr/RGr rates （ % ） of the weeds were significantly （P≤0. 05 ） decreased compared to those with chemical herbicide-glyphosate.