Controlled-Release of Plant Volatiles:New Composite Materials of Porous Carbon-Citral and Their Fungicidal Activity against Exobasidium vexans

Citral(Eo)exhibits excellent fungicidal activities.However,it is difficult to maintain long-term fungicidal activity due to its strong volatility.Herein,a controlled-release strategy by using biomass-derived porous carbon(BC)was developed to overcome the drawback of Eo.New composite materials were prepared by loading Eo on tea stem porous carbon(BC@Eo),and their controlled-release fungicidal activity against Exobasidium vexans was assessed.BC with a large specific surface area of 1001.6 m2/g and mesoporous structure was fabricated through carbonization tempera-ture of 700℃.The BC@Eo materials were characterized using Fourier-transform infrared spectroscopy and X-ray powder diffraction.The results suggested that chemical and physical interactions occurred in BC@Eo.The Eo release profile suggested a biphasic pattern with an initial fast release on days 1–14 and a subsequent controlled phase on days 14–30.The in vitro cumulative release percentage of Eo from BC@Eo was 51%during one month,and this result was significantly lower than that from free Eo(cumulative release percentage of Eo of 82%in one week).The anti-fungal activities of Eo and BC@Eo against E.vexans were determined using the inhibition zone method.The results indicated that Eo and BC@Eo formed large inhibition zones of 19.66±0.79 and 21.92±0.77 mm,respectively.The influence on the hyphal structure of E.vexans was observed by scanning electron microscopy on day 30.The hyphal structure of E.vexans treated with BC@Eo was more shrunken than that treated with Eo at 30 days,suggesting that BC@Eo prolongs the fungicidal activity against E.vexans.This study demonstrated that the encapsulation of Eo in BC for developing the BC@Eo materials could be a promising strategy to inhibit volatility and maintain the fungicidal activity of Eo and provide a potential alternative for the reuse of abundant tea biomass waste resources.

Synthesis and Antifungal Activity of 1-(1H-1,2,4-Triazole)-2-(2,4-diflurophenyl)-3-(N-methyl-N-substituted benzylamino)-2-propanols

Eleven 1-(1H-1,2,4-triazole)-2-(2,4-diflurophenyl)-3-(N-methyl-N-substituted benzylamino)-2-propanols were designed and synthesized, on the basis of the crystal structure of P450 cytochrome 14α-sterol demethylase(CYP51) and the docking results of inhibitors to the active site of the enzyme. All title compounds were first by reported. Results of preliminary biological tests showed that most of title compounds exhibited activity against the seven common pathogenic fungi. Compound 11 showed best antifungal activity with broad antifungal spectrum and proved to be more active against Cryptococcus neoformans, Candida albicans, Microsporum lanosum and Trichophyton rubrum than ketoconazole. Compounds 3, 10 and 4 also had high activities.

Synthesis,Crystal Structure and Antifungal Activity of 4-(5-((2,4-Dichlorobenzyl)thio)-4-phenyl-4H-1,2,4-triazol-3-yl)pyridine

The title compound 4-（5-（（2,4-dichlorobenzyl）thio）-4-phenyl-4H-1,2,4-triazol-3- yl）pyridine （C20HI4CI2N4S） was synthesized, and its structure was confirmed by 1H NMR, MS, elemental analyses and X-ray diffraction. It crystallizes in the monoclinic system, space group P21/c with a = 14.885（5）, b = 8.597（2）, c = 16.144（5）A,β= 114.505（4）°, V= 1879.8（10） A3, Z= 8 and R = 0.0320 for 3108 observed reflections with I 〉 2σ（I）. The preliminary biological test shows that the title compound has activities against Stemphylium lyeopersici （Enjoji） Yamamoto, Fusarium oxysporum, sp. cueumebrium, and Botrytis cinerea with inhibitory to be 53.57%, 66.67% and 24.44%, respectively.

Synthesis, Crystal Structure, Docking and Antifungal Activity of a New Pyrazole Acylurea Compound

The title compound N-（（3,5-dimethylphenyl）carbamoyl）-1-methyl-3-（trifluoromethyl）-1 H-pyrazole-4-carboxamide（C（15）H（15）F3N4O2） was synthesized, and its structure was confirmed by 1 H NMR, H RMS and X-ray diffraction. It crystallizes in the triclinic system, space group P1 with a = 11.7147（5）, b = 11.7935（5）, c = 13.6620（5） A, α = 69.755（7）°, β = 66.182（6）°, γ = 72.100（7）°, Dc = 1.423 g/cm^3, Z = 4, V = 1588.88（11） A^3, the final R = 0.0347 and wR = 0.1005 for 7171 observed reflections with I 〉 2σ（I）. The preliminary biological test showed that the title compound has antifungal activities against Fusarium oxysporum, Pseudomonas syringae, Corynespora mazei and Botrytis cinerea at 100 μg/mL as 5.19%, 53.50%, 88.55% and 70.62%, respectively. The docking results indicated the hydrogen bonds formed between the compound and SHD.

Synthesis and fungicidal activity of novel strobilurin analogues containing substituted N-phenylpyrimidin-2-amines

A number of novel strobilurin analogues containing substituted N-phenylpyrimidin-2-amines were synthesized. The structures of these new compounds were confirmed by ^1H NMR, IR and elemental analysis. Biological evaluation in the greenhouse showed several compounds have good fungicidal activities at 25 mg/L.

Synthesis, Crystal Structure and Biological Activity of 1,5-Bis(4-methoxyphenyl)-3-(4-methyl-1,2,3-thiadiazol-5-yl)pentane-1,5-dione

The title compound 1,5-bis（4-methoxyphenyl）-3-（4-methyl-1,2,3-thiadiazol-5-yl）-pentane-1,5-dione （C22H22N2O4S, Mr=410.49） has been synthesized by the reaction of 4-methyl-1,2,3-thiadiazole-5-carbaldehyde with 4-methoxyacetophenone, and its structure was characterized by IR, 1H NMR, H RMS, elemental analysis and single-crystal X-ray diffraction. The crystal of the title compound belongs to monoclinic, space group P21/c with a=11.159（3）, b=9.002（3）, c=20.192（6）, β=93.393（5）°, Z=4, V=2024.6（10） 3 , Dc=1.347 g/cm3 , μ=0.191 mm-1 , F（000）=864, R=0.0333 and wR （I〉2σ （I））=0.0840. In this molecule, the 1,2,3-thiadiazol ring is nearly vertical with both phenyl rings, and intermolecular weak hydrogen bonds of C-H…O and C-H…N types together with π-π stacking interactions and interactions between S（1）…N（2） are observed. The above three kinds of interactions extend the molecules into a two-dimensional layer framework. The preliminary biological test showed that the title compound had fungicidal activity.

Design, Synthesis, and Biological Activity of Novel Aromatic Amide Derivatives Containing Sulfide and Sulfone Substructures

In recent years,the damage caused by soil nematodes has become increasingly serious;however,the varieties and structures of the nematicides available on the market are deficient.Fluopyram,a succinate dehydrogenase inhibitor(SDHI)fungicide developed by Bayer AG in Germany,has been widely used in the prevention and control of soil nematodes due to its high efficiency and novel mechanism of action.In this paper,two series of novel target compounds were designed and synthesized with nematicidal and fungicidal fluopyram as the molecular skeleton in order to introduce sulfide and sulfone substructures.The structures were identified and characterized by 1H nuclear magnetic resonance(NMR),13C NMR,and high-resolution mass spectrometer(HRMS).The bioassays revealed that most of the compounds showed excellent nematicidal activities at 200 lgmL-1 in comparison with fluopyram,while the nematode mortality rate dropped sharply at 100μg·mL-1,except for compounds I-11 and II-6.In terms of fungicidal activity,compound I-9 was discovered to have an excellent inhibitory rate,and a molecular docking simulation was performed that can provide important guidance for the design and exploration of efficient fungicidal lead compounds.

Synthesis, Crystal Structure and Fungicidal Activity of N-(4-tert-buty)-5-(1,2,4-triazol-1-yl)thiazol-2-yl)propionamide

The title compound has been synthesized by the reaction of 4-tert-butyl-5-（1,2,4- triazol-1-yl）-2-aminothiazole with propionic anhydride, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the orthorhombic system, space group Pbca with α = 18.441（2）, b = 8.3284（9）, c = 19.257（2） A, Z = 8, V = 2957.5（5） A3, Mr = 279.37, Dc = 1.255 mg/m3, S = 1.033, μ =0.219 mm^-1, F（000） = 1184, the final R = 0.0349 and wR = 0.0876 for 2629 observed reflections （I 〉 2σ（I））. X-ray crystal structure presents the intermolecular N–H···N hydrogen bond, which plays an important role in stabilizing the crystal structure. The preliminary bioassay indicates that the title compound exhibits potent fungicidal activity against R. Solani （25 mg/L） with inhibition rate of 80.0%.

Synthesis, Crystal Structure and Fungicidal Activity of (Z)-3,3-Dimethyl-1-(1H-1,2,4-triazol-1-yl)butan-2-one O-2-Chlorobenzyl Oxime Nitrate

The title compound has been synthesized by the reaction of 3,3-dimethyl-1-（1H-1,2,4-triazol-1-yl）butan-2-one oxime with 2-chlorobenzyl chloride, and then treated with 65～68% HNO3. Its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group P21/c with a = 14.5481（8）, b = 9.3351（5）, c = 13.1911（7） , β = 98.9450（10）°, Z = 4, V = 1769.67（17） 3, Mr = 369.81, Dc = 1.388 g/cm3, S = 1.06, μ = 0.247 mm-1, F（000） = 776, the final R = 0.0352 and wR = 0.0960 for 3069 observed reflections （I 2σ（I））. X-ray crystal structure presents the intramolecular N–H…O hydrogen bond. The packing is nearly parallel without π-π stacking interactions between two adjacent phenyl rings and stabilized by Van der Waals force. The preliminary bioassay shows that the title compound possesses fungicidal activity against Gibberella zeae at the dosage of 25 mg/L.

Synthesis,Crystal Structure and Fungicidal Activity of(E)-2-[(4-tert-Butyl-5-(4-methoxybenzyl)thiazol-2-ylimino)methyl]phenol

The title compound （E）-2-[（4-tert-butyl-5-（4-methoxybenzyl）thiazol-2-ylimino）methyl]phenol was synthesized by the reaction of 5-（4-methoxybenzyl）-4-tert- butylthiazol-2-amine with salicylaldehyde, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group P21/c with a = 5.9362（8）, b = 11.5070（15）, c = 29.460（4）A, β= 97.326（3）°, V = 1995.9（5） A^3, Z = 4, F（000） = 808, C22H24N2O2S, Mr= 380.49, De= 1.266 g/cm^3, S = 1.031,μ = 0.181 mm^-1, the final R = 0.0474 and wR = 0.1441 for 4327 observed reflections （I 〉 2σ（I））. Intramolecular O-H…N hydrogen bond is observed in the crystal. The preliminary bioassay showed that the title compound exhibits 95% inhibition rate against Rhizoctonia solani at the test concentration of 500 mg/L.

Synthesis, Crystal Structure and Fungicidal Activity of 3-(4-Chloro-3-ethyl-1-methyl-1H-pyrazol-5-yl)-6-(E)phenylvinyltriazolo[3,4-b]-1,3,4-thiadiazole

The crystal structure of the title compound 3 (4 Chloro 3 ethyl 1 methyl 1H pyrazol 5 yl) 6 (E)phenylvinyltriazolo[3,4 b] 1,3,4 thiadiazole (C 17 H 15 ClN 6S, M r =370.87) was determined by single crystal X ray diffraction. The crystal is monoclinic, space group P2 1/n , a=10.862(2), b=11.541(2), c=14\^994(3), β=108.41(3)°, V=1783(1), Z=4, D x =1.381 g/cm -3 , μ =0.3361 mm -1 , and F (000)=768. The results confirmed that the title compound belongs to type E of stereochemistry. The dihedral angle between triazole and 1,3,4 thiadiaole ring is 3° and the torsion angle between 1,3,4 thiadiazole and pyrazole ring is 134.0°.

Essential Oil from Inula britannica Extraction with SF-CO_2 and Its Antifungal Activity

The aim of this study was to determine the extraction technique of supercritical fluid carbon dioxide（SF-CO 2） for the essential oil from Inula britannica flowers and its antifungal activities against plant pathogenic fungi for its potential application as botanical fungicide.The effects of factors,including extraction temperature,extraction pressure,SF-CO 2 flow rate,flower powder size,and time on the essential oil yield were studied using the single factor experiment.An orthogonal experiment was conducted to determine the best operating conditions for the maximum extraction oil yield.Adopting the optimum conditions,the maximum yield reached 10.01% at 40°C temperature,30 MPa pressure,60 mesh flower powder size,20 L h-1SF-CO 2 flow rate,and 90 min extraction time.The antifungal activities of I.britannica essential oil using the SF-CO 2 against the most important plant pathogenic fungi were also examined through in vitro and in vivo tests.Sixteen plant pathogenic fungi were inhibited to varying degrees at 1 mg mL-1concentration of the essential oil.The mycelial growth of Gaeumannomyces graminis var.tritici was completely inhibited.The radial growths of Phytophthora capsici and Fusarium monilifome were also inhibited by 83.76 and 64.69%,respectively.In addition,the essential oil can inhibit the spore germination of Fusarium oxysporum f.sp.vasinfectum,Phytophthora capsici,Colletotrichum orbiculare,and Pyricularia grisea,and the corresponding inhibition rates were 98.26,96.54,87.89,and 87.35% respectively.The present study has demonstrated that the essential oil of I.britannica flowers extracted through the SF-CO 2 technique is one potential and promising antifungal agent that can be used as botanical fungicide to protect crops.

Synthesis and Bioactivity of Novel Aminomethyl-2-(1,2,4-triazol)-4,4-dimethyl-3-pentanone(ol)

Dimethyl-1-(1, 2, 4-triazol) -2- butanone was treated with aqueous formaldehyde to give an additional product, and subsequent elimination by acetic anhydride yielded 4, 4-dimethyl-2-(1, 2, 4-triazol)-1-penten-3-one. Further addition with substituted amines provided a series of (1, 2, 4-triazol)-4, 4-dimethyl-3-pentanone, which were then reduced by KBH4 to obtain a series of (1, 2, 4-triazol)-4, 4-dimethyl-3-pentanol. Their structures were confirmed by 1HNMR and elemental analysis. The results of bioassay showed that the title products possess good fungicidal activities.

Synthesis, Crystal Structure and Biological Activity of 5-(2-Methylphenyl)-1,3,4-oxadiazol-2(3H)-one Derivatives

3-Methyl-5-（2-methylphenyl）-1,3,4-oxadiazol-2（3H）-one （6） and N,N-diethyl-2-（2- methylbenzoyl）-hydrazinecarboxamide （7） were designed and synthesized from 5-（2-methyl- phenyl）- 1,3,4-oxadiazol-2（3H）-one （5） by substituting and ring-opening, respectively. The target compounds were confirmed by IR, JH NMR spectroscopy, MS, elemental analysis and single-crystal X-ray diffraction. Compound 6 （Cl0Hl0N202, Mr = 190.20） crystallizes in the triclinic system, space group P1 with a = 7.4645（16）, b = 10.868（2）, c = 12.970（3） A, α= 110.542（2）, β= 98.142（2）, γ= 99.766（2）°, V = 947.7（3） A3, Z = 4, F（000） = 400, Dc = 1.333 g/cm3, μ = 0.095 mm-1, the final R = 0.0550 and wR = 0.1483 for 2956 observed reflections with I〉 2σ（1）. Compound 7 （C13HI9N302, Mr = 249.31） crystallizes in the monoclinic system, space group C2/e with a = 18.926（3）, b = 12.1853（17）, e = 14.740（2） A, fl = 125.6380（10）~, V= 2762.7（7） A3, Z = 8, F（000） = 1072, Dc = 1.199 g/cm3,μ = 0.083 mm-1, the final R = 0.0554 and wR = 0.1468 for 2395 observed reflections with I 〉 2σ（I）. The preliminary bioassay results indicate that compound 6 exhibits notable fungicidal activities against Fusarium graminearum, Botrytis cinerea, Rhizoctonia cerealis and Colletotrichum capsici at the concentration of 100 μg/mL.

Regioselective Synthesis, Crystal Structure and Biological Activity of Novel 2-Phenylsulfonylhydrazono-3-(3-trifluoromethylphenyl)-2(3H)-thiazoline Derivatives

The title compounds 2-phenylsulfonylhydrazono-3-（3-trifluoromethylphenyl）-2（3H）- thiazoline derivatives were designed and synthesized via the reaction of thiosemicarbazides with chloroacetaldehyde, and their chemical structures were characterized by ^1H NMR, ^13C NMR, elemental analysis and MS. Furthermore, 4a was characterized by single-crystal X-ray diffraction. The target compound 4a （C16H12F3N302S2, Mr = 399.41） crystallized in monoclinic system, P21/c space group with a = 7.7457（4）, b = 13.5850（7）, c = 16.5455（10） A, β= 99.698（2）°, V= 1656.30（16） A3, Dc = 1.602 g/cm^3, Z = 4, F（000） = 816, λ = 0.71070 A,μ（MoKa） = 0.370 mm^-1, R = 0.072 and wR = 0.0867. The crystal structure of 4a revealed the cyclization of thiosemicarbazide moiety with chloroacetaldehyde at the N（l） position. The title compounds exhibited good insecticidal activity against spider mite （Tetranychus cinnabarinus Boisduval） and favorable fungicidal activity against Corynespora cassiicola.

Microwave Assistant Synthesis,Crystal Structure and Biological Activity of 1-(2-Fluorobenzyl)-3-methoxy-4-methyl-1H-1,2,4-triazol-5(4H)-one

The title compound 1-（2-fluorobenzyl）-3-methoxy-4-methyl-lH-1,2,4-triazol- 5（4H）-one （CI1HI2FN302） was synthesized, and its structure was confirmed by 1H NMR, IR, MS, elemental analysis and X-ray diffraction. It crystallizes in the monoclinic system, space group Pi with a = 6.919（3）, b = 8.525（4）, c = 9.811（4） A, a = 84.22（2）, β = 71.028（19）, γ = 86.10（2）°, Dc = 1.448 g/cm3, Z = 2, V= 544.2（4） A3, F（000） = 248, the final R = 0.0379 and WR = 0.0913 for 1709 observed reflections with I〉 2σ（I）. The preliminary biological test shows that the title compound shows weak inhibitory activities against Phytophthora infestans, Botrytis cinerea, Corynespora cassiicola, Rhizoctonia solani and Pythium ultimum.

Synthesis and Fungicidal Activity of Chlorothalonil Derivatives

[Objective]The paper was to develop a novel fungicide with high efficacy and low toxicity.[Method]Chlorothalonil was used as the parent structure,and its 4-position substituent was converted to amino group.Totally 12 amide compounds not reported in the literature were designed and synthesized.Their structures were conformed by 1H NMR.[Result]The preliminary bioassay test showed that compounds JTCN-01,JTCN-05 and JTCN-07 had good control effect on corn rust at the concentration of 200 mg/L,and the control effect of compound JTCN-05 reached 95%.[Conclusion]Some chlorothalonil derivatives had the potential for further development.

Isolation and Identification of Cardenolide Compounds of Gomphocarpus sinaicus and Their Fungicidal Activity Against Soil Borne and Post Harvest Fungi

This study was undertaken to explore new antifungal compounds from the methanolic extract of G. sinaicus. Two cardenolide compounds were isolated and identified by GC-MS as cardenolide glycoside, 15-hydroxy-3,4,5,6-dehydrocalotropin and cardenolide genin, 3,4,5,6-dehydrocalotropagenin. The antifungal activity of these compounds was assessed. Results revealed that both compounds showed pronounced fungicidal activity against both soil borne fungi, R. solani, F. oxysporium, and postharvest fungi, R. stolonifer, P. digtatum, compared to the standard fungicides, flutolanil and copper oxychloride, respectively. The ECs0 values of the cardenolide genin were 0.703, 13.63 and 4.22, 8.403 lag/mL forR. solani, F. oxysporium andR. stolonifer, P. digtatum respectively. On the other hand, the ECs0 values of the standard fungicide, flutolanil, were 9.49 and 61.22 ~tg/mL against R. solani and F. oxysporium. While the ECso values of copper oxychloride were 279.94 and 187.13 p.g/mL against R. stolonifer and P. digtatum, respectively. The results showed that cellulase, PME, PPO of the tested fungi was more sensitive than to cardenolide genin. The strong antifungal activity of cardenolide genin reported in this study indicated that has a potential to be used as fungicides.

Antifungal Activities of Eight Fungicides against Fusarium oxysporum Schlecht

[Objective]The paper was to screen fungicides with strong antifungal activities against Fusarium oxysporum Schlecht,and to provide a theoretical basis for controlling root-rot of Rhodiola sachalinensis A. Bor. [Method]Using mycelial growth rate method,the indoor antifungal activities of eight fungicides against F. oxysporum were studied. [Result]Eight fungicides at different concentrations performed different antifungal activities. Toxicity test results showed that the EC_（50） value of Difenoconazole was the smallest（ 4. 267 4 mg/L）,followed by Mancozeb（ 6. 952 5 mg/L）,and the EC_（50） of Thiram,Captan and Procymidone were relatively small from 25 to 50 mg/L. [Conclusion]Among eight fungicides,Difenoconazole had the best antifungal effect against F. oxysporum,while Mancozeb,Thiram,Captan and Procymidone had good control effects as well.

Determination of Fungicidal Activities of Six Antagonistic Actinomycetes in Soil and Their Preliminary Identification

[ Objective] The paper was to preliminarily identify the species of six actinomyeetes strains, and to determine the fungicidal activities of their fermenta- tion products. E Method ] The species of six aefinomyeetes strains were identified by morphological method, and the fungicidal activities of the fermentation products of six aetinomycetes strains were systematically determined by series of methods including mycellal growth rate inhibition method, spore germination method, potting and field test. []Result] Morphological identification results showed that six strains belonged to Streptornyces. Biological determination results indicated that the in- hibition rates of the fermentation products of six actinomycetes strains with the concentration of 500μg/nd against the mycelial growth of Fusar/um oxysporum f. sp. Vasinfeetum were all greater than 90% ; the inhibition rates against the myeelial growth of Botrytis cinerea Pers. , A/ternar/a a/zernate and Fusarium oxysporum were also greater than 80%. The inhibition rates of the fermentation products of GZ-204 and GZ-331 strains against the spore germination of Bipolaria sorokiniana and Cercospora sorghl were 97. 8% , 98.2%, 99.5% and 94.6%, respectively. Potting test showed that the protection effects of the fermentation products of GZ-204 and GZ-331 strains on wheat powdery mildew（Erysiphe graminis） were 78.8% and 87.1% , and their cure effects were 62.4% and 68.5% , respectively. Field test showed that the control effects of 200 times fermentation liquids of GZ-204 and GZ-331 strains on wheat powdery mildew were 50.5% and 69. 2%, respective- ly. [Condusion] The research provided the reference for the development of new pesticides with actinomyeetes as the resource.