CN103755718B - Trichodermin C8 unsaturated acids ester derivant and application thereof - Google Patents
Trichodermin C8 unsaturated acids ester derivant and application thereof Download PDFInfo
- Publication number
- CN103755718B CN103755718B CN201410018923.XA CN201410018923A CN103755718B CN 103755718 B CN103755718 B CN 103755718B CN 201410018923 A CN201410018923 A CN 201410018923A CN 103755718 B CN103755718 B CN 103755718B
- Authority
- CN
- China
- Prior art keywords
- trichodermin
- unsaturated acids
- acids ester
- ester derivant
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 0 C[C@@]1([C@](C2)OC(C)=O)[C@@](C)(CC(C(C)=C3)O)[C@]3O[C@]2C11C*CC1 Chemical compound C[C@@]1([C@](C2)OC(C)=O)[C@@](C)(CC(C(C)=C3)O)[C@]3O[C@]2C11C*CC1 0.000 description 1
- ZBARBEICXHHHGS-HGGUMVSISA-N C[C@]1([C@@](C)(CC(C(C)=C2)O)C2O[C@H](C2)C11OC1)/C2=[O]\C(C)=O Chemical compound C[C@]1([C@@](C)(CC(C(C)=C2)O)C2O[C@H](C2)C11OC1)/C2=[O]\C(C)=O ZBARBEICXHHHGS-HGGUMVSISA-N 0.000 description 1
- GLBIKPKWQDIQCJ-ZZXKWVIFSA-N O=C(/C=C/c(cc1)ccc1F)Cl Chemical compound O=C(/C=C/c(cc1)ccc1F)Cl GLBIKPKWQDIQCJ-ZZXKWVIFSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/10—Spiro-condensed systems
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
Abstract
The invention discloses a kind of trichodermin C8 unsaturated acids ester derivant, the general structure of this trichodermin C8 unsaturated acids ester derivant is:
Description
Technical field
The invention belongs to the antibacterial initiative field in New pesticides discovery, be specifically related to a series of to plant pathogenic fungi tool
There is the trichodermin C8 unsaturated acids ester derivant of bacteriostatic activity.
Background technology
Since 21 century, quickly growing of antibacterial, insecticide proportion is the most gradually sterilized agent and catch up with, particularly
Fluoxastrobin, has become as the representative of antibacterial kind, and sales volume is doubled and redoubled.Currently, with natural product as parent, wide spectrum high
The antibacterial of effect, mechanism of action uniqueness has become the emphasis of recent development in the world.
Endogenetic fungus and natural product thereof have important application potential, trichothecene in modern biotechnology drug development
Compounds is the mycotoxin that a class is famous, for Fusarium (Fusarium), Trichothecium (Trichothecene),
The metabolite of the funguses such as trichoderma (Trichoderma), the paint mould genus of speckle (Myrothecium), these compounds have one
Similar sesquiterpene skeleton, usually contains a stable epoxy and alkene double bond structure in molecule.Trichothecene compounds
There is suppression or kill the function that fungus (including many phytopathogens) and suppression plant growing etc. merit attention.As
Trichodermin(formula III compound) Aspergillus flavus, A.niger, Cladosporium can be suppressed
Cucumerium, Rhizoctonia solani, R.bataticola, Candida albicans and Rhizopus
The various plants pathogen mycelial growths such as stolonifer, the trichodermin plumule to Nicotiana tabacum L., bean, wheat and barley etc.
Growth tool obvious inhibiting effect, it is possible to from root absorption, causes above-mentioned plant dead.
Trichodermol(Formula II compound) it is the simplest trichothecene compounds of structure, a large amount of in retrieval
Domestic and foreign literature is also found after the preliminary study of part Trichothecenes active substance by project team, with
Trichodermol is that the compound of basic framework not only has efficient suppression fungus and the activity of suppression plant growing, and
Its toxicity is low, safer to mammal, has huge potentiality to be exploited.
Trichodermin (Trichodermin, formula III compound) is that biotechnology research institute of agricultural college of Zhejiang University is from one
A kind of compound separated in the secondary metabolite of newfound endogenetic fungus-Trichoderma taxi, research finds this compound pair
Important plant pathogenic fungi Rhizoctonia solani Kuhn and the pathogen of Botrytis cinerea have the strongest inhibitory action, to rice blast and banded sclerotial blight also
There is good inhibitory action.Through indoor bioassay, greenhouse field control effectiveness test and acute experiment, show that trichodermin is plant
Biological control of diseases has good development prospect.
In the most authorized Chinese invention patent ZL200810162582.8 trichodermin derivant and application thereof, mention
The bacterial strain of trichodermin fermentable sources and preparation method.Zhang Chulong, Lin Fu in etc. reported first in 2007 generation Trichoderma spp.
A kind of novel new endogenetic fungus Trichoderma taxi Trichoderma being separated to from endogenetic fungus Taxus mairei of rhzomorph
Taxi bacterial strain ZJUF0986, its metabolite is exactly trichodermin (Trichodermin, formula III compound).(Chu-long
Zhang, Shu-peng Liu, Fu-cheng Lin, Christian P.Kubicek&Irina S.Druzhinina,
Trichoderma taxi sp.nov.,an endophytic fungus from ChineseyewTaxusmairei.FEMS
Microbiol Lett270 (2007) 90 96.) Chen Shaoyuan, Zhang Chulong, Lin Fu in etc. 2008 years reported first trichoderma
Crystal structure (Shao-Yuan Chen, a*Chu-Long Zhang, a Yu-Zhe Chenb and Fu-Cheng of element
Lin.Trichodermin(4b-acetoxy-12,13-epoxytrichothec-9-ene.Acta
Crystallographica Section E2008, E64, o702).
This seminar on this basis, in conjunction with practicable chemical synthesis process, launches trichodermin series and spreads out
Biological chemosynthesis and the antibacterial and structure activity study of suppression plant growing thereof, thus for initiative with trichodermin be
The novel agrochemical product of parent lays the foundation.
There is as agricultural antibiotic just because of trichodermin the feature of high efficiency and broad spectrum activity, and send out many trichoderma
Ferment product can be separated to, if so research further deeply, as carry out original strain transformation, fermentation technology, structure activity relationship,
Derivatization, in conjunction with field efficacy and safety etc. thereof, once obtains the trichodermin derivant that sexual valence is higher, the most great industrialization
Prospect.
Inventor place seminar early stage carries out the derivatization of various ester to trichodermin C4 position, finds that different ester group is to change
The bacteriostasis rate of compound is significantly different.Particularly, aromatic ester groups is higher than straight chained alkyl ester activity, and unsaturated ester group is than saturated ester group
Activity is high, is described in detail in patent CN101429203A.
Later, C8 position is modified again by inventor, finds C8 position in trichodermin (II) is connected ester group structure, and it is right
The inhibition of Pyricularia oryzae substantially increases.Especially when connect be cinnamate time, its EC50Value reaches 1.96mg/L, and
The trichodermin former medicine EC to Pyricularia oryzae50Value is 39.26mg/L.It is obvious that the ester group on C8 position can significantly improve chemical combination
The bacteriostasis rate of thing, concrete is described in detail in patent CN200810162582.8.
It is a reasonable active structure fragment in view of unsaturated acids ester structure, is in a lot of commercialization pesticide
Individual active group, such as antibacterial--Fluoxastrobin, ZEN 90160 etc., in structure, the existence of unsaturated acids ester structure is to preventing and treating agricultural
The phytopathogen etc. important with on gardens has good contribution function.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of trichodermin C8 unsaturated acid ester with bactericidal activity and spreads out
Biological and its production and use.
In order to solve above-mentioned technical problem, the present invention provides a kind of trichodermin C8 unsaturated acids ester derivant, this Trichoderma spp.
The general structure of rhzomorph C8 unsaturated acids ester derivant is:
R be following any one:
It is optionally substituted by halogen or by the substituted or non-substituted thiazolinyl of alkoxyl；
That replaced by halogen, alkyl, alkoxyl, nitro, haloalkyl or non-substituted cinnamyl group；
It is optionally substituted by halogen or alkyl replaces or replaced by alkoxyl or non-substituted heteroaryl.
Improvement as the trichodermin C8 unsaturated acids ester derivant of the present invention: the R in general structure be following arbitrarily
A kind of:
Vinyl, positive acrylic, isopropenyl, n-butene base, tertiary cyclobutenyl；
Methoxy-ethylene base, methoxvpropenvl, ethoxy ethylene base (ethoxy vinyl), methoxvpropenvl；
The C replaced by F2-C4-thiazolinyl, the C replaced by Cl2-C4-thiazolinyl；
The cinnamyl group that replaced by F, the cinnamyl group replaced by Cl, the cinnamyl group replaced by Br, replaced by nitro
Cinnamyl group, the cinnamyl group replaced by cyano group, the cinnamyl group by methyl substituted cinnamyl group, replaced by ethyl, by first
The substituted cinnamyl group of epoxide, the cinnamyl group replaced by trifluoromethyl；
The pyridine radicals replaced by F, the pyridine radicals replaced by Cl, by methyl substituted pyridine radicals.
Further improvement as the trichodermin C8 unsaturated acids ester derivant of the present invention: under the R in general structure is
Any one shown in table:
Table 1 trichodermin C8 unsaturated acids ester derivant
The present invention provides the purposes of above-mentioned trichodermin C8 unsaturated acids ester derivant the most simultaneously, is used for suppressing phytopathy
Fungal pathogens, as the antibacterial on agricultural and/or gardening.
The improvement of purposes as the trichodermin C8 unsaturated acids ester derivant of the present invention: described plant pathogenic fungi is
Fusarium graminearum (Gibberella zeae), wheat powdery mildew (Blumeria graminis), botrytis cinerea pers
(Botrytis cinerea), Rhizoctonia solani Kuhn (Rhizoctonia solani), rice blast fungus (Pyricularia
Or Ustilaginoidea virens (Ustilaginoidea oryzae) oryzae).
The trichodermin C8 unsaturated acids ester derivant of general structure I of the present invention, can single use or with separately
Outer bioactive compound is applied in combination, and many plant pathogenic fungis are had prevention effect.
Inventor is during the derivatization of compound II is invented, if finding, the ester connected on C8 position is unsaturated acids
Ester, such as olefin(e) acid ester, during cinnamate, compound has more preferable activity, and this content has no that document is reported.Concrete structure formula is as logical
Shown in Formulas I:
(I)
When the trichodermin C8 unsaturated acids ester derivant of the present invention is for agricultural or horticulture, can there is the system of various dosage form
Agent, such as it can be formulated into microgranule, trickle granule, wettable powder, dilute Emulsion, water or oil-based suspension or water or oil
Solution (it can Direct spraying or dilution after use), aerosol or polymer capsule.Used carrier can be natural or synthesis
, can be organic or inorganic, it is commonly used to help reactive compound to arrive processed position, and contributes to storage
Hide, transport or use reactive compound.Solid, liquid and carrier gas are selected from the load for such preparation known in the art
Body.
Such preparation can according to a conventional method, as by by active component and carrier or diluent (solvent) and, arbitrarily
Selecting, one or more surfactants closely mix and/or grind.
The suitably example of solvent includes: aromatic hydrocarbons, the fraction of C8 to C12 in special oil, such as xylene mixture or take
The naphthalene in generation；Aliphatic series or alicyclic, such as hexamethylene or paraffin；Alcohol, such as ethanol, 1,2 ethylene glycol, 1,2 ethylene glycol list
Methyl ether or 1,2-ethylidene list ether；Dihydroxylic alcohols or its ether；Ketone, such as Ketohexamethylene；Polar solvent, such as METHYLPYRROLIDONE,
Dimethyl sulfoxide or dimethylformamide；Optional epoxidised vegetable oil, such as epoxidised coconut oil or soybean oil, and
Water.
Examples of carriers in such as granule and dispersibility wettable powder includes: natural minerals filler, such as square solution
Stone, Talcum, Kaolin, montmorillonite or active hargil.In order to improve the physical property of compositions, it is possible to add the silicic acid of high dispersive
Or the adsorpting polymerization thing of high dispersive.The suitably example of granulating absorption carrier includes；Porous mass, such as Pumex, the brick ground,
Sepiolite and bentonit；And imporosity material, such as calcite and sand.Kind can be used widely, the grain of organic or inorganic
Compound matter, the example includes dolomite and the plant residue ground.
Can use in the preparations such as one or more agricultural chemicalses is conventional, has good emulsifying, dispersion and wettability
The cation of matter, cation and non-ionic compound are as surfactant.Can use single above-mentioned surfactant or on
State the mixture of surfactant.
Spendable nonionic surfactant includes: polyoxyethylene alkyl ether；Polyxyethylated ester；Polyoxyethylene alkane
Base aryl ether；Polyoxyethylene aryl ether；Polyoxyethylene sorbitan Arrcostab；Sorbitan alkyl esters；Fat
Fat acid sugar ester；Fatty glyceride or pentaerythritol ester；Pluronic type surfactant；Acetylene alcohol, acetylenediol, and
Their ethylene oxide adduct；Silicone surfactant；And alkyl androstanediol.
Spendable anion surfactant includes；Alkylbenzenesulfonate；Dialkyl sulfosuccinates；Alkylsurfuric acid
Salt；Alkyl methyl taurine salt；Sulphuric acid or phosphoric acid are esterified by above-mentioned non-ionic surface active material ethylene oxide adduct, if
Need, neutralize with suitable alkali, and the anion surfactant prepared；Lignosulphonates；Alkylnaphthalene sulfonate and condensation thereof
Thing；Phenolsulfonate and condensation substance thereof；The polycarboxylic acids of salt form or polysulfonate acid polysoap or itself and such as acrylic acid, maleic acid, benzene
Vinyl sulfonic acid or the polysoap of the condensation substance form with vinyl；By starch or dextrin and 1-(2-caprylyl) interpolation of-sodium succinate
The starch type surfactant of agent composition；Carboxymethyl cellulose salt；The sodium salt of soaps such as higher fatty acids or potassium salt, and α-alkene
Belong to sulfonate.
Spendable cationic surfactant includes amine salt or quaternary surfactant, and higher aliphatic amine or fat
The ethylene oxide adduct of fat amide.
Spendable amphoteric surfactant includes amino acid pattern or betaine type surfactant, or lecithin.
Have been found that the derivant of the above-mentioned various surfactants that one of them or more hydrogen atom replaced by fluorine has
Strong reduction shows the effect of tension force, is conducive to using in the present invention.
The compositions utilizing the trichodermin C8 unsaturated acids ester derivant of the present invention to be prepared also can contain one or many
Planting additive, selected from stabilizer, defoamer, viscosity modifier, cross-linking agent or binding agent or a combination thereof, and fertilizer is active with other
Material is to reach special-effect.
Bactericidal composition usually contains 0.01 to 99%, reactive compound (that is, the Trichoderma spp. of the present invention of preferably 0.1 to 95%
Rhzomorph C8 unsaturated acids ester derivant)；Containing solid or the liquid additive of 1 to 99.99%；And containing 0 to 25%, preferably
The surfactant of 0.1 to 25%.When commodity product(s) is sold with concentrate composition form, end user is generally diluted
Become the concentration (10 arrive 1ppm) of the weight ratio of 0.001 to 0.0001%.
Above-mentioned percentage ratio is the most by weight.
The trichodermin C8 unsaturated acids ester derivant of the present invention, actual usage and consumption be: is generally diluted to 0.001 and arrives
The concentration of the weight ratio of 0.0001% is sprayed, the effective dose (i.e. trichodermin C8 unsaturated acids ester derivant) of per hectare
Consumption be 50-200g.
The compounds of this invention can be with other reactive compounds, such as, insecticide, antibacterial, acaricide, nematicide,
Antifungal, plant growth regulator or herbicide mixed preparing or collaborative use.
The compounds of this invention also can be with synergist mixed preparing or collaborative use.The preparation of such chemicals and being used
Form be commercial use needed for.Synergist is without independent activities, and this is as the compound that can improve reactive compound activity.
The present invention is further by following non-limiting examples, and preparation example and example of formulations are illustrated, and they divide
Do not mentionlet alone some compound of the bright present invention, for preparing the raw material of the compounds of this invention, and contain the compounds of this invention some
The preparation of Agrotechnical formulation.
The compounds of this invention is represented by the numbering specified by aforementioned table 1.
It is an advantage of the current invention that: synthesized series and had no the new derivatives being different from trichodermin of report, because
Its precursor structure is the metabolite of natural endogenetic fungus, ferments through high efficient strain, and through extracting isolated, activity is fine,
So the series derivates that this precursor structure designs synthesis for lead compound all has certain biological activity, to gibberella saubinetii
Pathogenic bacteria (Gibberella zeae), wheat powdery mildew (Blumeria graminis), botrytis cinerea pers (Botrytis
Cinerea), Rhizoctonia solani Kuhn (Rhizoctonia solani), rice blast fungus (Pyricularia oryzae), water
Rice ustilaginoidea virens (Ustilaginoidea oryzae) has bactericidal activity in various degree.Wherein compound I-1, I-2 and I-
3 pairs of Rhizoctonia solani Kuhns, I-1, I-2, I-3, I-7 and I-8 are to wheat powdery mildew, and I-1, I-2 and I-3 are to fusarium graminearum
Show good inhibitory activity.
The present invention uses trichodermin (formula III compound) to be raw material, obtains formula IV chemical combination by selenium dioxide oxidation
Thing, formula IV compound performs the derivatization reaction further, obtains trichodermin C8 unsaturated acids ester derivant, and it is alive to carry out sterilization
Property measure, that selects suppression ratio more than 80% under 50mg/L concentration from general sieve carries out primary dcreening operation evaluation.
The synthesis of reaction equation main material IV
A) SeO2, aq. dioxane, backflow, 18h；32%
At room temperature, in the reaction bulb of 100mL, it is sequentially added into 2.92g (10mmol) trichodermin (III) and 80mL bis-
Oxygen six ring, after trichodermin (III) dissolves, adds 1.44g (13mmol) SeO in system2, it is eventually adding 8mL water.Instead
After answering liquid to react 18 hours under reflux, TLC trace point plate, the reaction of raw material point is completely.Filter out the solid in reactant liquor, so
Rear anhydrous Na2SO4(about 4.0g) is dried, the de-dioxane of decompression (5-50MPa), obtains thick liquid, uses 200～300 purposes
Silicagel column separates, and eluent is ethyl acetate: petroleum ether=1:5, (volume ratio), obtains the 4-β-acetyl of target compound 0.98g
Base-8-hydroxyl-12, the single-ended born of the same parents of 13-epoxy mould-9-alkene toxin (IV), 95%(volume %) ethyl alcohol recrystallization, filter to obtain compound
IV(0.90g), yield is 32%.Concrete structure confirmation data are as follows:
IV:Rf=0.55(silica gel,ethyl acetate/petroleum ether1:3);[α]D 18=47.5556
(c0.010,CH3OH);MS ES+m/z:309.12(M+H)+(100%);1H NMR(500MHz,CDCl3):δ5.52(dd,J=
3.5,7.5Hz,1H,H-4),4.345.48-5.46(m,1H,H-10),4.06(d,J=7.5Hz,1H,H-8),3.84(d,J=
5.0Hz,1H,H-2),3.63(d,J=5.5Hz,1H,H-11),3.13(d,J=4.0Hz,1H,H-13),2.85(d,J=4.0Hz,
1H,H-13),2.53-2.49(m,1H,H-3),2.08(s,3H,AcH),2.02-1.98(m,1H,H-3),1.86-1.84(m,
1H,H-7),1.70(s,3H,H-16),1.53-1.52(m,1H,H-7),0.98(s,3H,H-14),0.73(s,3H,H-15).
The synthesis general step of trichodermin C8 unsaturated acids ester derivant:
4-β-acetyl group-8-single-ended the born of the same parents of hydroxyl-12,13-epoxy mould-9-alkene toxin (IV) (1 equivalent), triethylamine (1～10
Equivalent, for IV) and the DMAP catalyst of catalytic amount be dissolved in dry dichloromethane, slowly drip under ice-water bath
The acyl chlorides (1.1 equivalents, for IV) of the various unsaturated acids needed.Reactant mixture at room temperature reacts to raw material base
(being reacted by TLC detecting and tracking) it is wholly absent on Ben.Wash respectively with 1M HCl, saturated aqueous common salt after reactant liquor dilution, use
Anhydrous Na2SO4 is dried.It is concentrated to give crude product, purifies with silica gel column chromatography and obtain target compound.
Detailed description of the invention
List representational specific embodiment separately below:
Embodiment 1, the synthetic method of a kind of trichodermin C8 position unsaturated acids ester derivant (I-1), its reaction equation is:
Concrete course of reaction is as follows:
Dichloromethane 10mL, 4-β-acetyl group-8-hydroxyl-12,13-epoxy single-ended born of the same parents enzyme-9-is added in twoport flask
Alkene toxin (IV) 0.5g, adds triethylamine 1.0g, 10mg DMAP catalyst, slowly instills 1.1 equivalent molar amount under ice-water bath
Acryloyl chloride, stirring reaction under room temperature, TLC detection reaction process (response time is about 3.0 hours).After reaction terminates, first use
10ml dichloromethane is diluted as solvent, then washs 3 times with the dilute hydrochloric acid of 1M, the most about 10ml, saturated aqueous common salt washing 2
Secondary, the most about 10ml, 3-5g anhydrous sodium sulfate is dried, and solvent is spin-dried for (being concentrated to dryness).Then (eluting is separated through silica gel column chromatography
Agent, ethyl acetate: the volume ratio of petroleum ether=1:3), obtain target compound I-1.
1H NMR(500MHz,CDCl3):δ6.45(dd,J=1.5,17.5Hz,1H,H-18),6.16(dd,J=10.5,
17.5Hz, 1H, H-17), 5.88 (dd, J=10.5,1.0Hz, 1H, H-18), 5.60-5.58 (m, 1H, H-8), 5.55 (q, J=
4.0,3.5Hz,1H,H-4),5.45(dd,J=6.0,10.0Hz,1H,H-10),3.86(d,J=5.5Hz,1H,H-2),3.66
(d,J=5.5Hz,1H,H-11),3.14(d,J=4.0Hz,1H,H-13),2.38(d,J=4.0Hz,1H,H-13),2.55(dd,J
=8.0,15.5Hz,1H,H-3),2.08(s,3H,CH3COO-),2.03-1.86(m,3H,H-3&H-7),1.71(s,3H,H-
16), 1.07 (s, 3H, H-14), 0.72 (s, 3H, H-15), MS ES+m/z:362.17(M+H)+(100%)。
Embodiment 2, the synthetic method of compound (I-2), its reaction equation is:
Concrete course of reaction is as follows:
Dichloromethane 10mL, 4-β-acetyl group-8-hydroxyl-12,13-epoxy single-ended born of the same parents enzyme-9-is added in twoport flask
Alkene toxin (IV) 0.5g, adds triethylamine 1.0g, 10mg DMAP catalyst, slowly instills 1.1 equivalent molar amount under ice-water bath
3-methacrylic chloride, stirring reaction under room temperature, TLC detects reaction process.After reaction terminates, first dilute with 10ml dichloromethane
Releasing, then wash 3 times with the dilute hydrochloric acid of 1M, the most about 10ml, saturated aqueous common salt washs 2 times, the most about 10ml, 3-5g anhydrous slufuric acid
Sodium is dried, and is concentrated to dryness.Then separate (eluant, ethyl acetate: the volume ratio of petroleum ether=1:3) through silica gel column chromatography, obtain
Target compound I-2.
1H NMR(500MHz,CDCl3):δ6.09(s,1H,CH=C-Me2), 5.53 (m, 2H, H-4 ＆ H-8), 5.41-
5.39(1H,m,H-10),3.83(d,J=5.5Hz,1H,H-2),3.62(d,J=5.5Hz,1H,H-11),3.09(d,J=
4.0Hz,1H,H-13),2.78(d,J=4.0Hz,1H,H-13),2.53(dd,J=7.5,15.5Hz,1H,H-3),2.18(s,
3H,-CH=C-CH3),2.08(s,3H,-COCH3), 2.01-1.97 (m, 3H, 1H-3 ＆ 2H-7), 1.91 (s, 3H ,-CH=C-
CH3),1.88(s,3H,H-16),1.05(s,3H,H-14),0.70(s,3H,H-15),MS ES+m/z:391.20(M+H)+
(100%).
Embodiment 3, the synthetic method of compound (I-3), its reaction equation is:
Concrete course of reaction is as follows:
Dichloromethane 10mL, 4-β-acetyl group-8-hydroxyl-12,13-epoxy single-ended born of the same parents enzyme-9-is added in twoport flask
Alkene toxin (IV) 0.5g, adds triethylamine 1.0g, 10mg DMAP catalyst, slowly instills 1.1 equivalent molar amount under ice-water bath
3,3-dimethyl acryloyl chlorides, stirring reaction under room temperature, TLC detects reaction process.After reaction terminates, first use 10ml dichloromethane
Dilution, then wash 3 times with the dilute hydrochloric acid of 1M, saturated aqueous common salt washs 2 times, and anhydrous sodium sulfate is dried, and is concentrated to dryness.Then through silicon
Plastic column chromatography separates (eluant, ethyl acetate: petroleum ether=1:3), obtains target compound I-3,1H NMR(500MHz,
CDCl3): δ 6.09 (s, 1H, CH=C-Me2), 5.53 (m, 2H, H-4 ＆ H-8), 5.41-5.39 (1H, m, H-10), 3.83 (d, J
=5.5Hz,1H,H-2),3.62(d,J=5.5Hz,1H,H-11),3.09(d,J=4.0Hz,1H,H-13),2.78(d,J=
4.0Hz,1H,H-13),2.53(dd,J=7.5,15.5Hz,1H,H-3),2.18(s,3H,-CH=C-CH3),2.08(s,3H,-
COCH3), 2.01-1.97 (m, 3H, 1H-3 ＆ 2H-7), 1.91 (s, 3H ,-CH=C-CH3),1.88(s,3H,H-16),1.05(s,
3H, H-14), 0.70 (s, 3H, H-15), MS ES+m/z:391.20(M+H)+(100%)。
Embodiment 4, the synthetic method of compound (I-8), its reaction equation is:
Concrete course of reaction is as follows:
Dichloromethane 10mL, 4-β-acetyl group-8-hydroxyl-12,13-epoxy single-ended born of the same parents enzyme-9-is added in twoport flask
Alkene toxin (IV) 0.5g, adds triethylamine 1.0g, 10mg DMAP catalyst, slowly instills 1.1 equivalent molar amount under ice-water bath
β-and to methylbenzene acryloyl chloride, stirring reaction under room temperature, TLC detects reaction process.After reaction terminates, first use 10ml dichloromethane
Dilution, then wash 3 times with the dilute hydrochloric acid of 1M, the most about 10ml, saturated aqueous common salt washs 2 times, the anhydrous sulfur of the most about 10ml, 3-5g
Acid sodium is dried, and is concentrated to dryness.Then (eluant, ethyl acetate: the volume ratio of petroleum ether=1:3) is separated through silica gel column chromatography,
To target compound I-8.1H-NMR(500MHz,CDCl3):δ7.68-7.65(d,J=15.5Hz,1H,C=CH-Ar),7.41-
7.39(d,J=8.0Hz,2H,H-2,6-Ar),7.18-7.16(d,J=8.0Hz,2H,H-3,5-Ar),6.39-6.35(d,J=
15.5Hz,1H,O=C-CH=),5.58-5.57(d,J=5.5Hz,1H,H-10),5.53-5.51(dd,J1=J2=3.5Hz,1H,H-
4),5.49-5.45(dd,J1=J2=1.5Hz,1H,H-8),,3.84-3.83(d,J=5.0Hz,1H,H-2),3.65-3.64(d,J
=5.0Hz,1H,H-11),3.11-3.10(d,J=4.0Hz,1H,H-13),2.81-2.80(d,J=4.0Hz,1H,H-13),
2.53-2.48(dd,J1=J2=8.0Hz,1H,H-3endo),2.35-2.34(d,J=5.0Hz,3H,H-4-CH3-Ar),2.13
(s,3H,O=CCH3),2.05-1.95(m,2H,H-7exo,3exo),1.91-1.87(dd,J1=J2=1.5Hz,1H,H-
7endo),1.72(s,3H,H-16),1.06(s,3H,H-14),0.70(s,3H,H-15);MS ESI+m/z:453.34(M+H)+
(100%).
Embodiment 5, the synthetic method of compound (I-9), its reaction equation is:
Concrete course of reaction is as follows:
Dichloromethane 10mL, 4-β-acetyl group-8-hydroxyl-12,13-epoxy single-ended born of the same parents enzyme-9-is added in twoport flask
Alkene toxin (IV) 0.5g, adds triethylamine 1.0g, 10mg DMAP catalyst, slowly instills 1.1 equivalent molar amount under ice-water bath
β-estragole acyl chlorides, stirring reaction under room temperature, TLC detects reaction process.After reaction terminates, first use 10ml dichloromethane
Alkane dilutes, then washs 3 times with the dilute hydrochloric acid of 1M, the most about 10ml, and saturated aqueous common salt washs 2 times, and the most about 10ml, 3-5g are anhydrous
Sodium sulfate is dried, and is concentrated to dryness.Then (eluant, ethyl acetate: the volume ratio of petroleum ether=1:3) is separated through silica gel column chromatography,
Obtain target compound I-9.1H-NMR(500MHz,CDCl3):δ7.69-7.66(d,J=15.5Hz,1H,C=CH-Ar),7.51-
7.48(dd,J1=9.0Hz,J2=3.0Hz,2H,H-2,6-Ar),6.93-6.91(dd,J1=8.5Hz,J2=2.5Hz,2H,H-3,
5-Ar),6.33-6.30(d,J=16.0Hz,1H,O=C-CH=),5.61-5.60(dd,J1=J2=1.5Hz,1H,H-8),5.55-
5.54(dd,J1=J2=3.5Hz,1H,H-4),5.51-5.48(d,J=5.5Hz,1H,H-10),3.88-3.87(d,J=5.0Hz,
1H,H-2),3.85(s,3H,H-Ar-OCH3),3.68-3.67(d,J=5.0Hz,1H,H-11),3.15-3.14(d,J=
4.0Hz,1H,H-13),2.84-2.83(d,J=4.0Hz,1H,H-13),2.57-2.52(dd,J1=J2=9.0Hz,1H,H-
3endo),2.09(s,3H,O=CCH3),2.04-1.98(m,2H,H-7exo,3exo),1.93-1.90(dd,J1=J2=1.5Hz,
1H,H-7endo),1.75(s,3H,H-16),1.09(s,3H,H-14),0.73(s,3H,H-15);MS ESI+m/z:469.34
(M+H)+(100%).
Embodiment 6, the synthetic method of compound (I-10), its reaction equation is:
Concrete course of reaction is as follows:
Dichloromethane 10mL, 4-β-acetyl group-8-hydroxyl-12,13-epoxy single-ended born of the same parents enzyme-9-is added in twoport flask
Alkene toxin (IV) 0.5g, adds triethylamine 1.0g, 10mg DMAP catalyst, slowly instills 1.1 equivalent molar amount under ice-water bath
β-(3,4,5-trimethoxy) acryloyl chloride, stirring reaction under room temperature, TLC detects reaction process.After reaction terminates, first use
10ml dchloromethane, then wash 3 times with the dilute hydrochloric acid of 1M, the most about 10ml, saturated aqueous common salt washing 2 times, the most about
10ml, 3-5g anhydrous sodium sulfate is dried, and is concentrated to dryness.Then through silica gel column chromatography separate (eluant, ethyl acetate: petroleum ether=
The volume ratio of 1:3), obtain target compound I-10.1H-NMR(500MHz,CDCl3):δ7.64-7.61(d,J=16.0Hz,1H,
C=CH-Ar),6.78-6.76(s,2H,H-2,6-Ar),6.36-6.33(d,J=16.0Hz,1H,O=C-CH=),5.61-5.60
(dd,J1=J2=1.5Hz,1H,H-8),5.55-5.53(dd,J1=J2=3.5Hz,1H,H-4),5.51-5.48(d,J=5.5Hz,
1H,H-10),3.89(s,6H,Ar-3,5-OCH3),3.88(s,3H,Ar-4-OCH3),3.86-3.85(d,J=5.0Hz,1H,H-
2),3.68-3.67(d,J=5.5Hz,1H,H-11),3.14-3.13(d,J=4.0Hz,1H,H-13),2.84-2.83(d,J=
4.0Hz,1H,H-13),2.56-2.51(dd,J1=J2=9.0Hz,1H,H-3endo),2.17(s,3H,O=CCH3),2.08-
1.97(m,2H,H-7exo,3exo),1.93-1.75(dd,J1=J2=1.5Hz,1H,H-7endo),1.75(s,3H,H-16),
1.08(s,3H,H-14),0.73(s,3H,H-15);MS ESI+m/z:529.38(M+H)+(100%).
Embodiment 7, the synthetic method of compound (I-15), its reaction equation is:
Concrete course of reaction is as follows:
Dichloromethane 10mL, 4-β-acetyl group-8-hydroxyl-12,13-epoxy single-ended born of the same parents enzyme-9-is added in twoport flask
Alkene toxin (IV) 0.5g, adds triethylamine 1.0g, 10mg DMAP catalyst, slowly instills 1.1 equivalent molar amount under ice-water bath
β-bromophenyl acryloyl chloride, stirring reaction under room temperature, TLC detects reaction process.After reaction terminates, first dilute with 10ml dichloromethane
Releasing, then wash 3 times with the dilute hydrochloric acid of 1M, the most about 10ml, saturated aqueous common salt washs 2 times, the most about 10ml, 3-5g anhydrous slufuric acid
Sodium is dried, and is concentrated to dryness.Then separate (eluant, ethyl acetate: the volume ratio of petroleum ether=1:3) through silica gel column chromatography, obtain
Target compound I-15.1H-NMR(500MHz,CDCl3):δ8.10-8.07(d,J=16.0Hz,1H,C=CH-Ar),7.64-
7.62(m,2H,H-3,5-Ar),7.36-7.33(dd,J1=J2=8.0Hz,1H,H-6-Ar),7.27-7.23(m,1H,H-4-
Ar),6.42-6.38(d,J=16.0Hz,1H,O=C-CH=),5.62-5.61(dd,J1=J2=1.5Hz,1H,H-8),5.57-
5.54(dd,J1=J2=3.5Hz,1H,H-4),5.51-5.48(dd,J1=J2=6.0Hz,1H,H-10),3.89-3.88(d,J=
5.0Hz,1H,H-2),3.69-3.68(d,J=5.5Hz,1H,H-11),3.16-3.15(d,J=4.0Hz,1H,H-13),2.85-
2.84(d,J=4.0Hz,1H,H-13),2.57-2.52(dd,J1=J2=9.0Hz,1H,H-3endo),2.09(s,3H,O=
CCH3),2.05-1.99(m,2H,H-7exo,3exo),1.96-1.93(dd,J1=J2=1.5Hz,1H,H-7endo),1.77(s,
3H,H-16),1.10(s,3H,H-14),0.74(s,3H,H-15);MS ESI+m/z:517.36(M+H)+(100%).
Embodiment 8, the synthetic method of compound (I-18), its reaction equation is:
Concrete course of reaction is as follows:
Dichloromethane 10mL, 4-β-acetyl group-8-hydroxyl-12,13-epoxy single-ended born of the same parents enzyme-9-is added in twoport flask
Alkene toxin (IV) 0.5g, adds triethylamine 1.0g, 10mg DMAP catalyst, slowly instills 1.1 equivalent molar amount under ice-water bath
β-and to fluorobenzene acryloyl chloride, stirring reaction under room temperature, TLC detects reaction process.After reaction terminates, first dilute with 10ml dichloromethane
Releasing, then wash 3 times with the dilute hydrochloric acid of 1M, the most about 10ml, saturated aqueous common salt washs 2 times, the most about 10ml, 3-5g anhydrous slufuric acid
Sodium is dried, and is concentrated to dryness.Then separate (eluant, ethyl acetate: the volume ratio of petroleum ether=1:3) through silica gel column chromatography, obtain
Target compound I-18.1H-NMR(500MHz,CDCl3):δ7.68-7.65(d,J=16.0Hz,1H,C=CH-Ar),7.54-
7.51(dd,J1=J2=5.5Hz,2H,H-2,6-Ar),7.11-7.07(dd,J1=J2=8.5Hz,2H,H-3,5-Ar),6.37-
6.34(d,J=16.0Hz,1H,O=C-CH=),5.61-5.60(dd,J1=J2=1.0Hz,1H,H-8),5.55-5.53(dd,J1=
J2=3.5Hz,1H,H-4),5.50-5.47(dd,J1=J2=6.5Hz,1H,H-10),3.87-3.86(d,J=5.5Hz,1H,H-
2),3.68-3.67(d,J=5.5Hz,1H,H-11),3.14-3.13(d,J=4.0Hz,1H,H-13),2.83-2.82(d,J=
4.0Hz,1H,H-13),2.56-2.54(dd,J1=J2=9.0Hz,1H,H-3endo),2.17(s,3H,O=CCH3),2.03-
1.97(m,2H,H-7exo,3exo),1.93-1.91(dd,J1=J2=1.5Hz,1H,H-7endo),1.74(s,3H,H-16),
1.08(s,3H,H-14),0.72(s,3H,H-15);MS ESI+m/z:457.25(M+H)+(100%).
Embodiment 9, the synthetic method of compound (I-19), its reaction equation is:
Concrete course of reaction is as follows:
Dichloromethane 10mL, 4-β-acetyl group-8-hydroxyl-12,13-epoxy single-ended born of the same parents enzyme-9-is added in twoport flask
Alkene toxin (IV) 0.5g, adds triethylamine 1.0g, 10mg DMAP catalyst, slowly instills 1.1 equivalent molar amount under ice-water bath
β-m-trifluoromethyl acryloyl chloride, stirring reaction under room temperature, TLC detects reaction process.After reaction terminates, first use 10ml dichloro
Methane dilutes, then washs 3 times with the dilute hydrochloric acid of 1M, the most about 10ml, saturated aqueous common salt washing 2 times, the most about 10ml, 3-5g without
Aqueous sodium persulfate is dried, and is concentrated to dryness.Then (eluant, ethyl acetate: the volume of petroleum ether=1:3 are separated through silica gel column chromatography
Than), obtain target compound I-19.1H-NMR(500MHz,CDCl3):δ7.77(s,1H,H-2-Ar),7.74-7.71(d,J=
16.0Hz,1H,C=CH-Ar),7.71-7.70(dd,J1=8.0Hz,J2=0.5Hz,1H,H-6-Ar),7.65-7.64(d,J=
7.5Hz,1H,H-4-Ar),7.55-7.52(m,1H,H-5-Ar),6.52-6.49(d,J=16.0Hz,1H,O=C-CH=),
5.62-5.61(dd,J1=J2=1.5Hz,1H,H-8),5.55-5.53(dd,J1=J2=3.5Hz,1H,H-4),5.51-5.49
(dd,J1=J2=6.0Hz,1H,H-10),3.88-3.87(d,J=5.0Hz,1H,H-2),3.68-3.67(d,J=5.5Hz,1H,H-
11),3.15-3.14(d,J=4.0Hz,1H,H-13),2.83-2.82(d,J=4.0Hz,1H,H-13),2.56-2.52(dd,J1
=J2=9.0Hz,1H,H-3endo),2.08(s,3H,O=CCH3),2.04-1.99(m,2H,H-7exo,3exo),1.93-1.90
(dd,J1=J2=1.5Hz,1H,H-7endo),1.75(s,3H,H-16),1.09(s,3H,H-14),0.73(s,3H,H-15)
.13C NMR(100MHz,CDCl3):170.89(O=CCH3),166.05(O=CCH),143.44(CH-Ar),138.71(C9),
135.07(C-1-Ar),131.13(C-2-Ar),129.51(C-3-Ar),126.83,126.81(C-4,5-Ar),124.62
(Ar-CF3),124.59(C10),119.90(O=CCH),79.38,74.31,71.41,69.89(C2,C11,C8,C4),
65.29(C12),49.14,47.70(C5,C6),42.19(C3),36.65(C13),30.95(C7),21.07(C16),18.78
(O=CCH3),16.95(C15),5.81(C14);MS ESI+m/z:507.36(M+H)+(100%).
Pesticidal preparations embodiment
When the compounds of this invention makees agricultural or horticultural applications, can be various ways or dosage form, real at following preparation
Execute in example and illustrate.Wherein, the compounds of this invention used is listed below each compound of table 1.All percents are all weights
Magnitude, the compounds of this invention is consistent with the number that above table 1 is given.
Example of formulations 1
Wettable powder
Containing 10% the compounds of this invention I-10,2.5% dodecylbenzene sodium sulfonate, 2.5% sodium lignosulfonate, 1% dispersant NNO
It is sufficiently mixed with 84% diatomaceous mixture and grinds makes wettable powder.
Example of formulations 2
Cream
20% the compounds of this invention I-1,2% agriculture breast 500,3% agriculture breast 602,3% emulsifying agent PE6200,3%PE2520 and 69% 2
The mixture of toluene is sufficiently mixed and makes emulsible cream.
Example of formulations 3
Granule
Containing 3% the compounds of this invention I-8,1% dispersant REAX88A, 3% dispersant Wgwin6100,5% sodium lignosulfonate and
The mixture of 88% clay is sufficiently mixed and grinds, kneaded with water, then granulating dry make granule.
Example of formulations 4
Aqueous emulsion
10% the compounds of this invention I-3,5% emulsifying agent PE6200,5% agriculture breast 603 and 1% emulsifying agent REAXWL, 1.0%BHT
(a kind of antioxidant) is dissolved in 20% Ketohexamethylene.By solution and the antifreeze glycol of 10.0% and 20.0% alcohols solvent and
The emulsifying equably of the mixed liquor of the water of 28% is sheared and is made emulsible aqueous emulsion.
Assays Example
With reference to " pesticide bioactivity evaluates SOP ".
Fusarium graminearum (Gibberella zeae), wheat powdery mildew (Blumeria graminis), Fructus Cucumidis sativi grey mold
Pathogenic bacteria (Botrytis cinerea), Rhizoctonia solani Kuhn (Rhizoctonia solani), rice blast fungus
(Pyricularia oryzae), Ustilaginoidea virens (Ustilaginoidea oryzae): survey standard method NY/ with reference to raw
T1156.2-2006, uses pastille medium therapy: take each compound medicinal liquid in table 1, adds in the PDA being cooled to 45 DEG C, system
Becoming pastille culture medium flat plate, concentration is 50mg/L.Then 6.5mm diameter mycelia is taken from cultured test pathogenic bacteria colony edge
Block, moves in pastille culture medium, often processes 4 times and repeats.It is disposed, is placed in the constant temperature biochemical cultivation case of 28 DEG C cultivation, 4 days
Rear measurement colony diameter, calculates growth inhibition ratio.
Test sets medicament comparison and solvent control.
Routine observation record blade, the incidence of plant and mycelial growth situation after process, according to disease index and bacterium
Filament diameter, calculates preventive effect and suppression ratio.
Growth inhibition ratio (%)=(comparison colony diameter-process colony diameter) × 100/ (comparison colony diameter-6mm).
Concrete result of the test and data (concentration is 50mg/L, suppression ratio >=85%) are shown in Table 2:
Table 2. all noval chemical compounds bactericidal activity virulence general sieve measurement result
Under the concentration of 50mg/L major part noval chemical compound to botrytis cinerea pers, fusarium graminearum, wheat powdery mildew,
Rhizoctonia solani Kuhn and Ustilaginoidea virens have bactericidal activity in various degree.Wherein compound I-1, I-2 and I-3 is to Oryza sativa L.
Sheath blight fungus, gibberellic hypha is shown well by I-1, I-2, I-3, I-7 and I-8 by wheat powdery mildew, I-1, I-2 and I-3
Inhibitory activity, being configured to activity after preparation can be higher, can be further developed as commodity antibacterial.
Finally, in addition it is also necessary to be only several specific embodiments of the present invention it is noted that listed above.Obviously, this
Bright it is not limited to above example, it is also possible to have many deformation.Those of ordinary skill in the art can be from present disclosure
The all deformation directly derived or associate, are all considered as protection scope of the present invention.
Claims (3)
1. trichodermin C8 unsaturated acids ester derivant, is characterized in that the structure of this trichodermin C8 unsaturated acids ester derivant is led to
Formula is:
R in described general structure is any one shown in following table:
The purposes of trichodermin C8 unsaturated acids ester derivant the most according to claim 1, is characterized in that: plant for suppression
Thing pathogenic fungi, as the antibacterial on agricultural and/or gardening.
The purposes of trichodermin C8 unsaturated acids ester derivant the most according to claim 2, is characterized in that: described phytopathy
Fungal pathogens is fusarium graminearum (Gibberella zeae), wheat powdery mildew (Blumeria graminis), Fructus Cucumidis sativi grey mold
Pathogenic bacteria (Botrytis cinerea), Rhizoctonia solani Kuhn (Rhizoctonia solani), rice blast fungus
(Pyricularia oryzae) or Ustilaginoidea virens (Ustilaginoidea oryzae).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410018923.XA CN103755718B (en) | 2014-01-15 | 2014-01-15 | Trichodermin C8 unsaturated acids ester derivant and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410018923.XA CN103755718B (en) | 2014-01-15 | 2014-01-15 | Trichodermin C8 unsaturated acids ester derivant and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103755718A CN103755718A (en) | 2014-04-30 |
| CN103755718B true CN103755718B (en) | 2016-08-17 |
Family
ID=50523076
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410018923.XA Active CN103755718B (en) | 2014-01-15 | 2014-01-15 | Trichodermin C8 unsaturated acids ester derivant and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103755718B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101429203A (en) * | 2008-12-04 | 2009-05-13 | 建德市大洋化工有限公司 | Trichodermin derivant and uses thereof |
| CN101787031A (en) * | 2010-03-04 | 2010-07-28 | 建德市大洋化工有限公司 | Trichodermin derivatives and application thereof in preventing and controlling pathogenic bacteria |
| CN103125506A (en) * | 2013-03-21 | 2013-06-05 | 浙江大洋生物科技集团股份有限公司 | Pyrimethanil-containing bactericide composition |
-
2014
- 2014-01-15 CN CN201410018923.XA patent/CN103755718B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101429203A (en) * | 2008-12-04 | 2009-05-13 | 建德市大洋化工有限公司 | Trichodermin derivant and uses thereof |
| CN101787031A (en) * | 2010-03-04 | 2010-07-28 | 建德市大洋化工有限公司 | Trichodermin derivatives and application thereof in preventing and controlling pathogenic bacteria |
| CN103125506A (en) * | 2013-03-21 | 2013-06-05 | 浙江大洋生物科技集团股份有限公司 | Pyrimethanil-containing bactericide composition |
Non-Patent Citations (1)
| Title |
|---|
| 新颖高效杀菌剂木霉菌素的衍生合成及生物活性研究;徐小军;《中国优秀硕士学位论文全文数据库（电子期刊）》;20130315;D046-102页，正文第18-19页表2.2.3.3，正文第70-74页第2.2.6.1节-第2.2.7.1节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103755718A (en) | 2014-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1993328B (en) | Quinoline derivative and insecticide containing same as active constituent | |
| RU2259356C2 (en) | Pyrazolcarboxamide and pyrazolthioamide derivatives as fungicides | |
| CN105849104B (en) | Strigolactone formulations and uses thereof | |
| MX2014004289A (en) | Solid forms of nematocidal sulfonamides. | |
| JP6272843B2 (en) | Solid form of pyridopyrimidinium inner salt | |
| CN103980129A (en) | Ethynylphenylamidine compound or salt thereof, method for producing same, and fungicide for agricultural and horticultural use | |
| Xu et al. | Design, synthesis and evaluation of novel cis-p-menthane type Schiff base compounds as effective herbicides | |
| CN104604927A (en) | Seed-treating agent containing clothianidin, pyraclostrobin and metconazole | |
| CN106922703A (en) | A kind of bactericidal composition | |
| KR20040094444A (en) | Siliconated phenyl amides derivatives useful as microbiocide | |
| CN104904721B (en) | A kind of microbicide compositions and preparation and its application | |
| CN102203086A (en) | Thienylamino pyrimidines for use as fungicides | |
| CN101787031B (en) | Trichodermin derivatives and application thereof in preventing and controlling pathogenic bacteria | |
| CN103755718B (en) | Trichodermin C8 unsaturated acids ester derivant and application thereof | |
| CN104542585A (en) | Fungicide composition and application thereof | |
| CN104926725B (en) | Naphthalimide arylurea compound and use thereof | |
| CN104663687B (en) | A kind of insecticide acaricide composition containing carbamate insecticides | |
| CN103524523B (en) | Trichodermin C8 oxime ether derivative and uses thereof | |
| KR20120016247A (en) | Compounds and methods for controlling fungi | |
| CN100415749C (en) | Silicon compounds with preventing microbiocidal activity | |
| RU2497361C1 (en) | Fungicidal preparation | |
| TW200418380A (en) | Fungicides | |
| CN105541632A (en) | Neryl ambrox ester bactericide | |
| CN105541830B (en) | A kind of Fungicidal compounds, preparation method and applications | |
| CN103408482B (en) | Phenyl volution oxime ether enol ester compounds and uses thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |