Background technology
According to national Eleventh Five-Year Plan development program, the agricultural chemicals innovation is the primary study content with initiative.And the discovery of current novel pesticide or guide's thing is a main path with roughly the same synthetic and natural active matter model still mainly.
Biogenic pesticide is the natural active matter category, is the important channel of novel pesticide initiative.Because of it is little to the person poultry toxicity, environmental compatible is good, and harmful organism be difficult for to produce outstanding advantage such as resistance and meets the requirement of modern society to agriculture production and agricultural chemicals, and this situation also will promote the fast development of biological pesticide.
Agricultural antibiotic (Agricultural antibiotics) always is the emphasis of biological pesticide research, as far back as mid-term in 20th century, in the state key scientific research planning has just been listed the research of agricultural antibiotic by developed countries such as U.S., moral, day, and successfully developed many outstanding products, as Avrmectin, pleocidin etc.In today that the environmental and ecological protection measure is continually strengthened; China's agricultural chemicals is faced with huge day by day update pressure and very stern challenge; for the needs of Sustainable development and help the outlet of agricultural products in China; that country has further strengthened is efficient, the R﹠D intensity of safety, harmless boilogical agricultural chemicals, and novel agricultural antibiotic research has been put into the Eleventh Five-Year Plan plan of diplomatizing of country's " 863 Program " and science and technology especially.
In recent years, be lead compound with the natural antibiotics, carry out the initiative research of novel pesticide in conjunction with chemical synthesising technology, become in the current novel pesticide initiative process one of effective means the most, obtained good effect.As, Dioxapyrrolomycin is all producible pyrrole ring microbiotic that contain of one kind of multiple microorganisms, tool antibacterium and fungi activity, but because stability etc. is many former thereby be difficult to commercialization, American Cyanamid Company is that parent has carried out substituent modification and transformation with its effective group, overcome unstable, developed the sterilant bromothalonil (Chlorfenapyr) that is described as one of world today's new pesticides three big pillars light; Avrmectin is that drug effect is the highest so far, one of sterilant that consumption is minimum, but owing to it is higher and limited its application in cultural control to the lepidoptera pest preventive effect is relatively poor to people and animals' acute toxicity, for this reason, the researchist has carried out structure of modification by chemical means to Avrmectin both at home and abroad, develop Ivermectin HCL (Ivermectin) in succession, emaricin (Emamectin), Ai Polinuo rhzomorph (Eprinomectin), the road draws rhzomorph (Doramectin), greatly reduce former medicine toxicity, improve activity, and enlarged the range of application of Avrmectin effectively.They are applied to agriculture desinsection (agricultural chemicals), expelling parasite for animals, health respectively with desinsection, human expelling parasite four major trades, can make more than 30 kind of hundreds of product of formulation, and market capacity is very big.With regard to present domestic and international market, annual sales amount over ten billion dollar.The world main husbandry country this medicine of widespread usage, as in countries and regions such as the U.S., South America, Australia, New Zealand, Europe, Ivermectin HCL accounts for insect repellent market more than 50%.
As seen, produce novel pesticide by the natural source material through the chemical structure transformation, reduce existing antibiotic toxicity, improve its biological activity and stability is not only significant to exploitation novel green Pesticidal products, and, promote that further the researchdevelopment of agricultural anti-class biological pesticide is significant to improving the comprehensive utilization value of existing antibiotic product.For the microbe metabolite that has some weak point, people are often by the chemical structure transformation is better with development effectiveness, security is higher, the more rational new medicament of physico-chemical property.
Simultaneously, this method of seeking novel pesticide from the natural source kind through chemical improvement has become one of important channel of current novel pesticide exploitation.There are many independently developed natural source materials in China, and (as toxicity, the stability etc.) for various reasons that have are difficult to industrialization, even if the industrialization that has but still have some deficiency, and can't form bulk product.In addition, also having the byproduct that the close but effect of structure differs very big in process of production produces.How to pass through chemical means, therefrom seek to have active new medicament.Merck ﹠ Co., Inc.'s successful example on Avrmectin is for we provide good enlightenment.Undoubtedly, this has also become us to formulate one of direction of novel pesticide.
Plant diseases brings about great losses to crop yield every year, although the method for controlling plant disease and measure are varied, sterilant still occupies an important position in the Plant diseases integrated control.A lot of chemical bactericides at present commonly used have the characteristics of wide spectrum, efficient, low toxicity, have improved the effect of sterilant controlling plant disease significantly.Yet some chemical bactericide has resistance, to problems such as environment, the pollutions of food cumulative bad, so to biogenic pesticide, particularly seek from natural phant, animal and microorganism and the development research of development of new sterilant is current research focus.
Endogenetic fungus and natural product thereof have the important use potentiality in modern bio-pharmaceutical exploitation, the trichothecene compounds is the famous mycotoxins of a class, meta-bolites for Fusarium (Fusarium), Trichothecium (Trichothecene), Trichoderma (Trichoderma), the mould genus of lacquer spot fungies such as (Myrothecium), these compounds all have a similar sesquiterpene skeleton, contain a stable epoxy and alkene double bond structure in the molecule usually.The trichothecene compounds has the function of inhibition or worth concerns such as kill fungi (comprising many phytopathogens) and inhibition plant-growth.Can suppress various plants pathogenic bacteria mycelial growths such as Aspergillus flavus, A.niger, Cladosporium cucumerium, Rhizoctonia solani, R.bataticola, Candida albicans and Rhizopus stolonifer as Trichodermin (formula III compound), trichodermin is to the obvious restraining effect of coleoptile growth tool of tobacco, bean, wheat class etc., and can absorb from root, cause above-mentioned plant death.
Trichodermol (formula II compound) is the simplest trichothecene compounds of structure, find at a large amount of domestic and foreign literatures of retrieval and after by the preliminary study of project team to part trichothecene class active substance, the compound that with trichodermol is basic framework not only has the activity that suppresses fungi efficiently and suppress plant-growth, and its toxicity is low, safer to Mammals, have huge potentiality to be exploited.
Trichodermin (Trichodermin, formula III compound) is a kind of known endogenous fungus metabolite, and corresponding report is arranged external morning.The patent of invention of the patent No. 200710106257.5 " a kind of yew trichoderma strain and the purposes in the preparation trichodermisin thereof " provides a kind of mould Trichoderma taxi of new endogenetic fungus yew bacterial strain ZJUF0986 that is separated to from the endogenetic fungus southerm yew, meta-bolites-the trichodermin of its fermentation (Trichodermin) is that the various plants pathogenic bacteria is had good prevention effect: it has very strong restraining effect to dry thread Pyrenomycetes and Botrytis cinerea bacterium, and rice blast and banded sclerotial blight are also had good inhibition effect.
Have the characteristic of agricultural antibiotic just because of trichodermin, it has the characteristics of antibiotic high efficiency and broad spectrum, and can be separated in many Trichoderma tunnings; Because it obtains by fermentation, extraction separation, for better screening is synthetic than its more highly active compound, this seminar carries out functional group's transformation to the precursor structure of trichodermin, synthetic preparation series derivates, in case the trichodermin derivative that acquired price ratio is higher then has industrialization prospect.
Through applicant's data-searching, series derivates of the present invention is the synthetic new compound, does not have its synthetic and use relevant report.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of trichodermin derivant with better sterilization effect and its production and use.
In order to solve the problems of the technologies described above, the invention provides a kind of trichodermin derivant, its general structure is:
R is (for convenience of description, as follows to the pairing trichodermin derivant numbering of each concrete R) in the formula:
Compound a-1 compound a-2 compound a-3 compound a-4
Compound a-5 compound b-1 compound b-2 compound b-3
Compound b-4 compound b-5 compound b-6 compound b-7 compound b-8
Compound b-9 compound b-10 compound b-11 compound b-12 compound b-13
Compound c-1 compound c-2 compound c-3 compound c-4 compound c-5 compound c-6
Compound c-7 compound c-8 compound c-9 compound c-10 compound c-11
Compound c-12 compound c-13 compound c-14
The present invention also provides the synthetic method of above-mentioned trichodermin derivant simultaneously: in acid binding agent and non-proton organic solvent, structural formula is
The trichodermin hydrolyzate and the structural formula acyl chlorides that is R-Cl or with R-OH at room temperature, react under the normal pressure, the reaction times is 0.4~24h, the mol ratio of trichodermin hydrolyzate and acyl chlorides (or and R-OH) is 1:1~6; The mol ratio of trichodermin hydrolyzate and acid binding agent is 1:1~6;
R is in the formula:
The gained reaction solution is separated, promptly get trichodermin derivant.
Improvement as the synthetic method of trichodermin derivant of the present invention: non-proton organic solvent and trichodermin hydrolyzate weight ratio are 3~30:1; Non-proton organic solvent is alkanes, ethers, arene or alkane substitute class, preferred normal hexane, hexanaphthene, ether, benzene, toluene, chloroform, methylene dichloride and 1,2-ethylene dichloride.Acid binding agent is alkaline reagentss commonly used such as triethylamine, pyridine, quadrol.
The present invention also provides the purposes of above-mentioned trichodermin derivant simultaneously, is used to kill plant pathogenic fungi.
Improvement as the purposes of trichodermin derivant of the present invention: described plant pathogenic fungi is botrytis cinerea Botrytis cinerea, the mould Pythium ultimum of ultimate corruption, sickle-like bacteria (cucumber specialized form) Fusarium oxysporum f.spcucumber, leaf mold, dry thread Pyrenomycetes, cotton is withered or rice blast fungus.
Further improvement as the purposes of trichodermin derivant of the present invention: trichodermin derivant is made into: the weight content of trichodermin derivant is that the weight content of 5~60% wettable powder, trichodermin derivant is 5~80% missible oil, microemulsion or aqueous emulsion.
The present invention sets out and different acyl chlorides or R-OH reactions from trichodermin hydrolysate (trichodermol, formula II compound), thereby prepares serial trichodermin derivant; Therefrom obtain to have the compound of better prevention plant pathogenic fungi with expectation.
The synthetic method of trichodermin derivant of the present invention can be illustrated with following equation:
The serial trichodermin derivant of gained of the present invention is carried out indoor determination of activity with fusarium graminearum Gibberella zeae, botrytis cinerea Botrytis cinerea, leaf muld of tomato bacterium Fulvia fulva, under 50 μ g/mL, all compounds all show good bacteriostatic activity, and inhibiting rate is up to more than 80%.Wherein compound a-1, compound c-4, compound c-5, compound c-6, compound c-7, compound c-10 etc. to concentration in the inhibition of graw mold of tomato all between 0.3~2.0 μ g/mL; The wettable powder, missible oil, microemulsion, aqueous emulsion or the suspension agent that are mixed with different concns use, and prevention effect is better.
During actual use, detailed directions and consumption are as follows in the field for trichodermin derivant of the present invention:
Trichodermin derivant is processed into wettable powder, missible oil, microemulsion or aqueous emulsion, when using in the field, each by every mu of effective constituent 0.5g~2g/, dilution back (after for example diluting 500-600 times by weight) sprays with miniaturised nebuliser, or be stained with lace and handle tomato, when having gray mold to occur on the blade, determine later on time of medication for the first time crop to be carried out whole sprayings handle in the tomato field planting; Engage later on and pour water and spraying sterilant 3 times before the rainy weather continuously, and all to spray number of times be 3 to 4 times that the spray intervals phase was controlled at 8-15 days in the season occurred frequently of disease.
The invention has the advantages that: synthesized the novel derivative compound that is different from Trichodermin that series is not appeared in the newspapers, because its precursor structure is the meta-bolites of natural endogenetic fungus, through efficient strain fermentation, obtain through extraction separation, active fine, so all have certain biological activity for lead compound designs the synthetic series derivates with this precursor structure, compound a-1 wherein, compound c-4, compound c-5, compound c-6, compound c-7, compound c-10 grade all between 0.3~2.0 μ g/mL, has the condition that further is developed as the commodity sterilant to concentration in the inhibition of graw mold of tomato.
Embodiment
Trichodermin (the Trichodermin that the present invention adopts fermentation to obtain, the formula III compound) is raw material, obtain trichodermol (trichodermol by hydrolysis, formula II compound, be the trichodermin hydrolyzate), further carry out derivative reaction, obtain compound a-1~c-14, and carry out fungicidal activity and measure, from general sieve, select inhibiting rate under the 50 μ g/mL concentration and carry out primary dcreening operation more than 60%, select inhibiting rate under the 25 μ g/mL concentration behind the primary dcreening operation and carry out multiple sieve more than 60%, obtain concentration in the inhibition.
The preparation of reaction raw materials trichodermol (trichodermol, formula II compound):
In reaction flask, add 2.0g (6.85mmol) trichodermin (formula III compound), the sodium hydroxide solution of 24mL 2mol/L, 35mL methyl alcohol, 20 ℃ of following stirring reaction 1.5h.Reaction solution ethyl acetate extraction three times, ethyl acetate layer washes with water 2 times, anhydrous Na
2SO
4Drying, concentrate the 1.72g product, reaction product is purer to be directly used in next step reaction.
1H-NMR(500MHz,CDCl
3,δppm):5.396-5.386(1H,m,-C=CH-),4.357-4.321(1H,t,-CH-OH),3.842-3.828(1H,d,-O-CH-CH
2-),3.516-3.503(1H,d,-C=C-CH-O-),3.123-3.113(1H,d,-O-CH
2),2.824-2.814(1H,d,-O-CH
2),2.646-2.589(1H,dd,-CH
2CHOH),2.001-1.955(2H,m,-CH=C-CH
2-),1.942-1.907(1H,dd,-CH=C-CH
2-CH
2-),1.896-1.882(1H,d,-CH
2CHOH),1.711(3H,s,-CH=C-CH
3),1.458-1.430(1H,m,-CH=C-CH
2-CH
2-),0.935(3H,s,CH
3-C-CH-OH),0.718(3H,s,CH
3-C-CH
2-)。
The synthetic method of embodiment 1, a kind of trichodermin derivant a-1, its reaction formula is:
Concrete reaction process is as follows:
In reaction flask, add the wooden mould hydrolyzate of 4.0g (16.0mmol) (structural formula is II), 6.0g (60.0mmol) triethylamine and 80mL methylene dichloride under the ice-water bath, drip 3.6g (19.3mmol) dimethyl chrysanthemum acyl chlorides again, (0~30 ℃) stirring reaction 0.5h under the room temperature.
Reaction solution is used saturated NaHCO again with the salt acid elution of 1% concentration three times
3Solution washing twice washes twice with water, anhydrous Na at last
2SO
4Drying, concentrate the 6.5g solid product, through ethyl alcohol recrystallization, after the filtering separation 5.8g product a-1, Y=90.6%.
1H-NMR(500MHz,CDCl
3,δppm):5.596-5.573(1H,m,-COOCH-),5.411-5.398(1H,m,-C=CH-),4.898-4.877(1H,m,Me
2C=CH-),3.830-3.819(1H,m,-O-CH-CH
2-),3.614-3.603(1H,d,-C=C-CH-O-),3.125-3.117(1H,d,-O-CH
2),2.833-2.825(1H,d,-O-CH
2),2.545-2.498(1H,m,-COOCH-CH
2),2.088-2.099(1H,d,-COCH),2.041-2.030(2H,m,-CH=C-CH
2-),2.010-1.978(1H,m,-COOCH-CH
2),1.960-1.950(1H,m,-CH=C-CH
2-CH
2-),1.937-1.925(1H,m,Cl
2C=CH-CH),1.713(3H,s,-CH=C-CH
3),1.460-1.452(1H,d,-CH=C-CH
2-CH
2-),1.263-1.254(3H,d,C-Me2),1.132-1.125(3H,d,C-Me2),0.960(3H,s,-Me),0.709(3H,s,-Me)。
The synthetic method of embodiment 2, a kind of trichodermin derivant c-2, its reaction formula is:
In reaction flask, add the wooden mould hydrolyzate of 4.0g (16.0mmol) (structural formula is II), 6.0g (60.0mmol) triethylamine and 80mL methylene dichloride under the ice-water bath, drip 3.28g (19.3mmol) 2-bromo propionyl chloro again, (0~30 ℃) stirring reaction 0.5h under the room temperature.
Reaction solution is used saturated NaHCO again with 1% salt acid elution three times
3Solution washing twice washes twice with water, anhydrous Na at last
2SO
4Drying, concentrate the 6.13g solid product, through ethyl alcohol recrystallization, after the filtering separation 5.25g product c-2, Y=85.5%.
1H-NMR(500MHz,CDCl
3,δppm):5.589-5.563(1H,m,-COOCH-),5.412-5.403(1H,d,-C=CH-),4,442-4.393(1H,m,Br-CH-),3.853-3.836(1H,m,-O-CH-CH
2-),3.596-3.585(1H,d,-C=C-CH-O-),3.132-3.124(1H,d,-O-CH
2),2.840-2.825(1H,m,-O-CH
2),2.589-2.542(1H,m,-COOCH-CH
2),1.999-1.989(1H,m,-COOCH-CH
2),1.999-1.989(2H,d,-CH=C-CH
2-),1.999-1.989(1H,m,-CH=C-CH
2-CH
2-),1.843-1.823(2H,m,Br-CH-CH
3),1.717(3H,d,-CH=C-CH
3),1.702-1.688(1H,m,Br-CH-CH
3),1.467-1.433(1H,m,-CH=C-CH
2-CH
2-),0.943(3H,s,-Me),0.782-0.736(3H,m,-Me)。
The synthetic method of embodiment 3, a kind of trichodermin derivant c-5, its reaction formula is:
In reaction flask, add the wooden mould hydrolyzate of 4.0g (16.0mmol) (structural formula is II), 6.0g (60.0mmol) triethylamine and 80mL methylene dichloride under the ice-water bath, drip 2.0g (19.3mmol) 3 again, 3-dimethyl-butyrylchlorine acyl chlorides, (0~30 ℃) stirring reaction 6h under the room temperature.
Reaction solution is used saturated NaHCO again with 1% salt acid elution three times
3Solution washing twice washes twice with water, anhydrous Na at last
2SO
4Drying, concentrate the 5.67g solid product, through ethyl alcohol recrystallization, after the filtering separation 4.86g product c-5, Y=95.05%.
1H-NMR(500MHz,CDCl
3,δppm):7.036-6.963(H,m,-CH=CH-CH
3),5.903-5.862(H,dd,-CH=CH-CH
3),5.630-5.615(1H,m,-COOCH-),5.419-5.405(1H,m,-C=CH-),3.837-3.827(1H,d,-O-CH-CH
2-),3.632-3.621(1H,d,-C=C-CH-O-),3.130-3.122(1H,d,-O-CH
2),2.835-2.827(1H,m,-O-CH
2),2.577-2.530(1H,m,-COOCH-CH
2),2.011-2.003(1H,m,-COOCH-CH
2),2.000-1.992(2H,d,-CH=C-CH
2-),1.982-1.963(1H,m,-CH=C-CH
2-CH
2-),1.886-1.868(3H,dd,-CH=CH-CH
3),1.715(3H,d,-CH=C-CH
3),1.393-1.417(1H,d,-CH=C-CH
2-CH
2-),0.947(3H,s,-Me),0.719(3H,s,-Me)。
The synthetic method of embodiment 4, a kind of trichodermin derivant c-7, its reaction formula is:
With trifluoroacetic acid 2.4g (21mmol), N, N-dicyclohexyl carbon diimine (DCC) (4.3g, 21mmol) place the reaction flask of 150ml, add the methylene dichloride of doing (80ml), stir 1h under the room temperature, then add 4-dimethylaminopyridine (DMAP) and wooden mould hydrolyzate (structural formula is the II) (5g of catalytic amount (0.5g), 20mmol), stir 24h under the room temperature.Filter, gained filtrate is used saturated NaHCO again with 1% salt acid elution three times
3Solution washing twice washes twice with water, anhydrous Na at last
2SO
4Drying, concentrate the 3.92g solid product, through ethyl alcohol recrystallization, after the filtering separation 3.0g product c-7, Y=43.18%.
1H-NMR(500MHz,CDCl
3,δppm):5.710-5.688(1H,m,-COOCH-),5.420-5.403(1H,m,-C=CH-),3.888-3.877(1H,d,-O-CH-CH
2-),3.572-3.561(1H,d,-C=C-CH-O-),3.152-3.144(1H,d,-O-CH
2),2.851-2.843(1H,d,-O-CH
2),2.652-2.606(1H,m,-COOCH-CH
2),2.147-2.098(1H,m,-COOCH-CH
2),2.022-2.004(2H,m,-CH=C-CH
2-),1.973-1.937(1H,m,-CH=C-CH
2-CH
2-),1.579(3H,s,-CH=C-CH
3),1.456-1.423(1H,m,-CH=C-CH
2-CH
2-),0.947(3H,s,-Me),0.760(3H,s,-Me)。
The synthetic method of embodiment 5, a kind of trichodermin derivant c-10, its reaction formula is:
With cyanogen for acetate 2.55g (21mmol), N, N-dicyclohexyl carbon diimine (DCC) (4.3g, 21mmol) place the reaction flask of 150ml, add methylene dichloride (80ml), stir 1h under the room temperature, then add 4-dimethylaminopyridine (DMAP) and wooden mould hydrolyzate (structural formula is the II) (5g of catalytic amount (0.5g), 20mmol), stir 24h under the room temperature.Filter, gained filtrate is used saturated NaHCO again with 1% salt acid elution three times
3Solution washing twice washes twice with water, anhydrous Na at last
2SO
4Drying, concentrate 3.7g solid product c-10, Y=44.9%.
1H-NMR(500MHz,CDCl
3,δppm):5.574-5.551(1H,m,-COOCH-),5.397-5.383(1H,m,-C=CH-),3.822-3.812(1H,d,-O-CH-CH
2-),3.646-3.643(2H,d,-CH
2-CN),3.580-3.569(1H,d,-C=C-CH-O-),3.120-3.112(1H,d,-O-CH
2),2.815-2.807(1H,d,-O-CH
2),2.539-2.493(1H,m,-COOCH-CH
2),2.002-1.985(1H,m,-COOCH-CH
2),1.971-1.964(2H,d,-CH=C-CH
2-),1.954-1.906(1H,m,-CH=C-CH
2-CH
2-),1.701(3H,d,-CH=C-CH
3),1.403-1.375(1H,m,-CH=C-CH
2-CH
2-),0.901(3H,s,-Me),0.645(3H,s,-Me)。
Embodiment 6, growth velocity inhibiting rate method are measured the biological activity of compound
With test strain germ botrytis cinerea Botrytis cinerea, the mould Pythiumultimum of ultimate corruption, the leaf muld of tomato bacterium F.fulva that is stored in the paraffin oil, rhizoctonia cerealis R.cerealis, cotton-wilt fusarium F.oxysporumf.sp.vasinfectum, rice blast fungus P.oryzae is seeded to activation culture on the PDA substratum, 25 ℃ of lucifuges are cultivated 4d, inoculating needle picking part mycelia piece is transferred on the PDA culture plate, place 25 ℃ incubator growth, it is promptly available to treat that its bacterium colony covers with till the culture dish substantially.
Earlier test strain is cut the bacterium cake with the punch tool of Φ mm, insert PDA culture medium flat plate center (according to difference test bacteria growing speed control inoculation time), place 25 ℃ of incubators about 1-2d that grow.Get one of aseptic filter paper sheet, drip and go up (with 10 μ l rifles) 10 μ l sample solutions, treat that solvent volatilizes the back and moves on the PDA culture medium flat plate, the culture dish center is about about 30mm to the distance at filter paper center, again culture dish is placed 25 ℃ of incubators to grow then.During test,,, all positive control need be arranged in the every flat board with the positive contrast of trichodermin with sterilized water and the negative contrast of acetone.
The measurement of antibacterial circle diameter: according to the growing state of test bacterium, grasp the opportunity of measuring antibacterial circle diameter, during measurement, growing to filter paper with blank is foundation, measures the distance of colony edge to filter paper.When treating that the long diameter 5.0cm of arriving of blank part bacterium colony is big or small, measure the size of each bacterium colony, calculate its inhibiting rate according to the size of bacterium colony.General sieve as a result the inhibiting rate of each compound all more than 80%, further primary dcreening operation, inhibiting rate sees Table 1 under the 25 μ g/ml:
Table 1, numerical value are the inhibiting rate (%) of 25 μ g/ml
|
Tomato gray mould |
Ultimate corruption is mould |
Leaf mold |
Dry thread Pyrenomycetes |
Cotton is withered |
Rice blast fungus |
a-1 |
95 |
90 |
85 |
80 |
80 |
80 |
a-2 |
70 |
66 |
88 |
60 |
86 |
78 |
b-2 |
74 |
71 |
75 |
65 |
80 |
73 |
b-3 |
73 |
66 |
70 |
45 |
75 |
62 |
b-1 |
76 |
30 |
72 |
37 |
78 |
60 |
b-4 |
71 |
60 |
60 |
50 |
60 |
60 |
b-5 |
75 |
68 |
72 |
20 |
55 |
55 |
c-1 |
96 |
85 |
82 |
82 |
85 |
80 |
c-2 |
85 |
80 |
80 |
75 |
75 |
80 |
c-3 |
75 |
75 |
80 |
70 |
75 |
70 |
c-4 |
100 |
100 |
98 |
95 |
96 |
90 |
c-5 |
100 |
100 |
100 |
100 |
100 |
100 |
c-6 |
100 |
100 |
100 |
100 |
95 |
95 |
c-7 |
100 |
100 |
100 |
100 |
100 |
100 |
c-8 |
90 |
96 |
96 |
96 |
90 |
90 |
c-9 |
85 |
80 |
80 |
80 |
80 |
80 |
c-10 |
100 |
100 |
100 |
100 |
100 |
100 |
c-11 |
90 |
85 |
90 |
85 |
85 |
85 |
The Ck-trichodermin |
100 |
95 |
90 |
100 |
80 |
80 |
The EC of table 2, several high-activity compounds
50(μ g/ml)
|
Tomato gray mould |
Ultimate corruption is mould |
Leaf mold |
Dry thread Pyrenomycetes |
Cotton is withered |
Rice blast fungus |
a-1 |
2.0 |
16.3 |
8.6 |
12.1 |
2.2 |
10.9 |
c-4 |
1.1 |
6.2 |
7.5 |
7.3 |
0.6 |
2.6 |
c-5 |
0.9 |
2.2 |
1.7 |
2.4 |
1.4 |
1.8 |
c-6 |
1.1 |
4.8 |
2.2 |
1.7 |
1.2 |
2.6 |
c-7 |
1.1 |
2.3 |
1.8 |
1.7 |
3.0 |
2.4 |
c-10 |
1.0 |
2.0 |
1.2 |
1.6 |
1.8 |
3.2 |
The Ck-trichodermin |
1.2 |
9.3 |
11.0 |
1.2 |
12.4 |
16.1 |
Compound a-1, c-4, c-5, c-6, c-7, c-10 have good activity to the various plants pathogenic bacteria, prepare preparation after activity higher, can further be developed as the commodity sterilant.
The preparation of embodiment 7,30% trichodermin derivant a-1 wettable powder (WP)
Add 30g trichodermin derivant a-1 in mixing machine, commercially available filler white carbon black 10g, draws back powder 5.0g, saponin 10g, wilkinite 40g at dispersion agent NNO5g, and thorough mixing fully is crushed to 325 orders, makes the white powder preparation.Dispersiveness, dilution stability, cold and hot storage stability meet the requirement of commercially available agricultural chemical preparation in the said preparation water.
The preparation of embodiment 8,20% trichodermin derivant c-4 missible oil (EC)
20g trichodermin derivant c-4, agricultural newborn 500# (calcium dodecylbenzene sulphonate) 3.5g, emulsifier 600 series (vinylbenzene acid Soxylat A 25-7) 5g, penetrant azone 0.5g, dimethylbenzene 71g stir, and make faint yellow transparent oily preparation.Dispersiveness, dilution stability, cold and hot storage stability meet the requirement of commercially available agricultural chemical preparation in the said preparation water.
The preparation of embodiment 9,5% trichodermin derivant c-5 microemulsion (ME)
5g trichodermin derivant c-5, styrenated phenol Soxylat A 25-7 5g, oxyethane propylene oxide block copolymer 8g, solubility promoter Virahol 10g, deionized water 72g stirs, and makes faint yellow clear microemulsion agent.Dispersiveness, dilution stability, cold and hot storage stability meet the requirement of commercially available agricultural chemical preparation in the said preparation water.
The preparation of embodiment 10,10% trichodermin derivant c-7 aqueous emulsion (EW)
10g trichodermin derivant c-7, vinylbenzene acid Soxylat A 25-7 5g, oxyethane propylene oxide block copolymer 8g, isopropylcarbinol 2.0g, dispersion agent TamolNN8906 2.0g, water 73g stirs, at high-shear machine down cut emulsification 2hr, make pale emulsus preparation.Dispersiveness, dilution stability, cold and hot storage stability meet the requirement of commercially available agricultural chemical preparation in the said preparation water.
The preparation of embodiment 11,25% trichodermin derivant c-10 suspension agent (SC)
25g trichodermin derivant c-10, dispersion agent VanGeL B 2.5g, oxyethane propylene oxide block copolymer 5g, propylene glycol 5.0g, dispersion agent TamolNN8906 2.5g, thickening material xanthan gum 0.5g, preservative sodium benzoate 0.5g, water 59g, stir,, make pale emulsus preparation at high-shear machine down cut emulsification 2hr.Dispersiveness, dilution stability, cold and hot storage stability meet the requirement of commercially available agricultural chemical preparation in the said preparation water.
Embodiment 12, field test
With 10% trichodermin derivant c-7 aqueous emulsion among the embodiment 10 is example, and 10% trichodermin (formula III) aqueous emulsion of cofabrication same prescription is as the reference medicament.Consumption is with reference to actual field of the present invention consumption.
In experiment, the preparation of the various different ingredients of forming for compound by technical scheme preparation of the present invention, all can reach more satisfactory effect.
1200 times, 800 times of 10% trichodermin derivant c-7 aqueous emulsions and 1200 times, 800 times of the 10% trichodermin aqueous emulsions among the embodiment 10 established in test and common fungicide is executed 1200 and 800 times of good pleasure 40% suspension agents (SC) and clear water contrasts 6 processing, repeat for 4 times, district's group is arranged at random, experimental subjects is the tomato of general planting, about 30 strains in each sub-district, begin to spray medicine from the blade their early stage, every spray in 8 days 1 time, spray altogether 3 times, evenly spray the blade face during spray medicine, emphasis spray blade back is till dripping a little.
Investigation method is with reference to pesticide field efficacy medicine test criterion (one), according to the degree that is in a bad way of tomato leaf before the dispenser, determines before the dispenser that whether earlier the investigation disease refers to, refers to respectively investigating 1 disease in 7~10 days for the second time and after the dispenser for the third time then.Every sub-district random inspection 10~15 strains, 10 leaves are investigated in every strain from top to bottom, every leaf accounts for the long-pending percentage of leaf surface by scab and carries out classification, and each concentration of calculating reagent agent is handled average disease and referred to and preventive effect, and with the DMRT method test-results is carried out significance of difference analysis.
0 grade: fruit is not fallen ill;
1 grade: scab accounts for below 5% of whole fruit area;
3 grades: scab accounts for 6%~15% of whole fruit area;
5 grades: scab accounts for 16%~25% of whole fruit area;
7 grades: scab accounts for 26%~50% of whole fruit area;
9 grades: scab accounts for more than 50% of whole fruit area.
Table 3, reagent agent are to the preventive effect of graw mold of tomato
Presentation of results: under the prerequisite of identical effective dosage, the effect of 10% trichodermin derivant c-7 aqueous emulsion obviously is better than 10% trichodermin aqueous emulsion.
At last, it is also to be noted that what more than enumerate only is several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.