CN1015085B - Adopt cyclodextrin to improve the method for activation of plant preservatives - Google Patents
Adopt cyclodextrin to improve the method for activation of plant preservativesInfo
- Publication number
- CN1015085B CN1015085B CN86100966A CN86100966A CN1015085B CN 1015085 B CN1015085 B CN 1015085B CN 86100966 A CN86100966 A CN 86100966A CN 86100966 A CN86100966 A CN 86100966A CN 1015085 B CN1015085 B CN 1015085B
- Authority
- CN
- China
- Prior art keywords
- cyclodextrin
- benomyl
- composition
- active component
- fungicidal
- 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.)
- Expired
Links
Classifications
-
- 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
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
- A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
Abstract
The present invention is relevant antifungal plant protection composition, and it is mixed by the cyclodextrin of the Fungicidal active ingredient of 3-90% by weight and 1-90% by weight and optional usual auxiliaries and forms.
The advantage of cooperative compositions of the present invention is; Reaching under the prerequisite of identical fungicidal effect, can obviously reduce absorption of active ingredient, so just reducing and the active component cost related, and also reducing the danger of environmental pollution.
Description
The present invention is about compoistion and method of use new and improved plant protection product, particularly bactericide.
Several pieces of article and patent (Noev é nyv é delem, 19 volumes, 364 pages (1983) have been delivered recently about in the plant protection agent prescription, using cyclodextrin; J.Szejtli: cyclodextrin and comprise complex, Akad é miai Kiad ó, Budapest, 1982).Forming ordram (S-ethyl-N, N-hexa-methylene-thiocarbamate), benthiocarb (S-4-benzyl chloride base-diethyl thiocarbamate) and dichloro phosphide (2, during 2-dichloroethylene-dimethyl phosphate) complex compound, the volatility of active component significantly reduces, and the activity of agricultural chemicals still keeps long time (Mikasa Chemical Industrial Co. simultaneously; KOKAI No 80.81806; DOS No 2,422,316(1974); Acta chem.Acad.Sci.Hung.107 volume, 195 pages (1981)).In order to improve stability greatly to light and oxygen, parathion-methyl (0,0-dimethyl-0-4-nitrobenzophenone thiophosphate) and natural pyrethrins and the pyrethroid complex (Pestic.Sci.11 volume, 134 pages (1980) that change into cyclodextrin respectively; US Patent No 3,846,551(1974); Nippon Noyaku Gakkaishi 1 volume, 41 pages (1976); 2 volumes, 41 pages (1977)).Dichlobenil (2,6-dichloro-benzonitrile) active component distils easily, and when depositing, granular product can bond together, can be by forming generation (the 5th Int.Cong.Pesticide Chem.(IUPAC) Kyoto(1983 that complex prevents above-mentioned situation with cyclodextrin)).
When the complex that is formed by 2-chloromethane phosphonic acids and cyclodextrin contacts with plant tissue, the release of its ethene is a long-acting process, therefore it is than by discharging ethene more effective (Acta Chim.Acad.Sci.Hung.107 rolls up, 231 pages (1981)) in the instantaneous active component that works.
According to prior art is to can't see cyclodextrin can have synergistic to the effect of fungicide.
The purpose of this invention is to provide the Fungicidal composition of being made up of cyclodextrin, in this composition, cyclodextrin can produce very big synergy to the activity of known Fungicidal active ingredient.Therefore, use the Fungicidal active ingredient of equal dose, just can produce bigger activity; adopt active component in other words, just can obtain same fungicidal effect, simultaneously than low dosage; from economy and environmental protection two aspects, the present invention also has significant superiority.
One aspect of the present invention provides a kind of antifungal plant protection composition, and it is by forming for the Fungicidally active composition of 3-90% mixes with the general adjuvant of choosing wantonly with the cyclodextrin that is 1-90% by weight by weight.
According to the present invention, in Fungicidal composition, the ratio of Fungicidal active ingredient and cyclodextrin is 90: 1-1: 5, be preferably 2-5: 1.
According to the present invention, composition preferably is made up of following Fungicidal active ingredient:
Benomyl=1-butyl carbamyl-benzimidazolyl-2 radicals-methyl-carbamate;
Carbendazim=2-methoxycarbonyl amino-benzimidazole;
Metomeclan=1-(3, the 5-dichlorophenyl)-3-methoxyl methyl-pyrrolidines-2, the 5-diketone;
Phenarimmol=2,4 '-two chloro-α-(pyrimidine-5-yl)-benzohydrol.
As cyclodextrin, α-, β-and/or gamma-cyclodextrin can use.
According to optimum implementation of the present invention, the above-mentioned active component and the ratio of cyclodextrin are:
Benomyl: cyclodextrin=2-5: 1
Carbendazim: cyclodextrin=2-5: 1
Metomeclan: cyclodextrin=2-20: 1
Phenarimmol: cyclodextrin=1-100: 10.
Another aspect of the present invention provides a kind of mycocidal processing method, promptly adopts composition of the present invention to be sprinkling upon on plant or other surface, and its consumption is suitably 0.5-6 kilogram/hectare, is good with 1.2-1.6 kilogram/hectare especially.
The fact of institute of the present invention foundation is, known Fungicidal active ingredient and cyclodextrin can demonstrate synergistic effect, and this is produced by following one or two factor:
The system fungi activity of cyclodextrin itself;
Cyclodextrin can improve deliquescent effect.
The system fungi activity of cyclodextrin never disclosed in prior art.This activity can be by following evidence:
In Petri dish, prepare every milliliter respectively and contain 0.1,0.2,0.5,1.0,2.0,5.0,10.0,20.0,100.0,200.0,400.0,800.0,1200.0,1500.0, the agar medium of 2000.0,3000.0 microgram beta-schardinger dextrin-s.Three test moulds that the mycelium sheet is cultivated from the surface are separated, and they are placed on the agar medium in the Petri dish.In thermostat, cultivate, measure the growth of colony diameter then, and compare with the diameter of tester.The situation that the coloring matter of measuring the form of bacterium colony and being produced by mould spreads in medium.The result takes passages in table 1.
Table 1
The inhibition fungi effect of beta-schardinger dextrin-
Inhibiting rate %
Concentration Rhizoctonia solani Kuhn sclerotinite Alternaria tenuissima
（Rhizoctonia （Sclerotinia （Alternaria
Solani） sclerotiorum） tenuis）
3000 19 16 14
1500 17 14 12
400 6 12 10
200 3 12 7
When the dosage of beta-schardinger dextrin-was in the scope of 0.1-20 mcg/ml, its effect only had character qualitatively.The mould effect of the system of cyclodextrin can be showed by form, structure and the change in color of bacterium colony and the number of colors that is penetrated in the medium.Yet than higher dosage range the time, the effect of cyclodextrin has had quantitative characteristic, therefore can determine the minimizing of colony diameter, simultaneously, the quantity of the biomass of formation also reduce to can be determined degree (table 1).The beta-schardinger dextrin-that studies show that cultivate on the surface can suppress to breed the formation of organ.
Owing to making cyclodextrin have the main feature that improves the dissolubility effect, the formation inclusion complex is based on the following fact, promptly in the aqueous solution, except disperseing the active component of (promptly being actually dissolving) with molecular state and by some mycelium that perhaps polymolecular (crystallite, droplet) is formed, cyclodextrin one active component inclusion complex also is with the form appearance of molecular state dispersion.
Because above-mentioned system is (10 with significant kinetic balance
-8In/second the scope) be feature, fused active component in inclusion complex, from the viewpoint that absorbs, its effect is equivalent to the active component with the free state dissolving.
Therefore,, can improve the molecular concentration that is suitable for directly absorbing widely, so just quicken absorption rate, just use the active component of less dosage, can reach identical effect with the molecular state dispersion by means of the help of cyclodextrin.
Cyclodextrin can embody from the example of benomyl increasing the deliquescent beneficial effect of active component.This active component (1-butyl carbamyl-benzimidazolyl-2 radicals-methyl-carbamate) is a kind of interior fungicide of inhaling, its dissolubility in water is relatively poor, in the time of simultaneously in being dissolved in water, can resolve into the tolimidazole carbamate rapidly, though decomposer also has bactericidal effect, the dissolubility in water is still very little.
Under 25 ℃, shake benomyl and benomyl+cyclodextrin respectively in water, resulting solubility data is taken passages in table 2.(benomyl and benomyl+cycloheptaamylose (the benomyl content of dissolved in filtrate is measured with ultraviolet spectra for β-CD) shake under 25 ℃ in water respectively, filtered sample then).
The trade name that commercially available benomyl uses is Fundazol 50 WP, and wherein the benomyl active component content is 50%.In table 3, listed the solubility data of mixture, Fundazol 50 WP and Fundazol 50 WP and the cyclodextrin mixt of benomyl, benomyl and cyclodextrin.In every test, every milliliter of substances that adds 3000 micrograms, and under 25 ℃, shake.Benomyl is 100% active component, and in benomyl and cyclodextrin mixt, the content of benomyl accounts for 17.3%,
In Fundazol 50 WP, the content of benomyl accounts for 50%, and in the mixture of Fundazol 50 WP and cyclodextrin, the content of benomyl accounts for 8.65%.Show that from table 3 because the result of preparation, the dissolubility of benomyl has improved four times.
Cyclodextrin itself can cause that the dissolubility of the Fundazol 50WP of pure benomyl and preparation further brings up to 1.5-2 doubly.If notice that in the mixture of being made up of cyclodextrin, the benomyl absorption of active ingredient is less significantly, cause that the benomyl concentration of actual biological effect has increased significantly in the aqueous solution simultaneously, above-mentioned finding also should show the biological effect aspect.
Contain in the various materials of benomyl, the dissolubility of benomyl can in the time of 25 ℃, be measured by shaking sample in water.Take by weighing solid material by every milliliter 2000 microgram, wherein the consumption of benomyl is as follows respectively:
Under the situation of benomyl: 2000 mcg/ml
Under the situation of benomyl+β-CD: 350 mcg/ml+1650 microgram β-CD
Under the situation of Fundazol 50 WP: 1000 mcg/ml
Under the situation of Fundazol 50 WP+ β-CD: 175 mcg/ml+1650 microgram β-CD.
Following evidence has beyond thought synergy between known fungicide and beta-schardinger dextrin-.With the suspension liquid of aqueous phase of the test material of stable high degree of dispersion, concentration on request (0.1-200 mcg/ml) is added in the agar medium, subsequently medium is injected in the Petri dish.The mycelium sheet is separated from the test mould that cultivate on the surface, and cap is put into contains in the Petri dish of testing material.In thermostat, breed, measure the growth of colony diameter then, and with the diameter of tester relatively.Test repeats three times.
Having listed bactericide Fundazol 50 WP(benomyl content in table 4 is 50%) and the effect of the mixture of the beta-schardinger dextrin-of Fundazol 50 WP+10%.The result has clearly illustrated that the synergistic activity of beta-schardinger dextrin-, and is the most remarkable to Botrytis cinerea (Botrytiscineres) and the active raising of a kind of fruit, such as apple, pear, etc. clump stalk spore (Monilia fructigena).
Metomeclan (1-(3,5-dichlorophenyl)-3-methoxyl methyl-pyrrolidines-2,5-diketone) be a kind of in water undissolved contact fungicide.The adding cyclodextrin can obviously improve the activity of metomeclan.Table 5 has been listed the fungicidal effect of mixture of β-CD of metomeclan and metomeclan+10%.
Use the mixture of phenarimol (2,4 '-two chloro-α-(pyrimidine-5-yl)-benzohydrol) and beta-schardinger dextrin-, on wheat powdery mildew (host's parasite), carry out the test under the natural conditions.In seedling rearing room, (20 ℃, humidity 90%, luminous intensity 9000 luxs) carry out repeated test three times under common experimental system and environmental condition.In culture dish (11 centimetres of diameters), on average adopt 160 plant species (5-6 centimetre of vegetative stage), contain the stable suspension liquid of aqueous phase of testing material with 8 milliliters and handle.Result of the test is taken passages in table 6.Suppress efficient according to Xin Fule-Pa Pu (Hinfner-Papp) formula, adopt infectious index to calculate.
By other a series of tests, verify the known line dextrin that obtains with heat, enzyme or sour starch-splitting, whether show similar effect with cyclodextrin.Above-mentioned test clearly illustrates that to have only cyclodextrin to have above-mentioned sterilization synergy.
Because the synergistic effect of cyclodextrin is reaching same bactericidal effect, even the prerequisite that surpasses
Down, can make and knownly reduce significantly, so just reduce and the active component cost related, also reduce the danger of environmental pollution simultaneously with consumption normally used fungicidal activity composition.
In following example, can see more detailed description of the present invention, but protection domain is not limited to described example.
Embodiment 1
With the spray of benomyl as active component
Commercially available benomyl is that to contain active component be 50% wettable powdery spray, and its trade name is Fundazol 50 WP.Have identical activity, but active component content product still less can prepare by following method:
The anion surfactant (be preferably Genapol PGM, give hot to 50 ℃) that gives 15 kilograms of crystallization cycloheptaamyloses (water capacity 13%) giving first efflorescence in 35 kilograms of the benomyls of first efflorescence and the same airflow milling and 40 kilograms of winnofils, 5 kilograms of useless sulfide powders and contain 50% water in airflow milling mixes in the Jun Shi device for 5 kilograms.The material of homogenizing carries out drying, micronizing again, so that scatter-gather particle is together packed at last.
Embodiment 2
According to the method for embodiment 1, be about to each component micronizing, homogenizing, drying, also micronizing again, with preparing product.Composition components is as follows:
40 kilograms of benomyls (active component content is 100%)
40 kilograms of winnofils
Tensiofix BC
22.5 kilogram
5 kilograms of Totamine
12.5 kilograms of beta-schardinger dextrin-s
Embodiment 3
With the benomyl is the seed treatment composition of active component
A kind of product according to the preparation of the method for embodiment 1.Its composition components is as follows:
35 kilograms of benomyls
1 kilogram of Diotilan
1 kilogram of Evidet
1 kilogram of Tylose N20
0.5 kilogram of Aerosil " 300 "
2 kilograms of Safranin P additives
Change cyclodextrin mixt (beta-schardinger dextrin-into
Content about 48%; α-and gamma-cyclodextrin
Content is 2%, the content of starch that part is decomposed
About 50%) 38 kilograms in atomized drying material
21.5 kilograms of winnofils
Embodiment 4
With the amino benzimidazole of Abem(2-carbomethoxy) be the seed treatment compositions of active component
Under the condition of heating, the Abem active component is dissolved in the hydrochloric acid, use the emulsion of forming by ammonium hydroxide, paraffin oil and cycloheptaamylose mixture to neutralize then.Suspension is stablized with surfactant by known method.Seed treatment has following component:
Abem 15%
Paraffin oil 19.8%
Beta-schardinger dextrin-5%
Ethylene glycol 5.6%
Ammonium chloride (when the neutralized salt acid solution, forming) about 10%
Various surfactants:
Emulsogen M 0.24%
Atlox 4868B 1.6%
Triton X45 1.9%
Tensiofix L051 0.2%
Tensiofix 821 0.2%
Add water to 100%
Claims (8)
1, antifungal plant protection composition; it is characterized in that said composition is by Fungicidal active ingredient such as the benomyl of 3-90% by weight; carbendazim, metomclan or phenarimol and the cyclodextrin of 1-90% and optional usual auxiliaries mix by weight.
2, according to the described Fungicidal composition of claim 1, wherein comprise Fungicidal active ingredient and cyclodextrin, its ratio is 90: 1-1: 5, be preferably 2-5: 1.
3, according to the described Fungicidal composition of claim 1, wherein comprise α as cyclodextrin-, β-or gamma-cyclodextrin.
4, according to any one the described Fungicidal composition among the claim 1-4, wherein comprise benomyl and cyclodextrin, its ratio is 2-5: 1, be preferably 3.5: 1.5.
5, according to any one described Fungicidal composition of claim 1-4, wherein comprise carbendazim and cyclodextrin, its ratio is 2-5: 1, be preferably 3: 1.
6, according to any one described Fungicidal composition of claim 1-4, wherein comprise metomclan and cyclodextrin, its ratio is 2-20: 1, be preferably 10: 1.
7, according to any one described Fungicidal composition of claim 1-4, wherein comprise phenarimol and cyclodextrin, its ratio is 1: 4-90: 1.
8, antifungal processing method is characterized in that its consumption is preferably 1.2-1.6 kilogram/hectare when employing is handled plant or other surface according to the plant protection composition of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN86100966A CN1015085B (en) | 1985-01-07 | 1986-02-21 | Adopt cyclodextrin to improve the method for activation of plant preservatives |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HU8541A HU192907B (en) | 1985-01-07 | 1985-01-07 | Plant protective composition with fungicide activity |
| CN86100966A CN1015085B (en) | 1985-01-07 | 1986-02-21 | Adopt cyclodextrin to improve the method for activation of plant preservatives |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN86100966A CN86100966A (en) | 1987-09-02 |
| CN1015085B true CN1015085B (en) | 1991-12-18 |
Family
ID=10947616
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN86100966A Expired CN1015085B (en) | 1985-01-07 | 1986-02-21 | Adopt cyclodextrin to improve the method for activation of plant preservatives |
Country Status (5)
| Country | Link |
|---|---|
| KR (1) | KR900006520B1 (en) |
| CN (1) | CN1015085B (en) |
| AT (1) | ATE64816T1 (en) |
| DE (1) | DE3680039D1 (en) |
| HU (1) | HU192907B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114041421A (en) * | 2021-11-25 | 2022-02-15 | 中国热带农业科学院海口实验站 | Tissue rapid propagation method of avocados |
-
1985
- 1985-01-07 HU HU8541A patent/HU192907B/en not_active IP Right Cessation
-
1986
- 1986-01-07 DE DE8686900827T patent/DE3680039D1/en not_active Expired - Fee Related
- 1986-01-07 AT AT86900827T patent/ATE64816T1/en not_active IP Right Cessation
- 1986-01-07 KR KR1019860700619A patent/KR900006520B1/en not_active IP Right Cessation
- 1986-02-21 CN CN86100966A patent/CN1015085B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| ATE64816T1 (en) | 1991-07-15 |
| HU192907B (en) | 1987-07-28 |
| CN86100966A (en) | 1987-09-02 |
| HUT39563A (en) | 1986-10-29 |
| KR870700002A (en) | 1987-02-28 |
| DE3680039D1 (en) | 1991-08-08 |
| KR900006520B1 (en) | 1990-09-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1111477A (en) | Synergistic composition | |
| CN1094407A (en) | triazolopyrimidine derivative | |
| CN1516551A (en) | Use of fatty alcohol ethoxylates as penetration promoters | |
| CN1078043C (en) | Combinations of a fungicide having an azole group with an insecticide having a pyrazole, pyrrole or phenylimidazole group | |
| CN1870889A (en) | Formulation of a synergistic insecticidal composition as a cyclodextrin-complex | |
| JPH07500356A (en) | TCMTB supported on a powdery solid carrier, its production and use | |
| CN1066610C (en) | A plant-microbicidal composition having synergistic action, comprising at least two active ingredient components, eherein...... | |
| CN1033626A (en) | Thiazole derivative | |
| CN1261026C (en) | Bacteridal composition containing alkene oxime amine and triazole kind compound | |
| CN1105497C (en) | Insecticidal and miticidal compositions | |
| CN1218637C (en) | Insecticide-disinfectant composition containing zarilamid | |
| CN1015085B (en) | Adopt cyclodextrin to improve the method for activation of plant preservatives | |
| CN1918989A (en) | Bactericide composition | |
| CN1265708C (en) | Bactericide composition of SYP-Zo48 and thiocarbamate | |
| JP2022513968A (en) | Insecticidal products for controlling mediators and pests with increased contact effect | |
| CN1066717C (en) | 1-arylpyrazoles pesticide | |
| CN1173278A (en) | N-acetonylbenzamide fungicides | |
| CN86103679A (en) | The preparation method of phenanthrene derivatives | |
| CN1156953A (en) | Herbicidal compositions containing DMSO | |
| CN1565182A (en) | Bactericidal compositions of flumorph and enostroburin and synergist | |
| CN1287473A (en) | Bacteriocide compositions for agricultural and horticultural use | |
| CN1257669C (en) | Bactericide composition containing enostroburin | |
| CN1539285A (en) | Composite insect disinfestation micellar emulsion contaning triazophos and 'Ruijinte', and its preparation method | |
| CN1593143A (en) | Fenoxanil containing bactericide and insecticide compositions | |
| CN1127751A (en) | Isothiazole derivatives and their uses |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C13 | Decision | ||
| GR02 | Examined patent application | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: WD Ref document number: 1027055 Country of ref document: HK |