专利汇可以提供Synergistic insecticidal compositions containing .beta.-exotoxin专利检索,专利查询,专利分析的服务。并且A synergistic insecticidal composition comprises as a first ingredient the .beta.-exotoxin of Bacillus thuringiensis or a metal salt thereof and has a second ingredient of one or more of the following chemical insecticides:O,o-diethyl-O-(2-isopropyl-4-methyl-6-pyrimidyl) thionophosphate,O,o-dimethyl, .alpha.,.alpha.,.alpha.-trichloro-1-hydroxyethyl phosphonate,.alpha.-methoxy-4H-1,3,2-benzodioxaphosphorin-2-thione,O,o,-dimethyl S-(.alpha.-(ethoxycarbonyl)benzyl) phosphorodithioate,O,o-dimethyl S-(4-chlorophenyl) phosphorothioateThe first and second ingredients are used generally in a ratio of about 0.5:1 to 2.0:1 and may be dispersed in a major portion of an agronomically acceptable carrier.,下面是Synergistic insecticidal compositions containing .beta.-exotoxin专利的具体信息内容。
What is claimed is:1. An insecticidal composition consisting essentially of a first ingredient selected from the group consisting of .beta.-exotoxin and metal salts thereof and a second ingredient selected from the group consisting of O,O-diethyl-O-(2-isopropyl-4-methyl-6-pyrimidyl)-thionophosphate; O,O-dimethyl, .alpha.,.alpha.,.alpha.-trichloro-1-hydroxyethyl phosphonate; .alpha.-methoxy-4H-1,3,2-benzodioxaphosphorin-2-thione; O,O-dimethyl S-(.alpha.-(ethoxycarbonyl)benzyl) phosphorodithioate; and O,O-dimethyl S-(4-chlorophenyl) phosphorothioate; said first and second ingredients being present in the ratio of about 0.1:1 to about 10:1 by weight.2. The composition of claim 1 in which said second ingredient is O,O-diethyl O-(2-isopropyl-4-methyl-6-pyrimidyl)-thionophosphate; and said first and second ingredients are present in the ratio of about 0.5:1 to about 2.0:1.3. The composition of claim 1 in which said second ingredient is O,O-dimethyl, .alpha.,.alpha.,.alpha.-trichloro-1-hydroxyethyl phosphonate; and said first and second ingredients are present in the ratio of about 0.5:1 to about 2.0:1.4. The composition of claim 1 in which said second ingredient is .alpha.-methoxy-4H-1,3,2-benzodioxaphosphorin-2-thione; and said first and second ingredients are present in the ratio of about 0.5:1 to about 2.0:1.5. The composition of claim 1 in which said second ingredient is O,O-dimethyl S-(.alpha.-(ethoxycarbonyl)benzyl)phosphorodithioate; and said first and second ingredients are present in the ratio of about 0.5:1 to about 2.0:1.6. The composition of claim 1 in which said second ingredient is O,O-dimethyl S-(4-chlorophenyl)phosphorothioate; and said first and second ingredients are present in the ratio of about 0.5:1 to about 2.0:1.7. An insecticidal composition comprising a major portion of an agronomically acceptable carrier and about 1.0% to about 40%, based upon the weight of said composition, of active ingredients consisting essentially of a first ingredient selected from the group consisting of .beta.-exotoxin and metal salts thereof and a second ingredient selected from the group consisting of O,O-diethyl-O-(2-isopropyl-4-methyl-6-pyrimidyl)-thionophosphate; O,O-dimethyl, .alpha.,.alpha.,.alpha.-trichloro-1-hydroxyethyl phosphonate; .alpha.-methoxy-4H-1,3,2-benzodioxaphosphorin-2-thione; O,O-dimethyl S-(.alpha.-(ethoxycarbonyl)benzyl) phosphorodithioate; and O,O-dimethyl S-(4-chlorophenyl) phosphorothioate; said first and second ingredients are present in the ratio of about 0.1:1 to about 10.0:1.8. The composition of claim 7 in which said second ingredient is O,O-diethyl-O-(2-isopropyl-4-methyl-6-pyrimidyl) thionophosphate; said first and second ingredients are present in the ratio of about 0.5:1 to about 2.0:1.9. The composition of claim 7 in which said second ingredient is O,O-dimethyl, .alpha.,.alpha.,.alpha.-trichloro-1-hydroxyethyl phosphonate; said first and second ingredients are present in the ratio of about 0.5:1 to about 2.0:1.10. The composition of claim 7 in which said second ingredient is .alpha.-methoxy-4H-1,3,2-benzodioxaphosphorin-2-thione; said first and second ingredients are present in the ratio of about 0.5:1 to about 2.0:1.11. The composition of claim 7 in which said second ingredient is O,O-dimethyl S-(.alpha.-(ethoxycarbonyl)benzyl) phosphorodithioate; said first and second ingredients are present in the ratio of about 0.5:1 to about 2.0:1.12. The composition of claim 7 in which said second ingredient is O,O-dimethyl S-(4-chlorophenyl) phosphorothioate; said first and second ingredients are present in the ratio of about 0.5:1 to about 2.0:1.
BACKGROUND OF THE INVENTION
Organic phosphorous insecticides have appeared after the Second World War, playing the leading role in the eradication of hazardous insects. However, the disadvantages of these materials, such as development of insect resistance, the considerable toxicity of the material to humans and cattle, and simultaneous eradication of natural enemies, have been noticed in recent years. The most effective and widely used organic phosphorous insecticides are:
O,o-diethyl-O-(2-isopropyl-4-methyl-6-pyrimidyl)thionophosphate (referred to as Diazinon).
O,o-dimethyl, α,α,α-trichloro-1-hydroxyethyl phosphonate (referred to as DEP).
α-methoxy-4H-1,3,2-benzodioxaphosphorin-2-thione (referred to as Salithion.
O,o-dimethyl S-(α-(ethoxycarbonyl)benzyl)phosphorodithioate (referred to as PAP).
O,o-dimethyl S-(4-chlorophenyl) phosphorothioate (referred to as DMCP).
Bacillus thuringiensis, a spore forming microorganism with crystalline parasporal bodies, has been employed commercially as a microbial insecticide for the control of insects such as species of the order Lepidoptera and certain flies and mites. B. thuringiensis and its use as an insect pathogen is described inter alia, in C. L. Hannay and P. Fitz-James, "The Protein Crystals of Bacillus thuringiensis Berliner", Can. J. Microb., I, 694-710 (1955); A. M. Heimpel, "A Critical Review of Bacillus thuringiensis var. thuringiensis Berliner and Other Crystalliferous Bacteria", Ann. Rev. Entomology, 12, 287-322, (1967). B. thuringiensis insecticides are quite specific and are harmless to non-susceptible orders of insects, and relatively safe to animals and man.
"Endotoxin" is used by the art to define the toxicity associated with the water-insoluble crystals. "Exotoxin" denotes the so-called heat-stable, water-soluble fly toxin produced by Bacillus thuringiensis var. thuringiensis organisms. The water-soluble, heat-stable exotoxin was first reported in 1959 when its toxicity against the larvae of flies was noted. A review of the heat-stable exotoxin is contained in the previously mentioned article by A. M. Heimpel. This article summarizes the activity of the exotoxin (therein referred to as B.t. β-exotoxin) and concludes that exotoxin is effective against insects belonging to some species of the orders "Lepidoptera, Diptera, Hymenoptera, Coleoptera, and Orthoptera". It is also reported that exotoxin affects insects only at molting or during metamorphosis.
The probable chemical structure of Bacillus thuringiensis exotoxin has been elucidated by Bond et al., "A Purification and some Properties of an Insecticidal Exotoxin from Bacillus thuringiensis Berliner", R. P. M. Bond, C. B. C. Boyce and S. J. French, Biochem. J. (1969), 114, 477-488.
The proposed structure is: ##STR1##
Various processes are known for the production of exotoxin. All involve the fermentation of a Bacillus thuringiensis variety thuringiensis organism in a medium such as the following:
______________________________________Ingredient Weight (%)______________________________________Cane Molasses 0.5Beet Molasses 0.5Cottonseed Oil Meal 2.0Casein 1.0Corn Steep Liquor 3.33CaCO3 0.1______________________________________
The medium is adjusted to a pH of about 7.6 with ammonium hydroxide and then sterilized at about 120° C. for about 15 minutes. The medium is inoculated with Bacillus thuringiensis var. thuringiensis and the fermentation is conducted for about 24 hours at about 30° C. At the termination of the fermentation the cells in the broth are in the prespore stage of development and not more than about 1% of the total population contained spores.
The final whole culture is screened through a 200 mesh screen and the resulting mixture of cells and liquor is concentrated at about 125° F. with a vacuum of about 25 inches of mercury. Final drying and micropulverizing produced a 200 mesh powder which is characterized by a LD50 of 2.9 mg%.
Another process for the production of both the exotoxin and endotoxin of Bacillus thuringiensis is proposed by Drake et al. U.S. Pat. No. 3,087,865. Drake et al. further disclose the precipitation of exotoxin from aqueous supernatant fermentation liquor by addition of calcium chloride. The calcium salt thus produced, as well as corresponding magnesium and barium salts, are disclosed to possess insecticidal activity.
Other salts of β-exotoxin which evidence insecticidal activity and may also be used in accordance with this invention are the copper, cadmium, manganese, tin, zinc, lead, cobalt, aluminum and iron salts.
DESCRIPTION OF THE INVENTION
The present invention proposes to minimize the untoward side effects of organophosphorous insecticides and reserving their prominent insecticidal activity. The present invention is based on unexpected findings of marked synergistic insecticidal activity obtained by the combination of β-exotoxin originated from Bacillus thuringiensis with the organophosphorous chemicals, Diazinon, DEP, Salithion, PAP and DMCP. The combination exerts its pesticidal activity at far smaller concentrations as compared with the dosage required in sole applications of the respective ingredients. In addition, the combined composition thus obtained is effective against insects which have acquired resistance to the organophosphorous insecticidal compounds.
The influence on the natural enemies of the target insects is substantially reduced. The synergistic insecticidal composition according to the present invention provides a unique means of eradicating hazardous insects in view of marked insecticidal activity combined with secondary factors such as low toxicity to the man and cattle, and less influence on the natural enemies.
Briefly, the compositions of this invention comprise a first ingredient of the group consisting of β-exotoxin and metal salts thereof and a second ingredient of the group consisting of O,O-diethyl-O-(2-isopropyl-4-methyl-6-pyrimidyl)-thionophosphate; O,O-dimethyl, α,α,α-trichloro-1-hydroxyethyl phosphonate; α-methoxy-4H-1,3,2-benzodioxaphosphorin-2-thione; O,O-dimethyl S-(α-(ethoxycarbonyl)benzyl) phosphorodithioate; and O,O-dimethyl S-(4-chlorophenyl) phosphorothioate. The invention also contemplates admixtures of the defined ingredients with an agronomically acceptable carrier, the total active ingredients comprising preferably about 1% to 40% of the admixture of active ingredients and carrier.
Exotoxin is known to possess insecticidal activity against the larvae of fly. However, the activity is quite weak or nil against certain other hazardous insects, and it is practically of no use in eradication of parasitic insects. Nevertheless, blending exotoxin with Diazinon, DEP, Salithion, PAP or DMCP results in a tremendous potential and prolonged action of the insecticidal activity.
The dosage and concentration of the insecticidal composition vary depending on the modes of application. In the case of powdery moth, green caterpillar, cabbage armyworm, and aphid, 200 to 800 liters per acre of a liquid preparation containing 50-250 ppm of the organophosphorous insecticide, and 100-500 ppm of β-exotoxin gives excellent protection which persists for 1-3 months after spraying. Sole application of Diazinon and the like requires spraying 200-800 liters per acre in a concentration of more than 500 ppm. In the compositions of this invention the proportion of organophosphorous insecticide to exotoxin is in the range of 0.1:1 to 10:1, and most preferably 0.5:1 to 2:1.
The insecticidal compositions according to the present invention exert a marked eradicating effect against a variety of hazardous insects and are particularly useful for eradication of those insects which are difficult to treat by organophosphorous insecticides alone.
For example, the powdery moth has been observed to increase in vegetable fields. Quick development of insecticide resistance and short life cycle render eradication extremely difficult. However, application of the insecticidal composition according to the present invention provides satisfactory and persisting results.
For the eradication of sanitary hazardous insects, a typical example is shown by the cockroach. This insect is found to increase in the urban districts and exhibit marked resistance to the organophosphorous insecticides. Though it is sensitive to chlorine-containing insecticides such as Dieldrin, use of these chlorine-containing insecticides may be limited in the near future in view of the residual toxicity problem.
The synergistic insecticidal compositions of this invention provide a key to the solution of this problem. For example, a poison diet containing 0.1% of Diazinon and 0.5% of exotoxin gives rise to an extremely high eradication effect on cockroach. The insecticidal effect is far superior to the diet containing only 0.1% of Diazinon. Furthermore, the insecticidal effect of the preparation containing 0.5% of exotoxin alone is nil.
The toxicity of exotoxin against warm blooded animals and fish is extremely low. In addition, the toxicity to insects is obtained via the oral route. Accordingly, the effects on the natural enemies of the hazardous insects are small compared with contact poisons such as BHC.
The synergistic effect of this invention does not exist in the case of other types of organophosphorous compounds, including EPN, Parathion, Methyl parathion, and the like. Chlorine-containing insecticides such as DDT, BHC, Endrin, and the like, are also unaffected by exotoxin.
The invention is illustrated by the following examples:
EXAMPLE 1
Test solutions in an amount of 30 ml. and having the concentrations specified in Table 1 were sprayed onto cabbage cultivated in porcelain pots 12 cm in diameter. After 24 hours, the leaf was cut and placed in a petri dish having a diameter of 12 cm and 10 tobacco cutworm larvae (third stage) were allowed to eat the treated cabbage leaf for three days. This was followed by feeding with a fresh untreated leaf. The mortality after 1, 3, 5, and 9 days was determined. The results of Table 1 are the average of three such experiments.
Table 1__________________________________________________________________________ Concen- tration (Active Mortality after release ingredient) of the insectTest Preparation ppm 1 day 3 days 5 days 9 days__________________________________________________________________________Exotoxin alone 1000 0 % 5 % 20 % 65 % 500 0 5 20 60 100 0 0 16 20 50 0 0 5 20Diazinon alone 100 28 44 47 47Diazinon + exotoxin 100 + 100 100 100 100 100Diazinon + exotoxin 100 + 200 100 100 100 100DEP alone 100 9 14 18 32DEP + exotoxin 100 + 100 31 73 95 100DEP + exotoxin 100 + 200 68 90 100 100DEP + exotoxin 100 + 500 100 100 100 100Salithion alone 100 33 33 35 35Salithion + exotoxin 100 + 100 65 95 100 100Salithion + exotoxin 100 + 200 100 100 100 100PAP alone 100 42 53 58 63PAP + exotoxin 100 + 100 100 100 100 100DMCP alone 100 20 20 20 25DMCP + exotoxin 100 + 500 100 100 100 100__________________________________________________________________________
EXAMPLE 2
Thirty ml. of each test solution at the specified concentrations was sprayed onto cabbage cultivated in a pot. The cabbage leaves were cut off periodically and placed in petri dishes of 9 cm in diameter. Ten young larvae of powdery moth were placed in each dish and the mortality determined after 24 hours. The results of Table 2 are the average of two replications.
Table 2__________________________________________________________________________ Concen- Mortality tration 4 days 8 days 16 daysTest Preparation (ppm) 1st day after after after__________________________________________________________________________Exotoxin alone 200 10 % 3 % 0 % 0 %Diazinon alone 100 36 5 0 0Diazinon + exotoxin 100 + 200 100 100 100 95DEP alone 100 20 0 0 0DEP + exotoxin 100 + 200 100 100 76 43Salithion alone 100 40 10 0 0Salithion + exotoxin 100 + 200 100 100 100 63PAP alone 100 65 20 0 0PAP + exotoxin 100 + 200 100 100 100 100DMCP alone 100 40 0 0 0DMCP + exotoxin 100 + 200 100 100 100 20ControlEPN 100 50 40 20 0EPN + exotoxin 100 + 200 62 55 43 0Parathion 100 73 30 25 0Parathion + exotoxin 100 + 200 50 60 20 0BHC 500 80 40 45 20BHC + exotoxin 500 + 500 88 50 30 0Non-treatment -- 0 0 0 0__________________________________________________________________________
Diazinon, DEP, Salithion, PAP, and DMCP were found to be synergized by blending with exotoxin. A marked potentiation and improvement in residual effect with respect to the insecticidal activity against the young larvae of powdery moth are shown. Noticeable synergistic effect could not be observed upon blending exotoxin with EPN, parathion, BHC and the like.
EXAMPLE 3
Cabbage fields infested with powdery moth larvae were divided into separate areas of 3.3 square meters. Wettable powders containing 20% of exotoxin, emulsions containing 40% of Diazinon, and wettable powders containing 10% of exotoxin and 20% of Diazinon were diluted with water and sprayed in an amount of 300 ml. per area. The degree of dilution for each insecticide is shown in the table. The test was carried out in 3 replications, and the number of surviving insects was determined immediately prior to spraying and at 2, 6, 11, and 18 days after the spraying. The results are shown in Table 3.
Table 3__________________________________________________________________________ Surviving powdery moth (mean value for 3 districts) Test Dilution Concen- Immediately 2 6 11 18prepara- degree tration before days days days days tion times (ppm) spraying after after after after__________________________________________________________________________Exotoxin20% 1,000 200 34.7 20.3 14.7 13.6 41.4wettablepowderDiazinon40% 2,000 200 24.0 0 18.3 28.0 67.3emulsionExotoxin10%diazinon 1,000 100 + 200 40.3 0 0 1.1 020%emulsionNon-spraying -- -- 23.6 18.8 26.7 37.0 50.4__________________________________________________________________________
as seen from the above Table, the combination of exotoxin and Diazinon shows a very noticeable activity for preventing powdery moth larvae and such a combination apparently provides the synergistic activity as compared with the activity in the concentrations of the single uses.
EXAMPLE 4
In petri dishes of 9 cm diameter and 7 cm height were placed 200 g. of soybean cake medium mixed with the specified concentrations of test insecticide. Thirty third-stage fly larvae were placed in each dish and each dish was covered with gauze. After about 2 weeks, the total number of ecdyzed adult fly insects was determined. Each treatment was performed in 5 replications. The average of the results is shown in Table 4.
Table 4______________________________________ Concentration Number of in the medium Number of ecdyzedTest Insecticide (ppm) larvae tested adult insect______________________________________Exotoxin 20 150 61" 10 150 79Diazinon 20 150 63" 10 150 72Diazinon + exotoxin 10 + 10 150 0" 5 + 5 150 0DEP 20 150 43" 10 150 81DEP + exotoxin 10 + 10 150 0" 5 + 5 150 0Salithion 20 150 34" 10 150 58Salithion + exotoxin 10 + 10 150 0" 5 + 5 150 0PAP 20 150 24" 10 150 50PAP + exotoxin 10 + 10 150 0" 5 + 5 150 0DMCP 20 150 43" 10 150 87DMCP + exotoxin 10 + 10 150 0" 5 + 5 150 0ControlParathion 20 150 60" 10 150 101Parathion + exotoxin 10 + 10 150 111" 5 + 5 150 93Methyl parathion 20 150 41" 10 150 93Methyl parathion 10 + 10 150 70+ exotoxin" 5 + 5 150 94EPN 20 150 23" 10 150 64EPN + exotoxin 10 + 10 150 44" 5 + 5 150 58Non-treatment -- 150 99______________________________________
EXAMPLE 5
The bottom of petri dishes of 9 cm diameter, 7 cm height, was covered with filter paper. Smaller petri dishes of 3 cm diameter and containing 10 ml of test solutions diluted with milk to specified concentration, were placed on the large dishes. Five adult brown winged aphids were released in each dish which was then covered with a cover glass having an opening for air and allowed to stand at 25° C. for five days. Mortality was then determined. Each treatment was done with four replications. Average results are set forth in Table 5.
Table 5______________________________________ Concentraton Number of Mortality (%) insects tested after 5 days______________________________________Exotoxin 1.0 20 0 %Diazinon 0.1 20 25Diazinon + exotoxin 0.1 + 0.5 20 95" 0.2 + 0.5 20 100" 0.2 + 0.1 20 100DEP 0.1 20 10DEP + exotoxin 0.1 + 0.5 20 85" 0.2 + 0.5 20 100" 0.2 + 1.0 20 100______________________________________
The insecticidal composition of this invention can be prepared in the form of dust, wettable powder, emulsion, granule, or aqueous solution by blending the active ingredients with a suitable carried and, if desired, adding a surfactant, dispersing agent, spreader, or the like.
The present invention is further illustrated in detail by the following examples.
EXAMPLE 6
A. Exotoxin 15%, Diazinon 25%, white carbon 10%, clay 46.5%, sodium lignin sulfonate 1.5%, and sodium alkyl aryl sulfonate 1.5%, were mixed uniformly and pulverized to provide a wettable powder.
B. Exotoxin 20%, DEP 10%, methanol 30%, and dimethyl sulfoxide 30% were dissolved in polyoxy-ethylene alkyl ether.
C. Exotoxin 2%, Salithion 1%, clay (-300 mesh) 96%, and white carbon 1% were blended uniformly and subsequently pulverized to provide a dust.
D. Commercial cornstarch 44.4%, carboxymethyl cellulose 5%, starch 50%, exotoxin 0.5%, and Diazinon 0.1% were blended uniformly, kneaded after addition of water to make a dough, extruded through 5 cm.-holes, and dried and cut into 5 - 10 cm. lengths.
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