SYNERGISTIC AVERMECTIN COMBINATION

Abstract: A novel combination of one or more avermectin com­ pounds of formula where the broken line indicates either a single or a double bond at the 22,23-position; n is 0 or 1, and when n is 0 a hydrogen is present at the 13-position; R₁ is hydrogen or R₂ is hydrogen or hydroxy provided that R₂ is present only when the broken line indicates a single bond; R₃ is sec-butyl or isopropyl; and R₄ is hydrogen or methyl, with agricultural spray oil is synergistic in such a manner as to allow for a drastic reduction in the amount of active ingredient that is fully effective and also to provide a dramatic extension of the period over which such a combination is fully effective. The synergistic combination is useful as an agricultural insecti­ cide and miticide against a variery of insects and mites which infest a variety of plants.

Description: SYNERGISTIC AVERMECTIN COMBINATION The avermectins (formerly identified as C-076 compounds) are a family of macrocyclic lactones that are highly effective against a broad range of pests that infest and are an annoyance to plants and animals. The avermectins are active against ectoparasites and endoparasites of domestic animals, including pets and animals grown for food, also man. In addition, the compounds are very effective against arthropod pests, which affect plants while in storage or while growing, either in the aerial portion of the plant or from the soil in which they grow. The avermectin compounds are isolated from the fermentation broth of a microorganism, Streptomyces avermitilis. The isolation and purification of such compounds is described in U.S. Patent US-A-4,310,519 issued 12 January 1982. Several derivatives of the avermectin compounds have been prepared, specifically the 22,23-dihydro derivatives and the monosaccharide derivatives. The present invention is based on the discovery that a combination of certain avermectin compounds, including certain derivatives, e.g. some of those mentioned above, with an agricultural spray oil is significantly more effective at a lower dose of avermectin and over a longer period of time than either component alone. Compounds that are related to the avermectins, but which have significant chemical differences, are the milbemycins, which have also been found to be active miticides and insecticides. In tests, the ovicidal activity of such compounds has been enhanced by the addition of machine il. However, such activity has been demonstrated to be significantly different from synergistic activity against the motile (active) stages of agricultural insect and mite pests. The avermectin compounds that form part of the synergistic combination of the present invention have the following structural formula: EMI2.1 where the broken line indicates either a single or a double bond at the 22,23position; n is 0 or 1, and when n is 0 a hydrogen is present at the 13-position; R1 is hydrogen or EMI3.1 R2 is hydrogen or hydroxy provided that R2 is present only when the broken line indicates a single bond; R3 is sec-butyl or isopropyl; and R4 is hydrogen or methyl. In accordance with the present invention, a synergistic combination useful against motile stages of arthropods infecting plants comprises one or more avermectin compounds having the above formula, together with an agricultural spray oil. The avermectin compounds isolated from the Streptomyces avermitilis fermentation broth are obtained as described in the abovementioned U.S. Patent 4,310,519. Such compounds are those of the above formula in which n is 1; R1 is the sugar residue (which is a-L-oleandrose); the broken line indicates a single or double bond; R2 is hydroxy but is present only when the broken line indicates a single bond; R3 is sec-butyl or isopropyl; and R4 is hydrogen or methyl. The compounds are named using a combination of letters and numbers which coordinate with the structural variations of the substituents. The following table defines the avermectin natural product compounds: Avermectin R1/ 22,23 3 R4 Ala Double bond sec-butyl -CH3 Alb Double bond isopropyl -CH3 A2a -OH sec-butyl -CH3 A2b -OH isopropyl -CH3 Bla Double bond sec-butyl -H Blb Double bond isopropyl -H B2a -OH sec-butyl -H B2B -OH isopropyl -H Derivatives of the above 8 avermectin compounds can be prepared to form other compounds which are effective in the combination of the invention. In the Ala, Alb, Bla and Blb compounds (the "l-series" of compounds) the 22,23-double bond can be selectively reduced to a single bond to form the compounds where R2 is hydrogen. The catalyst selective in reducing the 22,23-double bond while not affecting the other 4 double bonds is Wilkinson's homogeneous catalyst, which is exemplified by triphenyl phosphine rhodium chloride. The procedures for making such 22,23-dihydro avermectin compounds and fully described in U.S. Patent US-A-4,199,569 issued 22 April 1980. In addition, the outer a-L-oleandrose group can be selectively hydrolysed to prepare the avermectin monosaccharide compounds; i.e., the compounds in which R1 is hydrogen. Hydrolysis is most readily and most selectively effected by treating the avermectin compounds with sulfuric acid in isopropanol. The procedures for preparing such monosaccharide compounds and fully described in U.S. Patent US-A-4,206,205 issued 3 June 1980. To prepare the compounds wherein n is 0, both oleandrosyl groups are removed by hydrolysis with 1% sulfuric acid in methanol to prepare the aglycone compound. The procedures are described in the above cited U.S. Patent 4,206,205. The resultinq 13-hydroxy group is removed in two steps; first hv preparing the 13-chloro compound with 2-nitro henzonesulfenyl chloride and reducing the 13-chloro compound to the 13-deoxy compound with tributyl tin hydride. The procedures for such reactions are described in U.S. Patents 4,171,314 and 4,173,571. The agricultural spray oils which form the second component of the instant combination, mav be highly refined hydrocarbon oils, specially processed to remove qulfonated residuss which may he toxic to plants. Generallv, oil with at least 92% unsulfonated residues is employed. The oils are narrow distillation fractions and are characterzed by a narrow range of physical properties. In particular, such oils are characterized in one instance hy their viscosity and one such test for viscosity is measured in seconds. One of the oils useful in the instant combination is rharacterized in being a narrow fraction yieldinq a viscosity test of 60 seconds. This commonly is called "60 second oil" and is also known bv the tradenamem of Sunsorav hN, Orchex, FMC NR 415, and the like and similar 60 second oils from Superior and Volk. This particular oil is also characterized in having a boiling point of 2130C or 4150F. Another nil sod in the instant combination is a similar oil however, hating a viscosity test of 70 seconds. This is called "70 second oil" and is also known by the tradenames nf Sunspray 7N, FMC NR 440, and the like and similar 70 second oils from Superior and Volk. This oil is also characterized in having a boiling point of 2270C or 4400F. Other typical characterizations of the instant agricultural spray oils are described in the literature. See, for example, Canadian Patent 964,482. The agricultural spray oils may also he a vegetable seed oil or a mixture of vegetable seed oils, which, as thev are known in the agricultural industry, are crop seed oils produced from the particular crop from which their name is derived. Included in the vegetable oils suitable for the compositions of the present invention are cotton soed oil, rapeseed, peanut oil, sunflower oil, linseed oil, safflower oil, soybean oil, corn oil, olive oil and blends of the above oils such as cotton seed oil plus soybean oil; cotton seed oil plus peanut oil; cotton seed oil plus olive oil; corn oil plus linseed oil; corn oil plus soybean oil; as well as blends of any two or more of the above disclosed vegetable oils. In addition, the instant agricultural stray oil may be a mixture of a vegetable oil or oils and the above described hydrocarbon oils. These oils have been used alone to combat mite infestations in plants however the concentrations used were generally in the order of 1 to 2%. In addition, such oil formulations at the 1 to 2% concentration were used in combination with insecticides. It is known that when it is used under these conditions, the oil physically smothers the eggs, thus preventing their maturing into the motile staaes of development. That is, the oil acts as an ovicide. In the instant invention the oil may he used in combination with the avermectin compound in concentrations similar to that used in the prior art, however, in such circumstances much less of the avermectin compound need be used. The combination of the agricultural spray oil and the avermectin provides effective protection against the motile stages of the mites and insects while the use of higher concentrations of the oil provides ovicidal effects. In the synergistic combination of the instant invention the agricultural spray oil is used in concentrations of from 0.03 to 2% on a volume-tovolume basis of the final formulation. Preferahlv concentrations of the agricultural spray oil are used from 0.06 to 0.5%, and most preferably at about 0.25%. The lower concentrations are nreferred when, because of the nature of a particular plant, or because of the sensitivity of a particular stage of growth of a plant, a spray containing hiqher concentrations cannot be used because of phytotoxicity. The avermectin compounds are employed in the synergistic combination at concentrations of from 0.03 to 8 parts per million (ppm). Perferably from 0.25 to 3 ppm are employed and most preferably from 1 to 3 ppm are employed in dilute solutions for optimum field control of the mite populations. The combination of the avermectin with the agricultural spray oil provides the unexpected benefits of being able to use less of each of the ingredients as well as providing a lonqer duration of action. It is also advantageous to use less of Pach of the ingredients since the avermectins are very expensive and the agricultural spray oils, under certain circumstances can be phytotoxic, or at least contraindicated. The surprising observation that the instant combination has a considerably prolonqed duration of action is a great benefit in that costly reapplications and reinfestations are avoided. The avermectin and the agricultural spray oil combination is prepared using a solvent solution or emulsion of the avermectin compound or compounds, the agricultural spray oil, a surfactant and sufficent water to dilute the mixture to the desired concentration. The surfactants which may be used to emulsify the oil and the avermectin in the aqueous formulations are any of the non-phytotoxic surfactants, which are customarily used in preparing formulations for use on agricultural crons. The surfactants or surface active agents particularly suited for use in the compositions of the present invention are ionic or nonionic surface active compounds generally well known to the art. Surface active agents are suitable as a class for use according to the present invention. The nature of surface activations is well known and such agents generally have an oleophilic portion of the molecule, usually of hydrocarbon nature, and another solar portion of the molecule, which may be provided by various functional groups such as hydroxyl, sulfate, carboxyl, carbonyl, amino, nitro, amide, ether, sulfonate, phosphate, phosphite, etc. Examples of suitable classes of surface active agents which can be employed are alkali metal salts of fatty acids, alkali metal salts of sulfated fatty acids, fatty acid glycerides, sulfonated or sulfated fatty acid esters or amides, alkali metal sulfates, alkali metal alkyl sulfonates, alkali metal aryl sulfonates, alkali metal alkyl lauryl sulfonates, quaternary ammonium halides, alkali metal salts of alkylated naphthalene, sulfonic acid, polyethylene sorbitol esters of fatty acids, fatty acid amides of alkanol amines, condensation products of ethylene oxide and polyalkylene glycols, sorbitan esters, alkyl substituted phosphoric acids, alkali metal salts of alkyl phenol sulfonates, etc. Examples of individual surface active agents which can be employed are given for example in Kirk et al., ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY, Volume 13, pages 515-517 (1954). The ingredients are combined using formulation techniques well known to those skilled in the art. The instant synergistic combination may be used against agricultural arthropod pests to provide effective protection from the motile stages of such mites and insects while the plant is growing or while the crops from such plants are in storage. In particular, this combination is effective against mites of the order acarina such as the two spotted spider mite (Tetranychus urticae), the citrus red mite (Panonychus citri), the citrus rust mite (Phyllocoptruta oleivora), and the like. Insects of the order homoptera, coleoptera and lepidoptera are likewise susceptible to this combination. In particular the black bean aphid (Aphis fabae), Colorado potato beetle (Leptinotarsa decemlineata), Mexican bean beetle (Epilachna varivestis); cabbage looper (Trichoplusia ni) and the like. In using the compounds of this invention, the individual avermectin components may be prepared and used in that form. Alternatively, mixtures of two or more of the individual avermectin components may be used, as well as mixtures of the parent avermectin compounds, other avermectin compounds, or other active compounds not related to the avermectins and the compounds of this invention. In the isolation of'the avermectin compounds, which serve as starting materials for the instant processes, from the fermentation broth, the various avermectin compounds will be found to have been prepared in unequal amounts. In particular an "a" series compound will be prepared in a higher proportion than the corresponding "b" series compound. The weight ratio of "a" series to the corresponding "b" series is about 75:25 to 99:1. The differences between the "a" series and "b" series is constant throughout the avermectin compounds and consists of a sec-butyl group and an iso-propyl group respectively at the 25-position. This difference, of course, does not interfere with any of the instant reactions. In particular, it may not be necessary to separate the "b" components from the related "a" component. Separation of these closely related compounds is generally not practiced since the "b" compound is present only in a very small percent by weight, and the structural difference has negligible effect on the reaction processes and biological activities. In particular, for the preferred B1 and Al compounds, it has been found that the starting materials for the compounds of this invention are very often prepared in a ratio of about 80% avermectin Bla and Ala and 20% avermectin Blb or Alb. Thus the preferred composition of this invention is one which contains at least 80% of the "a" component and not more than 20% of the "b" component. EXAMPLE 1 Effects of Avermectin Bla/Blb and Agricultural Spray Oil on Citrus Rust Mite on Oranges. In a test of the effectiveness of avermectin compounds and agricultural spray oil (Sunspray 6N) used alone and in combination against the citrus rust mite on Marrs oranges, the following results were observed after spraying the orange trees to runoff with the listed concentration of the ingredients. The data are given in Table I in terms of the mean numbers of rust mites observed per sq cm on the indicated number of days following the spraying. The agricultural spray oil was reapplied on day 53. The last column "% Russet" indicates the percent of fruit that were downqraded due to the effects of the mites. TABLE I Mean No. rust mite/sq. cm. (on fruit) Pre- % Treatment os./100 gal treatment day 13 day 26 day 52 day 67 day 77 day 96 Russet Avermectin Bla/Blb 0.04 1.52 0.00 0.00 0.14 4.56 5.78 15.13 35 Avermectin Bla/Blb 0.08 0.32 0.00 0.01 0.88 2.43 3.47 3.78 16 Avermectin Bla/Blb & BR< Agricultural 0.04+ 0.30 0.04 0.00 0.06 0.50 0.00 0.24 5 Spray Oil 0.25% Agricultural 0.25% 0.72 0.00 0.01 1.62 1.57 1.35 0.78 31 Spray Oil Control --- 0.68 10.41 19.85 51.88 24.58 23.05 5.31 51 EXAMPLE 2 Effects of Avermectin Bla/Blb and Agriculture Spray Oil on Citrus Rust Mite on Grapefruit The procedure followed in Example 1 is repeated on grapefruit trees except that both the 0.04 oz/100 gal treatment of avermectin and the agricultural spray oil were reapplied on day 53. The results are given in Table II. TABLE II Mean No. rust mite/sq. cm. (on fruit) Pre- % Treatment os./100 gal treatment day 13 day 26 day 52 day 67 day 77 day 96 Russet Avermectin Bla/Blb 0.04 7.84 4.31 4.97 12.85 0.01 2.03 1.35 23 Avermectin Bla/Blb 0.08 4.36 0.19 0.15 3.48 1.42 1.22 1.55 22 Avermectin Bla/Blb & BR< Agricultural 0.04+ 3.08 0.10 0.61 1.28 0.62 0.02 0.01 8 Spray Oil 0.25% Agricultural 0.25% 1.92 8.72 14.39 30.34 0.76 1.90 1.35 40 Spray Oil Control --- 9.28 55.05 30.24 11.68 2.00 .47 0.13 70 In analyzing the result of Examples 1 and 2 it is noted that the 2 concentrations of the avermectin applied without oil achieved only moderate control of the mites although the lower dosage in the grapefruiit had to be reapplied because of increasing mite population levels. The agricultural spray oil, also applied twice, achieved a level of control better than the control group, but not very effective considering the high percent of russet downgrading of the fruit. The combination of a low dose of the avermectin and the agricultural spray oil applied once achieved in the orange test a mite count 60 times better than the low dose and 15 times better than higher dose at the end of the test. Percent russet was only 5% for the combination and 16 and 35% for the high and low doses respectively, 31% for the oil alone and 51% for the control. For the grapefruit, compared with the avermectin results, the combination had 135 and 155 times less mites. The percent russet was likewise improved at 8% for the combination 22 and 23% for avermectin alone, 40% for the oil alone and 70% for the control. EXAMPLE 3 Effects of Avermectin and Agricultural Spray Oil Against Motile Stages of the Two-Spotted Spider Mite on Bean Plants in the Laboratory. In this test various concentrations of avermectin Bla/Blb alone and in combination with two different levels of agricultural spray oil were tested. In addition, the agricultural spray oil alone was tested at 2 different concentrations. Table III shows the results where avermectin Bla/Blb was sprayed onto the plants containing a mixed mite population of adults and nymphs. Mortality counts were taken 5 and 11 days post-spray. Table IV represents a similar test however the infestation was applied 7 days after the plant was sprayed to measure residual control. Table V is a compilation of the data of Tables III and IV and gives the estimated effective dosage for avermectin Bla/Blb alone and with the agricultural spray oil. TABLE III Contact miticidal efficacy of Avermectin Bla/Blb Agricultural Spray Oil combinations 5-DAYS POST-SPRAY 11 DAYS POST-SPRAY ADULTS NYMPHS ADULTS NYMPHS LARVE TREATEMENT RATE (ppm) Dead Alive % Dead Alive % Dead Alive % Dead Alive % Dead Alive % Avermectin Bla/Blb Cont. Cont. Cont. Cont. Cont. Avermectin .25 131 0 100 9 0 100 56 109 34 89 0 100 2 1 67 Bla/Blb .125 83 2 98 23 1 96 51 131 28 55 97 6 0 100 .063 126 32 80 23 0 100 NC 0 NC 0 NC 0 .031 66 16 81 11 0 100 NC 0 NC 0 NC 0 .015 56 40 58 3 0 100 NC 0 NC 0 NC 0 Avermectin .1 138 0 100 8 0 100 113 2 98 17 1 95 188 0 100 Bla/Blb with .05 79 0 100 10 0 100 75 0 100 26 0 100 100 0 100 0.125 % Agricul. .025 175 0 100 9 0 100 106 17 86 71 1 99 76 0 100 Spray Oil .0125 160 0 100 10 0 100 143 13 92 77 10 89 50 0 100 .0063 124 1 99 11 0 100 224 41 85 40 27 60 64 0 100 Avermectin .1 125 1 99 19 0 100 117 4 97 37 1 97 14 2 88 Bla/Blb with .05 223 0 100 17 1 95 174 1 100 50 2 96 6 0 100 0.031 % Agricul. .025 196 0 100 9 0 100 123 7 95 36 12 75 40 0 100 Spray Oil .0125 139 0 100 15 0 100 111 46 71 15 47 24 0 0 .0063 216 4 98 9 4 69 120 32 79 32 49 40 2 0 100 Controls: 0% 0 0 162 0 0 6 0 0 96 0 0 43 0 0 75 0 Agricul. .03% 0 2 99 2 0 2 0 NC 0 NC 0 NC 0 Spray Oil .125% 0 0 85 0 0 6 0 NC 0 NC 0 NC 0 NC = no control TABLE IV Residual miticidal efficacy of Avermectin Bla/Blb Agricultural Spray Oil combinations 4-DAYS POST-SPRAY 13 DAYS POST-SPRAY (11 days post-spray) (20 days post-spray) ADULTS NYMPHS ADULTS NYMPHS LARVE TREATEMENT RATE (ppm) Dead Alive % Dead Alive % Dead Alive % Dead Alive % Dead Alive % Avermectin Cont. Cont. Cont. Cont. Cont. Bla/Blb Avermectin 2.0 140 0 100 16 0 100 60 0 100 11 0 100 4 0 100 Bla/Blb 1.0 76 2 98 9 1 90 51 0 100 12 0 100 6 0 100 0.5 39 0 100 12 0 100 40 0 100 16 0 100 21 0 100 0.25 95 4 93 2 2 50 13 163 7 2 36 5 1 4 20 Avermectin 0.125 193 0 100 25 0 100 60 0 100 19 0 100 7 0 100 Bla/Blb 0.063 96 4 96 35 0 100 43 0 100 21 0 100 7 0 100 with 0.125% 0.031 75 4 95 24 3 89 73 20 78 15 10 60 4 0 100 Agricultural 0.015 49 49 50 8 14 36 25 140 15 4 41 9 0 5 0 Spray Oil Avermectin 0.125 83 2 98 14 7 67 43 33 57 13 13 50 0 0 0 Bla/Blb 0.063 91 2 98 6 2 75 34 37 48 8 7 53 1 0 0 with 0.031% 0.031 58 11 84 10 18 36 NC 0 NC 0 NC 0 Agricultural 0.015 17 26 40 5 16 24 NC 0 NC 0 NC 0 Spray Oil Controls: 0% 0 4 77 5 0 4 0 NC 0 NC 0 NC 0 Agricul. .03% 0 3 58 5 0 9 0 NC 0 NC 0 NC 0 Spray Oil .125% 0 0 86 0 0 5 0 NC 0 NC 0 NC 0 NC = no control TABLE V Estimated effective dosages of Avermectin Bla/Blb combinations. ED90s CONTACT TEST RESIDUAL TEST 5 Days 11 Days 4 Days 13 Days Post-Spray Post-Spray Post-Infestation Post-Infestation ADULTS Avermectin Bla/Blb .1 .25 .25 .4 Avermectin Bla/Blb .0063 .025 .03 .05 with .125% Agricultural Spray Oil Avermectin Bla/Blb .0063 .02 .03 .125 with .031% Agricultural Spray Oil NYMPHS Avermectin Bla/Blb .015 .1 .4 .2 Avermectin Bla/Blb .0063 .0125 .031 .125 with .125% Agricultural Spray Oil Avermectin Bla/Blb .01 .04 .125 .125 with .031% Agricultural Spray Oil LARVAE Avermectin Bla/Blb -- .1 -- .4 Avermectin Bla/Blb -- .0063 -- .02 with 125% Agricul larval Spray Oil Avermectin Bla/Blb -- .0063 -- .125 with .031% Agricultural Spray Oil In the above tests it is noted that the combination treatment is more effective than either treatment alone such that lower concentrations of the avermectin are effective for longer periods of time. In addition, since in the avermectin and combination treated plants many mites are recovered, although most are dead, it is apparent that the effect is not as an ovicide which would be expected with treatment with an oil. The presence of motile mites demonstrates that the egqs were not killed. However, the high mortality observed against the adults, nymphs and larvae populations also demonstrates that the treatment is highly effective aqainst the motile stages of the mite. EXAMPLE 4 Effects of Avermectins and Agricultural Spray Oil on the Two-spotted Spider Mite on Bean Plants Bean plants were treated with various concentrations of avermectin Bla/Blb, Sunspray 6N agricultural spray oil, and combinations thereof, and 7 days thereafter were challenged with a mixed population of the two-spotted spider mite. Table VI gives the results of observations made 6 and 12 days after the challenge. A significant improvement in activitv is noted when the combination is applied to the plant. TABLE VI EVALUATION OF AVERMECTIN Bla/Blb WITH AGRICULTURAL SPRAY OIL TWO-SPOTTED SPIDER MITE ---------------% Mortality ------------- --6-Day Reading ---------12-Day Reading----- Sunspray Avermectin 6N Oil Bla/Blb PPM % Adults Larvae Adults Nymphs Larvae 1.0 - 99 0 100 41 95 0.25 - 0 0 36 1 3 0.063 - 0 0 0 0 0 1.0 1.0 100 66 100 - 100 0.25 1.0 100 21 100 - 100 0.063 1.0 100 0 100 67 95 1.0 0.25 100 57 100 - 100 0.25 0.25 100 0 100 100 100 0.063 0.25 100 0 100 81 95 1.0 0.063 100 57 100 100 100 0.25 0.063 100 0 100 - 100 0.063 0.063 88 0 100 45 - ¯ 7 0 0 0 0 --- 1.0 0 0 0 0 0 --- 0.25 15 0 0 0 0 --- 0.063 0 0 - - Bean plants were challenged with mixed mite population seven days after treatment. EXAMPLE 5 Effects of Avermectin Bla/Blb, and Agricultural Spray Oil on the Citrus Red Mite on Lemon Trees Lemon trees with an ongoing population of citrus red mites were sprayed once with 8 ppm of avermectin Bla/Blb, agricultural sprav oil and a combination thereof. The agricultural spray oil was applied at a rate of 3 pints per 100 gallons of sorav (.375%). The data is summarized in Table VII. TABLE VII CITRUS RED MITE, Panonychus citri on Lemon plants. Material &num; Rate No. Mites per 32 Leaves Days Before or After Spraying -5 +7 +16 +30 +50 +70 Avermectin Bla/Blb, 8 ppm 26.7 0 0.3 24.7 15.0 18.3 Avermectin Bla/Blb, 8 ppm + Agricultural Spray Oil* 33.3 0 0 3.0 1.3 2.7 NR-415 Agricultural Spary Oli* 35 0 1.6 11.3 15.7 36.7 Water (Control) 11.3 11.7 31 81.7 58.3 26.7 *3 pints per 100 gallons (0.375%) EXAMPLE 6 Effects of Avermectins and Agricultural Spray Oils on Bean Aphids Bean plants infested with the Bean aphids were treated with avermectin Bla/Blb, agricultural spray oil and mixtures thereof and the results analyzed 1 and 5 days after treatment. The results are summarized in Tables VIII and IX, and demonstrate that the oil has very little effect alone, and together the treatment is greatly and synergistically improved. TABLE VIII THE EFFECT OF AGRICULTURAL SPRAY OIL ON THE INSECTICIDAL EFFICACY OF AVERMECTIN Bla/Blb Bean Aphid on Bean Plants Emulsifiable Concetration (PPM) % MortalityÚ Oil of avermectin Bla/Blb Day 1 Day5 .25 .5 0 90 .25 5 80 .125 0 85 .063 0 80 0 0 5 .063 .5 25 50 .25 30 50 .125 10 60 .063 15 55 0 5 0 0 1.0 30 35 0.5 20 25 0.25 25 0 0.125 10 0 0 0 0 1/ All values are means of 2 replicates TABLE IX Influence of an agricultural spray oil on the efficacy of avermectin Bla/Blb used against the bean aphid Percent avermectin Bla/Blb Percent Oil (ppm) Control a 0.25 0.5 87 0.125 53 0.031 17 0.0078 0 0 0 0.125 0.5 80 0.125 33 0.031 0 0.0078 0 0 0 0.063 0.5 73 0.125 30 0.031 0 0.0078 0 0 0 0 0.5 47 0.125 3 0.031 0 0.0078 0 0 0 a Mean of three replicates EXAMPLE 7 Preparation of an Aqueous Plant Spray Containing Avermectin Bla/Blb and an Agrict1tural Spray oil For evaluation of synergistie activitv in the laboratory, a 90% oil emulsion was formulated by adding 1 gram of Agrimul 26-B emulsifier to 9 grams of Sunspray 6N 60 sec spray oil. This oil emulsion was treated as a pure (100%) oil and added to solutions of avermectin Bla/Blb to prepare known concentrations of the avermectins and oil as shown in the foregoing examples. For dilute sprav applications under field conditions, 0.04 oz of avermectin Bla/Blb formulated as 0.03 lb per gallon soluble liquid was poured into 100 gal of water. To this resultinq solutinn was added with agitation 1 quart of agricultural spray oil to provide an emulsion containinq 0.04 oz avermectin Bla/Blb (3 ppm) and 0.25% oil in 100 gal of water.

Claims: WHAT IS CLAIMED IS: 1. A synergistic combination useful against motile stages of arthropods infecting plants which comprises one or more avermectin compounds having the formula: EMI29.1 wherein the broken line indicates either a sinqle or a double bond at the 22,23-position n is 0 or 1 such that when n is 0 a hydroqen is present at the 13-position; R1 is hydroqen or EMI29.2 R2 is hydrogen or hydroxy, provided that R2 is present only when the broken line indicates a single bond; R3 is sec-butyl or isopropyl; and R4 is hydrogen or methyl, and an agricultural spray oil. 2. A formulation containing a combination as claimed in Claim 1 in which the amount of avermectin compound or compounds is 0.03 to 8 ppm and the amount of agricultural spray oil is 0.03 to 2% v/v. 3. A formulation as claimed in Claim 2 in which the amount of avermectin compound or compounds is 0.25 to 3 ppm and the amount of agricultural spray oil is 0.06 to 0.5% vlv. 4. A formulation as claimed in Claim 3 in which the amount of avermectin compound or compounds is 1 to 3 ppm and the amount of agricultural spray oil is about 0.25% v/v. 5. A composition for use against the motile stages of mites and insect pests of plants comprising an inert carrier, a compound having the formula set forth in Claim 1, and an agricultural spray oil. 6. A composition as claimed in Claim 5 in which the amount of avermectin compound or compounds and the amount of agricultural spray oil are as defined in Claim 2, 3 or 4. 7. A composition as claimed in Claim 5 or 6 that also includes an anionic and/or a non-ionic surfactant. 8. A synergistic combination as claimed in Claim 1 for use in the treatment of the motile stages of arthropod pests of plants. 9. A formulation as claimed in Claim 2, 3 or 4 for use in the treatment of the motile stages of arthropod pests of plants.

Inventors: DYBAS, RICHARD A.
Applicants: MERCK & CO. INC.
Application year: 1983
Main classification: A01N43
IPC codes: A01N43, A01N63, A01N25