IL33014A - Fungicidal compositions comprising sucrose and 1-alkylaminocarbonyl-2-alkoxycarbonylaminobenzimidazoles - Google Patents

Description

ntina o o**Vi¾i **?*tp o-»i'©an *is«V»11a p*esisp*κ-2->»a anpi3 *01*?»pVK-1-1 Fungioidal compositions eGsa rieiB Bucrose and l-^lk laial_aocarbonyl~2-a koxycar onylamlno--bensltaiil aoXas D0 POST DB NEMOURS AND COMPANY 0: 3121 - la - Benzimidazole compounds are becoming well known as effective fungicides and mite ovicides. Some of these compounds are not easily converted into a form suitable for agricultural application. Conventional formulations have shown lack of stability which causes the compounds to decompose in storage under warehouse conditions in closed containers* !Dheee conventional formulations have also suffered from the serious problem of pressure build-up in storage. Enough pressure is generated to rupture or tear the containers, causing loss of protection of the product and hazard to the user.

The l-alkylaminocarbonyl--2-alko--:ycarbonylaminobenzimida-zoles of structure (A) or its tautomer (B) are outstandingly effective eradicant and preventive fungicides: FORMULA I (A) (B) where is methyl or ethyl and R2 is alkyl of 1 through 8 carbon atoms.

. For the p rposes of this invention, it is not Important whether the disubstituted benzimidazoles of formula I have a structure (A) or structure (B) or are mixtures thereof. For simplicity, all of the compounds are named and claimed as the 1-Csubstituted carbamoyl)-2-benzimidazolecarbamio acid, alk l esters (structure A) with the understanding that the invention covers the pure tautomers (A) and (B) and mixtures thereof as they are lrfeely to occur« Preferred compounds within the scope of formula I in view of their high activity are the following compounds: l-(n-butylcarbaraoyl)-2-benzimidazolecarbamic acid, methyl ester l-( .«-hexylcarbaraoyl)-2-benzimida2olecarbamio acid, methyl ester l-(a-octylcarbamoyi)-2-benzimldaa±ecarbamic acid, methyl ester It has been found that fungicidal compositions of these compounds, e.g., powders, dusts and granules, if they contain sucrose as a diluent, have outstanding stability, biological activity and excellent physical properties.

The compounds of ormula I can be prepared by any of a variety of methods known in the art. Thus they can be prepared by the reaotlon of an 2-benzimidazolecarbamate ester with the appropriate isocyanate. The preparation of these compounds is described in detail in Assignoets-pending-¾ρ.ρ11οτη ion Israel Patent No. 27824, granted July 29, 1971. and in French Patent 1,523,597, granted March 25, 1968. The preparation disclosure of these references is incorporated herein by reference . 1-A lk laminocarbonyl-2-alkoxycarbonylaminobenzlmida- zoles of Formula I are outstandingly effective eradieant and preventive fungicides. Their outstanding performance makes it possible to control fungus diseases with small amounts of material. Consequently, such small amounts must be accurately applied over large areas of ground or foliage, or must be accurately blended with large volumes of soil or seed, so that the benefit from their great activity may be suitably realized. Therefore, the quality of the formulations of 1-alkylaminocar-bonyl-2-alkoxycarbonylaminobenzimidazoles which are available to the user is particularly critical.

The compounds of Formula I are also highly effective mite ovicides.

As previously set forth, the compounds of Formula I are not easily converted into a form suitable for agricultural application in view of stability and pressure build-up problems. The reason for such chemical decomposition and pressure evolution is not understood but is connected with the chemical characteristics of the compounds of Formula I, with the effect of fine grinding necessary to obtain peak, biological activity and distribution of the compound, in small amounts, over areas and volumes which are to be protected against fungus attack, and with the well-recognized fact that in the intimate blend of agricultural pest control formulations, where surfactants, active ingredients and diluents are closely mixed, unexpected interactions can take place.

Agricultural formulations must meet many additional requirements in order to have adequate utility. In the case of wettable powders, for instance, the product must wet easily, and after the wetting has taken place, a good slurry must he obtainable with minimum agitation. This means that the active ingredient must be easily dispersed into a fine dispersion and must not settle rapidly under the many and diverse conditions of concentration, temperature, types of water, etc. which will be found in agricultural use. The powder must not deteriorate in these properties under the normal compression loading Inherent in packaging and in warehouse storage, and the desirable physical properties must remain after extended effects of time and temperature if, for example, a product is transported or stored in warm weather. Furthermore, the formulation must lend itself to easy manufacture, so that it can be blended, ground, conveyed and packaged with the efficiency that makes low cost possible. Finally, and obviously, any agricultural formulation must preserve, and if possible enhance the biological activity of the compound for its intended use.

Failure to rr.eet these requirements are frequently related. For example, chemical instability usually leads to loss of biological activity after storage and deterioration of physical properties. If the physical properties alone deteriorate, even though chemically the product is not changed, this often also causes reduction in biological performance.

Because of these complicated requirements and interactions, the development of an outstanding formulation of a fungicide requires many different studies and tests. Before a mixture can be considered acceptable, the variables which mast be studied include, for example, the ease of grinding of the candidate mixture, the possibility of mill smear, flow properties in manufacturing equipment, caking under load as in a package, wetting speed, ease of dispersion, flocculation , suspension stability, and many others. Storage tests must be conducted, the tendency to generate pressure must be measured, and not only the chemical decomposition in storage, but also the effect of time and temperature on the physical properties mentioned above must be determined. Biological tests in greenhouse and field are necessary. At the same time, the formulator is confronted by a vast number of ingredients which could be tried. For example, the "Handbook of Insecticide Dusts, Diluents and Carriers," second edition by Watkins, Norton, Weidhaus and Braun, (Dortland Books, Caldwell, 1955) lists 176 materials in its index. When this handbook was issued many other diluents were also available, and yet more have come on the market since.

Studies with the l-alkylaminocarbonyl-2-alkoxycarbonyl- , aminobenzimidazoles have shown that conventional diluents of different types, such as clays, talcs, carbonates, silicas, botanical flours, etc. etc. have deficiencies which make formulations containing them unacceptable. In general, they cause serious decomposition in storage with pressure evolution and loss of physical properties. Even when these deficiencies are not very pronounced, the biological performance of certain formulations containing these conventional diluents has been poorer than would be expected for products with the unusual potency of compounds of Formula I.

It has therefore been surprising and significant that sucrose, a widely available, inexpensive material, could be used as the diluent in formulations of these compounds to rovide roducts which are outs andin in their stabilit essentially free from evolution of pressure, and which possess outstanding biological activity and excellent physical properties .

Accordingly, this invention provides powders, dusts, and granules of l-alkylaminocarbonyl-2-alloxycarbonyiamino-benzimidazoles of Formula I which contain sucrose as the diluent. Other formulation ingredients can also be present providing certain requirements are met. These ingredients can include vertaln wetting and dispersing agents, certain anti-foam agents, and certain corrosion inhibitors. The formulations of this invention can also contain certain other fungicides as will be described below.

Wettable powder formulations of this invention contain from 15 to 905Ϊ active ingredient, from about 0.5 to 10J of one or more surface active agents, small amounts (e.g., up to about 1% each) of antifoam agents and/or corrosion Inhibitors, with the remainder, 9.5 to 8 .5 > being sucrose. These wettable powders are prepared by blending the ingredients and grinding the mixture to obtain fine particle size. Although hammer mills can be used, more powerful grinders such as pin mills or fluid energy mills are preferred. Preferred wettable powders contain from 30 to 75# active ingredients. Powders in which the active ingredient content is between O and 6556 are the most highly preferred .

In addition to active ingredient and sucrose, these wettable powder formulations also contain surface active agents to assure adequate wetting and dispersion in water. Suitable surface active agents include anionic, cationic and nonionic types, and many suitable Surfactants are shown in MeCutcheon's Detergents and Emulsifiers Annual , 1967. However, for optimum performance and stability, the choice of wetting and dispersing agents should be restricted to those which do not have highly acidic or highly basic groups or highly active hydrogens such as, for example, surface active agents with amine hydrogen atoms. In general, anionic and nonionic surface active agents are preferred. Furthermore, surface active agents are occasionally themselves formulated products, made to a standard wetting power, dispersing power, detergency by admixture with standardizing agents. For the compositions of this invention, it is preferred that the surface active agents not contain clays, silicas, and the like, but contain predominately inert standardizing agents, including sucrose.

Therefore, preferred wetting agents are salts of alk lbenzene and alkylnaphthalene sulfonates, saits of sulfated fatty alcohols, fatty acid esters of sodium isethionate, esters of sodium sulfosuccinate , salts of sulfated or sulfonated fatty acid esters, or salts of petroleum sulfonates and sulfonated vegetable oils. Other preferred surface active agents include ethylene oxide adducts to long chain alcohols, to mercaptans, to alkylated phenols, to fatty or resin acids, and to sorbitan or sorbitol esters of fatty or resin acids.

Preferred dispersants are methyl cellulose, polyvinyl alcohol, sodium, calcium, and magnesium lignin sulfonates, salts of polymeric alkylnaphthalene sulfonates, sodium naphthalene sulfonate, polyvinylpyrrolidone derivatives, polymethylene blsnaphthalenesul onate and sodium N-methyl-N-(long chain acid) taurates. Particularly preferred, because of improved handling and flow characteristics, are those wettable powder formulations in which the surface active agent is a solid rather than a liquid or soft wax.

Dusts are pulverulent mixtures which are usually applied without dilution with water. These dusts will usually contain from 0.5 to 2 active ingredient, and many also optionally contain small amounts (up to approximately 2%) of wetting and dispersing agents, the remainder being sucrose. Dusts containing from 2 to 1 # active ingredient are preferred. Such dusts can be made by diluting a wettable powder described above to the desired concentration with additional sucrose.

In this case the sucrose used for the final dilution will not be too finely ground, so that the settling characteristics of the product are improved and excessive drift is avoided.

In other instances the active ingredient, possibly with small amounts of sucrose and surface active agents, is finely ground as described above, then blended with the remainder of the sucrose to the desired concentration, and the entire charge is deagglomerated or coarsely ground to prepare the final dust.

For so»e applications, where very dilute applications are desired, it is sometimes desirable to dilute a dust composition further with additional sucrose to obtain a dust containing 0.05 to 0. # active ingredient.

The 1-alky laminocarbonyl-2-alkoxycarbony laminobenzimida- zoles of Formula I can also be formulated with sucrose as granules. Granules are particulate solids with a superficial particle size greater than powders. Usually such granules range in size from 14- to 60-mesh (e.g., from about 1 to 0.25 mm.). However, as is well known to those ekilled in the art, the active ingredient contained within such granules are usually in about the same very finely divided state as is the case for dust and wettable powder formulations. In other words, a granule is a composite containing very fine particles of active ingredient plus diluent and possibly other additives. from benzi i l / and dispersing agents to aid in the disintegration of the granule in soil. However, the amount of such wetting and dispersing agents will usually not exceed about 2% insofar as desired modification in physical characteristics of the granule is concerned. Granules containing from 2# to 15 active ingredient are preferred.

Such granules can be made by a number of different methods. For example, finely divided wettable powder or dust, or a special pulverulent granule premlx, can be blended with a small amount of liquid sufficient to cause the powder to granulate upon agitation as in a twin shell blender or a granulating pan. After granulation has proceeded to provide particles of adequate size and strength the carrier is evaporated, the mix is sifted, and unwanted particle size ranges are recycled. Similarly, finely divided pulverulent sucrose/active ingredient mixtures can be blended with a granulated sucrose carrier, and liquid is then added to fix the powder on the sur ace, followed again by removal of the liquid. Suitable liquids for these granulation processes are aliphatic and aromatic hydrocarbons, chlorinated hydrocarbons, alcohols and ketones, and the like. Water can also be used. In general, preferred liquids have high volatility to make removal after granulation convenient. It is also possible to prepare a pulverulent premix which is extruded or compacted into solid shapes. These are then cut or broken into granules of suitable size. If desired, larger bodies, usually called pellets, can be prepared from such extrusions, with particle sizes of 1/8 inch or even larger. Finally, a solution of the 1-alky laminocarbonyl-2-alkoxycarbonylamino- benzimldazoles can be applied to preformed granular sucrose to form a film over the available surfaces. The solvent is then removed .

In all of the formulations of this invention, be they wettable powders, dusts or granules, it is desirable that the moisture content be kept at a minimum. These compositions usually contain less than 1/2% moisture, and mixtures containing less than approximately 0.25¾ water are preferred.

Formulations of this invention may also contain fungicides other than the l-alkylaminocarbonyl-2-alkoxycarbonyl-aminobenzimidazoles of Formula I. Preferred such other fungicides are thiram, captan and sulfur, and others which have been found to be chemically compatible with these compounds. When such other fungicides are present they can replace some of the compounds of Formula I in the compositions above in such a way that the ratio of 1-alkylaminocarbony 1-2-alkoxy-carbonylaminobenzimidazoles to the other fungicide ranges from 1:Ί to Ί:1. For example, a wettable powder containing equal amounts of a compound of Formula I and thiram or a wettable powder containing one part of an 1-alkylaminocarbonyl-2-alkoxycarbonylaminobenzimidazole plus 3 parts of captan with wetting and dispersing agents and sucrose as described above, have many outstanding properties in the control of fungus diseases on economically important crops.

The formulations of this invention are usually applied as dusts, as granules, or as sprays in conventional application equipment. In such instances, the performance of the 1-alkyl-aminocarbonyl-2-alkoxycarbonylaminobenzimldazoles of Formula I can be enhanced further by the use of larger amounts of certain surface active agents and penetrants as will be described subse uentl .

As mentioned previously, it has been found that the compounds of Formula I possess outstanding fungicidal and mite ovicldal activity when employed to prevent or mitigate damage to plants and inanimate organic materials.

The paragraphs which follow describe in more detail the utility of these compounds.

The compounds control a wide variety of fungus diseases of foliage, fruit, stems and roots of growing plants without damage to the host. Fruits, tubers, bulbs, roots, seeds and other plant parts harvested for food, animal feed or for other purposes are protected from fungus deterioration during processing, distribution and storage. Seeds, tubers, cuttings and other plant propagation materials are protected from fungus attack during handling and storage, as well as in the soil after planting. Wood, fabric, fiber board, paper and other industrial materials are protected from unsightly stain and destructive decay caused by fungi. Luggage, shoes, shower curtains, carpets, mats, clothing and other useful household, public or industrial items are protected from rot, fungus stains and mold growth.

The many fungi against which the compounds of Formula I are active may be represented by, but is not intended to be limited to, the following: Venturia lnaequalls , which causes apple scab; Podosphaera leucotricha , which causes powdery mildew on apple; Uromyces phaseoli , which causes bean rust; Cercospora apil , which causes early blight of celery; Cercospora betlcola, which causes leaf spot of sugar beets; Sclerotinia sclerotiorum, which causes rot of vegetable crops, such as lettuce, beans, carrots, and celery; Colletotrlchum spp., which cause anthracnose of fruits and vegetables, such as beans, Plricularla sp. , which causes Johnson spot on banana; Erysiphe cichloracearum, which causes powdery mildew on cantaloupe and other cucurbit crops; Penicllllum dlgitatum, Phomopsls spp., and Dlplodla natalensls , which cause fruit rots on citrus; Ceratostomella ulml , which causes Dutch elm disease; Sphaerothec humull , which causes powdery mildew on roses; Diplocarpon rosae , which causes black spot on roses; Ramularia sp., which causes le spots on ornamental plants; Botrytls clnerea , which causes bloss and fruit rots of ornamentals, fruits and vegetables; Uncinula necator, which causes powdery mildew on grapes; Gulgnardla bidwe which causes grape black rot; Melonconlum fullgineum , which caus white rot of grapes; Coccomyces hlemalls , which causes cherry le spot; Cytospora sp., which cause cankers of trees; Cladosporium carpophllum, which causes peach scab; Fusicladium e usum, which causes pecan scab; Erysiphe graminis , which causes powdery milde on cereals; Monollnia (Sclerotlnia) laxa and . fructlcola, whic cause brown rot of stone fruits, such as peaches, cherries and apricots; Pseudopenziza rlbes , which causes leaf spot on goosebe Pirlcularia oryzae , which causes rice blast; Pucclnia recondita , P. coronata and P. glumarum, which cause leaf rusts of wheat, oa and grasses, respectively; Pucclnla gramlnis trlticl , which caus stem rust of wheat; Claviceps purpurea, which causes ergot of rye and grasses; Aspergillus nlger , which causes cotton boll rot as well as decay following wounding in many plant tissues; Aspergillus flavus , which causes mold growth on peanuts, as well as on other food and field materials; Aspergillus terreus , which is common in soil and attacks vegetable matter; Tllletia caries and other Tllletia species, which cause common bunt of wheat; Ustllago trlticl, Ustilago nigra, Ustllago avena (and other Ustllago species), which cause loose smut of wheat, barley, species, which cause loose smut of wheat; Sphacelotheca sorghi , which causes covered smut of sorghum; Ustllago horde! and Ustllago kollerl , which cause covered smut of barley and oats, respectively; Plthomycea chartorum, which is present in turf, pastures, and other grassy areas and is known to have several secondary effects; Gloeodes pomigena, which causes sooty blotch on apples; Physalospora obtusa , which causes black rot on apples Mlcrothyriella rubl , which causes flyspeck on apples; various species of Rhlzoctonla, Fusarium and Verticllllum present in soil and attacking the roots or other underground parts and the vascular system of a variety of plants; various species of Penicilllutn growing on such things as fabric, fiber board, leather goods and paint; species of yrotheclum attacking such items as shower curtains, carpets, mats and clothing.

The mite ovicidal action of the compounds of Formula I is useful in preventing the development of damaging populations of mites or in causing the gradual reduction of existing populations. The movement of mites is limited. Thus, an increase in population or the continuation of a high population in a particular locus depends largely upon the hatching of eggs laid in that locus.

Mite eggs do not hatch to produce living young if the eggs are treated with one of these compounds, or if they are laid on a surface containing one of these compounds. Further, the eggs will not hatch if they are laid by a female mite that has been in contact with one of these compounds , or are laid by a female mite that is ingesting or has recently ingested food such as plant juices containing one of these compounds. This interference with the hatching of eggs prevents the population from increasing significantly beyond that present at the time o . vidi on w an already infested area over a relatively short period of time. Further as long as the compounds are present on the surface the mites occupy or remain in their food supply, new populations cannot develop.

Many species of mites which cause damage to fruits, field crops, vegetables, and ornamentals under a wide variety of circumstances, are controlled by the compounds of Formula I. The extent of the practical utility of the mite control obtained is represented by, but is not intended to be limited to, the following listing of specific susceptible mites along with the types of damage that they can cause: Panonychus ulml (European red mite) and Tetranychus telarlus (two-spotted mite) which are commonly called "orchard mites"; these mites attack a great many deciduous tree fruits including apples, pears, cherries, plums and peaches; Tetranychus atlantlcus (Atlantic or strawberry mite), T. clnnabarinus (carmine spider mite) and T. paciflcus (Pacific mite); these mites attack cotton and numerous other crop plants; Paratetranychus cltrl (citrus red mite) and others which attack citrus; Phyllocuptruta slelvora which causes citrus rust; Bryobla praetlosa (clover mite) which attacks clover, alfalfa and other crops; Phyllosoptruta olelvora, the citrus rust mite; Acerla neocynodomls which attacks grasses and other plants; Tyrophagus lintneri which is a serious pest in stored foods and on cultivated mushrooms and Lepldoglyphus destructor which injures Kentucky bluegrass seed in storage.

The compounds of Formula I when applied enter and move freely within plants, i.e., they are systemic. Thus both fungi an mites can be controlled in plants in parts well removed from the point of application. In view of this activity the compounds can be applied to seeds; thus the treatment of cucumber seeds with a few grams per 50 kilograms of seed of a compound of this invention provides control of powdery mildew (Erysiphe clchoracearum) and spider mites such as Tetranychus urtlcae on the resulting plants for periods in excess of days.

Applications to soil also provides control of certain foliage diseases and mites on plants growing in the treated soil. Spray or dust treatments of plant foliage and stems Impart protection against both fungi and mites to other parts of the plant not actually sprayed and to new foliage developing later.

There are important practical advantages associated with the use of an effective systemic pesticide. Thus successful application to seed as described above, results in great savings in chemical and application costs. Soil applications which effectively protect entire plants for an extended period also represent similar savings. Distribution within the plant following foliage treatment eliminates the need for frequent retreat ent to protect rapidly growing tissue. Also, materials within the plant are not subject to removal by rainfall.

Similarly, movement or translocation of the chemical within the plant can provide protection to those parts of the plant that may not have been covered by the original spray application.

This is of particular importance with plants of dense growth character resisting the Intrusion of the spray and also to tall plants, such as shade trees, where the spray will not reach to the top.

An additional valuable characteristic of the compounds of Formula I is their ability to prevent the spread or to kill fungus infection already established within a plant, i.e. they are curative. Thus, the compounds need not be applied until after conditions develop which permit the actual initiation of fungus attack. This means that, under some circumstances, It is possible to avoid applying any chemical during the entire life of the crop. In other cases, only a part of the normal full schedule of pesticide is required.

Therefore great savings both in chemical cost and application labor are possible with compounds capable of systemic and curative performance. Another saving is afforded by the compounds of Formula I through the fact that both fungi and mites are controlled by applications of a single chemical.

The compounds of Formula I provide protection from damage caused by fungi, mites or both when applied to the proper locus by the methods described hereinafter and at a sufficient rate to exert the desired fungicidal and mite ovlcldal effect. They are especially suited for the protection of living plants such as fruit-bearing trees, nut-bearing trees, ornamental trees, forest trees, vegetable crops, horticultural crops (including ornamentals, small fruits and berries), fiber crops, grain and seed crops, sugarcane, sugar beets, pineapple, forage and hay crops, beans, peas, soybeans, peanuts, potatoes, sweetpotatoes , tobacco, hops, turf and pasture.

Living plants may be protected from fungi and mites by applying one or more of the compounds of this invention to the soil in which they are growing or in which they may subsequently be seeded or planted; or to seeds, tubers, bulbs or other plant reproductive parts prior to planting; as well as to foliage, stems and fruit of the living plant.

Soil applications are made from sprays, dusts or granules. Preferred rates for application of the compounds of this invention to soil in which plants are or will be growing range from 0.01 to 500 parts per million by weight of the soil In which the roots are or will be growing. More preferred use rates are in the range of 0.1 to 50 parts per million ¾ and the most preferred rates are in the ranr of 0.25 to 25 parts per million.

Preferred rates for application to seeds, tubers, 0 bulbs or other plant reproductive parts, range from 0.03 to 6000 grams of active compound of this invention per 50 kilograms of planting material treated. More preferred rates are in the range of 0.3 to 3000 grams of active compound per 50 kilograms. The most preferred rates are in the range of 2.8 to 1500 grams per 50 kilograms.

Applications can be made from dusts or slurries.

Such treatments protect the treated parts themselves from damage due to fungi, mites, or both, and in addition, impart extended protection against both types of pests to the resulting new plants.

Preferred rates for application of the compounds of Formula I to foliage, stems and fruit of living plants range from 0.012 to 60 kilograms of active ingredient per hectare More preferred rates are in the range of 0.025 to 30 kilograms per hectare and the most preferred rates are in the range of 0.05 to 15 kilograms per hectare. The optimum amount within this range depends upon a number of variables which are well known to those skilled in the art of plant protection. These variables include, but are not limited to, the disease to be controlled, -}Q weather conditions expected, the type of crop, stage of development of the crop, and the interval between applications. Applications within the range given may need to be repeated one or many more times at Intervals of 1 to όθ days. Applications are made from dusts or slurries.

Wood, leather, fabric, fiber board, paper and other industrial materials of an organic nature can be protected from decomposition or discoloration by fungi and Infestation by mites by coating with an effective amount of one or more of the compounds of this invention. The coating can be accomplished by dusting the material to be protected with a suitable composition containing the active ingredient. The preferred use rates for the active ingredient in the treating preparation actually applied to the material to be protected are in the range of 0.025 to 9 # b weight.

More preferred rates are in the range of 0.05 to 0 > with the most preferred rates being in the range of 0.1 to .

Where incorporation or impregnation procedures are to be employed, use rates may be expressed in terms of the amount of active ingredient introduced into the material to be protected. The preferred use rates for these types of applications are in the range of 0.001 to 30 percent by weight of active ingredient in the final product. More preferred rates are in the range of 0.005 to 15¾ with the most preferred rates being in the range of 0.01 to 7%.

Luggage, shoes, shower curtains, carpets, mats, clothing and other useful household, public or industrial items are protected from rot, fungus stains and unsightly mold growth as well as infestation by mites by the active compounds.

Surface t c ^^^* M)i be accomnlis d by dust aopl 1 cations . Duste containing from 2 to 1 $ active ingredient are preferred.

As was previously set forth, the compounds of Formula I ire especially suited for use on living plants. rate indicated above is generally accomplished by employing sprays or dusts containing the proper amount of active ingredient For the control of mites and funri which are regularly present, applications often start prior to the time that the problem actually appears and continue on a re-determined schedule.

Such a procedure is termed "preventive" or "protective.'' With the compounds of Formula I , successful control of plant diseases can also be accomplished by applications made after they are present. Fungus mycelia within the plant tissue are actually killed. This approach or effect is termed "curative" or "eradicant" and permits the user to realize considerable savings.

Curative control of plant diseases with the compounds of this invention is enhanced if the treated plant parts are moist for one or more periods of 2 to 12 hours each soon after the active compound is applied. Often the slow drying of an original spray treatment or naturally occuring rains, mists, fogs or dews will accomplish this. Under other circumstances, such as during dry periods or in shelters such as greenhouses, it is necessary to keep the plants moist by some special effort for best results.

When the compounds of Formula I are applied, their activity can be enhanced by using certain adjuvants, for example in the water in which the benzimidazole fungicides are dispersed. These adjuvants may be surface active agents, oils, humectants, enzymes, carbohydrates, and organic acids.

They improve the performance on tubers, on foliage, in treatments used for dip application to roots of living plants, in the case of liquids used for injection into the roots or stems of living plants, or in mixtures used to treat fruits, tubers, bulbs roots and the like after harvest.

Surface active agents that enhance fungus control and mite control by the active compounds include sulfonated and sulfated amines and amides, dlphenyl sulfonate derivatives, ethoxylated alcohols, ethoxylated alkylphenols , ethoxylated fatty acids, ethoxylated fatty esters and oils, polyethylene oxide polypropylene oxide combinations, alkyl-sulfonates, fluorocarbon surfactants, glycerol esters, ethoxylated alcohol sulfates, glycol esters, isethionates , sulfated ethoxylated alkylphenols, lanolin derivatives, lecithin and lecithin derivatives, alkanol amides, phosphate derivatives, monoglycerldes and derivatives, quaternaries, sorbitan and sorbitol derivatives, sulfosucclnates , alcohol sulfates, sulfated fatty esters, sulfated and sulfonated oils and fatty acids, alkyl benzene sulfonates, imidazolines, taurates , ethoxylated mercaptans, ethoxylated amines and amides, modified phthalic glycerol alkyl resins, and similar materials. The oils include nonphytotoxic aliphatic spray oils and triglycerides, either with or without emulslfier to permit dispersion in water. Humectants such as glycerin or ethylene glycols, enzymes such as bromelin, and carbohydrates such as glucose, lactose, and dextrose are also useful. Organic acids of interest include glycollic and gluconic acids.

Although the precise manner in which these additives improve the performance of the fungicides of this invention is not known, the effect is, nevertheless, startling, and it is possible that these additives improve the penetration Into the plant or translocation throughout the plant of the fungicides of this invention.

Preferred surface active agents to improve the fungi cldal and mite ovicidal activity of these compounds are products such as dioctyl sodium sulfosucclnates ("Aerosol" OT and "Aerosol" OT-B), blends of aromatic sulfonates and ethylene oxide derivatives ("Argrimul" G , "Aprimul" A-100, "Agrimul" N-100, "Emcol" H50A, "Emcol" H53), polyoxyeth lene sorbitol oleate/laurate ("Atlox" 1045A), sodium lauryl sulfate ("Duponol" ME) , polyoxyethylated vegetable oils ("Emulphor" EL719), lecithin derivatives ("Emultex" R) , acidic complex organic phosphate esters ("Gafac" RE-610, "Victawet" ) , aliphatic amide alkyl sulfonates ("Hyfoam" Base LL) , oleic acid esters of sodium isethionate ("Igepon" AP78), sodium N-methyl-N-oleoyl taurate ("Igepon" T77), sodium salt of sulfated lauryl and myristyl colamide ( "Intramine" Y) , polyethylene glycol OQ oleic acid ester ("Nonisol" 210), sodium dodec lbenzene sulfonate ( "Sul-Fon-Ate" AA 10, "Ultrawet" K), polyoxyethylene ethers with long-chain alcohols ("Surfonic" LR 30, "Alfonic" 1012-6, "Brij" 30, "Tergitol" TMN) , ethylene oxide condensates with propylene oxlde/eth lene diamine condensates ("Tetronic" 504), polyhydric alcohol esters ("Trem" 01*1), modified phthalic glycerol alkyl resins ("Triton" B 1956), quaternaries ("Zelec" DP), alkylphenol ethylene oxide condensate ("Dowfax" 9N*J , "Dowfax" 9N10, "Hyonic" 9510, "Tergitols" ) and the like.

Examples given in parentheses are illustrative and do not exclude other unnamed commercial products. Examples of other surface active agents In each of these several categories are listed In "Detergents and Emulsifiers" , 1965 Annual, or 1966 Annual, published by John W. McCutcheon Inc., 236 t. Kemble Avenue, Morristown, New Jersey.

Preferred oils include spray oils such as "Orchex" 796 made emulsifiable with "Triton" X-¾5» castor oil made emulsifiable with "Triton" X-ll^, corn oil made emulsifiable wi "Triton" X-ll^, Volck Oil #70, Sunoco Oil No. 7E and similar nonphytotoxic spray oils of vegetable, animal or mineral origin The preferred rates for these surfactants when used in sprays is in the range from 10 to 10,000 parts per million of the spray fluid. More preferred rates are in the range of 30 to 3,000 parts per million and the most preferred rates are in the range of 100 to 1,000 parts per million.

For dusts, the preferred surfactant rates are in the range of 1,000 to 300,000 parts per million of the material actually applied. More preferred rates are in the range of 5,000 to 200,000 parts per million with the most preferred rates being in the range of 10,000 to 100,000 parts per miUion.

As previously mentioned, the active compounds are systemic. For systemic applications to above-ground parts, such as foliage, stems and fruit, the presence of a surface-active agent in the spray or dust enhances activity. Use rates for the surface active agent here are the same as for sprays and dusts for preventive or curative control as discussed above. Systemic effect from the treatment of above-ground parts is also enhanced by moisture on the treated surfaces for one or more periods of 2 to 12 hours each .

Systemic control of both mites and fungi on plants is also accomplished by applications to seeds, tubers, bulbs other reproductive parts prior to planting as well as by application of the chemical to the soil in which the plants to be protected are, or will be, growing. Application to reproductive parts prior to planting is effected through the use of sprays or dusts containing one or more of the compounds of this invention. Treatment of soil is accomplished by physical mixing prior to planting, distribution in the furrow at planting time, application in transplant water, placement in the soil EXAMPLE 1 A powder is prepared by first blending the following ingredients : l-(n-butylcarbamoy1 )-2-benzimidazole- carbamic acid, methyl ester 30? sodium dioctylsulfosucclnate ("Aerosol" OT-B) 2% methylcellulose ( "Methocel" 15 MC) 0.5* sucrose 67. ? The mixture is then micropulverized and is air-milled until at least 50% by weight of the active ingredient consists of particles less than 2 microns, as determined by Andreasen pipette sedimentation.

A uniform field planting of sugar beets in Ohio is selected. Alternate rows are sprayed with water containing a suspension of the wettable powder described above along with a dioctyl sodium sulfosucclnate surface active agent ("Aerosol" OT). The amount of the wettable powder used is such as to provide one gram of the active compound per liter of water. The amount of "Aerosol" OT used is such as to provide 250 ppm in the final spray. The spray is applied at weekly intervals at the rate of 1000 liters per hectare.

The remaining rows are left unsprayed.

Twelve weeks after the initiation of the test, the sprayed rows of sugar beets are healthy and growing rapidly. The untreated rows, on the other hand, are heavily infected with the leaf spot fungus, Cercospora beticola. As a consequence of this fungus Infection, the plants in the untreated rows are growing slowly and will clearly provide less yield.

All the compounds of Formula I can be so formulated and used.

EXAMPLE 2 A powder of the following composition is prepared: 1_( n-but lcarbamoyl )-2-benzimidazole- carbamic acid, methyl ester 50 sodium dioctylsulfoeuccinate ("Aerosol" OT-B) 3% methylcellulose ("Methocel" 15 HC) 0.5% sucrose ^6.5% The ingredients, after blending, are ground in a pin mill and are further ground in a fluid energy mill such as a Micronizer until more than half of the active ingredient is in the form of particles less than about 2 microns in size, as determined by a Fischer Sub-Sieve Sizer.

The above 50$ wettable powder formulation is dispersed in water to give an active ingredient concentration of 3.6 grams per liter of water. Eight uniform apple trees of the same variety are selected for testing. Pour of these are sprayed to run-of , which is approximately 2850 liters per hectare, at weekly intervals during the growing season with the above formulation, and the other four trees are left un-sprayed .

By the end of the season the unsprayed trees have developed very high populations of orchard mites and are highly infected with apple scab, Venturla lnaequalis . Due to the feeding of the mites, the foliage is russeted and drops prematurely. Also, the untreated trees have poor twig growth and small, spotted fruit.

The trees sprayed with methyl l-(¾-butylcarbamoyl)-2-benzimidazo3e carbamate are essentially free of mites, their eggs and apple scab. As a result of the excellent mite control, the sprayed trees have foliage of a thrifty, dark green color, and they exhibit good twig growth and fruit EXAMPLE 3 A formulation as shown in Example 2 is prepared, using the same ingredients and procedures, except that the active ingredient is replaced by 1- (n-hexylcarbamoyl )-2-benzimidazolecarbamic acid, methyl ester.

A uniform field planting of cantaloupe in North Carolina is inoculated with the powdery mildew fungus (Erysiphe cichoracearum) . After 10 days this organism has become well established in the plants.

At tnis time alternate rows are sprayed with water containing a suspension of the wettable powder prepared as described above and an added amount of a polyhydric alcohol ester surface active agent ("Trem" Ol ) . The concentration of this chemical suspension is such as to give 227 grams of the active compound of this formulation per 378 liters of water (0.06¾) and 400 ppm of the surfactant. The spray is applied at a volume of I IQ liters per hectare. The remaining rows are left unsprayed.

After another 15 days the unsprayed rows are heavily damaged by powdery mildew and some of the plants are dying.

The sprayed rows, however, are healthy and growing rapidly. The results indicate that the active compound of the suspension acts as a curative fungicide.

EXAMPLE ¾ A formulation as shown in Example 2 is prepared by analagous methods, except that 1- (n-octylcarbamoyl )-2-benzimidazolecarbamic acid, methyl ester is used as the active ingredient .

Test plots are established in a rice field. The 33014/2 26 alcohol ester surface active agent ("Trem" 014). The amount of the wettable powder used is such as to provide 1.5 grams of the active compound of this invention per liter of water. The amount of "Trem" 014 is 400 ppm in the final spray.

The spray is applied at weekly intervals at the rate of 900 liters per hectare. The remainder of the field is left un- sprayed. Three months after the start of the test, the sprayed plots are healthy and growing well. The untreated plots on the other hand, are seriously damaged by the rice blast fungus, Plricularia oryzae which greatly reduces yield.

EXAMPLE 5 A dust is prepared as follows: Wettable powder of Example 2 / 16? sucrose 84% The incredients are blended and then hammer-milled in a micropulverlzer having a screen with 1/8 inch (3.-2 mm.) round hole openings.

Sugar cane seed pieces cut in November are divided into eight lots. Four of these lots are dusted in such a way as to cover all surfaces with the dust prepared as described above. The other four lots are dusted with the inert diluent only. All lots are stored under similar conditions until the following February at which time they are examined. The four lots that had been treated with the dust described above are in good condition. The four uii- protected lots, on the contrary, are so badly rotted by fungi of the genus Fusarlum that they cannot be planted. 33014 2 - 27 EXAMPLE 6 Dusts are prepared from the following compounds: 1-(methylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester 1-(butylcarbamoyl)-2-benzimidazolecarbamic acid, isopropyl ester Active compound 65 % dodecylbenaenesulfonic acid, sodium salt 3$ sucrose After blending the ingredients are milled until substantially all of the active ingredient is in the form of particles smaller than 4 microns.

This pre-mix is then diluted with pulverulent sucrose in the following ratio to obtain a 10 dust: Pre-mix ' 16% sucrose 84% 35014/2 Alternate rose bushes growing In a greenhouse are dusted lightly at weekly intervals with the formulation described above. After two months of this program the treated plants are healthy, with dark green attractive foliage and are growing well. The untreated plants, on the other hand, have much foliage discolored and curled due to infection by the rose powdery mildew organism, Sphaerotheca humuli. Other foliage on the untreated plants is yellowed due to attack by the Atlantic mite (Tetranvchus atlantlcus) . Due to the extensive foliage damage, the plants not treated with the dusts grow more slowl than the protected plants.

EXAMPLE 7 A pre-mix of the following composition is prepared by blending the ingredients and milling twice in a hammer»mlll fitted with an 0.020 Inch («0.5 mm.) round-hole screen: 1- (n-butylcarbamoy1 )-2-benzimidazole- carbamic acid, methyl ester 9055 sodium alkylnaphthalene sulfonate ("Alkanol"" B) 1* polyvinylalcohol ("Elvanol" 51-05) 155 sucrose 855 The pre-mix is then blended with sucrose in granular form having a particle size of 20-40 mesh ( 40.4 to 0.8 mm.): pre-mix 11. ¾ ' granular sucrose 88.5% When the finely-divided pre-mix has become evenl distributed, about 1855 dry methylene chloride is sprayed on, and blending is continued until the methylene chloride has become distributed. The granules are then dried in a warm stream of dry air.

A field in California is seeded with cotton in the normal manner, except that granules prepared as set forth above are added to alternate rows. These granules are dropped in such a way that some fall into the furrow and some are mixed with the covering soil. The rate of granule application is such as to employ 0.45 kilograms of active chemical per 3600 meters or row. The remaining rows are untreated.

Six weeks after planting, many of the plants in the rows without the granules are dead, and other show soreshin lesions caused by Rhizoctonla solani as well as supporting heavy populations of the Pacific mite (Tetranychus pacificus). In the rows that had received the granules, all plants remain alive and are healthy, and further they are free of mites.

The effect on mites is clearly systemic. 8 EXAMPLE l-(n-butylcarbamoyl)-2-benzimidazole- carbamic acid, methyl ester 30$ thiram 30% methylated cellulose ("Methocel"15 MC) 0.5* sodium alkylnaphthalene sulfonate ("Alkanol" B) 3% sucrose 36.5$ The inn"edients are blended and ground in a manner analagous to Example 2.

The wettable powder is added to water at the rate of 4 grams of the active ingredients per 378 liters of water.

A modified phthalic glycerol alkyd resin surface active agent ; 33014/2 - 30 - point of run-off) alternate trees in a field planting of apples. Sprays are applied at weekly intervale from April 25 until June 6. From June 6 until the end of the season, the sprays are applied at intervals of two weeks. The remaining trees in the planting are left unsprayed.

In early September all trees are carefully examined.

Trees that were sprayed with the active compound are healthy and free of mite infestation and fungus damage. The fruit on the sprayed trees is unblemished and of good size. The foliage of the unsprayed trees, on the other hand, is heavily Infested with the apple scab fungus (Venturla lnaequalla, the cclar-apple rust fundus, Gymnosporanglum Junlperl - ylrglnlanae and the powdery mildew fungus (Podosphaera leucotrlcha) . Also, 'the leaves of the unsprayed plants are badly infested with European red mites (Panonychus ulmi) .

The fruit on the unsprayed trees is spotted with scab, rust lesions and of small size.

EXAMPLE 9 l-(n-butylcarbamoyl)-2-benzimidazole- carbamic acid, methyl ester 12.5% captan 37.5% 8odium dioctylsulfosucinnate ("Aerosol" OT-B) 3% methylated cellulose ("Methocel" 15 MC) 0.5* sucrose 16.5* *" The ingredients are blended, hammer-milled, and then air milled in an Air Reductionizer until substantially all of the ' active ingredient consists of particles smaller than about 5 microns.

The above formulation is dispersed in water at a rate of 1 kilogram of formulation to 400 liters of water. A modified phthalic glycerol alkyd resin surface active agent ( "Triton" B* of run-off) alternate vines in a grape vineyard. Sprays are applied at intervals of two weeks from May 1 until harvest.

The remaining vines in the vineyard are left unsprayed.

At harvest all vines are carefully examined. Vines that were sprayed with the formulation of the invention are healthy and free of mite infestation and fungus damage. The grapes on the sprayed vines are unblemished and of good size. The foliage on the unsprayed vines, on the other hand, is heavily infested with European red mites (Panonychus ulml ) , and badly damaged from infestation by the powdery mildew fungus (Uncinula necator) and the downy mildew fungus (Plasmopera ylticola) . The grapes on the unsprayed vines were small, broken open and rotted due to fundus infestation.

EXAMPLE W In lieu of the 1- (n-butylcarbamoyl )-2-benzimidazole- 9 carba ic acid, methyl ester of Example yj. , the following compound can be used with like results: l-(n-hexylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester l-(n-octylcarbamoyl )-2-benzimidazolecarbamic acid, methyl ester ¾~^"Bw ho-x he.ny-3.--Mtfttamoy1 ) ^2~b^aaim-idaao3f»»a.a^am «--'a-e 4ji In each case the products are mixed and ground in a manner similar to Example .

The above formulation is dispersed in water at a rate of 1 kilogram of formulation to 400 liters of water. A modified phthalic glycerol alkyd resin surface active agent ("Triton" 3 1956) is added in an amount to give 400 ppm. in the final spray. This suspension is used to spray (to the point of run-off) alternate vines in a grape vineyard. Sprays are lied t vals At harvest all vines are carefully examined. Vines that were sprayed with the formulation of the invention are healthy and free of mite infestation and fungus damage. The grapes on the sprayed vines are unblemished and of good size. The foliage on the unsprayed vines, on the other hand, is heavil infested with European red mites (Panonychus ulml), and badly damaged from infestation by the powdery mildew fungus (Unclnula necato) and the downy mildew fungus (Plasmopera ylticola) . The grapes on the unsprayed vines were small, broken open and rotted due to fungus infestation. 11 EXAMPLE I In lieu of the captan in Example the following fungicides can be used: thiram sublimed sulfur (flowers of sulfur) The above formulation is dispersed In water at a rate of 1 kilogram of formulation to MOO liters of water.

A polyhydric alcohol ester surface active agent ("Trem" 014) is added to the spray in an amount equivalent to 300 parts per million of the final suspension.

Eight uniform apple trees of the same variety are selected for testing. Pour of these are sprayed to run-off, which is approximately 2850 liters per hectare at weekly intervals during the growing eeason with the above formulation and the other four trees are left unsprayed. By the end of the season the unsprayed trees have developed very high populations of orchard mites and are highly infected with apple scab, Venturia inaequalls . Due to the feeding of the mites, the foliage is russeted and drops prematurely. Also, the untreated trees have poor twig growth and small spotted fruit . The trees sprayed with the active Ingredient are essentially free of mites, their eggs and apple scab. As a result of the excellent mite control, the sprayed trees have foliage of a thrifty, dark green color, and they exhibit good twig growth and fruit size. 33014/3

Claims (1)

1. CLAIMS Stable pesticidal compositions comprising an effective amount of a of either of the tautomeric formulae H where is methyl or ethyl and is alkyl of 1 to 8 carbon atoms with sucrose as the diluent and containing less than Compositions according to Claim being wettable powders containing 15 to preferably 30 to by weight o the to by weight of and to by weight of a surface active Compositions according to Claim being dusts containing to by weight of the aminobenzimidazole and 75 to by weight of Compositions according to Claim being granules containing to of and 75 to by weight of Compositions according to any of Claims 1 to wherein the 1B acid methyl according to any of Claims 1 to containing in addition sulfur in the ratio of to sulfur of lr4 to Compositions according to any of Claims 1 to containing addition thiran the ratio of to thirajn of to for Applicants insufficientOCRQuality