IL27824A - Substituted 2-aminobenzimidazoles - Google Patents

Description

27824/2 Substituted. 2-aminobenzimidazoles DU PONT DE NEMOURS AND COMPANY C. 26404 DESCRIPTION OF THE XNVEUTION This invention relates to substituted 2-amino- benzlmidazoles and to methods of using these compounds to prevent or mitigate damage to plants and inanimate organic materials by fungi and mites. ^ The survival of man has for a long time been dependent in a large measure upon his ability to protect from the various agents of destruction, plants and their products which satisfy his basic needs. With the rapidly increasing population of the world it becomes imperative that there be continuing great improvements in the efficiency of the materials and the methods employed to provide this protection. These improvements can be in the form of effective control of more kinds of pests or in the form of requiring less material or work. The materials and methods of this invention represent marked advances in both of these possible areas of improvement, as will be explained more fully.

I have discovered that application of the compounds of this invention by the methods of this invention, surprising entirely precludes or reduces damage to plants and inanimate organic materials due to both fungi and mites. Fungus mycelia are killed or prevented from developing further by the presenc of one or more of the compounds, i.e., the compounds are fungicidal or fungistatic. The compounds further prevent mite populations from expanding or reduce them to a low level or even eliminate them by preventing the normal hatching of their eggs, i.e., the compounds are mite ovicides.

The com ou and mites with an amazingly small amount of chemical and with surprisingly little effort. These advantages are due in large measure to the fact that the compounds when properly applied, can enter and move about in plants. This mean3 that an entire plant can be protected from mitea and fungi with a simple application of the chemical to only a part of it, i.e. the compounds are systemic. Further, if the compoundo are applied after a disease causing fungus is already established within a plant, they can enter the tissues and eradicate the infection, i.e. the compounds are curative.

Thus, the need for applications prior to the actual incidence of the disease is eliminated under many circumstances.

It has been found that the above outstanding fungicidal and mite ovicidal activity can be obtained by applying to the locus of mite or fungus infestation, the compounds represented by the following formula: R-L is alkyl of 1 through 4 carbon atoms and R3 is alkyl of 1 through 12 carbon atoms; phenyl; phenyl substituted with methyl, ethyl, methoxy, ethoxy, nitro, cyanoor halogen; benzyl; benzyl substituted v/ith methyl, nitro, methoxy or halogen; (cycloalkyl) alkyl of 7 through 8 carbon r cyclohexyl substituted withmethyl; alkenyl of 3 through 10 carbon atoms; or (alkoxycarbonyl)alkyl of 3 through 6 carbon atoms.

Preferred because of its high order of fungicidal activity is methyl l-(butylcarbamoyl) -2-benzimidazolecarbamate.

It will be understood that the above structure may exist in two tautomeric forms.

Formula II H I The compounds of the invention can be prepared by a number of routes. For example, the 1-carbamoyl substituted 2-benzim.idazolecarbamates can be prepared by reacting 2-benzimidazolecarbamates with isocyanates in accordance v?ith the following reaction. (1) 1 C - NHR3 I 0 II -NHC-OR The reaction as set forth in (1) above can be carried out in different inert solvents such as chloroform, carbon tetrachloride, methylene chloride, benzene, or cyclo- hexane. Mixtures of these solvents can also be used. ____ The reaction temperature, in general, is not critical and can be anywhere in between the freezing point and the boiling point of the reaction mixture, provided this boiling point is below the temperature at which reactants and products decompose. Ambient temperature is preferred.

As mentioned previously, it has been found that the compounds of this invention possess outstanding fungicidal and mite ovicidal activity when employed to prevent or mitigat damage to plants and inanimate organic materials.

A further aspect of this invention involves methods which when used in conjunction with the compounds of this invention, resul in advances in mite and fungus control of great practical importance. The paragraphs which follow describe in more detai the utility of this invention.

. The compounds of the invention control a wide variety o fungus diseases of foliage, fruit, stems and roots of growin plants without damage to the host. Fruits, tubers, bulbs, root seeds and other plant parts harvested for food, animal feed or for other purposes are protected from fungus deterioration duri 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 curtainG, carpets, mats, clothing and other useful households public or industrial items are protected from rot, fungus stains and mold growth. Painted surfaces are protected from stain and discoloration by incorporation of a compound of this Invention in the paint formulation.

The many fungi against which the compounds of this invention are active may be represented by, but is not intended to be limited to, the following: Venturia lnaequalis, which causes apple scab; Podosphaera leucotricha, which causes powdery mildew on apple, Uromyces phaseoli, which causes bean rust; Cercospora ap_ii> which causes early blight of celery; Cercospora betlcola, which causes leaf spot of sugar beets, Cercospora musae, which causes Sigotoka disease of banana; Plrlcularia sp. which causes Johnson spot on banana; Erysiphe clchoracearum, which causes powdery mildew on cantaloupe and other cucurbit crops; Penicillium digltatum, which causes green mold on citrus; Sphaerotheca humuli, which causes powdery midew on roses; Diplocarpon rosae, which causes black spot on roses; Uncinula necator, which causes powdery 0' mildew on grapes: Coccomyces hiemalis, which causes cherry leaf spot C adosporium carpophiluro. which causes peach scab; Erysiphe graainio hordei, which causes powdery mildew on barley: Monolinia (Sclerotinia) laxa which causes brown rot on apricot; _ _ Monolinia (Sclerotinia) fructlcola which causes brown rot on peac Piricularia oryzae, which causes rice blast; Puccinia recondita, P. coronata and P. glumarum which cause leaf rusts of wheat, oats and grasses respectively; Puccinia graminis tri ic , which causes stem rust of whe s Asperftll js _ni£er , which causes cotton boll rot as veil as decay £ollowing wounding in many plant tissues; Aspergillus tcrreus, which is common in soil and attacks vegetable matter; various species, of Rhizoctonia, •Fu'sariurn and Verticillium present in soil and attacking the roots or other underground parts of a variety of plants; various species of Penicillium growing on such. hings as fabric, fiber board, leather goods and paint; species of Myrothecium attacking such items as shower curtains, carpets, mats and clothing.

The mite ovicidal action of the compounds of this invention 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 these 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 of treatment. Also, this ovidical action, along with the high . natural mortality of adults, can largely eliminate mites from 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 and methods of this invention. The extent of the practical utility of the mite control obtained is represented by, but is no 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 atlanticus (Atlantic of strawberr mite), T. Clnnabarinus (carmine spider mite) and Ί\_ paclficus (Pacific mite); these mites attack cotton and numerous other crop plants; Paratetranychus citri (citrus red mite) and others which attack citrus; Bryobia praetiosa (clover mite) which attacks clover, alfalfa and other crops; Acerla neocynodomls which attacks grasses and other plants; Tyrophagus llntneri which is a serious pest i stored foods and on cultivated mushrooms and Lepidoglyphus destructor which injures Kentucky bluegrass seed in storage.

The compounds of this invention when applied by certain of the methods of this invention enter and move freely within plants, i.e., they are systemic. Thus both fungi and mites can be controlled in plants in parts well removed from the 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 contro of powdery mildew (Erysiphe ciehoracearum) and mites on the resulting plants for periods in excess of 40 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 saving 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 retreatment 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 this invention 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 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 application 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 this invention through the fact that both fungi and mites are controlled by applications of a single chemical.

The compounds of this invention 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 ovicidal 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. Living plants can also be protected by. dipping the root system or physically injecting the chemical or chemicals into roots or stems.

Soil applications are made from dusts, granules, pellets, slurries or solutions. Preferred rates for applica-tion 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, and the most preferred rates are in the range of 0.25 to 25 parts per million.

Preferred rates for application to seeds, tubers, bulbs or other plan 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 are made from dusts, slurries or soluti Such treatments protect the treated parts themselves from dam due to fungi, mites, or both, and in addition, impart extende protection against both types of pests to the resulting new plants.

Preferred rates for application of the compounds of this invention to foliage, stems and fruit of living plants range from 0.012 to 60 kilograms of active ingredient per hect 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 range depends upon a number of variables which are well-known those skilled in the art of plant protection. These variable include, but are not limited to, the disease to be controlled weather, conditions expected, the type of crop, stage of devel Preferred rates for dip applications to roots of living plants are in the range of 0 .5 to ΐθ,ΌΟΟ grams of active ingredient per 38Ο liters of water or other liquid carrier. More preferred rates are in the range of . 5 to 9 , 000 grams per 380 liters and the most preferred rates are in the range of ½ 5 to 00 grams per 380 liters.

Preferred rates for injection into the roots or stems of living plants are in the range of 0. 01 to 10, 000 parts per million of water or other liquid carrier. More preferred rates are in the range of 0 . 1 to 5, 000 parts per million. The most preferred rates are in the range of 1 to 1, 000 parts per million.

Plant parts such as fruits, tubers, bulbs, roots and th like, harvested for food or feed, are protected from decay and other deterioration caused by fungi or mites during processing, distribution and storage by treatment with an active compound of this invention. The plant parts to be so protected can be dipped in a liquid bath containing the active ingredient, dusted with a finely divided preparation of the active Ingredient, sprayed, misted with an aerosol containing the compound, or enclosed in wrapping or packing materials impregnated with the active compound.

If a liquid bath is used, it can contain an amount of the active ingredient in the range of 1 to 5, 000 parte per million of the weight of the fluid. A more preferred range for the bath is 5 to 2, 500 parts per million, and the most preferred range is 10 to 1, 000 p&rts per million.

Dusts as well as wrapping or packing materials used for this type of application can contain 0.01 to 10 of the active ingredient. More preferred rates are in the range of 0.1 to 5$ and the most preferred rates are in the range of 0. 2 to 2.5$.

Wood, leather, fabric, fiber board, paper and other industrial materials of an organic nature can be protected from decomposition or dis'coloration by fungi and infestation by mites, by coating, incorporating or impregnating with an effective amount of one or more of the compounds of this invention. The coating can be accomplished by dipping, sprayin flooding, misting (as with an aerosol) or dusting the material to be protected with a suitable composition containing the acti 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 95$ by weight* More preferred rates are in the range of 0.05 to 50$, with the most preferred rates being in the range of 0.1 to 25$.

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$ by weight of active ingredient in the final product. More preferred rates are in the range of 0.005 to 15$ 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 of this invention. Again, either surface or deep protection can be obtained* Surface treatment is by dips, washes, sprays, aerosols or dust applications. Deep treatment is accomplished by penetrating solutions. Sprays, dips and washes contain the active compound of the invention at rates of 10 to 5000 parts per million. Fluids for aerosol application and dusts contain 0.1 to 20$ by weight. Penetrating solvent solutions contain an amount of the active ingredient that results in a deposit of 5 to 20,000 parts per million in the material to be protected.

Painted surfaces can be protected from unsightly stain and mold growth by incorporating in the paint formulation, prior to application, 5 to 20,000 parts per million of an active compound of this invention. More preferred rates are in the range of 10 to 10,000 parts per million and the most preferred rates are in the range of 20 to ,000 parts per million. Such treatments x^rith the compounds of this invention also protect the paint while still in the can from deterioration by fungi.

Damage by mites to stored organic products such grain, seed, bulbs, tubers, meat or animal hides is kept to a minimum by treating the floors, walls, portions, and other parts of warehouses or other structures with one or more of the active compounds. Applications are made by the use of dusts, sprays, or aerosols with preferred use rates in the range of 0,05 to 1000 grams of the active compound of this invention per 95 square meters of surface As was previously set forth, the compounds of this invention are especiall suited for use on living plants, ^ Application to the foliage, stems and fruit of plants at the rate indicated above is generally accomplished by employing sprays, dusts or aerosols containing the proper amount of active ingredient. For the control of mites and fungi which are regularly present, applications often start prior to the time that the problem actually appears and continue on a predetermined schedule. Such a procedure is termed "preventive" or "protective".

With the compounds of this invention, 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 occurring 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 this invention are applied, their activity can be enhanced by using certain adjuvants, for example in the water in which the benzimldazole fungicides are dispersed. These adjuvants may be surface active agents, oils, huraectants, enzymes, carbohydrates, · and organic acids. They improve the performance on tubers, on foliage, in treat r 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 compounds of this invention include sulfonated and sulfated amines and amides, diphenyl 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, iaethionates, sulfated ethoxylated alkylphenols, lanolin derivatives, lecithin and lecithin derivatives, alkanol amides, phosphate derivatives, monoglycerides and derivatives, quaternaries, sorbltan and sorbitol derivatives, sulfosuccinates, alcohol sulfates, sulfated fatty esters, sulfated and sulfonated oils and fatty acids, alky1 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 enmlsifier 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 Preferred surface active agents to improve the fung cidal and mite ovicidal activity of these compounds are products such as dioctyl sodium sulfosuccinates ("Aerosol" OT and "Aerosol" OT-B), blends of aromatic sulfonates and ethylene oxide derivatives ("Argrimul" GM, "Agrimul" A-100, "Agrimul" N-100, "Emcol" H50A, "Emcol" H53), polyoxyethylene sorbitol oleate/laurate ("Atlox" 10 5A), sodium lauryl sulfate ("Duponol" ME), polyoxyethlated vegetable oils ("Emulphor" EL719), lecithin derivatives ("Emultex" R), acidic complex organic phosphate esters ("Gafac" RE-61C , "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 laury and myristyl colamide (" Int amine" Y), polyethylene glycol 400 oleic acid ester ("Nonisol" 210), sodium dodecylbenzone sulfonate ("Sul-Fon-A e" AA 10, "Ultrawet" K), polyoxyethylene ethers with long-chain alcohols ("Surfonlc" LR 30, "Alfonic" 1012-6, "Brij" 30, "Tergitol" TMN), ethylene oxide condensates with propylene oxide/ethylene diamine condensates ("Tetronic" 504), polyhydric alcohol esters (" rem" 01 ), modified phthalic glycerol allcyl resins ("Triton" B 1 56 ), quaternaries ("Zelec" DP), alkylphenol ethylene oxide condensate ("Dowfax" 9N4, "Dowfax" 9N10, "Hyonic" 9510, "Tergltols" ) 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 V/. McCutcheon Inc., 236 Mt. Kemble Avenue, Morrlstown, New Jersey.

Preferred oils- include spray oils such as "Orchex" 796 made emulsi.fiable with "Triton" X- 5, castor oil made emulsifiable with "Triton" X-114, corn oil made emulsifiable wi "Triton" X-11 , 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 o 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 million As previously mentioned, the compounds of the invention are systemic. For systemic applications to above-ground parts, such as foliage, stems and fruit, the presence of a sur ace-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 or other reproductive parts prior to planting as well as by applic tion of the chemical to the soil in which the plants to be protected are, or will be, growing. Application to reproductive p prior to planting is effected through the use of sprays, dips, dusts or aerosols 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 in a band or sheet with specialized equipment, injection through irrigation water or by distribution on the field surface.

The fungicidal and mite ovicidal compositions of the invention contain in sufficient amount to exert fungicidal or mite ovicidal action, one or more compounds of this •invention in admixture with a carrier material or conditioning agent of the kind used and commonly referred to in the art as an adjuvant or modifier. The general classes of adjuvants applicable to the compounds of this invention are inert solids, organic liquid solvents, organic liquid or aqueous diluents and surface-active agents. Formulations adapted for ready and efficient application using conventional applicator equipment are prepared by compounding the compounds of this invention with suitable adjuvants by mixing, grinding, stirring or other conventional processes. Normally, the active ingredient composes 1-95$ by weight of the fungicidal or mite ovicidal composition.

Solid compositions can be in the form of water-dispersible powders, dusts, pellets and granules. Water-dispersible powders are particularly useful and can be prepared by simple mixing and grinding steps and can be either used as such, diluted with inert solids to form dusts or granul or suspended in a suitable liquid medium for spray or seed treatment application. The powders usually comprise active ingredient admixed with var in amounts of conditionin a ents surface-active agents and stabilizers. The classes of extenders suitable for the wettable powders of this invention are clays, such as the kaolins, diatoraaceous earths, calcium carbonates and also synthetic silicas and silicates. Diluents that have been surface reacted, such as organic acid coated calcium carbonate, can also be used. Diluents of organic origin such as walnut shell flour, can also be used.

The active ingredient usually makes up from about - 0 of these wettable powder compositions. These wettable powders can also be converted to dusts containing 1-25$ o active material by mixing or grinding with pyrophyllite,. volcanic ash and other dense, rapid-settling inert solids.

Alternatively, dusts can be prepared cy grinding the dust diluents with the active ingredient, or by preparing dust concentrates for further dilution. These dust concentrates can contain from 80-95% of the active ingredient,, blended and ground with diluents and, if desired, small amounts of surface active agents.

For the granule compositions of this invention, the most suitable carriers are of two types. The first are porous, adsorptive, preformed granules, such as preformed and screened granular kaolinite clays, heat expanded, granular, screened veraiculite, or granular botanicals. O any of these, a solution or aqueouc suspension of the active agent can be sprayed at concentrations up to 2 weight percent of the total weight,, In addition to the active component, the solutions or suspensions can contain surfactant and also binders such as swollen starch to aid in adhering small particles of dispersed product to the dried granules* Such adhesive materials may also be surfactants and include such products ao polyvinyl alcohol, calcium, and magnesium lignin sulfonate in admixture with wood sugars, acrylate and asphalt emulsions, abietates, etc. Oils or other non-volatile liquids like glycols can also be used to improve adhesion.

The second suitable type of carrier is the powdered kaolinitic clays, Or bentonitic clays in the sodium, calcium or magnesium forms. These clays are blended with the active components and optionally surfactants to give mixtures that are granulated and dried to yield granular material with the active component distributed uniformly throughout the mass. Such granules can also be made with 25 to 50 weight percent active component, but more requently a concentration of about 10 weight percent is desired for optimum distribution. Similar compositions can be made by extruding the mixture in the presence of moisture, and converting the extrusions into granules or pellets by a suitable combination of cutting, drying, and crushing steps. The granular compositions o^ this invention are most useful in a size range of 15-6o mesh.

Liquid compositions employing one or more of the active compounds of this invention are prepared by admixing the active ingredient with a suitable liquid diluent medium. The active ingredient can be either in solution or in suspension in the liquid medium. Typical of the liquid media which can be us are water, paraffinic spray oils, alkylated naphthalenes, xylen alcohols, chlorinated hydrocarbons and ketones. The active ingredient usually makes up from about 0.5 to 50^ of these liquid compositions. In addition, surface-active agents, particularly emulsifiers, can be present to aid in the suspensi or dispersion or to emulsify the composition into water.

Compositions of the invention,, especially liquids and wettable powders, contain as a conditioning agent one or more surface-active' agents in amounts sufficient to render a given composition readily dispersible in water or in oil. By the term "surface-active agent", it is understood that wetting agents, dispersing agents, suspending agents and emulsifying agen are included.

Suitable surface-active agents Include anionic, catloni and non-ionic types. In general, less than 10 by weight of the surface-active agent is present in the compositions of this invention, although frequently the amount of surface-active agent in these compositions is less than 2 by weight.

Preferred wetting agent3 are alkylbenzene- and alkylnaphthalene sulfonates, sulfated fatty alcohols, amines or acid amides, long chain acid esters of sodium isethionate, esters of sodium sul osuccinate, sulfated or sulfonated fatty acid esters, petroleum sulfonates, sulfonated vegetable oils, and ditertiary acetylenic glycols'. Preferred dispersants are methyl cellulose, polyvinyl alcohol, sodium, calcium, and magnesium lignin sulfonates, polymeric alkylnaphthalene sulfonates, sodium naphthalene sulfonate, polyvinylpyrrolidone derivatives, polymethylene bisnaphthalenesul onate and sodium-N-methyl-N-(long chain acid) taurates.

Wetting and dispersing agents in these preferred wettable powder compositions of this invention are usually present at concentrations of from about 0.5 weight percent to 5 weight percent. The inert extender then completes the formulation. "Where needed, 0.1 weight percent to 1.0 weight ercent of the extender can be re laced b a corrosion inhibitor or an antifoaming agent, or both. In some instances, it may be advantageous to use larger amounts of dispersants such as the lignin sulfonates in ettable powder, pellet, granule and dust compositions.,,- , In such a case, the lignin sulfonates additionally act as diluents for powders and as binder for granules and pellets,...

Emulsifying agents most suitable for the liquid compositions of this invention are alkylaryl polyethoxy alcohols, - condensation products of ethylene oxide with long-chain alkyl alcohols, me captans or amines, sorbitan fatty acid esters, polyethylene glycol fatty esters, fatty alkylol amide condensates, amine salts of fatty alcohol sulfates, and oil soluble salts of petroleum sulfonates. Mixtures of emulsifying agents are often preferred. Such emulsifying agents will comprise from about > to to 10 weight percent of the total composition. As described above, however, much greater amounts of emulsifying agent can be used to give improved results.

" The compounds of this invention, and the oils, humeetants, enzymes, carbohydrates, and acids useful to enhance the fungicidal and mlte-ovicidal activity of these ' compounds can be brought together in several ways. For example, the additive which will enhance activity can be mixed with compounds of the invention when spray slurries are being . prepared. It is often also possible and convenient to produce formulations in which the additive and the compound of the invention will both be present in the composition, which is then convenient to apply. Such compositions can be powders, granules, suspensions, or even solutions, depending upon the physical and chemical characteristics of the components that are to . be prepared. It will be readily understood by those skilled in the trade and in the light of the above teachings that the ratios of active Ingredient compound to additives may vary widely. Thus, the additive may be present in such mixtures within the range of from 33 to 10, 000 parts per 100 parts of the compounds of this invention.' More preferred are rates of from 40 to 5, 000 parts of additive per 100 parts of active ingredient and a range of ratios from 50 to 3, 500 per 100 parts of compound is even more preferred.

Among non-ionic and anionic surfactants, those most suitable for the preparation of the dry, wettable products of this invention are solid forms of compounds known to the art as wetters and dispersants. Occasionally a liquid, non-ionic compound classified primarily as an emulsifxer can serve as both wetter and dispersant.

Such compositions can contain, in- addition to the active Ingredient of this invention, conventional insecticide miticides, bactericides, ' ernatLcides, fungicides, or other agricultural chemicals such as fruit set agents, fruit thinni compounds, fertilizer ingredients and the like, so that the compositions can serve useful purposes in addition to the control of fungi and mite infestations.

The following are illustrative of the agricultural chemicals that may be included in the compositions or, additionally, that may be added to sprays containing one or more of the active compounds. l>2,5J,i,10,10-hexachloro-l, J1iaJ5>8,8a-hexahydro-l>1l-endo-exo-5>8~dimethanonaphthalene (aldrin); 1,2,3,4, 5, 6-hexachlorocyclohexane (lindane) ; 2,?,¾J5,6J7j8,8-octachlpro-¾,7-methano-?a-Jt,7i7a-tetrahydro-indane: · l,l,l-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT) ; 1,2,3,4, 10, 10-hexachloro-6,7-ep0xy-l, 4 ,4a-5,6,7,8,8a-octahydro-l,4-endo-exo-5,8-dimethanonaphthalene · (dieldrin) ; l,2,3,4,10,10-hexachloro-6,7-epoxy-l, ,4a,5i6,7,8,8a-octahyd l,4-endo-endo-5, 6-dimethanonaphthalene (endrin) ; 1 (or 3a),4,5,6,6,8,8-heptachloro-3a-4,7,7a-tetrahydro-4,7-methanoindene l,l,l-trichloro-2, 2-bls (p-methoxyphenyl)ethane (methoxychlor l,l-dichloro-2, 2-bis (p-chlorophenyl ) ethane; chlorinated camphene having a chlorine content of 67-69^; 2-nitro-l, 1-bis (p-chlorophenyl )butane; 1-naphthyl-N-methylcarbamate ("Sevin"®); methylcarbamic acid, ester with phenol, 4- (dimethylamino) -3, dimethyl; methylcarbamic acid, ester v.'ith l,3-dithiolan-2-one oxime; 0,0-diethyl-0-(2-isopropyl-ii-methylpyrimid-6-yl) thiophosphat 0,0-dimethyl-l-hydroxy-2, 2, -trichloroethyl phosphonate; 0,0-dimethyl-S- (l, -dicarbethoxyethyl)dithiophosphate (malathion); 0,0-dimethyl-O-p-nitrophenyl thiophosphate (methyl parathion 0, O-dimethyl-0- (3-chloro~ -ni ropheny1)thiophosphate; 0,0-diethyl-O-p-nitrophenyl thiophosphate (parathion); ' ί di-2-cyclopentenyl-½-hydroxy-3-methyl-2--cyclopenten-l-one chrysanthemate; . · 0,0-dimethyl-0-(2J -dichlorovinyl)ph9sphatei (DDVP); mixture containing 53. "Bulan" 2-nitro-l,l-bls~(p_-chloro-phenyl)butane, 26.7 "Prolan" 2-nitro-l, l-bis-(p_-chloro-phenyl)propane, and 20„C$ related compounds 0,O-dimethyl-0- (2, 4,5-trichlorophenyl )phosphorothioate; 0,0-dimethyl-S-(4-oxo-l,2,3-benzotriazine-3( H)-yl-methyl)-phosphorodithioate ( "Guthion" ®) j bis ^di ethylamino)phosphonous anhydride; 0,0-diethyl-0- (2-keto-4-methyl-7-a' -pyranyl)thiophosphate; 0,0-dlethyl (S-ethyl mercaptomethyl)dithiophosphate; calcium arsenate; sodium alumlnofluoridej dibasic lead arsenate] 21 - chloroethyl-l-methyl-2-(p-tert-butylphenoxy)ethyl sulfite azobenzene; ethyl 2-hydroxy-2,2-bis(ii-chlorophenyl)acetate; 0,0-diethyl-O- (2- (ethylmercapto)-ethyl)thiophosphate; 2,4-dinitro-6-sec-butyl phenol; toxaphene, octachlorocamphefiA ; .. ■ 0-ethyl-O-p-nitrophenylbenzenethiophosphonate; 4-chlorophenyl-4-chlorobenzenesulfonate; p-chlorophenyl-phenyl sulfone; tetraethyl pyrophosphate; 1, 1-bis (p-chlorophenyl) ethanol; l,l~bis( p-chlorophenyl) -2,2,2-trichloroethanol; P-chlorophenyl-p-chlorobenzyl sulfide; bis (p-chlorophenoxy)methane; 3-(l-methyl-2-pyrrolidyl)pyridine; · ^mixed ester of pyrethrolone and cinerolone keto-alcohols and two chrysanthemum acids; cube and derris, both whole root and powdered; mixture of alkaloids known as . veratrine; dl~2-allyl-4-hydroxy-2-methyl-2-cyclopenten-l~one esterified with a mixture of cis and trans dl-chrysanthemum mpnocarbpxylic acids; butoxypolypropylene glycol; p-dichlorobenzene 2-butoxy-2' -thiocyanodiethyl ether; naphthalene; ' · methyl O-carbamylthiolacetohydroxamate: l,l-dichloro-2> 2-bis(p-ethylphenyl)ethane ·■ methyl 0- (methylcarba yl)thiolacetohydroxamate; p-dimethylaminobenzenediazo sodium sulfonate, quinone oxyaminobenzooxohydrazone tetraalkyl thiuram disulfides such as tetramethyl thiuram disulfide or tetraethyl thiuram disulfide; metal salts of ethylene bisdithiocarbamic acid, e.g. manganese, zinc, iron and sodium salts; pentachloronitrobenzene; · n-dodecylguanidine acetate (dodine); N~trichloromethylthiotetrahydrophthalimide (captan).. phenylmercury acetate; (o-chloroaniline)-s-triazine ( "Dyrene" N-methylmercury p-toluenesul onanilide; chlorophenolmercury hydroxides; nitrophenolmercury hydroxides; ethylmercury acetate; ethylmercury 2, 3-dihydroxypropyl mercaptide; methylmercury acetate; methylmercury 2, 3-dihydroxypropyl mercaptide; ,3'-ethylenebis(tetrahydro-4,6-dimethyl-2H-lJ3J5-thiodi-azine-2-thione) , methylmercury dicyandiamide; N-ethylmercury~p-toluenesulfonilide ; l,i-dichloro-2> 5-dimethoxy benzene; metal (e.g. iron, sodium and zinc), ammonium and amine salts of dialkyl dithiocarbamic acids; tetrachloronitroanisole ; hexachlorobenzene j he.xachlorophene methylmercury nitrile; tetrachloroquinone _ N-trichloromethylthiophthalimide l,2-dlbromo-2-chloropropene; dichloropropane - dlchloropropene mixture; ethylene dibromide; chloropicrin; eodium dimethyl dithiocarbamate ; tetrachloroisophthalonitrile; 1-benzlmidazole carboxylic acid, 2-carboxyamlno-dimethyl es ei streptomycin; 2- (2>,l,5-trichlorophenoxy)propionic acid; p-chlorophenoxyacetic acid; 1-naphthalene acetamide; and N~ (1-naphthyl) acetamide .

The agricultural chemicals listed above are merely exemplary of the compounds which can be mixed with the active compounds and are not intended to any way limit the invention.

The use of pesticides such as those listed above in •combination with a compound within the scope of this invention sometimes appears to greatly enhance the activity of the activ compound. In other words, an unexpected degree of activity is sometimes seen when another pesticide is used along with the active compound.

In order that this invention can be better understood, the following examples are offered. The amounts are given in terms of parts by weight unless otherwise specified.

Example 1 Preparation of Methyl 1- (butylcarbamoyl) -2~benzimidazolecarba^ .To a slurry of 19.1 parts of methyl-2-benzimidazole-carbamate and 600 parts of chloroform are added 9.9 parts of n-butylisec nate. The reaction is stirred at room temperature until a clear solution is present or until only a. small amount of solid is present.

Any solids present are removed by filtration. The solvent is removed from the filtrate under reduced pressure The following compounds are prepared in accordance "with the procedure set forth above by replacing n-butyliso-cyanate with the indicated isocyanate. The table shows not the relative proportions of the indicated isocyanates needed for 1 .1 parts by weight of methyl-2-benzimidazolecarbamate but also the product obtained.

Isocyanate Parts by Weight Name Product propylisocyanate methyl l-(propylcarbamoyl)- benziraidazolecarbamate m.p. 293-295°C dec isopropylisocyanate methyl l-(isopropylcarbamoy benzimidazolecarbamate m.p. 293-319°C ethylisocyanate methyl l-(ethylcarbamoyl)-2 benzimidazolecarbainate m.p. 295-320°C. methylisocyanate methyl l-(methylcarbamoyl)- benzimidazolecarbamate m.p. 280°C. + hexylisocyanate methyl 1-(hexylcarbamoyl) -2 benzimidazolecarbamate m.p. 506-3l6°C. cyclohexylisocyanate methyl l-(cyclohexylcarbamo benzimidazolecarbamate m.p. 29½~320°C. 2-methylcyclohexyl methyl l-[ (2-methylcyclohex isocyanate carbamoyl] -2-benzimidazole- carbamate m.p. 310-320°C. cyclohexylmethyl methyl 1-[ (cyclohexylmethyl isocyanate carbamoyl]-2-benzimidazole- carbamate m.p. 251-305°C. octylisocyanate methyl l-[ (octy~lcarbamoyl]- benzimidazolecarbamate m.p. 295-300°C. benzylisocyanate methyl l-(benzylcarbamoyl)- benzimidazolecarbamate m.p. 302-312°C. phenylisocyanate methyl l-(phenylcarbamoyl)- benzimidazolecarbamate ° Isocyanate' Parts by Weight Name Product 13.3 o-tolylisocyanate methyl. l-[ (o-tolyl)carbamoy 2-benzimidazolecarbamate Analysis Calculated" Found C 62.94 .62.93 H 4.94 4.85 N 17.28 17.50 13.3 p_-tolylisocya ate methyl l-[ (p_-tolyl) carbamoyl 2-benzimidazolecarbamate m.p. 300°C + . o-chlorophenyliso- methyl l-[o-chlorophenyl) - cyanate carbamoyl] -2-benzimidazolecarbamate m.p. 295-300°C. de 14,9 £-methoxyphenyliso- methyl l-[ (p-methQxyphenyl)- cyanate carbamoyl] -'2~-be zimidazole- carbamate m.p. 320°C. + 14,4 P_-cyanophenylisocyanate methyl 1-Γ ( -cyanophenyl) - carbamoyl] -2"-benzimidazole- carbamate, m.p. 320°C. 16.4 p_-nitrophenylisocyanate methyl 1-Γ (p-nitrophenyl) - carbamoyl] -2"-benzimidazole- carbamate m.p. j515- l6°C. de 16 e4 m-nltrophenylisocyanate methyl l-[ (m-nitrophenyl)- carbamoyl] -!2~-benzimidazole- carbamate m.p. 320°C. + 18.8 54-dichlorophenyliso- methyl l-[ (3,4-dichloro- cyanate phenyl)carbamoyl] -2-benzimidazolecarbamate m.p. 320°C 16.8 3-chloro -4-methyl- methyl l-[ (3-chloro-4-methyl pheny 1isoc a ate phenyl)carbamoyl] -2-benzi- mldazolecarbamate 9.9 isobutylisocyanate methyl l-( isobutylcarbaraoyl) -2-benzimidazolecarbamate m.p. 300°C.

Example 2 The following compounds are prepared in accordance wi Example X by replacing the 19. 1 parts of methyl- 2-benzimidazole carbamate and 9 · 9 parts of n-butylisocyanate with the equivalen parts of the properly substituted benzimidazol'e and isocyanate necessary to prepare each named product.

Product ethyl l-(isopropylcarbamoyl) -2-benzimidazolecarbamates m.p. 300°C methyl l~(sec-butylcarbamoyl) -2-benziraidazolecarbamatei ethyl l-(he:xylcarbamoyl) -2-benzimidazolecarbamate, m,p.llO°C. methyl l-( -meth©2ybenzylcarbamoyl) -2-benzlmidazolecarbamatei m.p. 28 -302°C.

Isopropyl l-(raethylcarbamoyl) -2-benzimidazolecarbamate, m.p. I55-I56°C- . isopropyl l-(butylcarbamoyl) -2-benzimidazolecarbamate, m.p. 99-100°C. isopropyl l-(hexylcarbamoyl) -2-benzimidazolecarbamate, m.p. 95-97°C. isopropyl l-(p-nitrophenylcarbamoyl) -2-benzimidazolecarbamate, m.p. l 0-l¾5°Ce. isopropyl l-(cyclohexylcarbamoyl) -2-benzimidazolecarbamate, m.p. l 0~l 3°C. isopropyl l-[ (p_-methoxyphenyl) carbamoyl] -2-benzimidazolecarbamate, m.p. l40-l4l„5°C. isopropyl l-[ (p_-cyanophenyl)carbamoyl] -2-benzimidazolecarbamate, m.p.- 00°Π.+ sec-butyl l-(methylcarbamoyl) -2-benzimidazolecarbamate, m.p. I3 -I36 °C. ' methyl l-(o-nitrophenylcarbamoyl) -2-benzimidazolecarbamate, m.p. 3lB-319°C. ' isobutyl l-(methylcarbamoyl) -2-benzimidazolecarbamate, butyl l-(hexylcarbamoyl) -2-benzimidazolecarbamate, m.p. 95-97°C. butyl l-(methylcaxbamoyl) -2-benzimidazolecarbamate methyl l-(p-ethoxyphenylcarbamoyl) -2-benzimidazolecarbaraate, m.p. 270°C.+ sec-butyl 1-(butylcarbaraoyl) -2-benzimidazolecarbamate, isobutyl l-(hexylcarbamoyl) -2-benzimidazolecarbaraate, m.p. 101-103 C. methyl 1-( thoxycarbonylmethylcarbamoyl) -2-benzimidazole- carbamate, m«p» 267 -270°C. dec. isopropyl l-(ethoxycarbonylmethylcarbamoyl) -2-benzimidazole- carbamate, m.p. 89-91. 5 c. " isobutyl 1-(ethoxycarbonylmethylcarbamoyl) - -benzimidazole- carbamate, m.p. 151-152°C. ethyl l-(ethoxycarbonylmethylcarbamoyl) -2-benzimidazole- isopropyl l-(butoxycarbonylmethylcarbamoyl) -2-benzimidazole- carbamate, m.p. 103 -105 « 5°C. isopropyl l-(allylcarbamoyl) -2-benzimidazolecarbamate? m.p. 134-136°C. butyl 1-(allylcarbamoyl) -2-benzimidazolecarbamate, m.p. 135°C. dec. methyl 1-(allylcarbamoyl) -2-benzimidazolecarbamate, m.p. 293 -297°C. dec. ethyl 1-(allylcarbamoyl) -2-benzimidazolecarbamate, m.p. 290°C. dec. methyl 1-(dodecylcarbamoy 1 ) -2-benzimidazolecarbamate, m.p. 195-215°C. methyl l- ( 9-decenylcarbamoyl) -2-benzimidazolecarbajiiate, m.p. 72 -80°C.

The effectiveness of the compounds of the invention in preventing mite reproduction, controlling mite infe-st tion, and controlling fungus diseases is clearly demonstra ed by the field and laboratory tests of the following examples.

- Example 3 A wettable powder formulation is prepared as follows: methyl l-/("m-tolyl)carbamoyl] -2-benzljnidazole- carbamate 70. 0 diatomaceous earth 28.7 alkylaryl sodium sulfonates 1 . 0 methyl cellulose 0 . 3 The above ingredients are blended and micropulverized o a particle size below 50 microns, followed by reblending.

The wettable powder thus prepared is added to water at the rate of 1 pound of the active ingredient per 100 gallons of water ( .03$) . A modified phthalic glycerol alkyd resin surface active agent ("Triton" B 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 trees in a field planting of apples. Sprays are applied at weekly intervals from April 25 until June 6. From June 6 until the end of the season, the sprays are applied at intervals of turo weeks.

The remaining trees in the planting are left unsprayed.

In early September all trees are carefully examined.

Trees that were sprayed with the compound of this invention 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 (Venturia inaequalis) and the powdery mildew fungus (Podosphaera leucotricha) . 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 and of small size.

The following compounds may be similarly formulated and when used as above give similar results, methyl l-(methylcarbaoyl) -2-benzimidazolecarbamate methyl l-(ethylcarbamoyl)-2-benzimidazolecarbamate methyl l-(propylcarba oyl) -2-benzimidazolecarbamate methyl l-(butylcarbamoyl)-2-benzi:r>idazolecarbamate methyl l-(pentylcarbamoyl) "2-benzimidazolecarbamate methyl l-(hexylcarbamoyl) -2-benzimidazolecarbamate methyl l-(octylcarbamoyl ) -2-benzimidazolecarbamate methyl l-[(p_-nitrophenyl) carbamoyl ] -2-benzimidazolecarbamate Also in the above example, the following surface active agents may be substituted with similar results: sodium lauryl sulfate ("Duponol" ME) polyoxethylene.sorbitol oleate/laurate , (."Attox" , 10 5A) Example -4 A wettable powder formulation is prepared from the following ingredients: methyl 1- (hexylcarbamoyl )-2-benzimidazolecarbamate 50.0 kaolinite 0 sodium lignin sulfonate . I*Q dioctyl sodium sulf'osuccinate ' 2^0 finely divided synthetic silica 2^0 Th£5e~ Ingredients are mixed, blended and raicronized to a particle size below 10 microns, followed by reblending.

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 this 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 is such as to give 227 grams of the active compound of this formulation per 378 liters of water (Q .06 ) and 400 ppm of the surfactant. The spray is applied at a volume of I4l0 liters per hectareβ The remaining rows are left unsprayed.

After another 15 days the unsprayed rows are heavil damaged by powdery mildew and some of the plants are dying. sprayed rows, however, are healthy and growing rapidly. The results indicate that the active compound o;* the suspension a as a curative fungicide.

Example 5 The followin formulation is prepared by intimatel blending the ingredients and grinding the blend in an air attrition mill until the particle size is substantially less than 5 microns and then reblending. methyl l-(methy..carbamoyl ) -2-benzimidazolecarbamate $0.0 dioctyl sodium 3ulf succinate 1.0 low viscosity methylcellulose 0. 3 silica 48.7 Acid delinted cotton seed, already treated with 85 grams of tetramethylthiuram disulfide per 45.3 kilograms of seed, is overtreated in a slurry treater with the formulation described above, in such a way as to provide 113 grams of the active ingredient per .3 kilograms of seed. A similar lot of seed, treated with tetramethylthiuram disulfide only, is used for purposes of comparison. The two lots of seed are planted in alternating rows in the same field.

The seed treated with tetramethylthiuram disulfide only emerges to a good stand but many seedlings die later due to post-emergence damping off, and growth of the surviving plants is poor due to Rhizoctonia solani. Most of the seedlings that do survive exhibit soreshin lesions caused b Rhizoctonia. The seeds over-treated with the above formu Example 6 The following formulation is prepared by intimately blending the follov/ing ingredients and micropulverizing them until the particles are substantially all below 20. microns. methyl 1- (propylcarbamoyl )-2~benzimidazolecarbamate 50. oleic acid ester of sodium isethlonate 2. sodium lauryl sulfate - 1. synthetic fine silica ' 47.

The above 50$ wettable powder formulation is dis-persed 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-off, which is approximately 28 0 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, Venturia inaequalis. 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 1--(propylcarbamoyl)-2-benzimidazolecarbamate 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.

Any of the compounds named in Examples 1 to 3 may be ormulated as described in this example and when used as indicated give similar results.

Example A wet able powder formulation is prepared from the following ingredients in the proportions given: methyl l-(butylcarbamoyl)-2-benzimldazolecarbamate 25 methyl 0-(metnylcarbamyl)thiolacetohydroxamate 10 oleic acid ester of sodium isethionate 2 sodium lauryl sulfate . 2 diato aceous silica 61 ■ All ingredients are combined and rotated in a blend until uniformly admixed. The total mix is then air- milled tc produce particles most of which are less than 10 microns in particle size.

A sufficient amount of the above wettable powder is added to water such that there are 2,5 grams per liter of water of the methyl 0-(methylcarbamoyl ) thloacetohydroxamat The resulting suspension is then sprayed at weekly intervals one pair of similar, adjacent plots in a" greenbean field in Florida at the rate of two kilograms of methyl 1 -( butylcarbam 2-benzimidazolecarbamate per hectare. The test area is selec as one in which there is a high infestation of the two-spotte mite, Tetranychus- bimaculatus, and the Mexican bean beetle, Epilachna varivestis. The plot sprayed with the above formulation remains free of both the two-spotted mite and the Mexican bean beetle for the entire growing season and provides a good yield of greenbeans. The unsprayed plot is attacked by both of the above pests and is damaged to the extent that the yield is greatly reduced. Similar areas ,sprayed with methyl 0- (methylcarbamyl)thiolacetohydroxamate alone are free from attack by the Mexican bean beetle but are damaged. by the two- spotted mite.

In the above example methyl 0- (carbamyl) hiolaceto- hydroxamate may be substituted for methyl 0- (methylcarbam oyl ) A wettable powder formulation is prepared from the following ingredients in the proportions given: methyl l-( isobutylcarbamoyl ) -2-benzimidazolecarbamate 30-0 methoxychlor 30.0 sodiumlauryl sulfate 1·0 oleic acid ester of sodium isethionate 2.0 non-swelling montmorillonoid clay 37·0 All of the ingredients are combined and rotated in a blender until uniformly mixed. The total mix is then air-milled to product particles essentially less than 40 microns in size.

The wettable powder prepared above is addea to water in an amount such that there are 2.5 grams of each of the active ingredients per liter of water. The resulting suspension is sprayed at the rate of 10 kilograms per hectare for each of the active Ingredients over a plot in a Bermuoagrass turf area in Florida. The area selected for the test is heavily infested with a plant-feeding mite, Aceria neocynodomis and chinch bugs, Blissus leucopterus inoularis . The chinch bug.s are killed in the treated plot and the mite infestation soon disappears. The turf quickly returns to a healthy and attractive condition.

. In a similar untreated plot both the mites and the chinch bugs continue to multiply and, by their feeding, the . Ber udagrass becomes discolored and the turf reflects many unsightly dead spots. Similar plots sprayed with methoxychlor only are free of damage due to chinch bugs but are injured by "t high mite infestation.

The following compounds can be substituted for the methyl l-(isobutylcarb moyl)-2-benzimidazolecarbamate and similarly formulated. When used as set forth above they ive similar results methyl l- (2-methylcyclohexyl ) carbamoyl/-2-benzimidazolecarbaii methyl l-(butylcarbamoyl)-2-benzimidazolecarbama-te Example g) The following formulation is prepared by intimately blending the ingredients and grinding the blend in an air attrition mill until the particle size is substantially less than 5 microns and then reblending. methyl 1- (butylcarbamoyl ) -1-benzimidazolecarbamate 85- alk lnapthalene sulfonic acid, sodium salt 1. sodium N-methyl-ri-oleoyl taurate 2. synthetic fine silica . ■ . 11- Four similar potted bean plants (one plant per pot) are selected. The soil in two of these pots is drenched with a water suspension of the wettable powder formulation described above at a rate to provide 30 parts per million by weight in the total amount of soil in the pot. The remaining two pots are left untreated, 'Five days after treatment 50 adult mites (Tetranychu telarius) are placed on a terminal leaf on each of the test plants. Twenty-four hours later these adult mites, all still alive, are transferred to untreated bean foliage. After another twenty-four hours all of the adult mites are removed in a way which causes no damage to the eggs that have been lai during the twenty-four hour period on the. untreated foliage.

The number of eggs laid by each batch of 0 mites is essentially the same. A sufficient time is allowed for all viable eggs to hatch. Counts demonstrate that none of the egg hatch from among those laid by mites that had fed on foliage from pots with soil containing the compound of this formulatio Hatch to provide living young was complete, on the other hand, among eggs laid by mites similarly handled except that the plants providing sustenance were not in contact with the compo The following compound can be similarly formulated and when used as above gives like results., methyl 1- (hexylcarbamoyl ) -1-benzlmidazolecarbamate Example 10- A dust concentrate is prepared as follows: methyl l-(phenylcarbamoyl ) -2-benzimidazolecarbamate 80 synthetic fine silica 20 The above ingredients are blended and milled to a particle size below 10 microns, followed by reblendlng.

Two experimental lots of house paint are prepared a similar manner except that 0.¾& by weight of the active compound of this formulation is milled with the dry ingredi in one lot, whereas none of the concentrate was added to th other lot. Test boards were painted with each lot. After one year of exposure in Florida, the board with the paint t which the concentrate was not added was badly stained by fungus growth Including species of Penicillium and other ge The board with the paint containing the compound of this inv tlon remained bright. - Example 11- ' - · - A dilute dust is prepared as follows: dust concentrate formulation of Example lo 10 ground phosphate rock' 90 The above ingredients are blended to form a free flowing dust.

A uniform cherry orchard in Michigan is selected for the test. Alternate trees are dusted every 14 days at t rate of 2 pounds per tree with the above dust formulation . The remaining trees are left unprotected.

On September 1 the trees are examined. The trees that had been dusted with the compound of this invention. are green and healthy, with all leaves remaining on the trees. At this time the foliage of the unprotected trees is largely discolored due to attack by the leaf spot fungus ( Coccomyces hiemaliS] and the two spotted mite (Tetranychus telarius). Furth much of the foliage of the unprotected trees has fallen due' to the effect of the two pests. · The following compounds may be similarly formulated and whan used as above give like results, methyl 1- (isopropylcarbamoyl )-2-benzimidazolecarbamate methyl 1- (isobutylcarbamoyl) -2-benzimldazolecarbamate methyl l-(octylcarbamoyl)-2-benzimidazolecarbamate Example 12 A dilute dust is prepared as follows : ethyl 1- (ethylcarbamoyl)-2-benzimidazolecarbamate 5 pyrophyllite 95 The active ingredient and an equal amount of pyrophyllite are first blended and micropulverized to a particle size. smaller than 100 microns, then reblended with the remainder of the diluent.

Sugar cane seed pieces cut in November are divided into eight lots. Four of these lots are dusted in such a way ao to cover all surfaces with the dust prepared as deocribed ab The other four lots are dusted with the inert diluent only.

All lots are stored under similar conditions until the followin February at which time they are examined. The four lots that had been treated with the compound of this invention are in goo condition. The four unprotected lota, on the contrary, are DO badly rotted by fungi of the genus Fusarlum that they cannot be Example 13 The following ingredients are converted into a dust as indicated: methyl l-(ethylcarbamoyl )-2-benzlmidazolecarbamate 20 Pyrophyllite * ■ 79 alkylnaphthalene sulfonic acid, sodium salt 1 Equal parts of the active ingredient and the diluent are milled with the surfactant and then diluted with the remain pyrophyllite in a ribbon blender. The components are then blend until they are homogeneous.

Cotton plants in selected plots are thoroughly dusted a rate of 10 kilograms of dust per hectare for each application June 20 and at two-week intervals thereafter until mid-August with the above dust formulation in addition to a regular insecticidal program. Similar plots receive the insecticidal application only. By late August the plots receiving the insecticide only have a high incidence of boll rot caused by Aspergillus niger and high populations of spider mites, Tetranyc sp . , which cause the leaves of the cotton plants to turn rusty brown, twist and drop to the ground. Many bolls are completely rotted and loss of leaves results in the shedding of small boll and prevents the lint from becoming fully developed. Cotton plants treated with the above' dust formulation retain healthy foliage and produce a heavy crop of healthy full-sized bolls. <. The following compounds may be similarly formulated a when used as above give like results. methyl l-[jD-chlorophenyl) carbamoyl] -2-benzimidazolecarbamate methyl l-(isopropylcarbamoyl) -2-benzimidazolecarbamate Example 1 A dust formulation is prepared from the following methyl 3-(heptylcarbamoyl)-2-benzimiclazolecarbamate 5 methoxychlor , · 5 sodium alkylnaphthalenesul ate · ' 1 pyrophyllite clay 89 The above ingredients are combined and rotated in a blender until uniformly mixed. The composition io then milled to produce particles essentially lees than 5 microns in diameter. The above -prepared dust is then applied to a special planting of tea roses. The planting consists of uniform plots each with three varieties of rose. The tes period extends from June 1 through August >1. At the end of the test period the roses in all unprotected plots are seriously damaged by the spider mite, Tetranychus telarius , the rose blackspot, Diplocarpon rosae, and the Japanese beetle, Popillla ,1aponlca. Randomly selected plots dusted at weekly intervalo with the above prepared composition to the extent that thorough coverage of the plant is obtained with the formulation, remain free from damage, and produce good yields of bloom throughout the test period.

Plots treated with a dust containing methoxychlor but without methyl l-(heptylcarbamoyl )-?-benzimidazole-carbamate show no Jananese beetle in.lury. However, they are seriously damaged by mited and blackspot.

The followincr compounds can be substituted for methyl l-(heptylr.arbamoyl )-2-benzimldazolecarbamate and when similarly formulated and used as above, dve like results, methyl l-(phenylcarbamoyl )-2-benzimidazolecarbamate methyl 1- ^ , 4-dlchlorophenyl )carbamoyl/-2-benzimldazole-carbamate · .... .' methyl l-(p_-nitrophenylcarbamoyl) -2-benzimidazolecarbamate Example 15.

An aqueous suspension concentrate is prepared as follov/s : methyl 1- ( cyclohexylcarbamoyl )-2-benzimldazolecarbamate 30. polyacrylic acid, sodium salt Ο. low viscosity polyvinyl alcohol 1. water -f (sodium hydroxide to a pK of 7.0 added last) 68.

The active component is ground to pass a 30 mesh screen and is then mixed with the remaining formulation ingredients and milled in a sand grinder until the particle size is below 5 microns.

Six field creates of oranges are picked from a commercial grove in Florida. Three of these crates are dipped for three minutes in a water bath containing a suspension made from the above formulation, in an amount to give 300 parts per million by weight of the active ingredient of this invention .

A polyethylene glycol ester of oleic acid surface active agent is present at the rate of 150 pp of total liquid.. The remaining three crates are dipped in a similar fashion in water with the surface active agent only. All crates are set aside in a citrus storage house for three weeks. At the end of this time all fruit are examined. The frui that has been dip-treated with the compou of this invention is still in good condition, but the fruit that is not so protected is largely rotted by the blue mold fungus (Penicjilliu digitatum).

Example l6 An aqueous suspension concentrate is prepared as follows methyl 1- (butylcarbamoyl)-2-benzirnida olecarbamate 30.00 polyacrylic acid, sodium salt · 0.35 lo viscosity polyvinyl alcohol 1.50 . water + (sodium hydroxide to a pH of 7.0. added last) 68.15 The active compound is ground to pass a 0 mesh screen and is then mixed with the remainin formulation in redients and Green pine lumber co ing from the saw in a mill is . dipped' for two minutes in a bath containing a suspension of the formulation prepared as described above. The amount of suspensi concentrate used is such as to provide 400 parts per million of active compound in the bath. Similar lumber is not dipped. All of the lumber is piled together in a seasoning yard. After three months the lumber is examined. The lumber that has been dip- treated was all bright and clean. The unprotected lumber. as heavily covered with green mold (Pern cillium sp . ) .

Rxamnle 17"· A granular formulation is prepared as follows: granular corn cob (lS-^O mesh) 90 • methyl l-(pentylcarbamoyl )-2-benzimldazole- carbamate 10 The active compound is dissolved in warm chloroform and the chloroform, solution is sprayed on the granular corn cob which is being tumbled in a mixer. Evaporation of the chloroform yields a finished granule in which the active ingredient is absorbed.

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 of this invention per 3β00 meters of 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 lesic caused by Rhizoctonl solani as well as heavy populations of the Pacific mite (Tetranychus pacificus ) . In the rows that had received the ranules all lants remain al v The followin compounds may be similarly formulat and when used as above give similar results, methyl l-(butylcarbamoyl)-2-benzimidazolecarbamate methyl l-(5-chloro- -methylphenyl)-2-benzimidazolecarbamate Example l8 An aerosol is prepared from the following ingredients in the proportions given: ethyl l~(lsopropylcarbarnoyl)-2-benzimidazolecarbamate 3.0 methylene chloride 22.0 Preon 11 ( trichlorom'onofluoromethane ) 37.5 Preon 12 dlchlorodlfluoromethane) 37» 5 The active ingredient is dissolved in the methylene chloride and then loaded into the aerosol container. This is followed by cold loading of the Freons. · .

Alternate rose bushes growing in a greenhouse are mist ligtitly at weekly intervals with the aerosol 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 discolore and curled due to infection by the rose powdery mildew organism^ Sphaerotheca. hummli . Other foliage on the untreated plants is yellowed due to attack by the Atlantic mite (Tetranychus atlanti Due to the extensive foliage damage, the plants not treated with the compound of this invention grow more slowly than the protect plants .

The following compounds may be similarly formulated an when used as above give good results: ethyl 1- (butylcarbamoyl)-2-benzimidazolecarbamate methyl 1 -(hexylcarbamoyl)-2-benzlmidazolecarbamate methyl l-(benzylcarbamoyl ) -2-benzimidazolecarbamate » Exam le 19 l-butylcarbamoyl-2-benzlmldazolecarbamic acid methyl ester 51.6^ Alkyl Naphthalene sulfonate, sodium salt (T,Alkanol" B) 5.0 Polyvinylpyrolidone derivative ( "Ganex" V 904) 1.0 Calcium carbonate surface-reacted with propionic acid 42.4 The mixture is prepared by blending, mlkropulverizlng, and finally air-milling until the particle size is below about five microns,, Test plots are established in a rice field. These are sprayed with water containing a suspension of the wettable powder described above along with an aliphatic amide alkyl sulfonate surface active agent ("Hyfoam" Base LL). 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 "hyfoam" Base LL used 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 unsprayed.

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, Pivicularia oryzae which greatly reduces yield.

Example ZQL_ . ' The formulation of Example 1.9 is also useful in controlling Sigatoka disease of banana caused by the fungus Cercospora musae. This is demonstrated by a field test in which designated areas in a banana plantation are treated with 400 grams of the active ingredient of this invention per hectare and an equal amount of a polyhydric alcohol ester surface active agent ("Trem" 014) applied in an amount of water sufficient to assure good distribution. The treatment is applied at intervals Four months after the start of the test the banana plants in the treated plots are free from disease, whereas, the untreated plantB are heavily damaged by Sigatoka disease.

Example .23. . l-(p_-nitrophenylcarbamoyl) -2-benzimidazole- carbainic acid, methyl ester 72.2 Sodium lauryl sulfate ( "Duponol" WA) 1.5 Oleic acid ester of sodium isethlonate ("lgepan"AP 73) · 2.0 Diatoroaceous earth ("Celite" 209) .2 .3 The mixture is prepared by blending the ingredients, hammer-milling, and then air-milling twice to obtain a very finely divided powder. .

• A test is established in a field planting of celery in Florida. Randon plots established in the field are sprayed with water containing a suspension of the wettable pov/der described above along with a blend of aromatic sulfonate and ethylene oxide derivatives ("Agrimul" GM) . The amount of wettable pov/der used is such as to provide two grams of active compound of this invention per liter of water. The amount of "Agrimol" GM used is such as to provide 300 ppm in. he final spray. The spray is applied weekly at the rate of 1000 liters per hectare. The remainder of the field is left unsprayed.

Three months after the first spray application, the sprayed celery plots are in a healthy condition and obviously growing well. The untreated portions of the field on the other hand are seriously infested with the early blight fungus (Cercospora opli) . The disease causes the death of much of the foliage and reduces the growth and market volume of the plants.

Example 22 The formulation of Example 21 is also useful in controlling peach scab caused by the fungus Cladosporlum carpophUum, This is demonstrated by a field study in which random trees in a peach planting are sprayed, starting in the spring, with water containing a suspension of the wettable . powder described in the example along with an acid complex organic phosphate ester surface active agent ( " Gafac " RE-610) .

The amount of the wettable powder used is such as to provide 2.5 grams of the active compound of this invention per liter of water. The amount of "Gafac " rcE-610 employed is 400 ppm in the final spray.

The spray is applied on a normal peach fungicide schedule at the rate of 2000 liters per hectare of peach trees. The remaining trees in the planting are left unsprayed.

At the time of harvest fruit on the treated trees are healthy and attractive to consumers. Conversely, fruit from the untreated trees is spotted with scab and of reduced market value.

Example 23 l-butylcarbamoyl-2-benzimldazolecarbamlc acid, methyl ester 51.6 Alkylnaphthalene sulfonate, sodium salt (Petro Ag Special) 4.0 Neutral, partially desulfonated sodium lignin sulfonate ( "Marasperse" ) 44.4 The surfactants are heated to remove free moisture, and after again being cooled they are blended with the active ingredient.

The mixture is air-milled to obtain a homogeneous wettable powder of fine particle size.

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 sulfosuccinate surface active agent ("Aerosol" OT) . The amount of the wettable powder used is such as to provide one gram of the active compound of this invention 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.

Example .24 The formulation of Example 25 is also useful in controlling .powdery mildew of grapes caused by the fungus Uncinula necator. This is demonstrated by a field test in which alternate rows of -grapes growing in California are sprayed with a water suspension of the wettable powder containing two grams of the active ingredient per liter. To the spray suspension is also added 300 ppm of sodium N-methyl-N-oleoyl taurate (" Igepon " T 77 ) The sprays are applied to the treated rows weekly at the rate of 1200 liters per hectare.

Near the end of the growing season (after 14 weekly treatments) the grape vines in the treated rows are healthy and growing well. The untreated rows, hov.-ever, are heavily diseased with powdery mildew and, as a consequence, growing

Claims (1)

1. CLAIMS : lc A composition useful as a mite ovicide and a fungicide characterized in that the active ingredient is of the formula: H t where ! R-j^ is alkyl of 1 through carbon atoms and is alkyl of 1 through 12 carbon atoms; phenyl; phenyl substituted withmethyl, ethyl, methoxy, ethoxy, nitro, cyano or halogen; benzyl, benzyl substituted with methyl, nitro, methoxy or halogen; (cycloalkyl) alkyl of 7 through 8 carbon atoms; (cycloalkyl) alkyl of 7 through 8 carbon atoms substituted with methyl; cyclohexyl; -. cyclohexyl substituted with methyl; alkenyl of 3 through 10 carbon atoms; or (alkoxycarbonyl)alkyl of 3 through 6 carbon atoms. A composition useful as a mite ovicide and a fungicide characterized in that it contains as the active ingredient methyl l-(butylcarbamoyl)-2-benzimidazolecarbamate . 3e Methyl l-(butylcarbamoyl)-2-benzimidazole-carbamate, 4. A compound represented by the formula: H where R-^ is alkyl of 1 through 4 carbon atoms and R^ is alkyl of 1 through 12 carbon atoms; phenyl; phenyl substituted with methyl, ethyl, methoxy, ethoxy, nitro, cyano or halogen; benzyl; benzyl substituted-with methyl, nitro, methoxy or halogen; (cycloalkyl) alkyl of 7 through 8 carbon ■ atoms; (cycloalkyl) alkyl of 7 through 8 carbon atoms substituted with methyl; cyclohexyl; cyclohexyl substituted with methyl; alkenyl of 3 through 10 carbon atoms; or (alkoxycarbonyl)alkyl of 3 through 6 carbon atoms* 5. A process for making the compounds of claim 4 comprising reacting a 2-benzimidazolecarbamate of the formula with (1) an isocyanate of the formula NCO