IL33340A - Metal complexes of 2-benzimidazolecarbamic acid esters their preparation and use as fungicides - Google Patents

Description

nsninn ο»ηοοκ a*'nana o*oaVt>»ip Metal complexes of 2-benaitnidazolecar¾amie acid esters their preparation and use ae furtgioides PONT DE NEMOURS AND COMPANY 33340/2 ^ This invention relates to new, fungicidally active derivatives of 2«-benzimidazolecarbamic acid alkyl esters,.

Alkyl 2-benzimidazole carbamates of the formula .

- G -0'.alkyl and their fungicidal properties are known.

The present invention provides new derivatives thereof, in which R is methyl, ethyl, isopropyl or sec-butyl: n is 1 or 2} M is zinc or copper q. is 1 when M is copper and q is equal to n when M is zinc; in which \ihe n is 2, X is chloride or bromide ion; and when n is 1, )C is chloride, bromide, acetate or propionate when M is copper and when M is zinc,, X is acetate or propionate*.

These new complexes have been found to possess outstanding fungicidal properties,.

In accordance with the invention the new complexes can be prepared by a process in one or two equivalents of a 2-benzimidazole-carbamic acid ester of the formula: where R has the same meaning as above, are reacted with one equivalent of zinc or copper (II) chloride, bromide, acetate or propionate in the presence of water.

It should be understood that benzimidazole-carbamates exist in tautomeric forms, i.e., H H H H ° wherein ; R is methyl, ethyl, isopropyl, or sec-butyl; and In carrying out the reaction, the order of addition is not critical. In some cases, the 2-benzimida- solecarbamate is hard to wet with a concentrated solution of the salt, in these cases, it is advantageous to first thoroughly wet the 2-benziraidazolecarbamate with water before mixing same with the salt solution. Also, it is permissible, but not necessary, to use an organic solvent such as ethyl acetate: to wet the benzimidazolecarbamate. The solvent may be left in the reaction mixture during the subsequent reaction.

The concentration of the 2-benzimidazolecarbamate in the. aqueous slurry is not critical and can vary from very dilute to about 20% by weight. However, very dilute concentrations are not economical in light of the large amount of water hich must be used and the large ¾size of equipment required. Concentrations above about 20% are difficult to stir efficiently. The concentration of the metal salt is not critical, although it is preferred to use concentrated or saturated solutions, e.g., 66% by weight or higher in the case of zinc chloride. Since the salt solutions often contain large excesses of metal salt, it is economically advantageous to recover any filtrates for use in subsequent operations. While concentrated solutions are preferred, good results can be obtained by using dilute solutions of the salt. The total quantity of metal salt present in the reaction mixture can vary from the theoretical amount to an excess of well over 1000$.

The particle size of the 2-benzimidazolecarbamate suspended in the metal salt solution is not critical. Small particle sizes are advantageous in bringing about an increase in rate of reaction; however, at very small particle sizes the 2-benzimidazole may be hard to wet with the salt solution. Accordingly, inert wetting, dispersing,' or emulsifying agents can in some cases be useful in improving the reaction condi The time required to complete the reaction is not critical and can vary, for example, from a few seconds to l6 hours or more. Many factors influence reaction time, such as: temperature, concentration of reactants, particle size of the 2-benzimidazolecarbamate, etc. In each case the optimum conditions can be determined experimentally.1 Completeness of the reaction is best determined by the appearance and disappearance of certain peaks in the IR spectrum, as described in the . examples .

The temperature at which the reaction proceeds is significant in some cases In regard to the product formed, whereas in other cases the temperature. effects only the rate of reaction. For example, in reacting 2-benzimidazolecarbamic acid esters, with copper(II) chloride at a temperature of about 100°C., a 1:1 complex with copper(II) monochloride is obtained, while at room temperature a 2:1 qomplex with copper(II chloride is obtained as shown in Examples 3 and 4. In general, the reaction temperature can vary between around room temperature to about 130°C..

The presence of foreign ions, such as those which are produced during the production of the 2-benzimidazolecarbamic acid esters from alkyl chloroformates, cyanamide, and ortho-phenylene diamine, do not interfere with the complex c¾nip3r±nrg- formation. Thus, it is not necessary to purify the starting 2-benzimidazolecarbamate prior to starting the reaction.

The complexes of this invention can be made either batchwise or on a continuous basis.

The following examples illustrate the preparation of the complexes of Formula I. The amounts are given in terms of parts by weight unless otherwise specified.

Example 1 Preparation of 2-benzlmidazolecarbamic acid, methyl eater, 2:1 complex with zinc chloride Five hundred seventy-three parts of 2-benzImidazole-carbamic acid, methyl ester is mixed with a solution of 273 parts of zinc chloride in 25G0 parts of water. With vigorous stirring, the mixture is heated to reflux and kept at reflux . temperature for 30 minutes. Then, the mixture is cooled and filtered, and the filter cake is washed thoroughly with water and dried, giving 696 parts of the product.

In the infrared spectrum the peaks at 5.84 and 7·90μ, which are characteristic for 2-benziraidazolecarbamic acid, methyl ester, are no longer present and new peaks at .75 and 8.07M., which are characteristic for the zinc chloride complex, have appeared. This product may be used as such or in formulated form for antifungal application, even though it contains approximately 10# of starting material.

Analysis; Calculated for a mixture of {"30°j» by weight of 2:1 ester, zinc chloride complex and # by weight of organic starting .15; H, 3.6; N, 16.6; CI, 12.3; Zn, 11.3.

Product of Example 1 found: C, 42.92; H, 3.6l; N, 16.58; CI, 12.6¾ Zn 11.3.

The above product is purified as follows. 5.0 parts of the material is extracted with 200 parts of boiling acetonitrile and the hot mixture filtered. The insoluble material (0.5 parts) exhibits an IR spectrum identical with that of 2-benzimidazolecarbamic acid, methyl ester. The acetonitrile filtrate is vacuum-concentrated to a small volume, cooled, and the precipitated solid (4 parts after air-drying) is collected on a filter. It consists of purely white fluffy needles, and its IR spectrum is essentially the same as that of the crude product (characteristic peaks at 5.75 and 6 .07μ) . Evaporation of the mother liquor affords another 0.5 parts of somewhat impure product..

The air-dried needles analyze for a product containing approximately 2 water, as shown by the following results : Analysis ; Calculated for 2-benzimidazolecarbamic acid, methyl ester, 2 : 1 complex with zinc chloride containing 2% water: ■ ' _ C, 0.9; H, 3.65 N, 15.91; CI, 13.4 zn, 12.35. Found: C, 41.19 H, 3.40; N, 15.91; CI, 13.12; zn, 12 .3. probably has the structure shown in Formula . . ·' ¾ ' ' if- Example 2 Preparation of 2-benzimidazolecarbaraic acid, methyl ester, ltl complex with zinc monoacetate Fifty-seven parts of 2-benzimidazolecarbamic acid, methyl ester is mixed with a solution of 367 parts of anhydrous zinc acetate in 600. parts of water. With vigorous stirring, the slurry is heated to reflux and kept at reflux temperature. for 2 1/2 hours. The mixture is then cooled, filtered, the solid washed thoroughly with water, and air dried. The product consists of 70 parts of a white powder. The IR spectrum showed characteristic peaks at approximately 5.7 and 8.1μ. Peaks at 5. £4 and 7 · 90μ·, which are characteristic for the organic starting material, were absent.

Analysis : Calculated for 2-benzimidazolecarbamic acid, methyl ester, 1 :1 complex with zinc monoacetate (CllHilN3°4Zn) containinS 1. ^ HgO: C, 41.4; H, 3.6 ; N, 13 - 55; Zn, 20.5.

: Example 3 Preparation of 2-benzimidazolecarbaraic acid, methyl ester, 1:1 complex with copper(II) monochloride To a solution of 340 parts of copper(II) chloride dihydrate in 250 parts of water is added 57 parts of finely ground 2-benzimidazolecarbamic acid, methyl ester. The mixture is stirred and heated on a steambath for '4 hours. The very dark reaction mixture is cooled and diluted with water, whereby the color changes to green. The mixture is filtered, and the solid is washed thoroughly with water and air-dried to 57 parts of the product, a green powder.

Analysis : Calcd. for C9H9 502CUC1: C, 37.3; H, 3»1; N, 14.5.

Pound: C, 37 .09; H, 3.66 ; N, 14.

The infrared spectrum shows characteristic peaks at 5.7 and 8.04μ.

This complex probably has the formula : Example 5 Preparation of 2-benz Imidazolecarbamic .acid, Isopropyl ester, 2 ;1 complex with zinc chloride Thirty-one parts of 2-benzimldazolecarbamic acid, isopropyl ester is stirred with 200 parts of water until the solid is thoroughly wetted and suspended in the water. Then, a. solution of Ι9Ί parts of zinc chloride in 3θ0 parts of water lis added, and the mixture is heated to reflux combined with stirring. After boiling under reflux for two hours, the mixture is cooled and filtered and the solid is washed with water and dried, giving 37 parts of the product as a white solid. The IR spectrum shows characteristic peaks at 5.75 and 8.05μ and very weak peaks at 5.9 and 7.9M-, indicating the presence of some organic starting material.

In 1, the product in this case ' is insoluble acetone) whereas the starting material (the isopropyl ester) is soluble in acetohitrile and particularly in acetone. Therefore, in order to remove . the organic starting material, the crude product is stirred in 300 parts of acetone, filtered, washed with 300 parts of acetone, and dried. The infrared spectrum no longer shows the weak peaks at 5 · 9. and 7·9 · but the strong peaks at 5.75 and £ .05μ are still present.

Example 6.

Preparation of 2-benzimidazolecarbamic acid, methyl ester 2 :1 complex with zinc chloride, starting from a crude aqueous slurry of 2-benzimldazolecarbamic acid, methyl ester Methyl chloroformate (79·5 parts) and 50$ sodium hydroxide (131 parts) are added simultaneously with good agitation to a solution of cyanaraide (3 .6 parts) in 165 parts of water. The separate addition rates are controlled so that the pH remains between 6.5 and 7.5 ; The temperature To this reaction mass are added o-phenylenediamine (75.5 parts) and enough concentrated hydrochloric acid to give a pH of 4.0. The mixture is then heated and stirred for an hour at 95°C. while the pH is maintained at 4.0 by the intermittent addition of concentrated hydrochloric acid. The resulting slurry contains 123.0 parts of 2-benzimidazole-carbamlc acid, methyl ester.

Zinc chloride (275 parts) is added to the hot slurry. The mixture is stirred at 95°C. for another 20 minutes, cooled to 50eC. and filtered. The product is washed with water and dried in a vacuum oven at 100°C. The infrared spectrum of this product is identical with that of Example 1.

Examples 7-17.

Using the indicated starting materials and the . method of the example indicated, several complexes of this invention are prepared.

Procedure of Exam le Example Starting Materials 2-BenzimldazOlecarbamlc acid, methyl ester zinc bromide 2-Benzlmidazolecarbamic acid, methyl ester zinc propionate 2-Benzlmidazolecarbamic acid, ethyl ester a w zinc chloride 2-Benzlmidazolecarbamic 2 acid, ethyl ester copper(II) chloride Cont'd Procedure of Example Example Starting Materials 11 (a 2-Benz imidazolecarbamic 2 acid, iso ropy1 ester a c m copper(II) chloride 12 (a 2-Benzimidazolecarbamic 2 acid, isopropyl ester copper(II) chloride 13 (a 2-Benzimidazolecarbamic acid, ae£-butyl ester zinc chloride Cont'd Procedure of Example Example Starting Materials 14 a 2-Benzimidazolecarbamic acid, methyl ester b copper(II) bromide a 2-Benzimldazolecarbamlc acid, methyl ester b copper(II) propionate I 16 a 2-Benzimidazolecarbamic acid, methyl ester b copper(II) bromide 17 a 2-Benzimidazolecarbamic acid, methyl ester b copper(ll) acetate Utility of the Complexes The present complexes are useful for controlling the effects of fungi.

There are many fungi against which the complexes are active. These may be represented by, but are not -limited to, the following: Venturia Inaequalis, which causes apple scab; Podosphaera leucotrlcha, which causes powdery mildew on apple, Uromyces phaseoli, which causes bean rust; Cercospora apii, which causes early blight of celery; Septorla apll-graveolentis , which causes late blight of celery; Sclerotlnla sclerotiorua which causes white mold on beans and other crops; Cercospora musae, which causes Sigatoka disease of banana; Monllinla fructlcola and M. laxa, which cause brown rot of stone fruits; Eryslphe clchoracearum, which causes powdery mildew on cantaloupe and other cucurbit crops; Penlcillium digitatum, which causes green mold on citrus; Sphaerotheca humull, which causes powdery mildew on roses; Diplocarpon rosae, which causes black spot on roses; Uniclnula necator, which causes powdery mildew on grapes; CoccOmyces hiemalls, which causes cherry leaf spot; Clado-sporium carpophllum, which causes peach scab; Pithomyces chartorum, which grows on turf and pasture grasses and indirectly causes. a malady in sheep; Eryslphe graminls hordel, which causes powdery mildew on barley; Plricularia oryzae, which causes rice blast; Puceinia rubigo-vera trltici, P. Coronat and P. glumarum, which cause leaf rusts of wheat, oats and grasses respectively; Pucclnla graminls tritici, which causes stem rust of wheat; Aspergillus nlger, which causes cotton , boll rot as well as decay following wounding in many plant tissues; Aspergillus terreus, which is common in soil and attacks vegetable matter; various species of Rhlzoctonla, Fusarlum and Verticlillum present in soil and attacking the roots or other underground parts of a variety of plants; flyrothecium attacking such items as shower curtains, carpets, mats and clothing.

The complexes of this invention when applied by the.^methods of this invention enter and move freely within plants, i.e., they are systemic.: Thus, fungi can be controlled in plant parts well removed from the point, of application. In view of such -movement, the complexes can be applied beneficially to certain seeds. For example, 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 (Eryslphe clchoracearum) .,. on the resulting plants for periods in excess of 40 "days. Applications to soil also -provide control of certain foliage diseases on plants growing in the treated soil. Spray or dust treatments of plant foliage Impart protection . against fungi to other foliage on the plant not actually sprayed and to new foliage developing later.

There are important practical advantages associated with the use of an effective systemic fungicide.. Suc-cessful 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 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 complexes 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 complexes 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 an 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.

The complexes of this invention provide protection from damage caused by fungi, when applied to the proper locus by the methods described hereinafter and at a sufficient rate to exert the desired fungicidal 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, sweet potatoes, tobacco, hops, turf and pasture.

Living plants may be protected from fungi by applying one or more of the complexes of this invention to the soil in which they are growing or in which they may subsequently be seeded oi* 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 b dipping the root system or physically injecting the chemical or chemicals Soil applications are made with dusts, granules, pellets, slurries or solutions. Preferred rates for application of the compounds of this invention to soil in which plants are or will be growing range from 1 to 200 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 2 to 50 parts per million.

Preferred rates for application to seeds, tubers, bulbs or other, plant reproductive parts, range from 0 to 2000 grams of active compound of this invention per 50 kilograms of planting material treated. More preferred rates are in the range of ICO to 1000 grams of active compound per 5,0 kilograms. Applications are made from dusts, slurries or solutions. Such treatments protect the treated parts themselves from.damage due to fungi and in addition,"impart extended protection 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 20 to 4000 grams of active ingredient per hectare. More preferred rates are in the range of o to 2000 grams 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, 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 6o days. ' Preferred rates for dip applications to roots of living plants are in the range of 20 to 1000 grams of active ingredient per 100 liters of water or other liquid carrier.

Preferred rates for injection into the roots or stems of living plants are in the range of 1 to 1000 parts per million of water or other liquid carrier.

Plant parts such as fruits, tubers, bulbs, roots and the like, harvested for food or feed; are protected from decay and other deterioration caused by fungi during processing, distribution and storage by treatment with an active comple 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 complex or enclosed in wrapping or packing materials impregnated with the active complex.

If a liquid bath is used, it car. contain an amount of the active ingredient in the range of 1 to 5000 parts per million of the Weight of the liquid.

Dusts as well as wrapping or packing materials used for this type of application can contain 0.1 to 10£ of the active ingredient.

Wood, leather, fabric, fiber board, paper and other Industrial materials of an organic nature can be protected from decomposition or discoloration by fungi by coating, incorporating and impregnating with, an effective amount of one or more of the complexes of this invention. The coatin can be accomplished by dipping, spraying, flooding, misting (as with an aerosol) or dusting the material to be protected with a suitable composition •containing the active ingredient.

Wherev 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 0.1 percent by Surface treatment is by dips, washes, sprays, aerosols or dust applications... Sprays, dips and washes contain the active completes 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.

Painted surfaces can be protected from unsightly, stain, and mold growth by incorporating in the paint formulation, prior to application, 5 to 2,000 parts per million of an active complex of this, invention. Such treatments with the complex of this invention also protect the paint while still in the can from deterioration by fungi.

As was previously set forth, the complexes of this invention are especially 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 fungi which are regularly present, applications often start prior to the time that the problem actually appears and continue on a pre-determined schedule. Such a procedure is termed "preventive" or "protective".

With the complexes of this invention, successful control of plant diseases can also be accomplished by applica tions 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 complexes 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.

Curative? disease control .with the complexes of this invention is improved by including. a \ proper quantity of a selected surface active agent in the spray or dust applied to the plant. The most preferred surface active agents for this purpose include: modified phthalic glycerol alkyd resins, glycol esters, ethoxylated fatty ' acids, alcohol sulfates, lecithin and lecithin derivatives, isethionates, certain phosphate derivatives and taurates. .

Somewhat less preferred but, nevertheless, effective surface active agents include: sulfosuccinate derivatives, ethoxylated fatty, esters and oils, ethoxylated alcohols, and dodecyl and tridecyl benzene sulfonates and free acids.

Examples of specific surface active agents in each of these several categories are listed in "Detergents and Emulsifiers— 167 Annual" published by John W. McCutcheon, Inc.

. The preferred rates for these surfactants when are used in sprays -Le- in the range from 10 to 1000 parts per million of the spray fluid.

For dusts, the preferred surfactants rates are in the range of 1000 to 100,000 parts per million of the material actually applied.

As previously mentioned, the complexes of the invention are systemic, thus applications to plants can be accomplished by spraying or dusting above-ground parts, such as foliage, stems and fruits. For such applications, 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 Systemic control of fungi on plants , is also accomplished by applications to seeds, tubers, bulbs, or 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. Applications to reproductive parts 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.

Compositions Compositions can be formed by mixing a complex of this invention with an adjuvant. The complexes of this invention can often be u»ed to advantage in combinations or mixtures with one or more of the fungicides, bactericides, insecticides, acaricides, or nematocidee available on the market today. The combinations or mixtures can be made by the applicator Just prior to use (as in the tank of a sprayer) or included in a single composition by the manufacturer or a subsequent processor. Illustrative of the materialB that may be included in such combinatione or mixtures are the following: 1* 2, 3, 4, 10, 10-hexachloro-l, 4, 4a, , 8, 8a-hexahydro- 1, 4-endo- exo-5, 8-dimethanonaphthalene (aldrin); 1, 2, 3, 4, 5» 6-hexachlorocyclohexane (lindane); 1, 2*4, 5, , 7* 8, 8-octachloro-2/3* 3a, 4, 7* 7a-hexahydro-4, 7- methanoindene (chlordane); l,l,l-trichloro-2, 2-bis(p-chlorophenyl)ethane (DDT) j l* 2,5, 4, 10, 10-hexachloro-6, 7-epoxy-l,4,4a, 5» 6, 7* 8, 8a-octa- dibasic lead arsenate; 2'-chloroethyl-l-meth l-2-(p-tert-butylphenoxy) ethyl sulfite; azobenzene; ethyl 2-hydroxy-2,2-bis(4-chlorophenyl) acetate; tnio . 0,0-diethyl-0-(2-(ethylBaQaa-pto)ethyl) thiophoephate; 2, -dinitro-6- sec-butyl phenol; O-ethyl O-p-nitrophenylbenzenethiophosphonate (EPN); -chlorophenyl- -chlorobenzene sulfonate; p-chlorophenyl phenyl sulfone; tetraethyl pyrophosphate; 1,1-bis- (p-chlorophenyl )ethanbl; l,l«-bie-(chlorophenyl)-2,2,2-trichioroethanol p-chlorophenyl p-chlorobenzyl sulfide bis- (p-chlorophenoxy)methane; 3- (1-methyl- -pyrrolidyl)pyridine; mixed esters of pyrethrolone and clnerolone keto-alcohols and two chrysanthemum acids; cube and derris, both whole root and powdered; ryanodine; mixture of alkaloids known as veratrine; d1-2-allyi-4-h droxy-3-methy1-2-cyclopenten-1-one esteri led with a mixture of cis and trans dl-chrysanthemum . monocarboxylic acids; butoxypolypropylene glycolj p-dichlorobenzene; 2-butoxy-2'-thiocyanodiethyl ether; naphthalene; 1, l-dichloro-2,2-bis (p-ethylphenyl)ethane £-dlmethylaminobenzenediazo sodium sulfonate; quinone oxyaminobenzooxohydrazone; tetramethyl thluram monosulflde; tetramethyl thiuram disulfide (tSiiram) metal salts of ethylene bisdithiocarbamic acid, e.g., manganese, zinc, iron and sodium salts; pentachlbronitrobenzene; - 2.3-dihydro-5-carboxyanilido-6-methyl-1, -oxathiin n-dodecylguanidine acetate (dodlne) N-trlehloromethylthiotetrahydrophthallmlde (captan); phenylmercury acetate; 2. -dichloro-6-(o-chloroanilino)-8-triazine (Pyrene e); N-methylmercury p_-toluenesulfonanilide; chlorophenolmercury hydroxides; nitrophenolmercury hydroxides; ethylmercury acetate'; ethylmercury 2,3-dihydroxypropy1 mercaptlde; methylmercury acetate; methylmercury 2,3-dihydroxypropyl mercaptlde (Ceresan*L); 3,3 '-ethylenebis(tetrahydro-4,6-dimethyl-2H-1,3, 5-thiadl- ? azine-2-thione) (Cylan®); N-ethylmercury p_-toluenesulfonanilide; l,4-dichloro-2,5-dimethoxy benzene (chloroneb); metal (e.g., iron, sodium and zinc), ammonium and amine salts of dialkyldithiocarbamic acids; tetrachloronltroanisole; hexachlorobenzene ; hexachlorophene; methylmercury nitrile; tetrac loroquinone ; N-1richloromethy1thiophthaiimide ; -ethoxy-5-trichloromethyl-l,2, -thiadiazole; l,2-dibromo° -chloropropene; dlchloropropane - dichloropropena mixture; ethylene dibromide; 1-chloro- -nitropropane; chloropicrin; sodium dimethyldithiocar amate; tetrachlorolsophthalonitrlle; 2-carbo¾amino-l-benzimidazolecarboxylic acid, dimethyl ester streptomycin; 2-(2,4,5-trichlorophenoxy)propionic acid; _-chlorophenoxyacetic acid; 1-naphthaleneacetamide ; N-l-naphthylacetamlde ; S-methyl-N-[ (methylcarbamoyl)-oxy]thiolacetimidate; and S-meth l-N[ (carbamoyl) -oxy] thiolacetimidate .

Sulfur fixed coppers Bordeaux mixture The additional ρ··ticides are employed in mixtures or combinations in amounts ranging from one-tenth to ten times that of the compound or compounds of this invention.

The proper choice of amounts for the added pesticides is readily made by one skilled in the art of protecting plants from pest depredations.

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

Specific illustrations of useful combinations and mixtures, along with representative (but not restrictive) applications, follow: (a) 2-Benzimidazolecarbamic acid, methyl ester 2:1 complex with zinc chloride and carbaryl in ratios ranging from 1:5 to 1:1 for use on snap beans to control white mold (Sclerotinia sclerotiorum) along with insects such as the Mexican bean beetle and flea beetles. Where aphids are a factor, parathion or Diazinon® may also be added to the mixture at rates ranging from one-tenth to one-half the level of the carbaryl. The 2-benzimidazolecarbamic acid, methyl ester 2:1 complex with zinc chloride in the mixture can be replaced by other compounds of this invention. (b) 2-Benzimidazolecarbamic acid, isopropyl ester, 2:1 complex with zinc bromide and DDT in ratios ranging from 1:6 to 1:1 for use on apple trees to control diseases such as scab ■ -r - insects including the coaling moth, the fall, webworm, and the apple red bug. The 2- benzimidazoiecarbamic: acid, isopropyl ester, 2:1 complex with zinc bromide may be replaced in the combination by other compounds of this invention. The DDT may be replaced by methoxychlor or Guthion®. TDE can be added at the same rate as the other insecticide where the red-banded leaf roller is a particu- lar problem. Thiram can be added to the mixture at the same rate as the compound of this invention to improve control of certain of the late-season fruit spot diseases. "(c) 2-Benzimidazolecarbamic acid, methyl ester, 1:1 complex with copper(ll) monochloride and .' (g) ...- Kelthane dicofol in ratios ranging from 1:5 to 1:1 for use on squash to control powdery mildew along with red spider mites.

The 2-benzimidazolecarbamic acid, methyl 0 ester, 1:1 complex with copper(ll) mono- chloride may be replaced in this combination by any other compound of this invention. (d) 2-Benzimidazolecarbamic acid, et yl ester, , · ■.. ^ 1:1 complex with zinc monopropionate and maneb in ratios of 1:6 to 1:1 for use on tomatoes to control a disease complex . involving late blight, early blight (Alternarla), anthracnose (Colletotrichum) , and gray leaf (S) spot (Stemphylium) . Lannate** methorny1 may be added to the mixture in insecticidal amounts to provide control of tomato fruitworm and hornworra. The 2-benzimidazolecarbamic acid, ethyl ester, 1:1 complex with zinc monopropionate may be replaced in the mixture by any other compound of the invention. (e) 2-Benzimldazolecarbamic acid, methyl ester, 1:1 complex with copper-(II) -monoacetate and EPN in ratios ranging from 1:6 to 1:1 for uee on grape vines in the field to control pow- dery mildew, and the grape berry moth. The 2-benzimidazolecarbamic acid, methyl ester, 1:1 complex with copper(ll) monoacetate may be replaced in such a combination by any other compound, of this invention.

Captan and folpet may be added to the combination at rates ranging from one-half to four times . .that of the compound of this invention to provide improved control of dead arm. (f) 2-Benzimidazolecarbamic acid, sec-butyl ester, 1:1 complex with zinc monoacetate along with dodlne and wettable sulfur in ratios ranging from 1:3:6 to 1:1:6 for the superlative control of scab, powdery mildew, black rot, cedar apple rust, and frog-eye leaf spot. Other compounds of this invention may be substituted for 2-benzimidazolecarbamic acid, sec-butyl ester, 1:1 complex with zin monoacetate in such combinations. (g) 2-Benzlmldazolecarbamic.acldj sec-butyl ester. 2:1 complex with zinc chloride and toxaphene in ratios ranging from 1:3 to 3:1 for use on lima beans to control powdery mildew and anthracnosej as well as insects such as cutworms, lygus bugs, and caterpillars.. Copper sulfate or streptomycin sulfate may be added to the combination at active levels where bacterial diseases are a factor. Other compounds, of this invention may be substituted for 2-benzimidazolecarbamic acid, sec butyl ester, 2:1 complex with zinc chloride in such combinations.

Compositions of this invention can be formulated by mixing a complex of this invention with other adjuvants such as one or more surface active agents.

The surface active agents used in this invention can be wetting, dispersing or emulsifying agents. They may act as wetting agents for wettable powders and dusts or as dispersing agents for wettable powders and granules.

Surfactants may also enhance the biological activity of the 2-benzimidazolecarbamic acid ester metal complexes of this invention. Such surface active agents can include such anionic, cationic and nonionic agents as have heretofore been generally employed in plant disease control compositions of similar type. Suitable surface active agents are set out, for example , in "Detergents and Emulsifiers Annual - I967" by John W. McCutcheon, Inc. Other surface active agents not listed by McCutcheon but still effective dispersants by virtue of protective colloid action include methyl cellulose, polyvinyl alcohol, hydroxyethylcellulose, and alkyl substituted polyvinyl pyrrolidones .

Suitable surface active agents for use in compositions of this invention include polyethylene glycol esters with fatty and rosin acids, polyethylene glycol esters with: alkyl phenols or with long-chain aliphatic alcohols, polyethylene glycol ethers with sorbitan fatty acid esters, and polyoxyethylenethio ethers. Other suitable surfactants, include alkali and alkaline earth salts of alkyl aryl sulfonic acids, alkali and. alkaline earth fatty alcohol sulfates, dialkyl esters of alkali metal sulfosucclnates, fatty acid esters of alkali and alkaline earth isethionates and taurates, alkali and alkaline earth salts of llgnin sulfonic acids, methylated or hydroxyethylated cellulose, polyvinyl alcohols, alkyl substituted polyvinyl pyrrolidone, alkali and alkaline earth salts of polymerized alk lnaphthalene sulfonic acids, and long-chain quaternary ammonium compounds. Anionic and nonionic surface active agents are preferred.

Among preferred wetting agents are sodium alkyl naphthalene sulfonates, sodium dioctylsulfosuccinate, sodium dodecylbenzene sulfonate, ethylene oxide condensates with alkylated phenols such as octyl, nonyl and dodecyl phenol, sodium lauryl sulfate; and trimethylnonyl polyethylene glycols. Among preferred dispersing agents are sodium, calcium and magnesium lignin sulfonates, low-viscosity methyl cellulose, low-viscosity polyvinyl alcohol, alkylated polyvinyl pyrrolidone, polymerized alkyl naphthalene sulfonates, sodium N-oleyl or N-lauryl isethionates, sodium N-methyl-N- . palmitoyl taurate and dodecylphenol polyethylene glycol - ' · Compositions of this invention will contain, in addition to surface active agents, solid diluents to produce wettable powders, dusts, or granules as desired A. Wettable Powders ettable powders are compositions which usually contain inert solid diluents In addition to surfactants.

These , inert diluents may serve several purposes. They can act as grinding aids to prevent mill smear and screen blinding, they can aid rapid dispersion of the mix when placed in water, they can adsorb liquid or low melting solid active material to produce a free flowing solid product, they can prevent agglomeration into lumps upon prolonged hot storage and they can permit preparation of compositions with a controlled amount of active ingredient so that proper dosage is easily measured by the consumer.

Suitable diluents may be either inorganic or organic in origin. These include the natural clays, diatomaceous earth, synthetic mineral fillers derived from silica or silicates, insoluble salts produced by precipitation in fluffy form such as tricalcium phosphate or calcium carbonate, and powdered organic diluents such as shell flours, wood flours, corn cob flour or sucrose. Preferred fillers for the compositions of this invention include kaolin clays, attapulgite clay, nonswelling "calcium magnesium montmorillonites, synthetic silicas, synthetic calcium and magnesium silicates, diatomaceous silica, cob flour, and sucrose.

Wettable powders will normally contain both a wetter and a dispersant. Mos!t preferred for dry wettable powders are those anionic and nonionic surfactants which exist in solid form. Occasionally a liquid, nonionic surfactant, normally considered an emulsifying agent can be used to produce both wetting and dispersion.

Wettin and dis ersin a ents in wettable owders composition. The active component will be present at a concentration of from about 25% to 90% and diluent makes up the balance to 100%. Where needed a corrosion inhibitor or foaming inhibitor may be added at rates of 0.1% to 1.0% with a corresponding reduction in diluent.

When surfactants are used to enhance biological activity, they are most commonly added as a separate component to the spray tank and are normally present at concentrations of 50-1000 ppm based upon the water in the tank.

B. Dusts Dust compositions are those intended for application in dry form with suitable dusting equipment. Since wind drift is undesirable when applying dusts, the most suitable dust diluents are those which are dense and rapid settling. These include kaolinites, talcs, pyrophyllites, ground phosphate rock, Sericite, and ground tobacco stems. However, dusts are usually most easily prepared by diluting an existing high-strength wettable powder with a dense diluent so that the final dust will frequently contain a fraction of light, absorptive diluent as well as the more desirable dense filler.

A wetting agent is desirable in dust formulations so that adhesion to dew-covered foliage is enhanced. Dusts made from wettable powders will usually contain sufficient wetter, but dusts made directly from unformulated active can contain an added wetting agent. Dry solid anionic or nonionic wetters are preferred.

Dust formulations will normally contain from 5.0. ; weight percent to 25 weight percent of active material, from 0% to 1.0% wetting agent, from 3 to 20$ light grindin aid diluent and the balance dense, rapid settling diluent.

If made by diluting a prepared wettable powder it will also contain a small amount 6f dispersing agent which. has no C. Granules Soil treatments with fungicides can frequently be most readily applied with granules. Granular products wit the complexes of this invention, can' be made in a number of ways. The active materials can be dissolved in a volatile carrier and sprayed upon preformed granules. They may be mixed as powders with suitable diluents and binders, then moistened and granulated followed by drying. Powders may also be applied to preformed granules by tumbling together and applying a binder, for example a nonvolatile liquid such as oil, glycol or a liquid nonionic surfactant. Rates of granule disintegration and dispersion of active material in moist soil can be controlled by choice of added surfactants or selection of the binders used to form the granule.

Suitable preformed granules include those made from attapulgite clay, granular expanded vermiculite, ground corn cobs, ground nut shells or preformed kaolinite granules. When active fungicide is placed upon euch carriers the concentration may range from 1# to 25#. However, it is difficult to prevent segregation of active and carrier in concentration ranges above about 10# on preformed granules. When higher concentrations of active are desired best results are obtained by premixing powdered active, diluents, binders and surfactants then granulating so that the active is distributed throughout the granule and not solely upon its surface .

Suitable diluents for the preparation of granules by granulation or extrusion include kaolin clays, nonswelllng calcium, magnesium montomorrillonltes, and gypsum. Cohesion to a firm granule is usually obtained by moistening compacting and drying, with or without some binding agents. Kaolin clays form firm granules if bound together with gelatinous agents such as methylcellulose, natural clays or swelling and gypeum can be made to form firm granules with either the addition of plaster of Paris or certain salts such as ammonium sulfate, potassium sulfate or urea which form double salts with gypsum.

The active content of formed granules can range from 1-90$ although 75# active represents about the upper level if controlled disintegration of the granule in moist soil is desired. Control of disintegration rate is attained by controlled compaction, e.g., controlled extrusion pressure and by the addition of inert water soluble components such as sodium sulfate which can leach away.

Any of the forms of granules described are suitable for use with the compounds of this invention, the one of choice being dependent upon the intended use.

The following examples illustrate the use of the complexes of this invention. Amounts are in parts by weight unless otherwise noted.

Example l8 Percent 2-Benzimidazolecarbamic acid, methyl 70 ester, 2:1 complex with zinc chloride Alleylnaphthalene sulfonic acid, sodium salt 1.5 Oleyl ester of sodium isethionate 2.0 Diatomaceous silica 26.5 The above components are blended and micro.pul-verized, then remilled in a fluid energy mill until the active fungicide is substantially all below 5 microns.

The resulting wettable formulation is added to water at a rate to provide 300 parts per million by weight of the active component in the total slurry. This dilute preparation is then sprayed on randomly selected apple trees in a commercial orchard. The spray procedure is such as to at the rate of 900 grams per hectare. Applications start at the time that the first spring foliage growth appears and continue at weekly or semimonthly intervals until one month prior to the normal harvest date for apples. At the time of harvest, trees that had been treated in this manner have healthy foliage of good color and provide a good yield of high quality fruit having a good finish. Similar and adjacent trees left unsprayed, on the other hand, have foliage, showing disease caused b the fungi Venturia inaequalis (scab fungus) and Podosphaera leucotricha (powdery mildew fungus). The unsprayed trees yield only a few small fruit with diseased spots caused by the fungus Venturia inaequalis . Thus, the 2-benzimidazolecarbamic acid, methyl ester, 2:1 complex with zinc chloride applied in the form and by the method described effectively prevents damage to crop plants caused by certain fungi.

Example 19 Percent 2-Benzimidazolecarbamic acid, isopropyl- 70 ester, 2:1 complex with zinc bromide Sodium salt of sulfonated lignin 2 Alkylnaphthalenesulfonic acid, sodium salt 1 Kaolin clay (ASP 100-Minerals and Chemicals Co.) 27 Components are blended, mlcropulverized and air milled as in Example l6. The resulting wettable powder formulation is added to water at a rate to provide 1,000 parts per million by weight of active ingredient in the final solution. This solution is sprayed on alternate rows of grape vines in a vineyard at the rate of £00 liters per hectare. Such applications start with the earliest growth In the spring and continue at intervals of 12 to 14 days until harvest time. At harvest time the foliage on the treated vines is healthy and the yield of marketable fruit is high. The alternate unsprayed grape rows, to the contrary, have foliage heavily diseased with powdery mildew (caused by the fungus Uncinula necator) . Thus, the compound of this invention applied in the proper form and by the method described effectively controls powdery mildew.

Example 20 Percent 2-Benzimidazolecarbamic acid, methyl ester, 1:1 complex with copper- ill) monochloride 50 Dioctyl sodium sulfosuccinate 3 Sodium N-methyl-N-pamltoyltaurate (44 ) 4 Sucrose Components are blended and micropulverized, then double air milled for minimum particle size.

This wettable powder is added to water in an amount to provide 300 parts per million of the active component in the final spray suspension. This liquid preparation is then used to spray randomly selected orange trees in an otherwise untreated grove in California. The application volume is at the rate of 6,000 liters per hectare. The first application is made Just after bloom and it is repeated at monthly intervals until harvest time. Frult from tne treated trees retains its quality during transportation and storage. Much of the fruit from the untreated trees is damaged during storage and transit the untreated trace is domagod during storage and fcyam>ll by green mold caused by Fenicllliuni digltatum. Therefore, the compound of this invention applied in the form and by the method described effectively prevents damage by fungi.

Example 21 Percent 2-Benzimidazolecarbamic acid, ethyl ester, , 1:1 complex with zinc monopropionate 70 Dodecyl phenol polyethylene oxide condensate Synthetic fine silica 26 The liquid surfactant is first blended with the active component, followed by the diluent. The mix is then micropulverized and air milled until substantially all of the particles of active ingredient have a particle size less than 3 microns .

The wettable powder thus prepared is added to water in an amount to provide 1,000 parts per million of the active ingredient in the total preparation. This ie used to spray alternate rows in a cherry orchard in Wisconsin. Applications at the rate of 1,000 liters per hectare are made starting with the earliest green tissue in the spring and continuing at intervals of two weeks until just prior to harvest. The rows of trees thus treated remain healthy and vigorous throughout the growing season and produce good quality fruit that keeps well during storage. The trees in the untreated rows show damage to blossoms and fruit caused by the brown rot fungi (Monlllnia fructicola and M. laxa ) . Also, the foliage of the untreated trees is damaged by the cherry leaf spot organism (Coccomyces hlemalls) . The complex of this invention, applied in the proper composition and by the method described protects Example 22 Percent 2-Benzimidazolecarbamic acid, methyl ester, 1:1 complex with copper(lj) mono- acetate Alkyl naphthalene sulfonic acid, sodium salt Attapulgite Micaceous talc The active, attapulgite and surfactant are first blended, micropulverized and air milled. This fine particled product is then blended with the micaceous talc to form a dust.

The active, sugar and surfactant are first blended, micropulverized and air milled. This fine particled product is then blended with the micaceous talc to form a dust.

The above dust is applied with a hand duster to in designated plots with/a large cucumber field. Each applica- . tlon is at the rate of 10 kilograms of the formulation per which hectare. The application is made on the plants/start to form runners and are known to be already infected with the powdery mildew fungus (Eryslphe clchoraclarum) . At harvest the plants within the treated plots are healthy and yield well. The untreated areas outside the plots, on the other hand, contain only cucumber plants heavily diseased with powdery mildew. The compound of this invention formulated and applied as described provides curative or eradicant control of cucurbit powdery mildew.

Example 23 Percent 2-Benzimidazolecarbamic acid, sec -butyl ester, 1:1 complex with zinc, mono- acetate Sodium lauryl sulfate Kaolin clay The first three components are first mixed and finely ground, then blended with the tobacco dust.

Selected plots in a rice field are dusted with the formulation described above employing a hand dust applicator. Application is at the rate of15 kilograms of the formulation per hectare. The first application is made when the rice plants are about 10 inches tall and it is repeated at intervals of two weeks until about 14 days prior to harvest. The rice within the treated plots remains healthy and yields well. The untreated areas outside the test plots, however, are heavily infected with the rice blast fungus (Pirlcularla oryzae ) and provide only a negligible yield of low quality grain. The compound of this invention applied by the method described controls rice blast disease.

Example 24 Percent Wettable powder of Example l5 14.

Expanded vermiculite (0.25-Ο.βθ mm) 77.7 Polyethylene glycol 400 di-trlricinoleate £.0 The wettable powder and vermiculite are first blended briefly. The liquid surfactant is then sprayed upon the tumbling solids to prevent segregation in storage and handling. The resulting granules contain 10 active fungicide.

The above granular formulation is applied to the covering soil in the planting of potato seed-pieces. The granules are dropped over a 10-centimeter band at the rate of 6,000 grams of commodity per 400 meters of row as the covering soil is pushed into place. This results in the applications of approximately JO parts per million of active ingredient in the soil above the seed pieces. Rows treated plants with fungus lesions on the stems near the surface of the soil that yield poorly. The damage in the untreated rows is caused by the soil borne fungus, Rhlzoctonla. The compound of this invention applied in the compositions and manner described protects potato plants from attack by Rhlzoctonla present in the soil.

Example 25 Percent 2-Benzimidazolecarbamic acid, sec-butyl ester, 2:1 complex with zinc chloride 15 Kaolin clay 62 Methyl cellulose (15 cps) The components are blended, micropulverized and air milled. The resulting powder is moistened with l6-200 water and granulated. After drying the granules are screened to recover the fraction having a particle size range of 0.25 to 0.6o mm.

The granular formulation described above is applied to a pasture paddock in New Zealand at a rate to provide 2,000 grams of the active component per hectare. The application is made early in the moist portion of the growing period. Sheep grazing in the paddock remain healthy and grow well. Sheep in an adjacent untreated paddock are unhealthy and develop symptoms known as "face exzema" due to contact with and consumption of mycelia and spores of the fungus Plthomyces chartorum growing on the grass plants. The compound of this invention applied in the composition and by the method described ontrols Plthomyces chartorum.

Claims (1)

1. CLAIMS Complexes of the which R is isopropyl or a is 1 or is zinc or q is whe is copper and q is equal to n when is in which when n is X is chloride ion or and when is X is propionate when is copper and when is X is acetate or Complexes according to Claim being complexes wherein is zinc or copper and X is chloride or Complexes according to Claim being complexes wherein is zinc and X is an acetate or propionate Complexes according to Claim being complexes wherein is copper and X is acetate or A method for preparing complexes according to any of Claims to 4 wherei one or two equivalents of a carbamic aoid of the where R has same meaning as in Claim are reacted with one equivalent of zinc or copper acetate or propionate the presence of Methods for complexes according to any of to substantially as described herein with reference to any of Examples 1 to Fungicidal comprising as an active agent a complex according to Claims Fungicidal comprising as an active agent a 3 comple according to Claims substantially as described Fungicidal comprising as ah active agent a complex according to Claims substantially as described with reference to any Examples 18 to 25 A method controlling in plants or in inanimate comprising applying to the plants or materials a complex according to any of Claims 1 to or composition accordin to Claims 8 or For the Applicants insufficientOCRQuality