DE1957712A1 - Metal complexes of 2-benzimidazole carbamic acid esters - Google Patents

Description

Patent attorneys
. Ing.Waiter AbitZ Dr. Dieter "F. Morf Dr-Hans-A. Brauns

SMfmcJien86, Pienzei »uerstr. 28

November 17, 1969 2821 / 2821-1 / 2-G

EGG. YOU PONO? DE NEMOURS AND COMPANY Wilmington, Delaware 19898, V.St.A.

Metal complexes of 2-benzimidazole carbamic acid esters

Ss was found to be through. Implementation of (l) organic compounds with the general formula ⁱ

H

I Il N-C-O-

where R denotes lower alkyl, metal complexes prepared with (2) metal salts, such as zinc carbonide or copper acetate, can be used as metals.

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The present invention thus relates to a group of Köm · «plexes which are produced by reacting (1) JS-benzimidazole carbamide · acid esters with (2) salts, processes for the production of these complexes and processes for the application of the ser complexes for combating fungi.

The protection of plants and products necessary for satisfaction of basic needs are essential before various means of destruction, such as fungi, is for the People essential to life. Due to the rapidly increasing population of the world, continued improvements in effectiveness * The eligibility of the materials and working methods used to create this protection is imperative. These improvements can take the form of an effective fight against multiple. ren pest species or in the form that less Material or labor is required. The materials and procedures of the invention deliver in both of these possible improvement directions distinct advantages, as will be explained in detail below.

It has been found that the use of the complexes according to the invention according to the working methods according to the invention, the damage to plants and inanimate organic materials by fungi completely excludes or belittles. Fungal mycelia are killed by the presence of one or more of the compounds tet or prevented from further development, i.e. the connection ..

fertilizers are fungicidal or fungistatic. -.

The compounds and methods of operation according to the invention also enable the damage caused by fungi to be combated a surprisingly small amount of chemicals and surprisingly little effort.

It has now been found that an excellent fungicidal Akti can be vitat obtained when the point a · Fungusbefallee an effective amount of a complex tone (1) an or-

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Gallic compound with the general formula I.

wherein R is methyl, ethyl, isopropyl or sec-butyl, and (2) a salt chosen from

(A) zinc chloride (ZnCl ₂ ),

(B) zinc bromide (ZnBr ₂ ) *

(C) zinc acetate [Zn (OC-CH ₅ ) ₂ ],. ·

(D) zinc propionate [Zn (0-C-CH ₂ CH ₃ ) ₂ ],

(E) copper (II) chloride (CuCl ₂ ), (P) copper (I3) bromide (CuBr ₂ ),

0 (G) copper (II) acetate [Cu (OC-CH ₃ ) ₂ J and

0
(H) Copper (II) propionate [Cu (OC-CH ₂ GH ₃ ) ₂ ]. .

is applied.

The most preferred complex is the 2: 1 complex of 2-benzimida-. zolcarbamic acid methyl ester with zinc chloride. <

Έβ it should be noted that benzimidazole carbamates in tautomeric forms, ie,.

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W -te

W-!

W-!

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exist.

The invention is described in detail below.

With the method according to the invention, different com ₇ . plexes are formed. The complexes can be either 2: 1 or; be l: l complexes. A 2: 1 complex is a complex that has 2 molecules of the 2-ben ζ imidazole and 1 molecule of the salt. ·. while a 1: 1 complex contains 1 molecule of the 2-benzimidazole and 1 Mo IeMiI of the salt.

2:! - complexes

Complexes with 2 molecules of 2-benzimidazole carbamate and 1 molecule The salt can be selected from any suitable 2-benzimidazole carbamate and one of zinc chloride, zinc bromide, copper (II) chloride and copper (II) bromide selected salt can be prepared. The zinc 2: 1 complexes according to the invention have the former Formula II

Il

- O - R

ZnX,

(II)

where R is methyl, ethyl, isopropyl or sec-butyl and X is chlorine or bromine.

They copper 2: 1 complexes have the chemical formula III

0-R

Ou

- 5 -

R-O-ö-N-d

(III)

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where R is methyl, ethyl, isopropyl or sec-butyl and Y is chlorine or bromine.

The exact chemical structure and bonding of these 2; 1 complexes * is not known with certainty, but in the case of the zinc complexes it is believed that the salt is probably associated with four coordinate bonds attached to the 2-benzimidazole carbamate is. The zinc 2: 1 complexes can thus provide the general Structural formula IV

have, in which R and X have the meanings given above ", ben.

It is thus assumed that a 2-benzimidazole carbamic acid '' methyl ester-2zl complex with zinc chloride has the formula V: * '

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- O - C

- O - CH,

(V)

It should be noted that in the case of these zinc 2: 1 complexes Metal is in the form of an electrically neutral salt.

The exact chemical structure of the copper 2: 1 complexes is true also not known, but it is believed that they have the general structural formula VI

R-O-

-D-R

(VI)

in which R is methyl, ethyl, isopropyl or sec-butyl and Z is chlorine or bromine, can be represented. It is believed that three coordinate and one ionic bond link the Eupfer atom and the BenBimidazole carbamic acid group.

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A methyl 2-benzimidazole carbamate 2: 1 complex with copper (II) monochloride has the formula VII

(VII)

1;! - complexes

Complexes with 1 molecule of 2-benzimidazole and 1 molecule of metal salt can be selected from any suitable 2-benzimidazole and one of zinc acetate, zinc propionate, copper (II) chloride, copper (II) bromide, Copper (II) acetate and copper (II) propionate selected salt are produced. You have one-to-one complexes chemical formula VIII

- 0 - R

(viii;)

where R is methyl, ethyl, isopropyl or sec-butyl, M _{1 is} zinc or copper and X is acetate or propionate when M is zinc, and chlorine, bromine, acetate or propionate when M _{1 is} copper . As in the PalIe of the lil complexes insecure. The lil complexes can struc- '

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door IX have:

O - O - R

(IX)

where R is methyl, ethyl, isopropyl ■ or sec-butyl, M ₁ zinc or copper and X, when E is zinc, acetate or propionate, or, when M is copper, chlorine, bromine, acetate or propionate " A mean 2-Benzimidazolcarbamidsäuremethylester-l. l-Kom plex with copper (II) monoacetate can follow ones shown, · provides are:

• N,

σ - ο -

(X)

CH ₃ -CO

In this pail the salt is ionic and coordinative Bond bound to the 2-benzimidazole carbamate. Since zero, If an acetate ion is present, the 1: 1 complex is converted to methyl 2-benziimidazole carbamate-ltl complex with copper (II) - 'designated monoacetate.

The complexes according to the invention are prepared by reacting a 2-benzimidazoloarbamic acid ester of the formula I with one of the eight salts given above. The reaction can be carried out in such a way that a slurry of the 2-Benss-

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imidazole carbamate reacted with an aqueous solution of the salt will.

When carrying out the reaction, the order of addition is not critical. In some cases this is 2-benzimidazole carbamate difficult to wet with a concentrated solution of the salt. In these cases it is advantageous to use the Wet 2-benzimidazole carbamate thoroughly with water first before mixing it with the saline solution. It is also possible, although not necessary, an organic solvent, such as ethyl acetate, to wet the benzimidazole carbide ^ amats to use. The solvent can be used during the subsequent Implementation are left in the reaction mixture.

The concentration of the 2-benzimldazole carbamate 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 view of the large amount of water that must be used and the size of the equipment required. Concentrations above about $ 20 are difficult to stir effectively. The concentration of the metal salt is not critical, although preferably concentrated or saturated solutions be used, for example, 66 wt .-? 6 or more in the case of zinc chloride "the salt solutions often ψ Because a large excess of metal salt contain, it is economically advantageous, all filtrates to be recovered for use in subsequent implementations. Concentrated solutions are preferred, but good results can also be obtained when using dilute solutions of the salt. The total amount of metal salt present in the reaction mixture can vary from the theoretical amount to an excess of well over 1000 pounds.

The particle size of the 2-BenzimidazoloarbamatB suspended in the metal salt solution is not critical. Small particle sizes are advantageous with a view to increasing the

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Reaction rate, however, the 2-benzimidazole can be difficult to wet with the salt solution if the particle sizes are very small. Accordingly, inert wetting, dispersing or emulsifying agents can in some cases be useful in improving the reaction conditions.

The time required to complete the implementation is not critical and can be, for example, a few seconds vary up to 16 hours or more. Many factors influence the reaction time, for example temperature, concentration of the reactants, particle size of the 2-benzimidazole carbamate and the same. In either case, the optimal conditions can be determined experimentally. the Completeness of implementation is best determined by the appearance and disappearance of certain peaks in the IR spectrum, as described below in the examples.

The temperature at which the reaction takes place is in some cases important with regard to the product formed, while in other cases the temperature only influences the rate of the reaction. For example, a 1: 1 complex with copper (II) monochloride is obtained in the reaction of 2-benzimidazole carbamic acid esters with copper (II) chloride at a temperature of about 100 ^{0, while a 2: 1 complex is obtained at room temperature} with copper (II) chloride, as shown in Examples 3 and 4 below. The reaction temperature can generally between about Raumtem- 'temperature and about 130 ⁰ O vary.

The presence of foreign ions, for example those which are generated during the preparation of the 2-benzimidazole carbamic acid esters from alkyl chloroformates, cyanamide and o-phenylenediamine, do not interfere with the formation of the coupling. It is therefore not necessary to purify the 2-benzimidazoloarbamate used as starting material before the start of the reaction.

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

The following examples illustrate the preparation of the complexes of formula I. The | specified "amounts ~ J are parts by weight, unless otherwise specified.

example 1

Preparation of 2-benzimidazole carbamic acid methyl ester-2: 1-. · Complex with zinc chloride

573 parts of 2-Benzimidazolcarbamidsäuremethylester are with. . a solution of 273 parts of zinc chloride mixed in 2500 parts of water. The mixture is refluxed with vigorous stirring heated and held at reflux temperature for 30 minutes. Then the mixture is cooled and filtered and the filter cake is washed thoroughly with water and dried to give 696 parts of product.

In the infrared spectrum the peaks are at 5.84 and 7.90 / u,. which are characteristic of the methyl 2-benzimidazole carbamate are no longer present and there are new peaks at 5.75 and 8.07 / u. that are characteristic of the zinc chloride complex. This product can be used as such or in a formulated form for application against fungi, even if it contains about 10 % of the starting material.

Analysis ; Calculated for a mixture of 90% by weight of the 2: 1 ester / zinc chloride complex (O ₁₈ H ₁₈ N ₆ O ₄ ZnOl ₂ ) and 10% by weight of organic starting material

CHN Cl Zn 43.15 3.6 16.8 12.3 11.3 %

found for the product of example 1: 42.92 3.61 16.58 12.63 11.3 t

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The above product is purified by extracting 5.0 parts of the material with 200 parts of boiling acetonitrile

and filtering the hot mixture. The insoluble material (0.5 parts) shows an IR spectrum which is similar to that of des. '. 2-Benzimidazole carbamic acid methyl ester is identical. That Acetonitrile filtrate is reduced to a small volume in vacuo. centered, cooled and the precipitated solid (4 parts after air drying) is collected on a filter. It consists of pure white, flaky needles and its IR spectrum is essentially the same as that of the raw product (characteristic peaks at 5.75 and 8.07, u). Evaporation the mother liquor provides a further 0.5 parts of a somewhat impure product.

The air-dried needles set according to the analysis, a PRP. · Domestic product represents, which is about $ 2> water contains' as the following results.

Analysis ; Calculated for the methyl 2-benzimidazole carbamate 2: 1 complex with zinc chloride (C ₁₈ H ₁₈ N ₆ O _{4 ZnOl 2} ), which contains 2 $> water:. '

σ 3 H 15th N Cl 4th 12th Zn 40, 9 3 , 65 15th , 91 13, 12th 12th , 35 41-, 19th , 40 , 91 13, , 3

found:

The complex probably has the formula III shown structure. '

Example 2

Preparation of ethyl 2-benzimidazole carbamate 1: 1 complex with zinc monoacetate

57 parts of methyl 2-benzimidazole carbamate are mixed with a solution of 367 ropes of anhydrous zinc acetate in 600 ropes of water. The slurry is under vigorous

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Stirring heated to reflux and refluxed for 2 1/2 hours kept river temperature. The mixture is then cooled, filtered, the pest is washed thoroughly with water and air-dried. The product consists of 70 parts of a white powder. The IR spectrum shows characteristic peaks at about 5.7 and 8, l, u. Peaks at 5.84 and 7.90 λι, the are characteristic of the organic starting material are not available.

Analysis ; Calculated for. the methyl 2-benzimidazole carbamate l: l complex with zinc monoacetate (C ₁₁ H ₁₁ N ^ O.Zn), which contains 1.5 $> H ₂ O:

C H N Zn

41.4 3.6 13.55 20.5 # found: 41.34 3.94 13.56 19.26

This complex probably has the following structure:

(XI)

Example 3

Production of ^ -Benz'imidazolcarbamidsäuremethylester-III complex with copper (II) monochloride

To a solution of 340 parts of copper (II) chloride dihydrate in 250 ropes of water, 57 parts of finely ground methyl 2-benzene imide sulfamic acid are added. The mixture is

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stir and heat on a steam bath for 4 hours. The very dark reaction mixture is cooled and diluted with water, which changes the color to green. The mixture is filtered and the pesticide is washed thoroughly with water and air dried, being 57 parts of the product, a green powder.

analysis

calculated: found:

37.3
37.09

3.1 3.68

14.5 % 14.53

The infrared spectrum shows characteristic peaks at 5.75 and 8.04 / U. This complex probably has the formula:

C-O-CH,

(XII)

Example 4

Preparation of 2-benzimidazole carbamic acid methyl ester 2: 1 complex with copper (II) monochloride

57 parts of finely divided methyl 2-benzimidazole carbamate are added to a solution of 340 parts of copper (II) chloride dihydrate in 400 parts of water. The mixture is stirred at room temperature for 16 hours, then filtered, the solid is washed with water (the color changes from green to brown) and then with acetone and air-dried. The infrared spectrum shows a peak at

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5.85 / U, which is much stronger than that of the starting material,
and a characteristic peak at 8.05 / rev.

Analysis : Calculated for methyl 2-benzimidazole carbamic acid. ester-2: l complex with copper (II) monochloride (
which contains 1 1/2 f> H ₃ O .:

C H N

44.3 3.9 17.2 #

found: 44.29 3.98 17.37

Example 5

Preparation of 2-benzimidazole carbamic acid isopropyl ester-2: 1 complex with zinc chloride

31 parts of isopropyl 2-benzimidazole carbamate are added. 200 parts of water are stirred until the pesticide is thoroughly wetted and suspended in the water. Then a solution of
191 parts of zinc chloride in 380 parts of water are added and the mixture is refluxed with stirring. After refluxing for 2 hours, the mixture is cooled and filtered and the pesticide is washed with water and dried to give 37 parts of the product as a white pesticide. The IR spectrum shows characteristic peaks at
5.75 and 8.05 / U and very weak peaks at 5.9 and 7.9 / U, which indicate the presence of some organic starting material

The product in this package is in contrast to Example 1
insoluble in acrylonitrile (and acetone), while the starting material (the isopropyl ester) is soluble in acetonitrile and especially in acetone. The crude product is therefore stirred in 300 parts of acetone to remove the organic starting material, filtered, washed with 300 parts of acetone and dried. The infrared spectrum shows the peaks at

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5.9 and 7.9 / u no longer, but the strong peaks are at 5.75 and 8.05 / U still available.

Example 6

Preparation of 2-benzimidazole carbamic acid methyl ester 2: 1 complex with zinc chloride starting from a crude aqueous slurry of methyl 2-benzimidazole carbamate

79.5 parts of methyl chloroformate and 131 parts of 50% sodium hydroxide are added simultaneously with thorough stirring to a solution of 34.6 parts of cyanamide in 165 parts of water. The separate rates of addition are regulated so that the pH remains between 6.5 and 7.5. The temperature is maintained by external cooling at 50 ⁰ C or less.

To this reaction mass are added 75.3 parts of o-phenylenedlamine and enough concentrated hydrochloric acid to give a pH of 4.0. The mixture is then heated and ^{stirred for 1 hour at 95 °} C., while the pH is kept at 4.0 by intermittent addition of concentrated hydrochloric acid. The resulting slurry contains 123.0 parts of 2-benzimidazole carbamic acid methyl ester.

275 parts of zinc chloride are added to the hot slurry. The mixture is stirred for another 20 minutes at 95 ° C, cooled to 50 ^0C and filtered. The product is washed with water and dried ^{at 100 °} C. in a vacuum oven. The infrared spectrum of this product is identical to that of Example 1.

Example 7 to 17

Using the specified starting materials and the Procedure in the example given, various complexes according to the invention are prepared.

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example

ο I. O H co O ro I. to cn K> O -a

10

11th

Working method of example

Raw materials

(a) 2-Benzimidazole carbamic acid methyl ester

(b) zinc bromide

(a) 2-Benzimidazole carbamic acid methyl ester

(b) zinc propionate

(a) 2-Benzimidazole carbamidsätireätb-ylester

(b) zinc chloride

(a) - 2-Benzimidazole carbamic acid ethyl ester

(b) copper (II) chloride

(a) Isopropyl 2-benzimidazole carbamate

(b) copper (II) chloride

resulting complex

2-Benzimidazole carbamic acid methyl ester 2: 1 complex with zinc bromide

2-Benzimidazole carbamic acid methyl ester 1: 1 complex with zinc monopropionate

2-Benzimidazolcarbamidsäu re-ethyl ester 2: 1 complex with zinc chloride

Ethyl 2-benzimidazole carbamate 1: 1-component with copper (II) monochloride

Isopropyl 2-benzimidazole carbamate 2: 1 complex with copper (II) monochloride

1 \ 5

ω ro

-ν »ro

Example How Example works

12th

σ ι ο H co VO CO I. fs » Oil ro ο

13th

16

Continuation of starting materials

(a) Isopropyl 2-benzimidazole carbamic acid ester

(b) Copper (II) chloride

(a) 2-Benzimidazole carbamic acid sec-butyl ester

(b) zinc chloride

(a) 2-Benzimidazole carbamic acid methyl ester

(b) copper (II) bromide

(a) 2-Benzimidazole carbamic acid methyl ester

(b) copper (II) propionate

(a) 2-Benzimidazole carbamic acid methyl ester

(b) copper (II) bromide

(a) 2-Benzimidazole carbamic acid methyl ester

(b) copper (II) acetate

resulting complex

Isopropyl 2-benzimidazole carbamate 1: 1 complex with copper (II) monochloride

2-Benzimidazole carbamic acid sec-butyl ester 2: 1 complex with zinc chloride

2-Benzimidazole carbamic acid methyl ester-2: l-complex: with copper (II) bromide

2-Benzimidazole carbamic acid methyl ester 1: 1 complex with copper (II) monopropionate

2-Benzimidazole carbamic acid methyl ester 1: 1 complex with copper (II) monobromide

2-Benzimidazole carbamic acid methyl ester 1: 1 complex with copper (II) monoacetate

ro H

ro Φ no H

- ^. ro

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The complexes according to the invention can be used for combating the influences or effects of fungi.

There are many fungi that the complexes are active against. Examples of this are the following, albeit this list is not a restriction: Venturia inaequalis, which causes apple scab, Podosphaera leucotricha, which causes Apples cause powdery mildew, Uromyces phaseoli, which causes bean rust, Cercospora apii, the early fire in celery caused, Septoria apii-graveolentis, the late fire at Celery causes, Sclerotinia slerotiorum, the white mold

P mel causes in beans and other crops, Cercospora musae, which causes sigatoka disease in bananas, Monilinia fructicola and M. laxa, the brown rot in stone fruits cause, Erysiphe cichoracearum, which causes powdery mildew in cantaloupe and other pumpkin fruits, Penicillium digitatum, which causes green mold in citrus fruits, ·. Sphaerotheca humuli, which causes powdery mildew in roses, Diplocarpon rosae, which causes star soot in roses, Unicinula necator, which causes powdery mildew in grapes, Coccomyces hiemalis, which causes cherry leaf spots, Oladosporium carpophilum, which causes peach scab; Pithomyces chartorum, which grows on lawns and pasture grasses

* and indirectly causing disease in sheep, Erysiphe graminis hordei, which causes mildew in barley, Piricularia oryzae, which causes rice blight, Puccinia rubigovera tritici, P. Coronata and P. glumarum, which cause leaf rust in wheat, oats and grasses, respectively, Puccinia graminis tritici, which causes stalk rust in wheat, Aspergillus niger, the cotton boll rot and rot in the wake of a, Injury to many plant tissues causes Aspergillus terreus common in the soil and plant matter attacks different species of Rhizoctonia, Fusarium and Verticillium that are present in the soil and the roots or other subterranean dent in a variety of plants

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attack different types of Penicillium that are on objects such as fabrics, fibreboard, leather articles and paints, and Myrothecium species that grow Attack objects such as shower or rain curtains, carpets, mats and clothing.

When used by means of the methods according to the invention, the complexes according to the invention enter the plants and move freely therein, ie they are systemic. Fungi can thus be controlled in parts of plants that are removed from the application parts. With regard to such a movement, the complexes can advantageously be applied to certain seeds or seeds, for example the treatment of cucumber seeds with a few grams per kilogram of a compound according to the invention provides control of powdery mildew (Erysiphe cichoracearum on the resulting Plants for periods of time over 40 days. Applications to the soil also provide control of certain leaf diseases in plants growing in the treated soil. Spray or dust treatments of plant leaves give other leaves of the plant that have not actually been sprayed are, and the later developing leaves protection against fungi.

There are significant practical advantages associated with the use of an effective systemic fungicide. Successful application to seeds, as described above, results in great cost savings in terms of chemicals and. Use. Ground applications to protect in an efficient way, the entire plant for an extended span tent, bring also similar savings. The distribution within the plant following treatment of the leaves eliminates the need for frequent renewed treatment to protect rapidly growing tissue. Materials within the plant are also not removed by rain. The movement or relocation of the chemical

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within the plant can also protect the parts of the plant that could not be covered by the original spray application. This is of particular importance in Plants with a dense growth character that allows penetration. of the spray material, and also with large plants, like shade trees where the spray material does not reach the top.

Another valuable property of the complexes according to the invention is their ability to prevent the spread of a fungus infectious disease. * tion that is already present within a plant, or to kill such a fungus infection, i.e., it are healing. The complexes therefore do not need to be applied until conditions that correspond to actual ones have developed Allow onset of fungus attack. This means that in some circumstances it is possible to use avoiding a chemical throughout the life of the crop or harvest. In other cases it is only one Part of the normal full pesticide application required. It is therefore with connections that are systemic and have healing effects, both in terms of chemical costs and application work possible.

w The complexes of the invention provide protection against damage caused by fungi if the procedures described below and are applied in an amount sufficient to the right place according to the desired fungicidal activity exercise. They are particularly suitable for protecting living plants, such as fruit-bearing trees, nut-bearing trees, ornamental trees, forest trees, vegetable plants or crops, horticultural plants or crops (including small plants and berries), fiber plants and crops, grain and seed harvests, sugar cane, sugar beet, pineapple, fodder and hay harvests, beans »peas, soybeans, peanuts, potatoes, potatoes, tobacco, hops,

Lawn and pasture grass.

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Live plants can be protected from fungi by one or more of the complexes according to the invention on the soil in which they grow or in which they subsequently become Can be sown or planted, or on seeds, bulbs, bulbs or other plant propagation parts before Planting as well as on leaves, stems and fruits of the living. applied to the plant. Live plants can too protected by immersing the root system or the chemical or chemicals in roots or stems physically introduced.

Applications to the ground are made with dusts, granules, tar pellets, slurries or solutions. Preferred Application amounts of the compounds according to the invention. Soil in which plants are present or will grow in the range of 1 to 200 ppm by weight of the soil in which the Roots are present or will grow. More preferred use amounts are in the range from 2 to 50 ppm.

Preferred application amounts for seeds, tubers, bulbs or other parts of plant reproduction are in the range of 50 to 2000 g of the active compound of the invention per 50 kg of treated planting material. More preferred amounts are in the range of 100 to 1000 g of active compound per 50 kg. The applications are made from dusts, slurries or Solutions. Such treatments protect the treated parts themselves from damage by fungi and also impart extended protection to the resulting new plants.

Preferred amounts for the application of the compounds according to the invention to leaves, stems and fruits of living plants are in the range from 20 to 4000 g of active constituent per hectare. More preferred amounts range from 40 to 2000 grams per hectare. The optimal amount within this range depends on a number of variables known to those skilled in the crop protection art. to

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These variables include, but are not limited to, the disease to be controlled, the expected weather conditions, the type of plant, the stage of development of the plant and the space between applications. It may be necessary that applications are within the specified range repeated once or many times at intervals of 1 to 60 days.

Preferred amounts for immersion applications on roots of living plants are in the range of 20 to 1000 g more active Component per 100 liters of water or other liquid vehicle. More preferred amounts range from 40 to 500 grams per 100 ltr.

Preferred amounts for introduction or injection into the. Roots or stems of living plants are in the area from 1 to 1000 ppm water or other liquid vehicle.

Plant parts, such as fruits, tubers, onions, roots and the » Same that have been harvested as food or putter are treated with an active according to the invention Complex protected from rot and other destruction caused by fungi during processing, distribution and storage will. The parts of the plant to be protected in this way can be immersed in * a liquid bath containing the active ingredient, dusted with a finely divided preparation of the active ingredient, sprayed with an aerosol, which the complex contains, misted or in Umhüllungs- or Packmat'erialien impregnated with the active complex.

When a liquid bath is used, it can contain an amount of the active ingredient in the range of 1 to 5000 ppm by weight of the liquid.

Dusts as well as wrapping or paok materials »those for this

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Application type can be used, 0.1 to 10 # of the active Component included.

Wood, leather, fabric or tissue, fiberboard, paper and other industrial materials of an organic nature can be protected from decomposition or discoloration by fungi through coating, incorporation. processing and impregnation with an effective amount of one or. several of the complexes of the invention are protected. That
Coating can be done by dipping, spraying, pouring over the material to be protected in .. a suitable composition containing the active ingredient,
is misted (for example with an aerosol) or dusted.

If incorporation or impregnation methods are to be used, the application rates may be greater than those specified in the to
protective material introduced amount of active ingredient
be expressed. The preferred application amounts for these types of application are in the range from 0.001 to 0.1
Wt .- # of active ingredient in the final product.

A surface treatment is carried out by dipping, washing,
Spray, aerosol or dust applications. Spray, dip and washing compositions contain the active complexes according to the invention in amounts of 10 to 5000 ppm. Flowable media
for aerosol application and dusts contain 0.1 to 20 wt. ,

Painted surfaces can prevent unsightly stains--. , formation and mold growth are protected by in the. · Paint formulation before application 5 to 2000 ppm
an active complex according to the invention can be incorporated. Such treatments with the complex according to the invention
also protect the paint while it is still in the can ^. exists, before the destruction or deterioration by Fungi / ¹

They bind complexes according to the invention, as already mentioned above, '

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Particularly suitable for use with living plants, · Application to the leaves, stems and fruits of Pflan zen with the amount specified above is generally carried out using spray preparations, dusts or aerosols, which contain the appropriate amount of active ingredient. To "combat fungi that are regularly present, the" '" Applications often before the point in time when the problem did- '. occurs and are carried out according to a predetermined plan continued. Such a method is called preventive or 'protective,

^ With the complexes according to the invention can also be successful. before control of plant diseases can be achieved if the applications are carried out after they are present. Fungus mycelia within the plant tissue are actually killed. This behavior or effect is said to be healing or eradicating and allows the user to make substantial savings.

The curative control of plant diseases with the inventive Complex will improve when treated. Plant parts for one or more periods of time from 2 to 12, Hours soon after the active compound has been applied. Often times this is done by slowly drying one original spray treatment or by naturally occurring rainfall, fog, haze or dew. Among other Circumstances, for example during dry periods or in shelters such as greenhouses, it is necessary to keep the plants take special precautions to keep moist at best. Achieve results. ·

The curative disease control with the complexes according to the invention is improved if a suitable amount of a ·. selected surfactant is introduced into the Sprühpräparat or in the dust, the or applied to the plant "The bevorzugtesten grenefläohenak-

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Active agents for this purpose include modified phthalic acid glycerine alkyd resins, glycol esters, ethoxylated fatty acids. ren, alcohol sulfates, lecithin and lecithin derivatives, isethionates, certain phosphate derivatives and taurates. Somewhat less preferred, but nonetheless effective, surfactants include sulfosuccinate derivatives, ethoxylated fatty acid esters and oils, ethoxylated alcohols, and dodecyl and tridecylbenzenesulfonates and free acids. Examples of special acids. specific surfactants in each of these various categories are compiled in "Detergents and Emulsifiers, 1967 · ■ Annual ¹ *, edited by John W. McCutcheon, Inc.,"

The preferred amounts for these surfactants when used in spray formulations are in the range of 10 to 1000 ppm of the spray fluid. .

Pure dusts are the preferred amounts of surface-active ·; ven agents in the range from 1000 to 100,000 ppm of the actual ■ ". lent applied material. '

As already mentioned above, the complexes according to the invention are systemic, which is why applications can be carried out on plants by spraying or dusting parts above ground, such as leaves, stems and fruits. In such applications, the presence of a surfactant in the spray or dust "increases the activity. The application amounts for the surfactant here are the same as for the spray preparations and dusts for preventive or curative control described above. The systemic effect When treating above-ground parts, the smoothness on the treated surfaces is also increased for one or more periods of time of 2 to 12 hours each.

The eyetemisohe control of fungi on plants is also

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by applications on seeds, tubers, bulbs or other reproductive parts before planting and by application the chemical reaches the soil in which the plants to be protected exist or will grow. The applica- Propagation parts before planting are done by using spray preparations, immersion preparations, dusts or aerosols which contain one or more of the compounds according to the invention. The soil is treated ' by physically mixing before planting, by distributing. development in the furrow at the time of planting, through application in the water used in transplanting, by placing it in the ground in a tape or in a film with a special Equipment, by introduction by irrigation water "or by distribution on the field surface.

Compositions or agents can be formed by a inventive complex is mixed with an auxiliary. The complexes according to the invention can often advantageously be used in combinations or mixtures with one or more of the fungicides, bactericides, insecticides, acaricides or nematocides used ". available in the market. The combinations. · Or mixtures can be used by the user immediately before use (for example in the container of a spray device) or by the manufacturer or a later processor can be incorporated into a single composition. Examples of the materials used in such combinations

or mixtures can be introduced are:

1,2,3,4,10,10-hexachloro-l, 4,4a, 5 1 8,8a-hexahydro-l, 4-endoexo-5,8-dimethanonaphthalene (Aldrin). ·

1,2,3,4,5, e-hexachlorocyclohexane (lindane),

1,2,4,5,6,7,8,8-octachlor-2,3,3a, 4,7,7a-hexahydro-4 »7-mβthatlO-inden (Chlordane),

l, l, l-trichloro-2,2-bis- (p-chlorophenyl) -ethane (DDT),

1,4-endoexo-5,8-dimethanonaphthalene (Dieldrin),

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1,2,3,4,10,1O-hexachloro-6,7-epoxy-1,4,4a, 5,6,7,8,8a-ootahydrol, 4-endoendo-5,6-dimethanonaphthalene (Endrin), ".

l (or 3a) ^^, o ^ S ^ -heptaohlor ^ a ^^^ a-tetrahydro - ^^ · -. ·· methanoinden, '.

l, l, l-trichloro-2,2-bis (p-methoxyphenyl) ethane (methoxychlor), ' , 2-bis- (p-chlorophenyl) -ethane (TDE), '"

chlorinated camphene with a chlorine content of 67 Ms 69 i » (loxaphen),

chlorinated derpenes with a chlorine content of about 66 Ji · ' (Strobane ^), '' * ·

2-nitro-l, 1-bis- (p-chlorophenyl) -butane, l-liaphthyl-N-methylcarbamate (carbaryl), · ·

Methyl carbamic acid ester with 4- (dimethylamino) -3,5-dimethylphenol,

Methyl carbamic acid ester with 1,3-dithiolan-2-one oxime, methyl H-methylthiöl carbamate,

Methyl methylthiol carbamate,

0, O-diethyl 0- [2-isopropyl-4-methylpyrimid-6-yl] thiophosphate (Diazinon),

0, O-dimethyl-1-hydroxy-2,2,2-trichloroethylphosphonate,

0, O-dimethyl-S- (1,2-dicarbethoxyethyl) dithiophosphate. (MaIathion),

0, O-dimethyl-Op-nitrophenylthiophosphate (methyl parathion) »0,0-diethyl-Op-nitrophenylthiophosphate (parathion), 0, O-dimethyl-O- (3-chloro-4-nitrophenyl) thiophosphate _f

Di ^ -cyclopentenyl ^ -hydroxy-S-metbyl ^ -cyclopenten-l-onchrysanthemat,

0,0-dimethyl-O- (2,2-dichlorovinyl) -phosphate (BlNF),

Mixture containing 53.3 % "Bulan", 26.7 t "Prolan" and 20.0 ί vtr- * '. contains turned compounds,

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O, O-dimethyl-O- (2,4,5-trichlorophenyl) -phosphorothioate,

0, O-Dimethyl-S- (4-oxo-1,2,3-benzotriazine-3 (4H) -yl-methyl) -phos phorodithioate (Guthion v-9),

Bi B- (dimethyl amino) -pho s'phonigsäureanhydrid,

0, O-diethyl-0- (2-keto-4-methyl-7-a »-pyranyl) thiophosphate, OjO-diethyl-CS-ethylmercaptomethylJ-dithiophosphate. (Phorate),.

Calcium arsenate,

Sodium alumiriof luoride, dibasic.ee lead arsenate,

2 «-chloroethyl-l-methyl-2- (p-tert.-butylphenoxy) ethyl sulfite,

Azobenzenes

A * ethyl-2-hydroxy-2,2-bis (4-chlorophenyl) acetate,

0,0-diethyl-0- (2- (ethylmercapto) -ethyl) -thiophosphate,

2,4-dinitro-6-sec-butylphenol, O-ethyl-O-p-nitrophenylbenzenethiophosphonate (BPN), 4-chlorophenyl-4-chlorobenzenesulfonate, p-chlorophenylphenylsulfone,

Tetraethyl pyrophosphate,

1,1-bis (p-chlorophenyl) ethanol,

l, l-bis (chlorophenyl) -2,2,2-trichloroethanol,. .

p-chlorophenyl-p-chlorobenzyl sulfide, Bis (p-chlorophenoxy) methane, 3- (l-methyl-2-pyrrolidyl) pyridine,

mixed esters of pyrethrolone and cinerolone keto alcohols. and two chrysanthemum acids,

Cube * and Derris, both whole roots and pulverized, Ryanodine,

Mixture of alkaloids known as veratrine, dl ^ -alllyl ^ -hydroxy ^ -methyl ^ -cyclopenten-l-one, esterified with a mixture of ice cream and tranB-dl-Ohryeanthömummonooar * carboxylic acids,

* a poisonous American tropical plant ·, special dtr genus LoQohooarpue (? am. Oaeealpiniaoea ·).

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Butoxy polypropylene glycol,

p-dichlorobenzene, · ·

2-butoxy-2-thiocyanodiethyl ether, Naphthalene,

1, l-dichloro-2,2-bis- (p-ethylphenyl) -ethane, p-Mmethylaminobenzoldiazo-sodium sulfonate, Quinonoxyaminobenzooxohydrazone, tetramethylthiuram monosulfide, Tetramethylthiuram di-sulfide (thiram),

Metal salts of ethylene bisdithiocarbamic acid, e.g. manganese,

Zinc, iron and sodium salts,

Pentachloronitrobenzene, 2,3-dihydro-5-carboxyanilido-6-methyl-1,4-oxathiin, n-Dodecylguanidine acetate (Eodin), N-Trichloromethylthiotetrahydrophthalimide (Captan),

Phenyl mercury acetate, _ ^

2,4-dichloro-6- (o-chloroanilino) -s-triazine (Dyrene ^),

N-methylmercury-p-toluenesulfonanilide, Chlorophenol mercury hydroxides, nitrophenol mercury hydroxides,

Ethyl mercury acetate,. "

Ethyl mercury 2,3-dihydroxypropyl mercaptide,

Methyl mercury acetate, ^

Methylmercury-2,3-dihydroxypropylmercaptid (Ceresan ^ L), 3,3'-ethylene-bis- (tetrahydro-4,6-dimethyl-2H-l, 3, 5-thiadiazine

2-thione (Cylan®),
Methylmercury dicyandiamide, ₍

N-ethylmercury-p-toluenesulfonanilide, 1,4-dichloro-2,5-dimethoxybenzene (Chloroneb),

Metal (e.g. iron, sodium and zinc), ammonium and amine salts of dialkyldithiocarbamic acids,

Tetrachlomitroanisole, hexachlorobenzene, Hexachlorophene, Methyl mercury bilbemitrile,

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Tetrachloroquinone,

N-trichloromethylthiophthalimide, 5-ethoxy-3-trichlorine thyl-1,2,4-thiadiazole, 1,2-dibromo-3-chloropropene, dichloropropane / dichloropropene mixture, Ethylene dibromide,

l-chloro-2-nitropropane, chloropicrin,

Sodium dimethyldithiocarbamate, tetrachloroisophthalonitrile,

2-Carboxyamino-1-benzimidazolecarboxylic acid dimethyl ester, ·.

Streptomycin,

2- (2,4,5-trichlorophenoxy) propionic acid, '.

p-chlorophenoxyacetic acid, 1-naphthalene acetamide, N-1-Naphthylacetamld, S-Methyl-N - [(methylcarbamoyl) -oxy] -thiolacetimidat,

S-methyl-N - [(carbamoyl) oxy] thiol acetimidate,. . _t

Sulfur,

Fixed copper (fixed coppers) and copper lime broth (Bordeaux broth).

The additional pesticides are used in mixtures or combinations in amounts ranging from 1/10 to 10 times the
Amount of the compound or compounds according to the invention. turns. The appropriate choice of the amounts of added pesticides will be made by those skilled in the art of protecting ·. Plants easily hit from damage by pests. '

The use of pesticides such as those enumerated in. . Combination with a compound of the invention appears
sometimes to greatly increase the activity of the compound of the invention. In other words, it sometimes becomes an unexpected ·. Dead activity level observed when another peetioid "

Buaammen is used with a compound of the invention

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Specific examples of useful combinations are given below and mixtures given along with representative, but, non-limiting uses:. . '

(a) 2-Benzimidazole carbamic acid methyl ester 2: 1 complex with, ■ Zinc chloride and garbaryl in proportions in the range of 1: 5 to 1: 1 for use on green beans to control white mold (Sclerotinia sclerotLorum) along with. ' Insects like the spotted ladybug and earth fleas. If aphids are to be expected, parathion can also occur or Diazinonvü / der.Mixture in amounts in the range from 1/10 to 1/2 the amount of carbaryl are added. The methyl 2-benzimidazole carbamate 2: 1 complex with ·. Zinc chloride in the mixture can be replaced by other compounds according to the invention.

(b) 2-Benzimidazole carbamic acid isopropyl ester 2: 1 complex with zinc bromide and DDT in ratios in the range from 1: 6 to 1: 1 for use on apple trees to control diseases such as scab and powdery mildew as well as a variety of Insects including the apple wiokler, the fall caterpillar and the larvae of apple mites (apple red bug). The 2-benzimidazole carbamic acid isopropyl ester 2: 1 complex with zinc bromide in the combination can by other invention, appropriate connections are replaced. The DDT can be through meth-. oxychlor or Buthion ^ / to be replaced. TDE can be used in the the same amount as the other insecticide can be added, if the red-banded leaf curler is a particular problem represents. Thiram may mix in the same ' Amount as the compound according to the invention can be added in order to combat certain late salon fruit spot diseases to improve. '*

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(c) Methyl 2-benzimidazole carbamate 1: 1 complex with copper (II) monochloride and KeIthane ^ S / Dicofol in ratios in the range from 1: 5 to 1: 1 for use in pumpkins Combating powdery mildew and leaf spider mites \ ·· The 2-benzimidazole carbamic acid methyl ester 1: 1 complex with copper (II) monochloride can be replaced in this combination by any other compound according to the invention.

(d) Ethyl 2-benzimidazole carbamate 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, late burn, early burn (Alternaria), anthracosis (Oolletotrichum) and rough leaf spots (Stemphylium) includes. Lannate ^ Methomyl can of the mixture can be added in insecticidal quantities to combat tomato, fruit worms and hawk worms. The ethyl 2-benzimidazole carbamate 1: 1 complex with zinc monopro— ·. pionate can be added to the mixture by any other according to the invention Connection to be replaced.

(e) 2-Benzimidazole carbamic acid methyl ester 1: 1 complex with copper (II) monoacetate and EPN in ratios in the range from 1: 6 to 1: 1 for use on vines in the field to control powdery mildew and to control cross-cut, ten grape moth. The 2-benzimidazole carbamic acid methyl. Ester-1: 1 complex with copper (II) monoate can be used in such a combination by any other according to the invention. ' Connection to be replaced. Oaptan and Folpet can do that Combination in quantities * ranging from 1/2 to 4 times. are added to the amount of the compound according to the invention, to give improved grapevine rot control.

(f) 2-Benzimidazolcarbamidsäure-sec-butyleater-l l-complex with Zinkmonoacetat together with dodine and wettable sulfur * ■ in ratios Bereioh of 1: 3: 8 to 1: 1: 6 for the · ";

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excellent control of scab, powdery mildew, black rot, grate cones and prospect eye leaf spots. In the-" Other compounds according to the invention for the 2-benzimidazole carbamic acid sec-butyl ester 1: 1 complex can be used in similar combinations can be used with zinc acetate.

(g) 2-Benzimidazole carbamic acid 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 for control from powdery mildew and anthracosis as well as from insects such as owl butterfly caterpillars (cut worms), Lygus bugs and caterpillars. Copper sulfate or streptomycin sulfate can be added to the combination in active concentrations when bacterial diseases are to be considered. In such combinations, other compounds according to the invention can be used for the 2-benzimidazole carbamic acid sec-butyl ester 2: 1 complex with zinc chloride.

Compositions or agents according to the invention can formu-; be lated by a complex according to the invention with other auxiliaries, such as one or more surface-active agents, is mixed.

The surfactants used in the present invention can be wetting, dispersing or emulsifying agents. They can serve as wetting agents for wettable powders and dusts or as dispersants for wettable powders and granules. Surface-active agents can also increase the biological activity of the 2-benzimidazole carbamic acid ester-metal complexes according to the invention. The / -like surfactant may include such anionic, cationic and nonionic agents as have heretofore been generally used in similar type control agents for plant diseases. Suitable surface- active agents are, for example, in "Detergents and

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Emulsifiers Annual -. 1967 _"f John W. McGutcheon, Inc ,, beschrie ben Other surfactants not listed in this reference, represent the basis of the protective colloid effect is still effective dispersants include methyl cellulose, polyvinyl alcohol, hydroxyethyl cellulose and alkyl-substituted polyvinylpyrrolidones.

Suitable surface-active agents for use in compositions according to the invention include polyethylene glycol esters with fatty and resin acids, polyethylene glycol esters with alkyl phenols or with long-chain aliphatic alcohols, polyethylene glycol ethers with sorbitan fatty acid esters and polyoxyethylene thioethers. Other suitable surfactants include alkali and alkaline earth salts of alkylarylsul-. . ' fonsäuren, alkali metal and Erdalkalifettalkoholsulfate, dialkyl esters of Alkalimetallsulfosuccinaten, fatty acid ester of alkali and Erdalkaliisäthionaten and -tauraten, alkali metal and alkaline earth metal salts of lignosulfonic acids, methylated, or hydroxyäthylierte cellulose, polyvinyl alcohols, alkyl substituted polyvinyl pyrrolidone, alkali and alkaline earth of polymerize alkylnaphthalenesulfonic acids and long chain quaternary ammonium compounds. Anionic and nonionic surfactants are preferred.

Preferred wetting agents are sodium alkylnaphtha- g linsulfonate, sodium dioctyl sulfosuccinate, sodium dodecylbenzenesulfonate, ethylene oxide condensates with alkylated phenols such as octyl, nonyl and dodecyl phenol, sodium lauryl sulfate and

Trimethylnonyl polyethylene glycols. Preferred dispersants are sodium, calcium and magnesium lignin sulfonates, low viscosity methyl cellulose, low viscosity polyvinyl alcohol, alkylated polyvinylpyrrolidone, polymerized alkyl naphthalene sulfonates, sodium N-oleyl or N-lauryl ethionates, sodium N-methyl-N-palmitoyl taurol ester, sodium N-methyl-N-palmitoyl taurol ester, sodium N-methyl-N-palmitoyl taurol.

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Compositions according to the invention contain for the production, of wettable powders, dusts or granules, if desired, solid diluents in addition to the surface-active agents.

(A) Wettable powders

Wettable powders are compositions which usually contain inert solid diluents in addition to surfactants. These inert diluents can serve a variety of purposes. They can act as grinding aids to prevent smearing in the mill and clogging of the sieve, they can quickly disperse the mixture. support after introduction into water, they can _liquid-# Siges or low melting solid active material to form a free-flowing solid product adsorb, they can prevent agglomeration into lumps in long hot storage and them. may allow the preparation of compositions with a regulated amount of active ingredient so that the correct dosage is easily metered out by the consumer.

Suitable diluents can be either inorganic or organic in origin. These include the natural clays, diatomaceous earth, synthetic mineral fillers derived from silica or silicon dioxide or silicates, insoluble salts produced by precipitation in flaky form, such as tricalcium phosphate or potassium carbonate, and powdery organic diluents such as shell meal, wood flour or corn flour Sucrose. Preferred fillers for the compositions according to the invention include kaolir clays, attapulgite clays, non-swelling calcium-magnesium montages. morillonite, synthetic silica, synthetic calcium and magnesium lumellicates, diatomaceous silica, corncob meal and sucrose.

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Wettable powders usually contain both a wetting agent and a dispersing agent. Most preferred for dry wettable powders are the solid anionic and nonionic surfactants. Occasionally a liquid, nonionic surfactant, which is normally regarded as an emulsifying agent, be used to generate both wetting and dispersion ^1.

In wettable powders according to the invention, wetting * and dispersants together about 0.5 to 5.0% by weight of the total composition the end. The active component is in a concentration of about 25 to 90 # and the rest to 100 # ' consists of thinner. If necessary, a ·. Corrosion inhibitor or a foam inhibitor in amounts of 0.1 to 1.0 96 with a corresponding reduction in the diluent can be added.

When surfactants are used to increase biological activity, they are most commonly considered to be a separate component is added to the spray container and they are usually in concentrations of 50 to 1000 ppm based on the water in the container.

'(B) dusts

Dust compositions are for application in dry ·. in a form with suitable atomizing equipment. Since wind downforce is undesirable when applying dust, dense and rapidly settling dust diluents are the most suitable. These include kaolin, talc, pyrophyllite, ground phosphate rock, sericite and ground tobacco stalks. Dusts, however, are usually most easily produced by diluting a present highly concentrated wettable powder with a diluent diluent so that the final dust often becomes a

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Contains fraction of light absorbent diluent and the more desirable dense I ¹ UlIstoff.

A wetting agent is desirable in dust formulations to increase adhesion to dew-covered leaves. Dusts made from wettable powders usually contain sufficient wetting agent, while dusts made directly from unformulated powders Active material produced dusts may contain an added wetting agent. Dry solid anionic or nonionic wetting agents are preferred.

Dust formulations usually contain 5.0 to 25 wt .- ^ active material, 0 to 1.0 Ji wetting agents, 3 to 20 light $> Mahlhilfsverdünnungsmittel and remaining dense, rapidly sedimenting diluent. If they are made by diluting a prepared wettable powder, they also contain a small amount of dispersant which has no active role to play when the. Composition is used as a dry dust.

(C) granules

Soil treatments with fungicides are often easiest to use with granules. Granular products with the complexes of the invention can be made in a number of ways. The active materials can be dissolved in a volatile carrier and sprayed onto preformed granules. They can be used as a powder with suitable diluents. materials and binders mixed, then moistened and granulated and then dried. It can aufgebracht.werden also PUI ₇ ver on preformed granules, by being rounded up, and a binder is applied, for example, a nonvolatile liquid, such as oil, glycol, or a liquid nonionic surfactant you · speed of Granulaauflösung and Dis persion of the active material in wet soil can be duroh

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the choice of surfactants added or regulated by the choice of binders used for Formation of the granules are used.

Suitable preformed granules include those formed from attapulgite clay, granular expanded vermiculite, ground corn on the cob, ground nutshells, or preformed kaolinite granules. If active Pungicid is brought to such a carrier, the concentration in the range of 1 to 25 may be 1 ". However, it is difficult to prevent separation of active material and carrier in concentration ranges above about 10 »on preformed granules. When higher concentrations of active material are desired, best results are obtained when powdered active material, diluent, binder and surfactant are premixed and then granulated so that the active material is distributed within the granules, not just on their surface.

Suitable diluents for making granules by granulation or extrusion include kaolin clays, non-swelling calcium-magnesium montmorrillonites and gypsum. The cohesion for forming a solid grain becomes common obtained by moistening, compacting and drying with or without some binders. Kaolin clays form solid granules, when used with gelatinous agents, such as methyl cellulose, natural Clays or swelling bentonite are bonded together, calcium-magnesium bentonites do not require a binding agent and plaster of paris can be obtained either by adding plaster of paris or by adding certain salts, such as ammonium sulphate, or potassium sulphate Urea, which form double salts with gypsum, can be made to form solid granules.

The content of the granules formed of active material can be in the range of 1 to 90 i ", although 75 i" active material represents approximately the upper concentration when regulated

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lated dissolution of the granules in moist soil is desirable. The rate of dissolution is controlled by controlled compaction, for example by controlled Extrusion pressure, and by adding inert water-soluble components, such as sodium sulfate, which are washed out can, achieved.

All of the forms of granules described are suitable for use with the compounds according to the invention, the aus-; chosen form depends on the intended application.

The following examples illustrate the use of the complexes according to the invention. The quantities given are parts by weight, unless otherwise stated.

Example 18

2-benzimidazole carbamic acid methyl

ester-2: l complex with zinc chloride. 70

Alkylnaphthalenesulfonic acid sodium salt 1.5

Oleyl ester of sodium isethionate 2.0

Diatomaceous earth 26.5

The above components are mixed and micropulverized and then re-milled in a jet mill until the active fungicide is essentially below 5 / U total.

The resulting (wettable) formulation is added to water in an amount to provide 300 ppm by weight of the active component in the total slurry. This diluted preparation is then sprayed onto randomly selected apple trees in a commercial orchard. The spraying process is such that it leads to the application of liquid in the amount of 3000 liters per hectare . The active component is thus applied in an amount of 900 g per hectare. The Appiika

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tions begin at the time when the first spring,. leaf growth occurs, and are repeated at weekly or bi-monthly intervals up to a month before normal ■ · Harvest time for apples continued. At harvest time, trees treated in this way have healthy foliage with good color and gives a good yield of fruits with high quality and good taste. Similar and unsprayed In contrast, neighboring trees that have been left in place have foliage that shows diseases caused by the Fungi Venturia inaequalis (scab fungus) and Podosphaera leucotricha (powdery mildew) are caused. The unsprayed trees yield only a few small fruits with disease spots that through Fungus Venturia inaequalis. The 2-benzimidazole carbamic acid methyl ester 2: 1 complex with zinc chloride thus effectively prevents damage to crops caused by certain fungi when used in the described Form and according to the method of operation described is applied. '

Example 19

Isopropyl 2-benzimidazole carbamate 2: 1 complex with zinc bromide 70

Sulfonated lignin sodium salt 2

Alkylnaphthalenesulfonic acid sodium salt 1

Kaolin clay (ASP 100-Minerals and Chemicals Co.) 27

The components are mixed, micropulverized and air-milled as in Example 18. The resulting wettable powder formulation is added to water in an amount to provide 1000 ppm by weight active ingredient in the final solution. This solution is sprayed in an amount of 800 liters per hectare on alternating rows of grapevines in a vineyard. Such applications begin früheβten growth in Prühlung and fortgesetet in intervals 12-14 ₁ Say to aur harvest time. It is harvest time

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The foliage on the treated vines is healthy and the yield of marketable fruits is high. In contrast, the alternating, unsprayed rows of vines have foliage that is seriously affected by powdery mildew (caused by the fungue üncinula necator). The compound according to the invention thus combats powdery mildew in an effective manner when it is used in the suitable form described and in accordance with the procedure described. *

Example 20

2-Benzimidazole carbamic acid methyl ester-l: l-

Complex with copper (II) monochloride 50

Dioctyl sodium sulfosuccinate 3

Sodium N-methyl-N-palmitoyl taurate (44, 56) 4

Sucrose 43

The components are mixed and micropulverized and then subjected to double air milling treatment to achieve minimum particle size.

This wettable powder is added to water in an amount to provide 300 ppm 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 California grove. The application volume is 6000 liters per hectare. The first application is carried out immediately after flowering and repeated at monthly intervals until harvest time. Fruits from the treated trees maintain their quality during transportation and storage. Much of the fruit from the untreated trees is damaged during storage and transport by green mold caused by Penicill ium digitatum. The compound according to the invention applied in the form described and in accordance with the method of operation described therefore effectively prevents Sohädi

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by Fungi.
Example 21

Ethyl 2-benzimidazole carbamate-l: l-

Complex with zinc monopropionate 70

Dodecylphenol polyethylene oxide condensate 4

synthetic fine silica 26

The liquid surfactant mixes with the active first Component mixed followed by the diluent. The mixture is then micropulverized and air milled, until virtually all of the particles of the active ingredient have a particle size below 3 / U.

The wettable powder so prepared is then added to water in an amount to provide 1000 ppm of the active ingredient in the total preparation. This is used to sprinkle alternate rows in a cherry orchard in Wisconsin. Applications in an amount of 1000 liters per hectare are carried out, starting with the earliest green tissue in the spray and continued at intervals of two weeks until immediately before the harvest. The rows of trees so treated remain healthy and vigorous during the growing season and produce good quality fruit that stays well during storage. The trees in the untreated rows show damage to flowers and fruits caused by the brown rot fungi (Monilinia fructicola and M. laxa). The foliage of the untreated trees is also damaged by the cherry leaf spot organism (Coccomyces hiemalis). The complex of the invention protects, when in the appropriate composition and according to the procedure described is applied, cherry trees from attack by fungi.

. - 44 -00982B / 2072

2821 / 2821-1 / 2-G Example 22

2-Benzimidazole carbamic acid methyl ester-l: l-

Complex with copper (II) monoacetate 10

Alkylnaphthalenesulfonic acid sodium salt 0.5

Attapulgite 10.0

Glimmertalk 79.5

The active component, attapulgite and surfactant are first mixed, micropulverized and aired ground. This product, in the form of fine particles, is then used to form a dust preparation with the mica talc mixed.

The above dust preparation is applied with a hand dusting device to designated areas in a large cucumber field. Each application takes place in an amount of 10 kg of the formulation per hectare. The application is used with the Plants which are beginning to form runners and which are known to have already developed with powdery mildew (Erysiphe cichoraciarum) are infected. When harvested, the plants within the treated areas are healthy and bearable Well. In contrast, the untreated areas outside the spots only contain cucumber plants, which are difficult are sick with powdery mildew. The compound according to the invention, formulated and used in the manner described, provides curative or eradicating control of cucumber powdery mildew.

• Example 23

2-Benzimidazole carbamic acid sec-butyl ester: 1 complex with zinc monoacetate 5

Sodium Lauryl Sulphate 0.5

Kaolin clay 10

Tobacco stem dust 84 , 5

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2821 / 2821-1 / 2-G

The first three components are mixed and ground first and then mixed with the tobacco dust.

Selected areas in a rice field are dusted with the formulation described above using a hand dust applicator. The application takes place in the amount of iron 15 kg of the formulation per hectare. The first application is made when the rice plants are about 25.4 cm (10 inches) tall and repeated at intervals from 2 weeks to about 14 days prior to harvest. The rice within the treated areas remains healthy and carries well. The untreated areas outside the test areas, on the other hand, are strongly mi +; Rice blight fungus (Piricularia oryzae) infect and provide negligible yield of low quality grains. The compound according to the invention applied in accordance with the method of operation described thus combats rice blight »

Example 24

wettable powder of Example 18 expanded vermiculite (0.25-0.60 mm) Polyethylene glycol 400 ditriricinoleate

The wettable powder and vermiculite are first mixed briefly. The liquid surfactant is then sprayed onto the solids moving in the drum to prevent separation during storage and handling. The resulting granules contain $ 10 active fungicide.

The above granular formulation is applied to the top soil when planting pieces of potato seed. The granules are scattered over a 10 cm band with the amount of 6000 g of material per 400 m row, while the covering soil is pushed in place. This results in applications of about 30 ppm active ingredient in the soil above the

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14, 3 77 7th 8th, 0

2821 / 2821-1 / 2-G

Saw pieces. Rows treated in this way produce healthy ones Plants that bear well. In contrast, neighboring untreated rows produce yellowish plants with fungus injuries on the stems near the surface of the soil, which bear poorly. The damage in the untreated rows is caused by the fungus Rhizoctonia produced in the soil. The in the compositions described and in the The compound according to the invention applied in the manner described protects potato plants from attack by in the soil present Rhizoctonia.

Example 25

2-Benzimidazole carbamic acid sec-butyl ester 2: 1 complex with zinc chloride 15

Kaolin clay 82

Methyl cellulose (15 cP) 3

The components are mixed, micropulverized and air milled. The resulting powder is moistened with 18-20 # water and granulated. After drying, the granules become sieved to recover the fraction with a particle size range of 0.25-0.60 mm.

The granular formulation described above is applied to a pasture paddock in New Zealand in such an amount that there are 2000 g of the active component per hectare. The application is carried out early in the moist part of the growing season. Sheep grazing in the paddock stay healthy and grow well. Sheep in an adjacent untreated paddock are not healthy and develop symptoms known as "facial eczema" from contact with and ingestion of mycelia and spores of the fungus Pithomyces chartorum that grows on the grass plants. The compound according to the invention used in the composition described and in accordance with the procedure described is combated

Pithomyces chartorum.

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Claims (1)

2821 / 2821-1 / 2-G November 17, 1969 PATENT CLAIMS Complexes of the general formula H
ι \ H O 0 - R ^ -N - σ - ZnX, wherein R is methyl, ethyl, isopropyl or eek-butyl and X is chlorine or bromine. 2. Complex with the formula - O - CH, ZnCl, 3. Complexes with the general formula H
N Vn-cor ₍
r ■ • Cu 0 H Il t R.O-C-N - 48 - 009825/2072 2821 / 2821-1 / 2-G where R is methyl, ethyl, isopropyl or sefc.-butyl and Y is chlorine or bromine. Complexes with the general formula - 0 - R V ⁺ h ' where R is methyl, ethyl, isopropyl or sefc.-butyl, M _{1 is} zinc or copper and X _{1 is} acetate or propionate when M- is zinc, and chlorine, bromine, acetate or propionate when M- is copper . 5. Process for the preparation of complexes, characterized in that that in the presence of water (l) an organic Compound with the general formula Il C-O - R where R is methyl, ethyl, isopropyl or sec-butyl,) and (2) one of zinc chloride, zinc bromide, zinc acetate ,. Zinc propionate, Copper (II) chloride, copper (II) bromide, copper (II) acetate and converting copper (II) propionate selected salt. J; 6. Process for the preparation of the complex according to claim 2, characterized in that in the presence of water (1) the compound having the formula - 49 - 0 0 9825/20 7 2 2821 / 2821-1 / 2-G N-C-O-OH and (2) zinc chloride reacts. 7. Agent, characterized by a content of (1) one Complex according to claim. 1 and (2) an excipient. ^ 8. Means, characterized by a content of (l) dem Complex according to claim 2 and (2) an adjuvant. 9 * Means, characterized »by a content of (1) one Complex according to claim 3 and (2) an adjuvant. 10. Means, characterized by a content of (l) one Complex according to claim 4 and (2) an adjuvant. 11. A method of combating fungi, characterized in that a fungicide is applied to a site to be protected Amount of a complex according to claim 1 applies. W 12. A method for combating fungi, characterized in that a fungicidal amount of the complex according to claim 2 is applied to a site to be protected. j 13. Method of combating fungi, thereby identifying » draws that a fungioid amount of a complex according to claim 3 is applied to a place to be protected » 14 * Method for combating fungi, characterized in that a fungicidal amount of a complex according to claim 4 is applied to a site to be protected. - 50 - 009825/2072