DE965608C - Fungicides - Google Patents

Description

ISSUED JUNE 13, 1957

E 5222 IVa / 451

Fungicides

The invention relates to novel pesticides. In particular, it relates to the protection of substances exposed to fungal attack by incorporating the invention as pesticides effective triazine compounds in these or by applying these compounds on these substances. The invention is also directed to methods of incorporating such compounds into their Use form as a pesticide, as well as methods for their application.

Those forming a large group and as i, 3, 5-triazines or s-triazines known compounds have been used as chemical intermediates for some time known. It was also already known that formaldehyde condensation products of cyanuric acid amide (MeI-amine) as an admixture to pesticides and triallyl ester of cyanuric acid as a pesticide to use. Before the present invention, however, it was not known that certain derivatives of the 1, 3, 5-triazines could also be used as pesticides relatively ineffective surfactants are extremely effective fungicides.

The term "fungicide" includes not only the property of destroying fungi, but also the Property, the germination of the spores or the spore

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to prevent the formation of fungi understood; this property is sometimes called fungistatic designated.

The fungitoxic substances in the pesticides according to the invention are C-substituted i, 3, 5-Triazines, in which at least one substituent Is chlorine and at least one substituent is an arylamine group. Although it is essential that at least such an arylamine group is present on the 1,3,5-triazine nucleus of the compounds according to the invention is, the meaning of the term "aryl" is intended to be omitted one hydrocarbon group still need to be restricted if two such aryl groups are present are these to be identical. So can to the invention, as pesticides effective 1, 3, 5-triazines in which the aryl group is attached the nitrogen atom outside the core is further substituted, negative or other radicals be appended. In addition, such aryl groups are not limited to the phenyl group, as polynuclear aromatic groups function as well and are preferred for some uses.

Among the simpler ones from the group of substances that have been found to be unusually effective the 2-chloro-4, 6-dianiline-s-triazine and the 2, 4-dichloro-6-aniline-s-triazine. The typical examples of the aryl groups attached to at least one of the exocyclic Nitrogen atoms of the pesticides according to the invention can be substituted, include the phenyl, the diphenyl, the a-naphthyl, the / 9-naphthyl, the phenanthryl and the anthracyl groups. In the latter examples, the polynuclear aryl group can be in any of several Positions are attached to the exocyclic nitrogen atom. Hydrocarbon-substituted derivatives the above typical aryl groups can also be used. For example, the aryl group by an unbranched aliphatic radical, such as. B. the methyl, the ethyl, the propyl, the Hexyl or the dodecyl group, or its branched isomers, such as. B. isopropyl, isobutyl, the secondary butyl radical, and the various branched radicals, such as the amyl, the Hexyl and the nonyl radical, as well as higher aliphatic radicals, etc. can be substituted. Farther can these aryl groups by endoaliphatic groups, 'such. B. the methylene, the ethylene, the Propylene and the butylene group, can be substituted to the corresponding phenyl-endomethylene, Phe-

So nyl-endoethylene, hydrindane and tetralin radicals too create. Likewise, the aryl group can be further substituted by the same or a different aryl group. Other examples of such embodiments of the compounds of the invention are those of the abovementioned triazines, in which the hydrogen on the exocyclic nitrogen atom is replaced by acenaphthene and fluorene groups is replaced.

The specific examples of such ^τ > 3.5-triazines which are effective as pesticides according to the invention include 2-chloro-4,6-bis- (p-phenylaniline) -s-triazine, 2,4-dichloro-6- (p-phenylaniline) - s-triazine, 2-chloro-4, 6-bis- (o-phenylaniline) -s-triazine, 2, 4-dichloro-6- (o-phenylanuine) -s-triazine, 2-chloro-4, 6- bis- (cc-naphthylamine) -s-triazine, 2, 4-dichloro-6- (a-naphthylamine) - s - triazine, 2-chloro - 4, 6 - bis - (ß - naphthylamine) -s-triazine, 2, 4-dichloro-6 - (/ S-naphthylamine) -s-triazine, 2-chloro - 4 - aniline - 6 - (a-naphthylamine) - s - triazine, 2-chloro-4- (p-phenylaniline) -6- (ß-naphthylamine) -s-triazine, 2-chloro-4,6-bis- (9-phenanthrylamine) -s-triazine, 2,4-dichloro-6- (p-toluidine) -s-triazine , 2-chloro-4- (2,4-dimethylaniline) -6-aniline-s-triazine, 2,4-dichloro-6- (3-dodecylaniline) -s-triazine, 2-chloro-4,6-bis - (p-cumidin) -striazine, 2, 4-dichloro-6- (4- [mixed] -amylaniline) -striazine, 2-chloro-4-aniline-6- (4-hydrindenylamine) -s-triazine, and 2,4-dichloro-6- (3-acenaphthylamine) -s-triazine.

In addition to such substituents, the aryl groups essential for the 1, 3, 5-triazines according to the invention can be used corresponding unsaturated radicals, such as. B. the vinyl, the propenyl, the alkyl group, etc. contain. Such typical triazines which are effective as pesticides according to the present invention Invention are z. B. 2-chloro-4,6-bis (p-vinylaniline) -triazine, 2,4-dichloro-6- (o-propenyl-aniline) -s-triazine, 2-chloro-4- (o-vinylaniline ) -6-aniline-s-triazine, 2, 4-dichloro-6- (p-allylaniline) -s-triazine and 2-chloro-4, 6-bis- (p-methallylaniline) -s-triazine, 2-chloro-4,6-bis (2-vinyl-a-naphthylamine) -s-triazine and 2,4-dichloro-6- (5-propenyl - /? - naphthylamine) -s-triazine.

However, the invention is not intended to be restricted to substituted i, 3, 5-triazines according to the above information stay. For example, the above aryl groups can be further represented by various negative Radicals are substituted and not only retain their effectiveness as found according to the invention Pesticides, but can in many cases have increased effectiveness and thereby forming a group of pesticides that are intended for certain uses is preferred. Among the examples of such negative groups that are contained in the aryl radicals can include the nitroso, nitro, amino, substituted amino, chlorine, bromine or iodine group as well the hydroxyl, the substituted hydroxyl, azo, cyano, thiocyan, acyloxy, aroyloxy, mercaptyl and substituted mercaptyl group. Furthermore, various combinations of the above can be used Hydrocarbon and negative radicals can be used.

Further examples of the chlorarylamine-i, 3, 5-triazines which are effective as pesticides according to the present invention are 2-chloro-4, 6-bis (4-chloroaniline) -s-triazine, 2,4-dichloro-6- (2-chloroaniline) -s-triazine, 2,4-dichloro-6- (4-bromaniline) -s-triazine, 2-chloro-4-aniline-6- (4-chloroaniline ) -s-triazine, 2-chloro-4, 6-bis- (2, 5-dichloroaniline) -s-triazine, 2-chloro-4- (4-chloroaniline) -6- (4-nitroaniline) -s-triazine; 2, 4-dichloro-6- (4-chloroaniline) - s - triazine, 2, 4 - dichloro - 6 - (p - anisidine) s - triazine, 2-chloro-4, 6-bis- (4-nitroaniline) -s-triazine, 2-chloro-4, 6-bis- (4-oxyaniline) -s-triazine, 2, 4-dichloro-6- (a- [4-chloronaphthylamine]) - s-triazine, 2-chloro-4- (o-anisidine) -6- (3-mercaptoaniline) -s-triazine, 2, 4-dichloro-6- (4-aminoaniline) -s-triazine, 2, 4-dichloro-6- (2-dimethylaminoaniline) -s-triazine, 2-chloro-4- (toluidine) -6- (4-nitro-2-chloroaniline) - s - triazine, 2, 4 - dichloro - 6 - (4 - dimethylaminonaphthylamine) -s-triazine, 2-chloro-4, 6-bis- (p-anisi-

din) -s-triazine, 2, 4-dichloro-6- (4 [/ 3-chloroethyl] aniline) -striazine, ζ - chlorine - 4, 6 - bis - (ρ - nitrosoaniline) - s - triazine, 2, 4-dichloro-6- (p-phenylazoaniline) -s-triazine, 2, 4-D1-chloro-6- (i, 2, 3-trichloro-4-nitroaniline) -s-triazine, 2, 4-D1- chloro-6- (i, 3, 4-trichloro-2-nitroaniline) -s-triazine, 2, 4-dichloro-6- (i, 2, 5-trichloro ^ -nitroaniline) -s-triazine, 2-chloro -4, 6-bis- (i, 2, 3-trichloro-4-nitroaniline) -s-triazine, 2-chloro-4, 6-bis- (i, 3, 4-trichloro-2-nitroaniline) -s -triazine, 2-chloro-4, 6-bis- (i, 2, 5-trichloro-4-nitroaniline) -s-triazine, 2-chloro-4- (i, 2, 3-trichloro-4-nitroaniline) -6- (i, 2, 5-trichloro-4-nitroa * iilin) -s-triazine, 2-chloro-4, 6-bis- (p-cyananiline) -s-triazm, 2, 4-dichloro-6 - (p-thiocyananiline) -striazine, 2-chloro-4, 6-bis- (p-acetoxy-o-toluidine) -s-triazine, 2,4-dichloro-6- (p-benzoyloxyaniline) -s-triazine and 2-chloro-4- (4-methylmercaptoanuine) -6- (p-anisidine) -s-triazine.

If you want to protect any material against fungal attack, it is generally not enough to just one To take means that destroy the fungi or their germination or the generation of fungal spores too able to prevent. Other properties, such as B. low mammalian toxicity, long-lasting Weather resistance, the ability not to stain or discolour, low toxicity to plants, low or controlled volatility must be taken into account before a pesticide can find commercial use. From these and for other reasons it is necessary in many cases to use the pesticides according to the invention to include other compounds in addition to the active ingredients. that they give pest control properties. While it is essential that at least one of the exocyclic nitrogen atoms of the pesticides according to the invention have an aryl substituent contains, the second substituent of this nitrogen atom can vary within wide limits without the compound loses the novel property found in accordance with the invention. For example it was found that compounds such as 2, 4-dichloro-6- (N-methylaniline) -s-triazine, 2-chloro-4, 6-bis- (N-methylaniline) - s - triazine, 2 - chlorine - 4, 6 - bis - (N - methyl-2,5- Dichloroaniline) - s - triazine, 2 - chloro - 4 - (N - methylaniline) -6- (a-naphthylamino) -s-triazine, 2-chloro-4- (2, 5-dichloroaniline) - 6 - (N - methyl - ρ - anisidiri) - s - triazine, 2 - chlorine - 4, 6 - bis - (diphenylamine) -s - triazine, 2 - chlpr-4, 6 - bis - (N - methyl - N - [4 - phenylaminophenylamine]) s-triazine and 2-chloro-4- (N- [p-tolyl "| -N- [p-methoxyphenylamine]) - 6 - (4 - nitroaniline) - s - triazine, when used according to the invention, are very strong pesticides are.

In the following examples of methods according to the invention in the production of typisehen Examples of 1, 3, 5-triazines which are effective as pesticides according to the invention all parts and percentages are by weight.

example 1
2,4-dichloro-6- (p-anisidine) -s-triazine

A solution of 75.5 parts of cyanuric chloride in 660 parts of dry benzene was placed in a reaction vessel with a stirrer and brought to a temperature Chilled from 5 to 10 °. A solution of 102 parts of p-anisidine in 440 parts of benzene was during added over a period of 1 hour with vigorous stirring. The mixture was then on 20 to 25 ° heated and stirred for a further 2 hours. The crude reaction product was on a filter collected, with 600 parts of 2N hydrochloric acid and 1000 Washed portions of water and then recrystallized from benzene. The dichloroanisidine triazine was in a yield of 75 parts (49%) as white crystals melting at 167 to 169.5 °.

Example 2
2,4-dichloro-6- (p-chloroaniline) -s-triazine

This compound was prepared according to the procedure of Example 1 using 74.5 parts of cyanuric chloride and 103 parts of p-chloroaniline. The yield of white crystals was 105 parts (95%); Mp. 183 to 185 ⁰ .

Example 3
2,4-dichloro-6- (a-naphthylamine) -s-triazine

A solution of 100 parts of cyanuric chloride in 320 parts of acetone was added to 1000 parts of crushed ice. A solution of 77.6 parts of α-naphthylamine in 120 parts of acetone was added to the vigorously stirred suspension of cyanuric chloride over a period of 2 hours at such a rate that the reaction ^temperature remained at 0-5 °. A solution of 21.7 parts of sodium hydroxide in 412 parts of water was then added over a period of 1 hour and the mixture was stirred for ι hour at a temperature of 0 ° and then for a further 30 minutes at 20 to 25 °. The solid product was collected on a filter, washed with 1500 parts of water and dried. The yield of triazine was 137.3 parts (87%); Mp. 144 to 148 ⁰ .

Example 4
2,4-dichloro-6- (jö-naphthylamine) -s-triazine

This compound was prepared according to the procedure of Example 3 using 100 parts of cyanuric chloride and 77.6 parts of β-naphthylamine. The yield of white crystals was 156 parts; M.p. 156 ⁰ .

Example 5
2,4-dichloro-6- (p-toluidine) -s-triazine

This compound was prepared according to the procedure of Example 3 using 144 parts of cyanuric chloride and 107.1 parts of p-toluidine. The yield of white crystals was 192.2 parts; Mp. 129 to 131 °. After recrystallization from benzene the product melted at 130-131 ^0th Analysis: Calculated for C ₁₀ H ₈ N ₄ Cl ₂ : Cl 27.8%; found: Cl 27.5%.

Example 6

2, 4 "dichloro-6- (N-methylaniline) -s-triazine

This compound was prepared using 110.7 parts of cyanuric chloride and 64.3 parts of N-methyl

aniline prepared by the method of Example 3. The yield of triazine was 135.2 parts; Mp. 118 to 126 ⁰ . After recrystallization from benzene, the product melted at 131 to 132 ⁰ .
5

Example 7

2-chloro-4, 6-bis- (2, 5-dichloroaniline) -s-triazine

In a reaction vessel with a stirrer, a suspension of 2760 parts of cyanuric chloride in 40,000 Parts of water made at a temperature of 3 to 8 '. The stirred suspension were during over a period of 30 minutes 4900 parts of solid 2, 5-Dichloranüin added. After that became a solution of 2520 parts of sodium bicarbonate in 20,000 parts of water were added. The reaction temperature was increased to 45 ° and held at 45 to 50 ° for 2 hours. After cooling to 25 ° was the product collected by filtration, washed with water and dried. The yield of white Crystals was 6700 parts (96.5%); Fp. 192 to

194 ⁰ . Analysis: Calculated for C ₁₅ H ₈ N ₅ Cl ₅ : 040.7%; found: Cl 41.3%.

Example 8

2-chloro-4, 6-bis- (p-nitroaniline) -s-triazine

This connection was made using

2760 parts of cyanuric chloride and 4150 parts of p-nitroaniline prepared by the procedure of Example 7.

The yellow product yield was 5700 parts; Mp. 382-383 ^0th

Example 9 2-chloro-4,6-bis- (p-anisidine) -s-triazine

This compound was prepared according to the procedure of Example 7 using 55.4 parts of cyanuric chloride and 76 parts of p-anisidine. The yield was 89 parts (83%); Fp. 200-201 ^0th

Example 10

2-chloro-4, 6-bis- (p-chloranuine) -s-triazine

A solution of 51 parts of cyanuric chloride in 250 parts of acetone would be added to 800 parts of crushed ice. With vigorous stirring, 70 parts of p-chloroaniline were added and the mixture was stirred for ι hour at a temperature of 5 °. A solution of 22 parts of sodium hydroxide in 250 parts of water was then added over a period of one hour. The reaction was brought to completion by stirring at 45 to 50 ° for one hour. After cooling, the product was collected on a filter, washed with water and dried. The yield of white crystals was 99 parts (98%); Mp. 218-219 ⁰ .

Example 11 z-Chloro-4,6-bis (aniline) -s-triazine

This compound was prepared according to the procedure of Example 10 using 69.3 parts of cyanuric chloride and 70 parts of aniline. The yield of white crystals was 109 parts (99 ° / _0); Mp 194-195 °. Analysis: Calculated for C ₁₅ H ₁₂ N ₅ Cl: CI 11.9%; found: Cl 11.5 "/".

Example 12

2-Chloro-4, 6-bis- (a-naphthylamine) -s-triazine This compound was prepared by treating cyanuric chloride with a-naphthylamine by the procedure of Example 10 in a yield of 99% and as white, at 209-210 ⁰ melting crystals obtained. Analysis: Calculated for C ₂₃ H ₁₆ N ₅ Cl: Cl8.91%; found: Cl 8.94%.

75 Example 13

2-chloro-4, 6-bis- (N-methylaniline) -s-triazine

This compound was obtained by treating cyanuric chloride with N-methylaniline by following the procedure of Example 10 in a yield of 89% and as white crystals melting at 84.5 to 87 °. Analysis: Calculated for C ₁₇ H ₁₆ N ₅ Cl: Cl 10.8%; found: Cl 10.8 ° / ₀ .

Example 14 ^8s

A solution of 73.8 parts of cyanuric chloride in 310 parts of acetone was placed in a reaction vessel which was provided with a stirrer, a temperature measuring device and a device for cooling the contents of the vessel and which contained 1000 parts of crushed ice. A solution of 51.2 parts of o-chloraniline in 150 parts of acetone was slowly added to the vigorously stirred suspension of the cyanuric chloride. After the o-chloroaniline had been added, a solution of 16 parts of sodium hydroxide in 300 parts of water was added over the course of half an hour. After this period of time, the temperature of the reaction mixture was allowed to rise to about 20 ° and the reaction mixture was stirred for a further hour. The precipitated 2,4-dichloro-6- (2-chloroaniline) -s-triazine was collected by filtration, washed with water and dried. The yield of the crude product, suitable for most uses, was 136 parts, which corresponds to a yield of 98.7 percent. After recrystallization from a mixture of benzene and isohexanes, the melting point of the crystalline product was 155 to 157 ⁰ . This material was found by analysis to contain 38.1% chlorine while the formula C ₉ H ₅ N ₄ Cl ₃ requires 38.6%.

In addition to the amino group, the 1, 3, 5-triazines which are effective as pesticides must be added of the present invention contain at least 1 chlorine atom on one carbon atom of the triazine nucleus. Whether ι or 2 chlorine atoms and one or two arylamino groups are provided depends largely on the type of application as well as the particular fungal organism that is destroying or affecting the The aim is to prevent the generation of spores. It has been found that all of the various embodiments of the triazines according to the invention, which are effective as pesticides, have little or no selectivity in their effectiveness Own mushrooms opposite. Since with regard to the

ratio in which the pesticides according to the invention attack different fungal organisms, there is a measurable difference, this can easily determined by experiment. This difference is of degree, and provided that that the minimum amount of pesticide is applied is ensured by any of the invention Means against a very large number of fungal organisms achieved a protective effect.

ίο To get out of the above i, 3, 5-triazines inherent effectiveness as a pesticide to be of practical use Compounds of the invention used in conjunction with relatively inert surfactants. In the pure state, the above compounds are far too potent or too potent to be to have any practical utility as a pesticide. For example, a Surface, such as a painted surface or a

ao wood surface or the surface of a fruit, stem or leaf or a concrete surface or Another surface to protect in the most effective way, the substances according to the invention must be thorough distribution on these surfaces are brought into intimate contact with them. It is the same in the treatment of more or less porous material, such as. B. cloth, felt textiles and woven fabrics Fibers, important that the fabrics according to the invention are distributed between the fine structure of these materials and be brought into intimate contact with it. Therefore, a much larger amount of relative inert surface-active agents incorporated into the active substances. Continue to effect such surface-active agents that to achieve a protective effect only very small amounts of connections listed above are necessary. Another benefit of stretching these connections is in that it enables fields to be treated by easily applicable methods, the treated material is still practically completely covered.

One method of using the pesticides of the invention is to Use of an aqueous suspension. For this purpose, according to the invention, one is used for dispersing and suspending the pesticide in a sufficient amount of a surfactant added. Examples of such surfactants used in the preparation of dispersions include salts of alkyl and alkyl aryl sulfonates, alkyl sulfates, alkyl amide sulfonates, the alkylaryl polyether alcohols, the fatty acid esters of polyhydric alcohols, the ethylene oxide addition products such esters and the addition products of long-chain mercaptans and ethylene oxide. Still other surfactants can be used; the above list contains only examples for the commonly used means.

The manufacturing processes described in the preceding examples are referred to in this context Invention claims no protection.

In the examples below, all parts are by weight.

Example 15

To produce a use form of 2-chloro-4, 6-bis- (2, 5-dichloroaniline) -s-triazine, 10 parts of this Compound finely ground and the resulting powder with vigorous stirring to 1000 parts of water added, the part of a Äthylenoxydanlagerungsproduktes to fatty acid ester polyvalent Contained alcohols. This concentrated dispersion was diluted a thousand times by adding water, to obtain a usage form of suitable concentration. Thus the resulting dispersion contained 10 parts of the pesticide according to the invention per million parts of the water dispersion.

In the same way, aqueous dispersions with a concentration of 0.1, 1, 10 and 100 parts / million were made the following pesticides according to the invention prepared: 2-chloro-4, 6-bis- (p-nitroaniline) -s-triazine 2, 4-dichloro-6- (p-chloroaniline) -triazine, 2,4 ~ dichloro-6- (p-anisidine) -s ~ triazine, 2,4-D1-chloro-6- (a-naphthylamine) - s-triazine, 2-chloro-4,6-bis- (2,5-dichloroaniline) -s-triazine and 2-chloro-4,6-bis- (p-anisidine) -s-triazine. Similar aqueous dispersions of the following pesticides according to the invention are also produced with equally good results: 2-chloro-4,6-bis- (9-phenanthrylamino) -s-triazine, 2, 4-dichloro-6- (3-dodecylaniline) -s-triazine, 2-chloro-4, 6-bis- (p-vinylaniline) -s-triazine, 2,4-dichloro-6- (p-allylaniline) -s-triazine, 2-chloro-4-aniline-6- (4 ~ chloroaniline) -s-triazine, 2-chloro-4- (o-anisidine) -6- (3-mercaptoaniline) -s-triazine and 2-chloro-4- (4-methylmercaptoaniline) -s-triazine.

Furthermore, the solubility of s-triazines in organic solvents allows them to be used with advantage Solutions in these types of solvents are used; for certain purposes this Application method preferred. For example, the pesticides of the invention are when treating cloth, leather or other fiber materials in a volatile solvent used solved. After use, the volatile solvent evaporates, leaving the pesticide in place as an impregnation on the entire surface of the object in fine distribution return. Likewise, when using the pesticides according to the invention on smooth surfaces, such as B. in the surface treatment of wood to protect against fungal attack or to prevent it of fungal growth on damp concrete surfaces, the use of a solution is the most practical method be for applying a protective film by brushing on, spraying on or swapping. Choosing one suitable solvent is largely determined by the concentration of the active one to be used Constituent, the required volatility of the solvent, its spray or flow properties and the type of material to be treated. Among the many organic solvents that act as carriers for the pesticides of the invention can be used include hydrocarbons, such as B. benzene, xylene or toluene; Ketones, such as ζ. B. acetone, methyl ethyl ketone and cyclohexanone; chlorinated solvents, such as. B. Carbon tetrachloride

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substance, trichlorethylene and perchlorethylene; Esters such as B. Ethyl, butyl and amyl acetate, and alcohols, such as. B. ethanol, isopropanol and amyl alcohols. Other Usable solvents are the monoalkyl ethers of diethylene glycol and the monoalkyl ethers of Ethylene glycol. In addition, combinations of these various typical solvents can be used which gives the use forms according to the invention special volatility and viscosity properties can be awarded.

Example i6

A solution of 5 parts of 2, 4-dichloro-6- (4-chloroanilino) -s-triazine in 250 parts of cyclohexanone was prepared by I5minutiges stirring the two components at a temperature of about 25 ^0th This concentrated solution, suitable for storage and transportation, was further diluted with 99,750 parts of kerosene to produce a final application dilution of 50 parts / million.

Similar concentrated solutions of 2-chloro-4, 6-dianiline-s-triazine, 2, 4-dichloro-6-aniline-s-triazine, 2-chloro-4, 6-bis- (a-naphthylamino) -s-triazine, 2-chloro ~ 4, 6-bis- (p-vinylaniline) - s-triazine, 2-chloro-4, 6-bis- (2, 5-dichloroaniline) -s-triazine, 2-ChIOr ^ - (o-anisidine) -6- (3-mercaptylaniline) -s-triazine, 2,4-dichloro-6- (N-methylaniline) -s-triazine and 2-chloro-4- (N-methylaniline) -6 - (/ 3-naphthylamino) -s-triazine are ethyl acetate, kerosene, perchlorethylene in each of the following solvents

and monoalkyl ethers, made from ethylene glycol. Ready-to-use solutions are produced with equally good results by adding additional quantities of kerosene.
In addition to the processes described above for the wet application of the 1, 3, 5-triazines, mixtures can be prepared in which the pesticides according to the invention are extended with talc, clay or other solid diluents. Such usage forms are particularly useful in treating seeds where the use of an aqueous usage form can cause premature germination or where the seed can be damaged by application in the form of a solution. Also for use on crops is

♦ 5 in certain cases the dust form preferred, where the Using a wet usage form could cause certain undesirable side effects. More specific examples of such typical inert solid carriers that act as diluents are included the use forms according to the invention can be used in dust form are fuller's earth, Pyrophillite, Attaclay and Fuller's Earth.

Example 17

A use form, in dust form, of one of the pesticides according to the invention was made as follows:

Part of 2-chlorine 4, 6-bis (4-nitroaniline) -s-triazine was ground together with 100 parts of fuller's earth in a cross beater mill for 1 hour and sieved ^{to obtain a material that passed through a sieve with 1600 meshes per cm 2} . This "product containing 1% by weight of active substance" can be used immediately or further diluted. Further dilution was prepared by repeating the above procedure with a further 9900 parts of fuller's earth.

Similar dust usage forms become apparent from the following Compounds made: 2, 4-dichloro-6-aniline-s-triazine, 2, 4-dichloro-6- (a-naphthylamine) -s-triazine, 2,4-dichloro-6- (3-dodecylaniline) -s-triazine, 2-chloro-4, 6-bis- (p-vinylaniline) -s-triazine, 2,4-dichloro-6- (4-chloroanine ) -s-triazine, 2 -Chlor-4- (4-methylmercaptoaniline) - 6 - (p - anisidine) - s - triazine, 2-chloro-4, 6 -bis - (N-methyl-2,5-dichloroaniline) -s-triazine and 2- Chlorine-4,6-bis- (Diphenylamine) -s-triazine, by mixing them in a cross beater mill as above with fuller's earth treated with equally good results.

For certain uses it is preferred to use the pesticides according to the invention to be used in the form of oil-in-water emulsions. So becomes a concentrate of the pesticide made in a water insoluble solvent; this solution is then turned into a surfactant Water containing agents dispersed or emulsified. Among the typical examples of such Solvents include hydrocarbons, such as. B. kerosene, benzene or naphtha; higher alcohols, like z. B. butanol, oleyl alcohol or ethers and esters of these, and chlorinated solvents, such as. B. perchlorethylene and trichlorethylene.

Example 18

An oil-in-water emulsion was made by dissolving 10 parts of 2,4-dichloro-6- (a-naphthylamino-s-triazine produced in 1000 parts of kerosene. This solution was stirred vigorously in 99,000 parts of water, containing a part of an alkylaryl polyether alcohol, dispersed to give a dispersion of 100 parts / To get a million of the active agent. If similar solutions of 2, 4-dichloro-6-aniline-s-triazine, 2-chloro-4-aniline-6- (4-hydrindenylamine) -s-triazine, 2,4-dichloro-6- (o-propenylaniline) -s-triazine, 2-chloro-4,6-bis- (2-vinyl-a-naphthylamine) -s-triazine, 2-chloro-4, 6-bis- (p-cyanoaniline) -s-triazine, and 2,4-dichloro-6- (p-benzoyloxyaniline) -s-triazine in kerosene, naphtha and trichlorethylene when subsequently dispersed in water are prepared in the same way obtain satisfactory emulsions.

It has further been found that it is possible to use a combination of the above application methods for to use the pesticides according to the invention. So can a surfactant be incorporated into the dust-use forms according to the invention to form a wettable powder result, which can then be suspended in an aqueous or other liquid medium. from Particularly useful for such forms of use are the alkyl- or alkyl aryl sulfonates.

Example 19

A mixture of 100 parts of 2, 4-dichloro-6- (p-anisidine) -s-triazine, 1000 parts of Attaclay and 0.1 part of one

Cleaning agents based on alkylarylsulfonate were ground in a cross beater mill and the resulting powder was passed through a sieve with 1600 meshes per cm ² . This 100% wettable powder gave a perfect water suspension when two parts of this powder were stirred in 10000 parts of water to produce a suspension with 100 parts / million active ingredient. Similar wettable powders with fuller's earth, fuller's earth and pyrophyllite are made by grinding 2-chloro-4, 6-bis- (N-methyl-2, 5-dichloroaniline) -s-triazine, 2, 4-dichloro-6- ( a- (4-Chloronaphthylamino)) - s-triazine, 2-chloro-4-aniline-6- (4-chloranilm) -s-triazine, 2-chloro-4,6-bis- (p-cyanoaniline) -s -triazine, 2,4-dichloro-6- (5-propenyl- | 8-naphthylamino) -s-triazine, 2,4-dichloro-6- (a-naphthylamino) -s-triazine and 2-chloro-4- (2,4-dimethylaniline) -6-aniline-s-triazine and emulsifier produced; after grinding they are sifted.

Likewise, one produced with a solvent can be used Usage form used together with water, or water and a surfactant will. Such surfactants are e.g. B. of the type of alkylaryl polyether alcohols, the addition products of ethylene oxide to these esters or to long-chain mercaptans.

Example 20

A solution of 1 part 2, 4-dichloro-6- (p-toluidine) -striazine, 100 parts of ethyl acetate and 0.1 part of an adduct from ethylene oxide to fatty acid esters of polyhydric alcohols was replaced by half an hour Stirring the ingredients at 25 °. This solution was then used to make a for the use of a suitable solution with stirring added 9900 parts of water.

Equally good dispersions are obtained if 2-chloro-4, 6-dianiline-s-triazine, 2, 4-dichloro-6-aniline-s- · triazine, 2, 4-dichloro-6- (p-phenylaniline) -s-triazine, 2, 4-dichloro-6- (o-propenylaniline) -s-triazine, 2,4-dichloro-6- (p-phenylazoaniline) -s-triazine, 2-chloro-4,6-bis- (N-methylaniline) -s-triazine and 2-chloro-4, 6-bis- (2, 5-dichloroaniline) -s-triazine in methanol, acetone and methyl ethyl ketone dissolved together with alkylaryl polyether alcohols and added water with stirring.

Table I.

It has also been found that an adhesive or adhesive, such as. B. vegetable oils, naturally occurring Gums or other adhesives in the 1, 3, 5-triazine usage forms according to the invention can be incorporated. Wetting agents can also be used in the use forms according to the invention will. Furthermore, these usage forms can be mixed with other pesticides or other biocidal agents, such as. B. insecticides, larvae killers, bactericidal agents, Worm and maggot killers or with other substances, together with the invention Pesticides are to be used, such as B. herbicides or fertilizers, be used.

The usefulness of the compounds according to the invention as a pesticide was explained by determining the concentration at which prevents the germination of 50% each of the spores of the fungi Alternaria oleracea and Sclerotinia fructicola will. The former causes the potato melt dew, the latter the peach rot. These mushrooms are representatives of mushroom species that are responsible for severe crop damage. The ability to affect these fungi is a reliable sign of the general applicability of the pesticides according to the invention to protect these and other important agricultural products. These attempts were carried out as follows:

An aqueous suspension of the pesticide in distilled water containing a dispersant was prepared by following the procedure of Example 14 manufactured. This suspension was in various dilutions with one drop of distilled water Added water containing the fungus to be examined and placed on a microscope slide found. In this way, the concentration at which half of the fungi germinated was determined was hindered by spores. This standard method of germination on a slide is through the "Committee on Standardization of Fungicidal Tests" of the "American Phytopathological Society" in "Phytopathology", 33, 627 (1943), has been described and accepted.

No.

Pesticides

Concentration (parts / million)

for contraception
of 50 ¹ Y ₀ of germination

A. oleracea S. fructicola

I.
2

4th
5
6th

2-chloro-4, 6-bis- (2, 5-dichloroaniline) -s-triazine 2-chloro-4, 6-bis- (4-nitroaniline) -s-triazine ...

2,4-dichloro-6- (p-anisidine) -s-triazine

2,4-dichloro-6- (4-chloroaniline) -s-triazine .... 2, 4-dichloro-6- (a-naphthylamine) -s-triazine .. 2, 4-dichloro-6 - (/ 5-naphthylamine) -s-triazine ..

2-chloro-4, 6-bis- (p-anisidine) -s-triazine

2-chloro-4, 6-bis- (4-chloroaniline) -s-triazine
Copper sulfate (common)

less than 1
less than 1
less than 1
less than 1
less than 1

100
10 to 100

100

ι to 10

10 to 100

10 to 100

ι to 10

ι to 10

10 to 100

100

10 to 100
100

Further evidence of the usefulness of the compounds according to the invention as pesticides was determined by the determination of the lowest

amount of active ingredients necessary for preventing spore germination by 95% of the in one Culture existing fungal organisms was required. This provision was based on the same Way done like the above.

Typical of such results is the compound 2-chloro-4, 6-bis- (2, 5-dichloroaniline) -s-triazm, generated a 95 ° / _o strength Keimungsverhinderung with the at a concentration of 10 parts / million, while Copper sulfate was only effective at a concentration of 20 parts / million.

Of particular importance in the treatment of agricultural crops against fungal diseases is the plant's sensitivity to damage from the pesticide used. The compounds according to the invention were particularly advantageous in this regard, since they are very diverse Attempts have not found any signs that they are toxic or toxic to plants that they interfere with the normal life of the plant or the germination of seeds if they are in the mixtures described above can be used. The harmlessness of the forms of use of the The pesticide of the present invention was made one at a time by dipping the whole leaf Corn, soybean, tomato, cucumber and cotton plants in suspensions of the invention Pesticides shown at concentrations up to 10,000 parts / million; there were on no harmful effects were observed on the plants treated in this way or on the leaves that have been immersed. Furthermore, each of these plants was treated with dispersions of the invention without the occurrence of harmful effects Pesticide in water at a concentration of 10,000 parts per million completely sprayed. Even when using the pesticides according to the invention in Lanolin paste form on the stem of young plants of the above species did not become harmful Effects noted.

The protective effect of the pesticides according to the invention against fungal attack in growing plants was demonstrated by controlling the early tomato meltau. In this experiment, the test plants with a o, 2 ° / ₀ by weight concentration of the pesticide are sprayed with spores of Alternaria solani vaccinated and found the number of developed disease damage. Bonny Best tomato plants grown in pots from 7.6 cm in diameter to 10 to 18 cm in size were used as host plants. Three plants with still developing leaves were used for each compound. The intended for spraying o, 2 ° / ₀ by weight suspension of the compounds was converted polyhydric alcohols in all cases to a o, oi ° / ₀ solution with an ethylene oxide-adduct of fatty acid ester. The tomato plants were treated with the pesticide suspension on a turntable using a De Vilbiss paint spray gun. Each batch of plants treated on the turntable was sprayed with 85 ecm of the spray suspension. Under these circumstances there was no significant drainage of pesticide from the plants. With the standard conditions used, a deposit of about 0.0015 g of pesticide per 100 cm ^{2 of} total leaf area (ie upper and lower leaf area) is achieved. After the pesticide deposit had dried, the plants were inoculated with a suspension of spores of the test fungus Alternaria solani. The spores derived from fungal cultures, the 7 to 14 days were drawn at 20 ⁰ to a salt-potato-dextrose agar. 20 ecm of a suspension with 50,000 spores per ecm were used to inoculate each turntable load of plants. The spores were sprayed onto the plants at an air pressure of 0.7 kg / cm ² by means of a De Vilbiss sprayer from a distance of about 30 cm. The upper and lower leaf areas were uniformly inoculated by this method. After inoculation, the plants were placed in an infection chamber which was maintained at a temperature of 20 ⁰ and a ioo ° / ₀ strength relative humidity. After staying in this chamber for 40 to 48 hours, the plants were placed in a greenhouse. Damage usually developed 3 to 4 days after vaccination. The total number of early meltau damage on three pinnate leaves per plant sprayed would be determined. Leaves with the same position on the plant were counted for all treatments and controls. The disease index was determined by dividing the average number of injuries per sprayed plant by the average number of injuries per control plant. For this purpose a number of young tomato plants were infected with Alternaria solani. This attempt is made by Wellman and McCallan in Contrib. Boyce Thompson Inst., 13, 171 (1943), further described.

Table II

No. Pesticides Disease Index Percentage
of damage in comparison
to untreated plants
(Formerly tomato melt dew) I.
2
3
4th
5
6th 2-chloro-4, 6-bis- (2, 5-dichloroaniline) -s-triazine
2-chloro-4, 6-bis- (4-nitroaniline) -s-triazine
2,4-dichloro-6- (p-anisidine) -s-triazine
2,4-dichloro-6- (4-chloroaniline) -s-triazine
Zinc dimethyldithiocarbamate
None (untreated) 6.6
7.6
1.0
31
100

From the above results, it can be seen that the pesticides of the present invention are extremely effective in treating a plant disease under conditions where a commercial pesticide (No. 5) is incapable of acting on the disease. Equally good results are achieved when 2-chloro-4,6-bis (/ ^ naphthylamino) -s-triazine, 2-chloro-4,6-bis- (9-phenanthrylamine) -s-triazine, 2-chlorine -4, 6-bis- (p-vinylaniline) -s-triazine, 2,4-dichloro-6- (5-propenyl- ^ naphthylamine) -s-triazine, 2-chloro-4,6-bis- (p -nitrosoaniline) -s-triazine, 2,4-dichloro-6- (4-aminoaniline) -s-triazine, 2-chloro-4- (N-methylaniline) -6- (ß-

naphthylamine) -s-triazine and 2-chloro-4- (o-anisidine) -6- (3-mercaptoaniline) -s-triazine can be used in the same way.

In general, the pesticides of the invention are effective in a wide range of concentrations. So even at concentrations of 10,000 parts / million of effective pesticides obtained without danger in can be used in agriculture, and will also be used at a concentration of only 0.1 part / million Protective effect achieved. Furthermore, when applied to inanimate objects in certain Cases even higher concentrations can be used, and stable forms of use can be used higher concentration, for storage or transport. In general, however, for the effective use as a pesticide according to the invention the range from 0.1 to 2000 parts / million preferred.

The invention is not restricted to the embodiments described here.

Claims (10)

Patent claims: 1. Fungicidal agents, characterized in that they are a 2-chloro-4, 6-di- (arylamino) -i, 3, 5-triazine or a 2,4-dichloro-6-arylamino-i, 3, 5-triazine, the aryl radical of which is unsubstituted or substituted may be as an active ingredient and a fungicidal relatively inert adjuvant as Contain carrier substance. 2. Fungicidal agents according to claim 1, characterized in that they are used as the active ingredient contain a 2-chloro-4, 6-di- (chloroaniline) -i, 3, 5-triazine or a 2, 4-dichloro-6-chloroaniline-i, 3, 5-triazine. 3. Fungicidal agents according to claim 1, characterized in that they are an active ingredient 2, 4-dichloro-6- (2-chloroaniline) -i, 3, 5-triazine contain. 4. Fungicidal agents according to Claims 1 to 3, characterized in that they are the effective ones Contain ingredients in amounts from 0.01 to 2000, preferably about 10 parts per million. 5. Fungicidal agents according to Claims 1 to 4, characterized in that the carrier substance a surfactant or a diluent is used. 6. Fungicidal agents according to Claims 1 to 5, characterized in that the triazine is an aqueous one Suspension is present in admixture with a surfactant. 7. Fungicidal agents according to claim 6, characterized in that they contain alkyl sulfonates, alkyl aryl sulfonates, Alkyl sulfates, alkyl amide sulfonates, alkylaryl polyether alcohols, Fatty acid esters of polyhydric alcohols or their ethylene oxide addition products or ethylene oxide addition products contain long chain mercaptans as surfactants. 8. Fungicidal agent according to claim 5, characterized in that the carrier substance is a hydrocarbon, such as benzene, xylene or toluene; a ketone such as acetone, methyl ethyl ketone or cyclohexanone; a chlorine-substituted solvent such as carbon tetrachloride, trichlorethylene or perchlorethylene; an ester such as ethyl, butyl or amyl acetic ester, or an alcohol such as ethanol or isopropanol or amyl alcohol is used. 9. Fungicidal agent according to claim 5, characterized in that an organic carrier substance Solvent such as ethylene or diethylene glycol monoalkyl ether is used. 85 10. Fungicidal agent according to claim 5, characterized in that the diluent is talc, Clay, bleaching earth and the like can be used. Considered publications:
French Patent No. 911178;
U.S. Patent No. 2,510,564. © 609 738/362 12.56 (709 534/154 6. 57)