DEE0005222MA - - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Registration date: March 18, 1952. Advertised on December 27, 1956

GERMAN PATENT OFFICE

The invention relates to novel pesticides. In particular, it relates to the protection of substances exposed to fungal attack by incorporating the triazine compounds according to the invention which are effective as pesticides in these or by applying these compounds to these substances. The invention is directed also on methods to put such compounds into use as pesticides bring, as well as procedures 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" does not only mean Property of destroying fungi, but also the property of spore germination 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" should not be limited to a hydrocarbon group, nor, if two such aryl groups are present, they must be identical. So can the 1, 3, 5-triazines according to the invention, effective as pesticides, 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 / 5-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 ones Isomers such as B. the isopropyl, the 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. are substituted. Furthermore, these aryl groups can be replaced by endoaliphatic Groups such as B. the methylene, ethylene, propylene and butylene groups are substituted, to the corresponding phenyl-endomethylene, phenyl-endoethylene, To create hydrindal and tetraline radicals. Likewise, the aryl group can through the same or another aryl group can be further substituted. Other examples of such embodiments of the compounds according to the invention are those of the abovementioned triazines in which the hydrogen is replaced on the exocyclic nitrogen atom by acenaphthene and fluorene groups.

The specific examples of those i, 3,5-triazines effective as pesticides according to the invention include 2-chloro-4,6-bis (p-phenyl-. Aniline) -s-triazine, 2,4-dichloro-6 ~ ( p-phenylaniline) -s-triazine, 2-chloro-4, 6-bis- (o-phenylaniline) -s-triazine, 2, 4-dichloro-6- (o-phenylaniline) -s-triazine, 2-chloro -4, 6-bis- (a-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 - ^ - [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- / S-naphthylamine) -s-triazine.

However, the invention is not intended to be restricted to substituted ^x >3> 5-triazines as specified above. For example, the above aryl groups can be further represented by various negative. Free radicals are substituted and not only retain their effectiveness as pesticides found according to the invention, but can in many cases have an increased effectiveness and thereby form a group of pesticides which is preferred for certain purposes. Examples of such negative groups that may be contained in the aryl radicals include the nitroso, nitro, amino, substituted amino, chlorine, bromine or iodine groups and the hydroxyl, substituted hydroxyl, azo , Cyano, thiocyan, acyloxy, aroyloxy, mercaptyl and substituted mercaptyl groups. Furthermore, various combinations of the hydrocarbon radicals and negative radicals listed above can be used.

Further examples of the chlorarylamine-i, 3, 5-triazines which are effective as pest control agents 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-chloro aniline) -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-dimethylaminoani-Hn) -s-triazine, 2-chloro-4- (toluidine) -6- (4-nitro-2-chloroaniline) - s - triazine, 2, 4 - dichloro - 6 - (4 - dimethylaminenaphthylamine) -s-triazine, 2-chloro-4, 6-bis- (p-anisi-

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din) -s-triazine, 2,4-dichloro-6- (4 [/ 3-chloroethyl] aniline) -striazine, 2 - chlorine - 4, 6 - bis - (p - 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-nitroanilm) -s-triazine, 2-chloro-4, 6-bis- (p-cyananiline) -s-triazine, 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-methylmercaptoaniline) - 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 have been found, 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 - met hylanilin) -6- (a-naphthylamino) -s-triazine, 2-chloro-4- (2, 5-dichloroaniline) - 6 - (N - methyl - ρ - anisidine) - s - triazine, 2 - chlorine - 4, 6 - bis - (diphenylamine) - s - triazine, 2 - chlorine-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, washed with 600 parts of 2N hydrochloric acid and 1000 parts of water and then recrystallized from benzene. The dichloroanisidine triazine was in a yield of 75 parts (49%) than 167 to 169.5 ° melting white. Get crystals.

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

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

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 ct-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 from ^{0 to} 50. 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 - (/? - naphthylamine) -s-triazine

This compound was prepared following the procedure of Example 3 using 100 parts of cyanuric chloride and 77.6 parts of 3-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 ₃ N ₄ Cl ₂ : Cl 27.8 ° / ,,; found: PI OA ₇ C O /

^ J- -vo / 0

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

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aniline prepared by the method of Example 3. The yield of triazine was 135.2 parts; M.p. 118 to 126 °. 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

A suspension of 2,760 parts of cyanuric chloride in 40,000 parts of water at a temperature of 3 to 8 ° was prepared in a reaction vessel with a stirrer. 4900 parts of solid 2,5-dichloroaniline were added to the stirred suspension over a period of 30 minutes. A solution of 2520 parts of sodium bicarbonate in 20,000 parts of water was then added. The reaction temperature was raised to 45 ° and held for 2 hours at 45 to 50 ^0th After cooling to 25 ° the product was collected by filtration, washed with water and dried. The yield of white crystals was 6700 parts (96.5%); Mp 192 to 194 °. Analysis: Calculated for C ₁₆ H ₈ N ₅ Cl ₅ : Cl 40.7%; . 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 using 55.4 parts of cyanuric chloride and 76 parts of p-anisidine prepared by the procedure of Example 7. The yield was 89 parts (83%); Mp. 200 to 201 °.

Example 10

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

A solution of 51 parts of cyanuric chloride in 250 parts of acetone was 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 performed by stirring at 45 to 50 ⁰ to the end. 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
2-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 to 195 °. Analysis: Calculated for C ₁₅ H ₁₂ N ₅ Cl: Cl 11.9%; found: Cl 11.5%.

Example 12

2-chloro-4, 6-bis- (a-naphthylamine) -s-triazine
This compound was obtained by treating cyanuric chloride with a-naphthylamine according to the procedure of Example 10 in a yield of 99 ° / ₀ and as white, at 209-210 ⁰ crystals melting. 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%. ·

Example 14 ·>

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. At the end of this time, the temperature of the reaction mixture was allowed to ^{rise to about 2p 0} and the reaction mixture was stirred for an additional hour. The precipitated 2,4-dichloro-6- (2-chloroaniline) -s-triazine was collected by filtration, washed with water and dried. The yield of crude product which was suitable for most Verwendungsarteil, was 105. 136 parts, corresponding to a yield of 98.7 ° / ₀ corresponded. After recrystallization from a mixture of benzene and isohexanes, the melting point of the crystalline product was 155 to 157 ⁰ . By analysis it was found that this material contained 38.1 ° / ₀ chlorine, while according to the formula · C ₉ H ₅ N ₄ Cl ₈ 38.6 ° / ₀ are required.

In addition to the amino group, the 1, 3, 5-triazines that are effective as pesticides must of the present invention at least 1 chlorine atom 115, contained on a carbon atom of the triazine nucleus. Whether ι or 2 chlorine atoms and one or two Arylamino groups provided depends largely on the type of application as well as the particular one Fungal organism that destroys or the iso 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

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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, like a painted surface or a wooden surface, or the surface of a fruit, a Trunk, or leaf, or a concrete surface, or other surface, in the most effective way protect, the substances according to the invention must be thoroughly distributed on these surfaces with them be brought into intimate contact. It is the same with the treatment of more or less porous Material such as B. cloth, felt textiles and woven fibers, important that the fabrics of the invention distributed between the fine structure of these materials and brought into intimate contact with them. Therefore, a much larger amount of relatively inert surfactants is included in the effective substances incorporated. Furthermore, such surfactants act to achieve A protective effect only very small amounts of the compounds listed above are necessary. Another The advantage of stretching these connections is that they allow the treatment of fields allows easy-to-use procedures, while the treated material is still practically perfect is 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 form of use of 2-chloro-4, 6-bis- (2, 5-dichloroaniline) -s-triazine, 10 parts of this were used 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) -striazine, 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- (g-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 back. 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 to apply a protective film by brushing on, spraying on or exchanging. 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 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-chloroaniline) -s-triazine in 250 parts of cyclohexanone was by stirring the two ingredients for 15 minutes produced at a temperature of about 25 °. These concentrated, suitable for storage and transport Solution was further diluted with 99,750 parts of kerosene to a final dilution suitable for the application of 50 parts / million to produce.

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-chloro-4- (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 made by adding further quantities of kerosene produced with equally good results.

In addition to the above-described method for Naßanwendung of 1, 3, 5-triazines mixtures can be prepared _t, in which pesticides according to the invention by talc, clay or other solid diluents are stretched. 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. Other specific examples of such typical inert solid supports; used as a diluent the use forms according to the invention can be used in dust form are fuller's earth, Pyrophillite, attaclay and bleaching 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-chloro-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 which passed through a sieve with 1600 meshes per cm 2} . This product, which contains 1 percent by weight of active substance, can be used immediately or diluted further. A further dilution was made by repeating the above procedure with a further 9,900 parts of fuller's earth.

Similar dust forms are made from the following compounds: 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-chloroaniline) -s-triazine, 2-chloro-4- (4-methylmercaptoaniline) -6- (p-anisidine ) -s-triazine, 2-chloro-4, 6-bis (N-methyl-2,5-dichloroaniline) -s-triazine and 2-chloro-4, 6-bis- (diphenylamino) -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, and2, 4-dichloro-6- (p-benzoyloxyaniline) -s-triazine in kerosene, naphtha and trichlorethylene 'When subsequently dispersed in water, they are produced 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

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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 io ° / ₀ sodium, wettable powder gave a flawless water suspension, as water was stirred to prepare a suspension with ioo parts / million active ingredient ii parts of this powder in ioooo parts. Similar wettable powders with fuller's earth, fuller's earth and pyrophyllite are obtained 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-chloroaniline) -s-triazine, 2-chloro-4,6-bis- (p-cyanoaniline) -s -triazine, 2,4-dichloro-6- (5-propenyl- / 3-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, a use form produced with a solvent can be used together with water, or Water and a surfactant can be used. Such surfactants are e.g. B. from the nature of the alkylaryl polyether alcohols, the addition products of ethylene oxide to these esters or of long-chain mercaptans.

Example 20

A solution of 1 part of 2, 4-dichloro-6- (p-toluidine) -s-triazine, 100 parts of ethyl acetate and 0.1 part of an adduct of ethylene oxide to fatty acid ester of polyhydric alcohols prepared by half-hour stirring the ingredients at 25 ^0th This solution was then added with stirring to 9900 parts of water to prepare a solution suitable for use.

Equally good dispersions are obtained if 2-chloro ~ 4,6-dianiline-s-triazine, 2,4-dichloro-6-aniline-striazine, 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-metlaylaniline) -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

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 pesticides has been established explained by determining the concentration at which the germination of each 50% of the spores of the fungi Alternaria oleracea and Sclerotinia fructicola is prevented. The former causes the potato meltdown, 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 a dispersant containing distilled Water was prepared following the procedure of Example 14. This suspension was in various Dilutions with distilled water are added to a drop of water containing the fungus under study and was on a microscope slide. That way the concentration became in which half of the fungi were prevented from germinating spores. This standard procedure germination on a slide is approved by the "Committee on Standardization of Fungicidal Tests" · the "American Phytopathological Society" · in "Phytopathology", 33, 627 (1943), has been described and accepted.

No.

Pesticides

Concentration (parts / million)

for contraception
from 5 ο ° / 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 - (/? - 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

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amount of active ingredients, which was necessary to prevent the germination of the spores of 95 ° / ₀ of existing in a culture fungal organisms rendered. This determination was made in the same manner as the above.

Typical of such results, the compound ■ 2-chloro-4, 6-bis- (2, 5-dichloroaniline) -s-triazine, a 95 ° / _o strength was achieved with the Keimungsverhinderung 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 3 to 4 inches in diameter

from 10 to 18 cm 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 in all cases to a o, oi ° / ₀ solution with an ethylene oxide-adduct of fatty acid ester 70 multi-hydric alcohols converted. 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. Under the standard conditions used, a deposition of approximately 0.0015 g of pesticide per 100 cm ^{2 of} total leaf area (ie top and bottom 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 came from fungal cultures which had been grown for 7 to 14 days at 20 ° on 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 sprayed plant was 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) 1.5
6.6
7.6
1.0
31
100

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From the above results it can be seen that the pesticides of the present invention contribute are extremely effective in treating a plant disease under conditions among which a commercial pesticide (No. 5) is unable to respond to the disease to act. Equally good results are achieved if 2-chloro-4,6-bis - (/ 3-naphthylamino) -s-triazine, 2-chloro-4,6-bis (o, -phenanthrylamine) -s-triazine, 2-chloro-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 - (/ S-

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 also at, a concentration of only 0.1 part / million will 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 used as the 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 Ingredients - in amounts from 0.01 to 2000, preferably contain about 10 parts / 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 suspension mixed with a surface-active one Means present. 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 agents according to claim, characterized characterized in that the carrier substance is an organic solvent such as ethylene or diethylene glycol monoalkyl ether is used. 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. 911 178;
U.S. Patent No. 2,510,564. © 609 738/362 12.56