DD298475A5 - FUNGICIDES CONTAINING CARBAMOYLATED GUANIDINE - Google Patents

Abstract

The invention relates to fungicidal agents containing carbamoylated guanidines for combating phytopathogenic fungi, in particular Oomycetes, on agricultural and agricultural crops. The fungicidal compositions according to the invention contain carbamoylated arylguanidines of the general formula I as active ingredients or their addition salts with inorganic or organic acids in addition to conventional carrier substances, solvents and / or formulation auxiliaries. They are characterized by high activity against Phytophthora infestans, Phytophthora cactorum, Gaeumannomyces graminis, Thyphula incarnata u. a. important phytopathogenic fungi. The compounds according to the invention can also be used together with other fungicides in the form of combined preparations. {Fungicides; agricultural crops; carbamoylated arylguanidines; Addition salts; carrier materials; Formulation auxiliaries; Phytophthora infestans; Phytophthora cactorum; Gaeumannomyces graminis; Thyphula incarnata; Kombinationspraeparat}

Description

Il

in which

R 1 -naphthyl or phenyl, which by one or more alkyl, alkoxy, nitro groups or

Halogen atoms substituted εβίη, R ^{1 is} cycloalkyl (preferably cyclohexyl) or phenyl which is represented by an alkyl, alkoxy or a

or a plurality of halogen atoms may be substituted, X is an acid anion equivalent to the guanidine cation, e.g. Cl ", SOu ~, CICH ₂ COO",

4-CH ₃ C ₆ H ₄ SOi, C ₁₅ H ₃₁ SOi, etc., η is the number 1 or 2

mean, in addition to customary carriers, solvents and / or formulation auxiliaries. 2. Fungicidal agent according to claim 1, characterized in that they additionally contain as active ingredients other fungicides, plant growth regulators and / or agrochemicals.

Field of application of the invention

The invention relates to fungicidal compositions containing carbamoylated guanidines, for controlling phytopathogenic fungi, in particular Oomycetes, on agricultural and horticultural crops.

Characteristic of the known state of the art

A number of effective fungicides from the class of alkylene-bis-dithiocarbamic acids are available for combating economically important pathogens of fungal parasitic plant diseases, such as potato late blight or brown rot of tomato caused by the fungus Phytophthora infestans. Especially against leaf diseases, the known under the names Zineb and Maneb ethylene-bis-dithiocarbaminsäuren zinc and manganese salts are used worldwide. In these compounds there is a risk of metabolisation to the environmental toxin ethylene thiourea (ETU), its teratogenic, mutagenic and carcinogenic potencies (see EPPO publ., Ser C, 46, Paris [1976] 1-33, abstracts 3. Intern Congr. Of Pesticide Chemistry, Helsinki [1974] 35.1; Bull. Environ. Contam Toxicol., New York 1β [1976] 5,546-555). After 1970, a number of nitrogen atom-alkylated anilides in which the alkyl group may be substituted by alkenyl, alkynyl, carbonylalkyl, alkoxycarbonyl, dialkylcarbamoyl, and also nitrile groups have been proposed as microbicidal agents (CH 600764.603041,606029,607888; DE 2836158, 2903612, DD 150421, EP 45049, US 4224050). Fungicides of this type often show undesirable phytotoxic side effects on the plants to be protected against fungal attack when applying the amounts required in practice. In addition, the more recently observed resistance phenomena increasingly limit the application of the selected from this class of compounds and technically used agents. From the series of carbamoylated and thiocarbamoylated guanidines, some representatives are known which have fungicidal and growth-regulating properties.

These are the carbamoylated and preferably thiocarbamoylated tetraalkylguanidines (Esso Research and Engineering Co .: US Pat. No. 3,759,991, DE 2122058), which are proposed as plant growth regulators. This invention further relates to the use of 1,1,3,3-tetramethyl-2- (dimethylthiocarbamoyl) guanidine and 1,1,3,3-tetramethyl-2- (dimethylcarbamoyl) guanidine for controlling the fungus Phytophthora infestans in tomato plants, albeit in concentrations (1000-2000ppm) that are uneconomical for practical use. Furthermore, unsubstituted or N-alkyl-substituted N'-alkylcarbamoylguanidines in which the alkyl radical may be substituted by an alkenyl, alkoxy, cycloalkyl or Morpholinoalkylgruppe, as active ingredients for bactericidal agents in human medicine and / or fungicidal agents for combating phytopathogenic Mushrooms claims (US 3652766,3692625,3798269,4009163). Due to their high concentrations of use and the difficult to obtain and z.T. technically complex starting material related economic burdens, these agents have so far found little place in plant protection practice.

The aim of the invention is to provide new effective fungicidal agents for controlling phytopathogenic fungi based on new principles of action, which have no undesirable side effects on the plants to be protected and meet the requirements of the strategic concept to prevent the development of resistant fungus pathotypes or to combat them.

Explanation of the essence of the invention

The invention has for its object to optimize by suitable substitutions, the structure of Guanldinmoleküls so that it is possible to use these compounds as active ingredients for the development of new fungicidal compositions with the required performance properties. The use of these agents is said to combine a fungicidal action with an increase in the natural defense potential of the plants against infection by microorganisms.

It has been found that carbamoylated arylguanidines of the general formula I or their addition salts with inorganic or organic acids of the general formula II

R-NH-

NH

NH-C-NH-R it O

R-NH-C

NH-C-NH-R

Il

in which

R 1-naphthyl or phenyl which may be substituted by one or more alkyl, alkoxy, nitro or halogen atoms

R ^{1 may be} cycloalkyl (preferably cyclohexyl) or phenyl represented by an alkyl, alkoxy or one or more halogen atoms

can be substituted, χ a guanidinium ation equivalent acid anion, z. Cl ", SO '", CICH ₂ COO ", 4-CH ₃ C ₆ H ₄ SOi, C | ₆ H ₃ , SO5 etc.

η denotes theZahH or 2

mean, in addition to a fungicidal effect induce the formation of phytoalexin in the plant cells by Sonsitizerwirkung and therefore are suitable as active ingredients for fungicidal agents for controlling phytopathogenic fungi, in particular Oomycetes. The increased formation of phytoalexinan, in which plants by the carbamoylated arylguanidines according to the invention is preferably carried out by sensitizing the plant cells, while their Elicitorwirkung plays only a minor role. The compositions of the invention are well plant compatible at their application concentration and have good efficacy against Oomycetes, such as. B. Phytophthora infestans.

The duration of action is extended due to the dual functional principle of the compounds compared to conventional fungicides. In addition, the use of the compounds due to their sensitizing effect in phytoalexin formation reduces the risk of developing resistance of the phytopathogenic microorganisms. The compounds of the invention thus represent a valuable enrichment of the prior art.

The carbamoylated arylguanidines of the formula I according to the invention can be prepared by generally known processes. The compounds of general formula I are accessible from the monosubstituted arylguanidines by reaction with aryl or cycloalkyl isocyanates in solvents which are inert to the reaction partners used. The reaction temperatures are between OX and the boiling point of the solvent used, preferably between O ⁰ C and the boiling point of the solvent used, preferably between ^{0 0} C and 80 ⁰ C. The serving as starting materials monosubstituted arylguanidines can be prepared by addition of aromatic amine salts ( preferably hydrochlorides) on cyanamide (compare A.Kämpf, Bar 37, 6882 [1904]; CE Braun et al., J. Org. Chem. 3 149 [1939]). Another possibility for the preparation of the compounds of the general formula I according to the invention is the method proposed by Curd, Davey and Richardson (J.Chem.Soc. 1949, 1732), according to which the conversion of the monosubstituted arylguanidine salts into the corresponding arylguanidine bases and their reaction with isocyanates in one and the same reaction medium (anhydrous acetone) is feasible.

The preparation of the addition salts of the carbamoylated arylguanidines of the general formula II according to the invention is carried out by reacting the carbamoylated arylguanidines of the formula I with the corresponding inorganic or organic acids in suitable solvents (preferably abs.

The novel compounds prepared by these process variants are summarized in Tables 1 and 2. The active compounds of the general formula I or II according to the invention can be formulated with suitable carriers and / or diluents and optionally with surface-active substances or other customary auxiliaries by conventional methods to dusts, wettable powders, mordants, granules, emulsifiable concentrates or solutions.

The fungicidal compositions according to the invention may contain other known active compounds to the compounds according to the invention or be used in combination with other crop protection and pest control agents or agrochemicals.

Depending on the intended use, the formulations generally contain between 1 and 90% by weight of active ingredient. The invention will be explained by the following embodiments, but without limiting it.

-3- 298 475 Ausführungsbelsplele

example 1 Preparation of N- (2,6-dimethylphenyl) -N'-phenylcarbamoylguanidine (Comp # 32) To a solution of 8.2 g (0.05 mol) of (2,6-dimethylphenyl) guanidine in 80 ml of benzene is added gradually with stirring Room temperature, a solution of 5.95g (0.05 mol) of phenyl isocyanate in 20ml of dry benzene. After the subsidence of

exothermic reaction is stirred for a further hour and allowed to stand at room temperature. The fancy freinkrictalline

Product is filtered after about three hours, washed with benzene and dried. By concentrating the filtrate is still

a certain amount of N- (2,6-dimethylphenyl) -N'-phenylcarbamoyl-guadinine won.

Yield: 13.2 g (93.3% of theory), F: 172-173'C (ethanol). Example 2

Preparation of N-cyclohexylcarbamoyl-N'-o-tolylguanidine (Comp. No. 29) 1.2 g of sodium are added in small portions in 80 ml of anhydrous acetone. After the reaction has subsided, the reaction mixture is refluxed for 8-10 minutes, cooled to room temperature and added with stirring 9.3 g (0.05 mol) of o-tolyl-guanidine hydrochloride. Thereafter, stirring is continued for one hour at room temperature, added dropwise 6.3 g (0.05 mol) of cyclohexylisocyanate in 20 ml of anhydrous acetone and stirred for a further two hours. Subsequently, the reaction mixture is heated to 35-40 ° C for one hour, concentrated in vacuo to about half of the original volume and poured into 300 ml of ice water with vigorous stirring. After about 30 minutes, the precipitated product is filtered off, washed with water several times and dried. The yield is 12.3 g (89% of theory), F: 177-179'C (benzene).

Example 3 Preparation of N- (4-tert-butylphenyl) -N'-cyclohexylcarbamoylguanidine hydrochloride (Compound No. 50a) To a suspension of 15.8 g (0.05 mol) of N-M-tert-butylphenyU-N'-cyclohexylcarbamoylguanidine (Comp. No. 50) in 60 ml abs. Ethanol is stirred at room temperature, a saturated solution of HCl in abs. Ethanol until reaching the Acid point added dropwise. From the resulting reaction solution, the solvent is removed in vacuo. The tough one

colorless residue is mixed with 50 ml of aqueous acetone and the crystallization initiated by trituration. After about two

Hours the fine crystalline product is filtered off with suction, washed with anhydrous acetone and dried in a vacuum desiccator. The N- (4-tert-butylphenyl) -N'-cyclohexylcarbamoylguanidine hydrochloride is obtained in almost quantitative yield; Q: 165 to

168 ^° C. (abs. Ethanol / abs. Ether).

Example 4 Preparation of N-cyclohexylcarbamoyl-N'-o-totylguanidinium chloroacetate (Comp. No. 29c) To a suspension of 13.7 g (0.05 mol) of N-cyclohexylcarbamoyl-N'-o-tolyl-guanidine (Comp. No. 29) in 60 ml abs. Ethanol wild

gradually with stirring at room temperature, a solution of 4.7g (0.05 mol) of chloroacetic acid in 20ml abs. Given ethanol.

The resulting reaction solution is filtered, the solvent removed in vacuo, the viscous residue in 20ml anhydrous Acetone dissolved and 80ml abs. Ether added. When rubbed gradually falls after about 20 minutes, a fine crystalline product

out. The mixture is allowed to stand overnight, the product is then filtered off with suction, abs. Ether washed and in

Vacuum desiccator dried. After processing the filtrate, the yield is 17.2 g (93.5% of theory), F: 144-146 ⁰ C (abs.

Ethanol).

Example 5 Preparation of N- (2,6-dimethylphenyl) -N'-phenylcarbamoylguanidinium p-toluenesulfonate (Compound No. 32a) To a suspension of 14.1 g (0.05 mol) of N- (2,6-dimethylphenyl) -N'-phenyl-carbamoylguanidine (Comp. No.32) in 60 ml abs. Ethanol is gradually added with stirring at room temperature, a solution of 8.6 g (0.05 mol) of p-toluenesulfonic acid in 30 ml abs. Ethanol added. The light brown colored reaction solution is boiled with charcoal at reflux, filtered hot and the Solvent removed in vacuo. The viscous residue is dried in a vacuum desiccator by heating in 40 ml of ethyl acetate

dissolved, filtered hot and the solvent removed in vacuo. After about 30 minutes, the crystalline product begins to precipitate, the amount of which grows rapidly on rubbing, so that a thick suspension forms after a few minutes.

The precipitated fine crystals are filtered off with suction, first with a little ethyl acetate, then with abs. Ether washed and in Vacuum desiccator dried. By working the filtrate, the yield is increased and is 19.4 g (85.5% of theory), F:

126-129 ° C (anhydrous acetone).

According to the methods explained in Examples 1-5, the remaining compounds of Tables 1 and 2

produce.

Example β

Fungicidal activity in mycelium growth test The compounds according to the invention were dissolved in concentrations of 0.0025 and 0.00025 mol, a liquefied one Agricultural broth added and poured into sterile Petri dishes. After evaporation of the solvent, the Inoculated agar plates with the test fungi. The test fungi were Phytophtora cantorum, Gaeumannomyces graminis and Typhula

incarnate, d. H. one representative of each of the major fungal classes (Phycomycetes, Ascomycetes and Basidiomycetes) and z. B.

Rhizoctonia solani, Fusarium culmorum, Phytopthora infestans, Monilinia fructugena, Pythium spee and Pseudocerosporella

herpotrichoides. After incubation in the incubation room for 9 days, the radial mycelial growth of the fungal colony was determined.

The inhibition of mycelium growth in% is given in Tables 3 and 4. Example 7 Fungicidal activity against Phylophthora infestans The substances according to the invention formulated as wettable powders with 20% active ingredient were placed in vessels approximately 10 cm in size

attracted grown tomato plants. After the spray coating has dried, the plants were inoculated with a

Zoosporensuspension of the pathogen. The plants were incubated under favorable conditions for disease development. In the course of the disease symptom development, the control success shown in Table 5 was scored. Example 8 Combined test of compounds of formula I for phytoalexin formation in plant cells, on fungicidal action and Resistance increase. From "Adretta" potato tubers which have been thoroughly washed, dried and disinfected with 70% ethanol,

15 slices (60g fresh mass, 3cm 0,0,5cm thick) are cut and placed on incubation grates. From a solution, with 1.5 mg of active substance (Table 1) in 3 ml of acetone are applied by both sides pipetting 200 μΙ per disc and evenly distributed. The treated discs are incubated in a sealed high humidity cabinet at 18-2O ⁰ C in the dark. After 24 hours, 5 discs (sensitizer test) on both sides or 5 discs (resistance or

Fungicide test) on top each with 100μΙ of a mycelium homogenate of Phythophthora infestans (mycelium cover a

inoculated with aquarium tube of distilled water = 2.5-3.0 × 10 ⁶ zoosparangia / ml) and then further incubated under the same conditions. After another 24 hours, the slices of the fungicide or resistance test become

turned and then incubated further.

96h. After incubation, the 5 non-infected discs (elicitor test) and the 5 discs of the sensitizer test are segmented, lyophilized and, after extraction with chloroform, the content of phytoalexins (rishitin, lubimine, phytuberin,

Phytuberol) by thin layer chromatography and gas chromatography. From the 6th day after the beginning of the incubation, the 5 slices of the fungicide or resistance test daily mycelium growth of P. infestans on the surface determined. The test results are summarized in Table 6, with the indicated values for the resistance or fungicidal effect

have the following meaning:

Bonitur mycelial growth of P. infestans in%

1 2 3 4 5

S10%

> 10-30%

> 30-50%

> 50-70%> 70%

Example 9 Production of a wettable powder with an active ingredient according to the invention The following components are mixed together and then finely ground:

Inventive active ingredient 20% kaolin 45% amorphous silica 25% sulfite waste liquor 5% alkylsulfonate 5%

Table 1

R-NH-

NH-C-NH-R 0

Connection no.

Molecular formula

F (O

1 4-FC ₆ H ₄ 4-CIC ₆ H ₄ C ₁₄ H ₁₂ FCIN ₄ O 183-184 2 4-FC ₆ H ₄ 3,4-CI ₂ C ₆ H ₃ C ₁₄ H ₁₁ FCI ₂ N ₄ O 149-150 3 4-FC ₆ H ₄ 3-CH ₃ OC ₆ H ₄ C ₁₆ H ₁₆ FN ₄ O ₂ 112 to 113.5 4 4-FC ₆ H ₄ CVcIo-C ₆ H ₁₁ C ₁₄ H ₁₉ FN ₄ O 189-190 5 4-CIC ₆ H ₄ C ₆ H ₆ C ₁₄ H ₁₃ CIN ₄ O 191-192 6 4-CIC ₆ H ₄ 3,4-CI ₂ C ₆ H ₃ C ₁₄ H ₁₁ CI ₃ N ₄ O 184-185 7 4-CIC ₆ H ₄ cyclo-C ₆ Hii C ₁₄ H ₁₉ CIN ₄ O 197-198 8th 2,4-CI ₂ C ₆ H ₃ C ₆ H ₆ C ₁₄ H ₁₂ CI ₂ N ₄ O 172 to 173.5

Table 1 (continued)

Connection no. R R ¹ Molecular formula FCC) 9 2,4-CI ₂ C ₆ H ₃ 4-CIC ₆ H ₄ C ₁₄ H ₁₁ CI ₃ N ₄ O 134-185 10 2,4-CI ₂ CH ₃ 2-CH ₃ OC ₆ H ₄ C ₁₆ H ₁₄ CI ₂ N ₄ O ₂ 136-138 11 2,4-CI ₂ C ₆ H ₃ cyclo-C ₆ H " C ₁₄ H ₁₉ Cl ₂ N ₄ O 201-202 12 3,4-CI ₂ C ₈ H ₃ CyClO-C ₆ H ₁₁ C ₁₄ H ₁₈ CI ₂ N ₄ O 198-201 13 4-BrC ₈ H ₄ C ₆ H ₆ C ₁₄ H ₁₃ BrN ₄ O 192-194 14 4-BrC ₆ H ₄ 3,4-CI ₂ C ₆ H ₃ C ₁₄ H ₁₁ Cl ₂ BrN ₄ O 191-192 15 3-O ₂ NC ₆ H ₄ C ₆ H ₆ C ₁₁ H ₁₃ N ₆ O ₃ 166 to 167.5 16 3-O ₂ NC ₆ H ₄ 4-CIC ₆ H ₄ C ₁₄ H ₁₂ CIN ₆ O ₃ 166-168 17 3-O ₂ NC ₆ H ₄ 3,4-CI ₂ C ₆ H ₃ C ₁₄ H ₁₁ Cl ₂ N ₆ O ₃ 182-183 18 2-CH ₃ OC ₆ H ₄ 4-CIC ₆ H ₄ C ₁₆ C ₁₆ CIN ₄ O ₂ 158-159 19 2-CH ₃ OC ₆ H ₄ 3,4-CI ₂ C ₆ H ₃ C ₁₆ H ₁₄ CI ₂ N ₄ O ₂ 157-158 20 2-CH ₃ OC ₆ H ₄ cyclo-C ₆ Hu C ₁₆ Hj ₂ N ₄ O ₂ 128-130 21 4-CH ₃ OC ₆ H ₄ C ₆ H ₅ C ₁₆ H ₁₆ N ₄ O ₂ 183-185 22 4-CH ₃ OC ₆ H ₄ 3-CIC ₈ H ₄ C ₁₆ H ₁₆ CIN ₄ O ₂ 186-188 23 2,5- (CH ₃ O) ₂ C ₆ H ₃ 4-CIC ₆ H ₄ C ₁₆ H ₁₇ CIN ₄ O ₃ 118-119 24 2,5- (CH ₃ O) ₂ CeH ₃ 3,4-CI ₂ C ₆ H ₃ C ₁₆ H ₁₆ CI ₂ N ₄ O ₃ 135,5-137- 25 2-CH ₃ C ₆ H ₄ C ₆ Hs C ₁₆ H ₁₈ N ₄ O 151-152 26 2-CH ₃ C ₆ H ₄ 3-CIC ₆ H ₄ C ₁₆ H ₁₆ CIN ₄ O 83-86 27 2-CH ₃ C ₆ H ₄ 4-CIC ₆ H ₄ C ₁₆ H ₁₆ CIN ₄ O 157-158 28 2-CH ₃ C ₆ H ₄ 3,4-CI ₂ C ₆ H ₃ C ₁₆ H ₁₄ CI ₂ N ₄ O 137-138 29 2-CH ₃ C ₆ H ₄ cycloAHn C ₁₆ H ₂₂ N ₄ O 177-179 30 4-CH ₃ C ₆ H ₄ C ₆ Hb C ₁₆ H ₁₆ N ₄ O 189-190 31 4-CH ₃ C ₆ H ₄ 4-CIC ₆ H ₄ C ₁₆ H ₁₆ CINO 215-216 32 2,6- (CH ₃ I ₂ C ₆ H ₃ C ₆ H ₆ C ₁₆ H ₁₈ N ₄ O 172-173 33 2,6- (CH ₃ J ₂ C ₆ H ₃ 3-CIC ₆ H ₄ C ₁₆ H ₁₇ CIN ₄ O 152 to 153.5 34 2,6- (CH ₃ J ₂ C ₈ H ₃ 4-Cl ₆ H ₄ C ₁₆ H ₁₇ CIN ₄ O 166 to 167.5 35 2,6- (CH ₃ I ₂ C ₆ H ₃ 3,4-CI ₂ C ₆ H ₃ C ₁₆ H ₁₆ CI ₂ N ₄ O 108-110 36 2,6- (CH ₃ ) AH ₃ 2-CH ₃ OC ₆ H ₄ C ₁₇ H ₂₀ N ₄ O ₂ 165.5 to 166.5 37 2,6- (CH ₃ J ₂ C ₆ H ₃ 3-CH ₃ OC ₆ H ₄ C ₁₇ H ₂₀ N ₄ O ₂ 86-88 38 2,6- (CH ₃ ) AH ₃ 3-CH ₃ C ₈ H ₄ C ₁₇ H ₂₀ N ₄ O 158-159 39 2,6- (CH ₃ ) AH ₃ CyCio-C ₆ Hi ₁ C ₁₆ H ₂₄ N ₄ O 178-180 40 4-CH (CH ₃ ) AH ₄ C ₆ H ₆ C ₁₇ H ₂₀ N ₄ O 183 to 184.5 41 4-CH (CH ₃ I ₂ C ₆ H ₄ 3-CIC ₆ H ₄ C ₁₇ H ₁₈ CIN ₄ O 178-179 42 4-CH (CH ₃ ) AH ₄ 4-CIC ₆ H ₄ C ₁₇ H _1S CIN ₄ O 189-190 43 4-CH (CH ₃ IjC ₆ H ₄ 3,4-CI ₂ C ₆ H ₃ C ₁₇ H ₁₈ Cl ₂ N ₄ O 179-181 44 4-CH (CH ₃ ) AH ₄ cycloAHn C ₁₇ H ₂₆ N ₄ O 200-201 45 4-C (CH ₃ J ₃ C ₈ H ₄ C ₆ H ₆ C ₁₈ H ₂₂ N ₄ O 183-184 46 4-C (CH ₃ ) AH ₄ 3-CIC ₆ H ₄ C ₁₈ H ₂₁ CIN ₄ O 157.5 to 158.5 47 4-C (CH ₃ ) AH ₄ 4-Cl ₆ H ₄ C ₁₈ H ₂₁ CIN ₄ O 200-202 48 4-C (CH ₃ ) AH ₄ 3,4-CI ₂ C ₆ H ₃ C ₁₈ H ₂₀ CI ₂ N ₄ O 182-183 49 4-C (CH ₃ ) AH ₄ 3-CH ₃ OC ₆ H ₄ C ₁₉ H ₂₄ N ₄ O ₂ 156-157 50 4-C (CH ₃ ) AH ₄ CyClO-C ₆ H ₁ ) C ₁₈ H ₂₈ N ₄ O 212.5 to 213.5 51 1-naphthyl C ₆ H ₆ C ₁₈ H ₁₆ N ₄ O 185-186 52 1-naphthyl 3-CIC ₆ H ₄ C ₁₈ H ₁₆ CIN ₄ O 184-185 53 1-naphthyl 4-CIC ₆ H ₄ C ₁₈ H ₁₆ CIN ₄ O 168-169 54 1-naphthyl 3,4-CI ₂ C ₈ H ₄ C ₁₈ H ₁₄ N ₄ O ₂ C 173-175 55 1-naphthyl 3-CH ₃ OC ₆ H ₄ C ₁₉ H ₁₈ N ₄ O ₂ 142-144 56 1-naphthyl cyclo-C ₈ Hu C ₁₈ H ₂₂ N ₄ O 207-209

Table 2

R-NH-C

^ NH-C-NHtR ¹

¹ O

connection R R ¹ X η F ( ⁰ C) No. 10a 2,4-CI ₂ C ₆ H, 2-CH ₃ OC ₆ H ₄ Cl 1 168-171 12a 3,4-CI ₂ C ₆ H ₃ CyClO-C ₆ H ₁₁ Cl 1 192-194 29 a 2-CH ₃ C ₆ H ₄ cyclo-CeHii Cl 1 126-129 29b 2-CH ₃ C ₆ H ₄ cyclo-CeHn SO ₄ 2 123-126 29c 2-CH ₃ C ₆ H ₄ CyCl-C ₈ H ₁ , CICH ₂ COO 1 144-146 29d 2-CH ₃ C ₆ H ₄ CyClO-C ₆ HtI 4-CH ₃ C ₆ H ₄ SO ₃ 1 110-113 32 a 2,6- (CH ₃ J ₂ C ₆ H ₃ C ₆ H ₆ Cl 1 153-156 32 b 2,6- (CH ₃ J ₂ C ₆ H ₃ C ₆ H ₆ 4-CH ₃ C ₆ H ₄ SO ₃ 1 126-129 34 a 2,6- (CH ₃ J ₂ C ₆ H ₃ 4-CIC ₆ H ₄ Cl 1 157-161 34 b 2,6- (CH ₃ J ₂ C ₆ H ₃ 4-CIC ₆ H ₄ C ₁₆ H ₃₁ SO ₃ 1 59-63 39 a 2,6- (CH ₃ J ₂ C ₆ H ₃ CyClO-C ₆ H ₁₁ Cl 1 161-166 39 b 2,6- (CH ₃ J ₂ C ₆ H ₃ CyClO-C ₆ H ₁₁ 4-CH ₃ C ₆ H ₄ SO ₃ 1 155-157 50 a 4-C (CH ₃ J ₃ C ₆ H ₄ CyClO-C ₆ H ₁₁ Cl 1 165-168 50 b 4-C (CH ₃ J ₃ C ₆ H ₄ CyClO-C ₆ H ₁₁ SO ₄ 2 150-152 50c 4-C (CH ₃ J ₃ C ₆ H ₄ CyClO-C ₆ H ₁₁ 4-CH ₃ C ₆ H ₄ SO ₃ 1 178-182 5Od 4-C (CH ₃ J ₃ C ₆ H ₄ CyClO-C ₆ H ₁₁ C ₁₆ H ₃₁ SO ₃ 1 soft product

Table 3 Inhibition of mycelial growth (in%)

active substance P. cactorum 0.00025 R. solani 0.00025 G.graminis 0.00025 T. incarnate 0.00025 mol (Verb.-Nr.) 0.0025 100 0.0025 25 0.0025 80 0.0025 92 26 100 94 97 17 100 89 100 80 27 100 98 90 20 99 85 98 98 33 100 100 86 12 98 90 100 35 100 100 86 47 98 90 not tested 30 36 100 92 32 100 100 Table 4 Inhibition of mycelial growth (in%) 95 80 active substance 92 75 Verb.-Nr. 95 25 F.culmorum 0.00025 G.graminis 0,00025 m 29 b 91 67 0.0025 5 0.0025 72 29 d 84 99 15 100 30 32a Ph. Cactorum 52 89 27 89 52 32b 100 5 93 15 100 60 34 a 100 35 93 35 98 85 39a 100 40 92 15 99 50 50a 100 100 86 10 96 95 50b 100 22 80 40 98 94 50c 100 99 89 5 99 94 5Od 100 97 87 15 95 92 100 98 89 95 29 b 100 97 Ph. Infestans 94 M.fructigena 27 29 d 99 100 45 100 7 32 a 99 45 100 10 32 b 100 68 100 10 34 a 100 62 97 80 39 a 100 71 96 5 50a 100 90 100 94 50b 100 93 99 100 50c 100 94 100 96 5Od 96 93 99 96 98 99

Table 4 (continued)

Inhibition of mycelial growth (in%)

active substance Pythium spec. 0.00025 T. mcarnata 0.00025 P. herpotrichoides 0,00025 m • Verb.-Nr. 0.0025 92 0.0025 15 0.0025 3 29 b 100 22 10Ü 4 95 5 29d 100 57 99 15 81 5 32a 100 71 100 25 95 8th 32 b 100 95 100 99 82 19 34 a 100 37 100 5 91 0 39 a 100 97 100 98 77 8th 50 a 98 98 100 99 74 8th 50 b 100 96 100 99 72 0 50c 98 95 100 65 5 3 5Od 97 91 19 Table 5 Control of Phytophthora infestans Efficiency> 95% at ... ppm (active substance) active substance (Verb.-Nr.)

(untreated control = 100% infestation)

27 300, no phytotoxicity

28 300, no phytotoxicity

29,200, no phytotoxicity 32,150, no phytotoxicity

34 300, no phytotoxicity

35 150, no phytotoxicity 39 150, no phytotoxicity 44 200, low phytotoxicity 50 100, no phytotoxicity

Table 6 Sensitizer effect phytoalexin content (μg / gFM) Ri Pi, Po Resistance or fungicidal effect Mycelium growth of Phytophthora infestans after days substance Lu 19.4 12.7 8.2 10.4 4.6 6 7 8 9 10 129.8 100.0 119.4 106.7 88.5 75.6 1 1 "2 3 ⁺ 3 ⁺ Γ2345 5 5 5 5 5 32 29 control FM = fresh mass Ri = Riahitin Lu = Lubimin Pi = Phytuberin Po = Phytuberol

Claims (1)

1. Fungicidal agents containing carbamoylated guanidines, for controlling phytopathogenic fungi, in particular of Oomycetes, on agricultural and horticultural crops, characterized by a content of active compounds from the class of carbamoylated arylguanidines of general formula I or their addition salts with inorganic or organic Acids of the general formula II R-NH-Cl s NH 'NH-C-NH-R ¹ Il INH R-NH-C