IL35440A - Amidophenylguanidines,their production and their use as fungicides - Google Patents

Description

in»"»©s ^aipo ana Amidophenylguaiiidinea, their producti and their use as fungicides FARBETODRIKEW BAYER AKTIENGESELLSCHAFT 35440/2 The present invention relates t o certain new amidophenyl-guanidines, to a process for their production and to their use as fungicides.

It is known that certain guanidine derivatives can be used as fungicides, for example dodecylguanidine acetate (see Belgian Patent Specification 568,612) which has attained a considerable importance in practice. The salts of phenyl-mercur , which are toxic to mammals, used hitherto in the cultivation of pip fruit for the control of scab (Venturia inaequalis and ?enturia pirina), may be replaced by the salts of dodecylguanidine for the curative combatting of many fungal diseases. However, the salts of dodecylguanidine are only very slightly effective against powdery mildew fungi from the ISryslphaceae family, such GS the causative organism of po^rdery raildew of apples, Podosphaera leucotricha.

The present invention provides amidophenylguanidines of the general formula in which each X independently is a halogen atom, or an alkyl or alkoxy radical with 1-4 carbon atoms, n is 0 or 1 R* is alkyl with 1-4 carbon atoms, and ΙΪ" denotes a hydrogen atom, alkyl raiih 1-18 carbon atoms (which may be substituted by phenoxy) cycloalkyl with 5-8 - 3 - 35440/2 The compounds of the formula (I) exhibit strong fungicidal properties.

The present invention also provides a process for the production of the amidophenylguanidines of the formula (I) in which a 2-aminoaniline derivative of the formula in which X,n, ". and RM have the meanings stated above, is reacted with an N,N '-bis-carboalkoxyisothiourea-S-alkyl ether of the formula R'0-C-N=C-NH-G-0R' 0 SR" 1 0 AA in which R' has the meaning stated above, and, RM ' stands for alkyl of 1-4 carbon atoms in the presence of a diluent (which term includes a solvent).

It is surprising that the amidophenyJLguanidines according to the invention possess a higher fungicidal activity against powdery mildew fungi than dodecylguanidine acetate. Also , interesting is the fact that compounds according to the invention also exhibit a genuine systemic effectiveness against some $ important fungus-parasitic diseases. Thus, for example it is possible, by supplying the compounds via the roots of the host plants, to protect cucumbers from powdery mildew of cucumbers (Erysiphe cichoracearum) , apples from apple scab (Venturia Le A 12 508 -3- inaequalis) and powdery mildew of apples (Podosphaera leucotricha), and horse beans (Vicia faba) from Botrytis cinerea. The above-mentioned agents of the prior art do not possess such a systemic activity. Owing to their protective, curative and systemic fungicidal activity against a large number of phytopathogenic fungi from various systematic groups, their high compatibility with plants and low toxicity to warm-blooded animals, the compounds according to the invention represent a valuable enrich» ment of the art.

If 2-amino-4-methylacetanilide and Ν, Ν'-bis-carbomethoxy-isothiourea-S-methyl ether are used as starting materials, the reaction course can be represented by the following equation: The 2-aminoaniline derivatives used as starting materials are defined by the formula (II). In this formula, as in formula (I), X stands preferably for chlorine, bromine, fluorine, methyl, ethyl, isopropyl, methoxy, ethoxy or isopropoxy, n stands preferably for 0 or 1, R a «fi^-preferabl-- >^-¾yd^^^ ox- ethyl, and Rn stands preferably for methyl, propyl, undecyl, heptadecyl, phenyl, p-chlorophenyl, p-methylphenyl, p-methoxy-phenyl, 1-furyl or phenoxymethyl. As examples of the 2-amino-anilij-!e derivatives, there may be mentioned: 2-aminoacetoknilide, 2-amino-4-methylacetanilide, 2-aminobutyranilide , 2-amino- (2-amino)-anilide, 2-furancarboxylic acid (2'-amino)-anilide, N-ethyl-N-acetyl-o-phenylenediamine, 2-amino-4-chloro-acetanilide, 2 amino-4-chloro-stearanilide. d.

The 2-amino-aniliae derivatives used as starting materials are for the most part known (see Beilsteina Handbuch der organi-schen Chemie, Volume 13_, page 20- 32, Berlin 1930; Volume 13_, 1. Brganzungswerk (1st Supplement), page 8 - 10, Berlin 1933; Volume 12, 2. Brganzungswerk (2nd Supplement), page 14 - 23, Berlin-Gottingen-Heidelberg, 1950). They can also be obtained by reduction or catalytic hydrogenation of the appropriate nitro compounds.

The isothiourea ethers used as starting materials are defined by the formula (III). In this formula, as in formula (I), R' stands preferably for methyl, ethyl or propyl. In formulae (I) and (III), the radicals R' may be the same or different.

RMI stands preferably for methyl or ethyl. Some of the isothiourea ethers are known (see Olin and Dains, J. Amer. chem.

Soc. £2, 3326 (1930) and U.S. Patent Specification 2,933,502); they can also be obtained from S-alkylisothiourea ethers and chloroformic acid alkyl esters in the presence of equivalent amounts of alkali.

As examples of the isothiourea ether, there may be mentioned: N, 1-bis-carbomethoxy-isothiourea-S-methyl ether, N,Nf-bis carbomethoxy-isothiourea-S-ethyl ether, Ν,Ν'-bis-carboethoxy-isothiourea-S-methyl ether, N,N,-bis-carbopropoxy-isothiourea-S-methyl ether.

All polar organic solvents are suitable as the diluent in the process according to the invention. These include alcohols, such as methanol, ethanol or isopropanol; mixtures of alcohols with water; ketones, such as acetone, (optionally mixed with wide range. In general, the work is carried out at from 50° to 120°C, preferably from 60° to 100°C.

When carrying out the process according to the invention, 1 mole of isothiourea ether is preferably used per mole of 2~ aminoaniline derivative. Amounts greater or lesser by up to 205* are possible without substantial diminution of the yield.

The reaction is preferably carried out in a boiling solvent, an alkylmercaptan being formed as a by-product. The end products are obtained in crystalline form when the reaction mixture is cooled, and can be separated by suction filtration and, optionally, purified by re-dissolving or recrystallisation.

The active compounds according to the invention exhibit a strong fungitoxic activity. In the concentrations necessary for the control of fungi, they do not damage cultivated plants, and have a low toxicity to warm-blooded animals. For these reasons, they are suitable as crop protection agents for the control of fungi. Fungitoxic agents in crop protection are used for the control of Archimycetes, Phycomycetes, Aseomycetes, Basldio-mycetes and Fungi Imperfect!.

Tbe active compounds according to the invention have a very broad activity spectrum and can be applied against parasitic fungi which infect above-the-soil parts of plants or attack the plant8 from the soil, as well as against seed-borne pathogenic agents.

They are particularly effective against fungi which cause powdery mildew diseases. To this group of fungi there belong predominantly representatives form the Brysiphaceae family with the most important genera being Brysiphe, Uncinula (Oidium) , Sphaerotheca and Podosphaera. As important fungi, there may be mentioned Brysiphe cichoracearum, Podosphaera leucotricha and good results in the control of rice diseases. Thus, they show an excellent activity against the fungi Piricularia oryzae and Pellicularia sasakii, by reason of which they can be used for the joint control of these two diseases. This means a substantial advance, since, up to now, agents of different chemical constitution were required against these two fungi. Surprisingly, the active compounds show not only a protective activity, but also a curative and systemic effect.

The compounds according to the invention, however, also act against other fungi which infect rice or other cultivated plants, such as Gochliobolus myiabeanus, Mycosphaerella musicola, Cercospora personata, Botrytis cinerea, Alternaria species, Verticillium alboatrum, Phialophora cinerescens and Fusarium species as well as against the bacterium Xanthomonas oryzae.

The active compounds according to the present invention can be converted into the usual ormulations, such as solutions, emulsions, emulsifiable concentrates, suspensions, powders, pastes and granulates. These may be produced in known manner, for example by mixing the active compounds with extenders, that is, liquid or solid diluents or carriers, optionally with the use of surface-active agents, that is, emulsifying agents and/or dispersing agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents.

As liquid diluents or carriers, there are preferably used aromatic hydrocarbons, such as xylenes or benzene, chlorinated aromatic hydrocarbons, such as chlorobenzenes, paraffins, such as mineral oil fractions, alcohols, such as methanol or butanol, or strongly polar solvents, such as dimethyl formamide or dimethyl sulphoxide, as well as water. or ground synthetic minerals, such as highly-dispersed silicic acid or silicates.

Preferred examples of emulsifying agents include non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylarylpolyglycol ethers, alkyl sulphonates and aryl sulphonates; and preferred examples of dispersing agents include lignin, sulphite waste liquors and methyl cellulose.

The active compounds according to the invention may be present in the formulations in admixture with other active compounds, such as other fungicides, insecticides, and acaricides.

The formulations contain, in general, from 0.1 to 95» preferably from 2 to 90, per cent by weight of active compound.

The active compounds may be applied as such, in the form of their formulations or in the application forms prepared therefrom, such as ready-to-use solutions, emulsifiable concentrates, emulsions, suspensions, spray powders, pastes, soluble powders, dusting agents and granulates. Application takes place in the usual manner, for example by squirting, spraying, atomising, dusting, scattering, fumigation, vaporisation, watering, dressing or incrustation.

The concentrations of active compound in the ready-to-apply preparations can be varied within a fairly wide range. In general, the concentrations are from 0.0001 to 10$, preferably 0.01 to 1 t by weight.

The active compounds can also be used with good results in the ultra-low-volume (U1V) process, where it is possible to apply formulations of up to 5$ of active compound or even the active compound alone.

In the case of use as seed dressings, applied amounts of 0.1 to 10 g, preferably 0.2 to 2 g, of active compound per kg of 1 to 500 g, preferably 10 to 200 g, per cubic metre of soil are usually necessary.

The active compounds according to the invention show also an insecticidal and acaricidal activity as well as an activity against some mould fungi and yeasts. In concentrations higher than those necessary for fungicidal activity, the substances inhibit plant growth.

The present invention also provides a fungicidal composition containing as active ingredient a compound of the invention in admixture with a solid diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.

The present invention also provides a method of combating fungi which comprises applying to the fungi or a fungus habitat a compound of the invention alone or in the form of a composition containing as active ingredient a compound of the invention in admixture with a solid or liquid diluent or carrier.

The present invention also provides crops protected from damage by fungi by being grown in areas in which immediately prior to and/or during the time of the growing a compound of the invention was applied alone or in admixture with a solid or liquid diluent or carrier. It will be seen that the conventional methods of providing a harvested crop may be enhanced by the present invention.

The following Examples illustrate the effectiveness of the compounds of the present invention: Example A Fusicladium test (apple scab) (Protective) Solvent: 4.7 parts by weight acetone Emulsifier: 0.3 parts by weight alkylaryl polyglycol ether Water: 95 parts by weight The amount of active compound required for the desired mixed with the stated amount of solvent, and the concentrate is diluted with the stated amount of water which contains the stated additions* Young apple seedlings in the 4 - 6 leaf stage are sprayed with the spray liquid until dripping wet. The plants remain in a greenhouse for 24 hours at 20°G and at a relative atmospheric humidity of 70$. They are then inoculated with an aqueous conidium suspension of the apple scab causative organism (Pusicladium dendriticum Puck) and incubated for 18 hours in a humidity chamber at 18 - 20°0 and at a relative atmospheric humidity of 100#.

The plants then again come into a greenhouse for 14 days. days after inoculation, the infestation of the seedlings is determined as a percentage of the untreated but also inoculated control plants.

Oft means no infestation; 100$ means that the infestation is exactly as great as in the case of the control plants.

The active compounds, the concentrations of the active compounds and the results can be seen from the following Table: Table A Pusicladium test / Protective Infection as a percentage of the infection of the untreated control with a concentration Active compound of active compound n- of 0.0062 —COOCH, NH-C NH-COOCH- 17 Table A (continued) Fusicladium test / Protective Infection as a percentage of the infection of the untreated control with a concentration of active compound (-i»- )- of 0.0062$ (6) Example B Fusicladium test (apple scab) [Curative] Solvent: 4.7 parts by weight acetone Emulsifier: 0.3 parts by weight alkylaryl polyglycol ether Water: 95 parts by weight The amount of active compound required for the desired concentration of the active compound in the spray liquid is mixed with the stated amount of solvent, and the concentrate is diluted with the stated amount of water which contains the stated additions.

Young apple seedlings in the 4 - 6 leaf stage are inoculated with an aqueous conldium suspension of the apple scab causative organism Fusicladium dendriticum Fuck and incubated for 18 hours in a humidity chamber at 18-20°C and at an atmospheric humidity of lOOji. The plants then come into a greenhouse. They dry.

After standing for a suitable period of time, the plants are sprayed dripping wet with the spray liquid prepared in the manner described above. The plants then again come into a greenhouse. days after inoculation, the infestation of the apple means no infestation; 100$ means that the infestation is exactly as great as in the case of the control plants.

The active compounds, the concentrations of the active compounds, the period of time between inoculation and spraying and the results obtained can be seen from the following Table: Table B Pusicladium test / Curative Infection as a percentage of the infection of the untreated control with a Residence concentration of active Active compound period in compound (-±«"#■) hours 42 of 0.025 0.0062£ (known) Example C Brysiphe test Solvent : 4.7 parts by weight acetone Bmulsifier: 0.3 parts by weight alkylaryl polyglycol ether Water: 95 parts by weight The amount of the active compound required for the desired concentration in the spray liquid is mixed with the stated amount of the solvent, and the concentrate is diluted with the stated amount of water containing the stated additions.

Young cucumber plants (Delikatess variety) with about three foliage leaves are sprayed with the spray liquid until dripping wet. The cucumber plants remain in a greenhouse for 24 hours to dry. They are then, for the purpose of inoculation, dusted with conidia of the fungus Brysiphe polyphaga. The plants are subsequently placed in a greenhouse at 23-24°C. and at a relative atmospheric humidity of about 7 .

After 12 days, the infestation of the cucumber plants is determined as a percentage of the untreated but also inoculated control plants. 0$ means no infestation; 100$ that the infestation is exactly as great as in the case of the control plants.

The active compounds, the concentrations of the active compounds and the results can be seen from the following Table: Table C Brysiphe test Infection as a percentage of the infection of the untreated control with a concentration of active Active compound compound of 0.0062$ Table C (continued) Erysiphe test Infection as a percentage of the infection of the untreated control of active Active compound Example D Fusicladium test (systemic) Solvent: 4.7 parts by weight acetone Emulsifieri. 0.3 parts by weight alkylaryl polyglycol ether concentration of the active compound in the liquid to be used for watering is mixed with the stated amount of solvent, and the concentrate is diluted with the stated amount of water which contains the stated additions.

Apple seedlings grown in standard soil are, in the 3 - 4 leaf stage, watered once in one week with 20 cc of the liquid to be used for watering, in the stated concentration of active compound, with reference to 100 cc of soil. The plants so treated are, after the treatment, inoculated with an aqueous conidium suspension of Fusicladium dendriticum Puck and incubated for 18 hours in a humidity chamber at 18 - 20°C and at a relative atmospheric humidity of 100 . The plants then again come into a greenhouse for 14 days. days after inoculation, the infection of the seedlings is determined as a percentage of the untreated but also inoculated control plants. Qffo means no infection; 100$ means that the infection is exactly as great as in the case of the control plants.

The active compounds, the concentrations of the active compounds and the results can be seen from the following Table: Table D Fusicladium test / systemic Infection as a percentage of the infection of the untreated control with a concentration of active Active compound compound of ppm 15 ppm (known) <+fi> Table D (continued) Fusicladium test / systemic Infection as a percentage of the infection of the untreated control with a concentration of active Active compound compound of ppm 15 ppm (2) a l e (Continuation) Fusicladium test / systemic Active Compound Infection as a percentage of the infection of the untreated control with a concentration of active compound of 30 ppm 15 ppm (7) (8) Example B Podosphaera test (systemic) Solvent: 4.7 parts by weight acetone Dispersing agent: 0.3 parts by weight alkylaryl polyglycol ether Water: 95 parts by weight The amount of active compound required for the desired concentration of the active compound in the liquid to be used for watering is mixed with the stated amount of solvent, and the concentrate is diluted with the stated amount of water which contains the stated additions.

Apple seedlings grown in standard soil are, in the 3 - 4 leaf stage, watered once/three times in one week with 20 cc of the liquid to be used for watering, in the stated concentration of active compound, with reference to 100 cc of soil. The plants so treated are, after the treatment, inoculated with conidia of Podosphaera leucotricha Salm and placed in a greenhouse at a temperature of 21 - 23°C and at a relative atmospheric humidity of about 70$. 10 days after the inoculation, the infection of the seedlings is determined as a percentage of the untreated but also inoculated control plants. 0# means no infection; 100$ means that the infection is exactly as great as in the case of the control plants.

The active compounds, the concentrations of the active compounds and the results can be seen from the following Table T a b l e E Podosphaera test / systemic Active compound Infection as a percentage of the infection of the untreated control with a concentration of active compound of 30 ppm 15 ppm 17 (known) (4-9) (2) Continuation T a b l e E Podosphaera test / systemic Active compound Infection as a percentage of the infection of the untreated control with a concentration of active compound of 30 ppm 15 ppm 31 (3) 0 (6) ^ — COOCH^ NH-C 41 Example F Botrytis test (systemic) Solvent: 4.7 parts by weight acetone Dispersing agent: 0.3 parts by weight alkylaryl polyglycol ether Water: 95 parts by weight.

The amount of active compound required for the desired concentration of the active compound in the liquid to be used for watering is mixed with the stated amount of solvent, and the concentrate is diluted with the stated amount of water which contains the stated additions.

Plants of Vicia faba grown in standard soil are, in the 1-2 leaf-pair stage, watered three times/once in one week with 20cc of the liquid to be used for watering, in the stated concentration of active compound, with reference to 100cc of soil.

After the treatment, the lower two leaf-pairs are removed and, in each case, placed in a Petri dish lined with moist filter paper. Small discs of filter paper of 1 cm diameter are then dipped into an aqueous conidium suspension of the grey mould causative organism Botrytis cinerea Pers. ex Fr. and laid on the leaves. After an incubation period of 48 hours in the closed dishes at 20°C, the necroses visible under the small discs are evaluated according to frequency of occurrence (evaluation scheme 0 - V). The evaluation values obtained are converted into percentage infection.

Of* means no infection; 100$ means that the infection is exactly as great as in the case of the control plants.

The active compounds, the concentrations of the active compounds and the results can be seen from the following a l e F Botrytis test / systemic Active compound Evaluation of leaf necroses 0 - V with the following concentrations of active compound in ppm 120 C, H C-NH-CT . CH,C00H 100 1 \ 5 •NH, 17 (known) (2) Example G Piricularia and Pellicularia test Solvent; 4 parts by weight acetone Dispersing agent; 0<>05 parts by weight sodium oleate Waters 95.75 parts by weight Other additives; 0.2 parts by weight gelatin The amount of active compound required for the desired concentration of active compound in the spray liquor is mixed with the stated amount of solvent, and the concentrate is diluted with the stated amount of water containing the stated additives. 2 batches each consisting of 30 rice plants about 2 - 4 weeks old are sprayed with the spray liquor until dripping wet. The plants remain in a greenhouse at temperatures of 22 to 24°0 and a relative atmospheric humidity of about 70$ until they are dry. One batch of the plants is then inoculated with an aqueous suspension of 100,000 to 200,000 spores/ml of Piricularia oryzae and placed in a chamber at 24 - 26°C and 100$ relative atmospheric humidity. The other batch of the plants is infected with a culture of Pellicularia sasakii grown on malt agar and placed at 28 - 30°C and 100$ relative atmospheric humidity. to 8 days after inoculation, the infection of all the leaves present at the time of inoculation with Piricularia oryzae is determined as a percentage of the untreated but also inoculated control plants* In the case of the plants infected with Pellicularia sasakii, the infection on the leaf sheaths after the same time is also determined in proportion to the untreated but infected control. o means no infection; 100 means that the infection is a l e G Piricularia(a) and Pellicularia(b) test pr. = protective cur» = curative Infection as a percentage of the infection of the untreated control Active compound 17 pr. 100 100 100 (knovm) (V2-) cur. 100 (2) Example H Agar plate test Test for fungitoxic effectiveness and breadth of the activity spectrum.

Solvent ί acetone Parts by weight: a) 1000 b) 100 To produce a suitable preparation of the active compound, 1 part by weight of the active compound is taken up in the stated amount of solvent.

The preparation of the active compound is added to potato dextrose agar (which has been liquefied by heating) in such an amount that the desired concentration of active compound is set up therein. After thorough shaking to achieve a uniform dispersion of the active compound, the agar is poured into Petri dishes under sterile conditions. When the mixture of substrate and active compound has solidified, test fungi from pure cultures are inoculated on to it in small discs of 5 mm diameter. The Petri dishes remain at 20°G for 3 days for incubation.

After this time, the inhibiting action of the active compound on the mycelium growth is determined in categories, taking into accound the untreated control. 0 means no mycelium growth, either on the treated substrate or on the inoculum, with the symbol - means mycelium growth on the inoculum only/no spread to the treated substrate; and the symbol + means mycelium growth from the inoculum o^to the treated substrate, similar to the spread to the untreated substrate of the control.

The active compounds, the concentration of the active compounds, the test fungi and the inhibition effects achieved untreated H-CS-S 18 ;Zn (known) 10 + 100 + NH-GS-S ( 4) Example I Seed dressing test/bunt of wheat (seed-born mycosis) To produce a suitable dry dressing, the active compound Is extended with a mixture of equal parts by weight of talc and kieselguhr to give a finely powdered mixture with the desired concentration of the active compound.

Wheat seed is contaminated with 5 g of the chlamydospores of Tilletia caries per kg of seed. To apply the dressing, the. seed is shaken with the dressing in a closed glass flask. The seed, on moist loam under a cover of a layer of muslin and 2 an of moderately moist compost soil, is exposed to optimum germination conditions for the spores for 10 days at 10°G in a refrigerator.

The germination of the spores on the wheat grains, each of which is contaminated with about 100, 000 spores, is subsequently determined microscopically. The smaller the number of spores which have germinated, the more effective is the active compound.

The active compounds, the concentrations of the active compounds in the dressing, the amounts of dressing used and the percentage spore germination can be seen from the following Table: Table I Seed dressing test/bunt of wheat Active compound Conc acti in t non-dressed >10 18 (known) Example K Soil treating agent test/soil-born mycoses.

To produce a suitable preparation of the active compound, the active compound is extended with talc to a content of 5$ and subsequently with quartz sand to a content of 0.5$ of active compound.

The preparation of the active compound is uniformly mixed with Fruhstorfer standard soil, which has first been sterilised and then inoculated with pure cultures of the test fungi.

The soil is filled into 5 pots, each of which is sown with 10 seeds of the host plants. The pots are placed in a greenhouse at the stated temperatures and kept normally moist. 3 weeks after sowing, the number of healthy plants is determined as a percentage of the number of seeds sown. 0$ means that no healthy plants have grown; 100$ means that healthy plants have resulted from all the seeds.

The active compounds, the concentrations of the active compounds in the soil, the test fungi, host plants, greenhouse temperatures and the results obtained can be seen from the following Table Table K H Soil treating agent test/soil-born myco Test fungi: Host plant: Temperature range: Concentration of Active compounds active compound, in Ό4 mg/litre soil O Pruhstorfer standard soil, sterilised untreated Paruhstorfer standard soil, sterilised and inoculated untreated Table (continued) H Soil treating agent test/soil-bo Test fungi: Host plant i Temperature range Active compounds Concentration of active compound in mg/litre soil (11) 100 The following examples illustrate the compounds and process of the present inventions Example 1 63 g (0.3 mole) of Ν,Ν'-bis-carbomethoxyisothiourea-S-methyl ether and 49.2 g (0.3 mole) of 3-amino-4-acetamidotoluene are boiled together for 4 hours in 300 ml of alcohol. The solution is filtered while hot. During cooling, 50 g of N-(2-acetamido-5-methylphenyl)-N' , rt-bis-methoxycarbonylguanidine of the melting point 165-167°C separate. The yield is 7# of the theory.

In similar manner, the following compounds are obtainedί Example Formula Melting point (°C) Example Formula Melting point (°C) decomp.) Example. Form la eltlpg point (°C) A 12 508 ft .33a -

Claims (1)

1. 34 Amidophenylguanidines of the formula in which each independently is a halogen or an alkyl or radical with 1 4 carbon n is 0 is alkyl with 1 4 carbon and is a hydrogen alkyl with 1 18 carbon atoms may be substituted by cyeloalkyl with 5 8 carbon phenyl or o The compound of the formula The compound of the The compound of the The compound of the The compound of the 0 Le A 12 508 35 The compound of the The compound of the The compound of the The compound of the Amidophenylguanidine compounds of formula I in Claim substantially described herein reference to the A process the production of according to any of Claims 1 to 11 in which a derivative of the formula H in which n and have the stated in Claim is reacted with an isothiourea ether of the formula i 0 in which has the meaning stated in Claim 1 and stands for with 1 4 carbon in the presence of a process according to Claim 12 in which the reaction is carried out at to and preferably at to process according to Claims 12 or 13 in which the derivative and the isothiourea ether are used in substantially process according to any of Claims 12 to 14 in which is methyl or process according to any of Claims 12 to 15 in which the reaction is carried out in the presence of a substantially polar organic A process for the production of compounds according to Claim 1 substantially as hereinbefore described in any of the Compounds according to Claim 1 whenever prepared by a process according to any of Claims 12 to Fungicidal compositions containing as active ingredient a compound according to any of Claims 1 to 11 and 18 in admixture with a solid diluent or carrier or in admixture with a liquid diluent or carrier containing a active A composition according to Claim 19 containing to and preferably 2 to of the active by A method of combaJihg fungi which comprises applying to the fungi or to a fungus habitat a compound according to any of Claims 1 to 11 and 18 alone or in the form of a sition according to Claim 19 or A method according to Claim 21 in which a composition is used containing from to of the active by A method according to Claim 22 in which a sition is used containing from to the active by A method according to any of Claims 21 to 23 in which the compound ia applied to soil in an amount of 1 to 500 g per cubic metre of A method according to Claim 24 in which the compound is applied in an amount of 10 to 200 g per cubic metre of A method according to any of Claims 2 o 23 in which the compound is as a to seeds in an amount of to 10 g per leg of A method according to Claim 26 in which the compound is applied in an amount of to 2 g per kg of A method according to any of Claims 21 to 24 in which the compound is according to any of Claims 1 to and A method according to any of Claims 21 to 27 in which the compound is one of those hereinbefore mentioned in any of Examples A to Crops protected from damage by fungi by being grown in areas in which immediately prior to during the time of the a compound according to any of Claims 1 to and 18 was applied alone or in admixture with a solid or liquid diluent or insufficientOCRQuality