US3869503A

US3869503A - Substituted amidophenylguanidines

Info

Publication number: US3869503A
Application number: US083159A
Authority: US
Inventors: Arno Widdig; Engelbert Kuhle; Ferdinand Grewe; Helmut Kaspers; Hans Scheinpflug; Paul-Ernst Frohberger
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1969-11-06
Filing date: 1970-10-22
Publication date: 1975-03-04
Anticipated expiration: 1992-03-04
Also published as: ZA707167B; GB1282374A; FR2069114A5; IL35440A0; NL7016232A; CH508603A; PL69661B1; ES385211A1; RO58034A; JPS4936705B1; IL35440A; MY7300142A; HU163069B; BG17537A3; JPS4811015B1; DK126499B; BE758607A; AT303751B; DE1955749A1

Abstract

IN WHICH EACH X independently denotes a halogen atom, lower alkyl or lower alkoxy, n denotes 0,1 or 2, R denotes a hydrogen atom, or lower alkyl, R'' denotes alkyl with 1-12 carbon atoms, and R'''' denotes a hydrogen atom, alkyl with 1-18 carbon atoms, which may be substituted, cycloalkyl with 5-8 ring carbon atoms, aralkyl, which may be substituted, aryl, which may be substituted, or 2-furyl, which possess fungicidal properties.

Substituted amidophenylguanidines of the formula

Description

ilnited States Patent [1 1 Widdig et al.

[ Mar.4,1975

[ SUBSTITUTED AMIDOPHENYLGUANIDINES [75] Inventors: Arno Widdig, Blecher; Engelbert K'tihle, Bergisch Gladbach; Ferdinand Grewe, Burscheid; Helmut Kaspers, Leverkusen; Hans Scheinpflug, Leverkusen; Paul-Ernst Frohberger, Leverkusen, Germany [73] Assignee: Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany [22] Filed: Oct. 22, 1970 [21] Appl. No.: 83,159

[30] Foreign Application Priority Data Jan. 8. 1970 Germany 1955749 [52] U.S. Cl 260/471 C, 71/88, 71/105,

71/111, 260/347.3, 260/404.5, 260/465.4 [51] Int. Cl. C07c 125/06 [58] Field of Search 260/471 C, 404.5

[56] References Cited UNITED STATES PATENTS 3,564,041 3/1971 Farrissey et a] 260/471 C Primary E.\'aminerLorraine A. Weinberger Assistant E.\'aminer L. A. Thaxton Attorney, Agent, or FirmBurgess, Dinklage & Sprung [57] ABSTRACT Substituted amidophenylguanidines of the formula in which each X independently denotes a halogen atom, lower alkyl or lower alkoxy, n denotes 0,1 or 2, R denotes a hydrogen atom, or lower alkyl, R denotes alkyl with l12 carbon atoms, and R" denotes a hydrogen atom, alkyl with 1-18 carbon atoms, which may be substituted, cycloalkyl with 58 ring carbon atoms, aralkyl, which may be substituted, aryl, which may be substituted, or 2-furyl, which possess fungicidal properties.

13 Claims, N0 Drawings SUBSTITUTED AMIDOPHENYLGUANIDINES The present invention relates to and has for its objects the provision of particular new substituted amidophenylguanidines which possess fungicidal properties, active compositions-in the form of mixtures of such compounds with solid and liquid dispersible carrier vehicles, and methods for producing such compounds and for using such compounds in a new way especially for combating fungi, with other and further objects becoming apparent from a study of the within specification and accompanying examples.

It is known that certain guanidine derivatives can be used as fungicides, for example dodecylguanidine acetate (A) (see Belgian Patent Specification No. 568,612) which has attained a considerable importance in practice. The salts of phenylmercury, which are toxic to mammals, used hitherto in the cultivation of pip fruit for the control of scab (Venturia inaequalis and Venturia pirina), may be replaced by the salts of dodecylguanidine for the curative combating of many fungal diseases. However, the salts of dodecylguanidine are only very slightly effective against powdery mildew fungi from the Erysiphaceae family, such as the causative organism of powdery mildew of apples, Podosp/zaera leut'orriclm.

The present invention provides amidophenylguanidines of the general formula each X independently denotes a halogen atom, lower alkyl or lower alkoxy,

n denotes 0, l or 2,

R denotes a hydrogen atom or lower alkyl,

R denotes alkyl with ll2 carbon atoms, and

R" denotes a hydrogen atom, alkyl with 1-18 carbon atoms (which may be substituted by halogen, cyano, lower alkoxy, alkoxycarbonyl with 2-5 carbon atoms, phenoxy, halophenoxy, alkylphenoxy or alkoxyphenoxy), cycloalkyl with 5-8 ring carbon atoms, aralkyl (which may be substituted by halogen, lower alkyl or lower alkoxy), aryl (which may be substituted by halogen, lower alkyl or lower alkoxy) or 2-furyl.

The compounds of the formula (1) exhibit strong fungicidal properties.

The present invention also provides a process for the production of the amidophenylguanidines of the formula (l) in which a Z-aminoaniline derivative of the formula in which:

I I RO'CINCNHCOR.

I ll 0 SR 0 in which:

R is the same as defined above, and R"" stands for alkyl of l-4 carbon atoms in the presence of a diluent (which term includes a solvent).

lt is surprising that the amidophenylguanidines according to the invention possess a higher fungidical 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 cichoracear'um), apples from apple scab (Venturia inaequalis) and powdery mildew of apples (Podosphaera leucotricha), and horse beans (Vicia faba) from Botrytis cinema. The abovementioned 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 systemic groups, their high compatibility with plants and low toxicity to warm-blooded animals, the compounds according to the invention represent a valuable enrichment of the art.

When 2-amino-4-methylacetanilide and N,N'-biscarbomethoxyisothiourea-S-methyl ether are used as starting materials, the reaction course can be represented by the following equation:

' 3 NH C U NH-CD-OCH3+ s NH-C-CH H 3 The Z-aminoaniline derivatives used as starting materials are defined by the formula (ll). In this formula, as in formula (I), X stands preferably for chlorine, bromine, fluorine, alkyl or alkoxy with 1-4 carbon atoms, and especially chlorine, methyl, ethyl, isopropyl, methoxy, ethoxy or isopropoxy; n stands preferably for 0 or I, R stands preferably for methyl, ethyl or especially hydrogen and R" stands preferably for alkyl with l] 8 carbon atoms, p-methylphenyl, p-chlorophenyl, pmethoxyphenyl, heptadecyl, phenyl and especially methyl, propyl, undecyl, l-furyl or phenoxymethyl. As examples of the 2-aminoaniline derivatives, there may be mentioned: 2-aminoacetoanilide, 2-amino-4- methylacetanilide, 2-amino-butyranilide, 2- aminolauranilide, 2-aminostearanilide, benzoic acid (2-am'ino-)-anilide, p-chlorobenzoic acid (2-amino)- anilide, phenoxyacetic acid (2-amino)-anilide, 2- furancarboxylic acid (2'-amino)-anilide, N-ethyl-N- acetyl-o-phenylenediamine, 2-amino-4- chloroacetanilide, and 2-amino-4-chloro-stearanilide.

The 2-amino-aniline derivatives used as starting materials are for the most part known (see Beilsteins Handbuch der organischen Chemie, Volume 13, pages 32, Berlin 1930; Volume 13, l. Erganzungswerk (1st Supplement), pages 8-10, Berlin 1933; Volume 13, 2.Erganzungswerk (2nd Supplement), pages l423, Berlin-G6ttingen-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 lower alkyl especially with 1-4 carbon atoms and most especially for methyl, ethyl or propyl. In formulae (I) and (III), the radicals R may be the same or different. R' stands preferably for methyl or ethyl. Some of the isothiourea ethers are known (see Olin and Dains, J., Amer. Chem. Soc. 52, 3326 (1930) and US. Pat. No. 2,933,502); they can also be obtained from S-alkyl-isothiourea 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,N-bis-carbomethoxy-isothiourea-S-methyl ether,

N-N-bis -carbomethoxy-isothiourea-S-ethyl ether,

N-N'-bis-carboethoxy-isothiourea-S-methyl ether,

and

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, isopropanol; mixtures of alcohols with water; ketones, such as acetone, (optionally mixed with water); and ethers, such as dioxane or tetrahydrofuran.

The reaction temperatures can be varied within a fairly wide range. In general, the work is carried out at from between about 50 to 120C, preferably from about 60 to 100C.

When carrying out the process according to the invention, 1 mole of isothiourea ether is preferably used per mole of Z-aminoaniline derivative. Amounts greater or lesser by up to 20% are possible without substantial diminution ofthe 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 re-crystallization.

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 warmblooded 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, Ascomycetes, Basidiomycetes and Fungi Imperfecti.

The active compounds according to the invention have a very broad activity spectrum and can be applied 4 against parasitic fungi which infect above-the-soil parts of plants or attack the plants 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 from the Erysiphaceae family with the most important genera being Erysiphe, Uncinula (Oidium), Sphaerotheca and Podosphaera. As important fungi, there may be mentioned Erysiphe cichoracearum, Podosplzaera leucotri- (ha and Uncinula necator.

The active compounds according to the invention also give good results in the control of rice diseases. Thus, they show an excellent activity against the fungi Piricularia oryzae and Pelli'cularia sasakii, by reason of which they can be used for 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 Cochliobolus myiabeanus, Mycosphaerella musicola, Cercospora personata, Bolry- [is cinerea, Alternaria species, Verticillium alboatrum, Phialophora cinerescens and Fusarium species as well as against the bacterium Xanthomonas oryzae.

The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with conventional inert (i.e. plant compatible or herbicidally inert) pesticide diluents or extenders, i.e. diluents or extenders of the type usable in conventional pesticide formulations or compositions, e.g. conventional pesticide dispersible carrier vehicles, such as solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granules, etc. These are prepared in known manner, for instance by extending the active compounds with conventional pesticide dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g. conventional pesticide surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purpose: inert dispersible liquid diluent carriers including inert organic solvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes, etc.), paraffins (e.g. petroleum fractions), chlorinated aliphatic hydrocarbons (e.g. methylene chloride, etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, etc.), amines (e.g. ethanolamine, etc.), ethers, ether-alcohols (e.g. glycol monomethyl ether, etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethyl sulfoxide, etc.), ketones (e.g. acetone, etc.), and/or water; as well as inert dispersible finely divided solid carriers, such as ground natural minerals (e.g. kaolins, alumina, silica, chalk, i.e. calcium carbonate, talc, kieselguhr, etc.) and ground synthetic minerals (e.g. highly dispersed silicic acid, silicates, e.g. alkali silicates, etc.); whereas the following may be chiefly considered for use as conventional carrier vehicle assistants, e.g. surface-active agents for this purpose: emulsifying agents, such as non-ionic and/or anionic emulsifying agents (e.g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfonates, aryl sulfonates, etc., and especially alkyl aryl-polyglycol ethers, magnesium stearate, sodium oleate, etc.); and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtures with one another and/or with sucht solid and/or liquid dispersible carrier vehicles and/or with other known conpatible active agents, especially plant protection agents, such as other fungicides, or herbicides, insecticides, bactericides, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 0.l95%, and preferably 290%, by weight of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 0.0001-10.0 preferably 001-1 .071, by weight of the mixture. Thus, the present invention contemplates over-all compositions which comprise mixtures of a conventional dispersible carrier vehicle such as (l) a dispersible carrier solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and/or water preferably including a surfaceactive effective amount of a carrier vehicle assistant, e.g. a su rface-active agent, such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally about 00001-9570, and preferably 0.0l-95'/r, by weight of the mixture.

Generally, 00001-107: by weight concentrations of the active compound are sufficiently effective, although aqueous preparations having concentrations of 0.014% by weight of the active compound are normally used.

In the case of use as seed dressings, applied amounts of0.1 to g, preferably 0.2 to 2 g, of active compound per kg of seed are suitable.

1n the case of use as soil treatment agents, applied amounts of 1 to 500 g, preferably 10 to 200 g, per cubic meter 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 active compound can also be used in accordance with the well-known ultra-low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment, in finely divided form, e.g. average particle diameter of from 50-100 microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/hectare are needed, and often amounts only up to about 1 quart/acre, preferably 2-16 fluid ounces/acre, are sufficient. In this process it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about 20 to about or by weight of the active compound, or even the active substance alone, e.g. about 20-100% by weight of the active compound,

In particular, the present invention contemplates methods of selectively killing, combating or controlling fungi, which comprises applying to at least one of (a) such fungi and (b) their habitat, i.e. the locus to be protected, a fungicidally effective or toxic amount of the particular active compound of the invention alone or together with a carrier vehicle as noted above. The instant formulations or compositions are applied in the usual manner, for instance by squirting, spraying, atomizing, vaporizing, scattering, dusting, watering, sprinkling, pouring, and the like.

It will be realized, of course, that the concentration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application. Therefore, in special cases, it is possible to go above or below the aforementioned concentration ranges.

The fungicidal effectiveness of the new compounds of the present invention is illustrated, without limitation, by the following Examples.

EXAMPLE 1 Fusicladiu n test (apple scab) (Protective) 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 four to six leaf stage are sprayed with the spray liquid until dripping wet. The plants remain in a greenhouse for 24 hours at 20C. and at a relative atmospheric humidity of 70%. They are then inoculated ith an aqueous conidiumsuspension of the apple scab causative organism (Fusicladium dendriticum el) and incubated for 18 hours in a humidity chamber at l8-20C. and at a relative atmospheric humidity of 100%.

The plants are then placed in a greenhouse for 14 days.

15 days after inoculation, the infestation of the seedlings is determined as a percentage of the untreated but also inoculated control plants.

0% 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 obtained can be seen from the following Table l Fusicladium test Protective Active Compound NH C H NH-C ca 000a NH (A) (known) 8 n--c-ooa Nit-c 5 mr-e-oca NH-C-C.H3

II o

' 9 NC-OCH Nit-c :1 mapper;

o mag-0 H EXAMPLE 2 Fusicladium test (apple scab) (Curarive) 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 Infection as a percentage of the infection of thd untreated control with r a concentration of active compound (in of 0.0062

chamber at 18-20C. and at an atmospheric humidity of The plants are then placed in a green house where 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 are again placed in a greenhouse.

15 days after inoculation, the infestation of the apple- TA BLE 2 Infection as a percentage of the infection of the untreated control. with a Residence concentration of active period in compound (in7.,) l Active compound hours 42 of 0.025 0.0062 1 (known) (A) l? 4 N NH C -C OCH E1 NH-E I-OCH NH-C-CH O (2) 4 32 9 c NIL-C OCZHS g?-0C H NH- 4 3s 0 N It NH C -C-OCH -c NH- 0 if 3? O 9 c NH C 4N C-OCH Ii--g;-o m NH-C-CH O i EXAMPLE 3 about three foliage leaves are sprayed with the spray liquid until dripping wet. The cucumber plants remain Erysiphe test in a greenhouse for 24 hours to dry. They are then, for s the purpose of inoculation, dusted with conidia of the olvent. 4.7 parts by weight acetone Emulsifier: 0.3 parts by weight alkylaryl polyglycol fungus y p polyphaga' The plants are Subsequently ether placed in a greenhouse at 2324C. and at a relative Water: parts by weight is diluted with the stated amount of water containing 65 the stated additions. V 7 Young cucumber plants (Delikatess variety) with atmospheric humidity of about 75%.

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; that the infestation is exactly as great as in the case of the control plants. 7

The active compounds, the concentrations of the active compounds and the results obtained can be seen from the following Table 3.

:IABLE 3 Erysiphe Test Infection as a percentage of the infection of the untreated control with a concentration of active compound (in of Actlve compound 0.0062

NH OOH C H NH-C CH C (known) (A) 87 .9 N-C-OCH NH-C-OCH 3 NH-C-CH I N Nmc -c OC H N U H 3 00 11 S? N c1 rut-c C 00113 na-g-ocH O Egg- (s 73 EXAMPLE 4 Apple seedlings grown in standard soil are, in the three to four leaf stage, watered once in one week with g 20 cc of the liquid to be used for watering, in the stated Fuslcladlum (system'cl concentration of active compound, with reference to Solvent; 4.7 parts by weight acetone 100 cc of soil. The plants so treated are, after the treat- Emulsifier: P t y weight Hlkyluryl p yg y ment, inoculated with an aqueous conidium suspension water: byweigm 60 of Fusicladium dendriticum el and incubated for 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 5 18 hours in a humidity chamber at l820C and at a relative atmospheric humidity of The plants are then placed in a greenhouse for 14 days.

15 days after inoculation, the infection of the seed lings 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 concentratione of the acfrom the following Table 4:

tive compounds and the results obtained can be seen TABLE 4 Fusiciadium test /systemic I Infection as a percentage of the infection 55 the umtreated control with a concentration of active compolmd Active compound 30 ppm NH-C \NH-C-OCH n N--C-OCH 3 lH-Ci 3 Nil-94311 15 ppm Water: 95

TABLE 4 (continued) Fusicladium tes t/systemic compound of Active compound ppm 15 ppm 9 l NH C N-C-0CH NH-C-OCH b 3 NH- f. NC-OCH NH-c 3 NH-C-OCH i 3 O NH-C EXAMPLE 5 three to four leaf stage, watered, once in one week with Podosphaera test (systemic) Solvent:

0.3 parts by weight alkylaryl polyglycol ether 40 parts by weight 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 treat ment, inoculated with conidia of Podosphaera leucorri- 'cha Salm and placed in a greenhouse at a temperature of 2l-23C and at a relative atmospheric humidity of about 10 days after the inoculation, the infection of the seedlings is determined as a percentage of the untreated but also inoculated control plants.

0% mean no infection; 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 obtained can be seen from the following Table 5 Podosphaera test/systemic Infection as a percentage of the infection of the untreated control with a concentration of active coinpound of Active compound 30 ppm 15 ppm 0 H NH 1 CH 0 r 2 25 H2 3 OOH (known) (A) 100 100 Podos Eha era tes t /sys temic Infection as a percentage of the infection of the untreated control with a concentration of active compound of Active compound 30 ppm 15 ppm NH- U i OCH3 0 .o.5

NH-C-CH O ll 3 o 9 N 3 NH C; C OCH KI -we 17 3O NH -C-CH O N 1 OCH 5 C H O NH-C 2 5 U NH-C-OCH 6 -ii' 1s 31 f. MFR-C I-i--C-OCH U NH-C-OCH B 3 I NH-g-C H 4, 5

u N-C-OCH NH-C: I I Nd-g-Uch5 V 41 1 O lIP.--C I EXAMPLE 6 The amount of active compound required for the desired concentration of the active compound in the liq- Botrytistcst (systemic) 65 uid to be used for watering is mixed with the stated I 4 V h I amount of solvent, and the concentrate is diluted with n i rs ii gem; the stated amount of water which contains the stated P y y Ether additions.

95 parts by weight Plants of Vicia faba grown in standard soil are, in the i one to two leaf-pair stage, watered once in 1 week with 20 cc 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 Botrytl's cinerea Pers. ex Fr. and laid on the leaves. After an incubation period of 48 hours in the closed dishes at 20C, the necroses visible under the small discs are evaluated according to frequency of occurrence (evaluation scheme O V). The evaluation values obtained are converted into percentage infection.

% means no infection; 100% means that the infec-' tion is exactly as great as in the case of the control plants.

The active compounds, the concentrations of the active compounds and the results obtained can be seen from the following Table 6:

TA BLE 6 Botrztis tes t/sys temic 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 rice plants about 24 weeks old are sprayed with the spray liquor until dripping wet. The plants remain in a green house at temperatures of 22 to 24C and a relative atmospheric humidity of about until they are dry. One batch of the plants is then inoculated with an aqueous suspension of l00,000 to 200,000 spores/ml of Piricularia oryzae and placed in a chamber at 24-26C and relative atmospheric humidity. The other batch of the plants is infected with a culture of PelIicuIaria sasakii grown on malt agar and placed at 2830C and 100% relative atmospheric humidity.

5 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 Evaluation of leaf necroses O-V with the following concentrations of active compound in ppm Active compound NH C H NH-C CH COOH (known) (A) 1 l M142 NC--OCH NHC-OCH n 3 NH-C-CH. o

N in

-C-OCH NHC f 3 U NH-(q-OCH -t; C H 18 EXAMPLE 7 of the plants infected with Pellicularia sasakii, the infection of the leaf sheaths after the same time is also deter- 65 mined in proportion to the untreated but infected control. Pmculana and Pelhculur' 0% means no infection; 100% means that the infec- Solvent: 4 parts by weight acetone tion is exactly as great in the case of the control plants. a/ispersing agent: 90.25 parts by weight sodium oleate The active compounds, the concentrations of the aco if 3: gelatin tive compounds and the results obtained can be seen TABLE 7 Piricularia (a) and Pellicularia (b) tes t 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.

pr: protective cur. curative Infection as a percentage of the infection of the. untreated control with a concentration of Active compound active compound (in Z) of 0.05 0.025 0.05 0.025

12 5 :H cooa pr. 100 100 l 100 wn) (A) cur. 100

9 NH- C N-C-OCH U NH-C-OCH n 3 NH-C-CH 0 tl 3 O N--COOCH c1 Nit-c 3 m NH-coooa mag-c11 P 0 0 cur. 13

EXAMPLE 8 tive compound, the agar is poured into Petri dishes 50 under sterile conditions. When the mixture of substrate and active compound has solidified, test fungi from Agar plate test Test for fungitoxic effectiveness and breadth of the activity spectrum. pure Cultures are Inoculated to It In Small discs of 5 s l t t mm diameter. The Petri dishes remain at 20C for 3 0 ven I a e e Parts by weight: al 1830 days OI' Incubation. i I I b) 100 55 After this time, the inhibiting action of the active compound on the mycelium growth is determined in categories, taking into account the untreated control. 0 means no mycelium growth, either on the treated substrate or on the inoculum, the symbol means mycelium growth on the inoculum only no spread to the treated substrate; and the symbol means mycelium growth from the inoculum on 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 can be seen from the following Table 8:

-i TUEIOS umpuzsng umlodsXxo o um txesng o UJHJOUITTIO o o urnfIEsn umxoqotza eloqqqdoz Kqd 0 12 0.)"; seq o o T 'P I 'PQL 655W TUI H- A o umstojcqoreras O 'etu-gqoxaras u negro: w I co 3 1 13 9 o q) Q H m U H o m 8 o a) 2 r: e:

m d u a o u u u o. o o 0 D H o o Ts -12 e H H :1 2:: m o u r: 0 w --4 m -U\ I m m a: U o o o O o o o O o o l I o u a o: 9- T I g T E n z E m o a o m I I I i l a u: w -o 0 0:0 0 'd O O o l U 3 I I A U1 2 m as E Z a E "J 5 N N 8 u 5 m 31 ,3 0-0 v A A A 8 S, 2',

EXAMPLE 9 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 To Produce a Suitable y dressing, the active 65 closed glass flask. The seed, on moist loam under a Pound is extended with a mixture of equal Parts y cover ofa layer ofmuslin and 2 cm of moderately moist Weight of talc and kieselguhr to give a finely Powdered compost soil, is exposed to optimum germination conmixture with the desired concentration of the active di i f h Spores f 1() d at 10C i a f i compound. {0L

Seed dressing test/bunt of wheat (seed-born mycosis) The germination of the spores on the wheat grains, 5 The preparation of the active compound is uniformly each of which is contaminated with about 100,000 mixed with Fruhstorfer standard soil. which has first spores, is subsequently determined microscopically. been sterilized and then inoculated with pure cultures The smaller the number of spores which have germiof the test fungi. nated, the more effective is the active compound. Thesoil is filled into 5 pots, each of which is sown m with 10 seeds of the host plants. The pots are placed in The active compounds, the concentrations ofthe aca greenhouse at the stated temperatures and kept nortive compounds in the dressing, the amounts of dressmally moist. ing used and the percentage spore germination can be 3 weeks after sowing. the number of healthy plants is seen from the following Table9: determined as a percentage of the number of seeds l ilei Active compound Concentration of Applied amount Spore active compound dressing in Germinain the dressing g/kg seed tion in Z. in Z.

non-dressed 7-10 ca -mr-cs-s (known) 9 NH C N-C-OCH I (2) HH-EE-OCH 30 1 0.000

O 10 1 0. 5 NH-CCH3 IIE-c N---COOC H 4 E1 NH-C0OC H 30 1 0.05

Nike-0 H E M 10 sown. 0% means that no healthy plants have grown; so treating agent test/somber mycoss 100% means that healthy plants have resulted from all the seeds.

To produce a suitable preparation of the active com- 65 The active compounds, the concentration of the acpound the active compound is extended with talc to a tive compounds in the soil, the test fungi, host plants, content of 5% and subsequently wth quartz sand to a greenhouse temperatures and the results obtained can content of 0.5% of active compound. be seen from the following Table 10:

Table 10 Soil treating agent test/soil-born mycoses Number of healthy plants Test fungi; Fusarium (in Z) culmorum Host plant: Pea

Temperature range: 22 25C Active compounds Concentration of active compound in mg/liter soil Fruhstorfer standard soil,

sterilized untreated 96 Fruhstorfer standard soil,

sterilized and inoculated untreated 10 NH c H xiii-o 12 2 ca 00 12 NH 3 OH 100 4 200 14 (known) NC-OCH mi-cf 3 (2) Qt NH-c-ocH 100 NH-O-CH o NH .C NCOOC H NH-COOC H 3 7 (ll EI 100 The following further examples are set forth to illustrate, without limitation, the process for producing the active compounds according to the present invention.

EXAMPLE ll H C%N-COOCH3 \NH-COOCH3 limp-CH 5 methylphenyl)-N,N"-bis-methoxycarbonylguanidine 'having the melting point of l65l67C separate. The

yield is 57% of the theory.

In analogous manner, hydrogen following compounds are obtained:

It will be realized by the artisan that all of the foregoing compounds contemplated by the present invention possess the desired strong fungicidal properties, with regard to a broad spectrum of activity, as well as a comparatively low toxicity toward warm-blooded creatures and a concomitantly low phytotoxicity, enabling such compounds to be used with correspondingly favorable compatibility with respect to warm-blooded creatures and plants for more effective control and/or elimination of fungi by application of such compounds to such fungi and/or their habitat.

It will be appreciated that the instant specification and examples are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit and scope of the present invention.

What is claimed is:

l. Amidophenylguanidines of the formula:

in which:

each X independently denotes a halogen atom, lower alkyl lower loer alkoxy, I

n denotes 0, l or 2,

R denotes a hhydrogen atom or lower alkyl,

R denotes alkyl with l-12 carbon atoms, and

R" denotes a hydrogen atom, alkyl with l-l 8 carbon atoms which may be substituted by lower alkoxy, alkoxycarbonyl with 2-5 carbon atoms, phenoxy, or alkoxyphenoxy, cycloalkyl with 5-8 ring carbon atoms, or phenyl which may be substituted by halogen, lower alkyl or lower alkoxy.

2. Compound according to claim 1 in which R denotes alkyl with l-l8 carbon atoms optionally substituted by alkoxy with l-4 carbon atoms, alkoxycarbonyl with 2-5 carbon atoms, phenoxy, alkoxyphenoxy cycloalkyl with 5-8 ring carbon atoms, or phenyl optionally substituted by halogen, alkyl with 1-4 carbon atoms or alkoxy with 1-4 carbon atoms.

3. Compound according to claim I in which X denotes a chlorine, bromine or fluorine atom or alkyl or alkoxy with l-4 carbon atoms; n denotes a hydrogen atom or methyl or ethyl; R denotes alkyl with l-4 carbon atoms; and R denotes alkyl with 1-18 carbon atoms, phenyl, p-chlorophenyl, p-methylphenyl, pmethoxyphenyl or phenoxymethyl.

4. Compound according to claim 1 in which X denotes chlorine, methyl or ethoxy; n denotes or I; R denotes hydrogen; R denotes methyl, ethyl or npropyl; and R denotes methyl, n-propyl, n-undecyl, phenyl or phenoxy-methyl.

5. Compound according to claim 1 wherein such compound is N-( Z-acetamido-S-methylphenyl)-N,N"- bis-methoxycarbonylguanidine of the formula cn m-c 13f mr-g-ocu Nil-EI-CH O compound methoxycarbonylguanidine of the formula 6. Compound according to claim 1 wherein. such is N-(Z-acetamidophenyU-N',N-biscompound is N-(2-acetamido-5-ethoxyphenyl)-N',N"- bis-metoxycarbonylguanidine of the formula rm a; 0011 3 NH O E B 8. Compound according to claim 1 wherein such compound is N-(2-propionamidophenyl)-N',N"-bisethoxycarbonylguanidine of the formula 9. Compound according to claim 1 wherein such compound is N-(2-propionamidophenyl)-N',N-bismethoxycarbonylguanidine of the formula 10. Compound according to claim I wherein such compound is N-(2-phenoxyacetomidophenyl)-N',N"- bis-methoxycarbonylguanidinc of the formula 11. Compound according to claim 1 wherein such '0 compound is N-(2-acetamido-5-chlorophenyl)-N',N- bis-methoxycarbonylguanidine of the formula NH-C \NH-C-OCII 1 u 4 N---C-OCH (8) u C1 NH-C O NH-C-OCH 3 13. Compound according to claim 1 wherein such v lo compound is N- (z-acetamidophenyl)N"N-bis- 3 3 V propoxycarbonylguanidme of the formula %N-COOC H 12. Compound according to claim 1 wherein such NH-C compound is N-(Z-benZamidOphenyIyN,N-bis- (ll) methoxycarbonylguanidine of the formula 3

Claims

1. AMIDOPHENYLGUANIDINES OF THE FORMULA:

2. Compound according to claim 1 in which R'''' denotes alkyl with 1-18 carbon atoms optionally substituted by alkoxy with 1-4 carbon atoms, alkoxycarbonyl with 2-5 carbon atoms, phenoxy, alkoxyphenoxy, cycloalkyl with 5-8 ring carbon atoms, or phenyl optionally substituted by halogen, alkyl with 1-4 carbon atoms or alkoxy wIth 1-4 carbon atoms.

3. Compound according to claim 1 in which X denotes a chlorine, bromine or fluorine atom or alkyl or alkoxy with 1-4 carbon atoms; n denotes a hydrogen atom or methyl or ethyl; R'' denotes alkyl with 1-4 carbon atoms; and R'''' denotes alkyl with 1-18 carbon atoms, phenyl, p-chlorophenyl, p-methylphenyl, p-methoxyphenyl or phenoxymethyl.

4. Compound according to claim 1 in which X denotes chlorine, methyl or ethoxy; n denotes 0 or 1; R denotes hydrogen; R'' denotes methyl, ethyl or n-propyl; and R'''' denotes methyl, n-propyl, n-undecyl, phenyl or phenoxy-methyl.

5. Compound according to claim 1 wherein such compound is N-(2-acetamido-5-methylphenyl)-N'',N''''-bis-methoxycarbonylguanidine of the formula

6. Compound according to claim 1 wherein such compound is N-(2-acetamidophenyl)-N'',N''''-bis-methoxycarbonylguanidine of the formula

7. Compound according to claim 1 wherein such compound is N-(2-acetamido-5-ethoxyphenyl)-N'',N'''' -bis-methoxycarbonylguanidine of the formula

8. Compound according to claim 1 wherein such compound is N-(2-propionamidophenyl)-N'',N''''-bis-ethoxycarbonylguanidine of the formula

9. Compound according to claim 1 wherein such compound is N-(2-propionamidophenyl)-N'',N''''-bis-methoxycarbonylguanidine of the formula

10. Compound according to claim 1 wherein such compound is N-(2-phenoxyacetomidophenyl)-N'',N''''-bis-methoxycarbonylguanidine of the formula

11. Compound according to claim 1 wherein such compound is N-(2-acetamido-5-chlorophenyl)-N'',N''''-bis-methoxycarbonylguanidine of the formula

12. Compound according to claim 1 wherein such compound is N-(2-benzamidophenyl)-N'',N''''-bis-methoxycarbonylguanidine of the formula

13. Compound according to claim 1 wherein such compound is N-(2-acetamidophenyl)-N'',N''''-bis-propoxycarbonylguanidine of the formula