GB2169283A - Fungicidal aniline derivatives - Google Patents

Abstract

Aniline derivatives of the formula: <IMAGE> wherein X and Y are alkylene or alkoxyalkylene; k, l, m and n are 0 or 1; R1 is nitro, 2-nitrovinyl, amino, isothiocyanato, alkylamino, -NHCA'R2, -NHCA'A''R2, -NHCA'NHR2, -NHCA'NR2R2, -NHSR2, -OSR2, -SA'R2, -N=C(A'R2)(A''R2'), -SO2A'R2, -SO2NHR2 or -S(O)nR2 (in which A' and A'' are O or S; R2 and R2' are alkyl, alkenyl, alkynyl, haloalkyl or alkoxyalkyl; and n is 0, 1 or 2); Z is H, alkyl, alkenyl, alkynyl, alkoxycarbonylalkyl, -COR3 or -SR4 (in which R3 is alkyl, cycloalkyl or phenyl and R4 is alkyl, phenyl or alkoxycarbonyl); A is O or S and B is alkyl, alkenyl, cycloalkyl, phenyl or -WR5 (in which W is O or S and R5 is alkyl, alkenyl, alkynyl, haloalkenyl, haloalkynyl, cycloalkyl, phenyl optionally substituted by halogen or alkyl substituted by halogen, cyano, phenyl, cycloalkyl or alkoxy), are useful as fungicidal agents against Phytopathogenic fungi, particularly strains resistant to benzimidazole, thiophanate and/or cyclic imide fungicides.

Description

SPECIFICATION Fungicidal aniline derivatives This invention relates to fungicidal aniline derivatives.

Benzimidazole and thiophanate fungicides such as Benomyl (methyl 1-)butylcarbamoyl)benzimidazol-2- ylcarbamate), Fubelidazol (2-(2-furyl)benzimidazole, Thiabendazole (2-(4-thiazolyl)benzimidazole, Carbendazim (methyl benzimidazol-2-ylcarbamate), Thiophanate-methyl(1 ,2-bis(3-methoxycarbonyl-2- thioureido)benzene), Thiophanate (1 ,2-bis(3-ethoxycarbonyl-2-thiou reido)benzene), 2-(O,S dimethyl phosphorylamino) -1 -(3'-methoxycarbonyl-2'-thioureido)benzene and 2-(O,O dimethylthiosphorylamino)-1 -(3'-methoxycarbonyl-2'-thioureido)benzene are known to show an excellent fungicidal activity against various plant pathogenic fungi, and they have been widely used as agricultural fungicides since 1970. However, their continuous application over a long period of time results in phytopathogenic fungi developing a tolerance to them, so that their plant disease preventive effect is much lowered. Furthermore, the fungi which gain a tolerance to certain benzimidazole or thiophanate fungicides also show a considerable tolerance to some other benzimidazole or thiophanate fungicides. Thus they are apt to obtain a cross-tolerance. Therefore, if any significant decrease in their plant disease-preventive effect in certain fields is observed, their application in such fields has to be discontinued. However, it is often observed that the density of drug-resistant organisms does not decrease even long after the discontinuation of the application.Although other types of fungicides have to be employed in these cases, only a few are as effective as benzimidazole or thiophanate fungicides in controlling various phytopathogenic fungi.

Cyclic imide fungicides such as Procymidone (3-(3',5'-dichlorophenyl)-1 ,2-dimethylcyclopropane-1 ,2- dicarboximide), Iprodione (3-(3',5'-dichlorophenyl)-1 -isopropyl carbamoylimidazolidine-2,4-dione), Vinchlozolin (3-(3',5'-(dichlornphenyl)-5-methyl-5-vinyloxazolidin-2A-dione), ethyl (RS)-3-(3',5'-dichlorophenyl)-5methyl-2,4-dioxooxazolidine-5-carboxylate, etc., which are effective against various plant diseases, particularly those caused by Botrytis cinerea, have the same defects as previously explained with respect to the benzimidazole thiophanate fungicides.

C.R. Acad. Sc. Paris, t. 289, S'erie D, pages 691-693 (1979) discloses that herbicides such as Barban (4-chloro-2-butynyl N-(3-chlorophenyl)carbamate), Chlorobufam (1 -methyl-2-propynyl N-(3chlorophenyl)carbamate), Chloropropham (isopropyl N-(3-chlorophenyl)carbamate) and Propham (isopropyl N-phenylcarbanate) exhibit a fungicidal activity against certain organisms tolerant to some benzimidazole or thiophanate fungicides. However, their fungicidal activity against the drug-resistant fungi is not strong enough, and hence, in practice they cannot be used as fungicides.

According to the present invention, there are provided aniline derivatives of the formula

wherein: X and Y are each independently a lower alkylene group or a lower alkoxy(lower)alkylene group; k, I, m and n are each independently 0 or 1; R1 is a nitro group, a 2-nitrovinyl group, an amino group, an isothiocyanato group, a lower alkylamino group or a group of the formula;

-NH-S-R2, -O-S-R2, -S-A'-R2,

(in which A' and A" are each independently an oxygen atom or a sulfur atom, R2 and B2 are each independently a lower alkyl group, a lower alkenyl group, a lower alkynyl group or a halo(lower)alkyl group or a lower alkoxy(lower)alkyl group and n is0, 1 or 2);; Z is a hydrogen atom, a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower alkoxycarbonyl(lower)alkyl group ora group of the formula:

or -S-R4 (in which R3 is a lower alkyl group, a cyclo(lower)alkyl group or a phenyl group and R 4 is a lower alkyl group, a phenyl group or a lower alkoxycarbonyl group); Ais an oxygen atom or a sulfur atom; and B is a lower alkyl group, a lower alkenyl group, a cyclo(lower)aklyl group, a phenyl group or a group of the formula -W-R5 (in which W is an oxygen atom or a sulfur atom and B5 is a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a halo(lower)alkenyl group, a halo(lower)alkynyl group, a cyclo(lower)alkyl group, a phenyl group optionally substituted with halogen or a lower alkyl group substituted with a least one member selected from the group consisting of halogen, cyano, phenyl, cyclo(lower)alkyl or lower alkoxy). The aniline derivatives of the invention shown an excellent fungicidal activity against plant pathogenic fungi which have developed a resistance to benzimidazole, thiophanate and/or cyclic imide fungicides.It is notable that their fungicidal potency against the organisms tolerant to benzimidazole, thiophanate and/or cyclic imide fungicides (hereinafter referred to as "drug-resistant fungi" or drug-resistant strains") is much higher than that against the organisms sensitive to benzimidazole, thiophanate and/or cyclic imide fungicides (hereinafter referred to as "drug-sensitive fungi" or "drugsensitive strains").

By the term "lower" as used herein in connection with organic radicals or compounds is meant that such groups each contain not more than 6 carbon atoms.

The compounds of the formula (I) are fungicidally effective against a wide scope of plant pathogenic fungi, of which examples are as follows: Podosphaera leucotricha, Venturia inaequalis, Mycosphaerella pomi, Marssonina mali and Scierotinia mali of apple, Phyllactinia kakicola and Gloeosporium kakiof persimmon, Cladosporium carpophilum and Phomopsis sp. of peach, Cercospora viticola, Unicinula necator, Elsinoe ampelina and Glomerella cingulata of grape, Cercospora beticola of sugarbeet, Cercospora arachidicola and Cercospora personata of peanut, Erysiphe graminis f. sp. hordei, Cercosporella herpotrichoides and Fusarium nivale of barley, Erysiphe graminis f. sp. tritici of wheat, Sphaerotheca fuliginea and Cladosporium cucumerinum of cucumber, Cladosporium fulvum of tomato, Corynespora melongenae of eggplant, Sphaerotheca humuli, Fusarium oxysporum f. sp. fragariae of strawberry, Botrytis alli of onion, Cercospora apii of cerely, Phaeoisariopsis griseola of kidney bean, Erysiphe cichoracearum of tobacco, Diplocarpon rosae of rose, Elsinoe fawcetti, Penicillium italicum, Penicillium digitatum of orange, Botrytis cinerea of cucumber, eggplant, tomato, strawberry, pimiento, onion, lettuce, grape, orange, cyclamen, rose or hop, Sclerotinia sclerotiorum of cucumber, eggplant, pimiento, lettuce, celery, kidney, azuki bean, potato or sunflower, Sclerotinia cinerea of peach of cherry, Mycosphaerella melonis of cucumber or melon, etc. Thus, the compounds of the formula (I) are highly effective in controlling drug-resistant strains of these fungi.

The compounds of the formula (I) are also fungicidally effective against fungi sensitive to the known fungicides as well as fungi against which the known fungicides are ineffective. Examples of such fungi are Pyricularia oryzae, Pseudoperonospora cubensis, Plasmopara, viticola, Phytophthora infestans, etc.

Advantageously, the compounds of the formula (I) are low in toxicity and have little detrimental effect on mammals and fish. Also, they may be applied to agricultural fields without causing any significant toxicity to important crop plants.

The compounds (I) can be prepared by one of the following procedures: Procedure (a): A compound of the formula (I) can be prepared by reacting a compound of the formula:

wherein R1, X, Y, k, I, m, n and Z are each as defined above with a compound of the formula:

wherein A and B are each as defined above and B6 is a halogen atom.

The reaction is usually carried out in an inert solvent (e.g. water, benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, chloroform, carbon tetrachloride, ethyl acetate, pyridine or N,Ndimethylformamide). The reaction may be carried out in the presence of a base (e.g. pyridine, triethylamine, N,N-diethylaniline, sodium hydride or potassium hydroxide). If desired, a phase transfer catalyst (e.g.

tetra-n-butylammonium bromide) can be used so as to obtain the compound (I) in a high yield. The reaction may be carried out at a temperature of 0 to 1 50"C within 10 hours.

Procedure (b): The compound (I) wherein Z is hydrogen and B is a group of the formula: -W-R5 (in which Wand B5 are each as defined above) can be prepared by reacting a compound of the formula:

Wherein X, Y, k, I, m, n, A and R1 are each as defined above with a compound of the formula: R5-W-H (V) wherein B5 and Ware each as defined above.

The reaction may be carried out in the presence of an inert solvent (e.g. benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, N,N-dimethylformamide, chloroform or carbon tetrachloride). If desired, a base (e.g. triethylamine, N,N-diethylaniline or 1,4-diazabicyclo[2.2.2]octane) may be used as a catalyst. The reaction normally proceeds at a temperaure of 0 to 50"C within 10 hours.

The compound (iv) may be obtained by reacting the corresponding aniline derivative with phosgene or thiophosgene. The reaction may be carried out in an organic solvent (e.g. benzene, toluene, xylene or ethyl acetate) at a temperature of 50"C to the boiling point of the solvent within 10 hours.

Procedure (c): The compound (I) wherein Z is other than hydrogen may be prepared by reacting a compound of the tormula:

wherein Rq, X, Y, k, I, m, n and A are each as defined above with a compound of the formula: Z-R7 wherein R7 is a leaving group (e.g. halogen, tosyloxy, mesyloxy) and Z is as defined above.

The reaction is usually carried out in the presence of an organic solvent (e.g. N,N-dimethylform-amide, dimethylsulfoxide, diethyl ether or tetrahydrofuran) with a base (e.g. sodium hydride or potassium hydroxide) at a temperature of 0 to 1000C within 12 hours.

Procedure (d): The compound (I) wherein R1 and

are the same and each represent a group of the formula:

(in which R2, A' and A" are each as defined above) can be prepared by reacting a diamino compound of the formula:

wherein X, Y, k, I, m and n are each as defined above with a compound of the formula:

wherein B8 is a halogen atom and R2, A' and A" are each as defined above.

The reaction may be accomplished in the same manner as in the procedure (a).

The compound (VII) is obtainable by reducing a compound of the formula:

wherein X, Y, k, I, m and n are each as defined above.

The reduction may be performed in an inert solvent (e.g. ethanol, ethyl acetate, dioxane) in the presence of a catalyst (e.g. platinum oxide, palladium on carbon) in hydrogen stream under a pressure of 1 to 100 atm at a temperature of 10 to 200"C within 12 hours. The compound (VIII) can be obtained by a per se known method (cf. J.Chem.Soc., 1931,2492).

Atypical example for preparation of the compound (I) is illustratively shown below.

Example 1 6,8-Diamino-1,3-benzodioxane (3.32 g) and N,N-diethylaniline (6.00 g) were dissolved in dioxane (50 ml).

To the resultant solution was dropwise added methyl chloroformate (3.78 g) in 5 minutes under ice-cooling.

The resultant mixture was allowed to stand at room temperature for 12 hours, poured into ice-water and extracted with ethyl acetate. The extract was washed with water, dried over magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography using a mixture of toluene and ethyl acetate as an fluent to give 6,8-bis(methoxycarbonylamino)-1,3-benzodioxane (Compound No. 44) (4.94 g) in a yield of 87.5 %. M.P., 156.5 157.5"C.

Specific examples of the compounds (I) of the invention, which can readily be prepared according to the aforesaid procedures, are shown in Table 1.

Table 1

Compound X Y k 1 m n R1 A B Z No.

1 - CH2 1 0 0 1 -NO2 -C2R5 H 2 CH2 CH2 0 1 1 1 -CR-CHH02 O -CH-CHCH3 H 3 CH2 CH2 O 1 1 1 -NH2 O II 4 CH2 CH2 O 1 1 1 -NCS o D H 5 CH2 CR2 O 1 1 1 -NECzH5 O -oti)C3H7 H 6 CH2 CH2 O 1 1 1 -NH-C-CH3 -O-CH-CH=CH2 H II I o CH3 7 CH2 CH2 O 1 1 1 -NHCOOCH3 O -O-CH-CrCH H CH3 3 8 CH2 CH2 0 1 1 1 -Ne-C-OCH3 O -OCH2CHICHCH2C1 H II S 9 CH2 CH2 O 1 1 1 -NH-9-SCH3 O -OCH2C=CCH2C1 H O 10 CH2 CH2 O 1 1 1 -NH-C-SCH3 O -oce2ce2r H S 11 CH2 CH2 O 1 1 1 -NH-C-NHCH3 O OCH2CH2CN H II 0 /CH3 12 CH2 CH2 O 1 1 1 -NH-C-NX 3 O -O-tH e H II \cU3 O CH3 13 CH2 CH2 O 1 1 1 -NH-C-CH-CH2 O -O-tH-CH20CH3 H 23 Oil CH2C1 14 CH2 CH2 O 1 1 1 -NH-C-OCH2CrCH O -O-tH-CH3 H 2 15 CH2 CH2 O 1 1 1 -NH-C-OCR2CR2F O F H O -0e II 16 CH2 CH2 O 1 1 1 -NR-C-OCR2CR20CR3 0 -o 0 17 CH2 CH2 O 1 1 1 -NHCOOCH3 O -O(i)C3H7 -CR3 18 CH2 CH2 O 1 1 1 -NHCOOCH3 O -o(i)C3R7 -CH2CH"CH2 19 CH2 CH2 O 1 1 1 -NHCOOCH3 O -o(i)C3R7 -CH2C-CH (Continued)

Compound X Y k 1 m n R A B Z No.

20 CH2 CH2 0 1 1 1 -NUCOOCH3 0 -O(i)C3H7 -CR-COOCU3 CR3 21 CH2 CH2 0 1 1 1 -uRCOOCH3 0 -o(i)C314 -C-CR3 0 22 CH2 CH2 0 1 1 1 -NHCOOCH3 0 O(i)C3H7 23 CH2 CH2 0 1 1 1 -NHCOOCH3 0 -O(i)C3H7 24 - CH2 1 0 0 1 -NHCOOCH3 0 -O(i)C3H7 -SCH3 25 CH2 CH2 0 1 1 1 -NUCOOCH3 0 -O(i)C3H7 26 - CK2 1 0 0 1 -NUCOOCH3 0 -O(i)C3H7 -SCO0C2H5 27 CH2 CH2 0 1 1 1 -NRSCU3 0 -OCi)C3H7 H 28 CH2 CH2 1 1 0 1 -OSCH3 0 -O(i)C3H7 H 29 CH2 CH2 0 1 1 1 -SOCH3 0 -0(i)C3U7 U /SCH3 30 - CH2 1 0 0 1 -N-C O -O(i)C3H7 U 3 31 - CH2 1 0 0 1 S020CR3 0 -O(i)C3H7 U 32 - CH2 1 0 0 1 -S02NHCH3 0 -O(i)C3H7 H 33 CH2 CH2 0 1 1 1 -SC2H5 -O(i)C3H7 H 34 TICH3 CH2 0 1 1 1 --C2U5 0 -O(i)C3H7 H j3 -CR- 0 0 35 CH2 iC2fl5 O 1 1 1 -S-C2H5 0 -O(i)C3H7 H 125 -CH- O 36 - - CH2 1 0 0 1 -NUCOOCH3 S -OCR3 H 37 CH2 Ce2 0 1 1 1 -NeCOOCH3 0 -SC2H5 H 38 - CH2 1 0 0 1 -NHCOOCH3 0 -O(i)C3H7 H 39 CH2 CH2CH2 0 1 0 0 -NHCOOCH3 0 -O(i)C3H7 H 40 CH2 CH2 0 1 0 1 -NHCOOCH3 0 -O(i)C3H7 H 41 CH2 CH2 0 1 1 1 -NUCOOCH3 0 -O-CH-CHZOCH3 H 23 CH3 42 CH2 CH2 0 1 1 1 -NHCOOCH3 0 -O(i)C3H7 U 43 CH2 CH2 0 1 1 1 -NHCOOCH3 0 -OC2H5 H 44 CH2 CH2 0 1 1 1 -NI1COOCIS 0 -0CR3 H

In the practical usage of the compounds (I) as fungicides, they may be applied as such or in a formulation form such as dusts, wettable powders, oil sprays, emulsifiable concentrates, tablets, granules, fine granules, aerosols orflowables. Such formulation form can be formulated in a conventional manner by mixing at least one of the compounds (I) with an appropriate solid or liquid carrier(s) or diluent(s) and, if necessary, an appropriate adjuvant(s) (e.g. surfactants, adherents, dispersants, stabilizers) for improving the dispersibility and other properties of the active ingredient. Examples of the solid carriers or diluents are botanical materials (e.g. flour, tobacco stalk powder, soybean powder, walnut-shell powder, vegetable powder, saw dust, bran, bark powder, cellulose powder, vegetable extract residue), fibrous materials (e.g. paper, corrugated cardboard, old rags), synthetic plastic powders, clays (e.g. kaolin, bentonite, fuller's earth), talcs, other inorganic materials (e.g. pyrophyllite, sericite, pumice, sulfur powder, active carbon) and chemical fertilizers (e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ammonium chloride). Examples of the liquid carriers or diluents are water, alcohols (e.g. methanol, ethanol), ketones (e.g. acetone, methylethylketone), ethers (e.g. diethyl ether, dioxane, cellosolve, tetrahydrofuran), aromatic hydrocarbons (e.g. benzene, toluene, xylene, methyl naphthalene), aliphatic hydrocarbons (e.g. gasoline, kerosene, lamp oil), esters, nitriles, acid amides (e.g. dimethylformamide, diemethylacetamide), halogen ated hydrocarbons (e.g. dichloroethane, carbon tetrachloride), etc. Examples of the surfactants are alkyl sulfuric esters, alkyl sulfonates, alkylaryl sulfonates, polyethylene glycol ethers, polyhydric alcohol esters, etc. Examples of the adherents and dispersants may include casein, gelatin, starch powder, carboxymethyl cellulose, gum arabic, alginic acid, lignin, bentonite, molasses, polyvinyl alcohol, pine oil and agar. As the stabilizers, there may be used PAP (isopropyl acid phosphate mixture), tricresyl phosphate (TCP), tolu oil, epoxydized oil, various surfactants, various fatty acids and their esters, etc. The foregoing formulations generally contain at least one of the compounds (I) in a concentration of about 1 to 95 % by weight, preferably of 2.0 to 80 % by weight. By using the formulations, the compounds (I) are generally applied in such amounts as 2 to 100 g per 10 are. When only the drug-resistant strains of phytopathogenic fungi are present, the compounds (I) may be used alone. However, when the drug-sensitive strains are present together with the drug-resistant strains, their alternate use with benzimidazole, thiophanate and/or cyclic imide fungicides or their combined use with benzimidazole thiophanate and/or cyclic imide fungicides is favorable. In such alternate or combined use, each active ingredient may be employed as such or in conventional agricultural formulation forms. the weight proportion of the compound (I) and the benzimidazole, thiophanate and/or cyclic imide fungicide may be from about 1 1: 0.1 to 1 to 1:10.0. Typical examples of the benzimidazole, thiophanate and cyclic imide fungicides are shown in Table 2. Table 2 Com pound Structure \ Name

Methyl l-(butyl- carbamoyl)benzimidazol-2-ylcarbamate 2-(4-Thiazolyl)benz imidazole Methyl benzimidazol2-ylcarbamate 2-(2-Furyl)benz imidazole 1,2-Bis(3-methoxycarbonyl-2-thioureido)benzene Com pound Structure Name Name

1,2-Bis(3-ethoxy carbonyl-2-thio ureido)benzene y2-(O,S-Dimethyl- phosphorylamino) - 1- (3'-methoxycarbonyl 2'-thioureido)benzene 2-(O,O-Dimethylthio- phosphorylamino) -1- (3 '-methoxycarbonyl- 2 '-thioureido) benzene N-(3',5'-Dichloro phenyl)-1,2-dimethyl cyclopropane-l, 2-di- carboximide 3-(3',5'-Dichloro phenyl) -1-isopropyl- carbamoylimida zolidin-2,4-dione 3-(3',5'-Dichloro phenyl)-5-methyl-5 vinyloxazolidin-2,4 dione Ethyl (RS)-3-(3',5'- dichlorophenyl)-5 methyl-2,4-dioxo- oxazolidine-5 carboxylate Besides, the compounds (I) may be also used in admixture with other fungicides, herbicides, insecticides, miticides, fertilizers, etc.

When the compounds (i) are used as fungicides, they may be applied in such amounts as 2 to 100 grams per 10 area. However, this amount may vary depending upon formulation forms, application times, application methods, application sites, diseases, crops and so on, and therefore, they are not limited to said particular amounts.

Some practical embodiments of the fungicidal composition according to the invention are illustratively shown in the following Examples wherein % and part(s) are by weight.

Formulation Example 1 Two parts of Compound no.44,88 parts of clay and 10 parts of talc are thoroughly pulverized and mixed together to obtain a dust formulation containing 2 % of the active ingredient. Formulation Example 2 Thirty parts of Compound No.44,45 parts of diatomaceous earth, 20 parts of white carbon, 3 parts of sodium laurylsulfate as a wetting agent and 2 parts of calcium ligninsulfonate as a dispersing agent are mixed while being powdered to obtain a wettable powder formulation containing 30 % of the active ingredient. Formulation Example 3 Fifty parts of Compound No.44,45 parts of diatomaceous earth, 2.5 parts of calcium alkylbenzene sulfonate as a wetting agent and 2.5 parts of calcium ligninsulfonate as a dispersing agent are mixed while being powdered to obtain a wettable powder formulation containing 50 % of the active ingredient. Formulation Example 4 Ten parts of Compound No. 44, 80 parts of cyclohexanone and 10 parts of polyoxyethylene alkylaryl ether as an emulsifier are mixed together to obtain an emulsifiable concentrate formulation containing 10% of the active ingredient. Formulation Example 5 One part of Compound No.44, 1 part of Compound 1,88 parts of clay and 10 parts of talc are thoroughly pulverized and mixed together to obtain a dust formulation containing 2 parts of the active ingredient. Formulation Example 6 Twenty parts of Compound No.44, 10 parts of Compound J, 45 parts of diatomaceous earth, 20 parts of white carbon, 3 parts of sodium laurylsulfate as a wetting agent and 2 parts of calcium ligninsulfonate as a dispersing agent are mixed while being powdered to obtain a wettable powder composition containing 30 % of the active ingredient. Formulation Example 7 Ten parts of Compound No.44,40 parts of Compound A, 45 parts of diatomaceous earth, 2.5 parts of calcium alkylbenzenesulfonate as a wetting agent and 2.5 parts of calcium ligninsulfonate as a dispersing agent are mixed while being powdered to obtain a wettable powder composition containing 50 % of the active ingredient. Typical test data indicating the excellent fungicidal activity of the compounds (I) are shown below. The compounds used for comparison are as follows: Compound /Remarks Swep Commercially available herbicide

Commercially available herbicide Commercially available herbicide Commercially available herbicide Compound Remarks

Commercially available herbicide Commercially available herbicide Commercially available fungicide Commercially available fungicide Commercially available fungicide Commercially available fungicide Experiment 1 Protective activity test on powdery mildew of cucumber (Sphaerotheca fuliginea) :- A flower pot of 90 ml volume was filed with sandy soil, and seeds of cucumber (var: Sagami-hanjiro) were sowed therein. Cultivation was carried out in a greenhouse for 8 days. Onto the resulting seedlings having cotyledons, the test compound formulated in emulsifiable concentrate or wettable powder and diluted with water was sprayed at a rate of 10 ml per pot. Then, seedlings were inoculated with a spore suspension of the drug-resistant or drug-sensitive strain of Sphaerotheca fuliginea by spraying and further cultivated in the greenhouse. Ten days thereafter, the infectious state of the plants was observed. The degree of damage was determined in the following manner, and the results are shown in Table 3.

The leaves examined were measured for a percentage of infected area and classified into the corresponding disease indices, 0,0.5, 1,2,4: Desease index Percentage of infected area 0 No infection 0.5 Infected area of less than 5 % 1 Infected area of less than 20 % 2 Infected area of less than 50 % 4 Infected area of not less than 50 % The disease severity was calculated according to the following equation: Disease - (Disease index) x (Number of leaves) x 100 severity 4 x (Total number of leaves or examined) (%) The prevention value was calculated according to the following equation:: Prevention (Disease severity in treated plot) value =100- (Disease severity in untreated plot) x 100 (%) TABLE 3 Compound Concentration Prevention Prevention No. ofactive value when value when ingredient inoculated inoculated (p pm) with drug- with drug resistant sensitive strain f /OJ strain (O/oj 44 500 100 0 Swep 200 0 0 Chlorpropham 200 0 0 Barban 200 25 0 CEPC 200 0 0 Propham 200 0 0 Chlorbufam 200 0 0 Benomyl 200 0 100 Thiophanate- 200 0 100 methyl Carbendazim 200 0 100 As understood from the results shown in Table 3, the compounds (I) of the invention show an excellent preventive effect on the drug-resistant strain but do not show any preventive effect on the tested drug-sensitive strain.To the contrary, commercially available known fungicides such as Benomyl, Thiophanate-methyl and Carbendazim show a notable controlling effect on the drug-sensitive strain but not on the drug-resistant strain. Other tested compounds structurally similar to the compounds (I) do not show any fungicidal activity on the drug-sensitive strain and the drug-resistant strain.

Experiment 2 Preventive effect on cercospora leaf spot of sugerbeet (Cercospora beticola) : A flower pot of 90 ml volume was filled with sandy soil, and seeds of sugarbeet (var: Detroit dark red) were sowed therein. Cultivation was carried out in a greenhouse for 20 days. Onto the resulting seedlings, the test compound formulated in emulsifiable concentrate or wettable powder and diluted with water was sprayed at a rate of 10 ml per pot. Then, the seedlings were inoculated with a spore suspension of the drug-resistant or drug-sensitive strain of Cercospora beticola by spraying. The pot was covered with a polyvinyl chloride sheet to make a condition of high humidity, and cultivation was continued in the greenhouse for 10 days. The degree of damage was determined in the same manner as in Experiment 1, and the results are shown in Table 4.

TABLE 4 Compound Concentration Prevention Prevention No. ofactive value when value when ingredient inoculated inoculated (ppm) with drug- with drug resistant sensitive strain {%J strain (%) 44 500 100 0 Swep 200 0 0 Chlorpropham 200 0 0 Barban 200 34 0 CEPC 200 0 0 Propham 200 0 0 Chlorbufam 200 0 0 Benomyl 200 0 100 Thiophanate- 200 0 100 methyl Carbendazim 200 0 100 As understood from the results shown in Table 4, the compounds (I) of the invention show an excellent preventive effect of the drug-resistant strain but do not show any preventive effect on the tested drug-sensitive strain. To the contrary, commecially available known fungicides such as Benomyl and Thiophanate-methyl show a notable controlling effect on the drug-sensitive strain but not on the drug-resistant strain.Other tested compounds structurally similar to the compounds (I) do not show any fungicidal activity on the drug-sensitive strain and the drug-resistant strain.

Experiment 3 Preventive effect on scab of pear (Venturia nashicola): A plastic pot of 90 ml volume was filled with sandy soil, and seeds of pear (var: Chojuro) were sowed therein. Cultivation was carried out in a greenhouse for 20 days. Onto the resulting seedlings, the test compound formulated in emulsifiable concentrate or wettable powder and diluted with water was sprayed at a rate of 10 ml per pot. Then, the seedlings were inoculated with a spore suspension of the drug-resistant or drug-sensitive strain of Venturia nashicola by spraying. The resulting plants were piaced at 20"C under a condition of high humidity for 3 days and then at 20"C under irradiation with a fluorescent lamp for 20 days.

The degree of damage was determined in the same manner as in Experiment 1, and the results are shown in Table 5.

TABLE 5 Compound Concentration Prevention Prevention No. ofactive value when value when ingredient inoculated inoculated (ppm) with drug- with drug resistant sensitive strain lO/ol strain /O/oJ 44 500 100 0 Benomyl 200 0 100 Thiophanate- 200 0 100 methyl As understood from the results shown in Table 5, the compounds (I) of the invention show an excellent preventive effect on the drug-resistant strain but do not show any preventive effect on the tested drug-sensitive strain. To the contrary, commercially available known fungicides such as Benomyl and Thiophanate-methyl show a notable controlling effect on the drug-sensitive strain but not on the drug-resistant strain.

Experiment 4 Preventive effect on brown leaf-spot of peanut (Cercospora arachidicola): Plastic pots of 90 ml volume was filled with sandy soil, and seeds of peanut (var: Chiba hanryusei) were sowed therein. Cultivation was carried out in a greenhouse for 14 days. Onto the resulting seedlings, the test compound formulated in emulsifiable concentrate or wettable powder and diluted with water was sprayed at a rate of 10 ml per pot. Then, the seedlings were inoculated with a spore suspension of the drug-sensitive strain of Cercospora arachidicola by spraying. The resulting plants were covered with a polyvinyl chloride sheet to make a condition of humidity and cultivated in the greenhouse for 10 days. The degree of damage was determined in the same manner as in Experiment land the results as shown in Table 6.

TABLE 6 Compound Concentration Prevention Prevention No. ofactive value when value when ingredient inoculated inoculated (pom) with drug- with drug resistant sensitive strain (%) strain { /0) 44 500 100 0 Benomyl 200 0 100 Thiophanate- 200 0 100 methyl As understood from the results shown in Table 6, the compounds (I) of the invention show an excellent preventive effect on the drug-resistant strain but do not show any preventive effect on the tested drug-sensitive strain. To the contrary, commercially available known fungicides such as Benomyl and Thiophanate-methyl show a notable controlling effect on the drug-sensitive strain but not on the drug-resistant strain.

ExperimentS Preventive effect on gray mold of cucumber (Botrytis cinerea): Plastic pots of 90 ml volume was filled with sandy soil, and seeds of cucumber (var: Sagami-hanjiro) were sowed therein. Cultivation was carried out in a greenhouse for 8 days to obtain cucumber seedlings expanding cotyledons. Onto the resulting seedlings, the test compound formulated in emulsifiable concentrate or wettable powder and diluted with water was sprayed at a rate of 10 ml per pot. After air-drying, the seedlings were inoculated with mycelial disks (5 mm in diameter) of the drug-resistant or drug-sensitive strain of Botrytis cinerea by putting them on the leaf surfaces. After the plants were infected by incubating under high humidity at 20"C for 3 days, the rates of disease severity were observed.The degree of damage was determined in the same manner as in Experiment 1, and the results are shown in Table 7.

TABLE 7 Compound Concentration Prevention Prevention No. ofactive value when value when ingredient inoculated inoculated (ppm) with drug- with drug resistant sensitive strain {%) strain {%) 44 500 100 0 Benomyl 200 0 100 Thiophanate- 200 0 100 methyl As understood from the results shown in Table 7, the compounds (I) of the invention show an excellent preventive effect on the drug-resistant strain but do not show any preventive effect on the tested drug-sensitive strain. To the contrary, commercially available known fungicides such as Benomyl and Thiophanate-methyl show a notable controlling effect on the drug-sensitive strain but not on the drug-resistant strain.

Experiment 6 Preventive effect on gummy stem blight of cucumber (Mycosphaerella melonis): Plastic pots of 90 ml volume was filled with sandy soil, and seeds of cucumber (var: Sagami-hanjiro) were sowed therein. Cultivation was carried out in a greenhouse for 8 days to obtain cucumber seedlings expanding cotyledons. Onto the resulting seedlings, the test compound formulated in emulsifiable concentrate of wettable powder and diluted with water was sprayed at a rate of 10 ml per pot. After air-drying, the seedlings were inoculated with mycelial disks (5 mm in diameter) of the drug-resistant or drug-sensitive strain of Mycosphaerella melonis by putting them on the leaf surfaces. After the plants were infected by incubating under high humidity at 25"C for 4 days, the rates of disease severity were observed.

The degree of damage was determined in the same manner as in Experiment 1, and the results are shown in Table 8.

TABLE 8 Compound Concentration Prevention Prevention No. ofactive value when value when ingredient inoculated inoculated (ppmJ with drug- with drug resistant sensitive strain { /OJ strain { /OJ 44 500 100 0 Benomyl 200 0 100 Thiophanate- 200 0 100 methyl As understood from the results shown in Table 8, the compounds (I) of the invention show an excellent preventive effect on the drug-resistant strain but do not show any preventive effect on the tested drug-sensitive strain. To the contrary, commercially available known fungicides such as Benomyl and Thiophanate-methyl show a notable controlling effect on the drug-sensitive strain but not on the drug-resistant strain.

Experiment 7 Preventive effect on green mold of orange (Penicillium italicum): Fruits of orange (var: Unshu) were washed with water and dried in the air. The fruits were immersed in a solution of the test compound prepared by diluting an emulsifiable concentrate comprising the test compound with water for 1 minute. After drying in the air, the fruits were inoculated with a spore suspension of the drug-resistant or drug-sensitive strain of Penicillium italicum by spraying and placed in a room of high humidity for 14 days.The degree of damage was determined in the following manner: The fruits examined were measured for a percentage of infected area and classified into the corresponding indices,0,1,2,3,4,5: Disease index Percentage of infected area 0 No infection 1 Infected area of less than 20 % 2 Infected area of less than 40 % 3 Infected area of less than 60 % 4 Infected area of less than 80 % 5 Infected area of not less than 80% Calculation of the degree of damage and the prevention value was made as in Experiment 1.

The results are shown in Table 9.

TABLE 9 Compound Concentration Prevention Prevention No. of active value when value when ingredient inoculated inoculated (ppmJ with drug- with drug resistant sensitive strain lO/ol strain f /OJ 44 500 100 0 Benomyl 200 0 100 Thiophanate- 200 0 100 methyl As understood from the results shown in Table 9, the compounds (I) of the invention show an excellent preventive effect on the drug-resistant strain but do not show any preventive effect on the tested drug-sensitive strain. To the contrary, commercially available known fungicides such as Benomyl and Thiophanate-methyl show a notable controlling effect on the drug-sensitive strain but not on the drug-resistant strain.

Experiment 8 Phytotoxicity on crop plants: Plastic pots of 150 ml volume were filled with sandy soil, and seeds of wheat (var: Norin No.61), apple (var: Kogyoku) and peanut (var: Chiba hanryusei) were sowed therein. Cultivation was carried out in a greenhouse. Onto the resulting seedlings, the test compound formulated in emulsifiable concentrate or wettable powder and diluted with water was sprayed. After cultivation in the greenhouse for additional 10 days, the phytotoxicity was examined on the following criteria: Extent Observation - No abnormality + Abnormality due to phytotoxicity observed in a part of crop plants ++ Abnormality due to phytotoxicity observed in entire crop plants +++ Crop plants withered due to phytotoxicity The results are shown in Table 10.

TABLE 10 Compound Concentration Phytotoxicity No. ofactive ingredient Wheat Apple Peanut (ppm) 44 1000 - - Barban 1000 - ++ ++ CEPC 1000 + ++ Swep 1000 + ++ + As understood from the results shown in Table 10, the compounds of the formula (I) of the invention produce no material phytotoxicity, while commercially available herbicides having a chemical structure similar thereto produce considerable phytotoxicity.

Experiment 9 Preventive effect on powdery mildew of cucumber (Sphaerotheca fuliginea): A plastic pot of 90 ml volume was filled with sandy soil, and seeds of cucumber (var: Sagami-hanjiro) were sowed therein. Cultivation was carried out in a greenhouse for 8 days. Onto the resulting seedlings having cotyledons, the test compounds(s) formulated in emulsifiable concentrate or wettable powder and diluted with water were sprayed at a rate of 10 ml per pot. Then, the seedlings were inoculated with a mixed spore suspension of the drug-resistant and drug-sensitive strain of Sphaerotheca fuliginea by spraying and further cultivated in the greenhouse. Ten days thereafter, the infectious state of the plants was observed. The degree of damage was determined in the same manner as in Experiment 1, and the results are shown in Table 11.

TABLE 11 Compound No. Concentration of Prevention active ingredient value /pom) ( /OJ 44 100 40 44 20 0 44+G 20+20 100 44+H 20+20 100 As understood from the results shown in Table 1 1,the combined use of the compounds (I) of the invention with benzimidazole, thiophanate and/or cyclic imide fungicides show much more excellent preventive effect than their sole use.

Experiment 10 Preventive effect on gray mold of tomato (Botrytis cinerea): A plastic pot of 90 ml volume was filled with sandy soil, and seeds of tomato (var: Fukuju No. 2) were sowed therein. Cultivation was carried out in a greenhouse for 4 weeks. Onto the resulting seedlings at the 4-leaf stage, the test compound(s) formulated in emulsifiable concentrate or wettable powder and diluted with water were sprayed at a rate of 10 ml per pot. Then, the seedlings were inoculated with a mixed spore suspension of the drug-resistant and drug-sensitive strain of Botrytis cinerea by spraying and piaced at 20"C in a room of high humidity for 5 days. The degree of damage was determined in the same manner as in Experiment 1, and the results are shown in Table 12.

TABLE 12 Compound No. Concentration of Prevention active ingredient value (pom) (O/oJ 44 100 36 44 20 0 1 100 48 1 20 20 J 500 44 J 100 16 K 100 40 K 20 18 L 500 42 L 100 10 44+1 10 + 20 100 44+J 10 + 20 100 44 + K 10 if 20 100 44 + L 10 + 20 100 As understood from the results shown in Table 12, the combined use of the compounds (I) of the invention with benzimidazole, thiophanate and/or cyclic imide fungicides show much more excellent preventive effect than their sole use.

Claims (14)

1. Acompound oftheformula:

wherein: X and Y are each independently a lower alkylene group or a lower alkoxy(lower)alkylene group; k, i, m and n are, each independently 0 or 1; R1 is a nitro group, a 2-nitrovinyl group, an amino group, an isothiocyanato group, a lower alkylamino group or a group of the formula::

(in which A' and A" are, each independently an oxygen atom or a sulfur atom, R2 and R2 are, each independently a lower alkyl group, a lower alkenyl group, a loweralkynyl group or a halo(lower)-alkyl group or a lower alkoxy(lower)alkyl group and n is 0, 1 or 2); Z is a hydrogen atom, a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower alkoxy-carbonyl(lower)alkyl group or a group of the formula:

or -S-R4 (in which B3 is a lower alkyl group, a cyclo(lower)alkyl group or a phenyl group and R4 is a lower alkyl group, a phenyl group or a lower alkoxycarbonyl group); A is an oxygen atom or a sulfur atom; and B is a lower alkyl group, a lower alkenyl group, a cyclo(lower)alkyl group, a phenyl group or a group of the formula: -W-R5 (in which W is an oxygen atom or a sulfur atom and B5 is a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a halo(lower)alkenyl group, a halo(lower)alkynyl group, a cyclo(lower)alkyl group, a phenyl group optionally substituted with halogen or a lower alkyl group substituted with at least one halogen, cyano, phenyl, cyclo(lower)alkyl or lower alkoxy).

2. A fungicidal composition which comprises as an active ingredient a fungicidally effective amount of a compound oftheformula:

wherein: X, Y, Z, R1, A, B, k, I, m and n are as defined in Claim 1, together with an inert carrier or diluent.

3. Afungicidal composition as claimed in Claim 2 which further comprises as an additional active ingredient(s) a benzimidazole, thiophanate and/or a cyclic imide fungicide.

4. A fungicidal composition as claimed in Claim 3 wherein the benzimidazole fungicide is methyl 1-(butylcarbamoyl)benzimidazol-2-ylcarbamate, 2-(2-furyl) benzimidazole, 2-(4-thiazoiyi)benzimidazole or methyl benzimidazol-2-ylcarbamate.

5. A fungicidal composition as claimed in Claim 3 wherein the thiophanate fungicide is 1,2-bis(3 methoxycarbonyl-2-thioureido)benzene, 2-(O,S-dimethylphosphorylamino)-1 -(3'-methoxycarbonyl-2'- thioureido)benzene or 2-(O,O-dimethylthiophosphorylamino)-1 -(3'-methoxycarbonyl-2'4hioureido)benzene.

6. A fungicidal composition as claimed in Claim 3 wherein the cyclic imide fungicide is 3-(3',5' dichloropheny)-1 ,2-dimethylcyclo-propane-1 2-dicarboximide, 3-(3',5'-dichlorophenyl)-1 - isopropylcarbamoylimidazolidine-2,4-dione, 3-(3',5'-dichlorophenyl)-5-methyl-5-vinyloxazoline-2,4-dione or ethyl (BS)-3-(3',5'-dichlorophenyl)-5-methyl-2,4-dioxooxazolidine-5-carboxylate.

7. A method for controlling plant pathogenic fungi which comprises applying a fungicidally effective amount of at least one compound of the formula:

wherein X, Y, Z, A, B, k, I, m, n and R1 are each as defined in claim 1, to plant pathogenic fungi.

8. A method as claimed in Claim 7, wherein the plant pathogenic fungi is a drug-resistant strain.

9. A method for controlling plant pathogenic fungi which comprises applying a fungicidally effective amount of a mixture of the compound of the formula:

wherein X, Y, Z, A, B, k, I, m, n and R1 are each as defined in claim 1 and a benzimidazole , thiophanate and/or a cylic imide fungicide, to plant pathogenic fungi.

10. A compound as claimed in Claim 1 for use as a fungicide.

11. A process for producing a compound of the formula:

wherein: X, Y, Z, A, B, k, I, m, n and R1 are as defined in Claim 1 which process comprises (a) reacting a compound of the formula:

wherein R1, X, Y, k, I, m, n and Z are each as defined above with a compound of the formula: R6-C-B B6-C-B (Ill) A wherein A and B are each as defined above and B6 is a halogen atom; (b) reacting a compound of the formula:

wherein X, Y, k, I, mn, A and R1 are each as defined above with a compound of the formula: RS-W-H (V) wherein B5 and Ware each as defined above; (c) reacting a compound of the formula:

wherein R1, X, Y, k, I, m, n and A are each as defined above with a compound of the formula Z-R7 wherein R7 is a leaving group and Z is as defined above; or (d) reacting a compound of the formula:

wherein X, Y, k, I, m and n are each as defined above with a compound of the formula:

wherein B8 is a halogen atom and A', A" and B2 are each as defined above.

12. A process as claimed in Claim 11 substantially as hereinbefore described with reference to Example 1.

13. A compound as claimed in Claim 1 whenever prepared by a process as claimed in Claim 11 or Claim 12.

14. A compound as claimed in Claim 1 as hereinbefore specifically exemplified.