GB2137191A - Fungicidal N-phenylimidates - Google Patents

Abstract

New N-phenylimidates of the formula: <IMAGE> are of use as fungicidal agents against phytopathogenic fungi, particularly their strains resistant to benzimidazole thiophanate fungicides and/or cyclic imide fungicides. In the formula X and Y represent specified substituent groups and Z represents hydrogen or a substituent group; A and B each represent an oxygen atom, a sulphur atom, or the group -NR<8>-.

Description

SPECIFICATION Fungicidal N-phenylimidates This invention relates to fungicidal N-phenylimidates.

Benzimidazole 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-methoxycarbonyl2-thioureido)benzene), Thiophanate (1 ,2-bis(3-ethoxycarbonyl-2-thioureido)benzene), 2-(O,S dimethylphosphorylamino)-1 -(3'-methoxycarbonyl-2'-thioureido)benzene and 2-(0,0- dimethylthiophosphorylamino)-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 1 970. However, their continuous application over a long period of time results in phytopathogenic fungi developing a tolerance to them, whereby their plant diseasepreventative effect is lowered. Furthermore, the fungi which gain tolerance to certain benzimidazole thiophanate also show considerable tolerance to some other benzimidazole thiophanate fungicides.

Thus, they are apt to develop cross-tolerance. Thus, if any significant decrease in their plant diseasepreventative 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 application is discontinued. Although other types of fungicides have to be used in this case, only a few are as effective as the benzimidazole 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'-dichloro-phenyl)-1 - isopropylcarbamoylimidazolidine-2,4-dione), Vinchlozoline (3-13',5'-(dichlorophenyl)-5-methyl-5- vinyloxazolidin-2,4-dione), and ethyl (RS)-3-(3 ,5-dichlorophenyl)-5-methyl-2,4 -dioxooxazolidine-5- carboxylate which are effective against various plant diseases, 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), Chlorpropham (isopropyi N-(3-chlorophenyl)carbamate) and Propham (isopropyl N-phenylcarbamate) exhibit a fungicidal activity against certain organisms tolerant to benzimidazole thiophanate fungicides. However, their fungicidal activity against the drug-resistant fungi is not strong enough, and thus, in practice, they cannot be used as fungicides.

We have now found that certain N-phenylimidates possess an excellent fungicidal activity against plant pathogenic fungi which have developed resistance to benzimidazole thiophanate fungicides and/or cyclic imide fungicides.

Accordingly the present invention provides an N-phenylimidate of the formula:

wherein X and Y are each independently a halogen atom, a lower alkyl group, a lower alkenyl group, a lower cyano alkenyl group, a lower alkynyl group, a lower alkoxy group, a cyano group, a lower alkyl group substituted with at least one halogen atom, hydroxy or cyano group or a group of the formula: -CH2OR3,

in which R3 is a lower alkyl group, a lower alkenyl group, a lower alkynyl group or a lower haloalkyl group, R4 and R5 are each independently a lower alkyl group, R6 is a hydrogen atom or a lower alkyl group and n is 2, 3 or 4;Z is a hydrogen atom, a fluorine atom or a group of the formula: -OR7 in which R7 is a lower alkyl group, a lower alkenyi group, a lower alkynyl group or a lower alkyl group substituted with at least one halogen atom, lower alkoxy or lower cycloalkyl group; A and B are each independently an oxygen atom, a sulfur atom or a group of the formula: -NR8 in which R8 is a hydrogen atom, a lower alkyl group, a lowercycloalkyl group, a lower cylcoalkenyl group, a lower cycloalkynyi group, a lower alkoxyalkyl group, a lower haloalkyl group, a lower hydroxyalkyl group or a lower aralkyl group;R1 and R2 are each independently a C1-C8 alkyl group, a C3-C6 alkenyl group, a C3-C8 alkynyl group, a lower cycloalkyl group, a lower haloalkenyl group, a lower haloalkynyl a phenyl group or a group of the formula:

SO2R9 or --SS-R9 in which L and M are, each independently an oxygen atom or a sulfur atom and R9 is a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a aralkyl group, a phenyl group, a heteroalkyi group, a lower alkyl group substituted with at least one halogen atom, cyano, lower alkoxy or phenoxy group, a phenyl group substituted with at least one halogen atom, cyano, nitro, lower alkyl or lower alkoxy group or a lower alkyl group substituted with at least one halogen atom, cyano, lower alkoxy, lower alkenyloxy, lower haloalkoxy, lower alkyloxyimino, phenoxy, lower alkyloxy, phenyl, lower cycloalkyl, naphthyl, heteroaryl, or phenyl substituted with at least one halogen atom, cyano, lower alkyl, lower alkoxy, phenoxy, lower haloalkyl, lower haloalkenyl, lower haloalkynyl, alkenyl, alkynyl, lower cycloalkyl, lower alkoxyalkyl, lower haloalkoxyalkyl, lower alkylcarbonyl, lower alkoxycarbonyl, lower alkylamino or lower alkylthio group, or R' and R2 may be combined together to form a group of the formula:

in which n is 2 or 3:: It is notable that the fungicidal potency of the compounds of the invention against organisms tolerant to benzimidazole thiophanate fungicides and/or cyclic imide fungicides (hereinafter referred to as "drugresistant fungi" or "drug-resistant strains") is much higher than that against the organisms sensitive to bezimidazole thiophanate fungicides and/or cyclic imide fungicides (hereinafter referred to as "drugsensitive fungi" or "drug-sensitive strains").

By the term "lower" as used herein in connection with organic groups or compounds is meant that such groups or compounds each contain not more than 6 carbon atoms. Similarly, by the term "heteroalkyl" as used herein in connection with organic groups or compounds is meant 5-membered heterocycles, condensed 5-membered heterocycles or 6-membered such as furyl thiophenyl, pyrrolyl, pyrazolyl, 1 2,3-triazolyl, 1 2,4-triazolyl, oxazoyl, isoxazolyl, thiazolyl, isothiazolyl, benzofuranyl, benzothiophenyl, indolyl, benzimidazolyl, indazolyl, benzoxazolyl, isoxazolyl, benzthiazoyl, pyridinyl, pyridazinyl, pyrimidinyl and pyrazinyl.

Thus, the present invention provides a fungicidal N-phenylimidate (i) and a fungicidal composition which comprises, as an active ingredient, a fungicidally effective amount of at least one N-phenylimidate (I), together with an inert carrier or diluent. It also provides a combination composition comprising as active ingredients an N-phenylimidate (i) together with a benzimidazole thiophanate fungicide and/or a cyclic imide fungicide, which is fungicidally effective against not only drug-sensitive fungi but also drugresistant fungi, and hence particularly effective for the prevention of plant diseases.It also provides a method of controlling plant pathogenic fungi including drug-resistant strains and drug-sensitive strains by applying a fungicidally effective amount of the N-phenylimidate (I) to plant pathogenic fungi, and a process for producing the N-phenylimidate (I).

The N-phenylimidates (I) can be prepared by either one of the following procedures: Procedure (a):- An N-phenylimidate (I) can be prepared by reacting an aniline derivative of the formula:

wherein X, Y, Z, A and R' are each as defined above, with a halide of the formula: X1-R2 (Ill) wherein R2 is as defined above and X' is a halogen atom.

The reaction is usually carried out in the presence of an inert solvent (e.g. benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, chloroform, tetrachloride, ethyl acetate, pyridine, dimethylformamide). If desired, the reaction may be carried out in the presence of an organic dehydrohalogenating agent (e.g. pyridine, triethylamine, diethylaniline) or an inorganic dehydrohalogenating agent (e.g. sodium hydroxide, potassium hydroxide) with a phase-transfer catalyst (e.g. tetra-n-butylammonium bromide, benzyl triethylammonium chloride, methyl trioctylammonium chloride), which is used in the absence or presence of water, so as to obtain the desired compound (i) in a high yield. The reaction may be carried out at a temperature in the range of from 0 to 1 500C, either instantaneously or within 10 hours.

Procedure (b):- An N-phenylimidate (I) can also be prepared by reacting an N-phenylimidoyl chloride of the formula:

wherein X, Y, Z, A and R1 are each as defined above, with a compound of the formula: HB-R2 (V) wherein B and R2 are each as defined above.

The reaction may be performed under substantially the same conditions as those of procedure (a).

Procedure (c):- An N-phenylimidate (I) can also be prepared by reacting an N-phenylimidoyl dihalide of the formula:

wherein X, Y and Z are each as defined above and Q is a halogen atom, with a compound of the formula: HA-R1 (Vll) or HB-R2 (V) wherein A, B, R1 and R2 are each as defined above.

The reaction may be performed under substantially the same conditions as those of procedure (a).

Procedure (d):- An N-phenylimidate (I) can also be prepared by reacting an N-phenyldithiocarbonimidate of the formula:

wherein X, Y, Z, R1 and R2 are each as defined above, with a compound of the formula: HA'-R1 (IX) or HA'-R2 (X) wherein R1 and R2 are each as defined above and A' is an oxygen atom or a group of the formula: -NR8 in which R8 is as defined above.

The reaction is usually carried out in the presence of an inert solvent (e.g. benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, chloroform, carbon tetrachloride, ethyl acetate, dimethylformamide) and may be carried out at a temperature in the range of from 40 to 1 500C, either instantaneously or within 20 hours.

Procedure (e):- An N-phenylimidate (I) can be prepared by reacting a compound of the formula:

wherein X, Y, Z, R1, R2 and R6 are each as defined above, with an amine of the formula:

wherein R2 and R8 are each as defined above.

The reaction may be performed under substantially the same conditions as those of procedure (c).

The n-phenylimidates (I) are fungicidally effective against a wide scope of plant pathogenic fungi, of which examples are as follows: Posdosphaera leucotricha, Venturia inaegualls, Mycdsphaerella pomi, Marssonina mali and Scterotinia mali of apple, Phyllactinia kakicola and Gloeosporium kaki of persimmon, Cladosporium carpophilum and Phomopsis sp. of peach, Cercospora viticola, Uncinula necator, Elsinoe ampelina and Glomerella cingulata of grape Cercospora beticola of sugarbeet, Cercospora arachidicola and Cercospora personata of peanut, Erysiphe graminis f. sp. horde, 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 celery, Phaeoisariopsis griseola of kidney bean, Erysiphe cichoracearum of tobacco, Diplo carp on 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, Scierotinia sclerotiorum of cucumber, eggplant, pimiento, lettuce, celery, kidney bean, soybean, azuki bean, potato or sunflower, Sclerotinia cinerea of peach or cherry, Mycosphaerella melonis of cucumber or melon, etc. Namely the N-phenylimidates (I) are highly effective in controlling the drug-resistant strains of said fungi.

The N-phenylimidates (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 Pyridularia oryzae, Pseudoperonospora cubensis, Plasmopara, viticola, Phytophthora infes tans, etc.

Advantageously, the N-phenylimidates (I) are low in toxicity and have little detrimental action on mammals and fish.

They may be applied to agricultural fields without causing any significant toxicity to important crop plants.

The process for the preparation of the N-phenylimidates (I) are illustratively shown in the following examples.

EXAMPLE 1 Preparation of S-isopropyl S'-benzyl-N-(3,4-diethoxy-5-methylphenyl)dithiocarbonimidate To a mixture of isopropyl N-(3,4-diethoxy-5-methylphenyl)dithiocarbamate (3.13 g; 0.01 mole) in 15 ml of methanol was added a sodium methylate solution prepared from metallic sodium (0.23 g; 0.01 mole) and methanol (30 ml) below 1 00C. Then, benzyl bromide (2.41 g; 0.013 mole) was added dropwise to the cold solution and the mixture was allowed to stand for 3 hours, poured into cold water (300 ml) and extracted with ethyl acetate (150 ml). The extract was washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure.The oily residue was purified by silica gel column chromatography using toluene/tetrahydrofuran (9/1) as an eluent to give Sisopropyl S'-benzyl-N-(3,4-diethoxy-5-methylphenyl)dithiocarbonimidate (3.79 g) in yield of 94%.

n28 = 1.5791. NMR (CDC13, TMS) : 1.2-1.6 (1 2H, m), 2.20 (3H, s) 3.65.30 (7H, m), 6.20 (2H, S), 7.22 (5H, s).

EXAMPLE 2 Preparation of methyl S-(m4luorobenzyl)-N-(3 ,4-diethoxy-5- methylphenyl)monothiocarbonimidate: To a mixture of methyl N-(3,4-diethoxy-5-methylphenyl)dithiocarbamate (2.69 g: 0.01 mole) in 1 5 ml of methanol was added a sodium methylate solution prepared from metallic sodium (0.23 g; 0.01 mole) and methanol (30 ml) below 1 OOC. Then, 3-fluorobenzyl bromide (2.84 g; 0.015 mole) was added dropwise to the cold solution and the mixture was allowed to stand for 3 hours, diluted with water (1 00 ml) and extracted with ethyl acetate (150 ml). The extract was washed with water (100 ml), dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The oily residue was purified by silica gel column chromatography using toluene/tetrahydrofuran (9/1) as an eluent to give methyl S-(m-fluorobenzyl)-N-(3,4-diethoxy-5-methylphenyl)monothiocarbonimidate (3.66 g) in a yield of 97%. nD5 = 1.5582. NMR (CDCl3, TMS) b: 1.32 (3H, t), 1.38 (3H, t), 2.17 (3H, s), 3.90 (3H, s), 3.72-4.13 (4H, m), 6.25 (2H, s), 6.80-7.50 (4H, m).

EXAMPLE 3 Preparation of ethyl S-methyl-N-(3-chloro-4-ethoxy-5 methoxymethylphenyl)monothiocarbonimidat To a mixture of methyl N-(3-chloro-4-ethoxy-5-methoxymethylphenyl)-1-chlorothioformimidate (3.08 g; 0.01 mole) in 15 ml of ethanol was added a sodium ethylate solution prepared from metallic sodium (0.23 g; 0.01 mole) and ethanol (20 ml) at 250C, and the mixture was kept at 350C for 8 hours and diluted with water (100 ml) and extracted with ethyl acetate (150 ml). The extract was washed with water (100 ml), dried over anhydrous magnesium sulfate and concentrated under reduced pressure.The oily residue was purified by silica gel column chromatography using toluene/tetrahydrofuran (9/1) as an eiuent to give ethyl S-methyl-N-(3-chloro-4-ethoxy-5-methoxymethyl phenyl) monothiocarbonimidate (3.02 g) in a yield of 95%. nD = 1.5482. NMR (CDCl3, TMS) N: 1.38 (3H, t), 1.52 (3H, t), 2.92 (2H, q), 3.35 (3H, s). 3.90 (3H, s), 3.80-4.20 (4H, m), 4.45 (2H, s) 6.83 (2H, s). 6.83 (2H, s).

EXAMPLE 4 Preparation of O-methyl O'-methyl-N-(3,5-dichlorophenyl)carbonimidate:- To a solution of N-(3,5-dichlorophenyl-carbonimidoyl dichloride (2.43 g; 0.01 mole) in 1 5 ml of methanol was added a sodium methyl ate solution prepared from metallic sodium (0.46 g; 0.02 mole) and methanol (30 ml) at 25 C, and the mixture was kept at 350C for 7 hours. The mixture was diluted with water (100 ml) and extracted with ethyl acetate (150 ml). The extract was washed with water (100 ml), dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The oily residue was purified by silica gel column chromatography using toluene/tetrahydrofuran (9/1) as an eluent to give O-methyl O'-methyl-N-(3,5-dichlorophenyl)carbonimidate (2.15 g) in a yield of 92%.

nD5 = 1.5897. NMR (CDCI3, TMS) b: 3.92 (6H, t), 6.73 (2H, d, J = 0.5), 7.00 (1 H, t, J = 0.4).

EXAMPLE 5 Preparation of methyl S-methoxycarbonyl-N-(3-chloro-4-ethoxy-5 methoxymethylphenyl)monothiocarbonimidate:- To a solution of methyl N-(3-chloro-4-ethoxy-5-methoxymethylphenyl)thionocarbamate (2.90 g; 0.01 mole) in 20 ml of dimethylformamide was added sodium hydride (0.24 g; 0.01 mole) at 200C.

Then, methyichloroformate (1.13 g; 0.012 mole) was added dropwise and the mixture was allowed to stand at 250C for 4 hours. The mixture was then diluted with water (100 ml) and extracted with ethyl acetate (150 ml). The extract was washed with water (100 ml), dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The oily residue was purified by silica gel column chromatography using toluene/tetrahydrofuran (9/1) as an eluent to give methyl S-methoxycarbonyl-N (3-chloro-4-ethoxy-5-methoxymethylphenyl)monothiocarbonimidate (3.34 g) in a yield of 96%.M.P., 70-71 OC. NMR (CDCI3) : 1.42 (3H, t), 3.35 (3H, s), 3.70 (3H, s). 4.03 (3H, s), 3.95 (2H, t), 4.43 (2H, s), 7.70 (2H, s).

According to the above procedures, the N-phenylimidate of the formula (I) as shown in Table 1 can be prepared.

TABLE 1

Compund No. X Y Z A B R R 1 -Cl -Cl -H -O- -S- -CH3 -CH3 2 -Cl -Cl -OCH2CH3 -O- -S- -CH3 -CO2CH3 3 -Cl -Cl -OCHF2 -O- -S- CH3 -COCH2Br -CH CH3 4 -Br -Br -OCH3 -O- -S- -CH2CH3 -CH2CH=CH2 5 -Cl -C2H5 -OCH2CH3 -S- -S- -(CH2)3CH3 -CH2-# 6 -CH3 -CH3 -H -O- -S- -CH2COCH3 -CH2-# 7 -CH3 -CH3 -OC2H5 -S- -S- -CH3 -CH3 8 -CH3 -CH3 -OC2H5 -O- -S- -CH2-# -CO2CH3 9 -CH3 -CH3 -OC2H5 -NH- -S- -CH2CH3 -CH2CH2-# 10 -CH3 -CH3 -OC2H5 -O- -O- -CH3 -CH3 11 -CH3 -CH3 -OC2H5 -O- -S- O -C-CH212 -CH3 -CH3 -OC2H5 -O- -S- -O-# -CO-# TABLE 1 (continued)

Compound No. X Y Z A B R R 13 -CH3 -CH3 -OC2H5 -S- -S- S -COCH2CH3 -C-OC2H5 14 -CH3 -CH3 -OC2H5 -NH- -NH- -# -CH3 15 -Cl -Cl -OC2H5 -NCH3- -NHCH2CH3- -CH3 -CH2CH3 16 -CH3 -CH3 -OC2H5 -O- -S- -CH2# -CH2C#CH 17 -CH3 -CH2CH3- -OCH2CH3 -O- -S- -CH3 -CH3 -CH2-# S 18 -CH3 -CH2CH3 -OCH2CH=CH2 -O- -S- -C-CH3 H3C CH3 -CH2CO2CH3 19 -CH3 -CH2CH3 -OCH2-# -O- -S- -CH CH3 20 -CH3 -CH2CH=CH2 -OC2H5 -O- -S- -CH3 -COCH2Cl 21 -CH3 -CH2CH2CH3 -OC2H5 -O- -S- -CH2CH=CH2 -COCH2OCH3 CH3 22 -Cl -OCH3 -OC2H5 -O- -S- -CHCH2 -CH2-#-Cl CH3 23 -Cl -OCH3 -OC2H5 -O- -S- -CH3 -CH2-# TABLE 1 (continued)

Compound No.

X Y Z A B R R 24 -Br -OCH3 -OCH2C=CH -O- -S- -CH2-# -## 25 -Cl -CH2OCH3 -OC2H5 -S- -S- -CH3 -CH3 26 -Cl -CH2OCH3 -OC2H5 -S- -S- -CH3 -CO2CH3 CH3 27 -Cl -CH2OCH3 -OC2H5 -S- -S- -CH -COCH3 CH3 S 28 -Cl -CH2OCH3 -OC2H5 -S- -S- -C-OC2H5 -CH3 S 29 -Cl -CH2OCH3 -OC2H5 -S- -S- -C-OC2H5 -CH3 30 -Cl -CH2OCH3 -OC2H5 -S- -S- -CH2CO2C2H5 -CH2-#-OCH3 31 -Cl -CH2OCH3 -OC2H5 -O- -S- -CH3 -CH2CH3 CH3 32 -Cl -CH2OCH3 -OC2H5 -O- -S- -CH -CH3 CH3 33 -Cl -CH2OCH3 -OC2H5 -O- -S- -(CH2)3CH3 -CO2CH3 34 -Cl -CH2OCH3 -OC2H5 -O- -S- -CH3 -COCH2Cl TABLE 1 (continued)

Compound No. X Y Z A B R R 35 -Cl -CH2OCH3 -OC2H5 -O- -S- -CH2COCH3 -SO2CH3 36 -Cl -CH2OCH3 -OC2H5 -O- -S- -CH2CH2NH3-# -CH2CH2CN 37 -Cl -CH2OCH3 -OCHF2 -O- -S- -CH2CH2CH2Br -CH2-H CH3 CH3 38 -Cl -CH2OCH3 -OCH2CH=CH2 -O- -S- -C-C=CH -CH2CH CH3 CH3 O 39 -Br -OCH3 -OCH2CH2Cl -O- -S- -CH(CH2)5CH3 -C-# 40 -Br -OC2H5 -OCH2CH=CH2 -O- -S- -CH3 -CH3 Br Cl Cl 41 -Br -OC2H5 OC2H5 -O- -S- -CH2-# -CH2-C=CH 42 -Cl -OC2H5 -OC2H5 -O- -O- -CH3 -COCH2Cl 43 -Cl -OCH5 OC2H5 -NH- -S- # -CH2COCH3 CH3 44 -Cl -OC2H5 -OC2H5 -NH- -S- -N# -C-CO2CH3 45 -Cl -OC2H5 -OCHF2 -NH- -NH- -CH2CF3 -CH2CF3 TABLE 1 (continued)

Compound No. X Y Z A B R R CH3 46 -CH3 -OC2H5 -OC2H5 -S- -S- -CH -CH2-# CH3 CH3 47 -CH3 -OC2H5 -OC2H5 -S- -S- -CH -CH2-#-C(CH3)3 CH3 48 -CH3 -OC2H5 -OC2H5 -S- -S- -CH -COCH3 49 -CH3 -OC2H5 -OC2H5 -O- -S- -CH -CH3 CH3 F 50 -CH3 -OC2H6 -OC2H5 -O- -S- -CH -CH2-# CH3 CH3 51 -CH3 -OC2H6 -OC2H5 -O- -S- -CH -CH3 CH3 CH3 52 -CH3 -OC2H6 -OC2H5 -O- -S- -CH -CO2CH3 CH3 TABLE 1 (continued)

Compound No. X Y Z A B R R CH3 CH3 53 -CH2 -OC2H5 -OC2H5 -O- -S- -CH -CO2CH CH3 CH3 CH3 54 -CH3 -OC2H5 -OC2H5 -O- -S- -CH -CO-# CH3 O 55 -CH3 -OC2H5 -OCH2CH=CH2 -O- -S- -C-CH2-#56 -CH3 -OC2H5 -OC2H5 -O- -S- -# -CH3 O 57 -CH2F -OC2H5 -OCH3 -O- -S- -CH2C#CCH2Cl -CH2-C-# CH3 58 -CH3 -OC2H5 -OC2H5 -O- -S- -CHCH2OCH3 -CH2-#-CH3 CH3 59 -CH3 -OC2H5 -OC2H5 -O- -S- -CHCH2O-# -CH2CH2OCH2CH3 60 -CH3 -OC2H5 -OC2H5 -NH- -S- -CH3 -CH3 61 -CH3 -OC2H5 -OC2H5 -NH- -S- -# -CH3 TABLE 1 (continued)

Compound No. X Y Z A B R R 62 -CH3 -OC2H5 -OC2H5 -NCH2CH3- -S- # -COCH2Cl 63 -CH3 -OC2H5 -OC2H5 -NH- -S- -CH2CH2OCH2CH3 -CH2-# 64 -CH3 -OC2H5 -OC2H5 -NH- -NH- -CH3 -CH3 65 -CH3 -OC2H5 -OC2H5 -NH- -S- # -COCH2CH2Cl 66 -CHF2 -OC2H5 -OCH3 -NH- -S- # -COCH2Cl 67 -CH3 -OC2H5 -OC2H5 -NH- -S- #-CH3 -CH2CO2CH3 68 -Cl -OC2H5 -CH2OCH3 -NH- -S- # -(CH2)4-# 69 -CH3 -OC2H5 -OC2H5- -NH- -S- # # CH3 70 -CH3 -OC2H5 -OC2H5 -NH- -S- # -CH2CH2COCH3 71 -CN -OC2H5 -OC2H5 -O- -S- -CH3 # CH3 72 -CHO -OC2H5 -OC2H5 -O- -S- -CH -COCH2CH2Cl CH3 TABLE 1 (continued)

Compound No. X Y Z A B R R 73 -CH=NOCH3 -OC2H5 -OC2H5 -O- -S- -CH3 -COCO2C2H5 74 -CH#CH -OC2H5 -O- -S- -CH2CH3 -CO2CH2Cl 75 -CH=CH2 -OC2H5 -OC2H5 -O- -S- -CH3 -CN 76 -COCH2CH3 -CH3 -OC2H5 -O- -S- -CH3 -COCH=CH2 CH3 77 -COCH3 -Cl -OCH3 -O- -S- -CH -CH2CO2-# CH3 78 -CF3 -Cl -OC2H5 -O- -S- -CH2F -CH2-# 79 -CHF2 -Cl -OC2H5 -O- -S- -CH2CH2-# -(CH2)3CH3 H3C CH3 CH3 80 -CONHCH3 -OC2H5 -OC2H5 -O- -S- -C-C#CH -CO2-C-CO2CH2-# CH3 CH3 81 -CH2OH -OC2H5 -OC2H5 -O- -S- -#-O-#-CF3 -CH2-# O 82 -CH2CH2CH3 -OC2H5 -OCH2CH=CH2 -O- -S- -C-CH3 -SO2CH3 TABLE 1 (continued)

Compound No. X Y Z A B R R 83 -CH3 -OC2H5 -OC2H5 -O- -S- -CH3 -SO2-# CH3 84 -Cl -CH2OCH3 -OC2H5 -O- -S- -CH -SO2CH2CH2CH3 CH3 85 -Cl -CH2OCH3 -OC2H5 -O- -S- -CH3 -CO-#-NO2 CH3 86 -CN -CH3 -OC2H5 -O- -S- -C2H5 -CH2CH2CH CH3 CH3 87 -C#C -CH3 -OC2H5 -O- -S- -CH -SCH2CH3 CH3 88 -CH3 -OC2H5 -OC2H5 -O- -S- -CH2-# -S-# 89 -Cl -CH2OCH3 -OC2H5 -O- -S- -CH2CH2OCH3 -CH2CH#CH2 90 -Cl -CH2OCH3 -OC2H5 -O- -S- -CH3 -CH3 F 91 -CH3 -OC2H5 -OC2H5 -O- -S- -CH3 -CH2-# TABLE 1 (continued)

Compound No. X Y Z A B R R 92 -CH3 -CH2OCH3 -OC2H5 -NH- -S- # -CH3 O CH3 93 -Cl -CH2OCH3 -OC2H5 -O- -S- -CH3 -CN CH3 94 -Cl -CH2OCH3 -OC2H5 -O- -S- -CH3 CO2CH3 95 -CH3 -CH3 -OC2H5 -O- -S- -CH3 -CH3 In the practical usage of the N-phenylimidates (I) as fungicides, they may be applied as such or in a preparation form such as dusts, wettable powders, oil sprays, emulsifiable concentrates, tablets, granules, fine granules, aerosols orflowables. Such preparation form can be prepared in a conventional manner by mixing at least one of the N-phenylimidates (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, dimethylacetamide), halogenated 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 inciude 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 aids and their esters, etc.

The foregoing preparations generally contain at least one of the N-phenylimidates (I) in a concentration of about 1 to 95% by weight, preferably of 2.0 to 80% by weight. By using the preparations, the phenylimidates (I) are generally applied in such amounts as 2 to 100 g per 10 ares When only the drug-resistant strains of phytopathogenic fungi are present, the N-phenylimidates (I) may be used alone. However, when the drug-sensitive strains are present together with the drugresistant strains, their alternate use with benzimidazole thiophanate fungicides and/or cyclic imide fungicides or their combined use with benzimidazole thiophanate fungicides 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 preparation forms.In case of the combined use, the weight proportion of the N-phenylimidates (I) and the benzimidazole thiophanate fungicide and/or the cyclic imide fungicide may be from about 1:0.1 to 1:10.0.

Typical examples of the benzimidazole thiophanate fungicides and the cyclic imide fungicides are shown in Table 2.

TABLE 2

Compound Structure Name A X \ > NHCOOCH3 Methyl 1 -(butylcarbamoyl)benz imidazol-2-yl-carbamate CONHC4H9 (n) B gXX1 2-(4-Thiazolyi)benzimidazole C k" \ > CHCOOCH3 Methyl benzimidazol 2-ylcarbamate H D < 0 2-(2-Furyl)benzimidazole H TABLE 2 (continued)

Compound Structure Name S il E ~ NHCNHCOOCH3 1,2-Bis(3-methoxycarbonyl lz, II 2-thioureido)benzene StttuNBCNHCOOCH3 Is" S II F ,~NHCNUCooc2H5 1 ,2-Bis(3-ethoxycarbonyl 25 2-thioureido)benzene < > > t XNHCNHCOOC2H5 S S G ,~ NHCNHCOOCH3 2-(O,S-Dimethyl 11 phosphorylamino)- 1 HP\SCH3 (3'-methoxycarbonyl O OCH3 2'-thioureido)benzene S II H / NHCNHCOOCH3 2-(0,0-Dimethylthio phosphorylamino)-1 NHP V XNHPx O-CH3 Ir \ 2-thioureido)benzene S OCH3 O CH, C1; 3 N-(3',5'-Dichlorophenyll \ ~ f X z 1,2-dimethylcyclopropane Cl,CH3 1 2-dicarboximide 0 0 0 II J , r% / > N-C-NHCH(CH3) Z 3-(3',5'-Dichiorophenyl) q N-C-NHCH (CH3) 1-isopropylcarbamoyl Oo/ , imidazolidin-2,4-dione C 0 Cl K ~ 2 -methyl-5-vinyl Cl H=CHZ S-methyl-S-vinyl oxazolidin-2,4-dione O CH3 0 L P COOCH Ethyl (RS)-3-(3',5'-dichloro r/ \ phenyi)-5-methyl 2.4-dioxooxazolidine O CH3 5-carboxylate Besides, the N-phenylimidates (I) may be also used in admixture with other fungicides, herbicides, insecticides, miticides, fertilizers, etc.

When the phenyiimidates (I) are used as fungicides, they may be applied in such amounts as 2 to 100 grams per 10 ares. However, this amount may vary depending upon preparation 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. 31, 88 parts of clay and 10 parts of talc are thoroughly pulverized and mixed together to obtain a dust preparation containing 2% of the active ingredient FORMULATION EXAMPLE 2 Thirty parts of Compound No. 94, 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 preparation containing 30% of the active ingredient.

FORMULATION EXAMPLE 3 One part of Compound No. 49, 1 part of Compound I, 88 parts of clay and 10 parts of talc are thoroughly pulverized and mixed together to obtain a dust preparation containing 2% of the active ingredient.

FORMULATION EXAMPLE 4 Twenty parts of Compound No. 52, 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 preparation containing 30% of the active ingredient.

Typical test data indicating the excellent fungicidal activity of the phenylimidates (I) are shown below. The compounds used for comparison are as follows:

Compound Remarks Swep 0 C19NEHCOCH3 Commercially available herbicide C Chlorpropham 0 (3NHCoCH CH3 Commercially available herbicide - CH Cl/ 3 Barban 0 QNHCOCH2C-CCH2Cl Commercially available herbicide Cl' CEPC 0 NHC010CH2CH2C 1 Commercially available herbicide Cl

Compound Remarks Propham 0 t 3 NHCOCH Commercially available herbicide - CH3 Chlorbufam /C=CH OCH OCH Commercially available herbicide > =2 XCH Cl NCH 3 Benonivi CONHC4H9 iAi$)HCooCH3 Commercially available fungicide Thioshanate-methyl S II NHCNHCOOCH3 NHCNHCOOCH3 Commercially available fungicide II S Carbendaz im H -NHCOOCH3 Commercially available fungicide Thiabendazole H g Commercially available fungicide I EdifenDhos ffiso \11 P-OC2H5 Commercially available fungicide ffiffis7 EXPERIMENT 1 Protective activity test on powdery mildew of cucumber (Sphaerotheca fuliginea):-- A flower pot of 90 ml volume is filled with sandy soil, and seeds of cucumber (var: Sagami-hanjiro) are sowed therein. Cultivation is 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 is sprayed at a rate of 10 ml per pot. Then, the seedlings are inoculated with a spore suspension of the drug-resistant or drug-sensitive strain of Sphaerotheca fuliginea by spraying and further cultivating in the greenhouse. Ten days thereafter, the infectious state of the plants is observed.

The degree of damage is determined in the following manner.

The leaves examined are measured for a percentage of infected area and classified into the corresponding disease indices, 0, 0.5, 1,2, 4: Disease index Percentage of infected area O 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 is calculated according to the following equation: Disease z (Disease index) x (Number of leaves) severity = x 100 %) 4 x (Total number of leaves examined) The prevention value was calculated according to the following equation:: Prevention (Disease severity in treated plot) value = 100 -- x 100 (%) (Disease severity in untreated plot) The results are shown in Table 3 TABLE 3

Prevention Prevention value when value when Concentration inoculated inoculated of active with drug- with drug ingredient resistant sensitive Compound No. (ppm) strain (%) strain (%) 31 200 100 0 46 200 100 0 49 200 100 0 50 200 . 100 0 52 200 100 0 54 200 100 0 89 200 100 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-methyl 200 0 100 Carbendazim 200 0 100 As understood from the results shown in Table 3, the N-phenylimidates (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 Nphenylimidates (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 sugarbeet (Cercospora beticola):-- A flower pot of 90 ml volume is filled with sandy soil, and seeds of sugarbeet (var: Detroit dark red) are sowed therein. Cultivation is 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 is sprayed at a rate of 10 ml per pot. Then, the seedlings are inoculated with a spore suspension of the drug-resistant or drug-sensitive strain of Cercospora beticola by spraying. The pot is covered with a polyvinyl chloride sheet to make a condition of high humidity, and cultivation is continued in the greenhouse for 10 days. The degree of damage is determined in the same manner as in Experiment 1.

The results are shown in Table 4.

TABLE 4

Prevention Prevention value when value when Concentration inoculated inoculated of active with drug- with drug ingredient resistant sensitive Compound No. (ppm) strain (%) strain (%) 46 200 100 0 49 200 100 0 50 200 100 0 54 200 100 0 89 200 100 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-methyl 200 0 100 Carbendazim 200 0 100 As understood from the results shown in Table 4, the N-phenylimidates (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. Other tested compounds Structurally similar to the N-phenylimidates (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 is filled with sandy soil, and seeds of pear (var: Chojuro) were sowed therein. Cultivation is 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 is sprayed at a rate of 10 ml per pot. Then, the seedlings are inoculated with a spore suspension of the drug resistant or drug-sensitive strain of Venturia nashicola by spraying. The resulting plants are placed at 200C under a condition of high humidity for 3 days and then at 200C under irradiation with a fluorescent lamp for 20 days. The degree of damage is determined in the same manner as in Experiment 1.

The results are shown in Table 5.

TABLE 5

Prevention Prevention value when value when Concentration inoculated inoculated of active with drug- with drug ingredient resistant sensitive Compound No. (ppm) strain (%) strain (%) 46 200 100 0 50 200 100 0 54 200 100 0 89 200 100 0 93 200 100 0 Benomyl 200 0 100 Thiophanate-methyl 200 0 100 As understood from the results shown in Table 5, the N-phenylimidates (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 gray mold of cucumber (Botrytis cinerea): Plastic pots of 90 ml volume is filled with sandy soil, and seeds of cucumber (var: Sagami-hanjiro) were sowed therein. Cultivation is carried outin 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 is sprayed at a rate of 10 ml per pot. After airdrying, the seedlings are 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 are infected by incubating under high humidity at 200C for 3 days, the rates of disease severity are observed.The degree of damage is determined in the same manner as in Experiment 1.

The results are shown in Table 6.

TABLE 6

Prevention Prevention value when value when Concentration inoculated inoculated of active with drug- with drug ingredient resistant sensitive Compound No. (ppm) strain (%) strain (%) 31 X 200 100 0 46 200 100 0 49 200 100 0 50 200 100 0 52 200 100 0 53 200 100 0 54 200 100 0 89 200 100 0 93 200 100 0 94 200 100 0 Benomyl 200 O 100 Thiophanate-methyl 200 0 100 As understood from the results shown in Table 6, the N-phenylimidates (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.

EXPERIMENT 5 Preventive effect on powdery mildew of cucumber (Sphaerotheca fuliginea):-- A plastic pot of 90 ml volume is filled with sandy soil, and seeds of cucumber (var: Sagamihanjiro) are sowed therein. Cultivation is carried out in a greenhouse for 8 days. Onto the resulting seedlings having cotyledons, the test compound(s) formulated in emulsifiable concentrate or wettable powder and diluted with water are sprayed at a rate of 10 ml per pot. Then, the seedlings are inoculated with a mixed spore suspension of the drug-resistant and drug-sensitive strain of Sphaerotheca fullginea by spraying and further cultivated in the greenhouse. Ten days thereafter, the infectious state of the plants is observed. The degree of damage is determined in the same manner as in Experiment 1.

The results are shown in Table 7.

TABLE 7

Concentration Prevention active ingredient value Compound No. (ppm) (%) 46 100 34 46 20 0 49 100 43 49 20 0 52 100 41 52 20 0 94 100 36 94 20 0 A 100 45 A 20 12 B 500 42 B 100 10 C 100 42 C 20 8 D 500 36 D 100 0 E 100 44 E 20 10 F 100 43 F 20 8 G 100 42 G 20 8 H 100 40 H 20 5 46 + A 20 + 20 100 46 + B 20 + 20 100 46 + E 20 + 20 100 46 + G 20 + 20 100 49 + C 20 It 20 100 49 + D 20 + 20 100 49+F 20+20 100 49 + H 20 + 20 100 52 + A 20 + 20 100 52 + D 20 + 20 100 52 + E 20 + 20 100 52 + G 20 + 20 100 94 + A 20 + 20 100 94 + B 20 + 20 100 94 + E 20 + 20 100 94 + G 20 + 20 100 As understood from the results shown in Table 7 the combined use ot the N-phenylimidates (i) of the invention with benzimidazole thiophanate fungicides and/or cyclic imide fungicides show much more excellent preventive effect than their sole use.

EXPERIMENT 6 Preventive effect on gray mold of tomato (Botrytis cinerea).

A plastic pot of 90 ml volume is filled with sandy soil, and seeds of tomato (var: Fukuji No. 2) are sowed therein. Cultivation is 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 are sprayed at a rate of 10 ml per pot. Then, the seedlings are inoculated with a mixed spore suspension of the drug-resistant and drug-sensitive strain of Botrytis cinerea by spraying and placed at 200C in a room of high humidity for 5 days. The degree of damage is determined in the same manner as in Experiment 1.

The results are shown in Table 8.

TABLE 8

Concentration of Prevention active ingredient value Compound No. (ppm) (%) 31 100 25 31 | 20 | 0 46 100 42 46 20 0 49 100 27 49 20 0 93 100 32 93 20 0 94 100 43 94 20 0 100 48 20 | 22 J 500 46 J 100 18 K 100 42 K 20 15 L 500 42 L 100 12 31+1 20+50 100 31+K 20+50 100 46+1 20+50 100 46 + J | 20 + 50 | 100 46 + K 20 + 50 100 46 + L | 20 + 50 | 100 49+1 20 + 50 100 49 + K 20 + 50 100 93+1 20+50 100 93 + J 20 + 50 100 94+1 20+50 100 94+J 20+50 100 94 + K 20 + 50 100 94 + L 20 + 50 100 As understood from the results shown in Table 8, the combined use of the N-phenylimidates (I) of the invention with benzimidazole thiophanate fungicides and/or cyclic imide fungicides show much more excellent preventive effect than their sole use.

Claims (13)

1. An N-phenylimidate of the formula:

wherein X and Y are each independently a halogen atom, a lower alkyl group, a lower alkenyl group, a lower cyano-alkenyl group, a lower alkynyl group, a lower alkoxy group, a cyano group, a lower alkyl group substituted with at least one halogen atom, hydroxy or cyano group, or a group of the formula:

in which R3 is a lower alkyl group a lower alkenyl group, a lower alkynyl group or a lower haloalkyl group, R4 and R5 are each independently a lower alkyl group, R6 is a hydrogen atom or a lower alkyl group and n is 2, 3 or 4;Z is a hydrogen atom, a fluorine atom or a group of the formula: -OR7 in which R7 is a lower alkyl group, a lower alkenyl group, a lower alkynyl group or a lower alkyl group substituted with at least one halogen atom, lower alkoxy or lower cycloalkyl group; A and B are each independently an oxygen atom, a sulfur atom or a group of the formula: -NR8 in which R8 is a hydrogen atom, a lower alkyl group, a lower cycloalkyl group, a lower cycloalkenyl group, a lower cycloalkynyl group a lower alkoxyalkyl group, a lower haloalkyl group, a lower hydroxyalkyl group or a lower aralkyl group;R1 and R2 are each independently a C,--C, alkyl group, a C3C8 alkenyl group, a C3C8 alkyl group, a lower cycloalkyl group, a lower haloalkenyl group, a lower haloalkynyl group, a phenyl group or a group of the formula::

--SO,R9 or --SS-R9 in which Land M are each independently an oxygen atom or a sulfur atom and R9 is a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower aralkyl group, a phenyl group, a heteroaryl group, a lower alkyl group substituted with at least one halogen atom, cyano, lower alkoxy or phenoxy group, a phenyl group substituted with at least one halogen atom, cyano, nitro, lower alkyl or lower alkoxy group or a lower alkyl group substituted with at least one halogen atom, cyano, lower alkoxy, lower alkenyloxy, lower haloalkoxy, lower alkyloxyimino, phenoxy, lower alkyloxy, phenyl, lower cycloalkyl, naphthyl, heteroaryl or phenyl substituted with at least one halogen atom, cyano, lower alkyl, lower alkoxy, phenoxy, lower haloalkyl, lower haloalkenyl, lower haloalkynyl, alkenyl, alkynyl, lower cycloalkyl, lower alkoxyalkyl, lower haloalkoxyalkyl, lower alkylcarbonyl, lower alkoxycarbonyl, lower alkylamino or lower alkylthio group, or R1 and R2 may be combined together to form a group of the formula:

in which n is 2 or 3.

2. A fungicidal composition which comprises as an active ingredient a fungicidally effective amount of an N-phenylimidate of the formula:

wherein X, Y, Z, A, B, R and R2 are as defined in claim 1, together with an inert carrier or diluent.

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

4. A fungicidal composition as claimed in claim 3, wherein the benzimidazole thiophanate fungicide is methyl 1 -(butylcarbamoyl)benzimidazol-2-ylcarbamate, 2-(2-furyl)benzimidazole, 2-(4- thiazoyl)benzimidazole. methyl benzimidazole-2-ylcarbamate, 1 ,2-bis(3-methoxycarbonyl-2- thioureido)benzene. 1 ,2-bis(3-ethoxycarbonyl-2-thioureido)benzene, 2-(O,S- dimethylphosphorylamino)-1 -(3'-methoxycarbonyl-2'-thioureido)benzene or 2-(0,0- dimethylthiophosphorylamino)-1 -3'-methoxycarbonyl-2'-thioureido)benzene.

5. A fungicidal composition as claimed in claim 3 wherein the cyclic imide fungicide is 3-(3',5'dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide,3-(3',5'-dichlorophenyl)-1isopropylcarbamoylimidazolidine-2,4-dione,3-(3',5'-dichlorophenyl)-5-methyl-5-vinyloxazolidone-2,4dione or ethyl (RS)-3-(3',5'-dichlorophenyl)-5-methyl-2,4-dioxooxazolidine-5-carboxylate.

6. A composition as claimed in any one of claims 2 to 5 which comprises from 1 to 95% by weight of the N-phenylimidate.

7. A method for controlling plant pathogenic fungi which comprises appiying a fungicidally effective amount of at least one of the N-phenylimidates of the formula:

wherein X, Y, Z, A, B, Rl and R2 are each as defined in claim 1, or of a composition as claimed in any one of claims 2 to 6, to plant pathogenic fungi.

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

9. A process for producing an N-phenylimidate of the formula:

wherein X, Y, Z, A, B, R1 and RZ are as defined in claim 1 which process comprises (i) reacting an aniline derivative of the formula:

wherein X, Y, Z, A and R1 are each as defined above, with a halide of the formula: X1-R2 wherein R2 is as defined above and X' is a halogen atom; (ii) reacting an N-phenylimidoyl chloride of the formula:

wherein X, Y, Z, A and R1 are each as defined above, with a compound of the formula: HB-R2 wherein B and R2 are each as defined above; (iii) reacting an N-phenylimidoyl dihalide of the formula:

wherein X, Y and Z are each as defined above and Q is a halogen atom, with a compound of the formula: HA-R1 or HB-R2 wherein A, B, R1 and R2 are each as defined above; (iv) reacting an N-phenyldithiocarbonimidate of the fr'rmiiI'

wherein X, Y, Z, R1 and RZ are each as defined above, with a compound of the formula: HA'-R1 or HA'-R2 wherein R' and R2 are each as defined above and A' is an oxygen atom or a group of the formula: --NR8 in which R8 is as defined above; or (v) reacting a compound of the formula:

wherein X, Y, Z, R', R2 and RB are each as defined above, with an amine of the formula:

wherein R2 and R8 are each as defined above.

10. A process as claimed in claim 9 substantially as hereinbefore described with reference to any one of Examples 1 to 5.

11. A compound as claimed in claim 1 whenever prepared by a process as claimed in claim 9 or claim 10.

1 2. A composition as claimed in claim 2 substantially as hereinbefore described with reference to any one of Formulation Examples 1 to 4.

13. A method as claimed in claim 7 substantially as hereinbefore described with reference to any one of Experiments 1 to 6.