BG60830B2 - FUNGICIDAL N-PHENYLCARBAMATES - Google Patents

Abstract

The N-phenylcarbamates have the formula and find application as a fungicide preparation against phytopathogenic fungi, in particular against strains resistant to benzylimidazole thiophanate fungicides and/or cyclic imide fungicides.

Description

The invention relates to fungicidal N-phenylcarbamates.

It is known that benzimidazole thiophanate fungicides such as benomyl (methyl 1-(butylcarbamoyl)benzimidazole-2-ylcarbamate), fubelidazole (2-(2-furyl)benzimidazole), thiabendazole (2-(4-thiazolyl)benzimidazole), carbendazim (methyl benzimidazole-2-ylcarbamate), thiophanate-methyl (1,2-bis(3-methoxycarbonyl-2-thiourea)benzene), thiophanate (1,2-bis(3-ethoxycarbonyl-2-thiourea)benzene), 2-(0,S-dimethylphosphorylamino)-1-1-(3 *-methoxycarbonyl-2’-thiourea)benzene and 2-(0,0-dimethylthiophosphorylamino)-1-(3’-methoxycarbonyl2’-thiourea)benzene show excellent fungicidal activity against various plant pathogenic fungi. and have been widely used as fungicides in agriculture since 1970. However, their continuous application over a long period of time allows phytopathogenic fungi to develop resistance to them. This leads to a decrease in the

- 2 plant protection effect. In addition, fungi that develop resistance to some types of benzimidazole thiophanate fungicides also show significant resistance to some other benzimidazole thiophanate fungicides. Therefore, they tend to show cross-resistance. Therefore, if a certain decrease in their protective effect against plant disease is observed in certain treated areas, their application to these areas should be discontinued. However, it is often observed that the infection by resistant organisms does not decrease even after a long time after the fungicide application is discontinued. Although other types of fungicides should be used in such a case, only a small number of them are as effective as benzimidazole thiophanate fungicides in controlling the various phytopathogenic fungi. Cyclic imide fungicides, such as procymidone (3-(3*,5’-dichlorophenyl)-1,2-dimethylcyclopropane-1,

2-dicarboximide), iprodione (3-(3 ¹ ,5'-dichlorophenyl)-1-isopropylcarbamoylimidazolidine-2,4-dione), vinchlorozin (3-(3*,5'-(dichlorophenyl)-5-methyl-5-vinyloxazolidine-2,4-dione), ethyl (E$)-3-(3*,5·'dichlorophenyl)-5-methyl-2,4-dioxazolidine-5-carboxylate, etc., which are effective against various plant diseases, especially those caused by Botrytis cinerea, have the same disadvantages as previously described with respect to benzimidazole thiophanate fungicides.

In C. R. Acad. Sc. Paris, vol. 289, series D, pages 691693 (1979), it is described that herbicides such as barban (4-chloro-2-butynyl N-(3-chlorophenyl)carbamate), chlorbufam (1-methyl-2-propynyl N-(3-chlorophenyl)carbamate), chlorpropham (isopropyl N-(3-chlorophenyl)carbamate) and propham (isopropyl N-phenylcarbamate) exhibit fungicidal activity against some organisms which are resistant to

- 3 to some benzimidazole thiophanate fungicides. However, their fungicidal activity against fungi resistant to certain preparations is not strong enough and therefore, they cannot be practically used as fungicides.

As a result of the search for new types of fungicides, it was found that N-phenylcarbamates with the formula

E' (I)

in which E1 and E2 are the same or different and represent a lower alkyl group, a lower alkenyl group, a lower alkynyl group or a lower alkyl group substituted with at least one halogen, lower alkoxy or lower cycloalkyl radical;

E^ represents C^alkyl, C^alkenyl, C^alkynyl, lower cycloalkyl group, lower haloalkyl group, lower haloalkynyl group, lower aralkyl group, lower alkyl group substituted with at least one halogen, cyano, lower alkoxy, lower alkenyloxy, lower haloalkoxy, phenoxy, lower aralkyloxy or lower cycloalkyl radical or a group of the formula:

- CH

in which m represents 0, 1 or 2; η represents 1, 2 or 3;

X and Y are the same or different and represent an oxygen or sulfur atom and Ζ represents a hydrogen atom, a lower alkyl group

- 4 pa, lower alkenyl group, lower alinyl group, lower cycloalkyl group, lower haloalkyl group, lower alkyl group substituted with at least one halogen, cyano, lower alkoxy or lower alkoxycarbonyl radical or a group of formula

-ΟΟΕ^ or -SC^E^ in which E represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower cycloalkyl group, a lower haloalkyl group, a lower alkyl group substituted with at least one halogen, cyano, lower alkoxy, lower cycloalkyl or phenoxy radical (the phenoxy radical may optionally be substituted with at least one halogen and/or with at least one alkyl), a phenyl group, a furyl group, a thienyl group, a phenyl group substituted with at least one halogen, cyano, nitro, trifluoromethyl, a lower alkyl or lower alkoxy radical or an aralkyl group (acrylic may optionally be substituted with at least one halogen and/or with at least one alkyl), provided that when E ¹ represents methyl, E ² is not methyl or butyl, exhibit excellent fungicidal activity against pathogenic fungi which have acquired resistance to benzimidazole thiophanate fungicides and/or to cyclic imide fungicides. It is noteworthy that their fungicidal activity against organisms resistant to benzimidazole thiophanate fungicides and/or cyclic imide fungicides (hereinafter referred to as "resistant fungi" or "resistant strains") is much greater than that against organisms sensitive to benzimidazole thiophanate fungicides and/or cyclic imide fungicides (hereinafter referred to as "sensitive fungi" or "sensitive strains").

The term lower used in relation to organic radicals or compounds means that each of these radicals or compounds has no more than 6 carbon atoms.

Some of the N-(3,4-dialkoxyphenyl)carbamates have been previously

- 5 synthesized, such as N-(3,4-dimethoxyphenyl)carbamates (C. A. 28, 2339; 50, 5674e), 2-chloroethyl N-(3-methoxy-4-octyloxyphenyl)carbamate (C. A., 55, 13376<f; 55, 21021b), 2-chloroethyl N-(3-methoxy-4-butoxyphenyl)carbamate (C. A., 64, 8063 j), ethyl N-(3-methoxy-4-octyloxyphenyl)carbamate (C. A., 68, 39300b) and others. However, none of these compounds showed significant fungicidal activity against resistant fungi or could be used as a fungicide.

The present invention provides a fungicidal composition which comprises as active ingredient a fungicidally effective amount of N-phenylcarbamate and an inert carrier or diluent. The invention also provides a combination composition comprising as active ingredients N-phenylcarbamate (I) together with a benzimidazole thiophanate fungicide and/or a cyclic imide fungicide which is effective not only against susceptible fungi but also against resistant fungi and is therefore particularly effective in protecting plants from disease. The invention also provides a method for controlling plant pathogenic fungi which may be resistant or susceptible strains by applying a fungicidally effective amount of N-phenylcarbamate (I) to the plant _pathogenic fungi. Furthermore, the invention relates to novel N-phenylcarbamates represented by the formula ρ x λα (I), in which E , E , E , X, Y and Z have the meanings indicated

I 2 above, with the proviso that when E is methyl, E is not methyl or butyl. The invention also relates to a process for the preparation of the novel N-phenylcarbamates (I).

N-phenylcarbamates (I) can be prepared by various methods, among which typical examples are shown below:

Method (a):

The N-phenylcarbamate (I) is obtained by reacting the (II) values indicated above,

3,4-dialkoxyaniline with formula:

NHZ

E ² and Z have in which E^ with chloroformate of formula

X!1

C1C-Y-E ³ in which e\ X and Y have the meanings indicated above.

(III)

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, pyridine, dimethylformamide). If desired, the reaction can be carried out in the presence of a hydrogen halide binding agent (e.g., pyridine, triethylamine, diethylaniline, sodium hydroxide, potassium hydroxide, sodium hydride) to obtain the target compound (I) in high yield. The reaction can be carried out at a temperature of from 0°C to 150°C, instantaneously or for 12 hours.

Method (b):

The N-phenylcarbamate (1), in which Z represents hydrogen, is obtained by reacting 3,4-dialkoxyphenyl isocyanate or isothiocyanate with the formula:

NC = X (IV)

- 7 (V)

T 7 in which E, E and X have the meanings specified above with an alcohol or thiol of formula:

wherein E^ and X have the meanings described above.

Typically, the reaction is carried out in the absence or presence of an inert solvent (e.g., benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, dimethylformamide, chloroform, carbon tetrachloride). A catalyst may be used if desired (e.g., triethylamine, diethylaniline, 1,4-diazabicyclo(2,2,2)octane). The reaction is typically carried out at a temperature of 0° C. to 50° C., either instantaneously or over a period of 12 hours.

Method (c):

The N-Phenylcarbamates (1), in which X does not represent hydrogen, are prepared by reacting a 1-(3,4-dialkoxyphenyl)carbamate with the formula:

X

II

(VI) τ ο ζ in which E , E , E , X and Y have the meanings described above, with a halide of formula:

(VII) in which X has the meanings given above, except hydrogen, and A represents halogen (e.g. chlorine, bromine).

The reaction is usually carried out in an inert solvent (e.g., benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, chloroform, carbon tetrachloride, ethyl acetate, pyridine, dimethylformamide). If desired, the reaction can be carried out in the presence of a hydrogen halide-binding agent (e.g., pyridine, triethylamine, diethylaniline, sodium hydroxide, potassium hydroxide, sodium hydride) and a catalyst (e.g., tetrabutylammonium bromide) to obtain the target compound (I) in high yield. The reaction can be carried out at a temperature of 0°C to 150°C, instantaneously or over a period of up to 12 hours.

As specific examples of the symbols used above in the formula I 2 , it is preferred that each of E and E represents methyl, ethyl, n-propyl, isopropyl, n-butyl, allyl, 2-butenyl, 3-butenyl, propargyl, 3-butynyl, difluoromethyl, 2-chloroethyl, 2,2,2-trifluoromethyl, 2-methoxyethyl or cyclopropylmethyl, R? to mean methyl, ethyl, n-propyl, isopropyl, sec-butyl, I-ethylpropyl, 1-methylbutyl, I-ethylbutyl, 1,3-dimethylbutyl, 1-methylheptyl, allyl, 1-methyl-2-propenyl, 2-butenyl, 3-butenyl, 2-methyl-2-propenyl, 1-ethyl2-propenyl, 1-methyl-3-butenyl, 1-pentyl-2-propenyl, propargyl,

1-methyl-2-propynyl, 2-butynyl, 3-butynyl, 1-ethyl-2-propynyl, Imethyl-3-butynyl, 1-butynyl-2-propynyl, 1-pentyl-2-propynyl, cyclobutyl, cyclopentyl, 2-fluoroethyl, 2-chloroethyl, 2,2-dichloroethyl, 1-methyl-2-bromoethyl, 1-fluoromethyl-2-fluoroethyl, 1-bromomethyl-

2-bromomethyl, 1-methyl-2,2,2-trichloroethyl, 1-ethyl-2-bromomethyl, 4chloro-2-butenyl, 4-chloro-2-butynyl, 2-cyanoethyl, 1-methyl-2-methoxyethyl, 1-methyl-2-butoxyethyl, 2-allyloxyethyl, 2-(2-chloroethoxy)ethyl, 2-benzyloxyethyl, 1-chloromethyl-2-methoxyethyl, cyclopropylmethyl, 1-cyclopropylethyl, 1-cyclopentylethyl, 3-furylmethyl, 1phenylethyl or 3-tetrahydrofuranyl, X and Y can each be oxygen or sulfur and Z represents hydrogen, methyl, ethyl, n-butyl, allyl, acetyl, propionyl, n-pentanoyl, sec-pentanoyl,' cyclopropanecarbonyl, benzoyl, 2-chlorobenzoyl, 2,4-dichlorobenzoyl, 4-methylbenzoyl, methanesulfonyl or ethoxycarbonylmethyl.

TH-Phenylcarbamates (I) are effective fungicides against

- 9 broad spectrum pathogenic fungi for plants, examples of which are the following: Podosphaera leucotricha, Ventura inaegualis, Mycosjihae-rella pomi, Marssonina mail and Sclerotinia mail in the apple, Phyllactinia kakicola and Gloeosporium kaki in the plum, Cladosporium carpophilum and Phomopsis sp. in peach, Cercospora viticola, Uncinula necator, Elsinoe ampelina u Glomerejla cingulata in grapes, Cercospora beticola in sugar beet, Cercospora arachidicola u Cercospora personate in ^peanuts » Erysiphe graminis f. sp. hordei,· Cercosporella herpotrichoides u Fusarium nivale in barley, Erysiphe graminis f. sp., tritici in wheat.

Sphaerotheca filiginea u Cladosporium cucumerinum in cucumbers, Cladosporium fulvum in tomatoes, Corynespora melogenae in eggplants, Sphaerotheca humuli, Fusarium oxysporum f. sp. fragariae in strawberries, Botrytis all! in onions, cercospora apii in WHEAT, Phaeoisariopsis griseola in beans, Erisiphe cichoracearum in TOBACCO, Diplocarpon rosae in pome, Elsinoe fawcetti, Penicillium italicum, Penicillium digitatum in oranges, Botrytis cinerea in cucumbers, eggplants, tomatoes, red peppers, onions, lettuce, grapes, hops, oranges, cyclamens, onion sclerotinia sclerotiorum in cucumbers, eggplants, beans, peppers, lettuce, celery, soybeans, potatoes H ^CJII>H40r §c?^?otinia cinerea in peaches and cherries, Mycosphaerella melonis in cucumbers and watermelons and others. N-Phenylcarbamates (I) are highly effective in combating resistant strains of fungi.

N-Phenylcarbamates (I) are effective fungicides against fungi that are sensitive to known fungicides, as well as against fungi on which known fungicides are inactive. Examples of such fungi are Pyricularia oryzae, Paeudoperonospora cubensis, Plasmopara viticola, Phytophthora infeatans etc.

It is advantageous that N-phenylcarbamates (I) have low toxicity and have negligible harmful effects on mammals, fish, etc. Also, they can be applied to agricultural crops without causing toxic effects on crop plants.

In view of their excellent fungicidal properties, compounds of formula (I) are preferred, in which E and ^E2 are independently methyl, ethyl, n-propyl, isopropyl, n-butyl, allyl, 2-butenyl, 3-butenyl, propargyl, 3-butenyl, difluoromethyl, 2-chloroethyl,

2,2,2-trifluoroethyl, 2-methoxyethyl or cyclopropylmethyl, means methyl, ethyl, n-propyl, isopropyl, sec-butyl, 1-ethylpropyl, 1-methylbutyl,_1-ethylbutyl, 1,3-dimethylbutyl, 1-methylheptyl, allyl, 1-methyl-2-propenyl, 2-butenyl, 3-butenyl, 2-methyl2-propenyl, 1-ethyl-2-propenyl, 1-methyl-3-butenyl, 1-pentyl-2-propenyl, propargyl, 1-methyl-2-propynyl, 2-butynyl, 3-butynyl,

1-ethyl-2-propynyl, 1-methyl-3-butynyl, 1-butynyl-2-propynyl, 1pentyl-2-propynyl, cyclobutyl, cyclopentyl, 2-fluoroethyl, 2-chloroethyl, 2,2-dichloroethyl, 1-methyl-2-bromomethyl, 1-fluoromethyl-2-fluoroethyl, 1-bromomethyl-2-bromomethyl, 1-methyl-2,2,2-trichloroethyl, 1-ethyl-2-bromomethyl, 4-chloro-2-butenyl, 4-chloro-2-butynyl, 2-cyanoethyl, 1-methyl-2-methoxyethyl, 1-methyl-2-butoxyethyl, 2-allyloxyethyl, 2-(2-chloroethoxy)ethyl, 2-benzyloxyethyl, 1-chloromethyl-2-methoxyethyl, cyclopropylmethyl, 1-cyclopropylethyl, 1-cyclopentylethyl, 2-furylmethyl, 1-phenylethyl or 3-tetrahydrofuranyl, X and Y are independently oxygen or sulfur and D represents hydrogen, methyl, ethyl, n-butyl, allyl, acetyl, propionyl, n-pentanoyl, sec.pentanoyl, cyclopropanecarbonyl, benzoyl, 2-chlorobenzoyl,

2,4-dichlorobenzoyl, 4-methylbenzoyl, methanesulfonyl or ethoxycar- II -

I 2 bonylmethyl with the proviso that when E is methyl, E is not methyl or butyl.

Particularly preferred are compounds of formula (1) _? where E and E are independently methyl, ethyl, n-propyl, allyl or propargyl, E^ denotes ethyl, isopropyl, sec.butyl, 1-methylbutyl, 1-ethylpropyl, 1-ethylbutyl, 1-methyl-2-propenyl, 1-methyl-3-butenyl, propargyl, 1-methyl-2-propynyl, 1-ethyl-2-propynyl, 3-butynyl, 1-methyl-3-butynyl, 1-butynyl-

2-propynyl, 2-fluoroethyl, 1-methyl-2-bromomethyl, 1-fluoromethyl-2fluoroethyl, 1-bromomethyl-2-bromomethyl, 4-chloro-2-butynyl, 1-methyl-2methoxyethyl, I-cyclopropylethyl or I-pentylethyl, X represents oxygen, Y represents oxygen or sulfur and X represents hydrogen, acetyl, propionyl, n-pentanoyl, sec.pentanoyl, cyclopropanecarbonyl, benzoyl, 2-chlorobenzoyl, 2,4-dichlorobenzoyl or 4-methylbenzoyl,

I 2 with the proviso that if E is methyl, E is not a methyl group. More preferred are compounds of formula (1) wherein E^

3 and E each represent ethyl, E represents ethyl, isopropyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, 1-methyl-3-butenyl, 1-methyl-2-propynyl, 4-chloro-2-butynyl or 1-phenylethyl, X represents oxygen, Y represents oxygen or sulfur and Z represents hydrogen, acetyl, cyclopropanecarbonyl, benzoyl or 2-chlorobenzoyl.

The following compounds are most preferred: isopropyl N-(3,4-diethoxyphenyl)carbamate; 1-methyl-2-propynyl N-(3,4-diethoxyphenyl)carbamate; 4-chloro-2-butynyl N-(3,4-diethoxyphenyl)carbamate; isopropyl N-(3,4-diethoxyphenyl)thiolcarbamate; 1-phenylethyl N-(3,4-diethoxyphenyl)carbamate;

isopropyl N-acetyl-N-(3,4-diethoxyphenyl)carbamate; isopropyl N-cyclopropanecarbonyl-N-(3,4-diethoxyphenyl)carbamate;

- 12 isopropyl N-benzoyl-N-(3,4-diethoxyphenyl)carbamate; isopropyl N-(2-chlorobenzoyl)-N-(3,4-diethoxyphenyl)carbamate

mat and others.

Some typical examples of methods for preparing the N-phenylcarbamates (I) are given for illustration below: EXAMPLE I.

Preparation of isopropyl N-(3,4-diethoxyphenyl)carbamate according to method (a)

3,4-Diethoxyaniline (1.8 g) and diethylaniline (1.5 g) were dissolved in benzene (20 ml). To the resulting solution was added dropwise isopropyl chloroformate (1.2 g) over 5 minutes under ice cooling. Then it was left at room temperature for 3 hours and the reaction mixture was poured onto ice and water and extracted with ether. The extract was washed with water, dried over magnesium sulfate and concentrated under reduced pressure. 2.6 g of crude crystals were obtained. After recrystallization from ethanol, isopropyl N-(3,4-diethoxyphenyl)carbamate (compound No. 13) (2.3 g) was obtained with a yield of 86% and mp 100-100.5° C. Elemental/analysis: Calculated for ^C I4 ^H 21W C- 62.90 H - 7.92%; N - 5.24 found: C - 62.75;

H - 7.96%; N - 5.41%.

EXAMPLE 2.

Preparation of isopropyl N-(3,4-diethoxyphenyl)thiolcarbamate according to method (b)

Triethylamine (1 g) and isopropyl mercaptan (0.8 g) were dissolved in toluene (20 ml). To the resulting solution was added dropwise over 5 minutes 3,4-diethoxyphenyl isocyanate (2.Ϊ g) under ice cooling. After leaving at room temperature for 12 hours, the reaction mixture was poured onto ice-water and extracted with toluene. The extracts were washed with water, dried

- 13 over magnesium sulfate and concentrated in vacuo. The residue was purified by chromatography on silica gel using toluene as eluent to give isopropyl N-(3,4-diethoxyphenyl)thiocarbamate (compound no. 88) (2.7 g) yield, mp PO - III ⁰ C.

Elemental analysis for ^C I4 ^H 2I ^N0 3 ^$: Calculated: C - 59.33 %;

Found: C - 59.02 %

H - 7.47 %\

H - 7.51%;

N - 4.94%;

N - 4.89% with 95% confidence interval

5- 11.32 %

11.70%.

EXAMPLE 3.

Preparation of isopropyl 11-benzoyl-1-(3,4-diethoxyphenyl)carbamate according to method (c)

Isopropyl 1-(3,4-diethoxyphenyl)carbamate (2.7 g) was dissolved in dimethylformamide (50 ml) and a dispersion of sodium hydride (50%, 0.5 g) was added. The mixture was heated at 60° C. for 15 minutes, benzoyl chloride (1.4 g) was added and heated for 30 minutes. The reaction mixture was poured onto a mixture of water and ice and extracted with ether. The extract was washed with sodium bicarbonate solution and saturated brine, dried over anhydrous magnesium sulfate and concentrated in vacuo. The residue was purified by chromatography on silica gel using hexane-acetone as eluent to give 1-(3,4-diethoxyphenyl)carbamate.

d) with yield

Elemental se vo (compound No. 99) (3.1,

Calculated:

% and mp 120-121° C. analysis for CgjHg^NO^;

H - 6.78 %\

H - 6.61 % (a), (b) or (c)

C - 67.90

N - 3.77%;

N - 3.90%.

Found:

According to the methods

The N-phenylcarbamates of formula (1) _are shown in Table I:

With - 68.11 can be obtained

- 14 TABLE I

compound- physical τ ο ζ ενία E ίγ Ir X Σ 2 constant №

¹ -sn ₃ ^2% -C ₃ H ₇ (iso) 0 0 H t.t. N4-N5°C 2 -sn ₃ -¾% C^CH 1 0 0 n t.t. 133-134°C -snsn ₃ 3 -sn ₃ -C ₂ H ₅ sn, f Z -snsn ₂ ax ₃ 0 0 n t.t. 54-55°C 4 -CH ₃ -C ₃ H ₇ (n) —C ₃ H ₇ (iso) 0 0 n t.t. 94-95°C 5 -sn ₃ -sn ₂ sn=sn ₂ —C ₃ H ₇ (iso) 0 0 n t.t. 79-80° C 6 -sn ₃ -sn ₂ sn=sn ₂ s^sn 1 -snsn ₃ 0 0 n t.t. South-107°C 7 -sn ₃ -CH ₂ C=CH —C ₃ H ₇ (iso) 0 0 n ^M D ¹⁹ 1.5269 b. 8 ^C 2 ^H 5 -sn ₃ —C ₃ H ₇ (iso) 0 0 n t.t. SW-S4°N 9 - ^C 2 ^H 5 -sn ₃ c=sn 1 -snsn ₂ sn ₃ 0 0 n t.t. II0.5- W.5°N 10 " ^C 2 ^H 5 -CH ₃ -CH ₂ C=CCH ₂ C1 0 0 n t.t. 96-97°C II “ ^C 2 ^H 5 -With ₂ and ₅ -CH ₃ 0 0 n t.t. 120-121°C 12 -with ₂ and ₅ -C ₂ ^H 5 -s ₂ n ₅ 0 0 n t.t. 90-91°C 13 -C ₂ ^H 5 " ^C 2 ^H 5 —C ₃ Hg, (iso) 0 0 n t.t. I00-I0Q.5°C 14 ^C 2 ^H 5 -S ₂ n ₅ - -C ₄ H ₉ (sec) 0 0 n t.t. 97-98°C 15 " ^C 2 ^H 5 CH ι 0 0 n t.t. 67-68°C

I

-CH(CH ₂ ) ₂ CH ₃

“ ^C 2 ^H 5 -s ₂ n ₅ ch ₂ ch ₃ 1 - ch ₂ ch ₃ ~ ^C 2 ^H 5 -C ₂ ^H 5 CH ₂ CH ₃ -CH(CH ₂ ) ₂ CH ₃ “ ^C 2 ^H 5 -0 ₂ ^H 5 SN, SN, ! > I 3 snsn ₂ snsn ₃ -s ₂ n ₅ ch, 1 ·> -CH(CH ₂ } ₅ CH ₃ “ ^C 2 ^H 5 “ ^C 2 ^H 5 -CH ₂ CH=CH ₂ · -s ₂ n ₅ -s ₂ n ₅ CH, 1 > -CHCH=CH ₂ -s ₂ n ₅ -s ₂ n ₅ -CH ₂ CH ₂ CH=CH ₂ -C ₂ ^H 5 -C ₂ ^H 5 sn, 1 b -sn ₂ sn=sn ₂ " ^C 2 ^H 5 -C2H5 sn ₂ sn ₃ -snsn=sn ₂ ^C 2 ^H 5 “θ2% sn, ! ⁵ -chch ₂ ch=gh ₂ " ^C 2 ^H 5 CH=CHn 1 £ -CH(CH ₂ ) ₄ CH ₃ “ ^C 2 ^H 5 ~ ^C 2 ^H 5 -sn ₂ s^sn ² 2% "θ2 ^H 5 sn, 1 > -snowy “ ^C 2 ^H 5 “ ^C 2 ^H 5 -sn ₂ sn ₂ s^sn " ^C 2 ^H 5 -s ₂ n ₅ snow ₂ snow ₃ -snowy -s ₂ n ₅ sn, -snsn ₂ s=sn ^C 2 ^H 5 ^By 2% C=CH 1 -CH(CH ₂ ) ₃ CH ₃

0 N mp 93-94°C

UN mp 87 - 88°C

0 H mp 56-57°C

UN mp 46.5-48°C

0 H mp 86-87°C

0 H mp 98-99.5°C

UN mp 92.5-93.5°C

UN mp 92-93°C

0 H mp 98.5-99.5°C

0 H mp 75-76°C

UN mp 46.5-48°C

UN mp N-112°C

UN p.p. P6-P7°C

UN mp 89-90°C

0 N mp P8-P9°C

0 H mp 99-100° C

O 0 H mp 120-121°C

33 -With ₂ and ₅ “ ^C 2 ^H 5 34 -s ₂ n ₅ -s ₂ n ₅

RSN ο ο

-CH( _CH2 ) _{4CH3 ο} ο

mp 96-97° C

mp 114-115.5%

35 -C ₂ H ₅ “ ^C 2 ^H 5 -CH ₂ CH ₂ P 0 0 36 -s ₂ n ₅ -C ₂ ^H 5 -CH ₂ CH ₂ C1 0 0 37 -C ₂ H ₅ ^C 2 ^H 5 -CH ₂ CH1 ₂ 0 0 38 -C ₂ H ₅ -s ₂ n ₅ sn, 1 -> -CHCH ₂ Br 0 0 39 -C ₂ H ₅ -s ₂ n ₅ CH ₉ P 1 £ -CHCH ₂ P 0 0 40 -C ₂ H5 CH ₉ Bg 1 ^ά -CHCH ₂ Bg 0 0 41 -C ₂ H ₅ “ ^C 2 ^H 5 sn, ! ·> -SNCC1 ₃ 0 0 42 -C ₂ H ₅ -C ₂ ^H 5 -CH ₂ CH=CHCH ₂ C1 0 0 43 -C ₂ H ₅ ^C 2 ^H 5 -CH ₂ C^CCH ₂ C1 0 0 44 -C ₉ Hs -SoNs -CH _o CH _o 0CH _o CH= CNO

45 -C ₂ H ₅ θ2 ^H 5 -CH ₂ CH ₂ 0CH ₂ CHgI 0 0 46 -C ₂ H ₅ -s ₂ n ₅ CH, 0 0 1 - ⁵ -CHCH ₂ 0CH ₃ 47 -C ₂ H ₅ ^C 2 ^H 5 CH, 0 0 1 - ⁵ -CHCH ₂ 0(CH ₂ ) ₃ CH ₃ 48 -C ₂ H ₅ -s ₂ n ₅ CH ₂ C1 0 0 -snsn ₂ osn ₃ 49 -C ₂ H ₅ -s ₂ n ₅ -CH ₂ CH ₂ CO1 0 0

mp 101-102°C

mp 89.5-90.5%

mp 73-74° C

mp 69-70°C

mp 89-90° C

mp 75-76° C

Sun ¹⁹ · ⁵ 1.5316

mp 82-83%

mp I2-113°C

mp 58-59° C

mp 77-78° C

mp 65-66.5%

mp 36-38%

mp 82-83%

mp 85.5-86.5%

”θ2^5 “^2^5 sn ₃ -si-O 0 0 H mp107-108°C -C ₂ H ₅ -C ₃ H _? (n) -s ₂ n ₅ 0 0 n mp 74-75°C ^— θ2% “C ₃ H ₇ (n) —C ₃ H ₇ (iso) 0 0 n mp 97-98°C ^2¾ ~θ2% C=CH 1 -CHCN ₃ 0 0 n mp 99-100°C “^2% -St|Sun(n) —C ₃ H ₇ (iso) 0 0 n mp II0-III°C “^2% ⁿ ) CH, 1 -> -snsn ₂ axis ₃ 0 0 n mp 87-88° -s ₂ n ₅ -sn ₂ s=sn —C ₃ H ₇ (iso) 0 0 n mp. 202-203°N -C ₃ H ₇ (n)-CH ₃ -C ₃ H ₇ (iso) 0 0 n ϊ.τ. Ј1-Ј2°С -C ₃ H ₇ (n)-C ₂ H ₃ -sn ₃ 0 0 n mp 85-86°C -C ₃ H _? (n)—C ₂ H ₃ -s ₂ n ₅ 0 0 n mp 76.5-77.5° —s ₃ n ₇ (n) -s ₂ n ₅ —C ₃ H ₇ (iso) 0 0 n mp 81-82°C -C ₃ H ₇ (n) —C ₂ H ₃ CHj 1 -CHCH ₂ CH ₂ Θ 0 n mp 83-84°C ~C ₃ H ₇ (n) ·”θ2% CH _? CH, «· f ь J -CHCH ₂ CH ₃ 0 0 n mp 90-91°C -C ₃ H ₇ (n) *θ2^5 сн, -СН <J 0 0 n mp 82-83°C -s ₃ n ₇ (n) -s ₂ n ₃ -CH ₂ CH ₂ P 0 0 n mp 82-83°C —C ₃ H ₇ (n) -C ₃ H ₇ (n) —C ₃ H ₇ (iso) 0 0 n mp 85-86°C —C ₃ H ₇ (iso) —C ₃ H ₇ (iso) 0 0 n Sun ¹⁹ I.5I2I ~ ^by 2% —C ₃ H ₇ (iso) CH, 1 ·> 0 0 n mp 100.5 - —C ₂ H ₃ -CHN=CH 102°C, —C ₃ H ₇ (iso) sn, 1 > -CHCH ₂ 0CH ₃ 0 0 n Sun ¹⁹ 1.5092 -C ₂ H ₅

69 -C ₄ H ₉ (n) -C ₂ H ₅ 70 -CH ₂ CH=CH ₂ *“0^Ηφ(Η3θ) 0 0 n t.t. 79.5-81°C -C ₃ H?(n) •“Ο-^Ηφζ iso) 0 0 n t.t. 82-83°C 71 -CH ₂ CH=CH ₂ -C^HgrCn) -sn ₂ sn=snsn ₃ 0 0 n t.t. 66-67°C 72 -CH ₂ CH=CH ₂ -C ₃ H ₇ (n) -sn ₂ s-ssn ₃ 0 0 n t.t. 92-93°C 73 -CH ₂ CH=CH ₂ s=сн I 0 0 n t.t. 84-85.5°C -C^H^(n) -snsn ₃ 74 -CH ₂ CH=CH ₂ -sn ₂ sn=sn ₂ -C ₃ H 2 O (iso) 0 0 n t.t. 83.5-84.5° 75 -CH ₂ C=CH ₂ “ ^C 2 ^H 5 -C ₃ H^(iso) 0 0 n t.t. 101-102°C 76 -CH ₂ C=CH ₂ -0Η ₂ 0Ξ0Η —C ₃ Hg?(iso) 0 0 n t.t. SW-S4°N 77 -CIS ₂ -C№ ₂ —C ₃ Hg;(iso) 0 0 n p ^{22 M} T I.467I 78 ~θ2^5 θ2% 0 0 n t.t. 73-74°C

79 -C ₂ H ₅ -C ₂ H ₅ -сн ₂ -<[ UN mp 95-96°C 80 -C ₂ H ₅ -C ₂ H ₅ CHj 0 0 H mp 105-106°C -0H-Q

81 -C ₂ H ₃ “^2% sn ₂ sn ₃ -CHCH ₂ Vg 0 0 n t.t. 68-£9°C 82 -CH ₂ CH ₂ C1 ^C 2 ^H 5 -C ₃ Nu(iso) 0 0 n t.t. P1-P2°C 83 ^2 ^H 5 “ ^C 2 ^H 5 -C ₃ Hg?(n) 0 0 n t.t. 79-80° C

UN

mp 17-18°C

85 -C ₂ H ₅ -C^Hg 0 0 Η ТоТ» III.5 - P2.5°С -snD 1 ^2X 0^ 86 -C ₂ B ₅ -s ₂ n ₅ sn, _tk 0 0 H mp 109-P0°C 87 -C ₂ H ₅ “θ2 ^H 5 -s ₂ n ₅ 0 S H mp 70-80°C 88 -C ₂ H ₅ " ^By 2% -C^H/iso) 0 5 N mp P0-Ш°С 89 -C ₂ H ₅ -s ₂ n ₅ -CH ₂ CH=CH ₂ 0 $ H mp 73-76° C 90 -C ₂ H ₅ ”^2% -C ₂ ^H 5 0 ^{0 CH} 3 Pd ²⁸ ' ⁵ 1.5059 91 -C ₂ H ₅ -s ₂ n ₅ —C^Nu(iso) 0 o -s ₂ n ₅ p _d ²⁸ ' ⁵ 1L9y 92 -C ₂ H ₅ " ^C 2 ^H 5 -C^H/iso) 0 0 -С^(c) Pd ²⁸ · ⁵ 1.4885 93 -C ₂ H ₅ - -With ₂ and ₅ -C/y(iso) 0 0 -CH ₂ CH=CH _{2 p} 26.5 _1e 5044 D o -sosn ₃ ζ.τ. 98-99°С 94 -C ₂ H ₅ -s ₂ n ₅ ? “S^Nu(iso) 0 95 -C ₂ H ₅ -s ₂ n ₅ -C^H/iso) 0 o -sos ₂ n ₅ p ²⁷ · ⁵ 1.5006 96 -C ₂ H ₅ -s ₂ n ₅ —C ^Hg?( iso) 0 0 -C0C ₄ H ₉ (n) m.p. 63-65°С 97 -C ₂ H ₅ -s ₂ n ₅ —C^Nu( iso) 0 0 -SOS/1/sec) Pd ²⁸ 1.4889 98 -C ₂ H ₅ -s ₂ n ₅ —C^Nu(iso) 0 0 mp 55-57°C -co<3 99 -C ₂ H ₅ ”^2 ^H 5 “C ^Hr; (and 30 ) 0 0 mp 120-121°

-co

100 -C ₂ ^H 5 -S ₂ n ₅ 101 -with ₂ n^ -with ₂ and ₅

—C ₃ Hg?(iso)

0 CI

-so^>

π ²⁸ I.5371

D ~ ^C 3 ^H 7 ⁽ iso)

0 0 CI Π ²⁸ · ^{5 p} d 1.5349 -co )-CI

_{102 -C2H5} “ ^C 2 ^H 5 —Ο^Ηψ(iso) 0 0 -C( m.p.t. 102- H§>-sn ₃ ¹⁰³ ° ^s 103 _{—- C2H5} -s ₂ n ₅ -CH ₃ -snch ₂ base ₃ 0 0 -C0C ₂ H ₅ π ²⁷ 1.4972 104 -C ₂ H ₅ -With ₂ and ₅ —C ₃ H^(iso) 0 0 -S0CH ₃ pp. 114- P5°C 105 -C ₂ H ₅ “ ^C 2 ^H 5 —C^H^(iso) 0 0 -sn ₂ soos ₂ n ₅ n| ⁷ * ⁵ 1.4948 yub -s ₂ n ₅ “ ^C 2 ^H 5 -C ₂ H5 S 0 n mp 74-75°C 107 -C ₂ H ₅ -s ₂ n ₅ 5 0 n mp 87-88°C 108. -C ₂ H ₅ -s ₂ n ₅ -C ₄ H ₉ (sec) 0 $ n mp 97-98°C 109 -C ₂ H ₅ -C ₂ ^H 5 —C^Hg/ iso) S $ n mp 64-65°C

When using the N-phenylcarbamates (I) as fungicides, they can be applied as compounds or in a preparative formulation such as, for example, powders, wettable powders, oil sprays, emulsifiable concentrates, tablets, granules, microgranules, aerosols or as a suspension. These preparative forms are obtained in the usual manner by mixing at least one N-phenylcarbamate (I) with a suitable solid or liquid carrier or carriers or one or more diluents and, if necessary, adding one or more auxiliaries (for example surfactants).

- 21 tive substances, adhesives, dispersants, stabilizers) to improve the dispersibility and other properties of the active ingredient or active ingredients.

Examples of solid carriers or diluents are natural products (e.g. flours, ground tobacco stalks, soybean meal, ground nut shells, powdered vegetables, wood chips, bran, cork flour, powdered cellulose, plant residues), fibrous materials (e.g. paper, cardboard, burlap), synthetic plastic powders, clays (e.g. kaolin, bentonite), talc, other inorganic products (e.g. pyrophyllite, powdered sulfur, pumice, activated carbon) and chemical fertilizers (e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ammonium chloride).

Examples of suitable carriers or diluents are water, alcohols (e.g. methanol, ethanol), ketones (e.g. acetone, methyl ethyl ketone), ethers (e.g. diethyl ether, dioxane, cellosolve, tetrahydrofuran), aromatic hydrocarbons (e.g. benzene, toluene, xylene, methylnaphthalene), aliphatic hydrocarbons (e.g. gasoline, kerosene, gas), esters, nitriles, acid amides (e.g. dimethylformamide, dimethylacetamide), halogenated hydrocarbons (e.g. dichloroethane, carbon tetrachloride), etc.

Examples of surfactants are alkyl sulfonic acid esters, alkyl sulfonates, aralkyl sulfonates, polyethylene glycol ethers, esters, etc. Examples of tackifiers and dispersants may be ceresin, gelatin, starch powder, carboxymethyl cellulose, gum arabic, alginic acid, lignin, bentonite, molasses, polyvinyl alcohol, pine turpentine, agar. As stabilizers, PAP (mixture of isopropyl acid phosphates), TCP (tricresyl phosphate),

epoxidized oils, balms, various surfactants and their esters, etc.

The above formulations typically contain at least one N-phenylcarbamate (I) in a concentration of about 1 to 95% by weight, preferably 2.0 to 80% by weight. When using the preparations, the N-phenylcarbamates are typically applied in an amount of 2 to 100 g per 10 are.

When only resistant strains of phytopathogenic fungi are present, the N-phenylcarbamates (I) can be used alone. However, when resistant strains are present together with sensitive strains, it is advantageous to use them alternatively with benzimidazole thiophanate fungicides and/or cyclic imide fungicides or to use them in combination with benzimidazole thiophanate fungicides and/or cyclic imide fungicides. In the alternative or combined use, each of the active ingredients can be applied as a compound or in a conventional preparation form. In the case of combined use, the weight ratios of the N-phenylcarbamate (I) *and the benzimidazole thiophanate fungicide and/or cyclic imide fungicide can be from about 1 : 0.1 to 1 : 10.0.

Typical examples of benzimidazole thiophanate fungicides and cyclic imide fungicides are given in Table 2:

TABLE 2

Compound Structural formula

Name

COB1HC ₄ H ₉ (n) methyl 1-(butylcarbamoyl)benzimidazol-2-ylcarbamate

^x/NHC5NHC00C ₂ H ₅

Ϊ ·

NHC5 PNSOOS ₂ H ₅

2-(4-thiazolyl)benzimidazole methyl benzimidazole-2-ylcarbamate

2-(2-furyl)benzimidazole

NHCNHC00CH ₃

NHP

II

1,2-bis(3-methoxycarbonyl-2-thiourea)benzene

1,2-bis(3-ethoxycarbonyl-2-thiocarbamido)benzene

2-(0,5-dimethylphosphorylamino)-1(3'-methoxycarbonyl2'-thiocarbamido)benzene

I

:oos ₂ n ₅

2-(0,0-dimethylthiophosphorylamino)-1-(3’-methoxycarbonyl2’-thiocarbamido)benzene

N-(3*,5'-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide

3-(3*,5'-dichlorophenyl)-1-isopropylcarbamoylimidazolidine-2,4-dione

3-(3*,5’-dichlorophenyl)-5-methyl-5-vinyloxazolidine-2,4· dione ethyl(Eb)-3-(3*,5*dichlorophenyl)-5-methyl-

2,4-dioxooxazolidine-5-carboxylate

Furthermore, the P-phenylcarbamates (I) can be applied in a mixture with other fungicides, herbicides, insecticides, miticides, fertilizers and the like.

When N-phenylcarbamates (I) are used as fungicides, they can be applied at a rate of 2 to 100 grams per 10 ares. However, this amount may vary depending on the formulation, time of application, method of application, location of application, disease, crop type and various other factors, and therefore these amounts are indicative.

Some formulations of the fungicidal compositions according to the invention are given for illustration in the examples below. In them, the parts and percentages are by weight.

PREPARATORY EXAMPLE I.

Two parts of compound No. 21, 88 parts of clay and 10 parts of talc are mixed and homogenized, resulting in a powder containing 2% of the active substance.

PREPARATORY EXAMPLE 2.

Thirty parts of compound No. II, 45 parts of diatomaceous earth; 20 parts of white carbon black, 3 parts of sodium lauryl sulfonate as a wetting agent and 2 parts of calcium lignin sulfonate as a dispersing agent are mixed by grinding to obtain a wettable powder containing 30% of the active ingredient.

PREPARATORY EXAMPLE 3.

Fifty parts of compound No. 13, 45 parts diatomaceous earth,

2.5 parts calcium alkylbenzenesulfonate as a wetting agent, and

2.5 parts of calcium lignin sulfonate as a dispersant are mixed during grinding to obtain a wettable powder containing 50% of the active substance.

PREPARATORY EXAMPLE 4.

Ten parts of compound No. 46, 80 parts of cyclohexanone and 10 parts of polyoxyethylene alkylaryl ether as emulsifier are mixed, thereby obtaining an emulsifiable concentrate containing 10% of the active substance.

PREPARATORY EXAMPLE 5.

One part of compound No. 7, 1 part of compound No. I, 88 parts of clay and 10 parts of talc are mixed and pulverized to produce a powder formulation containing 2% of the active ingredient.

PREPARATORY EXAMPLE 6.

Twenty parts of compound No. 86, 10 parts of compound J, 45 parts of diatomaceous earth, 20 parts of white carbon black, 3 parts of sodium lignin sulfonate as a wetting agent and 2 parts of calcium lignin sulfonate as a dispersant, are mixed and pulverized to obtain a wettable powder containing 30% of the active ingredient. *

PREPARATORY EXAMPLE 7.

Ten parts of compound No. 88, 40 parts of compound B, 45 parts of diatomaceous earth, 2.5 parts of calcium lignin sulfonate as a wetting agent and 2.5 parts of calcium lignin sulfonate as a dispersant are mixed and ground to obtain a wettable powder containing 50% active substance.

PREPARATORY EXAMPLE 8.

Twenty-five parts of compound No. 94, 50 parts of compound I, 18 parts of diatomaceous earth, 3.5 parts of calcium alkylbenzene sulfonate as a wetting agent and 3.5 parts of calcium lignin sulfonate as a dispersant _; are mixed by grinding to obtain

- 27 received a wettable powder containing 75% active ingredient.

PREPARATORY EXAMPLE 9.

Twenty parts of compound No. 50, 30 parts of compound A, 40 parts of powdered sugar, 5 parts of white carbon black, 3 parts of sodium lauryl sulfate as a wetting agent and 2 parts of calcium lignin sulfonate as a dispersant are mixed and ground to obtain a wettable powder containing 50% of the active ingredient.

Experimental data showing the excellent fungicidal activity of N-phenylcarbamates (I) are given below. The compounds used

called reference*are as follows: Compound Note Swep 0 Commercial herbicide accessible ^and red- p NHCOCH^ Chlorpropham p- CI' P ^/CH^ NHCOCH Commercial herbicide accessible Barban 0 π nhcoch ₂ c^cch ₂ ci Commercial accessible Oh- herbicide

CI

- 28 SERS

CI

Thiophanate methyl S

yes

Carbendazim _n

Commercially available herbicide

Commercially available herbicide

Commercially available herbicide

Commercially available fungicide

Commercially available fungicide

Commercially available fungicide

Thiabendazole

H

Commercially available fungicide ι

EXPERIENCE I.

Protective activity against powdery mildew of cucumbers (Sphaerotheca fuliginea)

Cucumber seeds (variety Sagami-hanjiro) were sown in a 90 ml flower pot filled with sandy soil. Cultivation was carried out in a greenhouse for 8 days. The resulting plants, having two leaves, were sprayed with the test compound formulated as an emulsion concentrate or wettable powder and diluted with water, in an amount of 10 ml per pot. The seeds were then inoculated with a spore suspension of resistant and susceptible strains of Sphaerotheca fuligineape3 by spraying and again cultivated in the greenhouse. After ten days, the degree of damage was recorded as follows, the results being shown in Table 3.

The examined leaves are measured for the percentage of infected area and classified according to the following disease indices: 0, 0.5, I, 2.4:

Disease index

Percentage of infected area

No infection

0.5

Infected area, less than 5%

Infected area less than 20%

Infected area less than 50%

Infected area, not less than 50%

Disease severity (%) =

Safety

S(disease index) x (number of leaves) •----------------------------------------------------- x 100 x (total number of leaves examined)

The precautionary value is calculated according to the following equation value (%) = (disease severity in the treated pot) ---------------------------------------------------- _{χ 100} (disease severity in the untreated pot)

TABLE 3

Concentration of

Compound - active compound No. compound (ppm)

Protective value for inoculation with a resistant strain (%)

Safety value when inoculating with a susceptible strain (%)

I 200 100 0 2 200 100 0 3 200 100 0 4 200 92 0 5 200 100 0 6 200 100 0 7 200 100 32 a 200 100 0 9 200 100 0 10 200 100 0 II 200 100 0 12 200 100 0

13 200 100 0 14 200 100 0 15 200 100 0 16 200 100 0 17 200 100 0 18 200 100 0 19 200 100 0 20 200 100 0 21 200 100 0 22 200 100 0 XU ⁷ 23 200 90 0 24 200 100 0 25 200 100 0 26 200 100 0 27 200 100 0 28 200 100 0 29 200 100 0 30 200 ί 100 0 31 200 100 0 © 32 200 100 0 33 200 84 0 34 200 100 0 35 200 100 26 36 200 97 0 37 200 100 0 38 200 100 34 39 200 100 0 40 200 100 0 41 200 100 0 42 200 82 0

43 200 100 0 44 200 100 0 45 200 100 0 46 200 100 0 47 200 100 0 48 200 100 0 49 200 100 0 50 200 100 0 51 200 100 0 X 52 200 100 0 it 53 200 100 0 54 200 100 0 55 200 90 0 56 200 100 0 57 200 100 0 58 200 100 0 59 200 100 0 60 200 100 0 61 200 100 0 5 62 200 100 0 63 200 100 0 64 200 100 0 65 200 86 0 66 200 100 0 67 200 100 52 68 200 100 23 69 200 88 0 70 200 100 0 71 200 100 0 72 200 100 0

73 200 100 74 200 100 75 200 100 76 200 100 77 200 90 78 200 92 79 200 94 80 200 100 81 200 100 82 200 100 83 200 100 84 200 97 85 200 94 86 200 100 87 200 100 88 200 100 89 200 92 90 200 88 91 200 84 92 200 88 93 200 90 94 200 100 95 200 100 96 200 100 97 200 100 98 200 100 99 200 100 100 200 100 ΙΟΙ 200 98 102 200 100

ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο

103 200 100 0 104 200 86 0 105 200 84 0 106 200 94 0 107 200 90 0 108 200 88 0 109 200 88 0 sweep 200 0 0 chlorpropham 200 Q 0 drummer 200 25 0 SERS 200 0 0 profam 200 0 0 chlorbufam 200 0 0 benomyl 200 0 100 THIOPHANE - METHYL 200 0 100 _carbendazim 200 0 100

---— ί.»

As can be seen from the results shown in Table 3, the 31-phenylcarbamates (I) according to the invention show an excellent protective effect on resistant strains, but have no protective effect on the tested susceptible strains. The opposite is true for commercially known and available fungicides such as benomyl, thiophanate-methyl and carbendazim, which show a good effect on the susceptible strain, but not on the resistant strain. Other tested compounds, structurally related to the N-phenylcarbamates (I), do not have fungicidal activity at all on the susceptible and resistant strains.

EXPERIENCE 2.

Protective effect against Cercospora beticola in sugar beet

- 35 Sugar beet seeds (Detroit dark red variety) are planted in a 90 ml pot filled with sandy soil. Cultivation is carried out in a greenhouse for

20 days. The resulting seeds are sprayed with the tested compound formulated as a wettable powder or emulsifiable concen- trat and diluted with water. in the norm of 10 ml: for a pot. Then it is- the menacheta are inoculated with suspension < from spores [ from sensitive or resistant strains of Gercospora beticola through a splash- The pots are covered with a sheet of .polyvinyl chloride to retains high humidity and cultivation continues in vegetation- this house another 10 days. The extent of the damage is determines by the same method, as in experiment I, and the results are given in table 4: TABLE 4 Compound- Concentration of Safety Value- Safety stand- we no active consumption ness at inoku- innocence in innocu- seasoning (ppm) liing with resist- touching with sensitivity tent strain (%) real strain (® 2 200 100 0 II 200 100 0 12 200 100 0 13 200 100 0 14 200 100 0 15 200 100 0 16 200 100 0 17 200 100 0 21 200 100 θ 24 200 100 0 25 200 100 0 27 200 100 0 28 200 100 0

30 200 31 200 32 200 35 200 36 200 38 200 39 200 40 200 42 200 43 200 46 200 50 200 52 200 53 200 56 200 60 200 61 200 62 200 68 200 73 200 75 200 76 200 80 200 81 200 83 200 86 200 87 200 88 200 94 200 95 200

ίοο

ΙΟΟ

ΙΟΟ

ΙΟΟ

ΙΟΟ

ΙΟΟ

ΙΟΟ

ΙΟΟ

ΙΟΟ

ΙΟΟ

ΙΟΟ

ΙΟΟ

ΙΟΟ

ΙΟΟ

ΙΟΟ

ΙΟΟ

ΙΟΟ

ΙΟΟ

ΙΟΟ

ΙΟΟ

ΙΟΟ

ΙΟΟ

ΙΟΟ

ΙΟΟ

ΙΟΟ

ΙΟΟ

ΙΟΟ ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο

96 200 97 0 98 200 100 0 99 200 100 0 100 200 100 0 ΙΟΙ 200 100 0 102 200 100 0 sweep 200 0 0 chlorpropham 200 0 0 drummer 200 34 0 SERS 200 0 0 profam 200 0 0 chlorbufam 2002 0 0 benomyl 200 0 100 thiophanate- 200 0 100 methyl carbendazim 200 0 100

As can be seen from the results shown in Table 4, the N-phenylcarbamates according to the invention show an excellent preventive effect on the resistant strain, but have no preventive effect on the tested susceptible strains. The opposite is true for commercially available known fungicides such as benomyl and thiophanate-methyl, which have a significant effect on the susceptible strain, but not on the resistant strain. Other tested compounds similar in structure to the N-phenylcarbamates (I) do not have fungicidal activity on either the susceptible or resistant strains.

EXPERIENCE 3.

Protective effect on pear against Venturia nashicola Plastic pots with a capacity of 90 ml are filled with porous soil and planted with pear seeds (var. chojuro).

- 38 Cultivation was carried out in a greenhouse for 20 days. The resulting seedlings were treated by spraying with the test compound, formulated as an emulsifiable concentrate or wettable powder and diluted with water, at a rate of 10 ml per pot. The seedlings were then inoculated with a suspension of spores of resistant and susceptible strains of Venturia nashicola. The seedlings were placed at 20° C under high humidity conditions for 3 days and then at 20° C under fluorescent lamp irradiation for another 20 days. The degree of damage was determined in the same way as in experiment I and the results are shown in Table 5.

TABLE 5.

Compound No. Concentration of active compound (ppm) Precautionary value when inoculating with a resistant strain (%) Precautionary value when inoculating with a susceptible strain (%) 2 200 100 0 3 200 100 0 7 200 100 0 II 200 100 0 12 200 100 0 13 200 100 0 14 200 100 0 15 200 100 0 16 200 100 0 17 200 100 0 21 200 100 0 24 200 100 0 25 200 100 0

27 200 100 0 28 200 100 0 35 200 100 0 36 200 97 0 42 200 91 0 43 200 100 0 46 200 100 0 50 200 100 0 53 200 100 0 56 200 100 0 Sy ^J 68 200 100 0 75 200 100 0 .76 200 97 0 80 200 100 0 81 200 100 0 83 200 97 0 86 200 100 0 87 200 100 0 88 200 100 0 94 200 100 0 95 200 97 0 96 200 94 0 97 200 97 0 98 200 100 0 99 200 100 0 100 200 100 0 ΙΟΙ 200 97 0 102 200 100 0 benomyl 200 0 100 thiophanate- methyl 200 0 100

- 40 As can be seen from the results shown in Table 5, the T-phenylcarbamates according to the invention show an excellent preventive effect against the resistant strain, but do not exhibit a preventive effect against the tested susceptible strains. The opposite is true for commercially available known fungicides such as benomyl and thiophanate-methyl, which have a good effect against the susceptible strains, but not against the resistant ones.

EXPERIENCE 4.

Protective effect in peanuts against Cercospora arachidicola.

Peanut seeds (var. Chiba haaryusel) were planted in a 90 ml plastic pot filled with sandy soil. Cultivation was carried out in a greenhouse for 14 days. The germinated seeds were treated with the test compound formulated as an emulsion concentrate or as a wettable powder and diluted with water by spraying 10 ml per pot. The seeds were then inoculated by spraying with a spore suspension of a resistant and a susceptible strain of Cercospora arachidicoia. The plants were covered with a polyvinyl chloride sheet to provide humidity conditions and cultivated in a greenhouse for 10 days. The degree of damage was determined in the same way as in experiment I, and the results are shown in Table 6:

TABLE b.

Compound No. Concentration of active substance (ppm) Precautionary value when inoculating with a resistant strain t Precautionary value when inoculating with a susceptible strain (%) 2 200 100 0 7 200 100 0

12 200 13 200 I? 200 25 200 27 200 28 200 31 200 32 200 35 200 38 200 s 39 200 40 200 46 200 50 200 53 200 56 200 60 200 62 200 64 200 © 73 200 76 200 86 200 87 200 88 200 94 200 98 200 99 200 100 200 benomyl 200 thiophanatemethyl 200

100 0 100 0 100 0 100 0 100 0 100 0 100 0 100 0 100 0 100 0 100 0 100 0 100 0 100 0 100 0 100 0 100 0 100 0 100 0 100 0 100 0 100 0 100 0 100 0 100 0 100 0 100 0 100 0 0 100 0 100

- 42 As can be seen from the results _? shown in Table b, the N-phenylcarbamates (I) according to the invention show an excellent protective effect on the resistant strain, but do not show efficacy on the tested susceptible strain. The opposite is observed with commercially available known fungicides such as benomyl and thiophanate-methyl, which are active against the susceptible strain, but not against the resistant one.

EXPERIENCE 5.

Protective effect against Botrytis cinerea in cucumbers Plastic pots with a volume of 90 ml were filled with sandy soil and cucumber seeds (var. Sagami hanjiro) were planted in them. Cultivation was carried out in a greenhouse for 8 days to obtain seedlings with cotyledons. The test compound, formulated as an emulsifiable concentrate or as a wettable powder and diluted with water, was sprayed onto them at a rate of 10 ml per pot. After air drying, the seedlings were inoculated with mycelial discs (5 mm in diameter) of a resistant and susceptible strain of Botrytis cinerea, the discs being placed on the leaf surface. The plants were infected by incubation for three days at high humidity at 20°C, after which the degree of disease was recorded. Damage was determined as described in experiment 1, the results being given in Table 7.

TABLE 7.

Concentration of

Active ingredient compound (ppm)

Protective value when inoculated with a resistant strain Protective value when inoculated with a susceptible strain (%)

200

100

50 94 2 200 100 50 100 3 200 100 50 94 4 500 98 5 200 100 6 200 91 7 200 100 50 100 8 200 100 9 200 100 ΙΟ 500 98 II 200 97 12 200 100 50 97 13 200 100 50 100 .12.5 100 14 200 100 50 100 15 200 100 50 100 12.5 100 16 200 100 50 100 17 200 100 50 100 18 200 97 19 200 100

The

Ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο

20 200 100 0 21 200 100 0 50 100 0 22 200 97 0 23 500 96 0 24 200 100 0 25 200 100 0 50 100 0 12.5 100 0 26 200 100 0 27 200 100 0 50 100 0 28 200 100 0 50 100 0 12.5 94 0 29 200 100 0 50 100 0 30 200 100 0 50 100 0 31 200 100 0 50 100 0 32 200 100 0 50 100 0 33 500 86 0 34 200 100 0 35 200 100 0 50 100 0 36 200 100 0 37 200 100 0 38 200 100 0

50 ΙΟΟ 39 200 ΙΟΟ 50 ΙΟΟ 40 200 ΙΟΟ 50 ΙΟΟ 41 200 94 42 500 82 43 200 ΙΟΟ 50 ΙΟΟ 12.5 94 44 200 ΙΟΟ 43 200 91 46 200 ΙΟΟ 50 ΙΟΟ 47 200 ΙΟΟ 48 200 ΙΟΟ 49 200 ΙΟΟ 50 200 ΙΟΟ 50 ΙΟΟ 51 200 ΙΟΟ 50 ΙΟΟ 52 200 ΙΟΟ 50 ΙΟΟ 53 200 ΙΟΟ 50 ΙΟΟ 54 200 95 55 500 97 56 200 ΙΟΟ 50 ΙΟΟ 57 200 97

Ο Ο Ο Ο Ο Ο Ο Ο Ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο

58 200 59 200 60 200 61 200 50 62 200 50 63 200 50 64 200 50 65 500 66 200 67 200 68 200 69 500 70 200 71 200 72 200 73 200 74 200 75 200 76 200 77 500 78 200 79 200 80 200 81 200 82 200 83 200

100

100

100

100

100

100

100

100

100

100

100

100

100

100

100

100

100

100

100

100

100

100

100

50 92 84 200 100 85 200 97 86 200 100 50 100 12.5 97 87 200 100 50 97 12.5 86 88 200 100 ' 50 100 12.5 88 89 200 94 90 200 88 91 200 92 92 200 92 93 . 200 94 94 200 100 50 97 12.5 94 95 200 100 50 97 96 200 100 50 94 97 200 100 50 94 98 200 100 50 100 12.5 97

Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο

99 200 100 0 50 97 0 12.5 94 0 100 200 100 0 50 97 0 12.5 97 ,0 ΙΟΙ 200 100 0 50 94 0 102 200 100 0 50 97 0 103 200 100 0 50 94 0 104 200 97 0 105 200 97 0 106 200 100 0 107 200 100 0 108 200 100 0 109 200 97 0 benomyl 200 0 100 thiophanatemethyl 200 0 100 As is sees from the results of table 7 I-phenylcar- bamates (I) according to the invention shows excellent safety effect in resistant strain, but are not active in tests sensitive-

In contrast, commercially available fungicides such as benomyl and thiophanate-methyl are effective against the susceptible strain but not against the resistant strain.

EXPERIENCE 6.

Protective effect in cucumbers against Mycosphaerella melonis

- 49 Plastic pots with a capacity of 90 ml were filled with sandy soil and planted with cucumber seeds (var. Sagamihanjiro). They were cultivated in a greenhouse for 8 days to obtain seedlings with cotyledons. The test compound, formulated as an emulsifiable concentrate or as a wettable powder and diluted with water, was sprayed onto the plants at a rate of

10 ml per pot. After air drying, the plant is inoculated with a mycelial disk (5 mm in diameter) of a resistant or susceptible strain of Mycosphaerella melonis, How the disc is places on the surface on the leaf. The plant behaves at high enmityTuTo be infect for 4 days at 25° C. Degree of disability on plants are determined by the way they are attempt I,as the results are shown in table 8. TABLE 8. Concentration of Precautionary value Safety stand- Compound the active substance when inoculated with innocence in innocu- No. thing (ppm) resistant strain feelings t tele strain (%) § 200 100 0 7 200 100 0 12 200 100 0 13 200 100 0 14 200 100 0 16 200 100 0 28 200 100 0 36 200 100 0 46 200 100 0 48 200 100 0 49 200 100 0

53 200 100 0 56 200 100 0 61 200 100 0 63 200 100 0 74 2G0 100 0 76 200 100 0 86 200 100 0 87 200 100 0 88 200 100 0 94 200 100 0 98 200 100 0 99 200 100 0 100 200 100 0 benomyl .200 0 100 thiophanate- 200 0 100

methyl

As can be seen from the results in Table 8, the N-phenylcarbamates (I) according to the invention show excellent protective activity against resistant strains, but have no such effect against the tested susceptible strain. The opposite is true for commercially available known fungicides such as benomyl and thiophanate-methyl, which have a very good effect against the susceptible strain, but not against the resistant one.

EXPERIENCE 7,

Protective effect in oranges against Penicillium italicum.

Orange fruits (var. Unaka) are washed with water and air dried. The fruits are immersed in a solution of the test compound obtained by diluting an emulsifiable concentrate containing the test compound. Melting is continued

I minute. After air drying, the fruits are inoculated with a suspension of spores of the above penicillin-resistant and -sensitive strains by spraying and then placed in a room with high humidity for 14 days. The degree of to get injured define as follows: The fruits studied are measured in terms of damaged- their area and ί are classified with the following indices: I, 2,3,4 and 5. index of illness Percentage of infected area 0 No infection I The infected area is less than 20% 2 The infected area is less than 40% 3 The infected area is less than 60% 4 The infected area is less than 80% 5 The infected area is not less than 80 % Calculating the degree of disability and on the safety value is performs as is described in experiment I. TABLE 9. Compound No. Concentration of active substance (ppm) Precautionary value when inoculating with a resistant strain (%) Precautionary value when inoculating with a susceptible strain {%) 2 200 100 0 5 200 100 0 9 200 100 0 II 200 100 0 13 200 100 about 21 200 100 0 28 200 97 0 46 200 100 0

50 200 100 0 53 200 100 0 56 200 100 0 61 200 100 0 62 200 100 0 63 200 100 0 64 200 100 0 67 200 100 0 70 200 100 0 73 200 100 0 74 200 100 . 0 75 200 100 0 76 200 100 0 86 200 100 0 87 200 100 0 88 200 100 0 94 200 100 0 98 200 100 0 99 200 100 0 100 200 100 0 benomyl 200 0 100 thiophanate- 200 0 100 methyl thiabenzazole 200 0 100

As can be seen from the results shown in Table 9, the N-phenylcarbamates (I) according to the invention show an excellent protective effect on the resistant strain, but have no such effect against the tested susceptible strain. The opposite is true for commercially available known fungicides such as benomyl, thiophanate-methyl and thiabendazole.

- 53 which are effective against the sensitive strain, but not against the resistant one.

EXPERIENCE 8.

Protective effect in cucumbers against Sphaerotheca fuliginea.

Plastic pots with a capacity of 90 ml were filled with sandy soil and planted with cucumber seeds (Bap.Sagamihanjiro). Cultivation was carried out in a greenhouse for 8 days. The germinated seedlings, which already had cotyledons, were sprayed with the test compound formulated as an emulsifiable concentrate or wettable powder and diluted with water, each pot being treated with 10 ml. The plants were then inoculated with a mixed spore suspension of a susceptible and resistant strain of the above pest by spraying and then cultivated in a greenhouse. After ten days, the degree of infection of the plants was recorded. The degree of damage was determined in the same way as in experiment I and the results are shown in Table 10.

TABLE 10.

Compound N° Concentration of active substance (PPm) Safety (%) 13 100 34 13 20 0 15 100 28 28 100 44 28 20 0 43 100 36 43 20 0 86 100 44 86 20 0

ΙΟΟ

ΙΟΟ

A

A

In

In with

with d

e

E

E

P

P

6&

n n

+ A + E + H + A

- 54,100

100

100

100

100

100

500

100

100

500

100

100

100

100

100 + 20 + 20 + 20 + 20 ge o

100

100

100

100

15 + P 20 + 20 100 28 + A 20 + 20 100 28 + In 20 + 20 100 28 + With 20 + 20 100 43 + D 20 + 20 100 43 + & 20 + 20 100 43 + n 20 + 20 100 86 + A 20 + 20 100 86 + In 20 + 20 100 86 + P 20 + 20 100 88 + with 20 + 20 100 88 + It is 20 + 20 100 88 + & 20 + 20 100 94 + A 20 + 20 100 94 + It is 20 + 20 100 94 + G 20 + 20 100 98 + With 20 + 20 100 98 + H 20 + 20 100 99 + A 20 + 20 100 99 + In 20 + 20 100 100 + A 20 + 20 100 100 + D 20 + 20 100 100 + It is 20 + 20 100

As can be seen from the results shown in Table 10, the combined use of N-phenylcarbamates (I) according to the invention with benzimidazole thiophanate fungicides and/or cyclic imide fungicides shows a much higher protective effect compared to the single application.

- 56 EXPERIENCE 9.

Protective effect in tomatoes against Batrytie cinerea.

A plastic pot with a capacity of 90 ml was filled with sandy soil and tomato seeds (var. Fukuji No. 2) were planted in it. Cultivation was carried out in a greenhouse for 4 weeks. The germinated seedlings were in the 4-leaf stage. The test compound or compounds, formulated as an emulsion concentrate or as a wettable powder and diluted with water, were sprayed onto the plants at a rate of 10 ml per pot. The plants were then inoculated with mixed spores of a susceptible and resistant strain of the top mold in the form of a suspension by spraying and the plants were placed in a room with high humidity for 5 days at 20° C. The degree of damage was determined in the same way as in Example I and the results are given in Table II.

Safety value (%)

TABLE II

Concentration of

Compound No. active substance (ppm)

13 100 44 13 20 0 25 100 27 25 20 0 28 100 38 28 20 · 0 43 100 38 43 20 0 86 100 42 86 20 0 88 100 42

- 57 - 88 20 0 94 100 42 94 20 0 98 100 40 98 20 0 99 100 44 99 20 0 100 100 38 100 ²⁰ 0 with I 100 48 I 20 22 Ί 500 46 J 100 18 κ 100 42 κ 20 15 L 500 42 L 100 12 13 + I <20+50 100 13 + I 20 + 50 100 © 13 + K 20 + 50 100 13 + L 20 + 50 100 25 + 1 20 + 50 100 25 + K 20 + 50 100 28 + 1 20 + 50 100 28 + L 20 + 50 100 43 + 1 20 + 50 100 43 + J 20 + 50 100 86 + I 20 + 50 100 86 + K 20 + 50 100 88 + 1 20 + 50 100

88 + 1 20 + 50 100 94 + Ϊ 20 + 50 100 94 +J 20 + 50 100 98 + 1 20 + 50 100 98 + K 20 + 50 100 99 + 1 20 + 50 100 99 +J 20 + 50 100 100 + I 20 + 50 100 100 + K 20 + 50 100

As can be seen from the results shown in Table II, the combined use of the N-phenylcarbamates (I) according to the invention with benzimidazole thiophanate fungicides and/or cyclic imide fungicides gives much better results than their separate application.

Claims (41)

Patent claims I. A fungicidal composition containing as active ingredient a fungicidally effective amount of H-phenylcarbamate with the formula: A I 2 in which E and E are the same or different and represent a lower alkyl, lower alkenyl, lower alkynyl or lower alkyl group substituted with at least one halogen, lower alkoxy or lower cycloalkyl; E^ represents C^alkyl, C^alkenyl, C^alkynyl, lower cycloalkyl, lower haloalkyl, lower haloalkynyl, aralkyl, alkynyl substituted with at least one halogen, cyano, lower alkoxy, lower alkenyloxy, lower haloalkoxyphenoxy, lower pyralkyloxy or lower cycloalkyl or a group of the formula: ^(C ⁿ ₂ )y -CH Ό in which m represents 0, 1 or 2; n means 1, 2 or 3 X and Y are the same or different and represent oxygen or a carbon atom and £ represents hydrogen, lower alkyl, lower alkenyl, lower alkynyl, lower cycloalkyl, lower haloalkyl, lower alkyl group substituted with at least one halogen, cyano group, lower alkoxy or lower alkoxycarbonyl or a group of formula -COE ²¹ · or -SO^E ²¹ , (¢0 in which E ²¹ represents a lower alkyl group, lower alkenyl, lower alkynyl, lower cycloalkyl, lower haloalkyl, lower alkyl group substituted with at least one halogen, cyano group, lower alkoxy, lower cycloalkyl or phenyloxy group (the phenyloxy group may optionally be substituted with at least one halogen and/or with at least one alkyl), phenyl, furyl, thienyl, phenyl group substituted with at least one halogen, cyano group, nitro, trifluoromethyl, lower alkyl or lower alkoxy group or aralkyl group (aralkyl may be optionally substituted with at least one halogen and/or at least one alkyl), provided that when E1 is methyl, ^E2 is not methyl or butyl, together with an inert carrier or diluent. 2. A fungicidal composition according to claim 1, which comprises as additional active substance or active substances a benzimidazole thiophanate fungicide and/or a cyclic imide fungicide, 3. A fungicidal composition according to claim 2, wherein the benzimidazole fungicide is methyl 1-(butylcarbamoyl)benzimidazol-2-ylcarbamate, 2-(2-furyl)benzimidazole, 2-(4-thiazolyl)benzimidazole, methyl benzimidazol-2-ylcarbamate, 1,2-bis(3-methoxycarbonyl-2-thiourea)benzene, 1,2-bis(3-ethoxycarbonyl-2-thiourea)benzene, 2-(0,$-Dimethylphosphorylamino)-1-(3*-methoxycarbonyl2'-thiourea)benzene or 2-(0,0-dimethylthiophosphorylamino)-1(3'-methoxycarbonyl-2'-thiourea)benzene, and the cyclic imide fungicides may be 3-(3} 5*-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide, 3-(3*,5*-dichlorophenyl)-1-isopropylcarbamoylimidazolidine-2,4-dione, 3-(3',5'-dichlorophenyl)-5-methyl- 5-vinyloxazolidine-2,4-dione or ethyl (E5)-3-(3’,5’-dichlorophenyl)- 5-methyl-2,4-dioxooxazolidine-5-carboxylate. ¹ 4. N-phenylcarbamate with formula: in which E1 and ^E2 may be the same or different and represent a lower alkyl, lower alkenyl, lower alkynyl or lower alkyl group, lower alkoxy or lower cycloalkyl; substituted with at least one halogen, E^ _{represents C-C alkyl, C 3-3 alkenyl, C 3-3 alkynyl , lower} cycloalkyl, lower haloalkyl, lower haloalkynyl, lower aralkyl, lower alkyl substituted with at least one halogen, cyano, lower alkoxy, lower alkenyloxy, lower oxy, phenoxy, lower aralkyloxy or lower cycloalkyl haloalkyl group of the formula in which m represents 0, 1 or 2; means 1, 2 or 3; and Y are the same or different and represent oxygen or sulfur; Z represents hydrogen, lower alkyl, lower alkenyl, lower alkynyl, lower cycloalkyl, lower haloalkyl, lower alkyl substituted with at least one halogen, cyano, lower alkoxy or lower alkoxycarbonyl or a group of the formula: -COE^ or -O ₂ e\v which represents lower alkyl, lower alkenyl, lower alkynyl, lower cycloalkyl, . lower haloalkyl, alkyl group substituted with at least one halogen, cyano group, lower alkoxy, lower cycloalkyl or phenoxy (the phenoxy group may optionally be substituted with at least one halogen and/or and at least one alkyl), phenyl, furyl, thienyl, a phenyl group substituted with at least one halogen, a cyano group, nitro, trifluoromethyl, lower alkyl or lower alkoxy or an aralkyl group (in which the aralkyl may be optionally substituted with at least one halogen and/or with at least one alkyl), provided that when E ¹ represents methyl, E ² is not methyl or butyl. 5. N-phenylcarbamates according to claim 4, wherein E1 and o E are independently methyl, ethyl, n-propyl, isopropyl, n-butyl, allyl, 2-butenyl, 3-butenyl, ¹ propargyl, 3-butenyl, difluoromethyl, 2-chloroethyl, 2,2,2-trifluoroethyl, 2-methoxyethyl or cyclopropylmethyl, means methyl, ethyl, n-propyl, isopropyl, sec.butyl, I-ethylpropyl, 1-methylbutyl, I-ethylbutyl, 2-butenyl, 3-butenyl, 2-methyl-2-propenyl, 1-ethyl-2-propenyl, 1-methyl-Zbutenyl, 1-pentyl-2-propenyl, propargyl, 1-methyl-2-propynyl, 2butynyl, 3-butynyl, 1-ethyl-2-propynyl, I-methyl-3-butynyl, Ibutynyl-2-propynyl, 1-pentyl-2-propynyl, cyclobutyl, cyclopentyl, 2-fluoroethyl, 2-chloroethyl, 2,2-dichloroethyl, 1-methyl-2-bromoethyl, 1-fluoromethyl-2-fluoroethyl, 1-bromomethyl-2-bromomethyl, 1-methyl- 2,2,2-trichloroethyl, 1-ethyl-2-bromomethyl, 4-chloro-2-butenyl, 4-chloro2-butynyl, 2-cyanoethyl, 1-methyl-2-methoxyethyl, 1-methyl-2-butoxyethyl, 2-allyloxyethyl, 2-(2-chloroethoxy)ethyl, 2-benzyloxyethyl, 1-chloromethyl-2-methoxyethyl, cyclopropylmethyl, 1-cyclopropylethyl, 1-cyclopentylethyl, 2-furylmethyl, 1-phenylethyl or 3-tetrahydrofuranyl; X and Y are independently oxygen or sulfur and Z represents hydrogen, methyl, ethyl, n-butyl, allyl, acetyl, propionyl, n-pentanoyl, sec-pentanoyl, cyclopropanecarbonyl, benzoyl, 2-chlorobenzoyl, 2,4-dichlorobenzoyl, ⁴ -methylbenzoyl, methanesulfonyl or ethoxycarbonylmethyl, provided that when E represents methyl, E is not methyl or butyl. Q2> 6. N-phenylcarbamate according to claim 5, wherein E ¹ and E ² independently of each other denote methyl, ethyl, n-propyl, allyl or propargyl, E 2 denotes ethyl, isopropyl, sec-butyl, I-methylbutyl, 1-ethylbutyl, I-ethylpropyl, 1-methyl-2-propenyl, I-ethyl-2-propenyl, I-methyl-3-butenyl, propargyl, 1-methyl-2-propynyl, 1-ethyl-2-propynyl, 3-butynyl, I-methyl-3-butynyl, 1-butyl2-propynyl, 2-fluoroethyl, 1-methyl-2-bromomethyl, 1-fluoromethyl-2-fluoroethyl, 1-bromomethyl-2-bromomethyl, 4-chloro-2-butynyl, 1-methyl-2-methoxyethyl, I-cyclopropylethyl or I-phenylethyl; X represents oxygen, Y represents oxygen or sulfur and Z represents hydrogen, acetyl, propionyl, n-pentanoyl, sec-pentanoyl, cyclopropanecarbonyl, benzoyl, 2-chlorobenzoyl, 2,4-dichlorobenzoyl or 4-methylbenzoyl with the proviso that when E ¹ represents methyl, E ² is not a methyl group. 7. The N-phenylcarbamate of claim 6, wherein E is ¹ and 2 3 E means ethyl, E means ethyl, isopropyl, sec-butyl, I-methylbutyl, I-ethylbutyl, I-methyl-3-butenyl, 1-methyl-2-propynyl, 4-chloro-2-butynyl or 1-phenylethyl, X represents oxygen, Y represents oxygen or sulfur and Z represents hydrogen, acetyl, cyclopropanecarbonyl, benzoyl or 2-chlorobenzoyl. 8. The N-phenyl carbamate according to claim 4, which is isopropyl N-(3,4-diethoxyphenyl)carbamate. 9. The N-phenylcarbamate of claim 4, which is 1-methyl-2-propynyl N-(3,4-diethoxyphenyl)carbamate. 10. The N-phenylcarbamate according to claim 4, which is 4-chloro-2-butynyl N-(3,4-diethoxyphenyl)carbamate. 11. The N-phenylcarbamate of claim 4, which is isopropyl N-(3,4-diethoxyphenyl)tricarbamate. 12. The N-phenylcarbamate of claim 4, which is 1-phenylethyl N-(3,4-diethoxyphenyl)carbamate. 13. The N-phenylcarbamate of claim 4, which is isopropyl N-acetyl-N-(3,4-diethoxyphenyl)carbamate. 14. The N-phenylcarbamate of claim 4, which is isopropyl N-cyclopropanecarbonyl-1-(3,4-diethoxyphenyl)carbamate. 15. The N-phenylcarbamate of claim 4, which is isopropyl N-benzoni-[1-(3,4-diethoxyphenyl)carbamate. 16. The N-phenylcarbamate of claim 4, which is isopropyl N-(2-chlorobenzoyl)-N-(3,4-diethoxyphenyl)carbamate. 17. A method for combating plant pathogenic fungi* comprising applying to them a fungicidally effective amount of at least one N-phenylcarbamate of the formula: in which E^, E ² , e\ X^ Y and Z have the meanings specified in claim I. 18. The method of claim 17, wherein the plant pathogenic fungus is a resistant strain. 19. A method for combating plant pathogenic fungi* which comprises applying a fungicidally effective amount of a mixture of N-phenylcarbamate having the formula: in which E^ E ^X 0 ¢5 tion I and benzimidazole thiophanate fungicide and/or cyclic imide fungicide. 20. Method for preparing N-phenylcarbamate of formula: in which 2 has the meaning specified in claim 4, except hydrogen, and E1, ^E2 , ^E5 , X and Y have the meanings given in claim 4, which consists in reacting a 3,4-dialkoxyphenylcarbamate of formula: 8¾ in which S^, B ² , c\ X^ and Y have the meanings indicated above, with a halide of formula: wherein A represents halogen and Z has the meanings given above. 21. A fungicidal composition comprising as active ingredient a fungicidally effective amount of N-phenylcarbamate of the formula: in which E ¹ and E ² are the same or different and represent a lower alkyl, lower alkenyl, lower alinyl or lower alkyl group substituted with at least one halogen, lower alkoxy or lower cycloalkyl; E^ represents C1-4alkyl, _C3-3alkenyl , _C1-4alkynyl , lower cycloalkyl, lower haloalkenyl, lower haloalkynyl, lower aralkyl, lower alkyl group substituted with at least one halogen, cyano group, lower alkoxy, lower alkenyloxy, lower haloalkoxy, phenoxy, lower aralkyloxy or lower cycloalkyl; X and Y are the same or different and represent oxygen or sulfur and X represents hydrogen, lower alkyl, lower alkenyl, lower alkynyl, lower cycloalkyl, lower haloalkenyl, lower alkyl group substituted with at least one halogen, cyano group, lower alkoxy or lower alkoxycarbonyl or with a group of formula: -COE ² * ^- or SC^E ² *, in which E represents lower alkyl, lower alkenyl, lower alkynyl, lower cycloalkyl, lower haloalkyl, lower alkyl group substituted with at least one halogen, cyano group, lower alkoxy, lower cycloalkyl I or a phenoxy radical (the phenoxy radical may be optionally substituted by at least one halogen and/or by at least one alkyl), phenyl, furyl, phenyl, substituted *by at least one halogen, cyano, nitro, trifluoromethyl^ ^and Oalkyl or a lower alkoxy or aralkyl group (the aralkyl may be optionally substituted by at least one halogen and/or by at least one alkyl), provided that when E represents methyl, E is not methyl or butyl, together with an inert carrier or diluent. 22. A fungicidal composition according to claim 21, which additionally comprises one or more active substances such as benzimidazole thiophanate fungicides and/or cyclic imide fungicides. 23. A fungicidal composition according to claim 22, wherein the benzimidazole thiophanate fungicide is methyl 1-(butylcarbamoyl)benzimidazol-2-ylcarbamate, 2-(2-furyl)benzimidazole, methyl benzimidazol-2-ylcarbamate, and the cyclic imide fungicides may be 3-( ^3' ,5'-dichlorophenyl)-1,2-dimethylcyclopropane-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 (E5)-3-(3*,5’-dichlorophenyl)-5-methyl-2,4-dioxooxazolidine-5-carboxylate. 24o Triphenylcarbamate with formula: in which E1 and ^E2 are the same or different and represent lower alkyl, lower alkenyl, lower alkynyl, lower alkyl substituted with at least one halogen, lower alkoxy or lower cycloalkyl; E represents C1-4alkyl, C1-4alkenyl, C1-4alkynyl, lower cycloalkyl, lower haloalkenyl, lower haloalkynyl, lower aralkyl, lower alkyl group substituted with at least one halogen, cyano, lower alkoxy, lower alkenyloxy, lower haloalkoxy, phenoxy, lower aralkyloxy or lower cycloalkyl; X and Y are the same or different and represent an oxygen or sulfur atom and Z represents hydrogen, lower alkyl, lower alkenyl, lower alkynyl, lower cycloalkyl, lower haloalkyl, lower alkyl group substituted with at least one halogen, cyano, lower alkoxy or lower alkoxycarbonyl or a group of formula: -COE^ or -30 ₂ e\ in which E ² * represents a lower alkyl group^kkenyl, lower alkynyl, lower cycloalkyl, lower haloalkyl, lower alkyl group substituted with at least one halogen, cyano, lower alkoxy, lower cycloalkyl or phenoxy group (the phenoxy group may be optionally substituted with at least one halogen and/or with at least one alkyl), phenyl, furyl, phenyl a group substituted with at least one halogen, cyano, nitro, trifluoromethyl, lower alkyl or lower alkoxy or aralkyl (wherein the aralkyl may optionally be substituted with at least one halogen and/or with at least methyl or butyl. 25. The N-phenylcarbamate of claim 24, wherein E1 and ^E2 are independently methyl, ethyl, n-propyl, isopropyl, n-butyl, allyl, 2-butenyl, 3-butenyl, propargyl, 3-butynyl, difluoromethyl, 2-chloroethyl, 2,2,2-trifluoroethyl, 2-methoxyethyl or cyclopropylmethyl, ^E5 is methyl, ethyl, _n -propyl, isopropyl, sec-butyl, 1-ethylpropyl, 1-methylbutyl, 1-ethylbutyl, 2-butenyl, 3-butenyl, 2-methyl-2-propenyl, 1-ethyl-2-propenyl, 1-methyl-3-butenyl, 1-pentyl-2-propenyl, propargyl, 1-methyl-2-propynyl, 2-butynyl, 3-butynyl, 1-ethyl-2-propynyl, 1-methyl-3-butynyl, 1-butyl2-propynyl, 1-pentyl-2-propynyl, cyclobutyl, cyclopentyl, 2-fluoroethyl, 2-chloroethyl, 2,2-dichloroethyl, 1-methyl-2-bromomethyl, 1-fluoromethyl-2-fluoroethyl, 1-bromomethyl-2-bromomethyl, 1-methyl-2,2,2trichloroethyl, 1-ethyl-2-bromomethyl, 4-chloro-2-butenyl, 4-chloro-2-butynyl, 2-cyanoethyl, 1-methyl-2-methoxyethyl, 1-methyl-2-butoxyethyl, 2-allyloxyethyl, 2-(2-chloroethoxy)ethyl, 2-benzyloxyethyl, 1-chloromethyl-2-methoxyethyl, cyclopropylmethyl, 1-cyclopropylethyl, 1-cyclopentylethyl, 2-furylmethyl, 1-phenylethyl or 3-tetrahydrofuranyl; X and Y are independently oxygen or sulfur and X represents hydrogen, methyl, ethyl, n-butyl, allyl, acetyl, propionyl, n-pentanoyl, sec-pentanoyl, cyclopropanecarbonyl, benzoyl, 2-chlorobenzoyl, 2,4-dichlorobenzoyl, 4-methylbenzoyl, methanesulfonyl or ethoxycarbonylmethyl with the proviso that when E^ represents methyl, E is not a methyl or butyl radical. 26. A 1-phenylcarbamate according to claim 25, wherein E 1 is ¢9 and are independently methyl, ethyl, n-propyl, allyl or propargyl, denotes ethyl, isopropyl, sec-butyl, 1-methylbutyl, 1-ethylpropyl, I-ethylbutyl, 1-methyl-2-propenyl, 1-ethyl-2-propenyl, I-methyl-3-butenyl, propargyl, 1-methyl-2-propynyl, I-ethyl-2-propenyl, 3-butynyl, 1-methyl-3-butynyl, 1-butynyl-2-propynyl, 2-fluoroethyl, 1-methyl-2-bromethyl, 1-fluoromethyl-2-fluoroethyl, 1-bromomethyl-2-bromethyl, 4-chloro-2-butynyl, 1-methyl-2-methoxyethyl, 1-cyclopropylethyl or 1-phenylethyl; X represents oxygen, Y represents oxygen or sulfur, and Z represents hydrogen, acetyl, propionyl, n-pentanoyl, sec-pentanoyl, cyclopropanecarbonyl, benzoyl, 2-chlorobenzoyl, 2,4-dichlorobenzoyl, or 4-methylbenzoyl, provided that when E ¹ represents methyl, it is not a methyl group. 27. An N-phenylcarbamate according to claim 26, wherein ^E1 and E2 are ethyl, E2 is ethyl, isopropyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, 1-methyl-3-butenyl, 1-methyl-2-propynyl, 4-chloro-2-butynyl or 1-phenylethyl, X is oxygen, Y is oxygen or sulfur and Z is hydrogen, acetyl, cyclopropanecarbonyl, benzoyl or 2-chlorobenzoyl. 28. The N-phenylcarbamate of claim 24, which is isopropyl N-(3,4-diethoxyphenyl)carbamate. 29. An N-phenylcarbamate according to claim 24, which is 1-methyl-2-propynyl N-(3,4-diethoxyphenyl)carbamate. 30. An N-phenylcarbamate according to claim 24, which is 2-chloro-2-butynyl N-(3,4-diethoxyphenyl)carbamate. 31. The N-phenylcarbamate of claim 24, which is isopropyl N-(3,4-diethoxyphenyl)thiolcarbamate. 32. The N-phenylcarbamate of claim 24, which is 1-phenylethyl N-(3,4-diethoxyphenyl)carbamate. 33. The N-phenylcarbamate of claim 24, which is isopropyl N-acetyl-1H-(3,4-diethoxyphenyl) _carbamate . 34. The N-phenylcarbamate of claim 24, which is isopropyl N-cyclopropanecarbonyl-N-(3,4-diethoxyphenyl)carbamate. 35. The N-phenylcarbamate of claim 24, which is isopropyl N-benzoyl-N-(3,4-diethoxyphenyl)carbamate. 36. The N-phenylcarbamate of claim 24, which is isopropyl N-(2-chlorobenzoyl)-N-(3,4-diethoxyphenyl)carbamate. 37. A method for controlling pathogenic fungi on plants, comprising applying a fungicidally effective amount of at least one N-phenylcarbamate of the formula: X I! PSUE ³ in which E^, ^E2 , ^E3 , X, Y and Z have the meanings specified in claim 21, to plant pathogenic fungi. 38. The method of claim 37, wherein the plant pathogenic fungus is a resistant strain. 39. A method for controlling pathogenic fungi on plants, which comprises applying a fungicidally effective amount of a mixture of N-phenylcarbamate having the formula: E' in which E ¹ , E ² , E ³ , X, Y and Z have the meanings specified in claim 21, and a benzimidazole thiophanate fungicide and/or a cyclic imide fungicide. Or 40. The N-phenylcarbamate of claim 24, which is ethyl-N-(3,4-diethoxyphenyl)carbamate. 41. A fungicidal composition according to claim 21, wherein the N-phenylcarbamate is ethyl N-(3,4-diethoxyphenyl)carbamate. 42. A method for controlling plant pathogenic fungi according to claim 37, wherein the phenylcarbamate ¹ is N-(3,4-diethoxyphenyl)carbamate.