BG60830B2 - Fungicide 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.

Benzimidazole thiophanate fungicides such as benomyl (methyl 1- (butylcarbamoyl) benzimidazol-2-ylcarbamate), fubelidazole (2- (2-furyl) benzimidazole), thiabendazole (2- (4-thiazolyl) benzimidobenzylbenzimidobenzylbenzimidylbenzimidobenzylbenzimidobenzylbenzimidobenzylbenzylidene) -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'-thiocarbamide) benzene show excellent fungicidal activity against pa personal pathogenic fungi in plants and are widely used as fungicides in agriculture since 1970. However, their continuous application over a long period of time enables the phytopathogenic fungi to develop resistance against them. This leads to a decrease in the number of times

- 2 plant-protecting effect. In addition, fungi that develop resistance to certain types of benzimidazole thiophanate fungicides also exhibit significant resistance to some other benzimidazole thiophanate fungicides. Therefore, they tend to exhibit cross-resistance. Therefore, if there is some decrease in their protective effect against plant disease in certain arable land, then their application in these areas should be discontinued. However, it is often observed that infection by resistant organisms does not decrease even after a long time after discontinuation of the fungicide. Although another type of fungicide would have to be used in this case, only a small number of them are as effective as 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 ^1, 5'-dichlorophenyl) -1-izopropilkarbamoilimidazolidin-2,4-dione), vinhlorozin (3- (3 'and 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 previously described with respect to benzimidazole thiophanate fungicides.

In C. R. Acad. Sc. Paris, vol. 289, series E, pages 691693 (1979), described that herbicides such as barban (4-chloro-2-butynyl N- (3-chlorophenyl) carbamate), chlorofufam (1-methyl-2-propynyl M - (3-chlorophenyl) carbamate), chloroprofam (isopropyl N- (3-chlorophenyl) carbamate) and propham (isopropyl N-phenylcarbamate) exhibit fungicidal activity against certain resistant organisms

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

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

E '(I)

in which E 1 · and E 4 are the same or different and denote a lower alkyl group, a lower alkenyl group, a lower alkynyl group or a lower alkyl group substituted by at least one halogen, lower alkoxy or lower cycloalkyl radical;

E1 represents C1-6 alkyl, C1-6 alkenyl, C1-6 alkynyl, lower cycloalkyl group, lower haloalkyl group, lower haloalkynyl group, lower aralkyl group, lower alkyl group substituted by at least one halogen, cyano, lower alkoxy, haloxy, haloxy , phenoxy, lower aralkyloxy or lower cycloalkyl radical or a group of the formula:

- CH

in which m is 0, I or 2; η stands for I, 2 or 3;

X and Y are the same or different and represent an oxygen or sulfur atom and Ζ means 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 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 a phenoxy radical (the phenoxy radical may be optionally substituted by at least one halogen and / or at least one alkyl), a phenyl group, a furyl group, a thienyl group, a phenyl group substituted by at least one halogen, cyano, nitro, trifluoromethyl, lower alkyl, or a lower alkoxy radical or an aralkyl group (acrylic m may be optionally substituted with at least one halogen and / or at least one alkyl), provided that when E ¹ means methyl, E ² is not methyl or butyl, exhibit excellent fungicidal activity against pathogenic fungi that have acquired resistance. ect with respect to benzimidazole thiophanate fungicides and / or cyclic imide fungicides. It is remarkable 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 that are sensitive thiophanate fungicides and / or cyclic imide fungicides (hereinafter referred to as susceptible fungi or susceptible strains).

The term lower in terms of organic radicals or compounds means that each of these radicals or compounds does not have more than 6 carbon atoms.

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

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

The present invention provides a fungicidal composition which contains, as an active substance, a fungicidally effective amount of N-phenylcarbamate, a Rinert carrier or diluent. The invention also provides a combination composition containing as active substances H-phenylcarbamate (I) together with benzimidazole thiophanate fungicide and / or cyclic imide fungicide, which is effective not only for sensitive mushrooms but also for resistant mushrooms and due to this is especially effective in protecting plants from disease. The invention also provides a method for controlling phytopathogenic fungi of crops which may be resistant or sensitive strains by applying a fungicidally effective amount of the N-phenylcarbamate (I) to the pathogenic _for plants fungi. In addition, the invention relates to novel N-phenylcarbamates represented by the formula ρ x la (I) in which E, E, E, X, Y and Z have the meanings indicated

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

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

Method (s):

N-Phenylcarbamate '(I) is obtained by reacting (II) the values mentioned above,

3,4-dialkoxyaniline of the formula:

NHZ

E ² and Z have in which E 2 is chloroformate of formula

X! 1

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

(III)

The reaction is usually carried out in the presence of an inert solvent (for example benzene, toluene, xylene, diethyl ether, trachydrofuran, dioxane, chloroform, tetrachloromethane, ethyl acetate, pyridine, dimethylformamide). If desired, the reaction may be carried out in the presence of a hydrogen halide-binding agent (for example pyridine, triethylamine, diethylaniline, sodium hydroxide, potassium hydroxide, sodium hydride) to give the high yield compound (I). The reaction may be carried out at a temperature of oAC50 ° C, instantaneously or for 12 hours.

Method (b):

N-Phenylcarbamate (1), wherein Z is hydrogen, is obtained by reacting 3,4-dialkoxyphenyl isocyanate or isothiocyanate of the formula:

NC = X (IV)

- 7 (V)

T 7 wherein E, E and X are as defined above with an alcohol or a thiol of the formula:

in which E1 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, tetrachloromethane). If desired, a catalyst (e.g. triethylamine, diethylaniline, 1,4-diazabicyclo (2,2, 2) octane) may be used. The reaction is usually carried out at a temperature of 0 ° C to 50 ° C, instantaneously [or for 12 hours.

Method (s):

N-Phenylcarbamates (1), in which X does not represent hydrogen, are prepared by reacting b1- (3,4-dialkoxyphenyl) carbamate of the formula:

X

II

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

(VII) in which X has the meanings given above with the exception of hydrogen and A represents halogen (eg chlorine, bromine).

Typically, the reaction is carried out in an inert solvent medium (e.g. benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, chloroform, tetrachloromethane, ethyl acetate, pyridine, dimethylformamide). If desired, the reaction can be carried out in the presence of a halogen-binding agent (e.g. pyridine, triethylamine, diethylaniline, sodium hydroxide, potassium hydroxide) and a catalyst (e.g. tetrabutylammonium bromide) to give the desired compound. (I) in high yield. The reaction can be carried out at a temperature of 150 DEG C., instantaneously or for up to 12 hours.

As specific examples of the symbols used above in the I 2 formula, 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-x-orethyl, 2,2,2-trifluoromethyl, 2-methoxyethyl or cyclopropylmethyl, R? denote 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, I-methyl-3-butenyl, 1-pentyl-2-propenyl, propargyl,

1- methyl-2-propynyl, 2-butynyl, 3-butynyl, 1-ethyl-2-propynyl, immethyl-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-bromethyl, 1-methyl-2,2,2-trichloroethyl, 1-ethyl-2-bromoethyl, 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, I-cyclopentylethyl, 3-furylmethyl, phenylethyl or 3-phenylethyl or 3-phenylethyl -tetrahydrofuranyl, X and Y can each be oxygen or sulfur and Z represents hydrogen, methyl, ethyl, nbutyl, allyl, acetyl, propionyl, n-pentanoyl, sec-pentanoyl, 'cyclopropanecarbonyl, benzoyl, 2-chlorobenzoyl, 2,4-dichlorobenzoyl, 4-methylbenzoyl, methane sulfonyl or ethoxycarbonylmethyl.

THA-Phenylcarbamates (I) are effective fungicides against

- 9 wide range of fungal pathogens for plants, examples of which are: Podosphaera leucotricha, Ventura inaegualis, Mycosjihae-r rella pomi, Marssonina mail u Sclerotinia mail at the apple, Phyllactinia kakicola u Gloeosporium kaki at the plum, Copsosporium carp. in peach, Cercospora viticola, Uncinula necator, Elsinoe ampelina u Glomerejla cingulata in grapes, Cercospora beticola in sugarbeet, Cercospora arachidicola u Cercospora personate in peanuts ^they »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 berries, Botrytis all! for onions, cercospora apii for cereals, Phaeoisariopsis griseola for beans, Erisiphe cichoracearum for tobacco, Diplocarpon rosae for pose, Elsinoe fawcetti, Penicillium italicum, Penicillium digitatum for oranges, Botrytis cinereata, chiliata, patella, grapes, hops, oranges, cyclamen, onions sclerotinia sclerotiorum in cucumbers, eggplants, beans, peppers, lettuce, kettle, soy, potatoes H ^{CJII> H40r §c} ? otinia cinerea in peaches and cherries, Mycosphaerella melis others. N-Phenylcarbamates (I) are highly effective in controlling resistant strains of fungi.

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

Advantageously, the N-phenylcarbamates (I) are of low toxicity and have little detrimental effect on mammals, fish and the like. They can also be applied to crops without causing toxic effects on crops.

In view of their excellent fungicidal properties, compounds of formula (I) in which E ² 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, 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, I-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 ,pentyl-2-propynyl, cyclobutyl, cyclopentyl, 2-fluoroethyl, 2-chloroethyl, 2,2-dichloroethyl, 1- methyl-2-bromoethyl, 1-fluoromethyl-2-fluoroethyl, 1-bromomethyl-2-bromoethyl, 1-methyl-2,2,2-trichloroethyl, ethyl-2-bromoethyl, 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, I-phenylethyl or 3-tetrahydrofuranyl, X and Y are independently acidic genus 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 provided that when E is methyl, E is not methyl or butyl.

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

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

I 2 provided that if E is methyl, E is not a methyl group. More preferred are compounds of formula (1) wherein E1

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

The most preferred compounds are: 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 1- (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) carb-

mat and others.

Some typical examples of methods for the preparation of H-phenylcarbamates (I) are illustrated below: EXAMPLE I.

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

3,4-Diethoxyaniline (1.8 g) and diethylamininiline (1.5 g) were dissolved in benzene (20 ml). Isopropyl chloroformate (1.2 g) was added dropwise to the resulting solution for 5 minutes under ice-cooling. It was then left at room temperature for 3 hours and the reaction mixture was poured. on 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 are obtained. Recrystallization from ethanol gave isopropyl N- (3,4-diethoxyphenyl) carbamate (compound No. 13) (2.3 g) in 86% yield, m.p. 100 - 100.5 ° C Elemental / analysis: Calculated for ^C I4 ^H 2lW 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.Ϊg) under ice-cooling. After being left 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 concentrate in vacuo. The residue was purified by chromatography on silica gel using toluene as the eluant to give isopropyl N- (3,4-diethoxyphenyl) thiocarbamate (compound 88) (2.7 g) yield, m.p. PO - III ⁰ C.

Elemental analysis for ^{C 14 H 2 I NO} 3 ^$: Calculated: C - 59.33%;

Found: C - 59.02%

H - 7.47% \

H, 7.51%;

N, 4.94%;

N - 4.89% from 95%

5- 11.32%

11.70%.

EXAMPLE 3

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

Isopropyl N1- (3,4-diethoxyphenyl) carbamate (2.7 g) was dissolved in dimethylformamide (50 ml) and sodium hydride dispersion (50%, 0.5 g) was added thereto. 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 yes 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 the eluent to give benzoyl-41- (3,4-diethoxyphenyl) carbamate

d) in yield

Elemental (compound 99) (3.1,

Calculated:

%, etc. 120-112 ° C. Analysis for C18H18N3O4;

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) _? shown in Table I:

C - 68.11 are obtainable

- 14 TABLE I

coupling-physical τ ο ζ tion E Yag Ir X Y 2 constant no

¹ -Sn ₃ ^ 2% -C ₃ H ₇ (iso) 0 0 N. mp 10-4 ° C 2 -Sn ₃ -¾% C ^ CH 1 0 0 n mp 133-134 ° C -snn ₃ 3 -Sn ₃ -C ₂ H ₅ ch, f Z -sn ₂ ch ₃ 0 0 n mp 54-55 ° C 4 -CH ₃ -C ₃ H ₇ (n) —C ₃ H ₇ (iso) 0 0 n mp 94-95 ° C 5 -Sn ₃ -sw ₂ ss = ss ₂ —C ₃ H ₇ (iso) 0 0 n mp 79-80 ° C 6 -Sn ₃ -sw ₂ ss = ss ₂ c ^ chn 1 -chn ₃ 0 0 n mp Jub-107 ° C 7 -Sn ₃ -CH ₂ C = CH —C ₃ H ₇ (iso) 0 0 n ^A L ¹⁹ 1.5269 s. 8 ^C 2 ^H 5 -Sn ₃ —C ₃ H ₇ (iso) 0 0 n mp SW-SW 4 ° C 9 - ^C 2 ^H 5 -Sn ₃ c = dream 1 - dream ₂ dream ₃ 0 0 n mp II0.5- W.5 ° C 10 ” ^C 2 ^H 5 -CH ₃ -CH ₂ C = CHCH ₂ Cl 0 0 n mp 96-97 ° C II “ ^With 2 ^H 5 -C ₂ and ₅ -CH ₃ 0 0 n mp 120-121 ° C 12 -with ₂ and ₅ -C ₂ ^H 5 -with ₂ n ₅ 0 0 n mp 90-91 ° C 13 -C ₂ ^H 5 ” ^C 2 ^H 5 —C ₃ Ng, (iso) 0 0 n mp I00-I0Q.5 ° C 14 ^C 2 ^H 5 -C ₂ n ₅ - -C ₄ H ₉ (sec) 0 0 n mp 97-98 ° C 15 ” ^C 2 ^H 5 CH ι 0 0 n mp 67-68 ° C

ι

-CH (CH ₂ ) ₂ CH ₃

“ ^With 2 ^H 5 -with ₂ n ₅ CH ₂ CH ₃ 1 -snsn ₂ CH ₃ ~ ^C 2 ^H 5 -C ₂ ^H 5 CH ₂ CH ₃ -CH (CH ₂ ) ₂ CH ₃ “ ^With 2 ^H 5 -0 ₂ ^H 5 CH, SN,! > I 3 ssn ₂ ssn ₃ -with ₂ n ₅ CH 1 CH ₂ (CH ₂ ) ₅ CH ₃ “ ^With 2 ^H 5 “ ^With 2 ^H 5 -CH ₂ CH = CH ₂ · -with ₂ n ₅ -with ₂ n ₅ CH, 1> -CHCH = CH ₂ -with ₂ n ₅ -with ₂ n ₅ -CH ₂ CH ₂ CH = CH ₂ -C ₂ ^H 5 -C ₂ ^H 5 dream, 1 b - dream ₂ dream = dream ₂ ” ^C 2 ^H 5 -C2H5 CH ₂ CH ₃ = CH ₂ -snsn ^C 2 ^H 5 “Θ2% dream,! ⁵ -chch ₂ ch = gh ₂ ” ^C 2 ^H 5 CH = CHn 1 £ -CH (CH ₂ ) ₄ CH ₃ “ ^With 2 ^H 5 ~ ^C 2 ^H 5 -sw ₂ s ^ ss ² 2% ”Θ2 ^Η 5 dream, 1> -snow “ ^With 2 ^H 5 “ ^With 2 ^H 5 -CH ₂ CH ₂ CH with N ” ^C 2 ^H 5 -with ₂ n ₅ dream ₂ dream _{3 -} snowy -with ₂ n ₅ dream, -ssn ₂ s = dream ^C 2 ^H 5 ^With 2% C = CH 1 -CH (CH ₂ ) ₃ CH ₃

0 N mp 93-94 ° C

UN so. 87-88 ° C

0 N mp 56-57 ° C

UN so. 46.5-48 ° C

0 N mp 86-87 ° C

0 N mp 98-99.5 ° C

UN so. 92.5-93.5 ° C

UN mp 92-93 ° C

0 N mp 98.5-99.5 ° C

0 N mp 75-76 ° C

UN so. 46.5-48 ° C

UN so. W-112 ° C

UN so. P6-P7 ° C

UN so. 89-90 ° C

0 N mp P8-P9 ° C

0 N mp 99-100 ° C

Ο 0 N mp 120-121 ° C

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

rsn ο ο

-CH (CH ₂ ) ₄ CH ₃ ο ο

mp 96-97 ° C

mp 114-115.5%

35 -C ₂ H ₅ “ ^With 2 ^H 5 -CH ₂ CH ₂ R 0 0 36 -c ₂ n ₅ -C ₂ ^H 5 -CH ₂ CH ₂ Cl 0 0 37 -C ₂ H ₅ ^C 2 ^H 5 -CH ₂ CHCl ₂ 0 0 38 -C ₂ H ₅ -with ₂ n ₅ CH 1 -> -CHCH ₂ Br 0 0 39 -C ₂ H ₅ -with ₂ n ₅ CH ₉ P 1 £ -CHCH ₂ P 0 0 40 -C ₂ H5 CH ₉ Br 1 ^ά- CHCH ₂ Br 0 0 41 -C ₂ H ₅ “ ^With 2 ^H 5 dream,! · -CNSS1 ₃ 0 0 42 -C ₂ H ₅ -C ₂ ^H 5 -CH ₂ CH = CHCH ₂ Cl 0 0 43 -C ₂ H ₅ ^C 2 ^H 5 -CH ₂ C ^ CHCH ₂ Cl 0 0 44 -C ₉ Ns -SoHs -CH _o CH _o 0CH _o CH = CHO

45 -C ₂ H ₅ θ2 ^Η 5 -CH ₂ CH ₂ 0CH ₂ CHgI 0 0 46 -C ₂ H ₅ -with ₂ n ₅ CH, O 0 ^1-5 -CHCH ₂ OCH 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 -with ₂ n ₅ CH ₂ Cl 0 0 -Sn ₂ Chn ₃ 49 -C ₂ H ₅ -with ₂ n ₅ -CH ₂ CH ₂ Cl 1 0 0

mp I0I-I02 ° C

mp 89.5-90.5%

mp 73-74 ° C

mp 69-70 ° C

mp 89-90 ° C

mp 75-76 ° C

PD ¹⁹ · ⁵ 1.5316

mp 82-83%

mp Mp -1-113 ° 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 dream ₃ -y-O 0 0 N. mp 107-108 ° C -C ₂ H ₅ -C ₃ H _? (n) -with 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 -CN 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 -> -sn ₂ Apr ₃ 0 0 n mp 87-88 ° -C ₂ H ₅ -CH ₂ C = CH —C ₃ H ₇ (iso) 0 0 n mp SO2-SW ° C -C ₃ H ₇ (n) -CH ₃ -C ₃ H ₇ (iso) 0 0 n ϊ.τ. 10-120 ° C -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 -with ₂ n ₅ 0 0 n mp 76.5-77.5 ° —With ₃ n ₇ (n) —with ₂ n ₅ —C ₃ H ₇ (iso) 0 0 n mp 81-82 ° C -C ₃ H ₇ (n) - C ₂ H ₃ CH 1 -CHCH ₂ CH ₂ Θ 0 n mp 83-84 ° C ~ C ₃ H ₇ (n) · ”θ2% CH _? CH, · · f J J -CHCH ₂ CH ₃ 0 0 n mp 90-91 ° C -C ₃ H ₇ (n) * θ2 ^ 5 dream, -CH <J 0 0 n mp 82-83 ° C -c ₃ n ₇ (n) -c ₂ n ₃ -CH ₂ CH ₂ R 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 Fri ¹⁹ I.5I2I ~ ^by 2% —C ₃ H ₇ (iso) CH, 1 ·> 0 0 n mp 100.5 - —C ₂ H ₃ -CHC = CH 102 ° C, —C ₃ H ₇ (iso) CH 1 CH ₂ CH ₂ O CH ₃ 0 0 n Fri 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 mp 79.5-81 ° C -C ₃ H? (N) • “Ο- ^ Ηφζ iz) 0 0 n mp 82-83 ° C 71 -CH ₂ CH = CH ₂ -C ^ NrSn) -sn ₂ ss = ssn ₃ 0 0 n mp 66-67 ° C 72 -CH ₂ CH = CH ₂ -C ₃ H ₇ (n) -sw ₂ s-ss ₃ 0 0 n mp 92-93 ° C 73 -CH ₂ CH = CH ₂ с = сн I 0 0 n mp 84-85.5 ° C -C ^ H ^ (n) -snn ₃ 74 -CH ₂ CH = CH ₂ -sw ₂ ss = ss ₂ -C ₃ Ng> (iso) 0 0 n mp 83.5-84.5 ° 75 -CH ₂ C = CH ₂ “ ^With 2 ^H 5 -C ₃ H 2 (iso) 0 0 n mp 101-102 ° C 76 -CH ₂ C = CH ₂ -0Η ₂ 0Ξ0Η —C ₃ Ng? (Iso) 0 0 n mp SW-SW 4 ° C 77 -CH ₂ -S№ ₂ -C ₃ H 2 (iso) 0 0 n n ^{22 N} E I.467I 78 ~ θ2 ^ 5 θ2% 0 0 n mp 73-74 ° C

79 -C ₂ H ₅ -C ₂ H ₅ -sn ₂ - <[ UN so. 95-96 ° C 80 -C ₂ H ₅ -C ₂ H ₅ CHj 0 0 N mp. 105-106 ° C -0H-Q

81 -C ₂ H ₃ "^ 2% CH ₂ CH ₃ Br ₂ -SNSN 0 0 n mp 68- 9 ° C 82 -CH ₂ CH ₂ Cl ^C 2 ^H 5 -C ₃ Well (iso) 0 0 n mp P1-P2 ° C 83 ^ 2 ^H 5 “ ^C 2 ^H 5 -C ₃ Ng? (N) 0 0 n mp 79-80 ° C

UN

mp 17-P8 ° C

85 -C ₂ H ₅ -C ^ Ng 0 0 Η ТоТ »III.5 - P2.5 ° C -SND 1 ^2X 0 ^ 86 -C ₂ B ₅ -with ₂ n ₅ dream, _tk 0 0 N mp 109-P0 ° C 87 -C ₂ H ₅ “Θ2 ^Η 5 -with ₂ n ₅ 0 S H mp. 10 ° C-10 ° C 88 -C ₂ H ₅ “ ^With 2% -C ^ N / iso)  0 5 N mp. P0-W ° C 89 -C ₂ H ₅ -with 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 Fri ²⁸ ' ⁵ 1.5059 91 -C ₂ H ₅ -with ₂ n ₅ —C ^ Well (iso) 0 o -c ₂ n ₅ n _d ²⁸ ' ⁵ 1L9gg 92 -C ₂ H ₅ ” ^C 2 ^H 5 -C ^ N / iso) 0 0 -C ^ (c) PD ²⁸ · ⁵ 1.4885 93 -C ₂ H ₅ - -C ₂ and ₅ -C / y (iso) 0 0 -CH ₂ CH = CH _{2 n} 26.5 _1e 5044 D o -sos ₃ ζ.τ. 98-99 ° C 94 -C ₂ H ₅ -with ₂ n ₅ ? “C ^ Well (iso) 0 95 -C ₂ H ₅ -with ₂ n ₅ -C ^ N / iso) 0 o -sos ₂ n ₅ n ²⁷ · ⁵ 1.5006 96 -C ₂ H ₅ -with ₂ n ₅ —C ^ Ng? (Iso) 0 0-C0 ₄ H ₉ (n) m.p. 63-65 ° C 97 -C ₂ H ₅ -with ₂ n ₅ —C ^ Well (iso) 0 0-COC / 1 / sec) PD ²⁸ 1.4889 98 -C ₂ H ₅ -with ₂ n ₅ —C ^ Well (iso) 0 0 mp 55-57 ° C -with <3 99 -C ₂ H ₅ "^ 2 ^H 5 CfH2; (and 30) 0 0 mp 120-121 °

-co

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

—C ₃ Ng? (Iso)

0 CI

-so ^>

π ²⁸ I.5371

D ~ ^C 3 ^H 7 ⁽ iso)

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

102 -C ₂ H ₅ “ ^With 2 ^H 5 —Ο ^ Ηψ (iso) 0 0 -C ( mp 102- N§> _-CH3 ¹⁰³ ° ^with 103 —— C ₂ H ₅ -with ₂ n ₅ -CH ₃ -sn _{2 2} -sn ₃ 0 0 - CO ₂ H ₅ π ²⁷ 1.4972 104 -C ₂ H ₅ -C ₂ AND ₅ —C ₃ H 2 (iso) 0 0 -S0CH ₃ mp 114- P5 ° C 105 -C ₂ H ₅ “ ^With 2 ^H 5 —C2H2N3 (iso) 0 0 CH ₂ COOC ₂ H ₅ n | ⁷ * ⁵ 1.4948 yub -c ₂ n ₅ “ ^With 2 ^H 5 -C ₂ H5 S 0 n mp 74-75 ° C 107 -C ₂ H ₅ -with ₂ n ₅ 5 0 n mp 87-88 ° C 108. -C ₂ H ₅ -with ₂ n ₅ -C ₄ H ₉ (sec) 0 $ n mp 97-98 ° C 109 -C ₂ H ₅ -C ₂ ^H 5 -C (Ng / iso) S $ n mp 64-65 ° C

When using N-phenylcarbamates (I) as fungicides, they can be administered as compounds or in a preparative formulation such as powders, wet powders, oily sprays, emulsifiable concentrates, tablets, granules, microgranules, aerosols or as a suspension. These formulations are prepared in the usual manner by mixing at least one Γί-φΟ-nylcarbamate (I) with a suitable solid or liquid carrier or carriers or one or more diluents and, if necessary, adding one or more excipients (e.g., surfactant).

- 21 active 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 (eg flour, shredded tobacco stalks, soybean flour, ground nut shells, powdered vegetables, sawdust, bran, cork flour, pulp powder, vegetable residues), fibrous materials (eg paperboard) , drape), synthetic plastics powders, clay (eg kaolin, bentonite), talc, other inorganic products (eg pyrophyllite, sulfur powder, pumice stone, activated carbon) and chemical fertilizers (eg ammonium sulfate, ammonium phosphate, ammonium nitrate,ammonium chloride).

Examples of bile carriers or diluents are water, alcohols (e.g. methanol, ethanol), ketones (e.g. acetone, methylethylketone), ethers (e.g. diethyl ether, dioxane, cellosol, tetrahydrofuran), aromatic hydrocarbons (e.g. benzene, toluene, xylene) xylene , aliphatic hydrocarbons (eg gasoline, kerosene, gas), esters, nitriles, acid amides (eg dimethylformamide, dimethylacetamide), halogenated hydrocarbons (eg dichloroethane, tetrachloromethane), etc.

Examples of surfactants are alkylsulfonic acid esters, alkyl sulfonates, aralkyl sulfonates, polyethylene glycol ethers, esters, etc. Examples of adhesives and dispersants may be ceresin, gelatin, starch powder, carboxylacetyl algylacetyl algylacetylglycerol, bentonite, molasses, polyvinyl alcohol, boron turpentine, agar. As stabilizers can be used PAP (mixture of isopropyl acid phosphates), TCP (tricresyl phosphate),

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

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

When only resistant strains of phytopathogenic fungi are present, the N-phenylcarbamates (I) can be used alone. However, when resistant together with susceptible strains, it is then advantageous to use alternatively with benzimidazole thiophanate fungicides and / or cyclic imidium fungicides or to use in combination with benzimidazole thiophanate fungicides and / or cyclic imide fungicides. For alternative or combined use, any of the active substances may be administered as a compound or in a conventional formulation. In the case of combination administration, the weight ratios of H-phenylcarbamate (I) * and benzimidazole thiophanate fungicide and / or cyclic imide fungicide may be from about I: 0.1 to I: 10.0.

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

TABLE 2

Compound Structural formula

Name

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

^ x / NHC5NHC00C ₂ H ₅

Ϊ ·

NHC5 ESAP ₂ H ₅

2- (4-Thiazolyl) benzimidazole methyl benzimidazol-2-ylcarbamate

2- (2-furyl) benzimidazole

NHCNHC00CH ₃

NHP

II

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

1,2-bis (3-ethoxy-carbonyl-2-thiourea) benzene

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

I

: oos ₂ n ₅

2- (0,0-dimethylthiophosphorylamino) -1- (3'-methoxycarbonyl2 '-thiourea) 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-vinyloxazolidin-2,4 · dione ethyl (E) -3- (3 *, 5 * dichlorophenyl) -5-methyl-

2,4-dioxooxacolidine-5-carboxylate

In addition, the N-phenylcarbamates (I) can be used in admixture 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 acres. However, this amount may vary depending on the formulation, the time of administration, the route of administration, the location of the application, the disease, the type of culture and various other factors, which makes these quantities indicative.

Some formulations of the fungicidal compositions of the invention are provided for illustration in the examples below. In these parts and percentages are by weight.

PREPARATION EXAMPLE I.

Two parts of compound 21, 88 parts clay and 10 parts talc were mixed and homogenized to give a powder containing 2% of the active substance.

PREPARATION EXAMPLE 2.

Thirty parts of compound No. II, 45 parts diam. 20 parts of white carbon black, 3 parts of sodium lauryl sulfonate as a wetting agent and 2 parts of calcium ligninsulfonate as a dispersing agent are mixed during milling to give a wet powder containing 30% of the active ingredient.

PREPARATION EXAMPLE 3.

Fifty parts of compound No. 13, 45 parts of infusional soil,

2.5 parts calcium alkylbenzenesulfonate as a wetting agent, and

2.5 parts of calcium ligninsulphonate as a dispersant are mixed on milling to give a wet powder containing 50% of the active substance.

PREPARATION EXAMPLE 4.

Ten parts of compound No. 46, 80 parts of cyclohexanone and 10 parts of polyoxyethylene alkylaryl ether as emulsifier were combined to give an emulsifiable concentrate containing 10% of the active substance.

PREPARATION EXAMPLE 5.

One part of compound No. 7, part I of compound No. I, 88 parts of clay and 10 parts of talc were mixed and nebulized to give a powder formulation containing 2% of the active ingredient.

PREPARATION EXAMPLE 6.

Twenty parts of compound 86, 10 parts of compound J, 45 parts of infusional soil, 20 parts of white carbon black, 3 parts of sodium ligninsulfonate as a wetting agent and 2 parts of calcium ligninsulfonate as a dispersant., Mixed and nebulized to form a wet powder containing 30% of the active ingredient. *

PREPARATION EXAMPLE 7.

Ten parts of compound 88, 40 parts of compound B, 45 parts of infusional soil, 2.5 parts of calcium ligninsulfonate as a wetting agent, and 2.5 parts of calcium ligninsulfonate as a dispersant are mixed and milled to give a wet powder containing 50% active substance.

PREPARATION EXAMPLE 8.

Twenty-five parts of compound 94, 50 parts of compound I, 18 parts infusional soil, 3.5 parts calcium alkylbenzenesulfonate as a wetting agent and 3.5 parts calcium ligninsulfonate as a dispersant _; are mixed on grinding to make

- 27 received a wet powder containing 75% of the active ingredient.

PREPARATION 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 ligninsulfonate as a dispersant are mixed and milled to form a wet powder, containing 50% of the active ingredient.

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

the reference * names are as follows: Compound Note Swap 0 Commercial herbicide available ^and cr- n NHCOCH ^ Chlorpropham p- CI ' N ^ / CH ^ NHCOCH Commercial herbicide available Barban 0 π nhcoch ₂ c ^ cch ₂ ci Commercial available Oh- herbicide

CI

- 28 CERTS

CI

Thiophanate methyl S

ό

Carbendazim _n

A commercially available herbicide

A commercially available herbicide

A commercially available herbicide

A commercially available fungicide

A commercially available fungicide

A commercially available fungicide

Thiabendazole

Η

Commercially available fungicide ι

EXPERIENCE I.

Protective activity against powdery mildew in cucumbers (Sphaerotheca fuliginea)

Seeds of cucumber (Sagami-hanjiro variant) are planted in a 90 ml flower pot filled with sandy soil. Growing is carried out in a growing house for 8 days. The resulting two-leaf plants were sprayed with the test compound formulated as an emulsion concentrate or wet 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 spray and re-cultured in the growing house. After ten days, report the degree of damage as follows, with the results shown in Table 3.

The test leaves were measured by percentage of contaminated area and classified according to the following disease indices: 0, 0.5, I, 2,4:

Disease index

Percentage of contaminated area

No contagion

0.5

Contaminated area less than 5%

Contaminated area less than 20%

Contaminated area less than 50%

Contaminated area of not less than 50%

Disease severity (%) =

Protective

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

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

TABLE 3

Concentration of

Coupling - Active Dreaming # dingy (ppm)

Protective value for foreign cooling with resistant strain (%)

Inoculation with sensitive 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 and 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

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 swap 200 0 0 chlorpropham 200 Q 0 barban 200 25 0 SERS 200 0 0 prof 200 0 0 Chlorbufam 200 0 0 benomyl 200 0 100 THIOPHANATE - methyl 200 0 100 carbendazim _and 200 0 100

---— ί. »

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

EXPERIENCE 2.

Protective effect against Cercospora beticola in sugar beet

- 35 In a 90 ml pot filled with sandy soil, sugar beet seeds are planted (Detroit dark red variety). The cultivation is carried out in a growing house

every 20 days. The resulting seeds are sprayed with the test compound formulated as wet powder or emulsify the conc- and diluted with water. in the norm of 10 ml: for the pot. After that, the beasts are inoculated with suspension < from disputes [sensitive] or resistant strains of Gercospora beticola through spray- bath. The pots are covered with a sheet of polyvinyl chloride to make maintain high humidity and cultivation continues in vegetation- that house another 10 days. The degree of damage is determines the same way, as in Experiment I, and the results are given Table 4: TABLE 4 Connect- Concentration of Protective Stand- Protective stand- we no actively ate night at inok- inoculation melting (ppm) casting with resist- sensing tent strain (%) a virulent 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

96 200 97 0 98 200 100 0 99 200 100 0 100 200 100 0 ΙΟΙ 200 100 0 102 200 100 0 swap 200 0 0 chlorpropham 200 0 0 barban 200 34 0 SERS 200 0 0 prof 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 ениphenylcarbamates of the present invention exhibit an excellent preserving effect on the resistant strain but have no protective effect on the susceptible strains tested. The opposite is the case with 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 N-phenylcarbamates (I) have no fungicidal activity in either susceptible or resistant strains.

EXPERIENCE 3.

Preventive effect on pear against Venturia nashicola 90 ml plastic pots are filled with sandy soil and planted with pear seeds (var chojuro).

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

TABLE 5.

Compound No Active compound concentration (ppm) Protective value for inoculation with resistant strain (%) Protective value for inoculation with a sensitive 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, TJ phenylcarbamates according to the invention exhibit an excellent protective effect against a resistant strain, but do not have a preventive effect against the susceptible strains tested. The opposite is the case with commercially available known fungicides such as benomyl and thiophanate-methyl, which have a good effect on susceptible strains but not on resistant strains.

EXPERIENCE 4.

Preventive effect in peanuts against Cercospora arachidicola.

Seeds of peanuts (var. Chiba haaryusel) are planted in a 90 ml plastic pot filled with sandy soil. The cultivation is carried out in a vegetation house for 14 days. Germinated seeds are treated with the test compound formulated as an emulsion concentrate or as a wet powder and diluted with water by spraying 10 ml per pot. The seeds are then inoculated by spraying with a spore suspension of a resistant and susceptible strain of Cercospora arachidicoia. Plants are covered with polyvinylchloride leaf to provide moisture conditions and cultivated in a growing house for 10 days. The extent of damage was determined in the same way as in Experiment I, and the results are shown in Table 6:

TABLE b.

Compound No Active substance concentration (ppm) Protective value for inoculation with resistant strain t Protective value for inoculation with a sensitive strain (%) 2 200 100 0 7 200 100 0

12 200 13 200 And? 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 showed excellent protective effect in resistant strain but did not show efficacy in the susceptible strain tested. The opposite is observed with commercially available known fungicides such as benomyl and thiophanate-methyl, which are active against the susceptible strain but not the resistant strain.

EXPERIENCE 5.

Protective effect against Botrytis cinerea in cucumbers Plastic pots with a volume of 90 ml are filled with sandy soil and seeded with cucumber seeds (var. Sagami hanjiro). Cultivation is carried out in a growing house for 8 days to obtain seedlings having cotyledons. The test compound formulated as an emulsifiable concentrate or as a wet powder and diluted with water is sprayed onto them at a rate of 10 ml for a pot. After being air-dried, the seeds were inoculated with mycelial discs (5 mm in diameter) from a resistant and sensitive strain of Botrytis cinerea, placing the discs on the leaf surface. The plants were infected by incubation for three days at high humidity at 20 ° C, after which the disease rate was recorded. The impairments were determined as described in Experiment 1, with the results given in Table 7.

TABLE 7.

Concentration of

Active substance compound (ppm)

Resistance inoculation with resistance strain Resistance inoculation with sensitive strain (%) 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

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

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 ο ο ο 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

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 it is sees from the results of Table 7 And-phenylcar- bamboos (I) according to the invention show excellent safety effect when resistant strain, but are not active in tests heard

a virulent strain. Conversely, commercially available known fungicides such as benomyl and thiophanate-methyl have an effect in the susceptible strain but not in the resistant strain.

EXPERIENCE 6.

Protective effect on cucumbers against Mycosphaerella melonis

- 49 Plastic pots of 90 ml capacity are filled with sandy soil and planted with cucumber seeds (var. Sagamihanjiro). They are cultured in a growing house for 8 days to produce cotyledons with seeds. The test compound, formulated as an emulsion concentrate or as a wet powder and diluted with water, is sprayed onto the plants at normal rate.

10 ml for a pot. After air-drying, the plant is inoculated with a micellar disk (5 mm in diameter) from resistant or a sensitive strain of Mycosphaerella melonis, AS the disc does placed on the surface on the leaf. The plant is held at high animosityTo be infections for 4 days at 25 ° S. Degree of disability by plants are defined in the manner of experience I, having the results are shown in Table 8. TABLE 8. Concentration of Safeguard value Protective stand- Compound the active multi- when inoculated with inoculation No substance (ppm) resistant strain sensing · t wire 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 exhibit excellent protective activity in resistant strains but have no such effect in the tested strain. Conversely, commercially available known fungicides such as benomyl and thiophanate-methyl, which have a very good effect on the susceptible strain but not the resistant strain.

EXPERIENCE 7,

Protective effect on oranges against Penicillium italicum.

Oranges (Unaka var.) 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 continues

I minute. After air drying, the fruits were inoculated with a spore suspension of a resistant and sensitive strain of the above penicillin, sprayed and then placed in a high humidity room for 14 days. The degree of damage defines as follows: The fruits studied are measure with respect to the damaged- their area and ί are classified with the following indices: I, 2,3,4 and 5. index of the disease Percentage of contaminated area 0 No contagion I The contaminated area is less than 20% 2 The contaminated area is less than 40% 3 The contaminated area is less than 60% 4 The contaminated area is less than 80% 5 The contaminated area is not less than 80% Calculation of the degree of damage and of the protective value up perform as is described in Experiment I. TABLE 9. Compound No Active substance concentration (ppm) Protective value for inoculation with resistance strain strain (%) Sensitive strain inoculation protection value {%) 2 200 100 0 5 200 100 0 9 200 100 0 II 200 100 0 13 200 100 Fr. 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 phenylcarbamates (I) according to the invention exhibit an excellent, protective effect on the resistant strain but do not have one against the tested sensitive strain. The opposite is the case with commercially available known fungicides such as benomyl, thiophanate-methyl and thiabendazole,

- 53 which are effective in the susceptible strain but not in the resistant strain.

EXPERIENCE 8.

Preventive effect on cucumbers against Sphaerotheca fuliginea.

90 ml plastic pots are filled with sandy soil and planted with cucumber seeds (Bap.Sagamihanjiro). The cultivation is carried out in a growing house for 8 days. Sprouted seed plants already having cotyledons are sprayed with the test compound formulated as an emulsifiable concentrate or wet powder and diluted with water, treating each pot with 10 ml each. The plants are then inoculated with a mixed spore suspension of a sensitive and resistant strain of the above pest by spraying and then cultivating in a growing house. After ten days, the degree of contamination of the plants is reported. The extent 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 the active substance (PPM) Protective capability (%) 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 the village

with e

e

Well

Well

R.

R.

6 &

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 + R. 20 + 20 100 28 + A 20 + 20 100 28 + IN 20 + 20 100 28 + P 20 + 20 100 43 + Yes 20 + 20 100 43 + & 20 + 20 100 43 + n 20 + 20 100 86 + A 20 + 20 100 86 + IN 20 + 20 100 86 + R. 20 + 20 100 88 + p 20 + 20 100 88 + Well 20 + 20 100 88 + & 20 + 20 100 94 + A 20 + 20 100 94 + Well 20 + 20 100 94 + Mr 20 + 20 100 98 + P 20 + 20 100 98 + N. 20 + 20 100 99 + A 20 + 20 100 99 + IN 20 + 20 100 100 + A 20 + 20 100 100 + Yes 20 + 20 100 100 + Well 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 showed a much higher safety effect than alone.

- 56 EXPERIENCE 9.

Protective effect on tomatoes against Batrytie cinerea.

A 90 ml plastic pot is filled with sandy soil and seeded with tomato seeds (var Fukuji No 2). The cultivation is carried out in a growing house for 4 weeks. The sprouted seeds are in phase 4 leaf. The test compound or test compounds formulated as an emulsion concentrate or as a wet powder and diluted with water are sprayed onto the plants at a rate of 10 ml for a pot. The plants are then inoculated with mixed spores of a sensitive and resistant upper mold mildew suspension by spraying and the plants are placed in a high humidity room for 5 days at 20 ° C. The degree of damage is determined in the same way as in Example I and the results are given in Table II.

Safeguard value (%)

TABLE II

Concentration of

Active substance compound (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 p 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 JM-phenylcarbamates (I) according to the invention with benzimidazole thiophanate fungicides and / or cyclic imide fungicides gives much better results than their individual application.

Claims (42)

Claims I. A fungicidal composition comprising as an active substance a fungicidally effective amount of N-phenylcarbamate of the formula: A I 2 in which E and E are the same or different and denote lower alkyl, lower alkenyl, lower alkynyl or lower alkyl substituted with at least one halogen, lower alkoxy or lower cycloalkyl; E ^ represents C1-6 alkyl, C1-6 alkenyl, C1-6 alkynyl, lower cycloalkyl group, lower haloalkyl group, lower haloalkynyl group, aralkyl, alkynyl substituted with at least one halogen, cyano, lower alkoxy, lower alkenyloxy, lower alkoxyloxy or lower cycloalkyl or a group of the formula: ^ (C ⁿ ₂ ) y -CH която in which m is 0, I or 2; n represents I, 2 or 3 X and Y are the same or different and represent oxygen or a combined atom and R represents hydrogen, lower alkyl, lower alkenyl, lower alkynyl, lower cycloalkyl, lower haloalkyl, lower alkyl substituted with at least one halogen, cyano group, lower alkoxy alkoxycarbonyl or a group of formula -COE ²¹ · or -SO 4 E ²¹ , (¢ 0 in which E ²¹ denotes 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 (phenyloxy mo may be optionally substituted by at least one halogen and / or at least one alkyl), phenyl, furyl, thienyl, phenyl group substituted by at least one halogen, cyano group, nitro, trifluoromethyl, lower alkyl or lower alkoxy group or aralkyl group ' (aralkyl may optionally be substituted by at least one halogen and-or at least one alkyl), provided that when E 1 is methyl, E ² is not methyl or butyl, together with an inert carrier or diluent. The fungicidal composition according to claim I, which comprises, as an additional active substance or active substances, benzimidazole thiophanate fungicide and / or cyclic imide fungicide, The fungicidal composition according to claim 2, wherein the benzimidazole fungicidal fungicide is methyl 1- (butylcarbamoyl) benzimidazol-2-ylcarbamate, 2- (2-furyl) benzimidazole, 2- (4-thiazolyl) benzimidazole, methyl-benzimidazol-2-benzimidazole, methyl-benzimidazol-2-benzimidazole. ylcarbamate, 1,2-bis (3-methoxycarbonyl-2-thiourea) benzene, 1,2-bis (3-ethoxycarbonyl-2-thiourea) benzene, 2- (0, $ - Dimethylphosphorylamino) -1- (3 * - methoxycarbonyl 2'-thiourea) benzene or 2- (0,0-dimethylthiophosphorylamino) -1 (3'-methoxycarbonyl-2'-thiourea) benzene, and the cyclic imide fungicides can be 3- (3} 5 * -dichlorophenyl) -1 , 2-dimethylcyclopropane-1,2-d carboxamide, 3- (3 *, 5 * dichlorophenyl) -1-izopropilkarbamoilimidazolidin-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 of the formula: wherein E 2 and E ² may be the same or different and denote lower alkyl, lower alkenyl, lower alkynyl or lower alkyl, lower alkoxy or lower cycloalkyl; substituted by at least one halogen, Eb represents C ^ alkyl, C ₃ _ ₃ alkenyl, C ₃ _ ₃ alkynyl, lower cycloalkyl lower halogenalkyl, lower haloalkynyl, lower aralkyl, lower alkyl group substituted with at least one halogen, cyano, lower alkoxy, lower alkenyloxy , a lower, phenoxy, lower aralkyloxy or lower cycloalkyl haloalkyl group of the formula wherein m is 0, I or 2; denotes I, 2 or 3; and Y are the same or different and denote oxygen or sulfur; Z represents hydrogen, lower alkyl, lower alkenyl, lower alkynyl, lower cycloalkyl, lower halogenoalkyl, lower alkyl substituted with at least one halogen, cyano, lower alkoxy or lower alkoxycarbonyl or a group of the formula: -COE4 or - O ₂ or C 0-6 in or - O ₂ or C 0-6 in or which means lower alkyl, lower alkenyl, lower alkynyl, lower cycloalkyl,. lower haloalkyl, an alkyl group substituted with at least one halogen, cyano group, lower alkoxy, lower cycloalkyl or phenoxy (the phenoxy group may optionally be substituted by at least one halogen and / or and at least one alkyl), phenyl, furyl, thienyl, phenyl group substituted by at least one halogen, cyano group, nitro, trifluoromethyl, lower alkyl or lower alkoxy or aralkyl group (in which aralkyl may be optionally substituted by at least one halogen and / or with at least one alkyl), provided that when E ¹ is methyl, E ² is not methyl or butyl. 5. N-phenylcarbamates according to claim 4, wherein E &lt; 1 &gt; and o E are independently methyl, ethyl, n-propyl, isopropyl, n-butyl, allyl, 2-butenyl, 3-butenyl, ¹ propargyl, 3-butynyl, 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-2-propenyl, 1-pentyl-2-propenyl, propargyl, 1-methyl-2-propynyl, 2-butynyl, 3-butynyl, 1-ethyl-2-propynyl, 1-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-bromoethyl-2-bromoethyl, 1-methyl- 2,2,2-trichloroethyl, 1-ethyl-2-bromoethyl, 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, I-phenylethyl or 3tetrahydrofuranyl; X and Y are independently oxygen or sulfur and Ζ denotes hydrogen, methyl, ethyl, n-butyl, allyl, acetyl, propionyl, n-pentanoyl, sec-pentanoyl, cyclopropanecarbonyl, benzoyl, 2-chlorobenzoyl, 2,4- dichlorobenzoyl, 4-methylbenzyl ¹ benzoyl, methanesulfonyl or ethoxycarbonylmethyl, with the proviso that when E is methyl, E is not methyl or butyl. Q2> 6. N-phenylcarbamate according to claim 5 wherein E ¹ and E ² independently of one another represent methyl, ethyl, n-propyl, allyl or propargyl, R @ represents ethyl, isopropyl, sec-butyl, Imetilbutil, 1-ethylbutyl, I-ethylpropyl, 1-methyl-2-propenyl, ethyl-2-propenyl, I-methyl-3-butenyl, propargyl, 1-methyl-2-propynyl, 1-ethyl-2-propynyl, 3-butynyl, I- methyl-3-butynyl, 1-butyl 2-propynyl, 2-fluoroethyl, 1-methyl-2-bromoethyl, 1-fluoromethyl-2-fluoroethyl, 1-bromomethyl-2-bromoethyl, 4-chloro-2-butynyl, 1- methyl-2-methoxyethyl, I-cyclopropylethyl or I-phenylethyl; X stands for oxygen, Y stands for oxygen or sulfur and Z stands for hydrogen, acetyl, propionyl, n-pentanoyl, sec-pentanoyl, cyclopropanecarbonyl, benzoyl, 2-chlorobenzoyl, 2,4-dichlorobenzoyl or 4-methylbenzoyl, provided that when E ¹ means methyl, E ² is not a methyl group. 7. N-phenylcarbamate according to claim 6, wherein E is ¹ and 2 3 E stands for ethyl, E stands for ethyl, isopropyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, 1-methyl-3-butenyl, 1-methyl-2-propynyl, 4-chloro-2-butynyl or 1-phenylethyl, X stands for oxygen, Y stands for oxygen or sulfur and Z stands for hydrogen, acetyl, cyclopropanecarbonyl, benzoyl or 2-chlorobenzoyl. 8. N-phenyl carbamate according to claim 4, which is isopropyl N- (3,4-diethoxyphenyl) carbamate. 9. N-Phenylcarbamate according to claim 4, which is 1-methyl-2-propynyl N- (3,4-diethoxyphenyl) carbamate. 10. N-phenylcarbamate according to claim 4, which is 4-chloro-2-butynyl N- (3,4-diethoxyphenyl) -carbamate. 11. N-phenylcarbamate according to claim 4, which is isopropyl N- (3,4-diethoxyphenyl) thi (isarbamate. 12. N-phenylcarbamate according to claim 4, which is 1-phenylethyl N- (3,4-diethoxyphenyl) carbamate. 13. N-phenylcarbamate according to claim 4, which is isopropyl N-acetyl-N- (3,4-diethoxyphenyl) carbamate. 14. N-phenylcarbamate according to claim 4, which is isopropyl N-cyclopropanecarbonyl-N- (3,4-diethoxyphenyl) carbamate. 15. N-phenylcarbamate according to claim 4, which is isopropyl N-benzoni-N- (3,4-diethoxyphenyl) carbamate. 16. N-phenylcarbamate according to 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 * indicated in claim I. The method of claim 17, wherein the plant-pathogenic fungus is a resistant strain. 19. A method of combating pathogenic fungi for plants * comprising administering a fungicidally effective amount of a mixture of N-phenylcarbamate of the formula: in which E ^ E ^X 0 ¢ 5 tion I and benzimidazole thiophanate fungicide and / or cyclic imide fungicide. 20. A process for the preparation of M-phenylcarbamate of the formula: in which 2 has the meaning given in claim 4, except for hydrogen, and E 1, E ² , E ⁵ , X and Y have the meanings given in claim 4 which consists of reacting 3,4-dialkoxyphenylcarbamate of formula : 8¾ in which 8 ^, B ² , c \ X ^ and Y have the meanings indicated above with a halide of the formula: in which A is halogen and Z has the meanings given above. 21. A fungicidal composition comprising, as an active ingredient, a fungicidally effective amount of N-phenylcarbamate of the formula: wherein E ¹ and E ² are the same or different and denote lower alkyl, lower alkenyl, lower alinyl or lower alkyl substituted with at least one halogen, lower alkoxy or lower cycloalkyl; Eb represents C ^ alkyl, C ₃ _ ₃ alkenyl, C ^ alkynyl, 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 denote oxygen or sulfur and X is hydrogen, lower alkyl, lower alkenyl, lower alkynyl, lower cycloalkyl, lower haloalkenyl, lower alkyl group substituted with at least one halogen, cyano, lower alkoxy or lower alkoxycarbonyl, or a group of the formula: -SOE ² * ^- or SC ^ E ² * in which E denotes 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 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 Ocyl or lower alkoxy or an aralkyl group (aralkyl may optionally be substituted by at least one halogen and / or at least one alkyl), provided that when E is methyl, E is not methyl or butyl, together with an inert carrier or diluent. The fungicidal composition of claim 21, further comprising one or more active substances such as benzimidazole thiophanate fungicides and / or cyclic imide fungicides. The fungicidal composition of claim 22, wherein the benzimidazole thiophanatefungicide is methyl 1- (butylcarbamoyl) benzimidazol-2-ylcarbamate, 2- (2-furyl) benzimidazole, methyl benzimidazol-2-ylcarbamate, and the cyclic imidazole (cyclic imidazole) l · be 3- (3 ^1, 5 '-dichlorophenyl) - !, 2-dimethylcyclopropane-1,2-dicarboximide, 3 / (3 *, 5 * dichlorophenyl) -1-izopropilkarbamoilimidazolidin-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-dioxoox zolidin-5-carbo xylate. 24o Τί-phenylcarbamate of the formula: wherein E 2 and E ² are the same or different and denote lower alkyl, lower alkenyl, lower alkynyl, lower alkyl group substituted with at least one halogen, lower alkoxy or lower cycloalkyl; E is C 1-6 alkyl, C 1-6 alkenyl, C 1-6 alkynyl, lower cycloalkyl, lower haloalkenyl, lower haloalkynyl, lower aralkyl, lower alkyl group substituted by at least one halogen, cyano, lower alkoxy, lower alkoxyloxyloxyloxyloxyloxyloxyloxyloxyloxy , lower aralkyloxy or lower cycloalkyl; X and Y are the same or different and denote 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 the formula: -SOE ^ or -30 ₂ \ in which E ² * means a lower alkyl group, phenyl, lower alkynyl, lower cycloalkyl, lower haloalkyl, lower alkyl group substituted with at least one halogen, cyano, lower alkoxy, lower cycloalkyl or phenoxy group (phenoxy group) may be 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 (the aralkyl being optionally substituted by at least one halogen and / or at least methyl or butyl. 25. N-phenylcarbamate according to claim 24, wherein E ^ and E ² 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, E ⁵ stands for methyl, ethyl ₅ 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-3-butenyl, 1-pentyl-2-propenyl, propargyl, 1-methyl-2-propynyl, 2-butynyl, 3-butynyl, 1-ethyl-2-propynyl, 1-methyl-3-butynyl, 1-butyl 2-propynyl, 1-pentyl-2-pro pinil, cyclobutyl, cyclopentyl, 2fluoroethyl, 2-chloroethyl, 2,2-dichloroethyl, 1-methyl-2-bromoethyl, Iffluoromethyl-2-fluoroethyl, 1-bromomethyl-2-bromoethyl, 1-methyl-2,2,2trichloroethyl, 1-ethyl-2-bromoethyl, 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, I-cyclonropylethyl, Icyclopentylethyl, 2-furylmethyl, I-phenylethyl or 3-tetrahydrofuranyl; X and Y are independently oxygen or sulfur and X is 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 E1 is methyl, E is not a methyl or butyl radical. 26. L1-Phenylcarbamate according to claim 25, wherein E1-9 and independently of one another methyl, ethyl, n-propyl, allyl or propargyl, initiates 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, ethyl-2-propynyl, 3-butynyl, I-methyl- 3-butynyl, 1-butynyl-2-propynyl, 2-fluoroethyl, 1-methyl-2-bromoethyl, 1-fluoromethyl-2-fluoroethyl, 1-bromomethyl-2-bromoethyl, 4-chloro-2-butynyl, 1- methyl-2-methoxyethyl, I-cyclopropylethyl or I-phenylethyl; X stands for oxygen, Y stands for oxygen or sulfur and Z stands for hydrogen, acetyl, propionyl, n-pentanoyl, sec-pentanoyl, cyclopropanecarbonyl, benzoyl, 2-chlorobenzoyl, 2,4-dichlorobenzoyl, or 4-methylbenzoyl, provided that when E ¹ means methyl, not methyl. 27. N-phenylcarbamate according to claim 26, wherein E ¹ and E, represent ethyl, R @ represents ethyl, isopropyl, sec-butyl, 1-methylbutyl, I-ethylbutyl, I-methyl-S-butenyl, 1-methyl- 2-propynyl, 4-chloro-2-butynyl or I-phenylethyl, X stands for oxygen, Y stands for oxygen or sulfur and Z stands for hydrogen, acetyl, cyclopropanecarbonyl, benzoyl or 2-chlorobenzoyl. 28. N-phenylcarbamate according to claim 24, which is isopropyl N- (3,4-diethoxyphenyl) carbamate. 29. N-phenylcarbamate according to claim 24, representing 1- methyl-2-propynyl N- (3,4-diethoxyphenyl) carbamate. 30. N-phenylcarbamate according to claim 24, representing 2-chloro-2-butynyl N- (3,4-diethoxyphenyl) carbamate. 31. N-phenylcarbamate according to claim 24, which is isopropyl N- (3,4-diethoxyphenyl) thiolcarbamate. 32. N-phenylcarbamate according to claim 24, which is 1-phenylethyl N- (3,4-diethoxyphenyl) carbamate. 33. N-phenylcarbamate according to claim 24, representing isopropyl-N-acetyl-1 H - (3,4-diethoxyphenyl) Car _b Amath. 34. N-phenylcarbamate according to claim 24, which is isopropyl N-cyclopropanecarbonyl-N- (3,4-diethoxyphenyl) carbamate. 35. N-phenylcarbamate according to claim 24, which is isopropyl N-benzoyl-N- (3,4-diethoxyphenyl) carbamate. 36. N-phenylcarbamate according to claim 24, which is isopropyl N- (2-chlorobenzoyl) -N- (3,4-diethoxyphenyl) carbamate. 37. A method of combating pathogenic fungi on plants, comprising administering a fungicidally effective amount of at least one N-phenylcarbamate of the formula: X I! SEP ³ in which E 1, E ² , E ³ , X, Y and Ζ have the meanings given in claim 21 to the pathogenic fungi of the plants. The method of claim 37, wherein the pathogenic fungus of the plant is a resistant strain. 39. A method of controlling pathogenic fungi of plants, comprising administering a fungicidally effective amount of a mixture of N-phenylcarbamate of the formula: E 'in which E ¹ , E ² , E ³ , X, Y and Ζ have the meanings given in claim 21, and benzimidazole thiophanate fungicide and / or cyclic imide fungicide. Ή 40. N-phenylcarbamate according to claim 24, which is ethyl-N- (3,4-diethoxyphenyl) carbamate. The fungicidal composition of claim 21, wherein the Mphenylcarbamate is ethyl N- (3,4-diethoxyphenyl) carbamate. The method of controlling pathogenic fungi of plants according to claim 37, wherein the phenylcarbamate ¹ is N- (3,4diethoxyphenyl) carbamate.