CS240976B2 - Fungicide agent - Google Patents

Description

The present invention relates to a fungicidal composition comprising, as an active ingredient, a mixture of novel N-phenylcarbamates and benzimidazole-thiophanate-type fungicides and / or cyclic imide fungicides.

Benzimidazole-thiophanate-type fungicides such as Benomyl {methyl-1- (butylcarbamoyl) benzimidazol-2-ylcarbamate 1, Fubelidazole [2- / 2-furyl / benzimidazole], Thiabendazole [2- (4-thiazolyl) benzimidazole], Carbendazim (methylbenzimidazol-2-ylcarbamate), Thiophanate-methyl [1,2-bis- (3-methoxycarbonyl-2-thioureido) benzene], Thiophanate [1,2-bis- (3-ethoxycarbonyl) nyl-2-thioureido] (benzene), 2- (O, S-dimethylphosphorylaraino) -1- (3'-methoxycarbonyl-2'-thioureido) benzene and 2- (0,0-dimethylthiophosphorylamino) -1- (3'-methoxycarbonyl) -2'-thioureido / benzene show excellent fungicidal activity against various phytopathogenic fungi and that they have been widely used as fungicides in agriculture since 1970.

However, as a result of the long-term use of these substances, resistenoe has formed in the phytopathogenic fungi, which considerably reduces the preventive effect of these substances against plant diseases. In addition, fungi that have formed resistenoids to certain types of benzimidazole-thiophanate-type fungicides also exhibit considerable resistance to other types of benzimidazole-thiophanate-type fungicides.

Thus, cross-resistenoids can easily develop in these fungi. Thus, if a substance is found to reduce its preventive activity against plant diseases in a particular area, its application in that area is discontinued.

However, it is often observed that the frequency of occurrence of organisms resistant to a substance does not decrease even after a long period of time after the administration of the substance has been stopped. Although in such i

In another case, fungicides of a different type are used, only a few of which have the same effectiveness in controlling various phytopathogenic fungi as the benzimidazole-thiophanate-type fungicides. Cyclic imide fungicides such as Procymidone [3- (3 ', 5'-dichlorophenyl) -1,2-dimethyloyclopropane-1,2-dicarboximide], Iprodione (3- (3', 5'-dichlorophenyl) -1- Isopropylcarhamoylimidazolidine-2,4-dione, Vinchlozoline [3- / 3 ', 5' - (dichlorophenyl) -5-methyl-5-vinyloxazolidine-2,4-dione, ethyl- (RS) -3- / 3 ', 5 di-chlorophenyl / -5-methyl-2,4-dioxooxazolidine-5-carboxylate, etc., which are effective against various plant diseases, in particular those caused by Botrytis cinerea, have the same disadvantages as explained above with respect to the benzimidazole fungicides. of the thiophanate type.

In C. R. Acad. Sat. Paris, t. 289, Series D, pp. 691-693 (1979), discloses such herbicides as Barban [4-chloro-2-butynyl-N- (3-chlorophenyl) carbamate], chlorobufam [1-methyl-2] -Propinyl N- (3-chlorophenyl) carbamate, Chlorpropham [isopropyl N- (3-chlorophenyl) carbamate, and Propham isopropyl N-phenylcarbamate, show fungicidal activity against certain organisms resistant to certain benzimidazole-thiophanate-type fungicides.

However, the fungicidal activity of these compounds against fungi is not sufficiently high and therefore they cannot be used as fungicides in practice.

It has now been found that the deficiencies of the prior art can be overcome by using a combination of the novel N-phenylcarbamates of the following general formula (I) of the benzimidazole-thiophanate-type fungicides or cyclic imide fungicides.

The present invention relates to a fungicidal composition comprising, as active ingredient (A), at least one N-phenylcarbamate of the general formula (I).

R ¹ 0

in which

2

R and R, which have the same or different meanings, are C 1 -C 4 alkyl, allyl, propargyl or C 1 -C 2 haloalkyl,

O

R is C 1 -C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 4 cycloalkyl, C 4 haloalkenyl, C 4 haloalkynyl, phenethyl, furylmethyl, C 2 -C 4 haloalkyl, cyanethyl, C 1 -C 4 alkoxyalkyl, C 2 -C 3 alkyl, allyloxyethyl, haloethoxyethyl, 3-methoxyhaloalkyl alkyl carbon atoms, benzyloxyethyl, cycloalkylalkyl of 3 to 5 carbon atoms in the cycloalkyl moiety and 1 to 2 carbon atoms in the alkyl moiety or tetrahydrofurahydro,

X and Y are the same or different from each other and are oxygen or sulfur, and

Z is hydrogen, (C 1 -C 4) alkyl, allyl, ethoxycarbonylmethyl, (C 2 -C 5) alkanoyl, oxy (propanecarbboryl), benzoyl, halobenzoyl, methylbenzoyl or methanesulfonyl;

and / B) at least one benzimidazole-thiophanate type fungicide or / and a cyclic imide fungicide selected from the group consisting of methyl 1- (butylcarbamoyl) benzimidazol-2-ylcarbamate, 2- (2-furyl) benzimidazole, 2- (4-thiazolyl) benzimidazole, methylbenzimidazol-2-ylcarbamate, 1,2-bis- (3-methoxycarbonyl-2-thioureido) benzene, 1,2-bis- (3-ethoxycarbonyl-2-thioureido) benzene, 2 - (O, S-dimethylphosphorylamino) -1- (3'-methoxycarbonyl-2'-thioureido) benzene, 2- (0,0-dimethylthiophosphorylamino) -1- (3'-methoxycarbonyl-2'-thioureido) benzene,

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 and ethyl- (RS) -3- (3', 5'-dichlorophenyl) -5-methyl-2,4-dioxooxazolidine- 5-carboxylate in a weight ratio of component (A) to component (B) of from 1 with one inert carrier or diluent.

0.1 to 110, together with at least

The fungicidal composition according to the invention exhibits excellent fungicidal activity against phytopathogenic fungi, both a susceptible strain and a resistant strain, so that it is particularly effective in protecting plants against fungal diseases.

In another part of the specification, organisms that are resistant to benzimidazole-thiophanate type fungicides and / or based on cyclic imides are referred to as resistant fungi or resistant strains.

While the N-phenylcarbamates of formula (I) (component A) alone have excellent fungicidal activity against phytopathogenic fungi that have developed resistance to benzimidazole-thiophanate-type fungicides and / or to cyclic imide fungicides, the combined fungicidal composition of the invention exhibits excellent activity against both both susceptible and resistant to a fungal strain.

Some N- (3,4-dialkoxyphenyl) carbamates have already been synthesized, such as N- (3,4-dimethoxyphenyl) carbamates / C. A., 2839; 50, 5674e), 2-chloroethyl N- (3-methoxy-4-octyloxyphenyl) carbamate (C). A., 55, 13376f; 21021b), 2-chloroethyl N- (3-methoxy-4-butoxyphenyl) carbamate (C). A., 64.863 g), ethyl N- (3-methoxy-4-octyloxyphenyl) carbamate (C). A., 68, 39300b) and are therefore known. However, none of these publications disclose anything about fungicidal activity against fungi.

The invention also relates to a method for combating phytopathogenic fungi, which comprises resistant and sensitive strains, comprising applying a fungicidally effective amount of the fungicidal composition of the invention to phytopathogenic fungi.

3

The phenylcarbamates of formula I wherein R, R, R, X, Y and Z are as defined above

1, with the proviso that R is not methyl or butyl, when R is methyl, are new compounds.

The process for the preparation of these novel N-phenylcarbamates of the formula I which are used as component (A) in the fungicidal composition according to the invention is described in U.S. Pat. patent file,

In formula I, the general symbols have the following preferred meanings:

R and R are each preferably: methyl; ethyl, n-propyl, isopropyl, n-butyl, allyl, propargyl, difluoromethyl, 2-chloroethyl, 2,2,2-trifluoromethyl »

R ³ is methyl, ethyl, n-propyl, isopropyl ·, sec. Butyl, 1-ethylpropyl, 1-methylbutyl, l-ethylbutyl, 1,3-almethylbutyl, 1-methylheptyl · ,. allyl, 1-methyl-2-propenyl, 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-propynyl, cyclobutyl, 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, 1-ethyl-2-bromoethyl, 4-chloro-2-butenyl, 4-chloro-2-butynyl-2-cyanethyl,

2-allyloxyethyl, 2- (2-chloroethoxy) ethyl, 2-benzyloxyethyl, 1-chloromethyl-2-methoxyethyl, cyclo240976

X and ϊ are each independently oxygen or sulfur i and

Z is hydrogen, methyl, ethyl, n-butyl, allyl, acetyl, propionyl, n-pentanoyl, sec-pentanoyl, cyclopropanecarbonyl, benzoyl, 2-chlorobenzoyl, 2,4-dichlorobenzoyl a 4-methylbenzoyl group, a methanesulfonyl group or an ethoxycarbonylmethyl group.

The fungicidal composition according to the invention comprising a combination of active ingredients A and B is active against a broad spectrum of phytopathogenic fungi, such as:

apple powdery mildew (Podosphaera leucotricha), apple scab (Venturia inaequalis), Mycosphaerella pomi, Harssonina had and Sclerotinla mail on apple trees, Fbyllactinia kakicola and Gloeosporium kaki on blackberry, Cladosporium carphophilum and Ph. on peach trees, Cercospora viticola, grape powdery mildew (Uncinula necator), anthracnose (Elsinoe ampelina) and Glomerella cingulata on the largest citrus tree, Cercospora arachidocola and cercospora personata on peanuts, sugar beetle (Cercospora betislí). properties Sp. hordei /, Cercosporella herpotrichoides and Fusarium nivale on barley, powdery mildew / Erysiphe graminis f. sp. tritici / on wheat, Sphaeroteca fuliginea and black cucumber / Cladosporium cucumerinum / on cucumber, Cladosporium fulvum on tomato, dry leaf blotch / Corynespóra.melongenae/ on aubergine, Sphaerotbeca humuli, fuzariumum rot. f .. sp. fragariae / on strawberry, Botrytis alli on onion, cercosporosis celery / Cercospora. appi / on celery, Phaeoisariopsis griseola on bean, powdery mildew / Erysiphe cichorácearum / naba, Diplocarpon rosae on roses, Elsionoe fawcetti, Penicilli um italicum, Penicillium dl.gltatum on orange trees, Botrytis cinerea on rucola, rucola, lilium, pepper, onion, lettuce, largest citrus, orange, cyclamen, roses or hops, tuber / sclerotinia sclerotiorum / on cucumbers, eggplant, paprika, lettuce, celery, bean, soybean, soybean or tomato. cinerea on peach or cherry, Mycosphaerella melonis on cucumber or melon, etc.

In particular, the N-phenylcarbamates of the formula I have a high activity in combating resistant strains of said fungal species.

The fungicidal compositions of the invention are also fungicidally active against fungi such as Pyricularia oryzae, Pseudoperonospora cubensis, Plasmopara viticola, Phytophthora infestans, etc.

The compositions according to the invention have a low toxicity and a low malignant effect on mammals, fish and the like. They can also be applied to agricultural land without the risk of toxicity to important crops _:

As component A in compositions of the invention preferred compounds of formula I in which R ¹ and R ² are independently methyl, ethyl, n-propyl, isopropyl, n-butyl, allyl, propargyl, difluoromethyl, 2-chloroethyl and 2,2,2-trifluoroethyl;

R ³ is methyl, ethyl, n-propyl, isopropyl, sec. Butyl, l-ethylpropyl, 1-methylbutyl, 1-ethylbutyl, i, 3-dimethylbutyl, 1-methylheptyl, allyl, l-methyl-2-propenyl, 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-butyhyl,

1-butyl-2-E-ropinyl, 1-pentyl-2-propynyl, cyclobutyl, 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, 1-ethyl-2-bromoethyl, 4-chloro-2; -butenyl, 4-chloro-2-butynyl, 2-cyanethyl,

2-Altyloxyethyl, 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 each independently oxygen or sulfur, and Z 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 12 with the restriction that when R is methyl, R is neither methyl nor butyl.

2

Particularly preferred are compounds of formula I wherein R and R are each independently methyl, ethyl, n-propyl, allyl or propargyl, R ³ is ethyl, isopropyl, sec-butyl 1-methylbutyl, 1-ethylpropyl, 1-ethylbutyl , 1-methyl-2-propenyl, 1-ethyl-2-propenyl, 1-methyl-3-butenyl, propargyl, 1-methyl-2-propynyl, 1-ethyl-2-propynyl, 3-butynyl, 1-methyl -S-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, 1-cyclopropylethyl or 1-phenylethyl, X is oxygen, Y is oxygen or sulfur, and Z is hydrogen, acetyl, propionyl, n-pentanoyl, sec pentanoyl, cyclopropanecarbonyl, benzoyl, 2-chlorobenzoyl 2,4-dichloro

1 benzoyl or 4-methoxybenzoyl with the proviso that R is not methyl when R is methyl.

Even more preferred compounds of formula I as component A are compounds of formula 2 2 3

Wherein R and R are each ethyl, R is ethyl, isopropyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, 1-methyl-3-butenyl, 1-methyl-2-propynyl, 4-chloro-2 -butinyl or 1-phenylethyl,

X is oxygen, Y is oxygen or sulfur and Z is hydrogen, acetyl, cyclopropanecarbonyl, benzoyl or 2-chlorobenzoyl.

The most preferred representatives of component A include the following compounds: 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, isopropyl-N-benzoyl-N- (3,4-diethoxyphenyl) carbamate, isopropyl- N- (2-chlorobenzoyl) -N- (3,4-diethoxyphenyl) carbamate, etc.

Table 1 shows typical examples of compounds of formula I which are used as active ingredient A in the fungicidal composition of the invention.

Table 1 rIq

R ² 0—— NCYR ³ Z

compound number R ¹ R ² R ³ X Y of physical Properties 1 ^CH 3 - ^C 2 ^H 5 -C ₃ H ₇ (iso) 0 0 H m.p. Mp 104-105 ° C 2 ” ^CH 3 ^_C 2 ^H 5 CSCH 1 - CHCH ₃ 0 0 H m.p. Mp 133-134 ° C 3 “ ^CH 3 - ^C 2 ^H 5 -CHCH ₃ CH ₂ OCH ₃ 0 0 H m.p. 54-55 ° C 4 “ ^CH 3 -C ₃ H _? / n / -C ₃ H ₇ (cis) 0 0 H m.p. Mp 94-95 ° C

continuation compound number Table R ¹ R ² R ³ X Y of physical Properties 5 “ ^CH 3 -ch ₂ ch = ch ₂ -C ₃ H ₇ (iso) 0 0 H m.p. . 79-80 ° C 6 ^CH 3 -CH ₂ CH = CH ₂ C = CH 1 -CHCH ₃ 0 0 H m.p. . 106-107 ° C 7 -CH ₃ -CH ₂ C = CH -C ₃ H ₇ (cis) 0 0 H 19 ⁿ D 1.5269 8 - ^C 2 ^H 5 ^CH 3 -C ₃ H ₇ (cis) 0 0 H m.p. . 103-104 ° C 9 - ^C 2 ^H 5 - ^CH 3 C = CH 1 -CHCH ₂ CH ₃ 0 0 H melting point 10 - ^C 2 ^H 5 - ^CH 3 CH ₂ C1 ₂ C5CCH 0 0 H 110, m.p. Mp 5-111.5 ° C 96-97 DEG 11 - ^C 2 ^H 5 ~ ^C 2 ^H 5 ^CH 3 0 0 H m.p. Mp 120-121 ° C 12 ^C 2 ^H 5 ^C 2 ^H 5 ^_C 2 ^H 5 0 0 H m.p. Mp 90-91 ° C 13 ^{- {} 2 ^ 5 ^_C 2 ^H 5 -C (H) (iso) 0 0 H m.p. 100-100.5 ° C 14 - ^C 2 ^H 5 ^-C 2 ^H 5 - ^c 4 ^H g / sec / 0 0 H. m.p. O 97-98 C 15 Dec - ^C 2 ^H 5 ^C 2 ^H 5 CH? 1 CH ³ / CH _2/2 CH ₃ 0 0 H m.p. 67-68 [deg.] C 16 - ^C 2 ^H 5 - ^C 2 ^H 5 CH ₂ CH ₃ -CHCH ₂ CH ₃ 0 0 H m.p. Mp 93-94 ° C 17 - ^C 2 ^H 5 ^-C 2 ^H 5 CH-CH 1 -CH / CH _2/2 CH ₃ 0 0 H m.p. 87-88 ° C 18 - ^C 2 ^H 5 - ^C 2 ^H 5 CH, CH, 3 3 -CHCH ₂ CHCH ₃ 0 0 H m.p. Mp 56-57 ° C 19 Dec ^_C 2 ^H 5 ^-C 2 ^H 5 I ^"3 -CH / CH _2/5 CH ₃ 0 0 H m.p. 46.5-48 ° C 20 May - ^C 2 ^H 5 ^C 2 ^H 5 -CH ₂ CH-CH ₂ 0 0 H m.p. M.p. 86-87 ° C 21 ^_C 2 ^H 5 - ^C 2 ^H 5 CH, 1 -CHCH = CH ₂ 0 0 H m.p. 98-99.5 ° C 22nd - ^C 2 ^H 5 - ^C 2 ^H 5 -CH ₂ CH ₂ CH = CH ₂ 0 0 H m.p. 92.5-93.5 ° C 23 ^C 2 ^H 5 - ^C 2 ^H 5 Γ ³ -CH ₂ C = CH ₂ 0 0 H m.p. Mp 92-93 ° C

tables

R ¹ R ² R ³ X Y physical OF Properties “ ^C 2 ^H 5 ^C 2 ^H 5 CH.CH, I -CHCH = CH ₂ 0 0 H m.p. 98.5-99.5 ° C ~ ^C 2 ^H 5 ^C 2 ^H 5 CH 1 -CHCH ₂ CH = CH ₂ 0 0 H m.p. 75-76 [deg.] C ^C 2 ^H 5 ^C 2 ^H 5 CH1 CH = CH ² / CH _2/4 CH ₃ O O H m.p. 46.5-48 ° C ^_C 2 ^H 5 ^_C 2 ^H 5 -CH ₂ CSCH 0 0 H m.p. Mp 111-112 ° C ^-C 2 ^H 5 - ^C 2 ^H 5 CH1 ³ -CHCSCH 0 0 H m.p. Mp 116-117 ° C ^C 2 ^H 5 - ^c 2 ^H 5 -ch ₂ ch ₂ csch 0 0 H m.p. Mp 89-90 ° C ^_C 2 ^H 5 ^C 2 ^H 5 CH _O CH-1 ^{2 3} -CHCSCH 0 0 H m.p. M.p. 118-119 ° C - ^C 2 ^H 5 ^_C 2 ^H 5 CH 1 -CHCH ₂ CSCH 0 0 H m.p. 99-100 ° C ^C 2 ^H 5 - ^C 2 ^H 5 C = CH 1 CH / CH _2/3 CH ₃ 0 0 H m.p. 120-121 ° Art - ^C 2 ^H 5 ^_C 2 ^H 5 C = CH 1 -CP / CH _2/4 CH ₃ 0 0 H m.p. 96-97 DEG - ^C 2 ^H 5 - ^C 2 ^H 5 0 0 H m.p. 114-115.5 ° C - ^C 2 ^H 5 ^-C 2 ^H 5 -CH ₂ CH ₂ F 0 0 H m.p. 101-102 ° C ^C 2 ^H 5 - ^C 2 ^H 5 -CH ₂ CH ₂ Cl 0 0 H m.p. 89.5-90.5 ° C - ^C 2 ^H 5 ^_C 2 ^H 5 -CH ₂ CHCl ₂ 0 0 H m.p. Mp 73-74 ° C ^C 2 ^H 5 ^-C 2 ^H 5 -3 -CHCHjBr 0 0 H m.p. 69-70 [deg.] C ^C 2 ^H 5 - ^C 2 ^H 5 CH, F 1 -CHCH ₂ F 0 0 H m.p. Mp 89-90 ° C - ^C 2 ^H 5 - ^C 2 ^H 5 CH Br 1 ² -CHCH ₂ Br 0 0 H m.p. 75-76 [deg.] C

 tables

- ^C 2 ^H 5

- ^C 2 ^H 5

- ^C 2 ^H 5 ^C 2 ^H 5 ^C 2 ^H 5

- ^C 2 ^H 5 ' ^C 2 ^H 5' ^C 2 ^H 5 ' ^C 2 ^H 5' ^C 2 ^H 5 ~ ^C 2 ^H 5

-C ₃ H _? (n) ^-C 2 ^H 5

-C ₃ H _? / n /

-C ₃ H _? / n /

-C ₄ Hg / n /

-C ₄ H _g / n /

-ch ₂ guild

-CH

R ³ X Y physical OF Properties -chcci ₃ 0 0 H n * ⁹ ' ⁵ 1.5316 -CH ₂ CH = CHCH ₂ Cl 0 G H m.p. Mp 82-83 ° C -CH ₂ C = CCH ₂ C 1 0 0 H m.p. 112-113 ° C -CH ₂ CH ₂ OCH ₂ CH = CH ₂ 0 0 H m.p. Mp 58-59 ° C -CH ₂ CH ₂ OCH ₂ CH ₂ Cl 0 0 H m.p. 77-78 [deg.] C CH, 1 ₂ -CHCH ₃ OCH 0 0 H m.p. 65-66.5 ° C f -CHCH 3 ^H ₂ O / CH _2/3 CH ₃ 0 0 H m.p. Mp 36-38 ° C CH-Cl 1 -CHCH ₂ OCH ₃ 0 0 H m.p. Mp 82-83 ° C -CH ₂ CH ₂ CN 0 0 H m.p. 85.5-86.5 ° CH, -L-o 0 0 H m.p. Mp 107-108 ° C ^C 2 ^H 5 0 0 H m.p. Mp 74-75 ° C -C ₃ H ₇ (1so) 0 0 H m.p. 97-98 [deg.] C C »CH AND 1 -CHCH ₃ 0 0 H m.p. 99-100 ° C -C ₃ H ₇ (cis) 0 0 H m.p. Mp 110-111 ° C CH. 1 -CHCH ₂ OCH ₃ 0 0 H m.p. 87-88 ° C -C ₃ H ₇ (1so) 0 0 H m.p. 102-103 ° C -C ₃ H ₇ (1so) 0 0 H m.p. Mp 101-102 ° C

continued table

compound number R ¹ R ² R ³ X Y of physical Properties 58 -C ₃ H ₇ / n / -C ₂ H ₅ -CH ₃ 0 0 H m.p. . Mp 85-86 ° C 59 -C ₃ H _? (n) -C ₂ H ₅ ^_C 2 ^H 5 0 0 H m.p. . 76.5-77.5 ° C 60 -C ₃ H ₇ (n) -C ₂ h ₅ -c ₃ h ₇ / number / 0 0 H m.p. . 81.82 ° C 61 -C ₃ H ₇ / n / -C ₂ H ₅ -3 -CHCH ₂ CH ₂ 0 0 H t.t, . 83-84 DEG 62 -C ₃ H ₇ / n / c ₂ H ₅ CH ₂ CH 1 ¹² -CHCH ₂ CH ₃ 0 0 H m.p. . Mp 90-91 ° C 63 -C ₃ H ₇ / n / -C ₂ H ₅ CH ₃ 'CH - <J 0 0 H m.p. 82-83 ° C 64 -C ₃ H ₇ / n / -C ₂ H ₅ -CH ₂ CH ₂ F 0 0 H m.p. Mp 82-83 ° C 65 -C ₃ H ₇ -C ₃ H ₇ / n / -C ₃ H ₇ (cis) 0 0 H m.p. Mp 85-86 ° C 66 -C ₃ H ₇ (iso) -C ₂ H ₅ -c ₃ h ₇ / 1so / 0 0 H 1,5121 67 -c ₃ h ₇ / number / -c ₂ h ₅ CH, ¹³ -CHC5CH 0 0 H m.p. 100.5-102 ° C 68 -c ₃ h ₇ / number / -c ₂ h ₅ CH, 1 ₂ -CHCH ₃ OCH 0 0 H '19 ⁿ D 1,5092 69 -C ₄ H _g / n / -C ₂ H ₅ -C ₃ H ₇ (cis) 0 0 H m.p. 79.5-81 ° C 70 -CH ₂ CH = CH ₂ -C ₃ H _? / n / -C ₃ H ₇ (cis) 0 0 H m.p. Mp 82-83 ° C 71 -CH ₂ CH = CH ₂ -C ₃ H ₇ (n) -CH ₂ CH = CHCH ₃ 0 0 H m.p. 66-67 [deg.] C 72 -CH ₂ CH = CH ₂ -C ₃ H _? / n / -CH ₂ CH = CCH ₃ 0 0 H m.p. Mp 92-93 ° C 73 -CH ₂ CH = CH ₂ -C ₃ H ₇ (n) C = CH 1 -CHCHj 0 0 H m.p. Mp 84-85.5 ° C 74 -ch ₂ ch = ch ₂ -ch ₂ ch = ch ₂ -C ₃ H ₇ (iso) 0 0 H m.p. 83.5-84.5 ° C 75 -CH ₂ C = CH ₂ -C ₂ H ₅ -C ₃ H ₇ (1so) 0 0 H m.p. 101-102 ° C

continued table

compound number R ¹ R ² R ³ X Y of physical Properties 76 -CH ₂ C ± CH ₂ -ch ₂ cbch -C ₃ H _? / iso / 0 0 H m.p. 103-104 ° C 77 -CHF ₂ -CHF ₂ -C ₃ H ₇ (1so) 0 0 H n ²² 1.4671 78 - ^C 2 ^H 5 - ^C 2 ^H 5 -ch ₂ ch ₂ and ₂ - 0 0 H m.p. Mp 73-74 ° C 79 - ^C 2 ^H 5 - ^C 2 ^H 5 - ^CH 2 ^ <] 0 0 H m.p. Mp 95-96 ° C 80 ~ ^C2 ^ 5 - ^C 2 ^H 5 CH- 0 0 H m.p. 105-106 ° C 81 - ^C 2 ^H 5 ^C 2 ^H 5 CH.CH, ¹³ -CHCH ₂ Br 0 0 H m.p. 68-69 [deg.] C 82 -CH3CH3Cl ~ ^C 2 ^H 5 -C ₃ H ₇ (iso) 0 0 H m.p. Mp 111-112 ° C 83 - ^C 2 ^H 5 ^C 2 ^H 5 -C ₃ H _? / n / 0 0 H m.p. 79-80 ° C 84 ^-C 2 ^H 5 - ^C 2 ^H 5 0 0 H m.p. M.p. 117-118 ° C 85 - ^C 2 ^H 5 - ^C 2 ^H 5 -ch ₂ - 0 0 H mp 111.5-112.5 ^C 86 - ^C 2 ^H 5 - ^C 2 ^H 5 OH 0 0 H m.p. Mp 109-110 ° C 87 - ^C 2 ^H 5 - ^C 2 ^H 5 - ^C 2 ^H 5 0 with H m.p. Mp 107-108 ° C 88 ^C 2 ^H 5 ~ ^C 2 ^H 5 -C ₃ H ₇ (ISO) 0 with H m.p. Mp 110-111 ° C 89 - ^C 2 ^H 5 - ^C 2 ^H 5 -CH ₂ CH = CH ₂ . 0 with H m.p. Mp 73-76 ° C 90 - ^C 2 ^H 5 - ^C 2 ^H 5 ^C 2 ^H 5 0 0 '-ch ₃ n ²⁸ ' ⁵ 1.5059 91 - ^C 2 ^H 5 - ^C 2 ^H 5 -C ₃ H ₇ (cis) 0 0 -c ₂ h ⁵ n ²⁸ ' ⁵ 1.4922 92 - ^C 2 ^H 5 ^-C 2 ^H 5 -C ₃ H ₇ (cis) 0 0 -c ₄ H ₉ / n /

n ²⁶ ' ⁵ 1.4885

24O97.'6 continued table compound number

R ¹ R ² physical

X Y & Properties

-C ₃ H ₇ (iso)

- ^C 2 ^H 5

-C ₃ H _? / íso /

-C ₃ H ₇ (cis) ^C 2 ^H 5

-C ₃ H ₇ / ISO / oo -CH ₂ CH = CH ₂ n ^26.5 1.5044

OO -coch ₃

m.p. 98-99 ° C

J

OO -COC ₂ H ₅ n ^27.5 1.5006 δ O -COC ₄ H ₉ / n /

m.p. 63-65 [deg.] C

- ^C 2 ^H 5 ^-C 2 ^H 5

-C ₃ H ₇ (cis)

-C ₃ H ₇ (cis)

OO-COCl 3 Hg / sec / n ²⁸ 1.4889

O O -CO -

mp 55-57 ° C ^_C 2 ^H 5 ^C 2 ^H 5

-C ₃ H _? / 0/0 ^ 0-0

100 ALIGN!

- ^C 2 ^H 5

-C ₃ H ₇ (cis)

101

-C ₃ H ₇ (cis)

102

-C ₂ ^H 5 " ^C 2 ^H 5

103

-C ₃ H ₇ (cis)

CH,

I ³

-CHCH ₂ 0CH ₃

m.p. 102-103 ° C

104 ^C 2 ^H 5

-C ₃ H ₇ / cis / ο o -coc ₂ h ₅ n ²⁷ 1.4972 oo -so ₂ ch ₃

m.p. Mp 114-115 ° C

105

- ^C 2 ^H 5

-C ₃ H ₇ (cis) o -ch ₂ cooc ₂ h ₅

1.4948

27.5

D

continuation tables compound physical number R ¹ R ² R ³ X y of Properties 106 “ ^C 2 ^H 5 - ^C 2 ^H 5 ^C 2 ^H 5 WITH 0 H m.p. Mp 74-75 ° C 107 ^-C 2 ^H 5 ^C 2 ^H 5 -ch ₃ WITH 0 H m.p. 87-88 ° C 108 - ^C 2 ^H 5 - ^C 2 ^H 5 -C ₄ H _{g /} sec./ 0 with H mp 97-98 ° C 109 ^_C 2 ^H 5 - ^C 2 ^H 5 -C ₃ H _? / iso / WITH with H m.p. Mp 64-65 ° C

Table 2 gives typical examples of benzimidazole-thiophanate-type fungicides and cyclic imide fungicides which are used as component (B) in the fungicidal composition of the invention:

Table 2 Compound

And the title

-NHCOOCH3

CONHC ₄ Hg

NHCOOCH3

with

AND!

NHCNHCOOCH,

NHCNHCOOCH, II ^d

WITH

NHCNHCOOC-Hil 2 5

With methyl 1- (butylcarbamoyl) benzimidazol-2-ylcarbamate

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

2- (2-furyl) benzimidazole

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

1,2-bis- (3-ethoxycarbonyl-2-thioureido) benzene plating table compound formula

With ll nhcnhcooch ₃

NHP-S-CH = H \ ³

O OCH ₃ p

II

NHCNHCOOCH ₃

NHP-O-CH, 11, ³ s and ₃

- (O, S-Dimethylphosphorylamino) -1 / 3'-methoxycarbonyl-2'-thioureido / benzene

2- (O, O-dimethylthiophosphorylamino) -1,3'-methoxycarbonyl-2'-thioureido] benzene.

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

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

3- (3 ', 5'-Diohlorophenyl) -5-methyl-5-vinyloxazolidine-2,4-dione ethyl- (RS) -3- (3', 5-dichlorophenyl) -5-methyl-2,4-dioxooxazolidine- 5-carboxylate

In practical use of the active ingredient combination A and B according to the invention as fungicides, they can be applied as such or in the form of dusts, wettable powders, oil sprays, emulsifiable concentrates, tablets, granules, microgranules, aerosols or suspensions.

Such compositions may be prepared in conventional manner by mixing the active compounds with suitable solid or liquid carriers or diluents, and optionally with suitable auxiliaries (such as surfactants, adhesives, dispersants or stabilizers) to improve the dispersibility or other properties of the active ingredient or active ingredients. substances.

Examples of solid carriers or diluents are plant materials / for example in the form of flour, tobacco stem powder, soybean powder, nutshell powder, powdered plants, sawdust, bran, ground tree bark, powdered cellulose, extract residues plants /, fibrous materials (e.g., paper, corrugated board, old rags), powdered plastics, clays (e.g., kaolin, bentonite, clay), talc, other inorganic materials (e.g., pyrophyllite, sericitum, pumice, powdered sulfur, active .240976 14: coal (and fertilizers) (e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ammonium chloride).

Examples of liquid carriers or diluents include water, alcohols (e.g. methanol, ethanol), ketones (e.g. acetone, methyl ethyl ketone), ethers (e.g. diethyl ether, dioxane, glycol ethylene ether, tetrahydrofuran), aromatic hydrocarbons (e.g. benzene, toluene, xylene, methylnaphthalene (), aliphatic hydrocarbons (e.g., gasoline, kerosene, light oil), esters, nitriles, acid amides (e.g., dimethylformamide, dimethylaetamide), halogenated hydrocarbons (e.g., dichloroethane, carbon tetrachloride), and the like.

Examples of surfactants include alkylsulfuric acid alkyl esters, alkylsulfonates, alkylarylsulfonates, polyethylene glycol ethers, polyhydric alcohol esters, etc. Examples of adhesives and dispersants may include cassin, gelatin, powdered starch, carboxymethylcellulose, acacia, alginic acid, lignin, bentonite, melasin, melanine , turpentine oil and agar.

Mixtures of isopropyl phosphates, tricresyl phosphates, epoxidized oil, various surfactants, various fatty acids and their esters, etc. can be used as stabilizers.

The aforementioned compositions generally comprise a combination of the active compounds according to the invention in a concentration of from 1 to 95% by weight, preferably from 2 to 80% by weight. In the application of these compositions, the active compound combination is generally used in an amount of from 20 to 1000 g ha per ha.

The individual components of the combination may also be applied as such or in the form of conventional formulations used in agriculture.

The weight ratio between the N-phenylcarbamate of formula I (component A) and the benzimidazole thifanate fungicide or / and the cyclic imide fungicide (i.e. component B / may range from about 1: 0.1 to 1: 10.

The compositions of the invention may also be used in admixture with other fungicides, herbicides, insecticides, acaricides, fertilizers, etc.

If the compositions according to the invention are used to combat phytopathogenic fungi, they can be applied in an amount of from 20 to 1000 g per ha. Said amount is dependent on the form of the preparation, the time of application, the method of application, the place of application, the degree of disease, the crop used and is therefore not limited to the exact amount mentioned above.

Some practical examples of the fungicidal compositions of the present invention are given below, in which percentages and parts are by weight and parts by weight.

Example 1 of Compound No. 7, 1 part of Compound 1, 88 parts of kaolin and 10 parts of talc are thoroughly mixed under grinding to obtain a dust containing 2% active ingredient.

Example 2 parts of Compound No. 86, 10 parts of Compound J, 45 parts of diatomaceous earth, 20 parts of colloidal silica, 3 parts of sodium lauryl sulfate as a wetting agent and 2 parts of ligninsulfonic acid calcium salt dispersants are mixed and ground to a powder. A wettable powder is obtained which contains 30% of the active ingredient.

Example 3 parts of compound No. 88, 40 parts of compound B, 45 parts of diatomaceous earth, 2.5 parts of alkylbenzene sulphonic acid calcium salt as a wetting agent and 2.5 parts of lignin sulphonic acid calcium salt dispersant are mixed, grinded to obtain a wettable powder, containing 50% of the active ingredient.

Example 4 parts of compound S. 94, 50 parts of compound I, 18 parts of diatomaceous earth, 3.5 parts of alkylbenzene sulphonic acid calcium salt as a wetting agent and 3.5 parts of lignin sulphonic acid calcium salt dispersant are mixed, grinded to obtain a wettable powder containing 75% active ingredient.

Example 5 parts of Compound No. 50, 30 parts of Compound A, 40 parts of sucrose powder, 5 parts of colloidal silica, 3 parts of sodium lauryl sulfate as a wetting agent and 2 parts of lignin sulphonic acid calcium dispersant are mixed and ground to obtain a wettable powder containing 50% of the active ingredient.

The results of typical tests illustrating the excellent fungicidal efficacy of the composition of the invention are given below:

Test 1

Preventive effect on powdery mildew of Sphaeroteca fuliginea on cucumbers

The plastic pots with a content of 90 ml are filled with sandy soil into which the cucumber seeds (variety Sagami-hanjiro) are sown. Cultivation is carried out in a greenhouse for 8 days. When the cotyledons unfold the uterine leaves, the test compound (s) / combination (s) are sprayed in the form of an emulsion concentrate or wettable powder diluted with water at 10 ml per pot.

Then, the seedlings are infected by spraying a suspension of a mixture of spores of a resistant and susceptible strain of Sphaeroteca fuliginea. The plants are then further cultivated in a greenhouse. 10 days thereafter, the degree of infestation of the plants is assessed.

The degree of damage is determined as follows. The test results are shown in Table 3

The contaminated area (expressed in%) is measured on the sheets examined and denoted with indexes 0, 0,5, 1, 2, and 4:

index

0,5 infested area in% without infection infested less than 5% infested less than 20% infested less than 50 i infested more than 50%

The extent of the disease is calculated according to the following formula:

extent of disease (i)

Σ / index /, x. /number of pages/.

x 100 x / total sheets examined /

Preventive efficacy is calculated using the following formula:

extent of disease on treated plants.

preventive efficacy /% / = 100 - —---— --- - -——. . ^{x 100 ť} / extent of disease on untreated plants /

Table 3

compound concentration preventive C. active substance efficiency / ppm / /% / 13 100 ALIGN! 34 13 20 May 0 15 Dec 100 ALIGN! 28 15 Dec 20 May 0 28 100 ALIGN! 44 28 20 May 0 43 100 ALIGN! 36 43 20 May 0 86 100 ALIGN! 44 86 20 May 0 88 100 ALIGN! 28 88 20 May 0 94 100, 32 94 20 May 0 98 100 ALIGN! 28 98 20 May 0 99 100 ALIGN! 28 99 20 May 0 100 ALIGN! 100 ALIGN! 36 100 ALIGN! 20 May 0 AND  100 ALIGN! 45 ^A l 20 May 12 (B) 500 42 (B) 100 ALIGN! 10 C 100 ALIGN! 42 C 20 May 8 D 500 36 D 100 ALIGN! 0 E 100 ALIGN! 44 E 20 May • 10 F 100 ALIGN! 43 F 20 May 8 G 100 ALIGN! 42 G 20 May 8 H 100 ALIGN! 40 H 20 May 5 13 + A 20 + 20 100 ALIGN! 13 + E 20 + 20 100 ALIGN! 13 + H 20 + 20 100 ALIGN! 15 + A 20 + 20 100 ALIGN! 15 + F 20 + 20 100 ALIGN! 28 + A 20 + 20 100 ALIGN! 28 + B 20 + 20 100 ALIGN! 28 + C 20 + 20 100 ALIGN!

'•' •• '• PV, table continuation

compound concentration active substance / Ex »» / preventive efficiency / »/ C. 43 + D 20 + 20 100 ALIGN! 43 + G 20 + 20 100 ALIGN! 43 + H 20 + 20 100 ALIGN! 86 + A 20 + 20 100 ALIGN! 86 + B 20 + 20 100 ALIGN! 86 + F 20 + 20 IOO 88 + c 20 + 20 100 ALIGN! 88 + E 20 + 20 100 ALIGN! 88 + G 20 + 20 100 ALIGN! 94 + A 20 + 20 100 ALIGN! 94 + E 20 + 20 100 ALIGN! 94 + G 20 + 20 100 ALIGN! 98 + C 20 + 20 100 ALIGN! 98 + H 20 + 20 100 ALIGN! 99 + A 20 + 20 100 ALIGN! 99 + B 20 + 20 100 ALIGN! 100 + A 20 + 20 100 ALIGN! 100 + D 20 + 20 100 ALIGN! 100 + E 20 + 20 100 ALIGN!

As can be seen from the results shown in Table 3, the combined use of the N-phenylcarbamates of the formula I according to the invention with benzimidazole-thiophianate-type fungicides and / or cyclic imide-based fungicides shows much better preventive activity than their use alone.

Test 2

Preventive activity on gray mold (Botrytis cinerea) on tomato

The plastic pots of 90 ml are filled with sandy soil and seeded with tomato seeds (Fekuji variety 2). The plants were grown in a greenhouse for 4 weeks. The resulting 4-leaf stage seedlings are sprayed with the test compound (s) in the form of an emulsion concentrate or wettable powder diluted with water at a rate of 10 ml per pot.

The plants are then sprayed with a suspension of a mixture of spores of a resistant and sensitive strain of the fungus Botrytis cinerea and tunis for 5 days in a high humidity room. The degree of damage was determined in the same manner as described in Test 1. The results of this test are shown in Table 4 below.

Table 4

compound C. active substance concentration (ppm) preventive / », 13 100 ALIGN! 44 13 20 May 0 25 100 ALIGN! 27 Mar: 25 20 May 0 28 100 ALIGN! 38 28 20 May 0 43 100 ALIGN! 38 43 20 May 0 86 100 ALIGN! 42 86 20 May 0 88 100 ALIGN! 42 88 20 May 0 94 100 ALIGN! 42 94 20 May 0 98 100 ALIGN! 40 98 20 May 0 99 100 ALIGN! 44 99 20 May 0 100 ALIGN! 100 ALIGN! 38 100 ALIGN! 20 May 0 AND 100 ALIGN! 48 AND 20 May 22nd J 500 46 J 100 ALIGN! 18 TO 100 ALIGN! 42 TO 20 May 15 Dec : X 500 42 X 100 ALIGN! 12 13 + 1 20 + 50 100 ALIGN! 13 + 3 20 + 50 100 ALIGN! 13 + K 20 + 50 100 ALIGN! 13 + X 20 + 50 100 ALIGN! 25 + 1 20 + 50 100 ALIGN! 25 + K 20 + 50 100 ALIGN!

continued table

compound concentration preventive C. active substances (ppm) efficiency /% / 28 + X 20 + 50 100 ALIGN! 28 + L 20 + 50 100 ALIGN! 43 + 1 20 + 50 • 100 43 + J 20 + 50 100 ALIGN! 86 + 1 20 + 50 100 86 + 1 20 + 50 100 ALIGN! 88 + 1 20 + 50 100 ALIGN! 88 + J 20 + 50 100 ALIGN! 94 + 1 20 + 50 * 100 ALIGN! 94 + J 20 + 50 ^{100 ALIGN!} 98 + 1 20 + 50 100 ALIGN! 98 + K 20 + 50 100 ALIGN! 99 + 1 20 + 50 100 ALIGN! 99 + J 20 + 50 100 ALIGN! X00 + I 20 + 50 100 ALIGN! 100 + K 20 + 50 100 ALIGN! As follows and the results in Table 4 , has a combination of active ingredients according to invention much better preventive effect than use of the components of the mixture themselves, ie N- -phenylcarbamate of formula I and the fungicide benzimidazole; of the thiophanate type and / or a fungicide

based on cyclic imide.

Claims (4)

SUBJECT OF THE INVENTION 1 2 · R @ 1 and R @ 2 having the same or different meanings denote a C1 -C4 alkyl group, an allyl group, a propargyl group or a halogen radical having 1 to 2 carbon atoms, an alkyl group having 1 to 8 carbon atoms, an alkenyl group with 3 to 8 carbon atoms, C 3 -C 8 alkynyl, 4-carbon cycloalkyl group, 4-carbon haloalkenyl, 4-carbon haloalkynyl, phenethyl, furylmethyl, haloalkyl of 2 to 4 carbon atoms, cyanethyl, C 1 -C 4 alkoxyalkyl and 2 to 3 carbon atoms in the alkyl moiety, allyloxyethyl, halenethoxyethyl, 3-carbon methoxyhaloalkyl, benzyloxyethyl, cycloalkylalkyl of 3 to 5 carbon atoms in the cycloalkyl moiety having 1 to 2 carbon atoms in the alkyl moiety or tetrahydrofuranyl group, X and Y are the same or different from each other and are oxygen or sulfur, and Z represents hydrogen, (C1-C4) alkyl, allyl, ethoxycarbonylmethyl, C2-C5 alkanoyl, cyclopropanecarbonyl, benzoyl, halobenzoyl, methylbenzoyl or methanesulfonyl; and / B / at least one a benzimidazole-thiophanate type fungicide and / or a cyclic imide fungicide selected from the group consisting of methyl 1- (butylcarbamoyl) benzimidazol-2-ylcarbamate, 2- (2-furyl) benzimidazole, 2- (4-thiazolyl) benzimidazole , methylbenzimidazol-2-ylcarbamate, 1,2-bis- (3-methoxycarbonyl-2-thioureido) benzene, 1,2-bis- (3-ethoxycarbonyl-2-thioureido) benzene, 2- (O, S-dimethylphosphorylamino) / -1- (3'-methoxycarbonyl-2'-thioureido) benzene, 2- (0,0-dimethylthiophosphorylamino) -1- (3'-methoxycarbonyl-2'-thiouride) benzene, / 1 / in which A fungicidal composition comprising as active ingredient (A) at least one N-phenylcarbamate of the formula (X) X. ... - II, R ² 0 nc-YR ³ I z 2. A composition according to claim 1, wherein the benzimidazole-thiophanate type is in claim 1. that it contains a fungicide as component (B) 3. A composition according to claim 2, characterized in that as component (A) it comprises at least 1 2 &apos; 3 one N-phenylcarbamate of the formula X in which R and R are each ethoxy, R is C1-C8alkyl. , C 3 -C 8 alkenyl, C 3 -C 8 alkenyl, C 4 haloalkenyl, C 4 haloalkynyl, C 2 -C 4 haloalkyl, C 1 -C 4 alkoxyalkyl in the alkoxy moiety having 2 to 3 carbon atoms in the alkyl moiety or a cycloalkylalkyl group having 3 to 5 carbon atoms in the cycloalkyl moiety and having 1 to 2 carbon atoms in the alkyl moiety, x is oxygen, Y is oxygen and Z is hydrogen. 3- (3 ', 5'-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboximide, 3- (3', 5'-dichlorophenyl) -1-isopropylcarbamoylimidazolidine-2,4-diol, 3- / 3 ', 5'-dichlorophenyl / -5-methyl-5-vinyloxazoline-2,4-dione and ethyl- (RS) -3- (3', 5'-dichlorophenyl) -5-methyl-2,4-dioxooxazolidine- 5-caxybtylate in a weight ratio of component (A) to component (B) of from 1: 0.1 to 1:10, together with at least one inert carrier or diluent. 4. A composition according to claim 2, comprising as component (A) at least one N-phenylcarbamate of formula (I) wherein R @ ¹ and R @ ² are each C1 -C4 alkyl, propargyl or haloalkyl. C 1 -C 2 alkyl, R ³ is C 1 -C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkenyl, C 4 cycloalkyl, C 4 haloalkenyl , C 4 -C 4 haloalkynyl, C 2 -C 4 haloalkyl, cyanethyl, C 1 -C 4 alkoxyalkyl and C 2 -C 3 alkyl, allyloxyethyl, haloethoxyethyl, methoxyhaloalkyl C 3 -C 5 alkyl, benzyloxyethyl or C 3 -C 5 cycloalkylalkyl moieties having 1 to 2 carbon atoms in the alkyl moiety, X is oxygen, Y is oxygen and Z is hydrogen.