CS227336B2 - Fungicide and method of preparing active substance the thereof - Google Patents

Description

(54) A fungicidal composition and a process for preparing its active ingredient

The present invention relates to a fungicidal composition comprising, in addition to an inert carrier, a certain N-phenylcarbamate described below as a fungioid active ingredient.

The invention further relates to a process for the preparation of N-phenylcarbamates which form the active ingredient of the fungicidal composition.

Benzimidazothiophanate fungicides such as Benomyl (methyl-1- (butylcarbemoyl / benzimidazol-2-ylcarbamate), Fubelidezole (2- / 2-furyl / benzimidazole), Thiabendazole (2- / 4-thiazolyl / benzimidazole), Carbendazim ( methylbenzimidazol-2-ylcarbamethyl), Thiophanetethyl (1,2-bis / 3-methoxycarbonyl-2-thioureido / benzene), Thlofenate (1,2-bis / 3-ethoxycarbonyl-2-thioureido / benzene), 2-0, S -dimetylfosforylamino) -l- (3 ^# methoxycarbonyl-2'-thioureido) benzene and 2- (O, 0-dimetylthiofosforylamino) -1- (3'-methoxycarbonyl-2'-thioureido) benzene show an excellent fungicidal activity against various fungi pathogenic to plants and since 1970 have been widely used as agricultural fungicides.

However, it is also known that their continuous long-term use results in phytopathogenic fungi developing resistance to them, thereby greatly reducing the preventive effect of these substances against the attack of plants. In addition, molds which have acquired resistance to certain types of benzimidazole thiophanate fungicides are also known to exhibit considerable resistance to certain other types of benzimidazole thiophanate fungicides.

Thus, these molds are prone to cross-resistance. When a significant decrease in the preventive effect of these substances against plant diseases is found in certain fields, their application to such a field must be discontinued. However, it is often observed that the density of organisms resistant to the substances used does not decrease long after discontinuation of application.

In such cases, other types of fungicides need to be used, but only a small number of them are as effective at controlling various phytopetogenic fungi such as benzimidazlthiophthane fungicides.

Cyclic imide fungicides such as Fromidone β- (3 ', 5'-dichlorophenyl) -1,2-dimethylcyclopropane-, 2-dicarboximide], Iprodione [3- (3', 5'-dichlorophenyl) -, -isopropyl- (5-methyl-5-vinyloxazoline-2,4-dione), ethyl- (RS) -3- ( 3 *, 5 ⁽ Dichlorophenyl) -5-methyl-2,4-dioxooxazolidine-5-carboxylate, etc., which are effective against various plant diseases, especially those caused by Botrytis cinerea, have the same disadvantages as the benzimidazole thiophenetic fungicides described in the above paragraph.

In Agriculturel Biological Chemlstry, vol. 35, pages 1 707 to 719 (1971), it is described that methyl N- (3,5-dichlorophenyl) carbamet and ethyl N- (3,5-dichlorophenyl) carbamet were tested for the potency of the antibiotic action against Sclerotinia sclerotiorum by the agar dilution method, but showed only very poor potency compared to other structurally similar compounds such as [alpha] -phenoxyisopropyl-N- (3,5-dichlorophenyl) carbamet and alpha-ethoxycarbonyl sopropyl poly- N- (3). (5-chlorophenyl) carbamet.

On the other hand, C. R. Acad, Sc. Paris, Vol. 289, Series D, pp. 691-693 (1979), discloses that herbicides such as Barban [4-chloro-2-butynyl-N- (3-chlorophenyl) carbamate], Chlorobufam [1-methyl] The 2-propynyl N- (3-chlorophenyl) carboxylate], Chlorprofam [ieopropyl-N- (3-chlorophenyl) carboxylate] and Profem [ieopropyl-N-phenylcarbemate] exhibit fungioid activity against certain organisms tolerating some benzimidazole thlophene fungicides. However, since they are also used as herbicides, it is clear that their foliar application to crops as fungicides will result in serious chemical damage to the crop. In addition, their fungioid activity against resistant fungi is not strong enough so that they cannot be used as fungicides.

It has now been found, based on extensive study, that the N-phenylcarberates of formula (I)

O

II

NHCOR (I) wherein each of X and Y, which are the same or different, represents an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a halogen atom, and

R is methyl or ethyl, exhibiting excellent fungioid activity against fungi pathogenic to plants that have built up resistance to benzimidezole thiophthane fungicides and / or to cyclic imide fungicides. It is noteworthy that the potency of their fungicidal action against benzimidezole thiophthane fungicides and / or cyclic imide fungicides (hereinafter referred to as resistant strains) is much higher than that of benzimidazole thlophenate fungicides and / or not cyclic amide fungicides (longer are these fungi are referred to as sensitive strains).

Accordingly, the present invention provides a fungioid composition comprising a fungididally effective amount of an active ingredient and a carrier, wherein the active ingredient comprises a compound of formula I as defined above.

The active ingredients of the formula (I) may be combined with benzimidazole / thiophenate fungicides and / or cyclic imide fungicides. Such compositions are then fungicidally effective not only against susceptible, but also resistant fungi, and are preventively effective against plant diseases.

Examples of benzimidazole thiophanate fungicides include Benomyl [methyl-1- (butylcarbamoyl) benzimidezol-2-ylcarbamet], Fubelidezole [2- / 2-furyl / benzimidazole], Thiabendazole [2- (4-thiazolyl) benzimidazole], Carbendazim [methylbenzimidazole] -2-ylcarbamethyl], Thiophanate-methyl [1,2-bis (3-methoxycarbonyl-2-thioureido) benzene], 2- (O, S-diaethylphosphorylamino) -1- (3'-methoxycarbonyl-2'-thloureido) benzene, Thiophanate [l, 2-bis- / 3-etoxykerbonyl-2-thioureido / -benzene], 2- / 0,0-di-metylthiofosforylamino) -! - ^{(3-methoxycarbonyl-2'-thioureido)} benzene, etc.

Examples of cyclic amide fungicides include Procymidone [3- (3 *, 5'-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboximide], Iprodione [3- (3 ', 5'-dichlorophenyl) -1 -isopropylcarbamoylimidazolidin-2,4-dione], Vinchlozolin [3- (3 ', 5'-dichlorophenyl) -5-methyl-5-vinyloxazoline-2,4-dione], ethyl (RS) -3- (3', 5 (dichlorophenyl) -5-methyl-2,4-dioxooxazolidine-5-carboxylate, etc.

Of the N-phenylcarbametes (I), those compounds in which X and X are both chlorine are known, the other compounds of formula I are novel, N-phenylcarbersates of formula Ij in which X is lower alkyl, lower alkoxy, chlorine, fluorine, bromine or iodine, ϊ is lower alkyl, lower alkoxy, fluorine, bromine or iodine, and R is methyl or ethyl are new.

The compositions of the invention are fungicidally active against a broad spectrum of plant pathogens, including, but not limited to: Podospaera leucotricha. Venturia inaequalis, Mycospaeralla pomi, Marssonia had and Sclerotinia mail on cablons, Phyllaetinia kakicole and Gloeosporium kaki on persimmon, Cladosporium carpophilum and Phooopsis sp on peach trees, Cercospora viticola, Grapevine, Cucospora, Cottonspoon, Elsinae necaera Cercospora arachidicola and Cercospora personata on peanuts, Erysiphe gramiňis f. Sp. hordei, Cercosporella herpotrichoi des and Fusarium nivale on barley, Erysiphe gramiňis f. sp. tritici on wheat, Sphaerotheca fuliginea and Cladosporium fulvum on tomatoes, Corynespora melonganae on eggplant, Sphaerotheca humuli, Fusarium oxysporum f. sp. fragariae on strawberries, Botrytis alli on onion, Cercospora apii on oerel, Phaepissriopsis griseola on bean, Erysiphe cícho racearum on tobacco, Dlplocarpon rosae on roses, Elsinoe fawcetti, Penlclllium itálicum, Penisilliumumcumumcumeacumumcumea tomatoes, strawberries, peppers, onions, lettuce, grapes, oranges, cyclamen, roses and hops, Sclerotonia sclerotiorum on cucumbers, aubergines, peppers, lettuce, / * celery, beans, soya, potatoes or sunflower, Sclerotinia cinerea with broskvkvia cinerea melts, Myeosphaerella melonis on cucumbers and melons, etc.

The composition of the invention is particularly effective in suppressing resistant strains of these fungi. The advantage is that the composition has my extremely low toxicity and my small detrimental effect on mammals and fish. It can be applied in fields without any significant toxic effect on important crops.

The present invention also provides a process for the preparation of an active ingredient of the formula (i 'x')

Y '

where

X 'is C 1 -C 2 alkyl, C 1 -C 3 alkoxy, chlorine, fluorine, bromine or iodine, ϊ C 1 -C 2 alkyl, C 1 -C 3 alkoxy, fluorine, bromine or iodine, with the proviso that X * and ϊ 'do not simultaneously represent methyl groups and

H is methyl or ethyl, characterized in that the aniline of formula II '

where

X 'is C 1 -C 2 alkyl, C 1 -C 3 alkoxy, chlorine, fluorine, bromine or iodine; and

Y 'is C 1 -C 2 alkyl, C 1 -C 3 alkoxy, fluoro, bromo or iodo, provided that X' and Y 'are not both methyl, react with ethyl chloroformate or methyl chloroformate in the presence of an inert solvent. Other compounds of formula I which are not within the scope of formula I 'may also be prepared in the same manner.

The reaction is usually carried out in the presence of an inert solvent (for example benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, chloroform, tetrahydrofuran, ethyl acetate, pyridine, dimethylformamide). If desired, the reaction can be carried out in the presence of a dehydrohelogenating agent (for example pyridine, triethylamine, diethylaniline, sodium hydroxide or potassium hydroxide) to give a compound of formula I in high yield. The reaction may be carried out at a temperature of from 0 to 150 ° C and may be carried out within a period of time or up to 10 hours.

The aniline of formula (II) used as starting material in the above process can be prepared according to the methods described in Yakugachi Zaschl, 8, 314-317 (1965) Ber., 34.

343 and 3,354 (1901).

In addition to the process of the invention described above, the reaction of the phenylisocyanate of the formula III is also possible for the preparation of the compounds of the formula I

NCO (III) where

X and Y are as defined above with methanol or ethanol.

The reaction is usually carried out either without a solvent or in the presence of an inert solvent (for example benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, N, N-dimethylformamide, chloroform, or tetrahydrofuran). If desired, a catalyst (e.g., triethylamine, diethylaniline or 1,4-diazabicyclo (2,2,2) octane) may be used. The reaction is normally carried out at a temperature of 0 to 50 ° C β proceeds immediately or for up to 10 hours .

The phenylisocyanate of formula III used in the above process can be prepared by reacting the aniline of formula II with phosgene. This reaction is usually carried out in the presence of an inert solvent (e.g. benzene, toluene, xylene, ethyl acetate) and at a temperature of from 50 ° C to the reflux temperature of the solvent. The reaction proceeds immediately or up to 10 hours.

Several embodiments of the process for preparing the N-phenylcarbamate of Formula I are illustrated by the following examples.

Example 1

Synthesis of ethyl N- (3,5-diisopropyloxyphenyl) kerbamate, (Compound No. 16, Procedure)

Dissolve 3,5-diisopropylaxyaniline (2 g) and diethylaniline (1.5 g) in benzene (20 mL).

To the resulting mixture was added dropwise ethyl chloroformate (1.2 g) from ice cooling. The reaction mixture was allowed to stand at room temperature for 12 hours and then poured into ice-water and extracted with ethyl acetate. The extract was washed with water, dried (MgSO4) and concentrated under reduced pressure. The residue was purified by chromatography on silica gel using a mixture of benzene and tetrahydrofuran as eluent. Give ethyl N- (3,5-diisopropyloxyfenyl) carbamate (1.9 g) in a yield of 67.6%, mp 81.5 DEG-82 DEG C. ^e

Elemental analysis for the calculated: 4.98% N, 64.03% 0, 8.24% H; _t Found: 4.93% N, 63.99% C, 8.32% H.

Example 2

Synthesis of methyl N- (3,5-dimethoxyphenyl) carbamate, (Compound No. 11), Procedure b)

A mixture of 3,5-dimethoxyaniline (8.4 g) and toluene (100 ml) was added dropwise to a toluene solution containing 20 g of phosgene at 10 to 20 ° C. The resulting mixture was gradually heated to reflux, refluxed for 30 minutes and then cooled to room temperature. The solvent was removed by distillation under reduced pressure to give (3,5-dimethoxy) phenyl isocyanate (9.8 g). To the crude product thus obtained was added a methanolic solution (50 ml) of triethylamine (1 g). The resulting mixture was allowed to stand at room temperature for 12 hours, poured into ice-water, and extracted with ethyl acetate. The extract was washed with water, dried over magnesium sulphate and concentrated under reduced pressure. The residue was purified by chromatography on a white gel using a mixture of benzene and tetrahydrofuran as eluent. Methyl N- (3,5-dimethoxyphenyl) kerbemeth (10.2 g) was obtained in a yield of 88% (based on starting 3,5-dimethoxyaniline). Mp 64.5-65 ° C.

Elemental analysis for C: CH ^O ^N calculated:

found:

N 6.63, N 6.65,

56.86% S, 56.97 * C,

6.20% H; 6.31% H.

A few typical in the same manner as the examples of the N-phenylcarbametes of formula I that can be prepared by the above compounds are shown in Table 1.

Table 1

X b- -NHCOR y ^z Compound number X X R Physical constant 1 Cl Cl ch ₃ mp 116.5-117 ° C 2 Cl Cl ^C 2 ^H 5 mp 70.5-71 ° C 3 Br Br ch ₃ mp 131-132 ° C 4 Br Br c ₂ h ₅ mp 118.5-119.5 ° C 5 AND AND ch ₃ mp 158-158.5 ° C 6 AND AND ^C 2 ^H 5 mp 133.5-134 ° C 7 CH ₃ ch ₃ ch ₃ mp 42-43 ° C 8 ch ₃ ch ₃ ^C 2 ^B 5 mp 69-70 ° C 9 ^C 2 ^H 5 ^C 2 ^H 5 CH ₃ nj · ¹ ' ⁵ 1.532 6 10 ^C 2 ^H 5 ^C 2 ^H 5 ^C 2 ^H 5 mp 31-31.5 ° C 11 OCH ₃ OCH ₃ CH ₃ mp 64.5-65 ° C 12 och ₃ OCH ₃ c ₂ h ₅ n * ³ ' ⁵ 1.541 8 13, oc ₂ h ₅ oc ₂ h ₅ CH ₃ n £ ⁵ ' ⁵ 1.533 6 , 4 oc ₂ h ₅ oc ₂ h ₅ ^C 2 ^H 5 n £ ⁵ 1,519 1 15 Dec 0C ₃ H _? (and) OC-iH (i) ch ₃ n £ ² '° 1.521 5 16 OC ₃ H ₇ (i) OC-jOjU) ^C 2 ^H 5 mp 81.5-82 ° C 17 Cl Br ch ₃ mp 102-102.5 ° C 18 Cl Br c ₂ h ₅ mp 84-85 ° C 19 Dec Cl CH ₃ CH ₃ mp 35-36 ° C 20 May Cl CH ₃ ^C 2 ^H 5 mp 78-80 ° C

In practical fungicidal application, the N-phenylcarbamate compounds of formula (I) may be used as such, but are generally used in the form of suitable agricultural compositions such as dusts, wettable sprays, oil sprays, emulsifiable concentrates, tablets, granules, fine granules, aerosols and suspensions. .

These compositions may be prepared by known methods by admixing at least one N-phenylcarbamethyl compound of formula I with a suitable solid or liquid carrier or carriers or diluents, optionally using one or more excipients such as surfactants, adhesives, dlspergers and stabilizers for improving the dispersing properties or other properties of the active ingredient in use.

Examples of solid carriers or diluents include vegetable origin (e.g., flour, tobacco stem powder, soy flour, walnut shell meal, wood flour, sawdust, bran, bark flour, cellulose flour, roet7 liner extraction residues), fibrous materials (eg paper, crushed cardboard, old rags), synthetic plastic powders, clays (eg kaolin, bentonite, fuller), talc, other inorganic materials (eg pyrophyllite, sericitum, pumice, sulfur powder, activated carbon) and chemical fertilizers (eg ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ammonium chloride) ·

Examples of liquid carriers include water, alcohols (e.g. methanol, ethanol), ketones (e.g. acetone, methyl ethyl ketone), ethers (e.g. diethyl ether, dioxane, cellosolv, tetrahydrofuran), aromatic hydrocarbons (e.g. benzene, toluene, xylene, methylnaphthalene), aliphatic hydrocarbons (e.g. petrol, kerosene), esters, nitriles, acid amides (e.g. dimethylformamide, dimethylacetamide), halogenated hydrocarbons (e.g. dichloroethane, carbon tetrachloride), etc.

Examples of surfactants include alkylsulfuric acid esters, alkylsulfonates, alkylarylsulfonates, polyethylene glycol ethers, polyhydric alcohol esters, etc. Examples of β-dispersant adherents include casein, gelatin, starch powder, carboxymethylcellulose, gum arabic, gum arabic, lignin, bentonite, molasses, polyvinyl alcohol, pine oil and agar. As a stabilizer, a flight called PAP (mixture of acidic isopropyl phosphates), a substance called TCP (tricresyl phosphate), toluene oil, epoxidized oil, various surfactants, various fatty acids and their esters, etc. can be used as stabilizers.

The above compositions typically contain at least one N-phenylcarbamethyl compound of formula I in a concentration of from about 1 to about 95% by weight, preferably from about 5 to about 80% by weight.

When only resistant strains of phytopathogenic fungi are present, the N-phenylcarbamate compounds of formula X alone may be used. However, when sensitive strains are present together with resistant strains, it is preferred that their use alternates with benz imidazole thiophthane fungicides and / or fungicides. or cyclic amide-based N-phenylcarbameth compounds are used in combination with benzimidazole thiophthane fungicides and / or cyclic imide fungicides. In such alternate or combined use, the active ingredients may be used alone or in a conventional formulation comprising the suitable carriers or diluents mentioned above.

In the case of combined use, the weight ratio of the N-phenylcarbamate compound of formula (X) to the benzimidazole thiophanate fungicide and / or fungicide on the cyclic imide may range from about 1: 0.1 to 1: 10.0. The concentration of these active ingredients in conventional agricultural compositions is usually from about 1.0 to 95.0% by weight, preferably from about 2.0 to 80.0% by weight.

Table 2 shows typical examples of benzimidazole thiophanate fungicides and cyclic imide fungicides that can be used in this context. The examples do not limit the range of drugs to be used.

Structure

Nézev

Table 2

Compound # N

N

CONHC ₃ H _g (n)

NHCOOCHg methyl-1- (butylkerbamoyl) benzimidazol-2-ylcarbamet

2- (4-thiazolyl) benzimidezole

NHCOOCHg methylbenzimidezol-2-ylcarbemet

O ^z

2- (2-furyl) benzimidazole

WITH

II

NHCNHCOOCH3

NHCNHCOOCH3 p

1,2-bi and (3-methoxycarbonyl-2-thioureido) benzene p

NHCNHCOOCjHg

NHCNHCOOC, H _R

II * ³ p

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

WITH

II 'NHCHCOOCH3' NHP-S-CH 2, 11 ', ⁰ and ₃ s

II nhcnhcooch ₃

NHP-OCH ₃ SOCHi

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

2- (O, O-dimethylthiophosphorylemino) -1- (3'-ethoxycarbonyl-2'-thio-eido) benzene

Structure

Table 2 continuation title

Compound number

N- (3 * 5 ^from dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboxamide

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

Hh 2 CH = CH ₂ Cl o ^CH 3

3- (3 ', 5'-dlchlorophenyl) -5-methyl-5-vinyloxazolidine-2,4-dione

Cl o

Λ

Cl

vs o

ethyl (RS) -3- (3 ', 5'-chlorophenyl) -5-methyl-2,4-dioxooxazolidine-5-carboxylate

A suitable amount of the composition to be used is generally about 10 to 100 g of N-phenylkerbamethyl compound or compounds of formula X per 10 ares. The concentration of the active ingredient (s) is preferably in the range of about 0.005 to 0.5% by weight. However, since the amount of formulation used and its concentration depend on the type of formulation at the time of application, method of administration, disease and crop, these values may increase or decrease beyond these ranges.

In addition, the N-phenylcarbamethyl compounds of the formula I can be used in admixture with other fungicides (except benzimldazole thiophanate fungicides and cyclic imide fungicides), herbicides, insecticides, ecaricides, fertilizers, etc.

Practical examples of the fungicidal compositions of the invention are given by way of illustration in the following examples. Parts and% are always parts and% by weight.

Formulation example 1 part of compound 4, 88 parts clay β 10 parts talc is thoroughly powdered and mixed to form a dust containing 2% active ingredient.

Formulation Example 2 parts of Compound No. 2, 45 parts of diatomaceous earth, 20 parts of white carbon black, 3 parts of sodium lauryl sulfate as a surfactant, and 2 parts of calcium lignin sulphate as a dispersant are mixed together to form a powder. A wettable powder containing 30% of the active ingredient is obtained.

Formulation Example 3 parts of Compound No. 1, 45 parts of diatomaceous earth, 2.5 parts of calcium alkylbenzenesulfonate as a surfactant, and 2.5 strengths of calcium ligninsulfonate as a dispersant are mixed together from the comminution to a powder. A wettable powder containing 50% of the active ingredient is obtained.

Example of device 4

10 parts of compound No. 3, 80 parts of cyclohexanone and 10 parts of polyoxyethylene alkylaryl ether as emulsifier are mixed together to form an emulsifiable concentrate containing 10% active ingredient.

Example of device 5

While mixing thoroughly into powder, 1 part of Compound No. 1, part of Compound No. C, 88 parts of clay and 10 parts of talc are mixed together. A dust containing 2% of the active ingredients is obtained.

Example of device 6

Two parts of Compound No. 4, two parts of Compound No. E, 86 parts of clay e, 0 parts of talc are mixed together with thorough processing as a powder. A dust containing 4% of the active ingredients is obtained.

Example of device 7

One part of Compound No. 13, two parts of Compound No. X, 87 parts of clay and .0 parts of talc are mixed intimately together with pulverization, not powder. A dust containing 3% of the active ingredients is obtained.

Formulation Example 8 parts of Compound No. 9, 0 parts of Compound No. G, 45 parts of diatomaceous earth, 20 parts of white carbon black, 3 parts of nontrium leuryl sulphate as a surfactant, and 2 parts of calcyl lignin sulphonate as a dispersant are mixed together. A wettable powder is obtained containing 30% of the active ingredients.

Example composition 9 t

0 parts of Compound No. 6, 40 parts of Compound No. A, 45 parts of diatomaceous earth, 2.5 parts of alkylbenzene sulphonate, as a wetting agent, and 2.5 parts of calcium lignin sulphonate as dispersant are mixed together with comminution to a powder. A wettable powder is obtained containing 50% of the active ingredients.

Formulation example 10 parts of compound No. 2, 50 parts of compound No. P, 8 parts of diatomaceous earth, 3.5 parts of calcium alkylbenzene sulphonate as a surfactant, and 3.5 parts of calcium lignin sulphonate as a dispersant are mixed together after mixing. simultaneous processing of no rainfall. A wettable powder containing 15% of the active ingredients is obtained.

Formulation example 11 parts of Compound No. 14, 30 parts of Compound No. J, 40 parts of powdered sucrose, 5 parts of white carbon black, 3 parts of sodium leuryl sulphate as a wetting agent, and 2 parts of calcium lignin sulphonate as dispersant are mixed together from simultaneous grinding přéěek.

A wettable powder was obtained containing 30% of the active ingredients.

Example composition 12 parts of Compound No. 13, 20 parts of Compound No. H, 45 parts of diatomaceous earth, 2.5 parts of calcium alkylbenzene sulphonate as a wetting agent, and 2.5 parts of calcium lignin sulphonate as dispersing agent are mixed with pulverization. A wettable powder was obtained containing 50% of the active ingredients.

Example composition 13 parts of compound No. 20, 25 parts of compound No. K, 8 parts of diatomaceous earth, 3.5 parts of calcium alkylbenzenesulfonate as a wetting agent, and 3.5 parts of calcium ligninsulfonate as a dispersant are mixed together while comminuting not powder. A wettable powder was obtained containing 75% of the active ingredients.

Example of device, 4

One part of Compound No. 18, part of Compound No. G, 88 parts of clay, and 10 parts of town were mixed from the simultaneous pulverization of no powders. A dust containing 2% of the active ingredients is obtained.

Example of a device

0.5 part of compound no. 7, 0.5 parts of Compound No. B, 89 parts of clay and 10 parts of talc are mixed together while comminuting the powder. Dust containing% active ingredients is obtained.

Example of 16 '

Two parts of Compound No. 13, 1 part of Compound No. A, 87 parts of clay and .0 parts of town were mixed together from the simultaneous pulverization of no powders. A dust containing 3% of the active ingredients is obtained.

Formulation example 17 parts of Compound No. 3, 30 parts of Compound No. D, 40 parts of powdered sucrose, 5 parts of white carbon black, 3 parts of sodium lauryl sulphonate, as a wetting agent, and 2 parts of calcium lignin sulphonate as dispersant are mixed together from simultaneous comminution to préšek.

A wettable powder was obtained containing 30% of the active ingredients.

Formulation Example 18 parts of Compound No. 10, 20 parts of Compound K, 45 parts of diatomaceous earth, 2.5 parts of calcium alkylbenzene sulphonate as a surfactant, and 2.5 parts of calcium lignin sulphonate as dispersant are mixed together from simultaneous pulverization. A wettable powder is obtained containing 50% of active ingredients.

Formulation Example 19 parts of Compound No. 8, 25 parts of Compound No. I, 18 parts of diatomaceous earth, 3.5 parts of calcium alkylbenzenesulfonate as a wetting agent, and 3.5 parts of calcium lignin sulphonate as dispersant are mixed together while grinding powder. A wettable powder was obtained containing 75 # active ingredients.

The following examples show some typical test data showing the excellent fungicidal activity of the N-phenylcarbametes of formula I. These compounds are used for comparative purposes.

Compound

Comment

Control Compound (s)

Synthesized for comparative purposes

Cl

NHCOCH3

Control Compound (b)

Synthesized for comparative purposes

Cl o

II

NHCOCH3

Control Compound (c)

Synthesized for comparative purposes

Oo

NHCOCHq

Cl

Control compound (d)

Synthesized for comparative purposes nhcoc ₂ h ₅

Cl

Control compound (s)

Synthesized for comparative purposes

Cl

O

II nhcoc ₂ h ₅ continued

Compound

Note

Control compound (f)

Synthesized for comparative purposes rynhcoc ₂ h ₅

Cl

Control compound (g)

Synthesized for comparative purposes

NHCOCH3

Br

Control compound (h)

Synthesized for comparative purposes

control compound (s)

in —nc (ch ₃ ) ₂

Agriculturel Biological Cheinietry, 1 707-1 719 (1971)

Control Compound (s)

Cl

Agriculture Biological Chemistry, 2Ϊ. '707 to 1,719 (1971)

Control compound (k)

O

II nhcoch ₂ ch ₂ ci

Agriculture Biological Chemistry, 2Z »707 to 1,719 (1971)

Cl continued

Compound

Note

Control Compound (1) Agricultural Blologcal Calami, JJ, 1 707-1 719 (1971)

O

II

NHCOCH ₂ CN

Cl

Swep »

Commercial herbicide available

Cl

O nhcoch ₃

Cl

Chlorprofam

Commercial herbicide available

Cl

Berban

Cl

CEPC o

II

NHCOCH ch ₃ ch ₃

Commercially available heribicide o

II

NHCOCH ₂ CsCCH ₂ Cl

Commercial herbicide available

CYnhcoch ₂ ch ₂ ci

Cl

Profham

Commercially available herbicide, _, O .CH,

NHCOCH 3 = / ^ ch ₃ continued

Compound

Note

Chlorbufám

Commercially available herbicide

Cl

Benomyl

Commercially available fungicide conhc ₄ h ₉

NHCOOCHj

Thiophonate-methyl

Commercially available fungicide

WITH

II

NHCNHCOOCH3

NHCNHCOOCH · »

II ³ p

Karbendazim

Commercially available fungicide

NHCOOCH3

Thiabendazole

Commercially available fungicide t

Test Example 1

Test of protective effect against powdery mildew of cucumber (Spheerotheca fuliginee)

A 90 ml pot is not filled with sandy soil in which the seeds of the cucumber (Segami-hanjiro variety) are sown. Cultivation is carried out in a greenhouse for 8 days. Non-obtained seedlings having cotyledons do not spray a test compound treated with an emulsifiable concentrate or wettable powder which is diluted with water in an amount of 10 ml per pot. The seedlings are then inoculated with a spore suspension of a resistant or susceptible strain of Spheerotheca fuliginea, which is sprayed onto it and cultivated in a greenhouse. The infection status on the plants is monitored after 10 days. The degree of damage is determined as described above. The results are shown in Table 3.

The percentage of infected area is measured on the scanned sheets and graded by one of the grades 0, 0.5, 1, 2, 4 according to the following scheme.

Degree of disease Percentage of leaf area affected by infection 0 no infection 0.5 Less than 5% of the area infected 1 less than 20% of the area infected 2 less than 50% of areal infected 4 infected with 50% areal or more

The sharpness of the disease is calculated according to the following equation:

degree of disease x number of leaves

Disease Sharpness = ———————— χ 100 (%) 4x total number of sheets examined

The prevention value is calculated using the following equation:

Disease Sharpness in the Test Pot Prevention value = 100 - - - Disease Sharpness in the untreated pot

Table 3

Compound Active ingredient concentration (ppm) Prevention value when inoculation resistant strain (%) Inoculation prevention value sensitive strain (*) 1 200 100 ALIGN! 0 2 200 100 ALIGN! 0 3 200 100 ALIGN! 0 4 200 100 ALIGN! . 0 5 200 100 ALIGN! 0 6 200 100 ALIGN! 0 7 200 100 ALIGN! 0 8 200 100 ALIGN! 0 9 200 98 0

continuation of Table 3

Compound Active ingredient concentration (ppm) Prevention value when inoculation resistant strain (%) Inoculation prevention value sensitive strain (») ' 10 200 100 ALIGN! 0 11 200 100 ALIGN! 0 12 200 95 0 13 200 98 0 14 200 100 ALIGN! 0 15 Dec 200 95 0 16 200 100 ALIGN! 0 17 200 100 ALIGN! 0 18 200 100 ALIGN! 0 19 Dec 200 100 ALIGN! 0 20 May 200 100 ALIGN! 0 Control Compound (s) 200 0 0 Control Compound (b) 200 0 0 Control Compound (c) 200 0 0 Control compound (d) 200 0 0 Control compound (s) 200 0 0 Control compound (f) 200 0 0 Control compound (g) 200 0 0 Control compound (h) 200 0 0 Control Compound (s) 200 0 0 Control Compound (s) 200 0 0 Control compound (k) 200 0 0 Control Compound (1) 200 0 0 Swep 200 0 0 Chlorprofam 200 0 0 Barban 200 25 0 ” CKPC 200 0 0 Profam 200 0 0 Chlorbufám 200 0 0 Benomyl 200 0 100 ALIGN! Thiethane-methyl 200 0 100 ALIGN! Karbendazim 200 0 100 ALIGN!

As is apparent from the results shown in Table 3, the N-phenylcarbamates of the formula I according to the invention show an excellent preventive effect on a resistant strain, but do not show a preventive effect on a susceptible strain. In contrast, commercially available fungicides such as Benomyl, Thiophenet-methyl and Carbendazim show a significant suppressive effect on the susceptible strain but not the resistant strain. Other compounds structurally similar to the N-phenylcarbemetes of the formula show no fungicidal effect on either the susceptible strain or the resistant strain.

Test Example 2

Testing of the protective effect against sugar beet (Cercospora beticola)

A flower pot of 90 ml is filled with sandy soil, in which the seeds of sugar beet (Detroit óark red.) Are sown. Cultivation is carried out in a greenhouse for 20 days. The resulting seedlings are sprayed at a rate of 10 ml per pot with the test compound formulated into an emulsifiable concentrate or wettable powder and diluted with water. Then the seedlings are inoculated with a spore suspension of a resistant or susceptible strain of Cercospora beticola which is sprayed onto them. The pot was covered with polyvinyl chloride foil to ensure high humidity, and cultivation in the greenhouse was continued for 10 days. The degree of deterioration is determined in the same manner as in Test Example 1. The results are shown in Table 4.

Table 4

Compound number Active ingredient concentration (ppm) Prevention value when inoculation resistant tribe (56) Prevention value when inoculated with a susceptible strain («) 1 200 100 ALIGN! 0 50 100 ALIGN! 0 2 200 100 ALIGN! 0 50 98 0 3 200 100 ALIGN! 0 50 100 ALIGN! 0 4 200 100 ALIGN! 0 50 94 0 5 200 100 ALIGN! 0 6 200 100 ALIGN! 0 7 200 100 ALIGN! 0 8 200 100 ALIGN! 0 9 200 100 ALIGN! 0 10 200 100 ALIGN! 0 11 200 100 ALIGN! 0 12 200 98 0 13 200 100 ALIGN! 0 14 200 100 ALIGN! 0 15 Dec 200 100 ALIGN! 0 16 200 95 0 17 200 100 ALIGN! 0 18 200 100 ALIGN! 0 19 Dec 200 100 ALIGN! 0

, 9 continued Table 4

Compound number Active ingredient concentration (ppm) Inoculation prevention value resistant strain ($) Inoculation prevention value sensitive strain (») 20 May 200 100 ALIGN! 0 Checklist 200 0 0 Compound (s) 50 0 0 Checklist 200 0 0 Compound (b) 50 0 0 Checklist 200 0 0 Compound (c) 50 0 0 Checklist 200 0 0 Compound (d) 50 0 0 Checklist 200 0 0 Compound (s) 50 0 0 Checklist 200 0 0 compound (f) 50 0 0 Checklist 200 0 0 Compound (g) 50 0 0 Checklist 200 0 0 Compound (h) 50 0 0 Checklist 200 0 0 Compound (s) 50 0 0 Checklist 200 0 0 Compound (s) 50 0 0 Checklist 200 0 0 compound (k) 50 0 0 Checklist 200 0 0 compound (1) 50 0 0 Swep 200 0 0 50 0 0 Chlorprofam 200 0 0 50 0 0 Barban 200 34 0 50 0 0 CEPC 200 0 0 50 0 0 Profam 200 0 0 50 0 0 Chlorbufám 200 0 0 50 0 0 Benomyl 200 0 100 ALIGN! 50 0 100 ALIGN! Thiophanate-methyl 200 0 100 ALIGN! 50 0 98

As can be seen from the results shown in Table 4, the N-phenylkerbemates of the formula I according to the invention show an excellent preventive effect on a resistant strain, but do not show a preventive effect on a susceptible strain. In contrast, commercially available fungicides such as Benomyl, Thiophanate-methyl and Carbendazira show a marked effect on a susceptible but not resistant strain. Other compounds structurally similar to the N-phenylcarbamates of the formula show no fungicidal effect on either the susceptible strain or the resistant strain.

Test Example 3

Test of preventive effect on pear scab (Venturia nashicola)

90 ml pots are not filled with sandy soil, where pear seeds (Chojuro varieties) are sown. Cultivation is carried out in a greenhouse for 20 days. No seedling seedlings are sprayed at 10 ml per pot with the test compound formulated into an emulsifiable concentrate or wettable powder and diluted with water. Then the seedlings are inoculated with a spore suspension of a resistant or susceptible strain of Venturia nashicola which is sprayed onto them. The plants are placed in a high humidity room at 20 ° C for 3 days and then irradiated with an ultraviolet lamp at 20 ° C for 20 days. The degree of damage was determined in the same manner as in Test Example 1. The results are shown in Table 5.

Table 5

Compound number Active ingredient concentration (ppm) Prevention value when inoculation resistant tribe (#) Prevention value when inoculated with a sensitive strain (#) 1 200 100 ALIGN! 0 50 100 ALIGN! 0 2 200 100 ALIGN! 0 50 100 ALIGN! 0 3 200 100 ALIGN! 0 50 ICO 0 4 200 100 ALIGN! 0 50 100 ALIGN! 0 5 200 100 ALIGN! 0 6 200 100 ALIGN! 0 7 200 100 ALIGN! 0 8 200 ioo 0 9 200 98 0 10 200 100 ALIGN! 0 11 200 100 ALIGN! 0 12 200 95 0 13 200 100 ALIGN! 0 14 200 100 ALIGN! 0 15 Dec 200 100 ALIGN! 0 16 200 100 ALIGN! 0 17 200 100 ALIGN! 0 18 200 100 ALIGN! 0 19 Dec 200 100 ALIGN! 0 20 May 200 100 ALIGN! 0 Benomyl 200 0 100 ALIGN! 50 0 100 ALIGN! Thi ofenét-me tulle 200 0 100 ALIGN! 50 0 100 ALIGN!

As can be seen from the results shown in Table 5, the N-phenylcarbamates of the formula I according to the invention show an excellent preventive effect on a resistant strain, but do not show a preventive effect on a susceptible strain. In contrast, commercially available fungicides such as Benomyl, Thiophanomethyl and Carbendazim show a significant suppressive effect on the susceptible strain but not on the resistant strain.

Test Example 4

Test of preventive effect on cercospora of groundnut (Cercospora arechidicola)

A 100 ml plastic pot is not filled with a sandy soil in which peanuts are sown in oil (variety Chiba hanryusei). Cultivation is carried out in a greenhouse for 14 days. The resulting seedlings are sprayed at a rate of 10 ml per pot with the test compound treated as an emulsifiable concentrate or wettable powder and diluted with water.

2,

Then the seedlings are inoculated with a spore suspension of a resistant or susceptible strain of Cercospore arechidicole and sprayed onto them. The pot was covered with polyvinyl chloride foil to ensure high humidity and cultivation in the greenhouse was continued for 10 days. The degree of damage is determined in the same manner as in Test Example 1. The results are shown in Table 6.

Compound number Active ingredient concentration (ppm) Prevention value when inoculation resistant strain (%) Prevention value when inoculated with a susceptible strain W) 1 200 100 ALIGN! 0 50 100 ALIGN! 0 2 200 100 ALIGN! 0 50 , 00 0 3 200 100 ALIGN! 0 50 100 ALIGN! 0 4 200 100 ALIGN! 0 50 100 ALIGN! 0 5 200 100 ALIGN! 0 6 200 100 ALIGN! 0. 7 200 , 00 0 8 200 100 ALIGN! 0 9 200 , 00 0 10 200 100 ALIGN! 0 11 200 100 ALIGN! 0 12 200 , 00 0 13 200 96 0 14 200 100 ALIGN! 0 15 Dec 200 98 0 16 200 100 ALIGN! 0 17 200 98 0 18 200 100 ALIGN! 0 19 Dec 200 100 ALIGN! 0 20 May 200 100 ALIGN! 0 Benomyl 200 0 100 ALIGN! 50 0 100 ALIGN! Thanothan-methyl 200 0 100 ALIGN! 50 0 , 00

How. It can be seen from the results shown in Table 6 that the N-phenylcarbamates of the formula I according to the invention show excellent. a preventive effect on the resistant strain, but do not show a preventive effect on the responsive strain. In contrast, commercially available fungicides such as Benomyl, Thiophanate-methyl and Carbendazim show a significant suppressive effect on the susceptible strain but not the resistant strain.

Test Example 5

Test of preventive effect against blue orange rot (Penicillium italieum)

Orange fruits (Unshu varieties) are washed with water and air dried. The fruits are ee immersed in a solution of the test compound prepared by diluting an emulsifiable concentrate containing the test compound with water for 1 minute. After air-drying, the fruits are inoculated by spraying a suspension of spores of a resistant strain and a sensitive strain of Penicillium italieum. The oranges are placed in a high humidity area for 14 days. The degree of damage is determined as follows:

The percentages of the infected area are measured on the fruit examined and graded by one of the grades 0, 1, 2, 3, 4 and 5 according to the following scheme:

Degree diseases Percentage of area infected with Infection t fetus 0 no infections 1 less than 20% infected areas 2 less than 40% infected areas 3 less than 60% infected area ^r 4 less than 80% infected areas 5 infected with 80% of the area or more

Calculation of the degree of damage and preventive value is performed as in Test Example 1. The results are shown in Table 7.

Table 7

Compound number Concentration of the active ingredient (ppm) Prevention value when inoculation resistant strain (*) Prevention value when inoculated with a sensitive strain (») 1 200 100 ALIGN! 0 50 100 ALIGN! 0 2 200 100 ALIGN! 0 50 (00 0 3 200 100 ALIGN! 0 50 100 ALIGN! 0 4 200 100 ALIGN! 0 50 100 ALIGN! 0 5 200 100 ALIGN! 0 6 200 100 ALIGN! 0 7 200 100 ALIGN! 0 8 200 100 ALIGN! 0 9 200 100 ALIGN! 0 10 200 98 0 11 200 100 ALIGN! 0 12 200 100 ALIGN! 0 13 200 100 ALIGN! 0 14 200 100 ALIGN! 0 15 Dec 200 100 ALIGN! 0 16 200 100 ALIGN! 0 17 200 100 ALIGN! 0

continuation of Table 7

Compound number Active ingredient concentration (ppm) Prevention value when inoculation resistant strain (%) Prevention value when inoculated with a susceptible strain W) 1Θ 200 100 ALIGN! 0 19 Dec 200 100 ALIGN! 0 20 May 200 100 ALIGN! 0 Benomyl 200 0 100 ALIGN! 50 0 100 ALIGN! Thiophanate-methyl 200 0 100 ALIGN! 50 0 100 ALIGN! Thiabendazole 200 0 , 00 50 0 , 00

Jpk is shown in Table 7, the N-phenylcarbamates of the formula I show an excellent preventive effect against a resistant strain, while commercially available known fungicides such as Benomyl, Thiophanot-methyl and Thiabendazole show a remarkable preventive effect against a susceptible strain.

Test Example 6

Non-crop phytotoxicity test

150 ml plastic pots are not filled with sandy soil in which the seeds of wheat (Norin No 61), apple (Kogyoku variety) and peanuts (Chiba henzyusei variety) are sown. The cultivation is carried out in a greenhouse. The resulting seedlings are sprayed with the test compound prepared by diluting the appropriate emulsifiable concentrate or wettable powder with water. The ee seedlings are cultivated for an additional 10 days in a greenhouse and then phytotoxicity is assessed according to the following criteria:

Range phytotoxicity Observation results - no abnormality + abnormality due to phytotoxicity observed in part of the crop ++ abnormality due to phytotoxicity observed in all test crops +++ crop plants wither due to phytotoxicity

Table 8

Compound number Concentration of the active ingredient (ppm) Phytotoxicity wheat apple tree peanuts oil 1 1 000 2 1 000 - - - 3 1 000 - - - 4 1 000 - - - 5 1 000 - - - 6 1 000 - - - 7 1 000 - - - 8 1 000 - - - 9 1 000 - - - 10 1 000 - - - 11 1 000 - - - 12 1 000 - - - 13 1 000 - - - 14 1 000 - - - 15 Dec 1 000 - - - 16 1 000 - - - 17 1 000 - - - 18 1 000 - - - 19 Dec 1 000 - - - 20 May 1 000 - - - Barben 1 000 - ++ ++ CEPC 1 000 - ++ ++ Swap 1 000 ++ ++ +

As is apparent from the results shown in Table 8, the N-phenylcarbamates of the formula I according to the invention show no substantial phytotoxicity, while commercially available herbicides of similar structure exhibit considerable phytotoxicity.

Test Example 7

Test of preventive effect against cucumber powdery mildew in cucumbers (Spheerothece fuliginee)

The 90 ml plastic pot is not filled with sandy soil, in which cucumber seeds (Sagami-hanjiro varieties) are sown. Cultivation is carried out in a greenhouse for 8 days. No seedlings having cotyledons were sprayed with 10 ml of the test compound or compounds formulated into an emulsifiable concentrate or wettable powder and diluted with water in an amount of 10 ml. Then the seedlings are inoculated with a spore suspension of a resistant or susceptible strain of Spheerothece fuliginee, which is sprayed on and cultivated in a greenhouse. The infection status on the plants is monitored after 10 days. The degree of damage was determined in the same manner as in Test Example 1. The results are shown in Table 9.

Table 9

Compound number Active ingredient concentration (ppm) Prevention value (») 1 100 ALIGN! 42 1 20 May 0 4 100 ALIGN! 44 4 20 May 0 5 100 ALIGN! 38 5 20 May 0 9 100 ALIGN! 36 9 20 May 0 10 100 ALIGN! 28 10 20 May 0 11 100 ALIGN! 24 ti 20 May 0 13 100 ALIGN! 36 13 20 May 0 14 100 ALIGN! 28 14 20 May 0 15 Dec 100 ALIGN! 36 15 Dec 20 May 0 16 100 ALIGN! 32 16 20 May 0 19 Dec 100 ALIGN! 36 19 Dec 20 May 0 20 May 100 ALIGN! 32 20 May 20 May 0 AND 100 ALIGN! 43 A, 20 May 12 F 100 ALIGN! 43 F 20 May 8 G 100 ALIGN! 42 G 20 May 8 H 100 ALIGN! 40 H 20 May 5 11 + A 20 -¼ 20 100 ALIGN! 1 + F 20 + 20 100 ALIGN! 4 + A 20 + 20 100 ALIGN! 4 + F 20 + 20 100 ALIGN! 5 + A 20 + 20 100 ALIGN! 5 + F 20 * 20 100 ALIGN! 5 + G 20 + 20 100 ALIGN! 5 + H 20 + 20 100 ALIGN! 8 + G 20 + 20 100 ALIGN! 8 + H 20 + 20 100 ALIGN! 9 + A 20 + 20 100 ALIGN! 9 + F 20 + 20 100 ALIGN! 9 and G 20 + 20 100 ALIGN! 9 + H 20 + 20 100 ALIGN! 10 + A 20 + 20 100 ALIGN! 10 + F 20 + 20 100 ALIGN! 11 + A 20 20 100 ALIGN! 11 + F 20 + 20 100 ALIGN!

continuation of Table 9

Compound number Active ingredient concentration (ppm) The value of ^ prevention , 3 + G 20 + 20 100 ALIGN! 13 + H 20 + 20 100 ALIGN! 14 + G 20 + 20 100 ALIGN! 14 + H 20 + 20 100 ALIGN! 15 + A 20 + 20 100 ALIGN! 15 + P 20 + 20 , 00 15 + G 20 + 20 , 00 15 + H 20 + 20 , 00 16 + A 20 + 20 100 ALIGN! 16 + F 20 + 20 100 ALIGN! 19 + G 20 + 20 100 ALIGN! 19 f H 20 + 20 100 ALIGN! 20 + G 20 + 20 100 ALIGN! 20 + H 20 + 20 100 ALIGN!

As can be seen from the results shown in Table 9, the co-use of the N-phenylcarbenates of the formula I according to the invention with benzimidazole thiophanate fungicides and / or cyclic imide fungicides exhibits a much better preventive effect than their use alone.

Test Example 8

Test of preventive effect against gray tomato mold (Botrytis cineree)

90 ml plastic pots are not filled with sandy soil into which tomato seeds (Fukuju variety 2) are sown. Cultivation is carried out for 4 weeks in a greenhouse. The resulting four-leaf seedlings are sprayed with 10 ml per pot into the test compound or compounds formulated into an emulsifiable concentrate or wettable powder and diluted with water. The seedlings are inoculated with a suspension of spores of a resistant or sensitive strain of Botrytis cinerea which is sprayed onto them. The seedlings are then placed in a high humidity and 20 ° C room for 5 days. The degree of damage was determined in the same manner as in Test Example 1. The results are shown in Table 10.

Table 10

Compound * # Active ingredient concentration (ppm) Prevention value («) 1 50 36 1 , 0 0 2 50 40 2 , 0 0 3 50 32 3 , 0 0 4 50 38 4 , 0 0 5 , 00 42 5 20 May 0

continuation of Table 10

Compound number Active ingredient concentration (ppm) Value 6 100 ALIGN! 35 6 20 May 0 7 50 28 7 10 0 8 50 32 8 10 0 9 50 44 9 10 0 10 50 36 10 10 0 11 50 38 11 10 0 12 50 30 12 10 0 13 «00 42 13 20 May 0 14 100 ALIGN! 39 14 20 May 0 15 Dec 250 45 15 Dec 50 12 16 250 42 16 50 8 17 100 ALIGN! 40 , 7 20 May 0 18 , 00 38 18 20 May 0 19 Dec 50 26 , 9 10 0 20 May 50 32 20 May , 0 0 AND 100 ALIGN! 46 AND 20 May , 8 J 100 ALIGN! 42 J 20 May 15 Dec TO 100 ALIGN! 40 TO 20 May 8 L 100 ALIGN! 38 L 20 May 7 1 + I 10 + 20 , 00 1 + J 10 + 20 , 00 1 + K 10 + 20 100 ALIGN! 1 + L 10 + 20 , 00 2 + 1 , 0 + 20 100 ALIGN! 2 + K 10 + 20 100 ALIGN! 3 + 1 10 + 20 100 ALIGN! 3 + L 10 + 20 , 00 4 + 1 10 + 20 100 ALIGN! 5 + 1 20 + 20 100 ALIGN! 5 + J 20 + 20 , 00 6 + 1 20 + 20 100 ALIGN! 6 + K 20 + 20 , 00

continued table, 0

Compound number Concentration of the active ingredient (ppm) Prevention value (#) 7 + 1 10 + 20 100 ALIGN! 7 + J , 0 + 20 100 ALIGN! 8 + 1 10 + 20 100 ALIGN! 9 + 1 10 + 20 100 ALIGN! 10 + 1 10 + 20 100 ALIGN! 11 + 1 10 + 20 100 ALIGN! 12 + X 10 + 20 100 ALIGN! 13 + 1 20 + 20 100 ALIGN! 14 + 1 20 + 20 100 ALIGN! 15 + 1 50 + 20 100 ALIGN! 16 + 1 50 + 20 100 ALIGN! 17 + 1 20 + 20 100 ALIGN! 18 + 1 20 + 20 100 ALIGN! 19 + 1 10 + 20 100 ALIGN! 20 + 1 10 + 20 100 ALIGN!

As can be seen from the results shown in Table 10, the combined use of the N-phenylcarbamates of the formula I according to the invention with benzimidazole thiophenetic fungicides and / or cyclic imide fungicides exhibits a much better preventive effect than their use alone.

Test Example 9

Test of preventive action against sugar beet (Cercospora beticola)

90 ml ee pots are filled with sandy soil, where the seeds of sugar beet (Detroit dark red.) Are sown. Cultivation is carried out in a greenhouse for 20 days.

The resulting seedlings are not sprayed at a rate of 10 ml per pot with the test compound or compounds formulated into an emulsifiable concentrate or wettable powder and diluted with water. Then the seedlings are inoculated with a suspension of spores of a resistant or susceptible strain of Cercospora beticola and sprayed onto them.

The pot was covered with polyvinyl chloride foil to ensure high humidity and the cultivation in the greenhouse was continued for 10 days ... The degree of damage was determined in the same manner as in Test Example 1. The results are shown in Table 11.

Table ,,

Compound number Active ingredient concentration (ppm) Prevention value (*) 1 40 38 1 10 0 2 40 44 2 10 0 3 40 42 3 10 2 4 40 36 4 10 0 5 40 36 5 10 0 6 40 42 6 10 0 7 40 32 7 10 0 8 40 35 8 10 0 10 40 38 10 10 0 11 40 35 11 40 0 12 40 35 12 10 0 13 40 36 13 it 0 14 40 34 14 10 0 16 100 ALIGN! 27 Mar: 16 20 May 0 17 40 36 17 10 0 18 40 34 18 10 0 C 20 May 26 C 5 0 E 40 42 E 10 0 G 40 46 G , 0 8 H 20 May 27 Mar: H 5 0 1 + C 10 + 5 100 ALIGN! 1 + E 10 + 10 100 ALIGN! 1 + G 10 + 10 100 ALIGN! 1 + H 10 + 5 100 ALIGN! 2 + C 10 + 5 100 ALIGN! 2 + E , 0 + 10 100 ALIGN! 2 + G 10 + 10 100 ALIGN! 2 + H 10 + 5 100 ALIGN! 3 + C 10 + 5 100 ALIGN! 3 + E 10 + 10 100 ALIGN! 3 + G 10 + 10 100 ALIGN! 3 + H 10 + 5 , 00 4 + G 10 + 10 , 00 4 + H 10 + 5 100 ALIGN! 5 + G 10 + 10 100 ALIGN! 5 + H 10 + 5 , 00 6 + C 10 + 5 100 ALIGN! 6 + E 10 + 10 100 ALIGN! 6 + G 10 + 10 , 00 6 + H 10 + 5 100 ALIGN!

'227336 continuation of Table 1,

Compound number. Concentration of the active ingredient (ppa) Prevention value ») 7 + C 10 + 5 100 ALIGN! 7 + E 10 + 10 100 ALIGN! 7 + G 10 + 10 100 ALIGN! 7 + H 10 + 5 100 ALIGN! 8 + C 10 + 5 100 ALIGN! 8 + E 10 + 10 100 ALIGN! 10 + G 10 +, 0 100 ALIGN! 10 + H 10 + 5 100 ALIGN! 11 + G 10 + 10 100 ALIGN! 11 + H 10 + 5 100 ALIGN! 12 + C 20 + 5 , 00 12 + E 20 + 20 100 ALIGN! 12 + G 10 +, 0 100 ALIGN! 12 + H 10 + 5 100 ALIGN! 13 + C 10 + 5 , 00 13 + E 10 + 10 100 ALIGN! 14 + C , 0 + 5 100 ALIGN! 14 + E 10 +, 0 100 ALIGN! , 6 + G 20 + 10 100 ALIGN! 16 + H 20 + 5 > 00 17 + G , 0 +, 0 100 ALIGN! 17 + H , 0 + 5 100 ALIGN! , 8 + G , 0 + 10 100 ALIGN! 18 + H , 0 + 5 100 ALIGN!

As can be seen from the results in Table 11, the combined use of the Formula I N-phanylcarbamates of the present invention with benzimidazole thlophenate fungicides and / or cyclic imide fungicides exhibits a much better preventive effect than their actual use.

Test Example 10

Test of preventive effect against blue orange rot (Penicillium itelicum)

The orange fruits (Unshu varieties) are washed with water and air-dried. The fruits are immersed in a solution of the test compound prepared by diluting an emulsifiable concentrate containing the test compound with water for 1 minute.

After air-drying, the fruits are inoculated by spraying a suspension of spores of a resistant strain and a sensitive strain of Penicillium italicum. The oranges are placed in a high humidity area for 14 days. The degree of damage ee is determined in the same manner as in Test Example 5. The results are shown in Table 2.

♦ • 3,

Table 12

Compound Concentration Prevention value of active ingredient number '(&) (ppm)

1 1 40 10 35 0 2 40 43 2 10 0 3 40 42 3 10 0 4 40 46 4 10 0 5 40 36 5 10 0 7 40 30 7 10 0 (B) 40 38 (B) 10 0 D 80 23 D 20 May 0 H 80 42 H 20 May 0 1 + B 10 + 10 100 ALIGN! 1 + D 10 + 20 100 ALIGN! 1 + H 10 + 20 100 ALIGN! 2 + B 10 + 10 100 ALIGN! 2 + D 10 + 20 100 ALIGN! 2 + H 10 + 20 100 ALIGN! 3 + B 10 + 10 100 ALIGN! 3 + C 10 + 20 100 ALIGN! 3 + H 10 + 20 100 ALIGN! 4 + B 10 + 10 100 ALIGN! 4 + D 10 + 20 100 ALIGN! 4 + H 10 + 20 100 ALIGN! 5 + B 10 + 10 100 ALIGN! 5 + D 10 + 20 , 00 7 + B 10 + 10 , 00 7 + D 10 + 20 100 ALIGN!

As can be seen from the results shown in Table 12, the combined use of the N-phenylcarbamates of the formula I according to the invention with benzimidazole thiophenate fungicides β / or cyclic imide fungicides shows a much better preventive effect than their use alone.

Claims (7)

SUBJECT OF THE INVENTION What is claimed is: 1. A fungicidal composition comprising a fungicidally effective amount of an active ingredient and a carrier, which comprises as an active ingredient a compound of formula (I): II NHCOR ÍX), 227336 32 wherein each of X and Y, which are the same or different, represents an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a halogen atom; and R is methyl or ethyl. 2. The fungicidal composition of claim 1, wherein the compound of formula (I) is a compound wherein each of X and Y, which are the same or different, is methyl, ethyl, methoxy, ethoxy, propoxy, chloro, a bromine atom or an iodine atom o R is methyl or ethyl. 3. A fungicidal composition according to claim 4, wherein the compound of formula (X) comprises a compound in which each of X and Y, which are the same, represents a chlorine atom or a bromine atom, and R is as defined above. 4. A fungicidal composition according to claim 1, wherein the compound of formula (I) comprises a compound wherein each of X and Y, which are the same or different, is C1-C2alkyl, C1-C3alkoxy. carbon or halogen atoms, with the proviso that X and Y do not simultaneously represent chlorine or bromine atoms. 5. A process for the preparation of an active ingredient of the formula (I ') according to (I) Y 'where. X 'is C 1 -C 2 alkyl, C 1 -C 3 alkoxy, chlorine, fluorine, bromine or iodine, Y 'is C 1 -C 2 alkyl, C 1 -C 3 alkoxy, fluoro, bromo or iodo, provided that X' and Y 'are not simultaneously methyl e R is methyl or ethyl, characterized in that the aniline of formula II ' X ' X \ -nh ₂ (II ') Y ‘where X 'is C 1 -C 2 alkyl, C 1 -C 3 alkoxy, chlorine, fluorine, bromine or iodine; and Y 'represents an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine atom, a bromine atom or an iodine atom, provided that X' and Y 'are not simultaneously methyl, react with ethyl chloroformate or methyl chloroformate presence of an inert solvent. ♦ 6. The process of claim 5, wherein the compound of formula (II) is aniline, wherein each of X'and Y ', which are the same, represents a bromine atom. 7. The process of claim 5, wherein the compound of formula (II ') is aniline, wherein each of x'and y', which are the same or different, represents an alkyl group containing 1 to 2 carbon atoms, an alkoxy group containing 1-3 carbon atoms or halogen, with the proviso that X'and Y 'are not simultaneous chlorine or bromine or methyl.