GB2106895A

GB2106895A - N-[1-Triazol-(1)-YL-2,2,2-Trichloroethyl]- substituted carboxamides for controlling mildew

Info

Publication number: GB2106895A
Application number: GB08212326A
Authority: GB
Inventors: Katsumichi Aoki; Susumu Shimizu; Keigo Satake; Shiro Yamazaki
Original assignee: Kureha Corp
Current assignee: Kureha Corp
Priority date: 1981-10-06
Filing date: 1982-04-28
Publication date: 1983-04-20
Also published as: FR2513997A1; FR2513997B1; JPS5859975A; JPH0226632B2; DK179182A; GB2106895B; DE3215771A1; NL8201794A

Abstract

Derivatives of N-[1-triazol-(1)-yl- 2,2,2-trichloroethyl]-substituted carboxamide represented by the general formula (I): <IMAGE> wherein R represents hydrogen, methyl, ethyl, 2-trifluoromethylphenyl, 2-hydroxyphenyl, 2-acetoxyphenyl, 4-isopropylphenyl, 4-t-butylphenyl, 2-chloro-4-nitrophenyl, benzyl, or the radical <IMAGE> wherein R<1> and R<2> are the same or different from each other and represent hydrogen, fluorine, chlorine, bromine, iodine, methyl or methoxy, are useful in combating or preventing mildew in plants.

Description

SPECIFICATION N -Triazol-(l )-YL-2,2,2-Trichloroethyll-su substituted carboxamides for controlling mildew The present invention relates to a derivative of N-[1-triazol-(1)-yl-2,2,2-trichlornethyl]-substituted carboxamide represented by the general formula (I):

wherein R represents hydrogen, methyl, ethyl, 2-trifluoromethylphenyl, 2-hydroxyphenyl, 2acetoxyphenyl, 4-isopropylphenyl, 4-t-butylphenyl, 2-chloro-4-nitropheyl, benzyl, or the radical

wherein R' and R2 are the same or different from each other and represent respectively a hydrogen, fluorine, chlorine, bromine, iodine, methyl or methoxy, and a powdery mildewcontrolling agent containing the compound represented by the general formula (i) as an active ingredient.

Hitherto, a number of compounds having a triazole group as a substituent have been known as an agent for controlling plant diseases and some of them have been patented, for instance, in Japanese Patent Applications Laying-Open No. 52-148073 (1977) and No. 55-17390 (1980).

In addition, although anti-eumycetic activity has been partly known on derivatives of N (azolylhalogenoalkyl)-carboxamide, for instance, on derivatives of N-(l-imidazolyl-2,2,2-trichloro- ethyl)-carboxamide (refer to Chemical Abstract, 83, 114405e (1975)), there is no literature referring to their function as an agricultural or horticultural fungicide. Although it has been disclosed that derivatives of N-(1-azolyl-2,3,3-trichloropropyl)-carboxamide have a fungicidal activity in Japanese Patent Application Laying Open No. 52-17473 (1977) (refer to Chemical Abstract, 87, 1522219 (1977)), there is no disclosure of the data as an agricultural or horticultural fungicide. As another instance, a similar compound to the compounds of the present invention has been disclosed as an example in Japanese Patent Publication No.5224003 (1977), however, the exemplified compound is N-[1-(1 ,2,4-triazol-4-yl)-2,2,2-trichloroeh- tyl]-formamide and the triazole group is not bonded at 1-position of the triazole group as in the compounds of the present invention.

As a result of extensive studies in synthesizing and screening novel derivatives of N-[1 -triazol- (1)yl-2,2,2,-trichlorn-ethylj-carboxamide with an intention of developing a novel fungicide for use in agriculture and horticulture, the inventors of the present invention have found that the compounds represented by the general formula (I) specifically show excellent fungicidal function against powdery mildew on cereals, vegetables, fruit trees and flowering plants and have accomplished the present invention based on their findings.

Since the compound according to the present invention is excellent in preventive and curative effects against the disease as well as its strong systemic function within the plant body to which it is applied, the plant disease can be controlled directly or systemically. In other words, the systemic function of the compound of the present invention into the plant tissues produces numerous advantages in the field of plant diseases control. For instance, it is possible to effectively control the phytopathogenic fungus which has invaded into the inner parts of plant bodies and also the phytopathogenic fungus of seed infection by utilizing such a systemic fungicide.In addition, in the case where a fungicide is applied on the aerial parts of the crop plants, even if the coverage of the surface of the plant body by the fungicide is not uniform, the systemic fungicide can control the disease infallibly. It means that such a systemic fungicide can be applied by soil-treatment or seed-treatment resulting in power-saving in the application of the fungicide.

On the other hand, the compound according to the present invention is highly safe to vertebrates including human beings and to fishes and can be applied on agricalturally useful crop plants without causing any practical harm thereon.

The object of the present invention is to provide a novel derivative of N-1-triazol-(1)-yl-2,2,2- trichloroethyl]-carboxamide represented by the general formula (I) and a powdery mildewcontrolling agent having excellent systemic function.

The present invention relates to a novel derivative of N-[1-triazol-(1)yl-2,2,2-trichloroethyl]- substituted carboxamide represented by the general formula (I):

wherein R represents hydrogen, methyl, ethyl 2-trifluoromethylphenyl, 2-hydroxyphenyl, 2acetoxyphenyl, 4-isopropylphenyl, 4-t-butylphenyl, 2-chloro-4-nitrophenyl, benzyl, or the radical

wherein R' and R2 are the same or different from each other and represent respectively hydrogen, fluorine, chlorine, bromine, iodine, methyl or methoxy, and a powdery mildewcontrolling agent containing the compound represented by the general formula (I) as an active ingredient.

The derivatives of N-[1-triazol-(1)-yl-2,2,2-trichloroethyl]-carboxamide which can be used as the active ingredient of the controlling agent against powdery mildew are exemplified in Table 1.

Table 1: Some of the compounds according to the present invention No. of the Melting Point compound Chemical name of the compound ( C) 1 N-[1-(1,2,4-triazol-1-yl)-2,2,2-trichloroethyl]-formamide 115 - 117 2 N-[1-(1,2,4-triazol-1-yl)-2,2,2-trichloroethyl]-acetamide 172 - 174 3 N-[1-(1,2,4-triazol-1-yl)-2,2,2-trichloroethyl]-propionamide 157 - 158 4 N-[1-(1,2,4-triazol-1-yl)-2,2,2-trichloroethyl]-benzamide 105 - 108 5 N-[1-(1,2,4-triazol-1-yl)-2,2,2-trichloroethyl]-2-chlorobenzamide 140 - 142 6 N-[1-(1,2,4-triazol-1-yl)-2,2,2-trichloroethyl]-3-chlorobenzamide 171 - 172 7 N-[1-(1,2,4-triazol-1-yl)-2,2,2-trichloroethyl]-4-chlorobenzamide 179 - 181 8 N-[1-(1,2,4-triazol-1-yl)-2,2,2-trichloroethyl]-2,4-dichlorobenzamide 164 - 166 9 N-[1-(1,2,4-triazol-1-yl)-2,2,2-trichloroethyl]-3,4-dichlorobenzamide 171 - 173 10 N-[1-(1,2,4-triazol-1-yl)-2,2,2-trichloroethyl]-2,6-dichlorobenzamide 195 - 196 11 N-[1-(1,2,4-triazol-1-yl)-2,2,2-trichloroethyl]-3,5-dichlorobenzamide 194 - 196 12 N-[1-(1,2,4-triazol-1-yl)-2,2,2-trichloroethyl]-2-bromobenzamide 149 - 151 13 N-[1-(1,2,4-triazol-1-yl)-2,2,2-trichloroethyl]-2-methylbenzamide 146 - 149 14 N-[1-(1,2,4-triazol-1-yl)-2,2,2-trichloroethyl]-4-methylbenzmaide 149 - 111 Table 1 (continued) No. of the Melting Point compound Chemical name of the compound ( C) 15 N-[1-(1,2,4-triazol-1-yl)-2,2,2-trichloroethyl]-2-methoxybenzmaide 176 - 178 16 N-[1-(1,2,4-triazol-1-yl)-2,2,2-trichloroethyl]-2-fluorobenzamide 158 - 160 17 N-[1-(1,2,4-triazol-1-yl)-2,2,2-trichloroethyl]-2,6-difluorobenzamide 170 - 172 18 N-[1-(1,2,4-triazol-1-yl)-2,2,2-trichloroethyl]-2-trifluoromethylbenzamide 153 - 156 19 N-[1-(1,2,4-triazol-1-yl)-2,2,2-trichloroethyl]-2-iodobenzamide 157 - 158 20 N-[1-(1,2,4-triazol-1-yl)-2,2,2-trichloroethyl]-2-hydroxybenzamide 171 - 172 21 N-[1-(1,2,4-triazol-1-yl)-2,2,2-trichloroethyl]-2-acetoxybenzamide 154 - 156 22 N-[1-(1,2,4-triazol-1-yl)-2,2,2-trichloroethyl]-4-isopropylbenzamide 151 - 152 23 N-[1-(1,2,4-triazol-1-yl)-2,2,2-trichloroethyl]-4-t-butylbenzamide 142 - 144 24 N-[1-(1,2,4-triazol-1-yl)-2,2,2-trichloroethyl]-2,6-dimethylbenzamide 178 - 179 25 N-[1-(1,2,4-triazol-1-yl)-2,2,2-trichloroethyl]-2-chloro-4-nitrobenzamide 189 - 191 26 N-[1-(1,2,4-triazol-1-yl)-2,2,2-trichloroethyl]-phenylacetamide 175 - 176 27 N-[1-(1,2,4-triazol-1-yl)-2,2,2-trichloroethyl]-2,5-dichlorobenzamide 166 - 168 The compound for use as the active ingredient in the present invention can be synthesized generally by the following.

wherein R represents the same as above. Namely, by stirring N-(1,2,2,2-tetrachloroethyl)carboxamide in an organic solvent such as acetonitrile at a room temperature for a few hours after the addition of an equimolar to a little excess amount of 1 2,4-triazole and of an equimolar amount of triethylamine thereto, the object compound can be obtained.

The present invention will be concretely explained more in detail while referring to examples as follows: Example 1 Synthesis of N-[(1-(1-,2,4-triazol-1-yl)-2,2,2-trichloroethyl]-furmamide (Compound no. 1): Into a solution of 3.1g (0.015 mol) of N-(l ,2,2,2-tetrachloroetyl)-formamide in 40 ml of acenonitrile, 1g (0.015 mol) of 1,2,4-triazole was added, and after adding 1 .5g (0.015 mol) of triethylamine to the mixture, the whole system was stirred for 2 hours at a room temperature.

The solid substance white in colour obtained by condensing the reaction mixture under a reduced pressure was washed well with water and after being dried, it was recrystallized from benzene to be Compound No. 1 melting at 115 to 117 C as white crystals in an amount of 2.0g (55% of the theoretical yield).The analytical data by infrared absorption and nuclear magnetic resonance of the thus obtained Compound No. 1 are as follows: Infrared absorption bands (KBr tablet): 3140(NH) and 1700(CO) cm NMR spectrum (d6 in acetone), #(ppm): 7.30(1 H, d, J = 11 Hz, oC-H) 8.10 and 8.99 (each 1 H, s, proton of the triazole ring), and 8.48(1 H, s, COH) and 9.30 (1 H, m, NH) EXAMPLE 2 Synthesis of N-[1-(1,2,4-triazol-1-yl(-2,2,2-trichloroethyl]-acetamide (Compound No. 2) Into a solution of 3.3g (0.015 mol) of N-(1 ,2,2,2-tetrachloroethyl)-acetamide in 40 ml of aceyonitrile, 1 g (0.015 mol) of 1 2,4-triazole was admixed, and after further admixing 1.5 g (0.015 mol) of triethylamine with the mixture, the whole system was stirred for 4 hours at a room temperature. The solid substance white in colour obtained by condensing the reaction mixture under a reduced pressure was washed well with water, dried and then recrystallized from benzene 2.99 (76% of the theoretical yield) of Compound No. 2 melting at 172 to 174 C as white crystals. The analytical data by infrared absorption and nuclear magnetic resonance of the thus obtained Compound No. 2 are as follows: Infrared absorption bands (KBr tablet): 31 30H and 1690(CO) cm-'.

Nuclear Magnetic Resonance spectrum(d6 in acetone), S(ppm): 2.13 (3H, s, CH3) 7.30(1 H,d,J=11 Hz, #C-H).

8.14 and 9.02 (each (1 H, s, proton of the triazole ring), and 9.03 (1 H, m, NH).

EXAMPLE 3 Synthesis of N-fl -(1,2, 4-triazol-1-yl)-2. 2, 2-trichloroethyl7-propionemide (Compound No. 3): In a similar manner to that in Example 1 while starting from 3.6 g of N-(1,2,2,2- tetrachloroethyl)-propionamide (0.015 mol) in 50 ml of acetonitrile, 1 g (0.015 mol) of 1,2,4triazole and 1.5 g (0.015 mol) of triethylamine, Compound No. 3 was synthesized by stirring the whole system for 3 hours at a room temperature. After recrystallizing the dried white substance obtained by condensing the reaction mixture under a reduced pressure and washing well with water from ethanol, Compound No. 3 was obtained as purified white crystals melting at 157 to 158 C amounting to 3.0 9 (75% of the theoretical yield).The data by analyses of infrared absorption and nuclear magnetic resonance of Compound No. 3 are shown below.

Infrared absorption bands (KBr tablet): 3140(NH) and 1700(CO) cm Nuclear magnetic resonance (d6 in acetone), (ppm): 1.15(3 H, t, J = 8 Hz, CH2CH3), 2.53(2 H, q, J=8 Hz, CH2CH3), 7.41(1 H, d, J = 11 Hz, oCH), 8.27 and 9.18 (each 1 H, s, proton of triazole ring), and 9.00 (1 H, m, NH).

EXAMPLE 4 Synthesis of N-[1-(1,2,4-triazol-1-yl)-2,2,2-trichloroethyl]-2-chlorobenzamide (Compound No. 5): After suspending 2g (0.006 mol) of N-1 ,2,2,2-tetrachloroethyl)-2-chlorobenzamide in 100 ml of benzene, 0.42g (0.006 mol) of 1 2,4-triazole, and 0.649 (0.006 mol) of triethylamine were successively admixed with the suspension, and the whole system was stirred for one hour at a room temperature. After removing the separated white crystals by filtration, the filtrate was condensed under a reduced pressure to obtain an oily substance pale yellow in colour.By purifying the oily substance by column chromatography while using Wako-gel c-200 as a column material and an eluting mixture of benzene and acetone of a volume ratio of 10:1, 1 .6g of white crystals of Compound No. 5 melting at 140 to 142"C was obtained in a yield of 76%.

The results of analyses by infrared absorptions and nuclear magnetic resonance spectoscopies of the thus obtained Compound No. 5 are as follows: Infrared absorption bands (KBrtablet): 3140(NH) and 1678(CO) cm-1.

Nuclear Magnetic Resonance (d6 in acetone, Gppm): 7.3-7.58 (5 H, m, oC-H + proton of benzene ring 8.02 and 9.00 (each (1, s, proton of triazole ring) and 9.50(1 H, broad d, J = 10 Hz, NH) EXAMPLE 5 Synthesis of N-[ 1-(1,2, 4-triazol- 1 -yl)-2, 2, 2-trichloroethyl]-2, 4-dichlorobenzamide (Compound No.

8) After suspending 3.5 g (0.01 mol) of N-(1 ,2,2,2-tetrachloroethyl)-2,4-dichlorobenzamide in 50 ml of acetonitrile, 0.76g (0.011 mol) of 1,2,4-triazole and 1.1g (0.011 mol) of triethylamine were succesively admixed with the suspension and the whole system was stirred for 7 hours at a room temperature. Then, the filtrate was condensed under a reduced pressure to obtain a solid substance while in colour.The substance was washed with water to obtain white crystals, which were then recrystallized from a small amount of acetonitrile to obtain 2.3 g of Compound No. 8 melting at 164 to 166"C in a yield of 60.5% The results of analyses of the thus obtained Compound No. 8 by infrared absorptions and nuclear magnetic resonance spectroscopies are shown as follows: Infrared absorption bands (KBrtablet): 3150 (NH) and 1690(CO) cm-'.

Nuclear magnetic resonance spectrum (d6 in dimethylsulfoxide), d(ppm) 7.40(1 H, d, J = 10 Hz, eC-H), 7.5-7.8(3 H, m, proton of benzene ring), 8.20 and 9.12(each 1 H, s, proton of triazole ring), and 10.49(1 H, J = 10 Hz, NH).

EXAMPLE 6 Synthesis of N-[1-(1, 2, 4-triazol- 1-yl)-2, 2, 2-trichloroethyl]-2, 6-dichlorobenzamide (Compound No.

10) After suspending 2g (0.056 mol) of N-(1 ,2,2,2-tetrachloroethyl)-2,6-dichlorobenzamide in 100 ml of benzene, 0.43g (0.006 mol) of 1,2,4-triazole and 0.64g (0.006 mol) of triethylamine were successively admixed with the suspension and the whole system was stirred for 8 hours at a room temperature. Then, after removing the separated white crystals by filtration, the benzene layer was washed two times with water, dried on anhydrous sodium sulfate and benzene was distilled off under a reduced pressure to obtain 1 .2g of white crystals, which were then recrystallized from a small amount of benzene to obtain 0.6 g of Compound No. 10 melting at 195 to 196"C in a yield of 30%.

The results of analyses of the thus obtained Compound No. 10 by infrared absorptions and nuclear magnetic resonance spectroscopies are shown as follows: Infrared Absorption bands (KBr tablet): 3110(NH) and 1685(CO) cm-l.

Nuclear magnetic resonance spectrum (d6 in dimethylsulfoxide), #(ppm) 7.38(1 H, d, J = 10 Hz, oC-H), 7.48(3 H, s, proton of benzene ring), 8.13 and 9.09(each 1 H, s, proton of triazole ring), and 10.78(1 H, J = 10 Hz, NH).

EXAMPLES 7 to 11 In a similar manner to that of Example 6, the respective compounds shown in Table 2 were synthesized under the conditions shown also in Table 2.

The reaction in Example 7 was carried out at a room temperature, however, in Examples 8 to 11, 1,2,4-triazole and triethylamine were added to the suspension cooled by ice water, of each substituted benzamide in acetonitrile, and the stirring was carried out until the temperature of the reaction mixture returned to a room temperature.

The results of analyses of the thus obtained Compounds by infrared absorptions and nuclear magnetic resonance spectroscopies are shown as Table 3.

Table 2: Conditions of synthesizing Compounds Nos. 13, 17, 18, 21 and 24 in Examples 7 to 11:

No. of Amount of reagent Example Hour of Solvent for Yield of compound Reagent A* Reagent B** Reagent C*** stirring recrystalli- product (g and mol) (hour) zation (g and %) 7 13 1.7 0.43 0.64 4 acetonitrile 1.0; 50 0.0056 0.006 0.006 8 17 4.8 1.1 1.5 3 acetonitrile 2.9; 55 0.015 0.015 0.005 9 18 2.5 0.53 0.78 4 acetonitrile 1.7; 63 0.007 0.0077 0.0077 10 21 5.2 1.1 1.5 1 acetonitrile 5.5; 95 0.015 0.015 0.015 11 24 3.1 0.76 1.1 3.5 acetonitrile 1.4; 41.2 0.01 0.011 0.011 Notes: Reagent A* : N-(1,2,2,2-tetrachloroethyl)-2-methylbenzamide in Example 7, N-(1,2,2,2-tetrachloroethyl)-2,6-difluorochbenzamide in Example 8, N-(1,2,2,2-tetrachloroethyl)-2-trifluoromethylbenzamide in Example 9, N-(1,2,2,2-tetrachloroethyl)-2-acetoxybenzamide in Example 10 and N-(1,2,2,2-tetrachloroethyl)-2,6-dimethylbenzamide in Example 11.

Reagent B** : 1,2,4-triazle in all Examples 7 to 11.

Reagent C*** : triethylamine in all Examples 7 to 11.

Table 3

Example 7 8 9 10 11 3410 (NH), Infrared Absorption 3140 (NH), 3110 (NH) 3130 (NH) 1780 (OCO), 3140 (NH) bands (KBr tablet) 1670 (CO) 1680 (CO) 1660 (CO) 1665 (CO) 1675 (CO) Nuclear magnetic 2.28 (3H, s, -CH3), 7.0-7.9 (3H, m, 7.4 (1H, d, J=10 2.23 (3H, s, 2.15 (6H, s, 7.06-7.49 (5H. protone of Hz, #), COCH3) CH3 x 2), resonance spectrum m, #+protone benzene ring), 7.58-7.98 (4H, m, 7.28-7.91 7.0-7.41 (3H, (d6 in of benzene ring), 7.42 (1H, d, proton of (5H, m, pro- m, proton of dimethylsulfoxide), 8.10 and 9.05 J=10 Hz, #), benzene ring), ton of benzene), # (ppm) (each 1H, s, proton 8.20 and 9.11 8.2 and 9.1 benzene ring + 7.48 (1H,d, f triazole ring), (each 1H, s, (each 1H, s, #), J=10 Hz,#), 10.21 (1H, d, proton of proton of tria- 8.32 an 9.29 8.28 and 9.2 J=10 Hz, NH) triazole ring), zole ring), (each 1H, s, (each 1H, s, 10.87 (1H, d, 10.7 (1H, d, J= proton of proton of J=10 Hz, NH) 10 Hz, NH) triazole ring) triazole ring) 10.25 (1H, d, 10.48 (1H, d, J=10 Hz, NH). J=10 Hz, NH) Melting point 146 - 148 170 - 172 153 - 156 154 - 156 178 - 179 ( C) The following Examples 1 2 and 1 3 show the preparation of two powdery mildew controlling agents according to the present invention, namely a wettable powder in Example 1 2 and a granular composition in Example 1 3: EXAMPLE 12: A wettable powder was prepared by pulverising and mixing the following components and then sifting the mixture: 50 parts by weight of Compound No. 5, 5 parts by weight of sodium ligninsulfonate, 3 parts by weight of sodium alkylsulfonate and 42 parts by weight of diatomaceous earth.

EXAMPLE 13: A granular composition was prepared by uniformly mixing the following components, kneading the mixture while adding a small amount of water, shaping the kneaded material into granular form by extrusion and drying the extruded granules followed by sifting the dried granules: 8 parts by weight of Compound No. 10, 40 parts by weight of bentonite, 45 parts by weight of clay, and 7 parts by weight of sodium ligninsulfonate.

The following Example 14 shows the effectiveness of the powdery mildew-controlling agent according to the present invention against Erysiphe graminis DC.f. sp.tritici, the pathogenic ascomycetes on wheat, in vivo when applied on the aerial part of wheat plants.

EXAMPLE 14: Onto the seedlings of wheat(variety: Norin 64) grown in pots of 10 cm in diameter (16 seedlings/pot) at their three leaf-stage, each of the wettable powders of the recipe similar to that in Example 1 2 was sprayed after diluting and dispersing in water at a concentration of the active ingredient in water of 250 ppm. After natural drying of the leaves, an aqueous suspension of spores of Erysiphe graminis DC.f.sp. tritici collected from the leaves of wheat plant suffering from powdery mildew was sprayed on the treated plants in the pots. After leaving the pots in a glass house at about 25"C for 10 days, the morbidity of the seedlings was investigated by observing the morbid state of the seedlings and judging according to the following standard: Morbidity Extent of morbid state O No occurrence of lesion 0.5 Less than 10% of the area of lesion to the total area of leaves 1 Between 10 and 25% 2 Between 26 and 50% 3 Between 51 and 75% 4 Larger than 75% The result of investigation is shown in Table 4.

Table 4: Results of Controlling Powdery mildew by treating aerial parts of wheat seedling Active Ingredient No of compound Morbidity Phytotoxicity 1 0.5 None 2 0 None 3 0 None 4 0.5 None 5 0 None 6 3 None 7 2 None 8 0 None 9 0.5 None 10 0 None 11 1 None 12 1 None 13 0.5 None 14 3 None 15 1 None 16 0 None 17 0 None 18 0 None 19 0 None 20 0 None 21 0 None 22 0.5 None 23 0.5 None 24 0.5 None 25 0 None 26 0 None 27 0 None Control(non treatment) 4 None 1) Comparative 1 None Note; 1) Comparative powdery mildew-controlling agent containing N-tridecyl-2, 6-dimethyltetrahy- dro-1,4-oxazine as an active ingredient, sprayed as an aqueous suspension at a concentration of the active ingredient of 250 ppm.

The following Example 1 5 shows the effectiveness of the powdery mildew-controlling agent according to the present invention against Erysiphe graminis DC. f.sp. tritici, in vivo when applied on the seeds of wheat.

EXAMPLE 15: After soaking 30 seeds of wheat plant (variety; Norin 64) in an aqueous suspension of each of the wettable powders of the recipe similar to that in Example 1 2 at a concentration of the active ingredient of 250 ppm, the thus treated seeds were sown in pots of 10 cm in diameter and the pots were kept in a glass house at about 25"C for 10 days to confirm the germination and growth of the seeds to their two leaf-stage. Then, an aqueous suspension of the spores of the same pathogenic ascomycete as in Example 1 4 collected from the wheat plants suffering from powdery mildew was sprayed onto the seedlings at their two leaf-stage, and the pots were left in the glass house at about 25"C for 10 days.The morbidity of the wheat plants in the pots was investigated as in Example 1 4 and the result is shown in Table 5.

Table 5; Results of Controlling Powdery Mildew by treating seeds of wheat plant Active ingredient No. of compound Morbidity Phytotoxicity 1 1 None 2 0 None 3 0 None 4 0.5 None 5 0 None 6 1 None 7 2 None 8 1 None 10 0 None 12 0.5 None 13 0 None 16 0 None 17 0 None 18 0 None 19 0 None 20 0 None 21 0 None 22 0.5 None 23 0.5 None 24 0 None 25 0 None 26 0 None 27 1 None Control 4 None Comparative') 1 None Note: Comparative 1): the same as in Table 4.

The following Example 1 6 shows the effectiveness of the powdery mildew-controlling agent according to the present invention against Podosphaera leucotricha, the pathogenic ascomycete of powdery mildew on apple trees, in vivo on apple seedlings.

EXAMPLE 16: An aqueous suspension of each of the wettable powders of the recipe similar to that in Example 1 2 was sprayed onto the seedlings of apple tree grown in pots sufficiently well to wet both the surfaces of their leaves, and the pots were left for two weeks in a polyvinyl chloride green house at about 25"C for natural infection to Podosphaera leucotricha, the pathogenic ascomycete of apple trees. Then, the rate of morbidity of the apple seedlings was assessed according to the appearance of ascomycetic colonies on the leaves of the apple seedlings classified by the following standard and the rate of morbidity was calculated by the following formula (III), and the results are shown in Table 6.

Index of morbidity Morbid state O No fungal colonies are found on the surfaces of leaves 0.5 Colonies occupy less than 5% of the area of the surfaces of leaves 1 Colonies occupy less than 20% of the area of the sur faces of leaves 2 Colonies occupy less than 50% of the area of the sur faces of leaves 4 Colonies occupy more than 50% of the surfaces of leaves E[(index of morbidity) X (Ni) Rate of morbidity (%) = (Ill) 4x(N) wherein Nj represents the number of leaves with the index of morbidity of i (for instance, 0; 0.5; 1; 2 or 4), and N represents the total number of the leaves examined.

Table 6: Results of Controlling Powdery Mildew by treating apple seedlings Active ingredient Rate of morbidity Phytoxicity No. of compound (%) 1 34.4 None 2 15.1 None 3 12.3 None 4 9.8 None 5 2.5 None 6 38.4 None 7 23.2 None 8 10.7 None 10 0.4 None 12 4.4 None 13 3.8 None 15 18.7 None 16 0 None 17 0 None 18 0 None 19 0 None 20 9.7 None 21 0 None 22 24.3 None 23 19.1 None 24 0 None 25 0 None 26 0 None 27 3.5 None Control (not treated) 71.6 None The following Example 1 7 shows the effectiveness of the powdery mildew-controlling agent against Erysiphe cichoracearum, the pathogenic ascoymte of tomato plant, in vivo when applied on tomato plant.

Example 17: An aqueous suspension of each of the wettable powders of the recipe similar to that in Example 1 2 was sprayed at a concentration of the active ingredient of 250 ppm onto tomato seedlings of the five leaf stage grown in three pots with one plant/pot. After natural drying the leaves, an aqueous suspension of the spores of the pathogenic ascomycete collected from the leaves of the tomato plants suffering from powdery mildew was sprayed onto the tomato plants, and after 10 days of the spraying, the morbidity of the plants was assessed by the observation of the thus treated tomato plant according to the standard shown in the Example 14.

The result in shown in Table 7.

Table 7: Results of Controlling Powdery mildew by treating seedling of tomato Active ingredient Morbidity Phytotoxicity No. of compound (%) 4 1 None 5 0 none 10 0 None 12 1.5 None 13 0.5 None 16 0 None 17 0 None 18 0 None 19 0 None 20 0 None 21 0 None 22 0.5 None 23 0 None 24 0 None 25 0 None 26 0 None Control (not treated) 4 None The following Example 1 8 shows the effectiveness of the powdery mildew-controlling agent according to the present invention against Sphaerotheca fuliginea, the pathogenic ascomycete on cucumber plant, in vivo when applied on cucumber plants.

Example 10 An aqueous suspension of each of the wettable powders of the recipe similar to that in Example 1 2 at a concentration of the active ingredient of 250 ppm was sprayed onto the seedlings of cucumber grown in pots of 10 cm in diameter at their two leaf stage (variety: Sagami-hanjiro, one seedling/pot, three pots).

After natural drying of the leaves of the seedlings, spores of Sphaerotheca fulginea collected from the cucumber plants suffering from powdery mildew was scattered on the potted cucumber plants with a small brush, and the pots were left in a green house at about 25"C for inoculation.

After 7 days of leaving in the green house, the morbidity of the thus treated plants was assessed based on the standards shown below.

Morbidity Morbid stated O No lesion is found 0.5 Less than 10% of the surface area of leaves is occupied by the lesions 1 From 10 to 19% of the surface area of leaves is occupied by the lesions 2 From 20 to 39% of the surface area of leaves is occupied by the lesion 3 From 40 to 59% of the surface area of leaves is occupied by the lesion 4 From 60 to 79% of the surface area of leaves is occupied by the lesion 5 More than 80% of the surface area is occupied The result is shown in Table 8.

Table 8: Results of Controlling Powdery mildew by treating seedling of cucumber Active ingredient Morbidity Phytotoxicity No. of compound (%) 1 1 None 2 0 None 3 0 None 4 0.5 None 5 0 None 7 1 None 8 0 None 10 0 None 12 0.5 None 13 0.5 None 27 0 None Control (Not treated) 5 None Comparative') 0.5 None Note: Comparative '): the same as in Table 4 The following Example 1 9 shows the effectiveness of the powdery mildew-controlling agent according to the present invention against Sphaerotheca pannosa, the pathogenic ascomycete of powdery mildew of rose plant in vivo when applied on the rose plant.

Example 19: Onto the rose plants (variety:peace) grown in pots of 30 cm in diameter, on which powdery mildew naturally occurred, an aqueous suspension of each of the wettable powders of the recipe similar to that in Example 1 2 was sprayed. After natural drying the rose plant,the pots were left in a polyvinyl chloride house and after 10 days of the spraying, the morbidity of powdery mildew on the test plant was assessed based on the observation and the standards shown below and the rate of morbidity was calculated as in Example 16, the result being shown in Table 9.

Table 9: Results of Controlling Powdery mildew by treating rose trees Active ingredient Rate of morbidity Phytotoxicity No of compound (%) 1 28.4 None 2 10.6 None 3 9.5 None 4 6.6 None 5 0 None 6 23.7 None 7 19.8 None 8 12.5 None 10 0 None 12 3.6 None 13 1.2 None 15 13.5 None 16 0 None 17 0 None 18 0 None 19 1.9 None 20 4.3 None 21 0 None 22 17.7 None 23 21.8 None 24 11.1 None 25 0 None 26 0 None 27 10.6 None Control (Not treated) 68.9 None

Claims

1. A derivative of N-[1-triazol-(1)-yl-2,2,2-tri-chloroethyl] substituted carboxamide represented by the general formula (I):

wherein R represents hydrogen, methyl, ethyl, 2-trifluoromethylphenyl, 2-hydroxyphenyl, 2acetoxyphenyl, 4-isopropyl-phenyl, 4-t-butylphenyl,2-chloro-4-nitrophenyl, benzyl or the radical

wherein R' and R2 are the same or different from each other and represent hydrogen, fluorine, chlorine, bromine, iodine, methyl or methoxy.

2. A derivative according to claim 1, wherein R represents 2-chlorophenyl, 2,6-dichlorophenyl, 2-fluorophenyl, 2,6-difluorophenyl, 2-trifluoromethylphenyl, 2-acetoxyphenyl, 2-chloro-4-nitrophenyl or benzyl.

3. N-( 1 -(1, 2,4-triazol-1 -yl)-2, 2,2-trichloroethyl]-2-chlorobenzamide.

4. N-(1-(1,2,4-triazol-1-yl)-2,2,2-trichlorethyl]-2,6-dichlorobenzamide

5. N-[ 1 -(1,2, 2,4-triazol-I-yl)-2, 2, 2-trichloroethyl]-2-fluorobenzamide.

6. N-[1-(1,2,4-triazol-1-yl)-2,2,2-trichloroethyl]-2,6-difluorobenzamide

7. N-[ 1 -(1, 2,4-triazol- 1 -yl)-2, 2, 2-trichloroethyl]-2-trifluoromethylbenzamide.

8. N-[ 1 -(1, 2,4-triazol- 1 -yl)-2,2, 2-trichloroethyl]-2-acetoxybenzamide.

9. N-[1-(1,2,4-triazol-1-yl)-2,2,2-trichloroethyl]-2-chloro-4-nitrobencamide.

10. N-[1-(1,2,4-triazol-1-yl)-2,2,2-trichloroethyl]-phenylacetamide.

11. Any one of Compounds Nos. 1 to 4, 6 to 9, 11 to 15, 19, 20, 22 to 24 and 27 hereinbefore specified.

12. A process for producing an N-[1-triazol-(1)-yl-2,2,2-trichlorethylsubstituted carboxamide derivative as claimed in claim 1, which process comprises reacting an N-(1,2,2,2- tetrachloroethyl)-carboxamide of formula:

wherein R is as defined in claim 1, with 1,2,4-triazol in the presence of triethylamine and in an organic solvent.

13. A process for producing an N-[1-triazol-(1)-yl-2,2,2-trichloroethyl]-substituted carboxamide derivative as claimed in claim 1, said process being substantially as hereinbefore described in any one of Examples 1 to 11.

14. A fungicidal composition for use in agriculture or horticulture comprising an N-(1-triazol- (1)-yl-2,2,2-trichlorethyl]-carboxamide derivative as claimed in any one of claims 1 to 11 or which has been produced by a process as claimed in claim 1 2 or 1 3 as active ingredient, together with a carrier or diluent.

1 5. A fungacidal composition according to claim 14 for use in the treatment of mildew and in the form of a powder.

1 6. A fungicidal composition substantially as hereinbefore described in Example 1 2 or 1 3.

1 7. A method of combating or preventing mildew in monocotyledonous or dicotyledonous plants, which method comprises applying to a locus to be treated an N-[1-triazol-(1)-yl-2,2,2trichlorethyl]-carboxamide derivative as claimed in any one of claims 1 to 11 or which has been produced by a process as claimed in claim 1 2 or 13.

18. A method according to claim 17 wherein said derivative is applied to the aerial parts of plants in said locus by spraying.

19. A method according to claim 17 wherein the ground of said locus is treated with said derivative.

20. A method of combating or preventing mildew in monocotyledonous or dictoyledonous plants, which method comprises treating the seeds of said plants prior to planting with an N-[l- triazol-(1)-yl-2,2,2-trichloroethyl] carboxamide derivative as claimed in any one of claims 1 to 11 or which has been produced by a process as claimed in claim 12 or 13.

21. A method of combating or preventing mildew in monocotyledenous or dicotyledenous plants, which method being substantially as herein before described in any one of Examples 14 to 19.