DK164548B - Azolylmethylpentane derivatives, process for preparing them, and agricultural and horticultural agents which comprise these derivatives as active constituent - Google Patents

Description

in

DK 164548 B

The present invention relates to an azolylroethylpentane derivative represented by formula I

/ * = \

HO, CHn-N

5 2 V == tn r \ (I)

I_p-B

wherein B is a 2-chlorophenyl group, 3-chlorophenyl group, 2,4-10 difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluoro-phenyl group, 2-fluoro-4-chlorophenyl group, 2,3,4,5,6 penta-fluorophenyl group, 4-bromophenyl group, 4-nitrophenyl group, 4-methylphenyl group, 4-t-butylphenyl group, p-biphenylyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group and 4-cyanophenyl group or a methine group, a process for the preparation of the azolylmethyl derivative, and an agricultural or horticultural agent having fungicidal activity, a plant growth regulating and a herbicidal activity, and containing the azolylmethyl derivative as an active ingredient.

Field crops are severely damaged every year by plant diseases and agricultural chemicals to control them cause serious environmental problems. Therefore, there has been a great need for a new fungicide for agriculture and horticulture, which has low toxicity to humans, animals, birds and fish, and which also has a low degree of phytotoxicity to the utility plants. Such a fungicide must be very safe to handle, have very little detrimental effect on the environment, and provide excellent pest control for many different plant diseases. In the efforts to develop such an epidemic fungicide for agriculture and horticulture, according to the present invention, new compounds have been investigated instead of merely modifications of existing compounds.

For this purpose, a large number of derivatives of azole were synthesized and their utility in practical use was reduced

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tried. As a result, it was found that azolylmethylcyclopentane derivatives represented by formula I have the above properties.

5 HO \ .CH2-N ^ 1

B

Wherein B is a 2-chlorophenyl group, 3-chlorophenyl group, 2,4-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluoro-phenyl group, 2- fluoro-4-chlorophenyl group, 2,3,4, 5,6-penta-fluorophenyl group, 4-bromophenyl group, 4-nitrophenyl group, 4-methylphenyl group, 4-t-butylphenyl group, p-biphenylyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group or 4-cyanophen a nitrogen atom or a methine group.

In addition, and surprisingly, it was found that the azolylmethylcyclopentane derivative exerts not only a fungicidal effect, but also a plant growth regulating and herbicidal effect. These findings led to the present invention.

25

The object of the invention is to provide a fungicide for agriculture and horticulture which is effective against a large number of different plant diseases, with low toxicity to humans, animals, birds and fish and low phytotoxicity against beneficial plants, which further exerts a plant growth regulating effect and herbicidal action and is better in terms of risk-free handling and in protecting the environment.

The invention is further illustrated in the drawing, in which Figures 1-28 show infrared absorption spectra of the derivatives of azole according to the invention. The figure numbers correspond to the respective connection numbers shown in Table 1.

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The azolylmethylcyclopentane derivative of the invention has the formula I

HO CH-N ^ I

5 * 27 wherein B is a 2-chlorophenyl group, 3-chlorophenyl group, 2,4-10 difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluoro-phenyl group, 2-fluoro-4-chlorophenyl group, 2,3,4, 5,6-penta-fluorophenyl group, 4-bromophenyl group, 4-nitrophenyl group, 4-methylphenyl group, 4-t-butylphenyl group, p-biphenylyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group or 4-cyanophenyl group a nitrogen atom

or a methine group. The invention also relates to a process for preparing the azolylmethylcyclopentane derivative by reacting a derivative of oxirane represented by formula II

The invention also relates to an agricultural and horticultural agent containing as an active ingredient a derivative of azole, 20 20 0 (T * - B (II) where B has the same meaning as in formula I) with 1,2,4-triazole 25 or imidazole. represented by Formula I and having a fungicidal effect, a plant growth regulating effect and a herbicidal effect.

30

A derivative of azole represented by formula I is a novel compound and some of the derivatives are shown in Table 1 below with their melting points.

35 A detailed description of the process for the preparation of a derivative of azole represented by the formula I and the use of the derivative of azole as an agricultural and horticultural agent is given below.

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A derivative of azole represented by formula I is prepared by reacting a derivative of oxirane represented by formula II with 1,2,4-triazole or imidazole represented by formula III in the presence of a diluent 5 / A = l A »; I (III)

\ = N

Wherein M is a hydrogen atom or an alkali metal and A is a nitrogen atom or a methine group.

^ A = I

HO CH2-N

V (I)

15 I_ | CH2 B

(b = HØrxn, 25 30 35 5

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TABLE 1.

Preparation of Bin- Signs of Formula I Phenyl Radical ,, Part See --------------- of Formula I Melting Point,

No. X η A where X is ° C

5 ------------------------------------------------- --------------- 1 t-C4H9 IN 4 129 - 130 2 t-C4H9 1 CH 4 123 - 124 3 C6H5 IN 4 146 - 147 4 CcEc 1 CH 4 182 - 183 6 b 10 5 CF3 1 N 3 152 - 153 6 CF3 1 CH 3 87 - 88 7 Cl 1 N 3 152 - 153 8 Cl 1 CH 3 105 - 106 9 N02 1 N 4 131 - 132 15 10 F 2 N 2.6 104 - 105 11 F 2 CH 2.6 150 - 151 12 Br 1 N 4 106 - 107 13 Br 1 CH 4 119 - 120 14 Cl 1 N 2 154 - 155 20 15 Cl 1 CH 2 103 - 104 16 CH 3 1 N 4 128 - 129 17 CH3 1 CH 4 122 - 123 18 F 2 N 2.4 118 - 119 25 19 F 2 CH 2.4 144 - 145 20 F 2 N 3.4 119 - 121 21 F 2 CH 3.4 103 - 105 22 CN 1 N 4 115 - 116 23 CN 1 CH 4 103 - 104 30 24 F, C1 2 N 2 (F), 4 (Cl) 125 - 127 25 F, C1 2 CH 2 (F), 4 (Cl) 141 - 143 26 F 5 N 2,3,4,5,6 118 - 120 27 CF3 1 N 4 102 - 103 28 CF3 1 CH 4 91-92 35 6

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The infrared spectrum of each compound in Table 1 above is shown in Figure 1-28 of the drawing.

A derivative of oxirane represented by formula II, which is the starting material for the reaction, is prepared by reaction of a ketone represented by formula IV

ISLAND

10 [j - CH2 b (IV) where B has the same meaning as in formula I, with e.g. dimethyl-oxosulfonium methylide or dimethylsulfonium methylide in the presence of a diluent.

An example of the compound represented by formula IV is 2-substituted benzylcyclopentanone. It can be prepared from 2-alkoxycarbonylcyclopentanone and a similarly substituted benzyl halide by the method described in Org.Syn. 45, 7 (1965) and J.Chem.Soc. (1950), 325. It can also be prepared from a corresponding substituted benzyl halide and an enamine of cyclopentanone. (See J.Pharm.Sci.

68, 1501 (1979)).

25

The diluent used in the process of preparing the compound represented by Formula I includes hydrocarbons such as benzene, toluene, xylene and hexane, halogenated hydrocarbons such as methylene chloride, chloroform 30 and tetrachloro carbon, alcohols such as methanol and ethanol, ethers such as diethyl ether, diisopropyl ether and diisopropyl ether. and other compounds such as acetonitrile, acetone, dimethylformamide and dimethylsulfoxide.

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The process of the invention may be carried out in the presence of the above diluent together with a base. Examples of the base include alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal hydroxide such as sodium hydroxide and potassium hydroxide, alkali metal alcoholates such as sodium methylate, sodium ethylate and potassium t-butylate, alkali metal hydrides such as sodium hydride and potassium hydride and potassium hydride.

The process according to the invention is carried out as follows.

An azole represented by the formula III is dissolved in a diluent as exemplified above, and to the solution is added an oxirane represented by the formula II in an amount of 0.5 - 1.0 equivalent. If necessary, the solution may contain a base as exemplified above. Alternatively, the oxyrane may be dissolved in the diluent first, and to the resulting solution an alkali metal salt of the azole may be added.

The reaction temperature ranges from the freezing point to the boiling point of the above diluent, but the preferred reaction temperature is from 0 to 100 ° C. The reaction time is 20 from 1 to 3 hours. The reaction is preferably carried out with stirring.

After the reaction is complete, the reaction mixture is cooled and extracted with an organic solvent such as ethyl acetate, chloroform or benzene in ice-cooled water. The organic layer is separated, washed with water and dried. The solvent is distilled off under reduced pressure. The residues are purified to form the desired compound. Purification can be performed by recrystallization or chromatography on silica gel.

A derivative of azole (a derivative of azolylcyclopentanol) represented by Formula I exerts the following effects as an active ingredient of agricultural and horticultural agents: 8

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(1) Fungicidal effect on plant diseases.

A derivative of azole according to the invention exerts a controlling effect on many different plant diseases listed below.

Rice plants: Pyricularia oryzae, Cochliobolus miyabeanus,

Xanthomonas oryzae, Rhizoctonia solani, Helminthosporium sigmoideum and Giberella 10 fujikuroi.

Apple tree: Podosphaera leucotricha, Venturia inaequalis,

Sclerotinia mali, Alternaria mali and Valsa mal i.

Pear tree: Alternaria kikuchiana, Phyllactinia pyri, 15 Gymnosporangium haraeonum and Venturia nashicola.

Grapes: Onccinula necator and Phakospora ampelopsidis.

Build: Erysiphe graminis f.sp.hordei, Rhynchosporium secalis, Puccinia graminis and Puccinia 20 triformis.

Wheat: Puccinia recondita, Septoria tritici,

Puccinia triformis and Erysiphe graminis f.sp. tritici.

Oriental melon plant: Sphaerotheca fuliginea.

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Watermelon plant: Fusarium oxysporum.

Tomato plant: Erysiphe cichoracearum and Alternaria solani.

Eggplant: Erysiphe cichoracearum.

Strawberry plant: Sephaerotheca humuli.

5 Tobacco plant: Erysiphe cichoracearum and Alternaria longipes.

Beetroot: Cercospora beticola.

Potato plant: Alternaria solani.

Soybean plant: Cercospora kikuchii and Septoria glycines.

Stone fruit plant: Sclerotinia cinerea.

10 Other crop plants: Botrytis cinerea and Sclerotinia sclerotiorum.

A derivative of azole according to the invention provides not only the protective effect, but also the therapeutic effect on some of the aforementioned plant diseases.

(2) Plant growth regulating effect.

Recently, plant growth regulators have come into common use in agriculture and horticulture after the mechanism controlling plant growth regulation with plant hormones f has been elucidated. The use of plant hormones includes e.g.

20 production of core-free grapes using gibberellin, forth 10

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acceleration of rooting on cuttings by means of α-naphtha-lenacetic acid and washing of wheat with 2-chloroethyltrimethylammonium chloride (trade name: "CCC").

The use of various techniques to regulate the environment of plants by using plant growth regulators is now applied not only to field crops, vegetables and fruit trees, but also to ornamental plants such as flowers and also to a wider range of plants such as trees. There is an increasing opportunity for the effect of plant growth regulators to spread to accelerate root formation, flowering regulation, fruit bearing and fruit development, growth acceleration, growth retardation and metabolism regulation. Plant growth regulators are growing in terms of species and quantity used in recent years, but not as much as could be expected from the 15 opportunities mentioned above.

The derivative of azole (derivative of azolylcyclopentanol) of the invention produces the plant growth regulating effect (including herbicidal effect) on many different plants as shown below: 1) Suppression of vegetative growth of plants, especially under pressure of height growth.

2) Increase of available nutrients in plants.

3) Regulation of ripening stage or flowering time of plants.

25 The first of the above activities is useful for suppressing weed growth (weed kill function), suppressing lawn growth, preventing bedding of rice plants and wheat, suppressing the height of soybean and 11

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cotton plants which enable harvesting by machine, suppression of shaft buds which promote the growth of tobacco leaves, suppression of the growth of hedge plants which reduce the frequency of cutting, and retardation of the growth of ornamental plants, 5 leading to increased trade value.

The other activity mentioned above contributes to the improvement of sugar beet, sugar cane and citrus through increasing the sugar content, and also to improving crops and soybean through increasing the protein.

10 third activity mentioned above allows fresh fruits and flowers to be shipped at any time as needed.

A derivative represented by formula I can be used as a fungicide, plant growth regulator or herbicide in the form of dust, wettable powder, grain, emulsifiable concentrate or solution, with or without admixture with a carrier (or diluent). It may also be used as such, as the composition may contain, in addition to a carrier, additives such as spreading agents, emulsifying agents, wetting agents and adhesives to ensure the effect.

Furthermore, the derivative of the invention can be used in the form of inorganic salt, organic salt or metal complex because it contains the 1,2,4-triazole ring or the imidazole ring.

The azole derivative of the invention has an azolylmethyl group and a substituted benzyl group at the 1-position and 2-position, respectively, in the cyclopentane ring. It may therefore exist in the form of stereoisomers, e.g. geometric isomers (cis-shape and trans-form) and optical isomers. According to 12

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In the invention, the derivative of azole may be a single isomer or a mixture thereof in any ratio. Thus, the agricultural and horticultural chemical of the invention may contain one of the isomers or a mixture of the isomers as an active ingredient.

The invention is further illustrated by the following examples which show the preparation of derivatives of azole and the effect of agricultural and horticultural chemicals containing an derivative of azole as active ingredient.

EXAMPLE 1.

Preparation of 2- (2,6-difluorobenzyl) -1 (1H-imidazol-1-yl-methyl) cyclopentan-1-ol (Compound No. 11 in Table 1).

To 20 ml of anhydrous dimethylformamide were added with stirring 15 and under a helium atmosphere 432 mg of sodium hydride (prepared by washing 60% oily sodium hydride with dried benzene), and after adding 1220 mg of 1 H-imidazole to the resulting mixture, the whole mixture was stirred at room temperature until the bubbling was over. A solution of 2, and 20 of 4- (2,6-difluorobenzyl) -1-oxaspiro [2,4-heptane in 10 ml of anhydrous dimethylformamide was added dropwise to the resulting solution and the whole mixture was stirred for 2 hours at 80 ° C.

After the resulting reaction mixture was allowed to cool, it was poured into ice-cooled water and the mixture was extracted with ethyl acetate to obtain an organic layer. After washing the organic layer with water and drying the layer on anhydrous sodium sulfate, the solvent was distilled off from the layer under reduced pressure to form a residue.

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Recrystallization of the residue with a mixture of hexane and ethyl acetate yielded 1.58 g of the title compound.

The results of determining the physical properties of the compound prepared are as follows, and in addition, the NMR spectrum of the compound was determined using TMS as the internal standard, and the results are shown by the following characters (the same characters are used in the other examples) ): 10 s: singlet d: doublet m: multiplet b: wide line

Physical Properties: 15 (1) Melting point 150 - 151 ° C.

(2) Infrared absorption spectrum (KBr method): 9max.

3400, 3180, 2930, 1620, 1580, 1460, 1220, 1070 cm "1.

(3) NMR spectrum (CDCl 3, ppm): δ 1.27-2.27 (bs, 7H), 2.60-2.90 (m, 2H), 3.30 (bs, 1H), 3.83 (d, 1H, J = 14 Hz), 4.17 (d, 1H, J = 14 Hz) and 6.60-7.63 (m, 6H).

EXAMPLE 2.

Preparation of 2- (4-bromobenzyl) -1- (1H-1,2,4-triazol-1-yl-methyl) cyclopentan-1-ol (Compound No. 12 in Table 1).

40 ml of anhydrous dimethylformamide were dissolved in 3.0 g of 4- (4- 14)

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bromobenzyl) -1-oxaspiro [2,4] heptane with stirring and under a helium atmosphere, and to the solution thus prepared was slowly added 1.12 g of sodium salt of 1H-1,2,4-triazole with a purity of 90% ( commercial product, manufactured by ALDRICH CO.). The mixture was stirred for 2 hours at 60 ° C.

After the reaction mixture thus obtained was allowed to cool, the cooled mixture was poured into water and the mixture was extracted with ethyl acetate to form an organic layer. After washing the layer with water and drying it 10 on anhydrous sodium sulfate, the solvent was distilled off from the layer under reduced pressure to form a residue.

Upon purification of the residue through a silica gel column, 2.7 g of the title compound were obtained, the physical properties of which are as follows:

Physical Properties: (1) Melting point 106 - 107 ° C.

(2) Infrared absorption spectrum (KBr method): 0 max.

3260, 3100, 2930, 1620, 1270, 1130 and 660 cm -1.

(3) NMR Spectrum (CDCl3, ppm): <δ 1.45-3.15 (m, 10H), 4.27 (s, 2H), 7.20 (d, 2H, J = 9 Hz ), 7.60 (d, 2H, J = 9 Hz), 8.13 (s, 1H) and 8.28 (s, 1H).

The following two examples (Examples 3 and 4) are examples of preparation of a fungicide for use in agriculture and horticulture containing a derivative of azole according to the invention as an active ingredient.

EXAMPLE 3.

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By pulverizing and mixing 3 parts by weight of one of the present compounds (Compound No. 12 in Table 1), 40 parts by weight of clay and 57 parts by weight of talc, a fungicidal dust was prepared.

The fungicidal dust thus produced was used in spreading at the desired site.

EXAMPLE 4.

By pulverizing and blending 50 parts by weight of one of the present compounds (Compound No. 14 in Table 1), 5 parts by weight 10 parts of a salt of lignin sulfonic acid, 3 parts by weight of a salt of an alkyl sulfonic acid and 42 parts by weight of diatomaceous earth, a fungicidal wettable powder.

The fungicidal wettable powder thus produced is used after dilution with water.

The following five examples (Examples 5-9) are examples showing the fungicidal effect of the fungicide for use in agriculture and horticulture according to the invention.

EXAMPLE 5.

Trial against Erysiphe graminis f.sp.tritici on wheat.

20 on the leaves of wheat seedlings (varieties of NORIN No. 64, 16 seedlings per pot) at the second leaf stage, grown in unglazed 16

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pot, a fungicidal wettable powder prepared by the procedure of Example 4, diluted with water to a predetermined concentration, was sprayed at an amount of 5 ml / pot (control pot was only sprayed with water). After 5 natural drying of the leaves thus sprayed, an aqueous suspension of the spores of Erysiphe graminis f.sp. tritici, collected from infested leaves of wheat, sprayed on the dried leaves of wheat in the pot, and the seedlings thus treated were kept for 24 hours at a temperature of 20 to 25 ° C in a very humid atmosphere. Then the seedlings thus treated were placed in a greenhouse. After 10 days of grafting, the mortality of the seedlings was investigated on the basis of the following standard and the control value was calculated with the following formula based on the average mortality per day. leaf: 15 Examination standard: Mortality index Scope of illness 0 Uninfected 0.5 A is less than 10% 1 A is from 10 to less than 20% 20 2 A is from 20 to less than 40% 3 A is from 40 to less than 60% 4 A is from 60 to less than 80% 5 A is greater than 80% xl)

Note ': A is the disease-infected area on the surface 25 of the seeded leaf.

mortality on treated pot

Control value = (1 - -) x 100%.

mortality on control pot

The results are shown in Table 2.

TABLE 2.

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Compound Concentration # * of the liquid (as shown in Table 1) Control value (ppm) (%) 1 125 95 2 125 90 5 3 125 95 4 125 95 5 125 100 6 125 100 7 125 100 10 8 125 100 9 125 100 10 125 100 11 125 100 12 125 100 15 13 125 50 14 125 65 15 125 70 16 125 75 17 125 70 20 18 125 100 19 125 68 20 125 100 21 125 100 22 125 100 25 23 125 62 24 125 100 25 125 75 26 125 100 27 125 100 30 28 125 100

Triadimphone 125 100

Control - 0 18

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xl)

Note: Triadimefon is a commercially available fungicide containing the following compound as active ingredient: 0 ch3

Cl-y-O-CH-I - CH3 CH3

h iiN

NOW

EXAMPLE 6.

5 Specimen against Sphaerotheca fuliginea on cucumber plant.

On the leaf of cucumber seedlings (variety: SAGAMI-HAMPAKU, one seedling per pot, 3 pots by sample of one compound) on the 2 leaf stage, grown in unglazed pot with a diameter of 10 cm, a fungicidal humidifier was sprayed 10 powder, prepared by the procedure of Example 4, diluted with water to a predetermined concentration, in an amount of 5 ml / pot (control pots were sprayed only with water), and then the traces of Sephaerotheca fuliginea from cucumber were spread on the sprayed leaves of the infected cucumber-15 leaves by using a brush to graft the leaf, and the thus-treated pots were placed in a greenhouse.

Seven days after grafting, the mortality of the seedling's leaf (1 leaf / pot, 3 pots / compound) was examined to the following standard, and the control value was calculated from the 20 average mortality per day. sheet using the same formula as in Example 5.

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Examination Standard: Mortality Index Scope of Disease 0 Uninfected y |) 0.5 A is less than 10% 5 1 A is from 10 to less than 20% 2 A is from 20 to less than 40% 3 A is from 40 to less than 60% 4 A is from 60 to less than 80% 5 A is greater than 80% y] \ 10 Note: A is the infected disease area on the surface of the seeded leaf.

The results are shown in Table 3.

TABLE 3.

Compound Concentration # * of the liquid (as shown in Table 1) Control value (ppm) (%) 15 1 62.5 98 2 62.5 70 3 62.5 100 4 62.5 90 5 62.5 100 20 6 62 5 60 7 62,5 100 8 62,5 100 Commercial fungicide χ1) 125 100 25 Control ~ 0

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Note: A quinoxaline series fungicide represented by the following formula: EXAMPLE 7.

Trial against Puccinia recondita f.sp. tritici on wheat.

5 On the leaves of wheat seedlings (variety: NORIN No. 64, 16 seedlings per pot) at the 2nd leaf stage, grown in unglazed pot of 10 cm diameter, a fungicidal wettable powder was produced by the procedure of Example 4 , diluted with water to a predetermined concentration, 10 in an amount of 5 ml / pot (control pots were only sprayed with water). After natural drying of the sprayed leaves, an aqueous suspension of the summer spores of Puccinia recondita f.sp.tritici, collected from infested leaves of wheat, was sprayed on the dried leaves of the potted wheat and the seedlings thus treated were kept in 24 hours at a temperature of 20 to 25 ° C in a very humid atmosphere. Thereafter, the treated seedlings were placed in a greenhouse and after 7 days mortality was examined on the basis of the following standard. The control value for each of the fungicides was calculated by the formula shown in Example 5, based on the average mortality per day. leaf of the 10 seedlings per pot.

Investigation Standard: Same as in Example 6.

The results are shown in Table 4.

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TABLE 4.

Compound Concentration r 'of the liquid (as shown in Table 1) Control value (ppm) (%) 1 200 78 2 200 95 5 3 200 73 4 200 88 5 200 50 6 200 75 7 200 45 2q q 200 200 9 200 90 10 200 75 11 200 68 12 200 100 15 13 200 65 14 200 45 15 200 75 16 200 75 17 200 83 20 18 20 0 88 19 200 65 20 200 100 21 200 100 22 200 88 25 23 200 68 24 200 100 25 200 70 26 200 85

Triadimefon 200 100 30 Control - 0 EXAMPLE 8.

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Specimen against Cochliobolus miyabeanus on rice plant.

In unglazed pots with a diameter of 10 cm, seeds of the rice plant (variety: SASANISHIKI) were sown in an amount of 16 seeds. pot, and at the 4-5 leaf stage, the fungicidal wettable powder prepared by the procedure of Example 4, diluted with water to a predetermined concentration, was sprayed onto the seedlings in an amount of 5 ml / pot. After naturally drying the treated leaves of the rice seedlings, an aqueous suspension of the spores of Cochliobolus miyabeanus (at a concentration of 15 spores within the field of view in a 150x magnification microscope), which was preparatively grown, was sprayed onto the leaves of the seedlings. an amount of 5 ml / pot for grafting. After grafting, the 2 ^ 5 pots were immediately taken into a seed room at 25 ° C and saturated humidity, and after staying there for 2 days the pots were moved to a greenhouse. On the 5th day after grafting, the number of disease spots was 10 leaves per day. pot counted, and the fertilizer value for each of the fungicides was calculated by the following formula:

A

Combat value (%) = (1 -) x 100,

B

where A is the number of disease spots in the treated pots and B is the number in the control pots (which were not sprayed with the fungicide).

The results are shown in Table 5.

TABLE 5.

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Relations

Concentration # * of the liquid (as shown in Table 1) Control value (ppm) (%) 1 300 100 2 300 100 5-3 300 99 4 300 98 5 300 99 6 300 98 7 300 100 10 8 300 100 9 300 80 10 300 95 11 300 98 12 300 97 15 13 300 100 14 300 90 15 300 99 16 300 100 17 300 100 20 18 300 100 19 300 100 20 300 100 21 300 100 22 300 100 25 23 300 98 24 300 100 25 300 100 26 300 100 EDDP Xl) 300 88 30 Control - 0 24

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Note x1 ^: A commercially available fungicide containing the following compound as an active ingredient:

0 ~ s '!' S Oh

EXAMPLE 9.

In vitro test against multiple fungal species.

The antifungal properties of the present compounds against several fungal species were investigated as follows.

After thorough mixing of each of the present compounds with the PSA culture medium at a predetermined concentration, the mixture thus prepared was poured into 10 cm diameter dishes in an amount of 10 ml per ml. bowl to make plate culture medium. On the other hand, each of the fungal species was grown in a plate culture medium, punched with a 6 mm diameter drill bit, and seeded on the plate culture medium thus prepared in the dishes. After grafting 15, each of the thus grafted fungi was grown for 1 - 3 days at a temperature suitable for each fungus and the growth of the fungus was determined by the diameter of each fungal colony. The results were compared with the results of the control (culture medium containing no fungicide) and on the basis of the following formula the degree of control of mycelial growth was calculated: 100 R = (d - d) - c * d c 25

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where R represents the degree of control of the mycelial growth of a fungus is the diameter of the fungal colony on the culture media plate containing each of the present compounds, and d is the diameter of the fungal colony on the culture media plate containing no fungicide (control).

The results thus obtained were judged on the basis of the following standard in 5 categories and are shown in Table 6.

Rated Default:

Growth control index Degree of control of mycelial growth 10 5 From 100 to 90% 4 From 89 to 70% 3 From 69 to 40% 2 From 39 to 20% 1 Less than 20% 26

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eh i ft 3 i 13 EXAMPLE 10.

28

DK 164548 B

Preparation of plant growth regulators and herbicidal agents containing a derivative of azole as active ingredient.

(1) Wettable powder.

The following components were pulverized and mixed to make a wettable powder that could be used after dilution with water.

Compound of the Invention (Compound No. 3 in Table 1) 50 parts by weight

Lignin sulfonate 5 parts by weight Alkyl sulfonate 3 parts by weight

Diatomaceous earth 42 parts by weight (2) Emulsifiable concentrate.

The following components were mixed uniformly to produce an emulsifiable concentrate which could be used after dilution with water.

Compound of the Invention (Compound No. 20 in Table 1) 25 parts by weight

Xylene 65 parts by weight

Polyoxyethylene alkyl aryl ether 10 parts by weight 20 (3) Cereals.

The following components were mixed uniformly with water, 29

DK 164548 B

and the mixture was granulated with an extrusion granulator, followed by drying.

Compound of the Invention (Compound No. 11 in Table 1) 8 parts by weight 5 Bentonite 40 parts by weight

Clay 45 parts by weight

Lignin Sulfonate 7 parts by weight Example 11.

Inhibition of plant length of wheat.

10 wheat grains were sown in a glass-petri dish, 8.5 cm in diameter, containing 5 ml of a 50 ppm solution of the compound being tested. (The wheat variety is AOBA # 3). After growing indoors at 27 ° C for 7 days, plant length was measured. The results are shown in Table 7.

15 It will be seen from Table 7 that all the compounds tested gave a pronounced effect towards inhibition of plant length growth, especially in the case of triazole type compounds. No phytotoxicity was observed.

TABLE 7.

30

DK 164548 B

Compound Inhibition of No. * Plant Length (as in Table 1) (%) Phytotoxicity 1 3.8 None 2 3.1 None 5 3 13.7 None 4 3.5 None 5 20.4 None 6 35.7 None 7 7, 2 None 10 8 11.9 None 9 45.6 None 10 81.8 None 11 16.5 None 12 63.4 None 15 13 3.7 None 14 54.1 None 15 15.2 None 16 85.4 None 17 38.1 None 2 18 18.8 No 19 11.8 None 20 62.6 None 21 19.6 None 22 46.6 None 25 23 11.2 None 24 79.0 None 25 14.7 None 26 72.5 None 27 35.5 None 30 28 14.3 None

The average length of wheat in the control group was 80.5 mm.

EXAMPLE 12.

31

DK 164548 B

Sample weed killing (soil treatment before germination).

Several types of weed seeds were sown in sandy clay soil, filled in a tray (650 x 210 x 220 mm). The day after seeding, the soil surface was sprayed with a suitably diluted liquid of the emulsifiable concentrate prepared by the procedure of Example 10 (2).

The weed plants were grown in a greenhouse and the weed-killing effect was observed on the 21st day after treatment. The weed killing effect was assessed according to the following standard.

The results are shown in Table 8.

Index Kill rate 0 No kill effect 15 1 Kill effect of 30% 2 Kill effect of 31 - 50% 3 Kill effect of 51 - 70% 4 Kill effect of 71 - 90% 5 Kill effect of 91 - 100% TABLE 8.

32

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Compound No. ________ Weed __ (see_riot) _________ (as in Table 1) A.r. B.p. S.N. E. F. S. V.

1 4 4 4 3 3 2 4 4 4 3 3 5 3 5 5 5 4 4.

5 5 5 5 5 5 6 5 5 5 5 5 5 5 5 5 4 4 8 5 5 4 4 10 9 5 5 5 5 5 5 5 5 5 5 11 5 5 5 5 5 5 5 5 5 5 5 5 5 5 4 4 15 14 5 5 5 5 5 15 5 5 5 5 5 16 5 5 5 5 17 5 5 5 5 5 18 5 5 5 5 20 20 5 5 5 5 5 20 5 5 5 5 5 5 5 5 5 5 5 22 5 5 5 4 4 23 5 5 5 5 5 25 24 5 5 5 5 5 5 5 5 5 5 26 5 5 5 5 5 27 5 5 5 5 5 28 5 5 5 5 5 5 30 Control 00000

Claims (27)

33 DK 164548 B Note: The abbreviations in Table 8 denote the following weed species: A.r .: Amaranthus retroflexus. 1. Azolylmethylcyclopentane derivative of formula I 15 / * ==. | ρ <32-B (I) 20 where B is a 2-chlorophenyl group, 3-chlorophenyl group, 2,4-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluoro-phenyl group, 2-fluoro-4-chlorophenyl group, 2 , 3,4,5,6-penta-fluorophenyl group, 4-bromophenyl group, 4-nitrophenyl group, 4-methylphenyl group, 4-t-butylphenyl group, p-biphenylyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group or 4- cyanophenyl group, and A is a nitrogen atom or a methine group. Azolylmethylcyclopentane derivative according to claim 1, characterized in that B is a 4-bromophenyl or 4-methylphenyl group and A is a nitrogen atom. Azolylmethylcyclopentane derivative according to claim 1, characterized in that B is a 3,4-difluorophenyl group or 2,4-difluorophenyl group and A is a nitrogen atom. 34 DK 164548 B Azolylmethylcyclopentane derivative according to claim 1, characterized in that B is a 2,3,4,5,6-pentafluorophenyl group and A is a nitrogen atom. A process for the preparation of an azolylmethylcyclopentane derivative of the formula I / A = j HO / CH2 "NC * X2 5 BC: Bidets pilosa. Sen: Solanum nigrum. Example: Echinochloa frumentaceum. SW: Setar ia vi ridis. 6. Agricultural and horticultural products having fungicidal, plant growth regulating and herbicidal activity, characterized in that it contains as an active ingredient an azolylmethylcyclopentane derivative of the formula I 5 / A "- I HQV CH - N ν '- ^ = - n (I ) In pCH 2 -B 10 '-' where B is a 2-chlorophenyl group, 3-chlorophenyl group, 2,4-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluoro-phenyl group, 2-fluoro-4-chlorophenyl group, 2 , 3,4,5,6-penta-fluorophenyl group, 4-bromophenyl group, 4-nitrophenyl group, 4-methylphenyl group, 4-t-butylphenyl group, p-biphenylyl group, 3-trifluoromethylphenyl group, 4-trifluomethylphenyl group or 4-trifluomethylphenyl group and A is a nitrogen atom or a methine group, as well as an agricultural and horticultural acceptable carrier. 7. Fungicide for use in agriculture and horticulture, characterized in that it contains an azolylmethylcyclo-of formula I as active ingredient 25 A = j HO 2 CH - N 1 1 \ = NI pCH 2 -B (1) 30 wherein B is a 2-chlorophenyl group, 3-chlorophenyl group, 2,4-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluoro-phenyl group, 2-fluoro-4-chlorophenyl group, 2,3,4,5,6-penta -35 fluorophenyl group, 4-bromophenyl group, 4-nitrophenyl group, 4-methylphenyl group, 4-t-butylphenyl group, p-biphenylyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group and 4-cyanophenyl nitrogen atom or a methine group, as well as a fungicidal acceptable carrier. Fungicide according to claim 7, characterized in that B is a 4-bromophenyl group, 4-methylphenyl group or 4-t-butylphenyl group or p-biphenylyl group, and A is a nitrogen atom. Fungicide according to claim 7, characterized in that B is a 4-bromophenyl group, 4-t-butylphenyl group or p-biphenylyl group, and A is a staple group. The fungicide according to claim 7, characterized in that B is a 2,4-difluorophenyl group, 3,4-difluorophenyl group or 2-fluoro-4-chlorophenyl group, and A is a nitrogen atom. 10 Patent Claims. Fungicide according to claim 7, characterized in that B is a 2,4-difluorophenyl group or 2-fluoro-4-chlorophenyl group and A is a methine group. 11-β2-B (I) wherein B is a 2-chlorophenyl group, 3-chlorophenyl group, 2,4-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluoro-phenyl group, 2-fluoro-4-chlorophenyl group, 2, 3,4,5,6-penta-fluorophenyl group, 4-bromophenyl group, 4-nitrophenyl group, 4-methylphenyl group, 4-t-butylphenyl group, p-biphenylyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group or 4-cyanophenyl group and A is a nitrogen atom or a methine group, characterized in that a derivative of oxirane of the formula II t is in CH 1 -B 2 (II} where B is as defined above) reacted with a 1,2,4 triazole or an imidazole of formula III I (III) \ = N 35 where M is a hydrogen atom or an alkali metal atom and A is a nitrogen atom or a methine group. Fungicide according to claim 7, characterized in that B's have a 2,3,4,5,6-pentafluorophenyl group and A is a nitrogen atom. Fungicide according to claim 8, characterized in that B is a 4-bromophenyl group or 4-methylphenyl group. 30 Fungicide according to claim 10, characterized in that B is a 2,4-difluorophenyl group, 3,4-difluorophenyl group or 2-fluoro-4-chlorophenyl group. Fungicide according to claim 13, characterized in that B is a 4-bromophenyl group. 37 DK 164548 B Fungicide according to claim 14, characterized in that B is a 3,4-difluorophenyl group. Plant growth regulator for use in agriculture and horticulture, characterized in that it contains as an active ingredient an azolylmethylcyclopentane derivative of formula I HO, CH, -tr 10 κ \ α, 2-b (I) where B is a 2-chlorophenyl group, 3-chlorophenyl group, 2,4-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl group, 2-fluoro-4-chlorophenyl group, 2,3,4,5,6-penta-fluorophenyl group, 4-bromophenyl group, 4 -nitrophenyl group, 4-methylphenyl group, 4-t-butylphenyl group, p-biphenylyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group or 4-cyanophenyl group, and A is a nitrogen atom or methane group, as well as an acceptable carrier for plant. Plant growth regulator according to claim 17, characterized in that B is a 4-bromophenyl group, 2-chlorophenyl group, 4-methylphenyl group or 4-cyanophenyl group, and A is a nitrogen atom. Plant growth regulator according to claim 17, characterized in that B is a 2,6-difluorophenyl group, 3,4-difluorophenyl group or 2-fluoro-4-chlorophenyl group, and A is a nitrogen atom. Plant growth regulator according to claim 17, characterized in that B is a 2,3,4,5,6-pentafluorophenyl group and A is a nitrogen atom. 38 DK 164548 B Plant growth regulator according to claim 18, characterized in that B is a 4-methylphenyl group. Plant growth regulator according to claim 19, characterized in that B is a 2,6-difluorophenyl group or 2-fluoro-4-chlorophenyl group. 23. Herbicide for use in agriculture and horticulture, characterized in that it contains as active ingredient 10 an azolylmethylcyclopentane derivative of the formula IH ° x \ y 4 \ 1 - ^ in Λόη, - b (i> 15 _ 2 where B is a 2-chlorophenyl group, 3-chlorophenyl group, 2,4-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl group, 2-fluoro-4-chlorophenyl group, 2,3,4,5,6-penta-fluorophenyl group , 4-bromophenyl group, 4-nitrophenyl group, 4-methylphenyl group, 4-t-butylphenyl group, p-biphenylyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group or 4-cyanophenyl group, and A is a nitrogen atom or an acceptable carrier for a herbicide. Herbicidal agent according to claim 23, characterized in that B is a 4-bromophenyl group or 4-methylphenyl group and A is a nitrogen atom. Herbicidal agent according to claim 23, characterized in that B is a 3-trifluoromethylphenyl group or 4-trifluoromethylphenyl group and A is a methine group. 35 Herbicidal agent according to claim 23, characterized in that B is a 2,4-difluorophenyl group or 2-fluoro-4-chlorophenyl group and A is a nitrogen atom. 39 DK 164548 B Herbicidal agent according to claim 23, characterized in that B is a 2,3,4,5,6-pentafluorophenyl group and A is a nitrogen atom. 5 10 15 20 25 30 35