CS241472B2 - Fungicide,herbicide or plant growth influencing preparation - Google Patents

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DESCRIPTION OF THE INVENTION

PATENT (22) Registered 19 03 80 (21) (PV 1903-80) (32) (31) (33) Priority from 20 03 79 (32876), from 06 08 79 (100547), from 25 09 79 ( 123485), from 10 09 79 (116576) and from 30 01 80 (10568) Japan (40) Published 16 07 85 (45) Published 15 09 87 241472 (11) (M) (51) Int. Cl.4A 01 N 43 / 64C 07 D 249/08 FUNAKI YUJI, TOYONAKA, · OSHITA HIROFUMI, TOYONAKA / YAMAMOTO SHIGEO, IKEDA; TANAKA SHIZUYA, MINOO; KATO TOSHIRO, TAKARAZUKA (Japan) SUMITOMO CHEMICAL COMPANY, LIMITED, HIGASHI (Japan) (54) Fungicide, Herbicide and / or Plant Growing Agent 1

The present invention relates to one of the two isometric isomers (a compound defined as isomer IA in the description below) of the triazole derivatives of general formula I

where

R 1 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 3 or 4 carbon atoms, or a 2-propynyl group, R 2 is a group having 1 to 6 carbon atoms or a cyclopropyl or 1-methylcyclopropyl group, R 3, which are the same or different, halogen-labeled, (C1 -C4) alkyl, (C1 -C3) alkyl, (C1 -C4) alkoxy, phenoxy, phenyl, cyano or. nitrosCupine, n is an integer from 0 to 3, and halogen is chlorine, bromine, fluorine, its salts, a process for their production and fungicides, herbicides and / or plant growth modifying agents for agriculture and horticulture, which contain thio compounds as active ingredients.

Each thiazole derivative of Formula I has two geometric isomeric forms, the E-form represented by the general formulas 9Ri

H CH-R

Z-formORi /) / c = cx "ΰ E-form 241472

At present it is not clear which of the two-isomeric forms belongs to the compounds of the invention, and therefore the properties of the compounds can only be expressed conditionally. These isomers can be distinguished from each other by the melting temperature. NMR spectrum or gas-chromatography, but the difference between them can be characterized more generally and more clearly by the starting material, a triazole-general derivative of the formula II wherein:

R 2, R 5 and n are as defined above. The triazole derivative of formula (I) is obtained by reducing the triazole derivative of formula (II) to give the triazole derivative of formula (I) wherein R 1 is a hydrogen atom, which is then etherified to the resulting compound. compound:

o I! reduction 11 - CH = C- II)

Oty R <eth.eřifík <RTIgt; 3

(I) (RfH) '1 R 1' R 3> tx. 1A, (I) (R 1: substituents other than hydrogen), where

R 1, R 2, R 3 and n are as defined above.

One of the two geometric isomers of the triazole compound of formula II in which the olefin proton has a higher magnetic field on the NMR spectrum in deuterochloroform defines its isomer IIAa and the second one, whose olefin proton exhibits a lower magnetic field of the NMR spectrum. in de-terochloroform, is defined as isomer IIB.

Further, a compound of formula I wherein R 1 is a hydrogen atom produced by the reduction of the isomer IIA is defined as isomeric A 1. The compound of formula (I) wherein R 1 is defined as a substituent other than the hydrogen atom produced by etherification of the isomer Ia is defined as isomer I "A". Isomer I'A and isomer l 'A are species-defined as isomer IA. The corresponding compounds derived from the isomer IIB in the same manner as above are defined as iso-mer I'B, isomer I 'B and isomer IB. The present invention relates to isomer IA and isomer IIA, which is an intermediate after isomer IA.

To date, a large number of organic synthetic compounds have been developed which present great benefits as agricultural chemicals for the sustained supply of agricultural and horticultural production by their antifungal and anti-harvesting fungi. The reality is, however, that there are a number of problems to be improved. Such problems are sometimes solved, for example by the development of new and more suitable pesticides, or it can be assumed that they are also

S solved by discovering the usual pesticides, determining the correct use of agricultural chemicals.

There are few organic synthetic compounds that may also be present in the form of geometric or optical isomers. In fact, there are many cases where pesticides containing these isomers are practically used as agricultural chemicals. Not only in agricultural chemicals, but also in many other areas, it is well known that in the case of many active isomeric forms, differences in the biological effects of isomers are observed in the individual isomers. Recently, environmental pollution has become serious in the field of agriculture and horticulture and it is important to alleviate this problem by using one of the paired Isomers, which has a stronger effect. Also, the more economical effect of compound production as well as its use as agricultural chemistry should be taken into account. From this point of view, the authors further studied compounds previously discovered (published by Japanese Patent Laid-open Publication No. 130 661/1978, Belgian Patent No. 870 243 [published Japanese Patent Publication No. 41 875/1979 The result is that the present compounds defined as isomer IA, which are one of the two isomeric isomers of the triazole compound of formula I, have a higher fungicidal effect over a wide range of plant pathogens, as well as higher herbicidal activity and higher an effect affecting plant growth than compounds defined as IB isomer. In other words, these compounds possess properties such as agricultural chemistry.

There are a number of other well-known triazole derivatives disclosed in British Patent No. 1,364,619, Belgian Patent No. 845,433, NSR Patent Nos. 26,102,226, 54,890, and 27,334,426, and U.S. Pat. However, it is characteristic of the present invention that this new information has been found: One of the two geometric isomers of the triazole compound of formula I, characterized in that it has both (1J double bond (benzylidene group) and (2) a hydroxy group or ethers thereof having the structure r - ---- - OR;

6 characteristics differing from the previously known compounds and, in addition, have better properties when compared to conventional compounds. Accordingly, the present invention is based on the fact that it has never been possible to assume that the compounds are based on previous data.

As diseases to which the compounds according to the invention (IAJ isomer can be used in a superior protective action, rice rice (Pyricularia oryzaej, Pellicularia sasa-kii), apple-tree blight (Valsa malij, sclerotinia had ), apple apple powdery mildew (Podosphaera leucotricha), apple tree species (Venturia inaequalis), apple tree spots (Mycosphaerella pomi), apple almond tree (Algernaria mali), alternarial (Alternaria kikuchianaj, corn powdery mildew (Phyllactinia pyrij, pear tree (Gymnosporangium haraeanum); anthracite-grape vine (Elsinoe ampelina), grape mold (Glomerella cingulata), urea grape varieties (Botritys cinereaj, padlírévové (Uncinula necatórj, cut on grapevine (Phakopsorá ampelopsidis), oat (Puc-cinia coronata) cut, barley powdery mildew (Erysiphe graminis), barley rhynchosporial stain (Rhynchosporium secalisj, barley stripe) (Helminthosporiumgramineum), barley dust (Usti-lago nuda), barley (Ustilago hor-deij, barley gangrene (Typhula incarnata), black barley (Puccinia graminis), wheat grove (Puccinia recondita), dust-dust (Ustilago tritici), pungent wheat (Tilletia caries), wheat blotch (Septoria tritici and Septoria nodorum), wheat yellow (Puccinia striiforrnis J, black wheat (Puccinia graminis), wheat powdery mildew (Erysiphe graminis), powdery mildew (Sphaerotheca fuliginea), gray cucumber mold (Botrytis cinerea), cucumber gangrene (Mycosphaerella melonis), willow plant (Sclerotinia sclerotiorum), anthracone in cucumber (Colletotrichum laganerium), yellowish black on tomatoes (Cladosporiumfulvum), powdery mildew of tomatoes (Erysiphe cichoracea-rum), brown blotch of potato leaves (Alternaria solani), mildew on eggplant (Botrytis cinerea), verticiliózabrambor in eggplant (Verticillium albo -atrum), powdery mildew of eggplant (Erysiphe cichoracea-rum), powdery mildew of myrtle (Le-veillula taurica) ^ gray mold (Bot-rytis cinerea), powdery mildew (Sphae-rotheca humuli), alternarie tobacco (Alter-naria longipes), powdery mildew of tobacco (Ery-siphe cichoracearum), spotted spotted beetle (Cersospora beticola), has much better properties than agricultural chemicals compared to the second geometry isomer. In this respect, the present compounds have different structures (Cercospora personata and Cerco-spora arachidicola) and the like. From further study of the antimicrobial effect of the present compounds, it is clear that the compounds are also antimicrobial against Trychophyton rubrum. Thus, it has been found that the present compounds can be used as parasitic fungus-induced anti-disease agents. Further, the compounds of the invention, iso-IA, can be used as plant growth-modifying agents because they control plant growth. For example, the compounds may be used to prevent the expulsion of rice, wheat, lawn, hedge and fruit trees and potted chrysanthemums. When rice and grain are grown, lodges and grains caused by the use of fertilizer fertilizers are often dangerous. The use of the compounds of the invention at the appropriate time is effective to suppress the growth of rice and grain to a height and to prevent lodging. In the cultivation of potted chrysanthemums, the use of the present compounds is desirable to increase the commercial value of the precipitants, since the height of the stem can be shortened without affecting the flower.

Isomer IA of the compound of the invention has a potent herbicidal action against grass field weeds such as Echinochloa crus-galli, Digitaria sanguinalis and Setaria viridis; broadleaf field weeds, such as Cyperus difformis Lj, Amaranthus retroflexus, Chenopodium album, Portulaca oleracea, and Stellaria media, and annual and perennial bales in fields such as hedgehog chickens foot (Echinochloa crus-galli), Monochoria viaginalis, Rotala indica Koehne, Dopatriumjunceum, scirpus junco- des var. Hotarui ohwi and Eleocha-ris acicularis.

If the compounds of this invention are applied in the field, they are also very good for the following reasons: they have a strong herbicidal effect on the antifungal weeds growing in the field, they have the effect of either treating the soil prior to emergence or treating the leaf after the onset and beyond they can be safely applied without damaging the main plant (for example, rice, soybean, cotton, grain, groundnut, sunflower, beet), as well as vegetables (such as lettuce, radish, tomato). If the compounds of the present invention are applied to the cultivated field, they also exhibit a strong herbicidal effect on the anti-weed weeds either in pre-treatment or leaf-on-treatment and in addition! are highly safe for rice plants.

In addition, the compounds of the present invention are particularly useful as herbicides not only for unshelled rice, but also for various harvested crops, vegetables, orchards, lawns, pastures, tea plantations, mulberries and rubber trees, forest and uncultivated areas. Furthermore, it is evident that the compounds of the invention are very safe for mammals and in addition to being able to be used in practice without endangering the agricultural product.

The triazole compounds of formula (IIA), which are intermediates for the compounds of formula (IA), also have a fungicidal action against various pathogens that they train in agriculture, as well as the herbicidal and plant growth-promoting action. However, it is also a fact that the compounds of formula (IA) present have a much stronger effect against large-scale pathogenic pathogens, as well as a more potent herbicidal and plant-growth effect than the general formula IIA compounds. Further, more precise methods for producing the compounds of the invention are given below:

Method A

Reduction of the triazole compound of formula II

O>/> Reducers /> —CH-C C Rt — —— · - “1

isomer IIA

Ofi 1 C-CH-R. isomer I * A (R 1 = H) 241472 9 10 where

R 2, R 3 and n are as defined above. The I A isomer is produced by reduction of the isomer IIA in a suitable solvent with a complex metal hydride (e.g., lithium aluminum hydride, sodium borohydride or aluminum alkoxide (e.g., alumina isopropoxy)). can be obtained in pure form, for example, by fractional crystallization or by column chromatography of mixtures of geometric isomers of the triazole compound of formula (II) produced according to the following reaction formula: The isomer IIA can also be obtained in good yield by, for example, irradiation with a mixture of ultraviolet radiation to effect photo-isomerization. A more detailed explanation will be given below in connection with Methods C and D.

(III)

. O

(IV) o

II

CH-CC

..And where (where) where

R 2, R 5 and n are as defined above. Among the solvents used in the metal complex hydride reduction, for example, ethers (such as diethyl ether, tetrahydrofuran, and alcohols (e.g., methanol, ethanol, isopropanol) are included. The reaction is carried out by mixing 1 mol of isomer IIA and 0.25 to 2 moles of narium borohydride in a solvent, preferably from 0 DEG C. to about 50 DEG C. The solvents used include, for example, ethers (such as diethyl ether, tetrahydrofuran). and alcohols (e.g., methanol, ethanol, isopropanol) When lithium aluminum hydride is used as the complex hydride, the reaction is carried out by dissolving lithium aluminum hydride in a 0.25- to 0.8-fold amount of solvent based on the isol IIA isomer and the resulting solution. the isomer solution in the same solvent is added. The reaction temperature is preferably in the range of -60 to 70 ° C The solvents used include ethers (e.g., diethyl ether, tetrahydrofuran). Upon completion of the reaction, water or acid is added to the reaction solution by dilution, and after optionally neutralizing the alkali, the precipitated crystals are filtered off or extracted with an organic solvent which is sparingly soluble in water. The following processing is performed by conventional methods.

When aluminum isopropoxide is used as the reducing agent, it is preferred to use such solvents as alcohols (e.g. isopropanol) or aromatic hydrocarbons (e.g. benzene). Generally, one mole of IIA isomer with 1 to 2 moles of aluminum isopropoxide is reacted at room temperature to 100 [deg.] C. The resulting alkaline compound is quenched with dilute sulfuric acid or aqueous sodium hydroxide solution and then extracted with an organic solvent which is sparingly soluble in water. Further processing is carried out by conventional methods.

The salts of the isomer I * A relate to those salts obtained with plant-physiologically acceptable acids such as halodic acid (e.g. hydrobromic acid, hydrochloric acid and hydroiodic acid), carboxylic acids (e.g. sulfonic acids (e.g. p-toluenesulfonic acid and methanesulfonic acid), nitric acid, sulfuric acid and phosphoric acid. If desired, these salts are produced by conventional methods.

Method B

etherification isomer I'A (Ri = H) 241472 11 12 ORi jQ> -ch = c-ch-r2 1 R3'fi L-ii

Isomer I "A (R 1: substituents different from hydrogen) where

R 1, R 2, R 5 and n are as defined above.

The isomer I ' A of the present compounds is obtained by reacting the I'A isomer with a reactive derivative containing 1 to 4 carbon atoms, alkenyl of 3 or 4 carbon atoms, or 2-propynyl, in a suitable solvent in the presence of a base. . Reactive derivatives include, for example, alkyl, alkenyl, or alkynyl halides (e.g., methyl iodide, alkyl bromide, propargyl bromide), sulfates (e.g., dimethyl sulfate, diethyl sulfate) and sulfonates (e.g., p-toluenesulfonate, naphthalenesulfonate). such as diethyl ether, tetrahydrofuran, dioxane, benzene, toluene, xylene and dimethylformamide. The reaction may be carried out in the presence of water using a phase transfer catalyst such as a reaction accelerator (e.g., triethylbenzylammonium chloride, trimethylbenzyl ammonium bromide). Bases include, for example, strong bases (for example, alkali metal hydrides such as sodium hydride, alkali metal amides, for example sodium amide), carbonates (e.g., sodium carbonate and potassium carbonate), and alkali metal hydroxides (e.g., potassium hydroxide and sodium hydroxide) ).

This reaction is carried out by admixing an isomer, a C 1 -C 4 -alkyl reactive derivative, an alkenyl of 3 or 4 carbon atoms, or a 2-propynyl base, preferably in an equimolar ratio, in a suitable solvent. The reaction is carried out at a temperature ranging from 0 to 100 ° C, preferably from 20 to 60 ° C. It is sometimes advantageous to first react the isomer of IA with a suitable strong base (for example, alkali metal hydrides or alkali metal amides) in the internal solvent, and the resulting alkaline salt is then not reacted with the reactive derivative contained therein. C 1 -C 4 alkyl, 3 or 4 carbon alkenyl, or 2-propynyl. In some cases, the following is suitable for the isolation of compounds of formula (I):

The reaction mixture is freed from the solvent by evaporation and water and water-soluble solvent are added to the residue, the organic layer is separated after extraction and then purified by suitable methods.

The salts of isomer I &quot; refer to those salts which are obtained with physiologically acceptable acids, such as hydrohalic acids (e.g. hydrobromic acid, hydrochloric acid and hydroiodic acid), carboxylic acids (e.g. acetic acid, trichloroacetic acid, maleic acid and succinic acid, sulfonic acids (e.g., p-toluenesulfonic acid and methanesulfonic acid), nitric acid, sulfuric acid, and phosphoric acid. If desired, these salts are produced by conventional methods.

The present invention is illustrated in more detail by the following examples. Unless otherwise stated, the NMR spectrum of the examples is given in δ with deuterochloroform as solvent and tetramethylsilane as an inert standard. Přikladl

Synthesis of 1- (4-chlorophenyl) -4,4-dimethyl-2- (1,2,4-triazol-1-yl) -1-penten-3-ol isomer I'A (Compound No. 1) Method A, 2.9 g (0.01 mole) of IIA isomer (m.p. 108-109 ° C, 1- (4-chlorophenyl) -4,4-dimethyl-2- (1,2,4-triazole-1 1-penten-3-one (Compound No. 1 &apos;) was dissolved in 50 mL of methanol and 0.38 g (0.01 mol) of sodium borohydride was added to the mixture while cooling the temperature. The reaction mixture is maintained at 20 ° C for 3 hours and then quenched by the addition of 100 ml of water and 1 ml of acetic acid, the organic layer is extracted with 100 ml of ethyl acetate and the extract is washed with 50 ml of 5% aqueous water. The solvent is evaporated off under reduced pressure and the residue obtained is recrystallized from isopropanol to give 2.0 g (69% yield) of isomer I'A having a melting point. 153-155 ° C Elemental analysis and NMR spectra of the compound are shown H, N, 14.40; N, 12.15. Found: C, 61.82; H, 6.33; H, 14.38. % N, 12.15% Cl. NMR Spectrum:

8.52 (1H, s, triazole proton L 7.98 (1H, s, triazole proton), 241472 13 7.30 (4H, s, phenyl proton), 6.91 (1H, s, olefin proton), 4.56 (2H, broad singlet, hydroxyl proton and methine proton at OH group), 0.66 (9H, s, butyl proton).

Comparative Example 1

1- (4-Chlorophenyl) -4,4-dimethyl-2- (1,2,4-triazol-1-yl) -1-penten-3-ol isomer I'B isomer synthesis (Compound No. 1) 2.9 g (0.01 mol) of IIB isomer (m.p. 78-79 ° C) 1- (4-chlorophenyl) -4,4-dimethyl-2- (1,2,4-triazole-1) -yl) -1-penten-3-one (Compound No. 1 ') is dissolved in 50 ml of methanol. The isomer is reacted with na- triumborohydride and then treated in the same manner as in Example 1. The obtained residue is recrystallized from a 1:10 mixture of carbon tetrachloride and n-hexane to give 2.2 g (76% yield). isomer ΓΒ (melting point 116-117 CC) of Compound No. 1. The elemental analysis and NMR spectrum are as follows.

Elemental analysis for C15H18N3OCl: calculated: 61.74% C, 6.23% H, 14.40% N, 12.15% Cl, found: 61.80% C, 6.25% H, 14.52% N Cl NMR Spectrum: 7.92 (s, triazole proton), 7.77 (1H, s, triazole proton), 7.05 (2H, d, phenyl proton, J = 9Hz), 6.58 (2H) , d, phenyl proton, J = 9Hz), 6.66 (1H, s, olefin proton), 4.28 (1H, d, methine proton at OH group, J = 6Hz), 3.21 (1H, d, hydroxyl proton, J = 6Hz), 0.80 (9H, s, butyl proton). Example 2

Synthesis of the isomer IA of 3- (4-chlorophenyl) -1- (1-methylcyclopropyl) -2- (1,2,4-triazol-1-yl) -2-propen-1-ol (Compounds No. 30) method A? 2.9 g (0.01 mol) of IIA isomer (mp 89-92 ° C) 3- (4-chlorophenyl) -1- (1-methylcyclopropyl) -2- (1,2,4) -triazol-1-yl) -2-propen-1-one (Compound No. 29 '), characterized by the NMR spectrum described below, was dissolved in 50 mL of methanol. Sodium borohydride (0.38 g, 0.01 mol) was added to the mixture, while cooling the reaction temperature to 20 ° C or less. The reaction mixture was kept at 20 ° C for 3 hours and then quenched by the addition of 100 mL of water and 2 mL of acetic acid. The organic layer was extracted with 100 mL of chloroform and the extract was washed with 50 mL of 5%. aqueous sodium bicarbonate solution and dried with anhydrous magnesium sulfate. The solvent is then evaporated under reduced pressure and the residue obtained is crystallized from 5 ml of a 1: 1 mixture of carbon tetrachloride and n-hexane. 2.4 g (yield 85%) of the title compound are obtained.

The starting material NMR spectrum of 3- (4-chlorophenyl) -1- (1-methylcyclopropyl) -2- (1,2,4-triazol-1-yl) -2-propen-1-one isomer IIA is 8.28 (1H, s, triazole proton), 8.07 (1H, s, triazole proton), 7.32 (4H, s, phenyl proton), 7.19 (1H, s, olefin proton), 1, 45-1.15 (2H, m, methylene proton cyclopropyl group), 1.25 (3H, s, methyl proton), 0.99-0.75 (2H, m, methylene protonocyclopropyl group).

Comparative Example 2

Synthesis of 3- (4-chlorophenyl) -1- (1-methylcyclopropyl) -2- (1,2,4-triazol-1-yl) -2-propen-1-ol isomer I'B (Compounds No. 30) 2 g (0.007 mol) of isomer IIB (m.p. 74-75 ° C) 3- (4-chlorophenyl) -1- (1-methylcyclopropyl) -2- (1,2,4-triazol-1-yl) 2-propen-1-one (Compound No. 29 '), characterized by the NMR spectrum described below, was reacted in the same manner as in Example 2 with 0.27 g (0.007 mol) of sodium borohydride in 50 ml methanol. 1.7 g (85% yield) of the title compound are obtained.

Starting material NMR spectrum of 3- (4-chlorophenyl) -1- (1-methylcyclopropyl) -2- (1,2,4-triazol-1-yl) -2-propen-1-one isomer IIB the following: 8.12 (1H, s, triazole proton), 8.03 (1H, s, triazole proton), 7.55 (1H, s, olefin proton), 7.21 (2H, d, phenyl proton, J = 8Hz), 6.81 (2H, d, phenyl proton, J = 8Hz), 1.50-1.25 (2H, m, methylene protonclopropyl), 1.28 (3H, s, methyl proton), 0.90 0.65 (2H, m, methylene proton of the cyclopropyl group). Example 3

Synthesis of Isomer I "A 1- (4-Chlorophenyl) -4,4-dimethyl-3-methoxy-2- (1,2,4-triazol-1-yl) -1-pentene (Compound No. 35 ) by Method B 2 g of β-chlorophenyl-4,4-dimethyl-2- (1,2,4-triazol-1-yl) -1-penten-3-ol isomer (Compound No. 1) dissolved in 20 ml of dimethylformamide and 0.26 g of 65% sodium hydride in oil added. After stirring for one hour at room temperature, the reaction mixture was cooled to 10 ° C and 1 g of methyl iodide was added. After standing at room temperature for 20 hours, the solvent was removed under reduced pressure and the residue obtained was extracted with 100 g of ice water and 100 ml of 241472 13 16 chloroform. The organic layer was dried over anhydrous magnesium sulfate and the solvent was evaporated under reduced pressure. The oily crude product obtained is purified by column chromatography on silica gel (acetone: n-hexane = 1:10) and further recrystallized from carbon tetrachloride / n-hexane (1: 2). 1.6 g of the title compound is obtained (m.p. 63-66 ° C).

Comparative Example 3

Synthesis of Isomer I “B 1p-chlorophenyl-4,4-dimethyl-3-methoxy-2- (1,2,4-triazol-1-yl) -1-pentene (Compound No. 35) 2g Isomer I * B of 1- (4-chlorophenyl) -4,4-dimethyl-2- (1,2,4-triazol-1-yl) penten-3-ol (Compound No. 1) was dissolved in 20 ml of dimethylformamide and 0.26 to 65% of Na-trihydride. After stirring at room temperature for 1 hour, the reaction mixture was cooled to 10 ° C and 1 g of methyl iodide was added. The reaction mixture was kept at 10 [deg.] C. for 1 hour and then allowed to stand at room temperature for 16 hours. The dimethylformamide was evaporated under reduced pressure and the residue was extracted with 100 g of ice water and 100 ml of chloroform. The organic layer was dried over anhydrous magnesium sulfate and the solvent removed under reduced pressure. The resulting crude product was purified by silica gel column chromatography (acetone: n-hexane = 1: 10). 1.0 g of the title compound is obtained in the form of an oily product.

Refractive index nD27 1.5435.

H, 6.60; N, 13.77; N, 11.50; C, calculated: C, 62.84; H, 6.59; N, 13.74. , 11.59 O / O Cl.

The compounds (isomer IA) obtained by Method A and B are shown in Table 1. For comparison, the isomer IB data are reported together. Unless otherwise indicated, the NMR spectrum in the table is S with de-terochloroform as solvent and te-tetrethylsilane as internal standard. The isomer 1A and isomer I "A are generically referred to as isomer IA and the isomer isB and isomer. "B is also generically referred to as isomerIB. Species features are also used in the test examples described below.

241472 TABLE 1

OR 1 CH = C-CH-R 2

M

III

Compound No. Ri R2 (Rs) n Geometric isomer type Physical constant 1 HC (CH 3) 3 4-Cl IA tt 153-155 ° C IB tt 116-117 ° C 2 HC (CH3) 3 2.4 -di-Cl IA tt 148 to 149 ° C IB tt 146 to 147 ° C 3 HC (CHs) with 4-Br IA tt 146 to 149 ° C IB tt 127 to 128 ° C 4 HC (CH3) 3 4-F IA tt 203 to 204 ° C IB tt 82 to 85 ° C 5 HC (CH3) 3 2-C1 IA tt 168 to 170 IB tt 109 to 110 ° C 6 HC (CH 3) 3 4-phenyl IA mp 158-161 ° C IB tt 172-173 ° C 7 HC (CH 3) 3 -OCH 3 IA tt 162-163 qC IB tt 102-104 ° C 8 HC (CH3) 3-CN IA tt 191-195 IB tt 111-114 ° C 9 HC (CH 3) 3 H IA tt 153 to 155 ° C IB tt 88 to 90 ° C 10 HC (CH 3) S 4-CH 3 IA • tt 155 to 157 ° C IB tt 127 to 128 ° C 11 HC (CH3) ) 3 4-NO 2 IA tt 194 to 195 ° C IB tt 123 to 124 ° C 12 HC (CH3) S 4-phenoxyl IA tt 164 to 165 ° C 13 H CH3 4-C1 IA tt 88 to 89 ° C XCh2- CH | 141h 142 ° C 14H 4- <Cl IA IB tt 110-112%! nD26 1.5 600 CH3 / 15 H-CH 4-Cl IA tt 127 to 128.5 ° C CH 3 IB tt 106 to 107 ° C

16 HC (CH 3) 3 3-CF 3 IA nD25 1.5 055 IB tt 117-119 CG 241472 NMR spectrum OR 1

Triazole Proton Olefin | proton — CH — Rz

Rz proton 8.52, 7.92, 7.98 7.77 6.91 6.60 4.56 4.28 (d, J = 6 Hz) 0.66 0.80 8.45, 7.97 6 , 80 4.35 0.63 7.90, 7.65 6.72 4.36 (d, J = 6 Hz) 0.88 8.55, 8.02 6.90 4.58 (d, J = 9 Hz) 0.70 7.98, 7.82 6.62 4.30 (d, J = 5 Hz) 0.80 8.82, 8.09 7.04 4.61 (d, J = 4 Hz ) 0.63 7.93, 7.76 7.14 4.25 0.81 8.90, 8.11 7.08 4.50 [d, J = 4 Hz] 0.59, X5 8.02, 7.75 6.89 4.95 0.82 8.50, 8.01 6.97 4.73 (d, J = 9 Hz) 0.70 7.98, 7.84 6.68 4.30 0 , 82 8.36, 7.95 6.82 4.63 (d, J = 9 Hz) 0.68 8.10, 7.95 6.72 4.25 0.84 8.56, 8.00 6 , 98 4.54 (d, I = 8 Hz) 0.68 8.09, 7.94 6.79 4.40 0.85 8.45, 7.95 6.92 4.63 0.66 7, 91, 7.62 6.65 4.28 0.83 8.50, 7.99 6.92 4.80 to 4.30 (m) 0.68 8.05 7.85 6.70 4.30 0 , 82 8.90, 8.23 7.15 4.69 (d, J = 5 Hz) 0.66, X5 8.09, 7.99 6.85 4.46 (d, J = 5 Hz) 0 , 85 8.47 7.98 7.43—6.80 4.80 to 4.25 (m) 0.70 (m) xi 8.52, 8.02 6.90 5.11 (m) 1 35 (d, J = 6 Hz) 8.07, 7.84 6.77 4.95 to 4.50 (m) 1.31 (d, J = 6 Hz) 8.62, 8.02 6.96 4.14 (d, J = 7 Hz) 1.10 to 0.65 (1H, m) 0.60 to 0.01 (4H, m) 8.08, 7.92 6.84 4 00 to 3.65 (m) 1.15 to 0.65 (1H, m) - 0.60 to 0.01 (4H, m) 8.59, 8.02 7.01 4.36 (d, J = 9 Hz) 1.54 (1H, m), 1.01 (3H, d, J = 6 Hz), 0.72 (3H, d, J = 6 Hz) 8.10, 7.89 6.75 4.23 (dd, J = 6 Hz, 7 Hz) 1.52 (1H, m), 1.00 (3H, d, J = 6 Hz), 0.97 (3H, d, J) = 6 Hz) 8.73, 8.06 7.10 5.00 to 4.50 (m) 0.74 8.05, 7.88 6.78 4.36 0.85 241472 Compound no. R1 R2 (R5) n Type1 The physical constant of the geometric isomer

17 18 HHC ('CH5) 3 C (CH3) 3 2- CI-5-NO2 3- F-4-OCH3 IA IB IA IB tt 136 to 139 tt 192 to 194 ° C tt 167 to 168 8C tt 67 to 70 ° C 19 HC (CH 3) 3 -OCH 3 IA IB tt 176.5 ° Ct. 187 20 H - (CH 2) 5 - CH 3 4 --C 1 IA IB nD26 1.5 500t. mp 70-73 ° C 21 HC (CH 3) 3 2,3-di-Cl IA IB tt 164-166 ° C. 84 to 85 22 H - (CH 2) s CH 3 4 -C 1 IA IB nD 26 1.5 413 t. 70 to 72 QC 23 HC (CH 3) 3 -CH (CH 3) 2 IA IB nD24 1.5 288nD24 1.5 392 24 HC (CH 3) 3 CH 2/4-OCH 2 CH 3 IA IB mp 142-144 ° Ct. 131 to 132 QC 25 H -CH 2 CH CH 3 CH 3/4-Cl IA IB. tt 126 to 128 ° C tt 109 to 110 ° C 26 H — CH 2 CH 3 4-C1 IA IB tt 74 to 75.5 ° CnD23 1.5 452 27 HC (CH3) 3 4-C1 IA IB tt 151-152 CCt. mp 168-169 ° C 28 H CH 2 CH 2 CH 3 CH 3/4-Cl IA IB nD 24 1.5 639 t. mp 114-115 ° C 29 H-CH 2 CH 3 2,4-di-Cl IA IB mp 125-127 ° Ct. mp 127-130 ° C

30 H - <- - 4-C1 IA IB tt 103 to 105 ° C mp 120 to 122 ° C - VH3U 31 H -C-CH2 / 2,4-di-Cla IA tt 118 to 119 8C ch2 IB tt 139 to 140 ° C 241472 NMR spectrum of OR 1

Triazole Proton Olefin | proton — CH — R 2 proton 8.79 5–7.90 (m) x2 7.05 6.87 4.43 (d, J = 8 Hz) 4.43 (d, J = 5 Hz) 0.71 0.88 8.42, 7.96 8.52, 8.00 7.30-6.80 4.80 to 4.40 (m) 0.70 (m) xi 8.09, 7.98 6, 90-6.35 4.40 to 4.10 (m) 0.81 (m) M 8.55, 8.01 6.95 4.57 0.67 7.93, 7.76 6.81 4, 37 (d, J = 5 Hz) 0.81 8.55, 8.01 6.95 5.10 to 4.70 (m) 1.70 to 0.60 (m) 8.06, 7.86 6 , 76 4.90 to 4.30 (m) 1.70 to 0.70 (m) 8.72, 8.05 7.00 4.41 (d, J = 8 Hz) 0.67 7.99, 7.73 6.86 4.45 (d, J = 6 Hz) 0.85 8.56, 7.99 6.96 5.10 to 4.60 (m) 1.80 to 0.70 (m) 8.03, 7.84 6.74 4.70 to 4.20 (m) 1.70 to 0.70 (m) 8.49, 7.95 6.91 4.90 to 4.40 (m) 0.70 8.04, 7.94 6.71 4.32 0.82 8.40, 7.96 6.81 4.61 0.68 8.14, 7.99 6.75 4.30 (d , J = 6 Hz 0.82 8.50, 8.02 6.89 5.20 to 4.70 (m) 1.90 to 1.25 (3H, m), 0.82 (6H, dd, J = 6 Hz, 2 Hz) 8.08, 7.85 6.75 4.82-4.46 (m) 1.90-1.20 (3H, m), 0.93 (6H, dd, J = 6 Hz, 2 Hz) 8.57, 8.00 6.98 4.70 to 4.00 (m) 1.40 to 0.60 (m) 8.03, Vl 7.81 6.80 4.50 up to 4.10 (m) 1.60 to 0.60 (m) A4 X4 8.60, 7, 88 6.95 5.10 to 4.70 (m) 2.00 to 0.60 (m) 8.06, 7.84 6.72 4.70 to 4.30 (m) 1.70 to 0, 70 (m) 8.55, 8.02 6.93 4.25 (t, J = 9 Hz) 1.80 to 0.50 (m) 7.98, 7.70 6.80 4.70 to 4.20 (m) 1.60 to 0.80 (m) 8.00 8.08, 8.50 6.96 5.00 to 4.70 (m) 0.88 (3H, S), 0, 60 to 0.30 (m) 0.25 to 0.00 (2H, m) 7.86 6.94 4.01 1.06 (3H, S), 0.50 to 0.00 (4H, m) 8.46, 8.01 6.90 4.56 to 5.52 (m) 0.82 (3H, S), 0.42 (3H, S), 0.05 (3H, S) 7.96, 7.70, 7.02 4.11 (d, J = 4 Hz) 1.11 (3H, S), 0.65 to 0.00 (4H, m) 241472 Compound # Ri Rz (R5) n Type 1 geometric isomer Physical constant ch3 32 H4-Br IA tt 105 to 107 ° C / CH2 IB tt 123 to 125 ° C 33 H-c ^ -ch2 ch2 4-F IA tt 120 to 124 ° C IB mp 81-83 ° C CH 3 34 H -C-CH 2 H 1 H t t 125-127 ° C CH 9 mp 120-121 ° C. IB 35 CHs C (CH 3) S 4-Cl IA tt 63 to 66 ° C IB nD27 1.5 435 36 CH 2 CH 3 C (CH 3) 3 4-Cl IA nD26 1.5 452 IB nD27 1.5 380 37 - (CH 2) ) SCH3 C (CH3) 3 4-C1 IA nD26 1.5 390 38 CH2CB = CH2 C (CH3) 3 4-C1 IA n, · 26 1.5 464 IB nD27 1.5 310 39 CH2CH = CHCHs C ( CH3] 3 4-C1 IA nD26 1.5 503 IB X3 40 CH3 C (CH3) 3-F IA mp 72-73 ° C 41 CH 2 CH 2 CH 3 C (CH 3) 3 4-F IA nD25 1.5195 42 CH 2 CH = CH 2 C (CH 3) 4-F IA n,> 25 1.5 220 43 CHS C (CH 3) 3 H IA nD 26 1.5 382 IB nD25 1.5 355 44 CHS C (CH 3) 3 4-Br IA n ,, 26 1.5 619 45 CH 2 CH = CH 2 C (CH 3) 3 4-Br IA n, 26 1.5 638 46 CHS C (CH 3) 3 4-NO 2 IA nD26 1.5 520 47 CH 2 C = CH C (CH 2) 3 4-C1 IA nD23 1.5 550 IB nD26 1.5 450 CHS Z nn21 1.5 360 48 CHS C (CH 3) 3 -CH IA CH 49 CH 2 CH = CH 2 C (CH 3) 3 2 , 3-di-Cl 1 IA nD 22 1.5 570 50 CH 2 CH = CH 2 CH 3 O 3 2-OCHS IA nD22 1.5 380 R 1 proton 241472 NMR spectrum OR 1

Trlazole Proton Olefin | proton — CH — R2 8.51, 8.01 6.95 4.95 to 4.75 (m) 0.86 (3H, S), 0.55 (2H, m), 0.20 to 0.00 (2H, m) 8.15, 7.92 6, 96 4.10 to 3.90 (m) 1.06 (3H, S), 0.35 to 0.00 (4H, m) 8.54 , 8.05 7.55-6.80 (m) x 4.86 (d, J = 8 Hz) 0.90 (3H, S), 0.50 to 0.35 (2H, m) 0.20 up to 0.00 (2H, m) 8.04, 7.81 6.98-6.70 (m) xi 4.10 to 3.95 (m) 1.06 (3H, S), 0.40 to 0.00 (4H, m) 8.49, 7.92 7.00 4.91 (d, J = 7 Hz) 0.85 (3H, S), 0.60 to 0.30 (2H, m) 0.25 and 0.00 (2H, m) 8.09, 7.83 7.30 (m) xi 4.04 (d, J = 4 Hz) 1.06 (3H, S), 0.35 to 0.00 (4H, m) 8.56, 8.00 7.35 4.10 0.73 - - - 8.58, 7.95 7.29 4.16 0.74 - - - 8.60, 7.95 7.27 4.13 0.74 8.52, 7.93 7.27 4.23 0.77 8.57, 7.94 7.25 4.22 0.75 8.57, 8.00 2 , 23 4.09 0.74 8.68, 8.03 7.24 '4.17 0.75 8.55, 7.96 7.19 4.24 0.77 8.51, 7.98 7, 36 4.12 0.74 8.50, 7.93 7.27 4.00 0.72 8.54, 7.94 7.23 4.25 0.79 7.96, 7.32 6.69 3 , 85 0.85 8.52, 7.94 7.31 4.44 0.75 8.52, 8.00 7.35 4.20 '0.75 8.61, 7.99 7.30 4, 10 0.75 8.52, 7.96 7.35-7.15 (m} x 4.20 0.75 241472

Compound No. R1 R2 (Rs) "Geometry Isomer Crushing Physical Constant 51 CHs C (CH3) 5 2,4-Cl IA nD25 1,5 535 IB nD27 1,5 461 52 CH2CH-CH? C (CH 3) 3 2.4-Cl. IA nD25 1.5 510 53 HC (CH3) 5 3,5-dPCl IA tt 161 to 162 C'C IB tt 120 to 121 ° C 54 HC (CH3) 3 4-C2HS IA tt 85 to 86 IB tt 136 to 137 ° C 55 HC (CH3) 3 2-F-4-C1 IA tt 159 to 160 ° C IB tt 128 to 129 ° C 56 HC (CHs) 3 3,4,5-tri-OCHs IA tt 155 to 156 QC IB mp 113-114 °

Note: xi Olefin proton and phenyl proton are in the same position. X2 The triazole proton and the phenyl proton are in the same position. Hydrochloric acid salt. X5 Solvent: (CD3SO4, 241472 NMR spectrum of ORi

Triazole Proton Olefin | proton — CH — R2 Rž proton 8.68, 8.07 7.40 3.97 0.76 8.62, 8.00 7.30 4.08 0.75 8.60, 8.00 6.88 4 , 54 0.73 '8.02, 7.84 6.72-6.55 (m) xi 4.30 (d, J = 6 Hz) 0.81 8.52, 8.00 6.92 4, 71 (d, J = 7 Hz) 0.70 8.03, 7.84 6.69 4.26 (d, J = 6 Hz) 0.81 8.61, 8.02 7.52-6.80 (m) xi 4.51 0.71 8.04, 7.95 6.75 4.42 (d, J = 6 Hz) 0.82 8.61, 8.00 6.94 5.00 to 4, 60 (m) 0.74 8.07, 8.02 6.60 4.40 to 4.10 (m) 0.81 241472 18 mer ΓA triazole compounds of Formula I. 17 The following is a method for producing the triazole isomer III. of formula (II), which is the starting material for iso-

Method C

Isomerization of isomer IIB or a mixture of isomers IIB and IIA of the triazole compound IIO

isomer IIB or a mixture of isomers IIB and IIA ^ -ch = cc-r2

IL-W

isomer IIA where

Ra, R3 and n are as defined above. Isomer IIA can be obtained by irradiating the isomer IIB or a mixture of isomers IIB and IIA from ultraviolet or xenon lamps, or by radiation from fluorescent lamps or in a solvent that is inert to radiation. Solvents commonly used include, for example, alcohols (e.g., methanol, ethanol, propanol, ethers (e.g., tetrahydrofuran, dioxane, ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, aliphatic hydrocarbons (e.g. for example hexane, cyclohexane, petroleum ether and aromatic hydrocarbons (for example benzene, toluene, xylene) The reaction can be carried out at temperatures at which photoisomerization is carried out normally, but conventional temperatures between 0 and 100 CC are preferred. for use in conventional photoreactions, for example phenylketones such as acetophenone and propiophenone, but are not particularly advantageous, the process for the preparation of the thiazole derivatives represented by the general formula (II) will be further illustrated.

Method D Production of a mixture of the geometric isomers of the triazole derivative of the general formula (II) and the isomers (IIB, IIA)

CteC-fy (iv)

O

CH = CC-R 2 where R 2, R 5 and n are as defined above.

The triazole derivative of formula (II) is reacted by reacting 1 mole of a ketone of formula (IV) with 1-2 moles of benzaldehyde of formula III in a suitable solvent in the presence of a basic catalyst. The basic catalysts include, for example, alkali metal or alkaline earth metal hydroxides (e.g., sodium, potassium, calcium), alkali metal alkoxides (e.g., sodium methoxide, sodium ethoxide, potassium methoxide), carbonates ( for example, sodium carbonate, potassium carbonate, acetates (e.g., sodium acetate, potassium acetate), secondary amines (e.g., diethylamine, di-propylamine, pyrrolidine, piperidine, morpholine) and tertiary amines (e.g., triethylamine, tributylamine, pyridine, picoline, dimethylamine) Solvents include, for example, alcohols (e.g., methanol, ethanol), aromatic hydrocarbons (e.g., benzene, toluene, xylene), ethers (e.g., diethyl ether, tetrahydrofuran, dioxane), water and mixtures thereof The reaction is carried out at a temperature between 0 ° C and the temperature of the solvent.

When a catalyst (e.g. sodium, potassium, carbonate, e.g. carbonate, potassium), tertiary amines, glacial acetic acid or acetic anhydride is used as the basic catalyst, it can also be used as a reaction solvent.

The triazole derivative of general formula (II) thus obtained is generally a mixture of two geometrical isomers, i.e. isomer IIA and isomer IIB, and each of these isomers can be isolated by column chromatography or traction crystallization. The mixture of geometric isomers usually contains a greater proportion of the isomer IIB than the isomer IIA. Of course, all of the IIA isomer compounds are new compounds. IIB isomers in which R 2 is a 1-methylcyclopropyl group are also novel compounds. The following examples illustrate C and D in more detail. Example 4

Synthesis of 1- (4-chlorophenyl) -4,4-dimethyl-2- (1,2,4-triazol-1-yl) -1-penten-3-one (Compound No. 1 ') by Method D 50 g of α- (1,2,4-triazol-1-yljpinacolone, 41 g of anhydrous potassium carbonate, 200 ml of acetic anhydride and 46.3 g of 4-chlorobenzaldehyde are mixed and heated to 90 DEG C. for 12 hours). The filtrate is added dropwise to 500 ml of hot water at 60 DEG C. to decompose the acetic anhydride and the solution is then basified by successive addition of potassium carbonate, extracted with 500 ml of ethyl acetate, dried over anhydrous sodium sulfate and evaporated under reduced pressure. the residue is dissolved in acetone and the acetone solution is subjected to gas chromatography under the conditions described below, whereupon the peak corresponding to the isomer II is determined at a residence time of 300 s and the peak corresponding to the isomer IIB at a residence time of 360 s. 61.2, ie. about 1: 3 as calculated from the percentage of each area.

Gas chromatography conditions are as follows:

Equipment:

Gas chromatograph Nippon Denshi 20K equipped with FID detector.

Column:

Glass column 1 m long, liquid phase 5% XE-60, carrier Chromosorb W.

Temperature (column): 200 ° C.

Temperature (Injection): 240 ° C.

Carrier gas: nitrogen gas at 98 kPa.

The residue is dissolved in 100 ml of benzene. The solution is passed through a column filled with 1.2 kg of silica gel of 100-200 mesh size and column chromatography with 10: 1 hexane / acetone as the eluent. The fraction corresponding to each isomer is recrystallized from carbon tetrachloride; 36 g (41.6% yield) of pure IIB isomer (m.p. 78-79 ° C) and 10 g (11.5% yield) of pure isomer IIA (m.p. 108-109 ° C) were obtained. Further elution with n-hexane / acetone (10: 3) was added to the column and 8 g of α- (1,2,4-triazol-1-yl-pinpinone) were obtained. The NMR spectrum is measured in deuterochloroform as the solvent and the chemical displacement is expressed as S with tetramethylsilane as internal standard.

1- (4-Chlorophenyl) -4,4-dimethyl-2- (1,2-4-triazol-1-yl) -1-penten-3-one isomer IIA (Compound No. Γ) .

Elementary analysis for H, 5.58;% H, 14.50; N, 12.23; Found: C, 62.32; H, 5.60; N, 14.41. Cl, 12.20. NMR Spectrum: 8.11 (1H, s, triazole proton), 7.90 (1H, s, triazole proton), 7.15 (4H, s, phenyl proton), 6.99 (1H, s, olefin proton) , 0.99 (9H, s, butyl proton).

Isomer IIB 1- (4-chlorophenyl) -4,4-dimethyl-241472 21 -2- (1,2,4-triazol-1-yl) -1-penten-3-one (Compound No. Γ) :

Elemental analysis: Found: 62.35%, O%, 5.59% N, 14.38% N, 12.18% Cl. NMR Spectrum: 8.14 (1H, s, triazole proton), 7.98 (1H, s, triazole proton), 7.22 (2H, d, phenyl proton, J = 8 Hz), 6.73 (2H, d, phenyl proton, J = 8 Hz), 7.49 (1H, s, olefin proton), 1.22 (9H, s, butyl proton). Example 5

Synthesis of 1- (4-chlorophenyl) -4,4-dimethyl-2- (1,2,4-triazol-1-yl) -1-penten-3-one isomer IIA by method C 8.0 g of isomer IIB The 1- (4-chlorophenyl) -4,4-dimethyl-2- (1,2,4-triazol-1-yl) penten-3-one obtained in Example 4 is dissolved in 500 acetone and isomerized. at 45 ° C by means of an ultraviolet generator equipped with a 500W high pressure mercury discharge lamp. During the reaction, trace amounts of the reaction solution are taken several times as samples and the isomer ratio (isomer IIB: isomer IIA) is measured by gas chromatography under the same conditions as in Example 4. The following results are obtained:

Time (min.) Isomer Ratio (IIB: IIA) 0 100: 0 20 10: 90 60 6:94 120 6: 94

After 2.5 hours, the reaction solution was transferred to a 500 ml eggplant flask and the acetone removed under reduced pressure to give 7.9 g of crystals. The crystals were recrystallized from carbon tetrachloride to give 6.2 g (78% yield) of crystalline solid, m.p. 108-109 ° C. This compound is dissolved in acetone and subjected to gas chromatography under the conditions described above, but no peak corresponding to isomer IIB is observed. Example 6

Synthesis of isomer IIA to a mixture of geometric isomers of 1- (4-chlorophenyl) -4,4-dimethyl-2- (1,2,4-triazol-1-yl) -1-penten-3-one (Compound No. 1 ') )

10 g of a reaction mixture containing 1: 3 isomers of IIA and IIB obtained in Example 4 were irradiated with UV radiation under the same conditions as in Example 5. After 1.5 hours, the ratio of IIA to isomer is determined by gas chromatography. IIB and found to be about 19: 1.

After evaporation of the solvent, the crystals obtained are recrystallized from carbon tetrachloride. 5.1 g of the IIA isomer are isolated. Example 7 A. Synthesis of 3- (4-chlorophenyl) -1- (1-methyl-cyclopropyl) -2- (1,2,4-triazol-1-yl) -2- 2-propen-1-one

(Compound No. 29 ') by method C 10 g (0.06 mole) of 1- (1-methylcyclopropyl-2- (1,2,4-triazol-1-yl) ethan-1-one, 9 g (0%). Of 4-chlorobenzaldehyde, 18 g (0.06 mol) of anhydrous potassium carbonate and 100 ml of acetic anhydride are mixed and heated to 100 ° C for 6 hours with stirring. The oily product was extracted with 300 ml of chloroform and the extract was washed with 300 ml of saturated sodium bicarbonate solution, the organic layer was dried over anhydrous sodium sulfate and evaporated under reduced pressure.

One drop of the residue is dissolved in acetone and the acetone solution is subjected to gas chromatography under the conditions described below. The peak corresponding to the isomer of IIA is then determined at a residence time of 250 and the peak corresponding to the isomer IIB at a residence time of 300 s. The ratio of the two isomers is 19.1: 63.5, i.e. about 1: 3 as calculated from the percentage of each area -chy.

Gas chromatography conditions are as follows:

Equipment:

Nippon Denashi 20K gas chromatograph equipped with FID detector.

Column:

Glass column 1 m long, liquid phase 5% XE-60, carrier Chromosorb W.

Temperature (columns): 181 ° C.

Temperature (Injection): 240 ° C.

Carrier gas: nitrogen gas at 98 kPa.

The residue is dissolved in 100 ml of benzene. The solution is passed through a column filled with 300 g silica gel of 100-200 mesh size and column chromatography with 10: 1 hexane / acetone as the eluent. The fraction corresponding to each isomer is recrystallized from carbon tetrachloride to separate the two geometric isomers of the title compound. The NMR spectra of the isomers are shown in Table 2.

Isomer IIA: 1.7 g (10% yield).

Isomer IIB: 6.7 g (38% yield). B. Synthesis of Starting Material, 1- (1-Methylcyclopropyl) -2- (1,2,4-triazol-1-yl) ethan-1-one

To a mixture of 28 g of 1-methylcyclopropyl ketone [a compound well known in Bull. Soc. Chim.Fr., 1708 (1960)], 5.8 g of potassium chlorate and 70 ml of water were added at 40-50 ° C over 4 hours with vigorous stirring and then the reaction solution was stirred at room temperature. room 2 hours. Then the reaction solution is extracted with two 200 ml portions of ether, the organic layer is dried with calcium chloride and evaporated under reduced pressure. 53 g of crude product are obtained, 1- (1-methylcyclopropyl) -2-bromoethane-1-one.

A mixture of 18.3 g of 1,2,4-triazole, 37 g of potassium bicarbonate and 250 ml of acetonitrile was refluxed for 1 hour and then cooled to 60 ° C. Then 53 g of crude 1- (1-methylcyclopropyl) -2-bromoethane-1-one was added over 2 hours and stirred overnight at room temperature. The precipitate was filtered off from the reaction solution and the filtrate evaporated under reduced pressure (100 ml of water and 300 ml of chloroform). The organic layer was dried over anhydrous magnesium sulfate and evaporated under reduced pressure. The resulting oily residue was crystallized from 100 ml of petroleum ether to give 27 g of 1- (1-methyl-cyclopropyl) -2- (1,2,4-triazol-1-yl-jethan-1-one (57% yield, based on to methyl 1-methylcyclopropyl ketone, mp 57-60 ° C

Synthesis of isomer IIA 3- (4-chlorophenyl) -1-

- (1-methylcyclopropyl) -2- (1,2,4-triazol-1-yl) -2-propen-1-one from its isomer IIB Method C 4 g of isomer IIB 3- (4-chlorophenyl) -1- (1-methylcyclopyl) -2- (1,2,4-triazol-1-yl) -2-propen-1-one obtained in Example 7, dissolved in 500 ml acetone and isomerized to 45 ° C for 2 hours by means of generator-ultraviolet radiation, colored with 500 W high pressure mercury vapor lamps. The ratio of isomer IIA to isomer IIB is determined by gas-flash chromatography in the same manner as in Example 7. The ratio is found to be 81.2: 18.1. The reaction solution was evaporated under reduced pressure to give 3.9 g of crystals. These were recrystallized from carbon tetrachloride; 2.8 g (70% yield) of isomer IIA are obtained

Synthesis of 3- (4-chlorophenyl) -1- (1-methylcyclopropyl) -2- (1,2,4-triazol-1-yl) -2-propen-1-one isomer IIA from a mixture of its geometrical of isomers of 3 g of the reaction mixture formed by the isomers IIA and IIB (ratio of isomer IIA: isomer IIB = 1: 3) obtained in Example 7 is irradiated with ultra violet radiation for 1.5 hours under the same conditions as in Example 8. Then , isomer IIA to isomer IIB is determined by gas chromatography. This ratio is found to vary from 1: 3 to 7: 3. After evaporation of the solvent, the crystals obtained are recrystallized from carbon tetrachloride. 1.5 g of the IIA isomer are obtained. Example 10

Synthesis of 1- (4-chlorophenyl) -2- (1,2,4-triazol-1-yl) heptene-3-one compound IIB isomer D by method D

To a mixture of 50 g of 2-hexanone and 300 ml of methanol is added 80 g of bromine at 0 DEG C. and the mixture is then kept at 10 DEG C. for 2 hours. Then 200 ml of water and 50 g of concentrated sulfuric acid are added to the mixture. The reaction mixture was transferred to a separatory funnel and extracted with 500 mL of ether. The organic layer was washed with 5% aqueous potassium carbonate solution and dried with calcium chloride. The solvent was evaporated under reduced pressure to give 89 g of crude 1-bromo-2-hexanone as an oily product.

A mixture of 35 g of triazole, 69 g of anhydrous potassium carbonate and 300 ml of acetonitrile was refluxed for 1 hour and then allowed to cool to 50 ° C. 89 g of crude 1-bromo-2-hexanone obtained above were added dropwise and the mixture was then stirred for 16 hours. The precipitate was filtered off from the solution and the solvent was evaporated to a reduced pressure. 200 ml of water and 200 ml of chloroform are added to the obtained residue and the mixture is transferred to a separatory funnel and then extracted. The organic layer was dried over anhydrous magnesium sulfate and the solvent was evaporated under reduced pressure. 77 g of dry 1- (1,2,4-triazolyl) -2-hexanone are obtained in the form of an oily product. 20 g of the resulting 1- (1,2,4-triazolyl) -2-hexanone, 20 g of anhydrous potassium carbonate, 20 g of p-chlorobenzaldehyde and 200 ml of acetic anhydride are mixed and heated to 90 ° C. The reaction mixture is then evaporated under reduced pressure and the residue is then dissolved in 500 ml of ethyl acetate and transferred to a separatory funnel, the ethyl acetate solution is washed with 200 ml of water saturated with potassium carbonate and the organic layer is separated. the pressure and the residue were loaded with a 0.5 kg silica gel column (100-200 mesh) and column chromatographed with a 10: 1 n-hexanone / acetone mixture as eluent to obtain 3.7 g of ΠΒ isomer (temperature mp 117-120 ° C 1- (4-chlorophenyl) -2- (1,2,4-triazol-1-yl) -1-hepten-3-one and 9 g 1- (4-chlorophenyl) -2- (1,2,4-triazol-1-yl) -3-acetoxy-1,3-heptaene (m.p. 112-113 ° C) To 9 g of the resulting 1- (4-chlorophenyl) -2- (1,2,4-triazol-1-yl) Of 3-acetoxyl-1,3-heptadiene is added 100 ml of concentrated hydrochloric acid, the mixture is heated to 50 DEG C. for 1 hour and poured into 500 ml of ice water. The water-containing liquid phase was neutralized with potassium carbonate and extracted with 300 ml of ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and evaporated in vacuo. The crystalline residue is recrystallized from a 1: 1 mixture of carbon tetrachloride and n-hexane. 6 g of 1- (4-chlorophenyl) -2- (1,2,4-triazol-1-yl) -1-hepten-3-one isomer IIB are obtained. Example 11

Synthesis of Isomer IA of 1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) -4,4-dimethyl-1-penten-3-ol (Compound No. 2)

First stage (condensation), method D

A mixture of 200 g of α- (1,2,4-triazol-1-yl) -pinacolone, 220 g of 2,4-dichlorobenzaldehyde and 700 acetic anhydride was heated to 50 DEG C. and then 255 g of triethylamine were added. The mixture was maintained at 70 ° C for 7 hours and the acetic hydride evaporated under reduced pressure. Water (3 L) was added to the residue, the resulting crystals were filtered, washed with water and dried. The resulting product is recrystallized from 600 ml of ethanol to give 304 g of isomer IIB 1-

- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) -4,4-dimethyl-1-penten-3-one (Compound No. 2 '). (Photoisomerization) Method C 300 g of Compound # 2 'isomer IIB obtained in the first step is dissolved in 2 liters of acetone and isomerized at 30 ° C for 26 hours using an ultra-violet generator equipped with 500 W high -pressure mercury lamp. Solvent

then evaporated under reduced pressure to give an oil (300 g). Gas chromatography revealed that this product was a mixture of 75% isomer IIA of Compound No. 2 'and 25% of Isomer IIB of the same compound. This product is transferred to the next step without isolating the isomers. Third step (reduction), method A 300 g of the geometric isomer mixture of compound # 2 'obtained in the second step are suspended in 1 kg of methanol and then added in portions. 38 g of sodium borohydride, cooling the reaction mixture to 10 ° C. After stirring at room temperature for one hour, the reaction solution was evaporated under reduced pressure. The residue obtained is extracted by adding 2 liters of a 10% aqueous solution of acetic acid and 3 liters of ethyl acetate. The separated organic layer was washed with 1 L of 5% aqueous potassium carbonate solution and dried over 100 g of anhydrous magnesium sulfate. After filtering off the drying agent, the solvent was evaporated under reduced pressure to give 280 g of crude product as crystals. This product is a mixture of IA and IB isomers of Compound No. 2 (molar ratio IA: isomer IB = 75:25). 280 g of the crude product are recrystallized from 600 ml of carbon tetrachloride to give 209 g of the title compound (isomer IA of Compound 2). The mother liquor from the recrystallization was evaporated to give 25 g of the isomer IB of compound 2 as secondary crystals.

The isomers IIA of the ketone compound of formula II obtained by methods C and D are shown in Table 2 together with isomers IIB. The NMR spectrum in this table is given in the same form as in Table 1. 27 23 241472 In the practical use of the compounds of the invention, these compounds can be used alone without other components or in mixtures with carriers for ease of use. , such as fungicides, herbicides and plant growth modifying agents. Generally used and prepared forms include, for example, powders, wettable powders, oil sprays, emulsifiable concentrates, tablets, granules, fine granules, aerosols and liquid preparations. Typically, the foregoing compositions contain from about 0.1% to about 95.0% by weight of the active ingredient (including other admixtures). The active ingredient is generally used in a preferred amount of 200 to 50,000 g per hectare. Preferably, the active ingredient is used in a range of 0.001 to 1.0%. However, since the amount of concentration depends on the form of the composition, the time of use, the application technique, the use of the land, the diseases, and the crop being treated, it can be appropriately increased or decreased irrespective of the aforementioned cutoff doses. In the preparation of the fungicide, herbicide and plant growth-modifying agent according to the invention, stirring is carried out with a solid or liquid carrier. As solid carriers, for example, inorganic substances (for example clays selected from kaolin, montmorillonite or attapulgite groups, talc, mica, pyrophyllite, pumice, vermi-culite, gypsum, calcium carbonate, dolomite, diatomaceous earth, magnesium oxide, lime, calcium, lime, calcium, lime) -no, apatite, zeolite, silicic anhydride, synthetic calcium silicate), plant organic substances (for example, soy powder, tobacco powder, walnut powder, flour, wood dust, starch, cellulose in crystalline form) ), high molecular weight synthetic or natural compounds (for example, coumarone resins, petroleum resins, alkyd resins, polyvinyl chloride, polyalkylene glycol, keto-resins, rosin esters, copolymer resins, dammar resins), waxes (e.g., carnaubonic wax, beeswax) and urea .

Liquid carriers include paraffin or naphthenic hydrocarbons (e.g., kerosene, petroleum, spindle oil, white oil), aromatic hydrocarbons (e.g., benzene, toluene, xylene, ethylbenzene, cumene, methylnaphthalene), halogenated hydrocarbons (e.g., carbon tetrachloride, chloroform) , tri-chloroethylene, monochlorobenzene, o-chloro-toluene), ethers (e.g. dioxane, tetrahydrofuran), ketones (e.g. acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, acetoenone, isophorone), esters (for example ethyl acetate, amyl acetate, ethylene glycol) tate, diethylene glycol acetate, dibutyl maleate, diethyl succinate), alcohols (for example methanol, n-hexanol, ethylene glycol, diethylene glycol, cyclohexanol, benzyl alcohol), ether alcohols (e.g. ethylene glycol ethyl ether, ethylene glycol phenyl ether, diethylene glycol ethyl ether, diethylene glycol ethyl ether, polar solvents (e.g. dimethylformamide, dimethylsulfoxide) and water.

Nonionic, anionic, cationic and amphoteric surfactants can be used as surfactants used for emulsifying, dispersing, wetting, spreading, bonding, controlling disintegration, stabilizing the active ingredient, improving flowability and corrosion. but usually nonionic and / or anionic surfactants are used. Suitable nonionic surfactants include, for example, those obtained by polymerizing ethylene oxide and a higher alcohol (e.g., lauryl alcohol, stearyl alcohol, oleyl alcohol), ethylene oxide, and alkyl phenol (e.g., isooctylphenol, nonylphenol), ethylene oxide, and alkyl naphthol (e.g. butylnaphthol, octyl naphthol), ethylene oxide and higher fatty acids (e.g. palmitic, stearic, olefinic), ethylene oxide and mono- or dialkyl phosphate (e.g. stearyl phosphate, dilauryl phosphate), or ethylene oxide and amine (e.g. dodecylamine, stearic acid amide), a higher fatty acid ester and a polyhydric alcohol (e.g., sorbitan), and those obtained by polymerizing said ethylene oxide esters and apropylene oxide ethylene oxide polymers Suitable salts of anionic surfactants include, for example, alkyl sulfate salts ( for example sodium lauryl sulphate, amine salts of oleyl sulphate), alkyl sulphonate u (for example sodium dioctyl sulfosuccinate, sodium 2-ethylhexasulfonate) and arylsulfonate (for example sodium isopropylnaphthalenesulfonate, sodium methylenebisnaphthalenesulfonate, sodium lignosulfonate, na-triodododecylbenzenesulfonate).

Compositions containing a compound of the invention may contain high molecular weight compounds and other adjuvants to improve their performance and biological effect. High molecular weight compounds include, for example, casein, gelatin, albumin, glue, sodium alginate, carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, and polyvinyl alcohol.

Advantageously, the aforementioned carriers and excipients are used alone or in combination according to the intended use, taking into account the form of the composition and the technique used.

The dust content of the active ingredient is generally 1 to 25% and the remainder is a solid carrier.

In wettable powders, the content of the active ingredient is generally 25 to 90% by weight. The remainder consists of a solid support and a dispersing wetting agent, and optionally a colloid, a thixotropic agent and a foaming agent are added.

The active ingredient content of the granules is generally 1 to 35% by weight and most of the residue is a solid carrier. The active ingredient is uniformly mixed with the solid carrier or uniformly fixed or adsorbed onto the top of the solid support. The particles have a diameter of about 0.2 to about 1.5 mm.

Emulsified concentrates generally contain the active ingredient in an amount of 5 to 30% by weight, the emulsifier in an amount of generally 5 to 20%, and the remainder being a liquid carrier. Further, the compounds of the present invention can be used in admixture with other fungicides, herbicides and plant growth regulating agents without reducing the suppressing effect of each of the active ingredients in the composition. Examples of functionalities are N- (3,5-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboximide, Sn-butyl (Sp-tert-butylbenzyldithiocarbimimidate, O, O-dimethyl [O ((2,6-dichloro-4-methylphenylphosphorothioate), methyl (1-butylcarbamoyl-1H-benzimidazol-2-ylcarbamate), N-trichloromethylthio-4-cyclohexene-1,2-dicarboximide, cis-N- (1,1,2,2-tetrachloroethylthio) -4-cyclohexene-1,2-dicarboximide,

Polyoxin,

Streptomycin, zinc salt of ethylenebisodithiocarbamic acid], zinc salt of dimethylthiocarbamic acid, magnesium salt of ethylenebisdithiocarbamic acid J, bis (N, N-dimethylthiocarbamoyl) disulfide, tetrachloroisophthalonitrile, 8-hydroxyquinoline, dodecylguanidine acetate, 5.6-dihydro-2-methyl 1,4-oxathiine-3-carboxililide, N '-dicblorofluoromethylthio-N, N-dimethyl-N' - phenylsulfamide, 1- (4-chlorophenoxy) -3,3-dimethyl-l- (1, 2,4-triazol-1-yl-2-butanone, 1,2-bis (3-methoxycarbonyl-2-thioureido) -benzene, methyl N- (2,6-dimethylphenyl) -N-methoxy acetyl-2-methylglycinate], aluminumethyl phosphite and the like.

Herbicides include herbicidesphenoxy series such as 2,4-dichlorophenoxyacetic acid; 2-methyl-4-chlorophenoxyacetic acid, 2-methyl-4-chlorophenoxybutyric acid and 2-methyl-4-chlorophenoxyacetic acid (including esters and salts), diphenyl ether herbicides such as 2,4-dichlorophenyl-4'-nitrophenyl ether, 2.4 6-trichlorophenyl-4'-nitrophenyl ether, 2-chloro-4-trifluoromethylphenyl-3'-ethoxy-4'-nitrophenyl ether, 2,4-dichlorophenyl-4'-nitro-3'-methoxyphenyl ether and 2,4-dichlorophenyl-3 '-methoxycarbonyl-4' - nitrophenyl ether, triazine series herbicides such as 2-chloro-4,6-bisethylamino-1,3,5-triazine, 2-chloro-4-ethylamino-6-isopropylamino-1,3 , 5-triazine, 2-methylthio-4,6-bisethylamino-1,3,5-triazine, 2-methylthio-4,6-bisisopropylamino-1,3,5-triazine, urea herbicides such as 3- (3,4-dichlorophenyl) -1,1-dimethylurea, 3- (3,4-dichlorophenyl) -1-methoxy-1-methylurea, 1- (α, α-dimethylbenzyl) -3-p-tolylurea and 1- (2-benzothiazolyl] -1,3-dimethylurea, carbamate series herbicides such as isopropyl- [N- (3-chlorophenylcarbamate) amethyl [N- (3 4-dichlorophenyl) carbamate], thiolcarbamate herbicides, such as S- (4-chlorobenzyl) - [Ν, Ν-diethylthiolcarbamate, and S-ethyl (Ν, Ν-hexamethylenethiolcarbamate), acid anilide herbicides such as 3.4 - dichloropropionanilide, 2-chloro-N-methoxymethyl-2 ', 6'-diethylacetanilide, 2-chloro-2', 6'-diethyl-N- (butoxymethyl) acetanilide, 2-chloro-2 ', 6 n -diethyl-N- (n-propoxyethyl) acetanilide and N-chloroacetyl-N- (2,6-diethylphenylglycine) ethyl ester, uracil series herbicides such as 5-bromo-3-sec-butyl-6-methyluracil and 3-cyclohexyl-5,6-trimethylenuracil, herbicides of the series consisting of pyridinium salts such as 1,1'-dimethyl-4,4'-bipyridinium chloride, herbicides composed of a number of phosphorus compounds such as N- (phosphonomethyl Jglycine, Ν , Ν-bis (phosphonomethyl) glycine, [O-ethyl-O- (2-nitro-5-methylphenyl) -N-sec-butyl] phosphoramidothioate, [S- (2-methyl-1-piperidylcarbonylmethyl)] - -0.0-di-n-propyldithiophosphate and 241472 ΰ by 4-4 o

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The compounds of the invention may also be used in admixture with other insecticides without reducing the suppressing effect of each individual active ingredient in the mixture. Insecticides which may be mentioned are insecticides based on organic phosphorus compounds such as Ο, Ο-dimethyl- [O- (4-nitro-3-methylphenyl) phosphorothioate], O- (4-cyanophenyl) - [ Ο, Ο-dimethylphosphorothioate], O- (4-cyanophenyl) - [O-ethylphenylphosphonothioate, Ο, Ο-dimethyl [S- (N-methylcarbamoylmethyl) phosphorodithiate], 2-methoxy-4H-1,3,2-benzodioxaphosphorine-2-sulfide and Ο, Ο-dimethyl [S- (1-ethoxycarbonyl-1-phenylmethyl) phosphorodithioate], Name of barley barley (Helminthosporiumgramineumj blue rot) (Penicillium italicum) Apple scab (Venturia inaequalis) Apple tree gangrene (Valsa small) Cucumber gangrene (Mycosphaerella melonis) Citrus melanosis (Diaporthe citri) Barley dust (Ustilago nuda) Potato verticillosis (Verticillium albo-atrum) Septoria tritici (Cersospora beticola) Potato fusariosis (Fusarium oxysporum f. Sp. Lycopersici) Alternaria pear (Alternaria kikuchiana)

Growth suppression steps with test compounds are evaluated in four categories, designated A, B, C and D. A: Growth Suppression Level 100%. B: Growth suppression degree 90% or more. C: Growth suppression degree 89 to 50 ° / o. D: Growth suppression degree 40% or less. pyrethroid series insecticides such as α-cyano-3-phenoxybenzyl- [2- (4-chlorophenyl) -isovalerate], 3-phenoxybenzyl [2,2-dimethyl-3- (2,2-dihydro-vinyl)] cyclopropanecarboxylate] and α-cyano-3-phenoxybenzyl [2,2-dimethyl-3- (2,2-dibrominyl) cyclopropanecarboxylate].

Therefore, two or more kinds of diseases and weeds can be suppressed. Further synergistic effects can be expected in consistent mixing. Furthermore, the utility of the compounds of the invention as fungicides, herbicides and plant growth modifiers for agriculture and horticulture is illustrated by the following test examples and preparation examples.

Test Example 1

Fungitoxic effect

The medium containing 5 g of polypepton, 20 g of malt extract, 20 g of sucrose and 20 g of agar per liter of water is transferred to the solution by heating. To this end, the test compound is added and the emulsifiable concentrate is prepared by dilution, so that the concentration of the test compound in the medium is predetermined. After thoroughly washing the medium, this medium is poured into a glazed Petri dish and an agar layer is formed. After the agar solidifies, it is inoculated with the mycelial disc or; sus-pension spores of tested fungi. The name of the fungus to be tested and the culture time from inoculation to observation are given below. The culture temperature is 20 ° C for scab apple (Venturia inaequalis) and 28 ° C for other fungi.

Abbreviation Time of Culture

Hg 6 days Pi 6 days Vi 7 days Vm 4 days Mm 4 days Dc 6 days Un 6 days Va 7 days Wed 7 days Cb 7 days Fo 4 days If 4 days

As can be seen from Table 3, the isomer IA of the present invention has been found to have a markedly broad antimicrobial spectrum. As well as remarkably high activity when compared to the isomers IB, IIA and IIB. TABLE 3

Tested Concentration Degree of growth inhibition compound of active ingredient Hg Pi Vi Vm Mm Dc, Un Va St Gb Fo Ak (ppm)

IA Isomer Compound No. 1 5 AAAAAABAAA - - 2 5 AAAAAACCAA - - 3 5 AAAAAA, CAAA - - 4 5 BACCCACCCA - - 5 5 AAAAABCCAA - - 6 | 5 GBAACBCCAC - - 7 '5 BAACABCCAB - - 5 5 BBBCCBCCCB • - - 9 5 BBA' c BB <c CAA - - 10 5 AAABAB c CAB - - 11 5 BBBCBBCCCB - - 12 5 BCBCBB cc BC - - 13 20 BCBACC cc AA - - 5 5 BBB! CBB cc BB - - 15 5 BBBBBC cc BC - - 16 5 BBBBBB BC BC - - 17 5 IB BBBBB 'C c BB -. - 18 5 ACACBA cc CB - - 5 BBABBB c BAB - - 20 5 BBBCBB c CCB - - 21 5 IC CAACBCCAC - - 22 5 c CAACB cc AC -. - 23 5 IC CAA C CC AC - - 24 '5 BCACBB cc ACBB 25 5 ABACCB cc ACCC 26 5 AAABBB c BAB - - 27 5 AAAAAAAAAA - - 28 5 AAACCCCCACCB 29 30 5 5 AAAAABABB 31 5 AAA - AA - BA - BB 32 5 AAA - AA - BA - BB 33 5 BBA - BB - CA - CB 34 5 BBA - BB - CA - CB 35 5 BBAA - A - - ABB - 40 5 BCAA - B - - ACA - 43 5 BCBA - B - - BCB - (Reference Compound) Isomer IB Compounds No. 1 5 DDDDDDDDDD 2 5 DDDDDDDDDD - - 5 5 DDDDDDDDDD - - 4 '.. 5 DDDDDDDDDD - - 5 * 5 DDDDDDDDDD - - 5 5 DDDDDDDDDD - -, 9 5 DDDDDDDDDD - - 10 5 DDDDDDDDDD - - 11 5 DDD • DDDDDD, D - - 12 5 DDDDDDDDDD - - 13 20 DDDDDDDDDD - -. 14 5 DDUDDDDDDD _ 15 5 DDDDDDDDDD - - 16 5 DDDDDDDDDD - - 5 5 DDDDDDDDDD - - 18 '9 DDDDDDDDDD - - 19 5' DDDDDDDDD, D - 20 5 DDDDDDDDDD - - 241472

Tested Concentration Compound of Active Ingredient Hg (ppm)

Growth suppression degree

P rin t i n d i n c i n i cb fo ac

Isiomer IB Compounds No. 2122 23 24 25 26 27 28 30 31 32 33 34 3543

Isomer IIA compounds no 1 '2' 3 '4' 5 '6' 7 '8' 9 'l'0' 11 '12 * 13 * 14 * 15 * 16 *, 17 * 18 * 19 * 20 * 21 * '22 * 23 * 24 * 25 * 26 * 27 * 28 * 29 * 30 * 31 * 32 * 33 * 5 and 5 5; 5 5 5 5. 5; 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5

D DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD

D DD DD DD DD DD DD D D D D D D D

DDD

DDD

DDD

DDD

DDD

DDD

DDD

DDDDD - DD - DD - DD - DD - - D - - D -

D

D

D

D

D

D

D

D

D

D

D

D

D

D DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD

D DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD

DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

DDDD —DDD DDDDDDDDDDDD'DDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDD D -DDD -DDD -Dd; D - DDDD DDDD —DDD DDDD DDDD DDDD —DDD —DDD —DDD DDDD —DDD DDDD --DDD —DDD-DDD - —DDD- - 241472

Tested Concentration Compound of Active Ingredient Hg (ppm)

Growth suppression degree

Pi Vi Vm Mm Dc Un Va St Cb Fo

Ak

Isomer IIB compounds no 1 * 2 * 3 '4' 5 * 6 * 7 * 8 * 9 * 10 * 11 * 12113 * 14 * 15 * 16 * 17 * 18 * 19 * 20 '21 * 22 * 23 * 24 * 25 * 26 * 27 * 28 * 29 * 30 * 31 * 32 * 33 * 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D

D DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD

D DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD

D DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DD DDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDD. —DD —DD —DD —DD —DD —DD —DD —DD —DD —DD —DD —DD —DD —DD —DD —DD —DD —DD —DD —DD - 241472

Mergers- R2 (R3) n Species Physical nina No. geome- constant Triazole Olefin R2 proton proton proton ison S .6

tc CO tc CM CMc CM CM

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what is it — Ί >> CM '—'CO in

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S 0.95-0.75 (2H, IIB nD2S 1.5849 8.14.8.03 7.65 1.50-1.25 (2H, 1.31 (3H, S), 0.90— 0.68 (2H, oi)

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Merger- R2 (R3) n Species Physical nina No. geome- constant Triazole Olefin R2 proton proton proton isomer

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In 241472 33 34, the percentage of infested area is measured and the corresponding disease indicator is 0.05, 1, 2 and 4. The strength of the disease is calculated according to the equation below.

Test Example 2

Cercospora arachidicola (Cercospora arachidicola) The soil is filled into 150 ml plastic rootstocks into which peanuts are sown (variety: Hanritsu-seij in 1 seed per pot and cultivated 12 days in a greenhouse with air conditioning (25 to 30 ° C) to give young seedlings at the stage of the third true leaf, at which time the emulsifiable concentrate of each test compound diluted with water is sprayed with 10 ml per pot. the young seedlings are spotted (Cercospora arachichicola j, covered with a polyvinyl chloride moisture retention film and placed in an air-conditioned glass that is kept at 25-30 ° C. Seedlings are cultivated for another 10 days in a greenhouse to the disease has been sufficiently infected and the disease appearance of the leaves is observed.

Indicator Disease appearance 0 No cluster or infected area is observed on the leaf surface 0.5 Clusters or infected areas less than 5% are observed on the leaf surface 1 Observe noise or infected area less than 20% on the leaf surface 2 Observe noise or infected area smaller on the leaf surface than 50% 4 Clusters or infected areas are observed on the leaf surface that are not less than 50% disease strength (%) = Σ (disease indicator) x (number of leaves) 4x (sum of examined leaves) x 100

The disease suppression is then calculated according to the following equation: (disease strength in treated pot) disease suppression (%) = 100 ————: —-— τντγ (disease potency in neosetren pots) x 100 Result of Table 4 is that the isomer IA of the compound of this invention has a clearly high protective effect, comparing with the isomer IB. TABLE 4

Test Compound Active Component Concentration (ppm) Disease Suppression (%) Illusion No. Geometrical Isomer 1 Isomer IA 250 100 2 Isomer IA 250 100 3 Isomer IA 250 100 4 Isomer IA 250 100 5 Isomer IA 250 100 9 Isomer IA 250 100 20 Isomer IA 250 100 21 Isomer IA 250 100 23 Isomer IA 250 100 26 Isomer IA 250 100 27 Isomer IA 250 100 29 Isomer IA 250 100 30 Isomer IA 250 100 31 Isomer IA 250 100 32 Isomer IA 250 100 33 Isomer IA 250 100 34 Isomer IA 250 250 100 241472 35 36

Test Compound Concentration Effective Disease Suppression Compound No. Geomerisomer Type Component (ppm) (%) (Reference Compound) 1 Isomer IB 250 0 2 Isomer IB 250 0 3 Isomer IB 250 0 4 Isomer IB 250 0 5 Isomer IB 250 0 9 Isomer IB 250 0 20 Isomer IB 250 0 23 Isomer IB 250 0 30 Isomer IB 250 0 23 Isomer IB 250 0 30 Isomer IB 250 0 30 Isomer IB 250 0 30 Isomer IB 250 0 32 Isomer IB 250 0 34 Isomer IB 250 0 Cl CN Commercial Fungicide 250 100 / Cl CN Test Example 3 in an amount of 10 ml per! flowerpot. After air-drying, young seedlings are inoculated with a protective mold against gray mold in cucumbers (Botrytis cinerea) and placed in (Botrytis cinerea) a humidified constant temperature chamber maintained at 20 ° C. After 3 days, the appearance of the sand soil is observed to be filled into plastic cucumber diseases. A 150 ml test for infections and discharges in which the disease is suppressed is carried out with a cucumber (variety: Sagani-hanjiro) in the same manner as in the test sample of 3 seeds per pot and cultivated 2. 8 days in a greenhouse to obtain small sepses. As can be seen from Table 5, the isoenzymes are in the uterine stage. At this time, compound IA of compound 1 has a remarkably emulsifiable concentrate of each tested protective effect, sprayed onto sheet IB compared to isomeric compounds diluted with water. 241472 37 38 TABLE 5

Compound Effective Ingredient Disease Suppression (ppm) (%)

Isomer IA of Compound No. 1Isomer IB of Compound No. 1 conhc ^ H, Q ^^ nhcooch, 500 500 500 100 10 90

Note: 1) commercial fungicide

Test Example 4

Wheat Rust Protection (Pucciniarecondita) (Therapeutic Effect) (Young Seedling Test) Sandy soil is filled into 150 ml plastic kneaders into which wheat is sown (variety: Norin No. 61) 10 to 15 seeds per pot and cultured for 7 days in a greenhouse with air conditioning (18 to 23 ° C) to obtain young seedlings in the middle right leaf. At this time, the emulsifiable concentrate of each test compound diluted with water was sprayed at 10 ml per pot, and the seedlings were cultured for 10 days at constant room temperature (23 DEG C.) under fluorescent light Examination of disease and calculation of disease suppression is carried out in the same manner as in Test Example 2. It is clear from Table 6 that the isomer IA of the compounds of the invention has a clearly high protective effect not only compared to isomer IB, but also a commercial fungicide and a well known compound. TABLE 6

Test compound Disease suppression ('%)

Compound Type of geometrical concentration of active ingredient isomer 100 ppm 20 ppm 5 ppm T IA IB 100 100 100 95 100 '25 2 IA 100 100 100' IB 100 93 21 3 IA 100 100 100 IB 100 95 30 4 IA 100 99 86 IB 100 64 0 9 IA 100 85 27 IB 94 60 0 17 IA 100 87 36 IB 72 63 0 21 IA 100 89 15 IB 78 56 0 26 IA 100 100 100 IB 100 60 0 27 IA 100 100 100 IB 100 95 20 29 IA 100 100 100 IB 100 75 0 30 IA 100 100 100 IB 100 0 0 31 IA 100 100 100 100 IB 100 64 0 241472

Test Compound Compound Type of geometric isomer number

33 IA IB 34 IA IB 36 IA IB 39 IA IB

Disease suppression (i%) Active ingredient concentration 100 ppm 20 ppm 5 ppm 100 100 100 100 32 0 100 90 36 100 0 0 100 100 96 100 73 0 100 100 30 93 63 0 table 6 - continued

Test compound Reference known compound

Disease Suppression (%) Active substance concentration 100 ppm 20 ppm 5 ppm

Ct ~ ζ. / V — O "CH" C "C fCHnhy J, J 5 Λ l, 4 56 50 '

XI

64 53 58 58 X3 X4

X5

N 50 14

W-ch _Q ϊΑ

OH 1. 241472 39 40

Disease Control ('%)

Active substance concentration 100 ppm 20 ppm 5 ppm

Test compound Reference known compound

100 0 0 0 0 0 X7

Note: xt Commercial fungicide, compound described by brit. X2 A compound disclosed in German Patent Specification No. 27 34 426. X3 A compound disclosed in Belgian Patent No. 1 364 619. X45 A compound disclosed in NSR Patent No. 26 10 022. X5 A compound disclosed in NSR Patent No. 26 54 890. X6 A compound disclosed in U.S. Patent No. 4,086,351. X7 A compound disclosed in U.S. Pat. No. 1,464,224.

Test Example 5

Protective effect against wheat rust (Puccinia graminis) (therapeutic effect) (test of young seedlings)

Young wheat seedlings (NorinNo. 61) are obtained in the same manner as in Test Example 4. Seedlings are then inoculated with grass fungi (Puccinia graminis) and infected by placing them for 16 hours in a humid chamber at a temperature of 23 at that time. of the compound to be diluted with water is sprayed at 10 ml per pot. Seedlings cultivate for 10 days in a greenhouse with air conditioning maintained at 23 ° C and then the appearance of disease on the first right-hand leaf is observed. Disease testing and disease suppression calculations are performed in the same manner as in Test Example 2. The result of Table 7 is that the isomer IA of the compound of the invention is a distinctly high protective effect compared to not only the isomer IB but also the commercial fungicide and well known compound. TABLE 7

Test compound

Compound Concentration Effective Disease Suppression No. Geometric Type Component Component (ppm) (%) 100 100 IA 20 100 5 100 100 100 IB 20 95 5 25 100 100 IA 20 100 5 100 100 100 IB 20 93 5 21 241472 42

Disease Suppression (%) 41

Test compound

Compound Concentration Effective No. Geometric Isomer Species Component (ppm) 100 100 3 IA 20 100 5 100 100 100 IB 20 95 5 30 100 100 20 IA 20 100 5 100 IB 50 0 100 100 i26 IA 20 100 5 100 IB 50 0 100 100; 27 IA 20 100 5 100 100 100 IB 20 90 5 30 100 100 30 'IA 20 100 5 100 IB 50 0 100 100 IA 20 100 5 100 32 IB 50 0

Reference well known compound

XI

X2I

W // o O-CH-CC (CH3) 3 100 20 5

50 84 13

87 87 0 xi

Note: xi Commercial fungicide, compound described by brit. No. 2,964,619. X2 The compound disclosed in German Patent Application Ser. 27 34 426. 241472 43 44 X3 The compound disclosed in U.S. Pat. No. 4,086,351.

Test Example 6

Protection against powdery mildew powdery mildew (Erysiphe graminis) made by molds (test of young seedlings) Sand soil is filled into 150 ml plastic pots into which barley (variety Goseshikoku) is seeded in quantities of 10 to 15 seeds per pot and cultures for 7 days in a greenhouse with air conditioning (18 to 23 qC) to obtain young seedlings in the middle right leaf. Thereafter, the emulsifiable concentrate of each test compound diluted with water is sprayed onto the sheet at a rate of 10 ml per pot. After air-drying, young seedlings are inoculated with Erysiphe graminis and cultured at constant room temperature (23 ° C) under fluorescent light for 10 days. Then the appearance of the disease is observed on the first right leaf; the strength of the disease is calculated as follows: For leaves, the percentage of infested area is measured and the corresponding disease indicator is 0, 0.5, 1, 2 and 4. The strength of the disease is calculated according to the equation below.

Indicator Disease disease 0 No clump of 0.5 is observed on the surface of the leaf No less than 5 kyο 1 clumps are observed on the leaf surface. Noise less than 20% is observed on the leaf surface 2 Noise less than 50% is observed on the leaf surface 4 Noise on the leaf surface 4 On the leaf surface clumps that are not less than 50% are observed. disease strength (%) Σ (disease indicator) x (number of sheets) 4x (number of sheets examined) x 100

The disease suppression is then calculated by the following equation: "". , "(disease potency in osetren pots)""" suppression of disease%) = 100 - 7—-7: —-- c —-—; c — x 100 (disease strength in neosetren pots) is that the compounds of the invention have an excellent protective effect against barley powdery mildew (Erysiphe graminis) and that the effect is equal to or greater than that of the reference compound. TABLE 8

Test compound Compound e. Geometric isomer type Active ingredient concentration (ppm) Disease suppression (%) 1 isomer IA 500 100 2 isomer IA 500 100 3 isomer IA 500 100 4 isomer IA 500 100 5 isomer IA 500 100 6 isomer IA 500 100 7 isomer IA 500 100 8 isomer IA 500 100 9 isomer IA 500 100 10 isomer IA 500 100, 11 isomer IA 500 100 12 isomer IA 500 100 13 isomer IA 500 100 14 isomer IA 500 100 15 isomer IA 500 100 16 isomer IA 500 100 17 isomer IA 500 100 18 isomer IA 500 100 19 isomer IA 500 100 20 isomer IA 500 100 21 isomer IA 500 100 22 isomer IA 500 100 23 isomer IA 500 100 24 isomer IA 500 100 25 isomer IA 500 100 241472 compound

Geometric isomer type Active ingredient concentration (ppm) Disease suppression (%) isomer IA 500 100 isomer IA 500 100 isomer IA 500 100 isomer IA 500 100 isomer IA 200 100 isomer IA 200 100 isomer IA 200 100 isomer IA 200 100 isomer IA 200 100 isomer IA 50 100 isomer IA 50 100 isomer IA 50 100 isomer IA 50 100 isomer IA 50 100 isomer IA 50 90 isomer IA 50 91 isomer IA 50 89 isomer IA 50 93 isomer IA 50 100 isomer IA 50 100 isomer IA 50 95 isomer IA 50 100 isomer IA 50 95 isomer IA 50 100 isomer IA 50 80 isomer IA 50 100 isomer IA 50 100 isomer IB 500 100 isomer IB 500 100 isomer IB 500 100 isomer IB 500 100 isomer IB 500 100 isomer IB 500 100 isomer IB 500 100 isomer IB 500 100 isomer IB 500 100 isomer IB 500 100 isomer IB 500 100 isomer IB 500 100 isomer IB 500 100 isomer IB 500 100 isomer IB 500 100 isomer IB 500 100 isomer IB 500 100 isomer IB 500 100 isomer IB 500 100 isomer IB 500 100 isomer IB 500 100 isomer IB 500 100 i IB 500 100 isomer IB 500 100 isomer IB 500 100 isomer IB 500 100 isomer IB 500 100 isomer IB 500 100 isomer IB 500 100 isomer IB 500 100 isomer IB 500 100 isomer IB 500 100 241472

Test compound Compound No. Geometric isomer type Active ingredient concentration (ppm) Disease suppression (%) 38 isomer IB 500 100 39 isomer IB 500 100 43 isomer IB 500 100 47 isomer IB 500 100 51 isomer IB 500 100 1 * isomer IIA 500 100 2 * isomer IIA 500 100 3 * isomer IIA 500 100 4 * isomer IIA 500 100 5 * isomer IIA 500 100 6 * isomer IIA 500 100 7 * isomer IIA 500 100 8 * isomer IIA 500 100 9 * isomer IIA 500 100 10 * isomer IIA 500 100 11 'isomer IIA 500 100 12 * isomer IIA 500 100 13 * isomer IIA 500 100 14 * isomer IIA 500 100 15 * isomer IIA 500 100 16 * isomer IIA 500 100 17 * isomer IIA 500 100 18 * isomer IIA 500 100 19 * isomer IIA 500 100 20 * isomer IIA 500 100 21 * isomer IIA 500 100 22 * isomer IIA 500 100 23 * isomer IIA 500 100 24 * isomer IIA 500 100 25 * isomer IIA 500 100 26 * isomer IIA 500 100 27 * isomer IIA 500 100 28 * isomer IIA 500 100 29 * isomer IIA 500 100 30 * isomer IIA 500 100 31 * isomer IIA 500 100 32 * isomer IIA 500 100 33 * isomer IIA 500 100 1 * isomer IIB 500 100 2 * isomer IIB 500 100 3 * isomer IIB 500 100 4 * isomer IIB 500 100 5 * isomer IIB 500 100 6 * isomer IIB 500 100 7 * isomer IIB 500 100 8 'isomer IIB 500 100 9 * isomer IIB 500 100. 10 * isomer IIB 500 100 11 * isomer IIB 500 100 12 * isomer IIB 500 100 13 * isomer IIB 500 100 14 * isomer IIB 500 100 15 * isomer IIB 500 100 16 * isomer IIB 500 100 17 * isomer IIB 500 100 18 * isomer IIB 500 100 19 * isomer IIB 500 100 20 * 1 isomer IIB 500 100 21 * isomer IIB 500 100 22 *, isomer IIB 500 100 23 * isomer IIB 500 100 24 * isomer IIB 500 100 241472 45 46

Test compound

Compound No. A Geometric isomer type Active ingredient concentration (ppm) Disease suppression (%) 25 * isomer IIB 500 100 26 * isomer IIB 500 100 27 * isomer IIB 500 100 28 * isomer IIB 500 100 29 * isomer IIB 500 100 30 * isomer IIB 500 100 31 * isomer IIB 500 100 32 * isomer IIB 500 100 33 * isomer IIB 500 100

Reference compound ch3 ch3 (commercial fungicide) λ 500 100 / "200 81 50 43

Test Example 7 500 g of a soil mixture consisting of sea bream, mountain soil and peat are filled with 13 cm diameter openings in which daisy chrysanthemum morpholium ramat is cultivated. Two weeks after sowing, the plants are cleaved and cultured in the form of 3 stems and new buds are grown. Two weeks of cleavage, an aqueous liquid of predetermined concentration of each test compound is applied to the plants and 42 days after application of the pesticide, the plant growth inhibiting effect is tested. The results are shown in Table 9. The effect is evaluated as follows:

The increase in plant height is calculated as the difference between the original plant height at time of application and the plant height at forty-eight days after application and is expressed by the height index, with the corresponding difference in the unopened pot being 100. The values in the table are the average of the three repeated determinations .

The reference compound used is B-Nine (N, N-dimethylaluminosubstituted succinamide). 241472 47 43 TABLE 9

Stunt test

Compound Concentration of the active ingredient (ppm) Height (%) Maximum length of leaf, (%) Diameter (%) Phyto-toxicity Isomer IA of Compound No. 1 500 65 97 98 No Isomer IB of Compound 6. 1 500 81 102 105 no Isomer IA of Compound No. 4 500 73 100 101 no Isomer IB of Compound No. 4 500 85 101 102 no Isomer IA of Compound No. 9 500 67 99 98 no Isomer IB of Compound No. 9 500 88 100 100 no Isomer IA of Compound No. 11 500 57 95 95 no Isomer IB of Compound No. 11 500 81 102 100 no Isomer IA of Compound No. 21 500 73 97 99 no Isomer IB of Compound No. 21 500 86 97 101 no Isomer IA of Compound No. 26 500 75 101 100 no Isomer IB Compound No. 26 500 88 100 98 no Isomer IA of Compound No. 30 1000 63- - no Isomer IA of Compound No. 31 1000 65- - no Isomer IA of Compound No. 35 500 64 101 98 no Isomer IA of Compound No. 43 500 62 98 100 no Isomer IB Compounds No. 35 500 89 102 101 no B-Nine χι 4 000 86 98 103 no No treatment - 100 100 100 no

Note: xi Commercial fungicide reference compound CH3 II /

CH 2 NH 3 CH 3

CH2C-OH

. 'II: o

Test Example 8

Herbicidal Effect Test on Field Plants The soil is mixed with the seeds of the bloody squirrel (Digitaria sanguinalis), the Amaranth Retroflexus and the Chenopodium album, and filled into a 1.50 m 2 Wagner pot. Thereafter, the hay sprays the soil surface with a hand sprayer an emulsifiable concentrate diluted with water with a predetermined amount of active ingredient. After application, seedlings of beetroot (variety: Monohil) were transferred to the Wagner pot in a five-petalled stage, which were cultivated in a paper pot. Then the seedlings are cultivated in a greenhouse. The herbicidal effect and phytotoxicity of the plants are observed 20 days after application. The results are shown in Table 10. The herbicidal effect is expressed as 0-5, as follows, provided that phytotoxicity is also expressed to the same standard. 0 Percent inhibition 0 to 9% 1 Percent inhibition 10 to 29% 2 Percent inhibition 30 to 49% 3 Percent inhibition 50 to 69% 4 Percent inhibition 70 to 89% 5 Percent inhibition 90 to 100%

As shown in Table 10, the isomer IA of the present compound has a much stronger herbicidal effect compared to isomer B. 241472 TABLE 10

Compound 'Dose (g / ha) Rosemary Herbicidal Effectskin Bee Goosefoot White Phytotoxicitapro Beetle Isomer IA 4 000 5 5' 5 0 Compound No. 1 2 000 4 5 5 0 Isomer IB 4 000 3 4 4 0 Compound No. 1 2 000 2 3 3 0 Isomer IA '4 000 4 5' · 5 0 Compound No. 2 2 000 4 4 5 0 Isomer B 4 000 3 3 3 0 Compound No. 2 2 000 1 3 ·· 3 0 Isomer IA 4 000 5 5 5 0 Compound No. 3 2 000 4 5 5 0 Isomer B 4 000 3 3 3 0 Compound No. 3 2 000 2 3 3 0 Isomer IA 4 000 5 5 5 0 Compound No. 4 2 000 4 5 5 0 Isomer B 4 000 3 3 3 0 Compound No. 4 2 000 1 2 3 0 Isomer IA 4 000 4 5 '5 0 Compound No. 5 2 000 4 4 5 0' Isomer B 4 000 2 2 3 0 Compound No. 5 2 000 2 2 1 0 Isomer IA 16,000. 4 5 5 0 Compound No. 6 8 000 4 5 5 0 Isomer B 16 000 2 3 2 0 Compound No. 6 8 000 1 1 2 0 'Isomer IA 4 000 5 5' 5 Compound No. 7 2 000 4 4 5 0 Isomer B 4 000 3 3 3 0 Compound No. 7 2 000 2 3 3 0 Isomer IA 4 000 4 5 5 0 Compound No. 8 2 000 4 4 4 0 Isomer B 4 000 2 3 4 0 Compound No. 8 2 000 1 2 3 0 Isomer IA 4 000 5 5 5 0 Compound No. 9 2 000 4 5I 5 0 Isomer B 4 000 2 3 3 0 Compound No. 9 2 000 2 1 3 0 Isomer IA 4 000 5 4 5 0 Compound No. 10 2 000 4 4 4 0 Isomer B 4 000 2 3 3 0 Compound No. 10, 2 000 2 2 3 0 Isomer IA 4 000 5 5 · 5 0 Compound No. 11 2 000 4 5 5 0 Isomer B 4 000 3 4 4 0 Compound No. 11 2 000 3 2 2 0 Isomer IA 16 000 4 4 4 0 Compound No. 12 8 000 4 4 4 0 Isomer IA 16 000 4 5; 5 3 Compound No. 13 8 000 4 4 5 3 Isomer IB 16 000 2 4 3 0 Compound No. 13 8 OOO 1 1 2 0 Isomer IA 8 000 4 5 5 0 Compound No. 14 4 000 4 5 5 0 Isomer IB 8 000 3 4 3 0 Compound No. 14 4 000 2 3 3 0 Isomer IA 4 000! 5 5 5 0 Compound No. 15 2 000 4 4 4 0 Isomer IB 4 000 3 4 3 0 (Compound No. 15 2 000 3 3 2 0. Isomer IA 8 000 5 5 5 0 Compound No. 16 4 000 4 5 5 0 Isomer IB 8 OOO 1 3 3 0 Compound No. 16 4 000 0 3 3 0 241472

Compound Dose (g / ha) Herbicidium action Goosefoot white Phytotoxicity1 for beetroot rosemary bloody amaranth bent Isomer IA 4 000 5 5 0 0 Compound No. 17 2 000 4 4 5 0 Isomer IB 4 000 1 2 2 0 Compound No. 17 2 000 0 1 2 0 Isomer 000 8 000 4 5 '4 0 Compound No. 18 4 000 4 4 4 0 Isomer IB 8 000 0 1 2 0 Compound No. 18 4 000 0 1 1 0 Isomer IA 8 000 5 5 5 0 Compound No. 19 4 000 4 5 5 0 Isomer IB 8 000 3 3 3 0 Compound No. 19 4 000 2 1 3 0 Isomer IA 16 000 4 5 5 0 Compound No. 20 8 000 4 4 4 0 Isomer IB 16 000 2 4 3 ΰ Compound No. 20 8 000 0 2 1 0 Isomer IA 16 000 5 5 5 0 Compound No. 21 8 000 4 5 5 0 Isomer IB 16 000 3 3 2 0 Compound No. 21 8 000 2 1 2 0 Isomer IA 16 000 4 4 4 0 Compound No. 22 8 000 4 4 4 0 Isomer IB 16 000 2 4 3 0 Compound No. 22 8 000 1 1 2 '0 Isomer IA 8 000 4 5 5 0 Compound No. 23 4 000 4 5 5 0 Isomer IB 8 000 2 2 2 0 Compound No. 23 4 000 0 1 '2 0 Isomer IA 8 000 4 4 5 0 Compound No. 24 4 000 4 4 4 0 Isom er IA 16 000 5 5 5 0 Compound No. 25 8 000 4 5 4 0 Isomer IB 16 000 2 4 3 0 Compound No. 25 8 000 0 2 3 0 Isomer IA 4 000 5 5 '5 0 Compound No. 26 2 00'0 4 5 5 0 Isomer IA 4 000 5 5 5 0 Compound No. 27 2 000 4 5 5 0 Isomer IA 4 000 5 5 5 0 'Compound No. 35 2 000 5 5' 5 0 Isomer IA 8 000 5 5 '5 0 Compound No. 36 4 000 4 4 5 0 Isomer IA 16 000 5 5 5 0 Compound No. 37 8 000 4 5 5 0 Isomer IA 8 000 5 5 5 0 Compound No. 38 4 000 4 4 4 0 Isomer IA 8 000 4 5 5 0 Compound No. 39 4 000 4 5 5 0 Isomer IA 4 000 5 5 '5 0 Compound No. 40 2 000 4 5 4 O1 Isomer IA 8 000 5 5 5 0 Compound No. 41 4 000 5 4 4 0 Isomer IA 4 000 4 5 5 0 Isocene No 42 2 000 4 4 5 0 Isomer IA 8 000 5 5 5 0 Compound No 43 4 000 5 5 5 0 Isomer IA 8 000 5 5 5 0 Compound No. 44 4 000 4 5 5 0 Isomer IA 16 000 5 5 5 0 Compound No. 45 8 000 4 5 5 0 Isomer IA 16 000 4 5 5 0 Compound No. 40 8000 4 5 4 0 241472 48 30

Compound Dose (g / ha) "Herbicidal action Goosefoot white Phytotoxicity1for the sugar beet Rosemary amaranth bent Isomer IA 8 000 5 5 0 0 Compound No. 47 4 000 5 5 5 0 Isomer IA 16 000 4 5 5 0 Compound No. 48 8 000 4 5 5 · 0 Isomer IA 16 000 4 5 4 0 Compound No. 49 8000 4 4 4 0 Isomer IA 8 000 5 5 5 0 Compound No. 50 4 000 4 5 5 0 'Isomer IB 4 000 2 3 3 θ Compound No. 35 2 000 1 2 2 0 'Isomer IB 8 000 3 3 3 0 Compound No. 43 4 000 2 3 1 0 Test Example 9 measures the height of each plant. The results are shown in Table 11. Numerical Values The high affecting effect on soybean in the table represents the average height of two and barley soybean plants and three barley plants that is Sand soil is filled into a 500 ml plastic hatch. The upper half of the pot is removed, mixed with 10 ml of the emulsifiable concentrate of each test compound diluted with water and returned to the pot. The soybean and barley beans 3 and 5 seeds per pot are then sown in the treated soil. Soy and barley are cultured in a greenhouse kept at 25 ° C and, after 14 days, expressed as a percentage of the corresponding average height in untreated pots, rated as 100.

The result is that the isomer IA of the compounds of the invention exhibits a remarkably high suppressive effect compared to the isomer IB serving as the reference compound. In addition, any of the ΓΑ and IB isomers do not detect phytotoxicity, such as chlorosis and necrosis, and it is observed that the leaves have a dark green color. TABLE 11

Test compound Dose size (g / ha) Soybean Bob (%) Barley (%) Isomer IA 1000 18 17 Compound No. 1 500 22 18 250 37 26 Isomer IB 1 000 22 52 Compound No. 1 500 28 47 250 46 89 1000 20 7CE Isomer IA 500 33 88 Compound No. 35 250 54 95 1000 21 57 Isomer IA 500 28 78 Compound No. 40 250 47 102 1000 19 76 Isomer IA 500 24 100 Compound No. 43 250 50 102 1 000 33 89 Isomer IA 500 45 98 Compound No. 47 250 72 97 1000 44 77 Isomer IA 500 65 89 Compound No. 50 250 97 98 1000 85 98 Isomer IB 500. 93 102 Compound No. 35 250 99 100 Test Example 10 On November 20 at the field and next year sprayed on the leaf with an emulsified concentrate iso- Control effect on the growth of inter-barley bar IA of Compound # 1 by diluted water, both once (4) April) and two-barley (variety: Goseshikoku) are sown times (April 4 and April 24). In addition, the total length of the blades in the treated area is also shortened.

Phytotoxicity, such as yellowing and sterility, is by no means observed.

The barley of each area is cut at the 28th of May and the length of the barley is measured at 30 barley stalks. As shown in Table 12, the length of the main fourth and fifth intercosts of the treated area is significantly shorter in the TABLE 12

Tested Intercollar. Total Compound Treatment 1. (cm) 2. (cm) 3. (cm) 4. (cm) 5. (cm) 6. (cm) 7. (cm) length (cm) No treatment - 32.1 17, 5 15,7 13,7 11,4 9,5 6,5 106,4 Isomer IA 25 ppm Compound No. 1 twice 35,0 19,1 14,7 12,0 9,2 8,7 5,7 104 , 4 Isomer IA 50 ppm ico, 2 compound No. 1 once 36.2 20.7 15.0 10.0 6.6 6.3 5.4 Isomer IA 50 ppm Compound No. 1 twice 36.8 19.1 12.8 9.2 7.4 7.1 6.1 98.5

Test Example 11 Effect of Turf Growth Control A 3: 1 soil and peat soil mixture is filled into a 1/50 m 2 Wagner pot and grass Zoysia matrella L is transferred to it on 6 December.

The grass of Zoysia matrella L. is cultivated in a 30K CC maintained by repeated fertilization with artificial fertilizer and cosmos until its growth becomes uniform. Immediately grassing of Zoysia matrella L. on May 9th, hand spraying with an emulsifiable concentrate of each test compound was applied to the diluted water in an amount of 10 ml of pot.

On June 2, the increase in grass height is measured and the effect of affecting growth of the compound to be measured is evaluated. The effect is expressed by the height index, which corresponds to the increase in comparison with the untreated pot laid down in 100. The results are shown in Table 13. It will be appreciated from the table that the compounds of the present invention have an effect on the growth of grass grass Zoysia matrella L.

Test compound

Isomer IA of Compound No. 1 Isomer IA of Compound No. 27Isomer IB of Compound No. 1Non-treated TABLE 13Dose Size (g / ha) 2,0002,0002,000

Height Index (%} 71 74 86 100 (7.0 cm)

Test Example 12

Test for herbicidal action against growing field weeds

The Wagner pots of 1/50 m2 are always filled with 1.5 kg of field soil and maintain the condition of excessive irrigation. The rice seedlings are transferred to the third leaf stage and the seeds of the hedgehog (Echinochloa crus-galli) and the creeper (Scirpus puncoides var. Hotarui Oh-wij) are sown. 25 days after application, the herbicidal action of the test compound was detected on the weed as well as on the broadleaf weed and on the palm (Eleocharis acicularis), which spontaneously arose. When the test compounds are applied, a predetermined amount of each compound is processed into a wettable powder and pipetted with a dose of 10 ml per pot Herbicidal effect is expressed in a number range from 0 to 5. 0% inhibition 0 to 9% 1 Percent inhibition 10 up to 29% 2 Percentage inhibition 30-49% 3 Percentage inhibition 50-69% 4 Percentage inhibition 70-89% 5 Percentage inhibition 90-100% None to the plants, rice is not phytotoxic and does not, for example, cause malformation, yellowing and chlorosis. 241472 53 54 TABLE 14

Test Compound Dose Size (g / ha) Herbicidal Effect * 1 2 * 4 Hedgehog Foot Broad-leaved Weed Swamp Grip Palach Isomer IA 2 000 5 5 5 Compound No. 1 5 000 5 5 5 _ Isomer IA 2 000 15 5 5 Compound # 1 3 1 000 4 5 4 Isomer IA 2 000 6 5 5 Compound No 4 1 000 4 5 4 Isomer IA 2 000 5 5 5 _ Compound No. 2 1 000 5 5 5 _ Isomer IA 2 000 5 5 5 __ Compound No. 27 1000 5 5 4 _ Isomer IA 2 000 5 5 5 _ Compound No. 5 1 000 4 5 5 —— Isomer IA 2 000 5 5 5 _ Compound No. 9 1000 5 5 5 - Isomer IB 2 000 3 3 3 - Compound No. 1Isomer IA 1000 2 3 2 - Compound No. 30Isomer IB 4 000 5 5 - 5 Compound No. 30Isomer IA 4 000 5 5 - 5 Compound No. 31Isomer IB 4 000 5 5 - 5 Compound No. 31Isomer IA 4 000 5 5 - 5 Compound No. 32Isomer IB 4 000 5 5 - 5 Compound No. 32Isomer IA 4 000 5 5 - 5 Compound No. 33Isomer IB 4 000 5 5 - 5 Compound No. 33Isomer IA 4 000 5 5 - 5 of Compound No. 34Isomer IB 4,000 '-5-5 Compound No. 34 4,000 5 5 - 5

Test Example 13

Protective effect test for root-root beet on rice (Rhizoctonia solani)

The emulsifiable concentrate of each compound diluted with water is sprayed onto the plants (varieties: Kinki No. 33) grown in the root, which have been cultivated in a greenhouse for 2 months. mycellia (5 cm in diameter) After inoculation of the serostyle, the rice is infected in a wet chamber (28 ° Celsius) for 4 days and the appearance of the disease is determined. 2, 4 and 8. The strength of the disease is calculated according to the equation below.

Indicator Disease Appearance 0 Uninfected Area and No Cluster Growth 1 Uninfected Area and Agglomeration 2 Area Infected Less than 0.5cm 4 Infected Area 0.5 to 2cm 8 Area infected with more than 2 centimeters. For leaf sheath, the percentage of the population is measured - 241472 55 X 100 X 100 Disease Strength (%) = X (X Disease Indicator 8X (total number of leaf sheaths examined)

Disease suppression is then calculated by the following equation: disease suppression (%) (disease potency in treated pot) (disease potency in untreated pot)

As shown in Table 15, the isomer IA of the compounds of the invention has been found to have a remarkably high protective effect compared to the isomer IB and that the effect of the reference compound effect or the effect of the reference compound is superior. TABLE 15

Test compound Active ingredient concentration (ppm) Suppression i (% Isomer IA of Compound No. 38,500 95 Isomer IA of Compound No. 44,500 95 Isomer IA of Compound No. 45,500 95 Isomer IA of Compound No. 46,500 80 Isomer IA of Compound No. 47,500 100 (Reference compound) Isomer IB of Compound No. 38 500 0 Isomer IB of Compound No. 43 500 0 Isomer IB of Compound No. 47 500 0 Validamycin xi 30 78 Note: xi Reference Compound (Commercial Fungicide) Preparation Example 1 Preparation Example 4 Dust Wettable Powder 1 part of the IA isomer of each of the compounds 1 to 52 according to the invention, 89 parts of clay and 10 parts of the mixture is mixed well until it has a powdered form.

The dust of 3 parts of the isomer IA of each of the compounds 1 to 52 of the invention, 67 parts of clay and 30 parts of talc is stirred well until it has a powder form. A dust containing 3% of the active ingredient is obtained. Preparation example 3

Wettable powder 30 parts of the isomer IA of each of compounds 1 to 52 of the invention, 45 parts diatomaceous earth, 20 parts colloidal silicon dioxide, 3 parts wetting agent (sodium lauryl sulfate) and 2 parts dispersant (calcium lignosulfonate is well stirred until powdered) 50 parts of the isomer IA of each of the compounds 1 to 52 of the invention, 45 parts of diatomaceous earth, 2.5 parts of a wetting agent (calcium alkylbenzene sulfonate) and 2.5 parts of a dispersing agent (kaleium lignosulfonate) are obtained. ) is stirred until it has a powdered form, and a wettable powder containing 50% of the active ingredient is obtained.

The emulsifiable concentrate of 10 parts of the isomer IA of each of compounds 1 to 51 of the invention, 80 parts of cyclohexane and 10 parts of emulsifier (polyoxyethylene-alkyl ether) is mixed to give an emulsifiable concentrate containing 10% of the active ingredient. Preparation example 6

Granules of 5 parts by weight of the isomer IA of each of the compounds 1 to 52 of the invention, 40 parts by weight of bentonite, 50 parts by weight of clay and 5 parts by weight of sodium-

Claims (12)

241472 37 of the lignosulfonate is well mixed until a powder form is obtained. The mixture is well kneaded with water, granulated and dried. This gives a granule. Preparation Example 7 Dust 2 parts of IIA isomer of each of the compounds 1 to 33 ‘of the invention, 88 parts of clay and 10 parts of talc are stirred well until a powder form is obtained. A powder containing 2% of the active ingredient is obtained. Preparation Example 8 Dust 3 parts of IIA isomer of each of the compounds 1 to 33 ‘of the invention, 67 parts of clay and 30 parts of talc are mixed well until a powder form is obtained. A powder containing 3% of the active ingredient is obtained. Preparation Example itelný Wettable powder 30 parts of the isomer IA of each of compounds 1 to 33 'of the invention, 45 parts diatomaceous earth, 20 parts colloidal silicon dioxide, 3 parts wetting agent (sodium lauryl sulphate and 2 parts dispersing agent (calcium lignosulphonate) well It gives a wettable powder containing 30% of the active ingredient Preparation Example 10 Wettable powder 50 parts of the IIA isomer of each of the compounds 1 to 33 'of the invention, 45 parts diatomaceous earth 58, 2.5 parts The wetting agent (calcium alkylbenzene sulfonate) and 2.5 parts of the dispersant (calcium lignosulfonate) are blended until a powder form is obtained. A wettable powder containing 50% of the active ingredient is obtained Preparation Example 11 Emulsifiable concentrate of 10 parts of the IIA isomer of each of the compounds 33 to 33 ', 80 parts cyclohexane and 10 parts emulsions The polyoxyethylene alkylaryl ether is mixed to give an emulsifiable concentrate containing 10% of the active ingredient Preparation Example 12 Granules of 5 parts by weight of the isomer IIA of each of the compounds Γ to 33 'of the invention, 40 parts by weight of bentonite, 50 parts by weight clay and 5 parts by weight of sodium lignosulfonate are well mixed until a powder form is obtained. The mixture is well kneaded with water, granulated and dried. This gives granules containing 5% of the active ingredient. Preparation Example 13 Wettable powder 80 parts of the isomer IA of each of compounds 1 to 52 of the present invention, 15 parts of diatomaceous earth, 2.5 parts of a wetting agent (calcium alkylbenzene sulphonate) and 2.5 parts of a dispersant (calcium lignosulphonate) are mixed, until it is in powder form. A wettable powder containing 80% of the active ingredient is obtained. OBJECT What is claimed is: 1. A fungicidal composition, a herbicidal composition and / or a plant growth regulating agent for agriculture and horticulture comprising the geometric isomer of formula (I) as an active ingredient. or 4-carbon or-2-propynyl, R 2 is C 1 -C 6 alkyl, cyclopropyl or 1-methyl-cyclopropyl, R 1, which are the same or different, atomhalogen, alkyl of 1 to 3 carbon atoms substituted with a halogen atom, an alkyl group having from 1 to 4 carbon atoms, an alkoxy group having from 1 to 4 carbon atoms, a phenoxy group, a phenyl group, a cyano group or a nitro group, n 0, 1, 2, 3, 4 or 5; its salt. 2. A fungicidal composition, a herbicidal composition and / or a plant growth agent for agriculture and horticulture, characterized in that it comprises, as active ingredient, a geometric isomer of the general formula (N wherein R1 represents a hydrogen atom, an alkyl group having 1-4 carbon atoms) carbon atoms, alkenyl having 3 241472 59 ce 1, wherein R 1 is hydrogen, R 2 is tert-butyl, R 5 is halogen and number 1 or 2. 3. A fungicidal composition, a herbicidal composition and / or a plant-modifying agent for agriculture and horticulture comprising the geometric isomer of formula I, wherein R1 is hydrogen, R2 is tertiary. -butyl, R 3 is halogen and null, number 1 or 2. 4. A fungicidal composition, a herbicidal composition and / or a plant-modifying agent for agriculture and horticulture, characterized in that it comprises as an active ingredient a geometric isomer of formula I wherein R1 is hydrogen, R2 is alkyl- (C 1 -C 6) or cyclopropyl, R 3 is halogen, C 1 -C 4 alkyl, C 1 -C 3 alkyl is halogen, C 1 -C 4 alkoxy, phenoxy, phenyl a cyano group, n nu-lu, a number 1, 2, 3, 4, 5. 5. A fungicidal composition, herbicidal composition and / or plant growth agent for agriculture and horticulture comprising the geometric isomer of formula I wherein R1 is hydrogen, R2 &lt; 1 &gt; -methylcyclopropyl group, Rs atom-logen and zero, number 1 or 2. 6. A fungicidal composition, a herbicidal composition and / or a plant growth agent for agriculture and horticulture comprising the geometric isomer of formula (I) as the active ingredient, wherein R1 is an alkyl group of 1 to 4 carbon atoms, or an alkenyl group having 3 or 4 carbon atoms or 2-propinyl group, R 2 is tert-butyl group, R 3 is halogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms or nitro, n-ol, number 1 or 2. 7. A process for the preparation of a geometric isomer of formula (I) wherein R1, R2, R5a and n are as defined in claim 1, wherein one of the two geometric isomers of the triazole compound is reduced. of formula II 80 wherein R 2, R 3 and n are as defined above, wherein the olefin proton has a higher magnetic field on the NMR spectrum in deuterochloroform and when R 1 is C 1 -C 4 alkyl, the 3 or 4 alkenyl group carbon atoms or 2-propynyl groups, etherify the reduced product. 8. A process for the preparation of a geometric isomer of formula (I) wherein R1, R8, R3 and R are as defined in claim 2, wherein one of the two geometric isomers of the triazole compound of general formula (I) is reduced. of formula II wherein R 2, R 5 and n are as defined above, the olefin proton having a higher magnetic field on the NMR spectrum in deuterochloroform. 9. A process for the preparation of a geometric isomer of formula (I) wherein R1, R2, R3 and R3 are as defined in claim 3, wherein one of the two geometric isomers is reduced triazole compounds of formula (II) wherein R 2, R 3 and n are as defined above, the olefinic proton of which exhibits a higher magnetic field on the NMR spectrum of de-terochloroform. 10. A process for the preparation of a geometric isomer of formula (I) wherein R1, R2, R3 and (4) are as defined in claim 4, wherein one of the two geometric isomertriazole compounds of formula (II) is reduced. wherein R 2, R 3 and n are as defined above, the olefinic proton having a higher magnetic field on the NMR spectrum in deuterochloroform. 11. A process for the preparation of a geometric isomer of formula (I) wherein R1, R2, R5 and R are as defined in claim 5, wherein one of the two geometric triazole isomers of the general formula is reacted wherein II2, R5 and n are as defined above, the olefinic proton of which exhibits a higher magnetic field on the NMR spectrum in deuterochloroform. 12. A process for the preparation of a geometric isomer of formula (I) wherein R1, R2, R3 and R6 are as defined in claim 6, wherein one of the two geometric isomers of the triazole compound of formula (I) is reacted II, wherein R2, R5 and n are as defined above, the olefinic proton of which exhibits a higher magnetic field on the NMR spectrum in deuterochloroform, and the resulting reduced product is etherified.