FI95571B - Fungicidal azol compounds containing polysubstituted cyclohexanol structure - Google Patents

Description

α 95571

This invention relates to novel azole compounds having a polysubstituted cyclohexanol structure and to their use as fungicides.

A number of fungicides containing an imidazole or 1,2,4-triazole group are known. Typically, in addition to the azole group, they have a substituted phenyl group as a structural member. The aliphatic portion of the molecule is typically open-chain, but some alicyclic structures are also known. British application GB-2,153,355 describes compounds having the structure cyclohexanol and cyclohep-15, which are characterized in that the structure has an aryl group bonded to a hydroxyl carbon and that the azole group is in the 2-position.

EP-324 646 describes cyclohexanol and cyclo-20 heptanol structures having an azole group attached to a hydroxyl carbon via methylene and a 4-chlorobenzyl group in the 2-position. The cycloalkanol ring is otherwise unsubstituted and, in the case of cyclohexanol, contains 9 hydrogens.

According to the examples of EP-324 646, these structures, which are only slightly substituted in the cyclohexane ring, give good biological performance at a concentration of 100-500 ppm (0.01-0.05%). With the more substituted compounds of the invention in the cyclohexane ring according to the invention, good biological efficacy is typically achieved at one tenth of the above concentration.

U.S. Patent 4,684,396 describes cyclopentane and cyclohexane structures in which the azole group is attached to the ring via a single carbon and the linking carbon does not bind the hydroxyl group. U.S. Pat. No. 4,725,614, U.S. Pat. No. 4,547,214, U.S. Pat. No. 4,503,062, EP-125,409 and FI-87,774 also have ring structures which differ from those of the present invention. Patents 2 95571 tit GB-2 180 236, EP-294 222 and EP-267 778 describe cyclopentane structures.

It has now been found that the novel multisubstituted cyclohexanol-structured azole group-containing compounds of the general formula I 5 shown below are very fungicidally active.

R-7 .R8 10

4 Rf / COH ~ N-Z

is r 2 r, / y N 'wherein 20 of the groups R 1 -R 8 may be hydrogen, 1 of the groups R 1 R 8 may be alkyl of 1 to 4 carbon atoms, 2 of the groups R 1 -R 8 together may be methylene, 2 R 1 to R 3 may together be tetramethylene, R 1, R 2, R 3 and R 4 together with the carbon atoms to which they are attached may form a benzene ring optionally substituted by one halogen atom, or R 1 and R 2 may together form a benzylidene group substituted by one or two halogen atoms, R 9 is hydrogen and R10 is phenoxy substituted by one or two halogen atoms, or R9 and R10 together form a benzylidene group substituted by one trifluoromethyl group or one or two halogen atoms, a 2-phenyl group having a phenyl group or a furfurylidene group optionally substituted by one halogen atom, up to 4 ) an oxymethylene group having a phenyl group substituted with one or two ha and Z is N or CH, 3 95571 wherein up to 8 of the groups R 1 -R 9 are hydrogen, and provided that if R 9 and R 10 together form a substituted benzylidene group as defined above, the groups R 1 -R 9 form a methylene or R 1 group as defined above. a tetramethylene-5 group or a benzene ring, or R 1 and R 2 together form a substituted benzylidene group as defined above.

In the cyclohexanol structures of the general formula I, the side chain containing the azole group is attached to the alcohol carbon. Optical isomerism occurs in the compounds of formula 10 I unless the substitution happens to be completely symmetrical. Optical and other stereoisomers have different biological activities, as is known for many azole fungicides and growth regulators. Thus, the various isomers of formula I are equally within the scope of this invention.

Alkyl having 1 to 4 carbon atoms is preferably methyl.

Halogen is preferably fluorine, chlorine or bromine.

20

Compounds of formula I may be prepared by reacting an epoxy compound of formula II

R7 β-s 25 R6 R9 - ^ 10

II

7XV

3 0 R2 Rj

wherein RrR10 is as defined above, is reacted with a compound of formula III

35 / ΚΓΗ \ '40 or an alkali metal salt thereof.

4,95571

Compounds of formula I may also be prepared by reacting a cyclohexanone compound of formula IV

^ 7 Rg 5 R6 R9

X. 10 IV

R3 / \ TO

10 r2 r,

wherein R1-R10 are as defined above, is reacted with a compound of formula V

15

V

Wherein Y is a reactive group such as a silyl group or a magnesium halide (Grignard reagent).

25

The starting material of formula II can be prepared by reacting a cyclohexanone compound of formula IV with either trimethylsulfonium iodide followed by treatment with a strong base such as potassium tert-butoxide or di-methyl sulfide and dimethyl sulfate in the presence of a base.

The following reaction scheme shows synthetic routes for compounds of formula I wherein R 1 and R 10 t 35 together form a substituted benzylidene group (Formula Ia), and further modification of these compounds by epoxidation (Formula Via). 1; : * 11.4. bone 11 i il · 5 95571 *,, R, 1, h | V ^ 2 IVa

Method a) ν 'cis or trans

R P

.1 Method b)

O

Method c) ir

Rv .Rv f Method d) HO | lf //

N —V

Epoxidation 'r

Rx Ry φό

O

N - '

Via 6 95571

In the above scheme, Rx represents the substituents R 1 -R 9 of the cyclohexane ring as defined above and Ry represents the substituent or substituents of the phenyl ring as defined above.

5

An intermediate of formula IVa is prepared by reacting a cyclohexanone compound with a benzaldehyde compound in the presence of a base. Numerous analogous aldol condensation products containing a cyclohexanone structure can be prepared by similar methods mentioned in the literature.

Compounds of formula I which contain an oxygen substituent, i.e. epoxy derivatives, can be prepared from the corresponding double bond compounds by oxidizing the double bond or adding water thereto and further processing by conventional further reactions.

The invention is described in more detail below by means of exemplary embodiments 20. Preparations 1-4 describe the preparation of intermediates of formulas II and IV and Examples 1-2 describe the preparation of final products of formula I.

Preparation 1 25 Preparation of 2- (2,4-dichlorobenzylidene) -6,6-dimethylcyclohexanone

To a solution of 109 g (0.85 moles) of 2,2-dimethylcyclohexanone and 150 g (0.85 moles) of 2,4-dichlorobenzaldehyde in 210 ml of methanol are added with stirring 140 ml of 15% potassium hydroxide. The mixture is heated and stirred in a water bath for 2 hours, cooled and extracted with chloroform. The organic layer is washed with dilute hydrochloric acid and water, dried and the solvent is evaporated off under reduced pressure. After crystallization from iso-35 propanol, 131 g (51%) of 2- (2,4-dichlorobenzylidene) -6,6-dimethylcyclohexanone are obtained, m.p. 61-63 ° C. IR (petrolatum, cm-1): 1685, 1630 (C = O, C = C).

NMR (acetone-d 6, δ): 1.30 s (6H, 2 CH 3), 1.86-1.98 m (4H, 2795571 CH 3), 2.75-2.88 m (2H, CH 2), 7.31 m (1H, CH =), 7.4-7.7 m (3H,

Ar).

Preparation 2 In analogy to Preparation 1, 2- (4-chlorobenzyl'-ylidene) -6,6-dimethylcyclohexanone is obtained, yield 54%, m.p.

94-97 ° C. IR (petrolatum, cm-1): 1685, 1630 (C = O, C = C). NMR (acetone, δ): 1.11 s (6H, 2 CH 3), 1.7-1.8 m (4H, 2 CH 3), 2.78-2.85 m (2H, CH 2), 7.21 m (1H, CH =), 7.43 m (4H, Ar).

10

Preparation 3 Preparation of 1,1-oxamethylene-2- (2,4-dichlorobenzylidene) -6,6-dimethylcyclohexane Method a)

A mixture of 96 g (0.34 mol) of 2- (2,4-dichlorobenzylidene) -6,6-dimethylcyclohexanone, 97 g (0.48 mol) of trimethylsulfonium iodide and 210 ml of dimethyl sulfoxide is stirred for 15 min under a nitrogen atmosphere. 53.3 g of potassium tert-butylate (0.42 mol) in 210 ml of dimethyl sulfoxide are added over 1 hour. The mixture is cooled and 1 l of water is added over 30 minutes with cooling. After 30 minutes, the mixture is extracted with ether, the extract is washed with water, dried over magnesium sulphate and the solvent is evaporated. After crystallization from isooctane, 76 g (75%) of 1,1-oxamethylene-2- (2,4-dichlorobenzylidene) -6,6-dimethylcyclohexane are obtained, m.p.

63-65 ° C.

Method b) To a mixture of 58 g (0.205 moles) of 2- (2,4-dichlorobenzylidene) -6,6-dimethylcyclohexanone, 76 ml of dimethyl sulfide and 3.8 g (0.21 moles) of water are added 38 g of 38.6 g (0.62 mol) of dimethyl sulfate dropwise at 2 ° C over 2 hours. The mixture is kept for 2 hours at 38 [deg.] C., cooled to 25 [deg.] C. and 34.8 g (0.62 mol) of potassium hydroxide are added over 1 hour at such a rate that the temperature does not exceed 38 [deg.] C. The reaction mixture is stirred for 10 hours while the dimethyl sulfide evaporates and then 95571

O

160 ml of water, and the organic layer is separated. The aqueous phase is extracted with ether, the combined organic phases are washed with water and dried over magnesium sulphate and the solvent is evaporated off under reduced pressure. Crystallization from isooctane gives 42 g of 5 (70%) 1,1-oxamethyl-2- (2,4-dichlorobenzylidene) -6,6-dimethylcyclohexane, m.p. 63-65 ° C. IR (petrolatum, cm-1): 1580 (C = C), 850 (epoxy). NMR (CDCl 3, δ): 1.0 S (3H, CH 3), 1.07 s (3H, CH 3), 1.5-1.7 m (4H, 2 CH 2), 2.2-2.8 m (2H , CH 2), 2.7 d, J = 6 Hz (1H, CH), 3.1 d, J = 6 Hz (1H, CH), 6.53 m (1H, 10 CH =), 7.1-7, 5 m (3H, Ar).

Preparation 4

In analogy to Preparation 3, 1,1-oxamethylene-2- (4-chlorobenzylidene) -6,6-dimethylcyclohexane is obtained in a yield of 81% (method a), m.p. 65-67 ° C. IR (petrolatum, cm -1): 1580 (C = C), 845 (epoxy). NMR (acetone-d 6, δ): 0.85 s (3H, CH 3), 1.57-1.70 m (4H, 2 CH 2), 2.1-2.8 m (2H, CH 2), 2, 44 d, J = 6 Hz (1H, CH), 2.99 d, J = 6 Hz (1H, CH), 6.44 m (1H, CH =), 7.2-7.4 m (Ar) .

20

Analogous epoxy compounds can also be prepared by known methods, for example from the corresponding double bond compounds.

25 Reference Example 1

Reference compound 1: 2- (2,4-dichlorobenzylidene) -1- (1- (1,2,4-triazolyl) methyl) -6,6-dimethylcyclohexanol

Method c) A mixture of 32 g (77 mmol) of 1,1-oxamethylene-2- (2,4-dichlorobenzylidene) -6,6-dimethylcyclohexane, 5.35 g (77.4 mmol) 1.2, 4-Triazole, 33 ml of N-methylpyrrolidone, 1.03 g (25.7 mmol) of sodium hydroxide and 0.5 ml of water are kept at 120 ° C for 4 hours. The mass is concentrated under reduced pressure and the residue is dissolved in methylene chloride, washed neutral with water, dried over magnesium sulfate and evaporated. After crystallization from alcohol, 16 g of <9,95571 (58%) of 2- (2,4-dichlorobenzylidene) -1- (1- (1,2,4-triazolyl) methyl) -6,6-dimethylcyclohexanol are obtained, m.p. 189-190 ° C.

Method d) A mixture of 40 g (0.14 moles) of 2- (2,4-dichlorobenzylidene) -6,6-dimethylcyclohexanone, 43.4 g (0.28 moles) of 1- (1,2,4 moles). -triazolylmethyl) silane and 200 ml of tetrahydrofuran, cooled to 0 ° C and 28 ml of 1 M aqueous tetrabutylammonium fluoride solution are added. The mass is kept for 12 to 10 hours at room temperature and then water and solvent are distilled off and the mixture is heated briefly under reduced pressure. After crystallization from alcohol, 9 g (18%) of 2- (2,4-dichlorobenzylidene) -1- (1- (1,2,4-triazolyl) methyl) -6,6-dimethylcyclohexanol are obtained, m.p. 189-190 ° C. NMR (acetone-d 6, δ): 1.05 S (3H, CH 3), 1.19 S (3H, CH 3), 1.5-1.9 m (4H, 2 CH 2), 2.2-2 , 5 m (2H, CH 2), 2.84 s (1H, OH), 4.41 d, J = 15 Hz (1H, CH), 5.1 d, J = 15 Hz (1H, CH), 6 , 35 m (1H, CH =), 7.25-7.42 m (3H, Ar), 7.85 S (1H, CH = N), 8.35 S (1H, CH = N).

20 Example 1

In analogy to Reference Example 1, the following compounds can be prepared. The imidazole compounds are prepared by replacing the triazole with an equivalent amount of imidazole. Many substances exhibit cis-trans isomerism and contain asymmetric carbon of 25 meters. Isomer ratios have also been observed to change with prolonged exposure to substances. The melting point and crystallinity of the substances depend on the isomer ratios.

Reference compound 2 is mentioned in Example IX of Example IX of FI patent application 896315 30 (corresponding to EP-378 953).

Reference compound 2: 2- (4-chlorobenzylidene) -1- (1- (1,2,4-triazolyl) methyl) -6,6-dimethylcyclohexanol, yield 62% (method c), m.p. 183-184 ° C.

35

Compound 1: 2- (4-chlorobenzylidene) -1- (1- (1,2,4-triazolyl) methyl) -6,6-tetramethylenecyclohexanol, m.p. 214-: 215 ° C.

10 95571

Compound 2: 2- (2,4-dichlorobenzylidene) -1- (1- (1,2,4-triazolyl) methyl) -6,6-tetramethylenecyclohexanol, m.p. 203-2 04 ° C.

Compound 3: 2- (2,4-dichlorobenzylidene) -1- (1-imidazolylmethyl) -6,6-tetramethylenecyclohexanol, m.p. 212-213 ° C (isomer mixture 3: 1).

Compound 4: 2- (4-chlorobenzylidene) -1- (1- (1,2,4-triazolyl-10-yl) methyl) -6-methyl-5,6-tetramethylene-cyclohexanol, m.p. 207-208 ° C (cis: trans = 64:36).

Compound 5: 2- (2,4-dichlorobenzylidene) -1- (1- (1,2,4-triazolyl) methyl) -6-methyl-5,6-tetramethylene-cyclohex-15-ol.

Compound 6: 2- (4-chlorobenzylidene) -1- (1- (1,2,4-triazolyl) methyl) -4,4,6,6-tetramethyl-3,5-methylene-cyclohexanol.

20

Compound 7: 2- (2,4-dichlorobenzylidene) -1- (1- (1,2,4-triazolyl) methyl) -4,4,6,6-tetramethyl-3,5-methylene cyclo- hexanol.

Compound 8: 2,6-bis- (4-chlorobenzylidene) -1- (1- (1,2,4-triazolyl) methyl) cyclohexanol.

Compound 9: 2,6-bis- (2,4-dichlorobenzylidene) -1- (1- (1,2,4-triazolyl) methyl) cyclohexanol.

30

Compound 10: 2- (4-chlorophenoxy) -1- (1- (1,2,4-triazolyl) methyl) -6-methylcyclohexanol, m.p. 165-166 ° C.

Compound 11: 2- (2,4-dichlorophenoxy) -1- (1- (1,2,4-triazolyl-35-yl) methyl) -6-methylcyclohexanol, m.p. 170-171 ° C.

Compound 12: 2- (4-chlorophenoxy) -1- (1- (1,2,4-triazolyl) methyl) -4,4,6,6-tetramethyl-3,5-methylene-cyclohexanol.

and 95571

Compound 13: 2- (2,4-Dichlorophenoxy) -1- (1- (1,2,4-triazolyl) methyl) -4,4,6,6-tetramethyl-3,5-methylene-cyclohexane noli.

Compound 14: 2- (5-chloro-2-thienylmethylidene) -1- (1- (1,2,4-triazolyl) methyl) -6,6-dimethyl-cyclohexanol, m.p.

126-127 ° C.

Compound 15: 2- (2-furfurylidene) -1- (1- (1,2,4-triazolyl) -10 methyl) -6,6-dimethylcyclohexanol.

Compound 16: 2- (4-chlorobenzylidene) -1- (1- (1,2,4-triazolyl) methyl) -5-benzocyclohexanol, m.p. 208.5-209.5 ° C (i-PrOH), 231-233 ° C (acetone).

15

Compound 17: 2- (2,4-dichlorobenzylidene) -1- (1- (1,2,4-triazolyl) methyl) -5-benzocyclohexanol, m.p. 198.5 to 199.5 ° C

(benzene).

Compound 18: 2- (4-chlorophenoxy) -1- (1- (1,2,4-triazolyl) methyl) -5-benzocyclohexanol.

Compound 19: 2- (2,4-dichlorophenoxy) -1- (1- (1,2,4-triazolyl-1 H) methyl) -5-benzocyclohexanol.

25

Compound 20: 2-Isobutylidene-1- (1- (1,2,4-triazolyl) methyl) -5-benzocyclohexanol.

Compound 21: 2,6-bis- (4-bromobenzylidene) -1- (1- (1,2,4-tri-azolyl) methyl) -cyclohexanol, m.p. 174-175 ° C.

Compound 22: 1-hydroxy-2- (4-chlorobenzylidene) -1- (1- (1,2,4-triazolyl) methyl) -1,2,3,4-tetrahydro-5-chloronaphthalene, m.p. 197-199 ° C.

Compound 23: 2- (4-chlorobenzylidene) -1- (1- (1,2,4-triazolyl) methyl) -5,6-tetramethylenecyclohexanol, m.p. 197-198 ° C (i-PrOH).

35 12 95571

Compound 24: 2- (4-trifluoromethylbenzylidene) -1- (1- (1,2,4-triazolyl) methyl) -5,6-tetramethylenecyclohexanol, m.p.

215-217 ° C.

Compound 25: 2- (4-trifluoromethylbenzylidene) -1- (1- (1,2,4-triazolyl) methyl) -6-methyl-5,6-tetramethylenecyclohexanol, m.p. 227-230 ° C (cis: trans = 95: 5).

Compound 26: 2- (4-fluorobenzylidene) -1- (1- (1,2,4-triazol-10-yl) methyl) -6-methyl-5,6-tetramethylenecyclohexanol, m.p. 208-209 ° C.

Example 2

Compound 27: 2,2- (1 ', 2' - (2 '- (4-chlorophenyl)) oxymethylene) -15- (1- (1,2,4-triazolyl) methyl) -6,6-dimethylcyclohexane - noli

Reference compound 2 (1 g) is dissolved in methylene chloride (ca. 15 ml) and formic acid (1 ml) and 30% hydrogen peroxide (2 ml) are added. The mixture is stirred overnight, the phases are separated and the solvent is evaporated. Crystallization from ethanol gives compound 36, m.p. 158-161 ° C.

Other known methods can also be used. Such a classical method for preparing alcohols from ketones is; The use of Grignard-type compounds, which in this case would be, for example, azolylmethylmagnesium chloride.

Funcricidal activity The fungicidal activity of the substances according to the invention in comparison with the known substances in use, triadimenol and triadimefon, is described in the following Experimental Examples 1-6. The experimental setup is shown in Reference Experimental Example 1.

35 Reference Test Example 1

Fungicidal activity was measured on pure fungal cultures. The experiments were performed on potato agar medium to which dissolved test substance was added to a concentration of 0.001% active ingredient. After 17-20 μl 1 m »lit 1» 13 95571 hours, the fungal mycelium was inoculated onto an agar plate. On the third day, the diameter of the fungal growth was measured and the percentage of mycelium growth inhibition was calculated according to Ebbot's formula: 5

A - B

K = - * 100%

A

10 K = percentage inhibition of mycelium growth A = diameter of the fungal growth in the untreated test B = diameter of the fungal mycelium in the test substance-treated test.

15 The experiment was performed on 16 test subjects: Fusarium nivale (Fn), Fusarium graminearum (Fg), Fusarium moniliforme (Fm), Fusarium culmorum (Fc), Fusarium oxysporum (Fo) f Fusarium sambucinum (Fs), Botrytis cinerea (Bc), Sclerotinia sclerotiorum (Ss), Venturia inaequalis (Vi), Helmintho-20 sporium sativum (Hs), Pyricularia oryzae (Po), Cladosporium Herbarum (Cl.h.), Aspergillus flavus (Af), Aspergillus niger (An), Penicillium sp. (P.sp.), Rhizoctonia solani (Rh.s.).

25 The results are shown in Table 1.

table 1

Inhibition of fungal mycelium growth%

Test subject Reference compound 1 Reference compound 2 Triadimenol 30 F.n. 82 100 72 F.g. 28 100. 56 F.m. 91 100 82 F.C. 83 100 35 35 F.o. 79 93 63 F.s. 78 96 88 B.C. 100 100 100 S.s. 100 100 78 V.i. 55 82 51 40 H.s. 92 95 93 P.o. 100 100 100

Cl.h. 24 81 61 A.f. 47 100 28 A.n. 81 100 45 45 P.sp. 84 92 39

Rh.s. 98 100 38 95571 14

Experimental Example 1

The activity of the compounds of the invention against wheat brown rust at four different application rates is compared below. For comparison, the widely used long-acting fungicide triadimefon has been taken. The results are shown in the following table. (In the untreated sample, the contamination percentage was 69.1.)

Disease inhibition percentage 10 Compound no: application concentration% 0.02 0.01 0.005 0.0025 1 98.4 92.3 84.3 69.8 2 88.5 87.6 82.6 79.4 15 3 96.4 95.3 88.1 79 , 7

Triadimefon 99.8 96.6 91.4 81.3

Experimental Example 2 The following describes the efficacy of the substances according to the invention against sore throat at three different application concentrations. Percent disease inhibition is measured at 10 and 15 days after treatment. The reference substance is triadimefon. (The contamination rate of the untreated test member was 82.9 after 10 days and 87.5 after 15 to 25 days.)

Disease prevention percentage Use concentration% 0.005 0.0025 0.0012 30 Days 10 / 15_10 / 15_10 / 15

Compound No: 1 66.8 / 46.5 57.7 / 42.8 54.0 / 38.0 2 90.1 / 88.0 71.0 / 70.0 54.7 / 50.0 35 3 66 , 8 / 53.0 55.0 / 42.0 49.0 / 38.0

Triadimefon 93.9 / 86.8 87.3 / 80.0 78.8 / 73.7

Experimental Example 3 40 The following describes the efficacy of the compounds of the invention against five fungal diseases at a concentration of 15 ppm. The abbreviations are the same as in Reference Experimental Example 1. The numbers are percent growth inhibition compared to the control experiment.

Compound no: S.s. F. G. Rh.s. H. S. V.I.

15 95.571 1 77 77 75 100 75 2 64 66 93 75 41 5 3 55 57 60 69 50 10 17 20 0 20 17 11 52 30 0 37 31 14 100 100 93 87 78 16 100 100 65 100 86 10 17 64 69 40 78 48 21 40 56 40 32 34

Triadimefon 76 66 30 37 41

Test methods for pickling agents for the control of wheat and rice roots and patches

The products are tested by the humid chamber method using paper rolls. The principle of the method is that the seeds are germinated under both optimal conditions for germination and for the growth and development of pathogens inside or on the outer surface of the seeds.

Naturally contaminated (30-60%) wheat and rice and artificially fungal growths of 10-14 days old in Helminthosporium oryzae, Bipolaris sorokiniana and

Fusarium oxysporum-contaminated seeds are wet-covered with test products; 1 g / 1 kg of seeds as active substance and 2 g / 1 kg of seeds as preparation.

30

To germinate the seeds, take two-layer strips of 25 x 100 cm filter paper. The paper strips are soaked in distilled water. The pickled seeds are placed at a distance of 6-8 cm from the top of the sheet of paper at intervals of 1-1.5 cm 35 embryos downwards (with wheat). To facilitate the detection of sprouts, the seeds are covered with moistened tissue paper, (lev.

8-10 cm, pit. 100 cm). The strip of filter paper on which the seeds are • placed is rolled up and placed in a closed container with water. The rolls are immersed in water at a depth of 2-3 40 cm at the bottom for wheat and deeper for rice. The rollers are kept in light at room temperature. After 8-10 days, the germination of the seeds is determined and the contamination with Helminthosporium, Fusarium and surface mold is calculated.

Seed contamination is defined in%. The effect of the products on the development of sprouts, shoots and roots is monitored.

For comparison, an unpainted sample is taken.

At the same time, the effect of the test products 10 on the sowing properties of the seeds is determined in the experiment.

Experimental Example 4

The following compares the fungicidal activity of some of the tetrain and decalin derivatives according to the invention with pathogens causing root rot, cob or leaf diseases in cereals and rice (in vitro). The monocyclo structure and the compound in use are compared. Figures are percent disease inhibition at a concentration of 15 ppm. The abbreviations are the same as in Reference Experimental Example 1 and in addition Scleroti-20 nia graminearum (S.g.), Bipolaris sorokiniana (B.s.) and Helminthosporium oryzae (H.o.).

Compound F.n. F. G. S.g. B.s. Rh.s. B.C. V.I. Po H.O. F.o.

25 4 100 100 100 100 98 100 100 100 100 90 16 100 100 100 100 95 100 100 100 100 90 17 63 66 90 78 88 78 63 90 80 70 22 100 90 100 100 95 100 90 100 100 90 23 96 100 100 96 100 100 100 100 100 100 30 24 98 100 100 98 100 90 98 100 100 90 25 90 100 100 99 100 100 95 100 100 100 100 100 100 95 100 100 100 100 100 100 95 100 90 90 100 100 95 Reference Compound 2 100 100 100 100 95 100 100 100 100 90 Triadi- menol 100 56 80 93 40 100 50 50 100 63

Experimental Example 5 40 The following compares the efficacy of the bicyclo compounds of the previous experimental example in an in vivo experiment with the pathogens causing wheat mildew and rust Erysiphe graminis il 'fcttrl IIIi: tel »·> 2 17 95571 (E.g.) and Puccinia triticina (P.t.). The table shows the percentage inhibition of the disease at a concentration of 500 ppm.

Compound E.g. P.t.

54 99 97 16 100 100 17 90 96 22 90 93 23 100 100 10 24 100 90 25 100 97 26 100 93

Reference compound 2 90 89 15 Triadimefon 98.5 93 Control 62.5 20 (% disease development) 20 Experimental Example 6

The following table compares bicyclo compounds as rice seed dressings, as in the previous examples. The application rate is 0.3 kg of substance per tonne of seed.

25 Fusarium oxysporum Helminthosporium oryzae

Compound germination% damage% germination% damage% 4 80 23 85 18 16 84 12 82 10 30 17 80 30 80 20 22 82 20 80 19 23 80 26 85 15 24 84 21 80 20 25 83 20 82 23 35 26 84 20 82 18 reference compound 2 80 26 85 15

Baitan universal 80 24 86 25 40 control (without seed treatment with substances) 70 51 75 55

Claims (5)

5 R7 Rg vs * - R4 — Λν. Λ 1 Wherein R 1 -R 8 may be hydrogen, 1-4 of R 1 -R 8 may be alkyl of 1 to 4 carbon atoms, 2 of R 1 -R 8 together may be be methylene, 2 of R 1 -R 3 together may be tetramethylene, R1f R2, R3 and R4 together with the carbon atoms to which they are attached may form a benzene ring optionally substituted by one halogen atom, or R1 and R2 may together form a benzylidene group substituted by one or two halogen atoms, R9 is hydrogen and R10 is phenoxy substituted by one or two halogen atoms, or R9 and R10 together form a benzylidene group substituted by one trifluoromethyl group or one or two halogen atoms, optionally a thienylmethylidene or furienyl group substituted by one halogen atom, an alkylidene group or a 1,2- (2-phenyl) oxymethylene group having a phenyl group substituted by one or two halogen atoms, and Z is N or CH, up to 8 of the groups R 1, R 1, are hydrogen, and provided that if R 9 and R 10 together form a substituted benzylidene group as defined above, then the groups R 1 -R 8 form a methylene or tetramethylene group or a benzene ring as defined above, or R 10 and R 2 together form a substituted benzylidene group as defined above. R iH · Rilli I t t M i <19 95571 Azole compound according to Claim 1, characterized in that it is 2- (4-chlorobenzylidene) -1- (1- (1,2,4-triazolyl) methyl) -5-benzocyclohexanol. Azole compound according to Claim 1, characterized in that it is 2- (4-chlorobenzylidene) -1- (1- (1,2,4-triazolyl) methyl) -6-methyl-5,6-tetramethylenecyclohexanol. Azole compound according to Claim 1, characterized in that it is 2- (4-chlorobenzylidene) -1- (1- (1,2,4-triazolyl) methyl) -5,6-tetramethylenecyclohexanol. Use of an azole compound according to any one of the preceding claims as a fungicide. 15