FI100797B - Intermediates for use in the preparation of (benzylidene) -azolylmethylcycloalkanes or alkenes - Google Patents

Description

100797 Intermediates for the preparation of (benzylidene) -azolylmethylcycloalkanes or alkenes - Mellanprodukter för användning i framställning av (benzyliden) -azolylmethylcycloalkaner eller -alkaner 5 This application is divided by application 896315.

The present invention relates to novel plant protection compounds having 10 (benzylidene) -azolylmethylcycloalkane or cycloalkene groups. It also applies to processes for the preparation of said compounds and to substances which may be used as intermediates in the processes of preparation. It also relates to the use of these compounds as fungicides, to fungicidal compositions based on these compounds and to methods for controlling fungal diseases in cultures using these compounds. It also relates to a crop propagation product which has been treated with a compound of the invention.

Several substances containing triazole groups are already known, in particular fingering bonds. In particular, EP-151,084, 246,982, 121,979, 89,100 disclose triazole fungicides having a tetrahydrofuran ring. Triazole fungicides with a cyclopentane ring are known from patent applications EP-272 895, 267 778, DE-3 630 840 and BE-867 245. Triazole fungicides having a cycloalkane group are known from patent application EP-324 646 and U.S. Pat. No. 4,684,396. U.S. Pat. No. 4,160,838 discloses triazole fungicides having a dioxolane ring.

'25. · 1 ·. In view of the prior art, it is an object of the present invention:. is to propose other broad-spectrum fimgicide compounds which * 1 1 can be used specifically for the treatment of plant root diseases such as root rot or leaf diseases such as frostbite, septoriosis, pyriculosis, fusariosis, rhinosporiosis, which are pathogenic. diseases caused by fungi such as Botrytis, Phoma and Aschochyta, • · · ·· [1 in various crops such as cereals, vine, * .1 1 rice, maize and soybeans.

t · • · • I «2 100797 These compounds are known to correspond to formulas IA or IB: r \ 10 / /

Rl ° 3 «12 Rl 15 RW \ £ ^ X> n '! Ϋ [^' X '“ V A __ / L R3 V AiJ — R3 \ r4 20

IA IB

wherein A is -CR6R7- or -CRgRyCRgRg- or -CRgRyCRgRgCR ^ O ^ 11- / A ^ On -CRy =, -CRgRy-CRg = or -CRgRy-CRgRg-CRjj =, i.e. the cycloalkane may be cyclopentane or cyclohexane or cycloheptane or cyclopentene, cyclohexene or cycloheptene,

X is a halogen atom, preferably fluorine, bromine, chlorine or a cyano or nitro group, or a group C 1 -C 4 alkyl or C 1 -C 4 alkoxy optionally halogenated, n is a positive integer or 0, less than 6, and the groups X

; ***; can be identical or different when n is • · ·:, ··. greater than 1, .-, 35 W represents a trivalent group consisting of either the group • · · «CH- or the nitrogen atom -N-,„. R 1 and R 2, which may be identical or different, represent a hydrogen atom or a group C 1 -C 4 alkyl which may be

• I

V · optionally substituted (as substituent e.g. one or more atoms or groups such as halogen atoms, C 1 -C 4 alkoxy, mono- or polyhalo (C 1 -C 4 alkoxy), C 3 -C 4 alkenyl, C 2 -C 4 alkynyl) , mono- or polyhalo (C 2 -C 4 alkenyl), mono- or polyhalo (C 2 -C 4 alkynyl)), C 1 -C 4 alkoxy, which may optionally have a substituent (e.g. one or more atoms) or groups such as halogen atoms, C 1 -C 4 alkoxy, mono- or polyhalo (C 1 -C 4 alkoxy), C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, mono- or polyhalo (C 2 -C 4 alkenyl) and mono- or polyha-5-logene (C2-C4-alkynyl)), or C3-C7-cycloalkyl, C6-C10-aryl. (especially phenyl), CyCn-aralkyl (especially benzyl), and these various groups may be optionally substituted as a substituent e.g. one or more atoms or groups such as halogen atoms, C1-C4-10 alkyl, mono- or polyhalogen (C1- C 4 -C 4 alkyl), C 1 -C 4 alkoxy and mono- or polyhalo (C 1 -C 4 alkoxy)) and and R 2 may together form a C 2 -C 5 hydrocarbon chain which forms a ring with the carbon atom to which R 1 and R 2 and this ring may be optionally substituted, such as C 8 -C 10 aryl groups as mentioned above, or R 1 and R 2 together may form a C 2 -C 5 dioxolane hydrocarbon chain with the carbon to which R 1 and R 2 are attached and this the chain may be optionally substituted, such as the aforementioned R 9 -C 10 aryl groups / R 3 and R 6 'R 11' J0-tlca may be identical or different, represent a hydrogen atom or a group C 1 -C 4 alkyl optionally substituted (e.g. one ta i more atoms or groups, such as halogen atoms or groups C1-C4-alkoxy, mono- or polyhalogen (C1-C4-alkoxy-25 si)), groups C3-C7-cycloalkyl, Οβ-Οιο- & ΙΎΥϋ (specifically phenyl), C7 -C 1-4 aralkyl (specifically benzyl), and these various groups may be optionally substituted (substituent). as a support, for example, one or more atoms or groups, such as · * · »·. ·; . halogen atoms, C1-C4-alkyl, mono- or polyhalo-gene (C1-C4-alkyl), C1-C4-alkoxy and mono- or polyhalo-

. . gene (C 1 -C 4 alkoxy)) or alternatively two chains of A

r. · The adjacent group together with the atoms of A to which they are attached form a phenyl ring fused to a cycloalkane, "35 R 5 represents a hydrogen atom, an optionally substituted group C 1 -C 4 alkyl (as a substituent e.g. one or more atoms or groups such as halogen atoms, C1-C4-alkoxy, mono- or polyhalo (C1-C4-alkoxy), C2-C4-4 100797 alkenyl, C2-C4-alkynyl, mono- or polyhalo (C2-C4-alkenyl) , mono- or polyhalogen (C 2 -C 4 alkynyl)), or C 3 -C 7 cycloalkyl, C 8 -C 7 aryl (specifically phenyl), C 7 -C 11 aralkyl (specifically benzyl), and these various the groups may be optionally substituted (for example, one or more atoms or groups such as halogen atoms, C1-C4-alkyl, mono- or polyhalo (C1-C4-alkyl), C1-C4-alkoxy and mono- or polyhalogen (C 1 -C 4 alkoxy)) or R 5 represents a group C (= O) -10 r 13 'wherein R 13 represents a group C 1 -C 4 alkyl optionally s substituted (as a substituent e.g. one or more atoms or groups such as halogen atoms, C 1 -C 4 alkoxy, mono- or polyhalo (C 1 -C 4 alkoxy), C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, mono- or polyhalo) (C2-C4-15 alkenyl), and mono- or polyhalogen (C2-C4-alkynyl)), C3-C7-cycloalkyl, C8-C18-aryl (specifically phenyl), C7-Cn-aralkyl ( specifically benzyl), and these various groups may be optionally substituted (for example, one or more atoms or groups such as halogen atoms, C 1 -C 4 alkyl, mono- or polyhalo (C 1 -C 4 alkyl), C 1 -C 4 alkoxy and mono- or polyhalo (C1-C4-alkoxy)), C2-C4-ethynyl, C2-C4-acetynyl, mono- or polyhalo (C2-C4-ethynyl), mono- or • "· * polyhalogen (C2-C4-acetynyl), '..25 Railia has one of the meanings given by Rg except C («O) -Ri3, ***** R4 represents a hydrogen atom, a halogen atom, especially chlorine • ·»! , or bromine, a group C 1 -C 4 alkyl, which is optionally ¥ * * · ·. (substituted (as a substituent e.g. one or more atoms-30 and or groups such as halogen atoms, groups C1-C4-alkoxy,.. mono- or polyhalo (C1-C4-alkoxy), C2-C4-alkenyl, * ·· C2 -C4-alkynyl, mono- or polyhalogen (C2-C4-alkenyl), V * mono- or polyhalo (C2-C4-alkynyl)), groups C3-C7-cycloalkyl, C8-C18-aryl (specifically phenyl), ¢ 7-O-C 'aralkyl (specifically benzyl), and these various groups may be optionally substituted (as a substituent e.g.

* * one or more atoms or groups, such as halogen atoms, • · · * * * and, groups C1-C4-alkyl, groups mono- or polyhalo (C3-500797 C4-alkyl), groups C1-C4-alkoxy and groups mono- or poly-halogen (C1-C4-alkoxy)).

The invention also relates to salt-5 forms of the compounds of the invention. The compounds in the form of salts are suitable for use in agriculture and may be mentioned: hydrochloride, sulphate, oxalate, nitrate or aryl sulphonate as well as addition complexes of these compounds with metal salts, especially iron, chromium, copper, manganese, zinc, cobalt, tin, magnesium and aluminum salts.

For example, complexes with zinc are obtained by reacting a compound of formula 1 with zinc chloride. 15

In the present text, where no further definition is given, it is meant that the groups in question may be branched or straight-chain. The term "optionally halogenated" means optionally mono-20 or polyhalogenated.

In formula IA or IB, the symbol:: ^ r12 or H: / .: 25 - ^ - <x> n • · ·:. ·. that the stereochemistry of the double bond may be without difference E or • · · • · · · Z or a mixture of the two. Given the etheric stresses, there will be more of that form where R12. is in the E position with respect to i and re. The E-part is practically * ". * The only form obtained when Rio is H.

«4 (• · ·

The compounds of formula I and the compounds which may be used as intermediates in the preparation processes and which will be defined in connection with these processes may exist in one or more isomeric forms depending on the number of asymmetric centers of the molecule 6 100797. Thus, the invention also relates to all these optical isomers as well as to their racemic mixtures and corresponding diastereoisomers. Separation of diastereoisomers and / or optical isomers can be carried out according to methods known in the art.

With a view to use as a fungicide, it has been found that the invention preferably relates to those compounds of the formula IA or IB in which n 1, 2 or 3 and X are preferably a halo-10 gene selected from chlorine, bromine or fluorine.

It has also been found that it is more preferable to use those compounds of formula IA or IB in which n = 1 or 2 and X is a halogen atom in the para position when n = 1 and in the meta-para position or in the ortho-para position when when n = 2, preferably n = 1 and X is in the para position.

X is very preferably a chlorine atom.

In view of the limitations defined above, it has been found, either individually or in combination, that it is preferable to use those compounds of the formula I in which W is -N = because of their fungicidal properties.

• · ''25 In view of the limitations defined above, either individually or in combination, or in spite of them, it has been found that it is preferable to use them due to their fungicidal properties: compounds of the formula IA or IB in which Ro, Rg, Ro and : T: R10 represents a hydrogen atom and preferably R4, Ry, R8 and 30 represent a hydrogen atom or a group C1-C4-alkyl.

O · »« '· *! .. Subject to the limitations defined above, either one tel- *. It has been found that, together with or in spite of, fungicidal properties, it is preferred to use compounds of formula IA or IB in which R1 and R2 are selected from methyl, ethyl or hydrogen.

7 100797

In view of the limitations defined above, either individually or in combination, or in spite of them, it has been found that it is preferable to use compounds in which R5 is a hydrogen atom or C1-C4-alkyl, very preferably R5j is a hydrogen atom, due to their fungicidal properties.

In view of the limitations defined above, either individually or in combination, or in spite of them, it has been found that, due to their fungicidal properties, it is preferable to use compounds in which R 2 is a hydrogen atom.

In view of the limitations defined above, either individually or in combination, or in spite of them, it has been found that, due to their fungicidal properties, it is preferable to use those compounds of the formula IA in which A is CR5R7 or CR5R7 CRgR8.

Due to their effect on the foliage (primarily antibotrytis effect) and / or their non-phytotoxicity, so that they can be used for the treatment of grains, those triazoles of the formula IA are used in which A is CR5R7 and R1 and R2 are selected from the group consisting of methyl and ethyl, R3, R5-R7 and R12 represent a hydrogen atom, R4 is methyl, ethyl, n-propyl, i-propyl or a hydrogen atom, or A is CRgRyCRgRg, * R1 and R2 are selected from methyl, ethyl or hydrogen, • · R3, R5-R9 and R12 represent a hydrogen atom, R4 is methyl, ethyl, n-propyl, i-propyl or a hydrogen atom.

«· • · e • t» • · · ·

The following compounds are considered preferred:. # 2- (4-chlorobenzylidene) -5-methyl-5-ethyl-1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclopentanol, 2- [4- chlorobenzylidene) -5,5-dimethyl-1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclopentanol, 35 2- (4-chlorobenzylidene) -6-methyl-1- (1H -1,2,4-Triazol-1-ylmethyl) -1-cyclohexanol, 2- (4-chlorobenzylidene) -6,6-dimethyl-1- (1H-1,2,4-triazol-1-ylmethyl) ) -1-cyclohexanol, δ 100797 2- (4-chlorobenzylidene) -1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclohexanol.

The present invention also relates to processes for the preparation of the compounds of the invention.

In the following description, the substituents shown below have the same meaning as indicated above, unless otherwise stated.

A. A Case of Compounds of Formula IA In this method, an omega-alkenoic acid chloride of the formula R 3, R 2, R 2, R 3, R 3, wherein R 1, R 3 cannot represent a group C 1 -C 4 alkyl having one or more several groups C2-C4-alkenyl, C2-C4-alkynyl, mono- or polyhalo (C2-C4-alkenyl), mono- or polyhalogen (C2-C4-alkynyl) or a group C1-C4-· .. alkoxy, react with aluminum chloride in an inert solvent such as dichloromethane or carbon disulfide or nitromethane as described in. in addition, K.R. Kopecky et al., Can. J. Chem. 59, 3273. ** ’. 30 (1981) and W.C. Agosta et al., J. Am. Soc. 9j3, 5513 (1971), • «"!. * So as to obtain a mixture of cycloalkanone and cycloalkenone having the formula

O O

.35 I I

= · ·!; ^ A — Λ VA1iH ^ —R3 40 R3 Ce

III IV

9 100797

In the compound of formula IV, A 2 H corresponds to the groups -CR 7 H or -CR 8 R y -CR 9 H or -CR 9 R y -CR 9 R 9 -CR 2 H and is thus only obtained when A is A 1 H.

In the case where it is desired to obtain a compound of formula V wherein R 4 is a hydrogen atom, the compound of formula III is first subjected to catalytic hydrogenation to give the compound:

10 O

Rl ^^ \

r2 ^ T

15 V ^ ArR3 v A \ R4

In the case where it is desired to obtain a compound of formula V as above, wherein R 4 is other than a halogen atom or a hydrogen atom, a magnesium derivative of formula R 4 M (M - MgHal) is obtained, which is obtained in a known manner by e.g. reacting the compound with magnesium in the presence of an ether, reacting with a cycloalkenone of formula 25 in the presence of a catalytic amount of copper iodide at low temperature in a polar solvent in a known manner.

Water is then added to the mixture to isolate the compound of formula V.

Γ50 • · *:, * The cycloalkanone of formula V thus obtained, having the reminder- # # · ·. forge yet, and R2 have the same meaning as in the general formula with the exception that they cannot mean. . C1-C4-alkyl substituted with one or more C2-C4-alkenyl, C2-C4-alkynyl, mono- • · * ·] * or polyhalogen (C2-C4-alkenyl), mono- or polyhalo- (C2-C4-alkynyl) or a group C1-C4-alkoxy, R4 is the same as in the general formula except that it cannot be a halogen atom, R3, Rg, Ry have the same meaning as in the general formula, 40 are well to a known aldolisation / crotonization reaction by condensation with benzaldehyde of the formula

\ _ / (X) n VI

to give compounds of formula VII in which R13 is a hydrogen atom:

15 R ^ (Vj ^^ ix) n VII

r3 20

To obtain a compound of formula VII in which r12 is other than a hydrogen atom, a silyl ether of formula XI is administered: 25 OSiOe3

RlX ^ i r2 | /..30 l

A "\ ^ R4 XI

··· N

R3; / 35 • · 4 * to react with a ketal of formula XII: • · · <x> n / - \ / OR16 "Τ '©) -« i' • / o \ _ / ^ ~ R7 where R ^ g is C 1 -C 4 alkyl, by premixing a ketal of formula XII with titanium tetrachloride in a halogenated solvent such as dichloromethane at about 0 ° C and then adding 11,100797 silyl ethers of formula XI at about 0 ° C, followed by hydrolysis With HCl as described by T. Nukaiyana et al., J. Am. Chem. Soc. 1974, 96, 7503.

To obtain a compound of formula VII wherein R 1 is alkyl or aralkyl optionally substituted as defined in the general formula, R 2 is other than a hydrogen atom or C 1 -C 4 alkyl substituted with one or more groups C2-C4-alkenyl, C2-C4-alkynyl, mono- or polyhalogen (C2-C4-alkynyl), according to another method, a ketone of the formula III, V or VII prepared above, in which R1 is a hydrogen atom and R2 is other than a hydrogen atom or a group C1-C4-alkyl substituted with one or more groups C2-C4-alkenyl, C2-C4-alkynyl, mono- or polyhalo- (C2-C4-alkynyl), reacting with the alkylating agent R With R 1 -Y, wherein R 1 is a group alkyl or aralkyl, optionally substituted as defined in the general formula and Y is a leaving group such as halogen, sulphonate or sulphate, e.g. in the presence of an organic or inorganic base, which are preferably an alkali metal - or alkaline earth metal hydroxides, alcoholates and hydrides, in protic or aprotic solvents or solvent mixtures, whether or not saturated or aromatic,:. * ,: 25 optionally halogenated hydrocarbons, alcohols, amides, nitriles, solvents containing oxygen derived from sulphides such as DMSO or sulfolane. Thus, other ketones of formula III, V and VII are obtained. In the event that ketones of formula III or V are obtained, which is possible by one of the methods described above, this; . then the above-mentioned modification procedure is followed to obtain • · “... ketones of formula VII.

»» »•

To obtain a compound of formula VII wherein identical R 1 and R 2 represent alkyl or aralkyl as defined in the general formula, there is another method of administering a ketone of formula III, V and VII prepared as above wherein R and R 2 represent a hydrogen atom, react with an alkylating agent R 1 -Y having alkyl or aralkyl as defined in the general formula and Y is a leaving group such as halogen, sulphonate or sulphate, e.g. organic or inorganic-5. in the presence of a base which is preferably alkali or alkaline earth metal hydroxides, alcoholates and hydrides in a protic or aprotic solvent or solvent mixture, which are saturated or unsaturated or aromatic, optionally halogenated hydrocarbons, alcohols, sulphide derivatives, nitrides, nitriles oxygen-containing solvents such as DMSO or sulfolane.

It is sometimes possible to isolate an intermediate in which only one of R 1 and R 2 is an alkyl or aralkyl group, as defined above. These compounds VII are also suitable for use in the processes described for the preparation of the compounds I. In the event that ketones of formula III or V are obtained, which is possible by one of the methods described above, the above-mentioned modification procedure is continued to obtain ketones of formula VII.

In the case where R 1 and R 2 form a C 2 -C 5 hydrocarbon chain, in the same manner as above, a compound of the formula Y-R 8 -; 25 Y, wherein R 9 is a C 2 -C 5 hydrocarbon group, is optionally substituted (e.g. one or more atoms or groups, such as halogen atoms, groups

• M

: C 1 -C 4 alkyl, mono- or polyhalo (C 1 -C 4 alkyl), · «· · ·; groups C1-C4-alkoxy and groups mono- or polyhalo (C1-C4-alkoxy), react with a ketone of the formula III, V, VII. with where R 1 and Ro represent a hydrogen atom, according to the method indicated above.

• · · • «• · ·

In the case where R 1 and / or R 2 represent an allyl group, there is another method of reacting a ketone of formula V wherein R 1 and R 2 are hydrogen atoms with two moles of allyl alcohol and 1 mole of 2,2-dimethoxypropane to catalytic an amount of paratoluene sulfonic acid in the presence of an inert solvent such as toluene to give the corresponding monoallyl ketone as described by WL Howard and N.B. Lorette, Org. Synth. 42, 34 (1964). This ketone is then reacted with a compound of formula 5 VI as described above, and the addition of the second allyl is performed by the method described above by alkylation.

In the case where and / or R 2 represents a group C 1 -C 4 alkoxy, it is preferred to start from a cycloalkanone of the formula V into which the alkoxy group (s) has already been introduced according to a method known to the person skilled in the art (e.g. by reaction of α-bromoketones with alkali alcoholates) .

15

In another general method for preparing ketones of formula VII wherein at least one of R 1 and R 2 is hydrogen, an enamine is prepared from a cycloalkanone of formula V wherein at least one of R 1 and R 2 is hydrogen, B.C. McKusick and F.E. According to Nurford, Org. Synth.

Coll. Part V, 808 and condensing the latter with a benzaldehyde of formula VI, L. Birkoffer, S.M. Kim and H.D. According to Engels, Chem. Ber. (1962), 9 £>, 1495. According to this article, acid hydrolysis then results in

To ketones according to 25 wherein at least one of R 1 and R 2 is hydrogen.

··· • · «·» · ·: *, * · The said compound of formula VII is reacted «· ·. with a sulfonium ylide, as described by E.j. Corey, 30 M. Chaykovsky, J. Am. Chem. Soc. 87, 1313, (1965), which • leads to oxiranes of formula IX: * 3,. 100797 14

The oxirane of formula IX is then reacted with unsubstituted imidazole or triazole in the presence of an organic or inorganic base such as, for example, pyridine, triethylamine, sodium hydroxide, callus hydroxide, alkali metal alkali metal carbide , such as alcohols, ketones, amides, nitriles, aromatic, optionally halogenated, hydrocarbons, at a temperature between 80 ° C and the reflux temperature of the solvent and in a molar ratio of IX / imidazole or triazole, preferably between 1.1 -0.2 to give compounds of formula I in which R5 is a hydrogen atom and R4 is other than halogen and the other substituents have the same meaning as indicated for the general formula.

Compounds of formula I in which R4 represents a halogen atom and R5 is a hydrogen atom are obtained by allyl halogenation of compounds of formula I in which R4 and R5 are hydrogen atoms, NBS (N-bromosuccinimide), NCS (N-chlorosuccinimide) di), with t-BuOCl in CCl4 in the presence of peroxides or under UV light, L. Horner and EH According to Winkelmann, Angew. Chem. 71, 349 (1959).

25

A compound of formula I in which R5 is other than a hydrogen atom: ***: and R4 is a non-halogen atom is obtained by etherification; or by esterification of compounds of formula I in which R5 is a hydrogen atom and R4 is a non - halogen atom by conventional methods well known to those skilled in the art:. ethers can be obtained by treating an alkali salt of an ψ · · * - * alcohol of formula I (e.g. a lithium or sodium salt · · '• · * /' with a suitable halide of formula R5Hal. Esters can be obtained by conventional treatment of a compound of formula I an alkali metal salt with a suitable acid chloride of the formula RgOOCl or a corresponding anhydride of the formula ^ 5) 2 () 200.

15 100797

Compounds of formula I wherein R 4 is a halogen atom and R 5 is other than a hydrogen atom are obtained as a first step by esterification or etherification as described above of a compound of formula I wherein R 5 and R 4 are hydrogen atoms and then halogenating the resulting compound of formula 1 as described above, e.g. with NBS.

Compounds of formula X1 and XII are obtained in a manner known to those skilled in the art. For example, the corresponding benzophenone can be acetalized in an acidic medium with an alcohol RiqOH in the case of a compound of formula XII. Trimethylsilyl chloride may be added to the corresponding cyclopentanone in the presence of dimethylformamide and triethylamine in the case of a compound of formula XII.

B. The Case of Compounds of Formula IB A cyclic ketone of formula IV is subjected to a well known aldolization / crotonization reaction by condensation with a benzaldehyde of formula VI to give a compound of formula VIII.

/ 30.30 Ce 1:.

• · * · * / Said compound of formula VIII is reacted with a sulfonium ylide as described by E.J. Corey, • M. Chaykovsky, J. Am. Chem. Soc. 87, 1313, (1965), whereby • ··. '; 3.5 is obtained an oxirane of formula X: R2> C ^? @_ <x) n * * 16 100797

The oxirane of formula X is reacted with an unsubstituted imidazole or trazole in the presence of an organic or inorganic base, e.g. pyridine, triethylamine, sodium hydroxide, potassium hydroxide, alkali metal carbonates and bicarbonates, and the like in the following. : alcohols, ketones, amides, nitriles, aromatic, optionally halogenated hydrocarbons, at a temperature between 80 ° C and the reflux temperature of the solvent and in a molar ratio of 10 X: imidazole or triazole, preferably between 1.1 and 0.2, where to give compounds of formula IB: ιΓ \ 15 II w \ 0R5 j 20 Ri 25 where R5 = H.

The same methods for alkylating or allylating the α-position (R 1, R 2) relative to the hydroxy group as described above are used in the same manner as for the methods for obtaining a compound in which R 5 is 1 · ... other than B.

• f • <«• t • j * r .: i Other manufacturing methods can of course also be used.

The invention also relates to compounds which can be ; may be used as intermediates in the processes for the preparation of compounds of formula III, IV, V, VII, VIII, IX, X described above, in which the substituents A, A 1, X, 40 n, R 1 -R 5, R 2 have the same meaning as in claim 1. .

17 100797

The present invention likewise relates to the use of compounds of formula I as a fungicide.

The compounds according to the invention can be used for both prophylactic and curative control of fungi, in particular those of the type Basidiomycetes, ascomycetes, adelomycetes or fungilmperfecti, in particular rust, mold, root rot, Fusarium rose, Fusarium roseum, Fusarium nivale, rhinosynporosis, helminthosporlos , rhizoctones in plants and seedlings in general and especially in cereals such as wheat, barley, rye, oats and their hybrids and rice and corn. The compounds of the invention are particularly effective in controlling fungi, in particular of the type Basidiomycetes, ascomycetes, adelo-15 mycetes or fungilmperfecti, such as:

Botrytis cinerea, Erysiphe graminis, Puccinia recondite, Piricularia oryzae, Cercospora beticola, Puccinia strrifor-mis, Erysiphe cichoracearum, Fusarium oxysporum (melonis), Pyrenophora avenae, Sceniciae, Septoria tritici, Venturia inaequalis, , Alternaria solani, Aspergillus niger, Cercospora arachidicola, Cladosporium Herbarum, Helminthosporium oryzae, Penicillium expansum, Pestalozzia sp., Phialophora cinerescens, Phoma betae rolf- · ** '· sii, Phomopsis viticola, Sclerotinia sclerotiorum, Scleroti-% «v J nia minor, Coryneum Cardinale and Rhizoctonia solani.

A: 30 They are also effective against the following fungi: oe, * Acrostalagmus koningi, Alternariat, Colletotrichumit, Corti- «'*' 'cium rolfsii, Diplodia natalensis, Gaeumannomyces graminis, Gibberella fujikuroi, Hormodendron cladosporioides, Lentinus 35 Degener or tigrinus quercina, Memnoniella echinacea, Myrothecium verrucaria, Paecylomyces varioti, Pellicularia sasakii, Phellinus megaloporus, Polystictus sanguineus, Poria vaporaria, Sclerotium rolfsii, Stachybotris 18 100797 atra, Stereum, Stilbum sp.

The compounds of the invention are particularly useful due to their wide spectrum of cereal diseases (mold, rust, root rot, helminthosporiosis, septoriosis and fusariosis). They are also very useful due to their effectiveness against Botrytis and cercosporiosis and therefore can be applied to a wide variety of crops, such as vines, vegetable and orchards, and tropical crops, such as peanut, banana, coffee, pecan.

Because the compounds do not have phytotoxicity, they can be used to protect plant reproductive products from fungal diseases.

Thus, the invention further relates to propagation products of crops which have been treated with a compound of the invention.

The term "reproductive product" means all parts of a plant which can be used for its reproduction. Mention should be made, for example, of grains (in the narrower sense, seeds), roots, fruits, tubers, bulbs, rhizomes, parts of the stem, seedlings and other parts of the plant. Mention should also be made of: *** · germinated seedlings and young seedlings to be moved • «·: ·. after germination or when taken from the soil. These • · · /./ young seedlings can be fully or partially protected before transfer by immersion treatment. Usually these compounds are applied from 0.1 g to 500 g / 100 kg of grains.

•> · · *. * * These compounds can thus be used for seed treatment (e.g. cereals, cotton bush, beet, oilseed rape, 35 feed grains, vegetable seeds) e.g. in the form of a coating or film. A use can be found in US-3,989,501, column 7, 11-23, as well as in FR-A-2,588,442. Concentrated suspensions can also be used.

19 100797 These formulations are generally already known, cf. e.g., "Catalog of Pesticide Formulation Types and International Coding System", GIFAP technical monograph no 2, pages 12-5 14, revised in January 1984.

In addition to the uses described above, the compounds of the invention have excellent biocidal activity against a number of other microorganisms, of which, without limitation, fungi belonging to the following genera may be mentioned:

Pullularia, such as P. pullulans,

Chaetomium, such as C. globosum, Aspergillus, such as Aspergillus niger, and Coniophora, such as C. puteana.

Due to their biocidal activity, the compounds according to the invention can effectively kill microorganisms, the proliferation of which causes numerous problems in agriculture and industry.

They are therefore particularly well suited for the protection of plants or industrial products such as wood, leather, paints, paper, ropes, plastics and industrial water systems.

• · · «· • · n '/ They are very suitable for lignocellulosic products. and in particular wood, be it furniture or building wood or exposed to weathering. . va wood, such as wooden fences, vine support poles and '·. * · sleepers.

• · ·

The compounds of the invention, used alone or in the form of compositions as defined above for the treatment of wood, are usually used in organic solvents and may optionally be combined with one or more known biocides, for example: pentachlorophenol, inorganic or carboxylic acids (heptane- , octanoic and naphthenic acids) metal salts especially copper, manganese, cobalt, chromium and zinc salts; tin 5 organic complexes, mercaptobenzothiazole, insecticides such as pyrethroids or organochlorine compounds.

The invention also relates to a method for treating cultures which are contaminated with fungi or which can be easily obtained, the method being characterized in that an effective dose of a compound according to the invention is applied to the leaves.

The compounds are preferably applied at doses of 0.002-5 kg / ha 15 and more particularly 0.005-1 kg / ha.

The compounds of the invention are rarely used alone. Most often they are part of the compositions. These compositions, which can be used to protect plants from fungal diseases or to control plant growth, contain as active ingredient a compound according to the invention, as described above, in combination with solid or liquid, agriculturally acceptable carriers and / or surfactants which are likewise in agriculture. t 25 acceptable. Particularly suitable are inert and conventional carriers and conventional surfactants.

These compositions usually contain from 0.5 to 95% of a compound of the invention.

'30

As used herein, the term "carriers" refers to an organic or inorganic substance, either naturally occurring or synthetic, to which the active ingredient is incorporated to facilitate its application to a plant, seed or soil. This carrier is therefore normally inert and must be acceptable in agriculture, in particular to the crop in question. The carrier can be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, etc.) or liquid (water, alcohols, ketones, petroleum fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons, liquefied gases, etc.).

5

The surfactant may be an emulsifying, dispersing or wetting agent, of the ionic or non-ionic type. Mention may be made, for example, of salts of polyacrylic acids, salts of lignosulphonic acids, salts of phenosulphonic acids or salts of naphthalenesulphonic acids, polycondensates of ethylene oxide with fatty alcohols or fatty acids or fatty amines, esters of sulfenes, derivatives (especially alkyl taurates), phosphoric acid esters of alcohols 15 or polyethoxylated phenols.

The presence of at least one surfactant is usually necessary when the active ingredient and / or the inert carrier are insoluble in water and water is used as a vector in the application.

These compositions may also contain all kinds of other ingredients, such as, for example, protective colloids, adhesives, thickeners, thixotropic agents, plant penetration enhancers, stabilizing agents, sequestering agents, etc., as well as other active ingredients which are * · · ... known for their pesticide properties (especially insecticides, fungicides) or for properties that promote the growth of plants (especially fertilizers) or for the control of plant growth. growth.

The compounds of the invention can usually be combined with: T: all solid or liquid additives which correspond to conventional formulation techniques.

‘: .35]: *; · The compounds of formula I are therefore normally

• I

: '·· for which purpose in the form of compositions. The compositions of the invention 22 100797 themselves are in very different forms, either solid or liquid.

Solid form compositions include powders for dispersing or dispersing (up to 100% of the compound of formula I) and granules, in particular those obtained by impregnating, compressing or impregnating a carrier in the form of granules or granulating a powder of a compound of formula I. the concentration of 10 in these granules is between 1-80% in the latter cases).

According to an example of a granular composition, the following ingredients are used: 15

Example F 9

Active substance 50 g

Epichlorohydrin 2.5 g 20 Ketyl ether and polyglycol ether 2.5 g

Polyethylene glycol 35 g

Kaolin (granulometry: 0.3-0.8 mm) 910 g In this special case, the active ingredient is mixed with epichlorohydrin and dissolved in 60 g of acetone, then polyethylene glycol and ketyl ether and polyglycol ether are added. Kaolin is moistened with the resulting solution. and then evaporate the acetone off in vacuo. Such microgranules are preferably used to control soil fungi.

• · o · i · »j .::

The compounds of formula I can also be used in spray form. „In the form of powders; a composition containing 50 g of active ingredient and 950 g of talc may also be used; • * '• 35 a composition containing 20 g of active ingredient, 10 g of finely divided silica and 970 g of talc can also be used; these ingredients are mixed and ground and the mixture is used for spraying.

23 100797

Formulations of liquid compositions or those intended to be liquefied during application include solutions, especially water-soluble concentrates, emulsifiable concentrates, emulsions, concentrated suspensions, aerosols, wettable powders (or sprayable powders) and pastes.

Emulsifiable or soluble concentrates usually contain 10-80% of active ingredient, while ready-to-use emulsions 10 or solutions contain 0.01-20% of active ingredient.

For example, in addition to the solvent, emulsifiable concentrates may contain, where necessary, 2-20% of suitable additives such as stabilizers, surfactants, plant penetration enhancers, corrosion inhibitors, colorants or the aforementioned adhesives.

The following are examples of the composition of some concentrates.

Example F (formulation) 1

Active substance 400 g / l

Alkaline dodecylbenzenesulphonate 24 g / l 25 Nonylphenol condensed with 10 molecules of ethylene oxide 16 g / l

Cyclohexanone 200 g / l • '·· Aromatic solvent g.s. 1 liter »» · • · • <a ··· [^ 0 According to another formula for the preparation of emulsifiable concentrate i *; ’· the following is used:: Example F 2 • a,"

Active substance 250 g: .i35 Epoxidised vegetable oil 25 g. A mixture of alkyl aryl sulfonate and V 'polyglycol ether and fatty alcohols 100 g. Dimethylformamide 50 g · 'Xylene 575 g i''40 «24 100797 These concentrates are obtained by diluting emulsions with water, which can be of any desired concentration and which are particularly suitable for application to leaves.

5

Concentrated suspensions, which can also be applied by spraying, are prepared to give a stable flowable product which does not settle and usually contains 10-75% of active ingredient, 0.5-15% of surfactants, 0.1-10 % thixotropic agents, 0-10% of suitable additives such as antifoams, anti-corrosion agents, stabilizers, plant penetration enhancers and adhesives and, as a carrier, water or an organic liquid in which the active ingredient is sparingly or not at all soluble; some solid organic substances or inorganic salts can be dissolved in the carrier, which helps to prevent sedimentation or freezing of the water.

Wettable powders (or sprayable powders) are usually prepared in such a way that they contain 20-95% of active ingredient and usually contain, in addition to a solid carrier, 0-5% of wetting agent, 3-10% of dispersant and, then when necessary, 0-10% of one 2b or more of a stabilizing agent and / or other additives, such as plant penetration enhancers, adhesives. substances or anti-clumping agents, • colors, etc.

• · · • · * I * • 30 The following are examples of different compositions of wettable powders: • »•« • ·· · Example F 3

Active substance 50% '• 35 Calcium lignosulphonate (flocculant) 5%

Isopropyl naphthalene sulfonate (anionic wetting agent) 1%

Silica (disintegrant) 5%. "40 Kaolin (filler) 39% 25 100797

In a 70% spray powder composition, the following ingredients are used: 5 Example F 4

Active substance 700 g

Sodium dibutyl naphthyl sulfonate 50 g

Condensation product of naphthalenesulphonic acid, phenolsulphonic acid and formaldehyde in a ratio of 3/2/1 30 g 10. Kaolin 100 g

Champagne join 120 g

A 40% spray powder composition uses the following ingredients: 15

Example F 5

Active substance 400 g

Sodium lignosulfonate 50 g

Sodium dibutyl naphthalene sulfonate 10 g Silica 540 g

Another 25% spray powder composition uses the following ingredients: Example F 6

Active substance 250 g

Calcium lignosulphonate 45 g, a mixture of equal amounts of Champagne chalk and hydroxyethylcellulose 19 g *, 30 Sodium dibutylnaphthalene sulphonate 15 g

Silica 195 g

Champagne chalk 195 g. · *: Kaolin 281 g • · '• * 35 Another 25% spray powder composition uses the following ingredients: • · • <.

• · · ·· «·: l: Example F 7

Active substance 250 g '40 Iso-octylphenoxy-polyoxyethylene-ethanol 25 g

Mixture of equal amounts of Champagne chalk and hydroxyethylcellulose 17 g

Sodium aluminosilicate 543 g

Milk 165 g 26 100797

Another 10% spray powder composition uses the following ingredients: Example 5 F 8

Active substance 100 g

Mixture of sodium sulphate salts of saturated fatty acids 30 g

Condensation product of naphthalenesulfonic acid and formaldehyde 10 50 g

Kaolin 820 g In the preparation of these sprayable powders or wettable powders, the active ingredients are mixed very thoroughly in suitable mixing equipment with additives and ground in mills or other suitable grinding equipment. This gives sprayable powders with advantageous wettability and suspending properties; they can be suspended in water at any desired concentration and these suspensions can be used very advantageously, in particular for application to the leaves of plants.

Instead of wettable powders, pastes can be prepared. The conditions and uses of these pastes are similar to those of wettable powders or sprayable powders.

27 100797

Compositions containing 0.5-5000 ppm of active ingredient are generally well suited; these values are given for ready-to-use compositions, ppm means "parts per million". The range 0.5-5000 ppm corresponds to 5 x 10 "- 0.5% (w / w).

The compositions to be stored and transported, on the other hand, more preferably contain 0.5 to 95% by weight of active ingredient.

Thus, the compositions according to the invention for use in agriculture may contain the active ingredients according to the invention in a very wide range, from 5 * 10% to 95% (by weight).

The following examples illustrate detailed procedures for the preparation of the compounds of the invention as well as the compounds themselves.

The names of the compounds are given according to French norms 20 except for the numbering of the substituents, which is in front of the substituents themselves.

Example I

Preparation of 2- (4-chlorobenzylidene) -5,5-dimethyl-1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclopentanol. To a mixture of 10 g of 2,2-dimethylcyclopentanone and; · 13.8 g of 4-chlorobenzaldehyde in 100 ml of ethanol at 0 ° C, • · * ··, add 100 ml of 10% aqueous sodium hydroxide solution.

It * ‘30 ports. After 30 min, this thick liquid solution is filtered. . and the solid is washed and then dried. 12.5 g of • · · · 2,2-dimethyl-5- (4-chlorobenzylidene) -1-cyclopentanone are obtained, * · * * m.p. is 120eC. This compound is dissolved in 50 ml of THF and added to a solution formed as follows: * 35 ways: 1.9 g of sodium hydride (80% dispersion in mineral oil) in 50 ml of anhydrous DMSO are heated to 80 ° C until the solid is completely dissolved. The solution is then diluted with 100 mL of THF and then cooled to 28-10797 -10 ° C. A solution of 11.5 g of trimethylsulfonium iodide in 80 ml of dimethyl sulfoxide is added over 10 minutes and the mixture is stirred for 15 minutes at -10 ° C. A solution of 11.8 g of 2,2-dimethyl-4-chloro-5- (4-chlorobenzyl-5-diene) -1-cyclopentanone is then added to 100 ml of THF.

The mixture thus prepared is allowed to return to ambient temperature and then poured into water and extracted with ether, washed with water, dried and distilled. 7- (4-Chloro-10-benzylidene) -4,4-dimethyl-1-oxaspiro (2,4) heptane is obtained, which is used immediately in the next step.

A mixture of 5 g of this substance and 2.8 g of 1,2,4-triazole and 11 g of potassium carbonate is heated in 40 ml of N, N-15 dimethylformamide for 4 h. The mixture is poured into water, extracted with ethyl acetate. The organic phase is washed, dried and recrystallized to give the title compound, m.p. is 154 ° C (Compound No. 1).

In a similar manner, the following compounds are obtained: 2- (4-fluorobenzylidene) -5,5-dimethyl-1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclopentanol (m.p. 147 ° C) ), compound 2, 25 2- (2,4-dichlorobenzylidene) -5,5-dimethyl-1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclopentanol (m.p. 130 ° C) , united ···. te no 3, • r 2- (4-trifluorobenzylidene) -5,5-dimethyl-1- (1H-1,2,4- (triazol-1-ylmethyl) -1-cyclopentanol (m.p. 132 ° C), Compound:: • 30- [2- (4-Chlorobenzylidene) -1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclopentanol (oil) Compound No. 5, V; 2-Benzylidene-1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclopentanol (oil), Compound No. 6 2- (4-Bromobenzylidene) -5,5- dimethyl-1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclopentanol (m.p. 152 ° C), compound i '·· no 7, I · 29 100797 2-benzylidene-5.5 -dimethyl-1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclopentanol (m.p. 137 ° C), compound no. 8, 2- (3,4-dichlorobenzylidene) -5, 5-Dimethyl-1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclopentanol (m.p. 157 ° C), Compound No. 9, 2- (4-chlorobenzylidene) -5-methyl- 1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclopentanol (oil), compound no. 10, 2- (2-chlorobenzylidene) -5,5-dimethyl-1- (1H- 1,2,4-Triazol-1-ylmethyl) -1-cyclopentanol (oil), Compound No. 11,10 2- (4-phenylbenzylidene) -5,5-dimethyl-1- (1H-1,2, 4-Triazol-1-ylmethyl) -1-cyclopentanol (m.p. 167 ° C), Compound No. 12,2- (4-chlorobenzylidene) -5-methyl-5-ethyl-1- (1H-1,2 , 4-triazol-1-ylmethyl) -1-cyclopentanol (m.p. 144 ° C), compound 13, 2- (4-chlorobenzylidene) ) -5,5-dimethyl-1- (1H-1,2,4-triazol-1-ylmethyl) -1-methoxy-cyclopentane (m.p. 84 ° C), compound no. 14, 2- (4-chlorobenzylidene) -4,5,5-trimethyl-1- (1H-1,2,4-20 triazol-1-ylmethyl) -1-cyclopentanol (m.p. 148 ° C), Compound No. 15, 2- (4-chlorobenzylidene) -5-methyl-5-methoxymethyl-1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclopentanol (m.p. 109 ° C ), ,,, compound no. 16, 2- (4-chlorobenzylidene) -5,5-di-n-propyl-1- (1H-1,2,4-; triazol-1-ylmethyl) -1-cyclopentanol (m.p. 123 ° C), compound 17, M <9 '... 2- (4-chlorobenzylidene) -5,5-diethyl-1- (1H-1,2,4-triazole-1- ylmethyl) -1-cyclopentanol (m.p. 171 ° C), compound • · JJ30 no 18, 2- (4-fluorobenzylidene) -5,5-diethyl-1- (1H-1,2,4-tria- sol-1-ylmethyl) -1-cyclopentanol (m.p. 166 ° C), compound • * · no 19, • · · * 2- (4-fluorobenzylidene) -5,5-di-n-propyl-1- ( 1H-1,2,4-35 triazol-1-ylmethyl) -1-cyclopentanol (m.p. 127 ° C), Compound No. 20, 2- (4-cyanobenzylidene) -5,5-dimethyl-1- (1H- 1,2,4-Triaza-100-sol-1-ylmethyl) -1-cyclopentanol (m.p. 137 ° C), Compound No. 21, 2- (4-chlorobenzene) cycidene) -5,5-dimethyl-3-ethyl-1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclopentanol (m.p. 58eC), Compound No. 22, 2- (4-parachlorophenoxybenzylidene) -5,5-dimethyl-1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclopentanol (m.p. 112eC), Compound No. 23 , 2- (4-chlorobenzylidene) -3-isopropyl-5,5-dimethyl-1-10 (1H-1,2,4-triazol-1-ylmethyl) -1-cyclopentanol (oil), Compound No. 24.

Example II

Preparation of 2- (4-chlorobenzylidene) -5,5-dimethyl-1- (1H-imidazolyl-15-methyl) -1-cyclopentanol_

A mixture of 5 g of 7- (4-chlorobenzylidene) -4,4-dimethyl-1-oxaspiro (2,4) heptane prepared according to the previous example and 2.8 g of imidazole and 11 g of potassium carb-20 the carbonate is heated in 40 ml of N, N-dimethylformamide for 4 h. The mixture is poured into water and extracted with ethyl acetate. The organic phase is washed, dried and recrystallized to give the indicated compound, m.p. is 174 ° C, compound no.

I i: 25

In a similar manner, the following compounds were obtained: ··· • · • «• · · 31 100797

To a mixture of 10 g of 2,2-dimethyl-4-chloro-1-cyclopentanone and 8.4 g of 4-fluorobenzaldehyde in 100 ml of ethanol at 0 ° C is added 50 ml of 10% aqueous sodium hydroxide solution. After 30 min, the thick liquid is filtered and the solid is washed and then dried. 11.8 g are obtained

2,2-dimethyl-4-chloro-5- (4-fluorobenzylidene) -1-cyclopentanone, m.p. is 69eC. 3.1 g of sodium hydride (80% dispersion in mineral oil) in 50 ml of dry DMSO

Heat to 80 ° C until the solid is completely dissolved. The solution is then diluted with 100 mL of THF and then cooled to -10 ° C. Add to the mixture for 10 min. a solution of 11.5 g of trimethylsulfonium iodide in 80 ml of dimethyl sulfoxide and the mixture is stirred for 15 min at -10 ° C. A solution of 11.8 g of 2,2-dimethyl-4-chloro-5- (4-fluorobenzylidene) -1-cyclopentanone was then added to 100 ml of THF. The mixture thus obtained was allowed to return to ambient temperature and then poured into water and extracted with ether, washed with water, dried and distilled.

7- (4-Fluorobenzylidene) -4,4-dimethyl-1-oxaspiro [2,4] -5-heptene is obtained, which was used immediately in the next step.

A mixture of 5.5 g of the substance obtained and 2 g of 1,2,4-triazole and 6.6 g of potassium carbonate was heated in 50 ml of N, N-dimethylformamide for 4 h. The mixture was poured into water · ***; and extracted with ethyl acetate. The organic phase was washed, dried and recrystallized to give 2.4 g. the indicated compound having a m.p. is 168 ° C, compound no.

• «* 30. . In a similar manner the following compounds were obtained: 2- (4-chlorobenzylidene) -5,5-dimethyl-1- (1H-1,2,4-triazol-1-ylmethyl) - 1-hydroxy-3-cyclopentene (m.p. 203 ° C), i '35 compound no. 30,

I «I

2- (2,4-dichlorobenzylidene) -5,5-dimethyl-1- (1H-1,2,4-β-triazol-1-ylmethyl) -1-hydroxy-3-cyclopentene (m.p.

182 ° C), compound no.

32 100797

Example IV

Preparation of 2- (4-fluorobenzylidene) -5,5-dimethyl-1- (1H-imidazolylmethyl) -1-hydroxy-3-cyclopentene 5

A mixture of 5.5 g of 7- (4-fluorobenzylidene) -4,4-dimethyl-1-oxaspiro (2,4) -5-heptene prepared according to the above example and 2 g of imidazole and 6.6 g of potassium carbonate, heated in 50 ml of N, N-dimethyl-10 formamide for 4 h. The mixture is poured into water and extracted with ethyl acetate. The organic phase is washed, dried and recrystallized to give the title compound, m.p. is 172 ° C, compound no.

15 Example V

Preparation of 2- (4-chlorobenzylidene) -3,5,5-trimethyl-1- (1H-1,2,4-trazol-1-ylmethyl) -1-cyclopentanol

A mixture of 2.3 g of sodium hydride and 120 ml of DMSO is heated at 75 ° C until the solid has dissolved.

120 ml of THF are added and the solution is cooled to -5 ° C. 16 g of trimethylsulfonium iodide in 50 ml of DMSO are added and the temperature is kept below 0 ° C. 15.8 g of 2- (4-chlorobenzylidene) -3,5,5-trimethylcyclopentanone dissolved in 20 ml of THF, 25 are added and the solution is allowed to return to ambient temperature.

* t ... Prepare a solution of triazolyl sodium starting from 5.3 g of 1H-1,2,4-triazole, 2.3 g of sodium hydride in 100 ml of DMSO and add it, then heat the mixture * 30 at 130eC for 2 h. The solution is washed with water, extracted with ethyl acetate, dried and purified on silica. 2.4 g of a yellow solid are obtained, m.p. is 148 ° C.

2- (4-chlorobenzylidene) -3,5,5-trimethylcyclopentanone 35 is obtained as follows: To 2.7 g of magnesium in 50 ml of ether is added 7 ml of methyl iodide. When the organomagnesium compound is formed, the solution is cooled to -5 ° C and 1 g of cuproiodide is added.

33 100797

10 g of 5,5-dimethyl-2-cyclopentanone in 30 ml of ether are added, keeping the temperature below 0 ° C. 14 g of chlorobenzaldehyde in ether are then added. Then 50 ml of conc. Hydrochloric acid are added, then 50 ml of water. The aqueous phase 5 is then extracted with ether. The organic phase is washed, dried and purified on a silica column. 15.8 g of oily compound are obtained. 5,5-Dimethyl-2-cyclopentenone is obtained in a known manner.

10 Example VI

Preparation of 2- (4-chlorobenzylidene) -5,5-diallyl-1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclopentanol

A mixture of 2.7 g of sodium hydride and 120 ml of DMSO is heated at 75 ° C until dissolved. 120 ml of THF are added and the solution is cooled to -5 ° C. 12.6 g of trimethylsulfonium iodide in 50 ml of DMSO are added and the temperature is kept below 0 ° C. 16.5 g of 2- (4-chlorobenzylidene) -5,5-diallylcyclopentanone in 20 ml of THF are added and the solution is allowed to return to ambient temperature.

A solution of triazolyl sodium is prepared starting from 8.3 g of 1H-1,2,4-triazole, 4.8 g of sodium hydride in 100 ml of DMSO and added, followed by heating to 80 ° C: for 2 h. The solution is washed with water, extracted with ethyl acetate, dried and purified on a silica column. 6.2 g of a yellow solid are obtained, m.p. is . - 128 ° C, compound no. 33.

• 4 «· * ♦ '«.

t 'r' 30 2- (4-chlorobenzylidene) -5,5-diallyl-cyclopentanone is obtained as follows: • · • * * •.

t ·· · * · * * 2.5 g of sodium hydride are washed with 50 ml of heptane.

Add 100 ml of toluene and 6.7 ml of tert-amyl alcohol.35 and heat at 50 ° C. When the evolution of hydrogen has ceased, 15 g of 2- (4-chlorobenzylidene) -5-allyl are added.

cyclopentanone and 8.1 ml of allyl chloride. The solution is heated to reflux, cooled, washed with water. The organic phase is dried. After evaporation, 16.5 g of liquid are obtained. 5-Allylcyclopentanone is obtained from W.L. Howard and N.B. According to Lorette, Org. Synth. 42, 34.

In a similar manner there was obtained 2- (4-fluorobenzylidene) -5,5-diallyl-1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclopentanol, m.p. 112 ° C, compound no.

Example VII

Preparation of 2- (4-chlorobenzylidene) -5,5-dimethyl-1- (1H-1,2,4-triazol-1-ylmethyl) -1-methoxy-cyclopentanol 4.2 g of powdered potassium hydroxide and 5, 2 g of 2- (4-chlorobenzylidene) -5,5-dimethyl-1- (1H-1,2,4-triazolemethyl) -15 cyclopentan-1-ol in 32 ml of DMSO are stirred at ambient temperature. 2 ml of methyl iodide are added and the mixture is stirred. The solution is poured into water and extracted with ethyl acetate. The organic phase is washed again with water and dried. Purify on a silica column to give 4.9 g of pure compound. Sp. is 84 ° C.

2- (4-Chlorobenzylidene) -5,5-dimethyl-1- (1H-1,2,4-triazolemethyl) -cyclopentan-1-ol is obtained as follows: To a mixture of 10 g of 2,2- dimethylcyclopentanone and 13.8 g of 4-chlorobenzaldehyde in 100 ml of ethanol at 0 ° C,? *** · 100 ml of a 10% aqueous solution of sodium hydroxide are added. After 10 min the thick liquid is filtered and solid c «» ·. *. the substance is washed and then dried. 12.5 g of 2,2-dimethyl-3-yl-5- (4-chlorobenzylidene) -1-cyclopentanone are obtained, which,. mp. is 120eC.

This compound dissolved in 50 ml of THF is added to a solution formed as follows: 1.9 g of sodium hydride (80% dispersion in mineral oil) in 50 ml of anhydrous DMSO are heated at 80 ° C until complete dissolution of the solid. until. The solution is then diluted with 100 mL of THF and then cooled to -10 ° C. A solution of 11.5 g of trimethylsulfonium iodide in 80 ml of dimethyl sulfoxide is added to the mixture over 10 minutes and the mixture is stirred for 15 minutes at -10 ° C.

A solution of 11.8 g of 2,2-dimethyl-4-chloro-5- (4-chlorobenzylidene) -1-cyclopentanone in 100 ml of THF is then added. The mixture thus formed is left to return to ambient temperature and then poured into water and extracted with ether, washed with water, dried and distilled. 7- (4-Chlorobenzylidene) -4,4-dimethyl-1-oxaspiro (2,4) -heptane is obtained, which is used directly in the next step. A mixture of 5 g of this substance and 2.8 g of 1,2,4-triazole and 11 g of potassium carbonate is heated in 40 ml of N, N-dimethylformamide for 4 h. The mixture is poured into water and extracted with ethyl acetate. The organic phase is washed, dried and recrystallized to give the indicated substance, m.p. is 154 ° C, compound no.

To illustrate, the following compounds are given as melting points for the following compounds: 2,2-dimethyl-4-chloro-5- (4-fluorobenzylidene) -1-cyclopen-: tannone, m.p. 69 ° C, 2,2-dimethyl-4-chloro- 5- (4-chlorobenzylidene) -1-cyclopene-25-tannone, mp 68 DEG C., 2,2-dimethyl-4-chloro-5- (2,4-dichlorobenzylidene) -1-; · · Cyclopentanone, mp 68eC, • · · 2,2-dimethyl-5- (4-fluorobenzylidene) -1-cyclopentanone, mp 69eC, 30,2-dimethyl-4-chloro-5- (4-chlorobenzylidene) -1-cyclopentene-tannone, mp 120 ° C, N, N-2,2-dimethyl-5- (4-trifluoromethylbenzylidene) -1-cyclopentanone, mp 107 ° C, 2,2-dimethyl-5- (2,4-dichlorobenzylidene) -1-cyclopentanone, which is an oil, 2,2-dimethyl-4-chloro-5- (4-chlorobenzylidene) -1 -cyclopentan-tannone, mp 60eC, 2- (4-chlorobenzylidene) -1-cyclopentanone, mp 63eC, 36 100797 2-Benzylidene-1-cyclopentanone, which is an oil, 2- (4-bromobenzylidene) - 1-cyclopentanone, mp 97eC, 2,2-dimethyl-5-benzylidene-1-cyclopentanone as an oil, 2,2-dimethyl-5- (3,4-dichlorobenzylidene) -1-cyclopentanone as an oil, 2- (3,4- dichlorobenzylidene) -1-cyclopentanone, which is an oil, 2-methylethyl-5- (4-chlorobenzylidene) -1-cyclopentanone, m.p.

10 107 ®C, 2-methyl-5- (2-chlorobenzylidene) -1-cyclopentanone, which is an oil, 2,2-dimethyl-5- (2-chlorobenzylidene) -1-cyclopentanone, which is an oil, 2-phenylbenzylidene) -1-cyclopentanone, m.p. 146 ° C, 2,2-dimethyl-5-phenylbenzylidene-1-cyclopentanone, m.p. 120 ° C, 2-ethyl-2-methyl-5- (4-chlorobenzylidene) -1-cyclopentanone, m.p. 85 ° C, 2-allyl-5- (4-chlorobenzylidene) -1-cyclopentanone, m.p.

60 ° C, 2,2-diallyl-5- (4-chlorobenzylidene) -1-cyclopentanone, which is an oil, • *:. * ·· 2,2,4-trimethyl-5- (4-chlorobenzylidene) -1-cyclopentanone , 25 which is an oil: 2-methyl-2-methoxymethyl-5- (4-chlorobenzylidene) -1- ···: cyclopentanone which is an oil, • · · 2-allyl-5- (4-chlorobenzylidene) - 1-cyclopentanone, m.p. llleC, #. 2,2-diallyl-5- (4-fluorobenzylidene) -1-cyclopentanone,: ·:: which is an oil, · «* *. * * 2,2-diethyl-5- (4-chlorobenzylidene) -1- cyclopentanone,: which is an oil, • ·. · · ·. 2,2-diethyl-5- (4-fluorobenzylidene) -1-cyclopentanone, »· 35 which is an oil, 2- (4-cyanobenzylidene) -1-cyclopentanone, which is an oil, • · 2,2-dimethyl-5 - (4-cyanobenzylidene) -1-cyclopentanone, which is an oil, 37 100797 2,2-dimethyl-4-ethyl-5- (4-chlorobenzylidene) -1-cyclopentanone, which is an oil, 2- (4-p- chlorophenoxybenzylidene) -1-cyclopentanone, m.p. 92 ° C, 5,2-dimethyl-5- (4-p-chlorophenoxybenzylidene) -1-cyclopentanone, which is an oil, 2,2-dimethyl-4-isopropyl-5- (4-chlorobenzylidene) -1-cyclopentanone, which is an oil, 2,2-dimethyl-5- (4-chlorobenzylidene) -1-cyclopentanone, 10 m.p. 60 ° C, 2,2-dimethyl-5- (2,4-dichlorobenzylidene) -1-cyclopentanone, m.p. 68 ° C, 2,2-dimethyl-5- (4-fluorobenzylidene) -1-cyclopentanone, m.p. 69 ° C.

15

Example VIII

Preparation of 2- (4-chlorobenzylidene) -6-methyl-1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclohexanol To a mixture of 22.4 g of 2-methylcyclohexanone and 28.1 g of g of para-chlorobenzaldehyde in 250 ml of ethanol at 0 ° C, add 10% aqueous sodium hydroxide solution] 100 ml. Stir for 15 h and then dilute the medium with • · · ’· ** water and extract with ethyl acetate.

25

The organic phase is dried over Na2SO4 and concentrated: and the residue is chromatographed on a column of silica using heptane / ethyl acetate 90/10 as eluent. A yellow oil is obtained. It is crystallized from pentane to give a pale:. 30 yellow powder (17.1 g) of 2- (4-chlorobenzylidene) -6-methylcyclohexanone, m.p. at 59 ° C.

• · · • ·. * ·; 3.8 g of this compound dissolved in anhydrous THF (33 ml) · *, · are added at -5 ° C to a reaction medium prepared as follows: 0.8 g of sodium hydride (60% dispersion) is heated to 70 ° C 26 in 1 ml of dry DMSO, then 33 ml of 38 100797 anhydrous THF are added. The mixture is cooled to -5 ° C and treated with trimethylsulfonium iodide (3.9 g) dissolved in 20 ml of DMSO.

After 1 h at -5 ° C, the 8- (4-chlorobenzylidene) -4-methyl-1-oxaspiro (2.5) octane thus formed is treated with triat-Sol (2.2 g) and triazolyl sodium (0.28 g). .

The medium is heated to 93 ° C for 1 h after distilling off 30 ml of THF and adding 50 ml of DMF.

Dilute with water (1 L) and extract the compounds with dichloromethane and purify the residue by chromatography (eluent heptane / ethyl acetate 1: 1). 15

First there is a diastereoisomer which is more numerous and in which the substituents methyl and hydroxyl are in the cis position and which melts at 139 ° C (compound no. 35), then a diastereoisomer which is less and in which the substituents methyl and hydroxyl are in the trans position are in syrupy form (Compound No. 36).

Stereochemistry is based on nuclear magnetic resonance imaging according to techniques well known to those skilled in the art.

25

Example IX

:. ·. Preparation of 2- (4-chlorobenzylidene) -6,6-dimethyl-1- (1H-1,2,4-triazole-2-yl-sol-1-ylmethyl) -1-cyclohexanol · ♦ 30 To a reaction medium prepared from toluene • • · · ϊ · Σ · ethylene (25 ml), tert-amyl alcohol (3.6 ml) and sodium ··· *. '* Hydride (1.35 g dispersion) 60% in oil) and heated to 45 ° C, successively 2- (4-chlorobenzylidene) -6-methylcyclohexanone prepared above 35 (7.0 g), then methyl iodide (5.1 g) . The mixture is refluxed (1 h), poured into water and extracted with ethyl acetate.

: · Dry and concentrate and recrystallize the residue from 39,100797 methanol to give 2- (4-chlorobenzylidene) -6,6-dimethylcyclohexanone (4.7 g), melting at 92 ° C.

The procedure of Example 1 is then followed with 4 g of this ketone to give, after chromatography, the expected compound, melting at 179 ° C (compound no. 37).

In a similar manner the following compounds were obtained: 2- (4-fluorobenzylidene) -6,6-dimethyl-1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclohexanol. Isomer A, Compound No. 38, m.p. 154 ° C, 2- (4-chlorobenzylidene) -1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclohexanol. Isomer A, Compound No. 39, m.p. 117 ° C, 2- (4-chlorobenzylidene) -6-cyclohexyl-1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclohexanol. Isomer A, Compound No. 40, m.p. 206 ° C, 2- (4-chlorobenzylidene) -6-cyclohexyl-1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclohexanol. Isomer B, Compound 20 of 41, m.p. 197 ° C, 2- (4-chlorobenzylidene) -6-t-butyl-1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclohexanol. Isomer A, Compound No. 42, m.p. 144 ° C, • ♦ 2- (4-chlorobenzylidene) -6-sec. -butyl-1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclohexanol. Isomers A + B, Compound No. 43, m.p. 171 ° C, «* 0: 2- (4-chlorobenzylidene) -6-sec-butyl-1- (1H-1,2,4-triazole-1-ylmethyl) -1-cyclohexanol. Isomers C + D, Compound No. 44, m.p. 148 ° C,. 2- (4-chlorobenzylidene) -6-methyl-6-phenyl-1- (1H-1,2,4 - (', 11') triazol-1-ylmethyl) -1-cyclohexanol. Isomer A, compound • · · ** [* te no 45, m.p. 177 ° C, 2- (4-chlorobenzylidene) -6-methyl-6-phenyl-1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclohexanol. Isomer B, compound-35 te no 46, m.p. 133 ° C, 2- (4-chlorobenzylidene) -6-methyl-6-ethyl-1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclohexanol. Isomers A + B, Compound No. 47, m.p. 175 ° C, 40 100797 2- (4-chlorobenzylidene) -6-methyl-6-isopropyl-1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclohexanol. Isomer A, Compound No. 48, m.p. 154 ° C, 2- (4-chlorobenzylidene) -6-methyl-6-isobutyl-1- (1H-5 1,2,4-triazol-1-ylmethyl) -1-cyclohexanol. Isomer A, Compound No. 49, m.p. 163®C, 2- (4-chlorobenzylidene) -6-methyl-6-isobutyl-1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclohexanol. Isomer B, Compound No. 50, m.p. 184 ° C, 10 2- (4-chlorobenzylidene) -1- (1H-1,2,4-triazol-1-ylmethyl) -1-cycloheptanol, Compound No. 54, m.p. 104®C, 2- (4-chlorobenzylidene) -7,7-dimethyl-1- (1H-1,2,4-triazol-1-ylmethyl) -1-cycloheptanol, Compound No. 54, m.p.

143 ° C, 15 2- (4-fluorobenzylidene) -1- (1H-1,2,4-triazol-1-ylmethyl) -1-cycloheptanol, Compound No. 55, m.p. 91®C, 2- (4-chlorobenzylidene) -7-methyl-1- (1H-1,2,4-triazol-1-ylmethyl) -1-cycloheptanol, Compound No. 56, m.p. 166 ° C.

20 The following are typical physical properties of the cycloalkanones used in some of the starting materials.

General methods for preparing these compounds are reported, as noted, in the literature. The following documents can advantageously be used as source works:. DE-OS 2 245 518, D.A. Whiting, J. Chem. Soc. (1971), 3396, G. Le Guillanton (1969), Bull. Soc. Chim., 2871, • · · * Pal Perjesi et al., Chem. Ber. (1987), 120, 1449, 30 J.M. Conia et al., Bull. Soc. Chim. (1970), 2972.

• · * · ♦ ♦ ···: 2- (4-fluorobenzylidene) -1-cyclohexanone, b.p. 0.02 mm Hg,. · *. : 140 ° C, • · · '. · * 2- (4-chlorobenzylidene) -1-cyclohexanone, m.p. 54®C, 35 2-methyl-6- (4-chlorobenzylidene) -1-cyclohexanone, m.p.

59 ° C, 2,2-dimethyl-6- (4-chlorobenzylidene) -1-cyclohexanone, m.p. 92®C, 41 100797 2,2-dimethyl-6- (4-fluorobenzylidene) -1-cyclohexanone, m.p. 51 ° C, 2-cyclohexyl-6- (4-chlorobenzylidene) -1-cyclohexanone, m.p. 97 ° C, 5-t-butyl-6- (4-chlorobenzylidene) -1-cyclohexanone, b.p. 0.06 mm Hg 180 ° C, 2-sec-butyl-6- (4-chlorobenzylidene) -1-cyclohexanone, m.p. 46 ° C, 2-phenyl-6- (4-chlorobenzylidene) -1-cyclohexanone, m.p.

1012 ° C, 2-methyl-2-phenyl-6- (4-chlorobenzylidene) -1-cyclohexanone, m.p. 77 * C, 11-dimethyl-3- (4-chlorobenzylidene) -2-tetralone, which is an oil, 2-methyl-2-ethyl-6- (4-chlorobenzylidene) -1-cyclohexanone, m.p. 70 ° C, 2-methyl-2-isobutyl-6- (4-chlorobenzylidene) -1-cyclohexanone, which is an oil, 2-methyl-2-sopropyl-6- (4-chlorobenzylidene) -1-cyclo-20 hexanone, which is an oil, 6- (4-chlorobenzylidene) -spiro (4,5) decan-5-one, which is ...: oil,] 2- (4-fluorobenzylidene) -1-cycloheptanone, m.p. 62 ° C, • 2- (4-chlorobenzylidene) -1-cycloheptanone, m.p. 75 ° C, "2-methyl-7- (4-chlorobenzylidene) -1-cycloheptanone, m.p.

: i. ": 74 ° C, ·: *: 2,2-dimethyl-7- (4-chlorobenzylidene) -1-cyclohexanone, m.p. 63 ° C, 2,2-dimethyl-7- (4-chlorobenzylidene) -1-cyclohexanone,: · 30 ° 63eC.

• · * • · · · • · · ·

The following examples illustrate the use of the compounds of the invention as fungicides.

In these examples, sprays of solutions or suspensions of the active compounds are carried out under conditions such that the spraying of a solution or suspension at a concentration of 1 g / l corresponds to an average application of about 2 micrograms of active substance per cm 2 of plant leaf.

The compounds described under the conditions of Examples X-XVI have not shown phytotoxicity.

In these examples, a compound is considered to provide complete protection against fungal disease when the protection is at least 95%; protection is considered good when it is always at least 10% (but less than 95%), fairly good when it is at least 70% (but less than 85%), average when it is at least 50% (but less than 70%).

15 In the present description, percentages are by weight unless otherwise indicated and except for yields. In the case where percentages are given stoichiometrically, these are mole percentages. Some concentrations are expressed in ppm (parts per million), which corresponds to 20 mg / l.

The experiments have been performed at doses of 1 g / l or 0.3 g / l without this prejudicing the value of the compounds themselves.

25

Example X

; [·. in vivo test for 'Botrytis cinerea' from cut tomato leaves i:: - 30 Prepared by finely grinding an aqueous emulsion of the active substance to be tested, the composition of which is as follows: • ♦ · • · * • · ·. : Active substance to be tested 60 mg * · * · Tween 80 (surfactant consisting of polyethoxylated sorbitan monooleate diluted to 10% with water in 0.3 ml

Water, make up to 60 ml with 40 43 100797

This aqueous emulsion is then diluted with water to obtain the desired concentration.

Tomatoes grown in a greenhouse (Marmande variant), 5 to 40 d years old, are treated by spraying with aqueous emulsions (spray liquid) containing the test composition at various concentrations of active substance.

The experiment is repeated twice at each concentration.

After 24-48 h, the leaves are cut and placed in 2 petri dishes (14 cm in diameter) with a pre-set sheet of moist filter paper (5 leaves per dish).

The inoculum is then introduced by means of a syringe by placing the spore-15-pension in drops, 3 drops per leaf. This spore suspension of Botrytis cinerea is obtained from a 15 d old culture which is then suspended in a nutrient solution (100,000 units / cm 2). The control is performed 3-6 d after infection by comparison with an untreated control dish.

Under these conditions, good or complete protection with compounds 1 and 3 and 0.3 g / l with good or complete protection with compounds 2, · 7 ·: 15, 16, 35, 38 and 39.

25

Example XI

: in vivo test for "Erysiphe graminis" causing • · · · _ "- - '" "“ f ™ r - f „W -" - —I- - - causing barley mildew

• · · «I» I .1 ———— I

. m. " 30 Barley sown in pots in a 50/50 mixture of peat and pozzolan at a height of 10 cm is treated by spraying • · · • · · with the above-mentioned aqueous emulsion (called spray • · V *: liquid), the concentration of which is indicated. behind.

The experiment is repeated twice. After 24 h, barley seedlings are sprinkled with Erysiphe graminis spores, sprinkling from diseased plants.

Reading is performed 8-14 d after contamination.

44 100797 Under these conditions, the following results are observed:

At 1 g / l good or complete protection for compounds 1, 2, 3, 14 and 26 and at 0.3 g / l for compounds 4, 11, 38, 5 53 and 55.

At 1 g / l fairly good or moderate protection for compounds 10, 25 and 33 and at 0.3 g / l for compounds 8, 15, 22, 29 and 39.

10

Example XII

in vivo test for "Puccinia recondita" causing wheat rust 15 Wheat planted in pots in a 50/50 mixture of enriched peat and pozzolan is treated at a height of 10 cm by spraying aqueous emulsions of the same composition as shown in Example IV above and with different concentrations of test compound.The experiment was repeated 20 times at each concentration.

After 24 h, an aqueous spore suspension (50,000 spores / cm 2) is sprayed onto the wheat; this suspension is obtained from contaminated seedlings. The wheat is then incubated for 48 h in an incubation chamber at a temperature of about 18 ° C and a relative humidity of 100%.

• · 1 · · * · · • · · After these two days, the relative humidity is reduced to 60%. Plant condition control is done between 11-15 d. 30 after contamination by comparison with an untreated reference *; *. * Plant.

• · · • · ·

At a dose of 1 g / l, good or complete protection was obtained with compounds 1, 2, 3, 10, 14, 25, 26, 27 and 33 and at a dose of 0.3 35 g / l with compounds 4, 7, 9, 13, 14, 15, 18, 19, 28, 34, 35, 37, 38, 43, 47 and 53.

45 100797

A dose of 2 g / l gave fairly good or moderate protection for compound 5 and a dose of 0.3 g / l for compounds 8, 10, 11, 20, 22, 42, 44 and 49.

5 Example XIII

in vivo test for "Piricularia oryzae" causing rice pirlcularosis (rice plague)

Rice sown in pots in a 50/50 mixture of enriched peat and pozzolan is treated at a height of 10 cm by spraying with an aqueous emulsion of the concentration defined above. The experiment is repeated twice. After 48 h, the plants are treated by applying to the leaves a suspension of spores obtained from pure cultivation. 15

The reading is performed 8 d after contamination. Under these conditions, the following results are observed:

At 1 g / l good or complete protection for compounds 1, 20 2, 4, 25 and 28 and at 0.3 g / l for compounds 7, 9, 11, 12, 13, 14, 22, 29, 30, 33, 34 , 38, 39, 43, 44 and 47.

] At 1 g / l fairly good or moderate protection for compounds 5, 26 and 27 and at 0.3 g / l for compounds 15, 16, 25 18, 23, 31, 32, 42, 48 and 49 .

* ·

: Example XIV

• · · · ™ in vivo test for "Puccinia recondita" by treatment

Grains:. *. 30 ♦ · ·

Wheat grains, from the Talent variant, are treated with the spray liquid of the example • · · above at a dose of 75 g / 100 kg, they are • · ·. * ·· sown in a substrate formed of a 50/50 mixture of peat and pozzolan. 15 d after sowing

35 heet are inoculated with Puccinia recondita in Example XII

according to the instructions described. Reading of results is performed 30 d and 45 d after sowing.

46 100797

At the reported doses, compounds Nos. 1, 2, 3, 4, 13, 28, 29, 30, 31, 32, 35, and 37 have a zero infection rate of 30 d after sowing, whereas growth subjects from untreated grains were 100% contaminated.

5

Example XV

in vivo test for "Fusarium roseum" by treatment

Grain 10 Wheat grains of the Talent variant naturally contaminated with Fusarium roseum are treated with the spray liquid defined in Example X above at a dose of 10, 25, 50 and 100 g per 100 kg of grains. A batch of 50 g of treated grains is placed in a medium containing 200 grains containing gelatin and malt at a concentration of 2% and 1%, respectively. The grains are stored at 20 ° C for 10 days. The condition of the grains is controlled by comparison with untreated control grains with developed Fusarium roseum colonies.

20

At the reported doses, good or complete protection is observed with compounds 1, 2, 3, 4, 13, 15, 28, 29, 30, 31, 32, 35, 37, 52 and 54.

• <· 25 The following example illustrates the invention. the absence of phytotoxicity of the compounds with respect to grain growth; . ·. I do.

• · · • · · · • · ·%

Example XVI

30 Wheat grains, from the Talent variant, are treated with a spray liquid ··:: at doses of 2, 5, 10, 25, 50, 100, 200 and 400 g / 100 kg.

·· · • · · • · ·

The grains are placed on a filter paper soaked in water. After 15 d of incubation, coleoptiles and • | 35 the lengths of the first leaves with compounds Nos. 1, 13, 15, 35 and 37.

The results are shown in the following table: 47 100797

Length (cm)

Dose g / 100 kg_Coleoptiles and first leaves 0 13 12 13 5 25 13 50 13 100 12 200 13 400 12 10

Each value reported in the table above is the average of forty little trout.

«·« 1 · * · · • · · ΓΓ: • · • · · * · # • · · · ·· »• · · · · · 0 0

Claims (4)

Compounds which can be used in particular as intermediates for (benzylidene) -azolylmethylcycloalkanes or alkenes of the formula: Pk Λ, IA IB wherein 10. is -CH2-, -CH (CH3) -, -CH2CH2- or - CH 2 CH 2 CH 2 -, A 1 is -CH-, X is a halogen atom, preferably fluorine, bromine, chlorine or a cyano group, CF 3, phenyl or phenoxy, n is 0, 1 or 2, 15 and the groups X may be identical or different when n is 2, W is N or -CH-, R 1 is hydrogen, C 1 -C 4 alkyl, methoxymethyl, allyl, phenyl or cyclohexyl; R 2 is hydrogen or C 1 -C 4 alkyl or allyl; v - R 3 is hydrogen or C 1 -C 4 alkyl or allyl; · R4 R4 is hydrogen; : T: R5 is hydrogen or methyl and R12 is hydrogen, • * • · • ·· in the preparation of compounds of formulas VII, VIII, IX and X * '· * 25 ···: oh VII 49 100797 Rs \ ci VIII 1 vAJ / '* · DC 5 A. wherein J, X, R 1, R 2, A 1, R 4, A, R 3 and R 2 are as defined above; except for the following compounds:. 2-benzylidenecyclopentanone, '* 2- (4-chlorobenzylidene) cyclopentanothi,'. * '2-benzylidene-3-methylcyclopentanone,: · · · 2-benzylidene-5-methyl-cyclopentanone, «· · 2-benzylidenecyclohexanone, 6-cyclohexyl-2-benzylidenecyclohexanone, 2-benzylidene-6-benzylidene-6-benzylidene , 2-benzylidenecycloheptanone,:. 2-benzylidene-6,6-dimethyl-cyclohexanone, * ·; ·. 2-Benzylidene-3-methyl-6-isopropyl-cyclohexanone, • * · 20 2- (4-fluorobenzylidene) -3-methyl-6-isopropyl-cyclohexanone, »··: 2- (4-chlorobenzylidene) -3- methyl 6-isopropyl-cyclohexanone, 2- (4-bromobenzylidene) -3-methyl-6-isopropyl-cyclohexanone,. · · ·. 2- (4-cyanobenzylidene) -3-methyl-6-isopropyl-cyclohexanone, •, 2- (4-phenylbenzylidene) -3-methyl-6-isopropyl-cyclohexanone, 2- (4-fluorobenzylidene) -cyclohexanone, 2 - (4-chlorobenzylidene) -cyclohexanone, 2- (4-bromobenzylidene) -cyclohexanone, 100797 50 2- (4-cyanobenzylidene) -cyclohexanone, 2- (4-phenylbenzylidene) -cyclohexanone, 2- (4-chlorobenzylidene) -cyclohexanone , 2- (2,6-dichlorobenzylidene) -cyclohexanone. 5 For a specific species having an intermediate in the form of (benzylidene) -azolylmethylcycloalkane or -alkener with the form: / / // Λ 10 * IA IB i vilka A is -CH2-, -CH (CH3) -, -CH2CH2- or - CH2CH2CH2-, 15 A is -CH-, '·' X is a halogen atom, forethyl fluorine, Bromine, chlorine or cyano, CF3, phenyl: "or phenoxy,: .., n is 0, 1 or 2, and a group of X is an active substance if it was 2, WarN or CH, R1 is C1-C4 alkyl, methoxymethyl, allyl, phenyl or cyclohexyl; R2 is C1-C4-alkyl or allyl; [·: ·. R 3 is selected from C 1 -C 4 alkyl or allyl; «· · R4 is a statement; • · ·; 25 R5 is methyl or methyl and R12 is used, · «51 100797 for the weight of the form VH, VIII, DC and X o H Ri vA YR '^ rj VII OH R2 Y, hJ <" 5. ci VIII ° 7 R12 vAsJG r3 DC A, s ~ XX 10 • ·:.:: i vilka • «·:.:; substituentema n, X, Rj, R2, Aj, R4, A, R3 and R12 have the meaning given above in each case 2-benzylidenecyclopentanone,.:. 2- (4-chlorobenzylidene) cyclopentanone, • · · * · 1 1 2-benzylidene-3-methylcyclopentanone, 2-benzylidene -5-methylcyclopentanone, 2-benzylidenecyclohexanone, 6'-cyclohexyl-2-benzylidenecyclohexanone, 2-benzylidene-6-methylcyclohexanone, 2-benzylidenecycloheptanone, 2-benzylidene-6,6-dimethylidene-6,6-dimethylidene-6,6-dimethylidene 52 100797 2-Benzylidene-3-methyl-6-isopropyl-cyclohexanone, 2- (4-fluorobenzylidene) -3-methyl-6-isopropyl-cyclohexanone, 2- (4-chlorobenzylidene) -3-methyl-6-isopropyl- cyclohexanone, 2- (4-bromobenzylidene) -3-methyl-6-isopropyl-cyclohexanone, 5 2- (4-cyano benzylidene) -3-methyl-6-isopropyl-cyclohexanone, 2- (4-phenylbenzylidene) -3-methyl-6-isopropyl-cyclohexanone, 2- (4-fluorobenzylidene) -cyclohexanone, 2- (4-chlorobenzylidene) -cyclohexanone , 2- (4-bromobenzylidene) -cyclohexanone, 2- (4-cyanobenzylidene) -cyclohexanone, 2- (4-phenylbenzylidene) -cyclohexanone, 2- (4-chlorobenzylidene) -cyclohexanone, 2- (2,6- diklorbensyliden) -cyklohexanon. • · • · · • · · • · · ♦ · · • · · · · · c. • · · • · c • · · 1 · · • · · • ·