TW201930316A - Heterocyclic benzosultams and analogues - Google Patents

Abstract

The present disclosure relates to fungicidal active compounds, more specifically to heterocyclic benzosultams and analogues thereof, processes and, intermediates for their preparation and use thereof as fungicidal active compound, particularly in the form of fungicide compositions. The present disclosure also relates to methods for the control of phytopathogenic fungi of plants using these compounds or compositions comprising thereof.

Description

Heterocyclic benzene sulfonamide and the like

The present invention relates to fungicidal active compounds, more particularly to benzene sulfonamide and analogs thereof, to methods and intermediates therefor, and to fungicidal active compounds, especially fungicides Use of the composition form. The invention also relates to methods of using such compounds or compositions comprising the same to control phytopathogenic fungi.

Compounds containing nitrogen heterocycles are known to be useful as crop protection agents against or against microbial infections. For example, JP 2014/221747 and JP 2008/088139 disclose substituted quinoline derivatives useful as fungicides. JP 2017/001998 discloses other substituted quinoline derivatives which are useful as fungicides. In particular, JP 2017/001998 discloses 1,4-benzothiazin-1,3-dione or 1,4-benzothiazine-1,1 having a 3-position bonded to a quinoline ring, a compound of 3-trione ring. However, it does not disclose a compound having a heterocyclic ring containing two fused heterocyclic rings bonded to the 3-position of the quinoline ring. Therefore, the compounds disclosed in JP 2017/001998 are not only the isomers of the compounds of the present invention.

A variety of fungicides have been developed to date. However, there is still a need to develop novel fungicidal compounds per se in order to provide compounds that are effective against broad spectrum fungi, have lower toxicity, have higher selectivity, and are used at lower dosage rates, thereby reducing or avoiding adverse environmental or toxicological effects. At the same time, effective pest control is still allowed. Novel compounds may also be required to prevent fungicide resistance.

The present invention provides novel fungicidal compounds having advantages over known compounds and compositions in at least some of these aspects.

The present invention relates to a compound of formula (I) as described in the scope of the patent application and as disclosed herein, comprising a composition thereof for use as a fungicide and a process for its manufacture.

Accordingly, the present invention provides a heterocyclic benzenesulfonamide and analogs thereof as described below, which are useful as microbicides, preferably as fungicides.

Active ingredient The present invention provides a compound of formula (I)

Wherein A is a 5- or 6-membered unsaturated heterocyclic ring comprising 1, 2 or 3 heteroatoms independently selected from the list consisting of N, O and S;
● Group Z is selected from the group consisting of: a hydrogen atom, a halogen atom, C ₁ -C ₈ alkyl group, may contain up to 9 identical or different halogen atoms C ₁ -C ₈ haloalkyl, C ₂ -C ₈ alkenyl a C ₂ -C ₈ haloalkenyl group, a C ₂ -C ₈ alkynyl group containing up to 9 halogen atoms which may be the same or different, and a C ₂ -C ₈ halogen containing up to 9 halogen atoms which may be the same or different Generation alkynyl, C ₃ -C ₇ cycloalkyl, C _4- C ₇ cycloalkenyl, hydroxy, C ₁ -C ₈ alkoxy group, may contain up to 9 identical or different halogen atoms C ₁ -C ₈ Haloalkoxy, aryl, heterocyclic, indolyl, C ₁ -C ₈ alkylcarbonyl, (hydroxyimino) C ₁ -C ₈ alkyl, (C ₁ -C ₈ alkoxyimino) a C ₁ -C ₈ alkyl group, a carboxyl group, a C ₁ -C ₈ alkoxycarbonyl group, an amine carbenyl group, a C ₁ -C ₈ alkylamine carbenyl group, a di C ₁ -C ₈ alkylamine carbenyl group, Amino, C ₁ -C ₈ alkylamino, di C ₁ -C ₈ alkylamino, thiol, C ₁ -C ₈ alkyl thiol, C ₁ -C ₈ alkyl sulfinyl a C ₁ -C ₈ alkylsulfonyl group, a C ₁ -C ₆ trialkylsulfonyl group, a cyano group and a nitro group, wherein each of Z is optionally substituted;
● n is 0, 1, 2 or 3;
● X is independently selected from the lines of the group consisting of: a halogen atom, C ₁ -C ₈ alkyl group, may contain up to 9 identical or different halogen atoms C ₁ -C ₈ -haloalkyl, C ₂ -C ₈ alkenyl group a C ₂ -C ₈ haloalkenyl group, a C ₂ -C ₈ alkynyl group containing up to 9 halogen atoms which may be the same or different, a C ₂ -C ₈ halogenated group containing up to 9 halogen atoms which may be the same or different alkynyl group, C ₃ -C ₇ cycloalkyl group, comprising up to 9 identical or different halogen atoms of C ₃ -C ₇ halocycloalkyl, C ₃ -C ₇ cycloalkyl, -C ₁ -C ₈ alkyl a C ₄ -C ₇ cycloalkenyl group, a hydroxyl group, a C ₁ -C ₈ alkoxy group, a C ₁ -C ₈ haloalkoxy group, an aryl group, an aryl group-C containing up to 9 halogen atoms which may be the same or different ₁ -C ₈ alkyl, heterocyclyl, heterocyclyl -C ₁ -C ₈ alkyl, methyl acyl, C ₁ -C ₈ alkylcarbonyl group, containing up to C 9 can be the same or different halogen atoms ₁ -C ₈ haloalkylcarbonyl, (hydroxyimino) C ₁ -C ₈ alkyl, (C ₁ -C ₈ alkoxyimino) C ₁ -C ₈ alkyl, carboxyl, C ₁ -C ₈ alkane Oxycarbonyl group, C ₁ -C ₈ haloalkoxycarbonyl group containing at most 9 halogen atoms which may be the same or different, amine mercapto group, C ₁ -C ₈ alkylamine methyl sulfonyl, di C ₁ -C ₈ alkylamine carbhydryl, amine, C ₁ -C ₈ alkylamino, di C ₁ -C ₈ alkylamino, thiol, C mercapto ₁ -C ₈ alkyl, C ₁ -C ₈ alkylsulfinyl acyl, C ₁ -C ₈ alkylsulfonyl group, C ₁ -C ₆ trialkyl silicon based, C ₁ -C ₆ three An alkylthio-C ₁ -C ₆ alkyl group, a cyano group and a nitro group, wherein each of X is optionally substituted;
● W is CY ¹ or N, where:
- Y ¹ is selected from the group consisting of: a hydrogen atom, a halogen atom, C ₁ -C ₈ alkyl group, may contain up to 9 identical or different halogen atoms C ₁ -C ₈ -haloalkyl, C ₂ -C ₈ alkenyl a C ₂ -C ₈ haloalkenyl group, a C ₂ -C ₈ alkynyl group containing up to 9 halogen atoms which may be the same or different, and a C ₂ -C ₈ halogen containing up to 9 halogen atoms which may be the same or different Generation alkynyl, C ₃ -C ₇ cycloalkyl, C ₄ -C ₇ cycloalkenyl, hydroxy, C ₁ -C ₈ alkoxy group, may contain up to 9 identical or different halogen atoms C ₁ -C ₈ Haloalkoxy, aryl, heterocyclic, indolyl, C ₁ -C ₈ alkylcarbonyl, (hydroxyimino) C ₁ -C ₈ alkyl, carboxy, (C ₁ -C ₈ alkoxy Amino)C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxycarbonyl, aminecarbamyl, C ₁ -C ₈ alkylaminecarbamyl, di C ₁ -C ₈ alkylaminecarbamyl, Amino, C ₁ -C ₈ alkylamino, di C ₁ -C ₈ alkylamino, thiol, C ₁ -C ₈ alkyl thiol, C ₁ -C ₈ alkyl sulfinyl a C ₁ -C ₈ alkylsulfonyl group, a C ₁ -C ₆ trialkylsulfonyl group, a cyano group and a nitro group, wherein each of Y is optionally substituted;
^{● Y 2, Y 3, Y} 4 and Y ⁵ are independently selected from the system consisting of the group consisting of: a hydrogen atom, a halogen atom, C ₁ -C ₈ alkyl group, containing up to C 9 can be the same or different halogen atoms ₁ -C ₈ haloalkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ haloalkenyl, C ₂ -C ₈ alkynyl containing up to 9 halogen atoms which may be the same or different, containing up to 9 may be the same Or a different halogen atom of C ₂ -C ₈ haloalkynyl, C ₃ -C ₇ cycloalkyl, C ₄ -C ₇ cycloalkenyl, hydroxy, C ₁ -C ₈ alkoxy, containing up to 9 identical or different halogen atoms C ₁ -C ₈ haloalkoxy group, an aryl group, a heterocyclic group, carboxylic acyl, C ₁ -C ₈ alkylcarbonyl group, (hydroxyimino) C ₁ -C ₈ alkyl, Carboxyl group, (C ₁ -C ₈ alkoxyimino)C ₁ -C ₈ alkyl group, C ₁ -C ₈ alkoxycarbonyl group, amine carbenyl group, C ₁ -C ₈ alkylamine carbenyl group, two C ₁ -C ₈ alkylaminecarbamyl, amine, C ₁ -C ₈ alkylamino, di C ₁ -C ₈ alkylamino, thiol, C ₁ -C ₈ alkyl thiol , C ₁ -C ₈ alkylsulfinyl, C ₁ -C ₈ alkylsulfonyl, C ₁ -C ₆ trialkylindolyl, cyano and nitro, wherein each of Y is optionally Replace
● L ¹ is CR ^1a R ^1b , where:
- R ^1a and R ^1b are independently selected from the group consisting of a hydrogen atom, a halogen atom, a C ₁ -C ₈ alkyl group, a C ₁ -C ₈ haloalkyl group containing up to 9 halogen atoms which may be the same or different, C ₂ -C ₈ alkenyl group, may contain up to 9 identical or different halogen atoms C ₂ -C ₈ haloalkenyl, C ₂ -C ₈ alkynyl group, may contain up to 9 identical or different halogen atoms halo C ₂ -C ₈ alkynyl, C ₃ -C ₇ cycloalkyl group, comprising up to 9 identical or different halogen atoms of C ₃ -C ₇ halocycloalkyl, C ₃ -C ₇ cycloalkyl -C ₁ -C ₈ alkyl, aryl, aryl-C ₁ -C ₈ alkyl, heterocyclic, heterocyclyl-C ₁ -C ₈ alkyl, hydroxy, C ₁ -C ₈ alkoxy and a C ₁ -C ₈ haloalkoxy group containing up to 9 halogen atoms which may be the same or different, wherein each of R ^1a and R ^1b is optionally substituted, or
- R ^1a and R ^1b together with the carbon atom to which they are attached form a 3 member, 4 member, 5 member or 6 membered saturated or partially saturated optionally substituted carbocyclic or heterocyclic ring comprising at least one selected from the group consisting of N a hetero atom of the list of O and S, or
- R ^1a and R ^1b together with the carbon atom to which they are attached form an unsubstituted or substituted saturated or partially unsaturated bicyclo[m ¹ , m ² ,0]-C ₆ -C ₁₁ alkyl group, wherein m ² ≥ 1 and m ¹ + m ² = 4 to 9, or
- R ^1a and R ^1b together with the carbon atoms they are attached together form the unsubstituted or substituted saturated or partially unsaturated bicyclic heteroaryl ^{[m 1, m 2, 0} ] -C 6 -C 11 alkyl group, which comprises 1 to 4 heteroatoms independently selected from the list consisting of N, O and S, wherein m ² ≥ 1 and m ¹ + m ² = 4 to 9, or
- R ^1a and R ^1b together with the carbon atom to which they are attached form an unsubstituted or substituted saturated or partially unsaturated spiro[n ¹ ,n ² ]-C ₅ -C ₁₁ alkyl group, wherein n ¹ ≥ 2 And n ¹ + n ² = 4 to 10, or
- R ^1a and R ^1b together with the carbon atom to which they are attached form an unsubstituted or substituted saturated or partially unsaturated heterospiro[n ¹ ,n ² ]-C ₅ -C ₁₁ alkyl group, which comprises 1 to 4 heteroatoms independently selected from the list consisting of N, O and S, wherein n ¹ ≥ 2 and n ¹ + n ² = 4 to 10, or
- R ^1a and R ^1b together with the carbon atom to which they are attached form an unsubstituted or substituted methylene group;
● L ² is a direct key, CR ^2a R ^2b or C(=O), where
- R ^2a and R ^2b are independently selected from the group consisting of a hydrogen atom, a halogen atom, a C ₁ -C ₈ alkyl group, a C ₁ -C ₈ haloalkyl group containing up to 9 halogen atoms which may be the same or different, C ₂ -C ₈ alkenyl group, may contain up to 9 identical or different halogen atoms C ₂ -C ₈ haloalkenyl, C ₂ -C ₈ alkynyl group, may contain up to 9 identical or different halogen atoms halo C ₂ -C ₈ alkynyl, C ₃ -C ₇ cycloalkyl group, comprising up to 9 identical or different halogen atoms of C ₃ -C ₇ halocycloalkyl, C ₃ -C ₇ cycloalkyl -C ₁ -C ₈ alkyl, aryl, aryl-C ₁ -C ₈ alkyl, heterocyclic, heterocyclyl-C ₁ -C ₈ alkyl, hydroxy, C ₁ -C ₈ alkoxy, It may contain up to 9 identical or different halogen atoms C ₁ -C ₈ haloalkoxy, C ₂ -C ₈ alkenyl group, may contain up to 9 identical or different halogen atoms C ₂ -C ₈ haloalkenyl An oxy group, a C ₃ -C ₈ alkynyloxy group, a C ₃ -C ₈ haloalkynyloxy group containing up to 9 halogen atoms which may be the same or different, a C ₃ -C ₇ cycloalkoxy group, containing up to 9 C of the same or different halogen atoms, haloalkoxy of ₃ -C ₇ cycloalkoxy, C ₃ -C ₇ cycloalkyl, -C ₁ -C ₈ alkyl Group, an aryloxy group, an aryl group -C ₁ -C ₈ alkoxy, heterocyclyloxy, heterocyclyl -C ₁ -C ₈ alkoxy and contains 1 to 5 substituents independently selected from the group consisting of N, O and a partially saturated or unsaturated fused bicyclic 9 member, 10 member or 11 membered heterocyclyl-C ₁ -C ₈ alkoxy group of the list of S constituents, wherein each of R ^2a and R ^2b is optionally Replace, or
- R ^2a and R ^2b together with the carbon atom to which they are attached form an unsubstituted or substituted 3, 4, 5 or 6 membered saturated or partially saturated carbocyclic or heterocyclic ring comprising at least one selected a heteroatom of a list of free N, O and S, or
- R ^2a and R ^2b together with the carbon atom to which they are attached form an unsubstituted or substituted saturated or partially unsaturated bicyclo[m ¹ , m ² ,0]-C ₆ -C ₁₁ alkyl group, wherein m ² ≥1 and m ¹ + m ² = 4 to 9, or
- R ^2a and R ^2b together with the carbon atoms they are attached together form the unsubstituted or substituted saturated or partially unsaturated bicyclic heteroaryl ^{[m 1, m 2, 0} ] -C 6 -C 11 alkyl group, which comprises 1 to 4 heteroatoms independently selected from the list consisting of N, O and S, wherein m ² ≥ 1 and m ¹ + m ² = 4 to 9, or
- R ^2a and R ^2b together with the carbon atom to which they are attached form an unsubstituted or substituted saturated or partially unsaturated spiro[n ¹ ,n ² ]-C ₅ -C ₁₁ alkyl group, wherein n ¹ ≥ 2 And n ¹ + n ² = 4 to 10, or
- R ^2a and R ^2b together with the carbon atom to which they are attached form an unsubstituted or substituted saturated or partially unsaturated heterospiro[n ¹ ,n ² ]-C ₅ -C ₁₁ alkyl group, which comprises 1 to 4 heteroatoms independently selected from the list consisting of N, O and S, wherein n ¹ ≥ 2 and n ¹ + n ² = 4 to 10, or
- R ^2a and R ^2b together with the carbon atom to which they are attached form an unsubstituted or substituted methylene group;
And salts thereof, N-oxides, metal complexes, metalloid complexes, and optically active isomers or geometric isomers.

As used herein, when a variable (eg, X, Y ¹ , Y ² , Y ³ , Y ⁴ , Y ^{5 ,} or Z) is referred to as "optionally substituted," it should be understood that this variable applies to a moiety containing a carbon-hydrogen bond. Wherein a hydrogen atom is substituted with a corresponding substituent and is not suitable for a moiety such as hydrogen, halogen, CN or the like. The variables may be substituted by one or more substituents which may be the same or different. The expression "one or more substituents" refers to a plurality of substituents within a range of one to a plurality of substituents, possibly based on the number of available bonding sites, subject to conditions that satisfy stability and chemical feasibility. . The one or more substituents of the substitution variable may be independently selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a cyano group, an amine group, a thio group, a pentafluoro-λ ⁶ -thio group, a fluorenyl group. , amidyl, urethane, C ₁ -C ₈ alkyl, tri(C ₁ -C ₈ alkyl)indenyl, C ₃ -C ₇ cycloalkyl, having 1 to 5 halogen atoms C ₁ -C ₈ haloalkyl, C ₃ -C ₇ halocycloalkyl having 1 to 5 halogen atoms, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, C ₁ -C ₈ alkane amino group, di-C ₁ -C ₈ alkylamino, C ₁ -C ₈ alkoxy group having a C 1 to 5 halogen atoms ₁ -C ₈ haloalkoxy, C ₁ -C ₈ alkylcarbonyl, C ₁ -C ₈ haloalkylcarbonyl group having 1 to 5 halogen atoms, C ₁ -C ₈ alkylamine carbenyl group, di C ₁ -C ₈ alkylamine carbenyl group, C ₁ -C ₈ alkylcarbonyl group having a C 1 to 5 halogen atoms, haloalkoxy of ₁ -C ₈ alkoxycarbonyl, C ₁ -C ₈ alkylcarbonyloxy group having a C 1 to 5 halogen atoms, haloalkyl of ₁ -C ₈ alkylcarbonyloxy, C ₁ -C ₈ alkylcarbonyl group having a C 1 to 5 halogen atoms, haloalkyl of ₁ -C ₈ alkylcarbonyl group, C ₁ -C ₈ alkyl mercapto having 1 to 5 halogen atoms Haloalkyl of C ₁ -C ₈ alkylthio, C ₁ -C ₈ alkylsulfinyl acyl having a C 1 to 5 halogen atoms, haloalkyl of ₁ -C ₈ alkylsulfinyl acyl, C ₁ -C ₈ alkyl A sulfonyl group and a C ₁ -C ₈ haloalkylsulfonyl group having 1 to 5 halogen atoms.

As used herein, halogen means fluorine, chlorine, bromine or iodine; formazan means -C(=O)H; carboxyl means -C(=O)OH; carbonyl means -C(=O)-; Aminomethylidene means -C(=O)NH ₂ ; trifluoromethanesulfonyl means -SO ₂ -CF ₃ ; SO means an anthracene group; SO ₂ means an anthracene group; a hetero atom means sulfur, Nitrogen or oxygen; methylene means a divalent group = CH ₂ ; aryl usually means phenyl or naphthyl.

The term "heterocyclyl" as used in the expression "unsubstituted or substituted heterocyclic group", unless otherwise provided, means an unsaturated, saturated or partially saturated 5- to 7-membered ring, preferably 5 members. A 6-membered ring comprising from 1 to 4 heteroatoms independently selected from the list consisting of N, O and S. The term "heterocyclyl" as used herein encompasses a heteroaryl group.

The term "member" as used herein, for example, in the expression "5 to 7 member ring" or "9 member, 10 member or 11 member heterocyclic ring" means the number of skeleton atoms constituting the ring.

As used herein, the expression "a 9-membered, 10-membered or 11-membered heterocyclyl ring of a partially saturated or unsaturated fused bicyclic ring" means a thickened saturated ring or two fused unsaturated rings fused to an unsaturated ring. In the double loop system, the double loop system consists of 9 to 11 skeleton atoms.

As used herein, alkyl, alkenyl and alkynyl groups and moieties containing such terms may be straight or branched.

As used herein, the term "carbocycle" means a hydrocarbon ring.

When an amine group or any other amine group containing an amine group is substituted with two substituents which may be the same or different, the two substituents together with the nitrogen atom to which they are attached may form a heterocyclic group, preferably 5 A 7-membered heterocyclic group which may be substituted or may include other heteroatoms such as N-morpholinyl or piperidinyl.

Depending on the number of asymmetric centers in the compound, any of the compounds of the invention may exist in one or more optical or palmical isomer forms. Thus, the present invention is also concerned with optical isomers and racemic or non-racemic mixtures (the term "non-racemic" indicates mixtures of enantiomers in different ratios) and all possibilities in various ratios mixture. Diastereomers and/or optical isomers may be separated according to methods generally known per se to those skilled in the art.

Depending on the number of double bonds in the compound, any of the compounds of the invention may also exist in one or more geometric isomers. Accordingly, the invention is also to all geometric isomers and all possible mixtures in all ratios. Geometric isomers can be separated according to general methods known per se to those skilled in the art.

Depending on the relative position of the substituents of the chain or ring (ipsilateral/reverse or cis/trans), any of the compounds of the invention may also exist in one or more geometric isomers. Thus, the invention is also directed to all ipsilateral/reverse (or cis/trans) isomers and all possible ipsilateral/reverse (or cis/trans) mixtures in all ratios. The ipsilateral/reverse (or cis/trans) isomers can be separated according to the general methods known per se to those skilled in the art.

When the compounds of the invention may exist in tautomeric forms, such compounds are also to be understood above and in the following to include the corresponding tautomeric forms, where appropriate, even in each case without specifically mentioning such tautomerism. The same is true for the form.

The compound of formula (I) is referred to herein as the "active ingredient."

In the above formula (I), Z is preferably selected from the group consisting of a hydrogen atom, a halogen atom, an unsubstituted or substituted C ₁ -C ₆ alkyl group, and contains up to 9 halogen atoms which may be the same or different. the C ₁ -C ₆ haloalkyl, unsubstituted or substituted with of C ₁ -C ₆ alkoxy group, may contain up to 9 identical or different halogen atoms C ₁ -C ₆ haloalkyl alkoxy and cyano, more Preferably, a Z-based hydrogen atom, an unsubstituted or substituted C ₁ -C ₆ alkyl group (for example a methyl group) or a C ₁ -C ₆ haloalkyl group containing up to 9 halogen atoms which may be the same or different, even more Good place, Z series hydrogen atom

In the above formula (I), X is preferably independently selected from the group consisting of a halogen atom, an unsubstituted or substituted C ₁ -C ₆ alkyl group, and containing up to 9 halogen atoms which may be the same or different. C ₁ -C ₆ haloalkyl, unsubstituted or substituted C ₂ -C ₈ alkenyl, unsubstituted or substituted C ₂ -C ₈ alkynyl, unsubstituted or substituted C ₃ -C ₇ cycloalkyl, hydroxy, unsubstituted or substituted with of C ₁ -C ₆ alkoxy group, may contain up to 9 identical or different halogen atoms C ₁ -C ₆ haloalkyl alkoxy, unsubstituted or substituted with the Aryl, unsubstituted or substituted heterocyclic group, unsubstituted or substituted C ₁ -C ₆ alkylcarbonyl, unsubstituted or substituted C ₁ -C ₆ trialkylindenyl-C ₁ -C ₆ alkyl group and unsubstituted or substituted C ₁ -C ₆ trialkyl fluorenyl group, more preferably, X-type halogen atom (chlorine atom, bromine atom or fluorine atom), unsubstituted or substituted C ₁ -C ₆ alkyl (for example methyl), C ₁ -C ₆ haloalkyl (for example trifluoromethyl) containing up to 9 halogen atoms which may be the same or different, unsubstituted or substituted C ₁ - C ₆ alkoxy (e.g. methoxy), The unsubstituted or substituted by C ₁ -C ₆ haloalkoxy (e.g. trifluoromethoxy), or trimethyl silicon based, even more preferably, X is a halogen atom-based (e.g. a chlorine atom, a bromine atom or a fluorine atom), Unsubstituted C ₁ -C ₆ alkyl (for example methyl) or unsubstituted C ₁ -C ₆ alkoxy (for example methoxy).

In the above formula (I), n is preferably 0, 1, 2, more preferably 0 or 1.

In the above formula (I), W is preferably CY ¹ or N, wherein Y ^{1 is} preferably selected from the group consisting of a hydrogen atom, a halogen atom, an unsubstituted or substituted C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group containing up to 9 halogen atoms which may be the same or different, an unsubstituted or substituted C ₃ -C ₇ cycloalkyl group, a hydroxyl group, an unsubstituted or substituted C ₁ -C ₆ Alkoxy, C ₁ -C ₆ haloalkoxy containing up to 9 halogen atoms which may be the same or different, unsubstituted or substituted C ₁ -C ₆ alkoxycarbonyl, methyl ketone and cyano group, more preferably Ground, Y ¹ is a hydrogen atom.

In the above formula (I), W is preferably CY ¹ , wherein Y ^{1 is} selected from the group consisting of a hydrogen atom, a halogen atom, an unsubstituted or substituted C ₁ -C ₆ alkyl group, and contains at most 9 C ₁ -C ₆ haloalkyl which may be the same or different halogen atom, unsubstituted or substituted C ₃ -C ₇ cycloalkyl, hydroxy group, unsubstituted or substituted C ₁ -C ₆ alkoxy group, a C ₁ -C ₆ haloalkoxy group having up to 9 halogen atoms which may be the same or different, an unsubstituted or substituted C ₁ -C ₆ alkoxycarbonyl group, a decyl group and a cyano group, more preferably, Y ¹ Is a hydrogen atom.

In the above formula (I), Y ² , Y ³ , Y ⁴ or Y ^{5 is} preferably independently selected from the group consisting of a hydrogen atom, a halogen atom, an unsubstituted or substituted C ₁ -C ₆ alkyl group. a C ₁ -C ₆ haloalkyl group containing up to 9 halogen atoms which may be the same or different, an unsubstituted or substituted C ₃ -C ₇ cycloalkyl group, a hydroxyl group, an unsubstituted or substituted C ₁ -C ₆ alkoxy group, may contain up to 9 identical or different halogen atoms C ₁ -C ₆ haloalkyl alkoxy, unsubstituted or substituted with of C ₁ -C ₆ alkoxycarbonyl group, a cyano group and acyl methyl, more Preferably, Y ² , Y ³ , Y ⁴ or Y ^{5 is} independently a hydrogen atom, a halogen atom, an unsubstituted or substituted C ₁ -C ₆ alkyl group, and contains up to 9 halogen atoms which may be the same or different. C ₁ -C ₆ haloalkyl (for example, trifluoromethyl) or cyano, even more preferably, Y ² , Y ³ , Y ⁴ or Y ^{5 is} independently a hydrogen atom or a halogen atom. In some embodiments, Y ² , Y ^{3 ,} and Y ⁴ are hydrogen atoms, and Y ⁵ is a hydrogen atom or a halogen atom.

In the above formula (I), R ^1a and R ^1b , or R ^2a and R ^2b together with the carbon atom to which they are attached may form a three-member, four-member, five-member or six-member saturated or partially saturated, as appropriate. A carbocyclic or heterocyclic ring comprising at least one heteroatom selected from the list consisting of N, O and S.

Examples of optionally substituted carbocycles which are saturated or partially saturated with 3, 4, 5 or 6 members include cyclopropyl, cyclopentyl, cyclohexyl, cyclopropenyl, cyclopentenyl and cyclohexenyl. .

Examples of optionally substituted heterocyclic rings of 3, 4, 5 or 6 members which are saturated or partially saturated include oxiranyl, aziridine, tetrahydrofuranyl, tetrahydrothiophenyl, pyrrolidinyl, Hydrofuranyl, dihydrothienyl, pyrrolidinyl, piperidinyl, dioxanyl, tetrahydropyranyl, hexahydropyridazinyl, hexahydropyrimidinyl and piperazinyl.

In the above formula (I), R ^1a and R ^1b , or R ^2a and R ^2b together with the carbon atom to which they are attached may form an unsubstituted or substituted saturated or partially unsaturated bicyclic ring [m ¹ , m ² , 0]-C ₆ -C ₁₁ alkyl, wherein m ² ≥ 1 and m ¹ + m ² = 4 to 9. Examples of such materials include indane and decalin.

In the above formula (I), R ^1a and R ^1b , or R ^2a and R ^2b together with the carbon atom to which they are attached may form an unsubstituted or substituted saturated or partially unsaturated snail [n ¹ , n ² a -C ₅ -C ₁₁ alkyl group comprising from 1 to 4 heteroatoms independently selected from the list consisting of N, O and S, wherein n ¹ ≥ 2 and n ¹ + n ² = 4 to 10. Examples of such materials include spiro[2,2]pentane and spiro[2,3]hexane.

In the above formula (I), R ^1a and R ^1b , or R ^2a and R ^2b together with the carbon atom to which they are attached may form an unsubstituted or substituted saturated or partially unsaturated heterospiro [n ¹ , n ² ]-C ₅ -C ₁₁ alkyl group, which comprises 1 to 4 heteroatoms independently selected from the list consisting of N, O and S, wherein n ¹ ≥ 2 and n ¹ + n ² = 4 to 10. Examples of such materials include 2-oxaspiro[3,3]heptane.

In the above formula (I), R ^1a and R ^{1b are} preferably independently selected from the group consisting of a hydrogen atom, a halogen atom, an unsubstituted or substituted C ₁ -C ₆ alkyl group, unsubstituted or via Substituted C ₂ -C ₆ alkenyl, unsubstituted or substituted C ₂ -C ₆ haloalkenyl, unsubstituted or substituted C ₂ -C ₆ alkynyl, unsubstituted or substituted C _3- C ₇ cycloalkyl, unsubstituted or substituted C ₃ -C ₇ cycloalkyl-C ₁ -C ₆ alkyl, unsubstituted or substituted aryl, unsubstituted or substituted a cyclo-C ₁ -C ₆ alkyl group, an unsubstituted or substituted heterocyclic group, and an unsubstituted or substituted aryl-C ₁ -C ₈ alkyl group, or
R ^1a and R ^1b together with the carbon atom to which they are attached may preferably be preferred
Forming a suitably substituted carbocyclic or heterocyclic ring of 3, 4, 5 or 6 members which is saturated or partially saturated, comprising at least one heteroatom selected from the list consisting of N, O and S, or
- forming an unsubstituted or substituted saturated or partially unsaturated bicyclo[m ¹ , m ² ,0]-C ₆ -C ₁₁ alkyl group, wherein m ² ≥1 and m ¹ + m ² = 4 to 9, or
- forming an unsubstituted or substituted saturated or partially unsaturated heterobicyclo[m ¹ , m ² ,0]-C ₆ -C ₁₁ alkyl group, which comprises from 1 to 4 independently selected from N, O and S a list of heteroatoms, where m ² ≥ 1 and m ¹ + m ² = 4 to 9, or
Forming an unsubstituted or substituted saturated or partially unsaturated spiro[n ¹ ,n ² ]-C ₅ -C ₁₁ alkyl group, wherein n ¹ ≥ 2 and n ¹ + n ² = 4 to 10, or
Forming an unsubstituted or substituted saturated or partially unsaturated heterospiro[n ¹ ,n ² ]-C ₅ -C ₁₁ alkyl group comprising from 1 to 4 independently selected from the group consisting of N, O and S List of heteroatoms where n ¹ ≥ 2 and n ¹ + n ² = 4 to 10.

In the above formula (I), more preferably, R ^1a and R ^1b are each independently a hydrogen atom, an unsubstituted or substituted C ₁ -C ₆ alkyl group (e.g., methyl group), or R ^1a and R ^1b. Forming a substituted, partially saturated, optionally substituted carbocyclic ring (eg, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentenyl), or not, 3, 4, 5, or 6 Substituted or substituted saturated or partially unsaturated spiro[n ¹ ,n ² ]-C ₅ -C ₁₁ alkyl, wherein n ¹ ≥ 2 and n ¹ + n ² = 4 to 10 (eg, spiro[2, 2] pentane).

In the above formula (I), L ^{1 is} preferably CR ^1a R ^1b , wherein R ^1a and R ^{1b are} independently a hydrogen atom or an unsubstituted C ₁ -C ₈ alkyl group.

In the above formula (I), L ^{2 is} preferably C(=O) or CR ^2a R ^2b , wherein R ^2a and R ^{2b are} as described herein.

R ^2a and R ^2b, if present, are preferably independently a hydrogen atom, a halogen atom, a hydroxyl group, an unsubstituted or substituted C ₁ -C ₆ alkoxy group, an unsubstituted or substituted C ₁ -C ₆ Alkyl, unsubstituted or substituted aryl, hydroxy, unsubstituted or substituted C ₂ -C ₈ alkenyloxy, unsubstituted or substituted C ₃ -C ₈ alkynyloxy, unsubstituted Or substituted aryl C ₁ -C ₆ alkoxy, unsubstituted or substituted heterocyclyl-C ₁ -C ₆ alkoxy or consisting of 1 to 5 independently selected from N, O and S An unsubstituted or substituted partially saturated or unsaturated fused bicyclic 9 member, 10 member or 11 membered heterocyclyl-C ₁ -C ₆ alkoxy group of a hetero atom of the list. In some preferred embodiments, R ^2a and R ^2b together with the carbon atom to which they are attached may also form an unsubstituted or substituted methylene group.

Examples of unsubstituted or substituted aryl-C ₁ -C ₆ alkoxy include unsubstituted or substituted phenyl-C ₁ -C ₆ alkoxy, wherein the phenyl group may be selected by one or more the group the group consisting of substituted: the unsubstituted or substituted C ₁ -C ₆ alkyl group, comprising up to 9 halogen atoms may be the same or different C ₁ -C ₆ haloalkyl group, a cyano group, a halogen, Unsubstituted or substituted C ₁ -C ₆ alkylsulfonyl, unsubstituted or substituted C ₁ -C ₆ alkylthio, unsubstituted or substituted aryl (eg phenyl, naphthalene) group), the substituted or unsubstituted arylcarbonyl group, the unsubstituted or substituted C ₁ -C ₆ alkoxy group, may contain up to 9 identical or different halogen atoms C ₁ -C ₆ haloalkyl alkoxy An unsubstituted or substituted aryloxy group and an unsubstituted or substituted aryl-C ₁ -C ₆ alkoxy group, preferably an unsubstituted C ₁ -C ₆ alkyl group, containing up to 9 may be the same or different halogen atoms C ₁ -C ₆ haloalkyl group, halogen, unsubstituted of C ₁ -C ₆ alkoxy and may contain up to 9 identical or different halogen atoms C ₁ -C ₆ haloalkyl alkoxy base.

Examples of the unsubstituted or substituted heterocyclic-C ₁ -C ₆ alkoxy group include unsubstituted or substituted thiazolyl-C ₁ -C ₆ alkoxy group and unsubstituted or substituted furanyl group. -C ₁ -C ₆ alkoxy.

An unsubstituted or substituted partially saturated or unsaturated fused bicyclic 9 member, 10 member or 11 membered heterocyclyl-C ₁ containing from 1 to 5 heteroatoms independently selected from the list consisting of N, O and S Examples of the -C ₆ alkoxy group include an unsubstituted or substituted carbazolyl-C ₁ -C ₆ alkoxy group and an unsubstituted or substituted benzoxazolyl-C ₁ -C ₆ alkoxy group. .

R ^2a and R ^2b, if present, are more preferably independently a hydrogen atom, a halogen atom (e.g., a fluorine atom), a hydroxyl group, an unsubstituted or substituted C ₁ -C ₆ alkyl group (e.g., methyl group), unsubstituted. Or substituted aryl (eg unsubstituted or substituted phenyl), unsubstituted or substituted C ₁ -C ₆ alkoxy (eg methoxy), unsubstituted or substituted aryloxy An unsubstituted or substituted aryl-C ₁ -C ₆ alkoxy group (for example, an unsubstituted or substituted benzyloxy group), an unsubstituted or substituted C ₂ -C ₈ alkenyloxy group (eg allyloxy), unsubstituted or substituted C ₃ -C ₈ alkynyloxy (eg propynyloxy), unsubstituted or substituted aryl-C ₁ -C ₆ alkoxy (for example unsubstituted or substituted phenyl-C ₁ -C ₆ alkoxy or unsubstituted or substituted naphthyl-C ₁ -C ₆ alkoxy), unsubstituted or substituted heterocyclic ring a s-C ₁ -C ₆ alkoxy group, an unsubstituted or substituted partially saturated or unsaturated fused bicyclic 9 member comprising from 1 to 5 heteroatoms independently selected from the list consisting of N, O and S, 10 or 11-membered heterocyclic group -C ₁ -C ₆ alkoxy, or R ^2a and R ^2b connected Form an unsubstituted or substituted methylene group together with the carbon atoms they are attached.

In the above formula (I), L ^{2 is more} preferably CR ^2a R ^2b or C(=O), wherein R ^2a and R ^2b are independently selected from the group consisting of hydrogen atom, halogen atom, unsubstituted or Substituted C ₁ -C ₆ alkyl, hydroxy, unsubstituted or substituted C ₁ -C ₆ alkoxy, unsubstituted or substituted C ₂ -C ₆ alkenoxy, unsubstituted or via Substituted aryl-C ₁ -C ₆ alkoxy group and unsubstituted or substituted heterocyclic group -C ₁ -C ₆ alkoxy group.

In some embodiments, the active ingredient is a compound of formula (I) wherein:
● W is CY ¹ or N, where:
- Y ^{1 is} selected from the group consisting of a hydrogen atom, a halogen atom, an unsubstituted or substituted C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group containing up to 9 halogen atoms which may be the same or different , of unsubstituted or substituted C ₃ -C ₇ cycloalkyl, hydroxy, unsubstituted or substituted with of C ₁ -C ₆ alkoxy group, containing up to C 9 can be the same or different halogen atoms _1-- a C ₆ haloalkoxy group, an unsubstituted or substituted C ₁ -C ₆ alkoxycarbonyl group, a decyl group and a cyano group;
• Y ² , Y ³ , Y ⁴ or Y ⁵ are independently selected from the group consisting of a hydrogen atom, a halogen atom, an unsubstituted or substituted C ₁ -C ₆ alkyl group, containing up to 9 may be the same or C ₁ -C ₆ haloalkyl, unsubstituted or substituted C ₃ -C ₇ cycloalkyl, hydroxy, unsubstituted or substituted C ₁ -C ₆ alkoxy, containing up to 9 a C ₁ -C ₆ haloalkoxy group which may be the same or different halogen atom, an unsubstituted or substituted C ₁ -C ₆ alkoxycarbonyl group, a decyl group and a cyano group;
Z is selected from the group consisting of a hydrogen atom, a halogen atom, an unsubstituted or substituted C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group containing up to 9 halogen atoms which may be the same or different, Unsubstituted or substituted C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy and cyano group containing up to 9 halogen atoms which may be the same or different;
• A, L ¹ , L ² , X, W and n are as defined above.

In the above formula (I), the A group may be selected from the group consisting of pyrrolyl, furyl, thienyl, thiazolyl, isothiazolyl, oxazolyl, imidazolyl, isoxazolyl, pyrazolyl, Triazolyl, thiadiazolyl, oxadiazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl and triazinyl.

In some other embodiments, in Formula (I) above, A is a 5-membered or 6-membered unsaturated heterocyclic ring comprising one or two heteroatoms independently selected from the list consisting of N, O, and S.

In the above formula (I), A is preferably selected from the group consisting of:


Wherein X and n are as defined herein (it should be understood that n cannot exceed the number of available bonding sites), and X ^{a is} selected from the group consisting of C ₁ -C ₈ alkyl, containing up to 9 halogens which may be the same or different atoms C ₁ -C ₈ -haloalkyl, C ₂ -C ₈ alkenyl group, may contain up to 9 identical or different halogen atoms C ₂ -C ₈ haloalkenyl, C ₂ -C ₈ alkynyl group, containing up to 9 may be the same or different halogen atoms C ₂ -C ₈ haloalkynyl, C ₃ -C ₇ cycloalkyl group, comprising up to 9 identical or different halogen atoms of C ₃ -C ₇ halocycloalkyl , C ₃ -C ₇ cycloalkyl-C ₁ -C ₈ alkyl, C ₄ -C ₇ cycloalkenyl, aryl, aryl-C ₁ -C ₈ alkyl, heterocyclyl, heterocyclyl- C ₁ -C ₈ alkyl, methyl acyl, C ₁ -C ₈ alkylcarbonyl group, may contain up to 9 identical or different halogen atoms C ₁ -C ₈ -haloalkylcarbonyl, C ₁ -C ₈ alkoxycarbonyl a C ₁ -C ₈ haloalkoxycarbonyl group, an amine carbenyl group, a C ₁ -C ₈ alkylamine carbenyl group, a di C ₁ -C ₈ alkylamine group containing up to 9 halogen atoms which may be the same or different Sulfhydryl, C ₁ -C ₈ alkylsulfonyl, C ₁ -C ₆ trialkylsulfonyl and C ₁ -C ₆ trialkylsulfonyl-C ₁ -C ₆ Alkyl, and A is linked to L _{2 of} formula (I) via a bond identified by "*", and A is linked to the N-SO ₂ moiety of formula (I) via a bond identified by "#".

In the above formula (I), A may be a pyridyl group or a thienyl group.

In the above formula (I), A is more preferably selected from the group consisting of:

Where X and n are as defined herein (it should be understood that n cannot exceed the number of available bonding sites),
Preferably, n is 0 or 1, and X is selected from the group consisting of hydrogen, halogen, unsubstituted C ₁ -C ₈ alkyl, and unsubstituted C ₁ -C ₈ alkoxy.

In some embodiments, the compound according to the invention is a compound of formula (I)

Wherein A is selected from the group consisting of pyrrolyl, furyl, thienyl, thiazolyl, isothiazolyl, oxazolyl, imidazolyl, isoxazolyl, pyrazolyl, triazolyl, thiadiazolyl , oxadiazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl and triazinyl;
Z is selected from the group consisting of a hydrogen atom, a halogen atom, an unsubstituted or substituted C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group containing up to 9 halogen atoms which may be the same or different, Unsubstituted or substituted C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy and cyano group containing up to 9 halogen atoms which may be the same or different, preferably Z-based hydrogen atom, not a substituted or substituted C ₁ -C ₆ alkyl group (for example, a methyl group) or a C ₁ -C ₆ haloalkyl group containing up to 9 halogen atoms which may be the same or different, more preferably a Z-based hydrogen atom;
● n is 0, 1, 2, preferably 0 or 1;
X is independently selected from the group consisting of a halogen atom, an unsubstituted or substituted C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group containing up to 9 halogen atoms which may be the same or different, Unsubstituted or substituted C ₂ -C ₈ alkenyl, unsubstituted or substituted C ₂ -C ₈ alkynyl, unsubstituted or substituted C ₃ -C ₇ cycloalkyl, hydroxy, unsubstituted the unsubstituted or substituted C ₁ -C ₆ alkoxy group, may contain up to 9 identical or different halogen atoms C ₁ -C ₆ haloalkyl alkoxy, the unsubstituted or substituted aryl group, unsubstituted or Substituted heterocyclic group, unsubstituted or substituted C ₁ -C ₆ alkylcarbonyl group, unsubstituted or substituted C ₁ -C ₆ trialkylindenyl-C ₁ -C ₆ alkyl group and a substituted or substituted C ₁ -C ₆ trialkylsulfonyl group, preferably an X-based halogen atom (a chlorine atom, a bromine atom or a fluorine atom), an unsubstituted or substituted C ₁ -C ₆ alkyl group ( For example, methyl), a C ₁ -C ₆ haloalkyl group (for example, a trifluoromethyl group) containing up to 9 halogen atoms which may be the same or different, an unsubstituted or substituted C ₁ -C ₆ alkoxy group (for example, A) Oxyl), unsubstituted or taken Instead, a C ₁ -C ₆ haloalkoxy group (for example, a trifluoromethoxy group) or a trimethyl fluorenyl group, more preferably, an X-based halogen atom (for example, a chlorine atom, a bromine atom or a fluorine atom), an unsubstituted C _1- C ₆ alkyl (eg methyl) or unsubstituted C ₁ -C ₆ alkoxy (eg methoxy);
• W is CY ¹ or N, wherein Y ^{1 is} selected from the group consisting of a hydrogen atom, a halogen atom, an unsubstituted or substituted C ₁ -C ₆ alkyl group, and contains up to 9 halogen atoms which may be the same or different. C ₁ -C ₆ haloalkyl, unsubstituted or substituted C ₃ -C ₇ cycloalkyl, hydroxy, unsubstituted or substituted C ₁ -C ₆ alkoxy, containing up to 9 may be the same or a C ₁ -C ₆ haloalkoxy group having an unsubstituted halogen atom, an unsubstituted or substituted C ₁ -C ₆ alkoxycarbonyl group, a decyl group and a cyano group, preferably a Y ¹ -based hydrogen atom;
• Y ² , Y ³ , Y ⁴ and Y ⁵ are independently selected from the group consisting of a hydrogen atom, a halogen atom, an unsubstituted or substituted C ₁ -C ₆ alkyl group, containing up to 9 may be the same or C ₁ -C ₆ haloalkyl, unsubstituted or substituted C ₃ -C ₇ cycloalkyl, hydroxy, unsubstituted or substituted C ₁ -C ₆ alkoxy, containing up to 9 a C ₁ -C ₆ haloalkoxy group which may be the same or different halogen atom, an unsubstituted or substituted C ₁ -C ₆ alkoxycarbonyl group, a decyl group and a cyano group, preferably, Y ² , Y ³ And Y ⁴ and Y ^{5 are} independently a hydrogen atom, a halogen atom, an unsubstituted or substituted C ₁ -C ₆ alkyl group, and a C ₁ -C ₆ haloalkyl group containing up to 9 halogen atoms which may be the same or different ( For example, trifluoromethyl) or cyano, more preferably, Y ² , Y ³ , Y ⁴ and Y ^{5 are} independently a hydrogen atom or a halogen atom;
L ¹ is CR ^1a R ^1b , wherein R ^1a and R ^{1b are} independently a hydrogen atom or an unsubstituted C ₁ -C ₈ alkyl group;
• L ² is CR ^2a R ^2b or C(=O), wherein R ^2a and R ^2b are independently selected from the group consisting of a hydrogen atom, a halogen atom, an unsubstituted or substituted C ₁ -C ₆ alkane Alkyl, hydroxy, unsubstituted or substituted C ₁ -C ₆ alkoxy, unsubstituted or substituted C ₂ -C ₆ alkenyloxy, unsubstituted or substituted aryl-C ₁ -C ₆ alkoxy and unsubstituted or substituted heterocyclic-C ₁ -C ₆ alkoxy.

In some embodiments, the compound according to the invention is a compound of formula (I)

Wherein A is a pyridyl or thienyl group, preferably, A is selected from
;
Z is selected from the group consisting of a hydrogen atom, an unsubstituted or substituted C ₁ -C ₆ alkyl group (such as a methyl group), and a C ₁ -C ₆ haloalkane containing up to 9 halogen atoms which may be the same or different. a base, preferably a Z-based hydrogen atom;
● n is 0 or 1;
X is selected from the group consisting of a halogen atom (for example, a chlorine atom, a bromine atom or a fluorine atom), an unsubstituted or substituted C ₁ -C ₆ alkyl group (for example, a methyl group), containing up to 9 or the same or C ₁ -C ₆ haloalkyl (for example trifluoromethyl), unsubstituted or substituted C ₁ -C ₆ alkoxy (eg methoxy), unsubstituted or substituted C, of a different halogen atom _{a 1-} C ₆ haloalkoxy group (for example, a trifluoromethoxy group) and a trimethyl fluorenyl group, preferably an X-based halogen atom (for example, a chlorine atom, a bromine atom or a fluorine atom), and an unsubstituted C ₁ -C _{a 6} alkyl group (such as a methyl group) or an unsubstituted C ₁ -C ₆ alkoxy group (such as a methoxy group);
• W is CY ¹ , wherein Y ^{1 is} selected from the group consisting of a hydrogen atom, a halogen atom, an unsubstituted or substituted C ₁ -C ₆ alkyl group, and C containing up to 9 halogen atoms which may be the same or different _1- C ₆ haloalkyl, unsubstituted or substituted C ₃ -C ₇ cycloalkyl, hydroxy, unsubstituted or substituted C ₁ -C ₆ alkoxy, containing up to 9 may be the same or different a C ₁ -C ₆ haloalkoxy group of a halogen atom, an unsubstituted or substituted C ₁ -C ₆ alkoxycarbonyl group, a decyl group and a cyano group, preferably a Y ¹ -based hydrogen atom;
• Y ² , Y ³ , Y ⁴ and Y ⁵ are independently selected from the group consisting of a hydrogen atom, a halogen atom, an unsubstituted or substituted C ₁ -C ₆ alkyl group, containing up to 9 may be the same or a C ₁ -C ₆ haloalkyl group (for example, a trifluoromethyl group) and a cyano group of different halogen atoms, preferably, Y ² , Y ³ , Y ⁴ and Y ^{5 are each} independently a hydrogen atom or a halogen atom, more preferably , Y ² , Y ³ and Y ⁴ are hydrogen atoms, and Y ⁵ is a hydrogen atom or a halogen atom;
L ¹ is CR ^1a R ^1b , wherein R ^1a and R ^{1b are} independently a hydrogen atom or an unsubstituted C ₁ -C ₆ alkyl group;
• L ² is CR ^2a R ^2b or C(=O), wherein R ^2a and R ^2b are independently selected from the group consisting of a hydrogen atom, a halogen atom, an unsubstituted or substituted C ₁ -C ₆ alkane Alkyl, hydroxy, unsubstituted or substituted C ₁ -C ₆ alkoxy, unsubstituted or substituted C ₂ -C ₆ alkenyloxy, unsubstituted or substituted aryl-C ₁ -C ₆ alkoxy, and unsubstituted or substituted heterocyclyl group of -C ₁ -C ₆ alkyl;
And salts thereof, N-oxides, metal complexes, metalloid complexes, and optically active isomers or geometric isomers.

In some embodiments, the compound is a compound according to formula (Ii) according to the present invention (i.e., of formula (I) compounds in which line L ² CR ^2a R ^2b, wherein R ^2b based -OR ^2c):

among them
A, n, X, Y ² , Y ³ , Y ⁴ , Y ⁵ , W, Z, L ¹ and R ^{2a are} as defined herein, and
R ^2c is selected from the group consisting of: unsubstituted or substituted with of C ₁ -C ₆ alkyl group, may contain up to 9 identical or different halogen atoms C ₁ -C ₆ haloalkyl group, unsubstituted or substituted the C ₂ -C ₈ alkenyl group, comprising up to 9 halogen atoms may be the same or different C ₂ -C ₆ haloalkenyl group, unsubstituted or substituted with of C ₃ -C ₈ alkynyl group containing up to 9 C may be the same or different halogen atoms ₃ -C ₈ haloalkynyl, unsubstituted or substituted with of C ₃ -C _{cycloalkyl. 7,} comprising up to C 9 can be the same or different halogen atoms ₃ -C ₇ halocycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocyclic, unsubstituted or substituted C ₃ -C ₇ cycloalkyl-C ₁ -C ₈ alkane And unsubstituted or substituted aryl-C ₁ -C ₆ alkyl, unsubstituted or substituted heterocyclyl-C ₁ -C ₆ alkyl and containing from 1 to 5 independently selected from N, Unsubstituted or substituted partially saturated or unsaturated fused bicyclic 9 member, 10 member or 11 membered heterocyclic group -C ₁ -C ₆ alkyl group, or R ^2a and R ^2b together with the carbon atoms they are attached together form an The unsubstituted or substituted alkylene group, preferably, R ^2c is selected from the group consisting of: unsubstituted or substituted with of C ₁ -C ₆ alkyl, unsubstituted or substituted C ₂ -C ₈ alkenyl of a aryl group, an unsubstituted or substituted aryl C ₁ -C ₆ alkyl group, and an unsubstituted or substituted heterocyclic group -C ₁ -C ₆ alkyl group,
And salts thereof, N-oxides, metal complexes, metalloid complexes, and optically active isomers or geometric isomers.

Examples of the unsubstituted or substituted aryl-C ₁ -C ₆ alkyl group include a benzyl group and a phenyl-C ₁ -C ₆ alkyl group, wherein the phenyl group may be selected from the group consisting of one or more selected from the group consisting of substituted groups: unsubstituted or substituted alkyl group of C ₁ -C _6, can comprise up to nine identical or different a halogen atoms C ₁ -C ₆ haloalkyl group, a cyano group, halo, unsubstituted or Substituted C ₁ -C ₆ alkylsulfonyl, unsubstituted or substituted C ₁ -C ₆ alkylthio, unsubstituted or substituted aryl (eg phenyl, naphthyl), unsubstituted the unsubstituted or substituted arylcarbonyl, unsubstituted or substituted with of C ₁ -C ₆ alkoxy group, may contain up to 9 identical or different halogen atoms C ₁ -C ₆ haloalkyl alkoxy, unsubstituted or Substituted aryloxy and unsubstituted or substituted aryl-C ₁ -C ₆ alkoxy, preferably unsubstituted C ₁ -C ₆ alkyl, containing up to 9 which may be the same or different a halogen atoms C ₁ -C ₆ haloalkyl group, halogen, unsubstituted of C ₁ -C ₆ alkoxy group and a C 9 containing up can be the same or different halogen atoms, alkoxy of ₁ -C ₆ haloalkyl group.

Examples of the unsubstituted or substituted heterocyclic-C ₁ -C ₆ alkyl group include a furyl-C ₁ -C ₆ alkyl group wherein the furyl group may be via one or more groups selected from the group consisting of substituted: the unsubstituted or substituted C ₁ -C ₆ alkyl group, may contain up to 9 identical or different halogen atoms C ₁ -C ₆ haloalkyl group, a cyano group, halo, unsubstituted or substituted with the C _1- C ₆ alkylsulfonyl, unsubstituted or substituted C ₁ -C ₆ alkylthio, unsubstituted or substituted aryl (eg phenyl, naphthyl), unsubstituted or via the substituted arylcarbonyl, unsubstituted or substituted with of C ₁ -C ₆ alkoxy group, may contain up to 9 identical or different halogen atoms C ₁ -C ₆ haloalkyl alkoxy, unsubstituted or substituted with the An aryloxy group and an unsubstituted or substituted aryl-C ₁ -C ₆ alkoxy group, preferably an unsubstituted C ₁ -C ₆ alkyl group, containing up to 9 halogen atoms which may be the same or different C ₁ -C ₆ haloalkyl, halo non-substituted C ₁ -C ₆ alkoxy group and a C 9 containing up can be the same or different halogen atoms, alkoxy of ₁ -C ₆ haloalkyl group.

In some embodiments, the compound is a compound according to formula (Ii) according to the present invention (i.e., of formula (I) compounds in which line L ² CR ^2a R ^2b, wherein R ^2b based -OR ^2c):

Wherein A is a pyridyl or thienyl group, preferably, A is selected from
More preferably ;
Z is selected from the group consisting of a hydrogen atom, an unsubstituted or substituted C ₁ -C ₆ alkyl group (such as a methyl group), and a C ₁ -C ₆ haloalkane containing up to 9 halogen atoms which may be the same or different. a base, preferably a Z-based hydrogen atom;
● n is 0 or 1;
X is selected from the group consisting of a halogen atom (for example, a chlorine atom, a bromine atom or a fluorine atom), an unsubstituted or substituted C ₁ -C ₆ alkyl group (for example, a methyl group), containing up to 9 or the same or C ₁ -C ₆ haloalkyl (for example trifluoromethyl), unsubstituted or substituted C ₁ -C ₆ alkoxy (eg methoxy), unsubstituted or substituted C, of a different halogen atom _{a 1-} C ₆ haloalkoxy group (for example, a trifluoromethoxy group) and a trimethyl fluorenyl group, preferably an X-based halogen atom (for example, a chlorine atom, a bromine atom or a fluorine atom), and an unsubstituted C ₁ -C _{a 6} alkyl group (such as a methyl group) or an unsubstituted C ₁ -C ₆ alkoxy group (such as a methoxy group);
• W is CY ¹ , wherein Y ^{1 is} selected from the group consisting of a hydrogen atom, a halogen atom, an unsubstituted or substituted C ₁ -C ₆ alkyl group, and C containing up to 9 halogen atoms which may be the same or different _1- C ₆ haloalkyl, unsubstituted or substituted C ₃ -C ₇ cycloalkyl, hydroxy, unsubstituted or substituted C ₁ -C ₆ alkoxy, containing up to 9 may be the same or different a C ₁ -C ₆ haloalkoxy group of a halogen atom, an unsubstituted or substituted C ₁ -C ₆ alkoxycarbonyl group, a decyl group and a cyano group, preferably a Y ¹ -based hydrogen atom;
• Y ² , Y ³ , Y ⁴ and Y ⁵ are independently selected from the group consisting of a hydrogen atom, a halogen atom, an unsubstituted or substituted C ₁ -C ₆ alkyl group, containing up to 9 may be the same or a C ₁ -C ₆ haloalkyl group (for example, a trifluoromethyl group) and a cyano group of different halogen atoms, preferably, Y ² , Y ³ , Y ⁴ and Y ^{5 are each} independently a hydrogen atom or a halogen atom, more preferably , Y ² , Y ³ and Y ⁴ are hydrogen atoms, and Y ⁵ is a hydrogen atom or a halogen atom;
L ¹ is CR ^1a R ^1b , wherein R ^1a and R ^{1b are} independently a hydrogen atom or a C ₁ -C ₈ alkyl group;
• R ^2a is a C ₁ -C ₈ alkyl group;
● the group consisting of the following composition of R ^2c is selected from: unsubstituted or substituted with of C ₁ -C ₆ alkyl group, may contain up to 9 identical or different halogen atoms C ₁ -C ₆ haloalkyl group, unsubstituted or the substituted C ₂ -C ₈ alkenyl, C may contain up to 9 identical or different halogen atoms ₂ -C ₆ haloalkenyl group, unsubstituted or substituted with of C ₃ -C ₈ alkynyl group, containing up to 9 C may be the same or different halogen atoms ₃ -C ₈ haloalkynyl, unsubstituted or substituted with of C ₃ -C ₇ cycloalkyl group, containing up to C 9 can be the same or different halogen atoms ₃ - C ₇ halocycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocyclic, unsubstituted or substituted C ₃ -C ₇ cycloalkyl-C ₁ -C ₈ Alkyl, unsubstituted or substituted aryl-C ₁ -C ₆ alkyl, unsubstituted or substituted heterocyclyl-C ₁ -C ₆ alkyl and containing from 1 to 5 independently selected from N An unsubstituted or substituted partially saturated or unsaturated fused bicyclic 9 member, 10 member or 11 membered heterocyclyl-C ₁ -C ₆ alkyl group of a hetero atom of the list consisting of O and S, or R ^2a and R ^2b taken together with the carbon atom they are attached The group consisting of substituted or substituted alkylene group, preferably, R ^2c is selected from: unsubstituted or substituted with of C ₁ -C ₆ alkyl, the unsubstituted or substituted C ₂ -C ₈ Alkenyl, unsubstituted or substituted aryl-C ₁ -C ₆ alkyl and unsubstituted or substituted heterocyclyl-C ₁ -C ₆ alkyl,
And salts thereof, N-oxides, metal complexes, metalloid complexes, and optically active isomers or geometric isomers.

Non-limiting examples of R ^2c include any of the R ^2c groups disclosed in Table 1c.

Preferred A, L ¹ , L ² , n, X, W, Y ² , Y ³ , Y ⁴ , Y ⁵ and Z mentioned above may be combined in various ways. Thus, such combinations of preferred features provide a subclass of the compounds according to the invention. Examples of such subclasses of preferred compounds according to the invention are:
a preferred feature of A and one or more preferred features of L ¹ , L ² , n, X, W, Y ² , Y ³ , Y ⁴ , Y ⁵ and Z;
a preferred feature of L ¹ and one or more preferred features of A, L ² , n, X, W, Y ² , Y ³ , Y ⁴ , Y ⁵ and Z;
a preferred feature of L ² and one or more preferred features of A, L ¹ , n, X, W, Y ² , Y ³ , Y ⁴ , Y ⁵ and Z;
a preferred feature of -n and one or more preferred features of A, L ¹ , L ² , X, W, Y ² , Y ³ , Y ⁴ , Y ⁵ and Z;
a preferred feature of X and one or more preferred features of A, L ¹ , L ² , n, W, Y ² , Y ³ , Y ⁴ , Y ⁵ and Z;
a preferred feature of W and one or more preferred features of A, L ¹ , L ² , n, X, Y ² , Y ³ , Y ⁴ , Y ⁵ and Z;
a preferred feature of Y ² and one or more preferred features of A, L ¹ , L ² , n, X, W, Y ³ , Y ⁴ , Y ⁵ and Z;
a preferred feature of Y ³ and one or more preferred features of A, L ¹ , L ² , n, X, W, Y ² , Y ⁴ , Y ⁵ and Z;
- Y ⁴ and wherein the preferred ^{A, L 1, L 2,} n, X, W, Y 2, Y 3, Y 5 and one or more of the preferred features of Z;
- Y ⁵ and wherein the preferred ^{A, L 1, L 2,} n, X, W, Y 2, Y 3, Y 4 and one or more of the preferred features of Z;
- a preferred feature of Z and one or more preferred features of A, L ¹ , L ² , n, X, W, Y ² , Y ³ , Y ⁴ and Y ⁵ .

In such combinations of preferred features of the substituents of the compounds of the invention, such preferred features may also be selected from the group consisting of A, L ¹ , L ² , n, X, W, Y ² , Y ³ , Y ⁴ , Y The preferred features of each of ⁵ and Z are such that a preferred subclass of the compound according to the invention is formed.

Process for the preparation of active ingredients The invention also relates to a process for the preparation of a compound of formula (I).

Unless otherwise indicated, A, Z, n, X, W, Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , L ¹ , L ² , R ^1a , R ^2a , R ^1b , R ^2b have the above The meaning given for the compound of formula (I). These definitions apply not only to the final product of formula (I) but also to all intermediates.

The compounds of formula (Ia) - (I) are a plurality of subgroups of formula (I). Unless otherwise stated, all substituents of formula (Ia) - (I) are as defined above for formula (I).

Compounds of formula (I) can be prepared by a variety of routes analogous to known methods (see, for example, the references therein). Non-limiting examples of suitable methods are described herein.

Compounds of formula (I) may be obtained directly by carrying out process P1, P3, P5 or P8, or may be obtained by conversion or derivatization of another compound of formula (I) prepared according to the methods described herein. For example, a compound of formula (I) can be converted to another compound of formula (I) by substituting one or more substituents of the starting compound of formula (I) with another substituent. Non-limiting examples of such transformations or derivatives are described below (Methods P6, P7, P11, P12).

One of the compounds of formula (I), or a salt thereof, as defined herein, may be prepared by Process P1, which comprises reacting one of the compounds of Formula (II) or a salt thereof with Formula (III) as shown in the following reaction scheme The steps of the compound reaction:

Method P1
Wherein A, n, X, Y ² , Y ³ , Y ⁴ , Y ⁵ , W, Z, L ¹ and L ^{2 are} as defined herein, and U ¹ is a fluorine atom, a bromine atom, a chlorine atom, an iodine atom, A Sulfosyl, toluenesulfonyl, trifluoromethanesulfonyl or boron derivatives, such as acid, Acid ester or trifluoro Potassium salt derivatives.

Process P1 can be carried out in the presence of a transition metal catalyst such as a metal salt or a complex, and optionally in the presence of a ligand; suitably in the presence of a base and, where appropriate, in the presence of a solvent.

Suitable metal derivatives for this purpose are transition metals such as palladium or copper.

For this purpose, suitable palladium salts or complexes are, for example, palladium chloride, palladium acetate, ruthenium (triphenylphosphine) palladium. For this purpose, suitable palladium salts or complexes such as palladium chloride, acetic acid Palladium, ruthenium (triphenylphosphine) palladium (0), bis(dibenzylideneacetone)palladium (0), ginseng (dibenzylideneacetone) dipalladium (0), bis(triphenylphosphine)dichloride Palladium (II), [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride, bis(phenylallyl)palladium(II) chloride, bis(ene) Propyl)-palladium(II) dichloride or [1,1'-bis(di-tert-butylphosphino)ferrocene]palladium(II) chloride.

It is also possible to produce a palladium complex in the reaction mixture by separately adding a palladium salt such as the following to a ligand or a salt: triethylphosphine, tri-tert-butylphosphine, tetrafluoroborate, third, third Butyl hydrazine, tricyclohexylphosphine, 2-(bicyclohexylphosphino)biphenyl, 2-(di-tert-butylphosphine)biphenyl, 2-(dicyclohexylphosphino)-2'- (N,N-dimethylamino)biphenyl, 2-(t-butylphosphino)-2'-(N,N-dimethylamino)biphenyl, 2-di-t-butylphosphine-2 ',4',6'-Triisopropylbiphenyl, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, 2-dicyclohexylphosphino-2,6 '-Dimethoxybiphenyl, 2-dicyclohexylphosphino-2',6'-diisopropoxybiphenyl, tert-triphenyl-phosphine, gins-(o-tolyl)phosphine, 3-(two Sodium phenylphosphine), benzene-2-(methoxy-phenyl)phosphine, 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, 1,4-double ( Diphenylphosphino)butane, 1,2-bis(diphenylphosphino)ethane, 1,4-bis(bicyclohexylphosphino)butane, 1,2-bis(bicyclohexylphosphino) - ethane, 2-(bicyclohexylphosphino)-2'-(N,N-dimethylamino)-biphenyl, 1,1'-bis(diphenylphosphino)-ferrocene, (R)-(-)-1-[(S)-2-diphenylphosphino)ferrocenyl]ethylbicyclohexane Phosphine, ginseng-(2,4-t-butyl-phenyl)phosphite, bis(1-adamantyl)-2-morpholinylphenylphosphine or 1,3-bis(2,4) , 6-trimethylphenyl)imidazolium.

It is also preferred to select a suitable catalyst and/or ligand from a commercial catalog (such as "Metal Catalysts for Organic Synthesis" by Strem Chemicals) or "Phosphorous Ligands and Compounds" by Strem Chemicals.

Suitable copper salts or complexes and hydrates thereof for this purpose are, for example: copper metal, iodide for this purpose, suitable copper salts or complexes and hydrates thereof such as copper metal, iodine Cuprous (I), cuprous chloride (I), cuprous bromide (I), copper (II) chloride, copper (II) bromide, copper (II) oxide, cuprous oxide (I), Copper (II) acetate, copper (I) acetate, copper (I) thiophene-2-carboxylate, copper (I) cyanide, copper (II) sulfate, double (2,2,6,6-tetramethyl) Base-3,5-heptanedionate) copper (II), copper (II) trifluoromethanesulfonate, copper (I) hexafluorophosphate (acetonitrile), bismuth tetrafluoroborate (acetonitrile) copper (I ).

It is also possible to produce a copper complex in the reaction mixture by separately adding a copper salt such as the following and a ligand or salt to the reaction: ethylenediamine, N,N-dimethylethylenediamine, N,N' - dimethylethylenediamine, racemic-trans-1,2-diaminocyclohexane, racemic-trans-N,N'-dimethylcyclohexane-1,2-di Amine, 1,1'-binaphthyl-2,2'-diamine, N,N,N',N'-tetramethylethylenediamine, valine acid, N,N-dimethylglycine, Quinoline-8-ol, pyridine, 2-aminopyridine, 4-(dimethylamino)pyridine, 2,2'-bipyridine, 2,6-bis(2-pyridyl)pyridine, 2-picolinic acid , 2-(dimethylaminomethyl)-3-hydroxypyridine, 1,10-morpholine, 3,4,7,8-tetramethyl-1,10-morpholine, 2,9-dimethyl -1,10-morpholine, 4,7-dimethoxy-1,10-morpholine, N,N'-bis[(E)-pyridin-2-ylmethylene]cyclohexane-1, 2-diamine, N-[(E)-phenylmethylene], N-[(E)-phenylmethylene]-cyclohexylamine, 1,1,1-paraxyl (hydroxymethyl) Alkane, ethylene glycol, 2,2,6,6-tetramethylheptane-3,5-dione, 2-(2,2-dimethylpropenyl)cyclohexanone, etidylacetone, Diphenylmethylmethane, 2-(2-methylpropenyl)cyclohexanone, biphenyl-2-yl(di-tert-butyl)phosphine, extens Ethyl bis-(diphenylphosphine), N,N-diethyl salicylamine, 2-hydroxybenzaldehyde oxime, pendant oxy[(2,4,6-trimethylphenyl)amino] Acetic acid or 1H-pyrrole-2-carboxylic acid.

It is also appropriate to select an appropriate one from a commercial catalog (such as "Metal Catalysts for Organic Synthesis" by Strem Chemicals) or a review (Chemical Society Reviews (2014), 43 , 3525; Coordination Chemistry Reviews (2004), 248 , 2337 and references therein). Catalyst and / or ligand.

Suitable bases for carrying out process P1 are the inorganic bases and organic bases customary for such reactions. Preferably, an alkaline earth metal or an alkali metal hydroxide such as sodium hydroxide, calcium hydroxide, potassium hydroxide or other ammonium hydroxide derivative; an alkaline earth metal, an alkali metal or ammonium fluoride such as potassium fluoride or fluorine is preferably used. Barium oxide or tetrabutylammonium fluoride; alkaline earth metal or alkali metal carbonate such as sodium carbonate, potassium carbonate, potassium hydrogencarbonate, sodium hydrogencarbonate or barium carbonate; alkali metal or alkaline earth metal acetate such as sodium acetate, acetic acid Lithium, potassium acetate or calcium acetate; alkali metal alkoxides such as potassium butoxide or sodium butoxide; alkali metal phosphates such as tripotassium phosphate; tertiary amines such as trimethylamine, triethylamine, tributyl Amine, N,N-dimethylaniline, N,N-dicyclohexylmethylamine, N,N-diisopropylethylamine, N-methylpiperidine, N,N-dimethylaminopyridine, two Azabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU); and aromatic bases such as pyridine, picoline, lutidine or tri Methyl pyridine.

The solvent suitable for carrying out the process P1 may be a conventional inert organic solvent. It is preferred to use halogenated, aliphatic, alicyclic or aromatic hydrocarbons as appropriate, such as petroleum ether, pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decahydro Naphthalene; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane or trichloroethane; ethers such as diethyl ether, diisopropyl ether, methyl third Butyl ether, methyl tertiary amyl ether, dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; Nitrile such as acetonitrile, propionitrile, n-butyronitrile or isobutyronitrile or benzonitrile; decylamine such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl Toluene aniline, N-methylpyrrolidone or hexamethylphosphonium triamine; urea, such as 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone; An ester such as methyl acetate or ethyl acetate; an anthracene such as dimethyl hydrazine; or an anthracene such as cyclobutyl hydrazine; and mixtures thereof.

Process P1 can be carried out in an inert atmosphere such as an argon or nitrogen atmosphere. When the method P1 is carried out, a compound of the formula (III) and a base of 1 to 5 moles per mole of the compound of the formula (II) can be used. When a palladium salt or a complex is used, a palladium complex of 0.01 to 20 mole percent may be employed per mole of the compound of the formula (II). When a copper salt or a complex is used, a copper complex of 0.01 to 200 mole percent can be used per mole of the compound of the formula (II). It is also possible to use other ratios of reaction components. Processing is performed by a known method.

One of the derivatives of formula (III) or a salt thereof can be prepared by Process P2 which comprises removing the protecting group of the derivative of formula (IV) as shown in the following reaction scheme:

Method P2
Wherein A, n, X, L ¹ and L ^{2 are} as defined herein, and V represents benzyl, 4-methoxybenzyl, allyl, unsubstituted or substituted C ₁ -C ₆ alkane Alkylsulfonyl (such as trifluoromethanesulfonyl), unsubstituted or substituted benzenesulfonyl (such as tolylsulfonyl), unsubstituted or substituted C ₁ -C ₆ alkoxycarbonyl ( For example, a third butoxycarbonyl group, an unsubstituted or substituted benzyloxycarbonyl group, an allyloxycarbonyl group or a 2-trimethyldecylethoxymethyl group.

The method P2 can be carried out according to a known method of removing a protecting group (Greene's Protective Groups in Organic Synthesis; Peter G. M. Wuts; Wiley; Fifth Edition; 2014; 895-1194). For example, the third butoxycarbonyl protecting group can be removed in an acidic medium (eg, with hydrochloric acid or trifluoroacetic acid). The benzyl and benzyloxycarbonyl protecting groups can be removed by hydrogen in the presence of a catalyst such as palladium on carbon.

The compound of the formula (IV) can be produced according to a known method (The Chemistry of Functional Groups - The Chemistry of sulphonic acids, esters and their derivatives; Saul Patai, Avi Rappoport; Wiley-Interscience; 1991; 851-878).

One of the compounds of formula (I) or a salt thereof as defined herein may be prepared by intermolecular cyclization from one of the compounds of formula (V) or a salt thereof by Method P3 as shown in the following reaction scheme. :

Method P3
Wherein A, n, X, Y ² , Y ³ , Y ⁴ , Y ⁵ , W, Z, L ¹ and L ^{2 are} as defined herein and U ² is a chlorine atom or a fluorine atom.

When appropriate, the method P3 can be carried out in the presence of a base and, where appropriate, in the presence of a solvent, preferably under anhydrous conditions.

The solvent suitable for carrying out the process P3 is not particularly limited. It may be a conventional inert organic solvent as long as it does not dissolve the compound with which it reacts or exhibits any specific interaction therewith. It is preferred to use halogenated, aliphatic, alicyclic or aromatic hydrocarbons as appropriate, such as petroleum ether, pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decahydro naphthalene, ISOPAR ^TM E or ISOPAR ^TM G, chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane or trichloroethane; ethers, such as diethyl ether, diisopropyl Propyl ether, methyl tert-butyl ether, methyl third amyl ether, dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxy Ethyl or anisole; nitrile such as acetonitrile, propionitrile, n-butyronitrile or isobutyronitrile or benzonitrile; decylamine such as N,N-dimethylformamide, N,N-dimethyl Acetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphonium triamine; urea, such as 1,3-dimethyl-3,4,5,6-tetrahydro- 2(1 H )-pyrimidinone; an ester such as methyl acetate or ethyl acetate; an anthracene such as dimethyl hydrazine; or an anthracene such as cyclobutyl hydrazine; and mixtures thereof.

Suitable bases for carrying out process P3 may be inorganic and organic bases customary for such reactions, such as the bases disclosed in relation to process P1. Other bases suitable for carrying out the process P3 according to the invention may be indoleamine or organometallic derivatives. Preferred are alkali metal guanamines such as sodium or potassium amide; organic guanamines such as lithium diisopropylamide (LDA), lithium tetramethylpiperidine, lithium hexamethyldiazepine (LiHMDS) ), hexamethyldiazepine potassium (KHMDS) or sodium hexamethyldisilazane (NaHMDS); organolithium derivatives such as methyl lithium, phenyl lithium, n-butyl lithium, second butyl lithium , isobutyl lithium or tert-butyl lithium.

When the method P3 is carried out, 1 to 5 moles of a base may be used per mole of the (V) compound. It is also possible to use other ratios of reaction components. Processing is performed by a known method.

One of the compounds of the formula (V) or a salt thereof as defined herein may be prepared by halogenation of one of the compounds of the formula (VI) or a salt thereof by the method P4 as shown in the following reaction scheme:

Method P4
Wherein A, L ¹ , L ² , L ³ , n, p, X, Y, Z are as defined herein and U ² is a chlorine atom or a fluorine atom, and k is 0, 1 or 2. When k = 0, U ³ is a hydrogen atom, a hydroxyl group, a chlorine atom, an unsubstituted or substituted C ₁ -C ₆ alkylcarbonyl group or an unsubstituted or substituted C ₁ -C ₆ alkylthio group, When k = 1, U ³ is a hydroxyl group, a chlorine atom or a fluorine atom, and when k = 2, U ³ is a hydroxyl group.

Process P4 can be carried out according to known methods (The Chemistry of Functional Groups - The Chemistry of sulphonic acids, esters and their derivatives; Saul Patai, Avi Rappoport; Wiley-Interscience; 1991; 351-399).

Once the procedure P4 is followed, the compound of formula (V) can be directly cyclized according to method P3 to give the compound of formula (I).

The compound of formula (VI) can be prepared according to known methods (The Chemistry of Functional Groups - The Chemistry of sulphonic acids, esters and their derivatives; Saul Patai, Avi Rappoport; Wiley-Interscience; 1991; 351-399; The Chemistry of Functional Groups - The Chemistry of sulphenic acids, esters and their derivatives; Saul Patai; Wiley-Interscience; 1990; 187-292; The Chemistry of Functional Groups - The Chemistry of the thiol group, Part 1; Saul Patai; Wiley-Interscience; 163-270; The Chemistry of Functional Groups - The Chemistry of sulphinic acids, esters and their derivatives; Saul Patai; Wiley-Interscience; 1990; 185-216 and 577-602).

One of the compounds of formula (I) or a salt thereof as defined herein may be prepared by intramolecular cyclization from one of the compounds of formula (VII) or a salt thereof by method P5:

Method P5
Wherein A, n, X, Y ² , Y ³ , Y ⁴ , Y ⁵ , W, Z, L ¹ and L ^{2 are} as defined herein, and U ⁴ is a bromine atom, a chlorine atom, an iodine atom or a methanesulfonyl group. , toluenesulfonyl, trifluoromethanesulfonyl or fluorine atom.

Process P5 can be in the presence of a transition metal catalyst such as palladium, and optionally in the presence of a phosphine ligand or an N-heterocyclic carbene ligand; or copper, and optionally in the presence of a ligand; and, where appropriate, a base Exist in the presence and/or where appropriate in the presence of a solvent.

When U ⁴ is a bromine atom, a chlorine atom, an iodine atom, a methanesulfonyl group, a toluenesulfonyl group or a trifluoromethanesulfonyl group, the process P5 can be carried out in the presence of a catalyst such as a metal salt or a complex. Suitable metal derivatives for this purpose are transition metals such as palladium or copper.

When U ⁴ is a chlorine atom or a fluorine atom, the method P5 can be carried out in the presence of only a base.

Suitable metal salts or complexes can be as disclosed in relation to method P1.

Suitable bases for carrying out process P5 can be inorganic and organic bases customary for such reactions, such as the bases disclosed in relation to process P1.

Suitable solvents for carrying out process P5 may be customary inert organic solvents, such as those disclosed in relation to process P1.

Process P5 can be carried out in an inert atmosphere such as an argon or nitrogen atmosphere. When the method P5 is carried out, 1 to 5 moles of a base per mole of the compound of the formula (VII) can be used. When a palladium salt or a complex is used, a palladium complex of 0.01 to 20 mole percent can be used per mole of the compound of the formula (VII). When a copper salt or a complex is used, a copper complex of 0.01 to 200 mole percent can be used per mole of the compound of the formula (VII). It is also possible to use other ratios of reaction components. Processing is performed by a known method.

The compound of the formula (VII) can be produced according to a known method (The Chemistry of Functional Groups - The Chemistry of sulphonic acids, esters and their derivatives; Saul Patai, Avi Rappoport; Wiley-Interscience; 1991; 351-399).

The formula (Ib) as defined herein, of one of those compound or a salt thereof (i.e., formula (I), wherein R ^1b is not hydrogen) can be prepared by the method P6, the method comprising the following reaction scheme represented by formula ( IA), or a salt thereof by one (i.e., formula (I), wherein the step of the reaction of R ^1b is hydrogen) of formula (VIII):

Method P6
Wherein A, n, X, Y ² , Y ³ , Y ⁴ , Y ⁵ , W, Z, L ² , R ^1a and R ^{1b are} as defined herein, the limitation is that R ^{1b is} not a hydrogen atom, and U ⁵ A bromine atom, a chlorine atom, an iodine atom, a methanesulfonyl group or a toluenesulfonyl group.

When appropriate, the process P6 can be carried out in the presence of a base and, where appropriate, in the presence of a solvent.

The solvent suitable for carrying out the process P6 is not particularly limited. It may be a conventional inert organic solvent as long as it does not dissolve the compound with which it reacts or exhibits any specific interaction therewith. Suitable solvents can be, for example, the solvents disclosed in relation to process P3.

Suitable bases for carrying out process P6 may be the inorganic and organic bases customary for such reactions, such as the bases disclosed with respect to processes P1 and P3.

When the process P6 is carried out, a compound of the formula (VIII) and 1 to 5 moles of a base may be used per mole of the compound of the formula (IA). It is also possible to use other ratios of reaction components. Processing is performed by a known method.

One of the compounds of the formula (Ia) or a salt thereof can be prepared according to the method P1, P3 or P5.
The formula (Id) as defined herein, of one of those compound or a salt thereof (i.e., formula (I), wherein L ¹ CH ₂ and R ^1a-based system R ^{1a 'and} R ^2a R ^{2a based')} prepared by the method Prepared by P7, the process comprising the step of reacting one of the compounds of formula (Ic) or a salt thereof with a compound of formula (IX) as shown in the following reaction scheme:

Method P7
Wherein A, n, X, Y ² , Y ³ , Y ⁴ , Y ⁵ , W, Z, L ^{2 are} as defined herein, and R ^{1a '} and R ^{1b '} together with the carbon atom to which they are attached form 3 members, 4 Optionally, 5 or 6 membered saturated or partially saturated, optionally substituted carbocyclic or heterocyclic ring containing at least one heteroatom selected from the list consisting of N, O and S, or formed as unsubstituted or substituted a saturated or partially unsaturated bicyclo[m ¹ , m ² ,0]-C ₆ -C ₁₁ alkyl group, wherein m ² ≥1 and m ¹ + m ² = 4 to 9, or formed unsubstituted or substituted a saturated or partially unsaturated heterobicyclo[m ¹ , m ² ,0]-C ₆ -C ₁₁ alkyl group comprising from 1 to 4 heteroatoms independently selected from the list consisting of N, O and S, wherein m ² ≥ 1 and m ¹ + m ² = 4 to 9, or an unsubstituted or substituted saturated or partially unsaturated spiro[n ¹ ,n ² ]-C ₅ -C ₁₁ alkyl group, wherein n ¹ ≥ 2 and n ¹ + n ² = 4 to 10, or an unsubstituted or substituted saturated or partially unsaturated heterospiro[n ¹ ,n ² ]-C ₅ -C ₁₁ alkyl group, which comprises 1 to 4 heteroatoms independently selected from the list consisting of N, O and S, wherein n ¹ ≥ 2 and n ¹ + n ² = 4 to 10, and U ⁵ and U ⁵ , which independently contains a bromine atom, a chlorine atom, an iodine atom, a methanesulfonyl group or a toluenesulfonyl group.

Process P7 can be carried out under reaction conditions similar to those disclosed in Method P6.

As defined herein, the formula (Ie) or a salt thereof by one of (i.e., formula (I), wherein L ² C (= O)) may be illustrated by the following reaction scheme by the method of P8 formula (X) One of the compounds or their salts is prepared by intramolecular cyclization:

Method P8
Wherein A, n, X, Y ² , Y ³ , Y ⁴ , Y ⁵ , W, Z, R ^1a and R ^{1b are} as defined herein, and the U ⁶ is a leaving group such as unsubstituted or substituted C. _1- C ₆ alkoxy, unsubstituted or substituted di C ₁ -C ₈ alkylamino group or unsubstituted or substituted N-[C ₁ -C ₆ alkoxy]-C ₁ -C ₆ alkylamino group.

When appropriate, the method P8 can be carried out in the presence of a base and, where appropriate, in the presence of a solvent, preferably under anhydrous conditions.

The solvent suitable for carrying out the process P8 is not particularly limited. It may be a conventional inert organic solvent as long as it does not dissolve the compound with which it reacts or exhibits any specific interaction therewith, such as the solvent disclosed in the method P3.

Suitable bases for carrying out process P8 may be inorganic and organic bases customary for such reactions, such as the bases disclosed with respect to processes P1 and P3.

When the method P8 is carried out, 1 to 5 moles of a base per mole of the (X) compound can be used. It is also possible to use other ratios of reaction components. Processing is performed by a known method.

One of the compounds of formula (X) or a salt thereof as defined herein may be prepared by Process P9 which comprises one of the compounds of formula (XI) and a salt thereof:

Wherein A, n, X, Y ² , Y ³ , Y ⁴ , Y ⁵ , W and Z are as defined herein, and U ⁶ represents a leaving group such as unsubstituted or substituted C ₁ -C ₆ alkoxy a substituted, unsubstituted or substituted di-C ₁ -C ₈ alkylamino group or an unsubstituted or substituted N-[C ₁ -C ₆ alkoxy]-C ₁ -C ₆ alkylamino group; Step of reacting with a derivative of formula (XIa) or a derivative of formula (XIb):

Wherein R ^1a and R ^{1b are} as defined herein, and U ⁷ is a fluorine atom or a chlorine atom.

When appropriate, the method P9 can be carried out in the presence of a base and, where appropriate, in the presence of a solvent, preferably under anhydrous conditions.

The solvent suitable for carrying out the process P9 is not particularly limited. It may be a conventional inert organic solvent as long as it does not dissolve the compound with which it reacts or exhibits any specific interaction therewith, such as the solvent disclosed in the method P3.

Suitable bases for carrying out process P9 may be the inorganic and organic bases customary for such reactions, such as the bases disclosed with respect to processes P1 and P3.

When the method P9 is carried out, a compound of the formula (XIIa) or (XIIb) and a base of 1 to 5 moles per mole of the compound of the formula (XI) can be used. It is also possible to use other ratios of reaction components. Processing is performed by a known method.

One of the compounds of formula (XI) or a salt thereof, as defined herein, may be prepared by the method P10a which comprises reacting one of the compounds of formula (II) or a salt thereof with the formula (XIII) as shown in the following reaction scheme The steps of the compound reaction:

Method P10a
Wherein A, n, X, Y ² , Y ³ , Y ⁴ , Y ⁵ , W and Z are as defined herein, U ¹ is a fluorine atom, a bromine atom, a chlorine atom, an iodine atom, a methanesulfonyl group, a toluenesulfonate Or a trifluoromethanesulfonyl group, and U ⁶ represents a leaving group such as an unsubstituted or substituted C ₁ -C ₆ alkoxy group, an unsubstituted or substituted di C ₁ -C ₈ alkylamine Alkyl or unsubstituted or substituted N-[C ₁ -C ₆ -alkoxy]-C ₁ -C ₆ alkylamino group.

Process P10a can be carried out under reaction conditions similar to those disclosed in Method P1.

One of the compounds of the formula (XI) or a salt thereof as defined herein may be prepared by the method P10b, which comprises one of the compounds of the formula (XIV) or a salt thereof, as shown in the following reaction scheme (XV) The steps of the compound reaction:

Method P10b
Wherein A, n, X, Y ² , Y ³ , Y ⁴ , Y ⁵ , W and Z are as defined herein, U ¹ is a fluorine atom, a bromine atom, a chlorine atom, an iodine atom, a methanesulfonyl group, a toluenesulfonate Or a trifluoromethanesulfonyl group, and U ⁶ represents a leaving group such as an unsubstituted or substituted C ₁ -C ₆ alkoxy group, an unsubstituted or substituted di C ₁ -C ₈ alkylamine Alkyl or unsubstituted or substituted N-[C ₁ -C ₆ -alkoxy]-C ₁ -C ₆ alkylamino group.

Process P10b can be carried out under reaction conditions similar to those disclosed in Method P1.

As defined herein, the formula (If) or a salt thereof by one of (i.e., formula (I), wherein L ² based CF ₂₎ prepared by the method P11 by the formula (Ie) as a compound represented by the following reaction scheme, or one salt prepared by the fluorination reaction (i.e., formula (I), wherein L ² based C (= O)) by:

Method P11
Wherein A, n, X, Y ² , Y ³ , Y ⁴ , Y ⁵ , W, Z, R ^1a and R ^{1b are} as defined herein.

Process P11 can be carried out in the presence of a fluorinating agent and, where appropriate, in the presence of a solvent.

The fluorinating agent suitable for carrying out the process P11 is not particularly limited, and the limitation is that it is used for fluorination. Examples of the fluorinating agent include sulfur fluoride such as sulfur tetrafluoride, diethylaminosulfur trifluoride, (N-morpholinyl)sulfur trifluoride, and bis(2-methoxyethyl) trifluoride. Aminothio, 2,2-difluoro-1,3-dimethylimidazolium or 4-tert-butyl-2,6-dimethylphenylsulfide.

The solvent suitable for carrying out the process P11 is not particularly limited. It may be a conventional inert organic solvent as long as it does not dissolve the compound with which it reacts or exhibits any specific interaction therewith. Suitable solvents can be, for example, the solvents disclosed in relation to process P3.

When the method P11 is carried out, 1 to 20 moles of a fluorinating agent may be used per mole of the (Ie) compound. It is also possible to use other ratios of reaction components. Processing is performed by a known method.

As defined herein formula (Ih) or a salt thereof by one of (i.e., formula (I), wherein L ² based CFR ^2a) may be illustrated by the following reaction scheme as P12 by the method of formula (Ig) compound (also i.e. of formula (I), wherein L ² based C (OH) R ^2a) or a salt thereof, one prepared by a fluorination reaction by:

Method P12
Wherein A, n, X, Y ² , Y ³ , Y ⁴ , Y ⁵ , W, Z, R ^2a and L ^{1 are} as defined herein.

Process P12 can be carried out under reaction conditions similar to those disclosed in Method P11.

One of the compounds of formula (Ig) or a salt thereof can be prepared from one of the compounds of formula (Ie) or a salt thereof by classical functional interconversion methods known to those skilled in the art, such as reduction or addition of organometallic reagents. .

The compounds as defined herein of formula (Ii) or a salt thereof by one of (i.e., formula (I), wherein L ² CR ^2a R ^2b based and R ^2b based OR ^2C) by the formula (Ig) or a salt of one (i.e., formula (the I), wherein L ² based C (OH) R ^2a) known by those skilled in the art of classical methods (such as alkylation, nucleophilic aromatic substitution or transition metal catalyzed the Reaction) preparation:

Wherein A, n, X, Y ² , Y ³ , Y ⁴ , Y ⁵ , W, Z, L ¹ and R ^{2a are} as defined herein, and R ^2c is C ₁ -C ₈ alkyl, comprising up to 9 identical or different halogen atoms C ₁ -C ₈ -haloalkyl, C ₂ -C ₈ alkenyl group, may contain up to 9 identical or different halogen atoms C ₂ -C ₈ haloalkenyl, C ₃ -C ₈ alkynyl group, may contain up to 9 identical or different halogen atoms C ₃ -C ₈ haloalkynyl, C ₃ -C _{cycloalkyl. 7,} comprising up to 9 C may be the same or different halogen atoms ₃ -C ₇ halocycloalkyl, C ₃ -C ₇ cycloalkyl-C ₁ -C ₈ alkyl, aryl, aryl-C ₁ -C ₈ alkyl, heterocyclyl, heterocyclyl-C ₁ -C ₈ and alkyl contains 1 to 5 substituents independently selected from the group consisting of N, the heteroatom O, and S list consisting of a saturated or unsaturated fused bicyclic 9, 10 or 11-membered heterocyclic group -C ₁ -C ₈ alkyl.

The corresponding N-oxides of the compounds of formula (I) can be prepared by classical oxidation methods known to those skilled in the art.

The methods P1, P2, P3, P4, P5, P6, P7, P8, P9, P10, P11 and P12 are generally carried out under atmospheric pressure. It is also possible to operate under high pressure or reduced pressure.

When the methods P1, P2, P3, P4, P5, P6, P7, P8, P9, P10, P11 and P12 are carried out, the reaction temperature can be varied within a relatively wide range. Generally, such processes are carried out at temperatures ranging from -78 ° C to 200 ° C, preferably from -78 ° C to 150 ° C. The method of controlling the temperature of the method uses microwave technology.

It is processed by a conventional method. In general, the reaction mixture is treated with water, and the organic phase is separated and concentrated under reduced pressure. Where appropriate, the remaining residue may be released from any impurities that may still be present by conventional methods such as chromatography, crystallization or distillation.

Compounds of formula (I) can be prepared according to the general preparation methods described above and by classical functional interconversion methods known to those skilled in the art. However, it should be understood that those skilled in the art will be able to adapt the methods to the particularity of each compound required for the synthesis based on their common knowledge and available disclosure.

Intermediates for the preparation of active ingredients The invention also relates to intermediates useful in the preparation of compounds of formula (I).

Accordingly, the present invention relates to compounds of formula (IIIa) and (IVa) and acceptable salts thereof:

among them:
A, n and L ^{2 are} as defined herein;
X ^b is independently selected from the system consisting of the group consisting of: a halogen atom, C ₁ -C ₈ alkyl group, may contain up to 9 identical or different halogen atoms C ₁ -C ₈ -haloalkyl, C ₂ -C ₈ alkenyl group a C ₂ -C ₈ haloalkenyl group, a C ₂ -C ₈ alkynyl group containing up to 9 halogen atoms which may be the same or different, a C ₂ -C ₈ halogenated group containing up to 9 halogen atoms which may be the same or different Alkynyl, C ₃ -C ₇ cycloalkyl, C ₄ -C ₇ cycloalkenyl, hydroxy, C ₁ -C ₈ alkoxy, C ₁ -C ₈ haloalkane containing up to 9 halogen atoms which may be the same or different Oxyl, decyl, C ₁ -C ₈ alkylcarbonyl, (hydroxyimino) C ₁ -C ₈ alkyl, (C ₁ -C ₈ alkoxyimino) C ₁ -C ₈ alkyl a carboxyl group, a C ₁ -C ₈ alkoxycarbonyl group, a thiol group, a C ₁ -C ₈ alkylthio group, a C ₁ -C ₈ alkylsulfinyl group, a C ₁ -C ₈ alkylsulfonyl group, a C ₁ -C ₆ trialkyl fluorenyl group, a C ₁ -C ₆ trialkyl fluorenyl-C ₁ -C ₆ alkyl group, a cyano group and a nitro group, wherein each X is optionally substituted;
L ^1a represents CR ^1a R ^1b , wherein R ^1a and R ^{1b are} as defined herein, and the restriction is that R ^1a or R ^{1b is} not aryl, aryl-C ₁ -C ₈ alkyl, heterocyclic, heterocyclic a base-C ₁ -C ₈ alkyl group, and
V-benzyl, 4-methoxybenzyl, allyl, unsubstituted or substituted C ₁ -C ₆ alkylsulfonyl, trifluoromethanesulfonyl, unsubstituted or substituted Benzosulfonyl, unsubstituted or substituted C ₁ -C ₆ alkoxycarbonyl, unsubstituted or substituted benzyloxycarbonyl, allyloxycarbonyl or 2-trimethyldecylethoxy methyl;
A compound whose condition is that formula (IIIa) or (IVa) does not mean:
- 3,4-Dihydro-1 H -pyrido[3,2-c][1,2]thiazine 2,2-dioxide [412338-54-6],
4- 4-bromo-7-nitro-1,3-dihydro[1,2]thiazolo[3,4-c]pyridine 2,2-dioxide [263887-69-0] and
1-Allyl-1 H -pyrido[2,3-c][1,2]thiazine-4( 3H )-one 2,2-dioxide [1418315-90-8].

The following compounds of formula (IIIa) or (IVa) are also mentioned in the chemical database and/or supplier database, but do not contain any references or information that enable the preparation and isolation of such compounds:
- 7-Methyl-1,7-dihydropyrazolo[3,4-c][1,2]thiazine-4(3 H )-one 2,2-dioxide [2137593-81-6 ],
- 1 H -thieno[3,2-c][1,2]thiazin-4(3 H )-one 2,2-dioxide [1710195-44-0],
- Benzyl-1 H -thieno[3,2-c][1,2]thiazin-4(3 H )-one 2,2-dioxide [950277-11-9],
- (2E)-(2,2-Dioxylyl-1H-thieno[3,2-c][1,2]thiazin-4(3H)-ylidene)ethyl acetate [2172611-23- 1] and
- (2E)-(2,2-Dioxylyl-1H-thieno[3,2-c][1,2]thiazin-4(3H)-ylidene)acetate [2169695-13- 8].

The invention also relates to compounds of formula (V) and (VI) and salts thereof:

among them:
A, n, X, Y ² , Y ³ , Y ⁴ , Y ⁵ , W, Z, L ¹ and L ^{2 are} as defined herein;
k is 0, 1 or 2;
U ² is a chlorine atom or a fluorine atom; and when k = 0, a U ³ -based hydrogen atom, a hydroxyl group, a chlorine atom, an unsubstituted or substituted C ₁ -C ₆ alkylcarbonyl group or unsubstituted or substituted A C ₁ -C ₆ alkylthio group, when k = 1, is a hydroxyl group, a chlorine atom or a fluorine atom, and when k = 2, it is a hydroxyl group.

The invention also relates to compounds of formula (VII) and salts thereof:

among them:
A, n, X, Y ² , Y ³ , Y ⁴ , Y ⁵ , W, Z, L ¹ and L ^{2 are} as defined herein;
U ⁴ is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyl group, a toluenesulfonyl group, a methanesulfonyl group or a trifluoromethanesulfonyl group.

The invention also relates to compounds of formula (X) and salts thereof:

among them:
^{A, n, X, Y 2} , Y 3, Y 4, Y 5, W, Z, R 1a and R ^1b as defined herein; and
U ⁶ is an unsubstituted or substituted C ₁ -C ₆ alkoxy group, an unsubstituted or substituted di C ₁ -C ₈ alkylamino group or an unsubstituted or substituted N-[C ₁ - C ₆ alkoxy]-C ₁ -C ₆ alkylamino group.

The invention also relates to compounds of formula (XIa) and salts thereof:

among them:
A, n, Y ² , Y ³ , Y ⁴ , Y ⁵ and W are as defined herein;
X ^b is independently selected from the system consisting of the group consisting of: a halogen atom, C ₁ -C ₈ alkyl group, may contain up to 9 identical or different halogen atoms C ₁ -C ₈ -haloalkyl, C ₂ -C ₈ alkenyl group a C ₂ -C ₈ haloalkenyl group, a C ₂ -C ₈ alkynyl group containing up to 9 halogen atoms which may be the same or different, a C ₂ -C ₈ halogenated group containing up to 9 halogen atoms which may be the same or different Alkynyl, C ₃ -C ₇ cycloalkyl, C ₄ -C ₇ cycloalkenyl, hydroxy, C ₁ -C ₈ alkoxy, C ₁ -C ₈ haloalkane containing up to 9 halogen atoms which may be the same or different Oxyl, decyl, C ₁ -C ₈ alkylcarbonyl, (hydroxyimino) C ₁ -C ₈ alkyl, (C ₁ -C ₈ alkoxyimino) C ₁ -C ₈ alkyl a carboxyl group, a C ₁ -C ₈ alkoxycarbonyl group, a thiol group, a C ₁ -C ₈ alkylthio group, a C ₁ -C ₈ alkylsulfinyl group, a C ₁ -C ₈ alkylsulfonyl group, a C ₁ -C ₆ trialkyl fluorenyl group, a C ₁ -C ₆ trialkyl fluorenyl-C ₁ -C ₆ alkyl group, a cyano group and a nitro group, wherein each X is optionally substituted;
The composition consisting of the following groups Z ^a is selected from: a hydrogen atom, C ₁ -C ₈ alkyl group, may contain up to 9 identical or different halogen atoms C ₁ -C ₈ -haloalkyl, C ₂ -C ₈ alkenyl group, containing up to 9 C ₂ -C ₈ haloalkenyl groups, C ₂ -C ₈ alkynyl groups which may be the same or different halogen atoms, C ₂ -C ₈ haloalkynyl groups containing up to 9 halogen atoms which may be the same or different, C ₃ -C ₇ cycloalkyl, C ₄ -C ₇ cycloalkenyl, aryl, heterocyclic, indolyl, C ₁ -C ₈ alkylcarbonyl, (hydroxyimino) C ₁ -C ₈ alkane , (C ₁ -C ₈ alkoxyimino)C ₁ -C ₈ alkyl, carboxy, C ₁ -C ₈ alkoxycarbonyl, amine carbhydryl, C ₁ -C ₈ alkylamine fluorenyl , a di C ₁ -C ₈ alkylamine carbenyl group;
U ⁶ is an unsubstituted or substituted C ₁ -C ₆ alkoxy group, an unsubstituted or substituted di C ₁ -C ₈ alkylamino group or an unsubstituted or substituted N-[C ₁ - C ₆ alkoxy]-C ₁ -C ₆ alkylamino group;
The restriction is that the compound of formula (X) does not mean:
- Methyl 4-methyl-2-(methylthio)-6-(quinolin-3-ylamino)pyrimidine-5-carboxylate [1586744-10-6].

References to compounds of formula (X) below in the chemical database and/or supplier database, but without any references or information enabling the preparation and isolation of such compounds:
- 4-Ethyl-5-methyl-2-[(3-methylquinoxalin-2-yl)amino]-3-decanoic acid ethyl ester [1908892-99-8],
2-Dimethyl-5-(quinoxalin-2-ylamino)furan-3,4-dicarboxylic acid diethyl ester [1908488-18-5],
- 1-methyl-5-(quinoxalin-2-ylamino)-1 H -pyrazole-4-carboxylic acid ethyl ester [1905396-34-0],
2-Diethyl 2-methyl-5-[(3-methylquinoxalin-2-yl)amino]furan-3,4-dicarboxylate [1900900-95-9],
1-ethyl-5-[(3-methylquinoxalin-2-yl)amino]-1 H -pyrazole-4-carboxylic acid ethyl ester [1900401-91-3],
4-ethyl 4-mercapto-5-methyl-2-(quinoxalin-2-ylamino)-3-decanoate [1898509-52-8], and
- 5-(quinolin-3-ylamino)-1,3-thiazole-4-carboxylic acid ethyl ester [1410431-43-4].

Compositions and Formulations The present invention is further directed to compositions, particularly compositions for controlling undesirable microorganisms, comprising one or more compounds of formula (I). The composition is preferably a fungicidal composition.

The compositions typically comprise one or more compounds of formula (I) and one or more acceptable carriers, especially one or more agriculturally acceptable carriers.

The carrier is a solid or liquid, natural or synthetic, organic or inorganic material which is generally inert. The carrier generally improves the application of the compound to, for example, plants, plant parts or seeds. Examples of suitable solid carriers include, but are not limited to, ammonium salts; natural stone powders such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth; and synthetic stone powder, Such as fine powdered ceria, alumina and citrate. Examples of solid carriers generally suitable for the preparation of granules include, but are not limited to, ground and graded natural rocks such as calcite, marble, pumice, sepiolite and dolomite; synthetic inorganic and organic powder granules; Particles of materials such as paper, sawdust, coconut shells, corn cobs and tobacco stems. Examples of suitable liquid carriers include, but are not limited to, water, organic solvents, and combinations thereof. Examples of suitable solvents include polar and non-polar organic chemical liquids from the following classes: for example, aromatic and non-aromatic hydrocarbons (such as cyclohexane, paraffin, alkylbenzene, xylene, tolyl naphthalene, chlorinated aromatics) a compound or a chlorinated aliphatic hydrocarbon such as chlorobenzene, vinyl chloride or dichloromethane), ethanol and a polyol (which may also be substituted, etherified and/or esterified, such as butanol or ethylene glycol), ketone (such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone), esters (including fats and oils) and (poly) ethers, unsubstituted and substituted amines, guanamines (such as Dimethylcarbendamine), indoleamine (such as N-alkylrrolidone) and lactones, hydrazine and hydrazine (such as dimethyl hydrazine). The carrier may also be a liquefied gaseous filler (i.e., a liquid that is gaseous at standard temperature and at standard pressure), such as an aerosol propellant such as a halogenated hydrocarbon, butane, propane, nitrogen, and carbon dioxide. The amount of the carrier is usually in the range of 1 to 99.99%, preferably 5 to 99.9%, more preferably 10 to 99.5%, and most preferably 20 to 99% by weight of the composition.

The composition may further comprise one or more acceptable auxiliaries conventionally used in formulating compositions (e.g., agrochemical compositions), such as one or more surfactants.

The surfactant can be an ionic (cationic or anionic) or nonionic surfactant such as an ionic or nonionic emulsifier, a foam former, a dispersant, a humectant, and any mixture thereof. Examples of suitable surfactants include, but are not limited to, salts of polyacrylic acid, salts of lignosulfonic acid, salts of phenolsulfonic acid or naphthalenesulfonic acid, ethylene and/or propylene oxide with fatty alcohols, fatty acids or fatty amines Polycondensate (polyoxyethylene fatty acid ester, polyoxyethylene fatty alcohol ether, such as alkylaryl polyglycol ether), substituted phenol (preferably alkyl phenol or aryl phenol), sulfobutane a salt of an acid ester, a taurine derivative (preferably an alkyl taurate), a polyethoxylated alcohol or a phosphate of a phenol, a fatty ester of a polyhydric alcohol, and a sulfate, a sulfonate and a phosphate Derivatives of the compounds (for example, alkyl sulfonates, alkyl sulfates, aryl sulfonates) and protein hydrolysates, lignin sulfite waste liquids and methyl cellulose. The surfactant is generally used when the compound of formula (I) and/or the carrier is insoluble in water and applied with water. The amount of surfactant is then typically in the range of from 5 to 40% by weight of the composition.

Other examples of auxiliaries useful in the formulation of agrochemical compositions include water repellents, desiccants, adhesives (adhesives, tackifiers, fixatives, such as carboxymethylcellulose, in the form of powders, granules or latexes). Forms of natural and synthetic polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate, natural phospholipids such as cephalin and lecithin and synthetic phospholipids, polyvinylpyrrolidone, polyvinyl acetate, poly Vinyl alcohol and tylose, thickeners, stabilizers (such as low temperature stabilizers, preservatives, antioxidants, light stabilizers or other agents that improve chemical and/or physical stability), dyes or pigments ( Such as inorganic pigments, such as iron oxide, titanium oxide and Prussian Blue; organic dyes such as alicarin, azo and metal phthalocyanine dyes, defoamers (such as polyfluorene defoamers and hard Magnesium sulphate), preservatives (such as dichlorophene and benzyl alcohol hemiformal), secondary thickeners (cellulose derivatives, acrylic acid derivatives, Sanxian gum, modified clay and fine powder) Chelated cerium oxide), Stickers, gibberellin and processing aids, mineral oils and vegetable oils, spices, waxes and nutrients (including trace nutrients such as iron salts, manganese salts, boron salts, copper salts, cobalt salts, molybdenum Salts and zinc salts), protective colloids, thixotropic substances, penetrants, chelating agents and complex forming agents.

The choice of adjuvant is related to the intended mode of application of the compound of formula (I) and/or its physical properties. In addition, the adjuvants can be selected to impart specific characteristics (industrial, physical, and/or biological properties) to the composition or the form of use from which it is prepared. The choice of adjuvants allows the composition to be tailored to specific needs.

The composition of the present invention may be in any conventional form such as a solution (for example, an aqueous solution), an emulsion, a wettable powder, a water-based and oil-based suspension, a powder, a dust, a paste, a soluble powder, a soluble granule, and a dispersion. Granules, suspoemulsion concentrates, natural or synthetic products impregnated with the compounds of the invention, fertilizers, and microcapsules in polymeric materials. The compounds of the invention may exist in suspended, emulsified or dissolved form.

The compositions of the present invention can be provided as ready-to-use formulations to end users, i.e., the compositions can be applied directly to plants or seeds by suitable means such as spraying or dusting means. Alternatively, the composition in the form of a concentrate can be provided to the end user, which must be diluted prior to use, preferably diluted with water.

The compositions of the present invention can be prepared in a conventional manner, for example by mixing a compound of the invention with one or more suitable auxiliaries, such as the adjuvants disclosed above.

The compositions according to the invention generally comprise from 0.01 to 99% by weight, from 0.05 to 98% by weight, preferably from 0.1 to 95% by weight, more preferably from 0.5 to 90% by weight, most preferably from 1 to 80% by weight of the compound of the invention.

The compounds and compositions of the present invention can be combined with other active ingredients such as fungicides, bactericides, acaricides, nematicides, insecticides, herbicides, fertilizers, growth regulators, safeners or message compounds. This can broaden the range of activity or prevent drug resistance. Examples of known fungicides, insecticides, acaricides, nematicides and bactericides are disclosed in the Pesticide Manual, 17th Edition.

Examples of particularly preferred fungicides which may be admixed with the compounds and compositions of the invention are:
1) Inhibitors of ergosterol biosynthesis, for example (1.001) cyproconazole, (1.002) difenoconazole, (1.003) epoxiconazole, (1.004) cycloheximide ( Fenhexamid), (1.005) fenpropidin, (1.006) fenpropimorph, (1.007) fenpyrazamine, (1.008) fluquinconazole, (1.009) Flutriafol, (1.010) imazalil, (1.011) imazalil sulfate, (1.012) ipconazole, (1.013) metconazole, (1.014) Myclobutanil, (1.015) paclobutrazol, (1.016) prochloraz, (1.017) propiconazole, (1.018) prothioconazole, (1.019) pyridoxine Pyrosoxazole, (1.020) spiroxamine, (1.021) tebuconazole, (1.022) tetraconazole, (1.023) triadimenol, (1.024) darfuren ( Tridemorph), (1.025) triticonazole, (1.026) (1R, 2S, 5S)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-( 1H-1,2,4-triazol-1-ylmethyl)cyclopentyl , (1.027) (1S, 2R, 5R)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazole- 1-ylmethyl)cyclopentanol, (1.028) (2R)-2-(1-chlorocyclopropyl)-4-[(1R)-2,2-dichlorocyclopropyl]-1-(1H -1,2,4-triazol-1-yl)butan-2-ol, (1.029) (2R)-2-(1-chlorocyclopropyl)-4-[(1S)-2,2-di Chlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.030) (2R)-2-[4-(4-chlorophenoxy) -2-(Trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol, (1.031) (2S)-2-(1-chloro Cyclopropyl)-4-[(1R)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.032) (2S)-2-(1-chlorocyclopropyl)-4-[(1S)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl ) butan-2-ol, (1.033) (2S)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4 -triazol-1-yl)propan-2-ol, (1.034) (R)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1 , 2-oxazol-4-yl](pyridin-3-yl)methanol, (1.035) (S)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluoro Phenyl)-1,2-oxazol-4-yl](pyridin-3-yl)methanol, (1.036) [3-(4-chloro-2-fluorophenyl)-5-(2,4-di Fluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl)methanol, (1.037) 1-({(2R,4S)-2-[ 2-Chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-1,3-dioxolan-2-yl}methyl)-1H-1,2,4- Triazole, (1.038) 1-({(2S,4S)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-1,3-dioxolane Pentane-2-yl}methyl)-1H-1,2,4-triazole, (1.039) 1-{[3-(2-chlorophenyl)-2-(2,4-di) Fluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole-5-ester, (1.040) 1-{[rel(2R,3R)-3 thiocyanate -(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole-5-ester, ( 1.041) 1-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl} thiocyanate -1H-1,2,4-triazole-5-ester, (1.042) 2-[(2R,4R,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6 ,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.043) 2-[(2R,4R,5S)- 1-(2,4-Dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole -3-thione, (1.044) 2-[(2R,4S,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4- 2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.045) 2-[(2R,4S,5S)-1-(2,4-dichlorobenzene 5-)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H -1,2,4-triazole-3-thione, (1.046) 2-[(2S,4R,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6, 6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.047) 2-[(2S,4R,5S)-1 -(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole- 3-thione, (1.048) 2-[(2S,4S,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl -2,4-Dihydro-3H-1,2,4-triazole-3-thione, (1.049) 2-[(2S,4S,5S)-1-(2,4-dichlorophenyl) )-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.050) 2- [1-(2,4-Dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-tri Oxazole-3-thione, (1.051) 2-[2-chloro-4-(2,4-dichlorophenoxy)phenyl]-1-(1H-1,2,4-triazole-1- Propyl-2-ol, (1.052) 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1-(1H-1,2,4-triazol-1-yl) Butan-2-ol, (1.053) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazole-1 -yl)butan-2-ol, (1.054) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-tri Zin-1-yl)pentan-2-ol, (1.055) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H -1,2,4-triazol-1-yl)propan-2-ol, (1.056) 2-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl) ring Oxyethane-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.057) 2-{[rel(2R,3R)-3 -(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-2,4-dihydro-3H-1,2,4-tri Oxazole-3-thione, (1.058) 2-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxirane-2- Methyl}-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.059) 5-(4-chlorobenzyl)-2-(chloromethyl) -2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol, (1.060) 5-(allylsulfonyl)-1-{[3- (2-Chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole, (1.061) 5-( Allylsulfonyl)-1-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl] Methyl}-1H-1,2,4-triazole, (1.062) 5-(allylsulfonyl)-1-{[rel(2R,3S)-3-(2-chlorophenyl)- 2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole, (1.063) N'-(2,5-dimethyl 4-{[3-(1,1,2,2-tetrafluoroethoxy)phenyl]sulfonyl}phenyl)-N-ethyl-N-methyliminocarbamidine, 1.064) N'-(2,5-dimethyl -4-{[3-(2,2,2-Trifluoroethoxy)phenyl]sulfonyl}phenyl)-N-ethyl-N-methyliminocarbamidine, (1.065) N'-(2,5-Dimethyl-4-{[3-(2,2,3,3-tetrafluoropropoxy)phenyl]sulfonyl}phenyl)-N-ethyl-N -methylimidocarbamide, (1.066) N'-(2,5-dimethyl-4-{[3-(pentafluoroethoxy)phenyl]sulfonyl}phenyl)-N -ethyl-N-methyliminocarbamamine, (1.067) N'-(2,5-dimethyl-4-{3-[(1,1,2,2-tetrafluoroethyl) Thio]phenoxy}phenyl)-N-ethyl-N-methyliminocarbamidine, (1.068) N'-(2,5-dimethyl-4-{3-[(( 2,2,2-Trifluoroethyl)thio]phenoxy}phenyl)-N-ethyl-N-methyliminocarbamidine, (1.069) N'-(2,5-di Methyl-4-{3-[(2,2,3,3-tetrafluoropropyl)thio]phenoxy}phenyl)-N-ethyl-N-methyliminocarbamidine, (1.070) N'-(2,5-Dimethyl-4-{3-[(pentafluoroethyl)thio]phenoxy}phenyl)-N-ethyl-N-methylimino Formamide, (1.071) N'-(2,5-dimethyl-4-phenoxyphenyl)-N-ethyl-N-methyliminocarbamidine, (1.072) N'- (4-{[3-(Difluoromethoxy)phenyl]sulfonyl}-2,5-dimethylphenyl)-N-ethyl-N-methyliminocarbamidine, ( 1.073) N'-(4-{3-[( Fluoromethyl)thio]phenoxy}-2,5-dimethylphenyl)-N-ethyl-N-methyliminocarbamidine, (1.074) N'-[5-bromo- 6-(2,3-Dihydro-1H-indol-2-yloxy)-2-methylpyridin-3-yl]-N-ethyl-N-methyliminocarbamidine, (1.075 N'-{4-[(4,5-Dichloro-1,3-thiazol-2-yl)oxy]-2,5-dimethylphenyl}-N-ethyl-N-methyl Iminocarbamide, (1.076) N'-{5-bromo-6-[(1R)-1-(3,5-difluorophenyl)ethoxy]-2-methylpyridine-3- }-N-ethyl-N-methyliminocarbamamine, (1.077) N'-{5-bromo-6-[(1S)-1-(3,5-difluorophenyl) Oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methyliminocarbamidine, (1.078) N'-{5-bromo-6-[(cis-4 -isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methyliminocarbamidine, (1.079) N'-{5-bromo-6 -[(trans-4-isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methyliminocarbamidine, (1.080) N' -{5-Bromo-6-[1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidocarba Indoleamine, (1.081) methyl triconazole, (1.082) yttrium triconazole.
2) Inhibitors of the respiratory chain at complex I or II, for example (2.001) benzovindiflupyr, (2.002) bixafen, (2.003) boscalid, (2.004) ) carboxin, (2.005) floopyram, (2.006) flutanil, (2.007) flumapyyroxad, (2.008) foraby (furametpyr ), (2.009) Isofetamid, (2.010) isopyrazam (anti-episomeric enantiomer 1R, 4S, 9S), (2.011) pyrazol Amine (anti-episomeric enantiomer 1S, 4R, 9R), (2.012) pyrazolamide (anti-isomeric racemate 1RS, 4SR, 9SR), (2.013) pyrazol naphthalene Insecticidal (Isotopic epimer race 1RS, 4SR, 9RS and anti-episomeric racemate 1RS, 4SR, 9SR mixture), (2.014) pyrazolamide (isolateral differential) Isomer Enantiomers 1R, 4S, 9R), (2.015) Pyrazolamide (Ipsilateral Epimerization Enantiomers 1S, 4R, 9S), (2.016) Pyrazolidine ( Ipsilateral epimer races 1RS, 4SR, 9RS), (2.017) penflufen, (2.018) penthiopyrad, (2.019) pydiflumetofen (2.020) Pyraziflumid, (2.021) sedaxane, (2.022) 1,3-dimethyl-N-(1,1,3-trimethyl-2, 3-Dihydro-1H-indol-4-yl)-1H-pyrazole-4-carboxamide, (2.023) 1,3-dimethyl-N-[(3R)-1,1,3-three Methyl-2,3-dihydro-1H-indol-4-yl]-1H-pyrazole-4-carboxamide, (2.024) 1,3-dimethyl-N-[(3S)-1, 1,3-trimethyl-2,3-dihydro-1H-indol-4-yl]-1H-pyrazole-4-carboxamide, (2.025) 1-methyl-3-(trifluoromethyl )-N-[2'-(trifluoromethyl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide, (2.026) 2-fluoro-6-(trifluoromethyl)-N -(1,1,3-trimethyl-2,3-dihydro-1H-indol-4-yl))benzamide, (2.027) 3-(difluoromethyl)-1-methyl- N-(1,1,3-trimethyl-2,3-dihydro-1H-indol-4-yl)-1H-pyrazole-4-carboxamide, (2.028) 3-(difluoromethyl )-1-methyl-N-[(3R)-1,1,3-trimethyl-2,3-dihydro-1H-indol-4-yl]-1H-pyrazole-4-carboxamide , (2.029) 3-(Difluoromethyl)-1-methyl-N-[(3S)-1,1,3-trimethyl-2,3-dihydro-1H-indol-4-yl] -1H-pyrazole-4-carboxamide, (2.030) 3-(difluoromethyl)-N-(7-fluoro-1,1,3-trimethyl-2,3-dihydro-1H-茚-4-yl)-1-methyl-1H-pyrazole-4-carboxamide, (2.031) 3-(difluoromethyl)-N-[(3R)-7-fluoro- 1,1,3-trimethyl-2,3-dihydro-1H-indol-4-yl]-1-methyl-1H-pyrazole-4-carboxamide, (2.032) 3-(difluoro Methyl)-N-[(3S)-7-fluoro-1,1,3-trimethyl-2,3-dihydro-1H-indol-4-yl]-1-methyl-1H-pyrazole 4-carbamamine, (2.033) 5,8-difluoro-N-[2-(2-fluoro-4-{[4-(trifluoromethyl)pyridin-2-yl])ethyl]quina Oxazolin-4-amine, (2.034) N-(2-cyclopentyl-5-fluorobenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl -1H-pyrazole-4-carbamide, (2.035) N-(2-tert-butyl-5-methylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5 -fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.036) N-(2-t-butylbenzyl)-N-cyclopropyl-3-(difluoromethyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.037) N-(5-chloro-2-ethylbenzyl)-N-cyclopropyl-3-(di) Fluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.038) N-(5-chloro-2-isopropylbenzyl)-N-cyclopropyl- 3-(Difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.039) N-[(1R,4S)-9-(dichloromethylene) -1,2,3,4-tetrahydro-1,4-methylnaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.040) N-[(1S,4R)-9-(Dichloromethylene)-1,2,3,4-tetrahydro-1,4-methyl bridge Naphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.041) N-[1-(2,4-dichlorophenyl) 1-methoxypropan-2-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.042) N-[2-chloro-6- (trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.043) N -[3-chloro-2-fluoro-6-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyridyl Oxazole-4-carboxamide, (2.044) N-[5-chloro-2-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro- 1-methyl-1H-pyrazole-4-carboxamide, (2.045) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-[5-methyl -2-(Trifluoromethyl)benzyl]-1H-pyrazole-4-carbamide, (2.046) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-( 2-fluoro-6-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.047) N-cyclopropyl-3-(difluoromethyl)-5- Fluorine-N-(2-isopropyl-5-methylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.048) N-cyclopropyl-3-(difluoro Methyl)-5-fluoro-N-(2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-thiocarbamine, (2.049) N-cyclopropyl-3-( Difluoromethyl)-5-fluoro-N-(2-isopropyl Benzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.050) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(5-fluoro- 2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.051) N-cyclopropyl-3-(difluoromethyl)-N-(2-B 4-,5-dimethylbenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.052) N-cyclopropyl-3-(difluoromethyl -N-(2-ethyl-5-fluorobenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.053) N-cyclopropyl-3-( Difluoromethyl)-N-(2-ethyl-5-methylbenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.054) N-cyclopropane -N-(2-cyclopropyl-5-fluorobenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.055 N-cyclopropyl-N-(2-cyclopropyl-5-methylbenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4- Formamide, (2.056) N-cyclopropyl-N-(2-cyclopropylbenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4 - formamide.
3) Inhibitors of the respiratory chain at the complex III, for example (3.001) ametoctradin, (3.002) oxasulbrom, (3.003) azoxystrobin, ( 3.004) coumethoxystrobin, (3.005) coumoxystrobin, (3.006) cyazofamid, (3.007) dimoxystrobin, (3.008) alkyl azoxystrobin (enoxastrobin), (3.009) 凡同同 (famoxadone), (3.010) imidacloprid (fenamidone), (3.011) flufenoxystrobin, (3.012) fluoxastrobin, (3.013) g Kresoxim-methyl, (3.014) metominostrobin, (3.015) oressastrobin, (3.016) picoxystrobin, (3.017) pyraclostrobin, (3.018) pyramitostrobin, (3.019) pyraoxystrobin, (3.020) trifloxystrobin, (3.021) (2E)-2-{2-[({[(1E)) 1-(3-{[(E)-1-fluoro-2-phenylvinyl]oxy}phenyl)ethylidene]amino}oxy)methyl]phenyl}-2-(A Ominoimido)-N-methylacetamide, (3.022) (2E,3Z)-5-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy}- 2- (methoxyimido)-N,3-dimethylpent-3-enylamine, (3.023) (2R)-2-{2-[(2,5-dimethylphenoxy)methyl Phenyl}-2-methoxy-N-methylacetamide, (3.024) (2S)-2-{2-[(2,5-dimethylphenoxy)methyl]phenyl} -2-methoxy-N-methylacetamide, (3.025) (3S,6S,7R,8R)-8-benzyl-3-[({3-[(isobutyloxy))) Oxy]-4-methoxypyridin-2-yl}carbonyl)amino]-6-methyl-4,9-di-oxy-1,5-dioxan-7-yl 2- Methyl propionate, (3.026) 2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}}-2-methoxy-N-methylacetamide, 3.027) N-(3-ethyl-3,5,5-trimethylcyclohexyl)-3-carboxamido-2-hydroxybenzamide, (3.028) (2E,3Z)-5-{ [1-(4-Chloro-2-fluorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-ene Indoleamine, (3.029) methyl {5-[3-(2,4-dimethylphenyl)-1H-pyrazol-1-yl]-2-methylbenzyl}carbamate.
4) Inhibitors of mitosis and cell division such as (4.001) carbendazim, (4.002) diehofencarb, (4.003) ethaboxam, (4.004) fluopyram, (4.005) ) pencycuron, (4.006) rot, (4.007) thiophanate-methyl, (4.008) zoxamide, (4.009) 3-chloro-4-(2,6- Difluorophenyl)-6-methyl-5-phenylpyridazine, (4.010) 3-chloro-5-(4-chlorophenyl)-4-(2,6-difluorophenyl)-6- Methylpyridazine, (4.011) 3-chloro-5-(6-chloropyridin-3-yl)-6-methyl-4-(2,4,6-trifluorophenyl)pyridazine, (4.012) 4-(2-Bromo-4-fluorophenyl)-N-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.013) 4-( 2-Bromo-4-fluorophenyl)-N-(2-bromo-6-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.014) 4-(2- Bromo-4-fluorophenyl)-N-(2-bromophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.015) 4-(2-bromo-4-fluorobenzene -N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.016) 4-(2-bromo-4-fluorophenyl) -N-(2-chlorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.017) 4-(2-bromo-4-fluorophenyl)-N-(2- Fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.018) 4-(2-chloro-4- Phenyl)-N-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.019) 4-(2-chloro-4-fluorophenyl) -N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.020) 4-(2-chloro-4-fluorophenyl)-N -(2-chlorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.021) 4-(2-chloro-4-fluorophenyl)-N-(2-fluorobenzene ))-1,3-dimethyl-1H-pyrazole-5-amine, (4.022) 4-(4-chlorophenyl)-5-(2,6-difluorophenyl)-3,6- Dimethylpyridazine, (4.023) N-(2-bromo-6-fluorophenyl)-4-(2-chloro-4-fluorophenyl))-1,3-dimethyl-1H-pyrazole -5-amine, (4.024) N-(2-bromophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, ( 4.025) N-(4-Chloro-2,6-difluorophenyl)-4-(2-chloro-4-fluorophenyl))-1,3-dimethyl-1H-pyrazole-5-amine .
5) Compounds capable of multi-site action, such as (5.001) purplish red mixture, (5.002) tetrachlordane, (5.003) captan, (5.004) tetrachloroisophthalonitrile, (5.005) copper hydroxide , (5.006) copper naphthenate, (5.007) copper oxide, (5.008) basic copper oxychloride, (5.009) copper (2+) sulfate, (5.010) nitrile sulfonium, (5.011) dodine (dodine) , (5.012) folfet, (5.013) zinc-manganese (mancozeb), (5.014) manganese peripur (maneb), (5.015) from ruin (metiram), (5.016) to avoid rotten zinc, (5.017 ) oxine-copper, (5.018) methyl zinc Naipu, (5.019) sulfur and sulfur preparations including calcium polysulfide, (5.020) thiram, (5.021) zinc napu ( Zineb), (5.022) Yisui (ziram), (5.023) 6-ethyl-5,7-di-oxy-6,7-dihydro-5H-pyrrolo[3',4':5,6 ][1,4]dithiazepine[2,3-c][1,2]thiazole-3-carbonitrile.
6) Compounds capable of inducing host protection, such as (6.001) activated ester-S-methyl, (6.002) isotianil, (6.003) probenazole, (6.004) tiadinil .
7) Inhibitors of amino acid and/or protein biosynthesis, for example, (7.001) cyprodinil, (7.002) kasugamycin, (7.003) hydrated kasugamycin hydrochloride, (7.004) Oxytetracycline, (7.005) pyrimethanil, (7.006) 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinoline- 1-yl)quinoline.
8) Inhibitors of ATP production, such as (8.001) silthiofam.
9) Inhibitors of cell wall synthesis, such as (9.001) benthiavalicarb, (9.002) dimethomorph, (9.003) flumorph, (9.004) iprovalicarb, (9.005) mandipropamid, (9.006) pyrimorph, (9.007) valifenalate, (9.008) (2E)-3-(4-third Butylphenyl)-3-(2-chloropyridin-4-yl)-1-(morpholin-4-yl)prop-2-en-1-one, (9.009)(2Z)-3-(4 -T-butylphenyl)-3-(2-chloropyridin-4-yl)-1-(morpholin-4-yl)prop-2-en-1-one.
10) Inhibitors of lipid and membrane synthesis, for example (10.001) propamocarb, (10.002) propamoxine hydrochloride, (10.003) tolclofos-methyl.
11) Inhibitors of melanin biosynthesis, such as (11.001) tricyclazole, (11.002) {3-methyl-1-[(4-methylbenzylidene)amino]butan-2-yl } 2,2,2-trifluoroethyl carbamic acid.
12) Inhibitors of nucleic acid synthesis, such as (12.001) benalaxyl, (12.002) Bendall-M (kiralaxyl), (12.003) metalaxyl, (12.004) Destroy-M (mefenoxam).
13) Inhibitors of signal transduction, such as (13.001) fludioxonil, (13.002) iprodione, (13.003) procymidone, (13.004) propoxyquinoline (proquinazid), (13.005) quinoxyfen, (13.006) vinclozolin.
14) A compound capable of acting as an uncoupler, such as (14.001) fluazinam, (14.002) meptyldinocap.
15) Other compounds, such as (15.001) Abscisic acid, (15.002) benthiazole, (15.003) piroxazin, (15.004) capsimycin, (15.004) 15.005) carvone, (15.006) chinomethionat, (15.007) cufraneb, (15.008) cyflufenamid, (15.009) cymoxanil, ( 15.010) cyprosulfamide, (15.011) flutianil, (15.012) fosetyl-aluminium, (15.013) fosetyl-calcium, (15.014) Fosetyl-sodium, (15.015) methyl isothiocyanate, (15.016) metrafenone, (15.017) mildiomycin, (15.018) natamycin , (15.019) nickel dimethyldithiocarbamate, (15.020) nitrothal-isopropyl, (15.021) oxamocarb, (15.022) Osip Oxathiapiprolin, (15.023) oxyfenthiin, (15.024) pentachlorophenol and salt, (15.025) phosphorous acid and its salt, (15.026 propamocarb-ethylphosphonate (propamoca) Rb-fosetylate), (15.027) pyriofenone (chlazafenone), (15.028) tebufloquin, (15.029) gram of tecloftalam, (15.030) Tolnifanide, (15.031) 1-(4-{4-[(5R)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazole -3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl] Ethyl ketone, (15.032) 1-(4-{4-[(5S)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl] -1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone, (15.033 2-(6-Benzylpyridin-2-yl)quinazoline, (15.034) 2,6-dimethyl-1H,5H-[1,4]dithiazino[2,3-c: 5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetraone, (15.035) 2-[3,5-bis(difluoromethyl)-1H-pyrazole-1 -yl]-1-[4-(4-{5-[2-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazole-3 -yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone, (15.036) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl ]-1-[4-(4-{5-[2-chloro-6-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazole -3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone, (15.037) 2-[3,5- (difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-fluoro-6-(prop-2-yn-1-yloxy)phenyl) ]-4,5-Dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone, (15.038) 2-[6-( 3-fluoro-4-methoxyphenyl)-5-methylpyridin-2-yl]quinazoline, (15.039) 2-{(5R)-3-[2-(1-{[3,5 -Bis(difluoromethyl)-1H-pyrazol-1-yl]ethenyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1, 2-oxazol-5-yl}-3-chlorophenylmethanesulfonate, (15.040) 2-{(5S)-3-[2-(1-{[3,5-bis(difluoromethyl) -1H-pyrazol-1-yl]ethenyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazole-5- -3--3-chlorophenylmethanesulfonate, (15.041) 2-{2-[(7,8-difluoro-2-methylquinolin-3-yl)oxy]-6-fluorophenyl }propan-2-ol, (15.042) 2-{2-fluoro-6-[(8-fluoro-2-methylquinolin-3-yl)oxy]phenyl}propan-2-ol, (15.043 2-{3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]ethenyl}piperidin-4-yl)-1,3 -thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenylmethanesulfonate, (15.044) 2-{3-[2-(1) -{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]ethenyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5 -dihydro-1,2-oxazol-5-yl }Phenylmethanesulfonate, (15.045) 2-phenylphenol and salt, (15.046) 3-(4,4,5-trifluoro-3,3-dimethyl-3,4-dihydroisoquine Polin-1-yl)quinoline, (15.047) 3-(4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)quinoline, (15.048) 4-Amino-5-fluoropyrimidin-2-ol (tautomeric form: 4-amino-5-fluoropyrimidine-2(1H)-one), (15.049) 4-sided oxy-4-[( 2-Phenylethyl)amino]butyric acid, (15.050) 5-amino-1,3,4-thiadiazole-2-thiol, (15.051) 5-chloro-N'-phenyl-N' -(prop-2-yn-1-yl)thiophene-2-benzenesulfonate, (15.052) 5-fluoro-2-[(4-fluorobenzyl)oxy]pyrimidine-4-amine, (15.053 5-fluoro-2-[(4-methylbenzyl)oxy]pyrimidine-4-amine, (15.054) 9-fluoro-2,2-dimethyl-5-(quinolin-3-yl) )-2,3-dihydro-1,4-benzoxazepine, (15.055) {6-[({[(Z)-(1-methyl-1H-tetrazol-5-yl))) Methyl]methylene]amino}oxymethyl]pyridin-2-yl}aminocarbamic acid but-3-yne-1-ester, (15.056) (2Z)-3-amino-2-cyano- Ethyl 3-phenylacrylate, (15.057) phenazine-1-carboxylic acid, (15.058) propyl 3,4,5-trihydroxybenzoate, (15.059) quinoline-8-ol, (15.060) quinoline- 8-alcohol sulfate (2:1), (15.061) {6-[({[(1-methyl-1H-four) -5-yl)(yl)methylene]amino}oxy)methyl]pyridin-2-yl}carbamic acid tert-butyl ester, (15.062) 5-fluoro-4-imino-3- Methyl-1-[(4-methylphenyl)sulfonyl]-3,4-dihydropyrimidin-2(1H)-one.

All of the proposed mixing partners of categories (1) to (15) as described herein above may be present in the form of free compounds and/or (if their functional groups enable) their agriculturally acceptable salt forms.

Methods and Uses The compounds and compositions of the present invention have potent microbicidal activity. It can be used to control undesirable microorganisms such as undesirable fungi and bacteria. As described in more detail herein below, it may be particularly useful for crop protection (which controls microorganisms that cause plant diseases) or particularly for protecting materials (eg, industrial materials, wood, storage goods). More specifically, the compounds and compositions of the present invention are useful for protecting seeds, germinating seeds, emerged seedlings, plants, plant parts, fruits, harvested goods, and/or soil from which plants are grown from undesirable microbes.

As used herein, control/controlling covers the protective, curative, and eradicative treatment of undesirable microorganisms. The undesirable microorganism may be a pathogenic bacterium, a pathogenic virus, a pathogenic oomycete or a pathogenic fungus, more specifically a phytopathogenic bacterium, a phytopathogenic virus, a phytopathogenic oomycete or a phytopathogenic fungus. As described in detail herein below, such phytopathogenic microorganisms are the causative cause of a wide range of plant diseases.

More specifically, the compounds and compositions of the invention are useful as fungicides. For the purposes of this specification, the term "fungicide" refers to fungi that can be used for crop protection for controlling undesirable (such as Plasmodiophoromycetes, Chytridiomycetes, Zygomycetes, Ascomycetes). Ascomycetes), Basidiomycetes and Deuteromycetes and/or compounds or compositions that control Oomycetes.

The invention also relates to a method for controlling undesirable microorganisms, such as undesirable fungi, oomycetes and bacteria, the method comprising the steps of: applying at least one compound of the invention or at least one composition of the invention to a microorganism And/or its habitat (applied to plants, plant parts, seeds, fruits or soil applied to plant growth).

In general, when the compounds and compositions of the present invention are used in curative or protective methods to control phytopathogenic fungi and/or phytopathogenic oomycetes, their effective amounts and plant compatible amounts are applied to plants, plants. Part, fruit, seed or soil or substrate applied to the growth of the plant. Suitable substrates for cultivating plants include inorganic based substrates such as mineral wool, especially rock wool, perlite, sand or gravel; organic substrates such as peat, pine bark or sawdust; and petroleum based substrates such as polymeric foam or plastic Beads. An effective amount and plant phase capacity means sufficient to control or destroy fungi present on or cultivated on the cultivated land without causing any significant phytotoxic symptoms of the crop. Depending on the fungus to be controlled, the type of crop, the stage of crop growth, the climatic conditions and the individual compounds or compositions of the invention used, such amounts may vary widely. This amount can be determined by systematic field trials within the skill of the art.

Plants and Plant Parts The compounds and compositions of the invention can be applied to any plant or plant part.

By plant is meant all plants and plant populations, such as desired and undesirable wild plants or crop plants (including naturally occurring crop plants). The crop plant may be a plant obtainable by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or a combination of such methods, including genetically modified plants (GMO or transgenic plants) and Protected by plant breeders from plant cultivars.

Plant parts are understood to mean all parts and organs of plants above and below the ground, such as buds, leaves, flowers and roots, examples of which include leaves, needles, stems, stems, flowers, fruit bodies, fruits and seeds. And roots, tubers and rhizomes. Plant parts also include harvested material and asexual and sexually propagated materials such as cuttings, tubers, rhizomes, young shoots and seeds.

Plants which can be treated according to the method of the invention include the following: cotton, flax, vine, fruit, vegetable, such as Rosaceae sp. (eg, pome fruit, such as apples and pears, and stone fruit, such as apricot, cherry, almond) And peaches, and soft fruits such as strawberries), Ribesioidae sp. , Juglandaceae sp. , Betulaceae sp. , Anacardiaceae sp. , Fagaceae sp .) , Moraceae sp. , Oleaceae sp. , Actinidaceae sp. , Lauraceae sp. , Musaceae sp. (eg banana tree and planted forest) Rubiaceae sp. (eg coffee), theaceae ( Theaceae sp.) , the genus Sterculiceae sp. , Rutaceae sp. (eg lemon, orange and grapefruit); Solanaceae Sp.) (eg tomato), Liliaceae sp. , Asteraceae sp. (eg lettuce), Umbelliferae sp. , Cruciferae sp. , Chenopodiaceae Sp.) , Cucurbitaceae sp. (eg courgette), onion ( Alliac Eae sp.) (eg leek, onion), Papilionaceae sp. (eg pea); main crop plant, such as Gramineae sp. (eg corn, turf, grain, such as wheat, rye) , rice, barley, oats, chestnut and triticale), Asteraceae sp. (eg sunflower), Brassicaceae sp. (eg white cabbage, red cabbage, broccoli, broccoli, spore cabbage) , cabbage, broccoli, radish and rapeseed, nitrogen mustard, horseradish and cress), Fabacae sp. (eg, kidney beans, peanuts), Papilionaceae sp. (eg soybean), Solanaceae ( Solanaceae sp.) (eg potato), Chenopodiaceae sp. (eg sugar beet, fodder beet, red cabbage, beet); suitable for plants and ornamental plants used in gardens and forests; and in such plants The genetically modified variety of each.

In some preferred embodiments, wild-type plant species and plant cultivars, or plants obtained by conventional biological breeding methods (such as hybridization or protoplast fusion), and portions thereof, are treated according to the methods of the present invention. .

In some other preferred embodiments, the transgenic plants and plant cultivars obtained by genetic engineering, in combination with conventional methods (genetically modified organisms), and portions thereof, are treated according to the methods of the present invention. More preferably, plants of commercially available or plant cultivars in use are treated in accordance with the present invention. Plant cultivars are understood to mean plants which have novel properties ("traits") and which have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. It can be a cultivar, a variety, a biotype or a genotype.

The method according to the invention can be used to treat genetically modified organisms (GMOs), such as plants or seeds. A genetically modified plant (or a transgenic plant) is a plant in which the heterologous gene has been stably integrated into the genome. The expression "heterologous gene" basically means that a gene is provided or combined outside the plant and when introduced into the nucleus, chloroplast or mitochondrial genome, the gene is expressed by expressing the protein or polypeptide of interest or by using, for example, antisense technology The co-suppression technique, RNA interference-RNAi technology or microRNA-miRNA technology) down-regulates or silences other genes present in the plant to confer novel or improved agronomic or other properties to the transformed plant. A heterologous gene located in the genome is also referred to as a transgenic gene. A transgenic gene defined by a specific location in the plant genome is referred to as a transformation or transgenic gene event.

Plants and plant cultivars which can be treated by the methods disclosed above include all plants (whether obtained by breeding and/or biotechnological means) having genetic material which confers particularly advantageous and suitable traits on such plants.

Plants and plant cultivars which can be treated by the methods disclosed above include plants and plant cultivars which are resistant to one or more biological stresses, that is, such plants exhibit better defense against animal and microbial pests, such as resistance Nematodes, insects, mites, phytopathogenic fungi, bacteria, viruses and/or viroids.

Plants and plant cultivars also treated by the methods disclosed above include those plants that are resistant to one or more abiotic stresses. Abiotic stress conditions can include, for example, drought, low temperature exposure, heat exposure, osmotic pressure, flooding, increased soil salinity, increased mineral exposure, ozone exposure, high light exposure, limited availability of nitrogen nutrients, limited availability of phosphorus nutrients Avoid the shade.

Plants and plant cultivars which can be treated by the methods disclosed above include those plants which are characterized by enhanced yield characteristics. Increases in the yield of such plants can be the result, for example, of improved plant physiology, growth and development (such as water use efficiency, water retention efficiency, improved nitrogen use, enhanced carbon assimilation, improved photosynthetic synthesis, increased germination efficiency, and accelerated maturation). Yield can be additionally influenced by improved plant type (under adverse and non-adversive conditions) including, but not limited to, early flowering, flowering control of hybrid seed production, seedling vigor, plant size, and Number and distance, root growth, seed size, fruit size, pod size, number of pods or ears, number of seeds per pod or ear, seed quality, enhanced seed filling, reduced seed dispersibility, reduced pod cracking And lodging resistance. Additional yield traits include seed compositions such as carbohydrate content and compositions such as cotton or starch, protein content, oil content and composition, nutritional value, reduction of anti-nutritional compounds, improved processability, and better storage stability. .

Plants and plant cultivars which can be treated by the methods disclosed above include plant and plant cultivars which are hybrid plants which have generally exhibited generally high yield, vigor, health and resistance to abiotics and abiotics. The heterosis of adversity or the characteristics of hybrid vigor.

Plants and plant cultivars (obtained by genetically engineered plant biotechnology methods) which can be treated by the methods disclosed above include plant and plant cultivars which are herbicide tolerant plants, ie Or a variety of plants that are tolerant to established herbicides. Such plants can be obtained by genetic transformation or by selection of plants containing mutations conferring tolerance to such herbicides.

Plants and plant cultivars (obtained by genetic engineering engineering plant biotechnology methods) which can be treated by the methods disclosed above include plants and plant cultivars which are insect resistant transgenic plants, ie Some target insects attack plants that are resistant. Such plants can be obtained by genetic transformation or by selection of plants containing mutations conferring resistance to such insects.

Plants and plant cultivars (obtained by genetic engineering engineering plant biotechnology) that can be treated by the methods disclosed above include plants and plant cultivars that are resistant to abiotic stresses. Such plants can be obtained by genetic transformation or by selection of plants containing mutations conferring resistance to such stress.

Plants and plant cultivars (obtained by biotechnological methods such as genetic engineering) that can be treated by the methods disclosed above include displaying the number, quality and/or storage stability and/or alteration of the products collected. Plant and plant cultivars that characterize the specific components of the product collected.

Plants and plant cultivars (obtained by genetically engineered plant biotechnology methods) that can be treated by the methods disclosed above include plants and plant cultivars (such as cotton plants) having altered elastic fiber characteristics. Such plants can be obtained by genetic transformation or by selection of plants containing mutations that confer such altered fiber characteristics.

Plant or plant cultivars (obtained by genetic engineering engineering plant biotechnology methods) which can be treated by the methods disclosed above, include plants and plant cultivars having altered oil profile characteristics, such as canola or related cabbage Type of plant. Such plants can be obtained by genetic transformation or by selection of plants containing mutations that confer such altered oil profile characteristics.

Plants or plant cultivars which can be treated by the methods disclosed above (obtainable by means of genetic engineering engineering such as plant biotechnology) include plants and plant cultivars having altered grain size characteristics, such as canola or related cabbage Type of plant. Such plants can be obtained by genetic transformation or by selection of plants containing mutations that confer such altered shattering characteristics, and include plants having a delayed or reduced shredding property, such as a canola plant.

Plants and plant cultivars (obtained by genetic engineering engineering plant biotechnology methods) that can be treated by the methods disclosed above include plants and plant cultivars, such as tobacco plants, having altered post-translational protein modification patterns.

Pathogens and Diseases The methods disclosed above can be used to control disease-causing microorganisms, particularly phytopathogenic microorganisms, such as phytopathogenic fungi, such as:
A disease caused by a powdery mildew pathogen such as: Blumeria genus (eg, Blumeria graminis), Podosphaera genus (eg, white crosshair) a monocapsule (Podosphaera leucotricha), a genus of the genus Sphaerotheca (for example, Sphaerotheca fuliginea), a genus of Uncinula (for example, Uncinula necator);
A disease caused by a rust pathogen such as the genus Gymnosporangium (for example, Gymnosporangium sabinae) or the genus Hemileia (for example, Hemileia vastatrix) )), Phakopsora genus (such as Phakopsora pachyrhizi or Phakopsora meibomiae), Puccinia genus (such as Puccinia recondita) ), Puccinia graminis or Puccinia striiformis, Uromyces (eg Uromyces appendiculatus);
Diseases caused by pathogens from the oomycete group, such as the genus Albugo (such as Albugo candida), the genus of the genus Bremia (such as the lettuce bacterium (Bremia) Lactucae)), genus Peronospora (such as Peronospora pisi or P. brassicae), Phytophthora (such as Phytophthora infestans), uniaxial Plasmopara genus (eg Plasmopara viticola), Pseudoperonospora genus (eg Pseudoperonospora humuli or Pseudoperonospora cubensis), Pythium (Pyudoperonospora humuli) Pythium) (eg Pythium ultimum);
Leaf spot disease and leaf wilting diseases caused by, for example, Alternaria (such as Alternaria solani) and Cercospora (such as Cercospora) Beticola)), genus Cladiosporium (eg Cladiosporium cucumerinum), genus Cochliobolus (eg Cochliobolus sativus) (spore form: inner umbilical Drechslera, synonymous: Helminthosporium or Cochliobolus miyabeanus, Colletotrichum (such as Colletotrichum lindemuthanium), Cycloconium Genus (such as Cycloconium oleaginum), genus Diaporthe (such as Diaporthe citri), Elsinoe (such as citrus sac) Elsinoe, Gloeosporium (eg Gloeosporium laeticolor), Glomerella (eg Glomerella cingulate), Guignardia (eg Guignardia bidwelli), genus Leptosphaeria (eg Leptosphaeria maculans), Magnaporthe genus (eg Magnaporthe grisea) )), Microdochium genus (such as Microdochium nivale), Mycosphaerella genus (such as Mycosphaerella graminicola, Mycosphaerella) Arachidicola) or Mycosphaerella fijiensis, Phaeosphaeria (eg Phaeosphaeria nodorum), Pyrenophora genus (eg Pyrenophora teres or Pyrenophora tritici repentis, Ramularia genus (eg, Ramularia collo-cygni or Ramularia areola), Pyrenophora genus (eg Rhynchosporium secalis, Septoria genus (eg Septoria apii or Septoria lycopersici), Stagonospora genus (eg Ying) Stagonospora nodorum, Typhula genus (eg Typhula incarnate), Venturia genus (eg Venturia inaequalis),
Root and stem diseases caused by, for example, the genus Corticium (for example, Corticium graminearum) and the genus Fusarium (for example, Fusarium oxysporum) , the genus of the genus Gaeumannomyces (eg, Gaeumannomyces graminis), the genus Plasmodiophora (such as Plasmodiophora brassicae), the genus Rhizoctonia (eg, Rhizoctonia solani, Sarocladium genus (such as Sarocladium oryzae), Sclerotium genus (such as Sclerotium oryzae), Tap a genus of Tapesia (for example, Tapesia acuformis), a genus Thielaviopsis (for example, Thielaviopsis basicola);
Ear and panicle diseases (including corn cobs) caused by, for example, the following species: Alternaria (such as Alternaria spp.), Aspergillus (such as Aspergillus flavus) , Cladosporium genus (such as Cladosporium cladosporioides), Claviceps genus (such as Claviceps purpurea), Fusarium genus (for example) Fusarium culmorum), Gibberella genus (eg Gibberella zeae), Monographella genus (eg Monographella nivalis), shell needle Stagnospora genus (eg Stagnospora nodorum);
A disease caused by smut fungi, such as the genus Sphacelotheca (such as Sphacelotheca reiliana) and the genus Tilletia (such as caries) Tilletia caries or Tilletia controversa, Urocystis genus (eg Urocystis occulta), Ustilago genus (eg, Ustilago nuda);
Fruit rot caused by, for example, the genus Fusarium (such as Aspergillus), the genus Botrytis (such as Botrytis cinerea), the genus Penicillium (such as Penicillium expansum) Penicillium purpurogenum, Rhizopus genus (eg Rhizopus stolonifer), Sclerotinia genus (eg Sclerotinia sclerotiorum), Verticillium sp. Verticilium) (eg Verticilium alboatrum);
For example, seed and soil vector blight and wilt disease caused by the following diseases, as well as seedling diseases: Alternaria (such as Alternaria brassicicola), Aphanomyces (such as Beans) Aphanomyces euteiches, Ascochyta genus (eg Ascochyta lentis), Aspergillus genus (eg Aspergillus flavus), Cladosporium genus (eg Cladosporium herbarum), genus Cochliobolus (eg Cochliobolus sativus (conidial form: Helminthosporium, Bipolaris) Synonymous: Helminthosporium)), Colletotrichum (such as Colletotrichum coccodes), Fusarium (such as Fusarium culmorum), Gibberella Genus (eg Gibberella zeae), Macrophomina (eg Macrophomina phaseolina), Microdochium genus (eg, Microdochium nivale) )), small line shell (Monographella) genus (example Such as Monographella nivalis, Penicillium (such as Penicillium expansum), Phoma genus (such as Phoma lingam), Phomopsis genus (Phomopsis) For example, Phomopsis sojae, Phytophthora (such as Phytophthora cactorum), Pyrenophora (such as Pyrenophora graminea), Pyricularia (such as Pyricularia oryzae), Pythium (Pythium ultimum), Rhizoctonia (such as Rhizoctonia) Solani)), Rhizopus genus (eg Rhizopus oryzae), Sclerotium genus (eg Sclerotium rolfsii), Septoria genus (eg sage) Septoria nodorum, Typhula genus (eg Typhula incarnate), Verticillium genus (eg Verticillium dahlia);
A cancer, worm, and arbuscular disease caused by, for example, the genus Nectria (for example, Nectria galligena);
a wilt disease caused by, for example, the genus Monilinia (for example, Monilinia laxa);
Deformation of leaves, flowers and fruits caused by, for example, the genus Exobasidium (e.g., Exobasidium vexans), the genus of Taphrina (e.g., Taphrina deformans);
Degenerative diseases of woody plants caused by, for example, Esca (eg Phaeomoniella chlamydospora, Phaeeocremonium aleophilum or Fomitiporia) Mediterranea)), Ganoderma genus (eg Ganoderma boninense);
a disease caused by flowers and seeds caused by, for example, Botrytis (such as Botrytis cinerea);
A disease caused by, for example, plant tubers of the following species: Rhizoctonia genus (eg Rhizoctonia solani), Helminthosporium genus (eg Helminthosporium solani) ;
A disease caused by a bacterial pathogen such as Xanthomonas (such as Xanthomonas campestris pv. Oryzae) or Pseudomonas (eg, Pseudomonas syringae pv. Lachrymans), Erwinia (eg, Erwinia amylovora).

Seed Treatment Methods for controlling undesirable microorganisms can be used to protect seeds from phytopathogenic microorganisms, such as fungi.

As used herein, the term "seed" includes dormant seeds, primed seeds, pre-germinated seeds, and seeds having erupted roots and leaves.

Accordingly, the present invention also relates to a method for protecting seeds and/or crops from undesirable microorganisms, such as bacteria or fungi, comprising treating the compounds with one or more compounds of formula (I) or compositions comprising the same The steps of the seed. Treatment of the seed with one or more compounds of formula (I) or compositions comprising the same not only protects the seed from phytopathogenic microorganisms, but also protects the germinating plants, the erupted seedlings and the plants after emergence.

Seed treatment can be carried out before sowing, at the time of sowing or shortly after sowing.

When the seed treatment is carried out prior to sowing (for example on a so-called seed application), the seed treatment can be carried out as follows: the seed can be placed in a desired amount of one or more compounds of the formula (I) or a composition comprising the same (as is Or in a mixer after dilution, the seed is mixed with the one or more compounds of formula (I) or a composition comprising the same until a homogeneous distribution on the seed is achieved. The seeds can be dried as appropriate.

The invention also relates to seeds treated with one or more compounds of formula (I) or compositions comprising the same. As described above, the use of treated seeds not only protects the seeds before and after sowing from undesirable microorganisms (such as phytopathogenic fungi), but also protects the germinating plants and young seedlings elicited from the treated seeds. . A large part of the damage to the crop caused by the harmful organism is triggered by the infection of the seed before sowing or after the plant has sprouted. Since the roots and shoots of growing plants are particularly sensitive, this stage is particularly critical and even minor damage can cause plant death.

Accordingly, the present invention also relates to methods for protecting seeds, germinating plants, and erupted seedlings, and more generally to methods for protecting crops from phytopathogenic microorganisms, the method comprising using one or more (I) a step of a compound or a seed treated with a composition thereof.

Preferably, the seed is treated in a state where the damage is not sufficiently stable during the treatment. In general, the seed can be processed at any time between harvesting and shortly after sowing. Seeds that have been isolated from plants and released from the flesh of the cob, shell, stem, rind, hair or fruit are used conventionally. For example, it is possible to use seeds that have been harvested, cleaned and dried to a moisture content of less than 15% by weight. Alternatively, it is also possible to use seeds which have been treated after drying, for example, have been treated with water and subsequently dried again, or seeds which have just been conditioned, or seeds or pre-germinated seeds stored under osmotic conditions, or in seedling trays, strips or Seeds sowed on paper.

The amount applied to one or more of the compounds of formula (I) or a composition comprising the same is generally such that the germination of the seed does not diminish or the resulting plant does not. This must be specifically determined to prevent the active ingredient from exhibiting a phytotoxic effect at certain applied levels. When determining the amount of one or more compounds of formula (I) to be applied to the seed or a composition comprising the same, in order to achieve optimal seed with a minimum amount of one or more compounds of formula (I) or compositions comprising the same In the protection of germinating plants, the intrinsic phenotype of the transgenic plants should also be considered.

As indicated above, the compound of formula (I) can be applied directly to the seed as it is, i.e. without any other components and without dilution, or a composition comprising a compound of formula (I) can be applied. Preferably, the composition in any suitable form is applied to the seed. Examples of suitable formulations include solutions, emulsions, suspensions, powders, foams, slurries or other coating compositions in combination with such coating compositions, such as film forming materials, granulation Materials, fine iron or other metal powders, granules, drapes for inactivation of seeds, and ULV formulations. The formulation may be a ready-to-use formulation or may be a concentrate that needs to be diluted prior to use.

These formulations are prepared in a known manner, for example by mixing the active ingredient or mixtures thereof with conventional additives such as conventional extenders and solvents or diluents, dyes, wetting agents, dispersing agents, emulsifications. Agents, defoamers, preservatives, secondary thickeners, viscosifiers, gibberellins and water.

These formulations are prepared in a known manner by combining the active ingredient or active ingredient in admixture with conventional additives such as conventional extenders and solvents or diluents, dyes, wetting agents, dispersing agents, Emulsifiers, defoamers, preservatives, secondary thickeners, viscosifiers, gibberellins and water.

Suitable dyes which may be present in the form of a seed dressing formulation are all dyes customary for such purposes. It is possible to use a slightly water-soluble pigment or a water-soluble dye. Examples include dyes known under the names Rhodamine B, C.I. Pigment Red 112, and C.I. Solvent Red 1. Suitable humectants which may be present in the form of a seed cocktail formulation are those which promote moist and conventional use in the formulation of active agrochemical ingredients. An alkyl naphthalenesulfonate such as diisopropyl naphthalenesulfonate or diisobutyl naphthalenesulfonate can be preferably used. Useful dispersing agents and/or emulsifiers which may be present in the form of a seed-mixing formulation are conventionally employed as nonionic dispersing agents, anionic dispersing agents and cationic dispersing agents for the formulation of active agrochemical ingredients. A nonionic dispersant or an anionic dispersant or a mixture of a nonionic dispersant or an anionic dispersant may preferably be used. Suitable nonionic dispersants include, in particular, ethylene oxide/propylene oxide block copolymers, alkylphenol polyglycol ethers and tristyrylphenol polyglycol ethers and their phosphated or sulfated derivatives. . Suitable anionic dispersants are, in particular, lignosulfonates, polyacrylates and arylsulfonate/formaldehyde condensates. Defoamers which may be present in the form of a seed cocktail formulation are conventionally used in all foam inhibiting substances of formulations of active agrochemical ingredients. Preferably, a polydecane defoamer and magnesium stearate can be used. Preservatives which may be in the form of a seed dressing formulation are all materials which can be used for such purposes of agrochemical compositions. Examples include dichlorophenol and benzyl alcohol hemiformal. Secondary thickeners which may be present in the form of a seed dressing formulation are all materials which are useful for such purposes of agrochemical compositions. Preferred examples include cellulose derivatives, acrylic acid derivatives, xanthan gum, modified clay, and finely divided cerium oxide. The viscous agent which can be present in the form of a seed dressing formulation can be used in all conventional adhesives for seed dressing products. Preferred examples include polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, and methyl cellulose.

The compounds of formula (I) and compositions comprising the same are suitable for use in protecting seeds of any plant species used in agriculture, in greenhouses, in forests or in horticulture. More specifically, seeds are cereals (such as wheat, barley, rye, chestnut, triticale, and oats), canola, corn, cotton, soybeans, rice, potatoes, sunflowers, kidney beans, coffee, peas, and beets (such as sugar). Beets and fodder beets), peanuts, vegetables (such as tomatoes, courgettes, onions and lettuce), lawns and ornamental plants. Of particular importance are the treatment of seeds of wheat, soybeans, canola, corn and rice.

The compounds of formula (I) or compositions comprising the same can be used to treat seed of a transgenic gene, in particular a plant capable of expressing a protein, which acts against pests, herbicidal damage or abiotic stresses, thereby increasing protection. Synergistic effects can also occur in interactions with substances formed by expression.

The application of the compounds of the invention can be carried out as such or, for example, in the form of solutions, emulsions, aqueous or oil-based suspensions, powders, wettable powders, pastes, soluble powders, dusts, soluble granules, Dispersed granules, suspoemulsion concentrates, natural products impregnated with the compounds of the invention, synthetic materials impregnated with the compounds of the invention, fertilizers or microcapsules in polymeric materials.

The application is effected in a conventional manner, for example by watering, spraying, atomizing, spreading, dusting, foaming, smearing and the like. The compounds of the invention may also be deployed by ultra-low volume methods via a drip irrigation system or irrigation application to apply or spray them along the furrow into the field or soil. In addition, the compounds of the invention may be applied by means of wound seals, coatings or other wound dressings.

The effective amount and plant compatible amount of the compound of the present invention applied to plants, plant parts, fruits, seeds or soil will depend on various factors such as the compound/composition employed, the treated subject (plant, plant part, fruit) , seed or soil), type of treatment (dusting, spraying, seed mixing), treatment purpose (curative and protective), microbial type, microbial development stage, microbial sensitivity, crop growth stage and environmental conditions.

When the compound of the present invention is used as a fungicide, the amount applied can vary within a relatively wide range depending on the type of application. For treating plant parts such as leaves, the application amount may be in the range of 0.1 to 10 000 g/ha, preferably 10 to 1000 g/ha, more preferably 50 to 300 g/ha (applied by watering or dripping) In this case, the amount applied can be even reduced, especially when using an inert substrate such as asbestos or perlite. For the treatment of seeds, the application amount may be from 0.1 to 200 g/100 kg of seed, preferably from 1 to 150 g/100 kg of seed, more preferably from 2.5 to 25 g/100 kg of seed, even more preferably from 2.5 to 12.5 g/100 kg of seed. Within the scope. For treating the soil, the amount applied may be in the range of 0.1 to 10 000 g/ha, preferably 1 to 5000 g/ha.

The amounts applied are merely examples and are not intended to limit the scope of the invention.

Material Protection The compounds and compositions of the present invention can also be used to protect materials, particularly industrial materials that are protected from attack and damage by undesirable microorganisms.

Additionally, the compounds and compositions of the present invention can be used as antifouling compositions, either alone or in combination with other active ingredients.

Industrial materials in this context are understood to mean non-biological materials that have been prepared for use in the industry. For example, industrial materials to be protected from microbial changes or damage can be adhesives, glues, paper, wallpaper and cardboard/cardboard, textiles, carpets, leather, logs, fibers and paper towels, paints and plastics, Cooling lubricants and other materials that can be affected or broken by microorganisms. It is also possible to mention in the context of the material to be protected the production equipment and parts of the building that are damaged by the proliferation of microorganisms (eg water cooling circuits, cooling and heating systems, and ventilation and air conditioning units). Industrial materials within the scope of the present invention preferably include adhesives, sizes, papers and cards, leather, logs, paints, cooling lubricants and heat transfer fluids, and better logs.

The compounds and compositions of the present invention prevent side effects such as spoilage, rot, discoloration or mold formation.

In the case of processing logs, the compounds and compositions of the invention may also be used to combat fungal diseases that are susceptible to growth on or in wood.

Wood means all types of logs, and all types of processing of the logs to be used in construction, such as solid logs, high-density logs, laminated logs and plywood. Additionally, the compounds and compositions of the present invention can be used to protect articles (especially skins, screens, nets, construction, mooring boats, and signaling systems) that come into contact with saline or brackish water from fouling.

The compounds and compositions of the invention may also be used to protect stored goods. A stored good should be understood to mean a natural substance of vegetable or animal origin or a processed product thereof that has a natural source and requires long-term protection. Storage goods from vegetable sources (eg plant or plant parts such as stalks, leaves, tubers, seeds, fruits, grains) may be dried, wetted, comminuted, ground, pressed or baked just after harvesting or by (pre) drying It is protected after treatment. The stored goods also include wood, which is untreated (such as construction timber, utility poles and barriers) or in finished form (such as furniture). Storage goods of animal origin are, for example, hides, leather, fur and hair. The compounds and compositions of the present invention prevent side effects such as spoilage, rot, discoloration or mold formation.

Microorganisms capable of degrading or modifying industrial materials include, for example, bacteria, fungi, yeast, algae, and mucous organisms. Compounds and compositions of the present invention is preferred to fungi, in particular molds, wood and wood destroying fungi bleaching (aurantiacus (Ascomycetes), Basidiomycetes (Basidiomycetes), fungi imperfecti (, Deuteromycetes) and Zygomycetes (Zygomycetes)) and for mucus Organisms and algae work. Examples include microorganisms of the genus: the genus Alternaria, such as Alternaria tenuis ; the genus Fusarium, such as Aspergillus niger ; Chaetomium , such as Chaetomium Genus ( Ceatomium globosum ); Coniophora , such as Coniophora puetana ; Lentinus , such as Lentinus tigrinus ; Penicillium, such as gray-green Penicillium glaucum ; Polyporus , such as Polyporus versicolor ; Aureobasidium , such as Aureobasidium pullulans ; Sclerophoma , such as a green roof nuclear Phoma (Sclerophoma pityophila); Trichoderma sp. (Trichoderma), such as Trichoderma viride sp. (Trichoderma viride); fungus Ceratocystis (Ophiostoma spp.); Ceratocystis (Ceratocystis spp.); rot Humicola spp .; Petriella spp .; Trichurus spp .; Coriolus spp .; Gloeophyl Lum spp. ); Pleurotus spp .; Poria spp .; Serpula spp. and Tyromyces spp .; Cladosporium spp. ); the genus Paecilomyces (Paecilomyces spp);. white Streptomyces (Mucor spp);. genus Escherichia (Escherichia), such as E. coli (Escherichia coli); Pseudomonas (Pseudomonas), such as Pseudomonas aeruginosa bacillus (Pseudomonas aeruginosa); Staphylococcus (Staphylococcus), such as Staphylococcus aureus (Staphylococcus aureus); (. Candida spp) Candida and Saccharomyces, such as Saccharomyces cerevisiae (Saccharomyces cerevisae) (Saccharomyces spp. ).

The teachings of the present invention are further understood by the following examples, which are not to be construed as limiting the scope of the teachings of the present invention.
Instance

Similar to the examples disclosed herein below and in accordance with the general description of the methods disclosed herein, the compounds of formula (I) shown in Table 1a have been obtained.

In Table 1a, the logP values were determined by HPLC (High Performance Liquid Chromatography) on a reverse phase column (C18) using the method described below according to EEC Directive 79/831 Annex V.A8:

^[a] Method A: temperature: 40 ° C; mobile phase: 0.1% aqueous formic acid and aqueous acetonitrile; linear gradient: 10% acetonitrile to 95% acetonitrile;

Calibration is performed using unbranched alkan-2-ones (containing from 3 to 16 carbon atoms) with known logP values (the determination of the logP value by the linear interpolation method between two consecutive alkanones) . The maximum lambda value was determined using a UV spectrum from 200 nm to 400 nm and the peak of the chromatographic signal.

In Table 1a, A is connected to L _{2 of} formula (I) via a key identified by "*", and A is connected to the N-SO ₂ portion of formula (I) via a bond identified by "#".
Table 1a :
Note: Me: methyl

Table 1b illustrates, by way of non-limiting example, an example of an N-oxide compound of formula (I) according to the invention:

In Table 1b, logP is as defined for Table 1a.

In Table 1b, A is connected to L _{2 of} formula (I) via a key identified by "*", and A is connected to the N-SO ₂ portion of formula (I) via a bond identified by "#".
Table 1b :
Note: Me: methyl

Table 1c illustrates, by way of non-limiting example, an example of a compound of formula (II) according to the invention:

In Table 1c, logP is as defined for Table 1a.

In Table 1c, A is connected to C(OR ^2c )(R ^2a ) of formula (Ii) via a key identified by "*", and A is connected to N- of formula (Ii) via a key identified by "#" SO2 part.
Table 1c :
Note: Me: methyl

Table 1d illustrates, in a non-limiting manner, an example of an N-oxide compound of formula (II) according to the invention:

In Table 1d, logP is as defined for Table 1a.

In Table 1d, A is connected to C(OR ^2c )(R ^2a ) of formula (Ii) via a key identified by "*", and A is connected to N- of formula (Ii) via a key identified by "#" SO ₂ part.
Table 1d :
Note: Me: methyl

Table 2 illustrates, by way of non-limiting example, an example of a compound of formula (IIIa) according to the invention:

In Table 2, the GCMS residence time was determined by a DB17ms (15m x 0.25μm x 0.25μm) column using a gradient of 40 ° C / min from 40 ° C to 310 ° C and a flow rate of 1.5 mL / min He gas.

In Table 2, A is connected to L ^{2 of the} formula (IIIa) via a bond identified by "*", and A is connected to the N-SO ₂ portion of the formula (IIIa) via a bond identified by "#".
Table 2 :

Table 3 illustrates, by way of non-limiting example, an example of a compound of formula (VII) according to the invention:

In Table 3, logP is as defined for Table 1a.

In Table 3, A is connected to L ^{2 of the} formula (VII) via a bond identified by "*".
Table 3 :

Table 4 illustrates, by way of non-limiting example, an example of a compound of formula (X) according to the invention:

In Table 4, logP is as defined for Table 1a.

In Table 4, A is connected to the C=O portion of the formula (X) via a key identified by "*", and A is connected to the N-SO ₂ portion of the formula (X) via a bond identified by "#".
Table 4 :
Note: Me: methyl

Table 5 illustrates, by way of non-limiting example, an example of a compound of formula (XIa) according to the invention:

In Table 5, logP is as defined for Table 1a.

In Table 5, A is connected to the C=O portion of the formula (XIa) via a key identified by "*", and A is connected to the NH portion of the formula (XIa) via a bond identified by "#".
Table 5 :
Note: Me: methyl

Table 6 provides NMR data ( ¹ H) for some of the compounds disclosed in Tables 1a, 1b, 1c, 1d, 2, 3, 4 and 5.

The ¹ H-NMR data of the selected examples are presented in the form of a list of ¹ H-NMR peaks. For each signal peak, the delta value in ppm and the signal intensity in square brackets are listed.

In the printed NMR spectrum example, the intensity of the sharp signal is related to the signal height (cm) and shows the actual relationship of the signal strength. The self-wide signal can show several peaks or intermediate values of the signal and its relative intensity compared to the densest signal in the spectrum.

^{The 1} H-NMR peak list is similar to classical ¹ H-NMR printing and therefore typically contains all of the peaks listed in the classical NMR interpretation. Further, it can exhibit a solvent signal, a stereoisomer of the target compound (which is also the object of the present invention), and/or a peak of impurities as in classical ¹ H-NMR printing. In order to display the compound signal in the delta-range of solvent and/or water, the peak of the commonly used solvent (for example, the peak of DMSO in DMSO-d6) and the peak of water are shown in the ¹ H-NMR peak of ours. It is usually in the list and usually has a higher intensity.

The peaks of the stereoisomers of the target compound and/or the peaks of the impurities generally have an average lower intensity than the peak of the target compound (for example, having a purity greater than 90%). Such stereoisomers and/or impurities may be typical for a particular method of preparation. Therefore, its peak can help identify the reproduction of the preparation process via the "by-product fingerprint".

An expert who calculates the peak of the target compound by known methods (MestreC, ACD simulation, and empirically evaluated expected values) can optionally separate the peak of the target compound as needed using an additional intensity filter. This separation will be selected similar to the correlation peaks in the classical ¹ H-NMR interpretation.

Further details of the NMR data description with the peak list can be found in the publication "Citation of NMR Peak List Data within Patent Applications" of the Research Disclosure Database Number 564025.
Table 6 : NMR Peak List

The following examples illustrate, in a non-limiting manner, the efficacy and efficacy of the compounds of formula (I) according to the present invention.

Preparation Example 1 : Preparation of 3-(2,2-dioxal[1,2]thiazolo[4,3-b]pyridine-1( 3H )-yl)-8-fluoroquinoline ((Compound I) .01)
To 100 mg (0.52 mmol) of (8-fluoroquinolin-3-yl) Add acid and 89 mg (0.52 mmol) of 1,3-dihydro[1,2]thiazolo[4,3-b]pyridine 2,2-dioxide in 10 mL of dichloromethane 0.29 mL (2.09 mmol) of triethylamine, 190 mg (1.04 mmol) of copper (II) acetate and 260 mg of 4 Å molecular sieve. The reaction mixture was stirred at rt for 4 h then diluted with EtOAc EtOAc &EtOAc The organic phase was concentrated under reduced pressure and purified mjjjjjjjjjjjj Dioxyl[1,2]thiazolo[4,3-b]pyridine-1(3 H )-yl)-8-fluoroquinoline. LogP = 1.86 [Method A]. (M+H) = 316.

Preparation Example 2 : Preparation of 4,4-difluoro-1-(8-fluoroquinolin-3-yl)-3,3-dimethyl-3,4-dihydro-1 H -pyrido[3,2 -c][1,2]thiazine 2,2-dioxide (compound I.08)
Step 1 : Preparation of methyl 3-[(8-fluoroquinolin-3-yl)amino]pyridine-2-carboxylate

Add 45 mg (0.04 mmol) of ginseng (dibenzylideneacetone) dipalladium (0), 85 mg (0.14 mmol) of 4,5-bis(diphenyl) in a 100 mL round bottom flask under argon. Phosphyl)-9,9-dimethyldibenzopyran and 0.75 g (2.30 mmol) of cesium carbonate. 34 mL of 1,4-dioxane, 250 mg (1.64 mmol) of methyl 3-aminopyridine-2-carboxylate and 1.35 g (4.92 mmol) of 8-fluoro-3-iodoquinoline were added in that order. The reaction mixture was stirred under reflux for 20 hours. The reaction mixture was cooled to room temperature, diluted with dichloromethane and filtered over Celite® 545. The organic phase was concentrated under EtOAcqqqHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHH Methyl morpho-3-ylamino)benzoate LogP = 1.94 [Method A]. (M+H) = 298.

Step 2 : Preparation of methyl 3-[(8-fluoroquinolin-3-yl)(methylsulfonyl)amino]pyridine-2-carboxylate Lithium bis(trimethylsulfonyl)amine at 0 ° C The solution (6.73 mL, 1.0 M tetrahydrofuran solution, 6.73 mmol) was added to 2.0 g (6.72 mmol) of methyl 3-[(8-fluoroquinolin-3-yl)amino]pyridine-2-carboxylate in 37 mL In a solution in tetrahydrofuran. The mixture was stirred for 10 min to give an orange solution, and 0.78 mL (10.00 mmol) of methanesulfonium chloride was added at 0 °C. The resulting pale yellow solution was stirred at 0<0>C for 4 h then quenched with saturated aqueous ammonium chloride. The crude mixture was extracted with ethyl acetate. The combined organic layers were washed with EtOAc EtOAc m. The residue was purified by EtOAc EtOAc EtOAc (EtOAc (EtOAc) (Methanesulfonyl)amino]pyridine 2-carboxylic acid methyl ester. LogP = 1.69 [Method A]. (M+Na) = 398.

Step 3 : Preparation of 1-(8-fluoroquinolin-3-yl)-1 H -pyrido[3,2-c][1,2]thiazin-4(3 H )-one 2,2-di Oxide (Compound I.02)

To a suspension of 15 mg (60% (w/w) dispersion in mineral oil, 0.38 mmol) of sodium hydride in 0.53 mL of N,N-dimethylformamide at 0 °C Add 100 mg (0.26 mmol) of methyl 3-[(8-fluoroquinolin-3-yl)(methylsulfonyl)amino]pyridine-2-carboxylate to 0.53 mL of N,N-dimethylmethyl A solution in guanamine. The reaction mixture was allowed to warm to rt and stirred for 1.5 h. The reaction mixture was quenched with 1 M aqueous HCI and diluted withEtOAc. Separate the layers. The aqueous phase was neutralized to pH 7 with a saturated aqueous solution of sodium bicarbonate and extracted twice with ethyl acetate. The combined organic layers were washed with EtOAcq. The residue was purified by EtOAc EtOAc EtOAc (EtOAc) -1 H -pyrido[3,2-c][1,2]thiazin-4(3 H )-one 2,2-dioxide. LogP = 1.72 [Method A]. (M+H) = 344.

Step 4 : Preparation of 1-(8-fluoroquinolin-3-yl)-3,3-dimethyl-1 H -pyrido[3,2-c][1,2]thiazine-4 (3 H )-keto 2,2-dioxide (compound I.05)
To 3.20 g (purity 83%, 5.86 mmol) of 1-(8-fluoroquinolin-3-yl)-1 H -pyrido[3,2-c][1,2]thiazine-4 (3 H )-keto 2,2-dioxide In a solution of 207 mL of N,N-dimethylformamide, 2.14 g (15.4 mmol) of potassium carbonate and 1.11 mL (17.7 mmol) of methyl iodide were added. The resulting suspension was stirred at room temperature for 3 hours. The reaction mixture was diluted with ethyl acetate and water. The layers were separated and the aqueous layer was neutralized to pH 7 and extracted twice with ethyl acetate. The combined organic layers were washed with EtOAc EtOAc m. The residue was purified by EtOAc EtOAc EtOAc EtOAc (EtOAc) -3,3-Dimethyl-1H-pyrido[3,2-c][1,2]thiazine-4( 3H )-one 2,2-dioxide. LogP = 2.11 [Method A]. (M+H) = 374.

Step 5 : Preparation of 4,4-difluoro-1-(8-fluoroquinolin-3-yl)-3,3-dimethyl-3,4-dihydro-1 H -pyrido[3,2- c][1,2]thiazine 2,2-dioxide (compound I.08)
To 150 mg (0.35 mmol) of 1-(8-fluoroquinolin-3-yl)-3,3-dimethyl-1H-pyrido[3,2-c][1,2] at room temperature To a solution of thiazide-4( 3H )-one 2,2-dioxide in 0.7 mL of toluene was added 0.52 mL (1.42 mmol) of bis(2-methoxyethyl)aminosulfur trifluoride. The reaction mixture was stirred at 80 ° C for 72 hours. The reaction mixture was cooled to room temperature and 0.26 mL (0.71 mmol) of bis(2-methoxyethyl)amine sulphur trifluoride was added. The reaction mixture was stirred at 80 ° C for 24 hours. The reaction mixture was cooled to 0.degree. C., diluted with EtOAc EtOAc. The aqueous phase was extracted twice with ethyl acetate. The combined organic extracts were washed with EtOAcq. The residue was purified by EtOAc EtOAc EtOAc EtOAc (EtOAc) Fluoroquinolin-3-yl)-3,3-dimethyl-3,4-difluoro-1 H -pyrido[3,2-c][1,2]thiazine 2,2-dioxide . LogP = 2.57 [Method A]. (M+H) = 394.

Preparation Example 3 : Preparation of 4-(benzyloxy)-1-(8-fluoroquinolin-3-yl)-3,3,4-trimethyl-3,4-dihydro-1 H -pyridine [3,2-c][1,2]thiazine 2,2-dioxide (compound I.28)

Step 1 : Preparation of 1-(8-fluoroquinolin-3-yl)-3,3,4-trimethyl-3,4-dihydro-1 H -pyrido[3,2-c][1, 2] thiazin-4-ol 2,2-dioxide (compound I.10)
50 mg (0.13 mmol) of 1-(8-fluoroquinolin-3-yl)-3,3-dimethyl-1 H -pyrido[3,2-c][1,2 at 0 °C A solution of 0.16 mL of methylmagnesium chloride (3 M tetrahydrofuran solution, 0.47 mmol) was added dropwise to a solution of thiazol-4( 3H )-one 2,2-dioxide in 1.4 mL of tetrahydrofuran. The reaction mixture was allowed to warm to room temperature and stirred for 1 hour. The reaction mixture was cooled to 0.degree. C. and was quenched with aq. The layers were separated and the aqueous layer was extracted twice with ethyl acetate. The combined organic layers were washed with EtOAc EtOAc m. The residue was purified by EtOAc EtOAc EtOAc (EtOAc) -3,3,4-Trimethyl-3,4-dihydro-1 H -pyrido[3,2-c][1,2]thiazin-4-ol 2,2-dioxide. LogP = 2.18 [Method A]. (M+H) = 388.

Step 2 : Preparation of 4-(benzyloxy)-1-(8-fluoroquinolin-3-yl)-3,3,4-trimethyl-3,4-dihydro-1 H -pyridine and [ 3,2-c][1,2]thiazine 2,2-dioxide (compound I.28)
70 mg (0.18 mmol) of 1-(8-fluoroquinolin-3-yl)-3,3,4-trimethyl-3,4-dihydro-1 H -pyrido[3] at 0 °C , 2-c][1,2]thiazin-4-ol 2,2-dioxide added to a solution of 4.5 mL of N,N-dimethylformamide 10 mg (60% (w/ w) a dispersion in mineral oil, 0.25 mmol) of sodium hydride and 32 μL (0.27 mmol) of benzyl bromide. The reaction mixture was allowed to warm to room temperature and stirred for 2 h. The reaction was quenched with aq. aq. The combined organic extracts were washed with EtOAc EtOAc m. The residue was purified by EtOAc EtOAc EtOAc (EtOAc) 8-fluoroquinolin-3-yl)-3,3,4-trimethyl-3,4-dihydro-1 H -pyrido[3,2-c][1,2]thiazine 2,2 - dioxide. LogP = 3.94 [Method A]. (M+Na) = 500.

Preparation Example 4: Preparation of 1-(8-fluoro-1-oxo-ylquinolin-3-yl)-4-methoxy-3,3,4-trimethyl-3,4-dihydro-1H- Pyrido[3,2-c][1,2]thiazine 2,2-dioxide (compound I.40) and 1-(8-fluoroquinolin-3-yl)-4-methoxy- 3,3,4-trimethyl-3,4-dihydro-1H-pyrido[3,2-c][1,2]thiazine 2,2,5-trioxide (Compound I.38)

126 mg (0.31 mmol) of 1-(8-fluoroquinolin-3-yl)-4-methoxy-3,3,4-trimethyl-3,4-dihydro-1H at 0 °C - a solution of pyridyl[3,2-c][1,2]thiazine 2,2-dioxide in 5 mL of dichloromethane, 90 mg (purity 60%, 0.31 mmol) A solution of benzoic acid in 5 mL of dichloromethane. The reaction was stirred at room temperature for 11 days. The reaction mixture was washed with EtOAc EtOAc. The residue was purified by EtOAc EtOAc EtOAc (EtOAc (EtOAc) 4-methoxy-3,3,4-trimethyl-3,4-dihydro-1H-pyrido[3,2-c][1,2]thiazine 2,2,5-trioxide Things. LogP = 1.94 [Method A]. The second fraction was further purified by preparative HPLC (gradient of acetonitrile / water + 0.1% HCO2H) to yield 9 mg (purity 95%, yield 6%) oily 1-(8-fluoro-1-oxo Quinolin-3-yl)-4-methoxy-3,3,4-trimethyl-3,4-dihydro-1H-pyrido[3,2-c][1,2]thiazine 2,2-dioxide. LogP = 1.87 [Method A].

Biological data
Example: live on Alternaria brassicae (Alternaria brassicae) (carrot or cabbage, leaf spot of) the <br/> vivo preventive test Solvent: 5% by volume of dimethyl sulfoxide
10% by volume of acetone emulsifier: 1 μl of Tween ^® 80 per mg of test compound

So that the test compound in dimethyl sulfoxide / acetone / Tween ^® 80 mixture of soluble and homogenized, and then diluted with water to the desired concentration.

Young plants of radish or kale are treated by spraying the test compound prepared as described above. Only acetone / dimethyl sulfoxide / Tween ^® 80 solution of the untreated control plants.

After 24 hours, the plants were contaminated by spraying the leaves with an aqueous suspension of Alternaria alternata. The contaminated radish or cabbage plants were incubated for 6 days at 20 ° C and at 100% relative humidity.

The test was evaluated 6 days after the inoculation. 0% means efficacy corresponding to the efficacy of the control plants, while 100% efficacy means no disease is observed.

In this test, the following compounds according to the invention exhibited an efficacy between 70% and 79% at a concentration of 500 ppm of the tested compound: I.27; I.29

In this test, the following compounds according to the invention exhibited an efficacy between 80% and 89% at a concentration of 500 ppm of the tested compound: I.06

In this test, the following compounds according to the invention exhibited an efficacy between 90% and 100% at a concentration of 500 ppm of the tested compound: I.03

Example : In vivo prophylactic test against Botrytis cinerea ( Gold mold ) Solvent: 5 vol% dimethyl hydrazine
10% by volume of acetone emulsifier: 1 μL of Tween ^® 80 per mg of test compound

So that the test compound in dimethyl sulfoxide / acetone / Tween ^® 80 mixture of soluble and homogenized, and then diluted with water to the desired concentration.

Young plants of cucumbers were treated by spraying the test compounds prepared as described above. Only acetone / dimethyl sulfoxide / Tween ^® 80 solution of the untreated control plants.

After 24 hours, the plants were contaminated by spraying the leaves with an aqueous suspension of Botrytis cinerea spores. The contaminated cucumber plants were incubated for 4 to 5 days at 17 ° C and at 90% relative humidity.

The test was evaluated 4 to 5 days after inoculation. 0% means efficacy corresponding to the efficacy of the control plants, while 100% efficacy means no disease is observed.

In this test, the following compounds according to the invention exhibited efficacy between 70% and 79% at a concentration of 500 ppm of the tested compound: I.06; I.08; I.32

In this test, the following compounds according to the invention exhibited an efficacy between 80% and 89% at a concentration of 500 ppm of the tested compound: I.20; I.21; I.22

In this test, the following compounds according to the invention exhibited an efficacy between 90% and 100% at a concentration of 500 ppm of the tested compound: I.09; I.11; I.25; I.27; I.28 ;I.29; I.30; I.31; I.37

Example : In vivo prophylactic test for powdery mildew of the monofilament shell ( Gourd powdery mildew ) Solvent: 5 vol% of dimethyl hydrazine
10% by volume of acetone emulsifier: 1 μL of Tween ^® 80 per mg of test compound

So that the test compound in dimethyl sulfoxide / acetone / Tween ^® 80 mixture of soluble and homogenized, and then diluted with water to the desired concentration.

Young plants of cucumbers were treated by spraying the test compounds prepared as described above. Only acetone / dimethyl sulfoxide / Tween ^® 80 solution of the untreated control plants.

After 24 hours, the plants were contaminated by spraying the leaves with an aqueous suspension of spores of the genus Aspergillus. The contaminated cucumber plants were incubated for 8 days at 20 ° C and at 70-80% relative humidity.

The test was evaluated 8 days after inoculation. 0% means efficacy corresponding to the efficacy of the control plants, while 100% efficacy means no disease is observed.

In this test, the following compounds according to the invention exhibited an efficacy between 70% and 79% at a concentration of 500 ppm of the tested compound: I.18; I.23; I.25

In this test, the following compounds according to the invention exhibit efficacy between 90% and 100% at a concentration of 500 ppm of the tested compound: I.17; I.27; I.35

Example: Kidney bean anthracnose In vitro cell test solvent: DMSO
Medium: 14.6 g anhydrous D-glucose (VWR), 7.1 g fungal peptone (Oxoid), 1.4 g granular yeast extract (Merck), QSP 1 liter inoculum: spore suspension

The compound to be tested is dissolved in DMSO and used to prepare a solution of the desired concentration range. The final concentration of DMSO used in the analysis was < 1%.

A spore suspension of the bean anthracnose is prepared and diluted to the desired spore density.

The ability of the compounds to inhibit spore germination and mycelial growth in liquid media assays was assessed. The compound is added to the medium with spores at the desired concentration. After 6 days of incubation, the fungal toxicity of the compounds was determined by spectroscopic measurements of mycelial growth. Inhibition of fungal growth was determined by comparing the absorbance values in wells containing the test compound to the absorbance in control wells without the test compound.

In this test, the following compounds according to the invention exhibited an efficacy between 70% and 79% at a concentration of 20 ppm of the tested compound: I.13; I.32

In this test, the following compounds according to the invention exhibited an efficacy between 80% and 89% at a concentration of 20 ppm of the tested compound: I.02; I.14; I.25

In this test, the following compounds according to the invention exhibited an efficacy between 90% and 100% at a concentration of 20 ppm of the tested compound: I.06; I.09; I.11; I.27; I.28 ;I.29; I.30; I.31

Example: In vitro cell test of P. sinensis Solvent: DMSO
Medium: 14.6 g anhydrous D-glucose (VWR), 7.1 g fungal peptone (Oxoid), 1.4 g granular yeast extract (Merck), QSP 1 liter inoculum: spore suspension

The compound to be tested is dissolved in DMSO and used to prepare a solution of the desired concentration range. The final concentration of DMSO used in the analysis was < 1%.

A spore suspension of P. oryzae was prepared and diluted to the desired spore density.

The ability of the compounds to inhibit spore germination and mycelial growth in liquid media assays was assessed. The compound is added to the medium with spores at the desired concentration. After 5 days of incubation, the fungal toxicity of the compounds was determined by spectroscopic measurements of mycelial growth. Inhibition of fungal growth was determined by comparing the absorbance values in wells containing the test compound to the absorbance in control wells without the compound to be tested.

In this test, the following compounds according to the invention exhibited an efficacy between 70% and 79% at a concentration of 20 ppm of the tested compound: I.19; I.25; I.29; I.36; I.37

In this test, the following compounds according to the invention exhibited an efficacy between 80% and 89% at a concentration of 20 ppm of the tested compound: I.09; I.22; I.34; I.38; I.39 ;I.40

In this test, the following compounds according to the invention exhibited an efficacy between 90% and 100% at a concentration of 20 ppm of the tested compound: I.06; I.11; I.32; I.35.

Claims (15)

a compound of formula (I), Wherein A is a 5- or 6-membered unsaturated heterocyclic ring comprising 1, 2 or 3 heteroatoms independently selected from the list consisting of N, O and S; Z is selected from the group consisting of: a hydrogen atom, a halogen atom a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group containing up to 9 halogen atoms which may be the same or different, a C ₁ -C ₆ alkoxy group, containing up to 9 halogen atoms which may be the same or different. C ₁ -C ₆ haloalkoxy and cyano, wherein each of Z is optionally substituted; n is 0, 1, 2 or 3; X is independently selected from the group consisting of: a halogen atom, C ₁ - alkyl _{C. 8,} may contain up to 9 identical or different halogen atoms C ₁ -C ₈ -haloalkyl, C ₂ -C ₈ alkenyl group, containing up to 9 C may be the same or different halogen atoms ₂ -C ₈ Haloalkenyl, C ₂ -C ₈ alkynyl, C ₂ -C ₈ haloalkynyl, C ₃ -C ₇ cycloalkyl, containing up to 9 halogen atoms which may be the same or different, containing up to 9 Or a different halogen atom of C ₃ -C ₇ halocycloalkyl, C ₃ -C ₇ cycloalkyl-C ₁ -C ₈ alkyl, C ₄ -C ₇ cycloalkenyl, hydroxy, C ₁ -C ₈ Alkoxy, containing up to 9 halogens which may be the same or different The C ₁ -C ₈ haloalkoxy, aryl, aryl -C ₁ -C ₈ alkyl, heterocyclyl, heterocyclyl -C ₁ -C ₈ alkyl, methyl acyl, C ₁ -C ₈ alkyl a carbonyl group, a C ₁ -C ₈ haloalkylcarbonyl group containing up to 9 halogen atoms which may be the same or different, a (hydroxyimino) C ₁ -C ₈ alkyl group, (C ₁ -C ₈ alkoxyimino group) ) C ₁ -C ₈ alkyl, carboxy, C ₁ -C ₈ alkoxycarbonyl group, comprising up to 9 halogen atoms may be the same or different C ₁ -C ₈ haloalkoxy group, a carbonyl group, a carbamoyl acyl, C ₁ - C ₈ alkylamine methyl fluorenyl, di C ₁ -C ₈ alkylamine methyl fluorenyl, amine group, C ₁ -C ₈ alkylamino group, di C ₁ -C ₈ alkylamino group, thiol group, C ₁ -C ₈ alkylhydrosulfanyl, C ₁ -C ₈ alkylsulfinyl, C ₁ -C ₈ alkylsulfonyl, C ₁ -C ₆ trialkyldecyl, C ₁ -C ₆ a trialkylsulfonyl-C ₁ -C ₆ alkyl group, a cyano group and a nitro group, wherein each of X is optionally substituted; W is a CH ₂ or N; Y ² , Y ³ , Y ⁴ and Y ⁵ systems is independently selected from the group consisting of: a hydrogen atom, a halogen atom, C ₁ -C ₈ alkyl group, may contain up to 9 identical or different halogen atoms C ₁ -C ₈ -haloalkyl, C ₂ -C ₈ alkenyl group Including up to 9 a C ₂ -C ₈ haloalkenyl group, a C ₂ -C ₈ alkynyl group of the same or different halogen atoms, a C ₂ -C ₈ haloalkynyl group containing up to 9 halogen atoms which may be the same or different, C ₃ - C ₇ cycloalkyl, C ₄ -C ₇ cycloalkenyl, hydroxy, C ₁ -C ₈ alkoxy group, may contain up to 9 identical or different halogen atoms C ₁ -C ₈ haloalkoxy group, an aryl group, Heterocyclyl, indolyl, C ₁ -C ₈ alkylcarbonyl, (hydroxyimino) C ₁ -C ₈ alkyl, carboxyl, (C ₁ -C ₈ alkoxyimino)C ₁ -C _8- alkyl, C ₁ -C ₈ alkoxycarbonyl, amine methyl sulfonyl, C ₁ -C ₈ alkylamine methyl fluorenyl, di C ₁ -C ₈ alkylamine carbhydryl, amine, C ₁ -C _8- alkylamino, di-C ₁ -C ₈ alkylamino, thiol, C ₁ -C ₈ alkylthiol, C ₁ -C ₈ alkylsulfinyl, C ₁ -C ₈ alkane a sulfonyl group, a C ₁ -C ₆ trialkyl fluorenyl group, a cyano group and a nitro group, wherein each of Y is optionally substituted; L ¹ is CR ^1a R ^1b , wherein: R ^1a and R ^1b are independently selected from the group consisting of: a hydrogen atom, a halogen atom, C ₁ -C ₈ alkyl group, comprising up to 9 identical or different halogen atoms C ₁ -C ₈ -haloalkyl, C ₂ -C ₈ alkenyl group, Included to 9 may be the same or different halogen atoms C ₂ -C ₈ haloalkenyl, C ₂ -C ₈ alkynyl group, may contain up to 9 identical or different halogen atoms, haloalkyl of C ₂ -C ₈ alkynyl group, C ₃ -C ₇ cycloalkyl group, comprising up to 9 identical or different halogen atoms of C ₃ -C ₇ halocycloalkyl, C ₃ -C ₇ cycloalkyl, -C ₁ -C ₈ alkyl, aryl , aryl-C ₁ -C ₈ alkyl, heterocyclyl, heterocyclyl-C ₁ -C ₈ alkyl, hydroxy, C ₁ -C ₈ alkoxy and containing up to 9 halogens which may be the same or different a C ₁ -C ₈ haloalkoxy group of the atom, wherein each of R ^1a and R ^1b is optionally substituted, or R ^1a and R ^1b together with the carbon atom to which they are attached form a 3 member, 4 member, 5 member or a 6-membered saturated or partially saturated, optionally substituted carbocyclic or heterocyclic ring comprising at least one heteroatom selected from the list consisting of N, O and S, or R ^1a and R ^1b together with the carbon atom to which they are attached An unsubstituted or substituted saturated or partially unsaturated bicyclo[m ¹ , m ² ,0]-C ₆ -C ₁₁ alkyl group, wherein m ² ≥ 1 and m ¹ + m ² = 4 to 9, are formed together. or R ^1a and R ^1b together with the carbon atoms they are attached form a unsubstituted or substituted with the Or partially unsaturated heterobicyclic ^{[m 1, m 2, 0} ] -C 6 -C 11 alkyl group, which comprises 1 to 4 heteroatoms independently selected from the list consisting of N, O and S consisting of heteroatoms, wherein m ² ≥ 1 and m ¹ + m ² = 4 to 9, or R ^1a and R ^1b together with the carbon atom to which they are attached form an unsubstituted or substituted saturated or partially unsaturated snail [n ¹ , n ² ] -C ₅ -C ₁₁ alkyl, wherein n ¹ ≥ 2 and n ¹ + n ² = 4 to 10, or R ^1a and R ^1b together with the carbon atom to which they are attached form an unsubstituted or substituted saturated or partially An unsaturated heterospiro[n ¹ ,n ² ]-C ₅ -C ₁₁ alkyl group comprising from 1 to 4 heteroatoms independently selected from the list consisting of N, O and S, wherein n ¹ ≥ 2 and n ¹ + n ² = 4 to 10, or R ^1a and R ^1b together with the carbon atom to which they are attached form an unsubstituted or substituted methylene group; and an L ² direct bond, CR ^2a R ^2b or C (= O), wherein R ^2a and R ^2b are independently selected from the system consisting of the group consisting of: a hydrogen atom, a halogen atom, C ₁ -C ₈ alkyl group, may contain up to 9 identical or different halogen atoms C ₁ -C ₈ haloalkyl, C ₂ -C ₈ alkenyl group, may contain up to 9 identical or different halogen atom The C ₂ -C ₈ haloalkenyl, C ₂ -C ₈ alkynyl group, may contain up to 9 identical or different halogen atoms C ₂ -C ₈ haloalkynyl, C ₃ -C ₇ cycloalkyl, C ₃ -C ₇ halocycloalkyl, C ₃ -C ₇ cycloalkyl-C ₁ -C ₈ alkyl, aryl, aryl-C ₁ -C containing up to 9 halogen atoms which may be the same or different ₈ alkyl, heterocyclyl, heterocyclyl -C ₁ -C ₈ alkyl, hydroxy, C ₁ -C ₈ alkoxy group, may contain up to 9 identical or different halogen atoms C ₁ -C ₈ haloalkoxy group, C ₂ -C ₈ alkenyl group, may contain up to 9 identical or different halogen atoms C ₂ -C ₈ haloalkenyl group, C ₃ -C ₈ alkynyl group, may contain up to 9 identical or halogen atoms different from C ₃ -C ₈ haloalkynyloxy, C ₃ -C ₇ cycloalkoxy, may contain up to 9 identical or different halogen atoms C ₃ -C ₇ halocycloalkyl alkoxy, C ₃ -C ₇ cycloalkyl-C ₁ -C ₈ alkoxy, aryloxy, aryl-C ₁ -C ₈ alkoxy, heterocyclyloxy, heterocyclyl-C ₁ -C ₈ alkane An oxy group and a partially saturated or unsaturated fused bicyclic 9 member, 10 member or 11 membered heterocyclyl-C ₁ -C comprising from 1 to 5 heteroatoms independently selected from the list consisting of N, O and S ₈ alkoxy, wherein each of R ^2a and R ^2b is optionally substituted, or R ^2a and R ^2b together with the carbon atom to which they are attached form an unsubstituted or substituted 3 member, 4 member, 5 member Or a 6-membered saturated or partially saturated carbocyclic or heterocyclic ring comprising at least one heteroatom selected from the list consisting of N, O and S, or R ^2a and R ^2b together with the carbon atom to which they are attached Substituted or substituted saturated or partially unsaturated bicyclo[m ¹ , m ² ,0]-C ₆ -C ₁₁ alkyl, wherein m ² ≥ 1 and m ¹ + m ² = 4 to 9, or R ^2a and R ^2b together with the carbon atom to which it is attached forms an unsubstituted or substituted saturated or partially unsaturated heterobicyclo[m ¹ , m ² ,0]-C ₆ -C ₁₁ alkyl group, which contains from 1 to 4 a hetero atom independently selected from the list consisting of N, O and S, wherein m ² ≥ 1 and m ¹ + m ² = 4 to 9, or R ^2a and R ^2b together with the carbon atom to which they are attached form an unsubstituted Or a substituted saturated or partially unsaturated spiro[n ¹ ,n ² ]-C ₅ -C ₁₁ alkyl group, wherein n ¹ ≥ 2 and n ¹ + n ² = 4 to 10, or R ^2a and R ^2b together The carbon atoms to which they are attached together form an unsubstituted or substituted saturated Or a partially unsaturated heterospiro[n ¹ ,n ² ]-C ₅ -C ₁₁ alkyl group comprising from 1 to 4 heteroatoms independently selected from the list consisting of N, O and S, wherein n ¹ ≥ 2 And n ¹ + n ² = 4 to 10, or R ^2a and R ^2b together with the carbon atom to which they are attached form an unsubstituted or substituted methylene group; and a salt, an N-oxide thereof, a metal complex thereof Metalloid complexes and optically active isomers or geometric isomers. A compound of claim 1 wherein A is pyridyl or thienyl. The compound of claim 1, wherein A is selected from the group consisting of: Where X and n are as described in claim 1. A compound according to any one of the preceding claims, wherein L ¹ is CR ^1a R ^1b , wherein R ^1a and R ^1b are independently selected from the group consisting of: a hydrogen atom, a halogen atom, an unsubstituted or substituted C _1- C ₆ alkyl, unsubstituted or substituted C ₂ -C ₆ alkenyl, unsubstituted or substituted C ₂ -C ₆ haloalkenyl, unsubstituted or substituted C ₂ -C ₆ alkynyl, unsubstituted or substituted C ₃ -C ₇ cycloalkyl, unsubstituted or substituted C ₃ -C ₇ cycloalkyl-C ₁ -C ₆ alkyl, unsubstituted or substituted Aryl, unsubstituted or substituted heterocyclic-C ₁ -C ₆ alkyl, unsubstituted or substituted heterocyclic group and unsubstituted or substituted aryl-C ₁ -C ₈ alkane base. A compound according to any one of the preceding claims, wherein L ¹ is CR ^1a R ^1b , wherein R ^1a and R ^{1b are} independently a hydrogen atom or an unsubstituted C ₁ -C ₆ alkyl group. A compound according to any one of the preceding claims, wherein L ² is C(=O) or CR ^2a R ^2b , wherein R ^2a and R ^{2b are} as described in claim 1. A compound according to any one of the preceding claims, wherein L ² is C(=O) or CR ^2a R ^2b , wherein R ^2a and R ^2b are independently selected from the group consisting of: a hydrogen atom, a halogen atom, Substituted or substituted C ₁ -C ₆ alkyl, hydroxy, unsubstituted or substituted C ₁ -C ₆ alkoxy, unsubstituted or substituted C ₂ -C ₆ alkenyloxy, unsubstituted Or a substituted aryl-C ₁ -C ₆ alkoxy group and an unsubstituted or substituted heterocyclic group -C ₁ -C ₆ alkoxy group. The compound according to any of the preceding claims, wherein X is independently selected from the group consisting of: a halogen atom, an unsubstituted or substituted C ₁ -C ₆ alkyl group, containing up to 9 which may be the same or different. C ₁ -C ₆ haloalkyl, unsubstituted or substituted C ₂ -C ₈ alkenyl, unsubstituted or substituted C ₂ -C ₈ alkynyl, unsubstituted or substituted C ₃ -C ₇ -cycloalkyl, hydroxy, unsubstituted or substituted with of C ₁ -C ₆ alkoxy group, may contain up to 9 identical or different halogen atoms C ₁ -C ₆ haloalkyl alkoxy, unsubstituted or Substituted aryl, unsubstituted or substituted heterocyclic group, unsubstituted or substituted C ₁ -C ₆ alkylcarbonyl, unsubstituted or substituted C ₁ -C ₆ trialkyl fluorenyl -C ₁ -C ₆ alkyl and unsubstituted or substituted C ₁ -C ₆ trialkylindenyl. A compound according to any one of the preceding claims, wherein the Z is a hydrogen atom. A compound according to any one of the preceding claims, wherein n is preferably 0, 1 or 2. The compound according to any one of the preceding claims, wherein Y ² , Y ³ , Y ⁴ and Y ⁵ are independently selected from the group consisting of a hydrogen atom, a halogen atom, an unsubstituted or substituted C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl containing up to 9 halogen atoms which may be the same or different, unsubstituted or substituted C ₃ -C ₇ cycloalkyl, hydroxy, unsubstituted or substituted C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy containing up to 9 halogen atoms which may be the same or different, unsubstituted or substituted C ₁ -C ₆ alkoxycarbonyl, formyl and cyanide base. A compound according to any one of the preceding claims, wherein Y ² , Y ³ , Y ⁴ and Y ^{5 are} independently a hydrogen atom or a halogen atom. A composition comprising one or more compounds of formula (I) according to any one of claims 1 to 12 and one or more acceptable carriers. A method for controlling undesirable phytopathogenic microorganisms, the method comprising the steps of: applying one or more compounds of formula (I) according to any one of claims 1 to 12 or a composition according to claim 13 to Plants, plant parts, seeds, fruits or soil applied to the growth of such plants. A process for the manufacture of a compound of formula (I) according to any one of claims 1 to 12, which comprises the step of reacting one of the compounds of formula (II) or a salt thereof with a compound of formula (III): Process P1 wherein A, n, X, Y ² , Y ³ , Y ⁴ , Y ⁵ , W, Z, L ¹ and L ^{2 are} as described in claim 1 and U ¹ is a fluorine atom, a bromine atom, a chlorine atom or an iodine Atom, methanesulfonyl, toluenesulfonyl, trifluoromethanesulfonyl or boron derivatives.