HK1050689A

HK1050689A - Picolinic acid derivatives and their use as fungicides

Info

Publication number: HK1050689A
Application number: HK03102917.3A
Authority: HK
Inventors: F‧尼托-罗曼; J‧P‧沃尔斯; A‧维利尔; H‧拉切斯; A‧莫斯克斯; B‧哈特曼; P‧胡丁; J‧L‧莫利纳; B‧穆勒
Original assignee: 阿方蒂农科股份有限公司
Priority date: 2000-01-06
Filing date: 2001-01-05
Publication date: 2003-07-04

Description

Picolinic acid derivatives and their use as fungicides

The present invention relates to novel picolinic acid derivatives, processes for their preparation, their use as fungicides, particularly as fungicidal compositions, and methods for the control of phytopathogenic fungi using these compounds or their compositions.

Picolinic acid derivatives having fungicidal action are known from the literature. In particular, The publications of patent applications WO-A-99/11127 and Kuzo S et al [ Journal of antibiotics, 51(12), (1998), 1113-1116], disclose The good efficacy of antimycin and certain derivatives thereof against phytopathogenic fungi. However, these compounds and the compounds reported in US-A-3,228,950 have no substituent at the 4-position of the pyridine nucleus.

The pyridine carboxamide derivatives proposed in patent application WO-A-00/26191 are optionally substituted with methoxy in position 4. Patent application WO-A-95/25723 proposes 3-pyridylcarboxylic acid derivatives.

However, these known compounds are toxic products, and this disadvantage makes them banned from being used in the agricultural field for eradicating phytopathogenic diseases of crops. In addition, these compounds are obtained from fermentation of musk and have relatively complex chemical structures. Thus, the preparation and purification of these compounds remains a very demanding and expensive operation, making them industrially non-synthetic or marketable.

Pyridine amide derivatives are also known from the patent application publication of JP-11228542. These derivatives have potential antifungal activity and low toxicity, and can be used in medicine. Other picolinic acid derivatives are also known from patent application EP-A-0690061, wherein such compounds are useful as synthetic intermediates for the preparation of pyridothiazoles.

A first object of the present invention therefore comprises a novel family of picolinic acid derivatives which does not have the above-mentioned drawbacks.

It is another object of the present invention to propose novel compounds having improved activity, both qualitatively and quantitatively, compared to known fungicides, antimycin or derivatives thereof. Activity means fungicidal activity; an improvement in quantitative terms means a better control of the phytopathogenic fungi on the plants and an improvement in qualitative terms means a broader spectrum of activity, that is to say a greater variety of phytopathogenic fungi can be controlled.

It is another object of the present invention to provide a novel family of compounds having improved toxicity and/or phytotoxicity and/or ecotoxicity compared to known fungicides, in particular antimycin and derivatives thereof.

It is a further object of the present invention to provide a novel family of compounds having the above characteristics, in particular having an effect on crops such as cereals, rice, maize, fruit trees, woodland trees, grapevines, oil-producing plants, protein producing plants, market garden crops, solanum crops, sugar beets, flax, citrus fruits, bananas, ornamentals and tobacco.

It is a further object of the present invention to provide a novel family of picolinic acid derivatives having the characteristics set forth above, and in particular having an effect on crops such as cereals, rice, maize, fruit trees, forestry trees, grapevines, oil-producing plants, protein-producing plants, market garden plants, solanum plants, sugar beets, flax, citrus fruits, bananas, ornamentals and tobacco.

It is another object of the present invention to propose a novel family of picolinic acid derivatives which are useful both in the treatment and in the protection of wood against fungal diseases. Wood used for the production of, for example, buildings and furniture (frames, walls, ceilings, floors, etc.) is subject to various damage by phytopathogenic fungi. The compounds of the present invention are resistant to these attacks.

It is another object of the present invention to propose a novel family of picolinic acid derivatives for use in the treatment of the human or animal body. In fact, due to its antifungal properties, the picolinic acid of the present invention proves useful in the treatment of fungal diseases, such as mycoses and candidiasis, of the human and animal body.

Surprisingly, it has been found that these objects can be achieved in whole or in part by the picolinic acid derivatives of the invention.

General definitions in the present invention

The present invention relates to picolinic acid derivatives represented by the general formula (I):wherein:

g represents an oxygen or sulphur atom,

n represents a number 0 or 1,

·Q₁selected from oxygen or sulfur atoms, radicals NR₁Or N-NR₄R₅，

·Q₂Selected from OR₂Or SR₃Or is-NR₄R₅Or is or

·Q₁And Q₂May together form a 5-7 membered ring containing 2-3 oxygen and/or nitrogen atoms, which may optionally be substituted by one or more identical or different groups selected from halogen or alkyl or haloalkyl,

z is chosen from a hydrogen atom, a cyano group or an alkyl group, an allyl group, an aryl group, an aralkyl group, a propargyl group, a cycloalkyl group, a halocycloalkyl group, an alkenyl group, an alkynyl group, a cyanoalkyl group, a haloalkyl group, an alkoxyalkyl group, a haloalkoxyalkyl group, an alkylthioalkyl group, an N-alkylaminoalkyl group, an N, N-dialkylaminoalkyl group, an acylaminoalkyl group, an alkoxycarbonylaminoalkyl group, an alkoxycarbonyl group, an N-alkylaminocarbonyl group, an N, N-dialkylaminocarbonyl group, an acyl group, a thioacyl group, an alkoxythiocarbonyl group, an N-alkylaminothiocarbonyl group, an N, N-dialkylaminothiocarbonyl group, an alkylsulfinyl group, a haloalkylsulfinyl group, an alkylsulfonyl group, a haloalkylsulfonyl group, an aminosulfonyl group, an N-alkylaminosu, n-dialkylaminosulfonyl, arylsulfinyl, arylsulfonyl, aryloxysulfonyl, N-arylaminosulfonyl, N, N-diarylaminosulfonyl or N, N-aralkylaminosulfonyl;

y is selected from the group consisting of a halogen atom, a hydroxyl, mercapto, nitro, thiocyanato, azido, cyano or pentafluorosulfonyl group, an alkyl, haloalkyl, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, cyanoalkyl, cyanoalkoxy, cyanoalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl or alkoxysulfonyl group, a cycloalkyl, halocycloalkyl, alkenyl, alkynyl, alkenyloxy, alkynyloxy, alkenylthio or alkynylthio group,

amino, N-alkylamino, N, N-dialkylamino, -NHCOR₁₀，-NHCSR₁₀N-alkylaminocarbonylamino, N, N-dialkylaminocarbonylamino, aminoalkyl, N-alkylaminoalkyl, N, N-dialkylaminoalkyl, acylaminoalkyl, thioacylamino, alkoxythiocarbonylamino, N-alkylaminothiocarbonylamino, N, N-dialkylaminosulfurCarbonylamino, N, N-aralkylaminocarbonylamino, N-alkylsulfinylamino, N-alkylsulfonylamino, N-alkyl (alkylsulfonyl) amino, N-arylsulfinylamino, N-arylsulfonylamino, N-alkoxysulfonylamino, N-alkoxysulfinylamino, N-haloalkyloxysulfinylamino, N-haloalkyloxysulfonylamino, N-arylamino, N, N-diarylamino, arylcarbonylamino, alkoxycarbonylamino, N-arylaminocarbonylamino, N, N-diarylaminocarbonylamino, arylthiocarbonylamino, aryloxythocarbonylamino, N-arylaminothiocarbonylamino, N, N-diarylaminothiocarbonylamino or N, an N-arylalkylaminothiocarbonylamino group,

acyl, carboxyl, carbamoyl, N-alkylcarbamoyl, N, N-dialkylcarbamoyl, lower alkoxycarbonyl, N-arylcarbamoyl, N, N-diarylcarbamoyl, aryloxycarbonyl or N, N-aralkylcarbamoyl and imino of the formula:

·X₁and X₂Identical or different, each independently from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl, mercapto, nitro, cyanato, azido, cyano or pentafluorosulfonyl group, or an alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, cyanoalkyl, cyanoalkoxy, cyanoalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl or alkoxysulfonyl group, or

·X₁And X₂Or may be linked together to form a saturated, partially saturated or fully unsaturated 4-to 8-membered ring, which may optionally contain one or more heteroatoms selected from sulfur, oxygen, nitrogen or phosphorus,

·R₂and R₃Are identical or different and are each independently selected from alkyl having 1 to 12 carbon atoms, halogenAlkyl, cycloalkyl, halocycloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxyaryl, alkylthioalkyl, haloalkylthioalkyl, cyanoalkyl or acyl, nitro, cyano, carboxyl, carbamoyl or 3-oxetanyloxycarbonyl (3-oxocarbonyloxy), and N-alkylcarbamoyl, N, N-dialkylcarbamoyl, alkoxycarbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl, alkylthiocarbonyl, alkenyl, alkynyl, N-alkylamino, N, N-dialkylamino, N-alkylaminoalkyl or N, N-dialkylaminoalkyl, or

Optionally substituted by one or more R, the same or different₉And/or aryl and/or aralkyl substituted radical selected from aryl, aralkyl, heterocycle and heterocycloalkyl, and/or the radical-T-R₈Or is or

·R₁，R₄，R₅，R₆And R₇Are identical or different and are each independently selected from the group consisting of a hydrogen atom, an optionally substituted straight-chain or branched alkyl group having from 1 to 12 carbon atoms, a haloalkyl, cycloalkyl, halocycloalkyl, alkoxy, aryloxy, arylalkoxy, haloalkoxy, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, cyanoalkyl or acyl, nitro, cyano, carboxyl, carbamoyl or 3-oxetanyloxycarbonyl, N-alkylcarbamoyl, N, N-dialkylcarbamoyl, alkoxycarbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, alkoxythiocarbonyl, haloalkyloxythiocarbonyl, alkylthiocarbonyl, alkenyl, alkynyl, N-alkylamino, N, N-dialkylamino, N-alkylaminoalkyl or N, n-dialkylaminoalkyl, or

Selected from the group consisting of₉And/or aryl and/or aralkyl-substituted aryl, aralkyl, heterocyclyl and heterocycloalkyl radicals, and/or the radicals-T-R₈Or is or

In one aspect R₄And R₅Or on the other hand R₆And R₇May be linked together to form a saturated, partially unsaturated or fully unsaturated 4-to 8-membered ring, optionally containing one or more heteroatoms selected from sulfur, oxygen, nitrogen and phosphorus,

t represents directly a bond, or represents a divalent radical selected from the group consisting of the radicals- (CH)₂) m- (m is 1-12, and is limited, and the group can be interrupted or terminated by one or two heteroatoms selected from nitrogen atom, oxygen atom and/or sulfur atom), and oxyalkenyl, alkoxyalkenyl, carbonyl (-CO-), oxycarbonyl (-O-CO-), carbonyloxy (-CO-O-), sulfinyl (-SO-), sulfonyl (-SO-)₂-, oxysulfonyl (-O-SO)₂-, sulfonyloxy (-SO)₂-O-), oxysulfinyl (-O-SO-), sulfinyloxy (-SO-O-), thio (-S-), oxy (-O-), vinyl (-C ═ C-), alkynyl (-C ≡ C-), -NR₉-，-NR₉O-，-ONR₉-，-N＝N-，-NR₉-NR₁₀-，-NR₉-S-，-NR₉-SO-，-NR₉-SO₂-，-S-NR₉-，-SO-NR₉-，-SO₂-NR₉-，-CO-NR₉-O-or-O-NR₉-a CO-group, in which,

·R₈selected from the group consisting of a hydrogen atom and an aryl or heterocyclic group,

·R₉and R₁₀Are identical or different and are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, a thiocyanato group, an azido group, a cyano group or a pentafluorosulfonyl group, and an alkyl group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkylthio group, a haloalkylthio group, an alkoxyalkyl group, a haloalkoxyalkyl group, an alkylthioalkyl group, a haloalkylthioalkyl group, an arylalkyl group, a cyanoalkyl group, a cyanoalkoxy group, a cyanoalkylthio group, an alkylsulfinyl group, a haloalkylsulfinyl group, an alkylsulfonyl group, a haloalkylsulfonyl group.

And optionally N-oxides, geometrical and/or optical isomers, enantiomers and/or diastereomers, tautomeric forms, salts and metal and non-metal complexes of the compounds of formula (I) as defined above,

when Q is₁G-Z represents oxygen, G-Z represents dialkylaminocarbonyloxy or dialkylaminothiocarbonyloxy, Y represents NH₂Radical or N₃Group, Q₂Represents the group-NR₄R₅，R₄When represents an alkyl group having 1 to 12 carbon atoms, then R₅And do not represent alkyl groups having 1 to 12 carbon atoms.

Tautomeric forms of the compounds of formula (I) as defined above are also encompassed by the invention. Tautomeric forms are understood as being all isomeric forms described in the literature "tautomeric isomerism of Heterocycles", "higher Heterocyclic Chemistry" (the Tautomerims of Heterocycles, Advances in Heterocyclic Chemistry), supplement 1, J.Elguero, C.Martin, A.R.Katritsky and P Linda, academic Press published, New York, 1976, pages 1-4 ].

The following terms have the following meanings:

halogen represents a fluorine, chlorine, bromine or iodine atom,

alkyl and the groups comprising these alkyl groups (alkoxy, alkylcarbonyl or acyl, etc.) which, unless otherwise stated, comprise from 1 to 6 carbon atoms in a straight or branched chain, which may optionally be substituted,

haloalkyl, alkoxy and halocycloalkyl groups may contain one or more halogen atoms which may be the same or different,

cycloalkyl contains 3 to 6 carbon atoms and is optionally substituted,

alkenyl and alkynyl groups, and groups comprising such groups, unless otherwise indicated, contain 2 to 6 carbon atoms in their straight or branched chain, which may optionally be substituted,

acyl represents alkylcarbonyl or cycloalkylcarbonyl, the alkyl part containing 1 to 6 carbon atoms and the cycloalkyl part containing 3 to 6 carbon atoms and being optionally substituted, unless otherwise stated,

alkenyl represents divalent- (CH)₂)_m-a group, wherein m represents an integer 1, 2, 3,4, 5 or 6,

the term "aryl" in "aryl" and "arylalkyl" denotes an optionally substituted phenyl or naphthyl,

"Heterocycloalkyl" in "heterocyclyl" and "heterocycloalkyl" denotes an optionally substituted 4-to 10-membered saturated, partially unsaturated or unsaturated ring which contains the same or different one or more heteroatoms selected from nitrogen, oxygen, sulfur, silicon or phosphorus,

when the amino group is disubstituted, the two substituents are identical or different or, together with the nitrogen atom they carry, form a saturated, partially unsaturated or unsaturated, nitrogen-containing heterocycle having a total of 5 or 6 atoms,

when carbamoyl is disubstituted, the two substituents are identical or different or, together with the nitrogen atom they bear, form a saturated, partially unsaturated or unsaturated, nitrogen-containing heterocycle having a total of 5 or 6 atoms,

unless otherwise stated, the expression "optionally substituted" modifying an organic group may be used for the different radicals constituting the group, meaning that the different radicals may optionally be substituted by one or more identical or different radicals R9 and/or aryl and/or arylalkyl groups.

According to one variant of the invention, the invention relates to a picolinic acid derivative of general formula (I) as defined above, in which:

·X₁and X₂Each represents a hydrogen atom, and each represents a hydrogen atom,

the other substituents are as defined above,

and optionally N-oxides, geometrical and/or optical isomers, enantiomers and/or diastereomers, tautomeric forms, salts and metal and non-metal complexes of said compounds of formula (I).

The limitation is that when Q₁G-Z represents oxygen, G-Z represents dialkylaminocarbonyloxy or dialkylaminothiocarbonyloxy, Y represents NH₂Or N₃Group, Q₂represents-NR₄R₅，R₄When represents an alkyl group having 1 to 12 carbon atoms, then R₅And may not represent an alkyl group having 1 to 12 carbon atoms.

According to another variant of the invention, the invention relates to a picolinic acid derivative of general formula (I) as defined above, in which:

·Q₁selected from the group consisting of oxygen and sulfur atoms,

the other substituents are as defined in claim 1,

and optionally N-oxides, geometrical and/or optical isomers, enantiomers and/or diastereomers, tautomeric forms, salts and metal and non-metal complexes of the compounds of formula (I),

according to a third variant of the invention, the invention relates to a picolinic acid derivative of general formula (I) wherein:

z is selected from alkyl and a hydrogen atom or a cleavable group capable of providing hydrogen, for example alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, N-alkylaminoalkyl, N, N-dialkylaminoalkyl, acylaminoalkyl, acyl, thioacyl, cyanoalkyl, alkoxythiocarbonyl, N-alkylaminothiocarbonyl, N, N-dialkylaminothiocarbonyl or alkylsulfinyl,

the other substituent is as defined above,

the limitation is that when Q₁G-Z represents oxygen, a dialkylaminocarbonyloxy group or a dioxaneAminothiocarbonyloxy radical, Y representing NH₂Or N₃Group, Q₂represents-NR₄R₅，R₄When represents an alkyl group having 1 to 12 carbon atoms, then R₅And may not represent an alkyl group having 1 to 12 carbon atoms.

Another variant of the invention relates to picolinic acid derivatives of general formula (I) wherein:

y is selected from the group consisting of a halogen atom, a hydroxyl, mercapto, nitro, thiocyanato, azido, cyano or pentafluorosulfonyl group, an alkyl, haloalkyl, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl or alkoxysulfonyl group, an amino, N-alkylamino, N-dialkylamino, -NHCOR₁₀、-NHCSR₁₀N-arylamino, N-diarylamino, arylcarbonylamino, arylthiocarbonylamino, aryloxythiocarbonylamino or N, N-arylalkylaminothiocarbonylamino,

the other substituents are as defined above,

According to another variant of the invention, the invention relates to picolinic acid derivatives of general formula (I) wherein:

·Q₂represents the group-NR₄R₅Wherein R is₄Represents a hydrogen atom, R₅Selected from optionally substituted, linear or branched alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkenyl or alkynyl having 1 to 12 carbon atoms, and from aryl, arylalkyl, heterocyclyl and heterocyclylalkyl groups, which may optionally be substituted by one or more identical or different radicals R₉And/or aryl and/or arylalkyl), and/or-T-R₈，

The other substituents are as defined above,

More particularly, the present invention relates to picolinic acid derivatives of general formula (I), and optionally N-oxides, geometrical and/or optical isomers, enantiomers and/or diastereomers, tautomeric forms, salts and metal and non-metal complexes of said compounds of formula (I), the picolinic acid derivatives having the following characteristics, alone or in combination:

z is selected from alkyl and a hydrogen atom or a cleavable group capable of providing hydrogen, for example alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, N-alkylaminoalkyl, N-dialkylaminoalkyl, acylaminoalkyl, acyl, thioacyl, cyanoalkyl, alkoxythiocarbonyl, N-alkylaminothiocarbonyl, N-dialkylaminothiocarbonyl or alkylsulfinyl,

y is selected from the group consisting of halogen, hydroxyl, mercapto, nitro, thiocyanato, azido, cyano or pentafluorosulfonyl, alkyl, haloalkyl, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl or alkoxysulfonyl, amino, and N-alkylamino, N, N-dialkylamino, -NHCOR₁₀，-NHCSR₁₀N-arylamino, N, N-diarylamino, arylcarbonylamino, arylthiocarbonylamino, aryloxythiocarbonylamino or N, N-arylalkylaminothiocarbonylamino,

·Q₁selected from the group consisting of an oxygen atom and a sulfur atom,

·Q₂represents the group-NR₄R₅Wherein R is₄Represents a hydrogen atom, R₅Selected from optionally substituted, linear or branched alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkenyl and alkynyl having 1 to 12 carbon atoms, and from aryl, arylalkyl, heterocyclyl and heterocyclylalkyl optionally substituted by one or more identical or different radicals R₉And/or aryl and/or arylalkyl substitution), and/or a group-T-R₈，

The other substituents are as defined above,

More particularly, the present invention relates to picolinic acid derivatives of formula (I) as defined above, and optionally N-oxides, geometrical and/or optical isomers, enantiomers and/or diastereomers, tautomeric forms, salts and metal and non-metal complexes of compounds of formula (I) as defined above, the picolinic acid derivatives having the following characteristics:

y is selected from the group consisting of a halogen atom, a hydroxyl, mercapto, nitro, thiocyanato, azido, cyano or pentafluorosulfonyl group, an alkyl, haloalkyl, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl or alkoxysulfonyl group, an amino group, and an N-alkylamino, N-dialkylamino, -NHCOR₁₀、-NHCSR₁₀N-arylamino, N-diarylamino, arylcarbonylamino, arylthiocarbonylamino, aryloxythiocarbonylamino or N, N-arylalkylaminothiocarbonylamino,

·Q₁selected from the group consisting of an oxygen atom and a sulfur atom,

·Q₂represents the group-NR₄R₅Wherein R is₄Represents a hydrogen atom, R₅Selected from optionally substituted straight-chain or branched alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkenyl and alkynyl radicals having 1 to 12 carbon atoms and from aryl, arylalkyl, heterocyclyl and heterocyclylalkyl radicals optionally substituted by one or more identical or different radicals R₉And/or aryl and/or arylalkyl substitution), and/or a group-T-R₈，

The other substituents are as defined above,

More particularly, the present invention relates to picolinic acid derivatives of formula (I) above, and optionally N-oxides, geometrical and/or optical isomers, enantiomers and/or diastereomers, tautomeric forms, salts and metal and non-metal complexes of the compounds of formula (I) as defined above, wherein:

y is selected from the group consisting of halogen atoms, hydroxyl, mercapto, azido, alkylthio and alkylsulfonyl, and amino, -NHCOR₁₀and-NHCSR₁₀A group of a nitrogen atom or a nitrogen atom,

·Q₁represents an oxygen atom, and is represented by,

·Q₂represents the group-NR₄R₅Wherein R is₄Represents a hydrogen atom, R₅Selected from aryl, arylalkyl, heterocyclyl and heterocyclylalkyl (optionally substituted by one or more identical or different groups R)₉And/or aryl and/or arylalkyl substitution), and/or a group-T-R₈，

The other substituents are as defined above.

As used herein, the term "aryl" refers to phenyl or naphthyl, the term"arylalkyl" means phenylalkyl or naphthylalkyl, more specifically benzyl, phenethyl, phenylpropyl, phenylbutyl, naphthylmethyl, naphthylethyl, naphthylpropyl or naphthylbutyl. It is to be understood that these radicals may optionally be substituted by one or more identical or different radicals R₉And/or aryl and/or arylalkyl.

The terms "heterocyclyl" and "heterocyclylalkyl" are defined similarly, it being understood that "heterocyclyl" means a saturated, partially unsaturated, or unsaturated, monocyclic or bicyclic ring containing 4 to 10 ring atoms including at least one ring atom selected from nitrogen, oxygen, sulfur, silicon, and phosphorus.

More specifically, the term "heterocycle" denotes the following rings (i) to (v):

a five-membered ring of formula (i):wherein B is¹，B²，B³，B⁴Each group of (a) is selected from carbon, nitrogen, oxygen and sulfur atoms such that the group comprises 0 to 3 carbon atoms, 0 to 1 sulfur atom, 0 to 1 oxygen atom and 0 to 4 nitrogen atoms;

a six-membered ring of formula (ii):wherein D¹，D²，D³，D⁴，D⁵Each group in (a) is selected from carbon and nitrogen atoms, such that the group comprises 1 to 4 carbon atoms and 1 to 4 nitrogen atoms;

two fused rings of formula (iii) below, each ring being a six-membered ring:wherein E¹，E²，E³，E⁴，E⁵，E⁶，E⁷，E⁸Each group in (a) is selected from carbon and nitrogen atoms, such that the group comprises 4 to 7 carbon atoms and 1 to 4 nitrogen atoms;

the 6-and 5-membered rings in formula (iv) below are fused together:wherein:

*J¹，J²，J³，J⁴，J⁵，J⁶each group in (a) is selected from carbon and nitrogen atoms, such that the group comprises 3 to 6 carbon atoms and 0 to 3 nitrogen atoms;

*L¹，L²，L³each group of (a) is selected from carbon, nitrogen, oxygen and sulfur atoms such that the group comprises 0 to 3 carbon atoms, 0 to 1 sulfur atom, 0 to 1 oxygen atom and 0 to 3 nitrogen atoms; and

selecting J in this way¹，J²，J³，J⁴，J⁵，J⁶，L¹，L²，L³Such that said group comprises 3 to 8 carbon atoms;

two fused rings of formula (v) below are each a five-membered ring:wherein M is¹，M²，M³Each group in (a) represents a carbon, nitrogen, oxygen or sulfur atom, such that said group comprises 0 to 3 carbon atoms, 0 to 1 sulfur atom, 0 to 1 oxygen atom and 0 to 3 nitrogen atoms;

T¹，T²，T³each group in (a) represents a carbon, nitrogen, oxygen or sulfur atom, such that said group comprises 0 to 3 carbon atoms, 0 to 1 sulfur atom, 0 to 1 oxygen atom and 0 to 3 nitrogen atoms;

Z¹represents a carbon atom or a nitrogen atom;

thus selecting M¹，M²，M³，T¹，T²，T³Such that the group contains 0 to 6 carbon atoms.

In the present invention, the term "heterocyclyl" more specifically means: furyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1, 2, 3-oxadiazolyl, 1, 2, 4-oxadiazolyl, 1, 2, 5-oxadiazolyl, 1, 3, 4-oxadiazolyl, 1, 2, 3-thiadiazolyl, 1, 2, 4-thiadiazolyl, 1, 2, 5-thiadiazolyl, 1, 3, 4-thiadiazolyl, 1, 2, 3-triazolyl, 1, 2, 4-triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, 1, 2, 3-triazinyl, 1, 2, 4-triazinyl, 1, 3, 5-triazinyl, 1, 2, 3, 4-tetrazinyl, 1, 2, 3, 5-tetrazinyl, 1, 2, 4, 5-tetrazinyl, Benzimidazolyl, indazolyl, benzotriazolyl, benzoxazolyl, 1, 2-benzisoxazolyl, 2, 1-benzisoxazolyl, benzothiazolyl, 1, 2-benzisothiazolyl, 2, 1-benzisothiazolyl, 1, 2, 3-benzoxazolyl, 1, 2, 5-benzoxazolyl, 1, 2, 3-benzothiadiazolyl, 1, 2, 5-benzothiadiazolyl, quinolinyl, isoquinolinyl, quinoxazolidinyl, quinazolinyl, 1, 2-naphthyridinyl or 2, 3-naphthyridinyl, pteridinyl, benzotriazolyl, 1, 5-naphthyridinyl, 1, 6-naphthyridinyl, 1, 7-naphthyridinyl, 1, 8-naphthyridinyl, imidazo [ 2, 1-b ] thiazolyl, benzimidazolyl, 1-b ] thiazolyl, Thieno [ 3, 4-b ] pyridyl, purine or pyrrolo [ 1, 2-b ] thiazolyl.

The invention relates more particularly to picolinic acid derivatives of general formula (I), and optionally N-oxides, geometrical and/or optical isomers, enantiomers and/or diastereomers, tautomeric forms, salts and metal and non-metal complexes thereof,

the derivatives are:

4-amino-3-hydroxy-N- [4- (4-methylphenoxy) phenyl ] -2-pyridinecarboxamide,

4- (formylamino) -3-hydroxy-N- {4- [ 3- (trifluoromethyl) -phenoxy ] -phenyl } -2-pyridinecarboxamide,

4-amino-3-hydroxy-N- {4- [4- (trifluoromethyl) phenoxy ] -phenyl } -2-pyridinecarboxamide,

n- [4- (4-chlorophenoxy) phenyl ] -4- (formylamino) -3-hydroxy-2-pyridinecarboxamide,

4- (formylamino) -3-hydroxy-N- {4- [4- (trifluoromethyl) -phenoxy ] phenyl } -2-pyridinecarboxamide, and

n- [4- (4-benzyloxy) phenyl ] -4- (carboxamido) -3-hydroxy-2-pyridinecarboxamide.

Compounds of formula (I) and compounds which are intermediates in the preparation of which the definition of the compound is made when describing the preparation. Depending on the number of double bonds present in the compound, one or more geometric isomeric forms may be present. In the general formula (I), Q in the formula₁is-NR₁or-N-NR₄R₅The compound of (c) may comprise 2 different geometric isomers (E) or (Z) depending on the configuration of the two double bonds. The symbols E and Z may be replaced by the terms "cis" and "trans", "syn" and "anti" or "cis" and "trans", respectively. See, inter alia, E.Eliel and S.Wilen, stereochemistry of organic compounds [ Wiley publication (1994)]The description and use of such symbols.

The compounds of formula (I) and useful intermediates in the preparation of the invention, which compounds are defined at the time of introduction of the preparation, may exist in one or more optical isomers or chiral forms depending on the number of chiral centers in the compound. The invention therefore also relates to all optical isomers and their racemates or scalemic (scalemic denotes a mixture of enantiomers in different proportions), and to mixtures of all possible stereoisomers in all proportions, including racemic mixtures. Separation of the diastereoisomers and/or optical isomers may be carried out by known methods (e.eliel, supra).

The invention also relates to a method for preparing the compound shown in the general formula (I) and an intermediate used in the preparation process. The compounds can be prepared according to the following general methods. Although very general, this preparation provides all the operating conditions for the synthesis of the compounds of formula (I) according to the invention. Clearly, one skilled in the art will be able to synthesize a particular compound for each need. To implement the method.

The preparation of a reagent for use in one or other of the general preparation methods is generally known and is generally described in detail in the art or in a manner that enables one of ordinary skill in the art to utilize it to its desired end. The prior art available to the skilled worker for establishing the conditions for preparing reagents can be found in many common chemical textbooks, such as "advanced organic chemistry" (J.March, Wiley publication (1992) ], "Methoden der organischen Chemie [ (Houben-weyl), Georg Thieme Verlag publication ] or" chemical abstracts "(published by the American society for chemistry), and publicly accessible information bases.

Compounds of formula (I) wherein G represents oxygen, Z represents hydrogen and n is equal to 0, can be prepared from compounds of formula (IIa) (e.g. according to the method described in R.H.Dodd, heterocycle, 47, (1998), 811):wherein X₁，X₂，Q₁And Q₂Is as defined above, W₁And W₂Which may be the same or different, each represents a halogen atom selected from fluorine, chlorine, bromine and iodine,

this compound is contacted with an azolydric acid salt, more specifically (but not exclusively sodium azide, the reaction preferably being carried out in a polar aprotic solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylpropyleneurea or dimethylsulfoxide, at a temperature of 20-200 ℃ to give a compound of formula (IIIa):wherein X₁，X₂，Q₁And Q₂Is as defined above, W₂Represents a halogen atom selected from fluorine, chlorine, bromine and iodine.

The azide of formula (IIIa) above is then optionally reduced to the corresponding amine derivative of formula (IVa) by the action of a reducing agent such as triphenylphosphine, sodium borohydride or hydrogen in the presence of a catalyst, or as described in j. march (supra) 1219-1220:

the compound of formula (IVa) is then hydrolyzed by the action of an inorganic base, such as (but not exclusively) alkali metal hydroxides and alkaline earth metal hydroxides (such as sodium hydroxide, potassium hydroxide, caesium hydroxide or calcium hydroxide) to the 3-hydroxypicolinic acid derivative (Va):wherein X₁，X₂，Q₁And Q₂The definition of (A) is the same as that of (B),

the reaction is generally carried out in a polar aprotic solvent, such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylpropyleneurea, dimethylsulfoxide or water, at a temperature of from 0 ℃ to the boiling point of the solvent.

The compound of formula (Va) may optionally be subjected to various alkylation reactions known in the art to give a compound of formula (VIa):wherein X₁，X₂，Z，Q₁And Q₂The definition of (A) is as above.

The compounds of the formula (I) in which G represents sulfur can also be prepared advantageously from compounds of the formula (IIb) [ for example, according to R.H.Dodd, heterocycle 47, (1998), p.811):wherein X₁，X₂，Q₁And Q₂Is as defined above, W₁Represents a halogen atom selected from fluorine, chlorine, bromine and iodine,

by reaction with an inorganic base such as (but not all) lithium diisopropylamide and sulfur, a compound of formula (IIIb) is obtained:wherein X₁，X₂，Q₁And Q₂The definition of (A) is as above.

Suitable solvents for this reaction are aliphatic hydrocarbons, such as pentane, hexane, heptane or octane; aromatic hydrocarbons such as benzene or toluene; ethers, such as diethyl ether, isopropyl ether or tetrahydrofuran. The reaction is carried out at a temperature of-100 ℃ to 0 ℃.

The thiol of formula (IIIb) may be converted to a compound of formula (IVb) by reaction with an alkylating agent, such as (but not all) methyl iodide or 4-methoxybenzyl chloride:wherein X₁，X₂，Q₁And Q₂The definition of (A) is as above.

The reaction requires the presence of an organic or inorganic base, such as sodium, potassium, cesium or calcium hydroxide, alkali metal alkoxides, such as potassium tert-butoxide, alkali metal hydrides and alkaline earth metal hydrides, such as sodium, potassium or cesium hydride, alkali metal carbonates and bicarbonates, or alkaline earth metal carbonates and bicarbonates, such as sodium, potassium or calcium carbonate, organic bases, preferably organic nitrogen bases, such as pyridine, alkylpyridine, alkylamines, such as trimethylamine, triethylamine or diisopropylethylamine, aza derivatives, such as 1, 5-diazabicyclo [ 4.3.0 ] non-5-ene or 1, 8-diazabicyclo [ 5.4.0 ] undec-7-ene. The reaction is generally carried out at a temperature of from-80 ℃ to 180 ℃ and preferably from 0 to 150 ℃ or at the boiling point of the solvent used. Suitable solvents for this reaction may be aliphatic hydrocarbons, such as pentane, hexane, heptane or octane; aromatic hydrocarbons such as benzene, toluene or xylene; ethers, such as diethyl ether, isopropyl ether, tetrahydrofuran, dioxane or dimethoxyethane; halogenated hydrocarbons such as dichloromethane, chloroform or 1, 2-dichloroethane; nitriles, such as acetonitrile, propionitrile or benzonitrile; aprotic dipolar solvents, such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylpropyleneurea, dimethylsulfoxide or water.

In the absence of a solvent or in a polar aprotic solvent, such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylpropyleneurea or dimethylsulfoxide, at a temperature of from 0 ℃ to the boiling point of the solvent, by reaction with a compound of formula R₆R₇NH or its corresponding alkali metal or alkaline earth metal salt to convert the compound of formula (IVb)To a 4-amino compound represented by the formula (Vb):wherein X₁，X₂，Q₁，Q₂，Z，R₆And R₇The definition of (A) is as above.

A compound of formula (Vb) [ wherein X is₁，X₂，Q₁，Q₂，R₆And R₇Wherein Z represents a 4-methoxydiphenylethanolic acid group (benzilic)]Conversion to the corresponding 3-thiopyridine to give the compound of formula (VIb), preferably in a polar protic solvent such as an alcohol, e.g. ethanol, methanol, propanol or cresol, at reflux temperature or at 20 deg.C to 200 deg.C:wherein X₁，X₂，Q₁，Q₂，R₆And R₇The definition of (A) is as above.

The compound of formula (IVb) may be converted to an azide of formula (VIIb) by reaction with an azolthydric acid salt, more particularly (but not exclusively) sodium azide, preferably in a polar aprotic solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylpropyleneurea or dimethylsulfoxide, at reflux temperature or at a temperature of 20-200 deg.C:wherein X₁，X₂，Q₁，Q₂And Z is as defined above.

The compound of formula (VIIb) may then be hydrolysed to the compound of formula (VIIIb) by the action of a reducing agent such as hydrogen in the presence of triphenylphosphine or a catalyst, or as described in j. march (supra) 1219-1220:wherein X₁，X₂，Q₁And Q₂The definition of (A) is as above.

The compounds of formulae (Va), (VIa) and (VIIIb) as defined above may optionally be contacted with an acylating agent in the presence of a solvent and optionally a base. The term "acylating agent" preferably, but not exclusively, denotes acyl halides, anhydrides, acids, esters, primary amides and their thio-homologues as described in j. march (supra, pages 417-424) to give the formula (IX)₁) And (IX)₂) A compound:wherein G, X₁，X₂，Q₁，Q₂Z and R₁₀The definition of (A) is as above.

The compounds of formulae (VIa) and (IVb) may optionally also be subjected to various substitution and/or addition reactions known in the art to give compounds of formula (X):wherein G, X₁，X₂，Q₁，Q₂Y and Z are as defined above, which are compounds in the specific case where n represents 0 in formula (I).

By making a compound represented by the formula (X) [ specific example of the formula (I) wherein n is 0%]March (supra, page 1200) with an oxidizing agent, in particular aqueous hydrogen peroxide or a carboxylic acid, boric acid or persulfuric acid, to give a compound of the formula (XI):it is a particular case of compounds of formula (I) in which n is equal to 1.

It will be appreciated that the reactions described above may be carried out in any other order suitable to give the desired compound of formula (I). The order of reaction can be determined by the matching requirements of the various substituents on the pyridine nucleus. The various groups and reagents used are well known to those skilled in the art and reference is made to the examples described below for the preparation of compounds of formula (I).

The invention also relates to fungicidal compositions comprising an effective amount of at least one active substance of formula (I). The fungicidal compositions according to the invention comprise, in addition to the active substance of formula (I), an agriculturally acceptable solid or liquid carrier and/or an agriculturally acceptable surfactant. In particular, a common inert carrier and a common surfactant may also be used. These compositions include not only compositions which are applied directly to the plants by suitable means, such as spraying or sowing devices, but also commercial concentrated compositions which must be diluted before application to the crop.

The fungicidal compositions of the invention may also contain other components, such as protective colloids, binders, thickeners, thixotropic agents, penetrants, stabilizers, sequestering agents, and the like. More generally, the active substance may be combined with any solid or liquid additive that may be used in the formulation art.

In general, the compositions of the invention generally comprise from 0.05% to 99% by weight of active substance, one or more solid or liquid carriers and optionally one or more surfactants.

In the present specification, the term "carrier agent" refers to natural or synthetic organic or inorganic substances which, when mixed with the active substance, can be applied more easily to the relevant parts of the plant. Thus, the carrier is generally inert and should be acceptable for agricultural use. The carrier may be a solid (clay, natural or synthetic silicate, silica, resin, wax, solid fertilizer, etc.) or a liquid (water, alcohols, particularly butanol, etc., organic solvents, mineral and vegetable oils, and their derivatives). Mixtures of such carriers may also be used.

The surfactant may be an emulsifier, dispersant or wetting agent, of ionic or non-ionic type, or a mixture of such surfactants. Surfactants which may be mentioned are, for example, polyacrylates, lignosulfonates, phenolsulfonic or naphthalenesulfonates, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (in particular alkylphenols or arylphenols), sulfosuccinates, taurine derivatives (in particular alkyl taurates), phosphoric esters of polyoxyethylene alcohols or phenols, fatty acid esters of polyalcohols, and derivatives of the abovementioned compounds which contain sulfate, sulfonate and phosphate functions. When the active substance and/or inert carrier is not water-soluble, and when the vehicle applied is water, at least one surfactant is generally required.

Thus, the agricultural compositions of the present invention may contain an extremely wide range of active substances from 0.05% to 99% by weight. Their surfactant content is advantageously from 5% to 40% by weight. Unless otherwise indicated, percentages in this specification are percentages by weight.

The compositions of the present invention are themselves in many solid or liquid forms. For the solid composition forms, mention may be made of powders for dusting (up to 100% active substance content) and granules, in particular granules obtained by extrusion, atomisation, compaction, impregnation of granulated carriers or by granulation from powders (0.5% to 80% active substance content in these granules).

The fungicidal compositions of the present invention may also be used to form powders for broadcast; a composition comprising 50 grams of active and 950 grams of talc; a composition comprising 20 grams of active, 10 grams of well-dispersed silica and 970 grams of talc; the components are mixed together and ground, and the mixture is applied by scattering.

As liquid composition forms or forms which tend to form liquid compositions when used, mention may be made of solutions, in particular water-soluble concentrates, emulsifiable concentrates, emulsions, concentrated suspensions and wettable powders (or powders for spraying).

The concentrated suspension applied by spraying is prepared to give a stable, fluid product which does not sediment and has good bioavailability of the active substance. These suspensions generally contain from 5% to 75%, preferably from 10% to 25%, of active substance, from 0.5% to 75%, preferably from 5% to 50%, of surfactant, from 0% to 10% of suitable additives, such as thickeners of organic or mineral origin, antifoams, corrosion inhibitors, binders, preservatives, for example Proxel GXL , anti-coagulants, and water or organic liquids as carrier, in which the active substance is insoluble or only sparingly soluble: certain organic solid materials or inorganic salts are soluble in the carrier to help prevent sedimentation, or act as anti-coagulants for water. In certain cases, particularly when the seed is treated with the formulation, one or more coloring agents may be added.

When applied to the leaves, the choice of surfactant is of paramount importance to obtain good bioavailability of the active substance; therefore, it is preferable to use a combination of a hydrophilic surfactant (HLB > 10) and a lipophilic surfactant (HLB < 5). Combinations of such surfactants are disclosed in hitherto unpublished French patent No. 00/04015.

The following exemplifies 3 possible concentrated suspension formulations suitable for use in various crops:

example CS1 (unit: g/kg):

this example is suitable for monocotyledonous crops (cereals, rice, etc.)

-an active substance 150

Hydrophilic surfactants (e.g. Rhodasurf 860P) 300

Lipophilic surfactants (e.g. Plurafac LF 700) 150

-ethoxylated tristyrylphenol phosphate 50

Anti-foaming agent 5

-propylene glycol 30

-Aerosil 200 20

-Attagel 50 40

Water (1 kg addition) 255

Example CS2 (units g/kg):

this example is quite suitable for dicotyledonous crops (grapevines, fruit trees, etc.)

-an active substance 150

Hydrophilic surfactants (e.g. Rhodasurf 860P) 150

-ethoxylated tristyrylphenol phosphate 50

Anti-foaming agent 5

-propylene glycol 30

-Aerosil 200 20

-Attagel 50 40

555 Water (1 kg added) 555

Example CS3 (in grams/kg):

this embodiment is particularly suitable for treating seeds.

-an active substance 50

Hydrophilic surfactants (e.g. Rhodasurf 860P) 5

Ethoxylated tristyrylphenol phosphate 15

Anti-foaming agent 1

-propylene glycol 30

-a colorant 20

-Rhodopol G 1.5

-Proxel GXL 1.5

Water (1 kg) 876

The following procedures are preferably carried out to prepare these formulations: mixing the selected surfactants (hydrophilic surfactant + lipophilic surfactant + ethoxylated tristyrylphenol phosphate) with the desired amount of water using a turbine mixer; after homogenization, the other components of the formulation, except for the active substance, are mixed together.

Subsequently, the active substance and optionally a thickener of mineral origin (Aerosol 200 and Attagel 50) are added, giving a viscous medium.

The resulting mixture was then high speed milled using a turbine mixer mill and then ball milled to a D50 of about 1-3 microns and a D90 of about 3-80 microns.

When no thickener of mineral origin is used, a thickener of natural origin (Rhodopol G) is added and the mixture is stirred to obtain a mixture of suitable viscosity.

Wettable powders (or powders for spraying) are generally prepared so that they contain from 20% to 95% of active substance, usually from 0 to 30% of wetting agent, from 3% to 20% of dispersing agent and, if desired, from 0.1% to 10% of one or more stabilizers and/or other additives, such as penetrants, binders, antiblocking agents, dyes, etc., in addition to the solid carrier.

To obtain a powder or wettable powder for spraying, the active substance is carefully mixed with the other substances in a suitable mixer and ground with a mill or other suitable mixer. This gives a sprayable powder having good wettability and forming a suspension; they can be placed in aqueous suspension at any desired concentration, and these suspensions can be applied preferably to the leaves or seeds of plants.

The following exemplifies various wettable powder compositions (or spray powder supplies):

example WP1

50% of active substance

Ethoxylated fatty alcohol (wetting agent) 2.5%

-ethoxylated phenethylphenol (dispersant) 5%

Chalk (inert carrier) 42.5%

Example WP 2:

10% of active substance

Branched, ethoxylated with 8 to 10 ethylene oxides Synthesis C130.75%

Oxygen-based alcohol (wetting agent)

Neutral calcium lignosulfonate (dispersant) 12%

Calcium carbonate (inert carrier) to 100%

Example WP 3:

the wettable powder contains the same components as the above examples in the following proportions:

-active substance 75%

-wetting agent 1.50%

-8% of dispersant

Calcium carbonate (inert filler) to 100%

Example WP 4:

90% of active substance

Ethoxylated fatty alcohol (wetting agent) 4%

Ethoxylated phenethylphenol (dispersant) 6%

Example WP 5:

50% of active substance

Mixture of cationic and nonionic surfactants (wetting agent) 2.5%

Sodium lignosulfonate (dispersant) 5%

Kaolin (inert carrier) 42.5%

Aqueous dispersions and emulsions, for example, compositions obtained by diluting the wettable powders of the invention with water, are included within the general scope of the invention. Emulsions may be of the oil-in-water or water-in-oil type, and they may have a consistency, such as a "mayonnaise" type.

It is also within the scope of the present invention that the fungicidal compositions of the present invention may be formulated as water-dispersible granules. These dispersible granules have an apparent density of about 0.3 to about 0.6 and generally have a particle size of about 150 to about 2000 microns, preferably 300 to 1500 microns.

The active content of these particles is generally from about 1% to 90%, preferably from 25% to 90%. The remainder of the granule consists essentially of a solid carrier and an optional surfactant adjuvant that provides water dispersibility to the granule. These particles are broadly classified into two types depending on whether the carrier selected is water-soluble or not. If the carrier is water soluble, it may be inorganic, preferably organic. Very good results have been obtained with urea. As insoluble carriers, preference is given to inorganic, for example kaolin or bentonite. It is also advantageous to add a surfactant [ 2% to 20% by weight of the particles ], more than half of which is constituted by at least one substantially anionic dispersing agent, such as an alkali or alkaline earth metal polynaphthalenesulfonate or an alkali or alkaline earth metal lignosulfonate, the remainder being a nonionic or anionic wetting agent, such as an alkali or alkaline earth metal alkylnaphthalenesulfonate. In addition, although not necessarily, other adjuvants, such as antifoams, may also be added.

The granules of the invention can be prepared as follows: the desired components are mixed together and then granulated according to several known techniques (granulator, fluidized bed, atomizer, extrusion, etc.). After this process is completed, a crushing operation is generally performed, and then particles having a specific particle diameter within the above-defined range are screened. Granules prepared as above and then impregnated with a composition containing the active substance may also be used.

Preferably, the pellets are obtained by extrusion, by the methods indicated in the series of examples.

Example DG 1: dispersible granules,

90% by weight of active substance and 10% of urea granules are mixed together in a mixer. The mixture was then ground in a serrated roller crusher. A powder was obtained, which was then moistened with about 8% by weight of water. The moist powder is extruded in a perforated roller extruder. Granules were obtained, dried, then crushed and sieved to retain particles of 150-2000 microns in size.

Example DG 2: dispersible granule

The following components were mixed together in a mixer:

-active substance 75%

Wetting agent (sodium alkylnaphthalenesulfonate) 2%

Dispersant (PolyNaphthalenesulfonic acid sodium salt) 8%

15% of non-water-soluble inert filler (kaolin)

The mixture is granulated in a fluidized bed in the presence of water, and then dried, crushed and sieved to obtain granules with a particle size of 0.15-0.80 mm.

These particles can be used alone or as a solution or dispersion in water to give the desired dosage. They may also be combined with other active substances, in particular fungicides, and these may be in the form of wettable powders, granules or aqueous suspensions.

The compounds of the invention may also be combined with one or more insecticides, fungicides, bactericides, acaricides, attractants or pheromones or other compounds having biological activity. The mixture thus obtained has a broad spectrum of activity. In particular, the compounds of the present invention do not have the problem of cross-resistance with derivatives of Strobilurin. In fact, the compounds of the present invention are active against different biochemical sites of the derivatives of Strobilurin.

Mixtures with other fungicides are particularly advantageous, in particular mixtures with the following fungicides: acebenzolar-S-methyl, azoxystrobin, benalaxyl, benomyl, blasticidin, bromuconazole, captafol, captan, carbendazim, carboxin, carpropamide, chlorothalonil, copper-based fungicidal compositions, copper derivatives such as copper hydroxide and cupric oxychloride, cyazofamide, cymoxanil, cyproconazole, cyprodinil, niclosamide, diclocymet, diethofencarb, difumetrozole, dimethomorph, diniconazole, discomobenzoin, dodecamorph, dodine, edifenfluramine, epoxyconazole, ethaboxam, ethirimol, famoxadone, fenaminolone, fenarimol, fenbuzazole, fenhexamide, fenpiclonil, fenpropidin, fenpropiconazole, fenflurazon, fenflurazone, flumizone, flumethazine, flumethofezin, flufenoxan, fenoxanil, fenoxaflufenoxanil, fenoxaprop-ethyl, flufenaminostrobilurin, fenoxaprop-ethyl, fenoxaprop-2, fenoxaprop-ethyl, fenoxa, metalaxyl and their diastereomeric forms, such as metalaxyl-M, metconazol, metsynephon, metamitron, oxadixyl, pefurazoate, penconazole, pencycuron, phosphoric acid and its derivatives, such as fosetyl-aluminium, tetrachlorophthalide, picoxystrobin, propiconazole, prochlloraz, procymidone, propamocarb, propiconazol, pyraclostrobinin, pyrimethanil, pyroquilon, quinoxyfen, silthiofam, simeconazole, spiroxamine, tebuconazole, tetraconazole, thiabendazole, thifluzazole, thiophanate, for example thiophanate-methyl, thiram, tricyclazole, tridemorph-morph, trifloxystrobin, triticonazole, derivatives of valinamide, such as iprovalicarb, zineb and zineb.

A further subject of the present invention is a method for the medical or prophylactic treatment of phytopathogenic fungi of crops, characterized in that an effective (agriculturally effective) and non-phytotoxic amount of an active substance of the formula (I), preferably in the form of the fungicidal composition according to the invention, is applied to the plant seeds or to the plant leaves and/or to the plant fruits or to the soil in which the plants are growing or in which the growth of the plants is desired.

The term "effective and non-phytotoxic amount" means an amount of the composition of the present invention sufficient to control or destroy fungi present or likely to be present on the crop plant, but without imparting any undesirable symptoms of phytotoxicity to the crop plant in question. Such amounts are of wide range depending on the fungus to be combated, the type of crop, the climatic conditions and the compounds in the fungicidal composition. This amount can be determined by field testing of the system as can be performed by one skilled in the art.

Finally, the invention relates to products for the preventive or curative protection of plant propagation, and to a method for the protection of plants obtained therefrom against fungal diseases, characterized in that said products are coated with an effective non-phytotoxic dose of a composition according to the invention.

The compositions according to the invention can be used for the treatment of the seeds of cereals, in particular wheat, rye, triticale and barley, or potatoes, cotton, peas, oilseed rape, maize or flax, or of woodland trees, in particular resin-containing trees, or of genetically modified seeds of these plants.

It should be noted that in the technical parlance of the present field, "seed treatment" in fact refers to the treatment of grains. The application techniques are well known in the art and do not cause the drawbacks mentioned in the present invention after use. Application methods which may be mentioned are, for example, film coatings or coatings. Among the products of plant propagation, mention may be made in particular of seeds or grains and tubers.

As mentioned above, methods for coating plant propagation products, in particular seeds, are well known in the art, in particular with respect to coating film techniques or coating techniques.

The products and compositions of the invention may also be applied to crops via the leaves, such as to the leaves, flowers, fruits and/or plant cuttings.

Among the target plants on which the method of the invention acts, mention may be made of rice, maize, cotton, cereals (e.g.wheat, barley, triticale), fruit trees, in particular apple trees, pear trees, peach trees, grape trees, banana trees, orange trees, lemon trees and the like, oil-producing crops, for example flax and sunflower, market garden crops and legume crops, tomatoes, lettuce, egg white crops, peas, solanaceae plants, for example potatoes, beetroot and flax, and forest trees, and genetically modified congeners of these crops.

Among the target plants on which the method of the invention acts, mention may be made of:

-wheat, for the control of seed diseases: fusarium (Microdochium nivale and fusarium), smut (t, or t), septoria nodorum (septoria tritici), septoria nodorum (septoria nodorum), and loose smut;

wheat, for controlling diseases of aerial parts of the following plants: corn-eye patches (Tapesia yallundae, Tapesia acutiformis), wheat take-all (gaeumannomyces graminis), root blight (f. culmorum, f. graminearum), melasma (Rhizoctonia cerealis), powdery mildew [ powdery mildew of gramineae in the form of specific truncations (Erysiphe graminis for example tritici), rust (pucciniae and Puccinia recondita) and septoria (septoria tritici and septoria nodorum);

wheat and barley, for the control of bacterial and viral diseases, such as barley yellow mosaic;

-barley, for the control of seed diseases: mottle (Pyrenophora graminicola, Pyrenophora teres and Citrobacter graminicola), loose smut (Umbillomyces nudus) and Fusarium (Microdochium nivale and Fusarium roseum);

-barley, for controlling diseases of aerial parts of the following plants: grain-eye marks (Tapesiayallundae), reticulum marks (Pyrenophora graminifolia and Sporotrichum graminifolium), powdery mildew (powdery mildew gramine in the form of specific truncations), Puccinia graminis (Puccinia hordeum) and Blots of leaves (Blastoma tritici);

potato, for the control of tuber diseases (in particular Helminthosporium solani, Phomatuberosa, Rhizoctonia solani, Fusarium solani), molds (Phytophthora infestans) and certain viruses (virus Y);

-potatoes, controlling the following leaf diseases: early blight (Alternaria sotani), mildew (phytophthora infestans);

-cotton, controlling the following diseases of young plants growing from seeds: seedling decay and root neck decay (moniliforme);

protein-producing crops, such as peas, for controlling the following seed diseases: anthracnose (Ascochyta pisi, physalospora pisi), fusarium (fusarium oxysporum), botrytis cinerea (botrytis cinerea) and mildew (peronospora pea);

the control of the following seed diseases in oil-bearing crops, such as oilseed rape: phoma nigripes, alternaria brassicae and sclerotinia sclerotiorum;

-cereals for the control of seed diseases (rhizopus, penicillium, trichoderma, aspergillus, and gibberella);

flax, for the prevention and treatment of seed diseases: alternaria linicola;

-forest trees, control of take-all (fusarium oxysporum, rhizoctonia solani);

-rice, controlling diseases of the aerial parts: blight (Magnaporthe grisea), sheath blotches (rhizoctonia solani);

-leguminous crops, controlling seed diseases or young plant diseases growing from seeds: take all the blight and root neck rot (fusarium oxysporum, fusarium roseum, rhizoctonia solani, pythium);

-leguminous crops, controlling diseases of the aerial parts: botrytis (botrytis), powdery mildew (in particular powdery mildew, erysiphe graminis, burlap and erysiphe graminis), Fusarium (micropochiamnivale and Fusarium roseum), cladosporium (cladosporium), alternaria (alternaria), anthracnose (colletotrichum), conidiobolus (conidiophora), nigrospora (rhizoctonia solani), mildews (for example, colletotrichum lactuca, peronospora, pseudoperonospora, phytophthora);

-fruit trees, diseases for the aerial parts: candida diseases (hypocrea reniformis, sclerotinia sclerotiorum), scabs (venturia inaequalis), powdery mildew (ascochyta albicans);

grapevine, diseases directed to the leaves, in particular botrytis cinerea (botrytis cinerea), ustilago (botrytis cinerea), black rot (botrytis cinerea) and mildew (plasmopara viticola);

beetroot, a disease that targets the aerial parts: tail spore blight (Tail Bullospora betanae), Ustilago (Erysiphe betacola), and Pilus foliatus (Ramularia betacola).

Wheat and rice are preferred plants for carrying out the process according to the invention, although all crops, plants, plant propagation products, flowers, wood in general, all plants which are attacked by phytopathogenic fungi can advantageously be treated by using one or more active, fungicidal compositions according to the invention.

If plant treatment is carried out, the compositions are applied at a dose of from 10 to 800 g/ha, preferably from 50 to 300 g/ha, of active substance for the treatment of the leaves. The dosage of the composition for seed treatment is 2-200 g of active ingredient per 100kg of seed, preferably 3-150 g per 100kg of seed treated. It should be understood that the above dosages are only provided for illustrating the present invention. One skilled in the art would know how to tailor the applied dose to the nature of the crop being treated.

The invention also relates to a method for the therapeutic or prophylactic treatment against fungal diseases in or on wood by means of one or more compounds according to the invention or a composition according to the invention. The term "wood" denotes all kinds of wood, which are used for the manufacture of wood products, such as solid wood, high-density wood, laminated wood, plywood, etc.

Thus, the method of treating wood of the present invention comprises contacting one or more compounds or compositions of the present invention with wood. Contact covers the broadest form such as direct application, spraying, dipping, injection or any other suitable means.

The invention also relates to methods of treating genetically modified plants with the compounds of the invention or the agricultural compositions of the invention. Genetically modified plants are those plants in whose genome a heterologous gene encoding a protein of interest has been stably integrated.

According to the invention, the expression "heterologous gene encoding a protein of interest" essentially denotes a gene conferring new agricultural properties to the transformed plant, or a gene improving the agricultural quality of the transformed plant.

Among the genes which confer new agronomic properties on the transformed plants, mention may be made of genes which confer tolerance to certain herbicides, genes which confer tolerance to certain pesticides, genes which confer tolerance to certain diseases and the like. Such genes are described in patent applications WO91/02071 and WO 95/06128.

Among the genes conferring tolerance to certain herbicides, mention may be made of the Bar gene which is tolerant to bialophos, the genes encoding suitable EPSPS and thus tolerant to EPSPS-targeted herbicides, such as glyphosate and its salts (U.S. Pat. No. 4,535,060, U.S. Pat. No. 4,769,061, U.S. Pat. No. 5,094,945, U.S. Pat. No. 4,940,835, U.S. Pat. No. 5,188,64 2, U.S. Pat. No. 4,971,908, U.S. Pat. No. 5,145,783, U.S. Pat. No. 5,310,667, U.S. Pat. No. 5,312,910, U.S. Pat. No. 5,627,061, U.S. Pat. No. 5,633,435 and FR 39389), or the gene encoding HPPD, thus conferring tolerance to HPPD-targeted herbicides, such as isoxazoles, in particular isoxaflutol (FR95/06800 and FR95/06800 and 95/13570), diketonitrile (EP-A-593 2) and EP-A-593 2). Such genes encoding HPPD which confer tolerance to herbicides targeting HPPD are described in patent application WO 96/38567.

For the genes encoding EPSPS or HPPD, more particularly the above-mentioned genes, the sequences encoding these enzymes preferably precede the sequences encoding the transforming peptides, in particular the transforming peptides known as optimized transforming peptides (as described in US5,510,471).

Among the genes which confer novel insect-resistant properties, mention may be made in particular of the genes encoding Bt proteins, which are well known in the literature and in the prior art. Mention may be made of genes encoding proteins extracted from bacteria such as Photorabdus (WO 97/17432 and WO 98/08932).

Among the genes conferring novel anti-disease properties, mention may be made in particular of the genes encoding chitinase, polyglucoside and oxalate oxidase, all these proteins and the sequences they encode, have been reported in the literature, or else encode antibacterial and/or antifungal peptides, in particular cysteine-rich peptides (containing less than 100 amino acids), such as phytothionine or defensine, more particularly cytolytic peptides of all origins which contain one or more disulfide bridges between cysteine and a region containing the basic amino acids, in particular the following cytolytic peptides: androctonine (WO 97/30082 and PCT/FR98/01814, filed 8/18/1998) or drosomicin (PCT/FR98/01462, filed 7/8/1998). Also mentioned are genes encoding fungal promoters (elicertors), peptides, and in particular elicertin (Kamount et al, 1993; Panabieres et al, 1995).

Among the genes which modify the structure of the plant to be modified, mention may be made in particular of genes which modify the content and quality of certain essential fatty acids (EP-A-0666918) or genes which modify the content and quality of proteins (in particular the leaves and/or the seeds of said plant). Mention may be made of genes encoding proteins rich in sulfur-containing amino acids (WO 98/20133; WO 97/41239; WO 95/31554; WO 94/20828 and WO 92/14822).

The invention more specifically relates to methods of treating genetically modified plants comprising heterologous genes that confer disease resistance properties to the plants. Preferably, the heterologous gene provides a spectrum of activity for the genetically modified plant that is complementary to the spectrum of activity of the compound of the invention. According to the invention, the term "complementary profile" means that the activity profile of the heterologous gene is different from that of the compound of the invention, or that the same or an improved spectrum of activity is obtained with respect to the same infectious agent, but at a lower dose, with application of the compound of the invention.

Finally, the invention relates to the use of the compounds according to the invention for the treatment of fungal diseases such as mycoses, skin diseases, trichopathies and candidiasis or diseases caused by aspergillus (e.g. aspergillus fumigatus) in the treatment of the human and animal body.

The following examples illustrate some examples of fungicidal compounds in a non-limiting manner. In the following examples, "MP" means "melting point" and is expressed in degrees Celsius.

Example a):

preparation of 2-cyano-3-methoxy-4-nitropyridine

12.5 g (12.5 mol) of N-oxide of 3-methoxy-4-nitropyridine, 7.72 ml (1.1 eq) of methyl sulfate and 70 ml of 1, 2-dichloroethane are heated at 70 ℃ for 2.5 hours. It was allowed to cool and 70 ml of water were added. Cooled in a salt and ice bath, 7.55 g (2.1 mol) of sodium cyanide are added in portions, and the temperature is controlled so that it does not exceed 10 ℃. After stirring for 4 hours, the reaction mixture is extracted with diethyl ether, the organic phase is washed with water, concentrated and the residue is chromatographed (ethyl acetate/dichloromethane). 7.06 g of a yellow oil are obtained (yield 53%).

Example b):

preparation of 4-bromo-2-cyano-3-methoxypyridine

A mixture of 6 g (0.0335 mol) of 2-cyano-3-methoxy-4-nitropyridinyl obtained in example a), 12.37 g (0.100 mol) of acetyl bromide and 36 ml of 1, 2-dimethoxyethane was heated at 85 ℃ for 1.5 hours. It was allowed to cool and the reaction mixture was poured into 100 g of crude ice. 30 ml of 1, 2-dichloroethane were added and the mixture was slowly neutralized to pH 8 with 28% aqueous ammonia. After extraction with 1, 2-dichloroethane, the residue is washed with water, dried and concentrated and chromatographed (ethyl acetate/heptane 3: 7) to give 5.32 g (75% yield) of a white solid (MP 116 ℃).

In a similar manner, acetyl chloride was used instead of acetyl bromide to give 4-chloro-2-cyano-3-methoxypyridine (83% yield) as a white solid (MP ═ 91 ℃).

Example c):

preparation of 4-azido-2-cyano-3-methoxypyridine

To a mass of 1 g (0.0155 mol) of sodium azide in 25 ml of dimethylformamide was added gently 3 g (0.0141 mol) of 4-bromo-2-cyano-3-methoxypyridine from example b) dissolved in 40 ml of dimethylformamide at 0 ℃. The mixture was stirred at room temperature for 6 hours. The reaction mixture was diluted in 200 ml of ice-water and extracted with dichloromethane. The organic phase is washed twice with water, dried, concentrated and the residue is chromatographed (ethyl acetate/heptane, 3: 7). 0.87 g (35% yield) of a white solid is obtained (MP 102 ℃ C.).

Example d):

preparation of 4-chloro-3-hydroxypyridylcarboxylic acid

A mixture of 2 g (0.012 mol) of 4-chloro-2-cyano-3-methoxypicolinic acid from example b) and 7 ml of 37% hydrochloric acid is heated at 100 ℃ for 12 hours. After cooling, the solid formed was filtered, washed once with water, 3 times with acetone and dried under vacuum for 8 hours to give 1.78 g (86% yield) of a yellow solid (MP ═ 228 ℃).

The following hydroxy acids were obtained in the same way:

yield of Y hydrogen acid, MP (. degree. C.)

HBr yellow solid, 82%, 230 ℃ 4-bromo-3-hydroxy-picolinic acid

4-azido-3-hydroxy-picolinic acid HCl purple solid, 63%

HBr white solid, 74%, 264 ℃ 3, 4-Dihydroxypicolinic acid

Example e): preparation of 2-cyano-3, 4-dimethoxypyridine

3 g (0.017 mol) of 2-cyano-3-methoxy-4-nitropyridine from example a) and a sodium methoxide solution prepared from 0.77 g (0.033 mol) of sodium and 65 ml of methanol were stirred at room temperature for 4 hours. 100 ml of water were added, the methanol was eliminated and the aqueous phase was extracted with dichloromethane. The organic phase is washed with water, dried and concentrated, and the residue is chromatographed (ethyl acetate/heptane, 1: 1) to give 1.96 g (72% yield) of a white solid (m.p.: 133 ℃).

Example f):

preparation of 2-cyano-3-hydroxy-4-thiomethoxy pyridine

A mixture of 2 g of 4-bromo-2-cyano-3-methoxypyridine from example b) and 2.16 g of sodium thiomethoxide in 40 ml of anhydrous dimethylformamide is heated at 85 ℃ for 5 hours. After cooling and addition of 20 ml of water, the reaction mixture is concentrated to dryness. The residue was extracted three times with hot methanol. The cooled methanol phase was filtered and concentrated. 1.51 g (97% yield) of brown syrup are obtained, which is used as crude product.

Example g):

preparation of 3-hydroxy-4-thiomethoxy picolinic acid

2.5 g (0.015 mol) of 2-cyano-3-hydroxy-4-thiomethoxypyridine from example f), 8.5 g of potassium hydroxide and 25 ml of water are heated under reflux for 2.5 hours. After cooling in an ice bath, the mixture was slowly neutralized with 1N hydrochloric acid to pH 2-3. The solid formed was filtered. Washing the solid once with water and three times with acetone; vacuum drying for 8 hours. 1.81 g (68% yield) of a white solid (MP 247 ℃) are obtained.

Example h):

preparation of 3, 4-dimethoxy pyridine carboxylic acid

1 g of 3, 4-dimethoxy-2-cyanopyridine from example e) and 3.5 g of potassium hydroxide in 15 ml of water are heated to 85 ℃ for half an hour. It was cooled in an ice bath and hydrochloric acid was slowly added to pH 2-3. After concentration to dryness, the residue was extracted three times with hot methanol, cooled, filtered and concentrated. A solid crude product is obtained.

Example i):

preparation of N-oxides of 3-hydroxypicolinic acid

To a mixture of 20 ml acetic acid and 20 ml hydrogen peroxide solution was added 2 g of 3-hydroxypicolinic acid; it was allowed to heat at 80 ℃ for 5 hours. After removal of the solvent in vacuo, the resulting solid was washed with hot methanol to give 2.02 g of the compound as a white solid (MP ═ 182 ℃).

Preparation examples:

3-hydroxy-4-methoxy-N-p-phenoxyphenylpyridinamides

0.046 g of p-phenoxyaniline, 0.04 g of 3-hydroxy-4-methoxypicolinic acid (obtained in a manner similar to example g), 0.034 g of 1-hydroxybenzotriazole and 0.060 g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride were heated to 75-85 ℃ in 2 ml of pyridine for 1-2 hours. After cooling, the residue was dissolved in a mixture of dichloromethane and 2 ml of 1N hydrochloric acid. After extraction with dichloromethane, concentration and chromatography on silica gel, 0.057 g of the title compound are obtained as a yellow solid (MP ═ 186 ℃).

Example 1: compound No. 76

4-amino-3-hydroxy-N-p-phenoxyphenylpyridinecarboxamide

To 0.14 g of 4-azido-3-hydroxy-N-p-phenoxyphenylpyridinecarboxamide (compounds of the preparation examples obtained in a similar manner to examples a) to g)) dissolved in an ethanol/ethyl acetate 1: 2 mixture, 10% palladium on carbon from a spatula tip was added. The hydrogenation is carried out at 20 bar pressure and room temperature for 4 to 5 hours. After filtration, the filtrate was concentrated and the residue was chromatographed on ethyl acetate to give 0.099 g of a white solid (MP: 197 ℃ C.).

Example 2: compound No. 111

4-carboxamido-3-hydroxy-N-p-phenoxyphenylpyridine carboxamide

61.2 mg of acetic anhydride and 27.6 mg of formic acid are refluxed for 4 hours, and 46 mg of 4-amino-3-hydroxy-N-p-phenoxyphenylpyridine carboxamide of example 1 dissolved in 5 ml of tetrahydrofuran are added. After 8 hours of reflux, the reaction mixture was concentrated and purified by chromatography to give 39 mg of a yellow solid, MP208 ℃.

Example 3: compound No. 108

4-amino-3-hydroxy-N-p- [4- (trifluoromethyl) phenoxy ] -phenylpyridine carboxylic acid amide

Stage 1:

4-azido-3-iodo-N-p- [4- (trifluoromethyl) phenoxy ] phenylpyridine carboxamide

A mixture of 25.9 g (0.05 mol) 4-chloro-3-iodo-N-p- [4- (trifluoromethyl) phenoxy ] -phenylpyridine carboxamide (prepared from picolinic acid according to the procedure described in Heterocycles, 47, (1998), 811) and 6.5 g (0.1 mol) sodium azide in 50 ml of dimethyl sulfone is heated to 70 ℃ for 8 hours. After cooling, the mixture was poured into 1 liter of water. The precipitate was filtered and washed with ether to give 22.5 g (85% yield) of a brown solid. Rf (heptane/ethyl acetate 50/50) 0.45.

And (2) stage:

4-amino-3-hydroxy-N-p- [4- (trifluoromethyl) phenoxy ] phenylpyridine carboxamide

A mixture of 21.0 g (0.04 mol) of 4-azido-3-iodo-N-p- [4- (trifluoromethyl) phenoxy ] phenylpyridine carboxamide and 21.0 g (0.08 mol) of triphenylphosphine in 80 ml of tetrahydrofuran was stirred at room temperature for 15 hours. The mixture was hydrolyzed under the action of 100 ml of 1N hydrochloric acid for 1 hour. The mixture was then poured into 200 ml of water and neutralized by adding 100 ml of 1N sodium hydroxide. After extraction with ethyl acetate, drying and concentration, the residue is chromatographed on silica gel (ethyl acetate/heptane 1: 1) to give 13.4 g (55% yield) of a yellow solid. Rf (heptane/ethyl acetate 50/50): 0.29.

and (3) stage:

4-amino-3-hydroxy-N-p- [4- (trifluoromethyl) -phenoxy ] phenylpyridine carboxylic acid amide

A mixture of 9.15 g (0.018 mol) 4-amino-3-iodo-N-p- [4- (trifluoromethyl) phenoxy ] phenylpyridinecarboxamide dissolved in 82 ml 50% aqueous potassium hydroxide and 20 ml dimethyl sulfone was heated at 90 ℃ for 8 hours. The medium is poured into 100 ml of water and extracted with ether. The organic phase was dried and separated. After recrystallization from methanol, 6.15 g (85% yield) of a white solid were obtained (MP ═ 202 ℃).

The compounds listed in tables 1 and 2 below were prepared in a similar manner: TABLE 1TABLE 2

Example 4: compound No. 171

4-chloro-3-mercapto-N-p- [ 3- (trifluoromethyl) phenoxy ] phenylpyridine carboxamide

To a solution of 100 mg (0.25 mmol) of 4-chloro-N-p- [ 3- (trifluoromethyl) phenoxy ] phenylpyridine carboxamide (prepared from picolinic acid according to the method described in Heterocycles, 47, (1998), 811) in 2 ml of anhydrous acid anhydride at-78 ℃ was added over 15 minutes 0.32 ml of a commercially available solution of lithium 2M diisopropylamide. After stirring at-78 ℃ for 1 hour, 103 mg (0.40 mmol) of sulfur were added. The mixture was stirred at-78 ℃ for a further 3 hours and then treated with a saturated aqueous solution of ammonium chloride. The ice bath was then removed. The phases were separated and the aqueous phase was extracted with dichloromethane (2 × 1 ml). The combined organic phases were dried over anhydrous magnesium sulfate and concentrated. The residue was purified by chromatography on silica gel (dichloromethane/methanol, 97: 3). 61 mg (57% yield) of an orange solid (APCI-, 423, M-1) are obtained.

Example 5: compound 186

4-chloro-3- { [ (4-methoxyphenyl) methyl ] thio } -N-p- [ 3- (trifluoromethyl) phenoxy ] phenylpyridine-carboxamide

To a solution of 3.71 g (8.73 mmol) of 4-chloro-3-mercapto-N-p- [ 3- (trifluoromethyl) phenoxy ] phenylpyridine carboxamide and 1.21 ml (1 eq) of triethylamine in 75 ml of tetrahydrofuran was slowly added 1.38 ml of 4-methoxybenzyl chloride. After stirring at room temperature for 24 hours, the reaction mixture was washed with water, and the organic phase was dried over anhydrous magnesium sulfate and evaporated. The residue was purified by silica gel chromatography (ethyl acetate/heptane, 50: 50). 2.94 g (62% yield) of a brown oil (APCI +, 545, M +1) are obtained.

Example 6: compound No. 199

4-azido-3- { [ (4-methoxyphenyl) methyl ] thio } -N-p- [ 3- (trifluoromethyl) phenoxy ] phenylpyridine-carboxamide

A mixture of 50 mg (0.092 mmol) of 4-chloro-3- { [ (4-methoxyphenyl) methyl ] thio } -N-p- [ 3- (trifluoromethyl) phenoxy ] phenylpyridine-carboxamide, 30 mg (5 equivalents) of sodium azide and 1 ml of dimethylformamide was heated at 60 ℃ for 5 days. After cooling, the solvent was evaporated in vacuo and the residue was purified by silica gel chromatography (ethyl acetate/heptylalkane 50: 50). 29 mg (57% yield) of a yellow oil (APCI +, 552, M +1) are obtained.

Example 7: compound No. 207

Preparation of 4-amino-3-mercapto-N-p- [ 3- (trifluoromethyl) phenoxy ] phenylpyridinecarboxamide

To a solution of 200 mg (0.36 mmol) of 4-azido-3- { [ (4-methoxyphenyl) methyl ] thio } -N-p- [ 3- (trifluoromethyl) phenoxy ] phenylpyridine carboxamide in 4 ml of tetrahydrofuran was added 228 mg (2.4 equivalents) of triphenylphosphine. The mixture was stirred at room temperature for 18 hours and then treated with 1 ml of 5% aqueous hydrochloric acid. After 10 minutes, the two phases were separated and the organic phase was washed with water, dried over anhydrous magnesium sulfate and concentrated. The residue was purified by silica gel chromatography (ethyl acetate/heptane, 50: 50). 99 mg (68% yield) of a white solid (APCI-, 404, M-1) are obtained.

Example 8: compound No. 190

4-isobutylamino-3- { [ (4-methoxyphenyl) methyl ] thio } -N-p- [ 3- (trifluoromethyl) phenoxy ] phenylpyridine-carboxamide

A solution of 50 mg (0.092 mmol) of 4-chloro-3- { [ (4-methoxyphenyl) methyl ] thio } -N-p- [ (3-trifluoromethyl) phenoxy ] phenylpyridine carboxamide in 1 ml of isobutylamine was heated at 60 ℃ for 24 hours. After cooling, the excess amine was evaporated and the residue was purified by silica gel chromatography (ethyl acetate/heptane, 50: 50). 29 mg (54% yield) of a colorless oil (APCI +, 582, M +1) were obtained.

Example 9: compound No. 198

4-isobutylamino-3-mercapto-N-p- [ 3- (trifluoromethyl) phenoxy ] phenylpyridine carboxamide

A solution of 25 mg (0.043 mmol) of 4-isobutylamino-3- { [ (4-methoxyphenyl) methyl) thio } -N-p- [ 3- (trifluoromethyl) phenoxy ] phenylpyridine carboxamide and 45 ml (10 equivalents) of m-cresol in 0.6 ml of trifluoroacetic acid was heated at 70 ℃ for 24 hours. After cooling, the trifluoroacetic acid is evaporated and the residue is basified slowly with saturated sodium bicarbonate solution. The mixture was neutralized to pH 7 with a saturated aqueous solution of ammonium chloride and extracted with dichloromethane. The combined organic phases were dried over anhydrous magnesium sulfate and concentrated. The residue was purified by silica gel chromatography (ethyl acetate/heptane, 50: 50). 12 mg (38% yield) of a yellow solid (APCI +, 462, M +1) are obtained.

The compounds listed in table 3 below were prepared in a similar manner. TABLE 3

Examples of biological Activity of Compounds of the invention

Example A:

testing of Alternaria brassicolor (Alternaria brassicolor) [ Leaf spot of Brassicaceae (Leaf spots of crucifers) ] under Natural conditions (in vivo)

An aqueous suspension with an active substance concentration of 2 g/l is obtained by finely grinding the following mixture:

-water

Tween 80 surfactant (polyoxyethylenated derivative of sorbitol oleate), diluted to 10% with water: 5 ml/mg active substance

-clay: inert carrier, adding to 100%

The aqueous suspension is then diluted with water to give the desired active substance concentration.

Radishes (of the species Pernot) in a starter cup (starter cup) were sown on a 50/50 peat soil-pozzolan matrix, grown at 18-20 ℃ and treated at the cotyledon stage by spraying the above aqueous suspension.

Plants used as controls were treated with an aqueous solution without active substance.

After 24 hours, by spraying with an aqueous suspension of Alternaria brassicae spores (40,000 spores/cm)³) To infect the plant. Spores were collected from 12-13 day old crops.

The infested radishes are incubated in a humid environment at about 18 ℃ for 6-7 days.

Grading is carried out 6 to 7 days after infection, in comparison with control plants.

Under these conditions, a dose of 250 g/ha of compound is used: 108, 110, 112, 115, 116, 130, 133, good (at least 50%) or full protection results can be obtained.

Example B: test on Septoria nodorum (Septoria nodorum) [ wheat rot (wheat rot) ], in Natural conditions (in vivo):

an aqueous suspension of 2 g/l active substance concentration tested was obtained by finely grinding the following mixture:

-water

-clay: inert carrier, adding to 100%

Wheat (Scipion variety) in the starter cup was sown on a 50/50 peat soil-pozzolan matrix, grown at 12 ℃ and treated by spraying the above aqueous suspension at the 1-leaf stage (10 cm height).

After 24 hours, the suspension was sprayed with an aqueous suspension of Septoria nodorum spores (500,000 spores/cm)³) To infect the plant. Spores were collected from 7 day old crops.

The infected wheat was incubated in a humid environment at about 18 ℃ for 72 hours and then at 90% relative humidity for 14 days.

15-20 days after infestation, grading is carried out in comparison with control plants.

Under these conditions, a dose of 250 g/ha of compound is used: 108, 110, 112, 133, good (at least 50%) or full protection results can be obtained.

Example C: testing Magnaposthe grisea (Fusarium oxysporum) under natural conditions:

an aqueous suspension with an active substance concentration of 50 mg/l is obtained by finely grinding the following mixture:

-water

-2% acetone.

Rice plants (Koshihirakari species) were sown on Kureha soil at 33 cm²Growing in plastic tank to 3-4 blade stage, and spraying the above water suspensionAnd (6) processing.

24 hours after the treatment, spraying with an aqueous suspension of Magnaporthe grisea spores (500,000 spores/cm)³) To infect the plant.

The infected wheat is cultured in an incubator at about 25 ℃ for 24 hours in a humid environment, and then cultured in an incubator at 20-25 ℃ and a relative humidity of 70-90% for 5-7 days.

5-7 days after infestation, grading is carried out by counting the damage of the first leaf of the plant.

Under these conditions, the following compounds were used in a dose of 50 mg/l: 62, 114, 115, good (at least 50%) or full protection results can be obtained.

Example D: test of Amylobacter graminicola (Erisyphe graminis f.sp.tritici) [ wheat flour mold (of wheat flour) ] under natural conditions (in vivo)

-water

-clay: inert carrier, adding to 100%

Wheat plants (Audace variety) in the starting cups were sown on a 50/50 peat soil-pozzolana matrix, grown at 12 ℃ and treated by spraying the above aqueous suspension at the 1-leaf stage (10 cm height).

After 24 hours, the plants are infected by sowing the powdery mildew spores, and the plants with the diseases are sown.

7-14 days after infestation, grading is carried out in comparison with control plants.

Under these conditions, a dose of 500 g/ha of compound is used: 108 good (at least 50%) or full protection results can be obtained.

Example E:

rhizoctonia solani (Rhizoctonia solani) [ rice sheath blight of rice) ] was tested under natural conditions:

an aqueous suspension with an active substance concentration of 100 mg/l is obtained by finely grinding the following mixture:

-water

-2% acetone.

Rice plants (Koshihirakari species) were sown on Kureha soil at 33 cm²Growing in plastic tank to 7-8 blade stage, and spraying the above water suspension for treatment.

24 hours after treatment, each plant was infested by placing an agar dish of the growing fungus from Rhizoctonia solani on PDA between the stem and sheath.

The infected plants are then cultured for 24 hours at 25 ℃ and 100% humidity and then for 5-7 days at 70-90% relative humidity.

7 days after infestation, the plants were rated by measuring the height of the lesions and comparing with controls.

Under these conditions, a dose of 100ppm of compound: 62, 133 good (at least 50%) or full protection results were obtained.

Example F: testing of Septoria tritici (Septoria tritici) under natural conditions:

by fine grinding of formulations of the concentrated suspension type, such as the above-mentioned example CS (formulations CS1, CS2 or CS3), an aqueous suspension is obtained with an active substance concentration of 1.5%:

the aqueous suspension is then diluted with water to give the desired active substance concentration, i.e. 2 g/l.

Wheat plants (Scipion species) in starter cups were sown on 50/50 peat soil-pozzolana substrate, grown at 12 ℃ and treated by spraying the above aqueous suspension at the 1-leaf stage (10 cm height).

24 hours after the treatment, the plants were infected by spraying (500,000 spores/ml) with an aqueous spore suspension of septoria tritici. Spores were collected from 15 day old crops and suspended in a nutrient solution of the following composition:

1.5 g/l gelatin

0.5 g/l sodium oleate

24 g/l PDB

The infected wheat was incubated at 100% relative humidity and about 20 ℃ for 72 hours and then at 80% relative humidity for 15 days.

15-20 days after infestation, grading is carried out by comparison with control plants.

Under these conditions, a dose of 50 g/ha of compound was used: 108 good (at least 50%) or full protection results can be obtained.

Claims

1. A compound of the general formula (I), and optionally N-oxides, geometrical and/or optical isomers, enantiomers and/or diastereomers, tautomeric forms, salts and metal and non-metal complexes thereof,wherein:

g represents an oxygen or sulphur atom,

n represents a number 0 or 1,

·Q₁selected from oxygen or sulfur atoms, radicals NR₁Or N-NR₄R₅，

·Q₂Selected from OR₂Or SR₃Or is-NR₄R₅Or is or

·Q₁And Q₂May together form a 5-7 membered ring containing 2-3 oxygen and/or nitrogen atoms, which may optionally be substituted by one or more identical or different substituents selected from halogen or alkyl or haloalkyl,

amino, N-alkylamino, N, N-dialkylamino, -NHCOR₁₀，-NHCSR₁₀N-alkylaminocarbonylamino, N, N-dialkylaminocarbonylamino, aminoalkyl, N-alkylaminoalkyl, N, N-dialkylaminoalkyl, acylAminoalkyl, thioacylamino, alkoxythiocarbonylamino, N-alkylaminothiocarbonylamino, N, N-dialkylaminothiocarbonylamino, N, N-aralkylaminocarbonylamino, N-alkylsulfinylamino, N-alkylsulfonylamino, N-alkyl (alkylsulfonyl) amino, N-arylsulfinylamino, N-arylsulfonylamino, N-alkoxysulfonylamino, N-alkoxysulfinylamino, N-haloalkyloxysulfinylamino, N-haloalkyloxysulfonylamino, N-arylamino, N, N-diarylamino, arylcarbonylamino, alkoxycarbonylamino, N-arylaminocarbonylamino, N, N-diarylaminocarbonylamino, arylthiocarbonylamino, aryloxythiocarbonylamino, N-arylaminothiocarbonylamino, N, N-diarylaminothiocarbonylamino or N, N-arylalkylaminothiocarbonylamino,

·X₁and X₂Identical or different, each independently from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl, mercapto, nitro, thiocyanato, azido, cyano or pentafluorosulfonyl group, or an alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, cyanoalkyl, cyanoalkoxy, cyanoalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl or alkoxysulfonyl group, or

·R₂and R₃Are identical or different and are each independently selected from the group consisting of 1 to 12 carbon atomsAlkyl, haloalkyl, cycloalkyl, halocycloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxyaryl, alkylthioalkyl, haloalkylthioalkyl, cyanoalkyl or acyl, nitro, cyano, carboxy, carbamoyl or 3-oxetanyloxycarbonyl (3-oxocarbonyloxy), and N-alkylcarbamoyl, N, N-dialkylcarbamoyl, alkoxycarbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl, alkylthiocarbonyl, alkenyl, alkynyl, N-alkylamino, N, N-dialkylamino, N-alkylaminoalkyl or N, N-dialkylaminoalkyl, or

Optionally substituted by one or more R, the same or different₉And/or aryl and/or aralkyl substituted radical selected from aryl, aralkyl, heterocyclyl and heterocycloalkyl, and/or the radical-T-R₈Or is or

On the one hand R₄And R₅Or on the other hand R₆And R₇May be linked together to form a saturated, partially unsaturated or fully unsaturated 4-to 8-membered ring, optionally containing one or more heteroatoms selected from sulfur, oxygen, nitrogen and phosphorus,

t represents directly a bond, or represents a divalent radical selected from- (CH)₂) m- (m is 1-12, and is limited, and the group can be interrupted or terminated by one or two heteroatoms selected from nitrogen atom, oxygen atom and/or sulfur atom), and oxyalkenyl, alkoxyalkenyl, carbonyl (-CO-), oxycarbonyl (-O-CO-), carbonyloxy (-CO-O-), sulfinyl (-SO-), sulfonyl (-SO-)₂-, oxysulfonyl (-O-SO)₂-, sulfonyloxy (-SO)₂-O-), oxysulfinyl (-O-SO-), sulfinyloxy (-SO-O-), thio (-S-), oxy (-O-), vinyl (-C ═ C-), alkynyl (-C ≡ C-), -NR₉-，-NR₉O-，-ONR₉-，-N＝N-，-NR₉-NR₁₀-，-NR₉-S-，-NR₉-SO-，-NR₉-SO₂-，-S-NR₉-，-SO-NR₉-，-SO₂-NR₉-，-CO-NR₉-O-or-O-NR₉-a CO-group, in which,

·R₉and R₁₀Are identical or different and are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, a thiocyanato group, an azido group, a cyano group or a pentafluorosulfonyl group, and an alkyl group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkylthio group, a haloalkylthio group, an alkoxyalkyl group, a haloalkoxyalkyl group, an alkylthioalkyl group, a haloalkylthioalkyl group, an arylalkyl group, a cyanoalkyl group, a cyanoalkoxy group, a cyanoalkylthio group, an alkylsulfinyl group, a haloalkylsulfinyl group, an alkylsulfonyl group, a haloalkylsulfonyl group,

2. The compound according to claim 1, and optionally N-oxides, geometric and/or optical isomers, enantiomers and/or diastereomers, tautomeric forms, salts and metal and non-metal complexes thereof. Characterized in that wherein

the other substituents are as defined in claim 1,

with the limitation that when Q₁G-Z represents oxygen, G-Z represents dialkylaminocarbonyloxy or dialkylaminothiocarbonyloxy, Y represents NH₂Or N₃Group, Q₂represents-NR₄R₅，R₄When represents an alkyl group having 1 to 12 carbon atoms, then R₅And may not represent an alkyl group having 1 to 12 carbon atoms.

3. The compound according to claim 1, and optionally N-oxides, geometrical and/or optical isomers, enantiomers and/or diastereomers, tautomeric forms, salts and metal and non-metal complexes thereof, wherein,

·Q₁selected from the group consisting of oxygen and sulfur atoms,

the other substituents are as defined in claim 1,

4. The compound according to claim 1, and optionally N-oxides, geometrical and/or optical isomers, enantiomers and/or diastereomers, tautomeric forms, salts and metal and non-metal complexes thereof, wherein,

z is selected from alkyl and hydrogen atoms or alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, N-alkylaminoalkyl, N, N-dialkylaminoalkyl, acylaminoalkyl, acyl, thioacyl, cyanoalkyl, alkoxythiocarbonyl, N-alkylaminothiocarbonyl, N, N-dialkylaminothiocarbonyl or alkylsulfinyl,

the other substituents are as defined in claim 1,

5. The compound according to claim 1, and optionally N-oxides, geometrical and/or optical isomers, enantiomers and/or diastereomers, tautomeric forms, salts and metal and non-metal complexes thereof, wherein,

the other substituents are as defined in claim 1,

6. The compound according to claim 1, and optionally N-oxides, geometrical and/or optical isomers, enantiomers and/or diastereomers, tautomeric forms, salts and metal and non-metal complexes thereof, wherein,

·Q₂represents the group-NR₄R₅Wherein R is₄Represents a hydrogen atom, R₅Selected from optionally substituted, linear or branched alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkenyl or alkynyl having 1 to 12 carbon atoms, and from aryl, arylalkyl, heterocyclyl and heterocyclylalkyl groups (which groups are optionally substituted by one or more identical or different radicals R₉And/or aryl and/or arylalkyl) and/or-T-R₈，

The other substituents are as defined in claim 1,

7. The compound according to claim 1, and optionally N-oxides, geometrical and/or optical isomers, enantiomers and/or diastereomers, tautomeric forms, salts and metal and non-metal complexes thereof, wherein the following features are individually established or combined together,

·Q₁selected from the group consisting of an oxygen atom and a sulfur atom,

·Q₂represents the group-NR₄R₅Wherein R is₄Represents a hydrogen atom, R₅Selected from optionally substituted, linear or branched alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkenyl and alkynyl having 1 to 12 carbon atoms, and from aryl, arylalkyl, heterocyclyl and heterocyclylalkyl which are optionally substituted by one or more identical or different radicals R₉And/or aryl and/or arylalkyl substitution), and/or a group-T-R₈，

The other substituents are as defined in claim 1,

8. The compound according to claim 1 or claim 7, and optionally N-oxides, geometrical and/or optical isomers, enantiomers and/or diastereomers, tautomeric forms, salts and metal and non-metal complexes thereof, wherein,

·Q₁selected from the group consisting of an oxygen atom and a sulfur atom,

·Q₂represents the group-NR₄R₅Wherein R₄Represents a hydrogen atom, R₅Selected from optionally substituted, linear or branched alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkenyl and alkynyl having 1 to 12 carbon atoms, and from aryl, arylalkyl, heterocyclyl and heterocyclylalkyl which are optionally substituted by one or more identical or different radicals R₉And/or aryl and/or arylalkyl substitution), and/or a group-T-R₈，

The other substituents are as defined in claim 1,

9. The compound according to any one of claims 1 to 8, and optionally N-oxides, geometrical and/or optical isomers, enantiomers and/or diastereomers, tautomeric forms, salts and metal and non-metal complexes thereof, wherein,

y is selected from a halogen atom, a hydroxyl group, an azido group, an alkylthio group, or an alkylsulfinyl group, and an amino group, -NHCOR₁₀，-NHCSR₁₀，

·Q₁Selected from the group consisting of an oxygen atom and a sulfur atom,

·Q₂represents the group-NR₄R₅Wherein R is₄Represents a hydrogen atom, R₅Selected from aryl, arylalkyl, heterocyclyl and heterocyclylalkyl optionally substituted with one or more identical or different groups R₉And/or aryl and/or arylalkyl substitution, and/or the group-T-R₈，

The other substituents are as defined in claim 1.

10. A compound according to any one of claims 1 to 9, and optionally N-oxides, geometrical and/or optical isomers, enantiomers and/or diastereomers, tautomeric forms, salts and metal and non-metal complexes thereof, wherein the compound is:

4-amino-3-hydroxy-N- [4- (4-methylphenoxy) phenyl ] -2-pyridinecarboxamide,

4-amino-3-hydroxy-N- {4- [4- (trifluoromethyl) phenoxy) -phenyl } -2-pyridinecarboxamide,

n- [4- (4-chlorophenoxy) phenyl) -4- (formylamino) -3-hydroxy-2-pyridinecarboxamide,

n- [4- (4-benzyloxy) phenyl) -4- (carboxamido) -3-hydroxy-2-pyridinecarboxamide.

11. A process for the preparation of a compound according to any one of claims 1 to 10, wherein G represents oxygen, characterized in that a compound of formula (IIa):wherein X₁，X₂，Q₁And Q₂Is as defined in claim 1, W₁And W₂Which may be the same or different, each represents a halogen atom selected from fluorine, chlorine, bromine and iodine,

with azothydric acid salt in a polar aprotic solvent at a temperature of 20-200 ℃ to give a compound of formula (IIIa):wherein X₁，X₂，Q₁And Q₂Is as defined above, W₂Represents a halogen atom selected from fluorine, chlorine, bromine and iodine,

optionally reducing the compound of formula (IIIa) to the corresponding amine derivative of formula (IVa) by the action of a reducing agent in the presence of a catalyst:wherein X₁，X₂，Q₁And Q₂Is as defined above, W₂Represents a halogen atom selected from fluorine, chlorine, bromine and iodine,

the halo derivative of formula (IVa) is then hydrolyzed by the action of an inorganic base to the 3-hydroxypicolinic acid derivative (Va):wherein X₁，X₂，Q₁And Q₂The definition of (A) is the same as that of (B),

the reaction is generally carried out in a polar aprotic solvent at a temperature of from 0 ℃ to the boiling point of the solvent,

the compound of formula (Va) may optionally be subjected to various alkylation reactions known in the art to give a compound of formula (VIa):wherein X₁，X₂，Z，Q₁And Q₂Is as defined in claim 1.

12. A process for the preparation of a compound according to any one of claims 1 to 10, wherein G represents sulphur, by reacting a compound of formula (IIb):wherein X₁，X₂，Q₁And Q₂Is as defined in claim 1, W₁Represents a halogen atom selected from fluorine, chlorine, bromine and iodine,

with an inorganic base to give a compound of formula (IIIb):wherein X₁，X₂，W₁，Q₁And Q₂Is as defined in claim 1, and is,

converting the thiol of formula (IIIb) to a compound of formula (IVb) by reaction with an alkylating agent:wherein X₁，X₂，Q₁And Q₂Is as defined in claim 1 and is,

by reaction with the formula R₆R₇Reacting the NH compound, or the corresponding alkali or alkaline earth metal salt thereof, with or without a polar aprotic solvent at a temperature from 0 ℃ to the boiling point of the solvent to convert the compound of formula (IVb) to a 4-amino compound of formula (Vb):wherein X₁，X₂，Q₁，Q₂，Z，R₆And R₇The same as defined in claim 1, Z represents 4-methoxydiphenylethanolic acid group, reacting the compound of formula (Vb) with an organic acid in a polar protic solvent at reflux temperature or at 20 ℃ to 200 ℃ to give a compound of formula (VIb):wherein X₁，X₂，Q₁，Q₂，R₆And R₇Is as defined in claim 1,

the compound of formula (IVb) may be converted to an azide of formula (VIIb) by reacting the compound of formula (IVb) with an azothydric acid salt in a polar aprotic solvent at reflux temperature or at a temperature of 20-200 ℃:wherein X₁，X₂，Q₁，Q₂And Z is as defined in claim 1,

hydrolyzing the compound of formula (VIIb) to a compound of formula (VIIIb) by the action of a reducing agent in the presence of a catalyst:wherein X₁，X₂，Q₁And Q₂The definition of (A) is as above.

13. A process for the preparation of a compound according to any one of claims 1 to 10, wherein a compound of formulae (Va), (VIa) and (VIIIb) according to claims 11 and 12 is contacted with an acylating agent in a solvent and optionally in the presence of a base to give a compound of formula (IX)₁) And (IX)₂)：Wherein G, X₁，X₂，Q₁，Q₂Z and R₁₀The definition of (A) is the same as that of (B),

the compounds of formulae (VIa) and (IVb) may also optionally be subjected to various substitution and/or addition reactions well known in the art to give compounds of formula (X):wherein G, X₁，X₂，Q₁，Q₂Y and Z have the same meanings as defined in claim 1, which is a specific series of compounds of the formula (I) in which n represents 0,

by contacting a compound of formula (X) with an oxidizing agent, a compound of general formula (XI):which is a special case of compounds of claim 1 in which n is equal to 1.

14. A fungicidal composition comprising an effective amount of at least one compound according to any one of claims 1 to 10, or agriculturally acceptable N-oxides, geometric and/or optical isomers, enantiomers and/or diastereomers, tautomeric forms, salts and metal and non-metal complexes thereof.

15. The fungicidal composition according to claim 14, characterized in that it comprises, in addition to the compound according to any one of claims 1 to 10 or its agriculturally acceptable N-oxides, geometric and/or optical isomers, enantiomers and/or diastereomers, tautomeric forms, salts and metal and non-metal complexes as active substance, an agriculturally acceptable solid or liquid carrier and/or an agriculturally acceptable surfactant, and optionally one or more other fungicides, insecticides, herbicides, acaricides, attractants or pheromones and other biologically active compounds.

16. The fungicidal compositions according to claim 14 or 15, comprising 0.05% to 99% by weight of active substance.

17. A method for preventively or curatively combating phytopathogenic fungi, characterised in that an effective (agriculturally effective) and a non-phytotoxic amount of an active substance of the formula (I) according to any one of claims 1 to 10 is applied to the soil, to the leaves, to the branches of the plants and/or to the fruits or seeds of the plants in which the plants are growing or in which they are growing.

18. The method according to claim 17, wherein rice, corn, cotton, cereals, fruit trees, oil-producing crops, market garden and grass crops, tomatoes, lettuce, protein crops, peas, solanaceae, beetroot, flax and woodland trees are treated, as well as genetically modified homologues of these crops.

19. The method according to claim 17 or 18, wherein seeds of rice, corn, cotton, cereals, fruit trees, woodland trees, oil-producing crops, protein crops, market garden crops, solanaceous plants, beetroot, flax, and genetically modified homologues of these crops are treated.

20. The method of any one of claims 17 to 19, wherein the plant is a genetically modified plant.

21. The method according to any one of claims 17-20, wherein the dosage of active substance in case of foliar treatment is 10-800 g active substance/ha.

22. The method according to claim 21, wherein the dosage of active substance in case of foliar treatment is 50-300 g active substance/ha.

23. The method according to any one of claims 17 to 20, wherein the dose of active substance, if seed treatment is carried out, is between 2 and 200 g of active substance per 100kg of seed.

24. The method according to claim 23, wherein the dose of active substance, if seed treatment is carried out, is between 3 and 150 g per 100kg of seed.

25. A method for the prophylactic or therapeutic treatment of wood against fungal attack by direct application, coating, impregnation or injection of a compound as claimed in any one of claims 1 to 10.

26. The use of a compound according to any one of claims 1 to 10 for the treatment of fungal diseases of the human and animal body.