AU3039299A - Fungicide compositions comprising a hydroximic or hydrazonic group - Google Patents

Fungicide compositions comprising a hydroximic or hydrazonic group Download PDF

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AU3039299A
AU3039299A AU30392/99A AU3039299A AU3039299A AU 3039299 A AU3039299 A AU 3039299A AU 30392/99 A AU30392/99 A AU 30392/99A AU 3039299 A AU3039299 A AU 3039299A AU 3039299 A AU3039299 A AU 3039299A
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Australia
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group
formula
given
atom
compound
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AU30392/99A
Inventor
Philippe Desbordes
Charles Ellwood
Vincent Gerusz
Benoit Hartmann
Joseph Perez
Tadashi Sakurai
Nobumitsu Sawai
Alain Villier
Jean-Pierre Vors
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Bayer CropScience SA
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Rhone Poulenc Agro SA
Rhone Poulenc Agrochimie SA
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Priority claimed from FR9804594A external-priority patent/FR2777002A1/en
Application filed by Rhone Poulenc Agro SA, Rhone Poulenc Agrochimie SA filed Critical Rhone Poulenc Agro SA
Publication of AU3039299A publication Critical patent/AU3039299A/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/30—Oxygen atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/20—N-Aryl derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00—Fungicides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/12—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D215/14—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/08—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/28—Halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Zoology (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Agronomy & Crop Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mycology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Microbiology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Heterocyclic Compounds Containing Sulfur Atoms (AREA)
  • Quinoline Compounds (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Other In-Based Heterocyclic Compounds (AREA)
  • Pyridine Compounds (AREA)

Description

WO 99/51579 PCT/FR99/00753 FUNGICIDAL COMPOUNDS CONTAINING A HYDROXIMIC OR HYDRAZONIC GROUP The present invention relates to novel compounds containing a hydroximic or hydrazonic 5 function, to a process for their preparation, to their use as fungicides, in particular in the form of fungicidal compositions, and to processes for controlling phytopathogenic fungi of crops using these compounds or these compositions. 10 A great number of compounds with fungicidal action are already known and widely used. By way of example, patent applications EP-A-0,463,488 and EP-A 370,629 describe, in particular, fungicidal compounds containing a hydroximic or hydrazonic function. 15 Documents EP-A-0,299,694, WO-A-96/33164 and JP-09,031,048 also describe similar fungicidal compounds. However, all of these compounds have drawbacks which are well known to a user of such 20 compounds, i.e. to a person confronted with the problems of controlling the fungal diseases of plants: low activity, compounds effective on a relatively small range of fungal diseases, low selectivity, toxicity, or even ecotoxicity. 25 In other words, the known fungicidal compounds are weakly active and/or have a relatively narrow spectrum of activity. In order to eradicate all of the various fungal species which attack plants, the - 2 user must, for example, use several products, whose spectrum and application doses he or she must know exactly. The use of several products moreover goes against the methods for treating crops recommended 5 nowadays, in which the application doses must be as low as possible, with the obvious aim of protecting the environment. Furthermore, the use of large amounts of fungicidal products and/or of several different 10 fungicidal products is quite often harmful to the crops (toxicity of the products). The use of large amounts of products in the treatment of fungicidal diseases entails, in some of them, the appearance of fungal strains which are 15 resistant to these products. One object of the present invention is to propose a novel family of compounds which has a broad spectrum of action on the phytopathogenic fungi of crops. 20 Another object of the present invention is to propose a novel family of compounds which has a broad spectrum of action on the phytopathogenic fungi of crops, allowing the specific problems encountered to be overcome. 25 Another object of the present invention is to propose a novel family of compounds which are active at low doses and which have a broad spectrum of action on the phytopathogenic fungi of crops.
-3 Another object of the present invention is to propose a novel family of compounds which have an improved broad spectrum of action on the phyto pathogenic fungi of crops. 5 Another object of the present invention is to propose a novel family of compounds which has an improved broad spectrum of action on the phyto pathogenic fungi of crops such as cereals, rice, fruit trees, woodland trees, grapevine, oleaginous crops, 10 market garden crops, solanaceous plants and beetroot. It has been found, surprisingly, that these objects can be achieved, totally or partially, by compounds containing a heterocyclic unit combined with the hydroximic or hydrazonic function, such as those 15 described in the present invention. General definition of the invention: The invention relates to compounds containing a heterocyclic unit A combined with a hydroximic or 20 hydrazonic function, of general formula (I): W, N R,
W
1 2- A G W, N 2 (I) in which G is chosen from the groups G1 to G9: -4 G1 G2 G3 02
R
6 0.., R RsSN, I I~k
(CH
2 )n CH 2 R Q2 02 02 G4 G5 G6 PI -- Y R4 Rio Q0. a-f0 Rio Q. 0 2 54NN R Re G7 G8 G9 in which: n represents 0 or 1 Qi is a nitrogen atom or a CH group, 10 Q2 is an oxygen or sulphur atom, Q3 is an oxygen or sulphur atom, Q4 is a nitrogen atom or a group CR 11 , Q5 is an oxygen or sulphur atom or a group NR12, 15 Y is an oxygen or sulphur atom or an amino (NH) or oxyamino (ONH) group
W
1 is an oxygen or sulphur atom or a sulphinyl (SO) or sulphonyl (SO 2 ) group, -5
W
2 is an oxygen atom or a group NR 1 3 , p represents 0, 1 or 2, A represents a mono- or bicyclic aromatic heterocyclic radical containing from 5 to 10 atoms, 5 among which 1 to 4 are hetero atoms chosen from oxygen, sulphur and nitrogen atoms, each sulphur or nitrogen atom optionally being in the oxidized state in the form of an N-oxide or sulphoxide group, this radical being attached to the carbon atom substituted with the groups 10 R 1 and R 2 in the case where p = 1 or p = 2, or attached to the group W 2 in the case where p = 0, with a carbon or nitrogen atom, and this radical optionally being substituted with 1 to 5 radicals Xi and/or X 2 and/or X 3 and/or X 4 and/or X 5 , preferably with 1 to 3 radicals X 1 15 and/or X 2 and/or X 3 ,
X
1 , X 2 , X3, X 4 and X 5 are, independently of each other, a hydrogen atom, a halogen atom; or a hydroxyl, mercapto, nitro, thiocyanato, azido, cyano or pentafluorosulphonyl group; or 20 a lower alkyl, lower haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, cyanoalkyl, cyanoalkoxy, cyanoalkylthio, alkylsulphinyl, haloalkylsulphinyl, alkylsulphonyl, 25 haloalkylsulphonyl or alkoxysulphonyl group; or a lower cycloalkyl, lower halocycloalkyl, alkenyl, alkynyl, alkenyloxy, alkynyloxy, alkenylthio or alkynylthio group; or -6 an amino, N-alkylamino, N,N-dialkylamino, acylamino, aminoalkyl, N-alkylaminoalkyl, N,N dialkylaminoalkyl or acylaminoalkyl group; or an acyl, carboxyl, carbamoyl, N 5 alkylcarbamoyl, N,N-dialkylcarbamoyl or lower alkoxycarbonyl group; the radical Xi optionally forming a 5- to 7-membered ring with R 1 3 in the case where W 2 is a group
NR
13 , or a 5- to 7-membered ring with R, in the case 10 where p = 1, or a 5- to 7-membered ring with R'i in the case where p = 2;
X
6 is a hydrogen atom, a halogen atom; or a lower alkyl, lower haloalkyl, alkoxy or haloalkoxy group; or 15 cyano or nitro radicals,
R
1 and R 2 are, independently of each other, a hydrogen atom, a lower alkyl or lower haloalkyl group, a lower cycloalkyl or lower halocycloalkyl group, an alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, 20 haloalkylthioalkyl or cyanoalkyl group; or a cyano, acyl, carboxyl, carbamoyl, N-alkylcarbamoyl or N,N-dialkylcarbamoyl group, a lower alkoxycarbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl or 25 alkylthiothiocarbonyl group; or an aminoalkyl, N-alkylaminoalkyl,
N,N
dialkylaminoalkyl or acylaminoalkyl group, or Ri and R 2 together can form a divalent radical such as an alkylene group, optionally substituted with one or more halogen atoms, or optionally substituted with one or more lower alkyl groups,
R
3 is a hydrogen atom, a lower alkyl or lower 5 haloalkyl group, a lower cycloalkyl or lower halocycloalkyl group, an alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl or cyanoalkyl group; or 10 a nitro, cyano, acyl, carboxyl, carbamoyl, N-alkylcarbamoyl, N,N-dialkylcarbamoyl, lower alkoxycarbonyl, 3-oxyethanyloxycarbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl or 15 alkylthiothiocarbonyl group; or an alkenyl, alkynyl, N,N-dialkylamino or N,N dialkylaminoalkyl group; or an optionally substituted phenyl or benzyl group, 20 R 4 is a lower alkyl or lower haloalkyl group, a lower cycloalkyl, lower halocycloalkyl or alkoxyalkyl group; or an alkoxy, haloalkoxy, alkylthio, alkylamino or dialkylamino group, 25 R 5 and R 6 represent, independently of each other, a lower alkyl or lower haloalkyl group,
R
7 is a lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl or alkynyl group, - 8 R 8 is a lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl, formyl or acyl group,
R
9 is a hydrogen atom, a lower alkyl or lower 5 haloalkyl group or a lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl or alkynyl group,
R
10 is a halogen atom, a lower alkyl or lower haloalkyl group, a lower cycloalkyl or lower 10 halocycloalkyl group or an alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulphinyl, haloalkylsulphinyl, alkylsulphonyl or haloalkylsulphonyl group,
R
11 and R 1 2 are, independently of each other, a 15 hydrogen atom, a lower alkyl or lower haloalkyl group or a lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl or alkynyl group,
R
13 is a hydrogen atom, a lower alkyl or lower haloalkyl group, a lower cycloalkyl, lower 20 halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl or haloalkylthioalkyl group, an optionally substituted allyl group, an optionally substituted propargyl group or an optionally substituted benzyl group; or 25 an acyl, N-alkylcarbamoyl,
N,N
dialkylcarbamoyl, lower alkoxycarbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl or - 9 alkylthiothiocarbonyl group; or an alkylsulphonyl, haloalkylsulphonyl or optionally substituted arylsulphonyl group, Q2 and R 4 can together form a ring of 5 to 7 5 atoms containing 2 to 3 oxygen and/or nitrogen atoms, optionally substituted with one or more radicals, such as a halogen or a lower alkyl or lower haloalkyl group, as well as the salts and the metal and metalloid complexes of the compounds of formula (I) as 10 have just been defined. When the compound of formula (I) is such that A represents a mono- or bicyclic aromatic heterocyclic radical as defined above, and when at least one of the radicals Xi and/or X 2 and/or X 3 and/or X 4 and/or X 5 is a 15 hydroxyl, mercapto, amino, N-alkylamino or N-acylamino group, this compound may be liable to accept a tautomeric form in chemical equilibrium, resulting from the displacement of the proton in the said hydroxyl, mercapto, amino, N-alkylamino or N-acylamino group. The 20 tautomeric forms of such compounds are included in the field of the invention. The possible tautomeric forms of the compounds of formula (I) in which p = 0 and W 2 is a group NR 13 , R 1 3 being a hydrogen atom, are also included in the invention. Such tautomeric forms are 25 defined in particular in the book "The tautomerism of heterocycles, Advances in Heterocyclic Chemistry, Supplement 1" by J. Elguero, C. Martin, A.R. Katritzky and P. Linda, published by Academic Press, New York, - 10 1976, pages 1-4. In the text of the present invention, the term "hydroximic group" includes both the "hydroximic group" per se (with the O-C=N-0 sequence) and the 5 "thiohydroximic group" (with the S-C=N-0 sequence). Similarly, the term "hydrazonic group" includes both the "hydrazonic group" per se (with the O-C=N-N sequence) and the "thiohydrazonic group" (with the S-C=N-N sequence). 10 In the case of the compounds of formula (I) for which p = 2, the radical -(CRiR 2
)
2 - must be understood as being the radical -(CRiR 2 )-(CR'iR' 2 )-, in which R' 1 and R' 2 have, independently of each other and independently of R 1 and R 2 , the same definitions as R 1 15 and R 2 ; it being possible for the pairs of radicals (Ri;R 2 ) and (R' 1
;R'
2 ) to be identical or different. Moreover, the following generic terms are used with the following meanings: - halogen atom means a fluorine, chlorine, 20 bromine or iodine atom, - the adjective "lower" qualifying an organic radical means that this radical contains from 1 to 6 carbon atoms, except for the cycloalkyl radical in which the adjective "lower" means from 3 to 6 carbon 25 atoms, - the alkyl radicals can be linear or branched, - the haloalkyl radicals can contain one or - 11 more identical or different halogen atoms, - acyl radical means alkylcarbonyl or cycloalkylcarbonyl, - the adjective "lower" qualifying the term 5 "acyl" applies to the alkyl or cycloalkyl part of this radical, - alkylene radical denotes the radical
-(CH
2 )m- where m = 2 to 5, - when the amino radical is disubstituted, 10 the two substituents can constitute a saturated or unsaturated nitrogenous heterocycle of 5 or 6 atoms, - when the carbamoyl radical is disubstituted, the two substituents can constitute a saturated or unsaturated nitrogenous heterocycle of 5 15 or 6 atoms, - the expression "optionally substituted" qualifying an organic group applies to the various radicals constituting that group, - alkyl, alkenyl and alkynyl groups and 20 radicals in the description and the corresponding claims are, unless otherwise stated, linear or branched and comprise up to 6 carbon atoms. Preferred embodiments of the invention are those in which the products of formula (I) also have 25 one and/or other of the following characteristics, taken separately or in combination: n is equal to 0 p is equal to 0, 1 or 2; - 12 Q2 is an oxygen atom, and/or Q3 is an oxygen atom, and/or Q4 is a nitrogen atom, and/or Q5 is an oxygen atom;
W
1 is an oxygen or sulphur atom 5 W 2 is an oxygen atom or an alkylamino, haloalkylamino, alkoxyalkylamino or allylamino group, Y is an oxygen atom, X1, X 2 , X 3 , X 4 , X 5 and X 6 are, independently of each other, a hydrogen atom, a lower alkyl group, a 10 halogen atom or cyano, trifluoromethyl, methoxy or nitro radicals,
R
1 and R 2 are, independently of each other, a hydrogen atom, a lower alkyl, lower cycloalkyl, lower haloalkyl, alkoxyalkyl, cyano, cyanoalkyl, 15 N-alkylaminoalkyl, N,N-dialkylaminoalkyl, acylaminoalkyl, lower alkoxycarbonyl, N-alkylcarbamoyl or N,N-dialkylcarbamoyl group,
R
3 is a hydrogen atom, a lower alkyl, lower cycloalkyl, lower haloalkyl or alkoxyalkyl group, 20 preferably a methyl, ethyl, propyl, isopropyl, cyclopropyl or methoxymethyl radical,
R
4 is a lower alkyl, alkoxy, alkylamino or dialkylamino group, preferably a methyl, ethyl, propyl, methoxy, ethoxy, methylamino or ethylamino radical, 25 R 5 , R 6 , R 8 and R 9 are, independently of each other, a lower alkyl or lower haloalkyl group, preferably a methyl, fluoromethyl, difluoromethyl, trifluoromethyl, ethyl, 2,2,2-trifluoroethyl or propyl - 13 radical,
R
7 is a lower alkyl or lower haloalkyl group, preferably a methyl, fluoromethyl, difluoromethyl, trifluoromethyl, ethyl, 2 ,2,2-trifluoroethyl or propyl 5 radical, or an allyl or propargyl group,
R
10 is a chlorine atom, a lower alkyl or lower haloalkyl group, preferably methyl, or an alkoxy or alkylthio group, preferably methoxy or methylthio, Rii and R 1 2 are, independently of each other, a 10 lower alkyl, lower haloalkyl, alkoxyalkyl, allyl or propargyl group,
R
13 is a hydrogen atom or a lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, allyl, propargyl or benzyl group. 15 A is chosen from a radical, optionally substituted with 1 to 5 radicals Xi and/or X 2 and/or X 3 and/or X 4 and/or X 5 , preferably with 1 to 3 radicals Xi and/or X 2 and/or X 3 , derived, by removal of a hydrogen atom, from one of the rings (i) to (v) below: 20 - a 5-membered ring described by formula (I): B2 B4 0i) in which each of the groups of the list B 1 , 2 3 4 25 B , B and B is chosen from carbon, nitrogen, oxygen - 14 and sulphur atoms such that the said list comprises from 0 to 3 carbon atoms, 0 or 1 sulphur atom, 0 or 1 oxygen atom and from 0 to 4 nitrogen atoms; or alternatively 5 - a 6-membered ring described by formula (ii): DI (ii) 10 in which each of the groups of the list D , D 2 , D 3 , D 4 and D 5 is chosen from carbon and nitrogen atoms such that the said list comprises from 1 to 4 carbon atoms and from 1 to 4 nitrogen atoms; or alternatively, - two fused rings, each 6-membered, described 15 by formula (iii): E E E E (iii) in which each of the groups of the list El, 2 3 4 5 6 78 20 E , E , E , E , E , E and E is chosen from carbon and nitrogen atoms such that the said list comprises from 4 to 7 carbon atoms and from 1 to 4 nitrogen atoms; or - 15 alternatively - a 6-membered ring and a 5-membered ring fused together, described by formula (iv): I 20j 6
QL
2 >' -L3 5 (iv) in which: - each of the groups of the list J 1 , J 2 ,.3 J 4, J5 and J is chosen from carbon and nitrogen atoms such that the said list comprises from 3 to 6 carbon 10 atoms and from 0 to 3 nitrogen atoms; and - each of the groups of the list L', L2 and L 3 is chosen from carbon, nitrogen, oxygen and sulphur atoms such that the said list comprises from 0 to 3 carbon atoms, 0 or 1 sulphur atom, 0 or 1 oxygen atom 15 and from 0 to 3 nitrogen atoms; and - each of the groups of the list J1, J 2 ' j3 J4, J5, J6, L, L2 and L is chosen such that the said list comprises from 3 to 8 carbon atoms; or alternatively 20 - two fused rings, each 5-membered, described by formula (v): - 16 ~o\T2 (V) in which: - each of the groups of the list M 1 , M 2 and M 3 5 represents carbon, nitrogen, oxygen or sulphur atoms such that the said list comprises from 0 to 3 carbon atoms, 0 or 1 sulphur atom, 0 or 1 oxygen atom and from 0 to 3 nitrogen atoms; - each of the groups of the list T', T 2 and T 3 10 represents carbon, nitrogen, oxygen or sulphur atoms such that the said list comprises from 0 to 3 carbon atoms, 0 or 1 sulphur atom, 0 or 1 oxygen atom and from 0 to 3 nitrogen atoms; - Z represents a carbon or nitrogen atom; 15 - each of the groups of the list M 1 , M 2 , M 3 , T1, T2 and T3 is chosen such that the said list comprises from 0 to 6 carbon atoms. It is clearly understood that, in formulae (i), (ii), (iii), (iv) and (v) indicated above, a group 20 representing a carbon or nitrogen atom bears the free valency which connects A to the carbon atom substituted with the groups R 1 and R 2 in the case where p = 1 or 2; or a group representing a carbon atom bears the 25 free valency which connects A to the group W 2 in the - 17 case where p = 0. Among the above variants, the following variants, taken alone or in combination, will be selected more particularly: 5 Wi is an oxygen atom,
R
1 is a hydrogen atom or a methyl radical,
R
2 is a hydrogen atom or a lower alkyl, cyano, cyanoalkyl, alkoxyalkyl, N,N-dialkylaminoalkyl, lower alkoxycarbonyl or lower N,N-dialkylcarbamoyl group, 10 A represents a heterocyclic radical, optionally substituted with 1 to 5 radicals X 1 and/or X 2 and/or X 3 and/or X 4 and/or X 5 , preferably with 1 to 3 radicals X 1 and/or X 2 and/or X 3 as defined above, A being chosen from the following list: 15 - furyl; pyrrolyl; thiophenyl; - pyrazolyl; imidazolyl; oxazolyl; isoxazolyl; thiazolyl; isothiazolyl; 1,2,3-oxadiazolyl; 1,2,4-oxadiazolyl; 1,2,5-oxadiazolyl; 1,3,4-oxadiazolyl; 20 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; 25 - 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; - 18 - benzimidazolyl; indazolyl; benzotriazolyl; benzoxazolyl; 1,2-benzisoxazolyl; 2,1-benzisoxazolyl; benzothiazolyl; 1,2-benzisothiazolyl; 2,1-benzisothiazolyl; 5 1,2,3-benzoxadiazolyl; 1,2,5-benzoxadiazolyl; 1,2,3-benzothiadiazolyl; 1,2,5-benzothiadiazolyl; - quinolyl; isoquinolyl; 10 - quinoxazolinyl; quinazolinyl; cinnolyl or phthalazyl; pteridinyl; benzotriazinyl; - 1,5-naphthyridinyl; 1,6-naphthyridinyl; 1,7-naphthyridinyl; 1,8-naphthyridinyl; - imidazo[2,1-b]thiazolyl; 15 thieno[3,4-b]pyridyl; purine; pyrrolo[1,2-b]thiazolyl. Advantageously, the compounds of formula (I) having the characteristics below are also preferred:
W
1 is an oxygen atom, 20 Ri is a hydrogen atom or a methyl radical,
R
2 is a hydrogen atom or a lower alkyl, cyano, cyanoalkyl, alkoxyalkyl, N,N-dialkylaminoalkyl, lower alkoxycarbonyl or lower N,N-dialkylcarbamoyl group, in which A, optionally substituted with 1 to 25 5 radicals X 1 and/or X 2 and/or X 3 and/or X 4 and/or X 5 , preferably with 1 to 3 radicals X 1 and/or X 2 and/or X 3 , is chosen from one of the following heterocycles - pyridyl; - 19 - pyridazinyl; pyrimidinyl; pyrazinyl; 1,3,5-triazinyl; 1,2,4-triazinyl; - quinolyl; isoquinolyl; - furyl; pyrrolyl; thiophenyl; 5 - oxazolyl; isoxazolyl; thiazolyl; isothiazolyl; imidazolyl; pyrazolyl. In a particularly advantageous manner, the compounds of formula (I) which have the characteristics below are also preferred: 10 Wi is an oxygen atom,
R
1 is a hydrogen atom or a methyl radical,
R
2 is a hydrogen atom or a lower alkyl, cyano, cyanoalkyl, alkoxyalkyl, N,N-dialkylaminoalkyl, lower alkoxycarbonyl or lower N,N-dialkylcarbamoyl group, 15 in which A, optionally substituted with 1 to 5 radicals Xi and/or X 2 and/or X 3 and/or X 4 and/or X 5 , preferably with 1 to 3 radicals Xi and/or X 2 and/or X 3 , represents a pyridyl radical. Compounds of formula (I) which are most 20 particularly advantageous in the context of the present invention are those for which G represents Gl, G2 or G3, G1 being the preferred group G, the other substituents being as defined above. Lastly, the compounds of formula (I) below 25 are preferred: - methyl (E,E)-2-(2-{1-[(2 pyridyl)methyloxyimino]-1-cyclopropylmethyloxy methyl}phenyl)-3-methoxypropenoate, - 20 - methyl (E,E)-2-(2-{1-[1-(2 pyridyl)propyloxyimino]-1-cyclopropylmethyloxy methyl}phenyl)-3-methoxypropenoate, - methyl (E,E)-2-(2-{1-[1-(2 5 pyridyl)propyloxyimino]propyloxymethyl}phenyl)-3 methoxypropenoate, and - methyl (E,E)-2-(2-{1-[1-(2-pyridyl)propyl oxyimino]isobutyloxymethyl}phenyl)-3-methoxypropenoate, as well as the salts and metal and metalloid 10 complexes thereof. Compounds which are even more particularly preferred are those in which the substituents W 1 and W 2 are in a trans position (see below) relative to the double bond -C(R 3 )=N-. 15 The compounds of general formula (I) and the compounds which can optionally be used as intermediates in the preparation processes, and which will be defined in the description of these processes, can exist in one or more forms of geometrical isomers depending on the 20 number of double bonds in the compound. The compounds of general formula (I) in which G is a group G1, G2 or G3 can contain four different geometrical isomers, noted as (E,E), (E,Z), (Z,E) or (Z,Z), depending on the configuration of the two double bonds. The notation E 25 and Z can be replaced, respectively, by the terms syn and anti, or cis and trans. Reference will be made in particular to the book by E. Eliel and S. Wilen "Stereochemistry of Organic Compounds" published by - 21 Wiley (1994) for the description and use of these notations. By convention, in the case of the present invention, the terms (E,E), (E,Z), (Z,E) and (Z,Z) 5 denote by the first letter the configuration of the double bond of the group G1, G2 or G3, and by the second letter the configuration of the hydroximic or hydrazonic group. The compounds of general formula (I) in which 10 G is a group G4 to G9 can contain two different geometrical isomers noted as (E) or (Z) depending on the configuration of the hydroximic or hydrazonic group. The compounds of general formula (I) and the 15 compounds which can optionally be used as intermediates in the preparation processes, and which will be defined in the description of these processes, can exist in one or more optical or chiral isomer forms depending on the number of asymmetric centres in the compound. The 20 invention thus relates equally to all the optical isomers and to their racemic or scalemic mixtures (the term "scalemic" denotes a mixture of enantiomers in different proportions), and to the mixtures of all the possible stereoisomers, in all proportions. The 25 diastereoisomers and/or the optical isomers can be separated according to the methods which are known per se (E. Eliel, ibid.).
- 22 Preparation processes: The compounds of the present invention of general formula (I) and the compounds which can optionally be used as intermediates in the preparation 5 processes, can be prepared by at least one of the general preparation methods described below: methods A to K. The preparation of the reagents used in one or other of the general preparation methods is usually 10 known per se and is usually described specifically in the prior art or in a manner such that a person skilled in the art can adapt it to the desired aim. The prior art which can be used by a person skilled in the art to establish the conditions for 15 preparing the reagents can be found in many general chemistry books, such as "Advanced Organic Chemistry" by J. March, published by Wiley (1992), "Methoden der organischen Chemie" (Houben-Weyl), published by Georg Thieme Verlag, or "Chemical Abstracts" published by the 20 American Chemical Society, as well as in the publicly accessible computer databases. Method A: The compounds of general formula (I) for which G is one of the groups G1 to G9, the other 25 substituents having the definition already indicated, can be obtained by a process which consists in placing a compound of formula (II)A: - 23 01 X6" V1 G (II)A in which G is one of the groups G1 to G9, the groups G1 to G9 having the same definitions as those 5 given for formula (I), X 6 having the same definition as that given for formula (I), Vi is a halogen atom (preferably chlorine or bromine), an alkylsulphonate or haloalkylsulphonate (preferably methylsulphonate or 10 trifluoromethylsulphonate), or an arylsulphonate (preferably 4-methylphenylsulphonate) group, in contact with a compound of formula (III)A: YI R, W, NNIW2 A
R
3 R2 (III)A 15
W
1 , W 2 , R 1 , R 2 , R 3 , p and A having the same definition as that given for formula (I), in the presence of an organic or inorganic base, in the absence or presence of a solvent. The 20 reaction is generally carried out at a temperature of between -80*C and 180*C (preferably between 0*C and 1500C) or at the boiling point of the solvent used. The appropriate solvent for this reaction can be an - 24 aliphatic hydrocarbon such as pentane, hexane, heptane or octane; an aromatic hydrocarbon such as benzene, toluene, xylenes or halobenzenes; an ether such as diethyl ether, diisopropyl ether, tetrahydrofuran, 5 dioxane or dimethoxyethane; a halogenated hydrocarbon such as dichloromethane, chloroform, 1,2-dichloroethane or 1,1,1-trichloroethane; an ester such as methyl acetate or ethyl acetate, a nitrile such as acetonitrile, propionitrile or benzonitrile; a dipolar 10 aprotic solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylpropyleneurea or dimethyl sulphoxide; or water. Mixtures of these various solvents can also be used. The reaction time depends on the conditions 15 used and is generally between 0.1 and 48 h. As organic or inorganic base which is suitable for this reaction, mention may be made of alkali metal and alkaline-earth metal hydroxides, such as sodium, potassium, caesium or calcium hydroxide; 20 alkali metal and alkaline-earth metal alkoxides, such as potassium tert-butoxide, alkali metal and alkaline earth metal hydrides, such as sodium, potassium or caesium hydride; alkali metal and alkaline-earth metal carbonates and bicarbonates such as sodium, potassium 25 or calcium carbonate or sodium, potassium or calcium bicarbonate; organic bases, which are preferably nitrogenous, such as pyridine, alkylpyridines, alkylamines such as trimethylamine, triethylamine or - 25 diisopropylethylamine, aza derivatives such as 1,5 diazabicyclo[4.3.0]non-5-ene or 1,8-diazabicyclo [5.4.0]undec-7-ene. There is no strict limitation as regards the 5 relative proportions of the compounds of formula (II)A and of formula (III)A. However, it is advantageous to choose a (III)A/(II)A molar ratio of between 0.1 and 10, preferably 0.5 to 2. Depending on the conditions used, the 10 compounds of general formula (I) are obtained in the form of a variable mixture of (E) and (Z) isomers or in the form of a single isomer (E) or a single isomer (Z) depending on the configuration of the hydroximic or hydrazonic group. If necessary, the compounds of 15 general formula (I) and of (E) or (Z) configuration, depending on the configuration of the hydroximic or hydrazonic group, can be isolated and purified according to methods which are known per se, such as, for example, extraction, crystallization or 20 chromatography. The compounds of formula (III)A in which W 1 ,
W
2 , R 1 , R 2 , R 3 , p and A have the same definition as that given for formula (I), can be obtained by a process which consists in placing a compound of formula (IV): 25 - 26 H 2 NsW2 A (IV)
W
2 , R 1 , R 2 , p and A having the same definition as that given for formula (I), 5 in contact with a compound of formula (V):
R
3 (V) Wi and R 3 having the same definition as that 10 given for formula (I), Ui being a halogen atom (preferably chlorine or bromine), or a hydroxyl, lower alkoxy or benzyloxy, lower alkylthio, amino, N-alkylamino, N,N-dialkylamino, N-acylamino or N,N-acylalkylamino radical or a group -O(C=0)Ra, Ra 15 having the same definition as that of R 3 given for formula (I) and being identical to or different from R 3 , Ui preferably representing a halogen atom, the compound of formula (V) then representing an acid halide. The condensation between the compound of 20 formula (IV) and the compound of formula (V) is generally carried out in the presence of an organic or inorganic base, or a dehydrating reagent such as carboxylic acid anhydrides, preferably acetic anhydride - 27 or propionic anhydride, in the absence or presence of a solvent. The general conditions for condensation between the compound of formula (IV) and the compound of formula (V) are similar or identical to the 5 conditions for condensation between the compound of formula (II)A and the compound of formula (III)A and are known per se according to "Houben-Weyl" ibid. volume E5, pages 1144-1149. The hydroxamic acid or hydrazonic acid 10 derivatives of formula (III)A in which W 1 is an oxygen atom, W 2 , R 1 , R 2 , R 3 , p and A having the same definition as that given for formula (I), can also be obtained by a process which consists in placing a compound of formula (VI): 15 R, V I+ R2P (VI)
R
1 , R 2 , p and A having the same definition as that given for formula (I), and Vi is a halogen atom 20 (preferably chlorine or bromine), an alkylsulphonate or haloalkylsulphonate (preferably methylsulphonate or trifluoromethylsulphonate) or an arylsulphonate (preferably 4-methylphenylsulphonate) group, in contact with a hydroxamic acid or 25 hydrazonic acid derivative, W 2 and R 3 having the same - 28 definition as that given for formula (I), of formula (VII): H O W2-H
R
3 (VII) 5 The condensation between the compound of formula (VI) and the compound of formula (VII) is generally carried out in the presence of an organic or inorganic base, in the absence or presence of a 10 solvent. The general conditions for condensation between the compound of formula (VI) and the compound of formula (VII) are similar or identical to the conditions for condensation between the compound of 15 formula (II)A and the compound of formula (III)A and are known per se according to "Houben-Weyl" volume E5, pages 1148-1149. The hydroxamic acid derivatives of formula (III)A in which Wi and W 2 are an oxygen atom and p = 1 20 or 2, R 1 , R 2 , R 3 and A having the same definition as that given for formula (I), can be obtained by a process which consists in placing a compound of formula
(VIII):
- 29 R1 HO- A R2 (ViII)
R
1 , R 2 and A having the same definition as that given for formula (I) and p = 1 or 2, 5 in contact with a hydroxamic acid derivative or formula (VII) in which W 2 is an oxygen atom, R 3 having the same definition as that given for formula (I). The condensation between the compound of 10 formula (VII), W 2 being an oxygen atom, R 3 having the same definition as that given for formula (I), and the compound of formula (VIII), R 1 , R 2 and A having the same definition as that given for formula (I), is generally carried out in the presence of a coupling agent such as 15 carbodiimides or bis-alkoxycarbonylazo or bis(N,N dialkyl)carbamoylazo derivatives, preferably diethyl azodicarboxylate and a trialkylphosphine or triarylphosphine, preferably triphenylphosphine, in the absence or presence of an aprotic solvent, for instance 20 ethers, in particular diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, or dimethoxyethane; for instance halogenated hydrocarbons, in particular dichloromethane, chloroform, 1,2-dichloroethane or 1,1,1-trichloroethane; or for instance nitriles, in 25 particular acetonitrile, propionitrile or benzonitrile.
- 30 Mixtures of these various solvents can also be used. The reaction is generally carried out at a temperature of between -80*C and 1200C (preferably between 00C and 600C) or at the boiling point of the 5 solvent used. The reaction time depends on the conditions used and is generally between 0.1 and 48 h. There is no strict limitation as regards the relative proportions of the compounds of formula (VII) and of formula (VIII). However, it is advantageous to 10 choose a (VII)/(VIII) molar ratio of between 0.1 and 10, preferably 0.5 to 2. The general conditions for this condensation are described in several reviews, in particular Synthesis (1981), 1 and Org. Prep. Proced. Int. (1996), 15 28, 127. The compounds of formula (IV), formula (V), formula (VI), formula (VII) and formula (VIII), W 1 , W 2 ,
R
1 , R 2 , R 3 , p and A having the same definition as that given for formula (I), Ui and Vi having the same 20 definition as that given in method A, can be prepared according to processes which are known per se, for example Tetrahedron (1995), 51, 11473 and Tetrahedron Lett. (1996), 37, 8045 for the compounds of formula (IV) and Synthesis (1980), 746 for the compounds of 25 formula (VI). The compounds of formula (VI) and of formula (VIII) can be prepared more particularly according a great many processes known per se and described in "The - 31 chemistry of heterocyclic compounds" volumes 1 to 52, published by J. Wiley & Sons, and "Advances in heterocyclic chemistry" volumes 1 to 70, published by Academic Press. 5 The compounds of formula (II)A in which G is one of the groups G1 to G9, the groups G1 to G9 having the same definition as that given for formula (I), X 6 having the same definition as that given for formula (I) and Vi is a halogen atom (preferably chlorine or 10 bromine), an alkylsulphonate (preferably methylsulphonate or trifluoromethylsulphonate) or an arylsulphonate group (preferably 4-methylphenyl sulphonate), will by convention, for the remainder of the description of the preparation methods, be denoted 15 by the generic term "benzyl halide derivatives". The benzyl halide derivatives of formula (II)A in which Vi is a halogen atom (preferably chlorine or bromine) can be obtained by halogenating a compound of formula (IX): 20 0 X CH 3 G G X) in which G is one of the groups Gl to G9, the groups Gl to G9 having the same definition as that 25 given for formula (I), X 6 having the same definition as - 32 that given for formula (I). Halogenation of the compound of formula (IX) can be carried out via a radical, thermal or photochemical route, the various processes not 5 excluding each other, with an N-haloacetamide such as N-bromosuccinimide, N-chlorosuccinimide or N-bromoacetamide, in an inert solvent such as benzene or carbon tetrachloride, or in the absence of solvent, with or without a free-radical initiator, at a 10 temperature of from 20*C to 170*C, preferably from 80*C to 100 0 C, according to J. March ibid. pages 689-697. The benzyl halide derivatives of formula (II)A in which Vi is a halogen atom (preferably chlorine or bromine) can also be obtained by halogenating a 15 compound of formula (II)B: O WrH G (II)B in which G is one of the groups G1 to G9, the 20 groups G1 to G7 having the same definition as that given for formula (I) and R 4 is an alkylamino or dialkylamino group, the groups G8 and G9 having the same definition as that given for formula (I), X 6 having the same definition as that given for formula (I), and 25 Wi is an oxygen atom, - 33 with a halogenating agent such as thionyl chloride, phosphorus oxytrichloride or phosphorus tribromide according to J. March ibid. pages 431-433 or with the lithium halide/mesyl halide/collidine reagent 5 according to J. Org. Chem. (1971), 36, 3044. The benzyl halide derivatives of formula (II)A in which V1 is a halogen atom (preferably chlorine or bromine) can also be obtained by cleaving a compound of formula (II)C: 10 G (II)C in which G is one of the groups Gl to G9, the groups Gl to G7 having the same definition as that 15 given for formula (I) and R 4 is an alkylamino or dialkylamino group, the groups G8 and G9 having the same definition as that given for formula (I), X 6 having the same definition as that given for formula (I), W1 is an oxygen atom and P is a protecting group for the 20 alcohol function, such as an ester, preferably acetic or benzoic, or an ether, preferably methyl, methoxymethyl, phenyl or benzyl (reference will be made advantageously to the book "Protective groups in Organic Synthesis" by W. Greene and P. Wuts, published 25 by Wiley (1991) for the choice and preparation of the - 34 said protecting groups), with a Lewis acid such as boron tribromide, or anhydrous hydracids such as hydrogen chloride. This cleavage reaction is known in particular from patent EP 5 525,516. The benzyl halide derivatives of formula (II)A and the compounds of formula (IX), (II)B and (II)C can be prepared according to methods which are known per se. These various methods or the prior art 10 relating thereto will be outlined in method K. Method B: The compounds of general formula (I) for which G is one of the groups Gl to G9, the groups G1 to G7 having the same definition as that given for formula 15 (I) and R 4 is an amino, alkylamino or dialkylamino group or radical, the groups G8 and G9 having the same definition as that given for formula (I), X 6 having the same definition as that given for formula (I), can be obtained by a process which consists in placing a 20 compound of formula (II)B, in which G is one of the groups G1 to G9, the groups G1 to G7 having the same definition as that given for formula (I) and R 4 is an amino, alkylamino or dialkylamino group or radical, the groups G8 and G9 having the same definition as that 25 given for formula (I), XE having the same definition as that given for formula (I) and W 1 is an oxygen or sulphur atom, in contact with a compound of formula (III)B: - 35 V, NW A R R R 2 (III)B
W
2 , R 1 , R 2 , R 3 , p and A having the same definition as that given for formula (I), Vi is a 5 halogen atom (preferably chlorine or bromine), an alkylsulphonate or haloalkylsulphonate (preferably methylsulphonate or trifluoromethylsulphonate) or an arylsulphonate (preferably 4-methyphenylsulphonate) group, it being possible for the double bond Vi-C(R 3
)=N
10 W 2 - to be of (E) or (Z) stereochemistry. This reaction is generally carried out in the presence of an organic or inorganic base, in the absence or presence of a solvent. The reaction is generally carried out at a temperature of between -80*C 15 and 180*C (preferably between 00C and 1500C) or at the boiling point of the solvent used. The appropriate solvent for this reaction can be an ether, such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane or dimethoxyethane, a nitrile, such as 20 acetonitrile, propionitrile or benzonitrile, a dipolar aprotic solvent, such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone or dimethylpropyleneurea, or dimethyl sulphoxide. Mixtures of these various solvents can also be used. 25 The reaction time depends on the conditions used and is generally between 0.1 and 48 h.
- 36 As organic or inorganic base which is suitable for this reaction, mention may be made of alkali metal and alkaline-earth metal hydrides, such as sodium hydride, potassium hydride or caesium hydride, 5 and alkali metal and alkaline-earth metal alkoxides, such as potassium tert-butoxide. There is no strict limitation as regards the relative proportions of the compounds of formula (II)B and of formula (III)B. However, it is advantageous to 10 choose a (III)B/(II)B molar ratio of between 0.1 and 10, preferably 0.5 to 2. Depending on the conditions used, the compounds of general formula (I) are obtained in the form of a variable mixture of (E) and (Z) isomers or in 15 the form of a single (E) isomer or a single (Z) isomer depending on the configuration of the hydroximic or hydrazonic group. If necessary, the compounds of general formula (I) and of (E) or (Z) configuration, depending on the configuration of the hydroximic or 20 hydrazonic group, can be isolated and purified according to methods which are known per se, such as, for example, extraction, crystallization or chromatography. The compounds of general formula (III)B are 25 prepared according to methods which are known per se, such as, for example, J. Org. Chem. (1985), 50, 993, J. Org. Chem. (1971), 36, 234, and Chem. Abstracts (1970), 73, 34750s.
- 37 Method C: The thiohydroxamic acid derivatives of formula (III)A in which W 1 is a sulphur atom and W 2 is an oxygen atom, or the thiohydrazonic acid derivatives 5 of formula (III)A in which W1 is a sulphur atom and W 2 is a group NR 13 , R 1 , R 2 , R 3 , R 13 , p and A having the same definition as that given for formula (I), are also a subject of the present invention. They can be obtained by thionation of the 10 hydroxamic acids of formula (III)A in which W1 is an oxygen atom and W 2 is an oxygen atom, or the hydrazonic acids of formula (III)A in which W1 is an oxygen atom and W 2 is a group NR1 3 , R 1 , R 2 , R 3 , R 13 , p and a having the same definition as that given for formula (I), with 15 thionating agents such as phosphorus pentasulphide or Lawesson's reagent, in an identical or similar manner to that of the processes described in "Houben-Weyl" volume E5, pages 1279-1280 and Synthesis (1984), 829. Method D: 20 The compounds of general formula (I), for which G is a group G3, Q2 being an oxygen atom, R 4 being an alkoxy, alkylamino or dialkylamino group, the other substituents having the same definition as that given for formula (I) and RE is a lower alkyl or lower 25 haloalkyl group, can be obtained by a process which consists in placing a compound of formula (X): - 38 W , N W 2 A 4 R3 R2 0(X in which R 4 is an alkoxy, alkylamino or dialkylamino group, the other substituents having the same definition as that given for formula (I), 5 in contact with a Wittig-Horner reagent of formula (XI)A:
R
6
-CH
2 -P (=O) (OR) 2 (XI)A 10 R 6 being a lower alkyl or lower haloalkyl group, Rb being a lower alkyl, phenyl or benzyl group, or alternatively with a Wittig reagent of formula (XI)B: 15 R 6
-CH
2 -P (Rd) 3*; Hal~ (XI)B
R
6 being a lower alkyl or lower haloalkyl group, Rd being an optionally substituted phenyl group, Hal~ being a halide ion, 20 by the action of one or more equivalents of a base such as alkali metal or alkaline-earth metal alkoxides, preferably sodium ethoxide, sodium methoxide or potassium tert-butoxide, or alkali metal and - 39 alkaline-earth metal hydrides, preferably sodium hydride or potassium hydride, or by the action of an organometallic derivative, such as alkyllithiums, preferably butyllithium, alkylmagnesium halides or 5 lithium diisopropylamide in an aprotic solvent such as ethers, preferably diethyl ether or tetrahydrofuran, at a temperature of from -78*C to 50*C, preferably -70*C to 200C, according to J. March, ibid. pages 956-963 or patent WO 95/29896. 10 The Wittig-Horner reagents of formula (XI)A and the Wittig reagents of formula (XI)B can be obtained according to processes which are known per se. Method E: The compounds of general formula (I) for 15 which G is a group Gl or G2, Qi being a nitrogen atom or a CH group, Q2 being an oxygen atom, R 4 being an alkoxy, alkylamino or dialkylamino group, the other substituents having the same definition as that given for formula (I) and R 5 is a lower haloalkyl group, can 20 be obtained by a process which consists in placing a compound of formula (XII): X W NW M- T R3 R2 Q 0 0 (XII) - 40 in which T is an oxygen or sulphur atom and M is an alkali metal or alkaline-earth metal ion, Q1 being a nitrogen atom or a CH group, R 4 being an alkoxy, alkylamino or dialkylamino group, W 1 , W 2 , R 1 , R 2 , R 3 , X 6 , 5 p and A having the same definition as that given for formula (I), in contact with a halogenated compound of formula CHq(Hal)4-q where q = 1 or 2 and Hal denotes halogen atoms which may be identical to or different 10 from each other and at least one of which is a chlorine or bromine atom, in a dipolar aprotic solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylpropyleneurea or dimethyl 15 sulphoxide, in the presence or absence of a catalytic amount of an iodide ion, at a temperature of between -20*C and 250*C, preferably 250C to 1500C or at the reflux point of the solvent. This reaction is described in particular in patents DE 4,424,788 and WO 96/06072. 20 The compounds of formula (XII), in which T is an oxygen atom and M is an alkali metal or alkaline earth metal ion, Qi being a nitrogen atom, R 4 being an alkoxy, alkylamino or dialkylamino group, W1, W 2 , R 1 , R 2 ,
R
3 , X 6 , p and A having the same definition as that given 25 for formula (I), can be readily obtained from the compounds of formula (X) in which R 4 is an alkoxy, alkylamino or dialkylamino group, the other substituents having the same definition as that given - 41 for formula (I), by the action of hydroxylamine and a base, according to J. March, ibid. pages 906-907. The compounds of formula (XII), in which T is an oxygen atom and M is an alkali metal or alkaline 5 earth metal ion, Qi being a CH group, R 4 being an alkoxy, alkylamino or dialkylamino group, and W 1 , W 2 ,
R
1 , R 2 , R 3 , X 6 , p and A having the same definition as that given for formula (I), can be prepared in particular in a similar manner to that of patent 10 EP-A-0178826. Method F: The compounds of general formula (I), for which G is a group G4 in which n = 1, Q2 being an oxygen atom, R 4 being an alkoxy, alkylamino or dialkylamino 15 group, the other substituents having the same definition as that given for formula (I), can be obtained by reaction between a compound of formula (XIII)A: XW N W2 HN
R
4 2 0 (XIII)A 20 in which R 4 is an alkoxy, alkylamino or dialkylamino group, the other substituents having the - 42 same definition as that given for formula (I), and a reagent of formula (XIV):
V<--'OR
5 (XIV) 5 in which Vi is a halogen atom (preferably chlorine or bromine), R 5 having the same definition as that given for formula (I), by the action of one or more equivalents of 10 base, such as alkali metal or alkaline-earth metal hydroxides, alkali metal or alkaline-earth metal alkoxides, alkali metal or alkaline-earth metal hydrides, alkali metal or alkaline-earth metal carbonates and bicarbonates, optionally in the presence 15 of a phase-transfer catalyst such as a quaternary ammonium, in an aprotic solvent such as ethers, preferably diethyl ether or tetrahydrofuran, at a temperature of from -78*C to 400C, preferably between -20 and 25'C. 20 The compounds of general formula (XIII)A, in which R 4 is an alkoxy, alkylamino or dialkylamino group, the other substituents having the same definition as that given for formula (I), can be obtained by reaction of a compound of general formula (XIII)B: 25 - 43 VI HN R4 (XIII)B in which R 4 is an alkoxy, alkylamino or dialkylamino group, X 6 having the same definition as 5 that given for formula (I), Vi is a halogen atom (preferably chlorine or bromine) or an alkylsulphonate (preferably methylsulphonate or trifluoromethylsulphonate) or arylsulphonate (preferably 4-methylphenylsulphonate) 10 group, with a compound of formula (III)A, W 1 , W 2 , R 1 ,
R
2 , R 3 , p and A having the same definition as that given for formula (I). The general conditions for condensation 15 between the compound of formula (XIII)B and the compound of formula (III)A are similar or identical to the conditions for condensation between the compound of formula (II)A and the compound of formula (III)A described in Method A. 20 The compounds of general formula (XIII)B can be obtained according to patent EP-A-0498396. Method G: The compounds of general formula (I), for which G is a group G1 to G7 and R 4 is an alkylamino or - 44 dialkylamino group, the other substituents having the same definition as that given for formula (I), can be obtained by a process which consists in placing a compound of general formula (I), for which G is a group 5 Gl to G7 and R 4 is an alkoxy or alkylthio group, the other substituents having the same definition as that given for formula (I), in contact with an alkylamine or dialkylamine, preferably methylamine, in an alcoholic 10 solvent, such as methanol, ethanol, propanol or isopropanol, at a temperature of from -50*C to 1000C or at the boiling point of the solvent chosen. It is generally advantageous to use an excess of from 1 to 5 equivalents, preferably 1.1 to 2 equivalents, of alkyl 15 or dialkylamine relative to the compound of general formula (I) for which G is a group G1 to G7 and R 4 is an alkoxy or alkylthio group, the other substituents having the same definition as that given for formula (I). 20 Method H: The compounds of general formula (I), for which Wi is a sulphoxide (SO) or sulphone (SO 2 ) group, G being one of the groups G1, G3, G4 and G6 to G9, Q2 and Q3 being an oxygen atom, the other substituents having 25 the same definition as that given for formula (I), can be obtained by oxidation of the compounds of general formula (I) for which W 1 is a sulphur atom, G being one of the groups G1, G3, G4 and G6 to G9, Q2 and Q3 being - 45 an oxygen atom, the other substituents having the same definition as that given for formula (I), using one or more equivalents of an oxidizing agent such as organic peroxides, preferably peracetic acid or 3 5 chloroperbenzoic acid, inorganic peroxides, hydroperoxides such as hydrogen peroxide, inorganic oxychlorides or oxygen, in the presence or absence of a catalyst, in an inert solvent, according to J. March, ibid. pages 1201-1203. 10 Method I: The compounds of general formula (I) for which G is one of the groups Gl to G9, the other substituents having the definition already given, can be obtained by a process which consists in placing a 15 compound of formula (XV)A: XW, N,Wr-H G R(XV)A in which G is one of the groups G1 to G9, the groups G1 to G9 having the same definitions as those 20 given for formula (I), X6, W 1 , W 2 and R 3 having the same definitions as those given for formula (I), in contact with a compound of formula (VI),
R
1 , R 2 , p and A having the same definition as that given for formula (I), and V 1 is a halogen atom (preferably - 46 chlorine or bromine), an alkylsulphonate or haloalkyl sulphonate (preferably methylsulphonate or trifluoromethylsulphonate) or an arylsulphonate (preferably 4-methylphenylsulphonate) group. 5 The condensation between the compound of formula (XV)A and the compound of formula (VI) is generally carried out in the presence of an organic or inorganic base, in the absence or presence of a solvent. 10 The general conditions for condensation between the compound of formula (XV)A and the compound of formula (VI) are similar or identical to the conditions for condensation between the compound of formula (VII) and the compound of formula (VI) 15 described in method A. The compounds of formula (XV)A in which G is one of the groups Gl to G9, the groups G1 to G9 having the same definitions as those given for formula (I), X 6 ,
W
1 , W 2 and R 3 having the same definitions as those given 20 for formula (I), are also a subject of the present invention. They can be obtained by cleavage of a compound of formula (XV)B: W,
W
2
GR
3
(XV)B
- 47 in which G is one of the groups G1 to G9, the groups Gl to G9 having the same definitions as those given for formula (I), X 6 , W 1 , W 2 and R 3 having the same definitions as those given for formula (I), and P is a 5 protecting group for the hydroxyl function, such as an ester, preferably an acetic or benzoic ester, a silyl ether, for instance trialkylsilyl ethers, dialkylaryl silyl ethers, alkyldiarylsilyl ethers or triarylsilyl ethers, preferably isopropyldimethylsilyl ether, 10 triethylsilyl ether, tert-butyldimethylsilyl ether, trityldimethylsilyl ether, tert-butyldiphenylsilyl ether, methyldiisopropylsilyl ether, methyldi-tert butylsilyl ether or triisopropylsilyl ether, or an ether such as triarylmethyl ethers, preferably 15 triphenylmethyl ether, di(4-methoxyphenyl)phenylmethyl ether or 4-methoxyphenyldiphenylmethyl ether, or a protecting group for the amino function, for instance an alkoxycarbonyl group, preferably tert butyloxycarbonyl or benzyloxycarbonyl (this list is not 20 limiting and reference will be made to the book by W. Greene and P. Wuts (ibid.) for the choice of the said protecting groups), with a cleaving agent which is specific for the protecting group P. The cleaving conditions which 25 are specific for each protecting group P are known per se according to W. Greene and P. Wuts (ibid.) and Synthesis (1985), 817. The compounds of formula (XV)B in which G is - 48 one of the groups G1 to G9, the groups G1 to G9 having the same definitions as those given for formula (I), X6,
W
1 , W 2 and R 3 having the same definitions as those given for formula (I) and P is a protecting group for the 5 hydroxyl function or a protecting group for the amino function, are also a subject of the present invention. They can be obtained by reaction between a compound of formula (II)A in which G is one of the groups Gl to G9, the groups G1 to G9 having the same 10 definitions as those given for formula (I), XE having the same definition as that given for formula (I) and V1 is a halogen atom (preferably chlorine or bromine), an alkylsulphonate or haloalkylsulphonate (preferably methylsulphonate or trifluoromethylsulphonate) or an 15 arylsulphonate (preferably 4-methylphenylsulphonate) group, with a compound of formula (XVI): W2 (XVI) 20 W1, W 2 and R 3 having the same definitions as those given for formula (I) and P being a protecting group for the hydroxyl function or a protecting group for the amino function. 25 The condensation between the compound of - 49 formula (II)A and the compound of formula (XVI) is generally carried out in the presence of an organic or inorganic base, in the absence or presence of a solvent. 5 The general conditions for condensation between the compound of formula (II)A and the compound of formula (XVI) are similar or identical to the conditions for condensation between the compound of formula (II)A and the compound of formula (III)A 10 described in method A and are known per se according to "Houben-Weyl" volume E5, pages 1148-1149. The compounds of formula (XVI), W 1 , W 2 and R 3 having the same definitions as those given for formula (I) and P being a protecting group for the hydroxyl 15 function or a protecting group for the amino function, can be prepared by condensation of a compound of formula (XVII):
H
2 (XVII) 20
W
2 having the same definitions as those given for formula (I) and P being a protecting group for the hydroxyl function or a protecting group for the amino function, 25 with a compound of formula (V), Wi and R3 having the same definition as that given for formula (I), Ui being a halogen atom (preferably chlorine or - 50 bromine) or a hydroxyl, lower alkoxy or benzyloxy, lower alkylthio, amino, N-alkylamino, N,N-dialkylamino, N-acylamino or N,N-acylalkylamino radical or a group -O(C=0)Ra, Ra having the same definition as that of R 3 5 given for formula (I) and being identical to or different from R 3 , U 1 preferably being a halogen atom, the compound of formula (V) then representing an acid halide. The general conditions for condensation 10 between the compound of formula (XVII) and the compound of formula (V) are similar or identical to the conditions for condensation between the compound of formula (IV) and the compound of formula (V) described in method A. 15 The compounds of formula (XVII) can be prepared according to methods which are known per se. Method J: The compounds of general formula (I) prepared according to Method A or Method B can be obtained with 20 the atoms or groups W 1 and W 2 , Wi and W 2 having the same meaning as for formula (I), in a cis position (see above) relative to the double bond -C(R 3 )=N- (hydroximic or hydrazonic group). The isomers of general formula (I) with the 25 atoms or group W 1 and W 2 in a trans position relative to the double bond -C(R 3 )=N- (hydroximic or hydrazonic group) can be prepared from the cis isomers by heating in a solvent, preferably under ultraviolet irradiation, - 51 with or without a catalyst, in particular an acid catalyst. The reaction time is chosen so as to obtain a total conversion of the cis isomer into the trans isomer. The reaction is generally carried out at a 5 temperature of between 0 0 C and the boiling point of the solvent. The appropriate solvent for this reaction can be an aliphatic hydrocarbon such as pentane, hexane, heptane or octane; an aromatic hydrocarbon such as benzene, toluene or xylenes, an ether such as diethyl 10 ether, diisopropyl ether, tetrahydrofuran, dioxane or dimethoxyethane; a halogenated hydrocarbon such as dichloromethane, chloroform, 1,2-dichloroethane or 1,1,1-trichloroethane; an ester such as methyl acetate or ethyl acetate; a nitrile such as acetonitrile, 15 propionitrile or benzonitrile; an alcohol such as methanol, ethanol, propanol or isopropanol; a dipolar aprotic solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylpropyleneurea or dimethyl sulphoxide; or water. 20 Mixtures of these various solvents can also be used. The solvent will preferably be an aromatic solvent such as toluene or xylenes or an ether such as diisopropyl ether. The catalyst, preferably an acid catalyst, will be chosen from anhydrous hydracids such 25 as hydrogenchloride, carboxylic acids such as acetic acid, propionic acid or trifluoroacetic acid, sulphonic acids such as methanesulphonic acid, trifluoromethanesulphonic acid or 4-methylphenyl- - 52 sulphonic acid, or sulphuric acid. Method K: (Benzyl halide derivatives of formula (II)A and the like) 5 The benzyl halide derivatives of formula (II)A and the compounds of formula (IX), (II)B and (II)C can be prepared according to a great many methods which are known per se. Mention will be made, as non-limiting and 10 non-exhausting examples, of various patents describing the processes for preparing the benzyl halide derivatives of formula (II)A or the compounds of formula (IX) or the compounds of formula (II)B or the compounds of formula (II)C: 15 The benzyl halide derivatives of formula (II)A and the like, in which G is a group G1 or G2 of (E) or (Z) stereochemistry, can be prepared according to that which is described in patents EP-A-0,426,460, EP-A-0,398,692, EP-A-0,617,014, EP-A-0,585,751, EP-A 20 0,487,409, EP-A-0,535,928 and DE 4,305,502, The benzyl halide derivatives of formula (II)A and the like, in which G is a group G1 or G2 of (E) or (Z) stereochemistry and Q2 and R 4 together form a ring of 5 to 7 atoms containing 2 to 3 oxygen and/or 25 nitrogen atoms, are known according to patent WO-A 95/04728, The benzyl halide derivatives of formula (II)A and the like, in which G is a group G3 of (E) or - 53 (Z) stereochemistry, are known according to patent WO 96/16943. The benzyl halide derivatives of formula (II)A and the like, in which G is a group G4, G5 or G6, 5 are known according to patents EP-A-0,498,396, EP-A-0,619,301 and WO-A-93/15046. The benzyl halide derivatives of formula (II)A and the like, in which G is a group G7, are known according to patents WO 95/27693 and WO 96/07633. 10 The benzyl halide derivatives of formula (II)A and the like, in which G is a group G8 or G9, are known according to patent WO 95/14009. The invention also relates to fungicidal compositions containing an effective amount of at least 15 one active material of formula (I). It has been discovered, entirely suprisingly, that the compounds of formula (I) according to the invention are fungicidal compounds which are active on a very wide range of phytopathogenic fungi of crops. 20 This activity proved to be very advantageous even when low doses of compounds of formula (I) were used. Also surprisingly for compounds with such activity (broad spectrum of action and low doses used), 25 these compounds of formula (I) are not or are only mildly phytotoxic. That is to say that they have very good selectivity with respect to the fungi to be controlled.
- 54 Lastly, the compounds of formula (I) behave very favourably with respect to the environment, in the sense that they are not or are only mildly ecotoxic. The fungicidal compositions according to the 5 invention comprise a compound of formula (I) or one of its agriculturally acceptable salts or a metal or metalloid complex of this compound, in association with an agriculturally acceptable solid or liquid support and/or a surfactant which is also agriculturally 10 acceptable. In particular, common inert supports and common surfactants can be used. These compositions include not only compositions which are ready to be applied to the plant or seed to be treated by means of a suitable device, such as a spraying or dusting 15 device, but also concentrated commercial compositions which must be diluted before they are applied to the crop. These fungicidal compositions according to the invention can also contain other ingredients of any 20 kind, such as, for example, protective colloids, adhesives, thickeners, thixotropic agents, penetration agents, stabilizers, sequestering agents, etc. More generally, the active materials can be combined with any solid or liquid additive which complies with the 25 usual formulation techniques. In general, the compositions according to the invention usually contain from 0.05 to 95% (by weight) of active material, one or more solid or liquid - 55 supports and, optionally, one or more surfactants. In the present specification, the term "support" denotes a natural or synthetic, organic or inorganic material with which the active material is 5 combined to make it easier to apply to the parts of the plant. This support is thus generally inert and should be agriculturally acceptable. The support can be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, etc.) or liquid (water, 10 alcohols, in particular butanol, etc.). The surfactant can be an emulsifier, a dispersing agent or a wetting agent of ionic or nonionic type or a mixture of such surfactants. Mention may be made, for example, of polyacrylic acid salts, 15 lignosulphonic acid salts, phenolsulphonic or naphthalenesulphonic acid salts, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (in particular alkylphenols or arylphenols), salts of 20 sulphosuccinic acid esters, taurine derivatives (in particular alkyl taurates), phosphoric esters of polyoxyethylated alcohols or phenols, fatty acid esters of polyols, and derivatives of the above compounds containing sulphate, sulphonate and phosphate 25 functions. The presence of at least one surfactant is generally essential when the active material and/or the inert support are water-insoluble and when the vector agent for the application is water.
- 56 Thus, the compositions for agricultural use according to the invention can contain the active material in a very wide range, from 0.05% to 95% (by weight). Their surfactant content is advantageously 5 between 5% and 40% by weight. Except where otherwise indicated, the percentages given in this description are weight percentages. These compositions according to the invention are themselves in quite diverse, solid or liquid forms. 10 As solid composition forms, mention may be made of powders for dusting (with an active material content which can be up to 100%) and granules, in particular those obtained by extrusion, by compacting, by impregnation of a granulated support or by 15 granulation from a powder (the active material content in these granules being between 0.5 and 80% for the latter cases). The fungicidal compositions according to the invention can also be used in the form of powders for 20 dusting; compositions comprising 50 g of active material and 950 g of talc can also be used; compositions comprising 20 g of active material, 10 g of finely divided silica and 970 g of talc can also be used; these constituents are mixed together and ground 25 and the mixture is applied by dusting. As liquid composition forms or forms intended to constitute liquid compositions when applied, mention may be made of solutions, in particular water-soluble - 57 concentrates, emulsions, concentrated suspensions and wettable powders (or powders for spraying). The concentrated suspensions, which can be applied by spraying, are prepared so as to obtain a 5 stable fluid product which does not become deposited, and they usually contain from 10 to 75% of active material, from 0.5 to 15% of surfactants, from 0.1 to 10% of thixotropic agents, from 0 to 10% of suitable additives, such as antifoaming agents, corrosion 10 inhibitors, stabilizers, penetration agents and adhesives, and, as support, water or an organic liquid in which the active material is insoluble or only sparingly soluble; certain organic solid materials or inorganic salts can be dissolved in the support to help 15 prevent sedimentation or as antifreezes for the water. By way of example, there follows a composition of a concentrated suspension: Example CS1: - Active material 500 g 20 - Polyethoxylated tristyrylphenol phosphate 50 g - Polyethoxylated alkylphenol 50 g - Polysodium carboxylate 20 g - Ethylene glycol 50 g 25 - Polyorganosiloxane oil (antifoaming agent) 1 g - Polysaccharide 1.5 g - Water 316.5 g - 58 The wettable powders (or powders for spraying) are usually prepared such that they contain 20 to 95% of active material, and they usually contain, in addition to the solid support, from 0 to 30% of a 5 wetting agent, from 3 to 20% of a dispersant and, when necessary, from 0.1 to 10% of one or more stabilizers and/or other additives, such as penetration agents, adhesives, anticaking agents, dyes, etc. In order to obtain the powders for spraying 10 or wettable powders, the active materials are intimately mixed with the additional substances in suitable mixers and are ground with mills or other suitable blenders. Powders for spraying with advantageous wettability and suspension formation are 15 thus obtained; they can be placed in suspension with water at any desired concentration and these suspensions can be used very advantageously, in particular for application, for example, to plant leaves or to seeds. 20 By way of example, there follow various wettable powder compositions (or powders for spraying): Example WP1: - Active material 50% 25 - Ethoxylated fatty alcohol (wetting agent) 2.5% - Ethoxylated phenylethylphenol (dispersant) 5% - 59 - Chalk (inert support) 42.5% Example WP2: - Active material 10% - Synthetic C13 oxo alcohol of 5 branched type, ethoxylated with 8 to 10 ethylene oxide (wetting agent) 0.75% - Neutral calcium lignosulphonate (dispersant) 12% - Calcium carbonate (inert filler) qs 100% 10 Example WP3: This wettable powder contains the same ingredients as in the above example, in the following proportions: - Active material 75% 15 - Wetting agent 1.50% - Dispersant 8% - Calcium carbonate (inert filler) qs 100% Example WP4: - Active material 90% 20 - Ethoxylated fatty alcohol (wetting agent) 4% - Ethoxylated phenylethylphenol (dispersant) 6% Example WP5: - Active material 50% 25 - Mixture of anionic and nonionic surfactants (wetting agent) 2.5% - Sodium lignosulphonate (dispersant) 5% - Kaolinic clay (inert support) 42.5% - 60 The aqueous dispersions and emulsions, for example the compositions obtained by diluting a wettable powder according to the invention with water, are included within the general scope of the present 5 invention. The emulsions can be of the water-in-oil or oil-in-water type and they can have a thick consistency, such as that of a "mayonnaise". The fungicidal compositions according to the invention can be formulated in the form of water 10 dispersible granules, which are also included within the scope of the invention. These dispersible granules, with an apparent density generally of between about 0.3 and about 0.6, have a particle size generally of between about 150 and 15 about 2000 and preferably between 300 and 1500 microns. The active material content of these granules is generally between about 1% and about 90% and preferably between 25% and 90%. The rest of the granule is essentially 20 composed of a solid filler and optionally of surfactant adjuvants which give the granule water-dispersibility properties. These granules can be essentially of two different types depending on whether the filler selected is soluble or insoluble in water. When the 25 filler is water-soluble, it can be inorganic or, preferably, organic. Excellent results have been obtained with urea. In the case of an insoluble filler, it is preferably inorganic, for example such as kaolin - 61 or bentonite. It is then advantageously accompanied by surfactants (in a proportion of from 2 to 20% by weight of the granule) more than half of which consists, for example, of at least one dispersant, which is 5 essentially anionic, such as an alkali metal or alkaline-earth metal polynaphthalene sulphonate or an alkali metal or alkaline-earth metal lignosulphonate, the remainder consisting of nonionic or anionic wetting agents such as an alkali metal or alkaline-earth metal 10 alkylnaphthalene sulphonate. Moreover, although this is not essential, other adjuvants can be added, such as antifoaming agents. The granule according to the invention can be 15 prepared by mixing together the required ingredients, followed by granulation according to several techniques which are known per se (granulator, fluid bed, sprayer, extrusion, etc.). The process generally ends by a crushing operation, followed by an operation of 20 screening to the particle size chosen within the limits mentioned above. Granules obtained as above and then impregnated with a composition containing the active material can also be used. Preferably, it is obtained by extrusion, by 25 performing the process as given in the examples below. Example DG1: Dispersible granules 90% by weight of active material and 10% of urea pellets are mixed together in a mixer. The mixture - 62 is then ground in a toothed roll crusher. A powder is obtained, which is moistened with about 8% by weight of water. The wet powder is extruded in a perforated roller extruder. A granulate is obtained, which is 5 dried and then crushed and screened, so as to retain, respectively, only the granules between 150 and 2000 microns in size. Example DG2: Dispersible granules The constituents below are mixed together in 10 a mixer: - Active material 75% - Wetting agent (sodium alkylnaphthalene sulphonate) 2% - Dispersant (polysodium naphthalene 15 sulphonate) 8% - Water-insoluble inert filler (kaolin) 15% This mixture is granulated in a fluid bed, in the presence of water, and then dried, crushed and screened so as to obtain granules between 0.15 and 20 0.80 mm in size. These granules can be used alone, or as a solution or dispersion in water so as to obtain the desired dose. They can also be used to prepare combinations with other active materials, in particular 25 fungicides, these being in the form of wettable powders, granules or aqueous suspensions. The compounds of the invention can also be mixed with one or more insecticides, fungicides, - 63 bactericides, attractant acaricides or pheromones or other compounds with biological activity. The mixtures thus obtained have a broadened spectrum of activity. Mixtures with other fungicides are particularly 5 advantageous, for example mixtures with carbendazim, thiram, diethofencarb, dodine, manebe, mancozebe, diflumetorim, ethirimol, benomyl, cymoxanil, fenpropidine, fenpropimorph, triadimefon, captane, captafol, folpel, thiophanate, thiabendazole, 10 phosphoric acid and its derivatives such as phosetyl-Al, chlorothalonil, copper-based fungicidal compositions, dichloran, metalaxyl, iprodione, fenamidone, oxadixyl, vinchlozoline, tebuconazole, bromuconazole, triticonazole, difenconazole, 15 diniconazole, metconazole, penconazole, propiconazole, prochloraz, fenarimol, triadimenol, furalaxyl, copper derivatives such as copper hydroxide and copper oxychloride, probenazole, azoxystrobin, kresoxim methyl, epoxyconazole, famoxadone, picoxystrobine, 20 fludioxonyl, pyrimethanil, neparipyrim, cyprodinyl, quinoxyfen, ferimzone, fluazinam, trifloxystrobine, dimethomorph, discostrobin, benalaxyl, blasticidin-S, fluquinconazole, tricyclazole, fluzilazole, valinamide derivatives such as, for example, iprovalicarb, 25 flutolanil, guazatine, hexaconazole, hymexazol, isoprothiolane, kazugamycin, pencycuron, phthalide, pyroquilon, tetraconazole, thifluzamide and carboxine. The compositions according to the invention - 64 are also useful for treating the seeds, for example of cereals (wheat, rye, triticale and barley in particular), potato, cotton, pea, rapeseed, corn or flax, or alternatively the seeds of woodland trees (in 5 particular resiniferous trees). It will be noted in this respect that, in the terminology of the person skilled in the art, the term "treatment of seeds" in fact relates to the treatment of the grains. The application techniques are well 10 known to those skilled in the art and they can be used without any drawback in the context of the present invention. Mention may be made, for example, of film cladding or coating. Another subject of the invention is a process 15 for curatively or preventively controlling the phytopathogenic fungi of crops, characterized in that the seeds, the leaves or the trunks of plants or the soils where these plants grow or are likely to grow are treated by applying, spraying or injecting an effective 20 (agronomically effective) and non-phytotoxic amount of an active material of formula (I) or one of its agriculturally acceptable salts or a metal or metalloid complex of this compound which is also agriculturally acceptable, preferably in the form of a fungicidal 25 composition according to the invention. The expression "effective and non-phytotoxic amount" means an amount of composition according to the invention which is sufficient to allow the fungi - 65 present or liable to appear on the crops to be controlled or destroyed, and which does not entail any appreciable symptom of phytotoxicity for the said crops. Such an amount can vary within a wide range 5 depending on the fungus to be combated, the type of crop, the climatic conditions and the compounds included in the fungicidal composition according to the invention. This amount can be determined by systematic field trials, which are within the capabilities of a 10 person skilled in the art. Lastly, the invention relates to a process for preventively or curatively protecting plant multiplication products, as well as the plants resulting therefrom, against fungal diseases, 15 characterized in that the said products are coated with an effective and non-phytotoxic dose of a composition according to the invention. Among the plant multiplication products concerned, mention may be made in particular of seeds 20 or grains, and tubers. As has been indicated above, the methods for coating the plant multiplication products, in particular seeds, are well known in the art and in particular involve film-cladding or coating techniques. 25 The products and compositions according to the invention can also be applied to the leaves of the plant crops. Among the plants targeted by the method - 66 according to the invention, mention may be made, as non-limiting examples, of: - wheat, as regards controlling the following seed diseases: fusaria (Microdochium nivale and 5 Fusarium roseum), stinking smut (Tilletia caries, Tilletia controversa or Tilletia indica) and septoria disease (Septoria nodorum); - wheat, as regards controlling the following diseases of the aerial parts of the plant: cereal 10 eyespot (Pseudocercosporella herpotrichoides), take-all (Gaeumannomyces graminis), foot blight (F. culmorum, F. graminearum), black speck (Rhizoctonia cerealis), powdery mildew (Erysiphe graminis forma specie tritici), rusts (Puccinia striiformis and Puccinia 15 recondita) and septoria diseases (Septoria tritici and Septoria nodorum); - wheat and barley, as regards controlling bacterial and viral diseases, for example barley yellow mosaic; 20 - barley, as regards controlling the following seed diseases: net blotch (Pyrenophora graminea, Pyrenophora teres and Cochliobolus sativus), loose smut (Ustilago nuda) and fusaria (Microdochium nivale and Fusarium roseum); 25 - barley, as regards controlling the following diseases of the aerial parts of the plant: cereal eyespot (Pseudocercosporella herpotrichoides), net blotch (Pyrenophora teres and Cochliobolus - 67 sativus), powdery mildew (Erysiphe graminis forma specie hordes), dwarf leaf rust (Puccinia hordes) and leaf blotch (Rhynchosporium secalis); - potato, as regards controlling tuber 5 diseases (in particular Helminthosporium solani, Phoma tuberosa, Rhizoctonia solani, Fusarium solani) and certain viruses (virus Y); - cotton, as regards controlling the following diseases of young plants grown from seeds: 10 damping-off and collar rot (Rhizoctonia solani, Fusarium oxysporum) and black root rot (Thielaviopsis basicola); - pea, as regards controlling the following seed diseases: anthracnose (Ascochyta pisi, 15 Mycosphaerella pinodes), fusaria (Fusarium oxysporum) and grey mould (Botrytis cinerea); - rapeseed, as regards controlling the following seed diseases: Phoma lingam and Alternaria brassicae; 20 - corn, as regards controlling seed diseases: (Rhizopus sp., Penicillium sp., Trichoderma sp., Aspergillus sp., and Gibberella fujikuroi); - flax, as regards controlling the seed disease: Alternaria linicola; 25 - forest trees, as regards controlling damping-off (Fusarium oxysporum, Rhizoctonia solani). Wheat and barley are the preferred plants for carrying out the method according to the invention.
- 68 The dose of composition applied is, generally, advantageously such that the dose of active material is between 2 and 200 g of active material per 100 kg of seed, preferably between 3 and 150 g per 5 100 kg in the case of seed treatments. In the case of plant treatments, doses of from 10 to 800 g/ha, preferably 50 to 300 g/ha, are generally applied as a foliar treatment. The examples which follow illustrate the 10 present invention: Example 1: Preparation of methyl (E,E)-2-(2-{1-[5 chloro-2-thiophenyl)methyloxyimino]ethoxy methyl}phenyl)-2-methoxyiminoethanoate 15 Step 1 Preparation of N-[(5-chloro-2 thiophenyl)methoxy]acetamide 7.1 ml of acetyl chloride are added, with stirring, to a solution at room temperature of 23.6 g 20 of 0-(5-chloro-2-thiophenyl)methylhydroxylamine hydrochloride and 24.2 ml of pyridine in 200 ml of dichloromethane. After 2 h, the reaction medium is taken up in ethyl acetate, washed with water, dried over magnesium sulphate, concentrated and then purified 25 by flash chromatography on silica, which gives 16.0 g of N-((5-chloro-2-thiophenyl)methoxy)acetamide in the form of a pale yellow liquid. Rf = 0.18 (eluent: 50/50 heptane/ethyl acetate) (in which Rf denotes the - 69 coefficient of retention on a chromatography plate on a thin layer of silica). Step 2: Preparation of methyl (E,E)-2-(2-{l-[(5 5 chloro-2-thiophenyl)methyloxyimino]ethoxy methyl}phenyl)-2-methoxyiminoethanoate A suspension of 2.10 g of methyl (E)-2-[2 (bromomethyl)phenyl]-2-methoxyiminoethanoate and 1.65 g of 0-(5-chloro-2-thiophenyl)methyl acetohydroxamate 10 with 3.20 g of caesium carbonate in 50 ml of acetonitrile is stirred at 50*C for 3 h and is then filtered and concentrated. The reaction medium is taken up in 20 ml of toluene containing a catalytic amount of acetic acid and is stirred at 1000C for 4 h. 15 Concentration followed by purification by flash chromatography on silica gives 1.30 g of methyl (E,E) 2-(2-{1-[(5-chloro- 2 -thiophenyl)methyloxyimino]ethoxy methyllphenyl)-2-methoxyiminoethanoate in the form of a white solid. m.p. = 630C (this expression denotes the 20 melting point). Example 2: Preparation of (E,E)-2-(2-{l-[(5-chloro-2 thiophenyl)methyloxyiminolethoxymethyl}phenyl)-2 methoxyimino-N-methylacetamide 25 0.80 g of methyl (E,E)-2-(2-{1-[(5-chloro-2 thiophenyl)methyloxyimino]ethoxymethyl}phenyl)-2 methoxyiminoethanoate is stirred for 5 h at room temperature in 10 ml of a solution of methylamine [2M] - 70 in methanol. After evaporation, 0.88 g of (E,E)-2-(2 {1-[(5-chloro-2-thiophenyl)methyloxyiminolethoxy methyl}phenyl)-2-methoxyimino-N-methylacetamide is obtained in the form of a pale yellow oil. nD = 1.5710 5 (24.0*C) (this expression denotes the refractive index at 24.00C, using the sodium D-line as light) Example 3: Preparation of methyl (E,E)-2-(2-{1-[(3,5 dimethyl-4-isoxazolyl)methyloxyimino]-1 10 cyclopropylmethyloxymethyl)phenyl)-3-methoxypropenoate Step 1: Preparation of N-[(3,5-dimethyl-4 isoxazolyl)methoxy]cyclopropanecarboxamide 10.9 ml of cyclopropanecarboxylic acid 15 chloride are added dropwise to a solution, cooled to 00C, of 18 g of O-(3,5-dimethyl-4 isoxazolyl)methylhydroxylamine hydrochloride and 30.9 ml of triethylamine in 250 ml of dichloromethane. The reaction medium obtained is stirred at room 20 temperature for 16 h and is then neutralized with an aqueous pH 7 buffer solution. The organic phase is dried, evaporated and then recrystallized from diisopropylether, which gives 12.9 g of N-[(3,5 dimethyl-4-isoxazolyl)methoxylcyclopropanecarboxamide 25 in the form of a white solid, m.p. = 92*C. Step 2: Preparation of methyl (E,E)-2-(2-{1-[(3,5- - 71 dimethyl-4-isoxazolyl)methyloxyimino]-1 cyclopropylmethyloxymethyl}phenyl)-3-methoxypropenoate 1.5 g of O-(3,5-dimethyl-4-isoxazolyl)methyl cyclopropanecarboxamate, 1.8 g of methyl (E)-2-[2 5 (bromomethyl)phenyl]-3-methoxypropenoate and 2.5 g of caesium carbonate are stirred for 4 h under an inert atmosphere in 10 ml of refluxing acetonitrile. After filtration of the caesium salts and evaporation of the solvent, the crude reaction product is stirred at 1000C 10 for 5 h in 15 ml of toluene containing 0.25 ml of glacial acetic acid. After neutralization with a pH 7 buffer solution, followed by filtration on phase separating paper and evaporation, flash chromatography on silica makes it possible to isolate 0.61 g of methyl 15 (E,E)-2-(2-{l-[(3,5-dimethyl-4-isoxazolyl)methyloxy iminol-1-cyclopropylmethyloxymethyl}phenyl)-3-methoxy propenoate in the form of a yellow oil. nD = 1.5300 (24.5*C). Example 4: 20 Preparation of methyl (E,E)-2-(2-{1-[(3,5 dimethyl-4-isoxazolyl)methyloxyimino]-1-cyclopropyl methyloxymethylIphenyl)-2-methoxyiminoethanoate Methyl (E,E)-2-(2-{1-[(3,5-dimethyl-4 isoxazolyl)methyloxyimino]-1-cyclopropylmethyloxy 25 methyl}phenyl)-2-methoxyiminoethanoate is prepared according to a procedure similar to that given in Example 3, step 2. 0.82 g of methyl (E,E)-2-(2-(1 ((3,5-dimethyl-4-isoxazolyl)methyloxyimino)-1- - 72 cyclopropylmethyloxymethyl)phenyl)-2 methoxyiminoethanoate is thus obtained in the form of an orange-coloured oil from 4 g of O-(3,5-dimethyl-4 isoxazolyl)methyl cyclopropanecarboxamate and 4.8 g of 5 methyl (E)-2-[2-(bromomethyl)phenyl]-2 methoxyiminoethanoate. nD = 1.5320 (25.70C) Example 5: Preparation of (E,E)-2-(2-{l-[(3,5-dimethyl 4-isoxazolyl)methyloxyimino]-1-cyclopropyl 10 methyloxymethyllphenyl)-2-methoxyimino-N methylacetamide (E,E)-2-(2-{l-[(3,5-Dimethyl-4 isoxazolyl)methyloxyimino]-1 cyclopropylmethyloxymethyl}phenyl)-2-methoxyimino-N 15 methylacetamide is prepared according to a procedure similar to that given in Example 2. 0.435 g of (E,E)-2 (2-{1-[(3,5-dimethyl-4-isoxazolyl)methyloxyiminol-1 cyclopropylmethyloxymethyl}phenyl)-2-methoxyimino-N methylacetamide is thus obtained in the form of a 20 yellow oil from 0.4 g of methyl (E,E)-2-(2-{l-[(3,5 dimethyl-4-isoxazolyl)methyloxyimino]-1 cyclopropylmethyloxymethylIphenyl)-2 methoxyiminoethanoate. nD = 1.5357 (26.10C) Example 6: 25 Preparation of methyl (E)-N-methoxy-N-(2-{l [(3, 5 -dimethyl-4-isoxazolyl)methyloxyimino]-1 cyclopropylmethyloxymethyl}phenyl)carbamate Methyl (E)-N-methoxy-N-(2-{l-[(3,5-dimethyl- - 73 4-isoxazolyl)methyloxyimino]-1 cyclopropylmethyloxymethyl}phenyl)carbamate is prepared according to a procedure similar to that given in Example 3, step 2. 0.366 g of methyl (E)-N-methoxy-N 5 (2-{1-[(3,5-dimethyl-4-isoxazolyl)methyloxyimino]-1 cyclopropylmethyloxymethyl}phenyl)carbamate is thus obtained in the form of an orange-coloured oil from 1.7 g of 0-(3,5-dimethyl-4-isoxazolyl)methyl cyclopropanecarboxamate and 1.95 g of methyl N-methoxy 10 N-(2-(bromomethyl)phenyllcarbamate. nD = 1.5266 (23.30C). Example 7: Preparation of methyl (E)-2-(2-{1-[(3,5 dimethyl-4-isoxazolyl)methyloxyimino]-e}phenyl)-2 15 methoxyethanoate Methyl (E)-2-(2-{1-[(3,5-dimethyl-4 isoxazolyl)methyloxyimino]-1 cyclopropylmethyloxymethyl}phenyl)-2-methoxyethanoate is prepared according to a procedure similar to that 20 given in Example 3, step 2. 0.23 g of methyl (E)-2-(2 {1-[(3,5-dimethyl-4-isoxazolyl)methyloxyimino]-1 cyclopropylmethyloxymethyl}phenyl)-2-methoxyethanoate is thus obtained in the form of an orange-coloured oil from 1.7 g of O-(3,5-dimethyl-4-isoxazolyl)methyl 25 cyclopropanecarboxamate and 1.94 g of methyl 2-[2 (bromomethyl)phenyl)-2-methoxyethanoate. nD = 1.5277 (23.90C).
-74 Example 8: Preparation of methyl (E,E)-2-(2-{1-[(3,5 dimethyl-4-isoxazolyl)methyloxyimino]-1 cyclopropylmethyloxymethyl}phenyl)-2-butenoate 5 Methyl (E,E)-2-(2-{1-[(3,5-dimethyl-4 isoxazolyl)methyloxyimino]-1 cyclopropylmethyloxymethyl}phenyl)-2-butenoate is prepared according to a procedure similar to that given in Example 3, step 2. 0.66 g of methyl (E,E)-2-(2-{1 10 [(3,5-dimethyl-4-isoxazolyl)methyloxyimino]-1 cyclopropylmethyloxymethyl}phenyl)-2-butenoate is thus obtained in the form of a yellow oil from 1.5 g of 0-(3,5-dimethyl-4-isoxazolyl)methyl cyclopropanecarboxamate and 1.6 g of methyl (E)-2-[2 15 (bromomethyl)phenyl]-2-butenoate. no = 1.5244 (25.6*C) Example 9: Preparation of methyl (E,E)-2-(2-{1-[l-(2 pyridyl)propyloxyimino]-1-cyclopropylmethyloxymethyl} phenyl)-3-methoxypropenoate 20 Step 1: Preparation of N-[l-(2-pyridyl)propyloxy] phthalimide A mixture of 14.4 g of 2-(1 chloropropyl)pyridine, 15.1 g of N-hydroxyphthalimide 25 and 12.8 g of potassium carbonate in 280 ml of dimethylformamide is stirred at 800C for 7 h. The crude reaction product is partitioned between an aqueous phase and ethyl acetate. The aqueous phase is extracted - 75 with ethyl acetate and the organic phases are combined and washed with saturated aqueous sodium chloride solution and then dried and evaporated. The solid obtained is recrystallized from diisopropyl ether, 5 which gives 11.52 g of N-[l-(2 pyridyl)propyloxy]phthalimide in the form of a white solid. m.p. = 1234C. Step 2: Preparation of N-[1-(2 10 pyridyl)propoxy]cyclopropanecarboxamide A mixture of 20.4 g of N-[l-(2 pyridyl)propyloxylphthalimide and 4.34 ml of hydrazine hydrate in 400 ml of ethanol is stirred at 35*C for 2 h and then filtered. The filtrate is rinsed with ethanol, 15 the mother liquors are combined, concentrated and then taken up in ethyl acetate and saturated aqueous sodium chloride solution. The aqueous phase is re-extracted with ethyl acetate and the organic phases are combined, dried and evaporated to give 11.65 g of crude reaction 20 product, which is added to a solution of 12.17 ml of triethylamine in 120 ml of dichloromethane. 7.98 ml of cyclopropanecarboxylic acid chloride are then added dropwise at 0 0 C, after which the reaction mixture is stirred for 1 h at room temperature. Saturated aqueous 25 sodium chloride solution is then added, the aqueous phase is extracted with dichloromethane and the organic phases are combined, dried and then evaporated. The crude product obtained is recrystallized from -76 diisopropyl ether and then purified by flash chromatography on a column of silica, to give 13 g of N-[1-(2-pyridyl)propoxy]cyclopropanecarboxamide in the form of a white solid. m.p. = 79"C. 5 Step 3: Preparation of methyl (E,E)-2-(2-{l-[1-(2 pyridyl)propyloxyimino]-1 cyclopropylmethyloxymethyl}phenyl)-3-methoxypropenoate 6.1 g of O-1-(2-pyridyl)propyl 10 cyclopropanecarboxamate, 7.89 g of methyl (E)-2-[2 (bromomethyl)phenyl]-3-methoxypropenoate and 9.02 g of caesium carbonate are stirred for 4 h under an inert atmosphere in 100 ml of refluxing acetonitrile. After filtration of the caesium salts, concentration of the 15 filtrate and uptake in an aqueous solution and ethyl acetate, the organic phase is dried and evaporated. The crude reaction product is purified by flash chromatography on silica. The product obtained is stirred at 100 0 C for 6 h in 50 ml of toluene containing 20 0.50 ml of glacial acetic acid. After neutralization with a buffer solution at pH = 7 followed by filtration on phase-separating paper and evaporation, flash chromatography on silica gives 0.96 g of methyl (E,E) 2-(2-{l-[1-(2-pyridyl)propyloxyimino]-1 25 cyclopropylmethyloxymethyllphenyl)-3-methoxypropenoate in the form of a brown oil. nD = 1.5366 (24.0*C).
- 77 Example 10: Preparation of methyl (E,E)-2-(2-{1-[1-(6 methyl-2-pyridyl)ethyloxyimino]-1 cyclopropylmethyloxymethylIphenyl)-2 5 methoxyiminoethanoate Step 1: Preparation of 2-(1-hydroxyethyl)-6 methylpyridine 50 ml of bromomethyl Grignard reagent 10 [3M/diethyl ether] are added, under an inert atmosphere, to a solution of 15 g of 6-methylpyridine 2-carboxaldehyde in 100 ml of diethyl ether at -78*C. After the addition, the reaction medium is stirred at room temperature for 1 h. A diethyl ether/hydrochloric 15 acid [1N] partition followed by neutralization of the aqueous phase with a pH 7 buffer solution and evaporation of the organic phases combined and dried over magnesium sulphate gives 14.6 g of crude 2-(1 hydroxyethyl)-6-methylpyridine in the form of a yellow 20 oil. Rf = 0.31 (30/70 heptane/ethyl acetate). Step 2: Preparation of N-[1-(6-methyl-2 pyridyl)ethyloxy]phthalimide 14.6 g of crude 2-(1-hydroxyethyl)-6 25 methylpyridine, 19.1 g of N-hydroxyphthalimide and 30.7 g of triphenylphosphine are diluted in 300 ml of tetrahydrofuran. 18.4 ml of diethyl azodicarboxylate are then added dropwise with stirring and under an - 78 inert atmosphere. The reaction mixture obtained is stirred at room temperature for 14 h and then evaporated and purified by flash chromatography on silica, to give a solid mixture corresponding to the 5 coupling product and to the reduced diethyl azodicarboxylate, which is used without further purification in the following step. Rf = 0.59 (30/70 heptane/ethyl acetate). Step 3: 10 Preparation of O-[1-(6-methyl-2 pyridyl)ethyl]hydroxylamine The above mixture of N-[1-(6-methyl-2 pyridyl)ethyloxy]phthalimide and of reduced diethyl azodicarboxylate is stirred in 200 ml of refluxing 15 ethanol in the presence of 5.8 g of hydrazine hydrate for 1 h. The filtrate is washed with ethanol and the mother liquors are then concentrated and taken up in diisopropyl ether. After 3 successive crystallizations, the supernatant diisopropyl ether solution is 20 evaporated to give 8.4 g of O-[1-(6-methyl-2 pyridyl)ethyl]hydroxylamine in the form of a pale yellow oil. Rf = 0.23 (100 [lacuna] ethyl acetate). Step 4: Preparation of N-[1-(6-methyl-2 25 pyridyl)ethoxy]cyclopropanecarboxamide 6.2 ml of cyclopropane carboxylic acid chloride are added dropwise, under an inert atmosphere, to a solution, cooled to 00C, of 8 g of 0-[1-(6-methyl- - 79 2 -pyridyl)ethyl]hydroxylamine and 9.6 ml of triethylamine in 100 ml of dichloromethane. The reaction mixture obtained is stirred at room temperature for 5 h and is then neutralized with pH 7 5 buffer solution. The organic phase is washed with pH 7 buffer solution and the combined aqueous phases are then extracted with ethyl acetate. After combining the organic phases and evaporation, flash chromatography on silica gives 2.9 g of N-[l-(6-methyl-2 10 pyridyl)ethoxy]cyclopropanecarboxamide in the form of a white solid. m.p. = 134*C. Step 5: Preparation of methyl (E,E)-2-(2-{1-[1-(6 methyl-2-pyridyl)ethyloxyimino]-1 15 cyclopropylmethyloxymethyl}phenyl)-2 methoxyiminoethanoate 1.3 g of O-1-( 6 -methyl-2-pyridyl)ethyl cyclopropanecarbohydroxamate, 1.7 g of methyl (E)-2-[2 (bromomethyl)phenyl]- 2 -methoxyiminoethanoate and 2.3 g 20 of caesium carbonate are stirred for 3 h under an inert atmosphere in 15 ml of refluxing acetonitrile. After filtration of the caesium salts and evaporation of the solvent, the crude reaction product is stirred at 1000C in 20 ml of toluene containing 0.24 ml of glacial 25 acetic acid. After neutralization with pH 7 buffer solution, followed by filtration on phase-separating paper and evaporation, flash chromatography on silica gives 0.701 g of methyl (E,E)-2-(2-{1-[1-(6-methyl-2- - 80 pyridyl)ethyloxyimino]-1 cyclopropylmethyloxymethyl}phenyl)-2 methoxyiminoethanoate in the form of a brown oil. nD = 1.5438 (24.20C). 5 Example 11: Preparation of methyl (E,E)-2-(2-{1-[l-(6 methyl-3-pyridyl)-1-(methoxycarbonyl)ethyloxyimino]-1 cyclopropylmethyloxymethyl}phenyl)-2 methoxyiminoethanoate 10 Step 1: Preparation of methyl 2-bromo-2-(6-methyl-3 pyridyl)propionate A mixture of 14 g of methyl 2-(6-methyl-3 pyridyl)propionate, 14 g of N-bromosuccinimide and 1 g 15 of benzoyl peroxide in 300 ml of carbon tetrachloride is stirred for 3 h under illumination with a halogen lamp. After filtration, the organic solution is washed with saturated aqueous sodium chloride solution and then with saturated aqueous sodium thiosulphate 20 solution and again with saturated aqueous sodium chloride solution, dried and evaporated. Purification by flash chromatography on silica gives 2.9 g of methyl 2 -bromo-2-(6-methyl-3-pyridyl)propionate in the form of a brown oil. Rf = 0.38 (50/50 heptane/ethyl acetate). 25 Step 2: Preparation of methyl 2 {[(cyclopropylcarbonyl)amino]oxy}-2-(6-methyl-3 pyridyl)propanoate - 81 A mixture of 2.9 g of methyl 2-bromo-2-(6 methyl-3-pyridyl)propionate, 1.13 g of cyclopropanecarboxamic acid and 0.6 g of sodium methoxide in 40 ml of methanol is heated at 50*C for 5 5 h. A suspension of 0.57 g of cyclopropanecarboxamic acid and 0.3 g of sodium methoxide in 2 ml of methanol is then added and the reaction mixture is stirred at 50*C for a further 2 h. After evaporation of the solvent, the crude reaction product is taken up in an 10 aqueous solution and ethyl acetate and the organic phase is dried, evaporated and purified by flash chromatography on silica to give 1.7 g of methyl 2 {[(cyclopropylcarbonyl)amino]oxy}-2-(6-methyl-3 pyridyl)propanoate in the form of a brown solid. 15 m.p. = 89*C. Step 3: Preparation of methyl (E,E)-2-(2-{1-[l-(6 methyl-3-pyridyl)-1-(methoxycarbonyl)ethyloxyimino]-1 cyclopropylmethyloxymethyl}phenyl)-2 20 methoxyiminoethanoate 1.4 g of O-1-(6-methyl-3-pyridyl)-l (methoxycarbonyl)ethyl cyclopropanecarboxamate, 1.43 g of methyl (E)-2-[2-(bromomethyl)phenyl]-2 methoxyiminoethanoate and 1.63 g of caesium carbonate 25 are stirred for 7 h under an inert atmosphere in 50 ml of refluxing acetonitrile. After filtration of the caesium salts and evaporation of the solvent, the crude reaction product is stirred at 50'C for 5 h in 20 ml of - 82 toluene containing 0.25 ml of glacial acetic acid. After neutralization with aqueous potassium carbonate solution, followed by extraction of the aqueous phase with ethyl acetate and evaporation of the combined and 5 dried organic phases, flash chromatography on silica gives 0.54 g of methyl (E,E)-2-(2-{1-[1-(6-methyl-3 pyridyl)-1-(methoxycarbonyl)ethyloxyimino]-1 cyclopropylmethyloxymethyl}phenyl)-2 methoxyiminoethanoate in the form of a pink solid. 10 m.p. = 95*C. Example 12: Preparation of methyl (E,E)-2-(2-{1-[1-(N oxido-2-pyridino)ethyloxyimino]ethoxymethyllphenyl)-3 methoxypropenoate 15 0.059 ml of aqueous 30% hydrogen peroxide solution is added dropwise to a solution at room temperature of 200 mg of methyl (E,E)-2-(2-{1-[1-(2 pyridyl)ethyloxyimino]ethoxymethyl}phenyl)-3 methoxypropenoate (cf. Example 50) and 0.65 mg of 20 methyltrioxorhenium in 1 ml of dichloromethane. The reaction mixture obtained is stirred at room temperature for 24 h and is then poured into a pH 7 buffer solution. After extraction of the aqueous phase with dichloromethane, combining of the organic phases 25 and then evaporation, flash chromatography on silica gives 172 mg of methyl (E,E)-2-(2-{1-[1-(N-oxido-2 pyridino)ethyloxyimino]ethoxymethyl}phenyl)-3 methoxypropenoate in the form of a colourless oil.
- 83 nD = 1.5629 (21.2 0 C). Example 13: Preparation of methyl (E,E)-2-(2-{1-[1-(4 quinolyl)ethyloxyimino]ethyloxymethyl}phenyl)-2 5 methoxyiminoethanoate Step 1: Preparation of methyl (E,E)-2-{2-[1-(tert butyldimethylsilyloxyimino)ethyloxymethyl]phenyl}-2 methoxyiminoethanoate 10 A mixture of 1.89 g of O-tert butyldimethylsilyl acetohydroxamate, 2.86 g of methyl (E)-2-[2-(bromomethyl)phenyl]-2-methoxyiminoethanoate and 3.91 g of caesium carbonate in 50 ml of acetonitrile is stirred at 500C for 5 h and then 15 filtered and concentrated. Purification by flash chromatography on silica gives 0.60 g of methyl (E,E) 2-{2-[1-(tert-butyldimethylsilyloxyimino)ethyloxy methyl]phenyl}-2-methoxyiminoethanoate in the form of a white solid. m.p. = 79*C. 20 Step 2: Preparation of methyl (E,E)-2-{2-[l (hydroxyimino)ethyloxymethyl]phenyl}-2 methoxyiminoethanoate A mixture of 0.19 g of methyl (E,E)-2-{2-[1 25 (tert-butyldimethylsilyloxyimino)ethyloxymethyl] phenyll-2-methoxyiminoethanoate, 0.086 g of acetic acid and 0.080 g of caesium fluoride in 10 ml of acetonitrile is stirred for 20 h at room temperature.
- 84 Concentration followed by purification by flash chromatography on silica gives 0.10 g of methyl (E,E) 2 -{2-[1-(hydroxyimino)ethyloxymethyl]phenyl}-2 methoxyiminoethanoate in the form of a white solid. 5 m.p. = 112*C. Step 3: Preparation of methyl (E,E)-2-(2-{l-[1-(4 quinolyl)ethyloxyimino]ethyloxymethylIphenyl)-2 methoxyiminoethanoate 10 A mixture of 0.4 g of methyl (E,E)-2-{2-[1 (hydroxyimino)ethyloxymethyl]phenyl}-2 methoxyiminoethanoate, 0.274 g of 4-(1 chloroethyl)quinoline and 0.513 g of caesium carbonate in 20 ml of acetonitrile is stirred at reflux for 5 h. 15 After filtration and evaporation of the solvent, the crude reaction product is purified by flash chromatography on silica to give 0.118 g of methyl (E,E)-2-(2-fl-[l-(4-quinolyl)ethyloxyiminolethyloxy methyl}phenyl)-2-methoxyiminoethanoate in the form of a 20 yellow syrup. Rf = 0.41 (30/70 heptane/ethyl acetate). Example 14: Preparation of methyl (E,E)-2-(2-{l-[(3 trifluoromethyl-2-pyridyl)oxyiminolethyloxymethyl} phenyl)-2-methoxyiminoethanoate 25 A mixture of 0.4 g of methyl (E,E)-2-{2-[1 (hydroxyimino)ethyloxymethyl]phenyl}-2 methoxyiminoethanoate (prepared according to the method described in the above example), 0.323 g of 2-bromo-3- - 85 (trifluoromethyl)pyridine and 0.513 g of caesium carbonate in 20 ml of acetonitrile is refluxed for 5 h. After filtration and evaporation of the solvent, the crude reaction product is purified by flash 5 chromatography on silica to give 0.510 g of methyl (E,E)-2-(2-{1-[(3-trifluoromethyl-2 pyridyl)oxyiminolethyloxymethylIphenyl)-2 methoxyiminoethanoate in the form of a white solid. m.p. = 760C 10 Example 15: Preparation of methyl (E,E)-2-(2-{1-[2-(2 pyridyl)ethoxyiminol-1-cyclopropylmethyloxy methyl}phenyl)-3-methoxypropenoate Step 1: 15 Preparation of N-[2-(2-pyridyl)ethoxy] phthalimide 20 g of 2-(2-hydroxyethyl)pyridine, 29.2 g of N-hydroxyphthalimide, 47 g of triphenylphosphine and 450 ml of anhydrous THF are introduced into a three 20 necked flask under an inert atmosphere. 29.4 ml of DEAD are then added dropwise with stirring. The THF is evaporated off and the residue is taken up in diisopropyl ether and ethyl acetate to give a white precipitate which is recrystallized to give 14 g of the 25 expected product. Step 2: Preparation of methyl (E,E)-2-(2-{1-[2-(2 pyridyl)ethoxyiminol-1-cyclopropylmethyloxy- - 86 methyl phenyl)-3-methoxypropenoate By repeating steps 2 and 3 described in Example 9 above, using the phthalimide prepared above, the expected compound is obtained in the form of a 5 viscous brown liquid. nD = 1.5605 (21.40C) Example 16: Preparation of methyl (E)-N-methoxy-N-(2-{l [2-(2-pyridyl)ethoxyimino]-1-cyclopropylmethyl oxymethyl}phenyl)carbamate 10 By repeating the procedure described in Example 15 above, but using methyl N-methoxy-N-[2 (bromomethyl)phenyl]carbamate instead of methyl (E)-2 [2-(bromomethyl)phenyl]-3-methoxypropenoate, the expected product is obtained in the form of a viscous 15 orange liquid. nD = 1.5435 (21.50C). The examples which follow are obtained according to similar processes. In the examples which follow, the groups Gl, G2 and G3 are of (E) stereochemistry and the substituents W 1 and W 2 are in a 20 trans position (E stereochemistry) relative to the double bond -C(R 3 )=N-. (In the following table, Pr means n-propyl, cPr means cyclopropyl, iPr means isopropyl, sBu means sec-butyl and He means n-hexyl) -87 E Gn XR 1 Wp RA 1 'R,A G1 H 0 Me 0 1 H H 2-pyridyl 17 Q 1 =CH; Q 2 =0 R,=Me; R 4 ,OMe GI H 0 Me 0 1 H H1 2-pyridyl 18 Q=N ; Q;O Rs=Me ; ,(.OMe GI H 0 Me 0 1 H H 2-pyridyl 19 Q,=N; Q 2 =0; R,=Me ; R 4 =NHMe GI H 0 cPr 0 1 H H 2-pyridyl 20 Q,=CH; Q 2 =0
R
5 =Me ; R.=OMe GI H 0 cPr 0 1 H H4 2-pyridyl 21 Q=;Q R,=Me; R 4 =OMe GI H 0 cPr 0 1 H H 2-pyridyl 22 QIN; Q 2 =0;
R
6 =Me; R 4 NHMe G8 H 0 cPr 0 1 H H 2-pyridyl 23 Q 3 =0; Q 4 =N
R
9 )=Me ; RIO0-Me 03 H 0 cPr 0 1 - H 2-pyridyl 24 Q?0O; R,=Me R 4 =OMe -88 Ex ~ Gn X>JVW R,, H' 3 p j R, A G4 H 0 cPr 0 1 H H 2-pyridyl 25 Q 2 0; n0O
R
3 =Me ; R 4 =OMe 61 H 0 Me 0 1 H H 3-pyridyl 26 Q 1 =CH ; Q 2 =0 R,=Me; R 4 -OMe G1 H 0 Me 0 1 Et H 4-pyridyl 27 QI=CH4 Q 2 =0 Rs=Me; R,=0Me GI H 0 cPr 0 1 Et H 3-pyridyl 28 QI=CH; Q 2 0 R,=Me ; R 4 =OMe G1 H 0 cPr 0 1 H H 3-pyridyl 29 Q,=CH; Q 2 =0 R,=Me; P 4 =OMe 63 H 0 Or 0 1 H H 3-pyridyl 30 Q 2 =O;
R
6 =Me; R,=OMe G3 H 0 Me 0 1 H H 3-pyridyl 31 =O
R
6 =Me; R 4 =OMe G1 H 0 cPr 0 1 H H 3-pyridyl 32 Q,=N:Q 2 =0 R5=Me ; R4=OMe G3 H 0 Me 0 1 H H 4-pyridyl 33Q20 Rg'Me; R4=0Me G3 H 0 cPr 0 1 Et H 2-pyridyl 34Q=0
&=
6 Me; R 4 =OMe G1 H 0 cPr 0 1 Et H 2-pyridyl 35 Q 1 =N; Q,=
R
5 =Me;- R,40Me -89 G! H 0 cPr 0 1 Me H 6-Me-2-pyridyl 36 QI=CH; Q 2 =O Rs=Me ; R,=OMe G8 H 0 cPr 0 1 Et H 2-pyridyl 37 Q 3 =0; Q 4 =N
R
9 =Me ; RO=0Me G1 H 0 oPr 0 1 Et H 2-pyridyl 38 Q 1 =N ;Q 2 =0:;
R
1 -- Me ; R4=NHMe 64 H 0 cPr 0 1 Et H 2-pyridyl 39 Q 2 =0; n-0
R
5 '=Me ;R 4 =0Me G I H 0 cPr 0 1 Me H 6-Me-2-pyridyl 40 Q 1 =N;Q=; Rg-Me R.=NHMe G61 H 0 cPr 0 1 H Et 4-pyridyl 41 Q,=C4; Q,=0 Rs=Me ; &=0Me 64 H 0 cOr 0 1 H Et 4-pyridyl 42 Q,=O; n=0 R,=Me ; R 4 =OMe G61 H4 0 cPr 0 1 H Et 4-pyridyl 43 Q 1
=N;-Q
2 -0O
R
5 =Me;R 4 =Ome G1 H 0 cPr 0 1 Me CN 2-pyridyl 44 Q 1 -N; Q 2 =0 R,=Me; R4=0Me 45 G1 H 0 cPr 0 1 CO 2 Me Me 6-methyl-3-pyridyl Q,=N ; Q 2 =0O;
&
6 =Me; R~tNHMe 46 GI H 0 cPr 0 1 CN Me 2-pyridyl Q.=N; 20 RO=Me ; R,=NHMe -90 Ex GmX ,-,: wi P R, R, A 47 GI H 0 cPr 0 1 CN Me 2-pyridyl
Q
1 -CH; Q 2 -0
R
5 i=Me ; R.'.OMe 48 GI H 0 oPr 0 1 Me H 2-pyridyl
Q
1 =CH; Q,=0
R
5 =Me; R.=OMe 49 GI H 0 cPr 0 1 Me H 2-pyridyl
Q
1 =N; Q 2 =0
R
5 =Me ; R,=0Me 50 G4 H 0 O~r 0 1 Me H 2-pyridyl Qz=0; n=0 &=~Me; R40Me 51 G I H 0 cPr 0 I Me H 2-pyridyl QIN; Q 2 =0; &=Me ; RNHMe 52 G8 H 0 cPr 0 1 CN Me 2-pyridyl Q,=0 ' Q 4 =N R,=Me R, 0 =OMe 53 G4 H 0 cPr 0 1 CN Me 2-pyridyl
Q
2 =0; n0O R,=Me; R,=-OMe 54 GI H 0 Me 0 I Me H 2-pyridyl Q,=CH ; Q 2 =0
R
5 =Me; R,=Me 55 GI H 0 Me 0 1 Me H 2-pyridyl Q.=N Q,=0
R
5 =Me ; R4=0Me 56 G4 H 0 Me 0 1 Me H 2-pyridyl Q,=Q; n=o R,=Mc; R?,OMe 57 GI H 0 Me 0 1 e H 2-pyridyl Q,=N; Q2=0;
&
6 =Me; R 4 =NHMe -91 ExGn X wJ.j 'R W,p v , A2.: A 58 GI H 0 Et 0 I Me H 2-pyridyt Q,-CH ; Q 2 =0
R
5 =Me; R 4 OMe 59 G4 H 0 Et 0 1 Me H 2-pyridyl Rs=Mc ; &=0Me 60 G I H 0 cPr 0 1 Me H 3-chloro-2-pyridyl QI=N ; Q 2 =0 Rs=Me ; R 4 =OMe 61 Gg H 0 cpr 0 1 Me H 2-pyridyl Q3=0; Q 4 =N
R
9 -Me ;R,.-OMe 62 GI H 0 cPr 0 1 Me 14 3-chloro-2-pyridyl
Q
1 =CH ; Q2=0
R
5 =Me; R 4 =OMe 63 GI H 0 cPr 0 1 Me H 4-pyridyl QI=CH ;Q 2 =0 Rs=Me; &=0Me 64 GI H 0 O~r 0 1 Me H 4-pyridyl Q=N; Q 2 =0
R
5 =Me ; R 4 =OMe 65 GI H 0 iPr 0 1 Me H 2-pyridyl
Q
3 =CH ;Q 2 =0 R5=Me R=0Me 66 GI H 0 Me 0 1 Me H N-oxido-2-pyridinio
Q
1 =N ; Q 2 =0 R,=Me; R,=0Me 67 G4 H 0 Me 0 1 Me H N-oxido-2-pyridinio
Q
2 0; n=o Rs=Me; &R-Me 68 GI H 0 irr 0 1 H 2-pyridyl Q=CH: Q 2 -0 R5=Me; R=OMe -92 ExGn X- ,R Ww R, R A 69 G1 H 0 Et 0 1 H H 2-pyridyl Q,=CI-l; Q,=O Rts=Me R4-0Me 70 GI H 0 Pr 0 1 H H 2-pyridyl Q,=CH; Q 2 =0
R
5 =Me ; R,=0Me 71 G1 H- 0 Me 0 1 Me H 3-chloro-2-pyridyl Q,=CH; Q 2 =0 R,=Me; R.=0Me1 72 G1 H 0 Me 0 1 Et H 2-pyridyl
Q,=CH;-Q
2 -0 R,=Me; R=OMe 73 GI H 0 Et 0 1 Et H 2-pyridyl Q,=CH ; Q 2 =O
R
5 =Me; R 1 ,=OMe 74 G1 H 0 iPr 0 1 Et H 2-pyridyl Q,=CH ;Q 2 =0 R,=Me; 1R.OMe 75 G1 H 0 Pr 0 1 Et H 2-pyridyl QCH; Q,=0
R
5 =Me R 4 =OMe 76 G7 H 0 cPr 0 1 Et H 2-pyridyl
Q
2 =0 ; R,=Me ; Y=0; R.=0Me 77 61 H 0 cPr 0 1 H H 2-quinolyl
Q
1 =CH; Q 2 =0
R
5 =Me; RK 6 OMe 78 G1 H 0 Me 0 1 H H 2-quinolyl Q.=C- Q 2 =o Rs=Me R,-OMe 79 G1 H 0 Me 0 1 H H N-oxido-2-pyridinio
Q.NQ
2 =0
R
5 =Me; R=0MeI -93 EX. Gn X, 1T, *j JV p A, Rj, A s0 GI H 0 Me 0 1 H H N-oxido-2-pyridinio Q,#4; Q 2 -0; Rk=Me -; R4-NHMe 81 01 H 0 cPr 0 1 H H N-oxido-2-pyridinio
Q
1 N; Q2=O R,=Me ; RA=OMc 82 G3 H 0 cPr 0 1 H H N-oxido-2-pyridinio Qi=0; R.=Me; RK=Me 83 G1 H 0 cPr 0 1 Et H N-oxido-2-pyridinio Q,=CH; Q2=0 R5=Me; R=OMe 84 G1 H 0 Me 0 1 Et H N-oxido-4-pyridinio Q H; Q 2 =0
R
5 =Me ; R 4 =OMe 85 01 H 0 cPr 0 1 Et H N-oxido-3-pyridinio
Q
1 =CH; Q2=0 R,=Me; R=0Me 86 G3 H 0 cPr 0 1 H H N-oxido-3-pyridinio
Q
2 =0; R,7-Me: R 4 =OMe 87 G3 H 0 cPr 0 1 Et H N-oxido-2-pyridinio R67Me -1R 4 =OMe 88 GI H 0 cPr 0 I Et H N-oxido-2-pyridinio Q,=N Q,=0 R,=Me ; R 4 -OMe 89 G1 H 0 cPr 0 1 Me H N-oxido-6-methyl-2-pyridinio
Q
1 N ; Q 2 =0
R
5 =Me; R,-0Me 90 GI H 0 cOr 0 1 Et H N-oxido-2-pyridinio Q=N ; Q 2 =0;
R
6 =Me; R 4 =NHMe -94 Gn E V~ 3 W p R, R 3 A 91 G4 H 0 cPr 0 1 Et H N-oxido-4-pyridinio
Q
2 0 ;n=O
R
5 =Me; R, 4 OMe 92 GI H 0 cPr 0 1 CN Me N-oxido-2-pyridinio Q,-N ; Q 2 =0 ; &=Me; RNHMe 93 GI H 0 cPr 0 1 Me H N-oxido-2-pyridinio Q,=N; Q 2 =O Rs=Me; R 4 =OMe 94 G4 H 0 cPr 0 1 Me H N-oxido-2-pyridinio Q,=0 n=O ]?,=Me ; R.-OMe 95 08 H 0 O~r 0 1 CN Me N-oxido-2-pyridinio Q,=0; Q.
4 N
R
9 =Me; R, 1 =OMe 96 GI H 0 Et 0 1 Me H N-oxido-2-pyridinio Q,=CH Q2=0
R
5 =Me; R 4 =OMe 97 G4 H 0 Et 0 1 Me H N-oxido-2-pyridinio
Q
2 0; n0 R,=Me; R 4 =OMe 98 GI H 0 ,Pr 0 1 Me H N-oxido-2-pyridinio Q,=CH4 Q 2 =0 R5=Me R.=0Me 99 G1 H 0 iPr 0 1 H H N-oxido-2-pyridinio Q,=CH; Q,=0
R
5 =Me R 4 =OMe l00 GI H 0 Et 0 1 H H NJ-oxido-2-pyridinio Q,=CH; Q 2 =0 R,=Me; R=OMe 101 G1 H 0 Pr 0 1 H H N-oxido-2-pyridinio Q,=CH;Q=
R
5 =Me; R 4 =OMe - 95 Er R, W 3 -W is w p R, R2 A 102 01 H 0 Me 0 1 Et H N-oxido-2-pyridinio
Q,--CH;Q
2 =0 Rs=Me; R=OMe 103 G1 H 0 Et 0 1 Et H N-oxido-2-pyridinio
Q
1 =CH ; Q 2 =O R,=Me R4=OMe 104 G1 H 0 iPr 0 1 Et H N-oxido-2-pyridinio Q,=CH;Q= R,=Me ; R 4 =OMe 105 01 H 0 Pr 0 1 Et H N-oxido-2-pyridinio QI-CH; Q 2 =0
R
5 =Mc ; R 4 =OMe 106 Gt H 0 cPr 0 1 Et H 2-methyl-4-thiazolyl Q,=CH ; Q 2 =0 R,=Me; R 4 -OMe 107 G1 H 0 Me 0 1 H H 1-pyrazolyl Q,=CH ; Q2=0 R,=Me; R 4 =OMe 108 G1 H 0 cPr 0 I H H 3,5-dimethyl-1-pyrazolyl
Q
1 =CH; Q 2 =0 R,=Me; R 4 =OMe 109 G01 H 0 cPr 0 1 H H I -pyrazolyl Q,=-CH4 Q,=
R
5 ,=Me ; R 4 =OMe 110 GI H 0 Me 0 1 H H 3,S-dimethyl-l-pyrazolyl
Q
1 =CH; Q 2 =0
R
5 =Me; R 4 =OMe III 01 H 0 Me 0 1 H H 4-bronio-3,5-dimethyl.- QI=CH; Q 2 0 pyrazolyl R,=Me R 4 =OMe 112 01 H 0 Me 0 1 H H 4-bromo-3,5-dimethyl-1
Q
1 =CI-; Q2=0 pyrazolyl Rs=Me R,=OMe -96 F. 'Gn X, -wI JR, .W p R, R, 2 A 113 GI H 0 cPr 0 I H 14 2-tliiazolyl QI'-CH ; Q2=0 Rs=Me; R4=OMe 114 GI H 0 iPr 0 1 H H 2-thiazolyl Q,=CH ; Q,=0 R3=Mc ; R,=0Mc 115 G0I H 0 Et 0 1 H H 2-thiazolyl Q,=CH; Q 2 =0
R
5 =Me ; R,-0Me 116 GI H 0 iPr 0, 1 Me H 2-thiazolyl
Q
3 =CH ; Q 2 =0 Rs=Me; R,-0Me 117 G1 H 0 Me 0 1 H H 2-oxo.1(211)-pyridyl
Q
1 -CH ; Q 2 =0
R
5 ,Me ; R,=0Me 11S G1 H 0 O~r 0 1 H H I -benzotriazolyl
Q
1 =CH; Q 2 =0 Rs=Me; Rt4=0Mc 119 G1 H 0 cPr 0 1 H H 2-oxo-1(211)-pyridyl Q,=CH; Q 2 =0 R,=Me; R 4 =OMe 120 03 H 0 cPr 0 1 H H 2-oxo-! I P)-pyridyl
Q
2 =0;
R
6 =Me; R 4 =-OMe 121 G1 H 0 cPr 0 1 H H 2-oxo-I(2H)-pyridyl
Q
1 =N ; Q 2 =0 R,=Me R 4 =OMe 122 01 H 0 iPr 0 1 Et H 2-thiazolyl
Q
1 =CH ; Q 2 =0 Rs=Me ; R,=OMe 123 GI H 0 cr 0 1 iPr H 2-pyrimidinyl Q=CH; Q 2 =0 R,=Me ; R,.OMe -97 Ex GnIK ', .Ri, W, P R, A, A 124 GI H 0 iPr 0 1 Me H 3-chloro-2-pyridyl
Q
2 =CH ; Q 2 =0 Rs=Me ; R4=0Me 125 GI H 0 iPr 0 1 Me H 3-chloro-2-pyridyl
Q,
1 N; Q, 2 =
R
5 =Me; R4=0Me 126 G1 H 0 iPr 0 1 Me H4 3-chloro-2-pyridyl Q,=CH; Q 2 =0 R,=Me; R 4 =OMe 127 61 H 0 iPr 0 1 Me H 3-chloro-2-pyridyl
Q
1 N; Q 2 =0 Rs=Me; R 4 =OMe 128 G3 H 0 Me 0 1 H H 2-oxo-I(2H)-pyridyl
Q
2 =0; R6=Me; &=Me 129 GI H 0 Me 0 1 H H 1-benzotriazolyl Q,=CH; %=0 Rs=Me ; R 4 =OMc 130 G3 H 0 Me 0 1 H H 1-benzotriazolyl
Q
2 =0; &=Me; ROMe 131 G1 H 0 Me 0 I H H 1-benzottiazolyl Q=N ; Q 2 =O Rs=Me ;R 4 =OMe 132 G1 H 0 cPr 0 1 Et H 2-pyrimidinyl
Q
1 =CH ; Qz=0 R,=Me R 4 =OMe 133 61 H 0 iPr 0 1 Et H 2-pyrimidinyl QI=CH; Q 2 =0 Rs=Me; R 4 ,OMe 134 G1 H 0 ePr 0 1 Et H 2-thiazolyl Q,=CH; Q 2 =0 Rs=Me ; R 4 =0Me -98 ExGn XW, R, IW 2 p P R Ri A 135 01 H 0 iPr 0 1 Me H 3-chloro-2-pyridyl
Q
1 =N ; %=O; &--Me; RY=NHMe 136 G1 H 0 iPr 0 1 iPr H 2-thiazolyl Q-'CH; Q 2 =0
R
5 t=Me ; R.=0Me 137 01 H 0 cPr 0 1 Me H 2-thiazolyl
Q
1
=CH;Q
2 0 Rs=Mc ; R.=0Me 138 G1 H 0 Et 0 1 H H 2-pyridyl QI=N; Q 2 =0
R
5 =Me; R 4 =OMe 139 01 H 0 Et 0 1 H H 2-pyridyl
Q
1 =N ; Q 2 =O;
R
4 =Me; R,=NHMe 140 G4 H 0 Et 0 1 H H 2-pyridyl
Q
2 =0 - n=0 Rs=Me ;, R4=0Mc 141 03 H 0 Et 0 1 H H 2-pyridyl
Q
2 =0; R,=Me R 4 =OMe 142 01 H 0 iPr 0 1 H H 2-quinolyl Q,=CH; 2
R
5 =Me; R.=OMe 143 G8 H 0 Et 0 1 H H 2-pyridyl Ql=0 ; Q 4 =N
R
9 =-Me; R,, 0 =OMe 144 04 H 0 Me 0 1 Et H 2-pyridyl
Q
2 =0; n=0 Rs=Me; l?,=OMe 145 G8 H 0 Me 0 1 Et H 2-pyridyl
Q
3 0o Q 4 =N R,=Me; R 10 =OMe -99 F Gn X, W* , 4. p A, R" A 146 G3 H 0 Me 0 1 Et H 2-pyridyl R,=Me; R 4 =OMe 147 GI H 0 Me 0 1 Et H 2-pyridyl Q=N; Q 2 =0O R,=Me; & 4 =OMe 148 GI H 0 Me 0 1 Me H 4-quinotyl Q,=CI-1 Q 2 =0 It =Me ;R 4 =OMe 149 GI H 0 sBu 0 1 Me H 2-thiazolyl Q,=CH; Q 2 =0 R5=Me R'0Me 150 GI H 0 Me 0 1 Et H 2-thiazolyl Q,=CH; Q 2 =0 R,=Me, R 4 =OMe 151 GI H 0 Me 0 1 Et H 2-pyridyl QI=N ; QY-O;
R
6 =Me; R=NHMe 152 G1I H 0 Et 0 1 Et H 2-pyridyl R,=Me; R4=0Me 153 G8 H 0 Et 0 1 Et H 2-pyridyl
Q
3 =0, Q.=N Rt=Me ; R,,=0Me 154 G4 H 0 Et 0 1 Et H 2-pyridyl
Q,
2 0 n0O
R
5 =Me; R.
4 =OMe 155 G1 H 0 Et 0 1 Et H 2-pyridyl QI=N ;Q 2 -O;
R
6 =Me R 4 =NHMe 156 G3 H 0 t 0 1 Et H 2-pyridyl
Q
2 0; &=Me; R 4 =OMe -100 'xGnv X,, AR W~ R, R.
157 GI H 0 cPr 0 1 Me H 3-chloro-5-triforomethyl-2 QI=CH ; Q 2 =0 pyridyl
R
5 =Me; R,=0Me 158 G I H 0 Me 0 1 Me H 3-chloro-5-trifuoromethyl-2 Q,-CH; Q,"'0 pyridyl Rs-Me, R=OMe 159 GI H 0 sBu 0 1 Et H 2-pyridyl
Q
1 =CH; Q,=0 Rs=Me; R,=Me 160 GI H 0 SBU 0 1 Et H 2-pyridyl QI=N ; Q 2 =0
R
3 =Me; R 4 =OMe 161 GI H 0 Pr 0 1 Et H 2-pyridyl
Q
1 =N -9 Q 2 =0 R,=Me R 4 =OMe 162 G1 H 0 cPr 0 1 Me H 2-thiazolyl Q,=N; Q 2 =0
R
5 =Me; R-0Me 163 G1 H 0 Me 0 1 iPr H 2-pyridyl Q,=CH; %=0 R,=Mc; R,=OMe 164 G4 H 0 Pr 0 1 Et H 2-pyridyl
Q
2 =0 n=0
R
5 =Me; R 4 =OMe 165 08 H 0 Pr 0 1 Et H 2-pyridyl
Q
3 =0 ; Q 4 =N R,=Me; R, 1 0 0Me 166 G1 H 0 Pr 0 1 Et H 2-pyridyl R6=Me: R4=NHMe 167 G1 H 0 sBu 0 1 Et H 2-pyridyl Q.=N, Q 2 =0 .
R
6 =Me ; R4=NHMe -101 EX. Gn X# J' ARf W 2 p R, R 2 -A. 169 01 H 0 nBu 0 1 Et H 2-pyridyl Q,=CH;Q0 R,=Me; R 4 =OMe 169 01 H 0 nBu 0 1 Et H 2-pyridyl
Q
1 -N ; Qi=O R5=Me; R 4 =-OMe 170 G4 H 0 nBu 0 1 Et H 2-pyridyl
Q
2 =0; n=0 Rs=Me ; R 4 =OMe 171 01 H 0 nBu 0 1 Et H 2-pyridyl Q,=N; ,O &=~Me ; R4=NHMe 172 01 H 0 cPr 0 1 H S,6,7,8-tetrahydro-8-quinolinyl
Q
1 =CH; Q 2 =0 Rs=Me; R.=OMe 173 G1 H4 0 cPr 0 1 H 6,7-dihydro-511
Q
1 =CH; Q 2 0 cyclopenta[b]pyridin-7-yl
R
3 =Me; R,=OMe 174 01 Cl 0 CPr 0 2 H Et 2-pyridyl
Q
1 =CH; Q 2 =0 R.,Me ; R,=OMe G2 H 0 cPr NMe I H Et 2-pyridyl 175 Q.=CH: Q,=0
R?
5 =Me ; R 4 =OMe G1 CF, 0 Me 0 1 H H 2-pyridyl 176 Q.=N; Q 2 =0
R
3 =Me; R 4 =OMe G1 OMe 0 Me 0 I H H 2-pyridyl 177 Q,-N; Q 2 =0;
R
6 =Me; R 4 =NHMe 01 Pr 0 cPr 0 1 H H 2-pyridyl 178 QI=CH ; Q 2 =0 Rs=Me; R,=OMe -102 Ex .Xn W, LRW 3 p R, A G5 H 0 cPr 0 1 H H 2-pyridyl 179 n=2; Q,=0 Rs=Me; ROMe G6 H 0 Pr NEt 2 H H 2-pyridyl 180 ,O R,=Me; R,-OMe 182 G1 cI S Et 0 2 Me H 2-pyridyl Q,=CH ; Q,=O
R
1 ,=Me; R 4 =OMe 183 G2 H S Ph 0 0 - -2-pyridyl QI0 ; Q 2 =S R,=Et; R.,OMe 184 64 H SO cPr 0 1 Me H 2-pyridyl %=O; n0O Rs=Me ; R 4 =OMe 185 GI cI 0 CPT 0 1 Me H 2-pyridyl Q,=N ;Q,=0:
R
6 =-Me ; R 4 =NHMe 186 G8 H 0 cPr 0 2 H H 2-pyridyl QI=O; Q4=N Rt,=Me; R,,=OMe 187 G4 H 0 cPr 0 1 CN Me 2-thiophenyl
Q
2 =O ; n=0
R
5 =Me; R,=OMe 188 G1 H 0 Me 0 1 Me H 2-quinolyl
Q
1 I=CH ; Q 2 =0 R,=Me R4OMe 189 G1 NO 2 0 Me 0 1 Me H 2-pyridyl Q=N; Q 2 =O Rs=Me; R.=OMe 190 G4 H 0 Me 0 1 Me H 3, -dimethyl-l-pyrazolyl
Q
2 ,"0; n0O
R
5 =Me; R 4 =OMe -103 Gn X wl' R., ~ p R R, A 191 G I CN 0 Me 0 1 Me Me I -benzotriazolyl
Q,
1 N; Q,=0; &-Me R 4 -NHMe 192 GS H 0 Et 0 1 Me H N-oxido-3-pyridinio n=1 ;Q 2 =S R,=Me R.=OEt 193 G9 H 0 Et 0 1 Me H 2-pyridyl
Q
3 =0 ; Q5=N R,=cPr; R,,=Me 194 G9 H 0 ipr 0 1 H H 2-thiazolyl
Q
3 =0 ; Q 5 =N R~qcPr; R 10 =Me 195 GS HI 0 Et 0 1 H H 2-thiazolyl Q,=0 Q.=N R,=-Me ; RO-=0Me 196 G4 H 0 iPr 0 1 Me H 2-thiazolyl Q=0 ; n0O R,=Me ; R-0Me 197 G7 H 0 Me 0 I H H 2-oxo-1(211)-pyridyl Y=NH; Q 2 0O
R
3 =Me; R 4 =0Me 198 G7 H 0 cPr 0 1 H H I -benzotriazolyl Y=NH4 Q 2 =0 R*=Me; R,=0Me 199 G7 H 0 cPr 0 1 H H 2-oxo-1(2H)-pyridyl Y=NH; Q2= R-Me; R.-OMe 200 G3 cI 0 cPr 0 2 H H 2 -oxo-l( 211 )-pyridyl R,=Me R,=OMe 201 GI CF, 0 He 0 1 H H 2 -oxo-I( 211 )-pyridyl Q=N ; Q 2 =0
R
5 =Me; R 4 =OMe -104 ExGa xi W, Rj Wp R, RI, A 202 GI H 0 iPr 0 1 Et H 2-benzitnidazolyl Q.=CH: Q 2 =0 R,=Me ;- R4=0Me 203 G I H 0 cPr 0 1 iPr Me 2-pyrimidinyl Q,=CH; Q,=0 R3=Me R4-0Me 204 GI H S iPr 0 1 Me H 3-chloro-2-pyridyl QI=CH ; Q 2 =S
R
1 ,=Me; k=0Me 205 G1 H 0 iPr 0 1 Me H 1,2,5-oxadiazolyl Q=N; Q,=0 R,=Mc R4=0Me 206 G1 H 0 iPr 0 1 Me H 8-purinyl Q,=CH; Q 2 =0
R
5 =Me ; R 4 =OMe 207 G1 H 0 iPr 0 1 Me H 2-pteridinyl Q,=N ;Q,=0 R,=Me; R 4 =QMe 208 G3 CI 0 Me 0 1 H H 4-pyridyl
Q
2 =0;
R
6 =Me; R,=OMe 209 G1 H 0 Me NPr 2 H H 1-benzotriazolyl
Q
1 =CH; Q 2 =0 Et,=Me; R.=OMe 210 G3 H S Me NH I H H I -benzotriazoiyl R67-Me -; R,=OMe 211 G I1 H S Me Net 2 H H 1-benzotriazolyl Q,=N Q,=O Rs=Me R 4 =OMe 212 G I CF, 0 cPr NH I Et H 2-pyrimidinyl
Q
1 =CH ; Q=O R,=Me R,=OMe -105 Gx n X~ H, WH, p, -it, RA 213 G) H 0 iPr NEt I Et Me 2-pyrimidinyl QI=CH; Q2=0 RkMe ; R 4 =OMe 214 GI H 0 cPr NWe I Et H 2-thiazolyl
Q
1 =N; Q 2 ,= Rs=Mc ; R4=0Et 215 GI H 0 iPr 0 2 H4 H 3-chloro-2-pyridyl
Q
1 -N; Q 2 -0; R,=Me -,R 4 =NHMe 216 G1 Cl 0 iPr 0 1 iPr H N-oxido-2-pyridinio
Q
1 =CH; Q2=0 Rs=Me; R4=0Me 217 G6 H 0 cPr 0 1 Me H 2-thiazolyl Q2=0
R
7 =Me ;R 4 =OMe 218 G6 H 0 Et 0 1 H H 2-pyridyl Q2=0 R7=Me ; R 4 =OMe 219 G I OCH, 0 Et 0 1 H H 2-pyridyl Q,=N Q 2 '=S; R,=Me; R 4 =NHMe 220 G4 H 0 Et 0 2 H H 2-pyridyl Q2=0; n0O R,=Me; R4=0Me 221 G3 H 0 Et 0 2 H H 2-pyridyl Qa=0;
R
6 =Me ; R&=0Me 222 GI H S cPr 0 1 H H 2-quinolyl
Q
1 =CH ;Q2=0
R
5 =Me, R 4 =OMe 223 G8 H 0 cPr 0 2 H H 2-pyridyt Q3=0 ; Q.=N &~=Me; R =0Me -106 Ga~~~X R~fr Wi 3 p , z 224 G4 H 0 Me 0 1 Et H N-oxido-2-pyridinio
Q
2 =0 ; n=1 R,=Et; R=OMe 225 G8 H 0 Me NPr I Et H 2-pyridyl Q3=O; Q 4 =N &=Me; R 10 =OMe 226 G3 OCH 3 0 Me NH I Et H 2-pyridyl R6=Me ; R4=OMe 227 G1 H SO, Me 0 1 Et H 2-pyridyl Q,=N ; Q 2 =0 R,=Me; R=OMe 228 G1 H4 SO Me 0 1 Me H 4-quinolyl QI-CH; Q 2 -0 R,=Me; R 4 =OMe 229 G1 H SO sBu 0 1 Me H 2-thiazolyl Q,=CH;Q= Rs=Me; R=OMe 230 GI CI 0 Me NEt I Et H 2-thiazolyl
Q
1 =CH; Q,=O Rs=Me; R 4 =OMe 231 01 H SO, Me 0 1 Et H 2-pyridyl QI=N; 20
R
6 =Me; R,=NHMe 232 01 OCH 3 0 Et 0 1 Et H 2-quinolyl QI=N ; Q 2 =O Rs=Me; R 4 =OMe 233 G8 H 0 Et 0 1 Et H 2-quinolyl Q3-0; Q 4 =N &=Et; R,,OMe 234 G4 H 0 Et NMe I Et H N-oxido-2-pyridinio
Q
2 =O; n=0 Rs=Me; R,=OMe - 107 Table of physicochemical analyses of the compounds m.p.: melting point (0C) nD: refractive index (measurement temperature *C) Rf: elution ratio 5 M: Molecular peak Example No. Physicochemical analysis 1 m.p. = 63 0 C 2 nD = 1.5710 (24.0*C) 3 nD = 1,5300 (24.5*C) 4 nD = 1.5320 (25.7*C) 5 nD = 1.5357 (26.1*C) 6 nD = 1.5266 (23.3*C) 7 nD= 1.5277 (23.9*C) 8 nD= 1.5244 (25.6*C) 9 nD = 1.5366 (24.0*C) 10 nD = 1.5438 (24.2*C) 11 m.p.= 95*C 12 nD = 1.5629 (21.2*C) 13 Rf= 0.41 (30/70 heptane/ethyl acetate) 14 m.p.= 76*C 15 no = 1.5605 (21.4*C) 16 nD = 1.5435 (21.5*C) 17 syrup 18 m.p.= 68*C 19 nD = 1.5610 (23*C) 20 syrup 21 nD = 1.5560 (230C) 22 nD=1.5640 (23*C) - 108 Example no. Physicochemical analysis 23 syrup 24 nD = 1.5540 (24*C) 25 syrup 26 nD = 1.5562 (24*C) 27 nD = 1.5460 (24*C) 28 nD = 1.5590 (24*C) 29 n= 1.5640 (24*C) 30 nD = 1.5528 (23*C) 31 n= 1.5500 (23*C) 32 m.p. = 76*C 33 syrup 34 nD = 1.5410 (22*C) 35 nD = 1.5356 (24*C) 36 m.p.= 72*C 37 nD = 1.5555 (23*C) 38 nD = 1.5558 (23*C) 39 nD = 1.5320 (23*C) 40 nD = 1.5520 (23*C) 41 syrup 42 syrup 43 syrup 44 nD = 1.5408 (21*C) 45 m.p. = 56*C 46 Rf= 0.24 (50/50 hept/EtOAc) 47 syrup 48 nD = 1.5560 (24.7 *C) 49 nD = 1.5520 (24.7 'C) - 109 Example no. Physicochemical analysis 50 nD = 1.5450 (24.6 *C) 51 nD = 1.5470 (25.0 *C) 52 Rf - 0.48 (AcOEt :100) 53 Rf= 0.42 (50/50 hept/EtOAc) 54 n, = 1.5520 (25.5 *C) 55 n= 1.5430 (25.6 *C) 56 n,= 1.5350 (25.7 *C) 57 nD = 1.5460 (25.8 *C) 58 nD = 1.5490 (25.2 *C) 59 nD = 1.5310 (25.3 *C) 60 m.p.= 92*C 61 nD = 1.5600 (26.6 *C) 62 nD = 1.5600 (24.8 *C) 63 nD = 1.5490 (19.3 *C) 64 n, = 1.5450 (19.1 *C) 65 m.p. = 64*C 66 nD= 1.5600 (20.5 *C) 67 n, = 1.5530 (20.5 *C) 68 nD = 1.5500 (20.6 *C) 69 nD = 1.5550 (20.7 *C) 70 no = 1.5470 (20.8 *C) 71 nD 1.5570 (25.4 *C) 72 no = 1.5480 (24.5 *C) 73 nD = 1.5460 (24.6 *C) 74 no = 1.5390 (24.6 *C) 75 nD = 1.5410 (24.5 *C) 76 Rf= 0.59 (30/70 hept/EtOAc) - 110 Example no. Physicochemical analysis 77 nD = 1.5940 (25.1 *C) 78 nD = 1.5910 (25.1 *C) 79 M = 387 80 M=386 81 M=413 82 M = 396 83 M=440 84 M=414 85 M = 440 86 M=396 87 M=424 88 M = 441 89 M=441 90 M = 440 91 M=429 92 M=451 93 M = 427 94 M=415 95 M=464 96 M = 414 97 M=403 98 M=428 99 M=414 100 M=400 101 M=414 102 M = 414 103 M=428 - 111 Example no. Physicochemical analysis 104 M=442 105 M=442 106 nD= 1.5530 (25 *C) 107 Rf= 0.52 (EtOAc : 100) 108 m.p. - 108*C 109 m.p.=89*C 110 m.p.=132*C ill m.p.= 120*C 112 m.p.= 120*C 113 syrup 114 nD = 1.5480 (25.1 *C) 115 nD = 1.5620 (24.2 *C) 116 nD = 1.5480 (24.5 *C) 117 m.p.= 120*C 118 m.p. = 148*C 119 Rf = 0.20 (EtOAc :100) 120 Rf = 0.34 (EtOAc :100) 121 Rf= 0.27 (EtOAc :100) 122 n, = 1.5430 (22 *C) 123 nD = 1.5250 (24 00) 124 nD 1.5500 (25.3 *C) 125 nD= 1.5430 (25.5 *C) 126 n= 1.5470 (25.6 *C) 127 nD= 1.5430 (25.6 C) 128 m.p. =92 0 C 129 m.p.= 142*C 130 syrup - 112 Example no. Physicochemical analysis 131 m.p. = 132*C 132 nD = 1.5190 (25.0 *C) 133 no = 1.5260 (25.0 *C) 134 m.p. = 72*C 135 nD = 1.5530 (25.2 *C) 136 nD = 1.5380 (27 *C) 137 nD = 1.5610 (27 *C) 138 nD= 1.5460 (25 *C) 139 nD = 1.5560 (25 *C) 140 nD = 1.5380 (25 *C) 141 nD = 1.5420 (25 *C) 142 Rf = 0.43 (50/50 hept/EtOAc) 143 nD = 1.5510 (24 *C) 144 nD = 1.5340 (24.8 *C) 145 nD = 1.5440 (24.9 *C) 146 nD = 1.5410 (24.7 *C) 147 nD = 1.5410 (23.5 *C) 148 nD= 1.5690 (23 *C) 149 nD = 1.5270 (23 *C) 150 nD = 1.5530 (22.8 *C) 151 nD = 1.5500 (23.2 *C) 152 nD= 1.5290 (23 *C) 153 nD = 1.5290 (23 *C) 154 nD = 1.5240 (23 'C) 155 nD = 1.5440 (23 *C) 156 nD = 1.5240 (23 *C) - 113 Example no. Physicochemical analysis 157 m.p. = 140 *C 158 nD = 1.5290 (25.5 *C) 159 nD = 1.5180 (23 *C 160 nD = 1.5260 (24 *C) 161 nD = 1.5180 (24 *C) 162 nD = 1.5330 (23.4 *C) 163 nD = 1.5360 (23.6 *C) 164 nD = 1.5240 (23 *C) 165 nD = 1.5310 (23 *C) 166 nD = 1.5340 (23 *C) 167 nD = 1.5300 (23 *C) 168 nD = 1.
5 3 10 ( 2 3 *C) 169 nD = 1.5300 (23 *C) 170 nD = 1.5230 (23 *C) 171 nD = 1.5350 (23 *C) 172 nD = 1.5565 (23.8 0 C) Example Bl: in vivo test on Puccinia recondita (wheat rust): 5 An aqueous suspension of the active material to be tested, having the composition below, is prepared by fine grinding: - active material: 60 mg - surfactant Tween 80 (polyoxyethylenated 10 derivative of sorbitan oleate) diluted to 10% in water: - 114 0.3 ml - acetone: 5 ml - completion to 60 ml with water. This aqueous suspension is then diluted with 5 water so as to obtain the desired concentration in ppm (parts per million). Wheat (Scipion variety) in plant pots, sown on a 50/50 pozzolana earth peat substrate and maintained at 120C, is treated at the 1-leaf stage 10 (height of 10 cm) by spraying with the above aqueous suspension. In this example, and in the following Examples B2 to B7, plants, used as controls, are treated with an aqueous solution which does not contain 15 the active material. After 24 hours, each plant is contaminated by spraying with an aqueous suspension of spores (150,000 spores per cm 3 ) of Puccinia recondita. This suspension is obtained from contaminated plants. 20 The contaminated wheat plants are then incubated for 24 hours at about 200C, in an atmosphere of saturated humidity and then for seven to fourteen days at 60% relative humidity. Reading is carried out between the 8th and 25 the 15th day after the contamination, by comparison with the control plants. In this example and in the following Examples B2 to B7, the results observed, under these conditions, - 115 at a dose of 40 ppm, for good (at least 75%) or total protection are given in the table of results which follows. Example B2: in vivo test on Septoria tritici 5 (septoria disease in wheat): An aqueous suspension of the active material to be tested is prepared, as in Example Bl. Wheat (Scipion variety) in plant pots, sown on a 50/50 pozzolana earth peat substrate and 10 maintained at 120C, is treated at the 1-leaf stage (height of 10 cm) by spraying with the above aqueous suspension. After 24 hours, each plant is contaminated by spraying with an aqueous suspension of spores (500,000 15 spores per cm 3) of Septoria tritici. The spores are harvested from a seven-day-old culture. The contaminated wheat plants are incubated for 72 hours at about 200C, in a humid atmosphere and then for twenty days at 90% relative humidity. 20 Reading is carried out twenty-one days after the contamination, by comparison with the control plants. Example B3: in vivo test on Septoria nodorum (septoria disease in wheat): 25 An aqueous suspension of the active material to be tested is prepared as in the previous Example Bl. Wheat (Scipion variety) in plant pots, sown on a 50/50 pozzolana earth peat substrate and - 116 maintained at 120C, is treated at the 1-leaf stage (height of 10 cm) by spraying with the above aqueous suspension. After 24 hours, each plant is contaminated by 5 spraying with an aqueous suspension of spores (500,000 spores per cm 3) of Septoria nodorum. The spores are harvested from a seven-day-old culture. The contaminated wheat plants are incubated for 72 hours at about 200C, in a humid atmosphere and 10 then for fourteen days at 90% relative humidity. Reading is carried out fifteen days after the contamination, by comparison with the control plants. Example B4: in vivo test on Erisyphe graminis fsp tritici (powdery mildew in wheat): 15 An aqueous suspension of the active material to be tested is prepared as in Example Bl. Wheat (Audace variety) in plant pots, sown on a 50/50 pozzolana earth peat substrate and maintained at 120C, is treated at the 1-leaf stage (height of 20 10 cm) by spraying with the above aqueous suspension. After 24 hours, the wheat plants are sprinkled with spores of Erisyphe graminis, the sprinkling being carried out using diseased plants. Reading is carried out seven to fourteen days 25 after the contamination, by comparison with the control plants. Example B5: in vivo test on Erisyphe graminis fsp hordes (powdery mildew in barley): - 117 An aqueous suspension of the active material to be tested is prepared as in the previous Example Bl. Barley (Express variety) in plant pots, sown on a 50/50 pozzolana earth peat substrate and 5 maintained at 12 0 C, is treated at the 1-leaf stage (height of 10 cm) by spraying with the above aqueous suspension. After 24 hours, the barley plants are sprinkled with spores of Erisyphe graminis, the 10 sprinkling being carried out using diseased plants. Reading is carried out seven to fourteen days after the contamination, by comparison with the control plants. Example B6: in vivo test on Pyrenophora teres 15 (net blotch in barley): An aqueous suspension of the active material to be tested is prepared as described in Example Bl. Barley (Express variety) in plant pots, sown on a 50/50 pozzolana earth peat substrate and 20 maintained at 120C, is treated at the 1-leaf stage (height of 10 cm) by spraying with the above aqueous suspension. After 24 hours, each plant is contaminated by spraying with an aqueous suspension of spores (12,000 25 spores per cm3) of Pyrenophora teres. This suspension is obtained from contaminated plants. The contaminated barley plants are then incubated for 24 hours at about 200C, in an atmosphere - 118 of saturated humidity and then for seven to fourteen days at 80% relative humidity. Reading is carried out between the 8th and the 15th day after the contamination, by comparison 5 with the control plants. Example B7: in vivo test on Rynchosporium secalis (leaf blotch in barley); An aqueous suspension of the active material to be tested is prepared as described in Example Bl. 10 Barley (Express variety) in plant pots, sown on a 50/50 pozzolana earth peat substrate and maintained at 12*C, is treated at the 1-leaf stage (height of 10 cm) by spraying with the above aqueous suspension. 15 After 24 hours, each plant is contaminated by spraying with an aqueous suspension of spores (800,000 spores per cm 3 ) of Rynchosporium secalis. This suspension is obtained from contaminated plants. The contaminated barley plants are then 20 incubated for 24 hours at about 200C, in an atmosphere of saturated humidity and then for seven to fourteen days at 80% relative humidity. Reading is carried out between the 8th and the 15th day after the contamination, by comparison 25 with the control plants.
- 119 Table of test results The sign "+" indicates a protection ranging from 75% to 100%. Example no. BI B2 B3 B4 B5 B6 B7 1 + + + + + 2 + + + + + + + 3 + + + + + + 4 + + + + + 5 + + + 6 + + + + 7 + + + 8 + + + + 9 + + + + + + 11 + + + - 120 Example no. BI B2 B3 B4 B5 B6 B7 12 + + 17 + + + + 18 + + + + 19 + + + + + 20 + + + + + + + 21 +- + + + + + 22 + + + + + + 23 + + + + + 24 + + + + + 25 + + + + 26 + + + 28 + + + + 30 + + 31 + 32 + 34 + + + 35 + + + + 36 + + + + + 37 + + + + + 38 + 39 + + + + 40 + + + + + 41 + + 42 + + 44 + + 45 + + + 46 + + 47 + + 48 + + ++ 49 + + + 50 + + + + - 121 Example no. BI B2 B3 B4 B5 B6 B7 51 + + + + 52 + +4 53 + + + 54 + + + 55 + + + 56 + + + + 57 + 58 + + + + + + 59 + + + 60 + + + 61 + + + 62 + + + + + 63 + + + 64 + + + 65 + + + + + 66 + 67 68 + + +- + 69 + + + 1 70 + + +4 + 71 + + + + + 72 + + + + 73 + + + + 74 + + 75 + + 76 + + 77 + + + + 78 + + + 79 + + 80 + + 82 + + - 122 Example no. BI B2 83 B4 B5 B6 B7 83 + + + + 24 + + 85 + + 86 + 87 + 90 + 93 + 94 + 96 + + + 97 + + 98 + 99 + + + 100 + 101 + 102 + + 103 + 104 + 105 + 106 + + + + + 107 + 108 + + - + 109 + + + 110 + + 112 + + + + 113 + + + + + 114 + + + + + 115 + + + +4 116 + + + + 117 + 118 + + 119 + + - 123 Example no. BI B2 B3 B4 B5 B6 B7 122 + + + + + 123 + + 126 + + + + + + 127 + + + 129 + + 132 + + 133 + 134 + + + + + 135 + + + + 136 + + + + + 137 + + + + + 138 + + 139 + 140 + + + 141 + + + 142 + 143 + + 144 + + + 145 + + 146 + ++ 147 + + 148 + + + + 149 + + + + 150 + + + +

Claims (25)

1. Compounds of general formula (I): V-4 1 W1 2R,A G 3 2G (I) 5 in which G is chosen from the groups G1 to G9: R 5 0 , ,R S.I IR 4R - ) 4 GI 2 G2 02 G3 02 R 6 0,,R Rs-S. I I (CH 2 )n (CH 2 )n R7 02 02 02 G4 G5 G6 10 Ri Q3 Rio Q3 02 --- - N G7 G8 G9 - 125 in which: n represents 0 or 1 Qi is a nitrogen atom or a CH group, Q2 is an oxygen or sulphur atom, 5 Q3 is an oxygen or sulphur atom, Q4 is a nitrogen atom or a group CR 11 , Q5 is an oxygen or sulphur atom or a group NR 12 , Y is an oxygen or sulphur atom or an amino (NH) or oxyamino (ONH) group 10 Wi is an oxygen or sulphur atom or a sulphinyl (SO) or sulphonyl (SO 2 ) group, W 2 is an oxygen atom or a group NR 13 , p represents 0, 1 or 2, A represents a mono- or bicyclic aromatic 15 heterocyclic radical containing from 5 to 10 atoms, among which 1 to 4 are hetero atoms chosen from oxygen, sulphur and nitrogen atoms, each sulphur or nitrogen atom optionally being in the oxidized state in the form of an N-oxide or sulphoxide group, this radical being 20 attached to the carbon atom substituted with the groups R 1 and R 2 in the case where p = 1 or p = 2, or attached to the group W 2 in the case where p = 0, with a carbon or nitrogen atom, and this radical optionally being substituted with 1 to 5 radicals Xi and/or X 2 and/or X 3 25 and/or X 4 and/or X 5 , preferably with 1 to 3 radicals Xi and/or X 2 and/or X 3 , X 1 , X 2 , X 3 , X 4 and X 5 are, independently of each other, a hydrogen atom, a halogen atom; or - 126 a hydroxyl, mercapto, nitro, thiocyanato, azido, cyano or pentafluorosulphonyl group; or a lower alkyl, lower haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkoxyalkyl, 5 haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, cyanoalkyl, cyanoalkoxy, cyanoalkylthio, alkylsulphinyl, haloalkylsulphinyl, alkylsulphonyl, haloalkylsulphonyl or alkoxysulphonyl group; or a lower cycloalkyl, lower halocycloalkyl, 10 alkenyl, alkynyl, alkenyloxy, alkynyloxy, alkenylthio or alkynylthio group; or an amino, N-alkylamino, N,N-dialkylamino, acylamino, aminoalkyl, N-alkylaminoalkyl, N,N dialkylaminoalkyl or acylaminoalkyl group; or 15 an acyl, carboxyl, carbamoyl, N-alkylcarbamoyl, N,N-dialkylcarbamoyl or lower alkoxycarbonyl group; the radical Xi optionally forming a 5- to
7-membered ring with R 1 3 in the case where W 2 is a group NR 13 , or a 5- to 7-membered ring with R 1 in the case 20 where p = 1, or a 5- to 7-membered ring with R' 1 in the case where p = 2; X 6 is a hydrogen atom, a halogen atom; or a lower alkyl, lower haloalkyl, alkoxy or haloalkoxy group; or 25 cyano or nitro radicals, R 1 and R 2 are, independently of each other, a hydrogen atom, a lower alkyl or lower haloalkyl group, a lower cycloalkyl or lower halocycloalkyl group, an - 127 alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl or cyanoalkyl group; or a cyano, acyl, carboxyl, carbamoyl, N-alkylcarbamoyl or N,N-dialkylcarbamoyl group, a lower 5 alkoxycarbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl or alkylthiothiocarbonyl group; or an aminoalkyl, N-alkylaminoalkyl, N,N dialkylaminoalkyl or acylaminoalkyl group, or 10 R 1 and R 2 together can form a divalent radical such as an alkylene group, optionally substituted with one or more halogen atoms, or optionally substituted with one or more lower alkyl groups, R 3 is a hydrogen atom, a lower alkyl or lower 15 haloalkyl group, a lower cycloalkyl or lower halocycloalkyl group, an alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl or cyanoalkyl group; or 20 a nitro, cyano, acyl, carboxyl, carbamoyl, N-alkylcarbamoyl, N,N-dialkylcarbamoyl, lower alkoxycarbonyl, 3-oxethanyloxycarbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl or 25 alkylthiothiocarbonyl group; or an alkenyl, alkynyl, N,N-dialkylamino or N,N dialkylaminoalkyl group; or an optionally substituted phenyl or benzyl - 128 group, R 4 is a lower alkyl or lower haloalkyl group, a lower cycloalkyl, lower halocycloalkyl or alkoxyalkyl group; or 5 an alkoxy, haloalkoxy, alkylthio, alkylamino or dialkylamino group, R 5 and R 6 represent, independently of each other, a lower alkyl or lower haloalkyl group, R7 is a lower alkyl, lower haloalkyl, 10 alkoxyalkyl, haloalkoxyalkyl, alkenyl or alkynyl group, R 8 is a lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl, formyl or acyl group, R 9 is a hydrogen atom, a lower alkyl or lower 15 haloalkyl group or a lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl or alkynyl group, R 10 is a halogen atom, a lower alkyl or lower haloalkyl group, a lower cycloalkyl or lower 20 halocycloalkyl group or an alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulphinyl, haloalkylsulphinyl, alkylsulphonyl or haloalkylsulphonyl group, R 11 and R 12 are, independently of each other, a 25 hydrogen atom, a lower alkyl or lower haloalkyl group or a lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl or alkynyl group, R 13 is a hydrogen atom, a lower alkyl or lower - 129 haloalkyl group, a lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl or haloalkylthioalkyl group, an optionally substituted allyl group, an optionally 5 substituted propargyl group or an optionally substituted benzyl group; or an acyl, N-alkylcarbamoyl, N,N dialkylcarbamoyl, lower alkoxycarbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, 10 alkoxythiocarbonyl, haloalkoxythiocarbonyl or alkylthiothiocarbonyl group; or an alkylsulphonyl, haloalkylsulphonyl or optionally substituted arylsulphonyl group, Q2 and R 4 can together form a ring of 5 to 7 15 atoms containing 2 to 3 oxygen and/or nitrogen atoms, optionally substituted with one or more radicals, such as a halogen or a lower alkyl or lower haloalkyl group, as well as the salts and the metal and metalloid complexes of the compounds of formula (I) as 20 have just been defined. 2. Compounds according to Claim 1, which have one or more of the following characteristics, taken separately or in combination: 25 n is equal to 0; p is equal to 0, 1 or 2; Q2 is an oxygen atom, and/or Q3 is an oxygen atom, and/or Q4 is a nitrogen atom, and/or Q5 is an - 130 oxygen atom; W 1 is an oxygen or sulphur atom W 2 is an oxygen atom or an alkylamino, haloalkylamino, alkoxyalkylamino or allylamino group, 5 Y is an oxygen atom, Xi, X 2 , X 3 , X 4 , X 5 and X 6 are, independently of each other, a hydrogen atom, a lower alkyl group, a halogen atom or cyano, trifluoromethyl, methoxy or nitro radicals, 10 R 1 and R 2 are, independently of each other, a hydrogen atom, a lower alkyl, lower cycloalkyl, lower haloalkyl, alkoxyalkyl, cyano, cyanoalkyl, N-alkylaminoalkyl, N,N-dialkylaminoalkyl, acylaminoalkyl, lower alkoxycarbonyl, N-alkylcarbamoyl 15 or N,N-dialkylcarbamoyl group, R 3 is a hydrogen atom, a lower alkyl, lower cycloalkyl, lower haloalkyl or alkoxyalkyl group, preferably a methyl, ethyl, propyl, isopropyl, cyclopropyl or methoxymethyl radical, 20 R 4 is a lower alkyl, alkoxy, alkylamino or dialkylamino group, preferably a methyl, ethyl, propyl, methoxy, ethoxy, methylamino or ethylamino radical, R 5 , R 6 , R 8 and R 9 are, independently of each other, a lower alkyl or lower haloalkyl group, 25 preferably a methyl, fluoromethyl, difluoromethyl, trifluoromethyl, ethyl, 2,2,2-trifluoroethyl or propyl radical, R 7 is a lower alkyl or lower haloalkyl group, - 131 preferably a methyl, fluoromethyl, difluoromethyl, trifluoromethyl, ethyl, 2,2,2-trifluoroethyl or propyl radical, or an allyl or propargyl group, R 10 is a chlorine atom, a lower alkyl or lower 5 haloalkyl group, preferably methyl, or an alkoxy or alkylthio group, preferably methoxy or methylthio, R 11 and R 1 2 are, independently of each other, a lower alkyl, lower haloalkyl, alkoxyalkyl, allyl or propargyl group, 10 R 13 is a hydrogen atom or a lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, allyl, propargyl or benzyl group. A is chosen from a radical, optionally substituted with 1 to 5 radicals Xi and/or X 2 and/or X 3 15 and/or X 4 and/or X 5 , preferably with 1 to 3 radicals Xi and/or X 2 and/or X 3 , derived, by removal of a hydrogen atom, from one of the rings (i) to (v) below: - a 5-membered ring described by formula (i): B2 B4 20 (i in which each of the groups of the list B 1 , B 2 , B3 and B 4 is chosen from carbon, nitrogen, oxygen and sulphur atoms such that the said list comprises from 0 25 to 3 carbon atoms, 0 or 1 sulphur atom, 0 or 1 oxygen - 132 atom and from 0 to 4 nitrogen atoms; or alternatively - a 6-membered ring described by formula (ii): I (ii) 5 1 2 in which each of the groups of the list D', D2 D , D and D5 is chosen from carbon and nitrogen atoms such that the said list comprises from 1 to 4 carbon atoms and from 1 to 4 nitrogen atoms; or alternatively, 10 - two fused rings, each 6-membered, described by formula (iii): -E4 E E F E ~OEE E E 8 (iii) 15 in which each of the groups of the list El, E 2 E 3 , E 4 , E 5 , E 6, E 7 and E 8 is chosen from carbon and nitrogen atoms such that the said list comprises from 4 to 7 carbon atoms and from 1 to 4 nitrogen atoms; or alternatively 20 - a 6-membered ring and a 5-membered ring fused together, described by formula (iv): - 133 5 (iv) in which: - each of the groups of the list J 1 , J 2 3 4 J5 and J6 is chosen from carbon and nitrogen atoms such 5 that the said list comprises from 3 to 6 carbon atoms and from 0 to 3 nitrogen atoms; and - each of the groups of the list L', L 2 and L 3 is chosen from carbon, nitrogen, oxygen and sulphur atoms such that the said list comprises from 0 to 3 10 carbon atoms, 0 or 1 sulphur atom, 0 or 1 oxygen atom and from 0 to 3 nitrogen atoms; and - each of the groups of the list J 1 , J2, 3, 4 J , J 6, L , L2 and L3 is chosen such that the said list comprises from 3 to 8 carbon atoms; or alternatively 15 - two fused rings, each 5-membered, described by formula (v): (v) 20 in which: - each of the groups of the list M , M2 and M 3 represents carbon, nitrogen, oxygen or sulphur atoms - 134 such that the said list comprises from 0 to 3 carbon atoms, 0 or 1 sulphur atom, 0 or 1 oxygen atom and from 0 to 3 nitrogen atoms; - each of the groups of the list T', T2 and T 3 5 represents carbon, nitrogen, oxygen or sulphur atoms such that the said list comprises from 0 to 3 carbon atoms, 0 or 1 sulphur atom, 0 or 1 oxygen atom and from 0 to 3 nitrogen atoms; - Z represents a carbon or nitrogen atom; 1 2 3 1 10 - each of the groups of the list M1, M , M , T T2 and T 3 is chosen such that the said list comprises from 0 to 6 carbon atoms; as well as the salts and metal and metalloid complexes thereof. 15 3. Compounds according to Claim 1 or 2, which have one or more of the following characteristics, taken separately or in combination: Wi is an oxygen atom, R 1 is a hydrogen atom or a methyl radical, 20 R 2 is a hydrogen atom or a lower alkyl, cyano, cyanoalkyl, alkoxyalkyl, N,N-dialkylaminoalkyl, lower alkoxycarbonyl or lower N,N-dialkylcarbamoyl group, A represents a heterocyclic radical, optionally substituted with 1 to 5 radicals X 1 and/or X 2 25 and/or X 3 and/or X 4 and/or X 5 , preferably with 1 to 3 radicals X 1 and/or X 2 and/or X 3 as defined above, A being chosen from the following list: - furyl; pyrrolyl; thiophenyl; - 135 - pyrazolyl; imidazolyl; oxazolyl; isoxazolyl; thiazolyl; isothiazolyl; 1,2,3-oxadiazolyl; 1,2,4-oxadiazolyl; 1,2,5-oxadiazolyl; 1,3,4-oxadiazolyl; 5 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; 10 - 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; 15 benzoxazolyl; 1,2-benzisoxazolyl; 2,1-benzisoxazolyl; benzothiazolyl; 1,2-benzisothiazolyl; 2,1-benzisothiazolyl; 1,2,3-benzoxadiazolyl; 1,2,5-benzoxadiazolyl; 20 1,2,3-benzothiadiazolyl; 1,2,5-benzothiadiazolyl; - quinolyl; isoquinolyl; - quinoxazolinyl; quinazolinyl; cinnolyl or phthalazyl; pteridinyl; benzotriazinyl; 25 - 1,5-naphthyridinyl; 1,6-naphthyridinyl; 1,7-naphthyridinyl; 1,8-naphthyridinyl; - imidazo[2,1-b]thiazolyl; thieno[3,4-b]pyridyl; purine; - 136 pyrrolo[1,2-bJthiazolyl, as well as the salts and metal and metalloid complexes thereof. 4. Compounds according to any one of Claims 5 1 to 3, which have the following characteristics: W 1 is an oxygen atom, R 1 is a hydrogen atom or a methyl radical, R 2 is a hydrogen atom or a lower alkyl, cyano, cyanoalkyl, alkoxyalkyl, N,N-dialkylaminoalkyl, lower 10 alkoxycarbonyl or lower N,N-dialkylcarbamoyl group, A, optionally substituted with 1 to 5 radicals Xi and/or X 2 and/or X 3 and/or X 4 and/or X 5 , preferably with 1 to 3 radicals X1 and/or X 2 and/or X 3 , is chosen from one of the following heterocycles 15 - pyridyl; - pyridazinyl; pyrimidinyl; pyrazinyl; 1,3,5-triazinyl; 1,2,4-triazinyl; - quinolyl; isoquinolyl; - furyl; pyrrolyl; thiophenyl; 20 - oxazolyl; isoxazolyl; thiazolyl; isothiazolyl; imidazolyl; pyrazolyl, as well as the salts and metal and metalloid complexes thereof. 5. Compounds according to any one of Claims 25 1 to 4, which have the following characteristics: W 1 is an oxygen atom, Ri is a hydrogen atom or a methyl radical, R 2 is a hydrogen atom or a lower alkyl, cyano, - 137 cyanoalkyl, alkoxyalkyl, N,N-dialkylaminoalkyl, lower alkoxycarbonyl or lower N,N-dialkylcarbamoyl group, A, optionally substituted with 1 to 5 radicals X, and/or X 2 and/or X 3 and/or X 4 and/or X 5 , preferably 5 with 1 to 3 radicals X, and/or X 2 and/or X 3 , represents a pyridyl radical; as well as the salts and metal and metalloid complexes thereof. 6. Compounds according to any one of Claims 10 1 to 5, for which G is chosen from G1, G2 and G3. 7. Compounds according to any one of Claims 1 to 5, for which G represents Gl.
8. Compound according to any one of Claims 1 to 7, chosen from: 15 - methyl (E,E)-2-(2-{1-[(2 pyridyl)methyloxyimino]-1-cyclopropylmethyloxy methylIphenyl)-3-methoxypropenoate, - methyl (E,E)-2-(2-{l-[1-(2 pyridyl)propyloxyimino]-1-cyclopropylmethyloxy 20 methyl}phenyl)-3-methoxypropenoate, - methyl (E,E)-2-(2-{1-[1-(2 pyridyl)propyloxyimino]propyloxymethyl}phenyl)-3 methoxypropenoate, and - methyl (E,E)-2-(2-{1-[1-(2-pyridyl)propyloxy 25 imino]isobutyloxymethyl}phenyl)-3-methoxypropenoate, as well as the salts and metal and metalloid complexes thereof.
9. Fungicidal compositions containing, as - 138 active material, an effective quantity of at least one compound of formula (I) or one of its agriculturally acceptable salts or a metal or metalloid complex of this compound which is also agriculturally acceptable 5 according to any one of the preceding claims.
10. Fungicidal compositions according to Claim 9 comprising, besides the active material of formula (I) or one of its agriculturally acceptable salts or a metal or metalloid complex of this compound 10 which is also agriculturally acceptable, a solid or liquid support, which is agriculturally acceptable, and/or a surfactant which is also agriculturally acceptable.
11. Fungicidal compositions according to 15 either of Claims 9 and 10, comprising from 0.05 to 95% by weight of active material.
12. Process for preventively or curatively controlling the phytopathogenic fungi of crops, characterized in that the seeds, the leaves or the 20 trunks of plants or the soils where these plants grow or are likely to grow are treated by applying, spraying or injecting an agronomically effective and non phytotoxic quantity of at least one compound of formula (I) or one of its agriculturally acceptable salts or a 25 metal or metalloid complex of this compound which is also agriculturally acceptable or of a fungicidal composition comprising an active material of formula (I) as defined in any one of Claims 1 to 8. - 139 13. Process for preventively or curatively treating plant multiplication products, as well as the plants resulting therefrom, against fungal diseases, characterized in that the said products are coated with 5 an effective and non-phytotoxic dose of compound or of composition according to one of the preceding claims.
14. Process according to Claim 13, in which cereals, rice, fruit trees, woodland trees, grapevine, oleaginous crops, market garden crops, solanaceous 10 plants or beetroot is/are treated.
15. Process according to either of Claims 13 and 14, in which rice, wheat, barley, rye, triticale, fruit trees, corn, cotton, flax, rapeseed, grapevine, woodland trees, pea, potato or beetroot is/are treated. 15 16. Process according to any one of Claims 13 to 15, in which wheat or barley is treated.
17. Process according to Claim 12, in which the seeds of cereals, potato, cotton, pea, rapeseed, corn or flax, or alternatively the seeds of woodland 20 trees are treated.
18. Process according to any one of Claims 12 to 17, in which the dose of active material applied is between 2 and 200 g of active material per 100 kg of seed, preferably between 3 and 150 g per 100 kg in the 25 case of seed treatments.
19. Process according to any one of Claims 12 to 17, in which the dose of active material applied is between 10 and 800 g of active material per hectare, - 140 preferably between 50 and 300 g of active material per hectare in the case of foliar treatments.
20. Process for preparing compounds according to any one of Claims 1 to 8, which consists 5 in placing a compound of formula (II)A: VI x G (II)A in which G is one of the groups G1 to G9, the 10 groups Gl to G9 having the same definitions as those given in Claim 1 and X 6 having the same definition as that given in Claim 1, Vi is a halogen atom or an alkylsulphonate, haloalkylsulphonate or arylsulphonate group, 15 in contact with a compound of formula (III)A: FII W N1s< W2f -4A R3 R 2 (III)A W 1 , W 2 , R 1 , R 2 , R 3 , p and A having the same 20 definition as that given in Claim 1, in the presence of an organic or inorganic base, in the absence or presence of a solvent, at a temperature of between -80 0 C and 180 0 C or at the boiling - 141 point of the solvent used, the reaction time depending on the conditions used and generally being between 0.1 and 48 h.
21. Process for preparing the compounds of 5 formula (III)A according to Claim 20, in which W 1 , W 2 , R 1 , R 2 , R 3 , p and A have the same definition as that given in Claim 1, which consists in placing a compound of formula (IV): H 2 N-W2 A 10 2 (IV) W 2 , R 1 , R 2 , p and A having the same definition as that given in Claim 1, in contact with a compound of formula (V): 15 WtzU1 R 3 ( W 1 and R 3 having the same definition as that given in Claim 1, U 1 being a halogen atom, or a 20 hydroxyl, lower alkoxy or benzyloxy, lower alkylthio, amino, N-alkylamino, N,N-dialkylamino, N-acylamino or N,N-acylalkylamino radical or a group -O(C=0)Ra, Ra having the same definition as that of R 3 given in Claim - 142 1 and being identical to or different from R 3 , the condensation between the compound of formula (IV) and the compound of formula (V) being carried out in the presence of an organic or inorganic 5 base, or of a dehydrating reagent, in the absence or presence of a solvent.
22. Process for preparing the hydroxamic acid or hydrazonic acid derivatives of formula (III)A according to Claim 20, in which W 1 is an oxygen atom, 10 W 2 , R 1 , R 2 , R 3 , p and A having the same definition as that given in Claim 1, which consists in placing a compound of formula (VI): R, R 2 P (VI) 15 R 1 , R 2 , p and A having the same definition as that given in Claim 1 and Vi being a halogen atom or an alkylsulphonate or arylsulphonate group, in contact with a hydroxamic acid or hydrazonic 20 acid derivative, W 2 and R 3 having the same definition as that given in Claim 1, of formula (VII): H Y W2-H R 3 - 143 the condensation between the compound of formula (VI) and the compound of formula (VII) being carried out in the presence of an organic or inorganic base, in the absence or presence of a solvent. 5 23. Process for preparing the hydroxamic acid derivatives of formula (III)A according to Claim 20, in which W 1 and W 2 are an oxygen atom and p = 1 or 2, R 1 , R 2 , R 3 and A having the same definition as that given in Claim 1, which consists in placing a compound 10 of formula (VIII): R1 HO A R2 (VIII) R 1 , R 2 and A having the same definition as that 15 given in Claim 1 and p = 1 or 2, in contact with a hydroxamic acid derivative of formula (VII) according to Claim 18 in which W 2 is an oxygen atom, R 3 having the same definition as that given in Claim 1. 20 24. Process for preparing the benzyl halide derivatives of formula (II)A according to Claim 20, in which Vi is a halogen atom, by halogenating a compound of formula (IX): - 144 0 X CH 3 G (IX) in which G is one of the groups G1 to G9, the groups G1 to G9 having the same definition as that 5 given in Claim 1, X 6 having the same definition as that given in Claim 1, it being possible for the halogenation of the compound of formula (IX) to be carried out via a radical, thermal or photochemical route, with an 10 N-haloacetamide, in an inert solvent or in the absence of solvent, with or without a free-radical initiator, at a temperature of from 200C to 170*C, it also being possible for the benzyl halide derivatives of formula (II)A, in which Vi is a halogen 15 atom, to be obtained by halogenation of a compound of formula (II)B: Oe WrH G (II)B 20 in which G is one of the groups G1 to G9, the groups G1 to G7 having the same definition as that given in Claim 1 and R 4 is an alkylamino or dialkylamino group, - 145 the groups G8 and G9 having the same definition as that given in Claim 1, X 6 having the same definition as that given in Claim 1, Wi being an oxygen atom, with a halogenating agent or with the lithium 5 halide/mesyl halide/collidine reagent.
25. Process for preparing the compounds according to any one of Claims 1 to 8, for which G is one of the groups G1 to G9, the groups G1 to G7 having the same definition as that given [lacuna] Claim 1 and 10 R 4 being an amino, alkylamino or dialkylamino group or radical, the groups G8 and G9 having the same definition as that given in Claim 1, X 6 having the same definition as that given in Claim 1, which consists in placing a compound of formula (II)B, in which G is one 15 of the groups Gl to G9, the groups Gl to G7 having the same definition as that given in Claim 1 and R 4 being an amino, alkylamino or dialkylamino group or radical, the groups G8 and G9 having the same definition as that given in Claim 1, X 6 having the same definition as that 20 given in Claim 1 and W 1 being an oxygen or sulphur atom, in contact with a compound of formula (III)B: R R R R2 (III)B 25 W 2 , R 1 , R 2 , R 3 , R 13 , X1, X 2 , X 3 , p and A having the same definition as that given for formula (I), Vi - 146 being a halogen atom, preferably a chlorine atom, or an alkylsulphonate or arylsulphonate group, it being possible for the double bond Vi-C(R 3 )=N-W 2 - to be of (E) or (Z) stereochemistry, 5 this reaction being carried out in the presence of an organic or inorganic base, in the absence or presence of a solvent, at a temperature of between -80*C and 1800C or at the boiling point of the solvent used.
26. Thiohydroxamic acid or thiohydrazonic 10 acid derivatives of formula (III)A: W, N "W2d* A R 3 R 2 (III)A in which W 1 is a sulphur atom and W 2 is an oxygen atom 15 or a group NR 13 , R 1 , R 2 , R 3 , R 13 , p and A having the same definition as that given in Claim 1.
27. Process for preparing the compounds according to one of Claims 1 to 8 for which G is a group G3, Q2 being an oxygen atom, R 4 being an alkoxy, 20 alkylamino or dialkylamino group, the other substituents having the same definition as that given in Claim 1 and R 6 being a lower alkyl or lower haloalkyl group, which consists in placing a compound of formula (X): - 147 R X s 'o W 1 N , ' W 2 A 4 R3 R2 0 (X) in which R4 is an alkoxy, alkylamino or dialkylamino group, the other substituents having the same definition as that given in Claim 1, 5 in contact with a Wittig-Horner reagent of formula (XI)A: R6-CH2-P (=0) (ORb) 2 (XI) A 10 R6 being a lower alkyl or lower haloalkyl group, Rb being a lower alkyl, phenyl or benzyl group, or alternatively with a Wittig reagent of formula (XI) B: 15 R6-CH2-P (Rd) 3*; Hal~ (XI) B R6 being a lower alkyl or lower haloalkyl group, Rd being an optionally substituted phenyl group, Hal being a halide ion, 20 by the action of one or more equivalents of a base in an aprotic solvent at a temperature of from -78*C to 50*C. - 148 28. Process for preparing the compounds according to one of Claims 1 to 8, for which G is a group G1 or G2, Qi being a nitrogen atom or a CH group, Q2 being a nitrogen atom, R 4 being an alkoxy, alkylamino 5 or dialkylamino group, the other substituents having the same definition as that given in Claim 1 and R 5 is a lower haloalkyl group, which consists in placing a compound of formula (XII): I R, X W N W2 M-,R4 R3 R2 0 (XII) 10 in which T is an oxygen or sulphur atom, M is an alkali metal or alkaline-earth metal ion, Qi being a nitrogen atom or a CH group, R 4 being an alkoxy, 15 alkylamino or dialkylamino group, W 1 , W 2 , R 1 , R 2 , R 3 , X 6 , p and A having the same definition as that given in Claim 1, in contact with a halogenated compound of formula CHq (Hal) 4-q where q = 1 or 2 and Hal denotes 20 halogen atoms which may be identical to or different from each other and at least one of which is a chlorine or bromine atom, - 149 in a dipolar aprotic solvent at a temperature between -20*C and 250 0 C or at the reflux point of the solvent.
29. Process for preparing the compounds 5 according to any one of Claims 1 to 8, for which G is a group G4 in which n = 1, Q2 being an oxygen atom, R 4 being an alkoxy, alkylamino or dialkylamino group, the other substituents having the same definition as that given in Claim 1, by reaction between a compound of 10 formula (XIII)A: Xs W N W Y 0 (XIII)A in which R 4 is an alkoxy, alkylamino or dialkylamino group, the other substituents having the 15 same definition as that given in Claim 1, and a reagent of formula (XIV): V;( OR 5 (XIV) 20 in which Vi is a halogen atom, R 5 having the same definition as that given in Claim 1, by the action of one or more equivalents of - 150 base, optionally in the presence of a phase-transfer catalyst, in an aprotic solvent at a temperature of from -78*C to 40*C, it being possible for the compounds of general 5 formula (XIII)A, in which R 4 is an alkoxy, alkylamino or dialkylamino group, the other substituents having the same definition as that given in Claim 1, to be obtained by reaction of a compound of general formula (XIII)B: 10 oq V1 HN R4 0 (XIII)B in which R 4 is an alkoxy, alkylamino or dialkylamino group, X 6 having the same definition as 15 that given in Claim 1, Vi being a halogen atom or an alkylsulphonate or arylsulphonate group, with a compound of formula (III)A according to Claim 16, W 1 , W 2 , R 1 , R 2 , R 3 , R 13 , Xi, X 2 , X 3 , p and A 20 having the same definition as that given in Claim 1.
30. Process for preparing the compounds of formula (I) according to one of Claims 1 to 8, for which G is a group Gl to G7 and R 4 is an alkylamino or - 151 dialkylamino group, the other substituents having the same definition as that given in Claim 1, which consists in placing a compound of general formula (I) according to Claim 1, for which G is a group G1 to G7 5 and R 4 is an alkoxy or alkylthio group, the other substituents having the same definition as that given in Claim 1, in contact with an alkylamine or dialkylamine, in an alcoholic solvent, at a temperature of from -50 0 C 10 to 100*C or at the boiling point of the solvent.
31. Process for preparing the compounds according to one of Claims 1 to 8, for which W 1 is a sulphoxide (SO) or sulphone (SO 2 ) group, G being one of the groups G1, G3, G4 or G6 to G9, Q2 and Q3 being an 15 oxygen atom, the other substituents having the same definition as that given in Claim 1, by oxidation of the compounds of general formula (I) according to Claim 1, for which Wi is a sulphur atom, G being one of the groups G1, G3, G4 or G6 to G9, Q2 and Q3 being an oxygen 20 atom, the other substituents having the same definition as that given in Claim 1, using one or more equivalents of an oxidizing agent, in the presence or absence of a catalyst, in an inert solvent.
32. Process for preparing the compounds 25 according to one of Claims 1 to 8, for which G is one of the groups G1 to G9, the other substituents having the same definition as in Claim 1, which consists in placing a compound of formula (XV)A: - 152 W, NW 2 -H G R, 3 (XV)A in which G is one of the groups G1 to G9, the groups G1 to G9 having the same definitions as those given in Claim 1, X6, W 1 , W 2 , R 3 and R 13 having the same 5 definitions as those given in Claim 1, in contact with a compound of formula (VI), R 1 , R 2 , p and A having the same definition as that given in Claim 1, and V1 is a halogen atom or an alkylsulphonate or arylsulphonate group, 10 the condensation between the compound of formula (XV)A and the compound of formula (VI) being carried out in the presence of an organic or inorganic base, in the absence or presence of a solvent.
33. Compounds of formula (XV)A: 15 XW1 NN Wy-H 6 2 G R(XV)A in which G is one of the groups G1 to G9, the groups Gl to G9 having the same definitions as those given in Claim 1, X 6 , W 1 , W 2 and R 3 having the same definitions as 20 those given in Claim 1.
34. Process for preparing the compounds of - 153 formula (XV)A according to Claim 33, which consists in cleaving a compound of formula (XV)B: W N Wj-P G ra G R(XV)B 5 in which G is one of the groups G1 to G9, the groups G1 to G9 having the same definitions as those given in Claim 1, X 6 , W 1 , W 2 and R 3 having the same definitions as those given in Claim 1, and P is a 10 protecting group for the hydroxyl function or a protecting group for the amino function, with a cleaving agent which is specific for the protecting group P.
35. Compounds of formula (XV)B: X W-P 6 2 R 3 (XV)B 15 in which G is one of the groups G1 to G9, the groups G1 to G9 having the same definitions as those given in Claim 1, X 6 , W 1 , W 2 and R 3 having the same 20 definitions as those given in Claim 1 and P is a
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FR9810934A FR2777003A1 (en) 1998-04-07 1998-08-28 NEW FUNGICIDE COMPOUNDS
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