USES OF FORMULA I COMPOUNDS, COMPOUNDS, PHYTOPATHOGENIC FUNGI METHODS, FORMULA I COMPOUND PREPARATIO

专利摘要:
use of compounds of formula i, method of combating phytopathogenic fungi, coated seed, process of preparing compounds of formula i, compounds of formula xi and agrochemical composition. The present invention relates to the use of alkyl-substituted 2- [2-chloro-4- (4-chlorophenoxy) -phenyl] -1- [1,2,4] triazol-1-ylethanol compounds of formula I according to the invention. defined in the descriptive report, its n-oxides and salts for the control of harmful fungi and seeds coated with at least one of these compounds. The present invention also relates to innovative alkyl-substituted 2- [2-, chloro-4- (4-chlorophenoxy) phenyl] -1- [1,2,4] triazol-1-ylethanol compounds, processes and intermediates preparation of such compounds as well as compositions comprising at least one such compound
公开号:BR112014000319B1
申请号:R112014000319-0
申请日:2012-07-11
公开日:2019-05-14
发明作者:Jochen Dietz；Bernd Müller；Egon Haden；Erica May Wilson Lauterwasser；Ian Robert Craig；Jan Klaas Lohmann；Nadege Boudet；Richard Riggs；Thomas Grote；Wassilios Grammenos
申请人:Basf Se；
IPC主号:

专利说明:

“USES OF FORMULA I COMPOUNDS, COMPOUNDS, METHOD OF COMBATING PHYTO-PATHOGEN FUNGI, PROCESSES FOR PREPARING COMPOUNDS OF FORMULA I AND AGRICULTURAL COMPOSITION” [001] The present invention relates to the use of 2 [2-chlorine-4- compounds (4-chlorophenoxy) -phenyl] -1 - [1,2,4] alkyl-substituted triazol-1-ethylanol and its N-oxides and salts to combat phytopathogenic fungi, methods of combating phytopathogenic fungi and seeds coated with hair least one of these compounds. The present invention also relates to innovative 2- [2chloro-4- (4-chlorophenoxy) -phenyl] -1 - [1,2,4] triazol-1-ylpropan-2-ol derivatives, processes for preparing these compounds and compositions comprising at least one such compound.
[002] The use of 2- [2-chloro-4- (4-chlorophenoxy) -phenyl] -1- [1,2,4] triazol1-ylethanol and certain derivatives of the formula:
ΓΎ ° Ί l 1 R ¹ CpA 1 N \ ^OH w
where R ¹ is, among others, methyl or a hydroxy, methoxy or amino-substituted methyl or aryl-substituted alkenyl derivative for controlling phytopathogenic fungi is known from EP 0.275.955 A1 and J. Agric. Food Chem. (2009) 57, 4854-4860.
[003] In addition, the fungicidal use of compounds of the formula mentioned above in which R ¹ is halogenoalkyl, such as fluoromethyl or 2,2,3,3-tetrachloropropyl, has been mentioned in EP 0.113.640 A2 and EP 0.470.466 A2 .
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2/103 [004] In addition, the fungicidal use of compounds with the formula mentioned above in which R ¹ is halogenoalyl, specifically 2,3dibromoalyl, was mentioned in DE 40 03 180 A1.
[005] The compounds according to the present invention differ from those described in the publications mentioned above, among others, by replacing the methyl, halogenoalkyl or halogenoalila groups mentioned above by the specific substituent R ¹ as defined herein.
[006] In many cases, particularly at low application speeds, the fungicidal activity of known fungicidal compounds is unsatisfactory. Based on this, it is the object of the present invention to provide compounds that have improved activity and / or a broader spectrum of activity against harmful phytopathogenic fungi.
[007] This object is achieved by the use of certain derivatives of 2- [2 chloro-4- (4-chlorophenoxy) -phenyl] -1 - [1,2,4] alkyl-substituted triazol-1-ethyl ethanol which have good activity fungicide against harmful phytopathogenic fungi.
[008] Consequently, the present invention relates to the use of compounds of Formula I:
on what:
- R ¹ is C2-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C8 cycloalkyl or C3-C8 cycloalkyl C1-C4 alkyl;
wherein the aliphatic groups R ¹ are unsubstituted or carry one, two, three or four CN substituents;
where the cycloalkyl moieties of R ¹ are unsubstituted or
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3/103 carry one, two, three or even the maximum number of identical or different R ^b groups that, independently of each other, are selected from:
- R ^b is halogen, CN, nitro, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl and C1-C4 haloalkoxy; and its N-oxides and salts acceptable for agricultural use;
to combat harmful phytopathogenic fungi.
[009] The preparation of 2- [2-chloro-4- (4-chlorophenoxy) -phenyl] -1 [1,2,4] triazole-1 -ilpent-4-in-2-ol is described in DE 40 03 180 A1.
[010] The compounds according to the present invention differ from those described in the publication mentioned above by the specific definition of R ¹ and by the proviso that formula I cannot be 2- [2-chloro-4- (4-chlorophenoxy) phenyl ] -1 - [1,2,4] triazole-1-ylpent-4-in-2-ol.
[011] According to a second aspect, therefore, the present invention provides compounds of Formula I that are represented by Formula I and have good fungicidal activity against harmful phytopathogenic fungi:
on what:
- R ¹ is C2-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl C1-C4 alkyl;
wherein the aliphatic groups R ¹ are unsubstituted or carry one, two, three or four CN substituents;
wherein the cycloalkyl moieties of R ¹ are unsubstituted or carry one, two, three or even the maximum number of identical or different R ^b groups which, independently of each other, are selected from:
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- R ^b is halogen, CN, nitro, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl and C1-C4 haloalkoxy; and its N-oxides and salts acceptable for agricultural use;
with the exception of 2- [2-chloro-4- (4-chlorophenoxy) -phenyl] -1- [1,2,4] triazol1-ilpent-4-in-2-ol.
[012] The term "compounds I" means compounds of Formula I. Similarly, this terminology applies to all sub-formulas; "Compounds I.A", for example, means compounds of Formula I.A or "compounds XI" means compounds of Formula XI etc.
[013] Compounds I can be obtained through several routes, analogous to known prior art processes (cf. J. Agric. Food Chem. (2009) 57, 4854-4860; EP 0.275.955 A1; DE 40 03 180 A1; EP 0.113.640 A2; EP 0.126.430 A2) and by means of the synthesis processes shown in the schemes below and in the experimental part of the present application.
[014] In a first process, for example, 4-chlorophenol II reacts, in the first step, with bromine III derivatives in which Y is F or Cl, preferably in the presence of a base. The resulting IV compounds are then transformed into Grignard reagents by reaction with transmetallation reagents such as isopropylmagnesium halides and then reacted with acetyl chloride, preferably under anhydrous conditions and, optionally, in the presence of a catalyst such as CuCl , AlCl3, LiCl and mixtures thereof, to obtain acetophenones V. These compounds V can be halogenated, for example, with bromine, preferably in an organic solvent such as diethyl ether, methyl tert-butyl ether (MTBE), methanol or acetic acid. The resulting VI compounds can then be reacted with 1H-1,2,4triazole, preferably in the presence of a solvent such as tetrahydrofuran (THF), dimethylformamide (DMF), toluene and in the presence of a base such as potassium carbonate, sodium hydroxide or sodium hydride to obtain
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5/103 compounds VII. These triazole VII compounds react with a Grignard R ¹ -M reagent of Formula VIII, where R ¹ is as defined above and M is MgBr, MgCI, Li or Na (such as phenylalkyl-MgBr reagent or phenylalkyl-Li organolithium) , preferably under anhydrous conditions to obtain compounds I, optionally using a Lewis acid such as LaCl3 x 2 LCI or MgBr2 x
0Et2. The preparation of compounds I can be illustrated by the following scheme:
Y = ForCI
+ CH ₃ COCI iPrMgBr
CuCI
AICI ₃ ch ₃ ^ ^J [015] In a second process of obtaining compounds I, derivatives of bromine III, in a first step, they react, for example, with isopropylmagnesium bromide followed by an agent of acyl chloride IX where R ¹ is as defined above (such as acetyl chloride), preferably under anhydrous conditions and, optionally, in the presence of a catalyst such as CuCI, AICI3, LiCI and mixtures thereof, to obtain compounds X. Alternatively, 1,3-dichlorobenzene of Formula 11bb can react with an acid chloride agent IX, where R ¹ is as defined above (such as acetyl chloride), preferably in the presence of a catalyst such as AICI 3. Then, ketones X react with phenols II, preferably in the presence of a base to obtain Va compounds.
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6/103 [016] Intermediates Va then react with trimethylsulf (ox) onide halides, preferably iodide and preferably in the presence of a base such as sodium hydroxide. Then, epoxides XI react with 1H-1,2,4-triazole, preferably in the presence of a base such as potassium carbonate and, preferably, in the presence of an organic solvent such as DMF to obtain compounds I. The preparation of compounds
III
I can be illustrated by the following diagram: IX + R-COCl ^Y or iPrMgBr CuCl
AlCl3
R ¹
Cl
O
X
IIIb Cl
Cl
IX + R-COCl
Go
AC3
R ¹ +
1,2,4-triazole base [017] Compound Va can be prepared generically using intermediate IV with a Grignard reagent such as iPrMgBr and the corresponding acyl chloride R1COCl, optionally in the presence of a catalyst such as CuCl, AlCl3 or LiCl .
[018] If the individual compounds I cannot be obtained via the routes described above, they can be prepared by derivation of other compounds I.
[019] N-oxides can be prepared from Compounds I according to conventional oxidation methods, for example, by treating Compounds I with an organic peracid, such as acid
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7/103 metachloroperbenzoic (cf. WO 03/64572 or J. Med. Chem. 38 (11), 1892-903, 1995); or with inorganic oxidizing agents such as hydrogen peroxide (cf. J. Heterocyc. Chem. 18 (7), 1305-8, 1981) or oxone (cf. J. Am. Chem. Soc. 123 (25), 5962- 5973, 2001). Oxidation can generate pure mono-N-oxides or a mixture of different N-oxides, which can be separated by conventional methods such as chromatography.
[020] If the synthesis generates mixtures of isomers, separation is generally not necessarily required because, in some cases, individual isomers can be interconverted during work for use or during application (such as under the action of light, acids or bases). These conversions can also take place after use, as in the case of plant treatment in the treated plant or in the harmful fungus to be controlled.
[021] In the definitions of the variables provided above, collective terms are used that are generally representative of the substituents in question. The term "Cn-Cm" indicates the number of possible carbon atoms in each case in the substituent or substituent portion in question.
[022] The term "halogen" means fluorine, chlorine, bromine and iodine.
[023] The term “C2-C6 alkyl” indicates straight-chain or branched saturated hydrocarbon groups that contain two to six carbon atoms, such as ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2methylpropyl, 1, 1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, hexyl, 1methylpentyl, 2-methylpentyl, 3- methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1, 2-trimethylpropyl, 1,2,2-trimethylpropyl, 1ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl. Similarly, the expression “alkyl
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C2-C4 ”means a straight or branched alkyl group containing two to four carbon atoms.
[024] The term "C2-C4 alkenyl" means a straight or branched chain unsaturated hydrocarbon radical containing two to four carbon atoms and a double bond in any position, such as ethylene, 1-propenyl, 2-propenyl ( alila), 1-methylethyl, 1-butenyl, 2-butenyl, 3butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl and 2-methyl2-propenyl. Similarly, the term "C2-C6 alkenyl" refers to a straight or branched chain unsaturated hydrocarbon radical that contains two to six carbon atoms and a double bond in any position.
[025] The term "C2-C4 alkynyl" means a straight or branched chain unsaturated hydrocarbon radical that contains two to four carbon atoms and contains at least one triple bond, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl and 1-methyl-2propynyl. Similarly, the term "C2-C6 alkynyl" means a straight or branched chain unsaturated hydrocarbon radical that contains two to six carbon atoms and at least one triple bond.
[026] The term "C3-C8 cycloalkyl" refers to monocyclic saturated hydrocarbon radicals that contain three to eight carbon ring members, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
[027] The term "C3-C8 cycloalkyl C1-C4 alkyl" means alkyl containing one to four carbon atoms (as defined above), where one hydrogen atom of the alkyl radical is replaced by a cycloalkyl radical containing three to eight carbon atoms (as defined above).
[028] Acceptable salts for agricultural use of compounds I include especially the salts of those cations or the acid addition salts of these
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9/103 acids whose cations and anions, respectively, have no adverse effect on the fungicidal action of compounds I. Suitable cations are particularly therefore the ions of alkali metals, preferably sodium and potassium, of alkaline earth metals, preferably calcium , magnesium and barium, of the transition metals, preferably manganese, copper, zinc and iron, and also the ammonium ion which, if desired, can carry one to four C1-C4 alkyl substituents and / or a phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, additionally phosphonium ions, sulfonium ions, preferably tri (C1-C4 alkyl) sulfonium and sulfoxonium ions, preferably tri (C1-C4 alkyl) sulfoxonium. Anions of useful acid addition salts are mainly chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and acid anions C1-C4 alkanoids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting a compound of Formula I with a corresponding anion acid, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
[029] Formula I compounds may be present in atropisomers due to restricted rotation around a single bond of asymmetric groups. They are also part of the object of the present invention.
[030] Depending on the substitution pattern, the compounds of Formula I and their N-oxides may have one or more chirality centers and, in this case, they are present in the form of pure enantiomers or pure diastereomers or mixtures of enantiomers or diastereomers. Both, pure enantiomers or diastereomers, and mixtures thereof are the subject of the present invention.
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10/103 [031] With respect to variables, the achievements of the intermediates correspond to the achievements of compounds I.
[032] Preference is given to compounds I and, where applicable, also to compounds of all sub-formulas and intermediates such as compounds XI, in which the substituents (such as R ¹ ) have, independently of one another or, to a greater extent. preferably, in combination, the following meanings:
[033] One embodiment relates to compounds I, wherein R ¹ is C2-C4 alkyl, C2-C4 alkenyl or C2-C4 alkynyl.
[034] Another embodiment concerns compounds I, where R ¹ is C2-C6 alkyl. Preferably, R ¹ is C2-C4 alkyl.
[035] In a further embodiment of the present invention, R ¹ is ethyl.
[036] In a further embodiment of the present invention, R ¹ is npropyl.
[037] In a further embodiment of the present invention, R ¹ is isopropyl.
[038] In a further embodiment of the present invention, R ¹ is nbutyl.
[039] In a further embodiment of the present invention, R ¹ is tert-butyl.
[040] An additional embodiment concerns compounds I, where R ¹ is ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, allyl, ethynyl, prop-1-inyl, but1-inyl, cyclopropyl or cyclopropylmethyl. A further embodiment concerns compounds I, where R ¹ is C2-C6 alkenyl. Preferably, R ¹ is C2-C4 alkenyl.
[042] In a further embodiment of the present invention, R ¹ is vinyl.
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11/103 [043] In a further embodiment of the present invention, R ¹ is allyl.
[044] An additional embodiment concerns compounds I, where R ¹ is C2-C6 alkynyl. Preferably, R ¹ is C2-C6 alkyl-1-ynyl.
[045] In a further embodiment of the present invention, R ¹ is isethynyl.
[046] In a further embodiment of the present invention, R ¹ is prop-1-inyl.
[047] In a further embodiment of the present invention, R ¹ is but-1-inyl.
[048] In a further embodiment of the present invention, R ¹ is 3 methylbut-1-inyl.
[049] In a further embodiment of the present invention, R ¹ is 3,3-dimethylbut-1-inyl.
[050] An additional embodiment relates to compounds I, where R ¹ is C2-C4 alkynyl, preferably C2-C4 alkyl-1-inyl and, preferably even greater, selected from ethynyl and but-1-inyl .
[051] An additional embodiment concerns compounds I, where R ¹ is C3-C8 cycloalkyl.
[052] In a further embodiment of the present invention, R ¹ is cyclopropyl.
[053] An additional embodiment concerns compounds I, where R ¹ is C3-C8 cycloalkyl C1-C4 alkyl.
[055] In a further embodiment of the present invention, R ¹ is cyclopropylmethyl.
[056] An additional embodiment concerns compounds I in which R ¹ carries no CN substituent.
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12/103 [057] An additional embodiment refers to compounds I in which R ¹ does not carry any group R ^b [058] An additional embodiment refers to compounds I, in which the cycloalkyl portion of R ¹ carries from one to three R ^b groups selected from halogen.
[059] Those skilled in the art will easily understand that the preferences provided with respect to compounds I apply to Formulas I and XI as defined above.
[060] With reference to its use, specific preference is given to the 48 compounds of formulas I.A and XI compiled in Table 1 below. At this point, the groups mentioned in the Tables for a substituent are still, regardless of the combination in which they are mentioned, a particularly preferred embodiment of the substituent in question.
Table 1 [061] Compounds 1 to 48 of Formula I, where the meaning of R ¹ for each individual compound corresponds, in each case, to a line in Table A.
Table A
No. R ¹ 1 -CH2CH3 2 -CH2CH2CH3 3 -CH (CH3) 2 4 -CH2CH2CH2CH3 5 -CH (CH2CH3) 2 6 -C (CH3) 3
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No. R ¹ 7 -CH2CH (CH3) 2 8 -CH2CH2CH2CH2CH3 9 -CH2CH2CH2CH2CH2CH3 10 -CH = CH2 11 -CH = CHCH3 12 -CH2CH = CH2 13 -C (CH3) = CH2 14 -CH = CHCH2CH3 15 -CH2CH = CHCH3 16 -CH2CH2CH = CH2 17 -CH (CH = CH2) 2 18 -CH = C (CH3) 2 19 -CH = CHCH2CH2CH3 20 -CH = CHCH2CH2CH2CH3 21 -CH = CHC (CH3) 3 22 -C CH 23 -C CCH3 24 -C CCH2CH3
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No. R ¹ 25 -CH2C CCH3 26 -CH2CH2C CH 27 -CH (C CH) 2 28 -C CCH2CH2CH3 29 -C CCH (CHa) 2 30 -C CCH2CH2CH2CH3 31 -C CC (CHa) a 32 - C3H5 (cyclopropyl) 33 1-Cl-cyclopropyl 34 1-F-cyclopropyl 35 -C4H7 36 -C6H11 (cyclohexyl) 37 -CH2-C3H5 38 -CH2-CN 39 -CH2CH2-CN 40 -CH2-C (CH3) = CH2 41 -C5H9 (cyclopentyl) 42 -CH (CH3) CH2CH3
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No. R ¹ 43 -CH2C CH 44 -CH2C CCH2CH3 45 -CH (CH3) C3H5 46 1-Methylcyclopropyl 47 1-CN-cyclopropyl 48 -CH (CH3) CN
[062] Compounds I and compositions according to the present invention, respectively, are suitable as fungicides. They are distinguished by their remarkable efficacy against a wide spectrum of phytopathogenic fungi, including soil fungi, derived especially from the classes of Plasmodiophoromycetes, Peronosporomycetes (sin. Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromyietes (sin. Some are systemically effective and can be used to protect crops such as foliar fungicides, seed cover fungicides and soil fungicides. In addition, they are suitable for the control of harmful fungi, which occur, among others, in wood or plant roots.
[063] Compounds I and the compositions according to the present invention are particularly important in the control of a series of phytopathogenic fungi on various cultivated plants, such as cereals, for example wheat, barley, rye, triticale, oats or rice; beet, such as sugar beet or fodder beet; fruits, such as apples, drupes or soft fruits, such as apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, black currants or gooseberries; plants
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16/103 legumes, such as lentils, peas, alfalfa or soy; oil plants, such as canola, mustard, olive, sunflower, coconut, cocoa beans, castor oil plants, oil palm, peanuts or soybeans; pumpkins, such as strawberry, pumpkin or melon; fiber plants, such as cotton, linen, hemp or jute; citrus fruits, such as oranges, lemons, grapefruits or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, squash or paprika; lauraceae, such as avocado, cinnamon or camphor; raw material and energy plants, such as corn, soy, canola, sugar cane or oil palm; corn; smoke; nuts; coffee, tea, bananas, grapes (table grapes and juice grapes); hop; grass; Stevia; natural rubber plants or forest and ornamental plants, such as flowers, shrubs, broadleaf trees or springs, such as conifers; and on plant propagating material, such as seeds, and the crop material of these plants.
[064] Preferably, compounds I and their compositions, respectively, are used to control a series of fungi on field crops, such as potatoes, beets, tobacco, wheat, barley, rye, oats, rice, corn, cotton, soybeans , canola, vegetables, sunflower, coffee or sugar cane; fruits; grape; ornamental plants; or vegetables, such as cucumbers, tomatoes, beans or pumpkins.
[065] The term “plant propagating material” should be understood as indicating all the plant's generating parts, such as seeds and plant plant material such as cuttings and tubers (for example, potatoes), which can be used for plant multiplication . This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, seedlings and other parts of the plants, including seedlings and young plants, which must be transplanted after germination or after the emergence of the soil. These
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17/103 young plants can also be protected before transplantation by total or partial treatment by immersion or dumping.
[066] Preferably, the treatment of plant propagation materials with compounds I and their compositions, respectively, is used to control a series of fungi in cereals, such as wheat, barley, rye and oats; rice, corn, cotton and soy.
[067] The term “cultivated plants” should be understood as including plants that have been modified through cultivation, mutagenesis or genetic engineering, including, but not limited to, agricultural biotechnology products on the market or in development (cf. http: / /www.bio.org/speeches/pubs/er/agri_products.asp).
[068] Genetically modified plants are plants whose genetic material has been modified by the use of recombinant DNA methods that, under natural circumstances, cannot be easily obtained through crosses, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant. Such genetic modifications also include, but are not limited to, the desired post-translational modification of protein (s), oligo or polypeptides, for example, through glycosylation or addition of polymers such as prenylated, acetylated or farnesylated portions or PEG portions.
[069] Plants that have been modified through cultivation, mutagenesis or genetic engineering, that have, for example, become tolerant to the application of specific classes of herbicides, such as auxin herbicides such as dicamba or 2,4-D; bleaching herbicides such as hydroxyphenylpyruvate dioxigenase inhibitors (HPPD) or phytoene desaturase inhibitors (PDS), acetolactate synthase inhibitors (ALS) such as sulfonyl ureas or imidazolinones; 3-phosphate synthase inhibitors
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18/103 enolpiruvilshikimato (EPSPS), such as glyphosate; glutamine synthase (GS) inhibitors such as glufosinate; protoporphyrinogen oxidase IX inhibitors; inhibitors of lipid biosynthesis, such as acetyl CoA carboxylase (ACCase) inhibitors; or oxyinyl herbicides (ie, bromoxynil or ioxynyl) as a result of conventional cultivation methods or genetic engineering. In addition, plants have become resistant to several classes of herbicides through multiple genetic modifications, such as resistance to glyphosate and glufosinate or both, glyphosate and a herbicide of another class, such as ALS inhibitors, HPPD inhibitors, auxin herbicides or ACCase inhibitors. These herbicide resistance technologies are described, for example, in Pest Managem. Sci. 61, 2005, 246; 61, 2005, 258; 61,2005, 277; 61,2005, 269; 61,2005, 286; 64, 2008, 326; 64, 2008, 332; Weed Sci. 57, 2009, 108; Austral. J. Agricult. Res. 58, 2007, 708; Science 316, 2007, 1185; and references mentioned there. Several cultivated plants have become tolerant to herbicides by means of conventional cultivation methods (mutagenesis), such as Clearfield® summer canola (Canola, BASF SE, Germany) which is tolerant to imidazolinones, such as imazamox, or ExpressSun® sunflowers ( DuPont, United States), which are tolerant to sulfonyl ureas, such as tribenuron. Genetic engineering methods have been used to make cultivated plants, such as soybeans, cotton, corn, beets and canola, tolerant to herbicides such as glyphosate and glufosinate, some of which are commercially available under the trade names RoundupReady® (glyphosate tolerant, Monsanto , United States), Cultivance® (imidazolinone tolerant, BASF SE, Germany) and LibertyLink® (glufosinate tolerant, Bayer CropScience, Germany).
[070] In addition, plants are also covered which, using recombinant DNA methods, are capable of synthesizing one or more insecticidal proteins, especially those known to the bacterial genus
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Bacillus, particularly from Bacillus thuringiensis, such as δ-endotoxins, for example CryIA (b), CryIA (c), CryIF, CryIF (a2), CryIIA (b), CryIIIA, CryIIIB (b1) or Cry9c; vegetable insecticidal proteins (VIP), such as VIP1, VIP2, VIP3 or VIP3A; insecticidal proteins from bacterial colonizing nematodes, such as Photorhabdus spp or Xenorhabdus spp; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins or other insect specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, vegetable lectins, such as pea or barley lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; ribosome deactivating proteins (RIP), such as ricin, corn RIP, abrina, lufina, saporina or briodina; steroid metabolism enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-IDPglycosyltransferase, cholesterol oxidases, ecdysone inhibitors or HMGCoA-reductase; ion channel blockers, such as sodium or calcium channel blockers; juvenile hormone esterase; diuretic hormone receptors (helicoquinine receptors); stylbene synthase, bibenzyl synthase, chitinases or glucanases. In the context of the present invention, these toxins or insecticidal proteins should also be understood expressly as pre-toxins, hybrid proteins or proteins truncated or otherwise modified. Hybrid proteins are characterized by a new combination of protein domains (see, for example, WO 02/015701). Additional examples of such toxins or genetically modified plants capable of synthesizing these toxins are described, for example, in EP-A 374.753, WO 93/007278, WO 95/34656, EP-A-427.529, EP-A 451.878, WO 03/18810 and WO 03/52073. The production methods of these genetically modified plants are generally known to those skilled in the art and are described, for example, in publications
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20/103 mentioned above. These insecticidal proteins contained in genetically modified plants provide plants producing these proteins with tolerance to harmful pests of all taxonomic groups of arthropods, especially beetles (coleopterans), insects with two wings (diptera), moths (lepidopterans) and nematodes. Genetically modified plants capable of synthesizing one or more insecticidal proteins are, for example, described in the publications mentioned above, some of which are commercially available, such as YieldGard® (corn cultivars producing the Cry1Ab toxin), YieldGard® Plus (corn cultivars producers of Cry1Ab and Cry3Bb1 toxins), Starlink® (corn cultivars producing Cry9c toxin), Herculex® RW (corn cultivars producing Cry34Ab1, Cry35Ab1 and the phosphinothricin n-acetyltransferase enzyme (PAT)); NuCOTN® 33B (corn cultivars producing the Cry1Ac toxin), Bollgard® I (cotton cultivars producing the Cry1Ac toxin), Bollgard® II (cotton cultivars producing the Cry1Ac and Cry2Ab2 toxins); VIPCOT® (cotton cultivars producing VIP toxin); NewLeaf® (potato cultivars producing the Cry3A toxin); Bt-Xtra®, NatureGard®, KnockOut®, BiteGard®, Protecta®, Bt11 (such as Agrisure® CB) and Bt176 from Syngenta Seeds SAS, France (corn cultivars producing the Cry1Ab toxin and PAT enzyme), MIR604 from Syngenta Seeds SAS, France (maize cultivars producing a modified version of the Cry3A toxin, cf. WO 03/18810), MON 863 from Monsanto Europe SA, Belgium (maize cultivars producing the Cry3Bb1 toxin), IPC 531 from Monsanto Europe SA, Belgium (maize cultivars producing a modified version of the Cry1Ac toxin) and 1507 from Pioneer Overseas Corporation, Belgium (maize cultivars producing the Cry1F toxin and PAT enzyme).
[071] In addition, plants are also covered which, using recombinant DNA methods, are capable of synthesizing one or more proteins to increase the resistance or tolerance of these plants to
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21/103 bacterial, viral or fungal pathogens. Examples of these proteins are the so-called “pathogenesis-related proteins” (PR proteins; see, for example, EP-A 392.225), genes for resistance to plant diseases (such as potato cultivars that express resistance genes that act against derived Phytophthora infestans Mexican wild potato Solanum bulbocastanum) or T4 lysozyme (such as potato cultivars capable of synthesizing these proteins with higher resistance against bacteria such as Erwinia amylvora). The production methods of these genetically modified plants are generally known to those skilled in the art and are described, for example, in the publications mentioned above.
[072] In addition, plants are also covered which, using recombinant DNA methods, are able to synthesize one or more proteins to increase productivity (such as biomass production, grain yield, starch content, oil content or protein content), drought tolerance, salinity or other growth limiting environmental factors or tolerance to fungal, bacterial or viral pests and pathogens of these plants.
[073] In addition, plants are also covered that contain, through the use of recombinant DNA methods, a modified quantity of substances of content or new substances of content, specifically to increase human or animal nutrition, such as oil crops that produce acids unsaturated omega-9 fatty acids or health-promoting long-chain omega-3 fatty acids (such as Nexera® canola, Dow Agro Sciences, Canada).
[074] In addition, plants are also covered which contain, through the use of recombinant DNA methods, a modified amount of substances of content or new substances of content, specifically to increase the production of raw material, such as potatoes that produce
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22/103 higher amounts of amylopectin (such as Amflora® potatoes, BASF SE, Germany).
[075] Compounds I and their compositions, respectively, are particularly suitable for controlling the following plant diseases:
[076] Albugo spp (white rust) in ornamental plants, vegetables (such as A. candida) and sunflowers (such as A. tragopogonis); Alternaria spp (Alternaria leaf spot) in vegetables, canola (A. brassicola or brassicae), beets (A. tenuis), fruits, rice, soy, potatoes (such as A. solani or A. alternata), tomatoes (such as such as A. solani or A. alternata) and wheat; Aphanomyces spp on beets and vegetables; Ascochyta spp in cereals and vegetables, such as A. tritici (anthracnose) in wheat and A. hordei in barley; Bipolaris and Drechslera spp (teleomorph: Cochliobolus spp), such as southern leaf spot (D. maydis) or northern leaf spot (B. zeicola) on corn, such as spot bubble (B. sorokiniana) on cereals and , for example, B. oryzae in rice and grass; Blumeria (formerly Erysiphe) graminis (mildew powder) on cereals (such as wheat or barley); Botrytis cinerea (teleomorph: Botryotinia fuckeliana: gray fungus) in fruits and berries (such as strawberries), vegetables (such as lettuce, carrots, celery and cabbage), canola, flowers, grapes, forest plants and wheat; Bremia lactucae (powdery mildew) on lettuce; Ceratocystis (sin. Ophiostoma) spp (rot or wither) in trees with broad leaves and springs, such as C. ulmi (Dutch elm disease) in elms; Cercospora spp (Cercospora leaf spots) on maize (such as gray leaf spot: C. zeae-maydis), rice, beet (such as C. beticola), sugar cane, vegetables, coffee, soy (such as C sojina or C. kikuchii) and rice; Cladosporium spp in tomatoes (such as C. fulvum: leaf mold) and cereals, such as C. herbarum (black ear) in wheat; Claviceps purpurea (ergot) in cereals; Cochliobolus (anamorph: Helminthosporium de Bipolaris) spp (leaf spots) in corn (C. carbonum), cereals (such as
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23/103 as C. sativus, anamorph: B. sorokiniana) and rice (such as C. miyabeanus, anamorph: H. oryzae); Colletotrichum (teleomorph: Glomerella) spp (anthracnose) on cotton (such as C. gossypii), corn (such as C. graminicola: anthracnose stem rot), soft fruits, potatoes (such as C. coccodes, black spots), beans (such as C. lindemuthianum) and soy (such as C. truncatum or C. gloeosporioides); Corticium spp, such as C. sasakii (cover spots) in rice; Corynespora cassiicola (leaf spots) in soybeans and ornamental plants; Cycloconium spp, such as C. oleaginum in olive trees; Cylindrocarpon spp (such as cancer of fruit trees and decline of young grapes, teleomorph: Nectria or Neonectria spp) in fruit trees, grapes (such as C. liriodendri, teleomorph: Neonectria liriodendri: black foot disease) and ornamental plants; Dematophora (teleomorph: Rosellinia) necatrix (stem and root rot) in soybean; Diaporthe spp., Such as D. phaseolorum (rot) in soybeans; Drechslera (sin. Helminthosporium, teleomorph: Pyrenophora) spp in corn, cereals, such as barley (for example, D. teres, liquid spot) and wheat (such as D. tritici-repentis: brown spot), rice and grass; Esca (fall, stroke) in grapes, caused by Formitiporia (sin. Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora (formerly Phaeoacremonium chlamydosporum), Phaeoacremonium aleophilum and / or Botryosphaeria obtusa; Elsinoe spp. in pomes (E. pyri), soft fruits (E. veneta: anthracnose) and grapes (E. ampelina: anthracnose); Entyloma oryzae (leaf soot) in rice; Epicoccum spp (black fungus) in wheat; Erysiphe spp (mildew powder) on beet (E. betae), vegetables (such as E. pisi), such as pumpkins (such as E. cichoracearum), cabbage, canola (such as E. cruciferarum); Eutypa lata (cancer or fall Eutypa, anamorph: Cytosporina lata, sin. Libertella blepharis) on fruit trees, grapes and ornamental woods; Exserohilum (sin. Helminthosporium) spp in maize (such as E. turcicum); Fusarium (teleomorph: Gibberella) spp (wither, root rot or
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24/103 stem) in various plants, such as F. graminearum or F. culmorum (root rot, scar or head spot) in cereals (such as wheat or barley), F. oxysporum in tomatoes, F. solani in soybeans and F. verticillioides in corn; Gaeumannomyces graminis (foot disease) in cereals (such as wheat or barley) and corn; Gibberella spp in cereals (such as G. zeae) and rice (such as G. fujikuroi: Bakanae disease); Glomerella cingulata in grapes, pomes and other plants and G. gossypii in cotton; grain stain complex in rice; Guignardia bidwellii (black rot) in grapes; Gymnosporangium spp in rosacea and juniper plants, such as G. sabinae (rust) in pears; Helminthosporium spp (sin. Drechslera, teleomorph: Cochliobolus) in corn, cereals and rice; Hemileia spp, such as H. vastatrix (coffee leaf rust) in coffee; Isariopsis clavispora (sin. Cladosporium vitis) in grapes; Macrophomina phaseolina (sin. Phaseoli) (root and stem rot) in soybeans and cotton; Microdochium (sin. Fusarium) nivale (pink snow mold) in cereals (such as wheat or barley); Microsphaera diffusa (mildew powder) in soybean; Monilinia spp, such as M. laxa, M. fructicola and M. fructigena (brown rot, flower and branch blotch) in drupes and other rose plants; Mycosphaerella spp in cereals, bananas, soft fruits and peanuts, such as M. graminicola (anamorph: Septoria tritici, Septoria patches) in wheat or M. fijiensis (black Sigatoka disease) in bananas; Peronospora spp (woolly mildew) in cabbage (such as P. brassicae), canola (such as P. parasitica), onions (such as P. destructor), tobacco (P. tabacina) and soy (such as P. manshurica); Phakopsora pachyrhizi and P. meibomiae (soybean rust) in soybean; Phialophora spp, for example, in grapes (such as P. tracheiphila and P. tetraspora) and soy (such as P. gregata: stem rot); Phoma lingam (root and stem rot) in canola and cabbage and P. betae (root rot, leaf spots and decay) in beet; Phomopsis spp on sunflower, grapes (such as P. viticola: leaf spot and cover) and soy
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25/103 (such as stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum); Physoderma maydis (brown spots) in corn; Phytophthora spp (wilt, root spots, leaves, fruits and stem) in various plants, such as paprika and pumpkins (such as P. capsici), soy (such as P. megasperma, sin. P. soye), potatoes and tomatoes (such as P. infestans: posterior spot) and trees with broad leaves (such as P. ramorum: sudden death of the oak); Plasmodiophora brassicae (heavy root) in cabbage, canola, radish and other plants; Plasmopara spp, such as P. viticola (grape downy mildew) in grapes and P. halstedii in sunflowers; Podosphaera spp (powdery mildew) in rose plants, hops, pomes and soft fruits, such as P. leucotricha in apples; Polymyxa spp, for example, in cereals, such as barley and wheat (P. graminis) and beet (P. betae) and viral diseases transmitted in this way; Pseudocercosporella herpotrichoides (bed, teleomorph: Tapesia yallundae) in cereals, such as wheat or barley; Pseudoperonospora (woolly mildew) on various plants, such as P. cubensis on pumpkins or P. humili on hops; Pseudopezicula tracheiphila (red fire disease, anamorph: Phialophora) in grapes; Puccinia spp (rust) in various plants, such as P. tricina (brown or leaf rust), P. striiformis (yellow rust or streaks), P. hordei (dwarf rust), P. graminis (black or stem rust) or P. recondita (leaf rust or brown) in cereals, such as wheat, barley or rye, P. kuehnii (orange rust) in sugar cane and P. asparagi in asparagus; Pyrenophora (anamorph: Drechslera) tritici-repentis (brown spot) in wheat or P. teres (liquid spot) in barley; Pyricularia spp, such as P. oryzae (teleomorph: Magnaporthe grisea, rice rust) in rice and P. grisea in grass and cereals; Pythium spp (rotting) in grass, rice, corn, wheat, cotton, canola, sunflower, soy, beet, vegetables and various other plants (such as P. ultimum or P. aphanidermatum); Ramularia spp, such as R. collo-cygni
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26/103 (Ramularia leaf spots, physiological leaf spots) in barley and R. beticola in beet; Rhizoctonia spp on cotton, rice, potatoes, grass, corn, canola, beet, vegetables and several other plants, such as R. solani (root and stem rot) in soy, R. solani (cover spots) in rice or R cerealis (spring spots of Rhizoctonia) in wheat or barley; Rhizopus stolonifer (black mold, soft rot) in strawberries, carrots, cabbage, grapes and tomatoes; Rhynchosporium secalis (yellowing) in barley, rye and triticale; Sarocladium oryzae and S. attenuatum (cover rot) in rice; Sclerotinia spp (stalk rot or white mold) in vegetables and field crops, such as canola, sunflower (such as S. sclerotiorum) and soy (such as S. rolfsii or S. sclerotiorum); Septoria spp in various plants, such as S. glycines (brown spot) in soy, S. tritici (Septoria spots) in wheat and S. (sin. Stagonospora) nodorum (Stagonospora spots) in cereals; Uncinula (sin. Erysiphe) necator (powdery mildew, anamorph: Oidium tuckeri) in grapes; Setospaeria spp (leaf spots) on maize (such as S. turcicum, sin. Helminthosporium turcicum) and grass; Sphacelotheca spp (rust) in maize (such as S. reiliana: upper rust), sorghum and sugar cane; Sphaerotheca fuliginea (powdery mildew) on pumpkins; Spongospora subterranea (dust scar) in potatoes and viral diseases transmitted in this way; Stagonospora spp in cereals, such as S. nodorum (Stagonospora spot, teleomorph: Leptosphaeria (sin. Phaeosphaeria) nodorum) in wheat; Synchytrium endobioticum in potatoes (potato wart disease); Taphrina spp, such as T. deformans (leaf curl disease) in peaches and T. pruni (plum pocket) in plums; Thielaviopsis spp (black root rot) in tobacco, pomes, vegetables, soybeans and cotton, such as T. basicola (sin. Chalara elegans); Tilletia spp (common cavity or smelly spot) in cereals, such as T. tritici (sin. T. caries, wheat cavity) and T. controversa (dwarf cavity) in wheat;
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Typhula incarnata (gray snow mold) in barley or wheat; Urocystis spp, such as U. occulta (stalk spot) in rye; Uromyces spp (rust) in vegetables, such as beans (for example, U. appendiculatus, sin. U. phaseoli) and beets (such as U. betae); Ustilago spp (loose spot) in cereals) (such as U. nuda and U. avaenae), corn (such as U. maydis: corn cavity) and sugar cane; Venturia spp (scar) in apples (such as V. inaequalis) and pears; and Verticillium spp (wither) in various plants, such as fruits and ornamental plants, grapes, soft fruits, vegetables and field crops, such as V. dahliae in strawberries, canola, potatoes and tomatoes.
[077] Compounds I and their compositions, respectively, are also suitable for controlling harmful fungi in protecting stored or harvested products and in protecting materials. The term “material protection” should be understood as indicating the protection of technical and non-living materials, such as adhesives, glues, wood, paper and cardboard, textile products, leather, paint dispersions, plastics, cooling lubricants, fibers or against infestation and destruction by harmful microorganisms, such as fungi and bacteria. With regard to the protection of wood and other materials, specific attention is paid to the following harmful fungi: Ascomycetes such as Ophiostoma spp, Ceratocystis spp, Aureobasidium pullulans, Sclerophoma spp, Chaetomium spp, Humicola spp, Petriella spp, Trichurus spp; Basidiomycetes such as Coniophora spp, Coriolus spp, Gloeophyllum spp, Lentinus spp, Pleurotus spp, Poria spp, Serpula spp and Tyromyces spp, Deuteromycetes such as Aspergillus spp, Cladosporium spp, Penicillium spp, Trichoromy spp, Trichoromy spp, Trichorma spp like Mucor spp and, in addition, in the protection of stored products and harvest, the following yeast fungi deserve observation: Candida spp and Saccharomyces cerevisiae.
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28/103 [078] Compounds I and their compositions, respectively, can be used to improve plant health. The present invention also relates to a method of improving plant health by treating plants, their propagation material and / or the place where the plant is growing or must grow with an effective amount of compounds I and their compositions , respectively.
[079] The term “plant health” should be understood as indicating a condition of the plant and / or its products that is determined by several indicators alone or in combination with each other, such as yield (eg higher biomass and / or increase of the content of valuable ingredients), vigor of the plant (such as increased plant growth and / or greener leaves (“lump-boosting effect”)), quality (such as higher content or composition of certain ingredients) and tolerance to stress biotic and / or abiotic. The indicators identified above for the health condition of the plants may be interdependent or may result from each other.
[080] The compounds of Formula I may be present in different crystal modifications whose biological activity may differ. Similarly, they are the subject of the present invention.
[081] Compounds I are used as such or in the form of compositions by treating fungi or plants, plant propagating materials such as seeds, soil, surfaces, materials or rooms to be protected against fungal attacks with a fungicidal amount of the active substances. The application can be carried out before and after plant infection, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by fungi.
[082] Plant propagation materials can be treated with compounds I as such or a composition that comprises at least one compound I prophylactically during or before planting or transplantation.
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29/103 [083] The present invention also relates to agrochemical compositions comprising an auxiliary and at least one compound I according to the present invention.
[084] An agrochemical composition comprises a fungicidal amount of a compound I. The term "effective amount" indicates an amount of the composition or compounds I, which is sufficient to control harmful fungi on cultivated plants or to protect materials and which it does not result in substantial damage to the treated plants. This amount can vary over a wide range and is dependent on several factors, such as the fungal species to be controlled, the treated material or cultivated plant, the climatic conditions and the specific compound I used.
[085] Compounds I, its N-oxides and salts can be converted into customary types of agrochemical compositions, such as solutions, emulsions, suspensions, dust, powders, pastes, granules, pressures, capsules and mixtures thereof. Examples of types of composition are suspensions (such as SC, OD, FS), emulsifiable concentrates (such as EC), emulsions (such as EW, EO, ES, ME), capsules (such as CS, ZC), pastes, tablets , wettable or dry powders (such as WP, SP, WS, DP, DS), pressures (such as BR, TB, DT), granules (such as WG, SG, GR, FG, GG, MG), insecticidal articles ( such as LN), as well as gel formulations for the treatment of plant propagating materials such as seeds (for example, GF). These and other types of composition are defined in the Catalog of Pesticide Formulation Types and International Coding System, Technical Monograph No. 2, 6th ^to Ed., May 2008, CropLife International.
[086] The compositions are prepared in a known manner, as described by Mollet and Grubemann, Formulation Technology, Wiley
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VCH, Weinheim, 2001; or Knowles, New Developments in Crop Protection Product Formulation, Agrow Reports DS243, T&F Informa, London, 2005.
[087] Examples of suitable auxiliaries are solvents, liquid vehicles, solid vehicles or fillers, surfactants, dispersants, emulsifiers, humectants, adjuvants, solubilizers, penetration amplifiers, protective colloids, adhesives, thickeners, humectants, repellents, attractions, stimulants food, compatibilizers, bactericides, antifreeze agents, antifoaming agents, dyes, adhesives and binders.
[088] Appropriate liquid solvents and vehicles are water and organic solvents, such as fractions of mineral oil with a medium to high boiling point, such as kerosene and diesel oil; animal or vegetable oils; aliphatic, cyclic and aromatic hydrocarbons, such as toluene, paraffin, tetrahydronaphthalene and alkylated naphthalenes; alcohols, such as ethanol, propanol, butanol, benzyl alcohol and cyclohexanol; glycols; DMSO; ketones, such as cyclohexanone; esters, such as lactates, carbonates, fatty acid esters and gamma butyrolactone; fatty acids; phosphonates; amines; amides, such as N-methylpyrrolidone, fatty acid dimethylamides; and their mixtures.
[089] Solid vehicles or appropriate loads are mineral lands, such as silicates, silica gel, talc, kaolin, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate and magnesium oxide; powdered polysaccharides, such as cellulose and starch; fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate and ureas; products of vegetable origin, such as cereal mass, mass of bark of trees, mass of wood, mass of nut shells and their mixtures.
[090] Suitable surfactants are active compounds on the surface, such as anionic, cationic, nonionic and
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31/103 amphoteric, block polymers, polyelectrolytes and their mixtures. These surfactants can be used as emulsifiers, dispersants, solubilizers, humectants, penetration amplifiers, protective colloids or adjuvants. Examples of surfactants are listed in McCutcheon’s, Vol. 1: Emulsifiers & Detergents, McCutcheonS Directories, Glen Rock, United States, 2008 (international edition or North American edition).
[091] Suitable anionic surfactants are ammonium, alkaline or alkaline earth salts of sulfonates, sulfates, phosphates, carboxylates and mixtures thereof. Examples of sulphonates are alkylaryl sulphonates, diphenyl sulphonates, alphaolefin sulphonates, lignin sulphonates, fatty acid sulphonates, ethoxylated alkylphenol sulphonates, alkoxylated arylphenol sulphonates, condensed naphthalene sulphonates, dodecyl sulphate sulphides and dodecyl sulphides. naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinates. Examples of sulfates are fatty acid and oil sulfates, ethoxylated alkylphenols, alcohols, ethoxylated alcohols or fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, carboxylated alcohol or alkylphenol ethoxylates.
[092] Suitable non-ionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters that have been alkoxylated to one to fifty equivalents. Ethylene oxide and / or propylene oxide can be used for alkoxylation, preferably ethylene oxide. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of
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32/103 surfactants based on sugar are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkyl polyglycosides. Examples of polymeric surfactants are vinylpyrrolidone homo or copolymers, vinyl alcohols or vinyl acetate.
[093] Suitable cationic surfactants are quaternary surfactants, such as quaternary ammonium compounds with one or two hydrophobic groups or salts of long chain primary amines. Suitable amphoteric surfactants are alkylbetaines and imidazolines. Suitable block polymers are block polymers of type A-B or A-B-A that comprise blocks of polyethylene oxide and polypropylene oxide, or of type A-B-C that comprise alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkaline salts of polyacid comb polymers or polyacrylic acids. Examples of polybases are polyvinylamines or polyethyleneamines.
[094] Appropriate adjuvants are compounds that, by themselves, have negligible or even non-existent pesticidal activity and that improve the biological performance of compound I on the target. Examples are surfactants, vegetable or mineral oils and other auxiliaries. Additional examples are listed by Knowles, Adjuvants and Additives, Agrow Reports DS256, T&F Informa, United Kingdom, 2006, chapter 5.
[095] Suitable thickeners are polysaccharides (such as xanthan gum, carboxymethylcellulose), inorganic clays (organically modified or unmodified), polycarboxylates and silicates.
[096] Suitable bactericides are derived from bronopol and isothiazolinone, such as alkylisothiazolinones and benzisothiazolinones.
[097] Suitable antifreeze agents are ethylene glycol, propylene glycol, urea and glycerin.
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33/103 [098] Suitable antifoam agents are silicones, long-chain alcohols and fatty acid salts.
[099] Appropriate dyes (such as red, blue or green) are pigments with low water solubility and water-soluble dyes. Examples of inorganic dyes (such as iron oxide, titanium oxide and iron hexacyanoferrate) and organic dyes (such as alizarin, azo and phthalocyanine dyes).
[0100] Suitable adhesives or binders are polyvinylpyrrolidones, polyvinyl acetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes and cellulose ethers.
[0101] Examples of types of composition and their preparation are:
i. Water-soluble concentrates (SL, LS):
10-60% by weight of a compound I and 5-15% by weight of wetting agent (such as alcohol alkoxylates) are dissolved in water and / or in a water-soluble solvent (such as alcohols) to 100% by weight. The active substance is dissolved by dilution with water.
ii. Dispersible concentrates (DC):
5-25% by weight of a compound I and 1-10% by weight of dispersant (such as polyvinylpyrrolidone) are dissolved in up to 100% by weight of organic solvent (such as cyclohexanone). Dilution with water generates a dispersion.
iii. Emulsifiable concentrates (EC):
15-70% by weight of a compound I and 5-10% by weight of emulsifiers (such as calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in up to 100% by weight of water-insoluble organic solvent (such as hydrocarbon aromatic). Dilution with water generates an emulsion.
iv. Emulsions (EW, EO, ES):
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5-40% by weight of a compound I and 1-10% by weight of emulsifiers (such as calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20-40% by weight of water-insoluble organic solvent (such as aromatic hydrocarbon). This mixture is introduced in up to 100% by weight of water through an emulsifying machine and made in a homogeneous emulsion. Dilution with water generates an emulsion.
v. Suspensions (SC, OD, FS):
In a stirred ball mill, 20-60% by weight of a compound I is broken up with the addition of 2-10% by weight of dispersants and wetting agents (such as sodium lignosulfonate and alcohol ethoxylate), 0.1-2 % by weight of thickener (such as xanthan gum) and up to 100% by weight of water to generate a suspension of fine active substances. Dilution with water generates a stable suspension of the active substance. For composition of type FS, up to 40% by weight of binder (such as polyvinyl alcohol) is added.
saw. Water-dispersible granules and water-soluble granules (WG, SG):
50-80% by weight of a compound I are finely ground with the addition of up to 100% by weight of dispersants and wetting agents (such as sodium lignosulfonate and alcohol ethoxylate) and prepared in the form of water-dispersible or water-soluble granules technical applications (such as extrusion, spray tower or fluidized bed). Dilution with water generates a stable solution or dispersion of the active substance.
vii. Water-dispersible powders and water-soluble powders (WP, SP, WS):
50-80% by weight of a compound I are ground in a rotor-stator mill with the addition of 1-5% by weight of dispersants (such as
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35/103 sodium lignosulfonate), 1-3% by weight of wetting agents (such as alcohol ethoxylate) and up to 100% by weight of solid carrier, such as silica gel. Dilution with water generates a stable solution or dispersion of the active substance.
viii. Gel (GW, GF):
In a stirred ball mill, 5-25% by weight of a compound I is broken up with the addition of 3-10% by weight of dispersants (such as sodium lignosulfonate), 1-5% by weight of thickener (such as carboxymethylcellulose) ) and up to 100% by weight of water to generate a fine suspension of the active substance. Dilution with water generates a stable suspension of the active substance.
iv. Microemulsion (ME):
5-20% by weight of a compound I are added to 5-30% by weight of organic solvent mixture (such as fatty acid dimethylamide and cyclohexanone), 10-25% by weight of surfactant mixture (such as alcohol ethoxylate and arylphenol ethoxylate) and water up to 100%. This mixture is stirred for one hour to spontaneously produce a thermodynamically stable microemulsion.
iv. Microcapsules (CS):
An oil phase comprising 5-50% by weight of compound I, 0-40% by weight of water-insoluble organic solvent (such as aromatic hydrocarbon), 2-15% by weight of acrylic monomers (such as methyl methacrylate) , methacrylic acid and a di or triacrylate) are dispersed in an aqueous solution of a protective colloid (such as polyvinyl alcohol). Polymerization of radicals initiated by a radical initiator results in the formation of poly (meta) acrylate microcapsules. Alternatively, an oil phase comprising 5-50% by weight of a compound I according to the present invention, 0-40% by weight of water-insoluble organic solvent (such as aromatic hydrocarbon) and an isocyanate monomer (such as like 4.4 '
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36/103 diphenylmethane diisocyanate) are dispersed in an aqueous protective colloid solution (such as polyvinyl alcohol). The addition of a polyamine (such as hexamethylenediamine) results in the formation of polyurea microcapsules. Monomers represent 1-10% by weight. The weight percentage refers to the total composition of CS.
ix. Sprinkles (DP, DS):
1-10% by weight of a compound I is finely ground and thoroughly mixed with up to 100% by weight of solid vehicle, such as finely divided kaolin.
x. Granules (GR, FG):
0.5-30% by weight of a compound I is finely ground and associated with up to 100% by weight of solid vehicle (such as silicate). Granulation is achieved by means of extrusion, spray drying or fluidized bed.
xi. Ultra low volume liquids (UL):
1-50% by weight of a compound I are dissolved in up to 100% by weight of organic solvent, such as aromatic hydrocarbon.
[0102] Composition types ia xi can optionally comprise additional auxiliaries, such as 0.1-1% by weight of bactericides, 5-15% by weight of antifreeze agents, 0.1-1% by weight of antifoaming agents and 0.1-1% by weight of dyes.
[0103] The agrochemical compositions generally comprise from 0.01 to 95%, preferably from 0.1 to 90% and, preferably more, from 0.5 to 75% by weight of active substance. The active substances are used in purity of 90% to 100%, preferably from 95% to 100% (according to the NMR spectrum).
[0104] Water-soluble concentrates (LS), suspoemulsions (SE), fluid concentrates (FS), dry treatment powders (DS), dispersible powders in
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37/103 water for treating syrup (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually used for the purpose of treating plant propagation materials, particularly seeds. The compositions in question generate, after dilution of two to ten times, concentrations of active substance from 0.01 to 60% by weight, preferably from 0.1 to 40%, in ready-to-use preparations. The application can be carried out before or during cultivation. Methods of application or treatment with compound I and its compositions, respectively, to plant propagation material, especially seeds, include methods of covering, coating, pelletizing, dusting, soaking and application in pits of the propagation material. Preferably, compound I or its compositions, respectively, are applied to the plant propagation material by means of a method such that germination is not induced, for example, by means of seed covering, pelletizing, coating and dusting.
[0105] When used in plant protection, the amounts of active substances applied are, depending on the type of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0 , 9 kg per ha, particularly from 0.1 to 0.75 kg per ha.
[0106] When treating plant propagation materials such as seeds, for example sprinkling, coating or spraying seeds, amounts of active substance from 0.1 to 1000 g, preferably from 1 to 1000 g, are most preferably from 1 to 100 g, preferably from 5 to 100 g, per 100 kg of plant propagation material (preferably seeds).
[0107] When used to protect stored materials or products, the amount of active substance applied depends on the type of application area and the desired effect. Quantities usually
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38/103 applied in the protection of materials are, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
[0108] Various types of oils, humectants, adjuvants, fertilizers or micronutrients and other pesticides (such as herbicides, insecticides, fungicides, growth regulators and safety agents) can be added to the active substances or compositions that comprise them in the form of pre-mixing or, if appropriate, not until immediately before use (tank mixing). These agents can be mixed with the compositions according to the present invention in a weight ratio of 1: 100 to 100: 1, preferably 1:10 to 10: 1.
[0109] The user applies the composition according to the present invention normally from a pre-metering device, a backpack sprayer, a spray tank, a spray plane or an irrigation system. Typically, the agrochemical composition is composed of water, buffer and / or additional auxiliaries up to the desired application concentration and thus the ready-to-use spray liquid or agrochemical composition according to the present invention is obtained. Normally, 20 to 2000 liters, preferably 50 to 400 liters, of the spray liquid ready for use are applied per hectare of area useful for agriculture.
[0110] According to one embodiment, individual components of the composition according to the present invention such as parts of a kit or parts of a binary or ternary mixture can be mixed by the user himself in a spray tank and additional auxiliary aggregates can be added, if appropriate.
[0111] The mixture of compounds I or compositions comprising them in the form of use as fungicides with other fungicides results,
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39/103 in many cases, in an expansion of the spectrum of fungicidal activity that is obtained or prevents the development of resistance to fungicides. In addition, in many cases, synergistic effects are achieved.
[0112] The following list of active substances, together with which compound I can be used, is intended to illustrate possible combinations, but without limitations:
The. Breathing inhibitors:
- Complex III inhibitors at the Qo site (such as strobilurins): azoxystrobin, coumetoxistrobin, coumoxystrobin, dimoxystrobin, enestroburin, phenaminstrobin, phenoxystrobin / fluphenoxystrobin, fluoxystrobin, cresoxymethyl, metominostrobin, pyroboxystrine, pyrobostrobin, pyrobostrobin, pyrobostrobin, pyrobostrobin, pyrobostrobin, pyrobstrobin, pyrobostrobin, pyrobostrobin, pyrimobstrobin, pyrobostrobin, pyrobostrobin, pyrobstrobin, pyrimobstrobin, pyrobostrobin, pyrimobstrobin, pyrimobstrobin 2- [2- (2,5-dimethylphenoxymethyl) -phenyl] -3-methoxyacrylic acid methyl ester and 2- (2- (3- (2,6dichlorophenyl) -1-methylalylideneamino-oxymethyl) -phenyl) -2- methoxyimino-Nmethylacetamide, pyribencarb, triclopyricarb / chlorodincarb, famoxadone, phenamidone;
- complex III inhibitors at the Qi site: cyazofamid, amisulfon; [(3S, 6S, 7R, 8R) -8-benzyl-3 - [(3-acetoxy-4-methoxypyridine-2-carbonyl) amino] -6-methyl-4,9-dioxo-1,5- 2-methylpropanoate dioxonan-7-yl], [(3S, 6S, 7R, 8R) -8-benzyl-3 - [[3- (acetoxymethoxy) -4methoxypyridine-2-carbonyl] amino] -6-methyl-4,9 2-methylpropanoate -dioxo-1,5-dioxonan-7-yl], [(3S, 6S, 7R, 8R) -8-benzyl-3 - [(3-isobutoxycarbonyloxy-4-methoxypyridine-2-carbonyl) amino-6-methyl 2-methylpropanoate -4,9-dioxo-1,5-dioxonan-7-yl], [(3S, 6S, 7R, 8R) -8-benzyl-3 - [[3- (1,3-benzodioxol-5ylmethoxy) 2-methylpropanoate] -4-methoxypyridine-2-carbonyl] amino] -6-methyl-4,9-dioxo-1,5-dioxonan-7yl]; (3S, 6S, 7R, 8R) -3 - [[((3-hydroxy-4-methoxy-2pyridinyl) carbonyl] amino] -6-methyl-4,9-dioxo-8- (phenylmethyl) 2-methylpropanoate - 1,5-dioxonan-7-yl;
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- complex II inhibitors (such as carboxamides): benodanil, bixafen, boscalid, carboxin, fenfuram, fluopyram, flutolanil, fluxpyroxad, furametpir, isopyrazam, mepronil, oxycarboxin, penflufen, pentiopirad, silkxane, keyboardoftalam, niflamam, -trifluoromethylthiobiphenyl-2-yl) -
3-difluoromethyl-1-methyl-1H-pyrazolo-4-carboxamide, N- (2- (1,3,3-trimethylbutyl) phenyl) -1,3-dimethyl-5-fluoro-1H-pyrazolo-4-carboxamide , N- [9- (dichloromethylene) -
1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl] -3- (difluoromethyl) -1-methyl-1H-pyrazole-
4-carboxamide, 3- (difluoromethyl) -1-methyl-N- (1,1,3-trimethylindan-4-yl) pyrazolo-4carboxamide, 3- (trifluoromethyl) -1-methyl-N- (1,1, 3-trimethylindan-4-yl) pyrazolo-4carboxamide, 1,3-dimethyl-N- (1,1,3-trimethylindan-4-yl) pyrazolo-4-carboxamide, 3 (trifluoromethyl) -1,5-dimethyl- N- (1,1,3-trimethylindan-4-yl) pyrazolo-4-carboxamide, 3 (difluoromethyl) -1,5-dimethyl-N- (1,1,3-trimethylindan-4-yl) pyrazole-4 -carboxamide,
1,3,5-trimethyl-N- (1,1,3-trimethylindan-4-yl) pyrazolo-4-carboxamide;
- other respiration inhibitors (such as complex I, uncouplers); diflumetorim, (5-8-difluoroquinazolin-4-yl) - {2- [2-fluoro-4- (4trifluoromethylpyridin-2-yloxy) -phenyl] -ethyl} -amine; nitrophenyl derivatives; binapacril, dinobuton, dinocap, fluazinam; ferinzone; organometallic compounds: phentin salts, such as phentin acetate, fentin chloride or fentin hydroxide; ametoctradine; and siltiofam;
B. Sterol biosynthesis inhibitors (SBI fungicides):
- C14 demethylase inhibitors (DMI fungicides): triazoles:
azaconazole, bitertanol, bromuconazole, cyproconazole, diphenoconazole, diniconazole (including diniconazole-M), epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazol, methanol, pacconazole, protonazole, metconazole, protonazole tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, re / - (2S, 3R) -3- (2-chlorophenyl) -2- (2,4-difluorophenyl) oxiranylmethyl] -5-thiocyanate-1H- [1, 2.4] triazole, 2- [re / - (2S, 3R) -3- (2-chlorophenyl) -2- (2.4 Petition 870190031114, from 04/01/2019, page 50/126
41/103 difluorophenyl) -oxyranylmethyl] -2H- [1,2,4] triazolo-3-thiol; imidazoles: imazalil, pefurazoate, prochloraz, triflumizole; pyrimidines, pyridines and piperazines: fenarimol, nuarimol, pyrifenox, triforin;
- Delta-14-reductase inhibitors: aldimorf, dodemorf, dodemorf acetate, fenpropimorf, tridemorf, fenpropidina, piperalina, spiroxamina;
- 3-keto reductase inhibitors: fenhexamid;
ç. Nucleic acid synthesis inhibitors:
- acyl amino acid phenylamides or fungicides: benalaxyl, benalaxyl-M, chiralaxyl, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixil;
- others: himexazole, octylinone, oxolinic acid, bupirimate,
5-fluorocytosine, 5-fluoro-2- (p-tolylmethoxy) pyrimidin-4-amine, 5-fluoro-2- (4-fluorophenylmethoxy) pyrimidin-4-amine;
d. Cell division and cytoskeleton inhibitors:
- Tubulin inhibitors, such as benzimidazoles, thiophanates:
benomyl, carbendazim, fuberidazole, thiabendazole, methyl thiophanate; triazolopyrimidines: 5-chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl)] 1,2,4] triazolo [1,5-a] pyrimidine;
- other cell division inhibitors: dietofencarb, etaboxam, pencicuron, fluopicolide, zoxamide, metrafenone, pyrophenone;
and. Protein and amino acid synthesis inhibitors:
- inhibitors of methionine synthesis (anilinopyrimidines): cyprodinil, mepanipyrim, pyrimethanil;
- protein synthesis inhibitors: blasticidin S, casugamycin, casugamycin hydrate / hydrochloride, mildiomycin, streptomycin, oxytetracycline, polyoxin, validamycin A;
f. Inhibitors of signal transduction:
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- MAP / histidine kinase inhibitors: fluoroimid, iprodione, procymidone, vinclozoline, fenpiclonil, fludioxonil;
- G protein inhibitors: quinoxifen;
g. Inhibitors of lipid and membrane synthesis:
- phospholipid biosynthesis inhibitors: edifenfós, iprobenfós, pyrazofós, isoprothiolane;
- lipid peroxidation: dichloran, quintozene, tecnazene, methyl tolclofós, biphenyl, cloroneb, etridiazole;
- phospholipid biosynthesis and cell wall deposition: dimetomorf, flumorf, mandipropamid, pyrimorf, bentiavalicarb, iprovalicarb, valifenalate and N- (1- (1- (4 (cyanophenyl) ethanesulfonyl) -but-2- acid ester (N-(1- (4-cyanophenyl) ethanesulfonyl) -but-2- il) carbamic;
- compounds that affect the permeability of cell membranes and fatty acids: propamocarb, propamocarb hydrochloride;
- fatty acid amide hydrolase inhibitors: 1- [4 [4- [5- (2,6-difluorophenyl) -4,5-dihydro-3-isoxazolyl] -2-thiazolyl] -1-piperidinyl] -2- [5methyl-3- (trifluoromethyl) -1H-pyrazol-1-yl] ethanone;
H. Inhibitors with action in multiple locations:
- inorganic active substances: mixture of Bordeaux, copper acetate, copper hydroxide, copper oxychloride, basic copper sulphate, sulfur;
- uncle and dithiocarbamates: ferbam, mancozeb, maneb, metam, metiram, propineb, tiram, zineb, ziram;
- organochlorine compounds (such as phthalimides, sulfamides, chloronitriles): anilazine, chlorothalonil, captafol, captan, folpet, diclofluanid, dichlorophen, flussulfamide, hexachlorobenzene, pentachlorphenol and their salts, phthalide, tolylfluanid, N- ) -N-ethyl-4methylbenzenesulfonamide;
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- guanidines and others: guanidine, dodine, dodine-free base, guazatin, guazatin acetate, iminoctadine, iminoctadine triacetate, iminoctadine tris (albesylate), dithianon, 2,6-dimethyl-1H, 5H [1,4] diti -ino [2,3-c; 5,6-c '] dipyrrolo-1,3,5,7 (2H, 6H) -tetraone;
i. Inhibitors of cell wall synthesis:
- glucan synthesis inhibitors: validamycin, polyoxin B; inhibitors of melanin synthesis: pyrokylone, tricyclazole, carpropamid, dicyclomethane, phenoxanil;
j. Plant defense inducers:
- acibenzolar-S-methyl, probenazole, isothianyl, thiadinyl, prohexadione calcium; phosphonates: fosetil, fosetil aluminum, phosphorous acid and its salts;
k. Unknown mode of action:
- bronopol, chinometionat, ciflufenamid, cymoxanil, dazomet, debacarb, diclomezine, dipenzoquat, diphenylat-sulfate methyl, diphenylamine, fempyrazamine, flumetover, flussulfamide, flutianyl, metassulfocarb, nitrapirin, nitrotoxin, trioxin, isopropyl, trioxin, isopropyl, trinochoxy 2butoxy-6-iodo-3-propylchromen-4-one, N- (cyclopropylmethoxy-imino- (6difluoromethoxy-2,3-difluorophenyl) -methyl) -2-phenyl acetamide, N '- (4- (4-chloro- 3trifluoromethylphenoxy) -2,5-dimethylphenyl) -N-ethyl-N-methyl formamidine, N '- (4- (4-fluoro3-trifluoromethylphenoxy) -2,5-dimethylphenyl) -N-ethyl-N-methyl formamidine, N '- (2-methyl-5trifluoromethyl-4- (3-trimethylsilanylpropoxy) -phenyl) -N-ethyl-N-methyl formamidine, N' - (5difluoromethyl-2-methyl-4- (3-trimethylsilanylpropoxy) -phenyl) - 2- {1- [2- (5-Methyl-3-trifluoromethylpyrazol-1-yl) methyl- (1,2,3,4-tetrahydronaphthalen-1-yl) -amide ) -acetyl] -piperidin4-yl} thiazole-4-carboxylic, methyl- (R) -
2- {1- [2- (5-methyl-3-trifluoromethylpyrazol-1-yl) -acetyl] -piperidin-4-yl} -thiazole 1,2,3,4-tetrahydronaphthalen-1-ylamide -4-carboxylic, 1- [4- [4- [5 (2,6-difluorophenyl) -4,5-dihydro-3-isoxazolyl] -2-thiazolyl] -1-piperidinyl] -2- [5 -methyl-3
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44/103 (trifluoromethyl) -1H-pyrazol-1-yl] ethanone, 6-tert-butyl-8-fluoro-2,3-dimethylquinolin-4yl methoxyacetic acid ester, M-methyl-2- [1 - [( 5-methyl-3-trifluoromethyl-1H-pyrazol1 -yl) -acetyl] -piperidin-4-yl] -M - [(1 R) -1,2,3,4-tetrahydronaphthalen-1-yl] - 4thiazolocarboxamide, 3- [5- (4-methylphenyl) -2,3-dimethylisoxazolidin-3-yl] -pyridine, 3- [5 (4-chlorophenyl) -2,3-dimethylisoxazolidin-3-yl] -pyridine (pyrisoxazol ), N- (6-methoxypyridin-3-yl) cyclopropanecarboxylic acid amide, 5-chloro-1- (4,6-dimethoxypyrimidin2-yl) -2-methyl-1H-benzoimidazole, 2- (4-chlorophenyl) - N- [4- (3,4-dimethoxyphenyl) -isoxazol5-yl] -2-prop-2-ynyloxyacetamide;
l. Antifungal biocontrol agents, plant bioactivators: Ampelomyces quisqualis (such as AQ 10® from Intrachem Bio GmbH & Co. KG, Germany), Aspergillus flavus (such as AFLAGUARD® from Syngenta, CH), Aureobasidium pullulans (such as BOTECTOR® from Bio -Ferm GmbH, Germany), Bacillus pumilus (as accession number NRRL B-30087 in SONATA® and BALLAD® Plus from AgraQuest Inc., United States), Bacillus subtilis (as isolated NRRL No. B-21661 in RHAPSODY® , SERENADE® MAX and SERENADE® ASO by AgraQuest Inc., United States), Bacillus subtilis var. amyloliquefaciens FZB24 (such as TAEGRO® by Novozyme Biologicals, Inc., United States), Candida oleophila I-82 (such as ASPIRE® by Ecogen Inc., United States), Candida saitoana (such as BIOCURE® (mixed with lysozyme) and BIOCOAT® by Micro Flo Company, United States (BASF SE) and Arysta), Chitosan (such as ARMOUR-ZEN by BotriZen Ltd., New Zealand), Clonostachys rosea f. catenulata, also called Gliocladium catenulatum (as isolated J1446: PRESTOP® from Verdera, Finland), Coniothyrium minitans (such as CONTANS® from Prophyta, Germany), Cryphonectria parasitica (such as Endothia parasitica from CNICM, France), Cryptococcus albidus (such such as YIELD PLUS® by Anchor Bio-Technologies, South Africa), Fusarium oxysporum (such as BIOFOX® by SIAPA, Italy, FUSACLEAN® by Natural Plant Protection, France), Metschnikowia fructicola
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45/103 (such as SHEMER® from Agrogreen, Israel), Microdochium dimerum (such as ANTIBOT® from Agrauxine, France), Phlebiopsis gigantea (such as ROTSOP® from Verdera, Finland), Pseudozyma flocculosa (such as SPORODEX® from Plant Products Co. Ltd., Canada), Pythium oligandrum DV74 (such as POLYVERSUM® by Remeslo SSRO, Biopreparaty, Czech Republic), Reynoutria sachlinensis (such as REGALIA® by Marrone BioInnovations, United States), Talaromyces flavus V117b (such as PROTUS® by Prophyta, Germany), Trichoderma asperellum SKT-1 (such as ECO-HOPE® by Kumiai Chemical Industry Co., Ltd., Japan), T. atroviride LC52 (such as SENTINEL® by Agrimm Technologies Ltd., New Zealand), T harzianum T-22 (such as PLANTSHIELD® by BioWorks Inc., United States), T. harzianum TH 35 (such as ROOT PRO® by Mycontrol Ltd., Israel), T. harzianum T-39 (such as TRICHODEX® and TRICHODERMA 2000® by Mycontrol Ltd., Israel and Makhteshim Ltd., Israel), T. harzianum and T. viride (as TRICHOPEL by Agrimm Technologies Ltd., New Zealand), T. harzianum ICC012 and T. viride ICC080 (such as REMEDIER® WP by Isagro Ricerca, Italy), T. polysporum and T. harzianum (such as BINAB® by BINAB Bio-Innovation AB, Sweden), T. stromaticum (such as TRICOVAB® from CEPLAC, Brazil), T. virens GL-21 (such as SOILGARD® from Certis LLC, United States), T. viride (such as TRIECO® from Ecosense Labs. (India) Pvt. Ltd., India, BIO-CURE® F. by T. Stanes & Co. Ltd., India), T. viride TV1 (such as T. viride TV1 by Agribiotec srl, Italy), Ulocladium oudemansii HRU3 (such as BOTRY-ZEN ^® by Botry-Zen Ltd., New Zealand);
m. Growth regulators:
- abscisic acid, amidochlor, ancimidol, 6-benzylaminopurine, brassinolide, butralin, clormequat (clormequat chloride), choline chloride, cyclanilide, daminozide, dikegulac, dimetipin, 2,6-dimethylpuridine, etefon, flumetralin, flumetralin, flumetralin, flumetralin, flumetralin, flumetralin, flumetralin, flumetralin , gibberellic acid, inabenfide,
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46/103 indole-3-acetic acid, maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), naphthalenoacetic acid, N-6-benzyladenine, paclobutrazol, prohexadione (pro-hexadione calcium), pro-hydrojasmon, thidiazuron, triapentenol, triapentenol tributyl, 2,3,5-triiodothenzoic acid, trinexapac-ethyl and uniconazole;
n. Herbicides:
- acetamides: acetochlor, alachlor, butachlor, dimetachlor, dimethanamid, flufenacet, mefenacet, metolachlor, metazachlor, napropamide, naproanilide, petoxamid, pretilachlor, propachlor and tenilchlor;
- amino acid derivatives: bilanafos, glyphosate, glufosinate, sulfosate;
- aryloxyphenoxypropionates: clodinafop, ci-halofop butyl, fenoxaprop, fluazifop, haloxifop, metamifop, propaquizafop, quizalofop, quizalofop-P-tefuril;
- bipyridyls: diquat, paraquat;
- (thio) carbamates: assulam, butylate, carbetamide, desmedipham, dimepiperate, eptam (EPTC), esprocarb, molinate, orbencarb, fenmedipham, prosulfocarb, pyributicarb, thiobencarb, trialate;
- cyclohexanediones: butroxidim, cletodim, cicloxidim, profoxidim, setoxidim, tepraloxidim, tralcoxidim;
- dinitroanilines: benfluralin, etalfluralin, orizalin, pendimetalin, prodiamine, trifluralin;
- diphenyl ethers: acifluorfen, aclonifen, bifenox, diclofop, ethoxyfen, fomesafen, lactofen, oxifluorfen;
- hydroxybenzonitriles; bomoxinil, diclobenyl, ioxynil;
- imidazolinones; imazametabenzo, imazamox, imazapic, imazapyr, imazaquin, imazetapyr;
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- phenoxyacetic acids: clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-DB, dichlorprop, MCPA, MCPA-thioethyl, MCPB, mecoprop;
- pyrazines; chloridazon, flufenpir ethyl, flutiacet, norflurazon, pyridate;
- pyridines: aminopyralid, clopyralid, diflufenican, dithiopir, fluridone, fluroxypyr, picloram, picolinafen, tiazopir;
- sulfonyl ureas: amidosulfuron, azinsulfuron, bensulfuron, chlorimuron-ethyl, chlorsulfuron, cinossulfuron, ciclossulfamuron, etoxissulfuron, flazassulfuron, flucetossulfuron, flupirsulfuron, foransulfuron, halossulfuron, imazossulfuron, iodossulfuron, mesossulfuron, metazossulfuron, metsulfuron-methyl, nicosulfuron, oxassulfuron, primisulfuron, prosulfuron, pyrazosulfuron, rinsulfuron, sulfometuron, sulfosulfuron, tifensulfuron, triasulfuron, tribenuron, trifloxysulfuron, triflussulfuron, tritosulfuron, 1 - ((2-chloro-6-propylimidazo [1,2b] pyridazin-3-yl) -3-3-yl) 6-dimethoxypyrimidin-2-yl) urea;
- triazines: amethrine, atrazine, cyanazine, dimetamethrin, ethiozine, hexazinone, metamitron, metribuzin, promethrin, simazine, terbuthylazine, terbutrin, triaziflam;
- ureas: chlorotoluron, daimuron, diuron, fluometuron, isoproturon, linuron, metabenzothiazuron, tebutiuron;
- other acetolactate synthase inhibitors: bispyribacsodium, chloransulam-methyl, diclosulam, florassulam, flucarbazone, flumetsulam, metosulam, orthosulfamuron, penoxsulam, propoxycarbazone, piribambenzopropil, pyribenzoximone, pyrysulfan, pyripyrine, pyripyrine, pyripyrine, pyripyrine, pyripyrine, pyripyrine, pyripyrine, pyripyrine, pyripyrine, pyridine, pyripyrine, pyripyrine, pyripyrine, pyripyrine, pyripyrine, pyripyrine, pyripyrine, pyripyrine, pyrimine, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine;
- others: amicarbazone, aminotriazole, anilofós, beflubutamid, benazolin, bencarbazone, benfluresate, benzofenap, bentazone, benzobicyclon, bicyclopyrone, bromacil, bromobutide, butafenacil, butamiphos, cafenstrol,
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48/103 carfentrazone, cinidon ethyl, chlortal, cinmetilin, clomazone, cumiluron, cyprosulfamide, dicamba, difenzoquat, diflufenzopyr, Drechslera monoceras, endotal, etofumesate, etobenzanid, fenoxassulfone, fentrazamide, flentochuram, flumiclorachoxo , isoxaflutol, lenacil, propanil, propizamide, quinclorac, quinmerac, mesotrione, arsenic methyl acid, naptalam, oxadiargil, oxadiazon, oxaziclomefone, pentoxazone, pinoxaden, piraclonil, piraflufen ethyl, pirassulfotyl, pyrazoxyl, pyrazoxyl, pyrazoxyl, pyrazoxyl, pyrazoxyl, pyrazoxyl, pyrazoxyl, pyrazoxyl, pyrazulfoxyl, pyrazoxyl, pyrazulfoxyl, pyrazoxyl, pyrazoxyl, pyrazoxamine terbacil, tefuryltrione, tembotrione, thiencarbazone, topramezone, ethyl acid ester (3- [2-chloro-4-fluoro-5- (3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H -pyrimidin-1-yl) phenoxy] -pyridin-2-yloxy) -acetic, 6-amino-5-chloro-2cyclopropylpyrimidine-4-carboxylic acid methyl ester, 6-chloro-3- (2-cyclopropyl-6- methylphenoxy) pyridazin-4-ol, 4-amino-3-chloro-6- (4-chloropheni) l) -5-fluoropyridine-2-carboxylic acid, 4-amino-3-chloro-6- (4-chloro-2-fluoro-3-methoxyphenyl) -pyridine-2-carboxylic acid methyl ester and 4-amino-3 acid methyl ester -chloro-6- (4chloro-3-dimethylamino-2-fluorophenyl) -pyridine-2-carboxylic.
O. Insecticides:
- organo (uncle) phosphates: acephate, azametiphos, methyl azinfos, chlorpyrifos, methyl chlorpyrifos, chlorfenvinfos, diazinon, dichlorvos, dicrotophos, dimetoate, disulfoton, etion, fenitrotion, fention, isoxation, malation, metamidophos, metamidophos, metamidophos, metamidophos, monocrophotós, oxidemeton methyl, paraoxon, paration, fentoate, fosalone, fosmet, fosfamidon, forato, foxim, methyl pyrimiphos, profenofós, protiofós, sulprofós, tetrachlorvinfós, terbufós, triazofós, triclorfon;
- carbamates: alanicarb, aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosulfan, phenoxicarb, furatiocarb, metiocarb, metomyl, oxamil, pyrimicarb, propoxur, tiodicarb, triazamate;
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- pyrethroids: alethrin, bifenthrin, cyflothrin, cyhalothrin, cyphenothrin, cypermethrin, alphaipermethrin, betacypermethrin, zetacipermethrin, deltamethrin, sphenoparrene, etofenprox, fenpropatrine, permethrin, imetretrine, prethetrothrin, prethetrothrin, prethetrothrin, prethetrothrin, prethetrothrin, prethetrothrin, prethetrin, pyrethetrin, prethetrin, pyrethetrin, prethetrothrin, silafluofen, taufluvalinate, teflutrin, tetramethrin, tralometrine, transflutrin, proflutrin, dimeflutrin;
- insect growth regulators: a) inhibitors of chitin synthesis: benzoylureas: chlorfluazuron, ciramazine, diflubenzuron, flucicloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron; buprofezin, diofenolan, hexitiazox, ethoxazole, clofentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide, azadiractin; c) juvenoids: pyriproxifen, methoprene, phenoxicarb; d) lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramat;
- nicotinic receptor agonist and antagonist compounds: clothianidin, dinotefuran, flupiradifurone, imidacloprid, thiametoxam, nitempiram, acetamiprid, thiacloprid, 1- (2-chlorothiazol-5-ylmethyl) -2-nitrimino-3,5dimethyl- [1,3,5 ] triazinane;
- GABA antagonist compounds: endosulfan, etiprol, fipronil, vaniliprol, pirafluprol, pyriprol, 5-amino-1- (2,6-dichloro-4methylphenyl) -4-sulfinamoyl-1H-pyrazolo-3-carbotioic acid amide;
- macrocyclic lactone insecticides: abamectin, emamectin, milbemectin, lepimectin, spinosad, espinetoram;
- mitochondrial electron transport inhibitor (METI) I acaricides: phenazaquin, pyridaben, tebufenpirad, tolfenpirad, flufenerim;
- METI II and III compounds: acequinocil, fluaciprim, hydramethylnon;
- uncouplers: chlorfenapyr;
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- inhibitors of oxidative phosphorylation: cyhexatin, diafentiuron, fenbutatin oxide, propargite;
- hair exchange suspension compounds: cryomain;
- mixed function oxidase inhibitors: piperonyl butoxide;
- sodium channel blockers: indoxacarb, metaflumizone;
- others: benclothiaz, biphenazate, cartap, flonicamid, pyridalil, pimetrozina, sulfur, thiocyclam, flubendiamide, chlorantraniliprol, ciazipir (HGW86), cienopirafen, flupirazofós, ciflumetofen, amidoflazon, amidoflazon, amidoflazone
[0113] The present invention also relates to agrochemical compositions that comprise a mixture of at least one compound I (component 1) and at least one additional active substance useful for plant protection, selected, for example, from groups a to o (component 2), particularly an additional fungicide, such as one or more fungicides from groups 1 to 1, as described above, and, if desired, an appropriate solvent or solid vehicle. These mixtures are of specific interest, as many of them at the same application rate exhibit higher efficiencies against harmful fungi. In addition, combating harmful fungi with a mixture of compounds I and at least one fungicide from groups a to 1, as described above, is more efficient than combating those fungi with individual compounds I or individual fungicides from groups a to 1. By applying compounds I together with at least one active substance from groups a to a, a synergistic effect can be obtained, that is, more than the simple addition of individual effects (synergistic mixtures) is obtained.
[0114] This can be achieved by applying compounds I and at least one additional active substance simultaneously, either together (as
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51/103 as in the form of a tank mixture), separately or successively, in which the time interval between individual applications is selected to ensure that the active substance applied in the first place still occurs at the site of action in sufficient quantity at the time of application. application of the additional active substance (s). The order of application is not essential to the work of the present invention.
[0115] In binary mixtures, that is, compositions according to the present invention comprising a compound I (component 1) and an additional active substance (component 2), such as an active substance from groups a to o, the ratio in weight between component 1 and component 2 generally depends on the properties of the active substances used and is usually in the range of 1: 100 to 100: 1, regularly in the range of 1:50 to 50: 1, preferably in the range of 1:20 to 20: 1, most preferably in the range of 1:10 to 10: 1 and, particularly, in the range of 1: 3 to 3: 1.
[0116] In ternary mixtures, that is, compositions according to the present invention comprising a compound I (component 1), a first additional active substance (component 2) and a second additional active substance (component 3), such as two active substances from groups a to o, the weight ratio between component 1 and component 2 depends on the properties of the active substances used and is preferably in the range of 1:50 to 50: 1, particularly in the range of 1:10 to 10 : 1, and the weight ratio between component 1 and component 3 is preferably in the range of 1:50 to 50: 1 and particularly in the range of 1:10 to 10: 1.
[0117] Preference is also given to mixtures comprising a compound I (component 1) and at least one active substance selected from group a (component 2) and particularly selected from azoxystrobin, dimoxystrobin, fluoxastrobin, methyl cresoxim, orysstrobin ,
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52/103 picoxystrobin, pyraclostrobin, trifloxystrobin; famoxadone, phenamidone; bixafen, boscalid, fluopyram, fluxpyroxad, isopyrazam, penflufen, pentiopirad, silkxane; ametoctradin, ciazofamid, fluazinam and fentin salts, such as fentin acetate.
[0118] Preference is given to mixtures comprising a compound of formula I (component 1) and at least one active substance selected from group b (component 2) and particularly selected from cyproconazole, diphenoconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, metconazole, myclobutanil, penconazole, propiconazole, protioconazole, triadimefon, triadimenol, tebuconazole, tetraconazole, triticonazole, prochloraz, phenarimol, triforin; dodemorf, fenpropimorf, tridemorf, fenpropidin, spiroxamine; fenhexamid.
[0119] Preference is given to mixtures comprising a compound of Formula I (component 1) and at least one active substance selected from group c (component 2) and particularly selected from metalaxyl (metalaxyl-M), mefenoxam and ofurace.
[0120] Preference is given to mixtures comprising a compound of Formula I (component 1) and at least one active substance selected from the group d (component 2) and particularly selected from benomyl, carbendazim, methyl thiophanate, etaboxam , fluopicolide, zoxamide, metrafenone and pyriophenone.
[0121] Preference is also given to mixtures comprising a compound I (component 1) and at least one active substance selected from the group e (component 2) and particularly selected from cyprodinil, mepanipyrim and pyrimethanil.
[0122] Preference is also given to mixtures comprising a compound I (component 1) and at least one selected active substance
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53/103 from group f (component 2) and particularly selected from iprodione, fludioxonil, vinclozolin and quinoxifen.
[0123] Preference is also given to mixtures comprising a compound I (component 1) and at least one active substance selected from the group g (component 2) and particularly selected from dimetomorf, flumorf, iprovalicarb, bentiavalicarb, mandipropamid and propamocarb.
[0124] Preference is also given to mixtures comprising a compound I (component 1) and at least one active substance selected from group h (component 2) and particularly selected from copper acetate, copper hydroxide, oxychloride copper, copper sulfate, sulfur, mancozeb, metiram, propineb, strip, captafol, folpet, chlorotalonil, diclofluanid and dithianon.
[0125] Preference is also given to mixtures comprising a compound I (component 1) and at least one active substance selected from group i (component 2) and particularly selected from carpropamid and phenoxanil.
[0126] Preference is also given to mixtures comprising a compound I (component 1) and at least one active substance selected from group j (component 2) and particularly selected from acibenzolar-S-methyl, probenazole, thiadinyl , fosetil, fosetil aluminum, H3PO3 and its salts.
[0127] Preference is also given to mixtures comprising a compound I (component 1) and at least one active substance selected from the group k (component 2) and particularly selected from cymoxanil, proquinazid and V-methyl-2 - {1 - [(5-methyl-3-trifluoromethyl-1H-pyrazol-1-yl) acetyl] -piperidin-4-yl} -V - [(1 R) -1,2,3,4-tetra- hydronaphthalen-1-yl] -4thiazolocarboxamide.
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54/103 [0128] Preference is also given to mixtures comprising a compound I (component 1) and at least one active substance selected from group 1 (component 2) and particularly selected from Bacillus subtilis strain NRRL n ° B-21661, Bacillus pumilus strain NRRL No. B-30087 and Ulocladium oudemansii.
[0129] Consequently, the present invention also relates to compositions comprising a compound I (component 1) and an additional active substance (component 2), in which that additional active substance is selected from the “Component 2” column of lines B-1 to B360 of Table B.
[0130] An additional embodiment refers to compositions B-1 to B-360 listed in Table B, in which a row of Table B corresponds, in each case, to a fungicidal composition comprising one of the compounds individualized according to the present invention of Formula I (component 1) and the corresponding additional active substance from groups a to (component 2) indicated in the row in question. Preferably, the described compositions comprise the active substances in synergistically effective amounts.
Table B [0131] Composition comprising an individualized compound I and an additional active substance from groups a to:
Mixture Component 1 Component 2 B-1 an individualized compound I Azoxystrobin B-2 an individualized compound I Coumetoxistrobina B-3 an individualized compound I Coumoxystrobin
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Mixture Component 1 Component 2 B-4 an individualized compound I Dimoxystrobin B-5 an individualized compound I Enstroburine B-6 an individualized compound I Phenaminastrobin B-7 an individualized compound I Phenoxystrobin / Fluphenoxystrobin B-8 an individualized compound I Fluoxastrobin B-9 an individualized compound I Cresoxim-methyl B-10 an individualized compound I Metominostrobin B-11 an individualized compound I Orisastrobina B-12 an individualized compound I Picoxystrobin B-13 an individualized compound I Pyraclostrobin B-14 an individualized compound I Pyramethostrobin B-15 an individualized compound I Piraoxystrobin B-16 an individualized compound I Piribencarb B-17 an individualized compound I Trifloxystrobin B-18 an individualized compound I T riclopiricarb / Chlorodinacarb B-19 an individualized compound I 2- [2- (2,5dimethylphenoxymethyl) -phenyl] -3methoxyacrylic acid methyl ester
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Mixture Component 1 Component 2 B-20 an individualized compound I 2- (2- (3- (2,6-dichlorophenyl) -1methylalylidanoamino-oxymethyl) phenyl) -2-methoxy-imino-N-methylacetamide B-21 an individualized compound I Benalaxil B-22 an individualized compound I Benalaxil-M B-23 an individualized compound I Benodanil B-24 an individualized compound I Bixafen B-25 an individualized compound I Boscalid B-26 an individualized compound I Carboxine B-27 an individualized compound I Fenfuram B-28 an individualized compound I Fenhexamid B-29 an individualized compound I Flutolanil B-30 an individualized compound I Fluxapiroxad B-31 an individualized compound I Furametpir B-32 an individualized compound I Isopirazam B-33 an individualized compound I Isothianil B-34 an individualized compound I Ciralaxil B-35 an individualized compound I Mepronil
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Mixture Component 1 Component 2 B-36 an individualized compound I Metalaxyl B-37 an individualized compound I Metalaxyl-M B-38 an individualized compound I Ofurace B-39 an individualized compound I Oxadixil B-40 an individualized compound I Oxycarboxine B-41 an individualized compound I Penflufen B-42 an individualized compound I Pentiopirad B-43 an individualized compound I Sedaxane B-44 an individualized compound I Tecloftalam B-45 an individualized compound I Tifluzamide B-46 an individualized compound I Tiadinail B-47 an individualized compound I 2-Amino-4- acid anilidemethylthiazole-5-carboxylic B-48 an individualized compound I N- (4'-trifluoromethylthiobiphenyl-2-yl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide B-49 an individualized compound I N- (2- (1,3,3-trimethylbutyl) -phenyl) -1,3-dimethyl-5-fluoro-1H-pyrazole-4-carboxamide
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Mixture Component 1 Component 2 B-50 an individualized compound I N- [9- (dichloromethylene) -1,2,3,4tetrahydro-1,4-methanonaphthalen-5yl] -3- (difluoromethyl) -1-methyl-1Hpyrazole-4-carboxamide B-51 an individualized compound I Dimetomorf B-52 an individualized compound I Flumorf B-53 an individualized compound I Pirimorf B-54 an individualized compound I Flumetover B-55 an individualized compound I Fluopicolide B-56 an individualized compound I Fluopiram B-57 an individualized compound I Zoxamide B-58 an individualized compound I Carpropamid B-59 an individualized compound I Diclocimet B-60 an individualized compound I Mandipropamid B-61 an individualized compound I Oxytetracycline B-62 an individualized compound I Siltiofam B-63 an individualized compound I N- (6methoxypyridin-3-yl) cyclopropanecarboxylic acid amide B-64 an individualized compound I Azaconazole
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Mixture Component 1 Component 2 B-65 an individualized compound I Bitertanol B-66 an individualized compound I Bromuconazole B-67 an individualized compound I Ciproconazole B-68 an individualized compound I Diphenoconazole B-69 an individualized compound I Diniconazole B-70 an individualized compound I Diniconazole-M B-71 an individualized compound I Epoxiconazole B-72 an individualized compound I Fenbuconazole B-73 an individualized compound I Fluquinaconazole B-74 an individualized compound I Flusilazole B-75 an individualized compound I Flutriafol B-76 an individualized compound I Hexaconazole B-77 an individualized compound I Imibenconazole B-78 an individualized compound I Ipconazole B-79 an individualized compound I Metconazole B-80 an individualized compound I Miclobutanil B-81 an individualized compound I Oxpoconazole B-82 an individualized compound I Paclobutrazol
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Mixture Component 1 Component 2 B-83 an individualized compound I Penconazole B-84 an individualized compound I Propiconazole B-85 an individualized compound I Protioconazole B-86 an individualized compound I Simeconazole B-87 an individualized compound I Tebuconazole B-88 an individualized compound I Tetraconazole B-89 an individualized compound I Triadimefon B-90 an individualized compound I Triadimenol B-91 an individualized compound I Triticonazole B-92 an individualized compound I Uniconazole B-93 an individualized compound I Ciazofamid B-94 an individualized compound I Imazalil B-95 an individualized compound I Imazalil sulfate B-96 an individualized compound I Pefurazoate B-97 an individualized compound I Procloraz B-98 an individualized compound I Triflumizole B-99 an individualized compound I Benomil B-100 an individualized compound I Carbendazim
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Mixture Component 1 Component 2 B-101 an individualized compound I Fuberidazole B-102 an individualized compound I Thiabendazole B-103 an individualized compound I Etaboxam B-104 an individualized compound I Etridiazole B-105 an individualized compound I Himexazole B-106 an individualized compound I 2- (4-Chlorophenyl) -N- [4- (3,4-dimethyl-oxyphenyl) -isoxazol-5-yl] -2-prop-2-inyloxyacetamide B-107 an individualized compound I Fluazinam B-108 an individualized compound I Pirifenox B-109 an individualized compound I 3- [5- (4-Chlorophenyl) -2,3-dimethylisoxazolidin-3-yl] -pyridine(pyrisoxazole) B-110 an individualized compound I 3- [5- (4-Methylphenyl) -2,3-dimethylisoxazolidin-3-yl] -pyridine B-111 an individualized compound I Bupirimate B-112 an individualized compound I Ciprodinil B-113 an individualized compound I 5-Fluorocytosine B-114 an individualized compound I 5-Fluoro-2- (p-tolylmethoxy) pyrimidin-4-amine
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Mixture Component 1 Component 2 B-115 an individualized compound I 5-Fluoro-2- (4-fluorophenylmethoxy) -pyrimidin-4-amine B-116 an individualized compound I Diflumetorim B-117 an individualized compound I (5,8-Difluoroquinaazolina-4-yl) -{2- [2-fluoro-4- (4trifluoromethylpyridin-2-yloxy) -phenyl] ethyl} -amine B-118 an individualized compound I Fenarimol B-119 an individualized compound I Ferinzona B-120 an individualized compound I Mepanipirim B-121 an individualized compound I Nitrapirin B-122 an individualized compound I Nuarimol B-123 an individualized compound I Pyrimethanil B-124 an individualized compound I Triforine B-125 an individualized compound I Fenpiclonil B-126 an individualized compound I Fludioxonil B-127 an individualized compound I Aldimorf B-128 an individualized compound I Dodemorf B-129 an individualized compound I Dodemorf acetate
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Mixture Component 1 Component 2 B-130 an individualized compound I Fenpropimorf B-131 an individualized compound I Tridamorf B-132 an individualized compound I Fenpropidin B-133 an individualized compound I Fluoroimid B-134 an individualized compound I Iprodiona B-135 an individualized compound I Procimidone B-136 an individualized compound I Vinaclozoline B-137 an individualized compound I Famoxadone B-138 an individualized compound I Fenamidone B-139 an individualized compound I Flutianil B-140 an individualized compound I Octyline B-141 an individualized compound I Probenazole B-142 an individualized compound I Fenpyrazamine B-143 an individualized compound I Acibenzolar-S-methyl B-144 an individualized compound I Ametoctradine B-145 an individualized compound I Amissulbrom
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Mixture Component 1 Component 2 B-146 an individualized compound I 2-Methylpropanoate[(3S, 6S, 7R, 8R) -8-benzyl-3 - [(3isobutyryloxymethoxy-4methoxypyridine-2-carbonyl) amino] -6-methyl-4,9dioxo- [1,5] dioxonan-7-yl] B-147 an individualized compound I 2-Methylpropanoate[(3S, 6S, 7R, 8R) -8-benzyl-3 - [(3acetoxy-4-methoxypyridine-2carbonyl) amino] -6-methyl-4,9dioxo-1,5-dioxonan-7-yl] B-148 an individualized compound I 2-Methylpropanoate[(3S, 6S, 7R, 8R) -8-benzyl-3 - [[3 (acetoxymethoxy) -4methoxypyridine-2-carbonyl] amino] -6-methyl-4,9dioxo-1,5-dioxonan-7-yl] B-149 an individualized compound I 2-Methylpropanoate[(3S, 6S, 7R, 8R) -8-benzyl-3 - [(3isobutoxycarbonyloxy-4methoxypyridine-2-carbonyl) amino] -6-methyl-4,9dioxo-1,5-dioxonan-7-yl]
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Mixture Component 1 Component 2 B-150 an individualized compound I 2-Methylpropanoate[(3S, 6S, 7R, 8R) -8-benzyl-3 - [[3 (1,3-benzodioxol-5-ylmethoxy) -4methoxypyridine-2-carbonyl] amino] -6-methyl-4,9-dioxo-1,5-dioxonan-7-yl] B-151 an individualized compound I Anilazine B-152 an individualized compound I Blasticidin-S B-153 an individualized compound I Captafol B-154 an individualized compound I Captan B-155 an individualized compound I Cinometionat B-156 an individualized compound I Dazomet B-157 an individualized compound I Debacarb B-158 an individualized compound I Diclomezina B-159 an individualized compound I Difenzoquat B-160 an individualized compound I Dipenzoquat methyl sulfate B-161 an individualized compound I Fenoxanil B-162 an individualized compound I Folpet B-163 an individualized compound I Oxolinasaure B-164 an individualized compound I Piperalin
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Mixture Component 1 Component 2 B-165 an individualized compound I Proquinazid B-166 an individualized compound I Piroquilon B-167 an individualized compound I Quinoxifen B-168 an individualized compound I Triazoxide B-169 an individualized compound I Tricyclazole B-170 an individualized compound I 2-Butoxy-6-iodo-3-propylchromene4-ona B-171 an individualized compound I 5-Chlorine-1- (4,6-dimethoxypyrimidin-2-yl) -2-methyl-1H-benzoimidazole B-172 an individualized compound I 5- Chlorine-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] tri-azolo [1,5-a] pyrimidine B-173 an individualized compound I Ferbam B-174 an individualized compound I Mancozeb B-175 an individualized compound I Maneb B-176 an individualized compound I Metam B-177 an individualized compound I Metasulfocarb B-178 an individualized compound I They met B-179 an individualized compound I Propineb
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Mixture Component 1 Component 2 B-180 an individualized compound I Take out B-181 an individualized compound I Zineb B-182 an individualized compound I Ziram B-183 an individualized compound I Dietofencarb B-184 an individualized compound I Bentiavalicarb B-185 an individualized compound I Iprovalicarb B-186 an individualized compound I Propamocarb B-187 an individualized compound I Propamocarb hydrochloride B-188 an individualized compound I Valiphenalate B-189 an individualized compound I (4-Fluorophenyl) N- acid ester(1 - (1 - (4-cyanophenyl) ethanesulfon-il) -but-2-yl) carbamic B-190 an individualized compound I Dodina B-191 an individualized compound I Dodine free base B-192 an individualized compound I Guazatina B-193 an individualized compound I Guazatin acetate B-194 an individualized compound I Iminoctadine B-195 an individualized compound I Iminoctadine triacetate B-196 an individualized compound I Iminoctadine tris (albesylate)
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Mixture Component 1 Component 2 B-197 an individualized compound I Casugamycin B-198 an individualized compound I Hydrochloride hydratecasugamycin B-199 an individualized compound I Polyoxin B-200 an individualized compound I Streptomycin B-201 an individualized compound I Validamycin A B-202 an individualized compound I Binapacril B-203 an individualized compound I Dicloran B-204 an individualized compound I Dinobuton B-205 an individualized compound I Dinocap B-206 an individualized compound I Nitrotalisopropyl B-207 an individualized compound I Tecnazen B-208 an individualized compound I Fentin salts B-209 an individualized compound I Ditianon B-210 an individualized compound I Isoprothiolane B-211 an individualized compound I Edifenfós B-212 an individualized compound I Fosetil, Fosetilalumin B-213 an individualized compound I Iprobenfós
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Mixture Component 1 Component 2 B-214 an individualized compound I Phosphorous acid (H3PO3) and derivatives B-215 an individualized compound I Pyrazophos B-216 an individualized compound I Tolclofós-methyl B-217 an individualized compound I Chlorothalonil B-218 an individualized compound I Diclofluanid B-219 an individualized compound I Dichlorophen B-220 an individualized compound I Flussulfamide B-221 an individualized compound I Hexachlorobenzene B-222 an individualized compound I Pencicuron B-223 an individualized compound I Pentachlorophenol and salts B-224 an individualized compound I Phthalide B-225 an individualized compound I Quinatozene B-226 an individualized compound I Methyl thiophanate B-227 an individualized compound I Tolylfluanid B-228 an individualized compound I N- (4-chloro-2-nitrophenyl) -N-ethyl-4-methylbenzenesulfonamide B-229 an individualized compound I Bordeaux mix
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Mixture Component 1 Component 2 B-230 an individualized compound I Copper acetate B-231 an individualized compound I Copper hydroxide B-232 an individualized compound I Copper oxychloride B-233 an individualized compound I Basic copper sulphate B-234 an individualized compound I Sulfur B-235 an individualized compound I Biphenyl B-236 an individualized compound I Bronopol B-237 an individualized compound I Ciflufenamid B-238 an individualized compound I Cymoxanil B-239 an individualized compound I Diphenylamine B-240 an individualized compound I Metrafenone B-241 an individualized compound I Pyrophenone B-242 an individualized compound I Mildiomycin B-243 an individualized compound I Oxy-copper B-244 an individualized compound I Prohexadione calcium B-245 an individualized compound I Spiroxamine B-246 an individualized compound I Tebufloquina B-247 an individualized compound I Tolylfluanid
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Mixture Component 1 Component 2 B-248 an individualized compound I N- (Cyclopropylmethoxy-imino- (6difluoromethoxy-2,3-difluorophenyl) methyl) -2-phenyl acetamide B-249 an individualized compound I N '- (4- (4-chloro-3trifluoromethylphenoxy) 2,5-dimethylphenyl) -N-ethyl-N-methyl formamidine B-250 an individualized compound I N '- (4- (4-fluoro-3trifluoromethylphenoxy) 2,5-dimethylphenyl) -N-ethyl-N-methyl formamidine B-251 an individualized compound I N '- (2-methyl-5-trifluoromethyl-4- (3-trimethylsilanylpropoxy) -phenyl) -Netyl-N-methyl formamidine B-252 an individualized compound I N '- (5-difluoromethyl-2-methyl-4- (3-trimethylsilanylpropoxy) -phenyl) -Netyl-N-methyl formamidine B-253 an individualized compound I Methyl- (1,2,3,4-tetrahydronaphthalen-1-yl) -amide2- {1- [2- (5-methyl-3-trifluoromethylpyrazol-1-yl) -acetyl] piperidin-4-yl} -thiazole-4-carboxylic
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Mixture Component 1 Component 2 B-254 an individualized compound I 2- {1- [2- (5-methyl-3trifluoromethylpyrazol-1-yl) -acetyl] piperidin-4-yl acid methyl- (R) -1,2,3,4-tetrahydronaphthalen-1-ylamide} - thiazole-4-carboxylic B-255 an individualized compound I 1- [4- [4- [5- (2,6-difluorophenyl) -4,5dihydro-3-isoxazolyl] -2-thiazolyl] -1piperidinyl] -2- [5-methyl-3- (trifluoromethyl) -1H-pyrazol-1-yl] ethanone B-256 an individualized compound I 6-Terc-butyl-8-fluoro-2,3dimethylquinolin-4-yl ester ofmethoxyacetic acid B-257 an individualized compound I M-Methyl-2- {1 - [(5-methyl-3-trifluoromethyl-1H-pyrazol-1-yl) -acetyl] piperidin-4-yl} -W - [(1 R) -1,2,3 , 4tetrahydronaphthalen-1-yl] -4thiazolcarboxamide B-258 an individualized compound I Bacilus subtilis NRRL N ° B-21661 B-259 an individualized compound I Bacilus pumilus NRRL N ° B-30087 B-260 an individualized compound I Ulocladium oudemansii
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Mixture Component 1 Component 2 B-261 an individualized compound I Carbaril B-262 an individualized compound I Carbofuran B-263 an individualized compound I Carbossulfan B-264 an individualized compound I Metomiltiodicarb B-265 an individualized compound I Bifenthrin B-266 an individualized compound I Cyfluthrin B-267 an individualized compound I Cypermethrin B-268 an individualized compound I alpha-Cypermethrin B-269 an individualized compound I zeta-Cypermethrin B-270 an individualized compound I Deltamethrin B-271 an individualized compound I Sphenvarelate B-272 an individualized compound I Lambdaci-halotrina B-273 an individualized compound I Permethrin B-274 an individualized compound I Teflutrin B-275 an individualized compound I Diflubenzuron B-276 an individualized compound I Flufenoxuron B-277 an individualized compound I Lufenuron B-278 an individualized compound I Teflubenzuron
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Mixture Component 1 Component 2 B-279 an individualized compound I Spirotetramato B-280 an individualized compound I Clothianidin B-281 an individualized compound I Dinotefuran B-282 an individualized compound I Imidacloprid B-283 an individualized compound I Thiamethoxam B-284 an individualized compound I Acetamiprid B-285 an individualized compound I Tiacloprid B-286 an individualized compound I Endosulfan B-287 an individualized compound I Fipronil B-288 an individualized compound I Abamectin B-289 an individualized compound I Emamectin B-290 an individualized compound I Espinosad B-291 an individualized compound I Espinetoram B-292 an individualized compound I Hydramethylnon B-293 an individualized compound I Clorfenapir B-294 an individualized compound I Fenbutatin oxide B-295 an individualized compound I Inadoxacarb B-296 an individualized compound I Metaflumizona
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Mixture Component 1 Component 2 B-297 an individualized compound I Flonicamid B-298 an individualized compound I Lubendiamide B-299 an individualized compound I Chlorantraniliprol B-300 an individualized compound I Ciazipir (HGW86) B-301 an individualized compound I Ciflumetofen B-302 an individualized compound I Acetochlor B-303 an individualized compound I Dimetenamid B-304 an individualized compound I Metolachlor B-305 an individualized compound I Metazachlor B-306 an individualized compound I Glyphosate B-307 an individualized compound I Glufosinate B-308 an individualized compound I Sulfosate B-309 an individualized compound I Clodinafop B-310 an individualized compound I Fenoxaprop B-311 an individualized compound I Fluazifop B-312 an individualized compound I Haloxifop B-313 an individualized compound I Paraquat B-314 an individualized compound I Fenmedifam
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Mixture Component 1 Component 2 B-315 an individualized compound I Cletodim B-316 an individualized compound I Cycloxidim B-317 an individualized compound I Profoxidim B-318 an individualized compound I Setoxidim B-319 an individualized compound I Tepraloxidim B-320 an individualized compound I Pendimethalin B-321 an individualized compound I Prodiamine B-322 an individualized compound I Trifluralin B-323 an individualized compound I Acifluorfen B-324 an individualized compound I Bromoxin B-325 an individualized compound I Imazametabenzo B-326 an individualized compound I Imazamox B-327 an individualized compound I Imazapic B-328 an individualized compound I Imazapir B-329 an individualized compound I Imazaquine B-330 an individualized compound I Imazetapir B-331 an individualized compound I 2,4-Dichlorophenoxyacetic acid(2,4-D)
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Mixture Component 1 Component 2 B-332 an individualized compound I Chloridazon B-333 an individualized compound I Clopiralid B-334 an individualized compound I Fluroxypyr B-335 an individualized compound I Picloram B-336 an individualized compound I Picolinafen B-337 an individualized compound I Bensulfuron B-338 an individualized compound I Chlorimuron-ethyl B-339 an individualized compound I Cyclosulfamuron B-340 an individualized compound I Iodosulfuron B-341 an individualized compound I Mesosulfuron B-342 an individualized compound I Metsulfuron-methyl B-343 an individualized compound I Nicosulfuron B-344 an individualized compound I Rimsulfuron B-345 an individualized compound I Triflussulfuron B-346 an individualized compound I Atrazine B-347 an individualized compound I Hexazinone B-348 an individualized compound I Diuron B-349 an individualized compound I Florassulam
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Mixture Component 1 Component 2 B-350 an individualized compound I Pyroxassulfone B-351 an individualized compound I Bentazona B-352 an individualized compound I Cinidon-ethyl B-353 an individualized compound I Cinamethylin B-354 an individualized compound I Dicamba B-355 an individualized compound I Diflufenzopyr B-356 an individualized compound I Quinachlorac B-357 an individualized compound I Quinamerac B-358 an individualized compound I Mesotrione B-359 an individualized compound I Saflufenacil B-360 an individualized compound I Topramezona B-361 an individualized compound I 2-Methylpropanoate(3S, 6S, 7R, 8R) -3 - [[((3-hydroxy-4-methoxy-2-pyridinyl) carbonyl] amino] -6-methyl4,9-dioxo-8- (phenylmethyl) -1,5dioxonan-7-yl B-362 an individualized compound I 1- [re / - (2S; 3R) -3- (2-chlorophenyl) -2 (2,4-difluorophenyl) -oxyranylmethyl] 5-thiocyanate-1H- [1,2,4] triazole
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Mixture Component 1 Component 2 B-363 an individualized compound I 2- [re / - (2S; 3R) -3- (2-chlorophenyl) -2-(2,4-difluorophenyl) -oxyranylmethyl] -2H- [1,2,4] triazole-3-thiol B-364 an individualized compound I 1- [4- [4- [5- (2,6-difluorophenyl) -4,5-dihydro-3-isoxazolyl] -2-thiazolyl] -1piperidinyl] -2- [5-methyl-3 (trifluoromethyl) -1H-pyrazol1-yl] ethanone B-365 an individualized compound I 2,6-dimethyl-1H, 5H- [1,4] dithi-ino [2,3-c: 5,6-c '] dipyrrol-1,3,5,7 (2H, 6H) -tetraone B-366 an individualized compound I flupiradifurone B-367 an individualized compound I 3- (difluoromethyl) -1-methyl-N-(1,1,3-trimethylinadan-4-yl) pyrazole-4- carboxamide B-368 an individualized compound I 3- (trifluoromethyl) -1-methyl-N-(1,1,3-trimethylinadan-4-yl) pyrazole-4- carboxamide B-369 an individualized compound I 1,3-dimethyl-N- (1,1,3-trimethylinadan-4-yl) pyrazol-4-carboxamide
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Mixture Component 1 Component 2 B-370 an individualized compound I 3- (trifluoromethyl) -1,5-dimethyl-N-(1,1,3-trimethylinadan-4-yl) pyrazole-4- carboxamide B-371 an individualized compound I 3- (difluoromethyl) -1,5-dimethyl-N-(1,1,3-trimethylinadan-4-yl) pyrazole-4- carboxamide B-372 an individualized compound I 1,3,5-trimethyl-N- (1,1,3trimethylinadan-4-yl) pyrazol-4carboxamide
[0132] The active substances indicated as component 2, their preparation and their activity against harmful fungi are known (cf. http://www.alanwood.net/pesticides/); these substances are commercially available. The compounds described by the IUPAC nomenclature, their preparation and their fungicidal activity are also known (cf. Can. J. Plant Sci. 48 (6), 587-94, 1968; EP-A 141.317; EP-A 152.031; EP-A 226,917; EP-A 243,970; EP-A 256,503; EP-A 428,941; EP-A 532,022; EP-A 1,028,125; EP-A 1,035,122; EP-A 1,201,648; EP-A 1,122,244, JP 2002316902; DE 19650197; DE 10021412; DE 102005009458; US 3,296,272; US 3,325,503; WO 98/46608; WO 99/14187; WO 99/24413; WO 99/27783; WO 00/29404; WO 00/29404;
WO 00/46148; WO 00/65913; WO 01/54501; WO 01/56358; WO 02/22583;
WO 02/40431; WO 03/10149; WO 03/11853; WO 03/14103; WO 03/16286;
WO 03/53145; WO 03/61388; WO 03/66609; WO 03/74491; WO 04/49804;
WO 04/83193; WO 05/120234; WO 05/123689; WO 05/123690; WO 05/63721; WO 05/87772; WO 05/87773; WO 06/15866; WO 06/87325; WO 06/87343;
WO 07/82098; WO 07/90624, WO 11/028657).
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81/103 [0133] Mixtures of active substances can be prepared in the form of compositions which comprise, in addition to the active ingredients, at least one active ingredient by usual means, such as the media provided for the compositions of compounds I.
[0134] With regard to the usual ingredients of these compositions, reference is made to the explanations provided for compositions containing compounds I.
[0135] The active substance mixtures according to the present invention are suitable as fungicides, as well as the compounds of Formula I. They are distinguished by remarkable efficacy against a wide spectrum of phytopathogenic fungi, especially of the classes of Ascomycetes, Basidiomycetes, Deuteromycetes and Peronosporomycetes (syn. Oomycetes). In addition, we indicate the explanations regarding the fungicidal activity of compounds and compositions containing compounds I, respectively.
I. Examples of synthesis:
With appropriate modification of the starting compounds, the procedures shown in the synthesis examples below were used to obtain additional compounds I. The resulting compounds, together with physical data, are listed in Table I below.
Example 1 [0136] Preparation of 2- [2-chloro-4- (4-chlorophenoxy) -phenyl] -1 [1,2,4] triazol-1-ylpentan-2-ol (compound I-2):
MgBr diethyl etherate (10.5 g, 40.2 mmol) was added to a solution of the aforementioned ethanone (6.0 g, 16.8 mmol) in dichloromethane (DCM, 65 ml) and the mixture was stirred at temperature environment for about ninety minutes. This mixture was then cooled to about 0 ° C and n-propylmagnesium chloride (22.8 ml of
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M in THF, 45.6 mmol). After stirring for about two hours, the mixture was kept under heating at room temperature and then cooled by adding a saturated ammonium chloride solution. The organic components were extracted three times with DCM, the organic phases were combined, washed again with saturated ammonium chloride solution, dried and the solvents were evaporated. The addition of diisopropyl ether resulted in the precipitation of the unreacted starting material, which was removed by filtration. The filtrate was then purified using reverse phase chromatography to generate the product as a light brown colored solid (2.5 g, 36%; Rt HPLC ¹ - 3.877 min).
Example 1 [0137] Preparation of 2- [2-chloro-4- (4-chlorophenoxy) -phenyl] -1 [1,2,4] triazol-1-ylpentan-2-ol (compound I-2):
Intermediate 1- [2-chloro-4- (4-chlorophenoxy) -phenyl] -2- [1,2,4] triazole-1-ethylanone was prepared as described in WO 2010/0146114.
[0138] MgBr diethyl etherate (10.5 g, 40.2 mmol) was added to a solution of the aforementioned ethanone (6.0 g, 16.8 mmol) in dichloromethane (DCM, 65 ml) and the mixture was stirred at room temperature for about ninety minutes. This mixture was then cooled to about 0 ° C and n-propylmagnesium chloride (22.8 ml of a 2 M solution in THF, 45.6 mmol) was added dropwise. After stirring for about two hours, the mixture was kept under heating at room temperature and then cooled by adding a saturated ammonium chloride solution. The organic components were extracted three times with DCM, the organic phases were combined, washed again with saturated ammonium chloride solution, dried and the solvents were evaporated. The addition of diisopropyl ether resulted in the precipitation of the unreacted starting material, which was removed by filtration. The filtrate was then purified using
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83/103 reverse phase chromatography, to generate the product as a light brown solid (2.5 g, 36%; Rt HPLC ² = 1.26 min, mass = 392).
Example 2 [0139] Preparation of 2- [2-chloro-4- (4-chlorophenoxy) phenyl] -1- (1,2,4triazol-1-yl) pent-3-in-2-ol (Compound I- 8):
Intermediate 1- [2-chloro-4- (4-chlorophenoxy) -phenyl] -2- [1,2,4] triazole-1-ethylanone was prepared as described in WO 2010/0146114.
[0140] To a solution of the ethanone mentioned above (75.5 g, 216.8 mmol) dissolved in THF (240 ml), a solution of LaCl3.2LiCl (395.9 ml, 0.6 M in THF) was added ) at room temperature and stirred for one hour. The resulting solution was added dropwise to 1propynylmagnesium bromide (650.5 ml, 0.5 M in THF) at room temperature. After one hour at room temperature, the resulting mixture was cooled with a 10% aqueous solution of HCl and extracted with MTBE. The organic phase was washed with brine, dried and evaporated. The crude compound was stirred in a solution of MTBE and diisopropyl ether and filtered to eliminate the starting material. The original liquids were evaporated and purified on silica gel to generate the title compound as a beige solid (31.1 g, Rt MS ² HPLC = 1.15 min, mass = 338, melting point = 137 ° C).
Example 3 [0141] Preparation of 2- [2-chloro-4- (4-chlorophenoxy) phenyl] -1- (1,2,4triazol-1-yl) butan-2-ol (Compound I-1):
Step 1:
To a solution of 1-bromo-2-chloro-4- (4-chlorophenoxy) benzene (410.0 g, 1.29 mol) in 1 l of THF, isopropyl magnesium chloride (1.289 l, 1.3 M in THF) at room temperature and stirred for thirty minutes. The reaction mixture was added dropwise then to a solution of propanoyl chloride (155.08 g, 1.68 mol), aluminum trichloride
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84/103 (5.66 g, 40 mmol), lithium chloride (3.6 g, 80 mmol) and copper chloride (4.2 g, 40 mmol) in 3 l of THF under light cooling (20 to 30 ° C). After thirty minutes at room temperature, the resulting mixture was cooled with an aqueous solution of ammonium chloride to 10 ° C and extracted with MTBE. The organic phase was washed successively with an aqueous solution of water and sodium chloride, then dried and evaporated to generate, after distillation, 1- [2-chloro-4- (4 chlorophenoxy) phenyl] propan-1-one (297, 0 g, bp = 162-168 ° C, P = 1 mbar).
[0142] Step 2:
To a solution of sodium hydride (35.72 g, 1.49 mol) in THF (1 l) and dry DMSO (2 l), a solution of trimethyl sulfonium iodide ( 290.5 g, 1.42 mol) in dry DMSO (2 l). The mixture was stirred for one hour at 5 ° C, followed by adding drops of 1- [2-chloro-4 (4-chlorophenoxy) phenyl] propan-1-one (199.0 g, 0.65 mol) in DMSO (500 ml). The resulting mixture was then warmed to room temperature, cooled with an aqueous solution of ammonium chloride and water with ice and extracted with MTBE. The organic solvents were washed with water, dried and evaporated to generate 2- [2-chloro-4- (4-chlorophenoxy) phenyl] -2-ethyloxirane as a yellowish solid (216.0 g, 97%). NMR 1H (CDCh; 400 MHz) □□ (ppm) = 0.9 (t, 3H); 1.75 (m, 1H); 2.10 (m, 1H); 2.80 (d, 1H); 3.05 (d, 1H); 6.85 (d, 1H); 6.95 (m, 3H); 7.30 (d, 2H); 7.40 (d, 1H).
[0143] Step 3:
To 2- [2-chloro-4- (4-chlorophenoxy) phenyl] -2-ethyloxirane (216.0 g, 0.63 mol) dissolved in M-methyl-2-pyrrolidone (2 l), hydroxide was added sodium (62.87 g, 1.57 mol) and triazole (217.1 g, 3.14 mol) at room temperature. The mixture was then stirred for twelve hours at 140 ° C. Then a solution of ammonium chloride and water with ice was added and the mixture was extracted with MTBE and washed with an aqueous solution of lithium chloride. The crude residue was purified by recrystallization from diisopropyl ether to generate compound
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2- [2-chloro-4- (4-chlorophenoxy) phenyl] -1- (1,2,4-triazol-1-yl) butan-2-ol as a colorless solid (127.0 g, 51% melting point = 140-142 ° C).
[0144] The compounds I listed in Table I were prepared in an analogous manner.
Table I
Ex. R ¹ Rt HPLC ¹ (min) Rt HPLC ² (min) point ofmelting (° C) I-1 -C2C3 140-142 I-2 -C2C2C3 3,877 1.26 132-135 I-3 -C (C3) 2 3,545 1.28 86-87 I-4 -C2C2C2C3 4,049 1.32 108-116 I-5 -C (C3) 3 3,480 1.38I-6 -C5H9 (cyclopentyl) 4,093 1.39I-7 -C C 3,398 1.10 150-151 I-8 -C CC3 3,498 1.15 139 I-9 -C3H5 (cyclopropyl)1.24 110 I-10 -C = C21.16 119 I-11 -C2C C1.14I-12 -C2C = C21.21
[0145] HPLC column ¹ : RP-18 column (Cromolith Speed ROD from Merck KgaA, Germany), 50 mm x 4.6 mm with eluent: acetonitrile + 0.1%
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86/103 trifluoroacetic acid (TFA) / water + 0.1% TFA (gradient from 5:95 to 95: 5 for five minutes at 40 ° C, flow of 1.8 ml / min).
[0146] HPLC column ² : column (Kinetex XB C18 1.7 pm), 50 mm x 2.1 mm with eluent: acetonitrile + 0.1% trifluoroacetic acid (TFA) / water; (gradient from 5:95 to 95: 5 for one and a half minutes at 60 ° C, flow of 1.8 ml / min).
II. Examples of action against harmful fungi:
The fungicidal action of the compounds of Formula I was demonstrated by the following experiments:
The. Greenhouse tests:
The active substances were formulated separately or together in the form of a standard solution comprising 25 mg of active substance that was made up to 10 ml using a mixture of acetone and / or DMSO and the emulsifier Wettol EM 31 (wetting agent that has an emulsifying action and dispersant based on ethoxylated alkylphenols) in volume ratio between solvent and emulsifier from 99 to 1. This solution was made up to 100 ml using water. This standard solution was diluted with the mixture of solvent, emulsifier and water described to the concentration of active substance provided below.
Usage Example 1 [0147] Preventive fungicidal control of early rust on tomatoes (Alternaria solani).
[0148] Young seedlings of tomato plants were grown in pots. These plants were sprayed to exhaustion with an aqueous suspension containing the concentration of active ingredient mentioned in the table below. The following day, the treated plants were inoculated with an aqueous suspension of Alternaria solani. Then, the test plants were transferred immediately to a moist chamber. After five days at 20 to 22 ° C and relative humidity close to 100%, the extent of fungal attack on
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87/103 the leaves were determined visually as a percentage of diseased leaf area.
[0149] In this test, plants that had been treated with 300 ppm of the active substance in Examples I-5 and I-5, respectively, exhibited infection less than or equal to 15%, while untreated plants suffered an infection of 90%.
Usage Example 2 [0150] Preventive control of gray mold (Botrytis cinerea) on green pepper leaves.
[0151] Young green pepper seedlings were grown in pots up to the stage of two to three leaves. These plants were sprayed to exhaustion with an aqueous suspension containing the concentration of active ingredient or mixture mentioned in the table below. The following day, the treated plants were inoculated with a spore suspension of Botrytis cinerea in a 2% aqueous bio-enamel solution. Then, the test plants were transferred immediately to a humid dark chamber. After five days at 22 to 24 ° C and relative humidity close to 100%, the extent of fungal attack on the leaves was determined visually as a percentage of diseased leaf area.
[0152] In this test, plants that had been treated with 150 ppm of the active substance of Examples I-1, I-2, I-3, I-7 and I-8, respectively, exhibited infection less than or equal to 15% , while the untreated plants suffered 90% infection.
Usage Example 3 [0153] Preventive control of brown rust on wheat caused by Puccinia recondita:
The first two leaves developed from wheat seedlings grown in pots were sprayed to exhaustion with a suspension
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88/103 aqueous solution containing the concentration of active ingredient as described below. The next day, the plants were inoculated with spores of Puccinia recondita. To guarantee the success of artificial inoculation, the plants were transferred to a humid chamber without light and with a relative humidity of 95 to 99% and 20 to 22 ° C for 24 hours. Then, the test plants were grown for six days in a greenhouse at 22-26 ° C and under 65 to 70% relative humidity. The extent of fungal attack on the leaves was determined visually as a percentage of diseased leaf area.
[0154] In this test, plants that had been treated with 300 ppm of the active substance of Examples I-1, I-2, I-3, I-4, I-5, I-6, I-7 and I- 8, respectively, exhibited infection less than or equal to 15%, while untreated plants suffered an infection of 90%.
Usage Example 4 [0155] Preventive control of soybean rust on soybeans caused by Fakopsora pachyrhizi:
Leaves of soybean seedlings grown in pots were sprayed to exhaustion with an aqueous suspension containing the concentration of active ingredient, as described below. The plants were kept to air dry. The next day, the plants were inoculated with spores of Fakopsora pachyrhizii. To guarantee the success of artificial inoculation, the plants were transferred to a humid chamber with a relative humidity of about 95% and 23 to 27 ° C for 24 hours. Then, the test plants were grown for 14 days in a greenhouse chamber at 23-27 ° C and under 60 to 80% relative humidity. The extent of fungal attack on the leaves was determined visually as a percentage of diseased leaf area.
[0156] In this test, plants that had been treated with 300 ppm of the active substance of Examples I-1, I-2, I-4, I-6, I-7 and I-8,
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89/103 respectively, showed infection less than or equal to 15%, while untreated plants suffered an infection of 90%.
Usage Example 5 [0157] Preventive control of leaf rust caused by Septoria tritici:
The first two leaves developed from wheat seedlings grown in pots were sprayed to exhaustion with an aqueous suspension containing the concentration of active ingredient, as described below. The next day, the plants were inoculated with an aqueous spore suspension of Septoria tritici. To guarantee the success of artificial inoculation, the plants were transferred for four days to a humid chamber with a relative humidity of 95 to 99% and 20 to 24 ° C. Then, the plants were grown for four weeks under 70% relative humidity. The extent of fungal attack on the leaves was determined visually as a percentage of diseased leaf area.
[0158] In this test, plants that had been treated with 300 ppm of the active substance of Examples I-1, I-2, I-3, I-4, I-6, I-7 and I-8, respectively, showed infection less than or equal to 15%, while untreated plants suffered infection of 90%.
B. Microtest:
The active compounds were formulated separately as a standard solution with a concentration of 10,000 ppm in dimethyl sulfoxide.
Example 1 [0159] Activity against the posterior rust pathogen Phytophthora infestans in the microtiter test:
[0160] The standard solutions were mixed according to the ratio, pipetted onto a microtiter plate (MTP) and diluted with water to the indicated concentrations. Then a suspension of
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90/103 spores of Phytophthora infestans containing an aqueous nutrient medium based on pea juice or DDC medium. The plates were placed in a chamber saturated with water vapor at a temperature of 18 ° C. Using an absorption photometer, MTPs were measured at 405 nm seven days after inoculation. The measured parameters were compared with the growth of the control variant free of active compounds (100%) and the standard value free of fungi and free of active compound to determine the relative growth in percentage of pathogens in the corresponding active compounds.
[0161] Pathogens treated with an aqueous active compound preparation comprising 32 ppm of active compounds I-11 and I-12 exhibited growth of 12% and 10%, respectively.
Example 2 [0162] Activity against gray mold Botrytis cinerea in the microtiter plate test:
The standard solutions were mixed according to the ratio, pipetted onto a microtiter plate (MTP) and diluted with water to the indicated concentrations. Then a suspension of Botrytis cinerea spores in an aqueous solution of bio enamel or yeast, bactopeptone and sodium acetate was added. The plates were placed in a chamber saturated with water vapor at a temperature of 18 ° C. Using an absorption photometer, MTPs were measured at 405 nm seven days after inoculation. The measured parameters were compared with the growth of the control variant free of active compounds (100%) and the standard value free of fungi and free of active compound to determine the relative growth in percentage of pathogens in the corresponding active compounds.
[0163] Pathogens treated with an aqueous active compound preparation comprising 32 ppm of active compounds I-11 and I-12 exhibited growth of 0% and 1%, respectively.
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Example 3 [0164] Activity against Pyricularia oryzae rice blast in the microtiter plate test:
The standard solutions were mixed according to the ratio, pipetted onto a microtiter plate (MTP) and diluted with water to the indicated concentrations. A suspension of Pyricularia oryzae spores in an aqueous solution of bio enamel or yeast, bactopeptone and glycerin was then added. The plates were placed in a chamber saturated with water vapor at a temperature of 18 ° C. Using an absorption photometer, MTPs were measured at 405 nm seven days after inoculation. The measured parameters were compared with the growth of the control variant free of active compounds (100%) and the standard value free of fungi and free of active compound to determine the relative growth in percentage of pathogens in the corresponding active compounds.
[0165] Pathogens treated with an aqueous active compound preparation comprising 32 ppm of active compounds I-11 and I-12 exhibited 0% growth.
Example 4 [0166] Activity against wheat leaf stains caused by Septoria tritici:
The standard solutions were mixed according to the ratio, pipetted onto a microtiter plate (MTP) and diluted with water to the indicated concentrations. A Septoria tritici spore suspension in an aqueous solution of bio enamel or yeast, bactopeptone and glycerin was used. The plates were placed in a chamber saturated with water vapor at a temperature of 18 ° C. Using an absorption photometer, MTPs were measured at 405 nm seven days after inoculation. The measured parameters were compared with the growth of the control-free variant
Petition 870190031114, dated 04/01/2019, p. 101/126
92/103 active compounds (100%) and the standard value free of fungi and free of active compound to determine the relative growth in percentage of pathogens in the corresponding active compounds.
[0167] Pathogens treated with an aqueous active compound preparation comprising 32 ppm of active compounds I-11 and I-12 exhibited growth of 9% and 17%, respectively.
Example 5 [0168] Activity against early rust caused by Alternaria solani:
The standard solutions were mixed according to the ratio, pipetted onto a microtiter plate (MTP) and diluted with water to the indicated concentrations. A spore suspension of Alternaria solani in an aqueous solution of bio enamel or yeast, bactopeptone and glycerin was used. The plates were placed in a chamber saturated with water vapor at a temperature of 18 ° C. Using an absorption photometer, MTPs were measured at 405 nm seven days after inoculation. The measured parameters were compared with the growth of the control variant free of active compounds (100%) and the standard value free of fungi and free of active compound to determine the relative growth in percentage of pathogens in the corresponding active compounds.
[0169] Pathogens treated with an aqueous active compound preparation comprising 32 ppm of active compounds I-11 and I-12 exhibited growth of 2% and 3%, respectively.
Example 6 [0170] Activity against wheat leaf stains caused by Leptosphaeria nodorum:
The standard solutions were mixed according to the ratio, pipetted onto a microtiter plate (MTP) and diluted with water until
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93/103 indicated concentrations. Then, a spore suspension of Leptosphaeria nodorum in an aqueous solution of bio enamel or yeast, bactopeptone and glycerin was added. The plates were placed in a chamber saturated with water vapor at a temperature of 18 ° C. Using an absorption photometer, MTPs were measured at 405 nm seven days after inoculation. The measured parameters were compared with the growth of the control variant free of active compounds (100%) and the standard value free of fungi and free of active compound to determine the relative growth in percentage of pathogens in the corresponding active compounds. The measured parameters were compared with the growth of the control variant free of active compounds (100%) and the standard value free of fungi and free of active compound to determine the relative growth in percentage of pathogens in the corresponding active compounds.
[0171] Pathogens treated with an aqueous active compound preparation comprising 32 ppm of active compounds I-11 and I-12 exhibited growth of 2% and 4%, respectively.
[0172] B. Comparative tests:
B.1 Microtest:
The active compounds were formulated separately as a standard solution with a concentration of 10,000 ppm in dimethyl sulfoxide.
Example 1 [0173] Activity against liquid rust Pyrenophora teres on barley in the microtiter test:
The standard solutions were mixed according to the ratio, pipetted onto a microtiter plate (MTP) and diluted with water to the indicated concentrations. A suspension of Pyrenophora ester spores in an aqueous solution of bio enamel or yeast, bactopeptone and glycerin was then added. The plates were placed in a saturated chamber
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94/103 with water vapor at 18 ° C. Using an absorption photometer, MTPs were measured at 405 nm seven days after inoculation.
Compound No. Structure Growth(%) at 8 pm According to the state of the art Oo o / 2V oíF 62 According to the state of the art0> 39 Compound of Table 1, 1 according to the present invention / ^Cl ÁTOQ cr pç ⁰ 0 --- 13 According to the state of the art / ^C. , The CC | ç 0 w 77 Compound from Table 1, 2 according to the present invention / Cl ιΓΥΤΎ° 4 '/ 57
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95/103
Example 2 [0174] Activity against early rust caused by Alternaria solani:
The standard solutions were mixed according to the ratio, pipetted onto a microtiter plate (MTP) and diluted with water to the indicated concentrations. Then a spore suspension of Alternaria solani in an aqueous solution of bio enamel or yeast, bactopeptone and glycerin was added. The plates were placed in a chamber saturated with water vapor at a temperature of 18 ° C. Using an absorption photometer, MTPs were measured at 405 nm seven days after inoculation.
Compound No. Structure Growth (%) at 0.5 pm According to the state of the art Λ -Cl IVOCuO cr ⁰ VzS 91 Compound ofTable 1, 10 ofaccording to the present invention / ^N = 0
Example 3 [0175] Activity against gray mold Botrytis cinerea in the microtiter plate test:
The standard solutions were mixed according to the ratio, pipetted onto a microtiter plate (MTP) and diluted with water to the indicated concentrations. Then a suspension of Botrytis cinerea spores in an aqueous solution of bio-enamel or yeast was added,
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96/103 bactopeptone and sodium acetate. The plates were placed in a chamber saturated with water vapor at a temperature of 18 ° C. Using an absorption photometer, MTPs were measured at 405 nm seven days after inoculation.
Compound No. Structure Growth (%) at 0.5 pm According to the state of the art The .Cl ____IJOCX) cr J 77 Compound from Table 1, 10 according to the present invention ^ Cl ΓΤΎΠΓ ° / ^ν = λ 0
Example 4 [0176] Activity against rice blast Pyricularia oryzae in the microtiter plate test:
The standard solutions were mixed according to the ratio, pipetted onto a microtiter plate (MTP) and diluted with water to the indicated concentrations. A suspension of Pyricularia oryzae spores in an aqueous solution of bio enamel or yeast, bactopeptone and glycerin was then added. The plates were placed in a chamber saturated with water vapor at a temperature of 18 ° C. Using an absorption photometer, MTPs were measured at 405 nm seven days after inoculation.
[0177] The measured parameters were compared with the growth of the control variant free of active compounds (100%) and the standard value free of fungi and free of active compound to determine the
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97/103 relative growth in percentage of pathogens in the corresponding active compounds.
[0178] These percentages have been converted into efficiencies.
Compound No. Structure Growth (%) at 0.5 pm According to the state of the art ° w 30 Compound from Table 1, 2 according to the present invention / Cl jTT ΊΓΧ 1 ^x NLN ^ / 4
Example 5 [0179] Activity against early rust caused by Alternaria solani:
The standard solutions were mixed according to the ratio, pipetted onto a microtiter plate (MTP) and diluted with water to the indicated concentrations. Then a spore suspension of Alternaria solani in an aqueous solution of bio enamel or yeast, bactopeptone and glycerin was added. The plates were placed in a chamber saturated with water vapor at a temperature of 18 ° C. Using an absorption photometer, MTPs were measured at 405 nm seven days after inoculation.
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98/103
Compound No. Structure Growth (%) at 0.000125 pm According to the state of the art XTOC. 45 According to the state of the art ΚΟρ.° W 83 Compound ofTable 1, 1 ofaccording topresent invention ^ ^Cl XTOQ o v> 1 Compound ofTable 1, 32 ofaccording to the present invention , σ'ΌΥ 1
Example 7 [0180] Activity against rice blast Pyricularia oryzae in the microtiter plate test:
The standard solutions were mixed according to the ratio, pipetted onto a microtiter plate (MTP) and diluted with water to the indicated concentrations. Then a suspension of Pyricularia oryzae spores in an aqueous solution of bio enamel or yeast, bactopeptone and glycerin was added. The plates were placed in a chamber saturated with water vapor at a temperature of 18 ° C. Using a
Petition 870190031114, dated 04/01/2019, p. 108/126
99/103 absorption photometer, MTPs were measured at 405 nm seven days after inoculation.
Compound No. Structure Growth (%) at 0.5 pm According to the state of the art ., σΧ / Ο 82 According to the state of the art xmL 47 Compound of Table 1, 1 according to the present invention .GXC 15
B.2. Greenhouse:
The spray solutions were prepared in several stages.
[0181] The standard solution was prepared: a mixture of acetone and / or dimethyl sulfoxide and the wetting / emulsifying agent Wettol, which is based on ethoxylated alkyl phenols, in a 99 to 1 ratio (volume) between solvent and emulsifier to 25 mg of the compound to generate a total of 5 ml.
[0182] Water was then added to a total volume of 100 ml.
[0183] This standard solution was diluted with the mixture of solvent, emulsifier and water described to the given concentration.
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100/103
Usage Example 1 [0184] Preventive control of leaf rust caused by Septoria tritici:
Leaves of wheat seedlings grown in pots were sprayed to exhaustion with an aqueous suspension of the active compound or its mixture, prepared as described. The plants were kept to air dry. The next day, the plants were inoculated with an aqueous spore suspension of Septoria tritici. Then, the test plants were immediately transferred to a humid chamber at 18-22 ° C under relative humidity close to 100%. After four days, the plants were transferred to a chamber at 18-22 ° C under relative humidity close to 70%. After four weeks, the extent of fungal attack on the leaves was determined visually as a percentage of diseased leaf area.
Compound No. Structure Disease (%) at 150ppm According to the state of the art Cl ^ ^N 60 According to the state of the art50 Compound ofTable 1, 1 ofaccording to the present invention OO 10 Control nottreated90
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101/103
Example 2 [0185] Fungicide control of rice rust caused by Pyricularia oryzae:
Leaves of rice seedlings grown in pots were sprayed to exhaustion with an aqueous suspension of the compound prepared as described. Seven days later, the plants were inoculated with an aqueous spore suspension of Pyricularia oryzae. Then, the test plants were transferred immediately to a moist chamber. After six days at 22 to 24 ° C and relative humidity close to 100%, the extent of fungal attack on the leaves was determined visually as a percentage of diseased leaf area.
Compound No. Structure Disease (%) a250 ppm According to the state of the art Cl íA ^N 60 Compound ofTable 1, 1 ofaccording to the present invention ^ N ^ A 20 Control nottreated90
Example 3 [0186] Control of millet stem rot caused by
Fusarium culmorum:
Millet seedlings grown in pots with two to three leaves were sprayed to exhaustion with an aqueous suspension of the prepared compound as described. The plants were kept to air dry. At the
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102/103 the following day, the plants were inoculated with a spore suspension of Fusarium culmorum in 2% aqueous malt solution. Then, the test plants were transferred immediately to a moist chamber. After six days at 23-25 ° C and relative humidity close to 100%, the extent of fungal attack on the leaves was determined visually as a percentage of diseased leaf area.
Compound No. Structure Disease (%) at 16 ppm According to the state of the art25 Compound of Table 1, 1 according to the present invention 0 1 Compound from Table 1, 32 according to the present invention5 According to the state of the art Cl í ^ ^N 30 Compound of Table 1, 1 according to the present invention OHO 0 Untreated control90
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103/103
Example 4 [0187] Preventive control of leaf rust caused by Septoria tritici:
Leaves of wheat seedlings grown in pots were inoculated with an aqueous spore suspension of Septoria tritici. Then, the test plants were immediately transferred to a humid chamber at 18-22 ° C under relative humidity close to 100%. After four days, the plants were transferred to a chamber at 18-22 ° C under relative humidity close to 70%. Seven days after inoculation, the plants were sprayed to exhaustion with aqueous suspension of the active compound or mixture prepared as described. Then, the plants were transferred back to the chamber at 18-22 ° C under relative humidity close to 70%. After four weeks, the extent of fungal attack on the leaves was determined visually as a percentage of diseased leaf area.
Compound No.According to the state of the art Structure Disease (%) a16 ppm xrc THE 70 Compound of Table 1, 1 of ΓΤΎΎ , CIaccording to this 40 invention0NUntreated control90
Petition 870190031114, dated 04/01/2019, p. 113/126

权利要求:
Claims (14)
[1]
Claims
1. USE OF FORMULA I COMPOUNDS:
on what:
- R ¹ is C2-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl and C3-C8 cycloalkyl;
wherein the aliphatic groups R ¹ are unsubstituted;
its N-oxides and salts acceptable for agricultural use, characterized by being for combating phytopathogenic fungi.
[2]
2. USE OF COMPOUNDS OF FORMULA I, their N-oxides and salts acceptable for agricultural use, as defined in claim 1, characterized by being for the protection of plant propagation material, seeds, roots and seedlings from seedlings against infestation by harmful fungi .
[3]
3. COMPOUNDS, characterized by being of formula I:
on what:
- R ¹ is C2-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, and C3-C8 cycloalkyl;
in which the aliphatic groups R ¹ are not substituted for their N-oxides and salts acceptable for agricultural use;
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2/5 except 2- [2-chloro-4- (4-chlorophenoxy) -phenyl] -1 - [1,2,4] triazole-1-ylpent-4in-2-ol.
[4]
COMPOUNDS according to claim 3, characterized in that R ¹ is C2-C6 alkyl, C2-C6 alkenyl or C2-C6 alkyl-1-alkyl.
[5]
5. COMPOUNDS according to claim 4, characterized in that R ¹ is C2-C4 alkyl.
[6]
6. COMPOUNDS according to claim 3, characterized in that R ¹ is C2-C6 alkenyl or C2-C6 alkyl-1-ynyl.
[7]
7. COMPOUNDS according to claim 3, characterized in that R ¹ is C3-C8 cycloalkyl.
[8]
8. COMPOUNDS according to claim 3, characterized in that R ¹ is ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, allyl, ethynyl, prop-1 -inyl, but-1 -inyl, cyclopropyl or cyclopropylmethyl .
[9]
9. METHOD OF FIGHTING PHYTOPATHOGENIC FUNGI, characterized by the treatment of fungi or materials, plants, soil or seeds to be protected against fungal attack with an effective amount of at least one compound of Formula I, as defined in claim 3, or a composition that understands you.
[10]
10. PROCESS OF PREPARING COMPOUNDS OF FORMULA I, as defined in any one of claims 3 to 8, characterized by comprising:
reaction of a compound of Formula III:
where Y is F or Cl;
with 4-chlorophenol of Formula II:
Petition 870190031114, dated 04/01/2019, p. 115/126
3/5 under basic conditions;
reaction of the compound resulting from Formula IV:
in the presence of an isopropylmagnesium bromide catalyst followed by reaction with acetyl chloride;
halogenation of the compound resulting from Formula V:
with bromine;
reaction of the compound resulting from Formula VI:
O under basic conditions with 1H-1,2,4-triazole; and reaction of the compound resulting from Formula VII:
with a compound of Formula VIII R ¹ -M;
wherein R ¹ is as defined in any of the claims
3 to 8 and M is MgBr, MgCI, Li or Na, to obtain compounds I.
[11]
11. PROCESS OF PREPARING COMPOUNDS OF
Petition 870190031114, dated 04/01/2019, p. 116/126
4/5
FORMULA I, as defined in any of claims 3 to 8, characterized by comprising:
reaction of a compound of Formula III:
where Y is F or Cl;
in the presence of an isopropylmagnesium halide catalyst followed by reaction with a compound of Formula IX R ¹ -COCI;
wherein R ¹ is as defined in any of claims 3a8 conversion of the compound resulting from Formula X
wherein Y is F or Cl and R ¹ is as defined in any one of claims 3 to 8;
under basic conditions with Formula II 4-chlorophenol:
reaction of the compound resulting from Formula Va:
The one where R ¹ is as defined in any of the claims
3 to 8;
with trimethylsulf (ox) onide halide; and reaction of the compound resulting from Formula XI:
Petition 870190031114, dated 04/01/2019, p. 117/126
5/5 where R ¹ is as defined in any of the claims
3 to 8, under basic conditions with 1H-1,2,4-triazole, to obtain compounds of Formula I.
[12]
12.
COMPOUNDS, characterized by being of formula XI:
wherein R ¹ is as defined in any one of claims 3 to 8.
[13]
13. AGROCHEMICAL COMPOSITION, characterized in that said composition comprises an auxiliary and at least one compound of Formula I, as defined in any one of claims 3 to 8, one of its N-oxides or salts acceptable for agricultural use.
[14]
COMPOSITION according to claim 13, characterized in that it further comprises another active compound.

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法律状态:
2018-08-07| B06T| Formal requirements before examination|

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2018-12-26| B15K| Others concerning applications: alteration of classification|Free format text: AS CLASSIFICACOES ANTERIORES ERAM: A01N 43/653 , C07D 249/08 , A61P 3/00 , A01N 43/20 , C07D 303/48 , C07D 303/18 , C07D 405/06 , A01N 43/02 Ipc: A01N 43/653 (1985.01), C07D 249/08 (1974.07), A01P |

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2019-01-02| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|

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2019-04-16| B09A| Decision: intention to grant|

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2019-05-14| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 11/07/2012, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 11/07/2012, OBSERVADAS AS CONDICOES LEGAIS |

优先权:

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申请号 | 申请日 | 专利标题

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US201161508084P| true| 2011-07-15|2011-07-15|

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US61/508,084|2011-07-15|

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EP11174174.0|2011-07-15|

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EP11174174|2011-07-15|

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