Pyrazolo[1,5-a]pyridine derivatives
Pyrazolo[1,5-a]pyridine derivatives provide a solution to control oomycetes in plants and crops by eradicating or preventing fungal infections, enhancing crop protection through targeted pesticide compositions.
Patent Information
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- SYNGENTA CROP PROTECITON AG
- Filing Date
- 2024-04-11
- Publication Date
- 2026-05-01
AI Technical Summary
Existing agricultural and horticultural practices lack effective compounds to control phytopathogenic microorganisms, particularly oomycetes, which cause significant damage to plants and harvested food crops.
Development of pyrazolo[1,5-a]pyridine derivatives with fungicidal activity, specifically targeting oomycetes, which can be used in pesticide compositions to eradicate, prevent, or control plant pathogens.
The pyrazolo[1,5-a]pyridine derivatives effectively reduce the pathogenicity of oomycetes, protecting plants and harvested crops by directly applying the compounds or compositions to the pathogens, habitats, or reproductive materials, thereby minimizing fungal damage.
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Figure 2026514034000001_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to a microbicidal pyrazolo[1,5-a]pyridine derivative having microbicidal activity, particularly fungicidal activity, more particularly activity against oomycetes, for example as an active ingredient. The present invention also relates to the preparation of the pyrazolo[1,5-a]pyridine derivative, an intermediate useful for the preparation of the pyrazolo[1,5-a]pyridine derivative, the preparation of the intermediate, a pesticidal composition comprising at least one of the pyrazolo[1,5-a]pyridine derivatives, the preparation of the composition, and the use of the pyrazolo[1,5-a]pyridine derivative or composition in agriculture or horticulture for controlling, preventing, or protecting plants, harvested food crops, seeds, or non-living materials from ectoparasitism by phytopathogenic microorganisms, particularly fungi, more particularly oomycetes.
Summary of the Invention
Means for Solving the Problems
[0002] Here, surprisingly, it has been found that certain novel pyrazolo[1,5-a]pyridine derivatives have advantageous fungicidal properties, particularly against oomycetes.
[0003] Thus, in a first aspect, the present invention provides a compound of formula (I)
Chemical Formula
[0004] In a second aspect, the present invention provides a pesticide composition comprising a compound of formula (I), more particularly a pesticide composition comprising a fungicidally effective amount of a compound of formula (I). The composition may further comprise at least one compound selected from additional active ingredients, suitable inert ingredients, carriers, auxiliaries, and any mixture thereof.
[0005] Compounds of formula (I) can be used to control plant pathogenic microorganisms. Therefore, to control plant pathogens, compounds of formula (I) according to the present invention, or compositions containing compounds of formula (I), can be applied directly to plant pathogens, to the habitats of plant pathogens, to plants particularly susceptible to attack by plant pathogens, or to the reproductive material of plants.
[0006] Therefore, in a third aspect, the present invention provides the use of a compound of formula (I), or a composition comprising a compound of formula (I), as described herein, for eradicating, preventing, or controlling plant pathogens.
[0007] In a fourth aspect, the present invention provides a method for eradicating, preventing, or controlling a plant pathogen, comprising applying a compound of formula (I) or a composition containing a compound of formula (I), as described herein, to the plant pathogen, to the habitat of the plant pathogen, particularly to plants susceptible to attack by the plant pathogen, or to the reproductive material of the plant. According to a fourth aspect of the present invention, methods of treating the human or animal body by surgery or treatment may be excluded from the method.
[0008] Compounds of formula (I) are particularly effective in eradicating, preventing, or controlling plant pathogenic fungi, especially Oomycetes. Therefore, in a fifth aspect, the present invention provides the use of compounds of formula (I) described herein, or compositions containing compounds of formula (I), for controlling plant pathogenic fungi, especially Oomycetes.
[0009] In a sixth aspect, the present invention provides a method for eradicating, preventing, or controlling plant pathogenic diseases such as plant pathogenic fungi, comprising applying a compound of formula (I) described herein or a composition containing a compound of formula (I) to the plant pathogenic fungi or the habitat of the plant pathogenic fungi (particularly plants susceptible to attack by plant pathogenic fungi, especially Oomycetes) or to the plant's reproductive material. According to this sixth aspect of the present invention, methods of treating the human or animal body by surgery or therapy can be excluded from the method.
[0010] When a group is indicated as substituted (e.g., alkyl), this includes a group that is part of another group (e.g., alkyl in alkylthio). [Modes for carrying out the invention]
[0011] Definition: - The term "halogen" or "halo" refers to fluorine (fluoro or F), chlorine (chloro or Cl), bromine (bromo or Br), or iodine (iod or I), preferably fluorine, chlorine, or bromine.
[0012] - The term "amino" refers to the -NH2 group.
[0013] - The term “alkyl” as used herein, either alone or as part of a chemical group, refers to a linear or branched hydrocarbon having preferably 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylpropyl, 1,3-dimethylbutyl, 1,4-dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, and 2-ethylbutyl. A alkyl group having 1 to 4 carbon atoms is preferred, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, or t-butyl.
[0014] - The term "alkenyl," either alone or as part of a chemical group, refers to a linear or branched hydrocarbon having preferably 2 to 6 carbon atoms and at least one double bond, such as vinyl, 2-propenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-2-butenyl, 2-methyl -2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-2-propenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2 -Pentenyl, 4-methyl-2-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl- This represents tyl-2-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, and 1-ethyl-2-methyl-2-propenyl. An alkenyl group having 2 to 4 carbon atoms is preferred, for example, 2-propenyl, 2-butenyl, or 1-methyl-2-propenyl.
[0015] - The term "alkynyl," either alone or as part of a chemical group, refers to a linear or branched hydrocarbon having preferably 2 to 6 carbon atoms and at least one triple bond, such as 2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1-methyl-2-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 2-hexynyl, and 3-hexynyl. This represents 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-4-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl, 1-ethyl-1-methyl-2-propynyl, and 2,5-hexadinyl. Alkynnyls having 2 to 4 carbon atoms are preferred, for example, ethynnyl, 2-propynyl, or 2-butynyl-2-propenyl.
[0016] - The term "haloalkyl" refers to an alkyl group, as commonly defined above, that is substituted by one or more identical or different halogen atoms, such as fluoromethyl, fluoroethyl, difluoromethyl, trifluoromethyl, or 2,2,2-trifluoroethyl.
[0017] - The term "cyanoalkyl" refers to an alkyl group that is substituted with one or more cyano groups, as generally defined above.
[0018] - The term "cycloalkyl," either alone or as part of a chemical group, refers to a saturated or partially unsaturated monocyclic, bicyclic, or tricyclic hydrocarbon having preferably 3 to 10 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl, or adamantyl. Cycloalkyls having 3, 4, 5, 6, or 7 carbon atoms are preferred, such as cyclopropyl or cyclobutyl.
[0019] - The term "halocycloalkyl" refers to a cycloalkyl ring, as generally defined above, that is substituted by one or more identical or different halogen atoms.
[0020] - The term "cyanocycloalkyl" refers to a cycloalkyl group, as generally defined above, that is substituted with one or more cyano groups.
[0021] - The term "alkoxy" is derived from the formula -OR a It refers to the base of, and in the formula, R a This refers to alkyl groups as generally defined above. Examples of alkoxys include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, and t-butoxy. The term "alkoxyalkyl" refers to alkyl groups (as mentioned above) substituted with the aforementioned alkoxy group. Examples include methoxymethyl, methoxyethyl, ethoxymethyl, and propoxymethyl.
[0022] - The term "alkylsulfanyl" is derived from the formula -SR a It refers to the base of, and in the formula, R a This is an alkyl group as generally defined above.
[0023] - The term "alkylsulfinyl" is derived from the formula -S(O)R a It refers to the base of, and in the formula, R a This is an alkyl group as generally defined above.
[0024] - The term "alkylsulfonyl" is derived from the formula -S(O)2R a It refers to the base of, and in the formula, R a This is an alkyl group as generally defined above.
[0025] - The term "alkylcarbonyl" is derived from the formula R a It refers to the C(O)- group, and in the formula, R a This is an alkyl group as generally defined above.
[0026] - The term "alkoxycarbonyl" is derived from the formula R a It refers to the OC(O)- group, and in the formula, R a This is an alkyl group as generally defined above.
[0027] - The term "alkylamino" is derived from the formula R a It refers to the NH- group, and in the formula, R a This is an alkyl group as generally defined above.
[0028] - The term "cycloalkylamino" is derived from the formula R a It refers to the NH- group, and in the formula, R a This is a cycloalkyl group as generally defined above.
[0029] - The term "alkoxyamino" is derived from the formula R a It refers to the NH- group, and in the formula, R a This is an alkyl group as generally defined above.
[0030] - The term "alkylaminocarbonyl" is derived from the formula R a It refers to the NHC(O)- group, and in the formula, R a This is an alkyl group as generally defined above.
[0031] - Hydroxyl or hydroxy represents the -OH group.
[0032] The terms “to eradicate,” “to prevent,” or “to control,” and their use, in relation to the present invention, mean reducing pathogenicity, more specifically plant pathogenicity, to a level in which improvement is demonstrated, to any undesirable effects, particularly those of fungi such as Oomycetes, exocytosis or attack on plants or plant-derived products, and pathogenic damage.
[0033] As used herein, the term "effective amount" refers to the amount of a compound, its salt, or N-oxide that produces the desired effect through a single or multiple application.
[0034] The effective dose can be readily determined by those skilled in the art by using known techniques and observing the results obtained under similar circumstances. Several factors are considered in determining the effective dose, including, but not limited to, the type of plant or derivative product to be applied; the pathogen to be controlled and its life cycle; the specific compound to be applied; the type of application; and other relevant circumstances.
[0035] Compounds of formula (I) having at least one basic center include, for example, strong inorganic acids, such as mineral acids, such as perchloric acid, sulfuric acid, nitric acid, nitrite, phosphoric acid, or hydrohalic acid, along with strong organic carboxylic acids, such as unsubstituted or halogenated C 1-4 Alkane carboxylic acids, such as acetic acid; saturated or unsaturated dicarboxylic acids, such as oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, or phthalic acid; hydroxycarboxylic acids, such as ascorbic acid, lactic acid, malic acid, tartaric acid, or citric acid; or together with benzoic acid, or with organic sulfonic acids, such as unsubstituted or substituted with halogens. 1-4Compounds of formula (I) having at least one acidic group can form salts with, for example, alkanes or aryl sulfonic acids, such as methane or p-toluenesulfonic acid, to form acid addition salts. Compounds of formula (I) having at least one acidic group can form salts with, for example, bases, such as mineral salts, such as alkali metal or alkaline earth metal salts, such as sodium, potassium, or magnesium salts, or salts with monamines or organic amines, such as morpholine, piperidine, pyrrolidine, mono-, di-, or tri-lower alkylamines, such as ethyl-, diethyl-, triethyl, or dimethylpropylamine, or salts with mono-, di-, or trihydroxy lower alkylamines, such as mono-, di-, or triethanolamine.
[0036] In each case, the compound of formula (I) according to the present invention exists in a free form, an oxidized form as an N-oxide, a covalently hydrated form, or a salt form, for example, an agriculturally usable or agrochemically acceptable salt form. The N-oxide is an oxidized form of a tertiary amine or an oxidized form of a nitrogen-containing heteroaromatic compound. These are described, for example, in the book "Heterocyclic N-oxides" by A. Albini and S. Pietra, CRC Press, Boca Raton 1991. The compound of formula (I) according to the present invention also includes hydrates that may be formed during salt formation.
[0037] Furthermore, the compounds of formula (I) according to the present invention include hydrates that may be formed during salt formation.
[0038] In further embodiments, a compound of formula (I) according to the present invention, R 1a C 1-6 Alkyl, C 3-6 Cycloalkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl and C 1-6 Alkoxy, preferably C 1-6 Compounds selected from alkyl groups are provided.
[0039] In further embodiments, a compound of formula (I) according to the present invention, R 1b , R 1c , and R 1d is hydrogen, C 1-6 Alkyl, C 3-6 Cycloalkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl and C 1-6 Selected independently of alkoxy; preferably, R 1b , R 1c , and R 1d A compound is provided in which hydrogen is present.
[0040] In a particular embodiment, a compound of formula (I) according to the present invention, R 1a These are hydroxy, halogen, CN, and C 1-6 Alkyl, C 3-6 Cycloalkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 1-6 Alkyl sulfanyl, C 1-6 Alkyl sulfinyl, C 1-6 Alkyl sulfonyl, C 1-6 Alkoxy, amino, and NHC(O)C 1-6 Selected from alkyl; R 1b , R 1c , and R 1d A compound is provided, which is hydrogen.
[0041] In further embodiments, a compound of formula (I) according to the present invention, R 2 These are hydrogen, hydroxyl, halogen, CN, and C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 1-6 Alkoxycarbonyl, C 1-6Alkylaminocarbonyl, diC 1-6 Alkylaminocarbonyl, and C 1-6 Independently selected from alkylcarbonyls, where C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 1-6 Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, diC 1-6 Alkylaminocarbonyl, and C 1-6 The alkylcarbonyl group may be optionally substituted with 1 to 3 substituents independently selected from halogen, hydroxyl, and CN; preferably R 2 Hydrogen, halogen, CN, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxycarbonyl and C 1-6 Alkoxy-C 1-6 Selected independently of alkoxy, where C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxycarbonyl and C 1-6 Alkoxy-C 1-6 Each of the alkoxy groups may be optionally substituted with 1 to 3 substituents independently selected from halogens, hydroxyls, and CNs; more preferably, R 2 Hydrogen, halogen, CN, C 1-6 Alkyl and C 1-6 Compounds are provided that are independently selected from alkoxys.
[0042] In further embodiments, a compound of formula (I) according to the present invention, R 3 These are hydrogen, hydroxyl, halogen, CN, and C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl, amino, C 1-6 Alkylamino, diC 1-6 -alkylamino and C 3-6 Selected from cycloalkylaminos, where C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl, amino, C 1-6 Alkylamino, diC 1-6 -alkylamino and C 3-6 Compounds are provided in which each of the cycloalkylamino groups may be optionally substituted with 1 to 3 substituents independently selected from halogens, hydroxyls, and CNs. In a preferred embodiment, R 3 It could be hydrogen.
[0043] In a further embodiment, a compound of formula (I) according to the present invention, wherein four A 2 CR 2 A 3 A compound is provided in which is N.
[0044] In further embodiments, a compound of formula (I) according to the present invention, [ka] teeth [ka] And, Preferably three A 2 CR 2 A 3 CR3 A compound is provided.
[0045] In further embodiments, a compound of formula (I) according to the present invention, [ka] teeth [ka] And, Preferably three A 2 CR 2 A 3 CR 3 A compound is provided.
[0046] In a further embodiment, a compound of formula (I) according to the present invention, wherein four A 2 CR 2 A 3 CR 3 Preferably [ka] teeth [ka] A compound is provided.
[0047] [ka] but [ka] In a particular embodiment, R 2 This is as defined in the present invention; preferably, R 2 These are hydrogen, hydroxyl, halogen, CN, and C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl, C 1-6 Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, diC 1-6 Alkylaminocarbonyl, and C 1-6 Independently selected from alkylcarbonyls, where C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl, C 1-6 Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, diC 1-6 Alkylaminocarbonyl, and C 1-6 Each alkylcarbonyl group may be optionally substituted with 1 to 3 substituents independently selected from halogens, hydroxyls, and CNs; preferably, R 2 Hydrogen, halogen, CN, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxycarbonyl and C 1-6 Alkoxy-C 1-6 Selected independently of alkoxy, where C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxycarbonyl and C 1-6 Alkoxy-C 1-6 Each of the alkoxy groups may be optionally substituted with 1 to 3 substituents independently selected from halogens, hydroxyls, and CNs; more preferably, R 2 Hydrogen, halogen, CN, C 1-6 Alkyl and C 1-6It is selected independently of alkoxy.
[0048] In further embodiments, a compound of formula (I) according to the present invention, R 4 C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 2-6 Alkenil, C 2-6 Alkinyl and C 1-6 Selected from alkoxy, where C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 2-6 Alkenil, C 2-6 Alkinyl and C 1-6 Each of the alkoxy groups may be optionally substituted with 1 to 3 substituents independently selected from halogens and CN; preferably R 4 C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl and C 1-6 Selected from alkoxy, where C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl and C 1-6 Each alkoxy group may be optionally substituted with 1 to 3 substituents independently selected from halogens and CN; Here, A 3 and R 4 Compounds are provided in which these components optionally combine to form a ring, more preferably a 5-8 membered heterocycle, and more preferably a 6 membered heterocycle.
[0049] In further embodiments, a compound of formula (I) according to the present invention, A 3 CR 3 And R 3 and R 4 These combine to form a ring, preferably a 5-8 membered heterocycle, preferably a 6 membered heterocycle, more preferably the following formula (I): [ka] A compound is provided which forms one of the rings W1, W2, or W3 described in the compound.
[0050] The carbon and / or nitrogen atoms forming the ring (W1, W2, or W3) are, in particular, R 3’ It can be substituted by the group, where R 3’ is hydrogen, C 1-6 Alkyl and C 3-6 Selected from cycloalkyl, C 1-6 Alkyl and C 3-6 Each cycloalkyl group may be optionally substituted with 1 to 3 substituents independently selected from halogens and CN. For example, the compound of formula (I-W3) may be as follows: [ka]
[0051] In preferred embodiments, the compounds of formulas (I-W1), (I-W2), and (I-W3) may be as follows: [ka]
[0052] The carbon and / or nitrogen atoms forming the ring (W1, W2, or W3) are, in particular, R 3’ It can be substituted by the group, where R 3’ is hydrogen, C 1-6 Alkyl and C 3-6 Selected from cycloalkyl, C 1-6Alkyl and C 3-6 Each cycloalkyl group may be optionally substituted with 1 to 3 substituents independently selected from halogens and CN. For example, the compound of formula (I-W3) may be as follows: [ka]
[0053] In further embodiments, a compound of formula (I) according to the present invention, R 5 C 1-6 Alkyl, C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl and C 1-6 Alkoxy C 1-6 A compound is provided, selected from alkyl groups, where each of the groups may be optionally substituted with 1 to 3 substituents independently selected from halogens and CN.
[0054] In certain embodiments, a compound of formula (I) according to the present invention is provided, wherein, Z is O; A 1 is N; R 1a C 1-6 Alkyl, C 3-6 Cycloalkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl and C 1-6 Selected from alkoxys, preferably C 1-6 It is alkyl; R 1b is hydrogen, C 1-6 Alkyl, C 3-6 Cycloalkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl and C 1-6 Selected from alkoxy, preferably hydrogen; R 1c is hydrogen, C 1-6 Alkyl, C 3-6 Cycloalkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl and C 1-6 Selected from alkoxy, preferably hydrogen; R 1d is hydrogen, C 1-6 Alkyl, C 3-6 Cycloalkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl and C 1-6 Selected from alkoxy, preferably hydrogen; 4 2 CR 2 And; R 2 These are hydrogen, hydroxyl, halogen, CN, and C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 2-6 Alkenil, C 2-6 Alkinyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl, C 1-6 Alkyl sulfanyl, C 1-6 Alkyl sulfinyl, and C 1-6 Independently selected from alkylsulfonyls, where C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 2-6 Alkenil, C 2-6 Alkinyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl, C1-6 Alkyl sulfanyl, C 1-6 Alkyl sulfinyl, and C 1-6 Each alkylsulfonyl group may be optionally substituted with 1 to 3 substituents independently selected from halogens, hydroxyls, and CNs; preferably, R 2 Hydrogen, halogen, CN, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxycarbonyl and C 1-6 Alkoxy-C 1-6 Selected independently of alkoxy, where C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxycarbonyl and C 1-6 Alkoxy-C 1-6 Each of the alkoxy groups may be optionally substituted with 1 to 3 substituents independently selected from halogens, hydroxyls, and CNs; more preferably, R 2 Hydrogen, halogen, CN, C 1-6 Alkyl and C 1-6 Selected independently of alkoxy; A 3 CR 3 And R 3 These are hydrogen, hydroxyl, halogen, CN, and C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 2-6 Alkenil, C 2-6 Alkinyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl, C 1-6 Alkyl sulfanyl, C 1-6 Alkyl sulfinyl, C 1-6 Alkylsulfonyl, amino, C 1-6Alkylamino, diC 1-6 -alkylamino and C 3-6 Selected from cycloalkylaminos, where C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 2-6 Alkenil, C 2-6 Alkinyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl, C 1-6 Alkyl sulfanyl, C 1-6 Alkyl sulfinyl, C 1-6 Alkylsulfonyl, amino, C 1-6 Alkylamino, diC 1-6 -alkylamino and C 3-6 Each of the cycloalkylamino groups may be optionally substituted with 1 to 3 substituents independently selected from halogens, hydroxyls, and CNs; preferably, R 3 is hydrogen; R 4 C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl and C 1-6 Selected from alkoxy, where C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl and C 1-6 Each of the alkoxy groups may be optionally substituted with 1 to 3 substituents independently selected from halogens and CN; A 3 and R 4 They can optionally come together to form a ring, more preferably a 5- to 8-membered complex ring, more preferably a 6-membered complex ring; R5 C 1-6 Alkyl, C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl, C 1-6 Alkoxy C 1-6 Alkyl, C 1-6 Alkylamino, diC 1-6 Alkylamino, and C 1-6 Alkyl C 1-6 Selected from alkoxyaminos, where each of the groups may be optionally substituted with 1 to 3 substituents independently selected from halogens and CN, preferably R 5 C 1-6 Alkyl, C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl and C 1-6 Alkoxy C 1-6 Selected from alkyl groups, each of which may be optionally substituted with 1 to 3 substituents independently selected from halogens and CN.
[0055] In a preferred embodiment, [ka] teeth [ka] And in the formula, R 2 This is as defined in the present invention; preferably, R 2 These are hydrogen, hydroxyl, halogen, CN, and C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl, C 1-6Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, diC 1-6 Alkylaminocarbonyl, and C 1-6 Independently selected from alkylcarbonyls, where C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl, C 1-6 Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, di C1-6 Alkylaminocarbonyl, and C 1-6 Each alkylcarbonyl group may be optionally substituted with 1 to 3 substituents independently selected from halogens, hydroxyls, and CNs; preferably, R 2 Hydrogen, halogen, CN, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxycarbonyl and C 1-6 Alkoxy-C 1-6 Selected independently of alkoxy, where C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxycarbonyl and C 1-6 Alkoxy-C 1-6 Each of the alkoxy groups may be optionally substituted with 1 to 3 substituents independently selected from halogens, hydroxyls, and CNs; more preferably, R 2 Hydrogen, halogen, CN, C 1-6 Alkyl and C 1-6 It is selected independently of alkoxy.
[0056] In further embodiments, compounds according to the present invention are: Methyl N-[5-[5-[(4-fluoro-3-methoxyphenyl)-methyl-carbamoyl]-7-methyl-pyrazolo[1,5-a]pyridin-3-yl]-2-pyridyl]carbamate; Methyl N-[5-[5-[(4-fluoro-3-methoxyphenyl)-(methoxymethyl)carbamoyl]-7-methyl-pyrazolo[1,5-a]pyridin-3-yl]-2-pyridyl]carbamate; Methyl N-[5-[5-(6-fluoro-4-methyl-2,3-dihydroquinoxaline-1-carbonyl)-7-methyl-pyrazolo[1,5-a]pyridine-3-yl]-2-pyridyl]carbamate; Methyl N-[5-[5-[(4-fluoro-2-methoxyphenyl)-methyl-carbamoyl]-7-methyl-pyrazolo[1,5-a]pyridin-3-yl]-2-pyridyl]carbamate, Methyl N-[5-[5-(7-fluoro-2,3-dihydro-1,4-benzoxazine-4-carbonyl)-7-methyl-pyrazolo[1,5-a]pyridine-3-yl]-2-pyridyl]carbamate; Methyl N-[5-[5-[(4-chloro-3-methylphenyl)-methyl-carbamoyl]-7-methyl-pyrazolo[1,5-a]pyridine-3-yl]-2-pyridyl]carbamate; Methyl 2-fluoro-5-[[3-[6-(methoxycarbonylamino)-3-pyridyl]-7-methyl-pyrazolo[1,5-a]pyridine-5-carbonyl]-methyl-amino]benzoate; Methyl N-[5-[5-[(4-acetamidophenyl)-methyl-carbamoyl]-7-methyl-pyrazolo[1,5-a]pyridin-3-yl]-2-pyridyl]carbamate; and Methyl N-[5-[5-[(4-chlorophenyl)-methyl-carbamoyl]-7-methyl-pyrazolo[1,5-a]pyridin-3-yl]-2-pyridyl]carbamate Selected from
[0057] Methods according to the present invention have advantageous properties for protecting plants from pathogenic attacks or ectoparasitization that cause disease and damage to plants, such as plant pathogenic fungi, particularly Oomycetes; in particular, in the case of plants, the present invention can control, limit, or prevent pathogenic damage to plants, parts of plants, plant propagation materials, and / or grown plants.
[0058] The compounds listed in Tables 1.1 to 1.315 below illustrate specific compounds of the present invention.
[0059] Table 1.1 shows equation (Ia) [ka] Compounds E1.1~E1.483 (wherein A 2a is N, and R 5 It is CH3, and R 1a It is CH3, and R 2 , R 3 , R 4 , A 1 , A 2b This provides (as defined in Table Z).
[0060] More specifically, Table Z is A 3 and R 4 This also includes compounds in which the atoms are combined to form a ring. In this case, the ring is formed by the amide atoms linked to the biring core of formula (Ia) being integrated together. 3 and R 4 This is shown in column (Table Z). For example, compound E1.36 A 3 and R 4 Please refer to the column.
[0061] [Table 1-1]
[0062] [Table 1-2]
[0063] Table 1-3
[0064] Table 1-4
[0065] Table 1-5
[0066] Table 1-6
[0067] Table 1-7
[0068] Table 1-8
[0069] Table 1-9
[0070] Table 1-10
[0071] Table 1-11
[0072] Table 1-12
[0073] Table 1-13
[0074] Table 1-14
[0075] Table 1-15
[0076] Table 1-16
[0077] Table 1-17
[0078] Table 1-18
[0079] Table 1-19
[0080] Table 1-20
[0081] Table 1-21
[0082] Table 1-22
[0083] Table 1-23
[0084] [Table 1-24]
[0085] [Table 1-25]
[0086] [Table 1-26]
[0087] [Table 1-27]
[0088] [Table 1-28]
[0089] Table 1.2 provides 483 compounds E2.1 to E2.483 of formula (Ia), where A 2a is N, and R 5 It is CH3, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0090] Table 1.3 provides 483 compounds E3.1 to E3.483 of formula (Ia), where A 2a is N, and R 5 It is CH3, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0091] Table 1.4 provides 483 compounds E4.1 to E4.483 of formula (Ia), where A 2a is N, and R 5 It is CH3, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0092] Table 1.5 provides 483 compounds E5.1 to E5.483 of formula (Ia), where A 2a is N, and R 5 It is CH3, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0093] Table 1.6 provides 483 compounds E6.1 to E6.483 of formula (Ia), where A 2a is N, and R 5 It is CH3, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0094] Table 1.7 provides 483 compounds E7.1 to E7.483 of formula (Ia), where A 2a is N, and R 5 It is CH3, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0095] Table 1.8 provides 483 compounds E8.1 to E8.483 of formula (Ia), where A 2a is N, and R 5 It is OCH3, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0096] Table 1.9 provides 483 compounds E9.1 to E9.483 of formula (Ia), where A 2a is N, and R 5 It is OCH3, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0097] Table 1.10 provides 483 compounds E10.1 to E10.483 of formula (Ia), where A 2a is N, and R 5 It is OCH3, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0098] Table 1.11 provides 483 compounds E11.1 to E11.483 of formula (Ia), where A 2a is N, and R 5 It is OCH3, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0099] Table 1.12 provides 483 compounds E12.1 to E12.483 of formula (Ia), where A2a is N, and R 5 It is OCH3, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0100] Table 1.13 provides 483 compounds E13.1 to E13.483 of formula (Ia), where A 2a is N, and R 5 It is OCH3, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0101] Table 1.14 provides 483 compounds E14.1 to E14.483 of formula (Ia), where A 2a is N, and R 5 It is OCH3, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0102] Table 1.15 provides 483 compounds E15.1 to E15.483 of formula (Ia), where A 2a is N, and R 5 It is cyclopropyl, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0103] Table 1.16 provides 483 compounds E16.1 to E16.483 of formula (Ia), where A 2a is N, and R 5 It is cyclopropyl, and R1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0104] Table 1.17 provides 483 compounds E17.1 to E17.483 of formula (Ia), where A 2a is N, and R 5 It is cyclopropyl, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0105] Table 1.18 provides 483 compounds E18.1 to E18.483 of formula (Ia), where A 2a is N, and R 5 It is cyclopropyl, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0106] Table 1.19 provides 483 compounds E19.1 to E19.483 of formula (Ia), where A 2a is N, and R 5 It is cyclopropyl, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0107] Table 1.20 provides 483 compounds E20.1 to E20.483 of formula (Ia), where A 2a is N, and R 5 It is cyclopropyl, and R 1a NHAc is R2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0108] Table 1.21 provides 483 compounds E21.1 to E21.483 of formula (Ia), where A 2a is N, and R 5 It is cyclopropyl, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0109] Table 1.22 provides 483 compounds E22.1 to E22.483 of formula (Ia), where A 2a is N, and R 5 It is CH2OCH3, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0110] Table 1.23 provides 483 compounds E23.1 to E23.483 of formula (Ia), where A 2a is N, and R 5 It is CH2OCH3, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0111] Table 1.24 provides 483 compounds E24.1 to E24.483 of formula (Ia), where A 2a is N, and R 5 It is CH2OCH3, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4, A 1 , A 2b This is as defined in Table Z.
[0112] Table 1.25 provides 483 compounds E25.1 to E25.483 of formula (Ia), where A 2a is N, and R 5 It is CH2OCH3, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0113] Table 1.26 provides 483 compounds E26.1 to E26.483 of formula (Ia), where A 2a is N, and R 5 It is CH2OCH3, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0114] Table 1.27 provides 483 compounds E27.1 to E27.483 of formula (Ia), where A 2a is N, and R 5 It is CH2OCH3, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0115] Table 1.28 provides 483 compounds E28.1 to E28.483 of formula (Ia), where A 2a is N, and R 5 It is CH2OCH3, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2bThis is as defined in Table Z.
[0116] Table 1.29 provides 483 compounds E29.1 to E29.483 of formula (Ia), where A 2a is N, and R 5 It is NHCH2CH3, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0117] Table 1.30 provides 483 compounds E30.1 to E30.483 of formula (Ia), where A 2a is N, and R 5 It is NHCH2CH3, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0118] Table 1.31 provides 483 compounds E31.1 to E31.483 of formula (Ia), where A 2a is N, and R 5 It is NHCH2CH3, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0119] Table 1.32 provides 483 compounds E32.1 to E32.483 of formula (Ia), where A 2a is N, and R 5 It is NHCH2CH3, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0120] Table 1.33 provides 483 compounds E33.1 to E33.483 of formula (Ia), where A 2a is N, R 5 is NHCH2CH3, R 1a is CH2cyclopropyl, R 2 , A 3 , R 4 , A 1 , A 2b is as defined in Table Z
[0121] Table 1.34 provides 483 compounds E34.1 to E34.483 of formula (Ia), where A 2a is N, R 5 is NHCH2CH3, R 1a is NHAc, R 2 , A 3 , R 4 , A 1 , A 2b is as defined in Table Z
[0122] Table 1.35 provides 483 compounds E35.1 to E35.483 of formula (Ia), where A<00Table 1.37 provides 483 compounds E37.1 to E37.483 of formula (Ia), where A 2a CH is, R 5 It is CH3, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0125] Table 1.38 provides 483 compounds E38.1 to E38.483 of formula (Ia), where A 2a CH is, R 5 It is CH3, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0126] Table 1.39 provides 483 compounds E39.1 to E39.483 of formula (Ia), where A 2a CH is, R 5 It is CH3, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0127] Table 1.40 provides 483 compounds E40.1 to E40.483 of formula (Ia), where A 2a CH is, R 5 It is CH3, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0128] Table 1.41 provides 483 compounds E41.1 to E41.483 of formula (Ia), wherein A 2a is CH, R 5 is CH3, R 1a is NHAc, R 2 , A 3 , R 4 , A 1 , A 2b are as defined in Table Z.
[0129] Table 1.42 provides 483 compounds E42.1 to E42.483 of formula (Ia), wherein A 2a is CH, R 5 is CH3, R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b are as defined in Table Z.
[0130] Table 1.43 provides 483 compounds E43.1 to E43.483 of formula (Ia), wherein A 2a is CH, R 5 [[ID=4�]]is OCH3, R 1a is CH3, R 2 , A 3 , R 4 , A 1 , A 2b are as defined in Table Z.
[0131] Table 1.44 provides 483 compounds E44.1 to E44.483 of formula (Ia), wherein A 2a is CH, R 5 is OCH3, R 1a is CH2CH3, R 2 , A 3 , R 4 , A 1 , A 2b are as defined in Table Z.
[0132] Table 1.45 provides 483 compounds E45.1 to E45.483 of formula (Ia), wherein A2a CH is, R 5 It is OCH3, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0133] Table 1.46 provides 483 compounds E46.1 to E46.483 of formula (Ia), where A 2a CH is, R 5 It is OCH3, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0134] Table 1.47 provides 483 compounds E47.1 to E47.483 of formula (Ia), where A 2a CH is, R 5 It is OCH3, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0135] Table 1.48 provides 483 compounds E48.1 to E48.483 of formula (Ia), where A 2a CH is, R 5 It is OCH3, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0136] Table 1.49 provides 483 compounds E49.1 to E49.483 of formula (Ia), where A 2a CH is, R 5It is OCH3, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0137] Table 1.50 provides 483 compounds E50.1 to E50.483 of formula (Ia), where A 2a CH is, R 5 It is cyclopropyl, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0138] Table 1.51 provides 483 compounds E51.1 to E51.483 of formula (Ia), where A 2a CH is, R 5 It is cyclopropyl, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0139] Table 1.52 provides 483 compounds E52.1 to E52.483 of formula (Ia), where A 2a CH is, R 5 It is cyclopropyl, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0140] Table 1.53 provides 483 compounds E53.1 to E53.483 of formula (Ia), where A 2a CH is, R 5 It is cyclopropyl, and R 1aIt is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0141] Table 1.54 provides 483 compounds E54.1 to E54.483 of formula (Ia), where A 2a CH is, R 5 It is cyclopropyl, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0142] Table 1.55 provides 483 compounds E55.1 to E55.483 of formula (Ia), where A 2a CH is, R 5 It is cyclopropyl, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0143] Table 1.56 provides 483 compounds E56.1 to E56.483 of formula (Ia), where A 2a CH is, R 5 It is cyclopropyl, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0144] Table 1.57 provides 483 compounds E57.1 to E57.483 of formula (Ia), where A 2a CH is, R 5 It is CH2OCH3, and R 1a It is CH3, and R 2 , A3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0145] Table 1.58 provides 483 compounds E58.1 to E58.483 of formula (Ia), where A 2a CH is, R 5 It is CH2OCH3, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0146] Table 1.59 provides 483 compounds E59.1 to E59.483 of formula (Ia), where A 2a CH is, R 5 It is CH2OCH3, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0147] Table 1.60 provides 483 compounds E60.1 to E60.483 of formula (Ia), where A 2a CH is, R 5 It is CH2OCH3, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0148] Table 1.61 provides 483 compounds E61.1 to E61.483 of formula (Ia), where A 2a CH is, R 5 It is CH2OCH3, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R4 , A 1 , A 2b This is as defined in Table Z.
[0149] Table 1.62 provides 483 compounds E62.1 to E62.483 of formula (Ia), where A 2a CH is, R 5 It is CH2OCH3, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0150] Table 1.63 provides 483 compounds E63.1 to E63.483 of formula (Ia), where A 2a CH is, R 5 It is CH2OCH3, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0151] Table 1.64 provides 483 compounds E64.1 to E64.483 of formula (Ia), where A 2a CH is, R 5 It is NHCH2CH3, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0152] Table 1.65 provides 483 compounds E65.1 to E65.483 of formula (Ia), where A 2a CH is, R 5 It is NHCH2CH3, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A2b This is as defined in Table Z.
[0153] Table 1.66 provides 483 compounds E66.1 to E66.483 of formula (Ia), where A 2a CH is, R 5 It is NHCH2CH3, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0154] Table 1.67 provides 483 compounds E67.1 to E67.483 of formula (Ia), where A 2a CH is, R 5 It is NHCH2CH3, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0155] Table 1.68 provides 483 compounds E68.1 to E68.483 of formula (Ia), where A 2a CH is, R 5 It is NHCH2CH3, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0156] Table 1.69 provides 483 compounds E69.1 to E69.483 of formula (Ia), where A 2a CH is, R 5 It is NHCH2CH3, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2bThis is as defined in Table Z.
[0157] Table 1.70 provides 483 compounds E70.1 to E70.483 of formula (Ia), where A 2a CH is, R 5 It is NHCH2CH3, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0158] Table 1.71 provides 483 compounds E71.1 to E71.483 of formula (Ia), where A 2a is CF, R 5 It is CH3, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0159] Table 1.72 provides 483 compounds E72.1 to E72.483 of formula (Ia), where A 2a is CF, R 5 It is CH3, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0160] Table 1.73 provides 483 compounds E73.1 to E73.483 of formula (Ia), where A 2a is CF, R 5 It is CH3, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0161] Table 1.74 provides 483 compounds E74.1 to E74.483 of formula (Ia), where A 2a is CF, R 5 It is CH3, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0162] Table 1.75 provides 483 compounds E75.1 to E75.483 of formula (Ia), where A 2a is CF, R 5 It is CH3, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0163] Table 1.76 provides 483 compounds E76.1 to E76.483 of formula (Ia), where A 2a is CF, R 5 It is CH3, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0164] Table 1.77 provides 483 compounds E77.1 to E77.483 of formula (Ia), where A 2a is CF, R 5 It is CH3, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0165] Table 1.78 provides 483 compounds E78.1 to E78.483 of formula (Ia), where A 2a is CF, R 5 It is OCH3, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0166] Table 1.79 provides 483 compounds E79.1 to E79.483 of formula (Ia), where A 2a is CF, R 5 It is OCH3, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0167] Table 1.80 provides 483 compounds E80.1 to E80.483 of formula (Ia), where A 2a is CF, R 5 It is OCH3, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0168] Table 1.81 provides 483 compounds E81.1 to E81.483 of formula (Ia), where A 2a is CF, R 5 It is OCH3, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0169] Table 1.82 provides 483 compounds E82.1 to E82.483 of formula (Ia), where A2a is CF, R 5 It is OCH3, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0170] Table 1.83 provides 483 compounds E83.1 to E83.483 of formula (Ia), where A 2a is CF, R 5 It is OCH3, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0171] Table 1.84 provides 483 compounds E84.1 to E84.483 of formula (Ia), where A 2a is CF, R 5 It is OCH3, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0172] Table 1.85 provides 483 compounds E85.1 to E85.483 of formula (Ia), where A 2a is CF, R 5 It is cyclopropyl, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0173] Table 1.86 provides 483 compounds E86.1 to E86.483 of formula (Ia), where A 2a is CF, R 5It is cyclopropyl, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0174] Table 1.87 provides 483 compounds E87.1 to E87.483 of formula (Ia), where A 2a is CF, R 5 It is cyclopropyl, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0175] Table 1.88 provides 483 compounds E88.1 to E88.483 of formula (Ia), where A 2a is CF, R 5 It is cyclopropyl, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0176] Table 1.89 provides 483 compounds E89.1 to E89.483 of formula (Ia), where A 2a is CF, R 5 It is cyclopropyl, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0177] Table 1.90 provides 483 compounds E90.1 to E90.483 of formula (Ia), where A 2a is CF, R 5 It is cyclopropyl, and R 1aNHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0178] Table 1.91 provides 483 compounds E91.1 to E91.483 of formula (Ia), where A 2a is CF, R 5 It is cyclopropyl, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0179] Table 1.92 provides 483 compounds E92.1 to E92.483 of formula (Ia), where A 2a is CF, R 5 It is CH2OCH3, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0180] Table 1.93 provides 483 compounds E93.1 to E93.483 of formula (Ia), where A 2a is CF, R 5 It is CH2OCH3, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0181] Table 1.94 provides 483 compounds E94.1 to E94.483 of formula (Ia), where A 2a is CF, R 5 It is CH2OCH3, and R 1a It is CH2OCH3, and R 2 , A3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0182] Table 1.95 provides 483 compounds E95.1 to E95.483 of formula (Ia), where A 2a is CF, R 5 It is CH2OCH3, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0183] Table 1.96 provides 483 compounds E96.1 to E96.483 of formula (Ia), where A 2a is CF, R 5 It is CH2OCH3, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0184] Table 1.97 provides 483 compounds E97.1 to E97.483 of formula (Ia), where A 2a is CF, R 5 It is CH2OCH3, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0185] Table 1.98 provides 483 compounds E98.1 to E98.483 of formula (Ia), where A 2a is CF, R 5 It is CH2OCH3, and R 1a is CN, R 2 , A 3 , R 4 , A1 , A 2b This is as defined in Table Z.
[0186] Table 1.99 provides 483 compounds E99.1 to E99.483 of formula (Ia), where A 2a is CF, R 5 It is NHCH2CH3, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0187] Table 1.100 provides 483 compounds E100.1 to E100.483 of formula (Ia), where A 2a is CF, R 5 It is NHCH2CH3, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0188] Table 1.101 provides 483 compounds E101.1 to E101.483 of formula (Ia), where A 2a is CF, R 5 It is NHCH2CH3, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0189] Table 1.102 provides 483 compounds E102.1 to E102.483 of formula (Ia), where A 2a is CF, R 5 It is NHCH2CH3, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A2b This is as defined in Table Z.
[0190] Table 1.103 provides 483 compounds E103.1 to E103.483 of formula (Ia), where A 2a is CF, R 5 It is NHCH2CH3, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0191] Table 1.104 provides 483 compounds E104.1 to E104.483 of formula (Ia), where A 2a is CF, R 5 It is NHCH2CH3, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0192] Table 1.105 provides 483 compounds E105.1 to E105.483 of formula (Ia), where A 2a is CF, R 5 It is NHCH2CH3, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0193] Table 1.106 provides 483 compounds E106.1 to E106.483 of formula (Ia), where A 2a is CCl, and R 5 It is CH3, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2bThis is as defined in Table Z.
[0194] Table 1.107 provides 483 compounds E107.1 to E107.483 of formula (Ia), where A 2a is CCl, and R 5 It is CH3, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0195] Table 1.108 provides 483 compounds E108.1 to E108.483 of formula (Ia), where A 2a is CCl, and R 5 It is CH3, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0196] Table 1.109 provides 483 compounds E109.1 to E109.483 of formula (Ia), where A 2a is CCl, and R 5 It is CH3, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0197] Table 1.110 provides 483 compounds E110.1 to E110.483 of formula (Ia), where A 2a is CCl, and R 5 It is CH3, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0198] Table 1.111 provides 483 compounds E111.1 to E111.483 of formula (Ia), where A 2a is CCl, and R 5 It is CH3, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0199] Table 1.112 provides 483 compounds E112.1 to E112.483 of formula (Ia), where A 2a is CCl, and R 5 It is CH3, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0200] Table 1.113 provides 483 compounds E113.1 to E113.483 of formula (Ia), where A 2a is CCl, and R 5 It is OCH3, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0201] Table 1.114 provides 483 compounds E114.1 to E114.483 of formula (Ia), where A 2a is CCl, and R 5 It is OCH3, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0202] Table 1.115 provides 483 compounds E115.1 to E115.483 of formula (Ia), where A 2a is CCl, and R 5 It is OCH3, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0203] Table 1.116 provides 483 compounds E116.1 to E116.483 of formula (Ia), where A 2a is CCl, and R 5 It is OCH3, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0204] Table 1.117 provides 483 compounds E117.1 to E117.483 of formula (Ia), where A 2a is CCl, and R 5 It is OCH3, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0205] Table 1.118 provides 483 compounds E118.1 to E118.483 of formula (Ia), where A 2a is CCl, and R 5 It is OCH3, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0206] Table 1.119 provides 483 compounds E119.1 to E119.483 of formula (Ia), where A 2a is CCl, and R 5 It is OCH3, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0207] Table 1.120 provides 483 compounds E120.1 to E120.483 of formula (Ia), where A 2a is CCl, and R 5 It is cyclopropyl, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0208] Table 1.121 provides 483 compounds E121.1 to E121.483 of formula (Ia), where A 2a is CCl, and R 5 It is cyclopropyl, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0209] Table 1.122 provides 483 compounds E122.1 to E122.483 of formula (Ia), where A 2a is CCl, and R 5 It is cyclopropyl, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0210] Table 1.123 provides 483 compounds E123.1 to E123.483 of formula (Ia), where A 2a is CCl, and R 5 It is cyclopropyl, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0211] Table 1.124 provides 483 compounds E124.1 to E124.483 of formula (Ia), where A 2a is CCl, and R 5 It is cyclopropyl, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0212] Table 1.125 provides 483 compounds E125.1 to E125.483 of formula (Ia), where A 2a is CCl, and R 5 It is cyclopropyl, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0213] Table 1.126 provides 483 compounds E126.1 to E126.483 of formula (Ia), where A 2a is CCl, and R 5 It is cyclopropyl, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0214] Table 1.127 provides 483 compounds E127.1 to E127.483 of formula (Ia), where A 2a is CCl, and R 5 It is CH2OCH3, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0215] Table 1.128 provides 483 compounds E128.1 to E128.483 of formula (Ia), where A 2a is CCl, and R 5 It is CH2OCH3, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0216] Table 1.129 provides 483 compounds E129.1 to E129.483 of formula (Ia), where A 2a is CCl, and R 5 It is CH2OCH3, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0217] Table 1.130 provides 483 compounds E130.1 to E130.483 of formula (Ia), where A 2a is CCl, and R 5 It is CH2OCH3, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0218] Table 1.131 provides 483 compounds E131.1 to E131.483 of formula (Ia), where A 2a is CCl, and R 5 It is CH2OCH3, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0219] Table 1.132 provides 483 compounds E132.1 to E132.483 of formula (Ia), where A 2a is CCl, and R 5 It is CH2OCH3, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0220] Table 1.133 provides 483 compounds E133.1 to E133.483 of formula (Ia), where A 2a is CCl, and R 5 It is CH2OCH3, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0221] Table 1.134 provides 483 compounds E134.1 to E134.483 of formula (Ia), where A 2a is CCl, and R 5 It is NHCH2CH3, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0222] Table 1.135 provides 483 compounds E135.1 to E135.483 of formula (Ia), where A 2a is CCl, and R 5 It is NHCH2CH3, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0223] Table 1.136 provides 483 compounds E136.1 to E136.483 of formula (Ia), where A 2a is CCl, and R 5 It is NHCH2CH3, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0224] Table 1.137 provides 483 compounds E137.1 to E137.483 of formula (Ia), where A 2a is CCl, and R 5 It is NHCH2CH3, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0225] Table 1.138 provides 483 compounds E138.1 to E138.483 of formula (Ia), where A 2a is CCl, and R 5 It is NHCH2CH3, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0226] Table 1.139 provides 483 compounds E139.1 to E139.483 of formula (Ia), where A 2a is CCl, and R 5 It is NHCH2CH3, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0227] Table 1.140 provides 483 compounds E140.1 to E140.483 of formula (Ia), where A 2a is CCl, and R 5 It is NHCH2CH3, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0228] Table 1.141 provides 483 compounds E141.1 to E141.483 of formula (Ia), where A 2a is CBr, and R 5 It is CH3, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0229] Table 1.142 provides 483 compounds E142.1 to E142.483 of formula (Ia), where A 2a is CBr, and R 5 It is CH3, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0230] Table 1.143 provides 483 compounds E143.1 to E143.483 of formula (Ia), where A 2a is CBr, and R 5 It is CH3, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0231] Table 1.144 provides 483 compounds E144.1 to E144.483 of formula (Ia), where A 2a is CBr, and R 5 It is CH3, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0232] Table 1.145 provides 483 compounds E145.1 to E145.483 of formula (Ia), where A 2a is CBr, and R 5 It is CH3, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0233] Table 1.146 provides 483 compounds E146.1 to E146.483 of formula (Ia), where A 2a is CBr, and R 5 It is CH3, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0234] Table 1.147 provides 483 compounds E147.1 to E147.483 of formula (Ia), where A 2a is CBr, and R 5 It is CH3, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0235] Table 1.148 provides 483 compounds E148.1 to E148.483 of formula (Ia), where A 2a is CBr, and R 5 It is OCH3, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0236] Table 1.149 provides 483 compounds E149.1 to E149.483 of formula (Ia), where A 2a is CBr, and R 5 It is OCH3, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0237] Table 1.150 provides 483 compounds E150.1 to E150.483 of formula (Ia), where A 2a is CBr, and R 5 It is OCH3, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0238] Table 1.151 provides 483 compounds E151.1 to E151.483 of formula (Ia), where A 2a is CBr, and R 5 It is OCH3, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0239] Table 1.152 provides 483 compounds E152.1 to E152.483 of formula (Ia), where A 2a is CBr, and R 5 It is OCH3, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0240] Table 1.153 provides 483 compounds E153.1 to E153.483 of formula (Ia), where A 2a is CBr, and R 5 It is OCH3, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0241] Table 1.154 provides 483 compounds E154.1 to E154.483 of formula (Ia), where A 2a is CBr, and R 5 It is OCH3, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0242] Table 1.155 provides 483 compounds E155.1 to E155.483 of formula (Ia), where A 2a is CBr, and R 5 It is cyclopropyl, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0243] Table 1.156 provides 483 compounds E156.1 to E156.483 of formula (Ia), where A 2a is CBr, and R 5 It is cyclopropyl, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0244] Table 1.157 provides 483 compounds E157.1 to E157.483 of formula (Ia), where A 2a is CBr, and R 5 It is cyclopropyl, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0245] Table 1.158 provides 483 compounds E158.1 to E158.483 of formula (Ia), where A 2a is CBr, and R 5 It is cyclopropyl, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0246] Table 1.159 provides 483 compounds E159.1 to E159.483 of formula (Ia), where A 2a is CBr, and R 5 It is cyclopropyl, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0247] Table 1.160 provides 483 compounds E160.1 to E160.483 of formula (Ia), where A 2a is CBr, and R 5 It is cyclopropyl, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0248] Table 1.161 provides 483 compounds E161.1 to E161.483 of formula (Ia), where A 2a is CBr, and R 5 It is cyclopropyl, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0249] Table 1.162 provides 483 compounds E162.1 to E162.483 of formula (Ia), where A 2a is CBr, and R 5 It is CH2OCH3, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0250] Table 1.163 provides 483 compounds E163.1 to E163.483 of formula (Ia), where A 2a is CBr, and R 5 It is CH2OCH3, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0251] Table 1.164 provides 483 compounds E164.1 to E164.483 of formula (Ia), where A 2a is CBr, and R 5 It is CH2OCH3, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0252] Table 1.165 provides 483 compounds E165.1 to E165.483 of formula (Ia), where A 2a is CBr, and R 5 It is CH2OCH3, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0253] Table 1.166 provides 483 compounds E166.1 to E166.483 of formula (Ia), where A 2a is CBr, and R 5 It is CH2OCH3, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0254] Table 1.167 provides 483 compounds E167.1 to E167.483 of formula (Ia), where A 2a is CBr, and R 5 It is CH2OCH3, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0255] Table 1.168 provides 483 compounds E168.1 to E168.483 of formula (Ia), where A 2a is CBr, and R 5 It is CH2OCH3, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0256] Table 1.169 provides 483 compounds E169.1 to E169.483 of formula (Ia), where A 2a is CBr, and R 5 It is NHCH2CH3, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0257] Table 1.170 provides 483 compounds E170.1 to E170.483 of formula (Ia), where A 2a is CBr, and R 5 It is NHCH2CH3, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0258] Table 1.171 provides 483 compounds E171.1 to E171.483 of formula (Ia), where A 2a is CBr, and R 5 It is NHCH2CH3, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0259] Table 1.172 provides 483 compounds E172.1 to E172.483 of formula (Ia), where A 2a is CBr, and R 5 It is NHCH2CH3, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0260] Table 1.173 provides 483 compounds E173.1 to E173.483 of formula (Ia), where A 2a is CBr, and R 5 It is NHCH2CH3, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0261] Table 1.174 provides 483 compounds E174.1 to E174.483 of formula (Ia), where A 2a is CBr, and R 5 It is NHCH2CH3, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0262] Table 1.175 provides 483 compounds E175.1 to E175.483 of formula (Ia), where A 2a is CBr, and R 5 It is NHCH2CH3, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0263] Table 1.176 provides 483 compounds E176.1 to E176.483 of formula (Ia), where A 2a It is CCH3, and R 5 It is CH3, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0264] Table 1.177 provides 483 compounds E177.1 to E177.483 of formula (Ia), where A 2a It is CCH3, and R 5 It is CH3, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0265] Table 1.178 provides 483 compounds E178.1 to E178.483 of formula (Ia), where A 2a It is CCH3, and R 5 It is CH3, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0266] Table 1.179 provides 483 compounds E179.1 to E179.483 of formula (Ia), where A 2a It is CCH3, and R 5 It is CH3, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0267] Table 1.180 provides 483 compounds E180.1 to E180.483 of formula (Ia), where A 2a It is CCH3, and R 5 It is CH3, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0268] Table 1.181 provides 483 compounds E181.1 to E181.483 of formula (Ia), where A 2a It is CCH3, and R 5 It is CH3, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0269] Table 1.182 provides 483 compounds E182.1 to E182.483 of formula (Ia), where A 2a It is CCH3, and R 5 It is CH3, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0270] Table 1.183 provides 483 compounds E183.1 to E183.483 of formula (Ia), where A 2a It is CCH3, and R 5 It is OCH3, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0271] Table 1.184 provides 483 compounds E184.1 to E184.483 of formula (Ia), where A 2a It is CCH3, and R 5 It is OCH3, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0272] Table 1.185 provides 483 compounds E185.1 to E185.483 of formula (Ia), where A 2a It is CCH3, and R 5 It is OCH3, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0273] Table 1.186 provides 483 compounds E186.1 to E186.483 of formula (Ia), where A 2a It is CCH3, and R 5 It is OCH3, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0274] Table 1.187 provides 483 compounds E187.1 to E187.483 of formula (Ia), where A 2a It is CCH3, and R 5 It is OCH3, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0275] Table 1.188 provides 483 compounds E188.1 to E188.483 of formula (Ia), where A 2a It is CCH3, and R 5 It is OCH3, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0276] Table 1.189 provides 483 compounds E189.1 to E189.483 of formula (Ia), where A 2a It is CCH3, and R 5 It is OCH3, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0277] Table 1.190 provides 483 compounds E190.1 to E190.483 of formula (Ia), where A 2a It is CCH3, and R 5 It is cyclopropyl, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0278] Table 1.191 provides 483 compounds E191.1 to E191.483 of formula (Ia), where A 2a It is CCH3, and R 5 It is cyclopropyl, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0279] Table 1.192 provides 483 compounds E192.1 to E192.483 of formula (Ia), where A 2a It is CCH3, and R 5 It is cyclopropyl, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0280] Table 1.193 provides 483 compounds E193.1 to E193.483 of formula (Ia), where A 2a It is CCH3, and R 5 It is cyclopropyl, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0281] Table 1.194 provides 483 compounds E194.1 to E194.483 of formula (Ia), where A 2a It is CCH3, and R 5 It is cyclopropyl, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0282] Table 1.195 provides 483 compounds E195.1 to E195.483 of formula (Ia), where A 2a It is CCH3, and R 5 It is cyclopropyl, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0283] Table 1.196 provides 483 compounds E196.1 to E196.483 of formula (Ia), where A 2a It is CCH3, and R 5 It is cyclopropyl, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0284] Table 1.197 provides 483 compounds E197.1 to E197.483 of formula (Ia), where A 2a It is CCH3, and R 5 It is CH2OCH3, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0285] Table 1.198 provides 483 compounds E198.1 to E198.483 of formula (Ia), where A 2a It is CCH3, and R 5 It is CH2OCH3, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0286] Table 1.199 provides 483 compounds E199.1 to E199.483 of formula (Ia), where A 2a It is CCH3, and R 5 It is CH2OCH3, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0287] Table 1.200 provides 483 compounds E200.1 to E200.483 of formula (Ia), where A 2a It is CCH3, and R 5 It is CH2OCH3, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0288] Table 1.201 provides 483 compounds E201.1 to E201.483 of formula (Ia), where A 2a It is CCH3, and R 5 It is CH2OCH3, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0289] Table 1.202 provides 483 compounds E202.1 to E202.483 of formula (Ia), where A 2a It is CCH3, and R 5 It is CH2OCH3, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0290] Table 1.203 provides 483 compounds E203.1 to E203.483 of formula (Ia), where A 2a It is CCH3, and R 5 It is CH2OCH3, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0291] Table 1.204 provides 483 compounds E204.1 to E204.483 of formula (Ia), where A 2a It is CCH3, and R 5 It is NHCH2CH3, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0292] Table 1.205 provides 483 compounds E205.1 to E205.483 of formula (Ia), where A 2a It is CCH3, and R 5 It is NHCH2CH3, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0293] Table 1.206 provides 483 compounds E206.1 to E206.483 of formula (Ia), where A 2a It is CCH3, and R 5 It is NHCH2CH3, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0294] Table 1.207 provides 483 compounds E207.1 to E207.483 of formula (Ia), where A 2a It is CCH3, and R 5 It is NHCH2CH3, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0295] Table 1.208 provides 483 compounds E208.1 to E208.483 of formula (Ia), where A 2a It is CCH3, and R 5 It is NHCH2CH3, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0296] Table 1.209 provides 483 compounds E209.1 to E209.483 of formula (Ia), where A 2a It is CCH3, and R 5 It is NHCH2CH3, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0297] Table 1.210 provides 483 compounds E210.1 to E210.483 of formula (Ia), where A 2a It is CCH3, and R 5 It is NHCH2CH3, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0298] Table 1.211 provides 483 compounds E211.1 to E211.483 of formula (Ia), where A 2a It is CCH2CH3, and R 5 It is CH3, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0299] Table 1.212 provides 483 compounds E212.1 to E212.483 of formula (Ia), where A 2a It is CCH2CH3, and R 5 It is CH3, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0300] Table 1.213 provides 483 compounds E213.1 to E213.483 of formula (Ia), where A 2a It is CCH2CH3, and R 5 It is CH3, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0301] Table 1.214 provides 483 compounds E214.1 to E214.483 of formula (Ia), where A 2a It is CCH2CH3, and R 5 It is CH3, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0302] Table 1.215 provides 483 compounds E215.1 to E215.483 of formula (Ia), where A 2a It is CCH2CH3, and R 5 It is CH3, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0303] Table 1.216 provides 483 compounds E216.1 to E216.483 of formula (Ia), where A 2a It is CCH2CH3, and R 5 It is CH3, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0304] Table 1.217 provides 483 compounds E217.1 to E217.483 of formula (Ia), where A 2a It is CCH2CH3, and R 5 It is CH3, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0305] Table 1.218 provides 483 compounds E218.1 to E218.483 of formula (Ia), where A 2a It is CCH2CH3, and R 5 It is OCH3, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0306] Table 1.219 provides 483 compounds E219.1 to E219.483 of formula (Ia), where A 2a It is CCH2CH3, and R 5 It is OCH3, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0307] Table 1.220 provides 483 compounds E220.1 to E220.483 of formula (Ia), where A 2a It is CCH2CH3, and R 5 It is OCH3, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0308] Table 1.221 provides 483 compounds E221.1 to E221.483 of formula (Ia), where A 2a It is CCH2CH3, and R 5 It is OCH3, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0309] Table 1.222 provides 483 compounds E222.1 to E222.483 of formula (Ia), where A 2a It is CCH2CH3, and R 5 It is OCH3, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0310] Table 1.223 provides 483 compounds E223.1 to E223.483 of formula (Ia), where A 2a It is CCH2CH3, and R 5 It is OCH3, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0311] Table 1.224 provides 483 compounds E224.1 to E224.483 of formula (Ia), where A 2a It is CCH2CH3, and R 5 It is OCH3, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0312] Table 1.225 provides 483 compounds E225.1 to E225.483 of formula (Ia), where A 2a It is CCH2CH3, and R 5 It is cyclopropyl, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0313] Table 1.226 provides 483 compounds E226.1 to E226.483 of formula (Ia), where A 2a It is CCH2CH3, and R 5 It is cyclopropyl, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0314] Table 1.227 provides 483 compounds E227.1 to E227.483 of formula (Ia), where A 2a It is CCH2CH3, and R 5 It is cyclopropyl, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0315] Table 1.228 provides 483 compounds E228.1 to E228.483 of formula (Ia), where A 2a It is CCH2CH3, and R 5 It is cyclopropyl, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0316] Table 1.229 provides 483 compounds E229.1 to E229.483 of formula (Ia), where A 2a It is CCH2CH3, and R 5 It is cyclopropyl, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0317] Table 1.230 provides 483 compounds E230.1 to E230.483 of formula (Ia), where A 2a It is CCH2CH3, and R 5 It is cyclopropyl, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0318] Table 1.231 provides 483 compounds E231.1 to E231.483 of formula (Ia), where A 2a It is CCH2CH3, and R 5 It is cyclopropyl, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0319] Table 1.232 provides 483 compounds E232.1 to E232.483 of formula (Ia), where A 2a It is CCH2CH3, and R 5 It is CH2OCH3, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0320] Table 1.233 provides 483 compounds E233.1 to E233.483 of formula (Ia), where A 2a It is CCH2CH3, and R 5 It is CH2OCH3, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0321] Table 1.234 provides 483 compounds E234.1 to E234.483 of formula (Ia), where A 2a It is CCH2CH3, and R 5 It is CH2OCH3, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0322] Table 1.235 provides 483 compounds E235.1 to E235.483 of formula (Ia), where A 2a It is CCH2CH3, and R 5 It is CH2OCH3, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0323] Table 1.236 provides 483 compounds E236.1 to E236.483 of formula (Ia), where A 2a It is CCH2CH3, and R 5 It is CH2OCH3, and R 1a It is CH2-cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0324] Table 1.237 provides 483 compounds E237.1 to E237.483 of formula (Ia), where A 2a It is CCH2CH3, and R 5 It is CH2OCH3, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0325] Table 1.238 provides 483 compounds E238.1 to E238.483 of formula (Ia), where A 2a It is CCH2CH3, and R 5 It is CH2OCH3, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0326] Table 1.239 provides 483 compounds E239.1 to E239.483 of formula (Ia), where A 2a It is CCH2CH3, and R 5 It is NHCH2CH3, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0327] Table 1.240 provides 483 compounds E240.1 to E240.483 of formula (Ia), where A 2a It is CCH2CH3, and R 5 It is NHCH2CH3, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0328] Table 1.241 provides 483 compounds E241.1 to E241.483 of formula (Ia), where A 2a It is CCH2CH3, and R 5 It is NHCH2CH3, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0329] Table 1.242 provides 483 compounds E242.1 to E242.483 of formula (Ia), where A 2a It is CCH2CH3, and R 5 It is NHCH2CH3, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0330] Table 1.243 provides 483 compounds E243.1 to E243.483 of formula (Ia), where A 2a It is CCH2CH3, and R 5 It is NHCH2CH3, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0331] Table 1.244 provides 483 compounds E244.1 to E244.483 of formula (Ia), where A 2a It is CCH2CH3, and R 5 It is NHCH2CH3, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0332] Table 1.245 provides 483 compounds E245.1 to E245.483 of formula (Ia), where A 2a It is CCH2CH3, and R 5 It is NHCH2CH3, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0333] Table 1.246 provides 483 compounds E246.1 to E246.483 of formula (Ia), where A 2a It is CCN, and R 5 It is CH3, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0334] Table 1.247 provides 483 compounds E247.1 to E247.483 of formula (Ia), where A 2a It is CCN, and R 5 It is CH3, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0335] Table 1.248 provides 483 compounds E248.1 to E248.483 of formula (Ia), where A 2a It is CCN, and R 5 It is CH3, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0336] Table 1.249 provides 483 compounds E249.1 to E249.483 of formula (Ia), where A 2a It is CCN, and R 5 It is CH3, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0337] Table 1.250 provides 483 compounds E250.1 to E250.483 of formula (Ia), where A 2a It is CCN, and R 5 It is CH3, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0338] Table 1.251 provides 483 compounds E251.1 to E251.483 of formula (Ia), where R 2a It is CCN, and R 5 It is CH3, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0339] Table 1.252 provides 483 compounds E252.1 to E252.483 of formula (Ia), where A 2a It is CCN, and R 5 It is CH3, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0340] Table 1.253 provides 483 compounds E253.1 to E253.483 of formula (Ia), where A 2a It is CCN, and R 5 It is OCH3, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0341] Table 1.254 provides 483 compounds E254.1 to E254.483 of formula (Ia), where A 2a It is CCN, and R 5 It is OCH3, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0342] Table 1.255 provides 483 compounds E255.1 to E255.483 of formula (Ia), where A 2a It is CCN, and R 5 It is OCH3, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0343] Table 1.256 provides 483 compounds E256.1 to E256.483 of formula (Ia), where A 2a It is CCN, and R 5 It is OCH3, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0344] Table 1.257 provides 483 compounds E257.1 to E257.483 of formula (Ia), where A 2a It is CCN, and R 5 It is OCH3, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0345] Table 1.258 provides 483 compounds E258.1 to E258.483 of formula (Ia), where A 2a It is CCN, and R 5 It is OCH3, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0346] Table 1.259 provides 483 compounds E259.1 to E259.483 of formula (Ia), where A 2a It is CCN, and R 5 It is OCH3, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0347] Table 1.260 provides 483 compounds E260.1 to E260.483 of formula (Ia), where A 2a It is CCN, and R 5 It is cyclopropyl, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0348] Table 1.261 provides 483 compounds E261.1 to E261.483 of formula (Ia), where A 2a It is CCN, and R 5 It is cyclopropyl, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0349] Table 1.262 provides 483 compounds E262.1 to E262.483 of formula (Ia), where A 2a It is CCN, and R 5 It is cyclopropyl, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0350] Table 1.263 provides 483 compounds E263.1 to E263.483 of formula (Ia), where A 2a It is CCN, and R 5 It is cyclopropyl, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0351] Table 1.264 provides 483 compounds E264.1 to E264.483 of formula (Ia), where A 2a It is CCN, and R 5 It is cyclopropyl, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0352] Table 1.265 provides 483 compounds E265.1 to E265.483 of formula (Ia), where A 2a It is CCN, and R 5 It is cyclopropyl, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0353] Table 1.266 provides 483 compounds E266.1 to E266.483 of formula (Ia), where A 2a It is CCN, and R 5 It is cyclopropyl, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0354] Table 1.267 provides 483 compounds E267.1 to E267.483 of formula (Ia), where A 2a It is CCN, and R 5 It is CH2OCH3, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0355] Table 1.268 provides 483 compounds E268.1 to E268.483 of formula (Ia), where A 2a It is CCN, and R 5 It is CH2OCH3, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0356] Table 1.269 provides 483 compounds E269.1 to E269.483 of formula (Ia), where A 2a It is CCN, and R 5 It is CH2OCH3, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0357] Table 1.270 provides 483 compounds E270.1 to E270.483 of formula (Ia), where A 2a It is CCN, and R 5 It is CH2OCH3, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0358] Table 1.271 provides 483 compounds E271.1 to E271.483 of formula (Ia), where A 2a It is CCN, and R 5 It is CH2OCH3, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0359] Table 1.272 provides 483 compounds E272.1 to E272.483 of formula (Ia), where A 2a It is CCN, and R 5 It is CH2OCH3, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0360] Table 1.273 provides 483 compounds E273.1 to E273.483 of formula (Ia), where A 2a It is CCN, and R 5 It is CH2OCH3, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0361] Table 1.274 provides 483 compounds E274.1 to E274.483 of formula (Ia), where A 2a It is CCN, and R 5 It is NHCH2CH3, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0362] Table 1.275 provides 483 compounds E275.1 to E275.483 of formula (Ia), where A 2a It is CCN, and R 5 It is NHCH2CH3, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0363] Table 1.276 provides 483 compounds E276.1 to E276.483 of formula (Ia), where A 2a It is CCN, and R 5 It is NHCH2CH3, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0364] Table 1.277 provides 483 compounds E277.1 to E277.483 of formula (Ia), where A 2a It is CCN, and R 5 It is NHCH2CH3, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0365] Table 1.278 provides 483 compounds E278.1 to E278.483 of formula (Ia), where A 2a It is CCN, and R 5 It is NHCH2CH3, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0366] Table 1.279 provides 483 compounds E279.1 to E279.483 of formula (Ia), where A 2a It is CCN, and R 5 It is NHCH2CH3, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0367] Table 1.280 provides 483 compounds E280.1 to E280.483 of formula (Ia), where A 2a It is CCN, and R 5 It is NHCH2CH3, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0368] Table 1.281 provides 483 compounds E281.1 to E281.483 of formula (Ia), where A 2a It is COCH3, and R 5 It is CH3, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0369] Table 1.282 provides 483 compounds E282.1 to E282.483 of formula (Ia), where A 2a It is COCH3, and R 5 It is CH3, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0370] Table 1.283 provides 483 compounds E283.1 to E283.483 of formula (Ia), where A 2a It is COCH3, and R 5 It is CH3, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0371] Table 1.284 provides 483 compounds E284.1 to E284.483 of formula (Ia), where A 2a It is COCH3, and R 5 It is CH3, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0372] Table 1.285 provides 483 compounds E285.1 to E285.483 of formula (Ia), where A 2a It is COCH3, and R 5 It is CH3, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0373] Table 1.286 provides 483 compounds E286.1 to E286.483 of formula (Ia), where A 2a It is COCH3, and R 5 It is CH3, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0374] Table 1.287 provides 483 compounds E287.1 to E287.483 of formula (Ia), where A 2a It is COCH3, and R 5 It is CH3, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0375] Table 1.288 provides 483 compounds E288.1 to E288.483 of formula (Ia), where A 2a It is COCH3, and R 5 It is OCH3, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0376] Table 1.289 provides 483 compounds E289.1 to E289.483 of formula (Ia), where A 2a It is COCH3, and R 5 It is OCH3, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0377] Table 1.290 provides 483 compounds E290.1 to E290.483 of formula (Ia), where A 2a It is COCH3, and R 5 It is OCH3, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0378] Table 1.291 provides 483 compounds E291.1 to E291.483 of formula (Ia), where A 2a It is COCH3, and R 5 It is OCH3, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0379] Table 1.292 provides 483 compounds E292.1 to E292.483 of formula (Ia), where A 2a It is COCH3, and R 5 It is OCH3, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0380] Table 1.293 provides 483 compounds E293.1 to E293.483 of formula (Ia), where A 2a It is COCH3, and R 5 It is OCH3, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0381] Table 1.294 provides 483 compounds E294.1 to E294.483 of formula (Ia), where A 2a It is COCH3, and R 5 It is OCH3, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0382] Table 1.295 provides 483 compounds E295.1 to E295.483 of formula (Ia), where A 2a It is COCH3, and R 5 It is cyclopropyl, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0383] Table 1.296 provides 483 compounds E296.1 to E296.483 of formula (Ia), where A 2a It is COCH3, and R 5 It is cyclopropyl, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0384] Table 1.297 provides 483 compounds E297.1 to E297.483 of formula (Ia), where A 2a It is COCH3, and R 5 It is cyclopropyl, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0385] Table 1.298 provides 483 compounds E298.1 to E298.483 of formula (Ia), where A 2a It is COCH3, and R 5 It is cyclopropyl, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0386] Table 1.299 provides 483 compounds E299.1 to E299.483 of formula (Ia), where A 2a It is COCH3, and R 5 It is cyclopropyl, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0387] Table 1.300 provides 483 compounds E300.1 to E300.483 of formula (Ia), where A 2a It is COCH3, and R 5 It is cyclopropyl, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0388] Table 1.301 provides 483 compounds E301.1 to E301.483 of formula (Ia), where A 2a It is COCH3, and R 5 It is cyclopropyl, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0389] Table 1.302 provides 483 compounds E302.1 to E302.483 of formula (Ia), where A 2a It is COCH3, and R 5 It is CH2OCH3, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0390] Table 1.303 provides 483 compounds E303.1 to E303.483 of formula (Ia), where A 2a It is COCH3, and R 5 It is CH2OCH3, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0391] Table 1.304 provides 483 compounds E304.1 to E304.483 of formula (Ia), where A 2a It is COCH3, and R 5 It is CH2OCH3, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0392] Table 1.305 provides 483 compounds E305.1 to E305.483 of formula (Ia), where A 2a It is COCH3, and R 5 It is CH2OCH3, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0393] Table 1.306 provides 483 compounds E306.1 to E306.483 of formula (Ia), where A 2a It is COCH3, and R 5 It is CH2OCH3, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0394] Table 1.307 provides 483 compounds E307.1 to E307.483 of formula (Ia), where A 2a It is COCH3, and R 5 It is CH2OCH3, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0395] Table 1.308 provides 483 compounds E308.1 to E308.483 of formula (Ia), where A 2a It is COCH3, and R 5 It is CH2OCH3, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0396] Table 1.309 provides 483 compounds E309.1 to E309.483 of formula (Ia), where A 2a It is COCH3, and R 5 It is NHCH2CH3, and R 1a It is CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0397] Table 1.310 provides 483 compounds E310.1 to E310.483 of formula (Ia), where A 2a It is COCH3, and R 5 It is NHCH2CH3, and R 1a It is CH2CH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0398] Table 1.311 provides 483 compounds E311.1 to E311.483 of formula (Ia), where A 2a It is COCH3, and R 5 It is NHCH2CH3, and R 1a It is CH2OCH3, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0399] Table 1.312 provides 483 compounds E312.1 to E312.483 of formula (Ia), where A 2a It is COCH3, and R 5 It is NHCH2CH3, and R 1a It is cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0400] Table 1.313 provides 483 compounds E313.1 to E313.483 of formula (Ia), where A 2a It is COCH3, and R 5 It is NHCH2CH3, and R 1a It is CH2 cyclopropyl, and R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0401] Table 1.314 provides 483 compounds E314.1 to E314.483 of formula (Ia), where A 2a It is COCH3, and R 5 It is NHCH2CH3, and R 1a NHAc is R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0402] Table 1.315 provides 483 compounds E315.1 to E315.483 of formula (Ia), where A 2a It is COCH3, and R 5 It is NHCH2CH3, and R 1a is CN, R 2 , A 3 , R 4 , A 1 , A 2b This is as defined in Table Z.
[0403] Compounds according to the present invention may have numerous advantages, including, in particular, advantageous levels of biological activity for protecting plants from fungal diseases, or excellent properties for use as agricultural chemical active ingredients (e.g., higher biological activity, advantageous activity spectrum, increased safety profile, improved physicochemical properties, or improved biodegradability). Compounds according to the present invention have particularly advantageous levels of biological activity for protecting plants from Oomycetes such as Phytophthora, Plasmopara, and Pythium.
[0404] Compounds of formula (I) where Z is O can be prepared as shown in schemes 1 to 19 below, where, unless otherwise specified, the definition of each variable site is as defined in this invention.
[0405] The compound of formula (I) is mixed with a base such as Cs2CO3, K2CO3, or NaOtBu, and a suitable palladium catalyst such as tetrakistriphenylphosphine palladium, [1,1-bis(diphenylphosphine)ferrocene]dichloropalladium(II), bis(diphenylphosphine)palladium(II) chloride, palladium dichloride, or palladium acetate, in a suitable solvent such as dimethylformamide, dioxane, tetrahydrofuran, ethanol, or water, with the compound of formula (II) where X is Cl, Br, or I, and R 6 Hydrogen and C are independent of each other. 1-6 Alkyl or two R 6together become C 3-8 It can be prepared by Suzuki cross-coupling with a compound of formula (III) that can form a cycloalkyl group. 6 Hydrogen and C are independent of each other. 1-6 Alkyl or two R 6 together become C 3-8 Compounds of formula (III) that can form cycloalkyl groups are prepared by known methods or are commercially available. This transformation is shown in Scheme 1. [ka] Scheme 1
[0406] The compound of formula (II) is used in the reagent of formula (V) (wherein X 1 It can be prepared by reacting a good leaving group (such as Cl, Br, I, triflate, tosyl, or mesyl) with a base such as Cs2CO3, K2CO3, NaH, or NaOtBu. In addition to this, R 7 However, the amide nitrogen can be functionalized using a compound of formula (VI) which is an electron-withdrawing group such as a cyano or ester. The compound of formula (IV) is X 2It can be prepared by a peptide coupling reaction between a compound of formula (VII) in which is OH and an amine of formula (VIII), and by activating the carboxylic acid functional group of the compound of formula (VII) (by converting the -OH of the carboxylic acid to a good leaving group such as a chloride group, for example by using (COCl)2 or SOCl2, preferably in a suitable solvent (e.g., N-methylpyrrolidone, acetonitrile, dimethylacetamide, dichloromethane, or tetrahydrofuran), preferably at a temperature of 25°C to 60°C, optionally in the presence of a base such as triethylamine or N,N-diisopropylethylamine; or otherwise, optionally in the presence of a base (e.g., triethylamine or N,N-diisopropylethylamine), in a suitable solvent (e.g., acetonitrile), under conditions described in the literature for amide coupling with cyclic anhydride of 1-propanephosphonic acid (T3P)). See, for example, Chem.Soc.Rev.2009,38,606 and Chem.Soc.Rev.2011,40,5084. In addition, compounds of formula (II) where X is Cl, Br, or I can be used with the above conditions. 2 These compounds can be obtained by amide coupling transformations between the compound of formula (VII), in which the OH group is , and the amine of formula (IX). These transformations are shown in Scheme 2. [ka] Scheme 2
[0407] The compound of formula (IX) is commercially available, or the compound of formula (VIII) is the compound of formula (V) (wherein X 1 This can be obtained by the reaction of a good leaving group such as Cl, Br, I, triflate, tosyl, or mesyl in the presence of a base such as Cs2CO3, K2CO3, NaH, or NaOtBu. In addition, the compound of formula (IX) can be obtained by the reaction of the compound of formula (VIII) with the compound of formula (VI) (wherein R 7The compound of formula (IX) can also be synthesized by reacting it with an electron-withdrawing group (such as a cyano or ester) in the presence of a base, optionally triethylamine or 1,8-diazabicyclo[5.4.0]undeca-7-ene. In addition, the compound of formula (IX) can be obtained from the amine of formula (VIII) by reductive amination with the aldehyde of formula (X) in a suitable solvent, optionally in the presence of a Brønsted acid or Lewis acid, such as acetic acid, in the presence of NaBH(OAc)3 or NaBH3CN [wherein R, R is an electron-withdrawing group such as a cyano or ester]. 10 C 1-5 Alkyl, C 1-5 Alkoxy-C 1-5 Alkyl, C 3-6 Cycloalkyl-C 1-3 Alkyl, C 2-5 Alkenil, C 2-5 Alkinyl, C 1-5 Alkoxy, C 1-6 Alkylsulfanyl-C 1-5 Alkyl, C 1-6 Alkylsulfinyl-C 1-5 Alkyl, C 1-6 Alkylsulfonyl-C 1-5 Alkyl, C 1-6 Alkoxycarbonyl-C 1-5 Alkyl, C 1-6 Alkylaminocarbonyl-C 1-5 Alkyl or diC 1-6 Alkylaminocarbonyl-C 1-6 Alkyl]. In addition to this, another reagent system for reductive amination uses a combination of titanium isopropoxide and NaBH4. The synthesis of the compound of formula (IX) from the amine of formula (VIII) is described in Scheme 3. [ka] Scheme 3
[0408] In addition, compounds of formula (II) where X is Cl, Br, or I can be prepared by the reaction of a compound of formula (XI) with a halogenating agent such as N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, or bromine in a suitable solvent such as dichloromethane, chloroform, tetrahydrofuran, or acetonitrile. Compounds of formula (XI) are formed from the amine of formula (IX), where X 2 This can be obtained by amide coupling conversion with a compound of formula (XII) in which is OH, and by activating the carboxylic acid functional group of the compound of formula (XII) (for example, by using (COCl)2 or SOCl2, preferably in a suitable solvent (e.g., N-methylpyrrolidone, acetonitrile, dimethylacetamide, dichloromethane, or tetrahydrofuran), preferably at a temperature of 25°C to 60°C, optionally in the presence of a base such as triethylamine or N,N-diisopropylethylamine; or otherwise, optionally in the presence of a base (e.g., triethylamine or N,N-diisopropylethylamine), in a suitable solvent (e.g., acetonitrile), under conditions described in the literature for amide coupling with cyclic anhydride of 1-propanephosphonic acid (T3P), thereby converting the -OH of the carboxylic acid to a good leaving group such as a chloride group). In addition to the above, the compound of formula (XI) is the compound of formula (XIII) in the presence of a base such as Cs2CO3, K2CO3, NaH, or NaOtBu, and the compound of formula (V) (where X is the base). 1 This can be obtained by alkylation with a good leaving group such as Cl, Br, I, triflate, tosyl, or mesyl. In addition, the compound of formula (XI) can be obtained by alkylating the compound of formula (XIII) with the compound of formula (VI) (wherein R 7 The compound can also be synthesized by reacting it with an electron-withdrawing group (such as a cyano or ester) in the presence of a base such as triethylamine or 1,8-diazabicyclo[5.4.0]undeca-7-ene, optionally. The compound of formula (XIII) is X 2From the compound of formula (XII) where is OH, it can be prepared by peptide coupling conversion with the amine of formula (VIII) using the above conditions. These conversions are shown in Scheme 4. [ka] Scheme 4
[0409] In addition, the compound of formula (XI) can be synthesized by reacting the compound of formula (XIV) (wherein X is Cl, Br, or I) with the amine of formula (IX) and carbon monoxide in the presence of a catalyst such as [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium(II) and optionally a base such as triethylamine. This transformation is shown in Scheme 5. [ka] Scheme 5
[0410] Compound of formula (XII) (wherein X 2 (where R is OH) is obtained by hydrolyzing the ester moiety under conventional acidic or basic conditions and heating the diacitic acid, resulting in a compound of formula (XV) (where R is OH). 8 is C 1-6 It can be obtained by decarboxylation of alkyl groups. 8 C 1-6 Compounds of formula (XV) that are alkyl are R in polar organic solvents such as dimethyl sulfoxide, N-methylpyrrolidine, or N,N-dimethylformamide in the presence of a base such as Na2CO3 or K2CO3. 9 A compound of formula (XVI) in which R is an (aryl)sulfonyl, (hetero)arylsulfonyl, or sulfonic acid group, for example, a sulfonic acid, tosylate, or a 2,4,6-trimethylbenzenesulfonyl group, and an alkyne of formula (XVII) (wherein R 8 is C 1-6 It can be synthesized by reaction with an alkyl group. The compound of formula (XVII) is commercially available or can be readily prepared by those skilled in the art according to the described method. 9However, the compound of formula (XVI), which is an (aryl)sulfonyl, (hetero)arylsulfonyl, or sulfonic acid group, for example, a sulfonic acid, tosylate, or 2,4,6-trimethylbenzenesulfonyl group, is converted in a polar aprotic solvent such as dimethyl sulfoxide, N-methylpyrrolidine, or N,N-dimethylformamide to the compound of formula (XVIII) and the compound of formula (XIX) (wherein R 9 This can be formed by reacting with a (aryl)sulfonyl, (hetero)arylsulfonyl, or sulfonic acid group (e.g., sulfonic acid, tosylate, or 2,4,6-trimethylbenzenesulfonyl group). Compounds of formula (XVIII) are commercially available or can be prepared by methods known to those skilled in the art. Compounds of formula (XII) (wherein X 2 (is OH) C 1-6 Further reaction with alkyl alcohol yields an ester of formula (XX) (wherein R 10 is C 1-6 A alkyl group can be obtained. These transformations are shown in Scheme 6. [ka] Scheme 6
[0411] Compound of formula (XII) (wherein X 2 (where R is OH) can be treated with an acid or base to form a compound of formula (XX) (where R is OH). 10 is C 1-6 It can be synthesized from alkyl compounds. This conversion is well known to those skilled in the art. Compounds of formula (XX) (wherein R 10 is C 1-6 A compound of formula (XXI) (wherein X is Cl, Br, or I, and R) is alkyl. 10 is C 1-6Compounds (which are alkyl) can be obtained by cross-coupling transformations using compounds of formula (XXII) (Suzuki cross-coupling) or compounds of formula (XXIII) (Still coupling). Suzuki cross-coupling can typically be achieved by using a suitable palladium catalyst, such as tetrakistriphenylphosphine palladium, [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium(II), bis(diphenylphosphine)palladium(II) chloride, palladium dichloride, or palladium acetate, in a suitable solvent such as dimethylformamide, dioxane, tetrahydrofuran, ethanol, or water, in the presence of a base such as Cs2CO3, K2CO3, or NaOtBu. Still coupling can be achieved by using a suitable palladium catalyst, such as tetrakistriphenylphosphine palladium, tris(dibenzylideneacetone)dipalladium, palladium dichloride, or palladium acetate, in a suitable solvent such as dimethylformamide, dioxane, or acetonitrile, in the presence of a base such as Cs2CO3 or sodium acetate. These transformations are shown in Scheme 7. [ka] Scheme 7
[0412] In addition to this, R 10 C 1-6 The alkyl compound of formula (XX) is obtained from the compound of formula (XXIV) in the presence of a base such as pyridine or diisopropylethylamine, and is obtained from the compound of formula (XXV) (wherein X is Cl or Br, and R 11 is C 1-6 It can be obtained by reaction with alkyl. 10 C 1-6 The alkyl amine of formula (XXIV) can be converted in a protic solvent such as methanol with an acid, typically hydrochloric acid, or sodium acetate and hydroxylamine hydrochloride to form the compound of formula (XXVI) (wherein R, R 10 is C 1-6 It can be prepared by treatment of alkyl. 10 C1-6 The alkyl compound of formula (XXVI) is obtained in the presence of a catalyst such as palladium acetate or tris(dibenzylideneacetone)dipalladium, optionally a ligand such as 1,1'v-[1,1'-binaphthalene]-2,2'-diylbis[1,1-diphenylphosphine] or (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine), and in the presence of a base such as cesium carbonate or sodium tert-butoxide, where X is Cl, Br, or I, and R 10 C 1-6 The alkyl compound of formula (XXI) can be synthesized by the reaction of diphenylmethaneamine (CAS number 1013-88-3). These transformations are shown in Scheme 8. [ka] Scheme 8
[0413] In addition to the above, the compound of formula (XI) can be obtained from the compound of formula (XXVII) where X is Cl, Br, or I, using the above conditions, R 6 They are independent of each other, hydrogen, C 1-6 Alkyl or two R 6 together C 3-8 These can be obtained by cross-coupling transformations using cycloalkyl compounds (Suzuki cross-coupling) or compounds of formula (XXII) that can form compounds of formula (XXIII) (Still coupling). These transformations are shown in Scheme 9. [ka] Scheme 9
[0414] In addition to the above, the compound of formula (XI) is obtained from the compound of formula (XXVIII) in the presence of a base such as pyridine or diisopropylethylamine, and the compound of formula (XXIX) is obtained from the compound of formula (XXVIII) (wherein X is Cl or Br, and R is R). 11 C 1-6It can be obtained by reaction with an alkyl group. The amine of formula (XXVIII) can be prepared by treatment of the compound of formula (XXX) with an acid, typically hydrochloric acid, or with sodium acetate and hydroxylamine hydrochloride in a protic solvent such as methanol. The compound of formula (XXX) can be synthesized by reaction of the compound of formula (XXVII) (wherein X is Cl, Br, or I) with diphenylmethaneimine (CAS number 1013-88-3) in the presence of a catalyst such as palladium acetate or tris(dibenzylideneacetone)dipalladium, optionally a ligand such as 1,1'-[1,1'-binaphthalene]-2,2'-diylbis[1,1-diphenylphosphine] or (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine), and a base such as cesium carbonate or sodium tert-butoxide. These transformations are shown in Scheme 10. [ka] Scheme 10
[0415] A compound of formula (XXVII) where X is Cl, Br, or I is an amine of formula (IX) where X is Cl, Br, or I, and X 2This can be obtained by amide coupling conversion with a compound of formula (XXXI) in which is OH, and by activating the carboxylic acid functional group of the compound of formula (XXXI) (for example, by using (COCl)2 or SOCl2, preferably in a suitable solvent (e.g., N-methylpyrrolidone, acetonitrile, dimethylacetamide, dichloromethane, or tetrahydrofuran), preferably at a temperature of 25°C to 60°C, and optionally in the presence of a base such as triethylamine or N,N-diisopropylethylamine; or otherwise, optionally in the presence of a base (e.g., triethylamine or N,N-diisopropylethylamine), in a suitable solvent (e.g., acetonitrile), under conditions described in the literature for amide coupling of 1-propanephosphonic acid cyclic anhydride (T3P), thereby converting the -OH of the carboxylic acid to a good leaving group such as a chloride group). In addition to the above, the compound of formula (XXVII) in which X is Cl, Br, or I is the compound of formula (XXXI) in which X is Cl, Br, or I, in the presence of a base such as Cs2CO3, K2CO3, NaH, or NaOtBu, and the compound of formula (V) (where X 1 This can be obtained by alkylation with a good leaving group such as Cl, Br, I, triflate, tosyl, or mesyl. In addition, the compound of formula (XXVII) in which X is Cl, Br, or I can be obtained by alkylating the compound of formula (XXVII) with the compound of formula (V) (wherein R 7 The compound of formula (XXXII) can also be synthesized by reacting it with an electron-withdrawing group (such as a cyano or ester) in the presence of a base such as triethylamine or 1,8-diazabicyclo[5.4.0]undeca-7-ene, optionally. 2 From the compound (where is OH), it can be prepared by peptide coupling conversion with the amine of formula (VIII) using the above conditions. Formula (XXXI) (wherein X is Cl, Br, or I, and X 2Compounds of formula (XXI) (wherein X is Cl, Br, or I, R) under basic or acidic conditions. 10 is C 1-6 It can be obtained by hydrolysis of the ester portion of the alkyl compound. These transformations are shown in Scheme 11. [ka] Scheme 11
[0416] Compound of formula (XXI) (wherein X is Cl, Br, or I, and R 10 is C 1-6 (It is alkyl) under basic or acidic conditions, C 1-6 By esterification with alkyl alcohol, or C 1-6 By activating the carboxylic acid functional group before treatment with alkyl alcohol, formula (XXXI) (wherein X is Cl, Br, or I, X 2 It can be synthesized from compounds of formula (XXXI) (wherein X is Cl, Br, or I, and X 2 (wherein X is OH) is a compound of formula (XXXIII) obtained by hydrolyzing the ester moiety under conventional acidic or basic conditions and heating the diacitic acid (wherein X is Cl, Br, or I, and R is OH). 8 C 1-6 It is synthesized by decarboxylation of alkyl compounds. Compound (XXXIII) of formula (wherein X is Cl, Br, or I, and R 8 is C 1-6 The alkyl compound (wherein X is Cl, Br, or I, R) is found in polar organic solvents such as dimethyl sulfoxide, N-methylpyrrolidine, or N,N-dimethylformamide in the presence of a base such as Na2CO3 or K2CO3, and the compound of formula (XXIV) (wherein X is Cl, Br, or I, R) 9 (wherein R is an alkyne of formula (XVII), which is an (aryl)sulfonyl, (hetero)arylsulfonyl, or sulfonic acid group, for example, a sulfonic acid, tosylate, or 2,4,6-trimethylbenzenesulfonyl group) 8 is C1-6 It can be prepared by reaction with alkyl. Compounds of formula (XVII) are commercially available or can be readily prepared by those skilled in the art according to the methods described. Compounds of formula (XXXIV) (wherein X is Cl, Br, or I, and R 9 (wherein X is an aryl)sulfonyl, (hetero)arylsulfonyl, or sulfonic acid group, e.g., sulfonic acid, tosylate, or 2,4,6-trimethylbenzenesulfonyl group) is dissolved in a polar aprotic solvent such as dimethyl sulfoxide, N-methylpyrrolidine, or N,N-dimethylformamide, and a compound of formula (XXXV) (wherein X is Cl, Br, or I) is dissolved in a compound of formula (XIX) (wherein R 9 These compounds can be formed by reacting them with (aryl)sulfonyl, (hetero)arylsulfonyl, or sulfonic acid groups (e.g., sulfonic acid, tosylate, or 2,4,6-trimethylbenzenesulfonyl group). Compounds of formula (XXXV) are commercially available or can be prepared by methods known to those skilled in the art. These transformations are shown in Scheme 12. [ka] Scheme 12
[0417] In addition to the above, the compound of formula (I) is such that X of the amine (IX) is Cl, Br, or I, and X 2This can be obtained by amide coupling conversion with a compound of formula (XXXVI) in which is OH, and by activating the carboxylic acid functional group of the compound of formula (XXXVI) (for example, by using (COCl)2 or SOCl2, preferably in a suitable solvent (e.g., N-methylpyrrolidone, acetonitrile, dimethylacetamide, dichloromethane, or tetrahydrofuran), preferably at a temperature of 25°C to 60°C, and optionally in the presence of a base such as triethylamine or N,N-diisopropylethylamine; or otherwise, optionally in the presence of a base (e.g., triethylamine or N,N-diisopropylethylamine), in a suitable solvent (e.g., acetonitrile), under conditions described in the literature for amide coupling of cyclic anhydride of 1-propanephosphonic acid (T3P), thereby converting the -OH of the carboxylic acid to a good leaving group such as a chloride group). In addition to the above, the compound of formula (I) is, in the presence of a base such as Cs2CO3, K2CO3, NaH, or NaOtBu, the compound of formula (XXXVII), and the compound of formula (V) (where X 1 This can be prepared by alkylation with a good leaving group such as Cl, Br, I, triflate, tosyl, or mesyl. In addition, the compound of formula (I) can be prepared by alkylating the compound of formula (XXXVII) with the compound of formula (VI) (wherein R 7 The compound can also be synthesized by reacting it with an electron-withdrawing group (such as a cyano or ester) in the presence of a base such as triethylamine or 1,8-diazabicyclo[5.4.0]undeca-7-ene, optionally. The compound of formula (XXXVII) is X 2 Compounds of formula (XXXVI) where the OH group can be prepared by peptide coupling conversion with the amine of formula (VIII) using the above conditions. These conversions are shown in Scheme 13. [ka] Scheme 13
[0418] Compound of formula (XXXVI) (wherein X2 (where R is OH) is a compound of formula (XXXVIII) (where R is in the formula) 10 is C 1-6 It can be obtained by hydrolysis of the ester portion (which is alkyl). 10 C 1-6 A compound of formula (XXXVIII) that is alkyl is prepared in the presence of a base such as Cs2CO3, K2CO3, or NaOtBu, and a suitable palladium catalyst such as tetrakistriphenylphosphine palladium, [1,1-bis(diphenylphosphine)ferrocene]dichloropalladium(II), bis(diphenylphosphine)palladium(II) chloride, palladium dichloride, or palladium acetate, in a suitable solvent such as dimethylformamide, dioxane, tetrahydrofuran, ethanol, or water, where X is Cl, Br, or I, and R 9 C 1-6 Compounds of formula (XXXIX) that are alkyl, and R 6 Hydrogen and C are independent of each other. 1-6 Alkyl or two R 6 together become C 3-8 It can result from a Suzuki cross-coupling reaction with a compound of formula (III) that can form a cycloalkyl group, where X is Cl, Br or I, and R 10 C 1-6 Compounds of formula (XXXIX) that are alkyl are prepared in a suitable solvent such as dichloromethane, chloroform, tetrahydrofuran, or acetonitrile, R 10 C 1-6 The alkyl compound of formula (VII) can be synthesized by reaction with a halogenating agent such as N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, or bromine. These transformations are shown in Scheme 14. [ka] Scheme 14
[0419] In addition to the above, the compound of formula (I) can also be synthesized by reacting the compound of formula (XL) (wherein X is Cl, Br is I) with the amine of (IX) and carbon monoxide in the presence of a catalyst such as [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium(II) and optionally a base such as triethylamine. The compound of formula (XL) where X is Cl, Br, or I can be synthesized by independently reacting the compound of formula (XLI) where X is Cl, Br, or I with a base such as Cs2CO3, K2CO3, or NaOtBu, and a suitable palladium catalyst such as tetrakistriphenylphosphine palladium, [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium(II), bis(diphenylphosphine)palladium(II) chloride, palladium dichloride, or palladium acetate in a suitable solvent such as dimethylformamide, dioxane, tetrahydrofuran, ethanol, or water, with R 6 Hydrogen and C are independent of each other. 1-6 Alkyl or two R 6 together become C 3-8 These compounds can be prepared via Suzuki cross-coupling with compounds of formula (III) that can form cycloalkyl groups. These transformations are shown in Scheme 15. [ka] Scheme 15
[0420] R 10 C 1-6 The alkyl compound of formula (XXXVIII) is found in the presence of a base such as Na2CO3 or K2CO3, and in polar organic solvents such as dimethyl sulfoxide, N-methylpyrrolidine, or N,N-dimethylformamide, R 10 C 1-6 It is alkyl and R 9However, it can be synthesized by the reaction of a compound of formula (XLII), which is an (aryl)sulfonyl, (hetero)arylsulfonyl, or sulfonic acid group, such as a sulfonic acid, tosylate, or 2,4,6-trimethylbenzenesulfonyl group, with an alkyne of formula (XLIII). Compounds of formula (XLII) are commercially available or can be readily prepared by those skilled in the art according to the methods described. 10 C 1-6 It is alkyl and R 9 However, the compound of formula (XLII), which is an (aryl)sulfonyl, (hetero)arylsulfonyl, or sulfonic acid group, for example, a sulfonic acid, tosylate, or a 2,4,6-trimethylbenzenesulfonyl group, in a polar aprotic solvent such as dimethyl sulfoxide, N-methylpyrrolidine, or N,N-dimethylformamide, the compound of formula (XLIV) (wherein R 10 C 1-6 (It is alkyl) is a compound of formula (XIX) (wherein R 9 These compounds can be formed by reacting them with (aryl)sulfonyl, (hetero)arylsulfonyl, or sulfonic acid groups (e.g., sulfonic acid, tosylate, or 2,4,6-trimethylbenzenesulfonyl group). Compounds of formula (XLIV) are commercially available or can be prepared by methods known to those skilled in the art. These transformations are shown in Scheme 16. [ka] Scheme 16
[0421] In addition to the above, the compound of formula (I) is used in the peptide coupling transformation of the compound of formula (XLV) to the compound of formula (XLVI) (wherein X 2The compound of formula (XLVI) can be prepared by reaction with (where is OH). The compound of formula (II) is reacted with a base such as Cs2CO3, K2CO3, or NaOtBu, and a suitable palladium catalyst such as tetrakistriphenylphosphine palladium, [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium(II), bis(diphenylphosphine)palladium(II) chloride, palladium dichloride, or palladium acetate, in a suitable solvent such as dimethylformamide, dioxane, tetrahydrofuran, ethanol, or water, and R 6 They are independent of each other, hydrogen, C 1-6 Alkyl or two R 6 together become C 3-8 It can be prepared by Suzuki cross-coupling with a compound of formula (XLVII) that can form a cycloalkyl group. 6 Hydrogen and C are independent of each other. 1-6 Alkyl or two R 6 together become C 3-8 Compounds of formula (XLVII) that can form cycloalkyl groups are prepared by known methods or are commercially available. These transformations are shown in Scheme 17. [ka] Scheme 17
[0422] Compounds of formula (Ib) where Z is S can be prepared by the reaction of compound (I) where Z is O with phosphorus pentasulfide or Lawson's reagent (CAS: 19172-47-5) in a suitable solvent such as toluene, xylene, or dichloromethane. This conversion is shown in Scheme 18. [ka] Scheme 18
[0423] In addition to the above, the compound of formula (Ib) where Z is S, using the above conditions, is X of the compound of formula (XLVb) in the peptide coupling transformation. 2The compound of formula (XLVI) can be prepared by reaction with the compound of formula (XLV) in which the OH group is OH. The compound of formula (XLVb) can be prepared by reaction of the compound of formula (XLV) with phosphorus pentasulfide or Lawson's reagent (CAS: 19172-47-5) in a suitable solvent such as toluene, xylene, or dichloromethane. This conversion is shown in Scheme 19. [ka] Scheme 19
[0424] When the term "compound according to the present invention" is used, it refers to a compound according to the present invention.
[0425] Beyond these, compounds according to the present invention can also be obtained by using standard synthetic techniques known to those skilled in the art. Non-exclusive examples include oxidation reactions, reduction reactions, hydrolysis reactions, coupling reactions, aromatic nucleophilic or electrophilic substitution reactions, nucleophilic substitution reactions, nucleophilic addition reactions, olefination reactions, oxime formation, alkylation, and halogenation reactions.
[0426] Compounds according to the present invention can be converted to other compounds according to the present invention in a manner known by conventional means by substituting one or more substituents of a starting compound according to the present invention with other substituents according to the present invention.
[0427] Depending on the appropriate reaction conditions and selection of starting materials in each case, for example, it may be possible to substitute only one substituent with another substituent according to the present invention in one reaction step, or it may be possible to substitute multiple substituents with other substituents according to the present invention in the same reaction step.
[0428] Salts of compounds according to the present invention can be prepared by methods known in themselves. For example, acid addition salts of compounds according to the present invention can be obtained by treatment with a suitable acid or a suitable ion exchange reagent, and salts with a base can be obtained by treatment with a suitable base or a suitable ion exchange reagent.
[0429] Salts of compounds according to the present invention can be converted to salts with bases by conventional methods, for example, by treatment of the free compound with a suitable basic compound or a suitable ion exchange reagent, and for example, by treatment of the acid addition salt with a suitable acid or a suitable ion exchange reagent.
[0430] Salts of compounds according to the present invention can be converted to other acid addition salts of compounds according to the present invention by methods known in themselves, for example, by treatment of an inorganic acid salt such as a hydrochloride salt with a suitable metal salt such as sodium, barium, or silver salt of the acid, for example with silver acetate, in a suitable solvent (for example, the inorganic salt forming silver chloride precipitates from the reaction mixture because it is insoluble).
[0431] Depending on the procedure or reaction conditions, compounds according to the present invention that have salt-forming properties can be obtained in free form or in salt form.
[0432] In each case, the compounds according to the present invention, in free form or in salt form, and, where appropriate, their tautomers, may exist in one form of possible isomers or as mixtures thereof, depending on the number, absolute and relative configuration of chiral carbon atoms present in the molecule and / or the stereoconfiguration of non-aromatic double bonds present in the molecule, for example, in the form of pure isomers such as anticonformities and / or diastereomers, or as stereoisomer mixtures such as racemic compounds, diastereomer mixtures, or racemic compound mixtures; the present invention relates to pure stereoisomers and also to all possible isomer mixtures, and in each case, even when the details of stereochemistry are not specifically described in each case, it should be understood in this sense in the above and below herein.
[0433] A diastereomer or racemic mixture of compounds according to the present invention can be separated into pure diastereomers or racemic compounds based on physicochemical differences of the components by known methods, for example by fractional crystallization, distillation, and / or chromatography, in free or salt forms, depending on the selected starting materials and procedures.
[0434] Enantiomer mixtures such as racemates obtained by a similar method can be decomposed into optical enantiomers by known methods, for example, by recrystallization from an optically active solvent, by chromatography with a chiral adsorbent, for example by high-performance liquid chromatography (HPLC) with acetylcellulose using appropriate microorganisms, for example by cleavage by specific immobilized enzymes via the formation of inclusion compounds using a chiral crown ether in which only one enantiomer is complexed, or by conversion to a diastereomer salt, for example by reacting the basic final product racemate with an optically active acid such as a carboxylic acid, for example, camphoric acid, tartaric acid, or malic acid, or a sulfonic acid, for example, camphor sulfonic acid, to obtain a diastereomer mixture that can thus be obtained by separating the diastereomer mixture, for example by fractional crystallization based on different solubility, and then using an appropriate substance, for example a basic substance, to obtain a diastereomer in which the desired enantiomer can be released.
[0435] Pure diastereomers or enantiomers can be obtained in accordance with the present invention not only by separating a suitable mixture of stereoisomers, but also by generally known methods of diastereoselective or enantioselective synthesis, for example, by carrying out a process according to the present invention with suitable stereochemical starting materials.
[0436] N-oxides can be prepared by reacting compounds according to the present invention with a suitable oxidizing agent, such as an H2O2 / urea adduct, in the presence of an acid anhydride, such as trifluoroacetic anhydride. Such oxidation is known from the literature, e.g., J.Med.Chem., 32(12), 2561-73, 1989 or International Publication No. 00 / 15615.
[0437] If individual components possess different biological activities, it is advantageous in each case to isolate or synthesize biologically more effective stereoisomers, such as enantiomers or diastereomers, or mixtures of stereoisomers, such as mixtures of enantiomers or diastereomers.
[0438] Compounds according to the present invention, and optionally their tautomers, may be obtained in free form or salt form, optionally in hydrate form, and / or in other solvents, such as solvents that can be used for crystallizing compounds that exist in solid form.
[0439] The following examples illustrate the present invention, but are not intended to limit it.
[0440] Furthermore, the present invention provides intermediates useful for preparing compounds according to the present invention.
[0441] The following intermediates form further embodiments of the present invention.
[0442] Formula (XI) [ka] The compound (wherein Z is O or S, preferably Z is O; R 1a These are hydroxy, halogen, CN, and C 1-6 Alkyl, C 3-6 Cycloalkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 1-6 Alkyl sulfanyl, C 1-6 Alkyl sulfinyl, C 1-6 Alkyl sulfonyl, C 1-6 Alkoxy, amino, and -NHC(O)C 1-6 Selected from alkyl groups; preferably, R 1a C 1-6 Alkyl, C 3-6 Cycloalkyl, C1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl and C 1-6 Selected from alkoxy; R 1b , R 1c , and R 1d These are hydrogen, hydroxyl, halogen, CN, and C 1-6 Alkyl, C 3-6 Cycloalkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 1-6 Alkyl sulfanyl, C 1-6 Alkyl sulfinyl, C 1-6 Alkyl sulfonyl, C 1-6 Alkoxy, amino, and -NHC(O)C 1-6 Selected independently of alkyl; preferably, R 1b , R 1c , and R 1d is hydrogen; A 2 CR is independent. 2 or N, provided there are 3 or fewer A 2 is N, preferably two or fewer A 2 is N, preferably one or less A 2 is N, and more preferably four A 2 CR 2 On the condition that; R 2 These are hydrogen, hydroxyl, halogen, CN, and C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 1-6 Alkyl sulfonyl, C 1-6 Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, diC 1-6 Alkylaminocarbonyl, and C 1-6Independently selected from alkylcarbonyls, where C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 1-6 Alkyl sulfonyl, C 1-6 Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, diC 1-6 Alkylaminocarbonyl, and C 1-6 The alkylcarbonyl group may optionally be substituted with one substituent independently selected from halogen, hydroxyl, and CN; preferably, R 2 Hydrogen, halogen, CN, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxycarbonyl and C 1-6 Alkoxy-C 1-6 Selected independently of alkoxy, where C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxycarbonyl and C 1-6 Alkoxy-C 1-6 Each alkoxy group may be optionally substituted with 1 to 3 substituents independently selected from halogens, hydroxyls, and CNs; provided that at least two Rs 2 Preferably not hydrogen; A 3 CR is independent. 3 or N; R 3 These are hydrogen, hydroxyl, halogen, CN, and C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C3-6 Cycloalkyl, C 1-6 Alkyl sulfonyl, C 1-6 Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, diC 1-6 Alkylaminocarbonyl, and C 1-6 Selected from alkylcarbonyl, where C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 1-6 Alkyl sulfonyl, C 1-6 Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, diC 1-6 Alkylaminocarbonyl, and C 1-6 Each alkylcarbonyl group may be optionally substituted with one substituent independently selected from halogen, hydroxyl, and CN; preferably, R 3 is hydrogen; R 4 C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 2-6 Alkenil, C 2-6 Alkinyl, C 1-6 Alkoxy, C 1-6 Alkylsulfanyl-C 1-6 Alkyl, C 1-6 Alkylsulfinyl-C 1-6 Alkyl, C 1-6 Alkylsulfonyl-C 1-6 Alkyl, C 1-6 Alkoxycarbonyl-C 1-6 Alkyl, C 1-6 Alkylaminocarbonyl-C 1-6 Alkyl, diC 1-6 Alkylaminocarbonyl-C 1-6Selected from alkyl and CN, where C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 2-6 Alkenil, C 2-6 Alkinyl, C 1-6 Alkoxy, C 1-6 Alkylsulfanyl-C 1-6 Alkyl, C 1-6 Alkylsulfinyl-C 1-6 Alkyl, C 1-6 Alkylsulfonyl-C 1-6 Alkyl, C 1-6 Alkoxycarbonyl-C 1-6 Alkyl, C 1-6 Alkylaminocarbonyl-C 1-6 Alkyl and diC 1-6 Alkylaminocarbonyl-C 1-6 Each alkyl group may be optionally substituted with 1 to 3 substituents independently selected from halogens and CN; Here, A 3 and R 4 (These elements can optionally come together to form a ring, preferably a 5-8 membered heterocycle, more preferably a 6-membered heterocycle.) or its salt or N-oxide.
[0443] Formula (II) [ka] The compound (wherein Z is O or S, preferably Z is O; R 1a These are hydroxy, halogen, CN, and C 1-6 Alkyl, C 3-6 Cycloalkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 1-6 Alkyl sulfanyl, C 1-6 Alkyl sulfinyl, C1-6 Alkyl sulfonyl, C 1-6 Alkoxy, amino, and -NHC(O)C 1-6 Selected from alkyl groups; preferably, R 1a C 1-6 Alkyl, C 3-6 Cycloalkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl and C 1-6 Selected from alkoxy; R 1b , R 1c , and R 1d These are hydrogen, hydroxyl, halogen, CN, and C 1-6 Alkyl, C 3-6 Cycloalkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 1-6 Alkyl sulfanyl, C 1-6 Alkyl sulfinyl, C 1-6 Alkyl sulfonyl, C 1-6 Alkoxy, amino, and -NHC(O)C 1-6 Selected independently of alkyl; preferably, R 1b , R 1c , and R 1d is hydrogen; A 2 CR is independent. 2 or N, provided there are 3 or fewer A 2 is N, preferably two or fewer A 2 is N, preferably one or less A 2 is N, and more preferably four A 2 CR 2 On the condition that; R 2 These are hydrogen, hydroxyl, halogen, CN, and C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6Alkoxy, C 3-6 Cycloalkyl, C 1-6 Alkyl sulfonyl, C 1-6 Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, diC 1-6 Alkylaminocarbonyl, and C 1-6 Independently selected from alkylcarbonyls, where C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 1-6 Alkyl sulfonyl, C 1-6 Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, diC 1-6 Alkylaminocarbonyl, and C 1-6 Each alkylcarbonyl group may be optionally substituted with one substituent independently selected from halogen, hydroxyl, and CN; preferably, R 2 Hydrogen, halogen, CN, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxycarbonyl and C 1-6 Alkoxy-C 1-6 Selected independently of alkoxy, where C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxycarbonyl and C 1-6 Alkoxy-C 1-6 Each alkoxy group may be optionally substituted with 1 to 3 substituents independently selected from halogens, hydroxyls, and CNs; provided that at least two Rs 2 Preferably not hydrogen; A 3 CR is independent. 3 or N; R3 These are hydrogen, hydroxyl, halogen, CN, and C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 1-6 Alkyl sulfonyl, C 1-6 Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, diC 1-6 Alkylaminocarbonyl, and C 1-6 Selected from alkylcarbonyl, where C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 1-6 Alkyl sulfonyl, C 1-6 Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, diC 1-6 Alkylaminocarbonyl, and C 1-6 Each alkylcarbonyl group may be optionally substituted with one substituent independently selected from halogen, hydroxyl, and CN; preferably, R 3 is hydrogen; R 4 C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 2-6 Alkenil, C 2-6 Alkinyl, C 1-6 Alkoxy, C 1-6 Alkylsulfanyl-C 1-6 Alkyl, C 1-6 Alkylsulfinyl-C 1-6 Alkyl, C 1-6 Alkylsulfonyl-C 1-6Alkyl, C 1-6 Alkoxycarbonyl-C 1-6 Alkyl, C 1-6 Alkylaminocarbonyl-C 1-6 Alkyl, diC 1-6 Alkylaminocarbonyl-C 1-6 Selected from alkyl and CN, where C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 2-6 Alkenil, C 2-6 Alkinyl, C 1-6 Alkoxy, C 1-6 Alkylsulfanyl-C 1-6 Alkyl, C 1-6 Alkylsulfinyl-C 1-6 Alkyl, C 1-6 Alkylsulfonyl-C 1-6 Alkyl, C 1-6 Alkoxycarbonyl-C 1-6 Alkyl, C 1-6 Alkylaminocarbonyl-C 1-6 Alkyl and diC 1-6 Alkylaminocarbonyl-C 1-6 Each alkyl group may be optionally substituted with 1 to 3 substituents independently selected from halogens and CN; Here, A 3 and R 4 They may optionally come together to form a ring, preferably a 5- to 8-membered heterocycle, more preferably a 6-membered heterocycle; X is Cl, Br, or I. or its salt or N-oxide.
[0444] The compounds of formula (I) as defined in this invention may be used in the agricultural sector and related fields of use, for example, as active ingredients for controlling plant pathogens, or as abiotic compounds for controlling potentially harmful microorganisms or organisms to humans. Novel compounds are distinguished by their excellent activity at low application rates, the sufficient tolerance exhibited by plants, and their environmental safety. These compounds possess highly useful curative, preventive, and systemic properties and can be used to protect a large number of cultivated plants. The compounds of formula (I) as defined in this invention can also be used to inhibit or eliminate pathogens appearing on plants or plant parts (fruits, flowers, leaves, stems, tubers, roots) of various useful plant crops, while simultaneously protecting later-growing plant parts from plant pathogenic microorganisms.
[0445] Compounds of formula (I) as defined in this invention may also be used as fungicides. As used herein, the term "fungicide" means a compound that controls, modifies, or prevents the growth of fungi. The term "fungicidal effective amount" means the amount of a compound or combination of compounds that can produce an effect on fungal growth. Controlling or modifying effects include all deviations from natural occurrence, such as death or delay, and prevention includes the formation of barriers or other defenses in or on plants to prevent fungal infection.
[0446] For protection against fungal infections and plant pathogenic fungi present in the soil, the compound of formula (I) as defined in this invention may also be used as a coating agent for treating plant propagation materials, such as seeds, fruits, tubers, or grains, or plant cuttings (e.g., rice). The propagation material may be treated with a composition containing the compound of formula (I) as defined in this invention before planting: for example, seeds may be coated before sowing. The compound of formula (I) as defined in this invention may also be applied (coated) to grains by impregnating the seeds in a liquid formulation or by coating the seeds with a solid formulation. The composition may also be applied to the planting site when the propagation material is planted, for example, in the sowing furrow during sowing. The present invention also relates to a method for treating plant propagation materials and plant propagation materials treated in this way.
[0447] Furthermore, the compounds of formula (I) as defined in the present invention can be used in related fields, for example, to control fungi in the protection of industrial materials, including wood and wood-related industrial products, in food storage, and in hygiene management.
[0448] In addition, the present invention can also be used to protect non-biological materials, such as sawn timber, wall panels, and paints, from fungal attacks.
[0449] Compounds of formula (I) as defined in the present invention, and fungicidal compositions containing such compounds, can be used to control plant diseases caused by broad-spectrum fungal plant pathogens. They are effective in controlling broad-spectrum plant diseases such as those caused by leaf pathogens of ornamental plants, lawns, vegetables, fields, grains, and fruit crops.
[0450] Examples of disease-causing fungi and fungal vectors, as well as plant pathogenic bacteria and viruses, that can be controlled include: This includes species such as Absidia corymbifera, Alternaria spp., Aphanomyces spp., Ascochyta spp., Aspergillus spp. (including A. flavus, A. fumigatus, A. nidulans, A. niger, and A. terrus), Aureobasidium spp. (including A. pullulans), Blastomyces dermatidis, Blumeria graminis, and Bremia lactucaea. (Lactucae), Botryosphaeria spp. (including B. dothidea and B. obtusa), Botrytis spp. (including B. cinerea), Candida spp. (including C. albicans, C. glabrata, C. krusei, C. lusitaniae, C. parapsilosis, and C. tropicalis), Cephaloascus fragrans, Ceratocystis spp., Cercospora genus (Examples include C. arachidicola), Cercosporidium personatum, and Cladosporium spp. (Examples include Claviceps purpurea). Coccidioides immitis, Cochliobolus spp., Colletotrichum spp. (including C. musae), Cryptococcus neoformans, species of the genus Diaporthe, species of Didymella, species of Drecxlera, species of Elsinoe, Species of the genus Epidermophyton, Erwinia amylovora, and Erysiphe (including E. cichoracearum) Eutypa lata, Fusarium spp. (including F. culmorum, F. graminearum, F. langsethiae, F. moniliforme, F. oxysporum, F. proliferatum, F. subglutinans, F. solani), Gaeumannomyces graminis, Gibberella fujikuroi, Gloeodes pomigena, Gloeosporium musarum musarum), Glomerella cingulate, Guignardia bidwellii, Gymnosporangium juniperi-virginianae, Helminthosporium spp., Hemileia spp., Histoplasma spp. (H. Capsulatum is an example), Laetisaria fuciformis, Leptographium lindbergi, Leveillula taurica, Lophodermium sediciosum seditiosum), Microdochium nivale, Microsporum spp., Monilinia spp., Mucor spp., Mycosphaerella spp. (M. graminicola, M. pomi)Examples include *P. pomi*, *Oncobasidium theobromaeon*, *Ophiostoma piceae*, species of the genera *Paracoccidioides*, *Penicillium* (including *P. digitatum* and *P. italicum*), species of the genera *Petriellidium*, *Peronosclerospora* (including *P. maydis*, *P. philippinensis*, and *P. sorghi*), species of the genera *Peronospora*, and *Phaeosphaeria nodorum*. *Phonophora nodorum*, *Phakopsora pachyrhizi*, *Phellinus igniarus*, *Phialophora* spp., *Phoma* spp., *Phomopsis viticola*, *Phytophthora* spp. (including *P. infestans*), *Plasmopara* spp. (including *P. halstedii* and *P. viticola*), *Pleospora* spp., *Podosphaera* Pseudomonas spp. (P. leucotricha is an example), polymyxa graminis, polymyxa betae, Pseudocercosporella herpotrichoides, Pseudomonas spp., Pseudoperonospora (P. cubensis, P. humli (P.Examples include Pseudopeziza humuli, Pseudopeziza tracheiphila, Puccinia spp. (P. hordei, P. recondita, P. striiformis, P. triticina), Pyrenopeziza spp., Pyrenophora spp., Pyricularia spp. (P. oryzae), Pythium spp. (P. ultimum), Ramularia spp., and Rhizoctonia. (spp.), Rhizomucor pusillus, Rhizopus arrhizus, Rhynchosporium spp., Scedosporium spp. (including S. apiospermum and S. prolificans), Schizothyrium pomi, etc. Species belonging to the genera Sclerotinia, Sclerotium, Septoria (including S. nodorum and S. tritici), Sphaerotheca macularis, Sphaerotheca fusca (Sphaerotheca fuliginea), Sporothorix, Stagonospora nodorum, Stemphylium, Stereum hirsutum, and Thanatephorus cucumeris. *Tillandsia cucumeris*, *Tillandsia basicola*, *Tillandsia spp.*, *Trichoderma spp.* (including *T. harzianum*, *T. pseudokoningii*, and *T. viride*), Species belonging to the genera Trichophyton, Typhula, Uncinula necator, Urocystis, Ustilago, Venturia (including V. inaequalis), Verticillium, and Xanthomonas.
[0451] In particular, the compounds of formula (I) as defined in the present invention, and fungicidal compositions containing such compounds, can be used to control plant diseases caused by broad-spectrum fungal plant pathogens in the classes Basidiomycete, Ascomycete, Oomycete, and / or Deuteromycete, Blasocladiomycete, Chrytidiomycete, Glomeromycete, and / or Mucoromycete. More specifically, the compounds of formula (I) as defined in the present invention can be used to control Oomycetes.
[0452] These pathogens may include the following: Oomycete (Phytophthora genus) diseases, such as Phytophthora capsici, Phytophthora infestans, Phytophthora sojae, Phytophthora fragariae, Phytophthora nicotianae, Phytophthora cinnamomi, Phytophthora citricola, Phytophthora citrophthora, and Phytophthora erythroseptica Diseases caused by erythroseptica; diseases of the genus Pythium, such as Pythium aphanidermatum, Pythium arrhenomanes, Pythium graminicola, Pythium irregulare, Pythium sylvaticum, and Pythium ultimum; diseases caused by Peronosporales, such as Peronospora destructor, Peronospora parasitica, Plasmopara viticola, and Plasmopara *Halstedii*, *Pseudoperonospora cubensis*, *Albugo candida*, *Sclerophthora macrospora*, and *Bremia lactucae*;Other examples include Aphanomyces cochlioides, Labyrinthula zosterae, Peronosclerospora sorghi, and Sclerospora graminicola. Ascomycetes (Ascomycetes, Ascomycetes, Leaf spot, Leaf spot, Bulb disease or Weak spot disease, and / or rot, e.g., Stemphylium solani, Stagonospora tainanensis, Spirocaea oleaginea, Setosphaeria turcica, Pyrenochaeta lycoperisici, Pleospora herbarum, Phoma destructiva, Phaeosphaeria herpotrichoides, Phaeocryptocus gaeumannii) Ophiosphaerella graminicola, Ophiobolus graminis, Leptosphaeria maculans, Hendersonia creberrima, Helminthosporium triticirepentis, Setosphaeria turcica, Drecslera glycines, Didymella bryoniae, Cycloconium oleagineum, Corynespora cassiicola, Cochliobolus sativus Pyrenophora sativus, Bipolaris cactivora, Venturia inaequalis, Pyrenophora teres, Pyrenophora triticilepentis*Alternaria tritici-repentis*, *Alternaria brassicicola*, *Alternaria brassicicola*, *Alternaria solani*, and *Alternaria tomatophila*, *Capnodiales*, for example, *Septoria tritici*, *Septoria nodorum*, *Septoria glycines*, *Cercospora arachidicola*, *Cercospora sojina*, *Cercospora zeae-maydis*, and *Cercosporella capsellae*. Mycosphaerella capsellae, Cercosporella herpotrichoides, Cladosporium carpophilum, Cladosporium effusum, Passalora fulva, Cladosporium oxysporum, Dothistroma septosporum, Isariopsis clavispora, Mycosphaerella fijiensis, Mycosphaerella graminicola, Mycosphaerella coepkei koepkeii), Phaeoisariopsis bataticola, Pseudocercospora vitis, Pseudocercosporella herpotrichoides, Ramularia beticolabeticola), Ramularia collo-cygni, Magnaporthales genus, for example Gaeumannomyces graminis, Magnaporthe grisea, Pyricularia oryzae, Diaporthales genus, for example Anisogramma anomala, Apiognomonia errabunda, Cytospora platani, Diaporthe phaseolorum, Discula destructiva, Gnomonia fructicola fructicola), Greeneria uvicola, Melanconium juglandinum, Phomopsis viticola, Sirococcus clavigignenti-juglandacearum, Tubakia dryina, Dicarpella spp., Valsa ceratosperma, and others such as Actinothyrium graminis, Ascochyta pisi, Aspergillus flavus, Aspergillus fumigatus fumigatus), Aspergillus nidulans, Asperisporium caricae, Blumeriella jaapii, Candida spp., Capnodium ramosum, Cephaloascus(spp.), Cephalosporium gramineum, Ceratocystis paradoxa, Chaetomium spp., Hymenoscyphus pseudoalbidus, Coccidioides spp., Cylindrosporium padi, Diplocarpon malae, Drepanopeziza campestris, Elsinoe ampelina, Epicoccum nigrum, Epidermophyton spp., Eutypa lata), Geotrichum candidum, Gibellina cerealis, Gloeocercospora sorghi, Gloeodes pomigena, Gloeosporium perennans; Gloeotinia temulenta, Griphospaeria corticola, Kabatiella lini, Leptographium microsporum, Leptosphaerulinia crassiasca, Lophodermium sediciosum seditiosum), Marssonina graminicola, wheat mold fungus (Microdochium nivale), Monilinia fructicola, Monographella albescens, Monosporascus canonvalsNaemacyclus cannonballus, Naemacyclus spp., Ophiostoma novo-ulmi, Paracoccidioides brasiliensis, Penicillium expansum, Pestalotia rhododendri, Petriellidium spp., Pezicula spp., Phialophora gregata, Phyllachora pomigena, Phymatotrichum omnivora, Physalospora abdita, Plectosporium tabacinum, Polyscytalum pustulans pustulans), Pseudopeziza medicaginis, Pyrenopeziza brassicae, Ramulispora sorghi, Rhabdocline pseudotsugae, Rhynchosporium secalis, Sacrocladium oryzae (rice leaf rot fungus), Scedosporium spp., Schizothyrium pomi, Sclerotinia sclerotiorum, Sclerotinia minor;Sclerotium species, Typhula ishikariensis, Seimatosporium mariae, Lepteutypa cupressi, Septocyta ruborum, Sphaceloma perseae, Sporonema phacidioides, Stigmina palmivora, Tapesia yallundae, Taphrina bullata, Thielviopsis basicola, Trichoseptria fructigena Powdery mildew disease, such as Blumeria graminis, Erysiphe polygoni, Uncinula necator, Sphaerotheca fuligena, apple powdery mildew fungus (Podosphaera leucotricha), Podospaera macularis, Golovinomyces cichoracearum, Leveillula taurica, Microsphaera diffusa, Oidiopsis gossipii Caused by powdery mildews such as gossypii, Phyllactinia guttata, and Oidium arachidis (Erysiphales);Molds, for example, Dothiorella aromatica, Diplodia seriata, Guignardia bidwellii, Botrytis cinerea, Botryotinia allii, Botryotinia fabae, Fusicoccum amygdali, Lasiodiplodia theobromae, Macrophoma theicola, Macrophomina phaseolina, and Phyllosticta cucurbitacearum. Anthracnose caused by Botryosphaeriales species such as cucurbitacearum; anthracnose caused by Glommerelales species such as Colletotrichum gloeosporioides, Colletotrichum lagenarium, Colletotrichum gossypii, Glomerella cingulata, and Colletotrichum graminicola;Furthermore, wilt disease or canker disease, for example, Acremonium strictum, Claviceps purpurea, Fusarium culmorum, Fusarium graminearum, Fusarium virguliforme, Fusarium oxysporum, Fusarium subglutinans, Fusarium oxysporum f.sp.cubense, Gerlachia nivale, Gibberella fujikuroi, Gibberella zeae Caused by Hypocreales species such as Gliocladium spp., Myrothecium verrucaria, Nectria ramulariae, Trichoderma viride, Trichothecium roseum, and Verticillium theobromae. Basidiomycete (including smut fungi, such as those caused by the Ustilaginales order, such as Ustilaginoidea virens, Ustilago nuda, Ustilago tritici, and Ustilago zeae); rust fungi, such as Cerotelium fici, Chrysomyxa arctostaphyli, Coleosporium ipomoeae, Hemileia vastatrix, Puccinia arachidis, and Puccinia cacabata) Puccinia cacabata), Puccinia graminis, Puccinia recondita, Puccinia sorghi, Puccinia hordei, Puccinia striiformis f.sp. Hordei, Puccinia striiformis f.sp. cecalisPucciniales, such as Secalis, Pucciniastrum coryli, or Cronartium ribicola, Gymnosporangium juniperi-viginianae, Melampsora medusae, Phakopsora pachyrhizi, Phragmidium mucronatum, Physopella ampelosidis, Tranzschelia discolor, and Uromyces viciae-fabee. Those caused by Uredinales species such as viciae-fabae; as well as other rots and diseases, such as Cryptococcus spp., Exobasidium vexans, Marasmiellus inoderma, and Mycena spp.), Sphacelotheca reiliana, Typhula ishikariensis, Urocystis agropyri, Itersonilia perplexans, Corticium invisum, Laetisaria fuciformis, Waitea circinata, Rhizoctonia solani, Thanetephorus cucurmeris, Entyloma dahliae, Entylomella microspora, Neovossia molliniae Caused by *Tillets* (*Moliniae*) and *Tillets* caries. Blastocladiomycetes, for example, Physoderma maydis. Mucoromycete, for example, Choanephora cucurbitarum; Mucor spp.; Rhizopus arrhizus. Furthermore, diseases caused by other species and genera closely related to those listed above.
[0453] In addition to their fungicidal activity, the compounds of formula (I) as defined in the present invention and compositions comprising such compounds may also be active against bacteria such as Erwinia amylovora, Erwinia caratovora, Xanthomonas campestris, Pseudomonas syringae, Streptomyces scabies, and other related species, as well as certain protozoa.
[0454] Within the scope of the present invention, target crops and / or useful plants to be protected are typically perennial and annual crops, e.g., berry plants, e.g., blackberries, blueberries, cranberries, raspberries, and strawberries; cereals, e.g., barley, maize (corn), millet, oats, rice, rye, sorghum, rye, and wheat; fiber plants, e.g., cotton, flax, hemp, jute, and sisal; crops, e.g., sugar and fodder beets, coffee, hops, mustard, rapeseed (canola), poppies, sugarcane, sunflowers, tea, and tobacco; fruit trees, e.g., apples, apricots, avocados, bananas, cherries, citrus fruits, nectarines, peaches, pears, and plums; pasture grasses, e.g., Bermuda grass, bluegrass, bentgrass, centipede grass, fescue, ryegrass , St. Augustine grass and Zoysia grass; herbs, such as basil, borage, chives, coriander, lavender, lavage, mint, oregano, parsley, rosemary, sage, and thyme; legumes, such as kidney beans, lentils, peas, and soybeans; nuts, such as almonds, cashews, peanuts, hazelnuts, peanuts, pecans, pistachios, and walnuts; palms, such as oil palms; ornamental plants, such as flowers, shrubs, and trees; other trees, such as cocoa, coconut, olive, and rubber; vegetables, such as asparagus, eggplant, broccoli, cabbage, carrots, cucumbers, garlic, lettuce, mallow, melon, okra, onions, pepper, potatoes, pumpkins, rhubarb, spinach, and tomatoes; and climbing plants, such as grapes.
[0455] Useful plants and / or target crops according to the present invention include conventional varieties and genetically enhanced or engineered varieties, such as insect-resistant (e.g., Bt. and VIP varieties), disease-resistant, herbicide-resistant (e.g., glyphosate and glufosinate-resistant maize varieties, commercially available under trade names RoundupReady® and LibertyLink®), and nematode-resistant varieties. Examples of appropriately genetically enhanced or engineered varieties include the Stoneville 5599BR cotton and Stoneville 4892BR cotton varieties.
[0456] The terms “useful plants” and / or “target crops” should be understood to also include useful plants that have been conferred resistance to herbicides or classifications of herbicides (e.g., HPPD inhibitors, ALS inhibitors, e.g., primisulfuron, prosulfuron, and trifloxysulfuron, EPSPS (5-enol-pyruvir-shikimic acid-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors, or PPO (protoporphyrinogen-oxidase) inhibitors) as a result of conventional breeding methods or genetic manipulation. Clearfield® summer rapeseed (canola) is an example of a crop conferred resistance to imidazolinone, e.g., imazamox, by conventional breeding methods (mutation). Examples of crops that have been genetically engineered to be resistant to herbicides or herbicide classifications include glyphosate and glufosinate-resistant maize varieties marketed under trade names RoundupReady®, Herculex I®, and LibertyLink®.
[0457] The terms “useful plants” and / or “target crops” should be understood to include plants that are naturally resistant to or conferred resistance to harmful insects. This includes plants transformed by the use of recombinant DNA technology, which can synthesize one or more selectively acting toxins, for example, known from toxin-producing bacteria. Examples of toxins that can be expressed include δ-endotoxin, vegetatively propagating insecticidal protein (Vip), insecticidal proteins from bacterial colonizing nematodes, and toxins produced by scorpions, arachnids, wasps, and fungi. An example of a crop modified to express Bacillus thuringiensis toxin is Bt maize KnockOut® (Syngenta Seeds). An example of a crop containing multiple genes that express multiple toxins in order to encode insecticide resistance is VipCot® (Syngenta Seeds). Furthermore, crops or their seed materials can exhibit resistance to multiple types of pests (so-called stacked transgenic events, which are produced by genetic modification). For example, plants may have the ability to express insecticidal proteins while simultaneously being herbicide resistant, such as Herculex I® (Dow AgroSciences, Pioneer Hi-Bred International).
[0458] The terms “useful plants” and / or “target crops” should be understood to include useful plants transformed by the use of recombinant DNA technology to enable the synthesis of selectively acting antipathogenic substances, such as so-called “pathogenicity-associated proteins” (PRPs, see, e.g., European Patent Application Publication No. 0 392 225). Examples of such antipathogenic substances and transgenic plants capable of synthesizing such antipathogenic substances are known, for example, from European Patent Application Publication No. 0 392 225, International Publication No. 95 / 33818, and European Patent Application Publication No. 0 353 191. Methods for producing such transgenic plants are generally known to those skilled in the art and are described, for example, in the aforementioned publications.
[0459] Toxins that may be expressed by transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as δ-endotoxin, such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C; or vegetative insecticidal proteins (Vip), such as Vip1, Vip2, Vip3, or Vip3A; or bacterial colony-forming nematodes, such as species of the genera Photorhabdus or Xenorhabdus, such as Photorhabdus luminescence. Insecticidal proteins of Xenorhabdus nematophilus (luminescens); toxins produced by animals, e.g., scorpion toxins, arachnid toxins, wasp toxins, and other insect-specific neurotoxins; toxins produced by fungi, e.g., Streptomycete toxins; plant lectins, e.g., pea lectin, barley lectin, or saxifrage lectin; aglutinin; proteinase inhibitors, e.g., trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome-inactivating proteins Examples include glycans (RIPs), such as lysine, maize-RIP, abrin, rufin, saporin, or briodin; steroid metabolic enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidase, ecdysone inhibitors, HMG-COA-reductase; ion channel blockers, such as sodium or calcium channel blockers; juvenile hormone esterase, diuretic hormone receptor, stilbenzyl synthase, bibenzyl synthase, chitinase, and glucanase.
[0460] Furthermore, in connection with the present invention, it should be understood that there are δ-endotoxins, e.g., Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C, or vegetatively reproducing insecticidal proteins (Vip), e.g., Vip1, Vip2, Vip3, or Vip3A, and more explicitly, hybrid toxins, cleaved toxins, and modified toxins. Hybrid toxins are produced by recombination through novel combinations of different domains of the protein (see, for example, International Publication No. 02 / 15701). Cleaved toxins, e.g., cleaved Cry1Ab, are known. In the case of modified toxins, one or more amino acids of a naturally occurring toxin are replaced. In such amino acid substitutions, preferably a protease recognition sequence that does not exist in nature is inserted into the toxin, for example, in the case of Cry3A055, and a cathepsin-G recognition sequence is inserted into the Cry3A toxin (see International Publication No. 03 / 018810).
[0461] Additional examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed, for example, in European Patent Publication No. 0374753, International Publication No. 93 / 07278, International Publication No. 95 / 34656, European Patent Publication No. 0427529, European Patent Publication No. 451878, and International Publication No. 03 / 052073.
[0462] The processes for preparing such transgenic plants are generally known to those skilled in the art and are described, for example, in the publications mentioned above. CryI-type deoxyribonucleic acid and its preparations are known, for example, from International Publication No. 95 / 34656, European Patent Application Publication No. 0367474, European Patent Application Publication No. 0401979, and International Publication No. 90 / 13651.
[0463] Toxins contained in transgenic plants confer resistance to harmful insects. Such insects can exist in any insect taxonomy, but are commonly found in beetles (Coleoptera), diptera, and butterflies (Lepidoptera).
[0464] Transgenic plants containing one or more genes encoding insecticide resistance and expressing one or more toxins are known, and some of them are commercially available. Examples of such plants include: YieldGard® (maize variety expressing Cry1Ab toxin); YieldGard Rootworm® (maize variety expressing Cry3Bb1 toxin); YieldGard Plus® (maize variety expressing Cry1Ab and Cry3Bb1 toxins); Starlink® (maize variety expressing Cry9C toxin); Herculex I® (maize variety expressing Cry1Fa2 toxin and the enzyme phosphinothrysin N-acetyltransferase (PAT) to achieve resistance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety expressing Cry1Ac toxin); Bollgard I® (cotton variety expressing Cry1Ac toxin); Bollgard Examples include II (registered trademark) (cotton varieties expressing Cry1Ac and Cry2Ab toxins); VipCot (registered trademark) (cotton varieties expressing Vip3A and Cry1Ab toxins); NewLeaf (registered trademark) (potato varieties expressing Cry3A toxin); NatureGard (registered trademark), Agrisure (registered trademark) GT Advantage (GA21 glyphosate resistance trait), Agrisure (registered trademark) CB Advantage (Bt11 corn borer (CB) trait), and Protecta (registered trademark).
[0465] Further examples of such genetically modified crops include: 1. Bt11 Maize, registration number C / FR / 96 / 05 / 10, Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France. Genetically modified maize (Zea mays) conferred resistance to attacks by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) through transgenic expression of the cleavage-type Cry1Ab toxin. Bt11 maize has also achieved resistance to the herbicide glufosinate ammonium through transgenic expression of the enzyme PAT. 2. Bt176 Maize, registration number C / FR / 96 / 05 / 10, from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St.Sauveur, France. This is a genetically modified maize (Zea mays) conferred with resistance to attacks by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) through transgenic expression of the Cry1Ab toxin. Bt176 maize has also achieved resistance to the herbicide glufosinate ammonium through transgenic expression of the enzyme PAT. 3. MIR604 Maize, registration number C / FR / 96 / 05 / 10, from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France. Maize conferred insect resistance by transgenic expression of modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G protease recognition sequence. The preparation of such transgenic maize plants is described in International Publication No. 03 / 018810. 4. MON 863 Maize, registration number C / DE / 02 / 9, from Monsanto Europe, SA270-272 Avenue de Tervuren, B-1150 Brussels, Belgium. MON 863 expresses the Cry3Bb1 toxin and is resistant to certain Coleoptera insects. 5. Monsanto Europe SA270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, IPC 531 Cotton, registration number C / ES / 96 / 02. 6. Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, 1507 Maize, registration number C / NL / 00 / 10. Genetically modified maize for expression of the protein Cry1F to achieve resistance to certain Lepidoptera insects, and for expression of the PAT protein to achieve resistance to the herbicide glufosinate ammonium. 7. NK603×MON810 Maize, registration number C / GB / 02 / M3 / 03, Monsanto Europe, SA270-272 Avenue de Tervuren, B-1150 Brussels, Belgium. This is a conventionally bred hybrid maize variety obtained by crossing genetically modified varieties NK603 and MON 810. The NK603×MON810 maize transgenically expresses the protein CP4 EPSPS obtained from the strain CP4 of the genus Agrobacterium, thereby conferring resistance to the herbicide Roundup® (containing glyphosate). It also transgenically expresses the Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki, thereby conferring resistance to certain Lepidoptera, including the European corn borer.
[0466] As used herein, the term “habitat” means a field in which plants grow or on which seeds of cultivated plants are sown or in which seeds will be sown in the soil. “Habitat” includes soil, seeds and seedlings, and established vegetation.
[0467] The term "plant" refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, leaves, and fruits.
[0468] The term "plant propagation material" is understood to refer to reproductive parts such as seeds, and vegetative propagation materials such as cuttings or tubers that can be used for plant propagation, such as potatoes. Examples include (strictly speaking) seeds, roots, fruits, tubers, bulbs, rhizomes, and parts of plants. Also, germinated plants and seedlings that will be transplanted after germination or emergence from the soil may be referred to. Such seedlings may be protected before transplantation by total or partial treatment by immersion. Preferably, "plant propagation material" is understood to mean seeds.
[0469] The pesticides referred to herein by their common names are publicly known, for example, from "The Pesticide Manual," 19th Ed., British Crop Protection Council 2021.
[0470] The compound of formula (I) as defined in the present invention may be used in an unmodified form, or preferably in combination with auxiliaries conventionally used in the art of formulation. For this purpose, the compound may be appropriately incorporated in known ways into emulsifiable concentrates, coating pastes, ready-to-spray or dilutable solutions or suspensions, diluted emulsions, wettable powders, soluble powders, powders, granules, and also into encapsulations in polymeric substances, for example. As with the type of composition, the method of application, such as spraying, misting, powdering, granulation, coating, or pouring, is selected according to the intended purpose and the circumstances at hand. The composition may also contain further auxiliaries such as stabilizers, defoamers, viscosity modifiers, binders, or tackifiers, as well as fertilizers, micronutrient donors, or other formulations for obtaining special effects.
[0471] For example, suitable carriers and / or auxiliaries for agricultural applications may be solids or liquids and are substances useful in compounding techniques, such as natural or recycled inorganic substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders, or fertilizers. Such carriers are described, for example, in International Publication No. 97 / 33890.
[0472] The suspension concentrate is an aqueous formulation in which finely ground solid particles of the active compound are suspended. Such formulations may further contain anti-settling agents and dispersants, wetting agents to enhance activity, and antifoaming agents and crystal growth inhibitors. When used, the concentrate is diluted with water and typically applied as a spray to the area to be treated. The amount of the active ingredient may range from 0.5% to 95% of the concentrate.
[0473] Wettable powders are in the form of finely ground particles that disperse easily in water or other liquid carriers. The particles contain the active ingredient held within a solid matrix. Typical solid matrices include Fuller's earth, kaolin clay, silica, and other easily humidifiable organic or inorganic solids. Wettable powders typically contain 5% to 95% of the active ingredient and small amounts of wetting agents, dispersants, or emulsifiers.
[0474] The emulsifying concentrate is a homogeneous liquid composition that is dispersible in water or other liquids, and may consist entirely of the active compound together with a liquid or solid emulsifier, or it may also contain a liquid carrier such as xylene, heavy aromatic naphtha, isophorone, and other non-volatile organic solvents. When used, the concentrate is dispersed in water or other liquid and typically applied as a spray to the area to be treated. The amount of the active ingredient may range from 0.5% to 95% of the concentrate.
[0475] Granular formulations include both extruded materials and relatively coarse particles and are typically applied undiluted to the area requiring treatment. Typical carriers for granular formulations include sand, fuller's soil, attapulgite clay, bentonite clay, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, gypsum, wood flour, crushed corn cobs, crushed peanut shells, sugar, sodium chloride, sodium sulfate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulfate, and other organic or inorganic materials that can absorb or be coated with the active compound. Granular formulations typically contain 5% to 25% active ingredients, which may include surfactants such as heavy aromatic naphtha, kerosene, and other petroleum fractions, or vegetable oils; and / or stickers such as dextrin, glue, or synthetic resins.
[0476] The powder is a free-flowing mixture of the active ingredient and finely pulverized solids such as talc, clay, powder, and other organic and inorganic solids that act as a dispersant and carrier.
[0477] Microcapsules are typically droplets or granules of an active ingredient encapsulated within an inert, porous shell that allows for the controlled release of the encapsulated material into the surroundings. Encapsulated droplets are typically 1 to 50 microns in diameter. The encapsulated liquid typically constitutes 50 to 95% of the capsule's weight and may contain a solvent in addition to the active compound. Encapsulated granules are generally porous granules having a porous membrane that seals the pore openings of the granules, retaining the active species in liquid form inside the granular pores. Granules are typically 1 millimeter to 1 centimeter in diameter, preferably 1 to 2 millimeters. Granules are formed by extrusion, agglomeration, or prilling, or they exist naturally. Examples of such materials include vermiculite, calcined clay, kaolin, attapulgite clay, sawdust, and granular carbon. Shell or membrane materials include natural and synthetic rubber, cellulosic materials, styrene-butadiene copolymers, polyacrylonitrile, polyacrylates, polyesters, polyamides, polyureas, polyurethanes, and starch xanthetes.
[0478] Other useful formulations for agricultural applications include simple solutions of the active ingredient in solvents such as acetone, alkylated naphthalene, xylene, and other organic solvents that dissolve completely at the desired concentration. Additionally, pressurized sprayers may be used in which the active ingredient is dispersed in a finely pulverized form as a result of evaporation of a low-boiling-point dispersible solvent carrier.
[0479] Suitable agricultural additives and / or carriers useful for formulating the compositions of the present invention in the above-mentioned formulation types are well known to those skilled in the art.
[0480] Examples of liquid carriers that can be used include water, toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetate, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidinone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-Trichloroethane, 2-Heptanone, Alpha-pinene, d-Limonene, Ethylene glycol, Ethylene glycol butyl ether, Ethylene glycol methyl ether, γ-Butyrolactone, Glycerol, Glycerol diacetate, Glycerol monoacetate, Glycerol triacetate, Hexadecane, Hexylene glycol, Isoamyl acetate, Isobornyl acetate, Isooctane, Isophorone, Isopropylbenzene, Isopropyl myristate, Lactic acid, Laurylamine, Mesityl oxide, Methoxypropanol, Methyl isoamyl ketone, Methyl isobutyl ketone, Methyl laurate, Methyl octanoate, Methyl oleate, Methylene chloride, m-Xylene, n-Hexane, n-Octylamine, Octadeca Examples include sodium phosphate, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG400), propionic acid, propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, methanol, ethanol, isopropanol and amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol and other high molecular weight alcohols, ethylene glycol, propylene glycol, glycerin, and N-methyl-2-pyrrolidinone. Water is generally a preferred carrier for diluting concentrates.
[0481] Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, diatomaceous earth (kieselguhr), white pigment, diatomaceous earth (diatomaxeous earth), lime, calcium carbonate, bentonite clay, fuller's earth, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, walnut shell flour, and lignin.
[0482] A wide range of surfactants are advantageously used in both liquid and solid compositions, particularly those designed to be diluted with a carrier before application. When used, these surfactants typically constitute 0.1% to 15% by mass of the formulation. They may be anionic, cationic, nonionic, or polymeric and can be used as emulsifiers, wetting agents, suspending agents, or for other purposes. Typical surfactants include alkyl sulfate salts, e.g., diethanolammonium lauryl sulfate; alkylaryl sulfonate salts, e.g., calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, e.g., nonylphenol-C.sub.18 ethoxylate; alcohol-alkylene oxide addition products, e.g., tridecyl alcohol-C.sub.16 ethoxylate; soaps, e.g., sodium stearate; alkylnaphthalene sulfonate salts, e.g., sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, e.g., sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, e.g., sorbitol oleate; quaternary amines, e.g., lauryltrimethylammonium chloride; polyethylene glycol esters of fatty acids, e.g., polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono and dialkyl phosphate esters.
[0483] Other additives commonly used in agricultural compositions include crystallization inhibitors, viscosity modifiers, suspending agents, spray droplet regulators, pigments, antioxidants, foaming agents, defoaming agents, light-shielding agents, compatibilizers, chelating agents, neutralizing agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, micronutrients, mitigating agents, lubricants, and fixing agents.
[0484] In addition, other biocides or compositions may be combined with the composition of the present invention and used in the method of the present invention, and may be applied simultaneously or sequentially with the composition of the present invention. When applied simultaneously, the further active ingredients may be compounded together with the composition of the present invention, or mixed, for example, in a spray tank. The further biocides may be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides, plant growth regulators, and / or biological formulations.
[0485] The following combinations of the compound of formula I with another active substance in a 1:1 weight ratio are preferred (where the abbreviation "TX" means "one compound selected from the compounds defined in Tables 1.1 to 1.315 and Table A"): (7E,9Z)-Dodeca-7,9-diene-1-ylacetate+TX, (9Z,11E)-Tetradeca-9,11-diene-1-ylacetate+TX, (9Z,12E)-Tetradeca-9,12-diene-1-ylacetate+TX, (E)-6-methylhepta-2-en-4-ol+TX, (E)-Deca-5-en-1-ol+TX, (E)-Trideca-4-en-1-ylacetate+TX, (E,Z)-Tetradeca-4,10-diene-1 -Illacetate+TX, (Z)-Dodeca-7-en-1-Illacetate+TX, (Z)-Hexadeca-11-en-1-Illacetate+TX, (Z)-Hexadeca-11-enal+TX, (Z)-Hexadeca-13-en-11-in-1-Illacetate+TX, (Z)-Icosa-13-en-10-on+TX, (Z)-Tetradeca-7-en-1-al+TX, (Z)-Tetradeca-9-en-1-all+TX, (Z)-Tetradeca-9-en-1-Illacetate+TX, 1,2-Dibromo- 1,2-dichloropropane, 1,3-dichloropropene + TX, 1,2-dichloropropane + TX, 1,3-dichloropropene + TX, 1,4-methyloctadeca-1-ene + TX, 1-hydroxy-1H-pyridine-2-thione + TX, 2-(octylthio)ethanol + TX, 2-chlorophenyl N-methylcarbamate (CPMC) + TX, 3-(4-chlorophenyl)-5-methylrhodanine + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide + TX, 4-(quinoxaline-2-ylamino)benzenesulfonamide + TX, 4-methylnonan-5-ol having 4-methylnonan-5-one + TX, 5-methyl-6-thioxo-1,3,5-thiadiadinane-3-ylacetic acid + TX, 6-isopentenylaminopurine + TX, 8-hydroxyquinoline sulfate + TX, abamectin + TX, acequinosyl + TX, acetamiprid + TX, acetoprole + TX, acrinatrin + TX, acinonapyr + TX, apple tortrix moth (Adoxophyes orana) GV + TX, afidopiropene + TX, afoxolaner + TX, Agrobacterium radiobacterRadiobacter) + TX, AKD-3088 + TX, Aranicarb + TX, Aldicarb + TX, Aldoxycarb + TX, Allethrin + TX, Alpha-cypermethrin + TX, Alpha-mesrin + TX, Alpha-multistriatin + TX, Amblyseius spp. + TX, Amidoflumet + TX, Amino Acids + TX, Aminocarb + TX, Anagrapha falcifera NPV + TX, Anagrus atomus + TX, Aphelinus abdominalis + TX, Aphidius colemani + TX, Aphidoletes aphidimyza + TX, Aphorate + TX, Autographa californica NPV + TX, AZ 60541+TX, Azadirachtin+TX, Azocyclotin+TX, Bacillus aizawai+TX, Bacillus chitinosporus AQ746 (NRRL accession number B-21 618)+TX, Bacillus firmus+TX, Bacillus kurstaki+TX, Bacillus mycoides AQ726 (NRRL accession number B-21664)+TX, Bacillus pumilus (NRRL accession number B-30087)+TX, Bacillus pumilus pumilus)AQ717(NRRL accession number B-21662)+TX, Bacillus sp. AQ175(ATCC accession number 55608)+TX, Bacillus sp. AQ177(ATCC accession number 55609)+TX, Bacillus sp. AQ178(ATCC accession number 53522)+TX, Bacillus sphaericus Neide+TX, Bacillus subtilis AQ153(ATCC accession number 55614)+TX, BacillusBacillus subtilis) AQ30002 (NRRL accession number B-50421) + TX, Bacillus subtilis AQ30004 (NRRL accession number B-50455) + TX, Bacillus subtilis AQ713 (NRRL accession number B-21661) + TX, Bacillus subtilis AQ743 (NRRL accession number B-21665) + TX, Bacillus subtilis (unspecified) + TX, Bacillus thuringiensis AQ52 (NRRL accession number B-21619) + TX, Bacillus thuringiensis (Bacillus Bacillus thuringiensis)BD#32 (NRRL procurement number B-21530) + TX, Bacillus thuringiensis Berliner + TX, Bacillus thuringiensis subsp. Aizawai + TX, Bacillus thuringiensis subsp. Israelensis + TX, Bacillus thuringiensis subsp. Japonensis + TX, Bacillus thuringiensis subsp. Kurstaki + TX, Bacillus thuringiensis subsp. tenebryonis subsp.Tenebrionis)+TX, Bacillus thuringiensis subsp.kurstaki BMP 123+TX, Beauveria bassiana+TX, Beauveria bronniartiibrongniartii)+TX, bencrotiaz+TX, benomyl+TX, bensultap+TX, benzoximate+TX, benzpyrimoxane+TX, beta-cyfluthrin+TX, beta-cypermethrin+TX, betoxazine+TX, bifenazate+TX, bifenthrin+TX, binapacril+TX, bioarethrin+TX, biorethmethrin+TX, tributyltin oxide+TX, bisagil+TX, bistriflurone+TX, bisulfurfen+TX, brevicomin+TX, brofla Nilide+TX, Broflutrinate+TX, Bromoacetamide+TX, Bromophosethyl+TX, Bronopol+TX, Busulfan+TX, Butocarboxime+TX, Butopyronoxyl+TX, Butoxy(Polypropylene Glycol)+TX, Butylpyridaben+TX, Kazusaphos+TX, Calcium Arsenate+TX, Carbaryl+TX, Carbofuran+TX, Carbon Disulfide+TX, Carbosulfan+TX, Cartape+TX, CAS No.: 1594624-87-9+TX, CAS No.: 19229 57-47-8+TX, CAS number: 1255091-74-7+TX, CAS number: 1365070-72-9+TX, CAS number: 1445683-71-5+TX, CAS number: 1445684-82-1+TX, CAS number: 1594626 -19-3+TX, CAS number: 1594637-65-6+TX, CAS number: 1632218-00-8+TX, CAS number: 1808115-49-2+TX, CAS number: 1922957-46-7+TX, CAS number: 1922957-48 -9+TX, CAS number:1956329-03-5+TX, CAS number:1990457-52-7+TX, CAS number:1990457-55-0+TX, CAS number:1990457-57-2+TX, CAS number:1990457-66-3+ TX, CAS number:1990457-77-6+TX, CAS number:1990457-85-6+TX, CAS number:2032403-97-5+TX, CAS number:2044701-44-0+TX, CAS number:2095470-94-1+TX, CAS number: 2128706-04-5+TX, CAS number: 2128706-05-6+TX, CAS number: 2133042-31-4+TX, CAS number: 2133042-44-9+TX, CAS number: 2171099-09-3+TX, CAS number: 2220132-55-6+TX, CAS number: 2396747-83-2+TX, CAS number: 2408220-91-5+TX, CAS number: 2408220-94-8+TX, CAS number: 2415706:16-8+TX, piperfuranilide (CAS number: 2615135-05-0)+TX, CAS number: 2719848-60-7+TX, CAS number: RNA (Colorado Leaf Beetle (Leptinotarsa) Decemlineata-specific recombinant double-strand interference GS2) + TX, chlorantraniliprole + TX, chlordane + TX, chlorfenapyr + TX, chloropicrin + TX, chloroprallethrin + TX, chlorpyrifos + TX, chromafenozide + TX, Chrysoperla carnea + TX, clenpyrin + TX, chloetocarb + TX, clothianidin + TX, kodrellul + TX, kodremon + TX, copper acetoarsenite + TX, copper dioctanoate + TX, copper hydroxide + TX, copper sulfate + TX, cresol + TX, curufomate + TX, Cryptolaemus Montrouzieri) + TX, Kyuelle + TX, Cyanophenphos + TX, Cyantraniliprole + TX, Sibutrin + TX, Cyclaniliprole + TX, Cyclobtriflurum + TX, Cycloprotrin + TX, Cycloxapride + TX, Codringa (Cydia pomonella) GV + TX, Cyenopyrafen + TX, Cietopyrafen + TX, Cyflumetofen + TX, Cyfluthrin + TX, Cyhalodimide + TX, Cylohalothrin + TX, Cypermethrin + TX, Cyphenothrin + TX, Cyprofuranilide + TX, Cyromazine + TX, Cytokinin + TX, Dacnusa sibirica sibirica)+TX, dazomet+TX, DBCP+TX, DCIP+TX, deltamethrin+TX, diafenthiuron+TX, dialiphos+TX, diamidaphos+TX, dibrom+TX, dibutyl adipate+TX, dibutyl phthalate+TX,Dibutyl succinate + TX, Diclofenthion + TX, Diclon + TX, Dichlorophene + TX, Dicriphos + TX, Dichloromezothiaz + TX, Diethyltoluamide + TX, Diflubenzuron + TX, Diglyphus isaea isaea)+TX, dimatif+TX, dimethoate+TX, dimethylcalvert+TX, dimethyl phthalate+TX, zinpropyridaz+TX, dinactin+TX, dinocap+TX, dinotefuran+TX, dioxabenzophos+TX, dipirithione+TX, disparure+TX, D-limonene+TX, dodeca-8-en-1-ylacetate+TX, dodeca-9-en-1-ylacetate+TX, dodeca-8,10-dien-1-ylacetate+TX, dodicine+TX, dominicalle+TX, doramectin+TX, emamectin+TX, emamectin benzoate+TX, empenthrin+TX, Encarsia (formosa)+TX, Endotar+TX, Endrin+TX, Eprinomectin+TX, Epsilon-Monfluorothrin+TX, Epsilon-Metofluthrin+TX, Desert Symphyta (Eretmocerus eremicus)+TX, Esfenvalerate+TX, Ethion+TX, Ethiprole+TX, Etoprophos+TX, 4-Methyloctanoate Ethyl+TX, Ethylhexanediol+TX, Ethylenedibromide+TX, Etofenprox+TX, Ethoxazole+TX, Etopylafen+TX, Eugenol+TX, Extracts of fermentation products obtained from seaweed and Melasse+TX, Extracts of fermentation products obtained from seaweed and Melasse containing urea+TX, Extracts of seaweed and fermented plant products+TX, Seaweed and plant hormones, Vitamins, EDTA cleavage Extracts of fermented plant products containing copper, zinc, and iron +TX, Famfur +TX, Phenaminosulf +TX, Phenamiphos +TX, Phenazaquin +TX, Fenflusrin +TX, Fenitrothion +TX, Fenmezodithiaz +TX, Phenobucarb +TX, Phenothiocarb +TX, Phenoxycarb +TX, Fenpropasrin +TX, Fenpyrad +TX, Fenpyroximate +TX, Fensulfothion +TX, Fenthion +TX, Fentin +TX, Fentin acetate +TX, Fenvalerate +TX, Iron phosphate +TX,Fipronil + TX, Flomethkin + TX, Flunicamide + TX, Fluacrypyrim + TX, Fluazindolidine + TX, Fluazuron + TX, Flubendiamide + TX, Flubendimine + TX, Fluchlordiniliprole + TX, Flucitrinate + TX, Flucycloxurone + TX, Flucitrinate + TX, Fluensulfone [318290-98-1] + TX, Fluensulfone + TX, Fluphenelim + TX, Flufenprox + TX, Flufiprole + TX, Fluhexaphon + TX, Flumethrin + TX, Fluopyram + TX, Flupyradiflon + TX, Flupyrimin + TX, Flupyroxystrobin + TX, Fluralane Lu+TX, Fluvalinate+TX, Fluxamethamide+TX, Formaldehyde+TX, Fosthiazate+TX, Fosthiethane+TX, Frontalin+TX, Furfural+TX, Gamma-cyhalotrin+TX, Gossyplure(registered trademark) (1:1 mixture of (Z,E) and (Z,Z) isomers of hexadeca-7,11-dien-1-yl acetate)+TX, Grandlua+TX, Grandlua I+TX, Grandlua II+TX, Grandlua III+TX, Grandlua IV+TX, Granulosis virus+TX, Guadipyr+TX, GY-81+TX, Halfenprox+TX, Halofenozide+TX, Harbin+TX, Helicoverpa Armigera) Polyhedrosis virus + TX, Helicoverpa zea NPV + TX, Helicoverpa zea Polyhedrosis virus + TX, Heliothis punctigera Polyhedrosis virus + TX, Heliothis virescens Polyhedrosis virus + TX, Hemel + TX, Hempa + TX, Heptafluthrin + TX, Heterophos + TX, Heterorhabditis bacteriophora and H. megidis + TX, Hexalle + TX, Hexamide + TX, Hexithiazox + TX, Hippodamia convergens + TX, Hydramethylnon + TX, Hydralgafen + TX, Slaked lime + TX,Imisiaphos + TX, Imidacloprid + TX, Imiprothrin + TX, Indazapiroxameth + TX, Indoxacarb + TX, Iodomethane + TX, Iprodione + TX, Ipsdienol + TX, Ipsenol + TX, Isamidophos + TX, Isazofos + TX, Isocycloseram + TX, Isoflualanum (CAS number: 2892524-05-7) + TX, Isothioate + TX, Ibamectin + TX, Japonilua + TX, Kappa-bifenthrin + TX, Kappa-tefluthrin + TX, Kasugamycin + TX, Kasugamycin hydrochloride hydrate + TX, Kinetin + TX, Lambda-cyhalotrin + TX, Redoprona + TX, Lepimectin + TX, Leptomastix Dactylopy dactylopii)+TX, lineatin+TX, liturua+TX, lupucurure+TX, rotilaner+TX, lufenuron+TX, Macrolophus caliginosus+TX, Mamestra brassicae NPV+TX, mecarfone+TX, medolua+TX, megatomoic acid+TX, metaflumizone+TX, metaldehyde+TX, metam+TX, metam potassium+TX, metam sodium+TX, Metaphycus helvolus+TX, Metarhizium anisopliae var. acridum+TX, Metarhizium anisopliae var. anisopliae+TX, Metarhizium species spp.)+TX, Metepa+TX, Methiocarb+TX, Methiotepa+TX, Methomyl+TX, Methquin-butyl+TX, Methoxyphenozide+TX, Methylaphorate+TX, Methylbromide+TX, Methyl eugenol + TX, methyl isothiocyanate + TX, methyl neodecanamide + TX, metofluthrin + TX, metholcarb + TX, mexacalbate + TX, milbemectin + TX, milbemycin oxime + TX, monfluorothrin + TX, molzide + TX, moxidectin + TX, muscarle + TX, Muscodor albus 620 (NRRL accession number 30547) + TX, Muscodor roseus A3-5 (NRRL accession number 30548) + TX, Myrothecium verrucaria composition + TX, Narbam + TX, NC-184 + TX, lilac-based products + TX, pine sawfly (Neodiprion) N. sertifer) NPV and N. lecontei NPV + TX, Nickel bis(dimethyldithiocarbamate) + TX, Niclosamide + TX, Niclosamide olamine + TX, Nicofluprole + TX, Nitenpyram + TX, Nichiazine + TX, Nitrapyrine + TX, Octadeca-2,13-diene-1-ylacetate + TX, Octadeca-3,13-diene-1-ylacetate + TX, Octylinone + TX, Omethoate + TX, Oriflurle + TX, Orius spp. + TX, Orictalle + TX, Ostramon + TX, Oxamate + TX, Oxamyl + TX, Oxazosulfyl + TX, Oxolinic acid + TX, Oxytetracycline + TX, Paecilomyces fumosoroseus fumosoroseus)+TX, Paecilomyces lilacinus+TX, parathion-ethyl+TX, Pasteuria nishizawae+TX, Pasteuria penetrans+TX, Pasteuria ramosa+TX, Pasteuria thornei+TX, Pasteuria usgaeUsgae)+TX, P-Cymene+TX, Penflurone+TX, Pentachlorophenol+TX, Permethrin+TX, Phenothrin+TX, Phorate+TX, Phosphamidone+TX, Phosphocarb+TX, Phytoseiulus persimilis+TX, Picalidine+TX, Bioxaniliprole+TX, Piperazine+TX, Piperonylbutoxide+TX, Pyrimicarb+TX, Pyrimiphosethyl+TX, Pyrimiphosmethyl+TX, Plutella xylostella granuloma virus+TX, Plutella xylostella nuclear polyhedra virus+TX, Polyhedra virus+TX, Potassium and molybdenum and EDTA-chelated manganese+TX, Potassium ethylxanthogenic acid+TX, Potassium hydroxyquinoline sulfate Sulfate) + TX, Prallethrin + TX, Probenazole + TX, Profenofos + TX, Profluthrin + TX, Propargit + TX, Propetamphos + TX, Propoxar + TX, Prothiofos + TX, Protriffenbuto + TX, Piflubmid + TX, Pymetrozine + TX, Pyraclofos + TX, Pyrafluprole + TX, Pyridaben + TX, Pyridaryl + TX, Pyridine-4-amine + TX, Pyrifluquinazone + TX, Pyrimidifen + TX, Pyriminostrobin + TX, Pyriprole [394730-71-3] + TX, Pyriprole + TX, Pyriproxyfen + TX, QRD 420 (Terpenoid Blend) + TX, QRD 452 (Terpenoid Blend) + TX, QRD 460 (Terpenoid Blend) + TX, Quillaya saponaria) + TX, quinoclamin + TX, quinonamide + TX, resmethrin + TX, Rhodococcus globulusgloberulus)AQ719 (NRRL accession number B-21663)+TX, sarolaner+TX, S-biorethrin+TX, cebuphos+TX, selamectin+TX, siglur+TX, silafluofen+TX, simazine+TX, pentachlorophenoxide sodium+TX, sordidine+TX, spidoxamat+TX, spinetoram+TX, spinosad+TX, spirobudifen+TX, spirodiclofen+TX, spiromesifen+TX, spiropidione+TX, spirotetramato+TX, Spodoptera exigua polycapsidoneurocyte virus+TX, Spodoptera frugiperda polycapsidoneurocyte virus+TX, Steinernema viviones (Spodoptera bibionis)+TX, Steinernema carpocapsae+TX, Steinernema feltiae+TX, Steinernema glaseri+TX, Steinernema riobrave+TX, Steinernema riobravis+TX, Steinernema scapterisci+TX, Steinernema spp.+TX, Streptomyces galbus (NRRL accession number 30232)+TX, Streptomycessp.) (NRRL accession number B-30145) + TX, Streptomycin + TX, Streptomycin sesquisulfate + TX, Strychnine + TX, Sulcatol + TX, Sulfiflumin (CAS number: 2377084-09-6) + TX, Sulfoxaflor + TX, Tadimucarb + TX, Tebufenozide + TX, Tebufenpyrad + TX, Tebupirimiphos + TX, Tecrophthalam + TX, Tefluthrin + TX, Temephos + TX, Tepa + TX, Terbam + TX, Terbuphos + TX, Terpenoid blend + TX, Tetrachlorantraniliprole + TX, Tetrachlorothiophene + TX, Tetradeca-11-en-1-yl acetate + TX, Tetradiphon + TX, Tetramethrin + TX, Tetramethylfluthrin + TX, Tetranactin + TX, Tetranilipro TX, Theta-cypermethrin+TX, Thiacloprid+TX, Thiafenox+TX, Thiamethoxam+TX, Thiocyclam+TX, Thiodicarb+TX, Thiofanox+TX, Thiohempa+TX, Thiomersal+TX, Thiometon+TX, Thionadin+TX, Thiophanate+TX, Thiosultap+TX, Thiotepa+TX, Tigolaner+TX, Thiolantraniliprole+TX, Thioxazafen+TX, Tolfenpyrad+TX, Toxaphene+TX, Tralomethrin+TX, Transfluthrin+TX, Tretamine+TX, Triazamate+TX, Triazophos+TX, Triazurone+TX, Tributyltin oxide+TX, Trichlorfon+TX, Trichloronate+TX, Trichlorfon+TX, Trichogramma species spp.)+TX, triphenmorph+TX, trifluenfronate+TX, triflumezopyrim+TX, trimedrua+TX, trimedrua A+TX, trimedrua B1+TX, trimedrua B2+TX, trimedrua C+TX, trimetacarb+TX, triphenyltin acetate+TX, triphenyltin hydroxide+TX, trunk-call+TX, cyclopyrazoflor+TX, Typhlodromus occidentalis+TX, uredepa+TX, Verticillium lecanii+TX, Verticillium species(spp.) + TX, xylenol + TX, YI-5302 + TX, zeatin + TX, zeta-cypermethrin + TX; N-[(1R)-1-benzyl-3-chloro-1-methylbuta-3-enyl]-8-fluoroquinoline-3-carboxamide+TX, N-[(1S)-1-benzyl-3-chloro-1-methylbuta-3-enyl]-8-fluoroquinoline-3-carboxamide+TX, N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine (These compounds are from the country (These compounds may be prepared by the method described in International Publication No. 2019 / 110427) + TX, (3'',4'',5''-trifluorobiphenyl-2-yl)-amide + TX, (3-methylisoxazole-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methanone (These compounds may be prepared by the method described in International Publication No. 2017 / 220485) + TX, (4-phenoxyphenyl )Methyl 2-amino-6-methylpyridine-3-carboxylate (this compound may be prepared from the method described in International Publication No. 2014 / 006945) + TX, (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methanone + TX, (7E,9Z)-dodeca-7,9-diene-1-ylacetate + TX, (9Z,11E)-tetradeca-9,11-diene-1-ylacetate (E)-deca-5-en-1-ylacetate having tate + TX, (9Z,12E)-tetradeca-9,12-diene-1-ylacetate + TX, (E)-6-methylhepta-2-en-4-ol + TX, (E)-deca-5-en-1-ol + TX, (E)-trideca-4-en-1-ylacetate + TX, (E,Z)-tetradeca-4,10-diene-1-ylacetate + TX, (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, (Z)-dodeca-7-en-1-ylacetate + TX, (Z)-hexadeca-11-en-1-ylacetate + TX, (Z)-hexadeca-11-enal + TX, (Z)-hexadeca-13-en-11-in-1-ylacetate + TX, (Z)-icosa-13-en-10-one + TX, (Z)-tetradeca-7-en-1-al + TX, (Z)-tetradeca-9-en-1-ol + TX, (Z)-tetradeca-9-en-1-ylacetate + TX, (Z,2 E)-5-[1-(2,4-dichlorophenyl)pyrazole-3-yl]oxy-2-methoxyimino-N,3-dimethyl-penta-3-enamide (this compound may be prepared from the method described in International Publication No. 2018 / 153707) + TX, (Z,2E)-5-[1-(4-chlorophenyl)pyrazole-3-yl]oxy-2-methoxyimino-N,3-dimethyl-penta-3-enamide + TX, [2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazole-1-yl]acetyl]-4-piperidyl]thiazole- 4-yl]-4,5-dihydroisoxazole-5-yl]-3-chlorophenyl]methanesulfonate + TX, 1-(4,5-dimethylbenzimidazole-1-yl)-4,4,5-trifluoro-3,3-dimethylisoquinoline + TX, 1-(4,5-dimethylbenzimidazole-1-yl)-4,4-difluoro-3,3-dimethylisoquinoline + TX, 1-(6,7-dimethylpyrazolo[1,5-a]pyridine-3-yl)-4,4,5-trifluoro-3,3-dimethylisoquinoline + TX, 1-(6,7-dimethylpyrazolo[1 ,5-a]pyridine-3-yl)-4,4,6-trifluoro-3,3-dimethylisoquinoline + TX, 1-(6-chloro-7-methyl-pyrazolo[1,5-a]pyridine-3-yl)-4,4-difluoro-3,3-dimethylisoquinoline (these compounds may be prepared from the method described in International Publication No. 2017 / 025510) + TX, 1,1-bis(4-chlorophenyl)-2-ethoxyethanol + TX, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane + TX, 1,2-dibromo-3-chloropropane + TX, 1,1,2-dichloropropane, 1,3-dichloropropene + TX, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]urea + TX, 1-[2-[[1-(4-chlorophenyl)pyrazole-3-yl]oxymethyl]-3-methylphenyl]-4-methyltetrazole-5-one + TX, 10-diene-1-ylacetate + TX, 14-methyloctadeca-1-ene + TX, 1-bromo-2-chloroethane + TX, 1- Dichloro-1-nitroethane + TX, 1-hydroxy-1H-pyridine-2-thione + TX, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]urea + TX, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazole-1-yl)phenoxy]methyl]phenyl]tetrazol-5-one + TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxy Samide + TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide + TX, 2-(1,3-dithiolan-2-yl)phenyldimethylcarbamate + TX, 2-(2-butoxyethoxy)ethylpiperonilate + TX, 2-(2-butoxyethoxy)ethylthiocyanate + TX, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenylmethylcarbamate + TX, 2-(4-chloro-3,5-xylyloxy)ethanol + TX, 2-(difluoromethyl (3R)-N-(3-ethyl-1,1-dimethylindan-4-yl)pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethylindan-4-yl]pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethylindan-4-yl]pyridine-3-carboxamide (this compound may be prepared from the method described in International Publication No. 2014 / 095675) + TX, 2-(difluoromethyl)-N-[3-ethyl-1,1-Dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, 2-(octylthio)ethanol + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate + TX, 2,2-dichlorovinyl 2-ethylsulfinylethylmethyl phosphate + TX, 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]acetamide + TX, 2,4-dichlorophenylbenzenesulfonate + TX, 2,6 -dimethyl-1H,5H-[1,4]ditiino[2,3-c:5,6-c'']dipyrrole-1,3,5,7(2H,6H)-tetron (this compound may be prepared by the method described in International Publication No. 2011 / 138281) + TX, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol + TX, 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazole-1-yl)propan- 2-ol (this compound may be prepared by the method described in International Publication No. 2017 / 029179) + TX, 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazole-1-yl)propan-2-ol (this compound may be prepared by the method described in International Publication No. 2017 / 029179) + TX, 2-chlorovinyl diethyl phosphate + TX, 2-fluoro-N-methyl-N-1-naphthylacetamide + TX, 2-imidazoly Don + TX, 2-Isovalerylindan-1,3-dione + TX, 2-Methyl(propa-2-inyl)aminophenylmethylcarbamate + TX, 2-Oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]acetamide (this compound may be prepared from the method described in International Publication No. 2018 / 065414) + TX, 2-Thiocyanatoethyl laurate + TX, 3-(4,4-Difluoro-3,3-dimethyl-1-isoquinolyl)-7,8-Dihydro-6H-cyclopenta[e]benzimidazole (these compounds may be prepared from the method described in International Publication No. 2016 / 156085) + TX, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinoline-1-yl)quinolone + TX, 3-(4-chlorophenyl)-5-methylrhodanine + TX, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxy SID + TX, 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile (this compound may be prepared by the method described in International Publication No. 2016 / 156290) + TX, 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile (this compound may be prepared by the method described in International Publication No. 2016 / 156290) + TX, 3-bromo-1 -Chloropropane + TX, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine + TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid + TX, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]urea + TX, 3-methyl-1-phenylpyrazole-5-yldimethylcarbamate + TX, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl Nyl)-1,3-dimethyl-1H-pyrazole-5-amine + TX, 4-(2,6-difluorophenyl)-6-methyl-5-phenylpyridazine-3-carbonitride + TX, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-2,5-dimethylpyrazole-3-amine + TX, 4-(quinoxaline-2-ylamino)benzenesulfonamide + TX, 4,4-difluoro-1-(5-fluoro-4-methyl-benzimidazole-1-yl)-3,3-dimethylisoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(6-methylpyrazolo[1,5-a]pyridine-3-yl)isoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a]pyridine-3-yl)isoquinoline + TX, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]isoxazolidine-3-one + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1 -Difluoro-2-hydroxy-3-(1,2,4-triazole-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazole-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4H- 1,2,4-Triazole-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, 4-Chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazine-3-one + TX, 4-Chlorophenylphenylsulfone + TX, 4-Methyl(propane-2-inyl)amino-3,5-xylylmethylcarbamate + TX, 4-methylnonan-5-one + TX, 4-methylnonan-5-ol, 5-(1,3-benzodioxane) (Lu-5-yl)-3-hexylcyclohexa-2-enone + TX, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]isoxazolidine-3-one + TX, 5,5-dimethyl-3-oxocyclohexa-1-enyldimethylcarbamate + TX, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt (2:1) + TX, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid + TX,6-Chloro-3-(3-cyclopropyl-2-fluorophenoxy)-N-[2-(2,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methylpyridazine-4-carboxamide (may be prepared from the method described in International Publication No. 2020 / 109391) + TX, 6-Chloro-3-(3-cyclopropyl-2-fluorophenoxy)-N-[2-(3,4-dimethylphenyl)-2,2-difluoro Ro-ethyl]-5-methylpyridazine-4-carboxamide (may be prepared from the method described in International Publication No. 2020 / 109391) + TX, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazole-1-yl)isoquinoline + TX, 6-chloro-N-[2-(2-chloro-4-methylphenyl)-2,2-difluoro-ethyl]-3-(3-cyclopropyl-2-fluoro- Phenoxy)-5-methylpyridazine-4-carboxamide (may be prepared from the method described in International Publication No. 2020 / 109391) + TX, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithiino[1,2-c]isothiazole-3-carbonitrile + TX, 6-isopentenylaminopurine + TX, 8-fluoro-N-[(1R)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl -Butyl]quinoline-3-carboxamide+TX, 8-fluoro-N-[(1S)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide+TX, 8-hydroxyquinoline sulfate+TX, acetylone+TX, acetoprole+TX, acibenzolar+TX, acibenzolar-S-methyl+TX, acrylonitrile+TX, apple tortrix (Adoxophyes) orana) GV+TX, Agrobacterium radiobacter+TX, Aldoxicarb+TX, Aldrin+TX, Allosamidin+TX, Alixicarb+TX, Alpha-chlorohydrin+TX, Alpha-ecdysone+TX, Alpha-multistriatin+TX, Aluminum phosphide+TX, Amblyseius spp.+TX, Amectotractin+TX, Ametoctrazine+TX,Amidithione + TX, Amidothioate + TX, Aminocarb + TX, Aminopyriphen + TX, Amisulbrom + TX, Amiton + TX, Amiton Hydroxate + TX, Amitraz + TX, Anabacin + TX, Anagrapha falcifera NPV + TX, Anagrus atomus + TX, Ancimidor + TX, Anilazine + TX, Anisifurupurine + TX, Anthraquinone + TX, Antu + TX, Aphelinus abdominalis + TX, Aphidius colemani + TX, Aphidoletes aphidimyza + TX, Aphorate + TX, Aramite + TX, Arsenic Trioxide + TX, Atidathion + TX, Autographa californica Bacillus californica NPV+TX, azobenzene azaconazole+TX, azamethiphos+TX, azobenzene+TX, azothoate+TX, azoxystrobin+TX, Bacillus sphaericus Neide+TX, Bacillus thuringiensis delta-endotoxin+TX, barium carbonate+TX, barium hexafluorosilicate+TX, barium polysulfide+TX, bartholin+TX, Bayer 22 / 190+TX, Bayer 22408+TX, Beauveria bronniartii brongniartii)+TX, Benalaxyl+TX, Bencrotiaz+TX, Benomyl+TX, Benoxaphos+TX, Bentiavaricarb+TX, Benzothiostrobin+TX, Benzovindiflupir+TX, Benzyl benzoate+TX, Beta-cyfluthrin+TX, Beta-cypermethrin+TX, Betoxazine+TX, Bioetanomethrin+TX, Biopermethrin+TX, Bis(2-chloroethyl) ether+TX, Tributyltin oxide+TX, Bisazil+TX, Bisthiosemi+TX, Vitertanol+TX, Bixafen+TX, Blastocydin-S+TX, Borax+TX, Bordeaux mixture+TX, Boscalid+TX, Brevicomin+TX, Brodifacum+TX, Brofenvalerate+TX,Bromadiolon + TX, Bromesalen + TX, Bromufenbinphos + TX, Bromoacetamide + TX, Bromocyclene + TX, Bromo-DDT + TX, Bromophos + TX, Bromopropylate + TX, Bromuconazole + TX, Bronopol + TX, Bufencarb + TX, Bupirimate + TX, Buprofezin + TX, Busulfan + TX, Buta-3-inyl N-[6-[[(Z)-[(1-methyltetrazole-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate + TX, Butacarb + T X, Butathiophos + TX, Butocarboxim + TX, Butonate + TX, Butopyronoxyl + TX, Butoxy(polypropylene glycol) + TX, Butoxycarboxim + TX, Butylpyridaben + TX, Calcium arsenate + TX, Calcium cyanide + TX, Polysulfide calcium + TX, Campechlor + TX, Captafor + TX, Captan + TX, Carbanolate + TX, Carbendazim + TX, Carbon disulfide + TX, Carbon tetrachloride + TX, Carbophenothion + TX, Carboxine + TX, Cartap hydrochloride + TX, CAS number: 2132414-04-9+TX, CAS number: 2344721-61-3+TX, Sebazin+TX, Quinomethionat+TX, Chloralose+TX, Chlorbenside+TX, Chlorbicurene+TX, Chlordane+TX, Chlordecone+TX, Chlordimeform+TX, Chlordimeform hydrochloride+TX, Chlorphenetol+TX, Chlorfensone+TX, Chlorfensulfide+TX, Chlorbenzilate+ TX, chloroform + TX, chloroinconazide + TX, chloromebform + TX, chloromethiurone + TX, chloroneb + TX, chlorofacinone + TX, chloropicrin + TX, chloropropylate + TX, chlorothalonil + TX, chlorfoxime + TX, chlorprazofos + TX, chlorthiofos + TX, clozolinate + TX, cholecalciferol + TX, Chrysoperla carnea + TX, synerin I + TX, synerin II + TX, synerin + TX, cismethrin + TX, cis-resmethrin + TX, crocitrin + TX, closantel + TX, kodrelle + TX, kodremon + TX, copper acetoarsenite + TX, copper arsenate + TX, copper dioctanoate + TX, copper hydroxide + TX,Copper naphthenate + TX, copper oleate + TX, copper oxide + TX, copper oxychloride + TX, copper sulfate + TX, coumaflyl + TX, coumaphos + TX, coumatetralyl + TX, spider methoxystrobin (dioxyanguine) + TX, coumithoate + TX, spideroxystrobin + TX, cresol + TX, crimidine + TX, crotamiton + TX, clotoxyphos + TX, clufomate + TX, cryolite + TX, ladybug (Cryptolaemus montrouzieri) + TX, CS 708 + TX, cuerule + TX, cufraneb + TX, cyanophenphos + TX, cyanophos + TX, cyanthoate + TX, cyazofamide + TX, sibutrin + TX, ciclethrin + TX, cyclobutriflurum + TX, chodringa (Cydia) Pomonella GV + TX, Cyflufenamid + TX, Simiazole + TX, Cymoxanil + TX, Cyproconazole + TX, Cyprodinil + TX, Cithioate + TX, Cytokinin + TX, Dacnusa sibirica + TX, DAEP + TX, Dazomet + TX, DCIP + TX, DCPM + TX, DDT + TX, Debacarb + TX, Decarbofuran+TX, Demefion+TX, Demefion-O+TX, Demefion-S+TX, Demeton-Methyl+TX, Demeton-O+TX, Demeton-O-Methyl+TX, Demeton-S+TX, Demeton-S-Methyl+TX, Demeton-S-Methylsulfone+TX, Diamidaphos+TX, Dibutyl Adipate+TX, Dibutyl Phthalate+TX, Dibutyl Succinate+TX, Dicapton+TX, Diclobentiazox+TX, Diclofenthion+TX, Diclofluanide+TX, Diclon+TX, Dichlorophen+ TX, Dichlorvos+TX, Diclozoline+TX, Dicrifos+TX, Diclosimet+TX, Diclomazine+TX, Dichloran+TX, Dicresil+TX, Dicyclanil+TX, Dicyclopentadiene+TX, Dierdrin+TX, Dienochlor+TX, Dietofencarb+TX, Diethyl 5-methylpyrazole-3-ylphosphate+TX, Diethyltoluamide+TX, Diphenacum+TX, Difenoconazole+TX, Difethiaron+TX, Diflovidazine+TX, Diglyphus isaea+TX, Dirol+TX, Dimatif+TX, Dimefluthrin+TX, Dimefox+TX, Dimethane+TX, Dimethilimol+TX, Dimethomorph+TX, Dimethrin+TX, Dimethylcarbate (dimethyl carboxymethyl Carbate) + TX, Dimethyl phthalate + TX, Dimethylvinphos + TX, Dimethilane + TX, Dimoxystrobin + TX, Dynex + TX, Dynex-Dicrexin + TX, Diniconasol + TX, Dinocap-4 + TX, Dinocap-6 + TX, Dinoctone + TX, Dinopenton + TX, Dinoprop + TX, Dinosam + TX, Dinoseb + TX, Dinosulfone + TX, Dinoterbone + TX, Diophenolane + TX, Dioxabenzophos + TX, Dioxathion +TX, Diphacinone +TX, Diphenylsulfone +TX, Dipimethitron +TX, Dipirithione +TX, Disparure +TX, Disulfiram +TX, Dithianone +TX, Diticlophos +TX, DNOC +TX, Dodeca-8-en-1-ylacetate +TX, Dodeca-9-en-1-ylacetate +TX, Dodeca-8 +TX, Dodemorph +TX, Dodicin +TX, Dozin +TX, Dofenapine +TX, Dominicalle +TX, Doramectin +TX, DSP +TX,d-tetramethrin + TX, ecdysterone + TX, edifenphos + TX, EI 1642 + TX, EMPC + TX, Encarsia formosa + TX, Endotar + TX, Endothion + TX, Enestrobrin + TX, Enoxastrobin + TX, EPBP + TX, Epoxyconazole + TX, Eprinomectin + TX, Eretmocerus eremicus)+TX, ergocalciferol+TX, ethafos+TX, etaboxam+TX, ethiofencarb+TX, etyrimol+TX, ethoatemethyl+TX, ethyl 1-[[4-[(Z)-2-ethoxy-3,3,3-trifluoropropa-1-enoxy]phenyl]methyl]pyrazole-3-carboxylate (may be prepared from the method described in International Publication No. 2020 / 056090)+TX, ethyl 1-[[4-[[ 2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]pyrazole-3-carboxylate (may be prepared from the method described in International Publication No. 2020 / 056090) + TX, ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]pyrazole-4-carboxylate + TX, ethyl 1-[[5-[5-(trifluoromethyl)-1,2,4 -Oxadiazole-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylate (this compound may be prepared by the method described in International Publication No. 2018 / 158365) + TX, ethyl 4-methyloctanoate + TX, ethyl formate + TX, ethyl hexanediol + TX, ethylene dibromide + TX, ethylene dichloride + TX, ethylene oxide + TX, etridiazole + TX, etrimphos + TX, eugenol + TX, E Farnesol containing XD+TX, famoxadone+TX, farnesol+TX, nerolidol+TX, phenamidone+TX, phenaminosulf+TX, phenaminestrobin+TX, phenalimol+TX, phenazaflor+TX, fenbuconazole+TX, fenbutatine oxide+TX, fenchlorfos+TX, phenetacarb+TX, fenflam+TX, fenhexamide+TX, fenitrothion+TX, phenothiocarb+TX,Phenoxacrim+TX, Phenoxanil+TX, Fenpiclonil+TX, Fenpicoxamide+TX, Fenpyritrin+TX, Fenpropidine+TX, Fenpropimorph+TX, Fenpyrad+TX, Fenpyrazamine+TX, Fenpyroximate+TX, Fenson+TX, Fensulfothione+TX, Fenthion+TX, Fenthion-ethyl+TX, Fentin+TX, Fentriphanil+TX, Ferbam+TX, Ferimzon+TX, Iron phosphate+TX, Furocumafen+TX, Florylpicoxamide+TX, Fluazinam+TX, Fluventeram+TX, Flubendimine+TX, Flucoflon+TX, Flucycloxlon+TX, Fludioxon Fluenyl+TX, Fluphenoxadiazam+TX, Fluphenoxystrobin+TX, Fluindapir+TX, Flumethylsulfolimu+TX, Flumorph+TX, Fluopicolide+TX, Fluopimomid+TX, Fluopyram+TX, Fluolbenside+TX, Fluoroacetamide+TX, Fluorimide+TX, Fluoxapiproline+TX, Fluoxastrobin+TX, Fluoxythioconazole+TX, Flupropazine+TX, Flupropazine hydrochloride+TX, Fluquinconazole+TX, Flusilazole+TX, Flusulfamide+TX, Fluthianil+TX, Flutranil+TX, Flutriafoll+TX, Fluxapiroxad+TX, FMC 1137+TX, Forpet+TX, Formaldehyde+TX, Formethanate+TX, Formetanate+TX, Formparanate+TX, Fosetyl-aluminum+TX, Fosmethilan+TX, Fosspire+TX, Fosthietan+TX, Frontalin+TX, Fuberidazole+TX, Flalaxil+TX, Flamethopyr+TX, Flathiocarb+TX, Fretolin+TX, Furfural+TX, Gamma-HCH+TX, Glyodin+TX, Grandlua+TX, Grandlua I+TX, Grandlua II+TX, Grandlua III+TX, Grandlua IV+TX, Guazatin+TX, Guazatin acetate+TX, Halfenprox+TX, HCH+TX, Hemel+TX, Hempa+TX, HEOD+TX, Heptachlor+TX, Heterophos+TX,Heterorhabditis bacteriophora and H. megidis + TX, hexaconazole + TX, hexadecylcyclopropane carboxylate + TX, hexalle + TX, hexamide + TX, HHDN + TX, and Hippodamia (concentrates) + TX, hydralgafen + TX, slaked lime + TX, hydrogen cyanide + TX, himexazole + TX, hikincarb + TX, imanin + TX, imazalil + TX, imibenconazole + TX, iminoctadine + TX, impulfluxam + TX, ipconazole + TX, ipfentrifluconazole + TX, ipflufenoquin + TX, iprobenphos + TX, iprodione + TX, iprovalicarb + TX, ipsdienol + TX, ipsenol + TX, IPSP + TX, isamidophos + TX, isazofos + TX, isobenzan + TX, isocarbophos + TX, isodrine + TX, isofe Nphos + TX, Isofetamide + TX, Isoflucipram + TX, Isolan + TX, Isoprothiolan + TX, Isopyrazam + TX, Isothianil + TX, Isoxathion + TX, Japonila + TX, Jasmolin I + TX, Jasmolin II + TX, Iodophenphos + TX, Juvenile Hormone I + TX, Juvenile Hormone II + TX, Juvenile Hormone III + TX, Cadetrin + TX, Kasugamycin + TX, Kasugamycin Hydrochloride Hydrate + TX, Kelevan + TX, Kinetin + TX, Quinoprene + TX, Kresoxim-Methyl + TX, Lead Arsenate + TX, Leptomastix Dactylopia dactylopii)+TX, leptophos+TX, lindan+TX, lineatin+TX, lilymphos+TX, liturrh+TX, lupulure+TX, rubenmixianan+TX, lithidathione+TX, Macrolophus caliginosus+TX, magnesium phosphide+TX, maronoben+TX, Mamestra brassicae NPV+TX, mancopper+TX, mancozeb+TX, mandestrobin+TX, mandipropamide+TX, maneb+TX, mazidox+TX, m-cumenylmethylcarbamate+TX, mecarbam+TX, mecarbhon+TX,Medrua + TX, mefentrifluconazole + TX, megatomoic acid + TX, menazone + TX, mepanipyrim + TX, meperfluthrin + TX, mephosphoran + TX, mepronil + TX, mercury oxide + TX, mercury chloride + TX, Mesulfen + TX, Mesulfenphos + TX, Metalaxyl + TX, Metam + TX, Metam potassium + TX, Metam sodium + TX, Metaphycus helvolus + TX, Metarhizium anisopliae var. acridum + TX, Metarhizium anisopliae var. anisopliae (var. anisoopliae) + TX, methallyl picoxamide + TX, metconazole + TX, metepa + TX, methacryphos + TX, methanesulfonyl fluoride + TX, metasulfocarb + TX, methiotepa + TX, metoclotophos + TX, methoprene + TX, metoquin-butyl + TX, methotrin + TX, methoxychlor + TX, methyl(Z)-2-(5-cyclohexyl-2-methylphenoxy)-3-methoxy C-propa-2-enoate + TX, methyl(Z)-2-(5-cyclopentyl-2-methylphenoxy)-3-methoxypropa-2-enoate (These compounds may be prepared from the method described in International Publication No. 2020 / 193387) + TX, methyl(Z)-2-[5-(3-isopropylpyrazole-1-yl)-2-methylphenoxy]-3-methoxypropa-2-enoate + TX, methyl ( Z)-3-Methoxy-2-[2-methyl-5-(3-propylpyrazole-1-yl)phenoxy]propa-2-enoate + TX, Methyl(Z)-3-Methoxy-2-[2-methyl-5-(4-propyltriazole-2-yl)phenoxy]propa-2-enoate + TX, Methyl(Z)-3-Methoxy-2-[2-methyl-5-[3-(trifluoromethyl)pyrazole-1-yl]phenoxy]propa-2-eno Eth (these compounds may be prepared from the method described in International Publication No. 2020 / 079111) + TX, methyl(Z)-3-methoxy-2-[2-methyl-5-[4-(trifluoromethyl)triazole-2-yl]phenoxy]propane-2-enoate + TX, methyl aphorate + TX, methyl bromide + TX, methyl eugenol + TX, methyl isothiocyanate + TX, methyl N-[[4-[1-(2,6-Difluoro-4-isopropylphenyl)pyrazole-4-yl]-2-methylphenyl]methyl]carbamate (may be prepared by the method described in International Publication No. 2020 / 097012) + TX, Methyl N-[[4-[1-(4-cyclopropyl-2,6-difluorophenyl)pyrazole-4-yl]-2-methylphenyl]methyl]carbamate (may be prepared by the method described in International Publication No. 2020 / 097012) (Also good) +TX, Methyl N-[[5-[4-(2,4-dimethylphenyl)triazole-2-yl]-2-methylphenyl]methyl]carbamate +TX, Methyl chloroform +TX, Methylene chloride +TX, Methylneodecanamide +TX, Methylram +TX, Methylcarb +TX, Metominostrobin +TX, Methoxadiazone +TX, Metraphenone +TX, Methyltetraprole +TX, MGK 264 +TX, Milbemycin oxime +TX, Mipafox +TX, Myrex +TX, Monoclotophos +TX, Morphothion +TX, Morzide +TX, Moxidectin +TX, Muscarle +TX, Mycrobutanil +TX, Mycrozolin +TX, Myrothecium bergaria (verrucaria) composition + TX, N-((1R)-1-benzyl-3-chloro-1-methyl-buta-3-enyl)-8-fluoro-quinoline-3-carboxamide (These compounds may be prepared by the method described in International Publication No. 2017 / 153380) + TX, N-((1S)-1-benzyl-3-chloro-1-methyl-buta-3-enyl)-8-fluoro-quinoline-3-carboxamide (These compounds may be prepared by the method described in International Publication No. 2017 / 153380) (may be manufactured) + TX, N''-(2,5-dimethyl-4-phenoxyphenyl)-N-ethyl-N-methyl-formamidine + TX, N''-(2-chloro-5-methyl-4-phenoxyphenyl)-N-ethyl-N-methyl-formamidine + TX, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]propanamide + TX, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-Oxadiazole-3-yl]phenyl]methyl]-1,2,4-triazole-3-amine (These compounds may be prepared by the methods described in International Publication Nos. 2017 / 055473, 2017 / 055469, 2017 / 093348, and 2017 / 118689) + TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoroquinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro- Quinoline-3-carboxamide+TX, N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoroquinoline-3-carboxamide+TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoroquinoline-3-carboxamide+TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-8-fluoroquinoline-3-carboxamide+TX, N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoroquinoline N-3-carboxamide + TX, N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]benzamide + TX, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]benzamide + TX, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]propanamide + TX, N-[2-[2,4-dichlorophenoxy]phenyl]-3-(difluoro Methyl)-1-methylpyrazole-4-carboxamide + TX, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methylpyrazole-4-carboxamide + TX, N''-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidine (this compound may be prepared from the method described in International Publication No. 2016 / 202742) + TX, N''-[4-(4,5-dichlorothiazole-2-yl)oxy-2,5-dimethylphenyl]-N-ethyl-N-methyl-formamidine + TX, N''-[5-bromo-2-methyl-6-(1-methyl-2-propoxyethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N''-[5-bromo-2-methyl-6-(1-methyl-2-propoxyethoxy)-3-pyridyl]-N-isopropyl-N-methyl-formamidine (These compounds are prepared by the method described in International Publication No. 2015 / 155075) (May be prepared from the method described in IPCOM000249876D) + TX, N''-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine (This compound may be prepared from the method described in IPCOM000249876D) + TX, N''-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxyethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N''-[5-bromo-2-methyl-6-[(1S)-1 -methyl-2-propoxyethoxy]-3-pyridyl]-N-ethyl-N-methylformamidine+TX, N''-[5-chloro-2-methyl-6-(1-methyl-2-propoxyethoxy)-3-pyridyl]-N-ethyl-N-methylformamidine+TX, N-[N-methoxy-C-methylcarbonimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]benzamide (These compounds are from International Publication No. 2018 / 202428) (These compounds may be prepared by the method described in International Publication No. 2018 / 228896) + TX, N'-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine (These compounds may be prepared by the method described in International Publication No. 2018 / 228896) + TX, Narbam + TX, Naphthalophos + TX, Nared + TX, Naphthalene + TX, NC-170 + TX, Neodiprion sertifer NPV and N. lecontei NPV + TX, Nerolidol + TX, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-Oxadiazole-3-yl]phenyl]methyl]propanamide + TX, N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)oxetane-2-yl]phenyl]-N-methyl-formamidine + TX, Nickel bis(dimethyldithiocarbamate) + TX, Niclosamide olamine + TX, Nicotin + TX, Nicotin sulfate + TX, Niflulidide + TX, Nikcomycin + TX, N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenyl-ethyl)phenyl]-N-methyl-formamidine + TX, Nichiazine + TX, Nitrapyrine + TX, Nitrilacarb + TX, Nitrilacarb 1:1 zinc chloride complex + TX, Nitrotar-isopropyl + TX, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]cyclopropanecarboxamide + TX, N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]benzamide + TX, N-methyl-4-[5-(triflu Oromethyl)-1,2,4-Oxadiazole-3-yl]benzenecarbothioamide + TX, norbolmid + TX, Nualimol + TX, O,O,O'',O''-Tetrapropyldithiopyrophosphate + TX, Octadeca-2,13-dien-1-yl acetate + TX, Octadeca-3,13-dien-1-yl acetate + TX, Octylinone + TX, Ofrace + TX, Oleic acid + TX, Omethoate + TX, Orflurole + TX, Orius species spp.)+TX, Orictalle+TX, Orysastrobin+TX, Ostramon+TX, Oxadixyl+TX, Oxamate+TX, Oxathiapiproline+TX, Oxine-copper+TX, Oxolinic acid+TX, Oxycarboxyne+TX, Oxideprophos+TX, Oxydisulfon+TX, Oxytetracycline+TX, Paclobutrazol+TX, Paecilomyces fumosoroseus+TX, Para-dichlorobenzene+TX, Parathion+TX, Parathion-methyl+TX, Pefurazoate+TX, Penconazole+TX, Pencyclon+TX, Penflufen+TX, Penflulon+TX, Pentachlorophenol+TX, Pentachlorophenyl laurate+TX, Penthiopyrad+TX, Permethrin+TX, pH 60-38+TX, phenamacryl+TX, fencapton+TX, fosacetim+TX, phosalon+TX, phosdiphen+TX, phosphoran+TX, phosglycine+TX, fosniclor+TX, phosphamidone+TX, phosphine+TX, phosphorus+TX, phoxim-methyl+TX, phthalide+TX, *Phytoseiulus*persimilis)+TX, picarbtrazox+TX, picaridin+TX, picoxystrobin+TX, pindone+TX, piperazine+TX, piperonyl butoxide+TX, piprotal+TX, pyrimetaphos+TX, polychlorodicyclopentadiene isomer+TX, polychloroterpene+TX, polynactin+TX, polyoxin+TX, potassium arsenite+TX, potassium ethylxanthogenicate+TX, potassium hydroxyquinoline sulfate+TX, potassium thiocyanate Mu+TX, pp''-DDT+TX, Precosen I+TX, Precosen II+TX, Precosen III+TX, Primidophos+TX, Probenazole+TX, Prochloraz+TX, Proclonol+TX, Procymidone+TX, Profluthrin+TX, Promacil+TX, Promecarb+TX, Propamocarb+TX, Propiconazole+TX, Propineb+TX, Propoxar+TX, Propropyl isomer+TX, Proquinazide+TX, Protidathion+TX, Prothioconazole Lu+TX, Prothiophos+TX, Protoate+TX, Pidiflumetofen+TX, Pyraclostrobin+TX, Pyramethrostrobin+TX, Pyraoxystrobin+TX, Pyrapropoin+TX, Pyraziflumid+TX, Pyrazophos+TX, Pyrethmetrin+TX, Pyrethrin I+TX, Pyrethrin II+TX, Pyrethrin+TX, Pyribencarb+TX, Pyridaclomethyl+TX, Pyridafenthion+TX, Pyridine-4-amine+TX, Pyriphenox+TX, Pyrim Tanyl+TX, Pyrimitate+TX, Pyrimorph+TX, Pyrinulone+TX, Pyriophenone+TX, Pyrisoxazole+TX, Pyrroquilon+TX, Quassia+TX, Quinalphos+TX, Quinalphos-methyl+TX, Quinoclamine+TX, Quinofumelin+TX, Quinonamide+TX, Quinotion+TX, Quinoxyfen+TX, Quinthiophos+TX, Quintozen+TX, R-1492+TX, Lafoxanide+TX, Resmethrin+TX, Japanese knotweed (Reynoutria)Sachalinensis extract + TX, Ribavirin + TX, Lumetalaxyl + TX, Rotenone + TX, Lianya + TX, Lianodine + TX, S421 + TX, Sabajira + TX, Shuradan + TX, Siriloside + TX, Seboctilamine + TX, Cebuphos + TX, Sedaxane + TX, Selamectin + TX, Sesamex + TX, Sesasmolin + TX, SI-0009 + TX, Siguru + TX, Simazine + TX, Simeconazole + TX, Sodium arsenite + TX, Sodium cyanide + TX, Sodium fluoride + TX, Sodium fluoroacetate + TX, Sodium hexafluorosilicate + TX, Sodium pentachlorophenoxide + TX, Sodium selenate + TX, Sodium tetrathiocarbonate + TX, Sodium thiocyanate + TX, Sofamide + TX, Solzidine + TX, Spiroxamine + TX, SSI-121 + TX, Steinernema vivionis (Spodoptera) bibionis)+TX, Steinernema carpocapsae+TX, Steinernema feltiae+TX, Steinernema glaseri+TX, Steinernema riobrave+TX, Steinernema riobravis+TX, Steinernema scapterisci+TX, Steinernema species(spp.) + TX, Streptomycin + TX, Streptomycin sesquisulfate + TX, Strychnine + TX, Sulcatol + TX, Sulcoflon + TX, Sulcoflon-sodium + TX, Sulfiram + TX, Sulfuramide + TX, Sulfotep + TX, Sulfoxide + TX, Sulfur + TX, Sulfuryl fluoride + TX, Sulprophos + TX, Tar oil + TX, Taufluvalinate + TX, Tadimucarb + TX, TDE + TX, Tebuconazole + TX, Tebufloxin + TX, Tebupyrimphos + TX, Tecrofta Ram+TX, Temephos+TX, Tepa+TX, TEPP+TX, Terarethrin+TX, Terbam+TX, tert-butyl N-[6-[[[(1-methyltetrazole-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate+TX, tetrachloroethane+TX, tetrachlorothiophene+TX, tetraconazole+TX, tetradeca-11-en-1-yl acetate+TX, tetradiphon+TX, tetramethylfluthrin+TX, tetrasul+TX, thallium sulfate+TX, thiabene Dazole + TX, Thiafenox + TX, Thiapronil + TX, Cyclophos + TX, Tifluzamide + TX, Thiocarboxyme + TX, Thiocyclam + TX, Thiocyclam hydrogen oxalate + TX, Thiodiazole copper + TX, Thiofanox + TX, Thiohempa + TX, Thiomersal + TX, Thiometon + TX, Thionadin + TX, Thiophanate + TX, Thiophanate-methyl + TX, Thioquinox + TX, Thiosultap + TX, Thiosultap-sodium + TX, Thiotepa + TX, Thyramine + TX, Thuringe Nsine + TX, Thiazinyl + TX, Tolchlorophos-methyl + TX, Tolprocarb + TX, Trilfluanide + TX, Tralomethrin + TX, Transpermethrin + TX, Tretamine + TX, Triadimefone + TX, Triadimenol + TX, Triamiphos + TX, Triatene + TX, Triazamate + TX, Triazophos + TX, Triazoxide + TX, Triazurone + TX, Tributyltin oxide + TX, Trichlormetaphos-3 + TX, Trichloronato + TX, Tricogramma speciesspp.)+TX, Triclopyricarb+TX, Tricyclazole+TX, Tridemorph+TX, Triphenmorph+TX, Triphenophos+TX, Trifloxystrobin+TX, Triflumizole+TX, Triforin+TX, Trimedrua+TX, Trimedrua A+TX, Trimedrua B1+TX, Trimedrua B2+TX, Trimedrua C+TX, Trimetacarb+TX, Trinactin+TX, Trinexapac+TX, Triphenyltin acetate+TX, Triphenyltin hydroxide+TX, Triplene+TX, Triticonazole+TX, Tranquol+TX, Typhlodromus occidentalis Occidentalis + TX, Uredepa + TX, Validamycin + TX, Valifenarate + TX, Bamidthion + TX, Vaniliprole + TX, Veratridine + TX, Veratrin + TX, Berbutin + TX, Verticillium lecanii + TX, Vinclozoline + TX, Warfarin + TX, XMC + TX, Xylenol + TX, Zeatin + TX, Zetamethrine + TX, Zhongshengmycin + TX, Zinc naphthenate + TX, Zinc phosphide + TX, Thiazole zinc + TX, Zineb + TX, Ziram + TX, Zolaprofos + TX; Acinetobacter lwoffii + TX, Acremonium alternatum + TX, Acremonium cephalosporium + TX, Acremonium diospyri + TX, Acremonium obclavatum + TX, Adoxophyes orana granulosis virus (AdoxGV) (Capex®) + TX, Agrobacterium radiobacter strain K84 (Galltrol-A®) + TX, Alternaria alternate + TX, Alternaria cassia + TX, Alternaria destoluene (Alternaria destruens) (Smolder(registered trademark))+TX, Ampelomyces quisqualis (AQ10(registered trademark))+TX, Aspergillus flavus AF36 (AF36(registered trademark))+TX, Aspergillus flavus NRRL 21882 (Aflaguard(registered trademark))+TX, Aspergillus spp. +TX, Aureobasidium pullulans +TX, Azospirillum (MicroAZ(registered trademark), TAZO B(registered trademark))+TX, Azotobacter +TX, Azotobacter croocuccum (Azotobacter Bacillus chroocuccum (Azotomeal®) + TX, Azotobacter cysts (Bionatural Blooming Blossoms®) + TX, Bacillus amyloliquefaciens + TX, Bacillus cereus (BacillusBacillus cereus) + TX, Bacillus chitinosporus strain AQ746 + TX, Bacillus chitinosporus strain CM-1 + TX, Bacillus circulans + TX, Bacillus firmus (BioSafe®, BioNem-WP®), especially strain CNMC 1-1582 (e.g., VOTIVO® from BASF SE) + TX, Bacillus licheniformis strain 3086 (EcoGuard®, Green Releaf®) + TX, Bacillus licheniformis (Bacillus Bacillus licheniformis) strain HB-2 (Biostart (trademark), formerly Rhizoboost (registered trademark)) + TX, Bacillus macerans + TX, Bacillus marismortui + TX, Bacillus megaterium + TX, Bacillus mycoides strain AQ726 + TX, Bacillus papilla (Milky Spore Powder (registered trademark)) + TX, Bacillus pumilus species + TX, Bacillus pumilus strain AQ717 + TX, Bacillus pumilus strain GB34 (Yield Shield (registered trademark)) + TX, Bacillus pumilus Bacillus pumilus) strain QST 2808 (Sonata®, Ballad Plus®) + TX, Bacillus sphaericus (VectoLex®) + TX, Bacillus spp. + TX, Bacillus spp. strain AQ175 + TX, Bacillus spp. strain AQ177 + TX, Bacillus spp. strain AQ178 + TX, BacillusBacillus subtilis strain AQ153+TX, Bacillus subtilis strain AQ743+TX, Bacillus subtilis strain QST 713 (CEASE®, Serenade®, Rhapsody®)+TX, Bacillus subtilis strain QST 714 (JAZZ®)+TX, Bacillus subtilis strain QST3002+TX, Bacillus subtilis strain QST3004+TX, Bacillus subtilis var. amyloliquefaciens strain FZB24 (Taegro®, Rhizopro®)+TX, Bacillus thuringiensis aizawai GC 91(Agree(registered trademark))+TX, Bacillus thuringiensis Cry 2Ae+TX, Bacillus thuringiensis Cry1Ab+TX, Bacillus thuringiensis israelensis (BMP123(registered trademark), Aquabac(registered trademark), VectoBac(registered trademark))+TX, Bacillus thuringiensis kurstaki (Javelin(registered trademark), Deliver(registered trademark), CryMax(registered trademark), Bondide(registered trademark), Scutella WP(registered trademark), Turilava WP(registered trademark), Astuto(registered trademark), Dipel WP (registered trademark), Biobit (registered trademark), Foray (registered trademark)) + TX, Bacillus thuringiensis kurstaki BMP 123 (Baritone (registered trademark)) + TX, Bacillus thuringiensis kurstakikurstaki)HD-1 (Bioprotec-CAF / 3P(registered trademark))+TX, Bacillus thuringiensis strain AQ52+TX, Bacillus thuringiensis strain BD#32+TX, Bacillus thuringiensis tenebrionis (Novodor(registered trademark), BtBooster)+TX, Bacillus thuringiensis var. aizawai (XenTari(registered trademark), DiPel(registered trademark))+TX, bacterial species (GROWMEND(registered trademark), GROWSWEET(registered trademark), Shootup(registered trademark))+TX, tomato canker (Clavipacter) Bacteriophage of michiganensis (AgriPhage®, Bakflor®) + TX, Beauveria bassiana (Beaugenic®, Brocaril WP®) + TX, Beauveria bassiana GHA (Mycotrol ES®, Mycotrol O®, BotaniGuard®) + TX, Beauveria brongniartii (Engerlingspilz®, Schweizer Beauveria®, Melocont®) + TX, Beauveria spp. + TX, Botrytis cineria + TX, Bradyrhizobium japonicum (TerraMax®) + TX, Brevibacillus brevis + TX, Burkholderia cepacia (Deny®, Intercept®, Blue Circle®) + TX, Burkholderia gladii + TX, Burkholderia gladioli + TX, Burkholderia spp. + TX, Canadian thistle fungus (CBH Canadian Bioherbicide®) + TX, Candida butyri + TX, Candida famata + TX, Candida fructus + TX, Candida glabrata + TX, Candida guirielmondi (Candida Candida guilliermondii) + TX, Candida melibiosica + TX, Candida oleophila strain O + TX, Candida parapsilosis + TX, Candida pelliculosa + TX, Candida pulcherrima + TX, Candida reukaufii + TX, Candida saitoana (Bio-Coat®, Biocure®) + TX, Candida sake + TX, Candida spp.) + TX, Candida tenius + TX, Cedecea davisae + TX, Cellulomonas flavigena + TX, Chaetomium cochliodes (Nova-Cide®) + TX, Chaetomium globosum (Nova-Cide®) + TX, Chromobacterium subtsugae strain PRAA4-1T (Grandevo®) + TX, Cladosporium chlorocephalum + TX, Cladosporium cladosporioides + TX, Cladosporium oxysporum (Cladosporium oxysporum)+TX, Cladosporium spp.+TX, Cladosporium tenuissimum+TX, Clonostachys rosea (EndoFine®)+TX, Colletotrichum acutatum+TX, Coniothyrium minitans (Cotans WG®)+TX, Coniothyrium spp.)+TX, Cryptococcus albidus)(YIELDPLUS(registered trademark))+TX, Cryptococcus humicola+TX, Cryptococcus infirmo-miniatus+TX, Cryptococcus laurentii+TX, Cryptophlebia leucotreta granulosis virus(Cryptex(registered trademark))+TX, Cupriavidus campinensis+TX, Codlinga (Cydia pomonella) granulosis virus(CYD-X(registered trademark), Madex(registered trademark), Madex(registered trademark)Plus, Madex Max, Carpovirusine®) + TX, Cylindrobasidium laeve (Stumpout®) + TX, Cylindrocladium + TX, Debaryomyces hansenii + TX, Drechslera hawaiinensis + TX, Enterobacter cloacae + TX, Enterobacteriaceae + TX, Entomophtora virulenta (Vektor®) + TX, Epicoccum nigrum + TX, Epicoccum purpurascens + TX, Epicoccum spp.)+TX, Filobasidium floriforme+TX, Fusarium acuminatum+TX, Fusarium chlamydosporum+TX, Fusarium oxysporum (Fusaclean®, Biofox C®)+TX, Fusarium proliferatum+TX, Fusarium spp.+TX, Galactomyces geotrichum+TX, Gliocladium catenulatum (Primastop®, Prestop®)+TX, Gliocladium roseum roseum)+TX, Gliocladium spp. (SoilGard®)+TX, Gliocladium virens (Soilgard®)+TX, Granulopathy virus (Granupom®)+TX, Halobacillus halophilus+TX, Halobacillus litoralis+TX, Halobacillus trueperi+TX, Halomonas spp.)+TX, Halomonas subglaciescola+TX, Halovibrio variabilis+TX, Hanseniaspora uvarum+TX, Helicoverpa armigera nuclear polyhedron virus (Helicovex®)+TX, Helicoverpa zea nuclear polyhedron virus (Gemstar®)+TX, Isaria fumosorosea (strain formerly known as Paecilomyces fumosoroseus, PFR-97®, PreFeRal®)+TX, Isoflavone formononetin formononetin)(Myconate(registered trademark))+TX, Kloeckera apiculata+TX, Kloeckera spp.)+TX, Lagenidium giganteum (Laginex®)+TX, Lecanicillium lecanii strain KV01 (formerly known as Verticillium lecanii) (Mycotal® conidia (e.g., Vertalec® by Koppert / Arysta))+TX, Lecanicillium longisporum (Vertiblast®)+TX, Lecanicillium muscarium (Vertikil®)+TX, Lymantria dispar nuclear polyhedron virus (Disparvirus®)+TX, Marinococcus halophilus+TX, Meira geuraconigi geulakonigii)+TX, Metarhizium anisopliae (Destruxin WP(registered trademark))+TX, Metarhizium anisopliae (Met52(registered trademark))+TX, Metschnikowia fruticola (Shemer(registered trademark))+TX, Metschnikowia pulcherrima+TX, Microdochium dimerum (Antibot(registered trademark))+TX, . Micromonospora coerulea +TX, Microsphaeropsis ochracea +TX, Muscodor albus 620 (Muscudor®) +TX, Muscodor roseus, especially strain A3-5 (accession number NRRL 30548) +TX, mycorrhizal fungi species (Mycorrhizae spp.) (AMykor®, Root Maximizer®) +TX, Myrothecium verrucaria strain AARC-0255 (DiTera®, BROS PLUS®) +TX, Ophiostoma pyriferum piliferum) strain D97 (Sylvanex®) + TX, Paecilomyces farinosus + TX, Paecilomyces lilacinus strain 251 (MeloCon WG®) + TX, Paecilomyces linacinus (Biostat WP®) + TX, Paenibacillus polymyxa + TX, Pantoea agglomerans (BlightBan C9-1®) + TX, Pantoea spp. + TX, Pasteuria nisizawae nishizawae), especially strain Pn1 (Syngenta / ChemChina's CLARIVA); +TX, Pasteuria spp.)(Econem(registered trademark))+TX, Penicillium aurantiogriseum+TX, Penicillium billai (Jumpstart(registered trademark), TagTeam(registered trademark))+TX, Penicillium brevicompactum+TX, Penicillium frequentans+TX, Penicillium griseofulvum+TX, Penicillium purpurogenum+TX, Penicillium spp.+TX, Penicillium viridicatum +TX, Phlebiopsis gigantean (Rotstop®) +TX, Phosphate-soluble bacteria (Phosphomeal®) +TX, Phytophthora cryptogea +TX, Phytophthora palmivora (Devine®) +TX, Pichia anomala +TX, Pichia guilliermondii +TX, Pichia membranaefaciens +TX, Pichia onychis +TX, Pichia stipites +TX, Pseudomonas aeruginosa)+TX, Pseudomonas aureofasciens (Spot-Less Biofungicide®)+TX, Pseudomonas cepacia+TX, Pseudomonas chlororaphis (AtEze®)+TX, Pseudomonas corrugate+TX, Pseudomonas fluorescens (Zequanox®)+TX, Pseudomonas fluorescens strain A506 (BlightBan A506®)+TX, Pseudomonas putida+TX, Pseudomonas reactans (Pseudomonas reactans)+TX, Pseudomonas spp.)+TX, Pseudomonas syringae (Bio-Save®)+TX, Pseudomonas viridiflava+TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex L®)+TX, Puccinia canaliculata+TX, Puccinia thlaspeos (Wood Warrior®)+TX, Pythium paroecandrum+TX, Pythium oligandrum (Polygandron®, Polyversum®)+TX, Pythium periprocum (Pythium periplocum)+TX, Rhanella aquatilis+TX, Rhanella spp.+TX, Rhizobia (Dormal®, Vault®)+TX, Rhizoctonia+TX, Rhodococcus globerulus strain AQ719+TX, Rhodosporidium diobovatum+TX, Rhodosporidium toruloides+TX, Rhodotorula glutinis+TX, Rhodotorula graminis+TX, Rhodotorula musiragnosa mucilagnosa)+TX, Rhodotorula rubra+TX, Rhodotorula spp.)+TX, Saccharomyces cerevisiae+TX, Salinococcus roseus+TX, Sclerotinia minor (SARRITOR®)+TX, Sclerotinia minor+TX, Scytalidium spp.+TX, Scytalidium uredinicola+TX, Serratia marcescens+TX, Serratia plymuthica+TX, Serratia spp.+TX, Sordaria fimicola+TX, Spodoptera exigua exigua) Nuclear Polyhedron Disease Virus (Spod-X®, Spexit®) + TX, Spodoptera littoralis Nuclear Polyhedron Disease Virus (Littovir®) + TX, Sporobolomyces roseus + TX, Stenotrophomonas maltophilia + TX, Streptomyces albaduncus + TX, Streptomyces exfoliates + TX, Streptomyces galbus + TX, Streptomyces griseoplanus + TX, Streptomyces griseoviridis (Mycostop®) + TX, . Streptomyces hygroscopicus + TX, Streptomyces lydicus (Actinovate®) + TX, Streptomyces lydicus WYEC-108 (ActinoGrow®) + TX, Streptomyces violaceus + TX, Tilletiopsis minor + TX, Tilletiopsis spp. + TX, Trichoderma asperellum (T34 Biocontrol®) + TX, Trichoderma atroviride (Plantmate®) + TX, Trichoderma Trichoderma gamsii) (Tenet(registered trademark)) + TX, Trichoderma hamatum TH 382 + TX, Trichoderma harzianum rifai (Mycostar(registered trademark)) + TX, Trichoderma harzianum T-22 (Trianum-P(registered trademark), PlantShield HC(registered trademark), RootShield(registered trademark), Trichoderma-G(registered trademark)) + TX, Trichoderma harzianum T-39 (Trichodex(registered trademark)) + TX, Trichoderma inhamatum + TX, Trichoderma koningii + TX, Trichoderma lignorm (Trichoderma Trichoderma lignorum)+TX, Trichoderma longibrachiatum+TX, Trichoderma polysporum (Binab T(registered trademark))+TX, Trichoderma spp.)LC 52 (Sentinel (registered trademark)) + TX, Trichoderma taxi + TX, Trichoderma virens (formerly Gliocladium virens GL-21) (SoilGuard (registered trademark)) + TX, Trichoderma virens + TX, Trichoderma viride + TX, Trichoderma viride strain ICC 080 (Remedier (registered trademark)) + TX, Trichosporon pullulans + TX, Trichosporon spp. + TX, Trichothecium roseum + TX, Trichothecium spp.)+TX, Typhula phacorrhiza strain 94670+TX, Typhula phacorrhiza strain 94671+TX, Ulocladium atrum+TX, Ulocladium oudemansii (Botry-Zen®)+TX, Ustilago maydis+TX, various bacteri and auxiliary micronutrients (Natural II®)+TX, various fungi (Millennium Microbes®)+TX, Verticillium chlamydosporium+TX, Vip3Aa20 (VIPtera®)+TX, Virgibaclillus marismortui marismortui) + TX, Xanthomonas campestris pv. Poae (Camperico®) + TX, Xenorhabdfus bovienii + TX, Xenorhabdus nematophilus + TX;. AGNIQUE® MMF + TX, Azadirachtin (Plasma Neem Oil®, AzaGuard®, MeemAzal®, Molt-X®, e.g., Certis, AZATIN XL in the US) + TX, Botanical IGR (Neemazad®, Neemix®) + TX, BugOil® + TX, Canola Oil (Lilly Miller Vegol®) + TX, American Antwort (Chenopodium ambrosioides near ambrosioides) (Requiem®) + TX, Chrysanthemum Extract (Crisant®) + TX, Lamiaceae Essential Oil (Botania®) + TX, Neem Oil Extract (Trilogy®) + TX, Clove, Rosemary, Peppermint and Thyme Oil Extract (Garden Insect) Killer (registered trademark)) + TX, Garlic + TX, Glycinebetaine (Greenstim) + TX, Kaolin (Screen) + TX, Lemongrass oil (GreenMatch (registered trademark)) + TX, Melaleuca alternifolia extract (also known as tea tree oil) (Timorex Gold (registered trademark)) + TX, Clove, peppermint, garlic oil, and mint mixture (Soil Shot (registered trademark)) + TX, Clove, rosemary, and peppermint extract mixture (EF 400 (registered trademark)) + TX, Rosemary, sesame, peppermint, thyme, and cinnamon extract mixture (EF 300 (registered trademark)) + TX, Neem oil + TX, Catnip (Nepeta Catnip oil + TX, Nepeta cataria + TX, Nicotine + TX, Oregano oil (MossBuster®) + TX, Pedaliaceae oil (Nematon®) + TX, Pine oil (Retenol®) + TX, Pyrethrum + TX, QuillajaSaponaria (NemaQ®) + TX, Japanese knotweed (Reynoutria sachalinensis) (Regalia®, Sakalia®) + TX, Rotenone (Eco Roten®) + TX, Rutaceae plant extract (Soleo®) + TX, soybean oil (Ortho ecosense®) + TX, brown algae storage glucum (Laminarin®) + TX, thyme oil + TX; (E,Z)-7,9-Dodecadiene-1-yl acetate + TX, (E,Z,Z)-3,8,11-Tetradecatrienylate + TX, (Z,Z,E)-7,11,13-Hexadecatrienal + TX, 2-Methyl-1-butanol + TX, Biolure® + TX, Blackheaded Fireworm Pheromone (3M Sprayable Blackheaded Fireworm Pheromone®) + TX, Calcium Acetate + TX, Check-Mate® + TX, Codlinga Pheromone (Paramount dispenser-(CM) / Isomate C-Plus®) + TX, Entostat Powder (Exosex CM®) (Extract from palm trees) + TX, Grapeberry Moss Pheromone (3M MEC-GBM Sprayable Pheromone(registered trademark))+TX, Lavanzuryl senecioate+TX, Leafroller pheromone (3M MEC-LR Sprayable Pheromone(registered trademark))+TX, Muskamon (Snip7 Fly Bait(registered trademark))+TX, Pear fruit moth pheromone (3M oriental fruit moth sprayable pheromone(registered trademark))+TX, Clearwing moth larva (Peachtree Borer) pheromone (Isomate-P(registered trademark))+TX, Scenturion(registered trademark)+TX, Starbar Premium Fly Bait(registered trademark))+TX, Tomato pinworm pheromone (3M Sprayable pheromone(registered trademark))+TX; Acerophagus papaya + TX, Adalia bipunctata (Adalia-System®) + TX, Adalia bipunctata (Adaline®) + TX, Adalia bipunctata (Aphidalia®) + TX, Ageniaspis citricola + TX, Ageniaspis fuscicollis + TX, Amblyseius andersoni (Anderline®, Andersoni-System®) + TX, Amblyseius californicus californicus) (Amblyline(registered trademark), Spical(registered trademark)) + TX, Amblyseius cucumeris (Thripex(registered trademark), Bugline cucumeris(registered trademark)) + TX, Amblyseius fallacis (Fallacis(registered trademark)) + TX, Amblyseius swirskii (Bugline swirskii(registered trademark), Swirskii-Mite(registered trademark)) + TX, Amblyseius womersleyi (WomerMite(registered trademark)) + TX, Amitus hesperidum + TX, Anagrus atomus + TX, Anagyrus fussiventris fusciventris)+TX, Anagyrus kamali+TX, Anagyrus loecki+TX, Anagyrus pseudococci (Citripar(registered trademark))+TX, Anicetus benefices+TX, Anisopteromaluscalandrae)+TX, Anthocoris nemoralis (Anthocoris-System(registered trademark))+TX, Aphelinus abdominalis (Apheline(registered trademark), Aphiline(registered trademark)),+TX, Aphelinus asychis+TX, Aphidius colemani (Aphipar(registered trademark))+TX, Aphidius ervi (Aphelinus-System(registered trademark))+TX, Aphidius ervi (Ervipar(registered trademark))+TX, Aphidius gifuensis+TX, Aphidius matricariae (Aphipar-M(registered trademark))+TX, Aphidoletes Aphidimyza (Aphidend®, Aphidoline®) + TX, Aphytis lingnanensis + TX, Aphytis melinus + TX, Aprostocetus hagenowii + TX, Atheta coriaria (Staphyline®) + TX, Bombus spp. + TX, Bombus terrestris (Beeline®, Tripol®) + TX, Bombus terrestris (Natupol Beehive®) + TX, Cephalonomia stephanoderis + TX, Chilocorus nigritus nigritus)+TX, Yamato lacewing (Chrysoperla carnea) (Chrysoline®, Chrysopa®)+TX, Chrysoperla rufirabris (Chrysoperlarufilabris)+TX, Cirrospilus ingenuus+TX, Cirrospilus quadristriatus+TX, Citrostichus phyllocnistoides+TX, Closterocerus chamaeleon+TX, Closterocerus spp.+TX, Coccidoxenoides perminutus (Planopar®)+TX, Coccophagus cowperi+TX, Coccophagus lycimnia+TX, Cotesia flavipes+TX, Cotesia plutellae plutellae)+TX, Cryptolaemus montrouzieri (Cryptobug®, Cryptoline®)+TX, Cybocephalus nipponicus+TX, Dacnusa sibirica (Minusa®, DacDigline®, Minex®)+TX, Delphastus catalinae (Delphastus®)+TX, Delphastus pusillus+TX, Diachasmimorpha krausii+TX, Diachasmimorpha longicaudata+TX, Diaparsis jucunda jucunda)+TX, Diaphorencyrtus aligarhensis+TX, Diglyphus isaeaeisaea) (Diminex(registered trademark), Miglyphus(registered trademark), Digline(registered trademark)) + TX, Diversinervus spp. + TX, Encarsia citrina + TX, Encarsia formosa (Encarsia max(registered trademark), Encarline(registered trademark), En-Strip(registered trademark)) + TX, Encarsia guadeloupae + TX, Encarsia haitiensis + TX, Episyrphus balteatus (Syrphidend(registered trademark)) + TX, Eretmoceris siphonini + TX, Eretmocerus californicus californicus)+TX, desert gall wasp (Eretmocerus eremicus) (Enermix(registered trademark), Ercal(registered trademark), Eretline e(registered trademark), Bemimix(registered trademark))+TX, Eretmocerus hayati+TX, Mundus gall wasp (Eretmocerus mundus) (Bemipar(registered trademark), Eretline m(registered trademark))+TX, Eretmocerus siphonini+TX, Exochomus quadripustulatus+TX, spider mite gall midge (Feltiella acarisuga) (Feltiline(registered trademark))+TX, spider mite gall midge (Feltiella acarisuga) (Spidend(registered trademark))+TX, Phopius alisanus (Fopius arisanus)+TX, Fopius ceratitivorus+TX, formononetin (Wirless Beehome®)+TX, Franklinothrips vespiformis (Vespop®)+TX, Galendromus occidentalisoccidentalis)+TX, Goniozus legneri+TX, Habrobracon hebetor+TX, Harmonia axyridis (HarmoBeetle®)+TX, Heterorhabditis bacteriophora (NemaShield HB®, Nemaseek®, Terranem-Nam®) Terranem (registered trademark), Larvanem (registered trademark), B-Green (registered trademark), NemAttack (registered trademark), Nematop (registered trademark)) + TX, Heterorhabditis megidis (Nemasys H (registered trademark), BioNem H (registered trademark), Exhibitline hm (registered trademark), Larvanem-M (registered trademark)) + TX, Heterorhabditis spp. (Lawn Patrol (registered trademark)) + TX, Hippodamia convergens (ladybug) + TX, Hypoaspis aculeifer (Aculeifer-System (registered trademark), Entomite-A (registered trademark)) + TX, Hypoaspis miles (Hypoline m (registered trademark), Entomite-M (registered trademark)) + TX, Rubalia leukospoides (Lbalia Leucospoides) + TX, Lecanoideus floccissimus + TX, Lemophagus errabundus + TX, Leptomastidea abnormis + TX, Leptomastix dactylopii (Leptopar®) + TX, Leptomastix epona + TX, Lindorus lophanthae + TX, Lipolexis oregmae + TX, Blowfly (Lucilia caesar) (Natufly®) + TX, Lysiphlebus testasepes testaceipes)+TX, Macrolophus caliginosus (Mirical-N(registered trademark), Macroline c(registered trademark), Mirical(registered trademark))+TX, Mesoseiulus longipeslongipes)+TX, Metaphycus flavus+TX, Metaphycus lounsburyi+TX, Micromus angulatus (Milacewing®)+TX, Microterys flavus+TX, Muscidifurax raptorellus and Spalangia cameroni (Biopar®)+TX, Neodryinus typhlocybae+TX, Neoseiulus californicus+TX, Neoseiulus cucumeris (THRYPEX®)+TX, Neoseiulus falasis (Neoseiulus fallacis)+TX, Nesideocoris tenuis (NesidioBug®, Nesibug®)+TX, Ophyra aenescens (Biofly®)+TX, Orius insidiosus (Thripor-I®, Oriline i®)+TX, Orius laevigatus (Thripor-L®, Oriline l®)+TX, Orius majusculus (Oriline m®)+TX, Orius strigicollis (Thripor-S®)+TX, Pauesia juniperorum Juniperorum) + TX, Pediobius foveolatus + TX, Phasmarhabditis hermaphrodita (Nemaslug®) + TX, Phymastichus copheuscoffea)+TX, Phytoseiulus macropilus+TX, Phytoseiulus persimilis (Spidex®, Phytoline p®)+TX, Podisus maculiventris (Podisus®)+TX, Pseudacteon curvatus+TX, Pseudacteon obtusus+TX, Pseudacteon tricuspis+TX, Pseudaphycus maculipennis+TX, Pseudleptomastix mexicana+TX, Psyllaephagus pilosus pilosus)+TX, Psyttalia concolor (complex)+TX, Quadrastichus spp.+TX, Rhyzobius lophanthae+TX, Rodolia cardinalis+TX, Rumina decollate+TX, Semielacher petiolatus+TX, Sitobion avenae (Ervibank®)+TX, Steinernema carpocapsae (Nematac C®, Millenium®, BioNem C®, NemAttack®, Nemastar®, Capsanem®)+TX, Steinernema feltiae (Steinernema feltiae) (NemaShield(registered trademark), Nemasys F(registered trademark), BioNem F(registered trademark), Steinernema-System(registered trademark), NemAttack(registered trademark), Nemaplus(registered trademark), Exhibitline)sf(registered trademark), Scia-rid(registered trademark), Entonem(registered trademark))+TX, Steinernema kraussei (Nemasys L(registered trademark), BioNem L(registered trademark), Exhibitline srb(registered trademark))+TX, Steinernema riobrave (BioVector(registered trademark), BioVektor(registered trademark))+TX, Steinernema scapterisci (Nematac S(registered trademark))+TX, Steinernema spp.+TX, Steinernematid spp. (Guardian Nematodes(registered trademark))+TX, Stethorus punctulum punctillum)(Stethorus(registered trademark))+TX, Tamarixia radiate+TX, Tetrastichus setifer+TX, Thripobius semiluteus+TX, Torymus sinensis+TX, Tricogramma brassicae(Tricholine b(registered trademark))+TX, Tricogramma brassicae(Tricho-Strip(registered trademark))+TX, Tricogramma evanescens+TX, Tricogramma minutum+TX, Tricogramma ostriniae+TX, Tricogramma platneri(Trichogramma platneri)+TX, Trichogramma pretiosum+TX, Xanthopimpla stemmator+TX; Abscisic acid + TX, Aminomite® + TX, BioGain® + TX, bioSea® + TX, CAS number: 2643947-26-4 + TX, Chondrostereum purpureum (Chontrol Paste®) + TX, Colletotrichum gloeosporioides (Collego®) + TX, Copper octanoate (Cueva®) + TX, Delta trap (Trapline d®) + TX, Erwinia amylovora (Harpin) (ProAct®) + TX, Ni-HIBIT Gold CST(registered trademark))+TX, fatty acids derived from natural by-products of extra virgin olive oil (FLIPPER(registered trademark))+TX, ferric phosphate (Ferramol(registered trademark))+TX, funnel trap (Trapline y(registered trademark))+TX, Gallex(registered trademark)+TX, Grower's Secret(registered trademark)+TX, Homo-brassonolide+TX, iron phosphate (Lilly Miller Worry Free Ferramol Slug & Snail Bait(registered trademark))+TX, MCP hail trap (Trapline f(registered trademark))+TX, Microctonus hyperodae+TX, Mycoleptodiscus terrestris (Des-X(registered trademark))+TX, Nosema locustae (Semaspore Organic Grasshopper) Control (registered trademark) + TX, pheromone trap (Thripline ams (registered trademark)) + TX, potassium bicarbonate (MilStop (registered trademark)) + TX, potassium iodide + potassium thiocyanate (Enzicur (registered trademark)) + TX, potassium salt of fatty acid (Sanova (registered trademark)) + TX, potassium silicate solution (Sil-Matrix (registered trademark)) + TX, spider venom + TX, sticky trap (TraplineYF(registered trademark), Rebell Amarillo(registered trademark))+TX, SuffOil-X(registered trademark)+TX, Trap(Takitrapline y+b(registered trademark))+TX; Bacillus mojavensis strain R3B (accession number NCAIM(P)B001389) (International Publication No. 2013 / 034938) (Certis, USA), LLC + TX, Bacillus pumilus, especially strain BU F-33 (with NRRL accession number 50185) (BASF's CARTISSA®, EPA Reg. No. 71840-19) + TX, Bacillus subtilis CX-9060 (Certis USA LLC), Bacillus sp., especially strain D747 (available from Kumiai Chemical Industry Co., Ltd. as DOUBLE NICKEL®) (accession number FERM) BP-8234 (US Patent No. 7,094,592) + TX, Bacillus subtilis strain BU1814 (VELONDIS® PLUS, VELONDIS® FLEX, and VELONDIS® EXTRA from BASF SE) + TX, Bacillus subtilis var. amyloliquefaciens strain FZB24 (accession number DSM 10271) (available from Novozymes as TAEGRO® or TAEGRO® ECO (EPA registration number 70127-5)) + TX, Bacillus subtilis, particularly strain QST713 / AQ713 (with NRRL accession number B-21661, described in US Patent No. 6,060,051) (Bayer CropScience) LP (available from the USA as SERENADE® OPTI or SERENADE® ASO) + TX, Paenibacillus polymyxa, especially strain AC-1 (e.g., TOPSEED® from Green Biotech Company Ltd.) + TX, Paenibacillus sp.) strain (accession number NRRL B-50972 or accession number NRRL B-67129, International Publication No. 2016 / 154297) + TX, Pantoea agglomerans, in particular strain E325 (accession number NRRL B-21856) (available from Northwest Agri Products as BLOOMTIME BIOLOGICAL® FD BIOPESTICIDE) + TX, Pseudomonas proradix (e.g., PRORADIX® from Sourcon Padena) + TX; Aureobasidium pullulans, in particular spores of strain DSM14940, spores of strain DSM14941, or mixtures of spores of strains DSM14940 and DSM14941 (e.g., bio-ferm, CH's BOTECTOR® and BLOSSOM PROTECT®) + TX; Pseudozyma aphidis (disclosed in International Publication No. 2011 / 151819 by Yissum Research Development Company of the Hebrew University of Jerusalem) + TX; Saccharomyces cerevisiae, in particular strains CNCM No. 1-3936, CNCM No. 1-3937, CNCM No. 1-3938, or CNCM No. 1-3939 (International Publication No. 2010 / 086790) + TX; Agrobacterium radiobacter strain K84 (e.g., AgBioChem, CA, GALLTROL-A®) + TX, Bacillus amyloliquefaciens isolate B246 (e.g., University of Pretoria, AVOGREEN®) + TX, Bacillus amyloliquefaciens strain F727 (also known as strain MBI110) (NRRL accession number B-50768, International Publication No. 2014 / 028521) (STARGUS®, Marrone Bio Innovations) + TX, Bacillus amyloliquefaciens Bacillus amyloliquefaciens strain FZB42, accession number DSM23117 (available as RHIZOVITAL® from ABiTEP, DE) + TX, Bacillus amyloliquefaciens, in particular strain D747 (available as Double Nickel® from Kumiai Chemical Industry Co., Ltd.) (accession number FERM BP-8234, U.S. Patent No. 7,094,592) + TX, Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (QUARTZO® (WG) and PRESENCE® (WP) (FMC Corporation) + TX), Bacillus licheniformis, in particular strain SB3086 (accession number ATCC 55406, International Publication No. 2003 / 000051 (available from Novozymes as ECOGUARD® Biofungicide and GREEN RELEAF®) + TX, Bacillus methylotrophicus strain BAC-9912 (Institute of Applied Ecology, Chinese Academy of Sciences) + TX, Bacillus mycoidesmycoides) isolate (accession number B-30890) (available from Certis USA LLC as BMJ TGAI® or WG and LifeGard®) + TX, Bacillus pumilus, in particular strain GB34 (available from Bayer AG, DE as Yield Shield®) + TX, Bacillus pumilus, in particular strain QST2808 (available from Bayer CropScience LP, USA as SONATA®) (accession number NRRL B-30087, described in U.S. Patent No. 6,245,551) + TX, Bacillus subtilis (CX-9060 from Certis USA LLC) + TX, Bacillus subtilis IAB / BS03 (AVIV® (STK Bio-Ag Technologies), PORTENTO® (Idai) Nature))+TX, Bacillus subtilis strain KTSB (FOLIACTIVE® (Donaghys))+TX, Bacillus subtilis strain BU1814 (available from BASF SE as VELONDIS® PLUS, VELONDIS® FLEX, and VELONDIS® EXTRA)+TX, Bacillus subtilis strain GB03 (available from Bayer AG, DE as Kodiak®)+TX, Bacillus subtilis strain MBI 600 (available from BASF SE as SUBTILEX) (Accession number NRRL B-50595, U.S. Patent No. 5,061,495)+TX, Bacillus subtilis Bacillus subtilis var. amyloliquefaciens strain Y1336 (available from Bion-Tech, Taiwan as BIOBAC® WP) (registered as a biocide under registration numbers 4764, 5454, 5096, and 5277) + TX, Bacillus subtilis var. amyloliquefaciens strain FZB24 (accession number DSM)10271 (available from Novozymes as TAEGRO® or TAEGRO® ECO (EPA registration number 70127-5)) + TX, Bacillus subtilis Y1336 (available from Bion-Tech, Taiwan as BIOBAC® WP) (registered as a biocide under registration numbers 4764, 5454, 5096, and 5277) + TX, Paenibacillus epiphyticus (International Publication No. 2016 / 020371) (BASF SE + TX), Paenibacillus polymyxa ssp. plantarum (International Publication No. 2016 / 020371) (BASF SE + TX), Paenibacillus species sp.) strain (accession number NRRL B-50972 or accession number NRRL B-67129, International Publication No. 2016 / 154297) + TX, Pseudomonas chlororaphis strain AFS009 (accession number NRRL B-50897, International Publication No. 2017 / 019448) (e.g., AgBiome Innovations, HOWLER® and ZIO® in the U.S.) + TX, Pseudomonas chlororaphis, in particular strain MA342 (e.g., CEDOMON®, CERALL® and CEDRESS® by Bioagri and Koppert) + TX, Pseudomonas fluorescein (Pseudomonas Fluorescens strain A506 (e.g., NuFarm's BLIGHTBAN® A506) + TX, Pseudomonas proradix (e.g., Sourcon Padena's PRORADIX®) + TX, Streptomyces griseoviridis strain K61 (also known as Streptomyces galbus strain K61) (Accession number DSM)7206) (Verdera's MYCOSTOP®, BioWorks' PREFENCE®, see Crop Protection 2006, 25, 468-475) + TX, Streptomyces lydicus strain WYEC108 (also known as Streptomyces lydicus strain WYCD108US) (Novozymes' ACTINO-IRON® and ACTINOOVATE®) + TX; Trichoderma atroviride strain T11 (IMI352941 / CECT20498) + TX, Ampelomyces quisqualis strain AQ10 (accession number CNCM 1-807) (e.g., AQ10® from IntrachemBio Italia) + TX, Ampelomyces quisqualis, especially strain AQ10 (e.g., AQ10® from IntrachemBio Italia) + TX, Aspergillus flavus strain NRRL 21882 (product known as AFLA-GUARD® from Syngenta / ChemChina) + TX, Aureobasidium pullulans, especially strain DSM 14941+TX spores, Aureobasidium pullulans, especially strain DSM 14940+TX spores, Aureobasidium pullulans, especially a mixture of spores of strains DSM 14940 and DSM 14941 (e.g., Bio-ferm, CH's Botector®)+TX, Chaetomium cupreum (accession number CABI 353812) (e.g., AgriLife's BIOKUPRUM®)+TX, Chaetomium globosum (available as Rivale's RIVADIOM®)+TX, Cladosporium cladospolioides Coniothyrium minitans, specifically strain CON / M / 91-8 (accession number DSM9660, e.g., Bayer CropScience Biologics) (Stichting Dienst Landbouwkundig Onderzoek) +TX, Coniothyrium minitans, particularly strain CON / M / 91-8 (accession number DSM9660, e.g., Bayer CropScience Biologics)Contans(registered trademark) of GmbH +TX, Cryptococcus flavescens strain 3C (NRRL Y-50378) +TX, Dactylaria candida, Dilophosphora alopecuri (available as TWIST FUNGUS(registered trademark)), Fusarium oxysporum strain Fo47 (available as FUSACLEAN(registered trademark) of Natural Plant Protection) +TX, Gliocladium catenulatum (synonym: Clonostachys rosea f. catenulate) strain J1446 (e.g., Prestop(registered trademark) of Lallemand) +TX, Gliocladium roseum (Also known as Clonostachys rosea f rosea) strain IK726 (Jensen DF, et al. Development of a biocontrol agent for plant disease control with special emphasis on the near commercial fungal antagonist Clonostachys rosea strain 'IK726', Australasian Plant Pathol. 2007, 36(2):95-101) + TX, Gliocladium roseum (Also known as Clonostachys rosea f rosea) (Especially strain 321U of Adjuvants Plus, Xue AG (Efficacy of Clonostachys rosea strain ACM941 and fungicide seed treatments for controlling the root tot complex of field pea + TX, Can Jour Plant Science)The following strains are disclosed in 2003+TX, 83(3):519-524): Metschnikowia fructicola, particularly strain NRRL Y-30752+TX, Microsphaeropsis ochracea, Penicillium steckii (DSM 27859, International Publication No. 2015 / 067800)+TX of BASF SE, Trichoderma asperellum strain ICC 012 (also known as Trichoderma harzianum ICC012) (accession number CABI CC IMI 392716), and Trichoderma hyacinthii. A mixture of T. gamsii (formerly known as T. viride) strain ICC 080 (accession number IMI 392151) (e.g., BIO-TAM® from Isagro USA+TX, Inc. or BIODERMA® from Agrobiosol de Mexico, SA de CV) + TX, Penicillium vermiculatum + TX, Phlebiopsis gigantea strain VRA 1992 (ROTSTOP® from Danstar Ferment) + TX, Pseudozyma flocculosa strain PF-A22 UL (available as SPORODEX® from Plant Products Co., CA) + TX, Saccharomyces cerevisiae Saccharomyces cerevisiae) strain LAS117 cell wall (CEREVISANE® of Lesaffre, ROMEO® of BASF SE) + TX, Saccharomyces cerevisiae strain (CNCM No. 1-3936, CNCM No. 1-3937, CNCM No. 1-3938 of Lesaffre et Compagnie, FR, CNCMNo.1-3939 (International Publication No. 2010 / 086790))+TX, Saccharomyces cerevisiae, especially strain LASO2 (Agro-Levures et Derives)+TX, Simplicillium lanosoniveum+TX, strain T34 (e.g., Biocontrol Technologies SL, ES T34 Biocontrol) or Isagro strain ICC 012)+TX, strain WRL-076 (NRRL Y-30842), US 7,579,183+TX, Talaromyces flavus strain V117b+TX, Trichoderma asperelloides JM41R (Accession No. NRRL B-50759) (BASF SE TRICHO PLUS(registered trademark))+TX, Trichoderma asperellum, especially strain SKT-1 (accession number FERM P-16510) (e.g., ECO-HOPE(registered trademark) of Kumiai Chemical Industry)+TX, Trichoderma asperellum, especially strain kd (e.g., T-Gro of Andermatt Biocontrol)+TX, Trichoderma atroviride strain 77B (T77 of Andermatt Biocontrol)+TX, Trichoderma atroviride strain ATCC 20476 (IMI 206040)+TX, Trichoderma atroviride strain LC52 (e.g., Agrimm Technologies) Tenet (Tenet) + TX, Trichoderma atroviride strain LU132 (e.g., Sentinel (Sentinel) of Agrimm Technologies Limited) + TX, Trichoderma atroviride strain NMI no. V08 / 002388 + TX, Trichoderma atroviride (TrichodermaTrichoderma atroviride strain NMI no.V08 / 002389+TX, Trichoderma atroviride strain NMI no.V08 / 002390+TX, Trichoderma atroviride strain no.V08 / 002387+TX, Trichoderma atroviride strain SKT-1 (FERM P-16510), Japanese Patent Publication No. 11-253151 + TX, Trichoderma atroviride strain SKT-2 (FERM P-16511), Japanese Patent Publication No. 11-253151 + TX, Trichoderma atroviride strain SKT-3 (FERM P-17021), Japanese Patent Publication No. 11-253151 + TX, Trichoderma atroviride, in particular strain SC1 (accession number CBS 122089, International Publication No. 2009 / 116106 and U.S. Patent No. 8,431,120 (Bi-PA)) + TX, Trichoderma atroviride strain CNCM 1-1237 (e.g., Agrauxine, Esquive® WP of FR) + TX, Trichoderma fertile (e.g., BASF product TrichoPlus) + TX, Trichoderma gamsii (formerly T. viride) + TX, Trichoderma gamsii (formerly T. viride) strain ICC 080 (IMI CC 392151 CABI) (available as BIODERMA® by AGROBIOSOL DE MEXICO, SADE CV), + TX, Trichoderma gamsii strain ICC080 (IMI CC 392151 CABI, e.g., AGROBIOSOL DE MEXICO, SADE CV BioDerma), +TX, Trichoderma harmatum +TX, Trichoderma harmatum (Accession number ATCC 28012 +TX), Trichoderma harzianum +TX, Trichoderma harzianum rifai T39 (e.g., Makhteshim, Trichodex®, a registered trademark in the US) +TX, Trichoderma harzianum strain CepaSimbT5 (Simbiose Agro) + TX, Trichoderma harzianum strain DB 103 (available as T-GRO® 7456 by Dagutat Biolab) + TX, Trichoderma harzianum strain ITEM 908 (e.g., Trianum-P by Koppert) + TX, Trichoderma harzianum strain T-22 (e.g., Trianum-P by Andermatt Biocontrol or Koppert) + TX, Trichoderma harzianum strain TH35 (e.g., Root-Pro by Mycontrol) + TX, Trichoderma polysporum strain IMI 206039 (e.g., Binab TF by Binab Bio-Innovation AB, Sweden) WP)+TX, Trichoderma stromaticum (accession number Ts3550 (e.g., Tricovab of CEPLAC, Brazil))+TX, Trichoderma virens (also known as Gliocladium virens), especially strain GL-21 (e.g., Certis, SoilGard, USA)+TX, Trichoderma virens strain G-41 (formerly known as Gliocladium virens) (accession number ATCC 20906) (e.g., BioWorks, ROOTSHIELD® PLUS WP and TURFSHIELD® PLUS WP, USA)+TX, Trichoderma viride, especially strain B35 (Pietr et al. al., 1993, Zesz. Nauk. AR w Szczecinie 161:125-137) + TX, Trichoderma viride strain TV1 (e.g., Trianum-P of Koppert) + TX, Ulocladium audemancyioudemansii) strain U3 (accession number NM 99 / 06216) (e.g., Botry-Zen Ltd, BOTRY-ZEN® of New Zealand and BOTRYSTOP® of BioWorks+TX, Inc.)+TX, Verticillium albo-atrum (formerly V. dahliae) strain WCS850 (accession number WCS850) (e.g., DUTCH TRIG® of Tree Care Innovations)+TX deposited with the Central Bureau for Fungi Cultures, Verticillium chlamydosporium+TX; A mixture of Azotobacter vinelandii and Clostridium pasteurianum (available from Agrinos as INVIGORATE®) + TX, a mixture of Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (available from FMC Corporation as QUARTZO® (WG), PRESENCE® (WP)) + TX, Azorhizobium caulinodans, especially strain ZB-SK-5 + TX, Azospirillum brasilense (e.g., VIGOR® from KALO, Inc.) + TX, Azospirillum lipoferum lipoferum) (For example, TerraMax, Inc.)VERTEX-IF(trademark))+TX, Azotobacter chroococcum, especially strain H23+TX, Azotobacter vinelandii, especially strain ATCC 12837+TX, Bacillus amyloliquefaciens BS27 (accession number NRRL B-5015)+TX, Bacillus amyloliquefaciens, especially strain FZB42 (e.g., ABiTEP, DE RHIZOVITAL(registered trademark))+TX, Bacillus amyloliquefaciens, especially strain IN937a+TX, Bacillus amyloliquefaciens Bacillus amyloliquefaciens)pm414 (LOLI-PEPTA® registered trademark of Biofilm Crop Protection) + TX, Bacillus amyloliquefaciens SB3281 (ATCC#PTA-7542, International Publication No. 2017 / 205258) + TX, Bacillus amyloliquefaciens TJ1000 (available from Novozymes as QUIKROOTS® registered trademark) + TX, Bacillus cereus family member EE128 (NRRL No. B-50917) + TX, Bacillus cereus family member EE349 (NRRL No. B-50928) + TX, Bacillus cereus Bacillus mycoides) particularly strain BP01 (ATCC 55675, e.g., Arysta Lifescience, MEPICHLOR® in the U.S.) +TX, Bacillus mycoides BT155 (NRRL No. B-50921) +TX, Bacillus mycoides BT46-3 (NRRL No. B-50922) +TX, Bacillus mycoides EE118 (NRRL No.B-50918)+TX, Bacillus mycoides EE141 (NRRL No. B-50916)+TX, Bacillus pumilus, especially strain GB34 (e.g., YIELD SHIELD® of Bayer Crop Science, DE),+TX, Bacillus pumilus, especially strain QST2808 (accession number NRRL No. B-30087)+TX, Bacillus siamensis, especially strain KCTC 13613T+TX, Bacillus subtilis, especially strain AQ30002 (accession number NRRL No. B-50421, described in US Patent Application No. 13 / 330,576)+TX, Bacillus Bacillus subtilis), particularly strain AQ30004 (NRRL No. B-50455, described in US Patent Application No. 13 / 330,576) + TX, Bacillus subtilis, particularly strain MBI 600 (e.g., SUBTILEX® from BASF SE) + TX, Bacillus subtilis rm303 (RHIZOMAX® from Biofilm Crop Protection) + TX, Bacillus subtilis strain BU1814 (available from BASF SE as TEQUALIS®) + TX, Bacillus tequilensis, particularly strain NII-0943 + TX, Bacillus thuringiensis BT013A (NRRL No. B-50924) (Bacillus thuringiensis (Bacillus thuringiensis)4Q7 also known as +TX, Bradyrhizobium japonicum (e.g., Novozymes' OPTIMIZE®) +TX, Delftia acidovorans, especially strain RAY209 (e.g., Brett Young Seeds' BIOBOOST®) +TX, Lactobacillus sp.) (e.g., LACTOPLANT® from LactoPAFI) + TX, Mesorhizobium cicer (e.g., NODULATOR from BASF SE) + TX, Paenibacillus polymyxa, especially strain AC-1 (e.g., TOPSEED® from Green Biotech Company Ltd.) + TX, Pseudomonas aeruginosa, especially strain PN1 + TX, Pseudomonas proradix (e.g., PRORADIX® from Sourcon Padena) + TX, Rhizobium leguminosarium biovar viciae (e.g., NODULATOR from BASF SE) + TX, Rhizobium leguminosarium * Myrothecium verrucaria strain AARC-0255 (e.g., DiTera® from Valent Biosciences) + TX, Penicillium bilaii strain ATCC 22348 (e.g., JumpStart® from Acceleron BioAg) + TX, Penicillium bilaii strain ATCC ATCC20851 + TX, Purpureocillium lilacinum (formerly known as Paecilomyces lilacinus) strain 251 (AGAL89 / 030550, e.g., BioAct from Bayer CropScience Biologics GmbH) + TX, Pythium origandrum Pythium oligandrum strain DV74+TX, Pythium oligandrum strain M1 (ATCC 38472, e.g., Polyversum of Bioprepraty, CZ)+TX, Rhizopogon amylopogon (Myco-Sol of Agri-Enterprise, LLC (formerly Helena Chemical Company))+TX, Rhizopogon fulvigleba (Myco-Sol of Agri-Enterprise, LLC (formerly Helena Chemical Company))+TX, Talaromyces flavus strain V117b+TX, Trichoderma asperellum strain (Plant Health Products, ZA Eco-T)+TX, Trichoderma asperellum strain kd (e.g., Andermatt Biocontrol T-Gro)+TX, Trichoderma atroviride, especially strain no.V08 / 002387+TX, Trichoderma atroviride strain CNCM 1-1237 (e.g., Agrauxine, Esquive® WP, FR)+TX, Trichoderma atroviride strain LC52 (also known as Trichoderma atroviride strain LU132, e.g., Sentinel, Agrimm Technologies Limited)+TX, Trichoderma atroviride strain no. NMI No. V08 / 002388+TX, Trichoderma atroviride strain no. NMI No. V08 / 002389+TX, Trichoderma atroviride strain no. NMI No.V08 / 002390+TX, Trichoderma atroviride strain SC1 (described in International Publication No. 2009 / 116106)+TX, Trichoderma harzianum strain 1295-22+TX, Trichoderma harzianum strain ITEM 908+TX, Trichoderma harzianum strain T-22 (e.g., Andermatt Biocontrol or KoppertTrianum-P)+TX, Trichoderma harzianum strain TSTh20+TX, Trichoderma virens strain GI-3+TX, Trichoderma virens virens) strain GL-21 (e.g., Certis, SoilGard® registered trademark in the US) + TX, Trichoderma viride strain B35 (Pietr et al., 1993, Zesz. Nauk. AR w Szczecinie 161:125-137) + TX, Verticillium albo-atrum (formerly V. dahliae (V.dahliae)) Stock WCS850 (CBS 276.92, e.g., Dutch Trig of Tree Care Innovations) + TX;. Agrobacterium radiobacter strain K84 (Galltrol, AgBiochem Inc.) + TX, Bacillus amyloliquefaciens, in particular strain PTS-4838 (e.g., Valent Biosciences, AVEO, USA) + TX, Bacillus mycoides isolate J. (e.g., BmJ, Certis USA LLC) + TX, Bacillus sphaericus, in particular serotype H5a5b strain 2362 (ABTS-1743) (e.g., Valent BioSciences, VECTOLEX®, USA) + TX, Bacillus thuringiensis israelensis strain BMP 144 (e.g., Becker Microbial Products) AQUABAC® (IL) + TX, Bacillus thuringiensis subsp. aizawai strain GC-91 + TX, Bacillus thuringiensis subsp. aizawai, especially serotype H-7 (e.g., Valent BioSciences, FLORBAC® WG in the US) + TX, Bacillus thuringiensis subsp. aizawai, especially strain ABTS-1857 (SD-1372, e.g., XENTARI® from Valent BioSciences) + TX, Bacillus thuringiensis subsp. israelensis (serotype H-14) strain AM65-52 (accession number ATCC) 1276) (e.g., Valent BioSciences, VECTOBAC®, USA) + TX, Bacillus thuringiensis subsp. crustachyBacillus thuringiensis subsp. Kurstaki strain ABTS 351+TX, Bacillus thuringiensis subsp. Kurstaki strain BMP 123 (Becker Microbial Products, IL, Bayer CropScience's BARITONE)+TX, Bacillus thuringiensis subsp. Kurstaki strain EG 2348 (Certis, LEPINOX, USA)+TX, Bacillus thuringiensis subsp. Kurstaki strain EG 7841 (Certis, CRYMAX, USA)+TX, Bacillus thuringiensis subsp. Kurstaki strain HD-1 (e.g., Valent BioSciences, DIPEL® (ES) + TX, Bacillus thuringiensis subsp. Kurstaki strain PB 54 + TX, Bacillus thuringiensis subsp. Kurstaki strain SA 11 (Certis, JAVELIN, USA) + TX, Bacillus thuringiensis subsp. Kurstaki strain SA 12 (Certis, THURICIDE, USA) + TX, Bacillus thuringiensis subsp. Tenebrionis strain NB 176 (SD-5428, e.g., NOVODOR® FC, BioFa DE) + TX, Bacillus thuringiensis variety Colmeli (Bacillus Bacillus thuringiensis var. Colmeri) (e.g., TIANBAOBTC at Changzhou Jianghai Chemical Factory) + TX, Bacillus thuringiensis var. japonensisjaponensis) strain Buibui+TX, Bacillus thuringiensis var. kurstaki strain EVB-113-19 (e.g., BIOPROTEC® from AEF Global)+TX, Brevibacillus laterosporus+TX, Burkholderia spp., especially Burkholderia rinojensis strain A396 (also known as Burkholderia rinojensis strain MBI 305) (accession number NRRL B-50319, international publications 2011 / 106491 and 2013 / 032693, e.g., MBI206 from Marrone Bio Innovations) TGAI and ZELTO (registered trademarks) + TX, Chromobacterium subtsugae, especially strain PRAA4-1T (e.g., MBI-203, e.g., GRANDEVO (registered trademark) of Marrone Bio Innovations) + TX, Lecanicillium muscarium Ve6 (MYCOTAL of Koppert) + TX, Paenibacillus popilliae (formerly known as Bacillus popilliae, e.g., St.Gabriel Laboratories' MILKY SPORE POWDER (trademark) or MILKY SPORE GRANULAR (trademark) + TX; Serratia entomophila (e.g., Wrightson Seeds' INVADE (registered trademark)) + TX; Serratia marcescens, especially strain SRM (accession number MTCC 8708) + TX; Trichoderma asperellum (Novozymes' TRICHODERMAX) + TX; Wolbachia pipientis ZAP strain (e.g., MosquitoMate's ZAP MALES (registered trademark)) + TX; Beauveria bassiana strain ATCC 74040 (e.g., NATURALIS® from Intrachem Bio Italia) + TX, Beauveria bassiana strain ATP02 (accession number DSM 24665), Apopka 97 (PREFERAL from SePRO) + TX, Beauveria bassiana strain GHA (accession number ATCC74250, e.g., BOTANIGUARD® ES and MYCONTROL-O® from Laverlam International Corporation) + TX, Metarhizium anisopliae 3213-1 (International Publication No. 2017 / 066094 (Pioneer Hi-Bred) (Deposited under NRRL accession number 67074, disclosed to International) +TX, Metalhizium robertsii 15013-1 (deposited under NRRL accession number 67073) +TX, Metalhizium robertsii 23013-3 (deposited under NRRL accession number 67075) +TX, Paecilomyces lilacinus strain 251 (Certis, MELOCON, USA) +TX; Codling moth (Cydia pomonella) granuloma virus (GV) + TX, tobacco budworm (Helicoverpa armigera) nuclear polyhedrosis virus (NPV) + TX, apple leafroller (Adoxophyes orana) granuloma virus (GV) + TX, Spodoptera exigua (white fall armyworm) mNPV + TX, Spodoptera frugiperda (white fall armyworm) mNPV + TX; Burkholderia spp., especially Burkholderia cepacia (formerly known as Pseudomonas cepacia) + TX, Gigaspora spp. + TX, Glomus spp. + TX, Laccaria spp. + TX, Lactobacillus buchneri + TX, Paraglomus spp. + TX, Pisolithus tinctorus + TX, Pseudomonas spp. + TX, Rhizobium spp., especially Rhizobium trifolii (trifolii)+TX, Rhizopogon spp.+TX, Scleroderma spp.+TX, Streptomyces spp.+TX, Suillus spp.+TX, Agrobacterium spp.+TX, Azorhizobium caulinodans+TX, Azospirillum spp.+TX, Azotobacter spp.+TX, Bradyrhizobium spp.+TX, Gigaspora monosporum+TX; Garlic (Allium sativum) (NEMGUARD by Eco-Spray, BRALIC by ADAMA) + TX, Armour-Zen + TX, Artemisia absinthium + TX, BioKeeper WP + TX, Brassicaceae extract, especially oilseed powder or mustard powder + TX, Cassia nigricans + TX, Celastrus angulatus + TX, Chenopodium anthelminticum + TX, Quinoa (Chenopodium quinoa) (quinoa seed-derived saponin extract) (e.g., Heads Up plant Protectants, Heads Up® by CA (quinoa saponin)) + TX, Chitin + TX, Dryopteris filix-mas)+TX, Equisetum arvense+TX, Fortune Azalea+TX, Fungustop+TX, Melaleuca alternifolia extract (STK's TIMOREX GOLD)+TX, Natural Blad polypeptide extracted from lupin seeds (FMC's FRACTURE®)+TX, Natural Blad polypeptide extracted from lupin seeds (Certis EU's PROBLAD®)+TX, Pyrethrin+TX, Quassia amara+TX, Quercus+TX, Quillaja extract (BASF's QL AGRI 35)+TX, Marrone Bio's REGALIA MAXX)+TX, Requiem® insecticide+TX, Japanese knotweed (Reynoutria) (Eden Research's CEDROZ) extract (regallia+TX, lianya / lianodine+TX, comfrey (Symphytum officinale)+TX, tansy (Tanacetum vulgare)+TX, thymol+TX, geraniol (Eden Research's CEDROZ)+TX mixed with thymol, geraniol and eugenol (EdenResearch's MEVALONE)+TX mixed with thymol, Triact 70+TX, TriCon+TX, Tropaeulum majus+TX, Urtica dioica+TX, Bellatrine+TX, Viscum album+TX; Mercury oxide + TX, octylinone + TX, thiophanate-methyl + TX; MGK 264+TX, 2-(2-butoxyethoxy)ethyl piperonylate+TX, 2-isovalerylindan-1,3-dione+TX, 4-(quinoxaline-2-ylamino)benzenesulfonamide+TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohexa-2-enone+TX, acibenzolar+TX, acibenzolar-S-methyl+TX, alpha-bromadiolone+TX, alpha-chlorohydrin+TX, aluminum phosphide+TX, anthraquinone+TX, antu+TX, arsenic trioxide+TX, barium carbonate+T X, Benoxacol + TX, Bisthiosemi + TX, Brodifacum + TX, Bromadiolon + TX, Bromesalen + TX, Calcium cyanide + TX, Chloralose + TX, Chlorophacinone + TX, Cholecalciferol + TX, Chloquintocet (Chloquintocet-Mexyl is an example) + TX, Copper naphthenate + TX, Copper oxychloride + TX, Coumaflyl + TX, Coumatetralyl + TX, Crimidine + TX, Cyprosulfamide + TX, Diazinon + TX, Dichlormid + TX, Dicyclopentadiene + TX, Diphena Cumm+TX, Difethiaron+TX, Difacinone+TX, Ergocalciferol+TX, Farnesol+TX, Nerolidol+TX, Fenchlorazole (Fenchlorazole-ethyl is an example)+TX, Fenchlorim+TX, Furocumafen+TX, Fluoroacetamide+TX, Flupropazine+TX, Flupropazine hydrochloride+TX, Fluxofenim+TX, Frillazole+TX, Gamma-HCH+TX, Guazatine+TX, Guazatine acetate+TX, HCH+TX, Hydrogen cyanide+TX, Imanin+TX , Iodomethane + TX, Isoxadifen (Isoxadifen-ethyl is an example) + TX, Lindan + TX, Magnesium phosphide + TX, MB-599 + TX, Mefenyphen (Mefenyphen-diethyl is an example) + TX, Metocamifen + TX, Methiocarb + TX, Methyl bromide + TX, Nerolidol + TX, Norbolmid + TX, Petroleum + TX, Fosacetim + TX, Phosphine + TX, Phosphate + TX, Pindone + TX, Piperonyl butoxide + TX, Piprotal + TX, Potassium arsenite + TX, Probenazole + TX, Propyl isomer + TX,Pyridine-4-amine + TX, pyrinulone + TX, Japanese knotweed (Reynoutria sachalinensis) extract + TX, ribavirin + TX, S421 + TX, siriloside + TX, sesamex + TX, sesamolin + TX, sodium arsenite + TX, sodium cyanide + TX, sodium fluoroacetate + TX, strychnine + TX, sulfoxide + TX, thallium sulfate + TX, thyram + TX, trimetacarb + TX, warfarin + TX, zinc naphthenate + TX, zinc phosphide + TX, ziram + TX.
[0486] In addition, the compositions of the present invention may be administered together with one or more systemic acquired resistance inducers ("SAR" inducers). SAR inducers are known, for example, described in U.S. Patent No. 6,919,298, and include, for example, salicylates and the commercially available SAR inducer acibenzolar-S-methyl.
[0487] The compounds of formula (I) as defined in the present invention are typically used in the form of compositions and can be applied simultaneously with or consecutively to a crop or plant to be treated with further compounds. These further compounds may be, for example, fertilizers or trace element donors, or other preparations that affect plant growth. They may also be selective or non-selective herbicides, and insecticides, fungicides, bactericidal agents, nematicides, molluskicides, or mixtures of these preparations, and may optionally include further carriers, surfactants, or application enhancers commonly used in the art of formulations.
[0488] The compounds of formula (I) as defined in the present invention can be used in the form of a (fungicidal) composition for the control or protection of plant pathogenic microorganisms, comprising, as an active ingredient, at least one compound of formula (I) as defined in the present invention, or at least one preferred individual compound as defined above in free form or in agrochemically usable salt form, and at least one of the above-mentioned auxiliary agents.
[0489] Accordingly, the present invention provides a composition, preferably a fungicidal composition, comprising at least one compound of formula (I) as defined in the present invention, an agriculturally acceptable carrier, and optionally an auxiliary agent. The agriculturally acceptable carrier is, for example, a carrier suitable for agricultural use. Agricultural carriers are well known in the art. Preferably, the composition may, in addition to the compound of formula (I) as defined in the present invention, comprise at least one or more pesticide compounds, such as additional fungicidal active ingredients.
[0490] Further aspects of the present invention relate to methods for controlling or preventing ectoparasitism of plants, such as useful plants, such as crop plants, their reproductive materials, such as seeds, harvested crops, such as harvested food crops, or non-biological materials, by plant pathogenic or putrefactive microorganisms or organisms, particularly fungi, that are potentially harmful to humans, and that methods include the application of compounds of formula (I) as defined in the present invention, or preferred individual compounds previously defined as active ingredients for plants, to plants, to parts of plants, or to their habitats, to their reproductive materials, or to any part of non-biological materials.
[0491] Control or prevention means reducing ectopic parasites by insects, plant pathogenic or putrefactive microorganisms, or organisms potentially harmful to humans, particularly fungi, to a level where improvement is demonstrated.
[0492] A preferred method for controlling or preventing ectoparasitism of crop plants by plant pathogenic microorganisms, particularly fungi, is foliar application, which includes the application of a compound of formula (I) as defined in the present invention, or a pesticide composition containing at least one of the said compounds. The frequency and amount of application depend on the risk of ectoparasitism by the corresponding pathogen or insect. However, the compound of formula (I) as defined in the present invention can also be introduced into plants through the soil via the roots (osmotic action) by drenching the plant habitat with a liquid formulation or by applying the compound to the soil in solid form, for example, in granular form (soil application). In rice crops, such granular material can be applied to flooded paddy fields. The compound of formula (I) as defined in the present invention can also be applied to seeds (coating) by either impregnating the seeds or tubers with a liquid formulation of the fungicide or coating the seeds or tubers with a solid formulation.
[0493] A composition containing, for example, a compound of formula (I) as defined in the present invention, and, if desired, a solid or liquid additive or a monomer for encapsulating the compound of formula (I) as defined in the present invention, can be prepared by known methods, typically by closely mixing and / or grinding the compound with an extender, such as a solvent, a solid carrier, and optionally a surfactant.
[0494] Methods of application for the composition, i.e., methods for controlling the above-mentioned types of pathogens, such as spraying, misting, dusting, brushing, coating, diffusion, or pouring (these should be selected according to the intended purpose of the general situation), and the use of the composition for controlling the above-mentioned types of pathogens are also subjects of the present invention. Typical concentration ratios are 0.1 to 1000 ppm, preferably 0.1 to 500 ppm of the active ingredient. The application rate per hectare is preferably 1 g to 2000 g of the active ingredient per hectare, more preferably 10 to 1000 g / ha, and most preferably 10 to 600 g / ha. When used as a seed drenching agent, a convenient dosage is 10 mg to 1 g of the active substance per kg of seed.
[0495] When the combination of the present invention is used for seed treatment, it is generally sufficient to use a ratio of the compound of formula (I) of 0.001 to 50 g per kg of seed, preferably 0.01 to 10 g per kg of seed.
[0496] Preferably, a composition comprising a compound of formula (I) according to the present invention as defined herein is administered either preventively (meaning before the onset of disease) or therapeutically (meaning after the onset of disease).
[0497] The compositions of the present invention can be in any conventional form, for example, two-component systems, dry seed treatment powders (DS), seed treatment emulsions (ES), seed treatment fluid concentrates (FS), seed treatment solutions (LS), water-dispersible seed treatment powders (WS), seed treatment capsule suspensions (CF), seed treatment gels (GF), emulsion concentrates (EC), suspension concentrates (SC), suspension emulsions (SE), capsule suspensions (CS), water-dispersible granules (WG), and emulsifying granules. It may be employed in the form of any technically feasible formulation, such as (EG), water-in-oil (EO) emulsion, oil-in-water (EW) emulsion, microemulsion (ME), oil dispersion (OD), oil-miscible flowable (OF), oil-miscible liquid (OL), soluble concentrate (SL), ultra-low volume suspension (SU), ultra-low volume liquid (UL), industrial concentrate (TK), dispersible concentrate (DC), wettable powder (WP), or in combination with agriculturally acceptable auxiliaries.
[0498] Such compositions can be produced by conventional methods, for example, by mixing an active ingredient with a suitable formulation deactivator (diluent, solvent, filler, and optionally other formulation components, such as surfactants, biocides, antifreezes, spreading agents, thickeners, and compounds that provide auxiliary effects). Conventional sustained-release formulations can also be used when sustained effectiveness over a long period is desired. In particular, formulations applied in spray form, such as water-dispersible concentrates (e.g., EC, SC, DC, OD, SE, EW, and EO), wettable powders, and granules, may contain surfactants, such as wetting agents and dispersants, and other compounds that provide auxiliary effects, such as condensation products of formaldehyde with naphthalene sulfonates, alkylaryl sulfonates, lignin sulfonates, fatty alkyl sulfates, and ethoxylated alkylphenols and ethoxylated fatty alcohols.
[0499] The seed coating formulation is applied to the seeds in a manner known to the present invention, using the combination and diluent of the present invention, in a suitable seed coating formulation form, for example, as an aqueous suspension, or in a dry powder form with good adhesion to seeds. Such seed coating formulations are known in the art. The seed coating formulation may contain a single active ingredient, or a combination of active ingredients in encapsulated form, for example, as a slow-release capsule or microcapsule.
[0500] Generally, a formulation comprises 0.01 to 90% by weight of an active agent, 0 to 20% of an agrochemically acceptable surfactant, and 10 to 99.99% of solid or liquid inert formulations and auxiliary agents, wherein the active agent consists of at least a compound of formula (I) as defined in this invention, together with components (B) and (C), and optionally other active agents such as microbiotacitists or preservatives. The concentrated form of the composition generally contains about 2 to 80% by weight, preferably about 5 to 70% by weight of the activator. The application form of the formulation may contain, for example, 0.01 to 20% by weight, preferably 0.01 to 5% by weight of the activator. Commercial products are preferably formulated as concentrates, but end users typically use diluted formulations.
[0501] While it is preferable to incorporate commercially available products as concentrates, end users typically utilize diluted formulations. [Examples]
[0502] The following examples illustrate the present invention. Certain compounds of the present invention can be distinguished from known compounds by their greater potency at lower doses, which can be verified by those skilled in the art using the experimental procedures outlined in the examples.
[0503] Combination example
[0504] [Table 2]
[0505] By thoroughly mixing the active ingredient with an auxiliary agent and then grinding the mixture in a suitable grinder, a wettable powder can be obtained that can be diluted with water to form a suspension of the desired concentration.
[0506] [Table 3]
[0507] The active ingredient is thoroughly mixed with an auxiliary agent, and the mixture is thoroughly ground in a suitable mill to obtain a powder that can be used directly for seed processing.
[0508] emulsifiable concentrate Active ingredient [compound of formula (I)] 10% Octylphenol polyethylene glycol ether 3% (4-5 mol of ethylene oxide) Calcium dodecylbenzenesulfonate 3% Castor oil polyglycol ether (ethylene oxide 35 mol) 4% Cyclohexanone 30% Xylene mixture 50%
[0509] Emulsions of any required dilution, suitable for plant protection, can be obtained from this concentrate by dilution with water.
[0510] [Table 4]
[0511] A readily usable powder can be obtained by mixing the active ingredient with a carrier and grinding the mixture in a suitable mill. Such a powder can also be used for drying and coating seeds.
[0512] Extruded granules Active ingredient [compound of formula (I)] 15% Sodium lignin sulfonate 2% Carboxymethylcellulose 1% Kaolin 82%
[0513] The active ingredient is mixed with an auxiliary agent and ground, and the mixture is moistened with water. The mixture is then extruded and dried in an airflow.
[0514] Coated granules Active ingredient [compound of formula (I)] 8% Polyethylene glycol (molecular weight 200) 3% Kaolin 89%
[0515] The finely ground active ingredient is uniformly applied to kaolin moistened with polyethylene glycol in a mixer. In this way, non-dusty coated granules are obtained.
[0516] Suspension concentrate Active ingredient [compound of formula (I)] 40% Propylene glycol 10% Nonylphenol polyethylene glycol ether (ethylene oxide 15 mol) 6% Sodium lignin sulfonate 10% Carboxymethylcellulose 1% Silicone oil (in the form of a 75% emulsion in water) 1% water 32%
[0517] The finely ground active ingredient is tightly mixed with an auxiliary agent to obtain a suspension concentrate. By diluting this with water, a suspension of the desired dilution can be obtained. Using such a diluted solution, not only growing plants but also plant propagation materials can be treated by spraying, pouring, or immersion to protect them from microbial ectoparasitism.
[0518] Fluidizing agent for seed treatment Active ingredient [compound of formula (I)] 40% Propylene glycol 5% Copolymer Butanol PO / EO 2% Tristyrenephenol 2% with 10-20 moles of EO 1,2-Benzisothiazolin-3-one (in the form of a 20% aqueous solution) 0.5% Monoazo pigment calcium salt 5% Silicone oil (in the form of a 75% emulsion in water) 0.2% Water 45.3%
[0519] The finely ground active ingredient is tightly mixed with an auxiliary agent to obtain a suspension concentrate. By diluting this with water, a suspension of the desired dilution can be obtained. Using such a diluted solution, not only growing plants but also plant propagation materials can be treated by spraying, pouring, or immersion to protect them from microbial ectoparasitism.
[0520] Sustained-release capsule suspension Mix 28 parts of the compound combination of formula (I) with 2 parts of aromatic solvent and 7 parts of a toluene diisocyanate / polymethylene-polyphenyl isocyanate mixture (8:1). Emulsify this mixture in a mixture of 1.2 parts polyvinyl alcohol, 0.05 parts defoamer, and 51.6 parts water until the desired particle size is reached. Add a mixture of 2.8 parts 1,6-diaminohexane in 5.3 parts water to this emulsion. Stir the mixture until the polymerization reaction is complete. Stabilize the resulting capsule suspension by adding 0.25 parts thickener and 3 parts dispersant. The capsule suspension formulation contains 28% active ingredient. The diameter of the medium capsules is 8 to 15 micrometers.
[0521] The resulting mixture is applied to the seeds as an aqueous suspension in an apparatus suitable for the purpose.
[0522] Analysis method: Throughout this specification, temperatures are expressed in degrees Celsius (°C), and "mp" indicates the melting point. LC / MS stands for liquid chromatography-mass spectrometry, and the apparatus and method are described below.
[0523] Method A: The spectra were recorded using a Waters Corporations ACQUITY mass spectrometer (SQD or SQDII single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive or negative ions, capillary: 3.0kV, cone: 30V, extractor: 3.00V, source temperature: 150°C, desolvation temperature: 400°C, cone gas flow rate: 60 L / h, desolvation gas flow rate: 700 L / h, mass range: 140~800 Da), as well as a Waters Corporations ACQUITY UPLC equipped with a solvent degasser, binary pump, heated column compartment, and diode array detector. Column: Waters UPLC HSS T3, 1.8 μm, 30 × 2.1 mm, Temperature: 60°C, DAD wavelength range (nm): 210~400, Solvent gradient: A = Water / Methanol 9:1 + 0.1% Formic Acid, B = Acetonitrile + 0.1% Formic Acid, Gradient: 0~100% B over 2.5 minutes, Flow rate (mL / min) 0.75.
[0524] Method B: Spectra were recorded using Multimode-Electron Spray and APCI (polarity: positive and negative ions), capillary: 4.00kV, corona current: 4.0μA, charging voltage: 2.00kV, nitrogen gas flow rate: 12.0L / min, nebulizer pressure: 40psi, mass range: 100~1000m / z), dry gas temperature: 250℃, vaporizer temperature: 200℃, and Waters UPLC: quaternary pump, heated column compartment, and diode array detector. Column: X-Bridge BEH C18, 2.5μm (2.1×50mm), column temperature: ambient, wavelength (nm): 215nm, gradient: A = 0.05% TFA in water, B = 0.05% TFA in acetonitrile. Gradient: Time / %B: 0 / 5, 1 / 5, 5 / 70, 7 / 95, 8.5 / 95, 8.6 / 5, 10 / 5; Flow rate: 0.6 mL / min.
[0525] Method C: Instrument: Shimadzu LCMS 2020 mass spectrometer; Column: HALO C18 2.7 μm, 3.0 mm × 30 mm; Mobile phase: MeCN (containing either 0.05% HCOOH or 0.05% TFA) - Water (containing either 0.05% HCOOH or 0.05% TFA); Gradient: 5% to 95% MeCN over 1.4 minutes, hold for 0.6 minutes, total run time 2.5 minutes; Flow rate: 1.8 mL / min; Column temperature: 50°C; Wavelength: PDA at 214 and 254 nm.
[0526] Table A below summarizes the compounds of formula (I): - LC / MS data, e.g., retention time (RT), [M+H] + , - Type of method, and / or - Melting point (mp).
[0527] [Table 5-1]
[0528] [Table 5-2]
[0529] [Table 5-3]
[0530] Example 1: Preparation of methyl N-[5-[5-[(4-fluoro-3-methoxyphenyl)-methyl-carbamoyl]-7-methyl-pyrazolo[1,5-a]pyridin-3-yl]-2-pyridyl]carbamate (Compound 1) [ka]
[0531] Step A: Preparation of tert-butyl N-(1-amino-2-methyl-4-pyridyl)carbamate [ka] A stirred suspension of tert-butyl N-(2-methyl-4-pyridyl)carbamate (CAS 1219112-94-3) (10.0 g, 48.0 mmol, 1.00 equivalent) and O-(2,6-dinitrophenyl)hydroxylamine (CAS: 38100-33-3) (9.56 g, 48.0 mmol, 1.00 equivalent) in acetonitrile (80.0 mL) was stirred at 50°C for 48 hours. The reaction mixture was concentrated under reduced pressure to obtain tert-butyl N-(1-amino-2-methylpyridine-1-ium-4-yl)carbamate, which was used as the crude material in the next step.
[0532] Step B: Preparation of ethyl 5-(tert-butoxycarbonylamino)-7-methylpyrazolo[1,5-a]pyridine-3-carboxylate [ka] Potassium carbonate (0.601 g, 4.35 mmol, 3.00 equivalent) was added at 0°C to a solution of tert-butyl N-(1-amino-2-methylpyridine-1-ium-4-yl)carbamate (0.650 g, 1.45 mmol, 1.00 equivalent) and ethylpropane-2-inoate (0.171 g, 1.74 mmol, 1.20 equivalent) in dimethylformamide (10.0 mL). The reaction mixture was stirred at room temperature for 16 hours. The reaction mixture was poured into water and extracted with ethyl acetate. The combined organic layers were dried over Na₂SO₄, filtered, and concentrated under reduced pressure. The crude residue was purified on a silica gel cartridge (eluted with cyclohexane / ethyl acetate) to obtain ethyl 5-(tert-butoxycarbonylamino)-7-methylpyrazolo[1,5-a]pyridine-3-carboxylate as a yellow solid. 1 H-NMR (400MHz, DMSO-d 6 ,ppm)δ=1.37(s,3H),1.51(s,9H),2.68(s,3H),4.28(q,2H),6.15(br.s,1H),7.09(m,1H),8.24(m,1H),8.32(s,1H).
[0533] Step C: Preparation of ethyl 5-amino-7-methyl-pyrazolo[1,5-a]pyridine-3-carboxylate [ka] 5.20 g, 13.0 mmol, 1.00 equivalent of ethyl 5-(tert-butoxycarbonylamino)-7-methyl-pyrazolo[1,5-a]pyridine-3-carboxylate (5.20 g, 13.0 mmol, 1.00 equivalent) was stirred in 50.0 mL of dichloromethane, to which 2,2,2-trifluoroacetic acid (4.84 mL, 65.1 mmol, 5.00 equivalent) was added. The reaction mixture was stirred at room temperature for 16 hours. The reaction mixture was washed with a sodium carbonate solution and extracted with dichloromethane. The combined organic layers were dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude residue was purified on a silica gel cartridge (eluted with cyclohexane / ethyl acetate) to obtain ethyl 5-amino-7-methyl-pyrazolo[1,5-a]pyridine-3-carboxylate as a yellow solid. 1 H-NMR (400MHz, DMSO-d 6 ,ppm)δ=1.30(t,3H),2.58(s,3H),4.21(q,2H),6.19(s,2H),6.40(s,1H),6.90(m,1H),8.11(s,1H).
[0534] Step D: Preparation of ethyl 5-bromo-7-methylpyrazolo[1,5-a]pyridine-3-carboxylate [ka] To a stirred solution of ethyl 5-amino-7-methyl-pyrazolo[1,5-a]pyridine-3-carboxylate (0.500 g, 2.05 mmol, 1.00 equivalent) in acetonitrile (10.0 mL), hydrogen bromide (1.78 g, 10.3 mmol, 5.00 equivalent) was added at 0°C, followed by sodium nitrite (0.425 g, 6.16 mmol, 3.00 equivalent). The reaction mixture was stirred at 0°C for 30 minutes. Next, copper(I) bromide (0.736 g, 5.13 mmol, 2.50 equivalent) was added. The reaction mixture was stirred at 50°C for 2 hours. The reaction mixture was cooled to 0°C, quenched with ice water, neutralized with 10% sodium hydroxide, and extracted with ethyl acetate. The combined organic layers were dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude residue was purified on a silica gel cartridge (eluting cyclohexane / ethyl acetate) to obtain ethyl 5-bromo-7-methyl-pyrazolo[1,5-a]pyridine-3-carboxylate as an off-white solid. 1 H-NMR (400MHz, DMSO-d 6 ,ppm)δ=1.32(t,3H),2.72(s,3H),4.31(q,2H),7.35(s,1H),8.11(s,1H),8.50(s,1H).
[0535] Step E: Preparation of 5-bromo-7-methylpyrazolo[1,5-a]pyridine (compound X-1) [ka] Ethyl 5-bromo-7-methyl-pyrazolo[1,5-a]pyridine-3-carboxylate (0.100 g, 0.318 mmol, 1.00 equivalent) and sulfuric acid (0.779 g, 0.318 mmol, 1.00 equivalent) were stirred at 100°C for 16 hours. The reaction mixture was cooled to 0°C, basicized with 3N sodium hydroxide solution, and extracted with ethyl acetate. The combined organic layers were dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude residue was purified on a silica gel cartridge (eluted with cyclohexane / ethyl acetate) to obtain 5-bromo-7-methyl-pyrazolo[1,5-a]pyridine as an off-white solid. 1 H-NMR (400MHz, DMSO-d 6 ,ppm)δ=2.75(s,3H),6.50(d,1H),6.74(s,1H),7.65(s,1H),7.96(s,1H).
[0536] Step F: Preparation of methyl 7-methylpyrazolo[1,5-a]pyridine-5-carboxylate [ka] A mixture of 5-bromo-7-methylpyrazolo[1,5-a]pyridine (compound X-1) (1.40 g, 5.97 mmol, 1.00 equivalent), N,N-diethylethaneamine (1.66 mL, 11.9 mmol, 2.00 equivalent), and [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.437 g, 0.597 mmol, 0.10 equivalent) in methanol was flushed with nitrogen in a high-pressure vessel. The vial was pressurized with nitrogen, then with CO gas. The reaction mixture was stirred at 110°C for 6 hours. The reaction mixture was filtered through Celite and concentrated under reduced pressure. The crude residue was purified on...
Claims
1. Equation (I) 【Chemistry 1】 The compound (wherein Z is O or S, preferably Z is O; A 1 is CH or N, preferably N; R 1a is selected from hydroxy, halogen, CN, C 1-6 alkyl, C 3-6 cycloalkyl, C 1-6 alkoxy-C 1-6 alkyl, C 3-6 cycloalkyl-C 1-4 alkyl, C 1-6 alkylsulfanyl, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, C 1-6 alkoxy, amino, and -NHC(O)C 1-6 alkyl; R 1b , R 1c , and R 1d These are hydrogen, hydroxyl, halogen, CN, and C 1-6 Alkyl, C 3-6 Cycloalkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 1-6 Alkyl sulfanyl, C 1-6 Alkyl sulfinyl, C 1-6 Alkyl sulfonyl, C 1-6 Alkoxy, amino, and NHC(O)C 1-6 Selected independently of alkyl; A 2 CR is independent 2 or N, provided there are three or fewer A's. 2 is N, preferably two or fewer A 2 is N, preferably one or less A 2 is N, and more preferably four A 2 CR 2 Provided that; R 2 These are hydrogen, hydroxyl, halogen, CN, and C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 2-6 Alkenil, C 2-6 Alkinyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl, C 1-6 Alkyl sulfanyl, C 1-6 Alkyl sulfinyl, C 1-6 Alkyl sulfonyl, C 1-6 Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, diC 1-6 Alkylaminocarbonyl, and C 1-6 Independently selected from alkylcarbonyls, where C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 2-6 Alkenil, C 2-6 Alkinyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl, C 1-6 Alkyl sulfanyl, C 1-6 Alkyl sulfinyl, C 1-6 Alkyl sulfonyl, C 1-6 Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, diC 1-6 Alkylaminocarbonyl, and C 1-6 Each alkylcarbonyl group is optionally substituted with one to three substituents independently selected from halogens, hydroxyls, and CNs; A 3 CR 3 or N; R 3 is selected from hydrogen, hydroxy, halogen, CN, C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 alkyl, C 1-6 alkoxy-C 1-6 alkoxy, C 2-6 alkenyl, C 2-6 alkynyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-6 alkyl, C 1-6 alkylsulfanyl, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, amino, C 1-6 alkylamino, diC 1-6 -alkylamino, and C 3-6 cycloalkylamino, wherein each of the C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 alkyl, C 1-6 alkoxy-C 1-6 alkoxy, C 2-6 alkenyl, C 2-6 alkynyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-6 alkyl, C 1-6 alkylsulfanyl, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, amino, C 1-6 alkylamino, diC 1-6 -alkylamino, and C 3-6 cycloalkylamino group is optionally substituted by 1 to 3 substituents independently selected from halogen, hydroxy, and CN; R 4 C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 2-6 Alkenil, C 2-6 Alkinyl, C 1-6 Alkoxy, C 1-6 Alkylsulfanyl-C 1-6 Alkyl, C 1-6 Alkylsulfinyl-C 1-6 Alkyl, C 1-6 Alkylsulfonyl-C 1-6 Alkyl, C 1-6 Alkoxycarbonyl-C 1-6 Alkyl, C 1-6 Alkylaminocarbonyl-C 1-6 Alkyl, diC 1-6 Alkylaminocarbonyl-C 1-6 Selected from alkyl and CN, where C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 2-6 Alkenil, C 2-6 Alkinyl, C 1-6 Alkoxy, C 1-6 Alkylsulfanyl-C 1-6 Alkyl, C 1-6 Alkylsulfinyl-C 1-6 Alkyl, C 1-6 Alkylsulfonyl-C 1-6 Alkyl, C 1-6 Alkoxycarbonyl-C 1-6 Alkyl, C 1-6 Alkylaminocarbonyl-C 1-6 Alkyl and diC 1-6 Alkylaminocarbonyl-C 1-6 Each alkyl group is optionally substituted with one to three substituents independently selected from halogens and CNs; Here, A 3 and R 4 They may optionally come together to form a ring, preferably a 5- to 8-membered heterocycle, more preferably a 6-membered heterocycle; R 5 C 1-6 Alkyl, C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl, C 1-6 Alkoxy C 1-6 Alkyl, C 1-6 Alkylamino, diC 1-6 Alkylamino, and C 1-6 Alkyl C 1-6 Selected from alkoxyaminos, where each of the groups is optionally substituted with one to three substituents independently selected from halogens and CNs. or its salt or N-oxide.
2. R 1a C 1-6 Alkyl, C 3-6 Cycloalkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl and C 1-6 Selected from alkoxys, preferably C 1-6 The compound according to claim 1, wherein it is alkyl.
3. R 1b , R 1c , and R 1d is hydrogen, C 1-6 Alkyl, C 3-6 Cycloalkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl and C 1-6 A compound according to claim 1 or 2, independently selected from alkoxys.
4. R 1a is hydroxy, halogen, CN, C 1-6 Alkyl, C 3-6 Cycloalkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 1-6 Alkyl sulfanyl, C 1-6 Alkyl sulfinyl, C 1-6 Alkyl sulfonyl, C 1-6 Alkoxy, amino, and NHC(O)C 1-6 Selected from alkyl groups; R 1b , R 1c , and R 1d The compound according to claim 1, wherein is hydrogen.
5. R 2 These are hydrogen, hydroxyl, halogen, CN, and C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 1-6 Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, diC 1-6 Alkylaminocarbonyl, and C 1-6 Independently selected from alkylcarbonyls, where C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 1-6 Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, diC 1-6 Alkylaminocarbonyl, and C 1-6 The compound according to any one of claims 1 to 4, wherein each alkylcarbonyl group is optionally substituted with one to three substituents independently selected from halogens, hydroxyls, and CNs.
6. R 3 These are hydrogen, hydroxyl, halogen, CN, and C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl, amino, C 1-6 Alkylamino, diC 1-6 - Alkylamino, and C 3-6 Selected from cycloalkylamino, where C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl, amino, C 1-6 Alkylamino, diC 1-6 - Alkylamino, and C 3-6 The compound according to any one of claims 1 to 5, wherein each cycloalkylamino group is optionally substituted with one to three substituents independently selected from halogens, hydroxyls, and CNs.
7. The four A's 2 CR 2 A 3 The compound according to any one of claims 1 to 6, wherein is N. 【Request Item 8】 【Chemistry 2】 teeth 【Transformation 3】 And, Preferably three A 2 CR 2 A 3 CR 3 The compound according to any one of claims 1 to 6. 【Request Item 9】 【Chemistry 4】 teeth 【Transformation 5】 And, Preferably three A 2 CR 2 A 3 CR 3 The compound according to any one of claims 1 to 6.
10. The four A's 2 CR 2 A 3 CR 3 Preferably 【Transformation 6】 teeth 【Transformation 7】 The compound according to any one of claims 1 to 6.
11. R 4 C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 2-6 Alkenil, C 2-6 Alkinyl and C 1-6 Selected from alkoxy, where C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 2-6 Alkenil, C 2-6 Alkinyl and C 1-6 The compound according to any one of claims 1 to 10, wherein each alkoxy group is optionally substituted with one to three substituents independently selected from halogens and CNs.
12. R 5 C 1-6 Alkyl, C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl and C 1-6 Alkoxy C 1-6 The compound according to any one of claims 1 to 11, wherein each of the alkyl groups is optionally substituted with one to three substituents independently selected from halogens and CNs.
13. A composition comprising an effective fungicidal amount of the compound described in any one of claims 1 to 12.
14. The composition according to claim 13, further comprising at least one compound selected from additional active ingredients, suitable inactive ingredients, carriers, auxiliaries, and any mixture thereof.
15. A method for eradicating, preventing, or controlling plant pathogenic diseases, comprising applying a fungicidal amount of a compound according to any one of claims 1 to 12, a composition containing a compound according to any one of claims 1 to 12, or a composition according to claim 13 or 14 to a plant pathogen, a habitat of a plant pathogen, a plant susceptible to attack by a plant pathogen, or a plant reproductive material thereof.
16. Formula (XI) 【Transformation 8】 The compound (wherein Z is O or S, preferably Z is O; R 1a is hydroxy, halogen, CN, C 1-6 Alkyl, C 3-6 Cycloalkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 1-6 Alkyl sulfanyl, C 1-6 Alkyl sulfinyl, C 1-6 Alkyl sulfonyl, C 1-6 Alkoxy, amino, and -NHC(O)C 1-6 Selected from alkyl groups; preferably, R 1a C 1-6 Alkyl, C 3-6 Cycloalkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl and C 1-6 Selected from alkoxy; R 1b , R 1c , and R 1d These are hydrogen, hydroxyl, halogen, CN, and C 1-6 Alkyl, C 3-6 Cycloalkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 1-6 Alkyl sulfanyl, C 1-6 Alkyl sulfinyl, C 1-6 Alkyl sulfonyl, C 1-6 Alkoxy, amino, and -NHC(O)C 1-6 Selected independently of alkyl groups; preferably, R 1b , R 1c , and R 1d is hydrogen; A 2 CR is independent 2 or N, provided there are three or fewer A's. 2 is N, preferably two or fewer A 2 is N, preferably one or less A 2 is N, and more preferably four A 2 CR 2 Provided that; R 2 These are hydrogen, hydroxyl, halogen, CN, and C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 1-6 Alkyl sulfonyl, C 1-6 Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, diC 1-6 Alkylaminocarbonyl, and C 1-6 Independently selected from alkylcarbonyls, where C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 1-6 Alkyl sulfonyl, C 1-6 Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, diC 1-6 Alkylaminocarbonyl, and C 1-6 The alkylcarbonyl group is optionally substituted with one substituent independently selected from halogens, hydroxyls, and CNs; preferably, R 2 Hydrogen, halogen, CN, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxycarbonyl and C 1-6 Alkoxy-C 1-6 Selected independently of alkoxy, where C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxycarbonyl and C 1-6 Alkoxy-C 1-6 Each alkoxy group is optionally substituted with one to three substituents independently selected from halogens, hydroxyls, and CNs; provided that at least two R groups are present. 2 Preferably not hydrogen; A 3 CR is independent 3 or N; R 3 These are hydrogen, hydroxyl, halogen, CN, and C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 1-6 Alkyl sulfonyl, C 1-6 Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, diC 1-6 Alkylaminocarbonyl, and C 1-6 Selected from alkylcarbonyl, where C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 1-6 Alkyl sulfonyl, C 1-6 Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, diC 1-6 Alkylaminocarbonyl, and C 1-6 Each alkylcarbonyl group is optionally substituted with one substituent independently selected from halogens, hydroxyls, and CNs; preferably, R 3 is hydrogen; R 4 C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 2-6 Alkenil, C 2-6 Alkinyl, C 1-6 Alkoxy, C 1-6 Alkylsulfanyl-C 1-6 Alkyl, C 1-6 Alkylsulfinyl-C 1-6 Alkyl, C 1-6 Alkylsulfonyl-C 1-6 Alkyl, C 1-6 Alkoxycarbonyl-C 1-6 Alkyl, C 1-6 Alkylaminocarbonyl-C 1-6 Alkyl, diC 1-6 Alkylaminocarbonyl-C 1-6 Selected from alkyl and CN, where C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 2-6 Alkenil, C 2-6 Alkinyl, C 1-6 Alkoxy, C 1-6 Alkylsulfanyl-C 1-6 Alkyl, C 1-6 Alkylsulfinyl-C 1-6 Alkyl, C 1-6 Alkylsulfonyl-C 1-6 Alkyl, C 1-6 Alkoxycarbonyl-C 1-6 Alkyl, C 1-6 Alkylaminocarbonyl-C 1-6 Alkyl and diC 1-6 Alkylaminocarbonyl-C 1-6 Each alkyl group is optionally substituted with one to three substituents independently selected from halogens and CNs; Here, A 3 and R 4 (These elements can optionally come together to form a ring, preferably a 5-8 membered heterocycle, more preferably a 6-membered heterocycle.) or its salt or N-oxide; Or Formula (II) 【Chemistry 9】 The compound (wherein Z is O or S, preferably Z is O; R 1a is hydroxy, halogen, CN, C 1-6 Alkyl, C 3-6 Cycloalkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 1-6 Alkyl sulfanyl, C 1-6 Alkyl sulfinyl, C 1-6 Alkyl sulfonyl, C 1-6 Alkoxy, amino, and -NHC(O)C 1-6 Selected from alkyl groups; preferably, R 1a C 1-6 Alkyl, C 3-6 Cycloalkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl and C 1-6 Selected from alkoxy; R 1b , R 1c , and R 1d These are hydrogen, hydroxyl, halogen, CN, and C 1-6 Alkyl, C 3-6 Cycloalkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 1-6 Alkyl sulfanyl, C 1-6 Alkyl sulfinyl, C 1-6 Alkyl sulfonyl, C 1-6 Alkoxy, amino, and -NHC(O)C 1-6 Selected independently of alkyl groups; preferably, R 1b , R 1c , and R 1d is hydrogen; A 2 CR is independent 2 or N, provided there are three or fewer A's. 2 is N, preferably two or fewer A 2 is N, preferably one or less A 2 is N, and more preferably four A 2 CR 2 Provided that; R 2 These are hydrogen, hydroxyl, halogen, CN, and C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 1-6 Alkyl sulfonyl, C 1-6 Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, diC 1-6 Alkylaminocarbonyl, and C 1-6 Independently selected from alkylcarbonyls, where C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 1-6 Alkyl sulfonyl, C 1-6 Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, diC 1-6 Alkylaminocarbonyl, and C 1-6 Each alkylcarbonyl group is optionally substituted with one substituent independently selected from halogens, hydroxyls, and CNs; preferably, R 2 Hydrogen, halogen, CN, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxycarbonyl and C 1-6 Alkoxy-C 1-6 Selected independently of alkoxy, where C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxycarbonyl and C 1-6 Alkoxy-C 1-6 Each alkoxy group is optionally substituted with one to three substituents independently selected from halogens, hydroxyls, and CNs; provided that at least two R groups are present. 2 Preferably not hydrogen; A 3 CR is independent 3 or N; R 3 These are hydrogen, hydroxyl, halogen, CN, and C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 1-6 Alkyl sulfonyl, C 1-6 Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, diC 1-6 Alkylaminocarbonyl, and C 1-6 Selected from alkylcarbonyl, where C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 1-6 Alkyl sulfonyl, C 1-6 Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, diC 1-6 Alkylaminocarbonyl, and C 1-6 Each alkylcarbonyl group is optionally substituted with one substituent independently selected from halogens, hydroxyls, and CNs; preferably, R 3 is hydrogen; R 4 C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 2-6 Alkenil, C 2-6 Alkinyl, C 1-6 Alkoxy, C 1-6 Alkylsulfanyl-C 1-6 Alkyl, C 1-6 Alkylsulfinyl-C 1-6 Alkyl, C 1-6 Alkylsulfonyl-C 1-6 Alkyl, C 1-6 Alkoxycarbonyl-C 1-6 Alkyl, C 1-6 Alkylaminocarbonyl-C 1-6 Alkyl, diC 1-6 Alkylaminocarbonyl-C 1-6 Selected from alkyl and CN, where C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 2-6 Alkenil, C 2-6 Alkinyl, C 1-6 Alkoxy, C 1-6 Alkylsulfanyl-C 1-6 Alkyl, C 1-6 Alkylsulfinyl-C 1-6 Alkyl, C 1-6 Alkylsulfonyl-C 1-6 Alkyl, C 1-6 Alkoxycarbonyl-C 1-6 Alkyl, C 1-6 Alkylaminocarbonyl-C 1-6 Alkyl and diC 1-6 Alkylaminocarbonyl-C 1-6 Each alkyl group is optionally substituted with one to three substituents independently selected from halogens and CNs; Here, A 3 and R 4 They may optionally come together to form a ring, preferably a 5- to 8-membered heterocycle, more preferably a 6-membered heterocycle; X is Cl, Br, or I. or its salt or N-oxide.