Pesticidally active aminoheterocycle derivatives
Novel aminoheterocycle derivatives provide effective pest control solutions for managing arthropod pests and parasites, addressing the limitations of existing methods by offering improved pesticidal activity and broad applicability in agricultural and animal health contexts.
Patent Information
- Application Number
- PCT/CN2025/094953
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2024-06-13
- Filing Date
- 2025-05-14
- Publication Date
- 2025-12-18
AI Technical Summary
Existing pest control methods are inadequate for effectively managing arthropod pests, particularly insects from the order Lepidoptera, and there is a need for novel compounds with improved pesticidal activity.
Development of pesticidally active aminoheterocycle derivative compounds, including specific structures and their agronomically acceptable salts, stereoisomers, and enantiomers, which can be applied in various forms to combat pests and parasites, with methods for their synthesis and formulation in compositions.
The compounds demonstrate effective pest control, reducing pest populations and preventing further damage to plants and plant-derived products, while being applicable in agricultural, horticultural, and ornamental settings, and for controlling ectoparasites on animals.
Smart Images

Figure CN2025094953_18122025_PF_FP_ABST
Abstract
Description
PESTICIDALLY ACTIVE AMINOHETEROCYCLE DERIVATIVES
[0001] The present invention relates to pesticidally active, in particular insecticidally active aminoheterocycle derivative compounds, to processes for their preparation, to compositions comprising those compounds, and to their use for controlling animal pests, including arthropods and in particular insects or representatives of the order Lepidoptera.
[0002] There have now been found novel pesticidally active aminoheterocycle derivative compounds.
[0003] The present invention accordingly relates, in a first aspect, to a compound of the Formula (I) :
[0004] wherein
[0005] R1 to R5 are independently selected from H, halogen, C1-6alkyl, C3-6cycloalkyl, C1-6alkoxy, C1-6haloalkyl, C1-6halocycloalkyl, and C1-6haloalkoxy;
[0006] R6 is H or CH3;
[0007] Q is selected from:
[0008] T is selected from:
[0009] R7 and R8 are independently selected from H, methyl, ethyl, isopropyl, cyclopropyl, cyclobutyl, 2- (acetamid) ethyl, 2-ethoxyethyl, oxolan-3-yl, thietan-3-yl, oxetan-3-yl, propen-2-yl, 2-methoxyethyl, 2, 2-diethoxyethyl, oxan-4-yl, 2-methyl-1, 3-dioxolane, 3-methoxypropyl, 2-hydroxyethyl, 3, 3-methoxypropyl, 2-cyanoethyl or 2-methylsulfonylethyl, or
[0010] R7 and R8 together with the nitrogen atom to which they are attached form an imidazole or morpholine group;
[0011] W is selected from
[0012] or is a direct bond,
[0013] with the proviso that if T is T5 then W is a direct bond;
[0014] A is a phenyl group, a C6cycloalkyl, or piperidine ring,
[0015] wherein A is optionally substituted by one or more of halogen, C1-6alkyl, C1-6cycloalkyl, C1-6alkoxy, C1-6haloalkyl, C1-6halocycloalkyl, C1-6haloalkoxy;
[0016] or an agronomically acceptable salt, stereoisomer, enantiomer, tautomer and / or N-oxide of the compound of Formula (I) .
[0017] Compounds of formula (I) which have at least one basic centre can form, for example, acid addition salts, for example with strong inorganic acids such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphorus acid or a hydrohalic acid, with strong organic carboxylic acids, such as C1-C4alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as C1-C4alkane-or arylsulfonic acids which are unsubstituted or substituted, for example by halogen, for example methane-or p-toluenesulfonic acid. Compounds of formula (I) which have at least one acidic group can form, for example, salts with bases, for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di-or tri-lower-alkylamine, for example ethyl-, diethyl-, triethyl-or dimethylpropylamine, or a mono-, di-or trihydroxy-lower-alkylamine, for example mono-, di-or triethanolamine.
[0018] In each case, the compounds of formula (I) according to the invention are in free form, in oxidized form as a N-oxide or in salt form, e.g. an agronomically usable salt form.
[0019] N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen containing heteroaromatic compounds. They are described for instance in the book “Heterocyclic N-oxides” by A. Albini and S. Pietra, CRC Press, Boca Raton 1991.
[0020] The compounds of formula (I) according to the invention also include hydrates which may be formed during the salt formation.
[0021] As used herein, the term "halogen" refers to fluorine (fluoro) , chlorine (chloro) , bromine (bromo) or iodine (iodo) .
[0022] As used herein, the term “hydroxyl” or “hydroxy” means an -OH group.
[0023] As used herein, the term “hydrosulfido” or “mercapto” means an -SH group.
[0024] As used herein, the term “cyano” means a -CN group.
[0025] As used herein, amino means an -NH2 group.
[0026] As used herein, nitro means an -NO2 group.
[0027] As used herein, acyl means a -C (O) CH3 group.
[0028] As used herein, formyl means a -C (O) H group.
[0029] As used herein, oxo means an =O group (eg, as in a carbonyl (C=O) group) .
[0030] As used herein, the term "C1-n alkyl" refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, having from one to n carbon atoms, and which is attached to the rest of the molecule by a single bond. The term "C1-6alkyl" is to be construed accordingly. Examples of C1-6alkyl include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl and the isomers thereof, for example, iso-propyl, iso-butyl, sec-butyl, tert-butyl or iso-amyl. A “C1-4alkylene” group refers to the corresponding definition of C1-4alkyl, except that such radical is attached to the rest of the molecule by two single bonds. The term “C1-2alkylene” is to be construed accordingly. Examples of C1-4alkylene, include, but are not limited to, -CH2-, -CH2CH2-and - (CH2) 3-.
[0031] As used herein, the term "C2-n alkenyl" refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one double bond that may be of either the (E) or (Z) configuration, having from two to n carbon atoms, which is attached to the rest of the molecule by a single bond. C2-6alkenyl is to be construed accordingly. Examples of C2-C6alkenyl include, but are not limited to, prop-1-enyl, allyl (prop-2-enyl) , and but-1-enyl.
[0032] As used herein, the term "C2-n alkynyl" refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one triple bond, having from two to n carbon atoms, and which is attached to the rest of the molecule by a single bond. The term "C2-6alkynyl" is to be construed accordingly. Examples of C2-6alkynyl include, but are not limited to, prop-1-ynyl, propargyl (prop-2-ynyl) , and but-1-ynyl.
[0033] As used herein, the term "C1-n haloalkyl" refers to a C1-n alkyl radical as generally defined above substituted by one or more of the same or different halogen atoms. C1-4haloalkyl and C1-2haloalkyl are to be construed accordingly. Examples of C1-6haloalkyl include, but are not limited to fluoromethyl, fluoroethyl, difluoromethyl, trifluoromethyl, and 2, 2, 2-trifluoroethyl.
[0034] As used herein, the term "C2-n haloalkenyl" refers to a C2-n alkenyl group as defined above substituted by one or more of the same or different halogen atoms. Examples of C2-6haloalkenyl include, but are not limited to 3, 3-dichloroallyl, 2, 3, 3-trichloroallyl, 2, 3-dichloroallyl, 3, 3-dibromoallyl, 2, 3, 3-tribromoallyl, and 2, 3-dibromoallyl.
[0035] As used herein, the term "C2-n haloalkynyl" refers to a C2-n alkynyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
[0036] As used herein, the term “cyanoC1-n alkyl” refers to a C1-n alkyl radical as generally defined above substituted by one or more cyano groups. CyanoC1-6alkyl is to be construed accordingly. Examples of cyanoC1-6alkyl include, but are not limited to, cyanomethyl.
[0037] As used herein, the term “hydroxyC1-n alkyl” refers to a C1-n alkyl radical as generally defined above substituted by one or more hydroxy groups.
[0038] As used herein, the term “aminoC1-n alkyl” refers to a radical of the formula H2NRa-wherein Ra is a C1-n alkylene radical as generally defined above.
[0039] As used herein, the term “C1-n alkylcarbonylC1-n alkyl” refers to a radical of the formula -RbC (O) Ra wherein Ra is a C1-n alkyl as generally defined above and Rb is a C1-n alkylene radical as generally defined above.
[0040] As used herein, the term “C1-n alkoxycarbonylC1-n alkyl” refers to a radical of the formula -RbC (O) ORa, wherein Ra is a C1-n alkyl radical as generally defined above and Rb is a C1-n alkylene radical as generally defined above.
[0041] As used herein, the term "C1-n alkoxy" refers to a radical of the formula -ORa wherein Ra is a C1-n alkyl radical as generally defined above. C1-6alkoxy is to be construed accordingly. Examples of C1-6alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, iso-propoxy, and tert-butoxy.
[0042] As used herein, the term "C1-n alkenoxy" refers to a radical of the formula RaO-, wherein Ra is a C1-n alkenyl radical as generally defined above.
[0043] As used herein, the term "C1-n haloalkoxy" refers to a C1-n alkoxy group as defined above substituted by one or more of the same or different halogen atoms. C1-6haloalkoxy is to be construed accordingly. Examples of C1-6haloalkoxy include, but are not limited to, fluoromethoxy, difluoromethoxy, fluoroethoxy, trifluoromethoxy, and trifluoroethoxy.
[0044] As used herein, the term "C1-n alkylcarbonyloxy" refers to a radical of the formula -OC (O) Ra wherein Ra is a C1-n alkyl radical as generally defined above. The term "C1-6alkylcarbonyloxy" is to be construed accordingly.
[0045] As used herein, the term "C1-n alkoxyC1-n alkyl" refers to a radical of the formula Rb-O-Ra-wherein Rb is a C1-n alkyl radical as generally defined above, and Ra is a C1-n alkylene radical as generally defined above.
[0046] As used herein, the term “C1-n alkoxyC1-n alkoxy” refers to a radical of the formula Ra-O-Rb-wherein Ra is a C1-n alkyl radical as generally defined above, and Rb is a C1-n alkoxy radical as generally defined above.
[0047] As used herein, the term "C1-n alkylcarbonyl" refers to a radical of the formula RaC (O) -, wherein Ra is a C1-n alkyl radical as generally defined above.
[0048] As used herein, the term "C1-Cn haloalkylcarbonyl" refers to a C1-Cn alkylcarbonyl radical as generally defined above, substituted by one or more of the same or different halogen atoms.
[0049] As used herein, the term “C1-n alkoxycarbonyl” refers to a radical of the formula RaOC (O) -, wherein Ra is a C1-n alkyl radical as generally defined above.
[0050] As used herein, the term “C1-Cn alkylaminocarbonyl” refers to a radical of the formula RaNHC (O) -wherein Ra is a C1-Cn alkyl radical as generally defined above.
[0051] As used herein, the term "C1-n alkylcarbonylamino" refers to a radical of the formula RaC (O) N (H) -wherein Ra is a C1-n alkyl radical as generally defined above.
[0052] As used herein, the term "C3-8cycloalkyl" refers to a stable, monocyclic ring radical which is saturated and contains 3 to 8 carbon atoms. C3-6cycloalkyl is to be construed accordingly. Examples of C3-8cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
[0053] As used herein, the term "C3-10cycloalkenyl" refers to a radical which is a monocyclic non-aromatic ring system consisting solely of carbon and hydrogen atoms and which contains 3 to 10 carbon atoms and 1 or 2 endocyclic double bonds. They may include bridged structures (e.g., norbornene and 2, 5-norbornadiene) . Examples of C3-C10cycloalkenyl include, but are not limited to, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl and cyclooctenyl.
[0054] As used herein, the term "C3-6halocycloalkyl" refers to a C3-6cycloalkyl ring as defined above substituted by one or more of the same or different halogen atoms.
[0055] As used herein, the term "C3-8cycloalkylC1-2alkyl" refers to a C3-8cycloalkyl ring as defined above attached to the rest of the molecule by a C1-2alkylene radical as defined above. The term "C3-6cycloalkylC1-2alkyl" should be construed accordingly. Examples of C3-8cycloalkylC1-2alkyl include, but are not limited to cyclopropyl-methyl and cyclobutyl-ethyl.
[0056] As used herein, the term "phenylC1-2alkyl" refers to a phenyl ring attached to the rest of the molecule by a C1-2alkylene radical as defined above. Examples of phenylC1-2alkyl include benzyl.
[0057] As used herein, the term "aryl" refers to an aromatic ring system consisting solely of carbon and hydrogen atoms which may be mono, bi or tricyclic. Examples of such ring systems include phenyl, naphthalenyl, anthracenyl, indenyl or phenanthrenyl.
[0058] As used herein, the term "heteroaryl" refers to a 5-or 6-membered aromatic monocyclic ring radical which comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O and S. Examples of heteroaryl include, but are not limited to, furanyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidyl or pyridyl.
[0059] As used herein, the term "heteroarylC1-2alkyl" refers to a heteroaryl ring as defined above which is attached to the rest of the molecule by a C1-2alkylene radical as defined above.
[0060] As used herein, the term "heterodiaryl" refers to a 9-or 10-membered bicyclic aromatic system which comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O and S. Examples of heterodiaryl include, but are not limited to, quinolinyl and indolinyl.
[0061] As used herein, the term "heterocyclyl" or "heterocyclic" refers to a stable 5-or 6-membered non-aromatic monocyclic ring radical which comprises 1, 2, or 3 heteroatoms individually selected from nitrogen, oxygen and sulfur. The heterocyclyl radical may be bonded to the rest of the molecule via a carbon atom or heteroatom. Examples of heterocyclyl include, but are not limited to, pyrrolinyl, pyrrolidyl, tetrahydrofuranyl, tetrahydrothienyl, tetrahydrothiopyranyl, piperidyl, piperazinyl, tetrahydropyranyl, dioxolanyl, morpholinyl, oxazinanyl, oxetanyl, or δ-lactamyl.
[0062] As used herein, the term "heterocyclylC1-2alkyl" refers to a heterocyclic ring as defined above which is attached to the rest of the molecule by a C1-2alkylene radical as defined above.
[0063] As used herein, the term "controlling" refers to reducing the number of pests, eliminating pests and / or preventing further pest damage such that damage to a plant or to a plant derived product is reduced.
[0064] As used herein, the term "pest" refers to pests that cause damage and / or inconvenience in agriculture, in horticulture, in ornamentals, in forests, in the storage of products of vegetable origin (such as fruit, grain and timber) including damage of man-made structures, or on organs, such as fruits, flowers, foliage, stalks, tubers, plant propagation material (such as seeds) , and roots, of such plants, and in some cases even plant organs which are formed at a later point in time. The term pest encompasses all stages in the life cycle of the pest. Examples of pests include arthropod pests, and nematodes; preferably insects, mites and acarina, particularly insects.
[0065] As used herein, the term "effective amount" refers to the amount of the compound, or a salt thereof, which, upon single or multiple applications provides the desired effect.
[0066] An effective amount is readily determined by the skilled person in the art, by the use of known techniques and by observing results obtained under analogous circumstances. In determining the effective amount a number of factors are considered including, but not limited to: the type of plant or derived product to be applied; the pest to be controlled &its lifecycle; the particular compound applied; the type of application; and other relevant circumstances.
[0067] Embodiments according to the invention are provided as set out below.
[0068] In an embodiment of each aspect of the invention R1 is halogen, C1-6alkyl, C3-6cycloalkyl or C1-6haloalkyl, preferably C1-3alkyl or C1-3haloalkyl; more preferably trifluoromethyl or isopropyl.
[0069] In an embodiment of each aspect of the invention R4 is H, halogen, C1-3alkyl, C3cycloalkyl, or C1-3alkoxy; preferably methyl.
[0070] In an embodiment of each aspect of the invention R2, R3, and R5 are H.
[0071] In an embodiment of each aspect of the invention Q is selected from Q1, Q2 or Q4, preferably Q1.
[0072] In an embodiment of each aspect of the invention A is substituted by halogen, C1-6haloalkoxy, or C1-6haloalkyl, preferably C1-3haloalkoxy; more preferably trifluoromethoxy.
[0073] In an embodiment of each aspect of the invention A is substituted at the 4 position.
[0074] In an embodiment of each aspect of the invention A is a phenyl group.
[0075] In an embodiment of each aspect of the invention A is C6cycloalkyl or piperidine and is doubly substituted at the 4 position.
[0076] In an embodiment of each aspect of the invention T is selected from T1, T3 or T4; preferably T1 or T3.
[0077] In an embodiment of each aspect of the invention W is selected from:
[0078] or a direct bond; preferably a direct bond or
[0079] In an embodiment, R7 and R8 are independently selected from hydrogen, methyl and 2-methyl-1, 3-dioxolane, preferably 2-methyl-1, 3-dioxolane.
[0080] In a second aspect, the present invention makes available a composition comprising a compound of formula (I) as defined in the first aspect, one or more auxiliaries and diluent, and optionally one more other active ingredient.
[0081] In a third aspect, the present invention makes available a method of combating and controlling one or more pests which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest a pesticidally effective amount of a compound of formula (I) as defined in the first aspect or a composition as defined in the second aspect.
[0082] In a fourth aspect, the present invention makes available a method for the protection of plant propagation material from the attack by one or more pests, which comprises treating the propagation material or the site, where the propagation material is planted, with an effective amount of a compound of formula (I) as defined in the first aspect or a composition as defined in the second aspect.
[0083] In a fifth aspect, the present invention makes available a plant propagation material, such as a seed, comprising, or treated with or adhered thereto, a compound of formula (I) as defined in the first aspect or a composition as defined in the second aspect.
[0084] The present invention in a further aspect provides a method of controlling parasites in or on an animal in need thereof comprising administering an effective amount of a compound of formula (I) of the first aspect. The present invention further provides a method of controlling ectoparasites on an animal in need thereof comprising administering an effective amount of a compound of formula (I) as defined om the first aspect. The present invention further provides a method for preventing and / or treating diseases transmitted by ectoparasites comprising administering an effective amount of a compound of formula (I) as defined in the first aspect, to an animal in need thereof.
[0085] In an embodiment, the uses and methods described herein exclude treatment of the human or animal body by surgery or therapy and diagnostic methods practised on the human or animal body. In an embodiment, the use is a non-therapeutic use. In an embodiment, the method is a non-therapeutic method.
[0086] A compound of Formula (I) can exist in different tautomeric forms and a skilled person would readily understand what they are.
[0087] Compounds of Formula (I) can be prepared by those skilled in the art following known methods. More specifically compounds of formulae I, and intermediates therefore can be prepared as described below in the schemes and examples.
[0088] The process according to the invention for preparing compounds of formula (I) is carried out by methods known to those skilled in the art.
[0089] General synthesis
[0090] T1: related
[0091] Compounds of formula (I) can be prepared from compounds of formula (II) , wherein X is a halogen, preferably Cl, Br or I, via treatment with compounds of formula (III) , in the presence of a base (e.g. K2CO3, Cs2CO3, or NaH) in a suitable solvent (eg, dimethylformamide or tetrahydrofuran) at a temperature between 25℃ and 110℃. In some cases, a better reaction performance may be gained from the use of a catalyst (eg, NaI or 4-dimethylaminopyridine) and with microwave irradiation. This reaction can also be catalysed by a copper salt such as copper (I) iodide and a chelator such as 8-hydroxyquinoline, both present in about 0.05 to about 0.25 equivalents, in the presence of caesium carbonate or potassium phosphate, in a polar aprotic solvent such as dimethylformamide at a temperature ranging between about 80℃ and about 140℃. This reaction is shown in Scheme 1.
[0092] Additionally, compounds of formula (I) can be prepared from compounds of formula (IV) , wherein X is a halogen, preferably Cl, Br or I, via treatment with compounds of formula (V) , in the presence of a base in a suitable solvent, such as tetrahydrofuran or ethanol, at a temperature between 25℃ and 75℃. Compounds of formula (Va) are known, synthesis is described in WO 2003 / 028729 and WO 2010 / 045251. This reaction is shown in Scheme 2.
[0093] As depicted in scheme 3, compounds of formula (Va) , where T is T1 can be prepared with different synthetic routes. Compounds of formula (Va) can be performed via Chan-Lam coupling reaction starting from an aryl boronic acid precursor and compounds of formula (VIIa) as described in Chem. A Eur. J., 2017, 23 (14) , 3285-3290. Alternatively, compounds of formula (Va) wherein R6 is hydrogen can be prepared by reduction of nitro compounds of formula (IIaa) using reducing agents such as SnCI2 in acid medium as shown. Alternatively, compounds of formula (Va) wherein R6 is hydrogen can also be prepared by reacting compounds of the formula (IIa) with ammonia in the presence of a metal catalyst or its salts, preferably copper or its salts as described in Chem. Commun., 2009, 3035-3037. Additionally, compounds of formula (Va) wherein R6 is hydrogen can also be prepared in two steps from compounds of the formula (IIa) . Treatment of compounds of formula (IIa) with tert-butyl carbamate in the presence of metal catalyst or its salts, preferably palladium or its salts to form compounds of formula (Vaa) , followed by Boc-deprotection using trifluoroacetic acid or diluted hydrochloric acid to form the desired compound (Va) . All these reactions are performed as described in March's Advanced Organic Chemistry 6'" edition, Michael B. Smith and Jerry March.
[0094] Compounds of formula (IIaa) can be prepared by analogy to the methods described in scheme 4. SNAr reaction between pyrazole (VIIa) and p-fluoro nitroarene as described in WO 2017 / 139274 or can be performed via Chan-Lam coupling reaction starting from an aryl boronic acid precursor as described in Chem. A Eur. J., 2017, 23 (14) , 3285-3290.
[0095] Compounds of formula (IIa) can be prepared by analogy to the methods described in scheme 5.
[0096] Synthesis can be performed via Chan-Lam coupling reaction starting from an aryl boronic acid precursor with pyrazole (VII) as described in Chem. A Eur. J., 2017, 23 (14) , 3285-3290. X as bromide is preferrable.
[0097] Compounds of formula (IIa) where T is pyrazole, W is -C (=O) -NH-, can be prepared by analogy to the methods described in scheme 5a. Compounds of formula (IIaa) can be prepared in two steps via intermediate of formula (XXa) , starting from commercially available beta keto ester derivative and aniline as described in Synthesis, 2019, 51 (6) , 1473-1481. Pyrazole synthesis for compounds of formula (IIaaaa) is described in Angew., Chem., int. Ed., 2010, 49 (42) , 7790-7794. Hydrolysis of ester to acid compounds of formula (IIaaa) using suitable bases like LiOH, NaOH, can be made as mentioned in WO 2011 / 050245. Amide coupling reactions with aniline derivatives (X) and acid (IIaaa) using suitable coupling reagents such as HATU or T3P and bases like DIPEA, can be performed analogous to as described in March's Advanced Organic Chemistry 6" edition, Michael B. Smith and Jerry March.
[0098] Additionally, compounds of formula (Ia) can be prepared from compounds of formula (VI) via treatment with compounds of formula (VIIa) . This reaction is shown in Scheme 6.
[0099] Additionally, compounds of formula (Ia) can be prepared from compounds of formula (VIIIa) via treatment with compounds of formula (IX) . This reaction is shown in Scheme 7.
[0100] Additionally, compounds of formula (Ia) can be prepared from compounds of formula (VIIIb) via treatment with compounds of formula (X) . This reaction is shown in Scheme 8.
[0101] Compounds of formula (VIIaa) where T is pyrazole, W is -C (=O) -NH-, can be prepared by analogy to the methods described in scheme 8a. Commercially available 3-methyl-4-amino-1H-pyrazole undergoes amide coupling reaction with acid compounds of formula (IX) using suitable coupling reagents such as HATU or T3P and bases like DIPEA, can be performed analogous to as described in March's Advanced Organic Chemistry 6" edition, Michael B. Smith and Jerry March.
[0102] Compounds of formula (VIIab) where T is pyrazole, W is -NH-C (=O) -, can be prepared by analogy to the methods described in scheme 8b. The step involves amide coupling reactions with aniline derivative (X) derivatives and commercially available 3-methyl-1H-pyrazole-4-carboxylic acid using suitable coupling reagents such as HATU or T3P and bases like DIPEA, analogous to as described in March's Advanced Organic Chemistry 6'" edition, Michael B. Smith and Jerry March.
[0103] Compounds of formula (VIIac) where T is pyrazole, W is -NH-C (=O) -NH-, can be prepared in analogy to the methods described in scheme 8c. Commercially available 3-methyl-4-amino-1H-pyrazole undergoes urea formation reaction with amino compounds of formula (X) using suitable reagents such as phosgene, diphosgene or triphosgene and bases like DIPEA to as described in March's Advanced Organic Chemistry 6" edition, Michael B. Smith and Jerry March.
[0104] T2: related:
[0105] Compounds of formula (Ib) can be prepared from compounds of formula (IIb) , wherein X is a halogen, preferably Cl, Br or I, via treatment with compounds of formula (III) , in the presence of a base (e.g. K2CO3, Cs2CO3, or NaH) in a suitable solvent (eg, dimethylformamide or tetrahydrofuran) at a temperature between 25℃ and 110℃. In some cases, a better reaction performance may be gained from the use of a catalyst (eg, NaI or 4-dimethylaminopyridine) and with microwave irradiation. This reaction can also be catalysed by a copper salt such as copper (I) iodide and a chelator such as 8-hydroxyquinoline, both present in about 0.05 to about 0.25 equivalents, in the presence of caesium carbonate or potassium phosphate, in a polar aprotic solvent such as dimethylformamide at a temperature ranging between about 80℃ and about 140℃. This reaction is shown in Scheme 9.
[0106] Additionally, compounds of formula (Ib) can be prepared from compounds of formula (IV) , wherein X is a halogen, preferably Cl, Br or I, via treatment with compounds of formula (Vb) , in the presence of a base in a suitable solvent, such as tetrahydrofuran or ethanol, at a temperature between 25℃ and 75℃. Compounds of formula (Vb) are known, synthesis is described in WO 2003 / 028729 and WO 2010 / 045251. This reaction is shown in Scheme 10.
[0107] The compounds of formula (Vb, Vbb) can be obtained via several routes for examples, via Suzuki cross-coupling reaction between a halo-azoles (XI) and corresponding phenyl boronic acids as described in WO 2016040449 or WO 2018233633. Suitable azoles of general formula (XI) (where X can be chlorine, bromine, iodine and triflate) and phenylboronic acids are commercially available or could be synthesized following known literatures. Coupling of the boronate esters with a bromoheterocycle can be accomplished using a palladium catalyst, such tetrakis (triphenylphosphine) palladium (0) , in the presence of a base, such as sodium bicarbonate, in a suitable solvent system, such as dioxane / water, at temperatures from about 50℃ to about 120℃. Compounds of formula (Vb1) can undergo reduction to compounds of formula (Vbb) using reducing agents such as SnCI2 in acid medium or Fe with NH4CI in a mixture of Ethanol and water. This reaction is illustrated in Scheme 11.
[0108] The compounds of formula (IIb) can be obtained via several routes for examples, via Suzuki cross-coupling reaction between a halo-azoles (XI) and corresponding phenyl boronic acids as described in WO 2016040449 or WO 2018233633. Suitable azoles of general formula (XI) (where X can be chlorine, bromine, iodine and triflate) and phenylboronic acids (1) are commercially available or could be synthesized following known literatures. This reaction is shown in Scheme 12.
[0109] Alternatively compounds of formula (IIb) can be obtained from (Vbb) via Sandmeyer reaction following known literatures. X can be chlorine, bromine and iodine. This reaction is shown in Scheme 13.
[0110] Compounds of formula (IIb) , where W is -NH-C (=O) -can be prepared from compounds of formula (XIIb) by using amide coupling reactions with compounds of formula (IX) analogues to as described in March's Advanced Organic Chemistry 6th edition, Michael B. Smith and Jerry March. Compounds of formula (XIIb) can be prepared from commercially available benzoic acid derivative of formula (XIIb4) through intermediary of compounds of formula (XIIb3) and (XIIb2) in three steps, as described in Eur. J. of Med. Chem., 2016, 113, 11-27, WO 2020 / 083733 A1. This reaction is shown in Scheme 14.
[0111] Compounds of formula (IIb2) , where W is -C (=O) -NH-can be prepared from methyl 3-halo-1H-1, 2, 4-triazole-5-carboxylate via N-alkylation to build compounds of formula (XVIIb) by using amide formation reactions with compounds of formula (X) as described in WO2022053453 using Me3Al in toluene or THF to form compound (XVIIc) . Next step involves Suzuki cross-coupling reaction between compounds of formula (XVIIc) and corresponding phenyl boronic acids as in WO2022053453. This reaction is shown in Scheme 14b.
[0112] Compounds of formula (IIb3) , where W is -O-may be prepared in three steps from from commercially available 3, 5-dibromo-1H-1, 2, 4-triazole as described in EP 4036083. Compound (IIbbb3) can be prepared in analogy to WO 2018 / 87018 by alkylation of 3, 5-dibromo-1H-1, 2, 4-triazole with halomethyl compound where X is Cl, Br, I in the presence of a base like potassium carbonate in an appropriate solvent like acetonitrile, DMF, at temperature from 20-150℃. Compounds of formula (IIIbb3) can be prepared by SNAr reaction with compounds of formula (Xb) in the presence of a base like potassium carbonate or sodium hydride in an appropriate solvent like DMA, DMF, at temperature from 20-150℃.
[0113] Compounds of formula (IIb3) can be prepared by via Suzuki cross-coupling reaction between a bromotriazole compound of formula (IIbb3) and corresponding phenyl boronic acids in analogy as described in EP 4036083. This reaction is shown in Scheme 14c.
[0114] T3: related:
[0115] Compounds of formula (Ic) can be prepared from compounds of formula (IIc) , wherein X is a halogen, preferably Cl, Br or I, via treatment with compounds of formula (III) , in the presence of a base (e.g. K2CO3, Cs2CO3, or NaH) in a suitable solvent (eg, dimethylformamide or tetrahydrofuran) at a temperature between 25℃ and 110℃. In some cases, a better reaction performance may be gained from the use of a catalyst (eg, NaI or 4-dimethylaminopyridine) and with microwave irradiation. This reaction can also be catalysed by a copper salt such as copper (I) iodide and a chelator such as 8-hydroxyquinoline, both present in about 0.05 to about 0.25 equivalents, in the presence of caesium carbonate or potassium phosphate, in a polar aprotic solvent such as dimethylformamide at a temperature ranging between about 80℃ and about 140℃. This reaction is shown in Scheme 15.
[0116] Additionally, compounds of formula (Ic) can be prepared from compounds of formula (IV) , wherein X is a halogen, preferably Cl, Br or I, via treatment with compounds of formula (Vc) , in the presence of a base in a suitable solvent, such as tetrahydrofuran or ethanol, at a temperature between 25℃ and 75℃. This reaction is shown in Scheme 16.
[0117] Intermediates of formula (IIc) , where W is a direct bond and X is chlorine, bromine, iodine and triflate, may be prepared in two steps from corresponding benzamide (XIIIc1) under conditions described (Crouse, et al., WO2009102736) . The triazole (XIIIc2) can then be coupled to an aryl halide such as for example 4-trifluoromethoxyphenyl iodobenzene (US2017 / 060362) in the presence of caesium carbonate or potassium phosphate, in a polar aprotic solvent such as dimethylformamide. This reaction is catalysed by a copper salt such as copper (I) iodide and a chelator such as 8-hydroxyquinoline, both present in about 0.05 to about 0.25 equivalents, at a temperature ranging between about 80℃ and about 140℃, to form the (IIc) . This reaction is shown in Scheme 17.
[0118] Compounds of formula (Vc) , where W is a direct bond and A is p-trifluoromethoxy (CAS1181214-75-4) is commercially available or can be prepared via Suzuki cross-coupling reaction between commercially available 3-Bromo-1- (4- (trifluoromethoxy) phenyl) -1H-1, 2, 4-triazole (CAS1417885-96-1) and corresponding phenyl boronic acids as described in as described in WO 2022 / 132609. This reaction is shown in Scheme 18.
[0119] Alternatively compounds of formula (Vc) , where W is a direct bond and A is p-trifluoromethoxy (CAS1181214-75-4) can be prepared in two steps from corresponding benzamide (XIIIc1’) under conditions described (Crouse, et al., WO2009102736) . The triazole (XIIIc2’) can then be coupled to an aryl halide such as for example 4-trifluoromethoxyphenyl iodobenzene (US2017 / 060362) . This reaction is shown in Scheme 19.
[0120] T4: related:
[0121] Compounds of formula (Id) can be prepared from compounds of formula (IId) , wherein X is a halogen, preferably Cl, Br or I, via treatment with compounds of formula (III) . This reaction is shown in Scheme 20.
[0122] Additionally, compounds of formula (Id) can be prepared from compounds of formula (IV) , wherein X is a halogen, preferably Cl, Br or I, via treatment with compounds of formula (Vd) , in the presence of a base in a suitable solvent, such as tetrahydrofuran or ethanol, at a temperature between 25℃ and 75℃. This reaction is shown in Scheme 21.
[0123] Intermediates of formula (IId) , where W is a direct bond and A is p-trifluoromethoxybenzene may be prepared in three steps from 3, 5-Dibromo-1H-1, 2, 4-triazole (XIV) under conditions described WO 2022033991. Compounds of formula (XV) were obtained via Chan-Lam reaction, followed by amine substitution, followed by Suzuki reaction as described in WO 2022033991. This reaction is shown in Scheme 22.
[0124] Intermediates of formula (Vd) , where W is a direct bond and A is p-trifluoromethoxybenzene may be prepared in three steps from 3, 5-Dibromo-1H-1, 2, 4-triazole (XIV) under conditions described WO 2022033991. Compounds of formula (XV) were obtained via Chan-Lam reaction, followed by amine substitution, followed by Suzuki reaction as described in WO 2022033991. This reaction is shown in Scheme 23.
[0125] T5: related
[0126] Compounds of formula (Ie) can be prepared from compounds of formula (IIe) , wherein X is a halogen, preferably Cl, Br or I, via treatment with compounds of formula (III) , in the presence of a base (e.g. K2CO3, Cs2CO3, or NaH) in a suitable solvent (eg, dimethylformamide or tetrahydrofuran) at a temperature between 25℃ and 110℃. In some cases, a better reaction performance may be gained from the use of a catalyst (eg, NaI or 4-dimethylaminopyridine) and with microwave irradiation. This reaction can also be catalysed by a copper salt such as copper (I) iodide and a chelator such as 8-hydroxyquinoline, both present in about 0.05 to about 0.25 equivalents, in the presence of caesium carbonate or potassium phosphate, in a polar aprotic solvent such as dimethylformamide at a temperature ranging between about 80℃ and about 140℃. This reaction is shown in Scheme 24.
[0127] Additionally, compounds of formula (Ie) can be prepared from compounds of formula (IV) , wherein X is a halogen, preferably Cl, Br or I, via treatment with compounds of formula (Ve) , in the presence of a base in a suitable solventat a temperature between 25℃ and 75℃. This reaction is shown in Scheme 25.
[0128] Intermediates of formula (IIe) , where W is a direct bond and A is p-trifluoromethoxybenzene may be prepared from commercially available compounds of formula (XVII) and (XVIII) . This reaction is shown in Scheme 26.
[0129] Intermediates of formula (Ve) , where W is a direct bond and A is p-trifluoromethoxybenzene may be prepared from commercially available compounds of formula (XVIIb) and (XVIII) . This reaction is shown in Scheme 27.
[0130] Intermediates of formula (III) may be prepared as exemplified in the preparation part.
[0131] Intermediates of formula (IV) may be prepared as exemplified in the preparation part.
[0132] Salts of compounds of Formula (I) can be prepared in a manner known per se. Thus, for example, acid addition salts of compounds of Formula (I) are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.
[0133] Salts of compounds of Formula (I) can be converted in the customary manner into the free compounds I, acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent.
[0134] Salts of compounds of Formula (I) can be converted in a manner known per se into other salts of compounds of formula I, acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.
[0135] Depending on the procedure or the reaction conditions, the compounds of formula I, which have salt-forming properties can be obtained in free form or in the form of salts.
[0136] The compounds of Formula (I) and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can be present in the form of one of the isomers which are possible or as a mixture of these, for example in the form of pure isomers, such as antipodes and / or diastereomers, or as isomer mixtures, such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms which occur in the molecule and / or depending on the configuration of non-aromatic double bonds which occur in the molecule; the invention relates to the pure isomers and also to all isomer mixtures which are possible and is to be understood in each case in this sense hereinabove and hereinbelow, even when stereochemical details are not mentioned specifically in each case.
[0137] Diastereomer mixtures or racemate mixtures of compounds of formula I, in free form or in salt form, which can be obtained depending on which starting materials and procedures have been chosen can be separated in a known manner into the pure diasteromers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and / or chromatography.
[0138] Enantiomer mixtures, such as racemates, which can be obtained in a similar manner can be resolved into the optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high-performance liquid chromatography (HPLC) on acetyl cellulose, with the aid of suitable microorganisms, by cleavage with specific, immobilized enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, where only one enantiomer is complexed, or by conversion into diastereomeric salts, for example by reacting a basic end-product racemate with an optically active acid, such as a carboxylic acid, for example camphor, tartaric or malic acid, or sulfonic acid, for example camphorsulfonic acid, and separating the diastereomer mixture which can be obtained in this manner, for example by fractional crystallization based on their differing solubilities, to give the diastereomers, from which the desired enantiomer can be set free by the action of suitable agents, for example basic agents.
[0139] Pure diastereomers or enantiomers can be obtained according to the invention not only by separating suitable isomer mixtures, but also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the process according to the invention with starting materials of a suitable stereochemistry.
[0140] N-oxides can be prepared by reacting a compound of the Formula (I) with a suitable oxidizing agent, for example the H2O2 / urea adduct in the presence of an acid anhydride, e.g. trifluoroacetic anhydride. Such oxidations are known from the literature, for example from J. Med. Chem., 32 (12) , 2561-73, 1989 or WO 2000 / 15615.
[0141] It is advantageous to isolate or synthesize in each case the biologically more effective isomer, for example enantiomer or diastereomer, or isomer mixture, for example enantiomer mixture or diastereomer mixture, if the individual components have a different biological activity.
[0142] The compounds of Formula (I) and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can, if appropriate, also be obtained in the form of hydrates and / or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form.
[0143] The compounds of formula I-Aaccording to the following Tables A-1 to A-42 can be prepared according to the methods described above. The examples which follow are intended to illustrate the invention and show preferred compounds of formula I, in the form of a compound of formula I-A.
[0144] Table A-1 provides 26 compounds A-1.001 to A-1.026 of formula I-Awherein Bx is (2-isopropylphenyl) , Qx is 1 and Cx are as defined in table A. For example, A-1.001 is
[0145] Substituent definitions of Qx:
[0146] Table A: Substituent definitions of Cx:
[0147] Table A-2 provides 26 compounds A-2.001 to A-2.026 of formula I-Awherein Bx is (2-isopropylphenyl) , Qx is 2 and Cx are as defined in table A.
[0148] Table A-3 provides 26 compounds A-3.001 to A-3.026 of formula I-Awherein Bx is (2-isopropylphenyl) , Qx is 3 and Cx are as defined in table A.
[0149] Table A-4 provides 26 compounds A-4.001 to A-4.026 of formula I-Awherein Bx is (2-isopropylphenyl) , Qx is 4 and Cx are as defined in table A.
[0150] Table A-5 provides 26 compounds A-5.001 to A-5.026 of formula I-Awherein Bx is (2-isopropylphenyl) , Qx is 5 and Cx are as defined in table A.
[0151] Table A-6 provides 26 compounds A-6.001 to A-6.026 of formula I-Awherein Bx is (2-isopropylphenyl) , Qx is 6 and Cx are as defined in table A.
[0152] Table A-7 provides 26 compounds A-7.001 to A-7.026 of formula I-Awherein Bx is (2-isopropyl-5-methyl-phenyl) , Qx is 1 and Cx are as defined in table A.
[0153] Table A-8 provides 26 compounds A-8.001 to A-8.026 of formula I-Awherein Bx is (2-isopropyl-5-methyl-phenyl) , Qx is 2 and Cx are as defined in table A.
[0154] Table A-9 provides 26 compounds A-9.001 to A-9.026 of formula I-Awherein Bx is (2-isopropyl-5-methyl-phenyl) , Qx is 3 and Cx are as defined in table A.
[0155] Table A-10 provides 26 compounds A-10.001 to A-10.026 of formula I-Awherein Bx is (2-isopropyl-5-methyl-phenyl) , Qx is 4 and Cx are as defined in table A.
[0156] Table A-11 provides 26 compounds A-11.001 to A-11.026 of formula I-Awherein Bx is (2-isopropyl-5-methyl-phenyl) , Qx is 5 and Cx are as defined in table A.
[0157] Table A-12 provides 26 compounds A-12.001 to A-12.026 of formula I-Awherein Bx is (2-isopropyl-5-methyl-phenyl) , Qx is 6 and Cx are as defined in table A.
[0158] Table A-13 provides 26 compounds A-13.001 to A-13.026 of formula I-Awherein Bx is (2-isopropyl-5-methoxy-phenyl) , Qx is 1 and Cx are as defined in table A.
[0159] Table A-14 provides 26 compounds A-14.001 to A-14.026 of formula I-Awherein Bx is (2-isopropyl-5-methoxy-phenyl) , Qx is 2 and Cx are as defined in table A.
[0160] Table A-15 provides 26 compounds A-15.001 to A-15.026 of formula I-Awherein Bx is (2-isopropyl-5-methoxy-phenyl) , Qx is 3 and Cx are as defined in table A.
[0161] Table A-16 provides 26 compounds A-16.001 to A-16.026 of formula I-Awherein Bx is (2-isopropyl-5-methoxy-phenyl) , Qx is 4 and Cx are as defined in table A.
[0162] Table A-17 provides 26 compounds A-17.001 to A-17.026 of formula I-Awherein Bx is (2-isopropyl-5-methoxy-phenyl) , Qx is 5 and Cx are as defined in table A.
[0163] Table A-18 provides 26 compounds A-18.001 to A-18.026 of formula I-Awherein Bx is (2-isopropyl-5-methoxy-phenyl) , Qx is 6 and Cx are as defined in table A.
[0164] Table A-19 provides 26 compounds A-19.001 to A-19.026 of formula I-Awherein Bx is (5-cyclopropyl-2-isopropyl-phenyl) , Qx is 1 and Cx are as defined in table A.
[0165] Table A-20 provides 26 compounds A-20.001 to A-20.026 of formula I-Awherein Bx is (5-cyclopropyl-2-isopropyl-phenyl) , Qx is 2 and Cx are as defined in table A.
[0166] Table A-21 provides 26 compounds A-21.001 to A-21.026 of formula I-Awherein Bx is (5-cyclopropyl-2-isopropyl-phenyl) , Qx is 3 and Cx are as defined in table A.
[0167] Table A-22 provides 26 compounds A-22.001 to A-22.026 of formula I-Awherein Bx is (5-cyclopropyl-2-isopropyl-phenyl) , Qx is 4 and Cx are as defined in table A.
[0168] Table A-23 provides 26 compounds A-23.001 to A-23.026 of formula I-Awherein Bx is (5-cyclopropyl-2-isopropyl-phenyl) , Qx is 5 and Cx are as defined in table A.
[0169] Table A-24 provides 26 compounds A-24.001 to A-24.026 of formula I-Awherein Bx is (5-cyclopropyl-2-isopropyl-phenyl) , Qx is 6 and Cx are as defined in table A.
[0170] Table A-25 provides 26 compounds A-25.001 to A-25.026 of formula I-Awherein Bx is (5-chloro-2-isopropyl-phenyl) , Qx is 1 and Cx are as defined in table A.
[0171] Table A-26 provides 26 compounds A-26.001 to A-26.026 of formula I-Awherein Bx is (5-chloro-2-isopropyl-phenyl) , Qx is 2 and Cx are as defined in table A.
[0172] Table A-27 provides 26 compounds A-27.001 to A-27.026 of formula I-Awherein Bx is (5-chloro-2-isopropyl-phenyl) , Qx is 3 and Cx are as defined in table A.
[0173] Table A-28 provides 26 compounds A-28.001 to A-28.026 of formula I-Awherein Bx is (5-chloro-2-isopropyl-phenyl) , Qx is 4 and Cx are as defined in table A.
[0174] Table A-29 provides 26 compounds A-29.001 to A-29.026 of formula I-Awherein Bx is (5-chloro-2-isopropyl-phenyl) , Qx is 5 and Cx are as defined in table A.
[0175] Table A-30 provides 26 compounds A-30.001 to A-30.026 of formula I-Awherein Bx is (5-chloro-2-isopropyl-phenyl) , Qx is 6 and Cx are as defined in table A.
[0176] Table A-31 provides 26 compounds A-31.001 to A-31.026 of formula I-Awherein Bx is [5-chloro-2- (trifluoromethyl) phenyl] , Qx is 1 and Cx are as defined in table A.
[0177] Table A-32 provides 26 compounds A-32.001 to A-32.026 of formula I-Awherein Bx is [5-chloro-2- (trifluoromethyl) phenyl] , Qx is 2 and Cx are as defined in table A.
[0178] Table A-33 provides 26 compounds A-33.001 to A-33.026 of formula I-Awherein Bx is [5-chloro-2- (trifluoromethyl) phenyl] , Qx is 3 and Cx are as defined in table A.
[0179] Table A-34 provides 26 compounds A-34.001 to A-34.026 of formula I-Awherein Bx is [5-chloro-2- (trifluoromethyl) phenyl] , Qx is 4 and Cx are as defined in table A.
[0180] Table A-35 provides 26 compounds A-35.001 to A-35.026 of formula I-Awherein Bx is [5-chloro-2- (trifluoromethyl) phenyl] , Qx is 5 and Cx are as defined in table A.
[0181] Table A-36 provides 26 compounds A-36.001 to A-36.026 of formula I-Awherein Bx is [5-chloro-2- (trifluoromethyl) phenyl] , Qx is 6 and Cx are as defined in table A.
[0182] Table A-37 provides 26 compounds A-37.001 to A-37.026 of formula I-Awherein Bx is (2, 6-dimethylphenyl) , Qx is 1 and Cx are as defined in table A.
[0183] Table A-38 provides 26 compounds A-38.001 to A-38.026 of formula I-Awherein Bx is (2, 6-dimethylphenyl) , Qx is 2 and Cx are as defined in table A.
[0184] Table A-39 provides 26 compounds A-39.001 to A-39.026 of formula I-Awherein Bx is (2, 6-dimethylphenyl) , Qx is 3 and Cx are as defined in table A.
[0185] Table A-40 provides 26 compounds A-40.001 to A-40.026 of formula I-Awherein Bx is (2, 6-dimethylphenyl) , Qx is 4 and Cx are as defined in table A.
[0186] Table A-41 provides 26 compounds A-41.001 to A-41.026 of formula I-Awherein Bx is (2, 6-dimethylphenyl) , Qx is 5 and Cx are as defined in table A.
[0187] Table A-42 provides 26 compounds A-42.001 to A-42.026 of formula I-Awherein Bx is (2, 6-dimethylphenyl) , Qx is 6 and Cx are as defined in table A.
[0188] The compounds of formula I-B according to the following Tables B-1 to B-42 can be prepared according to the methods described above. The examples which follow are intended to illustrate the invention and show preferred compounds of formula I, in the form of a compound of formula I-B.
[0189] Table B-1 provides 26 compounds B-1.001 to B-1.026 of formula I-B wherein Bx is (2-isopropylphenyl) , Qx is 1 and Cx are as defined in table A.
[0190] Table B-2 provides 26 compounds B-2.001 to B-2.026 of formula I-B wherein Bx is (2-isopropylphenyl) , Qx is 2 and Cx are as defined in table A.
[0191] Table B-3 provides 26 compounds B-3.001 to B-3.026 of formula I-B wherein Bx is (2-isopropylphenyl) , Qx is 3 and Cx are as defined in table A.
[0192] Table B-4 provides 26 compounds B-4.001 to B-4.026 of formula I-B wherein Bx is (2-isopropylphenyl) , Qx is 4 and Cx are as defined in table A.
[0193] Table B-5 provides 26 compounds B-5.001 to B-5.026 of formula I-B wherein Bx is (2-isopropylphenyl) , Qx is 5 and Cx are as defined in table A.
[0194] Table B-6 provides 26 compounds B-6.001 to B-6.026 of formula I-B wherein Bx is (2-isopropylphenyl) , Qx is 6 and Cx are as defined in table A.
[0195] Table B-7 provides 26 compounds B-7.001 to B-7.026 of formula I-B wherein Bx is (2-isopropyl-5-methyl-phenyl) , Qx is 1 and Cx are as defined in table A.
[0196] Table B-8 provides 26 compounds B-8.001 to B-8.026 of formula I-B wherein Bx is (2-isopropyl-5-methyl-phenyl) , Qx is 2 and Cx are as defined in table A.
[0197] Table B-9 provides 26 compounds B-9.001 to B-9.026 of formula I-B wherein Bx is (2-isopropyl-5-methyl-phenyl) , Qx is 3 and Cx are as defined in table A.
[0198] Table B-10 provides 26 compounds B-10.001 to B-10.026 of formula I-B wherein Bx is (2-isopropyl-5-methyl-phenyl) , Qx is 4 and Cx are as defined in table A.
[0199] Table B-11 provides 26 compounds B-11.001 to B-11.026 of formula I-B wherein Bx is (2-isopropyl-5-methyl-phenyl) , Qx is 5 and Cx are as defined in table A.
[0200] Table B-12 provides 26 compounds B-12.001 to B-12.026 of formula I-B wherein Bx is (2-isopropyl-5-methyl-phenyl) , Qx is 6 and Cx are as defined in table A.
[0201] Table B-13 provides 26 compounds B-13.001 to B-13.026 of formula I-B wherein Bx is (2-isopropyl-5-methoxy-phenyl) , Qx is 1 and Cx are as defined in table A.
[0202] Table B-14 provides 26 compounds B-14.001 to B-14.026 of formula I-B wherein Bx is (2-isopropyl-5-methoxy-phenyl) , Qx is 2 and Cx are as defined in table A.
[0203] Table B-15 provides 26 compounds B-15.001 to B-15.026 of formula I-B wherein Bx is (2-isopropyl-5-methoxy-phenyl) , Qx is 3 and Cx are as defined in table A.
[0204] Table B-16 provides 26 compounds B-16.001 to B-16.026 of formula I-B wherein Bx is (2-isopropyl-5-methoxy-phenyl) , Qx is 4 and Cx are as defined in table A.
[0205] Table B-17 provides 26 compounds B-17.001 to B-17.026 of formula I-B wherein Bx is (2-isopropyl-5-methoxy-phenyl) , Qx is 5 and Cx are as defined in table A.
[0206] Table B-18 provides 26 compounds B-18.001 to B-18.026 of formula I-B wherein Bx is (2-isopropyl-5-methoxy-phenyl) , Qx is 6 and Cx are as defined in table A.
[0207] Table B-19 provides 26 compounds B-19.001 to B-19.026 of formula I-B wherein Bx is (5-cyclopropyl-2-isopropyl-phenyl) , Qx is 1 and Cx are as defined in table A.
[0208] Table B-20 provides 26 compounds B-20.001 to B-20.026 of formula I-B wherein Bx is (5-cyclopropyl-2-isopropyl-phenyl) , Qx is 2 and Cx are as defined in table A.
[0209] Table B-21 provides 26 compounds B-21.001 to B-21.026 of formula I-B wherein Bx is (5-cyclopropyl-2-isopropyl-phenyl) , Qx is 3 and Cx are as defined in table A.
[0210] Table B-22 provides 26 compounds B-22.001 to B-22.026 of formula I-B wherein Bx is (5-cyclopropyl-2-isopropyl-phenyl) , Qx is 4 and Cx are as defined in table A.
[0211] Table B-23 provides 26 compounds B-23.001 to B-23.026 of formula I-B wherein Bx is (5-cyclopropyl-2-isopropyl-phenyl) , Qx is 5 and Cx are as defined in table A.
[0212] Table B-24 provides 26 compounds B-24.001 to B-24.026 of formula I-B wherein Bx is (5-cyclopropyl-2-isopropyl-phenyl) , Qx is 6 and Cx are as defined in table A.
[0213] Table B-25 provides 26 compounds B-25.001 to B-25.026 of formula I-B wherein Bx is (5-chloro-2-isopropyl-phenyl) , Qx is 1 and Cx are as defined in table A.
[0214] Table B-26 provides 26 compounds B-26.001 to B-26.026 of formula I-B wherein Bx is (5-chloro-2-isopropyl-phenyl) , Qx is 2 and Cx are as defined in table A.
[0215] Table B-27 provides 26 compounds B-27.001 to B-27.026 of formula I-B wherein Bx is (5-chloro-2-isopropyl-phenyl) , Qx is 3 and Cx are as defined in table A.
[0216] Table B-28 provides 26 compounds B-28.001 to B-28.026 of formula I-B wherein Bx is (5-chloro-2-isopropyl-phenyl) , Qx is 4 and Cx are as defined in table A.
[0217] Table B-29 provides 26 compounds B-29.001 to B-29.026 of formula I-B wherein Bx is (5-chloro-2-isopropyl-phenyl) , Qx is 5 and Cx are as defined in table A.
[0218] Table B-30 provides 26 compounds B-30.001 to B-30.026 of formula I-B wherein Bx is (5-chloro-2-isopropyl-phenyl) , Qx is 6 and Cx are as defined in table A.
[0219] Table B-31 provides 26 compounds B-31.001 to B-31.026 of formula I-B wherein Bx is [5-chloro-2- (trifluoromethyl) phenyl] , Qx is 1 and Cx are as defined in table A.
[0220] Table B-32 provides 26 compounds B-32.001 to B-32.026 of formula I-B wherein Bx is [5-chloro-2- (trifluoromethyl) phenyl] , Qx is 2 and Cx are as defined in table A.
[0221] Table B-33 provides 26 compounds B-33.001 to B-33.026 of formula I-B wherein Bx is [5-chloro-2- (trifluoromethyl) phenyl] , Qx is 3 and Cx are as defined in table A.
[0222] Table B-34 provides 26 compounds B-34.001 to B-34.026 of formula I-B wherein Bx is [5-chloro-2- (trifluoromethyl) phenyl] , Qx is 4 and Cx are as defined in table A.
[0223] Table B-35 provides 26 compounds B-35.001 to B-35.026 of formula I-B wherein Bx is [5-chloro-2- (trifluoromethyl) phenyl] , Qx is 5 and Cx are as defined in table A.
[0224] Table B-36 provides 26 compounds B-36.001 to B-36.026 of formula I-B wherein Bx is [5-chloro-2- (trifluoromethyl) phenyl] , Qx is 6 and Cx are as defined in table A.
[0225] Table B-37 provides 26 compounds B-37.001 to B-37.026 of formula I-B wherein Bx is (2, 6-dimethylphenyl) , Qx is 1 and Cx are as defined in table A.
[0226] Table B-38 provides 26 compounds B-38.001 to B-38.026 of formula I-B wherein Bx is (2, 6-dimethylphenyl) , Qx is 2 and Cx are as defined in table A.
[0227] Table B-39 provides 26 compounds B-39.001 to B-39.026 of formula I-B wherein Bx is (2, 6-dimethylphenyl) , Qx is 3 and Cx are as defined in table A.
[0228] Table B-40 provides 26 compounds B-40.001 to B-40.026 of formula I-B wherein Bx is (2, 6-dimethylphenyl) , Qx is 4 and Cx are as defined in table A.
[0229] Table B-41 provides 26 compounds B-41.001 to B-41.026 of formula I-B wherein Bx is (2, 6-dimethylphenyl) , Qx is 5 and Cx are as defined in table A.
[0230] Table B-42 provides 26 compounds B-42.001 to B-42.026 of formula I-B wherein Bx is (2, 6-dimethylphenyl) , Qx is 6 and Cx are as defined in table A.
[0231] The compounds of formula (I) according to the invention are preventively and / or curatively valuable active ingredients in the field of pest control, even at low rates of application, which have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish and plants. The active ingredients according to the invention act against all or individual developmental stages of normally sensitive, but also resistant, animal pests, such as insects or representatives of the order Acarina or class Nematoda. The insecticidal or acaricidal activity of the active ingredients according to the invention can manifest itself directly, i.e. in destruction of the pests, which takes place either immediately or only after some time has elapsed, for example during ecdysis, or indirectly, for example in a reduced oviposition and / or hatching rate.
[0232] Examples of the above mentioned pests are:
[0233] from the order Anoplurida, for example, Pthirus pubis, Pthirus spp., and Solenopotes capillatus; from the order Aphelenchida, for example, Bursaphelenchus lignicolus, Bursaphelenchus spp., and Bursaphelenchus xylophilus;
[0234] from the order Araneae, for example, Agelenopsis spp., Eratigena agrestis, Latrodectus mactans, Latrodectus spp., Loxosceles reclusa, Lycosidae spp., Parastatoda tepidariorum, and Pholcus spp.; from the order Architaenioglossa, for example, Ampullariidae spp.;
[0235] from the order Ascaridida, for example, Ascaris lumbricoides, Ascaris spp., and Heterakis spp.;
[0236] from the order Astigmata, for example, Chorioptes bovis, Chorioptes spp., Cytodites spp.,
[0237] Laminosioptes spp., Otodectes cynotis, Otodectes spp., and Pterolichus spp.;
[0238] from the order Bacillales, for example, Pasteuria penetrans;
[0239] from the order Basommatophora, for example, Biomphalaria spp., and Bulinus spp.;
[0240] from the order Blattaria, for example, Blatta orientalis, Blattella asahinai, Blattella germanica, Mastotermes darwiniensis, Mastotermes spp., Periplaneta americana, Periplaneta australasiae, Periplaneta fuliginosa, Shelfordella lateralis, Supella longipalpa, and Supella spp.;
[0241] from the order Blattodea, for example, Coptotermes spp., Incisitermes spp., and Leucophaea maderae;
[0242] from the order Caenogastropoda, for example, Pomacea canaliculata;
[0243] from the order Camallanida, for example, Dracunculus medinensis;
[0244] from the order Chilopoda, for example, Geophilus carpophagus, Geophilus spp., and Scutigera spp.;
[0245] from the order Coleoptera, for example, Acanthoscelides obtectus, Adelium brevicorne, Adelium spp.., Adoretus spp., Aeolus mellillus, Aeolus spp.., Agelastica alni, Agriotes brevis, Agriotes criddlei, Agriotes fuscicollis, Agriotes lineatus, Agriotes littigiosus, Agriotes mancus, Agriotes obscurus, Agriotes proximus, Agriotes rufipalpis, Agriotes sordidus, Agriotes spp., Agriotes sputator, Agriotes ustulatus, Agrypnus spp.., Agrypnus variabilis, Alphitobius diaperinus, Amphimallon solstitiale, Amphimallon majale, Anisoplia austriaca, Anobium punctatum, Anomala orientalis, Anomala rufocuprea, Anoplophora spp., Anthonomus consors, Anthonomus corvulus, Anthonomus elongatus, Anthonomus elutus, Anthonomus eugenii, Anthonomus grandis, Anthonomus haematopus, Anthonomus lecontei, Anthonomus molochinus, Anthonomus morticinus, Anthonomus musculus, Anthonomus nigrinus, Anthonomus phyllocola, Anthonomus pictus, Anthonomus pomorum, Anthonomus quadrigibbus, Anthonomus rectirostris, Anthonomus rubi, Anthonomus santacruzi, Anthonomus signatus, Anthonomus spp., Anthonomus subfasciatus, Anthonomus tenebrosus, Anthrenus spp., Aphodius spp., Apogonia spp., Astylus atromaculatus, Ataenius spp., Ataneus spretulus, Athous spp.., Atomaria linearis, Atomaria spp., Attagenus spp., Aulacophora femoralis, Bruchidius obtectus, Bruchus spp., Callosobruchus chinensis, Cerotoma arcuata, Cerotoma spp., Cerotoma trifurcata, Ceuthorhynchus assimilis, Ceuthorhynchus spp., Ceutorhynchus napi, Chaetocnema aridula, Chaetocnema minuta, Chaetocnema spp., Chaetocnema tibialis, Chyptohypnus nocturnus bicolor, Chyptohypnus spp.., Cleonus mendicus, Collops spp., Conoderus spp.., Conotrachelus nenupphar, Cosmopolites sordidus, Cosmopolites spp., Costelytra zealandica, Cotinis nitida, Cryptohypnus nocturnus (Eschscholtz) , Cryptorhynchus lapathi, Ctenicera aeripennis destructor, Ctenicera destructor, Ctenicera spp.., Curculio spp., Cyclocephala lurida, Cyclocephala spp., Cyclocephela borealis, Dermestes spp., Diabrotica speciosa, Diabrotica spp., Diabrotica virgifera, Dicladispa armigera, Dicladispa spp., Diloboderus abderus, Diloboderus spp., Epilachna spp., Epilachna varivestis, Epilachna vigintioctomaculata, Epitrix spp., Eremnus spp., Exomala orientalis, Faustinus cubae, Gibbium psylloides, Gonocephalum aequatoriale, Gonocephalum bilineatum, Gonocephalum carpentariae, Gonocephalum contractum, Gonocephalum depressum, Gonocephalum dorsogranosum, Gonocephalum elderi, Gonocephalum hoffmannseggii, Gonocephalum macleaya, Gonocephalum misellum, Gonocephalum patruele, Gonocephalum pusillum, Gonocephalum reticulatum, Gonocephalum rusticum, Gonocephalum seriatum, Gonocephalum setulosum, Gonocephalum simplex, Gonocephalum spp.., Gonocephalum torridum, Gonocephalum tuberculatum, Gonocephalum walker, Hadromorphus glaucus, Hadromorphus spp.., Heteronychus arator, Hispa spp., Holotrichia spp., Hylamorpha elegans, Hylotrupes bajulus, Hypera brunneipennis, Hypera postica, Hypnoidus abbreviates, Hypnoidus nocturnus, Hypnoidus spp.., Hypolithus bicolor, Hypothenemus hampei, Hypothenemus spp., Lachnosterna consanguinea, Lagria vilosa, Lema oryzae, Leptinotarsa decemlineata, Leptinotarsa spp., Limonius californicus, Limonius canus, Limonius infuscatus, Limonius pctoralis, Limonius spp., Liogenys fuscus, Liogenys spp.., Liogenys suturalis, Lissorhoptrus oryzophilus, Lissorhoptrus spp., Listronotus maculicollis, Lixus spp., Ludius aeripennis destructor, Ludius aeripennis tinctus, Ludius spp.., Maecolaspis spp., Maladera castanea, Maladera matrida, Megascelis calcarifera, Megascelis spp., Melanotus opacaicicollis leconte, Melanotus spp.., Meligethes aeneus, Meligethes spp., Melolontha melolontha, Melolontha spp., Metamasius hemipterus, Microtheca spp., Migdolus spp., Monochamus alternatus, Monochamus spp., Myochrous armatus, Naupactus xanthographus, Niptus hololeucus, Orycaephilus spp., Oryctes rhinoceros, Oryzaephilus surinamensis, Otiorhynchus spp., Otiorhynchus Sulcatus, Otiorrhynchus sulcatus, Oulema melanopus, Oulema oryzae, Oulema spp., Oxycetonia jucunda, Phaedon cochleariae, Pheletes californicus, Pheletes spp.., Phlyctinus spp., Phyllophaga cuyabana, Phyllophaga spp., Phyllotreta cruciferae, Phyllotreta spp., Phyllotreta striolata, Popillia japonica, Popillia spp., Premnotrypes spp., Psylliodes chrysocephala, Psylliodes spp., Pterohelaeus alternatus, Pterohelaeus spp.., Ptinus spp., Rhizobius ventralis, Rhizopertha dominica, Rhizopertha spp., Rhizotrogus majalis, Rhyssomatus aubtilis, Scarabeidae, Scelodonta strigicollis, Selatosomus aeripennis aeripennis, Selatosomus aeripennis destructor, Selatosomus destructor, Selatosomus spp.., Sitophilus spp., Sitophilus zeamais, Somaticus angulatus, Somaticus spp., Sphenophorus levis, Sphenophorus parvulus, Sphenophorus sp., Sphenophorus spp., Sphenophorus spp., Sternechus spp., Sternechus subsignatus, Symphyletes spp., Tenebrio molitor, Tenebrio spp., Tribolium castaneum, Tribolium spp., Trogoderma spp., Tychius spp., Xylotrechus spp., Zabrus spp., and Zabrus tenebrioides;
[0246] from the order Collembola, for example, Onychiurus armatus;
[0247] from the order Cyclophyllidea, for example, Echinococcus granulosus, Echinococcus multilocularis, Hymenolepis nana, Taenia saginata, and Taenia solium;
[0248] from the order Dermaptera, for example, Forficula auricularia;
[0249] from the order Dictyoptera, for example, Cryptotermes brevis, Incisitermes minor, Kalotermes flavicollis, Marginitermes hubbardi, and Neotermes spp.;
[0250] from the order Diplopoda, for example, Blaniulus guttulatus;
[0251] from the order Diptera, for example, Aedes aegypti, Aedes albopictus, Aedes japonicus, Aedes spp., Anopheles arabiensis, Anopheles funestus, Anopheles gambiae, Anopheles sinensis, Anopheles spp., Anopheles stephensi, Antherigona soccata, Atylotus spp., Bactrocea oleae, Bactrocera spp., Bibio hortulanus, Braula spp., Calliphora erythrocephala, Calliphora spp., Ceratitis capitata, Ceratitis spp., Chrysomya spp., Chrysops spp., Cochliomyia spp., Contarinia spp., Contarinia tritici, Cordylobia anthropophaga, Culex pipiens, Culex quinquefasciatus, Culex spp., Culex tritaeniorhynchus, Culicoides spp., Cuterebra spp., Dacus oleae, Dacus spp., Delia platura, Delia spp., Dermatobia hominis, Drosophila melanogaster, Drosophila spp., Drosophila suzukii, Eusimulium spp., Fannia spp., Gasterophilus spp., Geomyza tripunctata, Glossina spp., Haematobia irritans, Haematobia spp., Haematopota spp., Hippobosca spp., Hybomitra spp., Hydrellia griseola, Hydrellia philipina, Hydrellia spp., Hydrotaea spp., Hylemia platura, Hylemya spp., Hypoderma spp., Hyppobosca spp., Lipoptena spp., Liriomyza asclepiadis, Liriomyza brassicae, Liriomyza huidobrensis, Liriomyza sativae, Liriomyza spp., Liriomyza Trifoli, Liriomyza trifolii, Lucilia cuprina, Lucilia spp., Lutzomyia spp., Lyctus spp., Mayetiola spp., Melanagromyza spp., Melophagus spp., Morellia spp., Musca autumnalis, Musca domestica, Musca spp., Odagmia spp., Oestrus spp., Opomyza florum, Opomyza spp., Orseolia oryzae, Orseolia spp., Oscinella frit, Oscinella spp., Pegomyia hyoscyami, Pegomyia spp., Philipomyia spp., Phlebotomus spp., Phorbia spp., Rhagoletis spp., Rhinoestrus spp., Rivelia quadrifasciata, Sarcophaga spp., Scatella stagnalis, Sciara Bradysia, Sciara coprophila, Simulium spp., Sitodiplosis spp., Stomoxys calcitrans, Stomoxys spp., Tabanus spp., Tannia spp., Tipula oleracea, Tipula paludosa, Tipula spp., Trichosia spp., Wilhelmia spp., and Wohlfahrtia spp.;
[0252] from the order Dorylaimida, for example, Longidorus breviannulatus, Longidorus elongatus, Longidorus spp., Trichodorus primitivus, Trichodorus spp., and Xiphinema spp.;
[0253] from the order Echinostomida, for example, Faciola spp.;
[0254] from the order Hemiptera, for example, Acanthocoris scabrator, Acrosternum hilare, Acrosternum spp., Acyrthosiphon spp., Acyrthosium pisum, Adalges spp., Adelphocoris lineolatus, Aeneolamia spp., Agalliana ensigera, Agonoscena spp., Agonoscena targionii, Aleurocanthus spp., Aleurodes brassicae, Aleurodes spp., Aleurodicus spp., Aleurolobus barodensis, Aleurothrixus floccosus, Aleurothrixus spp., Aleyrodes brassicae, Amarasca biguttula, Amblypelta nitida, Amrasca biguttula, Amrasca spp., Amritodus atkinsoni, Anasa tristis, Antestiopsis orbitalus, Antestiopsis spp., Anuraphis cardui, Aonidiella aurantii, Aonidiella spp., Aphanostigma piri, Aphididae, Aphis citri, Aphis fabae, Aphis glycines, Aphis gossypii, Aphis nasturtii, Aphis pomi, Aphis spiraecola, Aphis spp., Arboridia apicalis, Aspidiella spp., Aspidiotus hederae, Aspidiotus spp., Atanus spp., Aulacorthum solani, Austroasca viridigrisea, Bactericera cockerelli, Bathycoelia thalassina, Bemisia argentifolii, Bemisia spp., Bemisia tabaci, Blissus insularis, Blissus insularis barber, Blissus Leucopterus, Blissus leucopterus hirtus, Blissus spp., Brachycaudus helichrysii, Brachycaudus spp., Brachycolus spp., Brevicoryne brassicae, Brevicoryne spp., Cacopsylla pyri, Cacopsylla pyricola, Cacopsylla spp., Calligypona marginata, Calocoris spp., Campylomma livida, Carneocephala fulgida, Cavariella aegopodii, Cavelerius spp., Ceratovacuna lanigera, Ceroplaster spp., Ceroplastes spp., Chaetosiphon fragaefolii, Chionaspis tegalensis, Chlorita onukii, Chromaphis juglandicola, Chrysomphalus dictyospermi, Chrysomphalus ficus / aonidum, Cicadella spp., Cicadulina mbila, Cicadulina spp., Cimex hemipterus, Cimex lectularius, Cimex spp., Clavigralla tomentosicollis, Coccomytilus halli, Coccus hesperidum, Coccus spp., Cofana spectra, Creontiades biseratense, Creontiades dilutus, Creontiades spp., Cryptomyzus ribis, Cryptomyzus spp., Dalbulus maidis, Dalbulus spp., Dasynus piperis, Dialeurodes spp., Diaphorina citri, Diaphorina spp., Diaspis spp., Diceraeus furcatus, Diceraeus melacanthus, Diceraeus spp., Dichelops furcatus, Dichelops melacanthus, Dichelops spp., Diconocoris hewetti, Distantiella theobroma, Diuraphis noxia, Diuraphis spp., Drosicha spp., Dysaphis plantaginea, Dysaphis spp., Dysdercus cingulatus, Dysdercus intermedius, Dysdercus spp., Dysmicoccus spp., Edessa meditabunda, Edessa spp., Empoasca fabae, Empoasca solana, Empoasca spp., Empoasca vitis, Eriosoma lanigerum, Eriosoma spp., Erythroneura Elegantula, Erythroneura spp., Euchistus spp., Eurydema pulchrum, Eurygaster integriceps, Eurygaster intergriceps, Eurygaster maura, Eurygaster spp., Euscelis bilobatus, Euschistus heros, Euschistus servus, Euschistus spp., Gascardia spp., Geococcus coffeae, Geocoris spp., Glycaspis brimblecombei, Halyomorpha halys, Halyomorpha spp., Helopeltis spp., Homalodisca coagulata / vitripennis, Horcias nobilellus, Hyadaphis pseudobrassicae, Hyalopterus arundinis, Hyalopterus spp., Hyperomyzus pallidus, Icerya spp., Idiocerus spp., Idioscopus clypealis, Idioscopus spp., Irbisia pacifica, Irbisia sp., Jacobiasca lybica, Labops hesperius, Labops sp., Laodelphax spp., Laodelphax striatellus, Lecanium corni, Lepidosaphes spp., Leptocorisa chinensis, Leptocorisa spp., Leptocorsia acuta, Leptocorsia oratorius, Leptodelphax maculigera, Leptodictya tabida, Leptoglossus phyllopus, Leptoglossus spp., Lipaphis erysimi, Lopaphis erysimi, Lyctus bruneus, Lygus hesperus, Lygus lineolaris, Lygus spp., Lyogenys maidis, Macropes excavatus, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphum rosae, Macrosiphum spp., Mahanarva fimbriolata, Mahanarva spp., Margarodes spp., Melanaphis sacchari, Metcalfa pruinosa, Metcalfiella spp., Metopolophium dirhodum, Metopolophium spp., Monellia costalis, Monelliopsis pecanis, Murgantia histrionic, Murgantia spp., Myndus crudus, Myzus persicae, Myzus spp., Nasonovia ribisnigri, Neomegalotomus spp., Neotoxoptera spp., Nephotettix cincticeps, Nephotettix malayanus, Nephotettix nigropictus, Nephotettix parvus, Nephottetix spp., Nephottetix virescens, Nesidiocoris tenuis, Neurocolpus nubilus, Nezara antennata, Nezara hilare, Nezara spp., Nezara viridula, Nilaparvata lugens, Nilaparvata spp., Nippolachnus piri, Nysius simulans, Odonaspis ruthae, Oebalus insularis, Oebalus mexicana, Oebalus poecilus, Oebalus pugnase, Oebalus pugnax, Oebalus spp., Oncometopia spp., Oregma lanigera, Orthezia praelonga, Orthezia spp., Parabemisia myricae, Paracoccus marginatus, Paratrioza cockerelli, Paratrioza spp., Parlatoria pergandei, Parlatoria spp., Pemphigus spp., Peregrinus maidis, Perkinsiella spp., Phenacoccus spp., Phloeomyzus passerinii, Phorodon humuli, Phylloxera spp., Phylloxera vastatrix, Piesma spp., Piezodorus guildinii, Piezodorus spp., Pinnaspis aspidistrae, Planococcus citri, Planococcus spp., Plautia crossota, Protopulvinaria pyriformis, Psallus seriatus, Pseudacysta persea, Pseudatomoscelis seriatus, Pseudaulacaspis pentagona, Pseudaulacaspis spp., Pseudococcus comstocki, Pseudococcus spp., Psylla pyri, Psylla pyricola, Psylla spp., Pulvinaria aethiopica, Pyrilla spp., Quadraspidiotus perniciosus, Quadraspidiotus spp., Quesada gigas, Rastrococcus spp., Recilia dorsalis, Rhodnius prolixus, Rhodnius spp., Rhopalosiphum graminum, Rhopalosiphum padi, Rhopalosiphum pseudobrassicas, Rhopalosiphum spp., Rhopalus maculatus, Riptortus clavatus, Sahlbergella singularis, Saissetia oleae, Saissetia spp., Sarucallis kahawaluokalani, Scaphoideus spp., Scaphoideus titanus, Scaptocoris castanea, Scaptocoris spp., Schizaphis graminum, Schizaphis spp., Scotinophara coarctata, Scotinophara lurida, Scotinophara spp., Scotinophora spp., Selenaspidus articulatus, Selenaspidus spp., Sitobion avenae, Sitobion spp., Sogatella furcifera, Sogatella spp., Sogatodes spp., Spissistilus festinus, Spissistilus spp., Stictocephala festina, Tarophagus Proserpina, Thyanta spp., Tibraca spp., Tinocallis caryaefoliae, Tomaspis spp., Toxoptera spp., Trialeurodes spp., Trialeurodes vaporariorum, Triatoma spp., Tridiscus sporoboli, Trionymus spp., Trioza spp., Typhlocyba spp., Unaspis citri, Unaspis spp., Unaspis yanonensis, Vatiga illudens, Viteus vitifolii, Zygina flammigera, and Zyginidia scutellaris;
[0255] from the order Heteroptera, for example, Piesma quadrata;
[0256] from the order Hygrophila, for example, Galba spp., Galba trunculata, and Lymnaea spp.;
[0257] from the order Hymenoptera, for example, Acromyrmex heyri, Acromyrmex lundii, Acromyrmex spp., Arge spp., Athalia rosae, Athalia spp., Atta bisphaerica, Atta capiguara, Atta laevigata, Atta sexdens rubropilosa, Atta spp., Brachymyrmex sp, Camponotus floridanus, Camponotus herculeanus, Camponotus ligniperdus, Camponotus pennsylvanicus, Camponotus spp., Cephus spp., Crematogaster spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius emarginatu, Lasius flavus, Lasius neglectus, Lasius Neoniger, Lasius niger, Lasius spp., Linepithema humile, Messor structor, Monomorium minimum, Monomorium pharaonis, Myrmica rubra, Neodiprion spp., Paratrechina spp., Pheidole megacephala, Pogonomyrmex spp., Pteromalus spp., Slenopsis invicta, Solenopsis geminata, Solenopsis invicta, Solenopsis molesta, Solenopsis spp., Tapinoma darioi, Tapinoma ibericum, Tapinoma magnum, Tapinoma melanocephalum, Tapinoma nigerrimum, Tapinoma sessile, Technomyrmex albipes, Tetramorium caespitum, Vespa spp., and Wasmania auropunctata;
[0258] from the order Isopoda, for example, Armadillidium vulgare, Oniscus asellus, and Porcellio scaber;
[0259] from the order Isoptera, for example, Caenorhabditis elegans, Coptotermes acinaciformis, Coptotermes curvignathus, Coptotermes formosanus, Cornitermes cumulans, Cornitermes spp.., Globitermes sulphureus, Heterotermes aureus, Heterotermes longiceps, Heterotermes spp.., Heterotermes tenuis, Macrotermes bellicosus, Macrotermes spp., Microtermes, Nasutitermes exitiosus, Nasutitermes walkeri, Neocapritermes opacus, Neocapritermes parvus, Odontotermes obesus, Odontotermes spp., Procornitermes spp., Procornitermes triacifer, Reticulitermes flavipes, Reticulitermes hageni, Reticulitermes hesperus, Reticulitermes lucifugus, Reticulitermes santonensis, Reticulitermes speratu, Reticulitermes speratus, Reticulitermes spp., Reticulitermes verginicus, Reticulitermes virginicus, Schedorhinotermes spp., and Termes obesus;
[0260] from the order Ixodida, for example, Amblyomma americanum, Amblyomma cajennense, Amblyomma hebraeum, Amblyomma maculatum, Amblyomma spp., Amblyomma variegatum, Argas persicus, Argas reflexus, Argas spp., Boophilus spp., Dermacentor albipictus, Dermacentor andersoni, Dermacentor marginatus, Dermacentor pictus, Dermacentor reticulatus, Dermacentor spp., Dermacentor variabilis, Haemaphysalis cinnabarina, Haemaphysalis concinna, Haemaphysalis leachi, Haemaphysalis longicorni, Haemaphysalis otophila, Haemaphysalis punctata, Haemophysalis spp., Hyalomma aegypticum, Hyalomma anatolicum, Hyalomma marginatum, Hyalomma mauritanicum, Hyalomma spp., Hyalomma transiens, Ixodes canisuga, Ixodes hexagonus, Ixodes holocyclus, Ixodes pacificus, Ixodes pilosus, Ixodes ricinus, Ixodes rubicundus, Ixodes scapularis, Ixodes spp., Ornithodoros spp., Ornithodorus moubata, Ornithodorus spp., Otobius megnini, Otobius spp., Rhiphicephalus (former Boophilus) microplus, Rhiphicephalus (former Boophilus) spp., Rhipicephalus annulatus, Rhipicephalus appendiculatus, Rhipicephalus bursa, Rhipicephalus calceratus, Rhipicephalus capensis, Rhipicephalus decoloratus, Rhipicephalus evertsi, Rhipicephalus microplus, Rhipicephalus sanguineus, Rhipicephalus spp., Rhipicephalus turanicus, and Rhipicephalus zambeziensis;
[0261] from the order Julida, for example, Julus hesperus, and Julus spp..;
[0262] from the order Lepidoptera, for example, Acleris spp., Adoxophyes orana, Adoxophyes spp., Aegeria spp., Agrotis fucosa, Agrotis ipsilon, Agrotis spp., Alabama argillacea, Amyelois transitella, Amylois spp., Anarsia lineatella, Anomis flava, Anticarsia gemmatalis, Anticarsia spp., Apamea spp., Archips spp., Argyresthia spp., Argyrotaenia spp., Autographa spp., Bucculatrix thurberiella, Bupalus piniarius, Busseola fusca, Cadra cautella, Capua reticulana, Carpocapsa pomonella, Carposina nipponensis, Cheimatobia brumata, Chilo auricilius, Chilo indicus, Chilo partellus, Chilo polychrysus, Chilo spp., Chilo suppressalis, Chlosyne lacinia, Choristoneura fumiferana, Choristoneura rosaceana, Choristoneura spp., Chrysodeixis includens, Chrysodeixis spp., Chrysoteuchia topiaria, Clysia ambiguella, Cnaphalocrocis medinalis, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Colias eurytheme, Colias lesbia, Conopomorpha cramarella, Cosmophila flava, Crambus praefectellus, Crambus sp., Crambus spp., Crocidolomia binotalis, Cryptophlebia leucotreta, Cydalima perspectalis, Cydia molesta, Cydia pomonella, Cydia spp., Damalinea spp., Diaphania spp., Diatraea saccharalis, Diatraea spp., Diparopsis castanea, Earias insulana, Earias spp., Elasmopalpus lignosellus, Elasmopalpus spp., Eldana saccharina, Ephestia cautella, Ephestia kuehniella, Ephestia spp., Epinotia spp., Estigmene acrea, Etiella zinckinella, Eucosma spp., Eupoecilia ambiguella, Eupoecilia spp., Euproctis chrysorrhoea, Euproctis spp., Euxoa auxiliaris, Euxoa messoria, Euxoa spp., Feltia jaculiferia, Feltia spp., Fissicrambus mutabilis, Galleria mellonella, Grapholita molesta, Grapholita spp., Hedya nubiferana, Helicoverpa armigera, Helicoverpa spp., Helicoverpa zea, Heliothis armigera, Heliothis spp., Heliothis virescens, Heliothis zea, Hellula undalis, Herpetogramma phaeopteralis, Herpetogramma spp., Hofmannophila pseudospretella, Homoeosoma electellum, Homoeosoma nebulella, Homoeosoma spp., Homona magnanima, Hyphantria cunea, Keiferia lycopersicella, Keiferia spp., Laphygma spp., Lasmopalpus lignosellus, Leucinodes spp., Leucoptera coffeella, Leucoptera scitella, Leucoptera spp., Lithocollethis spp., Lithophane antennata, Lobesia botrana, Lobesia spp., Loxagrotis albicosta, Loxostege bifidalis, Lymantria dispar, Lymantria spp., Lyonetia clerkella, Lyonetia spp., Malacosoma americanum, Malacosoma neustria, Mamestra brassicae, Mamestra spp., Manduca sexta, Marasmia spp., Maruca spp., Mocis latipes, Mocis repanda, Mythimna separata, Neoleucinodes spp., Noctua spp., Nymphula depunctalis, Omiodes indicatus, Operophtera spp., Oria spp., Orniodes indica, Ostrinia nubilalis, Ostrinia spp., Pammene spp., Pandemis spp., Panolis flammea, Papaipema nebris, Parapediasia teterrellus, Pectinophora gossypiella, Pectinophora spp., Pediasia trisecta, Peridroma saucia, Perileucoptera coffeella, Perileucoptera spp., Phthorimaea operculella, Phthorimaea spp., Phyllocnistis citrella, Phyllocnistis spp., Pieris brassicae, Pieris rapae, Pieris spp., Plusia spp., Plutella maculipennis, Plutella spp., Plutella xylostella, Prays citri, Prays spp., Prodenia spp., Pseudaletia spp., Pseudaletia unipuncta, Pseudoplusia includens, Pseudoplusia spp., Rachiplusia nu, Rachiplusia spp., Richia albicosta, Scirpophaga incertulas, Scirpophaga innotata, Scirpophaga spp., Scripophaga innotata, Scripophaga spp., Sesamia cretica, Sesamia inferens, Sesamia spp., Sitotroga spp., Sparganothis spp., Spodoptera cosmiodes, Spodoptera eridania, Spodoptera exigua, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Spodoptera spp., Sylepta derogata, Synanthedon spp., Telchin licus, Thaumetopoea spp., Thermesia gemmatalis, Tinea pellionella, Tineola bisselliella, Tortrix spp., Tortrix viridana, Trichoplusia ni, Trichoplusia spp., Tuta absoluta, Tuta spp., and Yponomeuta spp.;
[0263] from the order Littorinimorpha, for example, Oncomelania spp.;
[0264] from the order Lygaeidae, for example, Oxycarenus hyalinipennis;
[0265] from the order Mesostigmata, for example, Amblyseius fallacis, Dermanyssus gallinae, Dermanyssus spp., Ornithonyssus bursa, Ornithonyssus spp., Ornithonyssus sylviarum, Phytoseiulus, Pneumonyssoides caninum, Raillietia spp., Sternostoma spp., Typhlodromus occidentalis, Varroa jacobsoni, and Varroa spp.;
[0266] from the order Opisthorchiida, for example, Clonorchis spp., and Opisthorchis spp.;
[0267] from the order Orthoptera, for example, Acheta domesticus, Gryllotalpa Africana, Gryllotalpa spp., Locusta migratoria, Locusta spp., Melanoplus spp., Neocurtilla hexadactyla, Scapteriscus berellii, Scapteriscus vicinus, and Schistocerca gregaria;
[0268] from the order Oxyurida, for example, Enterobius vermicularis;
[0269] from the order Phthiraptera, for example, Bovicola bovis, Bovicola caprae, Bovicola limbata, Bovicola ovis, Bovicola spp., Damalinia spp., Felicola spp., Felicola subrostratus, Haematopinus asini macrocephalus, Haematopinus eurysternus, Haematopinus spp., Haematopinus suis, Lepikentron ovis, Lepikentron spp., Linognathus oviformis, Linognathus ovillus, Linognathus pedalis, Linognathus setosus, Linognathus spp., Linognathus stenopsis, Linognathus vituli, Pediculus capitis, Pediculus humanus, Pediculus spp., Solenopotes spp., Trichodectes canis, Trichodectes spp., Trimenopon spp., Trinoton spp., Werneckiella equi, and Werneckiella spp.;
[0270] from the order Plagiorchiida, for example, Dicrocoelium spp., and Paragonimus spp.;
[0271] from the order Prostigmata, for example, Aceria sheldoni, Aculus schlechtendali, Aculus spp., Eriophyes cynodoniensis, Halotydeus destructor, and Hemitarsonemus spp.;
[0272] from the order Pseudophyllidea, for example, Diphyllobothrium latum;
[0273] from the order Psocoptera, for example, Liposcelis spp.;
[0274] from the order Pulmonata, for example, Arion spp., Deroceras reticulatum, Deroceras spp., and Succinea spp.;
[0275] from the order Rhabditida, for example, Bunostomum spp., Bursaphelenchus spp., Bursaphelenchus xylophilus, Oesophagostomum spp., Ostertagia spp., Strongyloides fuelleborni, Strongyloides spp., Strongyloides stercoralis, and Trichostrongylus spp.;
[0276] from the order Rodentia, for example, Mus musculus, Rattus norwegicus, and Rattus rattus;
[0277] from the order Sarcoptiformes, for example, Acarus siro, Acarus spp., Caloglyphus spp., Dermatophagoides farinae, Dermatophagoides peteronyssinus, Knemidocoptes spp., Listrophorus spp., Notoedres cati, Notoedres spp., Psoroptes cuniculi, Psoroptes equi, Psoroptes ovis, Psoroptes spp., Rhizoglyphus spp., Sarcoptes bovis, Sarcoptes canis, Sarcoptes caprae, Sarcoptes equi, Sarcoptes ovis, Sarcoptes rupicaprae, Sarcoptes scabiei, Sarcoptes spp., Sarcoptes suis, and Tyrophagus spp.;
[0278] from the order Scorpiones, for example, Centruroides sculpturatus, Centruroides vittatus, Hadrurus arizonensis, and Scorpio maurus;
[0279] from the order Siphonaptera, for example, Ceratophyllus spp., Ctenocephalides canis, Ctenocephalides felis, Ctenocephalides spp., Echidnophaga gallinacea, Pulex irritans, and Xenopsylla cheopis;
[0280] from the order Spirurida, for example, Brugia malayi, Brugia timori, Loa loa, Onchocerca volvulus, and Wuchereria;
[0281] from the order Strongylida, for example, Ancylostoma braziliense, Ancylostoma ceylanicum, Ancylostoma duodenale, Ancylostoma spp., Cooperia spp., Dictyocaulus filaria, Haemonchus contortus, Haemonchus spp., Hyostrongulus spp., and Nematodirus spp.;
[0282] from the order Stylommatophora, for example, Arion ater, Arion circumscriptus, Arion hortensis, Arion rufus, Bradybaena fruticum, Bradybaenidae spp., Cepaea hortensis, Cepaea Nemoralis, Cepaea spp., Deroceras agrestis, Deroceras empiricorum, Deroceras laeve, Discus rotundatus, Discus spp., Euomphalia spp., Helicelia itala, Helicelia obvia, Helicelia spp., Helicidae spp., Helicigona arbustorum, Helicodiscus spp., Helix aperta, Helix spp., Limax cinereoniger, Limax flavus, Limax marginatus, Limax maximus, Limax spp., Limax tenellus, Milax gagates, Milax marginatus, Milax sowerbyi, Milax spp., Ochlodina spp., Opeas spp., Vallonia spp., and Zanitoides spp.;
[0283] from the order Symphyla, for example, Scutigerella immaculata;
[0284] from the order Thysanoptera, for example, Baliothrips biformis, Calliothrips phaseoli, Calliothrips spp., Enneothrips flavens, Enneothrips spp., Frankliniella accidentalis, Frankliniella fusca, Frankliniella occidental, Frankliniella occidentalis, Frankliniella schultzei, Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Hercinothrips spp., Kakothrips spp., Megalurothrips spp., Parthenothrips spp., Pezothrips kellyanus, Rhipiphorothrips cruentatus, Scirtothrips aurantii, Scirtothrips citri, Scirtothrips dorsalis, Scirtothrips spp., Sericothrips variabilis, Stenchaetothrips biformis, Taeniothrips cardamoni, Taeniothrips spp., Thrips palmi, Thrips parvispinus, Thrips spp., and Thrips tabaci; from the order Thysanura, for example, Ctenolepisma longicaudatum, Lepisma saccharifera, Lepisma saccharina, Lepisma semicylindrica, Lepisma vulgaris, and Thermobia domestica;
[0285] from the order Trematoda, for example, Schistosoma spp.;
[0286] from the order Trichocephalida, for example, Trichinella britovi, Trichinella nativa, Trichinella nelsoni, Trichinella pseudopsiralis, and Trichinella spiralis;
[0287] from the order Trichurida, for example, Trichuris trichuria;
[0288] from the order Triplonchida, for example, Paratrichodorus spp.;
[0289] from the order Trombidiformes, for example, Acalitus spp., Acarapis spp., Acarapis woodi, Acaricalus spp., Aceria Anthocoptes, Aculops pelekassi, Aculops spp., Brevipalpus spp., Bryobia praetiosa, Bryobia rubrioculus, Calipitrimerus spp., Cheyletiella blakei, Cheyletiella spp., Cheyletiella yasguri, Demodex bovis, Demodex caballi, Demodex canis, Demodex caprae, Demodex equi, Demodex ovis, Demodex spp., Demodex suis, Eotetranychus spp., Eotetranychus willamettei, Epitrimerus pyri, Eriophyes ribis, Eriophyes spp., Eriophyids’ spp., Eutetranychus spp., Myobia spp., Neoschongastia xerothermobia, Neotrombicula autumnalis, Neotrombicula desaleri, Oligonychus coffeae, Oligonychus ilicis, Oligonychus spp., Ornithocheyletia spp., Panonychus citri, Panonychus spp., Panonychus ulmi, Phyllocoptes gracilis, Phyllocoptruta oleivora, Phyllocoptruta spp., Phytonemus pallidus, Polyphagotarsone latus, Polyphagotarsonemus latus, Polyphagotarsonemus spp., Psorergates ovis, Psorergates spp., Steneotarsonemus spinki, Steneotarsonemus spp., Tarsonemus spp., Tetranychus cinnabarinus, Tetranychus spp., Tetranychus urticae, Trombicula akamushi, Trombicula spp., Vasates lycopersici, and Zetzellia mali;
[0290] from the order Tylenchida, for example, Anguina agrostis, Anguina pacificae, Anguina spp., Aphelenchoides besseyi, Aphelenchoides spp., Aphelenchoides spp., Belonolaimus longicaudatus, Belonolaimus spp., Criconema spp., Criconemella spp., Criconemella sp, Criconemoides onoensis, Criconemoides spp., Ditylenchus angustus, Ditylenchus destructor, Ditylenchus dipsaci, Ditylenchus spp., Dolichodorus spp., Globodera rostochiensis, Globodera spp., Helicotylenchus multicinctus, Helicotylenchus spp., Helicotylenchus spp., Heliocotylenchus multicinctus, Hemicriconemoides spp., Hemicycliophora spp., Heterodera avenae, Heterodera glycines, Heterodera leuceilyma, Heterodera schachtii, Heterodera spp., Heterodera trifolii, Hirschmanniella spp., Hirshmanniella spp., Hoploaimus spp., Hoplolaimus columbus, Hoplolaimus galeatus, Hoplolaimus spp., Hypsoperine spp., Macroposthonia spp., Macropostonia sp, Melinius spp., Meloidogyne arenaria, Meloidogyne graminis, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, Meloidogyne marylandi, Meloidogyne spp., Meloidogyne spp., Meloidogyne sp, Mesocriconema spp., Nacobbus spp., Pratylenchus agilis, Pratylenchus alleni, Pratylenchus brachyurus, Pratylenchus curvitatus, Pratylenchus goodeyi, Pratylenchus neglectans, Pratylenchus neglectus thornei, Pratylenchus penetrans, Pratylenchus sefaensis, Pratylenchus spp., Pratylenchus spp., Punctodera spp., Quinisulcius spp., Radopholus similis, Radopholus spp., Rotylenchulus brachyurus, Rotylenchulus reniformis, Rotylenchulus robustus, Rotylenchulus spp., Rotylenchus reniformis, Rotylenchus spp., Scutellonema spp., Subanguina spp., Tylenchorhynchus Claytoni, Tylenchorhynchus dubius, Tylenchorhynchus spp., Tylenchulus semipenetrans, and Tylenchulus spp.;
[0291] from the order Veneroida, for example, Dreissena spp..
[0292] The active ingredients according to the invention can be used for controlling, i.e. containing or destroying, pests of the abovementioned type which occur in particular on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forests, or on organs, such as fruits, flowers, foliage, stalks, tubers or roots, of such plants, and in some cases even plant organs which are formed at a later point in time remain protected against these pests.
[0293] Suitable target crops are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodder beet; fruit, for example pomaceous fruit, stone fruit or soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; leguminous crops, such as beans, lentils, peas or soya; oil crops, such as oilseed rape, mustard, poppies, olives, sunflowers, coconut, castor, cocoa or ground nuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or bell peppers; Lauraceae, such as avocado, Cinnamonium or camphor; and also tobacco, nuts, coffee, eggplants, sugarcane, tea, pepper, grapevines, hops, the plantain family and latex plants.
[0294] In a particular embodiment, a compound of the formula (I) controls mites, rust mites and spider mites in crops, tress, and plants selected from vegetables (especially tomatoes and cucurbits) , citrus, pome fruits, stone fruit, tree nuts, cotton, tropical crops, avocados, ornamentals, beans, soybean, strawberry, and grapes.
[0295] The compositions and / or methods of the present invention may be also used on any ornamental and / or vegetable crops, including flowers, shrubs, broad-leaved trees and evergreens.
[0296] For example the invention may be used on any of the following ornamental species: Ageratum spp., Alonsoa spp., Anemone spp., Anisodontea capsenisis, Anthemis spp., Antirrhinum spp., Aster spp., Begonia spp. (e.g. B. elatior, B. semperflorens, B. tubéreux) , Bougainvillea spp., Brachycome spp., Brassica spp. (ornamental) , Calceolaria spp., Capsicum annuum, Catharanthus roseus, Canna spp., Centaurea spp., Chrysanthemum spp., Cineraria spp. (C. maritime) , Coreopsis spp., Crassula coccinea, Cuphea ignea, Dahlia spp., Delphinium spp., Dicentra spectabilis, Dorotheantus spp., Eustoma grandiflorum, Forsythia spp., Fuchsia spp., Geranium gnaphalium, Gerbera spp., Gomphrena globosa, Heliotropium spp., Helianthus spp., Hibiscus spp., Hortensia spp., Hydrangea spp., Hypoestes phyllostachya, Impatiens spp. (I. Walleriana) , Iresines spp., Kalanchoe spp., Lantana camara, Lavatera trimestris, Leonotis leonurus, Lilium spp., Mesembryanthemum spp., Mimulus spp., Monarda spp., Nemesia spp., Tagetes spp., Dianthus spp. (carnation) , Canna spp., Oxalis spp., Bellis spp., Pelargonium spp. (P. peltatum, P. Zonale) , Viola spp. (pansy) , Petunia spp., Phlox spp., Plecthranthus spp., Poinsettia spp., Parthenocissus spp. (P. quinquefolia, P. tricuspidata) , Primula spp., Ranunculus spp., Rhododendron spp., Rosa spp. (rose) , Rudbeckia spp., Saintpaulia spp., Salvia spp., Scaevola aemola, Schizanthus wisetonensis, Sedum spp., Solanum spp., Surfinia spp., Tagetes spp., Nicotinia spp., Verbena spp., Zinnia spp. and other bedding plants.
[0297] For example the invention may be used on any of the following vegetable species: Allium spp. (A. sativum, A.. cepa, A. oschaninii, A. Porrum, A. ascalonicum, A. fistulosum) , Anthriscus cerefolium, Apium graveolus, Asparagus officinalis, Beta vulgarus, Brassica spp. (B. Oleracea, B. Pekinensis, B. rapa) , Capsicum annuum, Cicer arietinum, Cichorium endivia, Cichorum spp. (C. intybus, C. endivia) , Citrillus lanatus, Cucumis spp. (C. sativus, C. melo) , Cucurbita spp. (C. pepo, C. maxima) , Cyanara spp. (C. scolymus, C. cardunculus) , Daucus carota, Foeniculum vulgare, Hypericum spp., Lactuca sativa, Lycopersicon spp. (L. esculentum, L. lycopersicum) , Mentha spp., Ocimum basilicum, Petroselinum crispum, Phaseolus spp. (P. vulgaris, P. coccineus) , Pisum sativum, Raphanus sativus, Rheum rhaponticum, Rosemarinus spp., Salvia spp., Scorzonera hispanica, Solanum melongena, Spinacea oleracea, Valerianella spp. (V. locusta, V. eriocarpa) and Vicia faba.
[0298] Preferred ornamental species include African violet, Begonia, Dahlia, Gerbera, Hydrangea, Verbena, Rosa, Kalanchoe, Poinsettia, Aster, Centaurea, Coreopsis, Delphinium, Monarda, Phlox, Rudbeckia, Sedum, Petunia, Viola, Impatiens, Geranium, Chrysanthemum, Ranunculus, Fuchsia, Salvia, Hortensia, rosemary, sage, St. Johnswort, mint, sweet pepper, tomato and cucumber.
[0299] The term "crops" is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
[0300] Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, for example insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as δ-endotoxins, e.g. Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip) , e.g. Vip1, Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome-inactivating proteins (RIP) , such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.
[0301] In the context of the present invention there are to be understood by δ-endotoxins, for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip) , for example Vip1, Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02 / 15701) . Truncated toxins, for example a truncated Cry1Ab, are known. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid replacements, preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3A toxin (see WO 03 / 018810) .
[0302] Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93 / 07278, WO 95 / 34656, EP-A-0 427 529, EP-A-451 878 and WO 03 / 052073.
[0303] The processes for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. CryI-type deoxyribonucleic acids and their preparation are known, for example, from WO 95 / 34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90 / 13651.
[0304] The toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects. Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera) , two-winged insects (Diptera) and moths (Lepidoptera) .
[0305] Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: (maize variety that expresses a Cry1Ab toxin) ; YieldGard (maize variety that expresses a Cry3Bb1 toxin) ; YieldGard (maize variety that expresses a Cry1Ab and a Cry3Bb1 toxin) ; (maize variety that expresses a Cry9C toxin) ; Herculex (maize variety that expresses a Cry1 Fa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium) ; NuCOTN (cotton variety that expresses a Cry1Ac toxin) ; Bollgard (cotton variety that expresses a Cry1Ac toxin) ; Bollgard (cotton variety that expresses a Cry1Ac and a Cry2Ab toxin) ; (cotton variety that expresses a Vip3A and a Cry1Ab toxin) ; (potato variety that expresses a Cry3A toxin) ; GT Advantage (GA21 glyphosate-tolerant trait) , CB Advantage (Bt11 corn borer (CB) trait) and
[0306] Further examples of such transgenic crops are:
[0307] 1. Bt11 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated Cry1Ab toxin. Bt11 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
[0308] 2. Bt176 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a Cry1Ab toxin. Bt176 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
[0309] 3. MIR604 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Maize which has been rendered insect-resistant by transgenic expression of a 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 WO 03 / 018810.
[0310] 4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / DE / 02 / 9. MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects.
[0311] 5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / ES / 96 / 02.
[0312] 6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C / NL / 00 / 10. Genetically modified maize for the expression of the protein Cry1F for achieving resistance to certain Lepidoptera insects and of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium.
[0313] 7. NK603 × MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / GB / 02 / M3 / 03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810. NK603 × MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide (contains glyphosate) , and also a Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
[0314] Transgenic crops of insect-resistant plants are also described in BATS (Zentrum für Biosicherheit und Nachhaltigkeit, Zentrum BATS, Clarastrasse 13, 4058 Basel, Switzerland) Report 2003, (http: / / bats. ch) .
[0315] The term "crops" is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called "pathogenesis-related proteins" (PRPs, see e.g. EP-A-0 392 225) . Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-0 392 225, WO 95 / 33818 and EP-A-0 353 191. The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
[0316] Crops may also be modified for enhanced resistance to fungal (for example Fusarium, Anthracnose, or Phytophthora) , bacterial (for example Pseudomonas) or viral (for example potato leafroll virus, tomato spotted wilt virus, cucumber mosaic virus) pathogens.
[0317] Crops also include those that have enhanced resistance to nematodes, such as the soybean cyst nematode.
[0318] Crops that are tolerance to abiotic stress include those that have enhanced tolerance to drought, high salt, high temperature, chill, frost, or light radiation, for example through expression of NF-YB or other proteins known in the art.
[0319] Antipathogenic substances which can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers for sodium and calcium channels, for example the viral KP1, KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called "pathogenesis-related proteins" (PRPs; see e.g. EP-A-0 392 225) ; antipathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see e.g. WO 95 / 33818) or protein or polypeptide factors involved in plant pathogen defence (so-called "plant disease resistance genes" , as described in WO 03 / 000906) .
[0320] Further areas of use of the compositions according to the invention are the protection of stored goods and store rooms and the protection of raw materials, such as wood, textiles, floor coverings or buildings, and also in the hygiene sector, especially the protection of humans, domestic animals and productive livestock against pests of the mentioned type.
[0321] The present invention provides a compound of the first aspect for use in therapy. The present invention provides a compound of the first aspect, for use in controlling parasites in or on an animal. The present invention further provides a compound of the first aspect, for use in controlling ectoparasites on an animal. The present invention further provides a compound of the first aspect, for use in preventing and / or treating diseases transmitted by ectoparasites.
[0322] The present invention provides the use of a compound of the first aspect, for the manufacture of a medicament for controlling parasites in or on an animal. The present invention further provides the use of a compound of the first aspect, for the manufacture of a medicament for controlling ectoparasites on an animal. The present invention further provides the use of a compound of the first aspect, for the manufacture of a medicament for preventing and / or treating diseases transmitted by ectoparasites.
[0323] The present invention provides the use of a compound of the first aspect, in controlling parasites in or on an animal. The present invention further provides the use of a compound of the first aspect , in controlling ectoparasites on an animal.
[0324] The term "controlling" when used in context of parasites in or on an animal refers to reducing the number of pests or parasites, eliminating pests or parasites and / or preventing further pest or parasite infestation.
[0325] The term "treating" when used used in context of parasites in or on an animal refers to restraining, slowing, stopping or reversing the progression or severity of an existing symptom or disease. The term "preventing" when used used in context of parasites in or on an animal refers to the avoidance of a symptom or disease developing in the animal.
[0326] The term "animal" when used used in context of parasites in or on an animal may refer to a mammal and a non-mammal, such as a bird or fish. In the case of a mammal, it may be a human or non-human mammal. Non-human mammals include, but are not limited to, livestock animals and companion animals. Livestock animals include, but are not limited to, cattle, camellids, pigs, sheep, goats and horses. Companion animals include, but are not limited to, dogs, cats and rabbits.
[0327] A "parasite" is a pest which lives in or on the host animal and benefits by deriving nutrients at the host animal's expense. An "endoparasite" is a parasite which lives in the host animal. An "ectoparasite" is a parasite which lives on the host animal. Ectoparasites include, but are not limited to, acari, insects and crustaceans (e.g. sea lice) . The Acari (or Acarina) sub-class comprises ticks and mites. Ticks include, but are not limited to, members of the following genera: Rhipicaphalus, for example, Rhipicaphalus (Boophilus) microplus and Rhipicephalus sanguineus; Amblyomrna; Dermacentor; Haemaphysalis; Hyalomma; Ixodes; Rhipicentor; Margaropus; Argas; Otobius; and Ornithodoros. Mites include, but are not limited to, members of the following genera: Chorioptes, for example Chorioptes bovis; Psoroptes, for example Psoroptes ovis; Cheyletiella; Dermanyssus; for example Dermanyssus gallinae; Ortnithonyssus; Demodex, for example Demodex canis; Sarcoptes, for example Sarcoptes scabiei; and Psorergates. Insects include, but are not limited to, members of the orders: Siphonaptera, Diptera, Phthiraptera, Lepidoptera, Coleoptera and Homoptera. Members of the Siphonaptera order include, but are not limited to, Ctenocephalides felis and Ctenocephatides canis. Members of the Diptera order include, but are not limited to, Musca spp.; bot fly, for example Gasterophilus intestinalis and Oestrus ovis; biting flies; horse flies, for example Haematopota spp. and Tabunus spp.; haematobia, for example haematobia irritans; Stomoxys; Lucilia; midges; and mosquitoes. Members of the Phthiraptera class include, but are not limited to, blood sucking lice and chewing lice, for example Bovicola Ovis and Bovicola Bovis.
[0328] The term "effective amount" when used used in context of parasites in or on an animal refers to the amount or dose of the compound of the invention, or a salt thereof, which, upon single or multiple dose administration to the animal, provides the desired effect in or on the animal. The effective amount can be readily determined by the attending diagnostician, as one skilled in the art, by the use of known techniques and by observing results obtained under analogous circumstances. In determining the effective amount a number of factors are considered by the attending diagnostician, including, but not limited to: the species of mammal; its size, age, and general health; the parasite to be controlled and the degree of infestation; the specific disease or disorder involved; the degree of or involvement or the severity of the disease or disorder; the response of the individual; the particular compound administered; the mode of administration; the bioavailability characteristics of the preparation administered; the dose regimen selected; the use of concomitant medication; and other relevant circumstances.
[0329] The compounds of the invention may be administered to the animal by any route which has the desired effect including, but not limited to topically, orally, parenterally' and subcutaneously. Topical administration is preferred. Formulations suitable for topical administration include, for example, solutions, emulsions and suspensions and may take the form of a pour-on, spot-on, spray-on, spray race or dip. In the alternative, the compounds of the invention may be administered by means of an ear tag or collar.
[0330] Salt forms of the compounds of the invention include both pharmaceutically acceptable salts and veterinary acceptable salts, which can be different to agrochemically acceptable salts. Pharmaceutically and veterinary acceptable salts and common methodology for preparing them are well known in the art. See, for example, Gould, P.L., "Salt selection for basic drugs" , International Journal of Pharmaceutics, 33: 201 -217 (1986) ; Bastin, R.J., et al. "Salt Selection and Optimization Procedures for Pharmaceutical New Chemical Entities" , Organic Process Research and Development, 4: 427-435 (2000) ; and Berge, S.M., et al., "Pharmaceutical Salts" , Journal of Pharmaceutical Sciences, 66: 1-19, (1977) . One skilled in the art of synthesis will appreciate that the compounds of the invention are readily converted to and may be isolated as a salt, such as a hydrochloride salt, using techniques and conditions well known to one of ordinary skill in the art. In addition, one skilled in the art of synthesis will appreciate that the compounds of the invention are readily converted to and may be isolated as the corresponding free base from the corresponding salt.
[0331] The present invention also provides a method for controlling pests (such as mosquitoes and other disease vectors; see also http: / / www. who. int / malaria / vector_control / irs / en / ) . In one embodiment, the method for controlling pests comprises applying the compositions of the invention to the target pests, to their locus or to a surface or substrate by brushing, rolling, spraying, spreading or dipping. By way of example, an IRS (indoor residual spraying) application of a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention. In another embodiment, it is contemplated to apply such compositions to a substrate such as non-woven or a fabric material in the form of (or which can be used in the manufacture of) netting, clothing, bedding, curtains and tents.
[0332] In one embodiment, the method for controlling such pests comprises applying a pesticidally effective amount of the compositions of the invention to the target pests, to their locus, or to a surface or substrate so as to provide effective residual pesticidal activity on the surface or substrate. Such application may be made by brushing, rolling, spraying, spreading or dipping the pesticidal composition of the invention. By way of example, an IRS application of a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention so as to provide effective residual pesticidal activity on the surface. In another embodiment, it is contemplated to apply such compositions for residual control of pests on a substrate such as a fabric material in the form of (or which can be used in the manufacture of) netting, clothing, bedding, curtains and tents.
[0333] Substrates including non-woven, fabrics or netting to be treated may be made of natural fibres such as cotton, raffia, jute, flax, sisal, hessian, or wool, or synthetic fibres such as polyamide, polyester, polypropylene, polyacrylonitrile or the like. The polyesters are particularly suitable. The methods of textile treatment are known, e.g. WO 2008 / 151984, WO 2003 / 034823, US 5631072, WO 2005 / 64072, WO2006 / 128870, EP 1724392, WO 2005113886 or WO 2007 / 090739.
[0334] Further areas of use of the compositions according to the invention are the field of tree injection / trunk treatment for all ornamental trees as well all sort of fruit and nut trees.
[0335] The compositions according to the invention are also suitable for protecting against insect infestation in the case of materials such as wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and buildings.
[0336] The compositions according to the invention can be used, for example, against the following pests: from the order Coleoptera, for example, Meligethes aeneus, and Meligethes spp.;
[0337] from the order Hemiptera, for example, Ceroplastes spp., Chionaspis tegalensis, Coccus spp., Diceraeus furcatus, Diceraeus melacanthus, Diceraeus spp., Dichelops furcatus, Dichelops melacanthus, Dichelops spp., Orthezia praelonga, Protopulvinaria pyriformis, Saissetia oleae, Selenaspidus spp., and Trioza spp.;
[0338] from the order Lepidoptera, for example, Adoxophyes orana, Adoxophyes spp., Agrotis fucosa, Agrotis ipsilon, Agrotis spp., Amyelois transitella, Anarsia lineatella, Anomis flava, Anticarsia gemmatalis, Anticarsia spp., Apamea spp., Busseola fusca, Capua reticulana, Carpocapsa pomonella, Cheimatobia brumata, Chilo auricilius, Chilo indicus, Chilo partellus, Chilo polychrysus, Chilo spp., Chilo suppressalis, Chlosyne lacinia, Choristoneura fumiferana, Choristoneura rosaceana, Chrysodeixis includens, Chrysodeixis spp., Cnaphalocrocis medinalis, Cnaphalocrocis spp., Colias eurytheme, Cosmophila flava, Cydia molesta, Cydia pomonella, Cydia spp., Diaphania spp., Diatraea saccharalis, Diatraea spp., Diparopsis castanea, Earias insulana, Earias spp., Elasmopalpus lignosellus, Elasmopalpus spp., Epinotia spp., Etiella zinckinella, Eupoecilia ambiguella, Eupoecilia spp., Euproctis chrysorrhoea, Euxoa auxiliaris, Euxoa messoria, Euxoa spp., Feltia jaculiferia, Feltia spp., Grapholita molesta, Grapholita spp., Helicoverpa armigera, Helicoverpa spp., Helicoverpa zea, Heliothis armigera, Heliothis spp., Heliothis virescens, Heliothis zea, Homoeosoma nebulella, Homoeosoma spp., Homona magnanima, Keiferia spp., Laphygma spp., Lasmopalpus lignosellus, Leucinodes spp., Leucoptera coffeella, Leucoptera spp., Lithophane antennata, Lobesia botrana, Lobesia spp., Loxagrotis albicosta, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Mamestra spp., Marasmia spp., Maruca spp., Mocis latipes, Mocis repanda, Neoleucinodes spp., Nymphula depunctalis, Omiodes indicatus, Oria spp., Ostrinia nubilalis, Ostrinia spp., Pectinophora gossypiella, Pectinophora spp., Phthorimaea spp., Phyllocnistis citrella, Phyllocnistis spp., Pieris brassicae, Pieris rapae, Pieris spp., Plusia spp., Plutella maculipennis, Plutella spp., Plutella xylostella, Prays citri, Prodenia spp., Pseudoplusia includens, Pseudoplusia spp., Rachiplusia nu, Rachiplusia spp., Scirpophaga incertulas, Scirpophaga innotata, Scirpophaga spp., Scripophaga spp., Sesamia cretica, Sesamia inferens, Sesamia spp., Spodoptera cosmiodes, Spodoptera eridania, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Spodoptera spp., Thermesia gemmatalis, Tortrix spp., Tortrix viridana, Trichoplusia ni, Trichoplusia spp., Tuta absoluta, and Tuta spp..
[0339] In a preferred embodiment of each aspect, a compound TX (where the abbreviation “TX” means “one compound selected from the compounds defined in Tables A-1 to A-42, Tables B-1 to B-42, and Table P” ) controls one or more of pests selected from selected from the genus: Spodoptera spp, Plutella spp, Frankliniella spp, Thrips spp, Euschistus spp, Cydia spp, Nilaparvata spp, Myzus spp, Cnaphalocrocis spp, Chrysodeixis spp, Aphis spp, Diabrotica spp, Rhopalosiphum spp, Pseudoplusia spp and Chilo spp. In a preferred embodiment of each aspect, a compound TX (where the abbreviation “TX” means “one compound selected from the compounds defined in Tables A-1 to A-42, Tables B-1 to B-42, and Table P” ) controls one or more of pests selected from the genus: Spodoptera spp, Plutella spp, Frankliniella spp, Thrips spp, Euschistus spp, Cydia spp, Nilaparvata spp, Myzus spp, Cnaphalocrocis spp, Chrysodeixis spp, Aphis spp, Diabrotica spp, Rhopalosiphum spp, Pseudoplusia spp and Chilo spp.
[0340] The compounds of formula I, or salts thereof, are especially suitable for controlling one or more of Spodoptera littoralis, Plutella xylostella, Frankliniella occidentalis, Thrips tabaci, Euschistus heros, Cydia pomonella, Nilaparvata lugens, Myzus persicae, Cnaphalocrocis medinalis, Chrysodeixis incIudens, Aphis craccivora, Diabrotica balteata, Rhopalosiphum padi, and Chilo suppressalis.
[0341] In a preferred embodiment of each aspect, a compound TX (where the abbreviation “TX” means “one compound selected from the compounds defined in Tables A-1 to A-42, Tables B-1 to B-42, and Table P” ) controls one or more of Spodoptera littoralis, Plutella xylostella, Frankliniella occidentalis, Thrips tabaci, Euschistus heros, Cydia pomonella, Nilaparvata lugens, Myzus persicae, Cnaphalocrocis medinalis, Chrysodeixis incIudens, Aphis craccivora, Diabrotica balteata, Rhopalosiphum Padia, and Chilo Suppressalis, such as Spodoptera littoralis + TX, Plutella xylostella + TX; Frankliniella occidentalis + TX, Thrips tabaci + TX, Euschistus heros + TX, Cydia pomonella + TX, Nilaparvata lugens + TX, Myzus persicae + TX, Cnaphalocrocis medinalis + TX, Chrysodeixis incIudens + TX, Aphis craccivora + TX, Diabrotica balteata + TX, Rhopalosiphum Padi + TX, and Chilo suppressalis +TX.
[0342] In an embodiment, of each aspect, one compound from Tables A-1 to A-42, Tables B-1 to B-42, and Table P is suitable for controlling Spodoptera littoralis, Plutella xylostella, Frankliniella occidentalis, Thrips tabaci, Euschistus heros, Cydia pomonella, Nilaparvata lugens, Myzus persicae, Cnaphalocrocis medinalis, Chrysodeixis incIudens, Aphis craccivora, Diabrotica balteata, Rhopalosiphum Padia, and Chilo Suppressalis in cotton, vegetable, maize, cereal, rice and soya crops.
[0343] Compounds according to the invention may possess any number of benefits including, inter alia, advantageous levels of biological activity for protecting plants against insects or superior properties for use as agrochemical active ingredients (for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile (against non-target organisms above and below ground (such as fish, birds and bees) , improved physico-chemical properties, or increased biodegradability) . In particular, it has been surprisingly found that certain compounds of formula (I) may show an advantageous safety profile with respect to non-target arthropods, in particular pollinators such as honey bees, solitary bees, and bumble bees. Most particularly, Apis mellifera.
[0344] The compounds according to the invention can be used as pesticidal agents in unmodified form, but they are generally formulated into compositions in various ways using formulation adjuvants, such as carriers, solvents and surface-active substances. The formulations can be in various physical forms, e.g. in the form of dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent pellets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, oil-flowables, aqueous dispersions, oily dispersions, suspo-emulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water-miscible organic solvent as carrier) , impregnated polymer films or in other forms known e.g. from the Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, First Edition, Second Revision (2010) . Such formulations can either be used directly or diluted prior to use. The dilutions can be made, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.
[0345] The formulations can be prepared e.g. by mixing the active ingredient with the formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions. The active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof.
[0346] The active ingredients can also be contained in very fine microcapsules. Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g. slow-release) . Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 %by weight of the capsule weight. The active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution. The encapsulating membranes can comprise, for example, natural or synthetic rubbers, cellulose, styrene / butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art. Alternatively, very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated.
[0347] The formulation adjuvants that are suitable for the preparation of the compositions according to the invention are known per se. As liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, 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, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1, 1, 1-trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxy-propanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and alcohols of higher molecular weight, such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone and the like.
[0348] Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances.
[0349] A large number of surface-active substances can advantageously be used in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier prior to use. Surface-active substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol / alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol / alkylene oxide addition products, such as tridecylalcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di (2-ethylhexyl) sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono-and di-alkylphosphate esters; and also further substances described e.g. in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood New Jersey (1981) .
[0350] Further adjuvants that can be used in pesticidal formulations include crystallisation inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides, and liquid and solid fertilisers.
[0351] The compositions according to the invention can include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives. The amount of oil additive in the composition according to the invention is generally from 0.01 to 10 %, based on the mixture to be applied. For example, the oil additive can be added to a spray tank in the desired concentration after a spray mixture has been prepared. Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow. Preferred oil additives comprise alkyl esters of C8-C22 fatty acids, especially the methyl derivatives of C12-C18 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively) . Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10thEdition, Southern Illinois University, 2010.
[0352] The inventive compositions generally comprise from 0.1 to 99 %by weight, especially from 0.1 to 95 %by weight, of compounds of the present invention and from 1 to 99.9 %by weight of a formula-tion adjuvant which preferably includes from 0 to 25 %by weight of a surface-active substance. Whereas commercial products may preferably be formulated as concentrates, the end user will normally employ dilute formulations.
[0353] The rates of application vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop. As a general guideline compounds may be applied at a rate of from 1 to 2000 l / ha, especially from 10 to 1000 l / ha.
[0354] Preferred formulations can have the following compositions (weight %) :
[0355] Emulsifiable concentrates:
[0356] active ingredient: 1 to 95 %, preferably 60 to 90 %
[0357] surface-active agent: 1 to 30 %, preferably 5 to 20 %
[0358] liquid carrier: 1 to 80 %, preferably 1 to 35 %
[0359] Dusts:
[0360] active ingredient: 0.1 to 10 %, preferably 0.1 to 5 %
[0361] solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
[0362] Suspension concentrates:
[0363] active ingredient: 5 to 75 %, preferably 10 to 50 %
[0364] water: 94 to 24 %, preferably 88 to 30 %
[0365] surface-active agent: 1 to 40 %, preferably 2 to 30 %
[0366] Wettable powders:
[0367] active ingredient: 0.5 to 90 %, preferably 1 to 80 %
[0368] surface-active agent: 0.5 to 20 %, preferably 1 to 15 %
[0369] solid carrier: 5 to 95 %, preferably 15 to 90 %
[0370] Granules:
[0371] active ingredient: 0.1 to 30 %, preferably 0.1 to 15 %
[0372] solid carrier: 99.5 to 70 %, preferably 97 to 85 %
[0373] The following Examples further illustrate, but do not limit, the invention.
[0374] The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.
[0375] The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.
[0376] Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.
[0377] Ready-for-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.
[0378] The combination is mixed and ground with the adjuvants, and the mixture is moistened with water.
[0379] The mixture is extruded and then dried in a stream of air.
[0380] The finely ground combination is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
[0381] Suspension concentrate
[0382] The finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
[0383] Flowable concentrate for seed treatment
[0384] The finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
[0385] Slow Release Capsule Suspension
[0386] 28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate / polymethylene-polyphenylisocyanate-mixture (8: 1) . This mixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved. To this emulsion a mixture of 2.8 parts 1, 6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed. The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The capsule suspension formulation contains 28%of the active ingredients. The medium capsule diameter is 8-15 microns. The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.
[0387] Formulation types include an emulsion concentrate (EC) , a suspension concentrate (SC) , a suspo-emulsion (SE) , a capsule suspension (CS) , a water dispersible granule (WG) , an emulsifiable granule (EG) , an emulsion, water in oil (EO) , an emulsion, oil in water (EW) , a micro-emulsion (ME) , an oil dispersion (OD) , an oil miscible flowable (OF) , an oil miscible liquid (OL) , a soluble concentrate (SL) , an ultra-low volume suspension (SU) , an ultra-low volume liquid (UL) , a technical concentrate (TK) , a dispersible concentrate (DC) , a wettable powder (WP) , a soluble granule (SG) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.
[0388] The Examples which follow serve to illustrate the invention.Examples
[0389] The compounds of the invention can be distinguished from known compounds by virtue of greater efficacy at low application rates, which can be verified by the person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates, if necessary, for example 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm.
[0390] Compounds of Formula (I) may possess any number of benefits including, inter alia, advantageous levels of biological activity for protecting plants against diseases that are caused by fungi or superior properties for use as agrochemical active ingredients (for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile (including improved crop tolerance) , improved physico-chemical properties, or increased biodegradability) .
[0391] Throughout this description, temperatures are given in degrees Celsius (℃) and “mp. ” means melting point. LC / MS means Liquid Chromatography Mass Spectrometry and the description of the apparatus, and the method (Method A) is as follows:
[0392] The description of the LC / MS apparatus &the method A is:
[0393] Agilent (Single quad mass spectrometer)
[0394] Ionisation method: Multimode-Electron Spray &APCI
[0395] Polarity: positive &negative ions
[0396] Capillary (kV) 4.0, Corona Current 4.0μA, Charging Voltage, 2.00kV, Nitrogen Gas Flow: 12.0L / min, Nebulizer Pressure: 40psig, Mass range: 100 to 1000 m / z) , dry gas temperature 250℃, Vaporizer temperature 200℃.
[0397] Mass range: 100 to 900 Da
[0398] Mobile phase: 0.1%Formic acid in water: ACN (1: 1) (%v / v)
[0399] The description of the LC / MS apparatus &the method B is:
[0400] SQ Detector 2 from Waters
[0401] Ionisation method: Electrospray
[0402] Polarity: positive &negative ions
[0403] Capillary (kV) 3.2, Cone (V) 30.00, source temperature: 150℃, Desolvation temperature: 400℃, cone
[0404] gas flow: 50L / h, Desolvation gas flow: 1000 L / h,
[0405] Mass range: 100 to 1000 m / z.
[0406] Column: KINETEX EVO_50 MM (1.7 μm *50*2.1 mm)
[0407] column Temp: 40℃
[0408] Wavelength (nm) : 200 –400 nm
[0409] Solvents: A = ACN, B = 10 mM ammonium formate in water: ACN (95: 5) (%V / V) .
[0410] Gradient: time / %A: 0 / 2, 0.2 / 2, 1.5 / 45, 2.4 / 95, 3.2 / 2, 3.5 / 2
[0411] Flow rate: 0.5 ml / min.
[0412] The description of the LC / MS apparatus &the method C is:
[0413] Shimadzu LCMS-2050 (Single quad mass spectrometer)
[0414] Ion Mode: DUIS
[0415] Polarity: positive &negative ions,
[0416] Interface voltage: 3kV (positive ion) and 2kV (negative ion) ,
[0417] Nebulizer gas flow rate: 2.0 L / min,
[0418] Drying gas flow rate: 5.0 L / min,
[0419] Heating gas flow rate: 7.0 L / min,
[0420] DL temperature: 200 ℃,
[0421] Mass range: m / z 50 to 1000 (positive ion) and m / z 100 to 1000 (negative ion) ,
[0422] Mobile phase: 0.1%Formic acid in water / MeCN (1 / 1) (%v / v)
[0423] HPLC Method A conditions:
[0424] HPLC Method B conditions:
[0425] HPLC Method C conditions:
[0426] List of Abbreviations:AIBN = azobisisobutyronitrileDMF = dimethylformamideDIPEA = N, N-di-isopropylethylamineEt3N = TriethylamineEtOAc = ethyl acetateHCl = hydrochloric acidEDC. HCl = N- (3-Dimethylaminopropyl) -N′-ethylcarbodiimide hydrochlorideCu (OAc) 2. H2O = Copper (II) acetate monohydrateNH2OH. HCl = Hydroxylamine HydrochlorideNaOAc =Sodium acetateLiHMDS = Lithium bis (trimethylsilyl) amideCsF = Cesium FluoridePd (amphos) Cl2= Bis (di-tert-butyl (4-dimethylaminophenyl) phosphine) dichloropalladium (II)
[0427] 1. Pd2 (dba) 3 = Tris (dibenzylideneacetone) dipalladiumXantphos = 4, 5-Bis (diphenylphosphino) -9, 9-dimethylxanthenemp = melting point℃ = degrees CelsiusMeOH = methyl alcoholNaOH = sodium hydroxideNBS = N-bromosuccinimidemin = minutesRT = room temperatureh = hour (s)TFAA = trifluoroacetic acid anhydrideTHF = tetrahydrofurantR = retention time (in minutes)
[0428] LC / MS = Liquid Chromatography Mass Spectrometry (description of the apparatus &the methods used for LC / MS analysis are given above)
[0429] Preparation Examples
[0430] Example 1: This example illustrates the preparation of N- [1- [4- [ [4- (2-isopropylphenyl) oxazol-2-yl] amino] phenyl] -3-methyl-pyrazol-4-yl] -4- (trifluoromethoxy) benzamide (Compound 1 of Table P) .
[0431] Step 1: Preparation of 3-methyl-1H-pyrazol-4-amine
[0432] To a stirred solution of 3-methyl-4-nitro-1H-pyrazole (5.00 g, 37.4 mmol) in EtOH (12.0 mL) and EtOAc (12.0 mL) , was added Pd / C [10%pd / c (50%wet) (1.00 g, 20%w / w of starting material) ] to the reaction mixture. The resulting reaction mixture was stirred under H2 atmosphere at RT for 12 h. After completion of reaction, indicated by TLC (50%EtOAc / Hexane) , the resulting reaction mass was filtered over celite bed, washed with EtOAc (2 x 100 mL) . The filtrate was concentrated under reduced pressure to afford 3-methyl-1H-pyrazol-4-amine.
[0433] 1H NMR (400 MHz, DMSO-d6) 11.66 (br s, 1H) , 6.91 (s, 1H) , 3.49 (br s, 2H) , 2.02 (s, 3H) .
[0434] Step 2: Preparation of N- (3-methyl-1H-pyrazol-4-yl) -4- (trifluoromethoxy) benzamide
[0435] To a stirred solution of 3-methyl-1H-pyrazol-4-amine (3.50 g, 34.2 mmol) in THF (25.0 mL) , was added Et3N (15 mL, 103 mmol) &4- (trifluoromethoxy) benzoyl chloride (7.35 mL, 37.7 mmol) at 0 ℃. The resulting reaction mixture was stirred at RT for 5 h. After completion of reaction, indicated by TLC (50%EtOAc / Hexane) , the resulting mixture was quenched with water (50 mL) &extracted with EtOAc (2 X 50 mL) . The combined organic layers were washed with water (50 mL) , followed by brine solution (50 mL) , dried over anhydrous Na2SO4 &concentrated under reduced pressure to obtain the crude compound. The crude compound was purified by combi flash column chromatography (eluted with 50%EtOAc / Hexane) to afford N- (3-methyl-1H-pyrazol-4-yl) -4- (trifluoromethoxy) benzamide. 1H NMR (400 MHz, DMSO-d6) 12.46 -1237 (br d, 1H) , 9.79 (s, 1H) , 8.07 –8.04 (d, 2H) , 7.86 –7.56 (br d, 1H) , 7.57 –7.49 (d, 2H) , 2.18 (s, 3H) .
[0436] LC-MS (Method A) MS: [M + H] +. = 286.1.
[0437] Step 3: N- [1- (4-bromophenyl) -3-methyl-pyrazol-4-yl] -4- (trifluoromethoxy) benzamide
[0438] To a stirred solution of N- (3-methyl-1H-pyrazol-4-yl) -4- (trifluoromethoxy) benzamide (200 mg, 0.666 mmol) in DMF (10.0 mL) was added (4-bromophenyl) boronic acid (161 mg, 0.799 mmol) , the resulting reaction mixture was degassed with argon atmosphere for 5 min. After that pyridine (0.26 mL, 3.33 mmol) and Cu (OAc) 2. H2O (26.6 mg, 0.133 mmol) was added. The resulting reaction mixture was stirred at 90℃ for 16 h. After completion of reaction, indicated by TLC (60%EtOAc / Hexane) , the resulting mixture was quenched with water (20 mL) &extracted with EtOAc (2 X 30 mL) . The combined organic layers were washed with water (30 mL) followed by brine solution (30 mL) , dried over anhydrous Na2SO4 &concentrated under reduced pressure to obtain the crude compound. The crude compound was purified by combi flash column chromatography (eluted with 80%EtOAc / Hexane) to afford N- [1- (4-bromophenyl) -3-methyl-pyrazol-4-yl] -4- (trifluoromethoxy) benzamide.
[0439] 1H NMR (400 MHz, DMSO-d6) 10.07 (s, 1H) , 8.69 (s, 1H) , 8.09 –8.07 (d, 2H) , 7.78 –7.76 (d, 2H) , 7.66 –7.63 (d, 2H) , 7.55 –7.53 (d, 2H) , 2.29 (s, 3H) .
[0440] LC-MS (Method A) MS: [M + H] +. = 440, 442.
[0441] Step 4: Preparation of 2-isopropyl-N-methoxy-N-methyl-benzamide CAS Registry Number: 1137861-59-6
[0442] To a stirred solution of 2-isopropylbenzoic acid (10.0 g, 57.9 mmol) in DCM (150 mL) was added N-methoxymethanamine hydrochloride (6.53 g, 63.6 mmol) , cooled to -15 ℃, then added N-methymorpholine (7.28 mL, 63.6 mmol) followed by EDC. HCl (10.4 g, 63.6 mmol) subsequently at the same temperature. The resulting reaction mixture was stirred at 0 ℃ for 3 h. After completion of reaction, indicated by TLC (10%EtOAc / hexane) , the resulting mixture was diluted with ammonium chloride solution (100 ml) , extracted with DCM (3 x 100 ml) . The combined organic layers were washed with water (50 mL) , followed by brine solution (50 mL) , dried over anhydrous Na2SO4 &concentrated under reduced pressure to obtain the crude compound. The crude compound was purified by combi flash column chromatography (eluted with 20%EtOAc / Hexane) to afford 2-isopropyl-N-methoxy-N-methyl-benzamide.
[0443] 1H NMR (400 MHz, DMSO-d6) 7.38 (m, 2H) , 7.22 -7.19 (m, 2H) , 3.39 (m, 3H) , 3.26 (m, 3H) , 2.84 (m, 1H) , 1.18 -1.16 (d, 6H) .
[0444] Step 5: Preparation of 1- (2-isopropylphenyl) ethanone CAS Registry Number: 2142-65-6
[0445] To a stirred solution of 2-isopropyl-N-methoxy-N-methyl-benzamide (5.00 g, 22.9 mmol) in THF (50.0 mL) , was added CH3MgBr (1.00 mol / L, 34.4 mL, 34.4 mmol) at 0 ℃. The resulting reaction mixture was stirred at RT for 3 h. After completion of reaction, indicated by TLC (30%EtOAc / hexane) , the resulting mixture was qunched with ammonium chloride solution (50 mL) , diluted with water (50 mL) &extracted with EtOAc (3 x 50 mL) . The combined organic layers were dried over Na2SO4 &concentrated under reduced pressure to obtain the crude compound. The crude compound was purified by combi flash column chromatography (eluted with 30%EtOAc / Hexane) to afford 1- (2-isopropylphenyl) ethanone.
[0446] 1H NMR (400 MHz, CDCl3) 7.49-7.47 (m, 1H) , 7.43-7.41 (m, 2H) , 7.25-7.21 (m, 1H) , 3.47-3.44 (m, 1H) , 2.57 (s, 3H) , 1.25 –1.23 (d, 6H) .
[0447] LC-MS (Method A) MS: [M + H] +. = 163.1.
[0448] Step 6: Preparation of 2-bromo-1- (2-isopropylphenyl) ethenone CAS Registry Number: 1934707-09-1
[0449] To a stirred solution of 1- (2-isopropylphenyl) ethanone (3.30 g, 19.3 mmol) in DCM (50.0 mL) , was added pyridinium tribromide (7.16 g, 21.3 mmol) at 0 ℃ &the resulting reaction mixture was stirred at RT for 3 h. After completion of reaction, indicated by TLC (30%EtOAc / hexane) , the resulting mixture was diluted with water (50 mL) , extracted with DCM (3 x 50 mL) . The combined organic layers were dried over Na2SO4, concentrated under reduced pressure to obtain the crude compound. The crude compound was purified by combi flash column chromatography (eluted with 30%EtOAc / Hexane) to afford 2-bromo-1- (2-isopropylphenyl) ethenone.
[0450] 1H NMR (400 MHz, CDCl3) 7.48-7.44 (m, 3H) , 7.27-7.23 (m, 1H) , 4.40 (s, 2H) , 3.36-3.39 (m, 1H) , 1.26 –1.25 (d, 6H) .
[0451] Step 7: Preparation of 4- (2-isopropylphenyl) oxazol-2-amine
[0452] To a stirred solution of 2-bromo-1- (2-isopropylphenyl) ethanone (3.00 g, 11.8 mmol) in ACN (50.0 mL) , was added urea (7.01 g, 118 mmol) . The resulting reaction mixture was stirred at 85 ℃ for 16 h. After completion of reaction, indicated by TLC (40%EtOAc / hexane) , the resulting mixture was diluted with ice cold water (50 mL) , extracted with EtOAc (2 x 50 mL) . The combined organic layers were dried over Na2SO4 , concentrated under reduced pressure to obtain the crude compound. The crude compound was purified by combi flash column chromatography (eluted with 40%EtOAc / Hexane) to afford 4- (2-isopropylphenyl) oxazol-2-amine.
[0453] 1H NMR (400 MHz, DMSO-d6) 7.47 (s, 1H) , 7.44-7.42 (m, 1H) , 7.37-7.35 (m, 1H) , 7.30-7.26 (m, 1H) , 7.19 -7.15 (m, 1H) , 6.68 (d, 2H) , 3.56 –3.46 (m, 1H) , 1.17-1.15 (d, 6H) .
[0454] Step 8: Preparation of N- [1- [4- [ [4- (2-isopropylphenyl) oxazol-2-yl] amino] phenyl] -3-methyl-pyrazol-4-yl] -4- (trifluoromethoxy) benzamide
[0455] To a stirred solution of 4- (2-isopropylphenyl) oxazol-2-amine (0.1 g, 0.494 mmol) in 1, 4-dioxane (5.00 mL) , was added N- [1- (4-bromophenyl) -3-methyl-pyrazol-4-yl] -4- (trifluoromethoxy) benzamide (0.229 g, 0.494 mmol) , followed by Cs2CO3 (0.161 g, 0.494 mmol) at RT, degassed under N2 atmosphere for 5 min. After that Xantphos (28.6 mg, 0.049 mmol) , Pd2 (dba) 3 (28.4 mg, 0.031 mmol) were added to the reaction mixture and degassed under N2 atmosphere for another 5 min. The resulting reaction mixture was stirred at 120 ℃ for 1 h in microwave. After completion of reaction, indicated by TLC (30%EtOAc / Hexane) , the resulting mixture was quenched with water (10 mL) , extracted with EtOAc (2 X 10 mL) . The combined organic layers were washed with water (10 mL) , followed by brine solution (10 mL) , dried over anhydrous Na2SO4, concentrated under reduced pressure to obtain the crude compound. The crude compound was purified by combi flash column chromatography (eluted with 30%EtOAc / Hexane) to afford N- [1- [4- [ [4- (2-isopropylphenyl) oxazol-2-yl] amino] phenyl] -3-methyl-pyrazol-4-yl] -4- (trifluoromethoxy) benzamide.
[0456] 1H NMR (400 MHz, DMSO-d6) 10.33 (s, 1H) , 10.03 (s, 1H) , 8.56 (s, 1H) , 8.10-8.07 (d, 2H) , 7.81 (s, 1H) , 7.77-7.71 (m, 4H) , 7.55-7.52 (m, 3H) , 7.45-7.43 (d, 1H) , 7.37-7.33 (m, 1H) , 7.26-7.22 (m, 1H) , 3.53-3.48 (m, 1H) , 2.28 (s, 3H) , 1.25-1.23 (d, 6H) .
[0457] LC-MS (Method A) MS: [M + H] +. = 562.2.
[0458] HPLC (Method A) Retention time: 5.32 min;
[0459] Example 2: This example illustrates the preparation of N- [1- [4- [ [3- (2-isopropylphenyl) isoxazol-5-yl] amino] phenyl] -3-methyl-pyrazol-4-yl] -4- (trifluoromethoxy) benzamide (Compound 2 of Table P) .
[0460] Step 1: Preparation of methyl 2-isopropylbenzoate CAS Registry Number: 6623-98-9
[0461] To a stirred solution of 2-isopropylbenzoic acid (3.00 g, 17.4 mmol) in MeOH (30.0 mL) , was added H2SO4 (2.7 mL, 52.1 mmol) &the resulting reaction mixture was stirred at 85℃ for 5 h. After completion of reaction, indicated by TLC (40%EtOAc / hexane) , the resulting mixture was concentrated under reduced pressure, cooled to 0 ℃ &nutralized with NaHCO3 solution (upto pH ~7) , followed by extraction with ethyl acetate (3 x 50 mL) . The combined organic layers were washed with water (30 mL) , brine solution (30 mL) , dried over anhydrous Na2SO4 &concentrated under reduced pressure to obtain the crude compound. The crude compound was purified by combi flash column chromatography (eluted with 20%EtOAc / Hexane) to afford methyl 2-isopropylbenzoate.
[0462] 1H NMR (400 MHz, CDCl3) 7.72-7.70 (m, 1H) , 7.48-7.40 (m, 2H) , 7.23 -7.19 (m, 1H) , 3.89 (s, 3H) , 3.72 –3.68 (m, 1H) , 1.26-1.25 (d, 6H) .
[0463] Step 2: Preparation of 3- (2-isopropylphenyl) -3-oxo-propanenitrile CAS Registry Number: 2090145-61-0
[0464] To a stirred solution of ACN (1.48 mL, 26.7 mmol) in THF (10.0 mL) , cooled to -78 ℃, was added LiHMDS (1.00 mol / L, 10.7 mL, 10.7 mmol) in a drop wise manner &the resulting reaction mixture was stirred at same temperature for 1 h. After that methyl 2-isopropylbenzoate (1.00 g, 5.33 mmol) in THF (2.00 mL) was added at -78 ℃ into the main solution &the resulting mixture was stirred at same temperature for another 2 h. After completion of reaction, indicated by TLC (50%EtOAc / Hexane) , the resulting mixture was quenched with saturated NH4Cl solution (10 mL) , extracted with EtOAc (2 X 25 mL) . The combined organic layers were washed with water (30 mL) , followed by brine solution (30 mL) , dried over anhydrous Na2SO4 &concentrated under reduced pressure to obtain the crude compound. The crude compound was purified by combi flash column chromatography (eluted with 50%EtOAc / Hexane) to afford 3- (2-isopropylphenyl) -3-oxo-propanenitrile.
[0465] 1H NMR (400 MHz, CDCl3) 7.53-7.40 (m, 3H) , 7.31-7.27 (m, 1H) , 4.00 (s, 2H) , 3.52 –3.45 (m, 1H) , 1.26-1.24 (d, 6H) .
[0466] LC-MS (Method A) MS: [M + H] +. = 186.1.
[0467] Step 3: Preparation of 3- (2-isopropylphenyl) isoxazol-5-amine CAS Registry Number: 1897007-67-8 Preparation of 5- (2-isopropylphenyl) isoxazol-3-amine CAS Registry Number: 1891185-61-7
[0468] To a stirred solution of 3- (2-isopropylphenyl) -3-oxo-propanenitrile (500 mg, 2.54 mmol) in 1, 4-Dioxane (10.0 mL) , was added NH2OH. HCl (441 mg, 6.34 mmol) and NaOAc (416 mg, 5.07 mmol) subsequently. The resulting reaction mixture was stirred at 110 ℃ for 16 h. After completion of reaction, indicated by TLC (20%EtOAc / Hexane) , the resulting mixture was quenched with water (20 mL) , extracted with EtOAc (2 X 25 mL) . The combined organic layers were washed with water (30 mL) , followed by brine solution (30 mL) , dried over anhydrous Na2SO4 &concentrated under reduced pressure to obtain the crude compound. The crude compound was purified by combi flash column chromatography (eluted with 20%EtOAc / Hexane) to afford both regio-isomers.
[0469] Isomer A: 3- (2-isopropylphenyl) isoxazol-5-amine
[0470] .1H NMR (400 MHz, DMSO-d6) 7.44-7.37 (m, 2H) , 7.29-7.21 (m, 2H) , 6.74 (d, 2H) , 5.06 (s, 1H) , 3.35 –3.28 (m, 1H) , 1.16-1.14 (d, 6H) .
[0471] LC-MS (Method A) MS: [M + H] +. = 203.2.
[0472] Isomer B: 5- (2-isopropylphenyl) isoxazol-3-amine
[0473] 1H NMR (400 MHz, DMSO-d6) 7.48-7.41 (m, 3H) , 7.30 –7.26 (m, 1H) , 5.99 (s, 1H) , 5.65 (d, 2H) , 3.25 –3.18 (m, 1H) , 1.20-1.85 (d, 6H) .
[0474] LC-MS (Method A) MS: [M + H] +. = 203.2.
[0475] Step 4A: Preparation of N- [1- [4- [ [3- (2-isopropylphenyl) isoxazol-5-yl] amino] phenyl] -3-methyl-pyrazol-4-yl] -4- (trifluoromethoxy) benzamide
[0476] To a stirred solution of 3- (2-isopropylphenyl) isoxazol-5-amine (90.0 mg, 0.445 mmol) (Isomer A) in 1, 4-dioxane (5.00 mL) , was added N- [1- (4-bromophenyl) -3-methyl-pyrazol-4-yl] -4- (trifluoromethoxy) benzamide (206 mg, 0.445 mmol) , Cs2CO3 (290 mg, 0.890 mmol) °assed the reaction mixture under N2 atmosphere for 5 min. After that xantphos (25.7 mg, 0.044 mmol) , Pd2 (dba) 3 (25.6 mg, 0.027 mmol) were added to the reaction mixture, degassed under N2 atmosphere for another 5 min. The resulting reaction mixture was stirred at 150 ℃ for 2 h in microwave. After completion of reaction, indicated by TLC (30%EtOAc / Hexane) , the resulting mixture was quenched with water (10 mL) , extracted with EtOAc (2 X 10 mL) . The combined organic layers were washed with water (10 mL) , followed by brine solution (10 mL) , dried over anhydrous Na2SO4, concentrated under reduced pressure to obtain the crude compound. The crude compound was purified by combi flash column chromatography (eluted with 30%EtOAc / Hexane) to afford N- [1- [4- [ [3- (2-isopropylphenyl) isoxazol-5-yl]amino] phenyl] -3-methyl-pyrazol-4-yl] -4- (trifluoromethoxy) benzamide.
[0477] 1H NMR (400 MHz, DMSO-d6) 10.16 (s, 1H) , 10.04 (s, 1H) , 8.57 (s, 1H) , 8.10-8.07 (d, 2H) , 7.75 -7.72 (d, 2H) , 7.55-7.42 (m, 5H) , 7.34-7.27 (m, 3H) , 5.88 (s, 1H) , 3.39-3.36 (m, 1H) , 2.28 (s, 3H) , 1.20-1.18 (d, 6H) .
[0478] 1H NMR (400 MHz, CDCl3) δ ppm 8.54 (s, 1 H) 8.47 -8.47 (m, 1 H) 7.96 (d, J=8.72 Hz, 2 H) 7.66 (d, J=8.72 Hz, 2 H) 7.57 (s, 1 H) 7.34 -7.49 (m, 5 H) 7.23 -7.28 (m, 3 H) 6.87 (s, 1 H) 5.66 (s, 1 H) 3.30 -3.51 (m, 1 H) 2.42 (s, 3 H) 1.27 (d, J=6.90 Hz, 6 H)
[0479] 19F NMR (377 MHz, CDCl3) δ ppm -57.69 (s, 3 F)
[0480] LC-MS (Method A) MS: [M + H] +. = 562.0.
[0481] 19F NMR (400 MHz, DMSO-d6) δ ppm: -56.65 (s) .
[0482] HPLC (Method B) Retention time: 4.77 min;
[0483] Example 3: This example illustrates the preparation of N- [1- [4- [ [5- (2-isopropylphenyl) isoxazol-3-yl] amino] phenyl] -3-methyl-pyrazol-4-yl] -4- (trifluoromethoxy) benzamide (Compound 4 of Table P)
[0484] Step 4B: Preparation of N- [1- [4- [ [5- (2-isopropylphenyl) isoxazol-3-yl] amino] phenyl] -3-methyl-pyrazol-4-yl] -4- (trifluoromethoxy) benzamide.
[0485] To a stirred solution of 5- (2-isopropylphenyl) isoxazol-3-amine (Isomer B) (30.0 mg, 0.148 mmol) in 1, 4-dioxane (3.00 mL) , was added N- [1- (4-bromophenyl) -3-methyl-pyrazol-4-yl] -4- (trifluoromethoxy) benzamide (72.6 mg, 0.148 mmol) , Cs2CO3 (96.7 mg, 0.297 mmol) °assed the reaction mixture under N2 atmosphere for 5 min. After that xantphos (8.58 mg, 0.0148 mmol) , Pd2 (dba) 3 (8.53 mg, 0.009 mmol) were added to the reaction mixture and degassed under N2 atmosphere for another 5 min. The resulting reaction mixture was stirred at 120 ℃ for 2 h in microwave. After completion of reaction, indicated by TLC (30%EtOAc / Hexane) , the reaction mixture was quenched with water (10 mL) , extracted with EtOAc (2 X 10 mL) . The combined organic layers were washed with water (10 mL) , followed by brine solution (10 mL) , dried over anhydrous Na2SO4 &concentrated under reduced pressure to obtain the crude compound. The crude compound was purified by combi flash column chromatography (eluted with 30%EtOAc / Hexane) to afford N- [1- [4- [ [5- (2-isopropylphenyl) isoxazol-3-yl] amino] phenyl] -3-methyl-pyrazol-4-yl] -4- (trifluoromethoxy) benzamide.
[0486] 1H NMR (400 MHz, DMSO-d6) 10.04 (s, 1H) , 9.41 (s, 1 H) , 8.55 (s, 1H) , 8.10-8.08 (d, 2H) , 7.43 -7.71 (d, 2H) , 7.57-7.51 (m, 7H) , 7.36-7.32 (m, 1H) , 6.31 (s, 1H) , 3.26-3.23 (m, 1H) , 2.29 (s, 3H) , 1.24-1.22 (d, 6H) .
[0487] 13C NMR (151 MHz, DMSO-d6) δ ppm 12.1 (s, 1 C) 24.3 (s, 2 C) 30.0 (s, 1 C) 97.0 (s, 1 C) 117.7 (s, 2 C) 119.1 (s, 2 C) 120.8 (s, 1 C) 121.2 (s, 2 C) 121.7 (s, 1 C) 126.6 (s, 1 C) 126.6 (s, 1 C) 126.6 (s, 1 C) 129.7 (s, 1 C) 130.6 (s, 2 C) 131.1 (s, 1 C) 133.5 (s, 1 C) 133.9 (s, 1 C) 139.6 (s, 1 C) 143.0 (s, 1 C) 147.6 (s, 1 C) 150.9 (d, J=1 Hz, 1 C) 161.1 (s, 1 C) 164.4 (s, 1 C) 168.2 (s, 1 C) .
[0488] 19F NMR (565 MHz, DMSO-d6) δ ppm -56.6 (s, 3 F) .
[0489] LC-MS (Method A) MS: [M + H] +. = 562.2.
[0490] HPLC (Method B) Retention time: 4.84 min;
[0491] Example 4: This example illustrates the preparation of N- [1- [4- [ [5- (2-isopropylphenyl) -1, 2, 4-thiadiazol-3-yl] amino] phenyl] -3-methyl-pyrazol-4-yl] -4- (trifluoromethoxy) benzamide (Compound 3 of Table P) .
[0492] Step 1: Preparation of N- [3-methyl-1- (4-nitrophenyl) pyrazol-4-yl] -4- (trifluoromethoxy) benzamide CAS Registry Number: 2579028-45-6 &Preparation of N- [5-methyl-1- (4-nitrophenyl) pyrazol-4-yl] -4- (trifluoromethoxy) benzamide
[0493] To a stirred solution of N- (3-methyl-1H-pyrazol-4-yl) -4- (trifluoromethoxy) benzamide (1.00 g, 3.51 mmol) in ACN (10.0 mL) , was added Cs2CO3 (2.28 g, 7.01 mmol) , 1-fluoro-4-nitro-benzene (0.465 mL, 4.38 mmol) subsequently. The resulting reaction mixture was stirred at 85 ℃ for 16 h. After completion of reaction, indicated by TLC (50%EtOAc / Hexane) , the resulting mixture was quenched with water (20 mL) , extracted with EtOAc (2 X 25 mL) . The combined organic layers were washed with water (30 mL) , followed by brine solution (30 mL) , dried over anhydrous Na2SO4, concentrated under reduced pressure to obtain the crude compound. The crude compound was purified by combi flash column chromatography (eluted with 80%EtOAc / Hexane) to afford both regio-isomers.
[0494] Isomer A: N- [3-methyl-1- (4-nitrophenyl) pyrazol-4-yl] -4- (trifluoromethoxy) benzamide.
[0495] 1H NMR (400 MHz, DMSO-d6) 10.17 (s, 1H) , 8.90 (s, 1H) , 8.34 -8.32 (d, 2H) , 8.10-8.07 (m, 4H) , 7.56 -7.54 (d, 2H) , 2.35 (s, 3H) .
[0496] LC-MS (Method A) MS: [M + H] +. = 407.1.
[0497] Isomer B: N- [5-methyl-1- (4-nitrophenyl) pyrazol-4-yl] -4- (trifluoromethoxy) benzamide
[0498] 1H NMR (400 MHz, DMSO-d6) 10.09 (s, 1H) , 8.40-8.37 (d, 2H) , 8.12 -8.10 (d, 2H) , 7.99 (s, 1H) , 7.92 -7.90 (d, 2H) , 7.55 -7.53 (d, 2H) , 2.42 (s, 3H) .
[0499] LC-MS (Method A) MS: [M + H] +. = 407.0.
[0500] Step 2: Preparation of N- [1- (4-aminophenyl) -3-methyl-pyrazol-4-yl] -4- (trifluoromethoxy) benzamide (EXP-23-LS5056) CAS Registry Number: 2579028-46-7
[0501] To a stirred solution of N- [3-methyl-1- (4-nitrophenyl) pyrazol-4-yl] -4- (trifluoromethoxy) benzamide (Isomer A) (900 mg, 2.10 mmol) in EtOH: EtOAc (1: 1) (20.0 mL) , was added Pd / C (10.0 %, 336 mg, 0.316 mmol) &the resulting reaction mixture was stirred under H2 pressure at RT for 16 h. After completion of reaction, indicated by TLC (50%EtOAc / Hexane) , the resulting mass was filtered over celite bed &washed with EtOAc (2 x 30 mL) . The filtrate was concentrated under reduced pressure to obtain N- [1- (4-aminophenyl) -3-methyl-pyrazol-4-yl] -4- (trifluoromethoxy) benzamide.
[0502] 1H NMR (400 MHz, DMSO-d6) 9.97 (s, 1H) , 8.35 (s, 1H) , 8.09 –8.06 (d, 2H) , 7.54-7.52 (d, 2H) , 7.39-7.37 (d, 2H) , 6.63 –6.61 (d, 2H) , 5.18 (bs, 2H) , 2.24 (s, 3H) .
[0503] LC-MS (Method A) MS: [M + H] +. = 377.0.
[0504] Step 3: Preparation of 3-bromo-5- (2-isopropylphenyl) -1, 2, 4-thiadiazole
[0505] To a stirred solution of 3-bromo-5-chloro-1, 2, 4-thiadiazole (500 mg, 2.38 mmol) in 1, 4-Dioxane (10.0 mL) and water (1.00 mL) , was added (2-isopropylphenyl) boronic acid (469 mg, 2.86 mmol) . The resulting reaction mixture was degassed with argon atmosphere for 5 min. After that CsF (724 mg, 4.76 mmol) , Pd (amphos) Cl2 (84.3 mg, 0.119 mmol) were added into the main reaction mixture and stirred at 80℃ for 16h. After completion of reaction, indicated by TLC (30%EtOAc / Hexane) , the resulting mixture was quenched with water (20 mL) , extracted EtOAc (2 X 25 mL) . The combined organic layers were washed with water (30 mL) , followed by brine solution (30 mL) , dried over anhydrous Na2SO4 and concentrated under reduced pressure to obtain the crude compound. The crude compound was purified by combi flash column chromatography (eluted with 30%EtOAc / Hexane) to afford 3-bromo-5- (2-isopropylphenyl) -1, 2, 4-thiadiazole.
[0506] 1H NMR (400 MHz, DMSO-d6) 7.65-7.63 (m, 1H) , 7.55 -7.50 (m, 2H) , 7.33-7.29 (m, 1H) , 3.56 –3.53 (m, 1H) , 1.28-1.27 (d, 6H) .
[0507] LC-MS (Method A) MS: [M + H] +. = 283, 285.0.
[0508] Step 4: Preparation of N- [1- [4- [ [5- (2-isopropylphenyl) -1, 2, 4-thiadiazol-3-yl] amino] phenyl] -3-methyl-pyrazol-4-yl] -4- (trifluoromethoxy) benzamide.
[0509] To a stirred solution of N- [1- (4-aminophenyl) -3-methyl-pyrazol-4-yl] -4- (trifluoromethoxy) benzamide (100 mg, 0.239 mmol) in 1, 4-dioxane (5.00 mL) , was added 3-bromo-5- (2-isopropylphenyl) -1, 2, 4-thiadiazole (67.7 mg, 0.239 mmol) , Cs2CO3 (156 mg, 0.478 mmol) &the reaction mixture was degassed under N2 atmosphere for 5 min. After that xantphos (13.8 mg, 0.024 mmol) , Pd2 (dba) 3 (13.8 mg, 0.015 mmol) were added subsequently into the reaction mixture °assed under N2 atmosphere for another 5 min. The resulting reaction mixture was stirred at 120 ℃ for 1 h in microwave. After completion of reaction, indicated by TLC (30%EtOAc / Hexane) , the resulting mixture was quenched with water (20 mL) , extracted with EtOAc (2 X 20 mL) . The combined organic layers were washed with water (10 mL) , followed by brine solution (10 mL) , dried over anhydrous Na2SO4 and concentrated under reduced pressure to obtain the crude compound. The crude compound was purified by combi flash column chromatography (eluted with 30%EtOAc / Hexane) to afford N- [1- [4- [ [5- (2-isopropylphenyl) -1, 2, 4-thiadiazol-3-yl] amino] phenyl] -3-methyl-pyrazol-4-yl] -4- (trifluoromethoxy) benzamide.
[0510] 1H NMR (400 MHz, DMSO-d6) 10.51 (s, 1H) , 10.04 (s, 1H) , 8.57 (s, 1H) , 8.10-8.08 (d, 2H) , 7.88 –7.86 (d, 2H) , 7.74-7.72 (d, 2H) , 7.67-7.65 (m, 1H) , 7.61-7.53 (m, 4H) , 7.40-7.36 (m, 1H) , 3.68-3.64 (m, 1H) , 2.29 (s, 3H) , 1.25-1.23 (d, 6H) .
[0511] LC-MS (Method A) MS: [M + H] +. = 579.2.
[0512] 19F NMR (400 MHz, DMSO-d6) δ ppm: -56.65 (s) .
[0513] HPLC (Method B) Retention time: 5.07 min;
[0514] Example 5: This example illustrates the preparation of 3- (2-isopropyl-5-methylphenyl) -N- (4- (1- (4- (trifluoromethoxy) phenyl) -1H-1, 2, 4-triazol-3-yl) phenyl) isoxazol-5-amine (compound 5 of Table P)
[0515] Step 1: Preparation of 3-bromo-1- (4- (trifluoromethoxy) phenyl) -1H-1, 2, 4-triazole
[0516] A solution of 1-iodo-4- (trifluoromethoxy) benzene (8.0 g, 27.8 mmol) in DMSO (50 mL) was charged with 3-bromo-1H-1, 2, 4-triazole (4.93 g, 33.33 mmol) , copper (I) iodide (1.06 g, 5.56 mmol) and Cs2CO3 (13.58 g, 41.7 mmol) at room temperature and heated at 110 ℃ under N2 atmosphere for 16 h. After completion of reaction, the resulting mixture was quenched with water (2 × 100 mL) and extracted with EtOAc (2 × 100 mL) . The combined organic layers were washed with water (100 mL) and brine (100 mL) , dried over anhydrous Mg2SO4, and concentrated under reduced pressure. The residue was purified by column chromatography to afford 3-bromo-1- (4- (trifluoromethoxy) phenyl) -1H-1, 2, 4-triazole.
[0517] 1H NMR (400 MHz, CDCI3) : δ 8.44 (s, 1H) , 7.70 (d, 2H) , 7.38 (d, 2H) .
[0518] MS (method C) m / z: 307.96 [M + H] +.
[0519] Step 2: Preparation of 4- (1- (4- (trifluoromethoxy) phenyl) -1H-1, 2, 4-triazol-3-yl) aniline
[0520] A solution of 3-bromo-1- (4- (trifluoromethoxy) phenyl) -1H-1, 2, 4-triazole (2.0 g, 6.49 mmol) in 1, 4 dioxane (30 mL) and water (12 mL) was charged with 4- (4, 4, 5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) aniline (1.85 g, 8.44 mmol) , Pd [P (C6H5) 3] 4 (0.15 g, 0.13 mmol) and K2CO3 (1.80 g, 12.98 mmol) at room temperature and heated at 100 ℃ under N2 atmosphere for 6 h. After completion of reaction, the resulting mixture was quenched with water (2 × 50 mL) and extracted with EtOAc (2 × 80 mL) .
[0521] The combined organic layers were washed with water (80 mL) and brine (80 mL) , dried over anhydrous Mg2SO4, and concentrated under reduced pressure. The residue was purified by column chromatography to afford 4- (1- (4- (trifluoromethoxy) phenyl) -1H-1, 2, 4-triazol-3-yl) aniline.
[0522] 1H NMR (400 MHz, CDCI3) : δ 8.51 (s, 1H) , 7.99 (d, 2H) , 7.78 (d, 2H) , 7.37 (d, 2H) , 6.76 (d, 2H) , 3.87 (s, 2H) .
[0523] MS (method C) m / z: 321.14 [M + H] +.
[0524] Step 3: Preparation of 3- (4-bromophenyl) -1- (4- (trifluoromethoxy) phenyl) -1H-1, 2, 4-triazole
[0525] A solution of 4- (1- (4- (trifluoromethoxy) phenyl) -1H-1, 2, 4-triazol-3-yl) aniline (1.25 g, 3.89 mmol) in CH3CN (25 mL) was charged with copper (II) bromide (1.04 g, 4.67 mmol) and isopentyl nitrite (0.57 g, 4.67 mmol) at room temperature and stirred for 3 h. After completion of reaction, the resulting mixture was quenched with water (2 × 40 mL) and extracted with EtOAc (2 × 40 mL) . The combined organic layers were washed with water (30 mL) and brine (30 mL) , dried over anhydrous Mg2SO4, and concentrated under reduced pressure. The residue was purified by column chromatography to afford 3- (4-bromophenyl) -1- (4- (trifluoromethoxy) phenyl) -1H-1, 2, 4-triazole.
[0526] 1H NMR (400 MHz, CDCI3) : δ 8.61 (s, 1H) , 8.07 (d, 2H) , 7.80 (d, 2H) , 7.61 (d, 2H) , 7.39 (d, 2H) . MS (method C) m / z: 383.96 [M + H] +.
[0527] Step 4: Preparation of methyl 5-methyl-2- (prop-1-en-2-yl) benzoate
[0528] In a 50 mL pear-shaped flask, methyl 2-bromo-5-methylbenzoate (2.29 g, 10.00 mmol) , 4, 4, 5, 5-tetramethyl-2- (prop-1-en-2-yl) -1, 3, 2-dioxaborolane (2.69 g, 15.99 mmol) and cesium carbonate (3.91 g, 12.00 mmol) were dissolved in 1, 4-Dioxane (30.0 ml) and water (10.0 ml) to give a light yellow solution. Pd (Ph3P) 4 (0.289 g, 0.250 mmol) was added to the reaction mixture in one portion, and the reaction mixture was warmed to reflux with a heating mantle for 4 h under nitrogen. The reaction mixture was filtered through a celite and the filter cake was rinsed with ethyl acetate (10 mL x 3) .
[0529] The crude product was added to a silica gel column and was eluted with diethyl ether / pentane from 0%to 10%to give methyl 5-methyl-2- (prop-1-en-2-yl) benzoate.
[0530] 1H NMR (400 MHz, CDCI3) : δ 7.59 (dd, 1H) , 7.25 (ddd, 1H) , 7.14 (d, 1H) , 5.08 (quint., 1H) , 4.82-4.83 (m, 1H) , 3.85 (s, 3H) , 2.37 (s, 3H) , 2.06 (dd, 3H) .
[0531] MS (method C) m / z: 191.16 [M + H] +.
[0532] Step 5: Preparation of methyl 2-isopropyl-5-methylbenzoate
[0533] In a 50 mL pear-shaped flask, methyl 5-methyl-2- (prop-1-en-2-yl) benzoate (951 mg, 5.00 mmol) and palladium on carbon (106 mg, 0.100 mmol) were dissolved in methanol (20.0 ml) to give a black suspension. hydrogen was bubbled into the reaction mixture, and the reaction mixture was warmed to 60 ℃ with a heating mantle for 4~6 h. The reaction mixture was filtered through a celite and the filter cake was rinsed with ethyl acetate (10 mL x 3) . The crude product was added to a silica gel column and was eluted with diethyl ether / pentane from 0%to 10%to give methyl 2-isopropyl-5-methylbenzoate.
[0534] 1H NMR (400 MHz, CDCI3) : 7.53 (s, 1H) , 7.25-7.31 (m, 2H) , 3.89 (s, 3H) , 3.65 (hept., 1H) , 2.33 (s, 3H) , 1.24 (d, 6H) .
[0535] MS (method C) m / z: 193.21 [M + H] +.
[0536] Step 6: Preparation of 3- (2-isopropyl-5-methylphenyl) -3-oxopropanenitrile
[0537] In a 100 mL pear-shaped flask, acetonitrile (0.546 ml, 10.44 mmol) was mixed with anhydrous tetrahydrofuran (20 ml) at -78 ℃ to give a colorless solution. LHMDS (1.748 g, 10.44 mmol) was added at -78 ℃, and then methyl 2-isopropyl-5-methylbenzoate (2.008 g, 10.44 mmol) was dropped into the mixture, then the reaction mixture was stirred at -78 ℃ for 2 h. Saturated NH4Cl (50 mL) was added to the reaction mixture followed by adjusting to pH 7~8 with hydrochloric acid, then extraction with ethyl acetate (15 mL x 3) . The combined organic layers were washed with saturated NaCl (20 mL x 2) , dried MgSO4, filtered and concentrated. The crude product was added to a silica gel column and was eluted with ethyl acetate / hexane from 0%to 20%to give3- (2-isopropyl-5-methylphenyl) -3-oxopropanenitrile.
[0538] 1H NMR (400 MHz, CDCI3) : 7.38 (d, 1H) , 7.34 (dd, 1H) , 7.25 (d, 1H) , 4.00 (s, 2H) , 3.44 (hept., 1H) , 2.37 (s, 3H) , 1.23 (d, 6H) .
[0539] MS (method C) m / z: 200.14 [M -H] -.
[0540] Step 7: Preparation of 3- (2-isopropyl-5-methylphenyl) isoxazol-5-amine (target) and 5- (2-isopropyl-5-methylphenyl) isoxazol-3-amine (isomer A and B)
[0541] In a 100 mL pear-shaped flask, 3- (2-isopropyl-5-methylphenyl) -3-oxopropanenitrile (503 mg, 2.499 mmol) , hydroxylamine hydrochloride (868 mg, 12.50 mmol) and sodium acetate (1230 mg, 14.99 mmol) were mixed with ethanol (20 ml) , then the reaction mixture was stirred at reflux for 8 h. H2O (30 mL) was added to the reaction mixture, then extraction with ethyl acetate (15 mL x 3) . The combined organic layers were washed with saturated NaCl (20 mL x 2) , dried MgSO4, filtered and concentrated. The crude product was added to a silica gel column and was eluted with ethyl acetate / hexane from 0%to 25%to give 3- (2-isopropyl-5-methylphenyl) isoxazol-5-amine and 5- (2-isopropyl-5-methylphenyl) isoxazol-3-amine.
[0542] isomer A : 1H NMR (400 MHz, DMSO-d6) : 7.31 (d, 1H) , 7.20 (dd, 1H) , 7.10 (d, 1H) , 6.73 (s, 2H) , 5.04 (s, 1H) , 3.28 (hept., 1H) , 2.28 (s, 3H) , 1.13 (d, 6H) .
[0543] MS (method C) m / z: 217.20 [M + H] +.
[0544] Isomer B: 1H NMR (400 MHz, DMSO-d6) : 7.36 (d, 1H) , 7.26 (d, 1H) , 7.25 (s, 1H) , 5.97 (s, 2H) , 5.65 (s, 1H) , 3.18 (hept., 1H) , 2.30 (s, 3H) , 1.17 (d, 6H) .
[0545] MS (method C) m / z: 217.21 [M + H] +.
[0546] Step 8: Preparation of 3- (2-isopropyl-5-methylphenyl) -N- (4- (1- (4- (trifluoromethoxy) phenyl) -1H-1, 2, 4-triazol-3-yl) phenyl) isoxazol-5-amine
[0547] To a stirred solution of 3- (4-bromophenyl) -1- (4- (trifluoromethoxy) phenyl) -1H-1, 2, 4-triazole (350 mg, 0.911 mmol) in 1, 4-dioxane (10 mL) , was added 3- (2-isopropyl-5-methylphenyl) isoxazol-5-amine (217 mg, 1.002 mmol) , DBU (277 mg, 1.822 mmol) , Cs2CO3 (594 mg, 1.822 mmol) and degassed the reaction mixture under N2 atmosphere for 5 min. After that tBuBrettphos (88 mg, 0.182 mmol) , Xphos (87 mg, 0.182 mmol) , Pd2 (dba) 3 (83 mg, 0.091 mmol) were added to the reaction mixture, degassed under N2 atmosphere for another 5 min. The resulting reaction mixture was stirred at 150 ℃ for 4 h in microwave. After completion of reaction, the resulting mixture was quenched with water (20 mL) , extracted with EtOAc (2 x 20 mL) . The combined organic layers were washed with water (30 mL) and brine (30 mL) , dried over anhydrous Mg2SO4, and concentrated under reduced pressure. The residue was purified by column chromatography to afford 3- (2-isopropyl-5-methylphenyl) -N- (4- (1- (4-(trifluoromethoxy) phenyl) -1H-1, 2, 4-triazol-3-yl) phenyl) isoxazol-5-amine.
[0548] 1H NMR (400 MHz, DMSO-d6) : δ 10.34 (s, 1H) , 9.37 (s, 1H) , 8.08-8.04 (m, 4H) , 7.62 (d, 2H) , 7.40-7.36 (d, 3H) , 7.26 (d, 2H) , 5.98 (s, 1H) , 3.34-3.32 (m, 1H) , 2.32 (s, 3H) , 1.18 (s, 3H) , 1.16 (s, 3H) . MS (method C) m / z: 520.22 [M + H] +.
[0549] HPLC (Method C) Retention time: 7.32 min;
[0550] Example 6: This example illustrates the preparation of N- (2-fluoro-4- (1- (4- (trifluoromethoxy) phenyl) -1H-1, 2, 4-triazol-3-yl) phenyl) -3- (2-isopropyl-5-methylphenyl) isoxazol-5-amine (Compound 6 of Table P) .
[0551] Step 1: Preparation of 2-fluoro-4- (1- (4- (trifluoromethoxy) phenyl) -1H-1, 2, 4-triazol-3-yl) aniline
[0552] A solution of 3-bromo-1- (4- (trifluoromethoxy) phenyl) -1H-1, 2, 4-triazole (1.87 g, 6.07 mmol) in 1, 4 dioxane (30 mL) and water (15 mL) was charged with 2-fluoro-4- (4, 4, 5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) aniline (1.73 g, 7.28 mmol) , Pd [P (C6H5) 3] 4 (0.14 g, 0.12 mmol) and NaHCO3 (1.02 g, 12.14 mmol) at room temperature and heated at 100 ℃ under N2 atmosphere for 6 h. After completion of reaction, the resulting mixture was quenched with water (2 × 50 mL) and extracted with EtOAc (2 × 80 mL) . The combined organic layers were washed with water (80 mL) and brine (80 mL) , dried over anhydrous Mg2SO4, and concentrated under reduced pressure. The residue was purified by column chromatography to afford 2-fluoro-4- (1- (4- (trifluoromethoxy) phenyl) -1H-1, 2, 4-triazol-3-yl) aniline.
[0553] 1H NMR (400 MHz, CDCI3) : δ 8.51 (s, 1H) , 7.86-7.73 (m, 4H) , 7.37 (d, 2H) , 6.90-6.81 (m, 1H) , 3.91 (s, 2H) .
[0554] MS (method C) m / z: 339.13 [M + H] +.
[0555] Step 2: Preparation of 3- (4-bromo-3-fluorophenyl) -1- (4- (trifluoromethoxy) phenyl) -1H-1, 2, 4-triazole
[0556] A solution of 2-fluoro-4- (1- (4- (trifluoromethoxy) phenyl) -1H-1, 2, 4-triazol-3-yl) aniline (1.0 g, 2.96 mmol) in CH3CN (25 mL) was charged with copper (II) bromide (0.99 g, 4.43 mmol) and isopentyl nitrite (0.55 g, 4.43 mmol) at room temperature and stirred for 3 h. After completion of reaction, the resulting mixture was quenched with water (2 × 40 mL) and extracted with EtOAc (2 × 40 mL) . The combined organic layers were washed with water (30 mL) and brine (30 mL) , dried over anhydrous Mg2SO4, and concentrated under reduced pressure. The residue was purified by column chromatography to afford 3- (4-bromo-3-fluorophenyl) -1- (4- (trifluoromethoxy) phenyl) -1H-1, 2, 4-triazole.
[0557] 1H NMR (400 MHz, CDCI3) : δ 8.58 (s, 1H) , 7.96 (dd, 1H) , 7.87 (dd, 1H) , 7.82-7.76 (m, 2H) , 7.65 (dd, 1H) , 7.40 (d, 2H) .
[0558] MS (method C) m / z: 400.98 [M + H] +.
[0559] Step 3: Preparation of N- (2-fluoro-4- (1- (4- (trifluoromethoxy) phenyl) -1H-1, 2, 4-triazol-3-yl) phenyl) -3- (2-isopropyl-5-methylphenyl) isoxazol-5-amine
[0560] To a stirred solution of 3- (4-bromo-3-fluorophenyl) -1- (4- (trifluoromethoxy) phenyl) -1H-1, 2, 4-triazole (357 mg, 0.888 mmol) in 1, 4-dioxane (10 mL) , was added 3- (2-isopropyl-5-methylphenyl) isoxazol-5-amine (211 mg, 0.977 mmol) , DBU (270 mg, 1.775 mmol) , Cs2CO3 (578 mg, 1.775 mmol) and degassed the reaction mixture under N2 atmosphere for 5 min. After that tBuBrettphos (86 mg, 0.178 mmol) , Xphos (85 mg, 0.178 mmol) , Pd2 (dba) 3 (81 mg, 0.089 mmol) were added to the reaction mixture, degassed under N2 atmosphere for another 5 min. The resulting reaction mixture was stirred at 150 ℃ for 4 h in microwave. After completion of reaction, the resulting mixture was quenched with water (20 mL) , extracted with EtOAc (2 x 20 mL) . The combined organic layers were washed with water (30 mL) and brine (30 mL) , dried over anhydrous Mg2SO4, and concentrated under reduced pressure. The residue was purified by column chromatography to afford N- (2-fluoro-4- (1- (4-(trifluoromethoxy) phenyl) -1H-1, 2, 4-triazol-3-yl) phenyl) -3- (2-isopropyl-5-methylphenyl) isoxazol-5-amine.
[0561] 1H NMR (400 MHz, CDCI3) : δ 8.60 (s, 1H) , 8.04-7.95 (m, 2H) , 7.80 (d, 2H) , 7.61 (t, 1H) , 7.39 (d, 2H) , 7.33 (d, 1H) , 7.24 (s, 1H) , 7.05 (d, 1H) , 5.76 (s, 1H) , 3.35 (hept, 1H) , 2.36 (s, 3H) , 1.25 (s, 3H) , 1.23 (s, 3H) .
[0562] MS (method C) m / z: 538.18 [M + H] +.
[0563] HPLC (Method C) Retention time: 7.57 min;
[0564] Table P of prepared compounds:
[0565] The activity of the compositions according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding other insecticidally, acaricidally and / or fungicidally active ingredients. The mixtures of the compounds of formula (I) with other insecticidally, acaricidally and / or fungicidally active ingredients may also have further surprising advantages which can also be described, in a wider sense, as synergistic activity. For example, better tolerance by plants, reduced phytotoxicity, insects can be controlled in their different development stages or better behaviour during their production, for example during grinding or mixing, during their storage or during their use.
[0566] Suitable additions to active ingredients here are, for example, representatives of the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridinylmethyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations.
[0567] The following combinations of a compound of Formula (I) with another active substance in a weight ratio of 1: 1 are preferred (where the abbreviation “TX” means “one compound selected from the compounds defined in the Tables A-1 to A-42, Tables B-1 to B-42, and Table P” ) : (7E, 9Z) -dodeca-7, 9-dien-1-yl acetate + TX, (9Z, 11 E) -tetradeca-9, 11-dien-1-yl acetate + TX, (9Z, 12E) -tetradeca-9, 12-dien-1-yl acetate + TX, (E) -6-methylhept-2-en-4-ol + TX, (E) -dec-5-en-1-yl acetate with (E) -dec-5-en-1-ol + TX, (E) -tridec-4-en-1-yl acetate + TX, (E, Z) -tetradeca-4, 10-dien-1-yl acetate + TX, (Z) -dodec-7-en-1-yl acetate + TX, (Z) -hexadec-11-en-1-yl acetate + TX, (Z) -hexadec-11-enal + TX, (Z) -hexadec-13-en-11-yn-1-yl acetate + TX, (Z) -icos-13-en-10-one + TX, (Z) -tetradec-7-en-1-al + TX, (Z) -tetradec-9-en-1-ol + TX, (Z) -tetradec-9-en-1-yl acetate + TX, 1- (4-chlorophenyl) -2-fluoro-4-methyl-5- (2, 2, 2-trifluoroethylsulfanyl) benzene + TX, 1, 2-dibromo-3-chloropropane + TX, 1, 2-dichloropropane + TX, 1, 2-dichloropropane with 1, 3-dichloropropene + TX, 1, 3-dichloropropene + TX, 14-methyloctadec-1-ene + TX, 1-hydroxy-1H-pyridine-2-thione + TX, 2- (octylthio) ethanol + TX, 2- [5- (2-chloro-3, 3, 3-trifluoro-prop-1-enyl) -1-methyl-imidazol-2-yl] -5-cyclopropyl-3-ethylsulfonyl-pyridine + TX, 2-chlorophenyl N-methylcarbamate (CPMC) + TX, 3- (4-chlorophenyl) -5-methylrhodanine + TX, 3, 4-dichlorotetrahydrothiophene 1, 1-dioxide + TX, 4- (quinoxalin-2-ylamino) benzenesulfonamide + TX, 4-methylnonan-5-ol with 4-methylnonan-5-one + TX, 5-methyl-6-thioxo-1, 3, 5-thiadiazinan-3-ylacetic acid + TX, 6-isopentenylaminopurine + TX, 8-hydroxyquinoline sulfate + TX, abamectin + TX, acequinocyl + TX, acetamiprid + TX, acetoprole + TX, acrinathrin +TX, acynonapyr + TX, Adoxophyes orana GV + TX, afidopyropen + TX, afoxolaner + TX, Agrobacterium radiobacter + TX, AKD-3088 + TX, alanycarb + TX, aldicarb + TX, aldoxycarb + TX, allethrin + TX, alpha-cypermethrin + TX, alphamethrin + 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, apholate + TX, Autographa californica NPV + TX, AZ 60541 + TX, azadirachtin + TX, azocyclotin + TX, Bacillus aizawai + TX, Bacillus chitinosporus AQ746 (NRRL Accession No B-21 618) + TX, Bacillus firmus + TX, Bacillus kurstaki + TX, Bacillus mycoides AQ726 (NRRL Accession No. B-21664) + TX, Bacillus pumilus (NRRL Accession No B-30087) + TX, Bacillus pumilus AQ717 (NRRL Accession No. B-21662) + TX, Bacillus sp. AQ175 (ATCC Accession No. 55608) + TX, Bacillus sp. AQ177 (ATCC Accession No. 55609) + TX, Bacillus sp. AQ178 (ATCC Accession No. 53522) + TX, Bacillus sphaericus Neide + TX, Bacillus subtilis AQ153 (ATCC Accession No. 55614) + TX, Bacillus subtilis AQ30002 (NRRL Accession No. B-50421) + TX, Bacillus subtilis AQ30004 (NRRL Accession No. B-50455) + TX, Bacillus subtilis AQ713 (NRRL Accession No. B-21661) + TX, Bacillus subtilis AQ743 (NRRL Accession No. B-21665) + TX, Bacillus subtilis unspecified + TX, Bacillus thuringiensis AQ52 (NRRL Accession No. B-21619) + TX, Bacillus thuringiensis BD#32 (NRRL Accession No 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. Tenebrionis + TX, Bacillus thuringiensis subspec. kurstaki BMP 123 + TX, Beauveria bassiana + TX, Beauveria brongniartii + TX, benclothiaz + TX, benomyl + TX, bensultap + TX, bentioflumin (CAS Number: 2566451-67-8) + TX, benzoximate + TX, benzpyrimoxan + TX, betacyfluthrin + TX, beta-cypermethrin + TX, bethoxazin + TX, bifenazate + TX, bifenthrin + TX, binapacryl + TX, bioallethrin + TX, bioresmethrin + TX, bis (tributyltin) oxide + TX, bisazir + TX, bistrifluron + TX, bisulflufen + TX, brevicomin + TX, broflanilide + TX, brofluthrinate + TX, bromoacetamide + TX, bromophos-ethyl +TX, bronopol + TX, busulfan + TX, butocarboxim + TX, butopyronoxyl + TX, butoxy (polypropylene glycol) + TX, butylpyridaben + TX, cadusafos + TX, calcium arsenate + TX, carbaryl + TX, carbofuran + TX, carbon disulfide + TX, carbosulfan + TX, cartap + TX, CAS number: 1594624-87-9 + TX, CAS number: 1922957-47-8 + TX, CAS number: 1255091-74-7 + TX, CAS number: 1365070-72-9 + TX, CAS Number: 158062-71-6 + 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: 2128706-05-6 + 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, CAS Number: 2583740-14-9 + TX, CAS Number: 2583751-98-6 + TX, CAS number: 2719848-60-7 + TX, CAS Number: 2898489-71-7 + TX, CAS Number: 2922115-20-4 + TX, CAS Number: 3060345-80-1 + TX, CAS Number: 3061364-30-2 + TX, CAS Number: 34763-86-5 + TX, CAS number: RNA (Leptinotarsa decemlineata-specific recombinant double-stranded interfering GS2) + TX, chlorantraniliprole + TX, chlordane + TX, chlorfenapyr + TX, chloropicrin + TX, chloroprallethrin + TX, chlorpyrifos + TX, chromafenozide + TX, Chrysoperla carnea + TX, clenpirin + TX, cloethocarb + TX, clothianidin + TX, codlelure + TX, codlemone + TX, copper acetoarsenite +TX, copper dioctanoate + TX, copper hydroxide + TX, copper sulfate + TX, cresol + TX, crufomate +TX, Cryptolaemus montrouzieri + TX, cuelure + TX, cyanofenphos + TX, cyantraniliprole + TX, cybenzoxasulfyl (CAS Number: 2128706-04-5) + TX, cybutryne + TX, cyclaniliprole + TX, cyclobutrifluram + TX, cycloprothrin + TX, cycloxaprid + TX, Cydia pomonella GV + TX, cyenopyrafen + TX, cyetpyrafen + TX, cyflumetofen + TX, cyfluthrin + TX, cyhalodiamide + TX, cylohalothrin + TX, cypermethrin + TX, cyphenothrin + TX, cyproflanilide + TX, cyromazine + TX, cytokinins + TX, Dacnusa sibirica + TX, dazomet + TX, DBCP + TX, DCIP + TX, deltamethrin + TX, diafenthiuron +TX, dialifos + TX, diamidafos + TX, dibrom + TX, dibutyl adipate + TX, dibutyl phthalate + TX, dibutyl succinate + TX, dichlofenthion + TX, dichlone + TX, dichlorophen + TX, dicliphos + TX, dicloromezotiaz + TX, diethyltoluamide + TX, diflubenzuron + TX, Diglyphus isaea + TX, dimatif +TX, dimethoate + TX, dimethyl carbate + TX, dimethyl phthalate + TX, dimpropyridaz + TX, dinactin + TX, dinocap + TX, dinotefuran + TX, dioxabenzofos + TX, dipyrithione + TX, disparlure + TX, D-limonene + TX, dodec-8-en-1-yl acetate + TX, dodec-9-en-1-yl acetate + TX, dodeca-8, 10-dien-1-yl acetate + TX, dodicin + TX, dominicalure + TX, doramectin + TX, emamectin + TX, emamectin benzoate + TX, empenthrin + TX, Encarsia formosa + TX, endothal + TX, endrin + TX, eprinomectin + TX, epsilon -momfluorothrin + TX, epsilon-metofluthrin + TX, Eretmocerus eremicus + TX, esfenvalerate + TX, ethion + TX, ethiprole + TX, ethoprophos + TX, ethyl 4-methyloctanoate + TX, ethyl hexanediol + TX, ethylene dibromide + TX, etofenprox + TX, etoxazole + TX, etpyrafen + TX, eugenol + TX, Extract of seaweed and fermentation product derived from melasse + TX, Extract of seaweed and fermentation product derived from melasse comprising urea + TX, Extract of seaweed and fermented plant products + TX, Extract of seaweed and fermented plant products comprising phytohormones, vitamins, EDTA-chelated copper, zinc, and iron + TX, famphur + TX, fenaminosulf + TX, fenamiphos + TX, fenazaquin + TX, fenfluthrin + TX, fenitrothion + TX, fenmezoditiaz + TX, fenobucarb + TX, fenothiocarb + TX, fenoxycarb + TX, fenpropathrin + TX, fenpyrad + TX, fenpyroximate + TX, fensulfothion + TX, fenthion + TX, fentin + TX, fentinacetate + TX, fenvalerate + TX, ferric phosphate + TX, fipronil + TX, flometoquin + TX, flonicamid + TX, fluacrypyrim + TX, fluazaindolizine + TX, fluazuron + TX, flubendiamide + TX, flubenzimine + TX, fluchlordiniliprole +TX, flucitrinate + TX, flucycloxuron + TX, flucythrinate + TX, fluensulfone [318290-98-1] + TX, fluensulfone + TX, flufenerim + TX, flufenprox + TX, flufiprole + TX, fluhexafon + TX, flumethrin + TX, fluopyram + TX, flupentiofenox + TX, flupyradifurone + TX, flupyrimin + TX, flupyroxystrobin + TX, fluralaner + TX, fluvalinate + TX, fluxametamide + TX, formaldehyde + TX, fosthiazate + TX, fosthietan + TX, frontalin + TX, furfural + TX, galquin (CAS Number: 2644770-30-7) + TX, gamma-cyhalothrin + TX, (1: 1 mixture of the (Z, E) and (Z, Z) isomers of hexadeca-7, 11-dien-1-yl-acetate) + TX, grandlure + TX, grandlure I + TX, grandlure II + TX, grandlure III + TX, grandlure IV + TX, Granulovirus + TX, guadipyr + TX, GY-81 + TX, halfenprox + TX, halofenozide + TX, Harpin +TX, Helicoverpa armigera Nucleopolyhedrovirus + TX, Helicoverpa zea NPV + TX, Helicoverpa zea Nucleopolyhedrovirus + TX, Heliothis punctigera Nucleopolyhedrovirus + TX, Heliothis virescens Nucleopolyhedrovirus + TX, hemel + TX, hempa + TX, heptafluthrin + TX, heterophos + TX, Heterorhabditis bacteriophora and H. megidis + TX, hexalure + TX, hexamide + TX, hexythiazox +TX, Hippodamia convergens + TX, hydramethylnon + TX, hydrargaphen + TX, hydrated lime + TX, imicyafos + TX, imidacloprid + TX, imiprothrin + TX, Indazapyroxamet + TX, indoxacarb + TX, iodomethane + TX, iprodione + TX, ipsdienol + TX, ipsenol + TX, isamidofos + TX, isazofos + TX, isocycloseram + TX, Isoflualanam (CAS number: 2892524-05-7) + TX, isothioate + TX, ivermectin +TX, japonilure + TX, kappa-bifenthrin + TX, kappa-tefluthrin + TX, kasugamycin + TX, kasugamycin hydrochloride hydrate + TX, kinetin + TX, lambda-cyhalothrin + TX, ledprona + TX, lepimectin + TX, Leptomastix dactylopii + TX, lineatin + TX, litlure + TX, looplure + TX, lotilaner + TX, lufenuron + TX, Macrolophus caliginosus + TX, Mamestra brassicae NPV + TX, mecarphon + TX, medlure + 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 spp. + TX, metepa + TX, methiocarb + TX, methiotepa + TX, methomyl + TX, methoquin-butyl + TX, methoxyfenozide + TX, methyl apholate +TX, methyl bromide + TX, methyl eugenol + TX, methyl isothiocyanate + TX, methylneodecanamide + TX, metofluthrin + TX, metolcarb + TX, mexacarbate + TX, milbemectin + TX, milbemycin oxime +TX, momfluorothrin + TX, morzid + TX, moxidectin + TX, muscalure + TX, Muscodor albus 620 (NRRL Accession No. 30547) + TX, Muscodor roseus A3-5 (NRRL Accession No. 30548) + TX, Myrothecium verrucaria composition + TX, nabam + TX, NC-184 + TX, Neem tree based products + TX, Neodiprion sertifer NPV and N. lecontei NPV + TX, nickel bis (dimethyldithiocarbamate) + TX, niclosamide + TX, niclosamide-olamine + TX, nicofluprole + TX, nitenpyram + TX, nithiazine + TX, nitrapyrin + TX, octadeca-2, 13-dien-1-yl acetate + TX, octadeca-3, 13-dien-1-yl acetate + TX, octhilinone + TX, omethoate + TX, orfralure + TX, Orius spp. + TX, oryctalure + TX, ostramone + TX, oxamate + TX, oxamyl + TX, oxazosulfyl + TX, oxolinic acid + TX, oxytetracycline + TX, Paecilomyces fumosoroseus + TX, Paecilomyces lilacinus + TX, parathion-ethyl + TX, Pasteuria nishizawae + TX, Pasteuria penetrans + TX, Pasteuria ramosa + TX, Pasteuria thornei + TX, Pasteuria usgae + TX, P-cymene +TX, penfluron + TX, pentachlorophenol + TX, permethrin + TX, phenothrin + TX, phorate + TX, phosphamidon + TX, phosphocarb + TX, Phytoseiulus persimilis + TX, picaridin + TX, pioxaniliprole + TX, piperazine + TX, piperflanilide (CAS number: 2615135-05-0) + TX, piperonylbutoxide + TX, pirimicarb + TX, pirimiphos-ethyl + TX, pirimiphos-methyl + TX, Plutella xylostella Granulosis virus +TX, Plutella xylostella Nucleopolyhedrovirus + TX, Polyhedrosis virus + TX, potassium and molybdenum and EDTA-chelated manganese + TX, potassium ethylxanthate + TX, potassium hydroxyquinoline sulfate + TX, prallethrin + TX, probenazole + TX, profenofos + TX, profluthrin + TX, propargite + TX, propetamphos + TX, propoxur + TX, prothiophos + TX, protrifenbute + TX, pyflubumide + TX, pymetrozine + TX, pyraclofos + TX, pyrafluprole + TX, pyrethrum + TX, pyridaben + TX, pyridalyl + TX, pyridin-4-amine + TX, pyrifluquinazon + TX, pyrimidifen + TX, pyriminostrobin +TX, pyriprole [394730-71-3] + TX, pyriprole + TX, pyriproxyfen + TX, QRD 420 (aterpenoid blend) +TX, QRD 452 (aterpenoid blend) + TX, QRD 460 (aterpenoid blend) + TX, Quillaja saponaria + TX, quinoclamine + TX, quinonamid + TX, resmethrin + TX, Rhodococcus globerulus AQ719 (NRRL Accession No B-21663) + TX, sarolaner + TX, S-bioallethrin + TX, sebufos + TX, selamectin + TX, siglure + TX, silafluofen + TX, simazine + TX, sodium pentachlorophenoxide + TX, sordidin + TX, spidoxamat + TX, spinetoram + TX, spinosad + TX, spirobudifen + TX, spirodiclofen + TX, spiromesifen + TX, spiropidion + TX, spirotetramat + TX, Spodoptera exigua multicapsid nuclear polyhedrosis virus + TX, Spodoptera frugiperda Nucleopolyhedrovirus + TX, Steinernema 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 No. 30232) + TX, Streptomyces sp. (NRRL Accession No. B-30145) + TX, streptomycin + TX, streptomycin sesquisulfate + TX, strychnine + TX, sulcatol + TX, sulfiflumin + TX, sulfoxaflor + TX, tazimcarb + TX, tebufenozide + TX, tebufenpyrad +TX, tebupirimiphos + TX, tecloftalam + TX, tefluthrin + TX, temephos + TX, tepa + TX, terbam + TX, terbufos + TX, terpenoid blend + TX, tetrachlorantraniliprole + TX, tetrachlorothiophene + TX, tetradec-11-en-1-yl acetate + TX, tetradiphon + TX, tetramethrin + TX, tetramethylfluthrin + TX, tetranactin + TX, tetraniliprole + TX, theta-cypermethrin + TX, thiacloprid + TX, thiafenox + TX, thiamethoxam + TX, thiocyclam + TX, thiodicarb + TX, thiofanox + TX, thiohempa + TX, thiomersal + TX, thiometon + TX, thionazin + TX, thiophanate + TX, thiosultap + TX, thiotepa + TX, tiapyrachlor (CAS Number: 1255091-74-7) + TX, tigolaner + TX, tiorantraniliprole + TX, tioxazafen + TX, tolfenpyrad + TX, toxaphene + TX, tralomethrin + TX, transfluthrin + TX, tretamine + TX, triazamate + TX, triazophos + TX, triazuron + TX, tributyltin oxide + TX, trichlorfon + TX, trichloronate + TX, trichlorphon + TX, Trichogramma spp. + TX, trifenmorph + TX, trifluenfuronate + TX, triflumezopyrim + TX, trimedlure + TX, trimedlure A + TX, trimedlure B1 + TX, trimedlure B2 + TX, trimedlure C + TX, trimethacarb + TX, triphenyltin acetate + TX, triphenyltin hydroxide + TX, trunc-call + TX, tyclopyrazoflor + TX, Typhlodromus occidentalis + TX, uredepa + TX, Verticillium lecanii + TX, Verticillium spp. + TX, xylenols + TX, YI-5302 + TX, zeatin + TX, zeta-Cypermethrin + TX;
[0568] N- [ (1 R) -1-benzyl-3-chloro-1-methyl-but-3-enyl] -8-fluoro-quinoline-3-carboxamide + TX, N- [ (1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl] -8-fluoro-quinoline-3-carboxamide + TX, N-ethyl-N’- [5-methoxy-2-methyl-4- [ (2-trifuoromethyl) tetrahydrofuran-2-yl] phenyl] -N-methyl-formamidine (these compounds may be prepared from the methods described in WO2019 / 110427) + TX, (3-methylisoxazol-5-yl) - [4- [5- (trifluoromethyl) -1, 2, 4-oxadiazol-3-yl] phenyl] methanone (these compounds may be prepared from the methods described in WO 2017 / 220485) + TX, (4-phenoxyphenyl) methyl 2-amino-6-methyl-pyridine-3-carboxylate (this compound may be prepared from the methods described in WO 2014 / 006945) + TX, (5-methyl-2-pyridyl) - [4- [5- (trifluoromethyl) -1, 2, 4-oxadiazol-3-yl] phenyl] methanone + TX, (7E, 9Z) -dodeca-7, 9-dien-1-yl acetate + TX, (9Z, 11 E) -tetradeca-9, 11-dien-1-yl acetate + TX, (9Z, 12E) -tetradeca-9, 12-dien-1-yl acetate + TX, (E) -6-methylhept-2-en-4-ol + TX, (E) -dec-5-en-1-yl acetate with (E) -dec-5-en-1-ol + TX, (E) -tridec-4-en-1-yl acetate + TX, (E, Z) -tetradeca-4, 10-dien-1-yl acetate, + TX, (R) -3- (difluoromethyl) -1-methyl-N- [1, 1, 3-trimethylindan-4-yl] pyrazole-4-carboxamide + TX, (Z) -dodec-7-en-1-yl acetate + TX, (Z) -hexadec-11-en-1-yl acetate + TX, (Z) -hexadec-11-enal + TX, (Z) -hexadec-13-en-11-yn-1-yl acetate + TX, (Z) -icos-13-en-10-one + TX, (Z) -tetradec-7-en-1-al + TX, (Z) -tetradec-9-en-1-ol + TX, (Z) -tetradec-9-en-1-yl acetate + TX, (Z, 2E) -5- [1- (2, 4-dichlorophenyl) pyrazol-3-yl] oxy-2-methoxyimino-N, 3-dimethyl-pent-3-enamide (this compound may be prepared from the methods described in WO 2018 / 153707) + TX, (Z, 2E) -5- [1- (4-chlorophenyl) pyrazol-3-yl] oxy-2-methoxyimino-N, 3-dimethyl-pent-3-enamide + TX, , [2- [3- [2- [1- [2- [3, 5-bis (difluoromethyl) pyrazol-1-yl] acetyl] -4-piperidyl] thiazol-4-yl] -4, 5-dihydroisoxazol-5-yl] -3-chloro-phenyl] methanesulfonate + TX, 1- (4, 5-dimethylbenzimidazol-1-yl) -4, 4, 5-trifluoro-3, 3-dimethyl-isoquinoline + TX, 1- (4, 5-dimethylbenzimidazol-1-yl) -4, 4-difluoro-3, 3-dimethyl-isoquinoline + TX, 1- (6, 7-dimethylpyrazolo [1, 5-a] pyridin-3-yl) -4, 4, 5-trifluoro-3, 3-dimethyl-isoquinoline + TX, 1- (6, 7-dimethylpyrazolo [1, 5-a] pyridin-3-yl) -4, 4, 6-trifluoro-3, 3-dimethyl-isoquinoline + TX, 1- (6-chloro-7-methyl-pyrazolo [1, 5-a] pyridin-3-yl) -4, 4-difluoro-3, 3-dimethyl-isoquinoline (these compounds may be prepared from the methods described in WO2017 / 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, 2-dichloropropane with 1, 3-dichloropropene + TX, 1, 3-dichloropropene + TX, 1, 3-dimethoxy-1- [ [4- [5- (trifluoromethyl) -1, 2, 4-oxadiazol-3-yl] phenyl] methyl] urea + TX, 1- [2- [ [1- (4-chlorophenyl) pyrazol-3-yl] oxymethyl] -3-methyl-phenyl] -4-methyl-tetrazol-5-one + TX, 10-dien-1-yl acetate + TX, 14-methyloctadec-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-oxadiazol-3-yl] phenyl] methyl] urea + TX, 1-methyl-4- [3-methyl-2- [ [2-methyl-4- (3, 4, 5-trimethylpyrazol-1-yl) phenoxy] methyl] phenyl] tetrazol-5-one + TX, 2- (difluoromethyl) -N- ( (3R) -1, 1, 3-trimethylindan-4-yl) pyridine-3-carboxamide + TX, 2- (difluoromethyl) -N- ( (3R) -1, 1, 3-trimethylindan-4-yl) pyridine-3-carboxamide + TX, 2- (1, 3-dithiolan-2-yl) phenyl dimethylcarbamate + TX, 2- (2-butoxyethoxy) ethyl piperonylate + TX, 2- (2-butoxyethoxy) ethyl thiocyanate + TX, 2- (4, 5-dimethyl-1, 3-dioxolan-2-yl) phenyl methylcarbamate +TX, 2- (4-chloro-3, 5-xylyloxy) ethanol + TX, 2- (difluoromethyl) -N- (3-ethyl-1, 1-dimethyl-indan-4-yl) pyridine-3-carboxamide + TX, 2- (difluoromethyl) -N- [ (3R) -3-ethyl-1, 1-dimethyl-indan-4-yl] pyridine-3-carboxamide + TX, 2- (difluoromethyl) -N- [ (3S) -3-ethyl-1, 1-dimethyl-indan-4-yl] pyridine-3-carboxamide (this compound may be prepared from the methods described in WO 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-ethylsulfinylethyl methyl phosphate + TX, 2, 2-difluoro-N-methyl-2- [4- [5- (trifluoromethyl) -1, 2, 4-oxadiazol-3-yl] phenyl] acetamide + TX, 2, 4-dichlorophenyl benzenesulfonate + TX, 2, 6-Dimethyl-1H, 5H- [1, 4] dithiino [2, 3-c: 5, 6-c'] dipyrrole-1, 3, 5, 7 (2H, 6H) -tetrone (this compound may be prepared from the methods described in WO 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-triazol-1-yl) propan-2-ol (this compound may be prepared from the methods described in WO 2017 / 029179) + TX, 2- [6- (4-chlorophenoxy) -2- (trifluoromethyl) -3-pyridyl] -1- (1, 2, 4-triazol-1-yl) propan-2-ol (this compound may be prepared from the methods described in WO 2017 / 029179) +TX, 2-chlorovinyl diethyl phosphate + TX, 2-fluoro-N-methyl-N-1-naphthylacetamide + TX, 2-imidazolidone + TX, 2-isovalerylindan-1, 3-dione + TX, 2-methyl (prop-2-ynyl) aminophenyl methylcarbamate + TX, 2-oxo-N-propyl-2- [4- [5- (trifluoromethyl) -1, 2, 4-oxadiazol-3-yl] phenyl] acetamide (this compound may be prepared from the methods described in WO 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 methods described in WO2016 / 156085) + TX, 3- (4, 4-difluoro-3, 4-dihydro-3, 3-dimethylisoquinolin-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-dioxide + TX, 3- [2- (1-chlorocyclopropyl) -3- (2-fluorophenyl) -2-hydroxy-propyl] imidazole-4-carbonitrile (this compound may be prepared from the methods described in WO 2016 / 156290) + TX, 3- [2- (1-chlorocyclopropyl) -3- (3-chloro-2-fluoro-phenyl) -2-hydroxy-propyl] imidazole-4-carbonitrile (this compound may be prepared from the methods described in WO 2016 / 156290) + TX, 3-bromo-1-chloroprop-1-ene + TX, 3-chloro-6-methyl-5-phenyl-4- (2, 4, 6-trifluorophenyl) pyridazine + TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3', 4', 5'-trifluoro-biphenyl-2-yl) -amide + TX, 3-ethyl-1-methoxy-1- [ [4- [5- (trifluoromethyl) -1, 2, 4-oxadiazol-3-yl] phenyl] methyl] urea + TX, 3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate + TX, 4- (2-bromo-4-fluorophenyl) -N- (2-chloro-6-fluorophenyl) -1, 3-dimethyl-1H-pyrazol-5-amine + TX, 4- (2, 6-difluorophenyl) -6-methyl-5-phenyl-pyridazine-3-carbonitrile + TX, 4- (2-bromo-4-fluoro-phenyl) -N- (2-chloro-6-fluoro-phenyl) -2, 5-dimethyl-pyrazol-3-amine + TX, 4- (quinoxalin-2-ylamino) benzenesulfonamide + TX, 4, 4-difluoro-1- (5-fluoro-4-methyl-benzimidazol-1-yl) -3, 3-dimethyl-isoquinoline + TX, 4, 4-difluoro-3, 3-dimethyl-1- (6-methylpyrazolo [1, 5-a] pyridin-3-yl) isoquinoline + TX, 4, 4-difluoro-3, 3-dimethyl-1- (7-methylpyrazolo [1, 5-a] pyridin-3-yl) isoquinoline + TX, 4, 4-dimethyl-2- [ [4- [5- (trifluoromethyl) -1, 2, 4-oxadiazol-3-yl] phenyl] methyl] isoxazolidin-3-one + TX, 4- [ [6- [2- (2, 4-difluorophenyl) -1, 1-difluoro-2-hydroxy-3- (1, 2, 4-triazol-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-triazol-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-triazol-1-yl) propyl] -3-pyridyl] oxy] benzonitrile + TX, 4-chloro-2- (2-chloro-2-methyl-propyl) -5- [ (6-iodo-3-pyridyl) methoxy] pyridazin-3-one + TX, 4-chlorophenyl phenyl sulfone + TX, 4-methyl (prop-2-ynyl) amino-3, 5-xylyl methylcarbamate + TX, 4-methylnonan-5-ol with 4-methylnonan-5-one + TX, 5- (1, 3-benzodioxol-5-yl) -3-hexylcyclohex-2-enone + TX, 5, 5-dimethyl-2- [ [4- [5- (trifluoromethyl) -1, 2, 4-oxadiazol-3-yl]phenyl] methyl] isoxazolidin-3-one + TX, 5, 5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate +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-fluoro-phenoxy) -N- [2- (2, 4-dimethylphenyl) -2, 2-difluoro-ethyl] -5-methyl-pyridazine-4-carboxamide (may be prepared from the methods described in WO 2020 / 109391) + TX, 6-chloro-3- (3-cyclopropyl-2-fluoro-phenoxy) -N- [2- (3, 4-dimethylphenyl) -2, 2-difluoro-ethyl] -5-methyl-pyridazine-4-carboxamide (may be prepared from the methods described in WO 2020 / 109391) + TX, 6-chloro-4, 4-difluoro-3, 3-dimethyl-1- (4-methylbenzimidazol-1-yl) isoquinoline + TX, 6-chloro-N- [2- (2-chloro-4-methyl-phenyl) -2, 2-difluoro-ethyl] -3- (3-cyclopropyl-2-fluoro-phenoxy) -5-methyl-pyridazine-4-carboxamide (may be prepared from the methods described in WO 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- [ (1 R) -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, acethion + TX, acetoprole +TX, acibenzolar + TX, acibenzolar-S-methyl + TX, acrylonitrile + TX, Adoxophyes orana GV + TX, Agrobacterium radiobacter + TX, aldoxycarb + TX, aldrin + TX, allosamidin + TX, allyxycarb + TX, alpha-chlorohydrin + TX, alpha-ecdysone + TX, alpha-multistriatin + TX, aluminium phosphide + TX, Amblyseius spp. + TX, amectotractin + TX, ametoctradin + TX, amidithion + TX, amidothioate + TX, aminocarb + TX, aminopyrifen + TX, amisulbrom + TX, amiton + TX, amiton hydrogen oxalate + TX, amitraz + TX, anabasine + TX, Anagrapha falcifera NPV + TX, Anagrus atomus + TX, ancymidol +TX, anilazine + TX, anisiflupurin + TX, anthraquinone + TX, antu + TX, Aphelinus abdominalis + TX, Aphidius colemani + TX, Aphidoletes aphidimyza + TX, apholate + TX, aramite + TX, arsenous oxide + TX, athidathion + TX, Autographa californica NPV + TX, azaconazole + TX, azamethiphos + TX, azobenzene + TX, azothoate + TX, azoxystrobin + TX, Bacillus sphaericus Neide + TX, Bacillus thuringiensis delta endotoxins + TX, barium carbonate + TX, barium hexafluorosilicate + TX, barium polysulfide + TX, barthrin + TX, Bayer 22 / 190 + TX, Bayer 22408 + TX, Beauveria brongniartii + TX, benalaxyl + TX, benclothiaz + TX, benomyl + TX, benoxafos + TX, benthiavalicarb + TX, benzothiostrobin + TX, benzovindiflupyr + TX, benzyl benzoate + TX, beta-cyfluthrin + TX, beta-cypermethrin + TX, bethoxazin + TX, bioethanomethrin + TX, biopermethrin + TX, bis (2-chloroethyl) ether + TX, bis (tributyltin) oxide + TX, bisazir + TX, bisthiosemi + TX, bitertanol + TX, bixafen + TX, blasticidin-S+ TX, borax + TX, bordeaux mixture + TX, boscalid + TX, brevicomin + TX, brodifacoum + TX, brofenvalerate + TX, bromadiolone + TX, bromethalin + TX, bromfenvinfos + TX, bromoacetamide + TX, bromocyclen + TX, bromo-DDT + TX, bromophos + TX, bromopropylate +TX, bromuconazole + TX, bronopol + TX, bufencarb + TX, bupirimate + TX, buprofezin + TX, busulfan + TX, but-3-ynyl N- [6- [ [ (Z) - [ (1-methyltetrazol-5-yl) -phenyl-methylene] amino] oxymethyl] -2-pyridyl] carbamate + TX, butacarb + TX, butathiofos + TX, butocarboxim + TX, butonate + TX, butopyronoxyl + TX, butoxy (polypropylene glycol) + TX, butoxycarboxim + TX, butylpyridaben + TX, calcium arsenate + TX, calcium cyanide + TX, calcium polysulfide + TX, camphechlor + TX, captafol + TX, captan + TX, carbanolate + TX, carbendazim + TX, carbon disulfide + TX, carbon tetrachloride + TX, carbophenothion + TX, carboxin + TX, cartap hydrochloride + TX, CAS Number: 2049581-78-2 + TX, CAS Number: 2454319-63-0 + TX, CAS Number: 3052252-62-4 + TX, CAS Number: 3052252-63-5 + TX, CAS Number: 83-46-5 + TX, cevadine + TX, chinomethionat + TX, chloralose +TX, chlorbenside + TX, chlorbicyclen + TX, chlordane + TX, chlordecone + TX, chlordimeform + TX, chlordimeform hydrochloride + TX, chlorfenethol + TX, chlorfenson + TX, chlorfensulfide + TX, chlorobenzilate + TX, chloroform + TX, chloroinconazide + TX, chloromebuform + TX, chloromethiuron + TX, chloroneb + TX, chlorophacinone + TX, chloropicrin + TX, chloropropylate +TX, chlorothalonil + TX, chlorphoxim + TX, chlorprazophos + TX, chlorthiophos + TX, chlozolinate +TX, cholecalciferol + TX, Chrysoperla carnea + TX, cinerin I + TX, cinerin II + TX, cinerins + TX, cismethrin + TX, cis-resmethrin + TX, clocythrin + TX, closantel + TX, codlelure + TX, codlemone +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, coumachlor + TX, coumafuryl + TX, coumaphos + TX, coumatetralyl + TX, coumethoxystrobin (jiaxiangjunzhi) + TX, coumithoate + TX, coumoxystrobin + TX, cresol + TX, crimidine + TX, crotamiton + TX, crotoxyphos + TX, crufomate + TX, cryolite + TX, Cryptolaemus montrouzieri + TX, CS 708 + TX, cuelure + TX, cufraneb + TX, cyanofenphos + TX, cyanophos + TX, cyanthoate + TX, cyazofamid + TX, cybutryne + TX, cyclethrin + TX, cyclobutrifluram + TX, Cydia pomonella GV + TX, cyflufenamid + TX, cymiazole + TX, cymoxanil + TX, cyproconazole + TX, cyprodinil + TX, cythioate + TX, cytokinins + TX, Dacnusa sibirica + TX, DAEP + TX, dazomet + TX, DCIP + TX, DCPM + TX, DDT + TX, debacarb + TX, decarbofuran + TX, demephion + TX, demephion-O + TX, demephion-S+ TX, demeton-methyl + TX, demeton-O + TX, demeton-O-methyl + TX, demeton-S+ TX, demeton-S-methyl + TX, demeton-S-methylsulfon + TX, diamidafos + TX, dibutyl adipate + TX, dibutyl phthalate + TX, dibutyl succinate + TX, dicapthon + TX, dichlobentiazox + TX, dichlofenthion + TX, dichlofluanid + TX, dichlone + TX, dichlorophen + TX, dichlorvos + TX, dichlozoline + TX, dicliphos + TX, diclocymet + TX, diclomezine + TX, dicloran + TX, dicresyl + TX, dicyclanil + TX, dicyclopentadiene + TX, dieldrin + TX, dienochlor + TX, diethofencarb + TX, diethyl 5-methylpyrazol-3-yl phosphate + TX, diethyltoluamide + TX, difenacoum + TX, difenoconazole + TX, difethialone + TX, diflovidazin + TX, Diglyphus isaea + TX, dilor + TX, dimatif + TX, dimefluthrin +TX, dimefox + TX, dimetan + TX, dimethirimol + TX, dimethomorph + TX, dimethrin + TX, dimethyl carbate + TX, dimethyl phthalate + TX, dimethylvinphos + TX, dimetilan + TX, dimoxystrobin + TX, dinex + TX, dinex-diclexine + TX, diniconazole + TX, dinocap-4 + TX, dinocap-6 + TX, dinocton +TX, dinopenton + TX, dinoprop + TX, dinosam + TX, dinoseb + TX, dinosulfon + TX, dinoterbon +TX, diofenolan + TX, dioxabenzofos + TX, dioxathion + TX, diphacinone + TX, diphenyl sulfone + TX, dipymetitrone + TX, dipyrithione + TX, disparlure + TX, disulfiram + TX, dithianon + TX, dithicrofos +TX, DNOC + TX, dodec-8-en-1-yl acetate + TX, dodec-9-en-1-yl acetate + TX, dodeca-8 + TX, dodemorph + TX, dodicin + TX, dodine + TX, dofenapyn + TX, dominicalure + TX, doramectin + TX, DSP + TX, d-tetramethrin + TX, ecdysterone + TX, edifenphos + TX, EI 1642 + TX, EMPC + TX, Encarsia formosa + TX, endothal + TX, endothion + TX, enestroburin + TX, enoxastrobin + TX, EPBP + TX, epoxiconazole + TX, eprinomectin + TX, Eretmocerus eremicus + TX, ergocalciferol + TX, etaphos + TX, ethaboxam + TX, ethiofencarb + TX, ethirimol + TX, ethoate-methyl + TX, ethyl 1- [ [4- [ (Z) -2-ethoxy-3, 3, 3-trifluoro-prop-1-enoxy] phenyl] methyl] pyrazole-3-carboxylate (may be prepared from the methods described in WO 2020 / 056090) + TX, ethyl 1- [ [4- [ [2- (trifluoromethyl) -1, 3-dioxolan-2-yl] methoxy] phenyl] methyl] pyrazole-3-carboxylate (may be prepared from the methods described in WO 2020 / 056090) + TX, ethyl 1- [ [4- [5- (trifluoromethyl) -1, 2, 4-oxadiazol-3-yl] phenyl] methyl] pyrazole-4-carboxylate + TX, ethyl 1- [ [5- [5- (trifluoromethyl) -1, 2, 4-oxadiazol-3-yl] -2-thienyl] methyl] pyrazole-4-carboxylate (this compound may be prepared from the methods described in WO 2018 / 158365) +TX, ethyl 4-methyloctanoate + TX, ethyl formate + TX, ethyl hexanediol + TX, ethylene dibromide +TX, ethylene dichloride + TX, ethylene oxide + TX, etridiazole + TX, etrimfos + TX, eugenol + TX, EXD + TX, famoxadone + TX, farnesol + TX, farnesol with nerolidol + TX, fenamidone + TX, fenaminosulf + TX, fenaminstrobin + TX, fenarimol + TX, fenazaflor + TX, fenbuconazole + TX, fenbutatin oxide + TX, fenchlorphos + TX, feneptamidoquin (CAS Number: 2132414-04-9) + TX, fenethacarb + TX, fenfuram + TX, fenhexamid + TX, fenitrothion + TX, fenopyramid (CAS Number: 2344721-61-3) + TX, fenothiocarb + TX, fenoxacrim + TX, fenoxanil + TX, fenpiclonil + TX, fenpicoxamid + TX, fenpirithrin + TX, fenpropidin + TX, fenpropimorph + TX, fenpyrad + TX, fenpyrazamine + TX, fenpyroximate + TX, fenson + TX, fensulfothion + TX, fenthion + TX, fenthion-ethyl + TX, fentin + TX, fentrifanil + TX, ferbam + TX, ferimzone + TX, ferric phosphate + TX, flocoumafen + TX, florylpicoxamid + TX, fluazinam + TX, flubeneteram + TX, flubenzimine + TX, flucofuron + TX, flucycloxuron + TX, fludioxonil + TX, fluenetil + TX, flufenoxadiazam + TX, flufenoxystrobin + TX, fluindapyr + TX, flumetylsulforim + TX, flumorph + TX, fluopicolide + TX, fluopimomide + TX, fluopyram + TX, fluorbenside + TX, fluoroacetamide + TX, fluoroimide + TX, fluoxapiprolin + TX, fluoxastrobin + TX, fluoxytioconazole + TX, flupropadine + TX, flupropadine hydrochloride + TX, fluquinconazole + TX, flusilazole + TX, flusulfamide + TX, flutianil + TX, flutolanil + TX, flutriafol + TX, fluxapyroxad + TX, FMC 1137 + TX, folpet + TX, formaldehyde + TX, formetanate + TX, formetanate hydrochloride + TX, formparanate + TX, fosetyl-aluminium + TX, fosmethilan +TX, fospirate + TX, fosthietan + TX, frontalin + TX, fuberidazole + TX, furalaxyl + TX, furametpyr +TX, furathiocarb + TX, furethrin + TX, furfural + TX, gamma-HCH + TX, glyodin + TX, grandlure + TX, grandlure I + TX, grandlure II + TX, grandlure III + TX, grandlure IV + TX, guazatine + TX, guazatine acetates + TX, halfenprox + TX, HCH + TX, hemel + TX, hempa + TX, HEOD + TX, heptachlor + TX, heterophos + TX, Heterorhabditis bacteriophora and H. megidis + TX, hexaconazole + TX, hexadecyl cyclopropanecarboxylate + TX, hexalure + TX, hexamide + TX, HHDN + TX, Hippodamia convergens + TX, hydrargaphen + TX, hydrated lime + TX, hydrogen cyanide + TX, hymexazol + TX, hyquincarb + TX, imanin + TX, imazalil + TX, imibenconazole + TX, iminoctadine + TX, inpyrfluxam + TX, ipconazole + TX, ipfentrifluconazole + TX, ipflufenoquin + TX, iprobenphos + TX, iprodione + TX, iprovalicarb + TX, ipsdienol + TX, ipsenol + TX, IPSP + TX, isamidofos + TX, isazofos + TX, isobenzan + TX, isocarbophos + TX, isodrin + TX, isofenphos + TX, isofetamid + TX, isoflucypram +TX, isolane + TX, isoprothiolane + TX, isopyrazam + TX, isotianil + TX, isoxathion + TX, japonilure +TX, jasmolin I + TX, jasmolin II + TX, jodfenphos + TX, juvenile hormone I + TX, juvenile hormone II + TX, juvenile hormone III + TX, kadethrin + TX, kasugamycin + TX, kasugamycin hydrochloride hydrate + TX, kelevan + TX, kinetin + TX, kinoprene + TX, kresoxim-methyl + TX, lead arsenate +TX, Leptomastix dactylopii + TX, leptophos + TX, lindane + TX, lineatin + TX, lirimfos + TX, litlure +TX, looplure + TX, lvbenmixianan + TX, lythidathion + TX, Macrolophus caliginosus + TX, magnesium phosphide + TX, malonoben + TX, Mamestra brassicae NPV + TX, mancopper + TX, mancozeb +TX, mandestrobin + TX, mandipropamid + TX, maneb + TX, mazidox + TX, m-cumenyl methylcarbamate + TX, mecarbam + TX, mecarphon + TX, medlure + TX, mefentrifluconazole + TX, megatomoic acid + TX, menazon + TX, mepanipyrim + TX, meperfluthrin + TX, mephosfolan + TX, mepronil + TX, mercuric oxide + TX, mercurous chloride + TX, mesulfen + TX, mesulfenfos + TX, metalaxyl + TX, metam + TX, metam-potassium + TX, metam-sodium + TX, Metaphycus helvolus +TX, Metarhizium anisopliae var. acridum + TX, Metarhizium anisopliae var. anisopliae + TX, metarylpicoxamid + TX, metconazole + TX, metepa + TX, methacrifos + TX, methanesulfonyl fluoride + TX, methasulfocarb + TX, methiotepa + TX, methocrotophos + TX, methoprene + TX, methoquin-butyl + TX, methothrin + TX, methoxychlor + TX, methyl (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate + TX, methyl (Z) -2- (5-cyclopentyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate (these compounds may be prepared from the methods described in WO2020 / 193387) + TX, methyl (Z) -2- [5- (3-isopropylpyrazol-1-yl) -2-methyl-phenoxy] -3-methoxy-prop-2-enoate + TX, methyl (Z) -3-methoxy-2- [2-methyl-5- (3-propylpyrazol-1-yl) phenoxy] prop-2-enoate + TX, methyl (Z) -3-methoxy-2- [2-methyl-5- (4-propyltriazol-2-yl) phenoxy] prop-2-enoate + TX, methyl (Z) -3-methoxy-2- [2-methyl-5- [3- (trifluoromethyl) pyrazol-1-yl] phenoxy] prop-2-enoate (these compounds may be prepared from the methods described in WO2020 / 079111) + TX, methyl (Z) -3-methoxy-2- [2-methyl-5- [4- (trifluoromethyl) triazol-2-yl] phenoxy] prop-2-enoate + TX, methyl apholate + TX, methyl bromide + TX, methyl eugenol + TX, methyl isothiocyanate + TX, methyl N- [ [4- [1- (2, 6-difluoro-4-isopropyl-phenyl) pyrazol-4-yl] -2-methyl-phenyl] methyl] carbamate (may be prepared from the methods described in WO 2020 / 097012) + TX, methyl N- [ [4- [1- (4-cyclopropyl-2, 6-difluoro-phenyl) pyrazol-4-yl] -2-methyl-phenyl] methyl] carbamate (may be prepared from the methods described in WO 2020 / 097012) + TX, methyl N- [ [5- [4- (2, 4-dimethylphenyl) triazol-2-yl] -2-methyl-phenyl] methyl] carbamate + TX, methylchloroform + TX, methylene chloride + TX, methylneodecanamide + TX, metiram + TX, metolcarb + TX, metominostrobin + TX, metoxadiazone + TX, metrafenone + TX, metyltetraprole + TX, MGK 264 + TX, milbemycin oxime + TX, mipafox +TX, mirex + TX, monocrotophos + TX, morphothion + TX, morzid + TX, moxidectin + TX, muscalure + TX, myclobutanil + TX, myclozoline + TX, Myrothecium verrucaria composition + TX, N- ( (1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide (these compounds may be prepared from the methods described in WO2017 / 153380) + TX, N- ( (1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide (these compounds may be prepared from the methods described in WO2017 / 153380) + TX, N'- (2, 5-dimethyl-4-phenoxy-phenyl) -N-ethyl-N-methyl-formamidine + TX, N'- (2-chloro-5-methyl-4-phenoxy-phenyl) -N-ethyl-N-methyl-formamidine + TX, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1, 2, 4-oxadiazol-3-yl] phenyl] methyl] propanamide + TX, N, N-dimethyl-1- [ [4- [5- (trifluoromethyl) -1, 2, 4-oxadiazol-3-yl] phenyl] methyl] -1, 2, 4-triazol-3-amine (THESE COMPOUNDS may be prepared from the methods described in WO 2017 / 055473, WO 2017 / 055469, WO 2017 / 093348 and WO 2017 / 118689) + TX, N- [ (1 R) -1-benzyl-1, 3-dimethyl-butyl] -7, 8-difluoro-quinoline-3-carboxamide + TX, N- [ (1 R) -1-benzyl-1, 3-dimethyl-butyl] -8-fluoro-quinoline-3-carboxamide + TX, N- [ (1 R) -1-benzyl-3, 3, 3-trifluoro-1-methyl-propyl] -8-fluoro-quinoline-3-carboxamide + TX, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl] -7, 8-difluoro-quinoline-3-carboxamide + TX, N- [(1S) -1-benzyl-1, 3-dimethyl-butyl] -8-fluoro-quinoline-3-carboxamide + TX, N- [ (1 S) -1-benzyl-3, 3, 3-trifluoro-1-methyl-propyl] -8-fluoro-quinoline-3-carboxamide + TX, N- [ (E) -methoxyiminomethyl] -4- [5- (trifluoromethyl) -1, 2, 4-oxadiazol-3-yl] benzamide + TX, N- [ (Z) -methoxyiminomethyl] -4- [5- (trifluoromethyl) -1, 2, 4-oxadiazol-3-yl] benzamide + TX, N- [ [4- [5- (trifluoromethyl) -1, 2, 4-oxadiazol-3-yl] phenyl] methyl] propanamide + TX, N- [2- [2, 4-dichloro-phenoxy] phenyl] -3- (difluoromethyl) -1-methyl-pyrazole-4-carboxamide + TX, N- [2- [2-chloro-4- (trifluoromethyl) phenoxy] phenyl] -3- (difluoromethyl) -1-methyl-pyrazole-4-carboxamide + TX, N'- [2-chloro-4- (2-fluorophenoxy) -5-methyl-phenyl] -N-ethyl-N-methyl-formamidine (this compound may be prepared from the methods described in WO 2016 / 202742) + TX, N'- [4- (4, 5-dichlorothiazol-2-yl) oxy-2, 5-dimethyl-phenyl] -N-ethyl-N-methyl-formamidine + TX, N'- [5-bromo-2-methyl-6- (1-methyl-2-propoxy-ethoxy) -3-pyridyl] -N-ethyl-N-methyl-formamidine + TX, N'- [5-bromo-2-methyl-6- (1-methyl-2-propoxy-ethoxy) -3-pyridyl] -N-isopropyl-N-methyl-formamidine (these compounds may be prepared from the methods described in WO2015 / 155075) + TX, N'- [5-bromo-2-methyl-6- (2-propoxypropoxy) -3-pyridyl] -N-ethyl-N-methyl-formamidine (this compound may be prepared from the methods described in IPCOM000249876D) + TX, N'- [5-bromo-2-methyl-6- [ (1 R) -1-methyl-2-propoxy-ethoxy] -3-pyridyl] -N-ethyl-N-methyl-formamidine + TX, N'- [5-bromo-2-methyl-6- [ (1S) -1-methyl-2-propoxy-ethoxy] -3-pyridyl] -N-ethyl-N-methyl-formamidine + TX, N'- [5-chloro-2-methyl-6- (1-methyl-2-propoxy-ethoxy) -3-pyridyl] -N-ethyl-N-methyl-formamidine + TX, N- [N-methoxy-C-methyl-carbonimidoyl] -4- [5- (trifluoromethyl) -1, 2, 4-oxadiazol-3-yl] benzamide (these compounds may be prepared from the methods described in WO 2018 / 202428) + 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 from the methods described in WO2018 / 228896) + TX, nabam + TX, naftalofos + TX, naled + 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-oxadiazol-3-yl] phenyl] methyl] propanamide + TX, N-ethyl-N’- [5-methoxy-2-methyl-4- [ (2-trifluoromethyl) oxetan-2-yl] phenyl] -N-methyl-formamidine + TX, nickel bis (dimethyldithiocarbamate) + TX, niclosamide-olamine + TX, nicotine + TX, nicotine sulfate + TX, nifluridide + TX, nikkomycins + TX, N-isopropyl-N’- [5-methoxy-2-methyl-4- (2, 2, 2-trifluoro-1-hydroxy-1-phenyl-ethyl) phenyl] -N-methyl-formamidine + TX, nithiazine + TX, nitrapyrin + TX, nitrilacarb + TX, nitrilacarb 1: 1 zinc chloride complex + TX, nitrothal-isopropyl + TX, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1, 2, 4-oxadiazol-3-yl] phenyl] methyl] cyclopropanecarboxamide + TX, N-methyl-4- [5- (trifluoromethyl) -1, 2, 4-oxadiazol-3-yl] benzamide + TX, N-methyl-4- [5- (trifluoromethyl) -1, 2, 4-oxadiazol-3-yl] benzenecarbothioamide + TX, norbormide + TX, nuarimol + TX, O, O, O', O'-tetrapropyl dithiopyrophosphate + TX, octadeca-2, 13-dien-1-yl acetate + TX, octadeca-3, 13-dien-1-yl acetate +TX, octhilinone + TX, ofurace + TX, oleic acid + TX, omethoate + TX, orfralure + TX, Orius spp. +TX, oryctalure + TX, orysastrobin + TX, ostramone + TX, oxadixyl + TX, oxamate + TX, oxathiapiprolin + TX, oxine-copper + TX, oxolinic acid + TX, oxycarboxin + TX, oxydeprofos + TX, oxydisulfoton +TX, oxytetracycline + TX, paclobutrazole + TX, Paecilomyces fumosoroseus + TX, para-dichlorobenzene + TX, parathion + TX, parathion-methyl + TX, pefurazoate + TX, penconazole + TX, pencycuron + TX, penflufen + TX, penfluron + TX, pentachlorophenol + TX, pentachlorophenyl laurate + TX, penthiopyrad + TX, permethrin + TX, PH 60-38 + TX, phenamacril + TX, phenkapton +TX, phosacetim + TX, phosalone + TX, phosdiphen + TX, phosfolan + TX, phosglycin + TX, phosnichlor + TX, phosphamidon + TX, phosphine + TX, phosphorus + TX, phoxim-methyl + TX, phthalide + TX, Phytoseiulus persimilis + TX, picarbutrazox + TX, picaridin + TX, picoxystrobin + TX, pindone + TX, piperazine + TX, piperonyl butoxide + TX, piprotal + TX, pirimetaphos + TX, polychlorodicyclopentadiene isomers + TX, polychloroterpenes + TX, polynactins + TX, polyoxins +TX, potassium arsenite + TX, potassium ethylxanthate + TX, potassium hydroxyquinoline sulfate +TX, potassium thiocyanate + TX, pp'-DDT + TX, precocene I + TX, precocene II + TX, precocene III + TX, primidophos + TX, probenazole + TX, prochloraz + TX, proclonol + TX, procymidone + TX, profluthrin + TX, promacyl + TX, promecarb + TX, propamocarb + TX, propiconazole + TX, propineb + TX, propoxur + TX, propyl isomer + TX, proquinazid + TX, prothidathion + TX, prothioconazole +TX, prothiofos + TX, prothoate + TX, pydiflumetofen + TX, pyraclostrobin + TX, pyrametostrobin +TX, pyraoxystrobin + TX, pyrapropoyne + TX, pyraziflumid + TX, pyrazophos + TX, pyresmethrin +TX, pyrethrin I + TX, pyrethrin II + TX, pyrethrins + TX, pyribencarb + TX, pyridachlometyl + TX, pyridaphenthion + TX, pyridin-4-amine + TX, pyrifenox + TX, pyrimethanil + TX, pyrimitate + TX, pyrimorph + TX, pyrinuron + TX, pyriofenone + TX, pyrisoxazole + TX, pyroquilon + TX, quassia +TX, quinalphos + TX, quinalphos-methyl + TX, quinoclamine + TX, quinofumelin + TX, quinonamid +TX, quinothion + TX, quinoxyfen + TX, quintiofos + TX, quintozene + TX, R-1492 + TX, rafoxanide +TX, resmethrin + TX, Reynoutria sachalinensis extract + TX, ribavirin + TX, R-metalaxyl + TX, rotenone + TX, ryania + TX, ryanodine + TX, S421 + TX, sabadilla + TX, schradan + TX, scilliroside + TX, seboctylamine + TX, sebufos + TX, sedaxane + TX, selamectin + TX, sesamex + TX, sesasmolin + TX, SI-0009 + TX, siglure + 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, sophamide + TX, sordidin + TX, spiroxamine + TX, SSI-121 + TX, Steinernema bibionis + TX, Steinernema carpocapsae + TX, Steinernema feltiae + TX, Steinernema glaseri + TX, Steinernema riobrave + TX, Steinernema riobravis + TX, Steinernema scapterisci + TX, Steinernema spp. + TX, streptomycin + TX, streptomycin sesquisulfate + TX, strychnine + TX, sulcatol + TX, sulcofuron + TX, sulcofuron-sodium + TX, sulfiram + TX, sulfluramid + TX, sulfotep +TX, sulfoxide + TX, sulfur + TX, sulfuryl fluoride + TX, sulprofos + TX, tar oils + TX, tau-fluvalinate +TX, tazimcarb + TX, TDE + TX, tebuconazole + TX, tebufloquin + TX, tebupirimfos + TX, tecloftalam + TX, temephos + TX, tepa + TX, TEPP + TX, terallethrin + TX, terbam + TX, tert-butyl N- [6- [ [ [ (1-methyltetrazol-5-yl) -phenyl-methylene] amino] oxymethyl] -2-pyridyl] carbamate + TX, tetrachloroethane + TX, tetrachlorothiophene + TX, tetraconazole + TX, tetradec-11-en-1-yl acetate + TX, tetradifon + TX, tetramethylfluthrin + TX, tetrasul + TX, thallium sulfate + TX, thiabendazole +TX, thiafenox + TX, thiapronil + TX, thicrofos + TX, thifluzamide + TX, thiocarboxime + TX, thiocyclam + TX, thiocyclam hydrogen oxalate + TX, thiodiazole copper + TX, thiofanox + TX, thiohempa + TX, thiomersal + TX, thiometon + TX, thionazin + TX, thiophanate + TX, thiophanate-methyl + TX, thioquinox + TX, thiosultap + TX, thiosultap-sodium + TX, thiotepa + TX, thiram + TX, thuringiensin + TX, tiadinil + TX, tolclofos-methyl + TX, tolprocarb + TX, tolylfluanid + TX, tralomethrin + TX, transpermethrin + TX, tretamine + TX, triadimefon + TX, triadimenol + TX, triamiphos + TX, triarathene + TX, triazamate + TX, triazophos + TX, triazoxide + TX, triazuron + TX, tributyltin oxide + TX, trichlormetaphos-3 + TX, trichloronat + TX, Trichogramma spp. + TX, triclopyricarb + TX, tricyclazole + TX, tridemorph + TX, trifenmorph + TX, trifenofos + TX, trifloxystrobin + TX, triflumizole + TX, triforine + TX, trimedlure + TX, trimedlure A + TX, trimedlure B1 + TX, trimedlure B2 + TX, trimedlure C + TX, trimethacarb + TX, trinactin + TX, trinexapac + TX, triphenyltin acetate + TX, triphenyltin hydroxide + TX, triprene + TX, triticonazole + TX, trunc-call + TX, Typhlodromus occidentalis + TX, uredepa + TX, validamycin + TX, valifenalate + TX, vamidothion + TX, vaniliprole + TX, veratridine + TX, veratrine + TX, verbutin + TX, Verticillium lecanii + TX, vinclozoline + TX, warfarin + TX, XMC + TX, xylenols + TX, zeatin + TX, zetamethrin + TX, zhongshengmycin + TX, zinc naphthenate + TX, zinc phosphide + TX, zinc thiazole + TX, zineb + TX, ziram + TX, zolaprofos + TX, zoxamide + TX, α- (1, 1-dimethylethyl) -α- [4'- (trifluoromethoxy) [1, 1'-biphenyl] -4-yl] -5-pyrimidinemethanol + TX;
[0569] Acinetobacter lwoffii + TX, Acremonium alternatum + TX, Acremonium cephalosporium + TX, Acremonium diospyri + TX, Acremonium obclavatum + TX, Adoxophyes orana granulovirus (AdoxGV) + TX, Agrobacterium radiobacter strain K84 + TX, Alternaria alternate + TX, Alternaria cassia + TX, Alternaria destruens + TX, Ampelomyces quisqualis + TX, Aspergillus flavus AF36 + TX, Aspergillus flavus NRRL 21882 + TX, Aspergillus spp. + TX, Aureobasidium pullulans + TX, Azospirillum + TX, Azotobacter + TX, Azotobacter chroocuccum + TX, Azotobacter cysts (Bionatural Blooming ) + TX, Bacillus amyloliquefaciens + TX, Bacillus cereus + TX, Bacillus chitinosporus strain AQ746 + TX, Bacillus chitinosporus strain CM-1 + TX, Bacillus circulans + TX, Bacillus firmus in particular strain CNMC 1-1582 (e.g. from BASF SE) + TX, Bacillus licheniformis strain 3086 ( Green ) + TX, Bacillus licheniformis strain HB-2 (BiostartTM formerly ) + TX, Bacillus macerans + TX, Bacillus marismortui + TX, Bacillus megaterium + TX, Bacillus mycoides strain AQ726 + TX, Bacillus papillae (Milky Spore ) + TX, Bacillus pumilus spp. + TX, Bacillus pumilus strain AQ717 + TX, Bacillus pumilus strain GB34 (Yield ) + TX, Bacillus pumilus strain QST 2808 ( Ballad ) + TX, Bacillus sphaericus + TX, Bacillus spp. + TX, Bacillus spp. strain AQ175 + TX, Bacillus spp. strain AQ177 + TX, Bacillus spp. strain AQ178 + TX, Bacillus subtilis strain AQ153 + TX, Bacillus subtilis strain AQ743 + TX, Bacillus subtilis strain QST 713 + TX, Bacillus subtilis strain QST 714 + TX, Bacillus subtilis strain QST3002 + TX, Bacillus subtilis strain QST3004 + TX, Bacillus subtilis var. amyloliquefaciens strain FZB24 + TX, Bacillus thuringiensis aizawai GC 91 + TX, Bacillus thuringiensis Cry 2Ae + TX, Bacillus thuringiensis Cry1Ab + TX, Bacillus thuringiensis israelensis + TX, Bacillus thuringiensis kurstaki ( Scutella Turilav Dipel ) + TX, Bacillus thuringiensis kurstaki BMP 123 + TX, Bacillus thuringiensis kurstaki HD-1 + TX, Bacillus thuringiensis strain AQ52 + TX, Bacillus thuringiensis strain BD#32 + TX, Bacillus thuringiensis tenebrionis ( BtBooster) + TX, Bacillus thuringiensis var. aizawai + TX, bacteria spp. + TX, bacteriophage of Clavipacter michiganensis + TX, Beauveria bassiana + TX, Beauveria bassiana GHA (Mycotrol Mycotrol ) + TX, Beauveria brongniartii ( Schweizer ) +TX, Beauveria spp. + TX, Botrytis cineria + TX, Bradyrhizobium japonicum + TX, Brevibacillus brevis + TX, Burkholderia cepacia + TX, Burkholderia gladii + TX, Burkholderia gladioli + TX, Burkholderia spp. + TX, Canadian thistle fungus (CBH Canadian ) + TX, Candida butyri + TX, Candida famata + TX, Candida fructus + TX, Candida glabrata + TX, 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 + TX, Candida sake + TX, Candida spp. + TX, Candida tenius + TX, Cedecea davisae + TX, Cellulomonas flavigena + TX, Chaetomium cochliodes + TX, Chaetomium globosum + TX, Chromobacterium subtsugae strain PRAA4-1T + TX, Cladosporium chlorocephalum + TX, Cladosporium cladosporioides + TX, Cladosporium oxysporum + TX, Cladosporium spp. + TX, Cladosporium tenuissimum + TX, Clonostachys rosea + TX, Colletotrichum acutatum + TX, Coniothyrium minitans + TX, Coniothyrium spp. + TX, Cryptococcus albidus + TX, Cryptococcus humicola + TX, Cryptococcus infirmo-miniatus + TX, Cryptococcus laurentii + TX, Cryptophlebia leucotreta granulovirus + TX, Cupriavidus campinensis + TX, Cydia pomonella granulovirus ( Plus, Madex Max, + TX, Cylindrobasidium laeve + TX, Cylindrocladium + TX, Debaryomyces hansenii + TX, Drechslera hawaiinensis + TX, Enterobacter cloacae + TX, Enterobacteriaceae + TX, Entomophtora virulenta + TX, Epicoccum nigrum + TX, Epicoccum purpurascens + TX, Epicoccum spp. + TX, Filobasidium floriforme + TX, Fusarium acuminatum + TX, Fusarium chlamydosporum + TX, Fusarium oxysporum + TX, Fusarium proliferatum + TX, Fusarium spp. + TX, Galactomyces geotrichum + TX, Gliocladium catenulatum + TX, Gliocladium roseum + TX, Gliocladium spp. + TX, Gliocladium virens + TX, Granulovirus + TX, Halobacillus halophilus + TX, Halobacillus litoralis + TX, Halobacillus trueperi + TX, Halomonas spp. + TX, Halomonas subglaciescola + TX, Halovibrio variabilis + TX, Hanseniaspora uvarum + TX, Helicoverpa armigera nucleopolyhedrovirus + TX, Helicoverpa zea nuclear polyhedrosis virus +TX, Isaria fumosorosea (previously known as Paecilomyces fumosoroseus strain, ) + TX, Isoflavone formononetin + TX, Kloeckera apiculata + TX, Kloeckera spp. + TX, Lagenidium giganteum + TX, Lecanicillium lecanii (formerly known as Verticillium lecanii conidia of strain KV01 (e.g. by Koppert / Arysta) + TX, Lecanicillium longisporum + TX, Lecanicillium muscarium + TX, Lymantria Dispar nucleopolyhedrosis virus + TX, Marinococcus halophilus + TX, Meira geulakonigii + TX, Metarhizium anisopliae + TX, Metarhizium anisopliae + TX, Metschnikowia fruticola + TX, Metschnikowia pulcherrima + TX, Microdochium dimerum + TX, Micromonospora coerulea + TX, Microsphaeropsis ochracea + TX, Muscodor albus 620 + TX, Muscodor roseus in particular strain A3-5 (Accession No. NRRL 30548) + TX, Mycorrhizae spp. + TX, Myrothecium verrucaria strain AARC-0255 + TX, Ophiostoma piliferum strain D97 +TX, Paecilomyces farinosus + TX, Paecilomyces lilacinus strain 251 + TX, Paecilomyces linacinus + TX, Paenibacillus polymyxa + TX, Pantoea agglomerans + TX, Pantoea spp. + TX, Pasteuria nishizawae in particular strain Pn1 (CLARIVA from Syngenta / ChemChina) ; + TX, Pasteuria spp. + TX, Penicillium aurantiogriseum +TX, Penicillium billai + TX, Penicillium brevicompactum + TX, Penicillium frequentans + TX, Penicillium griseofulvum + TX, Penicillium purpurogenum + TX, Penicillium spp. +TX, Penicillium viridicatum + TX, Phlebiopsis gigantean + TX, phosphate solubilizing bacteria + TX, Phytophthora cryptogea + TX, Phytophthora palmivora +TX, Pichia anomala + TX, Pichia guilliermondii + TX, Pichia membranaefaciens + TX, Pichia onychis + TX, Pichia stipites + TX, Pseudomonas aeruginosa + TX, Pseudomonas aureofasciens + TX, Pseudomonas cepacia + TX, Pseudomonas chlororaphis + TX, Pseudomonas corrugate + TX, Pseudomonas fluorescens + TX, Pseudomonas fluorescens strain A506 + TX, Pseudomonas putida + TX, Pseudomonas reactans + TX, Pseudomonas spp. + TX, Pseudomonas syringae + TX, Pseudomonas viridiflava + TX, Pseudozyma flocculosa strain PF-A22 UL + TX, Puccinia canaliculata + TX, Puccinia thlaspeos + TX, Pythium paroecandrum + TX, Pythium oligandrum + TX, Pythium periplocum + TX, Rhanella aquatilis + TX, Rhanella spp. + TX, Rhizobia + TX, Rhizoctonia + TX, Rhodococcus globerulus strain AQ719 + TX, Rhodosporidium diobovatum + TX, Rhodosporidium toruloides + TX, Rhodotorula glutinis + TX, Rhodotorula graminis + TX, Rhodotorula mucilagnosa + TX, Rhodotorula rubra + TX, Rhodotorula spp. + TX, Saccharomyces cerevisiae + TX, Salinococcus roseus + TX, Sclerotinia minor + TX, Sclerotinia minor + TX, Scytalidium spp. + TX, Scytalidium uredinicola +TX, Serratia marcescens + TX, Serratia plymuthica + TX, Serratia spp. + TX, Sordaria fimicola + TX, Spodoptera exigua nuclear polyhedrosis virus + TX, Spodoptera littoralis nucleopolyhedrovirus + TX, Sporobolomyces roseus + TX, Stenotrophomonas maltophilia + TX, Streptomyces albaduncus + TX, Streptomyces exfoliates + TX, Streptomyces galbus + TX, Streptomyces griseoplanus + TX, Streptomyces griseoviridis + TX, Streptomyces hygroscopicus + TX, Streptomyces lydicus + TX, Streptomyces lydicus WYEC-108 + TX, Streptomyces violaceus + TX, Tilletiopsis minor + TX, Tilletiopsis spp. + TX, Trichoderma asperellum + TX, Trichoderma atroviride + TX, Trichoderma gamsii + TX, Trichoderma hamatum TH 382 + TX, Trichoderma harzianum rifai + TX, Trichoderma harzianum T-22 + TX, Trichoderma harzianum T-39 + TX, Trichoderma inhamatum + TX, Trichoderma koningii + TX, Trichoderma lignorum + TX, Trichoderma longibrachiatum + TX, Trichoderma polysporum + TX, Trichoderma spp. LC 52 + TX, Trichoderma taxi + TX, Trichoderma virens (formerly Gliocladium virens GL-21) + TX, Trichoderma virens + TX, Trichoderma viride + TX, Trichoderma viride strain ICC 080 + 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 + TX, Ustilago maydis + TX, various bacteria and supplementary micronutrients + TX, various fungi + TX, Verticillium chlamydosporium + TX, Vip3Aa20 + TX, Virgibaclillus marismortui +TX, Xanthomonas campestris pv. Poae + TX, Xenorhabdus bovienii + TX, Xenorhabdus nematophilus + TX;
[0570] MMF + TX, azadirachtin (Plasma Neem e.g. AZATIN XL from Certis, US) + TX, Botanical IGR + TX, + TX, canola oil + TX, Chenopodium ambrosioides near ambrosioides +TX, Chrysanthemum extract + TX, essentials oils of Labiatae + TX, extract of neem oil + TX, extracts of clove rosemary peppermint and thyme oil + TX, garlic + TX, Glycinebetaine + TX, kaolin + TX, lemongrass oil + TX, Melaleuca alternifolia extract (also called tea tree oil) + TX, mixture of clove pepermint garlic oil and mint + TX, mixture of clove rosemary and peppermint extract + TX, mixture of rosemary sesame pepermint thyme and cinnamon extracts + TX, neem oil + TX, Nepeta cataria (Catnip oil) + TX, Nepeta catarina + TX, nicotine + TX, oregano oil + TX, Pedaliaceae oil + TX, pine oil + TX, pyrethrum + TX, Quillaja saponaria + TX, Reynoutria sachalinensis + TX, rotenone + TX, Rutaceae plant extract + TX, soybean oil + TX, storage glucam of brown algae + TX, thyme oil + TX; (E, Z) -7, 9-Dodecadien-1-yl acetate + TX, (E, Z, Z) -3, 8, 11 Tetradecatrienyl acetate + TX, (Z, Z, E) -7, 11, 13-Hexadecatrienal + TX, 2-Methyl-1-butanol + TX, + TX, blackheaded fireworm pheromone (3M Sprayable Blackheaded Fireworm ) + TX, Calcium acetate + TX, + TX, Codling Moth Pheromone (Paramount dispenser- (CM) / Isomate ) + TX, Entostat powder (extract from palm tree) + TX, Grape Berry Moth Pheromone (3M MEC-GBM Sprayable ) + TX, Lavandulyl senecioate + TX, Leafroller pheromone (3M MEC –LR Sprayable ) + TX, Muscamone (Snip7 Fly + TX, Oriental Fruit Moth Pheromone (3M oriental fruit moth sprayable ) + TX, Peachtree Borer Pheromone + TX, + TX, Starbar Premium Fly ) + TX, Tomato Pinworm Pheromone (3M Sprayable ) + TX;
[0571] Acerophagus papaya + TX, Adalia bipunctata + TX, Adalia bipunctata + TX, Adalia bipunctata + TX, Ageniaspis citricola + TX, Ageniaspis fuscicollis + TX, Amblyseius andersoni + TX, Amblyseius californicus + TX, Amblyseius cucumeris + TX, Amblyseius fallacis + TX, Amblyseius swirskii + TX, Amblyseius womersleyi + TX, Amitus hesperidum + TX, Anagrus atomus + TX, Anagyrus fusciventris + TX, Anagyrus kamali + TX, Anagyrus loecki + TX, Anagyrus pseudococci +TX, Anicetus benefices + TX, Anisopteromalus calandrae + TX, Anthocoris nemoralis + TX, Aphelinus abdominalis + TX, Aphelinus asychis + TX, Aphidius colemani + TX, Aphidius ervi + TX, Aphidius ervi + TX, Aphidius gifuensis + TX, Aphidius matricariae + TX, Aphidoletes aphidimyza + TX, Aphytis lingnanensis + TX, Aphytis melinus + TX, Aprostocetus hagenowii + TX, Atheta coriaria + TX, Bombus spp. + TX, Bombus terrestris + TX, Bombus terrestris + TX, Cephalonomia stephanoderis + TX, Chilocorus nigritus + TX, Chrysoperla carnea + TX, Chrysoperla rufilabris + TX, Cirrospilus ingenuus + TX, Cirrospilus quadristriatus + TX, Citrostichus phyllocnistoides + TX, Closterocerus chamaeleon + TX, Closterocerus spp. + TX, Coccidoxenoides perminutus + TX, Coccophagus cowperi + TX, Coccophagus lycimnia + TX, Cotesia flavipes + TX, Cotesia plutellae + TX, Cryptolaemus montrouzieri + TX, Cybocephalus nipponicus + TX, Dacnusa sibirica + TX, Delphastus catalinae + TX, Delphastus pusillus + TX, Diachasmimorpha krausii + TX, Diachasmimorpha longicaudata + TX, Diaparsis jucunda + TX, Diaphorencyrtus aligarhensis + TX, Diglyphus isaea + TX, Diversinervus spp. + TX, Encarsia citrina + TX, Encarsia formosa + TX, Encarsia guadeloupae + TX, Encarsia haitiensis + TX, Episyrphus balteatus + TX, Eretmoceris siphonini + TX, Eretmocerus californicus + TX, Eretmocerus eremicus +TX, Eretmocerus hayati + TX, Eretmocerus mundus + TX, Eretmocerus siphonini + TX, Exochomus quadripustulatus + TX, Feltiella acarisuga + TX, Feltiella acarisuga + TX, Fopius arisanus + TX, Fopius ceratitivorus + TX, Formononetin + TX, Franklinothrips vespiformis + TX, Galendromus occidentalis + TX, Goniozus legneri + TX, Habrobracon hebetor + TX, Harmonia axyridis + TX, Heterorhabditis bacteriophora + TX, Heterorhabditis megidis + TX, Heterorhabditis spp. + TX, Hippodamia convergens + TX, Hypoaspis aculeifer + TX, Hypoaspis miles + TX, Lbalia leucospoides + TX, Lecanoideus floccissimus + TX, Lemophagus errabundus + TX, Leptomastidea abnormis + TX, Leptomastix dactylopii + TX, Leptomastix epona + TX, Lindorus lophanthae + TX, Lipolexis oregmae + TX, Lucilia caesar + TX, Lysiphlebus testaceipes + TX, Macrolophus caliginosus + TX, Mesoseiulus longipes + TX, Metaphycus flavus + TX, Metaphycus lounsburyi + TX, Micromus angulatus + TX, Microterys flavus + TX, Muscidifurax raptorellus and Spalangia cameroni + TX, Neodryinus typhlocybae + TX, Neoseiulus californicus + TX, Neoseiulus cucumeris + TX, Neoseiulus fallacis + TX, Nesideocoris tenuis + TX, Ophyra aenescens + TX, Orius insidiosus + TX, Orius laevigatus + TX, Orius majusculus +TX, Orius strigicollis + TX, Pauesia juniperorum + TX, Pediobius foveolatus + TX, Phasmarhabditis hermaphrodita + TX, Phymastichus coffea + TX, Phytoseiulus macropilus + TX, Phytoseiulus persimilis + TX, Podisus maculiventris + TX, Pseudacteon curvatus + TX, Pseudacteon obtusus + TX, Pseudacteon tricuspis +TX, Pseudaphycus maculipennis + TX, Pseudleptomastix mexicana + TX, Psyllaephagus pilosus +TX, Psyttalia concolor (complex) + TX, Quadrastichus spp. + TX, Rhyzobius lophanthae + TX, Rodolia cardinalis + TX, Rumina decollate + TX, Semielacher petiolatus + TX, Sitobion avenae + TX, Steinernema carpocapsae + TX, Steinernema feltiae + TX, Steinernema kraussei + TX, Steinernema riobrave + TX, Steinernema scapterisci + TX, Steinernema spp. +TX, Steinernematid spp. + TX, Stethorus punctillum + TX, Tamarixia radiate + TX, Tetrastichus setifer + TX, Thripobius semiluteus + TX, Torymus sinensis +TX, Trichogramma brassicae + TX, Trichogramma brassicae + TX, Trichogramma evanescens + TX, Trichogramma minutum + TX, Trichogramma ostriniae + TX, Trichogramma platneri + TX, Trichogramma pretiosum + TX, Xanthopimpla stemmator + TX; abscisic acid + TX, + TX, + TX, + TX, Chondrostereum purpureum + TX, Colletotrichum gloeosporioides + TX, Copper Octanoate + TX, Delta traps + TX, Erwinia amylovora (Harpin) ( Ni-HI BIT Gold ) + TX, fatty acids derived from a natural by-product of extra virgin olive oil + TX, Ferri-phosphate + TX, Funnel traps + TX, + TX, Grower's + TX, Homo-brassonolide + TX, Iron Phosphate (Lilly Miller Worry Free Ferramol Slug &Snail ) + TX, MCP hail trap + TX, Microctonus hyperodae + TX, Mycoleptodiscus terrestris + TX, Nosema locustae (Semaspore Organic Grasshopper ) + TX, Pheromone trap + TX, potassium bicarbonate + TX, potassium iodide +potassiumthiocyanate + TX, potassium salts of fatty acids + TX, potassium silicate solution + TX, Spider venom + TX, Sticky traps (Trapline Rebell ) + TX, + TX, Traps + TX, vadescana (CAS Number: 2643947-26-4) + TX, + TX;
[0572] Bacillus mojavensis strain R3B (Accession No. NCAIM (P) B001389) (WO 2013 / 034938) from Certis USA LLC + TX, Bacillus pumilus, in particular strain BU F-33, having NRRL Accession No. 50185 ( from BASF, EPA Reg. No. 71840-19) + TX, Bacillus subtilis CX-9060 from Certis USA LLC, Bacillus sp., in particular strain D747 (available as DOUBLE from Kumiai Chemical Industry Co., Ltd. ) , having Accession No. FERM BP-8234, U.S. Patent No. 7,094,592 + TX, Bacillus subtilis strain BU1814, ( PLUS, FLEX and EXTRA from BASF SE) + TX, Bacillus subtilis var. amyloliquefaciens strain FZB24 having Accession No. DSM 10271 (available from Novozymes as or ECO (EPA Registration No. 70127-5) ) + TX, Bacillus subtilis, in particular strain QST713 / AQ713 (having NRRL Accession No. B-21661 and described in U.S. Patent No. 6,060,051, available as OPTI or ASO from Bayer CropScience LP, US) + TX, Paenibacillus polymyxa, in particular strain AC-1 (e.g. from Green Biotech Company Ltd. ) + TX, Paenibacillus sp. strain having Accession No. NRRL B-50972 or Accession No. NRRL B-67129, WO 2016 / 154297 + TX, Pantoea agglomerans, in particular strain E325 (Accession No. NRRL B-21856) (available as BLOOMTIME BIOLOGICALTMFD BIOPESTICIDE from Northwest Agri Products) + TX, Pseudomonas proradix (e.g. from Sourcon Padena) + TX;
[0573] Aureobasidium pullulans, in particular blastospores of strain DSM14940, blastospores of strain DSM 14941 or mixtures of blastospores of strains DSM14940 and DSM14941 (e.g., and BLOSSOM from bio-ferm, CH) + TX, Pseudozyma aphidis (as disclosed in WO2011 / 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 (WO 2010 / 086790) from Lesaffre et Compagnie, FR + TX;
[0574] [Corrected under Rule 26, 12.06.2025]Agrobacterium radiobacter strain K84 (e.g. from AgBioChem, CA) + TX, Bacillus amyloliquefaciens isolate B246 (e.g. AVOGREENTM from University of Pretoria) + TX, Bacillus amyloliquefaciens strain F727 (also known as strain MBI110) (NRRL Accession No. B-50768, WO 2014 / 028521) ( from Marrone Bio Innovations) + TX, Bacillus amyloliquefaciens strain FZB42, Accession No. DSM 23117 (available as from ABiTEP, DE) + TX, Bacillus amyloliquefaciens, in particular strain D747 (available as Double NickelTM from Kumiai Chemical Industry Co., Ltd., having accession number FERM BP-8234, US Patent No. 7,094,592) + TX, Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 ( (WG) and (WP) from FMC Corporation) + TX, Bacillus licheniformis, in particular strain SB3086, having Accession No. ATCC 55406, WO 2003 / 000051 (available as Biofungicide and GREEN RELEAFTM from Novozymes) + TX, Bacillus methylotrophicus strain BAC-9912 (from Chinese Academy of Sciences’ Institute of Applied Ecology) + TX, Bacillus mycoides, isolate, having Accession No. B-30890 (available as BMJ or WG and LifeGardTM from Certis USA LLC) + TX, Bacillus pumilus, in particular strain GB34 (available as Yield from Bayer AG, DE) + TX, Bacillus pumilus, in particular strain QST2808 (available as from Bayer CropScience LP, US, having Accession No. NRRL B-30087 and described in U.S. Patent No. 6,245,551) + TX, Bacillus subtilis CX-9060 from Certis USA LLC + TX, Bacillus subtilis IAB / BS03 (AVIVTM from STK Bio-Ag Technologies, from Idai Nature) + TX, Bacillus subtilis KTSB strain ( from Donaghys) + TX, Bacillus subtilis strain BU1814, (available as PLUS, FLEX and EXTRA from BASF SE) + TX, Bacillus subtilis strain GB03 (available as from Bayer AG, DE) + TX, Bacillus subtilis strain MBI 600 (available as SUBTILEX from BASF SE) , having Accession Number NRRL B-50595, U.S. Patent No. 5,061,495 + TX, Bacillus subtilis strain Y1336 (available as WP from Bion-Tech, Taiwan, China, registered as a biological fungicide in Taiwan, China, under Registration Nos. 4764, 5454, 5096 and 5277) + TX, Bacillus subtilis var. amyloliquefaciens strain FZB24 having Accession No. DSM 10271 (available from Novozymes as or ECO (EPA Registration No. 70127-5) ) + TX, Bacillus subtilis Y1336 (available as WP from Bion-Tech, Taiwan, China, registered as a biological fungicide in Taiwan, China, under Registration Nos. 4764, 5454, 5096 and 5277) + TX, Paenibacillus epiphyticus (WO 2016 / 020371) from BASF SE + TX, Paenibacillus polymyxa ssp. plantarum (WO 2016 / 020371) from BASF SE + TX, Paenibacillus sp. strain having Accession No. NRRL B-50972 or Accession No. NRRL B-67129, WO 2016 / 154297 + TX, Pseudomonas chlororaphis strain AFS009, having Accession No. NRRL B-50897, WO 2017 / 019448 (e.g., HOWLERTM and from AgBiome Innovations, US) + TX, Pseudomonas chlororaphis, in particular strain MA342 (e.g. and by Bioagri and Koppert) +TX, Pseudomonas fluorescens strain A506 (e.g. A506 by NuFarm) + TX, Pseudomonas proradix (e.g. from Sourcon Padena) + TX, Streptomyces griseoviridis strain K61 (also known as Streptomyces galbus strain K61) (Accession No. DSM 7206) ( from Verdera, from BioWorks, cf. Crop Protection 2006, 25, 468-475) + TX, Streptomyces lydicus strain WYEC108 (also known as Streptomyces lydicus strain WYCD108US) ( and from Novozymes) + TX;
[0575] Trichoderma atroviride strain T11 (IMI352941 / CECT20498) + TX, Ampelomyces quisqualis strain AQ10, having Accession No. CNCM 1-807 (e.g., AQ by IntrachemBio Italia) + TX, Ampelomyces quisqualis, in particular strain AQ 10 (e.g. AQ by IntrachemBio Italia) + TX, Aspergillus flavus strain NRRL 21882 (products known as from Syngenta / ChemChina) + TX, Aureobasidium pullulans, in particular blastospores of strain DSM 14941 + TX, Aureobasidium pullulans, in particular blastospores of strain DSM14940 + TX, Aureobasidium pullulans, in particular mixtures of blastospores of strains DSM14940 and DSM 14941 (e.g. by bio-ferm, CH) +TX, Chaetomium cupreum (Accession No. CABI 353812) (e.g. BIOKUPRUMTM by AgriLife) + TX, Chaetomium globosum (available as by Rivale) + TX, Cladosporium cladosporioides, strain H39, having Accession No. CBS122244, US 2010 / 0291039 (by Stichting Dienst Landbouwkundig Onderzoek) + TX, Coniothyrium minitans, in particular strain CON / M / 91-8 (Accession No. DSM9660, e.g. from Bayer CropScience Biologics GmbH) + TX, Cryptococcus flavescens, strain 3C (NRRL Y-50378) , + TX, Dactylaria candida, Dilophosphora alopecuri (available as TWIST ) , Fusarium oxysporum, strain Fo47 (available as by Natural Plant Protection) + TX, Gliocladium catenulatum (Synonym: Clonostachys rosea f. catenulate) strain J1446 (e.g. by 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) , in particular strain 321 U from Adjuvants Plus, strain ACM941 as disclosed in Xue A. G. (Efficacy of Clonostachys rosea strain ACM941 and fungicide seed treatments for controlling the root tot complex of field pea, Can Jour Plant Sci 2003, 83 (3) : 519-524) + TX, Metschnikowia fructicola, in particular strain NRRL Y-30752 + TX, Microsphaeropsis ochracea, Penicillium steckii (DSM 27859, WO 2015 / 067800) from BASF SE +TX, mixtures of Trichoderma asperellum strain ICC 012 (also known as Trichoderma harzianum ICC012) , having Accession No. CABI CC IMI 392716 and Trichoderma gamsii (formerly T. viride) strain ICC 080, having Accession No. IMI 392151 (e.g., BIO-TAMTM from Isagro USA, Inc. or by Agrobiosol de Mexico, S.A. de C.V. ) + TX, Penicillium vermiculatum + TX, Phlebiopsis gigantea strain VRA 1992 ( C from Danstar Ferment) + TX, Pseudozyma flocculosa, strain PF-A22 UL (available as L by Plant Products Co., CA) + TX, Saccharomyces cerevisiae strain LAS117 cell walls ( from Lesaffre, from BASF SE) + TX, Saccharomyces cerevisiae strains CNCM No. 1-3936, CNCM No. 1-3937, CNCM No.1-3938, CNCM No. 1-3939 (WO 2010 / 086790) from Lesaffre et Compagnie, FR + TX, Saccharomyces cerevisiae, in particular strain LASO2 (from Agro-Levures et Dérivés) + TX, Simplicillium lanosoniveum + TX, strain T34 (e.g. T34 Biocontrol by Biocontrol Technologies S.L., ES) or strain ICC 012 from Isagro + TX, strain WRL-076 (NRRL Y-30842) , U.S. Patent No. 7,579,183 + TX, Talaromyces flavus, strain V117b + TX, Trichoderma asperelloides JM41 R (Accession No. NRRL B-50759) (TRICHO from BASF SE) + TX, Trichoderma asperellum, in particular strain SKT-1, having Accession No. FERM P-16510 (e.g. from Kumiai Chemical Industry) +TX, Trichoderma asperellum, in particular, strain kd (e.g. T-Gro from Andermatt Biocontrol) + TX, Trichoderma atroviride strain 77B (T77 from Andermatt Biocontrol) + TX, Trichoderma atroviride strain ATCC 20476 (IMI 206040) + TX, Trichoderma atroviride strain LC52 (e.g. Tenet by Agrimm Technologies Limited) + TX, Trichoderma atroviride strain LU132 (e.g. Sentinel from Agrimm Technologies Limited) + TX, Trichoderma atroviride strain NMI no. V08 / 002388 + TX, Trichoderma 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) , JP Patent Publication (Kokai) 11-253151 A + TX, Trichoderma atroviride strain SKT-2 (FERM P-16511) , JP Patent Publication (Kokai) 11-253151 A + TX, Trichoderma atroviride strain SKT-3 (FERM P-17021) , JP Patent Publication (Kokai) 11-253151 A + TX, Trichoderma atroviride, in particular strain SC1 (Accession No. CBS 122089, WO 2009 / 116106 and U.S. Patent No. 8,431,120 (from Bi-PA) ) + TX, Trichoderma atroviride, strain CNCM 1-1237 (e.g. WP from Agrauxine, FR) + TX, Trichoderma fertile (e.g. product TrichoPlus from BASF) + TX, Trichoderma gamsii (formerly T. viride) + TX, Trichoderma gamsii (formerly T. viride) strain ICC 080 (IMI CC 392151 CABI) (available as by AGROBIOSOL DE MEXICO, S.A. DE C.V. ) , + TX, Trichoderma gamsii strain ICC080 (IMI CC 392151 CABI, e.g. BioDerma by AGROBIOSOL DE MEXICO, S.A. DE C.V. ) , + TX, Trichoderma harmatum + TX, Trichoderma harmatum, having Accession No. ATCC 28012 + TX, Trichoderma harzianum + TX, Trichoderma harzianum rifai T39 (e.g. from Makhteshim, US) + TX, Trichoderma harzianum strain Cepa SimbT5 (from Simbiose Agro) , + TX, Trichoderma harzianum strain DB 103 (available as 7456 by Dagutat Biolab) + TX, Trichoderma harzianum strain ITEM 908 (e.g. Trianum-P from Koppert) + TX, Trichoderma harzianum strain T-22 (e.g. Trianum-P from 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 WP by BINAB Bio-Innovation AB, Sweden) + TX, Trichoderma stromaticum having Accession No. Ts3550 (e.g. Tricovab by CEPLAC, Brazil) + TX, Trichoderma virens (also known as Gliocladium virens) in particular strain GL-21 (e.g. SoilGard by Certis, US) + TX, Trichoderma virens strain G-41, formerly known as Gliocladium virens (Accession No. ATCC 20906) (e.g., PLUS WP and PLUS WP from BioWorks, US) + TX, Trichoderma viride in particular strain B35 (Pietr et al., 1993, Zesz. Nauk. A R w Szczecinie 161: 125-137) + TX, Trichoderma viride strain TV1 (e.g. Trianum-P by Koppert) + TX, Ulocladium oudemansii strain U3, having Accession No. NM 99 / 06216 (e.g., by Botry-Zen Ltd, New Zealand and from BioWorks, Inc. ) + TX, Verticillium albo-atrum (formerly V. dahliae) strain WCS850 having Accession No. WCS850, deposited at the Central Bureau for Fungi Cultures (e.g., DUTCH by Tree Care Innovations) + TX, Verticillium chlamydosporium + TX;
[0576] a mixture of Azotobacter vinelandii and Clostridium pasteurianum (available as from Agrinos) + TX, a mixture of Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (available as (WG) , (WP) from FMC Corporation) + TX, Azorhizobium caulinodans, in particular strain ZB-SK-5 + TX, Azospirillum brasilense (e.g., from KALO, Inc. ) + TX, Azospirillum lipoferum (e.g., VERTEX-IFTM from TerraMax, Inc. ) + TX, Azotobacter chroococcum, in particular strain H23 + TX, Azotobacter vinelandii, in particular strain ATCC 12837 + TX, Bacillus amyloliquefaciens BS27 (Accession No. NRRL B-5015) + TX, Bacillus amyloliquefaciens in particular strain FZB42 (e.g. from ABiTEP, DE) + TX, Bacillus amyloliquefaciens in particular strain IN937a + TX, Bacillus amyloliquefaciens pm414 ( from Biofilm Crop Protection) + TX, Bacillus amyloliquefaciens SB3281 (ATCC #PTA-7542, WO 2017 / 205258) + TX, Bacillus amyloliquefaciens TJ1000 (available as from Novozymes) + TX, Bacillus cereus family member EE128 (NRRL No. B-50917) + TX, Bacillus cereus family member EE349 (NRRL No. B-50928) + TX, Bacillus cereus in particular strain BP01 (ATCC 55675, e.g. from Arysta Lifescience, US) + 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 in particular strain GB34 (e.g. YIELD from Bayer Crop Science, DE) , + TX, Bacillus pumilus in particular strain QST2808 (Accession No. NRRL No. B-30087) + TX, Bacillus siamensis in particular strain KCTC 13613T + TX, Bacillus subtilis in particular strain AQ30002 (Accession No. NRRL No. B-50421 and described in U.S. Patent Application No. 13 / 330,576) + TX, Bacillus subtilis in particular strain AQ30004 (NRRL No.B-50455 and described in U.S. Patent Application No. 13 / 330,576) + TX, Bacillus subtilis in particular strain MBI 600 (e.g. from BASF SE) + TX, Bacillus subtilis rm303 ( from Biofilm Crop Protection) + TX, Bacillus subtilis strain BU1814 (available as from BASF SE) + TX, Bacillus tequilensis in particular strain NII-0943 + TX, Bacillus thuringiensis BT013A (NRRL No. B-50924) also known as Bacillus thuringiensis 4Q7 + TX, Bradyrhizobium japonicum (e.g. from Novozymes) + TX, Delftia acidovorans in particular strain RAY209 (e.g. from Brett Young Seeds) + TX, Lactobacillus sp. (e.g. from LactoPAFI) + TX, Mesorhizobium cicer (e.g., NODULATOR from BASF SE) +TX, Paenibacillus polymyxa in particular strain AC-1 (e.g. from Green Biotech Company Ltd. ) + TX, Pseudomonas aeruginosa in particular strain PN1 + TX, Pseudomonas proradix (e.g. from Sourcon Padena) + TX, Rhizobium leguminosarium biovar viciae (e.g., NODULATOR from BASF SE) + TX, Rhizobium leguminosarum in particular bv. viceae strain Z25 (Accession No. CECT 4585) + TX, Serratia marcescens in particular strain SRM (Accession No. MTCC 8708) , + TX, Sinorhizobium meliloti strain NRG-185-1 ( GOLD from Bayer CropScience) + TX, Thiobacillus sp. (e.g. from Cropaid Ltd UK) + TX;
[0577] Myrothecium verrucaria strain AARC-0255 (e.g. DiTeraTM from Valent Biosciences) + TX, Penicillium bilaii strain ATCC 22348 (e.g. from Acceleron BioAg) + TX, Penicillium bilaii strain ATCC ATCC20851 + TX, Purpureocillium lilacinum (previously known as Paecilomyces lilacinus) strain 251 (AGAL 89 / 030550, e.g. BioAct from Bayer CropScience Biologics GmbH) + TX, Pythium oligandrum strain DV74 + TX, Pythium oligandrum strain M1 (ATCC 38472 e.g. Polyversum from Bioprepraty, CZ) + TX, Rhizopogon amylopogon (Myco-Sol from Agri-Enterprise, LLC, formerly Helena Chemical Company) + TX, Rhizopogon fulvigleba (e.g. Myco-Sol from Agri-Enterprise, LLC, formerly Helena Chemical Company) + TX, Talaromyces flavus strain V117b + TX, Trichoderma asperellum strain (Eco-T from Plant Health Products, ZA) + TX, Trichoderma asperellum strain kd (e.g. T-Gro from Andermatt Biocontrol) + TX, Trichoderma atroviride in particular strain no. V08 / 002387 + TX, Trichoderma atroviride strain CNCM 1-1237 (e.g. WP from Agrauxine, FR) + TX, Trichoderma atroviride strain LC52 (also known as Trichoderma atroviride strain LU132, e.g. Sentinel from 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 WO2009 / 116106) + TX, Trichoderma harzianum strain 1295-22 + TX, Trichoderma harzianum strain ITEM 908 + TX, Trichoderma harzianum strain T-22 (e.g. Trianum-P from Andermatt Biocontrol or Koppert) + TX, Trichoderma harzianum strain TSTh20, + TX, Trichoderma virens strain GI-3 + TX, Trichoderma virens strain GL-21 (e.g. from Certis, USA) + TX, Trichoderma viride strain B35 (Pietr et al., 1993, Zesz. Nauk. A R w Szczecinie 161: 125-137) + TX, Verticillium albo-atrum (formerly V. dahliae) strain WCS850 (CBS 276.92, e.g. Dutch Trig from Tree Care Innovations) + TX;
[0578] Agrobacterium radiobacter strain K84 (Galltrol from AgBiochem Inc. ) , + TX, Bacillus amyloliquefaciens in particular strain PTS-4838 (e.g. AVEO from Valent Biosciences, US) , + TX, Bacillus mycoides, isolate J. (e.g. BmJ from Certis USA LLC) , + TX, Bacillus sphaericus in particular Serotype H5a5b strain 2362 (strain ABTS-1743) (e.g. from Valent BioSciences, US) , + TX, Bacillus thuringiensis israelensis strain BMP 144 (e.g. by Becker Microbial Products IL) + TX, Bacillus thuringiensis subsp. aizawai strain GC-91 + TX, Bacillus thuringiensis subsp. aizawai, in particular serotype H-7 (e.g. WG from Valent BioSciences, US) + TX, Bacillus thuringiensis subsp. aizawai, in particular strain ABTS-1857 (SD-1372, e.g. from Valent BioSciences) + TX, Bacillus thuringiensis subsp. israelensis (serotype H-14) strain AM65-52 (Accession No. ATCC 1276) (e.g. by Valent BioSciences, US) + TX, Bacillus thuringiensis subsp. kurstaki strain ABTS 351 + TX, Bacillus thuringiensis subsp. kurstaki strain BMP 123 (from Becker Microbial Products, IL, BARITONE from Bayer CropScience) + TX, Bacillus thuringiensis subsp. kurstaki strain EG 2348 (LEPINOX from Certis, US) + TX, Bacillus thuringiensis subsp. kurstaki strain EG 7841 (CRYMAX from Certis, US) + TX, Bacillus thuringiensis subsp. kurstaki strain HD-1 (e.g. ES from Valent BioSciences, US) + TX, Bacillus thuringiensis subsp. kurstaki strain PB 54 + TX, Bacillus thuringiensis subsp. kurstaki strain SA 11 (JAVELIN from Certis, US) + TX, Bacillus thuringiensis subsp. kurstaki strain SA 12 (THURICIDE from Certis, US) +TX, Bacillus thuringiensis subsp. tenebrionis strain NB 176 (SD-5428, e.g. FC from BioFa DE) + TX, Bacillus thuringiensis var. Colmeri (e.g. TIANBAOBTC by Changzhou Jianghai Chemical Factory) + TX, Bacillus thuringiensis var. japonensis strain Buibui + TX, Bacillus thuringiensis var. kurstaki strain EVB-113-19 (e.g., from AEF Global) + TX, Brevibacillus laterosporus + TX, Burkholderia spp. in particular Burkholderia rinojensis strain A396 (also known as Burkholderia rinojensis strain MBI 305) (Accession No. NRRL B-50319, WO 2011 / 106491 and WO 2013 / 032693, e.g. MBI206 TGAI and from Marrone Bio Innovations) , + TX, Chromobacterium subtsugae in particular strain PRAA4-1T (e.g. MBI-203, e.g. from Marrone Bio Innovations) + TX, Lecanicillium muscarium Ve6 (MYCOTAL from Koppert) + TX, Paenibacillus popilliae (formerly Bacillus popilliae, e.g. MILKY SPORE POWDERTM or MILKY SPORE GRANULARTM from St. Gabriel Laboratories) + TX, Serratia entomophila (e.g. by Wrightson Seeds) + TX, Serratia marcescens in particular strain SRM (Accession No. MTCC 8708) + TX, Trichoderma asperellum (TRICHODERMAX from Novozymes) + TX, Wolbachia pipientis ZAP strain (e.g., ZAP from MosquitoMate) + TX;
[0579] Beauveria bassiana strain ATCC 74040 (e.g. from Intrachem Bio Italia) + TX, Beauveria bassiana strain ATP02 (Accession No. DSM 24665) , Apopka 97 (PREFERAL from SePRO) + TX, Beauveria bassiana strain GHA (Accession No. ATCC74250, e.g. ES and from Laverlam International Corporation) + TX, Metarhizium anisopliae 3213-1 (deposited under NRRL accession number 67074 disclosed in WO 2017 / 066094, Pioneer Hi-Bred International) + TX, Metarhizium robertsii 15013-1 (deposited under NRRL accession number 67073) + TX, Metarhizium robertsii 23013-3 (deposited under NRRL accession number 67075) + TX, Paecilomyces lilacinus strain 251 (MELOCON from Certis, US) + TX, Zoophtora radicans + TX; Adoxophyes orana (summer fruit tortrix) granulosis virus (GV) + TX, Cydia pomonella (codling moth) granulosis virus (GV) + TX, Helicoverpa armigera (cotton bollworm) nuclear polyhedrosis virus (NPV) + TX, Spodoptera exigua (beet armyworm) mNPV + TX, Spodoptera frugiperda (fall armyworm) mNPV + TX, Spodoptera littoralis (African cotton leafworm) NPV + TX;
[0580] Burkholderia spp. in particular 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. in particular Rhizobium 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;
[0581] Allium sativum (NEMGUARD from Eco-Spray, BRALIC from ADAMA) + TX, Armour-Zen + TX, Artemisia absinthium + TX, Biokeeper WP + TX, Brassicaceae extract in particular oilseed rape powder or mustard powder + TX, Cassia nigricans + TX, Celastrus angulatus + TX, Chenopodium anthelminticum + TX, Chenopodium quinoa saponin extract from quinoa seeds (e.g. Heads (Saponins of Quinoa) from Heads Up plant Protectants, CA) + TX, Chitin + TX, Dryopteris filix-mas + TX, Equisetum arvense + TX, Fortune Aza + TX, Fungastop + TX, Melaleuca alternifolia extract (TIMOREX GOLD from STK) + TX, naturally occurring Blad polypeptide extracted from Lupin seeds ( from FMC) + TX, naturally occurring Blad polypeptide extracted from Lupin seeds ( from Certis EU) + TX, Pyrethrins + TX, Quassia amara + TX, Quercus + TX, Quillaja extract (QL AGRI 35 from BASF) + TX, REGALIA MAXX from Marrone Bio) + TX, RequiemTMInsecticide + TX, Reynoutria sachalinensis extract (REGALLIA + TX, ryania / ryanodine + TX, Symphytum officinale + TX, Tanacetum vulgare + TX, Thymol + TX, Thymol mixed with Geraniol (CEDROZ from Eden Research) + TX, Thymol mixed with Geraniol and Eugenol (MEVALONE from Eden Research) + TX, Triact 70 + TX, TriCon + TX, Tropaeulum majus + TX, Urtica dioica + TX, Veratrin + TX, Viscum album + TX;
[0582] mercuric oxide + TX, octhilinone + TX, thiophanate-methyl + TX;
[0583] MGK 264 + TX, 2- (2-butoxyethoxy) ethyl piperonylate + TX, 2-isovalerylindan-1, 3-dione + TX, 4- (quinoxalin-2-ylamino) benzenesulfonamide + TX, 5- (1, 3-benzodioxol-5-yl) -3-hexylcyclohex-2-enone + TX, acibenzolar + TX, acibenzolar-S-methyl + TX, alpha-bromadiolone + TX, alpha-chlorohydrin +TX, aluminium phosphide + TX, anthraquinone + TX, antu + TX, arsenous oxide + TX, barium carbonate + TX, benoxacor + TX, bisthiosemi + TX, brodifacoum + TX, bromadiolone + TX, bromethalin + TX, calcium cyanide + TX, chloralose + TX, chlorophacinone + TX, cholecalciferol +TX, cloquintocet (including cloquintocet-mexyl) + TX, copper naphthenate + TX, copper oxychloride + TX, coumachlor + TX, coumafuryl + TX, coumatetralyl + TX, crimidine + TX, cyprosulfamide + TX, diazinon + TX, dichlormid + TX, dicyclopentadiene + TX, difenacoum + TX, difethialone + TX, diphacinone + TX, ergocalciferol + TX, farnesol + TX, farnesol with nerolidol + TX, fenchlorazole (including fenchlorazole-ethyl) + TX, fenclorim + TX, flocoumafen + TX, fluoroacetamide + TX, flupropadine + TX, flupropadine hydrochloride + TX, fluxofenim + TX, furilazole + TX, gamma-HCH + TX, guazatine + TX, guazatine acetates + TX, HCH + TX, hydrogen cyanide + TX, imanin + TX, iodomethane + TX, isoxadifen (including isoxadifen-ethyl) + TX, lindane + TX, magnesium phosphide + TX, MB-599 + TX, mefenpyr (including mefenpyr-diethyl) + TX, metcamifen + TX, methiocarb + TX, methyl bromide + TX, nerolidol + TX, norbormide + TX, petroleum oils + TX, phosacetim + TX, phosphine + TX, phosphorus + TX, pindone + TX, piperonyl butoxide + TX, piprotal + TX, potassium arsenite + TX, probenazole + TX, propyl isomer + TX, pyridin-4-amine + TX, pyrinuron + TX, Reynoutria sachalinensis extract + TX, ribavirin + TX, S421 + TX, scilliroside + TX, sesamex + TX, sesasmolin + TX, sodium arsenite + TX, sodium cyanide + TX, sodium fluoroacetate + TX, strychnine + TX, sulfoxide + TX, thallium sulfate + TX, thiram + TX, trimethacarb + TX, warfarin + TX, zinc naphthenate + TX, zinc phosphide + TX, ziram + TX;
[0584] The references in brackets behind the active ingredients, e.g. [3878-19-1] refer to the Chemical Abstracts Registry number. The above described mixing partners are known. Where the active ingredients are included in "The Pesticide Manual" [The Pesticide Manual -A World Compendium; Thirteenth Edition; Editor: C. D. S. TomLin; The British Crop Protection Council] , they are described therein under the entry number given in round brackets hereinabove for the particular compound; for example, the compound "abamectin" is described under entry number (1) . Where " [CCN] " is added hereinabove to the particular compound, the compound in question is included in the "Compendium of Pesticide Common Names" , which is accessible on the internet via BCPC; http: / / www. bcpcpesticidecompendium. org / index. html; for example, the compound "abamectin" is described under the internet address http: / / www. bcpcpesticidecompendium. org / index_cn_frame. html.
[0585] Most of the active ingredients described above are referred to hereinabove by a so-called "common name" , the relevant "ISO common name" or another "common name" being used in individual cases. If the designation is not a "common name" , the nature of the designation used instead is given in round brackets for the particular compound; in that case, the IUPAC name, the IUPAC / Chemical Abstracts name, a "chemical name" , a "traditional name" , a "compound name" or a "development code" is used or, if neither one of those designations nor a "common name" is used, an "alternative name" is employed. “CAS Reg. No” means the Chemical Abstracts Registry Number.
[0586] The active ingredient mixture of the compounds of formula (I) with active ingredients described above comprises a compound selected from one compound defined in the Tables A-1 to A-42, Tables B-1 to B-42, and Table P and an active ingredient as described above, preferably in a mixing ratio of from 100: 1 to 1: 6000, especially from 50: 1 to 1: 50, more especially in a ratio of from 20: 1 to 1: 20, even more especially from 10: 1 to 1: 10, very especially from 5: 1 and 1: 5, special preference being given to a ratio of from 2: 1 to 1: 2, and a ratio of from 4: 1 to 2: 1 being likewise preferred, above all in a ratio of 1: 1, or 5: 1, or 5: 2, or 5: 3, or 5: 4, or 4: 1, or 4: 2, or 4: 3, or 3: 1, or 3: 2, or 2: 1, or 1: 5, or 2: 5, or 3: 5, or 4: 5, or 1: 4, or 2: 4, or 3: 4, or 1: 3, or 2: 3, or 1: 2, or 1: 600, or 1: 300, or 1: 150, or 1: 35, or 2: 35, or 4: 35, or 1: 75, or 2: 75, or 4: 75, or 1: 6000, or 1: 3000, or 1: 1500, or 1: 350, or 2: 350, or 4: 350, or 1: 750, or 2: 750, or 4: 750. The mixing ratios are by weight.
[0587] The compounds and compositions described above can be used in a method for controlling pests, which comprises applying a composition comprising a mixture as described above to the pests or their environment, with the exception of a method for treatment of the human or animal body by surgery or therapy and diagnostic methods practised on the human or animal body.
[0588] The mixtures comprising a compound of formula (I) selected from the compounds defined in the Tables A-1 to A-42, Tables B-1 to B-42, and Table P and one or more active ingredients as described above can be applied, for example, in a single “ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a “tank-mix” , and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days. The order of applying the compounds of formula (I) and the active ingredients as described above is not essential for working the present invention.
[0589] The compositions according to the invention can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil) , antifoams, for example silicone oil, preservatives, viscosity regulators, binders and / or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematicides, plant activators, molluscicides or herbicides.
[0590] The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and / or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and / or grinding the active ingredient with the auxiliary (auxiliaries) . These processes for the preparation of the compositions and the use of the compounds I for the preparation of these compositions are also a subject of the invention.
[0591] The application methods for the compositions, that is the methods of controlling pests of the abovementioned type, such as spraying, atomizing, dusting, brushing on, dressing, scattering or pouring -which are to be selected to suit the intended aims of the prevailing circumstances -and the use of the compositions for controlling pests of the abovementioned type are other subjects of the invention. Typical rates of concentration are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient. The rate of application per hectare is generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g / ha, preferably 10 to 600 g / ha.
[0592] A preferred method of application in the field of crop protection is application to the foliage of the plants (foliar application) , it being possible to select frequency and rate of application to match the danger of infestation with the pest in question. Alternatively, the active ingredient can reach the plants via the root system (systemic action) , by drenching the locus of the plants with a liquid composition or by incorporating the active ingredient in solid form into the locus of the plants, for example into the soil, for example in the form of granules (soil application) . In the case of paddy rice crops, such granules can be metered into the flooded paddy-field.
[0593] The compounds of formula (I) of the invention and compositions thereof are also be suitable for the protection of plant propagation material, for example seeds, such as fruit, tubers or kernels, or nursery plants, against pests of the abovementioned type. The propagation material can be treated with the compound prior to planting, for example seed can be treated prior to sowing. Alternatively, the compound can be applied to seed kernels (coating) , either by soaking the kernels in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the compositions when the propagation material is planted to the site of application, for example into the seed furrow during drilling. These treatment methods for plant propagation material and the plant propagation material thus treated are further subjects of the invention. Typical treatment rates would depend on the plant and pest / fungi to be controlled and are generally between 1 to 200 grams per 100 kg of seeds, preferably between 5 to 150 grams per 100 kg of seeds, such as between 10 to 100 grams per 100 kg of seeds.
[0594] The term seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corns, bulbs, fruit, tubers, grains, rhizomes, cuttings, cut shoots and the like and means in a preferred embodiment true seeds.
[0595] The present invention also comprises seeds coated or treated with or containing a compound of formula I. The term "coated or treated with and / or containing" generally signifies that the active ingredient is for the most part on the surface of the seed at the time of application, although a greater or lesser part of the ingredient may penetrate into the seed material, depending on the method of application. When the said seed product is (re) planted, it may absorb the active ingredient. In an embodiment, the present invention makes available a plant propagation material adhered thereto with a compound of formula I. Further, it is hereby made available, a composition comprising a plant propagation material treated with a compound of formula I.
[0596] Seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting. The seed treatment application of the compound formula (I) can be carried out by any known methods, such as spraying or by dusting the seeds before sowing or during the sowing / planting of the seeds.
[0597] The compounds of the invention can be distinguished from other similar compounds by virtue of greater efficacy at low application rates and / or different pest control, which can be verified by the person skilled in the art using the experimental procedures, using lower concentrations if necessary, for example 10 ppm, 5 ppm, 2 ppm, 1 ppm or 0.2 ppm; or lower application rates, such as 300, 200 or 100, mg of AI per m2. The greater efficacy can be observed by an increased safety profile (against non-target organisms above and below ground (such as fish, birds and bees) , improved physico-chemical properties, or increased biodegradability) .
[0598] In each aspect and embodiment of the invention, "consisting essentially" and inflections thereof are a preferred embodiment of "comprising" and its inflections, and "consisting of" and inflections thereof are a preferred embodiment of "consisting essentially of” and its inflections.
[0599] The disclosure in the present application makes available each and every combination of embodiments disclosed herein.
[0600] Biological Examples
[0601] Chilo suppressalis (Striped rice stemborer)
[0602] 24-well microtiter plates with artificial diet were treated with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions by pipetting. After drying, the plates were infested with L2 larvae (6-8 per well) . The samples were assessed for mortality, anti-feeding effect, and growth inhibition in comparison to untreated samples 6 days after infestation. Control of Chilo suppressalis by a test sample is given when at least one of the categories mortality, anti-feedant effect, and growth inhibition is higher than the untreated sample.
[0603] The following compounds resulted in at least 80%control at an application rate of 200 ppm:
[0604] P1, P2, P3, P4
[0605] Diabrotica balteata (Corn root worm)
[0606] Maize sprouts placed onto an agar layer in 24-well microtiter plates were treated with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions by spraying. After drying, the plates were infested with L2 larvae (6 to 10 per well) . The samples were assessed for mortality and growth inhibition in comparison to untreated samples 4 days after infestation.
[0607] The following compounds gave an effect of at least 80%in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm:
[0608] P2
[0609] Plutella xylostella (Diamond back moth)
[0610] 24-well microtiter plates with artificial diet were treated with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions by pipetting. After drying, Plutella eggs were pipetted through a plastic stencil onto a gel blotting paper and the plate was closed with it. The samples were assessed for mortality and growth inhibition in comparison to untreated samples 8 days after infestation. The following compounds gave an effect of at least 80%in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm:
[0611] P1, P2, P3, P4
[0612] Plutella xylostella (Diamond back moth)
[0613] The leaf-disc dipping method was used to assay the insecticidal activity of compounds to strains of Plutella xylostella. Solutions with different concentrations (i.e. 10, 1, and 0.1 ppm) from 10'000 ppm dimethylformamide stock solutions were prepared. Dip the leaf discs from cabbage leaves in the solution for 10 seconds and let them dry. Then place them in 9 cm Petri dish with 4 discs per dish. Put the filter paper into the Petri dish to moisturize it. Put ten 3rd-instar larvae of Plutella xylostella into each dish, three replicates in total. The dishes were placed in an illumination incubator and incubated at 25 ℃ with 14 hL: 10 hD illumination. The number of dead Plutella xylostella larvae was investigated on the first, second and third day after infestation, and the mortality was calculated.
[0614] The following compounds gave an effect of at least 80%at an application rate of 10 ppm on the third day:
[0615] P5
Claims
A compound of Formula (I) :whereinR1 to R5 are independently selected from H, halogen, C1-6alkyl, C3-6cycloalkyl, C1-6alkoxy, C1-6haloalkyl, C1-6halocycloalkyl, and C1-6haloalkoxy;R6 is H or CH3;Q is selected from:T is selected from:R7 and R8 are independently selected from H, methyl, ethyl, isopropyl, cyclopropyl, cyclobutyl, 2- (acetamid) ethyl, 2-ethoxyethyl, oxolan-3-yl, thietan-3-yl, oxetan-3-yl, propen-2-yl, 2-methoxyethyl, 2, 2-diethoxyethyl, oxan-4-yl, 2-methyl-1, 3-dioxolane, 3-methoxypropyl, 2-hydroxyethyl, 3, 3-imethoxypropyl, 2-cyanoethyl and 2-methylsulfonylethyl, orR7 and R8 together with the nitrogen atom to which they are attached form an imidazole or morpholine group;W is selected fromor is a direct bond,with the proviso that if T is T5 then W is a direct bond;A is a phenyl group, a C6cycloalkyl, or piperidine ring,wherein A is optionally substituted by one or more of halogen, C1-6alkyl, C1-6cycloalkyl, C1-6alkoxy, C1-6haloalkyl, C1-6halocycloalkyl, C1-6haloalkoxy;or an agronomically acceptable salt, stereoisomer, enantiomer, tautomer and / or N-oxide of the compound of Formula (I) .The compound according to claim 1, wherein R1 is halogen, C1-6alkyl, C3-6cycloalkyl or C1-6haloalkyl.The compound according to claim 1 or claim 2, wherein R4 is H, halogen, C1-3alkyl, C3cycloalkyl, or C1-3alkoxy.The compound according to any of the preceding claims, wherein R2, R3, and R5 are H.The compound according to any of the preceding claims, wherein Q is selected from Q1, Q2 and Q4.The compound according to any of the preceding claims, wherein A is substituted by halogen, C1-6haloalkoxy, or C1-6haloalkyl.The compound according to any of the preceding claims, wherein A is substituted at the 4 position.The compound according to any of the preceding claims, wherein A is a phenyl group.The compound according to any of claims 1 to 7, wherein A is C6cycloalkyl or piperidine and is doubly substituted at the 4 position.The compound according to any of the preceding claims, wherein T is selected from T1, T3 or T4.The compound according to any of the preceding claims, wherein W is selected from:or a direct bond.A composition comprising a compound of Formula (I) as defined in any of the preceding claims, one or more auxiliaries and diluent, and optionally one or more other active ingredient.A method of combating and controlling one or more pests which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest a pesticidally effective amount of a compound of Formula (I) as defined in any one of claims 1 to 11, or a composition as defined in claim 12.A method for the protection of plant propagation material from the attack by insects, acarines, nematodes or molluscs, which comprises treating the propagation material or the site, where the propagation material is planted, with an effective amount of a compound of Formula (I) as defined in any one of claims 1 to 11, or a composition as defined in claim 12.A plant propagation material, such as a seed, comprising, or treated with or adhered thereto, a compound of Formula (I) as defined in any one of claims 1 to 11, or a composition as defined in claim 12.A process for making a compound of Formula (I) as defined in any one of claims 1 to 11 by reacting a compound of Formula (IIa)with a compound of Formula (III)where X is a halogen and all other substituents as defined in claim 1.
Citation Information
Patent Citations
DNA sequences encoding polypeptides having beta-1,3-glucanase activity
EP0353191A2
Novel bacillus thuringiensis isolate denoted b.t. ps81gg, active against lepidopteran pests, and a gene encoding a lepidopteran-active toxin
EP0367474A1
Insecticidal toxines, genes coding therefor, antibodies binding them, transgenic plant cells and plants expressing these toxines
EP0374753A2
Disease-resistant transgenic plants
EP0392225A2
Novel bacillus thuringiensis isolates active against lepidopteran pests, and genes encoding novel lepidopteran-active toxins
EP0401979A2