CN118355017A - Bicyclic compounds for controlling invertebrate pests - Google Patents

Bicyclic compounds for controlling invertebrate pests Download PDF

Info

Publication number
CN118355017A
CN118355017A CN202280076682.7A CN202280076682A CN118355017A CN 118355017 A CN118355017 A CN 118355017A CN 202280076682 A CN202280076682 A CN 202280076682A CN 118355017 A CN118355017 A CN 118355017A
Authority
CN
China
Prior art keywords
alkyl
alkoxy
unsubstituted
substituted
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202280076682.7A
Other languages
Chinese (zh)
Inventor
P·迈蒂
R·S·夏克
B·施罗德
A·阿迪塞尚
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority claimed from PCT/EP2022/081036 external-priority patent/WO2023088718A1/en
Publication of CN118355017A publication Critical patent/CN118355017A/en
Pending legal-status Critical Current

Links

Landscapes

  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The present invention relates to compounds of formula (I) wherein the variables have the meanings as defined in the specification; to compositions comprising the same; to active compound combinations comprising the same; and to the use thereof for protecting growing plants and animals from attack or infestation by invertebrate pests; furthermore, it relates to seeds comprising such compounds.

Description

Bicyclic compounds for controlling invertebrate pests
The present invention relates to compounds of formula I and the N-oxides, tautomers, stereoisomers and agriculturally or veterinarily acceptable salts thereof,
Wherein the method comprises the steps of
R 1 is C 1-C6 -alkyl, C 1-C6 -alkoxy, C 2-C6 -alkenyl, C 2-C6 -alkynyl, C 1-C6 -alkoxy-C 1-C4 -alkyl, C 1-C6 -alkoxy-C 1-C4 -alkoxy, C 3-C6 -cycloalkyl, C 3-C6 -cycloalkyl-C 1-C4 -alkyl, or C 3-C6 -cycloalkoxy-C 1-C4 -alkyl, which is unsubstituted or halogenated;
Phenyl or benzyl, wherein the rings are unsubstituted or substituted with R F;
R F is halogen, OH, CN, NO 2、SCN、SF5、C1-C6 alkyl, C 1-C6 alkoxy, C 2-C6 -alkenyl, C 2-C6 alkynyl, C 1-C6 alkoxy-C 1-C4 alkyl, C 1-C6 alkoxy-C 1-C4 alkoxy, C 3-C6 cycloalkyl, C 3-C6 -cycloalkoxy, C 3-C6 cycloalkyl-C 1-C4 alkyl, C 3-C6 -cycloalkoxy-C 1-C4 alkyl, which groups are unsubstituted or substituted by halogen;
R 2 is H, halogen, C 1-C6 -alkyl, C 2-C6 -alkenyl, C 2-C6 -alkynyl, C 1-C6 -alkoxy, C 1-C6 -alkoxy-C 1-C6 -alkyl, C 3-C6 -cycloalkyl, C 3-C6 -cycloalkoxy, C 1-C6 -sulfenyl, C 1-C6 -sulfinyl, or C 1-C6 -sulfonyl, which groups are unsubstituted or halogenated; phenyl or benzyl, wherein the rings are unsubstituted or substituted with R F;
R 3 is H, halogen, C 1-C6 -alkyl, C 1-C6 -alkoxy, C 3-C6 -cycloalkyl, which is unsubstituted or substituted by R F; or alternatively
Phenyl or benzyl, wherein the aromatic ring of the above groups may be unsubstituted or substituted with R F;
g is phenyl or 6 membered heteroaryl;
r 4 is H, halogen, C (CN) R 41R42、C(R44)＝N-OR43、C(R44)＝N-N(R45R46),
C(O)R44、N＝S(O)(R41R42)、N(R43)C(O)R44、N(R43)C(＝N-OR43)R44;OC(CN)R41R42、C1-C6- Alkyl, C 1-C6 -alkoxy, C 3-C6 -cycloalkyl, C 2-C6 -alkenyl, C 2-C6 -alkynyl, phenyl, or six membered heteroaryl, which groups are unsubstituted or substituted by R G;
R G H, halogen, CN, NO 2、C1-C4 -alkyl, C 1-C4 -haloalkyl, C 1-C4 -alkoxy, C 1-C4 -haloalkoxy, N (R 12R13)、S(O)m-C1-C4 -haloalkyl, C 1-C4 -alkylcarbonyl, or C 1-C4 -haloalkylcarbonyl;
Or two radicals R G are bonded to two adjacent atoms to form a 4-to 6-membered carbocyclic or heterocyclic ring which is unsubstituted or partially or fully substituted by R F;
R 41、R42 is independently H, CN, C 1-C6 -alkyl, C 1-C6 -haloalkyl, C 3-C6 -cycloalkyl, C 1-C4 -alkoxy, C 1-C4 -alkoxy-C 1-C4 -alkyl, S (O) m-C1-C4 -alkyl, C 1-C4 -alkyl-S (O) m-C1-C4 -alkyl, or C 1-C4 -alkoxycarbonyl;
R 41 and R 42 may also form, together with the carbon atom to which they are bound, a C 3-C6 -cycloalkyl group which is unsubstituted or substituted by halogen, C 1-C4 -alkyl, C 1-C4 -haloalkyl, C 1-C4 -alkoxy or C 1-C4 -haloalkoxy;
R 43 is H, C 1-C6 -alkyl, C 2-C6 -alkenyl, C 2-C6 -alkynyl, C 1-C6 -alkoxy-C 1-C4 -alkyl, C 3-C6 -cycloalkyl, C 3-C6 -cycloalkyl-C 1-C4 -alkyl, C 3-C6 -cycloalkoxy-C 1-C4 -alkyl, which groups are unsubstituted or substituted by halogen and/or CN;
phenyl or benzyl, which are unsubstituted or substituted by R F;
R 44 is H, CN, OH, C 1-C6 -alkyl, C 2-C6 -alkenyl, C 2-C6 -alkynyl, C 1-C6 -alkoxy-C 1-C4 -alkyl, C 3-C6 -cycloalkyl, C 3-C6 -cycloalkyl-C 1-C4 -alkyl, C 3-C6 -cycloalkoxy-C 1-C4 -alkyl, which groups are unsubstituted or substituted by halogen;
phenyl or benzyl, which are unsubstituted or substituted by R F;
r 45、R46 is independently H, C 1-C6 -alkyl, C 2-C6 -alkenyl, C 2-C6 -alkynyl, C 1-C6 -alkoxy-C 1-C4 -alkyl, C 3-C6 -cycloalkyl, C 3-C6 -cycloalkyl-C 1-C4 -alkyl, C 3-C6 -cycloalkoxy-C 1-C4 -alkyl, C 1-C6 -alkyl-carbonyl, C 1-C6 -alkoxy-carbonyl, which groups are unsubstituted or substituted by halogen;
phenyl or benzyl, which are unsubstituted or substituted by R F;
NR 45R46 can also form an N-bonded saturated 5-to 8-membered heterocyclic ring which, in addition to nitrogen, can have 1 or 2 further heteroatoms selected from O, S (O) m and N-R ', where R' is H or C 1-C6 -alkyl and the heterocyclic ring is unsubstituted or substituted by halogen, C 1-C4 -alkyl, C 1-C4 -haloalkyl, C 1-C4 -alkoxy or C 1-C4 -haloalkoxy;
A is CH, CR A, or N;
R A is halogen, C 1-C4 -alkyl, C 3-C6 -cycloalkyl, C 1-C6 -haloalkyl, C 1-C6 -halocycloalkyl, OR 43、S(O)m-R43; wherein the ring is unsubstituted or substituted with R 42;
m is 0, 1, or 2
Y is O or NR Y;
r Y is H or C 1-C4 -alkyl;
R 5 is C 1-C4 -alkyl, C 3-C6 -cycloalkyl, C 3-C6 -cycloalkyl-C 1-C4 -alkyl.
The invention also provides an agricultural composition comprising at least one compound of formula I, a stereoisomer or tautomer thereof and/or an agriculturally acceptable salt thereof, and at least one liquid and/or solid carrier, in particular at least one inert liquid and/or agriculturally acceptable solid carrier.
The present invention also provides a veterinary composition comprising at least one compound of formula I, a stereoisomer and/or a veterinarily acceptable salt thereof, and at least one liquid and/or solid carrier, in particular at least one veterinarily inert liquid and/or acceptable solid carrier.
The present invention also provides a method for controlling invertebrate pests, which method comprises treating the pests, their food supply, their habitat or their breeding grounds or the cultivated plants in which the pests are growing or may grow, plant propagation material (e.g. seeds), soil, area, material or environment or the materials to be protected from attack or infestation by the pests, cultivated plants, plant propagation material (e.g. seeds), soil, surfaces or spaces with a pesticidally effective amount of a compound of formula I as defined herein or a salt thereof.
The invention also relates to a plant propagation material, in particular seeds, comprising at least one compound of formula I and/or an agriculturally acceptable salt thereof.
The invention further relates to a method for treating or protecting an animal from infestation or infection by parasites which comprises contacting the animal with a parasiticidally effective amount of a compound of formula I or a veterinarily acceptable salt thereof. Contacting an animal with compound I of the present invention, a salt thereof, or a veterinary composition means that it is administered to or given to the animal.
EP 3257853 and WO 2017167832 describe structurally related active compounds. These compounds are mentioned as useful against invertebrate pests.
However, there remains a need for agents that are highly effective and versatile for combating invertebrate pests. It is therefore an object of the present invention to provide compounds which have good pesticidal activity against a large number of different invertebrate pests, in particular against pests which are difficult to control, such as insects, and which exhibit a broad activity spectrum.
It has been found that these objects can be achieved by the compounds of the formula I as shown and defined below and stereoisomers, salts, tautomers and N-oxides thereof, in particular agriculturally acceptable salts thereof.
Preparation method
The compounds of formula (I) may be prepared by standard methods of organic chemistry. If certain derivatives cannot be prepared by the methods outlined below, they can be obtained by derivatization of other compounds of formula (I) obtainable by these methods. Unless otherwise specified, the definitions of the variables for the following compounds and intermediates are as defined for formula (I). The preferred meanings of the variables as defined herein also apply to the following formulae (II) to (XII).
Compound I can be obtained by oxidizing compound II with a suitable oxidizing agent III. The oxidation may be carried out under standard conditions known from the literature.
The conversion is typically carried out in an inert solvent at a temperature of from 0℃to 30℃in the presence of an oxidizing agent such as mCPBA, na 2WO4 or H 2O2, as described in Chemistry-A European Journal [ J.European Chemistry ],2017,23 (57), 14345-14357 or Biolog.Med.chem.Lett. [ biologicalorganic and pharmaceutical Chemistry rapid, 2012,22 (1), 547-552 or GREEN CHEMISTRY [ Green Chemistry ],2009,11 (9), 1401-1405).
Suitable solvents are halogenated hydrocarbons such as dichloromethane, chloroform and chlorobenzene, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, preferably dichloromethane, chloroform, meOH, preferably dichloromethane. Mixtures of the solvents mentioned can also be used. The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to use an excess of III (based on II).
Compound II (formula IIA) wherein A is CH or CR A can be obtained by reacting compound IIIA in the presence of a mineral or organic acid such as polyphosphoric acid (PPA) or AcOH (reagent IV). R AA is a group R A or H.
The conversion is generally carried out in an inert solvent (e.g. dioxane) in the presence of an acid at a temperature of 60℃and preferably 130℃to 150℃as described in U.S. Pat. No. 3, 4048184 or Polish Journal of Chemistry [ journal of Polish chemistry ],1983,57 (10), 1219-1230.
Suitable acids and acidic catalysts are generally inorganic acids, such as phosphoric acid, and also organic acids, such as formic acid, acetic acid, propionic acid, toluene sulfonic acid and trifluoroacetic acid, preferably Polyphosphoric Acid (PPA). The acid is generally used in catalytic amounts; however, they may also be used in equimolar amounts, in excess or, if appropriate, as solvents. The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to use an excess of IV (based on IIIA).
The compound IIIA can be obtained by condensation of the beta-keto compound IVA with 3-aminopyrazole V.
The conversion is generally carried out in a protic solvent at a temperature of from 25℃to 120℃and preferably at 80℃as described in Polish Journal of Chemistry [ journal of Polish chemistry ],1983,57 (10), 1219-30.
Suitable solvents are polar protic solvents such as alcohols, e.g., methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert-butanol. Mixtures of the solvents mentioned can also be used. The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to use an excess of V (based on IVA).
Compound V is commercially available.
Compound IVA can be obtained from compound VIA by alkylating it with compound VII (wherein Y is a halide or another suitable nucleophilic leaving group).
The conversion is generally carried out in an inert solvent in the presence of a base at a temperature of from 25℃to 100℃and preferably at 60℃as described in Chemistry-A European Journal [ J.European Chemistry ],2010,16 (31), 9457-9461 or Angew.chem.int.ed. [ International edition of applied Chemistry ],2018,57 (4), 1039-1043.
Suitable solvents are nitriles such as acetonitrile and propionitrile. Mixtures of the solvents mentioned can also be used. Suitable bases are generally inorganic compounds such as alkali and alkaline earth metal carbonates, e.g. Na 2CO3、K2CO3, or Cs 2CO3, preferably K 2CO3. The base is generally used in equimolar amounts, or even in excess. The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to use an excess of VII (based on VIA).
Compound VII is commercially available.
Compound VIA can be obtained from ketone VIIIA by reaction with a carbonic acid derivative, such as ester IX.
The conversion is generally carried out in an inert solvent in the presence of a base at a temperature of from 0℃to 100℃and preferably from 70℃to 100℃as described in Org.Lett. [ organic flash report ],2017,19 (23), 6344-6347 or J.Med.chem. [ J. Pharmaceutical chem., 1999,42 (20), 4081-4087).
Suitable solvents are aliphatic hydrocarbons such as hexane, heptane, cyclohexane, and petroleum ether or ethers such as diethyl ether (DEE), tert-butyl methyl ether (TBME), dioxane, or Tetrahydrofuran (THF), preferably heptane. Mixtures of the solvents mentioned can also be used. Suitable bases are generally inorganic compounds, such as alkali metal and alkaline earth metal hydrides, such as NaH, KH and CaH 2, particularly preferably alkali metal hydrides, such as NaH. The base is generally used in equimolar amounts, or in excess.
The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to use an excess of IX (based on VIIIA).
The ketone VIIIA can be obtained from ketone X by substitution with an alkyl thiolate XI, as is known from the literature (see WO 2015091945). In formula X, "Hal" represents a halogen atom, preferably Cl or F, and in formula XI M represents a cation, such as an alkali metal.
The conversion is generally carried out in an inert solvent in the presence of a base at a temperature of from 25℃to 60℃and preferably from 20℃to 25℃in accordance with the conditions as described in WO 2015091945 or WO 2018095795.
Suitable solvents are ethers, such as DEE, TBME, dioxane, and THF, in addition to dimethyl sulfoxide (DMSO), dimethylformamide (DMF), or Dimethylacetamide (DMA), preferably DMF, or ethers such as THF. Mixtures of the solvents mentioned can also be used.
Suitable bases are generally inorganic compounds, such as alkali metal hydroxides (e.g. NaOH, KOH), or alkali metal hydrides (e.g. NaH, KH), or alkali metal and alkaline earth metal carbonates (e.g. Na 2CO3、K2CO3, or Cs 2CO3, or Na or K tert-butoxide). The base is typically in equimolar amounts or even in excess.
The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to use an excess of XI (based on X).
Compound II (formula IIB) wherein a is N can be obtained by reaction of compound IIIB with XII ((pivaloyloxy) urethane) wherein OR is a leaving group such as alkoxy) as carbamoylating agent.
The conversion is generally carried out in an inert solvent in the presence of a catalyst at a temperature of from 25 ℃ to 100 ℃, preferably at 60 ℃, under mildly acidic conditions as described in org.lett. [ organic flash ],2020,22 (22), 8993-8997.
Suitable solvents are halogenated hydrocarbons, such as dichloromethane, dichloroethane, chloroform, and chlorobenzene, preferably dichloroethane. Mixtures of the solvents mentioned can also be used. Suitable acids are generally organic acids, such as acetic acid, propionic acid, toluene sulfonic acid and trifluoroacetic acid, preferably pivalic acid. The acid is generally used in catalytic amounts; however, they may also be used in equimolar amounts, even in excess. The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to use an excess of XII (based on IIIB).
Compound XII is commercially available or known from the cited literature.
The compound IIIB can be obtained by condensation of aldehyde IVB with 3-aminopyrazole V.
The conversion is generally carried out in a protic solvent at a temperature of from 25℃to 70℃and preferably at 70℃as described in WO 2020075706.
Suitable solvents are generally alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert-butanol, preferably ethanol. Mixtures of the solvents mentioned can also be used. The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to use an excess of V (based on IVB).
Compound V is commercially available.
Aldehyde IVB can be obtained from aldehyde XII by substitution with an alkyl thiolate XI, as outlined above (see WO 2000034258). In formula XII, "Hal" represents a halogen atom, preferably Cl or F.
The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to use an excess of XI (based on XII).
Aldehyde XII is commercially available or known from the cited literature.
Compounds I wherein Y is NR 121 can be obtained from similar thioether compounds of formula II by use of a suitable oxidizing agent XIII.
The conversion is generally carried out in the presence of an amine source and an oxidant such as PhI (OAc) 2 in a protic solvent at a temperature of from 0℃to 25℃and preferably from 20℃to 25℃in analogy to the process described, for example, in Org.Lett. [ organic flash ],2020,22 (19), 7470-7474 or CHEMISTRY SELECT [ chemical selection ],2017,2 (4), 1620-1624.
Suitable solvents are polar protic solvents such as alcohols, e.g. methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert-butanol, preferably methanol. Mixtures of the solvents mentioned can also be used. Suitable amine sources are, for example, ammonia, ammonium formate, (NH 4)2CO3、NH4 F, ammonium oxalate, preferably (NH 4)2CO3) suitable oxidizing agents are generally hypervalent iodine reagents such as PhI (OAc) 2 or PhI (TFA) 2 the oxidizing agents are generally used in equimolar amounts, or in excess.
The reaction mixture is worked up in a conventional manner, for example by mixing with water, extraction with a suitable organic solvent, separation of the phases and, if appropriate, chromatographic purification of the crude product. Some of the intermediates and end products are obtained as colorless or light brown viscous oils which are purified or freed of volatile components under reduced pressure and at mildly elevated temperatures. If the intermediates and final products are obtained as solids, purification can also be carried out by recrystallisation or digestion.
If individual compounds I cannot be obtained by the above-described route, they can be prepared by derivatization of other compounds I.
However, if a mixture of isomers is synthesized, separation is generally not necessarily required, as in some cases the individual isomers may be interconverted during work-up for use or during application (e.g. under the action of light, acid or base). Such transformation may also take place after use, for example in the case of plant treatment in the treated plants, or in the pests to be controlled.
The organic moiety groups mentioned in the above definition of variables-like the term halogen-are collective terms of a single enumeration of individual group members. Prefix C n-Cm indicates in each case the number of possible carbon atoms in the group.
For example, the term "substituted with … …" as used in "partially or fully substituted with … …" means that one or more, e.g., 1,2, 3, 4, or 5, or all, of the hydrogen atoms of a given group are replaced with one or more identical or different substituents (e.g., halogen). Thus, for a substituted cyclic moiety, such as a 1-cyanocyclopropyl group, one or more of the hydrogen atoms of the cyclic moiety may be replaced by one or more identical or different substituents.
If a variable indicating that it is possible to occur more than once in formula I may be selected from several alternatives, this means that each may be independently selected from the alternatives. Thus, the phrase "R 4 is H, halogen, C (CN) R 41R42、C(R44)＝N-OR43", etc., means that each "R" is independently selected from H, halogen, C (CN) R 41R42、C(R44)＝N-OR43, etc.
The term "halogen" denotes in each case fluorine, bromine, chlorine or iodine, in particular fluorine, chlorine or bromine.
The term "alkyl" as used herein and in the alkyl portion of alkylamino, alkylcarbonyl, alkylthio, alkylsulfinyl, alkylsulfonyl and alkoxyalkyl denotes in each case straight-chain or branched alkyl groups having generally from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, more preferably from 1 to 3 carbon atoms. Examples of alkyl groups are methyl (Me), ethyl (Et), n-propyl (n-Pr), isopropyl (iPr), n-butyl, 2-butyl, isobutyl, tert-butyl (tBu), n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2-dimethylbutyl, 2, 3-dimethylbutyl, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 2-trimethylpropyl, 1, 2-trimethylpropyl, 1-ethyl-1-methylpropyl, and 1-ethyl-2-methylpropyl.
The term "haloalkyl" as used herein and in the haloalkylcarbonyl, haloalkoxycarbonyl, haloalkylthio, haloalkylsulfonyl, haloalkylsulfinyl, haloalkoxy and haloalkoxyalkyl haloalkyl moiety denotes in each case a straight-chain or branched alkyl radical having generally from 1 to 10 carbon atoms, often from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, in which the hydrogen atoms of the radical are replaced in part or in whole by halogen atoms. Preferred haloalkyl groups are selected from C 1-C4 -haloalkyl, more preferably from C 1-C3 -haloalkyl or C 1-C2 -haloalkyl, in particular from C 1-C2 -fluoroalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-difluoroethyl, 2-trifluoroethyl, pentafluoroethyl and the like.
The term "alkoxy" as used herein denotes in each case a straight-chain or branched alkyl radical bonded via an oxygen atom and generally having from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms. Examples of alkoxy groups are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, 2-butoxy, isobutoxy, tert-butoxy and the like.
The term "alkoxyalkyl" as used herein refers to an alkyl group generally comprising from 1 to 10, often from 1 to 4, preferably from 1 to 2 carbon atoms, wherein 1 carbon atom carries an alkoxy group generally comprising from 1 to 4, preferably 1 or 2 carbon atoms as defined above. Examples are CH 2OCH3、CH2-OC2H5, 2- (methoxy) ethyl, and 2- (ethoxy) ethyl.
The term "haloalkoxy" as used herein denotes in each case a straight-chain or branched alkoxy radical having from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, in which the hydrogen atoms of the radical are replaced in part or completely by halogen atoms, in particular fluorine atoms. Preferred haloalkoxy moieties include C 1-C4 -haloalkoxy, especially C 1-C2 -fluoroalkoxy, such as fluoromethoxy, difluoromethoxy, trifluoromethoxy, 1-fluoroethoxy, 2-difluoroethoxy, 2-trifluoroethoxy 2-chloro-2-fluoroethoxy, 2-chloro-2, 2-difluoroethoxy, 2 dichloro-2-fluoroethoxy, 2-trichloroethoxy, pentafluoroethoxy and the like.
The term "alkylthio" (alkylsulfanyl: S-alkyl) as used herein refers to a straight or branched chain saturated alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms (=c 1-C4 -alkylthio), more preferably 1 to 3 carbon atoms, attached via a sulfur atom.
The term "haloalkylthio" as used herein refers to an alkylthio group as described above wherein the hydrogen atoms are partially or fully substituted with fluorine, chlorine, bromine and/or iodine.
The term "alkylsulfinyl" (alkylsulfinyl: S (=o) -alkyl) as used herein refers to a straight or branched saturated alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms (=c 1-C4 -alkylsulfinyl), more preferably 1 to 3 carbon atoms, bonded through the sulfur atom of the sulfinyl group at any position in the alkyl group (as described above).
The term "haloalkylsulfinyl" as used herein refers to an alkylsulfinyl group as described above, wherein the hydrogen atoms are partially or completely substituted by fluorine, chlorine, bromine and/or iodine.
The term "alkylsulfonyl" (S (=o) 2 -alkyl) as used herein refers to a straight or branched chain saturated alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms (=c 1-C4 -alkylsulfonyl), preferably 1 to 3 carbon atoms, bonded via the sulfur atom of the sulfonyl group at any position in the alkyl group.
The term "haloalkylsulfonyl" as used herein refers to alkylsulfonyl groups as described above wherein the hydrogen atoms are partially or completely substituted by fluorine, chlorine, bromine and/or iodine.
The term "alkylcarbonyl" refers to an alkyl group as defined above which is bonded to the rest of the molecule via a carbon atom of the carbonyl group (c=o).
The term "haloalkylcarbonyl" refers to an alkylcarbonyl group as described above wherein the hydrogen atoms are partially or fully substituted with fluorine, chlorine, bromine and/or iodine.
The term "alkoxycarbonyl" refers to an alkylcarbonyl group as defined above, which is bonded to the rest of the molecule via an oxygen atom.
The term "haloalkoxycarbonyl" refers to an alkoxycarbonyl group as described above wherein the hydrogen atoms are partially or fully substituted with fluorine, chlorine, bromine and/or iodine.
The term "alkenyl" as used herein denotes in each case monounsaturated hydrocarbon radicals having generally from 2 to 10, often from 2 to 6, preferably from 2 to 4, carbon atoms, such as vinyl, allyl (2-propen-1-yl), 1-propen-1-yl, 2-propen-2-yl, methallyl (2-methylpropan-2-en-1-yl), 2-buten-1-yl, 3-buten-1-yl, 2-penten-1-yl, 3-penten-1-yl, 4-penten-1-yl, 1-methylbutan-2-en-1-yl, 2-ethylprop-2-en-1-yl and the like.
The term "haloalkenyl" as used herein refers to an alkenyl group as defined above wherein a hydrogen atom is partially or fully replaced by a halogen atom.
The term "alkynyl" as used herein denotes in each case monounsaturated hydrocarbon radicals having generally from 2 to 10, often from 2 to 6, preferably from 2 to 4, carbon atoms, such as ethynyl, propargyl (2-propyn-1-yl), 1-propyn-1-yl, 1-methylpropan-2-yn-1-yl), 2-butyn-1-yl, 3-butyn-1-yl, 1-pentyn-1-yl, 3-pentyn-1-yl, 4-pentyn-1-yl, 1-methylbutan-2-yn-1-yl, 1-ethylpropan-2-yn-1-yl and the like.
The term "haloalkynyl" as used herein refers to an alkynyl group as defined above wherein a hydrogen atom is partially or fully replaced by a halogen atom.
The term "cycloalkyl" as used herein and in the cycloalkyl portion of the cycloalkoxy and cycloalkylthio groups denotes in each case a monocyclic cycloaliphatic radical having generally 3 to 10 or 3 to 6 carbon atoms, such as cyclopropyl (cC 3H5), cyclobutyl (cC 4H7), cyclopentyl (cC 5H9), cyclohexyl (cC 6H11), cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl, or cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
The term "halocycloalkyl" as used herein and in the halocycloalkyl portion of the halocycloalkoxy and halocycloalkylthio groups denotes in each case a monocyclic cycloaliphatic radical having typically 3 to 10C atoms or 3 to 6C atoms, wherein at least one of the hydrogen atoms (e.g. 1,2, 3,4 or 5) is replaced by halogen, in particular by fluorine or chlorine. Examples are 1-and 2-fluorocyclopropyl groups, 1,2-, 2-and 2, 3-difluorocyclopropyl groups, 1, 2-trifluorocyclopropyl groups, 2, 3-tetrafluorocyclopropyl, 1-and 2-chlorocyclopropyl, 1,2-, 2-and 2, 3-dichlorocyclopropyl, 1, 2-trichlorocyclopropyl, 2, 3-tetrachlorocyclopropyl, 1-, 2-, and 3-fluorocyclopentyl, 1,2-, 2,3-, 3,4-, 2, 5-difluorocyclopentyl, 1-, 2-, and 3-chlorocyclopentyl, 1,2-, 2,3-, 3,4-, 2, 5-dichlorocyclopentyl, and the like.
The term "halocycloalkenyl" as used herein and in the halocycloalkenyl portion of the halocycloalkenyloxy and halocycloalkenyl groups denotes in each case a monocyclic monounsaturated non-aromatic group having generally 3 to 10 (e.g. 3 or 4) or 5 to 10 carbon atoms, preferably 3 to 8 carbon atoms, wherein at least one of the hydrogen atoms (e.g. 1,2,3, 4 or 5) is replaced by halogen, in particular by fluorine or chlorine. Examples are 3, 3-difluorocyclopropen-1-yl and 3, 3-dichloro-cyclopropen-1-yl.
The term "cycloalkenylalkyl" refers to a cycloalkenyl group as defined above which is bonded to the remainder of the molecule via an alkyl group, such as C 1-C5 -alkyl or C 1-C4 -alkyl, in particular methyl (=cycloalkenylmethyl).
The term "carbocycle" or "carbocyclyl" generally includes 3-to 12-membered, preferably 3-to 8-membered, or 5-to 8-membered, more preferably 5-to 6-membered, monocyclic non-aromatic rings containing 3-to 12-membered, preferably 3-to 8-membered, or 5-to 8-membered, more preferably 5-to 6-membered carbon atoms. Preferably, the term "carbocycle" encompasses cycloalkyl and cycloalkenyl groups as defined above.
The term "heterocycle" or "heterocyclyl" generally includes 3-to 12-membered, preferably 3-to 6-membered, especially 6-membered, monocyclic heterocyclic non-aromatic groups. The heterocyclic non-aromatic group typically comprises 1,2, 3, 4 or 5, preferably 1,2 or 3 heteroatoms selected from N, O, and S as ring members, wherein the S atom as ring member may be present as S, SO, or SO 2. Examples of 5-or 6-membered heterocyclic groups include saturated or unsaturated non-aromatic heterocycles such as oxetanyl, thietanyl-S-oxide (S-oxathietanyl), thietanyl-S-dioxide (S-dioxathietanyl), pyrrolidinyl, pyrrolinyl, pyrazolinyl, tetrahydrofuranyl, dihydrofuranyl, 1, 3-dioxanyl, thietanyl, S-oxathiolanyl, S-dioxathiolanyl, dihydrothienyl, S-oxadihydrothienyl, S-dioxathiolanyl, piperidyl, piperazinyl, pyranyl, dihydropyranyl, tetrahydropyranyl, 1, 3-and 1, 4-dioxanyl, thiopyranyl, S-oxothiopyranyl, S-dioxathiopyranyl, dihydrothiopyranyl, S-dioxathiopyranyl, thiodioxathiopyranyl, thiothiodioxanyl, thiothiopyranyl, S-thiothiopyranyl, thiodioxanyl, thiothiopyranyl, piperazinyl, thiothiopyranyl, thiothiothiopyranyl, piperazinyl, thiothiothiopyranyl, S-thiothiothiothiopyranyl, and the like. Examples of the heterocyclic ring further containing 1 or 2 carbonyl groups as ring members include pyrrolidine-2-one, pyrrolidine-2, 5-dione, imidazolidine-2-one, oxazolidin-2-one, thiazolidine-2-one and the like.
The term "heteroaryl" includes monocyclic 5-or 6-membered heteroaromatic groups containing 1,2,3 or 4 heteroatoms selected from N, O, and S as ring members. Examples of 5-or 6-membered heteroaromatic groups include pyridyl, i.e.2-, 3-or 4-pyridyl, pyrimidinyl, i.e.2-, 4-or 5-pyrimidinyl, pyrazinyl, pyridazinyl, i.e.3-or 4-pyridazinyl, thienyl, i.e.2-or 3-thienyl, furyl, i.e.2-or 3-furyl, pyrrolyl, i.e.2-or 3-pyrrolyl, oxazolyl, i.e.2-, 3-or 5-oxazolyl, isoxazolyl, i.e.3-, 4-or 5-isoxazolyl, thiazolyl, i.e.2-, 3-or 5-thiazolyl, isothiazolyl, i.e.3-, 4-or 5-isothiazolyl, pyrazolyl, i.e.g.1-, 3-, 4-or 5-pyrazolyl, i.e.g.1-, 2-, 4-or 5-imidazolyl, oxadiazolyl, e.g.2-or 5- (1, 2, 3-oxadiazolyl), 3-or 5- (1, 2, 4-or 5-oxadiazolyl, 3-or 3-triazolyl, e.g.g.1, 2, 3-or 4-triazolyl, 1, 3-or 4-H, 4-or 5-triazolyl, e.g. 1, 3-or 4-or 5-triazolyl, H, 1, 3-or 4-or 5-triazolyl, and tetrazolyl, i.e., 1H-or 2H-tetrazolyl. The term "heteroaryl" also includes bicyclic 8-to 10-membered heteroaromatic groups comprising 1,2 or 3 heteroatoms selected from N, O, and S as ring members, wherein the 5-or 6-membered heteroaromatic ring is fused to a benzene ring or a 5-or 6-membered heteroaromatic group. Examples of 5-or 6-membered heteroaromatic rings fused to a benzene ring or a 5-or 6-membered heteroaromatic group include benzofuranyl, benzothienyl, indolyl, indazolyl, benzimidazolyl, benzoxathiyl, benzoxadiazolyl, benzothiadiazolyl, benzoxazinyl, quinolinyl, isoquinolinyl, purinyl, 1, 8-naphthyridinyl, pteridinyl, pyrido [3,2-d ] pyrimidinyl, or pyridoimidazolyl, and the like. These fused heteroaryl groups may be bonded to the remainder of the molecule via any ring atom of a 5-or 6-membered heteroaromatic ring or via a carbon atom of the fused phenyl moiety.
The terms "heterocyclylalkyl" and "heteroarylalkyl" refer to a heterocyclyl or heteroaryl group as defined above bonded to the remainder of the molecule via C 1-C5 -alkyl or C 1-C4 -alkyl, especially methyl (heterocyclylmethyl or heteroarylmethyl, respectively).
The terms "arylalkyl" and "phenylalkyl" refer to aryl and phenyl groups as defined above bonded to the remainder of the molecule via C 1-C5 -alkyl or C 1-C4 -alkyl, in particular methyl (=arylmethyl or phenylmethyl), respectively, examples including benzyl, 1-phenylethyl, 2-phenoxyethyl and the like.
The terms "alkylene", "cycloalkylene", "heterocycloalkylene", "alkenylene", "cycloalkenyl", "heterocycloalkenylene" and "alkynylene" refer to alkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl and alkynyl groups, respectively, as defined above, which are bonded to the rest of the molecule via two atoms of the respective groups, preferably via two carbon atoms of the respective groups, and thus represent a linker between the two parts of the molecule.
In particular embodiments, the variables of the compounds of formula I have the following meanings, both as such and in combination with one another are particular embodiments of the compounds of formula I.
Examples and preferred compounds of the invention for the purpose of pesticidal methods and insecticidal applications are outlined in the following paragraphs.
Particularly preferred embodiments of intermediates for variables correspond to those of the compounds of formula I.
Preferably R 1 is C 1-C6 -alkyl, or C 3-C6 -cycloalkyl, more preferably C 1-C3 -alkyl or cyclopropyl, such as CH 3 or cyclopropyl, especially CH 3.
Preferably R 2 is C 1-C4 -haloalkyl, or C 3-C6 -cycloalkyl, more preferably C 1-C3 -haloalkyl or cyclopropyl, such as CHF 2、CF3、CF2CH3, or cyclopropyl, in particular CF 3 or cyclopropyl. In another embodiment, R 2 is H, C 1-C4 -haloalkyl, or C 3-C6 -cycloalkyl, more preferably H, C 1-C3 -haloalkyl or cyclopropyl.
Preferably R 3 is H. In another embodiment, R 3 is H or phenyl, wherein the phenyl is unsubstituted or substituted with halogen, preferably H or phenyl substituted with halogen.
R 5 is preferably C 1-C4 -alkyl, more preferably C 1-C3 -alkyl, in particular ethyl.
A is preferably CH or CR A, preferably wherein R A is C 1-C3 -alkyl or halogen, in particular CH or C-CH 3. Such compounds correspond to formula IA.
In another embodiment, a is N. Such compounds correspond to formula IB.
G is preferably a six membered heteroaryl group, such as pyridinyl, preferably 2-pyridinyl.
In another embodiment, G is phenyl.
Such compounds correspond to formula IG, wherein Q is CH or N:
R 4 is preferably at the para position (bicyclic attachment relative to the 6 membered ring) and is preferably selected from halogen, such as F, cl, br; a CN; n (R 43)C(O)R44、N＝S(O)(CH3)2;C1-C4 -alkyl, C 3-C6 -cycloalkyl, or C 1-C4 -alkoxy, both unsubstituted or substituted by CN or halogen, C 2-C4 -alkenyl or C 2-C4 -alkynyl, both unsubstituted or substituted by C 3-C6 -cycloalkyl;
Phenyl or pyridinyl, which are unsubstituted or substituted by R G (preferably selected from halogen, CN, C 1-C4 -alkyl, C 1-C4 -alkoxy, C 1-C4 -haloalkyl, C 1-C4 -haloalkoxy); or two radicals R G are bonded to two adjacent ring atoms to form a 4-to 6-membered carbocyclic or heterocyclic ring which is unsubstituted or partially or fully substituted by R F (preferably halogen).
In another embodiment, R 4 is selected from H, halogen such as F, cl, br; a CN; n=s (O) (CH 3)2;
Phenyl or pyridinyl, which are unsubstituted or substituted by R G (preferably selected from halogen, CN, C 1-C4 -alkoxy, C 1-C4 -haloalkoxy);
Or two radicals R G are bonded to two adjacent ring atoms to form a 4-to 6-membered carbocyclic or heterocyclic ring which is unsubstituted or partially or fully substituted by R F (preferably halogen).
In another embodiment, R 4 is selected from H, halogen such as F, cl, br; a CN; n=s (O) (CH 3)2;
Phenyl or pyridinyl substituted with R G (selected from halogen, CN, or C 1-C3 -haloalkoxy);
Or two radicals R G are bonded to two adjacent ring atoms to form a 5-membered carbocyclic or heterocyclic ring which is unsubstituted or partially or fully substituted by R F (preferably halogen).
In another embodiment, R 4 is selected from H, halogen such as F, cl, br; a CN; n=s (O) (CH 3)2;
Phenyl or pyridinyl substituted with R G (selected from halogen, CN, or C 1-C3 -haloalkoxy);
or two radicals R G are bonded to two adjacent ring atoms to form a 5-membered carbocycle or heterocycle containing two O-atoms as ring members, which carbocycle or heterocycle is substituted with R F (preferably halogen).
The subscript n is preferably 1 or 2, especially 1.Y is preferably O. The subscript m is preferably 2.
In particular, the compounds of formula I listed in the following table are preferred, in view of their use, these compounds corresponding to formula I.G. Furthermore, each group mentioned in the table for a substituent is itself (independently of the mentioned combination) a particularly preferred aspect of the substituent.
TABLE 1
Compounds of the formula IG, where A is CH, R 1 is CH 3,R2 is CF 3 and the combination of Q and R 4 corresponds in each case to one line of Table A for the compounds
TABLE 2
Compounds of the formula IG, where A is C-CH 3,R1 is CH 3,R2 is CF 3 and the combination of Q and R 4 corresponds in each case to one line of Table A for the compounds
TABLE 3 Table 3
Compounds of the formula IG, where A is N, R 1 is CH 3,R2 is CF 3 and the combination of Q and R 4 corresponds in each case to one line of Table A for the compounds
TABLE 4 Table 4
Compounds of the formula IG, where A is C-Br, R 1 is CH 3,R2 is CF 3 and the combination of Q and R 4 corresponds in each case to one line of Table A for the compounds
TABLE 5
A compound of formula G, wherein a is CH, R 1 is C-C 3H5,R2 is CF 3 and the combination of Q and R 4 corresponds in each case to one row of table a for the compound
TABLE 6
Compounds of the formula IG, where A is C-CH 3,R1 is C-C 3H5,R2 is CF 3 and the combination of Q and R 4 corresponds in each case to one line of Table A for the compounds
TABLE 7
Compounds of the formula IG, where A is N, R 1 is C-C 3H5,R2 is CF 3 and the combination of Q and R 4 corresponds in each case to one line of Table A for the compounds
TABLE 8
Compounds of the formula IG, where A is CH, R 1 is CH 3,R2 is CHF 2 and the combination of Q and R 4 corresponds in each case to one line of Table A for the compounds
TABLE 9
Compounds of the formula IG, where A is C-CH 3,R1 is CH 3,R2 is CHF 2 and the combination of Q and R 4 corresponds in each case to one line of Table A for the compounds
Table 10
Compounds of the formula IG, where A is N, R 1 is CH 3,R2 is CHF 2 and the combination of Q and R 4 corresponds in each case to one line of Table A for the compounds
TABLE 11
A compound of formula G, wherein a is CH, R 1 is C-C 3H5,R2 is CHF 2 and the combination of Q and R 4 corresponds in each case to one row of table a for the compound
Table 12
Compounds of the formula IG, where A is C-CH 3,R1 is C-C 3H5,R2 is CHF 2 and the combination of Q and R 4 corresponds in each case to one line of Table A for the compounds
TABLE 13
Compounds of the formula IG, where A is N, R 1 is C-C 3H5,R2 is CHF 2 and the combination of Q and R 4 corresponds in each case to one line of Table A for the compounds
TABLE 14
Compounds of the formula IG, where A is CH, R 1 is CH 3,R2 is C-C 3H5 and the combination of Q and R 4 corresponds in each case to one line of Table A for the compounds
TABLE 15
Compounds of the formula IG, where A is C-CH 3,R1 is CH 3,R2 is C-C 3H5 and the combination of Q and R 4 corresponds in each case to one line of Table A for the compounds
Table 16
Compounds of the formula IG, where A is N, R 1 is CH 3,R2 is C-C 3H5 and the combination of Q and R 4 corresponds in each case to one line of Table A for the compounds
TABLE 17
Compounds of the formula IG, where A is C-Br, R 1 is CH 3,R2 is C-C 3H5 and the combination of Q and R 4 corresponds in each case to one line of Table A for the compounds
TABLE 18
A compound of formula G wherein a is CH, R 1 is C-C 3H5,R2 is C-C 3H5 and the combination of Q and R 4 corresponds in each case to one row of table a for the compound
TABLE 19
Compounds of the formula IG, where A is C-CH 3,R1 is C-C 3H5,R2 is C C-C 3H5 F3 and the combination of Q and R 4 corresponds in each case to one line of Table A for the compounds
Table 20
Compounds of the formula IG, where A is N, R 1 is C-C 3H5,R2 is C-C 3H5 and the combination of Q and R 4 corresponds in each case to one line of Table A for the compounds
Table A
"#" Indicates a linkage to the remainder of formula (I).
The term "one or more compounds of the invention" refers to one or more compounds of formula I or "one or more compounds I" and includes salts, tautomers, stereoisomers, and N-oxides thereof.
The invention also relates to agrochemical compositions comprising an adjuvant and at least one compound I.
The agrochemical composition comprises a pesticidally effective amount of compound I.
The compounds I can be converted into agrochemical compositions of the usual type, such as solutions, emulsions, suspensions, dusts, powders, pastes, granules, compressed tablets, capsules, and mixtures thereof. Examples of types of compositions are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, lozenges, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), tabletting agents (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal products (e.g. LN) and gel formulations (e.g. GF) for treating plant propagation material (e.g. seeds). These and additional composition types are defined in "Catalogue of pesticide formulation types and international coding system [ pesticide formulation types and international code system catalogue ]", TECHNICAL MONOGRAPH [ technical monograph ] phase 2,6 th edition, month 5 of 2008, international association of crop lives. These compositions are prepared in a known manner, for example as described below: mollet and Grubemann, formulation technology [ formulation technology ], wiley VCH [ Weili VCH Press ], wei Yinhai mu (Weinheim), 2001; or Knowles, new developments in crop protection product formulation [ new developments in crop protection product formulations ], agrow Reports DS243, T & F Informa [ Informa taylor-francissi press ], london, 2005.
Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetting agents, adjuvants, solubilizers, permeation enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, antifreeze agents, defoamers, colorants, tackifiers and binders.
Suitable solvents and liquid carriers are water and organic solvents. A suitable solid carrier or filler is mineral earth.
Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes. Such surfactants can be used as emulsifiers, dispersants, solubilizers, wetting agents, permeation enhancers, protective colloids or adjuvants. Surfactants are listed in McCutcheon, volume 1, emulsifiers & Detergents, mcCutcheon's directors [ emulsifying and Detergents, makakino catalogue ], greenlock, U.S. A.C., glen Rock, USA, 2008 (International or North AMERICAN ED (International or North America)). Suitable anionic surfactants are alkali metal, alkaline earth metal, or ammonium salts of sulfonic, sulfuric, phosphoric, carboxylic acids. Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants. Suitable cationic surfactants are quaternary ammonium surfactants.
The agrochemical composition generally comprises between 0.01% and 95% by weight, preferably between 0.1% and 90% and most preferably between 0.5% and 75% of active substance. The active substances are used in a purity of from 90% to 100%, preferably from 95% to 100%.
Various types of oils, wetting agents, adjuvants, or fertilizers may be added as a premix or (if appropriate) not added (tank mix) to the active or to the composition comprising them until just before use. These agents may be mixed with the composition according to the invention in a weight ratio of 1:100 to 100:1.
The user typically applies the composition according to the invention from a pre-dosing device, a backpack sprayer, a spray can, a spray aircraft, or an irrigation system. Typically, the agrochemical composition is made up of water, buffer and/or further adjuvants to the desired application concentration and the ready-to-use spray liquid or agrochemical composition according to the invention is thus obtained. Typically, 20 to 2000 liters of ready-to-use spray liquid are applied per hectare of agricultural useful area.
The compounds I are suitable for protecting crops, plants, plant propagation material (e.g. seeds) or soil or water in which plants are growing from attack or infestation by animal pests. The invention therefore also relates to a plant protection method comprising contacting a crop, a plant, plant propagation material (e.g. seed), or soil or water in which plants are growing, to be protected from attack or infestation by animal pests with a pesticidally effective amount of compound I.
The compounds I are also suitable for combating or controlling animal pests. The invention therefore also relates to a method of combating or controlling animal pests, which comprises contacting the animal pests, their habitat, breeding grounds, or food supply, or the crops, plants, plant propagation material (e.g. seeds), or the soil, or the area, material or environment in which the animal pests are growing or are likely to grow, with a pesticidally effective amount of compound I.
Compound I is effective for any and all developmental stages, such as eggs, larvae, pupae, and adults, by both contact and ingestion.
The compounds I may be applied as such or in the form of compositions comprising them.
The application can be carried out both before and after the crop, plant propagation material is infested with pests.
The term "contacting" includes both direct contact (application of the compound/composition directly to animal pests or plants) and indirect contact (application of the compound/composition to the locus).
The term "animal pest" includes arthropods, gastropods, and nematodes. Preferred animal pests according to the invention are arthropods, preferably insects and arachnids, in particular insects.
The term "plant" includes grains such as durum wheat and other wheat, rye, barley, triticale, oats, rice, or maize (forage and sweet maize/sweet corn and field corn); beet, such as sugar beet, or fodder beet; fruits, such as pomes, stone fruits, or soft fruits, such as apples, pears, plums, peaches, nectarines, almonds, cherries, papaya, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as beans, lentils, peas, alfalfa, or soybeans; oil plants, such as rapeseed (oilseed rape), cabbage type rape, mustard, olive, sunflower, coconut, cocoa beans, castor oil plants, oil palm, peanut, or soybean; cucurbitaceae plants such as cucurbits, squash, cucumber or melon; fiber plants, such as cotton, flax, hemp, or jute; citrus fruits, such as orange, lemon, grapefruit or mandarin orange; vegetables, such as eggplant, spinach, lettuce (e.g. cabbage), chicory, cabbage, asparagus, cabbage, carrot, onion, garlic, leek, tomato, potato, cucurbit or sweet pepper; laurel-like plants, such as avocado, cinnamon, or camphor; energy and raw plants, such as corn, soybean, rapeseed, sugarcane or oil palm; tobacco; nuts, such as walnuts; pistachio nuts; coffee; tea; bananas; vine; hops; stevia rebaudiana (Stevia); natural rubber plants or ornamental and forestry plants, shrubs, broad-leaved trees or evergreen plants, eucalyptus; turf; a lawn; grass. Preferred plants include potato, sugar beet, tobacco, wheat, rye, barley, oat, rice, corn, cotton, soybean, rapeseed, legumes, sunflower, coffee or sugarcane; fruit; vine; ornamental plants; or vegetables, such as cucumbers, tomatoes, beans or cucumbers.
The term "seed" includes seeds and plant propagules, including true seeds, seed slices (SEED PIECE), shoots, bulbs, fruits, tubers, grains, cuttings, cut shoots (cut shoots), and preferably means true seeds.
By "pesticidally effective amount" is meant the amount of active ingredient required to achieve an observable effect on growth, including necrosis, death, retardation, prevention and elimination, destruction, or otherwise reducing the appearance and activity of the target organism. The pesticidally effective amount may vary for the various compounds/compositions used in the present invention. The pesticidally effective amount of the composition will also vary depending upon the prevailing conditions, such as the desired pesticidal effect and the duration, climate, target species, locus, mode of application.
For use in the treatment of crop plants, for example by foliar application, the application rate of the active ingredient of the invention may be in the range from 0.0001g to 4000g per hectare, for example from 1g to 2kg per hectare or from 1g to 750g per hectare, ideally from 1g to 100g per hectare.
The compounds I are also suitable for combating non-crop insect pests. For use against such non-crop pests, compound I can be used as bait composition, gel, normal insect spray, aerosol, as ultra-low volume application and mosquito net (dipping or surface application).
The term "non-crop insect pest" refers to a pest that is particularly relevant to a non-crop target, such as ants, termites, wasps, flies, ticks, mosquitoes, bed bugs, cricket, or cockroaches, such as: aedes aegypti (AEDES AEGYPTI), house flies (Musca domestica), anthropomorphic species (Tribolium spp.); termites such as North America Alternaria longifolia (Reticulitermes flavipes), taiwan white ants (Coptotermes formosanus); cockroaches, such as german cockroaches (Blatella germanica), american cockroaches (PERIPLANETA AMERICANA); ants such as solenopsis invicta (Solenopsis invicta), argentina (LINEPITHEMA HUMILE) and Blackwood workers (Camponotus pennsylvanicus).
The bait may be a liquid, solid or semi-solid formulation (e.g., a gel). For use in bait compositions, the active ingredient is typically present in an amount of from 0.001wt% to 15wt%, desirably from 0.001wt% to 5wt% of the active compound.
The compounds I and their compositions can be used for protecting wooden materials, such as trees, wooden fences, sleepers, frames, artwork and the like, as well as buildings, but also building materials, furniture, leather, fibres, vinyl, wires and cables and the like, against ants, termites and/or beetles which destroy wood or textiles, and for controlling ants and termites from damaging crops or humans (for example when pests invade houses and public facilities or nest in yards, orchards or parks).
Conventional application rates in protective materials are, for example, from 0.001g to 2000g or from 0.01g to 1000g of active compound per m 2 of treated material, desirably from 0.1g to 50g per m 2.
The insecticidal composition for impregnating materials typically contains 0.001 to 95wt%, preferably 0.1 to 45wt%, and more preferably 1 to 25wt% of at least one repellent and/or insecticide.
Harmful organisms
The compounds of the invention are particularly suitable for effective against animal pests, such as arthropods and nematodes, including:
Insects from the following sub-orders: subgenosis (Auchenorrhyncha), such as, for example, leafhoppers (Amrasca biguttula), leafhoppers species (Empoasca spp.), leafhoppers (Nephotettix virescens), hawk-tail planthoppers (Sogatella furcifera), leafhoppers species (MAHANARVA spp.), brown planthoppers (Laodelphax striatellus), brown planthoppers (NILAPARVATA LUGENS), citrus psyllids (Diaphorina citri);
Lepidoptera (Lepidoptera), such as Spodoptera species (Helicoverpa spp.), spodoptera frugiperda (Heliothis virescens), plutella xylostella (lobisia botrana), corn borer (Ostrinia nubilalis), plutella xylostella (Plutella xylostella), spodoptera sojae (Pseudoplusia includens), trytis cinerea (Scirpophaga incertulas), spodoptera species (Spodoptera spp.), spodoptera frugiperda (Trichoplusia ni), tomato leaf miner (Tuta absoluta), cnaphalocrocis medinalis (Cnaphalocrocis medialis), codling moth (Cydia pomonella), chilo suppressalis (Chilo suppressalis), soybean noctuid (ANTICARSIA GEMMATALIS), spodoptera frugiperda (Agrotis ipsilon), huang Douyin noctuid (Chrysodeixis includens);
Stinkbugs (True bugs), such as Lygus species (Lygus spp.), stinkbugs (stinkbugs) such as Lygus species (euschisttus spp.), lygus sinensis (Halyomorpha halys), lygus lucorum (Nezara viridula), lygus kafimbriae (Piezodorus guildinii), stinkbug (Dichelops furcatus);
Thrips (threads), e.g. Frankliniella spp, thrips spp, frankliniella Dichromothrips corbettii;
Aphids (Aphids), such as Aphis pisiformis (Acyrthosiphon pisum), aphis species (Aphis spp), myzus persicae (Myzus persicae), aphis species (rhopalosihum spp.), myzus gracilis (Schizaphis graminum), cercospora spinosa (Megoura viciae);
whiteflies, for example, white fly in the greenhouse (Trialeurodes vaporariorum), bemisia species (Bemisia spp.);
coleoptera (Coleoptera), such as phyllostachys species (Phyllotreta spp.), click beetle species (Melanotus spp.), coriolus versicolor (MELIGETHES AENEUS), potato leaf beetle (Leptinotarsa decimlineata), tortoise species (Ceutorhynchus spp.), phyllostachys species (Diabrotica spp.), cotton bolo beetle (Anthonomus grandis), beet cryptosporidium (Atomaria linearia), click beetle species (Agriotes spp.), ladybug species (EPILACHNA spp.);
Flies, for example, geotrichum species (Delia spp.), medfly (CERATITIS CAPITATA), fruit fly species (Bactrocera spp.), liriomyza spp.);
the general family of scale (Coccoidea), such as orange round kidney scale (Aonidiella aurantii), double-strip haired scale (FERRISIA VIRGATE);
Arachnids (ARACHNIDA) arthropods (mites), such as, for example, round wheat She Zhaoman (Penthaleus major), tetranychus spp;
Nematodes, such as soybean cyst nematode (Heterodera glycines), root knot nematode species (Meloidogyne spp.), brachyotus species (Pratylenchus spp.), caenorhabditis elegans (Caenorhabditis elegans).
Animal health
The compounds I are suitable for treating or protecting animals against infestation or infection by parasites. The invention therefore also relates to the use of a compound according to the invention for the manufacture of a medicament for treating or protecting animals against infestation or infection by parasites. Furthermore, the present invention relates to a method for treating or protecting animals against infestation and infection by parasites which comprises orally, topically or parenterally administering or applying to the animals a parasiticidally effective amount of compound I.
The invention also relates to the non-therapeutic use of the compounds of the invention for treating or protecting animals against infestation and infection by parasites. Furthermore, the present invention relates to a non-therapeutic method for treating or protecting animals against infestation and infection by parasites which comprises applying to the locus a parasiticidally effective amount of compound I.
The compounds of the invention are further suitable for combating or controlling parasites in and on animals. Furthermore, the invention relates to a method for combating or controlling parasites in and on animals, which method comprises contacting the parasites with a parasiticidally effective amount of compound I.
The invention also relates to the non-therapeutic use of the compounds I for controlling or combating parasites. Furthermore, the invention relates to a non-therapeutic method for combating or controlling parasites, which comprises applying to the locus a parasiticidally effective amount of compound I.
Compound I may be effective by both contact (via soil, glass, wall, mosquito net, carpet, blanket or animal site) and ingestion (e.g. bait). Furthermore, compound I may be administered at any and all stages of development.
The compounds I may be applied as such or in the form of compositions comprising them.
The term "locus" means a habitat, food supply, breeding ground, area, material or environment in which parasites are growing or are likely to grow outside animals.
As used herein, the term "parasite" includes endoparasites and ectoparasites. In some embodiments of the invention, endoparasites may be preferred. In other embodiments, ectoparasites may be preferred. Infestation in warm-blooded animals and fish includes lice, biting lice, ticks, sheep nose fly maggots, sheep ticks, chelating flies, house flies, maggot larvae, chiggers, gnats, mosquitoes and fleas.
The compounds of the invention are particularly useful against the following parasites: warm zone bed bugs (Cimex lectularius), rhipicephalus hemangiocarpus (Rhipicephalus sanguineus) and Chlamydia felis (Ctenocephalides felis).
As used herein, the term "animal" includes warm-blooded animals (including humans) and fish. Preferably mammals such as cattle, sheep, pigs, camels, deer, horses, pigs, poultry, rabbits, goats, dogs and cats, buffalo, donkeys, deer and reindeer, and also fur-bearing animals such as mink, chinchilla and raccoon, birds such as hens, geese, turkeys and ducks, and fish such as freshwater fish and salted fish such as salmon, carp and eel. Particularly preferred are domestic animals such as dogs or cats.
Compound I may be administered in a total amount of 0.5mg/kg to 100mg/kg per day, preferably 1mg/kg to 50mg/kg per day.
For oral administration to warm-blooded animals, compound I can be formulated as animal feed, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, infusions, gels, tablets, boluses and capsules. For oral administration, the dosage form selected should provide the animal with 0.01mg/kg to 100mg/kg animal body weight/day, preferably 0.5mg/kg to 100mg/kg animal body weight/day of compound I.
Alternatively, compound I may be administered parenterally to the animal, for example by intracavity, intramuscular, intravenous or subcutaneous injection. For subcutaneous injection, compound I may be dispersed or dissolved in a physiologically acceptable carrier. Alternatively, compound I may be formulated as an implant for subcutaneous administration. In addition, compound I may be administered transdermally to an animal. For parenteral administration, the dosage form selected should provide the animal with 0.01mg/kg to 100mg/kg animal body weight/day of compound I.
Compound I may also be topically applied to animals in the form of infusion, dust, powder, collar, wall-tag (medallion), spray, shampoo, spray-on and pour-on formulations, as ointments or oil-in-water or water-in-oil emulsions. For topical application, dips and sprays generally contain from 0.5ppm to 5,000ppm and preferably from 1ppm to 3,000ppm of compound I. In addition, compound I can be formulated as an ear tag for animals, in particular quadruped animals (e.g. cattle and sheep).
The oral solution is administered directly.
The solution for application to the skin is applied dropwise, spread, rubbed, sprinkled or sprayed.
The gel is applied or coated on the skin or introduced into a body cavity.
The pour-on formulation is poured or sprayed onto a defined area of skin and the active compound penetrates the skin and is inhaled to act. Pour-on formulations are prepared by dissolving, suspending or emulsifying the active compound in a suitable skin-compatible solvent or solvent mixture.
The emulsion may be administered orally, transdermally or as an injection.
The suspension may be administered orally or topically/transdermally.
Semisolid formulations may be administered orally or topically/transdermally.
To produce solid preparations, the active compound is admixed with suitable excipients, if appropriate with auxiliaries, and made into the desired dosage forms.
The compositions that may be used in the present invention may generally comprise from about 0.001% to 95% of compound I.
The ready-to-use formulation contains the compound acting on the parasite, preferably the ectoparasite, in a concentration of from 10ppm to 80% by weight, preferably from 0.1% to 65% by weight, more preferably from 1% to 50% by weight, most preferably from 5% to 40% by weight.
The formulations diluted prior to use contain the compound acting on the ectoparasite in a concentration of 0.5% to 90% by weight, preferably 1% to 50% by weight.
Furthermore, the formulations comprise the compounds of the formula I against endoparasites in a concentration of from 10ppm to 2% by weight, preferably from 0.05% to 0.9% by weight, very particularly preferably from 0.005% to 0.25% by weight.
The solid formulations which release the compounds of the invention in a total amount of 10mg/kg to 300mg/kg, preferably 20mg/kg to 200mg/kg, most preferably 25mg/kg to 160mg/kg of body weight of the treated animal in three weeks can be administered.
A. Preparation example
Materials: unless otherwise indicated, reagents and solvents were purchased at the highest commercial quality and used without further purification. Purchase acetonitrile (MeCN) from commercial suppliers; anhydrous Tetrahydrofuran (THF), ethyl acetate (EtOAc), diethyl ether (DEE), dimethyl sulfoxide (DMSO), acetone, ethanol (EtOH), benzene, dimethylformamide (DMF), diisopropylethylamine (DIPEA), hexafluorophosphate Azabenzotriazole Tetramethylurea (HATU), pyridine, and CH 2Cl2 (DCM).
The compounds are characterized by melting point determination, NMR spectroscopy or by mass to charge ratio ([ m/z ]) and retention time (R t; [ min ]), as determined by Mass Spectrometry (MS) in combination with HPLC analysis (HPLC-ms=high performance liquid chromatography-mass spectrometry) or LC analysis (LC-ms=liquid chromatography-mass spectrometry).
Characterization: the compounds were characterized by high performance liquid chromatography combined with mass spectrometry (HPLC/MS).
All reactions were monitored by Thin Layer Chromatography (TLC) using Merck silica gel 60F 2 pre-coated plates (0.25 mm). Flash chromatography was performed on Kanto Chemical silica gel (Kanto Chemical Co., ltd., silica gel 60N, spherical neutral, 0.040-0.050mm, catalog number 37563-84). If not otherwise indicated, 1 H NMR spectra were recorded on JEOL JNM-ECA-500 (500 MHz). Chemical shift to be relative to acetone-d 6(1 H; δ=2.05 ppm) and CD 3OD(1 H; δ=3.30 ppm) and J values are given in hertz. The following abbreviations are used to explain the multiplicity: s=singlet, d=doublet, t=triplet, q=quartet, dd=doublet, dt=doublet, m=multiplet, br=broad. High resolution mass spectra were measured on a JEOL JMS-T100 LP.
Method A: AGILENT ECLIPSE Plus C18, 50X 4.6mm, ID 5 μm; eluting: a=10 mM ammonium formate (0.1% formic acid), b=acetonitrile (0.1% formic acid), flow rate=1.2 ml/min at 30 ℃; gradient: 10% B to 100% B-3min, 1min-10% B. Run time = 5.01min; MS: ESI is positive; mass range (m/z): 100-700.
Method B: LC (liquid crystal): shimadzu LC-30ad, esi; column: kinetex EVO C18.5.5 μm 2.1X10 mm; mobile phase: a: water+0.04% TFA; b: acn+0.02% TFA; temperature: 40 ℃; gradient: within 2.5min, 5% B to 100% B; within 0.02min, 100% B to 5% B;5% B, for 0.5min; flow rate: 0.8mL/min; MS: ESI is positive; the mass range is as follows: 100-2000.
Abbreviations: mL (milliliters); g (g); h (hours); min (min).
Example 1: synthesis of 5- (5-bromo-3-ethylsulfonyl-2-pyridinyl) -1-methyl-2- (trifluoromethyl) pyrazolo [1,5-a ] pyrimidin-7-one (I-1)
Step 1: synthesis of 5-bromo-3-ethylsulfanyl-pyridine-2-carbonitrile
To a stirred solution of 5-bromo-3-nitro-pyridine-2-carbonitrile (5.0 g) in anhydrous THF (45 mL) and water (5 mL) at-10 ℃ was added sodium ethanethiolate (2.17 g). The resulting reaction mixture was stirred for 2h at a gradient from 0 ℃ to about 20 ℃ to 25 ℃. After the reaction was completed, the reaction mixture was quenched with saturated aqueous NH 4 Cl (250 mL) and extracted with ethyl acetate (2×500 mL). The organic layer was separated, dried over Na 2SO4, and concentrated under reduced pressure to give the crude material. It was crystallized from isopropanol (100 mL) to give the title compound (4.2 g) as a brown solid.
1H-NMR(300MHz,DMSO-d6)δ8.66(d,J＝2.0Hz,1H),8.35(d,J＝2.0Hz,2H),3.24(q,J＝7.3Hz,2H),1.28(t,J＝7.3Hz,3H).
Step 2: synthesis of 1- (5-bromo-3-ethylsulfanyl-2-pyridyl) ethanone
A stirred solution of 5-bromo-3-ethylsulfanyl-pyridine-2-carbonitrile (4.0 g) in anhydrous THF (50 mL) was cooled to 0deg.C, and CH 3 MgBr (3M, 10.97mL in DEE) was then added dropwise. The resulting reaction mixture was stirred at 0℃for 2h. After the reaction was completed, the reaction mixture was quenched with saturated aqueous NH 4 Cl (250 mL) and extracted with ethyl acetate (2×500 mL). The organic layer was separated, dried over Na 2SO4, and concentrated under reduced pressure to give the crude material. It was purified by column chromatography using ethyl acetate and heptane as eluent to give the title compound (3.8 g) as an off-white solid.
1H-NMR(300MHz,CDCl3)δ8.33(d,J＝1.9Hz,1H),7.69(d,J＝1.9Hz,1H),2.83(q,J＝7.4Hz,2H),2.60(s,3H),1.33(t,J＝7.4Hz,3H).
Step 3: synthesis of ethyl 3- (5-bromo-3-ethylsulfanyl-2-pyridyl) -3-oxo-propionate
A stirred solution of 1- (5-bromo-3-ethylsulfanyl-2-pyridyl) ethanone (3.8 g) in heptane (40 mL) was cooled to 0deg.C, then NaH 60% (1.75 g) was added in portions, and then diethyl carbonate (7.2 mL) was added. The reaction mixture was heated at 85℃for 6h. After the reaction was completed, the reaction mixture was quenched with ice-cold water (150 mL) and extracted with ethyl acetate (2×250 mL). The organic layer was separated, dried over Na 2SO4, and concentrated under reduced pressure to give the crude material. It was purified by column chromatography using ethyl acetate and heptane as eluent to give the title compound (3.0 g) as a yellow liquid.
LC/MS (method a): r t：2.44min;m/z＝334(M+2)+
1H-NMR(500MHz,CDCl3)δ8.41(t,J＝1.5Hz,1H),7.80(d,J＝1.9Hz,1H),4.20(q,J＝7.1Hz,2H),4.13(s,2H),2.94(q,J＝7.4Hz,2H),1.44(t,J＝7.4Hz,3H),1.26(td,J＝7.1,1.0Hz,3H).
Step 4: synthesis of 5- (5-bromo-3-ethylsulfanyl-2-pyridyl) -1-methyl-2- (trifluoromethyl) pyrazolo [1,5-a ] pyrimidin-7-one (I-12)
To a stirred solution of ethyl 3- (5-bromo-3-ethylsulfanyl-2-pyridyl) -3-oxo-propionate (3 g) and 1-methyl-5- (trifluoromethyl) pyrazol-3-amine (2.0 g) in 1, 4-dioxane (1.0 mL) was added polyphosphoric acid (2.0 mL) at 20℃to 25 ℃. The reaction mixture was heated to 130 ℃ for 5h. The progress of the reaction was monitored by LCMS analysis. After the reaction was completed, the reaction mixture was quenched with 1N NaOH solution (150 mL) and extracted with ethyl acetate (2×100 mL). The combined organic layers were dried over Na 2SO4 and concentrated under reduced pressure. The crude product was purified by column chromatography using ethyl acetate and heptane as eluent to give the desired product (1.5 g) as an off-white solid.
1H-NMR(500MHz,DMSO-d6)δ8.53(d,J＝2.2Hz,1H),8.07(d,J＝2.2Hz,1H),7.43(s,1H),6.48(d,J＝1.9Hz,1H),4.35(s,3H),3.01(q,J＝7.5Hz,2H),1.20(dd,J＝8.3,6.4Hz,3H).
Step 5: synthesis of 5- (5-bromo-3-ethylsulfonyl-2-pyridinyl) -1-methyl-2- (trifluoromethyl) pyrazolo [1,5-a ] pyrimidin-7-one (I-1)
A stirred solution of 5- (5-bromo-3-ethylsulfanyl-2-pyridyl) -1-methyl-2- (trifluoromethyl) pyrazolo [1,5-a ] pyrimidin-7-one (1.5 g) in DCM (20 mL) was cooled to 0℃and m-chloroperoxybenzoic acid (1.54 g) was added portionwise. The reaction mixture was stirred at 20 ℃ to 25 ℃ for 16h. After the reaction was completed, the reaction mixture was quenched with saturated Na 2S2O3 solution (70 mL) and extracted with ethyl acetate (2×100 mL). The combined organic layers were dried over Na 2SO4 and concentrated under reduced pressure. The crude product was purified by column chromatography using ethyl acetate and heptane as eluent to give the title compound (0.9 g) as an off-white solid.
1H-NMR(500MHz,DMSO-d6)δ9.6(d,J＝2.3Hz,1H),8.6(dd,J＝8.2,2.4Hz,1H),7.57(dd,J＝8.2,2.1Hz,1H),6.4(d,J＝2.0Hz,1H),4.37(d,J＝1.9Hz,3H),3.80-3.71(m,2H),1.19(td,J＝7.4,2.1Hz,3H).
Example 2: synthesis of 5- [5- [ [ dimethyl (oxo) - λ6-sulfinyl ] amino ] -3-ethylsulfonyl-2-pyridinyl ] -1-methyl-2- (trifluoromethyl) pyrazolo [1,5-a ] pyrimidin-7-one (compound I-2)
To a stirred solution of 5- (5-bromo-3-ethylsulfonyl-2-pyridinyl) -1-methyl-2- (trifluoromethyl) pyrazolo [1,5-a ] pyrimidin-7-one (0.15 g) in 1, 4-dioxane (2 mL) was added K 2CO3 (0.157 g), dimethyl-sulfonylimide (0.032 g) and 4, 5-bis-diphenylphosphine-9, 9-dimethylxanthene (xanthphos) (0.018 g), the reaction mixture was degassed under nitrogen for 10min, and then Pd 2(dba)3 (0.015 g) was subsequently added. The reaction mixture was heated to 120 ℃ for 5h. After the reaction was completed, the reaction mixture was concentrated under reduced pressure. The crude product was purified by column chromatography using methanol and DCM as eluent to give the title compound (0.1 g) as an off-white solid.
1H-NMR(300MHz,DMSO-d6)δ8.45(d,J＝2.5Hz,1H),7.87(d,J＝2.5Hz,1H),7.46(s,1H),6.36(s,1H),4.36(s,3H),3.93(t,J＝7.4Hz,2H),2.96(s,6H),1.24(t,J＝7.4Hz,3H).
Example 3: synthesis of 5- [ 3-ethylsulfonyl-5- (4-fluorophenyl) -2-pyridyl ] -1-methyl-2- (trifluoromethyl) pyrazolo [1,5-a ] pyrimidin-7-one (I-3)
To a stirred solution of 5- (5-bromo-3-ethylsulfonyl-2-pyridinyl) -1-methyl-2- (trifluoromethyl) pyrazolo [1,5-a ] pyrimidin-7-one (0.15 g) in 1, 4-dioxane (2 mL) was added K 2CO3 (0.134 g) and 4-fluorophenylboronic acid (0.09 g), the reaction mixture was degassed under nitrogen for 10min, and then 1,1' -bis (diphenylphosphino) ferrocene ] palladium (II) dichloride (0.019 g) was subsequently added. The reaction mixture was heated to 120 ℃ for 5h. After the reaction was completed, the reaction mixture was concentrated under reduced pressure. The crude product was purified by column chromatography using ethyl acetate and heptane as eluent to give the title compound (0.1 g) as an off-white solid.
1H-NMR(300MHz,DMSO-d6)δ9.27(d,J＝2.2Hz,1H),8.56(d,J＝2.2Hz,1H),7.96(dd,J＝8.6,5.3Hz,2H),7.51(s,1H),7.43(t,J＝8.8Hz,2H),6.45(s,1H),4.40(s,3H),3.95(q,J＝7.4Hz,2H),1.29(t,J＝7.4Hz,3H).
Example 4: synthesis of 5- [5- [4- (difluoromethoxy) phenyl ] -3-ethylsulfonyl-2-pyridinyl ] -1-methyl-2- (trifluoromethyl) pyrazolo [1,5-a ] pyrimidin-7-one (I-4)
To a stirred solution of 5- (5-bromo-3-ethylsulfonyl-2-pyridinyl) -1-methyl-2- (trifluoromethyl) pyrazolo [1,5-a ] pyrimidin-7-one (0.15 g) in 1, 4-dioxane (2 mL) was added K 2CO3 (0.134 g) and 2- [4- (difluoromethoxy) phenyl ] -4, 5-tetramethyl-1, 3, 2-dioxaborolan (0.09 g), the reaction mixture was degassed under nitrogen for 10min, and then bis (diphenylphosphino) ferrocene ] palladium (II) dichloride (0.019 g) was subsequently added. The reaction mixture was heated to 120 ℃ for 5h. After the reaction was completed, the reaction mixture was concentrated under reduced pressure. The crude product was purified by column chromatography using ethyl acetate and heptane as eluent to give the title compound (0.1 g) as an off-white solid.
1H-NMR(300MHz,DMSO-d6)δ9.36(d,J＝2.2Hz,1H),8.65(d,J＝2.2Hz,1H),8.18-8.02(m,2H),7.62(m,1H),7.52(s,1H),7.3(m,2H),6.46(s,1H),4.40(s,3H),3.96(q,J＝7.4Hz,2H),1.28(q,J＝8.7,8.1Hz,3H).
Example 5: synthesis of 5- (4-bromo-2-ethylsulfonyl-phenyl) -1-methyl-2- (trifluoromethyl) pyrazolo [1,5-a ] pyrimidin-7-one (I-7)
Step 1: synthesis of 1- (4-bromo-2-ethylsulfanyl-phenyl) ethanone
A stirred solution of 1- (4-bromo-2-fluoro-phenyl) ethanone (4.0 g) in anhydrous THF (50 mL) was cooled to 0deg.C and NaSC 2H5 (2.2 g) and a catalytic amount (0.05 g) of 18-crown-6-ether was added. The reaction mixture was stirred at 20 ℃ to 25 ℃ for 16h. After the reaction was completed, the reaction mixture was quenched with saturated aqueous NH 4 Cl (250 mL) and extracted with ethyl acetate (2×500 mL). The organic layer was separated, dried over Na 2SO4, and concentrated under reduced pressure. The crude product was purified by column chromatography using ethyl acetate and heptane as eluent to give the title compound (3.8 g) as an off-white solid.
1H-NMR(300MHz,DMSO-d6)δ7.89(d,J＝8.3Hz,1H),7.53(d,J＝1.9Hz,1H),7.46(dd,J＝8.3,1.9Hz,1H),2.95(q,J＝7.4Hz,3H),2.55(s,3H),1.25(t,J＝7.3Hz,3H).
Step 2: synthesis of ethyl 3- (4-bromo-2-ethylsulfanyl-phenyl) -3-oxo-propionate
A stirred solution of 1- (4-bromo-2-ethylsulfanyl-phenyl) ethanone (3.8 g) in heptane (40 mL) was cooled to 0deg.C, and NaH 60% (1.75 g) was added in portions, and then diethyl carbonate (7.2 mL) was added subsequently. The reaction mixture was heated at 85℃for 6h. After the reaction was completed, the reaction mixture was quenched with ice-cold water (150 mL) and extracted with ethyl acetate (2×250 mL). The organic layer was separated, dried over Na 2SO4, and concentrated under reduced pressure. The crude product was purified by column chromatography using ethyl acetate and heptane as eluent to give the title compound (3 g) as a yellow liquid.
LC/MS (method a): r t：2.42min;m/z＝334(M+2)+
1H-NMR(300MHz,CDCl3)δ7.64(d,J＝8.4Hz,1H),7.51(d,J＝1.8Hz,1H),7.40-7.34(m,1H),4.22(q,J＝7.0Hz,2H),3.99(s,2H),2.96(q,J＝7.5Hz,2H),1.35-1.21(m,3H),0.88(dd,J＝8.1,5.3Hz,3H).
Step 3: the synthesis of 5- (4-bromo-2-ethylsulfanyl-phenyl) -1-methyl-2- (trifluoromethyl) pyrazolo [1,5-a ] pyrimidin-7-one was achieved by previous methods.
LC/MS (method a): r t：2.22min;m/z＝433(M+1)+
1H-NMR(500MHz,DMSO-d6)δ7.57(d,J＝2.5Hz,1H),7.45(d,J＝8.1Hz,1H),7.40(s,1H),7.37(dd,J＝8.3,1.9Hz,1H),6.25(d,J＝2.0Hz,1H),4.32(s,3H),2.99(dd,J＝7.3,1.9Hz,2H),1.19(td,J＝7.4,2.1Hz,3H).
Step 4: synthesis of 5- (4-bromo-2-ethylsulfonyl-phenyl) -1-methyl-2- (trifluoromethyl) pyrazolo [1,5-a ] pyrimidin-7-one (I-7)
A stirred solution of 5- (4-bromo-2-ethylsulfanyl-phenyl) -1-methyl-2- (trifluoromethyl) pyrazolo [1,5-a ] pyrimidin-7-one (1.5 g) in DCM (20 mL) was cooled to 0℃and m-chloroperoxybenzoic acid (1.54 g) was added in portions. The reaction mixture was stirred at 20 ℃ to 25 ℃ for 16h. After the reaction was completed, the reaction mixture was quenched with saturated Na 2S2O3 solution (70 mL) and extracted with ethyl acetate (2×100 mL). The combined organic layers were dried over Na 2SO4 and concentrated under reduced pressure. The crude product was purified by column chromatography using ethyl acetate and heptane as eluent to give the title compound (0.9 g) as an off-white solid.
1H-NMR(500MHz,DMSO-d6)δ8.11(d,J＝2.3Hz,1H),8.06(dd,J＝8.2,2.4Hz,1H),7.57(dd,J＝8.2,2.1Hz,1H),7.45(d,J＝2.0Hz,1H),6.29(d,J＝2.0Hz,1H),4.37(d,J＝1.9Hz,3H),3.80-3.71(m,2H),1.19(td,J＝7.4,2.1Hz,3H).
Example 5: synthesis of 5- (5-bromo-3-ethylsulfonyl-2-pyridinyl) -2-cyclopropyl-1-methyl-pyrazolo [1,5-a ] pyrimidin-7-one (I-10)
Step 1: synthesis of 5-cyclopropyl-1-methyl-pyrazol-3-amine
To a stirred solution of 5-cyclopropyl-1H-pyrazol-3-amine (2 g) in DCM (20 mL) at 0deg.C was added tBuOK (2.7 g) and CH 3 I (0.103 mL) dropwise. The reaction mixture was stirred at 20℃to 25℃for 3h. After the reaction was completed, the reaction mixture was diluted with water (150 mL), and then extracted with ethyl acetate (2×150 mL). The combined organic layers were dried over Na 2SO4 and concentrated under reduced pressure. The crude product was purified by column chromatography using ethyl acetate and heptane as eluent to obtain the title compound (1.5 g) as a brown liquid.
LC/MS (method a): r t：0.789min;m/z＝138(M+1)+
1H-NMR(500MHz,CDCl3)δ5.10(dd,J＝7.0,1.7Hz,1H),3.61(d,J＝1.7Hz,3H),3.49(d,J＝1.8Hz,2H),1.48(s,1H),0.91-0.80(m,2H),0.64-0.47(m,2H).
Step 2: synthesis of 5- (5-bromo-3-ethylsulfanyl-2-pyridyl) -2-cyclopropyl-1-methyl-pyrazolo [1,5-a ] pyrimidin-7-one
PPA (2 mL) was added to a stirred solution of ethyl 3- (5-bromo-3-ethylsulfanyl-2-pyridinyl) -3-oxo-propanoate (0.7 g) and 5-cyclopropyl-1-methyl-pyrazol-3-amine (0.434 g) in 1, 4-dioxane (0.5 mL) at 20℃to 25 ℃. The reaction mixture was heated to 130 ℃ for 5h. After the reaction was completed, the reaction mixture was quenched with 1N NaOH solution (50 mL) and extracted with ethyl acetate (2×75 mL). The combined organic layers were dried over Na 2SO4 and concentrated under reduced pressure. The crude product was purified by column chromatography using ethyl acetate and heptane as eluent to give the title compound (0.5 g) as an off-white solid.
LC/MS (method a): r t：2.16min;m/z＝406(M+1)+
1H-NMR(500MHz,DMSO-d6)δ8.27(d,J＝2.4Hz,1H),7.81(d,J＝2.8Hz,1H),6.06(d,J＝2.1Hz,1H),5.97(d,J＝2.0Hz,1H),4.10(d,J＝2.0Hz,3H),2.76(dd,J＝7.5,1.9Hz,2H),1.78(d,J＝2.1Hz,1H),1.18(t,J＝7.4Hz,3H),1.05-0.82(m,2H),0.78-0.69(m,2H).
Step 3: synthesis of 5- (5-bromo-3-ethylsulfonyl-2-pyridinyl) -2-cyclopropyl-1-methyl-pyrazolo [1,5-a ] pyrimidin-7-one
A stirred solution of 5- (5-bromo-3-ethylsulfanyl-2-pyridyl) -2-cyclopropyl-1-methyl-pyrazolo [1,5-a ] pyrimidin-7-one (0.5 g) in DCM (10 mL) was cooled to 0℃and meta-chloroperoxybenzoic acid (0.54 g) was added. The reaction mixture was stirred at 20 ℃ to 25 ℃ for 16h. After the reaction was completed, the reaction mixture was quenched with saturated Na 2S2O3 solution (70 mL) and extracted with ethyl acetate (2×100 mL). The combined organic layers were dried over Na 2SO4 and concentrated under reduced pressure. The crude product was purified by column chromatography using ethyl acetate and heptane as eluent to give the title compound (0.3 g) as an off-white solid.
1H-NMR(500MHz,DMSO-d6)δ9.09(s,1H),8.51(s,1H),6.31(s,1H),6.09(d,J＝1.8Hz,1H),4.35(s,3H),3.94(q,J＝7.5Hz,2H),2.12(s,1H),1.23(t,J＝7.4Hz,3H),1.15(d,J＝8.0Hz,2H),0.96(d,J＝5.3Hz,2H).
Example 6: synthesis of 5- [ 5-bromo-3- (ethylsulfonylimino) -2-pyridinyl ] -1-methyl-2- (trifluoromethyl) pyrazolo [1,5-a ] pyrimidin-7-one (I-13)
A stirred solution of 5- (5-bromo-3-ethylsulfanyl-2-pyridyl) -1-methyl-2- (trifluoromethyl) pyrazolo [1,5-a ] pyrimidin-7-one (0.12 g) in methanol (50 mL) was cooled to 0℃and ammonium carbamate (0.022 g) and (diacetoxyiodo) benzene (0.089 g) were added. The reaction mixture was stirred at 20℃to 25℃for 2h. After the reaction was completed, the reaction mixture was concentrated under reduced pressure. The crude product was purified by column chromatography using methanol and DCM as eluent to give the title compound (0.09 g) as an off-white solid.
1H-NMR(500MHz,DMSO-d6)δ9.02(s,1H),8.54(s,1H),7.46(s,1H),6.30(s,1H),4.43(s,1H),4.37(s,3H),3.70(q,J＝7.4Hz,2H),1.19(t,J＝7.4Hz,3H).
Example 7: synthesis of 5- (5-bromo-3-ethylsulfonyl-2-pyridinyl) -1, 6-dimethyl-2- (trifluoromethyl) pyrazolo [1,5-a ] pyrimidin-7-one (I-16)
Step 1: synthesis of ethyl 3- (5-bromo-3-ethylsulfanyl-2-pyridyl) -2-methyl-3-oxo-propionate
To a stirred solution of ethyl 3- (5-bromo-3-ethylsulfanyl-2-pyridyl) -3-oxo-propionate (1.2 g) in MeCN (10 mL) at 0 ℃ was added K 2CO3 (0.75 g) and CH 3 I (0.22 mL). The reaction mixture was heated to 50 ℃ for 3h. After the reaction was completed, the reaction mixture was diluted with water (150 mL), and then extracted with ethyl acetate (2×150 mL). The combined organic layers were dried over Na 2SO4 and concentrated under reduced pressure. The crude product was purified by column chromatography using ethyl acetate and heptane as eluent to obtain the title compound (0.9 g) as a brown liquid.
LC/MS (method a): r t：2.54min;m/z＝344(M-2)+
1H-NMR(500MHz,CDCl3)δ8.41(t,J＝1.5Hz,1H),7.80(d,J＝1.9Hz,1H),4.6(t,J＝8.2Hz,1H),4.20(d,J＝7.1Hz,2H),2.94(q,J＝7.4Hz,2H),1.44(t,J＝7.4Hz,6H),1.26(td,J＝7.1,1.0Hz,3H).
Step 2: the synthesis of 5- (5-bromo-3-ethylsulfanyl-2-pyridyl) -1, 6-dimethyl-2- (trifluoromethyl) pyrazolo [1,5-a ] pyrimidin-7-one was accomplished according to the previous method.
LC/MS (method a): r t：2.32min;m/z＝448(M+1)+
1H-NMR(300MHz,DMSO-d6)δ8.60-8.48(m,1H),8.13(d,J＝2.0Hz,1H),7.35(s,1H),4.27(s,3H),3.04(q,J＝7.3Hz,2H),1.18(t,J＝7.2Hz,3H),1.26(td,J＝7.1,1.0Hz,3H).
Step 3: synthesis of 5- (5-bromo-3-ethylsulfonyl-2-pyridinyl) -1, 6-dimethyl-2- (trifluoromethyl) pyrazolo [1,5-a ] pyrimidin-7-one (I-16)
A stirred solution of 5- (5-bromo-3-ethylsulfanyl-2-pyridyl) -1, 6-dimethyl-2- (trifluoromethyl) pyrazolo [1,5-a ] pyrimidin-7-one (0.5 g) in DCM (10 mL) was cooled to 0deg.C and meta-chloroperoxybenzoic acid (0.54 g) was added. The reaction mixture was stirred at 20 ℃ to 25 ℃ for 16h. The progress of the reaction was monitored by TLC. After the reaction was completed, the reaction mixture was quenched with saturated Na 2S2O3 solution (70 mL) and extracted with ethyl acetate (2×100 mL). The combined organic layers were dried over Na 2SO4 and concentrated under reduced pressure. The crude product was purified by column chromatography using ethyl acetate and heptane as eluent to give the title compound (0.1 g) as an off-white solid.
1H-NMR(500MHz,DMSO-d6)δ9.15(s,1H),8.58(s,1H),7.39(s,1H),4.30(s,3H),3.61(d,J＝7.4Hz,2H),1.82(s,3H),1.17(t,J＝7.3Hz,3H).
Additional compound I was obtained using the procedure given in the synthesis instructions, with appropriate changes to the starting materials. The compounds obtained in this way are listed in the following table together with the physical data.
1 H-NMR data for the compounds of Table A:
biological example
If not otherwise stated, the test solution was prepared as follows:
the active compound is dissolved in a desired concentration in a 1:1 (volume: volume) mixture of distilled water and acetone. Test solutions were prepared on the day of use.
The activity of the compounds of formula I of the present invention can be demonstrated and evaluated by the following biological tests.
B.1 green peach aphid (GREEN PEACH APHID) (peach aphid)
For evaluation of control of green peach aphids (myzus persicae) by systematic method, the test unit consisted of 96-well microtiter plates containing liquid artificial feed under artificial membranes.
The compound was formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of the formulated compound were pipetted onto the aphid feed using a custom-made pipette, and repeated twice.
After application, 5-8 adult aphids were placed on the artificial membrane inside the microtiter plate wells. The aphids are then allowed to suck on the treated aphid feed and incubated for 3 days at about 23 ℃ ± 1 ℃ and about 50% ± 5% relative humidity. Aphid mortality and fertility were then assessed visually.
In this test, compounds I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-11, I-14, I-15, I-16 and I-21 showed at least 75% mortality at 2500ppm, respectively, as compared to untreated controls.
B.2 Spodoptera frugiperda (Tobacco budworm) (Spodoptera frugiperda)
For evaluation of control of spodoptera littoralis (spodoptera littoralis), the test unit consisted of 96-well microtiter plates containing insect feed and 15-25 spodoptera littoralis eggs.
The compound was formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of the formulated compound were sprayed onto the insect feed at 10 μl using a custom micro-nebulizer, and repeated twice.
After application, the microtiter plates were incubated at about 28 ℃ ± 1 ℃ and about 80% ± 5% relative humidity for 5 days. Eggs and larval mortality were then assessed visually.
In this test, compounds I-1, I-3, I-4, I-5, I-6, I-8, I-9, I-11, I-14 and I-15 showed at least 75% mortality at 2500ppm, respectively, as compared to untreated controls.
B.3 boll weevil (Boll weevil) (boll weevil)
To evaluate control of bollworm (bollworm), the test unit consisted of a 96-well microtiter plate containing insect feed and 5-10 bollworm eggs.
The compound was formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of the formulated compound were sprayed onto the insect feed at 5 μl using a custom micro-nebulizer, and repeated twice.
After application, the microtiter plates were incubated at about 25 ℃ ± 1 ℃ and about 75% ± 5% relative humidity for 5 days. Eggs and larval mortality were then assessed visually.
In this test, compounds I-1, I-2, I-3, I-4, I-5, I-6, I-8, I-11, I-14, I-15, I-16 and I-21 showed at least 75% mortality at 2500ppm, respectively, as compared to untreated controls.
B.4. subtropical armyworm (Southern armyworm) (subtropical armyworm (Spodoptera eridania)), 2 nd instar larvae
The active compound was formulated into a 10,000-ppm solution supplied as a tube in 100% cyclohexanone by a Tecan liquid processor. The 10,000-ppm solution was serially diluted in 100% cyclohexanone to prepare a transition solution. These were used as stock solutions, which were made into final dilutions by Tecan in 50% acetone: 50% water (v/v) into 10ml or 20ml glass vials. Nonionic surfactant [ ]) Contained in the solution in a volume of 0.01% (v/v). The vials were then inserted into an automated electrostatic sprayer equipped with an atomizing nozzle for application to plants/insects. 2 lima bean plants (variety: sieva) were planted in the pot and selected for treatment at stage 1 true leaves. The test solution was sprayed onto the leaf surfaces by an automatic electrostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in a sprayer fume hood and then removed from the sprayer. Each basin was placed in a perforated plastic bag with a zipper seal. Between 10 and 11 armyworm larvae were placed in bags and the bags were zipper closed. The test plants were kept in the growth chamber at about 25℃and about 20% -40% relative humidity for 4 days, avoiding direct exposure to fluorescence (14:10 bright: dark photoperiod) to prevent heat from stagnating in the bag. Mortality and eating-down were assessed 4 days after treatment compared to untreated control plants.
In this test, compounds I-3, I-4, I-5, I-6, I-7, I-8, I-11, I-14 and I-15 showed at least 75% mortality at 300ppm, respectively, as compared to untreated controls.
B.5 yellow fever mosquito (Yellow fever mosquito) (Aedes aegypti)
To evaluate control of aedes albopictus (aedes aegypti) the test unit consisted of 96-well microtiter plates containing 200 μl of tap water and 5-15 newly hatched aedes aegypti larvae per well.
The active compound was formulated using a solution containing 75% (v/v) water and 25% (v/v) DMSO. Different concentrations of the formulated compound or mixture were sprayed onto the insect feed at 2.5 μl using a custom micro-nebulizer, and repeated twice.
After application, the microtiter plates were incubated at 28 ℃ ± 1 ℃, 80% ± 5% RH for 2 days. Larval mortality was then assessed visually.
In this test, compounds I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-14 and I-15 showed at least 75% mortality at 2500ppm, respectively, as compared to untreated controls.

Claims (14)

1. A compound of formula I and the N-oxides, tautomers, stereoisomers and agriculturally or veterinarily acceptable salts thereof,
Wherein the method comprises the steps of
R 1 is C 1-C6 -alkyl, C 1-C6 -alkoxy, C 2-C6 -alkenyl, C 2-C6 -alkynyl, C 1-C6 -alkoxy-C 1-C4 -alkyl, C 1-C6 -alkoxy-C 1-C4 -alkoxy, C 3-C6 -cycloalkyl, C 3-C6 -cycloalkyl-C 1-C4 -alkyl, or C 3-C6 -cycloalkoxy-C 1-C4 -alkyl, which is unsubstituted or halogenated;
Phenyl or benzyl, wherein the rings are unsubstituted or substituted with R F;
R F is halogen, OH, CN, NO 2、SCN、SF5、C1-C6 alkyl, C 1-C6 alkoxy, C 2-C6 -alkenyl, C 2-C6 alkynyl, C 1-C6 alkoxy-C 1-C4 alkyl, C 1-C6 alkoxy-C 1-C4 alkoxy, C 3-C6 cycloalkyl, C 3-C6 -cycloalkoxy, C 3-C6 cycloalkyl-C 1-C4 alkyl, C 3-C6 -cycloalkoxy-C 1-C4 alkyl, which groups are unsubstituted or substituted by halogen;
R 2 is H, halogen, C 1-C6 -alkyl, C 2-C6 -alkenyl, C 2-C6 -alkynyl, C 1-C6 -alkoxy, C 1-C6 -alkoxy-C 1-C6 -alkyl, C 3-C6 -cycloalkyl, C 3-C6 -cycloalkoxy, C 1-C6 -sulfenyl, C 1-C6 -sulfinyl, or C 1-C6 -sulfonyl, which groups are unsubstituted or halogenated; phenyl or benzyl, wherein the rings are unsubstituted or substituted with R F;
R 3 is H, halogen;
C 1-C6 -alkyl, C 1-C6 -alkoxy, C 3-C6 -cycloalkyl which is unsubstituted or substituted by R F; or alternatively
Phenyl or benzyl, wherein the aromatic ring of the above groups may be unsubstituted or substituted with R F;
g is phenyl or 6 membered heteroaryl;
r 4 is H, halogen, C (CN) R 41R42、C(R44)＝N-OR43、C(R44)＝N-N(R45R46),
C(O)R44、N＝S(O)(R41R42)、N(R43)C(O)R44、N(R43)C(＝N-OR43)R44;OC(CN)R41R42、C1-C6- Alkyl, C 3-C6 -cycloalkyl, C 1-C6 -alkoxy, C 2-C6 -alkenyl, C 2-C6 -alkynyl, phenyl, or six membered heteroaryl, which groups are unsubstituted or substituted by R G;
R G H, halogen, CN, NO 2、C1-C4 -alkyl, C 1-C4 -haloalkyl, C 1-C4 -alkoxy, C 1-C4 -haloalkoxy, N (R 12R13)、S(O)m-C1-C4 -haloalkyl, C 1-C4 -alkylcarbonyl, or C 1-C4 -haloalkylcarbonyl;
Or two radicals R G are bonded to two adjacent atoms to form a 4-to 6-membered carbocyclic or heterocyclic ring which is unsubstituted or partially or fully substituted by R F;
R 41、R42 is independently H, halogen, CN, C 1-C6 -alkyl, C 1-C6 -haloalkyl, C 3-C6 -cycloalkyl, C 1-C4 -alkoxy, C 1-C4 -alkoxy-C 1-C4 -alkyl, S (O) m-C1-C4 -alkyl, C 1-C4 -alkyl-S (O) m-C1-C4 -alkyl, or C 1-C4 -alkoxycarbonyl;
R 41 and R 42 may also form, together with the carbon atom to which they are bound, a C 3-C6 -cycloalkyl group which is unsubstituted or substituted by halogen, C 1-C4 -alkyl, C 1-C4 -haloalkyl, C 1-C4 -alkoxy or C 1-C4 -haloalkoxy;
R 43 is H, C 1-C6 -alkyl, C 2-C6 -alkenyl, C 2-C6 -alkynyl, C 1-C6 -alkoxy-C 1-C4 -alkyl, C 3-C6 -cycloalkyl, C 3-C6 -cycloalkyl-C 1-C4 -alkyl, C 3-C6 -cycloalkoxy-C 1-C4 -alkyl, which groups are unsubstituted or substituted by halogen and/or CN;
phenyl or benzyl, which are unsubstituted or substituted by R F;
R 44 is H, CN, OH, C 1-C6 -alkyl, C 2-C6 -alkenyl, C 2-C6 -alkynyl, C 1-C6 -alkoxy-C 1-C4 -alkyl, C 3-C6 -cycloalkyl, C 3-C6 -cycloalkyl-C 1-C4 -alkyl, C 3-C6 -cycloalkoxy-C 1-C4 -alkyl, which groups are unsubstituted or substituted by halogen;
phenyl or benzyl, which are unsubstituted or substituted by R F;
r 45、R46 is independently H, C 1-C6 -alkyl, C 2-C6 -alkenyl, C 2-C6 -alkynyl, C 1-C6 -alkoxy-C 1-C4 -alkyl, C 3-C6 -cycloalkyl, C 3-C6 -cycloalkyl-C 1-C4 -alkyl, C 3-C6 -cycloalkoxy-C 1-C4 -alkyl, C 1-C6 -alkyl-carbonyl, C 1-C6 -alkoxy-carbonyl, which groups are unsubstituted or substituted by halogen;
phenyl or benzyl, which are unsubstituted or substituted by R F;
NR 45R46 can also form an N-bonded saturated 5-to 8-membered heterocyclic ring which, in addition to nitrogen, can have 1 or 2 further heteroatoms selected from O, S (O) m and N-R ', where R' is H or C 1-C6 -alkyl and the heterocyclic ring is unsubstituted or substituted by halogen, C 1-C4 -alkyl, C 1-C4 -haloalkyl, C 1-C4 -alkoxy or C 1-C4 -haloalkoxy;
A is CH, CR A, or N;
R A is halogen, C 1-C4 -alkyl, C 3-C6 -cycloalkyl, C 1-C6 -haloalkyl, C 1-C6 -halocycloalkyl, OR 43、S(O)m-R43; wherein the ring is unsubstituted or substituted with R 42;
m is 0, 1, or 2;
n is 0, 1, or 2;
y is O or NR Y;
r Y is H or C 1-C4 -alkyl;
R 5 is C 1-C4 -alkyl, C 3-C6 -cycloalkyl, C 3-C6 -cycloalkyl-C 1-C4 -alkyl.
2. A compound of formula I according to claim 1, wherein R 1 is CH 3 or cC 3H5.
3. A compound of formula I according to claim 1 or 2, wherein R 2 is H, C-C 3H5 or CF 3.
4. A compound of formula I according to any one of claims 1 to 3, wherein R 3 is H or phenyl substituted by halogen.
5. A compound of formula I as claimed in any one of claims 1 to 4, wherein,
G is phenyl or pyridyl.
6. A compound of formula I as claimed in any one of claims 1 to 5, wherein,
A is CH, or CR A, wherein R A is C 1-C3 -alkyl or halogen.
7. A compound of formula I according to any one of claims 1 to 6, wherein R 4 is H, halogen, C 1-C4 -alkyl, C 2-C4 -alkenyl, C 2-C4 -alkynyl, which is unsubstituted or substituted by R G; c (CN) R 41R42、N＝S(O)(R41R42), or phenyl, CN, C 1-C4 -alkyl, C 1-C4 -haloalkyl, C 1-C4 -alkoxy, or C 1-C4 -haloalkoxy, which are unsubstituted or substituted by halogen.
8. A compound of formula I according to any one of claims 5 to 7, wherein n is 1 and the attachment of R 4 to the bicyclic backbone is in para-position.
9. An agricultural or veterinary composition comprising at least one compound according to any one of claims 1 to 8 and/or at least one agriculturally or veterinarily acceptable salt thereof, and at least one inert liquid and/or an agriculturally or veterinarily acceptable solid carrier.
10. An agricultural composition for combating animal pests, comprising at least one compound as defined in any one of claims 1 to 8 and at least one inert liquid and/or acceptable solid carrier and, if desired, at least one surfactant.
11. A method for combating or controlling invertebrate pests, which method comprises contacting said pests or their food supply, habitat or breeding grounds with a pesticidally effective amount of at least one compound as defined in any of claims 1 to 8.
12. A method for protecting a growing plant from attack or infestation by invertebrate pests, which method comprises contacting the plant, or the soil or water in which the plant is growing, with a pesticidally effective amount of at least one compound as defined in any of claims 1 to 8.
13. A seed comprising a compound as defined in any one of claims 1 to 8, or an enantiomer, diastereomer or salt thereof, in an amount of 0.1g to 10kg per 100kg of seed.
14. A method for treating or protecting an animal from an invertebrate pest infestation or infection comprising contacting the animal with a pesticidally effective amount of at least one compound of formula I, a stereoisomer thereof and/or at least one veterinarily acceptable salt thereof as defined in any of claims 1 to 8.
CN202280076682.7A 2021-11-19 2022-11-08 Bicyclic compounds for controlling invertebrate pests Pending CN118355017A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP21209300.9 2021-11-19
EP21209301 2021-11-19
EP21209301.7 2021-11-19
PCT/EP2022/081036 WO2023088718A1 (en) 2021-11-19 2022-11-08 Bicyclic compounds for the control of invertebrate pests

Publications (1)

Publication Number Publication Date
CN118355017A true CN118355017A (en) 2024-07-16

Family

ID=78709317

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202280076682.7A Pending CN118355017A (en) 2021-11-19 2022-11-08 Bicyclic compounds for controlling invertebrate pests

Country Status (1)

Country Link
CN (1) CN118355017A (en)

Similar Documents

Publication Publication Date Title
KR100741632B1 (en) Insecticidal Anthranilamides
US20240140917A1 (en) Substituted isoxazoline derivatives
KR20230006482A (en) Imidazo-pyrimidone compounds as pesticides
EP4433479A1 (en) Bicyclic compounds for the control of invertebrate pests
CN118355017A (en) Bicyclic compounds for controlling invertebrate pests
CN112585133A (en) Substituted glutarimide derivatives
CN117957221A (en) Heterocyclic compounds for combating invertebrate pests
CN118871437A (en) Substituted isoxazoline derivatives
US20230180754A1 (en) Heterocyclic compounds for the control of invertebrate pests
CN117642390A (en) Triazole compounds for controlling invertebrate pests
CN117980299A (en) Pyrazine compounds for controlling invertebrate pests
WO2024061665A1 (en) N-(3-(aminomethyl)-phenyl)-5-(4-phenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-amine derivatives and similar compounds as pesticides
WO2024223373A1 (en) Pyrimidine compounds for the control of invertebrate pests
WO2023041422A1 (en) Heterocyclic compounds for the control of invertebrate pests
WO2023110473A1 (en) Heterocyclic compounds for the control of invertebrate pests
WO2023165854A1 (en) Substituted isoxazoline derivatives
JP2024532329A (en) Pyrazine compounds for invertebrate pest control.
WO2024132636A1 (en) Heteroaryl compounds for the control of invertebrate pests
CN117836279A (en) Pyrazine compounds for controlling invertebrate pests
EP4370508A1 (en) Triazole compounds for the control of invertebrate pests
WO2023104564A1 (en) Pyrazine compounds for the control of invertebrate pests
CN116888101A (en) Substituted isoxazoline derivatives
WO2023025602A1 (en) Pyrazine compounds for the control of invertebrate pests
KR20230155452A (en) Tricyclic insecticidal compounds

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication