# US 10,869,477 B2 · Insecticidal compounds

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- Number: US 10,869,477 B2
- Document ID: US10869477B2
- Status: Granted
- Kind: B2
- Application number: 15/888,289
- Filed: 2018-02-05
- Published: 2018-06-07
- Granted: 2020-12-22
- Earliest claimed: 2011-05-31
- Assignees: Syngenta Participations AG
- Applicants: Syngenta Participations AG
- Inventors: Jerome Yves Cassayre; Peter Renold; Myriem El Qacemi; Thomas Pitterna; Julie Clementine Toueg
- Web page: https://patentgrep.com/patent/US10869477B2

## CPC

- A01N 43/80: five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
- A61P 33/14: Ectoparasiticides, e.g. scabicides
- C07D 261/02: not condensed with other rings
- C07D 327/02: one oxygen atom and one sulfur atom
- C07D 411/12: linked by a chain containing hetero atoms as chain links
- C07D 413/12: linked by a chain containing hetero atoms as chain links
- C07D 413/14: containing three or more hetero rings
- A01N: PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF (preservation of food or foodstuff A23); BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES (preparations for medical, dental or toiletry purposes which kill or prevent the growth or proliferation of unwanted organisms A61K); PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A61P: SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)

## Abstract

The present invention provides compounds of formula (I): wherein A1, A2, A3 and A4 are independently of one another C—H, C—R5, or nitrogen; B1-B2-B3-B4 is —CH2—C═N—CH2—, —CH2—N—CH2—CH2—, —CH2—C═CH—O— or —CH═C—CH2—O—; G1 is oxygen or sulfur; L is a single bond or C1-C8alkylene; R1 is hydrogen, C1-C8alkyl, C1-C8alkylcarbonyl-, C1-C8alkoxy, C2-C8alkenyl, C2-C8alkynyl, C1-C8alkoxy-C1-C8alkyl, aryl or aryl substituted by one to three R6, or R1 is heterocyclyl or heterocyclyl substituted by one to three R6 or C1-C8alkoxycarbonyl-; R2 is hydrogen, C1-C8haloalkyl or C1-C8alkyl; R3 is C1-C8haloalkyl; R4 is aryl or aryl substituted by one to three R6, or R4 is heterocyclyl or heterocyclyl substituted by one to three R6; Y1 is CR7R8, C—O or C═S; Y2, Y3 and Y4 are independently CR7R8, C═O, C═S, N—R9, O, S, SO or SO2; wherein at least two adjacent ring atoms in the ring formed by Y1, Y2, Y3 and Y4 are heteroatoms; each R7 and R8 is independently hydrogen, halogen, C1-C8alkyl, or C1-C8haloalkyl; and R5, R6, R7, R8 and R9 are as defined in the claims. The invention also relates to processes and intermediates for preparing these compounds, to insecticidal, acaricidal, nematicidal and molluscicidal compositions comprising these compounds and to methods of using these compounds to control insect, acarine, nematode and mollusc pests.

## Claims

### Claim 1

A compound of formula (I)
wherein
A2, A3, and A4 are independently C—H or N, wherein no more than one of A2, A3, and A4 is N;
B1-B2-B3-B4 is —CH2—C═N—CH2— or —CH2—N—CH2—CH2—;
R5 is hydrogen, halogen, C1-C4alkyl, C3-C4cycloalkyl, C2-C4alkenyl or C1-C4haloalkyl;
each R6 is independently hydrogen, halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, or C1-C4haloalkoxy;
Y1 is C═O, Y2 is N—R9, Y3 is O, and Y4 is CH2; or
Y1 is CH2, Y2 is S═O, Y3 is O, and Y4 is CH2; and
each R9 is independently hydrogen, cyano, cyano-C1-C4alkyl, C1-C4alkyl, C1-C4haloalkyl, C3-C8cycloalkyl, C3-C8cycloalkyl where one carbon atom is replaced by O, S, S(O) or SO2, or C3-C8cycloalkyl-C1-C4alkyl, C3-C8cycloalkyl-C1-C4alkyl where one carbon atom in the cycloalkyl group is replaced by O, S, S(O) or SO2, or C3-C8cycloalkyl-C1-C4haloalkyl, C1-C4hydroxyalkyl, C1-C4alkoxy-C1-C4alkyl, C2-C6alkenyl, C2-C4haloalkenyl, C2-C4alkynyl, C2-C4haloalkynyl, phenyl, phenyl substituted by one to three R10, heteroaryl, heteroaryl substituted by one to three R10, phenyl-C1-C4alkyl, phenyl-C1-C4alkyl wherein the phenyl moiety is substituted by one to three R10, heteroaryl-C1-C4alkyl or heteroaryl-C1-C4alkyl wherein the heteroaryl moiety is substituted by one to three R10, or C1-C4alkyl-(C1-C4alkyl-O—N═)C—CH2—;
each R10 is independently halogen, cyano, nitro, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, or C1-C4haloalkoxy, or a salt or N-oxide thereof.

### Claim 2 (depends on 1)

The compound according to claim 1, wherein B1-B2-B3-B4 is —CH2—C═N—CH2—.

### Claim 3 (depends on 1)

The compound according to claim 1, wherein B1-B2-B3-B4 is —CH2—N—CH2—CH2—.

### Claim 4 (depends on 1)

The compound according to claim 1, wherein each R5 independently is bromo, chloro, fluoro, cyclopropyl, trifluoromethyl, vinyl, or methyl.

### Claim 5 (depends on 1)

The compound according to claim 1, wherein each R9 is independently hydrogen, cyano-C1-C4alkyl, C1-C4alkyl, C3-C8cycloalkyl, C3-C8cycloalkyl where one carbon atom in the cycloalkyl group is replaced by O, S, S(O) or SO2, or C1-C4haloalkyl, C1-C4hydroxyalkyl, C2-C4alkenyl, C2-C4alkynyl, phenyl-C1-C4alkyl or phenyl-C1-C4alkyl wherein the phenyl moiety is substituted by one to three R10, 5-6 membered heteroaryl-C1-C4alkyl or 5-6 membered heteroaryl-C1-C4alkyl wherein the heteroaryl moiety is substituted by one to three R10, and wherein the heteroaryl is pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, pyrazolyl, furanyl, thiophenyl, oxazolyl, isoxazolyl or thiazolyl.

### Claim 6 (depends on 1)

The compound according to claim 1, wherein each R9 is independently hydrogen, C1-C4alkyl, C3-C6cycloalkyl, C1-C4haloalkyl, C1-C4hydroxyalkyl, C1-C4alkoxy-C1-C4alkyl, phenyl- or phenyl-CH2— wherein the phenyl moiety is substituted by one to three R10, furanyl or furanyl substituted by one to three R10, thietanyl, oxetanyl, oxo-thietanyl, or dioxo-thietanyl.

### Claim 7 (depends on 1)

A method of combating and/or controlling an invertebrate animal pest which comprises applying to the pest, to a locus of the pest, or to a plant susceptible to attack by the pest a pesticidally effective amount of a compound of formula (I) as defined in claim 1.

### Claim 8 (depends on 1)

A composition comprising a pesticidally effective amount of a compound of formula (I) as defined in claim 1 optionally comprising an additional pesticidally active ingredient.

### Claim 9 (depends on 1)

A combination product comprising a pesticidally effective amount of a component A and a pesticidally effective amount of component B, wherein component A is a compound of formula (I) as defined in claim 1, and component B is imidacloprid, enrofloxacin, praziquantel, pyrantel embonate, febantel, penethamate, moloxicam, cefalexin, kanamycin, pimobendan, clenbuterol, fipronil, ivermectin, omeprazole, tiamulin, benazepril, milbemycin, cyromazine, thiamethoxam, pyriprole, deltamethrin, cefquinome, florfenicol, buserelin, cefovecin, tulathromycin, ceftiour, selamectin, carprofen, metaflumizone, moxidectin, methoprene (including S-methoprene), clorsulon, pyrantel, amitraz, triclabendazole, avermectin, abamectin, emamectin, eprinomectin, doramectin, selamectin, nemadectin, albendazole, cambendazole, fenbendazole, flubendazole, mebendazole, oxfendazole, oxibendazole, parbendazole, tetramisole, levamisole, pyrantel pamoate, oxantel, morantel, triclabendazole, epsiprantel, fipronil, lufenuron, ecdysone or tebufenozide.

### Claim 10 (depends on 1)

The compound of claim 1, wherein the compound of formula (I) is selected from:

### Claim 11 (depends on 1)

The compound of claim 1, wherein the compound of formula (I) is selected from:

### Claim 12

A compound of formula (I)
wherein
A2, A3, and A4 are independently C—H or N, wherein no more than one of A2, A3, and A4 is N;
B1-B2-B3-B4 is —CH2—C═CH—O— or —CH═C—CH2—O—;
R5 is hydrogen, halogen, nitro, C1-C4alkyl, C3-C4cycloalkyl, C2-C4alkenyl or C1-C4haloalkyl;
each R6 is independently hydrogen, halogen, cyano, nitro, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, or C1-C4haloalkoxy;
Y1 is C═O, Y2 is N—R9, Y3 is O, and Y4 is CH2; or
Y1 is CH2, Y2 is S═O, Y3 is O, and Y4 is CH2; and
each R9 is independently hydrogen, cyano, cyano-C1-C4alkyl, C1-C4alkyl, C1-C4haloalkyl, C3-C8cycloalkyl, C3-C8cycloalkyl where one carbon atom is replaced by O, S, S(O) or SO2, or C3-C8cycloalkyl-C1-C4alkyl, C3-C8cycloalkyl-C1-C4alkyl where one carbon atom in the cycloalkyl group is replaced by O, S, S(O) or SO2, or C3-C8cycloalkyl-C1-C4haloalkyl, C1-C4hydroxyalkyl, C1-C4alkoxy-C1-C4alkyl, C2-C4alkenyl, C2-C4haloalkenyl, C2-C4alkynyl, C2-C4haloalkynyl, phenyl, phenyl substituted by one to three R10, heteroaryl, heteroaryl substituted by one to three R10, phenyl-C1-C4alkyl, phenyl-C1-C4alkyl wherein the phenyl moiety is substituted by one to three R10, heteroaryl-C1-C4alkyl or heteroaryl-C1-C4alkyl wherein the heteroaryl moiety is substituted by one to three R10, or C1-C4alkyl-(C1-C4alkyl-O—N═)C—CH2—;
each R10 is independently halogen, cyano, nitro, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, or C1-C4haloalkoxy, or a salt or N-oxide thereof providing that Y1-Y2-Y3-Y4 is not —CH2—O—N(Ra)—C(═O)—, wherein Ra is hydrogen, methyl, ethyl, propyl, isopropyl, butyl, cyclopropyl, cyclopropyl-methyl, cyclobutyl, cyclobutyl-methyl, oxetanyl, thietanyl, trifluoroethyl, difluoroethyl, allyl, propargyl, cyanomethyl, benzyl, benzyl substituted by one to three Rb, or Ra is pyridyl-methyl- or pyridyl-methyl-substituted by one to three Rb; and each Rb is independently fluoro, chloro, bromo, trifluoromethyl, trifluoromethoxy, cyano or methoxy.

### Claim 13 (depends on 12)

The compound according to claim 12, wherein B1-B2-B3-B4 is —CH2—C═CH—O—.

### Claim 14 (depends on 13)

The compound according to claim 13, wherein B1-B2-B3-B4 is —CH═C—CH2—O—.

### Claim 15 (depends on 12)

The compound according to claim 12, wherein each R5 independently is bromo, chloro, fluoro, cyclopropyl, trifluoromethyl, vinyl, or methyl.

### Claim 16 (depends on 12)

The compound according to claim 12, wherein each R9 is independently hydrogen, cyano-C1-C4alkyl, C1-C4alkyl, C3-C8cycloalkyl, C3-C8cycloalkyl where one carbon atom in the cycloalkyl group is replaced by O, S, S(O) or SO2, or C1-C4haloalkyl, C1-C4hydroxyalkyl, C2-C4alkenyl, C2-C4alkynyl, phenyl-C1-C4alkyl or phenyl-C1-C4alkyl wherein the phenyl moiety is substituted by one to three R10, 5-6 membered heteroaryl-C1-C4alkyl or 5-6 membered heteroaryl-C1-C4alkyl wherein the heteroaryl moiety is substituted by one to three R10, and wherein the heteroaryl is pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, pyrazolyl, furanyl, thiophenyl, oxazolyl, isoxazolyl or thiazolyl.

### Claim 17 (depends on 12)

The compound according to claim 12, wherein each R9 is independently hydrogen, C1-C4alkyl, C3-C6cycloalkyl, C1-C4haloalkyl, C1-C4hydroxyalkyl, C1-C4alkoxy-C1-C4alkyl, phenyl- or phenyl-CH2— wherein the phenyl moiety is substituted by one to three R10, furanyl or furanyl substituted by one to three R10, thietanyl, oxetanyl, oxo-thietanyl, or dioxo-thietanyl.

### Claim 18 (depends on 12)

A method of combating and/or controlling an invertebrate animal pest which comprises applying to the pest, to a locus of the pest, or to a plant susceptible to attack by the pest a pesticidally effective amount of a compound of formula (I) as defined in claim 12.

### Claim 19 (depends on 12)

A composition comprising a pesticidally effective amount of a compound of formula (I) as defined in claim 12 optionally comprising an additional pesticidally active ingredient.

### Claim 20 (depends on 12)

A combination product comprising a pesticidally effective amount of a component A and a pesticidally effective amount of component B, wherein component A is a compound of formula (I) as defined in claim 12, and component B is imidacloprid, enrofloxacin, praziquantel, pyrantel embonate, febantel, penethamate, moloxicam, cefalexin, kanamycin, pimobendan, clenbuterol, fipronil, ivermectin, omeprazole, tiamulin, benazepril, milbemycin, cyromazine, thiamethoxam, pyriprole, deltamethrin, cefquinome, florfenicol, buserelin, cefovecin, tulathromycin, ceftiour, selamectin, carprofen, metaflumizone, moxidectin, methoprene (including S-methoprene), clorsulon, pyrantel, amitraz, triclabendazole, avermectin, abamectin, emamectin, eprinomectin, doramectin, selamectin, nemadectin, albendazole, cambendazole, fenbendazole, flubendazole, mebendazole, oxfendazole, oxibendazole, parbendazole, tetramisole, levamisole, pyrantel pamoate, oxantel, morantel, triclabendazole, epsiprantel, fipronil, lufenuron, ecdysone or tebufenozide.

### Claim 21 (depends on 12)

The compound of claim 12, wherein the compound of formula (I) is selected from: