# US 12,595,266 B2 · Pesticidally active heterocyclic derivatives with sulfur containing substituents

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- Number: US 12,595,266 B2
- Document ID: US12595266B2
- Status: Granted
- Kind: B2
- Application number: 18/043,740
- Filed: 2021-09-01
- Published: 2023-08-24
- Granted: 2026-04-07
- Earliest claimed: 2020-09-02
- Assignees: Syngenta Crop Protection AG
- Applicants: Syngenta Crop Protection AG
- Inventors: Vikas Sikervar; Swarnendu Sasmal; Michel Muehlebach; André Stoller; Daniel Emery; André Jeanguenat; Anke Buchholz; Benedikt Kurtz
- Web page: https://patentgrep.com/patent/US12595266B2

## CPC

- C07D 491/056: with two or more oxygen atoms as ring hetero atoms in the oxygen-containing ring
- A01N 43/40: six-membered rings
- A01N 43/50: 1,3-Diazoles; Hydrogenated 1,3-diazoles
- A01N 43/54: 1,3-Diazines; Hydrogenated 1,3-diazines
- A01N 43/653: 1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- A01N 43/76: 1,3-Oxazoles; Hydrogenated 1,3-oxazoles
- A01N 43/80: five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
- A01N 43/90: having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
- A01N 53/00: Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
- A01P 5/00: Nematocides
- A01P 7/00: Arthropodicides
- A01P 7/04: Insecticides
- C07D 213/73: Unsubstituted amino or imino radicals
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- 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
- A01P: BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS

## Abstract

Compounds of the formula (I) wherein Q is as defined in claim 1. Furthermore, the present invention relates to agrochemical compositions which comprise compounds of formula (I), to preparation of these compositions, and to the use of the compounds or compositions in agriculture or horticulture for combating, preventing or controlling animal pests, including arthropods and in particular insects, molluscs, nematodes or representatives of the order Acarina.

## Claims

### Claim 1

A compound of formula (I):
wherein
Q is a radical selected from the group consisting of formula Qa, Qb and Qc,
wherein the arrow denotes the point of attachment to the nitrogen atom of the tricyclic ring;
and wherein A represents CH or N;
X is S, SO, or SO2;
R1 is C1-C4alkyl, or C3-C6cycloalkyl-C1-C4alkyl;
Q1 is hydrogen, halogen, C1-C6haloalkyl, C3-C6cycloalkyl, C3-C6cycloalkyl monosubstituted by cyano, C1-C6cyanoalkyl, C1-C6cyanoalkoxy, C1-C6haloalkoxy, —N(R3)2, —N(R3)C(═O)R4, —N(R3)CON(R3)2, (oxazolidin-2-one)-3-yl, or 2-pyridyloxy; or
Q1 is a five- to six-membered aromatic or heteroaromatic ring system, linked via a ring carbon atom to the ring which contains the substituent A, said ring system is unsubstituted or is mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylsulfanyl, C1-C4alkylsulfinyl and C1-C4alkylsulfonyl; and said ring system can contain 1, 2 or 3 ring heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, where said ring system may not contain more than one ring oxygen atom and may not contain more than one ring sulfur atom; or
Q1 is a five-membered heteroaromatic ring system linked via a ring nitrogen atom to the ring which contains the substituent A, said ring system is unsubstituted or is mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylsulfanyl, C1-C4alkylsulfinyl and C1-C4alkylsulfonyl; and said ring system contains 1, 2 or 3 ring heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, where said ring system contains at least one ring nitrogen atom and may not contain more than one ring oxygen atom and may not contain more than one ring sulfur atom;
R2 is hydrogen or C1-C4alkyl;
each R3 independently is hydrogen, C1-C4alkyl, C1-C6haloalkyl or C3-C6cycloalkyl;
R5 is C1-C4alkyl;
R6 is hydrogen, halogen, C1-C4alkyl, C1-C6haloalkyl, C3-C6cycloalkyl, C3-C6cycloalkyl monosubstituted by cyano, C1-C6cyanoalkyl, C1-C6alkoxy, C1-C6haloalkoxy, —CO(NR3R4), —NR3COR4, (C3-C5) cycloalkyl-(C1-C6)alkyl-, (C3-C5) cycloalkyl monosubstituted by cyano-(C1-C6)alkyl-; or
R6 is a five- to six-membered saturated, partially saturated, or heteroaromatic ring system, linked via a ring nitrogen atom to the imidazole ring which is connected to the substitutent R5, said ring system is unsubstituted or is mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylsulfanyl, C1-C4alkylsulfinyl and C1-C4alkylsulfonyl; C3-C6cycloalkyl, C3-C6cycloalkyl monosubstituted by cyano, C1-C6cyanoalkyl, (C3-C5) cycloalkyl-(C1-C6)alkyl-, (C3-C5) cycloalkyl monosubstituted by cyano-(C1-C6)alkyl-, and said ring system contains 1, 2 or 3 ring heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, where said ring system contains at least one ring nitrogen atom and may not contain more than one ring oxygen atom and may not contain more than one ring sulfur atom; or R6 is a five- to six-membered saturated, partially saturated, aromatic or heteroaromatic ring system linked via a ring carbon atom to the imidazole ring which is connected to the substitutent R5, said ring system is unsubstituted or is mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylsulfanyl, C1-C4alkylsulfinyl and C1-C4alkylsulfonyl; C3-C6cycloalkyl, C3-C6cycloalkyl monosubstituted by cyano, C1-C6cyanoalkyl, (C3-C5) cycloalkyl-(C1-C6)alkyl-, (C3-C5) cycloalkyl monosubstituted by cyano-(C1-C6)alkyl-, and said ring system can contain 1, 2 or 3 ring heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, where said ring system may not contain more than one ring oxygen atom and may not contain more than one ring sulfur atom; and
R4 is C3-C6cycloalkyl-C1-C4alkyl, C1-C6haloalkyl, C1-C6haloalkoxy or C3-C6cycloalkyl;
or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of a compound of formula I.

### Claim 2 (depends on 1)

A compound of formula I according to claim 1, represented by the compounds of formula I-A1:
wherein A, R1, R2, X, Q1, R3 and R4 are as defined under formula I in claim 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof.

### Claim 3 (depends on 1)

A compound of formula I according to claim 1, represented by the compounds of formula I-A2:
wherein A, R1, R2, X, Q1, R3 and R4 are as defined under formula I in claim 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof.

### Claim 4 (depends on 1)

A compound of formula I according to claim 1, represented by the compounds of formula I-B1:
wherein X, R1, R3, R4, R5 and R6 are as defined under formula I in claim 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof.

### Claim 5 (depends on 1)

A compound according to claim 1,
wherein: X is S or SO2.

### Claim 6 (depends on 1)

A compound according to claim 1,
wherein: R1 is ethyl or cyclopropylmethyl.

### Claim 7 (depends on 1)

A compound according to claim 1, wherein:
Q is Qa;
Q1 is hydrogen, halogen, trifluoromethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, trifluoroethoxy, (oxazolidin-2-one)-3-yl, 2-pyridyloxy, N-linked pyrazolyl which can be mono-substituted by chloro or trifluoromethyl, N-linked triazolyl, C-linked pyrimidinyl, —N(R3)2, —N(R3)COR4, or —N(R3)CON(R3)2, in each of which R3 is independently either hydrogen or methyl and R4 is either methyl, ethyl or cyclopropyl and
R2 is hydrogen or C1-C4alkyl.

### Claim 8 (depends on 1)

A compound according to claim 1, wherein:
Q is Qb;
Q1 is hydrogen, halogen, cyclopropyl, (oxazolidin-2-one)-3-yl, N-linked pyrazolyl which can be mono-substituted by chloro or trifluoromethyl, N-linked triazolyl, C-linked pyrimidinyl, —N(R3)2, —N(R3)COR4, or —N(R3)CON(R3)2, in each of which R3 is independently either hydrogen or methyl and R4 is either methyl, ethyl or cyclopropyl; and
R2 is hydrogen or C1-C4alkyl.

### Claim 9 (depends on 1)

A compound according to claim 1, wherein:
Q is Qc;
R6 is hydrogen, halogen, cyclopropyl, trifluoroethoxy, —CO(NR3R4) or —NR3COR4, in each of which R3 is methyl and R4 is trifluoroethoxy, N-linked pyrazolyl which can be mono-substituted by chloro, cyclopropyl or trifluoromethyl, C-linked pyrimidinyl, C-linked pyrazolyl which can be mono-substituted by cyclopropyl, difluoromethyl, difluoroethyl, cyanocyclopropylmethyl or cyclopropylmethyl, C-linked dihydroisoxazole which can be mono-substituted by chloro, trifluoromethyl or cyclopropyl, phenyl which can be mono-substituted by chloro, fluoro, cylopropyl or cylopropyl mono-substituted with cyano; and
R5 is C1-C4alkyl.

### Claim 10 (depends on 9)

A compound according to claim 9, wherein:
R6 is hydrogen, cyclopropyl, 2,2,2-trifluoroethoxy, —CONCH3(CH2CF3), —N(CH3)COCH2CF3, or a substituent selected from J1 to J12

### Claim 11 (depends on 1)

A compound of formula I according to claim 1, represented by the compounds of formula I-C:
wherein
Q is a radical selected from the group consisting of formula Qa-1, Qb-1 and Qc-1,
wherein the arrow denotes the point of attachment to the nitrogen atom of the tricyclic ring; and wherein
R5 is C1-C6alkyl; and
each of Q1 and R6 are independently selected from the group consisting of cyclopropyl; cyanocyclopropyl; cyanoisopropyl; cyanoisopropoxy; C1-C6haloalkyl; C1-C6haloalkoxy; —N(CH3)COCH3; N-linked triazolyl; C-linked pyrimidinyl; phenyl which can be mono-substituted by cyanocylopropyl; N-linked pyrazolyl which can be mono-substituted by chloro; C-linked pyrazolyl which is N-substituted by cyclopropyl, —CHF2, —CH2CHF2, —CH2CF3, —(CH2)-cyclopropyl, or —(CH2)-cyanocyclopropyl; C-linked dihydroisoxazole which can be mono-substituted by cyclopropyl; and C-linked isoxazole which can be mono-substituted by cyclopropyl.

### Claim 12 (depends on 1)

A compound according to claim 1, wherein:
Q1 is selected from the group consisting of cyclopropyl; 1-cyanocyclopropyl; 1-cyano-1-methyl-ethyl; 1-cyano-1-methyl-ethoxy; trifluoromethyl; 1,1-difluoroethyl; 2,2,2-trifluoroethoxy; 2,2-difluoropropoxy; —N(CH3)COCH3; 1,2,4-triazol-1-yl; pyrimidin-5-yl; pyrimidin-2-yl; 4-(1-cyanocyclopropyl)phenyl; 3-chloro-pyrazol-1-yl; 1-cyclopropylpyrazol-4-yl; 1-difluoromethylpyrazol-4-yl; 1-(2,2-difluoroethyl) pyrazol-4-yl; 1-(2,2,2-trifluoroethyl) pyrazol-4-yl; 1-cyclopropylmethylpyrazol-4-yl; 1-(1-cyanocyclopropylmethyl) pyrazol-4-yl; 3-cyclopropyl-4,5-dihydro-isoxazol-5-yl; and 3-cyclopropyl-isoxazol-5-yl.

### Claim 13 (depends on 1)

A compound according to claim 1, wherein:
R6 is selected from the group consisting of cyclopropyl; 1-cyanocyclopropyl; 1-cyano-1-methyl-ethyl; 1-cyano-1-methyl-ethoxy; trifluoromethyl; 1,1-difluoroethyl; 2,2,2-trifluoroethoxy; 2,2-difluoropropoxy; —N(CH3)COCH3; 1,2,4-triazol-1-yl; pyrimidin-5-yl; pyrimidin-2-yl; 4-(1-cyanocyclopropyl)phenyl; 3-chloro-pyrazol-1-yl; 1-cyclopropylpyrazol-4-yl; 1-difluoromethylpyrazol-4-yl; 1-(2,2-difluoroethyl) pyrazol-4-yl; 1-(2,2,2-trifluoroethyl) pyrazol-4-yl; 1-cyclopropylmethylpyrazol-4-yl; 1-(1-cyanocyclopropylmethyl) pyrazol-4-yl; 3-cyclopropyl-4,5-dihydro-isoxazol-5-yl; 3-cyclopropyl-isoxazol-5-yl; 3-(1-cyanocyclopropyl)phenyl; and 4-chloro-pyrazol-1-yl.

### Claim 14 (depends on 1)

A compound of formula I, according to claim 1, selected from the group consisting of:
1-[6-(2,2-difluoro-7-oxo-5H-[1,3]dioxolo[4,5-f]isoindol-6-yl)-5-ethylsulfonyl-3-pyridyl]cyclopropanecarbonitrile (compound P1);
1-[4-[4-(2,2-difluoro-7-oxo-5H-[1,3]dioxolo[4,5-f]isoindol-6-yl)-5-ethylsulfonyl-1-methyl-imidazol-2-yl]phenyl]cyclopropane-carbonitrile (compound P2);
6-[2-(3-cyclopropyl-4,5-dihydroisoxazol-5-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P3);
6-[2-[1-(2,2-difluoroethyl) pyrazol-4-yl]-5-ethylsulfonyl-1-methyl-imidazol-4-yl]-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P4);
1-[[4-[4-(2,2-difluoro-7-oxo-5H-[1,3]dioxolo[4,5-f]isoindol-6-yl)-5-ethylsulfonyl-1-methyl-imidazol-2-yl]pyrazol-1-yl]methyl]cyclopropanecarbonitrile (compound P5);
6-[5-ethylsulfonyl-1-methyl-2-(2,2,2-trifluoroethoxy) imidazol-4-yl]-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P6);
6-(5-ethylsulfonyl-1-methyl-2-pyrimidin-5-yl-imidazol-4-yl)-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P7);
6-[3-ethylsulfonyl-5-(2,2,2-trifluoroethoxy)-2-pyridyl]-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P8);
6-[2-[1-(cyclopropylmethyl) pyrazol-4-yl]-5-ethylsulfonyl-1-methyl-imidazol-4-yl]-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P9);
6-(6-cyclopropyl-3-ethylsulfonyl-2-pyridyl)-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P10);
6-[3-ethylsulfonyl-6-(1,2,4-triazol-1-yl)-2-pyridyl]-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P11);
6-[5-(2,2-difluoropropoxy)-3-ethylsulfonyl-2-pyridyl]-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P12);
6-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P13);
6-[5-ethylsulfonyl-1-methyl-2-[1-(2,2,2-trifluoroethyl) pyrazol-4-yl]imidazol-4-yl]-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P14);
6-(5-ethylsulfonyl-1-methyl-2-pyrimidin-2-yl-imidazol-4-yl)-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P15);
6-(3-ethylsulfonyl-6-pyrimidin-2-yl-2-pyridyl)-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P16);
6-[2-(1-cyclopropylpyrazol-4-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P17);
N-[6-(2,2-difluoro-7-oxo-5H-[1,3]dioxolo[4,5-f]isoindol-6-yl)-5-ethylsulfonyl-3-pyridyl]-N-methyl-acetamide (compound P18);
6-(5-cyclopropyl-3-ethylsulfonyl-2-pyridyl)-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P19);
6-[2-[1-(difluoromethyl) pyrazol-4-yl]-5-ethylsulfonyl-1-methyl-imidazol-4-yl]-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P20);
6-[2-(3-chloropyrazol-1-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P21);
2-[6-(2,2-difluoro-7-oxo-5H-[1,3]dioxolo[4,5-f]isoindol-6-yl)-5-ethylsulfonyl-3-pyridyl]-2-methyl-propanenitrile (compound P22);
6-[5-(1,1-difluoroethyl)-3-ethylsulfonyl-2-pyridyl]-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P23);
6-(2-cyclopropyl-5-ethylsulfonyl-1-methyl-imidazol-4-yl)-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P24);
2-[[6-(2,2-difluoro-7-oxo-5H-[1,3]dioxolo[4,5-f]isoindol-6-yl)-5-ethylsulfonyl-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P25); and
6-[2-(3-cyclopropylisoxazol-5-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P26).

### Claim 15 (depends on 1)

A composition comprising an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, as defined in claim 1 and, optionally, an auxiliary or diluent.

### Claim 16 (depends on 1)

A method of combating and controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, as defined in claim 1.

### Claim 17 (depends on 15)

A method for the protection of plant propagation material from the attack by insects, acarines, nematodes or molluscs, which comprises treating the propagation material or the site, where the propagation material is planted, with the composition according to claim 15.

### Claim 18

A compound of formula IX-a
wherein
X is S, SO or SO2;
R1 is C1-C4alkyl, or C3-C6cycloalkyl-C1-C4alkyl; and
Q1a is trifluoromethyl, 1,1-difluoroethyl or —N(CH3)COCH3.

### Claim 19

A compounds of formula VI
wherein
LG2 is a leaving group; and
R is C1-C6alkyl, benzyl or phenyl.

### Claim 20 (depends on 1)

A compound according to claim 1, wherein X is SO2, and R1 is ethyl.

### Claim 21 (depends on 1)

A compound according to claim 1, wherein Q is Qa or Qb, and R2 is hydrogen or methyl.

### Claim 22 (depends on 1)

A compound according to claim 1, wherein Q1 is selected from the group consisting of cyclopropyl; 1-cyanocyclopropyl; 1-cyano-1-methyl-ethyl; 1-cyano-1-methyl-ethoxy; trifluoromethyl; 1,1-difluoroethyl; 2,2,2-trifluoroethoxy; 2,2-difluoropropoxy; —N(CH3)COCH3; 1,2,4-triazol-1-yl; 1,2,4-triazol-4-yl; pyrimidin-5-yl; and pyrimidin-2-yl.

### Claim 23 (depends on 19)

The compound of claim 19, wherein
LG2 is bromine or chlorine; and
R is methyl or ethyl.