阅读说明：本技术 双环农药化合物 (Bicyclic pesticidal compounds ) 是由 M·J·麦克劳格林 A·纳里尼 W·冯德恩 B·戈科尔 于 2018-05-07 设计创作，主要内容包括：本发明涉及式(I)化合物,其中各变量如说明书和权利要求书中所给而限定。本发明进一步涉及就化合物I而言的用途、方法和组合物。<Image he="341" wi="700" file="DDA0002242331690000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The present invention relates to compounds of formula (I) wherein the variables are as defined in the description and claims. The invention further relates to uses, methods and compositions for compound I.)

1. Compounds of formula I and the N-oxides, stereoisomers, tautomers and agriculturally or veterinarily acceptable salts thereof:

Wherein

x is O or S;

Rx is selected from C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy-C1-C4 alkyl, C1-C6 alkoxy-C1-C4 alkoxy, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C4 alkyl, C3-C6 cycloalkoxy-C1-C4 alkyl, which is unsubstituted or substituted by halogen,

C (O) -ORa, NRbRc, C1-C6 alkylene-NRbRc, O-C1-C6 alkylene-NRbRc, C1-C6 alkylene-CN, NH-C1-C6 alkylene-NRbRc, C (O) -Rd, SO2NRbRc, S (═ O) mRe, phenyl and benzyl, wherein the phenyl ring is unsubstituted or substituted with a group Rf;

R1 is H, C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkoxy, C1-C6 alkylthio, C1-C6 alkylsulfinyl or C1-C6 alkylsulfonyl, which is unsubstituted or substituted by halogen;

R2, R3 are each independently selected from the group consisting of H, halogen, N3, CN, NO2, -SCN, -SF5, C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, tri-C1-C6 alkylsilyl, C2-C6 alkynyl, C1-C6 alkoxy-C1-C4 alkyl, C1-C6 alkoxy-C1-C4 alkoxy, C3-C6 cycloalkyl, C3-C6 cycloalkoxy, C3-C6 cycloalkyl-C1-C4 alkyl, C3-C6 cycloalkoxy-C1-C4 alkyl, which is unsubstituted or substituted by halogen,

C (O) -ORa, NRbRc, C1-C6 alkylene-NRbRc, O-C1-C6 alkylene-NRbRc, C1-C6 alkylene-CN, NH-C1-C6 alkylene-NRbRc, C (O) -Rd, SO2NRbRc and S (═ O) mRe, one of which may also be phenyl, phenoxy, phenylcarbonyl, phenylthio or benzyl, wherein the phenyl ring is unsubstituted or substituted by a group Rf;

ar is phenyl or 5-or 6-membered heteroaryl,

RAr is independently from each other selected from halogen, N3, OH, CN, NO2, -SCN, -SF5, C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, tri C1-C6 alkylsilyl, C2-C6 alkynyl, C1-C6 alkoxy-C1-C4 alkyl, C1-C6 alkoxy-C1-C4 alkoxy, C3-C6 cycloalkyl, C3-C6 cycloalkoxy, C3-C6 cycloalkyl-C1-C4 alkyl, C3-C6 cycloalkoxy-C1-C4 alkyl, which is unsubstituted or substituted by halogen,

c (O) -ORa, NRbRc, C1-C6 alkylene-NRbRc, O-C1-C6 alkylene-NRbRc, C1-C6 alkylene-CN, NH-C1-C6 alkylene-NRbRc, C (O) -Rd, SO2NRbRc and S (═ O) mRe, one of which may also be phenyl, phenoxy, phenylcarbonyl, phenylthio or benzyl, wherein the phenyl ring is unsubstituted or substituted by a group Rf;

Het is a 5-or 6-membered heteroaryl or a 5-or 6-membered heterocyclyl, unsubstituted or substituted by R;

R is halogen, oxo (═ O), N3, OH, CN, NO2, SCN, SF5, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy-C1-C4 alkyl, C1-C6 alkoxy-C1-C4 alkoxy, C1-C6 alkoxycarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkoxy, C3-C6 cycloalkyl-C1-C4 alkyl, C3-C6 cycloalkoxy-C1-C4 alkyl, phenyl, 5-or 6-membered heteroaryl, or 5-or 6-membered heterocyclyl, wherein the cyclic group of R is unsubstituted or substituted by an Rf group;

provided that neither RAr nor Het are present on the same atom of Ar;

Ra are each selected from H, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy-C1-C4 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C4 alkyl, C3-C6 cycloalkoxy-C1-C4 alkyl, which is unsubstituted or substituted by halogen, C1-C6 alkylene-NRbRc, C1-C6 alkylene-CN, phenyl and benzyl, wherein the phenyl ring is unsubstituted or substituted by a group Rf;

Rb are each selected from H, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy-C1-C4 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C4 alkyl, C3-C6 cycloalkoxy-C1-C4 alkyl, unsubstituted OR substituted by halogen, - (C ═ O) R, -C (═ O) OR and-C (═ O) NR, C1-C6 alkylene-CN, phenyl and benzyl, wherein phenyl is unsubstituted OR substituted by a group Rf;

rc are each selected from H, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy-C1-C4 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C4 alkyl, C3-C6 cycloalkoxy-C1-C4 alkyl, which is unsubstituted or substituted by halogen,

C1-C6 alkylene-CN, phenyl and benzyl, wherein the phenyl ring is unsubstituted or substituted by a group Rf;

the moieties NRbRc may also each form an N-bonded saturated 3-8 membered heterocyclic ring which may have, in addition to the nitrogen atom, 1 or 2 further heteroatoms or heteroatom moieties selected from O, S (═ O) m and N-R ', wherein R' is H or C1-C6 alkyl, and wherein the N-bonded heterocyclic ring is unsubstituted or substituted by a group selected from halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy and C1-C4 haloalkoxy;

rd are each selected from H, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy-C1-C4 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C4 alkyl, C3-C6 cycloalkoxy-C1-C4 alkyl, which is unsubstituted or substituted by halogen,

Phenyl and benzyl, wherein the phenyl ring is unsubstituted or substituted by a group Rf;

Re is independently selected from C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C4 alkyl,

Which is unsubstituted or substituted by halogen,

Phenyl and benzyl, wherein the phenyl ring is unsubstituted or substituted by a group Rf;

Rf is independently selected from halogen, N3, OH, CN, NO2, SCN, SF5, C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy-C1-C4 alkyl, C1-C6 alkoxy-C1-C4 alkoxy, C3-C6 cycloalkyl, C3-C6 cycloalkoxy, C3-C6 cycloalkyl-C1-C4 alkyl, C3-C6 cycloalkoxy-C1-C4 alkyl, which is unsubstituted or substituted with halogen;

m is 0,1 or 2;

n is 0,1 or 2.

2. compounds of formula I according to claim 1, wherein X is O.

3. a compound of formula I according to claim 1 or 2, wherein Het is selected from thienyl, oxazolidinyl, imidazolidinyl, pyrrolidinyl, piperidinyl, pyridinyl, oxazolyl, thiazolyl, pyrazolyl, imidazolyl, triazolyl, oxadiazolyl, tetrazolyl and thiadiazolyl, wherein Het is unsubstituted or substituted with R selected from halo, oxo (═ O), C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 alkoxy-C1-C4 alkyl, C1-C6 alkoxy-C1-C4 alkoxy and C1-C6 alkoxycarbonyl.

4.A compound of formula I according to any one of the preceding claims, wherein

Rx is selected from C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl and C1-C6 haloalkyl;

R1 is selected from the group consisting of partially or fully halogenated C1-C6 alkyl, C1-C6 alkylthio, C1-C6 alkylsulfinyl, and C1-C6 alkylsulfonyl;

r2 is selected from H, halogen, C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C3-C6 cycloalkyl and C3-C6 cycloalkoxy;

R3 is selected from H, halogen, C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C3-C6 cycloalkyl and C3-C6 cycloalkoxy;

Ar is phenyl or 5-or 6-membered heteroaryl;

n is 1 or 2;

RAr is selected from halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, S (═ O) mRe, phenyl, phenoxy, phenylcarbonyl, phenylthio and benzyl, wherein the phenyl ring is unsubstituted or substituted with a group Rf;

Re is selected from C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 haloalkyl, and C3-C6 halocycloalkyl;

Rf is selected from halogen, C1-C6 alkyl, C1-C6 alkoxy, C3-C6 cycloalkyl, C2-C6 alkenyl, and C2-C6 alkynyl, unsubstituted or substituted with halogen;

m is 0,1 or 2.

5. a compound of formula I according to any one of the preceding claims, wherein Ar is a 5-or 6-membered heteroaryl group containing one heteroatom selected from O, N and S.

6.A compound of formula I according to any one of the preceding claims, wherein

rx is C1-C6 alkyl;

R1 is selected from the group consisting of partially or fully halogenated C1-C6 alkyl, C1-C6 alkylthio, C1-C6 alkylsulfinyl, and C1-C6 alkylsulfonyl;

r2 is selected from H, halogen and C1-C6 alkyl;

R3 is selected from H, halogen and C1-C6 alkyl;

Ar is pyridyl or thienyl, which is substituted with RAr as S (═ O) mRe ortho to the bond linking the 9-membered heteroaryl group of the compound of formula I, and optionally further substituted with 1 RAr selected from halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, phenyl and benzyl, wherein the phenyl ring of RAr is unsubstituted or substituted with a group Rf;

re is selected from C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 haloalkyl, and C3-C6 halocycloalkyl;

Rf is selected from halogen, C1-C6 alkyl, C1-C6 alkoxy, C3-C6 cycloalkyl, C2-C6 alkenyl, and C2-C6 alkynyl, unsubstituted or substituted with halogen;

m is 0,1 or 2;

Het is selected from thienyl, oxazolidinyl, imidazolidinyl, pyrrolidinyl, piperidinyl, pyridinyl, oxazolyl, thiazolyl, pyrazolyl, imidazolyl, triazolyl, oxadiazolyl and thiadiazolyl;

Wherein Het is unsubstituted or substituted by R;

r is selected from halogen, oxo (═ O), C1-C6 haloalkyl, C1-C6 alkoxy and C1-C6 alkoxycarbonyl.

7. A compound of formula I according to any one of the preceding claims, which corresponds to a compound of formula I-a:

wherein a circle in a ring containing Q indicates that the ring is an aromatic ring;

Q is S or N;

Rx is C1-C6 alkyl;

r1 is selected from the group consisting of partially or fully halogenated C1-C6 alkyl, C1-C6 alkylthio, C1-C6 alkylsulfinyl, and C1-C6 alkylsulfonyl;

RAr is S (═ O) mRe; wherein

Re is C1-C6 alkyl;

Het is selected from thienyl, oxazolidinyl, imidazolidinyl, pyrrolidinyl, piperidinyl, pyridinyl, oxazolyl, thiazolyl, pyrazolyl, imidazolyl, triazolyl, oxadiazolyl and thiadiazolyl;

Wherein Het is unsubstituted or substituted by R;

R is selected from halo, oxo (═ O), C1-C6 haloalkyl, C1-C6 alkoxy, and C1-C6 alkoxycarbonyl;

m is 0,1 or 2;

o is 1 or 2.

8. compounds of formula I according to any one of claims 1 to 6, wherein

X is O;

R1 is partially or fully halogenated C1-C6 alkyl;

rx is C1-C6 alkyl;

r2 is H;

R3 is H or C1-C6 alkyl;

het is selected from thienyl, pyrrolidinyl, piperidinyl, pyrazolyl, pyridinyl, triazolyl and tetrazolyl;

Wherein Het is unsubstituted or substituted by R;

r is selected from halo, oxo (═ O), and C1-C6 haloalkyl;

Ar is pyridyl, substituted with RAr as S (═ O) mRe ortho to the bond linking the 9-membered heteroaryl group of the compound of formula I;

Re is C1-C6 alkyl.

9.A composition comprising at least one compound of the formula I as defined in any one of claims 1 to 8 and the N-oxides or the agriculturally acceptable salts thereof.

10. A composition according to claim 9, additionally comprising another active substance.

11. a method for controlling or combating invertebrate pests, which method comprises contacting the pests or their food supply, habitat or breeding grounds with a pesticidally effective amount of at least one compound of the formula I according to any of claims 1 to 8 or a composition according to claim 9 or 10.

12.a method for protecting growing plants from attack or infestation by invertebrate pests, which method comprises contacting the plants or the soil or water in which the plants are growing with a pesticidally effective amount of at least one compound of the formula I according to any of claims 1 to 8 or a composition according to claim 9 or 10.

13. Seed comprising a compound of formula I as defined in any one of claims 1 to 8 or an enantiomer, diastereomer or salt thereof or a composition as defined in claim 9 or 10 in an amount of 0.1g to 10kg per 100kg of seed.

14. The use of compounds of the formula I as defined in any of claims 1 to 8 and their agriculturally acceptable salts or of compositions as defined in claims 9 or 10 for protecting growing plants from attack or infestation by invertebrate pests.

15. A method for treating or protecting animals against infestation or infection by invertebrate pests, which comprises contacting the animals with a pesticidally effective amount of at least one compound of the formula I as defined in any of claims 1 to 8, a stereoisomer thereof and/or at least one veterinarily acceptable salt thereof.

examples

The invention will now be described in more detail by the following examples without imposing any limitation thereon.

Other compounds of formula I were obtained using the procedures described in the examples below with appropriate modifications of the starting materials. The compounds obtained in this way are listed in the table below, together with the physical data.

LC/MS method:

a machine: shimadzu Nexera UHPLC + Shimadzu LCMS 20-20, ESI

column: phenomenex Kinetex 1,7 μm XB-C18100A, 50X 2,1mm "

The method comprises the following steps:

mobile phase: a: water +0, 1% TFA; b: ACN

temperature: 60 deg.C

Gradient: 5% B to 100% B within 1,50 min; 100% B0, 25min

Flow rate: 0,8ml/min to 1,0ml/min within 1,51min

The MS method comprises the following steps: ESI positive

Mass range (m/z): 100-700