阅读说明：本技术 具有杀虫活性的芳(杂)环醚类化合物及其制备方法和用途 (Aromatic (hetero) cyclic ether compound with insecticidal activity and preparation method and application thereof ) 是由 李忠 董建生 徐晓勇 郭建法 王正荣 李鹏涛 于 2019-02-02 设计创作，主要内容包括：本发明公开了一种具有杀虫活性的芳(杂)环醚类化合物,或其光学异构体、顺反异构体或农药学上可接受的盐。本发明还公开了包含上述化合物的农用组合物。本发明的化合物结构新颖、具有良好的杀虫杀卵活性,并且具有高效、低毒和环境相容性好等优点。<Image he="154" wi="700" file="DDA0001967140150000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention discloses an aromatic (hetero) cyclic ether compound with insecticidal activity, or an optical isomer, a cis-trans isomer or an agriculturally and pharmaceutically acceptable salt thereof. The invention also discloses an agricultural composition containing the compound. The compound has the advantages of novel structure, good insecticidal and ovicidal activity, high efficiency, low toxicity, good environmental compatibility and the like.)

1. A compound having a structure represented by general formula (I) or an optical isomer, cis-trans isomer or agriculturally pharmaceutically acceptable salt thereof:

in the formula:

ring α is a substituted or unsubstituted phenyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted 5-or 6-membered heterocyclyl, or a substituted or unsubstituted 8-to 12-membered heterobicyclic heteroaryl;

ring β is a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted 5-or 6-membered heterocyclylene group, or a substituted or unsubstituted 8-to 12-membered heteroarylenedicyclic group;

ring γ is a substituted or unsubstituted naphthyl group, a substituted or unsubstituted 5-or 6-membered heterocyclic group, or a substituted or unsubstituted 8-to 12-membered heteroaromatic bicyclic group;

the substituents of the ring α, the ring β and the ring gamma are selected from the group consisting of halogen, cyano, nitro, hydroxyl and substituted or unsubstituted C_1-6Alkyl or alkoxy, substituted or unsubstituted C_2-6Alkenyl, substituted or unsubstituted C_2-6Alkynyl, or substituted or unsubstituted C_3-7Cycloalkyl, substituted or unsubstituted C_5-7A cycloalkenyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted 5-or 6-membered heterocyclyl group, or a substituted or unsubstituted 8-to 12-membered heteroaryl bicyclic group;

L₁、L₃may be the same or different and each is independently selected from the group consisting of: -NR' -, -O-, -S-;

L₂is a group selected from: -CR 'R "-, R' R" may be the same or different;

n is an integer of 1 to 8; preferably an integer of 1 to 5; more preferably an integer of 1 to 3; most preferably 1;

g is a substituent independently located at any one or more (preferably 1 to 3) positions of ring γ, and G is selected from the group consisting of: halogen, cyano, nitro, hydroxy, substituted or unsubstituted C_1-6Alkoxy, substituted or unsubstituted C_1-6Alkyl, substituted or unsubstituted C_2-6Alkenyl, substituted or unsubstituted C_2-6Alkynyl, or substituted or unsubstituted C_3-7Cycloalkyl, substituted or unsubstituted C_5-7Cycloalkenyl group, trimethylsilylethynyl group,Substituted OR unsubstituted phenyl, substituted OR unsubstituted naphthyl, substituted OR unsubstituted 5-OR 6-membered heterocyclyl, substituted OR unsubstituted 8-to 12-membered heteroaromatic bicyclic ring system, OR ', Si (R')₃、NR’R”、C(O)R’、C(O)OR’、C(O)NR’R”、SR’、S(O)_nR’、S(O)₂NR’R”、OC(O)R’、OC(O)NR’R”、OS(O)₂R’、OS(O)₂NR’R”、N(R”)C(O)R’、NCH₂R’、N(R”)C(O)NR’R”、N(R”)S(O)₂R 'or N (R') S (O)₂NR’R”；

The substitution refers to substitution by one or more groups selected from the following group: halogen, cyano, nitro, C_1-6Alkyl radical, C_1-6Alkoxy radical, C_1-6Haloalkyl, C_2-6Alkenyl radical, C_2-6Haloalkenyl, C_2-6Alkynyl, C_2-6Halogenated alkynyl, hydroxy C_1-4Alkyl, R ', OR ', Si (R ')₃、NR’R”、C(O)R’、C(O)OR’、C(O)NR’R”、SR’、S(O)_mR’、S(O)₂NR’R”、OC(O)R、OC(O)NR’R”、OS(O)₂R’、OS(O)₂NR’R”、N(R’)C(O)R’、N(R’)C(O)NR’R”、N(R’)S(O)₂R 'or N (R') S (O)₂NR' R ", or substituted or unsubstituted C_3-7Cycloalkyl, substituted or unsubstituted C_5-7A cycloalkenyl group, a substituted or unsubstituted 6-10 membered aryl group, a substituted or unsubstituted 5-or 6-membered saturated or unsaturated heterocyclyl group, or a substituted or unsubstituted 8-to 12-membered heteroaromatic bicyclic ring system; wherein the substitution on the cycloalkyl, cycloalkenyl, aryl, heterocyclyl, heteroaryl bicyclic ring system is by one or more groups selected from the group consisting of: oxy (═ O), halogen, cyano, nitro, hydroxy, C_1-6Alkyl or cycloalkyl, C_1-6Haloalkyl, C_2-6Alkenyl radical, C_2-6Haloalkenyl, C_2-6Alkynyl, C_2-6Halogenated alkynyl, hydroxy C_1-4An alkyl group;

wherein R 'and R' are each independently H, C_1-6Alkyl radical, C_3-6Cycloalkyl radical, C_1-6Haloalkyl, C_3-6Halogenocycloalkyl, C_2-6Alkenyl radical, C_2-6Haloalkenyl, C_2-6Alkynyl, C_2-6Haloalkynyl, or substituted or unsubstituted C_3-7Cycloalkyl, substituted or unsubstituted C_5-7A cycloalkenyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted 5-or 6-membered saturated or unsaturated heterocyclyl group, or a substituted or unsubstituted 8-to 12-membered heteroaromatic bicyclic ring system; wherein the substituents on R ', R' are one or more groups selected from the group consisting of: oxy (═ O), halogen, cyano, nitro, hydroxy, C_1-6Alkyl or cycloalkyl, C_1-6Haloalkyl, C_2-6Alkenyl radical, C_2-6Haloalkenyl, C_2-6Alkynyl, C_2-6Halogenated alkynyl, hydroxy C_1-4An alkyl group.

2. The compound of claim 1, wherein said compound has the structure shown in formula II:

in the formula:

X₁、X₂、X₃each is C (Ra), N (Ra) or S; x₁、X₂、X₃Is not S at the same time;

X₄、X₅、X₆each is C (Ra), N (Ra); x₄、X₅、X₆May be the same or different;

L₁、L₃may be the same or different and are each O, NH, S;

L₂is CH₂；

n is 1,2 or 3;

m is 0 or 1;

ra is selected from the group consisting of: H. halogen, cyano, nitro, hydroxy, substituted or unsubstituted C_1-6Alkoxy, substituted or unsubstituted C_1-6Alkyl, substituted or unsubstituted C_3-6Cycloalkyl, substituted or unsubstituted C_2-6Alkenyl, substituted orUnsubstituted C_2-6Alkynyl, or substituted or unsubstituted C_3-7Cycloalkyl, substituted or unsubstituted C_5-7Cycloalkenyl, trimethylsilylethynyl, substituted OR unsubstituted phenyl, substituted OR unsubstituted naphthyl, substituted OR unsubstituted 5-OR 6-membered heterocyclyl, substituted OR unsubstituted 8-to 12-membered heteroaromatic bicyclic ring system, OR ', Si (R')₃、NR’R”、C(O)R’、C(O)OR’、C(O)NR’R”、SR’、S(O)mR’、S(O)₂NR’R”、OC(O)R’、OC(O)NR’R”、OS(O)₂R’、OS(O)₂NR’R”、N(R”)C(O)R’、NCH₂R’、N(R”)C(O)NR’R”、N(R”)S(O)₂R 'or N (R') S (O)₂NR’R”；

Rb is selected from the group consisting of: H. halogen, cyano, nitro, hydroxy, substituted or unsubstituted C_1-6Alkoxy, substituted or unsubstituted C_1-6Alkyl, substituted or unsubstituted C_3-6Cycloalkyl, substituted or unsubstituted C_2-6Alkenyl, substituted or unsubstituted C_2-6Alkynyl, or substituted or unsubstituted C_3-7Cycloalkyl, substituted or unsubstituted C_5-7Cycloalkenyl, trimethylsilylethynyl, substituted OR unsubstituted phenyl, substituted OR unsubstituted naphthyl, substituted OR unsubstituted 5-OR 6-membered heterocyclyl, substituted OR unsubstituted 8-to 12-membered heteroaromatic bicyclic ring system, OR ', Si (R')₃、NR’R”、C(O)R’、C(O)OR’、C(O)NR’R”、SR’、S(O)mR’、S(O)₂NR’R”、OC(O)R’、OC(O)NR’R”、OS(O)₂R’、OS(O)₂NR’R”、N(R”)C(O)R’、NCH₂R’、N(R”)C(O)NR’R”、N(R”)S(O)₂R 'or N (R') S (O)₂NR’R”。

3. The compound of claim 1, wherein the compound has the structure shown in formula iii below:

in the formula:

V₁、V₂、V₃、V₄、V₅each is C (Ra), N (Ra) or S; v₂、V₃、V₄Is not S or N at the same time;

X₄、X₅、X₆may be the same or different and are each C (Ra), N (Ra);

L₁、L₃may be the same or different and are each O, NH, S;

L₂is CH₂；

n is 1,2 or 3;

each m is 0 or 1;

ra is selected from the group consisting of: H. halogen, cyano, nitro, hydroxy, substituted or unsubstituted C_1-6Alkoxy, substituted or unsubstituted C_1-6Alkyl, substituted or unsubstituted C_3-6Cycloalkyl, substituted or unsubstituted C_2-6Alkenyl, substituted or unsubstituted C_2-6Alkynyl, or substituted or unsubstituted C_3-7Cycloalkyl, substituted or unsubstituted C_5-7Cycloalkenyl, trimethylsilylethynyl, substituted OR unsubstituted phenyl, substituted OR unsubstituted naphthyl, substituted OR unsubstituted 5-OR 6-membered heterocyclyl, substituted OR unsubstituted 8-to 12-membered heteroaromatic bicyclic ring system, OR ', Si (R')₃、NR’R”、C(O)R’、C(O)OR’、C(O)NR’R”、SR’、S(O)mR’、S(O)₂NR’R”、OC(O)R’、OC(O)NR’R”、OS(O)₂R’、OS(O)₂NR’R”、N(R”)C(O)R’、NCH₂R’、N(R”)C(O)NR’R”、N(R”)S(O)₂R 'or N (R') S (O)₂NR’R”；

Rb is selected from the group consisting of: H. halogen, cyano, nitro, hydroxy, substituted or unsubstituted C_1-6Alkoxy, substituted or unsubstituted C_1-6Alkyl, substituted or unsubstituted C_3-6Cycloalkyl, substituted or unsubstituted C_2-6Alkenyl, substituted or unsubstituted C_2-6Alkynyl, or substituted or unsubstituted C_3-7Cycloalkyl, substituted or unsubstituted C_5-7Cycloalkenyl, trimethylsilylethynyl, substituted or unsubstituted phenyl, substituted or unsubstitutedSubstituted naphthyl, substituted OR unsubstituted 5-OR 6-membered heterocyclyl, substituted OR unsubstituted 8-to 12-membered heteroaromatic bicyclic ring system, OR ', Si (R')₃、NR’R”、C(O)R’、C(O)OR’、C(O)NR’R”、SR’、S(O)mR’、S(O)₂NR’R”、OC(O)R’、OC(O)NR’R”、OS(O)₂R’、OS(O)₂NR’R”、N(R”)C(O)R’、NCH₂R’、N(R”)C(O)NR’R”、N(R”)S(O)₂R 'or N (R') S (O)₂NR’R”。

4. The compound of claim 1, wherein said building blockHas a structure selected from the group consisting of:

5. the compound of claim 1, or an optical isomer, cis-trans isomer, or agriculturally pharmaceutically acceptable salt thereof, wherein the structural unitHas a structure selected from the group consisting of:

6. the compound of claim 1, or an optical isomer, cis-trans isomer, or agriculturally pharmaceutically acceptable salt thereof, wherein said structural elementHas a structure selected from the group consisting of:

7. the compound of claim 1, wherein said compound is selected from the group consisting of:

8. an agricultural composition, characterized in that it comprises: 0.001-99.99 wt% of the compound of any one of claims 1-7, or an optical isomer, a cis-trans isomer, or an agriculturally pharmaceutically acceptable salt of the compound, or a combination thereof; and an agriculturally pharmaceutically acceptable carrier and/or excipient.

9. Use of a compound according to any one of claims 1 to 7, or an optical isomer, a cis-trans isomer or an agriculturally pharmaceutically acceptable salt of said compound or an agricultural composition according to claim 8, for combating pests or for preparing a pesticidal composition.

10. A process for the preparation of a compound according to any one of claims 1 to 7, or an optical isomer, a cis-trans isomer, or an agriculturally pharmaceutically acceptable salt of said compound, characterized by:

in an inert solvent withAndreacting to obtain a compound shown in a formula II;

in an inert solvent withAndreacting to obtain a compound shown in a formula III;

wherein LG is a leaving group and the other groups are as defined in claim 1.

Technical Field

The invention relates to the field of pesticides, in particular to an aromatic heterocyclic ether compound, a preparation method and application thereof.

Background

The aromatic ether compound is used as an insecticide for a long time, has an action mechanism of disturbing the growth of insects, belongs to a novel insecticide of juvenile hormone analogues, and has the characteristics of systemic transfer activity, low toxicity, long lasting period, safety to crops, low toxicity to fishes, small influence on ecological environment and the like. The unique action mode and the obvious prevention and treatment effect are considered as one of effective means for comprehensive control of the pesticides, and become a hotspot field for research and creation of the pesticides.

There are many agricultural pest control means, and chemical pest control is the main point at present. The main parts of the widely used chemical insecticides are organophosphorus or carbamate, pyrethroid pesticides such as cadusafos, fenamiphos, fosthiazate, aldicarb, carbofuran, cyhalothrin and the like, the safety to human beings and other non-target organisms is low, the pollution to soil, water sources and agricultural products can be caused to different degrees, and the widely used chemical insecticides comprise neonicotinoid insecticides, ryanodine receptor inhibitors and the like. Because various insecticides are used excessively and frequently, serious drug resistance is caused, so that the difficulty of pest control is increased day by day.

In addition, the adult insects have reproductive capacity due to the fact that all parts of the bodies have developed, the resistance of the adult insects to agricultural pesticides is strongest, and the adult insects have the greatest influence on crops. In particular, juvenile hormone analogs are often less than desirable as insecticides for adult insects.

Therefore, the search for chemical pesticides with high efficiency, low toxicity and good environmental compatibility and novel structure is a technical problem which needs to be solved urgently in the field.

Disclosure of Invention

The invention aims to provide a chemical insecticide with high efficiency, low toxicity and good environmental compatibility and a novel structure, in particular to a novel aromatic (hetero) cyclic ether compound with insecticidal activity on adult insects.

In a first aspect, the present invention provides a compound having a structure represented by general formula (I) or an optical isomer, cis-trans isomer, or agriculturally pharmaceutically acceptable salt thereof:

in the formula:

ring α is a substituted or unsubstituted phenyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted 5-or 6-membered heterocyclyl, or a substituted or unsubstituted 8-to 12-membered heterobicyclic heteroaryl;

ring β is a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted 5-or 6-membered heterocyclylene group, or a substituted or unsubstituted 8-to 12-membered heteroarylenedicyclic group;

ring γ is a substituted or unsubstituted naphthyl group, a substituted or unsubstituted 5-or 6-membered heterocyclic group, or a substituted or unsubstituted 8-to 12-membered heteroaromatic bicyclic group;

the substituents of the ring α, the ring β and the ring gamma are selected from the group consisting of halogen, cyano, nitro, hydroxyl and substituted or unsubstituted C_1-6Alkyl or alkoxy, substituted or unsubstituted C_2-6An alkenyl group,Substituted or unsubstituted C_2-6Alkynyl, or substituted or unsubstituted C_3-7Cycloalkyl, substituted or unsubstituted C_5-7A cycloalkenyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted 5-or 6-membered heterocyclyl group, or a substituted or unsubstituted 8-to 12-membered heteroaryl bicyclic group;

L₁、L₃may be the same or different and each is independently selected from the group consisting of: -NR' -, -O-, -S-;

L₂is a group selected from: -CR 'R "-, R' R" may be the same or different;

n is an integer of 1 to 8; preferably an integer of 1 to 5; more preferably an integer of 1 to 3; most preferably 1;

g is a substituent independently located at any one or more (preferably 1 to 3) positions of ring γ, and G is selected from the group consisting of: halogen, cyano, nitro, hydroxy, substituted or unsubstituted C_1-6Alkoxy, substituted or unsubstituted C_1-6Alkyl, substituted or unsubstituted C_2-6Alkenyl, substituted or unsubstituted C_2-6Alkynyl, or substituted or unsubstituted C_3-7Cycloalkyl, substituted or unsubstituted C_5-7Cycloalkenyl, trimethylsilylethynyl, substituted OR unsubstituted phenyl, substituted OR unsubstituted naphthyl, substituted OR unsubstituted 5-OR 6-membered heterocyclyl, substituted OR unsubstituted 8-to 12-membered heteroaromatic bicyclic ring system, OR ', Si (R')₃、NR’R”、C(O)R’、C(O)OR’、C(O)NR’R”、SR’、S(O)_nR’、S(O)₂NR’R”、OC(O)R’、OC(O)NR’R”、OS(O)₂R’、OS(O)₂NR’R”、N(R”)C(O)R’、NCH₂R’、N(R”)C(O)NR’R”、N(R”)S(O)₂R 'or N (R') S (O)₂NR’R”；

The substitution means substitution by one or more groups selected from the group consisting of: halogen, cyano, nitro, hydroxy, C_1-6Alkyl radical, C_1-6Alkoxy radical, C_1-6Haloalkyl, C_2-6Alkenyl radical, C_2-6Haloalkenyl, C_2-6Alkynyl, C_2-6Halogenated alkynyl, hydroxy C_1-4Alkyl, R'、OR’、Si(R’)₃、NR’R”、C(O)R’、C(O)OR’、C(O)NR’R”、SR’、S(O)_mR’、S(O)₂NR’R”、OC(O)R、OC(O)NR’R”、OS(O)₂R’、OS(O)₂NR’R”、N(R’)C(O)R’、N(R’)C(O)NR’R”、N(R’)S(O)₂R 'or N (R') S (O)₂NR' R ", or substituted or unsubstituted C_3-7Cycloalkyl, substituted or unsubstituted C_5-7A cycloalkenyl group, a substituted or unsubstituted 6-10 membered aryl group, a substituted or unsubstituted 5-or 6-membered saturated or unsaturated heterocyclyl group, or a substituted or unsubstituted 8-to 12-membered heteroaromatic bicyclic ring system; wherein the substitution on the cycloalkyl, cycloalkenyl, aryl, heterocyclyl, heteroaryl bicyclic ring system is by one or more groups selected from the group consisting of: oxy (═ O), halogen, cyano, nitro, hydroxy, C_1-6Alkyl or cycloalkyl, C_1-6Haloalkyl, C_2-6Alkenyl radical, C_2-6Haloalkenyl, C_2-6Alkynyl, C_2-6Halogenated alkynyl, hydroxy C_1-4An alkyl group;

wherein R 'and R' are each independently H, C_1-6Alkyl radical, C_3-6Cycloalkyl radical, C_1-6Haloalkyl, C_3-6Halogenocycloalkyl, C_2-6Alkenyl radical, C_2-6Haloalkenyl, C_2-6Alkynyl, C_2-6Haloalkynyl, or substituted or unsubstituted C_3-7Cycloalkyl, substituted or unsubstituted C_5-7A cycloalkenyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted 5-or 6-membered saturated or unsaturated heterocyclyl group, or a substituted or unsubstituted 8-to 12-membered heteroaromatic bicyclic ring system; wherein the substituents on R ', R' are one or more groups selected from the group consisting of: oxy (═ O), halogen, cyano, nitro, hydroxy, C_1-6Alkyl or cycloalkyl, C_1-6Haloalkyl, C_2-6Alkenyl radical, C_2-6Haloalkenyl, C_2-6Alkynyl, C_2-6Halogenated alkynyl, hydroxy C_1-4An alkyl group.

In a specific embodiment, the compound has the structure shown in formula II below:

in the formula:

X₁、X₂、X₃each is C (Ra), N (Ra) or S; x₁、X₂、X₃Is not S at the same time;

X₄、X₅、X₆each is C (Ra), N (Ra); x₄、X₅、X₆May be the same or different;

L₁、L₃may be the same or different and are each O, NH, S;

L₂is CH₂；

n is 1,2 or 3;

m is 0 or 1;

ra is selected from the group consisting of: H. halogen, cyano, nitro, hydroxy, substituted or unsubstituted C_1-6Alkoxy, substituted or unsubstituted C_1-6Alkyl, substituted or unsubstituted C_3-6Cycloalkyl, substituted or unsubstituted C_2-6Alkenyl, substituted or unsubstituted C_2-6Alkynyl, or substituted or unsubstituted C_3-7Cycloalkyl, substituted or unsubstituted C_5-7Cycloalkenyl, trimethylsilylethynyl, substituted OR unsubstituted phenyl, substituted OR unsubstituted naphthyl, substituted OR unsubstituted 5-OR 6-membered heterocyclyl, substituted OR unsubstituted 8-to 12-membered heteroaromatic bicyclic ring system, OR ', Si (R')₃、NR’R”、C(O)R’、C(O)OR’、C(O)NR’R”、SR’、S(O)mR’、S(O)₂NR’R”、OC(O)R’、OC(O)NR’R”、OS(O)₂R’、OS(O)₂NR’R”、N(R”)C(O)R’、NCH₂R’、N(R”)C(O)NR’R”、N(R”)S(O)₂R 'or N (R') S (O)₂NR’R”；

Rb is selected from the group consisting of: H. halogen, cyano, nitro, hydroxy, substituted or unsubstituted C_1-6Alkoxy, substituted or unsubstituted C_1-6Alkyl, substituted or unsubstituted C_3-6Cycloalkyl, substituted or unsubstituted C_2-6An alkenyl group,Substituted or unsubstituted C_2-6Alkynyl, or substituted or unsubstituted C_3-7Cycloalkyl, substituted or unsubstituted C_5-7Cycloalkenyl, trimethylsilylethynyl, substituted OR unsubstituted phenyl, substituted OR unsubstituted naphthyl, substituted OR unsubstituted 5-OR 6-membered heterocyclyl, substituted OR unsubstituted 8-to 12-membered heteroaromatic bicyclic ring system, OR ', Si (R')₃、NR’R”、C(O)R’、C(O)OR’、C(O)NR’R”、SR’、S(O)mR’、S(O)₂NR’R”、OC(O)R’、OC(O)NR’R”、OS(O)₂R’、OS(O)₂NR’R”、N(R”)C(O)R’、NCH₂R’、N(R”)C(O)NR’R”、N(R”)S(O)₂R 'or N (R') S (O)₂NR’R”。

In a specific embodiment, the compound has the structure shown in formula iii below:

in the formula:

V₁、V₂、V₃、V₄、V₅each is C (Ra), N (Ra) or S; v₂、V₃、V₄Is not S or N at the same time;

X₄、X₅、X₆may be the same or different and are each C (Ra), N (Ra);

L₁、L₃may be the same or different and are each O, NH, S;

L₂is CH₂；

n is 1,2 or 3;

each m is 0 or 1;

ra is selected from the group consisting of: H. halogen, cyano, nitro, hydroxy, substituted or unsubstituted C_1-6Alkoxy, substituted or unsubstituted C_1-6Alkyl, substituted or unsubstituted C_3-6Cycloalkyl, substituted or unsubstituted C_2-6Alkenyl, substituted or unsubstituted C_2-6Alkynyl, or substituted or unsubstituted C_3-7Cycloalkyl, substituted or unsubstituted C_5-7Cycloalkenyl, trimethylsilylethynyl, substituted OR unsubstituted phenyl, substituted OR unsubstituted naphthyl, substituted OR unsubstituted 5-OR 6-membered heterocyclyl, substituted OR unsubstituted 8-to 12-membered heteroaromatic bicyclic ring system, OR ', Si (R')₃、NR’R”、C(O)R’、C(O)OR’、C(O)NR’R”、SR’、S(O)mR’、S(O)₂NR’R”、OC(O)R’、OC(O)NR’R”、OS(O)₂R’、OS(O)₂NR’R”、N(R”)C(O)R’、NCH₂R’、N(R”)C(O)NR’R”、N(R”)S(O)₂R 'or N (R') S (O)₂NR’R”；

Rb is selected from the group consisting of: H. halogen, cyano, nitro, hydroxy, substituted or unsubstituted C_1-6Alkoxy, substituted or unsubstituted C_1-6Alkyl, substituted or unsubstituted C_3-6Cycloalkyl, substituted or unsubstituted C_2-6Alkenyl, substituted or unsubstituted C_2-6Alkynyl, or substituted or unsubstituted C_3-7Cycloalkyl, substituted or unsubstituted C_5-7Cycloalkenyl, trimethylsilylethynyl, substituted OR unsubstituted phenyl, substituted OR unsubstituted naphthyl, substituted OR unsubstituted 5-OR 6-membered heterocyclyl, substituted OR unsubstituted 8-to 12-membered heteroaromatic bicyclic ring system, OR ', Si (R')₃、NR’R”、C(O)R’、C(O)OR’、C(O)NR’R”、SR’、S(O)mR’、S(O)₂NR’R”、OC(O)R’、OC(O)NR’R”、OS(O)₂R’、OS(O)₂NR’R”、N(R”)C(O)R’、NCH₂R’、N(R”)C(O)NR’R”、N(R”)S(O)₂R 'or N (R') S (O)₂NR’R”。

In a specific embodiment, said building blockHas a structure selected from the group consisting of:

in a preferred embodiment, L is₁A structure selected from the group consisting of: o, S; said L₃A structure selected from the group consisting of: o, NH, S.

In a preferred embodiment, L is₁The selected structure of the group is O; said L₃The selected structure of the group is O.

In a specific embodiment, said building blockHas a structure selected from the group consisting of:

in a preferred embodiment, the G group has a structure selected from the group consisting of: none, halogen, cyano, CF₃Methyl, N-methylcarboxamide group.

In a specific embodiment, said building blockHas a structure selected from the group consisting of:

in a preferred embodiment, the G group has a structure selected from the group consisting of: none, halogen, cyano, CF₃OCF3, alkyl or alkoxy, N-methylcarboxamide.

In a preferred embodiment of the present invention,has a structure selected from the group consisting of: -CH₂-、-CH₂CH₂-。

In a preferred embodiment of the present invention,is-CH₂-。

In particular embodiments, the compound is selected from the group consisting of:

in a preferred embodiment, the compound is selected from the group consisting of:

in a second aspect, the present invention provides an agricultural composition comprising: 0.001 to 99.99 wt% of the compound of the first aspect, or an optical isomer, a cis-trans isomer, or an agriculturally pharmaceutically acceptable salt of the compound, or a combination thereof; and an agriculturally pharmaceutically acceptable carrier and/or excipient.

In a third aspect, the present invention provides the use of a compound of the first aspect, or an optical isomer, a cis-trans isomer, or an agriculturally pharmaceutically acceptable salt of said compound or an agricultural composition of the second aspect, for combating pests or for preparing a pesticidal composition.

In a preferred embodiment, the composition is used to kill or prevent an agricultural or forestry pest, particularly a hemipteran pest.

In a fourth aspect, the present invention provides a process for preparing a compound of the first aspect, or an optical isomer, a cis-trans isomer, or an agriculturally pharmaceutically acceptable salt of the compound, characterized in that:

in an inert solvent withAndreacting to obtain a compound shown in a formula II;

in an inert solvent withAndreacting to obtain a compound shown in a formula III;

wherein LG is a leaving group and the other groups are as defined in claim 1.

In a preferred embodiment, the process further comprises the step of optionally resolving the resulting compound into the corresponding optical isomer or cis-trans isomer.

It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.

Detailed Description

The inventors have conducted long-term and intensive studies and have unexpectedly found and synthesized a series of aryl (hetero) cyclic ether compounds having a novel structure and a remarkable pesticidal activity. On this basis, the inventors have completed the present invention.

Radical definition

The term "C_1-6Alkyl "means a straight or branched chain alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, or the like.

The term "C_2-6Alkenyl "means a straight or branched chain alkenyl group having 2 to 6 carbon atoms, such as vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, or the like.

The term "C_2-6Alkynyl "means a straight chain having 2 to 6 carbon atomsOr a branched alkynyl group such as ethynyl, propynyl, or the like.

The term "C_3-7Cycloalkyl "refers to a cyclic alkyl group having 3 to 7 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, or the like.

The term "C_5-7Cycloalkenyl "refers to a cyclic alkenyl group having 5 to 7 carbon atoms with one or more double bonds, such as cyclopentenyl, cyclohexenyl, cycloheptenyl, 1, 3-cyclohexadienyl, 1, 4-cyclohexadienyl, or the like.

As used herein, the term "C_1-4Alkoxy "means a straight or branched chain alkoxy group having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, or the like.

The term "halogen" refers to fluorine, chlorine, bromine, or iodine. The term "halogenated" refers to a group substituted with one or more of the above halogen atoms, which may be the same or different, such as trifluoromethyl, pentafluoroethyl, heptafluoroisopropyl, or the like.

The term "ring" or "ring system" refers to a carbocyclic or heterocyclic ring. The term "heterocycle" means that at least one of the atoms forming the skeleton of the heterocycle is not carbon, and is nitrogen, oxygen or sulfur. Typically, the heterocyclic ring contains no more than 4 nitrogens, no more than 2 oxygens, and/or no more than 2 sulfurs. Unless otherwise indicated, the heterocyclic ring may be a saturated, partially unsaturated, or fully unsaturated ring. In a particular embodiment, the term "ring system" refers to fused rings where two or more rings are joined together.

The term "5-or 6-membered heterocyclic group" as used herein means a five-or six-membered ring containing one or more heteroatoms selected from nitrogen, oxygen or sulfur, for example, pyridyl, thiazolyl, isothiazolyl, thienyl, furyl, pyrrolyl, pyrazolyl, pyrimidinyl, tetrahydrofuryl, 4, 5-dihydrothiazol-2-yl, 2-cyanoimino-4-oxo-1, 3-thiazolidin-3-yl, 2-cyanoimino-4-oxo-1, 3-thiazinan-3-yl, oxazolyl, isoxazolyl, 1H-tetrazolyl, 1H-1,2, 3-triazolyl, 4H-1,2, 4-triazolyl, 1,2, 3-thiadiazolyl, 1,2, 4-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,2, 4-oxadiazolyl, 1,2, 5-oxadiazolyl, 1,3, 4-oxadiazolyl, tetrazolyl, or the like.

The term "heterocyclic ring system" refers to a ring system in which at least one ring in the ring system is heterocyclic. Similarly, the term "heteroaromatic ring system" refers to systems in which at least one ring in the ring system is aromatic.

As used herein, the term "8-to 12-membered heteroaromatic bicyclic ring system" or "8-to 14-membered heteroaromatic bicyclic or tricyclic ring system" may be selected from the group consisting of: benzofuran, benzo [ b ] thiophene, indole, quinoline, isoquinoline, 1H-indazole, 1H-benzo [ d ] imidazole, benzo [ d ] thiazole, benzo [ d ] oxazole, benzo [ d ] isoxazole, benzo [ d ] [1,2,3] thiadiazole, 2, 3-dihydroimidazo [1,2-a ] pyridine, quinazoline, quinoxaline, cinnoline, phthalazine, 1, 8-naphthyridine, 4,5,6, 7-tetrahydrobenzo [ b ] thiophene, benzo [ b ] thiophene-1, 1-dioxane, 8H-indeno [2,1-b ] thiophene, 7, 8-dihydro-6H-cyclopenta [4,5] thieno [2,3-d ] pyrimidine, 3,5,6, 7-tetrahydro-4H-cyclopenta [4,5] thieno [2,3-d ] pyrimidin-4-one, spiro [ indoline-3, 2 '- [1,3] dioxolane ] -2-one, spiro [ indoline-3, 2' - [1,3] dioxane ] -2-one, indoline-2, 3-dione, or the like.

The term "alkyl" refers to a group derived from an alkane molecule by the removal of one hydrogen atom; the term "alkylene" refers to a group of an alkane molecule lacking two hydrogen atoms. Similarly, "alkenylene", "alkynylene", "cycloalkylene", "cycloalkenylene", "phenylene", "naphthylene", "heterocyclylene" or "heteroarylene bicyclic or tricyclic ring system" are defined analogously.

Unless specifically stated to be "substituted or unsubstituted", the groups of the present invention may be substituted with a substituent selected from the group consisting of: halogen, cyano, nitro, hydroxy, C_1-6Alkyl radical, C_1-6Haloalkyl, C_2-6Alkenyl radical, C_2-6Haloalkenyl, C_2-6Alkynyl, C_2-6Halogenated alkynyl, hydroxy C_1-4Alkyl, OR ', Si (R')₃、NR’R"、C(O)R’、C(O)OR’、C(O)NR’R"、SR’、S(O)mR’、S(O)₂NR’R”、OC(O)R’、OC(O)NR’R”、OS(O)₂R’、OS(O)₂NR’R”、N(R”)C(O)R’、NCH₂R’、N(R”)C(O)NR’R”、N(R”)S(O)₂R 'or N (R') S (O)₂NR 'R' and the like, wherein R 'and R' are as defined above, and m is 1 or 2.

The inert solvent refers to various solvents which do not react with the raw materials, including various straight chain, branched chain or cyclic alcohols, ethers or ketones, alkyl halides, 1, 4-dioxane, acetonitrile, tetrahydrofuran, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO) and the like.

The compounds of the present invention may contain one or more asymmetric centers and thus occur as racemates, racemic mixtures, single enantiomers, diastereomeric compounds and individual diastereomers. Asymmetric centers that may be present depend on the nature of the various substituents on the molecule. Each such asymmetric center will independently produce two optical isomers and all possible optical isomers and diastereomeric mixtures and pure or partially pure compounds are included within the scope of the invention. The present invention includes all isomeric forms of the compounds.

Compounds of the invention and their pesticidal activity

The term "compound of the invention", "active substance of the invention" or "active compound of the invention" means a compound of the invention, an optical isomer, cis-trans isomer or an agriculturally pharmaceutically acceptable salt thereof, which has significantly improved pesticidal activity, as well as an extended pesticidal spectrum.

Specifically, the compound of the invention is a compound shown in a general formula (I) or an optical isomer, a cis-trans isomer or an agriculturally and pharmaceutically acceptable salt thereof:

in a preferred embodiment, the compounds of the present invention have the structure shown in formula II below:

in a further preferred embodiment, the compound has the structure shown in formula iii below:

wherein the structural unitHas a structure selected from the group consisting of:

the structural unitHas a structure selected from the group consisting of:

or

The structural unitHas a structure selected from the group consisting of:

in a preferred embodiment, the compounds of the invention are selected from the group consisting of:

in a preferred embodiment, the compounds of the invention are represented by the formula:

the term "agriculturally pharmaceutically acceptable salt" as used herein means that the anion of the salt is known and acceptable in forming a pharmaceutically acceptable salt of a pesticide. The salt is preferably water soluble. Suitable acid addition salts formed by compounds of formula i include salts with inorganic acids, such as hydrochloride, phosphate, sulfate, nitrate; and salts comprising organic acids, such as acetates, benzoates.

According to the conventional understanding in the art, aromatic ether compounds are more suitable for eggs or larvae, but may have a weaker effect on adults. However, the present inventors have found that the aromatic ether compound of the present invention is not only suitable for eggs or larvae, but also has excellent insecticidal activity against adults.

The active substance of the present invention can be used for controlling and exterminating a wide range of agricultural and forestry plant pests, pests of stored cereals, public health pests, pests harmful to animal health, and the like. In the present specification, "pesticide" is a general term for a substance having an effect of controlling all the pests mentioned above. The compounds of the present invention are useful for controlling and exterminating a wide range of pests, Sucking insects, biting insects and other plant parasites, pests of stored cereals and health pests causing health hazards.

Examples of pests are as follows: coleopteran insects: elephant of maize (Sitophilus zeamais), tribolium castaneum (herbsts)), ladybug of potato (henosepilaphthalein intricaculata), click beetle (agriotesfuscipoli Miwa), cuora trifasciata, leptospora trifasciata (monochamatum Hope), elephant of rice (echinococcus quadratus Billberg), elephant of rice (echinococcus bipunctatus), elephant of rice (rinocopherus), elephant of rice (brown flour stupid). Lepidopteran insects: gypsy moth (Lymantria dispar), tsingtaurus (Malacosma neustriatesta Motschulsky), prodenia litura, cabbage looper, chilo suppressalis, ostrinia nubilalis, pink plumeria sticalis, cotton bollworm, chestnut leaf roller moth, black cutworm (agrotis fucosa), wax moth, cabbage moth, and citrus fruit moth. Hemipteran insects: leafhopper nigricans (nephotettixcinceps), nilaparvata lugens (Nilaparvatalugens), laodelphax striatellus (Laodelphaxstriatellus), bemisia tabaci (Bemisiatabaci), mealybugs conraddea, arrowhead geckos (unaspiyanonensis), green peach aphids (myzuspersica), apple aphids, cabbage aphids (praevicerbionyynebsicae), radish aphids (lipaphiserpsiseisuseudobisinae), pennisetum minitans (stephanis nasutum et takeya), Nazara pests, bed bugs, greenhouse whitefly, and pediculosis pests (psyle SPP.). Orthoptera insects: german cockroach (b. germanica line), american cockroach (p. american line), mole cricket africana (gryllotapaafricana palisot et Beauvois), and locusta migratoria asia (Locus migratoria). Insects of the order isoptera: termites (coptottermes formusanus). Insects of the order diptera: musca domestica (Musca do medicalinnac us), Aedes aegypti (Aedes aegypti), Dietus spp, Culex, Anopheles sinensis Wiedemann, and Triplostex peduncularis, Acarina red spider (Tetranychus nabarinus).

The compound of the invention has special effect on piercing-sucking and scraping-sucking mouthpart pests, such as bemisia tabaci, scale insects, diamond back moths, beet armyworms, pear psyllids, thrips and the like.

In a preferred embodiment, the compounds of the present invention have excellent insecticidal activity against thrips, preferably thrips palmi (thripsphalmi) and bemisia tabaci.

The active compounds can be formulated in the customary formulations, for example solutions, emulsions, suspensions, powders, granules, foams, pastes, aerosols; in particular soluble solid and liquid preparations with good environmental compatibility, such as water-dispersible granules, aqueous solvents and emulsions, ultra-low-volume preparations, etc., natural and synthetic materials impregnated with active substances, microcapsules in polymers, coating compositions for seeds, and preparations for use with combustion devices, such as smoking cartridges, smoking cans and discs, and ULV cold and hot mist preparations. These formulations can be produced by known methods, for example by mixing the active compounds with extenders, that is, liquid or liquefied gas or solid diluents or carriers, and optionally surfactants, that is, emulsifiers and/or dispersants and/or foam formers. Organic solvents may also be used as adjuvants, for example when water is used as extender.

When a liquid solvent is used as the diluent or carrier, it is basically suitable, for example: aromatic hydrocarbons such as xylene, toluene or alkylnaphthalene; chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzene, vinyl chloride or dichloromethane; aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions; alcohols, such as ethanol or ethylene glycol and their ethers and lipids; ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexane; or less commonly polar solvents such as dimethylformamide and dimethylsulfoxide, and water.

By a diluent or carrier for liquefied gases is meant a liquid which will become gaseous at ambient temperature and pressure, for example aerosol propellants such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.

The solid carrier can be selected from the group consisting of naturally occurring minerals, such as kaolin, clay, talc, quartz, activated clay, montmorillonite, or diatomaceous earth, and synthetic minerals, such as highly dispersed silicic acid, alumina, and silicates. Solid carriers for granules are ground and classified natural marble, such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic materials, such as sawdust, coconut shells, corn cobs and tobacco stalks, etc.

Nonionic and anionic emulsifiers can be used as emulsifiers and/or foam formers. Such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, such as alkylaryl polyethylene glycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and albumin hydrolysates. Dispersant coatings such as lignosulfite waste liquors and methylcellulose.

Binders such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or emulsions, for example gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.

Colorants such as inorganic fuels, e.g., iron oxide, cobalt oxide and prussian blue; organic dyes such as azo dyes or metal titanyl cyanine dyes; and with trace nutrients such as salts of iron, manganese, boron, copper, cobalt, aluminum, and zinc, and the like.

These preparations usually contain 0.1 to 95% by weight of active compound, preferably 0.5 to 90%.

The active compounds according to the invention can be present in their commercial formulations in a mixture with other active compounds, such as insecticides, baits, bactericides, acaricides, nematicides, fungicides, growth control agents, etc., or in the use forms prepared from these formulations. Pesticides include, for example, phosphates, carbamates, pyrethrins, chlorinated hydrocarbons, benzoylureas, nereistoxin and substances produced by microorganisms, such as avermectins.

Furthermore, the active compounds according to the invention can also be formulated with synergists in a mixture in their commercial preparations in the use forms prepared from these preparations. The synergist is a compound which improves the action of the active compound, and the active compound has activity, so that the synergist is not required to be added. The concentration of the active compound in the dosage form prepared from commercial preparations for use can vary within wide limits. The concentration of active compound in the dosage form used may be from 0.0000001 to 100% (by weight of active compound), preferably between 0.0001 and 1%.

The main advantages of the invention include:

1. the invention provides a chemical pesticide with high efficiency, low toxicity and good environmental compatibility and novel structure;

2. compared with diphenyl ether juvenile hormone analogues, the compound provided by the invention has killing activity on adults particularly; and

3. the compound has good control effect on hemiptera pests.

The technical solution of the present invention will be further described with reference to the following specific embodiments, but the following embodiments are not intended to limit the present invention, and all of the various application methods adopted according to the principles and technical means of the present invention belong to the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. Unless otherwise indicated, percentages and parts are by weight.