Isoxazoline derivative and its application in agricultural

文档序号：1750690 发布日期：2019-11-29 浏览：45次中文

阅读说明：本技术 异噁唑啉衍生物及其在农业中的应用 (Isoxazoline derivative and its application in agricultural ) 是由李义涛林健池伟林曾水明任佳宁邱鹏飞郭晓丹于 2019-05-21 设计创作，主要内容包括：本发明提供异噁唑啉衍生物及其在农业中的应用；具体地,本发明提供式(Ia)所示的化合物或式(Ia)所示化合物的立体异构体、氮氧化物或其盐,及其制备方法；其中R1、R2、R3、R4、n、R5、R6、X和Y具有如本发明所述的含义。进一步地,本发明提供含有这些化合物的组合物及其在农业中的应用,特别是作为除草剂活性成分用于防治不想要的植物的用途。<Image he="382" wi="700" file="DDA0002066360960000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>。(The present invention provides isoxazoline derivative and its application in agricultural；Specifically, the present invention provides stereoisomer, nitrogen oxides or its salt of compound shown in formula (Ia) compound represented or formula (Ia), and preparation method thereof；Wherein R 1 、R 2 、R 3 、R 4 、n、R 5 、R 6 , X and Y there is meaning as described in the present invention.Further, the present invention provides the composition containing these compounds and its application in agricultural, is used to prevent and treat the purposes of undesired plant especially as herbicide active active ingredients. 。)

1. a kind of compound is stereoisomer, the nitrogen oxygen of the compound as shown in formula (Ia) compound represented or formula (Ia) Compound or its salt:

Wherein:

R¹And R²It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, alkyl, halogenated alkyl, ring Alkyl or cycloalkyl alkyl；Or R¹、R²It is formed together with the carbon atom being connected with them by 3-12 former molecular ring；

R³And R⁴It is each independently hydrogen, bromine, iodine, amino, nitro, hydroxyl, carboxyl, alkyl, naphthenic base or cycloalkyl-alkyl；Or Person R³、R⁴It is formed together with the carbon atom being connected with them by 3-12 former molecular ring；

N is 0,1 or 2；

R⁵And R⁶It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, alkyl, alkenyl or alkynyl； Or R⁵、R⁶It is formed together with the carbon atom being connected with them by 3-12 former molecular ring；

X is fluorine, chlorine or bromine；

Y is alkyl, halogenated alkyl, alkoxyalkyl, alkyl amino alkyl, alkenyl, halogenated alkenyl, alkynyl, halo alkynyl, cycloalkanes Base, cycloalkyl-alkyl, heterocycle, heterocyclylalkyl group, aryl, aryl alkyl, heteroaryl, heteroaryl alkyl ,-C (=O)-alkane Base ,-S (=O)₂Alkyl ,-C (=O)-naphthenic base ,-S (=O)₂Naphthenic base ,-C (=O)-heterocycle ,-S (=O)₂Heterocycle Base ,-C (=O)-aryl ,-S (=O)₂Aryl ,-C (=O)-heteroaryl or-S (=O)₂Heteroaryl；

Wherein Y is optionally selected from Y by 1,2,3,4,5 or 6^aSubstituent group replaced；Each Y^aIt independently is fluorine, chlorine, bromine, iodine, ammonia Base, nitro, cyano, hydroxyl, carboxyl, alkyl, halogenated alkyl, alkenyl, halogenated alkenyl, alkynyl, halo alkynyl, alkoxy, alkane ammonia Base, alkylthio group, naphthenic base, heterocycle, aryl or heteroaryl；

Condition is:

(1) when Y is methyl, X is chlorine, R⁵And R⁶It is hydrogen, n 0,1 or 2, R³And R⁴It is hydrogen, R¹When for methyl, R²It is not first Base or chloromethyl；

(2) when Y is methyl, X is chlorine, R⁵And R⁶It is hydrogen, n 0,1 or 2, R³And R⁴It is hydrogen, R²When for methyl, R¹It is not first Base or chloromethyl；

(3) when Y is unsubstituted phenyl, X is chlorine, R⁵And R⁶It is hydrogen, n 0,1 or 2, R³And R⁴It is hydrogen, R¹When for methyl, R²It is not methyl or chloromethyl；

(4) when Y is unsubstituted phenyl, X is chlorine, R⁵And R⁶It is hydrogen, n 0,1 or 2, R³And R⁴It is hydrogen, R²When for methyl, R¹It is not methyl or chloromethyl；

(5) when Y is ethyl or isopropyl, X is chlorine and at 5 of pyrazole ring, R⁵And R⁶It is hydrogen, n is 0 or 2, R³And R⁴It is Hydrogen, R¹When for methyl, R²It is not chloromethyl；Or

(6) when Y is ethyl or isopropyl, X is chlorine and at 5 of pyrazole ring, R⁵And R⁶It is hydrogen, n is 0 or 2, R³And R⁴It is Hydrogen, R²When for methyl, R¹It is not chloromethyl.

2. compound according to claim 1, being the compound as shown in formula (II) compound represented or formula (II) Stereoisomer, nitrogen oxides or its salt:

Wherein:

X is fluorine, chlorine or bromine；

N is 0,1 or 2；

R⁸、R⁹、R¹⁰、R¹¹And R¹²Be each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, alkyl, Halogenated alkyl, alkenyl, halogenated alkenyl, alkynyl, halo alkynyl, alkoxy, alkylamino, alkylthio group, naphthenic base, heterocycle, aryl Or heteroaryl；

Or R⁸、R⁹The former molecular ring of 3-12 optionally replaced is formed together with the carbon atom being attached thereto；

Or R⁸、R⁹- C (=O)-is formed together with the carbon atom being attached thereto；

Or R¹⁰、R¹¹、R¹²- C ≡ CR is formed together with the carbon atom being attached thereto¹³Or-CR¹⁴=CR¹⁵R¹⁶；Wherein R¹³、R¹⁴、 R¹⁵And R¹⁶It is each independently hydrogen, alkyl, halogenated alkyl, alkenyl, halogenated alkenyl, alkynyl or halo alkynyl；

Or R¹⁰、R¹¹、R¹²The C optionally replaced is formed together with the carbon atom being attached thereto_6-14Aryl, the C optionally replaced_1-9It is miscellaneous Aryl, the C optionally replaced_3-12Naphthenic base or the C optionally replaced_2-12Heterocycle；

Or-CR⁸R⁹-CR¹⁰R¹¹R¹²Indicate the C optionally replaced_10-14Aryl, the C optionally replaced_1-9Heteroaryl optionally replaces C_3-12Naphthenic base, the C optionally replaced_2-12Heterocycle, unsubstituted phenyl or substituted phenyl；

The substitution optionally replaces, and substituent group number is 1,2,3,4,5 or 6；Substituent group can be identical or different；Wherein take Dai Jiwei fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, alkyl, halogenated alkyl, alkenyl, halogenated alkenyl, alkynyl, Halo alkynyl, alkoxy, alkylamino, alkylthio group, naphthenic base, heterocycle, aryl or heteroaryl；

Condition is:

(a) as-CR⁸R⁹-CR¹⁰R¹¹R¹²Indicate that unsubstituted phenyl, X are chlorine, R⁵And R⁶It is hydrogen, n 0,1 or 2, R³And R⁴ For hydrogen, R¹When for methyl, R²It is not methyl or chloromethyl；

(b) as-CR⁸R⁹-CR¹⁰R¹¹R¹²Indicate that unsubstituted phenyl, X are chlorine, R⁵And R⁶It is hydrogen, n 0,1 or 2, R³And R⁴ For hydrogen, R²When for methyl, R¹It is not methyl or chloromethyl；

(c) as-CR⁸R⁹-CR¹⁰R¹¹R¹²Indicate ethyl or isopropyl, X is chlorine and at 5 of pyrazole ring, R⁵And R⁶It is hydrogen, n 0 Or 2, R³And R⁴It is hydrogen, R¹When for methyl, R²It is not chloromethyl；Or

(d) as-CR⁸R⁹-CR¹⁰R¹¹R¹²Indicate ethyl or isopropyl, X is chlorine and at 5 of pyrazole ring, R⁵And R⁶It is hydrogen, n 0 Or 2, R³And R⁴It is hydrogen, R²When for methyl, R¹It is not chloromethyl.

3. compound according to claim 1 or 2 is the chemical combination as shown in formula (IIa) compound represented or formula (IIa) Stereoisomer, nitrogen oxides or its salt of object；Or it is the chemical combination as shown in formula (IIb) compound represented or formula (IIb) Stereoisomer, nitrogen oxides or its salt of object:

4. compound according to claim 1 or 2 is the chemical combination as shown in formula (IIc) compound represented or formula (IIc) Stereoisomer, nitrogen oxides or its salt of object；Or it is the chemical combination as shown in formula (IId) compound represented or formula (IId) Stereoisomer, nitrogen oxides or its salt of object:

5. compound according to any one of claims 1-4, wherein

R¹And R²It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C_1-6Alkyl, halogenated C_1-6 Alkyl, C_3-6Naphthenic base or C_3-6Naphthenic base C_1-6Alkyl；Or R¹、R²It is formed together with the carbon atom being connected with them by 3-8 Former molecular ring；

R³And R⁴It is each independently hydrogen, bromine, iodine, amino, nitro, hydroxyl, carboxyl, C_1-6Alkyl, C_3-6Naphthenic base or C_3-6Cycloalkanes Base C_1-6Alkyl；Or R³、R⁴It is formed together with the carbon atom being connected with them by 3-8 former molecular ring；

R⁵And R⁶It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C_1-6Alkyl, C_2-6Alkenyl Or C_2-6Alkynyl；Or R⁵、R⁶It is formed together with the carbon atom being connected with them by 3-8 former molecular ring.

6. according to compound described in claim 2-4 any one, wherein

R⁸、R⁹、R¹⁰、R¹¹And R¹²It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C_1-6Alkane Base, halogenated C_1-6Alkyl, C_2-6Alkenyl, halogenated C_2-6Alkenyl, C_2-6Alkynyl, halogenated C_2-6Alkynyl, C_1-6Alkoxy, C_1-6Alkylamino, C_1-6Alkylthio group, C_3-6Naphthenic base, C_2-8Heterocycle, C_6-10Aryl or C_1-9Heteroaryl；

Or R⁸、R⁹The former molecular ring of 3-10 optionally replaced is formed together with the carbon atom being attached thereto；

Or R⁸、R⁹- C (=O)-is formed together with the carbon atom being attached thereto；

Or R¹⁰、R¹¹、R¹²- C ≡ CR is formed together with the carbon atom being attached thereto¹³Or-CR¹⁴=CR¹⁵R¹⁶；Wherein R¹³、R¹⁴、 R¹⁵And R¹⁶It is each independently hydrogen, C_1-6Alkyl, halogenated C_1-6Alkyl, C_2-6Alkenyl, halogenated C_2-6Alkenyl, C_2-6Alkynyl is halogenated C_2-6Alkynyl；

Or R¹⁰、R¹¹、R¹²The C optionally replaced is formed together with the carbon atom being attached thereto_6-14Aryl, the C optionally replaced_1-9It is miscellaneous Aryl, the C optionally replaced_3-10Naphthenic base or the C optionally replaced_2-10Heterocycle；

Or-CR⁸R⁹-CR¹⁰R¹¹R¹²Indicate the C optionally replaced_10-14Aryl, the C optionally replaced_1-9Heteroaryl optionally replaces C_3-10Naphthenic base, the C optionally replaced_2-10Heterocycle, unsubstituted phenyl or substituted phenyl；

The substitution optionally replaces, and substituent group number is 1,2,3,4,5 or 6；Substituent group can be identical or different；Wherein take Dai Jiwei fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C_1-6Alkyl, halogenated C_1-6Alkyl, C_2-6It is alkenyl, halogenated C_2-6Alkenyl, C_2-6Alkynyl, halogenated C_2-6Alkynyl, C_1-6Alkoxy, C_1-6Alkylamino, C_1-6Alkylthio group, C_3-8Naphthenic base, C_2-10Heterocycle Base, C_6-14Aryl or C_1-9Heteroaryl.

7. compound according to claim 1 or 2, for such as formula (II-1) compound represented or formula (II-1) shownization Close stereoisomer, nitrogen oxides or its salt of object:

Wherein:

N is 0,1 or 2；

X is fluorine, chlorine or bromine；

R⁸And R⁹It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, alkyl, halogenated alkyl, alkene Base, halogenated alkenyl, alkynyl, halo alkynyl, alkoxy, alkylamino, alkylthio group, naphthenic base, heterocycle, aryl or heteroaryl；

R¹³For hydrogen, alkyl, halogenated alkyl, alkenyl, halogenated alkenyl, alkynyl or halo alkynyl.

8. compound according to claim 7, for such as formula (IIa-1) compound represented or formula (IIa-1) shownization Close stereoisomer, nitrogen oxides or its salt of object；Or it is such as formula (IIa-2) compound represented or formula (IIa-2) institute Show the stereoisomer, nitrogen oxides or its salt of compound:

Wherein:

R⁸And R⁹It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C_1-6Alkyl, halogenated C_1-6 Alkyl, C_2-6Alkenyl, halogenated C_2-6Alkenyl, C_2-6Alkynyl, halogenated C_2-6Alkynyl, C_1-6Alkoxy, C_1-6Alkylamino, C_1-6Alkylthio group, C_3-6Naphthenic base, C_2-8Heterocycle, C_6-10Aryl or C_1-9Heteroaryl；

R¹³For hydrogen, C_1-6Alkyl, halogenated C_1-6Alkyl, C_2-6Alkenyl, halogenated C_2-6Alkenyl, C_2-6Alkynyl or halogenated C_2-6Alkynyl.

9. compound according to claim 1 is the chemical combination as shown in formula (II-5) compound represented or formula (II-5) Stereoisomer, nitrogen oxides or its salt of object:

Wherein:

N is 0,1 or 2；

X is fluorine, chlorine or bromine；

Condition is:

(i) when X is chlorine, R⁵And R⁶It is hydrogen, n 0,1 or 2, R³And R⁴When being hydrogen, R¹And R²It cannot simultaneously be methyl；

(ii) when X is chlorine and at 5 of pyrazole ring, R⁵And R⁶It is hydrogen, n 0,1 or 2, R³And R⁴It is hydrogen, R²When for methyl, R¹It is not chloromethyl；Or

(iii) when X is chlorine and at 5 of pyrazole ring, R⁵And R⁶It is hydrogen, n 0,1 or 2, R³And R⁴It is hydrogen, R¹When for methyl, R²It is not chloromethyl.

10. compound according to claim 9, for as shown in formula (IIa-17) compound represented or formula (IIa-17) Stereoisomer, nitrogen oxides or its salt of compound；Or it is such as formula (IIa-18) compound represented or formula (IIa- 18) stereoisomer, nitrogen oxides or its salt of compound shown in:

Wherein:

X is fluorine, chlorine or bromine；

Condition is:

(1) when X is chlorine, R⁵And R⁶It is hydrogen, R³And R⁴When being hydrogen, R¹And R²It cannot simultaneously be methyl；

(2) when X is chlorine and at 5 of pyrazole ring, R⁵And R⁶It is hydrogen, R³And R⁴It is hydrogen, R²When for methyl, R¹It is not chloromethane Base；Or

(3) when X is chlorine and at 5 of pyrazole ring, R⁵And R⁶It is hydrogen, R³And R⁴It is hydrogen, R¹When for methyl, R²It is not chloromethane Base.

11. according to claim 1-5 or claim 7-10 any one described in compound, wherein

R¹And R²It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C_1-4Alkyl, halogenated C_1-4 Alkyl, C_3-6Naphthenic base or C_3-6Naphthenic base C_1-3Alkyl；Or R¹、R²It is formed together with the carbon atom being connected with them by 3-6 Former molecular ring；

R³And R⁴It is each independently hydrogen, bromine, iodine, amino, nitro, hydroxyl, carboxyl, C_1-3Alkyl, C_3-6Naphthenic base or C_3-6Cycloalkanes Base C_1-3Alkyl；Or R³、R⁴It is formed together with the carbon atom being connected with them by 3-6 former molecular ring；

R⁵And R⁶It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C_1-4Alkyl, C_2-4Alkenyl Or C_2-4Alkynyl；Or R⁵、R⁶It is formed together with the carbon atom being connected with them by 3-6 former molecular ring.

12. compound according to claim 11, wherein

R¹And R²It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, methyl, ethyl, positive third Base, isopropyl ,-CH₂F、-CH₂Cl、-CH₂Br or-CF₃；

R³And R⁴It is each independently hydrogen or bromine；

R⁵And R⁶It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl or methyl.

13. compound according to claim 1 to 3, for such as formula (IIIa) compound represented or formula (IIIa) stereoisomer, nitrogen oxides or its salt of compound shown in:

14. compound according to claim 1 to 3, for such as formula (IIIb) compound represented or formula (IIIb) stereoisomer, nitrogen oxides or its salt of compound shown in:

15. according to claim 1-2 or claim 4 any one described in compound, for as shown in formula (IIIc) change Close stereoisomer, nitrogen oxides or its salt of compound shown in object or formula (IIIc):

16. according to claim 1-2 or claim 4 any one described in compound, for as shown in formula (IIId) change Close stereoisomer, nitrogen oxides or its salt of compound shown in object or formula (IIId):

17. according to compound described in claim 6 or claim 13-16 any one, wherein

R⁸、R⁹、R¹⁰、R¹¹And R¹²It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C_1-4Alkane Base, halogenated C_1-4Alkyl, C_2-4Alkenyl, halogenated C_2-4Alkenyl, C_2-4Alkynyl, halogenated C_2-4Alkynyl, C_1-4Alkoxy, C_1-4Alkylamino, C_1-4Alkylthio group, C_3-6Naphthenic base, C_2-6Heterocycle, C_6-10Aryl or C_1-5Heteroaryl；

Or R⁸、R⁹The former molecular ring of 3-8 optionally replaced is formed together with the carbon atom being attached thereto；

Or R⁸、R⁹- C (=O)-is formed together with the carbon atom being attached thereto；

Or R¹⁰、R¹¹、R¹²- C ≡ CR is formed together with the carbon atom being attached thereto¹³Or-CR¹⁴=CR¹⁵R¹⁶；Wherein R¹³、R¹⁴、 R¹⁵And R¹⁶It is each independently hydrogen, C_1-4Alkyl, halogenated C_1-4Alkyl, C_2-4Alkenyl, halogenated C_2-4Alkenyl, C_2-4Alkynyl is halogenated C_2-4Alkynyl；

Or R¹⁰、R¹¹、R¹²The C optionally replaced is formed together with the carbon atom being attached thereto_6-10Aryl, the C optionally replaced_1-6It is miscellaneous Aryl, the C optionally replaced_3-8Naphthenic base or the C optionally replaced_2-6Heterocycle；

Or-CR⁸R⁹-CR¹⁰R¹¹R¹²Indicate the C optionally replaced_10-14Aryl, the C optionally replaced_1-6Heteroaryl optionally replaces C_3-8Naphthenic base, the C optionally replaced_2-6Heterocycle, unsubstituted phenyl or substituted phenyl；

The substitution optionally replaces, and substituent group number is 1,2,3,4,5 or 6；Substituent group can be identical or different；Wherein take Dai Jiwei fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C_1-6Alkyl, halogenated C_1-4Alkyl, C_2-4It is alkenyl, halogenated C_2-4Alkenyl, C_2-4Alkynyl, halogenated C_2-4Alkynyl, C_1-4Alkoxy, C_1-4Alkylamino, C_1-4Alkylthio group, C_3-6Naphthenic base, C_2-6Heterocycle Base, C_6-10Aryl or C_1-5Heteroaryl.

18. compound according to claim 17, wherein

R⁸、R⁹、R¹⁰、R¹¹And R¹²It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl ,-CH₃、- CH₂CH₃、-CH₂CH₂CH₃、-CH(CH₃)₂、-CH₂F、-CHF₂、-CH₂Cl、-CH₂Br、-CF₃、-CH₂CF₃、-CH₂CH₂F、- CH₂CH₂Cl、-CH₂CH₂Br、-CH₂CHF₂、-CH₂CH₂CF₃、-CH₂CH₂CH₂F、-CH₂CH₂CH₂Cl、-CH₂CH₂CH₂Br、- CHFCH₂CH₃、-CHClCH₂CH₃,-CH=CH₂、-CH₂CH=CH₂、CH₃- CH=CH- ,-C ≡ CH ,-C ≡ CCH₃、-CH₂-C≡ CH、-OCH₃、-OCH₂CH₃、-OCH₂CH₂CH₃、-OCH(CH₃)₂、-NHCH₃、-N(CH₃)₂、-SCH₃、-SCH₂CH₃、- SCH₂CH₂CH₃, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl or phenyl；

Or R⁸、R⁹C is formed together with the carbon atom being attached thereto_3-6Naphthenic base；

Or R⁸、R⁹- C (=O)-is formed together with the carbon atom being attached thereto；

Or R¹⁰、R¹¹、R¹²- C ≡ CH or-CH=CH is formed together with the carbon atom being attached thereto₂；

Or R¹⁰、R¹¹、R¹²C is formed together with the carbon atom being attached thereto_3-6Naphthenic base, the phenyl being optionally optionally substituted by halogen contain The C of one oxygen_2-6Heterocycle；

Or-CR⁸R⁹-CR¹⁰R¹¹R¹²Indicate C_3-6The phenyl that naphthenic base or halogen replace.

19. compound according to claim 1 or 2, for as shown in formula (IIIe) compound represented or formula (IIIe) Stereoisomer, nitrogen oxides or its salt of compound:

Wherein:

R⁵And R⁶It is each independently hydrogen or fluorine；

X is fluorine or chlorine；

R^mFor hydrogen, C_1-3Alkyl or halogenated C_1-3Alkyl；

R^vFor hydrogen, C_1-3Alkyl or halogenated C_1-3Alkyl；

R^wFor C_1-3Alkyl or halogenated C_1-3Alkyl.

20. compound according to claim 19, in which:

R^mFor hydrogen or methyl；

R^vFor hydrogen or methyl；

R^wFor methyl, isopropyl, difluoromethyl or four fluoro ethyls.

21. compound according to claim 1 or 2, for as shown in formula (IIIf) compound represented or formula (IIIf) Stereoisomer, nitrogen oxides or its salt of compound:

Wherein:

R⁵And R⁶It is each independently hydrogen or fluorine；

X is fluorine or chlorine；

R^mFor hydrogen, C_1-3Alkyl or halogenated C_1-3Alkyl；

R^vFor hydrogen, C_1-3Alkyl or halogenated C_1-3Alkyl；

R^wFor C_1-3Alkyl or halogenated C_1-3Alkyl.

22. compound according to claim 21, in which:

R^mFor hydrogen or methyl；

R^vFor hydrogen or methyl；

R^wFor methyl, isopropyl, difluoromethyl or four fluoro ethyls.

23. compound according to claim 1 or 2, for as shown in formula (IIIg) compound represented or formula (IIIg) Stereoisomer, nitrogen oxides or its salt of compound:

Wherein: X is fluorine or chlorine.

24. compound according to claim 1 is the chemical combination as shown in formula (IIIh) compound represented or formula (IIIh) Stereoisomer, nitrogen oxides or its salt of object:

Wherein: X is fluorine, chlorine or bromine.

25. compound described in -24 any one according to claim 1 is compound or tool with one of following structure There are the stereoisomer, nitrogen oxides or its salt of one of following structural compounds:

26. a kind of Herbicidal combinations, wherein with the vertical of compound described in claim 1-25 any one or the compound Body isomers, nitrogen oxides or its salt are as active component.

27. Herbicidal combinations described in compound described in claim 1-25 any one or claim 26 are in agriculture weeding In application.

28. a kind of method of weed growth in control useful plant, it includes a effective amount of such as to weeds location preemergence application Compound described in claim 1-25 any one.

29. according to the method for claim 28, the weeds include broad-leaved section weeds and gramineae weed.

30. according to the method for claim 29, broad-leaved section weeds include piemarker, Amaranthus retroflexus, Eclipta prostrata；The grass family Weeds include herba digitariae, barnyard grass and herba setariae viridis.

31. according to the method for claim 28, the useful plant includes soybean, peanut and sunflower.

Technical field

The present invention provides a kind of new isoxazoline derivative and preparation method thereof；Composition containing these compounds and Its application in agricultural.

Background technique

Isoxazoles compound is a kind of compound with excellent bioactivity, and activity of weeding is reported in such as WO 2002062770, it is described in WO 2003000686 and WO 2003010165.However, the present inventionization being described in more detail below Object is closed not describe in those references.

Known active constituent has a disadvantage that in use from cited documents above, such as (a) right The ruderal plant spectrum that ruderal plant or does not only have inadequate herbicide effect, (b) to be prevented and treated is narrow or (c) useful Selectivity in plant crop is too low.

Accordingly, it is desirable to provide the chemical active ingredient of herbicide or plant growth regulator can be advantageously used for.

Summary of the invention

The present invention provides a kind of new isoxazoles compound, with excellent herbicide effect and crops with it is miscellaneous Fine selectivity between grass.

On the one hand, the present invention provides stereoisomer, the nitrogen of compound shown in formula (Ia) compound represented or formula (Ia) Oxide or its salt:

Wherein:

R¹And R²It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, alkyl, alkyl halide Base, naphthenic base or cycloalkyl-alkyl；Or R¹、R²It is formed together with the carbon atom being connected with them former molecular by 3-12 Ring；

R³And R⁴It is each independently hydrogen, bromine, iodine, amino, nitro, hydroxyl, carboxyl, alkyl, naphthenic base or naphthenic base alkane Base；Or R³、R⁴It is formed together with the carbon atom being connected with them by 3-12 former molecular ring；

N is 0,1 or 2；

R⁵And R⁶Be each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, alkyl, alkenyl or Alkynyl；Or R⁵、R⁶It is formed together with the carbon atom being connected with them by 3-12 former molecular ring；

X is fluorine, chlorine or bromine；

Y is alkyl, halogenated alkyl, alkoxyalkyl, alkyl amino alkyl, alkenyl, halogenated alkenyl, alkynyl, halo alkynyl, ring Alkyl, cycloalkyl-alkyl, heterocycle, heterocyclylalkyl group, aryl, aryl alkyl, heteroaryl, heteroaryl alkyl ,-C (=O)-alkane Base ,-S (=O)₂Alkyl ,-C (=O)-naphthenic base ,-S (=O)₂Naphthenic base ,-C (=O)-heterocycle ,-S (=O)₂Heterocycle Base ,-C (=O)-aryl ,-S (=O)₂Aryl ,-C (=O)-heteroaryl or-S (=O)₂Heteroaryl；

Wherein Y is optionally selected from Y by 1,2,3,4,5 or 6^aSubstituent group replaced；Each Y^aIndependently be fluorine, chlorine, bromine, Iodine, amino, nitro, cyano, hydroxyl, carboxyl, alkyl, halogenated alkyl, alkenyl, halogenated alkenyl, alkynyl, halo alkynyl, alkoxy, Alkylamino, alkylthio group, naphthenic base, heterocycle, aryl or heteroaryl；

Condition is:

(1) when Y is methyl, X is chlorine, R⁵And R⁶It is hydrogen, n 0,1 or 2, R³And R⁴It is hydrogen, R¹When for methyl, R²No For methyl or chloromethyl；

(2) when Y is methyl, X is chlorine, R⁵And R⁶It is hydrogen, n 0,1 or 2, R³And R⁴It is hydrogen, R²When for methyl, R¹No For methyl or chloromethyl；

(3) when Y is unsubstituted phenyl, X is chlorine, R⁵And R⁶It is hydrogen, n 0,1 or 2, R³And R⁴It is hydrogen, R¹For methyl When, R²It is not methyl or chloromethyl；

(4) when Y is unsubstituted phenyl, X is chlorine, R⁵And R⁶It is hydrogen, n 0,1 or 2, R³And R⁴It is hydrogen, R²For methyl When, R¹It is not methyl or chloromethyl；

(5) when Y is ethyl or isopropyl, X is chlorine and at 5 of pyrazole ring, R⁵And R⁶It is hydrogen, n is 0 or 2, R³And R⁴ It is hydrogen, R¹When for methyl, R²It is not chloromethyl；Or

(6) when Y is ethyl or isopropyl, X is chlorine and at 5 of pyrazole ring, R⁵And R⁶It is hydrogen, n is 0 or 2, R³And R⁴ It is hydrogen, R²When for methyl, R¹It is not chloromethyl.

In some of embodiments, the present invention provides a kind of compound, is formula (II) compound represented or formula (II) stereoisomer, nitrogen oxides or its salt of compound shown in:

Wherein:

X is fluorine, chlorine or bromine；

N is 0,1 or 2；

R⁸、R⁹、R¹⁰、R¹¹And R¹²It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, alkane Base, halogenated alkyl, alkenyl, halogenated alkenyl, alkynyl, halo alkynyl, alkoxy, alkylamino, alkylthio group, naphthenic base, heterocycle, virtue Base or heteroaryl；

Or R⁸、R⁹The former molecular ring of 3-12 optionally replaced is formed together with the carbon atom being attached thereto；

Or R⁸、R⁹- C (=O)-is formed together with the carbon atom being attached thereto；

Or R¹⁰、R¹¹、R¹²- C ≡ CR is formed together with the carbon atom being attached thereto¹³Or-CR¹⁴=CR¹⁵R¹⁶；Wherein R¹³、 R¹⁴、R¹⁵And R¹⁶It is each independently hydrogen, alkyl, halogenated alkyl, alkenyl, halogenated alkenyl, alkynyl or halo alkynyl；

The substitution optionally replaces, and substituent group number is 1,2,3,4,5 or 6；Substituent group can be identical or different；Its Middle substituent group is fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, alkyl, halogenated alkyl, alkenyl, halogenated alkenyl, alkynes Base, halo alkynyl, alkoxy, alkylamino, alkylthio group, naphthenic base, heterocycle, aryl or heteroaryl；

Condition is:

(a) as-CR⁸R⁹-CR¹⁰R¹¹R¹²Indicate that unsubstituted phenyl, X are chlorine, R⁵And R⁶It is hydrogen, n 0,1 or 2, R³With R⁴It is hydrogen, R¹When for methyl, R²It is not methyl or chloromethyl；

(b) as-CR⁸R⁹-CR¹⁰R¹¹R¹²Indicate that unsubstituted phenyl, X are chlorine, R⁵And R⁶It is hydrogen, n 0,1 or 2, R³With R⁴It is hydrogen, R²When for methyl, R¹It is not methyl or chloromethyl；

(c) as-CR⁸R⁹-CR¹⁰R¹¹R¹²Indicate ethyl or isopropyl, X is chlorine and at 5 of pyrazole ring, R⁵And R⁶It is Hydrogen, n are 0 or 2, R³And R⁴It is hydrogen, R¹When for methyl, R²It is not chloromethyl；Or

(d) as-CR⁸R⁹-CR¹⁰R¹¹R¹²Indicate ethyl or isopropyl, X is chlorine and at 5 of pyrazole ring, R⁵And R⁶It is Hydrogen, n are 0 or 2, R³And R⁴It is hydrogen, R²When for methyl, R¹It is not chloromethyl.

In some of embodiments, the present invention provides a kind of compound, for such as formula (IIa) compound represented or formula (IIa) stereoisomer, nitrogen oxides or its salt of compound shown in:

Wherein: R¹、R²、R³、R⁴、R⁵、R⁶、R⁸、R⁹、R¹⁰、R¹¹And R¹²With meaning as described in the present invention.

In other embodiment, the present invention provides a kind of compound, for such as formula (IIa) compound represented or formula (IIa) stereoisomer, nitrogen oxides or its salt of compound shown in, in which:

R¹And R²It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C_1-6It is alkyl, halogenated C_1-6Alkyl, C_3-6Naphthenic base or C_3-6Naphthenic base C_1-6Alkyl；Or R¹、R²It is formed together with the carbon atom being connected with them by 3-8 A molecular ring of original；

R³And R⁴It is each independently hydrogen, bromine, iodine, amino, nitro, hydroxyl, carboxyl, C_1-6Alkyl, C_3-6Naphthenic base or C_3-6 Naphthenic base C_1-6Alkyl；Or R³、R⁴It is formed together with the carbon atom being connected with them by 3-8 former molecular ring；

R⁵And R⁶It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C_1-6Alkyl, C_2-6 Alkenyl or C_2-6Alkynyl；Or R⁵、R⁶It is formed together with the carbon atom being connected with them by 3-8 former molecular ring；

R⁸、R⁹、R¹⁰、R¹¹And R¹²Be each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C_1-6Alkyl, halogenated C_1-6Alkyl, C_2-6Alkenyl, halogenated C_2-6Alkenyl, C_2-6Alkynyl, halogenated C_2-6Alkynyl, C_1-6Alkoxy, C_1-6Alkane ammonia Base, C_1-6Alkylthio group, C_3-6Naphthenic base, C_2-8Heterocycle, C_6-10Aryl or C_1-9Heteroaryl；

Or R⁸、R⁹The former molecular ring of 3-10 optionally replaced is formed together with the carbon atom being attached thereto；

Or R⁸、R⁹- C (=O)-is formed together with the carbon atom being attached thereto；

Or R¹⁰、R¹¹、R¹²- C ≡ CR is formed together with the carbon atom being attached thereto¹³Or-CR¹⁴=CR¹⁵R¹⁶；Wherein R¹³、 R¹⁴、R¹⁵And R¹⁶It is each independently hydrogen, C_1-6Alkyl, halogenated C_1-6Alkyl, C_2-6Alkenyl, halogenated C_2-6Alkenyl, C_2-6Alkynyl or halogen For C_2-6Alkynyl；

Or-CR⁸R⁹-CR¹⁰R¹¹R¹²Indicate the C optionally replaced_10-14Aryl, the C optionally replaced_1-9Heteroaryl optionally takes The C in generation_3-10Naphthenic base, the C optionally replaced_2-10Heterocycle, unsubstituted phenyl or substituted phenyl；

The substitution optionally replaces, and substituent group number is 1,2,3,4,5 or 6；Substituent group can be identical or different；Its Middle substituent group is fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C_1-6Alkyl, halogenated C_1-6Alkyl, C_2-6Alkenyl, halogen For C_2-6Alkenyl, C_2-6Alkynyl, halogenated C_2-6Alkynyl, C_1-6Alkoxy, C_1-6Alkylamino, C_1-6Alkylthio group, C_3-8Naphthenic base, C_2-10It is miscellaneous Ring group, C_6-14Aryl or C_1-9Heteroaryl；

Condition is:

(a) as-CR⁸R⁹-CR¹⁰R¹¹R¹²Indicate unsubstituted phenyl, R⁵And R⁶It is hydrogen, R³And R⁴It is hydrogen, R¹For methyl When, R²It is not methyl or chloromethyl；

(b) as-CR⁸R⁹-CR¹⁰R¹¹R¹²Indicate unsubstituted phenyl, R⁵And R⁶It is hydrogen, R³And R⁴It is hydrogen, R²For methyl When, R¹It is not methyl or chloromethyl；

(c) as-CR⁸R⁹-CR¹⁰R¹¹R¹²Indicate ethyl or isopropyl, R⁵And R⁶It is hydrogen, R³And R⁴It is hydrogen, R¹For methyl When, R²It is not chloromethyl；Or

(d) as-CR⁸R⁹-CR¹⁰R¹¹R¹²Indicate ethyl or isopropyl, R⁵And R⁶It is hydrogen, R³And R⁴It is hydrogen, R²For methyl When, R¹It is not chloromethyl.

In some of embodiments, the present invention provides a kind of compound, for such as formula (IIb) compound represented or formula (IIb) stereoisomer, nitrogen oxides or its salt of compound shown in:

Wherein: R¹、R²、R³、R⁴、R⁵、R⁶、R⁸、R⁹、R¹⁰、R¹¹And R¹²With meaning as described in the present invention.

In other embodiment, the present invention provides a kind of compound, for such as formula (IIb) compound represented or formula (IIb) stereoisomer, nitrogen oxides or its salt of compound shown in, in which:

Or R⁸、R⁹The former molecular ring of 3-10 optionally replaced is formed together with the carbon atom being attached thereto；

Or R⁸、R⁹- C (=O)-is formed together with the carbon atom being attached thereto；

Or R¹⁰、R¹¹、R¹²- C ≡ CR is formed together with the carbon atom being attached thereto¹³Or-CR¹⁴=CR¹⁵R¹⁶；Wherein R¹³、 R¹⁴、R¹⁵And R¹⁶It is each independently hydrogen, C_1-6Alkyl, halogenated C_1-6Alkyl, C_2-6Alkenyl, halogenated C_2-6Alkenyl, C_2-6Alkynyl or halogen For C_2-6Alkynyl；

The substitution optionally replaces, and substituent group number is 1,2,3,4,5 or 6；Substituent group can be identical or different；Its Middle substituent group is fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C_1-6Alkyl, halogenated C_1-6Alkyl, C_2-6Alkenyl, halogen For C_2-6Alkenyl, C_2-6Alkynyl, halogenated C_2-6Alkynyl, C_1-6Alkoxy, C_1-6Alkylamino, C_1-6Alkylthio group, C_3-8Naphthenic base, C_2-10It is miscellaneous Ring group, C_6-14Aryl or C_1-9Heteroaryl；

Condition is:

(a) as-CR⁸R⁹-CR¹⁰R¹¹R¹²Indicate unsubstituted phenyl, R⁵And R⁶It is hydrogen, R³And R⁴It is hydrogen, R¹For methyl When, R²It is not methyl or chloromethyl；Or

(b) as-CR⁸R⁹-CR¹⁰R¹¹R¹²Indicate unsubstituted phenyl, R⁵And R⁶It is hydrogen, R³And R⁴It is hydrogen, R²For methyl When, R¹It is not methyl or chloromethyl.

In some of embodiments, the present invention provides a kind of compound, for such as formula (IIc) compound represented or formula (IIc) stereoisomer, nitrogen oxides or its salt of compound shown in:

Wherein: R¹、R²、R³、R⁴、R⁵、R⁶、R⁸、R⁹、R¹⁰、R¹¹And R¹²With meaning as described in the present invention.

In other embodiment, the present invention provides a kind of compound, for such as formula (IIc) compound represented or formula (IIc) stereoisomer, nitrogen oxides or its salt of compound shown in, in which:

Or R⁸、R⁹The former molecular ring of 3-10 optionally replaced is formed together with the carbon atom being attached thereto；

Or R⁸、R⁹- C (=O)-is formed together with the carbon atom being attached thereto；

Or R¹⁰、R¹¹、R¹²- C ≡ CR is formed together with the carbon atom being attached thereto¹³Or-CR¹⁴=CR¹⁵R¹⁶；Wherein R¹³、 R¹⁴、R¹⁵And R¹⁶It is each independently hydrogen, C_1-6Alkyl, halogenated C_1-6Alkyl, C_2-6Alkenyl, halogenated C_2-6Alkenyl, C_2-6Alkynyl or halogen For C_2-6Alkynyl；

The substitution optionally replaces, and substituent group number is 1,2,3,4,5 or 6；Substituent group can be identical or different；Its Middle substituent group is fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C_1-6Alkyl, halogenated C_1-6Alkyl, C_2-6Alkenyl, halogen For C_2-6Alkenyl, C_2-6Alkynyl, halogenated C_2-6Alkynyl, C_1-6Alkoxy, C_1-6Alkylamino, C_1-6Alkylthio group, C_3-8Naphthenic base, C_2-10It is miscellaneous Ring group, C_6-14Aryl or C_1-9Heteroaryl.

In some of embodiments, the present invention provides a kind of compound, for such as formula (IId) compound represented or formula (IId) stereoisomer, nitrogen oxides or its salt of compound shown in:

Wherein: R¹、R²、R³、R⁴、R⁵、R⁶、R⁸、R⁹、R¹⁰、R¹¹And R¹²With meaning as described in the present invention.

In other embodiment, the present invention provides a kind of compound, for such as formula (IId) compound represented or formula (IId) stereoisomer, nitrogen oxides or its salt of compound shown in, in which:

Or R⁸、R⁹The former molecular ring of 3-10 optionally replaced is formed together with the carbon atom being attached thereto；

Or R⁸、R⁹- C (=O)-is formed together with the carbon atom being attached thereto；

Or R¹⁰、R¹¹、R¹²- C ≡ CR is formed together with the carbon atom being attached thereto¹³Or-CR¹⁴=CR¹⁵R¹⁶；Wherein R¹³、 R¹⁴、R¹⁵And R¹⁶It is each independently hydrogen, C_1-6Alkyl, halogenated C_1-6Alkyl, C_2-6Alkenyl, halogenated C_2-6Alkenyl, C_2-6Alkynyl or halogen For C_2-6Alkynyl；

The substitution optionally replaces, and substituent group number is 1,2,3,4,5 or 6；Substituent group can be identical or different；Its Middle substituent group is fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C_1-6Alkyl, halogenated C_1-6Alkyl, C_2-6Alkenyl, halogen For C_2-6Alkenyl, C_2-6Alkynyl, halogenated C_2-6Alkynyl, C_1-6Alkoxy, C_1-6Alkylamino, C_1-6Alkylthio group, C_3-8Naphthenic base, C_2-10It is miscellaneous Ring group, C_6-14Aryl or C_1-9Heteroaryl.

In some of embodiments, the present invention provides a kind of compound, is formula (II-1) compound represented or formula (II-1) stereoisomer, nitrogen oxides or its salt of compound shown in:

Wherein:

N is 0,1 or 2；

X is fluorine, chlorine or bromine；

R⁸And R⁹It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, alkyl, alkyl halide Base, alkenyl, halogenated alkenyl, alkynyl, halo alkynyl, alkoxy, alkylamino, alkylthio group, naphthenic base, heterocycle, aryl or heteroaryl Base；

R¹³For hydrogen, alkyl, halogenated alkyl, alkenyl, halogenated alkenyl, alkynyl or halo alkynyl.

In some of embodiments, the present invention provides a kind of compound, for such as formula (IIa-1) compound represented or Stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIa-1):

Wherein: R¹、R²、R³、R⁴、R⁵、R⁶、R⁸、R⁹And R¹³With meaning as described in the present invention.

In other embodiment, the present invention provides a kind of compound, for such as formula (IIa-1) compound represented or Stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIa-1), in which:

R⁸And R⁹It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C_1-6It is alkyl, halogenated C_1-6Alkyl, C_2-6Alkenyl, halogenated C_2-6Alkenyl, C_2-6Alkynyl, halogenated C_2-6Alkynyl, C_1-6Alkoxy, C_1-6Alkylamino, C_1-6Alkane sulphur Base, C_3-6Naphthenic base, C_2-8Heterocycle, C_6-10Aryl or C_1-9Heteroaryl；

R¹³For hydrogen, C_1-6Alkyl, halogenated C_1-6Alkyl, C_2-6Alkenyl, halogenated C_2-6Alkenyl, C_2-6Alkynyl or halogenated C_2-6Alkynyl.

In some of embodiments, the present invention provides a kind of compound, for such as formula (IIa-2) compound represented or Stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIa-2):

Wherein: R¹、R²、R³、R⁴、R⁵、R⁶、R⁸、R⁹And R¹³With meaning as described in the present invention.

In other embodiment, the present invention provides a kind of compound, for such as formula (IIa-2) compound represented or Stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIa-2), in which:

R¹³For hydrogen, C_1-6Alkyl, halogenated C_1-6Alkyl, C_2-6Alkenyl, halogenated C_2-6Alkenyl, C_2-6Alkynyl or halogenated C_2-6Alkynyl.

In some of embodiments, the present invention provides a kind of compound, for such as formula (II-5) compound represented or Stereoisomer, nitrogen oxides or its salt of compound shown in formula (II-5):

Wherein:

N is 0,1 or 2；

X is fluorine, chlorine or bromine；

Condition is:

(i) when X is chlorine, R⁵And R⁶It is hydrogen, n 0,1 or 2, R³And R⁴When being hydrogen, R¹And R²It cannot simultaneously be methyl；

(ii) when X is chlorine and at 5 of pyrazole ring, R⁵And R⁶It is hydrogen, n 0,1 or 2, R³And R⁴It is hydrogen, R²For methyl When, R¹It is not chloromethyl；Or

(iii) when X is chlorine and at 5 of pyrazole ring, R⁵And R⁶It is hydrogen, n 0,1 or 2, R³And R⁴It is hydrogen, R¹For first When base, R²It is not chloromethyl.

In some of embodiments, the present invention provides a kind of compound, for such as formula (IIa-17) compound represented Or stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIa-17):

Wherein: R¹、R²、R³、R⁴、R⁵、R⁶There is meaning as described in the present invention with X.

In other embodiment, the present invention provides a kind of compound, for such as formula (IIa-17) compound represented Or stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIa-17), in which:

X is fluorine, chlorine or bromine；

Condition is:

(1) when X is chlorine, R⁵And R⁶It is hydrogen, R³And R⁴When being hydrogen, R¹And R²It cannot simultaneously be methyl；

(2) when X is chlorine, R⁵And R⁶It is hydrogen, R³And R⁴It is hydrogen, R²When for methyl, R¹It is not chloromethyl；Or

(3) when X is chlorine, R⁵And R⁶It is hydrogen, R³And R⁴It is hydrogen, R¹When for methyl, R²It is not chloromethyl.

In some of embodiments, the present invention provides a kind of compound, for such as formula (IIa-18) compound represented Or stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIa-18):

Wherein: R¹、R²、R³、R⁴、R⁵、R⁶There is meaning as described in the present invention with X.

In other embodiment, the present invention provides a kind of compound, for such as formula (IIa-18) compound represented Or stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIa-18), in which:

X is fluorine, chlorine or bromine；

Condition is:

(1) when X is chlorine, R⁵And R⁶It is hydrogen, R³And R⁴When being hydrogen, R¹And R²It cannot simultaneously be methyl.

In other embodiment, R¹And R²It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl Base, carboxyl, C_1-4Alkyl, halogenated C_1-4Alkyl, C_3-6Naphthenic base or C_3-6Naphthenic base C_1-3Alkyl；Or R¹、R²It is connected with them Carbon atom be formed together by 3-6 former molecular ring；

R³And R⁴It is each independently hydrogen, bromine, iodine, amino, nitro, hydroxyl, carboxyl, C_1-3Alkyl, C_3-6Naphthenic base or C_3-6 Naphthenic base C_1-3Alkyl；Or R³、R⁴It is formed together with the carbon atom being connected with them by 3-6 former molecular ring；

R⁵And R⁶It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C_1-4Alkyl, C_2-4 Alkenyl or C_2-4Alkynyl；Or R⁵、R⁶It is formed together with the carbon atom being connected with them by 3-6 former molecular ring.

In other embodiment, R¹And R²It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl Base, carboxyl, methyl, ethyl, n-propyl, isopropyl ,-CH₂F、-CH₂Cl、-CH₂Br or-CF₃；

R³And R⁴It is each independently hydrogen or bromine；

R⁵And R⁶It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl or methyl.

In other embodiment, the present invention provides a kind of compound, for such as formula (IIIa) compound represented or Stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIIa):

Wherein: R⁸、R⁹、R¹⁰、R¹¹And R¹²With meaning as described in the present invention.

In other embodiment, the present invention provides a kind of compound, for such as formula (IIIb) compound represented or Stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIIb):

Wherein: R⁸、R⁹、R¹⁰、R¹¹And R¹²With meaning as described in the present invention.

In other embodiment, the present invention provides a kind of compound, for such as formula (IIIc) compound represented or Stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIIc):

Wherein: R⁸、R⁹、R¹⁰、R¹¹And R¹²With meaning as described in the present invention.

In other embodiment, the present invention provides a kind of compound, for such as formula (IIId) compound represented or Stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIId):

Wherein: R⁸、R⁹、R¹⁰、R¹¹And R¹²With meaning as described in the present invention.

In other embodiment, R⁸、R⁹、R¹⁰、R¹¹And R¹²It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitre Base, cyano, hydroxyl, carboxyl, C_1-4Alkyl, halogenated C_1-4Alkyl, C_2-4Alkenyl, halogenated C_2-4Alkenyl, C_2-4Alkynyl, halogenated C_2-4Alkynes Base, C_1-4Alkoxy, C_1-4Alkylamino, C_1-4Alkylthio group, C_3-6Naphthenic base, C_2-6Heterocycle, C_6-10Aryl or C_1-5Heteroaryl；

Or R⁸、R⁹The former molecular ring of 3-8 optionally replaced is formed together with the carbon atom being attached thereto；

Or R⁸、R⁹- C (=O)-is formed together with the carbon atom being attached thereto；

Or R¹⁰、R¹¹、R¹²- C ≡ CR is formed together with the carbon atom being attached thereto¹³Or-CR¹⁴=CR¹⁵R¹⁶；Wherein R¹³、 R¹⁴、R¹⁵And R¹⁶It is each independently hydrogen, C_1-4Alkyl, halogenated C_1-4Alkyl, C_2-4Alkenyl, halogenated C_2-4Alkenyl, C_2-4Alkynyl or halogen For C_2-4Alkynyl；

Or R¹⁰、R¹¹、R¹²The C optionally replaced is formed together with the carbon atom being attached thereto_6-10Aryl optionally replaces C_1-6Heteroaryl, the C optionally replaced_3-8Naphthenic base or the C optionally replaced_2-6Heterocycle；

Or-CR⁸R⁹-CR¹⁰R¹¹R¹²Indicate the C optionally replaced_10-14Aryl, the C optionally replaced_1-6Heteroaryl optionally takes The C in generation_3-8Naphthenic base, the C optionally replaced_2-6Heterocycle, unsubstituted phenyl or substituted phenyl；

The substitution optionally replaces, and substituent group number is 1,2,3,4,5 or 6；Substituent group can be identical or different；Its Middle substituent group is fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C_1-6Alkyl, halogenated C_1-4Alkyl, C_2-4Alkenyl, halogen For C_2-4Alkenyl, C_2-4Alkynyl, halogenated C_2-4Alkynyl, C_1-4Alkoxy, C_1-4Alkylamino, C_1-4Alkylthio group, C_3-6Naphthenic base, C_2-6Heterocycle Base, C_6-10Aryl or C_1-5Heteroaryl.

In other embodiment, R⁸、R⁹、R¹⁰、R¹¹And R¹²It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitre Base, cyano, hydroxyl, carboxyl ,-CH₃、-CH₂CH₃、-CH₂CH₂CH₃、-CH(CH₃)₂、-CH₂F、-CHF₂、-CH₂Cl、-CH₂Br、- CF₃、-CH₂CF₃、-CH₂CH₂F、-CH₂CH₂Cl、-CH₂CH₂Br、-CH₂CHF₂、-CH₂CH₂CF₃、-CH₂CH₂CH₂F、- CH₂CH₂CH₂Cl、-CH₂CH₂CH₂Br、-CHFCH₂CH₃、-CHClCH₂CH₃,-CH=CH₂、-CH₂CH=CH₂、CH₃- CH=CH- ,- C≡CH、-C≡CCH₃、-CH₂-C≡CH、-OCH₃、-OCH₂CH₃、-OCH₂CH₂CH₃、-OCH(CH₃)₂、-NHCH₃、-N(CH₃)₂、- SCH₃、-SCH₂CH₃、-SCH₂CH₂CH₃, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl or phenyl；

Or R⁸、R⁹C is formed together with the carbon atom being attached thereto_3-6Naphthenic base；

Or R⁸、R⁹- C (=O)-is formed together with the carbon atom being attached thereto；

Or R¹⁰、R¹¹、R¹²- C ≡ CH or-CH=CH is formed together with the carbon atom being attached thereto₂；

Or R¹⁰、R¹¹、R¹²C is formed together with the carbon atom being attached thereto_3-6Naphthenic base, the phenyl being optionally optionally substituted by halogen Or the C containing an oxygen_2-6Heterocycle；

Or-CR⁸R⁹-CR¹⁰R¹¹R¹²Indicate C_3-6The phenyl that naphthenic base or halogen replace.

In some of embodiments, the present invention provides a kind of compound, for such as formula (IIIe) compound represented or Stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIIe):

Wherein:

R⁵And R⁶It is each independently hydrogen or fluorine；

X is fluorine or chlorine；

R^mFor hydrogen, C_1-3Alkyl or halogenated C_1-3Alkyl；

R^vFor hydrogen, C_1-3Alkyl or halogenated C_1-3Alkyl；

R^wFor C_1-3Alkyl or halogenated C_1-3Alkyl.

In other embodiment, the present invention provides a kind of compound, for such as formula (IIIe) compound represented or Stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIIe), wherein R^mFor hydrogen or methyl；R^vFor hydrogen or methyl；R^w For methyl, isopropyl, difluoromethyl or four fluoro ethyls.

In some of embodiments, the present invention provides a kind of compound, for such as formula (IIIf) compound represented or Stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIIf):

Wherein:

R⁵And R⁶It is each independently hydrogen or fluorine；

X is fluorine or chlorine；

R^mFor hydrogen, C_1-3Alkyl or halogenated C_1-3Alkyl；

R^vFor hydrogen, C_1-3Alkyl or halogenated C_1-3Alkyl；

R^wFor C_1-3Alkyl or halogenated C_1-3Alkyl.

In other embodiment, the present invention provides a kind of compound, for such as formula (IIIf) compound represented or Stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIIf), wherein R^mFor hydrogen or methyl；R^vFor hydrogen or methyl；R^w For methyl, isopropyl, difluoromethyl or four fluoro ethyls.

In some of embodiments, the present invention provides a kind of compound, for such as formula (IIIg) compound represented or Stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIIg):

Wherein: X is fluorine or chlorine.

In some of embodiments, the present invention provides a kind of compound, for such as formula (IIIh) compound represented or Stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIIh):

Wherein: X is fluorine, chlorine or bromine.

On the other hand, the present invention provides a kind of composition, includes compound of the present invention or chemical combination of the present invention Stereoisomer, nitrogen oxides or its salt of object, optionally further comprising at least one auxiliary agent pesticide-acceptable.

Further, the present invention provides a kind of Herbicidal combinations, wherein with compound of the present invention or institute of the present invention The stereoisomer, nitrogen oxides or its salt of compound are stated as active component, optionally further comprising at least one pesticide Upper acceptable auxiliary agent.

On the other hand, the present invention provides compound of the present invention or the composition comprising compound of the present invention in agriculture Application in industry.

Further, the present invention provides compound of the present invention or the composition comprising compound of the present invention is being planted Application in object disease control.

Further, the present invention provides compound of the present invention or the composition comprising compound of the present invention exists Application in agriculture weeding.

In some of embodiments, the present invention provides compound of the present invention or comprising compound of the present invention Composition is used to prevent and treat the purposes of undesired plant.

Also on the one hand, the present invention provides a kind of method of weed growth in control useful plant, and it includes to where weeds A effective amount of compound of the present invention of ground preemergence application.

In some of embodiments, the weeds include broad-leaved section weeds and gramineae weed.Further, described wealthy Leaf section weeds include piemarker, Amaranthus retroflexus or Eclipta prostrata；The gramineae weed includes herba digitariae, barnyard grass or herba setariae viridis.

In some of embodiments, the useful plant includes soybean, peanut or sunflower.

On the other hand, the present invention provides the method for preventing and treating undesired plant, by a effective amount of compound of the present invention Be applied to plant, vegetable seeds, growing plant in which or on which soil or cultural area.

Formula (Ia), formula (II), formula (IIa), formula (IIb), formula (IIc), formula (IId), formula (II-1), formula (IIa-1), formula (IIa-2), formula (II-5), formula (IIa-17), formula (IIa-18), formula (IIIa), formula (IIIb), formula (IIIc), formula (IIId), formula (IIIe), formula (IIIf), formula (IIIg) or formula (IIIh) compound represented may be different with different stereoisomers or optics Structure body or tautomeric form exist.The present invention includes the mixing of all such isomers and tautomer and its various ratios Object and for example deuterated compound of isotope form.

The structure that the general formula that there is the compound of isotope enrichment the present invention to provide is described, in addition to one or more atom quilts It is replaced with selected atomic weight or the atom of mass number.The Exemplary isotopes that can be introduced into the compounds of this invention include hydrogen, Carbon, nitrogen, oxygen, phosphorus, sulphur, fluorine and chlorine isotope, such as²H,³H,¹¹C,¹³C,¹⁴C,¹⁵N,¹⁷O,¹⁸O,¹⁸F,³¹P,³²P,³⁵S,³⁶Cl With¹²⁵I。

Any asymmetric atom (for example, carbon etc.) of disclosed compound of present invention can be enriched with racemic or enantiomer Form exist, such as (R)-, (S)-or (R, S)-configuration exist.

Content noted earlier only outlines certain aspects of the invention, but be not limited to these aspect and it is otherwise in Appearance will make more specific complete description below.

Detailed description of the invention definition and general terms

It will now be described in more detail certain embodiments of the present invention, the example is by the structural formula and chemical formula explanation that are appended.This Invention is intended to cover all replacement, modification and equivalent technical solutions, they are included in the present invention defined such as claim In range.Those skilled in the art will appreciate that many can be used in similar or equivalent method and material of the present invention The practice present invention.The present invention is not limited to method of the present invention and material.In document, patent and the similar material combined One or more or contradict in the case where (including but not limited to defined in term, term application, institutes different from the application Technology of description, etc.), it is subject to the application.

It will further be appreciated that certain features of the invention, be it is clearly visible, carry out in a number of independent embodiments Description, but can also provide in combination in a single embodiment.Conversely, various features of the invention, for brevity, It is described in a single embodiment, but can also be individually or with the offer of any suitable sub-portfolio.

Unless otherwise stated, all scientific and technical terminologies used in the present invention have with those skilled in the art of the invention's It is generally understood identical meaning.All patents of the present invention and public publication are integrally incorporated this hair by reference It is bright.

Unless otherwise stated, following definition used in the present invention should be applied.For purposes of the present invention, chemical element With the periodic table of elements CAS editions, and " Handbook of Chemistry and Physics ", the 75th edition, 1994 is consistent.In addition, organic chemistry General Principle can With reference to " Organic Chemistry ", Thomas Sorrell, University Science Books, Sausalito: 1999, and " March's Advanced Organic Chemistry " by Michael B.Smith and Jerry Description in March, John Wiley&Sons, New York:2007, entire contents are incorporated by reference into the present invention.

There is apparent conflict unless otherwise indicated or in context, the article " one " used herein, " one (kind) " " described " is intended to include "at least one" or " one or more ".Therefore, these articles used herein refer to one or The article of more than one (i.e. at least one) object.For example, " component " refers to one or more components, it is possible to have more than one Component be taken into account in the embodiment of the embodiment and use or use.

Term "comprising" is open language, that is, includes content specified by the present invention, but be not precluded otherwise Content.

" stereoisomer " refers to identical chemical constitution, but the spatially different change of arrangement mode of atom or group Close object.Stereoisomer includes enantiomter, diastereoisomer, conformer (rotational isomer), geometric isomer (cis/trans) isomers, atropisomer, etc..

" enantiomter " refers to two isomers that cannot be overlapped but be mutually mirror of a compound.

" diastereoisomer " refer to there are two or multiple chiral centres and its molecule not alloisomerism of mirror image each other Body.Diastereoisomer has different physical properties, such as fusing point, boiling point, spectral property and reactivity.Diastereoisomer is mixed Such as electrophoresis and chromatography, such as HPLC can be operated by high resolution analysis to separate by closing object.

Stereochemical definitions used in the present invention and rule generally follow S.P.Parker, Ed., McGraw-Hill Dictionary of Chemical Terms(1984)McGraw-Hill Book Company,New York；and Eliel,E.and Wilen,S.,“Stereochemistry of Organic Compounds”,John Wiley&Sons, Inc., New York, Stereochemical definitions described in 1994 and rule.

Many organic compounds exist with optical active forms, i.e., they, which have, rotates the plane of linearly polarized light Ability.When describing optically active compound, indicate molecule about one or more hand using prefix D and L or R and S The absolute configuration at property center.Prefix d and l or (+) and (-) are the symbols for the rotation of linearly polarized light caused by appointed compound, Wherein (-) or l indicate that compound is left-handed.Prefix is (+) or the compound of d is dextrorotation.A kind of specific alloisomerism Body is enantiomter, and the mixture of this isomers is referred to as enantiomeric mixture.The 50:50 mixture of enantiomter Referred to as racemic mixture or racemic modification, when chemical reaction or in the process without stereoselectivity or stereospecificity when, It may occur in which such case.

" room temperature " refers to temperature at about 15 DEG C -35 DEG C or about 20 DEG C -30 DEG C or about 23 DEG C -28 DEG C or about 25 ℃.In the context of the present invention, wordings, all numbers being disclosed such as " about " or " about " are close whether or not using Like value.The numerical value of each number is possible to will appear the differences such as 1%, 2%, 3%, 4% or 5%.

As described in the invention, the compound of the present invention can be optionally replaced one or more substituent groups, such as General formula compound above, or as example special inside embodiment, subclass, and a kind of compound that the present invention is included. It should be appreciated that this term can be used interchangeably " optionally replacing " this term with " substituted or non-substituted ".In general, art " substituted " the one or more hydrogen atoms indicated in given structure of language are replaced specific substituent group.Unless other aspect tables Bright, an optional substituent group can be replaced at various substitutable position of that group.When in given structural formula not Only a position can be replaced one or more substituent groups selected from specific group, then substituent group can identical or differently Replace at various locations.Wherein the substituent group can be, but be not limited to, deuterium, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitre Base, amino, carboxyl, alkyl, alkoxy, alkoxyalkyl, alkyloxy-alkoxy, alkoxy alkylamino, aryloxy group, heteroaryl oxygen Base, heterocycle oxygroup, alkoxy aryl, heteroarylalkoxy, heterocyclylalkoxy, cycloalkyl alkoxy, alkylamino, alkylamino Alkyl, alkylamino alkylamino, cycloalkyl amino, amino-n-cycloalkyl, alkylthio group, halogenated alkyl, halogenated alkoxy, hydroxyl replace Alkyl, hydroxyl replace alkylamino, cyano replace alkyl, cyano replace alkoxy, cyano replace alkylamino, amino Substituted alkyl, alkyl acyl, miscellaneous alkyl, naphthenic base, cycloalkenyl, cycloalkyl-alkyl, heterocycle, heterocyclylalkyl group, heterocycle Acyl group, aryl, aryl alkyl, fragrant amino, heteroaryl, heteroaryl alkyl, heteroaryl amino, amide groups, sulfonyl, aminosulfonyl Base etc..

In addition, it is necessary to explanation, unless otherwise explicitly point out, in the present invention used by describing mode " each ... independently be " and " ... be each independently " and " ... independently be " can be interchanged, and shall be understood in a broad sense, both may be used To refer among the different groups, does not influence mutually, can also indicate in phase between expressed specific option between the same symbol In same group, do not influenced mutually between expressed specific option between the same symbol.

It is disclosed in the substituent group of each section of this specification, disclosed compound of present invention according to radical species or range.It is special It does not point out, the present invention includes each independent sub-combinations thereof of each member of these radical species and range.For example, term “C₁-C₆Alkyl " or " C_1-6Alkyl " refers in particular to the methyl being individually disclosed, ethyl, C₃Alkyl, C₄Alkyl, C₅Alkyl and C₆Alkyl.

Terminology used in the present invention " alkyl " or " alkyl group ", indicate contain 1 to 20 carbon atom, the straight chain of saturation or Branch univalent hydrocarbyl group；Replaced the substituent group that wherein alkyl group is optionally described by one or more present invention. Unless otherwise detailed instructions, alkyl group contains 1-20 carbon atom.In one embodiment, alkyl group contains 1-12 carbon Atom；In one embodiment, alkyl group contains 1-10 carbon atom；In one embodiment, alkyl group contains 1-8 Carbon atom；In another embodiment, alkyl group contains 1-6 carbon atom；In yet another embodiment, alkyl group contains 1-4 carbon atom；Also in one embodiment, alkyl group contains 1-3 carbon atom.

The example of alkyl group includes, but is not limited to, methyl (Me ,-CH₃), ethyl (Et ,-CH₂CH₃), n-propyl (n- Pr、-CH₂CH₂CH₃), isopropyl (i-Pr ,-CH (CH₃)₂), normal-butyl (n-Bu ,-CH₂CH₂CH₂CH₃), isobutyl group (i-Bu ,- CH₂CH(CH₃)₂), sec-butyl (s-Bu ,-CH (CH₃)CH₂CH₃), tert-butyl (t-Bu ,-C (CH₃)₃), n-pentyl (- CH₂CH₂CH₂CH₂CH₃), 2- amyl (- CH (CH₃)CH₂CH₂CH₃), 3- amyl (- CH (CH₂CH₃)₂), 2- methyl -2- butyl (- C (CH₃)₂CH₂CH₃), 3- methyl -2- butyl (- CH (CH₃)CH(CH₃)₂), 3- methyl-1-butyl (- CH₂CH₂CH(CH₃)₂), 2- first Base -1- butyl (- CH₂CH(CH₃)CH₂CH₃), n-hexyl (- CH₂CH₂CH₂CH₂CH₂CH₃), 2- hexyl (- CH (CH₃) CH₂CH₂CH₂CH₃), 3- hexyl (- CH (CH₂CH₃)(CH₂CH₂CH₃)), 2- methyl -2- amyl (- C (CH₃)₂CH₂CH₂CH₃), 3- first Base -2- amyl (- CH (CH₃)CH(CH₃)CH₂CH₃), 4- methyl -2- amyl (- CH (CH₃)CH₂CH(CH₃)₂), 3- methyl -3- penta Base (- C (CH₃)(CH₂CH₃)₂), 2- methyl -3- amyl (- CH (CH₂CH₃)CH(CH₃)₂), 2,3- dimethyl -2- butyl (- C (CH₃)₂CH(CH₃)₂), 3,3- dimethyl -2- butyl (- CH (CH₃)C(CH₃)₃), n-heptyl, n-octyl, etc..

Term " alkenyl " indicates the linear chain or branched chain monovalent hydrocarbon containing 2-12 carbon atom, wherein at least one insatiable hunger And site, that is, there is a carbon-to-carbon sp²Double bond, wherein the alkenyl group can be retouched optionally by one or more present invention Replaced the substituent group stated comprising the positioning of " cis " and " tans ", or the positioning of " E " and " Z ".In one embodiment, Alkenyl group includes 2-10 carbon atom；In one embodiment, alkenyl group includes 2-8 carbon atom；In another embodiment party In case, alkenyl group includes 2-6 carbon atom；In yet another embodiment, alkenyl group includes 2-4 carbon atom.Alkenyl base The example of group includes, but is not limited to, vinyl (- CH=CH₂), allyl (- CH₂CH=CH₂), acrylic (CH₃- CH= CH-) ,-CH₂CH₂CH=CH₂、-CH₂CH=CHCH₃、-CH₂CH₂CH₂CH=CH₂、-CH₂CH₂CH=CHCH₃、-CH₂CH₂CH₂CH =CHCH₃Etc..

Term " alkynyl " indicates the linear chain or branched chain monovalent hydrocarbon containing 2-12 carbon atom, wherein at least one carbon- Tri- key of carbon sp, wherein the alkynyl group can be optionally replaced one or more substituent groups described in the invention.In In one embodiment, alkynyl group includes 2-10 carbon atom；In one embodiment, alkynyl group includes 2-8 carbon atom； In another embodiment, alkynyl group includes 2-6 carbon atom；In yet another embodiment, alkynyl group includes 2-4 carbon Atom.The example of alkynyl group includes, but is not limited to ,-C ≡ CH ,-C ≡ CCH₃、-CH₂-C≡CH、-CH₂-C≡CCH₃、- CH₂CH₂-C≡CH、-CH₂-C≡CCH₂CH₃、-CH₂CH₂-C≡CH₂CH₃Etc..

Term " alkoxy " indicates that alkyl group is connected by oxygen atom with molecule rest part, and wherein alkyl group has Meaning as described in the present invention.Unless otherwise detailed instructions, the alkoxy base contains 1-12 carbon atom.In an embodiment party In case, alkoxy base contains 1-10 carbon atom；In one embodiment, alkoxy base contains 1-8 carbon atom；One In embodiment, alkoxy base contains 1-6 carbon atom；In another embodiment, it is former to contain 1-4 carbon for alkoxy base Son；In yet another embodiment, alkoxy base contains 1-3 carbon atom.The alkoxy base can be optionally by one Or replaced the substituent group that describes of multiple present invention.

The example of alkoxy base includes, but is not limited to, methoxyl group (MeO ,-OCH₃), ethyoxyl (EtO ,- OCH₂CH₃), 1- propoxyl group (n-PrO, n- propoxyl group ,-OCH₂CH₂CH₃), 2- propoxyl group (i-PrO, i- propoxyl group ,-OCH (CH₃)₂), 1- butoxy (n-BuO, n- butoxy ,-OCH₂CH₂CH₂CH₃), 2- methyl-l- propoxyl group (i-BuO, i- fourth oxygen Base ,-OCH₂CH(CH₃)₂), 2- butoxy (s-BuO, s- butoxy ,-OCH (CH₃)CH₂CH₃), 2- methyl -2- propoxyl group (t- BuO, t- butoxy ,-OC (CH₃)₃), 1- amoxy (n- amoxy ,-OCH₂CH₂CH₂CH₂CH₃), 2- amoxy (- OCH (CH₃) CH₂CH₂CH₃), 3- amoxy (- OCH (CH₂CH₃)₂), 2- methyl -2- butoxy (- OC (CH₃)₂CH₂CH₃), 3- methyl -2- fourth Oxygroup (- OCH (CH₃)CH(CH₃)₂), 3- methyl-l- butoxy (- OCH₂CH₂CH(CH₃)₂), 2- methyl-l- butoxy (- OCH₂CH(CH₃)CH₂CH₃), etc..

Term " alkyl amino " or " alkylamino " include " N- alkyl amino " and " N, N- dialkyl amido ", wherein amino base Group is separately replaced one or two alkyl group.Some of embodiments are that alkyl amino is one or two C_1-6Alkyl is connected to the alkylamino group of the lower level on nitrogen-atoms.Other embodiment is that alkyl amino is C_1-3's The alkylamino group of lower level.Suitable alkylamino group can be alkyl monosubstituted amino or dialkyl amido, such reality Example includes, but is not limited to, N- methylamino, N- ethylamino, N, N- dimethylamino, N, N- lignocaine etc..

Term " alkylthio group " refers to that the alkyl of linear chain or branched chain is connected on the sulphur atom of divalent, and wherein alkyl group has such as Meaning of the present invention.The example of alkylthio radicals includes, but is not limited to ,-SCH₃、-SCH₂CH₃、-SCH₂CH₂CH₃Deng Deng.

Term " halogen " refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

Term " halogenated alkyl " indicates alkyl group replaced one or more halogen atoms.The example packet of halogenated alkyl It includes, but is not limited to ,-CH₂F ,-CHF₂,-CH₂Cl ,-CH₂Br ,-CF₃,-CH₂CF₃,-CH₂CH₂F ,-CH₂CH₂Cl ,- CH₂CH₂Br ,-CH₂CHF₂,-CH₂CH₂CF₃,-CH₂CH₂CH₂F ,-CH₂CH₂CH₂Cl ,-CH₂CH₂CH₂Br ,-CHFCH₂CH₃,- CHClCH₂CH₃, etc..

Term " four fluoro ethyls " expression-CF₂CHF₂Or-CHFCF₃。

Term " halogenated alkoxy " indicates alkoxy base replaced one or more halogen atoms.Halogenated alkoxy Example includes, but is not limited to ,-OCH₂F ,-OCHF₂,-OCH₂Cl ,-OCH₂Br ,-OCF₃,-OCH₂CF₃,-OCH₂CH₂F ,- OCH₂CH₂Cl ,-OCH₂CH₂Br ,-OCH₂CHF₂,-OCH₂CH₂CF₃,-OCH₂CH₂CH₂F ,-OCH₂CH₂CH₂Cl ,- OCH₂CH₂CH₂Br ,-OCHFCH₂CH₃,-OCHClCH₂CH₃, etc..

Term " halogenated alkylamino " indicates alkylamino radicals replaced one or more halogen atoms.

Term " halogenated alkylthio " indicates alkylthio radicals replaced one or more halogen atoms.

Term " halogenated alkenyl " indicates alkenyl group replaced one or more halogen atoms.

Term " halo alkynyl " indicates alkynyl group replaced one or more halogen atoms.

Term " x former molecular ring ", wherein x is integer, the number of ring member nitrogen atoms in molecule is typically described, in institute The number for stating ring member nitrogen atoms in molecule is x.For example, piperidyl is 6 molecular heterocycles of original.

Term " 3-12 former molecular ring " refers to 3-12 former molecular carbocyclic ring, heterocycle or armaticity ring system, I.e. optionally comprising one or more hetero atoms, it is saturated, part is unsaturated or complete unsaturated ring system.

Term " 3-10 former molecular ring " refers to 3-10 former molecular carbocyclic ring, heterocycle or armaticity ring system, I.e. optionally comprising one or more hetero atoms, it is saturated, part is unsaturated or complete unsaturated ring system.

Term " 3-8 former molecular ring " refers to 3-8 former molecular carbocyclic ring, heterocycle or armaticity ring system, i.e., Optionally comprising one or more hetero atoms, it is saturated, part is unsaturated or complete unsaturated ring system.

Term " 3-6 former molecular ring " refers to 3-6 former molecular carbocyclic ring, heterocycle or armaticity ring system, i.e., Optionally comprising one or more hetero atoms, it is saturated, part is unsaturated or complete unsaturated ring system.

Term " carbocylic radical " or " carbocyclic ring " indicate containing 3-12 carbon atom, monovalent or multivalence nonaromatic saturation Or part unsaturated monocycle, bicyclic or three-ring system.Carbon bicyclic group includes spiral shell carbon bicyclic group and condensed carbon bicyclic group, suitably Carbocylic radical group includes, but is not limited to, naphthenic base, cycloalkenyl and cycloalkynyl radical.The example of carbocylic radical group further comprises ring Propyl, cyclobutyl, cyclopenta, 1- cyclopenta -1- alkenyl, 1- cyclopenta -2- alkenyl, 1- cyclopenta -3- alkenyl, cyclohexyl, 1- Cyclohexyl -1- alkenyl, 1- cyclohexyl -2- alkenyl, 1- cyclohexyl -3- alkenyl, cyclohexadienyl, suberyl, cyclooctyl, ring nonyl Base, cyclodecyl, ring undecyl, cyclo-dodecyl, etc..

Term " naphthenic base " indicates containing 3-12 carbon atom, monovalent or multivalence saturation monocyclic, bicyclic or tricyclic body System.In one embodiment, naphthenic base includes 3-12 carbon atom；In one embodiment, naphthenic base includes that 3-10 carbon is former Son；In another embodiment, naphthenic base includes 3-8 carbon atom；In yet another embodiment, naphthenic base includes 3-6 carbon Atom.The group of naphthene base is optionally replaced one or more substituent groups described in the invention.Such example packet It includes, but is not limited to, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl, cyclononyl, cyclodecyl, ring 11 Alkyl, cyclo-dodecyl, adamantyl, etc..

Term " cycloalkyl-alkyl " indicates that alkyl group is replaced by group of naphthene base, wherein alkyl group and group of naphthene base With meaning as described in the present invention.

Term " cycloalkenyl " indicates containing 3-12 carbon atom, monovalent or multivalence monocyclic, bicyclic or tricyclic system, until It less include a carbon-carbon double bond, the ring system is nonaromatic.In one embodiment, cycloalkenyl includes that 3-10 carbon is former Son；In another embodiment, cycloalkenyl includes 3-8 carbon atom；In yet another embodiment, cycloalkenyl includes 3-6 carbon Atom.The cycloalkenyl groups are optionally replaced one or more substituent groups described in the invention.Such example packet It includes, but is not limited to, cyclobutane base, cyclopentenyl, cyclohexenyl group, cyclohexadienyl etc..

Contain one or more degrees of unsaturation in " unsaturated " the expression group of term as used in the present invention.

Term " hetero atom " refers to O, S, N, P and Si, the form including any oxidation state of N, S and P；Primary, secondary, tertiary amine and season The form of ammonium salt；Or the substituted form of hydrogen in heterocycle on nitrogen-atoms, for example, N is (as in 3,4- dihydro-2 h-pyrrole base N), NH (as the NH in pyrrolidinyl) or NR (NR in pyrrolidinyl replaced as N-).

Term " heterocycle " and " heterocycle " are used interchangeably here, all refer to the saturation comprising 3-15 annular atom or portion Divide unsaturated monocyclic, bicyclic or tricyclic, does not include aromatic rings, and at least one annular atom in monocyclic, bicyclic or tricyclic wherein Selected from nitrogen, sulphur and oxygen atom.In some embodiments, C_2-12Heterocycle refers to comprising 2-12 carbon atom as the full of annular atom And/or the unsaturated monocyclic, bicyclic or tricyclic in part, do not include aromatic rings, and at least one in monocyclic, bicyclic or tricyclic wherein Annular atom is selected from nitrogen, sulphur and oxygen atom.In other embodiments, C_2-10Heterocycle refers to comprising 2-10 carbon atom conduct The unsaturated monocyclic, bicyclic or tricyclic of the saturation of annular atom or part does not include aromatic rings wherein in monocyclic, bicyclic or tricyclic, And at least one annular atom is selected from nitrogen, sulphur and oxygen atom.In other embodiments, C₂- 8 heterocycles refer to comprising 2-8 Carbon atom does not wrap in monocyclic, bicyclic or tricyclic wherein as the unsaturated monocyclic, bicyclic or tricyclic of the saturation of annular atom or part Containing aromatic rings, and at least one annular atom is selected from nitrogen, sulphur and oxygen atom.Also in other embodiments, C_2-6Heterocycle refers to Comprising 2-6 carbon atom as the unsaturated monocyclic, bicyclic or tricyclic of the saturation of annular atom or part, wherein monocycle, it is bicyclic or Aromatic rings is not included in tricyclic, and at least one annular atom is selected from nitrogen, sulphur and oxygen atom.Unless otherwise stated, heterocycle can be with It is carbon-based or nitrogen base, and-CH₂Group can be substituted optionally by-C (=O)-.The sulphur atom of ring can be optionally oxidized to S- oxide.The nitrogen-atoms of ring can optionally be oxidized to N- oxygen compound.The example of heterocycle includes, but are not limited to ring Oxirane group, azelidinyl, oxetanylmethoxy, thietanyl, pyrrolidinyl (such as 2- pyrrolidinyl), 2- pyrrolinyl, 3- pyrrolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, tetrahydrofuran base, dihydrofuryl, tetrahydro-thienyl, dihydro thiophene Pheno base, 1,3- dioxy cyclopenta, two sulphur cyclopenta, THP trtrahydropyranyl, dihydro pyranyl, 2H- pyranose, 4H- pyranose, tetrahydro Thiapyran base, piperidyl (2- piperidyl, 3- piperidyl, 4- piperidyl), morpholinyl, thio-morpholinyl, (1- oxo)-thiomorpholine Base, (1,1- dioxo)-thio-morpholinyl, piperazinyl, dioxanes base, dithianyl, thiophene oxane base, high piperazine base, high piperidines Base, oxepane alkyl, thia cycloheptyl alkyl, 2- oxa- -5- azabicyclo [2.2.1] hept- 5- base, tetrahydro pyridyl.Heterocycle - CH in base₂Group includes, but are not limited to 2- oxo-pyrrolidine base, oxo -1,3-thiazoles alkane by-C (=the O)-example replaced Base, 2- piperidone base, 3,5- dioxy piperazine piperidinyls.The example that sulphur atom is oxidized in heterocycle includes, but are not limited to sulfolane Base, 1,1- dioxothiomorpholinyl.The heterocyclyl groups are optionally by one or more substituent groups described in the invention It is replaced.

Term " the C containing an oxygen_2-6Heterocycle ", which refers to, to be made of 2-6 carbon atom and an oxygen atom as annular atom Heterocycle, such example includes, but are not limited to

Term " heterocyclylalkyl group " refers to the alkyl that heterocycle replaces；Wherein heterocycle and alkyl group have such as the present invention The meaning.

Term " heterocycle oxygroup " includes that the heterocycle optionally replaced is connected on oxygen atom as defined herein, And it is connected by oxygen atom with molecule rest part, wherein heterocyclyl groups have meaning as described in the present invention.

Term " aryl " indicates the monocycle containing 6-14 annular atom or 6-12 annular atom or 6-10 annular atom, double The carbocyclic ring system of ring and tricyclic, wherein at least one ring system be it is aromatic, wherein each ring system include 3-7 original Molecular ring, and there are one or more attachment points to be connected with the rest part of molecule.Term " aryl " can be with term " fragrance Ring " is used interchangeably.The example of aryl group may include phenyl, indenyl, naphthalene and anthryl.The aryl group is optionally by one Replaced a or multiple substituent groups described in the invention.

Term " aryl alkyl " or " aralkyl " indicate alkyl replaced one or more aryl groups, wherein alkyl and Aryl group has meaning as described in the present invention.

Term " aryloxy group " or " aryloxy " include that the aryl optionally replaced is connected to oxygen as defined herein On atom, and it is connected by oxygen atom with molecule rest part, wherein aryl group has meaning as described in the present invention.

Monocycle of term " heteroaryl " expression containing 5-12 annular atom or 5-10 annular atom or 5-6 annular atom, Bicyclic and three-ring system, wherein at least one ring system are aromatic, and at least one ring system includes one or more miscellaneous Atom, wherein each ring system includes 5-7 former molecular ring, and has one or more attachment points and molecule rest part It is connected.Term " heteroaryl " can be used interchangeably with term " hetero-aromatic ring " or " heteroaromatics ".The heteroaryl groups are appointed Selection of land is replaced one or more substituent groups described in the invention.

In one embodiment, 5-10 former molecular heteroaryl is independently selected from the miscellaneous of O, S and N comprising 1,2,3 or 4 Atom.

In another embodiment, the annular atom of heteroaryl includes the miscellaneous original that 1-9 carbon atom and 1-4 are selected from N, O or S Son；In another embodiment, the annular atom of heteroaryl includes the hetero atom that 1-5 carbon atom and 1-4 are selected from N, O or S.

In yet another embodiment, heteroaryl basis representation heteroatomic 5- or 6-membered heteroaryl containing 1-4 N；In another implementation In scheme, heteroaryl basis representation is selected from heteroatomic 5 unit's heteroaryl of N, O or S containing 1-3；In yet another embodiment, heteroaryl Indicate heteroatomic 5 unit's heteroaryl that N or O is selected from containing 1-3；In yet another embodiment, heteroaryl basis representation is selected from containing 1-3 Heteroatomic 5 unit's heteroaryl of N or S.

In one embodiment, C_1-9Heteroaryl basis representation contains heteroaryl of the 1-9 carbon atom as annular atom.Another In embodiment, C_1-6Heteroaryl basis representation contains heteroaryl of the 1-6 carbon atom as annular atom.In yet another embodiment, C_1-5Heteroaryl basis representation contains heteroaryl of the 1-5 carbon atom as annular atom.

The example of heteroaryl groups includes, but is not limited to, 2- furyl, 3- furyl, TMSIM N imidazole base, 2- imidazole radicals, 4- imidazole radicals, 5- imidazole radicals, 3- isoxazolyl, 4- isoxazolyl, 5- isoxazolyl, 2- oxazolyl, 4- oxazolyl, 5- oxazole Base, N- pyrrole radicals, 2- pyrrole radicals, 3- pyrrole radicals, 2- pyridyl group, 3- pyridyl group, 4- pyridyl group, 2- pyrimidine radicals, 4- pyrimidine radicals, 5- Pyrimidine radicals, pyridazinyl (such as 3- pyridazinyl), 2- thiazolyl, 4- thiazolyl, 5- thiazolyl, tetrazole radical (such as 5- tetrazole radical), triazole Base (such as 2- triazolyl and 5- triazolyl), 2- thienyl, 3- thienyl, pyrazolyl, isothiazolyl, 1,2,3-oxadiazoles base, 1, 2,5- oxadiazoles bases, 1,2,4- oxadiazoles base, 1,2,3-triazoles base, 1,2,3- thio biphosphole base, 1,3,4- thio biphosphole base, 1, 2,5- thio biphosphole bases, pyrazinyl, 1,3,5-triazines base, pyrimidine ketone group, pyriconyl；It also include below bicyclic, but never It is bicyclic to be limited to these: benzimidazolyl, benzofuranyl, benzo tetrahydrofuran base, benzothienyl, indyl (such as 2- indoles Base), etc..

Term " heteroaryl alkyl " indicate alkyl group replaced one or more heteroaryl groups, wherein alkyl group There is meaning as described in the present invention with heteroaryl groups.

Term " heteroaryl oxygroup " includes that the heteroaryl optionally replaced is connected on oxygen atom as defined herein, And it is connected by oxygen atom with molecule rest part, wherein heteroaryl groups have meaning as described in the present invention.

The number of pyrazole ring of the present invention is as follows:

When the compound of the present invention includes an acid moieties, the salt of compound of the present invention, including derived from alkali gold Belong to or those of alkaline-earth metal and is derived from those of ammonia and amine.Preferred cation includes sodium, potassium, magnesium and has chemistry Formula N⁺(R¹⁹R²⁰R²¹R²²) ammonium cation, wherein R¹⁹、R²⁰、R²¹And R²²Independently selected from hydrogen, C₁-C₆Alkyl and C₁-C₆Hydroxyl alkane Base.With formula (I), formula (Ia), formula (II), formula (IIa), formula (IIb), formula (IIc), formula (IId), formula (II-1), formula (IIa- 1), formula (IIa-2), formula (II-5), formula (IIa-17), formula (IIa-18), formula (IIIa), formula (IIIb), formula (IIIc), formula (IIId), the salt of formula (IIIe), formula (IIIf), formula (IIIg) or formula (IIIh) compound represented can be by with metal hydrogen-oxygen Compound (such as sodium hydroxide) or amine (such as ammonia, trimethylamine, diethanol amine, 2- methyl mercapto propylamine, diallyl amine, 2- fourth oxygen Base ethamine, morpholine, ring lauryl amine or benzylamine) to formula (I), formula (Ia), formula (II), formula (IIa), formula (IIb), formula (IIc), Formula (IId), formula (II-1), formula (IIa-1), formula (IIa-2), formula (II-5), formula (IIa-17), formula (IIa-18), formula (IIIa), Formula (IIIb), formula (IIIc), formula (IIId), formula (IIIe), formula (IIIf), formula (IIIg) or formula (IIIh) compound represented into Row processing is to prepare.

When the compound of the present invention includes an alkali part, acceptable salt can be formed by organic acid and inorganic acid, Such as acetic acid, propionic acid, lactic acid, citric acid, tartaric acid, succinic acid, fumaric acid, maleic acid, malonic acid, mandelic acid, malic acid, neighbour Phthalic acid, hydrochloric acid, hydrobromic acid, phosphoric acid, nitric acid, sulfuric acid, methanesulfonic acid, naphthalene sulfonic acids, benzene sulfonic acid, toluenesulfonic acid, camphorsulfonic acid with And similarly known acceptable acid.

The detailed description of the compounds of this invention

The purpose of the present invention is to provide a kind of novel isoxazoles compound, contain the combinations of herbicides of the compound Object and preparation and its application.

On the one hand, the present invention provides a kind of compound, is the compound as shown in formula (I) compound represented or formula (I) Stereoisomer, nitrogen oxides or its salt:

Wherein:

R¹And R²It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, alkyl, naphthenic base Or cycloalkyl-alkyl；Or R¹、R²It is formed together with the carbon atom being connected with them by 3-12 former molecular ring；

R³And R⁴It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, alkyl, naphthenic base Or cycloalkyl-alkyl；Or R³、R⁴It is formed together with the carbon atom being connected with them by 3-12 former molecular ring；

N is 0,1 or 2；

R^aAnd R^bIt is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, alkyl, alkenyl, alkynes Base, halogenated alkyl, halogenated alkenyl, halo alkynyl, alkoxy, alkylamino, alkylthio group, naphthenic base, heterocycle, aryl or heteroaryl Base；

Or R⁸、R⁹The former molecular ring of 3-12 optionally replaced is formed together with the carbon atom being attached thereto；

Or R⁸、R⁹- C (=O)-is formed together with the carbon atom being attached thereto；

Or R¹⁰、R¹¹、R¹²- C ≡ CR is formed together with the carbon atom being attached thereto¹³Or-CR¹⁴=CR¹⁵R¹⁶；Wherein R¹³、 R¹⁴、R¹⁵And R¹⁶It is each independently hydrogen, alkyl, halogenated alkyl, alkenyl, halogenated alkenyl, alkynyl or halo alkynyl；

Or R¹⁰、R¹¹、R¹²The C optionally replaced is formed together with the carbon atom being attached thereto_6-14Aryl optionally replaces C_1-9Heteroaryl, the C optionally replaced_3-12Naphthenic base or the C optionally replaced_2-12Heterocycle is (i.e.It indicatesIts Middle Ay1 is the C optionally replaced_6-14Aryl, the C optionally replaced_1-9Heteroaryl, the C optionally replaced_3-12Naphthenic base optionally replaces C_2-12Heterocycle)；

Or-CR⁸R⁹-CR¹⁰R¹¹R¹²Indicate the C optionally replaced_10-14Aryl, the C optionally replaced_1-9Heteroaryl optionally takes The C in generation_3-12Naphthenic base, the C optionally replaced_2-12Heterocycle, unsubstituted phenyl or substituted phenyl are (i.e.It indicatesWherein Ay2 is the C optionally replaced_10-14Aryl, the C optionally replaced_1-9Heteroaryl, the C optionally replaced_3-12Naphthenic base, The C optionally replaced_2-12Heterocycle, unsubstituted phenyl or substituted phenyl)；

Condition is (i) R^aIt is not-CF₃；(ii)R^bIt is not-CF₃；(iii) work as R^aWhen for phenyl, R^bIt is not Cl；(iv)R^aAnd R^b It cannot simultaneously be Cl；(v) work as R^aWhen for alkyl, R⁸、R¹⁰The ring of the 3-12 member formed with the carbon atom being attached thereto is not phenyl ring； (vi) as-CR⁸R⁹-CR¹⁰R¹¹R¹²Indicate unsubstituted phenyl, R^aFor chlorine, R^bFor difluoromethyl, R⁵And R⁶Be hydrogen, n 0,1 or 2, R³And R⁴It is hydrogen, R¹When for methyl, R²It is not methyl or chloromethyl；(vii) as-CR⁸R⁹-CR¹⁰R¹¹R¹²Indicate unsubstituted Phenyl, R^bFor chlorine, R^aFor difluoromethyl, R⁵And R⁶It is hydrogen, n 0,1 or 2, R³And R⁴It is hydrogen, R¹When for methyl, R²It is not first Base or chloromethyl；(viii) as-CR⁸R⁹-CR¹⁰R¹¹R¹²Indicate unsubstituted phenyl, R^aFor chlorine, R^bFor difluoromethyl, R⁵And R⁶ For hydrogen, n 0,1 or 2, R³And R⁴It is hydrogen, R²When for methyl, R¹It is not methyl or chloromethyl；Or (ix) as-CR⁸R⁹- CR¹⁰R¹¹R¹²Indicate unsubstituted phenyl, R^bFor chlorine, R^aFor difluoromethyl, R⁵And R⁶It is hydrogen, n 0,1 or 2, R³And R⁴It is Hydrogen, R²When for methyl, R¹It is not methyl or chloromethyl.

On the other hand, the present invention provides a kind of compound, for such as formula (Ia) compound represented or formula (Ia) shownization Close stereoisomer, nitrogen oxides or its salt of object:

Wherein:

N is 0,1 or 2；

X is fluorine, chlorine or bromine；

Condition is:

(1) when Y is methyl, X is chlorine, R⁵And R⁶It is hydrogen, n 0,1 or 2, R³And R⁴It is hydrogen, R¹When for methyl, R²No For methyl or chloromethyl；

(2) when Y is methyl, X is chlorine, R⁵And R⁶It is hydrogen, n 0,1 or 2, R³And R⁴It is hydrogen, R²When for methyl, R¹No For methyl or chloromethyl；

(3) when Y is unsubstituted phenyl, X is chlorine, R⁵And R⁶It is hydrogen, n 0,1 or 2, R³And R⁴It is hydrogen, R¹For methyl When, R²It is not methyl or chloromethyl；

(4) when Y is unsubstituted phenyl, X is chlorine, R⁵And R⁶It is hydrogen, n 0,1 or 2, R³And R⁴It is hydrogen, R²For methyl When, R¹It is not methyl or chloromethyl；

(5) when Y is ethyl or isopropyl, X is chlorine and at 5 of pyrazole ring, R⁵And R⁶It is hydrogen, n is 0 or 2, R³And R⁴ It is hydrogen, R¹When for methyl, R²It is not chloromethyl；Or

(6) when Y is ethyl or isopropyl, X is chlorine and at 5 of pyrazole ring, R⁵And R⁶It is hydrogen, n is 0 or 2, R³And R⁴ It is hydrogen, R²When for methyl, R¹It is not chloromethyl.

In some of embodiments, Y C_1-8Alkyl, halogenated C_1-8Alkyl, C_1-8Alkoxy C_1-8Alkyl, C_1-8Alkylamino C_1-8Alkyl, C_2-8Alkenyl, halogenated C_2-8Alkenyl, C_2-8Alkynyl, halogenated C_2-8Alkynyl, C_3-10Naphthenic base, C_3-10Naphthenic base C_1-8Alkyl, C_2-12Heterocycle, C_2-12Heterocycle C_1-8Alkyl, C_6-14Aryl, C_6-14Aryl C_1-8Alkyl, C_1-9Heteroaryl, C_1-9Heteroaryl C_1-8Alkane Base ,-C (=O)-C_1-8Alkyl ,-S (=O)₂-C_1-8Alkyl ,-C (=O)-C_3-10Naphthenic base ,-S (=O)₂-C_3-10Naphthenic base ,-C (=O)-C_2-12Heterocycle ,-S (=O)₂-C_2-12Heterocycle ,-C (=O)-C_6-14Aryl ,-S (=O)₂-C_6-14Aryl ,-C (= O)-C_1-9Heteroaryl or-S (=O)₂-C_1-9Heteroaryl；

Wherein Y is optionally selected from Y by 1,2,3,4,5 or 6^aSubstituent group replaced；Each Y^aIndependently be fluorine, chlorine, bromine, Iodine, amino, nitro, cyano, hydroxyl, carboxyl, C_1-6Alkyl, halogenated C_1-6Alkyl, C_2-6Alkenyl, halogenated C_2-6Alkenyl, C_2-6Alkynyl, Halogenated C_2-6Alkynyl, C_1-6Alkoxy, C_1-6Alkylamino, C_1-6Alkylthio group, C_3-6Naphthenic base, C_2-6Heterocycle, C_6-10Aryl or C_1-9It is miscellaneous Aryl.

In other embodiment, Y C_1-6Alkyl, halogenated C_1-6Alkyl, C_1-6Alkoxy C_1-6Alkyl, C_1-6Alkylamino C_1-6Alkyl, C_2-6Alkenyl, halogenated C_2-6Alkenyl, C_2-6Alkynyl, halogenated C_2-6Alkynyl, C_3-8Naphthenic base, C_3-8Naphthenic base C_1-6Alkyl, C_2-8Heterocycle, C_2-8Heterocycle C_1-6Alkyl, C_6-10Aryl, C_6-10Aryl C_1-6Alkyl, C_1-6Heteroaryl, C_1-6Heteroaryl C_1-6Alkane Base ,-C (=O)-C_1-6Alkyl ,-S (=O)₂-C_1-6Alkyl ,-C (=O)-C_3-8Naphthenic base ,-S (=O)₂-C_3-8Naphthenic base ,-C (= O)-C_2-8Heterocycle ,-S (=O)₂-C_2-8Heterocycle ,-C (=O)-C_6-10Aryl ,-S (=O)₂-C_6-10Aryl ,-C (=O)-C_1-6 Heteroaryl or-S (=O)₂-C_1-6Heteroaryl；

Wherein Y is optionally selected from Y by 1,2,3,4,5 or 6^aSubstituent group replaced；Each Y^aIndependently be fluorine, chlorine, bromine, Iodine, amino, nitro, cyano, hydroxyl, carboxyl, C_1-4Alkyl, halogenated C_1-4Alkyl, C_2-4Alkenyl, halogenated C_2-4Alkenyl, C_2-4Alkynyl, Halogenated C_2-4Alkynyl, C_1-4Alkoxy, C_1-4Alkylamino, C_1-4Alkylthio group, C_3-6Naphthenic base, C_2-6Heterocycle, C_6-10Aryl or C_1-6It is miscellaneous Aryl.

In other embodiment, Y C_1-4Alkyl, halogenated C_1-4Alkyl, C_1-4Alkoxy C_1-4Alkyl, C_1-4Alkylamino C_1-4Alkyl, C_2-4Alkenyl, halogenated C_2-4Alkenyl, C_2-4Alkynyl, halogenated C_2-4Alkynyl, C_3-6Naphthenic base, C_3-6Naphthenic base C_1-3Alkyl, C_2-4Heterocycle, C_2-4Heterocycle C_1-3Alkyl, C_6-10Aryl, C_6-10Aryl C_1-4Alkyl, C_1-6Heteroaryl, C_1-6Heteroaryl C_1-3Alkane Base ,-C (=O)-C_1-4Alkyl ,-S (=O)₂-C_1-4Alkyl ,-C (=O)-C_3-6Naphthenic base ,-S (=O)₂-C_3-6Naphthenic base ,-C (= O)-C_2-4Heterocycle ,-S (=O)₂-C_2-4Heterocycle ,-C (=O)-C_6-10Aryl ,-S (=O)₂-C_6-10Aryl ,-C (=O)-C_1-5 Heteroaryl or-S (=O)₂-C_1-5Heteroaryl；

Wherein Y is optionally selected from Y by 1,2,3,4,5 or 6^aSubstituent group replaced；Each Y^aIndependently be fluorine, chlorine, bromine, Iodine, amino, nitro, cyano, hydroxyl, carboxyl, C_1-3Alkyl, halogenated C_1-3Alkyl, C_2-3Alkenyl, halogenated C_2-3Alkenyl, C_2-3Alkynyl, Halogenated C_2-3Alkynyl, C_1-3Alkoxy, C_1-3Alkylamino, C_1-3Alkylthio group, C_3-6Naphthenic base, C_2-6Heterocycle, C_6-10Aryl or C_1-5It is miscellaneous Aryl.

Also in some embodiments, Y is-CH₃、-CH₂CH₃、-CH₂CH₂CH₃、-CH(CH₃)₂、-CH₂CH(CH₃)₂、-C (CH₃)₃、-CH₂CHF₂、-CH₂CF₃、-CH₂CF₂CHF₂、-CH₂CH=CH₂、-CH₂- C ≡ CH ,-C (=O) CH₃、-CH₂OCH₃、- CH₂OCH₂CH₃, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, 2- fluorophenyl, 3- fluorophenyl, 4- fluorophenyl, 2,4 difluorobenzene Base, benzyl, 2- chlorobenzyl, 3- chlorobenzyl, 4- chlorobenzyl, benzoyl or benzenesulfonyl；Or

Y is following subformula:

In some of embodiments, the present invention provides a kind of compound, for such as formula (II) compound represented or formula (II) stereoisomer, nitrogen oxides and the salt of compound shown in:

Wherein: X is fluorine, chlorine or bromine；

R¹、R²、R³、R⁴、n、R⁵、R⁶、R⁸、R⁹、R¹⁰、R¹¹And R¹²With meaning as described in the present invention.

In some of embodiments, the present invention provides a kind of compound, for such as formula (II-1) compound represented or Stereoisomer, nitrogen oxides or its salt of compound shown in formula (II-1):

Wherein: X is fluorine, chlorine or bromine；

R¹、R²、R³、R⁴、n、R⁵、R⁶、R⁸、R⁹And R¹³With meaning as described in the present invention.

In some of embodiments, the present invention provides a kind of compound, for such as formula (II-2) compound represented or Stereoisomer, nitrogen oxides or its salt of compound shown in formula (II-2):

Wherein: X is fluorine, chlorine or bromine；

R¹、R²、R³、R⁴、n、R⁵、R⁶、R⁸、R⁹、R¹⁴、R¹⁵And R¹⁶With meaning as described in the present invention.

In some of embodiments, the present invention provides a kind of compound, for such as formula (II-3) compound represented or Stereoisomer, nitrogen oxides or its salt of compound shown in formula (II-3):

Wherein: X is fluorine, chlorine or bromine；

R¹、R²、R³、R⁴、n、R⁵、R⁶、R⁸、R⁹There is meaning as described in the present invention with Ay1.

In some of embodiments, the present invention provides a kind of compound, for such as formula (II-4) compound represented or Stereoisomer, nitrogen oxides or its salt of compound shown in formula (II-4):

Wherein: X is fluorine, chlorine or bromine；

R¹、R²、R³、R⁴、n、R⁵、R⁶There is meaning as described in the present invention with Ay2.

Wherein: X is fluorine, chlorine or bromine；

R¹、R²、R³、R⁴、n、R⁵And R⁶With meaning as described in the present invention.

In some of embodiments, the present invention provides a kind of compound, for such as formula (III-1) compound represented or Stereoisomer, nitrogen oxides or its salt of compound shown in formula (III-1):

Wherein: R¹、R²、R³、R⁴、n、R⁵、R⁶、R⁸、R⁹、R¹⁰、R¹¹And R¹²With meaning as described in the present invention.

In some of embodiments, the present invention provides a kind of compound, for such as formula (III-2) compound represented or Stereoisomer, nitrogen oxides or its salt of compound shown in formula (III-2):

Wherein: R¹、R²、R³、R⁴、n、R⁵、R⁶、R⁸、R⁹、R¹⁰、R¹¹And R¹²With meaning as described in the present invention.

Wherein: R¹、R²、R³、R⁴、R⁵、R⁶、R⁸、R⁹、R¹⁰、R¹¹And R¹²With meaning as described in the present invention.

Wherein: R¹、R²、R³、R⁴、R⁵、R⁶、R⁸、R⁹And R¹³With meaning as described in the present invention.

In some of embodiments, the present invention provides a kind of compound, for such as formula (IIa-3) compound represented or Stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIa-3):

Wherein: R¹、R²、R³、R⁴、R⁵、R⁶、R⁸、R⁹、R¹⁴、R¹⁵And R¹⁶With meaning as described in the present invention.

In some of embodiments, the present invention provides a kind of compound, for such as formula (IIa-4) compound represented or Stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIa-4):

Wherein: R¹、R²、R³、R⁴、R⁵、R⁶、R⁸、R⁹、R¹⁴、R¹⁵And R¹⁶With meaning as described in the present invention.

In some of embodiments, the present invention provides a kind of compound, for such as formula (IIa-5) compound represented or Stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIa-5):

Wherein: R¹、R²、R³、R⁴、R⁵、R⁶、R⁸、R⁹There is meaning as described in the present invention with Ay1.

In some of embodiments, the present invention provides a kind of compound, for such as formula (IIa-6) compound represented or Stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIa-6):

Wherein: R¹、R²、R³、R⁴、R⁵、R⁶、R⁸、R⁹There is meaning as described in the present invention with Ay1.

In some of embodiments, the present invention provides a kind of compound, for such as formula (IIa-7) compound represented or Stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIa-7):

Wherein: R¹、R²、R³、R⁴、R⁵、R⁶There is meaning as described in the present invention with Ay2.

In some of embodiments, the present invention provides a kind of compound, for such as formula (IIa-8) compound represented or Stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIa-8):

Wherein: R¹、R²、R³、R⁴、R⁵、R⁶There is meaning as described in the present invention with Ay2.

In some of embodiments, the present invention provides a kind of compound, for such as formula (IIa-9) compound represented or Stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIa-9):

Wherein: R¹、R²、R³、R⁴、R⁵、R⁶、R⁸、R⁹And R¹³With meaning as described in the present invention.

In some of embodiments, the present invention provides a kind of compound, for such as formula (IIa-10) compound represented Or stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIa-10):

Wherein: R¹、R²、R³、R⁴、R⁵、R⁶、R⁸、R⁹And R¹³With meaning as described in the present invention.

In some of embodiments, the present invention provides a kind of compound, for such as formula (IIa-11) compound represented Or stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIa-11):

Wherein: R¹、R²、R³、R⁴、R⁵、R⁶、R⁸、R⁹、R¹⁴、R¹⁵And R¹⁶With meaning as described in the present invention.

In some of embodiments, the present invention provides a kind of compound, for such as formula (IIa-12) compound represented Or stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIa-12):

Wherein: R¹、R²、R³、R⁴、R⁵、R⁶、R⁸、R⁹、R¹⁴、R¹⁵And R¹⁶With meaning as described in the present invention.

In some of embodiments, the present invention provides a kind of compound, for such as formula (IIa-13) compound represented Or stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIa-13):

Wherein: R¹、R²、R³、R⁴、R⁵、R⁶、R⁸、R⁹There is meaning as described in the present invention with Ay1.

In some of embodiments, the present invention provides a kind of compound, for such as formula (IIa-14) compound represented Or stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIa-14):

Wherein: R¹、R²、R³、R⁴、R⁵、R⁶、R⁸、R⁹There is meaning as described in the present invention with Ay1.

In some of embodiments, the present invention provides a kind of compound, for such as formula (IIa-15) compound represented Or stereoisomer, nitrogen oxides and the salt of compound shown in formula (IIa-15):

Wherein: R¹、R²、R³、R⁴、R⁵、R⁶There is meaning as described in the present invention with Ay2.

In some of embodiments, the present invention provides a kind of compound, for such as formula (IIa-16) compound represented Or stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIa-16):

Wherein: R¹、R²、R³、R⁴、R⁵、R⁶There is meaning as described in the present invention with Ay2.

Wherein: X, R¹、R²、R³、R⁴、R⁵And R⁶With meaning as described in the present invention.

In some of embodiments, the present invention provides a kind of compound, for such as formula (IV) compound represented or formula (IV) stereoisomer, nitrogen oxides and the salt of compound shown in:

Wherein:

Ay2 is the C optionally replaced_10-14Aryl, the C optionally replaced_1-9Heteroaryl, the C optionally replaced_3-12Naphthenic base, optionally Substituted C_2-12Heterocycle, unsubstituted phenyl or substituted phenyl；It is described substitution or optionally replace, substituent group number be 1,2, 3,4,5 or 6；Substituent group can be identical or different；Wherein substituent group be fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, Carboxyl, C_1-6Alkyl, halogenated C_1-6Alkyl, C_2-6Alkenyl, halogenated C_2-6Alkenyl, C_2-6Alkynyl, halogenated C_2-6Alkynyl, C_1-6Alkoxy, C_1-6Alkylamino, C_1-6Alkylthio group, C_3-6Naphthenic base, C_2-8Heterocycle, C_6-10Aryl or C_1-9Heteroaryl；

R¹、R²、R³、R⁴、n、R⁵And R⁶With meaning as described in the present invention；

Condition is, when Ay2 indicates unsubstituted phenyl, R⁵And R⁶It is hydrogen, n 0,1 or 2, R³And R⁴It is hydrogen, R¹For first When base, R²It is not methyl or chloromethyl；Or when Ay2 indicates unsubstituted phenyl, R⁵And R⁶It is hydrogen, n 0,1 or 2, R³And R⁴ It is hydrogen, R²When for methyl, R¹It is not methyl or chloromethyl.

In some of embodiments, R¹And R²It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl Base, carboxyl, C_1-6Alkyl, halogenated C_1-6Alkyl, C_3-6Naphthenic base or C_3-6Naphthenic base C_1-6Alkyl；Or R¹、R²It is connected with them Carbon atom be formed together by 3-8 former molecular ring.

In some of embodiments, R³And R⁴It is each independently hydrogen, bromine, iodine, amino, nitro, hydroxyl, carboxyl, C_1-6 Alkyl, C_3-6Naphthenic base or C_3-6Naphthenic base C_1-6Alkyl；Or R³、R⁴It is formed together with the carbon atom being connected with them by 3-8 Former molecular ring.

In some of embodiments, R⁵And R⁶It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl Base, carboxyl, C_1-6Alkyl, C_2-6Alkenyl or C_2-6Alkynyl；Or R⁵、R⁶It is formed together with the carbon atom being connected with them by 3-8 Former molecular ring.

In some of embodiments, R⁸、R⁹、R¹⁰、R¹¹And R¹²It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitre Base, cyano, hydroxyl, carboxyl, C_1-6Alkyl, halogenated C_1-6Alkyl, C_2-6Alkenyl, halogenated C_2-6Alkenyl, C_2-6Alkynyl, halogenated C_2-6Alkynes Base, C_1-6Alkoxy, C_1-6Alkylamino, C_1-6Alkylthio group, C_3-6Naphthenic base, C_2-8Heterocycle, C_6-10Aryl or C_1-9Heteroaryl.

In some of embodiments, R⁸、R⁹The 3-10 atom optionally replaced is formed together with the carbon atom being attached thereto The ring of composition；The optional substitution, substituent group number are 1,2,3,4,5 or 6；Substituent group can be identical or different；Wherein take Dai Jiwei fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C_1-6Alkyl, halogenated C_1-6Alkyl, C_2-6It is alkenyl, halogenated C_2-6Alkenyl, C_2-6Alkynyl, halogenated C_2-6Alkynyl, C_1-6Alkoxy, C_1-6Alkylamino, C_1-6Alkylthio group, C_3-8Naphthenic base, C_2-10Heterocycle Base, C_6-14Aryl or C_1-9Heteroaryl.

In some of embodiments, R⁸、R⁹- C (=O)-is formed together with the carbon atom being attached thereto.

In some of embodiments, R¹⁰、R¹¹、R¹²- C ≡ CR is formed together with the carbon atom being attached thereto¹³Or-CR¹⁴ =CR¹⁵R¹⁶；Wherein R¹³、R¹⁴、R¹⁵And R¹⁶It is each independently hydrogen, C_1-6Alkyl, halogenated C_1-6Alkyl, C_2-6Alkenyl, halogenated C_2-6 Alkenyl, C_2-6Alkynyl or halogenated C_2-6Alkynyl.

In some of embodiments, R¹⁰、R¹¹、R¹²The C optionally replaced is formed together with the carbon atom being attached thereto_6-14 Aryl, the C optionally replaced_1-9Heteroaryl, the C optionally replaced_3-10Naphthenic base or the C optionally replaced_2-10Heterocycle is (i.e.It indicatesWherein Ay1 is the C optionally replaced_6-14Aryl, the C optionally replaced_1-9Heteroaryl optionally replaces C_3-10Naphthenic base or the C optionally replaced_2-10Heterocycle)；The optional substitution, substituent group number are 1,2,3,4,5 or 6；It takes It can be identical or different for base；Wherein substituent group is fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C_1-6Alkyl, Halogenated C_1-6Alkyl, C_2-6Alkenyl, halogenated C_2-6Alkenyl, C_2-6Alkynyl, halogenated C_2-6Alkynyl, C_1-6Alkoxy, C_1-6Alkylamino, C_1-6Alkane Sulfenyl, C_3-8Naphthenic base, C_2-10Heterocycle, C_6-14Aryl or C_1-9Heteroaryl.

In some of embodiments ,-CR⁸R⁹-CR¹⁰R¹¹R¹²Indicate the C optionally replaced_10-14Aryl optionally replaces C_1-9Heteroaryl, the C optionally replaced_3-10Naphthenic base, the C optionally replaced_2-10Heterocycle, unsubstituted phenyl or substituted phenyl (i.e.It indicatesWherein Ay2 is the C optionally replaced_10-14Aryl, the C optionally replaced_1-9Heteroaryl, optionally Substituted C_3-10Naphthenic base, the C optionally replaced_2-10Heterocycle, unsubstituted phenyl or substituted phenyl)；The substitution is optional Replace, substituent group number is 1,2,3,4,5 or 6；Substituent group can be identical or different；Wherein substituent group be fluorine, chlorine, bromine, iodine, Amino, nitro, cyano, hydroxyl, carboxyl, C_1-6Alkyl, halogenated C_1-6Alkyl, C_2-6Alkenyl, halogenated C_2-6Alkenyl, C_2-6It is alkynyl, halogenated C_2-6Alkynyl, C_1-6Alkoxy, C_1-6Alkylamino, C_1-6Alkylthio group, C_3-8Naphthenic base, C_2-10Heterocycle, C_6-14Aryl or C_1-9Heteroaryl Base.

In other embodiment, R³And R⁴It is each independently hydrogen, bromine, iodine, amino, nitro, hydroxyl, carboxyl, C_1-3 Alkyl, C_3-6Naphthenic base or C_3-6Naphthenic base C_1-3Alkyl；Or R³、R⁴It is formed together with the carbon atom being connected with them by 3-6 Former molecular ring.

In other embodiment, R⁵And R⁶It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl Base, carboxyl, C_1-4Alkyl, C_2-4Alkenyl or C_2-4Alkynyl；Or R⁵、R⁶It is formed together with the carbon atom being connected with them by 3-6 Former molecular ring.

In other embodiment, R³And R⁴It is each independently hydrogen or bromine.

In other embodiment, R⁵And R⁶It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl Base, carboxyl or methyl.

In some of embodiments, the present invention provides a kind of compound, for such as formula (IIIa) compound represented or Stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIIa):

Wherein: R⁸、R⁹、R¹⁰、R¹¹And R¹²With meaning as described in the present invention.

In some of embodiments, the present invention provides a kind of compound, for such as formula (IIIb) compound represented or Stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIIb):

Wherein: R⁸、R⁹、R¹⁰、R¹¹And R¹²With meaning as described in the present invention.

In some of embodiments, the present invention provides a kind of compound, for such as formula (IIIc) compound represented or Stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIIc):

Wherein: R⁸、R⁹、R¹⁰、R¹¹And R¹²With meaning as described in the present invention.

In some of embodiments, the present invention provides a kind of compound, for such as formula (IIId) compound represented or Stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIId):

Wherein: R⁸、R⁹、R¹⁰、R¹¹And R¹²With meaning as described in the present invention.

In some of embodiments, R⁸、R⁹、R¹⁰、R¹¹And R¹²It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitre Base, cyano, hydroxyl, carboxyl, C_1-4Alkyl, halogenated C_1-4Alkyl, C_2-4Alkenyl, halogenated C_2-4Alkenyl, C_2-4Alkynyl, halogenated C_2-4Alkynes Base, C_1-4Alkoxy, C_1-4Alkylamino, C_1-4Alkylthio group, C_3-6Naphthenic base, C_2-6Heterocycle, C_6-10Aryl or C_1-5Heteroaryl.

In some of embodiments, R⁸、R⁹The 3-8 atom optionally replaced is formed together with the carbon atom being attached thereto The ring of composition；The optional substitution, substituent group number are 1,2,3,4,5 or 6；Substituent group can be identical or different；Wherein take Dai Jiwei fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C_1-6Alkyl, halogenated C_1-4Alkyl, C_2-4It is alkenyl, halogenated C_2-4Alkenyl, C_2-4Alkynyl, halogenated C_2-4Alkynyl, C_1-4Alkoxy, C_1-4Alkylamino, C_1-4Alkylthio group, C_3-6Naphthenic base, C_2-6Heterocycle Base, C_6-10Aryl or C_1-5Heteroaryl.

In some of embodiments, R⁸、R⁹- C (=O)-is formed together with the carbon atom being attached thereto.

In some of embodiments, R¹⁰、R¹¹、R¹²- C ≡ CR is formed together with the carbon atom being attached thereto¹³Or-CR¹⁴ =CR¹⁵R¹⁶；Wherein R¹³、R¹⁴、R¹⁵And R¹⁶It is each independently hydrogen, C_1-4Alkyl, halogenated C_1-4Alkyl, C_2-4Alkenyl, halogenated C_2-4 Alkenyl, C_2-4Alkynyl or halogenated C_2-4Alkynyl.

In some of embodiments, R¹⁰、R¹¹、R¹²The C optionally replaced is formed together with the carbon atom being attached thereto_6-10 Aryl, the C optionally replaced_1-6Heteroaryl, the C optionally replaced_3-8Naphthenic base or the C optionally replaced_2-6Heterocycle is (i.e. It indicatesWherein Ay1 is the C optionally replaced_6-10Aryl, the C optionally replaced_1-6Heteroaryl, the C optionally replaced_3-8Cycloalkanes Base or the C optionally replaced_2-6Heterocycle)；The optional substitution, substituent group number are 1,2,3,4,5 or 6；Substituent group can phase It is same or different；Wherein substituent group is fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C_1-6Alkyl, halogenated C_1-4Alkane Base, C_2-4Alkenyl, halogenated C_2-4Alkenyl, C_2-4Alkynyl, halogenated C_2-4Alkynyl, C_1-4Alkoxy, C_1-4Alkylamino, C_1-4Alkylthio group, C_3-6 Naphthenic base, C_2-6Heterocycle, C_6-10Aryl or C_1-5Heteroaryl.

In some of embodiments ,-CR⁸R⁹-CR¹⁰R¹¹R¹²Indicate the C optionally replaced_10-14Aryl optionally replaces C_1-6Heteroaryl, the C optionally replaced_3-8Naphthenic base, the C optionally replaced_2-6Heterocycle, unsubstituted phenyl or substituted phenyl are (i.e.It indicatesWherein Ay2 is the C optionally replaced_10-14Aryl, the C optionally replaced_1-6Heteroaryl optionally takes The C in generation_3-8Naphthenic base, the C optionally replaced_2-6Heterocycle, unsubstituted phenyl or substituted phenyl)；The substitution optionally takes Generation, substituent group number are 1,2,3,4,5 or 6；Substituent group can be identical or different；Wherein substituent group is fluorine, chlorine, bromine, iodine, ammonia Base, nitro, cyano, hydroxyl, carboxyl, C_1-6Alkyl, halogenated C_1-4Alkyl, C_2-4Alkenyl, halogenated C_2-4Alkenyl, C_2-4It is alkynyl, halogenated C_2-4Alkynyl, C_1-4Alkoxy, C_1-4Alkylamino, C_1-4Alkylthio group, C_3-6Naphthenic base, C_2-6Heterocycle, C_6-10Aryl or C_1-5Heteroaryl Base.

In other embodiment, R⁸、R⁹C is formed together with the carbon atom being attached thereto_3-6Naphthenic base.

In other embodiment, R⁸、R⁹- C (=O)-is formed together with the carbon atom being attached thereto.

In other embodiment, R¹⁰、R¹¹、R¹²- C ≡ CH or-CH=is formed together with the carbon atom being attached thereto CH₂。

In other embodiment, R¹⁰、R¹¹、R¹²C is formed together with the carbon atom being attached thereto_3-6Naphthenic base, optionally The phenyl being optionally substituted by halogen or the C containing an oxygen_2-6Heterocycle.

In other embodiment ,-CR⁸R⁹-CR¹⁰R¹¹R¹²Indicate C_3-6The phenyl that naphthenic base or halogen replace.

Wherein:

R⁵And R⁶It is each independently hydrogen or fluorine；

X is fluorine or chlorine；

R^mFor hydrogen, C_1-3Alkyl or halogenated C_1-3Alkyl；

R^vFor hydrogen, C_1-3Alkyl or halogenated C_1-3Alkyl；

R^wFor C_1-3Alkyl or halogenated C_1-3Alkyl.

Also in some embodiments, the present invention provides a kind of compound, for such as formula (IIIe) compound represented or Stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIIe), wherein R^mFor hydrogen or methyl；R^vFor hydrogen or methyl； R^wFor methyl, isopropyl, difluoromethyl or four fluoro ethyls.

Wherein:

R⁵And R⁶It is each independently hydrogen or fluorine；

X is fluorine or chlorine；

R^mFor hydrogen, C_1-3Alkyl or halogenated C_1-3Alkyl；

R^vFor hydrogen, C_1-3Alkyl or halogenated C_1-3Alkyl；

R^wFor C_1-3Alkyl or halogenated C_1-3Alkyl.

Also in some embodiments, the present invention provides a kind of compound, for such as formula (IIIf) compound represented or Stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIIf), wherein R^mFor hydrogen or methyl；R^vFor hydrogen or methyl； R^wFor methyl, isopropyl, difluoromethyl or four fluoro ethyls.

Also in some embodiments, the present invention provides a kind of compound, for such as formula (IIIg) compound represented or Stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIIg):

Wherein: X is chlorine.

Also in some embodiments, the present invention provides a kind of compound, for such as formula (IIIh) compound represented or Stereoisomer, nitrogen oxides or its salt of compound shown in formula (IIIh):

Wherein: X is chlorine.

In some of embodiments, the present invention provides a kind of compound, for such as formula (IVa) compound represented or formula (IVa) stereoisomer, nitrogen oxides or its salt of compound shown in:

Wherein: Ay2 has meaning as described in the present invention.

In some of embodiments, the present invention provides a kind of compound, for such as formula (IVb) compound represented or formula (IVb) stereoisomer, nitrogen oxides or its salt of compound shown in:

Wherein: Ay2 has meaning as described in the present invention.

In some of embodiments, Ay2 is the C optionally replaced_10-14Aryl, the C optionally replaced_1-5Heteroaryl optionally takes The C in generation_3-8Naphthenic base, the C optionally replaced_2-10Heterocycle or substituted phenyl；The substitution optionally replaces, substituent group number It is 1,2,3,4,5 or 6；Substituent group can be identical or different；Wherein substituent group be fluorine, chlorine, bromine, iodine, amino, nitro, cyano, Hydroxyl, carboxyl, C_1-4Alkyl, halogenated C_1-4Alkyl, C_2-4Alkenyl, halogenated C_2-4Alkenyl, C_2-4Alkynyl, halogenated C_2-4Alkynyl, C_1-4Alcoxyl Base, C_1-4Alkylamino, C_1-4Alkylthio group, C_3-6Naphthenic base, C_2-6Heterocycle, C_6-10Aryl or C_1-5Heteroaryl.

In other embodiment, Ay2 is the C optionally replaced_3-6Naphthenic base, the C optionally replaced_2-6Heterocycle or substitution Phenyl；The substitution optionally replaces, and substituent group number is 1,2,3,4,5 or 6；Substituent group can be identical or different；Its Middle substituent group is fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, methyl, ethyl, n-propyl, isopropyl, methoxy Base, ethyoxyl, difluoromethyl, trifluoromethyl, difluoro-methoxy or trifluoromethoxy.

In some of embodiments, the present invention provides a kind of compound, for such as formula (IVc) compound represented or formula (IVc) stereoisomer, nitrogen oxides or its salt of compound shown in:

Wherein: Ay1 has meaning as described in the present invention.

In some of embodiments, the present invention provides a kind of compound, for such as formula (IVd) compound represented or formula (IVd) stereoisomer, nitrogen oxides and the salt of compound shown in:

Wherein: Ay1 has meaning as described in the present invention.

In some of embodiments, Ay1 is the C optionally replaced_6-10Aryl, the C optionally replaced_1-6Heteroaryl optionally takes The C in generation_3-8Naphthenic base or the C optionally replaced_2-8Heterocycle；The optional substitution, substituent group number are 1,2,3,4,5 or 6；It takes It can be identical or different for base；Wherein substituent group is fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C_1-4Alkyl, Halogenated C_1-4Alkyl, C_2-4Alkenyl, halogenated C_2-4Alkenyl, C_2-4Alkynyl, halogenated C_2-4Alkynyl, C_1-4Alkoxy, C_1-4Alkylamino, C_1-4Alkane Sulfenyl, C_3-6Naphthenic base, C_2-6Heterocycle, C_6-10Aryl or C_1-5Heteroaryl.

In other embodiment, Ay1 is the phenyl optionally replaced, the C optionally replaced_3-6Naphthenic base optionally replaces C_2-6Heterocycle；The optional substitution, substituent group number are 1,2,3,4,5 or 6；Substituent group can be identical or different；Wherein Substituent group be fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, methyl, ethyl, n-propyl, isopropyl, methoxyl group, Ethyoxyl, difluoromethyl, trifluoromethyl, difluoro-methoxy or trifluoromethoxy.

In other embodiment, Ay1 C_3-6Naphthenic base, the phenyl being optionally optionally substituted by halogen or the C containing an oxygen_2-6 Heterocycle.

In some of embodiments, the present invention provides a kind of compound, is the compound with one of following structure Or stereoisomer, nitrogen oxides or its salt with one of following structural compounds:

In some of embodiments, composition of the present invention optionally further includes can at least one pesticide The auxiliary agent of receiving.

In other embodiment, composition of the present invention is Herbicidal combinations.

On the other hand, the present invention provides compound of the present invention or the composition comprising compound of the present invention in agriculture Application in industry.

Further, the present invention provides compound of the present invention or the composition comprising compound of the present invention is being planted Application in object disease control.

Further, the present invention provides compound of the present invention or the composition comprising compound of the present invention exists Application in agriculture weeding.

In some of embodiments, the useful plant includes soybean, peanut or sunflower.

Compound provided by the invention, being a kind of pair, weeds are more effective, cost is lower, toxicity is smaller, environmentally safe New compound.

The composition and preparation of the compounds of this invention

The compound of the present invention is generally useful as the herbicide active active ingredients in composition or preparation, the composition or system Agent has at least one auxiliary agent pesticide-acceptable, and the auxiliary agent is selected from surfactant, solid diluent and liquid diluting Agent etc., the auxiliary agent for meeting Pesticide use requirement belong to the scope of the present invention.Select the preparation or composition components, with institute The physical characteristic, method of application and environmental factor (such as soil types, humidity and temperature) for stating active constituent are consistent.

Useful preparation includes liquid composition and solid composite.Liquid composition includes solution (including missible oil), hangs Supernatant liquid, lotion (including microemulsion and/or suspended emulsion) etc., they can optionally be crowded into gel.Aqueous liquid composition General type be solubility concentrate, suspension-concentrates, capsule suspension liquid, concentrated emulsion, microemulsion and suspended emulsion.It is non-aqueous Property liquid composition general type be missible oil, microemulsifiable concentrate, dispersibles concentrate and oil dispersion.

The general type of solid composite is pulvis, powder, particle, pellet, spherolite, pastille, tablet, filling film (packet Include seed pelleting) etc., they can be the (" wettable ") or water-soluble of water dispersible.By film forming solution or flowable The film and coating that suspension is formed are used especially for seed treatment.Active constituent can be by (micro-) capsule encapsulating, and further shape At suspension or solid pharmaceutical preparation；Or it can be by entire active agent preparation capsule encapsulating (or " cladding ").Capsule encapsulating can be controlled The release of system or delay active constituent.The advantages of emulsifiable particle combines both cream preparation and dry granular preparation.It is highly concentrated Degree composition is mainly used as the intermediate of other preparations.

Sprayable preparation is usually dispersed in suitable medium before the spraying.By such liquid preparation and solid pharmaceutical preparation It is configured to be easy to the diluted preparation in spraying medium (usually water).Sprayed volume can rise to several kilolitres in per hectare about one In the range of, but more typically in the range of per hectare about ten rises to several hundred liters.Sprayable preparation can in the sink with water Or another suitable medium mixing, leaf is handled for applying by air or ground, or be administered to the growth of plant In medium.Liquid and dry preparation can be added in drip irrigation system with direct quantitative, or furrow is quantitatively adding during plantation In.

The preparation usually will include a effective amount of active constituent, diluent and surfactant, and summation is by weight 100%.

Solid diluent include for example clay such as bentonite, montmorillonite, attapulgite and kaolin, gypsum, cellulose, Titanium dioxide, zinc oxide, starch, dextrin, sugar (such as lactose, sucrose), silica, talcum, mica, diatomite, urea, carbonic acid Calcium, sodium carbonate and sodium bicarbonate and sodium sulphate.Typical solid diluent is described in the Handbook of of Watkins et al. Insecticide Dust Diluents and Carriers, second edition, Dorland Books, Caldwell, New In Jersey.

Liquid diluent includes such as water, N, N- dimethyl alkane amide (such as N,N-dimethylformamide), limonene, two Methyl sulfoxide, ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, gathers N- alkyl pyrrolidone (such as N-Methyl pyrrolidone) Propylene glycol, propylene carbonate, butylene carbonate, paraffin (such as white mineral oil, normal paraffin hydrocarbons, isoparaffin), alkylbenzene, alkyl Naphthalene, glycerol, glyceryl triacetate, sorbierite, aromatic hydrocarbons, dearomaticized aliphatic compound, alkylbenzene, alkylnaphthalene, ketone (such as hexamethylene Ketone, 2-HEPTANONE, isophorone and 4- hydroxy-4-methyl-2-pentanone), acetic acid esters (such as isoamyl acetate, hexyl acetate, acetic acid heptan Ester, octyl acetate, nonyl acetate, acetic acid tridecane base ester and isobornyl acetate), other esters (as alkylation lactate, binary Ester and gamma-butyrolacton) and can be straight chain, branch, saturated or unsaturated alcohol (such as methanol, ethyl alcohol, normal propyl alcohol, Isopropanol, n-butanol, isobutanol, n-hexyl alcohol, 2-Ethylhexyl Alcohol, n-octyl alcohol, decyl alcohol, isodecanol, i-octadecanol, cetanol, the moon Cinnamic alcohol, tridecanol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol and benzylalcohol).Liquid diluent further include saturation and not The glyceride of the fatty acid (usually C6-C22) of saturation, such as oil (such as olive oil, castor oil, the Asia of vegetable seeds and fruit Flaxseed oil, sesame oil, corn oil, peanut oil, sunflower oil, grape seed oil, safflower oil, cottonseed oil, soya-bean oil, rapeseed oil, coconut palm Seed oil and palm-kernel oil), animal sources fatty (such as tallow, lard, lard, cod-liver oil, fish oil) and their mixing Object.Liquid diluent further includes the fatty acid of alkylation (such as methylation, ethylization, butylation), and wherein fatty acid can lead to It crosses the glycerol ester hydrolysis from plant and animal to obtain, and can be purified by distillation.Typical liquid diluent is retouched It is set forth in the Solvents Guide of Marsden, second edition, Interscience, New York, in 1950.

Solid composite and liquid composition of the invention generally comprises one or more surfactants.When adding liquid When middle, surfactant (also referred to as " reagent with surface-active ") usually changes, and most commonly reduces the surface tension of liquid. According to the property of hydrophilic radical and lipophilic group in surfactant molecule, surfactant can be used as wetting agent, dispersing agent, Emulsifier or defoaming agent.

Surfactant can be divided into nonionic surfactant, anionic surfactant or cationic surfactant. The nonionic surfactant that can be used as composition of the invention includes but is not limited to: alcohol alkoxylates, is such as based on natural alcohol With synthol (it is branch or straight chain) and by pure and mild ethylene oxide, propylene oxide, epoxy butane or their mixing The alcohol alkoxylates of object preparation；Amine ethoxylation, alkanolamide and ethoxylation alkanolamide；It is alkoxylated sweet Oily three esters, such as the soybean, castor-oil plant and rapeseed oil of ethoxylation；Alkyl phenol alkoxylates, as octyl phenol ethoxylation, Nonyl phenol ethoxy, dinonyl phenol ethoxylate and dodecyl phenol ethoxylate are (by phenol and epoxy second Alkane, propylene oxide, epoxy butane or their mixture preparation)；By ethylene oxide or propylene oxide and reversed block polymer The block polymer of preparation, wherein the end-blocks are prepared by propylene oxide；The fatty acid of ethoxylation；The rouge of ethoxylation Fat race ester and oil；The methyl ester of ethoxylation；Ethoxylation triphenyl vinyl phenol (including by ethylene oxide, propylene oxide, Those of epoxy butane or their mixture preparation)；Aliphatic ester, glyceride, the derivative of wool aliphatic radical, more ethoxylations Ester, such as Span and more ethyoxyls of the sorbitan fatty acid esters of more ethoxylations, more ethoxylations Change fatty acid glyceride；Other dehydrated sorbitol derivatives, such as sorbitan ester；Polymeric surfactant is such as random total Polymers, block copolymer, alkyd PEG (polyethylene glycol) resin, grafting or dressing polymer and star-type polymer；Polyethylene glycol (PEG)；Cithrol；The surfactant of silicone base；And sugar derivatives, such as sucrose ester, alkyl polydextrose Glycosides and alkyl polysaccharide.

Available anionic surfactant includes but is not limited to: the salt of alkyl aryl sulphonic acid and they；The alcohol of carboxylation or Alkyl phenol ethoxylate；Diphenyl sulfonate derivatives；Lignin and lignin derivative, such as lignosulfonates；Horse Come sour or succinic acid or their acid anhydrides；Alkene sulfonic acid ester；Phosphate, phosphate, the alkyl phenol alkane of such as alcohol alkoxylates The phosphate of oxygroup compound and the phosphate of styrylphenol ethoxylates；The surfactant of protein base；Sarcosine Derivative；Styrylphenol ether sulfate；The sulfate and sulfonate of oil & fat acid；The sulfate of ethoxylated alkylphenol And sulfonate；The sulfate of alcohol；The sulfate of ethoxylated alcohol；The sulfonate of amine and amide, such as N, N- alkyltaurate； The sulfonate of benzene, isopropyl benzene,toluene,xylene and detergent alkylate and tridane；The sulfonate of polycondensation naphthalene；Naphthalene and The sulfonate of alkylnaphthalene；The sulfonate of petroleum distillate；Sulphosuccinamate；And the derivative of sulfosuccinate and they Object, such as dialkyl sulfosuccinates.

Available cationic surfactant includes but is not limited to: amide and amide ethoxylates；Amine, such as N- alkyl the third two Amine, three propylidene triamines and dipropylene tetramine and ethoxylated amine, ethoxylation diamines and propoxylation amine (by amine and Ethylene oxide, propylene oxide, epoxy butane or their mixture preparation)；Amine salt, such as amine acetate and diamine salts；Quaternary ammonium salt, Such as quaternary salt, ethoxylation quaternary salt and two quaternary salts；And amine oxide, such as alkyl dimethyl amine oxide and two-(2- hydroxyl second Base)-alkyl amine oxide.

Can also be used in composition of the invention is the mixture of nonionic surfactant and anionic surfactant, Or the mixture of nonionic surfactant and cationic surfactant.Nonionic, anion and cationic surfactant And their recommended purposes are disclosed in multiple bibliography announced, including by McCutcheon ' s Division, McCutcheon ' s Emulsifiers published by The Manufacturing Confectioner Publishing Co. And Detergents, North America and international yearbook version；The Encyclopedia of Surface Active of Sisely and Wood Agents, Chemical Publ.Co., Inc., New York, 1964；And A.S.Davidson and B.Milwidsky Synthetic Detergents, the 7th edition, John Wiley and Sons, New York, 1987.

Composition of the invention also may include the formulation auxiliary agents and additive known to those skilled in the art for auxiliary agent (some of them are also considered as playing solid diluent, liquid diluent or Action of Surfactant).Such preparation helps Agent and additive are controllable: blistering (defoaming agent such as polysiloxane), active constituent in pH (buffer), process Sedimentation (suspending agent), viscosity (thixotropic thickening agent), the microorganism growth (antimicrobial) in container, product freezing are (antifreeze Agent), color (dyes/pigments dispersion), elution (film forming agent or adhesive), evaporation (anti-evaporant) and other preparation categories Property.Film forming agent includes that such as polyvinyl acetate, polyvinyl acetate copolymer, polyvinylpyrrolidone-vinyl acetate are total Polymers, polyvinyl alcohol, polyvinyl alcohol copolymer and wax.The example of formulation auxiliary agents and additive includes by McCutcheon ' s McCutcheon ' s published by Division, The Manufacturing Confectioner Publishing Co. Volume2:Functional Materials, North America and international yearbook version；And listed in PCT Publication WO03/024222 Those.

Usually by by active constituent be dissolved in solvent or by liquid diluent or dry diluent grind activity at Divide and the compound of the present invention and any other active constituent are incorporated into composition of the invention.It can be by simply mixing The ingredient prepares solution, including missible oil.If be used as missible oil liquid composition solvent be it is unmixing with water, lead to Being commonly incorporated into emulsifier emulsifies the solvent containing active constituent when being diluted with water.Medium mill can be used to carry out wet lapping partial size At most 2,000 μm of active component slurry, to obtain the particle that average diameter is lower than 3 μm.It is water-soluble serous to be prepared as into Product suspension-concentrates (see, for example, U.S.3,060,084) are further processed to form water dispersible by spray drying Particle.Dry preparation usually requires dry milling procedures, generates the average grain diameter in 2 μm to 10 μ ms.Pulvis and powder can To be prepared by mixing, and usually by grinding (such as with hammer-mill or fluid energy mill).It can be by the way that active material be sprayed Particle and pellet are prepared on pre-formed granules carrier or through agglomeration technique.Referring to Browning's " Agglomeration " (Chemical Engineering, 4 days, the 147-48 pages December in 1967；The Chemical of Perry Engineer ' s Handbook, the 4th edition, McGraw-Hill, New York, 1963, the 8-57 pages and page and WO91/ thereafter 13546.Pellet can be prepared as described in U.S.4,172,714.Water dispersible and water-soluble particle can be as It is prepared proposed in U.S.4,144,050, U.S.3,920,442 and DE.3,246,493.Tablet can such as U.S.5, 180,587, it is prepared proposed in U.S.5,232,701 and U.S.5,208,030.Film can such as GB2,095,558 and It is prepared proposed in U.S.3,299,566.

Other information relevant to formulation art, referring to " The Formulator ' the s Toolbox- of T.S.Woods Product Forms for Modern Agriculture ", Pesticide Chemistry and Bioscience, The Food-Environment Challenge, T.Brooks and T.R.Roberts are edited, Proceedings of the9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, the 120-133 pages.Referring also to U.S.3,235,361 the 6th columns, the 16th row to the 7th column, the 19th row and Embodiment 10-41；U.S3,309,192 the 5th columns, the 43rd row to the 7th column, the 62nd row and embodiment 8,12,15,39,41,52, 53,58,132,138-140,162-164,166,167 and 169-182；U.S.2,891,855 the 3rd columns, the 66th row to the 5th column, 17th row and embodiment 1-4；Weed Control as a Science, John the Wiley and Sons of Klingman, Inc., New York, 1961, the 81-96 pages；The Weed Control Handbook of Hance et al., the 8th edition, Blackwell Scientific Publications, Oxford, 1989；And Developments in formulation Technology, PJB Publications, Richmond, UK, 2000.

The application of the compounds of this invention

Herbicide of the present invention can by plant spray, be applied in soil, be applied on water surface and to use.Suitably Determine the dosage of active component to meet application purpose.The content of active component is suitably determined according to the purpose.

The dosage of the compounds of this invention is according to the type of compound used therefor, target weeds, the trend of weeds appearance, environment item Part and the type of herbicide etc..When herbicide of the present invention itself form for example in the form of powder or particle in use, its use Amount is suitably chosen for 1g-50kg, preferably 10g-10kg/1 hectares of active component.When herbicide of the invention in liquid form Such as in use, its dosage is suitably chosen in the form of emulsifiable concentrate, wettable powder or flowable formulation 0.1-50,000ppm, preferably 10-10,000ppm.

The method for the weeds in crop that the present invention provides a kind of for controlling useful plant, this method include to described Weeds apply chemical combination of the invention to the place of the weeds or to the useful plant or to the place of the useful plant Object or composition.

The present invention also provides the method for grass and/or weeds in a kind of crop of selectivity control useful plant, the party Method includes to useful plant or its place or having such as formula (I), formula (Ia), formula to cultural area application herbicidally effective amount (II), formula (II-1), formula (II-2), formula (II-3), formula (II-4), formula (II-5), formula (III-1), formula (III-2), formula (IIa), formula (IIb), formula (IIc), formula (IId), formula (IIa-1), formula (IIa-2), formula (IIa-3), formula (IIa-4), formula (IIa- 5), formula (IIa-6), formula (IIa-7), formula (IIa-8), formula (IIa-9), formula (IIa-10), formula (IIa-11), formula (IIa-12), Formula (IIa-13), formula (IIa-14), formula (IIa-15), formula (IIa-16), formula (IIa-17), formula (IIa-18), formula (IIIa), formula (IIIb), formula (IIIc), formula (IIId), formula (IIIe), formula (IIIf), formula (IIIg), formula (IIIh), formula (IV), formula (IVa), Formula (IVb), formula (IVc) or formula (IVd) compound represented or its stereoisomer, nitrogen oxides or its salt.

Term " herbicide " means a kind of compound controlled or change plant growth.Term " herbicidally effective amount " means energy The amount of the composition of enough such a compounds for generating control or changing plant growth effect or such compound.Control or The effect of change includes the deviation of all organic growths, for example, murdering, postponing, leaf is burnt, albinism, dwarfing etc..Term " plant " refers to all tangible parts of plant, including seed, seedling, shoot, root, stem tuber, stem, stalk, leaf and fruit.Term " location " is intended to include soil, seed and seedling, together with the plant (established vegetation) having built up And the region that may have not only been grown including weeds, but also the region not yet occurred including weeds, and further include closing In the region of the plantation of useful plant crop." region of plantation " includes the soil that crop plants have been grown on it, and It is intended to plant the soil of such crop plants.Term " weeds " as used herein means any undesirable plant, and And therefore not only including important agronomy weeds as described below, but also including volunteer crops plant.

The useful plant crop that may have been used composition according to the present invention includes but is not limited to perennial crop, such as Citrus fruit, vine, nut, oil palm, olive, pomaceous fruits fruit, drupe and rubber and it is annual can farming object, Such as cereal (such as barley and wheat), cotton, rape, corn, rice, soybean, beet, sugarcane, sunflower, ornamental plant, willow Branch millet, turf and vegetables, especially cereal, corn and soybean.

The grass to be controlled and weeds are either monocotyledonous species, such as Agrostis, amur foxtail category, Avena, arm Shape grass category, Brome, Cenchrus, Cyperus, knotgrass, Echinochloa, wild Panicum, Lolium, Monochoria, Panicum, precocity Standing grain category, Rottboellia exaltata L. F category, Sagittaria, Scirpus, setaria, chrysanthemum harvest spp and sorghum, are also possible to dicots species, example Such as hemp category, Amaranthus, Chenopodium, Chrysanthemum, Euphorbia, galium, Ipomoea, Kochia, Nasturtium, arsesmart, chrysanthemum Harvest category, sinapsis alba category, Solanum, Stellaria, Veronica, Viola and Xanthium.

The compounds of this invention can show the tolerance to important crops, and the crops include but is not limited to clover, big Wheat, cotton, wheat, rape, sugar beet, corn (maize), sorghum, soybean, rice, oat, peanut, vegetables, tomato, Ma Ling Potato, perennial long-term cropping include coffee, cocoa, oil palm, rubber, sugarcane, citrus, grape, fruit tree, nutwood, banana, Chinese herbaceous peony Such as by tree and coniferous tree (such as torch pine) and turf species, (such as meadow is precocious for grass, pineapple, hops, tea and forest Standing grain, saint augustine grass (St.Augustine grass), Kentucky fescue and bermudagrass grass).

If necessary, it is according to the present invention have as formula (I), formula (Ia), formula (II), formula (II-1), formula (II-2), Formula (II-3), formula (II-4), formula (II-5), formula (III-1), formula (III-2), formula (IIa), formula (IIb), formula (IIc), formula (IId), formula (IIa-1), formula (IIa-2), formula (IIa-3), formula (IIa-4), formula (IIa-5), formula (IIa-6), formula (IIa-7), Formula (IIa-8), formula (IIa-9), formula (IIa-10), formula (IIa-11), formula (IIa-12), formula (IIa-13), formula (IIa-14), formula (IIa-15), formula (IIa-16), formula (IIa-17), formula (IIa-18), formula (IIIa), formula (IIIb), formula (IIIc), formula (IIId), formula (IIIe), formula (IIIf), formula (IIIg), formula (IIIh), formula (IV), formula (IVa), formula (IVb), formula (IVc) or formula (IVd) compound represented or its stereoisomer, nitrogen oxides or its salt, can also with other active components, such as other Herbicide and/or insecticide and/or acaricide and/or nematicide and/or invertebrate poison and/or fungicide and/ Or plant growth regulator is applied in combination.These mixtures and these mixtures to control weeds and/or undesirable The purposes of the growth of plant forms other aspects of the invention again.To avoid query, mixture of the invention also includes two Kind or more is different to be had such as formula (I), formula (Ia), formula (II), formula (II-1), formula (II-2), formula (II-3), formula (II- 4), formula (II-5), formula (III-1), formula (III-2), formula (IIa), formula (IIb), formula (IIc), formula (IId), formula (IIa-1), formula (IIa-2), formula (IIa-3), formula (IIa-4), formula (IIa-5), formula (IIa-6), formula (IIa-7), formula (IIa-8), formula (IIa- 9), formula (IIa-10), formula (IIa-11), formula (IIa-12), formula (IIa-13), formula (IIa-14), formula (IIa-15), formula (IIa- 16), formula (IIa-17), formula (IIa-18), formula (IIIa), formula (IIIb), formula (IIIc), formula (IIId), formula (IIIe), formula (IIIf), formula (IIIg), formula (IIIh), formula (IV), formula (IVa), formula (IVb), formula (IVc) or formula (IVd) compound represented Or the mixture of its stereoisomer, nitrogen oxides or its salt.Specifically, the invention further relates to a kind of composition of the invention, The composition remove as formula (I), formula (Ia), formula (II), formula (II-1), formula (II-2), formula (II-3), formula (II-4), formula (II-5), Formula (III-1), formula (III-2), formula (IIa), formula (IIb), formula (IIc), formula (IId), formula (IIa-1), formula (IIa-2), formula (IIa-3), formula (IIa-4), formula (IIa-5), formula (IIa-6), formula (IIa-7), formula (IIa-8), formula (IIa-9), formula (IIa- 10), formula (IIa-11), formula (IIa-12), formula (IIa-13), formula (IIa-14), formula (IIa-15), formula (IIa-16), formula (IIa- 17), formula (IIa-18), formula (IIIa), formula (IIIb), formula (IIIc), formula (IIId), formula (IIIe), formula (IIIf), formula (IIIg), formula (IIIh), formula (IV), formula (IVa), formula (IVb), formula (IVc) or formula (IVd) compound represented or its solid are different Except structure body, nitrogen oxides or its salt, include at least one other herbicide.

General synthesis process

In the present specification, if there are any difference between chemical name and chemical structure, structure is dominant.Generally Ground, the compound of the present invention described method can be prepared through the invention, unless there are further instruction.Preparation is originally Raw material used in the compound of invention, reagent etc. can be commercially available, or can pass through the method for this field routine It is prepared.

The test condition of nuclear magnetic resonance spectroscopy of the present invention is: under room temperature, Brooker (Bruker) 400MHz or The nuclear magnetic resonance spectrometer of 600MHz, with CDC1₃, d⁶- DMSO, CD₃OD or d⁶Acetone is solvent (report is as unit of ppm), uses TMS (0ppm) or chloroform (7.26ppm) are used as reference standard.When there is multiplet, following abbreviation: s will be used (singlet, unimodal), d (doublet, bimodal), t (triplet, triplet), q (quartet, quartet), m (multiplet, multiplet), br (broadened, broad peak), dd (doublet of doublets, double doublet), dt (doublet of triplets, double triplets).Coupling constant is indicated with hertz (Hz).

Mass spectrometric analysis method used in the present invention are as follows: use Agilent 1260HPLC；Agilent 6120ESI.

A phase: water (contains 0.1% formic acid)；B phase: acetonitrile (contains 0.1% formic acid).

Gradient elution: 0-3min, 5-100%B；3-6min, 100%B.

Flow velocity: 0.6mL/min.

Detection wavelength: 254nm.

MS parameter: ESI is just scanned, collision induced dissociation: 70V.

Drying nitrogen: 12L/min, atomization gas pressure: 40psi, gas temperature: 350 DEG C.

Appropriate amount of sample is taken, 0.5mL methanol is dissolved in, sample introduction carries out level-one MS full scan under positive ESI mode and obtains quasi-molecule Quasi-molecular ions [M+H]⁺Reading.

Following logogram word paraphrase is through the present invention:

Petroleum ether: petroleum ether

DMF:N, dinethylformamide, dimethylformamide

EtOAc: ethyl acetate

HBr: hydrogen bromide

K₂CO₃: potassium carbonate

M-CPBA: metachloroperbenzoic acid

NFSI:N- fluoro bis benzene sulfonamide

THF: tetrahydrofuran

TLC: thin-layered chromatography

Following synthetic schemes and embodiment 1-16 is for being further illustrated the contents of the present invention.

Synthetic schemes one

Formula (5a) compound can be prepared by synthetic schemes one, wherein R^cFor C_2-10Alkyl, halogenated alkyl or cycloalkanes Base.(a ') compound reacts to obtain formula (b ') compound in HBr with thiocarbamide；Difluoro ethyl acetoacetate is first anti-with hydrazine hydrate It answers, then with phosphorus oxychloride reaction, obtained intermediate and R^c- I reacts to obtain formula (1a) compound and formula (1b) compound；Formula (1a) compound occurs reduction reaction and obtains formula (2a) compound；Formula (2a) compound and bromo-hydrocarbons (such as carbon tetrabromide) occur anti- It should obtain formula (3a) compound；Formula (3a) compound (such as K under alkaline condition₂CO₃Deng) anti-with the generation condensation of formula (b ') compound It should obtain formula (4a) compound；Formula (4a) compound further occurrence aoxidizes to obtain formula (5a) compound.

Synthetic schemes two

Formula (5b) compound can be prepared by synthetic schemes one, wherein R^cFor C_2-10Alkyl, halogenated alkyl or cycloalkanes Base.Formula (1b) compound occurs reduction reaction and obtains formula (2b) compound；Formula (2b) compound and bromo-hydrocarbons (such as carbon tetrabromide) It reacts to obtain formula (3b) compound；Formula (3b) compound (such as K under alkaline condition₂CO₃Deng) and the generation of formula (b ') compound Condensation reaction obtains formula (4b) compound；Formula (4b) compound further occurrence aoxidizes to obtain formula (5b) compound.

Embodiment

86页详细技术资料下载

上一篇：一种医用注射器针头装配设备

下一篇：一种催化茚虫威关键中间体合成的催化剂及其应用

Isoxazoline derivative and its application in agricultural

相关技术

网友询问留言