Pyrazole derivatives containing a quinazolin dione fragment, their use and a pesticidal herbicide

Abstract

The present application relates to the field of pesticide herbicide, and discloses a pyrazole derivative containing a quinazolinone fragment, application of the pyrazole derivative and a pesticide herbicide, the pyrazole derivative has a structure shown in formula (I), and the pyrazole derivative has the advantages of wide weed spectrum and high safety to crops.

Description

Technical Field

[0001] This invention relates to the field of pesticides and herbicides, specifically to a pyrazole derivative containing a quinazolinidone fragment, the application of the pyrazole derivative, and a pesticide and herbicide containing the pyrazole derivative. Background Technology

[0002] p-Hydroxyphenylpyruvate dioxygenase (4-HPPD) was identified as a target for herbicides in the 1990s.

[0003] 4-HPPD is widely present in aerobic organisms and is mainly involved in the metabolism of tyrosine. In plants, the tyrosine metabolite p-hydroxyphenylpyruvate is converted into hydantoin by 4-HPPD, and hydantoin is further converted into plastoquinone and tocopherol. Plastoquinone and tocopherol are important precursors for plant photosynthesis. Therefore, by inhibiting the synthesis of plastoquinone and tocopherol in plants, normal photosynthesis is hindered, leading to bleaching symptoms and death.

[0004] Herbicides targeting 4-HPPD are characterized by high efficiency, low toxicity, environmental friendliness, and good safety for subsequent crops.

[0005] Therefore, 4-HPPD herbicides are a class of herbicides with significant research value and development prospects, and an increasing number of pesticide companies are investing in their research and development. In recent years, patent reports on this type of herbicide have also shown a year-on-year increasing trend. As an important target for the development of novel herbicides, there are currently 16 commercially available 4-HPPD herbicides and several HPPD inhibitor molecules in the product development stage.

[0006] During the application of herbicides, repeated overuse of single herbicides and genetic mutations in weeds can lead to severe herbicide resistance. For example, ACCase and AHAS herbicides have become ineffective against some noxious weeds even with increased dosages due to severe resistance issues in the field. Therefore, it is necessary to develop novel targeted herbicides that avoid weed resistance problems to address the control of resistant weeds in the field.

[0007] To address this issue, in 2015, our research group applied for a patent application for triketone compounds and their preparation methods and applications (CN104557739A). Building upon this, through innovative research, we designed and synthesized a series of novel 4-HPPD inhibitor molecules. These compounds exhibit excellent herbicidal activity against a wide range of weeds and demonstrate good safety for crops, showing promising application prospects. Summary of the Invention

[0008] The purpose of this invention is to overcome the aforementioned deficiencies of the prior art and provide a new pyrazole derivative containing a quinazolinidone fragment that has the advantages of broad-spectrum herbicidal activity and high crop safety.

[0009] To achieve the above objectives, a first aspect of the present invention provides a pyrazole derivative containing a quinazolinidone fragment, the pyrazole derivative having the structure shown in formula (I).

[0010]

[0011] In equation (I),

[0012] R1 is selected from H, substituted or unsubstituted phenyl, or substituted or unsubstituted C1-C6 alkyl;

[0013] R2 is selected from H, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, substituted or unsubstituted C1-C6 alkyl;

[0014] R3 is selected from H, C1-C6 alkyl, C1-C6 alkenyl, C1-C6 alkynyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl;

[0015] R4 is H or methyl;

[0016] Z is either O or S;

[0017] Y is a C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, substituted or unsubstituted naphthyl, substituted or unsubstituted indenyl, substituted or unsubstituted five-membered heterocycle containing at least one element of N, O and S, substituted or unsubstituted six-membered heterocycle containing at least one element of N, O and S, substituted or unsubstituted benzo-five-membered heterocycle containing at least one element of N, O and S, or substituted or unsubstituted benzo-six-membered heterocycle containing at least one element of N, O and S.

[0018] Furthermore, the optional substituents in R1, R2, R3, and Y are each independently selected from halogens, C1-C6 alkyl groups, C1-C6 alkoxy groups, C1-C6 alkyl groups substituted with halogens, C1-C6 alkoxy groups substituted with halogens, phenoxy groups, nitro groups, and amino groups.

[0019] X is any group selected from X1-X14 below, or X is a protected or deprotected sugar residue, wherein the protecting group in the sugar residue is selected from at least one of acetyl, formyl, propionyl, butyryl, unsubstituted or C1-C6 alkyl and / or halogen-substituted benzoyl, and unsubstituted or C1-C6 alkyl and / or halogen-substituted benzyl:

[0020]

[0021] Among them, A in X1-X14 1 A 2a A 2b A 3 A 4 A 5 A 6a A 6b A 7 A 8 A 9a A 9b A 10a A 10b A 11a A 11b A 12a A 12b A 13a A 13b A 14a and A 14b Each is independently selected from H, C1-C 12 Alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C substituted with halogen 12 Alkyl, C1-C 12 Alkoxy, phenyl, phenyl substituted with C1-C6 alkyl and / or halogen, phenyl substituted with C1-C6 alkoxy, naphthyl, naphthyl substituted with alkylamino, pyridyl, furanyl, thiophene, thiophene substituted with C1-C6 alkyl and / or halogen, pyrazolyl, pyrazolyl substituted with C1-C6 alkyl, imidazolyl, imidazolyl substituted with C1-C6 alkyl, amino substituted with C1-C6 alkyl;

[0022] Furthermore, each of the n values ​​in X1-X14 is an independent integer from 0 to 6.

[0023] Preferably, in formula (I),

[0024] R1 is selected from H, substituted or unsubstituted phenyl, or substituted or unsubstituted C1-C6 alkyl;

[0025] R2 is selected from H, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, substituted or unsubstituted C1-C6 alkyl;

[0026] R3 is selected from H, C1-C6 alkyl, C1-C6 alkenyl, C1-C6 alkynyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl;

[0027] R4 is H or methyl;

[0028] Z is either O or S;

[0029] Y is C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyrroleyl, substituted or unsubstituted furanyl, substituted or unsubstituted tetrahydrofuranyl, substituted or unsubstituted thiophenyl, substituted or unsubstituted thiazolyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted pyrazolyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted valproicinyl, substituted or unsubstituted pyridinyl, substituted or unsubstituted pyranyl, substituted or unsubstituted piperidinyl, substituted or unsubstituted piperazineyl, substituted or unsubstituted pyridazineyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted caprolactamyl;

[0030] X is any group selected from X1-X14 below, or X is a protected or deprotected sugar residue, wherein the protecting group in the sugar residue is selected from at least one of acetyl, formyl, propionyl, butyryl, unsubstituted or C1-C6 alkyl and / or halogen-substituted benzoyl, and unsubstituted or C1-C6 alkyl and / or halogen-substituted benzyl:

[0031]

[0032]

[0033] Among them, A in X1-X14 1 A 2a A 2b A 3 A 4 A 5 A 6a A 6b A 7 A 8 A 9a A 9b A 10a A 10b A 11a A 11b A 12a A 12b A 13a A 13b A 14a and A 14b Each is independently selected from H, C1-C 12 Alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C substituted with halogen 12 Alkyl, C1-C 12Alkoxy, phenyl, phenyl substituted with C1-C6 alkyl and / or halogen, phenyl substituted with C1-C6 alkoxy, naphthyl, naphthyl substituted with alkylamino, pyridyl, furanyl, thiophene, thiophene substituted with C1-C6 alkyl and / or halogen, pyrazolyl, pyrazolyl substituted with C1-C6 alkyl, imidazolyl, imidazolyl substituted with C1-C6 alkyl, amino substituted with C1-C6 alkyl;

[0034] Furthermore, each of the n values ​​in X1-X14 is an independent integer from 0 to 6.

[0035] The derivatives provided by this invention have excellent weed control efficacy and very good safety for crops such as rice, corn, wheat, cotton, and peanuts. They are expected to be developed into new HPPD herbicides to solve the current weed control problem.

[0036] In this invention, the "sugar residue" refers to the portion of a sugar molecule that is connected to the parent nucleus structure of formula (I) via a glycosidic bond; the sugar in the sugar residue of this invention can be a monosaccharide, disaccharide, or polysaccharide, such as glucose.

[0037] In this invention, "alkylamino" in "naphthyl substituted with alkylamino" means an amino group substituted with an alkyl group, and the alkyl group in "alkylamino" can be a C1-C6 alkyl group.

[0038] In this invention, the term "substituted or unsubstituted benzopentacyclic heterocycle containing at least one of N, O and S" refers to a bicyclic compound formed by benzene and a five-membered heterocycle sharing a single chemical bond, and the bicyclic compound contains at least one of N, O and S.

[0039] In this invention, the term "substituted or unsubstituted benzohexa-membered heterocycle containing at least one of N, O and S" refers to a bicyclic compound formed by benzene and a six-membered heterocycle sharing a single chemical bond, and the bicyclic compound contains at least one of N, O and S.

[0040] In this invention, "halogen" means at least one element selected from fluorine, chlorine, bromine and iodine.

[0041] In this invention, "C" 1-6 "alkyl" indicates an alkyl group having 1-6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, cyclopropyl, methylcyclopropyl, ethylcyclopropyl, cyclopentyl, methylcyclopentyl, and cyclohexyl.

[0042] In this invention, "C" 1-6"alkoxy group" refers to an alkoxy group with 1-6 carbon atoms, such as methyloxy, ethyloxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, tert-butyloxy, n-pentyloxy, isopentyloxy, n-hexyloxy, cyclopropyloxy, methylcyclopropyloxy, ethylcyclopropyloxy, cyclopentyloxy, methylcyclopentyloxy, and cyclohexyloxy.

[0043] In this invention, "C" 2-6 "Alkenyl" indicates a monoalkenyl, dienyl, or polyalkenyl group having 1-6 carbon atoms, such as vinyl, n-propenyl, isopropenyl, n-butenyl, n-dibutenyl, isobutenyl, tert-butenyl, n-pentenyl, 1,3-pentadienyl, isopentenyl, n-hexenyl, 1,3-hexadienyl, cyclopropenyl, methylcyclopropenyl, ethylcyclopropenyl, cyclopentenyl, methylcyclopentenyl, and cyclohexenyl.

[0044] In this invention, "C" 2-6 "Alynyl" indicates a mono-, di-, or poly-alynyl group with 1-6 carbon atoms, such as ethynyl, n-propynyl, isopropynyl, n-butynyl, n-dibutynyl, isobutynyl, tert-butynyl, n-pentynyl, 1,3-pentadiynyl, isopentenynyl, n-hexynyl, 1,3-hexadiynyl, cyclopropynyl, methylcyclopropynyl, ethylcyclopropynyl, cyclopentynyl, methylcyclopentynyl, and cyclohexynyl.

[0045] "Integers from 0 to 6" include: 0, 1, 2, 3, 4, 5, and 6.

[0046] In a preferred embodiment, in formula (I), Y is a C1-C6 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyrroleyl, substituted or unsubstituted furanyl, substituted or unsubstituted tetrahydrofuranyl, substituted or unsubstituted thiophenyl, substituted or unsubstituted thiazolyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted pyrazolyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted valproicinyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyranyl, substituted or unsubstituted piperidinyl, substituted or unsubstituted piperazineyl, substituted or unsubstituted pyridazineyl, substituted or unsubstituted pyrimidinyl, or substituted or unsubstituted caprolactamyl.

[0047] According to the first preferred embodiment, in formula (I), X is a group represented by X1 below.

[0048]

[0049] In X1, A 1 Selected from C1-C 12Alkyl, C2-C6 alkenyl, C2-C6 alkynyl, phenyl substituted with C1-C6 alkyl and / or halogen, unsubstituted or substituted benzyl, unsubstituted or substituted naphthyl, unsubstituted or substituted pyrroleyl, unsubstituted or substituted furanyl, unsubstituted or substituted tetrahydrofuranyl, unsubstituted or substituted thiophenyl, unsubstituted or substituted thiozolyl, unsubstituted or substituted thiazolyl, unsubstituted or substituted imidazolyl, unsubstituted or substituted C1-C6 alkyl and / or halogenyl, -C6 alkyl and / or halogen-substituted pyrazolyl, unsubstituted or substituted oxazolyl, unsubstituted or substituted valeronyl, unsubstituted or substituted pyridyl, unsubstituted or substituted pyranyl, unsubstituted or substituted pyranyl, unsubstituted or substituted pyridinyl, unsubstituted or substituted pyridinyl, unsubstituted or substituted pyridinyl, unsubstituted or substituted pyrimidinyl, unsubstituted pyrimidinyl, unsubstituted pyrimidinyl, and unsubstituted pyrrolimyl.

[0050] Preferably, in X1, A 1 Selected from C1-C 12 Alkyl groups, phenyl groups substituted with C1-C6 alkyl groups and / or halogens.

[0051] Preferably, in X1, A 1 Phenyls selected from C1-C8 alkyl groups and substituted with C1-C6 alkyl groups.

[0052] According to the second preferred embodiment, in formula (I), X is a group represented by X2 below.

[0053]

[0054] In X2, A 2a and A 2b Each is independently selected from H, C1-C 12 Alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C substituted with halogen 12Alkyl, phenyl, phenyl substituted with C1-C6 alkyl and / or halogen, phenyl substituted with C1-C6 alkoxy, unsubstituted or substituted with C1-C6 alkyl and / or halogen, unsubstituted or substituted with C1-C6 alkyl and / or halogen, unsubstituted or substituted with C1-C6 alkyl and / or halogen, unsubstituted or substituted with C1-C6 alkyl and / or halogen, unsubstituted or substituted with C1-C6 alkyl and / or halogen, tetrahydrofuranyl, unsubstituted or substituted with C1-C6 alkyl and / or halogen, unsubstituted or substituted with C1-C6 alkyl and / or halogen, unsubstituted or substituted with C1-C6 alkyl and / or halogen, thiophenyl, unsubstituted or substituted with C1-C6 alkyl and / or halogen, imidazolyl, unsubstituted or substituted with C1-C6 alkyl and / or halogen, 1-C6 alkyl and / or halogen-substituted pyrazolyl, unsubstituted or substituted oxazolyl, unsubstituted or substituted valeronyl, unsubstituted or substituted pyridyl, unsubstituted or substituted pyranyl, unsubstituted or substituted pyranyl, unsubstituted or substituted pyridinyl, unsubstituted or substituted pyridinyl, unsubstituted or substituted pyridinyl, unsubstituted or substituted pyrimidinyl, unsubstituted or substituted pyrimidinyl, unsubstituted or substituted pyrimidinyl, unsubstituted or substituted pyrrolimyl.

[0055] Preferably, in X2, A 2a and A 2b Each is independently selected from H, C1-C 12 Alkyl groups, halogen-substituted C1-C 12 Alkyl, phenyl, phenyl substituted with C1-C6 alkyl and / or halogen, phenyl substituted with C1-C6 alkoxy.

[0056] Preferably, in X2, A 2a and A 2b Each is independently selected from H, C1-C 12 Alkyl groups, phenyl groups substituted with C1-C6 alkyl groups, and A 2a and A 2b They are not both H.

[0057] According to the third preferred embodiment, in formula (I), X is a group represented by X3 below.

[0058]

[0059] In X3, A 3 Selected from H, C1-C 12 Alkyl, C2-C6 alkenyl, C2-C6 ynyl, C1-C 12Alkylthio, phenyl, unsubstituted or C1-C6 alkyl and / or halogen-substituted benzyl, halogen-substituted C1-C 12 Alkylthio, unsubstituted or C1-C6 alkyl and / or halogenated naphthyl, unsubstituted or C1-C6 alkyl and / or halogenated pyrroleyl, unsubstituted or C1-C6 alkyl and / or halogenated furanyl, unsubstituted or C1-C6 alkyl and / or halogenated tetrahydrofuranyl, unsubstituted or C1-C6 alkyl and / or halogenated thiopheneyl, unsubstituted or C1-C6 alkyl and / or halogenated thiazolyl, unsubstituted or C1-C6 alkyl and / or halogenated imidazolyl, unsubstituted or C1-C6 alkyl and / or halogenated pyrazolyl, unsubstituted or C1-C6 alkyl and / or halogenated alkyl, unsubstituted or C1-C6 alkyl Oxazolyl group substituted with alkyl and / or halogen, valeronyl group unsubstituted or substituted with C1-C6 alkyl and / or halogen, pyridyl group unsubstituted or substituted with C1-C6 alkyl and / or halogen, pyranyl group unsubstituted or substituted with C1-C6 alkyl and / or halogen, piperidinyl group unsubstituted or substituted with C1-C6 alkyl and / or halogen, piperazine group unsubstituted or substituted with C1-C6 alkyl and / or halogen, pyridazine group unsubstituted or substituted with C1-C6 alkyl and / or halogen, caprolactam group unsubstituted or substituted with C1-C6 alkyl and / or halogen.

[0060] Preferably, in X3, A 3 Selected from H, C1-C 12 Alkyl, phenyl, C1-C 12 Alkylthio or halogen-substituted C1-C 12 Alkylthio group.

[0061] Preferably, in X3, A 3 Selected from H, C1-C 10 Alkyl, C1-C 12 Alkylthio or halogen-substituted C1-C 12 Alkylthio group.

[0062] According to the fourth preferred embodiment, in formula (I), X is a group represented by X4 below.

[0063]

[0064] In X4, A 4 Selected from C1-C 12 Alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C substituted with halogen 12Alkyl, phenyl, phenyl substituted with C1-C6 alkyl and / or halogen, unsubstituted or substituted benzyl, unsubstituted or substituted naphthyl, unsubstituted or substituted pyrroleyl, unsubstituted or substituted furanyl, unsubstituted or substituted tetrahydrofuranyl, unsubstituted or substituted thiopheneyl, unsubstituted or substituted thiazolyl, unsubstituted or substituted thiazolyl, unsubstituted or substituted imidazolyl, unsubstituted or substituted thiozolyl / or halogen-substituted pyrazolyl, unsubstituted or C1-C6 alkyl and / or halogen-substituted oxazolyl, unsubstituted or C1-C6 alkyl and / or halogen-substituted valeramide, unsubstituted or C1-C6 alkyl and / or halogen-substituted pyridyl, unsubstituted or C1-C6 alkyl and / or halogen-substituted pyranyl, unsubstituted or C1-C6 alkyl and / or halogen-substituted piperidinyl, unsubstituted or C1-C6 alkyl and / or halogen-substituted piperazine, unsubstituted or C1-C6 alkyl and / or halogen-substituted pyridazine, unsubstituted or C1-C6 alkyl and / or halogen-substituted pyrimidinyl, unsubstituted or C1-C6 alkyl and / or halogen-substituted caprolactam.

[0065] Preferably, in X4, A 4 Selected from C1-C 12 Alkyl groups, halogen-substituted C1-C 12 Alkyl, phenyl, phenyl substituted with C1-C6 alkyl and / or halogen.

[0066] Preferably, in X4, A 4 Selected from C1-C 10 Alkyl groups, and phenyl groups substituted with C1-C6 alkyl groups.

[0067] According to the fifth preferred embodiment, in formula (I), X is a group represented by X5 below.

[0068]

[0069] In X5, A 5 Selected from C1-C 12 Alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C substituted with halogen 12Alkyl, phenyl, phenyl substituted with C1-C6 alkyl and / or halogen, unsubstituted or substituted benzyl, unsubstituted or substituted naphthyl, unsubstituted or substituted pyrroleyl, unsubstituted or substituted furanyl, unsubstituted or substituted tetrahydrofuranyl, unsubstituted or substituted thiopheneyl, unsubstituted or substituted thiazolyl, unsubstituted or substituted thiazolyl, unsubstituted or substituted imidazolyl, unsubstituted or substituted thiozolyl / or halogen-substituted pyrazolyl, unsubstituted or C1-C6 alkyl and / or halogen-substituted oxazolyl, unsubstituted or C1-C6 alkyl and / or halogen-substituted valeramide, unsubstituted or C1-C6 alkyl and / or halogen-substituted pyridyl, unsubstituted or C1-C6 alkyl and / or halogen-substituted pyranyl, unsubstituted or C1-C6 alkyl and / or halogen-substituted piperidinyl, unsubstituted or C1-C6 alkyl and / or halogen-substituted piperazine, unsubstituted or C1-C6 alkyl and / or halogen-substituted pyridazine, unsubstituted or C1-C6 alkyl and / or halogen-substituted pyrimidinyl, unsubstituted or C1-C6 alkyl and / or halogen-substituted caprolactam.

[0070] Preferably, in X5, A 5 Selected from C1-C 12 Alkyl groups, halogen-substituted C1-C 12 Alkyl, phenyl, phenyl substituted with C1-C6 alkyl and / or halogen.

[0071] Preferably, in X5, A 5 Selected from C1-C 10 Alkyl groups, and phenyl groups substituted with C1-C6 alkyl groups.

[0072] According to the sixth preferred embodiment, in formula (I), X is a group represented by X6 below.

[0073]

[0074] In X6, A 6a and A 6b Each is independently selected from C1-C 12 Alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C substituted with halogen 12Alkyl, phenyl, unsubstituted or C1-C6 alkyl and / or halogenated benzyl, unsubstituted or C1-C6 alkyl and / or halogenated naphthyl, unsubstituted or C1-C6 alkyl and / or halogenated pyrroleyl, unsubstituted or C1-C6 alkyl and / or halogenated furanyl, unsubstituted or C1-C6 alkyl and / or halogenated tetrahydrofuranyl, unsubstituted or C1-C6 alkyl and / or halogenated thiopheneyl, unsubstituted or C1-C6 alkyl and / or halogenated thiazolyl, unsubstituted or C1-C6 alkyl and / or halogenated imidazolyl, unsubstituted or C1-C6 alkyl and / or halogenated pyrazolyl Oxazolyl, unsubstituted or substituted by C1-C6 alkyl and / or halogen; valeronyl, unsubstituted or substituted by C1-C6 alkyl and / or halogen; pyridyl, unsubstituted or substituted by C1-C6 alkyl and / or halogen; pyranyl, unsubstituted or substituted by C1-C6 alkyl and / or halogen; piperidinyl, unsubstituted or substituted by C1-C6 alkyl and / or halogen; piperazine, unsubstituted or substituted by C1-C6 alkyl and / or halogen; pyridazine, unsubstituted or substituted by C1-C6 alkyl and / or halogen; caprolactam, unsubstituted or substituted by C1-C6 alkyl and / or halogen.

[0075] Preferably, in X6, A 6a and A 6b Each is independently selected from C1-C 12 Alkyl groups, halogen-substituted C1-C 12 Alkyl, phenyl, phenyl substituted with C1-C6 alkyl and / or halogen, pyridyl, furanyl, thiophene.

[0076] Preferably, in X6, A 6a and A 6b Each is independently selected from C1-C8 alkyl, phenyl substituted with C1-C6 alkyl and / or halogen, and pyridyl.

[0077] According to the seventh preferred embodiment, in formula (I), X is a group represented by X7 below.

[0078]

[0079] In X7, A 7 Selected from C1-C 12 Alkyl, C2-C6 alkenyl, C2-C6 ynyl, C1-C 12 Alkoxy groups, C1-C groups substituted with halogens 12Alkyl, phenyl, phenyl substituted with C1-C6 alkyl and / or halogen, phenyl substituted with C1-C6 alkoxy, pyridyl, furanyl, thiophene, thiophene substituted with C1-C6 alkyl and / or halogen, pyrazolyl, pyrazolyl substituted with C1-C6 alkyl, imidazolyl, imidazolyl substituted with C1-C6 alkyl, unsubstituted or substituted with C1-C6 alkyl and / or halogen, unsubstituted or substituted with C1-C6 alkyl and / or halogen, piperidinyl, unsubstituted or substituted with C1-C6 alkyl and / or halogen, pyridazinyl, unsubstituted or substituted with C1-C6 alkyl and / or halogen, pyrimidinyl, unsubstituted or substituted with C1-C6 alkyl and / or halogen, or A 7 The group is shown in X15, and n is an integer from 0 to 6.

[0080]

[0081] And in X15, A 15a and A 15b Each independently is C1-C 12 Alkyl, C2-C6 alkenyl, C2-C6 ynyl, C1-C 12 Alkoxy groups, C1-C groups substituted with halogens 12 Alkyl, phenyl, phenyl substituted with C1-C6 alkyl and / or halogen, phenyl substituted with C1-C6 alkoxy, pyridyl, furanyl, thiophene, thiophene substituted with C1-C6 alkyl and / or halogen, pyrazolyl, pyrazolyl substituted with C1-C6 alkyl, imidazolyl, imidazolyl substituted with C1-C6 alkyl, unsubstituted or substituted with C1-C6 alkyl and / or halogen, unsubstituted or substituted with C1-C6 alkyl and / or halogen The following are substituted pyranyl groups, unsubstituted or C1-C6 alkyl and / or halogen-substituted piperidinyl groups, unsubstituted or C1-C6 alkyl and / or halogen-substituted piperazine groups, unsubstituted or C1-C6 alkyl and / or halogen-substituted pyridinyl groups, unsubstituted or C1-C6 alkyl and / or halogen-substituted pyrimidinyl groups, unsubstituted or C1-C6 alkyl and / or halogen-substituted thiazolyl groups, benzyl groups, and benzyl groups substituted with C1-C6 alkyl and / or halogen.

[0082] Preferably, in X7, A 7 Selected from C1-C 12 Alkyl, C1-C 12 Alkoxy groups, C1-C groups substituted with halogens 12Alkyl, phenyl, phenyl substituted with C1-C6 alkyl and / or halogen, phenyl substituted with C1-C6 alkoxy, pyridyl, furanyl, thiophene, thiophene substituted with C1-C6 alkyl and / or halogen, pyrazolyl, pyrazolyl substituted with C1-C6 alkyl, imidazolyl, imidazolyl substituted with C1-C6 alkyl, or A 7 The group is shown in X15, and n is an integer from 0 to 3.

[0083]

[0084] And in X15, A 15a and A 15b Each of the following is independently C1-C8 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, halogen-substituted C1-C8 alkyl, phenyl, benzyl, phenyl substituted with C1-C6 alkyl and / or halogen, or benzyl substituted with C1-C6 alkyl and / or halogen.

[0085] Preferably, in X7, A 7 Selected from C1-C8 alkyl, C1-C8 alkoxy, halogen-substituted C1-C8 alkyl, phenyl, phenyl substituted with C1-C6 alkyl and / or halogen, phenyl substituted with C1-C6 alkoxy, pyridyl, furanyl, thiophene, thiophene substituted with C1-C6 alkyl and / or halogen, pyrazolyl, pyrazolyl substituted with C1-C6 alkyl, imidazolyl, imidazolyl substituted with C1-C6 alkyl, or A 7 The group is shown in X15, and n is an integer from 0 to 2.

[0086]

[0087] And in X15, A 15a and A 15b Each of the following is independently C1-C8 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, halogen-substituted C1-C8 alkyl, phenyl, benzyl, phenyl substituted with C1-C6 alkyl and / or halogen, or benzyl substituted with C1-C6 alkyl and / or halogen.

[0088] According to the eighth preferred embodiment, in formula (I), X is a group represented by X8 below.

[0089]

[0090] In X8, A 8 Selected from C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, phenyl, phenyl substituted with C1-C6 alkyl and / or halogen, pyridyl, furanyl, thiophene, naphthyl, pyranyl, piperidinyl, piperazine, pyridazinyl, pyrimidinyl, thiazolyl, and C1-C6 substituted with halogen.12 Alkyl, C1-C 12 Alkoxy, pyrazolyl substituted with C1-C6 alkyl, imidazolyl, furanyl, thiophene, pyrroleyl, imidazolyl substituted with C1-C6 alkyl, naphthyl substituted with alkylamino, or A 8 The group is shown in X16;

[0091]

[0092] And in X16, A 16a and A 16b Each independently is C1-C 12 Alkyl, C2-C6 alkenyl, C2-C6 ynyl, C1-C 12 Alkoxy groups, C1-C groups substituted with halogens 12 Alkyl, phenyl, phenyl substituted with C1-C6 alkyl and / or halogen, phenyl substituted with C1-C6 alkoxy, pyridyl, furanyl, thiophene, thiophene substituted with C1-C6 alkyl and / or halogen, pyrazolyl, pyrazolyl substituted with C1-C6 alkyl, imidazolyl, imidazolyl substituted with C1-C6 alkyl, unsubstituted or substituted with C1-C6 alkyl and / or halogen, unsubstituted or substituted with C1-C6 alkyl and / or halogen The following are substituted pyranyl groups, unsubstituted or C1-C6 alkyl and / or halogen-substituted piperidinyl groups, unsubstituted or C1-C6 alkyl and / or halogen-substituted piperazine groups, unsubstituted or C1-C6 alkyl and / or halogen-substituted pyridinyl groups, unsubstituted or C1-C6 alkyl and / or halogen-substituted pyrimidinyl groups, unsubstituted or C1-C6 alkyl and / or halogen-substituted thiazolyl groups, benzyl groups, and benzyl groups substituted with C1-C6 alkyl and / or halogen.

[0093] Preferably, in X8, A 8 Selected from phenyl, phenyl substituted with C1-C6 alkyl and / or halogen, pyridyl, furanyl, thiophene, and C1-C6 substituted with halogen. 12 Alkyl, C1-C 12 Alkoxy, pyrazolyl substituted with C1-C6 alkyl, imidazolyl, imidazolyl substituted with C1-C6 alkyl, naphthyl substituted with alkylamino, or A 8 The group is shown in X16;

[0094]

[0095] And in X16, A 16a and A 16b Each independently is C1-C 12 Alkyl, C2-C6 alkenyl, C2-C6 ynyl, C1-C 12 Alkoxy groups, C1-C groups substituted with halogens 12Alkyl, phenyl, phenyl substituted with C1-C6 alkyl and / or halogen, phenyl substituted with C1-C6 alkoxy, pyridyl, furanyl, thiophene, thiophene substituted with C1-C6 alkyl and / or halogen, pyrazolyl, pyrazolyl substituted with C1-C6 alkyl, imidazolyl, imidazolyl substituted with C1-C6 alkyl, unsubstituted or substituted with C1-C6 alkyl and / or halogen, unsubstituted or substituted with C1-C6 alkyl and / or halogen The following are substituted pyranyl groups, unsubstituted or C1-C6 alkyl and / or halogen-substituted piperidinyl groups, unsubstituted or C1-C6 alkyl and / or halogen-substituted piperazine groups, unsubstituted or C1-C6 alkyl and / or halogen-substituted pyridinyl groups, unsubstituted or C1-C6 alkyl and / or halogen-substituted pyrimidinyl groups, unsubstituted or C1-C6 alkyl and / or halogen-substituted thiazolyl groups, benzyl groups, and benzyl groups substituted with C1-C6 alkyl and / or halogen.

[0096] Preferably, in X8, A 8 Selected from phenyl, phenyl substituted with C1-C6 alkyl and / or halogen, pyridyl, furanyl, thiophene, pyrazolyl substituted with C1-C6 alkyl, imidazolyl substituted with C1-C6 alkyl, C1-C8 alkyl substituted with halogen, C1-C8 alkoxy, naphthyl substituted with dimethylamino, naphthyl substituted with diethylamino, or A 8 The group shown in X16,

[0097]

[0098] And in X16, A 16a and A 16b Each independently is C1-C 12 Alkyl, C2-C6 alkenyl, C2-C6 ynyl, C1-C 12 Alkoxy groups, C1-C groups substituted with halogens 12 Alkyl, phenyl, phenyl substituted with C1-C6 alkyl and / or halogen, phenyl substituted with C1-C6 alkoxy, pyridyl, furanyl, thiophene, thiophene substituted with C1-C6 alkyl and / or halogen, pyrazolyl, pyrazolyl substituted with C1-C6 alkyl, imidazolyl, imidazolyl substituted with C1-C6 alkyl, unsubstituted or substituted with C1-C6 alkyl and / or halogen, unsubstituted or substituted with C1-C6 alkyl and / or halogen The following are substituted pyranyl groups, unsubstituted or C1-C6 alkyl and / or halogen-substituted piperidinyl groups, unsubstituted or C1-C6 alkyl and / or halogen-substituted piperazine groups, unsubstituted or C1-C6 alkyl and / or halogen-substituted pyridinyl groups, unsubstituted or C1-C6 alkyl and / or halogen-substituted pyrimidinyl groups, unsubstituted or C1-C6 alkyl and / or halogen-substituted thiazolyl groups, benzyl groups, and benzyl groups substituted with C1-C6 alkyl and / or halogen.

[0099] According to the ninth preferred embodiment, in formula (I), X is a group represented by X9 below.

[0100]

[0101] In X9, A 9a and A 9b Each is independently selected from C1-C 12 Alkoxy, C1-C6 alkyl and / or halogen-substituted phenyl, benzyl, or A 9a A 9b Each is an independent group represented by X17;

[0102]

[0103] And in X17, A 17a and A 17b Each independently is C1-C 12 Alkyl, C2-C6 alkenyl, C2-C6 ynyl, C1-C 12 Alkoxy groups, C1-C groups substituted with halogens 12 Alkyl, phenyl, phenyl substituted with C1-C6 alkyl and / or halogen, phenyl substituted with C1-C6 alkoxy, pyridyl, furanyl, thiophene, thiophene substituted with C1-C6 alkyl and / or halogen, pyrazolyl, pyrazolyl substituted with C1-C6 alkyl, imidazolyl, imidazolyl substituted with C1-C6 alkyl, unsubstituted or substituted with C1-C6 alkyl and / or halogen, unsubstituted or substituted with C1-C6 alkyl and / or halogen The following are substituted pyranyl groups, unsubstituted or C1-C6 alkyl and / or halogen-substituted piperidinyl groups, unsubstituted or C1-C6 alkyl and / or halogen-substituted piperazine groups, unsubstituted or C1-C6 alkyl and / or halogen-substituted pyridinyl groups, unsubstituted or C1-C6 alkyl and / or halogen-substituted pyrimidinyl groups, unsubstituted or C1-C6 alkyl and / or halogen-substituted thiazolyl groups, benzyl groups, and benzyl groups substituted with C1-C6 alkyl and / or halogen.

[0104] Preferably, in X9, A 9a and A 9b Each is independently selected from C1-C 12 alkoxy, or A 9a A 9b The group shown in X17,

[0105]

[0106] And in X17, A 17a and A 17b Each independently is C1-C 12 Alkyl, C1-C 12Alkoxy groups, C1-C groups substituted with halogens 12 Alkyl, phenyl, phenyl substituted with C1-C6 alkyl and / or halogen, phenyl substituted with C1-C6 alkoxy, pyridyl, furanyl, thiophene, thiophene substituted with C1-C6 alkyl and / or halogen, pyrazolyl, pyrazolyl substituted with C1-C6 alkyl, imidazolyl, imidazolyl substituted with C1-C6 alkyl, unsubstituted or substituted with C1-C6 alkyl and / or halogen, unsubstituted or substituted with C1-C6 alkyl and / or halogen The following are substituted pyranyl groups, unsubstituted or C1-C6 alkyl and / or halogen-substituted piperidinyl groups, unsubstituted or C1-C6 alkyl and / or halogen-substituted piperazine groups, unsubstituted or C1-C6 alkyl and / or halogen-substituted pyridinyl groups, unsubstituted or C1-C6 alkyl and / or halogen-substituted pyrimidinyl groups, unsubstituted or C1-C6 alkyl and / or halogen-substituted thiazolyl groups, benzyl groups, and benzyl groups substituted with C1-C6 alkyl and / or halogen.

[0107] Preferably, in X9, A 9a and A 9b Each is independently selected from C1-C8 alkoxy groups, or A 9a A 9b The group shown in X17,

[0108]

[0109] And in X17, A 17a and A 17b Each independently is C1-C 12 Alkyl, C1-C 12 Alkoxy groups, C1-C groups substituted with halogens 12 Alkyl, phenyl, phenyl substituted with C1-C6 alkyl and / or halogen, phenyl substituted with C1-C6 alkoxy, pyridyl, furanyl, thiophene, thiophene substituted with C1-C6 alkyl and / or halogen, pyrazolyl, pyrazolyl substituted with C1-C6 alkyl, imidazolyl, imidazolyl substituted with C1-C6 alkyl, unsubstituted or substituted with C1-C6 alkyl and / or halogen, unsubstituted or substituted with C1-C6 alkyl and / or halogen The following are substituted pyranyl groups, unsubstituted or C1-C6 alkyl and / or halogen-substituted piperidinyl groups, unsubstituted or C1-C6 alkyl and / or halogen-substituted piperazine groups, unsubstituted or C1-C6 alkyl and / or halogen-substituted pyridinyl groups, unsubstituted or C1-C6 alkyl and / or halogen-substituted pyrimidinyl groups, unsubstituted or C1-C6 alkyl and / or halogen-substituted thiazolyl groups, benzyl groups, and benzyl groups substituted with C1-C6 alkyl and / or halogen.

[0110] According to the tenth preferred embodiment, in formula (I), X is a group represented by X10 below.

[0111]

[0112] In X10, A 10a and A 10b Each independently is C1-C 12 Alkyl, C2-C6 alkenyl, C2-C6 ynyl, C1-C 12 Alkoxy, phenyl, benzyl, C1-C6 substituted with alkyl and / or halogen 12 Alkyl groups, phenyl groups substituted with C1-C6 alkyl groups and / or halogens, and benzyl groups substituted with C1-C6 alkyl groups and / or halogens.

[0113] Preferably, in X10, A 10a and A 10b Each independently is C1-C 12 Alkyl groups, halogen-substituted C1-C 12 alkyl.

[0114] Preferably, in X10, A 10a and A 10b Each is independently a C1-C6 alkyl group.

[0115] According to the eleventh preferred embodiment, in formula (I), X is a group represented by X11 below.

[0116]

[0117] In X11, A 11a and A 11b Each independently constitutes H, C1-C 12 Alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C substituted with halogen 12 Alkyl, phenyl, benzyl, phenyl substituted with C1-C6 alkyl and / or halogen, benzyl substituted with C1-C6 alkyl and / or halogen, and n is an integer from 0 to 6.

[0118] Preferably, in X11, A 11a and A 11b Each independently constitutes H, C1-C 12 Alkyl groups, halogen-substituted C1-C 12 Alkyl, phenyl, phenyl substituted with C1-C6 alkyl and / or halogen, and n is an integer from 0 to 2.

[0119] Preferably, in X11, A 11a and A 11b Each is independently H, C1-C6 alkyl, or phenyl, and A 11a and A 11b It is not simultaneously H, and n is 0 or 1.

[0120] According to the twelfth preferred embodiment, in formula (I), X is a group represented by X12 below.

[0121]

[0122] In X12, A 12a and A 12b Each is independently H, phenyl, benzyl, phenyl substituted with C1-C6 alkyl and / or halogen, or benzyl substituted with C1-C6 alkyl and / or halogen.

[0123] Preferably, in X12, A 12a and A 12b Each is independently H, phenyl, or phenyl substituted with C1-C6 alkyl and / or halogen.

[0124] Preferably, in X12, A 12a and A 12b Each is independently H, phenyl, or phenyl substituted with a C1-C4 alkyl group, and A 12a and A 12b They are not both H.

[0125] According to the thirteenth preferred embodiment, in formula (I), X is a group represented by X13 below.

[0126]

[0127] In X13, A 13a and A 13b Each is independently selected from H, C1-C 12 Alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C substituted with halogen 12 Alkyl, phenyl, benzyl, phenyl substituted with C1-C6 alkyl and / or halogen, benzyl substituted with C1-C6 alkyl and / or halogen, and n is an integer from 0 to 6.

[0128] Preferably, in X13, A 13a and A 13b Each is independently selected from H, C1-C 12 Alkyl groups, halogen-substituted C1-C 12 Alkyl, phenyl, phenyl substituted with C1-C6 alkyl and / or halogen, and n is an integer from 0 to 3.

[0129] Preferably, in X13, A 13a and A 13b Each is independently selected from H, C1-C8 alkyl, phenyl, phenyl substituted by C1-C6 alkyl and / or halogen, and A 13a and A 13bIt is not simultaneously H, and n is an integer from 0 to 2.

[0130] According to the fourteenth preferred embodiment, in formula (I), X is a group represented by X14 below.

[0131]

[0132] In X14, A 14a and A 14b Each independently is C1-C 12 Alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C substituted with halogen 12 Alkyl, phenyl, benzyl, phenyl substituted with C1-C6 alkyl and / or halogen, benzyl substituted with C1-C6 alkyl and / or halogen, and n is an integer from 0 to 6.

[0133] Preferably, in X14, A 14a and A 14b Each independently is C1-C 12 Alkyl group, and n is an integer from 0 to 2.

[0134] Preferably, in X14, A 14a and A 14b Each is independently a C1-C8 alkyl group, and n is 0 or 1.

[0135] According to the fifteenth preferred embodiment, the pyrazole derivative shown in formula (I) is selected from at least one of the compounds shown in compound 1 to compound 1512.

[0136] The present invention does not particularly limit the method for synthesizing the pyrazole derivatives shown in formula (I). Those skilled in the art can obtain suitable methods for preparing the pyrazole derivatives shown in formula (I) by combining the compound structure provided by the present invention with the synthesis methods in the field of chemistry. The present invention will not elaborate on these methods here.

[0137] The second aspect of the present invention provides the application of the pyrazole derivatives described in the first aspect in the control of weeds.

[0138] The weeds include at least one of the following: foxtail grass, barnyard grass, barnyard grass, crabgrass, jointed barley, wild oat, wild oat, Japanese wild oat, ryegrass, rice grass, cassia, morning glory, cocklebur, sedge, vetch, amaranth, false groundcherry, angelica, purslane, spiny amaranth, beggar-ticks, double-spike barnyard grass, rice grass, water bamboo leaf, wild arrowhead, water plantain, raindrop, dayflower, duck tongue grass, fireweed, and sedge.

[0139] A third aspect of the present invention provides the use of the pyrazole derivatives described in the first aspect above in the control of broadleaf weeds and / or grass weeds.

[0140] In this invention, the broadleaf weeds include at least one of the following: amaranth, lamb's quarters, velvetleaf, rice-leaf grass, cassia seed, morning glory, cocklebur, reverse-branch amaranth, false groundcherry, angelica sinensis, purslane, spiny amaranth, water bamboo leaf, wild arrowhead, water plantain, rain-flower, dayflower, duck tongue grass, etc., and sedges: firefly iris, sedge, etc.

[0141] Preferably, in this invention, the grassy weeds include at least one of the following: foxtail grass, barnyard grass, barnyard grass, crabgrass, jointed goatgrass, wild oat, wild oat, Japanese wild oat, ryegrass, sedge, vetch, beggar-ticks, double-spike barnyard grass, and rice grass.

[0142] The fourth aspect of the present invention provides the application of the pyrazole derivatives described in the first aspect as pesticide herbicides.

[0143] A fifth aspect of the present invention provides a pesticide herbicide composed of an active ingredient and excipients, wherein the active ingredient includes at least one of the pyrazole derivatives described in the first aspect above.

[0144] The pyrazole derivatives provided by this invention have shown excellent crop safety for corn, wheat, peanuts and cotton.

[0145] The pyrazole derivatives provided by this invention have high herbicidal activity against broadleaf weeds, grass weeds and sedge weeds. Detailed Implementation

[0146] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0147] According to a preferred embodiment, the pyrazole derivatives of the present invention are synthesized using the following route:

[0148]

[0149] In the above synthetic routes, the substituents in Formula I-1, Formula I-2, Formula I-3, and Formula I-4 are defined in the same way as the corresponding groups in Formula (I) of the present invention.

[0150] In the above synthetic route, in step A, the synthesis method of formula I-2 can be, for example, as follows: Dissolve intermediate I-1 in a solvent, add oxalyl chloride, and stir the reaction at low temperature. After the reaction is complete, remove the solvent, and dissolve the remaining solid in a solvent for later use. At low temperature, dissolve pyrazolone in a solvent, add triethylamine, stir, and then add the acyl chloride solution dissolved in the solvent dropwise to the reaction system. Monitor the reaction by TLC. After the reaction is complete, add saturated NaHCO3 solution to the reaction system, extract and combine the organic layers, dry and concentrate, and perform column chromatography to obtain intermediate I-2.

[0151] In the above synthetic route, in step B, the synthesis method of formula I-3 can be, for example, as follows: intermediate I-2 and acetonitrile are added to a flask, stirred, and Et3N and acetone cyanohydrin are added. The reaction is monitored by TLC. After the reaction is complete, HCl solution is added to the reaction system, stirring is continued, and the precipitated solid is filtered.

[0152] In the above synthetic route, in step C, the synthesis method of formula I-4 can be, for example, as follows: intermediate I-3 and solvent are added to a flask, stirred, and POCl3 is slowly added, and the mixture is heated to reflux. The reaction is monitored by TLC. After the reaction is complete, the solvent is removed by vacuum distillation, diethyl ether is added to the remaining solid, stirring is continued, and the precipitated solid is filtered.

[0153] The present invention will be described in detail below through examples. In the following examples, unless otherwise specified, all raw materials used are commercially available.

[0154] Preparation Example 1: Synthesis of Compounds 1-3a

[0155]

[0156] Intermediate I-1a (5 mmol) was added to a 50 mL single-necked flask, followed by 18 mL of dry THF. SOCl2 (8 mmol) was slowly added dropwise at room temperature. After the addition was complete, the mixture was refluxed at 75 °C for approximately 1.5 h, and the reaction was monitored by TLC. After the reaction was complete, the solvent was removed. 20 mL of dry CHCl3, 1,3-dimethyl-5-pyrazolone (6 mmol), and Et3N (10 mmol) were added, and the reaction was continued for approximately 0.5 h, monitored by TLC until the acyl chloride disappeared. After the reaction was complete, the mixture was washed once with 20 mL of water, twice with 10 mL of 1 mol / L HCl, and twice with 10 mL of saturated NaHCO3. The mixture was dried over anhydrous Na2SO4 and purified by column chromatography to obtain intermediate I-2b.

[0157] Intermediate I-2b (1 mmol) was added to a 50 mL two-necked flask, followed by 28 mL of anhydrous acetonitrile. Under N2 protection, Et3N (2 mmol) and acetone cyanohydrin (0.1 mmol) were added. The reaction was carried out at room temperature for 8 h, monitored by TLC until the reactants disappeared. After the reaction was complete, the acetonitrile was removed, and the mixture was washed with approximately 30 mL of CHCl3 and 30 mL of 1 mol / L hydrochloric acid. The mixture was separated, and the organic phase was washed three times with saturated sodium chloride solution. The organic layer was dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure to obtain a pale yellow oil. The oil was recrystallized from 10 mL of methanol to give compounds 1-3a.

[0158] Preparation Example 2: Synthesis of Compound 8

[0159] At 0 °C, compound I-3a (1.5 mmol) was dissolved in anhydrous dichloromethane, and triethylamine (3 mmol) was added. After stirring to dissolve, cyclopropylformyl chloride (2 mmol) was added to the reaction system, and stirring was continued for 3–6 h. After the reaction was complete, saturated sodium bicarbonate solution (15 ml) was slowly added to the reaction system, and the reaction solution was extracted with dichloromethane. The organic phase was washed twice with saturated brine. The organic phase was dried over anhydrous sodium sulfate, and the solvent was removed by vacuum distillation to obtain the crude product, which was then purified by column chromatography.

[0160] Preparation Example 3: Synthesis of Compound 46

[0161] At 0°C, intermediate I-3a (1 mmol) was dissolved in ultra-dry DCM, and Et3N (1.5 mmol) was added. The mixture was stirred for 15 min, and 2-thiophene sulfonyl chloride (1.5 mmol) solution was slowly added dropwise to the reaction system. The mixture was stirred at 0°C for another 30 min, and then the reaction was allowed to proceed at room temperature for 3 h. After the reaction was complete, saturated sodium bicarbonate solution (15 ml) was added to the reaction system, and the organic phase was collected by separation. The organic phase was washed twice with saturated brine. The organic phase was dried over anhydrous sodium sulfate, and the solvent was removed by vacuum distillation to obtain the crude product, which was then purified by column chromatography.

[0162] Preparation Example 4: Synthesis of Compound 100

[0163]

[0164] At 0°C, intermediate I-3b (1 mmol) was dissolved in ultra-dry DCM, and triethylamine (1.5 mmol) was added. The mixture was stirred for 15 min, and N,N-diallylformyl chloride (1.5 mmol) was slowly added dropwise to the reaction system. The mixture was stirred at 0°C for another 30 min, and then allowed to return to room temperature for 3 h. After the reaction was complete, saturated sodium bicarbonate solution (15 ml) was added to the reaction system, and the organic phase was collected by separation. The organic phase was washed twice with saturated brine. The organic phase was dried over sodium sulfate, and the solvent was removed by vacuum distillation to obtain the crude product, which was then purified by column chromatography.

[0165] The derivative containing the quinazolinidone fragment of the present invention was synthesized according to the above method.

[0166] Table 1 below lists the structural characterization data of some of the compounds of this invention.

[0167] Table 1

[0168]

[0169]

[0170]

[0171]

[0172]

[0173]

[0174]

[0175]

[0176]

[0177]

[0178]

[0179]

[0180]

[0181]

[0182]

[0183]

[0184]

[0185]

[0186]

[0187]

[0188]

[0189]

[0190]

[0191]

[0192]

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203]

[0204]

[0205]

[0206]

[0207] Test Example 1: Herbicidal Activity Test Experiment (Artificial Climate Chamber)

[0208] Preliminary screening test (pot method): Take a 6cm inner diameter flowerpot, fill it with composite soil (garden soil: seedling substrate, 1:2, v / v) to 3 / 4 full, directly sow the weed targets shown in Table 2 (germination rate ≥85%), cover with 0.2cm of soil, and wait until the weeds grow to about the 3-leaf stage before use. After applying each compound according to the dosage shown in Table 2 in an automatic spray tower, after the pesticide solution on the crop leaves has dried, transfer it to a greenhouse for cultivation (25℃-28℃, humidity 70%), and investigate the results after 30 days. The results are listed in Table 2.

[0209] Investigation method: After 30 days of experimental treatment, the symptoms of damage and growth inhibition of the target were visually observed, and the fresh weight of the aboveground parts was measured. The fresh weight inhibition rate (%) was calculated and the control effect (%) was expressed by the fresh weight inhibition rate.

[0210] Fresh weight inhibition rate (%) = (Control fresh weight - Treatment fresh weight) / Control fresh weight × 100

[0211] Herbicidal activity evaluation (symptoms include resistance, slight inhibition, slight bleaching, slight deformity, severe deformity, complete bleaching, and complete mortality):

[0212] Grade G - Same as control, resistant, with a control efficacy of less than 10%;

[0213] Grade F - Growth is slightly affected, mildly inhibited, with poor activity and a control efficacy of 10% to less than 20%;

[0214] Grade E - Growth is affected, slight whitening, poor activity, and control efficacy is 20% to less than 50%;

[0215] Grade D - Growth is affected, slight deformities occur, activity is moderate, and the efficacy is 50% to less than 70%.

[0216] Grade C - Relatively sensitive, severely deformed, with good activity and a protective efficacy of 70% to less than 90%;

[0217] Grade B - Extremely sensitive, completely whitened, with good activity, suitable for screening, with a control efficacy of 90% to less than 100%;

[0218] Grade A - Completely dead, highly active, 100% effective.

[0219] Table 2

[0220]

[0221]

[0222]

[0223]

[0224]

[0225]

[0226]

[0227]

[0228]

[0229]

[0230]

[0231]

[0232]

[0233]

[0234]

[0235] The results showed that the herbicidal activity inhibition rates (%) of the derivatives containing the quinazolinidone fragment of the present invention were all high (most of the compounds of the present invention had a control effect of more than 50% on the target weeds tested, and most of the compounds tested had a better control effect on broadleaf weeds than on grass weeds), and had excellent control effects on the tested weeds.

[0236] Meanwhile, the tested compounds also showed excellent herbicidal activity against weeds in wheat fields.

[0237] Test Example 2: Herbicidal Activity Spectrum Test

[0238] Herbicidal activity spectrum test (post-emergence foliar spray treatment): Common weeds were selected as test targets. 7.5cm inner diameter flowerpots were filled with composite soil (garden soil: seedling substrate, 1:2, v / v) to 3 / 4 full. Seeds of the target weeds listed in Table 3 (germination rate ≥85%) were directly sown, covered with soil, and watered to keep the soil moist. The plants were left to mature to the 3-4 leaf stage. Each compound was applied at the dosage shown in the table using an automatic spray tower. Afterward, the plants were transferred to a greenhouse for cultivation. The results were visually assessed after 30 days and are listed in Table 3.

[0239] The investigation methods and herbicidal activity evaluation methods were the same as those in Test Example 1.

[0240] Table 3: Results of initial screening herbicidal activity tests for some compounds

[0241]

[0242]

[0243]

[0244]

[0245]

[0246]

[0247] "--" indicates that the test was not conducted.

[0248] The results show that the derivatives of the present invention containing the quinazolinidone fragment have the advantage of a broad spectrum of herbicidal activity, comparable to the commercial herbicide mesotrione. Therefore, the compounds of the present invention have very good application prospects.

[0249] Test Example 3: Crop Safety Determination

[0250] Crop safety testing (post-emergence foliar spray treatment): The target crops for testing are shown in Table 4. Take 9.0 cm inner diameter flowerpots, fill them with composite soil (garden soil: seedling substrate, 1:2, v / v) to 3 / 4 full, directly sow the target crop seeds (germination rate ≥85%) as shown in Table 4, cover with soil, and add water to keep the soil moist. Once the target crops have grown to the 3-5 leaf stage, they are ready for use. Each compound is applied according to the dosage shown in Table 4 using an automatic spray tower (model: 3WPSH-700E), and then transferred to a greenhouse for cultivation. Results are investigated after 30 days.

[0251] The investigation methods and herbicidal activity evaluation methods are the same as those in Test Example 1.

[0252] Table 4: Results of crop safety experiments for some compounds in the initial screening

[0253]

[0254]

[0255]

[0256]

[0257]

[0258]

[0259] "--" indicates that the test was not conducted.

[0260] The results showed that the derivatives containing the quinazolinidone fragment of the present invention have good crop selectivity and good crop safety for corn, wheat, peanut and cotton, respectively, and have important application prospects.

[0261] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A pyrazole derivative containing a quinazolinidone fragment, the pyrazole derivative having the structure shown in formula (I), wherein the pyrazole derivative shown in formula (I) is selected from at least one of the following compounds: Equation (I) Compound 35: R1 is -CH3; R2 is -CH3; R3 is -CH3; R4 is -CH3; Z is O; Y is 2-CH3-Ph; X is... ; Compound 39: R1 is -CH3; R2 is -CH3; R3 is -CH3; R4 is -CH3; Z is O; Y is 2-CH3-Ph; X is... ; Compound 46: R1 is -CH3; R2 is -CH3; R3 is -CH3; R4 is -CH3; Z is O; Y is 2-CH3-Ph; X is... .

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