A quinazolinedione-containing compound, and a preparation method and application thereof

Abstract

The application relates to the technical field of new pesticide compounds, and discloses a quinazolin-2,4-dione-containing compound, a preparation method and application thereof, and the compound has a structure shown in formula (I). The quinazolin-2,4-dione-containing compound provided by the application has excellent herbicidal activity, and has excellent herbicidal activity on weeds in major crops such as rice and wheat and some important economic crops, especially on resistant weeds, and has good safety on non-target crops.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of new pesticide compounds, in particular to a quinazolinone-containing compound and a preparation method and application thereof. BACKGROUND

[0002] The high dose and long-term single use of traditional herbicides have led to an explosive trend of weed resistance, which seriously hinders the sustainable development of modern agriculture, and the creation of super-efficient herbicides with new action mechanisms and low resistance risk is the fundamental way to solve the problem of weed resistance.

[0003] Hydroxyphenylpyruvate dioxygenase (HPPD) is widely present in various aerobic organisms and is a divalent iron-dependent dioxygenase. HPPD can convert its substrate, hydroxyphenylpyruvic acid (HPPA), into hydroquinone acid (HGA).

[0004] In higher plants, hydroquinone acid is further converted into plastoquinone and tocopherol. Plastoquinone and tocopherol are essential substances for electron chain transmission in plant photosynthesis. If the HPPD in the plant body is inhibited, the synthesis of plastoquinone will be blocked, thereby affecting photosynthesis, and ultimately leading to the appearance of albino symptoms in plants and death.

[0005] Currently, commercial HPPD inhibitor herbicides have the advantages of high efficiency, broad spectrum, low toxicity, and environmental friendliness, and have low resistance risk. There is no cross-resistance with other types of herbicides, and they can specifically inhibit some resistant weeds. These advantages make HPPD inhibitor herbicides a hot spot in pesticide chemical research in recent years.

[0006] Therefore, HPPD inhibitor herbicides are a class of herbicides with great research value and development prospects.

[0007] In 2015, Professor Yang Guangfu's team first disclosed HPPD inhibitor molecules containing quinazolinone fragments in WO2015058519A1. The structures of representative substances in the two substances are as follows, which are mainly used for controlling weeds in sorghum fields and corn fields:

[0008]

[0009] Subsequently, WO2017140612A, CN110357859A, CN110357862A, CN110963973A and WO2019196908A1 and other prior art disclose a series of high-herbicidal-activity triketone or pyrazole HPPD inhibitor molecules containing quinazolinone structures on this basis.

[0010] However, the above-mentioned compounds are all quinazolin-6-carbonyl derivatives, and the structural characteristics thereof result in the inability to introduce more types of substituents at the 5th position of the quinazolin-6-carbonyl group, such as the connection of substituents such as a chlorine atom and a nitro group at the 5th position during synthesis. Thus, the structural optimization space and substrate diversity of the quinazolin-6-carbonyl derivatives are limited, which may in turn restrict the herbicidal activity and crop safety thereof.

[0011] In addition, the safety of such substances to major crops such as rice and wheat needs to be further improved, and the substances cannot be used in rice and wheat fields at present. However, at the present stage, the serious growth of weeds such as barnyard grass, dogtail grass and leafflower in rice fields and the serious growth of weeds such as dogtail grass, oat and wild oat in wheat fields seriously affect the normal growth of rice and wheat.

[0012] Therefore, it is of important practical significance and great market value to develop new HPPD inhibitors with good control effect on weeds in rice and wheat fields and high safety. SUMMARY

[0013] The present application aims to overcome the aforementioned defects in the prior art and provide a new type of HPPD inhibitor with good control effect on weeds in rice and wheat fields and high safety.

[0014] The inventors of the present application accidentally found that, when the cyclohexanedione fragment or the pyrazole fragment provided in the 6th position of the quinazolin-6-carbonyl group in the HPPD inhibitor molecules of the prior art is moved to the 7th position and a characteristic substituent is introduced or not introduced at the 6th position, the new compounds thus obtained have excellent inhibitory activity on weeds. More importantly, compared with the prior art, the safety of the new compounds of the present application to crops is obviously improved. That is, the present application can provide a new type of HPPD inhibitor herbicide with both crop safety and high inhibitory activity on weeds. In view of this, the inventors provide the solution of the present application.

[0015] In order to achieve the above-mentioned purpose, the first aspect of the present application provides a quinazolin-6-carbonyl-containing compound or an agrochemically acceptable salt, hydrate, solvate, or enantiomeric, optically active derivative thereof, the compound having the structure shown in formula (I):

[0016]

[0017] In formula (I), X is selected from H, C1-C6 alkyl, C1-C6 alkyl substituted by halogen, C1-C6 alkoxy, halogen, nitro, cyano, -S(O)

[0018] X is selected from H, C1-C6 alkyl, C1-C6 alkyl substituted by halogen, C1-C6 alkoxy, halogen, nitro, cyano, -S(O) m CH3; m is 0, 1 or 2;

[0019] R 1 It is a C1-C6 alkyl group, -C6H5 or -CH2C6H5;

[0020] R 2 Selected from C1-C 12 Alkyl groups, C1-C substituted with halogens 12 Alkyl groups, C2-C groups substituted with C1-C6 alkoxy groups 12 Alkyl, -C1-C6 alkylene, -O-C1-C6 alkyl, C3-C 10 cycloalkyl groups, halogen-substituted C3-C 10 cycloalkyl groups, C3-C containing at least one double bond 12 Hydrocarbon group, C3-C containing at least one triple bond 12 The hydrocarbon group, a C3-C group containing at least one triple bond substituted with a trimethylsilyl group. 12 hydrocarbon group, -C1-C6 alkylene group, -C3-C 10 Cycloalkyl, -C1-C6 alkylene-C3-C7 heterocyclic groups containing at least one O atom as a cyclic atom, C3-C7 saturated heterocyclic groups containing at least one O atom as a cyclic atom, substituted methylpyrazolyl, substituted or unsubstituted pyridinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted pyrazinyl, C1-C 12 alkoxy, substituted or unsubstituted phenyl, substituted or unsubstituted phenyl-CH2-; R 2 The substituents present therein are each independently selected from at least one of the following: C1-C6 alkyl, C3-C6 cycloalkyl, halogen-substituted C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkathio, halogen-substituted C1-C6 alkoxy, nitro, cyano, halogen, -SO2-CH3, and C2-C6 alkynyl;

[0021] R 3 and R 4 Each is independently selected from H, C1-C6 alkyl, C1-C6 alkoxy, halogen, and nitro groups;

[0022] Q is a group represented by formula (Q1) or formula (Q2), and R 11 R 12 R 13 R 14 Each is independently selected from H, C1-C6 alkyl groups; R 21 R 22 R 23 Each is independently selected from H, C1-C6 alkyl groups, and C3-C6 cycloalkyl groups.

[0023] The second aspect of the present application provides a method for preparing the quinazolin- dione-containing compound described in the first aspect, comprising:

[0024] The compound shown in formula (II) is subjected to rearrangement reaction in the presence of a basic substance, a catalyst and a solvent;

[0025]

[0026] In formula (II), W is a group shown in formula (W1) or formula (W2), and R

[0027] W is a group shown in formula (W1) or formula (W2), and R 1 , R 2 , R 3 , R 4 , X, formula (W1) and formula (W2) are the same as the definitions in the first aspect of the present application.

[0028] The third aspect of the present application provides the use of the quinazolin-dione-containing compound described in the first aspect or an agrochemically acceptable salt, hydrate, solvate, or an enantiomeric, optically active derivative thereof in inhibiting the activity of HPPD.

[0029] The present application provides a novel quinazolin-dione-7-carbonyl derivative, and a novel compound obtained by connecting a hydrogen atom, a chlorine atom, a methyl group and a nitro group as substituents at the 6th position, which has excellent herbicidal activity on weeds and good safety on major crops such as rice and wheat and some economic crops.

[0030] Specifically, the quinazolin-dione-containing compound provided by the present application has excellent herbicidal activity on weeds in major crops such as rice and wheat and some important economic crops (such as peanuts, soybeans, cotton, etc.), especially on resistant weeds, and has good safety on non-target crops.

[0031] Further, the quinazolin-dione-containing compound provided by the present application shows very excellent herbicidal effect on six common grass and broadleaf weeds such as barnyard grass, dogtail grass, crabgrass, amaranth, gooseweed and jute, and has obviously better effect than mesotrione.

[0032] Therefore, the novel HPPD inhibitor provided by the present application has important practical significance and great market value. DETAILED DESCRIPTION

[0033] 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.

[0034] The terminology involved in this invention will be explained below.

[0035] In the structural formulas involved in this invention, both wavy lines and dashed lines represent connection points.

[0036] "C1-C6 alkyl" refers to straight-chain or branched alkyl groups with a total of 1, 2, 3, 4, 5, or 6 carbon atoms. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc. "C1-C6" 12 Alkyl group, C2-C 12 "alkyl" has a similar definition, only the total number of carbon atoms is different.

[0037] "H-atom substituted C1-C6 alkyl group" means that at least one H atom in the "C1-C6 alkyl group" is substituted by any one or more halogens. 12 "alkyl" has a similar definition, only the total number of carbon atoms is different.

[0038] "Halogen" refers to fluorine, chlorine, bromine, and iodine.

[0039] "C1-C6 alkoxy groups" refers to straight-chain or branched alkoxy groups with a total number of carbon atoms of 1, 2, 3, 4, 5, or 6. Examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, and tert-butoxy. 12 The definition of "alkoxy group" is similar, except that the total number of carbon atoms is different. The definition of "C1-C6 alkoxy group" is also similar, except that the O atom is replaced by the S atom.

[0040] "C6H5" represents phenyl. Similarly, "C6H4", "C6H3", etc., all represent phenyl, differing only in the number of substituents on the phenyl group.

[0041] "C2-C substituted with alkoxy groups from C1-C6" 12 "alkyl" indicates that in C2-C 12 At least one H atom on the alkyl group is replaced by a C1-C6 alkoxy group.

[0042] An exemplary structure of "-C1-C6 alkylene-O-C1-C6 alkylene" is -CH2-O-CH3, wherein the C1-C6 alkylene can be a straight-chain alkylene or a branched-chain alkylene.

[0043] “C3-C 10 "Cycloalkyl" refers to a saturated cycloalkyl group with 3-10 carbon atoms in the ring. "C3-C6 cycloalkyl" has a similar definition, except that the total number of carbon atoms is different.

[0044] "C3-C replaced by halogen" 10 "Cycloalkyl" indicates that in "C3-C 10 In a cycloalkyl group, at least one H atom is substituted by any halogen. "C1-C6 alkyl group substituted by halogen" has a similar definition, except that the group is changed from "cycloalkyl" to "alkyl". "C1-C6 alkoxy group substituted by halogen" also has a similar definition, except that the group is changed from "cycloalkyl" to "alkoxy".

[0045] “C3-C 12 "Hydrocarbon group" refers to a straight-chain or branched hydrocarbon group containing only carbon and hydrogen atoms, with a total number of carbon atoms of 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12. It includes saturated and unsaturated hydrocarbon groups. Examples include n-propyl, isopropyl, n-butyl, isobutyl, propenyl, propynyl, and hexenyl.

[0046] "C3-C containing at least one double bond" 12 "hydrocarbon group" indicates "C3-C 12 The hydrocarbon group contains at least one carbon-carbon double bond.

[0047] "C3-C containing at least one triple bond" 12 "hydrocarbon group" indicates "C3-C 12 The hydrocarbon group contains at least one carbon-carbon triple bond.

[0048] "C3-C containing at least one triple bond, substituted with a trimethylsilyl group" 12 "hydrocarbon group" means "a C3-C group containing at least one triple bond". 12 At least one H atom in the hydrocarbon group is replaced by a trimethylsilyl group.

[0049] "-C1-C6 alkylene group-C3-C" 10 An exemplary structure of "cycloalkyl group" is -CH2-C4H7, where C4H7 is cyclobutyl, and the "C1-C6 alkylene group" can be a straight-chain alkylene group or a branched alkylene group, and the alkylene group is directly connected to the parent core structure.

[0050] "C3-C7 heterocyclyl containing at least one O atom as a ring-forming atom" means that the group can be a saturated or unsaturated heterocyclyl group, and wherein at least one or more O atoms are ring-forming atoms. "C3-C7 saturated heterocyclyl containing at least one O atom as a ring-forming atom" has a similar definition, except that "heterocyclyl" is defined as a saturated heterocyclyl group.

[0051] An exemplary structure of "-C1-C6 alkylene-C3-C7 heterocyclyl containing at least one O atom as a ring-forming atom" is -CH2-C3H5O, wherein C3H5O is an epoxide butyl group, and wherein the C1-C6 alkylene group is directly attached to the parent structure.

[0052] "Substituted methylpyrazolyl" means that at least one H on a methylpyrazolyl group is replaced with a substituent, and that any position of the substituted methylpyrazolyl group that is capable of bonding to a parent structure is capable of bonding to a parent structure. "Substituted or unsubstituted pyridyl", "substituted or unsubstituted pyridazinyl", "substituted or unsubstituted pyrimidinyl", "substituted or unsubstituted pyrazinyl", and "substituted or unsubstituted phenyl" have similar definitions, and in the absence of a specific indication, any position of the group that is capable of bonding to a parent structure is capable of bonding to a parent structure.

[0053] First Aspect

[0054] As previously described, the first aspect of the present application provides a quinazolinedione-containing compound, or an agrochemically acceptable salt, hydrate, solvate, or an enantiomeric, optically active form thereof, having a structure represented by Formula (I):

[0055]

[0056] wherein, in Formula (I),

[0057] X is selected from the group consisting of H, C1-C6 alkyl, C1-C6 alkyl substituted with halogen, C1-C6 alkoxy, halogen, nitro, cyano, -S(O)0-2- m CH3; m is 0, 1, or 2;

[0058] R 1 is C1-C6 alkyl, -C6H5, or -CH2C6H5;

[0059] R 2 is selected from the group consisting of C1-C 12 alkyl, C1-C 12 alkyl substituted with halogen, C2-C 12 alkyl substituted with C1-C6 alkoxy, -C1-C6 alkylene-O-C1-C6 alkyl, C3-C10 cycloalkyl groups, halogen-substituted C3-C 10 cycloalkyl groups, C3-C containing at least one double bond 12 Hydrocarbon group, C3-C containing at least one triple bond 12 The hydrocarbon group, a C3-C group containing at least one triple bond substituted with a trimethylsilyl group. 12 hydrocarbon group, -C1-C6 alkylene group, -C3-C 10 Cycloalkyl, -C1-C6 alkylene-C3-C7 heterocyclic groups containing at least one O atom as a cyclic atom, C3-C7 saturated heterocyclic groups containing at least one O atom as a cyclic atom, substituted methylpyrazolyl, substituted or unsubstituted pyridinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted pyrazinyl, C1-C 12 alkoxy, substituted or unsubstituted phenyl, substituted or unsubstituted phenyl-CH2-; R 2 The substituents present therein are each independently selected from at least one of the following: C1-C6 alkyl, C3-C6 cycloalkyl, halogen-substituted C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkathio, halogen-substituted C1-C6 alkoxy, nitro, cyano, halogen, -SO2-CH3, and C2-C6 alkynyl;

[0060] R 3 and R 4 Each is independently selected from H, C1-C6 alkyl, C1-C6 alkoxy, halogen, and nitro groups;

[0061] Q is a group represented by formula (Q1) or formula (Q2), and R 11 R 12 R 13 R 14 Each is independently selected from H, C1-C6 alkyl groups; R 21 R 22 R 23 Each is independently selected from H, C1-C6 alkyl groups, and C3-C6 cycloalkyl groups.

[0062] Preferably, X is selected from H, C1-C4 alkyl, halogen-substituted C1-C4 alkyl, C1-C4 alkoxy, halogen, nitro, cyano; more preferably, X is selected from H, C1-C3 alkyl, halogen, nitro; particularly preferred, X is selected from H, methyl, halogen, nitro.

[0063] Preferably, R 1 It is a C1-C4 alkyl group, -C6H5 or -CH2C6H5; more preferably, R 1 It is a C1-C3 alkyl group or -C6H5; more preferably, R1 It is a methyl group.

[0064] Preferably, R 2 Selected from C1-C 10 Alkyl groups, C1-C substituted with halogens 10 Alkyl groups, C2-C groups substituted with C1-C6 alkoxy groups 10 Alkyl groups, -C1-C6 alkylene groups, -O-C1-C6 alkyl groups, C3-C8 cycloalkyl groups, halogen-substituted C3-C8 cycloalkyl groups, and C3-C8 alkyl groups containing at least one double bond. 10 Hydrocarbon group, C3-C containing at least one triple bond 10 The hydrocarbon group, a C3-C group containing at least one triple bond substituted with a trimethylsilyl group. 10 Hydrocarbon group, -C1-C6 alkylene group, -C3-C8 cycloalkyl group, -C1-C6 alkylene group, -C3-C7 heterocyclic group containing at least one O atom as a cyclic atom, -C3-C7 saturated heterocyclic group containing at least one O atom as a cyclic atom, substituted methylpyrazolyl group, substituted or unsubstituted pyridinyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted pyrazinyl group, C1-C 10 alkoxy, substituted or unsubstituted phenyl, substituted or unsubstituted phenyl-CH2-; R 2 The substituents present may be selected independently from at least one of methyl, ethyl, n-propyl, isopropyl, cyclopropyl, trifluoromethyl, trifluoromethoxy, nitro, cyano, methoxy, methylthio, halogen, -SO2-CH3, and C2-C6 alkynyl groups.

[0065] Preferably, R 3 and R 4 Each is independently selected from H, C1-C3 alkyl, C1-C3 alkoxy, halogen, and nitro; more preferably, R 3 and R 4 Each is independently selected from H, C1-C3 alkyl groups; more preferably, R 3 and R 4 All are H.

[0066] Preferably, Q is a group represented by formula (Q1) or formula (Q2), and R 11 R 12 R 13 R 14 Each is independently selected from H, C1-C3 alkyl groups; R 21 R 22 R 23 Each group is independently selected from H, C1-C3 alkyl groups, and C3-C6 cycloalkyl groups. More preferably, Q is a group represented by formula (Q1) or formula (Q2), and R... 11 R12 , R 13 , R 14 each independently selected from H, C1-C3 alkyl; R 21 , R 22 , R 23 each independently selected from H, C1-C3 alkyl, C3-C5 cycloalkyl. Further preferably, Q is a group of formula (Q1) or (Q2) and R 11 , R 12 , R 13 , R 14 are each H; R 21 , R 22 , R 23 each independently selected from H, methyl, ethyl, n-propyl, i-propyl, cyclopropyl.

[0067] According to a preferred embodiment, in formula (I),

[0068] X is selected from H, C1-C4 alkyl, C1-C4 alkyl substituted by halogen, C1-C4 alkoxy, halogen, nitro, cyano;

[0069] R 1 is C1-C4 alkyl, -C6H5 or -CH2C6H5;

[0070] R 2 is selected from C1-C 10 alkyl, C1-C 10 alkyl substituted by halogen, C2-C 10 alkyl substituted by C1-C6 alkoxy, -C1-C6 alkylene-O-C1-C6 alkyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl substituted by halogen, C3-C 10 hydrocarbon group containing at least one double bond, C3-C 10 hydrocarbon group containing at least one triple bond, C3-C 10 hydrocarbon group substituted by trimethylsilyl, -C1-C6 alkylene-C3-C8 cycloalkyl, -C1-C6 alkylene-C3-C7 heterocyclic group containing at least one O atom as a ring-forming atom, C3-C7 saturated heterocyclic group containing at least one O atom as a ring-forming atom, substituted methylpyrazolyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyrazinyl, C1-C 10 alkoxy, substituted or unsubstituted phenyl, substituted or unsubstituted phenyl-CH2-; R 2The substituents present therein are each independently selected from at least one of methyl, ethyl, n-propyl, isopropyl, cyclopropyl, trifluoromethyl, trifluoromethoxy, nitro, cyano, methoxy, methylthio, halogen, -SO2-CH3, and C2-C6 alkynyl groups;

[0071] R 3 and R 4 Each is independently selected from H, C1-C3 alkyl, C1-C3 alkoxy, halogen, and nitro groups;

[0072] Q is a group represented by formula (Q1) or formula (Q2), and R 11 R 12 R 13 R 14 Each is independently selected from H, C1-C3 alkyl groups; R 21 R 22 R 23 Each is independently selected from H, C1-C3 alkyl groups, C 3-6 cycloalkyl groups.

[0073] According to another preferred embodiment, in formula (I),

[0074] X is selected from H, C1-C3 alkyl groups, halogens, and nitro groups;

[0075] R 1 It is a C1-C3 alkyl group or -C6H5;

[0076] R 2 Selected from C1-C 10 Alkyl groups, C1-C substituted with halogens 10 Alkyl groups, C2-C groups substituted with C1-C6 alkoxy groups 10 Alkyl groups, -C1-C6 alkylene groups, -O-C1-C6 alkyl groups, C3-C8 cycloalkyl groups, halogen-substituted C3-C8 cycloalkyl groups, and C3-C8 alkyl groups containing at least one double bond. 10 Hydrocarbon group, C3-C containing at least one triple bond 10 The hydrocarbon group, a C3-C group containing at least one triple bond substituted with a trimethylsilyl group. 10 Hydrocarbon group, -C1-C6 alkylene group, -C3-C8 cycloalkyl group, -C1-C6 alkylene group, -C3-C7 heterocyclic group containing at least one O atom as a cyclic atom, -C3-C7 saturated heterocyclic group containing at least one O atom as a cyclic atom, substituted methylpyrazolyl group, substituted or unsubstituted pyridinyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted pyrazinyl group, C1-C 10 alkoxy, substituted or unsubstituted phenyl, substituted or unsubstituted phenyl-CH2-; R 2The substituents present therein are each independently selected from at least one of methyl, ethyl, n-propyl, isopropyl, cyclopropyl, trifluoromethyl, trifluoromethoxy, nitro, cyano, methoxy, methylthio, halogen, -SO2-CH3, and C2-C6 alkynyl groups;

[0077] R 3 and R 4 Each is independently selected from H, C1-C3 alkyl groups;

[0078] Q is a group represented by formula (Q1) or formula (Q2), and R 11 R 12 R 13 R 14 Each is independently selected from H, C1-C3 alkyl groups; R 21 R 22 R 23 Each is independently selected from H, C1-C3 alkyl groups, and C3-C5 cycloalkyl groups.

[0079] According to a further preferred embodiment, in formula (I),

[0080] X is selected from H, methyl, halogen, and nitro;

[0081] R 1 It is methyl;

[0082] R 2 Selected from C1-C 10 Alkyl groups, C1-C substituted with halogens 10 Alkyl groups, C2-C groups substituted with C1-C6 alkoxy groups 10 Alkyl groups, -C1-C6 alkylene groups, -O-C1-C6 alkyl groups, C3-C8 cycloalkyl groups, halogen-substituted C3-C8 cycloalkyl groups, and C3-C8 alkyl groups containing at least one double bond. 10 Hydrocarbon group, C3-C containing at least one triple bond 10 The hydrocarbon group, a C3-C group containing at least one triple bond substituted with a trimethylsilyl group. 10 Hydrocarbon group, -C1-C6 alkylene group, -C3-C8 cycloalkyl group, -C1-C6 alkylene group, -C3-C7 heterocyclic group containing at least one O atom as a cyclic atom, -C3-C7 saturated heterocyclic group containing at least one O atom as a cyclic atom, substituted methylpyrazolyl group, substituted or unsubstituted pyridinyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted pyrazinyl group, C1-C 10 alkoxy, substituted or unsubstituted phenyl, substituted or unsubstituted phenyl-CH2-; R 2each of the optional substituents is independently selected from at least one of methyl, ethyl, n-propyl, i-propyl, cyclopropyl, trifluoromethyl, trifluoromethoxy, nitro, cyano, methoxy, methylthio, halogen, -SO2-CH3, C2-C6alkynyl;

[0083] R 3 and R 4 are each H;

[0084] Q is a group represented by formula (Q1) or formula (Q2), and R 11 , R 12 , R 13 , R 14 are each H; R 21 , R 22 , R 23 are each independently selected from H, methyl, ethyl, n-propyl, i-propyl, cyclopropyl.

[0085] According to one particularly preferred embodiment, the compound represented by the structure of formula (I) is selected from any one of compounds 1 to 1564.

[0086] According to another particularly preferred embodiment, the compound represented by the structure of formula (I) is selected from any one of compounds 1565 to 1760.

[0087] The present application does not have any particular requirement for the method of preparing the compound described in the first aspect, and a person skilled in the art can determine a suitable synthetic route to obtain the compound described in the first aspect of the present application according to the structural formula provided by the present application in combination with the known knowledge in the field of organic synthesis. However, in order to achieve significantly higher yield and purity, the present application provides a preferred method described in the second aspect for preparing the compound described in the first aspect of the present application.

[0088] Second aspect

[0089] As described previously, the second aspect of the present application provides a method for preparing the quinazolinedione-containing compound described in the first aspect, comprising:

[0090] subjecting a compound represented by the structure of formula (II) to a rearrangement reaction in the presence of a basic substance, a catalyst and a solvent;

[0091]

[0092] wherein, in formula (II),

[0093] W is a group represented by formula (W1) or formula (W2), and R 1 , R 2 , R 3 , R 4The definitions of X, formula (W1) and formula (W2) in the above-mentioned preparation method are the same as those in the first aspect of the present application.

[0094] Preferably, the conditions of the rearrangement reaction include: the reaction temperature is 0-100℃; the reaction time is 0.5-24h.

[0095] Preferably, the catalyst is selected from at least one of sodium cyanide, potassium cyanide, acetone cyanohydrin, trimethylsilyl cyanide, 1,2,4-triazole and benzene 1,2,4-triazole.

[0096] Preferably, the solvent is selected from at least one of dichloromethane, trichloromethane, dichloroethane, acetonitrile, toluene, tetrahydrofuran and benzene.

[0097] Preferably, the basic substance is selected from at least one of potassium carbonate, sodium carbonate, cesium carbonate, triethylamine, N,N-diisopropyl ethylamine and pyridine.

[0098] The present application does not have special requirements for the amount and proportion of the raw materials and solvents and catalysts involved in the above-mentioned preparation method, and those skilled in the art can adjust according to the known parameters in the field of organic synthesis, or those skilled in the art can also reasonably adjust according to the examples provided later in the present application to determine.

[0099] In addition, some conventional post-treatments can also be carried out in the synthesis method involved in the above-mentioned second aspect of the present application, such as filtration, solvent removal, drying, column chromatography, etc., which are well known to those skilled in the art, and the present application will not be described here, and those skilled in the art should not be understood as a limitation of the present application.

[0100] Third aspect

[0101] As described above, the third aspect of the present application provides the use of the quinazolin-2,4-dione-containing compound or its agrochemically acceptable salt, hydrate, solvate, or its enantiomer, optically active form of derivative in the first aspect in inhibiting HPPD activity.

[0102] The weeds described in the present application are plants growing in places harmful to human survival and activity, which can be non-cultivated wild plants or plants useless to humans. For example, it can be various wild plants in crop planting land.

[0103] Preferably, the quinazolin-2,4-dione compound provided by the present application has excellent effect in the application of preventing and treating broadleaf weeds and / or gramineous weeds.

[0104] Preferably, the weed is at least one of barnyardgrass, crabgrass, large crabgrass, leaffoxtail, kikuyugrass, pigweed, goosefoot, lambsquarters, palmer's amaranth, redrootpigweed, brome, wildrye, ryegrass, ripgutgrass, Japanesebrome, and speedwell, chickweed, henbit, and cornspeedwell.

[0105] The present application will be described in detail below by way of examples. In the following examples, the raw materials used are all ordinary commercially available analytical pure products, unless otherwise specified.

[0106] Preparation Example 1

[0107]

[0108] Preparation of intermediate 1-2: 100 g of compound 1-1 was added to a 1 L reaction flask at room temperature (room temperature as described herein means 25±2℃), 500 mL of toluene was added, 1.2 equivalents of acetic anhydride was added to the reaction system, and the temperature was raised to reflux for 5 h. After the reaction was completed, the temperature was stopped, and a large amount of solid was precipitated after cooling to room temperature. The reaction system was filtered and dried to obtain intermediate 1-2 with a yield of 99%.

[0109] Preparation of intermediate 1-3: 100 g of intermediate 1-2 was added to a 2 L flask, 800 mL of concentrated sulfuric acid was added, and the mixture was stirred at 0℃. 20 mL of fuming nitric acid (dissolved in 100 mL of concentrated sulfuric acid) was added dropwise slowly. The reaction was carried out at 0℃ for 9 h. After the raw material was completely reacted, the reaction system was poured into 5 L of ice water, and the mixture was stirred to room temperature and then filtered. The solid was dried to obtain intermediate 1-3 with a yield of 80%.

[0110] Preparation of intermediate 1-4: 99 g of intermediate 1-3 was added to a 1 L single-neck flask, 600 mL of anhydrous methanol was added, and 0.1 equivalent of concentrated sulfuric acid was added dropwise with stirring. The temperature was raised to reflux, and the reaction was carried out for 6 h. After the raw material was completely reacted, the temperature was stopped, and the mixture was cooled to room temperature and then filtered to obtain intermediate 1-4 with a yield of 83%.

[0111] Preparation of intermediate 1-5: 90 g of intermediate 1-4 was added to a 1 L flask, 1.5 equivalents of p-nitrochloroformic acid phenyl ester was added, followed by the addition of 650 mL of acetonitrile. The temperature was raised to reflux, and the reaction was carried out for 7 h. After the raw material was completely reacted, the mixture was cooled to room temperature, filtered, and the solid was dried to obtain intermediate 1-5 with a yield of 85%.

[0112] Preparation of intermediate 1-6: 1 g of common intermediate 1-5 was added to a 100 mL round bottom flask, 30 mL of tetrahydrofuran was added, then 1.2 equivalents of aniline were added to the reaction system, 0.1 equivalent of triethylamine was added, and the temperature was raised to 70°C for 6 hours of reaction. After the reaction was completed, the system solvent was evaporated under reduced pressure, 15 mL of methanol and 2 equivalents of sodium methoxide were added, and the reaction was carried out at room temperature for 30 min. After the reaction was completed, the solvent was evaporated under reduced pressure, 1N HCl solution was added to acidify to pH 3, and then the product was dried by suction filtration to obtain intermediate 1-6 with a yield of 92%.

[0113] Preparation of intermediate 1-7: 1 g of intermediate 1-6 was added to a 100 mL single-neck flask, 2 equivalents of Cs2CO3 and 15 mL of DMF were added, and the reaction was stirred at room temperature for about 30 min. Then 2 equivalents of iodomethane were added dropwise to the reaction system, and the reaction was carried out at room temperature for 1 hour. After the reaction was completed, 60 mL of water was added to the system, a large amount of solid was precipitated, and the product was dried by suction filtration to obtain intermediate 1-7 with a yield of 95%.

[0114] Preparation of intermediate 1-8: 1 g of intermediate 1-7 and 2 equivalents of LiOH·H2O were added to a 100 mL single-neck flask, 15 mL of tetrahydrofuran and 15 mL of water were added. The temperature of the system was maintained at 30°C, and the reaction was carried out for 30 min. After the raw material was completely reacted, the tetrahydrofuran was removed by evaporation under reduced pressure, and 1N HCl was added to the reaction flask after cooling to acidify to pH 4. A large amount of solid was precipitated, and the product was dried by suction filtration to obtain intermediate 1-8 with a yield of 91%.

[0115] Preparation of intermediate 1-9: 0.9 g of intermediate 1-8 was added to a 50 mL reaction flask, 25 mL of super-dry dichloromethane, 0.45 mL of SOCl2, and then 4 drops of DMF were added with stirring. The reaction was carried out at room temperature for 2-4 hours, and the solvent of the reaction system was evaporated under reduced pressure. Another 50 mL round-bottom flask was prepared, 1.5 equivalents of 1,3-cyclohexanedione were added, 10 mL of super-dry dichloromethane and 2 equivalents of triethylamine were added; the above dried system was dissolved in 10 mL of super-dry dichloromethane and then slowly added to the 1,3-cyclohexanedione reaction system, and the reaction was carried out at room temperature for 30 min. After the reaction was completed, the product was washed with saturated NaHCO3 solution for 3 times, extracted with 20 mL of dichloromethane for 3 times, and then the organic layers were combined and dried with anhydrous Na2SO4. The organic layer was purified by column chromatography to obtain intermediate 1-9 with a yield of 83%.

[0116] Preparation of compound 1: 0.5 g of intermediate 1-9 was added to a 50 mL single neck flask, 20 mL of anhydrous acetonitrile was added, 2 equivalents of triethylamine was added under N2 protection, and a catalytic amount of acetone cyanohydrin was added. The reaction was carried out at room temperature for 15 h, and TLC tracking was performed until the reaction raw material was consumed. After the reaction was completed, the acetonitrile was evaporated under reduced pressure, and 20 mL of dichloromethane was used for dissolution, and 20 mL of 1 N hydrochloric acid was used for washing, and the water layer was extracted with 20 mL of dichloromethane for 3 times. The organic phase was combined and dried with anhydrous sodium sulfate. The solvent was evaporated under reduced pressure to obtain a light yellow oil, and the obtained oil was recrystallized with 10 mL of methanol to obtain the target compound 1. The yield was 90%.

[0117] Preparation example 2

[0118]

[0119] Preparation of intermediate 1-10: 100 g of compound 1-1 was added to a 1 L reaction flask at room temperature, 500 mL of isopropyl alcohol was added, and then 1.3 equivalents of N-chlorosuccinimide was added to the reaction system, and the temperature was increased to reflux, and the reaction was carried out for about 5 h. After the reaction was completed, the temperature was stopped, and column chromatography was used for purification to obtain intermediate 1-10, and the yield was 65%.

[0120] Preparation of intermediate 1-11: 90 g of intermediate 1-10 was added to a 1 L flask, 1.5 equivalents of p-nitrochloroformic acid phenyl ester was added, then 650 mL of acetonitrile was added, the temperature was increased to reflux, and the reaction was carried out for 9 h. After the raw material was consumed, the temperature was cooled to room temperature, and filtration was performed, and the solid was dried to obtain intermediate 1-12, and the yield was 90%.

[0121] Preparation of intermediate 1-12: 1 g of intermediate 1-11 was added to a 100 mL round-bottom flask, 30 mL of tetrahydrofuran was added, then 1.2 equivalents of aniline was added to the above system, 0.1 equivalents of triethylamine was added, the temperature was increased to 70°C, and the reaction was carried out for 10 h. After the reaction was completed, the solvent in the system was evaporated under reduced pressure, 15 mL of methanol and 2 equivalents of sodium methoxide were added, the reaction was carried out at room temperature for 30 min, the reaction was completed, the solvent was evaporated under reduced pressure, 1 N HCl solution was added to acidify to pH 3, filtration was performed, and drying was performed to obtain intermediate 1-12, and the yield was 92%.

[0122] Preparation of intermediate 1-13: 1 g of intermediate 1-12 was added to a 100 mL single neck flask, 15 mL of DMF was added, 2 equivalents of Cs2CO3 was added under stirring, and the stirring was continued for about 30 min. Then 2 equivalents of iodomethane was added dropwise to the reaction system, and the reaction was carried out at room temperature for 8 h. After the reaction was completed, 60 mL of water was added to the system, a large amount of solid was precipitated, filtration was performed, and drying was performed to obtain intermediate 1-13, and the yield was 95%.

[0123] Preparation of intermediate 1-14: 1 g of intermediate 1-13 and 2 equivalents of LiOH-H2O were added to a 50 mL single-neck flask, and 15 mL of tetrahydrofuran and 15 mL of water were added. The system was maintained at 30°C, and the reaction was carried out for 30 min. After the raw material was completely reacted, tetrahydrofuran was removed by distillation under reduced pressure, and 1 N HCl was added to the reaction flask after cooling to acidify to pH 4. A large amount of solid was precipitated, and after filtration and drying, intermediate 1-14 was obtained in a yield of 91%.

[0124]

[0125] Preparation of intermediate 1-15: 0.9 g of intermediate 1-14 was added to a 50 mL reaction flask, and 25 mL of super-dry dichloromethane, 0.45 mL of SOCl2, and 4 drops of DMF were added dropwise while stirring. The reaction was carried out at room temperature for 2-4 hours, and the solvent of the reaction system was evaporated under reduced pressure. Another 50 mL round-bottom flask was prepared, 1.5 equivalents of 1,3-cyclohexanedione were added, 10 mL of super-dry dichloromethane and 2 equivalents of triethylamine were added; the above evaporated system was dissolved in 10 mL of super-dry dichloromethane and slowly added to the 1,3-cyclohexanedione reaction system, and the reaction was carried out at room temperature for 30 min. After the reaction was completed, the reaction system was washed with saturated NaHCO3 solution 3 times, and the water layer was extracted with 20 mL of dichloromethane 3 times. The organic layer was combined and dried with anhydrous Na2SO4, and column chromatography was used for purification to obtain intermediate 1-15 in a yield of 83%.

[0126] Preparation of compound 267: 0.5 g of intermediate 1-15 was added to a 50 mL single-neck flask, 20 mL of anhydrous acetonitrile was added, 2 equivalents of triethylamine was added under N2 protection, and a catalytic amount of acetone cyanohydrin was added. The reaction was carried out at room temperature for 15 h, and TLC tracking was used to track the disappearance of the raw material. After the reaction was completed, the acetonitrile was evaporated under reduced pressure, dissolved in 20 mL of dichloromethane, washed with 20 mL of 1 N hydrochloric acid, and the water layer was extracted with 20 mL of dichloromethane 3 times. The organic phase was combined and dried with anhydrous sodium sulfate. The solvent was evaporated under reduced pressure to obtain a light yellow oil, and the oil was recrystallized with 10 mL of methanol to obtain the target compound 267. The yield was 91%.

[0127] Preparation Example 3

[0128]

[0129] Preparation of intermediate 1-16: 0.9 g of intermediate 1-14 was added to a 50 mL reaction flask, 25 mL of super dry dichloromethane was added under stirring, 0.45 mL of SOCl2was added, followed by dropwise addition of 4 drops of DMF. The reaction was carried out at room temperature for 2-4 hours, and the reaction system was evaporated under reduced pressure to dryness. Another 50 mL round bottom flask was prepared, 1.5 equivalents of 1,3-dimethyl-5-pyrazolone was added, 10 mL of super dry dichloromethane and 2 equivalents of triethylamine were added; the above dried system was dissolved in 10 mL of super dry dichloromethane and slowly added to the 1,3-dimethyl-5-pyrazolone reaction system, and the reaction was carried out at room temperature for 30 min. After the reaction was completed, it was washed with saturated NaHCO3solution for 3 times, and the water layer was extracted with 20 mL of dichloromethane for 3 times. The combined organic layer was dried over anhydrous Na2SO4, and column chromatography was used for purification to obtain intermediate 1-16 with a yield of 79%.

[0130] Preparation of compound 1640: 0.5 g of intermediate 1-16 was added to a 50 mL single-neck flask, 20 mL of anhydrous acetonitrile was added, 2 equivalents of triethylamine was added under N2protection, and a catalytic amount of acetone cyanohydrin was added. The reaction was carried out at room temperature for 15 h, and TLC tracking was used to track the disappearance of the raw material. After the reaction was completed, the acetonitrile was evaporated under reduced pressure to dryness, dissolved in 20 mL of dichloromethane, washed with 20 mL of 1N hydrochloric acid, and the water layer was extracted with 20 mL of dichloromethane for 3 times. The combined organic phase was dried over anhydrous sodium sulfate. The solvent was evaporated to dryness under reduced pressure to obtain a light yellow oil, and the obtained oil was recrystallized with 10 mL of methanol to obtain the target compound 1640. The yield was 89%.

[0131] Preparation Example 4

[0132]

[0133] Preparation of intermediate 2-2: 100 g of compound 2-1 was added to a 1 L reaction flask at room temperature, 450 mL of concentrated sulfuric acid was added, 14 mL of fuming nitric acid was mixed with 50 mL of concentrated sulfuric acid to prepare a mixed acid, and the mixed acid was added dropwise to the reaction system at 0°C. The reaction was carried out for about 7 h. After the reaction was completed, the reaction system was slowly added to 2 L of ice, a large amount of white solid was precipitated, and after being extracted under reduced pressure, it was washed with a large amount of water and dried to obtain intermediate 2-2 with a yield of 90%.

[0134] Preparation of intermediate 2-3: 120 g of intermediate 2-2 was added to a 1 L flask, 600 mL of methanol was added, a catalytic amount of concentrated sulfuric acid was added dropwise, and the temperature was raised to reflux state, and the reaction was carried out for 16 hours. After the reaction was completed, the temperature was cooled to room temperature, a large amount of solid was precipitated, and after being extracted, a white solid was obtained, which was dried to obtain intermediate 2-3 with a yield of 91%.

[0135] Preparation of intermediate 2-4: 100 g of intermediate 2-3 was taken in a 1 L flask, 3 equivalents of Cs2C03and 0.1 equivalent of Pd(PPh3)4was added. The air was replaced three times and 500 mL of heavy toluene solvent was added under nitrogen atmosphere, 1.5 equivalents of trimethyltrisboroxine was added, the temperature was raised to 100-110 °C and the reaction was carried out for 8 h, the progress of the reaction was monitored by TLC, after the completion of the reaction, the filtrate was evaporated under reduced pressure and purified by column chromatography to obtain intermediate 2-4, yield: 90%.

[0136] Preparation of intermediate 2-5: 80 g of intermediate 2-4 was taken in a 500 mL flask, 5 equivalents of reduced iron powder, 150 mL of ethanol and water were added. The temperature was raised to reflux, 2 equivalents of 6N concentrated HC1 was added, the progress of the reaction was monitored by TLC, after 5 min the reaction was completed. The filtrate was filtered through celite, the mother liquor was extracted with ethyl acetate, the organic layer was washed with saturated Na2C03solution, concentrated and purified by column chromatography to obtain intermediate 2-5, yield: 85%.

[0137] Preparation of intermediate 2-6: 80 g of intermediate 2-5 was taken in a 1 L flask, 1.5 equivalents of p-nitrophenyl chloroformate was added, followed by the addition of 650 mL of acetonitrile, the temperature was raised to reflux and the reaction was carried out for 6-10 h, after the completion of the reaction, the temperature was cooled to room temperature, the solid was dried under reduced pressure to obtain intermediate 2-6, yield: 90%.

[0138] Preparation of intermediate 2-7: 1 g of common intermediate 2-6 was taken in a 100 mL round bottom flask, 30 mL of tetrahydrofuran was added, followed by the addition of 1.2 equivalents of aniline to the above system, 0.1 equivalent of triethylamine was added, the temperature was raised to 70 °C and the reaction was carried out for 10 h. After the completion of the reaction, the solvent was evaporated under reduced pressure, 15 mL of methanol and 2 equivalents of sodium methoxide were added, the reaction was carried out at room temperature for 30 min, after the completion of the reaction, the solvent was evaporated under reduced pressure, 1 N HC1 solution was added to acidify the pH to 3, the solid was filtered and dried to obtain intermediate 2-7, yield: 92%.

[0139] Preparation of intermediate 2-8: 1 g of intermediate 2-7 was taken in a 100 mL single neck flask, 15 mL of DMF was added, 2 equivalents of Cs2C03was added with stirring and the reaction was carried out for about 30 min. Then 2 equivalents of iodomethane was added dropwise to the reaction system, after the addition was complete, the reaction was carried out at room temperature for 8 h. After the completion of the reaction, 60 mL of water was added to the system, a large amount of solid was precipitated, which was filtered and dried to obtain intermediate 2-8, yield: 95%.

[0140] Preparation of intermediate 2-9: 1 g of intermediate 2-8 and 2 equivalents of LiOH-H2O were added to a 100 mL single-neck flask, and 15 mL of tetrahydrofuran and 15 mL of water were added. The system was kept at 30°C, and the reaction was carried out for 30 min. After the raw material was completely reacted, the tetrahydrofuran was removed by distillation under reduced pressure, and 1 N HCl was added to the reaction flask after cooling to acidify to pH 4. A large amount of solid was precipitated, and the solid was filtered and dried to obtain intermediate 2-9 in a yield of 90%.

[0141] Preparation of intermediate 2-10: 0.9 g of intermediate 2-9 was added to a 50 mL reaction flask, and 25 mL of super-dry dichloromethane, 0.45 mL of SOCl2, and 4 drops of DMF were added dropwise under stirring. The reaction was carried out at room temperature for 2-4 hours, and the solvent of the reaction system was evaporated under reduced pressure. Another 50 mL round-bottom flask was prepared, 1.5 equivalents of 1,3-cyclohexanedione were added, 10 mL of super-dry dichloromethane was added, and 2 equivalents of triethylamine were added. The above dried system was dissolved in 10 mL of super-dry dichloromethane and slowly added to the 1,3-cyclohexanedione reaction system, and the reaction was carried out at room temperature for 30 min. After the reaction was completed, the system was washed with saturated NaHCO3 solution for 3 times, and the water layer was extracted with 20 mL of dichloromethane for 3 times. After the extraction was completed, the organic layers were combined, and then the organic layer was dried with anhydrous Na2SO4. The organic layer was purified by column chromatography to obtain intermediate 2-10 in a yield of 75%.

[0142] Preparation of compound 533: 0.5 g of intermediate 2-10 was added to a 50 mL single-neck flask, 20 mL of anhydrous acetonitrile was added, 2 equivalents of triethylamine was added under N2 protection, and a catalytic amount of acetone cyanohydrin was added. The reaction was carried out at room temperature for 15 h, and TLC tracking was performed until the raw material disappeared. After the reaction was completed, the acetonitrile was evaporated under reduced pressure, dissolved in 20 mL of dichloromethane, washed with 20 mL of 1 N hydrochloric acid, and the water layer was extracted with 20 mL of dichloromethane for 3 times. The organic phases were combined and dried with anhydrous sodium sulfate. The solvent was evaporated under reduced pressure to obtain a light yellow oil, and the oil was recrystallized with 10 mL of methanol to obtain the target compound 533. The yield was 89%.

[0143] Preparation Example 5

[0144]

[0145] Preparation of intermediate 3-2: 100 g of intermediate 1-1 was added to a 1 L flask, 1.5 equivalents of p-nitrophenyl chloroformate was added, and then 650 mL of acetonitrile was added. The temperature was raised to reflux, and the reaction was carried out for 9 hours. After the raw material was completely reacted, the system was cooled to room temperature, filtered, and the solid was dried to obtain intermediate 3-2 in a yield of 94%.

[0146] Preparation of intermediate 3-3: 1 g of intermediate 3-2 was added to a 100 mL round bottom flask, 30 mL of tetrahydrofuran was added, then 1.2 equivalents of aniline were added to the system, 0.1 equivalent of triethylamine was added, and the temperature was raised to 70°C for 10 hours. After the reaction was completed, the system solvent was evaporated under reduced pressure, 15 mL of methanol and 2 equivalents of sodium methoxide were added, and the reaction was carried out at room temperature for 30 min. After the reaction was completed, the solvent was evaporated under reduced pressure, 1 N HCl solution was added to acidify to pH 3, and then the product was dried by suction filtration to obtain intermediate 3-3 with a yield of 92%.

[0147] Preparation of intermediate 3-4: 1 g of intermediate 3-3 was added to a 100 mL single-neck flask, 15 mL of DMF was added, and 2 equivalents of Cs2CO3 were added with stirring, and the reaction was continued for about 30 min. Then 2 equivalents of iodomethane were slowly added to the reaction system, and after the addition was completed, the reaction was stirred at room temperature for 8 hours. After the reaction was completed, 60 mL of water was added to the system, and a large amount of solid was precipitated. The product was dried by suction filtration to obtain intermediate 3-4 with a yield of 96%.

[0148] Preparation of intermediate 3-5: 1 g of intermediate 3-4 and 0.5 g of LiO·H2O were added to a 50 mL single-neck flask, 15 mL of tetrahydrofuran and 15 mL of water were added. The temperature of the system was maintained at 30°C, and the reaction was carried out for 30 min. After the raw material was completely reacted, the tetrahydrofuran was removed by evaporation under reduced pressure, and 1 N HCl was added to the reaction flask after cooling to acidify to pH 4. A large amount of solid was precipitated, which was dried by suction filtration to obtain intermediate 3-5 with a yield of 91%.

[0149] Preparation of intermediate 3-6: 0.9 g of intermediate 3-5 was added to a 50 mL reaction flask, 25 mL of super dry dichloromethane, 0.45 mL of SOCl2, and 4 drops of DMF were added with stirring. The reaction was carried out at room temperature for 2-4 hours, and the solvent of the reaction system was evaporated under reduced pressure. Another 50 mL round bottom flask was prepared, 1.5 equivalents of 1,3-cyclohexanedione were added, 10 mL of super dry dichloromethane was added, and 2 equivalents of triethylamine was added. The above dried system was dissolved in 10 mL of super dry dichloromethane and slowly added to the 1,3-cyclohexanedione reaction system, and the reaction was carried out at room temperature for 30 min. After the reaction was completed, the product was washed with saturated NaHCO3 solution for 3 times, extracted with 20 mL of dichloromethane for 3 times, and then the organic layer was combined. The organic layer was dried with anhydrous Na2SO4, and then the organic layer was purified by column chromatography to obtain intermediate 3-6 with a yield of 79%.

[0150] Preparation of compound 799: 0.5 g of intermediate 1-9 was taken in a 50 mL single necked flask, 20 mL of dry acetonitrile was added, 2 equivalents of triethylamine was added under N2protection, catalytic amount of acetone cyanohydrin was added. The reaction was carried out at room temperature for 15 h, TLC was followed till the starting material was consumed. The reaction was completed, acetonitrile was distilled off under reduced pressure, dissolved in 20 mL of dichloromethane, washed with 20 mL of IN hydrochloric acid, the aqueous layer was extracted with 20 mL of dichloromethane for 3 times. The organic layers were combined and dried over anhydrous sodium sulphate. The solvent was distilled off under reduced pressure to get an oil which was recrystallized from 5 mL of methanol to get the desired compound 799. The yield was 93%.

[0151] The characterization data of some of the compounds of the present application is given in Table 1.

[0152] Table 1

[0153]

[0154]

[0155]

[0156]

[0157]

[0158]

[0159]

[0160]

[0161]

[0162]

[0163]

[0164]

[0165]

[0166]

[0167]

[0168]

[0169]

[0170]

[0171]

[0172]

[0173] Test Example 1

[0174] Preliminary screening test (pot method):

[0175] The inhibition rates of some of the compounds of the present application on the test targets were tested, and the test targets are shown in Table 3 and Table 4;

[0176] The safety of some of the compounds of the present application on the test crops was evaluated by inhibition levels, and the test crops are shown in Table 6 and Table 7;

[0177] The post-emergence stems and leaves of the test targets or the test crops were sprayed: a paper cup with an inner diameter of 7 cm was filled with a mixture of soil (garden soil: seedling substrate, 1:2, v / v) to ¾, and weeds were directly sown, and the soil was covered with 0.2 cm. When the weeds grew to 4-5 leaves, they were used for the test. Some of the compounds of the present application were applied at a dose of 320 g a.i. / ha (grams per hectare), and after the spray liquid on the leaves of the weeds or crops was dried, the samples were moved to a greenhouse (humidity 70%) for culture. After 30 days, the results were investigated;

[0178] The growth inhibition rate evaluation method was visual observation, and the inhibition levels were rated according to the conditions shown in Table 2. The results of the inhibition level rating test are shown in Table 3 and Table 4;

[0179] Furthermore, some of the compounds of the present application were further screened by reducing the application amount, and the results are shown in Table 5.

[0180] The safety evaluation results of some of the compounds of the present application on the crops are shown in Table 6 and Table 7.

[0181] Table 2

[0182] (％) Evaluation (inhibition, deformation, whitening, etc.) Growth inhibition rate level 0-5 No effect on weed or crop growth, no phytotoxic symptoms. 0 5-20 Slight effect on weed or crop growth, no obvious phytotoxic symptoms. 1 20-40 Inhibition of weed or crop growth, no obvious phytotoxic symptoms. 2 40-60 Effect on weed or crop growth, with obvious phytotoxic symptoms. 3 60-85 Weed or crop growth is severely inhibited. 4 85-100 Weed or crop death. 5

[0183] Table 3

[0184]

[0185]

[0186]

[0187]

[0188]

[0189]

[0190] Note: " / " means not tested.

[0191] Table 4

[0192]

[0193]

[0194]

[0195]

[0196] Table 5

[0197]

[0198]

[0199]

[0200] Note: " / " means not tested.

[0201] Table 6

[0202]

[0203] Note: " / " means not tested.

[0204] Table 7

[0205]

[0206] From the above results, it can be seen that most of the compounds provided by the present application exhibit very excellent herbicidal effects on 7 common grasses and broadleaf weeds of Echinochloa crus-galli, Digitaria sanguinalis, Digitaria ischaemum, Amaranthus retroflexus, Chenopodium album, Atriplex hortensis and Abutilon theophrasti, and meanwhile, some of the compounds of the present application exhibit good safety on Zea mays, Oryza sativa indica, Oryza sativa japonica, Triticum aestivum, Sorghum bicolor, Setaria italica and Arachis hypogaea.

[0207] Among them, most of the compounds can achieve an inhibition rate of 85% or more on weeds such as Echinochloa crus-galli, Digitaria sanguinalis, Digitaria ischaemum, Amaranthus retroflexus and Abutilon theophrasti at a dosage of 320 g a.i. / ha; and can also exhibit obvious herbicidal effects when the dosage is as low as 30 g a.i. / ha. Therefore, the compounds provided by the present application can be used for preventing and controlling at least one weed in the fields of Zea mays, Oryza sativa indica, Oryza sativa japonica, Triticum aestivum, Sorghum bicolor, Setaria italica and Arachis hypogaea.

[0208] In particular, some of the compounds provided by the present application exhibit good safety on rice (Oryza sativa indica and Oryza sativa japonica) at a dosage of 150 g a.i. / ha, and exhibit excellent effects on malignant weeds such as Echinochloa crus-galli in rice fields. Therefore, the compounds of the present application can be developed as herbicides for rice fields.

[0209] In addition, at a dose of 150 g a.i. / ha, the partial compounds provided by the present application exhibit good safety to wheat and excellent control effect on harmful weeds such as dogtail grass in wheat fields. Therefore, the compounds of the present application can also be developed as herbicides for wheat fields.

[0210] The compounds provided by the present application can improve the herbicidal activity of the inhibitor molecules on one hand, and improve the crop safety of the inhibitor molecules on the other hand. The subsequent development is expected to be applied to the control of various field weeds, has important practical significance and great market value. The compounds provided by the present application can also be used as candidate drug molecules of HPPD herbicides, and have important significance for creating super-efficient herbicides and controlling weeds.

[0211] The preferred embodiments of the present application are described in detail above, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as disclosed by the present application and belong to the protection scope of the present application.

Claims

1. A quinazolinedione-containing compound or an agrochemically acceptable salt thereof, characterized in that, The compound has a structure shown in formula (I): Formula (I), Formula (Q1), Formula (Q2), In formula (I), X is selected from H, C1-C6 alkyl groups, halogen-substituted C1-C6 alkyl groups, C1-C6 alkoxy groups, halogens, nitro groups, cyano groups, and -S(O). m CH3; m is 0, 1, or 2; R 1 is Ci-C6alkyl, -C6H5, or -CH2C6H5; R 2 Selected from C1-C 12 Alkyl groups, C1-C substituted with halogens 12 Alkyl groups, C2-C groups substituted with C1-C6 alkoxy groups 12 Alkyl, -C1-C6 alkylene, -O-C1-C6 alkyl, C3-C 10 cycloalkyl groups, halogen-substituted C3-C 10 cycloalkyl groups, C3-C containing at least one double bond 12 Hydrocarbon group, C3-C containing at least one triple bond 12 The hydrocarbon group, a C3-C group containing at least one triple bond substituted with a trimethylsilyl group. 12 hydrocarbon group, -C1-C6 alkylene group, -C3-C 10 Cycloalkyl, -C1-C6 alkylene-C3-C7 heterocyclic groups containing at least one O atom as a cyclic atom, C3-C7 saturated heterocyclic groups containing at least one O atom as a cyclic atom, substituted methylpyrazolyl, substituted or unsubstituted pyridinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted pyrazinyl, C1-C 12 alkoxy, substituted or unsubstituted phenyl, substituted or unsubstituted phenyl-CH2-; R 2 The substituents present therein are each independently selected from at least one of the following: C1-C6 alkyl, C3-C6 cycloalkyl, halogen-substituted C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkathio, halogen-substituted C1-C6 alkoxy, nitro, cyano, halogen, -SO2-CH3, and C2-C6 alkynyl; R 3 and R 4 each independently is selected from H, C1-C6 alkyl, C1-C6 alkoxy, halogen, nitro; Q is a group of formula (Q1) or (Q2) and R 11 , R 12 , R 13 , R 14 each independently selected from H, C1-C6 alkyl; R 21 , R 22 , R 23 each independently selected from H, C1-C6 alkyl, C3-C6 cycloalkyl.

2. The compound of claim 1, wherein, In formula (I), X is selected from H, C1-C4 alkyl, C1-C4 alkyl substituted by halogen, C1-C4 alkoxy, halogen, nitro, cyano; R 1 is CrC4alkyl, -C6H5or -CH2C6H5; R 2 alkyl, C1-C 10 alkyl substituted with halogen, C1-C 10 alkyl substituted with C1-C6alkoxy, C2-C 10 alkyl, -C1-C6alkylene-O-C1-C6alkyl, C3-C8cycloalkyl, C3-C 10 alkyl containing at least one triple bond, C3-C 10 alkyl containing at least one triple bond substituted with trimethylsilyl, C3-C 10 alkyl, -C1-C6alkylene-C3-C8cycloalkyl, -C1-C6alkylene-C3-C7heterocyclyl containing at least one O atom as a ring-forming atom, C3-C7saturated heterocyclyl containing at least one O atom as a ring-forming atom, substituted methylpyrazolyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyrazinyl, C1-C 10 alkoxy, substituted or unsubstituted phenyl, substituted or unsubstituted phenyl-CH2-; R 2 each of the optional substituents in R is independently selected from at least one of methyl, ethyl, n-propyl, i-propyl, cyclopropyl, trifluoromethyl, trifluoromethoxy, nitro, cyano, methoxy, methylthio, halogen, -SO2-CH3, C2-C6alkynyl; R 3 and R 4 each independently is selected from H, C1-C3alkyl, C1-C3alkoxy, halogen, nitro; Q is a group of formula (Q1) or formula (Q2), and R 11 , R 12 , R 13 , R 14 each independently is selected from H, C1-C3 alkyl; R 21 , R 22 , R 23 each independently is selected from H, C1-C3 alkyl, C3-C6 cycloalkyl.

3. The compound of claim 2, wherein, In formula (I), X is selected from H, C1-C3 alkyl, halogen, nitro; R 1 is CrC3alkyl or -C6H5; R 2 Selected from C1-C 10 Alkyl groups, C1-C substituted with halogens 10 Alkyl groups, C2-C groups substituted with C1-C6 alkoxy groups 10 Alkyl groups, -C1-C6 alkylene groups, -O-C1-C6 alkyl groups, C3-C8 cycloalkyl groups, halogen-substituted C3-C8 cycloalkyl groups, and C3-C8 alkyl groups containing at least one double bond. 10 Hydrocarbon group, C3-C containing at least one triple bond 10 The hydrocarbon group, a C3-C group containing at least one triple bond substituted with a trimethylsilyl group. 10 Hydrocarbon group, -C1-C6 alkylene group, -C3-C8 cycloalkyl group, -C1-C6 alkylene group, -C3-C7 heterocyclic group containing at least one O atom as a cyclic atom, -C3-C7 saturated heterocyclic group containing at least one O atom as a cyclic atom, substituted methylpyrazolyl group, substituted or unsubstituted pyridinyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted pyrazinyl group, C1-C 10 alkoxy, substituted or unsubstituted phenyl, substituted or unsubstituted phenyl-CH2-; R 2 The substituents present therein are each independently selected from at least one of methyl, ethyl, n-propyl, isopropyl, cyclopropyl, trifluoromethyl, trifluoromethoxy, nitro, cyano, methoxy, methylthio, halogen, -SO2-CH3, and C2-C6 alkynyl groups; R 3 and R 4 each independently is selected from H, C1-C3 alkyl; Q is a group of formula (Q1) or formula (Q2), and R 11 , R 12 , R 13 , R 14 each independently is selected from H, C1-C3 alkyl; R 21 , R 22 , R 23 each independently is selected from H, C1-C3 alkyl, C3-C5 cycloalkyl.

4. The compound of claim 3, wherein, In formula (I), X is selected from H, methyl, halogen, nitro; R 1 is methyl; R 2 alkyl, C1-C 10 alkyl substituted with halogen, C1-C 10 alkyl substituted with C1-C6alkoxy, C2-C 10 alkyl, -C1-C6alkylene-O-C1-C6alkyl, C3-C8cycloalkyl, C3-C8cycloalkyl substituted with halogen, C3-C 10 alkyl containing at least one triple bond, C3-C 10 alkyl containing at least one triple bond substituted with trimethylsilyl, C3-C 10 alkyl, -C1-C6alkylene-C3-C8cycloalkyl, -C1-C6alkylene-C3-C7heterocyclyl containing at least one O atom as a ring-forming atom, C3-C7saturated heterocyclyl containing at least one O atom as a ring-forming atom, substituted methylpyrazolyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyrazinyl, C1-C 10 alkoxy, substituted or unsubstituted phenyl, substituted or unsubstituted phenyl-CH2-; R 2 each of the optional substituents in R is independently selected from at least one of methyl, ethyl, n-propyl, i-propyl, cyclopropyl, trifluoromethyl, trifluoromethoxy, nitro, cyano, methoxy, methylthio, halogen, -SO2-CH3, C2-C6alkynyl; R 3 and R 4 are each H; Q is a group of formula (Q1) or (Q2), and R 11 , R 12 , R 13 , R 14 are each independently H; R 21 , R 22 , R 23 are each independently selected from H, methyl, ethyl, n-propyl, i-propyl, cyclopropyl.

5. The compound according to any one of claims 1-4, wherein, The compound of the structure of formula (I) is selected from any one of the following compounds, wherein Q is formula (Q1), R 3 , R 4 , R 11 , R 12 , R 13 , R 14 are each H. 。 6. The compound of any one of claims 1-4, wherein, The compound of the structure of Formula (I) is selected from any one of the following compounds, wherein Q is Formula (Q2), R 3 , R 4 , R 23 are each H. 。 7. A process for preparing a quinazolinedione-containing compound according to any one of claims 1 to 6, characterized in that, Comprising: In the presence of a basic substance, a catalyst and a solvent, a compound having a structure shown in formula (II) is subjected to a rearrangement reaction; Formula (II), Formula (W1), Formula (W2), In formula (II), W is a group represented by formula (W1) or formula (W2), and R 1 , R 2 , R 3 , R 4 , X, the definitions in formula (W1) and formula (W2) are the same as the definitions in any one of claims 1-6.

8. The method of claim 7, wherein, The conditions of the rearrangement reaction include: the reaction temperature is 0-100℃; the reaction time is 0.5-24h.

9. The method of claim 7, wherein, The catalyst is selected from at least one of sodium cyanide, potassium cyanide, acetone cyanohydrin, trimethylsilyl cyanide, 1,2,4-triazole and benzene 1,2,4-triazole.

10. The method of claim 7, wherein, The solvent is selected from at least one of dichloromethane, trichloromethane, dichloroethane, acetonitrile, toluene, tetrahydrofuran and benzene.

11. Use of a quinazolinedione-containing compound according to any one of claims 1 to 6 or an agrochemically acceptable salt thereof as a herbicide for inhibiting HPPD activity.

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