Tetrasubstituted benzene compound containing diazo substituent and preparation method and application thereof

Abstract

The invention discloses a tetra-substituted benzene compound containing diazo substituent and a preparation method and application thereof, the tetra-substituted benzene compound has a structure as shown in a formula I, and the definition of each substituent in the compound as shown in the specification. The compound shown in the formula I has excellent herbicidal activity and crop safety, and can be used for preventing and treating agricultural weeds.

Description

Technical Field

[0001] This invention belongs to the field of herbicides, specifically relating to a tetrasubstituted benzene compound containing a diazo substituent, its preparation method, and its application. Background Technology

[0002] Weeds cause enormous economic losses globally by reducing crop yields and quality. Worldwide, crops must contend with hundreds of weed species. Due to the succession and transformation of weed populations, the emergence and rapid development of resistance to chemical pesticides, and the increasing awareness of chemical pesticide pollution and environmental protection issues, research and development of more effective and / or more selective herbicides remains necessary.

[0003] With the gradual decrease in the world's arable land area, the continuous growth of the population, and the increasing demand for food, people are forced to rapidly develop agricultural production technology, improve and perfect farming systems, and continuously invent new and improved herbicides and compounds in order to kill or inhibit weed growth, thereby increasing crop yield and quality and meeting the ever-growing human demand for food. Summary of the Invention

[0004] The object of this invention is to provide a novel tetrasubstituted benzene compound containing a diazo substituent, and a herbicidal composition using this compound as the active ingredient. The compound exhibits superior herbicidal activity at lower application rates and high crop safety at higher application rates. The object of this invention can also be extended to provide novel compounds for use as desiccants or defoliants.

[0005] The technical solution adopted in this invention is as follows:

[0006] This invention provides a novel tetrasubstituted benzene compound containing a diazo substituent, having the structure shown in Formula I:

[0007]

[0008] in,

[0009] Het is selected from 3- to 7-membered monocyclic or 6- to 10-membered bicyclic substituents, each ring substituent containing a ring member selected from carbon atoms and 0 to 5 heteroatoms, these heteroatoms being independently selected from a maximum of 2 O atoms, a maximum of 2 S atoms and a maximum of 5 N atoms, each ring substituent being optionally substituted by a maximum of 5 substituents, the substituents on the ring being independently selected from halogen, cyano, amino, hydroxy, nitro, mercapto, C1 to C6 alkyl, C2 to C8 alkenyl, C2 to C8 alkynyl, C3 to C8 cycloalkyl, C1 to C6 haloalkyl, C1 to C6 alkoxy, C1 to C6 alkylamino, C1 to C6 alkylthio, C1 to C6 alkylsulfinyl, C1 to C6 alkylsulfonyl, C1 to C6 alkoxy-C1 to C6 alkyl, C3 to C8 cycloalkyl-C1 to C6 alkyl, phenyl or benzyl;

[0010] X is selected from hydrogen, halogen, C1-C6 alkyl or C1-C6 alkoxy;

[0011] Y is selected from halogen, cyano, nitro, C1-C6 alkyl, C1-C6 alkoxy, CONH2 or CSNH2;

[0012] R is selected from C1-C6 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C1-C6 haloalkyl, C1-C6 alkoxy-C1-C6 alkyl, C1-C6 alkylthio-C1-C6 alkyl, C1-C6 alkylamino-C1-C6 alkyl, C3-C8 cycloalkyl-C1-C6 alkyl, C2-C8 oxecycloalkyl-C1-C6 alkyl, C1-C6 alkoxycarbonyl-C1-C6 alkyl, phenyl or benzyl, and the above groups may be further replaced by any combination of one or more halogens, cyano, nitro, C1-C6 alkoxy, C1-C6 haloalkyl or C1-C6 haloalkoxy.

[0013] The preferred compound of this invention is that in Formula I:

[0014] Het is selected from 5- or 6-membered monocyclic substituents or 8- to 10-membered bicyclic substituents, each cyclic substituent containing a ring member selected from a carbon atom and 0 to 5 heteroatoms, these heteroatoms being independently selected from a maximum of 2 O atoms, a maximum of 2 S atoms, and a maximum of 5 N atoms, each cyclic substituent being optionally substituted by a maximum of 5 substituents, the substituents being independently selected from halogens, cyano, amino, hydroxyl, nitro, mercapto, C1-C6 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 alkylamino, C1-C6 alkylthio, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 alkoxy-C1-C6 alkyl, C3-C8 cycloalkyl-C1-C6 alkyl, phenyl, or benzyl;

[0015] X is selected from hydrogen or halogen;

[0016] Y is selected from halogen, cyano, nitro, CONH2 or CSNH2;

[0017] R is selected from C1-C6 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C1-C6 haloalkyl, C1-C6 alkoxy-C1-C6 alkyl, C1-C6 alkylthio-C1-C6 alkyl, C1-C6 alkylamino-C1-C6 alkyl, C3-C8 cycloalkyl-C1-C6 alkyl, C2-C8 oxecycloalkyl-C1-C6 alkyl, C1-C6 alkoxycarbonyl-C1-C6 alkyl, phenyl or benzyl, and the above groups may be further replaced by any combination of one or more halogens, cyano, nitro, C1-C6 alkoxy, C1-C6 haloalkyl or C1-C6 haloalkoxy.

[0018] The preferred compound of this invention is that of formula I:

[0019] Het is selected from

[0020]

[0021] in,

[0022] W1, W2, and W3 are each independently oxygen or sulfur;

[0023] A is selected from N or CR5;

[0024] R1 and R2 are each independently selected from hydrogen, cyano, amino, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 haloalkoxy, C3-C7 cycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, benzyl, C2-C6 cyanoalkyl or OR7, or R1 and R2 together with the atoms they are attached to form a 3- to 7-membered ring, and the 3- to 7-membered ring formed by R1 and R2 together with the atoms they are attached to may be further substituted by any combination of one or more halogens, nitro, cyano, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylamino or C1-C4 alkylthio;

[0025] R3 and R4 are each independently selected from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 haloalkoxy, C3-C7 cycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, OR7, and S(O). nR7, OSO2R7 or NR7R8, or R3 and R4 together with the atoms to which they are attached form a 3- to 7-membered ring, and the 3- to 7-membered ring formed by R3 and R4 together with the atoms to which they are attached may be further substituted by any combination of one or more halogens, nitro, cyano, C1 to C4 alkyl, C1 to C4 alkoxy, C1 to C4 alkylamino or C1 to C4 alkylthio, where n is 0, 1 or 2;

[0026] R5 is selected from hydrogen, halogen, or C1-C6 alkyl;

[0027] R6 is selected from hydrogen, halogens, C1-C6 alkyl groups, OR7, SR7, and S(O). n R7, OSO2R7 or NR7R8, where n is 0, 1 or 2;

[0028] R7 and R8 are each independently selected from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C7 cycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, phenyl or benzyl, and the other groups mentioned above, except for hydrogen, may be further replaced by any combination of one or more halogens, nitro, cyano, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylamino or C1-C4 alkylthio.

[0029] X is selected from hydrogen, fluorine, or chlorine;

[0030] Y is selected from fluorine, chlorine, bromine, or cyano groups;

[0031] R is selected from C1-C6 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C1-C6 haloalkyl, C1-C6 alkoxy-C1-C6 alkyl, C1-C6 alkylthio-C1-C6 alkyl, C1-C6 alkylamino-C1-C6 alkyl, C3-C8 cycloalkyl-C1-C6 alkyl, C2-C8 oxecycloalkyl-C1-C6 alkyl, C1-C6 alkoxycarbonyl-C1-C6 alkyl, phenyl or benzyl, and the above groups may be further replaced by any combination of one or more halogens, cyano, nitro, C1-C6 alkoxy, C1-C6 haloalkyl or C1-C6 haloalkoxy.

[0032] A more preferred compound of the present invention is, in formula I:

[0033] Het is selected from Het1, Het2, Het3, Het4, Het6, Het8, Het 10 Het 11 Het 12 Or Het 14 ;

[0034] X is selected from hydrogen, fluorine, or chlorine;

[0035] Y is selected from fluorine, chlorine, bromine, or cyano groups;

[0036] Z is selected from oxygen or sulfur;

[0037] R is selected from C1-C6 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C1-C6 haloalkyl, C1-C6 alkoxy-C1-C6 alkyl, C1-C6 alkylthio-C1-C6 alkyl, C1-C6 alkylamino-C1-C6 alkyl, C3-C8 cycloalkyl-C1-C6 alkyl, C2-C8 oxecycloalkyl-C1-C6 alkyl, C1-C6 alkoxycarbonyl-C1-C6 alkyl, phenyl or benzyl, and the above groups may be further replaced by any combination of one or more halogens, cyano, nitro, C1-C6 alkoxy, C1-C6 haloalkyl or C1-C6 haloalkoxy.

[0038] The most preferred compound of this invention is that in Formula I:

[0039] When Het is selected from Het1 or Het3, R1 and R2 together with the atoms they are attached to form a 6-membered ring, and W1 and W2 are selected from oxygen; when Het is selected from Het6, R1 and R2 are selected from methyl, W1 and W2 are selected from oxygen, and W3 is selected from sulfur; when Het is selected from Het8, R1 is selected from methyl, R3 is selected from trifluoromethyl, R4 is selected from hydrogen, and W1 and W2 are selected from oxygen; when Het is selected from Het... 10 In this case, R3 is selected from trifluoromethyl, R4 and R6 are selected from hydrogen or methyl, and W1 is selected from oxygen; Het is selected from Het. 11 In this case, R1 and R4 are selected from hydrogen, R3 is selected from trifluoromethyl, R6 is selected from chlorine, and A is selected from nitrogen; Het is selected from Het. 12 In this case, R3 and R4 together with the atoms they are attached to form a 6-membered ring, W1 and W2 are selected from oxygen; Het is selected from Het. 14 In this case, R6 is selected from tert-butyl and W1 is selected from oxygen;

[0040] X is selected from hydrogen, fluorine, or chlorine;

[0041] Y is selected from fluorine or chlorine;

[0042] R is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl, or cyclohexyl.

[0043] The compounds particularly preferred by this invention are tetrasubstituted benzene compounds containing diazo substituents as described in Formula I, selected from any one of the following compounds:

[0044] 2-(2-chloro-4-fluoro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)phenyl)-2-diazoacetic acid methyl ester (compound 1-1);

[0045] 2-(2-chloro-4-fluoro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)phenyl)-2-diazoethyl ester (compounds 1-2);

[0046] 2-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenyl)-2-diazocarboxylate (compound 2-1);

[0047] 2-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenyl)-2-diazoethyl acetate (compound 2-2);

[0048] 2-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenyl)-2-diazoacetic acid isopropyl ester (compounds 2-4);

[0049] 2-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenyl)-2-diazoacetic acid cyclopentyl ester (compound 2-10);

[0050] 2-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenyl)-2-diazoacetic acid allyl ester (compound 2-13);

[0051] 2-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenyl)-2-diazoacetic acid (2-methoxyethyl) ester (compound 2-18).

[0052] The meanings of the substituents Ak, R, and R1 to R8 mentioned in Formula I, or when they are collective terms representing groups on phenyl, benzyl, or heterocyclic rings, are as follows:

[0053] Halogens refer to fluorine, chlorine, bromine, or iodine.

[0054] All carbon chains, i.e., the alkyl portion in all alkyl, haloalkyl, alkenyl, and alkynyl groups, can be straight-chain or branched. For example, C1 to C6 alkyl groups can be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, 2-methylbutyl, tert-pentyl, neopentyl, 1,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, isohexyl, sec-hexyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 2-methylpentyl, 3-methylpentyl, tert-hexyl, 1,3-dimethylbutyl, neohexyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-methyl-1-ethylpropyl, or 2-methyl-1-ethylpropyl, etc. Similarly, C2-C8 alkenyl groups can be vinyl, propenyl, allyl, 1-methylvinyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methylpropenyl, 2-methylpropenyl, 1-methylallyl, 2-methylallyl, 2,2-dimethylvinyl, etc. C2-C8 alkynyl groups can be ethynyl, propynyl, propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpropynyl, etc. The multiple bonds in the alkenyl or alkynyl groups can be at any position in each unsaturated group. C3-C8 cycloalkyl groups refer to saturated carbocyclic substituents with 3 to 8 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.

[0055] Halogenated alkyl, halogenated alkoxy, or halogenated alkenyl refers to an alkyl, alkoxy, or alkenyl group that is substituted with one or more halogen atoms, wherein the substituted halogen atoms may be the same or different.

[0056] If one group is substituted by another group, it should be understood that the group is substituted by one or more identical or different groups selected from those mentioned. Furthermore, the identical or different substitution characters contained in identical or different substituents can be chosen independently. This also applies to cyclic substituents formed from different atoms and units.

[0057] Furthermore, depending on the nature of the substituents and the manner in which they are attached, compounds of Formula I and their derivatives can exist as tautomers. For example, in a molecule of Formula I, the different distribution of positive and negative charges of the diazo substituents on the molecule can produce tautomers as shown in Formula I′.

[0058]

[0059] The compound of formula I of the present invention can be prepared by the following method, wherein, unless otherwise specified, the definitions of the other groups in the reaction formula are the same as above.

[0060] Compound I can be prepared by diazotization of compound II with corresponding azide reagents containing easily leaving groups.

[0061]

[0062] The azide reagent is prepared by reacting at a temperature of -30°C to the solvent's boiling point for 0.5–48 hours in a suitable solvent. Azide reagents are typically selected from acyl azide reagents (such as acetyl azide, benzoyl azide, p-nitrobenzoyl azide, etc.) or sulfonyl azide reagents (such as p-toluenesulfonyl azide, benzenesulfonyl azide, p-nitrobenzenesulfonyl azide, methanesulfonyl azide, trifluoromethanesulfonyl azide, etc.). Solvents can be selected from dichloromethane, chloroform, carbon tetrachloride, acetonitrile, n-hexane, cyclohexane, benzene, toluene, ethyl acetate, DMF, DMA, diethyl ether, methyl tert-butyl ether, THF, DMSO, or dioxane, etc. The addition of alkaline substances, such as triethylamine, DIEA, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,4-diazabicyclo[2.2.2]octane (triethylenediamine, DABCO), pyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, potassium phosphate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide, or potassium tert-butoxide, is beneficial to the reaction.

[0063] Compounds of Formula II can be prepared from compounds of Formula III by the method described below, depending on the different heterocyclic substituents.

[0064]

[0065] Among them, when Het is selected from Het1, W1 and W2 are oxygen, X is fluorine, Y is chlorine, and R1 and R2 are cyclic with the atoms they are attached to, such as methyl 2-chloro-4-fluoro-5-(1,3-dioxohexahydroimidazo[1,5-a]pyridin-2-yl)benzoate (CAS No. 91623-93-7), it can be synthesized and prepared with reference to EP104532A1.

[0066] Compounds of Formula II where Het is selected from Het2, W1 is oxygen, X and Y are both chlorine, R1 is difluoromethyl, and R2 is methyl, such as methyl 2,4-dichloro-5-(4-difluoromethyl-2,4-dihydro-5-methyl-3H-3-oxo-1,2,4-triazol-2-yl)benzoate (CAS No. 90208-80-3), can be synthesized according to JP58225070A; Additionally, compounds of Formula II where Het is selected from Het2, W1 is oxygen, X is fluorine, Y is chlorine, and R1 and R2 are cyclic with the atoms they are attached to, such as isopropyl 2-chloro-4-fluoro-5-(5,6,7,8-tetrahydro-3-oxo-1,2,4-triazolo[4,3-a]pyridin-2(3H)-yl)benzoate (CAS No. 90208-80-3), can be synthesized according to JP58225070A. No. 104799-38-4) can be used as a reference for synthesis and preparation of WO9422860A1.

[0067] When Het is selected from Het3, W1 is oxygen, X is fluorine, Y is chlorine, and R1 and R2 are cyclic with the atoms they are attached to, such as ethyl 2-chloro-4-fluoro-5-(1,3-dioxotetrahydro-1H-[1,2,4]triazolo[1,2-a]pyridazine-2(3H)-yl)benzoate (CAS No. 91150-86-6), it can be synthesized with reference to EP104484A1 and WO9527698A1.

[0068] When Het is selected from Het6, W1 and W2 are both oxygen, W3 is sulfur, X is fluorine, Y is chlorine, and R1 and R2 are both methyl compounds of formula II, such as isopropyl 2-chloro-4-fluoro-5-(3,5-dimethyl-4-thio-1,3,5-triazine-2,6(1H,3H)-dione-1-yl)benzoate (CAS No. 289883-20-1), it can be synthesized by referring to WO2000050409A1.

[0069] When Het is selected from Het8, W1 and W2 are both oxygen, X is fluorine, Y is chlorine, R1 is methyl, R2 is trifluoromethyl, and R4 is hydrogen, such as isopropyl 2-chloro-4-fluoro-5-(3,6-dihydro-3-methyl-2,6-dioxo-4-trifluoromethyl-1(2H)-pyrimidinyl)benzoate (CAS No. 105756-82-9), it can be synthesized by referring to EP195346A2, WO8810254A1 and WO2004009561A1.

[0070] When Het is selected from Het 10 Compounds of formula II, where W1 is oxygen, X is fluorine, Y is chlorine, R3 is trifluoromethyl, R4 is methyl, and R8 is hydrogen, such as ethyl 2-chloro-4-fluoro-5-(5-methyl-6-oxo-4-trifluoromethyl-1(6H)-pyridazinyl)benzoate (CAS No. 188489-20-5), can be synthesized by referring to WO9707104A1.

[0071] When Het is selected from Het 11 X is fluorine, Y is chlorine, R1 and R3 are hydrogen, R3 is trifluoromethyl, and R8 is a chlorine compound of formula II, such as isopropyl 2-chloro-4-fluoro-5-(3-chloro-5-trifluoromethylpyridin-2-yl)benzoate (CAS No. 372136-87-3), which can be synthesized by referring to DE4323916A1 and WO2001083459A2.

[0072] When Het is selected from Het 12Compounds of formula II, where W1 and W2 are oxygen, X is fluorine, Y is chlorine, and R1 and R2 are cyclic with the atoms they are attached to, such as ethyl 2-chloro-4-fluoro-5-(1,3,4,5,6,7-hexahydro-1,3-dioxo-2H-isoindol-2-yl)benzoate (CAS No. 81663-35-6), can be synthesized with reference to GB2071100A and EP97056A2.

[0073] When Het is selected from Het 13 Compounds of formula II, where W1 is oxygen, R1 is isopropyl, R5 is methyl, X is fluorine, and Y is chlorine, such as methyl 2-chloro-4-fluoro-5-(1,5-dihydro-3-methyl-1-isopropyl-5-oxo-1,2,4-triazol-4-yl)benzoate (CAS No. 136143-93-6), can be synthesized with reference to JP03106865A.

[0074] When Het is selected from Het 14 Compounds of formula II, where W1 is oxygen, X is fluorine, Y is chlorine, and R8 is tert-butyl, such as ethyl 2-chloro-4-fluoro-5-(5-tert-butyl-2-oxo-1,3,4-oxadiazol-3(2H)-yl)benzoate (CAS No. 95089-50-2), can be synthesized by referring to JP59148769A.

[0075] When Het is selected from Het 15 In a compound of formula II, where X is fluorine, Y is chlorine, R1 is difluoromethoxy, R2 is methyl, and R8 is chlorine, such as methyl 2-chloro-4-fluoro-5-(4-chloro-5-difluoromethoxy-1-methyl-1H-pyrazol-3-yl)benzoate (CAS No. 129631-27-2), it can be synthesized by referring to EP361114A1, EP443059A1, and EP647399A1; additionally, when Het is selected from Het... 15 Compounds of formula II, where X is fluorine, Y is chlorine, R8 is chlorine, and R1 and R2 are cyclic with the atoms they are attached to, such as methyl 2-chloro-4-fluoro-5-(3-chloro-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridin-2-yl)benzoate (CAS No. 153098-75-0), can be synthesized with reference to JP2022078425A.

[0076] Compound III can be prepared by reducing the nitro group of compound IV, which is usually commercially available.

[0077]

[0078] Compound of Formula III (commercially available) is reacted with a suitable reducing agent in a suitable solvent at a temperature of -30°C to the solvent's boiling point for 0.5–48 hours to prepare compound of Formula IV. The solvent can be an alcohol, such as methanol, ethanol, or isopropanol, or an ether, such as diethyl ether, tetrahydrofuran, or dioxane. The reducing agent is selected from hydrogen, a catalytic amount of a transition metal, or a catalytic amount of a transition metal compound; among which, transition metals are particularly suitable as compounds from Group VIII of the periodic table, preferably Ni, Pd, or Pt (used directly or supported by media such as activated carbon, alumina, or silica); hydrogen can be supplied from hydrogen storage cylinders, or it can be produced in situ by an active metal (such as reduced iron powder or reduced zinc powder) under acidic conditions (such as hydrochloric acid or sulfuric acid) and participate in the reduction reaction.

[0079] Compounds of Formula I and their salts, whether in the form of mixtures of isomers or pure isomers, can be used as herbicides. Herbicidal compositions containing compounds of Formula I effectively control plants in non-crops, especially at high application rates. Compounds of Formula I of the present invention exhibit good herbicidal activity against many important monocot and dicot weeds. While compounds of Formula I of the present invention exhibit excellent herbicidal activity against monocot and dicot weeds, they cause little or no damage to important economic crops such as wheat, barley, rye, rice, corn, soybeans, and cotton, and do not significantly affect these crops. This effect is particularly noticeable at low application rates. Therefore, the present invention also includes the use of compounds of Formula I for weed control in economic crops.

[0080] The present invention also includes a herbicidal composition using a compound of formula I as the active ingredient. The active ingredient in this herbicidal composition comprises 1 to 99% by weight. The herbicidal composition also includes an agriculturally acceptable carrier.

[0081] The herbicidal compositions of the present invention can be applied in various formulations. Typically, the compounds of the present invention are dissolved or dispersed in a carrier to formulate a formulation that facilitates dispersion when used as a herbicide. For example, these chemical formulations can be made into wettable powders or emulsifiable concentrates. Therefore, at least one liquid or solid carrier is added to these compositions, and a suitable surfactant is usually required.

[0082] Another embodiment of the present invention is a method for controlling weeds, comprising applying an effective amount of the herbicidal composition of the present invention to the surface of the weeds, the site of weed growth, or the growth medium thereof. A commonly chosen effective amount is typically 1 to 500 grams per hectare, preferably 2 to 250 grams per hectare. For certain applications, one or more other herbicides may be added to the herbicidal composition of the present invention, thereby producing additional advantages and effects.

[0083] The compounds of the present invention can be used alone or in combination with other known insecticides, fungicides, plant growth regulators or fertilizers.

[0084] It should be clearly stated that various modifications and alterations can be made within the scope defined by the claims of this invention. Specific implementation methods

[0085] The following synthetic examples, bioassay examples, and other experimental results are provided to further illustrate the present invention, but are not intended to limit the invention. Those skilled in the art should not construe this as limiting the scope of the above-described subject matter to the following compounds and / or bioassay results.

[0086] Synthesis Examples

[0087] Synthetic Example 1: Preparation of methyl 2-(2-chloro-4-fluoro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)phenyl)-2-diazoacetate (Compound 1-1)

[0088]

[0089] Step a) Synthesis of intermediate methyl 2-(2-chloro-4-fluoro-5-nitrophenyl)acetate

[0090]

[0091] 2-Chloro-4-fluoro-5-nitrophenylacetic acid (3.50 g, 15.0 mmol) was dissolved in 30 mL of toluene to form a suspension. Thionyl chloride (2.0 mL, 3.28 g, 27.6 mmol) was added, and the solution was refluxed for 3 h to form a clear solution. The solvent and excess thionyl chloride were removed by rotary evaporation. The remaining acyl chloride was diluted with an appropriate amount of dichloromethane for later use.

[0092] A solution of methanol (0.53 g, 16.5 mmol) and triethylamine (2.2 mL, 1.60 g, 15.8 mmol) was prepared by mixing in 15 mL of dichloromethane. The prepared acyl chloride solution was then added dropwise at room temperature. After the addition was complete, the reaction was continued at room temperature for 2 hours. The reaction was monitored by TLC until the endpoint was reached (product point: SiO2, EtOAc:PE = 1:9, R...). f After adding 0.33 mL of water to separate the layers, add 30 mL of water.

[0093] The aqueous layer was extracted with dichloromethane (20 mL × 3). The combined organic phases were washed sequentially with sat.NaHCO3 (20 mL), water (20 mL), and sat.NaCl (20 mL), dried over anhydrous MgSO4, concentrated, and separated by chromatography (SiO2, EtOAc:PE = 1:9) to obtain 2.30 g of yellow oil, with a yield of 62%.

[0094] Synthesis of intermediate methyl 2-(2-chloro-4-fluoro-5-aminophenyl)acetate in step b)

[0095]

[0096] 1.24 g (5.0 mmol) of methyl 2-(2-chloro-4-fluoro-5-nitrophenyl)acetate was dissolved in 15 mL of tetrahydrofuran to form a solution. After adding reduced iron powder (0.92 g, 16.5 mmol), the solution was cooled in an ice bath. Hydrochloric acid (3.5 mL, ~41.0 mmol) was slowly added dropwise, and the mixture was allowed to return to room temperature for 4 h. The reaction was monitored by TLC until the endpoint (product point: SiO2, EtOAc:PE = 1:3, R...). f =0.40).

[0097] After the reaction was stopped, the solvent was evaporated under reduced pressure. The residue was separated into two layers with 15 mL of ethyl acetate and 30 mL of water. The aqueous layer was extracted with ethyl acetate (15 mL × 3). The combined organic phases were washed with Sat. NaCl (25 mL × 2), dried over anhydrous MgSO4, concentrated, and chromatographically separated (SiO2, EtOAc:PE = 1:9 → 1:4) to obtain a yellow oil. Upon cooling, approximately 0.67 g of a pale yellow waxy solid precipitated, which was the reduction product, with a yield of ~62%.

[0098] Step c) Synthesis of intermediate methyl 2-(2-chloro-4-fluoro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)phenyl)acetate

[0099]

[0100] Methyl 2-(2-chloro-4-fluoro-5-aminophenyl)acetate (653 mg, 3.0 mmol) was dissolved in 10 mL of ethyl acetate to form a solution. Triethylamine (364 mg, 3.6 mmol) and carbonyl diimidazole (1.17 g, 7.2 mmol) were added, and the mixture was refluxed for 0.5 h. Then, 1,3-dimethylthiourea (375 mg, 3.6 mmol) was added, followed by reflux for 2 h. The reaction was monitored by TLC until the endpoint (product point: SiO2, EtOAc:PE = 1:3, R...). f=0.10), then water (40 mL) was added, and the mixture was extracted with ethyl acetate (30 mL × 3). The combined organic phases were washed with sat.NaCl (30 mL × 2), dried over anhydrous MgSO4, and concentrated to obtain a yellow oil. The oil was separated by column chromatography (SiO2, EtOAc:PE = 1:9 → 1:4) to obtain 729 mg of the yellow oil, which was the target product, with a yield of ~65%.

[0101] Step d) Synthesis of compound 1-1

[0102]

[0103] Methyl 2-(2-chloro-4-fluoro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)phenyl)acetate (748 mg, 2.0 mmol) was dissolved in 7 mL of acetonitrile to form a solution. Phthalimide 1,8-diazabicyclo[5.4.0]undec-7-ene salt (228 mg, 1.5 mmol) and p-toluenesulfonyl azide (394 mg, 2.0 mmol) were added, and the reaction was carried out at room temperature for 4 h. The reaction was monitored by TLC until the endpoint (product point: SiO2, EtOAc:PE = 1:3, R f =0.70).

[0104] After the reaction was stopped, the solvent was evaporated under reduced pressure. The residue was separated into two layers with 15 mL of ethyl acetate and 30 mL of water. The aqueous layer was extracted with ethyl acetate (15 mL × 3). The combined organic phases were washed with Sat. NaCl (25 mL × 2), dried over anhydrous MgSO4, concentrated, and separated by chromatography (SiO2, EtOAc:PE = 1:9 → 1:4) to obtain 0.66 g of yellow oil, which was the target product, with a yield of ~82%.

[0105] Synthetic Example 2: Preparation of ethyl 2-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenyl)-2-diazoethyl acetate (compound 2-2)

[0106]

[0107] Step a) Synthesis of intermediate 2-(2-chloro-4-fluoro-5-nitrophenyl)acetic acid

[0108]

[0109] 2-(2-chloro-4-fluoro)phenylacetic acid (3.77 g, 20.0 mmol) was dissolved in 10 mL of concentrated sulfuric acid to form a suspension. Fuming nitric acid (1.4 mL, 95%, ~30 mmol) was added dropwise to the suspension under ice bath conditions. After the addition was complete, the ice bath was removed, and the reaction was allowed to proceed at room temperature for 2 h. After the reaction was stopped, the reaction mixture was poured into 100 mL of an ice-water mixture to precipitate a solid. The solid was filtered, washed with water, and dried to obtain 4.40 g of a pale yellow solid, which was the nitration product, with a yield of 94%.

[0110] Step b) Synthesis of intermediate ethyl 2-(2-chloro-4-fluoro-5-nitrophenyl)

[0111]

[0112] 2-Chloro-4-fluoro-5-nitrophenylacetic acid (3.50 g, 15.0 mmol) was dissolved in 30 mL of toluene to form a suspension. Thionyl chloride (2.0 mL, 3.28 g, 27.6 mmol) was added, and the solution was refluxed for 3 h to form a clear solution. The solvent and excess thionyl chloride were removed by rotary evaporation. The remaining acyl chloride was diluted with an appropriate amount of dichloromethane for later use.

[0113] A solution of ethanol (0.76 g, 16.5 mmol) and triethylamine (2.2 mL, 1.60 g, 15.8 mmol) was prepared by mixing in 15 mL of dichloromethane. The prepared acyl chloride solution was then added dropwise at room temperature. After the addition was complete, the reaction was continued at room temperature for 2 hours. The reaction was monitored by TLC until the endpoint was reached (product point: SiO2, EtOAc:PE = 1:9, R...). f After adding 0.33 mL of water to separate the layers, add 30 mL of water.

[0114] The aqueous layer was extracted with dichloromethane (20 mL × 3). The combined organic phases were washed sequentially with sat.NaHCO3 (20 mL), water (20 mL), and sat.NaCl (20 mL), dried over anhydrous MgSO4, concentrated, and separated by chromatography (SiO2, EtOAc:PE = 1:9) to obtain 2.40 g of yellow oil, which was the esterification product, with a yield of 64%.

[0115] Step c) Synthesis of intermediate ethyl 2-(2-chloro-4-fluoro-5-aminophenyl)

[0116]

[0117] Ethyl 2-(2-chloro-4-fluoro-5-nitrophenyl)acetate (1.31 g, 5.0 mmol) was dissolved in 15 mL of tetrahydrofuran to form a solution. Reduced iron powder (0.92 g, 16.5 mmol) was added, and the solution was cooled in an ice bath. Hydrochloric acid (3.5 mL, ~41.0 mmol) was slowly added dropwise, and the reaction was allowed to return to room temperature for 4 h. The reaction was monitored by TLC until the endpoint (product point: SiO2, EtOAc:PE = 1:3, R...). f =0.40).

[0118] After the reaction was stopped, the solvent was evaporated under reduced pressure. The residue was separated into two layers with 15 mL of ethyl acetate and 30 mL of water. The aqueous layer was extracted with ethyl acetate (15 mL × 3). The combined organic phases were washed with Sat. NaCl (25 mL × 2), dried over anhydrous MgSO4, concentrated, and separated chromatographically (SiO2, EtOAc:PE = 1:9, then 1:4) to obtain a yellow oil. Upon cooling, approximately 0.72 g of pale yellow waxy solid precipitated, which was the reduction product, with a yield of ~62%.

[0119] Step d) Synthesis of intermediate ethyl 2-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenyl)

[0120]

[0121] Ethyl 2-(2-chloro-4-fluoro-5-aminophenyl)acetate (695 mg, 3.0 mmol) was dissolved in 10 mL of acetic acid to form a solution. Ethyl 3-(3,3-dimethylurea)-4,4,4-trifluorocrotonate (915 mg, 3.6 mmol) was added, and the mixture was refluxed for 4 h. The reaction was monitored by TLC until the endpoint (product point: SiO2, EtOAc:PE = 1:3, R...). f =0.10), remove acetic acid by rotary evaporation, add water (40 mL) to the residue, extract with ethyl acetate (30 mL × 3), wash the combined organic phases with sat.NaCl (30 mL × 2), dry with anhydrous MgSO4, concentrate to obtain yellow oil, which is used directly in the next reaction without further purification.

[0122] The intermediate obtained in the previous step was dissolved in 10 mL of DMF to form a solution. Potassium carbonate (622 mg, 4.5 mmol) was added at room temperature, followed by the addition of iodomethane (639 mg, 4.5 mmol), and the reaction was allowed to proceed overnight. The reaction progress was monitored by TLC (product spot: SiO2, EtOAc:PE = 1:3, R). f =0.45).

[0123] After the reaction was stopped, 30 mL of ethyl acetate and 30 mL of saturated brine were added to separate the layers. The aqueous layer was extracted with ethyl acetate (20 mL × 3). The combined organic phases were washed successively with water (30 mL) and sat.NaCl (30 mL × 2). After drying with anhydrous MgSO4, an appropriate amount of silica gel was added for concentration. Column chromatography (SiO2, EtOAc:PE = 1:9 → 1:4) yielded 1026 mg of yellow oil, which was the target product, with a yield of ~84%.

[0124] Step e) Synthesis of compound 2-2

[0125]

[0126] Ethyl 2-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenyl)acetate (409 mg, 1.0 mmol) was dissolved in 5 mL of acetonitrile to form a solution. Then, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, 91 mg, 0.6 mmol) and p-toluenesulfonyl azido (217 mg, 1.1 mmol) were added sequentially. The reaction was carried out overnight at room temperature, and the reaction progress was monitored by TLC (product spot: SiO2, EtOAc:PE = 1:3, R...). f =0.60).

[0127] After the reaction was complete, 20 mL of dichloromethane and 20 mL of saturated brine were added to separate the layers. The aqueous layer was extracted with dichloromethane (10 mL × 3). The combined organic phases were washed successively with water (20 mL) and sat.NaCl (20 mL × 2). After drying with anhydrous MgSO4, an appropriate amount of silica gel was added for concentration. Column chromatography (SiO2, EtOAc:PE = 1:9) was used to separate the compounds, yielding 300 mg of compound 2-2 as a yellow oil, with a yield of 69%.

[0128] Other compounds of Formula I can be obtained by replacing the starting material and / or intermediate reagent according to the method described above. The structures and physicochemical properties of some compounds of Formula I are shown in Tables 1 to 2.

[0129]

[0130] Table 1

[0131]

[0132]

[0133] Table 2

[0134]

[0135] Biometrics Example

[0136] Example 1: Testing of herbicidal activity

[0137] Stem and leaf activity test: Sow the seeds of broadleaf weeds (amaranth, shepherd's purse, black nightshade), grass weeds (barnyard grass, barnyard grass, sedge) or sedge weeds (sedge) into plastic cups with a diameter of 5cm filled with nutrient soil. After sowing, cover with 0.1-0.5cm of soil, press down, and let the plastic cup absorb enough water from the bottom. Place in a greenhouse and cultivate using conventional methods. After the weeds have 2-3 leaves, spray the stems and leaves.

[0138] Soil activity test: The sowing method was the same as that for the stem and leaf activity test, and soil spraying was carried out 24 hours after sowing.

[0139] Test and efficacy evaluation methods: The technical grade drug was dissolved in N,N-dimethylformamide solvent, and then the required concentration of the test solution was prepared using 0.1% Tween 80 water according to the experimental requirements. The solution was sprayed at the designed dosage using a 3WP-2000 mobile spray tower (manufactured by Nanjing Agricultural Machinery Research Institute) (spray pressure 0.3 MPa, spray volume 45 mL / m²). 2 The nozzle model was TP6501E, the spray height was 300mm, and the nozzle travel speed was 320mm / s. The experiment was repeated three times. After the pesticide-treated material was allowed to air dry naturally, it was transferred to a greenhouse and cultivated using conventional methods. The weed reaction symptoms were observed and recorded regularly. The efficacy of the pesticide against weeds was investigated 14 days after application, expressed as 0-100%, where "0" indicates no efficacy and "100%" indicates that the weeds were completely killed.

[0140] The Chinese, English, and Latin names of the weeds used in the experiment are listed below:

[0141] Amaranth (three-colored amaranth, Amaranthus tricolor);

[0142] Shepherd's purse (Capsella bursa-pastoris);

[0143] Black nightshade (Solanum nigrum);

[0144] Crabgrass (large crabgrass, Digitaria sanguinalis);

[0145] Barnyard grass (Echinocloa crus-galli);

[0146] Chinese sprangletop, Leptochloa chinensis;

[0147] Rice flatsedge (Cyperus iria).

[0148] The herbicidal activity test results of foliar application showed that compounds of formula I generally had good control efficacy against broadleaf weeds. Some of the tested compounds showed good control efficacy at an application rate of 37.5 g ai / hm². 2 It has excellent control efficacy against amaranth, with a control efficacy of not less than 70%. Such compounds are 2-1, 2-2, 2-3, 2-4, 2-5, 2-9, 2-10, 2-11, 2-13 and 2-16.

[0149] The herbicidal activity test results of foliar application showed that compounds of formula I generally had good control efficacy against broadleaf weeds. Some of the tested compounds showed good control efficacy at an application rate of 37.5 g ai / hm². 2 It has excellent control efficacy against shepherd's purse, with a control efficacy of no less than 70%. Such as compounds 2-1, 2-2, 2-3, 2-5 and 2-9.

[0150] The herbicidal activity test results of foliar application showed that compounds of formula I generally had good control efficacy against broadleaf weeds. Some of the tested compounds showed good control efficacy at an application rate of 37.5 g ai / hm². 2 It has excellent control efficacy against black nightshade, with a control efficacy of not less than 70%. Such as compounds 2-1, 2-2, 2-3, 2-4, 2-5, 2-9, 2-11, 2-13 and 2-18.

[0151] The herbicidal activity test results of foliar application showed that compounds of formula I generally had good control efficacy against grassy weeds. Some of the tested compounds showed good control efficacy at an application rate of 37.5 g ai / hm². 2 These compounds, such as compounds 2-1, 2-2, and 2-9, exhibit good control efficacy against crabgrass, with an efficacy of no less than 50%.

[0152] The herbicidal activity test results of foliar application showed that compounds of formula I generally had good control efficacy against grassy weeds. Some of the tested compounds showed good control efficacy at an application rate of 37.5 g ai / hm². 2 These compounds, such as compounds 2-1 and 2-2, have good control efficacy against barnyard grass, with a control efficacy of no less than 50%.

[0153] The herbicidal activity test results of foliar application showed that compounds of formula I generally had good control efficacy against grassy weeds. Some of the tested compounds showed good control efficacy at an application rate of 37.5 g ai / hm². 2The following compounds exhibit excellent control efficacy against Echinochloa crus-galli, with a control efficacy of no less than 50%. Examples include compounds 2-1, 2-2, 2-3, 2-4, 2-5, and 2-18.

[0154] The herbicidal activity test results of foliar application showed that compounds of formula I generally had good control efficacy against sedges. Some of the tested compounds showed good control efficacy at an application rate of 37.5 g ai / hm. 2 The following compounds exhibit excellent control efficacy against *Cyperus diffusa*, with a control efficacy of no less than 70%. Examples include compounds 2-1, 2-2, 2-3, 2-5, and 2-18.

[0155] Soil-applied herbicidal activity tests showed that compounds of formula I generally exhibited good control efficacy against broadleaf weeds. Some of the tested compounds showed good control efficacy at an application rate of 37.5 g ai / hm². 2 The following compounds exhibit excellent control efficacy against amaranth, with a control efficacy of no less than 70%. Examples include compounds 1-2, 2-1, 2-2, 2-3, 2-4, 2-5, 2-9, 2-13, 2-16, and 2-18.

[0156] Soil-applied herbicidal activity tests showed that compounds of formula I generally exhibited good control efficacy against broadleaf weeds. Some of the tested compounds showed good control efficacy at an application rate of 37.5 g ai / hm². 2 The following compounds exhibit excellent control efficacy against shepherd's purse, with a control efficacy of no less than 70%. Examples include compounds 1-2, 2-1, 2-2, 2-3, 2-4, 2-13, 2-16, and 2-18.

[0157] Soil-applied herbicidal activity tests showed that compounds of formula I generally exhibited good control efficacy against broadleaf weeds. Some of the tested compounds showed good control efficacy at an application rate of 37.5 g ai / hm². 2 The following compounds exhibit excellent control efficacy against black nightshade, with a control efficacy of no less than 70%. Examples include compounds 1-1, 1-2, 2-1, 2-2, 2-3, 2-4, 2-5, 2-9, 2-10, 2-11, 2-13, 2-16, and 2-18.

[0158] Soil-applied herbicidal activity tests showed that compounds of formula I generally exhibited good control efficacy against grassy weeds. Some of the tested compounds showed good control efficacy at an application rate of 37.5 g ai / hm². 2 The following compounds exhibit good control efficacy against barnyardgrass, with an efficacy of no less than 50%. Examples include compounds 1-1, 1-2, 2-1, 2-2, 2-3, 2-4, 2-5, 2-9, 2-11, 2-13, 2-16, and 2-18.

[0159] Soil-applied herbicidal activity tests showed that compounds of formula I generally exhibited good control efficacy against grassy weeds. Some of the tested compounds showed good control efficacy at an application rate of 37.5 g ai / hm². 2These compounds, such as compounds 2-1, 2-2, 2-4, 2-9, and 2-18, have good control efficacy against barnyard grass, with a control efficacy of no less than 50%.

[0160] Soil-applied herbicidal activity tests showed that compounds of formula I generally exhibited good control efficacy against grassy weeds. Some of the tested compounds showed good control efficacy at an application rate of 37.5 g ai / hm². 2 The following compounds have good control efficacy against Echinochloa crus-galli, with a control efficacy of not less than 50%. Examples include compounds 1-1, 1-2, 2-1, 2-2, 2-3, 2-4, 2-5, 2-9, 2-10, 2-11, 2-13, 2-16, and 2-18.

[0161] Soil-applied herbicidal activity tests showed that compounds of formula I generally exhibited good control efficacy against sedges. Some of the tested compounds showed good control efficacy at an application rate of 37.5 g ai / hm². 2 The following compounds, such as compounds 1-1, 1-2, 2-1, 2-2, 2-3, 2-4, 2-5, 2-9, 2-11, 2-13, and 2-18, have good control efficacy against Cyperus rotundus, with a control efficacy of not less than 70%.

Claims

1. A tetrasubstituted benzene compound containing a diazo substituent, characterized in that, The tetrasubstituted benzene compound containing a diazo substituent has the structure shown in Formula I: in: Het is selected from 3- to 7-membered monocyclic or 6- to 10-membered bicyclic substituents, each ring substituent containing a ring member selected from carbon atoms and 0 to 5 heteroatoms, these heteroatoms being independently selected from a maximum of 2 O atoms, a maximum of 2 S atoms and a maximum of 5 N atoms, each ring substituent being optionally substituted by a maximum of 5 substituents, the substituents on the ring being independently selected from halogen, cyano, amino, hydroxy, nitro, mercapto, C1 to C6 alkyl, C2 to C8 alkenyl, C2 to C8 alkynyl, C3 to C8 cycloalkyl, C1 to C6 haloalkyl, C1 to C6 alkoxy, C1 to C6 alkylamino, C1 to C6 alkylthio, C1 to C6 alkylsulfinyl, C1 to C6 alkylsulfonyl, C1 to C6 alkoxy-C1 to C6 alkyl, C3 to C8 cycloalkyl-C1 to C6 alkyl, phenyl or benzyl; X is selected from hydrogen, halogen, C1-C6 alkyl or C1-C6 alkoxy; Y is selected from halogen, cyano, nitro, C1-C6 alkyl, C1-C6 alkoxy, CONH2 or CSNH2; R is selected from C1-C6 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C1-C6 haloalkyl, C1-C6 alkoxy-C1-C6 alkyl, C1-C6 alkylthio-C1-C6 alkyl, C1-C6 alkylamino-C1-C6 alkyl, C3-C8 cycloalkyl-C1-C6 alkyl, C2-C8 oxecycloalkyl-C1-C6 alkyl, C1-C6 alkoxycarbonyl-C1-C6 alkyl, phenyl or benzyl, and the above groups may be further replaced by any combination of one or more halogens, cyano, nitro, C1-C6 alkoxy, C1-C6 haloalkyl or C1-C6 haloalkoxy.

2. The tetrasubstituted benzene compound containing a diazo substituent according to claim 1, characterized in that, In the structure of Equation I: Het is selected from 5- or 6-membered monocyclic substituents or 8- to 10-membered bicyclic substituents, each cyclic substituent containing a ring member selected from a carbon atom and 0 to 5 heteroatoms, these heteroatoms being independently selected from a maximum of 2 O atoms, a maximum of 2 S atoms, and a maximum of 5 N atoms, each cyclic substituent being optionally substituted by a maximum of 5 substituents, the substituents being independently selected from halogens, cyano, amino, hydroxyl, nitro, mercapto, C1-C6 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 alkylamino, C1-C6 alkylthio, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 alkoxy-C1-C6 alkyl, C3-C8 cycloalkyl-C1-C6 alkyl, phenyl, or benzyl; X is selected from hydrogen or halogen; Y is selected from halogen, cyano, nitro, CONH2 or CSNH2; R is selected from C1-C6 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C1-C6 haloalkyl, C1-C6 alkoxy-C1-C6 alkyl, C1-C6 alkylthio-C1-C6 alkyl, C1-C6 alkylamino-C1-C6 alkyl, C3-C8 cycloalkyl-C1-C6 alkyl, C2-C8 oxecycloalkyl-C1-C6 alkyl, C1-C6 alkoxycarbonyl-C1-C6 alkyl, phenyl or benzyl, and the above groups may be further replaced by any combination of one or more halogens, cyano, nitro, C1-C6 alkoxy, C1-C6 haloalkyl or C1-C6 haloalkoxy.

3. The tetrasubstituted benzene compound containing a diazo substituent according to claims 1-2, characterized in that, In the structure of Equation I: Het is selected from in, W1, W2, and W3 are each independently oxygen or sulfur; A is selected from N or CR5; R1 and R2 are each independently selected from hydrogen, cyano, amino, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 haloalkoxy, C3-C7 cycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, benzyl, cyanoC2-C6 alkyl or OR7, or R1 and R2 together with the atoms they are attached to form a 3- to 7-membered ring, and the 3- to 7-membered ring formed by R1 and R2 together with the atoms they are attached to may be further substituted by any combination of one or more halogens, nitro, cyano, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylamino or C1-C4 alkylthio; R3 and R4 are each independently selected from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 haloalkoxy, C3-C7 cycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, OR7, and S(O). n R7, OSO2R7 or NR7R8, or R3 and R4 together with the atoms to which they are attached form a 3- to 7-membered ring, and the 3- to 7-membered ring formed by R3 and R4 together with the atoms to which they are attached may be further substituted by any combination of one or more halogens, nitro, cyano, C1 to C4 alkyl, C1 to C4 alkoxy, C1 to C4 alkylamino or C1 to C4 alkylthio, where n is 0, 1 or 2; R5 is selected from hydrogen, halogen, or C1-C6 alkyl; R6 is selected from hydrogen, halogens, C1-C6 alkyl groups, OR7, SR7, and S(O). n R7, OSO2R7 or NR7R8, where n is 0, 1 or 2; R7 and R8 are each independently selected from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C7 cycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, phenyl or benzyl, and the other groups mentioned above, except for hydrogen, may be further replaced by any combination of one or more halogens, nitro, cyano, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylamino or C1-C4 alkylthio. X is selected from hydrogen, fluorine, or chlorine; Y is selected from fluorine, chlorine, bromine, or cyano groups; R is selected from C1-C6 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C1-C6 haloalkyl, C1-C6 alkoxy-C1-C6 alkyl, C1-C6 alkylthio-C1-C6 alkyl, C1-C6 alkylamino-C1-C6 alkyl, C3-C8 cycloalkyl-C1-C6 alkyl, C2-C8 oxecycloalkyl-C1-C6 alkyl, C1-C6 alkoxycarbonyl-C1-C6 alkyl, phenyl or benzyl, and the above groups may be further replaced by any combination of one or more halogens, cyano, nitro, C1-C6 alkoxy, C1-C6 haloalkyl or C1-C6 haloalkoxy.

4. The tetrasubstituted benzene compound containing a diazo substituent according to claims 1-3, characterized in that, In the structure of Equation I: Het is selected from Het1, Het2, Het3, Het4, Het6, Het8, Het 10 , Het 11 , Het 12 or Het 14 ; X is selected from hydrogen, fluorine, or chlorine; Y is selected from fluorine, chlorine, bromine, or cyano groups; Z is selected from oxygen or sulfur; R is selected from C1-C6 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C1-C6 haloalkyl, C1-C6 alkoxy-C1-C6 alkyl, C1-C6 alkylthio-C1-C6 alkyl, C1-C6 alkylamino-C1-C6 alkyl, C3-C8 cycloalkyl-C1-C6 alkyl, C2-C8 oxecycloalkyl-C1-C6 alkyl, C1-C6 alkoxycarbonyl-C1-C6 alkyl, phenyl or benzyl, and the above groups may be further replaced by any combination of one or more halogens, cyano, nitro, C1-C6 alkoxy, C1-C6 haloalkyl or C1-C6 haloalkoxy.

5. The tetrasubstituted benzene compound containing a diazo substituent according to claims 1-4, characterized in that, In the structure of Equation I: When Het is selected from Het1 or Het3, R1 and R2 together with the atoms they are attached to form a 6-membered ring, and W1 and W2 are selected from oxygen; when Het is selected from Het6, R1 and R2 are selected from methyl, W1 and W2 are selected from oxygen, and W3 is selected from sulfur; when Het is selected from Het8, R1 is selected from methyl, R3 is selected from trifluoromethyl, R4 is selected from hydrogen, and W1 and W2 are selected from oxygen; when Het is selected from Het... 10 In this case, R3 is selected from trifluoromethyl, R4 and R6 are selected from hydrogen or methyl, and W1 is selected from oxygen; Het is selected from Het. 11 In this case, R1 and R4 are selected from hydrogen, R3 is selected from trifluoromethyl, R6 is selected from chlorine, and A is selected from nitrogen; Het is selected from Het. 12 In this case, R3 and R4 together with the atoms they are attached to form a 6-membered ring, W1 and W2 are selected from oxygen; Het is selected from Het. 14 In this case, R6 is selected from tert-butyl and W1 is selected from oxygen; X is selected from hydrogen, fluorine, or chlorine; Y is selected from fluorine or chlorine; R is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl, or cyclohexyl.

6. The tetrasubstituted benzene compound containing a diazo substituent according to claims 1-5, characterized in that, The tetrasubstituted benzene compounds containing diazo substituents are selected from any one of the following compounds: 2-(2-chloro-4-fluoro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)phenyl)-2-diazoacetic acid methyl ester (compound 1-1); 2-(2-chloro-4-fluoro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)phenyl)-2-diazoethyl ester (compounds 1-2); 2-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenyl)-2-diazocarboxylate (compound 2-1); 2-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenyl)-2-diazoethyl acetate (compound 2-2); 2-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenyl)-2-diazoacetic acid isopropyl ester (compounds 2-4); 2-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenyl)-2-diazoacetic acid cyclopentyl ester (compound 2-10); 2-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenyl)-2-diazoacetic acid allyl ester (compound 2-13); 2-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenyl)-2-diazoacetic acid (2-methoxyethyl) ester (compound 2-18).

7. The use of the tetrasubstituted benzene compound containing a diazo substituent according to any one of claims 1-6 in the control of weeds.

8. A herbicidal composition, characterized in that, The herbicidal composition comprises an active ingredient and an agriculturally acceptable carrier, wherein the active ingredient is a tetrasubstituted benzene compound containing a diazo substituent as described in any one of claims 1-6.

9. The herbicidal composition according to claim 8, characterized in that, The active ingredient in the herbicidal composition has a weight percentage of 1% to 99%.

10. A method for controlling weeds, characterized in that, Applying a herbicidal effective dose of a tetrasubstituted benzene compound containing a diazo substituent as described in any one of claims 1-6, or a herbicidal composition as described in claims 8 and / or 9, to weeds or the weed growing medium or site.

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