CN111961041A - Thiotriazinone isoxazoline compound, preparation method and application thereof, protoporphyrinogen oxidase inhibitor and herbicide - Google Patents

Thiotriazinone isoxazoline compound, preparation method and application thereof, protoporphyrinogen oxidase inhibitor and herbicide Download PDF

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CN111961041A
CN111961041A CN201910419966.1A CN201910419966A CN111961041A CN 111961041 A CN111961041 A CN 111961041A CN 201910419966 A CN201910419966 A CN 201910419966A CN 111961041 A CN111961041 A CN 111961041A
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CN111961041B (en
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席真
张瑞波
王大伟
于淑一
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Nankai University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
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Abstract

The invention relates to the field of pesticides, in particular to a thiotriazinone isoxazoline compound, a preparation method and application thereof, and a herbicide containing the thiotriazinone isoxazoline compound and protoporphyrinogen oxidase inhibitor. The thiotriazinone-containing isoxazoline compound has a structure shown in a formula (I), wherein R is1、R2Each independently selected from H, -NH2、C1‑C6Alkyl or C1‑C6A haloalkyl group of (a); and the like. The thiotriazineone isoxazoline compound provided by the invention can effectively inhibit the activity of plant protoporphyrinogen oxidase and has good performanceHerbicidal activity and crop safety.

Description

Thiotriazinone isoxazoline compound, preparation method and application thereof, protoporphyrinogen oxidase inhibitor and herbicide
Technical Field
The invention relates to the field of agricultural agents, in particular to thiotriazinone isoxazoline compounds, a preparation method and application thereof, and a herbicide containing the thiotriazinone isoxazoline compounds and protoporphyrinogen oxidase inhibitors.
Background
The history of use of herbicides dates back to around 60 th in the 20 th century, and over half a century of research, a very wide variety of herbicides have been developed which exert an inhibitory effect on the growth of weeds through various mechanisms. Some of these herbicides are directed against one or more enzymes in the weeds, which act normally by inhibiting these enzymes, thereby preventing the weeds from growing normally. With the widespread and prolonged use of these herbicides, weeds have increasingly developed resistance to these enzyme-inhibiting herbicides, exhibiting a tendency to be difficult to inhibit. The discovery of compounds with novel structures and higher enzyme inhibitory activity is an important approach to address weed resistance.
Prior art CN105753853A discloses a compound having herbicidal action as shown in the following structure,
Figure BDA0002065692300000011
although herbicides of this structure have a good herbicidal effect, it is expected that weeds will also develop resistance to such herbicides in the near future.
In addition, most of the existing herbicides (including the herbicide with the structure disclosed in CN 105753853A) not only have inhibition effect on weeds, but also have strong inhibition effect on crops. This makes these herbicides not applicable in the growing process of crops. However, in actual production, there is a high demand for weeding during the growth of crops.
Therefore, it is very important to find a herbicide with high crop safety. And it is also very important to constantly search for new herbicides to combat weed resistance.
Disclosure of Invention
The invention aims to overcome the problems and provide a thiotriazineone isoxazoline compound, a preparation method and application thereof, and a protoporphyrinogen oxidase inhibitor and a herbicide containing the thiotriazineone isoxazoline compound.
The thiotriazineone isoxazoline compound can efficiently inhibit the activity of protoporphyrinogen oxidase, so that the compound has good herbicidal activity; meanwhile, the thiotriazinone isoxazoline compound has high crop safety, establishes good selectivity for key crops such as corn, rice and the like, and can effectively remove weeds in crop fields on the premise of ensuring safe growth of the crops.
The inventor of the invention finds that the compound with a specific structure can generate very strong inhibition effect on protoporphyrinogen oxidase (PPO, EC1.3.3.4, which is the last common enzyme in the same biosynthesis step of chlorophyll and heme, is widely existed in various organisms, can catalyze and oxidize protoporphyrinogen IX into protoporphyrin IX, and the protoporphyrin IX is an important substance for synthesizing chlorophyll) in weeds, and is better than herbicides with inhibitory activity on PPO reported in the prior art. The action mechanism is as follows: inhibition of PPO enzyme activity in plants results in rapid accumulation and spill of the substrate protoporphyrinogen IX into the cytoplasm. Protoporphyrinogen IX can be auto-oxidized to protoporphyrin IX in the cytoplasm, and protoporphyrin IX reacts with oxygen under irradiation of light and generates a large amount of singlet oxygen, thereby causing peroxidation of lipids and albino death of plants.
The invention provides a thiotriazinone isoxazoline compound, which has a structure shown in a formula (I),
Figure BDA0002065692300000021
wherein:
R1、R2each independently selected from H, -NH2、C1-C6Alkyl or C1-C6A haloalkyl group of (a);
R3、R4、R5、R6each independently selected from H, halogen, -CN, C1-C6Alkyl group of (C)1-C6Haloalkyl) -O-or (C)1-C6Alkyl) -SO of2-；
R7、R8Each independently selected from H, -CN, C1-C6Alkyl or C1-C6A haloalkyl group of (a);
R9、R10each independently selected from H, -CN, C1-C6Alkyl of (C)1-C6Haloalkyl, -CO-OR11、 -CH2OR12、-CONR13R14Phenyl or benzyl;
R11selected from H, C1-C6Alkyl of (C)1-C6Halogenoalkyl of, C3-C6Alkenyl of, C3-C6Alkynyl (C)1-C6Alkyl) -O- (C of1-C6Alkyl of (C) -, (C)1-C6Alkyl) -CO-O- (C)1-C4Alkyl group of (C), (C)1-C6Alkyl) -CO-NH- (C)1-C4Alkyl of (2), benzyl, having 1 to 4 substituents R3A benzyl group of,
Figure BDA0002065692300000022
Wherein the substituent R3Each independently selected from: halogen, -CN, -NO2、C1-C8Alkyl of (C)1-C8Haloalkyl of (A), (B), (C)1-C8Alkyl group of (A) O-, (C)1-C8Haloalkyl) -O-, (C)1-C8Alkyl group of (A) O-CO-, (C)1-C8Alkyl) -S-or (C)1-C8Alkyl) -SO of2-; wherein R is15、R16Each independently selected from the group I consisting of15/16: H. -CN, halogen, substituted or unsubstitutedC of (A)1-C10Alkyl, substituted or unsubstituted C1-C10Alkoxy, substituted or unsubstituted C3-C10Substituted or unsubstituted C containing 0 to 3 heteroatoms selected from at least N, O and S5-C10Aryl, substituted or unsubstituted pyridyl, substituted or unsubstituted thienyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, substituted or unsubstituted-CO- (C)1-C12Alkyl of (a) -, substituted or unsubstituted- (C)1-C5Alkyl) -CO- (C)1-C5Alkyl of (a) -, substituted or unsubstituted- (C)1-C3Ester group of (1) - (C)1-C3Alkyl of (a) -, the group I15/16The substituent in (A) is selected from one or more of halogen, nitro, cyano and amino; or, R15And R16Are first selected from the above group I15/16Then connecting to form a ring; r15And R16Not H at the same time;
R12selected from H, C1-C6Alkyl of (C)1-C6Haloalkyl of (A), (B), (C)1-C6Alkyl group of (A) O-CO-, (C)1-C6Alkyl group of (2) - (C)1-C6Haloalkyl) -CO-, (C)3-C6Cycloalkyl) -CO-, (C)3-C6Halocycloalkyl) -CO-, (C)1-C6Alkyl) -SO of2-、(C1-C6Haloalkyl) -SO of2-、(C1-C6Alkyl) -NH-SO of2-、(C1-C6Alkyl of (2)2-N-SO2-、 (C1-C6Alkyl) -NH-CO-, (C)1-C6Alkyl of (2)2-N-CO-、(C1-C6Alkyl of (2)2-N-CS-、(C1-C6Alkyl) -S- (C of2-C6Alkyl) -CO-, phenyl with 1-4 substituents R4Phenyl and phenyl- (C)1-C2Alkyl group of (a) -, with 1-4 substituents R5Phenyl- (C)1-C2Alkyl of (2) -, phenyl- (C)2-C4Alkenyl) with 1-4 substituents R6Phenyl- (C)2-C4Alkenyl of (a), phenyl-CO-, with 1-4 substituents R7phenyl-CO-, phenyl- (C)1-C2Alkyl) -CO-having 1-4 substituents R8Phenyl- (C)1-C2Alkyl) -CO-, phenyl-O- (C)1-C2Alkyl) -CO-having 1-4 substituents R9phenyl-O- (C)1-C2Alkyl) -CO-, phenyl- (C)2-C4Alkenyl) -CO-having 1-4 substituents R10Phenyl- (C)2-C4Alkenyl) -CO-, heteroaryl having 1-4 substituents R11Heteroaryl, heteroaryl- (C) of1-C2Alkyl group of (a) -, with 1-4 substituents R12Heteroaryl of (A) - (C)1-C2Alkyl) -, heteroaryl-CO-or with 1-4 substituents R13heteroaryl-CO-of said substituent R4、R5、R6、R7、R8、R9、R10、R11、R12And R13Each independently selected from halogen, -CN, -NO2、C1-C4Alkyl of (C)1-C4Haloalkyl of (A), (B), (C)1-C4Alkyl group of (A) O-, (C)1-C4Haloalkyl) -O-, (C)1-C4Alkyl group of (A) O-CO-, (C)1-C4Alkyl group of (a) - (C) — S —, (C)1-C4Alkyl) -SO of2-, phenyl-O-or having 1-4 substituents R14phenyl-O-of said substituent R14Each independently selected from halogen, -CN, -NO2、C1-C4Alkyl of (C)1-C4Haloalkyl of (A), (B), (C)1-C4Alkyl group of (A) O-, (C)1-C4Haloalkyl) -O-;
R13、R14each independently selected from H, C1-C6Alkyl of (C)1-C6Halogenoalkyl of, C1-C6Alkenyl of, C1-C6Alkynyl (C)1-C6Alkyl) substituted benzeneO-CO-(C1-C6Alkyl of (b) -, -SO2-(C1-C6Alkyl of (b), -SO)2-N(C1-C6Alkyl of (2)2(ii) a Or, R13、R14Is firstly independently selected from H, C1-C6Alkyl of (C)1-C6Haloalkyl of (A), (B), (C)1-C6Alkyl) -O-CO- (C)1-C6Alkyl of (b) -, -SO2-(C1-C6Alkyl of (b), -SO)2-N(C1-C6Alkyl of (2)2And then connected by an N atom to form a five-membered ring or a six-membered ring.
In a second aspect, the present invention provides a process for the preparation of thiotriazinone isoxazolines according to the invention, which comprises: in the presence of activated carbonic acid, a first base and a first solvent, carrying out contact reaction on isocyanate shown in a formula (II) and thiourea shown in a formula (III),
Figure BDA0002065692300000031
in a third aspect, the invention provides the use of the thiotriazinone isoxazoline-containing compounds in protoporphyrinogen oxidase inhibitors.
According to a fourth aspect of the present invention, there is provided a protoporphyrinogen oxidase inhibitor comprising the thiotriazinone isoxazoline-based compound of the present invention.
In a fifth aspect, the invention provides the application of the thiotriazinone isoxazoline compound in weed control.
According to a sixth aspect of the present invention, there is provided a herbicide comprising the thiotriazinone isoxazoline compound of the present invention.
The thiotriazinone isoxazoline compound has at least the following advantages:
(1) can be used in protoporphyrinogen oxidase (PPO) inhibitor and produce better PPO inhibition effect than the existing herbicide which takes PPO inhibition as main mechanism;
(2) can be used in herbicides and produces a very excellent herbicidal effect;
(3) the crop safety is higher, and the weeds in the crop field can be effectively removed on the premise of ensuring the safe growth of the crops.
The thiotriazinone isoxazolines according to the invention are therefore particularly suitable for use in the prevention and removal of weeds in crop fields during crop growth.
Other features and advantages of the present invention will be described in more detail in the following detailed description of the invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a thiotriazinone isoxazoline compound, which has a structure shown in a formula (I),
Figure BDA0002065692300000041
wherein:
R1、R2each independently selected from H, -NH2、C1-C6Alkyl or C1-C6A haloalkyl group of (a);
R3、R4、R5、R6each independently selected from H, halogen, -CN, C1-C6Alkyl group of (C)1-C6Haloalkyl) -O-or (C)1-C6Alkyl) -SO of2-；
R7、R8Each independently selected from H, -CN, C1-C6Alkyl or C1-C6A haloalkyl group of (a);
R9、R10each independently selected from H, -CN, C1-C6Alkyl of (C)1-C6Haloalkyl, -CO-OR11、-CH2OR12、-CONR13R14Phenyl or benzyl;
R11selected from H, C1-C6Alkyl of (C)1-C6Halogenoalkyl of, C3-C6Alkenyl of, C3-C6Alkynyl (C)1-C6Alkyl) -O- (C of1-C6Alkyl of (C) -, (C)1-C6Alkyl) -CO-O- (C)1-C4Alkyl group of (C), (C)1-C6Alkyl) -CO-NH- (C)1-C4Alkyl of (2), benzyl, having 1 to 4 substituents R3A benzyl group of,
Figure BDA0002065692300000051
Wherein the substituent R3Each independently selected from: halogen, -CN, -NO2、C1-C8Alkyl of (C)1-C8Haloalkyl of (A), (B), (C)1-C8Alkyl group of (A) O-, (C)1-C8Haloalkyl) -O-, (C)1-C8Alkyl group of (A) O-CO-, (C)1-C8Alkyl) -S-or (C)1-C8Alkyl) -SO of2-; wherein R is15、R16Each independently selected from the group I consisting of15/16: H. -CN, halogen, substituted or unsubstituted C1-C10Alkyl, substituted or unsubstituted C1-C10Alkoxy, substituted or unsubstituted C3-C10Is a substituted or unsubstituted C containing 0 to 3 (when 0, this means no) at least one hetero atom selected from the group consisting of N, O and S5-C10Aryl, substituted or unsubstituted pyridyl, substituted or unsubstituted thienyl, substituted or unsubstituted phenylSubstituted or unsubstituted benzyl, substituted or unsubstituted-CO- (C)1-C12Alkyl of (a) -, substituted or unsubstituted- (C)1-C5Alkyl) -CO- (C)1-C5Alkyl of (a) -, substituted or unsubstituted- (C)1-C3Ester group of (1) - (C)1-C3Alkyl of (a) -, the group I15/16The substituent in (A) is selected from one or more of halogen, nitro, cyano and amino; or, R15And R16Are first selected from the above group I15/16Then connecting to form a ring; r15And R16Not H at the same time; in the present invention, said group I15/16Is used to represent R only15、R16The ranges are chosen without any limiting effect on the other aspects of the invention;
R12selected from H, C1-C6Alkyl of (C)1-C6Haloalkyl of (A), (B), (C)1-C6Alkyl group of (A) O-CO-, (C)1-C6Alkyl group of (2) - (C)1-C6Haloalkyl) -CO-, (C)3-C6Cycloalkyl) -CO-, (C)3-C6Halocycloalkyl) -CO-, (C)1-C6Alkyl) -SO of2-、(C1-C6Haloalkyl) -SO of2-、(C1-C6Alkyl) -NH-SO of2-、(C1-C6Alkyl of (2)2-N-SO2-、 (C1-C6Alkyl) -NH-CO-, (C)1-C6Alkyl of (2)2-N-CO-、(C1-C6Alkyl of (2)2-N-CS-、(C1-C6Alkyl) -S- (C of2-C6Alkyl) -CO-, phenyl with 1-4 substituents R4Phenyl and phenyl- (C)1-C2Alkyl group of (a) -, with 1-4 substituents R5Phenyl- (C)1-C2Alkyl of (2) -, phenyl- (C)2-C4Alkenyl) with 1-4 substituents R6Phenyl- (C)2-C4Alkenyl of (a), phenyl-CO-, with 1-4 substituents R7phenyl-CO-, phenyl- (C)1-C2Alkyl) -CO-having 1-4 substituents R8Phenyl- (C)1-C2Alkyl) -CO-, phenyl-O- (C)1-C2Alkyl) -CO-having 1-4 substituents R9phenyl-O- (C)1-C2Alkyl) -CO-, phenyl- (C)2-C4Alkenyl) -CO-having 1-4 substituents R10Phenyl- (C)2-C4Alkenyl) -CO-, heteroaryl having 1-4 substituents R11Heteroaryl, heteroaryl- (C) of1-C2Alkyl group of (a) -, with 1-4 substituents R12Heteroaryl of (A) - (C)1-C2Alkyl) -, heteroaryl-CO-or with 1-4 substituents R13heteroaryl-CO-of said substituent R4、R5、R6、R7、R8、R9、R10、R11、R12And R13Each independently selected from halogen, -CN, -NO2、C1-C4Alkyl of (C)1-C4Haloalkyl of (A), (B), (C)1-C4Alkyl group of (A) O-, (C)1-C4Haloalkyl) -O-, (C)1-C4Alkyl group of (A) O-CO-, (C)1-C4Alkyl group of (a) - (C) — S —, (C)1-C4Alkyl) -SO of2-, phenyl-O-or having 1-4 substituents R14phenyl-O-of said substituent R14Each independently selected from halogen, -CN, -NO2、C1-C4Alkyl of (C)1-C4Haloalkyl of (A), (B), (C)1-C4Alkyl group of (A) O-, (C)1-C4Haloalkyl) -O-;
R13、R14each independently selected from H, C1-C6Alkyl of (C)1-C6Halogenoalkyl of, C1-C6Alkenyl of, C1-C6Alkynyl (C)1-C6Alkyl) -O-CO- (C)1-C6Alkyl of (b) -, -SO2-(C1-C6Alkyl of (b), -SO)2-N(C1-C6Alkyl of (2)2(ii) a Or, R13、R14Is firstly independently selected from H, C1-C6Alkyl of (C)1-C6Haloalkyl of (A), (B), (C)1-C6Alkyl) -O-CO- (C)1-C6Alkyl of (b) -, -SO2-(C1-C6Alkyl of (b), -SO)2-N(C1-C6Alkyl of (2)2And then connected by an N atom to form a five-membered ring or a six-membered ring.
For R1Preferably, R1Selected from H, -NH2Or C1-C6Alkyl groups of (a); more preferably, R1Selected from H, -NH2or-CH3. According to a particular embodiment of the invention, R1is-CH3。
For R2Preferably, R2Selected from H, -NH2Or C1-C6Alkyl groups of (a); more preferably, R2Selected from H, -NH2、-CH3or-CH2CH3. According to a preferred embodiment of the invention, R2is-CH3or-CH2CH3。
For R3Preferably, R3Selected from H, halogen or-CN; more preferably, R3Is H or halogen. According to one embodiment of the invention, R3Is H or-F.
For R4Preferably, R4Selected from H, halogen or-CN. According to one embodiment of the invention, R4Is H.
For R5Preferably, R5Selected from H, halogen or-CN; more preferably, R5Selected from halogen or-CN. According to one embodiment of the invention, R5Is selected from-Cl or-CN.
For R6Preferably, R6Selected from H, halogen or-CN. According to one embodiment of the invention, R6Is H.
For R7Preferably, R7Selected from H, C1-C6Alkyl or C1-C8A haloalkyl group; more preferably, R7Selected from H, -CH3、 -CH2CH3Or a halomethyl group. According to one embodiment of the invention, R7Is selected from H or-CH3。
For R8Preferably, R8Selected from H, C1-C6Alkyl radical, C1-C8A haloalkyl group; more preferably, R8Selected from H, -CH3、 -CH2CH3Or a halomethyl group. According to one embodiment of the invention, R8Is selected from H or-CH3。
For R9Preferably, R9Selected from H, -CN, C1-C6Alkyl of (C)1-C6Haloalkyl, -CO-OR11、 -CH2OR12、-CONR13R14Or phenyl; more preferably, R9Selected from H, C1-C3Alkyl or-CH of2OR12. According to a preferred embodiment of the invention, R9Selected from H, -CH3or-CH2OCH3。
For R10Preferably, R10Is selected from-CN, C1-C6Alkyl of (C)1-C6Haloalkyl, -CO-OR11、 -CH2OR12、-CONR13R14Or a phenyl group. According to a preferred embodiment of the invention, R10Selected from-CO-OR11、 -CH2OR12or-CONR13R14。
For R11Preferably, R11Selected from H, C1-C3Alkyl of (C)1-C3Halogenoalkyl of, C3-C4Alkenyl of, C3-C4Alkynyl (C)1-C6Alkyl) -CO-O- (C)1-C4Alkyl of (a) or (C)1-C6Alkyl) -CO-NH- (C)1-C4Alkyl of) or
Figure BDA0002065692300000061
In the structure
Figure BDA0002065692300000062
In, preferably, R15、R16Each independently selected from H, -CN, substituted or unsubstituted C1-C10Alkyl, substituted or unsubstituted C1-C10Alkoxy, substituted or unsubstituted C3-C10A substituted or unsubstituted phenyl group, a substituted or unsubstituted benzyl group or a substituted or unsubstituted- (C)1-C3Ester group of (1) - (C)1-C3Alkyl) -wherein the substituents are selected from one or more of halogen, nitro, cyano and amino; r15And R16Not H at the same time.
For R12Preferably, R12Selected from H, (C)1-C2Alkyl group of (2) - (C)1-C2Haloalkyl) -CO-, phenyl- (C)1-C2Alkyl) -CO-, phenyl- (C)1-C2Haloalkyl) -CO-or phenyl-O- (C)1-C2Alkyl) -CO-.
For R13And R14Preferably, R13、R14Each independently selected from H, C1-C4Alkyl of (C)1-C4Halogenoalkyl of, C1-C6Alkenyl of, C1-C6Alkynyl, -SO2-(C1-C6Alkyl of) or-SO2-N(C1-C6Alkyl of (2)2。
In the formula (I) of the present invention, the selection of each group satisfying "-" indicates a site at which the group is bonded to the structure of the formula (I), for example, "(C)1-C8Alkyl) -O- "of (A) means that the structure is linked to the structure of formula (I) through an oxygen atom; and is as in "(C)1-C6Alkyl) -CO-O- (C)1-C4Alkyl group of (c)' "does not define a linking site, and indicates both ends. The alkyl, haloalkyl, alkenyl, alkynyl and the like groups are not limited to straight or branched chains. All the terms in the invention can be used asAs explained in a manner conventional in the art.
The thiotriazinone-containing isoxazolines of the present invention having the structure represented by formula (1) can be illustrated by the specific compounds listed in Table 1, but the present invention is not limited to these compounds. In Table 1, R4、R6、R7、R8Are each H. Structure "CO" in Table 12"represents" -CO-O- ".
TABLE 1
Figure BDA0002065692300000071
Figure BDA0002065692300000081
Figure BDA0002065692300000091
Figure BDA0002065692300000101
Figure BDA0002065692300000111
Figure BDA0002065692300000121
Figure BDA0002065692300000131
In a second aspect, the present invention provides a process for the preparation of thiotriazinone isoxazolines according to the invention, which comprises: in the presence of activated carbonic acid, a first base and a first solvent, carrying out contact reaction on isocyanate shown in a formula (II) and thiourea shown in a formula (III),
Figure BDA0002065692300000141
the reaction process of the contact reaction of the isocyanate shown in the formula (II) and the thiourea shown in the formula (III) is shown in the chemical formula I.
Figure BDA0002065692300000142
In the preparation method of the invention, R in the chemical structural formula1-R16The definitions of the compounds are the same as those of the thiotriazinone-containing isoxazoline compounds of the present invention, and are not described herein again.
According to the method of the present invention, the amounts of the isocyanate, thiourea, activated carbonic acid and the first base can be adjusted within a wide range, and in order to obtain the thiotriazinone-containing isoxazoline compound with higher purity, yield and herbicidal activity, the molar ratio of the amounts of the isocyanate, thiourea, activated carbonic acid and the first base is preferably 1: 1-2: 1-4: 1-5, more preferably, the isocyanate, thiourea, activated carbonic acid and the first base are used in a molar ratio of 1: 1-1.5: 1.05-2: 1-3.
According to the process of the present invention, the activated carbonic acid may be selected within a wide range in the art, and is preferably selected from one or more of N' N-carbonyldiimidazole, phosgene, diphosgene, triphosgene, methyl chloroformate, ethyl chloroformate and phenyl chloroformate in order to be combined with the other reaction materials of the present invention to obtain a thiotriazinone-containing isoxazoline compound having higher purity, yield and herbicidal activity.
According to the process of the present invention, the first base may be selected within the scope of the art, and is preferably selected from one or more of triethylamine, N-diisopropylethylamine, pyridine, 1, 8-diazabicycloundece-7-ene, 4-dimethylaminopyridine, more preferably from triethylamine and/or N, N-diisopropylethylamine in order to be combined with the other reaction materials of the present invention to obtain thiotriazinone-containing isoxazolines of higher purity, yield and herbicidal activity.
According to the process of the present invention, the first solvent may be selected within a wide range in the art, and is preferably selected from one or more of toluene, xylene, dioxane, ethyl acetate, tetrahydrofuran and dichloroethane, more preferably one or more of toluene, xylene and dioxane, in order to be combined with the other reaction materials of the present invention to obtain the thiotriazinone-containing isoxazoline compound having higher purity, yield and herbicidal activity.
According to the method of the present invention, the amount of the first solvent is not particularly limited, and may be an amount that provides a sufficient reaction environment for the contact reaction. Preferably, the first solvent is used in an amount of 1 to 10mL, more preferably 2 to 8mL, relative to 1mmol of isocyanate.
According to the method of the present invention, in order to obtain thiotriazinone isoxazolines with higher purity, yield and herbicidal activity, preferably, the contact reaction comprises the following steps: dissolving the thiourea and the first base in the first solvent to obtain a first reaction material, dissolving the isocyanate in the first solvent to obtain a second reaction material, gradually adding the first reaction material into the second reaction material within 0.1-0.5 hours to obtain a third reaction material, and contacting the third reaction material with the active carbonic acid at 50-100 ℃ for 6-18 hours.
In the process of the contact reaction, preferably, the first reaction material is gradually added into the second reaction material to obtain a third reaction material, wherein the gradual addition does not distinguish laboratories, small tests, pilot tests and large tests, and the addition is finished within 0.1-0.5 hour according to the required dosage; more preferably within 0.1 to 0.3 hours. The stepwise addition may be carried out in portions or at a uniform rate, preferably at a uniform rate.
During the contact reaction, the third reaction material is preferably prepared and then reacted with the active carbonic acid, and more preferably, the third reaction material is contacted with the active carbonic acid at 80-90 ℃ for 8-12 hours.
According to the method of the present invention, preferably, the material obtained by the contact reaction is purified to obtain the thiotriazinone-containing isoxazoline compound shown in formula (I). The purification method is not particularly limited, and may be carried out according to a method conventional in the art, for example, the material obtained by the contact reaction is sequentially subjected to extraction, washing, drying and solvent removal, and the extraction may be carried out, for example, by adding a mixture of water and an organic solvent (e.g., ethyl acetate) and then extracting with an organic solvent; the washing may be performed, for example, with a saturated saline solution; the drying may be carried out, for example, with a solid drying agent (e.g., anhydrous sodium sulfate, anhydrous magnesium sulfate, and molecular sieves); the solvent removal can be carried out, for example, by concentrating the solvent under reduced pressure.
According to the process of the present invention, the isocyanate of the structure represented by the formula (II) can be obtained commercially or can be prepared.
According to the process of the present invention, preferably, the isocyanate of formula (II) is prepared by a process comprising: in the presence of a second solvent and a second alkali, carrying out isocyanation reaction on a raw material A shown in a formula (IV) and triphosgene shown in a formula (V),
Figure BDA0002065692300000151
according to the method of the present invention, the reaction process for preparing isocyanate is shown in the reaction formula II,
Figure BDA0002065692300000161
in the above-mentioned process for preparing isocyanates, the amounts of the second base, the raw material A and the triphosgene can be adjusted within a wide range, and in order to obtain isocyanates with better purity and yield and to obtain thiotriazinone-containing isoxazolines with higher herbicidal activity, the raw material A, the triphosgene and the second base are preferably used in a molar ratio of 1: 0.1-1: 0.005-1, more preferably 1: 0.25-1: 0.006-0.8.
In the above-described process for the preparation of isocyanates, the second base may be selected within the scope of the art, and in order to be compatible with the other reaction materials of the present invention to obtain isocyanates having better purity and yield and to obtain more herbicidally active thiatriazinone-containing isoxazolines, in preferred cases the second base is selected from one or more of triethylamine, N-diisopropylethylamine, pyridine, 1, 8-diazabicycloundece-7-ene, 4-dimethylaminopyridine, more preferably from one or more of triethylamine, N-diisopropylethylamine, pyridine.
In the above-mentioned process for preparing isocyanate, the amount of the second solvent is not particularly limited, and may be sufficient to provide a reaction environment for the reaction for preparing isocyanate. Preferably, the amount of the second solvent is 1 to 10mL, more preferably 2 to 8mL, relative to 1mmol of triphosgene.
In the above-mentioned process for preparing isocyanates, in order to obtain isocyanates with better purity and yield and to obtain thiotriazinone-containing isoxazolines with higher herbicidal activity, preferably, the isocyanation reaction comprises: dissolving the triphosgene in the second solvent to obtain a second reaction material B, mixing the raw material A with the second alkali to obtain a first reaction material A, gradually adding the first reaction material B into the first reaction material within 0.1-0.5 hour, and then sequentially carrying out three-stage reaction: the first stage of reaction, wherein the contact reaction is carried out for 0.2 to 0.8h at the temperature of between 4 ℃ below zero and 10 ℃; the second stage reaction, the contact reaction is carried out for 0.2 to 0.8h at the temperature of between 15 and 30 ℃; and (3) carrying out a third stage of reaction, namely heating for carrying out reflux reaction for 8-14 h.
In the above process for preparing isocyanate, preferably, the reaction material B is gradually added into the reaction material A, and the gradual addition does not distinguish laboratories, small tests, pilot tests and large tests, and the addition is finished within 0.1 to 0.5 hours according to the required dosage; more preferably within 0.2-0.3 hours. The stepwise addition may be carried out in portions or at a uniform rate, preferably at a uniform rate.
In the process for preparing the isocyanate, in order to enable the prepared isocyanate to have better purity and yield and to prepare the thiotriazinone-containing isoxazoline compound with higher herbicidal activity, three-stage reaction is sequentially carried out at different temperatures and time.
More preferably, the conditions of the first stage reaction include: the contact reaction is carried out for 0.1 to 2 hours at the temperature of between 10 ℃ below zero and 20 ℃.
More preferably, the conditions for the second stage reaction include: the contact reaction is carried out for 0.1 to 2 hours at the temperature of between 10 and 50 ℃.
More preferably, the conditions for the third stage reaction include: contact reaction is carried out for 6 to 18 hours at the temperature of between 50 and 100 ℃.
In the above-mentioned process for preparing isocyanate, it is preferable that after the isocyanation reaction, the solvent is removed to obtain the isocyanate represented by formula (IV), and then the subsequent reaction is carried out. The solvent removal method may be performed according to a method conventional in the art, for example, a method of concentrating the solvent removal under reduced pressure.
The compound represented by the formula (IV) may be obtained commercially or may be prepared by, for example, a conventional method using a reducing agent such as iron, zinc, palladium on carbon, stannous oxide or the like from the compound represented by the formula (VI), and specifically, reference is made to EP 2044006; US 20070155738; european Journal of Medicinal Chemistry, 2013, 65, 32-40; synlett, 2010, (20), 3019-3022; HETEROCYCLES, 2008, 75(1):57-64, etc. The compounds of formula (VI) can be synthesized from the compounds of formula (IX) in three steps as described in the literature, for example J.Agric.food Chem.2005,53,8639-8643 or WO 2006090234.
Figure BDA0002065692300000171
Unless otherwise indicated, each group in the reaction formula is as defined above.
Since the thiotriazinone-containing isoxazolines of the first aspect of the present invention having the structure of formula (I) are very complex and various, the preparation method of the second aspect of the present invention may further comprise some conventional steps for adjusting the terminal functional groups, which are conventional in the art. These steps, which can be carried out by a person skilled in the art on the basis of routine procedures, are within the scope of protection of the method of the second aspect of the invention.
For example, when R is11Is composed of
Figure BDA0002065692300000172
In structure, the method of the present invention further comprises:
first prepared to obtain R10A compound of formula (I) which is-CO-OH, and then adding R10A compound of formula (I) which is-CO-OH and
Figure BDA0002065692300000173
carrying out condensation reaction on the compound with the structure to obtain R10is-CO-OR11And R is11Is composed of
Figure BDA0002065692300000174
A compound of the structure formula (I).
The process of the above condensation reaction can be illustrated by the following chemical equation III.
Figure BDA0002065692300000181
According to a preferred embodiment of the invention, the condensation reaction comprises the following steps:
the first step is as follows: in the presence of a third solvent, reacting R10Carrying out acyl chlorination reaction on a compound shown as a formula (I) which is-CO-OH and an acyl chlorination reagent to obtain an acyl chlorination intermediate;
the second step is that: reacting the acylchlorinated intermediate with a second base in the presence of a second solvent
Figure BDA0002065692300000182
The compound of structure (I) undergoes a chemical reaction.
In the first step, preferably, R is10The dosage molar ratio of the compound shown in the formula (I) which is-CO-OH to the acyl chlorination reagent is 1 (1.05-3).
In the first step, preferably, the process of the acyl chlorination reaction comprises the following two stages, wherein the 1 st to 1 st stages are: at 0-5 ℃, adding the third solvent and R10The compound shown in the formula (I) which is-CO-OH and the acyl chlorination reagent are mixed and contacted for 0.5 to 1.5 hours; stages 1-2 are: the materials obtained by the mixed contact of the stages 1-1 react for 1.5-4 hours at the temperature of 10-120 ℃. Wherein the mixing and contacting of stages 1-1 is preferably carried out by stepwise addition of the acid chloride reagent, which may be carried out in a stepwise manner as previously described.
In the first step, preferably, the acylchlorinating agent is selected from one or more of oxalyl chloride, thionyl chloride, phosphorus trichloride, phosphorus pentachloride and phosphorus oxychloride.
In the first step, preferably, R is10The dosage ratio of the compound shown in the formula (I) which is-CO-OH and the third solvent is 1mol (8-15 mL).
In the first step, preferably, the third solvent is an aprotic solvent, more preferably one or more selected from the group consisting of dichloromethane, dichloroethane, acetonitrile, chloroform, tetrahydrofuran, toluene, and xylene.
Preferably, the first step further comprises removing the solvent from the acyl chloride intermediate prior to performing the second step.
In a second step, the acylchlorination intermediate is reacted with
Figure BDA0002065692300000183
The chemical reaction of the compound with the structure comprises the following two stages, wherein the 2 nd to 1 st stages are as follows: the acylchlorination intermediate, the fourth solvent, the third base, and the third base are reacted at 0-5 ℃
Figure BDA0002065692300000184
The compound with the structure is mixed and contacted for 0.2 to 1 hour; the 2 nd to 2 nd stages are as follows: the materials obtained by the mixed contact of the 2 nd to 1 st stage react for 1.5 to 4 hours at the temperature of between 15 and 30 ℃. Wherein the step 2-1 of said mixing and contacting preferably comprises a step-wise addition of said acid chloride intermediate and/or said third base, which step-wise addition may be arranged in a manner referred to the step-wise addition described above.
In the second step, preferably, the acylchlorination intermediate is reacted with the carboxylic acid
Figure BDA0002065692300000191
The dosage molar ratio of the compounds with the structure is 1 (0.9-1.2).
In the second step, preferably, the acyl chloride intermediate, the third base and the fourth solvent are used in a ratio of 1mol (1.5-2.5mol) to 8-15 mL.
In the second step, preferably, the fourth solvent is selected from one or more of dichloromethane, dichloroethane, acetonitrile, chloroform, tetrahydrofuran, toluene, and xylene.
In the second step, preferably, the third base is selected from one or more of triethylamine, N-diisopropylethylamine, pyridine, 1, 8-diazabicycloundec-7-ene, 4-dimethylaminopyridine.
The second step of the present invention also includes the post-treatment processes, such as washing, drying, solvent removal under reduced pressure, etc., which can be performed in the manner described above or conventional in the art, and will not be described herein again.
In a third aspect, the invention provides the use of the thiotriazinone isoxazoline-containing compounds in protoporphyrinogen oxidase inhibitors.
Protoporphyrinogen oxidase is a key enzyme in plants for photosynthesis. If the enzyme is inhibited, the synthesis process of chlorophyll in plants is hindered, and the plants are finally killed. The compound provided by the invention has high inhibitory activity on plant protoporphyrinogen oxidase.
According to a fourth aspect of the present invention, there is provided a protoporphyrinogen oxidase inhibitor comprising the thiotriazinone isoxazoline-containing compound according to the first aspect of the present invention.
In the present invention, the thiotriazinone-containing isoxazoline compound is preferably contained in an amount of 0.001 to 10% by weight, more preferably 0.005 to 5% by weight, based on the weight of the protoporphyrinogen oxidase inhibitor.
When the thiotriazinone-containing isoxazoline compound is used for preparing protoporphyrinogen oxidase inhibitors, the concentration required is lower because the protoporphyrinogen oxidase inhibitors directly act on experimental products. When the thiotriazinone-containing isoxazoline compound of the present invention is used for preparing herbicides, since most of the herbicides are not sprayed to the weeds during spraying, the proportion of the herbicides actually acting is low, and therefore, a higher concentration can be used for preparing the herbicides.
In a fifth aspect, the invention provides the application of the thiotriazinone isoxazoline compound in weed control.
The weeds of the present invention are plants that grow in a place that is harmful to human survival and activity, and may be non-cultivated wild plants or plants that are not useful to humans. For example, various wild plants in the field in which the crop is planted may be used.
Preferably, the weeds are broadleaf weeds and/or grassy weeds. The thiotriazinone-containing isoxazoline compound has good herbicidal activity when being used for controlling broadleaf weeds and/or grassy weeds.
According to the use of the present invention, in order to achieve a better weed control effect, it is preferable that the thiotriazinone isoxazoline compound is used in an amount of 5 to 150 g/ha, more preferably 15 to 80 g/ha.
According to the application of the invention, in order to achieve better weed control effect, the thiotriazinone isoxazoline compound is preferably dissolved in an organic solvent to prepare an organic solution for use. The solvent used for dissolving the thiotriazineone isoxazolines is preferably selected from one or more of N, N-dimethylformamide, dimethyl sulfoxide, toluene, xylene and acetone. Preferably, the concentration of the organic solution of the thiotriazineone isoxazoline compound obtained by dissolution is 0.005-0.2g/L, more preferably 0.03-0.08 g/L.
According to the use of the present invention, in order to achieve a better effect of controlling weeds, it is preferable to use an organic solution of the above thiotriazinone isoxazoline compound diluted with water or an aqueous solution. Further preferably, the volume ratio of the organic solution of the thiotriazinone isoxazoline compound to water or the aqueous solution is 1: 1-100, more preferably 1: 5-60.
The thiotriazinone isoxazoline compound can be used alone or in combination with other additives or herbicides.
In a sixth aspect, the present invention provides a herbicide comprising the thiotriazinone isoxazoline-containing compound of the present invention.
The herbicide according to the present invention contains the thiotriazinone-containing isoxazoline compound in an amount of preferably 0.5 to 90% by weight, more preferably 0.5 to 75% by weight, and still more preferably 5 to 60% by weight, based on the weight of the herbicide.
The herbicides according to the present invention may also comprise other adjuvants commonly used in the art, such as carriers, surfactants, and the like. The amount of adjuvant may be selected in a manner conventional in the art.
The herbicides according to the invention may also comprise further herbicides, for example selected from the group consisting of 2, 4-d-butyl ester, clodinafop-propargyl, pinoxaden, carfentrazone-ethyl, butafenacil, isoprothiolane, pyraflufen-ethyl, cyhalofop-butyl, indolyfen-ethyl, flumiclorafen, oxadiazon, oxadiargyl, clomazone, mesotrione, bisphenoxydim, pendimethalin, trifluralin, benazolin, acifluorfen-ethyl, benfurazolin, metofen-ethyl, oxyfluorfen, pyrithion, fomesafen, pyraflufen-ethyl, pyribenzoxim, bispyribac-methyl, metolachlor, pretilachlor, butachlor, mebutachlor, mefenacet, quinclorac, lactofen, pyraflufen-ethyl, pyrafluazifop-ethyl, and pyraflufen-ethyl, One or more of fluazifop-p-butyl, oxadiargyl, quizalofop-p-ethyl, haloxyfop-p-butyl, cyanazine, prometryn, ametryn, atrazine, clethodim, mesotrione, amicarbazone, sethoxydim, isoproturon, nicosulfuron, rimsulfuron, pyrazosulfuron-ethyl, bensulfuron-methyl, ethametsulfuron-methyl, thifensulfuron-methyl, imazasulfuron-methyl, trifloxysulfuron sodium, sulfosulfuron, cyclosulfamuron, amidosulfuron, flazasulfuron, broadleaf blight, paraquat, benazolin, mediben, bentazone, diuron, imazethapyr, 2-methyl-4-sodium chloride, aprazanide, bensulfuron-methyl, flumetsulfos, glufosinate, glyphosate and glufosinate.
The inventor of the invention finds that when the thiotriazinone-containing isoxazoline compound disclosed by the invention is matched with one or more of the herbicides, a good compound effect can be realized, and the effect of the activity, safety and application range (the type of the weeds to be controlled) for controlling the weeds is far more than the sum of the two herbicides when used independently.
The method of using the protoporphyrinogen oxidase inhibitor and/or herbicide of the present invention may be carried out according to a method conventional in the art, for example, by spraying the protoporphyrinogen oxidase inhibitor and/or herbicide onto the stems and/or leaves of weeds, or onto the soil surface.
The protoporphyrinogen oxidase inhibitor and/or herbicide has good safety to crops, and the crops do not need to be specially avoided when the protoporphyrinogen oxidase inhibitor and/or herbicide are sprayed.
The present invention will be described in detail below by way of examples. In the following examples, the various starting materials used in the examples are commercially available and all purity grades are analytical, unless otherwise specified. The compounds prepared in the following examples are the corresponding numbers in table 1.
EXAMPLE 3 preparation of Compound 3
The reaction process shown in the following formula IV is carried out,
Figure BDA0002065692300000211
this example was carried out to prepare compound 3 shown in Table 1, wherein R in the above formula (IX) to formula (I) is shown in Table 11＝CH3，R2＝CH3，R3＝F，R4＝H，R5＝Cl，R6＝H，R7＝H，R8＝H，R9＝CH3，R10＝CO-OC2H5。
For further visualization, formula IV above is specifically rewritten as a procedure for preparing compound 3, as shown below in formula V.
Figure BDA0002065692300000212
The specific process comprises the following steps:
1) preparation of Compound IV
0.206mol of the compound represented by the formula (IX) was dissolved in 200mL of ethanol, cooled to 0 ℃ and stirred dropwise with an aqueous solution of 0.25mol of hydroxylamine hydrochloride, followed by warming to room temperature and stirring for reaction. After 2 hours, the reaction was completed by TLC, poured into water, and filtered to obtain a solid containing the compound represented by the formula (VIII).
The solid obtained above was dissolved in 150mL of N, N-dimethylformamide, heated to 35 ℃ and 0.24mol of NCS was added in portions at this temperature, and the solution was kept at 35 ℃ for 1 hour to obtain a material containing the compound represented by the formula (VII). The temperature was lowered to room temperature, 300mL of ethyl acetate was added, followed by washing twice with 1N hydrochloric acid, washing twice with saturated brine, drying over anhydrous magnesium sulfate, suction filtration, lowering the ethyl acetate solution to 0-5 ℃ and dropwise adding a mixture of 0.3mol of ethyl methacrylate and 0.3mol of triethylamine, and the reaction was carried out at that temperature for 1 hour. The organic phase was dried over anhydrous magnesium sulfate, desolventized, and subjected to column chromatography (ethyl acetate: petroleum ether: 1:3) to obtain a solid containing the compound represented by the formula (VI). Dissolving the compound shown in the formula (VI) in 300mL of 90% ethanol solution, heating to 60 ℃, adding 0.3mol of reduced iron powder in 3 batches, keeping the temperature for reaction for 4 hours, cooling to room temperature after the reaction is finished, filtering, adding 200mL of saturated saline water and 300mL of ethyl acetate after the filtrate is dried, violently stirring for 10min, separating an organic layer, washing the water layer once with 200mL of ethyl acetate, and combining the organic layers. And drying the organic layer, and removing the solvent under reduced pressure to obtain the compound shown in the formula (IV).
2) Preparation of Compound II
0.026mol of triphosgene was dissolved in 40mL of toluene and the temperature was reduced to 0 ℃. A mixed solution of 0.052mol of the compound represented by the formula (VI) prepared above and 0.010mol of triethylamine is added dropwise while stirring. Continuously controlling the temperature to be 0 ℃ for reaction for 0.5h, transferring to room temperature for reaction for 0.5h, then heating to reflux reaction for 10h, and monitoring the reaction completion by TLC. Cooled to room temperature, and concentrated under reduced pressure to remove the solvent. Directly feeding the next step for reaction.
3) Preparation of Compound I (i.e., Compound 3)
Dissolving 0.062mol of the compound represented by the formula (III) and 0.052mol of triethylamine in 40mL of toluene, dropwise adding the prepared mixed solution of the compound represented by the formula (II) and 120mL of toluene while stirring at room temperature, adding 0.103 mol of N', N-carbonyldiimidazole after dropwise adding, heating to 85 ℃ for reaction for 10h, and monitoring the reaction completion by TLC. Cooling to room temperature, adding purified water and ethyl acetate, extracting with ethyl acetate, washing with saturated salt water, drying with anhydrous sodium sulfate, concentrating under reduced pressure, and performing column chromatography (V)Petroleum ether：VEthyl acetate1:5) to give a solid, i.e. compound 3 represented by formula (I). The nuclear magnetism of the alloy is characterized as follows:1H NMR (400MHz,CDCl3)7.74(d,J＝7.6Hz,1H),7.36(d,J＝8.8Hz,1H),4.27(q,J＝7.2Hz, 2H),4.01(d,J＝17.2Hz,1H),3.77(s,6H),3.39(d,J＝17.2Hz,1H),1.71(s,3H),1.32(t,J＝ 7.2Hz,3H)。
EXAMPLE 311 preparation of Compound 311
Compound 311 was further prepared using compound 3 prepared in example 1.
The specific process is shown in formula VI below.
Figure BDA0002065692300000221
1) To obtain Compound 1
Compound 3(10mmol) prepared in example 1, 20mL of glacial acetic acid, 20mL of H2O and 20mL of concentrated sulfuric acid were added to the reaction flask. Heating to 100 ℃ under stirring for reaction for 4h, after the reaction is finished, cooling the system to room temperature, pouring the cooled system into 500g of crushed ice, stirring vigorously for 30min, filtering the obtained solid, washing with water, and drying to obtain the compound 1. The nuclear magnetic characterization data is1H NMR(400MHz,CDCl3)7.74(d,J＝7.6Hz,1H),7.40(d,J＝8.8Hz,1H), 4.04(d,J＝17.6Hz,1H),3.80(s,6H),3.51(d,J＝17.6Hz,1H),1.81(s,3H)。
2) Synthesis of Compound 311
Compound 1(2mmol) obtained in step 1) was dissolved in 20mL of dichloromethane and cooled to 0 ℃. Oxalyl chloride (2.5mmol) was slowly added dropwise to the reaction solution with stirring, and the reaction was continued for 1 hour after the dropwise addition. And (3) moving the reaction liquid to room temperature, slowly heating to reflux for reaction for 2 hours, cooling to room temperature after the reaction is finished, and removing the solvent under reduced pressure. The resulting acid chloride was dissolved in 20mL of dichloromethane and cooled to 0 deg.C and α -benzaldoxime (2mmol) and triethylamine (4mmol) were added. After the addition is finished, stirring and reacting for 30min, moving to room temperature, and continuing stirring and reacting for 2 h. After the reaction was completed, 20mL of water was added to the system, and vigorously stirred for 10 min. The organic layer was separated, the aqueous layer was extracted once more with 20mL of dichloromethane, and the organic layers were combined. The organic layer was washed with water and saturated brine, dried over anhydrous sodium sulfate, and then the solvent was removed under reduced pressure. The residue was subjected to column chromatography to give compound 311. The nuclear magnetism of the alloy is characterized as follows:1H NMR(400MHz,CDCl3)8.49(s, 1H),7.75(dd,J＝7.2,1.6Hz,3H),7.53–7.42(m,3H),7.38(d,J＝9.0Hz,1H),4.16(d,J＝ 17.2Hz,1H),3.77(d,J＝2.0Hz,6H),3.49(d,J＝17.6Hz,1H),1.84(s,3H)。
examples 2 to 244
With reference to the procedures of examples 3 and 311 except that the starting materials used were different in order to prepare the compounds numbered 2,4, 5, 6, 7, 8, 9, 13, 14, 15, 17, 18, 19, 20, 21, 24, 25, 44, 53, 55 and 244 in table 1, respectivelyR in the compounds and the raw materials thereof1-R16The selection of (2) was performed as described in Table 1. The same numbers are used for the examples to prepare these compounds, and are identified as examples 2,4, 5, 6, 7, 8, 9, 13, 14, 15, 17, 18, 19, 20, 21, 24, 25, 44, 53, 55, and 244, respectively.
The nuclear magnetic data of the above-obtained compounds were individually measured, and the results are shown in table 2.
TABLE 2
Figure BDA0002065692300000231
Figure BDA0002065692300000241
Figure BDA0002065692300000251
Comparative example A
With reference to the procedure of example 1, a compound having a structure represented by formula (a) was prepared and designated as compound a.
Figure BDA0002065692300000252
Test example I
This test example is intended to illustrate the inhibitory activity of the compounds of the present invention against protoporphyrinogen oxidase.
The protoporphyrinogen oxidase used in the test is prepared by expressing and purifying tobacco mitochondrial PPO (NtPO). The preparation was carried out according to the method described in the literature (J aggregate Food Chem,2016,64(3), 552-562).
Specific test methods were carried out by the methods provided in (J aggregate Food Chem,2017,65(26), 5278-. This test was carried out on the compounds prepared in the above examples and comparative examples, respectively, to obtain Ki(kinetic constant of enzyme inhibition in. mu.M), this parameterIndicates the inhibitory ability of the inhibitor on the enzyme activity; it is generally accepted that KiThe smaller the value of (A) is, the higher the inhibitory ability against protoporphyrinogen oxidase activity is.
The test results are shown in table 3.
TABLE 3
Figure BDA0002065692300000253
Figure BDA0002065692300000261
As can be seen from Table 3, the compounds of the present invention have significantly higher PPO enzyme inhibitory activity than the control compound A. Therefore, when weeds are resistant to the compound A, the compound of the invention can still well inhibit the weeds by better PPO inhibition activity, thereby effectively replacing the compound A with poor weeding effect.
Test example II
This test example serves to illustrate the effect of the compounds according to the invention on controlling weeds.
The herbicidal activity inhibition (%) (the dose is 9.375 to 150 g/ha).
Test methods (potting method):
(1) inhibition of weed growth at a dose of 150 g/ha
The test targets are as shown in table 4, and the specific test method includes:
and (3) taking a flowerpot with the inner diameter of 6cm, filling composite soil (vegetable garden soil: seedling culture medium is 1:2, v/v) to the position 3/4 of the flowerpot, directly sowing the weed target (the bud rate is more than or equal to 85%), covering 0.2cm of soil, and waiting until weeds grow to about 3-leaf stage for later use. The compounds prepared in the examples and the comparative examples were dissolved in N, N-dimethylformamide and diluted with distilled water at a dose of 150 g/ha, respectively, to prepare a 0.2g/L solution, which was applied by an automatic spray tower (model: 3WPSH-700E, manufactured by Nanjing agricultural mechanization institute), and after the solution on the leaf surface of the weeds was dried, the solution was transferred to a greenhouse for cultivation, and the inhibition rate of the growth of weeds was investigated 15 days later. The method for calculating the inhibition rate of the growth of the weeds comprises the following steps
Figure 2
Wherein E is1Inhibition of weed growth in% (% C)1Fresh weight (in g) of aerial parts of control weed plants, T1To treat the fresh weight (in g) of the aerial parts of the weed plants.
It can be seen that E1The higher the value of (a), the stronger the inhibitory effect of the compound on weeds.
(2) Inhibition of weed growth at a dose of 37.5 g/ha
The test was conducted by referring to the test method in (1) above, except that the compounds obtained in examples and comparative examples were changed to 37.5 g/ha.
(3) Inhibition of weed growth at a dose of 9.375 g/ha
The test was conducted by referring to the test method in (1) above, except that the compounds obtained in examples and comparative examples were changed to 9.375 g/ha.
The test results are classified as follows and are shown in table 4, and the classification method is as follows:
when 90% < E1When the content is less than or equal to 100 percent, grade A is evaluated;
when 80% < E1When the content is less than or equal to 90 percent, the grade B is evaluated;
when 60% < E1When the content is less than or equal to 80 percent, the grade C is evaluated;
when 40% < E1When the content is less than or equal to 60 percent, evaluating the grade D;
when E is1And when the content is less than or equal to 40 percent, evaluating the grade E.
TABLE 4
Figure BDA0002065692300000271
Figure BDA0002065692300000281
As can be seen from Table 4, the compounds according to the invention have comparable or even better weed-inhibiting effects than the control compound A.
Test example III
This test serves to illustrate the safety of the compounds of the invention against crop plants.
Rice and corn were selected as test targets. The specific test method for the safety of the post-emergence crop comprises the following steps:
a flowerpot with the inner diameter of 9cm is taken, composite soil (vegetable garden soil: seedling raising matrix is 1:2, v/v) is filled to the 3/4 height of the flowerpot, and a crop target (the bud rate is more than or equal to 85%) is directly sowed for later use. After the compounds prepared in examples and comparative examples were applied to an automatic spray tower at a dose of 150 g/ha, they were transferred to a greenhouse and the inhibition of crop growth was examined after 30 days. The method for calculating the inhibition rate of the growth of the crops comprises the following steps
Figure 1
Wherein E is2Inhibition of crop growth (% by C)2Fresh weight in g, T of aerial parts of control crop plants2For the treatment of the fresh weight (in g) of the aerial parts of the crop plants.
The test results are classified as follows and are shown in table 5, and the classification method is as follows:
when the content is less than or equal to 0 percent and less than or equal to E2When the content is less than or equal to 5 percent, grade A is evaluated;
when 5% < E2Rating B when the content is less than or equal to 10%;
when 10% < E2When the content is less than or equal to 20 percent, the grade C is evaluated;
when 20% < E2When the content is less than or equal to 30 percent, evaluating the grade D;
when 30% < E2When the content is less than or equal to 50 percent, the grade E is evaluated;
when 50% < E2When the content is less than or equal to 70 percent, evaluating the grade F;
when 70% < E2When the content is less than or equal to 90 percent, evaluating the G grade;
when 90% < E2When the content is less than or equal to 95 percent, evaluating the grade H;
when 95% < E2And when the content is less than or equal to 100 percent, evaluating the grade I.
TABLE 5
NO. Rice (Oryza sativa L.) with improved resistance to stress Corn (corn)
1 C A
2 C A
3 C A
4 C A
5 A A
6 B A
7 A A
8 A A
9 A A
13 A A
14 A A
15 A A
17 A A
18 A A
19 A A
20 A A
21 A A
24 A A
25 A A
44 A A
53 A A
55 A A
244 A A
311 A A
A I H
As can be seen from Table 5, the compounds of the present invention have excellent crop safety and show weak inhibitory effect on the growth of rice and corn, and thus are particularly suitable for use in crop fields during the growth of crops. Compared with the compound A, the compound A also has very strong inhibition effect on rice and corn, so that the compound A cannot be used on crops. Thus, it can be seen that the compounds of the present invention are more widely used and more practical than compound a.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (10)

1. A thiotriazinone isoxazoline compound, which has a structure shown in a formula (I),
Figure FDA0002065692290000011
wherein:
R1、R2each independently selected from H, -NH2、C1-C6Alkyl or C1-C6A haloalkyl group of (a);
R3、R4、R5、R6each independently selected from H, halogen, -CN, C1-C6Alkyl group of (C)1-C6Haloalkyl) -O-or (C)1-C6Alkyl) -SO of2-；
R7、R8Each independently selected from H, -CN, C1-C6Alkyl or C1-C6A haloalkyl group of (a);
R9、R10each independently selected from H, -CN, C1-C6Alkyl of (C)1-C6Haloalkyl, -CO-OR11、-CH2OR12、-CONR13R14Phenyl or benzyl;
R11selected from H, C1-C6Alkyl of (C)1-C6Halogenoalkyl of, C3-C6Alkenyl of, C3-C6Alkynyl (C)1-C6Alkyl) -O- (C of1-C6Alkyl of (C) -, (C)1-C6Alkyl) -CO-O- (C)1-C4Alkyl group of (C), (C)1-C6Alkyl) -CO-NH- (C)1-C4Alkyl of (2), benzyl, having 1 to 4 substituents R3A benzyl group of,
Figure FDA0002065692290000012
Wherein the substituent R3Each independently selected from: halogen, -CN, -NO2、C1-C8Alkyl of (C)1-C8Haloalkyl of (A), (B), (C)1-C8Alkyl group of (A) O-, (C)1-C8Haloalkyl) -O-, (C)1-C8Alkyl group of (A) O-CO-, (C)1-C8Alkyl) -S-or (C)1-C8Alkyl) -SO of2-; wherein R is15、R16Each independently selected from the group I consisting of15/16: H. -CN, halogen, substituted or unsubstituted C1-C10Alkyl, substituted or unsubstituted C1-C10Alkoxy, substituted or unsubstituted C3-C10Substituted or unsubstituted C containing 0 to 3 heteroatoms selected from at least N, O and S5-C10Aryl, substituted or unsubstituted pyridyl, substituted or unsubstituted thienyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, substituted or unsubstituted-CO- (C)1-C12Alkyl of (a) -, substituted or unsubstituted- (C)1-C5Alkyl) -CO- (C)1-C5Alkyl of (a) -, substituted or unsubstituted- (C)1-C3Ester group of (1) - (C)1-C3Alkyl of (a) -, the group I15/16Wherein the substituents are selected from the group consisting of halogen, nitro, cyano andone or more of amino groups; or, R15And R16Are first selected from the above group I15/16Then connecting to form a ring; r15And R16Not H at the same time;
R12selected from H, C1-C6Alkyl of (C)1-C6Haloalkyl of (A), (B), (C)1-C6Alkyl group of (A) O-CO-, (C)1-C6Alkyl group of (2) - (C)1-C6Haloalkyl) -CO-, (C)3-C6Cycloalkyl) -CO-, (C)3-C6Halocycloalkyl) -CO-, (C)1-C6Alkyl) -SO of2-、(C1-C6Haloalkyl) -SO of2-、(C1-C6Alkyl) -NH-SO of2-、(C1-C6Alkyl of (2)2-N-SO2-、(C1-C6Alkyl) -NH-CO-, (C)1-C6Alkyl of (2)2-N-CO-、(C1-C6Alkyl of (2)2-N-CS-、(C1-C6Alkyl) -S- (C of2-C6Alkyl) -CO-, phenyl with 1-4 substituents R4Phenyl and phenyl- (C)1-C2Alkyl group of (a) -, with 1-4 substituents R5Phenyl- (C)1-C2Alkyl of (2) -, phenyl- (C)2-C4Alkenyl) with 1-4 substituents R6Phenyl- (C)2-C4Alkenyl of (a), phenyl-CO-, with 1-4 substituents R7phenyl-CO-, phenyl- (C)1-C2Alkyl) -CO-having 1-4 substituents R8Phenyl- (C)1-C2Alkyl) -CO-, phenyl-O- (C)1-C2Alkyl) -CO-having 1-4 substituents R9phenyl-O- (C)1-C2Alkyl) -CO-, phenyl- (C)2-C4Alkenyl) -CO-having 1-4 substituents R10Phenyl- (C)2-C4Alkenyl) -CO-, heteroaryl having 1-4 substituents R11Heteroaryl, heteroaryl- (C) of1-C2Alkyl group of (a) -, with 1-4 substituents R12Heteroaryl of (A) - (C)1-C2Alkyl) -, heteroaryl-CO-or with 1-4 substituents R13heteroaryl-CO-of said substituent R4、R5、R6、R7、R8、R9、R10、R11、R12And R13Each independently selected from halogen, -CN, -NO2、C1-C4Alkyl of (C)1-C4Haloalkyl of (A), (B), (C)1-C4Alkyl group of (A) O-, (C)1-C4Haloalkyl) -O-, (C)1-C4Alkyl group of (A) O-CO-, (C)1-C4Alkyl group of (a) - (C) — S —, (C)1-C4Alkyl) -SO of2-, phenyl-O-or having 1-4 substituents R14phenyl-O-of said substituent R14Each independently selected from halogen, -CN, -NO2、C1-C4Alkyl of (C)1-C4Haloalkyl of (A), (B), (C)1-C4Alkyl group of (A) O-, (C)1-C4Haloalkyl) -O-;
R13、R14each independently selected from H, C1-C6Alkyl of (C)1-C6Halogenoalkyl of, C1-C6Alkenyl of, C1-C6Alkynyl (C)1-C6Alkyl) -O-CO- (C)1-C6Alkyl of (b) -, -SO2-(C1-C6Alkyl of (b), -SO)2-N(C1-C6Alkyl of (2)2(ii) a Or, R13、R14Is firstly independently selected from H, C1-C6Alkyl of (C)1-C6Haloalkyl of (A), (B), (C)1-C6Alkyl) -O-CO- (C)1-C6Alkyl of (b) -, -SO2-(C1-C6Alkyl of (b), -SO)2-N(C1-C6Alkyl of (2)2And then connected by an N atom to form a five-membered ring or a six-membered ring.
2. The thiotriazinone-containing isoxazoline compound of claim 1, wherein R1Selected from H, -NH2Or C1-C6Alkyl groups of (a);
preferably, R2Selected from H, -NH2Or C1-C6Alkyl groups of (a);
preferably, R3Selected from H, halogen or-CN;
preferably, R4Selected from H, halogen or-CN;
preferably, R5Selected from H, halogen or-CN;
preferably, R6Selected from H, halogen or-CN;
preferably, R7Selected from H, C1-C6Alkyl or C1-C8A haloalkyl group;
preferably, R8Selected from H, C1-C6Alkyl or C1-C8A haloalkyl group;
preferably, R9Selected from H, -CN, C1-C3Alkyl or-CH of2OR12；
Preferably, R10Is selected from-CN, C1-C6Alkyl of (C)1-C6Haloalkyl, -CO-OR11、-CH2OR12、-CONR13R14Or a phenyl group.
3. The thiotriazinone-containing isoxazoline compound of claim 2, wherein R1is-CH3；
Preferably, R2is-CH3or-CH2CH3；
Preferably, R3Is H or-F;
preferably, R4Is H;
preferably, R5is-Cl or-CN;
preferably, R6Is H;
preferably, R7Is selected from H or-CH3；
Preferably, R8Is selected from H or-CH3；
Preferably, the first and second electrodes are formed of a metal,R9selected from H, -CH3or-CH2OCH3；
Preferably, R10Selected from-CO-OR11、-CH2OR12or-CONR13R14。
4. The thiotriazinone-containing isoxazoline compound according to any one of claims 1 to 3, wherein R11Selected from H, C1-C3Alkyl of (C)1-C3Halogenoalkyl of, C3-C4Alkenyl of, C3-C4Alkynyl (C)1-C6Alkyl) -CO-O- (C)1-C4Alkyl of (a) or (C)1-C6Alkyl) -CO-NH- (C)1-C4Alkyl of) or
Figure FDA0002065692290000041
Preferably, R15、R16Each independently selected from H, -CN, substituted or unsubstituted C1-C10Alkyl, substituted or unsubstituted C1-C10Alkoxy, substituted or unsubstituted C3-C10A substituted or unsubstituted phenyl group, a substituted or unsubstituted benzyl group or a substituted or unsubstituted- (C)1-C3Ester group of (1) - (C)1-C3Alkyl) -wherein the substituents are selected from one or more of halogen, nitro, cyano and amino; r15And R16Not H at the same time;
preferably, R12Selected from H, (C)1-C2Alkyl group of (2) - (C)1-C2Haloalkyl) -CO-, phenyl- (C)1-C2Alkyl) -CO-, phenyl- (C)1-C2Haloalkyl) -CO-or phenyl-O- (C)1-C2Alkyl) -CO-;
preferably, R13、R14Each independently selected from H, C1-C4Alkyl of (C)1-C4Halogenoalkyl of, C1-C6Alkenyl of, C1-C6Alkynyl, -SO2-(C1-C6Alkyl of) or-SO2-N(C1-C6Alkyl of (2)2。
5. A process for the preparation of thiotriazinone isoxazolines as claimed in any one of claims 1 to 4, which comprises: in the presence of activated carbonic acid, a first base and a first solvent, carrying out contact reaction on isocyanate shown in a formula (II) and thiourea shown in a formula (III),
Figure FDA0002065692290000042
6. the method of claim 5, wherein the isocyanate of formula (II) is prepared by a process comprising: in the presence of a second solvent and a second alkali, carrying out isocyanation reaction on a raw material A shown in a formula (IV) and triphosgene shown in a formula (V),
Figure FDA0002065692290000051
7. use of a thiotriazinone isoxazoline compound according to any one of claims 1 to 4 in protoporphyrinogen oxidase inhibitors.
8. A protoporphyrinogen oxidase inhibitor comprising the thiotriazinone isoxazoline-containing compound according to any one of claims 1 to 4;
preferably, the thiotriazinone-containing isoxazoline compound is contained in an amount of 0.001 to 10% by weight based on the weight of the protoporphyrinogen oxidase inhibitor.
9. Use of the thiotriazinone-containing isoxazolines of any one of claims 1 to 4 for controlling weeds;
preferably, the weeds are broadleaf weeds and/or grassy weeds.
10. A herbicide comprising the thiotriazinone isoxazoline compound according to any one of claims 1 to 4;
preferably, the thiotriazinone-containing isoxazoline compound is present in an amount of from 0.5 to 75% by weight, based on the weight of the herbicide.
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