CN111072573A - Uracil compound containing aminomethyl thioacetyl fragment, preparation method and application thereof, and pesticide herbicide - Google Patents

Uracil compound containing aminomethyl thioacetyl fragment, preparation method and application thereof, and pesticide herbicide Download PDF

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CN111072573A
CN111072573A CN201911409980.XA CN201911409980A CN111072573A CN 111072573 A CN111072573 A CN 111072573A CN 201911409980 A CN201911409980 A CN 201911409980A CN 111072573 A CN111072573 A CN 111072573A
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alkyl
formula
compound
alkenyl
fragment
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CN111072573B (en
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席真
王大伟
薛志远
于淑一
杨光富
王现全
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Shandong Cynda Chemical Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/52—Two oxygen atoms
    • C07D239/54—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof

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Abstract

The invention relates to the field of pesticide compounds, and discloses a uracil compound containing an aminomethyl thioacetyl fragment, a preparation method and application thereof, and a pesticide herbicide. The uracil compound containing the aminomethyl thioacetyl fragment provided by the invention has excellent effects on controlling weeds, particularly on controlling broadleaf weeds and/or grassy weeds, and is safe to crops such as corn, wheat, rice and the like.

Description

Uracil compound containing aminomethyl thioacetyl fragment, preparation method and application thereof, and pesticide herbicide
Technical Field
The invention relates to the field of pesticide compounds, in particular to a uracil compound containing an aminomethyl thioacetyl fragment, a preparation method thereof, application of the uracil compound containing the aminomethyl thioacetyl fragment as a protoporphyrinogen oxidase inhibitor and a herbicide, and a pesticide herbicide containing the uracil compound containing the aminomethyl thioacetyl fragment.
Background
Protoporphyrinogen oxidase (PPO, EC 1.3.3.4) is capable of catalyzing the oxidation of protoporphyrinogen IX to protoporphyrin IX, a key enzyme in the same biosynthetic step of chlorophyll and heme.
Inhibition of PPO in plants will eventually lead to accumulation and leakage of the substrate protoporphyrin IX into the cytoplasm, leading to cytoplasmic lipid peroxidation and albino death of the plant.
In the past decades, PPO has been widely studied as an important herbicide target, and thirty or more commercial herbicides including diphenyl ethers, N-phenylphthalimide, pyrimidinediones, triazolinones, phenylpyrazoles, oxadiazoles, thiadiazoles, and oxazolinediones have been developed.
The PPO-targeted herbicide has the advantages of high efficiency, broad spectrum, short action time, lasting drug effect, low toxicity, environmental friendliness and the like.
Therefore, the discovery of compounds with high PPO enzyme inhibitor activity with novel structures remains an important target in the current research field of PPO herbicides.
Disclosure of Invention
The invention aims to provide a novel structural compound with high PPO enzyme inhibitor activity.
In order to achieve the above object, a first aspect of the present invention provides a uracil compound containing an aminomethylthioacetyl moiety, which has a structure represented by formula (I):
Figure BDA0002349712020000021
wherein, in the formula (I),
R1、R2and R3Each independently selected from H or C1-C5Alkyl groups of (a);
R4is selected from-OR5or-NR6R7；
R5Selected 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 of (C) -, (C)1-C6Alkyl) -CO-NH- (C)1-C4Alkyl of (a), substituted or unsubstituted benzyl;
R6and R7Each independently selected from H, C1-C6Alkyl of (C)1-C6Halogenoalkyl of, C3-C6Alkenyl and C3-C6Alkynyl of (a);
the optional substituents on the benzyl radical are selected from C1-C6Alkyl of (C)1-C6At least one of a halogenated alkyl group and a halogen.
In a second aspect, the present invention provides a process for preparing the aforementioned uracil compound containing an aminomethylthioacetyl fragment, which comprises: in the presence of a solvent, an amine compound shown in a formula (II) is in contact reaction with an aldehyde shown in a formula (III) and a sulfhydryl-substituted compound shown in a formula (IV),
Figure BDA0002349712020000022
wherein, in the formula (II), the formula (III) and the formula (IV), R is involved1、R2、R3And R4The definitions of (a) are the same as those in the preceding paragraph.
In a third aspect, the present invention provides the use of the aforementioned uracil compound containing an aminomethyl thioacetyl fragment as a protoporphyrinogen oxidase inhibitor.
In a fourth aspect, the present invention provides the use of a uracil compound containing an aminomethylthioacetyl moiety as described above as a herbicide.
In a fifth aspect, the present invention provides a pesticidal herbicide, which consists of an active ingredient and an adjuvant, wherein the active ingredient comprises at least one of the aforementioned uracil compounds containing an aminomethylthioacetyl fragment.
The uracil compound containing the aminomethyl thioacetyl fragment provided by the invention has excellent effects on controlling weeds, particularly on controlling broadleaf weeds and/or grassy weeds, and is safe to crops such as corn, wheat, rice and the like.
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.
As described above, the first aspect of the present invention provides a uracil compound containing an aminomethylthioacetyl moiety, which has a structure represented by the formula (I):
Figure BDA0002349712020000031
wherein, in the formula (I),
R1、R2and R3Each independently selected from H or C1-C5Alkyl groups of (a);
R4is selected from-OR5or-NR6R7；
R5Selected 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 of (C) -, (C)1-C6Alkyl) -CO-NH- (C)1-C4Alkyl of (a), substituted or unsubstituted benzyl;
R6and R7Each independently selected from H, C1-C6Alkyl of (C)1-C6Halogenoalkyl of, C3-C6Alkenyl and C3-C6Alkynyl of (a);
the optional substituents on the benzyl radical are selected from C1-C6Alkyl of (C)1-C6At least one of a halogenated alkyl group and a halogen.
"C" as described herein1-C5The alkyl group of (1) represents an alkyl group having 1 to 5 carbon atoms in total, and includes a straight-chain alkyl group, a branched-chain alkyl group or a cyclic alkyl group, and may be, for example, a straight-chain alkyl group, a branched-chain alkyl group or a cyclic alkyl group having 1,2, 3, 4 or 5 carbon atoms in total, and may be, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a n-hexyl group. "C1-C4The definition of alkyl group(s) is similar except that the total number of carbon atoms is different.
"C" as described herein1-C6The alkyl group of (1) represents an alkyl group having 1 to 6 carbon atoms in total, and includes a straight-chain alkyl group, a branched-chain alkyl group or a cyclic alkyl group, and may be, for example, a straight-chain alkyl group, a branched-chain alkyl group or a cyclic alkyl group having 1,2, 3, 4, 5 or 6 carbon atoms in total, and may be, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a n-hexyl group, a cyclopropyl group, a methylcyclo. "C1-C6Is defined analogously to the definition of "haloalkyl" merely as "C1-C6At least one H on the "alkyl group(s)" is substituted with at least one halogen atom selected from fluorine, chlorine, bromine and iodine.
The "halogen" as used herein means at least one element selected from fluorine, chlorine, bromine and iodine.
As described herein "C3-C6The "alkenyl group" of (a) means an alkenyl group having 3 to 6 carbon atoms in total and containing at least one ethylenic bond, and may be, for example, a propenyl group, a butenyl group, etc. "C3-C6The alkynyl group of (1) is similarly defined, except that it is "C3-C6The "alkynyl group" of (a) is an alkynyl group.
According to a preferred embodiment, in formula (I),
R1、R2and R3Each independently selected from H or C1-C3Alkyl groups of (a);
R4is selected from-OR5or-NR6R7；
R5Selected 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 of (C) -, (C)1-C6Alkyl) -CO-NH- (C)1-C4Alkyl of (ii);
R6and R7Each independently selected from H, C1-C6Alkyl of (C)1-C6Halogenoalkyl of, C3-C6Alkenyl and C3-C6Alkynyl group of (1).
According to another preferred embodiment, in formula (I),
R1and R2Are all H, R3Is H or methyl;
R4is selected from-OR5or-NR6R7；
R5Selected from H, C1-C6Alkyl of (C)1-C6Halogenoalkyl of, C3-C6Alkenyl of, C3-C6Alkynyl of (a), (b)C1-C6Alkyl) -O- (C of1-C6Alkyl of (C) -, (C)1-C6Alkyl) -CO-O- (C)1-C4Alkyl of (C) -, (C)1-C6Alkyl) -CO-NH- (C)1-C4Alkyl of (ii);
R6and R7Each independently selected from H, C1-C6Alkyl of (C)1-C6Halogenoalkyl of, C3-C6Alkenyl and C3-C6Alkynyl group of (1).
According to yet another preferred embodiment, the compound of formula (I) is selected from any one of the following:
Figure BDA0002349712020000051
Figure BDA0002349712020000061
as mentioned above, the second aspect of the present invention provides a process for preparing the aforementioned uracil compound containing an aminomethylthioacetyl fragment, which comprises: in the presence of a solvent, an amine compound shown in a formula (II) is in contact reaction with an aldehyde shown in a formula (III) and a sulfhydryl-substituted compound shown in a formula (IV),
Figure BDA0002349712020000062
wherein, in the formula (II), the formula (III) and the formula (IV), R is involved1、R2、R3And R4The definitions of (a) are the same as those in the preceding paragraph.
In the second aspect of the present invention, the groups in formula (II), formula (III) and formula (IV) are not repeatedly defined, and those skilled in the art should not be construed as limiting the present invention.
Preferably, the conditions of the contact reaction include: the temperature is 20-160 ℃, and more preferably 50-140 ℃; the time is 2h to 15h, more preferably 3h to 12 h.
Preferably, the solvent is selected from at least one of 1, 2-dioxane, toluene, o-xylene, m-xylene, p-xylene, n-heptane, n-octane, and n-nonane.
Preferably, the amine compound of formula (II) is used in a molar ratio to the aldehyde of formula (III) and the mercapto-substituted compound of formula (IV) of 1: (1-4): (1-3); more preferably 1: (1.5-3):(1.1-2).
The method of the present invention may further comprise the steps of performing the necessary pretreatment of the raw materials and performing the necessary post-treatment operation on the reaction product, wherein the pretreatment and post-treatment operations include but are not limited to drying, washing, filtering, column chromatography, recrystallization and the like. Several specific processing means are provided in the example section of the present invention and the person skilled in the art should not be understood as a limitation of the present invention.
As mentioned above, the third aspect of the present invention provides the use of the aforementioned uracil compound containing an aminomethyl thioacetyl fragment as a protoporphyrinogen oxidase inhibitor.
As mentioned above, a fourth aspect of the present invention provides the use of the aforementioned uracil compounds containing an aminomethylthioacetyl moiety as herbicides.
Preferably, the weed is at least one of a broadleaf weed or a grass weed.
For example, broadleaf weeds: descurainia sophia, shepherd's purse, Chenopodium album, Abutilon, Galium aparine, speedwell, Stellaria mediae, Acalypha australis, Solanum nigrum, Physalis alkekengi, purslane, Amaranthus retroflexus, and Cyprinus carpio; grassy weeds: barnyard grass, goosegrass, setaria viridis, digitaria sanguinalis, alopecurus, japanese alopecurus, jiejia, wild oat, brome, moleplant seed, paspalum distichum; cyperaceae: flutter and shaped Cyperus rotundus L.
More preferably, the weeds are at least one of abutilon, redroot amaranth, eclipta prostrata, crab grass, barnyard grass and green bristlegrass.
As described above, the fifth aspect of the present invention provides a pesticidal herbicide composed of an active ingredient including at least one of the aforementioned uracil compounds containing an aminomethylthioacetyl fragment and an adjuvant.
Preferably, the content of the active ingredient in the pesticidal herbicide is 1 to 99.99% by weight.
The invention is not particularly limited to the specific type of the adjuvant in the herbicide, and examples thereof include various surfactants, solvents and the like which are generally used in the field of herbicides.
For example, the uracil compound containing an aminomethylthioacetyl moiety according to the present invention can be dissolved in a solvent and diluted for use, and the concentration of the dissolved and diluted uracil compound in the solvent is preferably 0.05 to 0.4 g/L. The solvent for dissolving the uracil compound containing the aminomethylthioacetyl moiety may include at least one of dimethylsulfoxide and N, N-dimethylformamide, and the diluting agent may be water or the like containing a conventional additive. Preferably, one or more additives commonly used in herbicides in the art, such as surfactants, emulsifiers, etc., may also be added to the solution in which the uracil compound is dissolved.
In order to enhance the control effect and increase the application range of the uracil compound containing an aminomethyl thioacetyl fragment, the uracil compound containing an aminomethyl thioacetyl fragment of the present invention may be used alone, or may be used in combination with other commonly used herbicides (such as atrazine, fentrazamide, bromoxynil, pentoxazone, mesotrione, etc.), and the ratio of the combination is not particularly limited, and may be selected according to the ratio conventionally used in the art, as long as the control effect after combination can be enhanced, the application range can be increased, and the safety can be improved.
The present invention will be described in detail below by way of examples. In the following examples, unless otherwise specified, the various starting materials used are all common commercial products, and all purity levels are analytical grade.
Example 1: synthesis of Compound 1
Figure BDA0002349712020000081
Intermediate 3- (5-amino-4-chloro-2-fluorophenyl) -1-methyl-6- (trifluoromethyl) pyrimidine-2, 4(1 hydrogen, 3H) -dione (0.5g), 37 wt% aqueous formaldehyde (0.22g), thioglycolic acid (0.2g) and toluene (20mL) were added to a 50mL two-necked flask. The system was slowly heated to reflux with stirring for 2 h. After the reaction is finished, the solvent is removed by rotary evaporation, and the compound 1 is obtained by column chromatography.
Example 2: synthesis of Compound 2
Figure BDA0002349712020000091
Intermediate 3- (5-amino-4-chloro-2-fluorophenyl) -1-methyl-6- (trifluoromethyl) pyrimidine-2, 4(1 hydrogen, 3H) -dione (0.5g), 37 wt% aqueous formaldehyde (0.22g), methyl thioglycolate (0.24g) and toluene (20mL) were added to a 50mL two-necked flask. The system was slowly heated to reflux with stirring for 2 h. After the reaction is finished, the solvent is removed by rotary evaporation, and the compound 2 is obtained by column chromatography.
Example 3: synthesis of Compound 14
Figure BDA0002349712020000092
Intermediate 3- (5-amino-4-chloro-2-fluorophenyl) -1-methyl-6- (trifluoromethyl) pyrimidine-2, 4(1 hydrogen, 3H) -dione (0.5g), 37 wt% aqueous formaldehyde (0.22g), 2-mercaptoacetamide (0.26g) and toluene (20mL) were added to a 50mL two-necked flask. The system was slowly heated to reflux with stirring for 2 h. After the reaction is finished, the solvent is removed by rotary evaporation, and the compound 14 is obtained by column chromatography.
Example 4: synthesis of Compound 20
Figure BDA0002349712020000093
Intermediate 3- (5-amino-4-chloro-2-fluorophenyl) -1-methyl-6- (trifluoromethyl) pyrimidine-2, 4(1 hydrogen, 3H) -dione (0.5g), 37 wt% aqueous formaldehyde (0.22g), 2-mercaptopropionic acid (0.24g) and toluene (20mL) were added to a 50mL two-necked flask. The system was slowly heated to reflux with stirring for 2 h. After the reaction is finished, the solvent is removed by rotary evaporation, and the compound 20 is obtained by column chromatography.
Example 5: synthesis of Compound 22
Figure BDA0002349712020000101
Intermediate 3- (5-amino-4-chloro-2-fluorophenyl) -1-methyl-6- (trifluoromethyl) pyrimidine-2, 4(1 hydrogen, 3H) -dione (0.5g), 37 wt% aqueous formaldehyde (0.22g), ethyl 2-mercaptopropionate (0.30g) and toluene (20mL) were added to a 50mL two-necked flask. The system was slowly heated to reflux with stirring for 2 h. After the reaction is finished, the solvent is removed by rotary evaporation, and the compound 20 is obtained by column chromatography.
Some of the compounds of the present invention were synthesized in a similar manner to the above-described examples 1 to 5, and all of the synthesized compounds were confirmed to have undergone nuclear magnetic resonance and are specifically shown in Table 1.
TABLE 1
Figure BDA0002349712020000102
Figure BDA0002349712020000111
Figure BDA0002349712020000121
Comparative compound W:
Figure BDA0002349712020000131
taken from prior art US 5084084A.
Test example 1
This test example is intended to demonstrate the inhibitory activity of the uracil compounds containing an aminomethyl thioacetyl fragment 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.Agric.food chem.2019,67, 9254-9264).
Specific test methods were carried out using the method provided in (J.Agric.food chem.2019,67, 12382-12392). Kinetic constant (K) of inhibition of NtPPO enzyme by compoundi) The results are shown in Table 2.
Test example 2
The test example is intended to show the herbicidal activity inhibition (%) of the compound of the formula (I) (at a dose of 37.5 to 150 g/ha).
Test methods (potting method):
the test target is as shown in table 2, a flowerpot with an inner diameter of 6cm is taken, composite soil (garden soil: seedling culture medium is 1:2, v/v) is filled to the position of 3/4 of the flowerpot, the weed target is directly sown (the bud rate is more than or equal to 85%), soil is covered for 0.2cm, and the weed is kept for standby when the weed grows to about 3 leaves. According to at least one dosage of 150 g/hectare, 75 g/hectare and 37.5 g/hectare, dissolving with N, N-dimethylformamide and diluting with distilled water to prepare a liquid medicine with the concentration of 0.2g/L, applying the liquid medicine by an automatic spraying tower (model: 3WPSH-700E, produced by Nanjing agricultural mechanization research institute), airing the liquid medicine of the leaf surfaces of the weeds, transferring the liquid medicine into a greenhouse for culturing, and investigating the result after 15 days. The results of inhibition (%) are shown in Table 2 below. The inhibition rate is calculated by the following method (in the formula, E: fresh weight inhibition rate, C: fresh weight of overground part of a control plant, and T: fresh weight of overground part of a treated plant):
Figure BDA0002349712020000141
test example 3
This test example is intended to demonstrate the post-emergence crop safety (dose of 150 g/ha) of a partial compound of the structure shown in formula (I).
The method for testing the safety of the post-emergence crop comprises the following steps:
the test targets are shown in table 3. A flowerpot with the inner diameter of 9.0cm is taken, composite soil (vegetable garden soil: seedling raising matrix, 1:2, v/v) is filled to 3/4 positions, and a crop target (the bud ratio is more than or equal to 85 percent) is directly sown for later use. After the application of each compound at a dose of 150 g/ha in an automatic spray tower, the mixture was transferred to a greenhouse and the growth inhibition (%) of the crop was investigated after 30 days, and the results are shown in Table 3. The growth inhibition rate is calculated by the following method (in the formula, E: fresh weight inhibition rate, C: fresh weight of overground part of a control plant, and T: fresh weight of overground part of a treated plant):
Figure BDA0002349712020000142
TABLE 2
Figure BDA0002349712020000143
Figure BDA0002349712020000151
Figure BDA0002349712020000161
In table 2, a represents an inhibition ratio of 85% or more and less than 100%, B represents an inhibition ratio of 70% or more and less than 85%, C represents an inhibition ratio of 60% or more and less than 70%, and D represents an inhibition ratio of less than 60%.
TABLE 3
Compound numbering Corn (corn) Rice (Oryza sativa L.) with improved resistance to stress Wheat (Triticum aestivum L.)
1 C D D
2 C C D
15 D C D
17 D D D
18 D C D
19 D C D
25 D D D
26 D D D
W B B B
In table 3, a represents an inhibition ratio of 60% or more to 100% or less, and B represents an inhibition ratio of 50% or more to 60% or less; c represents an inhibition rate of 20% or more and 50% or less, and D represents an inhibitor of 20% or less.
Through the PPO enzyme inhibitory activity, the herbicidal activity and the crop safety experiment, the PPO enzyme inhibitory activity of the compound is in a nanomolar level, most of the compounds have good control effect on the herbicidal activity of weeds under the dosage of 37.5-150g ai/ha, and meanwhile, part of the compounds show high crop safety on tested crops at 150 gai/ha.
From the above results, it can be seen that the uracils containing an aminomethylthioacetyl fragment provided by the present invention have excellent effect of controlling weeds and are safe for crops.
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. An aminomethyl thioacetyl fragment-containing uracil compound having the structure of formula (I):
Figure FDA0002349712010000011
wherein, in the formula (I),
R1、R2and R3Each independently selected from H or C1-C5Alkyl groups of (a);
R4is selected from-OR5or-NR6R7；
R5Selected 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 of (C) -, (C)1-C6Alkyl) -CO-NH- (C)1-C4Alkyl of (a), substituted or unsubstituted benzyl;
R6and R7Each independently selected from H, C1-C6Alkyl of (C)1-C6Halogenoalkyl of, C3-C6Alkenyl and C3-C6Alkynyl of (a);
the optional substituents on the benzyl radical are selected from C1-C6Alkyl of (C)1-C6At least one of a halogenated alkyl group and a halogen.
2. The compound according to claim 1, wherein, in formula (I),
R1、R2and R3Each independently selected from H or C1-C3Alkyl groups of (a);
R4is selected from-OR5or-NR6R7；
R5Selected 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 of (C) -, (C)1-C6Alkyl) -CO-NH- (C)1-C4Alkyl of (ii);
R6and R7Each independently selected from H, C1-C6Alkyl of (C)1-C6Of (2)Alkyl radicals, C3-C6Alkenyl and C3-C6Alkynyl of (a);
preferably, in formula (I),
R1and R2Are all H, R3Is H or methyl;
R4is selected from-OR5or-NR6R7；
R5Selected 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 of (C) -, (C)1-C6Alkyl) -CO-NH- (C)1-C4Alkyl of (ii);
R6and R7Each independently selected from H, C1-C6Alkyl of (C)1-C6Halogenoalkyl of, C3-C6Alkenyl and C3-C6Alkynyl group of (1).
3. The compound of claim 2, wherein the compound of formula (I) is selected from any one of the following:
Figure FDA0002349712010000021
Figure FDA0002349712010000031
4. a process for the preparation of a uracil compound containing an aminomethylthioacetyl moiety according to any one of claims 1 to 3, which comprises: in the presence of a solvent, an amine compound shown in a formula (II) is in contact reaction with an aldehyde shown in a formula (III) and a sulfhydryl-substituted compound shown in a formula (IV),
Figure FDA0002349712010000032
wherein, in the formula (II), the formula (III) and the formula (IV), R is involved1、R2、R3And R4Are as defined in claims 1-3.
5. The method of claim 4, wherein the conditions of the contact reaction comprise: the temperature is 20-160 ℃, preferably 50-140 ℃; the time is 2h-15h, preferably 3h-12 h.
6. The method according to claim 4, wherein the solvent is selected from at least one of 1, 2-dioxane, toluene, o-xylene, m-xylene, p-xylene, n-heptane, n-octane, and n-nonane;
preferably, the amine compound of formula (II) is used in a molar ratio to the aldehyde of formula (III) and the mercapto-substituted compound of formula (IV) of 1: (1-4): (1-3); preferably 1: (1.5-3):(1.1-2).
7. Use of the aminomethyl thioacetyl fragment-containing uracil compound according to any one of claims 1 to 3 as protoporphyrinogen oxidase inhibitor.
8. Use of the uracil compound containing an aminomethylthioacetyl moiety as described in any one of claims 1 to 3 as a herbicide.
9. The use of claim 8, wherein the weed is at least one of a broadleaf weed or a grass weed;
preferably, the weeds are at least one of abutilon, redroot amaranth, eclipta prostrata, crab grass, barnyard grass and green bristlegrass.
10. A pesticidal herbicide, which is characterized by being composed of an active ingredient comprising at least one of the uracil compounds containing an aminomethylthioacetyl fragment according to any one of claims 1 to 3 and an adjuvant.
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Citations (2)

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US20060089262A1 (en) * 2002-05-02 2006-04-27 Hans-Georg Schwarz Substituted (thioxo)carbonylamino phenyl uraciles

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