CN107353238A - Substituted benzoylcyclohexan cyclohexadione compounds or its dynamic isomer, salt, preparation method, Herbicidal combinations and application - Google Patents

Substituted benzoylcyclohexan cyclohexadione compounds or its dynamic isomer, salt, preparation method, Herbicidal combinations and application Download PDF

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CN107353238A
CN107353238A CN201710707265.9A CN201710707265A CN107353238A CN 107353238 A CN107353238 A CN 107353238A CN 201710707265 A CN201710707265 A CN 201710707265A CN 107353238 A CN107353238 A CN 107353238A
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alkyl
group
carbonyl
alkoxy
substituted
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CN107353238B (en
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连磊
征玉荣
何彬
彭学岗
金涛
崔琦
刘娜
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Qingdao Qing Yuan Compound Co Ltd
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Qingdao Qing Yuan Compound Co Ltd
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Priority to PCT/CN2017/110610 priority patent/WO2019033590A1/en
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    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

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Abstract

The invention belongs to technical field of pesticide, and in particular to a kind of substituted benzoylcyclohexan cyclohexadione compounds or its dynamic isomer, salt, preparation method, Herbicidal combinations and application.Substituted the benzoylcyclohexan cyclohexadione compounds or its dynamic isomer, salt, as shown in formula I：In formula, R1R2N is representedR is represented

Description

Substituted benzoylcyclohexan cyclohexadione compounds or its dynamic isomer, salt, preparation Method, Herbicidal combinations and application
Technical field
The invention belongs to technical field of pesticide, and in particular to a kind of substituted benzoylcyclohexan cyclohexadione compounds or its Dynamic isomer, salt, preparation method, Herbicidal combinations and application.
Background technology
The preventing and treating of weeds is to realize a vital link during high-efficiency agriculture, although the herbicide kind of in the market Class is various, for example, patent WO97/46530 A1 disclose ketone compounds shown in below formula I as herbicide：Patent CN1416422 A disclose the substituted benzoylcyclohexenones shown in below formula (I) Compound is used as herbicide：But due to the continuous expansion in market, weeds it is anti- The problems such as economy of property, the service life of medicine and medicine and people are to the pay attention to day by day of environment, it is necessary to scientists Constantly study and then develop new efficient, safety, economy and the herbicide kind with the different modes of action.
The content of the invention
For a kind of property of medicine of exploitation is higher, activity profile is wider, the more preferable pharmaceutical actives of security, the invention provides one kind Substituted benzoylcyclohexan cyclohexadione compounds or its dynamic isomer, salt, preparation method, Herbicidal combinations and application.
The technical solution adopted by the present invention is as follows：
A kind of substituted benzoylcyclohexan cyclohexadione compounds or its dynamic isomer, salt, as shown in formula I：
In formula,
R1R2N is representedWherein,
Het is selected from three to eight circle heterocycles, also following former containing 0-3 in addition to the N atoms on the ring on containing C and 1- positions The part of son or group as ring：O、NRb、S、SO、SO2, C=O, C=NRbOr C=NORb, and work as C=O, C=NRbOr C =NORbAt 2- positions, 3- positions can not be N or S；
RbSelected from hydrogen, C1~6Alkyl, halo C1~6Alkyl, C2~6Alkenyl, halo C2~6Alkenyl, C1~6Alkoxy C1~6Alkyl, Halo C1~6Alkoxy C1~6Alkyl, C1~6Alkyl-carbonyl, halo C1~6Alkyl-carbonyl, C1~6Alkyl sulphonyl, C1~6Alkoxy carbonyl Base, C1~6Alkyl amino-carbonyl, C1~6Alkyl-carbonyl C1~6Alkyl, C1~6Alkoxy carbonyl C1~6Alkyl, C1~6Alkyl amino-carbonyl C1~6Alkane It is base, unsubstituted or halogen, nitro, cyano group, C are independently selected from by 1-31~6Alkyl, halo C1~6Alkyl, C1~6Alkoxy, halogen For C1~6Alkoxy, C1~6Aryl that group in alkyl-carbonyl is substituted, heteroaryl, aryl carbonyl, Heteroarylcarbonyl, aryl Sulfonyl, arylmethyl, hetervaromatic methyl；
RaSelected from one or more of following group group：Hydrogen, halogen, cyano group, nitro, hydroxyl, carboxyl, amino, C1- C6Alkyl sulphonyl, C1~6Alkyl, halo C1~6Alkyl, C2~6Alkenyl, halo C2~6Alkenyl, C1~6Alkoxy, halo C1~6Alcoxyl Base, C1~6Alkylamino, C2~6Alkenyloxy group, halo C2~6Alkenyloxy group, C2~6Enamino, halo C2~6Enamino, C1~6Alkyl-carbonyl, halogen For C1~6Alkyl-carbonyl, C1~6Alkoxy carbonyl, C1~6Alkyl amino-carbonyl, C1~6Alkoxy C1~6Alkyl, halo C1~6Alkoxy C1~6 Alkyl, C1~6Alkyl carbonyl epoxide C1~6Alkyl, C1~6Alkoxy C1~6Alkoxy, halo C1~6Alkoxy C1~6Alkoxy, C1~6Alkane Epoxide carbonyl C1~6Alkoxy, C1~6Alkyl carbonyl epoxide, halo C1~6Alkyl carbonyl epoxide, C1~6Alkyl-carbonyl-amino, C1~6Alkane Base sulfonyl epoxide, C1~6Alkyl sulfonyl-amino, C1~6Alkyl-carbonyl C1~6It is alkoxy, unsubstituted or independent selected by 1-3 From halogen, nitro, cyano group, C1~6Alkyl, halo C1~6Alkyl, C1~6Alkoxy, C1~6The virtue that group in alkyl-carbonyl is substituted Base, heteroaryl, aryl carbonyl epoxide, aryl sulfonyl epoxide, arylmethyl epoxide, hetervaromatic methyl epoxide, aryl-amino-carbonyl, Arlysulfonylamino, arylmethyl amino or hetervaromatic methyl amino；
Or R1、R2Represent hydrogen respectively, containing be with or without halogen substitution contain 0~4 heteroatomic C1~8Alkyl, C1~8Alkene Base or C1~8Alkynyl, containing be with or without halogen substitution contain 0~4 heteroatomic C1~4Acyl group, it is unsubstituted or by selected from halogen, Containing be with or without halogen substitution contain 0~4 heteroatomic C1~4The C that one or more of alkyl group is substituted3~6Cycloalkanes Base；
R is representedWherein,
R11Selected from hydrogen, C1-C6Alkyl, C3-C6Cycloalkyl, C1-C6Alkoxy, C1-C6Alkoxy C1-C6Alkyl, C1-C6Alkyl Carbonyl, C1-C6Alkoxy carbonyl, C1-C6Alkylthio group, containing be with or without the 6-10 members aryl of halogen substitution, containing being with or without halogen The heteroatomic 5-10 unit's heteroaryls containing 1-3 O, S, N of substitution, n=0-6；
Y is selected from C, N, O or S；
Z is selected from C, N, O, S, SO, SO2Or C=O；
Or as n=2 and when Z and/or Y are selected from C, two R on different C atoms11Connect into CH2、(CH2)2、 (CH2)3、(CH2)4、(CH2)5、(CH2)6、O、O(CH2)2O、O(CH2)3O、O(CH2)4O、S(CH2)2S or S (CH2)3S；
Or as n=2, two R on same C atoms11Connect into following group：(CH2)2、(CH2)3、(CH2)4、 (CH2)5、(CH2)6、O、O(CH2)2O、O(CH2)3O、O(CH2)4O、S(CH2)2S or S (CH2)3S；
R12Selected from-OR13Or-SR13, wherein, R13Selected from hydrogen, C1-C6Alkyl, C1-C6Alkyl-carbonyl, C1-C6Alkyl sulfonyl Base, C2-C6Alkenyl, halo C2-C6Alkenyl, C2-C6Alkynyl, C1-C6Alkoxy carbonyl C1-C6Alkyl, C1-C6Alkyl amino-carbonyl C1-C6 It is alkyl, unsubstituted or halogen, nitro, cyano group, C are independently selected from by 1-31-C6Alkyl, halo C1-C6Alkyl, C1-C6Alcoxyl Base or halo C1-C6Aryl that group in alkoxy is substituted, arylmethyl, aryl carbonyl, aryl sulfonyl, heteroaryl, heteroaryl Base carbonyl or aryl carbonyl methyl.
Preferably, Het is selected from 4~8 membered lactams bases, imidazole radicals, pyrazolyl, RaSelected from C1~4Alkyl, C1~4Alkoxy, nitre Base, halogen, cyano group, amino, C1~6Alkylamino, C1~6One or more of alkyl sulphonyl group；
Or R1、R2In one represent containing the C containing 0~4 O, S, N for being with or without halogen substitution1~4Acyl group；It is another It is individual to represent hydrogen, containing the C containing 0~4 O, S, N for being with or without halogen substitution1~8Alkyl, C1~8Alkenyl or C1~8Alkynyl, it is unsubstituted Or contained 0~4 heteroatomic C selected from halogen, containing be with or without that halogen substitutes1~4One or more of alkyl group institute Substituted C3~6Cycloalkyl；
As n=2 and when Z and/or Y are selected from C, two R on different C atoms11Connect into CH2、(CH2)2、 (CH2)3、(CH2)4、(CH2)5、(CH2)6、O、O(CH2)2O、O(CH2)3O、O(CH2)4O、S(CH2)2S or S (CH2)3S；
Or as n=2, two R on same C atoms11Connect into following group：(CH2)2、(CH2)3、(CH2)4、 (CH2)5、(CH2)6、O、O(CH2)2O、O(CH2)3O、O(CH2)4O、S(CH2)2S or S (CH2)3S。
It is highly preferred that Het be selected from butyrolactam base, valerolactamyl, caprolactam base, oenantholcatam base, piperazine ketone group, Morpholine ketone group, thiomorpholine ketone group, imidazole radicals, pyrazolyl, RaSelected from fluorine, chlorine, methyl, ethyl, methoxyl group, ethyoxyl, nitro, Cyano group, amino, C1~6Alkylamino, C1-C6One or more of alkyl sulphonyl group；
Or R1Represent acetyl group, acetyl fluoride base, difluoro acetyl group, trifluoroacetyl group, methoxyacetyl, ethoxy acetyl Base, methoxy propiono, ethoxy propiono, R2Represent hydrogen or unsubstituted or by selected from fluorine, methoxyl group, ethyoxyl, propoxyl group, fourth Methyl that one or more of epoxide, methoxyethoxy group is substituted, ethyl, propyl group, butyl, amyl group, cyclopropyl；
As n=2 and when Z and/or Y are selected from C, two R on different C atoms11Connect into CH2、(CH2)2、 (CH2)3、O、O(CH2)2O、O(CH2)3O、S(CH2)2S or S (CH2)3S；
Or as n=2, two R on same C atoms11Connect into following group：(CH2)2、(CH2)3、O、O (CH2)2O、O(CH2)3O、S(CH2)2S or S (CH2)3S。
It is further preferred that R is selected from one of group shown in following formula：
R11Selected from hydrogen, C1-C6Alkyl, C3-C6Cycloalkyl, C1-C6Alkoxy, C1-C6Alkoxy C1-C6Alkyl, C1-C6Alkyl Carbonyl, C1-C6Alkoxy carbonyl, C1-C6Alkylthio group, containing be with or without the 6-10 members aryl of halogen substitution, containing being with or without halogen The heteroatomic 5-10 unit's heteroaryls containing 1-3 O, S, N of substitution, n=0-6；
R12Selected from hydroxyl, C1-C3Alkoxy, C1-C3Alkyl carbonyl epoxide, C1-C3Alkyl sulphonyl epoxide, C2-C4Alkene oxygen Base, halo C2-C4Alkenyloxy group, it is unsubstituted or by 1-3 be independently selected from fluorine, chlorine, bromine, nitro, cyano group, methyl, trifluoromethyl, Phenoxy group that group in methoxyl group or trifluoromethoxy is substituted, benzyl epoxide, thiophenyl, benzyl sulfenyl, benzoyloxy, Benzenesulfonyl epoxide, benzoyl methoxyl group, containing the heteroatomic 5-10 unit's heteroaryls epoxide of 1-3 O, S, N or containing 1-3 O, S, The heteroatomic 5-10 unit's heteroaryls carbonyl epoxides of N.
Described salt is sylvite, sodium salt, ammonium salt, calcium salt, pyridiniujm or choline salt.
In the definition of general formula compound given above, collect term used and be defined as follows：
Described aryl is 6-10 member aryl, including phenyl or naphthyl etc.；Described heteroaryl is containing 1-3 O, S, N Heteroatomic 5-10 unit's heteroaryls, such as pyridine radicals, pyrimidine radicals, pyrazinyl, furyl, thienyl, pyrrole radicals, pyrazolyl, thiophene Oxazolyl, oxazolyl, isoxazolyls, imidazole radicals, triazolyl, oxadiazoles base, thiadiazolyl group, pyridazinyl, triazine radical, quinolyl, quinoline Quinoline base, indyl, BTA base, benzothienyl, benzofuranyl, isoquinolyl, tetrahydric quinoline group etc..
In the compound of the present invention, because tautomerism etc. may have a variety of dynamic isomers, the present invention includes institute There are dynamic isomer and its mixture of any ratio.
Described salt is acceptable salt in Pesticide Science, is preferably that this class compound is carried out with chemically acceptable acid Acid-addition salts made from reaction, or compound and the salt of alkali compounds reaction generation wherein with acidic-group.Wherein, Described acid is preferably selected from inorganic acid (such as hydrochloric acid, sulfuric acid, phosphoric acid or hydrobromic acid) and organic acid (such as oxalic acid, maleic acid, richness Horse acid, malic acid, tartaric acid, citric acid or benzoic acid etc.)；Described alkali compounds is preferably selected from sodium hydroxide, hydrogen-oxygen Change potassium, calcium hydroxide, sodium carbonate, potassium carbonate, sodium acid carbonate or saleratus etc..Above-mentioned pharmaceutically acceptable salt easily divides From conventional separation methods being used to purify, such as solvent extraction, dilution, recrystallization, column chromatography and prepare thin-layer chromatography.
It is a kind of to prepare the substituted benzoylcyclohexan cyclohexadione compounds or its dynamic isomer, the method for salt, its Comprise the following steps：
(1) using the compound and compound as shown in formula IIReacted, prepared such as formula I-1 institutes The compound shown；
(2) by the compound and compound R as shown in formula I-113X or R13S-M is reacted, and is made such as formula I-2 institutes The compound shown；
Wherein, X represents halogen, hydroxyl, and M represents alkali metal or alkaline-earth metal (preferably Na, Li, K, Ca, Mg etc.), reaction side Formula is as follows：
The step (1) is carried out in non-protonic solvent, in the presence of alkali and catalyst.
In the step (2) with R13X is carried out when reacting in non-protonic solvent, in the presence of alkali, with R13S-M reacts When carried out in non-protonic solvent, in the presence of alkali and activator.
Reaction temperature is -30 DEG C -180 DEG C, preferably -5 DEG C -90 DEG C.
Wherein, when X represents hydroxyl, need to add dehydrating agent, such as thionyl chloride, DCC or CDI in reaction.
The solvent is dichloromethane, 1,2- dichloroethanes, acetonitrile, toluene, tetrahydrofuran, 1,4- dioxane, acetic acid Combination more than one or both of non-protonic solvents such as ethyl ester, preferably dichloromethane, 1,2- dichloroethanes or toluene.
The alkali is sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium acid carbonate, saleratus, three Ethamine, DIPEA or DBU, preferably triethylamine or potassium carbonate.
The catalyst is acetone cyanohydrin.
The activator be mesyl chloride, paratoluensulfonyl chloride, trim,ethylchlorosilane, trifluoro-acetyl chloride, TFAA, Trifluoromethanesulfchloride chloride,Deng the carbonyl for activating on cyclohexanedione makes its easy Reacted with other reagents.
A kind of Herbicidal combinations, contain described substituted benzoylcyclohexan cyclohexadione compounds or its tautomerism At least one of body, salt are used as active component.
The weight percentage of the active component is 0.1-99%.
A kind of method for controlling noxious plant, including the described substituted benzoylcyclohexan diketone by herbicidally effective amount At least one of class compound or its dynamic isomer, salt or described Herbicidal combinations use are on plant or harmful plant Object area.
At least one of described substituted benzoylcyclohexan cyclohexadione compounds or its dynamic isomer, salt or institute Application of the Herbicidal combinations stated on control weeds.
Described substituted benzoylcyclohexan cyclohexadione compounds or its dynamic isomer, salt are used to prevent and kill off to be used as Weeds in thing.
The crop that the useful crop is genetically modified crops or genome editing technique treats.
For many economically important unifacial leaves and dicotyledonous harmful plants, compound of formula I of the invention, which has, to be protruded Activity of herbicide.The active material of the present invention is effective also for perennial weeds, and these weeds are from rhizome, root-like stock or other Perennial organ on grow out, it is difficult to control.On this point, if prior to seeding, sprout before or sprout after using should Material is typically inessential.The controllable unifacial leaf of specifically mentioned the compounds of this invention and the representation example of broadleaf weed group, The species for the determination being not limited to.The example of the weed species of active material useful effect includes monocotyledon：It is annual In Avena, rye, careless category, amur foxtail category, farad this, barnyard grass, knotgrass, setaria and Cyperus, and perennial wheatgrass Category, Cynodon, cogon and sorghum and perennial Cyperus.
On dicotyldenous weed species, its act on for example annual Bedstraw of species that can be expanded to, Viola, Veronica, lamium, Stellaria, Amaranthus, sinapsis alba category, Ipomoea, chrysanthemum harvest spp, Matricaria and abutilon, and it is perennial Weeds japanese bearbind genus, Cirsium, Rumex and artemisia.Active material of the present invention rice growing it is this it is undetermined under the conditions of effectively control have Evil plant, such as barnyard grass, Sagittaria, Waterplantain, Eleocharis, sugarcane grass and Cyperus.If the compounds of this invention is applied before rudiment For soil surface, the rice shoot of weeds can be prevented completely before weeds grow, or just be stopped growing when weeds grow cotyledon, It is finally completely dead after three to four weeks.The compounds of this invention especially resists the good activity of following plants, and A Pila is careless, small White dead nettle, volume stem smartweed, chickweed, Changchun cane leaves Veronica, Veronica persica, heartsease and amaranth, Bedstraw and summer cypress.
Although the compounds of this invention has excellent activity of herbicide for unifacial leaf and dicots weeds, for important Economy class crop plants, such as wheat, barley, rye, rice, corn, beet, cotton and soybean do not damage but at all, Either infringement is inappreciable.It is compatible particularly with cereal crops very well, such as wheat, barley and corn, particularly Wheat.Therefore, the compounds of this invention is very suitable for the useless plant being selectively controlled in agricultural crop or ornamental plant.
Due to their deweeding property, in the plant cultivation of genetic engineering that is known or will occurring, these active matters Matter can be used for controlling noxious plant.Genetically modified plants generally have superior character, such as particularly special to specific insecticide The resistance of herbicide is determined, to plant disease or the resistance of the pathogenic microorganisms of plant disease, such as specific insect or true The microorganism of bacterium, bacterium or virus.Other especially characters are relevant with following conditions of product, for example, quantity, quality, storage Stability, component and special composition.So, it is known that the transgenic plant product of acquisition have increased content of starch or Improved starch quality or different Fatty acid components.
The compound of formula I or its salt of the present invention is preferred for, the crop and ornamental plant of economically important transgenosis, example Such as cereal, such as wheat, barley, rye, oat, grain, rice, cassava and corn or for beet, cotton, soybean, rape Seed, the cultivation of potato, tomato, pea and other vegetable plants.Compound of formula I is preferred for the weeding of useful plant cultivation Agent, these plants are with the resistance to the action of a drug or by toxic action of the genetic engineering to herbicide with the resistance to the action of a drug.
It is traditional to breed with including than known plants with the method for improving shape plant, such as traditional mating method Bred with mutant strain.In other words, can be by means of the method for genetic engineering (see, e.g. EP-0221044 A, EP- 0131624 A) come obtain with improve character new plant.Such as, it has been described that several methods：
- in order to improve the Starch synthesis in plant, change crop plants (such as WO 92/11376, WO using genetic engineering 92/14827, WO 91/19806)；
- the transgenic crop plant resistant to specific herbicide, to careless fourth phosphine herbicide (such as EP-0242236 A, EP-0242246 A) or to glyphosate-class herbicides (WO 92/00377), or to sulfonylurea herbicide (EP-0257993 A, US-5013659 A)；
The transgenic crop plant of-such as cotton, it can produce bacillus thuringiensis toxin (Bt toxin), and this toxin can To defend the infringement of specific pests on plants (EP-0142924 A, EP-0193259 A)；
- the transgenic crop plant (WO91/13972) with improved Fatty acid component.
Known many can prepare with improve character genetically modified plants molecular biotechnologies (see, e.g. Sambrook etc., 1989, molecule amplification, the laboratory manual second edition, Cold Spring Harbor Laboratory publication, Cold SpringHarbor, New York；Or Winnacker " Gene und Klone " [gene and clone], VCH Weinheim, the second edition 1996 or Christou, " plant The trend of science " 1 (1996) 423-431)).In order to realize the operation of genetic engineering, nucleic acid molecules may be introduced plasmid, led to The restructuring of DNA sequence dna is crossed, undergos mutation or sequence changes.Using above-mentioned standard method, such as substrate, removing unit can be exchanged Sub-sequence increases the sequence naturally or synthesized.In order to which DNA fragmentation is interconnected, it is possible to be accompanied with combination in fragment Body or connector.
The plant cell for the gene prod for reducing activity can be prepared with following methods, for example, it is at least one suitable by expressing When antisense-RNA, justice-RNA reach the effect of co-suppression, or by expressing the ribozyme of at least one appropriate structuring, it The transcription product of specific cleavage said gene product.
For this purpose, it is possible to use including the DNA molecular of gene outcome whole coded sequence, include that may be present Any flanking sequence, and using including the DNA molecular of only only a part coded sequence, these parts must long enough to reach The effect of antisense in cell.Can also use has high homology but incomplete same sequence with gene outcome coded sequence Row.
When the express nucleic acid molecule in plant, the protein of synthesis can be determined in any desired plant cell room Position.But in order to be positioned in specific room, it is possible to for example connect code area with DNA sequence dna, to ensure to determine in ad-hoc location Position.These sequences be known to those skilled in the art (see, e.g. Braun etc., EMBO J.11 (1992) 3219- 3227；Wolter etc., Proc.Natl.Acad.Sci.USA 85 (1988), 846-850；The Plant such as Sonnewald are J.1 (1991), 95-106).
Transgenic plant cells can be recombinated using known technology onto whole plant.Genetically modified plants can be to appoint What desired plant variety, i.e. unifacial leaf and dicotyledon.In such a way, by overexpressing, forbidding or suppress homologous (=naturally) gene or gene order, or pass through (=outside) gene or the expression of gene order of xenogenesis, it is possible to Obtain the genetically modified plants for improving character.
When using the active material of the present invention on the crop in transgenosis, except with can be observed on other crops Suppression noxious plant effect outside, special effect is often had on corresponding genetically modified crops, for example, can improve or Expand the scope of control weeds, improve amount of application during application, the preferably resistance to the action of a drug of genetically modified crops and the performance of herbicide very Good combination, and the growth of the crop plants of transgenosis and the influence of yield.Therefore present invention provides the compound Purposes, as herbicide control transgenic crop plant in noxious plant.
Other the compounds of this invention can substantially adjust the growth of crop plants.Plant metabolism is participated in by adjusting, is used The component of these compound oriented control plants and promotion harvest, such as make plant desiccation and stunted growth.And they are also fitted In adjusting and suppressing undesirable plant growth, the growth without destroying crop.The many unifacial leaves that are grown in for suppressing plant are planted Play very important effect in thing and dicotyledon crop because can so reduce or completely pre- lodging-prevention.
The compound of the present invention can be applied using in general preparation, wettable powder, emulsifiable concentrates can be used, can spray Solution, powder or the particle spilt.So present invention provides the herbicidal composition including compound of formula I.According to common The physical parameter of biology and/or chemistry, compound of formula I can be prepared with various ways.Suitable preparation selection example for：Can WP (WP), water miscible powder (SP), water miscible concentrate, emulsifiable concentrates (EC), for example oil in water disperse and Water in oil disperse emulsion (EW), sprayable solution, suspending agent concentrate (SC), dispersible oil-suspending agent (OD), with oil or Water is suspension, miscible oily solution, powder (DP), capsule suspension liquid (CS), the bag core (seeddressing) of diluent Composition, for broadcasting sowing with the particle of soil pesticide, injection particle, coated particle and absorbing particles, dispersible particle in water (WG), water miscible particle (SG), ULV (ultra-low volume) formulas, micro-capsule and wax work.These single preparation types are known , it is described in the following references, for example, Winnacker-K ü chler, " Chemische Techonologie " [chemical works Skill], volume 7, C.Hauser Verlag Munich, the 4th edition 1986；Wade van Valkenburg, " Pesticide Formulations ", Marcel Dekker, N.Y., 1973；K.Martens, " Spray Drying " handbooks, the 3rd edition 1979, G.Goodwin Ltd.London。
Necessary formulation auxiliary agents, such as inert substance, surfactant, solvent and other additives are similarly known, And described in following files, such as Watkins " powder diluent insecticide and carrier handbook ", the second edition, Darland books Caldwell N.J.；H.v.01phen " introduction of Clay Colloids chemistry ", the second edition, J.Wiley and Sons, N.Y.； C.Marsden " solvent guide " second edition, Interscience, N.Y.1963；McCutcheon " detergent and emulsifying agent Annual report ", MC distributing and releasing corporations, Ridgewood N.J.；Sisley and Wood, " surfactant encyclopedia ", chemistry is published public Department, N.Y.1964；'s[ethylene oxide adduct surface Activating agent], Wiss.Verlagagesell.Stuttgart 1976；Winnacker-K ü chler " Chemische Technologie " [chemical technology], volume 7, C.Hauser Verlag Munich, the 4th edition 1986.
Wettable powder equably can be dispersed in water, except active material, in addition to diluent or inert substance, from Son and nonionic surface active agent (wetting agent, dispersant), such as polyethoxy alkylphenol, polyethoxy fatty alcohol, polyoxy Ethyl fatty race amine, poly alkyl alcohol ether sulfates, alkylsulfonate, alkyl benzene sulfonate, wooden sodium sulfonate, 2,2 '- Dinaphthyl methane -6,6 '-sodium disulfonate, nekal or oleoyl N-methyltaurine sodium., will in order to prepare wettable powder The active material fine grinding of herbicide, such as using conventional instrument, hammer-mill, fan grater and jet-propelled grater such as are used, Simultaneously or sequentially it is mixed into auxiliary agent.
Active material dissolving is prepared into emulsifiable concentrates, solvent such as butanol, cyclohexanone, dimethyl formyl in organic solvent Amine, the aromatic compounds of dimethylbenzene or higher or the mixture of hydrocarbon or solvent, and add one or more Ion and/or nonionic surface active agent (emulsifying agent).The example for the emulsifying agent that can be used is such as detergent alkylate The alkyl aryl sulphonic acid calcium of sulfoacid calcium, or nonionic emulsifier, for example, fatty acid polyglycol diol ester, alkylaryl polyglycol ether, Poly alkyl alcohol glycol ethers, propylene oxide-oxirane condensation product, alkyl, polyether, the mountain of such as sorbitan fatty acid ester Pears glycan ester, or the polyoxyethylene sorbitan ester of such as Polyoxyethylene sorbitan fatty ester.
Active material and solid matter in small, broken bits are ground to obtain powder, such as solid matter such as talcum, kaolin, bentonite With the natural clay or diatomite of pyrophyllite.It can be prepared with water or oil for the suspension of substrate by following methods, such as profit Wet-milling is carried out with commercial general bead mill, adds or be added without the surfactant of another above-mentioned preparation type.
The emulsion of such as oil-water emulsifiers (EW) is prepared, aqueous organic solvent can be used, use agitator, colloid Mill and/or static mixer, if it is desired, add the surfactant of another preparation type as described above.
Granule is prepared with following methods, active material is sprayed onto on adsorbate, using inert material particle, or will be living Property material be concentrated to for example husky, surface of kaolinite carrier, inert material is granulated by adhesive, adhesive such as polyethylene Alcohol, Sodium Polyacrylate or mineral oil.Suitable active material can be granulated with the method for preparing fertiliser granulates agent, if desired Fertilizer can be mixed with.Aqueous suspension granule is prepared using usual way, such as sprinkling-drying, fluidized bed prilling, mill are made Grain, mixed using high-speed mixer, and extruded in the case of without solid, inert material.
On using mill, fluid bed, extruder and the preparation method of sprayed particle agent, referring to following techniques, such as " Spray Drying handbooks " third edition 1979, G.Goodwin Co., Ltds, London；J.E.Browning, " Agglomeration ", chemistry and engineering 1967,147ff pages；" engineer's handbook of Perry ' s chemistry ", the 5th edition, McGraw-Hill, New York 1973,8-57 pages.If it is to be understood that the preparation on crop protection products, see, for example, G.C.Klingman, " Weed Control as a Science ", John Wiley and Sons companies, New York, 1961 81-96 Page and J.D.Freyer, S.A.Evans " weed control handbook ", the 5th edition, Blackwell Scientific Rublications, Oxford University 1968,101-103 pages.
Agrochemical formulation generally comprises the active material Formulas I of by weight 0.1 to 99%, particularly 0.1 to 95%. The concentration of active material is in wettable powder, and by weight for example from about 10 to 99%, common formulation components are formed and pressed Weight meter surplus is to 100%.Concentration by weight of the active material in emulsifiable concentrates can be about 1 to 90%, preferably 5 To 80%.Powder formulation includes by weight 1 to 30% active material, it is usually preferred to by weight 5 to 20% active matter Matter, but sprayable solution includes by weight about 0.05 to 80%, preferably 2 to 50% active material.Hanged on water The content of active material in floating particles agent, be mainly liquid or solid-state according to active material, and use when being granulated auxiliary agent, fill out Material etc..The content of active material is for example by weight between 1 to 95% in aqueous suspension granule, preferably by weight 10 To between 80%.
The preparation of described active material can include tackifier, wetting agent, dispersant, emulsifying agent, bleeding agent, anti-in addition Rotten agent, antifreezing agent, solvent, filler, carrier, colouring agent, defoamer, evaporation suppressor and generally all conventional in all cases PH and viscosity modifier.
Based on these preparations, it is also possible to and other biocidal activity materials for example insecticide, acaricide, herbicide and Bactericide mixes, and can also be mixed with safener, fertilizer and/or plant growth regulator, hybrid mode can be to be pre-mixed Good or filling mixing.
In mixture preparation or bucket mix formulation, can be with the suitable active material of the active material mixing of the present invention, Such as《World pesticide new varieties technology is complete works of》, Scientia Agricultura Sinica technology publishing house, 2010.9 and document incorporated herein in Known substance.Such as herbicidal activity material mentioned below can mix with Formulas I mixture, (remarks：The name of compound Claim, be either according to the common name of International Organization for standardization (ISO) or be chemical name, there is code name when appropriate)： Acetochlor, butachlor, alachlor, propisochlor, isopropyl methoxalamine, S-metolachlor, pretilachlor, propachlor, kecaoan, naphthalene Propionyl grass amine, the left-handed naphthalene propionyl grass amines of R-, propanil, mefenacet, diphenamide, diflufenican, N-alpha-chloroacetyl-N-isopropyl-o ethylaniline, fluorine butyryl Careless amine, bromobutide, dimethenamid, dimethenamidP, ethobenzanid, flufenacet, thenylchlor, pyrrole grass Amine, isoxaben, flampropMmethyl, flampropMisopropyl, allidochlor, pethoxamid, chloranocryl, the grass of ring third Amine, mefluidide, monalide, delachlor, prynachlor, terbuchlor, xylachlor, dimethachlor, amine of taking to the greenwood, Front three ring grass amine, clomeprop, propyzamide, valeryl benzene grass amine, the careless amine of card, suffer, three rings match careless amine, butylene grass Amine, tebutam, benzyl grass amine, quinone duckweed amine, dichlofluanid, naproanilide, acetyl alachlor, quinclorac, fenacet, pyrrole cyanogen grass amine, benzene More grams of grass is dead, chlorothiamid, chlorine phthalimide, fourth amidine amine, fluorine metazachlor, atrazine, Simanex, prometryn, cyanatryn, symetryne, Ametryn, propazine, dipropetryn, SSH-108, terbutryn, Garagard, triaziflam, cyprazine, proglinazine, trietazine, flutter Go out net logical, Gesadrual, nitrine, desmetryn, dimethametryn, third blue or green Tianjin of ring, green bristlegrass of going out Tianjin, another Ding Jin, Zhong Dingtong, Te Dingtong, methoxy Third is net, cyanatryn, ipazine, chlorazine, atraton, weed eradication are logical, radix glycyrrhizae Tianjin, cyanuric acid, Indaziflam, green sulphur are grand, first Sulphur is grand, bensulfuron-methyl, chlorimuron, tribenuron-methyl, thifensulfuron methyl, pyrazosulfuron, mesosulfuron, iodosulfuron-methyl-sodium, formyl Amino Sulfometuron Methyl, cinosulfuron, triasulfuron, sulfometuronmethyl, nicosulfuron, ethametsulfuron, amidosulfuron, ethoxysulfuron, ring Third Sulfometuron Methyl, rimsulfuron, azimsulfuron, pyridine ethyl methyl, monosulfmeturon, single phonetic sulphur ester, flucarbazone, flupyrsulfuron-methyl-sodium, Fluorine pyrazosulfuron, oxasulfuron, imazosulfuron, primisulfuronmethyl, procarbazone, prosulfuron, Sulfosulfuron, trifluoro pyridine Sulphur is grand, triflusulfuronmethyl, tritosulfuron, metsulfuron-methyl sodium salt, flucetosulfuron, Sulfonylurea, orthosulfamuron, Propyrisulfuron (promazine Sulfometuron Methyl), piperazine pyrazosulfuron, acifluorfen, fomesafen, lactofen, second carboxylic AKH7088, Oxyfluorfen, Mo 9 granular, aclonifen, ethoxyfen-ethyl, bifenox, fluoroform grass ether, methoxy weeding Ether, fluorodifen, fluorination nitrofen, fluorine furan grass ether, nitrofen, first grass ether, diformazan grass ether, fluorine lactazone grass ether, AKH7088 ester, Halosafen, chlortoluron, isoproturon, linuron, diuron, Sha flutter grand, fluometuron, benzthiazuron, methabenzthiazuron, cumyluron, Ethidimuron, isouron, terbufos benzthiazuron, buturon, bromax, methyldymron, phenobenzuron, methoxy daimuron, metobromuron, first Oxygen is grand, afesin, telvar, Tupersan, fenuron, fluorine sulphur are grand, neburea, chloroxifenidium, herban, isonoruron, Alipur-O, Thiazfluron, tebuthiuron, difenoxuron, to fluon, methylamine methabenz thiazuron, Long Caote, front three isourea, dimefuron, Monisouron, Anisuron, Methiuron, Chloreturon, four fluon, phenmedipham, phenmedipham-ethyl ester, desmedipham, the spirit of sulphur grass, special grass Spirit, oatax, Chem hoe, chlorpropham, benzyl dichloride grass ester, swep, chlorbufam, Carboxazole, Chlorprocarb, Fenasulam, BCPC, CPPC, Carbasulam, Ding Caote, benthiocarb, vernolate, molinate, tri-allate, dimepiperate, dogstail Fear, pyributicarb, cycloate, Avadex, bactericide, the careless spy of second sulphur, orbencarb, pebulate, prosulfocarb, tiocarbazil, sulfuric acid, Dimexan, Isopolinate, Methiobencarb, 2,4- d butyl ester, the chlorine sodium of 2 first 4, the different monooctyl ester of 2,4- drops, the chlorine of 2 first 4 are different pungent Ester, 2,4- drops sodium salt, 2,4- drops dimethylamine salt, the chloroethene thioesters of 2 first 4, the chlorine of 2 first 4,2,4- drops propionic acid, high 2,4- drops propionate, 2, 4- Embutoxs, Vi par, Vi par salt, Thistrol, 2,4,5- tears, 2,4,5- tears propionic acid, 2,4,5- tears fourths Acid, the chloramines salt of 2 first 4, Mediben, erbon, Fenac, match pine, trichlorobenzoic acid, chloramben, methoxy trichlorobenzoic acid, dogstail Spirit, fluazifop, efficient fluazifop, haloxyfop-P-methyl, efficient haloxyfop, quizalofop-ethyl, Quizalotop-ethyl, oxazole dogstail Spirit, fenoxapropPethyl, propaquizafop, cyhalofop-butyl, metamifop, clodinafop-propargyl, diclofop-methyl thiazole, chloroazifoppropynyl, the standing grain of hydroxyl penta spirit, Trifluoro dogstail oxime, isoxapyrifop, paraquat, diquat dibromide, oryzalin, ethalfluralin, isopropalin, nitralin, the fluorine of ring third Spirit, prodiamine, benfluralin, fluchloraline, the spirit of amino second fluorine, dipropalin, chloroethene dipropalin, Methalpropalin, Third nitre phenol, glyphosate, Sha barnyard grass phosphine, glufosinate-ammonium, amiprophos-methyl, sulphosate, piperazine grass phosphine, bialaphos, bensulide, butamifos, Creeping weed phosphorus, cut down ridge phosphorus, double first amiprophos, dow crabgrass killer, imazapyr, imazethapyr, imazaquin, imazamox, first Oxygen Imazethapyr ammonium salt, AC 263222, miaow grass ester, fluroxypyr, the different monooctyl ester of fluroxypyr, clopyralid, ammonia Chloropyridine acid, trichlopyr, dithiopyr, halogen grass are determined, phenolate trichloropyridine, thiazopyr, fluridone, chlorine Fampridine are sour, Diflufenzopyr, triclopyr butoxyethyl ester, Cliodinate, sethoxydim, clethodim, cycloxydim, alloxydimsodium, ring benzene grass Ketone, butroxydim, tralkoxydim, tepraloxydim, Buthidazole, metribuzin, hexazinone, metamitron, ethiozin, Ametridione, Amibuzin, Brominal, bromoxynil octanoate, ioxynil octanoate, ioxynil, dichlobenil, diphenatril, polybenzobisoxazole Oxalic acid dinitrile, chloroxynil, Iodobonil, Flumetsulam, florasulam, penoxsuam, metosulam, cloransulammethyl, Diclosulam, pyroxsulam, fluorine straw colour, bispyribac-sodium, pyribenzoxim, pyriftalid, KIH 6127, pyrithiobacsodium, bicyclic sulphur It is humulone, mesotrione, sulphur humulone, Tembotrione, Tefuryltrione, Bicyclopyrone, Ketodpiradox, different Oxazole humulone, isoxachlorotole, Fenoxasulfone, Methiozolin, fluazolate, pyraflufen-ethyl, pyrazolate, wild swallow Withered, pyrazoxyfen, benzofenap, pyrrole chlorine grass amine, Pyrasulfotole, topramezone, Pyroxasulfone, cafenstrole, fluorine amine grass Azoles, Amrol, amicarbazone, azafenidin, profluazone, sulfentrazone, Bencarbazone, benzfendizone, fluorine third are phonetic Careless ester, bromacil, isoprocil, lenacil, terbacil, Flupropacil, cinidon-ethyl, Flumiclorac pentyl, flumioxazin, Alkynes grass amine, phthalein benzyl oxide, Flumezin, pentachlorophenol (sodium), dinoseb, dinoterb, dinoterb acetate, dinosam, Chemox PE, chlorine nitre phenol, Medinoterb acetate, Di Lete, oxadiargyl, oxadiazon, pentoxazone, profluazol, fluthiacet, fentrazamide, fluorine Pyridazine grass ester, pyrazon, brompyrazon, diformazan reach careless volt, Kusakira, careless pyridazone, grass and rattled away pine, norflurazon, Pyridafol, dichloro Quinolinic acid, quinmerac, Bentazon, pyridate, oxaziclomefone, benazolin, clomazone, cinmethylin, iso-propyl-ester nitrofen, Propyl-ester nitorfen, indanofan, sodium chlorate, Dalapon, trichloroacetic acid, monochloroacetic acid, hexachloroacetone, tetrafluoro propionic acid, herbage are fast, bromine phenol Oxime, triazole sulphur, kill azoles, flurtamone, benfuresate, ethofumesate, phonetic careless amine, chlorine phthalandione, fluorochloridone, barnyard grass, methacrylaldehyde, Bentranil, tridiphane, Bidisin, thiadiazoles grass amine, phenisopham, hydroxyl humulone, dioxybenzone, benzene flumetsulam, chlorine acyl grass phosphine, three Chloropropionic acid, Alorac, Diethamquat, Etnipromid, Iprymidam, Ipfencarbazone, Thiencarbazone- Methyl, Pyrimisulfan, Chlorflurazole, Tripropindan, Sulglycapin, first sulphur nitralin, Cambendichlor, the pyrimidine acid of ring third, rodethanii, benoxacor, fenclorim, flurazole, fenchlorazole, the careless quinoline of solution, oxabetrinil, MG191, cyometrinil, DKA_24, mefenpyrdiethyl, furilazole, fluxofenim, isoxadifen, allyl dichloride amine, fluorine Chloropyridine ester, DOW chlorine fluorine pyridine ester, UBH-509, D489, LS 82-556, KPP-300, NC-324, NC-330, KH-218, DPX-N8189、SC-0744、DOWCO535、DK-8910、V-53482、PP-600、MBH-001、KIH-9201、ET-751、 KIH-6127 and KIH-2023.
When deployed, if it is desired, commercially available preparation is diluted in a manner of common, such as in wettable powder, concentration When emulsion, suspension and the particle to suspend in water, make to be diluted with water.Granule used in powder, soil pesticide or broadcast sowing and The solution of sprinkling, further it need not be diluted typically before use with inert substance.With the change of external condition, it is desirable to formula The usage amount of I is also different, and external condition is, such as temperature, humidity, property of herbicide for using etc..It can be with Have a big amplitude of variation, such as 0.001 between 1.0kg/ha, or more active material, but preferably arrived 0.005 Between 750g/ha, particularly 0.005 between 250g/ha.
Embodiment
Following examples are used to illustrate the present invention, should not regard it as limiting the invention in any way.The present invention Claimed interest field is illustrated by claims.
In view of the economy and diversity of compound, some compounds that we are preferably synthetic, in many chemical combination of synthesis In thing, selected part is listed in the table below in 1.Specific compound structure and corresponding compound information are as shown in table 1.In table 1 Compound is intended merely to better illustrate the present invention, but does not limit the present invention, for a person skilled in the art, should not The scope that this is interpreted as to the above-mentioned theme of the present invention is only limitted to following compound.
The compound structure of table 1 and its HNMR data
Note：Compound 41,43,48,64,65,106,108,113,130,131,134,140-142,147,151,154- 162nd, 206,210,212,214,234-236,243,245, the mixture that 247-249 is a variety of isomers, wherein, when When due to exist two chiralitys Center and produce isomers.
The several methods detailed annotation for preparing the compounds of this invention is illustrated in following scheme and embodiment.Raw material can be through market Buying can either be prepared by known in the literature method or as shown in detailed annotation.Those skilled in the art should manage Solution, the compound of other synthetic routes synthesis present invention can also be utilized.Although hereinafter to the tool in synthetic route Body raw material and condition are illustrated, however, it is possible to easily be replaced with other similar raw materials and condition, these are right Modification or the variant of preparation method of the present invention and various isomeries of caused compound etc. are included in the scope of the invention It is interior.In addition, method, which is prepared as described below, to be routinized according to the disclosure of invention, using well known to those skilled in the art Method is further modified.For example, during the course of the reaction appropriate group protect etc..
Embodiment of the method presented below is used to promote further appreciating that to the preparation method of the present invention, and what is used is specific Material, species and condition are determined as the further explanation to the present invention, are not the limitation to its zone of reasonableness.In the following table The reagent used in the synthesis compound shown can either be bought with market or can be light by those of ordinary skill in the art Easily it is prepared.
The embodiment of representative compound is as follows：
The synthesis of compound 001：
12.3g 1, hydroresorcinol and 20mL triethylamines are dissolved in 100mL 1, in 2- dichloroethanes, are cooled to 0 DEG C, stir Mix the lower solution for being added dropwise and being made up of 32.1g raw material As 1 and 50mL 1,2- dichloroethanes.Drip off and continue 0~5 DEG C of stirring 0.5h of insulation Afterwards, 10mL triethylamines and 1mL acetone cyanohydrins are added into reaction solution.Reaction solution is warming up to 55 DEG C of stirring reactions 1 hour, is down to room Temperature.Then plus 1N hydrochloric acid adjusts pH to 3 or so.Liquid separation, aqueous phase are extracted with 1,2- dichloroethanes.Organic phase merges, successively with water, full Washed with sodium chloride solution, anhydrous sodium sulfate drying, concentration, obtain 38g off-white powders.HPLC purity>95%.
Compound 002 to 040 is according to said method prepared.
The synthesis of compound 043：
2.3g raw material As 2 are dissolved in 10mL dichloromethane, and stirring is cooled to 0 DEG C, add 2.0g Anhydrous potassium carbonates, stirring 30min.5mL is added dropwise into reaction solution dissolved with the dichloromethane solution of 0.4g chloroacetic chlorides, 0~5 DEG C of controlling reaction temperature.Drip off slow Slowly it is warmed to room temperature stirring reaction 2h.Reaction solution is filtered, and filter cake is washed with 10mL dichloromethane.Organic phase merges, and uses saturation successively Sodium bicarbonate solution, water, saturated nacl aqueous solution washing, anhydrous sodium sulfate drying, concentration, obtain 2.0g off-white powders. HPLC purity>95% (the ratio 69 of both front and back isomers:31).
The synthesis of compound 044：
4.0g compounds 001 are added to 25mL1, and in 2- dichloroethanes, stirring is cooled to 0 DEG C, and the second of 2.5mL tri- is slowly added dropwise Amine, insulation reaction 10min.The solution of 1.2g mesyl chlorides and 5mL1,2- dichloroethanes composition is slowly added dropwise into reaction solution.Drop It is complete to continue 0~5 DEG C of stirring 4h of insulation.1.4g benzenethiol sodium salts are slowly added into reaction solution, are then slowly increased to room temperature.Reaction Reaction 16h is stirred at room temperature in liquid.Then plus 1N hydrochloric acid adjusts pH to 3 or so.Liquid separation, aqueous phase are extracted with 1,2- dichloroethanes.It is organic Mutually merge, washed successively with water, saturated nacl aqueous solution, anhydrous sodium sulfate drying, concentrated.Crude product purifies through column chromatography, obtains 1.8g off-white powder.HPLC purity>95%.
The synthesis of compound 046：
2.2g compounds 001 and 0.85g raw material As 3 are dissolved in 10mL dichloromethane, and stirring is cooled to 0 DEG C, and 5mL is added dropwise Dissolved with 1.0g N, the dichloromethane solution of N'- Dicyclohexylcarbodiimides (DCC), 0~5 DEG C of controlling reaction temperature.Drip off slowly It is warmed to room temperature stirring reaction 16h.Reaction solution is filtered, and filter cake is washed with 10mL dichloromethane.Merge filter, washing lotion, concentration, crude product warp Column chromatography purifies, and obtains 2.0g yellow solids.HPLC purity>98%.
The synthesis of compound 062：
2.2g compounds 001 are dissolved in 10mL dichloromethane, and stirring is cooled to 0 DEG C, add 1.0g triethylamines, stirring 30min.5mL is added dropwise into reaction solution dissolved with the dichloromethane solution of 0.7g pyridine -4- formyl chlorides, controlling reaction temperature 0~5 ℃.Drip off and be slowly warmed to room temperature stirring reaction 16h.Reaction solution is filtered, and filter cake is washed with 10mL dichloromethane.Organic phase merges, Washed successively with saturated sodium bicarbonate solution, water, saturated nacl aqueous solution, anhydrous sodium sulfate drying, concentrate, it is white to obtain 2.0g classes Color solid.HPLC purity>95%.
The synthesis of compound 137：
2.3g compounds 011 are dissolved in 10mL dichloromethane, and stirring is cooled to 0 DEG C, add 1.0g triethylamines, stirring 30min.0.9g bromobenzyls, 0~5 DEG C of controlling reaction temperature are added dropwise into reaction solution.Drip off and be slowly warmed to room temperature stirring reaction 30h. 1N hydrochloric acid is added into reaction solution and adjusts pH to 3 or so, liquid separation, aqueous phase is extracted with dichloromethane.Organic phase merges, and uses saturation successively Sodium bicarbonate solution, water, saturated nacl aqueous solution washing, anhydrous sodium sulfate drying, concentration, obtained crude product are pure through column chromatography Change, obtain 1.5g off-white powders.HPLC purity>97%.
The synthesis of compound 139：
2.5g raw material As 4 are dissolved in 10mL dichloromethane, and stirring is cooled to 0 DEG C, instill 1.5g triethylamines, stirring 30min.0.7g mesyl chlorides, 0~5 DEG C of controlling reaction temperature are added dropwise into reaction solution.Drip off and be slowly warmed to room temperature stirring reaction 16h.1N hydrochloric acid is added into reaction solution and adjusts pH to 3 or so, liquid separation, aqueous phase is extracted with dichloromethane.Organic phase merges, and uses successively Saturated sodium bicarbonate solution, water, saturated nacl aqueous solution washing, anhydrous sodium sulfate drying, concentration, obtain 2.6g pale yellow colored solids Body.HPLC purity>95%.
Biological evaluation：
The active class criteria that noxious plant destroys (growing control rate) is as follows：
10 grades：It is completely dead；
9 grades：Control rate is grown more than 95%；
8 grades：Control rate is grown more than 90%；
7 grades：Control rate is grown more than 80%；
6 grades：Control rate is grown more than 70%；
5 grades：Control rate is grown more than 60%；
4 grades：Control rate is grown more than 50%；
3 grades：Control rate is grown more than 20%；
2 grades：Control rate is grown in 5-20%；
1 grade：Control rate is grown below 5%；
Growth control rate is fresh weight control rate above.
Unifacial leaf and broadleaf weed seed and crop seed corn are placed in the plastic tub equipped with soil, then 0.5-2 centimetres of soil is covered, it is grown in good greenhouse, sowing handles test in the 4-5 leaf phases and planted after 2-3 weeks Thing, respectively by the compounds of this invention acetone solution for trying, Tween 80 is then added, finite concentration is diluted to certain water Solution, sprayed application to spray tower on plant.The experiment effect of weeds is listed in table 2 after being cultivated 3 weeks, 3 weeks in greenhouse after dispenser.
The after seedling weeds of table 2. are tested
Note：Application dosage is 300 grams/ha of active ingredient.
It is small particularly with corn by experiment we have found that compound of the present invention generally has preferable Weed-control effect The main broad leaved weeds such as Descurainia sophia that wheatland occurs extensively, piemarker have good effect, possess good commercial value.Especially It is it was noted that having high activity for broad leaved weeds such as the resistant Descurainia sophias of ALS inhibitor.In addition, this hair after tested Bright compound also has activity and crop safety well under suitable dosage to live and transplanting rice field key weeds.
Contrast experiment：
Control compounds 1：(coming from patent WO97/46530A1)
Control compounds 2：(coming from patent WO97/46530A1)
Control compounds 3：(coming from patent CN1416422A)
Control compounds 4：(coming from patent CN105218449A)
After seedling test condition is same as above, and test and measuring is 50 grams/ha；After observing time is experiment 20 days.
The contrast and experiment of table 3.
Compound Big fringe amur foxtail Hard grass Triticum tauschii Descurainia sophia Piemarker
Compound 237 8 9 5 10 10
Compound 109 10 10 6 10 10
Compound 153 5 6 3 8 8
Compound 66 10 10 8 10 10
Control compounds 1 0 0 0 1 1
Control compounds 2 0 0 0 0 0
Control compounds 3 1 1 2 4 3
Control compounds 4 4 5 1 7 7
As can be seen from Table 3, compound of the invention is substantially better than control compounds on activity of weeding.
Find that compound of the present invention is much to Korea lawn grass, Bermuda grass, Festuca Arundinacea, precocity by many tests simultaneously The Gramineae lawns such as standing grain, rye grass, seashore paspalum have good selectivity, can prevent and kill off many crucial grassy weeds and broad-leaved Weeds.Fabulous choosing is also showed that to tests such as the soybean under different insecticide-applying way, cotton, oily certain herbaceous plants with big flowers, potato, fruit tree, vegetables Selecting property and commercial value.

Claims (12)

1. a kind of substituted benzoylcyclohexan cyclohexadione compounds or its dynamic isomer, salt, as shown in formula I：
In formula,
R1R2N is representedWherein,
Het is selected from three to eight circle heterocycles, in addition to the N atoms on the ring on containing C and 1- positions, also containing 0-3 following atoms or Part of the group as ring：O、NRb、S、SO、SO2, C=O, C=NRbOr C=NORb, and work as C=O, C=NRbOr C= NORbAt 2- positions, 3- positions can not be N or S；
RbSelected from hydrogen, C1~6Alkyl, halo C1~6Alkyl, C2~6Alkenyl, halo C2~6Alkenyl, C1~6Alkoxy C1~6Alkyl, halo C1~6Alkoxy C1~6Alkyl, C1~6Alkyl-carbonyl, halo C1~6Alkyl-carbonyl, C1~6Alkyl sulphonyl, C1~6Alkoxy carbonyl, C1~6Alkyl amino-carbonyl, C1~6Alkyl-carbonyl C1~6Alkyl, C1~6Alkoxy carbonyl C1~6Alkyl, C1~6Alkyl amino-carbonyl C1~6Alkyl, It is unsubstituted or halogen, nitro, cyano group, C are independently selected from by 1-31~6Alkyl, halo C1~6Alkyl, C1~6Alkoxy, halo C1~6Alkoxy, C1~6Aryl that group in alkyl-carbonyl is substituted, heteroaryl, aryl carbonyl, Heteroarylcarbonyl, aryl sulphur Acyl group, arylmethyl, hetervaromatic methyl；
RaSelected from one or more of following group group：Hydrogen, halogen, cyano group, nitro, hydroxyl, carboxyl, amino, C1-C6Alkane Base sulfonyl, C1~6Alkyl, halo C1~6Alkyl, C2~6Alkenyl, halo C2~6Alkenyl, C1~6Alkoxy, halo C1~6Alkoxy, C1~6Alkylamino, C2~6Alkenyloxy group, halo C2~6Alkenyloxy group, C2~6Enamino, halo C2~6Enamino, C1~6Alkyl-carbonyl, halo C1~6Alkyl-carbonyl, C1~6Alkoxy carbonyl, C1~6Alkyl amino-carbonyl, C1~6Alkoxy C1~6Alkyl, halo C1~6Alkoxy C1~6Alkane Base, C1~6Alkyl carbonyl epoxide C1~6Alkyl, C1~6Alkoxy C1~6Alkoxy, halo C1~6Alkoxy C1~6Alkoxy, C1~6Alcoxyl Base carbonyl C1~6Alkoxy, C1~6Alkyl carbonyl epoxide, halo C1~6Alkyl carbonyl epoxide, C1~6Alkyl-carbonyl-amino, C1~6Alkyl Sulfonyl epoxide, C1~6Alkyl sulfonyl-amino, C1~6Alkyl-carbonyl C1~6It is alkoxy, unsubstituted or be independently selected from by 1-3 Halogen, nitro, cyano group, C1~6Alkyl, halo C1~6Alkyl, C1~6Alkoxy, C1~6The virtue that group in alkyl-carbonyl is substituted Base, heteroaryl, aryl carbonyl epoxide, aryl sulfonyl epoxide, arylmethyl epoxide, hetervaromatic methyl epoxide, aryl-amino-carbonyl, Arlysulfonylamino, arylmethyl amino or hetervaromatic methyl amino；
Or R1、R2Represent hydrogen respectively, containing be with or without halogen substitution contain 0~4 heteroatomic C1~8Alkyl, C1~8Alkenyl or C1~8Alkynyl, containing be with or without halogen substitution contain 0~4 heteroatomic C1~4Acyl group, it is unsubstituted or by selected from halogen, contain Or contain 0~4 heteroatomic C without halogen substitution1~4The C that one or more of alkyl group is substituted3~6Cycloalkyl；R RepresentWherein,
R11Selected from hydrogen, C1-C6Alkyl, C3-C6Cycloalkyl, C1-C6Alkoxy, C1-C6Alkoxy C1-C6Alkyl, C1-C6Alkyl oxycarbonyl Base, C1-C6Alkoxy carbonyl, C1-C6Alkylthio group, containing being with or without the 6-10 members aryl of halogen substitution, take containing being with or without halogen The heteroatomic 5-10 unit's heteroaryls containing 1-3 O, S, N in generation, n=0-6；
Y is selected from C, N, O or S；
Z is selected from C, N, O, S, SO, SO2Or C=O；
Or as n=2 and when Z and/or Y are selected from C, two R on different C atoms11Connect into CH2、(CH2)2、(CH2)3、 (CH2)4、(CH2)5、(CH2)6、O、O(CH2)2O、O(CH2)3O、O(CH2)4O、S(CH2)2S or S (CH2)3S；
Or as n=2, two R on same C atoms11Connect into following group：(CH2)2、(CH2)3、(CH2)4、 (CH2)5、(CH2)6、O、O(CH2)2O、O(CH2)3O、O(CH2)4O、S(CH2)2S or S (CH2)3S；
R12Selected from-OR13Or-SR13, wherein, R13Selected from hydrogen, C1-C6Alkyl, C1-C6Alkyl-carbonyl, C1-C6Alkyl sulphonyl, C2- C6Alkenyl, halo C2-C6Alkenyl, C2-C6Alkynyl, C1-C6Alkoxy carbonyl C1-C6Alkyl, C1-C6Alkyl amino-carbonyl C1-C6Alkyl, It is unsubstituted or halogen, nitro, cyano group, C are independently selected from by 1-31-C6Alkyl, halo C1-C6Alkyl, C1-C6Alkoxy or halogen For C1-C6Aryl that group in alkoxy is substituted, arylmethyl, aryl carbonyl, aryl sulfonyl, heteroaryl, Heteroarylcarbonyl Or aryl carbonyl methyl.
2. a kind of substituted benzoylcyclohexan cyclohexadione compounds or its dynamic isomer, salt according to claim 1, It is characterized in that：
Het is selected from 4~8 membered lactams bases, imidazole radicals, pyrazolyl, RaSelected from C1~4Alkyl, C1~4Alkoxy, nitro, halogen, cyanogen Base, amino, C1~6Alkylamino, C1~6One or more of alkyl sulphonyl group；
Or R1、R2In one represent containing the C containing 0~4 O, S, N for being with or without halogen substitution1~4Acyl group；Another is represented Hydrogen, containing the C containing 0~4 O, S, N for being with or without halogen substitution1~8Alkyl, C1~8Alkenyl or C1~8Alkynyl, it is unsubstituted or selected From halogen, containing be with or without halogen substitution contain 0~4 heteroatomic C1~4One or more of alkyl group is substituted C3~6Cycloalkyl；
As n=2 and when Z and/or Y are selected from C, two R on different C atoms11Connect into CH2、(CH2)2、(CH2)3、 (CH2)4、(CH2)5、(CH2)6、O、O(CH2)2O、O(CH2)3O、O(CH2)4O、S(CH2)2S or S (CH2)3S；
Or as n=2, two R on same C atoms11Connect into following group：(CH2)2、(CH2)3、(CH2)4、 (CH2)5、(CH2)6、O、O(CH2)2O、O(CH2)3O、O(CH2)4O、S(CH2)2S or S (CH2)3S。
3. a kind of substituted benzoylcyclohexan cyclohexadione compounds according to claim 1 or 2 or its dynamic isomer, Salt, it is characterised in that：
Het is selected from butyrolactam base, valerolactamyl, caprolactam base, oenantholcatam base, piperazine ketone group, morpholine ketone group, thio Morpholine ketone group, imidazole radicals, pyrazolyl, RaSelected from fluorine, chlorine, methyl, ethyl, methoxyl group, ethyoxyl, nitro, cyano group, amino, C1~6 Alkylamino, C1-C6One or more of alkyl sulphonyl group；
Or R1Represent acetyl group, acetyl fluoride base, difluoro acetyl group, trifluoroacetyl group, methoxyacetyl, ethoxyacetyl, methoxy Propiono, ethoxy propiono, R2Represent hydrogen or unsubstituted or by selected from fluorine, methoxyl group, ethyoxyl, propoxyl group, butoxy, first Methyl that one or more of oxygen ethyoxyl group is substituted, ethyl, propyl group, butyl, amyl group, cyclopropyl；
As n=2 and when Z and/or Y are selected from C, two R on different C atoms11Connect into CH2、(CH2)2、(CH2)3、O、O (CH2)2O、O(CH2)3O、S(CH2)2S or S (CH2)3S；
Or as n=2, two R on same C atoms11Connect into following group：(CH2)2、(CH2)3、O、O(CH2)2O、O (CH2)3O、S(CH2)2S or S (CH2)3S。
4. a kind of substituted benzoylcyclohexan cyclohexadione compounds or its change according to claim 1-3 any one Isomers, salt, it is characterised in that：
R is selected from one of group shown in following formula：
R11Selected from hydrogen, C1-C6Alkyl, C3-C6Cycloalkyl, C1-C6Alkoxy, C1-C6Alkoxy C1-C6Alkyl, C1-C6Alkyl oxycarbonyl Base, C1-C6Alkoxy carbonyl, C1-C6Alkylthio group, containing being with or without the 6-10 members aryl of halogen substitution, take containing being with or without halogen The heteroatomic 5-10 unit's heteroaryls containing 1-3 O, S, N in generation, n=0-6；
R12Selected from hydroxyl, C1-C3Alkoxy, C1-C3Alkyl carbonyl epoxide, C1-C3Alkyl sulphonyl epoxide, C2-C4Alkenyloxy group, halogen For C2-C4It is alkenyloxy group, unsubstituted or fluorine, chlorine, bromine, nitro, cyano group, methyl, trifluoromethyl, methoxyl group are independently selected from by 1-3 Or phenoxy group, benzyl epoxide, thiophenyl, benzyl sulfenyl, benzoyloxy, the benzene sulfonyl that the group in trifluoromethoxy is substituted Base epoxide, benzoyl methoxyl group, containing the heteroatomic 5-10 unit's heteroaryls epoxide of 1-3 O, S, N or containing the miscellaneous original of 1-3 O, S, N The 5-10 unit's heteroaryl carbonyl epoxides of son.
5. a kind of substituted benzoylcyclohexan cyclohexadione compounds or its change according to claim 1-4 any one Isomers, salt, it is characterised in that：Described salt is sylvite, sodium salt, ammonium salt, calcium salt, pyridiniujm or choline salt.
6. a kind of prepare the benzoylcyclohexan cyclohexadione compounds substituted described in claim 1-5 any one or its mutually variation The method of structure body, salt, it comprises the following steps：
(1) using the compound and compound as shown in formula IIReacted, prepare the change as shown in formula I-1 Compound；
(2) by the compound and compound R as shown in formula I-113X or R13S-M is reacted, and is made as shown in formula I-2 Compound；
Wherein, reaction equation is as follows：
X represents halogen, hydroxyl, and M represents alkali metal, alkaline-earth metal, preferably Na, Li, K, Ca or Mg.
7. substituted benzoylcyclohexan cyclohexadione compounds or its dynamic isomer, salt are prepared according to claim 6 Method, it is characterised in that：The step (1) is carried out in non-protonic solvent, in the presence of alkali and catalyst；The step (2) in R13X is carried out when reacting in non-protonic solvent, in the presence of alkali, with R13In non-protonic solvent when S-M reacts In, carry out in the presence of alkali and activator；Reaction temperature is -30 DEG C -180 DEG C, preferably -5 DEG C -90 DEG C.
8. substituted benzoylcyclohexan cyclohexadione compounds or its dynamic isomer, salt are prepared according to claim 7 Method, it is characterised in that：The solvent is dichloromethane, 1,2- dichloroethanes, acetonitrile, toluene, tetrahydrofuran, 1,4- dioxies six Combination more than one or both of ring and ethyl acetate, preferably dichloromethane, 1,2- dichloroethanes or toluene；The alkali is Sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium acid carbonate, saleratus, triethylamine, DIPEA or DBU, It is preferred that triethylamine or potassium carbonate；The catalyst is acetone cyanohydrin；The activator is mesyl chloride, paratoluensulfonyl chloride, three Methylchlorosilane, trifluoro-acetyl chloride, TFAA, trifluoromethanesulfchloride chloride,
A kind of 9. Herbicidal combinations, it is characterised in that：Contain the substituted benzoyl basic ring described in claim 1-5 any one At least one of acetyl butyryl class compound or its dynamic isomer, salt are used as active component, it is preferable that the active component Weight percentage is 0.1-99%.
A kind of 10. method for controlling noxious plant, it is characterised in that including the claim 1-5 of herbicidally effective amount is any one At least one of substituted benzoylcyclohexan cyclohexadione compounds or its dynamic isomer, salt described in or claim Herbicidal combinations use described in 9 is on plant or noxious plant region.
11. the substituted benzoylcyclohexan cyclohexadione compounds or its tautomerism as described in claim 1-5 any one Application of the Herbicidal combinations on control weeds described at least one of body, salt or claim 9.
12. application according to claim 11, it is characterised in that by described substituted benzoylcyclohexan diones Compound or its dynamic isomer, salt are used to prevent and kill off the weeds in useful crop, it is preferable that the useful crop is genetically modified crops Or the crop that genome editing technique is treated.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112409263A (en) * 2019-08-23 2021-02-26 东莞市东阳光农药研发有限公司 Substituted benzoyl compound and application thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997046530A1 (en) * 1996-06-06 1997-12-11 E.I. Du Pont De Nemours And Company Herbicidal pyridinyl and pyrazolylphenyl ketones
JPH1121280A (en) * 1997-06-27 1999-01-26 Nippon Soda Co Ltd New benzene derivative and herbicide
WO2000005221A1 (en) * 1998-07-24 2000-02-03 Bayer Aktiengesellschaft Substituted benzoylcyclohexandiones
WO2001047894A1 (en) * 1999-12-24 2001-07-05 Bayer Aktiengesellschaft Substituted benzoylcyclohexane diones for use as herbicides
CN1416422A (en) * 2000-03-06 2003-05-07 拜尔公司 Substituted benzoylcyclohexenones
CN102464630A (en) * 2010-11-19 2012-05-23 中国中化股份有限公司 Nitrogen heterocyclic substituent-containing benzoyl compound and application thereof
CN105218449A (en) * 2015-11-06 2016-01-06 青岛清原化合物有限公司 Pyrazolone compound or its salt, preparation method, herbicidal composition and purposes

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4797150A (en) * 1986-06-09 1989-01-10 Stauffer Chemical Company Certain 2-(2-substituted benzoyl)-1,3,5-cyclohexanetriones
US4780127A (en) * 1982-03-25 1988-10-25 Stauffer Chemical Company Certain 2-(substituted benzoyl)-1,3-cyclohexanediones and their use as herbicides
JP2003506443A (en) * 1999-08-10 2003-02-18 バイエルクロップサイエンス株式会社 Herbicidal tetrazolinone derivatives

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997046530A1 (en) * 1996-06-06 1997-12-11 E.I. Du Pont De Nemours And Company Herbicidal pyridinyl and pyrazolylphenyl ketones
JPH1121280A (en) * 1997-06-27 1999-01-26 Nippon Soda Co Ltd New benzene derivative and herbicide
WO2000005221A1 (en) * 1998-07-24 2000-02-03 Bayer Aktiengesellschaft Substituted benzoylcyclohexandiones
WO2001047894A1 (en) * 1999-12-24 2001-07-05 Bayer Aktiengesellschaft Substituted benzoylcyclohexane diones for use as herbicides
CN1416422A (en) * 2000-03-06 2003-05-07 拜尔公司 Substituted benzoylcyclohexenones
CN102464630A (en) * 2010-11-19 2012-05-23 中国中化股份有限公司 Nitrogen heterocyclic substituent-containing benzoyl compound and application thereof
CN105218449A (en) * 2015-11-06 2016-01-06 青岛清原化合物有限公司 Pyrazolone compound or its salt, preparation method, herbicidal composition and purposes

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112409263A (en) * 2019-08-23 2021-02-26 东莞市东阳光农药研发有限公司 Substituted benzoyl compound and application thereof
CN112409263B (en) * 2019-08-23 2024-04-05 东莞市东阳光农药研发有限公司 Substituted benzoyl compounds and application thereof

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