CN102395556A - Carboxylate compound and use thereof - Google Patents

Carboxylate compound and use thereof Download PDF

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Publication number
CN102395556A
CN102395556A CN2010800163780A CN201080016378A CN102395556A CN 102395556 A CN102395556 A CN 102395556A CN 2010800163780 A CN2010800163780 A CN 2010800163780A CN 201080016378 A CN201080016378 A CN 201080016378A CN 102395556 A CN102395556 A CN 102395556A
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alkyl
halo
compound
group
formula
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CN102395556B (en
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刘长令
周银平
崔东亮
张金波
马宏娟
刘远雄
张志国
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Shenyang Sinochem Agrochemicals R&D Co Ltd
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Shenyang Research Institute of Chemical Industry Co Ltd
Sinochem Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/10—Aromatic or araliphatic carboxylic acids, or thio analogues thereof; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P13/00—Drugs for disorders of the urinary system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D247/00—Heterocyclic compounds containing rings having two nitrogen atoms as the only ring hetero atoms, according to more than one of groups C07D229/00 - C07D245/00
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
    • C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D257/08—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems

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  • Organic Chemistry (AREA)
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  • Chemical & Material Sciences (AREA)
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  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental Sciences (AREA)
  • Plant Pathology (AREA)
  • Dentistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Agronomy & Crop Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Urology & Nephrology (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Pharmacology & Pharmacy (AREA)
  • Animal Behavior & Ethology (AREA)
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  • Plural Heterocyclic Compounds (AREA)
  • Pyridine Compounds (AREA)

Abstract

Disclosed is a kind of carboxylate compound, shown as general formula I, wherein the definition of each group is seen in the description. The compound has excellent herbicidal activity, and can effectively control barnyard millet, crabgrass, piemarker and bristlegrass and so on, even at low dosage. So it can be used as agricultural herbicide.

Description

Carboxylate compound and use thereof
Plant carboxylic acid ester compound and application thereof technical field
The invention belongs to field of agricultural herbicide.Specifically related to a kind of carboxylic acid ester compound and application thereof.Present invention additionally comprises the composition containing such compound, their purposes and application method.Background technology
Weeds are to crops, especially for agricultural product, such as cotton such as the grains and fiber that disclosure satisfy that mankind's primary demand, paddy rice, corn, wheat, and soybean etc. causes very big infringement.It is a kind of effective way for improving agricultural production to kill or suppress the infringement for avoiding or reducing to crop while weed growth.Therefore need to continually develop more effective new herbicides.Carboxylic acid ester compound such as Quizalotop-ethyl, Imazethapyr etc. are known herbicides, but the carboxylic acid ester compound of structure as representative of the present invention has no document report.The content of the invention
In order to meet requirement agriculturally, the composition the invention provides the application method of a kind of novel carboxylic acid ester compound of structure and its management of weeds and containing these compounds is in application agriculturally.The compound of the present invention can effectively control the weeds such as barnyard grass, lady's-grass, piemarker as herbicide.
Technical scheme is as follows：
A kind of carboxylic acid ester compound, as shown in formula I：
In formula：
A=B=carbon；
When A is connected with B for double bond, A is connected with ^ for singly-bound, OR3, general structure is as shown in 1-1:
Z/E- formulas
When A is connected with B for singly-bound, A is connected with ^ for double bond, and 0, general structure is as shown in 1-2:
X is selected from 0 or NH; R2Selected from H, K, Na, d-C12Alkyl, cyano group d-C12Alkyl, halo d-C12Alkyl, C2-C6Alkenyl, C2-C6Block base, halo C2-C6Alkenyl, halo C2-C6Block base, CrC12Alkyl-carbonyl, CrC12Alkoxy carbonyl group, C3-C8Cycloalkyl, CrC12Alkyl sulfoxide base, CrC12Alkyl sulphonyl, CrC12Alkoxy CrC12Alkyl, Ci-Ci2 Ci- Ci2 ^, C1-C12 Ci- Ci2 ^, Ci-Ce ^ $ Μ C1-C12 ^ bases, phenyl, pyridine radicals, phenyl d-C6Alkyl, pyridine radicals d-C6Alkyl or phenyl carbonyl d-C6Alkyl, wherein phenyl ring or pyridine ring hydrogen can be replaced by 1-3 following radicals：Halogen, N02、 CN、 d-C12Alkyl, halo CrC12Alkyl, d-C12Alkoxy, halo d-C12Alkoxy, d-C12Alkylamino, halo d-C12Alkylamino,12Alkylthio group, halo d-C12Alkylthio group, d-C12Alkyl-carbonyl, d-C12Alkyl sulfoxide base or d-C12Alkyl sulphonyl；
R3Selected from H or d-C12Alkyl；
Q is selected from any one group of Q1 as follows to Q18：
R- bodies Q1-
Compound more preferred is in the present invention：In formula I
X is selected from 0;
R2Selected from H, K, Na, d-C6Alkyl, cyano group d-C6Alkyl, halo CrC6Alkyl, C2-C6Alkenyl, C2-C6Block base, halo C2-C6Alkenyl, halo C2-C6Block base, d-C6Alkyl-carbonyl CrC6Alkane, Ci-C6 Ci-C6The Ci-Ci2 sulfonyls of C3-Cg i C1-C12 M 1, CrC6Alkoxy d-C6Alkyl, phenyl, pyridine radicals, phenyl d-C6Alkyl or pyridine radicals CrC6Baked base；
R3Selected from H or d-C12Alkyl；
Q any one group into Q18 selected from Q1.Further preferred compound is：
Formula 1-1 stereochemical structure is E- formulas；
X is selected from 0;
R2Selected from H, K, Na, d-C6Alkyl, halo d-C6Alkyl, C2-C6Alkenyl, C2-C6Block base, halo C2-C6Alkenyl or ^ are for C2-C6Block base；
R3Selected from H or d-C6Alkyl；
Q any one group into Q18 selected from Q1.Compound still more preferably is：
R2Selected from H, K, Na or d-C6Alkyl；
R3Selected from CH3;
Q any one group into Q16 selected from Ql.In the definition of general formula compound given above, collect term used and be defined as follows: Halogen：Refer to fluorine, chlorine, bromine or iodine.
Alkyl：Straight or branched alkyl, such as methyl, ethyl, propyl group, isopropyl or the tert-butyl group.
Haloalkyl：Straight or branched alkyl, the hydrogen atom on these alkyl partly or entirely can be replaced by halogen atom, for example, haloalkyl such as chloromethyl, dichloromethyl, trichloromethyl, methyl fluoride, difluoromethyl or trifluoromethyl.
Alkyl sulphonyl：Refer to alkyl-so2, such as methyl sulphonyl.
Alkyl sulfoxide base：Refer to alkyl-so, such as methyl sulfoxide base.
Cycloalkyl：Refer to the compound of fatty race's cyclic structure, such as cyclopropane, pentamethylene, hexamethylene.Alkoxy：Straight or branched alkyl, is connected in structure through oxygen atom key.
Alkylamino radical：Straight or branched alkyl, is connected in structure through nitrogen-atoms key.
Alkylthio group：Straight or branched alkyl, is connected in structure through sulphur atom key.
Halogenated alkoxy：Straight or branched alkoxyl, the hydrogen atom on these alkoxies partly or entirely can be replaced by halogen atom.For example, halogenated alkoxy such as chloromethane epoxide, dichloro methoxyl group, trichloromethoxy, fluorine methoxyl group, difluoro-methoxy, trifluoromethoxy, chlorine fluorine methoxyl group or trifluoro ethoxy.
^ is for alkylamino radical：Straight or branched alkylamino radical, the hydrogen atom on these alkylamino radicals partly or entirely can be replaced by halogen atom.For example, halo alkylamino radical such as chloromethane amido, dichloro methylamino, trichlorine methylamino, fluorine methylamino, difluoro methylamino, trifluoro methylamino, chlorine fluorine methylamino or trifluoroethylamine base.
Halogenated alkylthio：Straight or branched alkylthio group, the hydrogen atom on these alkylthio groups partly or entirely can be replaced by halogen atom.For example, halogenated alkylthio such as chloromethane sulfenyl, dichloro methyl mercapto, trichloro-methylthio, fluorine methyl mercapto, difluoro methyl mercapto, trifluoromethylthio, chlorine fluorine methyl mercapto or trifluoro ethylmercapto group.
Alkenyl：Straight or branched simultaneously can there are double bond, such as vinyl or pi-allyl on any position.Block base：Straight or branched simultaneously can there are three keys, such as second block base or block propyl group on any position.In the compound of the present invention, stereoisomer (representing different configurations with Z and E, R and S respectively) can be formed due to connecting different substituents.The present invention includes Z-type isomers and E-isomer, R types isomers and S types isomers and its mixture of any ratio.
The general formula compound 1-1 and 1-2 of the present invention can be prepared in accordance with the following methods：
II III (Z/E- formulas) 1-1 (Z/E- formulas)
II IV 1-2
In above-mentioned reaction equation, L is leaving group, selected from chlorine or bromine；Other each groups are defined as above.Compound is commercially available in addition to dated self-control in formula.
Raw material II is (commercially available or pass through corresponding ester（It is commercially available）Hydrolysis is made）With III (or It is IV, commercially available）In suitable solvent such as tetrahydrofuran, acetonitrile, toluene, dimethylbenzene, benzene, N, in dinethylformamide, dimethyl sulfoxide, acetone or butanone, reacted in the presence of suitable alkali such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium acid carbonate, triethylamine, pyridine, sodium methoxide, caustic alcohol, sodium hydride, potassium tert-butoxide or sodium tert-butoxide, 1-1 (or 1-2) can be made.
Raw material II I is commercially available, can also refer to document Tetrahedron (2002), 58 (14), 2763-2775；Tetrahedron Letters (2005), 46 (3), 525-529) method self-control.
Each step reaction temperature can be in the range of room temperature to solvent boiling point above.Reaction time is 30 minutes to 20 hours, preferred reaction time 1 10 hours.The present invention can be illustrated with the compound listed in table the following, but do not limit the present invention.
" Ph-4-Cl " represents 4- chlorphenyls, CH in table2Ph-4-Cl represents 4- chlorobenzyls, and Pyr represents pyridine radicals, CH2- 3-Pyr-6-Cl represents chloro- 3- mouthfuls of 6- than pyridine benzyl.
R in formula I2The specific substituent in part is shown in Table 1, table 2;
Table 2
R2 R2 R2 R2
Na CH2CF3 CH2Ph-4-F CH2CH2CH3
K CH(CH3)2 CH2CH=CFC1 CH2COCH3
H CH2COPh CH2CH=CH2 CH2CH(CH3)2
CH3 CH2C≡CH CH2CH=C(C1)2 CH2CH2CH2CH3
CH2CH3 CH2CH=CHF CH2COCH2CH3 CH2CH=CH-CH3
CH2Ph CH2CH2CH3 CH2C≡C-CH3 CH2Ph-2,4-2F
CH2CH2Ph-4-Cl CH2CH2OCH3 CH2COPh-4-Cl CH2Ph-3,4-2Cl
CH2Ph-2,4-2Cl CH2CH2OCH2CH3 CH2COPh-2-Cl CH2Ph-3,5-2Cl
CH2Ph-2-N02 CH2Ph-4-C(CH3)3 CH2COPh-2-CH3 CH2Ph-2-S02CH3
CH2Ph-2-CH3 CH2CH(CH3)CH3 CH2COPh-4-CH3 CH2Ph-4-S02CH3
CH2Ph-2,4-2CH3 CH2Ph-2-COCH3 CH2Ph-2,4,6-3CH3 CH2Ph-2-CH2CH3
CH2C02CH3 CH2CH2N(CH2CH3)2 CH2CH2N(CH3)2 CH2CH2C02CH3 CH2C≡CC1 CH2COCH(CH3)2 C(CH3)3 CF3
CH2CH=CHC1 CH2-5-Pyr-2,3-2Cl CH2-5-Pyr-2-Cl CH2CN
CH2CH=C(F)2 CH(CH3)CH2CH3 CH2CH2CH2Br CH2COCH2COOCH2CH3
CH2CH2OPh CH2CH2OPh-4-Cl CH2CH2C1 CH2CH2Formulas of the F in the present invention（1-1) in compound, preferably spatial configuration is E- bodies, X preferably 0, R2、 R3It is preferred that moieties be shown in Table 3.
Table 3
63 Q7 CH3 CH2CH3
64 Q7 CH2CH3 CH3
65 Q7 CH2CH3 CH2CH3
66 Q8 CH3 CH3
67 Q8 CH3 CH2CH3
68 Q8 CH2CH3 CH3
69 Q8 CH2CH3 CH2CH3
70 Q9 CH3 CH3
71 Q9 CH3 CH2CH3
72 Q9 CH2CH3 CH3
73 Q9 CH2CH3 CH2CH3
74 Q10 CH3 CH3
75 Q10 CH3 CH2CH3
76 Q10 CH2CH3 CH3
77 Q10 CH2CH3 CH2CH3
78 Q12 CH3 CH3
79 Q12 CH3 CH2CH3
80 Q12 CH2CH3 CH3
81 Q12 CH2CH3 CH2CH3
82 Q13 CH3 CH3
83 Q13 CH3 CH2CH3
84 Q13 CH2CH3 CH3
85 Q13 CH2CH3 CH2CH3
86 Q14 CH3 CH3
87 Q14 CH3 CH2CH3
88 Q14 CH2CH3 CH3
89 Q14 CH2CH3 CH2CH3
90 Q15 CH3 CH3
91 Q15 CH3 CH2CH3
92 Q15 CH2CH3 CH3
93 Q15 CH2CH3 CH2CH3
94 Q16 CH3 CH3
95 Q16 CH3 CH2CH3
96 Q16 CH2CH3 CH3
97 Q16 CH2CH3 CH2CH3In the formula of the present invention（1-2) in compound, X preferably 0, R2It is preferred that moieties be shown in Table 4. Table 4
Tested by bioactivity screening, inventor proves that the compound of Formula I that the present invention is provided has good activity of weeding first.The compound of the present invention can efficiently control the weeds such as barnyard grass, lady's-grass, piemarker, and good effect is obtained with low dosage.Meanwhile, compound of Formula I of the invention for example has good security to crop safety to corn.
Present invention also offers a kind of Herbicidal combinations, the weight percentage that active component in the compound of Formula I as active component, composition is contained in said composition is 0.1-99%.Therefore it is used for the purposes for controlling weeds present invention additionally comprises said composition. The composition of the present invention can be prepared using method well known to those skilled in the art.This composition can contain the single compound of the present invention or the mixture of several compounds.
Carrier system in the present composition meets the material of following conditions：It is easy to be applied to pending site after preparing with active component, for example, can be plant, seed or soil；Or be conducive to storing, transport or operating.Carrier can be solid or liquid, including be usually the material of gas but Yi Ya Shrink into liquid, and generally carrier used in Herbicidal combinations are prepared can be used.
Suitable solid carrier includes natural and synthesis clay and silicate, such as diatomite, talcum, Attagel, alumina silicate (kaolin), montmorillonite and mica；Calcium carbonate；Calcium sulfate；Ammonium sulfate；The silica and synthetic calcium silicate or alumina silicate of synthesis；Element such as carbon and sulphur；Natural and synthesis resin such as cumarone resin, polyvinyl chloride and styrene polymer and copolymer；Solid polystream phenol；Pitch；Wax such as beeswax, paraffin.
Suitable liquid-carrier includes water；Alcohol such as isopropanol and ethanol；Ketone such as acetone, methyl ethyl ketone, methyl isopropyl Ketone, cyclohexyl ketone；Ether；Aromatic hydrocarbons such as benzene,toluene,xylene；Petroleum distillate such as kerosene and mineral oil；Chlorohydrocarbon such as carbon tetrachloride, perchloroethylene and trichloro ethylene.Generally, the mixture of these liquid is also suitable.
Composition is generally processed into the form of Nong Shrink things and is used to transport with this, is diluted before administration by user.The presence of a small amount of supporting surfactant contributes to dilution.So, it is preferably surfactant according at least a kind of carrier in the composition of the present invention.For example composition can contain at least two carriers, and wherein at least one is surfactant.
Surfactant can be emulsifying agent, dispersant or wetting agent；It can be non-ionic or ion surfactant.The example of suitable surfactant includes the sodium salt or calcium salt of polyacrylic acid and lignin sulfonic acid；Aliphatic acid or fatty amine or acid amides and oxirane and/or expoxy propane Shrink compounds containing at least 12 carbon atoms in molecule.Glycol, sorbierite, sucrose or pentaerythritol fatty ester and these esters and oxirane and/or expoxy propane Shrink compounds；Fatty alcohol or alkylphenol such as POP or to octyl group cresols and oxirane and/or expoxy propane Shrink compounds；Zhe Xie Shrink close the sulfate and sulfonate of product；At least contain in the molecule10The sulfuric acid of individual carbon atom or the alkali metal of sulphonic acid ester or alkali salt, such as particular certain cancers, sulfuric acid laurate sodium, the secondary Arrcostab sodium of sulfuric acid, sulfonated castor oil sodium salt, such as alkyl aryl sulfonic acid ester sodium, pelopon A.
The example of the composition of the present invention is wettable powder, pulvis, granule, aqua, emulsifiable Nong Shrink agent, emulsion, aerosol and smoke agent.Wettable powder generally wt. Active ingredient containing 25-75%, and generally in addition to solid inert carrier, the also dispersant containing 3-10% weight, and if desired can add the stabilizer and/or other additives such as bleeding agent or sticker of 0-10% weight.Pulvis generally may be molded to the composition with the composition similar to wettable powder, the generally component of weight activity containing 0.5-10%.Granula is generally prepared as having 10 to 100 mesh (1.676-0.152mm) size, and can be prepared with agglomerating or injection technique.The active component and 0-10% weight additive of usual granula weight containing 0.5-75% such as stabilizer, surfactant, sustained release modifying agent.Can Ruization Nong Shrink agent except solvent sunset foretell, cosolvent, 1-50%W/V active components, 2-20%W/V emulsifying agents and the other additives of 0-20%W/V such as stabilizer, bleeding agent and corrosion inhibitor are usually contained when needed.Xuan Fu Nong Shrink agent usually contains the active component of 10-75% weight, the dispersant of 0.5-15% weight, other additives such as defoamer, corrosion inhibitor, stabilizer, bleeding agent and the sticker of 0.1-10% weight.
Water dispersant and emulsion, the composition for example obtained by the wettable powder or dense Shrink things that are diluted with water according to the present invention, are also included in the scope of the invention.Described emulsion can have two types of Water-In-Oil or oil-in-water.
By adding other one or more herbicides in the composition, there can be broader spectrum of activity than single compound of Formula I.In addition, other herbicides can the activity of weeding of mutual-through type I there is synergistic effect, Can be by compound of Formula I and other herbicide mixtures, the changes of contents scope of active ingredient is very big in mixture, and active constituent content is general in 1%-95% in mixture, and convenient content is in 5%-60%.
The compound of the present invention has the following advantages that：
Because the compound of Formula I of the present invention not only has good activity of weeding, and there is good security to crop, therefore available for preventing and treating weeds in various crop, be specifically adapted for preventing and kill off weeds in corn field.It can be applied using insecticide-applying way well known to those skilled in the art and contain compound of Formula I of the present invention as the composition of active component, reach the purpose of control weeds.Embodiment
Specific examples below is used to further illustrate the present invention, but is not intended to limit the present invention.
Prepare embodiment
The preparation of the compound 4 of example 1
0.3 gram of reactant II-1 and 0.14 gram of reactant III-1 and 0.12 gram of triethylamine in 50 milliliters of toluene in
80 °C of stirring reactions, TLC is tracked, reaction is finished for 3 hours, heating under reduced pressure sloughs toluene, adds 200 milliliters of water and 100 milliliters of ethyl acetate, separates organic layer, and with 200 milliliters of saturated common salt water washings 2 times, Hou Nong Shrink are dried, purify to obtain 0.3 g of compound 4, thick thing with silica gel column chromatography.
Nuclear magnetic data (^HNMR, 300MHz, internal standard TMS, solvent C DC13) as follows：
5ppm 8.24 (s, 1H), 7.96 (s, 1H), 7.06 (d, 2H), 6.96 (d, 2H), 5.34 (s, 2H), 5.12 (s, 1H),
4.78 (m, 1H), 3.68 (s, 3H), 3.61 (s, 3H).
The preparation of the compound 70 of example 2
0.40 gram of reactant Π -2 and 0.228 gram of reactant III-1 and 0.19 gram of potassium carbonate are in 50 milliliters of N, in 60 °C of stirring reactions in dinethylformamide, TLC is tracked, and reaction is finished for 5 hours, and reaction solution is cooled into room temperature, add 200 milliliters of water and 100 milliliters of ethyl acetate, separate organic layer, and with 200 milliliters of saturated common salt water washings 2 times, dense Shrink after drying, purify to obtain 0.35 g of compound 70, pale yellow oil with silica gel column chromatography.
Nuclear magnetic data (^HNMR, 300MHz, internal standard TMS, solvent C DC13) as follows：
5ppm 8.55 (s, 1H), 7.73 (s, 1H), 5.46 (m, 2H), 5.20 (s, 1H), 3.70 (d, 6H), 2.76 (q, 2H), 2.06 (m, 1H), 1.35 (s, 3H), 1.28 (t, 3H), 1.07 (d, 3H), 0.87 (d, 3H).
0.50 gram of reactant Π -2 and 0.284 gram of reactant IV-1 and 0.24 gram of potassium carbonate are in 50 milliliters of Ν, in 80 °C of stirring reactions in Ν-dimethylformamide, TLC is tracked, and reaction is finished for 5 hours, and reaction solution is cooled into room temperature, add 200 milliliters of water and 100 milliliters of ethyl acetate, separate organic layer, and with 200 milliliters of saturated common salt water washings 2 times, dense Shrink after drying, purify to obtain 0.42 g of compound 125, thick thing with silica gel column chromatography.
Nuclear magnetic data (^HNMR, 300MHz, internal standard TMS, solvent C DC13) as follows：
5ppm 8.76 (s, lH), 8.55 (s, 1H), 7.79 (s, 1H), 4.93 (m, 2H), 4.20 (m, 2H), 3.52 (s, 2H), 2.04 (m, 2H), 1.36 (m, 6H), 0.94 (m, 3H), 0.83 (m, 3H).
The preparation of the compound 131 of example 4
0.4 gram of reactant II-1 and 0.183 gram of reactant IV-1 and 0.12 gram of triethylamine in 50 milliliters of toluene in
80 °C of stirring reactions, TLC is tracked, reaction is finished for 4 hours, heating under reduced pressure sloughs toluene, and add water 200 milliliters and 100 milliliters of ethyl acetate, separates organic layer, and with 200 milliliters of saturated common salt water washings 2 times, Hou Nong Shrink are dried, purify to obtain 0.28 g of compound 131, thick thing with silica gel column chromatography.
Nuclear magnetic data (^HNMR, 300MHz, internal standard TMS, solvent C DC13) as follows：
5ppm 8.26 (s, lH), 7.96 (s, 1H), 7.10 (d, 2H), 6.99 (d, 2H), 4.9 l (m, 3H), 4.20 (m, 2H),
3.47 (s, 2H), 1.72 (m, 3H), 0.84 (m, 3H).The preparation method provided according to the present invention can synthesize other compound of Formula I.
Part of compounds fusing point and nuclear magnetic data (^HNMR, 300MHz, internal standard TMS, solvent C DC13) as follows：Compound 38:Thick thing, 5ppm 7.61 (d, 1H), 7.48 (d, 1H), 7.37 (m, 1H), 5.69 (s, 1H),
5.44 (s, 2H), 5.10 (s, 1H), 3.69 (s, 6H), 3.68 (s, 3H), 3.63 (s, 3H).
Compound 50：Thick thing, 5ppm 7.34 (d, 1H), 7.12 (d, 1H), 5.53 (s, 2H), 5.21 (s, 1H), 3.90 (s 3H), 3.71 (s, 6H).
Compound 54:Yellow solid, 5ppm 8.03 (d, 1H), 7.81 (s, 1H), 7.62 (d, 1H), 7.16 (d, 1H), 7.07 (q, 1H), 5.46 (s, 2H), 5.19 (s, 1H), 3.70 (d, 6H).
Compound 58:Thick thing, 5ppm 7.76 (d, 1H), 7.49 (m, 3H), 7.05 (m, 2H), 5.46 (s, 2H), 5.19(s, 2H), 3.68(m, 6H)。
Compound 66：Thick thing, 5ppm 8.30 (m, 2H), 7.46 (m, 4H), 7.13 (m, 1H), 5.49 (s, 2H), 5.18 (s, 2H), 3.69 (s, 3H), 3.66 (s, 3H).
Compound 74:Thick thing, Sppm 8.42 (s, 1H), 7.86 (d, 1H), 7.04 (d, 2H), 6.93 (d, 2H), 5.34 (s, 2H), 5.13 (s, 1H), 4.78 (m, 1H), 3.68 (s, 3H), 3.61 (s, 3H), 1.65 (m, 3H).
Compound 86：Thick thing, 5ppm 7.47 (d, 1H), 7.35 (d, 1H), 6.97 (m, 5H), 5.33 (s, 2H), 5.14 (s, 1H), 4.76 (m, 1H), 3.68 (s, 3H), 3.62 (s, 3H), 1.65 (m, 3H).
Compound 90:Thick thing, 5ppm 8.67 (s, 1H), 8.04 (s, 1H), 7.65 (m, 2H), 7.17 (d, 2H), 6.96 (d, 2H), 5.36 (s, 2H), 5.13 (s, 1H), 4.81 (m, 1H), 3.69 (s, 3H), 3.62 (s, 3H), 1.66 (m, 3H).
Compound 94:Mp 91-93 °C, 5ppm7.42 (d, lH), 7.37 (s, 1H), 7.30 (d, 2H), 7.25 (d, 1H),
6.96 (d, 2H), 5.34 (s, 2H), 5.13 (s, 1H), 4.79 (m, 1H), 3.69 (s, 3H), 3.62 (s, 3H), 1.66 (d, 3H).
Compound 107：Thick thing, 5ppm 8.85 (m, 1H), 8.17 (d, 1H), 7.80 (m, 1H), 7.6 l (m, 1H), 5.12 (s, 2H), 4.24 (m, 2H), 3.80 (s, 2H), 1.27 (m, 3H).
Compound 110：Thick thing, 5ppm 7.40 (d, 1H), 7.14 (d, 1H), 5.03 (s, 2H), 4.20 (m, 2H), 3.92 (s, 3H), 3.61 (s, 2H), 1.27 (m, 3H).
Compound 128:Thick thing, 5ppm 8.42 (s, 1H), 7.85 (d, 1H), 7.06 (d, 2H), 6.95 (m, 3H), 4.9 l (m, 1H), 4.75 (m, 2H), 4.20 (m, 2H), 3.47 (s, 2H), 1.71 (m, 3H), 1.26 (m, 3H).
Compound 143：Thick thing, 5ppm 8.67 (s, 1H), 8.04 (s, 1H), 7.67 (d, 2H), 7.61 (d, 2H), 7.20 (d, 2H), 7.00 (d, 2H), 4.9 l (m, 3H), 4.20 (m, 2H), 3.48 (s, 2H), 1.73 (m, 3H), 1.27 (m, 3H).
Compound 146：Mp 78-80 °C, 5ppm 7.43 (d, 1H), 7.38 (s, 1H), 7.31 (d, 2H), 7.23 (s, 1H), 7.01 (d, 2H), 4.90 (d, 2H), 4.87 (q, 1H), 4.23 (q, 2H), 3.47 (s, 2H), 1.72 (d, 3H), 1.28 (t, 3H).
Example of formulations
Active component folding hundred is post-dised in formula, and all percentage compositions are weight percentage.
The % missible oil of example 5 35
Compound 4 35%
Phosphorous acid 10%
Ethoxylated triglycerides 15%
Cyclohexanone complements to 100%
Phosphorous acid is dissolved in cyclohexanone, compound 4 and ethoxylated triglycerides is then added, obtains transparent solution.
The wettable powder of example 6 60%
Compound 70 60%
Dodecyl sodium naphthalene sulfonate 2%
Sodium lignin sulfonate 9%
Kaolin complements to 100%
By compound 70, dodecyl sodium naphthalene sulfonate, sodium lignin sulfonate and kaolin（It is solid）Mix, crushed in pulverizer, until particle reaches standard.
The % aqueous suspensions of example 7 30
The % of compound 125 30 Dodecyl sodium naphthalene sulfonate 4%
Hemicellulose 2%
Expoxy propane 8%
Water complements to 100%
By compound 125 with that should add water：80% and dodecyl sodium naphthalene sulfonate in ball mill（1mm pearls）In play crushing.Hemicellulose and expoxy propane are dissolved in remaining 20% water, and then stirring adds said components.The % suspension concentrates of example 8 40
The % of compound 131 40
The % of ethylene glycol 10
The % of Nonoxynol-9 6
The % of sodium lignin sulfonate 10
The % of carboxymethyl cellulose 1
The % of 37 % formalins 0.2
The % of 75 % silicone oil aqueous emulsion 0.8
Water complements to 100%
Compound 131 and other components are sufficiently mixed, thus obtained suspension concentrates, the dilution that gained suspending agent can obtain any required concentration is diluted with water.
Biological activity determination
Herbicidal in the Room of example 9
Quantitative weed seed is sowed in a diameter of 7cm dixie cup equipped with Nutrition Soil respectively, rear earthing lcm is broadcast, in hot-house culture after suppression, water drenching, thinning, field planting after emerging（Plant/glass of grassy weed 10-20, plant/glass of broad leaved weed 2-4）, treat the grassy weed 2-3 leaf phases, broad leaved weed length to 2-4 leaf periods, by experimental design dosage crawler type crops sprayer（Britain Engineer Research Ltd. design productions）Carry out cauline leaf spraying treatment（The kg/cm of atomisation pressure 1.952, the ml/m of spouting liquid 502, the km/h of crawler track speeds 1.48).Experiment sets 3 repetitions.After after decoction natural air drying, it is placed in greenhouse and manages according to a conventional method, routine observation tries the situation of growing of material, and according to actual conditions, in preventive effect of the periodical visual inspection investigation reagent agent to weeds after processing.
Preventive effect grade scale：0 is invalid, and weeds is are killed or seriously suppressed by 100 % completely, and partial test the results are shown in Table 5.6 are shown in Table with herbicides imazethapyr (imazethapyr) expression activitiy result of the test.The part of compounds test result of table 5
200 100 40 35
1000 100 50 40
40 85 100 100 compounds 70 200 85 100 100
1000 85 100 100
40 30 10 5 compounds 90 200 45 100 98
1000 65 100 100
40 75 85 85 compounds 125 200 90 90 85
1000 90 90 90
40 0 50 80 compounds 128 200 0 50 75
1000 0 100 100
40 0 70 98 compounds 131 200 0 80 100
1000 0 100 100
Expression activitiy is tested
Quantitative corn, rice paddy seed are sowed in a diameter of 7cm dixie cup equipped with Nutrition Soil respectively, rear earthing l cm are broadcast, in hot-house culture after suppression, water drenching, thinning, field planting after emerging（1-2 plants/cup）, corn, paddy growth are treated to the leaf phases of 2- 4, by experimental design dosage crawler type crops sprayer（Britain Engineer Research Ltd. design productions）Carry out cauline leaf spraying treatment（The kg/cm of atomisation pressure 1.952, the ml/m of spouting liquid 502, the km/h of crawler track speeds 1.48), experiment sets 3 repetitions.After after decoction natural air drying, it is put in greenhouse and manages according to a conventional method, observation corn, the situation of growing of paddy rice, periodical visual inspection investigates reagent agent to corn, the security of paddy rice.Safety classification standard：0 is represented to crop without any damage, and crop is is killed or seriously suppressed by 100% completely, and partial test the results are shown in Table 7. Table 7 is tested corn, Security of rice

Claims (6)

  1. Substituted carboxylic ester compounds are planted, structure is as shown in formula I:
    In formula：
    A=B=carbon；
    When A is connected with B for double bond, A is connected with ^ for singly-bound, OR3, general structure is as shown in 1-1:
    1-1
    Z/E- formulas are when A is connected with B for singly-bound, and A is connected with ^ for double bond, and=0, general structure is as shown in 1-2:
    1-2
    X is selected from 0 or NH;
    R2Selected from H, K, Na, CRC12Alkyl, cyano group d-C12Alkyl, halo CRC12Alkyl, C2-C6Alkenyl, C2-C6Block base, ^ are for C2-C6Alkenyl, ^ are for C2-C6Block base, CRC12Alkyl-carbonyl, CRC12Alkoxy carbonyl group, C3-C8Cycloalkyl, d-C12Alkyl sulfoxide base, d-C12Alkyl sulphonyl, d-C12Alkoxy CRC12Alkyl,
    Ci- Ci2
    Base, phenyl, pyridine radicals, phenyl d-C6Alkyl, pyridine radicals d-C6Alkyl or phenyl carbonyl d-C6Alkyl, wherein phenyl ring or pyridine ring hydrogen can be replaced by 1-3 following radicals：Halogen, NO2、 CN、 d-c12Alkyl, halo d-c12Alkyl, d-c12Alkoxy, halo d-c12Alkoxy, d-c12Alkylamino, halo d-c12Alkylamino,12Alkylthio group, halo d-C12Alkylthio group, d-C12Alkyl-carbonyl, d-C12Alkyl sulfoxide base or d-C12Alkyl sulphonyl；
    R3Selected from H or d-C12Alkyl；
    Q is selected from any one group of Q1 as follows to Q18： 81
    ^0/0l03M3/I3d Or its stereoisomer.
    2nd, according to the compound described in claim 1, it is characterised in that in formula
    X is selected from 0;
    R2Selected from H, K, Na, d-C6Alkyl, cyano group d-C6Alkyl, halo CrC6Alkyl, C2-C6Alkenyl, C2-C6Block base, halo C2-C6Alkenyl, halo C2-C6Block base, d-C6Alkyl-carbonyl CrC6Alkane, Ci-C6 Ci-C6The Ci-Ci2 sulfonyls of C3-Cg i C1-C12 M 1, CrC6Alkoxy d-C6Alkyl, phenyl, pyridine radicals, phenyl d-C6Alkyl or pyridine radicals CrC6Baked base；
    R3Selected from H or d-C12Alkyl；
    Q any one group into Q18 selected from Q1.
    3rd, according to the compound described in claim 2, it is characterised in that：
    Formula 1-1 stereochemical structure is E- formulas；
    X is selected from 0;
    R2Selected from H, K, Na, CrC6Alkyl, halo CrC6Alkyl, C2-C6Alkenyl, C2-C6Block base, halo C2-C6Alkenyl or ^ are for C2-C6Block base；
    R3Selected from H or d-C6Alkyl；
    Q any one group into Q18 selected from Q1.
    4th, according to the compound described in claim 3, it is characterised in that：
    R2Selected from H, K, Na or d-C6Alkyl；
    R3Selected from CH3 ;
    Q any one group into Q16 selected from Ql.
    5th, a kind of compound according to described in claim 1 is used for the purposes for controlling weeds.
    6th, a kind of Herbicidal combinations, it is characterised in that：Contain compound of Formula I described in claim 1 as active component, the weight percentage of the active component in composition is 0.1-99%.
    7th, a kind of Herbicidal combinations according to claim 6 are used for the purposes for controlling weeds.
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CN111888803B (en) * 2020-06-30 2021-10-29 浙江传化华洋化工有限公司 Oleate modified organic silicon defoaming agent for coating and preparation method thereof

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