CN108997325B - Aryl bithiazole compound and application thereof - Google Patents
Aryl bithiazole compound and application thereof Download PDFInfo
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- CN108997325B CN108997325B CN201810737628.8A CN201810737628A CN108997325B CN 108997325 B CN108997325 B CN 108997325B CN 201810737628 A CN201810737628 A CN 201810737628A CN 108997325 B CN108997325 B CN 108997325B
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- C07—ORGANIC CHEMISTRY
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- C07D417/00—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
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- 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
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
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Abstract
The invention discloses an aryl bithiazole compound and application thereof. A series of aryl-isothiazole compounds are prepared and researched, and from biological activity test results, the aryl-isothiazole compounds provided by the invention have good herbicidal activity and a wide herbicidal spectrum, and the inhibition rate of wheat, sorghum, barnyard grass, cucumber, rape and radish on dicotyledonous weeds is high, and particularly the aryl-isothiazole compounds have obvious inhibition effects on amaranthus retroflexus and snakehead intestines.
Description
Technical Field
The invention relates to an aryl-bithiazole compound and application thereof.
Background
The pesticide brings benefits to human beings and also brings harm to human beings. The increase of the usage amount of the pesticide inevitably causes harm to human bodies, organisms and environment to a certain degree. In the future, the greening, high-efficiency and economical scientific and reasonable use of pesticides is realized, scientific and technological progress is relied on a novel agricultural operation main body, scientific and technological innovation is enhanced, and the popularization and application force of novel green, low-toxicity and high-efficiency pesticides is increased, so that new pesticides with new action mechanisms are required to be continuously discovered.
The pyridine herbicide Thiazopyr (Thiazopyr)1, which inhibits cell division by interfering with spindle microtubule formation, primarily controls grassy weeds and some broadleaf weeds, and is used pre-emergence. Aminopyralid herbicide Aminopyralid (Aminopyralid)2 has low toxicity and high efficiency, and is mainly used for weeding in mountainous regions and uncultivated areas. The chemical structural formulas of the thiazole nicotinic acid and the aminopyralid are as follows:
2016 prenanti Carter et al in WO 2016046078 report tri-substituted thiazole derivatives and their herbicidal activity, most of the compounds showed good activity against Avena sativa, Echinochloa crusgalli, Chrysanthemum coronarium, Amaranthus retroflexus and Setaria viridis, and the data shows that when R is in the compound of the general structure 31＝CH3The activity of the compound is better than that of the compound substituted by other groups, and is 10The control effect on wild oat, barnyard grass, crowndaisy hemp, redroot amaranth and setaria viridis reaches more than 80 percent under the dosage of 0 mg/L.
In patent CN 106831638, it is reported that 5-substituted thiazole amide compounds are synthesized by survivors and the like in 2017, and the compounds with the general formula 4 are found to have better inhibitory activity on gramineous weeds. And has the active structure of brassinolide, so the brassinolide can be used as a plant growth regulator for application and development.
In the development of herbicides, structures containing substituted aryl-linked heterocycles are also one of the hotspots of current research. The PPO herbicides act through a mechanism that causes protoporphyrinogen IX to rapidly accumulate in chloroplasts and permeate into cytoplasm, and protoporphyrinogen IX is oxidized to protoporphyrin IX through a non-enzymatic mechanism or by other oxidases (ER enzymes or PM enzymes) to generate singlet oxygen under light conditions, which in turn causes fatty acid peroxidation of cell membranes, pigment destruction, and the like, and finally causes leaf death. There are many commercial products on the market, such as indoxyl (Cinidon-ethyl)5, isopyrachlor (isopopazol) 6, Saflufenacil (Saflufenacil)7, flupyridazinyl (Flufenpyr-ethyl)8, and so on.
The prior art does not disclose the aryl-bithiazole compound provided by the invention, and the compound has good activity in weeding.
Disclosure of Invention
The invention provides a novel aryl bithiazole compound, a preparation method and application thereof, and the compound has good herbicidal activity.
The aryl-bis-thiazole compound is characterized in that the chemical structural formula is shown as a formula (I);
formula (I)) In, X1Is selected from
X2And X3Each independently selected from nitrogen, oxygen or sulfur; x4And X5Each independently selected from carbon or nitrogen; y is selected from fluorine, chlorine, bromine, iodine, nitro or methylsulfonyl;
wherein R is1、R2、R3、R4Each independently selected from hydrogen and C1－C20Alkyl of (C)1－C20Halogenoalkyl of, C1－C20Alkoxy group of (C)1－C20Cycloalkyl of, C1－C20Haloalkoxy or phenyl of (a);
R5selected from hydrogen, halogen, nitro, nitrile, hydroxyl, mercapto and C1－C20Alkyl of (C)2－C20Alkenyl of, C2－C20Alkynyl of (A), C1－C20Halogenoalkyl of, C2－C20Haloalkenyl of (A), C2－C20Halogenated alkynyl of (A), C1－C20Alkoxy group of (C)1－C20Halogenoalkoxy of (C)1－C20Alkylthio, carboxylic acid, C1－C20Alkyl esters of (a).
The aryl bithiazole compound is characterized in that R1Selected from hydrogen, C1－C20Alkyl of (C)1－C20Is preferably hydrogen or C1－C20More preferably hydrogen or methyl.
The aryl bithiazole compound is characterized in that R2Is selected from C1－C4Alkyl of (C)1－C4The haloalkyl or substituted aryl of (1) is preferably methyl, hydrogen, ethyl, isopropyl, isobutyl, propyl, cyclopropyl, cyclopentyl, 2-methylcyclopentyl, cyclohexyl, 2,4, 4-tetramethylbutyl, phenethyl, phenylmethylene, 4-bromophenyl, 4-nitrophenyl, 2, 4-bis-phenylFluorophenyl group, 2-methylphenyl group, 4-tert-butylphenyl group, 2-methyl-6-ethylphenyl group, 3-methoxyphenyl group, 2-chlorophenyl group, 2, 5-dimethylphenyl group, 3-isopropylphenyl group, 2, 4-dichlorophenyl group, 2-fluoro-4-bromophenyl group, 3-fluorophenyl group, 1-phenylethyl group, 2-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 3, 4-difluorophenyl group, 3-methylphenyl group, 2-fluoro-4-iodophenyl group, 4-trifluoroethyl benzoate group, 2, 4-dimethylphenyl group, 2-methyl-3-chlorophenyl group, 3-trifluoromethylphenyl group, 3, 5-dichlorophenyl group, 2-chloro-4-methylphenyl group, 2-methyl-6-ethylphenyl group, 3-methoxyphenyl group, 2-chlorophenyl group, 3, 5-dichlorophenyl group, 3-chloro, 2-fluoro-4-methylphenyl, 4-oxytrifluoromethylphenyl, 4-methylphenyl, 2, 4-difluorophenyl or 3, 4-dichlorophenyl.
The aryl bithiazole compound is characterized in that R3Selected from hydrogen, C1－C20Alkyl of (C)1－C20Haloalkyl or substituted aryl of, preferably C1－C4Alkyl of (C)1－C4More preferably methyl, ethyl, propyl, isobutyl, cyclopentyl, 2-methylphenyl, 2, 5-dimethylphenyl, 3-methyl-4-fluorophenyl, 4-ethylphenyl or phenyl.
The aryl bithiazole compound is characterized in that R4Selected from hydrogen, C1－C20Alkyl of (C)1－C20Haloalkyl or substituted aryl of, preferably C1－C4Alkyl of (C)1－C4Or substituted aryl.
The aryl bithiazole compound is characterized in that R4Is selected from C1－C4The alkyl group of (3) is preferably a methyl group.
The aryl bithiazole compound is characterized in that X2、X3、X4And X5Are each selected from nitrogen, sulfur, carbon and nitrogen.
The aryl-bis-thiazole compound is characterized in that Y is selected from fluorine, chlorine or bromine, and is preferably chlorine.
The aryl bithiazole compound is characterized in that R5Selected from hydrogen.
The application of the aryl-bithiazole compound in herbicides is provided.
A series of aryl-isothiazole compounds are prepared and researched, and from biological activity test results, the aryl-isothiazole compounds provided by the invention have good herbicidal activity and a wide herbicidal spectrum, and the inhibition rate of wheat, sorghum, barnyard grass, cucumber, rape and radish on dicotyledonous weeds is high, and especially the aryl-isothiazole compounds have obvious inhibition effects on redroot amaranth and snakehead.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example (b):
the aryl-bithiazole compound provided by the invention has a structural formula shown in a formula (I), and most preferably has structures of two forms of compounds shown in a formula (K) and a formula (L), wherein the structural formula is as follows:
the synthetic routes for the compounds of formula (K) and formula (L) above are as follows:
by way of example, the intermediates of the above formula may be prepared by:
(1) the synthesis of an intermediate represented by the formula (B):
100g (0.496mol) of 2-chloro-5-nitro-benzoic acid of the formula (A) as starting material and 1000m L of technical acetone are added into a 2000m L three-neck flask, dissolved and mechanically stirred, and then K is added2CO3205.6g (1.488mol), then slowly dropwise adding 62.5g (0.496mol) dimethyl sulfate, after about 20min of dropwise adding, heating the reaction solution to 35 ℃ and keeping the temperature constant, reacting for 2h, tracking and detecting the reaction process by T L C, after the reaction is finished, filtering, taking the filtrate, and carrying out rotary evaporation on the filtrateAfter the acetone was evaporated to dryness, 500m L ethyl acetate and 350m L water were added to extract, the organic layer was separated, washed with water for 3 times, dried over anhydrous magnesium sulfate, and then ethyl acetate was evaporated to obtain 101.55g of a yellow solid, which was the intermediate represented by formula (B), with a crude yield of 95.0%.
(2) The synthesis of an intermediate represented by the formula (C):
adding 101.55g (0.471mol) of 2-chloro-5-nitro-methyl benzoate shown in a formula (B) into a 1000m L three-neck flask, adding 350m L ethanol and 70m L water, then adding 65.94g (1.178mol) of iron powder, mechanically stirring and heating to reflux, slowly adding 50m L saturated ammonium chloride aqueous solution, detecting by T L C after 1 hour, continuously adding 28g (0.5mol) of iron powder, continuously reacting for 30 minutes, detecting by tracking by T L C, completely reacting, and having an impurity point, filtering the reaction liquid by using a sand core funnel filled with silica gel while the reaction liquid is hot, washing filter residues by using 50m L ethanol, combining the filtrate and the washed ethanol, evaporating the ethanol on a rotary evaporator, extracting by using ethyl acetate, separating an organic layer, and sequentially washing the organic layer by water, washing by saturated salt water, drying by anhydrous magnesium sulfate and evaporating the ethyl acetate to obtain 82.91g of red brown liquid;
for the synthesis of the intermediate represented by the formula (C), a variety of methods have been reported in the literature, for example, reduction methods such as palladium-carbon catalytic hydrogenation, hydrazine hydrate, raney nickel hydrogenation, sulfide reduction, metal hydride, stannous chloride, and the like. Because the benzene ring contains halogen Cl atoms, the Cl atoms are prevented from falling off, and the price of the catalyst is considered, in the experiment, mild iron powder is selected as a reducing agent, and the reduced iron powder is added for several times, so that the phenomenon that the reaction is too violent to cause material flushing can be relieved, and the risk degree of the experiment is reduced. And meanwhile, saturated ammonium chloride aqueous solution is added to promote electron transfer, so that the reaction is promoted.
(3) Synthesis of an intermediate represented by formula (E):
adding 37.12g (0.2mol) of 2-chloro-5-amino-methyl benzoate shown in formula (C), 100m L hydrochloric acid and 70m L water into a 500m L three-neck flask, mechanically stirring, freezing at low temperature to-5-0 ℃, precipitating light yellow solid, dissolving 13.8g (0.2mol) of sodium nitrite in 20m L water, slowly dropwise adding into the three-neck flask, completely dissolving the light yellow solid in the three-neck flask within 45min, keeping the temperature of the reaction solution at-2-0 ℃, stirring the mixture in the three-neck flask for 15min, dropwise adding 45.7g (0.25mol of HBF4) of 48% tetrafluoroboric acid solution, dropwise adding about 30min, keeping the temperature of the reaction solution at 0-2 ℃, continuously stirring for 2 hours, after the reaction is finished, filtering the reaction solution, washing filter residues by using dilute tetrafluoroboric acid solution, washing by 50% ethanol (50m L), washing by using anhydrous ethanol (50m L), drying by using 50m L g of the light yellow solid, and washing by using 596.6 g of the light yellow solid, and obtaining yield of 596.6.
Adding 67.5g (0.68mol) of isopropenyl acetate, 30.75g (0.38mol) of anhydrous sodium acetate and 3.86g (0.04mol) of cuprous chloride into a 500m L three-neck flask, carrying out magnetic stirring, slowly adding the light yellow solid obtained in the previous step, wherein the temperature of the reaction liquid obviously rises, placing the three-neck flask into an ice water bath, keeping the temperature of the reaction liquid at 20-25 ℃, stirring at room temperature for 2 hours after the light yellow solid is added, tracking two impurity points in the reaction process by T L C, carrying out column chromatography separation, carrying out dry sampling, carrying out gradient elution, and obtaining 27.6g of red-brown oily liquid by a washing and dehydrating machine sequentially comprising V (petroleum ether), V (ethyl acetate) being 10:1, 6:1 and 4:1, wherein the total yield is 52.8%;
the mechanism of the above reaction process is: nitrous acid is unstable and sodium nitrite, hydrochloric acid and tetrafluoroboric acid are generally used, and nitrous acid generated during the reaction immediately reacts with the aromatic amine to produce a solid fluoroborate diazonium salt. Removing one molecule of N from solid fluoborate diazonium salt under catalysis of cuprous chloride2To generate benzene radical with Cu+Oxidized Cu2+. Double bond addition of phenyl radical and ethyl isopropoxide to obtain radical intermediate, which is reacted in Cu2+Oxidation under catalysis to form carbenium ion intermediate, and Cu2+Is reduced to Cu+. The carbocation intermediate transfers acyl cation to obtain the target product as the intermediate shown in formula (E), and the acyl cation reacts with acetate to generate acetic anhydride.
(4) Synthesis of an intermediate represented by formula (F):
dissolving 11.12g (49mmol) of methyl 2-chloro-5- (2-oxopropyl) benzoate shown in formula (E) by 100m L dichloromethane, magnetically stirring under ice bath conditions, slowly dropwise adding a mixed solution of 7.94g (59mmol) of sulfonyl chloride and 15m L dichloromethane into a 50m L constant pressure dropping funnel, taking out the ice bath after dropwise adding, stirring at room temperature, tracking and detecting by T L C, wherein two impurity points exist, adding 40m L saturated saline water to separate an organic phase after the reaction is finished, washing, drying and evaporating dichloromethane on a rotary evaporator to obtain 12.25g of reddish brown liquid, and the crude yield is 96.5%.
(5) Synthesis of an intermediate represented by formula (G):
adding 52g (500mmol) of 3-pyridine carbonitrile and 105m L (500mmol) of 40% ammonium sulfide solution into a 1000m L round-bottom flask, adding 500m L methanol as a solvent, reacting at room temperature for 18h, separating out a golden yellow solid, filtering, and drying to obtain 66.5g of a target product with a yield of 96.4%.
(6) Synthesis of an intermediate represented by formula (H):
adding 7.88G (30mmol) of methyl 2-chloro-5- (1-chloro-2-oxopropyl) benzoate shown in formula (F) and 4.14G (30mmol) of pyridine-3-thiocarboxamide (G) into a 150m L round-bottom flask, adding 50m L of anhydrous acetic acid and 4.95G (60mmol) of anhydrous sodium acetate, magnetically stirring, heating to 70-80 ℃ for reaction for 2 hours, heating to reflux, reacting for 3 hours, detecting that the reaction is complete by T L C, stopping heating, distilling off part of anhydrous acetic acid, cooling to room temperature, pouring the reaction into 300m L water, extracting with ethyl acetate (100m L× 2), separating an organic phase, washing the organic phase with saturated saline (50m L× 3), separating the organic phase, drying with anhydrous dry magnesium sulfate, filtering, separating by column chromatography, loading, gradient elution, and washing-dewatering machine sequentially obtaining V (petroleum ether V (ethyl acetate): 10:1 and 4:1, 6.28G of white solid, and obtaining 6.63.63.126-121 m.126 ℃.
(7) The synthesis of an intermediate represented by formula (I):
dissolving 6.5g of methyl 2-chloro-5- (4-methyl-2- (pyridine-3-yl) thiazole-5-yl) benzoate shown in the formula (F) by using 60m L Tetrahydrofuran (THF), adding the dissolved methyl 2-chloro-5- (4-methyl-2- (pyridine-3-yl) thiazole-5-yl) benzoate into a 100m L round-bottom flask, adding 12m L NaOH aqueous solution (10 mass percent of NaOH), heating to reflux, reacting for 2 hours, evaporating to remove THF, pouring the reaction solution into 20m L water, adjusting the pH value to 4-5 by using dilute hydrochloric acid, separating out white solid, filtering, washing a filter cake by water, and drying to obtain 5.90g of a compound shown in the formula (I), wherein the yield is 94.0%, and m.p.179-182 ℃.
The following aryl-bithiazole compounds are listed as compounds represented by formula (K) and formula (L), as shown in tables 1 and 2, respectively, and the hydrogen spectrum data and mass spectrum data are shown in table 3:
TABLE 1 Arylbis-thiazole compounds represented by the formula (K)
TABLE 2 Arylbis-thiazole compounds represented by the formula (L)
TABLE 3 characterization data for arylisothiazoles of formula (K) and (L)
Example 1 preparation of 2-chloro-N-methyl-5- (4-methyl-2- (pyridin-3-yl) thiazol-5-yl) benzamide as shown in compound No. K1:
adding 2-chloro-5- (4-methyl-2- (pyridine-3-yl) thiazole-5-yl) benzoyl chloride (0.1g,2.9mmol) shown in formula (J) into a 25m L single-neck flask, adding 10m L tetrahydrofuran for dissolving, adding 33% methylamine aqueous solution (0.09g,2.9mmol) and triethylamine (0.39g,5.8mmol), stirring at room temperature for reacting 2 h.T L C to detect the reaction progress, filtering after the reaction is finished, taking filtrate for desolventizing, and recrystallizing in petroleum ether to obtain the target compound shown in formula (K1);
example 2 preparation of 2-chloro-5- (4-methyl-2- (pyridin-3-yl) thiazol-5-yl) benzamide as shown in compound No. K2:
adding 2-chloro-5- (4-methyl-2- (pyridine-3-yl) thiazole-5-yl) benzoyl chloride (0.1g,2.9mmol) shown in a formula (J) into a 25m L single-neck flask, adding 10m L tetrahydrofuran for dissolving, adding 0.1g of ammonia (the molar weight of the ammonia is 2.9mmol) and triethylamine (0.39g,5.8mmol), stirring at room temperature for reacting 2 h.T L C to detect the reaction progress, filtering after the reaction is finished, taking filtrate for desolventizing, and recrystallizing in petroleum ether to obtain a target compound shown in a formula (K2);
example 3 preparation of methyl 2-chloro-5- (4-methyl-2- (pyridin-3-yl) thiazol-5-yl) benzoate as shown in compound No. L49:
adding 2-chloro-5- (4-methyl-2- (pyridine-3-yl) thiazole-5-yl) benzoyl chloride (0.1g,2.9mmol) shown in a formula (J) into a 25m L single-neck flask, adding 10m L tetrahydrofuran for dissolving, adding methanol (0.09g,2.9mmol) and triethylamine (0.39g,5.8mmol) for stirring at room temperature for reacting 2 h.T L C, detecting the reaction progress, after the reaction is finished, filtering, taking filtrate for desolventizing, and recrystallizing in petroleum ether to obtain a target compound shown in a formula (L49);
example 4 preparation of ethyl 2-chloro-5- (4-methyl-2- (pyridin-3-yl) thiazol-5-yl) benzoate as shown in compound No. L50:
adding 2-chloro-5- (4-methyl-2- (pyridine-3-yl) thiazole-5-yl) benzoyl chloride (0.1g,2.9mmol) shown in a formula (J) into a 25m L single-neck flask, adding 10m L tetrahydrofuran for dissolving, adding ethanol (0.14g,2.9mmol) and triethylamine (0.39g,5.8mmol) for stirring at room temperature for reacting 2 h.T L C to detect the reaction progress, after the reaction is finished, filtering, taking filtrate for desolventizing, recrystallizing in petroleum ether, and recrystallizing in petroleum ether to obtain the target compound shown in a formula (L50);
example 5 (the following "gai/ha" refers to per gram of active per hectare):
compared with a control group prepared by using clear water as a control group, after the prepared aryl-bithiazole compound liquid medicine is applied, the herbicidal activity and the safety to crops of the compound are visually observed according to the expression degree of plant damage symptoms (inhibition, deformity, yellowing and whitening), 0 represents no herbicidal effect or safety to crops, 100 percent represents complete weed or crop killing, and the evaluation criteria of the herbicidal activity and the crop safety visual method are shown in table 4;
TABLE 4
In table 4, the herbicidal activity of the applied aryl-isothiazole compound liquid reaches 70-100%, and the aryl-isothiazole compound liquid can be used; can be used when the toxicity to crops reaches 0-20%.
The method for determining the herbicidal activity of the aryl-bithiazole compounds with the numbers of K1-48 and L49-58 by adopting a pesticide bioassay SOP method mainly comprises the following steps:
(1) performing primary screening on a target organism by using a target aryl-isothiazole compound under the dosage of 200 mg/L concentration, testing the activity of the target compound, observing by a visual method, and performing next-step re-screening on the compound with the activity of more than 80%;
(2) re-screening: the toxicological research of the target compound and the safety test of crops are carried out, and then the comparison with a contrast medicament is carried out, so as to preliminarily judge the action mode and the prevention and treatment spectrum of the compound.
The general sieve comprises the specific steps of firstly adopting a culture dish method to carry out general sieve, wherein test targets are seeds of radish, cucumber, rape, wheat, sorghum and barnyard grass, wherein the seeds of the wheat, the sorghum and the radish are subjected to pregermination in advance, uniform and consistent exposed white seeds are taken for testing, the target seeds are put into a culture dish with the inner diameter of 9cm and paved with double layers of filter paper, 10m L (the aryl isothiazole compounds are respectively numbered as K1-48 and L49-58) of aryl isothiazole compound liquid medicine with the concentration of 200 mg/L is added into each culture dish, the filter paper is uniformly and fully wetted, clear water is set for comparison, the treated filter paper is respectively numbered and marked, the treated filter paper is placed into an artificial climate box for culture, the artificial climate box is set at the temperature of 28 ℃, the illumination temperature of 3000L ux, the illumination time of 16L: 8D, RH 75% and the target root and stem inhibition rate is observed by an eye test method after 7 days, and the biological activity test;
TABLE 6 results of tests on active dishes of arylbithiazole compounds in target crops (200 mg/L, activity/%)
If the general screening result shows better activity, further carrying out a pot screening test. The test targets for pot screening were abutilon, redroot amaranth, snakehead, crab grass, barnyard grass, and green bristlegrass. And (3) taking a flowerpot with the inner diameter of 7.5cm, filling composite soil (V vegetable garden soil: V seedling culture medium is 1:2) to 3/4 positions of the flowerpot, directly and respectively sowing the six weed targets (the bud rate is more than or equal to 85%), covering 0.2cm of soil, and waiting until weeds grow to about 3-leaf stage for later use. The pots treated in the pre-seedling test were subjected to a soil surface spray treatment one day after seeding. After each compound is applied by an automatic spray tower (model: 3WPSH-700E) according to the dosage of 150g.a.i./ha, the weed foliage liquid medicine is air-dried and then is transferred to a greenhouse for culture, and the activity (%) of weeds is checked after 25 days, and the contrast medicine is: mesotrione (Mesotrione).
As can be seen from Table 6, the activity of the aryl-bithiazole compounds with the numbers of K1-49 on target crops exceeds 80%, namely the activity enters a primary screening step and is subjected to a herbicidal activity test.
The weed and crop species selected for the bioactivity determination test of this example are shown in table 5 below;
TABLE 5
| Name of Chinese | Name of English | Name of science |
| Barnyard grass | barnyardgrass | Echinochloa crusgalli |
| Tang style food | Crabgrass | Digitaria sanguinalis |
| Herb of common Setaria | Giant foxtail | Setaria viridis |
| Amaranthus retroflexus (lour.) Merr | Amaranth pigweed | Amaranthus retroflexus |
| Abutilon | Chingma abutilon | Abutilon theophrasti |
| Snakehead intestine | False daisy | Eclipta prostrata |
| Wheat (Triticum aestivum L.) | Wheat | Triticum aestivum |
| Rape seed | Rape | Brassica napus |
| Sorghum grain | Sorghum | Sorghum bicolor |
| Cucumber (Cucumis sativus) | Cucumber | Cucumis sativus |
| Radish (radish) | Radish | Raphanus sativus |
Table 7 results of herbicidal Activity test of Compounds No. K1-48 (150 g. ai/ha, inhibition/%) after emergence
According to the biological activity test result, the aryl-isothiazole compound provided by the invention has good herbicidal activity, a wider herbicidal spectrum and higher inhibition rate on dicotyledonous weeds, and particularly has an obvious inhibition effect on Amaranthus retroflexus and snakehead intestine.
The description is given for the sole purpose of illustrating embodiments of the inventive concept and should not be taken as limiting the scope of the invention to the particular forms set forth in the embodiments, but rather as being limited only to the equivalents thereof as may be contemplated by those skilled in the art based on the teachings herein.
Claims (2)
1. An aryl-bis-thiazole compound is characterized in that the chemical structural formula is shown as a formula (K) or a formula (L);
in the formula, R1Is H or methyl;
R2is methyl, hydrogen, ethyl, isoPropyl, isobutyl, propyl, cyclopropyl, cyclopentyl, 2-methylcyclopentyl, cyclohexyl, 2,4, 4-tetramethylbutyl, phenethyl, phenylmethylene, 4-bromophenyl, 4-nitrophenyl, 2, 4-difluorophenyl, 2-methylphenyl, 4-tert-butylphenyl, 2-methyl-6-ethylphenyl, 3-methoxyphenyl, 2-chlorophenyl, 2, 5-dimethylphenyl, 3-isopropylphenyl, 2, 4-dichlorophenyl, 2-fluoro-4-bromophenyl, 3-fluorophenyl, 1-phenylethyl, 2-trifluoromethylphenyl, 4-trifluoromethylphenyl, 3, 4-difluorophenyl, 3-methylphenyl, 2-fluoro-4-iodophenyl, 2-methyl-cyclopentyl, cyclohexyl, 2-methyl-butyl, 4-methylphenyl, 4-trifluoromethyl-phenyl, 3, 4-difluoro-phenyl, 3-methylphenyl, 2-fluoro-4-iodophenyl, 4-trifluoroethyl benzoate, 2, 4-dimethylphenyl, 2-methyl-3-chlorophenyl, 3-trifluoromethylphenyl, 3, 5-dichlorophenyl, 2-chloro-4-methylphenyl, 2-fluoro-4-methylphenyl, 4-oxytrifluoromethylphenyl, 4-methylphenyl, 2, 4-difluorophenyl or 3, 4-dichlorophenyl;
R3is methyl, ethyl, propyl, isobutyl, cyclopentyl, 2-methylphenyl, 2, 5-dimethylphenyl, 3-methyl-4-fluorophenyl, 4-ethylphenyl or phenyl.
2. An arylisothiazole compound according to claim 1, which is used as a herbicide.
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| CN101945856A (en) * | 2007-12-21 | 2011-01-12 | 杜邦公司 | The weedicide pyridazinone derivative |
| WO2015191630A1 (en) * | 2014-06-10 | 2015-12-17 | Sanford-Burnham Medical Research Institute | Metabotropic glutamate receptor negative allosteric modulators (nams) and uses thereof |
| CN105916849A (en) * | 2014-01-16 | 2016-08-31 | 纳幕尔杜邦公司 | Pyrimidinyloxy benzene derivatives as herbicides |
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| CN101945856A (en) * | 2007-12-21 | 2011-01-12 | 杜邦公司 | The weedicide pyridazinone derivative |
| CN105916849A (en) * | 2014-01-16 | 2016-08-31 | 纳幕尔杜邦公司 | Pyrimidinyloxy benzene derivatives as herbicides |
| WO2015191630A1 (en) * | 2014-06-10 | 2015-12-17 | Sanford-Burnham Medical Research Institute | Metabotropic glutamate receptor negative allosteric modulators (nams) and uses thereof |
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| 苯并噻唑类化合物设计合成及生物活研究.;陈瑞希等，;《中国化学会第九届全国有机化学学术会议》;20150728;第1页. * |
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