CN108997325A - A kind of aryl connection thiazole compound and application - Google Patents
A kind of aryl connection thiazole compound and application Download PDFInfo
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- CN108997325A CN108997325A CN201810737628.8A CN201810737628A CN108997325A CN 108997325 A CN108997325 A CN 108997325A CN 201810737628 A CN201810737628 A CN 201810737628A CN 108997325 A CN108997325 A CN 108997325A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
- C07D417/02—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
- C07D417/04—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 directly linked by a ring-member-to-ring-member bond
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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 a kind of aryl connection thiazole compound and applications.A series of aryl connection thiazole compounds are prepared in the present invention, and it is applied to study, it was found from from biological activity test result, aryl connection thiazole compound provided by the invention not only has good activity of weeding, and there is wider degrass spectrum, wheat, sorghum, barnyard grass, cucumber, rape, radish, it is higher to the inhibiting rate of broadleaf weed, especially Amaranthus retroflexus and Eclipta prostrata are significantly inhibited.
Description
Technical field
The present invention relates to a kind of aryl connection thiazole compound and applications.
Background technique
While pesticide brings interests to the mankind, harm also is brought to the mankind.The usage amount of pesticide increases, will necessarily one
Determine degree to cause damages to human body, organism, environment.Future will realize the greenization of pesticide science reasonable employment, high efficiency, warp
Jiization will rely on scientific and technological advances and rely on novel agricultural management body, strengthen the sci-tech innovation, and increase novel green, low toxicity, efficient agriculture
The popularization and application dynamics of medicine, therefore it is required that constantly discovering the novel pesticide with the new mechanism of action.
Pyridines herbicide thrizopyr (Thiazopyr) 1, thrizopyr are pressed down by interfering the formation of spindle microtubule
Cell division processed, it is main to prevent and treat gramineae weed and some broadleaf weeds, it is used before seedling.Aminopyridine acid herbicides chlorine ammonia pyrrole
Pyridine acid (Aminopyralid) 2, it is less toxic and efficient, it is mainly used for mountainous region and bare place weeding.Thrizopyr and chlorine Fampridine
The chemical structural formula of acid is as follows:
2016 Syngenta Carter et al. reported in patent WO 2016046078 trisubstituted thiazole derivative and
Its activity of weeding, majority of compounds show good activity to wild avena sativa, barnyard grass, Tong fiber crops, Amaranthus retroflexus, faber bristlegrass herb, number
According to display, in the compound with general formula structure 3, work as R1=CH3When compound activity got well when activity when other groups replace,
80% or more is reached to wild avena sativa, barnyard grass, Tong fiber crops, Amaranthus retroflexus, faber bristlegrass herb preventive effect under 100mg/L dosage.
Report that Duan Liusheng in 2017 et al. has synthesized a series of 5- substituted thiazole amides in patent CN 106831638
Object is closed, the compound for being found to have general formula 4 has preferable inhibitory activity to gramineae weed.And the work with brassinosteroid
Property structure, therefore can also be used as plant growth regulator with exploitation.
In the initiative exploitation of herbicide, the structure of the connection heterocycle containing substituted aryl is also one of the hot spot of current research.With
Proporphyrinogen oxidase (PPO) is that the inhibitor of target is representative, and PPO class herbicide action mechanism is that protogen IX is caused to exist
It is accumulated rapidly in chloroplaset, to penetrate into cytoplasm, protogen IX is by non-enzyme mechanism or by other oxidizing ferment (ER enzyme
Or PM enzyme) it is oxidized to protoporphyrin IX, singlet oxygen is generated under illumination condition, and then cause the fatty acid peroxidase of cell membrane,
Pigment destruction etc. eventually leads to blade death.Occur very more commercially produced products in the market, such as: cinidon-ethyl
(Cinidon-ethyl) 5, fluazolate (Isopropazol) 6, benzene flumetsulam (Saflufenacil) 7, fluorine pyridazine grass
Ester (Flufenpyr-ethyl) 8 etc..
A kind of aryl provided by the invention joins thiazole compound, and the prior art does not disclose, also without disclosing describedization
Close object has good activity in weeding.
Summary of the invention
The present invention provides a kind of new aryl connection thiazole compounds and its preparation method and application, such compound is very
Preferable activity of weeding.
A kind of aryl joins thiazole compound, it is characterised in that shown in its chemical structural formula such as formula (I)；
In formula (I), X1It is selected fromX2And X3It is each independently selected from nitrogen, oxygen or sulphur；X4With
X5It is each independently selected from carbon or nitrogen；Y is selected from fluorine, chlorine, bromine, iodine, nitro or methylsulfonyl；
Wherein R1、R2、R3、R4It is each independently selected from hydrogen, C1- C20Alkyl, C1- C20Halogenated alkyl, C1- C20's
Alkoxy, C1- C20Naphthenic base, C1- C20Halogenated alkoxy or phenyl；
R5Selected from hydrogen, halogen, nitro, itrile group, hydroxyl, sulfydryl, C1- C20Alkyl, C2- C20Alkenyl, C2- C20's
Alkynyl, C1- C20Halogenated alkyl, C2- C20Halogenated alkenyl, C2- C20Halo alkynyl, C1- C20Alkoxy, C1- C20
Halogenated alkoxy, C1- C20Alkylthio group, carboxylic acid, C1- C20Arrcostab.
A kind of aryl joins thiazole compound, it is characterised in that R1Selected from hydrogen, C1- C20Alkyl, C1- C20's
Halogenated alkyl perhaps substituted aryl preferably hydrogen or C1- C20Alkyl, more preferably hydrogen or methyl.
A kind of aryl joins thiazole compound, it is characterised in that R2Selected from C1- C4Alkyl, C1- C4It is halogenated
Alkyl or substituted aryl, preferably methyl, hydrogen, ethyl, isopropyl, isobutyl group, propyl, cyclopropyl, cyclopenta, 2- methyl ring
Amyl, cyclohexyl, 2,2,4,4- tetramethyl butyl, phenethyl, phenylmethylene, 4- bromophenyl, 4- nitrobenzophenone, 2,4- difluoro
Phenyl, 2- aminomethyl phenyl, 4- tert-butyl-phenyl, 2- methyl -6- ethylphenyl, 3- methoxyphenyl, 2- chlorphenyl, 2,5- diformazan
The fluoro- 4- bromophenyl of base phenyl, 3- isopropyl phenyl, 2,4 dichloro benzene base, 2-, 3- fluorophenyl, 1- phenylethyl, 2- trifluoromethyl
The fluoro- 4- iodophenyl of phenyl, 4- trifluoromethyl, 3,4- difluorophenyl, 3- aminomethyl phenyl, 2-, 4 benzoic acid trifluoro ethyl ester base,
2,4- 3,5-dimethylphenyl, 2- methyl -3- chlorphenyl, 3- trifluoromethyl, 3,5- dichlorophenyl, the chloro- 4- aminomethyl phenyl of 2-, 2-
Fluoro- 4- aminomethyl phenyl, 4- oxygen trifluoromethyl, 4- aminomethyl phenyl, 2,4 difluorobenzene base or 3,4- dichlorophenyl.
A kind of aryl joins thiazole compound, it is characterised in that R3Selected from hydrogen, C1- C20Alkyl, C1- C20's
Halogenated alkyl or substituted aryl, preferably C1- C4Alkyl, C1- C4Halogenated alkyl or substituted aryl, more preferably
Methyl, ethyl, propyl, isobutyl group, cyclopenta, 2- aminomethyl phenyl, 2,5- 3,5-dimethylphenyl, 3- methyl -4- fluorophenyl, 4- ethyl
Phenyl or phenyl.
A kind of aryl joins thiazole compound, it is characterised in that R4Selected from hydrogen, C1- C20Alkyl, C1- C20's
Halogenated alkyl or substituted aryl, preferably C1- C4Alkyl, C1- C4Halogenated alkyl or substituted aryl.
A kind of aryl joins thiazole compound, it is characterised in that R4Selected from C1- C4Alkyl, preferably methyl.
A kind of aryl joins thiazole compound, it is characterised in that X2、X3、X4And X5Be respectively selected from nitrogen, sulphur, carbon and
Nitrogen.
A kind of aryl joins thiazole compound, it is characterised in that Y is selected from fluorine, chlorine or bromine, preferably chlorine.
A kind of aryl joins thiazole compound, it is characterised in that R5Selected from hydrogen.
A kind of application of aryl connection thiazole compound in herbicide.
A series of aryl connection thiazole compounds are prepared in the present invention, and are applied to study, and live from from biology
Property test result it is found that aryl provided by the invention connection thiazole compound not only has good activity of weeding, but also have
Wider degrass spectrum, wheat sorghum barnyard grass cucumber rape radish is higher to the inhibiting rate of broadleaf weed, especially to Amaranthus retroflexus
It is significantly inhibited with Eclipta prostrata.
Specific embodiment
The present invention is further explained in the light of specific embodiments, but the scope of protection of the present invention is not limited thereto.
Embodiment:
Aryl provided by the invention joins thiazole compound, shown in structural formula such as formula (I), most preferably just like formula (K) and
The structure of the compound of two kinds of forms as shown in formula (L), structural formula are as follows:
It is above-mentioned such as formula (K) and the synthetic route such as formula (L) compound represented is as follows:
As an example, the preparation method of structure above intermediate may is that
(1) synthesis of the intermediate as shown in formula (B):
The starting material such as chloro- 5 Nitro-benzoic acid 100g of 2- shown in formula (A) is added in 2000mL three-necked flask
Then K is added in (0.496mol) and 1000mL industrial acetone, dissolution, mechanical stirring2CO3205.6g (1.488mol), then delays
It is slow that 62.5g (0.496mol) dimethyl suflfate is added dropwise, after about 20min is added dropwise, reaction solution is heated to 35 DEG C and keeps temperature
Spend constant, reaction 2 hours, TLC tracing detection reaction process.After completion of the reaction, it filters, filtrate is taken to be evaporated on the rotary evaporator
After acetone, 500mL ethyl acetate is added and 350mL water is extracted, isolate organic layer, organic layer is washed 3 times, then through nothing
Water magnesium sulfate is dry, and ethyl acetate is then evaporated off, and obtains yellow solid 101.55g to get intermediate shown in formula (B), slightly
Yield: 95.0%.
(2) synthesis of the intermediate as shown in formula (C):
It is added in 1000mL three-necked flask such as the chloro- 5- nitro-benzoic acid methyl ester 101.55g of 2- shown in formula (B)
(0.471mol), 350mL ethyl alcohol and 70mL water is added, adds 65.94g (1.178mol) iron powder, mechanical stirring is simultaneously heated to
Reflux, is slowly added to 50mL saturated aqueous ammonium chloride, and TLC is detected after 1 hour, and raw material point exists, and continues to add 28g
(0.5mol) iron powder, after the reaction was continued 30min, TLC tracing detection, fully reacting has an impure point.With the sand for being packed into silica gel
Core funnel filters reaction solution while hot, and filter residue is rinsed with 50mL ethyl alcohol, the ethyl alcohol after merging filtrate and flushing, in rotary evaporation
It after being evaporated ethyl alcohol on device, is extracted with ethyl acetate, isolates organic layer, organic layer is successively washed, saturated common salt is washed,
Anhydrous magnesium sulfate is dry and ethyl acetate is evaporated off, and obtains rufous liquid 82.91g；
The synthesis of the intermediate as shown in formula (C), existing literature report a variety of methods, such as palladium carbon catalytic hydrogenation,
Hydrazine hydrate, Raney's nickel add a variety of methods such as the restoring method such as hydrogen, sulfide reduction, metal hydride, stannous chloride.Because of phenyl ring
It is upper to contain halogen Cl atom, it prevents Cl atom from falling off while considering the price of catalyst, we select more mild in experiment
Iron powder as reducing agent, reduced iron powder point is added several times, and it is excessively fierce and cause slug to alleviate reaction, reduces test
Degree of danger.Saturated aqueous ammonium chloride is added simultaneously and promotes electronics transfer, so that reaction be promoted to carry out.
(3) synthesis of the intermediate as shown in formula (E):
37.12g (0.2mol) such as chloro- 5- amino-benzoic acid first of 2- shown in formula (C) is added in 500mL three-necked flask
Ester, 100mL hydrochloric acid and 70mL water, mechanical stirring, cryogenic freezing have faint yellow solid precipitation, by 13.8g to -5-0 DEG C
(0.2mol) sodium nitrite is dissolved in 20mL water, is then slowly dropped in above-mentioned three-necked flask, is added dropwise in 45min
Afterwards, faint yellow solid all dissolves in three-necked flask, and solution is in crocus, and reacting liquid temperature is maintained at -2-0 DEG C.Three mouthfuls are burnt
Mixture stirs 15min in bottle.Then 48% tetrafluoro boric acid solution 45.7g (0.25mol HBF4) is added dropwise, about on the left side 30min
The right side is added dropwise, and keeps reacting liquid temperature at 0-2 DEG C, continues stirring 2 hours.After reaction, reaction solution is filtered, filter residue according to
Secondary rinse through the washing of dilute tetrafluoro boric acid solution, 50% ethyl alcohol (50mL) is rinsed with dehydrated alcohol (50mL), dries to obtain pale yellow colored solid
Body 43.2g, yield 75.6%.
Methylvinyl acetate 67.5g (0.68mol), 30.75g (0.38mol) anhydrous second are added in 500mL three-necked flask
Sour sodium and 3.86g (0.04mol) stannous chloride, magnetic agitation are slowly added faint yellow solid obtained in the previous step, at this moment
Reacting liquid temperature rises obviously, and the three-necked flask is placed in ice-water bath, keeps reacting liquid temperature at 20-25 DEG C, faint yellow
After solid adds, then it is stirred at room temperature 2 hours.TLC tracks reaction process there are two impure point, column chromatography for separation, dry method loading,
Gradient elution, washing and dehydrating integrated machine are followed successively by V (petroleum ether): V (ethyl acetate)=10:1,6:1 and 4:1 and obtain 27.6g rufous oily
Liquid, total recovery 52.8%；
The mechanism of above-mentioned reaction process is: nitrous acid is unstable, usually using sodium nitrite, hydrochloric acid and tetrafluoro boric acid, makes
The nitrous acid generated when reaction with arylamine reaction, generates NITRODIAZONIUM FLUOROBORATE solid immediately.NITRODIAZONIUM FLUOROBORATE solid is in chlorination
A molecule N is sloughed under cuprous catalysis2, generate benzene radical, while Cu+It is oxidized Cu2+.Phenyl radical and different ethyl acrylate
Double bond addition obtains free radical intermediate, and free radical intermediate is in Cu2+The lower oxidation of catalysis forms carbocationic intermediate, simultaneously
Cu2+It is reduced into Cu+.Carbocationic intermediate transfer acylium cation obtains target product intermediate as shown in formula (E), acyl
Base cation and acetate reaction generate acetic anhydride.
(4) synthesis of the intermediate as shown in formula (F):
The chloro- 5- of 2- (2- oxopropyl) the methyl benzoate 11.12g as shown in formula (E) is dissolved with 100mL methylene chloride
(49mmol), the magnetic agitation under condition of ice bath are slowly added dropwise with 50mL constant pressure funnel into 7.94g (59mmol) sulfonic acid chloride
It with 15mL methylene chloride mixed liquor, after being added dropwise, takes ice bath away, is stirred at room temperature, TLC tracing detection, there are two impure points.Instead
After answering, 40mL saturated salt solution is added and separates organic phase, organic phase on washing, drying and rotary evaporator successively through being evaporated
Methylene chloride obtains rufous liquid 12.25g, thick yield 96.5%.
(5) synthesis of the intermediate as shown in formula (G):
52g (500mmol) 3- pyridine carbonitrile, 40% ammonium sulfide of 105mL (500mmol) are added into 1000mL round-bottomed flask
Solution adds 500mL methanol as solvent, reacts at room temperature 18h.There is bright yellow solid precipitation, filters, dry to obtain target product
66.5g, yield 96.4%.
(6) synthesis of the intermediate as shown in formula (H):
The chloro- 5- of 2- as shown in formula (F) (1- chloro-2-oxo propyl) methyl benzoate is added into 150mL round-bottomed flask
(7.88g, 30mmol) and pyridine -3- thioformamide (G) 4.14g (30mmol), adds anhydrous acetic acid 50mL and anhydrous second
Sour sodium 4.95g (60mmol), magnetic agitation are simultaneously heated to 70~80 DEG C of reaction 2h, are then heated to reflux, react 3h, TLC inspection
Stop heating after surveying fully reacting, part anhydrous acetic acid be evaporated off, is then cooled to room temperature and pours into reactant in the water of 300mL,
(100mL × 2) are extracted with ethyl acetate, isolate organic phase, organic phase washes (50mL × 3) with saturated common salt, then has separated
Machine phase is simultaneously dried, filtered, column chromatography for separation with anhydrous magnesium sulfate, dry method loading, gradient elution, and washing and dehydrating integrated machine is followed successively by V (petroleum
Ether): V (ethyl acetate)=10:1 and 4:1 obtains 6.28g white solid, yield 63.3%.m.p.121~126 DEG C.
(7) synthesis of the intermediate as shown in formula (I):
(4- methyl -2- (pyridin-3-yl) thiazole-of the chloro- 5- of 2- as shown in formula (F) is dissolved with 60mL tetrahydrofuran (THF)
5- yl) methyl benzoate 6.5g is added in 100mL round-bottomed flask, and 12mLNaOH aqueous solution is added, and (mass fraction of NaOH is
10%) it is heated to flowing back, after reacting 2h, THF is evaporated off, then reaction solution is poured into 20mL water, adjusting pH value with dilute hydrochloric acid is 4-
5, there is white solid precipitation, filter, 5.90g such as formula (I) compound represented, yield 94.0% are dried to obtain in filter cake washing；
M.p.179~182 DEG C.
It is exemplified below such as formula (K) and joins thiazole compound such as the aryl of formula (L) compound represented, respectively such as 1 He of table
Shown in table 2, hydrogen modal data and mass spectrometric data are as shown in table 3:
The aryl as shown in formula (K) of table 1 joins thiazole compound
The aryl as shown in formula (L) of table 2 joins thiazole compound
The characterize data of the aryl as shown in formula (K) and (L) of table 3 connection thiazole compound
2- chloro-n-methyl-the 5- as shown in compound number K1 of embodiment 1 (4- methyl -2- (pyridin-3-yl) thiazole -5-
Base) benzamide preparation:
(4- methyl -2- (pyridin-3-yl) thiazole -5- of the chloro- 5- of 2- as shown in formula (J) is added into 25mL single-necked flask
Base) chlorobenzoyl chloride (0.1g, 2.9mmol), be added 10mL tetrahydrofuran dissolution, add 33% methylamine water solution (0.09g,
2.9mmol) with triethylamine (0.39g, 5.8mmol), reaction 2h is stirred at room temperature.TLC detects extent of reaction, after reaction, mistake
Filter, takes filtrate precipitation, and recrystallization is in petroleum ether to get the target compound as shown in formula (K1)；
Such as chloro- 5- of 2- shown in compound number K2 of embodiment 2 (4- methyl -2- (pyridin-3-yl) thiazole -5- base) benzene first
The preparation of amide:
(4- methyl -2- (pyridin-3-yl) thiazole -5- of the chloro- 5- of 2- as shown in formula (J) is added into 25mL single-necked flask
Base) chlorobenzoyl chloride (0.1g, 2.9mmol), the dissolution of 10mL tetrahydrofuran is added, adds the ammonium hydroxide 0.1g (mole of ammonia
2.9mmol) with triethylamine (0.39g, 5.8mmol), reaction 2h is stirred at room temperature.TLC detects extent of reaction, after reaction, mistake
Filter, takes filtrate precipitation, and recrystallization is in petroleum ether to get the target compound as shown in formula (K2)；
Such as chloro- 5- of 2- shown in compound number L49 of embodiment 3 (4- methyl -2- (pyridin-3-yl) thiazole -5- base) benzene
The preparation of methyl formate:
(4- methyl -2- (pyridin-3-yl) thiazole -5- of the chloro- 5- of 2- as shown in formula (J) is added into 25mL single-necked flask
Base) chlorobenzoyl chloride (0.1g, 2.9mmol), the dissolution of 10mL tetrahydrofuran is added, adds methanol (0.09g, 2.9mmol) and three
Reaction 2h is stirred at room temperature in ethamine (0.39g, 5.8mmol).TLC detects extent of reaction, and after reaction, filtering takes filtrate precipitation,
Recrystallization is in petroleum ether to get the target compound as shown in formula (L49)；
Such as chloro- 5- of 2- shown in compound number L50 of embodiment 4 (4- methyl -2- (pyridin-3-yl) thiazole -5- base) benzene
The preparation of Ethyl formate:
(4- methyl -2- (pyridin-3-yl) thiazole -5- of the chloro- 5- of 2- as shown in formula (J) is added into 25mL single-necked flask
Base) chlorobenzoyl chloride (0.1g, 2.9mmol), the dissolution of 10mL tetrahydrofuran is added, adds ethyl alcohol (0.14g, 2.9mmol) and three
Reaction 2h is stirred at room temperature in ethamine (0.39g, 5.8mmol).TLC detects extent of reaction, and after reaction, filtering takes filtrate precipitation,
It is recrystallized in petroleum ether, recrystallization is in petroleum ether to get the target compound as shown in formula (L50)；
Embodiment 5 (following " gai/ha " refers both to every gram of active matter/hectare):
It is control group relative to clear water, after the aryl connection thiazole compound medical fluid application of preparation, with hazard of plant symptom
(inhibition, deformity, yellow, albefaction) shows the activity of weeding of degree range estimation compound and the safety to crop, and 0 indicates not remove
Careless effect evaluates crop safety, the complete kill weeds of 100% expression or crop, activity of weeding and crop safety ocular estimate
Standard is as shown in table 4；
Table 4
From table 4, the aryl connection thiazole compound medical fluid activity of weeding after application reaches 70~100%, can be used；
When reaching 0~20% to the toxicity of crop, it can be used.
Use pesticide is raw to survey SOP method to number as the connection thiazole compound progress weeding of the aryl of K1~48 and L49~58
Determination of activity is broadly divided into following level:
(1) general sieve: concentration be 200mg/L dosage under, with desired aryl connection thiazole compound to target organisms into
Row preliminary screening, test target compound activity, ocular estimate sight are looked into, and compound when to activity more than 80% carries out multiple in next step
Sieve；
Then and comparison medicament (2) secondary screening: carrying out toxicologic study and to the security test of crop to target compound,
It compares, tentatively distinguishes compound effects mode and prevention spectrum.
The specific steps of general sieve are as follows: general sieve is first carried out using culture dish method, for examination target be radish, cucumber, rape, wheat,
The seed of sorghum and barnyard grass, wherein wheat, sorghum and radish seed carry out vernalization in advance, take the uniform seed progress that shows money or valuables one carries unintentionally
Test.Above-mentioned target seed is put into the internal diameter 9cm culture dish of paving double-layer filter paper, every culture dish is added concentration 200mg/L's
(aryl connection thiazole compound is respectively the change that number is K1~48 and L49~58 to aryl connection thiazole compound medical fluid 10mL
Close object), filter paper uniformly and is sufficiently soaked, if clear water processing is control；Number marks respectively after processing, is placed in growth cabinet
Middle culture is arranged 28 DEG C of temperature；Illumination 3000Lux, light application time 16L:8D, RH 75%, after 7 days ocular estimate sight look into target root,
Stem inhibiting rate (%).General sieve biological activity test result such as table 6；
6 aryl of table joins thiazole compound and surveys test result (200mg/L, activity/%) in Target crops activity ware
If general sieve result performance preferably activity, further carries out potting screening test.It is piemarker that potting, which is screened for examination target,
Amaranthus retroflexus, Eclipta prostrata, herba digitariae, barnyard grass and herba setariae viridis.Take internal diameter 7.5cm flowerpot, dress composite earth (V vegetable garden soil: seedling medium=1 V:
2) to above-mentioned six kinds of weeds targets (bud rate >=85%) at flowerpot 3/4, are directly sowed respectively, earthing 0.2cm is long to 3 to weeds
Or so the leaf phase is spare.The basin alms bowl of test process carries out soil surface spraying treatment in sowing one day after before seedling.Each compound according to
After 150g.a.i./ha dosage is administered with auto spraying tower (model: 3WPSH-700E), after weeds blade face, medical fluid moves into after drying
The activity (%) to weeds, comparison medicine: mesotrione (Mesotrione) are investigated in hot-house culture after 25 days.
As can be seen from Table 6, number is that the aryl connection thiazole compound of K1~49 is more than to the activity of Target crops
80%, that is, enter primary dcreening operation step, carries out activity of weeding test.
The weeds of the biological activity determination test of the present embodiment selection and crop species such as the following table 5；
Table 5
| Chinese name | English name | Scientific name |
| Barnyard grass | barnyardgrass | Echinochloa crusgalli |
| Herba digitariae | Crabgrass | Digitaria sanguinalis |
| Herba setariae viridis | Giant foxtail | Setaria viridis |
| Amaranthus retroflexus | Amaranth pigweed | Amaranthus retroflexus |
| Piemarker | Chingma abutilon | Abutilon theophrasti |
| Eclipta prostrata | False daisy | Eclipta prostrata |
| Wheat | Wheat | Triticum aestivum |
| Rape | Rape | Brassica napus |
| Sorghum | Sorghum | Sorghum bicolor |
| Cucumber | Cucumber | Cucumis sativus |
| Radish | Radish | Raphanus sativus |
The number of table 7 is the activity of weeding test result of the compound of K1~48 (after seedling, 150g.ai/ha, inhibiting rate/%)
From biological activity test result it is found that aryl provided by the invention connection thiazole compound not only has good remove
Careless activity, and there is wider degrass spectrum, it is higher to the inhibiting rate of broadleaf weed, especially have to Amaranthus retroflexus and Eclipta prostrata
Apparent inhibiting effect.
Content described in this specification is only to enumerate to inventive concept way of realization, and protection scope of the present invention is not answered
When the concrete form for being seen as limited by embodiment and being stated, protection scope of the present invention is also only in those skilled in the art's root
According to present inventive concept it is conceivable that equivalent technologies mean.
Claims (10)
1. a kind of aryl joins thiazole compound, it is characterised in that shown in its chemical structural formula such as formula (I)；
In formula (I), X1It is selected fromOr；X2And X3It is each independently selected from nitrogen, oxygen or sulphur；X4And X5Respectively
Independently selected from carbon or nitrogen；Y is selected from fluorine, chlorine, bromine, iodine, nitro or methylsulfonyl；
Wherein R1、R2、R3、R4It is each independently selected from hydrogen, C1- C20Alkyl, C1- C20Halogenated alkyl, C1- C20Alcoxyl
Base, C1- C20Naphthenic base, C1- C20Halogenated alkoxy or phenyl；
R5Selected from hydrogen, halogen, nitro, itrile group, hydroxyl, sulfydryl, C1- C20Alkyl, C2- C20Alkenyl, C2- C20Alkynyl,
C1- C20Halogenated alkyl, C2- C20Halogenated alkenyl, C2- C20Halo alkynyl, C1- C20Alkoxy, C1- C20Halogen
For alkoxy, C1- C20Alkylthio group, carboxylic acid, C1- C20Arrcostab.
2. a kind of aryl according to claim 1 joins thiazole compound, it is characterised in that R1Selected from hydrogen, C1- C20Alkane
Base, C1- C20Halogenated alkyl perhaps substituted aryl preferably hydrogen or C1- C20Alkyl, more preferably hydrogen or methyl.
3. according to a kind of aryl connection thiazole compound described in claim 1, it is characterised in that R2Selected from C1- C4Alkyl, C1?
C4Halogenated alkyl or substituted aryl, preferably methyl, hydrogen, ethyl, isopropyl, isobutyl group, propyl, cyclopropyl, cyclopenta,
2- methylcyclopentyl, cyclohexyl, 2,2,4,4- tetramethyl butyl, phenethyl, phenylmethylene, 4- bromophenyl, 4- nitrobenzene
Base, 2,4 difluorobenzene base, 2- aminomethyl phenyl, 4- tert-butyl-phenyl, 2- methyl -6- ethylphenyl, 3- methoxyphenyl, 2- chlorobenzene
The fluoro- 4- bromophenyl of base, 2,5- 3,5-dimethylphenyl, 3- isopropyl phenyl, 2,4 dichloro benzene base, 2-, 3- fluorophenyl, 1- phenyl second
The fluoro- 4- iodophenyl of base, 2- trifluoromethyl, 4- trifluoromethyl, 3,4- difluorophenyl, 3- aminomethyl phenyl, 2-, 4- benzene
Methanoic acid trifluoro ethyl ester base, 2,4- 3,5-dimethylphenyl, 2- methyl -3- chlorphenyl, 3- trifluoromethyl, 3,5- dichlorophenyl, 2-
The fluoro- 4- aminomethyl phenyl of chloro- 4- aminomethyl phenyl, 2-, 4- oxygen trifluoromethyl, 4- aminomethyl phenyl, 2,4 difluorobenzene base or 3,
4- dichlorophenyl.
4. according to a kind of aryl connection thiazole compound described in claim 1, it is characterised in that R3Selected from hydrogen, C1- C20Alkyl,
C1- C20Halogenated alkyl or substituted aryl, preferably C1- C4Alkyl, C1- C4Halogenated alkyl or substituted aryl,
More preferably methyl, ethyl, propyl, isobutyl group, cyclopenta, 2- aminomethyl phenyl, 2,5- 3,5-dimethylphenyl, 3- methyl -4- fluorobenzene
Base, 4- ethylphenyl or phenyl.
5. according to a kind of aryl connection thiazole compound described in claim 1, it is characterised in that R4Selected from hydrogen, C1- C20Alkyl,
C1- C20Halogenated alkyl or substituted aryl, preferably C1- C4Alkyl, C1- C4Halogenated alkyl or substituted aryl.
6. joining thiazole compound according to a kind of aryl described in claim 5, it is characterised in that R4Selected from C1- C4Alkyl, it is excellent
It is selected as methyl.
7. a kind of aryl according to claim 1 joins thiazole compound, it is characterised in that X2、X3、X4And X5It is respectively selected from
Nitrogen, sulphur, carbon and nitrogen.
8. a kind of aryl according to claim 1 joins thiazole compound, it is characterised in that Y is selected from fluorine, chlorine or bromine, excellent
It is selected as chlorine.
9. a kind of aryl according to claim 1 joins thiazole compound, it is characterised in that R5Selected from hydrogen.
10. application of a kind of aryl connection thiazole compound in herbicide as described in claim 1 ~ 9 is any.
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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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