CN111892546A - Preparation and application of cyanoacrylate containing 1,2, 3-triazole biphenyl - Google Patents
Preparation and application of cyanoacrylate containing 1,2, 3-triazole biphenyl Download PDFInfo
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- CN111892546A CN111892546A CN202010918705.7A CN202010918705A CN111892546A CN 111892546 A CN111892546 A CN 111892546A CN 202010918705 A CN202010918705 A CN 202010918705A CN 111892546 A CN111892546 A CN 111892546A
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- cyanoacrylate
- triazole
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- 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
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/04—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles
- C07D249/06—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles with aryl radicals directly attached to ring atoms
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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
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
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- Chemical & Material Sciences (AREA)
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- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention relates to a preparation method and application of cyanoacrylate (I) containing 1,2, 3-triazole biphenyl. Is prepared by condensing 1,2, 3-triazole biphenyl compound and cyanoacrylate. The cyanoacrylate containing the 1,2, 3-triazole biphenyl group shows excellent control effect on weeds, and the compound can be used for preparing herbicides in the fields of agriculture, horticulture and the like.
Description
Technical Field
The invention relates to the field of chemical pesticides, in particular to preparation and application of cyanoacrylate containing 1,2, 3-triazole biphenyl.
Background
Herbicides account for a large proportion of pesticides. In recent years some weeds have developed resistance to traditional herbicides. Therefore, there is a need to find new efficient, safe herbicides.
Cyanoacrylate compounds are photosystem II (PS II) electron transfer inhibitors, cyanoacrylate derivatives have important application in the field of pesticides, for example, cyanoacrylate compounds NK-9717 reported by Wang and the like show excellent weeding effect, and through stem and leaf treatment, the control effect of NK-9717 on rape is 100% under the dosage of 300 g/ha.
The 1,2, 3-triazole compound is also an important compound and is widely applied to agricultural production.
In order to continuously search for a compound with good biological activity from cyanoacrylate derivatives, cyanoacrylate and a 1,2, 3-triazole fragment are combined together, and the invention discloses cyanoacrylate containing 1,2, 3-triazole biphenyl with agricultural weeding application value.
Disclosure of Invention
The invention aims to provide cyanoacrylate containing 1,2, 3-triazole biphenyl which has good preventing and removing effects on weeds and is efficient, safe and environment-friendly, so as to meet the requirement of crop protection on novel high-efficiency herbicides.
Another object of the present invention is to provide a process for the preparation of the above compounds.
It is a further object of the present invention to provide the use of the above compounds for the preparation of herbicides.
The object of the invention can be achieved by the following measures:
in order to solve the above technical problems, a first aspect of the present invention provides cyanoacrylate containing 1,2, 3-triazole biphenyl group, having the following structure:
the invention provides a preparation method of cyanoacrylate containing 1,2, 3-triazole biphenyl, which is characterized by comprising the following reaction steps:
the compound of the invention has good weed control effect, so the compound of the invention can be used for preparing herbicides and further protecting plants in agriculture, horticulture and the like. The broadleaf weeds comprise chenopodium quinoa, mustard and the like, and the grassy weeds comprise physalis pubescens, club grass and the like. Of course, the weeds that can be controlled by the compounds of the present invention are not limited to the above exemplified ranges.
When the compound of the present invention represented by the general formula I is used as a herbicide in the fields of agriculture, horticulture and the like, it can be used alone or in the form of a herbicidal composition, for example, by using the formula I as an active ingredient, and adding an agricultural chemical adjuvant commonly used in the field to prepare an aqueous emulsion, a suspension, a water dispersible granule, an emulsion and the like.
Commonly used pesticide adjuvants include liquid carriers such as water; organic solvents such as toluene, xylene, cyclohexanol, methanol, butanol, ethylene glycol, acetone, N-dimethylformamide, acetic acid, dimethyl sulfoxide, animal and vegetable oils and fatty acids; commonly used surface agents such as emulsifiers and dispersants, including anionic, cationic, nonionic and amphoteric surfactants; other adjuvants, such as wetting agents, thickeners, and the like.
When the compound of the present invention is used as an active ingredient in a herbicide, the content in the herbicide may be selected in the range of 0.1% to 99.5%, and an appropriate content of the active ingredient may be determined according to the formulation form and the application method. In general, the aqueous emulsion contains 5% to 50% (by weight, the same applies hereinafter) of the active ingredient, preferably 10% to 40%; the suspension concentrate contains 5% to 50% of active ingredient, preferably 5% to 40%.
For the use of the herbicides of the invention, the usual application methods can be selected, such as foliar spray, water surface application, soil application
Soil treatment, seed treatment and the like. For example, when stem and leaf spray is used, an aqueous emulsion, a suspension, a water-dispersible granule, or an emulsifiable concentrate of the compound represented by the general formula I as an active ingredient can be used in a concentration range of 75 to 1500g of a.i./ha, and the concentration thereof is preferably 150-1500g of a.i./ha.
The cyanoacrylate containing 1,2, 3-triazole biphenyl disclosed by the invention has a good weeding effect on certain weeds, so that the cyanoacrylate can be used for preparing herbicides in the fields of agriculture, horticulture and the like.
Detailed Description
To facilitate a further understanding of the invention, the following examples are provided to illustrate it in more detail. These examples are provided for illustrative purposes only and are not intended to limit the scope or the principles of the invention.
Example 1:
dissolving 2mmol of compound IIa in 20mL of methanol, slowly dropwise adding newly prepared 10mL of methanol solution containing 4mmol of sodium methoxide while cooling in ice bath, stirring for 5 hours in ice bath, removing the solvent, adding 20mL of water to the residue, extracting with ethyl acetate for several times, combining organic phases, washing with saturated aqueous sodium chloride solution, drying with anhydrous sodium sulfate, filtering, desolventizing under reduced pressure, and subjecting the residue to column chromatography [ V (petroleum ether): V (ethyl acetate): 5:1 ]]Separating to obtain a compound Ia;1H NMR(400MHz,CDCl3):9.78(s,1H,NH),8.09(d,J＝8.4Hz,2H,Ar-H),7.82(s,2H,1,2,3-Triazole-H),7.36(d,J＝7.6Hz,2H,Ar-H),4.54(d,J＝6.0Hz,2H,CH2),4.32(t,J＝4.8Hz,2H,CH2),4.24(s,3H,OCH3),3.66(t,J＝4.8Hz,2H,CH2),3.41(s,3H,OCH3).
example 2:
dissolving 2mmol of compound IIa in 35mL of ethanol, slowly dropwise adding a newly prepared 10mL of ethanol solution containing 6mmol of sodium ethoxide under ice-bath cooling, continuously stirring for 4 hours in ice bath, removing the solvent, adding 30mL of water into the residue, extracting with ethyl acetate for several times, combining organic phases, washing with a saturated sodium chloride aqueous solution, drying with anhydrous sodium sulfate, filtering, and performing reduced pressure desolventizing, and performing column chromatography on the residue [ V (petroleum ether): V (ethyl acetate) ═ 6:1 ]]Separating to obtain a compound Ib;1H NMR(400MHz,CDCl3):9.80(s,1H,NH),8.08(d,J＝8.8Hz,2H,Ar-H),7.82(s,2H,1,2,3-Triazole-H),7.36(d,J＝8.4Hz,2H,Ar-H),4.66(q,J＝7.0Hz,2H,CH2),4.55(d,J＝6.0Hz,2H,CH2),4.31(t,J＝5.0Hz,2H,CH2),3.66(t,J＝5.0Hz,2H,CH2),3.41(s,3H,OCH3),1.34(t,J＝7.0Hz,3H,CH3).
example 3:
dissolving 3mmol of compound IIb in 30mL of methanol, slowly dropwise adding newly prepared 10mL of methanol solution containing 8mmol of sodium methoxide under ice-bath cooling, heating and refluxing for 8 hours, removing the solvent, adding 30mL of water to the residue, extracting with ethyl acetate for several times, combining organic phases, washing with saturated aqueous sodium chloride solution, drying with anhydrous sodium sulfate, filtering, desolventizing under reduced pressure, and subjecting the residue to column chromatography [ V (petroleum ether): V (ethyl acetate): 8:1 ]]Separating to obtain a compound ic;1H NMR(400MHz,CDCl3):9.78(s,1H,NH),8.09(d,J＝8.4Hz,2H,Ar-H),7.82(s,2H,1,2,3-Triazole-H),7.35(d,J＝8.4Hz,2H,Ar-H),4.54(d,J＝6.0Hz,2H,CH2),4.31(t,J＝5.0Hz,2H,CH2),4.23(s,3H,OCH3),3.70(t,J＝5.2Hz,2H,CH2),3.58(q,J＝6.9Hz,2H,CH2),1.21(t,J＝7.0Hz,3H,CH3).
example 4:
dissolving 3mmol of compound IIb in 35mL of ethanol, slowly adding 13mL of newly prepared ethanol solution containing 7mmol of sodium ethoxide dropwise under ice-bath cooling, stirring at room temperature for 12 hours, removing the solvent, adding 30mL of water to the residue, extracting with ethyl acetate for several times, combining organic phases, washing with saturated aqueous sodium chloride solution, drying with anhydrous sodium sulfate, filtering, desolventizing under reduced pressure, and subjecting the residue to column chromatography [ V (petroleum ether): V (ethyl acetate): 5:1 ]]Separating to obtain a compound Id;1H NMR(400MHz,CDCl3):9.81(s,1H,NH),8.08(d,J＝8.4Hz,2H,Ar-H),7.82(s,2H,1,2,3-Triazole-H),7.36(d,J＝8.4Hz,2H,Ar-H),4.61(q,J＝7.0Hz,2H,CH2),4.55(d,J＝6.0Hz,2H,CH2),4.31(t,J＝5.0Hz,2H,CH2),3.70(t,J＝5.0Hz,2H,CH2),3.58(q,J＝6.0Hz,2H,CH2),1.34(t,J＝7.0Hz,3H,CH3),1.21(t,J＝7.0Hz,3H,CH3).
example 5:
dissolving 2mmol of compound IIb in 20mL of n-propanol, slowly dropwise adding a newly prepared 12mL of n-propanol solution containing 5mmol of sodium n-propoxide under ice-bath cooling, reacting at room temperature for 6 hours, removing the solvent, adding 30mL of water to the residue, extracting with ethyl acetate several times, combining the organic phases, washing with saturated sodium chloride water, drying with anhydrous sodium sulfate, filtering, desolventizing under reduced pressure, and subjecting the residue to column chromatography [ V (petroleum ether): V (ethyl acetate): 10:1 ]]Separating to obtain a compound ie;1H NMR(400MHz,CDCl3):9.82(s,1H,NH),8.08(d,J＝8.4Hz,2H,Ar-H),7.83(s,2H,1,2,3-Triazole-H),7.36(d,J＝8.4Hz,2H,Ar-H),4.51～4.57(m,4H,CH2),4.30(t,J＝5.2Hz,2H,CH2),3.70(t,J＝5.2Hz,2H,CH2),3.59(q,J＝6.9Hz,2H,CH2),1.69～1.78(m,2H,CH2),1.21(t,J＝7.0Hz,3H,CH3),0.96(t,J＝7.4Hz,3H,CH3).
example 6:
screening of herbicidal activity of compound on chenopodium quinoa, mustard, club grass and alopecurus
Compound preparation: weighing a certain mass of original drug by using an analytical balance (0.0001g), dissolving the original drug by using DMF containing 1% of Tween-80 emulsifier to prepare 1.0% of mother liquor, and diluting the mother liquor by using distilled water for later use. The test method comprises the following steps: pot culture (ordinary sieve), and post-emergence treatment of stems and leaves. The test subjects were chenopodium quinoa, mustard, club grass and alopecurus. A flowerpot with the inner diameter of 7.5cm is taken, composite soil (vegetable garden soil: seedling raising matrix, 1:2, v/v) is filled to 3/4 positions, the weed target is directly sown (the germination rate is more than or equal to 85 percent), soil is covered by 0.2cm, and the weed is reserved when the weed grows to about the 3-leaf stage. After the compounds were applied to an automatic spray tower (model: 3WPSH-700E) at a dose of 1500g a.i./ha, the weeds were allowed to dry on the foliage and cultured in a greenhouse, and the activity (%) of the weeds was examined 35 days later.
TABLE 1 herbicidal Activity data for Compounds Ia-Ie
As can be seen from the data in Table 1, the compounds Ia to Ie have excellent herbicidal effects on Chenopodium quinoa at a dosage of 1500g/ha, and the herbicidal activities are respectively 100%, 90%, 90%, 100% and 100%; the compounds Ia-Ie have good herbicidal activity on mustard under the dosage of 1500g/ha, and the inhibition rates are 100%, 85%, 90%, 100% and 90% respectively; the compounds Ia to Id show better weeding effect on the club grass at the dosage of 1500g/ha, and the inhibition rates are respectively 80 percent, 70 percent, 60 percent and 100 percent; the compounds Ia-Ie have better weeding effect on the alopecurus alternifolia under the dosage of 1500g/ha, and the inhibition rates are 85%, 70%, 70%, 100% and 90% respectively.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited by the foregoing examples, which are provided to illustrate the principles of the invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention, which is also intended to be covered by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (3)
1. The cyanoacrylate (I) containing 1,2, 3-triazole biphenyl is characterized by having the following structure:
2. the preparation method of cyanoacrylate containing 1,2, 3-triazole biphenyl as claimed in claim 1 is characterized by comprising the following steps:
3. use of the 1,2, 3-triazolyl group-containing cyanoacrylate derivative as claimed in claim 1 for the preparation of herbicides.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010918705.7A CN111892546A (en) | 2020-09-04 | 2020-09-04 | Preparation and application of cyanoacrylate containing 1,2, 3-triazole biphenyl |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010918705.7A CN111892546A (en) | 2020-09-04 | 2020-09-04 | Preparation and application of cyanoacrylate containing 1,2, 3-triazole biphenyl |
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| CN202010918705.7A Withdrawn CN111892546A (en) | 2020-09-04 | 2020-09-04 | Preparation and application of cyanoacrylate containing 1,2, 3-triazole biphenyl |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276551A (en) * | 2010-06-10 | 2011-12-14 | 南开大学 | Synthesis of heterocyclic long-chain amino substitution-containing cyanoacrylate compound and application thereof to pesticide |
| CN107474015A (en) * | 2017-08-23 | 2017-12-15 | 南通大学 | Cyanoacrylate compound containing pyrrazole structure and its production and use |
| CN107556253A (en) * | 2017-08-07 | 2018-01-09 | 南通大学 | Cyanoacrylate compound of the heterocyclic substituted containing triazole and its production and use |
| CN107602494A (en) * | 2017-08-24 | 2018-01-19 | 南通大学 | The preparation and application of the cyanacrylate derivant of the group containing tetrazole |
| CN110818649A (en) * | 2019-09-16 | 2020-02-21 | 南通大学 | Preparation and application of 2-cyanoacrylate derivative containing 1, 2, 4-triazole benzylamine unit |
-
2020
- 2020-09-04 CN CN202010918705.7A patent/CN111892546A/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276551A (en) * | 2010-06-10 | 2011-12-14 | 南开大学 | Synthesis of heterocyclic long-chain amino substitution-containing cyanoacrylate compound and application thereof to pesticide |
| CN107556253A (en) * | 2017-08-07 | 2018-01-09 | 南通大学 | Cyanoacrylate compound of the heterocyclic substituted containing triazole and its production and use |
| CN107474015A (en) * | 2017-08-23 | 2017-12-15 | 南通大学 | Cyanoacrylate compound containing pyrrazole structure and its production and use |
| CN107602494A (en) * | 2017-08-24 | 2018-01-19 | 南通大学 | The preparation and application of the cyanacrylate derivant of the group containing tetrazole |
| CN110818649A (en) * | 2019-09-16 | 2020-02-21 | 南通大学 | Preparation and application of 2-cyanoacrylate derivative containing 1, 2, 4-triazole benzylamine unit |
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