CN110372618B - Preparation method and application of cyanoacrylate compound containing benzotriazole phenyl unit - Google Patents
Preparation method and application of cyanoacrylate compound containing benzotriazole phenyl unit Download PDFInfo
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- CN110372618B CN110372618B CN201910814716.8A CN201910814716A CN110372618B CN 110372618 B CN110372618 B CN 110372618B CN 201910814716 A CN201910814716 A CN 201910814716A CN 110372618 B CN110372618 B CN 110372618B
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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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- 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
- C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
- C07D249/18—Benzotriazoles
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- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
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- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to a preparation method and application of a cyanoacrylate compound (I) containing benzotriazole phenyl units. The benzotriazole benzylamine compound is obtained by reacting with 2-cyano-3, 3-bis (methylthio) acrylate. The cyanoacrylate compound containing benzotriazole phenyl units has a good control effect on broadleaf weeds, and 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, and particularly relates to a preparation method and application of a cyanoacrylate compound containing benzotriazole phenyl units.
Background
Herbicides are a widely used class of pesticides. In the herbicide market all over the world, the traditional herbicides still occupy the main position, and make great contribution to social development. However, in recent years, with the increasing awareness of food safety and environmental protection, the status of traditional types of herbicides has become more and more challenging. In view of its various drawbacks, the search for novel herbicides is an urgent task. However, the higher and higher herbicide standards not only require that these new herbicides be effective in killing weeds, but also require that the new herbicides have low toxicity and green safety characteristics.
Cyanoacrylate compounds are electron transfer inhibitors of photosystem II (PS II), and can interfere with the electron transfer in plant photosystem to make plant unable to carry out photosynthesis, so as to achieve the goal of weeding. The special action mechanism ensures that the cyanoacrylate compounds have extremely high safety to animals and meet the requirements of the current market on novel herbicides. With the intensive research on cyanoacrylate compounds, bioassay results show that some cyanoacrylate derivatives have good herbicidal activity.
The benzotriazole derivatives, which are important members of the nitrogen-containing heterocyclic ring family, exhibit excellent biological activity in agricultural production.
Therefore, the benzotriazole phenyl unit and the cyanoacrylate segment are reasonably combined together, and a compound with excellent weeding effect is expected to be found.
The invention discloses a cyanoacrylate compound containing benzotriazole phenyl units, which has agricultural weeding application value.
Disclosure of Invention
The invention aims to provide a cyanoacrylate compound containing benzotriazole phenyl units, which has excellent control effect on broadleaf weeds, is efficient, safe and environment-friendly, and meets the requirement of crop protection on efficient 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.
In order to solve the technical problems, the invention provides a cyanoacrylate compound containing benzotriazole phenyl units, which has a structure shown in a general formula I,
preferably, the cyanoacrylate compound of the benzotriazole phenyl unit has the following structure:
the invention provides a preparation method of a cyanoacrylate compound of a benzotriazole phenyl unit, which is characterized by comprising the following steps:
dissolving the compound III in an organic solvent, adding the intermediate II, reacting for a period of time, cooling the reaction solution to room temperature, filtering, concentrating the mother solution under reduced pressure, separating the obtained crude product by silica gel column chromatography to obtain a target product,
preferably, the preparation method of the cyanoacrylate compound of the benzotriazole phenyl unit comprises the following steps:
among them, the intermediate 2-cyano-3, 3-dimethylsulfanylacrylate substituted ester II was synthesized according to the conventional method reported in the literature (j.agric.food chem.2003,51,5030), and the intermediate III was synthesized according to the method reported in the literature (chi.j.org.chem.2015, 35,2399).
When the compound of the invention is used as a herbicide in the fields of agriculture, horticulture and the like, the compound can be used alone or in a weeding composition mode, for example, the compound of the formula I is used as an active ingredient, and is added with pesticide auxiliary agents commonly used in the field to be processed into an aqueous emulsion, a suspending agent, 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, 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 herbicide of the present invention, a commonly used application method such as foliage spray, water surface application, soil treatment, seed treatment, and the like can be selected. 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 compound has excellent inhibiting activity on broadleaf weeds, so that the compound can be used for preparing herbicides to protect plants in agriculture, horticulture and the like. The broadleaf weeds comprise mustard, small goosebeery 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.
The cyanoacrylate compound of the benzotriazole phenyl unit disclosed by the invention has an excellent control effect on certain broadleaf weeds, so that the cyanoacrylate compound 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:
5mmol of the compound IIa was dissolved in 25mL of THF, 5mmol of the intermediate III was added at room temperature, and then the reaction was refluxed at elevated temperature for 8 hours. After the solvent is concentrated, the obtained crude product is purified to obtain a target compound Ia;1H NMR(400MHz,CDCl3):δ10.45(s,1H,N-H),8.16(d,J＝8.4Hz,1H,Ar-H),7.83(d,J＝8.8Hz,2H,Ar-H),7.76(d,J＝8.4Hz,1H,Ar-H),7.44～7.60(m,4H,Ar-H),4.91(d,J＝6.0Hz,2H,CH2),4.33(t,J＝4.8Hz,2H,CH2),3.67(t,J＝4.8Hz,2H,CH2),3.42(s,3H,CH3),2.71(s,3H,CH3).
example 2:
6mmol of compound IIb was dissolved in 25mL of DMSO, 7mmol of intermediate III was added thereto, and after the addition, the reaction was allowed to warm to 90 ℃ for 10 hours. After the solvent is removed, the crude product is purified to obtain a target compound Ib;1H NMR(400MHz,CDCl3):δ10.46(s,1H,NH),8.16(d,J＝8.4Hz,1H,Ar-H),7.83(d,J＝8.4Hz,2H,Ar-H),7.76(d,J＝8.4Hz,1H,Ar-H),7.44～7.60(m,4H,Ar-H),4.90(d,J＝6.0Hz,2H,CH2),4.32(t,J＝4.8Hz,2H,CH2),3.71(t,J＝4.8Hz,2H,CH2),3.57(q,J＝7.2Hz,2H,CH2),2.71(s,3H,CH3),1.22(t,J＝7.2Hz,3H,CH3).
example 3:
3mmol of compound IIc were dissolved in 30mL of ethanol, 5mmol of intermediate III were added, and the reaction was heated under reflux for 12 hours. After the solvent is removed, the obtained crude product is purified to obtain a target compound Ic;1H NMR(400MHz,CDCl3):δ10.44(s,1H,NH),8.17(d,J＝8.4Hz,1H,Ar-H),7.83(d,J＝8.8Hz,2H,Ar-H),7.76(d,J＝8.4Hz,1H,Ar-H),7.28～7.60(m,6H,Ar-H),6.92～6.98(m,3H,Ar-H),4.92(d,J＝6.0Hz,2H,CH2),4.53(t,J＝4.8Hz,2H,CH2),4.25(t,J＝4.8Hz,2H,CH2),2.72(s,3H,CH3).
example 4:
4mmol of compound Id was dissolved in 30mL of DMF, 6mmol of intermediate III was added, and the reaction was allowed to warm to 80 ℃ for 15 hours. After the solvent is removed, the obtained crude product is purified to obtain a target object Id;1H NMR(400MHz,CDCl3):δ10.43(s,1H,NH),8.17(d,J＝8.4Hz,1H,Ar-H),7.84(d,J＝8.4Hz,2H,Ar-H),7.76(d,J＝8.4Hz,1H,Ar-H),7.45～7.60(m,4H,Ar-H),7.35(d,J＝2.8Hz,1H,Ar-H),7.18～7.21(m,1H,Ar-H),6.96(d,J＝8.8Hz,1H,Ar-H),4.92(d,J＝5.6Hz,2H,CH2),4.57(t,J＝4.8Hz,2H,CH2),4.29(t,J＝4.8Hz,2H,CH2),2.72(s,3H,CH3).
example 5:
6mmol of compound IIe are dissolved in 35mL of dichloromethane and 8mmol of intermediate III are added. The reaction was then heated to reflux for 20 hours. After desolventizing, purifying the obtained crude product to obtain a target object Ie;1H NMR(400MHz,CDCl3):δ10.43(s,1H,NH),8.17(d,J＝8.4Hz,1H,Ar-H),7.84(d,J＝8.4Hz,2H,Ar-H),7.76(d,J＝8.4Hz,1H,Ar-H),7.45～7.60(m,4H,Ar-H),6.40～6.46(m,3H,Ar-H),4.92(d,J＝6.0Hz,2H,CH2),4.52(t,J＝4.8Hz,2H,CH2),4.21(t,J＝4.8Hz,2H,CH2),2.73(s,3H,CH3).
example 6:
the sample is used for carrying out activity screening on leaf weeds of mustard and small gooseberry.
Compound preparation: a certain mass of the original drug is weighed by an analytical balance (0.0001g), dissolved by DMF containing 1% of Tween-80 emulsifier to prepare 1.0% of mother liquor, and then diluted by 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 targets were mustard and chenopodium album. 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 spraying treatment of the stem leaves after seedlings is carried out when the weeds grow to about 3-leaf stage. According to the amount of the provided samples, after the compounds are applied to an automatic spray tower (model: 3WPSH-700E) according to the dosage of 150-1500g a.i./ha, the compounds are transferred to room temperature for culture after the weed leaf surface drugs are dried, and the activity (%) of the compounds on weeds is checked after 35 days.
TABLE 1 preliminary herbicidal Activity data for Ia-Ie
As can be seen from the results of herbicidal activity (Table 1), the compounds Ia to Ie exhibited good herbicidal activity against both the broadleaf weeds mustard and Chenopodium quinoa. At the dosage of 1500g of a.i./ha, the inhibition rates of the compounds Ia to Ie on mustard are respectively 100%, 100%, 100%, 100% and 100%, and the inhibition rates of the compounds Ia to Ie on chenopodium quinoa are respectively 100%, 100%, 100%, 100% and 100%; at a dose of 750g a.i./ha, the inhibition rates of the compounds Ia to Ie on mustard were 100%, 100%, 90%, 70% and 70%, respectively, and the inhibition rates of the compounds Ia to Ie on mustard were 100%, 100%, 100%, 80% and 90%, respectively. The test results show that the new compound obtained by organically linking the benzotriazole phenyl unit and the cyanoacrylate segment has better weeding effect.
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. A cyanoacrylate compound I containing benzotriazole phenyl unit is characterized in that the structure is as follows:
2. the preparation method of cyanoacrylate compound I containing benzotriazole phenyl units according to claim 1, which is characterized by comprising the following steps:
3. the use of cyanoacrylate compounds I containing benzotriazole phenyl units according to claim 1 in the preparation of herbicides, wherein the weeds are Chenopodium quinoa.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0107216A1 (en) * | 1982-09-20 | 1984-05-02 | Shell Internationale Researchmaatschappij B.V. | Heterocyclic compounds, their preparation, compositions containing them and method of controlling unwanted plant growth |
| CN1067061C (en) * | 1993-04-28 | 2001-06-13 | 泽尼卡有限公司 | Herbicidal substituted 1-phenyl or 1-pyridinyl-benzotriazoles |
| CN105732489A (en) * | 2016-03-18 | 2016-07-06 | 南通大学 | Preparation and application of cyanoacrylate compound with pyridine diarylamine structures |
| 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 |
-
2019
- 2019-08-30 CN CN201910814716.8A patent/CN110372618B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0107216A1 (en) * | 1982-09-20 | 1984-05-02 | Shell Internationale Researchmaatschappij B.V. | Heterocyclic compounds, their preparation, compositions containing them and method of controlling unwanted plant growth |
| CN1067061C (en) * | 1993-04-28 | 2001-06-13 | 泽尼卡有限公司 | Herbicidal substituted 1-phenyl or 1-pyridinyl-benzotriazoles |
| CN105732489A (en) * | 2016-03-18 | 2016-07-06 | 南通大学 | Preparation and application of cyanoacrylate compound with pyridine diarylamine structures |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 1-[4-(4-Methylpyrimidin-2-yl)piperazin-1-ylmethyl]-1H-benzotriazole;Feng-Qi He，等;《Acta Crystallographica Section E》;20050716;o2602-o2604 * |
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Effective date of registration: 20221223 Address after: 226000 Gangzha West Nantong Gangzha industrial and Trade Park Patentee after: NANTONG NTEC MONOFILAMENT TECHNOLOGY Co.,Ltd. Address before: 226019 Jiangsu city of Nantong province sik Road No. 9 Patentee before: NANTONG University |