CN107602494A - The preparation and application of the cyanacrylate derivant of the group containing tetrazole - Google Patents
The preparation and application of the cyanacrylate derivant of the group containing tetrazole Download PDFInfo
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- CN107602494A CN107602494A CN201710736310.3A CN201710736310A CN107602494A CN 107602494 A CN107602494 A CN 107602494A CN 201710736310 A CN201710736310 A CN 201710736310A CN 107602494 A CN107602494 A CN 107602494A
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- compound
- group containing
- tetrazole
- herbicide
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Abstract
The present invention relates to the preparation and application of a kind of cyanacrylate derivant (I) of group containing tetrazole.React to obtain with 4 (base of 1,2,3,4 tetrazoles of 1H 1) benzylamines and the dimethyl sulphur-based acrylic acid of 2 cyano group 3,3 substitution ester.The cyanacrylate derivant of the group containing tetrazole has preferable prevention effect to broad leaved weed, and the compound can be used for the herbicide for preparing the fields such as agricultural, gardening.
Description
Technical field
The present invention relates to chemical pesticide field, and in particular to a kind of cyanacrylate derivant of group containing tetrazole
Preparation and use.
Background technology
Herbicide is that relatively broad one kind is used in agricultural chemicals.On whole world herbicide market, traditional type herbicide
Still occupy main status, very big contribution is made that for social development.But in recent years, with people's food security and environmental consciousness
Enhancing, the status of traditional type herbicide is increasingly challenged.In view of its a variety of drawbacks, finding new herbicides turns into
The task of top priority.But higher and higher herbicide standard does not require nothing more than these new herbicides can efficiently go out and cut weeds, with greater need for
It has the characteristics of less toxic, green safe.
Cyanoacrylate compound is a kind of Photosystem I I (PS II) electron transfer inhibitor, and it can disturb plant
Electron transmission in photosynthetical system, plant can not be carried out photosynthesis, so as to reach the purpose of weeding.So special effect
Mechanism make it that cyanoacrylate compound is safe to the animal particularly mankind, meets existing market to new herbicides
Requirement, by the concern of agricultural chemicals worker.The various active cyanoacrylate derivatives in the research of nearly more than ten years
Developed, had a wide range of applications in terms of biological study in succession, such as Wang reports containing pyridine heterocycle unit
Cyanoacrylate compounds NK-9717 shows excellent activity of weeding, and under 300g/ha dosage, NK-9717 is to rape
Cauline leaf process inhibiting rate is up to 100%.
In addition, tetrazole heterocycle is the Typical reactive fragment in drug molecule and pesticide molecule, can effectively change
The physicochemical property of compound, and the compound containing tetrazole heterocycle has stronger physiologically active in vivo.
Therefore, in order to further find the compound with excellent bioactivity from cyanoacrylate compound,
Using active group joining method, reasonably tetrazole heterocyclic group is engaged togather with cyanoacrylate skeleton, this hair
The bright cyanoacrylate compound for disclosing a kind of heterocycle structure containing tetrazole with farm weeding application value.
The content of the invention
It is an object of the invention to provide there is excellent prevention effect for broad leaved weed and grassy weed, and efficiently, peace
Entirely, the cyanacrylate derivant of environment-friendly a kind of group containing tetrazole, to meet that crop protection removes to new and effective
Careless agent demand.
It is a further object of the present invention to provide the preparation method of above-claimed cpd.
It is a still further object of the present invention to provide purposes of the above-claimed cpd in terms of herbicide is prepared.
The object of the invention can be reached by following measures：
In order to solve the above technical problems, the first aspect of the present invention provides a kind of cyanoacrylate of the group containing tetrazole
Derivative, it has following structure：
The present invention provides the preparation method of the cyanacrylate derivant of the above-mentioned heterocyclic substituted containing tetrazole, and its feature exists
In comprising the following steps：
Wherein, intermediate tetrazole Biphenylmethyl amine can refer to document (J.Med.Chem.1998,41,2390；
Chin.Chem.Lett.2014,25,1014；Chin.J.Org.Chem.2016,36,2472 method) synthesizes to obtain；It is middle
Conventional method (the J.Agric.Food of the synthesis reference literature report of body 2- cyano group -3,3- dimethyl sulphur-baseds acrylic acid substitution ester
Chem.2003,51,5030)。
The compounds of this invention to broad leaved weed and and grassy weed there is excellent inhibitory activity, thus the change of the present invention
Compound can be used as preparing herbicide, and then protect the plants such as agricultural, gardening.For example small lamb's-quarters of described broad leaved weed, garden sorrel etc., grass
Section weeds such as amur foxtail, caput grass, annual bluegrass etc..Certainly, the weeds that compound of the invention can prevent and treat are not limited to the example above
Scope.
When the compound of the invention represented by formula I is used as the herbicide in the fields such as agricultural, gardening, can individually make
With, or used in a manner of Herbicidal combinations, such as using Formulas I as active component, it is processed into plus insecticides adjuvant commonly used in the art
Aqueous emulsion, suspending agent, water dispersion granule, missible oil etc..
Conventional insecticides adjuvant includes:Liquid-carrier, such as water；Organic solvent such as toluene, dimethylbenzene, cyclohexanol, methanol, fourth
Alcohol, ethylene glycol, acetone, dimethylformamide, acetic acid, dimethyl sulfoxide, animal and plant oil and aliphatic acid；Conventional superficiality agent
Such as emulsifying agent and dispersant, including anion surfactant, cationic surfactant, nonionic surfactant and both sexes
Surfactant；Other auxiliary agents, such as wetting agent, thickener.
When the compound of the present invention is used as the active component in herbicide, the content in the herbicide can be 0.1%
Selected in the range of to 99.5%, and appropriate active component content can be determined according to dosage form and application process.It is logical
Often, in aqueous emulsion containing the active component described in 5% to 50% (percentage by weight, similarly hereinafter), preferably its content be 10% to
40%；Containing 5% to 50% active component in suspending agent, preferably its content is 5% to 40%.
Use for the herbicide of the present invention, conventional application method may be selected, such as cauline leaf spraying, used for ponds, native
Earth processing and seed treatment etc..For example, when using cauline leaf spraying, the compound that is represented by formula I as active component
Aqueous emulsion, suspending agent, water dispersion granule, the missible oil that concentration range is 75-1500g a.i./ha, preferably its concentration can be used
For 150-1500g a.i./ha.
The cyanacrylate derivant of the group disclosed by the invention containing tetrazole is to some broad leaved weeds and and grass family
Weeds have excellent prevention effect, therefore can be used to prepare the herbicide for fields such as agricultural, gardening.
Embodiment
For the ease of being further appreciated that to the present invention, examples provided below has done more detailed description to it.This
A little embodiments are only not used for limiting the scope of the present invention or implementation principle for narration.
Embodiment 1：
6mmol compound III a and 8mmol intermediate IIs are added in a reaction bulb, and add appropriate DMF, are heated to
80 DEG C, react 13 hours, remove solvent under reduced pressure, residue is through column chromatography [V (petroleum ether):V (ethyl acetate)=1:1] separate
To target compound；1H NMR(400MHz,CDCl3):δ10.43(s,1H,NH),8.67(s,1H,Tetrazole-H),8.18
(d, J=8.4Hz, 2H, Ar-H), 7.46 (d, J=8.4Hz, 2H, Ar-H), 4.88 (d, J=6.0Hz, 2H, CH2),4.33(t,
J=4.8Hz, 2H, CH2), 3.67 (t, J=4.8Hz, 2H, CH2),3.41(s,3H,OCH3),2.69(s,3H,SCH3).
Embodiment 2：
3mmol compounds Ia and appropriate absolute methanol are added in a reaction flask, 8mmol first is added under room temperature condition
The mixed solution of sodium alkoxide and methanol, is finished, and continues to be stirred at room temperature 6 hours.Remove solvent under reduced pressure, added into residue appropriate
Water, it is extracted with ethyl acetate for several times, merges organic phase, anhydrous sodium sulfate drying, filter, depressurize precipitation, residue is through column chromatography
[V (petroleum ether):V (ethyl acetate)=3:1] isolated target compound Ib；1H NMR(400MHz,CDCl3):δ9.84(s,
1H, NH), 8.68 (s, 1H, Tetrazole-H), 8.16 (d, J=8.4Hz, 2H, Ar-H), 7.45 (d, J=8.8Hz, 2H, Ar-
), H 4.58 (d, J=6.0Hz, 2H, CH2), 4.33 (t, J=4.8Hz, 2H, CH2),4.26(s,3H,OCH3), 3.67 (t, J=
4.8Hz,2H,CH2),3.42(s,3H,OCH3).
Embodiment 3：
5mmol compound III c and 3mmol intermediate IIs are added in a reaction bulb, and add appropriate acetonitrile, room temperature is anti-
Answer 18 hours, remove solvent under reduced pressure, residue is through column chromatography [V (petroleum ether):V (ethyl acetate)=1:1] isolated target
Compound Ic；1H NMR(400MHz,CDCl3):δ10.43(s,1H,NH),8.67(s,1H,Tetrazole-H),8.17(d,J
=8.4Hz, 2H, Ar-H), 7.46 (d, J=8.4Hz, 2H, Ar-H), 4.88 (d, J=6.0Hz, 2H, CH2), 4.31 (t, J=
5.2Hz,2H,CH2), 3.70 (t, J=5.2Hz, 2H, CH2), 3.59 (q, J=6.8Hz, 2H, CH2),2.69(s,3H,SCH3),
1.21 (t, J=6.8Hz, 2H, CH3).
Embodiment 4：
2mmol compounds Ic is added in a reaction bulb, and adds appropriate DMSO, adds 2mmol sodium methoxides thereto,
Finish, be heated to 55 DEG C, react 9 hours.Suitable quantity of water is added into residue, is extracted with ethyl acetate for several times, merges organic phase,
Anhydrous sodium sulfate drying, filter, depressurize precipitation, residue is through column chromatography [V (petroleum ether):V (ethyl acetate)=3:1] separate
To target compound Id；1H NMR(400MHz,CDCl3):δ9.84(s,1H,NH),8.67(s,1H,Tetrazole-H),8.16
(d, J=8.8Hz, 2H, Ar-H), 7.44 (d, J=8.4Hz, 2H, Ar-H), 4.59 (d, J=6.0Hz, 2H, CH2),4.31(t,
J=5.2Hz, 2H, CH2),4.26(s,3H,OCH3), 3.70 (t, J=5.2Hz, 2H, CH2), 3.59 (q, J=6.8Hz, 2H,
CH2), 1.22 (t, J=6.8Hz, 3H, CH3).
Embodiment 5：
Sample is to the small lamb's-quarters of broad leaved weed, garden sorrel and grassy weed amur foxtail, caput grass, annual bluegrass screening active ingredients
Compound configures：The active compound of certain mass is weighed with assay balance (0.0001g), with containing 1% Tween-80 emulsifying agent
DMF dissolving be configured to 1.0% mother liquor, it is then standby with distilled water diluting.
Test method：Pot-culture method (general sieve), before seedling soil treatment and after seedling cauline leaf process.For examination target be leaf mustard, small lamb's-quarters,
Amur foxtail and caput grass.Internal diameter 7.5cm flowerpots are taken, fill composite earth (vegetable garden soil：Seedling medium, 1:2, v/v) at 3/4, directly
Above-mentioned five kinds of weeds targets (bud rate >=85%) are sowed, earthing 0.2cm, it is standby to or so the 3 leaf phases to treat that weeds grow.Each compound is pressed
According to 1500g a.i./ha dosage in auto spraying tower (model：3WPSH-700E) after dispenser, after weeds blade face, medicine moves into after drying
Hot-house culture, activity (%) of the investigation to weeds after 35 days.
Table 1.Ia-Id preliminary Herbicide activity data
As can be seen from Table 1, under 1500g a.i./ha dosage, compound Ia-Id is to the small lamb's-quarters of broad leaved weed and garden sorrel table
Reveal good activity of weeding, compound Ia, Ib, Ic and Id to the inhibitory activity of small lamb's-quarters and garden sorrel up to 100%, with comparison medicine
NK-9717 herbicidal effect is suitable；In addition, compound Ia-Id displays that to grassy weed amur foxtail, caput grass and annual bluegrass
Go out preferable activity of weeding, compound Ia, Ib, Ic and Id are respectively 45%, 45% to the inhibiting rate of amur foxtail, 45% He
60%, hence it is evident that be better than comparison medicine NK-9717 herbicidal effect (30%)；The suppression of compound Ia, Ib, Ic and Id to caput grass
Rate is respectively 40%, 40%, 45% and 55%, is higher than comparison medicine NK-9717 herbicidal effect (20%)；Compound Ia, Ib,
Ic and Id is respectively 40%, 45%, 40% and 45% to the inhibiting rate of annual bluegrass, is higher than comparison medicine NK-9717 weeding effect
Fruit (20%).Data above shows, will contain substituted tetrazole heterocycle and alpha-cyanoacrylate ester structure links together, obtained change
Compound has preferable activity of weeding, and wherein compound I d can make further structure derivative and structure-activity relationship as weeding guide
Research.This is also provided to be engaged in the MOLECULE DESIGN of Novel cyano acrylic ester compound, synthesis and bioactivity research from now on
Important structure choice pattern and theoretical foundation.
General principle, principal character and the advantages of the present invention of the present invention has been shown and described above.The technology of the industry
For personnel it should be appreciated that the present invention is not limited by examples detailed above, simply illustrating described in examples detailed above and specification is of the invention
Principle, various changes and modifications of the present invention are possible without departing from the spirit and scope of the present invention, these change and
Improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention is by appended claims and its is equal
Thing defines.
Claims (5)
1. the cyanacrylate derivant of a kind of group containing tetrazole, it is characterised in that it has the structure of Formulas I：
2. the cyanacrylate derivant of the group according to claim 1 containing tetrazole, it is characterised in that it has such as
Lower structure：
3. prepare the method for the cyanacrylate derivant of the group containing tetrazole as claimed in claim 1, it is characterised in that
Comprise the following steps：
4. use of the cyanacrylate derivant of the group containing tetrazole in terms of herbicide is prepared as claimed in claim 1
On the way, it is characterised in that：Using the compound of Formulas I as active component, it is processed into aqueous emulsion, suspending agent, moisture plus insecticides adjuvant and dissipates
Granule, missible oil.
5. purposes according to claim 3, it is characterised in that：When the compound of Formulas I is used as the active component in herbicide,
Scope of the content 0.1% to 99.5% in the herbicide.
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| CN201710736310.3A CN107602494B (en) | 2017-08-24 | 2017-08-24 | Preparation and application of cyanoacrylate derivative containing tetrazole group |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710736310.3A CN107602494B (en) | 2017-08-24 | 2017-08-24 | Preparation and application of cyanoacrylate derivative containing tetrazole group |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111892546A (en) * | 2020-09-04 | 2020-11-06 | 南通大学 | Preparation and application of cyanoacrylate containing 1,2, 3-triazole biphenyl |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101967115A (en) * | 2009-12-17 | 2011-02-09 | 南开大学 | Synthesis and herbicidal activity of 3-substituted phenoxybenzamine-2-cyanoacrylate ethoxyethyl compound |
| CN105732489A (en) * | 2016-03-18 | 2016-07-06 | 南通大学 | Preparation and application of cyanoacrylate compound with pyridine diarylamine structures |
-
2017
- 2017-08-24 CN CN201710736310.3A patent/CN107602494B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101967115A (en) * | 2009-12-17 | 2011-02-09 | 南开大学 | Synthesis and herbicidal activity of 3-substituted phenoxybenzamine-2-cyanoacrylate ethoxyethyl compound |
| CN105732489A (en) * | 2016-03-18 | 2016-07-06 | 南通大学 | Preparation and application of cyanoacrylate compound with pyridine diarylamine structures |
Non-Patent Citations (1)
| Title |
|---|
| 王宝雷等: "4-烷氧/苄氧基苯基四唑和1,3,4-噁二唑类化合物的合成及除草活性", 《高等学校化学学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110818649B (en) * | 2019-09-16 | 2021-10-22 | 南通大学 | Preparation and application of 2-cyanoacrylate derivative containing 1, 2, 4-triazole benzylamine unit |
| CN111892546A (en) * | 2020-09-04 | 2020-11-06 | 南通大学 | Preparation and application of cyanoacrylate containing 1,2, 3-triazole biphenyl |
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| Publication number | Publication date |
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| CN107602494B (en) | 2019-12-10 |
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Effective date of registration: 20201021 Address after: 226019 No.205, building 6, Nantong University, No.9, Siyuan Road, Nantong City, Jiangsu Province Patentee after: Center for technology transfer, Nantong University Address before: 226019 Jiangsu city of Nantong province sik Road No. 9 Patentee before: NANTONG University |
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Effective date of registration: 20201126 Address after: 239300 Yang Cun town Industrial Park, Anhui, Chuzhou, Tianchang Patentee after: Anhui xianshengda pesticide Co., Ltd Address before: 226019 No.205, building 6, Nantong University, No.9, Siyuan Road, Nantong City, Jiangsu Province Patentee before: Center for technology transfer, Nantong University |