CN107556253B - Cyanoacrylate compound of the heterocyclic substituted containing triazole and its preparation method and application - Google Patents
Cyanoacrylate compound of the heterocyclic substituted containing triazole and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to cyanoacrylate compounds (I) of a kind of heterocyclic substituted containing triazole and its preparation method and application.Ester (III) is replaced to react to obtain with 2- cyano -3,3- dimethyl sulphur-based acrylic acid with 4- (1H-1,2,3- triazole -1- base) benzylamine (II).The cyanoacrylate compound of the heterocyclic substituted containing triazole has preferable control efficiency to broadleaf weeds and gramineae weed, which can be used for preparing the herbicide in the fields such as agricultural, gardening.
Description
Technical field
The present invention relates to chemical pesticide fields, and in particular to a kind of cyanoacrylate of the heterocyclic substituted containing triazole
Close object and its preparation method and application.
Background technique
Herbicide is that relatively broad one kind is used in pesticide.On whole world herbicide market, traditional type herbicide
Still occupy main status, is made that very big contribution for social development.However in recent years, with people's food safety and environmental consciousness
Enhancing, the status of traditional type herbicide is increasingly challenged.In view of its various drawbacks, finding new herbicides becomes
The task of top priority.However 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 that less toxic, green safe.
Cyanoacrylate compound is a kind of Photosystem I I (PS II) electron transfer inhibitor, it can interfere plant
Electron transmission in photosynthetical system makes plant that can not carry out photosynthesis, to achieve the purpose that weeding.Effect special in this way
Mechanism make cyanoacrylate compound be to the animal especially mankind it is safe, meet existing market to new herbicides
Requirement, by the concern of pesticide worker.The various active cyanoacrylate derivatives in the research of nearly more than ten years
It developed, had a wide range of applications in terms of biological study in succession, such as Wang report 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, triazole heterocycle is the Typical reactive segment in drug molecule and pesticide molecule, can effectively change
The physicochemical property of compound, and the compound containing triazole heterocycle has stronger physiological activity in vivo.Such as three
Azole herbicide benzophenone azoles has efficient selectivity to rice, can be used for rice field except barnyard grass.
Therefore, in order to further find the compound with excellent bioactivity from cyanoacrylate compound,
Using active group joining method, reasonably triazole heterocyclic group is engaged togather with cyanoacrylate skeleton, this hair
It is bright to disclose a kind of cyanoacrylate compound containing triazole heterocyclic structure with farm weeding application value.
Summary of the invention
The object of the present invention is to provide have excellent control efficiency, and efficient, peace for broadleaf weeds and gramineae weed
Entirely, the cyanoacrylate derivative of environmental-friendly a kind of heterocyclic substituted containing triazole, to meet crop protection to novel
Highy potent herbicide demand.
It is a further object of the present invention to provide the preparation methods of above compound.
The purposes that it is a still further object of the present invention to provide above compounds in terms of preparing herbicide.
The object of the invention can be achieved by the following measures:
In order to solve the above technical problems, the first aspect of the present invention provides a kind of cyanoacrylate of heterocyclic substituted containing triazole
Acid esters analog derivative, with general formula I,
Preferably, the cyanoacrylate derivative of the heterocyclic substituted containing triazole has the following structure:
The present invention provides the preparation method of the cyanoacrylate derivative of the above-mentioned heterocyclic substituted containing triazole, feature
It is to include the following steps:
Compound III is dissolved in organic solvent, then intermediate II is being added, finally heated reaction a period of time, will be reacted
Liquid filters after being cooled to room temperature, and mother liquor is concentrated under reduced pressure, and gained residue obtains target compound through column chromatographic isolation and purification,
Preferably, the organic solvent is selected from chloroform, carbon tetrachloride, ethyl alcohol, Isosorbide-5-Nitrae-dioxane, 1,2- bis- chloroethene
Alkane.Heating reaction temperature is 35 DEG C~80 DEG C, and the reaction time is 4 hours~22 hours.
Preferably, the preparation method of the cyanoacrylate derivative of the heterocyclic substituted containing triazole, includes the following steps:
Wherein, intermediate triazole Biphenylmethyl amine can refer to document (J.Med.Chem.1998,41,2390-2410；
Chin.Chem.Lett.2014,25,1014-1016；Chin.J.Org.Chem.2016,36,2472-2478 method synthesis)
It obtains；Intermediate 2- cyano -3,3- dimethyl sulphur-based acrylic acid replaces the conventional method of the synthesis reference literature report of ester
(J.Agric.Food Chem.2003,51,5030)。
The compounds of this invention to broadleaf weeds and and gramineae weed there is excellent inhibitory activity, thus change of the invention
Closing object can be used as preparing herbicide, and then protect the plants such as agricultural, gardening.Described broadleaf weeds such as leaf mustard, small Chenopodiaceae etc., grass
Section weeds such as amur foxtail, caput grass etc..Certainly, the weeds that the compound of the present invention can prevent and treat are not limited to the range of the example above.
When the compound of the present invention indicated by general 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 constituent, in addition insecticides adjuvant commonly used in the art is processed into
Aqueous emulsion, suspending agent, water dispersion granule, missible oil etc..
Common 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 fatty acid；Common superficiality agent
Such as emulsifier and dispersing agent, including anionic 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 constituent in herbicide, the content in the herbicide can be 0.1%
It is selected in the range of to 99.5%, and can determine active component content appropriate according to dosage form and method of administration.It is logical
Often, in aqueous emulsion containing active constituent described in 5% to 50% (weight percent, similarly hereinafter), preferably its content be 10% to
40%；In suspending agent containing 5% to 50% active constituent, preferably its content be 5% to 40%.
Common application method may be selected in use for herbicide of the invention, as cauline leaf is spraying, used for ponds, native
Earth processing and seed treatment etc..For example, when spraying using cauline leaf, the compound indicated by general formula I as active constituent
It is aqueous emulsion, suspending agent, water dispersion granule, the missible oil of 75-1500g a.i./ha, preferably its concentration that concentration range, which can be used,
For 150-1500g a.i./ha.
The cyanoacrylate derivative of the heterocyclic substituted disclosed by the invention containing triazole to certain broadleaf weeds and and
Gramineae weed has excellent control efficiency, therefore can be used to prepare the herbicide for fields such as agricultural, gardening.
Specific embodiment
For the ease of further appreciating that examples provided below has done more detailed description to it to of the invention.This
A little embodiments are only not supposed to be a limitation to the present invention for narration or implementation principle.
Embodiment 1:
3mmol compound III a and 2mmol intermediate II is added in 50mL flask, and appropriate carbon tetrachloride is added, is added
Heat is reacted 6 hours to 35 DEG C.Evaporating solvent under reduced pressure, residue is through column chromatography [V (petroleum ether): V (ethyl acetate)=1:1] point
From obtaining target compound Ia；1H NMR(400MHz,CDCl3): δ 10.38 (s, 1H, NH), 8.11 (d, J=8.4Hz, 2H, Ar-
), H 7.83 (s, 2H, Triazole-H), 7.38 (d, J=8.4Hz, 2H, Ar-H), 6.90~7.10 (m, 4H, Ar-H), 4.85
(d, J=6.0Hz, 2H, CH2), 4.53 (t, J=5.2Hz, 2H, CH2), 4.32 (t, J=5.0Hz, 2H, CH2),2.68(s,3H,
SCH3).
Embodiment 2:
2mmol compound III b and 2.2mmol intermediate II is added in 50mL flask, and appropriate dehydrated alcohol is added,
Heating reflux reaction 4 hours, after reaction, evaporating solvent under reduced pressure, residue chromatographed [V (petroleum ether): V (acetic acid second through column
Ester)=1:1] isolated target compound；1H NMR(400MHz,CDCl3): δ 10.37 (s, 1H, NH), 8.11 (d, J=
8.4Hz, 2H, Ar-H), 7.83 (s, 2H, Triazole-H), 7.38 (d, J=8.4Hz, 2H, Ar-H), 7.06~7.00 (m,
1H, Ar-H), 6.88~6.77 (m, 2H, Ar-H), 4.85 (d, J=5.6Hz, 2H, CH2), 4.50 (t, J=4.8Hz, 2H,
CH2), 4.28 (t, J=4.8Hz, 2H, CH2),2.69(s,3H,SCH3).
Embodiment 3:
4mmol compound III c and 7mmol intermediate II is added in 50mL flask, and appropriate chloroform is added, is added
Heat is reacted 22 hours, evaporating solvent under reduced pressure to 45 DEG C, and residue is through column chromatography [V (petroleum ether): V (ethyl acetate)=1:1] point
From obtaining target compound；1H NMR(400MHz,CDCl3): δ 10.39 (s, 1H, NH), 8.11 (d, J=8.8Hz, 2H, Ar-
), H 7.83 (s, 2H, Triazole-H), 7.38 (d, J=8.8Hz, 2H, Ar-H), 6.92~7.31 (m, 5H, Ar-H), 4.84
(d, J=6.0Hz, 2H, CH2), 4.52 (t, J=5.0Hz, 2H, CH2), 4.24 (t, J=6.0Hz, 2H, CH2),2.68(s,3H,
SCH3).
Embodiment 4:
4mmol compound III d and 3mmol intermediate II is added in 50mL flask, and appropriate Isosorbide-5-Nitrae-dioxy six is added
Ring, is heated to 80 DEG C, reacts 18 hours, evaporating solvent under reduced pressure, residue chromatograph through column [V (petroleum ether): V (ethyl acetate)=
1:1] isolated target compound；1H NMR(400MHz,CDCl3): δ 10.40 (s, 1H, NH), 8.10 (d, J=8.4Hz,
2H, Ar-H), 7.83 (s, 2H, Triazole-H), 7.37 (d, J=8.4Hz, 2H, Ar-H), 4.84 (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=7.2Hz, 2H, CH2),
2.68(s,3H,SCH3), 1.21 (t, J=7.2Hz, 3H, CH3).
Embodiment 5:
4mmol compound III e and 6mmol intermediate II is added in 50mL flask, and appropriate 1,2-, bis- chloroethene is added
Alkane, is heated to 50 DEG C, reacts 17 hours, evaporating solvent under reduced pressure, residue chromatograph through column [V (petroleum ether): V (ethyl acetate)=
1:1] isolated target compound；1H NMR(400MHz,CDCl3): δ 10.39 (s, 1H, NH), 8.10 (d, J=8.4Hz,
2H, Ar-H), 7.83 (s, 2H, Triazole-H), 7.37 (d, J=8.4Hz, 2H, Ar-H), 4.83 (d, J=6.0Hz, 2H,
CH2), 4.15~4.23 (m, 3H, CH2And CH), 3.76~3.96 (m, 2H, CH2),2.68(s,3H,SCH3),
1.76~2.07 (m, 4H, 2 × CH2).
Embodiment 6:
Sample is to broadleaf weeds leaf mustard, small Chenopodiaceae and gramineae weed amur foxtail, caput grass screening active ingredients
Compound configuration: weighing the raw medicine of certain mass with assay balance (0.0001g), with containing 1% Tween-80 emulsifier
DMF dissolution be configured to 1.0% mother liquor, then with distilled water dilute it is spare.
Test method: pot-culture method (general sieve), soil treatment and stem and leaf treatment after seedling before seedling.For examination target be leaf mustard, small Chenopodiaceae,
Amur foxtail and caput grass.Take internal diameter 7.5cm flowerpot, at dress composite earth (vegetable garden soil: seedling medium, 1:2, v/v) to 3/4, directly
Above-mentioned four kinds of weeds targets (bud rate >=85%) are sowed, earthing 0.2cm is long to cauline leaf spray after 3 leaf phases or so progress seedling after weeds
Mist processing, and soil treatment then carries out sowing earthing on the day before spray and water is added to keep ground moistening before seedling.According to offer
Sample size, each compound according to 1500g a.i./ha dosage auto spraying tower (model: 3WPSH-700E) application after, to miscellaneous
Blade of grass face medicine, which dries, to be moved back into incubated at room temperature, and the activity (%) to weeds is investigated after 35 days.
The preliminary Herbicide activity data of table 1.Ia-Ij
As can be seen from Table 1, under 1500g a.i./ha dosage, compound Ia-Ie is to broadleaf weeds leaf mustard and small Chenopodiaceae table
Revealing good activity of weeding, compound Ia, Ib, Ic, Id and Ie are respectively 90%, 95% to the inhibitory activity of leaf mustard,
100%, 100% and 100%, it is suitable with the herbicidal effect of comparison medicine NK-9717；Compound Ia, Ib, Ic, Id and Ie are to small Chenopodiaceae
Inhibiting rate be respectively 90%, 100%, 100%, 100% and 100%, it is close with the herbicidal effect of comparison medicine NK-9717；This
Outside, compound Ia-Ie also shows that preferable activity of weeding to gramineae weed amur foxtail and caput grass, compound Ia, Ib,
Ic, Id and Ie are respectively 50%, 70%, 70%, 70% and 90% to the inhibiting rate of amur foxtail, hence it is evident that are better than comparison medicine NK-
9717 herbicidal effect (30%)；Compound Ia, Ib, Ic, Id and Ie are respectively 30%, 40% to the inhibiting rate of caput grass,
60%, 50% and 60%, it is higher than the herbicidal effect (20%) of comparison medicine NK-9717.Above data, which shows to contain, replaces three nitrogen
Azoles heterocycle and alpha-cyanoacrylate ester structure link together, and obtained compound has preferable activity of weeding, especially to standing grain
The activity of undergraduate course weeds amur foxtail and caput grass is better than comparison medicine NK-9717, and wherein compound I e can be used as weeding guide work
Further structure derivative and structure activity study.This is also to be engaged in the molecule of Novel cyano acrylic ester compound from now on to set
Meter, synthesis provide important structure choice mode and theoretical foundation with bioactivity research.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel only illustrate the present invention it should be appreciated that the present invention is not limited by examples detailed above described in examples detailed above and specification
Principle, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these variation 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
Object defines.
Claims (4)
1. a kind of cyanoacrylate compound I of heterocyclic substituted containing triazole, it is characterised in that structure are as follows:
2. a kind of preparation method of the cyanoacrylate compound I of the heterocyclic substituted containing triazole as described in claim 1,
It is characterized in that method is as follows:
3. the cyanoacrylate compound I of the heterocyclic substituted containing triazole prevents and kill off leaf mustard in preparation as described in claim 1
Purposes in terms of drug, it is characterised in that: the compound is used alone；Or using compound I in claim 1 as active constituent,
In addition insecticides adjuvant commonly used in the art be processed into aqueous emulsion, suspending agent, water dispersion granule, missible oil Herbicidal combinations side
Formula uses.
4. the cyanoacrylate compound I of the heterocyclic substituted containing triazole prevents and kill off leaf mustard in preparation as claimed in claim 3
Purposes in terms of drug, it is characterised in that: when compound I described in claim 1 is used as the active constituent for preventing and kill off leaf mustard drug,
It is selected in the range of the content prevented and kill off in leaf mustard drug is 0.1% to 99.5%.
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| CN111978302B (en) * | 2019-05-24 | 2022-03-22 | 帕潘纳(北京)科技有限公司 | Triazole cyanide compound and preparation method thereof |
| CN110372618B (en) * | 2019-08-30 | 2021-10-01 | 南通大学 | Preparation method and application of cyanoacrylate compound containing benzotriazole phenyl 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 |
Citations (2)
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|---|---|---|---|---|
| CN101659636A (en) * | 2009-03-24 | 2010-03-03 | 南开大学 | Synthesis and herbicidal activity of 2-cyano-3-alkoxy-3'-methyl acrylic acid ester |
| CN105732489A (en) * | 2016-03-18 | 2016-07-06 | 南通大学 | Preparation and application of cyanoacrylate compound with pyridine diarylamine structures |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101659636A (en) * | 2009-03-24 | 2010-03-03 | 南开大学 | Synthesis and herbicidal activity of 2-cyano-3-alkoxy-3'-methyl acrylic acid ester |
| 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)
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