CN106800534B - A kind of cinnamic acid naphthalimide ester type compound and application thereof - Google Patents
A kind of cinnamic acid naphthalimide ester type compound and application thereof Download PDFInfo
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- CN106800534B CN106800534B CN201710018077.5A CN201710018077A CN106800534B CN 106800534 B CN106800534 B CN 106800534B CN 201710018077 A CN201710018077 A CN 201710018077A CN 106800534 B CN106800534 B CN 106800534B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/04—Ortho- or peri-condensed ring systems
- C07D221/06—Ring systems of three rings
- C07D221/14—Aza-phenalenes, e.g. 1,8-naphthalimide
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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
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
- A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
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- Agronomy & Crop Science (AREA)
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Abstract
The invention discloses a kind of cinnamic acid naphthalimide ester type compounds that structure is shown in formula I, are used as plant growth regulator.Compound of formula I, which has, excellent to be inspired bud, takes root and increasing yield and improving quality effect, and there is good bactericidal effect, especially there is preventive and therapeutic effect in 200ppm etc. to phytoph-thora capsici leonian, wheat scab, ring rot of apple, cucumber fusarium axysporum, can be widely used for disease prevention, the volume increase of agricultural or forestry.
Description
The invention belongs to plant growth regulator fields in pesticide for technical field, and in particular to two formyl of cinnamic acid naphthalene is sub-
Amine ester and application thereof.
Background technique plant growth regulator is as the big classification in pesticide, in agricultural production and income, raising quality etc.
Aspect played an important role, Ensuring Food Safety, in terms of more and more attention has been paid to.Patent CN
103130663B discloses a kind of purposes of cinnamate derivative compound as plant growth regulator, patent CN
105481762B discloses a kind of purposes of cinnamic acid pyridine ethyl ester type compound as plant growth regulator.Patent CN
105669549A discloses a kind of aphthalimide base ethylnaphthalene acetate compounds and its as plant growth regulator
Purposes, patent CN 105669550A disclose a kind of aphthalimide base thylhexoic acid esters compound and its raw as plant
The purposes of long regulator.In the prior art, cinnamic acid naphthalimide ester (compound of formula I) as described in the present invention and its
Purposes is not disclosed at home and abroad.
The object of the present invention is to provide a kind of cinnamic acids for having both plant growth regulating activity and bactericidal activity for summary of the invention
Naphthalimide ester type compound promotes plant establishment germination, has obvious effect of increasing production, production and application is at low cost and uses peace
Entirely, it can be used for the increasing yield and improving quality of crops and fruits and vegetables.
Technical scheme is as follows:
A kind of cinnamic acid naphthalimide ester plant growth regulator, structure are shown in formula I:
Compound of formula I can be made by following reaction:
Specific preparation method is shown in that this specification synthesizes example.
Application of the formula Compound I as plant growth regulator: compound of formula I has water-insoluble, when application
It must be processed into emulsion, suspending agent, wettable powder etc., substance content is 1~80% in preparation, and when use can be according to reality
It needs for above-mentioned preparation to be watered the suspension or aqueous emulsion for being diluted to 0.1~1000 μ g/mL concentration, carries out leaching root, root dipping, leaching
Kind, seed dressing, seed pelleting spray cauline leaf.
Plant growth regulator composition the invention also includes compound of formula I as active component, it is living in the composition
Property component refer to that compound of formula I or compound of formula I and other active components such as sodium cinnamate, compound sodium nitrophenolate, indolebutyric acid sodium etc. are planted
The composition of a kind of, two or more compositions of object growth regulator further includes agricultural in the plant growth regulator composition
Or acceptable carrier in forestry.The invention also includes compound of formula I to have certain bactericidal activity, as germicide constituent,
It can be used alone, can also be used in compounding with other fungicide, to improve the comprehensive function of product.
The advantages and positive effects of the present invention: it is significant that indoor and field control effectiveness test shows that compound of formula I has crop
Promotion growth, increasing yield and improving quality effect, have for wheat, rice, corn, potato, cucumber, tomato, capsicum, apple etc. good
Good diseases prevention and volume increase double action.As respectively sprayed once under 100 μ g/mL concentration of compound of formula I in wheat tillering and heading stage,
Increase production 18-20%；It is respectively sprayed once in rice tillering and heading stage, increases production 15-18%；In red fuji apple young fruit period and fruit
Expanding stage respectively sprays once, one week precocious, 20% or more volume increase, and coloring and mouthfeel are obviously improved.Meanwhile compound of formula I pair
Agriculture Common fungi disease such as phytoph-thora capsici leonian, ring rot of apple, wheat scab, cucumber fusarium axysporum, the late blight of potato, water
Sheath and culm blight of rice etc. has preventive and therapeutic effect.The preparation of formula Compound I is simple, produce and use cost is low, not only disease prevention but also volume increase,
Production and use cost are low, and dosage is small, wide using concentration range, safe and convenient to use, can be widely used for various crops and fruit
Promoting root growth, volume increase, degeneration-resistant, upgrading, anti-fungus damage of vegetable etc. are multifunctional plant growth regulators rare at present, are had wide
Wealthy commercialization prospect and market potential.
It should be clear that various transformation and change can be carried out in scope defined by the claims of the present invention.
Specific embodiment
Following synthesis example, formulation examples and raw experimental result of surveying can be used to further illustrate the present invention, but not mean that
The limitation present invention.
Synthesize example
The preparation of example 1, compound of formula I
(1) preparation of cinnamoyl chloride
14.8g (0.1mol) cinnamic acid, 150mL toluene, 14.3g (0.12mol) are sequentially added in 250mL three-necked flask
Lower dropwise addition 0.2mL n,N-Dimethylformamide, temperature rising reflux 2h is stirred at room temperature in thionyl chloride.TLC monitoring reaction is completed, revolving
Solvent and excessive thionyl chloride out obtain 16.1g pale yellowish oil liquid, yield 96.4%.
(2) preparation of Formula II compound
19.8g (0.1mol) naphthalic anhydride and 8.34g (0.12mol) hydrochloric acid are separately added into 250mL three-necked flask
Azanol, 4.8g (0.1mol) sodium hydroxide, 150mL water as solvent, heating stirring reflux are cooling to take out after TLC monitors fully reacting
Orange red solid is filtered to obtain, dries, obtains 20.7g, yield 97.1%.
(3) preparation of compound of formula I
It is separately added into 21.3g (0.1mol) Formula II compound and 150mL toluene in 250mL three-necked flask, 20.0g is added dropwise
The solution of (0.12mol) cinnamoyl chloride and 30mL toluene composition, drop finish, are heated to reflux down and are stirred to react 4.5h, TCL detection reaction
After completely, chartreuse solid 23.4g is filtered to obtain, yield 71.0%, 180.1~212.3 DEG C of fusing point.
Compound of formula I1H NMR (500MHz, DMSO-d6), δ (ppm): 7.159-7.176 (d, 1H, CH), 7.486-
7.530 (q, 3H, Ar-H), 7.900-7.914 (d, 2H, Ar-H), 7.931-7.962 (t, 2H, Ar-H), 8.027-8.060 (d,
1H, CH), 8.571-8.593 (q, 4H, Ar-H).
Example of formulations
The preparation of example 2,10% compound of formula I suspending agent:
10g compound of formula I, 2g sodium lignin sulfonate, the 5 (Malaysia 3g polycarboxylate salt dispersant Sokalan CP are weighed respectively
Acid-acrylic acid sodium salt), 1g organosilicon cream defoaming agent (the aqueous silicon emulsified antifoam agent of THIX-108), 2g aluminium-magnesium silicate and 5g second two
Alcohol is added 77g water, stirs evenly in 250mL beaker, grinds 2h with sand mill, and revolving speed is 3000 revs/min, and detection granularity 3~
5 μm, obtain white mobility suspending agent.
One, plant adjusts activity test
Example 3, Seeds Germination Tests
It is carried out using paper bed sproutung method.Respectively by 30% compound of formula I suspending agent and DA-6 (the limited public affairs of Henan Zheng Shi chemical industry
Department produces) it is diluted to 5% compound of formula I suspending agent and 5%DA-6 aqua, being diluted with distilled water into concentration respectively is 10 μ g/
The plant growth regulator solution of mL, 20 μ g/mL, 30 μ g/mL, 60 μ g/mL and 120 μ g/mL.It is uniform, full to select Seed size
Full wheat seed after being sterilized with hypochlorite solution to seed, is soaked seed with above-mentioned dilution in beaker and cultivates 8h, every place
100 seeds are managed, seed is uniformly placed in the culture dish of double-layer filter paper after processing, one is kept between seed by 3 repetitions
Fixed distance is well placed seed and puts it into 25 DEG C of heat preservation vernalization processing in complete intelligent climate box later, to be during which periodically added
Distilled water makes filter paper keep wet, and the germination of each processing is observed during vernalization, and radicel length is about mark with the 1/2 of seed length
Standard in counting wheat seed germination percentage in each culture dish afterwards for 24 hours, while being compared with the DA-6 of same concentrations and clear water (CK),
Each dilution germination promotion rate is calculated simultaneously, as a result as shown in table 1 below.
The experiment of 1 wheat seed germinating of table
By 1 experimental data of table as it can be seen that the wheat germination rate of formula Compound I processing is better than contrast agents on the whole
DA-6 is more significantly better than the case where clear water handles (CK).
Example 4, seed soaking growth-promoting root experiment
30% suspending agent of compound of formula I and DA-6 (Henan Zheng Shi Chemical Co., Ltd. product) are diluted to 5% respectively
Compound of formula I suspending agent and 5%DA-6 aqua, be diluted with distilled water into respectively concentration be 10 μ g/mL, 20 μ g/mL, 30 μ g/mL,
The plant growth regulator solution of 60 μ g/mL and 120 μ g/mL.The wheat seed that Seed size is uniform, full is selected, with secondary chlorine
After acid solution sterilizes seed, is soaked seed in beaker with above-mentioned dilution and cultivate 8h, 20 wheats of every processing, 3 repetitions,
Seed is uniformly placed on wet paper bed after processing, is maintained a certain distance between seed, to guarantee that seed fully absorbs
Moisture, embryo portion is well placed after seed to put it into complete intelligent climate box and carries out vernalization upward towards the same side when setting bed
For 24 hours, distilled water, which is during which periodically added, makes paper bed keep wet for processing.Expose 2mm or so to wheat main root, by its kind
In the solid medium of solidification, it is then placed in complete intelligent climate box and is cultivated.It is high with calliper to measure main root, stem after 40h, and
Make detailed record.It is compared simultaneously with the DA-6 of same concentrations and clear water processing (CK), as a result as shown in table 2 below.
The experiment of 2 wheat seed growth-promoting root of table
The compounds of this invention reaches wheat seed soaking growth-promoting root effect in 30 μ g/mL concentration it can be seen from the result of table 2
To best, hence it is evident that better than control DA-6.
To sum up data, it can be seen that compound of formula I of the invention takes root aspect with significant effect in germination, seedling
Fruit.
Example 5, field experiment: 3 processing are set altogether to apple experiment, each processing selects new upper 3 lifes of Gala apple tree
The comparable bough of growing way carries out, and test takes strain, tree-plot, 3 repetitions, respectively in red fuji apple young fruit period and fruit at random
Expanding stage respectively sprays once, and foliage-spray clear water after harvest, measures the index of quality of apple, wherein VC contains as compareing respectively
Amount is measured using 2,6- dichloropheno-lindophenol method, and soluble sugar content is measured using anthrone colorimetry, as a result such as the following table 3.
3 apple quality index Test data of table
By compound of formula I it can be seen from 3 data of table to apple foliage-spray after so that the output increased 20.5% of apple,
The appearance and interior quality of apple are improved simultaneously, and VC and soluble sugar content are all significantly increased.
Two, bactericidal activity is tested
Example 6, by a certain amount of medicament dissolution in appropriate DMF, be then diluted to 2000mg/L with emulsified water.Using in vitro
Plating, for trying pathogen: rhizoctonia cerealis (Rhizotonia cerealis), fusarium graminearum (Fusarium
Graminearum), phytophthora infestans (Phytophthora infestans), cucumber fusarium axysporum (Fusarium
Oxysporum), tomato early blight bacterium (Alternaria solani), P. capsici (Phytophthora
Capsici), Botryosphaeria berengeriana f. sp (Physalospora piricola), Rhizoctonia solani Kuhn (Rhizoctonia
solani)。
Using biomass growth rate measuring method (mycelium growth rate test), detailed process is: in sterile item
It is respectively drawn under part in 1mL medical fluid injection culture dish, 9mLPDA culture medium is added, 200mg/L drug containing tablet is made after shaking up, to add
The plate of 1mL aqua sterilisa is added to do blank control.Bacterium disk is cut along mycelia outer rim with the punch of diameter 4mm, moves to drug containing tablet
On, it is per treatment in triplicate.Culture dish is placed on culture in 24 ± 1 DEG C of constant incubators, the extension of investigation bacterium disk is straight after 72h
Diameter is averaged.Bacteriostasis rate effect is listed in Table 4 below.
Preventive effect (%)=(blank colony diameter-processing colony diameter)/(blank colony diameter -4) × 100%
Table 4 sterilization test preventive effect (%) data
Compound of formula I is to fusarium graminearum, phytoph-thora capsici leonian, cucumber fusarium axysporum, apple it can be seen from 4 data of table
Fruit ring spot etc. has preventive and therapeutic effect, has the purposes of control fungus damage.
Claims (4)
1. a kind of cinnamic acid naphthalimide ester type compound, structure are shown in formula I:
2. the purposes of compound of formula I according to claim 1, it is characterised in that compound of formula I is used as plant growth regulating
Agent or as prevention and treatment phytoph-thora capsici leonian, wheat scab, ring rot of apple, cucumber fusarium axysporum fungicide.
3. a kind of plant growth regulator composition contains compound of formula I described in claim 1 as plant growth regulator
Active component and agricultural or the acceptable carrier of forestry.
4. the microbicide compositions of a kind of prevention and treatment phytoph-thora capsici leonian, wheat scab, ring rot of apple, cucumber fusarium axysporum, contain
Compound of formula I described in claim 1 is as fungicidal activity component and agricultural or the acceptable carrier of forestry.
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| CN201710018077.5A CN106800534B (en) | 2017-01-10 | 2017-01-10 | A kind of cinnamic acid naphthalimide ester type compound and application thereof |
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| CN106800534B true CN106800534B (en) | 2019-06-18 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669549A (en) * | 2016-02-25 | 2016-06-15 | 青岛科技大学 | Naphthalenedicarboxamide ethylnaphthalene acetic ester type compound and application thereof |
| CN105669550A (en) * | 2016-02-25 | 2016-06-15 | 青岛科技大学 | Naphthalenedicarboxamide ethylhexoate type compound and application thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669549A (en) * | 2016-02-25 | 2016-06-15 | 青岛科技大学 | Naphthalenedicarboxamide ethylnaphthalene acetic ester type compound and application thereof |
| CN105669550A (en) * | 2016-02-25 | 2016-06-15 | 青岛科技大学 | Naphthalenedicarboxamide ethylhexoate type compound and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 萘酰亚胺、吡啶、苯基脲类化合物的研制及应用研究;鞠光秀;《青岛科技大学博士学位论文》;20170610;45-46页表2-5,54-55页表2-11,55页第1-2段，129页表6-5 |
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