CN107827885A - A kind of 2,4 two cinnamoyl chloride thioureas of Pyrazolopyridine substitution and its application - Google Patents
A kind of 2,4 two cinnamoyl chloride thioureas of Pyrazolopyridine substitution and its application Download PDFInfo
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- CN107827885A CN107827885A CN201711142342.7A CN201711142342A CN107827885A CN 107827885 A CN107827885 A CN 107827885A CN 201711142342 A CN201711142342 A CN 201711142342A CN 107827885 A CN107827885 A CN 107827885A
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- pyrazolopyridine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
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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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
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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
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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- General Health & Medical Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
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Abstract
The invention discloses a kind of 2,4 two cinnamoyl chloride thioureas of Pyrazolopyridine substitution, its application as plant growth regulator is also disclosed.Germination percentage, hestening rooting are significantly improved by the use of the compound in the present invention as plant growth regulator, enter fissional effect, can effectively regulating plant growth.
Description
Technical field
The present invention relates to plant growth regulator technical field, and in particular to a kind of 2,4- dichloros of Pyrazolopyridine substitution
Cinnamoyl thiourea and its purposes as plant growth regulator.
Background technology
Plant growth regulator can influence the growth and development with Effective Regulation plant, and the volume increase to crops and fruits and vegetables carries
Matter has significant role.The B of CN 103719082 disclose a kind of cinnamide compound answering as plant growth regulator
With can be widely applied to plant and promote seed sprouting, promoting root growth, volume increase, degeneration-resistant and upgrading.The cell division agriculturally commonly used at present
Plain forchlorfenuron and Thidiazuron are the ureas basic element of cell division, but weak point is that synthesis step is long, production cost is high, production process
Three-waste pollution is serious etc., therefore Development and Production technique is simple, cost is low, the basic element of cell division kind of high-efficiency environment friendly has important meaning
Justice.
In the prior art, the cinnamoyl chloride Thioureas of 2,4- bis- that a kind of Pyrazolopyridine substitutes as described in the present invention
Compound and its not disclosed as the purposes of plant growth regulator.
The content of the invention
The technical problems to be solved by the invention are：In view of the shortcomings of the prior art, there is provided one kind promotes seed to sprout, promote
Take root, increase production, the cinnamoyl chloride thioureas of 2,4- bis- of Pyrazolopyridine safe to use substitution, using it for crops
It can significantly increase production with water fruits and vegetables and improve quality.
In order to solve the above technical problems, the technical scheme is that：
The cinnamoyl chloride thioureas of 2,4- bis- of Pyrazolopyridine substitution provided by the invention, its structure such as Formulas I institute
Show：
Wherein R1=H, CH3。
Compound of formula I can be made by following reaction, and specific preparation method is shown in present invention synthesis example.
It is living in said composition present invention additionally comprises plant growth regulator composition of the compound of formula I as active component
Property component refer to compound of formula I or compound of formula I and given birth to other active components such as plant such as Nafusaku, DA-6, indolebutyric acid sodium
The composition of a kind of, two or more compositions of long conditioning agent；
Also include acceptable carrier in agricultural or forestry in the plant growth regulator composition.Plant growth of the present invention
Regulating composition can also add one or more of other in the plant growth regulator composition of the present invention as needed
Insecticide, bactericide, a large amount of or trace-element fertilizer etc., thus can produce additional excellent results.
Wherein the formulation of plant growth regulator composition can be suspending agent, emulsion, microemulsion, wettable powder, water
Dispersive granule etc., in order to improve the utilization rate of active principle, appropriate surfactant is usually added into formulated.
After employing above-mentioned technical proposal, the beneficial effects of the invention are as follows：
The nitrogen heterocyclic ring cinnamamide carbamide compounds of present invention design synthesis, contain Pyrazolopyridine and cinnamoyl amino
Group, the group that activity is adjusted with different plants is attached by thiocarbamide key, obtains a kind of novel plant growth of structure
Conditioning agent, it can efficiently promote plant growth, and reaching makes crop yield, high-quality effect, and have certain bactericidal action,
And it is nontoxic to environment and people, animal, it has good biological degradability, and synthetic method is simple, cost is low, building-up process
Pollute small, belong to environmentally friendly product.Compound of formula I has the characteristics of efficient, safety, dosage is few, cost is low, has very high
Application value and commercialization potentiality.
Wheat seed 24h is soaked with the μ g/mL solution of plant growth regulator 30 of the present invention, is remarkably improved wheat germination
Rate, its promotion rate of germinateing is up to 34%, higher than the commodity such as DA-6,6-BA (see example 3, table 1)；It is substantially better than in terms of growth-promoting root
DA-6,6-BA (see example 4, table 2).Formula I is significantly better than control compounds thiophene to cucumber cotyledons expansion activity
Grand (see example 5, the table 3) field experiment of benzene shows, the plant growth regulator can make that wheat, the cane of corn crop be sturdy, leaf
Piece it is generous leaf color it is dark green, leaf longevity extend, improve drought resisting, waterlogging-resistant, resistance against diseases, wheat increase yield is reached 26-28%, make jade
Rice volume increase reaches 29-31%.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, below in conjunction with specific embodiment, to this
Invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, not
For limiting the present invention.
Embodiment 1 (preparation of compound of formula I)
(1) preparation of cinnamoyl chloride：
15.2g (0.1mol) cinnamic acids and 120mL toluene are separately added into 250mL three-necked flasks, is dripped in clean constant pressure
In liquid funnel add 18.15g (0.15mol) thionyl chloride, keep it is per second 1 drop speed be added dropwise thionyl chloride, be stirred at room temperature to
Thionyl chloride drop finishes.Backflow is warming up to, TLC detection reactions are completed；React and flaxen reaction solution is poured into clean nothing after terminating
In the single-necked flask of water, 80 DEG C of water-bath revolvings remove solvent, obtain cinnamoyl chloride 16.9g.
(2) preparation of cinnamoyl isothiocyanates：
Obtained cinnamoyl chloride is diluted with 60mL ethyl acetate, instills dropwise and the different sulphur cyanogen of 14.55g (0.15mol) is housed
In the 250mL there-necked flasks of sour potassium and 50mL ethyl acetate, backflow is warming up to, it is 1-2 drops/s to control rate of addition, reacts about 4h,
TLC detection reactions are completed；Now solution is orange-yellow suspension, filters, is washed with ethyl acetate, obtain brownish red filtrate.
(3) preparation of Formulas I a compounds：
13.4g (0.1mol) 3- amino -1H- pyrazolos [3,4-b] pyridine is added in 250mL three-necked flasks, then is added
Enter 18.9g (0.1mol) cinnamoyl isothiocyanates, agitating device and reflux are installed, be warming up to backflow, react about 5-
6h, TLC detection reaction are completed；Reaction solution is cooled to room temperature, there are a large amount of yellow solids to separate out.Filter, obtain yellow solid, use
Recrystallisation from isopropanol, drying, obtains product 32.7g, yield 86%.
Formulas I a compounds1HNMR/ (500MHz, DMSO-d6) δ (ppm):(6.906-6.948 d, 2H ,-CH=CH-),
7.233-7.335(m,3H,ArH),7.358-8.554(m,3H,ArH),12.004(s,1H,-NH),12.551(s,1H,-
NH),13.516(s,1H,-NH)。
By above method, by 1- methyl -3- amino-pyrazoles, simultaneously [3,4-b] pyridine reacts with cinnamoyl isothiocyanates,
Obtain Formulas I b compounds.
Formulas I b compounds1H NMR/ (500MHz, DMSO-d6) δ (ppm):3.586(s,3H,-CH3),6.908-6.951
(d, 2H ,-CH=CH-), 7.236-7.337 (m, 3H, ArH), 7.357-8.553 (m, 3H, ArH), 12.024 (s, 1H ,-NH),
12.562(s,1H,-NH)。
Embodiment 2
The preparation of 10% compound of formula I suspending agent：10g compound of formula I, 2g sodium lignin sulfonates, the poly- carboxylics of 3g are weighed respectively
Hydrochlorate dispersant Sokalan CP 5 (maleic-acrylic acid sodium salt), (the water-based silicon emulsifications of THIX-108 of 1g organosilicon breasts defoamer
Defoamer), 2g aluminium-magnesium silicates and 5g ethylene glycol add 77g water, stirred in 250mL beakers, and 2h is ground with sand mill,
Rotating speed is 3000 revs/min, detects 3-5 μm of granularity, obtains white mobility suspending agent.
In order to preferably confirm the plant growth regulator in the present invention have it is good promote seed to sprout, growth-promoting root
Effect, biological activity determination experiment has been done below.
Example 3 (Seeds Germination Tests)
Carried out using paper bed sproutung method：10% compound of formula I suspending agent prepared by embodiment 2 is diluted to 5% suspending agent,
By 5% compound of formula I suspending agent, 5%DA-6 aquas, 5%6-BA suspending agents, it is 10 μ g/ to be diluted with distilled water into concentration respectively
ML, 20 μ g/mL, 30 μ g/mL, 60 μ g/mL and 120 μ g/mL plant growth regulator solution.It is uniform, full to select Seed size
Full wheat seed, after being sterilized with hypochlorite solution to seed, soaked seed in beaker with above-mentioned dilution and cultivate 24h, often
100 seeds are handled, 3 repetitions, seed is uniformly placed in the culture dish of double-layer filter paper after processing, kept between seed
A certain distance, it is well placed seed and puts it into 25 DEG C of insulation vernalization processing in complete intelligent climate box afterwards, during which regularly to add
Entering distilled water makes filter paper keep moistening, and the germination of each processing is observed during vernalization, and radicel length is about with the 1/2 of seed length
Standard, wheat seed germination percentage in each culture dish is counted after 24h, while with DA-6,6-BA of same concentrations and clear water (CK)
Compare, while calculate each dilution germination promotion rate, it is as a result as shown in table 1 below.
The wheat seed germinating of table 1 is tested
From the experimental data of table 1, the wheat germination rate of formula I processing is at optium concentration (30 μ g/mL)
It is better than contrast agents DA-6 and 6-BA down, is more significantly better than the situation of clear water processing (CK).
Example 4 (experiment of seed soaking growth-promoting root)
10% compound of formula I suspending agent is diluted to 5% suspending agent, by 5% compound of formula I suspending agent, 5%DA-6 water
Agent, 5%6-BA suspending agents, concentration is diluted with distilled water into respectively as 10 μ g/mL, 20 μ g/mL, 30 μ g/mL, 60 μ g/mL and 120
μ g/mL plant growth regulator solution.The wheat seed that Seed size is uniform, full is selected, with hypochlorite solution to seed
After being sterilized, soaked seed in beaker with above-mentioned dilution and cultivate 8h, often handle 20 wheats, 3 repetitions, by seed after processing
Uniformly it is placed on the paper bed of moistening, is maintained a certain distance between seed, to ensure that seed fully absorbs moisture, embryo when putting bed
Portion is well placed seed and puts it into progress vernalization processing 24h in complete intelligent climate box afterwards, during which upward towards the same side
Timing, which adds distilled water, makes paper bed keep moistening.Treat that wheat main root exposes 2mm or so, by its kind in the solid culture solidified
In base, it is then placed in complete intelligent climate box and is cultivated.It is high with kind of calliper main root, stem after 40h, and do detailed record.
Compared simultaneously with DA-6,6-BA of same concentrations and clear water processing (CK), it is as a result as shown in table 2 below.
The wheat seed growth-promoting root of table 2 is tested
The compounds of this invention reaches in 30 μ g/mL concentration to wheat seed soaking rush rooting efficiency it can be seen from the result of table 2
To optimal, better than control DA-6,6-BA is significantly better than.
Example 5 (cucumber cotyledons augmentation test)
It is that Tianjin grinds No. 4 for examination cucumber variety, is sowed after seed soaking in the enamel tray with cover of 0.7% agar is filled, be placed in 26
72h is cultivated under DEG C dark situation, selects that complete cotyledon of uniform size is stand-by, and sample preparation uses phytohormone activity substance-measuring
In filter paper enzyme.Sample test concentration is 10,1,0.1 μ g/mL, and compound of formula I, Thidiazuron solvent are DMF.
Specific practice is：Sample is prepared as to 100,10,1 μ g/mL mother liquors respectively, takes each mother liquor 0.3mL uniformly to drip respectively
In on Φ 6cm filter paper, after solvent air-dries, in Φ 6cm culture dish, respectively it is put into the filter paper 1 containing sample and opens, adds
3mL distilled water, cotyledon 10, as 10,1,0.1 μ g/mL processing.Using distilled water as control, 26 DEG C are placed in, 3000Lx light intensity rings
Cultivated under border, every 10 slice, thin piece leaf fresh weight is measured after 72h.3 repetitions, results averaged are often handled, result of the test is shown in Table 3.
The cucumber cotyledons of table 3 expand contrast test
From the test data of table 3, formula I has good cell division activity, and cucumber cotyledons are expanded
Open activity and be significantly better than control compounds Thidiazuron.
Example 6 (bactericidal activity determination experiment)
By a certain amount of medicament dissolution in appropriate DMF (DMF), then use and contain a certain amount of polysorbas20
Emulsifier aqueous solution is diluted to 50mg/L.Using in vitro Plating, for trying pathogen：Botryosphaeria berengeriana f. sp (Physalospora
Piricola), rhizoctonia cerealis (Rhizotonia cerealis), tomato early blight bacterium (Alternation solani),
Phytophthora infestans (Phytophthora infestans), Rhizoctonia solani Kuhn (Rhizoctonia solani).Using
Biomass growth rate determination method, detailed process are：Aseptically respectively draw in 1mL decoctions injection culture dish, add
9mLPDA culture mediums (potato dextrose agar), 100mg/L drug containing flat boards are made after shaking up, to add 1mL sterilizings
The flat board of water does blank control.Bacterium disk is cut along mycelia outer rim with diameter 4mm card punch, is moved on drug containing flat board, every time place
Reason is in triplicate.Culture dish is placed in 24 ± 1 DEG C of constant incubators and cultivated, the diameter of bacterium disk extension everywhere is investigated after 72h, asks flat
Average, relative bacteriostasis rate is calculated compared with blank control, test concentrations are 100 μ g/mL, and test result is shown in Table 4.
Preventive effect (%)=(blank colony diameter-processing colony diameter)/(blank colony diameter -4) × 100%
Table 4 sterilization test preventive effect (%) data
From upper table data, compound of formula I is to Botryosphaeria berengeriana f. sp (Physalospora piricola), wheat line
Rot bacterium (Rhizotonia cerealis), tomato early blight bacterium (Alternaria solani), phytophthora infestans
(Phytophthora infestans), Rhizoctonia solani Kuhn (Rhizoctonia solani) have certain inhibitory action.
The upper only presently preferred embodiments of the present invention, is not intended to limit the invention, all spirit in the present invention
With all any modification, equivalent and improvement made within principle etc., it should be included in the scope of the protection.
Claims (3)
1. a kind of cinnamoyl chloride thioureas of 2,4- bis- of Pyrazolopyridine substitution, it is characterised in that the compound has
Structure shown in Formulas I：
Wherein R1For H or CH3。
2. a kind of cinnamoyl chloride thioureas of 2,4- bis- of Pyrazolopyridine substitution as claimed in claim 1 are as plant
The application of growth regulator.
3. a kind of cinnamoyl chloride thioureas of 2,4- bis- containing Pyrazolopyridine as claimed in claim 1 substitution and agriculture
The composition of acceptable carrier is configured to application of the preparation as plant growth regulator in industry or forestry.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103709158A (en) * | 2013-12-26 | 2014-04-09 | 青岛科技大学 | Pyrazolopyrimidine ureas compound and application thereof |
| CN103719082A (en) * | 2014-01-22 | 2014-04-16 | 杭州宇龙化工有限公司 | Application of taking cinnamamides compound as plant growth regulator |
| CN104351231A (en) * | 2014-10-11 | 2015-02-18 | 中国农业大学 | Application of 4-chlorocinnamaldehyde thiosemicarbazone in plant disease control |
-
2017
- 2017-11-17 CN CN201711142342.7A patent/CN107827885A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103709158A (en) * | 2013-12-26 | 2014-04-09 | 青岛科技大学 | Pyrazolopyrimidine ureas compound and application thereof |
| CN103719082A (en) * | 2014-01-22 | 2014-04-16 | 杭州宇龙化工有限公司 | Application of taking cinnamamides compound as plant growth regulator |
| CN104351231A (en) * | 2014-10-11 | 2015-02-18 | 中国农业大学 | Application of 4-chlorocinnamaldehyde thiosemicarbazone in plant disease control |
Non-Patent Citations (2)
| Title |
|---|
| 吕献海 等: "肉桂酰基硫脲衍生物的合成及杀菌活性", 《应用化学》 * |
| 薛思佳 等: "超声辐射合成桂皮酰基硫脲嘧啶衍生物", 《应用化学》 * |
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Application publication date: 20180323 |