CN109232436A - The synthetic method and its agricultural biological activity of cinnoline class compound - Google Patents
The synthetic method and its agricultural biological activity of cinnoline class compound Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
- C07D237/26—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings condensed with carbocyclic rings or ring systems
- C07D237/28—Cinnolines
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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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines
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Abstract
The present invention proposes the synthetic method and its agricultural biological activity of a kind of cinnoline class compound, belong to organic synthesis field, the synthetic method reaction system is simple, under illumination condition, bluestone catalyst, isopropanol is used only as solvent, reaction can be completed at room temperature, reaction time is short, catalyst amount is low, environmental-friendly, effectively meets the requirement of Green Chemistry.The technical solution includes that benzene hydrazine class compound and (diphenyl) acetylene compounds are separately added into reaction vessel, under copper sulphate and isopropanol effect, is reacted 1-2 hours under blue LED lamp illumination condition at 20-25 DEG C of room temperature；After reaction, water and methylene chloride extraction is added, merges organic layer and then removes organic solvent, obtain cinnoline class compound.The present invention can be applied in the application in ring rot of apple prevention and treatment.
Description
Technical field
The invention belongs to organic synthesis field more particularly to a kind of synthetic methods and its agricultural biological of cinnoline class compound
Activity.
Background technique
Cinnoline class compound has multiple biological activities, has obtained satisfied many-sided effect in recent years, and increasingly by
To the attention of whole world chemical research person.Currently, the preparation method of existing cinnoline class compound is to utilize benzene hydrazine class compound
It reacts and is prepared under high temperature heating conditions under metallic catalyst (rhodium, copper) effect with (diphenyl) acetylene compounds.However,
In above-mentioned preparation process, the metallic catalyst that uses is expensive and dosage is more, and metal residual in products therefrom after reacting
Measure higher, therefore, reaction cost is high and environment does not have, therefore at present provided by method and uneconomical, and can not be suitable for
Industrialized production.
Summary of the invention
The present invention proposes the synthetic method and its agricultural biological activity of a kind of cinnoline class compound, the synthetic method reactant
System is simple, under illumination condition, bluestone catalyst is used only, isopropanol is solvent, can be completed reaction at room temperature, when reaction
Between it is short, catalyst amount is low, environmental-friendly, effectively meets the requirement of Green Chemistry.
In order to achieve the above object, the present invention provides a kind of synthetic method of cinnoline class compound, include the following steps:
It is separately added into benzene hydrazine class compound and (diphenyl) acetylene compounds into reaction vessel, makees in copper sulphate and isopropanol
Under, reacted 1-2 hours under blue LED lamp illumination condition at 20-25 DEG C of room temperature；
After reaction, water and methylene chloride extraction is added, merges organic layer and then removes organic solvent, obtain cinnoline class
Compound.
Preferably, the benzene hydrazine class compound has following (A) structural formula:
Wherein, R1Selected from-H ,-F ,-Cl ,-CH3、-CF3Or-OCF3。
Preferably, the (diphenyl) acetylene compounds have following (B) structural formula:
Wherein, R2、R3It is selected from-H ,-Cl or-CH3。
Preferably, the cinnoline class compound has following (C) structural formula:
Wherein, R4Selected from-H ,-F ,-Cl ,-CH3、-CF3Or-OCF3, R5、R6It is selected from-H ,-Cl or-CH3, R7、R8Select
From-H ,-Cl or-CH3。
Preferably, a mM ratio for the benzene hydrazine class compound and (diphenyl) acetylene compounds is 1:2.
Preferably, a mM ratio for the benzene hydrazine class compound and copper sulphate is 1:0.003.
The present invention also provides a kind of compounds that the synthetic method as described in any of the above-described technical solution synthesizes
Application in ring rot of apple prevention and treatment.
Compared with prior art, the advantages and positive effects of the present invention are:
Synthetic method provided by the present invention uses benzene hydrazine class compound and (diphenyl) acetylene compounds for raw material, in sulfuric acid
Copper and the such compound of the lower synthesis of isopropanol effect, the synthetic method reaction system is simple, and under illumination condition, sulfuric acid is used only
Copper catalyst, isopropanol are solvent, and reaction can be completed at room temperature, and the reaction time is short, and catalyst amount is low, environmental-friendly, are had
Effect meets the requirement of Green Chemistry.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
The embodiment of the invention provides a kind of synthetic methods of cinnoline class compound, include the following steps:
S1: benzene hydrazine class compound and (diphenyl) acetylene compounds are separately added into reaction vessel, in copper sulphate and isopropyl
Under alcohol effect, reacted 1-2 hours under blue LED lamp illumination condition at 20-25 DEG C of room temperature；
In this step, cinnoline class compound is synthesized using benzene hydrazine class compound and (diphenyl) acetylene compounds, specifically
, copper sulphate and phenylhydrazine effect generate five-membered ring intermediate, and (diphenyl) acetylene compounds carry out intercalation reaction to five-membered ring, next
The hexichol acetylene compound for walking another molecule carries out intercalation reaction to the intermediate that previous step is reacted, and ultimately produces target product.
What needs to be explained here is that the step reaction without heating, can react under illumination condition, bluestone catalyst dosage is extremely low,
And the reaction time is short, solvent for use only needs a small amount of isopropanol to participate in, environmental-friendly；In addition, this method is selectively good, product
Yield may be up to 99%.It is understood that being in the light that blue LED lamp is 5W for the reaction time set in the step
It is set according under the conditions of, when those skilled in the art can adjust reaction according to blue LED lamp illumination condition combination real reaction situation
Between, as long as ensuring that reaction raw materials reaction is abundant.
S2: after reaction, water and methylene chloride extraction is added, merges organic layer and then remove organic solvent, obtains meat
Quinoline class compound.
Preferably, the benzene hydrazine class compound has following (A) structural formula:
Wherein, R1Selected from-H ,-F ,-Cl ,-CH3、-CF3Or-OCF3。
In a preferred embodiment, the (diphenyl) acetylene compounds have following (B) structural formula:
Wherein, R2、R3It is selected from-H ,-Cl or-CH3。
In a preferred embodiment, the cinnoline class compound has following (C) structural formula:
Wherein, R4Selected from-H ,-F ,-Cl ,-CH3、-CF3Or-OCF3, R5、R6It is selected from-H ,-Cl or-CH3, R7、R8Select
From-H ,-Cl or-CH3。
The concrete structure formula of cinnoline class compound used in specifically being defined in above-described embodiment, it is to be understood that
For cinnoline class compound defined in the present embodiment using cinnoline as parent nucleus, branched structure is relatively simple, but in the present embodiment simultaneously
It is not excluded for the cinnoline class compound being made of the more complicated branched structure of structure.
In a preferred embodiment, a mM ratio for the benzene hydrazine class compound and (diphenyl) acetylene compounds is 1:2.?
In one preferred embodiment, a mM ratio for the benzene hydrazine class compound and copper sulphate is 1:0.003.In above-described embodiment, provide
The specific ratios of benzene hydrazine class compound and (diphenyl) acetylene compounds and benzene hydrazine class compound and copper sulphate, wherein in order to
The mother nucleus structure of expecting compound can accurately be obtained, the ratio of benzene hydrazine class compound and (diphenyl) acetylene compounds is based on reaction
Mechanism requires to be fixed and invariable, and catalyst amount is extremely low, only 0.3%, and the additional amount of solvent isopropanol then it is opposite be can
With excessive, to ensure sufficiently to react.
The present invention also provides a kind of compounds that the synthetic method according to any of the above-described embodiment synthesizes
Application in ring rot of apple prevention and treatment.Specifically, the above-mentioned compound being prepared can be effectively applied to ring rot of apple
In prevention and treatment, medication alone or in combination may be selected as needed, Apple is protected and treated.
In order to become apparent from the synthetic method and its agriculture of introducing cinnoline class compound provided by the embodiment of the present invention in detail
With bioactivity, it is described below in conjunction with specific embodiment.
Embodiment 1
1mmol, 2mmol, 0.003mmol copper sulphate and 2ml isopropanol are separately added into reaction vessel, in room temperature 20-
Blue 5W LED lamplight is reacted 1 hour under the conditions of shining at 25 DEG C；After reaction, water and methylene chloride extraction is added, is associated with
Then machine layer removes organic solvent, obtain following C1 compound:
Magnetic resonance spectroscopy analysis is carried out to above-mentioned yellow solid, data are as follows:
1H NMR(500MHz,CDCl3) δ=8.53 (d, J=8.5Hz, 1H), 7.74 (s, 1H), 7.61 (d, J=8.2Hz,
1H), 7.58 (d, J=7.0Hz, 1H), 7.43-7.31 (m, 6H), 7.28 (d, J=4.1Hz, 1H), 7.11 (d, J=7.0Hz,
2H), 7.06-7.00 (m, 3H), 6.96 (t, J=7.4Hz, 1H), 6.92-6.87 (m, 2H), 6.85 (t, J=7.6Hz, 2H),
6.56 (d, J=7.3Hz, 2H), 6.23 (s, 1H)；
13C NMR(125MHz,CDCl3) δ=153.9,149.0,144.4,141.8,139.9,137.1,137.0,
133.6,133.0,132.1,131.2,130.7,130.5,129.7,129.6,129.1,128.3,128.1,127.8,
127.6,127.6,127.0,126.7,126.5,125.0,124.7；
After identified, spectral data is corresponding with structural formula, it was demonstrated that synthesis is 3- (2- (1,2- bis- phenyl vinyls)-
Phenyl) -4- phenyl cinnoline, yield 98%.
Embodiment 2
1mmol, 2mmol, 0.003mmol copper sulphate and 2ml isopropanol are separately added into reaction vessel, in room temperature 20-
Blue 5W LED lamplight is reacted 1 hour under the conditions of shining at 25 DEG C；After reaction, water and methylene chloride extraction is added, is associated with
Then machine layer removes organic solvent, obtain following C2 compound:
Magnetic resonance spectroscopy analysis is carried out to above-mentioned yellow solid, data are as follows:
1H NMR(500MHz,CDCl3) δ=7.54 (td, J=8.0,5.1Hz, 1H), 7.47-7.31 (m, 8H), 7.28
(s, 1H), 7.10 (d, J=7.8Hz, 2H), 7.05 (dd, J=5.1,1.5Hz, 3H), 7.00 (t, J=7.4Hz, 1H), 6.89
(t, J=7.6Hz, 4H), 6.58 (d, J=8.1Hz, 2H), 6.25 (s, 1H)；
13C NMR(125MHz,CDCl3) δ=158.6 (d, J=263.0Hz), 154.9,144.4,141.9,140.3,
140.2,139.9,137.2,136.7,133.4,132.5,132.0,131.4,130.8,130.7,130.6,129.8,
129.2,128.4,128.1,127.6,127.1,127.0,126.6,126.5,121.0,113.2；
After identified, spectral data is corresponding with structural formula, it was demonstrated that synthesis is 3- (2- (1,2- bis- phenyl vinyls)-
Phenyl) the fluorine-based cinnoline of -4- phenyl -8-, yield 95%.
Embodiment 3
1mmol, 2mmol, 0.003mmol copper sulphate and 2ml isopropanol are separately added into reaction vessel, in room temperature 20-
Blue 5W LED lamplight is reacted 1 hour under the conditions of shining at 25 DEG C；After reaction, water and methylene chloride extraction is added, is associated with
Then machine layer removes organic solvent, obtain following C3 compound:
Magnetic resonance spectroscopy analysis is carried out to above-mentioned yellow solid, data are as follows:
1H NMR(500MHz,CDCl3) δ=8.63 (d, J=8.8Hz, 1H), 7.98 (s, 1H), 7.91 (d, J=8.9Hz,
1H), 7.52-7.35 (m, 6H), 7.32-7.28 (m, 1H), 7.11 (d, J=7.3Hz, 2H), 7.07-7.00 (m, 3H), 6.96
(t, J=7.4Hz, 1H), 6.90-6.82 (m, 4H), 6.55 (d, J=7.3Hz, 2H), 6.21 (s, 1H)；
13C NMR(125MHz,CDCl3) δ=155.1,148.8,144.5,141.8,139.8,136.9,136.41,
133.7,132.6,132.2,131.9,131.5,131.3,130.7,129.6,129.6,129.2,128.7,128.5,
128.3,127.9,127.8,127.3,127.0,126.7,125.3,124.1,123.5,123.2；
After identified, spectral data is corresponding with structural formula, it was demonstrated that synthesis is 3- (2- (1,2- bis- phenyl vinyls)-
Phenyl) -4- phenyl -6- trifluoromethyl cinnoline, yield 97%.
Embodiment 4
1mmol, 2mmol, 0.003mmol copper sulphate and 2ml isopropanol are separately added into reaction vessel, in room temperature 20-
Blue 5W LED lamplight is reacted 1 hour under the conditions of shining at 25 DEG C；After reaction, water and methylene chloride extraction is added, is associated with
Then machine layer removes organic solvent, obtain following C4 compound:
Magnetic resonance spectroscopy analysis is carried out to above-mentioned yellow solid, data are as follows:
1H NMR(500MHz,CDCl3) δ=8.45 (d, J=9.0Hz, 1H), 7.69 (dd, J=9.0,2.1Hz, 1H),
7.59 (d, J=2.1Hz, 1H), 7.47-7.30 (m, 6H), 7.27 (s, 1H), 7.08 (d, J=7.1Hz, 2H), 7.03 (dd, J
=5.0,1.8Hz, 3H), 6.97 (t, J=7.4Hz, 1H), 6.90-6.80 (m, 4H), 6.60-6.48 (m, 2H), 6.22 (s,
1H)；
13C NMR(125MHz,CDCl3) δ=154.5,147.3,144.5,141.8,139.8,137.3,137.0,
136.7,133.1,132.3,132.0,131.6,131.3,130.9,130.7,130.5,129.7,129.2,128.4,
128.2,127.1,127.2,126.9,126.7,125.7,123.6；
After identified, spectral data is corresponding with structural formula, it was demonstrated that synthesis is 3- (2- (1,2- bis- phenyl vinyls)-
Phenyl) -4- phenyl -6- chloro cinnoline, yield 98%.
Embodiment 5
1mmol, 2mmol, 0.003mmol copper sulphate and 2ml isopropanol are separately added into reaction vessel, in room temperature 20-
Blue 5W LED lamplight is reacted 1 hour under the conditions of shining at 25 DEG C；After reaction, water and methylene chloride extraction is added, is associated with
Then machine layer removes organic solvent, obtain following C5 compound:
Magnetic resonance spectroscopy analysis is carried out to above-mentioned yellow solid, data are as follows:
1H NMR(500MHz,CDCl3) δ=8.58 (d, J=9.3Hz, 1H), 7.61 (dd, J=9.3,1.5Hz, 1H),
7.48-7.35 (m, 7H), 7.30-7.26 (m, 1H), 7.11-7.03 (m, 5H), 6.96 (t, J=7.4Hz, 1H), 6.90-6.83
(m,4H),6.59-6.53(m,2H),6.21(s,1H)；
13C NMR(125MHz,CDCl3) δ=154.4,150.1,147.1,144.6,141.7,139.8,137.0,
136.5,133.1,132.8,132.6,131.9,131.2,130.6,130.6,129.7,129.2,128.6,128.2,
127.7,127.1,126.9,126.7,125.7,123.6,120.3,114.53；
After identified, spectral data is corresponding with structural formula, it was demonstrated that synthesis is 3- (2- (1,2- bis- phenyl vinyls)-
Phenyl) -4- phenyl -6- trifluoromethoxy cinnoline, yield 99%.
Embodiment 6
1mmol, 2mmol, 0.003mmol copper sulphate and 2ml isopropanol are separately added into reaction vessel, in room temperature 20-
Blue 5W LED lamplight is reacted 1 hour under the conditions of shining at 25 DEG C；After reaction, water and methylene chloride extraction is added, is associated with
Then machine layer removes organic solvent, obtain following C6 compound:
Magnetic resonance spectroscopy analysis is carried out to above-mentioned yellow solid, data are as follows:
1H NMR(500MHz,CDCl3) δ=7.61 (d, J=6.9Hz, 1H), 7.54-7.49 (m, 1H), 7.43-7.35
(m, 5H), 7.24 (d, J=1.0Hz, 1H), 7.01 (dd, J=14.3,8.4Hz, 4H), 6.82 (d, J=8.4Hz, 2H), 6.78
(d, J=8.5Hz, 2H), 6.40 (d, J=8.4Hz, 2H), 6.16 (s, 1H), 3.01 (s, 3H)；
13C NMR(125MHz,CDCl3) δ=152.2,148.1,145.1,140.1,138.8,137.2,135.7,
134.7,134.5,133.5,133.3,133.0,132.2,132.3,131.6,131.1,130.9,130.5,130.2,
128.5,128.3,128.2,127.6,124.3,122.4,17.8；
After identified, spectral data is corresponding with structural formula, it was demonstrated that synthesis is 3- (2- (1,2- bis- (4- chlorphenyl) second
Alkenyl) -4- chlorphenyl) -4- (4- chlorphenyl) -8- methyl cinnoline, yield 93%.
Embodiment 7
1mmol, 2mmol, 0.003mmol copper sulphate and 2ml isopropanol are separately added into reaction vessel, in room temperature 20-
Blue 5W LED lamplight is reacted 1 hour under the conditions of shining at 25 DEG C；After reaction, water and methylene chloride extraction is added, is associated with
Then machine layer removes organic solvent, obtain following C7 compound:
Magnetic resonance spectroscopy analysis is carried out to above-mentioned brown solid, data are as follows:
1H NMR(500MHz,CDCl3) δ=8.52 (d, J=8.5Hz, 1H), 7.75-7.68 (m, 1H), 7.60 (d, J=
8.4Hz, 1H), 7.56-7.51 (m, 1H), 7.25 (s, 3H), 7.10 (d, J=7.6Hz, 1H), 7.06 (s, 1H), 6.89-6.83
(m, 3H), 6.79 (d, J=5.4Hz, 3H), 6.66 (s, 1H), 6.58 (d, J=7.3Hz, 1H), 6.35 (s, 1H), 6.15 (s,
1H),6.08(s,1H),2.34(s,3H),2.28(s,3H),2.09(s,3H),1.85(s,3H)；
13C NMR(125MHz,CDCl3) δ=154.3,149.0,141.5,140.1,137.4,137.2,136.9,
136.8,136.5,133.6,133.2,132.7,131.5,130.8,130.6,130.2,130.2,130.1,129.6,
129.5,128.7,127.8,127.5,127.4,127.3,127.1,126.8,126.0,125.3,125.0,21.3,21.1,
20.9,20.6；
After identified, spectral data is corresponding with structural formula, it was demonstrated that synthesis is 3- (2- (1,2- bis- (3- benzyl) second
Alkenyl) -5- benzyl) -4- (3- benzyl) cinnoline, yield 96%.
Performance test
Using fruit needle point method test target compound to the control efficiency of ring rot of apple.
Protective effect measurement: picking health is fresh, shapes and sizes are uniform, the consistent Apple of maturity, and surface is used
75% alcohol wipe disinfection, dries spare；It is 50mg/L, 20mg/L for reagent that target compound, which is configured to mass concentration,
Liquid dips in medicine with cotton and is gently applied to Apple surface, is placed in the plastic tub sterilized, and basin bottom paving is with filter paper and adds sterile water
Moisturizing, for 24 hours after fruit surface with needle point method be inoculated with Botryosphaeria berengeriana f. sp bacteria cake.
Therapeutic effect measurement: Apple processing is measured with protective effect.Difference is first to be inoculated with apple under the conditions of moisturizing
Target spot pathogen bacteria cake is coated afterwards for 24 hours for reagent liquid.3 repetitions of every processing, 1 Apple of every repetition are sky with solvent
White control.The lesion diameter that each processing fruit is measured after 6d, is calculated according to the following formula preventive effect, measurement result is shown in Table 1.
Lesion diameter/mm=measures lesion diameter average value-bacteria cake diameter；
Relative control effect=(control lesion diameter-processing lesion diameter)/control lesion diameter × 100%
Control efficiency of each compound of table 1 in 50mg/L and 20mg/L
From the data in table 1, it can be seen that C2-C3, C5-C6 compound as prepared by the above embodiment of the present invention are for apple wheel line
Disease has preferable control efficiency, wherein C2, C3, C6 show more outstanding treatment in 50mg/L and 20mg/L and make
With especially in 20mg/L, the therapeutic effect of C3 can reach 96%, and in 50mg/L, the therapeutic effect of C2, C3 be can reach
97%, C6 then show the effect of being more effectively protected in 50mg/L and 20mg/L, and effect can reach 98% or more.
Therefore, it in order to effectively play control efficiency, may be selected that compound prepared in the above embodiments is used alone or in combination, to obtain
Better control efficiency.
Claims (7)
1. the synthetic method of cinnoline class compound, which comprises the steps of:
It is separately added into benzene hydrazine class compound and (diphenyl) acetylene compounds into reaction vessel, is acted in copper sulphate and isopropanol
Under, it is reacted 1-2 hours under blue LED lamp illumination condition at 20-25 DEG C of room temperature；
After reaction, water and methylene chloride extraction is added, merges organic layer and then removes organic solvent, obtain cinnoline class chemical combination
Object.
2. synthetic method according to claim 1, which is characterized in that the benzene hydrazine class compound has following (A) structure
Formula:
Wherein, R1Selected from-H ,-F ,-Cl ,-CH3、-CF3Or-OCF3。
3. synthetic method according to claim 1, which is characterized in that the (diphenyl) acetylene compounds have following (B)
Structural formula:
Wherein, R2、R3It is selected from-H ,-Cl or-CH3。
4. synthetic method according to claim 1, which is characterized in that the cinnoline class compound has following (C) structure
Formula:
Wherein, R4Selected from-H ,-F ,-Cl ,-CH3、-CF3Or-OCF3, R5、R6It is selected from-H ,-Cl or-CH3, R7、R8Be selected from-
H ,-Cl or-CH3。
5. synthetic method according to claim 1, which is characterized in that the benzene hydrazine class compound and diphenyl acetylene class chemical combination
A mM ratio for object is 1:2.
6. synthetic method according to claim 1, which is characterized in that mM of the benzene hydrazine class compound and copper sulphate
Than for 1:0.003.
7. the compound that synthetic method according to claim 1-6 synthesizes is in ring rot of apple prevention and treatment
Using.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103044490A (en) * | 2012-10-16 | 2013-04-17 | 中科院广州化学有限公司 | Novel phenylcinnoline iridium complex as well as preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103044490A (en) * | 2012-10-16 | 2013-04-17 | 中科院广州化学有限公司 | Novel phenylcinnoline iridium complex as well as preparation method and application thereof |
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