CN106818770B - A kind of application of the formamide of azophenlyene 1 transformation compound 18 1 in Sclerotinia sclerotiorum is suppressed - Google Patents
A kind of application of the formamide of azophenlyene 1 transformation compound 18 1 in Sclerotinia sclerotiorum is suppressed Download PDFInfo
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- CN106818770B CN106818770B CN201710169174.4A CN201710169174A CN106818770B CN 106818770 B CN106818770 B CN 106818770B CN 201710169174 A CN201710169174 A CN 201710169174A CN 106818770 B CN106818770 B CN 106818770B
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- azophenlyene
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- VUTPKOBBLCZCCI-QLYXXIJNSA-N C=C(C(C(Nc1cccc2c1cccc2)=O)=CC#C1)/C1=N\c(cccc1)c1N Chemical compound C=C(C(C(Nc1cccc2c1cccc2)=O)=CC#C1)/C1=N\c(cccc1)c1N VUTPKOBBLCZCCI-QLYXXIJNSA-N 0.000 description 1
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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
- A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G13/00—Protecting plants
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
- C07D241/46—Phenazines
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- Agronomy & Crop Science (AREA)
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Abstract
A kind of application of the formamide of azophenlyene 1 transformation compound 18 1 in Sclerotinia sclerotiorum is suppressed, the formamide of azophenlyene 1 transformation compound 18 1 (structural formula is as follows) is using the formamide of azophenlyene 1 as parent, is obtained through structure of modification.The present invention determines the inhibitory action of 18 1 pairs of Sclerotinia sclerotiorums of transformation compound using growth rate method simultaneously, as a result shows：The inhibition of 18 1 pairs of Sclerotinia sclerotiorums of transformation compound is good, and the inhibition is better than its formamide of parental phenazine 1, shows that the transformation compound 18 1 can be as the lead compound of prevention and control sclerotinia sclerotiorum novel pesticide.
Description
Technical field
The invention belongs to pesticides discovery field, more particularly to a kind of azophenlyene -1- formamides transformation compound 18-1 is suppressing
Application in Sclerotinia sclerotiorum (Sclerotinia sclerotiorum).
Background technology
Rape is the important oil crops in China, and seed oil content has higher economic value between 33-55%.Oil
Dish can not only be used for squeezing edible oil and feed, but also have been widely used in medicine, industry, food etc. tool.Most
Near result of study shows that China is that rapeseed cultivation big country, its area are about 7,000,000 hectares in the world, is important rape life
Produce state.
The growth cycle length of rape, is often disturbed by various factors, and wherein sclerotinia sclerotiorum is the weight for influenceing rape yield increasing
Want factor.The disease is also known as stem rot, the mould root and stem of certain plants, white stalk, empty stalk etc., is a kind of fungal disease as caused by sclerotinite, can post
It is born in the various plants of section more than 70 400.The sick host in addition to crucifer, can also colonize in peanut, broad bean, sunflower,
On the crops such as lettuce.The presence of sclerotium is to cause the primary source of infection of sclerotinia sclerotiorum.Caused ascospore exists after sclerotial germination
Propagated in air, ascospore is typically fallen on the petal of plant first infects petal, is then fallen by the petal of bacteria infection
Plant is infected on to the cauline leaf of plant.The sick generation can cause rape mass of 1000 kernel to reduce, silique is reduced, the flat, plant of seed wrinkle
It is early withered etc., cause rape underproduction 10%-50%, or even up to 80%, to bringing massive losses in production.
The method that sclerotinia sclerotiorum is prevented and treated in production relies primarily on chemical prevention, the chemistry available for control sclerotinia sclerotiorum
Medicament has ergosterol biosynthesis inhibitor class such as prochloraz, Tebuconazole；Benzimidazole such as carbendazim, thiophanate methyl；
Substituted benzene such as Bravo；Dicarboximide class such as dimethachlon, procymidone, iprodione, vinclozolin；Triazole type such as the third ring
Azoles；Carbamates such as diethofencarb etc., but long-term a large amount of single use chemical agents, not only pollute environment, it is flat to destroy ecology
Weighing apparatus, and be also easy to cause germ to develop immunity to drugs.Therefore, the novel pesticide for seeking preventing and treating sclerotinia sclerotiorum is very urgent.
At present, developing the approach of novel pesticide mainly has chemical synthesis, the structure of modification of existing compound, from plant or micro- life
Novel compound of screening structure etc. in object, wherein the structure of modification of compound is the method for developing novel pesticide, not only
R＆D costs can be saved, and short-term benefit is notable.Azophenlyene -1- the formamides with bacteriostasis were once studied by this seminar,
But its bacteriostasis is limited, therefore, this seminar using azophenlyene -1- formamides as parent, by structure of modification and obtain azophenlyene -
1- formamides transformation compound 18-1.For the potentiality to be exploited of the clearly modification, the present invention have rated it to rape sclerotium first
The inhibition of germ and synergistic effect, it is intended to which the novel pesticide of horn of plenty preventing and treating sclerotinia sclerotiorum provides material base.
The content of the invention
The technical problem to be solved by the invention is to provide a kind of azophenlyene -1- formamides transformation compound 18-1 to suppress
Application in Sclerotinia sclerotiorum, transformation compound 18-1 are to be obtained using azophenlyene -1- formamides as parent through structure of modification, this
Invention determines inhibitory action of the transformation compound 18-1 to Sclerotinia sclerotiorum using growth rate method simultaneously, the results showed that
The transformation compound 18-1 is good to the inhibition of Sclerotinia sclerotiorum, and its inhibitory action to Sclerotinia sclerotiorum is better than it
Parental phenazine -1- formamides.
In order to solve the above technical problems, the technical solution adopted in the present invention is：A kind of azophenlyene -1- formamides transform chemical combination
Applications of the thing 18-1 in Sclerotinia sclerotiorum is suppressed.
Present invention simultaneously provides a kind of azophenlyene -1- formamides transformation compound 18-1 to prepare prevention and control sclerotinia sclerotiorum agricultural chemicals
In application.
Above-mentioned azophenlyene -1- formamides transformation compound 18-1 structural formula is as follows：
Above-mentioned azophenlyene -1- formamides transformation compound 18-1 is using azophenlyene -1- formamides as parent, by azophenlyene -1- formyls
Amine hydrolyzes generation phenazine-1-carboxylic acid in acid condition；Naphthalidine, three (trifluoro ethoxies) are added in the phenazine-1-carboxylic acid
Boron and acetonitrile, reaction.3. add 3ml DCM and 0.5ml water after reaction solution cooling.4. sequentially add Amberlyst A-26
(OH), Amberlyst 15, each 150mg of Amberlite IRA743 resins, react under room temperature condition and obtain.
Compared with prior art, the present invention have the advantage that for：This transformation compound 18-1 has to Sclerotinia sclerotiorum
Stronger virulence, its EC50For 11.79 μ g/mL, than the EC of comparison medicament azophenlyene -1- formamides50It is low；This transformation compound 18-1
There is preferable inhibition to Sclerotinia sclerotiorum, and its inhibition is better than its parental phenazine -1- formamides, is not easy to make disease
Bacterium develops immunity to drugs, and also enriches the novel pesticide of preventing and treating Sclerotinia sclerotiorum.
Brief description of the drawings
Fig. 1 is azophenlyene -1- formamides transformation compound 18-1 of the present invention mass spectrogram.
Embodiment
Technical scheme is described further with reference to specific experiment and embodiment, present invention experiment and real
It is mass percent to apply the percentage being related in example.
Azophenlyene -1- the formamides of embodiment 1 transformation compound 18-1 preparation
Transform compound 18-1 synthetic method：Azophenlyene -1- formamides are hydrolyzed into generation azophenlyene -1- carboxylics in acid condition
Acid；Take 1mmol phenazine-1-carboxylic acids (0.2282g), 1mmol naphthalidines (0.1467g), 2mmol tri- (trifluoro ethoxy) boron
(0.432ml), 2ml acetonitriles are added in 10ml sample bottles, magnetic agitation, and 80 DEG C are reacted 24 hours；3ml is added after reaction solution cooling
DCM and 0.5ml water；It is each to sequentially add Amberlyst A-26 (OH), Amberlyst 15, Amberlite IRA743 resins
150mg, stir 30 minutes under room temperature condition；Then the water removal of anhydrous slufuric acid magnesium dust is added, filtering, DCM washings are solid using drying
Body magnesium sulfate 3 times, revolving, obtains 0.1858g modification product 18-1, yield 53.18%.
Azophenlyene -1- the formamides of embodiment 2 transformation compound 18-1 Structural Identification
Using proton nmr spectra (1H NMR), transformation compound of carbon-13 nmr spectra (13C NMR) technology to acquisition
18-1 is measured.Compose through hydrogen (1H NMR (500MHz, CDCl3) δ 15.56-15.52 (m, 4H), 8.96 (dd, J=7.0,
1.3Hz,71H),8.63–8.54(m,7H),8.54–8.46(m,74H),8.46–8.28(m,85H),8.28–8.11(m,
79H), 8.11-7.56 (m, 356H), 7.52 (d, J=7.8Hz, 5H), 7.51-7.35 (m, 81H), 7.26 (dd, J=14.8,
8.4Hz, 83H), 6.76 (dt, J=9.4,4.7Hz, 34H), 3.49-3.45 (m, 4H), 2.50-2.42 (m, 5H), 1.55-
1.31 (m, 18H), 1.31-0.53 (m, 67H), 0.10 (s, 62H)), carbon spectrum (13C NMR (126MHz, CDCl3) δ 165.88
(s),144.04(s),143.32(s),142.01(s),139.98(s),139.77(s),137.35(s),135.06(s),
134.26 (d, J=19.5Hz), 133.17 (s), 131.69 (s), 131.19 (s), 130.22 (s), 130.04 (s), 128.94
(s), 128.47 (s), 128.28 (s), 127.93 (s), 126.55-125.68 (m), 124.86 (d, J=17.0Hz), 123.63
(s),121.56(s),120.75(s),118.92(s),109.69(s),77.31(s),77.06(s),76.80(s),1.03
(s)) and mass spectrum (molecular weight：349.12, Fig. 1) compound of detection synthesis is coincide with target, and its molecular formula is
C23H15N3O, structural formula are as follows.
Azophenlyene -1- the formamides of embodiment 3 transform inhibitory action of the compound 18-1 to Sclerotinia sclerotiorum
(1) instrument and associated materials
YJ-VS-2 types superclean bench (the net cleaning equipment Co., Ltd in Wuxi one), LDZX-30E autoclaves (are pacified Shanghai Shen
Medical apparatus and instruments factory), MPJ-250 types incubator (Shanghai gloomy reliable test Instrument Ltd.), QHX-400B-III type illumination cultivations
Case (Shanghai new talent medicine equipment Manufacturing Co., Ltd), electric furnace (Beijing Zhong Xing great achievements Instrument Ltd.) etc. and graduated cylinder, glass
Glass rod, beaker, triangular flask, ruler, pencil, label paper, sealed membrane, choose pin, volumetric flask, transfer needle, ph-101 watering cans, punching
Device, culture dish, kitchen knife, gauze.
(2) medicament
96% azophenlyene -1- formamide modification 18-1 the active compounds (hereinafter referred to as modification 18-1) that embodiment 1 is prepared；
The medicaments such as agar, glucose, acetone and Tween 80 are bought from Chinese medicines group.
(3) bacterial strain
Experiment is big by Agriculture in Hunan with the Sclerotinia sclerotiorum (Sclerotinia sclerotiorum) of wild responsive type
Learn the separation of plant pathology laboratory, identification and preserve.
(4) determinations of activity of the modification 18-1 to Sclerotinia sclerotiorum
Modification 18-1 is determined to Sclerotinia sclerotiorum (Sclerotinia sclerotiorum) using growth rate method
Bacteriostasis.Take proper amount of acetone to dissolve modification 18-1 active compounds, be then configured to the mother that mass concentration is 1000 μ g/mL
Liquid, by decoction and culture medium 1：9 volume ratio is configured to the drug containing flat board that final content of dispersion is 2.5,5,10,20,40 μ g/mL,
Beaten with diameter 5mm card punch in preculture 2d Sclerotinia sclerotiorum colony edge and take bacteria cake face down to be inoculated into drug containing to put down
On plate, often processing is repeated 3 times, and to make blank control without medicine flat board, is placed in 26-28 DEG C of incubator, colony diameter length to be compareed
During to 2/3 entirely cultivated, the colony diameter of each processing is measured using crossing method.Meanwhile tested using same method
Inhibitory action of the azophenlyene -1- formamides to rape sclerotium.Calculate inhibiting rate, EC50Value, coefficient correlation and regression equation, are as a result shown in
Tables 1 and 2.
(5) result and analysis
As shown in Table 1, modification 18-1 concentration is higher, and fungistatic effect is better.When modification 18-1 concentration is 40 μ g/mL
When, fungistatic effect is best, and its inhibiting rate is 83.33%；When modification 18-1 concentration is 20 μ g/mL, fungistatic effect takes second place；Other
The inhibiting rate of processing is less than 45%.This modification 18-1 has compared with strong virus force effect (EC to Sclerotinia sclerotiorum50For 11.79 μ g/
ML, regression equation Y=1.2266x+3.6858, coefficient correlation 0.9132), its virulence is better than comparison medicament azophenlyene -1- first
Acid amides (EC50For 14.31 μ g/mL, regression equation Y=1.2266x+3.6858, coefficient correlation 0.9132), illustrate the medicament
Can be as the lead compound of prevention and control sclerotinia sclerotiorum novel pesticide.
Inhibitory action of the azophenlyene -1- formamide modification 18-1 of table 1 to Sclerotinia sclerotiorum
Inhibitory action of the azophenlyene -1- formamides (comparison medicament) of table 2 to Sclerotinia sclerotiorum
Claims (3)
1. a kind of applications of azophenlyene -1- formamides transformation compound 18-1 in Sclerotinia sclerotiorum is suppressed, the azophenlyene -1- formyls
Amine transformation compound 18-1 structural formula is as follows：
2. a kind of applications of azophenlyene -1- formamides transformation compound 18-1 in prevention and control sclerotinia sclerotiorum agricultural chemicals is prepared, the azophenlyene -
1- formamides transformation compound 18-1 structural formula is as follows：
3. application as claimed in claim 1 or 2, it is characterised in that the azophenlyene -1- formamides transformation compound 18-1 be with
Azophenlyene -1- formamides are parent, and azophenlyene -1- formamides are hydrolyzed into generation phenazine-1-carboxylic acid in acid condition；In the azophenlyene-
Naphthalidine, three (trifluoro ethoxy) boron and acetonitrile are added in 1- carboxylic acids to be reacted, and DCM and water are added after reaction solution cooling, then
Amberlyst A-26 (OH), Amberlyst 15, Amberlite IRA743 resins are sequentially added, is reacted under room temperature condition
Arrive.
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| CN103343150B (en) * | 2013-07-22 | 2015-10-07 | 上海农乐生物制品股份有限公司 | A kind of preparation method of azophenlyene-1-formyl hydrazine biological bactericide |
| CN103834585B (en) * | 2013-10-24 | 2016-02-10 | 上海交通大学 | The rhizosphere pseudomonas of high yield phenazine-1-carboxylic acid and azophenlyene-1-acid amides |
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| Synthesis and bioactivities of Phenazine-1-carboxylic acid derivatives based on the modification of PCA carboxyl group;Zhipeng Xiong,et al.;《Bioorganic & Medicinal Chemistry Letters》;20170308;第2012页表1 * |
| Synthesis in phenazinecarboxylic acid series. III. Arylamides of 1-phenazinecarboxylic acid;Rozum,Yu.S.;《Ukrains＇kii Khemichnii Zhurnal》;19541231;STN摘要 * |
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Application publication date: 20170613 Assignee: Hunan Hewang Biotechnology Co.,Ltd. Assignor: Hunan Agricultural University Contract record no.: X2022980024840 Denomination of invention: Application of a Phenozin-1-formamide Modified Compound 18-1 in Inhibition of Sclerotinia sclerotiorum Granted publication date: 20180202 License type: Common License Record date: 20221206 |
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