CN108477170A - A kind of quinolines and preparation method thereof and the purposes in controlling plant diseases - Google Patents

A kind of quinolines and preparation method thereof and the purposes in controlling plant diseases Download PDF

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CN108477170A
CN108477170A CN201810291712.1A CN201810291712A CN108477170A CN 108477170 A CN108477170 A CN 108477170A CN 201810291712 A CN201810291712 A CN 201810291712A CN 108477170 A CN108477170 A CN 108477170A
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quinolines
chloride
400mhz
esi
chloroform
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CN108477170B (en
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刘映前
杨冠洲
马强
冯建雄
彭静文
李俊采
张晓帅
杨程杰
徐小山
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Lanzhou University
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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
    • 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
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/20—Oxygen atoms
    • C07D215/22—Oxygen atoms attached in position 2 or 4
    • C07D215/233—Oxygen atoms attached in position 2 or 4 only one oxygen atom which is attached in position 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
    • C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dentistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • General Health & Medical Sciences (AREA)
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  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Purposes the invention discloses a kind of quinolines and preparation method thereof and in controlling plant diseases.Test result shows：Such compound has excellent control effect to plant disease caused by cotton-wilt fusarium, gibberella saubinetii, Sclerotinia sclerotiorum, Rhizoctonia solani Kuhn and Pyricularia oryzae and to Pumpkin powdery mildew and cucumber white powder.Preparation process of the present invention is simple, raw material is cheap and easy to get, and product purity is high, and it is new fungicide to be expected to exploitation.

Description

A kind of quinolines and preparation method thereof and the purposes in controlling plant diseases
Technical field
The invention belongs to field of natural medicinal chemistry and technical field of pesticide, disclose the new use of one kind of quinoline On the way, and in particular to quinoline is in prevention by cotton-wilt fusarium (Fusarium oxysporum f.sp.vasinfectum (Atk.) Snyder＆Hansen), gibberella saubinetii (Fusarium graminearum), Sclerotinia sclerotiorum (Sclerotinia Sclerotiorum), Rhizoctonia solani Kuhn (Rhizoctonia solani) and Pyricularia oryzae (Magnaporthe oryzae) draw The plant disease risen and the field control effect to Pumpkin powdery mildew and cucumber white powder.
Background technology
Currently, being mainly controlled by chemical pesticides by fungus-caused plant disease, although many commercialization fungicide at present Control effect is preferable, but being widely used due to these chemical pesticides, and leading to " 3R ", (residue residuals, resistance are anti- Property, resurgence it is rampant once again) problem is on the rise, caused the very big concern of society.Therefore, research and development are efficient Safety pesticide comes the important topic that the prevention and control plant disease person that has become plant protection work faces and sustainable development of agricultural production Only way, and a part of the botanical pesticide as biogenic pesticide, because generally acknowledge its have low toxicity, noresidue, high selectivity, The advantages that easily decomposition, pest are not likely to produce drug resistance, and receive researcher's favor.Therefore, it finds and screens from plant resources Potential sterilization secondary metabolite, and becoming new type bactericide initiative using it as guide structure progress Optimal Structure Designing One of important channel.
Quinine is very famous alkaloids natural drug, is commonly called as quinine, is from madder wort golden pheasant earliest Extraction obtains in Na Shu (Cinchona ledgeriana (Howard) Moens ex Trim) and its bark of congener. Quinine is to treat the specific drug of malaria, and the life of countless malaria patients has once been saved in its discovery and application.Seminar early period It was found that quinine to Sclerotinia sclerotiorum at 50ppm, be 69.58% to the inhibitory activity of germ, we are further to similitude Molecule Mefloquine (antimalarial) has done carry out active testing evaluation, it is found that its antibacterial activity is obviously improved.According to its activity The selection result, we carry out derivative synthesis at its 4, have synthesized a series of new quinolines using it as parent nucleus guide structure Object is closed, its bactericidal activity is made to have significantly more raising, also more simple in its synthetic method, economical, synthesis cost is aobvious Writing reduces.Although the research report about quinine is more, text is had not yet to see to its application in terms of inhibiting agriculture germ Offer report.
The present invention is using quinine as clue, and by its structure optimization and derivative synthesis, design has synthesized a series of recruits, and It was found that target compound has preferably cotton-wilt fusarium, gibberella saubinetii, Sclerotinia sclerotiorum, Rhizoctonia solani Kuhn and Pyricularia oryzae Fungistatic effect find that it has preferable control effect to Pumpkin powdery mildew and cucumber white powder by field trial, can be used as A kind of novel wide-spectrum bactericide.
Invention content
The present invention provides following technical methods：One kind is for cotton-wilt fusarium, fusarium graminearum, sclerotinia sclerotiorum The drug of bacterium, Rhizoctonia solani Kuhn and Pyricularia oryzae, wherein any compound institute in KL-1~KL-26 containing therapeutically effective amount The quinoline (figure -2) shown.
Quinoline synthetic method of the present invention is shown in embodiment, is detached through conventional methods such as multiple silica gel column chromatographies Sterling is obtained, through the spectroscopic techniques such as mass spectrum and nuclear magnetic resonance, it is determined that right wants quinolines KL-1~KL-26, knot Structure formula is as shown in Figure 2.Show that quinoline of the present invention is red to cotton-wilt fusarium, wheat through active ingredients result Mildew bacterium, Sclerotinia sclerotiorum, Rhizoctonia solani Kuhn and Pyricularia oryzae show stronger inhibiting effect, can be used for preparing sterilization Agent.
Description of the drawings
Fig. 1 compounds are found and optimization process
Fig. 2 quinoline derivatives
Specific implementation mode
Embodiment 1
The synthesis of quinoline (KL-1)
Method one：
Method two：
Its specific synthetic operation is as follows：
Method one：By raw material 2,0.247 gram of bis- Trifluoromethylquinocarboxylics of 8- are added in 50mL single port bottles, molten with 20mL acetone Equimolar potassium carbonate is first added in solution, and equimolar benzyl chloroformate is then added, is heated to reflux 3 hours, filters to get filtrate, boil off Solvent purifies solvent (ethyl acetate with column chromatography:Petroleum ether=1:5) white solid is obtained.
Method two：By raw material 2,0.247 gram of bis- Trifluoromethylquinocarboxylics of 8- are added in 50mL single port bottles, and 5mL acetic acid is added Acid anhydride is heated to reflux 3h, and plate layer chromatography tracking reaction is completed, and extra acetic anhydride is boiled off under decompression, (solvent is detached with plate layer chromatography: Ethyl acetate:Petroleum ether=1:5) white solid is obtained.
KL-1:White solid, yield 85%；1H NMR (400MHz, Chloroform-d) δ 8.23 (dd, J=17.4, 7.9Hz, 2H), 7.80 (s, 1H), 7.75 (t, J=7.9Hz, 1H), 2.17 (s, 3H) .ESI-MS m/z:346.06[M+Na]+.
Embodiment 2
The synthesis of KL-2:Experimental procedure is changed to propionyl chloride with embodiment 1, by chloroacetic chloride.
KL-2 white solids, yield 83%；1H NMR (400MHz, Chloroform-d) δ 8.15 (dd, J=14.6, 7.9Hz, 2H), 7.74 (s, 1H), 7.67 (s, 1H), 2.77 (d, J=7.5Hz, 2H), 1.32 (t, J=7.6Hz, 3H) .ESI- MS m/z:360.08[M+Na]+.
Embodiment 3
The synthesis of KL-3:Experimental procedure is changed to chloracetyl chloride with embodiment 1, by chloroacetic chloride.
KL-3 white solids, yield 72%；1H NMR (400MHz, Chloroform-d) δ 8.19 (dd, J=20.8, 7.9Hz, 2H), 7.79 (s, 1H), 7.72 (t, J=7.9Hz, 1H), 4.43 (s, 2H) .ESI-MS m/z:380.02[M+Na]+.
Embodiment 4
The synthesis of KL-4:Experimental procedure is changed to n-butyryl chloride with embodiment 1, by chloroacetic chloride.
KL-4 white solids, yield 84%；1H NMR(400MHz,Chloroform-d)δ8.16(s,2H),7.73(s, 1H), 7.68 (s, 1H), 2.71 (t, J=7.4Hz, 2H), 1.90-1.75 (m, 2H), 1.06 (t, J=7.4Hz, 3H) .ESI-MS m/z:374.09[M+Na]+.
Embodiment 5
The synthesis of KL-5:Experimental procedure is changed to n-amyl chloride with embodiment 1, by chloroacetic chloride.
KL-5:White solid, yield 88%；1H NMR(400MHz,Chloroform-d)δ8.20–8.10(m,2H), 7.72 (s, 1H), 7.68 (s, 1H), 2.73 (t, J=7.5Hz, 2H), 1.79 (t, J=7.5Hz, 2H), 1.48-1.40 (m, 2H), 0.96 (t, J=7.3Hz, 3H) .ESI-MS m/z:388.11[M+Na]+.
Embodiment 6
The synthesis of KL-6：Experimental procedure is changed to isoveryl chloride with embodiment 1, by chloroacetic chloride.
KL-6 white solids, yield 89%；1H NMR (400MHz, Chloroform-d) δ 8.15 (dd, J=14.8, 7.9Hz, 2H), 7.72 (s, 1H), 7.67 (t, J=7.9Hz, 1H), 2.60 (d, J=7.1Hz, 2H), 2.34-2.22 (m, 1H), 1.07 (d, J=6.6Hz, 6H) .ESI-MS m/z:388.11[M+Na]+.
Embodiment 7
The synthesis of KL-7:Experimental procedure is changed to positive caproyl chloride with embodiment 1, by chloroacetic chloride.
KL-7 white solids, yield 86%；1H NMR (400MHz, Chloroform-d) δ 8.15 (dd, J=13.0, 7.9Hz, 2H), 7.73 (s, 1H), 7.67 (t, J=7.9Hz, 1H), 2.72 (t, J=7.5Hz, 2H), 1.80 (p, J=7.4Hz, 2H), 1.47-1.29 (m, 4H), 0.90 (t, J=6.9Hz, 3H) .ESI-MS m/z:402.13[M+Na]+..
Embodiment 8：
The synthesis of KL-8:Experimental procedure is changed to chlorobenzoyl chloride with embodiment 1, by chloroacetic chloride.
KL-8 white solids, yield 84%；1H NMR (400MHz, Chloroform-d) δ 8.24 (d, J=7.5Hz, 2H), 8.14 (d, J=7.3Hz, 1H), 8.12-8.00 (m, 1H), 7.83 (s, 1H), 7.68 (td, J=7.8,4.7Hz, 2H), 7.54 (t, J=7.7Hz, 2H) .ESI-MS m/z:408.09[M+Na]+..
Embodiment 9
The synthesis of KL-9:Experimental procedure is changed to phenyl chloroformate with embodiment 1, by chloroacetic chloride.
KL-9 white solids, yield 80%；1H NMR (400MHz, Chloroform-d) δ 8.40 (d, J=8.5Hz, 1H), 8.18 (d, J=7.3Hz, 1H), 8.00 (s, 1H), 7.75 (t, J=7.9Hz, 1H), 7.46-7.38 (m, 2H), 7.38- 7.32(m,1H),7.30–7.27(m,2H).ESI-MS m/z:441.57[M+K]+.
Embodiment 10
The synthesis of KL-10:Experimental procedure is changed to benzyl chloroformate with embodiment 1, by chloroacetic chloride.
KL-10 white solids, yield 88%；1H NMR (400MHz, Chloroform-d) δ 8.26 (dd, J=8.4, 1.4Hz, 1H), 8.13 (d, J=7.2Hz, 1H), 7.89 (s, 1H), 7.67 (t, J=7.9Hz, 1H), 7.42 (dq, J=4.5, 2.5Hz,2H),7.40–7.35(m,3H),5.32(s,2H).ESI-MS m/z:438.08[M+Na]+..
Embodiment 11
The synthesis of KL-11：Experimental procedure is changed to mesyl chloride with embodiment 1, by chloroacetic chloride.
KL-11 white solids, yield 74%；1H NMR (400MHz, Chloroform-d) δ 8.33 (d, J=8.5Hz, 1H), 8.19 (d, J=7.3Hz, 1H), 7.80 (s, 1H), 7.76 (s, 1H), 3.36 (s, 3H) .ESI-MS m/z:360.06[M+ H]+.
Embodiment 12
The synthesis of KL-12：Experimental procedure is changed to tosylate chloride with embodiment 1, by chloroacetic chloride.
KL-12 white solids, yield 79%；1H NMR(400MHz,Chloroform-d)δ8.14–8.07(m,2H), 7.93-7.87 (m, 2H), 7.69 (td, J=7.4,1.4Hz, 1H), 7.62 (t, J=7.9Hz, 1H), 7.57-7.50 (m, 3H) .ESI-MSm/z:444.06[M+Na]+..
Embodiment 13
The synthesis of KL-13:Experimental procedure is changed to tert-butyl chloro-silicane with embodiment 1, by chloroacetic chloride.
KL-13 white solids, yield 50%；1H NMR (400MHz, Chloroform-d) δ 8.13 (d, J=7.3Hz, 1H), 8.04 (d, J=7.6Hz, 1H), 7.54 (t, J=7.9Hz, 1H), 6.77-6.69 (m, 1H), 1.10 (s, 9H), 0.40 (s,2H).ESI-MS m/z:418.13[M+Na]+.
Embodiment 14
KL-14 is synthesized：Experimental procedure is changed to 1- chlorpromazine chlorides with embodiment 1, by chloroacetic chloride.
KL-14 white solids, yield 82%；1H NMR (400MHz, Chloroform-d) δ 8.21 (d, J=8.6Hz, 1H), 8.15 (d, J=7.3Hz, 1H), 7.76-7.67 (m, 2H), 3.91 (t, J=6.3Hz, 2H), 3.22 (t, J=6.3Hz, 2H).
ESI-MS m/z:409.98[M+K]+.
Embodiment 15
KL-15 is synthesized：Experimental procedure is changed to 2- chlorpromazine chlorides with embodiment 1, by chloroacetic chloride.
KL-15 white solids, yield 34%；1H NMR (400MHz, Chloroform-d) δ 8.52 (d, J=8.5Hz, 1H), 8.14 (d, J=7.3Hz, 1H), 7.65 (t, J=7.8Hz, 1H), 7.31 (s, 1H), 4.12 (s, 1H), 1.58 (s, 3H) .ESI-MSm/z:494.00[M+Na]+.
Embodiment 16
KL-16 is synthesized：Experimental procedure is changed to 1- chlorine n-butyryl chlorides with embodiment 1, by chloroacetic chloride.
KL-16 white solids, yield 68%；1H NMR(400MHz,Chloroform-d)δ8.28–8.18(m,2H), 7.81 (s, 1H), 7.76 (s, 1H), 3.74 (t, J=6.1Hz, 2H), 3.04 (t, J=7.2Hz, 2H), 2.43-2.24 (m, 2H).ESI-MSm/z:408.02[M+Na]+.
Embodiment 17
KL-17 is synthesized：Experimental procedure is changed to 1- chlorine n-amyl chlorides with embodiment 1, by chloroacetic chloride.
KL-17 white solids, yield 70%；1H NMR(400MHz,Chloroform-d)δ8.26–8.18(m,2H), 7.80 (s, 1H), 7.75 (t, J=7.9Hz, 1H), 3.65 (t, J=6.0Hz, 2H), 2.86 (t, J=7.1Hz, 2H), 2.16- 1.86(m,4H).ESI-MS m/z:422.07[M+Na]+.
Embodiment 18
KL-18 is synthesized：Experimental procedure is changed to isobutyryl chloride with embodiment 1, by chloroacetic chloride.
KL-18 white solids, yield 83%；1H NMR (400MHz, Chloroform-d) δ 8.21 (t, J=8.2Hz, 2H), 7.78 (s, 1H), 7.75 (t, J=8.4Hz, 1H), 1.47 (d, J=7.0Hz, 6H) .ESI-MS m/z:374.09[M+ Na]+.
Embodiment 19
KL-19 is synthesized：Experimental procedure is changed to 2- bromo propionyl chloros with embodiment 1, by chloroacetic chloride.
KL-19 white solids, yield 45%；1H NMR (400MHz, Chloroform-d) δ 8.60 (d, J=8.1Hz, 1H), 8.02 (d, J=7.5Hz, 1H), 7.52 (t, J=7.9Hz, 1H), 6.69 (d, J=1.9Hz, 1H), 4.87-4.74 (m, 2H), 2.06 (d, J=6.9Hz, 3H) .ESI-MS m/z:388.11[M+Na]+.
Embodiment 20
KL-20 is synthesized：Experimental procedure is changed to chloro-pivalyl chloride with embodiment 1, by chloroacetic chloride.
KL-20 white solids, yield 75%；1H NMR (400MHz, Chloroform-d) δ 8.28 (dd, J=8.5, 1.3Hz, 1H), 8.21 (d, J=7.3Hz, 1H), 7.77 (d, J=7.9Hz, 1H), 7.70 (s, 1H), 3.86 (s, 2H), 1.60 (s,6H).
ESI-MS m/z:422.07[M+Na]+.
Embodiment 21
KL-21 is synthesized：Experimental procedure is changed to isobutyryl chloride with embodiment 1, by chloroacetic chloride.
KL-21 white solids, yield 78%；1H NMR(400MHz,Chloroform-d)δ8.21(s,1H),8.19(s, 1H),7.78–7.71(m,2H),1.51(s,9H).ESI-MS m/z:388.11[M+Na]+.
Embodiment 22
KL-22 is synthesized：Experimental procedure is changed to ring propionyl chloride with embodiment 1, by chloroacetic chloride.
KL-22 white solids, yield 75%；1H NMR (400MHz, Chloroform-d) δ 8.20 (d, J=8.5Hz, 1H), 8.13 (d, J=7.3Hz, 1H), 7.72 (s, 1H), 7.69 (d, J=7.9Hz, 1H), 1.99 (tt, J=7.9,4.6Hz, 1H),1.30–1.22(m,2H),1.23–1.09(m,2H).ESI-MS m/z:372.07[M+Na]+.
Embodiment 23
KL-23 is synthesized：Experimental procedure is changed to ring butyl chloride with embodiment 1, by chloroacetic chloride.
KL-23 white solids, yield 73%；1H NMR (400MHz, Chloroform-d) δ 8.21 (dd, J=7.7, 5.4Hz, 2H), 7.80 (s, 1H), 7.74 (s, 1H), 3.62 (p, J=8.5Hz, 1H), 2.71-2.37 (m, 4H), 2.32-2.00 (m,2H).ESI-MS m/z:386.09[M+Na]+.
Embodiment 24
KL-24 is synthesized：Experimental procedure is changed to ring valeric chloride with embodiment 1, by chloroacetic chloride.
KL-24 white solids, yield 68%；1H NMR (400MHz, Chloroform-d) δ 8.22 (dd, J=13.5, 7.9Hz, 2H), 7.78 (s, 1H), 7.74 (s, 1H), 3.22 (p, J=8.0Hz, 1H), 2.21-2.13 (m, 3H), 2.11-2.02 (m,1H),1.89–1.82(m,2H),1.81–1.71(m,2H).ESI-MS m/z:400.11[M+Na]+.
Embodiment 25
KL-25 is synthesized：Experimental procedure is changed to Cyclohexanoyl chloride with embodiment 1, by chloroacetic chloride.
KL-25 white solids, yield 76%；1H NMR(400MHz,Chloroform-d)δ8.18–8.10(m,2H), 7.69 (s, 1H), 7.66 (d, J=7.9Hz, 1H), 2.72 (tt, J=11.3,3.7Hz, 1H), 2.20-2.07 (m, 2H), 1.83 (dt, J=12.9,3.6Hz, 2H), 1.76-1.54 (m, 3H), 1.33 (dtdd, J=29.2,17.0,7.7,4.4Hz, 3H) .ESI-MS m/z:414.13[M+Na]+.
Embodiment 26
KL-26 is synthesized：Experimental procedure is changed to methacrylic chloride with embodiment 1, by chloroacetic chloride.
KL-26 white solids, yield 82%；1H NMR (400MHz, Chloroform-d) δ 8.22 (dd, J=11.6, 7.9Hz, 2H), 7.82 (s, 1H), 7.75 (s, 1H), 6.57 (s, 1H), 6.09-5.92 (m, 1H), 2.18 (t, J=1.3Hz, 3H).ESI-MSm/z:372.08[M+Na]+.
Embodiment 27
Indoor antibacterial determination of activity and result
1) experiment material：
Chemical formula KL-1~KL-26 quinoline derivatives synthesize for this laboratory.
Phytopathogen used in this experiment is the strain of the 4 DEG C of preservations in laboratory, and the culture medium used is trained for potato Support base (abbreviation PDA).
PDA culture medium formula:Potato (peeling) 200g, glucose 20g, agar 15g, tap water 1000mL, natural PH.
Preparation method：Potato is cleaned into peeling, 200g is claimed to be cut into small pieces, adds boiling is rotten (to boil 20-30 minutes, energy quilt Glass bar is poked), with eight layers of filtered through gauze in beaker, is needed to add 15-20g agar according to experiment, 20g grapes are added Sugar stirs evenly, and slightly cooling water of supplying sterilizes 20 minutes for 121 DEG C to 1000mL after packing fully after dissolving, spare after cooling.
2) experimental method
Using growth rate method.
1, first by 5 kinds of phytopathogens, 25 DEG C of culture 6d or so are for use on PDA plate.
2, PDA culture medium heating is dissolved, is cooled to 45-50 DEG C, is separately added into the quinoline derivatives system of various concentration At the culture medium containing 50,25,10,5 and 2.5 μ g/mL liquids, and pour into respectively cooling in culture dish.
3, it with sterile working formality, is beaten at each bacterial strain mycelia edge (upgrowth situation is consistent as possible) of culture 6d with card punch Round bacteria cake (diameter 0.50cm) is taken, then is chosen to drug containing tablet center with transfer needle, culture dish is then inverted in incubator (25 DEG C) in culture.
4, after processing different time Observe and measure mycelia growing state, and measure diameter and locate using crossing method Data are managed, inhibiting rate is calculated.
5, inhibiting rate (%)=(control hyphal diameter-processing hyphal diameter)/control hyphal diameter × 100
6, each processing is repeated 3 times.
3) quinoline derivatives are to cotton-wilt fusarium, fusarium graminearum, Sclerotinia sclerotiorum, Rhizoctonia solani Kuhn and rice The fungistatic effect of seasonal febrile diseases bacterium mycelia growth
Cotton-wilt fusarium, fusarium graminearum, Sclerotinia sclerotiorum, Rhizoctonia solani Kuhn and Pyricularia oryzae are with reference to raw mark Quasi- method NY/T1156.2-2006 carries out indoor biological determination of activity using growth rate method, specifies quinoline derivatives Inhibitory activity of the KL-1~KL-26 to this five kinds of germs.Table 1 is quinoline derivatives to cotton-wilt fusarium, wheat scab The inhibitory activity test result that bacterium, Sclerotinia sclerotiorum, Rhizoctonia solani Kuhn and Pyricularia oryzae mycelia grow.
1 quinoline derivatives of table to cotton-wilt fusarium, fusarium graminearum, Sclerotinia sclerotiorum, Rhizoctonia solani Kuhn and The inhibitory activity test result of Pyricularia oryzae mycelia growth
Note:It each handles to set in experiment and repeat three times, data are the average value repeated three times in table, and "-" expression does not carry out Bacteriostatic experiment.
Embodiment 28
Field control effect evaluation to Pumpkin powdery mildew and powdery mildew of cucumber.
1) Pumpkin powdery mildew
1, experiment material：Cucurbita pepo, kind ' advantage '.Monofilament shell powdery mildew (Sphaerotheca fuliginea (Schl.) poll.) pick up from spontaneous bacterium source on Gansu Academy of Agricultural Science's temperature indoor pot cucurbita pepo.
2, control and reagent agent：Propiconazole, bulk myclobutanil, propiconazole, KL-1 compounds.
3, experimentation：
(1) sowing of cultivation management experimental plot, fertilizer and water management, the pervious insect pest preventing and controlling of experimental stage are consistent with local production.1 It is secondary
Other pesticides influential on powdery mildew are not applied before dispenser in 10d.
(2) bacterium method is connect：On September 16th, 2017, the fresh sick leaf of Pumpkin powdery mildew smash filtering to pieces, and spore suspension is in west
Cucurbit face of blade carries out even spraying and connects bacterium.
(3) medicament is arranged：15%KL-1 missible oil setting dilution 1500 times of liquid, 1 concentration, 12.5% nitrile bacterium azoles of comparison medicament Breast
Oil and 25% propiconazole emulsifiable concentrate set dilution 1500 times of liquid, 1 concentration, separately set clear water control.
(4) application method：September in 2017 connects dispenser in 48 hours after bacterium on the 18th.Every dispenser in 7 days 1 time, continuous 3 (Septembers 18 days, September 25 days, October 3).
(5) investigation method：(October 21) investigation disease refers to 18 days after last 1 dispenser, calculates preventive effect.It investigates simultaneously
Safety.Disease severity grade scale is：
0 grade-disease-free spot；
1 grade-lesion area accounts for 2% or less leaf area；
3 grades-lesion area accounts for the 2%~5% of leaf area；
5 grades-lesion area accounts for the 6%~20% of leaf area；
7 grades-lesion area accounts for the 21%~40% of leaf area；
9 grades-lesion area accounts for 40% of leaf area or more.
(6) control effect
(7) 1500 times of liquid blades of safety evaluatio propiconazole thicken be hardened, the green, petiole that darkens shortens, growing point is bad
Extremely.The same propiconazole of nitrile bacterium azoles symptom of chemical damage only shows relatively light.KL-1 safety, blade variation without exception.
2) powdery mildew of cucumber
1, experiment material：Cucumber variety is the close thorn in Xintai City.Cucumber powdery mildew's pathogen (Sphaerotheca fuliginea) is adopted From spontaneous bacterium source on Gansu Academy of Agricultural Science temperature indoor pot cucumber.
2, control and reagent agent：Bulk myclobutanil, propiconazole, Original Tebuconazole, difenoconazole, KL-1 chemical combination Object.
3, experimentation：
(1) sowing of cultivation management experimental plot, fertilizer and water management, the pervious insect pest preventing and controlling of experimental stage are consistent with local production. Other pesticides influential on powdery mildew of cucumber are not applied before 1 dispenser in 10d.
(2) bacterium method on October 7th, 2017 is connect, the fresh sick leaf of powdery mildew of cucumber smashs filtering to pieces, and spore suspension is in cucumber Face of blade carries out even spraying and connects bacterium.
(3) medicament setting 15%KL-1 missible oil, 12.5% nitrile bacterium azoles missible oil, 25% propiconazole emulsifiable concentrate, 430g/L Tebuconazoles Suspending agent, 25% difenoconazole missible oil are respectively provided with dilution 2500 times of liquid, 1 concentration (preparation dosage), separately set clear water control.
(4) application method temperature indoor pot cucumber, October 9 cucumber florescence powdery mildew initial phase (natural occurrence, put down Equal disease index：0 grade 56,1 grade 35,3 grades 4,7 grades 1, disease referred to 6.25) the 1st dispenser of beginning, every dispenser 1 in 7 days 3 times secondary, continuous (on October 9,16,23 days), 10 days after the 3rd dispenser (November 2) by 9 grades classification standard surveys fall ill feelings Condition calculates disease and refers to, and refers to calculating preventive effect according to disease.
(5) investigation on 10 days (November 22) disease refers to after last 1 dispenser of investigation method, calculates preventive effect.Investigate safety simultaneously Property.Disease severity grade scale is：
0 grade-disease-free spot；
1 grade-lesion area accounts for 2% or less leaf area；
3 grades-lesion area accounts for the 2%~5% of leaf area；
5 grades-lesion area accounts for the 6%~20% of leaf area；
7 grades-lesion area accounts for the 21%~40% of leaf area；
9 grades-lesion area accounts for 40% of leaf area or more.
(6) control effect
(7) safety evaluatio propiconazole dispenser blade thicken be hardened, darken, petiole shortens, leaf margin not yellow；Penta Azoles alcohol, nitrile bacterium azoles dispenser blade thicken and are hardened, and darken, petiole shortens, leaf margin yellow；Difenoconazole safety.KL-1 is applied Medicine plant lobus cardiacus leaf margin last volume has irregularly withered hickie, and symptoms are mild.

Claims (3)

1. a kind of application of the quinolines of the present invention in controlling plant diseases, compound structure feature is such as Under：
2. application of a kind of quinolines in preparing pathogenic bacteria inhibitor according to claim 1.
3. application according to claim 2, it is characterised in that：The plant disease is the plant caused by following pathogens Disease：Cotton-wilt fusarium, gibberella saubinetii, Sclerotinia sclerotiorum, Rhizoctonia solani Kuhn, Pyricularia oryzae, Pumpkin powdery mildew and Huang One or more of melon white powder arbitrarily combines.
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CN109467533A (en) * 2018-12-14 2019-03-15 兰州大学 A kind of 8-hydroxyquinoline class compound and preparation method thereof and the purposes in prevention and treatment agricultural disease
CN110156678A (en) * 2019-05-27 2019-08-23 兰州大学 A kind of purposes of the derivatives of bis- (trifluoromethyl) the quinolines 4- modifications of 2,8- in controlling plant diseases
CN110437146A (en) * 2019-07-17 2019-11-12 兰州大学 A kind of preparation of quinoline 4- hydroxy methacrylates class compound and its application in controlling plant diseases
CN112493244A (en) * 2019-09-16 2021-03-16 兰州大学 Application of quinoline 2-position derivative in preparation of agricultural plant disease prevention and treatment medicines
CN112939942A (en) * 2020-12-24 2021-06-11 聊城大学 Heterocyclic ester compound containing quinoline structure and preparation method and application thereof
CN112939942B (en) * 2020-12-24 2023-11-07 聊城大学 Heterocyclic ester compound containing quinoline structure, and preparation method and application thereof
CN112608275A (en) * 2020-12-29 2021-04-06 兰州大学 Application of 2, 8-bis (trifluoromethyl) -4-hydroxyquinoline derivative in preparation and prevention and treatment of agricultural diseases
CN114957116A (en) * 2022-07-01 2022-08-30 浙江工业大学 2, 3-dimethyl-8-fluoroquinoline-4-ester compound and preparation method and application thereof
CN115466212A (en) * 2022-10-26 2022-12-13 河南农业大学 2-trifluoromethyl quinoline compound and synthetic method and application thereof
CN115466212B (en) * 2022-10-26 2023-09-22 河南农业大学 2-trifluoromethyl quinoline compound and synthetic method and application thereof

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