CN106588836B - 2-环己烯酮衍生物及其在农药中的应用 - Google Patents
2-环己烯酮衍生物及其在农药中的应用 Download PDFInfo
- Publication number
- CN106588836B CN106588836B CN201611161787.5A CN201611161787A CN106588836B CN 106588836 B CN106588836 B CN 106588836B CN 201611161787 A CN201611161787 A CN 201611161787A CN 106588836 B CN106588836 B CN 106588836B
- Authority
- CN
- China
- Prior art keywords
- cyclohexenone derivates
- cyclohexenone
- derivates
- pesticide
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohex-2-enone Chemical compound O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000000575 pesticide Substances 0.000 title claims abstract description 17
- 244000000004 fungal plant pathogen Species 0.000 claims abstract description 14
- 240000008042 Zea mays Species 0.000 claims abstract description 12
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims abstract description 12
- 241001425390 Aphis fabae Species 0.000 claims abstract description 11
- 235000009754 Vitis X bourquina Nutrition 0.000 claims abstract description 11
- 235000012333 Vitis X labruscana Nutrition 0.000 claims abstract description 11
- 235000014787 Vitis vinifera Nutrition 0.000 claims abstract description 11
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims abstract description 11
- 235000005822 corn Nutrition 0.000 claims abstract description 11
- 241000409991 Mythimna separata Species 0.000 claims abstract description 10
- 240000006365 Vitis vinifera Species 0.000 claims abstract 2
- 241000894006 Bacteria Species 0.000 claims description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 230000002401 inhibitory effect Effects 0.000 claims description 8
- 241000221696 Sclerotinia sclerotiorum Species 0.000 claims description 7
- 241000607479 Yersinia pestis Species 0.000 claims description 7
- 235000013399 edible fruits Nutrition 0.000 claims description 7
- 241000223195 Fusarium graminearum Species 0.000 claims description 6
- 241000813090 Rhizoctonia solani Species 0.000 claims description 6
- 241000123650 Botrytis cinerea Species 0.000 claims description 5
- 241000238631 Hexapoda Species 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 230000001954 sterilising effect Effects 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 abstract description 26
- 235000007688 Lycopersicon esculentum Nutrition 0.000 abstract description 6
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 6
- 240000007594 Oryza sativa Species 0.000 abstract description 5
- 235000007164 Oryza sativa Nutrition 0.000 abstract description 5
- 235000009566 rice Nutrition 0.000 abstract description 5
- 231100000331 toxic Toxicity 0.000 abstract description 4
- 230000002588 toxic effect Effects 0.000 abstract description 4
- 241001530056 Athelia rolfsii Species 0.000 abstract description 3
- 241000223218 Fusarium Species 0.000 abstract description 3
- 241001558929 Sclerotium <basidiomycota> Species 0.000 abstract description 3
- 240000003768 Solanum lycopersicum Species 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 231100000135 cytotoxicity Toxicity 0.000 description 10
- 230000003013 cytotoxicity Effects 0.000 description 10
- 241000219095 Vitis Species 0.000 description 9
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- 125000005909 ethyl alcohol group Chemical group 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000543 intermediate Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 241000227653 Lycopersicon Species 0.000 description 5
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 230000005764 inhibitory process Effects 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000012937 correction Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 230000000857 drug effect Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 240000006677 Vicia faba Species 0.000 description 3
- 235000010749 Vicia faba Nutrition 0.000 description 3
- 235000002098 Vicia faba var. major Nutrition 0.000 description 3
- 201000010099 disease Diseases 0.000 description 3
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 3
- 229920000053 polysorbate 80 Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- -1 2- cyclohexene Ketone Chemical class 0.000 description 2
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 2
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 2
- 241001107116 Castanospermum australe Species 0.000 description 2
- 241001477928 Mythimna Species 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 206010039509 Scab Diseases 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 241000209140 Triticum Species 0.000 description 2
- 235000021307 Triticum Nutrition 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 235000021279 black bean Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical class CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- 230000000855 fungicidal effect Effects 0.000 description 2
- 239000000417 fungicide Substances 0.000 description 2
- 150000002240 furans Chemical class 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 231100000820 toxicity test Toxicity 0.000 description 2
- 241001124076 Aphididae Species 0.000 description 1
- 0 CC=CCC(C=C)c(cc1)ccc1C(CC(C1C(O*)=O)C2=CC=C*2)=CC1=O Chemical compound CC=CCC(C=C)c(cc1)ccc1C(CC(C1C(O*)=O)C2=CC=C*2)=CC1=O 0.000 description 1
- SGUCIVGSVWRYMH-UHFFFAOYSA-N CCOC(C(C(CC(c(cc1)ccc1-c1ccccc1)=C1)c2ccc[o]2)C1=O)=O Chemical compound CCOC(C(C(CC(c(cc1)ccc1-c1ccccc1)=C1)c2ccc[o]2)C1=O)=O SGUCIVGSVWRYMH-UHFFFAOYSA-N 0.000 description 1
- GFACJXOFXZVPIV-ISTTXYCBSA-N CCOC(CC(C(CC(c1ccc(C/C=C\C=C/C#C)cc1)=C1)C2SC=CC2)C1=O)=O Chemical compound CCOC(CC(C(CC(c1ccc(C/C=C\C=C/C#C)cc1)=C1)C2SC=CC2)C1=O)=O GFACJXOFXZVPIV-ISTTXYCBSA-N 0.000 description 1
- 239000005946 Cypermethrin Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000005906 Imidacloprid Substances 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 229960005424 cypermethrin Drugs 0.000 description 1
- KAATUXNTWXVJKI-UHFFFAOYSA-N cypermethrin Chemical compound CC1(C)C(C=C(Cl)Cl)C1C(=O)OC(C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 KAATUXNTWXVJKI-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229940056881 imidacloprid Drugs 0.000 description 1
- YWTYJOPNNQFBPC-UHFFFAOYSA-N imidacloprid Chemical compound [O-][N+](=O)\N=C1/NCCN1CC1=CC=C(Cl)N=C1 YWTYJOPNNQFBPC-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000013642 negative control Substances 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 230000001018 virulence Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- 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
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
- A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
-
- 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
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
- A01N43/10—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with sulfur as the ring hetero atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/24—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明涉及2‑环己烯酮衍生物及其在农药中的应用，属于农药技术领域。本发明解决的技术问题是提供新的2‑环己烯酮衍生物，该化合物的结构如式I所示。该化合物结构简单、新颖，易于合成，同时兼具杀虫和杀菌活性，对蚕豆蚜和粘虫以及水稻纹枯、小麦赤霉、玉米小斑、油菜菌核、番茄灰霉、葡萄白腐等植物病原真菌都有较好的毒杀效果。
Description
技术领域
本发明涉及2-环己烯酮衍生物及其在农药中的应用，属于农药技术领域。
背景技术
2-环己烯酮含有共轭的羰基和>C＝C<双键结构，是典型的α，β不饱和羰基化合物，能进行多种化学反应，是一种重要的精细化学品，也是重要的医药、农药中间体。因此，近年来对2-环己烯酮衍生物的研究非常活跃。
近年来，在农药的研究和开发过程中，杂环化合物，特别是含O、S、N等元素的化合物，显示出越来越重要的作用，使农药进入了一个超高效、无公害的新时代。由于其选择性好、活性高、用量少、毒性低以及在有害生物生理生化反应中的特异性而成为研究的主体。其中，呋喃、噻吩、吡咯、吡啶、哌啶、嘧啶、吡唑、咪唑和三唑等类化合物，因不断涌现出一些具有划时代意义的新颖药剂而引起人们的重视，也已成为农药领域研究与开发的热点和前沿。
现有的作为农药用的化合物，很少同时具有杀菌和杀虫作用，本发明将呋喃环、噻吩环等引入到2-环己烯酮中，设计合成了一些2-环己烯酮衍生物，发现了一些结构新颖、活性优异的活性化合物或活性先导化合物，为新农药的创制奠定了一定的基础。该2-环己烯酮衍生物同时具有杀虫和杀菌作用。到目前为止，还未见有2-环己烯酮衍生物作为农用杀虫剂和杀菌剂使用的报道。
发明内容
本发明解决的技术问题是提供新的2-环己烯酮衍生物，该化合物同时具有杀虫和杀菌作用。
本发明2-环己烯酮衍生物，其结构如式I所示：
其中，R1为甲基、乙基、正丙基或异丙基；X为N、O或S。
优选的，所述R1为甲基、乙基、正丙基或异丙基；X为O或S。
作为另一优选方案，所述R1为乙基；X为N、O或S。
更优选的，所述2-环己烯酮衍生物的结构式为：
本发明解决的第二个技术问题是提供本发明所述的2-环己烯酮衍生物在抑制或杀灭植物病原真菌中的应用。
优选的，所述植物病原真菌为水稻纹枯病、小麦赤霉病、玉米小斑病、油菜菌核病、番茄灰霉病或葡萄白腐病。
本发明解决的第三个技术问题是提供本发明所述的2-环己烯酮衍生物在防治作物虫害中的应用。
优选的，所述虫害为蚕豆蚜或粘虫。
本发明还提供一种兼具杀虫和杀菌功能的农药，其活性成分为本发明所述的2-环己烯酮衍生物。
与现有技术相比，本发明具有如下有益效果：
本发明的2-环己烯酮衍生物，其结构简单、新颖，易于合成，同时兼具杀虫和杀菌活性，对蚕豆蚜和粘虫以及水稻纹枯、小麦赤霉、玉米小斑、油菜菌核、番茄灰霉、葡萄白腐等植物病原真菌都有较好的毒杀效果。该2-环己烯酮衍生物在目前已知的杀虫剂和杀菌剂中未见报道，为新农药的创制奠定了一定的基础。
具体实施方式
本发明2-环己烯酮衍生物，其结构如式I所示：
其中，R1为甲基、乙基、正丙基或异丙基；X为N、O或S。
优选的，所述R1为甲基、乙基、正丙基或异丙基；X为O或S。
作为另一优选方案，所述R1为乙基；X为N、O或S。
更优选的，所述2-环己烯酮衍生物的结构式为：
本发明2-环己烯酮衍生物的制备方法，可以按照化学合成法，其合成工艺如下：
本发明所述的2-环己烯酮衍生物，可应用在抑制或杀灭植物病原真菌中。
优选的，所述植物病原真菌为水稻纹枯病、小麦赤霉病、玉米小斑病、油菜菌核病、番茄灰霉病或葡萄白腐病。
本发明所述的2-环己烯酮衍生物，也可应用在防治作物虫害中。
优选的，所述虫害为蚕豆蚜或粘虫。
此外，本发明所述的2-环己烯酮衍生物，还能作为活性成分制备成农药，该农药将同时具有杀虫和杀菌的功效。
本发明所述的2-环己烯酮衍生物，同时兼具杀虫和杀菌活性，对蚕豆蚜和粘虫以及水稻纹枯、小麦赤霉、玉米小斑、油菜菌核、番茄灰霉、葡萄白腐等植物病原真菌都有较好的毒杀效果。
下面结合实施例对本发明的具体实施方式做进一步的描述，并不因此将本发明限制在所述的实施例范围之中。
实施例1 化合物(C25H22O4)的制备
(1)中间体1-(4-联苯基)-3-(2-呋喃基)-2-丙烯-1-酮的合成
将0.01mol 4-苯基苯乙酮和10mL无水乙醇加到50mL三颈瓶中，再向其中加入5mL10％NaOH溶液。在冰浴搅拌下，将0.01mol 2-呋喃甲醛和10mL无水乙醇的混合液用恒压滴液漏斗慢慢滴入三颈瓶中，在0-5℃下反应，并用薄层硅胶板(TLC)检查反应是否完成。反应完成后，向混合物中加入3-4倍体积的蒸馏水，并用10％的HCl调节pH值至中性，有沉淀析出，过滤，洗涤，再用无水乙醇重结晶，即得到中间体1-(4-联苯基)-3-(2-呋喃基)-2-丙烯-1-酮。
(2)目标化合物的合成
将0.005mol自制的中间体溶解在20mL无水乙醇中，向其中加入5mL10％NaOH溶液。在搅拌条件下，将0.005mol乙酰乙酸乙酯和10mL无水乙醇的混合溶液用恒压滴液漏斗慢慢滴入上述混合溶液中，在60-70℃下反应20-24小时，并用TLC检查反应是否完成。反应完成后，向混合物中加入3-4倍体积的蒸馏水，并用10％的HCl调节pH值至中性，有沉淀析出，过滤，洗涤，再用无水乙醇重结晶，得到白色粉末状固体产物。产物的波谱数据如下：
IR(KBr)νmax(cm-1):2986,2924,1735,1663,1605,1487,1449,1372,829,769,695；1H NMR(400MHz,DMSO-d6)δ(ppm):7.86(d,J＝8.4Hz,2H),7.79(d,J＝8.4Hz,2H),7.75(d,J＝7.6Hz,2H),7.62(s,1H),7.51(t,J＝7.6Hz,2H),7.44–7.40(m,1H),6.62(d,J＝1.6Hz,1H),6.44–6.43(m,1H),6.31(d,J＝3.2Hz,1H),4.12–4.07(m,2H),3.92–3.81(m,2H),3.26–3.10(m,2H),1.13(t,J＝6.8Hz,3H)；13C NMR(100MHz,DMSO-d6)δ(ppm):193.77(1C),169.73(1C),158.55(1C),155.05(1C),142.59(1C),142.53(1C),139.45(1C),136.56(1C),129.53(2C),128.55(1C),127.69(2C),127.42(2C),127.18(2C),123.29(1C),110.92(1C),106.47(1C),60.89(1C),57.67(1C),37.34(1C),32.27(1C),14.45(1C)；HRMS(ESI)m/z:Calcd forC25H22O4[M+H]+:387.1584,Found:387.1591。
实施例2 化合物(C25H22O3S)的制备
(1)中间体1-(4-联苯基)-3-(2-噻吩基)-2-丙烯-1-酮的合成
将0.01mol 4-苯基苯乙酮和10mL无水乙醇加到50mL三颈瓶中，再向其中加入5mL10％NaOH溶液。在冰浴搅拌下，将0.01mol 2-噻吩甲醛和10mL无水乙醇的混合液用恒压滴液漏斗慢慢滴入三颈瓶中，在0-5℃下反应，并用薄层硅胶板(TLC)检查反应是否完成。反应完成后，向混合物中加入3-4倍体积的蒸馏水，并用10％的HCl调节pH值至中性，有沉淀析出，过滤，洗涤，再用无水乙醇重结晶，即得到中间体1-(4-联苯基)-3-(2-噻吩基)-2-丙烯-1-酮。
(2)目标化合物的合成
将0.005mol自制的中间体溶解在20mL无水乙醇中，向其中加入5mL 10％NaOH溶液。在搅拌条件下，将0.005mol乙酰乙酸乙酯和10mL无水乙醇的混合溶液用恒压滴液漏斗慢慢滴入上述混合溶液中，在60～70℃下反应20-24小时，并用TLC检查反应是否完成。反应完成后，向混合物中加入3-4倍体积的蒸馏水，并用10％的HCl调节pH值至中性，有沉淀析出，过滤，洗涤，再用无水乙醇重结晶，得到白色粉末状固体产物。产物的波谱数据如下：
IR(KBr)νmax(cm-1):2923,2853,1739,1660,1601,1384,830,767,701；1H NMR(400MHz,DMSO-d6)δ(ppm):7.85(d,J＝8.4Hz,2H),7.78(d,J＝8.8Hz,2H),7.75(d,J＝7.6Hz,2H),7.50(t,J＝7.2Hz,2H),7.44–7.40(m,2H),7.11(d,J＝2.8Hz,1H),7.03–7.01(m,1H),6.64(d,J＝1.2Hz,1H),4.06–3.96(m,4H),3.27–3.16(m,2H),1.07(t,J＝7.2Hz,3H)；13C NMR(100MHz,DMSO-d6)δ(ppm):193.95(1C),169.63(1C),158.89(1C),145.03(1C),142.51(1C),139.45(1C),136.57(1C),129.54(2C),128.56(1C),127.63(2C),127.43(2C),127.35(1C),127.19(2C),125.50(1C),124.94(1C),123.32(1C),60.78(1C),60.69(1C),39.17(1C),36.06(1C),14.39(1C)；HRMS(ESI)m/z:Calcd for C25H22O3S[M-H]-:401.1206,Found:401.1217。
试验例1 2-环己烯酮衍生物对蚕豆蚜的毒力测定
1、实验方法
根据张宗炳介绍的方法，以超高效杀虫剂吡虫啉为比较标准，将待测样品溶解于二甲亚砜并用0.1％吐温-80水溶液稀释成5个不同的浓度，以不加待测样品的相应溶液为阴性对照。采集虫口密度大的蚕豆叶，仔细挑选使健康的无翅成蚜(30-50头)留在叶面上，将带虫的蚕豆叶浸入待测溶液5s后拿开，沥干，将叶上的蚕豆蚜转入装有新鲜蚕豆叶的培养皿中，放置在温度为22～24℃，相对湿度为60％，光照时间为14:10h的实验室中继续饲养，24h后记录死亡情况，每一浓度的实验重复3次并按Abbott公式对死亡率进行校正。再根据几率值分析法，采用SPSS软件计算LC50值及其置信区间，并求出相关系数和毒力回归方程。
2、实验结果
实施例1和2化合物对蚕豆蚜的毒杀活性如表1～2所示。
表1 实施例1化合物对蚕豆蚜的毒杀活性
a 3次重复并按Abbott公式校正后的平均值。
从表1可知，实施例1化合物对蚕豆蚜有较好的毒杀活性，其LC50值为9.7mg L-1，而且浓度与药效间存在着显著的相关关系，其相关系数为0.9799。卡方(χ2＝4.442,df＝3,P＞0.05)检验表明测定结果是可靠的。
表2 实施例2化合物对蚕豆蚜的毒杀活性
a 3次重复并按Abbott公式校正后的平均值。
从表2可知，实施例2化合物对蚕豆蚜有较好的毒杀活性，其LC50值为10.1mg L-1，而且浓度与药效间存在着显著的相关关系，其相关系数为0.9708。卡方(χ2＝2.293,df＝3,P＞0.05)检验表明测定结果是可靠的。
试验例2 2-环己烯酮衍生物对粘虫的毒力测定
1、实验方法
根据张宗炳介绍的方法，以高效氯氰菊酯为比较标准，将待测样品溶解于二甲亚砜并用0.1％吐温-80水溶液稀释成5个不同的浓度。将玉米叶片剪成2×5cm的小段，在待测溶液中浸5s后拿开，沥干后放入底部铺有滤纸的培养皿(6cm)中，接入10头3龄幼虫，再将其放置在温度为22-24℃，相对湿度为60％，光照时间为14:10h的实验室中继续饲养，24h后记录死亡情况，每一浓度的实验重复3次并按Abbott公式对死亡率进行校正。再根据几率值分析法，采用SPSS软件计算LC50值及其置信区间，并求出相关系数和毒力回归方程。
2、实验结果
实施例1和2化合物对粘虫的毒杀活性如表3-4所示。
表3 实施例1化合物对粘虫的毒杀活性
a 3次重复并按Abbott公式校正后的平均值。
从表3可知，实施例1化合物对粘虫有较好的毒杀活性，其LC50值为13.2mg L-1，而且浓度与药效间存在着显著的相关关系，其相关系数为0.9919。卡方(χ2＝2.090,df＝3,P＞0.05)检验表明测定结果是可靠的。
表4 实施例2化合物对粘虫的毒杀活性
a 3次重复并按Abbott公式校正后的平均值。
从表4可知，实施例2化合物对粘虫有较好的毒杀活性，其LC50值为10.1mg L-1，而且浓度与药效间存在着显著的相关关系，其相关系数为0.9750。卡方(χ2＝0.736,df＝3,P＞0.05)检验表明测定结果是可靠的。
试验例3 2-环己烯酮衍生物对植物病原真菌的抑菌活性测定
1、供试植物病原真菌
水稻纹枯病菌、小麦赤霉病菌、玉米小斑病菌、油菜菌核病菌、番茄灰霉病菌和葡萄白腐病菌。
2、实验方法
将供试化合物溶于二甲亚砜中，再加入到含有0.1％吐温-80的自来水中，混合均匀后配成200mg/L的供试溶液。将此溶液加入到已灭菌的PDA培养基中，同时再加入浓度为50mg/L的链霉素。以不含供试化合物的相应溶液为空白对照，制成厚薄均匀的含药平板备用，重复三次。用已灭菌的打孔器选取Ф5mm生长良好、无污染、长势均匀的菌饼，在无菌条件下接入含毒培养基和对照培养基的中心(每个平板接种一个菌饼)，在28℃恒温条件下培养。当空白对照的菌落直径长到50mm左右时，采用十字交叉法测量菌落的直径，取其平均值，用下列公式计算相对抑菌率：
3、实验结果
2-环己烯酮衍生物对植物病原真菌的抑菌活性测定结果如表5-6所示。
表5 实施例1化合物在100mg L-1时对植物病原真菌的抑制活性
| 菌种 | 抑制率(％) | 菌种 | 抑制率(％) |
| 水稻纹枯病菌 | 98.3 | 小麦赤霉病菌 | 95.8 |
| 玉米小斑病菌 | 100.0 | 油菜菌核病菌 | 74.9 |
| 番茄灰霉病菌 | 91.4 | 葡萄白腐病菌 | 81.8 |
从表5可知，实施例1化合物对水稻纹枯病菌、小麦赤霉病菌、玉米小斑病菌和番茄灰霉病菌有很好的抑制效果；对油菜菌核病菌和葡萄白腐病菌有较好的抑制效果。
表6 实施例2化合物在100mg L-1时对植物病原真菌的抑制活性
| 菌种 | 抑制率(％) | 菌种 | 抑制率(％) |
| 水稻纹枯病菌 | 100.0 | 小麦赤霉病菌 | 96.7 |
| 玉米小斑病菌 | 93.2 | 油菜菌核病菌 | 94.8 |
| 番茄灰霉病菌 | 85.1 | 葡萄白腐病菌 | 80.6 |
从表6可知，实施例2化合物对水稻纹枯病菌、小麦赤霉病菌、玉米小斑病菌和油菜菌核病菌有很好的抑制效果；对番茄灰霉病菌和葡萄白腐病菌有较好的抑制效果。
Claims (9)
1.2-环己烯酮衍生物，其特征在于，其结构如式I所示：
其中，R1为甲基、乙基、正丙基或异丙基；
X为N、O或S。
2.根据权利要求1所述的2-环己烯酮衍生物，其特征在于：所述X为O或S。
3.根据权利要求1所述的2-环己烯酮衍生物，其特征在于：所述R1为乙基。
4.根据权利要求1所述的2-环己烯酮衍生物，其特征在于：其结构式为：
5.权利要求1～4任一项所述的2-环己烯酮衍生物在抑制或杀灭植物病原真菌中的应用。
6.根据权利要求5所述的2-环己烯酮衍生物在抑制或杀灭植物病原真菌中的应用，其特征在于：所述植物病原真菌为水稻纹枯病菌、小麦赤霉病菌、玉米小斑病菌、油菜菌核病菌、番茄灰霉病菌或葡萄白腐病菌。
7.权利要求1～4任一项所述的2-环己烯酮衍生物在防治作物虫害中的应用。
8.根据权利要求7所述的2-环己烯酮衍生物在防治作物虫害中的应用，其特征在于：所述虫害为蚕豆蚜或粘虫。
9.一种兼具杀虫和杀菌功能的农药，其特征在于：其活性成分为权利要求1～4任一项所述的2-环己烯酮衍生物。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611161787.5A CN106588836B (zh) | 2016-12-15 | 2016-12-15 | 2-环己烯酮衍生物及其在农药中的应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611161787.5A CN106588836B (zh) | 2016-12-15 | 2016-12-15 | 2-环己烯酮衍生物及其在农药中的应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106588836A CN106588836A (zh) | 2017-04-26 |
| CN106588836B true CN106588836B (zh) | 2018-09-18 |
Family
ID=58801660
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611161787.5A Active CN106588836B (zh) | 2016-12-15 | 2016-12-15 | 2-环己烯酮衍生物及其在农药中的应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106588836B (zh) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055926A (zh) * | 1989-04-28 | 1991-11-06 | 日本农药株式会社 | 环己烷衍生物，它的盐和用途以及应用方法 |
| US5076826A (en) * | 1990-10-19 | 1991-12-31 | Evanite Fiber Corporation | Apparatus and method for making glass fibers |
| US20050119129A1 (en) * | 2002-02-19 | 2005-06-02 | Hans-Georg Schwarz | Substituted aryl ketones |
| CN105884665A (zh) * | 2016-04-21 | 2016-08-24 | 潍坊先达化工有限公司 | 一种环己烯酮类化合物及其制备方法与应用 |
-
2016
- 2016-12-15 CN CN201611161787.5A patent/CN106588836B/zh active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055926A (zh) * | 1989-04-28 | 1991-11-06 | 日本农药株式会社 | 环己烷衍生物，它的盐和用途以及应用方法 |
| US5076826A (en) * | 1990-10-19 | 1991-12-31 | Evanite Fiber Corporation | Apparatus and method for making glass fibers |
| US20050119129A1 (en) * | 2002-02-19 | 2005-06-02 | Hans-Georg Schwarz | Substituted aryl ketones |
| CN105884665A (zh) * | 2016-04-21 | 2016-08-24 | 潍坊先达化工有限公司 | 一种环己烯酮类化合物及其制备方法与应用 |
Non-Patent Citations (4)
| Title |
|---|
| 2-(2-呋喃甲酰氨基)苯并噻唑的合成及其抑菌活性研究;高扬等;《西华大学学报（自然科学版）》;20161130;第35卷(第6期);第92-96页 * |
| Mechanochemical synthesis of cyclohexenones and indazoles as potential antimicrobial agents;Abdullah S. Al-Bogami;《Res Chem Intermed》;20151210;第42卷(第6期);第5457-5477页 * |
| Synthesis, Spectral Characterization, In-vitro Antibacterial and Antifungal Activities of Novel (2e)-Ethyl-2-(2-(2, 4-Dinitrophenyl) Hydrazono)-4-(Naphthalen-2-yl)-6-Arylcyclohex-3-Enecarboxylates;V. Kanagarajan et al;《Iranian Journal of Pharmaceutical Research》;20101231;第10卷(第4期);第711-725页 * |
| 环己烯酮除草剂;杨博友;《农药》;19911231;第30卷(第1期);第48-50页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106588836A (zh) | 2017-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112608307B (zh) | 一类杂环取代1,3,4-噁二唑酰肼类化合物及其制备方法和应用 | |
| CN102993097A (zh) | 吡唑酰胺类化合物及其应用 | |
| CN106588836B (zh) | 2-环己烯酮衍生物及其在农药中的应用 | |
| CN105384722B (zh) | 一种缩氨基硫脲类衍生物及其制备方法、应用 | |
| CN109503562A (zh) | 2-[4-(2-噻吩基)]嘧啶基脲衍生物及其制备方法和应用 | |
| CN109942561A (zh) | 4-(2-噻吩基)嘧啶衍生物及其制备方法和应用 | |
| CN111196785B (zh) | 三氮唑衍生物及其制备方法和用途 | |
| CN108849912A (zh) | 1,5-二芳基-3-三氟甲基吡唑类化合物在防治农业真菌病害中的应用 | |
| CN103524418B (zh) | 一组3-甲基吡唑化合物 | |
| CN105028435B (zh) | 一种天然化合物作为农业杀菌剂的用途 | |
| CN103535358B (zh) | 一组邻位取代苯甲酰化合物的杀菌剂用途 | |
| CN103524419B (zh) | 一组3-三氟甲基吡唑化合物 | |
| CN102617482A (zh) | 含三氟甲基嘧啶氨化合物、制备方法和作为杀菌剂的用途 | |
| CN106045982A (zh) | N’‑5‑（取代苯基)‑2‑呋喃甲酰基‑5‑丙基‑1h‑吡唑‑3‑甲酸乙酯类化合物及其制备方法和应用 | |
| CN102827025B (zh) | 2-甲氧基-n-(4-氟苯基)苯甲酰胺及其制备方法和用途 | |
| CN105367543B (zh) | 一种噻吩查尔酮缩氨基脲Schiff碱类化合物及其制备方法、应用 | |
| CN110437099A (zh) | 芳香酰肼类化合物及其制备方法和应用 | |
| CN105418549B (zh) | 一种联苯甲醇类化合物及其制备方法、应用 | |
| CN110447651A (zh) | 一种喹唑啉酮类化合物及在制备或防治农业植物病害中的应用 | |
| CN107286141A (zh) | N‑(3‑吡啶基)亚甲基‑2‑氰基‑3‑杂环基丙烯酰肼类衍生物及其应用 | |
| CN102827027B (zh) | 2-乙酰氧基-n-(3-硝基苯基)苯甲酰胺及其制备方法和用途 | |
| CN102827020B (zh) | 2-甲氧基-n-苯基苯甲酰胺及其制备方法和用途 | |
| CN105348231B (zh) | 2,4‑戊二烯‑1‑醇类化合物及其制备方法、应用 | |
| CN105439995B (zh) | 一种缩氨基脲类化合物及其制备方法、应用 | |
| CN105418579B (zh) | 噻吩丙烯醇类化合物及其制备方法、应用 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201116 Address after: 224300 No. 100, Beihuan West Road, Hede Town, Sheyang County, Yancheng City, Jiangsu Province Patentee after: Yancheng Silk Road Information Technology Service Co.,Ltd. Address before: 610039, No. 999, Jin Zhou road, Jinniu District, Sichuan, Chengdu Patentee before: XIHUA University |
|
| TR01 | Transfer of patent right | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20170426 Assignee: Yancheng Nuohao Xinxiang Technology Co.,Ltd. Assignor: Yancheng Silk Road Information Technology Service Co.,Ltd. Contract record no.: X2023980043986 Denomination of invention: 2-cyclohexanone derivatives and their applications in pesticides Granted publication date: 20180918 License type: Common License Record date: 20231024 |
|
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20170426 Assignee: Jiangsu Jiezhimeng New Energy Technology Co.,Ltd.|Yancheng Yuanshun Environmental Protection Technology Co.,Ltd.|Jiangsu Xingneng Environmental Protection Technology Co.,Ltd.|Tianneng carbon (Jiangsu) Co.,Ltd. Assignor: Yancheng Silk Road Information Technology Service Co.,Ltd. Contract record no.: X2023980047304 Denomination of invention: 2-cyclohexenone derivatives and their applications in pesticides Granted publication date: 20180918 License type: Common License Record date: 20231118 |
|
| EE01 | Entry into force of recordation of patent licensing contract | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240104 Address after: 336000 new century industrial city, Gao'an City, Yichun City, Jiangxi Province Patentee after: Jiangxi Zhongyuan crop protection Co.,Ltd. Address before: No. 100, Beihuan West Road, Hede Town, Sheyang County, Yancheng City, Jiangsu Province Patentee before: Yancheng Silk Road Information Technology Service Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| EC01 | Cancellation of recordation of patent licensing contract |
Assignee: Jiangsu Jiezhimeng New Energy Technology Co.,Ltd.|Yancheng Yuanshun Environmental Protection Technology Co.,Ltd.|Jiangsu Xingneng Environmental Protection Technology Co.,Ltd.|Tianneng carbon (Jiangsu) Co.,Ltd. Assignor: Yancheng Silk Road Information Technology Service Co.,Ltd. Contract record no.: X2023980047304 Date of cancellation: 20240425 Assignee: Yancheng Nuohao Xinxiang Technology Co.,Ltd. Assignor: Yancheng Silk Road Information Technology Service Co.,Ltd. Contract record no.: X2023980043986 Date of cancellation: 20240425 |
|
| EC01 | Cancellation of recordation of patent licensing contract |