CN110563744B - Compound for preventing and controlling noctuids in gardens and application - Google Patents
Compound for preventing and controlling noctuids in gardens and application Download PDFInfo
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- CN110563744B CN110563744B CN201910956782.9A CN201910956782A CN110563744B CN 110563744 B CN110563744 B CN 110563744B CN 201910956782 A CN201910956782 A CN 201910956782A CN 110563744 B CN110563744 B CN 110563744B
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- artemisia annua
- noctuids
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 18
- PLQMEXSCSAIXGB-SAXRGWBVSA-N (+)-artemisinic acid Chemical compound C1=C(C)CC[C@H]2[C@H](C)CC[C@@H](C(=C)C(O)=O)[C@H]21 PLQMEXSCSAIXGB-SAXRGWBVSA-N 0.000 claims abstract description 24
- 235000001405 Artemisia annua Nutrition 0.000 claims abstract description 17
- 240000000011 Artemisia annua Species 0.000 claims abstract description 17
- LZMOBPWDHUQTKL-RWMBFGLXSA-N artemisinic acid Natural products CC1=C[C@@H]2[C@@H](CCC[C@H]2C(=C)C(=O)O)CC1 LZMOBPWDHUQTKL-RWMBFGLXSA-N 0.000 claims abstract description 12
- PLQMEXSCSAIXGB-UHFFFAOYSA-N artemisininic acid Natural products C1=C(C)CCC2C(C)CCC(C(=C)C(O)=O)C21 PLQMEXSCSAIXGB-UHFFFAOYSA-N 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims abstract description 4
- 229920005989 resin Polymers 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 241000256259 Noctuidae Species 0.000 claims description 11
- 239000000706 filtrate Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 6
- 241000985245 Spodoptera litura Species 0.000 claims description 4
- 238000010828 elution Methods 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 238000001819 mass spectrum Methods 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003480 eluent Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 241000500437 Plutella xylostella Species 0.000 claims 1
- 239000003814 drug Substances 0.000 abstract description 7
- 230000002147 killing effect Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 241000607479 Yersinia pestis Species 0.000 abstract description 4
- 238000002474 experimental method Methods 0.000 abstract description 2
- 238000002953 preparative HPLC Methods 0.000 abstract 1
- 241000238631 Hexapoda Species 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 241000256251 Spodoptera frugiperda Species 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 235000013399 edible fruits Nutrition 0.000 description 3
- 241000255901 Tortricidae Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- OEBRKCOSUFCWJD-UHFFFAOYSA-N dichlorvos Chemical compound COP(=O)(OC)OC=C(Cl)Cl OEBRKCOSUFCWJD-UHFFFAOYSA-N 0.000 description 2
- 229950001327 dichlorvos Drugs 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 244000144730 Amygdalus persica Species 0.000 description 1
- 244000003416 Asparagus officinalis Species 0.000 description 1
- 235000005340 Asparagus officinalis Nutrition 0.000 description 1
- 240000000724 Berberis vulgaris Species 0.000 description 1
- 235000016068 Berberis vulgaris Nutrition 0.000 description 1
- 235000004936 Bromus mango Nutrition 0.000 description 1
- 235000003255 Carthamus tinctorius Nutrition 0.000 description 1
- 244000020518 Carthamus tinctorius Species 0.000 description 1
- 241000207199 Citrus Species 0.000 description 1
- 235000005206 Hibiscus Nutrition 0.000 description 1
- 235000007185 Hibiscus lunariifolius Nutrition 0.000 description 1
- 244000048199 Hibiscus mutabilis Species 0.000 description 1
- 235000003973 Hibiscus mutabilis Nutrition 0.000 description 1
- 244000284380 Hibiscus rosa sinensis Species 0.000 description 1
- 244000130592 Hibiscus syriacus Species 0.000 description 1
- 235000018081 Hibiscus syriacus Nutrition 0.000 description 1
- 241000659518 Lozotaenia capensana Species 0.000 description 1
- 240000000982 Malva neglecta Species 0.000 description 1
- 235000000060 Malva neglecta Nutrition 0.000 description 1
- 240000007228 Mangifera indica Species 0.000 description 1
- 235000014826 Mangifera indica Nutrition 0.000 description 1
- 241000167562 Pittosporum tobira Species 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- 235000014443 Pyrus communis Nutrition 0.000 description 1
- 241000256247 Spodoptera exigua Species 0.000 description 1
- 235000009184 Spondias indica Nutrition 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 210000003323 beak Anatomy 0.000 description 1
- 235000020971 citrus fruits Nutrition 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000009982 effect on human Effects 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
Images
Classifications
-
- 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
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/12—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains three hetero rings
- C07D493/20—Spiro-condensed systems
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- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Toxicology (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention belongs to the technical field of garden pest control, and relates to a compound for controlling noctuids in gardens and application thereof. Extracting fresh tender leaves of Artemisia annua with water, separating with macroporous resin, tracking with semi-preparative high performance liquid chromatography, preparing, and recrystallizing to obtain the compound, named as Artemisinic acid, as new compound. The compound for preventing and treating the noctuids in the gardens is prepared from natural medicine artemisia annua which is used as a medicine, an extract of the artemisia annua is used for clinic for many times, no obvious side effect is caused to a human body, the safety is good, and an activity experiment also shows that the artemisinic acid has a good killing effect on the noctuids and has a wide application prospect.
Description
Technical Field
The invention belongs to the technical field of garden pest control, and particularly relates to a compound for controlling noctuids in gardens and application thereof.
Background
Noctuids refer to a class of insects in the family noctuidae, most of which are phytophagous pests, and a few of which prey on other insects. Some kinds of adults have strong beaks and can puncture the peel to suck fruit juice, and a few kinds of adults can suck secretion of people and livestock. When a large number of species of noctuidae occur, great damage is caused to trees and crops. For example, the larvae of the Spodoptera exigua can damage leaves of plane barberry, citrus, shrubalthea, cotton rose, pittosporum tobira, mango, hibiscus, mallow, safflower and the like, and the leaves are eaten and polished, only veins are left, and the ornamental effect of flowers and trees is influenced. And leaf rollers are also harmful to apple, sand fruit, peach, pear, plum and other fruit trees, when larva of the leaf rollers are harmful to leaves, 2-3 leaves are strung together by spinning, and the leaves are eaten in the silk, and are netted or notched.
For preventing and treating garden diseases and insect pests, the main noctuid method comprises the following steps: scraping old tilted skin, shearing dead skin tissues around the saw cut and the wound in spring or in early winter to eliminate overwintering larvae; before the bud of the fruit tree is germinated, a 50-fold solution of dichlorvos or a 30-fold solution of duspi plus an auxiliary agent are smeared on a saw cut, a wound and an old upwarp skin, so that a large number of overwintering larvae can be killed. However, scraping the bark is troublesome and harmful to the trees, while the dichlorvos used for killing the noctuids is too toxic and harmful to operators and ornamental persons in gardens. Although more noctuid killing drugs are developed in the following, the noctuid killing drugs have low toxicity to human bodies and less drug which can kill noctuids efficiently.
Disclosure of Invention
In order to solve the technical problems, the invention discovers a compound for preventing and controlling noctuids in gardens. The compound is from natural products and has good killing effect on noctuids.
The compound for preventing and treating noctuid in gardens is named as artemisinic acid, and the structure of the artemisinic acid is as follows:
the preparation method of the artemisinic acid comprises the following steps: adding fresh tender leaves of Artemisia annua into 8-12 times of water, homogenizing, filtering to obtain filtrate, loading the filtrate on macroporous resin column, eluting with 70% ethanol for over 10 times of the dry extract weight of the filtrate, then eluting with 75-80% ethanol for 5 times of the dry extract weight, mixing the eluates, and removing solvent to obtain Artemisia annua preparation; dissolving the artemisia annua preparation in 30 times of methanol, filtering with a 0.22um filter membrane, taking filtrate, performing semi-preparation of high performance liquid phase, detecting the wavelength of 292nm, tracing by mass spectrum, performing gradient elution, performing flow rate of 1.0ml/min, performing elution time of 0.5h, performing mobile phase change from methanol to water ratio of 3:7 to methanol to water ratio of 9:1, collecting eluent containing 326.1366 molecular weight signals in a time period of 12-15min, concentrating, and recrystallizing to obtain the artemisia annua extract.
The application of the artemisinic acid is used for preventing and controlling the asparagus caterpillars in gardens. In particular to the silver looper, the prodenia litura, the small bridgeworm and the apple leaf roller.
The compound of the invention is a new compound, is derived from natural medicine artemisia annua which is used as a medicine, the extract of the artemisia annua is used for clinic for many times, has no obvious side effect on human bodies, has good safety, and activity experiments also show that the artemisia annua L acid has good killing effect on the noctuid and has wide application prospect.
Drawings
FIG. 1: the structural formula of the novel compound artemisinic acid is disclosed.
Detailed Description
The following examples are provided to further illustrate the compounds for controlling noctuid in gardens and gardens, but the scope of the present invention is not limited thereto.
Example 1
Adding 10 times of water into fresh artemisia annua tender leaves, homogenizing, filtering to obtain filtrate, loading the filtrate on a D101 macroporous resin column, eluting 10 times of column volume by using 70% ethanol, then eluting 5 times of column volume by using 75% ethanol, combining 75% ethanol eluates, and removing a solvent to obtain the artemisia annua preparation. Dissolving Artemisia annua preparation in 30 times of methanol, filtering with 0.22um filter membrane, collecting filtrate, performing semi-preparation of high performance liquid phase, detecting wavelength of 292nm, tracking with mass spectrum, gradient eluting at flow rate of 3.0ml/min for 0.5h, changing flow phase into methanol-to-water ratio of 3:7 to 9:1, collecting eluate containing molecular weight signal 326.1366 in 12-15min, concentrating, and recrystallizing. The structural identification of the novel compound of the artemisinic acid: colorless crystals, HRMS: 326.1362([ M-H) } M/z]-，calc.for C16H22O6325.1284)；1HNMR(300MHz，CDCl3)δppm：1.41(1H，J1-10α＝6.8，J1-10β＝11.2，C1-H)，1.46(1H，J2-14＝6.1Hz，C2-H)，1.79，1.09(1H，C3-H)，1.86，1.08(1H，C4-H)，1.79(1H，J5-11＝5.0，C5-H)，5.87(C7-H)，2.01，1.55(2H，J9α-9β＝14.6，J9α-10β＝3.8，J9α-10β＝13.4，C9-H)，2.31(H，J9α-10β＝3.8，J9α-10β＝13.4，C10-H)，3.40(1H，J11-13＝7.1，C11-H)，1.22(3H，C13-H)，1.01(3H，C15-H)，1.46(3H，C16-H)，11.23(1H，OH)。13C-NMR(300MHz，CDCl3)δppm：51.24，(C1)，37.87(C2)，34.08(C3)，23.11(C4)，46.04(C5)，80.03(C6)，91.44(C7)，104.92(C8)，22.84(C9)，53.21(C10)，32.84(C11)，172.23(C12)，12.65(C13)，182.12(C14)，19.98(C15)，26.02(C16)。
Activity assay
Diluting the artemisinic acid into solutions with mass concentrations of 2, 6, 18 and 54mg/ml respectively by using 50% ethanol, soaking 3-instar larvae of the Argyroma agnata, the prodenia litura, the Spodoptera litura and the Spodoptera frugiperda in the artemisinic acid solutions with different mass concentrations for 3s, placing the solutions on absorbent paper for airing, placing the solutions in 48-hole culture plates filled with artificial feed, treating 10 respectively different Spodoptera frugiperda on each plate, setting two holes by using 50% ethanol as a contrast, repeating the steps for 3 times, counting the death conditions of the Spodoptera frugiperda on the 3 rd and 7 th days after treatment respectively, and calculating the average death rate. If the insects are touched slightly, the dead or unable to crawl normally is counted as death. The results are shown in Table 1.
Table 1: siberinic acid killing effect on noctuid (average mortality,%)
Claims (3)
1. The compound for preventing and treating garden noctuids is named as artemisinic acid, and the structure of the artemisinic acid is shown as follows:
the preparation method of the compound comprises the following steps: adding fresh tender leaves of Artemisia annua into 8-12 times of water, homogenizing, filtering to obtain filtrate, loading the filtrate on macroporous resin column, eluting with 70% ethanol for over 10 times of the dry extract weight of the filtrate, then eluting with 75-80% ethanol for 5 times of the dry extract weight, mixing the eluates, and removing solvent to obtain Artemisia annua preparation; dissolving the artemisia annua preparation in 30 times of methanol, filtering with a 0.22um filter membrane, taking filtrate, performing semi-preparation of high performance liquid phase, detecting the wavelength of 292nm, tracing by mass spectrum, performing gradient elution, performing flow rate of 1.0ml/min, performing elution time of 0.5h, performing mobile phase change from methanol to water ratio of 3:7 to methanol to water ratio of 9:1, collecting eluent containing 326.1366 molecular weight signals in a time period of 12-15min, concentrating, and recrystallizing to obtain the artemisia annua extract.
2. Use of a compound according to claim 1 for the control of noctuid in plantations.
3. The use of claim 2, wherein the noctuid is a silver looper, a prodenia litura, a diamondback moth, or an apple leafroll moth.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910956782.9A CN110563744B (en) | 2019-10-10 | 2019-10-10 | Compound for preventing and controlling noctuids in gardens and application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910956782.9A CN110563744B (en) | 2019-10-10 | 2019-10-10 | Compound for preventing and controlling noctuids in gardens and application |
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| Publication Number | Publication Date |
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| CN110563744A CN110563744A (en) | 2019-12-13 |
| CN110563744B true CN110563744B (en) | 2021-10-26 |
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| EP1732500B1 (en) * | 2004-01-07 | 2018-11-21 | E-L Management Corporation | Cosmetic composition and method for retarding hair growth |
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| CN102010422B (en) * | 2010-11-23 | 2014-11-26 | 沈阳药科大学 | Guanidyl-containing artemisinin derivates and application thereof |
| CN105594764A (en) * | 2015-12-25 | 2016-05-25 | 郑州金土地能源科技有限公司 | Plant insecticide |
| CN108383851A (en) * | 2016-12-09 | 2018-08-10 | 新乡学院 | One kind having the active qinghaosu ester type compound of cardiovascular disease prevention, preparation method and its application |
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