CN114315551A - Compound and preparation method and application thereof - Google Patents
Compound and preparation method and application thereof Download PDFInfo
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- CN114315551A CN114315551A CN202210035181.6A CN202210035181A CN114315551A CN 114315551 A CN114315551 A CN 114315551A CN 202210035181 A CN202210035181 A CN 202210035181A CN 114315551 A CN114315551 A CN 114315551A
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Abstract
The invention discloses a structural formula, a preparation method and application of a novel compound (3Z,6Z) -nonadecadiene-9-ketone. In the invention, (3Z,6Z) -nonadecadiene-9-ketone can be used as a repellent to efficiently repel the insects of the family Bombycidae, particularly the male insects of the flower loopers, in forests, so that the population density of the male insects in the forests is reduced, the proportion of the male and female insects is inconsistent, the mating between the male and female insects is interfered, and the harm to host plants such as white birch and the like is reduced. The compound has high biological activity as a repellent, can be matched with an attractant for use, and can repel the Chilolidae pests such as the ectropis griseiformis and the like in areas with complex forest land conditions and unsuitable use of chemical pesticides, thereby achieving the purpose of prevention and control.
Description
Technical Field
The application relates to the technical field of pest control, in particular to a compound and a preparation method and application thereof.
Background
The superfamily of ulworms is the third major family of lepidopteran insects, and currently, pheromone components of a total of 93 species of ulworms of 158 species are identified. The pheromone component of the Dipteraceae insects is mainly unsaturated hydrocarbon and corresponding epoxy derivative or hydrocarbon compound (C) with methyl side chain17-C23) Small amount of alcohol, aldehyde, acetate, butyrate and ketone compounds. In the prior art, the application of the pheromone of the ulexidae insects is in the aspect of multi-concentration attraction, and although the pheromone repelling aspect is reported, the practical application is less.
The Ectropis griseus (Lareranis orthograpara (Wehrli)) is an insect of Lepidotera, Geometridae, Ennominae, the subfamily Geotrichu, Lepidoptera. The worm takes place 1 generation per year, overwintering with eggs in the bark cleft. Hatching larvae in the middle and last 5 months of the next year, enabling aged larvae to enter soil and pupate in the last 6 months, enabling pupae to begin to emerge in the last 10 months of the year, and mating and spawning. Hosts comprise various broad-leaved trees such as white birch, red birch, betula robusta, populus deltoides and salix integra, the larvae have large food consumption, tender shoots of the hosts can be completely eaten, and the influence on the growth of forest trees is great. The insect has been on the rise in recent years, and poses a serious threat to the production of natural forests.
At present, a chemical agent is the most important means for preventing and controlling the ectropis griseifolia, and in the larval stage, 50 percent of insecticidal oil purifier and 1:1(V/V) of diesel oil are mixed and sprayed, and the killing rate is more than 95 percent; in addition, biological agents can be used for preventing and treating, the bacillus thuringiensis emulsion and 50% of insecticidal neat oil are mixed and sprayed according to the ratio of 11:1, and the effect can reach 87%. At present, although chemical pesticides have quick effect, the method has high prevention and treatment cost, and is easy to generate pesticide residue, environmental pollution, drug resistance of pests and other problems.
The insect pest control agent utilizes the self information chemical substances of the insects to control the harm of the pests or interfere and prevent the pests from being harmed, and can achieve the aim of directly or indirectly controlling the pests. The product has the advantages of environmental protection, no residue, safety and no toxicity to human and livestock, and has wide application prospect.
Disclosure of Invention
The invention providesThe structural formula of the compound is shown as a formula I,
the preparation method of the compound comprises the steps of dissolving (3Z,6Z) -nonadienenitrile in tetrahydrofuran, then reacting with decyl magnesium bromide, and purifying to obtain (3Z,6Z) -nonadecadien-9-one, namely the compound.
Specifically, the preparation method of the compound comprises the following steps:
(1) in N2Every 2.70g of (3Z,6Z) -nonadienenitrile was dissolved in 30ml of tetrahydrofuran under protection to give a solution I;
(2) 20mg of CuI and 30ml of 1M decyl magnesium bromide were added in succession to the solution I, reacted at-20 ℃ for 24h and then reacted with saturated NH4Stopping the reaction by Cl to obtain a reaction solution;
(3) extracting the reaction solution with n-hexane, combining the organic phases, and purifying with anhydrous MgSO4Drying;
(4) removing an organic phase by reduced pressure distillation to obtain a crude product;
(5) the crude product is purified by a silica gel column by taking petroleum ether/ethyl acetate 20-10:1 as a mobile phase to obtain (3Z,6Z) -nonadecadiene-9-ketone.
The invention also provides application of the compound (3Z,6Z) -nonadecadiene-9-ketone in repelling insects in the family of the dipteraceae.
Specifically, the insects are loopers of the grey flower looper.
The invention also provides a repellent for the insects in the family of the diamond back moths, which comprises the compound.
The invention also provides a method for controlling the ulexidae insects, which adopts the repellent to control the ulexidae insects.
Specifically, the using amount of the repellent is 100-; the distance between every two repellents is 30-50 m. The insects are loopers of the grey flower.
Further, the control method further comprises the step of arranging an attractant on the periphery of the area where the repellent is arranged. Specifically, the attractant comprises (3Z,6Z,9Z) -heneicosyl triene 2500ug, (3Z,6Z,9Z) -nineteen triene 2500 ug; the distance between the attractant and the repellent is 50-100 m; the repellent is directly fixed on the tree; the repellent is set to be 1.5-3m away from the ground; the attractant is fixed between the two trees; the height of the attractant is 1.5-3m above the ground.
The beneficial effects of the invention include:
the novel compound (3Z,6Z) -nonadecadiene-9-ketone provided by the invention can be used as a repellent to effectively repel the insects of family Onychidae, particularly the male insects of the looper griseo, reduce the population density of the male insects in forests, ensure that the proportion of the male and female insects is not coordinated, interfere the mating between the male and female insects, and reduce the harm to host plants such as white birch and the like. The compound has high biological activity as a repellent, can be matched with an attractant for use, and can repel the Chilolidae pests such as the ectropis griseiformis and the like in areas with complex forest land conditions and unsuitable use of chemical pesticides, thereby achieving the purpose of prevention and control.
The repellent provides a new idea for researching and developing pest repellents and mating disruptors, has important application value and economic value in nuisanceless control of the ectropis griseiformis, and has remarkable social benefit and ecological benefit.
Drawings
FIG. 1 shows the repelling test results of the ectropis griseus repellent (100ug) on male imagoes of the ectropis griseus;
FIG. 2 shows the experimental results of repelling male adults of Ectropis griseiformis by the repellent (250ug) of Ectropis griseiformis;
FIG. 3 shows the repelling test results of the ectropis griseus repellent (1000ug) on male adults of the ectropis griseus;
FIG. 4 shows the repelling test results of the ectropis griseus repellent (2500ug) on male adults of the ectropis griseus;
FIG. 5 shows the repelling test results of the ectropis griseus repellent (5000ug) on male adults of the ectropis griseus;
FIG. 6 shows the trapping effect of the repellent (5000 ug)/attractant on male imagoes of loopers of quasipaa griseola;
FIG. 7 is a schematic diagram of woodland suspension of the repellent and attractant of Ectropis griseola;
FIG. 8 is a scheme showing the synthesis of (3Z,6Z) -nonadecadien-9-one, a compound of the present invention.
Detailed Description
The present invention will be further illustrated and described with reference to the following examples, but the examples described are only a part of the examples of the present invention, and not all of the examples. All other inventions and embodiments based on the present invention and obtained by a person of ordinary skill in the art without any creative effort belong to the protection scope of the present invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1 structural formula and Synthesis method of novel Compound (3Z,6Z) -nonadecadien-9-one
The structural formula of (3Z,6Z) -nonadecadien-9-one is shown as formula I:
preparation of (3Z,6Z) -nonadecadien-9-one
The preparation is carried out according to the synthetic route in figure 8, and the specific steps are as follows:
(1) in N2Under protection, 2.70g of (3Z,6Z) -nonadienenitrile was dissolved in 30ml of tetrahydrofuran to give a solution I.
(2) Adding 20mg of cuprous iodide (CuI) and 30ml of 1M decyl magnesium bromide into the solution I in sequence, reacting at-20 deg.C for 24h, and adding saturated NH4The reaction was terminated with Cl to obtain a reaction solution.
(3) Extracting the reaction solution with n-hexane, combining the organic phases, and purifying with anhydrous MgSO4And (5) drying.
(4) After removing the organic phase by evaporation under reduced pressure, a crude product was obtained.
(5) The crude product was purified by silica gel column using petroleum ether/ethyl acetate 20:1 as the mobile phase to give (3Z,6Z) -nonadecadien-9-one (3.34g, 60% yield).
3. Structure confirmation of novel Compound (3Z,6Z) -nonadecadien-9-one
(1) Nuclear magnetic data:1H-NMR(500MHz,CDCl3)δ0.87(3H,t,J＝7.5Hz),0.97(3H,t,J＝7.5Hz),1.25–1.35(14H,m),1.54(2H,m),2.05(2H,m),2.40(2H,m),2.80(2H,m),2.94(2H,m),5.29–5.52(4H,m).。
(2) mass spectrometry data: GC-MS (70eV, EI): 278.
The structure is identified to be correct.
Example 2 repellent Effect test of 100ug (3Z,6Z) -nonadecadien-9-one
In the embodiment, the griseous loopers are taken as repelling objects, and the repelling effect of (3Z,6Z) -nonadecadien-9-one on the insects in the family of the armyworms is researched.
1. Preparing materials:
(1) preparing an inchworm repellent of the griseo flower: 100ug of (3Z,6Z) -nonadecadien-9-one prepared in example 1 was added to a polyethylene plastic tube (commercially available) to prepare an inchworm (inchworm) ash repellent.
(2) Preparing a lure core of the ectropis obliqua attractant: adding (3Z,6Z,9Z) -heneicosyl-triene 2500ug and (3Z,6Z,9Z) -nineteen-triene 2500ug into a polyethylene plastic pipe (purchased in the market), and preparing into the looper attractant lure core.
(3) The trapper is a small boat-shaped trapper (purchased in the market) and is internally provided with a pest sticking plate.
2. And (3) experimental design:
(1) 1 blank carrier (blank), 1 repellent (repellent), 1 attractant and attractant attracting core (repellent/attractant) and 1 attractant attracting core (attractant) are respectively fixed in the interior of different boat-shaped traps by using thin iron wires to prepare 4 traps for 4 groups of test treatment.
(2) The test site was a hematoxylin mountain, and 4 traps were placed in the forest, respectively, i.e., 4 test treatments, each set of 3 replicates, with an intra-block trap spacing of approximately 50 meters and an inter-block trap spacing of 500 meters. The trap is fixed between the two trees and the trap is 150cm above the ground.
(3) Data investigation: investigators recorded the number of trapped male adults every 3-4 days and replaced the sticky trap. The average trapping number of the single traps for the gray loopers was counted from 18 months to 29 months in 2020, and the result is shown in FIG. 1.
From the data analysis in fig. 1, the looper griseo attractant has a very good trapping effect on the lure (compared with the blank group); 100ug (3Z,6Z) -nonadecadiene-9-ketone has strong repellency to male imagoes of the ectropis griseus, and can reduce the trapping amount of the lure of the ectropis griseus attractant by 42.7 percent.
Example 3250 ug (3Z,6Z) -nonadecadien-9-one repellent Effect test
In this example, the average trapping number of the ashbya inchworm is shown in FIG. 2, except that the (3Z,6Z) -nonadecadien-9-one content in the repellent for ashbya inchworm is 250 ug.
From the data analysis in FIG. 2, it is found that (3Z,6Z) -nonadecadiene-9-one shows strong repellency to male imagoes of ectropis griseus, and can reduce the trapping amount of the attractant core of the ectropis griseus attractant by 45.9%.
Example 41000 ug (3Z,6Z) -nonadecadien-9-one repellent Effect test
In this example, the average trapping number of the ashbya inchworm is shown in FIG. 3, except that the (3Z,6Z) -nonadecadien-9-one content in the repellent for ashbya inchworm is 1000ug, and the rest is the same as that in example 2.
From the data analysis in FIG. 3, it is found that (3Z,6Z) -nonadecadiene-9-one shows strong repellency to male adults of the ectropis griseus, and can reduce the trapping amount of the lure of the ectropis griseus attractant by 51.7%.
Example 52500 ug (3Z,6Z) -nonadecadien-9-one repellency test
In this example, the average trapping number of the ashbya inchworm is shown in FIG. 4, except that the (3Z,6Z) -nonadecadien-9-one content in the repellent for ashbya inchworm is 2500 ug.
From the data analysis in FIG. 4, it is found that (3Z,6Z) -nonadecadiene-9-one shows strong repellency to male adults of the ectropis griseus, and can reduce the trapping amount of the lure of the ectropis griseus attractant by 69.2%.
Example 65000 ug (3Z,6Z) -nonadecadien-9-one repellent Effect test
In this example, the results of the average trapping amount of the griseootheca arrestis are shown in FIG. 5, and the effect of trapping adults is shown in FIG. 6, except that the (3Z,6Z) -nonadecadien-9-one content in the griseootheca arrestis repellent was 5000 ug.
From the data analysis in FIG. 5, it is found that (3Z,6Z) -nonadecadiene-9-one shows strong repellency to male adults of the ectropis griseus, and can reduce the trapping amount of the lure of the ectropis griseus attractant by 71.5%.
From the above experiments on the repellent effect of examples 2-6, it can be found that when the ectropis griseus repellent and the attractant are used simultaneously, the trapping amount of the ectropis griseus can be remarkably inhibited, the trapping amount is reduced by 42.7% -71.5%, and the ectropis griseus repellent used alone in each example does not trap the ectropis griseus, which indicates that the (3Z,6Z) -nonadecadiene-9-one can be used as the repellent of the ectropis griseus in the field to prevent and control the ectropis griseus, and the content of the (3Z,6Z) -nonadiene-9-one is preferably 5000-ug.
Example 7 Effect test of coordinated use of repellent and attractant
The embodiment is used for evaluating the effect of the repellent (3Z,6Z) -nonadecadiene-9-one and the attractant in coordination for preventing and controlling the looper buzura suppressaria, and the test design is as follows:
(1) the total number of 2 treatments are set, wherein the treatment 1 is a cursoria cinerarius repellent ((3Z,6Z) -nonadecadiene-9-one 5000ug) + a cursoria cinerarius attractant ((3Z,6Z,9Z) -heneicosyl 2500ug, (3Z,6Z,9Z) -nonadecyl 2500ug), and the treatment 2 is a blank carrier + cursoria cinerarius attractant ((3Z,6Z,9Z) -henesyl 2500ug, (3Z,6Z,9Z) -nonadecyl 2500 ug).
(2) In the birch forest in the northern mountain forest farm in the Qinghai mutual-aid county, 6 areas are selected, the interval of each area is 300m, each area is provided with one treatment, each treatment is provided with 3 repetitions, and the specific settings are as follows:
treatment 1: 9 buzura griseki repellents are hung in each area (area 1,3 and 5) and are distributed in a square shape at intervals of 30m, and the repellents are directly fixed on the birch and have the height of 150cm above the ground. 4 traps loaded with the attractant for ectropis griseus were suspended around the periphery of the square repellent (as shown in fig. 7A), the attractant traps were fixed between two trees, 50m away from the repellent, and the traps were 1.5m higher from the ground.
And (3) treatment 2: this group replaced the repellent with a blank carrier and the hanging method was identical to treatment 1 (shown in fig. 7B, corresponding to zones 2,4, 6).
Data investigation: investigators recorded the number of trapped male adults every 3-4 days and replaced the sticky trap. The average trapping number of the single traps for the gray loopers were counted from 8 days 10 to 21 days 10 in 2021, and the results are shown in Table 1. As can be seen from the amounts of the insects to which the armyworm plates are adhered in Table 1 and FIG. 7, the synergistic use of the repellents and attractants for the loopers of the ashitaba flowers significantly increases the trapping amount of the loopers of the ashitaba flowers.
TABLE 1 evaluation of trapping Effect of treatments 1 to 2 of this example
Claims (10)
1. A compound has a structural formula shown in formula I,
2. a process for the preparation of a compound according to claim 1, which comprises dissolving (3Z,6Z) -nonadienenitrile in tetrahydrofuran, reacting with decylgagnesium bromide, and purifying to obtain (3Z,6Z) -nonadecadien-9-one, which is the compound according to claim 1.
3. The method of manufacturing according to claim 2, comprising the steps of:
(1) in N2Every 2.70g of (3Z,6Z) -nonadienenitrile was dissolved in 30ml of tetrahydrofuran under protection to give a solution I;
(2) 20mg of CuI and 30ml of 1M decyl magnesium bromide were added in succession to the solution I, reacted at-20 ℃ for 24h and then reacted with saturated NH4Stopping the reaction by Cl to obtain a reaction solution;
(3) extracting the reaction solution with n-hexane, combining the organic phases, and purifying with anhydrous MgSO4Drying;
(4) removing an organic phase by reduced pressure distillation to obtain a crude product;
(5) the crude product is purified by a silica gel column by taking petroleum ether/ethyl acetate 20-10:1 as a mobile phase to obtain (3Z,6Z) -nonadecadiene-9-ketone.
4. The use of a compound of claim 1 for repelling an insect from the family of moths.
5. The use according to claim 4, wherein the insect is ectropis griseus.
6. A repellent for insects of the family ophidiaceae comprising a compound of claim 1.
7. A method for controlling an insect of the family Meridae, characterized in that the repellent of claim 6 is used to control an insect of the family Meridae.
8. The control method as claimed in claim 7, wherein the amount of the repellent is 100-5000 ug/place, the number of forest suspenders is 1-5/mu, and the distance between every two repellent is 30-50 m; and/or the insect is an inchworm of flowers ichthyophthirius.
9. A method of controlling as claimed in claim 8, further comprising providing an attractant peripherally of the area in which the repellant is provided.
10. The method of claim 9, comprising one or more of the following (1) - (6):
(1) the attractant comprises (3Z,6Z,9Z) -heneicosyl-triene 2500ug, (3Z,6Z,9Z) -nineteen-triene 2500 ug;
(2) the distance between the attractant and the repellent is 50-100 m;
(3) the repellent is directly fixed on the tree;
(4) the repellent is set to be 1.5-3m away from the ground;
(5) the attractant is fixed between the two trees;
(6) the height of the attractant is 1.5-3m above the ground.
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Citations (4)
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|---|---|---|---|---|
| EP0183922A2 (en) * | 1984-09-05 | 1986-06-11 | BASF Aktiengesellschaft | Process and agent for combating the rhomboid looper Boarmia rhomboidaria |
| CA2041529A1 (en) * | 1991-04-30 | 1992-10-31 | Gerhard Johannes Gries | Method and composition for attracting and controlling hemlock loopers |
| CN102823590A (en) * | 2011-06-17 | 2012-12-19 | 信越化学工业株式会社 | Sex pheromone composition of peach fruit moth and attractant comprising the same |
| CN109970534A (en) * | 2019-04-24 | 2019-07-05 | 中国农业大学 | A method of synthesis sex pheromone of Carposina niponensis |
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2022
- 2022-01-13 CN CN202210035181.6A patent/CN114315551B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0183922A2 (en) * | 1984-09-05 | 1986-06-11 | BASF Aktiengesellschaft | Process and agent for combating the rhomboid looper Boarmia rhomboidaria |
| CA2041529A1 (en) * | 1991-04-30 | 1992-10-31 | Gerhard Johannes Gries | Method and composition for attracting and controlling hemlock loopers |
| CN102823590A (en) * | 2011-06-17 | 2012-12-19 | 信越化学工业株式会社 | Sex pheromone composition of peach fruit moth and attractant comprising the same |
| CN109970534A (en) * | 2019-04-24 | 2019-07-05 | 中国农业大学 | A method of synthesis sex pheromone of Carposina niponensis |
Non-Patent Citations (3)
| Title |
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| 刘天麟等: "茶尺蠖性信息素几种活性成分的合成", 《南开大学学报（自然科学版）》, no. 01, pages 1 - 5 * |
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| 杨明伟等: "蛾类昆虫雄性信息素及其功能", 《华东昆虫学报》, no. 03, pages 179 - 186 * |
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