CN110859180A

CN110859180A - Synthetic method, identification and intelligent release system of larch geometrid sex pheromone composition

Info

Publication number: CN110859180A
Application number: CN201911145209.6A
Authority: CN
Inventors: 刘福; 张真; 孔祥波; 张苏芳; 李如华; 张志林; 国志峰; 周福成; 张磊; 戴南; 岳志娟
Original assignee: Research Institute of Forest Ecology Environment and Protection of Chinese Academy of Forestry
Current assignee: Research Institute of Forest Ecology Environment and Protection of Chinese Academy of Forestry
Priority date: 2019-11-21
Filing date: 2019-11-21
Publication date: 2020-03-06

Abstract

The invention belongs to the technical field of research and development of pest attractants, and particularly relates to a looper largeflower sex pheromone attractant composition. An attractant composition for looper sex pheromone, said attractant composition comprising sex pheromone and auxiliary components, said sex pheromone being composed of a novel (Z, Z, Z) -3,6, 9-nonadecatriene component and its epoxypropane derivative [ (6Z,9Z) -cis-3, 4-epoxynonadiene: (3Z,9Z) -cis-6, 7-epoxynonadecadiene: (3Z,6Z) -cis-9, 10-epoxynonadecadiene ═ 1:1: 1] is prepared. The invention also relates to a three-step synthesis method of the attractant composition (Z, Z, Z) -3,6, 9-nonadecatriene, and a gas chromatography-antennal potentiometer analysis and identification method. The composition has the advantages of simple synthesis method, strong trapping capability, long lasting period, strong specificity, adjustable trapping capability, no harm to human and livestock and environmental friendliness. The intelligent delivery accurately achieves accurate delivery according to insect pest situations, and the delivery efficiency is greatly improved.

Description

Synthetic method, identification and intelligent release system of larch geometrid sex pheromone composition

Technical Field

The invention relates to the field of natural product sex pheromone compositions, in particular to a synthetic method and identification of an inchworm sex pheromone composition, and provides an intelligent throwing system of an inchworm sex pheromone composition of larch.

Background

Larch looper Erannisankeraria staudinger belongs to Lepidoptera Lepidotera, Geomeridae, and Elaeagnidae (Ennominae), which are one of larch leaf pests, are mainly distributed in Henan, Jilin, Shanxi, Heilongjiang, inner Mongolia, Shaanxi, Hebei and the like at home and are distributed in Hungary and other countries at abroad.

Larval feeding habits of larvas of dahurian larvas, larvas of long-white larvas, larvas of northChina and other larvas of China and quercus, and also the newly born needles of spruce. When the serious occurrence happens, all the needles of the larch are eaten, and the influence on the growth of the forest is obvious. The larch is damaged from leaf spitting, and leaves are spitted again after insect damage is finished, so that the tree body is quite weak due to insect damage, the coniferous leaves are yellow and weak, the tree grows high and stops, and if rainwater is insufficient, the tree withers in a large area. In the forest stand with large canopy density, the internal damage is heavy, and the 15-edge damage is light. The hazard rule of larch loopers is as follows: the larch pure forest is heavier than the mixed forest; thinning forest is heavier than dense forest; sunny slopes are heavier than cloudy slopes; the artificial forest is heavier than the natural forest.

At present, the utilization of chemical agents is the most important means for controlling larch geometrid. Among them, there are chemically synthesized pesticides and plant-derived pesticides. It is widely used because of its obvious control effect. The pesticide for preventing and controlling larch geometrid includes high-effective cypermethrin emulsifiable concentrate, bitter tobacco emulsifiable concentrate, hypertonic fenoxycarb, abamectin, 20 deltamethrin '741' intubation aerosol, omethoate, dichlorvos and kurarinone plant pesticide. In addition, the Sun Shi Ying and the like use the diseases and insects collected in the field to prepare virus crude extract and prepare the virus crude extract into different concentrations to perform a control experiment, and the occurrence of looper larch is obviously reduced.

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 cultivation and application of the virus is technically demanding. Therefore, the existing control technology is not satisfactory in effect, and a continuous and efficient control technology needs to be researched and developed urgently.

The insect sex pheromone has the advantages of high efficiency, durability, no toxicity, strong specificity, no harm to natural enemies, no environmental pollution and the like in pest control; in addition, the insect sex pheromone is matched with other pest control measures (especially biological control) to show good compatibility, has been highly valued by scholars at home and abroad, and is becoming one of important measures in comprehensive pest control.

However, although the existing technology of larch geometrid uses trienes of eighteen carbon series, the scholars do not notice the molecular structure of other structures with better quality as sex pheromone. Making the research progress in this field unsatisfactory. And the single pursuit of one-time elimination will inevitably cause drug resistance, so that the inchworm can perceive the difference with natural sex pheromone in long-term use, and further can cause resistance effect. Therefore, the invention considers different formulas to make the inchworm gradually accept the temptation of the sex pheromone. In addition, in different affected areas, the inchworm parts are different, and if the attractant with the same amount is thrown without considering the distribution situation, waste is caused. Therefore, the method aims to correspondingly control the throwing attractant amount according to the inchworm distribution situation of a throwing place.

Disclosure of Invention

The invention aims to solve the technical problem of providing a sex pheromone attractant composition for attracting larch geometrid. The composition uses a nineteen-carbon composition, and the trapping number is adjustable between 7 and 82 through reasonable proportioning, so that the acceptance degree of inchworm on the sex pheromone is realized, and the technical effect of gradually eliminating is further achieved.

Larch looper sex pheromone attractant composition

The composition provided by the invention has the following technical scheme: an attractant composition for looper sex pheromone, the attractant composition comprises sex pheromone and auxiliary components, wherein the sex pheromone is prepared from (Z, Z, Z) -3,6, 9-nonadecatriene and epoxypropane derivative thereof [ (6Z,9Z) -cis-3, 4-epoxynonadecadiene: (3Z,9Z) -cis-6, 7-epoxynonadecadiene: (3Z,6Z) -cis-9, 10-epoxynonadecadiene ═ 1:1:1, the mass ratio of the three components). The looper larch sex pheromone active ingredient is (Z, Z, Z) -3,6, 9-nonadecatriene and has a structure shown in a formula I:

preferably, the (Z, Z) -3,6, 9-nonadecatriene, and the epoxypropane derivative thereof [ (6Z,9Z) -cis-3, 4-epoxynonadecadiene: (3Z,9Z) -cis-6, 7-epoxynonadecadiene: (3Z,6Z) -cis-9, 10-epoxynonadecadiene ═ 1:1: 1] mass ratio of 0.8: 0.8-7.2.

Preferably, the auxiliary component is at least one of a light stabilizer, an antioxidant and a slow release carrier.

Preferably, the slow release carrier is at least one of rubber, a polyethylene slow release tube or bottle and a polyvinyl chloride slow release tube.

Preferably, the antioxidant is at least one of vitamin E, TBHQ, BHT and BHA.

Preferably, the light stabilizer is at least one of salicylic acid esters, benzophenones, benzotriazoles, substituted acrylonitriles, triazines and hindered amine ultraviolet absorbers.

Three-step synthesis method and identification method of di- (Z, Z, Z) -3,6, 9-nonadecatriene

In order to study the structure formula I of the novel sex pheromone in the composition, the invention provides a three-step synthesis method as follows:

(1) carrying out reduction reaction on α -linolenic acid ((Z, Z, Z) -9,12, 15-octadecatrienoic acid) under the action of a reducing agent to obtain (Z, Z, Z) -9,12, 15-octadecatrien-1-ol;

(2) reacting (Z, Z, Z) -9,12, 15-octadecatriene-1-ol with trifluoromethanesulfonic anhydride under the condition of a basic catalyst to obtain trifluoromethanesulfonic acid (Z, Z, Z) -9,12, 15-octadecatriene alcohol ester;

(3) under the conditions of low temperature and catalysis, the trifluoromethane sulfonic acid (Z, Z, Z) -9,12, 15-octadecatrienyl alcohol ester and the methyl metal reagent are subjected to coupling reaction to obtain the (Z, Z, Z) -3,6, 9-nonadecatriene.

Preferably, the reducing agent in step (1) comprises one or more of sodium triacetoxyborohydride, sodium borohydride, BH3, lithium tri-tert-butoxyaluminum hydride, and LiAlH 4;

the molar ratio of the α -linolenic acid ((Z, Z, Z) -9,12, 15-octadecatrienoic acid) to the reducing agent is 1: 1-6;

the temperature of the reduction reaction is-10-20 ℃, and the time is 2-24 h. 5

Preferably, the basic catalyst in the step (2) comprises pyridine, dicyclohexylcarbodiimide, triethylamine, 4-dimethylaminopyridine and the like;

the mol ratio of the (Z, Z, Z) -9,12, 15-octadecatrien-1-ol to the trifluoromethanesulfonic anhydride to the catalyst is 1: 1-4: 1-10;

the reaction temperature is-10-0 ℃ and the reaction time is 10-24 h. 10

Preferably, the molar ratio of the trifluoromethanesulfonic acid (Z, Z, Z) -9,12, 15-octadecatrienol ester to the methyl metal reagent and the catalyst is 2-4: 1: 0.01-0.04;

the coupling reaction is carried out at low temperature (-78-10 deg.C) for 1-24 h.

The invention also provides an identification method of the active ingredients of the looper larvas sex pheromone, which comprises the following steps:

s1, analyzing the looper sex pheromone gland extract and the (Z, Z, Z) -3,6, 9-nonadecatriene respectively by adopting a gas chromatography-electroantennogram instrument to obtain corresponding maps;

and S2, analyzing the spectrogram, and determining that the (Z, Z, Z) -3,6, 9-nonadecatriene is one of the main active components of the sex pheromone of the larch looper if the retention time of the (Z, Z, Z) -3,6, 9-nonatriene and the sex pheromone gland extract of the larch looper is similar and the (Z, Z, Z) -3,6, 9-nonatriene can cause the electrophysiological reaction of the feeler of the larch looper.

Thirdly, intelligent throwing system of larch looper sex pheromone attractant

The looper larvas inchworm sex pheromone attractant core using the attractant composition mainly comprises: the unmanned aerial vehicle is used for shooting a high-definition image of a launching place; the image acquisition system is used for acquiring high-definition images and is provided with an attractant core and a throwing vehicle of an information processing system; as well as wireless communication systems and software systems; the unmanned aerial vehicle transfers the acquired high-definition images to the image acquisition system through a wireless communication system installed on the unmanned aerial vehicle, then an information processing system on the throwing vehicle intelligently identifies the images, calculates the inchworm distribution density of the unmanned aerial vehicle flying throwing area through a software system, and controls the throwing vehicle to throw attractant attracting cores into the attractant attracting cores in the area and instruct throwing personnel to drive to the best throwing place for throwing.

Preferably, the optimal throwing place is a throwing place with an inchworm distribution density larger than a preset threshold value.

The specific releasing method comprises the steps that releasing personnel drive to a disaster area, an unmanned aerial vehicle is started to fly to the upper space of the area to make blanket type flight shooting high-definition images, image data are collected through an image collecting device, the data are sent to a releasing vehicle software system through a wireless communication device, an information processing system is controlled to intelligently identify and analyze the distribution of the inchworm in the area, the distribution density is calculated through software, the number of attractant cores released in the area is obtained, and the releasing vehicle is controlled to release the attractant cores.

The invention mainly has the following four beneficial effects: (1) the (Z, Z, Z) -3,6, 9-nonadecatriene and the epoxypropane derivative thereof are used for combining the sex pheromone attractant of the larch looper for the first time to form a composition, and when the sex pheromone-containing attractant lure core is used for trapping the larch looper, the larch looper has strong trapping capacity, long lasting period and strong specificity, and can not generate resistance; is harmless to human and livestock and environment-friendly; (2) the three-step synthesis method of key new structural components (Z, Z, Z) -3,6, 9-nonadecatriene is simple, the gas chromatography-antenna potential technology provided by the invention is adopted, and the active ingredients of the looper sex pheromone of the looper are determined by a method of contrastive analysis of synthesized standard substances and looper sex pheromone gland extracts, the identification method has short period and high result reliability; (3) different trapping numbers are realized by adjusting the proportion of (Z, Z, Z) -3,6, 9-nonadecatriene and the epoxypropane derivative thereof, so that inchworms can gradually accept the pheromone, and later-period resistance possibly generated by short-time large-scale use is eliminated; (4) through the other technologies of unmanned aerial vehicle and image, to the distribution density who accurately judges the region of puting in to the attractant lure core quantity of accurate input practices thrift the cost, puts in efficiency and improves greatly.

Drawings

FIG. 1 is a bar graph of the amount ratio of various (Z, Z, Z) -3,6, 9-nonadecatrienes and their propylene oxide-derived substances with respect to the number of traps, which is a bar graph showing the molecular structure of (Z, Z, Z) -3,6, 9-nonadecatriene of formula I;

FIG. 2 shows the synthetic route of the main active ingredient (Z, Z, Z) -3,6, 9-nonadecatriene of the looper sex pheromone of the larch as shown in the formula (1-3 in the figure are respectively indicated as the intermediate or target synthesized by each step of the three-step method);

FIG. 3 is a GC-EAD spectrum of the GC-electroantennogram analyzed by the GC-electroantennogram analyzer of the antennal moth feeler versus the n-hexane extract of sex pheromone glands of female moths of the invention;

FIG. 4 is a GC-EAD spectrum of the gas chromatography-electroantennogram analysis of synthetic compounds by the feeler of looper according to the present invention, wherein A is (Z, Z, Z) -3,6, 9-nonadecatriene;

FIG. 5 is a schematic diagram of a construction of an intelligent larval geometrid sex pheromone attractant delivery system designed by the invention;

FIG. 6 is a schematic diagram of a working flow of an intelligent larch geometrid sex pheromone attractant throwing system.

Wherein, the reference numeral 1 puts in the machine, 2 puts in the car, 3 unmanned aerial vehicle, 4, image data, 5 image acquisition system, 6 information processing system, 7 software system.

Detailed Description

The following detailed description of specific embodiments of the present invention is provided in conjunction with examples, but it should be understood that the scope of the present invention is not limited to the specific embodiments.

Example 1: propylene oxide derivatives [ (6Z,9Z) -cis-3, 4-epoxynonadecadiene: (3Z,9Z) -cis-6, 7-epoxynonadecadiene: preparation of (3Z,6Z) -cis-9, 10-epoxynonadecadiene ]:

the propylene oxide derivative of the present invention can be synthesized by the following route.

A solution of (3Z,6Z,9Z) -nonadecatriene (2.62g, 10mmol) in 10mL of dichloromethane was slowly added dropwise to a solution of m-chloroperoxybenzoic acid (2.06g, 12mmol) in dichloromethane with stirring at room temperature, the reaction was carried out for 1 hour with stirring, insoluble materials were filtered off, the solution was washed with saturated sodium bicarbonate solution, the solvent was evaporated and then the mixture was separated by column chromatography and petroleum ether/diethyl ether (30:1) to obtain an epoxy isomer mixture (2.08g, 75%). GC analysis showed (6Z,9Z) -cis-3, 4-epoxynonadecadiene: (3Z,9Z) -cis-6, 7-epoxynonadecadiene: (3Z,6Z) -cis-9, 10-epoxynonadecadiene ═ 1:1: 1.

Example 2: experiment for attracting and monitoring effects of larch loopers by different attractant formulas

The experimental site: the mechanical forest farm of Hebei Serpenba and the forest farm of inner Mongolia Huohan mountain and Haematoxian mountain.

The experimental method comprises the following steps: lure cores were prepared from the formulation in table 1 and placed in triangular traps spaced about 20m apart from the ground by 1.5m, using a random block design, repeating the treatment 4 times each time, continuously investigating for 10 days, counting the number of lure per trap every two days, and removing the adult lured by the traps.

TABLE 1 attractant formulation

The experimental results are as follows: the attraction effect is shown in figure 1.

As can be seen from fig. 1, the combination of (3Z,6Z,9Z) -nonadecatriene: propylene oxide derivatives [ (6Z,9Z) -cis-3, 4-epoxynonadecadiene: (3Z,9Z) -cis-6, 7-epoxynonadecadiene: (3Z,6Z) -cis-9, 10-epoxynonadecadiene ═ 1:1:1, the attracting effect is obviously improved when the mass ratio is 0.8: 0.8-7.2; in particular when the active ingredient (3Z,6Z,9Z) -nonadecatriene: propylene oxide derivatives [ (6Z,9Z) -cis-3, 4-epoxynonadecadiene: (3Z,9Z) -cis-6, 7-epoxynonadecadiene: (3Z,6Z) -cis-9, 10-epoxynonadecadiene ═ 1:1:1 ═ 0.8: at 2.4, the attracting effect was highest, and the average number per trap was 81.5 at the highest. Note that without the use of the traditional attractant of the formulation of the present invention, the number of traps was the lowest. The trapping number can be adjusted through different proportions, so that the temptation of the inchworm to pheromone is gradually stabilized, and the inchworm can finally accept the formula, thereby achieving the technical effect of stably killing.

Example 3

In the present invention, the synthetic route of the main active ingredients of the looper largeflower geometrid sex pheromone is shown in figure 2.

Step one, carrying out reduction reaction on α -linolenic acid (shown as a compound 1 in a structural formula a) at 20 ℃ for 3h under the action of sodium triacetoxyborohydride, wherein the molar ratio of the α -linolenic acid to the sodium triacetoxyborohydride is preferably 1:1, and the solvent of the reduction reaction is tetrahydrofuran to obtain (Z, Z, Z) -9,12, 15-octadecatrien-1-ol (shown as a topmost first arrow in a structural formula 2).

Dissolving a reducing agent in a solvent, slowly adding α -linolenic acid into the solution for reaction, wherein the reaction time is calculated from the time of adding α -linolenic acid, extracting n-hexane after the reaction is ended to obtain an organic phase, and drying with anhydrous sodium sulfate.

Step two: obtaining (Z, Z, Z) -9,12, 15-octadecatriene-1-ol, dissolving the (Z, Z, Z) -9,12, 15-octadecatriene-1-ol in anhydrous dichloromethane, adding an alkaline reagent, slowly dropwise adding trifluoromethyl sulfonic anhydride into the solution of the (Z, Z, Z) -9,12, 15-octadecatriene-1-ol at the temperature of-5-0 ℃, and carrying out esterification reaction at the temperature of-5-0 ℃ after dropwise adding to obtain an esterification reaction solution, thus obtaining the trifluoromethanesulfonic acid (Z, Z, Z) -9,12, 15-octadecatriene alcohol ester (the structural formula is the compound indicated by the middle arrow in figure 2). The mol ratio of the (Z, Z, Z) -9,12, 15-octadecatrien-1-ol to the trifluoromethanesulfonic anhydride to the catalyst is 1:1: 3

Step three: dissolving the triflic acid (Z, Z, Z) -9,12, 15-octadeca-5-trienyl alcohol ester obtained in the step two in anhydrous ether, adding dilithium tetrachlorocuprate as a catalyst at the low temperature of-50 ℃, and stirring for 20 min; then methyl metal reagent methyl magnesium chloride is slowly added to react for 30 min. The mol ratio of the trifluoromethanesulfonic acid (Z, Z, Z) -9,12, 15-octadecatrienol ester to the methyl to the metal reagent to the catalyst is 1:2: 1; the solvent for the iodination reaction is preferably anhydrous.

Wherein the product obtained in each step is extracted 3 times to obtain an organic phase, and dried by anhydrous sodium sulfate. The extraction step comprises the steps of n-hexane extraction, mixing of esterification reaction liquid and saturated sodium carbonate solution, ethyl acetate extraction, mixing with water and then n-hexane extraction.

Example 4

In contrast to example 3, a catalyst was added in the second reaction step, wherein the molar ratio of (Z, Z, Z) -9,12, 15-octadecatrien-1-ol, trifluoromethanesulfonic anhydride and catalyst was 1:4:10 or 1:3:6 or 1:2: 4. In the third step, the molar ratio of the trifluoromethanesulfonic acid (Z, Z, Z) -9,12, 15-octadecatrienol ester to the methyl, the metal reagent and the catalyst is 1:2: 1.

example 5

The identification method of the main active ingredients of the sex pheromone of the larch geometrid in the embodiment is as follows:

the instrument comprises the following steps: agilent 7890A gas chromatograph-Holland Syntech antenna potential combination instrument (GC-EAD) of Agilent USA; 5, chromatographic column: HP-5, 30m × 0.25mm × 0.25 μm, J & W scientific, Folsom, CA;

gas chromatography working conditions:

a detector: hydrogen flame ionization monitors (FID);

a combustor: hydrogen with the flow rate of 40 mL/min;

combustion-supporting gas: the air is dried. The flow rate is 400 mL/min; 10

Carrier gas: nitrogen with the flow rate of 2.5 mL/min;

sample inlet temperature: 250 ℃;

detector temperature: 280 ℃;

column procedure: the initial temperature is 80 ℃, the temperature is kept for 2min, the temperature is programmed to 280 ℃ at the speed of 10 ℃/min, and the temperature is kept for 20 min;

and (3) sample introduction mode: no shunt sample introduction, the sample introduction amount is 1 mu L, and the sample concentration is 10 ng/uL;

an outlet end flow divider: 0SS-2.SGE, Australia, split ratio 1: 2; the working conditions of the antennal potentiometer are as follows:

an EAG probe: PRG-2, forked antenna holders;

an IDAC converter: auto Spike, IDAC2/3, Syntech; 20

An amplifier: UN-06, Syntech;

the antenna source is as follows: 2-3 days after eclosion, the feeler of looper male moth;

length: 10 mm;

the treatment method comprises the following steps: the tip of the antenna is cut off by 0.5mm from the root by a dissecting scissors, and the antenna is connected with two silver electrodes of a fork-shaped antenna fixer of an EAG probe (PRG-2) by conductive adhesive. 25

The identification method of the active ingredients of the looper largeflower looper sex pheromone comprises the following steps:

extracting sex pheromone of larch geometrid: collecting 10 heads of un-mated female moths of loopers largehead loopers in the coupling stage, slightly pressing the abdomen of the female moths by hands when the gonads of the female moths extend outside, forcing the gonads of the female moths to extend completely, taking out the glands, combining extracting solutions, concentrating, sealing the concentrated extract, and storing at-20 ℃ for later use;

respectively carrying out gas chromatography-electroantennogram analysis on the sex pheromone gland extract of the larch looper and the compound (Z, Z, Z) -3,6, 9-nonadecatriene synthesized in example 1 to obtain a corresponding gas chromatography-electroantennogram analysis map, as shown in fig. 3 and 4, wherein fig. 3 is a gas chromatography-electroantennogram analysis GC-EAD map of the sex pheromone gland n-hexane extract of the male moth of the larch looper to the female moth; FIG. 4 is a GC-EAD spectrum of the GC-EAD analysis of the synthetic compounds by gas chromatography-electroantennogram for the antennal moth of larch looper.

As can be seen from FIGS. 3 and 4, the gland extract has a sex pheromone component which can make the contact angle of the looper significantly respond to the electrophysiological reaction, and the sex pheromone component which can cause the contact angle of the looper can be present at the retention time of 14.72 min; as can be seen from the analysis of the gas chromatography data in FIG. 4, the compound finally obtained in example 2 of the present invention has a retention time of 14.73min and is capable of inducing a significant antennal electrophysiological reaction, from which it can be determined that (Z, Z, Z) -3,6, 9-nonadecatriene is the main active ingredient of looper sex pheromone.

It can be seen from this example that the present invention provides for the first time that the structure of the sex pheromone active component of larch looper is (Z, Z) -3,6, 9-nonadecatriene, which can cause electrophysiological reaction of larch looper male moth, and the synthesis method provided by the present invention has the advantages of high yield, high purity, etc., and the identification method provided by the present invention has the advantages of short period, high result reliability, etc.

Example 6

Experiment for releasing attractant lure by using intelligent releasing system in disaster area

The experimental method comprises the following steps: after a release person drives a release vehicle 2 to a forest field, a camera (not shown) on an unmanned aerial vehicle 3 is started as shown in fig. 5, the unmanned aerial vehicle 3 is released to fly and shoot according to a set route of a software system 7 (shown in fig. 6), image data 4 are collected by an image collection system 5 through a Bluetooth (not shown) arranged on the unmanned aerial vehicle, the image collection system 5 transmits the image data 4 to an information processing system 6 (shown in fig. 6), and the information processing system 6 intelligently identifies the quantity distribution of inchworms in each picture, and 10-20 inchworm adults are distributed per square meter. When shooting is completed, the unmanned aerial vehicle 3 flies back, and the throwing personnel withdraws the unmanned aerial vehicle 3. At the moment, the software system 7 automatically calculates the density distribution of the regions according to the quantity distribution of the inchworms in each graph, the inchworms in the regions close to the central region are distributed greatly, and the distribution table 2 is automatically given. And meanwhile, the software system 7 controls the throwing machine 1 on the throwing vehicle 2 to throw the attractant lure and instructs throwing personnel to drive the vehicle to go deep into the forest farm for further throwing.

TABLE 2 Ectropis distribution of forest farm (Density unit: head/square meter)

Claims

1. An attractant composition for looper sex pheromone, which comprises sex pheromone and auxiliary components, wherein the sex pheromone is prepared from (Z, Z, Z) -3,6, 9-nonadecatriene and epoxypropane derivative thereof [ (6Z,9Z) -cis-3, 4-epoxynonadecadiene: (3Z,9Z) -cis-6, 7-epoxynonadecadiene: (3Z,6Z) -cis-9, 10-epoxy nonadecadiene.

2. The larch looper sex pheromone attractant composition as claimed in claim 1, wherein the (3Z,6Z,9Z) -nonadecatriene, and its propylene oxide derivative [ (6Z,9Z) -cis-3, 4-nonaepoxydecadiene: (3Z,9Z) -cis-6, 7-epoxynonadecadiene: (3Z,6Z) -cis-9, 10-epoxynonadecadiene ═ 1:1: 1] mass ratio of 1:1:1 or 0.8: 0.8-7.2.

3. The larch looper attractant composition according to claim 1, wherein the auxiliary ingredient is at least one of a solvent, a light stabilizer, an antioxidant, and a slow release carrier; the slow release carrier is at least one of rubber, a polyethylene slow release tube or bottle and a polyvinyl chloride slow release tube; the antioxidant is at least one of vitamin E, TBHQ, BHT and BHA; the light stabilizer is at least one of salicylic acid esters, benzophenones, benzotriazoles, substituted acrylonitrile, triazines and hindered amine ultraviolet absorbers; the light stabilizer is at least one of vegetable oil, dichloromethane and n-hexane.

4. A three-step synthesis method of (Z, Z) -3,6, 9-nonadecatriene in the attractant composition according to any one of claims 1 to 3, characterized in that:

s1, carrying out reduction reaction on α -linolenic acid ((Z, Z, Z) -9,12, 15-octadecatrienoic acid) under the action of a reducing agent to obtain (Z, Z, Z) -9,12, 15-octadecatrien-1-ol;

s2: reacting (Z, Z, Z) -9,12, 15-octadecatriene-1-ol with trifluoromethanesulfonic anhydride under the condition of a basic catalyst to obtain trifluoromethanesulfonic acid (Z, Z, Z) -9,12, 15-octadecatriene alcohol ester;

s3: under the conditions of low temperature and catalysis, the trifluoromethane sulfonic acid (Z, Z, Z) -9,12, 15-octadecatrienyl alcohol ester and the methyl metal reagent are subjected to coupling reaction to obtain the (Z, Z, Z) -3,6, 9-nonadecatriene.

5. The synthesis of claim 4The method is characterized in that the reducing agent in the step S1 comprises sodium triacetoxyborohydride, sodium borohydride and BH₃Lithium aluminum tri-tert-butoxyhydride, LiAlH₄One or more of the above;

the temperature of the reduction reaction is-10-20 ℃, and the time is 2-24 h.

6. The synthesis method of claim 4 or 5, wherein the basic catalyst in step S2 comprises one or a combination of pyridine, dicyclohexylcarbodiimide, triethylamine, and 4-dimethylaminopyridine; the mol ratio of the (Z, Z, Z) -9,12, 15-octadecatrien-1-ol to the trifluoromethanesulfonic anhydride to the catalyst is 1: 1-4: 1-10; the reaction temperature is-10-0 ℃ and the reaction time is 10-24 h.

7. The synthesis method of claim 6, wherein the methyl metal reagent comprises methyl magnesium bromide, methyl magnesium chloride, dimethyl copper lithium, etc., and the catalyst comprises one or a combination of cuprous chloride, cuprous bromide, cuprous 25 iodide, and dilithium tetrachlorocuprate;

in the step S3, the molar ratio of the trifluoromethanesulfonic acid (Z, Z, Z) -9,12, 15-octadecatrienol ester to the methyl metal reagent to the catalyst is 2-4: 1: 0.01-0.04;

the coupling reaction is carried out at-78 to-10 ℃ for 1 to 24 hours.

8. A method for identifying the looper-worm-like pheromone active ingredient (Z, Z) -3,6, 9-nonadecatriene in the attractant composition of any one of claims 1-8, comprising the steps of:

gas chromatography-electroantennometer analysis: respectively carrying out gas chromatography-electroantennogram analysis on the looper sex pheromone gland extract and (Z, Z, Z) -3,6, 9-nonadecatriene to obtain a corresponding gas chromatography-electroantennogram analysis map;

and (3) analyzing the spectrogram: if the spectrogram shows that the retention time of the (Z, Z, Z) -3,6, 9-nonadecatriene is similar to that of the larch inchworm sex pheromone gland extract and can cause the electrical physiological reaction of the feeler of the larch inchworm male moth, the (Z, Z, Z) -3,6, 9-nonadecatriene can be determined as the main active component of the larch inchworm sex pheromone.

9. An looper sex pheromone attractant cartridge comprising the attractant composition of claims 1-8, wherein each cartridge sex pheromone is present in an amount of 0.1-10 mg; the mass of the core-inducing sex pheromone accounts for 0.5-90 percent, and the mass of the auxiliary component accounts for 99.5-10 percent.

10. An intelligent larch looper sex pheromone attractant delivery system, comprising the attractant lure according to claim 9, and further comprising: the unmanned aerial vehicle is used for shooting a high-definition image of a launching place; an image acquisition system for acquiring high-definition images, a throwing vehicle provided with the attractant lure according to claim 9 and an information processing system; as well as wireless communication systems and software systems;

the unmanned aerial vehicle flies to the sky of a disaster-stricken area according to a route set by a software system to fly along a preset route, a high-definition image acquired is transferred to an image acquisition system through a wireless communication system installed on the unmanned aerial vehicle, then an information processing system on the throwing vehicle intelligently identifies the image, the inchworm distribution density of the unmanned aerial vehicle flying throwing area is calculated through the software system, and the throwing vehicle is controlled to throw attractant lure cores into the area and instruct throwing personnel to drive to the best throwing place to throw.

11. The intelligent delivery system of claim 10, wherein the optimal delivery site is a delivery site with an inchworm distribution density greater than a predetermined threshold.