JPS6039651B2 - 14-Methyl-1-octadecene, its production method, and insect attractant containing the compound as an active ingredient - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel compound useful as an attractant for Peach leafhopper moth and its neargreen species, a method for producing the same, and an attractant containing the compound as an active ingredient. Lyonetia clarerhella
Linn≦) is an important pest of peaches. When this pest infests a single leaf, it induces physiological defoliation of peach leaves, causing damage that significantly inhibits fruit enlargement and the formation of flower buds the following year. Since the larvae of this species live within the mesophyll, control is limited to the young larval stage, which is highly sensitive to insecticides. Therefore, it is extremely important to accurately know when this species appears. In addition, the number of outbreaks of this species is 4 to 7 times per year, which is extremely high for a Rhinopterygian snout.Furthermore, there are only a few types of insecticides that are effective for controlling this species, so resistance to these insecticides has increased. The emergence of sexual lineages is at risk. On the other hand, the chemical structures of so-called sex pheromones have recently been clarified for many pest insects, and it has become possible to use these sex pheromones to efficiently investigate the occurrence and fate of pests. Sex pheromone is a chemical substance generally secreted by female adults that exhibits a species-specific attracting effect on male adults of the same species. By clarifying the chemical structure of such attractive sex pheromone, chemically synthesizing this substance, and using it as a so-called sex attractant, it becomes possible to efficiently investigate the development and development of sex pheromone. Furthermore, by using this sexual attractant to kill a large number of males or disrupt the mating behavior of males and females, it is also possible to control pests targeting the adult stage. In view of these circumstances, the present inventors conducted research on sexual attractants of the peach leaf moth, extracted a component having male-attractive activity from virgin females of the peach leaf moth, and determined its chemical structure. Furthermore, we learned that a chemically synthesized compound exhibits an effective attracting effect on the peach leafhopper moth. The present invention was completed based on these findings. The novel compound in the present invention is represented by the following formula: This compound can be synthesized, for example, by the following method. <1) OH-C, 2 days 24-OH+HBr-
÷Br-C, 2 days 24-OH(2)(m)+triph-enylphosphine' [ph3P(C, 2 days 240H)]Br
When this compound is used as an active ingredient in an attractant for peach leafhopper, various forms are possible. Since this compound has a very characteristic chopstick effect and is a volatile oily liquid, it can be used directly (as is), or dissolved in an appropriate solvent such as hexane, and then dissolved in an appropriate carrier (various synthetic polymers). It is preferable to use it in the form of being adsorbed onto a material (such as body, natural rubber, synthetic rubber, etc.) or encapsulated in a molded product of these carrier materials. The content of the active ingredient can be determined as appropriate, but when it is adsorbed onto a damaged body or encapsulated in a molded carrier material, it is preferably about 0.1 to 100 active ingredients per carrier. A carrier containing such an active ingredient or a molded carrier material may be placed on a suitable support, for example, on a container containing another liquid (such as a vat) or on an object coated with a suitable adhesive substance. By placing it nearby, the peach leaf moth will be attracted, and will die if it falls into a container (such as a bat) or gets caught in the sticky substance. Next, isolation of the compound related to the present invention and determination of its mechanism will be explained. The cheeks collected from the field were placed under full light at 20:00, and 50 to 75 adult females were housed in 200-liter Erlenmeyer flasks, and after 9 hours at 20:00, they were placed in dichloromethane. The extract was obtained by macerating. The agitation activity of the samples was tested in the field where the peach leafhopper moth was infested. For the sample, absorbent cotton was soaked with 20 to 30% of the compost and placed on an adhesive board. This was placed in the peach garden between 10:00 and 1:00 p.m., and the number of insects captured on the sticky board was counted the next morning.
Isolation of the active substance was carried out as follows. Extracts from approximately 10,000 male and female mice were concentrated using a rotary evaporator, dehydrated using anhydrous sodium sulfate, and subjected to high performance liquid chromatography using a gel permeation chromatography (CPC) column to determine the molecular weight, including triglycerides. Large fraction and smaller fraction
Divided into two. Attractive activity was observed in the latter low molecular weight fraction. Therefore, this fraction was treated with a saturated sodium metasulfite solution to separate it into a fraction containing the carbonyl compound and a fraction not containing it. Since the attracting activity was found in the fraction containing no carbonyl compound, liquid chromatography using Florisil was next performed. When the attracting activity was examined by sequential elution with hexane, 5% ether/hexane, and 25% ether/hexane, activity was observed in the hexane eluted fraction. This fraction was heated from a temperature of 80oo to 22,000
Analysis was carried out by gas chromatography using a 3% OV-101 column under the condition of increasing the temperature at 5° C./min until the temperature reached 5° C., and the attracting activity was observed in the portion flowing out from 19.5 to 22.5 minutes. Under these conditions, tetradecenyl acetate was eluted at 18.7 minutes, and hexadecenyl acetate was eluted at 22.6 minutes. In addition, for the dichloromethane extract of a total of 20,000 male and female animals, Furo IJ Silcolumn, GP
Purification was performed using a C column and a silica gel column impregnated with silver nitrate, and then fractionation was performed using a gas chromatograph using a 10% PEG-2M column (open temperature 170qC), and the active ingredient that had already been purified using the OV-101 column was dissolved. Activity was observed at the same time as 6 to 8 minutes. The material thus isolated was hydrogenated and subjected to gas chromatography mass spectrometry (GC-M
According to analysis by S), the number of carbon atoms in the methyl side chain is 19.
It was presumed to be a hydrocarbon with a side chain at the 5th position, and the mass spectrum was consistent with this. Characteristic fragments of the mass spectra of the hydrogenated product and the 5-methyloctadecane synthesized product are shown in Table 1. Table 1
When the active substance was ozonolyzed, GC-MS analysis showed that the M/Z (relative temperature) of the parent ion (M0) was 268, so it was assumed that the double bond was at the end of the molecule. Ta. Therefore, when 5-methyl-1-heptadecanal was synthesized and GC-MS analysis was performed, the mass spectrum matched well with the mass spectrum of the ozone decomposition product of the active substance. Table 2 Furthermore, when a putative compound having the double bond and methyl side chain position estimated from these results was synthesized and its mass spectrum was compared with that of the natural product, the two coincided well. Table 3 Example 14-Synthesis of methyl-1-octadecene '1} OH-C, 2nd string 41OH → Br-C, 2nd day - 10th day (b) (○) 1.12 dodecanol (
0) was heated on the 19th night by lighting HBr 30' with a magnetic stirrer. Extraction was performed with hexane every 1 hour. The extract was concentrated and purified using a Florisil column,
- Bromo-1 dodecanol (m) was obtained. ■ Br-
C, 2 days 24-OH → (m) [ph3P (CI 2 days / 〇H)] Br (N) tl} The compound (m) obtained in (6.3 evening) and triphenylphosphine 6.69 was dissolved in 75°C of acetonitrile and refluxed for 2 days. 10.6 minutes (12-hydroxydodecyl)triphenylphosphonium bromide (W) was obtained with a yield of 83
%Met. Next, put NaH in a dry round bottom flask for 2 nights and add DM.
25 SOs

[In addition, I continued to perform the rope worship for an hour while brimming with joy. Cool to room temperature and add 40' of dry THF. This was cooled on ice and the phosphonium salt (W
)10.6 A solution of DMS025 was slowly added dropwise. After continuing the lantern worship for 1 hour with a magnetic stirrer, 2 drops of methyl butyl ketone were added little by little.
I worshiped the lights for another hour. To stop the reaction, the mixture was poured into an ice bath and extracted with ether. The ether layer was washed with saturated saline and dehydrated with Na2SO4, and then the ether was removed. The white oil was extracted three times with hexasol, concentrated, and purified with a Florisil column to obtain 13-methyl-12-heptadecen-1-ol (V). The yield was 31%. GC-MS results M/Z (relative temperature) 2iso [M+] (1.39%), 250 (0.08%),
211 (0.52%) Compound (V) obtained in step 3 was added to a mixture of hydrazine in step 24, 30% hydrogen peroxide in step 3.3, and ethanol in step 220 for 4.8 hours. In addition,
The reaction was maintained at 50oC for 7 days. The reaction was stopped by adding HCI and extracted with ether. After dehydration. Purified with lysyl column, 4th night 13
-Methyl-1-heptadecanol (W) was obtained. The yield was 83%. GC-MS results M/Z (relative temperature) 252 [M+-day 20] (0.24%), 210 (0.
76%), 195 (1.48%) 5 skin pyridine and 0.
Chromic anhydride was added thereto, and the compound (W) obtained in '4- was slowly added to carry out oxidation. 13-Methylheptadecanal (blood) was obtained with a yield of 49%. In a dry three-necked flask, 5 m of anhydrous cable and 3.6 m of a butyl lithium hexane solution were placed, and 1.4 m of a phosphonium salt was added thereto. After lantern worshiping with a magnetic stirrer for 1 hour, 13-methylheptadecanal (W) was added for 1 evening, and rope worshiping was continued for 2 hours. This was poured into ice water to stop the reaction, and extracted with ether. After dehydration, it was concentrated, extracted with hexane three times, and purified using a Florisil column. 66 capes of 14-methyl-1-octadeceso (1) were obtained, with a yield of 21
%Met. Test Example 1 A test was conducted on the attractivity of synthetic compounds in the field. Synthetic compound 14-methyl-1-octadecene (purity 93
1, 10, 100 U of %) and about 4 parts of virgin female extract were soaked in absorbent cotton as the attractant, and 1
Group 3 (April 27, 2015) Attractiveness to the male peach leaf moth was investigated in three peach orchards at the Fukushima Prefecture Fruit Tree Experiment Station. Place the yield source on a trap coated with adhesive, and place this on a branch at a height of 1.5 to 2 feet above the ground at intervals of about 10 cm.
The next morning, we surveyed the number of peach leaf moths caught. The number of fish caught in each area is shown in Table 4 below, and significant attracting activity was observed in the areas treated with 10 or more synthetic compounds. 10
In the area treated with 0 meta, the transfer activity was equivalent to or superior to that of 40 virgin female extracts. Table 4 *1 5% of cases with the same sign are determined by Tankan's multiple test
No significant difference in risk rate *2 Average value *3 Standard 4-station difference test example 2 Synthetic compound 14-methyl-1-octadecene (purity 93
%) 1 c was impregnated into a plastic capsule (manufactured by Yasumoto Kasei ■), and this was placed on an adhesive-type trub.
On April 5th, the tree was registered in the peach orchard at the Fukushima Prefecture Fruit Tree Experiment Station. As a control, traps without a source were also set up in the same garden, and the number of peach leaf moths caught in these traps was counted almost every day. We also compared the number of female and male leafhoppers killed by a preliminary light (100W mercury lamp, approximately 200 meters away from the adhesive trap) in the field. Synthetic product 1-9
Significantly more male ants were captured in the traps using the light as an attraction source than in the control traps and the warning lights, with 14
A remarkable attracting activity of -methyl-1-octadecene was observed. Table 5

Claims (1)

[Claims] 1. 14-Methyl-1-octadecene represented by the following formula (I): ▲There are numerical formulas, chemical formulas, tables, etc.▼. 2 Next steps: (a) 12-bromo- obtained by reacting 1,12-dodecanediol (II) and hydrogen bromide as shown in the following formula (i)
A step of reacting 1-dodecanol (III) with triphenylphosphine as shown in the following formula (ii) to produce (12-hydroxydodecyl)triphenylphosphonium bromide (iv), HO-C_1_2H_2_4-OH+
HBr(II) → Br-C_1_2H_2_4-OH+H
_2O (i) (III) Br-C_1_2H_2_4-O
H+(ph_3)P(III) → [ph_3P(C_1_
2H_2_4-OH)]Br (ii) (b) The (12-hydroxydodecyl)triphenylphosphonium bromide (iv) obtained in the above step (a) is reacted with methyl butyl ketone using the following formula (iii) using the Witteig reaction. ) to form 13-methyl-12-heptadecene-1-
The process of obtaining ol (v), ▲ includes mathematical formulas, chemical formulas, tables, etc. ▼ (c) 13-methyl-12-heptadecen-1-ol (V) obtained in the above step (b) is expressed by the following formula (iv)
After hydrogenation and reduction to form 13-methyl-1-heptadecanol (VI), it was oxidized with chromic acid to form 13-methyl-1-heptadecanol (VI).
The process of converting 13-methyl-heptadecanal (VII), ▲ mathematical formulas, chemical formulas, tables, etc. ▼ (d) Then, the 13-methyl-heptadecanal (V
II) is reacted with a triphenylmethylphosphonium salt as shown in the following formula (v) using the Witteitz reaction;
▲There are mathematical formulas, chemical formulas, tables, etc.▼ Indicative formula (I) characterized by the following: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ A method for producing 14-methyl-1-octadecene. 3 Indicative formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ An attractant for the peach leafhopper moth and its related species, which contains 14-methyl-1-octadecene as an active ingredient.