JPS6028941A - 14-methyl-1-octadecene, its preparation and insect attractant comprising it as active ingredient - Google Patents

Abstract

NEW MATERIAL:14-Methyl-1-ocatadecene shown by the formula I . USE: An attractant substance for Lyonetia elerhella Linne, an important insect pest for peach, and for its relative species. Having high effect with a very small amount of it. The compound is a volatile oily liquid, used directly, or dissolved in a proper solvent such as hexane, etc. and adsorbed on any of synthetic high polymer, etc., and used. PREPARATION:A compound obtained from 1,12-dodecanediol shown by the formula II and hydrogen bromide is reacted with triphenylphosphine. The reaction product is then reacted with methyl butyl ketone to give a compound shown by the formula III. In the following process, the compound shown by the formula IIIis hydrogenated and reduced, further oxidated with chromic acid to give 13-methyl-heptadecanal shown by the formula IV. In the following process, the compound shown by the formula IV is subjected to Wittig reaction with triphenylmethyl phosphonium salt shown by the formula IV, to give a compound shown by the formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel compound useful as a protective substance for Peach leafhopper moth and its related species, a method for producing the same, and an attractant containing the compound as an active ingredient.

Lyonetia clerhell
a Lin-n4) is an important pest of peaches. When several of these pests infest one leaf, they induce 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 aquatic species live within the mesophyll, control is limited to the young larval stage, which is highly sensitive to insecticides. For this reason, it is extremely important to accurately know when water species occur. The number of annual occurrences of water species is 4~
7 times, which is a very large number for insects in the order Phosphoroptera, and there are only a few types of insecticides that are effective for controlling car types.
There is concern that strains resistant to these insecticides will emerge.

On the other hand, the chemical structures of so-called sex pheromones have recently been clarified for many pest insects, and the use of these sex pheromones has begun to be used to efficiently investigate the development and development of pest insects.

Sex pheromones are chemicals generally secreted by adult female insects.
It exhibits a species-specific attracting effect on male adults of the same species. We clarified the chemical structure of these protective sex pheromones,
By chemically synthesizing this substance and using it as a so-called sex attractant, it becomes possible to efficiently investigate the development and development of this substance. Furthermore, by using this sex attractant to attract and kill a large number of males or to 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 has the following formula: CHm CHs -(CHt)s-CH-(CHt)s+ -C
Hm CHt (represented by rl). This compound can be synthesized, for example, by the following method.

fll 0H-C+tHt4-OH+HBr→Br-C
11H14-OH (Seal) +21 (Ca) +) rifhenylphosphine - → (p
hsP(C1tHnOH)) BrTff+ +31 (ff) + C,Ho -C-CHs1 (V) e C,H, -CH-C,,H,,OHVII (■) (A) This compound was used as an attractant for peach leafhopper. When used as active ingredient, various forms are possible. Since this compound is effective in extremely small amounts and is a volatile oily liquid, it can be used as it is or dissolved in an appropriate solvent such as hexane with a suitable carrier (such as various synthetic polymers).

It is advisable to adsorb it onto natural rubber, synthetic rubber, etc., or to use it in the form of being 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 carrier or encapsulated in a molded carrier material, the content is 0.11-1oo1r! in the carrier 1f. degree is preferred.

The carrier or carrier material molding containing such an active ingredient is placed on or near 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. If installed in a container, moths and moths will be attracted and die if they fall into containers (such as bats) or become trapped in sticky substances.

Next, the isolation and structure determination of the compound according to the present invention will be explained.

The moss collected from the field was placed under a temperature of 20°C, and 50 to 75 adult females were housed in 200 ml Erlenmeyer flasks at 20°C in the dark, and then immersed in dichloromethane. An extract was obtained.

The attractant activity of the samples was tested in the field where the peach leafhopper moth was infested. 20 to 30 samples were soaked in absorbent cotton and spread on an adhesive board. This was installed in a peach garden between 10:00 and 12:00 at night, 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 100 male and female mice were concentrated using a rotary evaporator, dehydrated with anhydrous sodium sulfate, and subjected to high performance liquid chromatography using a gel permeation chromatography (GPC) column. minute and two smaller minutes
Divided into two. Attractive activity was observed in both of the latter low molecular weight components. Therefore, these two parts were treated with a saturated sodium metasulfite solution and separated into two parts containing carbonyl compounds and two parts not containing carbonyl compounds. Since the attracting activity was found in both fractions that did not contain carbonyl compounds, we next performed liquid chromatography using Florisil. When the attracting activity was examined by elution sequentially with hexane, 5% ether/hexane, and 25% ether/hexane, activity was observed in the hexane eluted fraction. These two fractions were analyzed by gas chromatography using a 6% ov-1 oi column at a temperature increase of 5°C per minute from 80°C to 220°C. ζ It was observed in the outflowing part. Under these conditions, tetradecenyl acetate is 1
At 8.7 minutes, hexadecenyl acetate was eluted at 22.6 minutes. Furthermore, dichloromethane extracts from a total of 20,000 male and female animals were purified using a Florisil column, a GPC column, and a silver nitrate-impregnated silica gel column, and then fractionated by gas chromatography using a 10% Pg G-20M column (oven temperature 170°C). As a result, activity was observed at the same time that the active component purified using the 0V-101 column was eluted, that is, 6 to 8 minutes.

When the substance isolated in this way was hydrogenated and analyzed using a gas chromatograph mass spectrometer (GC-M8), it was estimated that it was a hydrocarbon with a methyl side chain of 19 carbon atoms, and the side chain was located at the 5th position. The mass sousvector of the object in is 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 Characteristic fragments of 5-methyloctadecane synthesized with the hydrogenation product of the active substance.
Since the result (relative strength) was 268, it was estimated that the double bond was at the end of the molecule. Therefore, when 5-methyl-1-heptadecanal was synthesized and subjected to GC-M8 analysis, it matched well with the mass spectrum of the ozone decomposition product of the active substance.

Table 2 Characteristic fragments of ozonolysis products of active substances and synthetic products of 5-methylheptadecanal Furthermore, putative compounds with double bonds and methyl side chain positions estimated from these were synthesized, and their When we compared the mass spectrum of the natural product, the two showed good agreement.

Table 3 Characteristic fragments of active substances and 14-methyl-1-octadecene synthetic compounds Example 1) 0H-C11H1+ -0H-Q r -Ct
*11z+-0H (■) (set 1.12-dodecanediol + III with 199 and HBr
30 m was stirred with a magnetic stirrer and heated.

Extractions were performed with hexane every 12 hours. After concentration, the extract was purified with a Florisil column, and 7t of 12-bromo-1
-Dodecanol (yam) was obtained.

2) Br-C+1H24-OH-+(phsP(C+
The compound (6,3f) obtained in 1) and triphenylphosphine 6.6f were dissolved in 75 ml of acetonitrile and refluxed for 2 days. -hydroxydodecyl)triphenylposphonium bromide (I
VI was obtained with a yield of 83%.

CHs −→C4HI −C= CH−CBH** −0H(V
l Next, put 2f of NaH into a dry round bottom flask, and
25 m of M80 was added, and stirring was continued for 1 hour while heating. The mixture was cooled to room temperature and 40 ml of anhydrous THF was added.

This was cooled on ice, and a solution of the phosphonium salt (ff) 1 o, 6t obtained in 2) above dissolved in DM8025 was slowly added dropwise thereto. After stirring with a magnetic stirrer for 1 hour, 2f of methyl butyl ketone was added dropwise little by little, and the mixture was further stirred for 1 hour. To stop the reaction, the mixture was poured into ice water and extracted with ether. The ether layer was washed with saturated brine and dehydrated with Na1SO4, and then the ether was distilled off. The white oil was extracted three times with hexane, concentrated, and then purified with a 70 lysyl column to obtain 13-
Methyl-12-hebutadecen-1-ol (Vl) was obtained. The yield was 31%.

GC-M8 result M/Z (relative strength) 26BCM+
) (139%), 250 (0,08%), 211 (
0,52%) 4) CH.

C4H@-C=CH-Cat Htt 0H(V) CH.

One C, H, -CH-CH, -C,, H□0H (Vl
To a mixture of l24sIl of hydrazine, 3.3ml of 30% hydrogen peroxide solution, and 220d of ethanol was added 4.81ml of the compound obtained in 3), and the reaction was allowed to proceed at 50°C for 7 days. The reaction was stopped by adding HC and extracted with ether. After dehydration, the product was purified using a Florisil column to obtain 4f of 13-methyl-1-heptadecanol tvn. The yield was 83%.

GC-M8 result M/Z (relative intensity) 252
Ha0) (0,24%), 210 (0,76%), 19
5 (1,48%) 5 ) CHa C, H, -CH-C1tH, 40H (■) - + C, H, -CH-C,, H mushroom, CHO (■) 0.5f in 5d'' pyridine Chromic anhydride was added thereto, and the compound (Vl) obtained in 4) was slowly added to carry out oxidation. 13-methyl-heptadecanal (■) was obtained in a yield of 49%.

6) CH.

(phs(CHs) )Br + C4H@-CH-C
11HHCHO(■) CH.

1〉C4-CH-CtIH□-CH=CH.

[11 15 m+# of anhydrous ether and 3.6 d of a butyllithium hexane solution were placed in a dry Mirofask, and 1.41 ml of a phosphonium salt was added thereto. After stirring with a magnetic stirrer for 1 hour, 1f of 13-methyl-heptadecanal was added and stirring was continued for 2 hours. This was poured into ice water to stop the reaction, and extracted with ether.

After dehydration, concentrate and extract with hexane three times.
Purified with Lysyl column. 66*14-methyl-1-
Octadecene tl+ was obtained with a yield of 21%.

Test example 1 The synthetic compounds were tested for their attractiveness in the field.

Synthetic compound 14-methyl-1-octadecene (purity 93
%) of 1.10,100μ2 and virgin female extract approx.
Using absorbent cotton soaked with female parts as an attraction source, 1
On April 27, 1983, we investigated the attractiveness of this plant to the male peach leaf moth in six peach orchards at the Fukushima Fruit Tree Experiment Station. Place the attraction source on the trap coated with adhesive, and place it on the ground.
．． They were placed on branches at a height of 5 to 2 m at approximately 10 m intervals, and the next morning, the number of captured peach leaf moths was investigated.

The number of fish captured in each plot is shown in Table 4 below, and significant attracting activity was observed in plots treated with 10 μ2 or more of the synthetic compound. 10 (virgin female extract 4 in Jar-treated plots)
It showed an attracting activity equal to or superior to that of 0 head.

Table 4 Comparison of attracting activity between synthetic compounds and virgin female extract *1 5% of those with the same sign were determined by Tankan's multiple test
There was no significant difference in the risk ratio.

*2 Average value *3 Standard deviation Test example 2 Synthetic compound 14-methyl-1-octadecene (purity 93
%) 1 piece in a plastic capsule (manufactured by Yasumoto Kasei Co., Ltd.)
and place it on an adhesive trap, 198
It was installed in the peach orchard at the Fukushima Fruit Tree Experiment Station on April 5, 2013. As a control, traps without any attractant were also set up in the same figure, and the number of peach leaf moths caught in these traps was monitored almost every day. We compared the number of female and male Momo leaf moths that were lured to death using a preliminary light (100 W mercury lamp, approximately 200 m away from the sticky trap) in the field.

In the trap using the synthetic product 1WIg as an attraction source, clearly more male moths were captured than in the control trap and the detection light, and the remarkable attracting activity of 14-methyl-1-octadecene was observed.

Table 5 Attractive activity of synthetic compounds

Claims (1)

[Claims] 1. Expression formula (1): 14-methyl-1-octadecene expressed as % formula % 2. The following steps: a) 1.12-Dodecanediol ttn and hydrogen bromide 12-bromo-1- obtained by reacting as shown in the following formula (1)
Dodecanol II + wo) Riphenylphosphine and the following formula [
React as in 111 (12-hydroxydodecyl)
Step of generating triphenylphosphonium bromide (IVI, 8O-CutTo4-OH+ HBr ull -→Br -CHH14-OH+H!O(+1(set Br-CHH14-OH+(phH)P(1) (phsP(CttH* +-0H))Br (Illb
) The (12-hydroxydodecyl)triphenylphosphonium bromide IIIVI obtained in step a) is reacted with methyl butyl ketone using the Witteig reaction using the following formula (
13-Methyl-12-heptadecen-1-ol (vl) is obtained by reacting as 13-methyl-12-heptadecen-1-ol (ml (iiil + (phs)P+HBr C) in step b) above. 1-ol (■ is represented by the following formula 6■) and reduced by hydrogenation to give 13-methyl-1-heptadecanol [VI
CHa CH3-(CH2)s -CH=CH-Cl, H,, O
H+V+ lll11 d) Then, a step of reacting the 16-methyl-hebutadecanal (■) with a triphenylmethylphosphonium salt using the Witteitz reaction as shown in the following formula (■), ? ” CHa-(CHI)j-C-C,lHt,・CHO-1
(ph3P(CHa))Br(■) A demonstrative formula [■]: CH. cn, -(CHt)s-C-c,,u,,c H=c
A method for producing 14-methyl-1-octadecene represented by n, ill. Formula (I): Hs CHs-CCHv)s-CH-CCH! >ll-CH=
An attractant for the peach leafhopper moth and its close relative 1, which contains 14-methyl-1-octadecene represented by CH2III as an active ingredient.