JPS6017793B2 - Sericolone, sericolol and sex attractants consisting of said compounds - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel compound that has a sex-attracting effect on tobacco beetles, which are pests of tobacco.

In recent years, it is well known that spraying insecticides to control pests has brought about various problems from a health and hygiene perspective. There is a strong need for the development of new technologies that can reduce usage.

As one method for this, research has recently become active on control methods such as cessation control using the so-called sex pheromone of insects and control methods by disrupting communication between the sexes. In general, the mating behavior of insects is controlled by highly concentrated odorants secreted by the insect itself (usually the female).

That is, the female adult releases volatile substances into the air, while the male adult begins to fly or walk towards the female adult that is the source of this odor, discovers the female adult, and engages in sexual activity. It gets excited and mates with it.

This odorant secreted by adult females is generally a sex pheromone or sex attractant (
It is an extremely important substance that controls mating behavior in insects. Therefore, it is possible to control pests by artificially using this sex pheromone to transfer male adults to a certain location and kill them, or by disrupting their normal mating behavior.

In addition, by investigating the occurrence of pests using this sex pheromone, it is possible to determine whether and when it is appropriate to spray insecticides, and thereby reduce the amount of insecticides used. Based on the above idea, the present inventors have conducted a search for the use of sex attractants for tobacco leaf beetles as part of the control of tobacco leaf beetles, which cause enormous damage to the tobacco industry every year as pests of dry tobacco leaves. They discovered the presence of a new substance in hexane extracts of adult female insects that has a strong sex-attracting effect on males, succeeded in isolating it, and confirmed its structure through synthesis, resulting in the present invention. I arrived at the eggplant.

That is, the present invention is a compound represented by the following structural formula (1) and a sex enhancer for tobacco beetles containing the compound as an active ingredient.

(In the formula, R,, R2 is R,=day, R2=OH or R,=
R2-, represents =0.

) The compounds represented by the formula (1) include the following two types of compounds depending on the difference in R and R2.

R,=R2=, compounds indicated by white 0 have chemical names 2 and 3.
-dihydro 3,5-dimethyl-2-ethyl-61 (1
-Methyl-2-oxobutyl)-4-pyran-4-one, commonly known as sericolone (hereinafter referred to as this compound (1-1
).

). In addition, the compound represented by R, = day "R2 = OH has the chemical name 2,3-dihydro-3,5-dimethyl-2-ethyl-6-(1-methyl-2-hydroxybutyl)-Misaki-pyran-4-one, and is commonly known as selicolor. (hereinafter referred to as the present compound (1-2)).The present compound (1-1) and (
As mentioned above, compounds 1-2) are novel compounds that were isolated for the first time from nature and have not been published in any literature, and the present inventors were able to synthesize them by the method described below. That is, in the presence of 5.4k9 boron trifluoride, 4.1
K9 diethyl ketone (compound [11)] and 7.5k9 propionic anhydride are reacted to obtain 3.5 kg of 4-methyl-hebutane-3,5-dione (compound ①). (yield 65%) Next, 3.5k9 diketone (compound '2'
) of 3.5X9: 2.3k in the presence of boron fluoride
By reacting parapropionaldehyde (9) with parapropionaldehyde (10) in ether, and incubating at 20-2yo for 1 hour,
．． 7k9 2,3-dihydro 3,5-dimethyl-2.
6-diethyl-cape-bilan-4-one (to obtain the compound 'Palisade').

(Yield 40%) The above pyranone 1.7k9 was converted into 2.4k
In the presence of 9 of ferric chloride and 0.1k9 of iodine, 0.5
In the chloroform, 3.9k9 propionic anhydride was reacted and incubated at 40 to 45o0 for 4 hours to produce 2,3-dihydro-3,5-dimethyl-2-ethyl-6-(1-methyl-2 -Oxobutyl) -Nagi-
Pyran-4-one (this compound (1-1)) is obtained.

(Yield 45%) Furthermore, this compound (1-1) was reacted with sodium borohydride in ethanol, and 2,3 dihydro 3,5-dimethyl-2-ethyl-61 (1-methyl-2-hydroxybutyl)-1 ' Pyran-4-one (the present compound (1-2)) is obtained once a day.

Compounds (1-1) and (1-2) of the present invention both exhibit strong pheromone activity against adult male tobacco beetles.

The properties of these compounds and data on mass spectrometry spectra, infrared absorption spectra, and proton nuclear magnetic resonance spectra are shown below. This compound (1-1), 2/3
-dihydro 3,5-dimethyl-2-ethyl-6-(1
-methyl-2-oxobutyl) one rainbow H-pyran-4-one.

Properties: Colorless and transparent liquid Mass spectrometry spectrum (intensity in parentheses) (skin/z) 2 spots (15) = M10, 57 (77)
, spots (18), 113 (31) 153 (10), 182
(100) Infrared absorption spectrum (in parentheses is absorption strength, s=Sro increase, m: middle, w weak)
(Hada-1) 2930 (S), 2850 (m), 1725
(S), 1660(s), 1605(s), 1460(
m), 1380 (m), 60 (m), 1350 (m),
1140 (m), 1050 (m) Broton nuclear magnetic resonance spectrum (number of protons and branches are shown in parentheses) (6 traces 3) o. 99 (phantom, t), 1.03 (thin, d), 1.
07 (lees, t), 1.31 (spot, d), 1.80 (spot,
s), 2.42 (crime, m), 3.70 (IH, q), 4
, 14 (IH, m) This compound (1-2), 2,3-dihydro-3,5-dimethyl-2-ethyl-6-(1-methyl-2-hydroxybutyl) Kazuya-pyran-4-one Properties: Colorless and transparent liquid content analysis spectrum (intensity in parentheses) (Desk/z) 240 (12) Ni M10, 57 (49), 5
9 (67), Satoshi (46), 109 (spot), 112 (99)
), 113 (100), 124 (37), 153 (28
), 182 (80) Infrared absorption spectrum (in the brackets is the absorption strength, s ni SUong, m = mid mountain e, w ni w
eak) (arc-1) 3400 (S), 2960 (S),
2920(S), 2860(m), 1650(s), 1
600 (s), 1460 (m), 1 total 0 (m), 119
0 (m), 1150 (m), 1065 (m), 975 (
m) Broton nuclear magnetic resonance spectrum (indicates the number of protons and branches) (6 plows) 1.0-1.2 (1 phantom, m), 1.75 (thin, s), 2.3 (IH, m), 2
．． 7 (IH, m), 3.6-4.0 (bait, m) The compound (1-1) or (1-2) of the present invention may be encapsulated as it is in a capsule made by Blastic, or synthesized. By mixing with resin, sand, algae, silica gel, and other powdered or granular carriers and adsorbing them to these carriers,
It can be used as a sex attractant for tobacco beetles.

As mentioned above, this sexual attractant can be used to attract and kill adult male insect pests in a certain location to reduce the pest population, or to volatilize a highly concentrated sexual attractant into the air. It can be used to control pests by disrupting communication and mating between males and females, thereby preventing their reproduction.

In the above, the present compounds (1-1) and (1-2) can be mixed to prepare a commercial insecticide.

In addition to the purpose of controlling pests as mentioned above,
This attractant can also be used in military investigations of pest outbreaks, ie timing and outbreaks. Next, the effects of the sex attractant according to the present invention will be specifically explained with reference to examples.

Example 1 Rolled paper (Toyo) cut into 1.5 pieces horizontally and 0.5 pieces vertically.

Paper no. 5) was folded into three layers to form a vertical shape, and a mixture of various amounts of this compound (1-1) was dissolved in hexane and the whole amount was left overnight for one night, and then added to each using a syringe and tested. Paper no. I made 1 to 8. This compound (1-1
) was synthesized using the method described in the main text above. On the other hand, 10 unmated male tobacco beetles 5 to 10 days after emergence were placed in 8 petri dishes each having a diameter of 10 skins, and each of the Testro papers mentioned above and hexane LR alone were added to each dish as a control. The discussion effect was compared using a similar vertically-shaped Japanese paper.

The results are shown in Table 1. The experiment was repeated three times and the average value is shown. Table 1 From Table 1, it was found that the present compound (1-1) had a strong attracting effect on unmated male tobacco beetles.

Example 2 Roll paper (Toyo Roll Paper No.
．． 5) was folded into three layers to form a vertical shape, and various amounts of the present compound (1-2) were dissolved in hexane to make a total volume of 1 μM, and then added to each using a syringe and tested. Paper No. It was set as 1 to 7.

The present compounds (1-2) were synthesized by the method described above. On the other hand, 5 to 1
Ten unmated females on day 0 were placed in each case, and each of the above-mentioned Testro paper and a similar freshly-tipped Ro paper to which only hexane 1R was added as a control were placed in each to compare the attraction effects.

The results are shown in Table 2. The experiment was repeated three times and the average value is shown. Table 2 From Table 2, it was found that the present compound (1-2) had a strong transfer effect on unmated male tobacco beetles.

Claims (1)

[Claims] 1. A compound represented by structural formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 and R_2 represent R_1=H, R_2=OH or R_1=R_2=, 0.)2 Tobacco beetles containing structural formula (I) as an active ingredient sexual attractant. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 and R_2 represent R_1=H, R_2=OH or R_1=R_2=,0.)