JPH0631204B2 - Stegobiole, method for producing the same, and sex attractant for Jinsanshibamushi containing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel compound 2,3-dihydro-2,3,5-trimethyl-6- (1-methyl-2-hydroxybutyl) -4H-pyran. -4-one (stegobiol), a method for producing the same, and a sex attractant for Jinsanshibanbushi containing the same as an active ingredient.

[Prior Art] Alnus chinensis is widely distributed all over the world, and its eating habits are extremely diverse including foods such as paper, fiber, feed, bread, and biscuits. It also favors parasitic herbs such as ginseng, which is the origin of its name, and is an important pest for stored products in pharmaceutical factories and food factories. Such indoor pests are closely related to humans, and as a matter of course, they are subject to many safety and health restrictions when they are taken, and even if they are effective pest control measures used for other pests. Often impossible. For example, in certain warehouses, fumigants such as hydrogen phosphide and methyl bromide which are highly toxic fumigants are used as control agents for Jinsenshibamushi, but the use of DDVP agent is slightly used in the workshops and warehouses where factories are crowded. Only allowed. However, since the DDVP agent has no residual effect or penetrability, it can kill adults that live in areas where it is easy to come into contact with the drug, but adults, eggs, larvae, and pupae hiding in the corners of the plant can be killed. Since it has almost no effect on larvae, it is necessary to frequently administer them, and even if it succeeds in temporarily reducing the population density of adult worms, new emergence causes adult habitat density in a short period of time. Has the drawback of recovering. As described above, the spraying of pesticides for controlling pests poses various problems that are not preferable from the viewpoint of health and hygiene.

On the other hand, recently, researches on attracting control using insect pheromone, control method by interfering male-female communication, etc. have been activated. Generally, the mating behavior of insects is controlled by extremely small amounts of odorants secreted by the insects themselves (usually females). Adult females release volatile substances into the air, while adult males begin to fly or walk towards the female source of this odor, discovering the female adult and causing sexual arousal. Raise and mate with this. This odorant secreted by adult females is commonly associated with sex pheromones.
It is called a romone or sex attractant and is a very important substance that controls the mating behavior of insects. Therefore, it is possible to control pests by using this sex pheromone to attract and kill adult males to a certain place or to artificially disturb the normal mating behavior of adult males. It is also possible to reduce the amount of pesticides used by attracting and killing pests by using this sex pheromone, and by investigating the occurrence status of the pests, it is possible to judge the suitability and time period of spraying pesticides. is there.

[Problems to be Solved by the Invention] The present invention provides a novel substance that can be used as a sex pheromone of Jinzanbushi, a method for producing the novel substance, and the novel substance as an active ingredient. It is intended to provide a sex attractant containing the same.

[Means for Solving Problems] The inventors of the present invention have tried to use a sex attractant as a part of the control of Jin-Sanshibaemushi, which causes a great deal of damage to the food industry as a pest of food, and have searched for it. As a result, a novel substance having a strong male sex-inducing effect was found in a hexane extract of an adult female, and its isolation was successful, which led to the present invention.

That is, the present invention provides 2,3-dihydro-2,3,5-trimethyl-6- (1-methyl-2-hydroxybutyl) -4H-pyran-4-one (stegobiol) represented by the formula [I]. I will provide a.

Expression [I] Further, the present invention provides 2,3-dihydro-2,3,5-trimethyl.
Provided is a method for producing a substance, which comprises reacting -6- (1-methyl-2-oxobutyl) -4H-pyran-4-one (stegovinone) with sodium borohydride to reduce the same.

Furthermore, the present invention provides a sex attractant for Jelly beetle, which contains the above-mentioned novel substance as an active ingredient.

[Effects of the Invention] As will be concretely shown in the following examples, the novel compound of the present invention functions as a strong sex attractant for Jinja bugs. Therefore, it is possible to control this pest by using this compound, by attracting and killing the male adult of Jinbeushibushi to a certain place, or by artificially disturbing the normal mating behavior of the male adult. .
It is also possible to reduce the amount of insecticides used by attracting and killing pests by using this sex attractant, and by investigating the occurrence status of the pests, it is possible to judge the suitability and time period of spraying the insecticides. Is.

[Detailed Description of the Invention] The compound of the present invention represented by the above formula [I] (hereinafter referred to as the present compound) is a novel compound isolated from nature for the first time.

This compound was isolated by subjecting adult females of Ginkgo biloba to hexane and subjecting it to column chromatography (final eluting solvent is, for example, ethyl ether) and then high performance liquid chromatography (eluting solvent is, for example, a mixed solvent of hexane and tetrahydrofuran). Can be separated.

Further, this compound is 2,3-dihydro-2,3,5-trimethyl-6.
It can also be synthesized by reacting-(1-methyl-2-oxobutyl) -4H-pyran-4-one (stegovinone) with sodium borohydride to reduce it. This reduction is carried out in an organic solvent such as ethyl ether or tetrahydrofuran (which is preferred) with about 0.25 to about 0.5 (most commonly about 0.5 mol) per mol of stegovinone.
Using sodium borohydride, the temperature is lower than room temperature.

The compound is a viscous liquid, for example about 1 mg to 30 mg per about 1 g of carrier consisting of polypropyran and pulp.
It is convenient to mix them at a ratio of 1 to form a tablet and set it under open conditions. In addition, since the activity period of Jinsanshibamushi is from April to October, it is applied at that time.

[Examples of the Invention] Examples showing the isolation and synthesis of the present compound and the sex-inducing effect of the present compound will be shown below.

Example 1 Isolation of this compound Approximately 100,000 adult beetle beetle adults (equivalent to 50,000 female adult) 4 to 6 days after emergence, which were grown in a medium, were treated with about 20 hexane.
Extraction was carried out by immersing it in 00 ml for a whole day and night, and the extract obtained by filtering this was concentrated under reduced pressure at 30 ° C to 35 ° C to obtain 5 g of the concentrate.
Got The concentrate was subjected to column chromatography using 100 g of silica gel (manufactured by Merck) in an amount equivalent to about 20 times. That is, after dissolving 5 g of the concentrate in 5 ml of hexane, it was adsorbed on a silica gel column and mixed with hexane and hexane / ethyl ether = 90:10 (volume), hexane /
250 ml of ethyl ether = 80: 20 mixed liquid, hexane / ethyl ether = 70: 30 mixed liquid, hexane / ethyl ether = 50: 50 mixed liquid, ethyl ether were successively eluted with 250 ml each.
Fractions eluted with ethyl ether from 30 ℃ ~
Concentration under reduced pressure at 50 ° C gave 10 mg of concentrate.

Zorbax sil (DuPont, 4.6 mm z 25c
m) High performance liquid chromatography equipped with a column was performed. Using a mixture of hexane / tetrahydrofuran = 85:15 as the mobile phase, the peak appearing at a retention time of 12 minutes (flow rate 2.0 ml / min) detected by absorption at UV270nm was collected to obtain 2m of this compound.
got g.

The compound was in the form of a colorless liquid, and its mass spectrum, proto, and carbon nuclear magnetic resonance spectrum data are shown.

High-resolution mass spectrum C ₁₃ H ₂₂ O ₃ Actual value 226.1535 Calculated value 226.1567 Mass spectrum (70eV) m / z (%): 226 (M ⁺ , 8), 168 (88), 141 (20), 139 ( 17), 124
(15), 113 (70), 112 (100), 109 (27), 101 (17), 85 (1
7), 84 (15), 83 (87), 70 (16), 59 (49), 57 (33), 56 (3
7), 55 (45), 43 (41), 41 (52) Proton nuclear magnetic resonance spectrum (500MHz), ppm, parentheses indicate the number of protons, branching and attribution. The number of each atom used in the assignment is defined as a number.

1.00 (3H, t, J = 7.4Hz, Me-10) 1.04 (3H, d, J = 7.3Hz, Me-12) 1.18 (3H, d, J = 7.1Hz, Me-14) 1.33 (3H, d , J ＝ 6.6Hz, Me-11) 1.42 (1H, m, H-9) 1.60 (1H, m, H-9 ′) 1.75 (1H, s, Me-13) 1.89 (1H, d, J = 7.4 Hz) 2.38 (1H, dq, J = 7.3,3.4Hz, H-3) 2.86 (1H, dq, J = 7.1,6.8Hz, H-7) 3.58 (1H, m, H-8) 4.49 (1H, dq, J = 6.6,3.4Hz, H-2) ¹³ C-nuclear magnetic resonance spectrum (125MHz), ppm 197.1,172.
7,109.5,75.5,43.8,40.9,28.3,15.9,14.8,10.1,9.4,9.3 Example 2 Synthesis of this compound Obtained according to the corrected Examples 1 and 2 described in JP-A-59-112981. 3-dihydro-2,3,5-trimethyl-6-
22.6 g (0.1 mol) of (1-methyl-2-oxobutyl) -4H-pyran-4-one (stegovinone) was dissolved in 100 ml of ethyl ether, and sodium borohydride 3.8 g (0.1 mol) and zinc chloride 10.1 g ( 0.1 mol) was added and the mixture was stirred at room temperature for 3 hours. The reaction solution is then 300 ml of ice water and 200 ml of ethyl ether.
It was poured in, stirred vigorously and washed with water. The ethyl ether phase was concentrated under reduced pressure to obtain 22 g of reaction occlusion. The reaction mixture was fractionated by silica gel column chromatography according to the method of Example 1 to obtain 14.3 g of the present compound. The compound obtained by this synthetic method consisted of a mixture of stereoisomers and was analyzed by gas chromatography (Carbowax 20M, 25m, 100 ℃ -210 ℃).
C., 2 ° C./min), but all mass spectrometric spectra were in agreement with those shown in Example 1.

Example 3 Sex-attracting effect of this compound 3 pieces of filter paper (Toyo filter paper No. 5) cut into 1.5 cm in width and 0.5 cm in length were used.
No.1 to NO.10 on the table to the one that is folded in a row and made into a vertical shape
Dissolve the amount of this compound in hexane and
This was added by syringe as l. This compound was used by being extracted and isolated from an adult female Jerusaper beetle by the method of Example 1 described above.

On the other hand, in a petri dish having a diameter of 10 cm, 10 unmated plants 4 to 6 days after emergence were placed, and in contrast to a filter paper to which the above compound was added, 1 μl of hexane was added to another petri dish in a similar manner. As a result of investigating the attracting effect of both of them by placing a filter paper in the form of a sheet, the results shown in Table 1 were obtained. The experiment was repeated three times and the average value was shown.

Example 4 Next, an example in which the present compound and stegovinone are compared with respect to the sexual attraction effect will be shown.

Place a filter paper of the same diameter in a petri dish with a diameter of 9 cm, and release 10 unmated male adults of the beetle, Jinsanshibamushi, at a temperature of 2
It was placed in a bright place at 8 ° C. and a humidity of 60%. A 5 mm x 2 cm piece of filter paper was folded, and the compound or stegovinone was added thereto and placed in a petri dish. Each addition amount is 10-10 ^-5 μ
It was g. The present compound and stegovinone used were those extracted from female gypsy bugs. The total number of attracted males per 10 minutes gathering on the filter paper pieces was compared.
The experiment was repeated 5 times, and the average value is shown in Table 2.
It was shown to.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Akihiro Kono 6 Umegaoka, Midori-ku, Yokohama, Kanagawa 2 Central Research Institute of Japan (72) Inventor Akio Onishi 6 Umegaoka, Midori-ku, Yokohama, Kanagawa Japan 2 Central Research Laboratory (72) Inventor Mikio Ono 3-5-8 Midorigaoka, Hamura-cho, Nishitama-gun, Tokyo Inside Fuji Flavor Co., Ltd. (56) Reference JP-A-59-163380 (JP, A)

Claims (3)

[Claims] 1. A 2,3-dihydro-2,3,5-represented by the formula [I].
Trimethyl-6- (1-methyl-2-hydroxybutyl) -4H-pyran-4-one. Expression [I] 2. Reduction of 2,3-dihydro-2,3,5-trimethyl-6- (1-methyl-2-oxobutyl) -4H-pyran-4-one with sodium borohydride. Consists of doing
A method for producing 2,3-dihydro-2,3,5-trimethyl-6- (1-methyl-2-hydroxybutyl) -4H-pyran-4-one. 3. Sex attraction of Jin-Sanshibamushi containing 2,3-dihydro-2,3,5-trimethyl-6- (1-methyl-2-hydroxybutyl) -4H-pyran-4-one as an active ingredient. Agent.