JPS6338965B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a cockroach attractant. Cockroaches are global sanitary pests and are distributed throughout Japan. As a way to get rid of cockroaches,
A known method is to place an exterminator in the path of cockroaches and trap them. In this method, a cockroach attractant is often placed inside the exterminator. As cockroach attractants, sex pheromones, which attract males, are known, and T-casinol, which excites both males and females, is known. The present inventors have conducted intensive studies to find a substance that has the same effect as a sex pheromone among synthesized substances, and as a result, they have discovered that a certain type of monoterbenoid compound has the above-mentioned effect, and have achieved the present invention. did. That is, the gist of the present invention resides in a cockroach attractant containing (+)-bervanylpropionate as an active ingredient. To explain the present invention in detail, (+)-bervanyl propionate

[Formula] As shown in the following formula, (+)-nopinone obtained by ozone oxidation of β-pinene is brominated to form 3β-
Bromonopinone was obtained, this was reacted with 1,8-diazabicyclo[5,4,0]-7-undecene (hereinafter abbreviated as DBU) to obtain apoberbenone, and (CH ₃ ) ₂ CuLi was added and the reaction was carried out in diethyl ether. Then, aluminum triisopropoxide is reacted in isopropyl alcohol to convert the ketone group to a hydroxyl group, and further reacted with propionic anhydride to convert the hydroxyl group to a propionyloxy group. Bye. Therefore, in the present invention, (+)-bervanyl propionate obtained as described above is used as a cockroach attractant. Its usage is
Approximately 0.01 mg to 2 mg is sufficient, and it is usually used by mixing it into feed. The agent is then usually placed on the cockroach exterminator. Specifically, the agent may be placed on the cockroach-trapping surface of the exterminator, such as the surface coated with an adhesive substance. This drug, as shown in the test column below,
Excite male cockroaches and attract them from their hiding places.
It moves around the drug violently, has a similar effect to sex pheromones, and is effective as an attractant. Hereinafter, the present invention will be explained in more detail using reference examples and test examples, but the present invention is not limited in any way by these examples. Reference example 1 (+) obtained by ozone oxidation of β-pinene
3 ml of bromine was added to a solution of 6.2 g of nopinone in 120 ml of ether and mixed for 30 minutes at room temperature. After the reaction, it was refluxed for 30 minutes and then washed with a solution of NaHSO ₃ and NaHCO ₃ . When the ether is removed, 3β-
6.0 g of bromonopinone was obtained. 2.7 g of DBU and 30 ml of dimethylformamide were added to 2.7 g of the above 3β-bromonopinone, and the mixture was stirred at 160° C. for 30 minutes under an argon atmosphere. The reaction mixture was poured into water and extracted with ether. After distilling off the ether, the residue was added to a silica gel column, and chromatography was performed using a mixed solvent of n-hexane and ethyl acetate in a ratio of 10:1. Crude apoberbenone 1.48
g was obtained. 2.8 g of crude apoberbenone was added to an ethereal solution of (CH ₃ ) ₂ CuLi prepared from 4.2 g cuprous iodide in 20 ml diethyl ether and 5% ethyllithium in 28 ml diethyl ether.
The mixture was stirred at room temperature under argon gas for 2 hours.
After the reaction mixture was washed with water and evaporated, the residue was added to a silica gel column and chromatographed using a mixed solvent of n-hexane and ethyl acetate in a ratio of 10:1. -1.6g of verbanone was obtained. 497 mg of this compound was dissolved in 1 ml of isopropanol, and an isopropanol solution containing aluminum triisopropoxide prepared from 450 mg of aluminum foil and 6 ml of isopropanol was added thereto, and the mixture was refluxed for 5 hours while distilling off the acetone produced. 1NHCl reaction mixture
and extracted with diethyl ether. The oily residue obtained by distilling off the ether was added to a silica gel column, and normal hexane:ethyl acetate=
Elution was performed with a 7:1 mixed solvent. [+]-450 mg of berbanol was obtained. [+] - Berbanol 39mg
was added to a pyridine solution of 0.3 ml of propionic anhydride,
The reaction was allowed to proceed overnight at room temperature. The reaction mixture was added to a silicic acid column, and normal hexane:ethyl acetate =
Column chromatography was performed using a 20:1 mixed solvent, and (+)-bervanylpropionate 40
mg was obtained. The specific optical rotation of this compound at a concentration of 1.0% by weight in benzene at 25° C. was measured using D-line (589 nm) and was found to be +11.2°. When the infrared absorption spectrum was measured by the film method, absorption was observed at 1730 cm ^-1 . When nuclear magnetic resonance absorption spectra were measured in deuterated chloroform, the results were 0.86ppm (3H, s) and 0.91ppm (3H, d, J=
6.5Hz), 1.10ppm (3H, t, J=7.0Hz), 1.24ppm
(3H, s) and 5.13ppm (1H, m). Here, ppm is a chemical shift, s, d, t, etc. are signal splitting modes, and J is a coupling constant. The mass spectrum is m/e224 (M ⁺ , C ₁₃ H ₂₂ O ₂ ), 195, 181,
155, 136, 121, 107, 93 (base peak), 85, 81
It was hot. Test Example 1 Approximately 25 adult male American cockroaches were reared in a breeding box containing a shelter made of seven sheets of paper placed at equal intervals, and this was used for a physiological activity test. 20μ of (+)-bervanylpropionate obtained in Reference Example 1
g was dissolved in an acetone solvent, absorbed by paper, and the solvent was evaporated, then placed in a breeding box and placed gently at a distance of 4 cm from the shelter and 3 cm from the side wall of the breeding box. Approximately 3 minutes after placing the paper, approximately 68% (17 cockroaches) of the cockroaches that had been stationary in the shelter started running out of the shelter, running around the paper impregnated with (+)-vervanyl propionate. It moved around violently with the behavior typical of sex pheromones.

Claims (1)

[Claims] 1. A cockroach attractant containing (+)-vervanyl propionate as an active ingredient.