JPH0366295B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel germacrene type compound and a cockroach attractant containing the compound as an active ingredient.

Cockroaches are global sanitary pests and are distributed throughout Japan. A known method for exterminating cockroaches is to place an exterminator in the path of the cockroaches and trap them, and in particular, cockroach-attracting substances are often placed inside the exterminator.

As cockroach attractants, sex pheromone, which attracts males, is known, and T-casinol, which excites both males and females, is known.

The present inventors, while searching for substances that have a cockroach-attracting effect, discovered that certain germacrene-type compounds have an excellent attracting effect and achieved the present invention.

That is, the gist of the first invention resides in 5S-isopropyl-2R-methyl-8-methylene-6-cyclodecen-1-one, and the gist of the second invention resides in a cockroach attractant containing the compound as an active ingredient. exists in

To explain the present invention in detail, 5S-isopropyl-2R-methyl-8-methylene-6-cyclodecen-1-one, which is a germacrene type compound of the present invention, is used, for example, in Sclidago
It can be easily produced from the well-known germacrene-D, which is contained in the aerial parts of L. altissima L. That is, first, as shown in the following formula, germacrene-D extracted and separated from the aerial part of Versaceae was epoxidized to epoxy germacrene-D (known substance) by a well-known method, and then the epoxy ring was opened to form epoxy germacrene-D. 5S−
Isopropyl-2,8-dimethylene-6-cyclodecen-1R-ol (known substance) is obtained.

In addition, the compound of formula [1] above is Agricultural
Biological Chemistry 39 , 1517-1518 (1975)
In addition, the compounds of formulas [2] and [3] are
Agricultural Biological Chemistry 42 , 79-82
(1978).

5S-isopropyl- represented by the above formula [3]
2,8-dimethylene-6-cyclodecene-1R-
When ol is dissolved in a solvent and oxidized with a suitable oxidizing agent, 5S-isopropyl-2,8-dimethylene-6-cyclodecene-1- shown by the following formula [4] is obtained.
On is obtained. Although this substance does not have a sex pheromone effect on cockroaches, it is a new substance that has not been described in any literature, and its structure was confirmed from the analysis results shown in Examples below.

5S-isopropyl-2R-methyl-8-methylene-6-cyclodecen-1-one represented by the following formula [5], which is a germacrene type compound of the present invention, is a 5S-isopropyl-2R-methyl-8-methylene-6-cyclodecen-1-one represented by the above formula [4]. ,8-dimethylene-6-cyclodecene-1-
can be produced by reduction treatment using a suitable reducing agent in a solvent.

The compound of formula [5] is also a compound that has not been described in any literature, and its structure was confirmed from the analysis results in the examples described later.

As mentioned above, the compound of formula [4] has no sex pheromone effect on cockroaches, whereas the compound of formula [5] of the present invention has been found to have an excellent cockroach attracting effect. That is, the compound of formula [5] of the present invention, as shown in the test example below, has an effect similar to that of a sex pheromone, excites male cockroaches, attracts them from their hiding places, and causes them to move around the compound. It is suitable as an attractant because it induces behavior similar to sex pheromones. When used as a cockroach attractant, the amount used is approximately 5 μg, and it is usually mixed into bait, etc. This agent is usually placed on the capture surface of a cockroach exterminator, such as a surface coated with an adhesive substance.

Hereinafter, the present invention will be explained in more detail with reference to production examples and test examples, but the present invention is not limited to these examples.

Production example (1) Production of germacrene-D Aerial parts of Solidago algae (excluding flowers) 19
kg into 5-10 cm pieces, extracted with methanol 72 at room temperature for 1 month, filtered, concentrated the liquid under reduced pressure at 40℃ to 6 cm, and the concentrated liquid (mostly water) was Extract with ethyl acetate.
The ethyl acetate layer was separated from the aqueous layer, dehydrated by adding anhydrous mirabilite, and then the mirabilite was separated and the liquid was divided into three equal parts. Graphical analysis was performed (column size: diameter 6 cm, length 60 cm; solvent: n-hexane; 1 fraction; 2). Since germacrene-D was present in fractions 1 to 3 of each chromatography (confirmed by gas chromatography described later), these were combined and concentrated under reduced pressure to obtain 14 g of a concentrate. 1 g of this concentrate was subjected to column chromatography using 180 g of Florisil impregnated with silver nitrate at a weight ratio of 10% (column size: diameter 3 cm, length 60 mm).
cm; solvent; 5% stepwise method of n-hexyne-chloroform-diethyl ether; 1 fraction; 30 ml).

In each chromatography, germacrene-D was included in the 50-100% ether concentration category in chloroform (confirmed by gas chromatography)
Therefore, combine these and concentrate under reduced pressure to obtain a concentrate.
8.8g was obtained.

Out of 8.8 g of this concentrate, 5.8 g was subjected to alumina micromatography (180 g of activated alumina) (column size: diameter 3.5 cm, length 40 cm; solvent: n-hexane).

Germacrene-D by gas chromatography
(containing about 90% or more) was collected to obtain 2.7 g of crude germacrene-D.

Crude germacrene-D 2.7g, Deperozil 30
-3 (Silica gel type manufactured by Nomura Chemical Co., Ltd., particle size 3 μ) Purification by repeated high performance liquid chromatography (Column size: diameter 4.6 mm, length 25 cm; solvent: n
-hexane) to obtain 1.9 g of pure germacrene-D [C ₁₅ H ₂₄ =204] represented by the above formula [1].
This product is a known substance and is also known to have a sex pheromone effect on American cockroaches.

Specific rotation of this product [α] ²⁵ _D °: -59.8° (C = 1.00,
n-hexane); Ultraviolet absorption spectrum UV (n-
(in hexane): λmax259nm (ε=4000); Infrared absorption spectrum IR (neat): νmax3070, 1630,
1605, 1390, 1375, 880cm ^-1 ; ^1H nuclear magnetic resonance spectrum PMR (in carbon tetrachloride); δppm0.81 (3H,
d, J=6Hz), 0.86 (3H, d, J=6Hz), 1.46
(3H, broads), 4.69 (2H, broads), 5.10 (1H,
m), 5.18 (1H, dd, J=16,9Hz), 5.73 (1H,
d, J = 16Hz); Mass spectrum (MS): m/
e204 (M ⁺ , C ₁₅ H ₂₄ ), 161 (M ⁺ −43, reference peak), 120, 105, 91, 81, 79, 41;

For gas chromatography (GC), column: (diameter 3 mm, length 2 m; packing material 4% OV-
1); Column temperature; 145°; Carrier gas; Nitrogen (flow rate, 50 ml/min); Retention time (t _R ): 7.1 minutes.

(2) Production of epoxy germacrene-D (epoxidation) 270 mg of germacrene-D was dissolved in 12 ml of methylene chloride and cooled to 0-2°C with stirring. After adding 0.15 ml of pyridine and 130 mg of solid sodium bicarbonate to this reaction solution, 100 mg of metachloroperbenzoic acid was added.
mg, 100 mg, and 50 mg were added at 5 minute intervals. After this,
After stirring under ice cooling for 1 hour, 0.1 ml of dimethyl sulfide was added thereto, and the mixture was stirred for 10 minutes. The reaction solution was transferred to a separatory funnel containing 10 ml of a saturated aqueous sodium hydrogen carbonate solution, and 10 ml of methylene chloride was further added, and the mixture was shaken well and then separated. The aqueous layer was further extracted twice with methylene chloride (20 ml, 10 ml), and all the methylene chloride layers were combined, washed with 10 ml of saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The obtained oil was chromatographed on 20 g of silica gel neutralized by trimethylamine treatment [solvent: n-hexane-ethyl acetate (10:
1)], 210 mg of epoxy germacrene-D (1α,2β-epoxygermacrene-D) [C ₁₅ H ₂₄ O=220] shown by the formula [2] above (yield 83%)
I got it.

This substance is a known substance and is also known to exert a sex pheromone effect on the American cockroach.

The specific optical rotation, UV, IR, and PMR measurements of this product were as follows.

[α] ²⁵ _D °: -14.6 ° ( C = 1.00, n-hexane); UV (n-hexane): λmax 234 nm (ε =
15900); IR (NEET): νmax3060, 1630, 1605,
1390, 1375, 975, 880 cm ^-1 ; PMR (CCl ₄ );
δppm0.82 (3H, d, J=6Hz), 0.87 (3H, d,
J=6Hz), 1.17 (3H, s), 4.84 (1H, broads),
5.46 (1H, dd, J = 15.5, 8.5Hz), 5.97 (1H, d,
J=15.5Hz) (3) 5S-isopropyl-2,8-dimethylene-
Production of 6-cyclodecen-1R-ol (ring opening of epoxy) A solution of 1.7 ml of diisopropylamine in 18 ml of anhydrous tetrahydrofuran was cooled to -75°C in a dry ice-acetone bath, and in an argon gas atmosphere, a solution of 1.6 N of n-butyllithium was added. -Hexane solution 7.2
ml was slowly added dropwise under stirring. After the addition, the cooling bath was removed and the solution was stirred at room temperature for 1 hour to form lithium diisopropylamide. The reaction solution was again cooled to -75°C, and a solution of 260 mg of epoxygermacrene-D in 6.2 ml of anhydrous tetrahydrofuran was added dropwise thereto, then the cooling bath was removed and the mixture was stirred at room temperature for 2.5 hours. The reaction mixture was transferred to a separatory funnel containing 20 ml of ice-water, 30 ml of n-hexane was added, and the mixture was shaken well and then separated. The aqueous layer was further extracted twice with n-hexane (30 ml, 30 ml), and all the hexane layers were combined and washed with 10 ml of saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The obtained residue is converted into alumina
Purified using 40 g of chromatography [solvent: n-hexane-ethyl acetate (6:1)] and preparative thin layer chromatography (alumina 150F ₂₅₄ ) to obtain 5S represented by the formula [3] above. -isopropyl-2,8-dimethylene-6-cyclodecene-
1R-ol [C ₁₅ H ₂₄ O = 220] 151 mg (yield 58%)
I got it. This substance is a known substance and has no sex pheromone effect on American cockroaches. The specific optical rotation, UV, IR, and PMR measurements of this product were as follows.

[α] ²⁵ _D °: -93 ° (C = 1.00, n-hexane);
UV (normal hexane): λmax237nm (ε=
13800); IR (NEET): νmax3320, 3060, 1630,
1605, 1390, 1375, 1275, 965, 880cm ^-1 ; PMR
(CCl ₄ ): δppm0.84 (3H, d, J=6Hz), 0.89
(3H, d, J=6Hz), 3.57 (1H, dd, J=5,
10Hz), 4.75 (1H, broads), 4.8412H, broads),
5.13 (1H, broads), 5.36 (1H, dm, J=15.5
Hz), 5.84 (1H, d, J = 15.5Hz); GC; t _R 16.3 minutes. (4) 5S-isopropyl-2,8-dimethylene-
Production of 6-cyclodecen-1-one (oxidation) 5S-isopropyl-2,8-dimethylene-6
In a solution of 90 mg of -cyclodecen-1R-ol in 7 ml of petroleum ether, 700 mg of active manganese dioxide was suspended and stirred at room temperature for 30 hours. The reaction mixture was centrifuged and the supernatant was collected. The precipitate was further washed several times with methylene chloride (total amount of methylene chloride 50 ml),
Each time, it was centrifuged and the supernatant liquid was collected. The entire organic phase was filtered through cotton to remove insoluble matter, and then concentrated under reduced pressure to obtain 5S-isopropyl-2,8-dimethylene-6-cyclodecene-1- represented by the above formula [4].
90 mg (quantitative yield) of _{C15H22O =} 218 were obtained as an oil. This substance is a new substance that has not been published in any literature, and has no sex pheromone effect on American cockroaches. Specific rotation, IR, PMR and
The MS measurement values were as follows.

[α] ²⁵ _D °: -8.3 ° (C = 1.00, n-hexane);
IR (NEET): νmax3060, 1670, 1630, 1605,
1390, 1375, 975, 890 cm ^-1 ; PMR (CCl ₄ ):
δppm0.80 (3H, d, J=6Hz), 0.86 (3H, d,
J = 6Hz), 4.73 (1H, broads), 4.80 (1H,
broads), 5.15 (1H, dd, J=16, 8.5Hz), 5.39
(1H, s), 5.59 (1H, s), 5.65 (1H, d, J=
16Hz); MS/m/e218 (M ⁺ , C ₁₅ H ₂₂ O), 203 (M ⁺
−15), 200 (M ⁺ −18), 190 (M ⁺ −28), 175 (M ⁺ −
43), 157, 147, 133, 119, 107, 105, 93, 91 (reference peak), 81, 79, 77, 71, 69, 67, 65, 43,
41; GC: t _R 13.3 min (5) Production of 5S-isopropyl-2R-methyl-8-methylene-6-cyclodecen-1-one (reduction) 5S-isopropyl-2,8-dimethylene-6
-9.0 mg of cyclodecen-1-one in 1 methanol
ml and add 9mg of sodium borohydride to this.
was added and stirred at 0°C for 50 minutes. 3 ml of water and 0.5 ml of 1N hydrochloric acid were added to the reaction mixture, and the mixture was extracted three times with hexane (10 ml, 5 ml, 5 ml). All organic layers were washed with 2 ml of saturated aqueous sodium bicarbonate solution and dried over magnesium sulfate. The obtained residue was subjected to column chromatography using 8 g of silica gel [solvent: n-
Hexane-ethyl acetate (15:1)] is purified to obtain the object of the present invention represented by the above formula [5], that is, 5S-isopropyl-2R-methyl-8-methylene-6-cyclodecen-1-one [ C ₁₅ H ₂₄ O=
220] 5.1 mg (yield 56°C) was obtained as a colorless oil. This substance is a new substance that has not been described in any literature, and as shown in the test examples below, it has an excellent sex pheromone effect on American cockroaches and is useful as a cockroach attractant. Specific rotation, IR and PMR of this product
The measured values were as follows.

[α] ²⁵ _D °: -24.0 ° (C = 1.00, normal hexane); IR (neat): νmax3060, 1700, 1640,
1605, 1390, 1375, 980, 880cm ^-1 ; PMR
(CCl ₄ ): δppm0.75−1.00 (9H). 4.76 (1H,
broads), 4.87 (1H, broads), 5.10 (1H, dd, J
= 16, 8.5Hz), 5.91 (1H, d, J = 16Hz); GC:
t _R 12.1 min Test Example Twenty-five adult male American cockroaches were isolated and reared in a breeding box equipped with a shelter in which seven sheets of paper were placed at regular intervals, and this was used for a physiological activity test.

A solution of 5 μg of 5S-isopropyl-2R-methyl-8-methylene-6-cyclodecen-1-one obtained in the production example dissolved in n-hexane was placed in a tube 2.5 cm long.
After absorbing the solvent on a 0.5 cm wide piece of paper and allowing the solvent to evaporate at room temperature, place it in a breeding box and place it 4 cm from the shelter.
The animal was placed gently 3 cm from the side wall of the rearing box.
One minute and 30 seconds after placing the paper, air was gently introduced through the hole in the side wall of the rearing box on the opposite side of the shelter.

Within 5 minutes after placing the paper on the paper, it started to exhibit characteristic sexual behavior (starting running from the shelter, moving violently around the paper, raising its wings and vibrating violently, and protruding the copulatory organ in its tail in an attempt to mate). Count the number of heads. As a result of 5 trials, the average number of animals that engaged in sexual behavior was 8 out of 25 animals. All tests were conducted in dim light, and
The breeding boxes that were once subjected to the test were not used for several days.

Claims (1)

[Claims] 1 5S-isopropyl-2R-methyl-8-methylene-6-cyclodecen-1-one 2 5S-isopropyl-2R-methyl-8-methylene-6-cyclodecen-1-one as an active ingredient cockroach attractant