JPH0881306A - Cockroach repellent containing sesquiterpene - Google Patents

Abstract

PURPOSE: To obtain a cockroach repellent containing a sesquiterpene-alcohol or a sesquiterpene-ketone contained in vetiver oil or elemioil as an active component. CONSTITUTION: This cockroach repellent contains a sesquiterpene having at least one group selected from among C(CH3 )2 OH, CH(CH3 )CH2 OH, CH2 OH, and a cyclic ketone group and at least one double bond, e.g. elemol, β-eudesmol or vetiselinenol as an active component.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a cockroach repellent containing sesquiterpene-alcohol or sesquiterpene-ketone contained in vetiver oil or eremi oil as an active ingredient.

[0002]

BACKGROUND OF THE INVENTION Chemical control methods for sanitary pests include insecticides, repellents, chemical infertility agents, attractants, etc. When handling foodstuffs, etc., or in places where humans can easily access it, its safety becomes a problem. Therefore, a repellent which is not insecticidal but relatively safe and is useful for preventing spawning and damage is used because harmful insects dislike and avoid its aroma and color. Diethyl toluamide (DEE) is a typical repellent in recent years.
T)) is mentioned, and it is known that it is fast-acting and exhibits repellent effect against various insects. However, it has been pointed out that it has a poor residual effect and is harmful to the human body, and it is being prohibited to use it.

On the other hand, the German cockroach, which is said to be originated in Africa, is currently the most widely distributed in the world. Because it is weak in cold resistance, it is only the Nansei Islands south of Amami Oshima that can indigenous to Japan's natural climate, but there are many sanitary pests throughout Japan, such as buildings and restaurants that have heating facilities and are capable of wintering. Is. Black cockroaches are often found in ordinary houses in Japanese houses.

[0004] Therefore, when a repellent active substance against German cockroaches or black cockroaches was sought, a diligent search was conducted for several kinds of plant essential oils, which are natural products that have little impact on the ecosystem and are highly safe to the human body. It was found that vetiver oil and Elemi oil are active.

A detailed report on the insect repellent activity of terpenoids has been made in monoterpenoids. In that case, it has been pointed out that an aldehyde group, a hydroxyl group, a carbonyl group, or an acetyl group is involved as the active group. However, it is also important for the repellent activity to be expressed, as it is a molecule that is easily gasified at room temperature.

The vetiver essential oil used in the present invention was mainly composed of sesquiterpene alcohol, and was also composed of sesquiterpene ketone and sesquiterpene hydrocarbon, but the main components of repellent activity were the sesquiterpene alcohol elemol and β. -Eudesmol and beticerinenol. Significant activity was also seen in the main ingredients, kushimol and betivone, but not as strong as the former.
The activity of elemol was similar to that of DEET, but elemol was superior in residual effect. Elemi oil is contained in about 15% in eremi oil.

Namely, repellent activity against German cockroaches _{are, -C (CH 3) 2 -OH} , -CH (CH 3) -CH 2 O
H, -CH ₂ OH and cyclic ketone group, more preferably, -C (CH _{3) 2} -OH and -CH (CH ₃₎ -CH ₂ O
It is strongly found in sesquiterpene alcohols or sesquiterpene ketones which, in addition to at least one group selected from H, have at least one double bond, more preferably a terminal methylene group.

Specific examples thereof include elemol, β-eudesmol, betiserinenol, 10-epi-γ-eudesmol, kushimol, nootkatone, β-vetibon, and the like, more preferably, elemol,
β-eudesmol and beticerinenol. In _{particular, -C (CH 3) 2 -OH} (3 alcohol groups) or -
Elemol, β-eudesmol and beticerinenol having CH (CH ₃ ) —CH ₂ OH (primary alcohol group) and terminal methylene show strong activity, and a strong relationship between repellent activity and chemical structure is found.

Elemol, 10-epi-γ-eudesmol, β-eudesmol, betiserinenol,
The repellent activities of ant other than cockroaches and mosquitoes such as kushimol, nootkatone and β-vetibon were examined, but no repellent activity was observed for these insects. Therefore, the above-mentioned sesquiterpene alcohol or sesquiterpene ketone has a specific repellent activity against cockroaches, suggesting that the active groups differ depending on the control insect species.

Materials 1. Vetiver and Vetiver Oil Vetiveria ( Vetiveria zizanioides Stapf.) Is a perennial plant of the Gramineae family that grows in the tropical and subtropical regions , and is cultivated in Java, Reunion, Haiti, Brazil, China, Japan and India. The shape of the grass is similar to Japanese pampas grass, but the length is up to 2m, and many gather to make a big plant. The leaves are long and slender, and the leaves are loosely folded, with a width of about 1 cm. A long conical spikelet with a length of 15 to 30 cm is placed upright on the shoot apex, and short branches are looped. Spikelets
There are no thorns and short thorns are lined up on the outside. He prefers high temperatures, but is extremely wind resistant and can withstand low temperatures. Also, the roots are pale yellow or reddish gray and twisted, but they are considerably long. Vetiver oil is obtained by steam distillation of this root, and leaves contain almost no essential oil. This essential oil is a dark brown viscous liquid with a good retention, with a heavy woody earthy scent reminiscent of roots and earth.

2. Elemi oil olivine family of elemi (Canarium luzonicum Miq.) Or Kenari nuts tree (Canarium commune Linne (Canar
ium indicum Linne)) resin is the origin, the origin is Philippines, Malaysia, Indonesia, Africa,
Central and South America. Essential oils are obtained by steam distillation of resins (20-30%). Essential oils are white or light yellow with a spicy, citrus-like flavor. Contains components such as remycin, elemol (about 15%), α-d-ferrandrene, dipentene.

3. German cockroaches and black cockroaches German cockroaches ( Blattella germanica Linne) are widely distributed throughout the world, and even in Japan. Body length is within 15mm and very small compared to other species. The body is characterized by a yellowish brown color and a pair of elongated black spots on the back of the anterior chest. There are many places such as buildings, restaurants, inns, wooden apartments where people live together, there are heating facilities, and where the fire is not extinguished. Egg period is about 20 days, larval period is about 100
Six days passed in a day. Adults have a lifespan of over 100 days. The number of tail and antennae nodes increases with age. The black cockroach ( Periplanetu fuliginosa Serville) has a body length of 30 to 40 mm and the whole body is blackish brown. The body and splashes are very shiny. The back of the chest is semicircular, lacking spots,
The blackness and gloss are the strongest. Both males and females are longer than the ventral edge. It is very similar to the American cockroach, but the whole body is rounded. This species is distributed in the south of Kanto, and is more abundant in the south. It is often found in ordinary houses in Japanese houses.

Next, the damage of cockroaches classified into three categories will be described. One of them is that it makes you feel uncomfortable. It looks ugly and filthy, and has a peculiar odor. Next is the transmission of pathogenic bacteria. Since various cockroaches eat dry feces and sputum, and also walk and defecate on food and tableware, digestive system infectious bacteria such as cholera, typhoid, and shigella, and sputum such as tuberculosis. Many experiments have shown that the pathogens and polioviruses appearing in the mosquito are scattered around. Some bacteria reproduce within the cockroaches, but many pathogens do not reproduce but appear alive in cockroach feces. The cyst of Entamoeba histolytica is also transmitted in this way. Lastly, it is harmful as an intermediate host of parasitic helminths. Cockroaches feed on fecal parasite eggs and develop larvae within their bodies to serve as intermediate hosts. Hookworm (Acanth
belongs to the ocephala), have also been found from people when Moni
Among the liformis moniliformis species, cockroaches and crickets are intermediate hosts, and the nematode Gongylonema scuitatum (cattle and sheep are the final hosts, rarely found in humans ), G. orienta.
The le (mouse is the final host) also develops larvae in the German cockroach, the American cockroach, and so on.

Method 1. Bioassay A repellent test against German cockroaches and black cockroaches was performed by the beaker method. Release 30 adults (♂: ♀ = 1: 1) of German cockroaches and black cockroaches into a transparent plastic pot (30 cm in diameter, 15 cm in height, butter is applied to the wall to prevent cockroaches from escaping),
An acetone solution of the sample was treated in the center of the pot and air-dried filter paper was placed for about 20 minutes, and an aluminum foil was covered on the filter paper.
A beaker with a volume of 00 ml was placed face down, and after standing still for 24 hours, the number of insects invading the beaker through the spout of the beaker was counted. Acetone alone was used as a control substance, and the repellent effect was determined by comparison with other samples. Figure 1 shows the equipment used for the beaker method.
Shown in

[Equation 1] Repellent rate (%) = (number of insects in control beaker [animal])
-Number of worms in sample beaker) x 100 Number of worms in control beaker [animal]

The main components of vetiver oil by production area (Table 1) and the results of the repellent activity test against German cockroaches and black cockroaches by the beaker method (Table 2) are shown below.

[Table 1] Table 1 Composition table of major alcohols and ketones in vetiver oil Sesquiterpene origin (%) * Haiti Java Brazil Bourbon Elemol 2.12 Tr 1.61 Tr 10-Epioidesmol 2.76 1. 87 1.55 1.63 β-eudesmol 2.83 0.86 2.03 0.89 Vetiverol 1.93 0.94 1.80 0.95 Cyclocopacanphenol 3.81 1.22 4.071 .62 Nootkatone 1.28 2.40 Tr 4.88 Betiserinenol 4.69 Tr 4.84 Tr β-Betibone 17.56 17.62 27.44 28.05 Cushimol 11.21 4.07 14.65 11.78 α-Betibone 3.23 2.73 Tr 5.14 *%: Percentage of total peak area Tr: Trace

The repellent activity of vetiver essential oils for each production area against German cockroaches and black cockroaches was examined. Table 2 shows the results.

TABLE 2 cockroach (A) and black cockroach (B) for repellent activity test sample usage repellent activity (g / m ²⁾ A B Activation after use start after 24 72 (hours) 24 72 (time) vetiver Bourbon 1.0 +++ +++ +0.1 0.1 + + + -Vetiver Java 1.0 +++-++-0.1 +-+ + -Vetiver Haiti 1.0 +++ + + + + + + + + 0.1 + + + + + + + Vetiver Brazil 1.0 ++++ ++ ++ ++ 0.1 ++ ++ DEET (control compound) * 1.0 ++++ +++++ ++ 0.1 +++ ++++++ : Evaluation of repellent activity of diethyl; strong (100 % -71%): +++ Medium (70% -41%): ++ Weak (40%-): + None:-

Vetiver oil from Haiti showed strong repellent activity against German cockroaches and black cockroaches. Therefore, the components of vetiver oil from Haiti were separated and refined.
Table 3 shows the gas chromatogram of vetiver oil from Haiti (Fig. 2) and the separation / purification procedure.

[Table 3]

Separation and purification of Vetiver oil from Haiti Vetiver essential oil (30 g) was subjected to silica gel column chromatography (Wakogel C-300, 350 g, column 38 m).
m × 90 cm), develop with hexane (3.0 l),
r-1 was obtained. Then hexane: ethyl acetate (8: 1,
4.5 l), and using gas chromatography as a monitor, Fr-2 (8.61 g) and Fr-3 (5.4
Fractionation into g). Further, the column was developed with methanol and eluted to obtain Fr-4. Fr-2 and Fr-3 were further purified by silica gel column chromatography and HPLC to obtain Fr-
2 to components 11, 13, 14 and Fr-3 to component 1
8, 19, 20, 21 and 22 were obtained. The structure of the isolated component was confirmed by IR, UV, NMR and GC-MS.・ GC-MS (Shimazu GC-MS QP-1000) column; OV-17 temperature; 90-160 ℃ (inj.250 ℃) Flow rate; 3 ℃ / min Electron energy; 70eV ・ UV (Shimazu UV-204) ・ IR (Shimazu FTIR-8200D) ・ NMR (NEC JNM-GSX 500) ・ Gas chromatography (Yanaco G2800) Column; OV-17, 0.25mmID, 25m Temperature; 50-160 ℃ (inj.230 ℃) Flow rate; 3 ℃ / min Detector; FID / HPLC (Nippon Analytical Industry LC-908) column; GPC column [Hitachi Chemical Co., Ltd. GL-P211N, GL
-P212N] Flow rate; 1.5 ml / min UV detector; 254 nm solvent; CHCl ₃

Next, the results of the repellent activity test of each fraction of Haiti vetiver oil against the German cockroach (Table 4) are shown.

[Table 4] Table 4 Repellent activity test sample of each fraction of vetiver oil from Haiti against German cockroach Use amount (g / m ² ) Repellent active vetiver oil 1.0 + + + 0.5 + Fr. 1 (hydrocarbon) 1. 0 ++ 0.5 - Fr.2 (ketones, alcohols) 1.0 +++ 0.5 +++ Fr.3 (main component) 1.0 +++ 0.5 ++ Fr.4 1.0 + 0.5 - DEET ( Control compound) 1.0 +++ 0.5 +++ 0.25 +++ 0.1 + * DEET = diethyltoluamide Evaluation of repellent activity; Strong (100% -71%): +++ Medium (70% -41%): ++ Weak (40%-): + None:-

Table 5 shows the main sesquiterpenoids contained in each fraction of vetiver oil produced in Haiti and their compositions.

[Table 5] Table 5 Major sesquiterpenoids contained in vetiver oil from Haiti Fraction Peak Sesquiterpenoids M ** Total peak area Method *** % against No. No. * 1 Unidentified 204 0.37 1,2 2 Aromadendrene 204 0.87 1,2,3 3 Cucimene 204 1.08 1,2,3 4 Aromadendrene 204 2.35 1,2 F-1 5 δ-Cadinene 204 3.03 1,2,3 6 Unidentified 204 1.85 1,2 7 Seton I 202 1.95 1,2,3 8 α-Calacolene 202 2.16 1,2,3 9 Seton II 202 1.75 1,2 10 Unidentified 202 3.86 1,2 A 11 Elemol 222 2.12 1,2,3,4,5 12 Not yet Identification 204 0.63 1,2 F-2 13 10-Epioidesmole 222 2.76 1,2,3 B 14 β-Oidesmole 222 2.83 1,2,4,5 15 Unidentified 222 1.59 1,2 16 Vetiverol 222 1.93 1 , 2,3,4 17 Unidentified 220 2.21 1,2 A 18 Cyclocopacanphenol 220 3.81 1,2,3 F-3 19 Nootkatone 218 1.28 1,2,3 20 Beticerinenol 220 4.69 1,2,3 21 β -Vetibone 218 17.56 1,2,3,4,5 B 22 Cymol 220 11.21 1,2,3,4,5 23 alpha-Bechibon 218 3.23 1, 2, 3 * using the molecular ion *** identified by numbers ** GC-MS analysis of the compounds corresponding to the peak in FIG. 2 Method: 1 = retention time in GC, 2 = GC-MC, 3 = cochromatography, 4 = IR, 5 = NMR

The structural formulas of the main sesquiterpene alcohols and sesquiterpene ketones of vetiver oil from Haiti are shown.

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Table 6 shows the repellent activity of major sesquiterpenoids contained in vetiver oil against German cockroaches and Black cockroaches.

[Table 6] Table 6 Repellent activity test of major sesquiterpenoids contained in vetiver oil against German cockroach (A) and black cockroach (B) Test compound Usage amount Repellent activity (g / m ² ) A B After use After use 24 72 (hours) 24 72 (hours) Elemol 1.0 ++++++++++++++ 0.1 +++++++ 10-ep-γ-eudesmol 1.0 ++ −− + − 0.1 + − + + β-oide Small 1.0 +++++ +++++ +0.1 + + + + + veticerinenol 1.0 +++ + + +++ +0.1 +-+-cyclocopacanphenol 1.0 +-+ + +0.1 x-l-kushimol 1 0.0 +++ + +++ + 0.1 +-+ + Nootkatone 1.0 + + + + + + 0.1 + + + + + + β-vetibon 1.0 + + + + + + + 0.1--+- DEET * 1.0 ++ + +++ + 0.1 + + + + + + *: diethyl toluamide

Results The main components having repellent activity were the sesquiterpene alcohols elemol, β-eudesmol and beticerinol. Significant activity was also seen in the main ingredients, kushimol and betivone, but not as strong as the former. The activity of elemol was similar to that of DEET, but elemol was superior in residual effect. That is, the repellent activity against German cockroaches is 1-methyl-1-hydroxy-
Ethyl group, 1-methyl-2-hydroxy-ethyl group, hydroxymethyl group and cyclic ketone group, more preferably 1-methyl-1-hydroxy-ethyl group (tertiary alcohol) or 1-methyl-2-hydroxy group. It is strongly found in sesquiterpene alcohols or sesquiterpene ketones which have at least one double bond, preferably a terminal methylene group, in addition to at least one group selected from -ethyl group (primary alcohol). In particular, elemol having a 1-methyl-1-hydroxy-ethyl group (tertiary alcohol) or a 1-methyl-2-hydroxy-ethyl group (primary alcohol) and a terminal methylene, β-
Oidesmole and beticerinenol show strong activity,
There is a strong relationship between repellent activity and chemical structure.

A repellent activity test was carried out on the main sesquiterpenoids contained in the above-mentioned vetiver oil against Amitaria and Aedes. Evaluation methods a) Amimeari (Pristomyrmex pungens MAYR) for Field colonies of the test Amimeari of repellent activity was assessed in a subject. Filter paper treated with 1 ml of acetone solution (1% and 5%) of each test substance and 1 ml of acetone as a control (Toyo Filter Paper No. 5
(3 × 3 cm) for 15 minutes to evaporate the acetone, and then the filter papers are juxtaposed near the entrance and exit of the preset colony at 10cm intervals, and honey is dripped at the center of each filter paper for 1 hour. After and 24 hours later, the number of insects collected on the filter paper was counted, and the repelling rate [(the number of insects on the control filter paper-the number of insects on the sample-treated filter paper / the number of insects on the control filter paper) x 100] was calculated. b) Aedes (Aedes albopictus Skuse) ethanol solution (1% test substance about 10 cm ² forearm of one arm of the human body in forest observed occurrence of the test Aedes for 0.1%) a 1 cm ² per Apply 0.5 ml, and after applying the sample 1
The number of mosquito bites for 10 minutes was measured after 4 hours and after 4 hours. The repellency rate was calculated from [(the number of bites in the control group-the number of bites in the sample application group / the number of bites in the control group) x 100] with the number of bites in one arm treated with ethanol alone as a control.

Table 7 shows the results of the repellent activity test of sesquiterpenoids contained in vetiver oil against Aedes edulis and Aedes mosquitoes.

[Table 7] Table 7 Repellent activity test of main sesquiterpenoids contained in vetiver oil against Amemari (A) and Aedes mosquito (B) Test compound Use amount Repellent activity (g / m ² ) A B After use 1 After use 1 24 (hours) 14 (hours) Elemol 1.0 +++ + − − 0.1 − − − − − 10-ep-γ-eudesmol 1.0 + + − − − 0.1 − − − − β-eudesmol 1.0 ++-+ +0.1 ---- Betiserenenol 1.0+ +-0.1 ---- Cyclocopacanphenol 1.0 ---- 0.1 ----- Cushimol 1. 0 +++ + + + 0.1 Nootkatone 1.0 + + + + +0.1----β-Vetibone 1.0 + + + + + 0.1 ---- DEET * 1.0 +++ ++++++ 0.1 ++++++++: Diethyl toluamide

Results Elemol, 10-epi-γ-eudesmol, β-eudesmol, betiserinenol, cyclocopacanphenol, kushimol, nootkatone and β-vetibon were:
Neither ants nor Aedes showed higher repellent activity as compared to the control compound, DEET. That is, it has a specific repellent activity against cockroaches, suggesting that the active groups differ depending on the control insect species.

[Brief description of drawings]

FIG. 1 is a diagram showing an apparatus used in a beaker method.

FIG. 2 is a diagram showing a chromatogram of Haitian vetiver oil.

Claims (5)

[Claims] 1. --C (CH ₃ ) ₂ --OH, --CH (CH ₃ )-
A cockroach repellent containing as an active ingredient a sesquiterpene having at least one group selected from the group consisting of CH ₂ OH, —CH ₂ OH and a cyclic ketone group and at least one double bond. 2. The sesquiterpene is elemol, β-
Eudesmol, beticerinenol, 10-epi-γ-
Oidesmall, Kushimol, Nootkaton or β-
The cockroach repellent according to claim 1, which is betivone. 3. --C (CH ₃ ) ₂ --OH or --CH (C
H ₃₎ cockroach repellent containing as an active ingredient a sesquiterpene alcohol with any one and terminal methylene groups of -CH ₂ OH. 4. The cockroach repellent according to claim 3, wherein the sesquiterpene alcohol is elemol, β-eudesmol or beticerinenol. 5. A cockroach repellent containing vetiver oil or eremi oil as an active ingredient, which comprises at least one of elemol, β-eudesmol and vetiselinenol.