JPH0753309A - Repellent moth-proofing agent for clothes containing amide compound as active ingredient - Google Patents

Abstract

PURPOSE:To provide a safer moth-proofing agent, having low fouling properties for clothes, repellent and inhibiting effects agains damage by moth, having high activities just after starting the use thereof and both the maintenance of potent and the retention of the activities at a low concentration. CONSTITUTION:This repellent moth-proofing agent for clothes contains a monoterpenyl amide compound expressed by the formula (R1 is monoterphenyl which is a residue after removing aldehyde group from a monoterpenylaldehyde selected from among citronellal, 1-p-menthen-9-al, alpha-camphorene-aldehyde and beta-camphorene-aldehyde; R2 and R3 are each H, iso or normal saturated or unsaturated hydrocarbon group, except that both are H) as an active ingredient. When the compound is used with p-dichlorobenzene, naphthalene or camphor which is a conventional insect repellent in combination, defects of the conventional insect repellent (malodor, fouling and toxicity) can be reduced. When the compound is used with empenthrin in combination, the anxiety about potency after starting the use can be eliminated.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an amide compound having excellent repellent effect and food damage inhibiting effect for protecting clothes from damage caused by clothes pests such as squid, koga, scabbard beetle, and beetle scuttle beetle, and in particular, a terpenyl group derived from a natural product. The present invention relates to a repellent clothing insect repellent containing an amide compound.

[0002]

Conventionally, sublimable insect repellents such as paradichlorobenzene, naphthalene and camphor have been widely used as insect repellents for clothing. Originally, these sublimable insect repellents have the main effect of repelling harmful insects and have a peculiar irritating odor, so the transfer of this odor to clothes causes discomfort during wearing. In addition, when these sublimable insect repellents are used inadvertently in the same space, there is a risk of discoloring and contaminating clothes and the inside of a storage device such as a closet. In addition, among these sublimable insect repellents, paradichlorobenzene and naphthalene have recently been regarded as problems in terms of toxicity.

As a means for solving such problems,
In recent years, insect repellents for clothes using empensulin, which is a pyrethroid insecticide that is volatile at room temperature, have been widely used. These pyrethroid insecticides are odorless and have a strong insecticidal effect against clothing pests, but since they are expensive drugs, they can only be used in very small amounts, and because they are liquid at room temperature, they are generally used. Since it is used as a dosage form that is impregnated and held in an impregnated body such as mat or non-woven fabric,
Compared with the above-mentioned sublimable insect repellents, the drug volatility is low, and the space concentration of the drug is not sufficiently increased in the clothes storage device such as a closet. Therefore, there is a drawback in that the insect repellent effect is low, especially after the start of use. . Also, kimonos that are chemically unstable to metals (particularly copper compounds) and that use copper compounds,
Bands, dolls, etc. have the drawback that they may be discolored or contaminated and their use is restricted.

In recent years, DEET (N, N-diethyl-m) has been used as a repellent against sanitary insects such as mosquitoes and cockroaches.
-Toluamide) is commercially available and widely used. However, the target pest species of DEET is limited in efficacy, and it has a low repellent effect against clothing pests such as squid, koga, scabbard beetle, and stag beetle, and has a short residual effect. I didn't get it. Therefore, in recent years, attention has been paid to the use of bioactive natural substances having a repellent action widely distributed in nature as insect repellents. The conditions under which these bioactive natural products are expected to be established as repellent substances are preferably (1) there is no restriction on the application site, (2) extremely low toxicity to humans and animals, and (3) shelf life. Is long,
And (4) small amount is effective.

Therefore, an object of the present invention is to be safer, to be less polluting to clothing, and to sublimate insects against clothing pests (paradichlorobenzene, naphthalene,
(Camphor etc.), Empensulin, and DEET to find physiologically active compounds having a high activity repellent effect or a food damage inhibitory effect. Further, the object of the present invention is to provide an insect repellent insect repellent having a repellent effect and a food damage inhibitory effect, which has a rapid onset of the effect immediately after the start of use, and a sustained effect persistence and an activity retention at a low concentration. Especially.

[0006]

Means and Actions for Solving the Problems The present inventors have
As a result of earnest research on physiologically active compounds, the following chemical formula 3

[Chemical 3] (In the formula, R ₁ is citronellal, 1-p-menthene-9
-A monoterpenyl group which is a residue excluding the aldehyde group of a monoterpenyl aldehyde selected from the group consisting of are, α-camphorene aldehyde and β-camphorene aldehyde, R ₂ and R ₃ are H and 1 carbon atoms. An iso- or normal saturated or unsaturated hydrocarbon group of 6 to 6 (provided that R ₂ and R ₃ are both H). ) The amide compound represented by the general formula (1) has a high activity of paradichlorobenzene, naphthalene, camphor and DEET or more, a repellent effect against clothing pests and a food damage inhibition effect, and is highly volatile, The present inventors have found that the activity-sustaining effect is high and have completed the present invention.

Among the amide compounds of the above general formula (1), amide compounds in which R ₂ and R ₃ are both a methyl group, an ethyl group or a propyl group are excellent in repellent effect and food damage inhibiting effect even at low concentration. It is advantageous because it has a high activity sustaining effect. Regarding the relationship between the basic skeleton of the compound and the persistence of repellent effect and feeding damage inhibiting effect, among terpenoids, those showing repellency to mosquitoes and cockroaches include menthol, citronellal, terpene alcohols such as linalool, or aldehydes, This time, by converting these compounds into compounds having an amide group, the activity against clothing pests and its persistence could be increased. However, among the terpenylamide compounds, the repellent activity, the food damage inhibition activity, and their persistence were found to be different depending on the terpene skeleton.

The pests on which the amide compound of the present invention effectively acts include, for example, squid, koga, beetle beetle, beetle beetle, beetle deer, beetle, and beetle beetle beetle. The amide compound of the present invention is suitable as an active ingredient. It can be used as a repellent clothing insect repellent by incorporating it into any other carrier such as paper, non-woven fabric, wood chips, silica gel, zeolite, sublimable solids, and plastics. Further, the amide compound of the present invention, if desired, a film forming agent, a moisturizer, a pH adjuster, a rust preventive agent, an emulsifier, a dispersant, a spreading agent, a stabilizer, a solvent,
Addition of antioxidants, propellants, volatilization regulators, gelling agents, etc., oils, emulsions, wettable powders, sprays, aerosols, smoke agents, coatings, electric vaporizers, powders, granules, It can be used in the form of a gel or the like.

Further, the amide compound of the present invention having a strong activity against repellent effect and food damage inhibitory effect is used in combination with a conventional insect repellent such as paradichlorobenzene, naphthalene, camphor, etc. By providing the agent, odor, pollution, which are the drawbacks of conventional insect repellents,
The toxicity problem can be reduced. Further, the amide compound of the present invention having a rapid repellent effect is used in combination with a pyrethroid-type room temperature volatile insect repellent (particularly empensulin) to provide a repellent clothing insect repellent in the above-mentioned form, thereby providing a pyrethroid insect repellent. It is possible to eliminate the anxiety of efficacy immediately after use, which is a drawback of the agent,
It is possible to further enhance the repellent activity against food pests and the food damage inhibition activity, and their persistence. In addition, since the odor of the amide compound of the present invention has a peculiar refreshing odor, there is no trouble such as attachment of a strange odor to clothes and the like, and thus it has excellent properties applicable to a wide range of places of use. However, unlike the odorless pyrethroid insect repellent, it also has the advantage of being able to confirm the persistence of the drug by the strength of the scent, that is, the sense of smell.

Hereinafter, the present invention will be described more specifically by showing a method for synthesizing the amide compound of the present invention and various potency tests. Synthetic method: First, a general synthetic method of the amide compound according to the present invention will be outlined. Monoterpenyl nitriles prepared from a starting material monoterpenyl aldehyde or camphor oxime are hydrolyzed to form a carboxylic acid. It is synthesized and the acid chloride is induced by chloridation. Then, the target monoterpenylamide compound is synthesized by a condensation reaction of the acid chloride with an alkylamine or a dialkylamine. The amide compound according to the present invention is not limited to those synthesized according to the above reaction route, and those synthesized according to other possible reaction routes are also within the scope of the present invention, and the reaction conditions and the like are also known to those skilled in the art. If so, an appropriate condition can be set by conducting a test.

As a representative example, FIG. 1 shows an overall reaction route diagram for the synthesis of the amide compound shown below. (1) Citronellyl amide represented by the following chemical formula 4

[Chemical 4] Compound A: R ₂ , R ₃ = CH ₃ Compound B: R ₂ , R ₃ = C ₂ H ₅ Compound C: R ₂ , R ₃ = C ₃ H ₇

(2) 1-p-menthene-9-amide represented by the following chemical formula 5

[Chemical 5] Compound D: R ₂ , R ₃ = CH ₃ Compound E: R ₂ , R ₃ = C ₂ H ₅ Compound F: R ₂ , R ₃ = C ₃ H ₇

(3) α-camphorenamide represented by the following chemical formula 6

[Chemical 6] Compound G: R ₂ , R ₃ = CH ₃ Compound H: R ₂ , R ₃ = C ₂ H ₅ Compound I: R ₂ , R ₃ = C ₃ H ₇

(4) β-camphorenamide represented by the following chemical formula 7

[Chemical 7] Compound J: R ₂ , R ₃ = CH ₃ Compound K: R ₂ , R ₃ = C ₂ H ₅ Compound L: R ₂ , R ₃ = C ₃ H ₇

Referring to FIG. 1, monoterpenyl nitriles [1b] (-)-3,7-dimethyl-2-octene nitrile (abbreviated as citronellyl nitrile) and [2].
b] (+)-1-p-menthene-9-nitrile is the corresponding aldehyde derivative [1a] citronellal and [2a] 1-p-menthen-9-al in β-form of dimethylhydrazine and methyl iodide. It can be easily synthesized by nitriding by elimination reaction and hydrolysis. On the other hand, [3b] α-camphorene nitrile and [4b] β
-Camphorene nitrile can be easily synthesized by treating camphor oxime obtained by reacting d-camphor with hydroxylamine in pyridine with 25% sulfuric acid (or formic acid) and concentrated hydrochloric acid, respectively.

The four kinds of terpenyl nitriles [1b] to [4b] thus obtained are hydrolyzed using a KOH-methanol solution, and the corresponding carboxylic acid [1c] (+)-is obtained. 3,7-Dimethyl-2-octenoic acid, [2c] (+)-1-p-menthen-9-yl = acetic acid, [3c] (+)-α-camphorenic acid and [4c].
Induces to β-camphorenic acid. The synthesized respective carboxylic acid performs chloride by thionyl chloride, after an acid chloride thereof rich in reactivity, each alkyl amine or dialkyl amines _{(R = -CH 3, -C 2} H
₅ performs a condensation reaction with the -C ₃ H _7), respectively led to the corresponding condensation product A to L. Regarding the chemical structures of these products, IR and ¹ H-NMR spectra were measured, and they were confirmed from the characteristic spectral data obtained. The R ₁ groups [1] to [4] shown in FIG. 1 correspond to the amide compounds (1) to (4) described above, and are referred to in the present specification as terpenyl groups (terpenyl as a starting material). It means a residue obtained by removing an aldehyde group from an aldehyde).

[0017]

EXAMPLES Hereinafter, specific synthesis examples of the amide compound will be shown. Synthesis of monoterpenyl nitriles [1b] to [4b]: Synthesis of [1b] (-)-3,7-dimethyl-2-octenenitrile: 0.2 mol of citronellal and 0.2 of N, N-dimethylhydrazine. 30 mole of a mixture of dry benzene
After dissolving in 0 ml, the mixture was heated to reflux until the theoretical amount of water was obtained. After cooling the reaction solution, 0.2 mol of methyl iodide was added and the mixture was heated under reflux for 4 hours. Then 0.1 M NaOH
-200 ml of methanol solution was added for hydrolysis. After completion of the reaction, the reaction mixture was operated according to a conventional method and distilled under reduced pressure to obtain (-)-3,7-dimethyl-2-octenenitrile in a yield of 80%. The structure of the product was confirmed by an infrared absorption spectrum (manufactured by JASCO Corporation, IR-810 type) and a nuclear magnetic resonance spectrum (manufactured by JEOL Ltd., JNM-MH-100), and the purity of the compound was confirmed. Is a gas chromatography (Yanaco Co., Ltd., G-
3800, OV-17, glass column φ3 mm x 2.5
m) (same for the following products). As a result, the boiling point is 60 to 63 ° C./5 mmHg, the refractive index n _D ²⁰ = 1.4490, and the density d ₄ ²⁰ = 0.856.
0, the specific rotation [α] _W ²⁰ = −7.7 ° (stock solution). The refractive index and the specific optical rotation were measured using an Abbe refractometer 2T type manufactured by Atago Co., Ltd. and an AA-5 type optical rotation meter manufactured by Atago Co., Ltd., respectively.

[2b] (+)-1-p-menthene-9-
Synthesis of nitrile: (+)-1-p-menthene-9-nitrile was obtained in a yield of 7 by the same operation as the nitration reaction of [1b] except that 1-p-menthene-9-ar was used.
Obtained at 1%. The boiling point of the obtained compound is 116 to 118 ° C.
/ 10 mmHg, refractive index n _D ²⁰ = 1.5021, density d
₄ ²⁰ = 1.0124, specific optical rotation [α] _W ²⁰ = + 108.
It was 6 ° (stock solution).

Synthesis of [3b] (+)-α-camphorenenitrile: 1M NaO per 100 g of (+)-camphor.
200 g of hydroxylamine hydrochloride in 1000 ml of H-ethanol solution was reacted at 100 ° C. for 24 hours (+).
-Camphor oxime was obtained in a yield of 92%, which was then treated with 300 ml of 25% sulfuric acid at 100 ° C for 30 minutes to obtain α-camphorene nitrile in a yield of 95%.
The obtained compound has a boiling point of 51 to 52 ° C./1 mmHg, a refractive index n _D ²⁰ = 1.4674, a density d ₄ ²⁰ = 0.855.
2. Specific rotation [α] _W ²⁰ = + 4.8 ° (stock solution).

[4b] Synthesis of β-camphorene nitrile: β-camphorene was prepared by the same procedure as the oximation reaction and nitration reaction of [3b] above except that 200 ml of concentrated hydrochloric acid was used instead of 25% sulfuric acid. Yield of nitrile 85
Earned in%. The boiling point of the obtained compound is 80 to 82 ° C / 5m.
mHg, refractive index n _D ²⁰ = 1.4672, density d ₄ ²⁰ =
It was 0.8211.

Monoterpenylcarboxylic acid [1c] to [4]
Synthesis of c]: Synthesis of [1c] (+)-3,7-dimethyl-2-octenoic acid: 300 m equipped with stirrer, reflux condenser, dropping funnel
In a 1-liter four-necked flask, (-)-3,7- of the above [1b].
Take a mixed solution of 10 g (0.066 mol) of dimethyl-2-octenenitrile and 70 ml of methanol, and add 0.4M
After adding 100 ml of KOH-methanol solution, 20
Heated to reflux for hours. After the completion of the reaction, the operation was carried out in the usual manner, and then distillation was carried out under reduced pressure to obtain (+)-3,7-dimethyl-2-octenoic acid in a yield of 89%. The obtained compound has a boiling point of 91 to 92 ° C./2 mmHg and a refractive index n _D ²⁰ = 1.465.
1, density d ₄ ²⁰ = 0.9308, specific rotation [α] _W ²⁰ =
It was + 5.5 ° (stock solution).

[2c] (+)-1-p-Menten-9-
Synthesis of yl = acetic acid: (+)-1-p-menthen-9-yl = acetic acid was collected from (+)-1-p-menthen-9-nitrile by the same operation as the hydrolysis reaction of the above [1c]. It was obtained at a rate of 78%. The boiling point of the obtained compound is 81 to 83 ° C /
4 mmHg, refractive index n _D ²⁰ = 1.4814, density d ₄ ²⁰
= 0.9164, specific rotation [α] _W ²⁰ = + 86 ° (stock solution).

Synthesis of [3c] (+)-α-camphorene acid: From (+)-α-camphorene nitrile, the above [1]
By the same operation as in the hydrolysis reaction of c], (+)-α-camphorenic acid was obtained with a yield of 80%. The boiling point of the obtained compound was 96 ° C./3 mmHg, and the refractive index n _D ²⁰ = 1.470.
1, density d ₄ ²⁰ = 0.8980, specific rotation [α] _W ²⁰ =
It was + 10.0 ° (stock solution).

Synthesis of [4c] β-camphorenic acid: β-
By the same operation as the above-mentioned hydrolysis reaction of [1c] from camphorene nitrile, β-camphorenic acid was obtained with a yield of 82%. The boiling point of the obtained compound is 160 ° C / 11 mmH.
g, refractive index n _D ²⁰ = 1.4712, density d ₄ ²⁰ = 1.0
It was 156.

Synthesis of Monoterpenylamide Compounds A to L: Synthesis of Citronellylamide: (1) Compound A: (+)-3 in a 50 ml four-necked flask equipped with stirrer, calcium chloride tube and dropping funnel. , 7
-Dimethyl-2-octenoic acid 1.0 g (0.006 mol) and HPMA (hexamethylphosphor (tolu) amide (amide solvent) 0.3 ml) were taken, and thionyl chloride was adjusted to 0. After dropping 86 g (0.007 mol), the mixture was stirred for 0.5 hours, thionyl chloride was distilled off under reduced pressure, 1.0 ml of 33% dimethylamine aqueous solution was added dropwise, and the mixture was stirred at room temperature for 1.5 hours. After the reaction,
The crude reaction oil obtained by the usual operation was distilled under reduced pressure to obtain (-)-N, N-dimethyl-3,7-dimethyl-6-
Octaenamide was obtained in a yield of 63%.

(2) Compound B: (-)-N, N- by the same procedure as the condensation reaction of (1) above except that 1 mL of 44% diethylamine aqueous solution was used in place of dimethylamine.
Diethyl-3,7-dimethyl-6-octaenamide was obtained in a yield of 72%. (3) Compound C: (-)-N, N- by the same operation as the condensation reaction of (1) above except that 1 mL of dipropylamine and triethylamine were used instead of dimethylamine.
Dipropyl-3,7-dimethyl-6-octaenamide was obtained with a yield of 85%.

Synthesis of 1-p-Menten-9-amide: Compounds D, E and F: (+)-3,7-dimethyl-2-
Instead of octenoic acid, the starting material was (+)-1-p-
(1) except that menten-9-yl = acetic acid is used,
By the same operation as the condensation reaction of (2) and (3), the corresponding N, N-dimethylamide compound D, N, N-
Diethylamide compound E and N, N-dipropylamide compound F were obtained.

Synthesis of α-camphorenamide: Compounds G, H and I: (+)-3,7-dimethyl-2-
By the same operation as the condensation reaction of the above (1), (2) and (3), except that (+)-α-camphorenic acid was used as a starting material instead of octenoic acid, the corresponding N, N-dimethylamide was obtained. Compound G, N, N-diethylamide compound H and N, N-dipropylamide compound I were obtained.

Synthesis of β-camphorenamide: Compounds J, K and L: (+)-3,7-dimethyl-2-
By the same operation as the condensation reaction of the above (1), (2) and (3) except that β-camphorenic acid was used as a starting material instead of octenoic acid, the corresponding N, N-dimethylamide compounds J and N were respectively obtained. , N-diethylamide compound K
And N, N-dipropylamide compound L were obtained. Table 1 shows the physical constants and yields of the 12 kinds of monoterpenylamide compounds obtained by the above operation, and Table 2 shows the spectrum data.

[Table 1]

[0030]

[Table 2] Compounds A to L have an IR spectrum of 16
Absorption of carbonyl around 25 to 1650 cm ^-1 , ¹ H
Trisubstituted olefin protons at -NMR spectrum, methylene derived from the third amide, structure was confirmed by distinctive absorption such as methyl protons, allyl methyl and gem-CH _3.

Below, several examples of preparation examples for various dosage forms using the above compounds will be shown.

Example 2 (matting agent) -matte (6 cm ×)
10 cm × 1.5 mm) In 1 sheet Inventive compound E 400 mg Solvent 100 mg BHT 20 mg Dye Trace amount

Example 3 (tablet) Inventive compound E 300 mg anhydrous calcium hydrogen phosphate 5.0 g BHT 20 mg

Example 4 (gel agent) Compound of the present invention H 500 mg Solvent 10 g Gelling agent (metal soap) 300 mg BHT 20 mg

Example 5 (Sheet formulation) Compound H of the present invention 300 mg Empensulin 100 mg Solvent 100 mg BHT 20 mg

Next, various efficacy tests were carried out on the above-mentioned monoterpenylamide compound with respect to the repellent effect and the food damage inhibiting effect. The results are shown below.

Test Example 1 Compounds B (citronellyl amide), E (1-p-menthene-9-amide), H (α-camphorenamide) were used against larvae of the squid (medium-aged) and Pseudomonas aeruginosa. ,
And K (β-camphorenamide) (both N, N-
Diethylamide compounds), and the repellent effect of paradichlorobenzene, camphor, DEET, and empensulin were tested. In addition, the additive repellent effect of the combination of the compound E with paradichlorobenzene, camphor or DEET was also tested. The test method is as follows.

Test method: As shown in FIG.
A filter paper (diameter 9 cm, Toyo Filter Paper No. 5A) is laid inside, and 0.5 ml of an acetone solution diluted with a prescribed concentration of the test sample is applied to the treatment area A so that the chemical treatment amount is 2.0 g / m ^2. And air dry. Then, the induction bait 2 (wool muslin cloth with yeast 2.5 × 2.5 cm) is set on the treated area A, and 10 test insects are released in the petri dish 1. After that, the number of test insects collected on the treated area A was measured over time, and the repellent rate was calculated according to the following formula. As for empensulin, when tested with a drug treatment amount of 2.0 g / m ² , the insecticidal effect is high and the test cannot be conducted.
The test was carried out at m ² . In addition, in the combination example, the respective chemicals were mixed at a ratio of 5: 5, and the same treatment was performed so that the total chemical treatment amount on the treatment area was 2.0 g / m ^2, and the test was conducted. In addition, the blank was tested in the same manner by using only the treated area coated with acetone. The above test was repeated 3 times in a constant temperature room at 22 ° C. (If the repellency rate is negative, the repellency rate is 0.)

The test results are shown in Tables 3 and 4 below.

[Table 3]

[0040]

[Table 4] As is clear from the test results shown in Tables 3 and 4,
It can be seen that the monoterpenylamide compound of the present invention is extremely excellent in activity and durability as a repellent, as compared with paradichlorobenzene, camphor, DEET, and empensulin. Furthermore, the monoterpenyl amide compound of the present invention and paradichlorobenzene, camphor, or DEET
It can be seen that the combination of and shows a repellent effect superior to the case where paradichlorobenzene, camphor and DEET are used alone.

Test Example 2 Larvae of squid (middle-aged) and larvae of Pseudococcidae (middle-aged)
In contrast, the compounds B (citronellyl amide), E
(1-p-menthene-9-amide), H (α-camphorenamide), and K (β-camphorenamide) (all are N, N-diethylamide compounds), paradichlorobenzene, camphor, and The food damage inhibition effect of DEET was tested. Further, the additive feeding inhibition effect of the combination of the compound K with paradichlorobenzene, camphor or DEET was also tested. The test method is as follows.

Test method: Wool muslin cloth (5 ×) on the bottom of a polypropylene (PP) cup (volume: 135 cm ³ ).
5 cm) and spread 10 test larvae therein. Then, 0.5 ml of an acetone solution obtained by diluting the test sample to a predetermined concentration so that the drug treatment amount is 4.0 g / m ² has a diameter of 7 cm.
Oriental filter paper No. 5A is applied and air-dried, and placed on the inner surface of the upper lid of the cup, and the lid is closed. Then, on the 10th day after the start of the test, the damage amount of the wool muslin cloth was measured, and the damage inhibition rate was calculated according to the following formula. In addition, in the combination example, the respective chemicals were mixed at a ratio of 5: 5, and treated in the same manner so that the total chemical treatment amount on the filter paper was 4.0 g / m ² . The blank was similarly tested using a filter paper coated with only acetone. The above test is 22 ℃
This was repeated 3 times in a thermostatic chamber.

The test results are shown in Table 5 below.

[Table 5] As is clear from the test results shown in Table 5, the monoterpenylamide compound of the present invention has an extremely excellent feeding-damage-inhibiting effect on larvae of squid and Pleurotus cornucopiae when compared with paradichlorobenzene, camphor and DEET. You can see that it has. Further, it can be seen that the combination of the monoterpenylamide compound of the present invention and paradichlorobenzene, camphor, or DEET exhibits a superior feeding inhibition effect as compared to the case where paradichlorobenzene, camphor, and DEET are used alone. .

Test Example 3 Inhibitory effect of insect repellent against larvae of squid (medium age) when a repellent insect repellent comprising a combination of the compound B (citronellylamide) and a room temperature volatile insect repellent (empensulin) was prepared. Was confirmed by a quasi-field test using the following method.

Test Method A certain amount of flannel cloth (about 200
g) and a sheet-shaped insect repellent (60 × 30 cm) coated and prepared according to the formulation shown in Table 6 below. After that, over time (0.5 to 1.0 months, 1.5 to 2.0 months, 2.
5-3.0 months, 4.0-4.5 months, and 5.5
A wire mesh ball containing 5 test insects and a wool muslin cloth (5 x 5 cm) is placed in the costume case at ~ 6.0 months. Two weeks after the installation, the wire netting balls were taken out, the amount of food damage was measured, and the food damage inhibition rate was calculated according to the following formula. In addition, blanking was performed in the same manner using a costume case that did not contain the insect repellent to be tested. The above test was repeated 3 times in a constant temperature room at 22 ° C.

[Table 6]

The test results are shown in Table 7 below.

[Table 7] As is clear from the test results shown in Table 7, the repellent property comprising a combination of the compound B of the present invention having a fast repellent effect and a pyrethroid insect repellent (empensulin), which is pointed out to have a poor onset of efficacy. It can be seen that by using the insect repellent, a stable food damage inhibiting effect can be obtained for a long period from immediately after the start of the test until the end thereof.

[0047]

INDUSTRIAL APPLICABILITY As described above, the terpenylamide compound according to the present invention is a paradichlorobenzene mainly having a repellent effect which has been widely commercially available from the past against clothing pests.
It has a repellent effect and a food damage inhibition effect superior to those of sublimable insect repellents such as naphthalene and camphor, and DEET which is widely used as a repellent for sanitary pests. Therefore, by using the terpenylamide compound according to the present invention as an active ingredient of a repellent clothing insect repellent, moth, koga,
It exerts an excellent repellent effect and a food damage-preventing effect immediately after the start of use against clothing pests such as Pleurotus cornucopiae and Pseudococculis similis. Further, by using the amide compound of the present invention in combination with a conventional insect repellent such as paradichlorobenzene, naphthalene, camphor and the like, and a room temperature volatile insect repellent such as a pyrethroid insect repellent (particularly empensulin), the conventional insect repellent has the disadvantages. It is possible to eliminate some odors, pollution, toxicity problems, and anxiety about the efficacy immediately after the start of use, and to further enhance the repellent activity against food pests, the food damage inhibition activity, and their persistence.

[Brief description of drawings]

1 is an overall reaction scheme for synthesizing the amide compound of the present invention.

FIG. 2 is a schematic configuration diagram showing a test device used in a test example.

Claims (5)

[Claims] 1. The following chemical formula 1 (In the formula, R ₁ is citronellal, 1-p-menthene-9
-A monoterpenyl group which is a residue excluding the aldehyde group of a monoterpenyl aldehyde selected from the group consisting of are, α-camphorene aldehyde and β-camphorene aldehyde, R ₂ and R ₃ are H and 1 carbon atoms. An iso- or normal saturated or unsaturated hydrocarbon group of 6 to 6 (provided that R ₂ and R ₃ are both H). ) A repellent clothing insect repellent comprising an amide compound represented by the general formula (1) as an active ingredient. 2. The amide compound is an amide compound in which R ₂ and R ₃ in the general formula are both a methyl group, an ethyl group or a propyl group.
A repellent clothing insect repellent as described in. 3. The following chemical formula 2 (In the formula, R ₁ is citronellal, 1-p-menthene-9
-A monoterpenyl group which is a residue excluding the aldehyde group of a monoterpenyl aldehyde selected from the group consisting of are, α-camphorene aldehyde and β-camphorene aldehyde, R ₂ and R ₃ are H and 1 carbon atoms. An iso- or normal saturated or unsaturated hydrocarbon group of 6 to 6 (provided that R ₂ and R ₃ are both H). ) A repellent insect repellent for clothing, which comprises a combination of an amide compound represented by the general formula (1) and a room temperature volatile insect repellent. 4. The amide compound according to claim 3, wherein R ₂ and R ₃ in the general formula are both a methyl group, an ethyl group or a propyl group.
A repellent clothing insect repellent as described in. 5. The repellent property according to claim 3, wherein the room temperature volatile insect repellent comprises at least one drug selected from the group consisting of camphor, paradichlorobenzene, naphthalene and empensulin. Insect repellent for clothing.