JP2803035B2 - Termite control agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a termite controlling agent containing a plant seed extract as an active ingredient.

[0002]

2. Description of the Related Art Damages on houses and trees caused by termites have been increasing steadily in recent years, and have become a serious economic problem. Conventionally, against such termites, toxic compounds (termiticides (termi
ticide)) or by fumigation with liquid nitrogen. However, the use of this toxic fumigant is a serious environmental problem.

[0003]

SUMMARY OF THE INVENTION The present invention is a naturally occurring feeding inhibitor for termites that can inhibit termite growth and viability by preventing termite feeding when the termites come into contact with them. It is intended to provide a termite controlling agent.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that the ginger plant Af
ramomum melegueta seed extract and ketones isolated from the extract and their synthetic analogs have been found to exhibit an antifeeding effect on termites, and the present invention has been completed based on the findings. . That is, the first of the present invention is:
General formula (1):

[0005]

Embedded image

(In the formula, Aryl represents a phenyl group substituted with at least one selected from the group consisting of a hydroxyl group, a lower alkoxy group and a methylenedioxy group, and R ¹ and R ² represent a hydrogen atom. R ³ represents an alkyl group or an alkenyl group having 5 to 20 carbon atoms which may be substituted with an oxo group or a hydroxyl group, or a phenyl group having a hydroxyl group, a lower alkoxy group and a methylenedioxy group. At least one selected from the group consisting of
Represents a 2-phenylvinyl group substituted by at least one species. ).

In the above formula (1), the lower alkoxy group which is a substituent on the phenyl group means an alkoxy group having 1 to 6 carbon atoms, such as methoxy, ethoxy, propoxy and isopropoxy. Also, R
^The alkyl group or alkenyl group represented by ³ may be substituted with an oxo group or a hydroxyl group, and particularly has 6 to 10 carbon atoms.
Are preferred.

Specific examples of the compound of the present invention represented by the above formula (1) include the following compounds. (1) In the above formula (1), Aryl is 4-hydroxy-3
A methoxyphenyl group, wherein R ¹ and R ² are hydrogen atoms,
A compound in which R ³ is a 2-oxooctyl group, that is, the following formula (3):

[0009]

Embedded image

(Hereinafter referred to as "T11-4A")
That. (2) In the above formula (1), Aryl is 4-hydroxy-3
A methoxyphenyl group, wherein R ¹ and R ² are hydrogen atoms,
A compound in which R ³ is a 2-hydroxyheptyl group, that is, the following formula (4):

[0011]

Embedded image

A compound represented by the following formula (hereinafter referred to as "T11-6A")
That. (3) In the above formula (1), Aryl is 4-hydroxy-3
A methoxyphenyl group, wherein R ¹ and R ² are hydrogen atoms,
A compound in which R ³ is a heptyl group, that is, the following formula (5):

[0013]

Embedded image

A compound represented by the formula (hereinafter referred to as "T11-8A")
That. (4) In the above formula (1), Aryl is 4-hydroxy-3
A methoxyphenyl group, wherein R ¹ and R ² are hydrogen atoms,
A compound in which R ³ is a 1-heptenyl group, that is, the following formula (6):

[0015]

Embedded image

(Hereinafter referred to as "T11-9A")
That. (5) In the above formula (1), Aryl is a 3,4-methylenedioxyphenyl group, R ¹ and R ² together represent a direct bond, and R ³ is 2- (3,4-methylenedioxy). A compound that is an (oxyphenyl) vinyl group, that is, the following formula (7):

[0017]

Embedded image

A compound represented by the formula (hereinafter referred to as "T11-SY
N ". ) Among the compounds of the present invention, T11-4A, T11-6A,
T11-8A and T11-9A can be produced, for example, by extracting the seeds of the ginger plant Aframomum melegueta with a solvent and collecting the compound from the extract. That is, the second aspect of the present invention is the ginger plant Aframo.
The seeds of mum melegueta are extracted with a solvent, and the general formula (1 ′):

[0019]

Embedded image Aryl-CH ₂ CH ₂ CO—R ³ (1 ′) (wherein, Aryl represents a 4-hydroxy-3-methoxyphenyl group, R ³ is a 2-oxooctyl group, 2-hydroxyheptyl) , A heptyl group or a 1-heptenyl group).

The extraction solvent used in the production method of the present invention is not particularly limited, but preferably includes hexane, methanol, acetone, ether, chloroform and ethyl acetate. At the time of extraction, the seeds of the plant can be used as they are, but it is preferable to crush or pulverize them to enhance the contact with the solvent.

The extraction temperature is preferably in the range from room temperature to the boiling point of the solvent under normal pressure. The extraction time varies depending on the extraction temperature and the like, and may be appropriately selected. Separation and purification of the ketones from the extract can be performed by, for example, thin-layer chromatography or column chromatography using silica gel.

Further, among the compounds of the present invention, T11-S
YN and its analogs can also be chemically synthesized.
That is, the third aspect of the present invention is that the general formula (2):

[0023]

Embedded image Aryl-CHO (2)

(Where Aryl represents a phenyl group substituted with at least one selected from the group consisting of a hydroxyl group, a lower alkoxy group and a methylenedioxy group), and an aromatic aldehyde represented by the formula: General formula (1 ″) characterized by reacting:

[0025]

Embedded image Aryl-CH ＝ CH—CO—CH ＝ CH-Aryl (1 ″) This is a method for producing ketones represented by the formula (2), wherein Aryl has the same meaning as in the above formula (2).

The compound of the present invention and the above-mentioned extract exhibit an action of suppressing feeding on termites, and are useful as termite control agents. That is, a fourth aspect of the present invention is a termite controlling agent containing the ketone represented by the formula (1) as an active ingredient, and a fifth aspect of the present invention is a ginger plant Aframomum mele.
It is a termite control agent containing an extract of gueta seed as an active ingredient.

The active ingredients may be used alone or in combination of two or more. These active ingredients can be used as they are, but they are usually diluted with water or a suitable organic solvent, and may be used as a water solvent or an oily agent.Moreover, emulsifiers, penetrants, stabilizers, extenders, A binder, a propellant or the like may be added to use as a dosage form such as emulsion, powder, granule, aerosol and the like.

The concentration of the active ingredient in the preparation and the application rate of the preparation are more appropriately determined according to the dosage form, application method, wood treatment or soil treatment, prevention or control, type of termite, degree of termite damage, and the like. Just choose. The termite controlling agent of the present invention is extremely effective for controlling termites such as Yamato termite and house termite.

The termite control agent of the present invention can be applied to an active ingredient itself or a preparation thereof for a site where a termite is generated or a nest, a base for preventing damage to the termite, a building member such as a pillar, a building, and soil around the same. Coating, spraying, dipping, pouring,
It can be applied by spraying, mixing and the like.

Further, it can be used in combination with other termite control agents depending on the condition of termite generation and damage. Since termite damage usually progresses simultaneously with decay by wood-rot fungi, it is particularly advantageous to use a preservative in combination. In addition, anti-humidifying agents can be used in combination.

The termite controlling agent of the present invention is useful for the prevention and control of termites, but is more suitable for prevention because of its inhibitory effect on termite feeding. Since the active ingredient of the termite control agent of the present invention is a naturally occurring compound or an analog thereof and does not contain harmful heavy metals or halogens, there is no possibility that the termite control agent will accumulate and concentrate in the natural environment.

[0032]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples, but the scope of the present invention is not limited to these Examples.

(Example 1) Preparation of extract Aframomum melegueta (Zingiberaceae) plant collected in the Ogbomosho region of the Federal Republic of Nigeria
32g of seeds were obtained from 85g of dried fruit of the above. The hard seed was ground to a fine powder and extracted first with 100 ml of hexane and finally with 100 ml of methanol. The extracts were combined and the solvent was distilled off to obtain 1.85 g of a irritating pale yellow oil.

Example 2 Separation / Purification of Active Compound Preliminary examination of the crude extract obtained in Example 1 by thin-layer chromatography showed the presence of 4 main compounds and 8 trace compounds. Was. 100 mg of this crude extract was used in solvent system B
Preparative thin layer chromatography using (hexane: ethyl acetate = 8: 2 (v / v)) gave T11-4.
A 17.7 mg, T11-6A 12.5 mg, T11-8A 8.7
mg and T11-9A 8.1 mg. Each compound was further purified by a short silica gel column. These compounds were identified by spectral analysis. The physical properties and the like of the obtained compound are shown below.

(1) T11-4A Property: colorless oil Molecular weight: 292 Molecular formula: C ₁₇ H ₂₄ O ₄ UV: λmax (nm) 369 (4790), 322 (3420), 280 (1)
1280), 248 (6550) IR spectrum: (KBr) cm ^-1 3450, 2950, 1700, 1620, 1520, 1460, 1360, 135
0, 1050, 1260, 1250, 1150, 1110, 1030, 800 (see FIG. 1) ¹ H-NMR spectrum: (270 MHz, CDCl ₃ , ppm
): 0.89 (3H, t, J = 6Hz), 1.25 (6H, m), 2.18 (2H, t, J = 7.5
Hz), 2.55 (1H, d, J = 8Hz), 2.57 (1H, d, J = 8Hz), 2.82 (1H, d, J = 8Hz)
J = 3Hz), 2.88 (1H, d, J = 8Hz), 3.86 (3H, s), 5.44 (1H, bs),
6.62 (1H, d, J = 2 Hz) 6.69 (1 H, dd, J = 2.8 Hz), 6.82 (1H, d, J = 8 Hz) (see FIG. 2) ¹³ C-NMR spectrum: (67 MHz, CDCl ₃ , ppm
): (OFR) 14.01 (q), 22.32 (t), 25.52 (t), 31.01 (t),
38.11 (t), 40.05 (t), 55.65 (q), 99.25 (s), 110.91 (d),
114.08 (d), 120.05 (d), 132.53 (s), 143.38 (s), 193.52
(s), 194.12 (s) (see FIG. 3) Mass spectrum (EI-MS): m / z: 292 (M ⁺ ), 25
9, 248, 233, 205, 191, 137, 119, 95, 77 Color reaction: vanillin sulfate, sulfuric acid (10%), F
eCl ₃ solubility: Dissolve in acetone, ether, ethyl acetate, chloroform and methanol.

(2) T11-6A Property: colorless oil Molecular weight: 294 Molecular formula: C ₁₇ H ₂₆ O ₄ UV: λmax (nm) 282 (3743), 259 (2875) IR spectrum: (KBr) cm ⁻¹ 3450 , 2950, 2890, 1710, 1700, 1690, 1540, 151
0, 1500, 1460, 1360, 1300, 1280, 1260, 1150, 1120,
1040, 800 (see FIG. 4) ¹ H-NMR spectrum: (270 MHz, CDCl ₃ , ppm
): 0.89 (3H, t, J = 6Hz), 1.20-1.59 (8H, m), 2.44 (1H, dd
d, J = 7,9,14Hz), 2.51 (1H, ddd, J = 6,10,14Hz), 2.71 (1H, dd
(dd, J = 4,7,10,14Hz), 2.74 (1H, dddd, J = 6,8,9,14Hz), 2.81
(1H, ddd, J = 8,9,14Hz), 2.86 (1H, dddd, J = 4,7,10,14Hz),
3.87 (3H, s), 6.68 (1H, dd, J = 2.8Hz) 6.71 (1H, d, J = 2Hz), 6.82 (1H, d, J = 8Hz) (see FIG. 5) ¹³ C-NMR spectrum : (67 MHz, CDCl ₃ , ppm
): (OFR) 14.02 (q), 22.59 (t), 22.13 (t), 29.27 (t),
31.72 (t), 36.39 (t), 45.43 (t), 45.9 (t), 48.3 (t), 6
7.64 (d), 110.94 (d), 114.36 (d), 120.72 (d), 132.61
(s), 143.95 (s), 146.42 (s), 211.45 (s) (see FIG. 6) Mass spectrum (EI-MS): m / z: 294 (M ⁺ ), 27
6, 205, 194, 179, 150, 137, 119, 107, 99, 91, 77 Color reaction: vanillin sulfate, sulfuric acid (10%), F
eCl ₃ solubility: Dissolve in acetone, ether, ethyl acetate, chloroform and methanol.

(3) T11-8A Property: colorless oil Molecular weight: 278 Molecular formula: C ₁₇ H ₂₆ O ₃ UV: λmax (nm) 281 (6180), 256 (3850) IR spectrum: (KBr) cm ⁻¹ 3400 , 2950, 2890, 1680, 1610, 1520, 1460, 136
0, 1350, 1260, 1250, 1150, 1030, 800 (see FIG. 7) ¹ H-NMR spectrum: (270 MHz, CDCl ₃ , ppm
): 0.90 (3H, t, J = 6Hz), 1.31 (10H, bs), 2.38 (2H, t, J = 7
Hz), 2.70 (2H, t, J = 7Hz), 2.85 (2H, t, J = 7Hz), 3.86 (3H,
s), 5.40 (1H, bs), 6.68 (1H, dd, J = 2,8Hz), 6.71 (1H, d, J = 2
Hz), 6.82 (1H, d, J = 8 Hz) (see FIG. 8) ¹³ C-NMR spectrum: (67 MHz, CDCl ₃ , ppm
): (OFR) 14.10 (q), 22.90 (t), 28.81 (t), 29.00 (t),
29.98 (t), 31.72 (t), 43.00 (t), 44.61 (t), 56.01 (q),
111.10 (d), 114.17 (d), 120.91 (d), 133.03 (s), 144.12
(s), 146.83 (s), 210.51 (s) (see FIG. 9) Mass spectrum (EI-MS): m / z: 278 (M ⁺ ), 17
9, 151, 137, 119, 107, 91, 77 Color reaction: vanillin sulfate, sulfuric acid (10%), F
eCl ₃ solubility: Dissolve in acetone, ether, ethyl acetate, chloroform and methanol.

(4) T11-9A Property: colorless oil Molecular weight: 276 Molecular formula: C ₁₇ H ₂₄ O ₃ UV: λmax (nm) 369 (2480), 281 (4140), 262 (3)
540) IR spectrum: (KBr) cm ^-1 3400, 2950, 2890, 1710, 1700, 1560, 1540, 150
0, 1460, 1360,1350, 1260, 1250, 1150, 1030, 800
(See FIG. 10) ¹ H-NMR spectrum: (270 MHz, CDCl ₃ , ppm
): 0.88 (3H, t, J = 6Hz), 1.29 (4H, m), 1.45 (2H, m), 2.1
8 (1H, dd, J = 4,7Hz), 2.21 (1H, dd, J = 4,7Hz), 2.86 (4H, t, J =
3.5Hz), 3.86 (3H, s), 5.51 (1H, bs), 6.10 (1H, d, J = 12Hz),
6.68 (1H, dd, J = 2,8Hz), 6.71 (1H, d, J = 2Hz), 6.81 (1H, d, J
= 8 Hz), 6.82 (1H, d, J = 12 Hz) (see FIG. 11) ¹³ C-NMR spectrum: (67 MHz, CDCl ₃ , ppm
): (OFR) 13.93 (q), 22.39 (t), 27.73 (t), 29.83 (t),
31.31 (t), 32.42 (t), 41.94 (t), 55.83 (q), 110.70 (d),
114.27 (d), 120.76 (d), 130.28 (d), 133.21 (s), 143.83
(s), 146.34 (s), 147.89 (d), 199.82 (s), (see FIG. 12) Mass spectrum (EI-MS): m / z: 276 (M ⁺ ), 20
5, 177, 151, 137, 125, 119, 107, 91, 81, 69 Color reaction: vanillin sulfate, sulfuric acid (10%), iodine, FeCl ₃ Solubility: acetone, ether, ethyl acetate, chloroform, methanol Dissolve in

Example 3 Synthesis of T11-SYN 3.75 g of 3,4-methylenedioxybenzaldehyde (purchased from Wako Pure Chemical Industries), 5 ml of a 10% aqueous sodium hydroxide solution,
A mixture of 2.5 ml of acetone was stirred in 50 ml of dimethoxyethane at room temperature overnight. The reaction mixture was diluted with water and extracted with ethyl acetate. The ethyl acetate layer was washed with water, diluted hydrochloric acid (1M) and water, and then dried over anhydrous sodium sulfate. Evaporation of the solvent gave quantitatively T11-SYN, which was recrystallized from ethyl acetate: hexane as yellow flakes.
The structure of T11-SYN was confirmed by analyzing the spectral data.

The physical properties of T11-SYN are shown below. Properties: Yellow crystalline flake Melting point: 198-200 ° C Molecular weight: 322 Molecular formula: C ₁₉ H ₁₄ O ₅ UV: λmax (nm) 479 (2650), 467 (2670), 360 (1
3650), 292 (4310), 262 (7490), 246 (6960) IR spectrum: (KBr) cm ^-1 1640, 1620, 1580, 1550, 1540, 1490, 1380, 131
0, 1260, 1180,1080, 1030, 980, 960, 920, 840, 820
(See FIG. 13) ¹ H-NMR spectrum: (270 MHz, CDCl ₃ , ppm
): 6.00 (4H, s), 6.75-6.85 (3H, m), 6.86 (2H, d, J = 15H
z), 7.05-7.16 (3H, m), 7.65 (2H, d, J = 15 Hz) (see FIG. 14) ¹³ C-NMR spectrum: (67 MHz, CDCl ₃ , ppm
): (OFR) 101.60 (t), 108.58 (d), 108.64 (d), 125.05
(d), 128.31 (s), 128.79 (d), 142.62 (d), 148.39 (s), 14
9.81 (s), 188.51 (s) (see FIG. 15) Mass spectrum (EI-MS): m / z: 322 (M ⁺ ), 20
0, 147, 135, 117, 89, 63 Color reaction: natural light Solubility: Dissolves in acetone, ether, chloroform and methanol.

Test Example 1 Behavior in Thin Layer Chromatography (Rf) The Active Compounds T11-4A, T11-6A, T11-
The behavior of 8A, T11-9A and T11-SYN in TLC was investigated in three separate solvent systems, A, B and C.
These compounds can be used at 254 nm and 365 nm under a UV lamp.
m was detected by observing the plate. Then, the TLC plate was sprayed with vanillin sulfate and heated at 110 ° C. for 5-10 minutes.

The solvent system used is as follows. Solvent system: A Hexane: ethyl acetate: chloroform = 5: 2.5: 2.5
(v / v / v) B Hexane: ethyl acetate = 8: 2 (v / v) C Benzene: ethyl acetate = 9: 1 (v / v)

As the plate, a silica gel plate 60F-254 Merck No. 5715 was used. The results are shown below.

Example 4 Feeding Inhibiting Effect on Termites Termites collected from the vicinity of Yokkaichi City, Mie Prefecture and Kagoshima City, Kagoshima Prefecture, Japan (Reticulitermes sperat)
us) (3 years old or older).

For the sample preparation, pure (more than 99% pure) compounds of the invention are diluted in acetone and the following series of dilutions (the following concentrations are expressed in ppm): 10000/7500/5000 / 2500/1000 was used.

The activity of the sample was determined by using circular filter paper (Whatman No. 1, fine, 2.0 cm in diameter, 0.18 mm in thickness) as a feeding substrate.
Using a selective feeding bioassay
oassay). For each experiment, 30 termite termites were placed in a 55 mm diameter plastic petri dish. The bottom of the dish was covered with a layer of gelified agar (10 g / l) covered with sand (Nacalai Tesque, sand C). In each dish, control circular filter paper treated with solvent only and circular filter paper treated with 25 μl of sample were placed on aluminum foil. The same experiment was performed three times for each dose.

The amounts of the compounds per circular filter paper are as follows. ppm: 10000 7500 5000 2500 1000 μg / filter paper: 250 187.5 125 62.5 25 μg / cm ² : 79.57 59.68 39.78 19.89 7.95 Termites fed the filter paper in the dark at 27 ° C. and 90% humidity for 14 days. Fourteen days later, the termites were removed, and the remaining filter paper was measured to evaluate the suppression of food intake.

The filter paper is a video interface (Hyp
erScanner adaptor A-WOK HSC-II ^R ) via APPLE M
The measurement was performed using a video camera (HITACHI ^R Camcorder VHSC VMS72) connected to an ACINTOSH SE 30 ^R computer. This method uses scanning software (VIDEO M
EDIATOR ^R 1.01 Interware Co. Ltd.). The data is stored in image editing software
tware) (SUPERPAINT ^R 1.1MS Silicon Beach Software In
c.) was used for accumulation. Individual filter paper surface is measured by using a different software (SCALER ^R Hachinohe Firmware System). I chose square dot as the surface unit.

For each set of experiments, an intact filter paper (N =
6) was measured, and an average standard plane was calculated. Then, by referring to this surface, the percentage of the eaten area was calculated. To measure the activity of the extract, Alkofahi et al. (Alkof
ahi A., et al., 1989, ACS Symposium series No.387:
(25-43, American Chemical Society; Washington D.C.)
The feeding inhibition index described by E.

[0050]

(Equation 1)

A value less than 20 indicates an antifeedant activity. A value of 0 indicates that the treated filter paper was not eaten.
Values above 80 indicate a strong feeding stimulating effect. Table 1 shows the Inhibition Index (mean of three replicates (IAVG)) for all doses tested along with their standard deviation (SD).

[0052]

[Table 1]

FIGS. 16-19 show dose response curves for all compounds tested. All compounds were found to exhibit a significant antifeedant effect. The most active compounds were T11-6A and T11-8A. The synthetic analog T11-SYN was also found to be active at a dose of 5000 ppm. A similar test was performed on a 1% acetone solution of the crude extract obtained in Example 1, and a strong antifeeding effect was observed.

[0054]

According to the present invention, it is possible to provide a termite controlling agent which is naturally derived, has high safety, and has a feeding-inhibiting effect on termites.

[Brief description of the drawings]

FIG. 1 is a view showing an IR spectrum of compound T11-4A of the present invention.

FIG. 2 is a chart showing ¹ H-NMR spectrum of compound T11-4A of the present invention.

FIG. 3 shows a ¹³ C-NMR spectrum of compound T11-4A of the present invention.

FIG. 4 is a view showing an IR spectrum of compound T11-6A of the present invention.

FIG. 5 is a chart showing ¹ H-NMR spectrum of compound T11-6A of the present invention.

FIG. 6 is a diagram showing a ¹³ C-NMR spectrum of compound T11-6A of the present invention.

FIG. 7 shows an IR spectrum of compound T11-8A of the present invention.

FIG. 8 shows a ¹ H-NMR spectrum of compound T11-8A of the present invention.

FIG. 9 is a view showing a ¹³ C-NMR spectrum of compound T11-8A of the present invention.

FIG. 10 is a view showing an IR spectrum of compound T11-9A of the present invention.

FIG. 11 shows ¹ H-NMR of compound T11-9A of the present invention.
It is a figure showing a spectrum.

FIG. 12 shows ¹³ C-NMR of compound T11-9A of the present invention.
It is a figure showing a spectrum.

FIG. 13 is a view showing an IR spectrum of compound T11-SYN of the present invention.

FIG. 14 shows ¹ H-NM of compound T11-SYN of the present invention.
It is a figure showing an R spectrum.

FIG. 15 ¹³ C-NM of compound T11-SYN of the present invention
It is a figure showing an R spectrum.

FIG. 16 shows a dose response curve for the compound T11-4A of the present invention.

FIG. 17 shows a dose response curve for compound T11-6A of the present invention.

FIG. 18 shows a dose response curve for the compound T11-8A of the present invention.

FIG. 19 shows a dose response curve for the compound T11-9A of the present invention.

Claims (1)

(57) [Claims] 1. A termite controlling agent comprising, as an active ingredient, an extract of seeds of the ginger plant Aframomum melegueta .