A method for killing insects by heating fumigation

Epigraph: Proc. for the preparation of wicks for the extermination of in: -classes by heating, containing C-methyl-4-oxo-4- (2-propynyl) -cyclopent-2-enyl chromosome

INVENTORS: Sliinobu Yamairoto, Kunihiro Oiled, .íáatoshi Ohi,

Shiro Oy.onia and YasuJiaru Takei.

Claim of right, priority under Article 42 of the Paric Union Convention of 20 March 1003.

Japan submitted on 18 July 1980, under the number

168.120/86.

<img file="PT85348B_D0001.tif" />

<img file="PT85348B_D0002.tif" />

<img file="PT85348B_D0003.tif" />

Patent Specification of SUMITOMO CHEMICAL COMPANY, LIMITEI), Japanese, Industrial and Commercial, headquartered in Kitahama-5-chome, Higashi-ku, Osaka, Japan (inventors: Shinobu Yamamoto, Kunihiro okada, Satoshi Ohi, Shiro Oyama and Yasuharu Takei, residing in Japan), FOR PROCESS FOR PREPARATION OF ARMS TO EXTERMINE HEATING FUMIGATION INSECTS CONTAINING 2-METHYL-4-OXO-3- (2-PRQPINYL) -CYCLOPENT- 2-ENILO.

DESCRIPTIVE MEMORY; The present invention relates to a method of

A method for the extermination of insects by heat fumigation, and more particularly, relates to a method for the extermination of insects by heat fumigation such that a portion of an absorbent porous swab is immersed in an insecticidal solution to allow absorption of the solution, and indirectly heated at the tip to fumigate the absorbed insecticide solution.

The electric fumigant is typically known as a method for the extermination of insects by heat fumigation, but has as its shortcomings that the amount of insecticides that can be impregnated into the plate is limited.

PAN

<img file="PT85348B_D0004.tif" />

It is therefore essential to replace the depleted plate with a new one, that the effective vaporization percentage of the impregnated insecticides is relatively low, and that it is difficult to maintain a stable insecticidal effect over a long period of time.

As a method capable of obviating these, a method for extermination has been known for a long time to exterminate a wick by heating fumigation in such a way.

The absorbent is partly immersed in an insecticidal solution to allow it to absorb the solution, and heated at the tip to fumigate the absorbed insecticidal solution. For example, a form of direct heating is referred to in Japanese Utility, patent publication N · 25081/1968, but in this case the decomposition¹Chemical activity is so violent that it is generally tended to employ indirect heating. As indirect heating forms, there are felt heating methods, etc. between the absorbent wick and the heater (Japanese Utility patent Publication Ns. 124-59 / 1961 and 22585/1971), and a method of heating with a defined distance between the absorbent wick and the heater (Japanese Patent Publication No. 26274/1968, 8361/1969, 14913/1970, 19801/1970, and 29244/1870 and japanese patent Application Kokai (open for public inspection) No. 57502/1980.

In the heat-fumigation method for which indirect heating, the porous wick absorbs the insecticidal solution at a rate that is generally made of cloth felt so that as the absorbed wick is heated, only the sun will come into solution. Insecticide vaporizes and sufficient vaporization of the insecticide solution becomes difficult. Also, the absorbent wick easily begins to clog due to the bubbling of substances formed by thermal decomposition of the chemicals contained in the solvent, so that it is difficult to maintain a high insecticidal effect over a long period of time.

In addition Japanese Patent Publication 23163/1986 proposes a method where allethrin or its isomers are used as an insecticide. An above insecticidal solution is used as an insecticidal solution in an insecusive extermination hydroxy solvent to the foregoing relatively high anterior absorbent form by glass, asbestos, etc, /. _ _ 9 -

<img file="PT85348B_D0005.tif" />

| carbide having a particular boiling point extent, | an absorbent porous wick being used is an absorbent wick selected from the group consisting of porous porcelains, which are prepared by making a cake of inorganic fibers with plaster and / or bentonite, which fibers are selected from glass and asbestos fibers, which are prepared by making a cake of

I; powdered inorganic substances with starch, substances selected from kaolin, talc, diatomaceous earth, perlite, bentonite, alumina, silica, alumina, asbestos; and the absorbent porous wick is heated on the upper side face to a relatively high temperature of 130 to 140 ° C. However in the case of heating to said relatively high temperature, problems arise because thermal decomposition and chemical polymerization become violent by lowering the vaporization percentage of the active ingredient, and also by the bubbling of substances formed by thermal decomposition and polymerization accumulating in the environment. absorbent wick facilitating&gt;&gt; obstruction of the wick.

¹ Accordingly, it is an object of the present invention to provide a safe and successive capillary action on the active ingredient through the absorbent wick (suction capillary method) for the extermination of insects by heat fumigation which may obviate the preceding ones. disadvantages, it does not cause much blocking of the absorbent wick, and can still effectively fumigate a sufficient amount of insecticide over a long period of time. ! 0 method for killing insec | The heat fumigation devices of the present invention is a method where, as described above, an absorbent porous swab is immersed in an insecticidal solution to allow it to be absorbed from the solution and indirectly heated on top to fumigate the absorbed insecticidal solution. characterized by, a C12-C18 saturated aliphatic hydrocarbon solution containing as an active ingredient 2-methyl-4-oxo-3- (2-propynyl) cyclopent-2-enyl chromatemate (hereinafter referred to as active ingredient compound) to be used as an insecticidal solution , and that the absorbent porous swab is prepared by making a cake of pulverulent inorganic substances with an agent

<img file="PT85348B_D0006.tif" />

<img file="PT85348B_D0007.tif" />

Binding is indirectly heated at the top to a temperature between 105 to 130 ° C, preferably 110 to 125 ° C.

Applicants, in the capillary suction method for heat fumigation insect extermination as described above, have found that using an absorbent porous strand prepared by making a cake of pulverulent inorganic substances with a binder like porous strand and a hydrocarbon solution aliphatic C12-C18 containing as an insecticidal solution the preceding active ingredient, which active ingredient compound, which may be sprayed at a temperature between 105 to 150 ° C in an amount sufficient to effect insecticidal activity, and furthermore that there is a small thermal decomposition of the insecticidal component with a high percentage of effective evaporation and that an effective and stable insecticidal effect may be present. be kept for a long time.

In order to facilitate understanding of the present invention a vertical sectional drawing will be shown illustrating an embodiment of the apparatus suitable for the procedure according to the present invention. Referring to the drawing, 1 is the container containing an insecticidal solution 2 which is adjustable and unreasonably contained and provided in container 3. Container 3 is opened at the top, and a circular heater (or a pair of semi-circular heaters) 4. It is fixed in the open part. 5th θ a rope connected to the heater 4. Container 1 has an inlet 6 for loading the insecticidal solution, and an absorbent porous wick 7 is almost always hermetically sealed within inlet 6 so that the top of the wick 7 is located at the center of the circular heater 4. The figure shown is an example of the apparatus necessary for the procedure according to the present invention, but other forms of apparatus may also be used without being limited to this example.

According to the present invention, a C12-C18 saturated aliphatic hydrocarbon solution containing the preceding active ingredient compound is used as an insecticidal solution. Which active ingredient compound has geometric isomers. According to the present invention these isómeΛ

<img file="PT85348B_D0008.tif" />

Rosins and mixtures thereof may also be used as an active ingredient. Saturated aliphatic hydrocarbons have an aggressive odor, so they are not desirable as solvents for the insecticidal solution of the present invention, but have no imortortance if they are contained in the preceding saturated aliphatic hydrocarbon solution so that their amount is such Do not cause aggressive odors. Of saturated aliphatic hydrocarbons those having 19 or more carbon atoms have a high viscosity or take on a gel or solid state, so that no light absorption of the insecticidal solution by the absorbent wick will occur. Consequently the number of carbon atoms needs to be less than or equal to 18. On the other hand, as will be deduced from the examples described later,

<img file="PT85348B_D0009.tif" />

the effective percentage of vaporization of the active ingredient compound tends to decrease with decreasing carbon atoms by ₍such that the number of carbon atoms needs to be less than or equal to 12 in order to ensure a sufficient percentage of vaporization. Of course, it does not matter if the hydrocarbons (aliphatic out of the above range are contained, as long as their amount in such range does not cause these problems.

The saturated aliphatic hydrocarbon solution used in the present invention includes dodecane (C12), triidecane (C13), tetradecane (C14), pentadecane (015), hexadecane (C16), heptadecane (017), octadecane (C18), and mixtures thereof. . • Commercially available solvents containing these hydrocarbons as a major component may also be used, and include N. Solvent H (produced by Nippon Oil Co. Ltd.), N. 0 Solvent M (produced by Nippon Oil Co. Ltd.), (produced by Sanseky, Texaco Chemioal Co.), Deotomizole Al (produced by Yoshitomi Pharmaceutical Industries, Ltd., IP Solvent 2028 (produced by idemitsu Petrochemical Co.), etc.

The concentration of the active ingredient compound in the insecticidal solution, as apparent from the comparison of the percent spraying described later, will preferably be by weight from 0.5 to 5%.

The concentration of the active ingredient compound in the insecticide solution, as is evident from the comparison of the percent spraying described below, will be

<img file="PT85348B_D0010.tif" />

<img file="PT85348B_D0011.tif" />

preferably in the range of 0.5 to 5% by weight, preferably in the range of 0.5 to 3% by weight.

In addition to the active ingredient compound described above, a stabilizer such as BHT, 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), etc. may be incorporated into the insecticidal solution as required. In addition, covert agents such as perfumes, etc. may be added.

For the absorbent porous wick, powdery inorganic substances made in a boll with a binding agent may be used and then molded. Inorganic powdery substances include clay, talc, kaolin, diatomaceous earth, plaster, perlite, bentonite, abla earth, glass fibers, asbestos, and mixtures thereof, etc., and the binding agent includes carboxymethyl cellulose, starch, gum arabic, gelatin, polyvinyl alcohol and mixtures thereof, etc. Such absorbent molded wicks are finely porous, and the amount of insecticidal solution absorbed by them is reasonably small compared to absorbent wicks made primarily of fibrous substances, so that they are suitable as absorbent wicks for long term use. Among these, plaster, clay, diatomaceous earth, abla earth, and perlite are preferable as powdery inorganic substances in terms of moldability, etc., and CMC is suitable as a bonding agent in terms of solvent insolubility, moldability, etc. The most preferred absorbent wick is that which is prepared by cake between two or more of the CMC powdered inorganic substances and shaping the resulting cake. In the production of such absorbent wicks, the amount of binding agent used will preferably be from 1 to 10% by weight of the swab.

Absorbent porous locks may incorporate pigments, dyes, antiseptics, etc., as required, provided that the lint characteristics are not impaired.

As described above, according to the method for the heat fumigation extermination of insects according to the present invention, the above insecticidal compound

<img file="PT85348B_D0012.tif" />

It may be sprayed in an amount sufficient to develop sufficient insecticidal activity and moreover in an effective high percentage of spraying and relatively low heating temperatures between 105 and 130 ° C, and an effective and insecticidal effect may be maintained over a long period of time. Also, according to the present invention, the heating temperature is relatively so low that the method is preferable in terms of safety in time of use.

Reference Example 1

Using an appliance as depicted

I _t t, in the figure, were immersed in the container containing a saturated aliphatic hydrocarbon liquid 015 porous molded wicks ^!• 7 mm diameter and 7 cm long absorbent absorbers having the conditions described in Tables 1 and 2. The wick was heated to

around the top at a temperature of 12 ° C, and the amount of vaporized (decreasing) saturated aliphatic hydrocarbon was measured. Results are described together in Tables 1 and 2.

!

Table 1

<td>]Composition</td><td>N2.1</td><td>N2.2</td><td>N2.3</td><td>N²-4</td><td>N^and.5</td><td></td><td>NQ.7</td>

<td>i Plaster</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td>

<td>f Clay</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td>

<td>Diatom Earth</td><td> 3</td><td> 3</td><td> 3</td><td> 3</td><td> 3</td><td> 3</td><td> 3</td>

<td>CMC</td><td> 0.1</td><td> 0.3</td><td> 0.5</td><td> 1.0</td><td> 1.5</td><td> 2.0</td><td> 3.0</td>

<td>Amount of vaporized solvent (ml / hr)</td><td> 0.22</td><td> 0.18</td><td> 0.16</td><td> 0.11</td><td> 0.08</td><td> 0.03</td><td> 0.01</td>

<img file="PT85348B_D0013.tif" />

CM

Table

<img file="PT85348B_D0014.tif" />

<img file="PT85348B_D0015.tif" />

<img file="PT85348B_D0016.tif" />

As is evident from the results of Table 1, the amount vaporized and in order, then, the amount i absorbed tends to decrease with the increase in quantity | WTO When the amount of CMC is greater than 1.5 parts by weight (10.3% by weight of the total weight of the wick), the amount of vaporized solvent is markedly small. It is difficult to achieve sufficient vaporization. Although in terms of absorbent wick moldability, it is appropriate to use CMC

I | in an amount by weight of 1% or more based on the total weight i of the wick. Accordingly, an appropriate amount by weight of said incorporated bonding agent is from 1 to 10% based on: total weight of the wick, considering the above absorbance, moldability.¹ tity, etc.

i

I As is evident from the results of Ta

In Table 2, various forms of pulverulent inorganic substances may be used with the amount of solvent vaporized. also moderate.

The present invention will be specific. illustrated by reference to the following examples.

EXAMPLE 1 | A 7 mm absorbent porous strand. in diameter and 7 cm in length was prepared from a material comprising 5 parts plaster, 5 parts by weight of^! clay, 3 parts by weight of diatomaceous earth, and 0,5 parts: by weight of CMC, and placed on the fumigator by heating | exposed in the figure. The container was placed 10 ml of a single! C14-C17 mixed saturated aliphatic hydrocarbon solution

(as described above) containing 1% by weight of (S) -2-methyl-4-oxo-3- (2-propynyl) -cyclopent-2-enyl (1R) -cis, transcrisantemate as an active ingredient compound. Current was passed to the heater to heat the absorbent wick around the top so that the wick surface had taken various temperatures described in Table 3, and the amount of vaporized / heated time of the active ingredient compound in the insecticide solution was measured. and the total percentage of evaporation effective. In addition, the time required for the solution to • decrease substantially to zero was measured. The results /

<img file="PT85348B_D0017.tif" />

Measurements of the following collected following a column are described in Table 3. The vaporized amount and the total percentage of effective evaporation were as follows.

Vaporized quantity;

steam was rapidly being collected at regular intervals by silica gel and extracted with chloroform; The chloroform extract was concentrated and quantitatively analyzed by gas chromatography, and the total values ​​then obtained were divided by the total vaporization time.

Total percentage effective evaporation (percentage recovery);

The total amount which, up to the amount sprayed per unit of time essentially zero, was obtained with the following test and the amount was sprayed to the extent that the following test was completed active ingredient present in the residual solution in the container (A mg ) and that of the active ingredient in the absorbent wick (B mg = concentration of residual solution in container *

I t

weight increase in the absorbent wick); and calculations were performed with the following equation with the amount of active ingredient present in the container before heating as G mg!

you

Total Percentage of Total Vaporized Quantity, Effective Evaporation ~

C - (A + B)

<img file="PT85348B_D0018.tif" />

<img file="PT85348B_D0019.tif" />

II tA

— R — 1

Φ &amp;

Ctí Fi

<img file="PT85348B_D0020.tif" />

<td>Period of time required for solution to decrease substantially up to zero (hr)</td><td>tocjcnc-Ln ^ i-Hcn o rH H i — I r — 1</td>

<td>Total effective evaporation percentage (%)</td><td>m H o- 'd- m cm o' t-cocococococot-c-</td>

<td>Amount of vaporized active ingredient compound (mg / hr)</td><td>r— v H m to cm ocm CMto ^ M-mkOc— cococn ooooooooo</td>

<td>aj o P-P 3 si -P Φ aj S Bread (OOP) Φ to 3 σ σ¹EH &lt;4</td><td>omomomoLPO OOr-lrMCMCMKStCxlc — 1 rH &lt;—ir-lr-lt ~ IrHt— {r — 1</td>

<img file="PT85348B_D0021.tif" />

| As can be deduced from the above results i

As described above, it is confirmed that the total effective evaporation percentage (recovery percentage) is markedly high at (a heating temperature between 105 and 130 ° C (both inclusive)), effectively vaporizing the active ingredient compound. At a heating temperature greater than 135 ° C, the total percentage of effective evaporation decreases, that is, decomposition resinization and polymerization become striking, and therefore such temperature is found to be inadequate. At a temperature of less than 105 ° C, both the total effective evaporation percentage and the amount of the active ingredient compound vaporized per unit time decreases, and therefore such temperature also proves to be unsuitable.

EXAMPLE 2 procedure was carried out analogously to Example 1 except that various solutions of saturated aliphatic hydrocarbons other than number of acid were used.

The carbon values ​​shown in Table 4 and the heating temperature was set at 120 ° C to measure the vaporized amount and the total percentage effective evaporation.

The results are described in Table 4.

ii Table 4

<td>Number of carbon atoms of solvent</td><td>Amount of vaporized active ingredient compound (mg / hr)</td><td>total percentage effective evaporation (%)</td>

<td>^Ç11</td><td> 0.83</td><td> 72</td>

<td>^Ç12</td><td> 0.78</td><td> 80</td>

<td>^Ç14</td><td> 0.67</td><td> 83</td>

<td> °16</td><td> 0.51</td><td> 83</td>

<td>^Ç18</td><td> 0.38</td><td> 81</td>

<img file="PT85348B_D0022.tif" />

; As is evident from the results shown in Table 4, the use as a solvent of a C12-C18 saturated aliphatic hydrocarbon was good from the point of view of^! such effective evaporation percentage and the vaporized amount of the active ingredient compound.

EXAMPLE 3

I

The test was performed in the same manner as in Example 1 except that the heating temperature

I! was 120 ° C and the concentration of the active ingredient compound i

i in solution varied as indicated in Table 5 to measure the quan. vaporized quantity and the total effective evaporation percentage of the active ingredient compound. The results are described in Table 5.

Table 5

<td>Concentration of active ingredient compound in solution (wt.¾)</td><td>Amount of vaporized active ingredient compound (mg / hr)</td><td>Total effective evaporation percentage (%)</td>

<td> 0.5 1 2 3 4 5</td><td> 0.58 0.63 0 · 71 0.79 0.83 0.92</td><td> 88 85 83 84 81 80</td>

<td> 10</td><td> 1.07</td><td> 72</td>

í As is evident from the above results

As described above, the concentration by weight of the active ingredient-containing compound is between 0.5 to 5% and is good from the point of view of the total effective evaporation percentage and the amount of va. of the active ingredient compound.

<img file="PT85348B_D0023.tif" />

i EXAMPLE 4

An absorbent wick (A) 7 mm in diameter and 7 cm in length was prepared by making a cake; 7 parts of plaster by weight, 5 parts of clay by weight and

I is one part powdery fiberglass (100 mesh) with 0.3 parts CMC. Similarly a wick was prepared | absorbent (b) of the same size by making a 2 part by weight fiberglass cake with 10 parts by weight plaster. Ca of the absorbent wick was subjected to a heat fumigation shown in the figure where the wick was heated to 110 ° C.¹ To this vessel was introduced 10 ml of a hydrocarbon solution; C14-C17 saturated aliphatic grandson (as described above) containing 1% by weight of (2) -2-methyl-4-oxo-3- (2-propynyl) -cyclopent-2-enyl (1R) -cis, transcrisantemate ( pralethrin). Using the preparation thus obtained, the amount of vaporized pralethrin was measured at each pass at 20, 40, 60, SO and 100 hours after the heat was supplied to the fumigator,

Table 6

<td rowspan="2">Real time ; after the power supply (hour)</td><td colspan="2">Amount of vaporized pralethrin (mg / hr)</td>

<td>Absorbent wick (A)</td><td>Absorbent wick (B)</td>

<td> 20</td><td> 0.47</td><td> 0.84</td>

<td> 40</td><td> 0.51</td><td> 0.63</td>

<td> 60</td><td> 0.45</td><td> 0.50</td>

<td> 80</td><td> 0.46</td><td> 0.42</td>

<td> 100</td><td> 0.42</td><td>No insecticide solution</td>

The results show that the absorbent wick (A) is suitable for the present preparation with proline as an active ingredient, and that the absorbent wick (B)

<img file="PT85348B_D0024.tif" />

<img file="PT85348B_D0025.tif" />

not appropriate therefore.

EXAMPLE 5

An absorbent porous wick 7 mm in diameter and 7 cm in length was prepared from a material comprising 7 parts by weight plaster, 4 parts by weight clay, 2 parts by weight diatomaceous earth and 0.4 weight CMC , and subjected to the heat fumigator shown in the figure where the mehha was heated to 115 ° C. 15 ml of each C14-C17 mixed aliphatic hydrocarbon solution (N · 0 Solvent H (as described above)) containing 200 mg of -2-methyl-4-oxo-3- (2-propynyl) was added to the container. ) -cyclopent-2-enyl (1R) -cys, transcrisantemate (pralethrin) and 200 mg of dl-5-allyl-2-methylcyclopent-2-eno-4-one-1-yl-d-cis / trans-chrysanthoma (d-allethrin), respectively. Using each preparation, the extermination time of adult female mosquitoes (Oulex pipiens pallens) was measured as follows according to the fourth test: each hour 0, 1, 3, 6, and 12 after the electrical supply to a fumigant by heating. located in a 30 m3 (8-tatami-room) room, 50 female adult mosquitoes were released into the room to examine the 50% extermination time. This test was repeated 5 times, and the result was expressed as the mean value.

Table 7

<td rowspan="2">Real time after power supply (Hour)</td><td colspan="2">Extermination Time</td>

<td>Pralethrin</td><td>d-Alethrin</td>

<td> 0</td><td> 15' 24</td><td> 51’ 43</td>

<td> 1</td><td> 1’ 54</td><td> 4' 11</td>

<td> 3</td><td> 1’ 47</td><td> 4' 22</td>

<td> 6</td><td> 1’ 45</td><td> 3' 49</td>

<td> 12</td><td> 1' 55</td><td> 4’ 16</td>

<img file="PT85348B_D0026.tif" />

This result shows that pralethrin is suitable for an active ingredient of the present preparation and therefore d-alethrin is not.