JPS63267706A - Insecticide containing benzyl alcohol ester for smoking combustion and thermal evaporation and production thereof - Google Patents

Abstract

PURPOSE:To obtain an insecticide for smoking combustion and thermal evaporation, stable in preparation or with time and having remarkably improved insecticidal efficacy, by using a relatively readily synthesized and inexpensive specific benzyl alcohol ester based pyrethroid with an antioxidant. CONSTITUTION:An insecticide for smoking combustion and thermal evaporation obtained by using a benzyl alcohol ester expressed by formula I (R1 is H or methyl; R2 is methyl or isobutenyl when R1 is H and R2 is also methyl when R1 is methyl; R3 is H, cyano or ethynyl; X is H, halogen, methyl or methoxy; n is 1-4; Y is halogen, alkyl, alkenyl, benzyl, etc.) (e.g. a compound expressed by formula II) as an active ingredient and adding 0.01-20% antioxidant, such as dibutylhydroxytoluene or butylhydroxyanisole, thereto. The compound expressed by formula I is prepared by esterifying carboxylic acids expressed by formula III with alcohols, expressed by formula IV and obtained by previously adding the antioxidant.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula (wherein 9 represents a hydrogen atom or a methoxyA7 group, and when & is a hydrogen atom, ru represents a methyl group or an isoptenyl ρ group,
When & is a methyl group, ru also represents a methyl group.

R represents a hydrogen atom, a cyano group, or an ethynyl group, or represents a hydrogen atom, a halogen atom, a methyl group, or a methoxy group, and n represents an integer of 1 to 4. Y is a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkynyl group, an alkynyl group, a haloalkenyl group, a haloalkenyl group, an alkoxy group. Represents a haloalkoxy group, alkoxyethyl group, alkoxyethyl group, nitro group, benzyl group or phenoxy group.

Moreover, X and Y may be bonded at the terminals to form a methylenedioxy group. The present invention relates to an insecticide for smoking and heat evaporation, which contains benzyl alcohol esthetic μ expressed by the following as an active ingredient and further contains an antioxidant, and a method for producing the same.

Conventionally, allethrin and flamethrin have been commonly used as active ingredients in insecticides for smoking and heating evaporation of mosquito coils and electric mosquito coils, and have been widely used in practical use. These compounds exhibit effective insecticidal efficacy when properly formulated into mosquito coils and electric mosquito repellent compositions, but they have the drawbacks of complex chemical structures and high manufacturing costs. There is. In the process of searching for more useful pyrethroids for smoking and heat evaporation, the present inventors focused on benzy-μ alcohol ester pyrethroids, which are relatively easy to synthesize and inexpensive, and as a result of intensive research, found that When the compound represented by formula (I) is used together with an antioxidant, its stability during the manufacture of the active ingredient, during the preparation of preparations such as mosquito coils, and even over time is significantly improved, and as a result, the insecticidal efficacy is greatly improved. found that it improved.

That is, when the compound represented by the general formula (I) is prepared and formulated without adding an antioxidant,
As exemplified in Japanese Patent No. 8396, it has become clear that although no particularly superior efficacy is obtained compared to allethrin or flamethrin, the addition of an antioxidant brings about the following significant benefits.

■When producing a compound, if an antioxidant is added to the alcohol component prior to the esthetic treatment and then distilled, the purity and yield of the product will be greatly improved. Therefore, if the alcohol component thus obtained is used in the esthetic mucinization step, it is possible to efficiently prepare a raw material with high purity as well, and when it is added to an insecticide, it is possible to suppress the reduction in insecticidal efficacy due to the presence of impurities.

In addition, when the antioxidant is removed from the system during the manufacturing process, it is preferable to further add the antioxidant after the completion of esterification in consideration of the stability of the raw material over time.

■When manufacturing mosquito coils and smoke agents, various organic and inorganic base materials are mixed with the pyrethroid raw material, and decomposition of the pyrethroid from the base material becomes a problem, but it is possible to manufacture products by adding antioxidants. By doing so, destabilization can be prevented and furthermore, it is extremely effective in terms of stability over time.

■ Decomposition due to the low concentration of active ingredients is a problem with heating transpiration agents such as electric mosquito repellent mats, but the addition of antioxidants is extremely useful in preventing decomposition.

■Addition of antioxidants suppresses the decomposition of active ingredients during combustion heating and contributes to increasing the volatilization rate.

■The combination of the above ■, ■, ■, ■ significantly enhances the insecticidal efficacy.

The knowledge that the addition of an antioxidant not only inhibits the oxidation of the compound but also provides various effects, especially for the compound of general formula (I), is completely unexpected from the conventional technology and has no practical application. This is an extremely useful discovery.

The compound represented by the formula (I) used as an active ingredient in the present invention is solid or liquid at room temperature; or isoptenyl μ group, and when R is a methyl group, R also represents a methyl group. , X represents a hydrogen atom, a halogen atom, a methyl group, or a methoxy group, and n represents an integer of 1 to 4. Y represents a halogen atom, a group, a〃kieμ, group, ha, loaμkenyl group, haloaμkiniρ group, alkoxy group, heroaμkoxy group, aμkoxy group, alkoxyethyl group, nitro group, benzyl group or represents a phenoxy group.Also,
X and Y may be bonded at the terminals to form a methylenedioxy group. ) or its reactive derivative; however, the feature of the present invention is that prior to esterification, the alcohol component is produced and distilled with an antioxidant added to it. . Examples of reactive derivatives of acidic acids include acid halides, acid anhydrides, lower alkali esters, alkali metal salts, and acid halides are preferred. Reactive derivatives of alcohol include, for example, clophyte, bromide, p-
Although toluene sulfonic acid ester may be used as a toluene sulfonic acid ester, it is preferable to use it for the esterification reaction immediately after distilling the alcohol component. The reaction is carried out in a suitable solvent, if necessary, in the presence of an organic or inorganic base or acid as a deoxidizing agent or catalyst, and if necessary, with heating. In the acid moiety of general formula (I), at least one asymmetric carbon is present, except when R and R are both methyl groups. Of course, each of these or any mixture thereof is also included in the present invention.

The same applies when an asymmetric carbon is present in the alcohol component. Representative examples of the compound represented by the above formula (I) are shown below, but the present invention is of course not limited to these.

4'-propargylbendi/I/2,2-dimethyf
v-3-Isophthynylcycloprobanca-boxylate n" 1.5273 4'-allyl penrift v 2.2-dimethy/l/-3
-Isopteni/! /V cloprobanca μ boxylate n
201.5268 4I-methoxymethylbenzi/L' 2.2-dimethy/L/-3-isobuteny cycloprobanca μboxylate n201.5104 2/, 4/-dimethylbenzi/I/ 2.2-dimethy/L '-3-Isoptenyl cyclozolobanca μ boxylate n201.5095 αε 3/, sl-methylenedioxy-6'-chlorobendi〃2.2-dimethy)v-3-isobutenylcyclopropanemethy A/-3 -isobutenyl cyclopropane carboxylate n 201.52
804'-(3,3-Shiffyoroa1JIv)benzi/
L/2.2-dimethy/&-3-isoptenylcyclopropanecapoxyv-) n2
01.52134'-(3-chloroprobargi/L/)
Benji/L/ 2. '2-dimefV-3-isobutene μcyclopropanecarboxylate
n201.5291-dimethy/l/-3-isobuty=μcyclopropanecarpoki VV-)
n201.54394'-(2-)p-oloethoxy)benzi/l/2,2-dimethy, 11/-
3-isobutene μcycloprobanca (boxy V-)
n”01.53162/,
6/-dimethoxy-4'-propylbenzyl 2.2
-Dimethyl-3-isobutenylcyclopropanecarboxylate n201.53082.2-dimethy/L'-3-isobutenylcyclopropanecarboxylate n201.53704'-probalgiμbenzi/l/2,2.3. 3-tetofumethy y cyclozolobanca μ boxylate n201.5132 zl, a/-dimethy) v-4'-probargi ρ benzy ρ
2.2.3.3-tetofmethylcyclopropanecarboxylate n2' 1.
51122'16'-dichloro-4'-aliμbenzi
v2,2.3-torino thousand p cyclopropanecarboxylate n201.5142 3'--phenoxybendiyv 2,2.3.3-f
ll'fy cyclopropane carboxylate n201.5507 31-benzyl-α'-ethynylbendi/I/I2.
2.3-trimethyl-/cyclopropanecarboxylate nD 1.5491 zl, 51-dimethyl-4'-methoxyethyl-α'
-Cyanobenzilv2.2,3.3-tetofmethylnchloderobankayLyHkiVv-) n20
1.53203'-(2,4-pentadienyl)benzi/l/2.2-dimethy/l/-3-isobutenylcyclopropanecarboxylate
n"1.53473'-IsoderohyeIV-5'-
Chloro-α'-ethynylbendi/L/ 2,2-dimethyl-3-isobutenylcycloderobanecarboxylate n201.53824'-Methoxymethylbendiyv 2,2,3.3-tetramethylcyclozolopanecarboxylate c ~ 3'-7z Tsukishi α'-Vl/Venji, 71/2
．． 2.3-Trimethycycloglobancarpoxylate n201.5484 3/, 41-methylenedioxy-6'-methylbenzyl 2.2.3.3-Tetramethyμcyclopropanecarboxylate n n 1.
52792'-Bromo-4'-nitropendi/l/
2,2,3.3-Tetramethylcyclozolopanecarboxylate n n 1-5068 4'-(1-methyl-2-fluoro-2-chloroviny/
L/) Benzylv2.2-dimethy A/-3-isoglobeniμ cyclopropanecarboxylate 4'-ethoxymethylbenzi/L/2.2-dimethyIv
-3-Isoptenyl cyclopropane hydroxylate n
D 1-5140 The above-mentioned compound used as an active ingredient can be blended in the formulation in an amount of KO, 01 to 90%.

On the other hand, the antioxidants used in the present invention are as follows, but of course they are not limited to these. One or two antioxidants are added during manufacturing or in the formulation.
It is usually added in an amount of 0.01 to 20% to achieve sufficient effects.

(A) BHT (dibutylhydroxytoluene) (
B) Bill A (butylhydroxyanisole) (C) DBH (2,5-ditertiarybutylhydroquinone) (D) Yoshinox 425 (E) Yoshinox BB (4,4'-butylidene-bis-(6-tertiarybutyl) -3-methylpheno-/I/
)) When using these as insecticides for smoking and heat evaporation, the above-mentioned mixed composition of benzyl alcohol ester pyrethroid and antioxidant can be made into a solution in its original form or with an appropriate solvent. It can be mixed with wood flour or other suitable base material and used as a dosage form such as a mosquito coil. Furthermore, there is a method in which the composition is mixed with a combustion agent and used as a so-called smoking agent in which the chemical is released by the combustion heat and smoke of the combustion agent, or a method in which the composition is mixed with an organic foaming agent and sealed in a bag and the mixture is heated indirectly. It is also possible to thermally decompose the organic blowing agent without combustion, and to effectively fumigate the agent by the action of the thermally decomposed gas. Furthermore, the composition can be applied as a heating transpiration agent to a form such as an electric mosquito repellent described later. In addition, the said composition also contains N-octylbicyclohep? dicarboximide (product name M
GK-264), mixture of N-octylbicyclohebutene dicarboximide and terrylsulfonate (trade name MGK-5026”), octachlorodipropyl ether, biveronyl butoxide, cinepirin 5001
β-Butoxy-β-thiocyanodiethyl ether/l/(
The insecticidal efficacy can be further enhanced by adding a synergist for pyrethroid such as Riesen 384 (trade name) or Sesamex.

Also, other active ingredients such as other pyrethroids, fenitrothion, DDVP, diazinon, globafos,
Organic phosphorus agents such as pyridafenthione, carbamate agents such as Sevin, Meopal, and Sancide, insecticides and acaricides such as Cartap, chlorzenamidine, and Mesomi μ,
By mixing fungicides, nematocides, herbicides, plant growth regulators, fertilizers, and other agricultural chemicals, highly effective multipurpose compositions can be obtained.

A particularly useful mixed composition is a combination with allethrone ester pyrethroids. That is, when the composition of the present invention is used as an insecticide for non-burning and heat evaporation,
Although it exhibits excellent insecticidal efficacy, especially high lethal efficacy, it suffers from a slight lack of knockdown effect, so when we tried to use it in combination with allethrone ester pyrethroid, we found that it was simply a fast-acting pyrethroid. We obtained a new finding that not only the effects of this drug are added, but also the lethal efficacy and knockdown effect work synergistically.

This remarkable synergistic effect is due to the use of free ester pyrethroids such as resmethrin and resmethrin.
It is not observed in imidomethymu-alcoholic ester ρ-based pyrethroids such as neopinamine, but is unique to allethrolone ester-based pyrethroids.

Preferred allethrone esters include allethrin, d-cis, trans-allethrin, d-trans-allethrin, and S-bio-μ. In addition, the mixing ratio of benzyl alcohol esthetic μ and A V Throlon A μ co esthetic is 10:1 to obtain a sufficient synergistic effect.
A ratio of 1:5 is appropriate.

The composition of the present invention can be used not only for susceptible pests but also for
It is extremely useful for controlling various pests resistant to organic phosphorus agents and carbamates, such as sanitary pests such as flies, mosquitoes, and cockroaches, as well as agricultural and horticultural pests, storage insects, and mites.

Next, the results of a rounding test clearly demonstrate the superiority of the composition provided by the present invention.

Test Example 1 5.5 g of 2.2-dimethylv-3-isoptenylcyclopropanecarboxylic acid chloride was dissolved in 15 m of dry benzene, and various test alcohol μ components were dissolved in 20 m of dry benzene. When this is added, and dry pyridine 3d is further added as a condensation station, pyridine hydrochloride is precipitated.

After standing overnight at room temperature, the crystals of pyridine hydrochloride were separated from each other, and the low-boiling fraction was removed, and the yield and purity of the resulting ester/l/ were examined, and the results were as follows.

Test alcohol-μ Produced esthetics Yield Purity Mu Antioxidant used during alcohol production (%) (%) (1) 2.9g
79 85/p BHT
4.0% 94 97# DBH3.0%
95 96(7) 3.7g81 78 #B HA 4. Q% 93 94ke Yoshinox 425 2.5% 95
97111G4.4g 7
7 80 The sample alcohol μ component is the same as that of the above compound example, and represents the alcohol constituting the esthetic μ.

As a result of the test, when alcohol produced by adding antioxidants was subjected to ester μ, the yield and purity of the ester was significantly better than that of Alny μ, which did not contain antioxidants. Ta.

It is assumed that this is because the addition of antioxidants suppressed the transition, decomposition, isomerization reactions, etc. that occur during the production of 7μ, which led to the production of high yield and high purity Esthe μ. Ru.

Test Example 2゜The benzyl alcohol esthetic μ of the M product of the present invention and an antioxidant were mixed with a base material such as pyrethrum meal powder or wood flour, and a binder was added and kneaded with a kneading machine, followed by an extruder. A mosquito coil was prepared by punching out a plate into a spiral shape and drying it. The decomposition rate during the manufacturing process was determined from the analysis value of the active ingredient after manufacturing and the preparation value of the active ingredient, and then it was placed in an fx greenhouse at 40'C for 2
After storage for several months, the stability of the mosquito coil over time was investigated and the results were as follows.The test result was to prepare a mosquito coil by adding an antioxidant to the active ingredient benzyl alcohol-μ ester μ. It has been found that the decomposition rate of the active ingredient during the process is significantly suppressed, and that it is also extremely effective in terms of stability over time.

This prevents factors that may promote decomposition of the active ingredient, such as mixing with organic or inorganic substrates, kneading under hydrostatic conditions, drying processes, or long-term contact with substrates. This shows that the anti-decomposition effect of antioxidants is extremely high.

The appropriate ratio between the amount of antioxidant added and the amount of active ingredient that gives good results in stabilizing the active ingredient in the preparation is 1:20 to 1O:1, and usually some of the antioxidant is added to the active ingredient. This includes those added during the production of the alcohol-μ component or those added to the bulk material after completion of ethyl.

Test Example 3 According to Test Example 2, mosquito coils containing the ingredients shown in the table below were prepared and tested for their effectiveness in making Culex mosquitoes fall on paper.

This experiment was conducted using the method of Nagahama and Katsuin et al. described in "Insect Control Science" Vol. 16 (1951), p. When the ratio was investigated, the following results were obtained.

The test insecticidal ingredient numbers are the same as those for the above compound examples, and those marked with * were prepared using active ingredients produced without adding an antioxidant to the alcohol component.

Note that the relative effectiveness of allethrin is 1.00.

As a result of the test, it is clear that the composition of the present invention to which an antioxidant has been added suppresses the decomposition of the active ingredient during the manufacture of mosquito coils or decomposition over time, and exhibits a higher insecticidal effect than the control composition without additives. became. It was also confirmed that adding an antioxidant during the production of the alcohol component contributes to increasing the purity and yield of NTEP, and as a result, improves the insecticidal efficacy.

Test Example 4 A test was conducted in the same manner as in Test Example 3 to investigate the synergistic effect of mixing with allethrone ester pyrethroid.

As a result of the test, by adding allethrin to the composition of the present invention, a remarkable synergistic effect with both the knockdown effect and the lethal effect was observed, and it became clear that the composition is extremely useful from a practical standpoint. This phenomenon is due to the isomers of allethrin, d-cis, tofunsu-allethrin, and d-) lance-
The same was true for allethrin and S-biol, but
On the other hand, it was not observed with other 7-lucoric ester pyrethroids such as resmethrin, resmethrin, and neopinamine, or with fenitrothion.

Test Example 5 An acetone solution of the components shown in the table below was placed in a 22 mm x 35 m
It is adsorbed onto a m×2.8 mm pulp board and air-dried. This pulp board was placed on a heating element heated to 160°C, and an electric mosquito repellent method was used to evaporate the mosquito by heating.Efficacy tests were conducted using adult house flies. In other words, a stainless steel cage in which 30 houseflies were released in a 25 trl room was placed at a height of J50 cm from the ceiling.
7) The relative effectiveness of the drug was calculated from the number of adult house flies that fell and turned upside down after being hung at a height and exposed for 4 hours, and the mortality rate after 24 hours was investigated, and the results were as follows. Also,
The volatilization rate of the active ingredient was also measured for each mat.

As a result of the test, the electric mosquito repellent mat prescription, similar to mosquito coils,
It was confirmed that the composition of the present invention containing an antioxidant suppresses the thermal decomposition of the insecticidal component during use, significantly improves the volatilization rate, and greatly enhances both the knockdown effect and mortality rate. In the case of electric mosquito repellent mats, the amount of active ingredients blended is low and the mat is continuously heated, so adding an antioxidant is extremely effective in preventing decomposition of the active ingredients.

Next, examples of the present invention will be shown, but it goes without saying that the present invention is not limited to these.

Example 1 0.15 g of compound (3), 0.5 g of BHTo, and 0.20 g of piperoni μ-butoxide, pyrethrum extract powder,
Mix uniformly with 99.6 g of a base material for mosquito coils such as wood flour and starch to prepare mosquito coils using a conventional method and obtain 0.15% of the active ingredient.
Obtain % Mosquito Coil.

Example 2゜ Compound (5) 0.12g, DBHo, 03g and β-butoxy-β'-thiocyanodiethyl ether 1, Og were mixed into a substrate for mosquito coils such as pyrethrum extract lees powder, wood flour, starch etc. 98
．． A mosquito coil was prepared by uniformly mixing 85 g of the above ingredients and using a conventional method.

Example 3 Compound (It) 4 g% Kerosene was added to a mixture of 11 g of DBII, 500 Log of Cynevirin, an appropriate amount of fragrance, and a blue dye to make 100-. After stirring and dissolving, this insecticidal liquid 1- was impregnated into a 22 mm x 35 mm x 2.8 mm pulp board and placed on an electric heating element, and heated to about 160°C.
Heat and evaporate.

Example 4゜ Compound 2θg1 Yoshinox 425 5g.

Sugar powder 25g 1 ash 7g, wood flour 11g 1 diatom ±11g
and 1.5 g of manganese dioxide were mixed uniformly, and an aqueous solution of 4.5 g of chloric acid and 100 g of water was added thereto, kneaded well, formed into a cylindrical shape, dried, and heated and fumigated. get the agent.

Example 5゜Compound logging 05g, BHA 0.4g, Bemethrin 5g,
Add 70 g of Azocica μponic acid amide and 5 g of 0M0, mix uniformly, and form into granules to obtain a heated fumigant.

Claims (3)

[Claims] (1) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼…(I) (In the formula, R_1 represents a hydrogen atom or a methyl group, and R_
When 1 is a hydrogen atom, R_2 represents a methyl group or an isobutenyl group, and when R_1 is a methyl group, R_2 also represents a methyl group. R_3 represents a hydrogen atom, a cyano group, or an ethynyl group, and
represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and n represents an integer of 1 to 4. Y is a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group, an alkynyl group, a haloalkenyl group, a haloalkynyl group, an alkoxy group, a haloalkoxy group, an alkoxymethyl group, an alkoxyethyl group, a nitro group, a benzyl group, or Represents a phenoxy group. Moreover, X and Y may be bonded at the terminals to form a methylenedioxy group. ) An insecticide for smoking and heat evaporation, characterized in that it contains a benzyl alcohol ester represented by the following as an active ingredient and further contains an antioxidant. (2) The insecticide for smoking and heat evaporation according to claim (1), which contains allethrone ester as an active ingredient. (3) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼…(II) (In the formula, R_1 represents a hydrogen atom or a methyl group, and R_
When 1 is a hydrogen atom, R_2 represents a methyl group or an isobutenyl group, and when R_1 is a methyl group, R_2 also represents a methyl group. ) A general formula prepared by adding an antioxidant or a carboxylic acid represented by or an ethynyl group; It represents an alkynyl group, a haloalkenyl group, a haloalkynyl group, an alkoxy group, a haloalkoxy group, an alkoxymethyl group, an alkoxyethyl group, a nitro group, a benzyl group, or a phenoxy group.Also, when X and Y are bonded at the terminal, methylenedioxy The general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, R_1, R_2, R_3, A method for producing an insecticide for smoking and heat evaporation, characterized by obtaining a benzyl alcohol ester represented by (X, Y, and n have the same meanings as above).