JPH02240066A - Perfluoroalkylimidazoline-poly(ethyleneoxy) compound, its production and use thereof - Google Patents

Abstract

NEW MATERIAL:The perfluoroalkylimidazoline.poly(ethyleneoxy) compound of formula I (m is integer of 2-10; q is integer of 1-5). EXAMPLE:1-(2-Hydroxyethyl)-2-(pentadecafluoroheptyl)-2-imidazoline. USE:An insecticide having excellent properties as a surfactant and exhibiting excellent insecticidal activity especially against dipterous vermin (e.g. housefly), hymenopterous vermin (e.g. German cockroach) and lepidopterous vermin (e.g. army worm). PREPARATION:The compound of formula I can be produced by reacting a compound of formula II under heating at >=100 deg.C usually in an inert gas atmosphere. The starting compound of formula II is obtained either by the aminolysis reaction of a compound of formula III (R is lower alkyl) with the compound of formula IV or by the ethylene oxide addition reaction of the compound of formula V and the compound of formula VI.

Description

[Detailed description of the invention] Industrial application field> The present invention provides perfluoroalkyl imidazoline poly(
The present invention relates to ethyleneoxy) compounds, their production methods, surfactants made of them, and insecticides containing them as active ingredients.

BACKGROUND ART AND PROBLEMS TO BE SOLVED BY THE INVENTION Although various surfactants have been known in the past, they are not always sufficient.

Means for Solving the Problems In view of the above circumstances, the present inventors have conducted various studies and found that a perfluoroalkylimidazoline poly(ethyleneoxy) compound represented by the following general formula (r) has surface activity. The present invention was completed based on the discovery that it not only has excellent properties as an agent but also has excellent insecticidal activity.

That is, the present invention is based on the general formula [wai (CtH40)Q H [where m represents an integer of 2 to 10 and q represents an integer of 1 to 5]. ] Perfluoroalkyl imidazoline poly(
The present invention provides a compound (hereinafter referred to as the compound of the present invention), a method for producing the same, a surfactant made of the same, and an insecticide containing the same as an active ingredient.

The method for producing the compound of the present invention will be explained in detail below.

That is, the compound of the present invention has the general formula (T1) CF, (C
F2) mCONHC,H,NH(C2H40)qH
(n) [wherein m and q represent the same meanings as above. ] can be obtained by subjecting an acylated N-monosubstituted amido amino alcohol to a heating reaction.

This reaction is usually accomplished by heating to 100° C. or higher in an inert gas atmosphere.

The N-substituted amidamino alcohol represented by general formula (II), which is a raw material compound for producing the compound of the present invention, can be obtained, for example, according to the following reaction method.

(Manufacturing method A) CF, (CF,)mCo, R + NH2C, H4N
H (C, H40) q H (IIl
-CF, (CF,)mCONHC, H4NH (C2
H40) qHII) [In the above formula, m and q represent the same meanings as above, and R
represents a lower alkyl group. ] This reaction is called an aminolysis reaction, and is usually carried out in a suitable solvent (for example, an alcohol such as ethanol).
) and diamine degree) at a temperature range of 5°C to 160°C.

(IfJ manufacturing method B) CF, (CF,)mCONHC, H4NH, . Q
, C, + CH, (V) (V
I) CF, cCF, >mCONHC2H, NH
cC2H. O) q HCI[) [In the above formula, m and q represent the same meanings as above. ] This reaction is an ethylene oxide addition reaction and rFPvf%, and is a reaction in which a predetermined amount of ethylene oxide (B) is added to N-(perfluoroacyl)ethylenediamine (V), and an appropriate amount of ethylene oxide (B) is added and reacted. using an inert solvent (e.g. benzene), closed or open (
This is achieved by heating in a temperature range of 50°C to 100°C, either batchwise or by blowing.

For example, the compounds of the present invention listed in Table 1 can be obtained by the production method described above.

Table 1 (C! Had) Q H The compound of the present invention has excellent properties as a surfactant and also has insecticidal activity, and is effective against, for example, the following pest insects.

Lepidopteran pests, moths such as the two-legged caterpillar moth (Nikameichi. cormorant), the brown borer moth, and the Japanese cutworm moth, the armyworms such as the fall armyworm, fall armyworm, and fall armyworm, and the Japanese armyworm. Agrothis sp.
p. ) % Heliothis genus pest (Heliothis
spp. ), Diptera pests such as the small moth, burr, and carp moth; Culex mosquitoes such as Culex mosquito, Culex mosquito; Aedes mosquitoes such as Aedes aegypti and Aedes aegypti; Anopheles mosquitoes such as Aedes albopictus; Chironomid mosquitoes; , fruit flies, fruit flies, s. When using the compound of the present invention as an active ingredient of an insecticide, the compound of the present invention may be used for insect pests of the order Pteroptera such as maggots, flies, flies, flies, blackflies, and stable flies, German cockroaches, black cockroaches, American cockroaches, brown cockroaches, and black cockroaches It is usually mixed with a solid carrier, liquid carrier, gaseous carrier, or feed, and if necessary, a surfactant or other formulation auxiliary agent is added to form an oil solution, emulsion, wettable powder, suspension in water, or in water. It is used by formulating it into flowable agents such as emulsions, granules, powders, aerosols, ULV agents, poison baits, etc.

These preparations usually contain 0.01% to 96% by weight of the compound of the present invention as an active ingredient.

Solid carriers used in formulation include, for example, clays (kaolin clay, diatomaceous earth, synthetic hydrated silicon oxide, bentonite, fubasami clay, acid clay, etc.), talcs, ceramics, and other inorganic minerals (sericite, quartz,
Sulfur, activated carbon, calcium carbonate, hydrated silica, etc.), chemical fertilizers (ammonium sulfate, ammonium phosphorus, ammonium nitrate, urea, ammonium chloride, etc.), and other fine powders or granules.As liquid carriers, for example, water, alcohol, etc. (methanol, ethanol, etc.), ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, methylnaphthalene, etc.), aliphatic hydrocarbons (hexane, cyclohexane, kerosene, light oil, etc.) , esters (
ethyl acetate, butyl acetate, etc.), nitriles (acetonitrile, isobutyronitrile, etc.), ethers (diisobrobyl ether, dioxane, etc.), acid amides (N,
N-dimethylformamide, N,N-dimethylacetamide, etc.), halogenated hydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride, etc.), dimethyl sulfoxide, vegetable oils such as soybean oil, cottonseed oil, etc.; Examples of propellants include chlorofluorocarbon gas, butane gas, LPG (liquefied petroleum gas), dimethyl ether, carbon dioxide, and the like.

Examples of surfactants include alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, alkylaryl ethers and their polyoxyethylenic products, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol derivatives, etc. can give.

Examples of formulation auxiliaries such as fixing agents and dispersants include vusein, gelatin, polyesters (starch powder, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, sugars, and synthetic highly water-soluble molecules (polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acids, etc.), and as stabilizers, for example, P
AP (isobrovir acid phosphate), BHT (2.6
-di-tert-buty7L'-4-methylphenol)
, BHA (a mixture of 2-tert-butyl-4-methoxyphenol and 8-tert-butyl-4-methoxyphenol), vegetable oil, mineral oil, surfactant, fatty acid or its ester, and the like.

Examples of base materials for poison bait include general food flour, plant essential oils, sugar,
Feed components such as crystalline cellulose, antioxidants such as dibutylhydroxytoluene and nordihydroguaiaretic acid, preservatives such as dehydroacetic acid, agents to prevent accidental ingestion such as chili pepper powder, and attractive flavorings such as cheese flavoring and onion flavoring, etc. can be given.

The formulation of flowables (suspensions or emulsions in water) generally comprises 1 to 75% of the compound, 0.6 to 15% of the dispersant, O. 1 to 10% of suspension aids (e.g., protective colloids and compounds imparting thixotropy), 0 to 10% of suitable auxiliaries (e.g., defoamers, rust inhibitors, stabilizers,
It can be obtained by finely dispersing it in water containing a spreading agent, penetration aid, antifreeze agent, antibacterial agent, anti-tlk agent, etc.). It is also possible to use an oil in which the compound hardly dissolves in place of water to form a suspension in oil. Examples of protective colloids used include gelatin, casein, gums, cellulose ether, and polyvinyl alcohol. Examples of compounds that impart thixotropy include bentonite, aluminum magnesium silicate, xanthan gum, and polyacrylic acid.

The preparation thus obtained is used as it is or diluted with water or the like. It may also be used with or without mixing with other insecticides, acaricides, nematicides, soil pest control agents, fungicides, herbicides, plant growth regulators, synergists, fertilizers, and soil conditioners. It can also be used at the same time.

When the compound of the present invention is used as an active ingredient of an agricultural insecticide, the application rate is usually 1 to 1000 per 10 ares.
9, and when applying emulsions, wettable powders, flowables, etc. diluted with water, the application concentration is 10 to 1000.
ppm, and granules, powders, etc. are applied as they are without any dilution.

In addition, when used as an active ingredient in insecticides for epidemic prevention, emulsions, hydrating agents, flowable agents, etc. should be used at a concentration of 10 to 1000 ppm in water.
For oils, aerosols, ULV agents, poison baits, etc., apply as is.

These application amounts and concentrations vary depending on the situation, such as the type of formulation, application time, application location, application method, type of pest, and degree of damage, and may be increased or decreased without regard to the above range. can be used.

Examples> The present invention will be explained in more detail below with reference to production examples, formulation examples, and test examples, but the present invention is not limited to these examples.

First, a production example of the compound of the present invention will be shown.

Production Example I N-2- and droxyethylenediamine (NA) 6.18
(5.OX10 mol) was dissolved in 64% dehydrated ethanol and kept at 6°C. On the other hand, ethyl pentadecafluorooctanoate 20F (4.5 x 10" mol) was dissolved in dehydrated ethanol 25", and NA was mixed and reacted with stirring. After 20 minutes, the solvent etc. were distilled off, and benzene was added. After treatment with
NFH) 19.52 was obtained. Then add this to 1mgH9
Distillation was carried out under the following reduced pressure while heating to 120°C to 240"C, and 1-(2-hydroxyethyl)-2
-(Pentadecafluoroheptyl)-2-imidazoline (IF) 11.79 was obtained. 29 of this product was subjected to gel permeation chromatography fractionation using high performance liquid chromatography to obtain pure IF product 1.212.

Properties: Colorless transparent viscous liquid Physical properties: d 1.674 n201.874020
D Production Example 2 N-(pentadecafluoro-octanoyl)ethylenediamine 1.7 1 P (8.7X 10 mol)
was added to dehydrated benzene 5-7°C (ζ After cooling, the temperature was reduced to 0°C.
of ethylene oxide2. After heating at a constant rate of 8 °C/min in an autoclave, heating at 90 °C for 8 hours, and then rapidly cooling to 50 °C to remove the solvent. After removal, 1.997 of N-(pentadecafluorooctanoyl)-N-hydroxyethylethylenediamine (NFH) was obtained. NFH 209 obtained by repeating this synthesis was subjected to the same operation as in Production Example 1, and 1-(2-hydroxyethyl)-2
A pure product of -(pentadecafluoroheptyl)-2-imidazoline 6.29 was obtained.

Next, some of the compounds of the present invention produced according to this production method are shown in Table 2.

Table 2 shows examples of formulations. Note that parts represent parts by W amount, and the compounds of the present invention are shown by the compound numbers listed in Table 2.

Formulation Example 1 Emulsion 10 parts of each of the compounds (1) and 12) of the present invention were added to 85 parts of xylene.
14 parts of polyoxyethylene styrylphenyl ether and 6 parts of calcium dodecylbenzenesulfonate were added thereto, and the mixture was thoroughly stirred and mixed to obtain each IOX emulsion.

Formulation Example 2 Wettable powder 20 parts each of the compounds of the present invention (1) and (2) are mixed with 4 parts of sodium lauryl sulfate, 2 parts of calcium lignin sulfonate, 20 parts of synthetic hydrated silicon oxide fine powder, and 54 parts of diatomaceous earth. Add to the liquid and stir and mix with a juice mixer to obtain each 20% permanent agent.

Formulation Example 8 Powder Compound of the Invention (1). Dissolve 1 part of each of (2) in an appropriate amount of acetone, add 5 parts of synthetic hydrated silicon oxide fine powder,
Add 0.8 parts of PAP and 98.7 parts of clay, stir and mix using a juice mixer, and remove acetone by evaporation to obtain 1% powder of each.

Formulation Example 4 Flowable Agent The compound of the present invention (2320 parts) and 1.5 parts of sorbitan trioleate were mixed with 28.5 parts of an aqueous solution containing 2 parts of polyvinyl alcohol, and the mixture was pulverized with a sand grazer.
(particle size: 8 μm or less), and then add 0.
05 parts and aluminum magnesium silicate 0.05 parts.
Add 40 parts of water-soluble FF containing 1 part, and further add 10 parts of propylene glycol and mix with stirring to obtain a 20% suspension in water.

Next, a test example is shown. The compounds of the present invention are indicated by the compound numbers listed in Table 2.

Test Example 1 Measurement of Surface Activity Properties as a surfactant were measured in terms of surface tension, foaming property, and emulsifying power. All measurements were performed at constant temperature and humidity (room temperature 2
The test was carried out at 5° C. and 60× humidity.

1) Surface tension: Using Rigosha's fiNRIA model (circular method), the sample aqueous solution was 2.OX10 to 1.0X10
The concentration of M was measured. Surface tension is Harkins
-Jordan correction. The results are shown in Table 8.

2) Foaming property: By semi-trace improved TK method, sample water solution 1'
l! For 2.0X10 M, immediately after foaming and 6
The foam volume after 6 minutes was measured, and the time immediately after was taken as foaming power, and the time after 6 minutes was taken as foam stability. The results are shown in Table 4.

8) Emulsifying power: 2.Pour OXIO M water-soluble gtO- into a 40rnl container attached to an emulsifier (Nippon Seiki Universal Homogenizer 1), then add 2 or 101 xylene as the emulsified oil and add it to the emulsifier. It was mounted, stirred for 5 minutes at a rotational speed of 8000±500 (rpm), allowed to stand for 5 minutes, and stirred again for 5 minutes to obtain an emulsion.

This emulsion was immediately transferred to a colorimetric tube with an 80i capacity scale, and after one hour of standing, the failure of the completely emulsified portion was read, and the emulsification rate was calculated using the following formula to determine the emulsifying power.

The results are shown in Table 5.

A) Surface tension Table 8 B) Foaming property Table 4 q Emulsifying power Table 6 Table 6 W. D. Harkins and H. F. J
ordan, J. Am. Chem. Soc. 52.1
75L (1980) Gomine Yano, Wasaburo Kimura.
Oil chemistry. 11,188 Test Example 2 (Insecticidal test against house flies) Place a filter paper of the same size at the bottom of a polyethylene cup with a diameter of 6.53, make an emulsion of the test compound according to Formulation Example 1, and dilute it 200 times with water. 500 [1m)0.
7- was dropped onto the filter paper, and 80 lIIP of silica was added uniformly as bait. Release 10 adult female house flies into it.
After 48 hours with the lid on, the 1ζ was examined to see if it was alive or dead, and the mortality rate was determined (2 repetitions). The results are shown in Table 6.

Test Example 8 (Insecticidal test against A. spp.) Strain the test compound in Emulsion I according to Formulation Example 1, dilute it 200 times with water, and add 0. 7- was added to 100-1 ion exchange water (active ingredient concentration 8.5 ppm). Twenty last-instar larvae of A. larvae were released into the larvae, and the mortality rate was investigated after one day. After that, feed until all the untreated areas have emerged, which takes about 8 days.
The birds were reared for one day and the rate of eclosion inhibition was examined.

The effectiveness criteria are (mortality rate) A: 90% or more B: 10% or more but less than 90% C: Less than 10% (Elosion inhibition rate) A: 90% or more B: so% or more but less than 90% C: Less than 80% And so. The results are shown in Table 7.

Table 7 Test Example 5 (Insecticidal test against Spodoptera trifoliata (ζ)) The test compound was made into an emulsion according to Formulation Example 1, and the emulsion was mixed with water for 20 minutes.
Test Example 4 (Insecticidal test against German cockroach) Diameter 5.
A P paper of the same size was placed on the bottom of a polyethylene cup (5001 prn)0. 7 rnl
Drop it onto the furnace paper and use it as bait. Approximately 80 cm of sugar was added. Two male German cockroaches were released into the container, the container was covered with a lid, and 6 days later, their survival and death were determined to determine the mortality rate. The results are shown in Table 8-1.

Table 8. I released 10 4th instar larvae of Spodoptera larvae into it, and 6
After a few days, the insects were examined to see if they were alive or dead, and the mortality rate was determined (2 repetitions).

The results are shown in Table 9.

Table 9 Effects of the Invention> The compound of the present invention has excellent properties as a surfactant, and is particularly effective against Diptera pests such as the house fly, Reticuloptera pests such as the German cockroach, and Lepidoptera pests such as the Japanese flycatcher. It has excellent insecticidal efficacy.

Claims (4)

[Claims] (1) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, m represents an integer from 2 to 10, and q represents an integer from 1 to 6. ] Perfluoroalkyl imidazoline poly(
ethyleneoxy) compound. (2) General formula CF_3(CF_2)_mCONHC_2H_4NH(
C_2H_4O)_qH [where m represents an integer of 2 to 10, and q represents an integer of 1 to 5. ] The method for producing a perfluoroalkylimidazoline poly(ethyleneoxy) compound according to claim 1, characterized in that the acylated N-substituted amido amino alcohol represented by: is subjected to a heating reaction. (3) A surfactant comprising the perfluoroalkylimidazoline poly(ethyleneoxy) compound according to claim 1. (4) An insecticide comprising the perfluoroalkylimidazoline poly(ethyleneoxy) compound according to claim 1 as an active ingredient.