RU2111664C1 - Insecticidal composition - Google Patents

Abstract

FIELD: organic chemistry; insecticides for control of household pests. SUBSTANCE: composition comprises, wt.-%: permetrin, carbophos or phenthione, 0.1-1.0; polyethylene glycol monooleate with 5-7 ethylene oxide units, 0.5-1.5; flavor additive and foamed of filtering pearlite, the balance. Composition has higher chemical stability as compared to analogue. EFFECT: higher biological activity. 9 tbl

Description

а в качестве фосфорорганических соединений - карбофос(малатион)- [0,0-диметил-S-(1,2-дикарбэтоксиэтил)]дитиофосфат формулы

или фентион-[0,0-диметил-0-(3-метил-4-меркаптофенил)]тиофосфат формулы

Известно, что синтетические пиретроиды, в том числе и перметрин, разлагаются при хранении, особенно под действием окислителей или УФ-излучения. Поэтому для повышения эффективности и продолжительности их действия в препаративные формы обычно добавляют синергисты, наиболее известным из которых является пиперонилбутоксид, антиоксиданты, например бутилокситолуол, трет-бутилгидрохинон, бутилоксианизол и др. , а также вещества, являющиеся абсорберами УФ-излучения, например октилдиметиламинобензоат и др. (патент США N 4668666).The invention relates to solid preparative forms of insecticides for controlling domestic (synanthropic) insects. More specifically, the invention relates to a preparation containing, as an active ingredient, a mixture of synthetic pyrethroids and organophosphorus compounds, with permethrin-3-phenoxyphenylmethyl-3- (2,2-dichloroethenyl) -2,2-dimethylcyclopropanecarboxylate of the formula being used as a synthetic pyrethride

and as organophosphorus compounds, karbofos (malathion) - [0,0-dimethyl-S- (1,2-dicarbethoxyethyl)] dithiophosphate of the formula

or fenthion- [0,0-dimethyl-0- (3-methyl-4-mercaptophenyl)] thiophosphate of the formula

Synthetic pyrethroids, including permethrin, are known to decompose upon storage, especially under the influence of oxidizing agents or UV radiation. Therefore, to increase the effectiveness and duration of their action, synergists are usually added to the formulations, the most famous of which are piperonyl butoxide, antioxidants, such as butyloxytoluene, tert-butyl hydroquinone, butyloxy anisole, etc., as well as substances that are absorbers of UV radiation, for example octyldimethylaminobenzoate and others . (US patent N 4668666).

 Various stabilizers are also used to prevent the decomposition of synthetic pyrethroids and increase the duration of their action, for example, polydimethylsiloxanes, tetramethyltetraphenylsiloxane and other liquid siloxane polymers (US Pat. No. 4,668,666), as well as oils containing linoleic acid, tall oil and tung oil containing conjugated double bonds (US Pat. U.S. N 4677117).

 The stabilizing effect on synthetic pyrethroids of certain phosphoric acid esters has also been established (EP 0313433).

 Organophosphorus components of the claimed composition also decompose under the action of acidic or alkaline agents or catalysts contained in fillers of solid formulations or the environment, and this applies more to karbofos than to fenthion (Melnikov N.N. Chemistry and technology of pesticides, 1974 .).

 For the stabilization of organophosphorus pesticides, including karbofos, various additives are used depending on the carriers used, such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol (US Pat. No. 2,927,882), ethyl silicate, thiourea (US Pat. No. 2,967,127), US Pat. N 3062709), low-volatile petroleum oils (US patent N 3390048), polyoxyethylated amines (DE N 3103774).

US Pat. No. 4,861,762 describes an insecticidal composition based on malathion or diazinone, containing as a synergistic additive olefinic acid or a mixture thereof with linoleic acid or Na, K, NH ₄ salts. The drug is used to combat leaf-eating insects.

 Insecticidal compositions containing mixtures of synthetic pyrethroids and organophosphorus compounds as active ingredients are used quite widely, since such compositions are often more effective than formulations based on individual compounds, and their use is cheaper and easier. It has also been found that phosphoric acid esters inhibit certain variants of enzymes that cause the metabolism of pyrethroids (EP N 0317433).

 For some species of insects, synergism was determined using a mixture of permethrin and malathion (DE N 2757769).

 In European patent N 304492 described stabilized solid pesticidal compositions based on a mixture of synthetic pyrethroids, such as cypermethrin, fenvalerate, etc., and organophosphorus pesticides, including malathion and fenthion. As stabilizing agents, alkali or alkaline earth salts of weak acids are used, such as carbonic, acetic, silicic, phosphoric, boric, for example calcium carbonate, sodium tripolyphosphate and others.

 The closest to the invention in terms of technical nature and the achieved effect are insecticidal compositions based on a mixture of permethrin and karbofos (malkord) and a mixture of permethrin and fenthion (bifentrin). In addition to the active substances, these compositions include fillers, a solvent and functional additives, lubricants, stabilizers, as well as perfumes to eliminate the specific unpleasant odor of organophosphorus compounds.

 The following are the compositions of the formulations in the form of dusts of mulkord and bifentrin-II in accordance with current standards.

Malkord (TU 113-04-57-003-93), wt.%:
Permethrim, active ingredient - 0.25
Karbofos, active ingredient - 0.25
Isopropyl alcohol, solvent - 1.0
Fragrance (to eliminate the smell of malathion) - 0.5
Polymethylsiloxane liquid or phenyl-triethylhexosilane or industrial oil, sizing, stabilizer - 2.0
Talc or talc magnesite - up to 100
Bifentrin-II (TU-400-19175-151-95)
Permethrim, active substance - 0.5 ± 0.05
Fenthion, active substance - 1.5 ± 0.15
Fragrance to eliminate odor - 0.5
Boric acid, active substance and stabilizer - 0.10 ± 0.1
Vaseline oil, sizing - 1.0 ± 0.1
Talc or talc magnesite - up to 100
Malkord and bifentrin-II are effective in combating household insects such as cockroaches, fleas, flies, bugs (A Handbook of Drugs Allowed for Use in Medical Disinfestation. Edited by Academician of the Russian Academy of Medical Sciences M.G. Shandaly, Tyumen, 1995) .

 However, both drugs are not stable enough during storage and quickly lose their insecticidal activity due to the decomposition of the active substances contained in them. Since the degree of decomposition of kalbofos in an industrial sample during natural storage for 30 days is 40 wt.%, Fenthion is more stable and its degree of decomposition under various storage conditions does not exceed 8 - 9 wt.%.

 Permethrin also decomposes under the influence of sunlight and other factors (see tab. 3, 4).

In accordance with the invention, an increase in stability and an increase in the insecticidal activity of dusts based on a mixture of permethrin with karbofos or fenthion is achieved by introducing polyethylene glycol monooleate, the structure of which is expressed by the formula: C ₁₇ H ₃₃ COO (C ₂ H ₄ O) _m H, where m = 5 or 7. These compounds are conventionally called Oleox-5 or Oleox-7 (TU 6-14-314-75) and are known as emulsifiers, dispersants, additives to detergents and cleansing compositions and to important agents in the textile industry. Previously, Oleox-5 and Oleox-7 were not used as functional additives to pesticides.

 At the same time, it was found that Oleoks-5 and Oleoks-7 are more effective if expanded perlite or a variety of perlite filter powder (GOST 10832-91 and TU 21-31-44-82) obtained from volcanic silicate is used as an inert filler origin by crushing and heat treatment (see N.N. Kolyanov, A.N. Muzlyak. Vermiculite and perlite. Moscow, 1961).

For the preparation of dusts, perlite of grades 100 and 150 is used (bulk density up to 150 g / dm ³ ).

 Introduction to the formulation of Oleox-5 or Oleox-7 dusts in combination with perlite instead of all functional additives (stabilizers, lubricants) and talc or talc magnesite, which are part of mulcord and bifentrin, increases the stability of the active substances and increases the duration and effectiveness of their insecticidal action, reduce expenditure rates of drugs. Perhaps this result is achieved not only due to the stabilizing effect of oleoxes on active substances, but also as a result of synergism arising from the combined use of oleox with these active substances. In the formulation with fenthion, for example, the need for the use of boric acid, which is an insecticide with a long residual effect for controlling cockroaches, is eliminated.

 To improve consumer properties, the fragrance, which is a multicomponent mixture of synthetic aromatic substances and essential oils, is introduced into the insecticidal composition as well as in the composition of mulcord and bifentrin-II.

 Example 1. Obtaining dusts based on a mixture of permethrin and karbofos or fenthion.

At a temperature of 35 - 40 ^o C are mixed in predetermined mass ratios Oleox-5 or Oleox-7, karbofos or fenthion, perfume and pre-heated to a temperature of 45 - 50 ^o C permethrin. The resulting mixture of active substances and functional additives (in a given mass ratio) is applied to the expanded perlite or sand with a perlite filter using mechanical nozzles. The process is carried out in a paddle mixer at a temperature of 35 - 40 ^o C.

Thus, the compositions of combined dusts based on:
permethrin and karbofos - D-1, D-2, D-3 and as a reference sample D-4 (without Oleox-5),
permethrin and fenthion - SF-1, SF-2, SF-3 and as a reference sample SF-4 (without Oleox-7).

 Compositions D-5 and SF-5 containing Oleox-5 and Oletx-7, as well as talc and talc magnesite, as fillers, were obtained in a similar manner.

 The components included in these compositions and their ratios are given in table. 1 and 2.

 The properties of the obtained compositions, the stability of the active substances during natural and artificial storage, the degree of decomposition under the influence of UV light in comparison with the standards D-4, D-5 and SF-4, SF-5 and dust samples Malkord and Bifentrin-II are given in tab. 3 and 4.

 As can be seen from the table. 3 and 4, the proposed compositions are stable during storage and under the influence of UV light, which is achieved by the introduction of Oleox-5 or Oleox-7 and an inert filler — expanded perlite sand or filter perlite.

 Example 2. Determination of insecticidal activity of dusts based on a combination of permethrin and karbofos (or fenthion) in the fight against red cockroaches.

 The biological activity of dusts was studied on red cockroaches (BI. Germanica) insect breeding NIIPTiD. The method of forced contact was used to determine the acute insecticidal activity of dusts and their residual effect.

On the surface of plywood 10 x 20 cm in size evenly applied with a brush dusts at the rate of 1, 2, 3, 5, 10 g / m ² . The cockroaches were contacted in Nabokov-Laryukhin exposure meters for 30 s. In the experiment, 30 insects were used. At the same time, control experiments were carried out in which pure filler sand, expanded perlite sand and talc were used to evaluate the insecticidal effect of dusts Malkord and Bifentrin. Each experiment was carried out in 5-fold repetition at an air temperature of 23 ± 2 ^o C and a relative humidity of 60 ± 5%.

 After contacting the insects were transferred to clean containers with food and water. The results were taken into account 15 minutes after contact and the percentage of death was determined.

 The duration of the insecticidal effect of dusts was studied on plywood surfaces measuring 10 x 20 cm. The surfaces were treated with minimal doses of dusts, which, when determining acute toxicity, provided 100% death of cockroaches 15 minutes after 30-second contact. Treated plates were stored indoors at room temperature in a horizontal position under diffused light. The cockroaches were in contact with the surfaces treated with dusts for the first time 24 hours after applying the dust, then after 5 days and then once every 5 days until the time when the number of dead cockroaches was less than 50%. Contact of insects was carried out for 30 days each time either with the surfaces of a new plate, or with the surface of the same plate in the same places where cockroaches had not previously been in contact. Analysis was carried out 24 hours after contact.

 Acute insecticidal activity and residual effect of dusts based on a combination of permethrin and karbofos, permethrin and fenthion, reference samples, dust malkord and bifentrin against red cockroaches are given in table. 5, 6, 7, 8.

 A study of the acute insecticidal activity of dusts based on a combination of permethrin and karbofos, permethrin and fenthion against red cockroaches (see Tables 5 and 7) showed that the dust formulation containing Oleox-5 or Oleox-7 (formulations: D-1, D -2, D-3 and SF-1, SF-2, SF-3) are significantly more effective than dusts D-4 and SF-4, which do not contain the above components, and the well-known dusts Malkord and Bifentrin-II.

The same results are observed when studying the residual insecticidal effect of the claimed compounds in relation to red cockroaches (see tables. 6 and 8) even at lower consumption rates for the sum of AI 1 m ² than the standards and dusts of Malkord and Bifentrin-II.

 Example 3. Determination of the insecticidal activity of dusts on rat fleas (Xenopsylla cheopis) and bed bugs (Cimex lectulavius) of insect dilution NIIPTiD.

Samples of unpainted plywood 10 x 20 cm in size were treated with dusts, evenly distributing them over the surface, at a flow rate of 0.5 and 1.0 g / m ² .

 The contacting of insects was carried out for 30 s and 5 min. The experiment was set simultaneously in three surfaces. In each repetition of the experiment, 30 insects were used. Each experiment was accompanied by control in triplicate.

 After contacting the insects were transferred to clean vessels: bed bugs in test tubes with filter paper in the form of an accordion, fleas were transplanted into glasses with sand, which were tied over with cloths moistened with water.

The experiments were carried out at an air temperature of 21 ± 2 ^o C and a relative humidity of 66 ± 3%. Results were recorded after 24 hours. When taking into account the results of the experiment, the number of live, paralyzed and dead insects was calculated. The death of insects in the experiment was calculated as a percentage in relation to the control.

 The results of determining the insecticidal activity of dusts against rat fleas are shown in tables 7 and 9.

 From the above results it can be seen that dusts containing Oleox-5 or Oleox-7 (compositions: D-1, D-2, D-3, and SF-1, SF-2, SF-3) are much more effective than D- 4 and SF-4, which do not contain the above components, and the known dusts Malkord and Bifentrin-II.

Claims (1)

An insecticidal composition comprising permethrin and karbofos or fenthion as an active ingredient, as well as functional additives, an inert carrier, perfume, characterized in that it contains a polyethylene glycol monooleate of the formula as a functional additive
C ₁₇ H ₃₃ COO (C ₂ H ₄ O) _m H,
where m = 5 and / or 7 (Oleox 5 or Oleox 7),
and as an inert carrier, expanded perlite or filter perlite powder in the following ratio of components, wt.%:
Permethrin - 0.1 - 1.0
Karbofos or fenthion - 0.1 - 1.0
Polyethylene glycol monooleate - 0.5 - 1.5
Fragrance - 0.2 - 0.8
Expanded perlite or perlite filter powder - Up to 100s

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