HU202370B - Synergetic composition for killing blatta orientalis population containing propethamphos and hydroprene - Google Patents

Abstract

Insecticidal compsn. comprises propetamphos (I) and hydroprene (II). The (II) may be in racemic form, with (I):(R5)-(II) wt. ratio pref. 1:1-18.7:1, esp. 3.3:1-6.2:1; or (II) may be the (S)-enantiomer, with (I):(S)-(II) wt. ratio pref. 2.6:1-224:1, esp. 7.7:1-41.7:1.

Description

BACKGROUND OF THE INVENTION The present invention relates to a novel pesticidal composition for controlling a cockroach population. More particularly, the present invention provides the active ingredient propetamphospho [chemical name (E) -3 - ([(ethylamino) methoxyphosphinothioyl] oxy} -2-butenoic acid (1-methylethyl) ester] and hydroprene [chemical name]. (2E, 4E) -3,7,11-trimethyl-2,4-dodecadienoic acid diethyl ester] for use in new insecticidal compositions for the control and / or prophylactic control of a squamous bug population.

The synthesis of propetamphos and its use as insecticides are disclosed in U.S. Patent No. 3,758,645.

The synthesis and insect growth control (IGR) properties of hydroprene are described in U.S. Patent 4,021,461. Hydroprene

The carbon at the 7-position is asymmetric and accordingly has R and S enantiomers. In the following, "(R, S) -hydroprene" means a racemate; "(S) -hydroprene" refers to the (S) - (+) - enantiomeric form of hydroprene, while "hydroprene" when used without specifying the enantiomeric content, refers to both (R, S) -hydroprene and refers to (S) -hydroprene.

The composition of the present invention allows for the eradication of the germinal population by administering to the site of the germinal population a combined amount of hydroprene and propetamphos effective to eradicate the germinal population.

The beetle is one of the most difficult to kill insects. This insect is "nocturnal", gathering its food in open spaces at night and finding shelter in hidden places during the day. The life cycle of the whooper beetle begins with eggs which are housed in a shell (called "ootheca"). Eggs turn into larvae in stage I, from which they develop into fully mature swabs in the following larval stages (II) to (VI), about 74 days later. The mature female cockroach lives for about 144 days, during which time it produces six ootheca containing about 40 eggs each; Thus, the reproductive capacity of the population is awesome.

If the three basic necessities - water, food, and hiding place - are sufficiently available, the swabian bug population will multiply in proportion to the geometric power. It is common for a cockroach population to stabilize numerically because one or more of the three basic needs are only available to a limited extent.

There are two possible ways to control the swabian infestation. One is that the cockroach population is repeatedly treated with insecticide. Alternatively, the population is repeatedly treated with an IGR (Insect Growth Controller) substance that interferes with the maturation and fertility of the mite.

It has been observed that if a stabilized population of cockroaches is exposed to stress - for example, by temporarily applying insecticide - and then relieves stress, for example, because the residual effect of the insecticide is unsatisfactory, than the size of the previously stabilized population. This population explosion always occurs when the insecticide loses its toxic effect on marmosets.

This is particularly true in cases where the insecticide does not affect or interfere with the survival of the surviving marmosets.

As a result, when an insecticide is used alone, it has a direct but short-term diminishing effect on the goblin population, since the residual effect of the insecticides on the goblin population generally does not last more than about eight weeks. In addition, due to the high toxicity of insecticides, it is often necessary and advantageous to limit the number of applications and thus prevent the treated areas from endangering human health.

Another option is to treat the insect infected area with an environmentally safe IGR compound such as hydroprene. The disadvantage of treatment with hydroprene or other IGR compounds is that it takes a long time for the insects to act. The reason for this delay is the mode of action of the IGRs. When an IGR-active substance is introduced into the cockroach population, the mature cockroaches are not affected at all, and the immature pupae appear to evolve into mature insects over the subsequent stages of development. However, when exposed to IGRs during the developmental stage of the pupae, mothbirds are irreversibly deformed and physiologically incapable of reproduction. This effect, along with the residual activity of the IGR agents, severely affects the cockroach population, as the viable reproductive insects begin to decline about 4 to 6 months after the application of the IGR agent to the cockroach population.

In a large-scale experiment in which a kitchen-imitating, 28,300-liter, medium-infested swab chamber was sprayed at a single dose of 1.2% (R, S) -hydroprene in a volume of 250 ml / 100 m ² , however, complete eradication was never achieved.

By "insect growth regulator" is meant below a compound that effectively regulates the growth and maturation process of an insect.

"Location of the Swabian Beetle Population" as used herein means areas such as a dwelling, a dwelling house, a restaurant, a house, a store, a theater, office space and office buildings that are infected with a stabilized or unstabilized population of a Swabian bog.

By "eradication of a mothbird population" we mean that the number of mothbirds in the unit under study decreases by a significant percentage. The number of mothbirds that are killed is the number of mothbirds that are acceptable to the inhabitants or users of that unit.

By "patch treatment" as used herein and in the claims, it is meant that the composition is applied in patches or in crevices or gaps, and not in the whole area or in all food collection areas of beetles.

We have found that when IGR-acting hydroprene and insecticidal-acting propetamphos are administered to the cockroach population in combination,

HU 202370 Β, we can achieve safe, fast, complete, long-lasting and effective eradication of the Swabian Beetle population. Surprisingly, the combination of hydroprene and propetamphos as active ingredients and application individually or in combination to the swab insects eliminates the disadvantages (in the case of propetamphos, the short duration of action, in the case of hydroprene, the delayed action after treatment) when used alone. When the two active ingredients are administered in combination to the location of the cockroach population, a significantly greater percentage reduction is achieved than with either the hydroprene or propetamphos alone, and the resulting reduction is greater than when the two active ingredients are administered alone. sum of the effects achieved.

Propetamphos has a moderate to favorable (about 60 days) residual effect. If propetamphosphate is administered alone to the mites infected with mothballs, the number of mothballs will be reduced by approximately 50-60% within a short period (within 1 month). The effect reaches its maximum after about 60 days, then gradually decreases so that after 120 days (4 months) the infection returns to 64-50% depending on the climate and other environmental conditions.

Hydroprene has no insecticidal or direct toxic effect at any stage of the insect's development. As a result, direct application of hydroprene to the swab beetle population does not result in a direct immediate beneficial effect. While mature insects remain intact, immature insects, although at a lower stage of developmental development, develop into infertile mature insects. As a result, the numerical decline of the cockroach population begins approximately six months after hydroprene treatment.

Presumably due to the initial stress state, the number of swallows increases in the first four months after the application of hydroprene, and only after these four months does the gradual decline begin.

It has been found that the combination of hydroprene and propetamphos results in a greater reduction in the cockroach population at the same intervals than would be expected from the addition of their effect.

Accordingly, the present invention relates to a novel insecticidal composition, characterized in that the active ingredient is 1.0-59.7% by weight of (E) -3 - [((ethylamino) methoxyphosphinothioyl) oxy] -2-. butene acid (1-methylethyl) ester (internationally known as propetamphos) and 0.12-7.2% (2E, 4E) -3,7,11-trimethyl-2,4-dodecadienoic acid diethyl ester (internationally) in the form of an oily solution of a butylated hydroxytoluene and butylated hydroxyanisole, an emulsifier, preferably an alkoxylated polyol fatty acid ester, a dispersant, preferably a methylene chloride, low molecular weight hydrocarbons, preferably 1,1,1-trichloroethane, solids, preferably aluminum silicate or silica, adhesives, preferably ethylene glycol and solvents, preferably water.

In practice, the active ingredient propetamphos and hydroprene may be administered either admixed or sequentially, but closely sequentially, one after the other. In the latter case, it is not critical to use the hydroprene formulation or the propetamphos formulation first. For the sake of time and practical reasons, it is preferable to first apply propetamphos in a patch and then immediately treat the entire area with hydroprene, which is delivered in the form of a mist-forming aerosol.

The hydroprene is conveniently administered in the form of a liquid formulation, such as a nebulizer, aerosol or emulsion concentrate. Propetamphos is preferably used in liquid form (e.g. emulsion concentrate) or solid form (wettable powder, granules or dusting agent).

Hydroprene is generally delivered to the habitat of the cockroach population by treating the entire area. The application is preferably effected by misting or aerosolization; the aerosol perfectly covers the insect's food collection area and hiding places. The hydroprene may also be administered in the form of an emulsion concentrate by means of a suitable spray device.

Propetamphetos are usually delivered to the swabian bog population by treatment of the entire area or by patch-like treatment. From a health point of view, spot treatment is beneficial. In both cases, the treatment is carried out in a spray, dusting or aerosol form which allows the insecticide to be applied with careful targeting. Propetamphetos are primarily delivered to hiding places in the cockroaches, such as structures, storage areas, toilets, along plumbing pipes, under and behind cupboards and the like.

The hydroprene is suitably added in an amount of from 1 to 50, preferably from 2 to 36, more preferably from 3 to 30 mg / m ² .

The (RS) -hydoprene is suitably added in an amount of 12 to 50, preferably 18 to 36, more preferably 20 to 30 mg / m ² .

The (S) -hydroprene is suitably added in an amount of 1 to 20, preferably 215, more preferably 3 to 13 mg / m ² .

The propetamdoszt preferably 52 to 224 mg / m ^2, preferably 76 to 148, is administered 100-124 mg / m ² being more preferred.

If necessary, the treatment is repeated, for example 4 months after the first treatment, in equal or smaller amounts. Even after complete eradication of the cockroach population, it is advisable to re-treat with the composition of the invention for prevention.

When the hydroprene and / or propetamphos formulation is in aerosol form, it is usually added in a volume of 250-1000 ml per 100 m ² . When the hydroprene and / or propetamphos formulation is an emulsion concentrate, it is usually added in a volume of 5002000 ml each. The concentration by weight of the composition to be administered will, of course, depend on the volume of application. For example, if 50 mg / m ^{2 is to} be applied, this can be achieved by using a 2% w / w formulation.

A volume of 250 ml is added per 100 msec from a volume of 202370% or a volume of 500 ml per 100 msec is added per 100% w / v.

A mixture of propetamphos and hydroprene can be administered by any suitable means by which the pesticides can be applied, for example by spraying, fogging, dusting, brushing, spraying; however, it is preferred to administer the propetamphos emulsion concentrate in admixture with the hydroprene concentrate.

The application is carried out in whole units, but especially in slits, crevices and patches.

A mixture of propetamphos and hydroprene may be formulated in any convenient form, such as a liquid form such as a ready-to-use form, an aerosol, an emulsion concentrate or a solid form.

A mixture of (R.S) -hydroprene and propetamphos, or a mixture of (S) -hydroprene and propetamphos, is conveniently prepared by admixing a concentrate of propetamphos with a suitable vehicle or technical (diluted, R, S) or (S) -hydrorpene.

The compositions of the invention, either alone or in admixture, may contain adjuvants, diluents, modifiers or conditioners commonly used in the formulation of insecticides, known as "suitable excipients", to form solutions, emulsions, dispersions, powders, and granular compositions. The liquid compositions of the present invention may contain one or more surfactants as conditioners to facilitate easy dispersion of the composition in water or other liquids. By "surfactants" we mean, for example, wetting agents, tackifiers, dispersants and emulsifiers. The solid compositions of the present invention, such as powders, dusts or granular compositions, are prepared using, for example, talc, naturally occurring materials, diatomaceous earth and silica, in particular finely divided silica (such as Hi-Sil).

The amount of active ingredient in the compositions of the present invention will vary with the type of formulation and method of application, but will generally be from about 0.1 to about 20% by weight for propetamphos and from 0.01 to 10% by weight for hydroprene. The propetamphetos are preferably used in a weight ratio of from 1: 1 to 214: 1, preferably from 3.3: 1 to 41.3: 1, relative to the hydroprene. Propetamphetos are generally present in a weight ratio of from about 1: 1 to about 18.7: 1, preferably from 3.3: 1 to 6.2: 1, relative to (R, S) -hydroprene, while propetamphetos are from (S) ) in a weight ratio of from about 224: 1 to about 41.3: 1, preferably from about 7.7: 1 to about 41.3: 1.

The invention is further illustrated by the following non-limiting examples. In the examples, unless otherwise noted, parts are parts by weight and percentages are by weight.

Example 1

Evaluation of the compositions of the invention by testing in buildings

In these experiments, four types of insecticidal agents - hydroprene, propetamphos, dichlorvos, and chlorpyrifos - and combinations thereof were tested in buildings, either alone or in a mixture, for their action against swallows. In this series of tests, in addition to the effects of various insecticides, the methods of application, the frequency of application and the different formulations (serum forms) were evaluated.

Methods

Estimation of the Swabian Beetle population

Test sites and control groups

Suitable residential blocks were selected for the study. A building block with a certain degree of Scabies infection was considered suitable for examination.

Both negative and positive controls were set up during the study. If the study was conducted in flats, the control units were selected in the same array, but in a separate location to prevent insect migration. Units with one part located on one side of a parking space, where the treated group was examined, were the most suitable, while the same number of units with the same structure were located on the other side of the parking space, where the control group was observed.

Particular care was taken to ensure that the blocks were completely separated from each other to avoid insect migration.

The test requirements

The test site was considered suitable if at least 15 swabs were found daily in three traps prior to treatment. If the majority of dwellings in a block were found to be suitable by this criterion, then all dwellings in that block were used to test one type of insecticide. Within one month prior to treatment, the total number of trapped swabs before treatment was determined, and this count was repeated monthly until the end of treatment. Thereafter, the results of each test period were expressed as the mean percentage reduction in the number of insects in all apartments in the single-drug-treated array.

After qualifying the residential blocks, we randomly assigned the blocks to be treated with the various active ingredients and informed all residents by letter explaining what we were doing in their homes.

Observation methods

Each test site was inspected at least one month prior to treatment to determine the extent of swabian infestation prior to treatment. In determining the level of infection before treatment, the method of counting trapped swabs was preferred. In some cases, this counting was supplemented with visual counting. The control groups were controlled in the same way as the treated groups.

HU 202370 Β

Counting insects with a trap

In most cases, three adhesive cockroach traps (usually Black Flag Roach motel *) were placed along with the attractant in the most heavily infected areas of the home; the three traps were kept in the kitchen of each apartment for 24 hours. The traps were placed at: 1) a counter located near the drain; 2) in the cupboard under the drain; and 3) in an area near the refrigerator. These traps were checked monthly at the same sites for 12 months. Trap counts were performed separately for each apartment throughout the study. If only one or two traps were used to determine the extent of pre-treatment infection, only these were checked throughout the study. After a 24-hour control period, the traps were collected and transported to the laboratory for counting.

The traps were allowed to stand for 24 hours and the number of normal mature insects, mature insects and larvae affected by 1GR was determined among the trapped swabs. From this raw data, the percent reduction was calculated using the following formula:

Tg-T,

T _o x 100 - percentage of decrease

In this formula, T _o represents the number of insects before treatment and T ₍ represents the number of insects at 30 i after treatment).

Interpretation of data

The data thus obtained is shown in Figures 2-14 below. Tables are expressed as a percentage reduction in pre-treatment insect count (R%); as a percentage of juvenile hormone-influenced mature insects (IGR) relative to normal mature insects only; as a percentage of mature insects (A) in the total population; and as the percentage of larvae (N) in the total population.

Visual counting

The main insect hiding places, especially their breeding sites, were visually observed and recorded for one month prior to the study period. The same areas were inspected throughout the study, that is, 9 months after application of the test product.

Materials used in the test

A. Propetamphos

Propetamphosphate was applied to selected residential building blocks in a solution prepared by diluting 50% emulsion concentrate (EC formulation) to 1.0% water. This 1.0% solution was applied either by spot spray to cracks and cracks, or by general field treatment according to the instructions on the label of the preparation with a low pressure compressed air operated hand sprayer.

The 50% propetamphos EC formulation was prepared as a tank mix using the following formulation auxiliaries.

Propetamphos 50% Emulsion Concentrate (EC)

components Crowd% Purchase source 90% Technical Propetamphos 56.11 Sandoz Cellosolve (ethylene glycol monoethyl ether 38.89 Union Carbide Sponto®N-140-B (emulsifier) 5.00 Witco

B. Hydroprene

The hydroprene applied to the designated blocks of flats was used in the following forms:

65.7% (R, S) -Hydroprene Emulsion Concentrate (EC) Components Weight% Purchase source 90% Technical (R.S) -hydroprene 74.56 Igepal * CO-630 (surfactant) 25.44 The 65.7% hydroprene EC formulation can be diluted with water. Zoecon GAF

(R, S) -Hydroprene 0.6% Concentrate A for fogging

Components T Omega% Purchase source 95.03% (R.S) -hydroprene 0.66 Zoecon Dichloromethane (stabilized, aerosol grade) 16.34 Commodity 1,1,1-Trichloroethane (stabilized, aerosol quality) 55.00 Commodity

HU 202370 Β (R.S) -Hydroprene 0.6% Concentrate B for fogging

components Crowd% Purchase source 95.03% (R.S) -hydroprene 0.89 Zoecon Dichloromethane (stabilized, aerosol grade) 22.72 Dow 1,1,1-Trichloroethane (stabilized, aerosol quality) 76.39 Dow 0.6% (R, S) -hydroprene "A" nebulizer components Crowd% Purchase spinning 15% production hydroprene concentrate * 4.81 Zoecon Dichloromethane (stabilized, aerosol grade) 12.91 Dow 1,1,1-Trichloroethane (stabilized, aerosol quality) 55.0 Dow Propellant A-70 28.0 Commodity

* The manufacturing hydroprene concentrate is a 15% solution of technical hydroprene in dichloromethane.

0.6% (R.S) -hydroprene "B" nebulizer components Crowd% Purchase form (R.S) -Hydroprene 0.6% mist B-A-70 propellant (hydrocarbon propellant) concentrate 72.0 28.0 Zoecon Commodity

Concentrate "A" of (R, S) -hydroprene 1.2% mist-forming agent

components Crowd% Purchase source 95.03% (R.S) -hydroprene 1.28 Zoecon Aerothene * MM 15.72 Commodity Aerothene * TT 55.00 Commodity

Concentrate B of (R.S) -Hydroprene 1.2% mist-forming B

components Crowd% Purchase source 95.03% (R.S) -hydroprene 1.8 Zoecon Dichloromethane (stabilized, aerosol grade) 21.8 Dow 1,1,1-Trichloroethane (stabilized, aerosol grade) 76.4 Dow (R.S) -hydroprene nebulizer components Crowd% Purchase source (R.S) -Hydroprene is a 1.2% fogging concentrate 72 Zoecon Propellant A-70 28 Commodity

0.6% (RS) -hydroprene aerosol The 0.6% (RS) -hydroprene aerosol is prepared as a 0.6% (RS) -hydroprene nebulizer and with a 0.05 cm aerosol dispenser 01-5018 (rather than a button on the mist generator).

(S) -Hydroprene 9.0% emulsion concentrate

components Crowd% Purchase source 91.0% technical (S) -hydroprene 10.09 Zoecon Tenox®4 [1] is an antioxidant 0.50 Eastman Atlox®847 [2] emulsifier 19.03 ICI Atlox®3404F [3] emulsifier 11.42 ICI Isopar®M [4] solvent 58.96 Exxon

HU 202370 Β [1] antioxidant; corn oil, a solution containing BHT (butylated hydroxytoluene) and BHA (butylated hydroxyanisole).

[2] Emulsifier; alkoxylated polyol fatty acid ester.

[3] Emulsifier; is a proprietary mixture of nonionic and ionic emulsifiers.

[4] Solvent; isoparaffinic in nature.

0.3% (S) -hydroprene nebulizer

components Crowd% Purchase source 91.0% technical (S) -hydroprene 0.40 Zoecon Dichloromethane (stabilized, aerosol grade) 16.55 Dow 1,1,1-Trichloroethane (stabilized, aerosol quality) 55.00 Dow Propellant A-70 28.00 Commodity ΒΗΤ-antioxidant (butylated hydroxytoluene) 0.05 Eastman

0.3% (S) -hydroprene aerosol 0.3% (S) -hydroprene aerosol is prepared as 0.3% (S) -hydroprene nebulizer, with the difference to be equipped with a manually operated aerosol dispenser attachment.

C. Mixtures of hydroprene-propetamphos

1. Tank mixes

Formulations containing hydroprene and propetamphos are prepared by mixing 65.7% by weight of a hydroprene EC formulation with a 50% propetamphos EC formulation in a water tank immediately before use. The EC tank mix to be used is dispensed according to the instructions for applying propetamphos.

2. Combination preparations

EC preparation containing 59.7% by weight of propetamphos and 7.2% by weight of (R, S) -hydroprene

components Crowd% Purchase source 90% Technical Propetamphos 76.2 Sandoz 94% technical (R.S) -hydroprene 6.5 Zoecon Tenox®4 (Antioxidant) 0.7 Eastman Atlox®3406F (emulsifier) 11.6 ICI Atlox * 3409 (emulsifier) 5.0 ICI

This composition is particularly advantageous for application to slits and crevices in the presence of whorl.

Aerosol formulation (propellant) containing propetamphos and (R, S) -hydroprene

components Crowd% Purchase source technical propetamphos 1.20 Sandoz (R, S) -Hydroprene, 15% manufacturing concentrate 4.81 Zoecon Dichloromethane 10.99 Dow 1,1,1-Trichloroethane 55.00 Dow A-46 Propellant 25.00 Commodity

This formulation is particularly advantageous for application to crevices and crevices of the site. Solid preparation containing propetamphos and (R.S) -hydroprene

components Crowd% Purchase source 90% Technical Propetamphos 1.33 Sandoz 88% technical (R.S) -hydroprene 0.14 Zoecon Barden * AG-l (Aluminum Silicate) 88.53 Commodity Hi-Sil®233 (Hard Acid) 5.00 Commodity ethylene glycol 5.00 Commodity

HU 202370 Β

Ready-to-use formulation containing propetamphos and (R.S) -hydro- prene

components Crowd% Purchase source 90% Technical Propetamphos 1.23 Sandoz 90% technical (R.S) -hydroprene 0.36 Zoecon Sponto®AK 31-568 0.40 Witco Sponto®AK 31-56A 1.60 Witco Water 94.58 Commodity Xylene (aromatic solvent grade) 1.00 Commodity BHT 0.44 Commodity Colloid 643 0.02 Commodity Ethylenediaminetetraacetic acid tetrasodium 0.2 Commodity Citric acid 0.1 Commodity Dowicil®75 (stabilizer) 0.07 Dow

EC preparation containing (S) -hydroprene and 59.7% propetamphos Components Weight% Purchase source 89% Technical Propetamphos 68.42 Sandoz 91% Technical (S) -hydroprene 4.75 Zoecon BHT (antioxidant) 5.00 Eastman Atlox® 3406F-XF (Trade Mark Mixture of Emulsifiers) 15.27 ICI Atlox® 3409F-XF (Trade Mark Mixture of Emulsifiers) 6.56 ICI

The hydroprene nebulizer was used in containers of approximately 140 ml and treated at 250 ml per 100 m ² of area. (RS) -hydroprene was used in the nebulizer at a concentration of 1.2% or 0.6% by weight, and (S) -hydroprene in a concentration of 0.3 to 40% by weight. At least one nebuliser was placed in the kitchen and bathroom of each unit, and the other nebulizers were placed elsewhere in the unit as needed. All cabinets and drawers were cleaned and left open to allow the fog to come in contact with the largest possible area.

The (RS) -hydroprene aerosol was placed in containers of approximately 140 mL in space at a concentration of 0.6% and delivered in an amount of 2.5 mL per 100 m ² . The aerosol is applied to cabinets, drawers, other furnishings and kitchens, as well as to the bathroom, to every possible hiding place for swabs.

During the entire study period, the trapping count was performed monthly as before treatment. In some of our studies, hydroprene and / or propetamphos were re-applied 3, 4 or 6 months after the first application. The percentage reduction was calculated using the formula used to evaluate the insect population described above. These studies were conducted over a period of 11 months.

Table 1 shows the effect of propetamphos alone, (R, S) -hydroprene alone, and different formulations containing mixtures of the two active substances on the Blatella germanica population of swabs in a unit infected with swabs for 9 months. To determine efficacy, the number of insects after treatment was compared to the number before treatment and expressed as a percentage of decrease or increase in the number of insects. The number of swabs before treatment corresponds to a 0% reduction.

In the following examples and tables, the following formulations were used (% symbol means% by weight):

H / P mixture: 1.0% solution in 50% propetamphos EC, 0.12% in 65.7% (R, S) -hydroprene EC and water fuel mixture;

"H / P combination" means treatment using a 1% solution of 0.6% (R.S) -hydroprene nebulizer and 50% propetamphos EC;

"(R, S) -hydroprene 0.12% EC" means a 0.12% solution of 65.7% (R, S) -hydroprene EC in water;

"Propetamphos 1.0% EC": 1.0% solution in water of 50% propetamphos EC.

HU 202370 Β

Table 1

Percentage reduction in the number of formulations used (number of dwellings treated) and the number of whorls

(R.S) -hydroprene EC 0.12% Number of dwellings (R.S) -hydroprene 0.6% mist-forming (20) Propetamphos EC 1% (16) H / P mixture EC 0.12 / 1% (19) H / P combination H-mist generator / P-EC (15) (16) Month 0 0% 0% 0% 0% 0% 1 -69% -33% 53% 78% 89% 2 -77% 21% 80% 75% 94% 3 -18% - 78% 80% 97% R 4 -56% - 61% R 88% R 95% 5 stopped - 67% 90% 96% 6 71% 22% 95% 97% 7 quenched quenched - - 8 94% 97% 9 99% 100%

R stands for repeated treatment with the same active ingredient

Table 1 shows that a mixture of propetamphos and (RS) -hydroprene in the form of an emulsion concentrate (H / P mixture) and a combination of the (R, S) -hydroprene nebulizer and the propetamphos emulsion concentrate ( H / P combination) are much more effective than either propetamphos alone or (RS) -hydroprene alone. The residual and toxic effects of both the H / P mixture and the H / P combination are enhanced. In addition, at 4 months after application of the H / P mixture, 89% of the surviving mature swabs are "IGR-influenced mature insects", i.e. abnormal and sterile swabs.

Treatment with propetamphos alone reduced the cockroach population by 80% in the second month, but from month 3, the propetamphos-induced decline began to slowly abate, and by month 6, the reduction was only 22% relative to the original number of cockroaches. did. Surviving normal mature swabs were always able to reproduce and were thus able to restore polulation shortly after residual levels were reduced to pre-treatment levels.

If the cockroach population was treated with (R, S) -hydroprene EC alone, 4-6 after treatment. (a) the cockroach population has increased by approximately 56% during the month; however, these swallows were abnormal, i.e., mature IGR insects, unable to reproduce.

Example 2

2-11. the results of our investigations in other buildings are presented in tables. In these tables: "% R" means the percentage reduction in the number of insects before treatment; "IGR" means the percentage of mature insects affected by the juvenile hormone relative to normal mature insects; "N" represents the percentage of larvae in the total population; "A" represents the percentage of mature insects in the total population.

A. Fairfield Inn flats were treated with 1.2% (R, S) hydroprene mist generator, 0.6% (R, S) -hydroprene aerosol and 1% propetamphos EC. We managed a total of 34 apartments. Our results are summarized in Table 2.

Table 2

Results from management of Fairfield homes

Pre-treatment insect count

At the beginning, 986

Percent decrease after treatment

% R IGR N In month 0 0 0 64 In the 1st month 71 52 50 In the 2nd month 78 84 43 In the 3rd month 86 77 34 In the 4th month 91 93 37 In the 5th month 95 92 27 In the 6th month 90 93 26 In the 7th month - - - In the 8th month 94 93 22 In the 9th month - - - In the 10th month - - - In the 11th month 100 0 100

B. The "Willows" flats were treated with 0.6% (R.S) -hydroprene nebulizer, 0.6% (R, S) -hydroprene aerosol and 1% propetamphos EC. The hydroprene treatment was repeated 4 months after the first treatment. Erosion was sprayed in the kitchen area, in the bathroom and in the toilet. A single nebulizer was then placed in the center of the room. Propetamphos was applied in a patch-like fashion. We managed a total of 24 apartments. Our results are summarized in Table 3.

HU 202370 Β

Table 3

Results from treatment of Willows homes

Pre-treatment insect count

At the start time 885

Percent decrease after treatment

THE 0th month 0 0 0 The First month 59 48 69 THE Second month 72 80 55 THE Third month 82 81 50 THE 4th month 85 87 45 The 5th month 92 89 40 THE 6th month 95 97 28 THE 7th month - - - THE 8th month 98 83 14 THE 11th month 99 75 0

C. Northwood Homes are government-assisted housing units with 2-4 bedrooms and 1-2 bathrooms. The 1.0% propetamphos EC formulation was tested in a group of 20 such apartments without (R.S) -hydroprene. Application was carried out with an average of about 1 liter of solution per apartment according to the directions for use indicated on the label of the preparation. The percentage decrease was highest at day 2, reaching 80% at that time, and then decreased to repeat treatment on heat day 4. In no case did the reduction rate reach the values obtained with the various treatments with (R, S) -hydroprene and propetamphos. The percentage reduction in propetamphet-treated dwellings deteriorated from month 9 onwards, so we were repeatedly treated with hydroprene and propetamphos. In Nothwood flats, the last treatment was done with a tank mix of 0.12% (R.S) -hydroprene EC and 1.0% propetamphos EC and applied according to the instructions given for propetamphos. For this purpose we used a 4.5 liter B and G type compressed air sprayer as well as a propetamphos EC application. This treatment resulted in moderately favorable control at baseline and led to a 99% reduction at month 9 after repeated treatment at month 4. The number of dwellings involved in each treatment is given in brackets.

Table 4

Results of treatment of Northwood homes (20) with 1% propetamphos EC

Pre - treatment insect count At initial time 290

Percent decrease after treatment % R IGR N In month 0 0 0 0 In the 1st month 53 1 45 In the 2nd month 80 0 50

Percentage decrease after treatment% R IGR N

THE 3 months 78 10 67 THE 4 months (repeated treatment) 61 7 60 The 5 months 67 2 57 THE 6 months 22 7 70 THE 8 months 77 17 66

Table 5

Results of treatment of Northwood homes (18) with 0.6% (R, S) -hydroprene mist generator and aerosol and 1% propetamphos EC

Insect count before treatment

At the initial time 641

Percentage decrease after treatment% R IGR N

THE 0 months 0 0 0 The 1st month 91 56 34 THE 2 months 96 71 26 THE 3 months 97 64 22 THE 4 months (repeated treatment) 99 75 50 The 5 months 99 33 40 THE 6 months 98 14 50 THE 7 months - - - THE 8 months 99 50 0 THE 9 months 100 100 0

Table 6

Results of treatment of Northwood homes (16) with 0.6% (R, S) -hydroprene aerosol and 1% propetamphos EC

Pre-treatment insect count

At the initial time 773 Percent reduction treatment after % R IGR N In month 0 0 0 0 In the 1st month 88 68 38 In the 2nd month 88 75 46 In the 3rd month 84 83 47 In the 4th month (repeated treatment) 82 83 53 In the 5th month 87 96 54 In the 6th month 90 85 29 In the 8th month 96 80 11 In the 9th month 99 100 33

Table 7

Results of treatment of Northwood homes (16) with 0.6% (R, S) -hydroprene mist generator and 1% propetamphos EC

Pre-treatment insect count

At the outset 593

-101

HU 202370 Β

< Percent decrease after treatment % R IGR N In month 0 0 0 0 In the 1st month 89 44 43 In the 2nd month 94 64 35 In the 3rd month 97 58 25 In the 4th month 95 79 32 In the 5th month 96 59 26 In the 6th month 97 67 37 In the 7th month - - - In the 8th month 97 50 48 In the 9th month 100 100 50

Table 8

Results of treatment of Northwood homes (16) with a mixture of 0.12% (R, S) Hydroprene EC and 1% Propetamphos EC

Pre-treatment insect count

At the initial time 1004

Percent decrease after treatment

% R IGR N In month 0 0 0 0 In the 1st month 78 51 42 In the 2nd month 75 58 47 In the 3rd month 80 94 36 In the 4th month 88 89 19 In the 5th month 90 94 8 In the 6th month 95 95 15 In the 8th month 94 83 21 In the 9th month 99 83 25

D. Half of the Chateau flats were treated with 0.5% ready-to-use chlorpyrifos from Mr. Scott's (see Table 10). Chlorpyrifos (international name) is chemically Ο, Ο-diethyl O- (3,5,6-trichloro-2-pyridinyl) phosphorothioate (see U.S. Patent No. 3,244,586). The other half of the flats were treated with 250 ml / 100 m ² of 0.6% (R, S) -hydroprene nebulizer and 0.6% (R, S) -hydroprene aerosol from a 5 liter tank, which were used in kitchens and bathrooms (see Table 9).

Our results show that both populations under study are growing at a slower rate in (R.S) -hydroprene-treated homes. Chlorpyrifos treatment was terminated at the end of month 6 for various reasons and these apartments were excluded from the study and then repeatedly treated with hydroprene and propetamphos. In this study 10 apartments were treated.

Table 9

Results of treatment of "Chateau" flats with 0.6% (R.S) -hydroprene mist generator and 0.6% aerosol and 0.5% chlorpyrifos formulation

Pre-treatment insect count

At the beginning 127

Percentage decrease after treatment% R IGR N

In month 0 0 0 0 In the 1st month -218 58 65 In the 2nd month -172 71 72 In the 3rd month -164 69 65 In the 4th month - - In the 5th month - - - In the 6th month -87 26 52

Table 10

Results of treatment of "Chateau" flats with 0.5% chlorpyrifos

Pre-treatment insect count

At the outset 103

Percentage decrease after treatment% R IGR N

In month 0 0 0 0 In the 1st month -242 36 73 In the 2nd month -561 45 73 In the 3rd month -451 57 72 In the 4th month - - - In the 5th month - - - In the 6th month -287 17 65

Example 3

In the manner and procedure described in Examples 1 and 2, two buildings which consisted of "Whitsonian" dwellings were treated. Treatments were performed as follows.

Building 1 (13 dwellings) and Building 5 (8 dwellings) were initially treated with 59.7% propetamphos EC and 7.2% (R, S) -hydroprene EC.

Building 1 was repeatedly treated at 6 months with 59.7% propetamphos EC and 7.2% (R, S) -hydroprene EC.

Building 5 was repeatedly treated at 6 months with 59.7% propetamphos EC and 3.6% (S) -hydroprene EC.

All. The results reported in Table I show that the cockroach population has decreased remarkably and continuously for 10 months and that by the 9th month, the (S) -hydroprene treated flats have completed the eradication.

Table 11

Results achieved with Whitsonian housing management

In Building 1 In Building 5

Pre-treatment insect count 999,252

Percentage decrease after treatment% R IGR% N% R IGR% N

In month 0 0 0 69 0 0 54 In the 2nd month 46 67 48 55 73 54 In the 3rd month 58 62 29 55 83 39 In the 4th month 80 79 31 84 83 44

-111

HU 202370 Β

Percentage decrease after treatment% R IGR% N% R IGR% N

Re-treatment at 6 months

Month 7 86 39 45 98 20 17

In the 8th month, 89 56 47 98 50 60

In the 9th month 93 56 49 100 0 0

In the 10th month 95 59 27 100 0 0

Example 4

In the manner and procedure described in Examples 1 and 2, patches were applied with 1% propetamphos EC, followed by treatment of the entire area with hydroprene EC or 0.6% hydroprene nebulizer concentrate or 0, With 6% hydroprene nebulizer or 1.2% hydroprene nebulizer concentrate or 1.2% hydroprene nebulizer or 0.6% hydroprene aerosol to eradicate the cockroach population.

The composition of the formulations used in this example is given in Example 1.

Example 5

Following the procedure and method described in Examples 1 and 2, general area treatment was performed with 1% propetamphos EC, followed by general area treatment with hydroprene EC or 0.6% hydroprene fogging concentrate or 0.6% by weight. Hydroprene Nebulizer or 1.2% Hydroprene Nebulizer Concentrate or 1.2% Hydroprene Nebulizer or 0.6% Hydroprene Nebulizer to Exterminate Swab Beetle Population.

The composition of the formulations used in this example is given in Example 1.

Claims (7)

PATENT CLAIMS Claims 1. A synergistic composition for controlling a cockroach population, characterized in that the active ingredient is 1.0- 59.7% by weight of (E) -3 - [(ethylamino) methoxyphosphinothioyl} oxy] -2-butenoic acid (1-methylethyl) ester and 0.12-7.2 by weight of (2E, 4E) -3.7,11-trimethyl-2,4-dodecadienoic acid diethyl ester, and from 98.88 to 33.1% by weight of carrier and excipients such as antioxidants, preferably butylated hydroxytoluene and butylated hydroxy anisole in oil, emulsifier, preferably alkoxylated polyol fatty acid esters, dispersants, preferably methylene chloride, propellant, preferably low molecular weight hydrocarbons, preferably 1,1,1-trichloroethane, solids, preferably aluminum silicate, or silica, excipients, preferably ethylene glycol, and solvents, preferably water. Composition according to claim 1, characterized in that the hydroprene is in racemic form. Composition according to claim 2, characterized in that the propetamphos is present in a weight ratio of from 1: 1 to 18.7 with respect to (R.S) -hydroprene. Composition according to claim 3, characterized in that the propetamphos is present in a weight ratio of 3.3: 1 to 6.2: 1 in relation to (R, S) -hydroprene. Composition according to claim 1, characterized in that the hydroprene is in the form of its (S) -enantiomer. 6. A composition according to claim 5, wherein the propetamphos is present in a weight ratio of from 2.6: 1 to 224: 1 relative to (S) -hydroprene. 7. The composition of claim 6, wherein the propetamphos is present in a weight ratio of 7.7: 1 to 41.7: 1 relative to (S) -hydroprene.