NOVEL COMPOSITION AND METHOD OF CONTROLLING OF COCKROACH POPULATION

Abstract: Insecticidal composition comprising propetamphos and hydroprene is useful for safe, fast, complete and long lasting control of cockroach populations. A method for control of the cockroach population comprises an administration of the novel composition to the locus of the cockroach population. Both hydroprene and propetamphos are administered in an effective, cockroach population controlling amount.

Description: NOVEL COMPOSITION AND METHOD OF CONTROLLING OF COCKROACH POPULATION This invention concerns insecticidal compositions comprising propetamphos and hydroprene. The novel compositions are useful for control of cockroach population and/or for prophylactic protection against cockroach infestation. "Propetamphos" as used herein is the common name for (E)-l-methylethyl-3-[[ (ethylamino)methoxyphosphinothioyl]- oxy]-2-butenoate. The use of propetamphos as an insecticid and the synthesis thereof is described by eber and Lutz, U Patent 3,758,645. "Hydroprene" as used herein is the common name for ethyl(2E,4E)-3,7,ll-trimethyl-2,4-dodecadienoate. The use hydroprene as an IGR and the synthesis thereof is described U.S. patent 4,021,461. There is an asymmetric carbon atom the C-7 in hydroprene and, accordingly, there are (R) and ( enantiomers of the compound. As used herein " (R,S)-hydroprene" refers to the racemic mixture and "(S)-hydroprene" refers to the (S)-{+) enantioroer form of hydroprene. Where "hydroprene" is used herein without reference to its enantio eric content, the term is inclusive of both (R,S)-hydroprene and (S)-hydroprene. The current invention is also directed to a method of controlling a cockroach population which method comprises applying to a locus of the cockroach population, in an effective cockroach population controlling aggregate amount (a) hydroprene, and (b) propetamphos. Background The cockroach is one of the most difficult insects to control. It is primarily a nocturnal insect which forages i exposed locations at night and finds hidden harborages during the day. The life cycle of the cockroach begins with eggs formed in capsules called ootheca. The eggs first hatch into Stage I nymphs which then progress over about 74 days through five more ny phal Stages II-VI to fully developed adult cockroaches, in her adult life span, the female adult cockroach lives for approximately 144 days and produces six ootheca containing about 40 eggs each. Thus the population growth potential is tremendous. A cockroach population continues to grow in a geometrica fashion as long as the three basic requirements of food, wate and harborage are sufficient. Oftentimes, a cockroach population will be found to have stabilized in number because of some limitation in one or more of the three basic requirements. There are two possible ways to deal with the cockroach infestation. One is to submit the cockroach population to a repeated treatment with insecticide. The second is to submit it to a repeated treatment with an insect growth regulant (IGR) which will interfere with cockroach maturation and fertility. It has been observed that if a stabilized cockroach population is under stress, for example when it is temporaril stressed by application of an insecticide, and the stress is ended (e.g., the residual activity of the insecticide has becoae ineffective) , the cockroach population responds to the end of the stress by producing increased numbers of young cockroaches much beyond the previously stabilized population level. The population explosion occurs whenever the insecticide looses its toxic effect on the cockroaches. That is particularly true in cases when the insecticide does not affect or interfere with the reproductive potential of surviving cockroaches. The application of insecticide alone thus has an immediate but short-term effect on reducing the cockroach population as the residual activity of an insecticide effective on a cockroach population generally does not las 5 for more than about eight weeks. In addition, because of high toxicity of insecticides, it is often necessary and preferable to restrict the number of applications and the areas to which the insecticide is applied to prevent a hea hazard to people. 1 Q An alternative to treatment with insecticides is to t the infested area with an environmentally safe IGR such as hydroprene. The drawback of treatment with hydroprene or other IGRs is the long time period before the effect on cockroaches is observed. Such delay is caused by the IGRs 5 mode of action. When an IGR is applied to the locus of cockroach infestation the adult cockroaches are not affect at all and the immature nymphs seemingly continue to devel through successive stages to adults. However, if the cockroaches during their nymphal development come into con 0 with an IGR they become irreversibly morphologically defor and physiologically unable to reproduce. This effect, together with the residual activity of IGRs, greatly impac the cockroach population as the viable reproducing individ begin to decline in number around four to six months after g first application of IGR to the locus of the population. Thus, a scaled-up test in a 1000 cubic foot testing chamber simulating a kitchen with a fairly heavy German cockroach infestation has shown that a single application 1.2% (R,S)-hydroprene fogger at 250 ml per 100 m 2 provides 0 some degree of βupression of the cockroach population. However, the complete eradication of cockroaches was never accomplished. Definitions An "insect growth regulator" as used herein, is a compound which is effective in regulating the growth and maturation processes of an insect. The term "locus of the cockroach population" as used herein refers to unit areas such as an apartment, apartment building, restaurant, house, warehouse, theater, office and office building, and the like wherein there exists an infestation of cockroaches which may or may not be a stabilized population of cockroaches. The term "control of a cockroach population " aβ used herein means a significant percentage decrease in the number of cockroaches in the tested facility. Controlled cockroach population means the number of cockroaches acceptable to the occupants or users of that particular facility. The term "spot treatment* as used herein and in the appended claims means that the formulation is applied as a spot or crack and crevice treatment and not to the general space or forage areas. It has now been found that combined application of the IGR hydroprene and the insecticide propetamphos to the locus of the cockroach population provides a safe, fast, complete, long-lasting and highly effective control of the cockroach population. Surprisingly, the combination of active ingredients hydroprene and propetamphos and their application individually or in admixture to cockroach infested places overcomes the disadvantages (short effect of propetamphos and long delay following the hydroprene treatment) of each active ingredient alone. The application of a combination of both active ingredients to the locus of a cockroach population produces a significantly greater percent reduction than the application of either hydroprene or propetamphos alone, and such reduction is greater than the additive effect of both active compounds when used separately. Propetamphos possesses moderate to good residual activit (ca. 60 days) . The application of propetamphos alone to cockroach infested apartments results in immediate (within one month) reduction of cockroaches by approximately 50-60%. The level of activity reaches its peak at approximately 60 days and the gradually decreases in efficacy so that at 120 days (4 mont the infestation may be back to 64-50% depending on the clim and other surrounding conditions. Hydroprene has no insecticidal activity or direct toxicity to the insect at any of the morphogenetic stages. Thus, the application of hydroprene to a population of cockroaches has no immediate, short term beneficial effect. The adult insects remain unaffected and immature insects although morphogenetically inferior still continue to devel to an infertile adult. As a consequence the cockroach population begins to show a decline in numbers about six months after the hydroprene treatment. Probably due to the initial stress, for the first four months, the application of hydroprene alone results in an increase of cockroaches. Only after four months does this level gradually decrease. It has now been found that the combination of hydropre and propetamphos decreases the cockroach population during same interval to an extent greater than the additive effect can account for. AwBinigtrat-pn and formula .. gn In practice, both the active ingredients propetamphos hydroprene may be administered either in admixture or individually in separate steps but in close time sequence s that one treatment follows immediately the other. In the latter case it does not appear to be critical as to whether the hydroprene formulation or the propetamphos formulation applied first. For convenience and saving of time, it is preferred to apply the spot treatment of propetamphos first and then immediately to apply the general space treatment using a hydroprene aerosol fogger. The hydroprene is conveniently in liquid formulation, e.g. in fogger, aerosol or e ulβifiable concentrate form. propetamphos is conveniently in liquid (e.g., emul β ifiable concentrate formulation form) or in solid formulation form (wettable powder, granule or dust). Hydroprene is usually applied to the locus of the cockroach population as a general space treatment. As such the preferred application is by use of a fogger or an aeros which provides excellent coverage of general forage areas a harborages of the cockroaches. Hydroprene can also be administered as an e ulsifiable concentrate using a suitabl sprayer. Propetamphos is usually applied to the locus of the cockroach population either as a general space treatment or a spot treatment. For health reasons the spot treatment is preferred. For both treatments, the usual mode of administration is by sprayer, duster or aerosol which permi careful direction of the application of the insecticide. T propetamphos is primarily applied to harborages such as baseboards, storage areas, closets, around water pipes, beh and under cabinets, and similar areas, Hydroprene is conveniently administered at a rate of f 1 to 50, preferably of from 2 to 36, more preferably of fro to 30 mg/m 2 . (RS)-hydroprene is conveniently administered at a rate from 12 to 50, preferably of from 18 to 36, more preferably from 20 to 30 mg/m 2 . (S)-hydroprene is conveniently administered at a rate from 1 to 20, preferably of from 2 to 15, more preferably o from 3 to 13 mg/m 2 . Propetamphos is conveniently administered at a rate of from 52 to 224 mg/m 2 , preferably of from 76 to 148, more preferably of from 100 to 124 mg/m 2 . Where necessary, the treatment is repeated, e.g. 4 mon after the initial treatment employing similar or lower application rates. Even after total eradication of the cockroach population it is advisable to prophylatically rep the treatment according to the invention. When the hydroprene and/or propetamphos formulation is aerosol, volume deliveries will in general vary from 250 ml 1000 ml per 100 2 . Where the hydroprene and/or propetamphos formulation is an emulsifiable concentrate, volume deliveries will in general vary from 500 ml to 2000 ml per 2 . The weight per weight concentration of the formulation to be applied will of course depend on the volume delivery. Thus an application rate of 50 mg/m 2 may be achieved with a 250 ml/100m 2 volume delivery of a 2.0% w w formulation, or with a 500 ml/m 2 volume delivery of a 1% wiw formulation, etc. The mixture of propetamphos and hydroprene is administered through any acceptable mode of the application o pesticides such as spraying, fogging, dusting, painting, spreading, etc.; however, the administration in the form of a propetamphos emulsifiable concentrate mixed with the hydroprene concentrate is preferred. Application is to the whole facility but particularly to cracks, crevices and spots. A mixture of propetamphos with hydroprene may be formulated in any suitable formulation form, e.g. in liquid form, as a ready-to-use formulation, an aerosol, an emulsifiable concentrate or in solid form * One suitable method of preparing the (RS)-hydroprene/ propetamphos mixture, or the (S)-hydroprene/propetamphoβ mixture is to blend concentrates of diluted propetamphos with a suitable carrier substance and then mix the resulting composition with technical or diluted (RS)- or (S)-hydroprene. The formulations of the present invention either individually or in the mixture may include conventional insect control formulation adjuvants, diluents, modifiers or conditioning agents, herein included in the term "suitable carrier substance" to provide formulations in the form of solutions, emulsions, dispersions, powders, dusts, granules and the like. The liquid formulations of the present invention can contain one or more surface active agents as a conditioning agent to render the formulation readily dispersible in water or other liquid. The term "surface active agents" includes wetting agents, sticking agents, dispersing agents, emulsifying agents, and the like. The solid formulations of the present invention in the form of powder, dust or granules can be prepared using such substan as talc, natural clay, diatomaceous earth and silica, particularly finely divided silica such as Hi-Sil, The amount of active ingredient in the formulations of the present invention will vary according to the formulatio and the manner in which the formulation is to be applied bu in general, will be from about 0.1-20% for propetamphos and 0.01-10% for hydroprene. The weight ratio of propetamphos hydroprene will conveniently vary within the range of from to 224:1, preferably from 3.3:1 to 41.3:1. The weight rati of propetamphos to (RS)-hydroprene is generally from about to 18.7:1, preferably from 3.3:1 to 6.2:1 by weight and for propetamphos to (S)-hydroprene from about 224:1, preferably from 7.7:1 to 41.3:1 by weight. The following examples are provided to illustrate how practice the present invention. They should not be constru as narrowing or limiting its scope. In all examples, all parts and percentages are by weight unless otherwise specified. EXAMPLE 1 Field Evaluation? Four types of insecticidal agents - hydroprene, propetamphos, dichlorvoβ and chlorpyrifoβ - an combinations thereof were tested individually or as a mixture in field trials for their effectiveness against cockroaches. In addition to the various insecticides, methods of application and the frequency of application, various formulations were also evaluated in this testing regime. Methods Cockroach Population Assessment Tasting Sites and Controls Suitable apartment complexes for testing were located. To qualify for testing, each apartment complex had to have a certain degree of cockroach infestation. Either a negative or positive control was maintained. I apartments were used in the test, the control units were in the same complex but separated so as to avoid migration. Complexes were ideally units in a single building on one side of a parking lot for the treated group and the same number of units of identical construction were on the other side of the parking lot for the control group. Special care was taken to assure that the complexes were completely separated from each other to prevent the migration of cockroaches. Qualifications for Testing Requirements To qualify as a test site, a minimum pretreat ent count of 15 cockroaches daily per three traps was required. If, using this criteria, the majority of the apartments in one coπ.plex qualified, all the apartments in the complex were used for testing of one type of insecticidal agent. The total number of pre-treat ent cockroaches trapped in the complex were counted within the month prior to treatment and such counting was repeated monthly during the treatment up to the end, Then, each testing period was expressed as the average percent reduction over all the apartments in a complex treated with one agent. Once the apartment complexes qualified, the random assignment to treat each complex with a different agent was made and a letter to that effect was sent out to all tenants to explain what would be done at their apartments. Monitoring Methods Each test site was monitored within at least one month prior to treatment to establish a pre-treat ent level of cockroach infestation. For the determination of pretreatment level of infestation the trap count monitoring method was preferred. In some instances, the trap count was supplemente by visual count. Controls were monitored identically to the treated groups. Trap counts In most instances, three sticky cockroach traps (usually Black Flag Roach Motel*) with attractant were placed in the apartment in areas of apparent heaviest infestation. The three traps were placed in the kitchen of each apartment for 24 hours. The trap locations were as follows: 1) on the counter near the sink, 2) in the cabinet underneath the sink, and 3) on the floor near the range or the refrigerator. The same locations of these traps were monitored monthly up to twelve months. Individual trap counts were made for each apartment over the entire study. If only one or two traps were used to determine pretreatment infestation levels, then throughout the whole study only that location was monitored. After 24 hours of monitoring, the traps were collected and brought back to the laboratory for counting* The traps were left out for 24 hours, then collected, an cockroaches were counted as normal adults, IGR adults and nymphs. The raw data were then recalculated for percent of reduction using the following formula: T 0 - Ti x 100 « Percent Reduction T 0 τ 0 a pretreatment count T^ ■» posttreatment count at the time i "In erpr tation of Data Obtained data were expressed in the following Tables 2 as the percent of reduction (R%) of pretreatment count; the percent of juvenile hormone affected adults (IGR) comparing with normal adults only; the percent of adults (A) in the total population and the percent of nymphs (N) in the total popu]ation. Visual counts Some areas of primary harborage, particularly that of breeding ground, were visually inspected and counts of the cockroaches were logged for the month prior to the testing period. The same areas were monitored throughout the whole testing period, i.e. up to nine months following the application of the tested formulation. Testing Mat_.ia.a A. Propetamphos The solution of propetamphos applied to designated apartment complexes was prepared from 50% propetamphos emulsifiable concentrate (EC) diluted with water to produce 1.0% solution. The 1.0% solution was applied with low pressure compressed air hand βprayer either as a spot, crac and crevice treatment or as a general space treatment according to the label instructions. 50% propetamphos EC was prepared as tank mix from the following formulating agents: iΔacfi-U-eiλtfi ( W/¥1). s 9H_fil Propetamphos Technical 56.11 sandoz (90%) Cellosolve* 38.89 Union (ethylene glycol ethyl ether) Carbide Sponto* N-140-B (emulsifier) 5.00 witco B. Hγdrcprene The hydroprene applied to designated apartment complexe was supplied in the following formulations: < SΪ-Hvdroorene - 65.7% Emulsifiable Concentrate (EC) Ingredients (v v £__ U X£ £ (RS)-Hydroprene Technical 74.56 Zoecon (90%) Igepal* CO-630 (surfactant) 25.44 GAF 65.7% hydroprene EC is suitable for dilution with water 0.6% (RS)-Hydroprene Fogger Concentrate A Ingredients (V/V)% __!_i_ £ ___- (RS)-Hydroprene 95.03% 0.66 Zoecon methylene chloride 16.34 Commodi (inhibited aerosol grade solvent) 1,1,1-trichloroethane 55.00 Commodi (inhibited aerosol grade solvent) 0.6. fRS)-Hydroprene fogger oncen rate B IngrsdigHtg W/W% Source (RS)-hydroprene (95.03%) 0.89 Zoecon Methylene chloride 22.72 Dow (inhibited aerosol grade solvent) 1,1,1-trichloroethane 76.39 Dow (inhibited aerosol grade solvent) Q.-t (RS)-Bydroprene Faggex.A IngredientB tv/v. *. source 15% Hydroprene Manufacturing 4.81 Zoecon Cone* Methylene Chloride 12.91 DOW (inhibited aerosol grade solvent) 1,1,1-trichloroethanβ 55.0 DOW (inhibited aerosol grade solvent) Propellant A-70 28.J Commod ♦ The hydroprene manufacturing concentrate is a dilutio of technical hydroprene in methylene chloride at the 15% level. 543 - 13 0.6% (RSI-Hydroprene Fogger B ingredjente W/W. source 0.6% (RS)-hydroprene fogger 72,0 Zoecon concentrate B Propellant A-70 (Hydrocarbon 28.0 Commodity Propellent) Aerothene* TT 55,00 Commod 1.2% ( SI-Hvdroorene Fogger Concentrate B ingredients H__H1 5CH ____ (RS)-hydroprene (95.03%) 1.8 Zoecon Methylene Chloride 21.8 DOW (inhibited aerosol grade solvent) 1,1,1-trichloroethane 76.4 Dow (inhibited aerosol grade solvent) 1.2 (PS)-Hydroprene Fogger Ingredients ( w/w.t Source 1.2% (RS)-Hydroprene fogger 72 Zoecon concentrate A-70 propellant 28 Commodi 0.6% (RS)-hydroprene aerosols are prepared as 0.6% (RS)-hydroprene foggers and fitted with 0.020 in. MBST #01-5018 aerosol actuators rather than fogger actuators. 9.0% (S)-Hydroprene Emulsifiable Concentrate ingredient! (S)-Hydroprene Technical (91.0%) 10.09 Zoecon Tenox 4 [1] Antioxidant 0.50 Eastman Atlox 847 [2] Emulsifier 19.03 I.C.I. Atlox 3404F [3] Emulsifier 11.42 I.C.I. Isopar M [4] Solvent 58.96 Exxon [lj Antioxidant - Corn oil solution of BHT (Butylated hydroxytoluene) and BHA (butylated hydroxyanisole) , [2] Emulsifier: Alkoxylated polyol fatty acid ester. [3] Emulsifier: Proprietary blend of nonionic and ionic e ulsif erβ [4] Solvent: Isoparraffinic solvent. 0.3% (S)-Hydroprene Fogger Ingredients / * Source (S)-hydroprene Technical (91.0%) 0.40 Zoecon Methylene Chloride 16.55 Dow (inhibited aerosol grade solvent) 1,1,1-trichloroethane 55.00 Dow (inhibited aerosol grade solvent) Propellant A-70 28.00 Commodity (hydrocarbon propellant) BHT-Antioxidant 0.05 Eastman (butylated hydroxytoluene) 0ι3. (S)-B ropren-..AejLO&aJ- 0.3% (S)-hydroprene aerosols are prepared as are the 0.3 (S)-hydroprene foggers except the actuators are suited to han held aerosol delivery. c. Hydroprene/Propetamphos Mixtures 1. Tank mixes Hydroprene/piopetamphos formulations were prepared by mixing 65.7% hydroprene EC with 50% propetamphos EC together in a tank of water just prior to use. The final EC tank mixture was applied according to instructions on the propetamphos label for application of propetamphos. 2. Combination Formulations 59 .7% Propetamphos/7 .2% fRS -Hydroprene EC Formulation Ingredients / % ££_U££ Propetamphos technical (90%) 76.2 Sandoz (RS)-Hydroprene technical (94%) 6.5 zoecon Tenox* 4 (anitoxidant) 0.7 Eastman Atlox* 3406P (emulsifier) 11.6 I I Atlox* 3409 (emulsifier) 5.0 ICI This formulation in particular is preferred for applications to crack and crevice areas of the 3ecus. rror-ct-arr.phOfr/fRS) -Hvdroorene Aerosol Formulation (Foggerl Tn q redi nfce /w% Source Propetamphos technical (90%) 3 ,20 Sanchez i$iS)-Hydroprene 4.81 Zoecon (manufacturing concentrate 15%) methylene chloride 10.99 DOW 1,1,1-trichloroethane 55.00 DOW A-46 propellant 25.00 Commodity The above formulation in particular is preferred for applications to crack and crevice areas of the locus, Propetamphos/ (RSI -Hydroprene SoUd Formulation w/w% &CU1I££ Propetamphos (technical 90%) 1.33 Sandoz (RS) -Hydroprene (technical 88%) 0.14 Zoecon Barden* AG-1 (aluminum silicate) 88.53 Commodity Hi-Sil* 233 (silica) 5.00 Commodity Ethylene glycol 5.00 Commodity Ready to Dse Formula - Propetamphos/fRS) -Hydroprene Ingredient w/w% Source Propetamphos Tech. (90%) 1.23 Sandoz (RS) -Hydroprene Technical (90%) 0.36 Zoecon Sponto* AK 31-568 0.40 Witco Sponto* AK 31-56A 1.60 Witco Water 94.58 Commodity Xylene Range Aromatic Solvent 1.00 Commodity BHT 0.44 C- * ϊ * >roodity Colloid 643 0.02 Commodity Tetrasodiu EDTA 0.2 Commodity Citric Acid 0.1 Commodity Dowicil* 75 (.-tabili zer) 0.07 DOW I.6% (S)-Uγdroprene/59.7% Propetamphos EC ingredient* Ki £β_i____e 5 Propetamphos Tech. (89%) 68.42 Sandoz (S)-hydroprene Tech. (91%) 4.75 Zoecon BHT Antioxidant 5.00 Eastman (butylated hydroxytoluene) Atlox 3406F-XF 15.27 ICI 0 (proprietary blend of emulsifiers) Atlox 3409 F-XF 6.56 ICI (proprietary blend of emulsifiers) In individual uee the hydroprene foggers were 5 oz, can 5 applied at a rate of 250 ml/100 m 2 of area to be treated. The percentage of (RS)-hydroprene in the foggers was either 1.2% or 0.6% and of (S)-hydroprene, 0.3%. At least one fogg was placed in the kitchen and bathroom of each unit, with th remaining foggers (if any) being placed throughout the unit 0 needed. All cabinets and drawers were cleaned out and left open so the fog would cover as much area as possible. The (RS)-hydroprene aerosol was a 5 oz, can of 0.6% a.i applied at a rate of 2.50 ml/100 m 2 of area to be treated. Aerosol was applied to cabinets, drawers, under appliances, 5 and any other possible cockroach harborage in the kitchen an bathroom. Trap counts were taken at monthly intervals throughout the test, in the same manner as pre-trβatment countβ. In so studies, re-application of the hydroprene and/or propetampho Q was done at either 3, 4, or 6 months after the initial application. The percent reduction was calculated using the formula disclosed herein in Roach Population Assessment. These tests ran for a period of up to 11 months. Table 1 illustrates the effect of application of 5 propetamphos alone, (RS)-hydroprene alone, and the mixture o both in various formulations on the German cockroach ( ftiatei germ n ea^ population in the cockroach infftRted facilities u to nine months. For determination of efficacy, post-treatme counts were compared to pretreatment counts and expressed in percent of the reduction or increase of the number of cockroaches. The initial pretreatment count of cockroaches equals to 0% reduction. In the following examples and tables, formulations used were as follows t "H/P Mixture" je a tank n<ix of a 1.0% solution from 50% propetamphos EC, a 0.12% solution from 65.7% (RS)-hydroprene FC, and water. "H/P Combination" is a combination treatment using 0.6% (RS)-hydroprene fogger and a 1% solution from 50% propetampho EC. "(RS)-hydroprene 0.12% EC" is a 0.12% solution from 65.7 (RS)-hydroprene EC in water. Propetamphos 1.0% EC is a 1.0% solution from 50% propetamphos EC in water. TABLE 1 Formulation (Number of Apartments Treated) Percent of Reduction of Coc roachβB (RS) (RS) Hydroprene Hydroprene Propetamphos H/PMixture H/PCombina EC Q .I2 lλ-J---eftgsie j NO.Apt. (201 (16) (191 (151 (16V. Months 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 term __. 67% 90% 96% 6 71% 22% 95% 97% 7 term term _.. — 8 94% 97% 9 99% 100% R = retreatment with the same agent Table 1 shows that in reducing the cockroach population, the mixture of propetamphos and (RS)-hydroprene in emulsifiable concentrate forms (H/P mixture) and the combination of (RS)-hydroprene fogger and propetamphos emulsifiable concentrate (H/P Combination) are highly supe to the treatment with propetamphos alone or (RS)-hydropren alone. The residual and toxic activity of the H/P Mixture of the H/P Combination were extended, In addition, 89% of surviving adult cockroaches at 4 months following the application of the H/P Mixture were "IGR adults", i.e. abnormal and infertile cockroaches. Treatment with propetamphos alone resulted in εupress of 80% of the cockroach population by the second month but from the third months on such reduction slowly ceased and months the reduction caused by propetamphos alone was only against the original number of cockroaches. Remaining surviving normal adult cockroaches were at all times capab of reproducing and hence able to rettore the population wi the short time after the residual levels decreased to the pretreatment levels. Treatment of a cockroach population by (RS)-hydropren alone actually increased the population of cockroaches by approximately 56% in four to six months following treatmen Nevertheless, these cockroaches were all IGF. efcnormal adul and were therefore unable to reproduce. EXAMPLE 2 Results obtained from other individual field testing illustrated in Tables 2-11. %R » percent reduction of pretreatment count. IGR * percent of juvenile hormone affected adults as compared with normal adults on]y. N * percent of nymphs in the tcta] population, A »■ percent of adults in the total population. A, The Fairfield Inn Apartments were treated with 1.2% (RS)-hydroprene fogger, 0.6% (RS)-hydroprene aerosol, and propetamphos EC, Thirty-four apartments total were treate Results are given in Table 2. TABLE 2 Fairfield Apartments PL,e--TreaJ ---QUJθJ-S Initial 986 Post-Tre^ment % Reduction 0 Months 1 Month 71 5 522 50 2 Month 78 8 844 43 3 Month 86 7 777 34 4 Month 91 9 933 37 5 Month 95 9 922 27 6 Month 90 9 933 26 7 Month - - 8 Month 94 93 22 9 Month - - 10 Month - - 11 Month 100 0 100 B. The Willows Apartments were treated with 0.6% (RS)-hydroprene fogger, 0.6% (RS) -hydroprene aerosol, and propetamphos EC. The hydroprene treatment was repeated at four months after the initial treatment. The aerosol was sprayed around the kitchen area, in the bathroom and in th closet in these types of units. Then a single fogger was placed in the center of the room. Propetamphos was applie a spot treatment. Twenty-four apartments were treated, Fesults are given in Table 3. TA&L.S _ Willows Apartments Fre-Treat Counts. Initial 885 E_}£j_: -Treatment % Reduction SLE ____B tt 0 Months 0 0 0 1 Month 59 48 69 2 Month 72 80 55 3 Month 82 81 50 4 Month 85 87 45 5 Month 92 89 40 6 Month 95 97 28 7 Month - - - 8 Month 90 83 14 11 Month 99 75 0 C. The Northwood Apartments are government subsidized uni from two to four bedrooms with one.or two baths. A group o 20 apartments was used to evaluate the effects of a 1.0% propetamphos E.C. treatment without any (RS)-hydroprene. T application was made per label directions using an average 1 Quart solution per apartment. The highest percent reduct was at 2 months with 80%, at which point it dropped until a re-treatment at 4 months. The level of control never reach as high as the various (RS)-hydroprene/propetamρhos treatments. The propetamphos units were dropped from testi at month 9 and re-treated with hydroprene and propetamphos. The last treatment at the Northwood apartments was a 0.12% (PS)-hydroprene E.C. tank mixed with a 1.0% propetamphos E. and applied according to the propetamphos label. A 1 gallo & G compressed air sprayer was used for this treatment as w as for the propetamphos E.C applications. This treatment provided fairly good control initially and with a 4 month re-treatment gave 99% reduction by the ninth month. Number apartments included in each treatment is in parenthesis. TABLE 4 Northwood Apartments ( 20 ) Propetamphos 1% EC EiLfi Xr Aβt .£oιu>J_e Ini tial 290 Post- -Treatment % Reduc ion IB 1_LR tt Month 0 0 0 Month 53 1 45 Month 80 0 50 Month 78 10 67 Month (retreated) 61 7 60 Month 67 2 57 Month 22 7 70 8 Month 77 17 66 TABLE 5 Northwood Apartments (18) (RS)-Hydroprene 0.6% Fogger and 0.6% aerosol; Propetamphos 1% EC Pre-Treat Counts Initial 641 Post- -Treatment * Per. e !on 22 IGR tt Month 0 0 0 Month 91 56 34 Month 96 71 26 Month 97 64 22 Month (retreated) 99 75 50 Month 99 33 40 Month 98 14 50 Month 8 Month 99 50 0 9 Month 100 100 0 Northwood Apartments (16) (RS)-Hydroprene 0.6% aerosol; Propetamphos 1% EC Pre-Treat Counts Initial 773 F et¬ -Treatment %. Reduction id IGB tt 0 Month 0 0 0 1 Month 88 68 38 2 Month 88 75 46 3 Month 84 83 47 4 Month (retreated) b2 83 53 5 Month 87 96 54 6 Month 90 85 29 8 Month 96 80 11 9 Month 99 100 33 TABLE 7. Northwood Apartn-ents (16) (RS)-Hydroprene 0.6% fogger; Propetamphos 1% EC Pre-Treat.Gaunt.* Initial 593 Hoa-m. -Treatment * Reduction J_B 3M tt 0 Month 0 0 0 1 Month 89 44 43 2 Month 94 64 35 3 Month 97 58 25 4 Month 95 79 32 5 Month 96 59 26 6 Month 97 67 37 7 Month P Month 97 50 48 9 Kcnth 100 100 50 .S__MF 8 Northwood Apartments (16) 0 , 12% (RS) -Hydroprene 5E; 1% Propetamphos EC (Tank Mi x) Pre-Treat Counf Initial 1004 ■Ppat-TreAtmerit..%..Rft iic J_i__n ii_ ι__a tt o Month 0 0 0 1 Month 78 51 42 2 Month 75 58 47 3 Month 80 94 36 4 Month 88 89 19 5 Month 90 94 ε 6 Kcnth 9 5 15 8 Month 94 83 21 9 Month 99 83 25 D. One half of the Chateau apartments were treated with Mr Scott's* 0.5% reody-to-υse chlorpyrifos (Table 10). Chlorpyrifoβ is the common name for the insecticide O r 0-άiethyl 0-(3,5,6-trichloro-2-py idinyl)phosphorothioate (USP 3,244,586). In the second half of the apartments 0.6% (RS)-hydroprene fυςςei &i. 250 ιr.J/100 m 2 and 0,6% 5 oz. (RS)-hydroprene aerosol for the kitchen and bathroom were us (Table 9) . The results show an inert-ase in both test populations, with the (RS)-hydroprene treated apartments increasing at a fcϋowet rate. After he ti* mo cT&t.a point the chlorpyrifo treatment was terminated for various reasons. Chateau Apartments (RS)-Hydroprene 0,6% fogger and 0.6% aerosol; Chlorpyrifos 0.5% Pre-T cat CoLintfr Initial 127 Po t-Treatment % Reduction J_R QZ tt 0 Month 0 0 0 1 Month -2 6 58 65 2 Month -172 71 72 3 Month -164 69 65 4 Month - 5 Month - - 6 Month -87 26 52 TABLE 10 Chateau Apartments Chlorpyrifos 0,5% Initial 103 0 72 Poet-Treatment % Reduction E Ififi tt 0 Month 0 0 0 1 Month -242 36 73 2 Month -561 45 73 3 Month -451 57 72 4 Month - 5 Month - 6 Month -ΣC7 17 65 FXOTLE.3 In a similar manner and following the procedures of Examples 1 and 2, two buildings of the Wloteoniati were treated as follows. Buildings 1 (13 units) and 5 (8 units) were treated wit 59.7% proρetamphos/7.2% (RS)-hydroprene EC at initial treatment. Building 1 was re-treated at 6 months with 59.7% proρet-θn>ρho&/7.2% (RS)-hydroprene EC. Building 5 was re-treated at 6 months with 59.7% propetamphoβ/3.6% (S)-hydroprene EC. Th l ftM..it£ in Table 11 show excellent and continuing reduction of the cockroach population through ten POri ht, v.i t i c ι>c:ιϋ at i t> iri t e (S)-hydroprene-treated apartments completely eradicated at nine months. TABT.F. 1 1 Whitsonian Apartments p u idino ι Building-? Pre-treat ent counts 999 252 fiuilj-Ung..!.. Buildin ,5 12. ISE itt IE TGR ifl 0 Month 0 0 69 0 0 54 ? Fcr.th 46 67 48 55 73 54 3 Month 58 62 29 55 P3 39 4 Month 80 79 31 84 83 44 Retreat at 6 Months 7 Month 86 39 45 98 20 17 πn-n-z ■ In a similar manner and following the procedures of Examples 1 and 2, the spot treatment with 1% propetamphos E j& followed with general space treatment using any one of hydroprene EC, hydroprene 0.6% fogger concentrate, hydropre 0.6% fogger, hydroprene 1.2% fogger concentrate, hydroprene 1.2% fogger and hydroprene 0.6% aerosol for control of cockroach population. A 3 formulations used in this example are disclosed in Example 1 in details, EΣABEI.B.S in a similar manner and following the procedures of Examples 1 and 2, the general space treatment with 1% propetamphos EC is followed with general space treatment i.t &r> ere of hydroprene EC, hydroprene 0.6% fogger concentrat hydroprene 0.6% fogger, hydroprene 1.2% fogger concentrate, hydroprene 1.2% fogger and hydroprene 0.6% aerosol is used control of cockroach population. All formulations used in this example are disclosed i Exam le 1 in details.

Claims: CLAIMS 1. An insecticidal composition cort'pr i s i ng proi 'etamph ar<3 hydroprene. 2. A compound according to Claim 1 wherein the hydroprene is in racemic form. 3. A composition according to Claim 2 wherein the weight ratio of propetamphos: (RS) -hydroprene is from 1;1 to 18.7J1, 4. A con-position according to CJaim 3 wherein the weight ratio of propetamphos: (RS) -hydroprene is from 3.3:1 6.2:1. 5. A compound according to Claim 1 wherein the hydroprene is the (S) enantiomer, 6. A compound according to Claim 5 wherein the weigh ratio of propetamphos: (S) -hydroprene is frcin 2.6:1 to 224:1 7. A compound according to Claim 7 wherein the weigh ratio of propetamphos: (S) -hydroprene is f op 7,7:1 to 41,7: 8. A method for the control of a cockroach populatio which method comprises applying to the locus of the cockroa infestation prop taiophos and hydroprene in an effective cockroach population controlling aggregate amount, 9. A method according to C3ain- 8 wherein the hydropr is in racemic form. 10. A method according to Claim 9 which comprises applying from 12 to 50 p.g c;f (FS) -hydroprene and from 52 to 224 g of propetamphos per 2 of cockroach locus. 11, A method according to Claim 10 which cop-pi_ 'ees eχ>plying from IS to 36 πg of (RS)-hydroprene and from 76 to 148 mg of propetamphos per 2 of cockroach locus. 1?, A mfct o -pcccr i to C.e-im 8 wherein the hydropre is the (S) enantio er. 13. A method according to Claim 12 which comprises applying fr n- 1 to ?.o mg of (S)-hydroprene and from 52 to 22 mg of propetamphos per m 2 of cockroach locus. 14. A method according to Claim 13 which cop-prises e p- inc: fron. 2 to 15 mg of (S)-hydroprene and from 76 to 14 mg of propetamphos per 2 of cockroach locus.

Inventors: RUDOLPH ROBIN R, RUDOLPH, ROBIN, R.
Applicants: SANDOZ AG, SANDOZ-PATENT-GMBH
Application year: 1988
Main classification: A01N57
IPC codes: A01N37, A01N49, A01N57, A01P7, A01P23, A23G9, C07C69, C07F9