USOO8273340B2

(12) United States Patent (10) Patent No.: US 8,273,340 B2 Vandermeer et al. (45) Date of Patent: Sep. 25, 2012

(54) METHODS AND COMPOSITIONS FOR FOREIGN PATENT DOCUMENTS ATTRACTING OR REPELLING DE 4.012224 A1 * 10, 1991 COCKROACHES OTHER PUBLICATIONS (75) Inventors: Robert KVandermeer, Newberry, FL Sugawara et al., “Attraction of the german cockroach to cyclohexyl (US); Richard J. Brenner, Severna alkanoates and n-alkyl cyclohexaneacetates' J. Insect. Physiol. 1975, Park, MD (US); Domonic A. Cataldo, vol. 21, pp. 957 to 964.* Kennewick, WA (US); Peter Van Voris, Groot et al., “Disruption of sexual communication in the mirid bug Daniel Island, SC (US); Edward S. Lygocoris pabulinus by hexyl butanoate' Agricultural and Forest Lipinsky, Fairview, NC (US) Entomology, 2001, vol. 3, pp. 49-55.* Jean L. Leblanc, "Nonlinear viscoelastic characterization of molten (73) Assignees: The United States of America, as thermoplastic Vulcanizates (TPV) through large amplitude harmonic represented by the Secretary of experiments' Rheol. Acta, 2007, vol. 46, pp. 1013-1027.* Agriculture, Washington, DC (US); Kite et al., “Potential Pollinator-attracting Chemicals from Victoria BioGuard Research and Development, (Nymphaeaceae)” Biochemical Systematics and Ecology, 1991, vol. Inc., Kennewick, WA (US) 19, No. 7, pp. 535-539.* Nojima, S. et al., “Identification of the Sex Pheromone of the German (*) Notice: Subject to any disclaimer, the term of this Cockroach, Blattella germanica”, Science 307, 2005, pp. 1104-1106. patent is extended or adjusted under 35 U.S.C. 154(b) by 1065 days. * cited by examiner (21) Appl. No.: 12/221,344 Primary Examiner — James H Alstrum Acevedo Assistant Examiner — Daniel L. Branson (22) Filed: Aug. 1, 2008 (74) Attorney, Agent, or Firm — John D. Fado; G. Byron Stover (65) Prior Publication Data US 201O/OO28294 A1 Feb. 4, 2010 (57) ABSTRACT A method for attracting cockroaches to an object or area, (51) Int. Cl. involving treating said objector area with a cockroach attract AOIN 25/00 (2006.01) ing composition containing a cockroach attractant effective AOIN37/02 (2006.01) amount of at least one compound selected from the group AOIP 7/00 (2006.01) consisting of methyl, ethyl, propyl, or butyl esters of C-7 AOIP 9/00 (2006.01) saturated or unsaturated carboxylic acids and mixtures (52) U.S. Cl...... 424/84: 514/557 thereof, and optionally a carrier material or carrier. A method (58) Field of Classification Search ...... None for repelling cockroaches from an object or area, involving See application file for complete search history. treating said object or area with a cockroach repelling com position containing a cockroach repelling effective amount of (56) References Cited at least one compound selected from methyl, ethyl, propyl, or U.S. PATENT DOCUMENTS butyl esters of C, Saturated or unsaturated carboxylic acids or mixtures thereof, and optionally a carrier material or car 3,523,101 A * 8, 1970 Reuter ...... 528/79 1. 4,156,067 A * 5/1979 Gould ...... 424/78.06 7,153,815 B2 * 12/2006 Kawata et al...... 504,344 2004/0231231 A1* 11/2004 Cataldo et al...... 43,132.1 25 Claims, 8 Drawing Sheets 2004/0238785 A1 12/2004 Van Driessche et al...... 252/68 (3 of 8 Drawing Sheet(s) Filed in Color) U.S. Patent Sep. 25, 2012 Sheet 1 of 8 US 8,273,340 B2

Fig. 1 U.S. Patent Sep. 25, 2012 Sheet 2 of 8 US 8,273,340 B2

Esters of Tiglic Acid

Benzyl- % Hexyl- % e Isopropyl- 2

k Allyl t Propyl-3 Methyl-66 40 50 60 70 8O 90 Roaches Responding (%)

Fig. 2 U.S. Patent Sep. 25, 2012 Sheet 3 of 8 US 8,273,340 B2

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. : 20 38 8: s: 8 go Rays teng 33°C U.S. Patent Sep. 25, 2012 Sheet 4 of 8 US 8,273,340 B2

Rexiosig. 88tweet {xifice is rete at: Keitasks Kats

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3rifice six-8ter era

Fig. 4 U.S. Patent Sep. 25, 2012 Sheet 5 of 8 US 8,273,340 B2

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10 83. %3. 3 :: 8 ss NNN % Sof S8 KSof KS8 KSof cNof CSlo KSof 2 S s 9 $9 S S & & 3° 3 S a SSS sé ^StS -S Sk88séw s U.S. Patent Sep. 25, 2012 Sheet 6 of 8 US 8,273,340 B2

Fig. 6 U.S. Patent Sep. 25, 2012 Sheet 7 of 8 US 8,273,340 B2

100 90 80 70 60 50 40 30 O.OO 0.25 0.50 0.75 1.OO Ethyl caproate (%) in mineral oil

Fig. 7 U.S. Patent Sep. 25, 2012 Sheet 8 of 8 US 8,273,340 B2

O.OO 0.25 0.50 0.75 1.00 Methyl Tiglate (%) in Mineral Oil

Fig. 8 US 8,273,340 B2 1. 2 METHODS AND COMPOSITIONS FOR Thus there is a need to develop cockroach attractants that ATTRACTING OR REPELLING are based on simple chemicals and processes and that provide COCKROACHES safe and effective cockroach attraction as well as delivery systems that can provide an effective dose over a reasonable BACKGROUND OF THE INVENTION period of time. The present invention relates to a method for attracting SUMMARY OF THE INVENTION cockroaches to an object or area, involving treating the object or area with a cockroach attracting composition containing a In accordance with the present invention there is provided cockroach attracting effective amount of at least one com 10 a method for attracting cockroaches to an object or area, pound selected from methyl, ethyl, propyl, or butyl esters of involving treating said objector area with a cockroach attract C-7 Saturated or unsaturated carboxylic acids or mixtures ing composition containing a cockroach attracting effective thereof, and optionally a carrier material or carrier. The amount of at least one compound selected from the group present invention also relates to a method for repelling cock consisting of methyl, ethyl, propyl, or butyl esters of C, roaches from an object or area, involving treating said object 15 saturated or unsaturated carboxylic acids and mixtures or area with a cockroach repelling composition containing a thereof, and optionally a carrier material or carrier. cockroach repelling effective amount of at least one com Also in accordance with the present invention is a method pound selected from methyl, ethyl, propyl, or butyl esters of for repelling cockroaches from an object or area, involving C-7 Saturated or unsaturated carboxylic acids or mixtures treating said object or area with a cockroach repelling com thereof, and optionally a carrier material or carrier. position containing a cockroach repelling effective amount of Cockroaches are perhaps the most common and trouble at least one compound selected from methyl, ethyl, propyl, or some household pest in the United States (ranked second butyl esters of C, Saturated or unsaturated carboxylic acids worst urban pest insect, just behind pestants) and most of the or mixtures thereof, and optionally a carrier material or car world. Cockroaches are not only a nuisance in the home but 1. also can spread disease organisms from garbage, sewers, and 25 other sources to human food that can then cause dysentery, BRIEF DESCRIPTION OF THE DRAWINGS food poisoning, and diarrhea. In addition, some of the most common allergens in homes are from the cockroach and its The patent or application file contains at least one drawing feces, which cause allergic rhinitis and asthma. executed in color. Copies of this patent or patent application Currently, there are two approaches to controlling cock 30 publication with color drawing(s) will be provided by the roaches. One approach uses liquid sprays containing pesti Office upon request and paymnet of the necessary fees. cide that are sprayed where cockroaches are likely to travel or FIG. 1 is a photograph of the Y-tube olfactometer used in seek harborage. This approach relies on the cockroach com the evaluation of compounds as cockroach attractants: ing in contact with the pesticide. The other approach is the use a=airflow into the olfactometer; b-sample or control loca of bait products, e.g. “roach motels'. The two methods may 35 tions; c-air baffle; d & e-ring seals which trap roaches in b: be used by themselves or in combination, and the applicator froach entrance arm. may be a pest control operator (PCO) or homeowner. It is FIG. 2 shows olfactometer results for esters of tiglic acid. estimated that over USS500 M worth of “roach motels’ are Results above 65% were significantly attractive and results sold every year worldwide, and it is estimated that the com below 35% were significantly repellent (mean of 3 repli bined “spray” and “roach motel market exceeds USS1.3 40 cates). billion annually. FIG. 3 shows release rates for bioactives sorbed into An attractant is a chemical that causes an organism (e.g., MP100 and released from a metalized polyethylene Sachet cockroach) to make oriented movement towards its source. containing a 0.5 mm orifice. Currently, there are no commercially available cockroach FIG. 4 shows relative release rates through pores based on attractants used in cockroach control. The term attractant is 45 orifice diameter and compound vapor pressure; propyl prop often erroneously used in reference to phagostimulants (food) rionate (upper curve), methyltiglate (middle), and butylhex that must be found randomly, e.g., by cockroaches, or must be anoate (lower). placed in an area known to be frequently visited by cock FIG.5 shows bioassay results for methyltiglate formulated roaches. Most of the published “attractant formulations have with four different polymers (T) and their corresponding involved the use of cockroach feces which is not commer 50 controls (C). Data is presented as the mean and standard error. cially practical and may add to allergic rhinitis and asthma *=Control and Treatment for a given formulation were sig problems already associated with cockroach feces. U.S. Pat. nificantly different. No. 5,665,370 describes methods to collect and to sterilize the FIG. 6 shows bioassay results for propyl propanoate (Pro active ingredients in cockroach feces and to separate them Prop) and butyl hexanoate (BuHe) formulated with three into sterilized attractants and aggregation pheromones. This 55 different polymers (T) and their corresponding controls (C). is an improvement but not commercially satisfactory. U.S. Data is presented as the mean and standard error. *-Control Pat. No. 5,505,591 describes numerous synthetic pyrans and and Treatment for a given formulation were significantly also mentions three sex pheromones: periplanone B, peripl different. anone A, and periplanone J.U.S. Pat. No. 5,126,128 describes FIG. 7 shows the response of German cockroaches to the Periplanone-B analogues with pheromone activity. Simpler 60 indicated concentration of ethyl caproate (ethylhexanoate) chemicals are found in U.S. Pat. No. 5,384.120 where propyl dissolved in mineral oil. A mean response of 65% or greater cyclohexyl acetate was utilized as an aggregation pheromone represents significant attraction. The dashed line is a refer for the German cockroach and the combination of isobornyl ence line at 65%. A response of 35% or below represents acetate and Santalol alone or in conjunction with propyl significant repellency. Significant attraction occurs between cyclohexyl acetate were utilized for attracting cockroaches. 65 0.25 and 0.85% (N=3). These acetates, pyrans, and pheromone analogues represent FIG. 8 shows the response of German cockroaches to the the state of the art. However, they are still inadequate. indicated concentration of methyltiglate dissolved in mineral US 8,273,340 B2 3 4 oil (N=1). A mean response of 65% or greater represents commercially useful compositions will combine an effective significant attraction. The dashed line is a reference line at amount of attractant with a carrier. The carrier or carrier 65%. A response of 35% or below represents significant material may be, for example, agronomically or physiologi repellency. cally or pharmaceutically acceptable carriers or carrier mate rial. The carrier may be liquid or solid and in either case DETAILED DESCRIPTION OF THE INVENTION release effective amounts of attractant over time periods greater than could be achieved with the attractant alone. The The present invention concerns a composition which carrier may be a cockroach food material (phagostimulant) attracts cockroaches, and contains methyl, ethyl, propyl, or already used in cockroach bait stations or may be inert. Inert butyl esters of C.7 Saturated or unsaturated carboxylic acids 10 or mixtures thereof, and optionally a carrier or carrier mate carriers may, for example, consist of diatomaceous earth, rial known in the art. The carboxylic acids range from three to alumina, clays, cornstarch, or cellulose. Slow release solid seven carbons and may contain an O, B-unsaturation (i.e., the carriers could consist of polymers, microencapsulation, or double bond is alpha, beta to the carboxylic acid carbon). other methods well developed in the controlled release indus Such compounds include ethyl propanoate, ethylpentanoate, 15 try. Two basic low cost sustained-release delivery (SRD) sys ethylhexanoate, propyl propanoate, butyl hexanoate, butyl tems were investigated: (A) the first involves absorbing the heptanoate, methyl tiglate, ethyl caproate, and mixtures active to a substrate (reservoir) that is then secondarily thereof. coated/encapsulated to limit diffusion of the volatile to air and The present invention also concerns a method for attracting control the release rate. Absorbents may consist of various cockroaches to an object (e.g., insect trap) or area (e.g., field, types of charcoal or amorphous silica. A secondary coating orchard), involving treating (or exposing) the object or area (methyl cellulose, polyvinyl acetate, cellulose acetate, ethyl with a composition containing a cockroach attracting effec ene adipate polyester, polyacrylates, carboxymethyl cellu tive amount of methyl, ethyl, or propyl esters of C, saturated lose, hydroxypropyl cellulose, poly(ethylene oxide), or unsaturated carboxylic acids or mixtures thereof, and crosslinked starch, or crosslinked cellulose) is then applied to optionally a carrier or carrier material. 25 the absorbed attractant. (B) The second delivery system is to The amount of attractant used will be at least an effective microcapsulate the attractant, which can then be absorbed amount. The term “effective amount, as used herein, means into the large pore spaces of a carrier reservoir. Such as amor the minimum amount of attractant needed to attract the cock phous silica. Secondary encapsulation may be-required to roaches to a treated area or object when compared to the same further reduce the rates of attractant loss and to increase area or object which is untreated. Effective concentrations of 30 longevity of the bioactive SRD system. the attractant in the compositions may vary between about The present invention also concerns a method for repelling 0.00001% to about 99.99% (preferably about 0.00001% to cockroaches from an object or area, involving treating said about 50%, more preferably about 0.00001% to about 10%, object or area with a cockroach repelling composition con more preferably about 0.00001% to about 1%, more prefer taining a cockroach repelling effective amount of at least one ably about 0.00001% to about 0.1%, more preferably about 35 compound selected from methyl, ethyl, propyl, or butyl esters 0.00001% to about 0.01%). Of course, the precise amount of C.7 Saturated or unsaturated carboxylic acids or mixtures needed will vary in accordance with the particular attractant thereof, and optionally a carrier material or carrier. Such composition used; the type of area or object to be treated; the compounds include propylbutanoate, butyl propanoate, butyl number of days of attractiveness needed; and the environment butanoate, hexylbutanoate, and mixtures thereof. in which the area or object is located. The precise amount of 40 The amount of repellant used will be at least an effective attractant can easily be determined by one skilled in the art amount. The term “effective amount, as used herein, means given the teaching of this application. For example, one the minimum amount of repellant needed to repel the cock skilled in the art could follow the procedures utilized below: roaches from a treated area or object when compared to the the attractant would attract more than 50% (or 65%) of the same area or object, which is untreated. Effective concentra cockroaches and would be statistically significant in compari 45 tions of the repellant in the compositions may vary between son to a control. The attractant composition may or may not about 0.00001% to about 99.99% (preferably about contain a control agent for cockroaches, such as a biological 0.00001% to about 50%, more preferably about 0.00001% to control agent or an insecticide known in the art to kill cock about 10%, more preferably about 0.00001% to about 1%, roaches. Other compounds may be added to the attractant more preferably about 0.00001% to about 0.1%, more pref composition provided they do not substantially interfere with 50 erably about 0.00001% to about 0.01%). Of course, the pre the intended activity of the attractant composition; whether or cise amount needed will vary in accordance with the particu not a compound interferes with attractant activity can be lar repellant composition used; the type of area or object to be determined, for example, by the procedure utilized below. treated; the number of days of repellant activity needed; and Such other compounds may be present generally from about the environment in which the area or object is located. The 0.0025% to about 20% in the composition. 55 precise amount of repellant can easily be determined by one The attractants, in combination with a suitable toxicant or skilled in the art given the teaching of this application. For toxic bait, could direct the target cockroaches to toxic baits, example, one skilled in the art could follow the procedures rather than have the discovery a random event. In this way utilized below; the repellant would repel more than 50% (or toxic baits will be quicker acting, could be placed in locations 65%) of the cockroaches and would be statistically significant away from human activity, or may be used as cockroach 60 in comparison to a control. The repellant composition may or infestation monitors that could trigger treatment. The attrac may not contain a control agent for cockroaches, such as a tants used in combination with contact toxicants or other biological control agent or an insecticide known in the art to non-toxic mechanisms to trap cockroaches may be able to kill cockroaches. Other compounds may be added to the effectively reduce cockroach populations below reaction lev repellant composition provided they do not substantially els. 65 interfere with the intended activity of the repellant composi While the compounds defined above were attractive to tion; whether or not a compound interferes with repellant cockroaches, they wereby nature volatile. It is envisioned that activity can be determined, for example, by the procedure US 8,273,340 B2 5 6 utilized below. Such other compounds may be present gener attractive, whereas 35% or less cockroaches going to the ally from about 0.0025% to about 20% in the composition. sample side represented significant repellent activity. Results The cockroaches include, for example, Blattella ger in-between were neutral. manica, Periplaneta americana, Blatta Orientalis, and Results: The results of the olfactometer bioassay for a Supella Supellectilium. 5 series of methyl, ethyl, propyl, and butyl esters and one hexyl Unless defined otherwise, all technical and scientific terms ester are shown in Table 1...Results are given as a percent used herein have the same meaning as commonly understood response to a 0.5% w/v solution of the test compound in by one of ordinary skill in the art to which the invention mineral oil. Results with an * after them were significantly belongs. Although any methods and materials similar or attractive; compounds with ** after them were significantly 10 repellent (mean of 3 replicates). The diameter of the Y part of equivalent to those described herein can be used in the prac the olfactometer provided a close fit for the cockroach, thus tice or testing of the present invention, the preferred methods keeping it in the center of the walkway. The cockroaches and materials are now described. readily walked up the entrance arm of the olfactometer. When The following examples are intended only to further illus they arrived at the Yijuncture each antenna was usually Sam trate the invention and are not intended to limit the scope of 15 pling the airflow from a different choice arm of the olfacto the invention as defined by the claims. meter (see FIG. 1). Six compounds were shown to signifi cantly attract cockroaches (percent response 2.65%). No EXAMPLES methyl esters of Saturated Straight chain carboxylic acids were active in the bioassay. However, there were active ethyl, The German cockroach (Blattela germanica) is one of the propyl and butyl esters. Three of the six active compounds most difficult cockroach species to control in homes and was were ethyl esters. Regarding the carboxylic acid moiety there used to illustrate the invention. The discovery of cockroach appears to be no pattern, as three, five, six and seven carbon attractants was made possible through the development of a chain lengths showed significant activity. Available homo Y-Tube olfactometer that gave quick and reliable results. The logues on either side of the active esters were inactive. Inter system is capable of determining if a test compound or extract 25 estingly, four esters showed significant repellant activity, is an attractant, neutral, or repellent. Since the cockroaches three of which were esters of butanoic acid (Table 1). never contact the test sample, their response is strictly to the The methyl ester of tiglic acid (trans-2-methyl-2-butenoic molecules in the air stream. acid (methyl tiglate)) showed excellent attractant activity Olfactometer Bioassay: The Y-tube bioassay apparatus was (80.0%, see FIG. 2). Ester homologues of methyltiglate were similar to that described by Vander Meer et al. (J. Chem. 30 also evaluated. None of the five homologues tested had sig Ecol., 14: 825-838 (1988)). Compressed air (breathing-air nificant activity at the concentration used (0.5% w/v). quality) was passed into the two choice arms at 0.2 l/min for Ethyl caproate was used to evaluate the effect of concen a total flow of 0.41/min. Flow rates were adjusted and con tration on cockroach attraction using the described olfacto trolled by two flow meters (Omega Engineering, Inc.). All meter. Concentrations ranging from 0.0 to 1.0% w/v in min tubing carrying the air was either copper or Teflon. Prior to 35 eral oil were evaluated. The results are shown in FIG. 7. evaluating treatment samples, a positive standard was put Significantactivity was found at concentrations between 0.25 through the bioassay procedure. The standard was initially an and 0.9%. Another example is shown in FIG.8 where methyl attractive food material (grape flavoring concentrate used at tiglate was evaluated at three concentrations (0.25 to 0.75). 0.33%) and later 0.5% (w/v) methyl tiglate, one of the com All concentrations attracted 65% or more of the responding pounds of the present invention, in white, light mineral oil 40 cockroaches and were therefore attractive. It is important to (Aldrich Chemical Co.). Treatment evaluations were not demonstrate a range of active concentrations because it shows started unless the positive standard showed significant cock what kind of flexibility can be incorporated into the release roach attraction. Test samples (10.0 ul) and the solvent blank rates of the formulated cockroach attractants. (mineral oil, 10.0 ul) were applied to filter paper strips (0.3x Controlled Release Formulations: Four esters found to be 1.0 cm, Whatman No. 1) and then each was placed into one of 45 significant cockroach attractants were selected for evaluation the two choice arms. Male cockroaches (Blattela germanica) in controlled release formulations-developed by BioGuard, were prepared for their introduction into the olfactometer by Inc. Six controlled release formulations from BioGuard were placing them in a Teflon tube (3 cmx0.8 cm) that had one end evaluated in the olfactometer. The attractants were methyl blocked with a piece of copper mesh screen. The open end of tiglate, butyl hexanoate, propyl propanoate, and butyl hep tube was closed with a lightly attached piece of tape. The 50 tanoate. The attractants were absorbed to either coconut shell cockroaches were introduced individually by removing the charcoal pellets or potassium Substituted crystalline Zeolite tape and quickly inserting the Teflon tube into the entrance pellets, and then coated with water soluble methylcellulose. arm of the olfactometer. The screen mesh did not block the The powdered methyl cellulose was dissolved in 80°C. water airflow and roaches generally moved upstream to the choice until saturation, cooled to approx 25°C., the pellets immersed arms. The initial choice of the cockroach was recorded. The 55 into the solution for a 30 sec, and removed and rapidly air cockroach was removed and the process was repeated 10 dried with 30° C. pre-dried air. The end products were pellets times with the same test and blank samples. The 10 choices (charcoal 2 mmx4 mm dia.; molecular sieve 4mmx1.5 mm usually required less than 5 minutes to complete. After each dia.). To prevent the possible confounding effects from the set of 10 cockroaches had made their choice, the olfactometer potentially high concentration of attractant accumulated in was rinsed with acetone, dried, and reassembled for the next 60 the vial holding the pellets, we placed the pellets needed for test. Each sample was retested with the same cockroaches, but evaluation in a fume hood for one hour prior to olfactometer with the sample and control in reverse positions. The sum of testing. A single pellet was used in place of the filter paper the results from the two tests represented one replicate. This described above. The control side was left blank. procedure minimized bias inherent in the apparatus. A null All fourformulations (methyltiglate, butylhexanoate, pro hypothesis of equal numbers of cockroaches in each arm was 65 pyl propanoate, and butyl heptanoate) using charcoal as the tested with chi-square analysis. Results where 65% or more absorbent were significantly active in the olfactometer after of the roaches choose the sample side were significantly one hour in the fume hood (Table 2). However, the two US 8,273,340 B2 7 8 molecular sieve formulations were no different than the con A different delivery system was developed for propyl pro trol (Table 2). Three of the active formulations shown in Table panoate. To get around the reactivity problem, we developed 2 were allowed to age for longer time periods in the fume a system using Devcon Flexane(R) 80 (a thermoset polymer hood to examine the longevity of their activity (Table 3). consisting of polypropylene glycol and methylene bis(4-cy Methyl tiglate and butyl hexanoate maintained attractant clohexylisocyanate), cured with diethyltoluenediamine). activity between 24 and 48 hours of aging, but butyl hep This thermoset polymer system required that the active com tanoate lost attractant activity between 1 and 24 hours. It pounds be preloaded into carrier particles (must remain fri should be noted that the samples were aged in a fume hood able prior to addition to polymer, not overloaded), and then with high air throughput, thus the longevity may be greater incorporated into the thermoset system. The carrier that was under more static conditions as might be expected in real 10 most effective was the Nanocor Nanomer R. I.30E (5 um usage situations. montmorillinite, octadecylammonium ion-Substituted nano Controlled or Sustained Release Systems for Cockroach clay), which can be loaded up to 50% by wt with active Attractants: Three cockroach attractants identified above compounds. Nanoclay/active loading rates into the polymer (propyl propanoate, butylhexanoate, and methyltiglate) were were at 2 gm nanoclay/active (1 gm active) per 20.5 gm selected for further formulation in controlled release formu 15 polymer. Release rates can be controlled by increasing or lations. The attractants are active at the ppb/ppm level in air, decreasing the cross linking by adjusting the ratio of catalyst and a system was needed to contain the active compounds to monomer. The preferred formulation for propyl propanoate while in storage (shelf-life) and also release effectively for at and butyl hexanoate, consisted of 90 parts propylene glycol, least 30 days when activated. Initial efforts to develop a 10 parts methylene bis(4-cyclohexylisocyanate) and cured Sustained release system yielded release durations of hours to with 38 parts of diethyltoluenediamine. For methyl tilgate 20 a few days, and were inadequate (Table 3). Common adsor parts curing agent is preferred. bents and microporous materials failed to achieve either While volatility losses of the active compounds due to adequate air concentration or longevity. These included vari vapor pressure can be dramatically reduced with these poly ous plant and animal charcoals, crystalline Zeolites, bentonite mer/carrier systems, we still needed the ability to store and and montmorillinite clays, microporous polyethylene poly 25 release at the bio-effective levels for specific cockroach con mers, and mineral- and silicone-based oils (data not shown). trol situations. Several secondary release rate control systems Without being bound by theory, the problem was related to were developed. The first was a sachet that can contain the their vapor pressures which resulted in rapid volatilization to above polymer releasing system. This Sachet can be either air, and/or their chemical reactivity. polyvinylidine chloride (PvdC) barrier film (e.g., SaranexTM) Attempts were made to directly incorporate the active com 30 enclosed in a thermally sealed metalized polyethylene con pounds into a variety of casting thermoset products, including tainer to eliminate release of active compounds, or a metal polydimethylsiloxsiane-, hexamethyldisilazane-, methhyltri ized polyethylene Sachet with a removable seal that covers a methoxysilane-, methyltriacetoxysilane-based silicones, vapor diffusion controlling orifice which when removed MDI (methylene diphenyl diisocyanate)-based urethanes, begins the release process from the internal polymer/carrier, polystyrene. These failed to provide significant increases in 35 or metalized polyethylene Sachet which contains a small vial release longevity. During these studies it was noted that the with a vapor controlling orifice. In the case of the SaranexTM active compounds were acting as plasticizers with a number sachet, the actual porosity of the SaranexTM control release is of thermoset urethane, styrene, and synthetic rubber materi based on type of PVdC and thickness of the film. In the case als, resulting in chemical incorporation into the polymerized of the metalized polyethylene sachet and internal polymer/ polymers, and drastically reducing the amount and release 40 carrier, a specific orifice size controlled the rate of diffusion of rate of active components. the active from the device, as shown in FIG. 4. An additional To alleviate the reactivity with the carrier polymers, we means of containing and reducing the release of the liquid attempted to load active compounds into a series of thermo active compounds and providing a solid Support for use in the plastic polymers including urethanes and synthetic rubbers, above delivery system involved sorbing the active com based on the behavior of the active compounds as plasticizers. 45 pounds into an inert absorbent such as Membrana GmbH’s While injection molding failed to provide a viable system due expanded microporous polyolefin Accurel(R) MP100 which to thermal losses and chemical pyrolysis, it was noted that are granular or pelletized polyethylenes that have 10-50 um there was a residual release that was better than other systems air pockets throughout and can contain up to 90% of their previously evaluated. Propyl propanoate, methylhexanoate, volume in active compounds. MP100 was easily loaded with and methyl tiglate were loaded into a series of thermoplastic 50 80% by wt active ingredient due to its porosity. Again, this granulated feed materials, including 4-(1,1,3,3-tetramethyl material simply held the active, but did not provide sufficient butyl) with ethylene-5-ethylidenebicyclo[2.2.1]hept-2-ene diffusion reduction for adequate longevity of a releasing sys propene thermoplastic synthetic rubber (SantoprenTM 203 tem. Thus, placement into the metalized polyethylene Sachet 40). SantopreneTM is a thermoplastic elastomer (TPE that is a with its diffusion regulating orifice was required. mixture of in-situ cross linking of EPDM rubber and polypro 55 FIG.3 shows the release rate profiles for three active com pylene compounds). Because of the longer life of Santo pounds. Active compounds (1 gm active in Accurel(R) MP100) prenTM in both extreme hot and cold environments, it is often were sealed within the metalized polyethylene sachet, and a preferred over the use of rubber. PellethaneTM 2102-55D is a 0.5 mm hole placed into the film, and sealed until use with a polyester polycaprolactone polyurethane. Methylhexanoate metalized tape. Release rates for propyl propanoate, methyl and methyl tiglate were sorbed using heat and pressure (60° 60 tiglate, and butylhexanoate were calculated at 15.5., 11.4, and C., 40 psi, 30 min) into the Santoprene(R) and were effective in 4.8 mg/day, respectively. Longevity of this system was cal bioassays for cockroach attraction. Dow PellethaneTM culated to be 64, 87, and 208 days, respectively. worked less well, and neither of these systems worked well Release rates for the thermoset urethane (Flexane R 80P) for propyl propanoate. Loading rates of active compounds and synthetic rubbers systems ranged from 0.055 to 0.2 into the Santoprene R, using slightly elevated temperature 65 mg/cm/day, depending on durometer/hardness that is a mea (60°C.) and 40 psi pressure, were 8-12% by wt for the two Sure of polymer crosslinking. Best results were obtained at compounds. durometer/hardness levels above D30. Release rates for the US 8,273,340 B2 10 Saranex system without the release control provided by the These results were obtained over a 6-month period of time metalized polyethylene and diffusion control orifice were using the same formulated materials, which demonstrated the 187,236, and 7 mg/day for propyl propanoate, methyltiglate, stability of the polymer attractant formulation. Sustained and butyl hexanoate, respectively. release formulations were shown to be effective in attracting The relative relationship between the size of a diffusion 5 and holding German cockroaches in a harborage. If the attrac regulating orifice and a wide range in Volatile compounds is tant was formulated with a suitable insecticide, or if the shown in FIG. 4. For lower to high pressure compounds, insecticide was formulated with a food product, then the below 10 mmHg, the release profiles were relatively linear result would be control of the target roaches. Roach attracta with pore size. At high vapor pressures, above 50 mmHg, nts can counteract behavioral avoidance of commercially release rates were not linear and showed a rapid depletion of 10 available cockroach baits, which has been the reason for the carrier reservoir. Secondary carrier design, as noted with many costly control failures. the thermoplastic absorbents and thermoset polymers, Competition in the cockroach control market is intense. restricted the amount of active compounds actually available Innovations are continually being sought to provide a com for diffusion through the regulating orifice. petitive advantage. This is the first report of the identification Thus, we have devised a number of options to contain 15 of cockroach attractants. Successful incorporation of this highly volatile bioactives, and provide a means for immobi invention into “roach motel type products will provide dis lizing the neat liquid compounds, that provide a means to tinct advantages over other products in the market; for employ various carriers to hold and restrict the volatility of example, increased speed and efficacy of action, action detec the actives. We have also devised a secondary package to tion thresholds, and elimination by attracting cockroaches to further control release rates and thus the concentration of the a “killing Zone'.The attractants are effective at low concen actives in air related to cockroach attraction. Our goal was to trations, 0.5% (W/V) in mineral oil, and are commercially optimize both the air concentration related to efficacy and the available at low cost, e.g. butyl hexanoate=S4.50/lb, propyl longevity of the package to deliver this dose for 30-60 days. propanoate-S14.00/lb. Several of these formulations were evaluated. All of the references cited herein, including U.S. Patents, Evaluation of sustained release formulations: Three cock 25 are incorporated by reference in their entirety. roach attractants (methyltiglate, butylheptanoate, and propyl Thus, in view of the above, the present invention concerns proprionate) were formulated in one or more polymerformu (in part) the following: lations (Urethane, Pellethane, Santoprene, and/or Polyethyl A method for attracting cockroaches to an object or area, ene) as indicated in Table 4. A sweater box (1.5x2.0x0.5 ft) comprising (or consisting essentially of or consisting of) provided the test arena. The sides of the arena were coated 30 treating said object or area with a composition comprising a with a blend of mineral oil and Vaseline petroleum jelly. The cockroach attracting effective amount of at least one (or two tops of two 8 oz paper ice cream cups were tapped to the arena or three or four or more than one) compound selected from the floor with masking tape and, prior to the addition of the test group consisting of methyl, ethyl, propyl, or butyl esters of cockroaches, inverted cups without holes were fixed to the C-7 Saturated or unsaturated carboxylic acids and mixtures tapped lids. Twenty-five laboratory reared late stage nymphs 35 thereof, and optionally a carrier material or carrier. or adult male German roaches (B. germanica), starved for 72 The above method, wherein said composition contains hrs, were added to the arena and allowed to calm down (ca. 1 ethyl propanoate, ethyl pentanoate, ethylhexanoate, propyl hour). The starting inverted ice cream cups were carefully propanoate, butyl hexanoate, butyl heptanoate, methyl removed and each ice cream cup top was then Supplied with tiglate, ethyl hexanoate, or mixtures thereof. The above a water tube (1.5 ml scintillation vial with water and stop 40 method, wherein said composition contains ethylpropanoate. pered with cotton), one lab chew food pellet, and either a test The above method, wherein said composition does not con attractant polymer formulation or the corresponding polymer tain ethyl propanoate. The above method, wherein said com blank control. The ice cream cups were replaced with differ position contains ethyl pentanoate. The above method, ent cups that had a roach entrance hole (1.5 cm diameter) cut wherein said composition does not contain ethylpentanoate. into it, just above the inverted cup top (near the arena floor). 45 The above method, wherein said composition contains ethyl The cups were oriented so that the holes were facing each hexanoate. The above method, wherein said composition other. The number of roaches that sought harborage in the does not contain ethylhexanoate. The above method, wherein cups was counted after 24 hours by plugging the entrance said composition contains propyl propanoate. The above holes with cotton, the roaches inside euthanized, and the method, wherein said composition does not contain propyl numbers in each cup counted. The experimental observer did 50 propanoate. The above method, wherein said composition not know the composition of the samples evaluated. contains butyl hexanoate. The above method, wherein said Results: The experiment evaluated the response of male composition does not contain butyl hexanoate. The above roaches to two potential harborages, one containing an attrac method, wherein said composition contains butylheptanoate. tant to be evaluated and the other a control harborage. The The above method, wherein said composition does not con results for methyl tiglate (MeTi) formulated with several 55 tain butylheptanoate. The above method, wherein said com sustained release polymer formulations are shown in FIG. 5. position contains methyl tiglate. The above method, wherein Methyl tiglate formulated with Santoprene showed signifi said composition does not contains methyltiglate. The above cant attraction and aggregation to the treatment harborage. method, wherein said composition contains ethylhexanoate. Results for propyl propanoate (ProProp) and butyl hex The above method, wherein said composition does not con anoate (Buhe) in several polymer formulations are shown in 60 tain ethylhexanoate. FIG. 6. Propyl propanoate was only formulated in urethane: The above method, wherein said cockroaches are selected however, the results showed significant attraction and Subse from-the group consisting of Blattella germanica, Periplan quent aggregation in the treatment harborage. Butyl hex eta americana, Blatta Orientalis, Supella Supellectilium, and anoate in Santoprene also gave significant attraction and Sub mixtures thereof. The above method, wherein said cock sequent aggregation in the treatment harborage. The other 65 roaches are Blattela germanica. attractant polymer formulations did not yield significant The above method, wherein said cockroaches are male attraction. cockroaches. US 8,273,340 B2 11 12 The above method, wherein said carrier is a thermoplastic The above composition, wherein said composition con polymer. tains a carrier or carrier material. The above method, wherein said carrier is a thermoplastic The above composition, wherein said composition com polymer comprised of 4-(1,1,3,3-tetramethylbutyl) and eth prises at least two compounds selected from the group con ylene-5-ethylidenebicyclo[2.2.1]hept-2-ene-propene ther sisting of methyl, ethyl, propyl, or butyl esters of C, satu moplastic synthetic rubber. rated or unsaturated carboxylic acids and mixtures thereof, The above method, wherein said carrier is a thermoplastic and optionally a carrier or carrier material. polymer comprised of a polyester polycaprolactone polyure The above composition, wherein said composition com thane. prises at least three compounds selected from the group con The above method, wherein said carrier is a thermoplastic 10 sisting of methyl, ethyl, propyl, or butyl esters of C, satu polymer comprised of polypropylene glycol and methylene rated or unsaturated carboxylic acids and mixtures thereof, and optionally a carrier or carrier material. bis(4-cyclohexylisocyanate). The above composition, wherein said composition com The above method according to claim 1, wherein said prises at least four compounds selected from the group con carrier is a octadecylammonium ion-substituted nanoclay. 15 sisting of methyl, ethyl, propyl, or butyl esters of C, satu A method for repelling cockroaches from an object or area, rated or unsaturated carboxylic acids and mixtures thereof, comprising (or consisting essentially of or consisting of) and optionally a carrier or carrier material. treating said object or area with a cockroach repelling com Other embodiments of the invention will be apparent to position comprising a cockroach repelling effective amount those skilled in the art from a consideration of this specifica of at least one (or two or three or four or more than one) tion or practice of the invention disclosed herein. It is compound selected from the group consisting of methyl, intended that the specification and examples be considered as ethyl, propyl, or butyl esters of C.7 Saturated or unsaturated exemplary only, with the true scope and spirit of the invention carboxylic acids and mixtures thereof, and optionally a car being indicated by the following claims. rier material or carrier. The above method, wherein said composition contains pro 25 TABLE 1 pyl butanoate, butyl propanoate, butyl butanoate, hexyl Olfactometer results (percent response to a 0.5% solution of the test butanoate, or mixtures thereof. The above method, wherein compound in mineral oil) for various esters. Results with an * after said composition contains propyl butanoate. The above them are significantly attractive; compounds with ** after them are method, wherein said composition does not contain propyl significantly repellent (mean of 3 replicates). 30 butanoate. The above method, wherein said composition con Test Compound Percent Response tains butyl propanoate. The above method, wherein said com Methyl Propanoate 60.0 position does not contain butyl propanoate. The above Methyl Butanoate 55.0 method, wherein said composition contains butylbutanoate. Methyl Pentanoate SO.O The above method, wherein said composition does not con Methyl Hexanoate 45.0 35 Methyl Heptanoate SO.O tain butylbutanoate. The above method, wherein said com Methyl Nonanoate 45.0 position contains hexyl butanoate. The above method, Methyl Decanoate 55.0 wherein said composition does not contain hexylbutanoate. Methyl Undecanoate 45.0 Methyl Dodecanoate 45.0 The above method, wherein said cockroaches are selected Ethyl Propanoate 65.0% from the group consisting of Blattella germanica, Periplan 40 Ethyl Butyrate 6.3.3 eta americana, Blatta Orientalis, Supella Supellectilium, and Ethyl Pentanoate 65.0% Ethyl Hexanoate 75.0% mixtures thereof. The above method, wherein said cock Ethyl Heptanoate 40.O roaches are Blattela germanica. Ethyl Octanoate SO.O The above method, wherein said cockroaches are male Propyl acetate 40.O cockroaches. 45 Propyl Propanoate 70.0% Propyl Butanoate 35.0* * The above method, wherein said carrier is a thermoplastic Butyl Acetate 45.0 polymer. Butyl Propanoate 15.0* * The above method, wherein said carrier is a thermoplastic Butyl Butanoate 35.0* * polymer comprised of 4-(1,1,3,3-tetramethylbutyl) and eth Butyl Pentanoate SO.O 50 Butyl Hexanoate 75.0% ylene-5-ethylidenebicyclo[2.2.1]hept-2-ene-propene ther Butyl Heptanoate 80.0% moplastic synthetic rubber. Butyl Octanoate 55.0 The above method, wherein said carrier is a thermoplastic Butyl Nonanoate 40.O polymer comprised of a polyester polycaprolactone polyure Hexyl Butanoate 35.0* * thane. The above method, wherein said carrier is a thermoplastic 55 polymer comprised of polypropylene glycol and methylene TABLE 2 bis(4-cyclohexylisocyanate). Olfactometer results for six controlled release formulations after The above method according to claim 1, wherein said aging in a fume hood for one hour (mean of 3 replicates). carrier is a octadecylammonium ion-substituted nanoclay. 60 A composition (for attracting or repelling cockroaches) Percent comprising (or consisting essentially of or consisting of) at Test Compound Absorbent Response least one compound (or two or three or four or more than one) methyltiglate Charcoal 76.6 butyl hexanoate Charcoal 82.O selected from the group consisting of methyl, ethyl, propyl, or propyl propanoate Charcoal 6S.O butyl esters of C.7 Saturated or unsaturated carboxylic acids 65 butyl heptanoate Charcoal 7O.O and mixtures thereof, and optionally a carrier or carrier mate Blank Charcoal 48.3 rial. US 8,273,340 B2 13 14 TABLE 2-continued 8. The method according to claim 1, wherein said carrier is a thermoplastic polymer comprised of polypropylene glycol Olfactometer results for six controlled release formulations after and methylene bis(4-cyclohexylisocyanate). aging in a fume hood for one hour (mean of 3 replicates). 9. The method according to claim 1, wherein said carrier is Percent a octadecylammonium ion-Substituted nanoclay. Test Compound Absorbent Response 10. A method for repelling cockroaches from an object or methyltiglate Molecular Sieve SO.O area, comprising treating said object or area with a cockroach propyl propanoate Molecular Sieve SO.O repelling composition comprising a cockroach repelling effective amount of at least one compound selected from the 10 group consisting of propylbutanoate, butyl propanoate, butyl butanoate, hexylbutanoate, allyl tiglate or mixtures thereof TABLE 3 and mixtures thereof, and optionally a carrier material or Olfactometer results for three controlled release formulations after carrier. aging in a fume hood for three time periods (mean of 3 replicates). 11. The method according to claim 10, wherein said cock 15 roaches are selected from the group consisting of Blattella Time Aged Percent germanica, Periplaneta americana, Blatta Orientalis, Supella Test Compound (Hours) Response supellectilium, and mixtures thereof. methyltiglate 1 76.6 12. The method according to claim 10, wherein said cock methyltiglate 24 66.7 roaches are Blattela germanica. methyltiglate 48 61.6 butylhexanoate 1 82.O 13. The method according to claim 10, wherein said cock butylhexanoate 24 7O.O roaches are male cockroaches. butylhexanoate 48 61.6 14. The method according to claim 10, wherein said carrier butylheptanoate 1 7O.O is a thermoplastic polymer. butylheptanoate 24 61.6 butylheptanoate 48 58.3 15. The method according to claim 10, wherein said carrier 25 is a thermoplastic polymer comprised of 4-(1,1,3,3-tetram ethylbutyl) and ethylene-5-ethylidenebicyclo[2.2.1]hept-2- ene-propene thermoplastic synthetic rubber. TABLE 4 16. The method according to claim 10, wherein said carrier is a thermoplastic polymer comprised of a polyester polyca Sustained release polymer formulated with the indicated 30 prolactone polyurethane. roach attractant. 17. The method according to claim 10, wherein said carrier ROACH is a thermoplastic polymer comprised of polypropylene gly POLYMER ATTRACTANT col and methylene bis(4-cyclohexylisocyanate). Urethane methyl tiglate 18. The method according to claim 10, wherein said carrier Urethane butyl heptanoate 35 is a octadecylammonium ion-substituted nanoclay. Urethane propyl propanoate 19. The method according to claim 1, consisting of treating Pellethane methyl tiglate Santoprene methyl tiglate said object or area with a composition comprising a cock Polyethylene methyl tiglate roach attracting effective amount of at least one compound Pellethane butyl heptanoate selected from the group consisting of ethyl propanoate, pro Santoprene butyl heptanoate 40 pyl propanoate, methyl tiglate, and mixtures thereof, and optionally a carrier material or carrier. We claim: 20. The method according to claim 1, wherein said com 1. A method for attracting cockroaches to an object or area, position does not contain ethyl propanoate and ethyl pen comprising treating said object or area with a composition tanoate. comprising a cockroach attracting effective amount of at least 45 21. The method according to claim 10, consisting of treat one compound selected from the group consisting of ethyl ing said object or area with a cockroach repelling composi propanoate, propyl propanoate, butyl hexanoate, butyl hep tion comprising a cockroach repelling effective amount of at tanoate, methyltiglate, and mixtures thereof, and optionally a least one compound selected from the group consisting of carrier material or carrier. propylbutanoate, butyl propanoate, butylbutanoate, hexyl 2. The method according to claim 1, wherein said cock 50 butanoate, allyl tiglate or mixtures thereof, and mixtures roaches are selected from the group consisting of Blattella thereof, and optionally a carrier material or carrier. germanica, Periplaneta americana, Blatta Orientalis, Supella 22. The method according to claim 10, wherein said com supellectilium, and mixtures thereof. position does not contain propylbutanoate, butylbutanoate, 3. The method according to claim 1, wherein said cock and hexylbutanoate. roaches are Blattela germanica. 55 23. The method according to claim 10, wherein said com 4. The method according to claim 1, wherein said cock position contains butyl propanoate, allyl tiglate, or mixtures roaches are male cockroaches. thereof. 5. The method according to claim 1, wherein said carrier is 24. The method according to claim 19, wherein said com a thermoplastic polymer. position contains propyl propanoate, methyl tiglate, or mix 6. The method according to claim 1, wherein said carrier is 60 tures thereof, and wherein said composition does not contain a thermoplastic polymer comprised of 4-(1,1,3,3-tetrameth ethyl propanoate and ethyl pentanoate. ylbutyl) and ethylene-5-ethylidenebicyclo[2.2.1]hept-2-ene 25. The method according to claim 21, wherein said com propene thermoplastic synthetic rubber. position does not contain propylbutanoate, butylbutanoate, 7. The method according to claim 1, wherein said carrier is and hexylbutanoate. athermoplastic polymer comprised of a polyester polycapro 65 lactone polyurethane.