Feeding deterrence of pests such as <i>Hemiptera, Lepidoptera </i>and <i>Coleoptera</i>

Abstract

Compounds are used as agents that deter feeding by insect pests, such as Hemiptera, Lepidoptera and Coleoptera. Feeding deterrence is obtained by contact of the insect pests with at least one of the compounds of the structure (I) ##STR00001##
wherein R is —OH, ═O, —OC(O)R.sub.4, —OR.sub.6, or —(OR.sub.6).sub.2, each R.sub.6 is independently an alkyl group containing from 1 to 4 carbon atoms and R.sub.4 is a branched or straight chain, saturated or unsaturated, hydrocarbyl group with zero to two double bonds and from 1 to 15 carbon atoms; X is O or CH.sub.2 with the proviso that when X is O, R can only be ═O; each Z is independently (CH) or (CH.sub.2); y is a numeral selected from 1 and 2; R.sub.1 is H or a branched or straight chain, saturated or unsaturated hydrocarbyl group with zero to two double bonds and from 1 to 15 carbon atoms; R.sub.2 is H or a branched or straight chain, saturated or unsaturated hydrocarbyl group with zero to three double bonds and from 1 to 15 carbon atoms; R.sub.3 is selected from H, a branched or straight chain, saturated or unsaturated hydrocarbyl group with zero to three double bonds and from 1 to 15 carbon atoms, —(CH.sub.2).sub.nOH, —C(O)OR.sub.5, —CH.sub.2C(O)OR.sub.7, —CH.sub.2C(O)R.sub.8, —C(O)NR.sub.9R.sub.10, and —CH.sub.2C(O)NR.sub.11R.sub.12 where each of R.sub.5, R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11 and R.sub.12 is independently selected from H and a branched or straight chain, saturated or unsaturated hydrocarbyl group with zero to three double bonds and from 1 to 15 carbon atoms and n is an integer of from 1 to 12; the bond between the 2 and 3 positions in the ring structure may be a single or a double bond; and wherein the compounds of structure (I) contain from 9 to 20 total carbon atoms in the compounds.

Claims

1. A method for deterring the feeding of one or more insect pests selected from the group consisting of the genera: Tineola, Sitotroga, Sitophilus, Cydia, Grapholita, Ostrinia, Plodia, Galleria, Manduca, Hyphantria, Lymantria, Agrotis, Trichoplusia, Spodoptera, Helicoverpa, Heliothis, Leptinotarsa, Popillia, Ips, Anthonomus, Cyclas, Crioceris, Oryzaephilus, Oulema, Anoplophora, Stegobium, Agroites, Agrilus, Epilachna, Dermestes, Lygus, Blissus, Euschistus, Nezara, Homalodisca, Circulifer, Typhlocyba, Diaphorina, Bactericera, Bemisia, Trialeurodes, Myzus, Aphis, Macrosiphum, Eriosoma, and Dysaphis, said method comprising: contacting of the pests with an effective amount of a formulation comprising at least one of the compounds selected from the group consisting of: ##STR00013## ##STR00014## ##STR00015##

2. A method for deterring the feeding of one or more insect pests selected from the group consisting of the genera: Tineola, Sitotroga, Sitophilus, Cydia, Grapholita, Ostrinia, Plodia, Galleria, Manduca, Hyphantria, Lymantria, Agrotis, Trichoplusia, Spodoptera, Helicoverpa, Heliothis, Leptinotarsa, Popillia, Ips, Anthonomus, Cyclas, Crioceris, Oryzaephilus, Oulema, Anoplophora, Stegobium, Agroites, Agrilus, Epilachna, Dermestes, Lygus, Blissus, Euschistus, Nezara, Homalodisca, Circulifer, Typhlocyba, Diaphorina, Bactericera, Bemisia, Trialeurodes, Myzus, Aphis, Macrosiphum, Eriosoma, and Dysaphis, said method comprising: contacting of the pests with an effective amount of a formulation comprising at least one of the compounds of the structure (I) ##STR00016## wherein: R is ═O; X is O; each Z is independently selected from the group consisting of (CH) and (CH.sub.2); y is a numeral selected from 1 and 2; R.sub.1 is selected from the group consisting of H and a branched or straight chain, saturated or unsaturated hydrocarbyl group with zero to two double bonds and from 1 to 15 carbon atoms; R.sub.2 is selected from the group consisting of H and a branched or straight chain, saturated or unsaturated hydrocarbyl group with zero to three double bonds and from 1 to 15 carbon atoms; R.sub.3 is selected from the group consisting of H and a branched or straight chain, saturated or unsaturated hydrocarbyl group with zero to three double bonds and from 1 to 15 carbon atoms; the bond between the 2 and 3 positions in the ring structure is a single bond, and wherein the compounds of structure (I) contain from 9 to 20 total carbon atoms in the compounds.

3. The method according to claim 2 wherein the compound comprises: R is ═O, X is O, y is 1 or 2, each Z is selected from the group consisting of (CH) and (CH.sub.2), the bond between positions 2 and 3 in the ring is a single bond, one of R.sub.1 and R.sub.2 is H or —CH.sub.3 and the other of R.sub.1 and R.sub.2 is a hydrocarbyl group containing from 9 to 15 carbon atoms and 0 to 3 double bonds, and R.sub.3 is H.

4. The method of claim 2 wherein the compound comprises: R is ═O, X is O, y is 1 or 2, each Z is selected from (CH) and (CH.sub.2), the bond between positions 2 and 3 in the ring is a single or double bond, one of R.sub.1 and R.sub.2 is H and the other of R.sub.1 and R.sub.2 is a hydrocarbyl group containing from 9 to 15 carbon atoms and 0 to 3 double bonds, and R.sub.3 is selected from the group consisting of —C(O)OR.sub.5 and —CH.sub.2C(O)R.sub.8 where R.sub.5 and R.sub.8 are each selected from a hydrocarbyl group containing from 1 to 6 carbon atoms.

5. The method according to claim 4 wherein R is ═O, y is 1, the bond between positions 2 and 3 in the ring is a single bond, and R.sub.2 and R.sub.5 are each —CH.sub.3.

6. The method according to claim 2 wherein the compound comprises: R is ═O, X is O, y is 1 or 2, each Z is selected from the group consisting of (CH) and (CH.sub.2), the bond between positions 2 and 3 of the rings is a single or double bond, one of R.sub.1 and R.sub.2 is H and the other of R.sub.1 and R.sub.2 is a hydrocarbyl group containing group containing from 9 to 15 carbon atoms and 0 to 3 double bonds, and R.sub.3 is selected from the group consisting of —C(O)OR.sub.5 and —CH.sub.2C(O)R.sub.8 where R.sub.5 and R.sub.8 are each selected from a hydrocarbyl group containing from 1 to 6 carbon atoms and wherein the total number of carbon atoms in the compounds of structure (I) is from 11 to 17.

7. The method according to claim 6 wherein the bond between positions 2 and 3 of the rings is a single bond and R.sub.5 and R.sub.7 are each selected from a hydrocarbyl group containing from 3 to 5 carbon atoms.

8. The method according to claim 6 wherein the bond between positions 2 and 3 of the rings is a single bond and R.sub.5 and R.sub.7 are each —CH.sub.3.

9. The method according to claim 2 wherein the at least one compound of structure (I) is a compound wherein: R is ═O, X is O, y is 1 or 2, each Z is selected from (CH) and (CH.sub.2), the bond between positions 2 and 3 in the ring is a single bond, R.sub.1 is an alkyl group containing from 5 to 13 carbon atoms, R.sub.2 is selected from the group consisting of H or —CH.sub.3, and R.sub.3 is H.

10. The method according to claim 9 wherein: R.sub.1 is an alkyl group of from 5 to 10 carbon atoms such that the compound of structure (I) contains from 11 to 14 total carbon atoms.

11. A method for deterring the feeding of one or more insect pests selected from the group consisting of the genera: Tineola, Sitotroga, Sitophilus, Cydia, Grapholita, Ostrinia, Plodia, Galleria, Manduca, Hyphantria, Lymantria, Agrotis, Trichoplusia, Spodoptera, Helicoverpa, Heliothis, Leptinotarsa, Popillia, Ips, Anthonomus, Cyclas, Crioceris, Oryzaephilus, Oulema, Anoplophora, Stegobium, Agroites, Agrilus, Epilachna, Dermestes, Lygus, Blissus, Euschistus, Nezara, Homalodisca, Circulifer, Typhlocyba, Diaphorina, Bactericera, Bemisia, Trialeurodes, Myzus, Aphis, Macrosiphum, Eriosoma, and Dysaphis, said method comprising: contacting of the pests with an effective amount of a formulation comprising at least one of the compounds selected from the group consisting of: ##STR00017## ##STR00018##

12. The method according to claim 2 wherein the at least one compound of structure (I) is selected from the group consisting of: ##STR00019## ##STR00020##

13. A method for deterring the feeding of one or more insect pests selected from the group consisting of the genera: Tineola, Sitotroga, Sitophilus, Cydia, Grapholita, Ostrinia, Plodia, Galleria, Manduca, Hyphantria, Lymantria, Agrotis, Trichoplusia, Spodoptera, Helicoverpa, Heliothis, Leptinotarsa, Popillia, Ips, Anthonomus, Cyclas, Crioceris, Oryzaephilus, Oulema, Anoplophora, Stegobium, Agroites, Agrilus, Epilachna, Dermestes, Lygus, Blissus, Euschistus, Nezara, Homalodisca, Circulifer, Typhlocyba, Diaphorina, Bactericera, Bemisia, Trialeurodes, Myzus, Aphis, Macrosiphum, Eriosoma, and Dysaphis, said method comprising: contacting of the pests with an effective amount of a formulation comprising at least one of the compounds selected from the group consisting of: ##STR00021## ##STR00022##

14. A method for deterring the feeding of one or more insect pests selected from the group consisting of the genera: Tineola, Sitotroga, Sitophilus, Cydia, Grapholita, Ostrinia, Plodia, Galleria, Manduca, Hyphantria, Lymantria, Agrotis, Trichoplusia, Spodoptera, Helicoverpa, Heliothis, Leptinotarsa, Popillia, Ips, Anthonomus, Cyclas, Crioceris, Oryzaephilus, Oulema, Anoplophora, Stegobium, Agroites, Agrilus, Epilachna, Dermestes, Lygus, Blissus, Euschistus, Nezara, Homalodisca, Circulifer, Typhlocyba, Diaphorina, Bactericera, Bemisia, Trialeurodes, Myzus, Aphis, Macrosiphum, Eriosoma, and Dysaphis, said method comprising: contacting of the pests with an effective amount of a formulation comprising at least one of the compounds selected from the group consisting of: ##STR00023## ##STR00024## ##STR00025##

15. A method for deterring the feeding of one or more insect pests selected from the group consisting of the genera: Tineola, Sitotroga, Sitophilus, Cydia, Grapholita, Ostrinia, Plodia, Galleria, Manduca, Hyphantria, Lymantria, Agrotis, Trichoplusia, Spodoptera, Helicoverpa, Heliothis, Leptinotarsa, Popillia, Ips, Anthonomus, Cyclas, Crioceris, Oryzaephilus, Oulema, Anoplophora, Stegobium, Agroites, Agrilus, Epilachna, Dermestes, Lygus, Blissus, Euschistus, Nezara, Homalodisca, Circulifer, Typhlocyba, Diaphorina, Bactericera, Bemisia, Trialeurodes, Myzus, Aphis, Macrosiphum, Eriosoma, and Dysaphis, said method comprising: contacting of the pests with an effective amount of a formulation comprising at least one of the compounds selected from the group consisting of: ##STR00026##

16. The method according to claim 1 wherein the compound is applied to or near crops, seeds, agricultural or ornamental trees, plants, vegetation, fibers, woven fibers, grains, processed grain, produce or packaging materials, by way of a formulation selected from the group consisting of direct spray formulations, fogger formulations, microencapsulated formulations, soil treatment formulations, seed treatment formulations, injectable formulations for injection into or onto plants or crops, granular pellets, release devices, clay-based powders, and formulations for evaporative devices.

17. The method of claim 2 wherein the at least one compound of structure (I) is selected from the group consisting of: gamma-dodecalactone, gamma-tridecalactone, gamma methyl dodecalactone, delta dodecalactone, and gamma methyl tridecalactone.

18. The method according to claim 1 wherein the compound is present in the formulation in an amount sufficient to provide increased pest repellency or mortality over control pest repellency or mortality of at least 1%.

19. The method of claim 1 wherein the formulation is used to treat food or crops such that the treated food or crops have from about 0.05 to about 500 mg/sq. in. of at least one of the compounds thereon.

20. The method according to claim 2 wherein the compounds of structure (I) have from 10 to 16 carbon atoms in the compound.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 graphically shows test results of the effects of certain test compounds on the larval feeding activity of European corn borer (Ostrinia nubialis), in accordance with the Examples.

(2) FIG. 2 graphically shows test results of the effects of certain test compounds on the larval feeding activity of fall armyworm (Spodoptera frugiperda), in accordance with the Examples.

(3) FIG. 3 graphically shows test results of the effects of certain test compounds on the larval feeding activity of black cutworm (Agrotis ipsilon) in accordance with the Examples.

(4) FIG. 4 graphically shows test results for repellency of certain test compounds against whitefly settling, in accordance with the Examples.

(5) FIG. 5 graphically shows test results for repellency of certain test compounds against whitefly settling, in accordance with the Examples.

(6) FIG. 6 graphically shows test results for repellency of certain test compounds against aphid settling, in accordance with the Examples.

(7) FIG. 7 graphically shows test results for repellency of certain test compounds against psyllid settling, in accordance with the Examples.

DETAILED DESCRIPTION OF EMBODIMENTS

(8) Deterrence of feeding by pests, such as Hemipteran, Lepidopteran and Coleopteran, and other pests, including, but not limited to, Tineola, Sitotroga, Sitophilus, Cydia, Grapholita, Ostrinia, Plodia, Galleria, Manduca, Hyphantria, Lymantria, Agrotis, Trichoplusia, Spodoptera, Helicoverpa, Heliothis, Leptinotarsa, Popillia, Ips, Anthonomus, Cyclas, Crioceris, Oryzaephilus, Oulema, Anoplophora, Stegobium, Agroites, Agrilus, Epilachna, Dermestes, Lygus, Blissus, Euschistus, Nezara, Homalodisca, Circulifer, Typhlocyba, Diaphorina, Bactericera, Bemisia, Trialeurodes, Myzus, Aphis, Macrosiphum, Eriosoma, and Dysaphis, is obtained by contact of the pests with at least one of the compounds of the structure (I)

(9) ##STR00003##
wherein
R is selected from —OH, ═O, —OC(O)R.sub.4, —OR.sub.6, and —(OR.sub.6).sub.2, wherein each R.sub.6 is independently selected from an alkyl group containing from 1 to 4 carbon atoms and R.sub.4 is a branched or straight chain, saturated or unsaturated hydrocarbyl group with zero to two double bonds and from 1 to 15 carbon atoms;
X is O or CH.sub.2 with the proviso that when X is O, R can only be ═O;
each Z is independently selected from (CH) and (CH.sub.2);
y is a numeral selected from 1 and 2;
R.sub.1 is selected from H or a branched or straight chain, saturated or unsaturated hydrocarbyl group with zero to two double bonds and from 1 to 15 carbon atoms;
R.sub.2 is selected from H and a branched or straight chain, saturated or unsaturated hydrocarbyl group with zero to three double bonds and from 1 to 15 carbon atoms;
R.sub.3 is selected from H, a branched or straight chain, saturated or unsaturated hydrocarbyl group with zero to three double bonds and from 1 to 15 carbon atoms —(CH.sub.2).sub.uOH, —C(O)OR.sub.5, —CH.sub.2C(O)OR.sub.7, —CH.sub.2C(O)R.sub.8, —C(O)NR.sub.9R.sub.10, and —CH.sub.2C(O)NR.sub.11R.sub.12 where each of R.sub.5, R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11 and R.sub.12 is independently selected from H and a branched or straight chain, saturated or unsaturated hydrocarbyl group with zero to three double bonds and from 1 to 15 carbon atoms, and n is n integer of from 1 to 12;
the bond between the 2 and 3 positions in the ring structure may be a single or a double bond; and
wherein the compounds of structure (I) contain from 11 to 20 total carbon atoms in the compounds. The disclosure also includes optical isomers, diastereomers and enantiomers of the named structures. Thus, at all stereocenters where stereochemistry is not explicitly defined, all possible epimers are envisioned.

(10) A preferred group of feeding deterrence compounds are those compounds of structure (I) wherein R is selected from —OH and ═O, X is CH.sub.2, y is 1 or 2, each Z is selected from (CH) and (CH.sub.2), the bond between positions 2 and 3 in the ring is a single bond, one of R.sub.1 and R.sub.2 is H or —CH.sub.3 and the other of R.sub.1 and R.sub.2 is a branched or straight chain, saturated or unsaturated hydrocarbyl group containing from 9 to 15 carbon atoms and 0 to 3 double bonds, and R.sub.3 is H.

(11) Another preferred group of feeding deterrence compounds are those compounds of structure (I) wherein R is selected from —OH and ═O, more preferably ═O, X is CH.sub.2, y is 1 or 2, more preferably 1, each Z is selected from (CH) and (CH.sub.2), the bond between positions 2 and 3 in the ring is a single or double bond, more preferably a single bond, one of R.sub.1 and R.sub.2 is H and the other of R.sub.1 and R.sub.2 is a branched or straight chain, saturated or unsaturated hydrocarbyl group containing from 9 to 15 carbon atoms and 0 to 3 double bonds, and R is selected from —C(O)OR.sub.5 and —CH.sub.2C(O)R.sub.8 where R.sub.5 and R.sub.8 are each selected from a straight chain or branched, saturated or unsaturated hydrocarbyl group containing from 1 to 6 carbon atoms, and more preferably 3 to 5 carbon atoms and still more preferably —CH.sub.3.

(12) Another preferred group of feeding deterrence compounds are those compounds of structure (I) wherein R is ═O, X is O, y is 1 or 2, each Z is selected from (CH) and (CH.sub.2), the bond between positions 2 and 3 of the rings is a single or double bond, more preferably a single bond, one of R.sub.1 and R.sub.2 is H and the other of R.sub.1 and R.sub.2 is a branched or straight chain, saturated or unsaturated hydrocarbyl group containing from 9 to 15 carbon atoms and 0 to 3 double bonds, and R.sub.3 is selected from —C(O)OR.sub.5 and —CH.sub.2C(O)R.sub.8 where R.sub.5 and R.sub.7 are each selected from a hydrocarbyl group containing from 1 to 6 carbon atoms, and more preferably 3 to 5 carbon atoms and still more preferably-CH.sub.3 and wherein the total number of carbon atoms in the compounds of structure (I) is from 9 to 20, more preferably from 9 to 14 total carbon atoms.

(13) Another preferred group of feeding deterrence compounds are those compounds of structure (I) wherein R is ═O, X is O, y is 1 or 2, each Z is selected from (CH) and (CH.sub.2), the bond between positions 2 and 3 in the ring is a single bond, R.sub.1 is a branched or straight chain, saturated or unsaturated alkyl group containing from 5 to 13 carbon atoms, R.sub.2 is H or —CH.sub.3, R.sub.3 is H, and more preferably where R.sub.1 is an alkyl group of from 5 to 10 carbon atoms such that the compound of structure (I) contains from 11 to 14 total carbon atoms.

(14) The active compounds of structure (I) may be employed in any suitable formulation, such as, but not limited to, direct spray formulations, fogger formulations, microencapsulated formulations, soil treatment formulations, seed treatment formulations, injectable formulation for injection into the plant, granular pellets, release devices, clay-based powders, and formulations for use in evaporative devices. The formulations of the active compounds will be such that the areas or materials being treated will have from about 0.05 to about 500 mg/sq. in., preferably about 0.25 to about 50 mg/sq. in., of the active compounds thereon.

(15) Representative examples of compounds of structure (I) include, but are not limited to,

(16) ##STR00004## ##STR00005## ##STR00006## ##STR00007## ##STR00008## ##STR00009## ##STR00010## ##STR00011## ##STR00012##

(17) Preferred compounds of structure (I) include apritone, methyl apritone, methyl dihydrojasmonate, methyl dihydrojasmolate, propyl dihydrojasmonate, gamma-dodecalactone, gamma-tridecalactone, gamma methyl dodecalactone, delta dodecalactone, gamma methyl tridecalactone, 3-methyl-5-propyl-2-cyclohexenone, 3-methyl-5-isobutyl-2-cyclohexenone, 3-methyl-5-isobutyl-2-cyclohexenol, 3-methyl-5-pentyl-2-cyclohexenone, 3-methyl-5-hexyl-2-cyclohexenone, and 3-methyl-5-heptyl-2-cyclohexenone.

(18) A test was designed to measure the repellency as feeding deterrence in brown marmorated stink bugs (BMSB). Five replicates of 5 BMSBs were introduced into test arenas, containing one 60 mm×15 mm Petri dish with treated filter papers in which a food source (green bean) was attached, at the start of the test. The small Petri dishes containing the treated filter paper and food source were covered with a fitted Petri dish lid in between observation times, and were removed 5 minutes before each observation time to prevent stink bugs from feeding until sated. The distribution of the BMSBs was observed and documented hourly for 5 hours. The results are set forth in Table 1.

(19) TABLE-US-00001 TABLE 1 Repellency averaged Compound in a 57% Ethanol:43% water solution over 5 hours Control (57% Ethanol:43% water solution) 38% Methyl Dihydrojasmonate (3.5%) 90% Methyl Dihydrojasmonate - Low epi (2.5%) 58% Methyl Dihydrojasmonate - High epi (2.5%) 39% Propyl Dihydrojasmonate (3.5%) 100%  Propyl Dihydrojasmonate - Low epi (2.5%) 74% Propyl Dihydrojasmonate - High epi (2.5%) 49% Para-Menthanediol (3.5%) 91% Gamma-Dodecalactone (3.5%) 82% Gamma-Methyl Tridecalactone (3.5%) 67%

(20) Another test was designed to measure the repellency as feeding deterrence in Codling Moth larvae. The treatment was applied to the surface of a proprietary laboratory media in a tray with wells for each compound. The media was allowed to dry for 30-60 minutes so that larvae were not exposed to it as a liquid. One first instar codling moth larva was then placed on the treated media. The cover film was placed on the tray to prevent escapes. Ten additional replicates treated with a 57% ethanol solution were prepared to serve as controls. The larvae were observed at 24 hours to determine if they burrowed into the media. After the 24 hour reading, the larvae were extracted from the media to record any mortality. The results are set forth in Table 2.

(21) TABLE-US-00002 TABLE 2 Compound at 3.5% in a 57% Ethanol:43% water Repellency at solution 24 hours Control (57% Ethanol:43% water solution)  8% Para-Menthanediol 10% Propyl Dihydrojasmonate 59% Prenyl Dihydrojasmonate 79% Gamma-Dodecalactone 46% Methyl Apritone 100%  3-Methyl-5-Propyl-2-Cyclohexenone 21% 3-Methyl-5-Propyl-2-Cyclohexenol 30% 3-Methyl-5-Heptyl-2-Cyclohexenone 95%

(22) Mortality observations were also made for the above protocol. The control was the 57% ethanol:43% water solution. The results are set forth in Table 3.

(23) TABLE-US-00003 TABLE 3 Increased Mortality Compound at 3.5% in a 57% Ethanol:43% water over Control Mortality solution at 24 hours Para-Menthanediol  3% Propyl Dihydrojasmonate 18% Prenyl Dihydrojasmonate 34% Gamma-Dodecalactone 37% Methyl Apritone 95% 3-Methyl-5-Propyl-2-Cyclohexenone  1% 3-Methyl-5-Propyl-2-Cyclohexenol  9% 3-Methyl-5-Heptyl-2-Cyclohexenone 93%

(24) Ten replicates of 30 kernels of wheat were immersed into the test compound and allowed to dry for 24 hours. The grains were then transferred to a test container, and 10 granary weevils were released. Test containers were secured and left for a 3 week period. At the end of this time, the wheat grains were examined for developing larvae and damage by larvae. The number of grains that contained developing larvae or that showed damage was recorded. Ten additional replicates treated with isopropyl alcohol were prepared to serve as controls. The results are set forth in Table 4.

(25) TABLE-US-00004 TABLE 4 Increased Increased Repellency Mortality Test compound, diluted in isopropyl vs. Control over Control alcohol Repellency Mortality Methyl Apritone (5%) 11% N/A Propyl Dihydrojasmonate (5%)  8% N/A Gamma Tridecalactone (5%) 40% N/A 3-Methyl-5-Propyl-2-Cyclohexenone (5%) 66% 57% 3-Methyl-5-Isobutyl-2-Cyclohexenol (5%) 86% 93%
Effects of Formulations of this Disclosure (BRI) on the Feeding Activity of Agricultural Pest Insects

(26) The effects of celery ketone (3ME5HCS), BRIMIX (PBRMIX01), high delta (KDBRIMIX), delta dodecalactone (463), methyl dihydro jasmolate (MDJSMLT), propyl dihydro jasmonate (PRPYLDJ), and apritone (499) on the larval feeding activity of European corn borer (Ostrinia mibialis), fall armyworm (Spodoptera frugiperda), and black cutworm (Agrotis ipsilon) was examined by exposing the larvae to an artificial diet treated (100% solution undiluted), or untreated (control), with the BRI formulations. Each of the 8 treatment groups consisted of 4 replicates of 6 third-instar larvae for each insect (24 larvae per treatment per species). Larvae were provided the treated and untreated artificial diet for 24 h. Following the exposure period, the total weight of treated or untreated artificial diet consumed was recorded to the nearest milligram and subtracted from the total weight of each artificial diet at the start of the experiments. Statistical analysis of differences in artificial diet consumption based on treatment was conducted using a one-way analysis of variance and Dunnett's multiple comparison test. All calculations and statistical analysis were conducted using GraphPad Prism 8 at a significance level (a) of 0.05.

(27) Bars represent mean diet consumed (%)±standard deviation (n=4). Asterisks indicate a significant difference between the formulation treatment and the respective untreated control based on a one-way analysis of variance and Dunnett's multiple comparison test where P<0.05 was considered significant.

(28) Test results showing the effects of celery ketone (3ME5HCX), BRIMIX (PBRMIX01), high delta (KDBRIMIX), delta dodecalactone (463), methyl dihydro jasmolate (MDJSMLT), propyl dihydro jasmonate (PRPYLDJ), and apritone (499) on the larval feeding activity of European corn borer (Ostrinia nubialis) are graphically shown in FIG. 1.

(29) Test results showing the effects of celery ketone (3ME5HCX), BRIMIX (PBRMIX01), high delta (KDBRIMIX), delta dodecalactone (463), methyl dihydro jasmolate (MDJSMLT), propyl dihydro jasmonate (PRPYLDJ), and apritone (499) on the larval feeding activity of fall armyworm (Spodoptera frugiperda) are graphically shown in FIG. 2.

(30) Test results showing the effects of celery ketone (3ME5HCX), BRIMIX (PBRMIX01), high delta (KDBRIMIX), delta dodecalactone (463), methyl dihydro jasmolate (MDJSMLT), propyl dihydro jasmonate (PRPYLDJ), and apritone (499) on the larval feeding activity of black cutworm (Agrotis ipsilon) are graphically shown in FIG. 3.

(31) Behavioral assays were conducted within an arena consisting of a 20×20×20 cm mesh cage. The cage borders were covered by non-reflective white screen to remove any potential visual cues. A single light was disposed above the arena. With a luxmeter, the luminosity was checked and it did not vary significantly in the different portions of the arena. Two plants (either a citrus branches or potted tomato) were placed 15 cm apart on each end of the arena. The experimental insects (whiteflies, Asian citrus psyllid or winged aphids) were collected by a mouth aspirator in a plastic vial. The vial was placed in the center of the arena at equal distance from each experimental plant. The vial was open and the insects were allowed to select the plant for 24 hours. After 24 hours, the insects were counted on each plant by the experimenter.

(32) Repellency of Test Compounds Against Whitefly Settling

(33) Forty whiteflies were placed in an arena with two tomato plants. Whitefly were allowed to choose between a tomato plant sprayed with a solution of 1% repellent chemical+tween 20 (1:1 ratio) in distilled water, and a control plant sprayed with of a solution of 1% tween 20 only. The results are graphically shown in FIG. 4.

(34) Forty whiteflies were placed in an arena with two tomato plants. Whiteflies were allowed to choose between a tomato plant treated with 0.5% repellent chemical in a carrier of kaolin clay. (3M5H2C=3-methyl-5-hexyl-2-cyclohexanone, DDL=delta dodecalactone, MDJ=Methyl dihydrojasmonate, Apritone=Apritone, Mix=mixture of delta dodecalactone, methyl dihydrojasmolate, propyl dihydrojasmonate). The results are graphically shown in FIG. 5.

(35) Repellency of Test Compounds Against Aphid Settling

(36) Forty aphids were placed in an arena with two tomato plants. The aphids were allowed to choose between a tomato plant sprayed with a solution of 1% repellent chemical+tween 20 (1:1 ratio) in distilled water, and a control plant sprayed with of a solution of 1% tween 20 only. (3M5H2C=3-methyl-5-hexyl-2-cyclohexanone, DDL=delta dodecalactone, Apritone=Apritone, Mix=mixture of delta dodecalactone, methyl dihydrojasmolate, propyl dihydrojasmonate). The results are graphically shown in FIG. 6.

(37) Repellency of Test Compounds Against Psyllid Settling

(38) Forty Asian citrus psyllids were placed in an arena with two citrus cuttings. The psyllid were allowed to choose between a citrus cutting sprayed with a solution of 1% repellent chemical+tween 20 (1:1 ratio) in distilled water, and a control cutting sprayed with of a solution of 1% tween 20 only. (3M5H2C=3-methyl-5-hexyl-2-cyclohexanone, Apritone=Apritone). The results are graphically shown in FIG. 7.

(39) Melon Aphid Repellency on Leaf Choice Assays

(40) Aphis gossypii are maintained on squash plants. Individual aphids (n=100) are given the choice between leaves with and without repellent treatments. A separate group of aphids are given a choice between untreated vs. untreated leaves as a control. The number of aphids choosing each leaf is counted both choice tests. The number of aphids choosing each treatment is compared to the control to determine the repellent effect. The results are set forth in Table 5.

(41) TABLE-US-00005 TABLE 5 Number of Aphids Treatments vs Control Choosing each Treatment 3% Compound in a Triton X:Water solution Untreated Treated Control (Triton X:water solution) 50 50 Apritone 70 30 Methyl Apritone 70 30 Apritol 70 30 Methyl dihydrojasmolate 70 30 Methyl dihydrojasmonate 70 30 Propyl dihydrojasmonate 70 30 3-methyl-5-hexyl-2-cyclohexanone 70 30 Gamma Tridecalactone 80 20 Delta-dodecalactone 80 20
Psyllid Repellency on Potato Choice Assays

(42) Potato plants are sprayed with either a 3% solution of repellent chemical in a 5%:95% ETOH:Water or only 5%:95% ETOH:Water as a control. Two plants are placed in a screen cage, either a treatment vs control tree or a control vs control tree, 100 psyllids are released into each cage. The number of psyllids choosing each leaf is counted for both choice tests. The number of psyllids choosing each treatment is compared to the control to determine if there is a repellent effect. The results are set forth in Table 6.

(43) TABLE-US-00006 TABLE 6 Number of Psyllids Treatments vs Control Choosing each Treatment 3% Compound in a Triton X:Water solution Untreated Treated Control (Triton X:water solution) 50 50 Apritone 70 30 Methyl Apritone 70 30 Apritol 70 30 Methyl dihydrojasmolate 70 30 Methyl dihydrojasmonate 70 30 Propyl dihydrojasmonate 70 30 3-methyl-5-hexyl-2-cyclohexanone 70 30 Gamma Tridecalactone 80 20 Delta-dodecalactone 80 20
Leafhopper Repellency on Citrus Choice Assays

(44) Citrus seedlings are sprayed with either a 3% solution of repellent chemical in a 5%:95% ETOH:Water or only 5%:95% ETOH:Water as a control. Two seedlings are placed in a screen cage, either a treatment vs control tree or a control vs control tree. 100 sharpshooters are released into each cage. The number of sharpshooters choosing each leaf is counted for both choice tests. The number of sharpshooters choosing each treatment is compared to the control to determine if there is a repellent effect. The results are set forth in Table 7.

(45) TABLE-US-00007 TABLE 7 Number of Psyllids Treatments vs Control Choosing each Treatment 3% Compound in a Triton X:Water solution Untreated Treated Control (Triton X:water solution) 50 50 Apritone 70 30 Methyl Apritone 70 30 Apritol 70 30 Methyl dihydrojasmolate 70 30 Methyl dihydrojasmonate 70 30 Propyl dihydrojasmonate 70 30 3-methyl-5-hexyl-2-cyclohexanone 70 30 Gamma Tridecalactone 80 20 Delta-dodecalactone 80 20

(46) To compare the feeding/resting preference of stink bug adults for different plant parts, 10 pots with soybean plants at the R.sub.6 (pod-filling) stage of development are used. 5 pots of soybeans are sprayed with 3% of treatment in a 2% Triton X:water solution and 5 pots of soybean are treated with 2% Triton X:water solution as controls. Thirty stink bugs are placed individually in each cage and allowed to feed for 48 hours. Insects are removed and plant parts are collected for visual analysis of damage. Feeding damage on the pods is counted for both treatments. The selective antifeeding rate (%) formula is [(C−T)/(C+T)]×100, and the non-selective antifeeding rate (%) formula is [(C−T)/C)]×100, where C and T are the numbers of feeding damages on the control and treated plant pods, respectively. The results are set forth in Table 8.

(47) TABLE-US-00008 TABLE 8 Euschistus heros-Neotropical Brown Stink Bugs % Antifeedent 3% Compound in a 5% Ethanol:95% water solution Activity Control (Triton X:water solution) 0 Apritone 60 Methyl Apritone 60 Apritol 60 Methyl dihydrojasmolate 90 Methyl dihydrojasmonate 90 Propyl dihydrojasmonate 100 3-methyl-5-hexyl-2-cyclohexanone 60 Gamma Tridecalactone 80 Delta-dodecalactone 80

(48) For choice feeding assays, 3% alcohol solutions of the tested compounds are prepared. Disks (4.0 cm in diameter) are cut from potato leaves and are dipped in the test solutions or alcohol alone as a control. After the complete evaporation of the solvent, the disks are offered to 10 larvae. Control and treated disks are placed at alternate corners in Petri dishes (150 by 20 mm) lined with moistened filter paper (choice test). All dishes are placed in an incubator. Four replicates and 40 larva are used for each chemical. In each replicate, the insects are allowed to feed ad libitum for 24 h at 24 C under a 16:8 (L:D) photoperiod. After 24 h, the remaining uneaten area of each potato leaf disk is measured using a scanner and software. The selective antifeeding rate (%) formula is [(C−T)/(C+T)]×100, and the non-selective antifeeding rate (%) formula is [(C−T)/C)]×100, where C and T are the areas consumed by the control and treated leaf disks, respectively. The results are set forth in Table 9.

(49) TABLE-US-00009 TABLE 9 Leptinotarsa decemlineata-Colorado Potatoe Beetles 3% Compound in a 5% Ethanol:95% water solution % Repellency Control (Triton X:water solution) 0 Apritone 15 Methyl Apritone 15 Apritol 15 Methyl dihydrojasmolate 15 Methyl dihydrojasmonate 15 Propyl dihydrojasmonate 15 3-methyl-5-hexyl-2-cyclohexanone 80 Gamma Tridecalactone 40 Delta-dodecalactone 40
Japanese Beetle Feeding Damage on Basil

(50) For choice feeding assays, 3% alcohol solutions of the tested compounds are prepared. Disks (4.0 cm in diameter) are cut from basil leaves and are dipped in the test solutions or alcohol alone as a control. After the complete evaporation of the solvent, the disks are offered to 1 adult beetle. All dishes are placed in an incubator. Four replicates are used for each chemical. After 24 h, the remaining uneaten area of each basil leaf disk is measured using a scanner and software. The selective antifeeding rate (%) formula is [(C−T)/(C+T)]×100, and the non-selective antifeeding rate (%) formula is [(C−T)/C)]×100, where C and T are the areas consumed by the control and treated leaf disks, respectively. The results are set forth in Table 10.

(51) TABLE-US-00010 TABLE 10 Popillia japonica 3% Compound in a 5% Ethanol:95% water solution % Repellency Control (Triton X:water solution) 0 Apritone 15 Methyl Apritone 15 Apritol 15 Methyl dihydrojasmolate 15 Methyl dihydrojasmonate 15 Propyl dihydrojasmonate 15 3-methyl-5-hexyl-2-cyclohexanone 80 Gamma Tridecalactone 40 Delta-dodecalactone 40
Dermestid Beetle Feeding Damage on Silk Fabric

(52) For feeding assays, 3% alcohol solutions of the tested compounds are prepared. Disks (4.0 cm in diameter) of undyed silk fabric are dipped in the test solutions or alcohol alone as a control. After the complete evaporation of the solvent, the disks are offered to 10 late instar larvae. All dishes are placed in an incubator. Four replicates are used for each chemical. After 1 week, the remaining uneaten area of each silk disk is measured using a scanner and software. The selective antifeeding rate (%) formula is [(C−T)/(C+T)]×100, and the non-selective antifeeding rate (%) formula is [(C−T)/C)]×100, where C and T are the areas consumed by the control and treated silk disks, respectively. The results are set forth in Table 11.

(53) TABLE-US-00011 TABLE 11 Dermestid spp. 3% Compound in a 5% Ethanol:95% water solution % Repellency Control (Triton X:water solution) 0 Apritone 15 Methyl Apritone 15 Apritol 15 Methyl dihydrojasmolate 15 Methyl dihydrojasmonate 15 Propyl dihydrojasmonate 15 3-methyl-5-hexyl-2-cyclohexanone 80 Gamma Tridecalactone 40 Delta-dodecalactone 40

(54) Ten replicates of 30 kernels of corn are immersed into the test compound and allowed to dry for 24 hours. The kernels are then transferred to a test container, and 10 saw tooth grain beetles are released. Test containers are secured and left for a 3 week period. At the end of this time, the wheat grains are examined for feeding damage. The number of grains that showed damage is recorded. Ten additional replicates treated with isopropyl alcohol are prepared to serve as controls. The results are set forth in Table 12.

(55) TABLE-US-00012 TABLE 12 Repellency of Test Compounds on Grain Beetles Increased Repellency Test compound, diluted in isopropyl alcohol vs. Control Repellency Methyl Apritone (5%) 10% Propyl Dihydrojasmonate (5%) 10% Gamma Tridecalactone (5%) 40% 3-Methyl-5-Propyl-2-Cyclohexenone (5%) 60% 3-Methyl-5-Isobutyl-2-Cyclohexenol (5%) 85%

(56) For feeding assays, 3% alcohol solutions of the tested compounds are prepared. Disks (2.0 cm in diameter) of undyed silk fabric are dipped in the test solutions or alcohol alone as a control. After the complete evaporation of the solvent, the disks are presented in a choice test to 10 late instar Tineola spp. larvae. All dishes are placed in an incubator in the dark. Four replicates are used for each chemical. After 24 hours, the number of individuals choosing to feed on each disk are counted. The results are set forth in Table 13.

(57) TABLE-US-00013 TABLE 13 Clothes Moth Feeding Damage on Silk Fabric Tineola spp. 3% Compound in a 5% Ethanol:95% water solution Untreated Treated Control (Triton X:water solution) 50 50 Apritone 80 20 Methyl Apritone 80 20 Apritol 80 20 Methyl dihydrojasmolate 80 20 Methyl dihydrojasmonate 80 20 Propyl dihydrojasmonate 80 20 3-methyl-5-hexyl-2-cyclohexanone 80 20 Gamma Tridecalactone 90 10 Delta-dodecalactone 90 10
Feeding Repellent Assay for Indian Meal Moth Larva

(58) One gram of rice is weighed and treated with 2% by weight of each test chemical or ethanol as a control for each treatment and replicate. The grains are allowed to dry and then weighed again. Treated or control rice grains are placed in a petri dish. Third instar larvae are starved for 8 h and gently introduced into the center of each compartment. 20 larva are screened per treatment, and each experiment is repeated three times. The weight of rice grains is measured again after 1 week. The selective antifeeding rate (%) formula is [(C−T)/(C+T)]×100, and the non-selective antifeeding rate (%) formula is [(C−T)/C)]×100, where C and T are the areas consumed by the control and treated leaf disks, respectively. The results are set forth in Table 14.

(59) TABLE-US-00014 TABLE 14 Plodia interpunctella % Antifeedent 10% Compound in a 5% Ethanol:95% water solution Activity Control (Triton X:water solution) 0 Apritone 70 Methyl Apritone 70 Apritol 70 Methyl dihydrojasmolate 60 Methyl dihydrojasmonate 60 Propyl dihydrojasmonate 60 3-methyl-5-hexyl-2-cyclohexanone 60 Gamma Tridecalactone 70 Delta-dodecalactone 70
Feeding Repellent Assay for Angoumois Larva

(60) One gram of rice is weighed and treated with 2% by weight of each test chemical or ethanol as a control for each treatment and replicate. The grains are allowed to dry and then weighed again. Treated or control rice grains are placed in a petri dish. Third instar larvae are starved for 8 h and gently introduced into the center of each compartment. 20 larva are screened per treatment, and each experiment is repeated three times. The weight of rice grains is measured again after 1 week. The selective antifeeding rate (%) formula is [(C−T)/(C+T)]×100, and the non-selective antifeeding rate (%) formula is [(C−T)/C)]×100, where C and T are the areas consumed by the control and treated leaf disks, respectively. The results are set forth in Table 15.

(61) TABLE-US-00015 TABLE 15 Sitostroga cerealella % Antifeedent 10% Compound in a 5% Ethanol:95% water solution Activity Control (Triton X:water solution) 0 Apritone 70 Methyl Apritone 70 Apritol 70 Methyl dihydrojasmolate 60 Methyl dihydrojasmonate 60 Propyl dihydrojasmonate 60 3-methyl-5-hexyl-2-cyclohexanone 60 Gamma Tridecalactone 70 Delta-dodecalactone 70

(62) The feeding deterrent compounds of this disclosure may be blended with active repellents or toxicants including, but not limited to, N,N-Diethyl-m-toluamide (DEET®) and p-Menthane-3,8-diol (PMD).

(63) While the disclosure has been described herein with reference to the specific embodiments thereof, it will be appreciated that changes, modification and variations can be made without departing from the spirit and scope of the inventive concept disclosed herein. Accordingly, it is intended to embrace all such changes, modification and variations that fall with the spirit and scope of the appended claims.