INSECT CONTROL AND REPELLENCY

Abstract

The control and repellency of biting insects, houseflies, ticks, ants, fleas, gnats, cockroaches, spiders, and foul-smelling insects is obtained by contact of the insects with at least one of the compounds of structure (I), (Formula I) where R is -OH, =O, -OC(O)R4, -OR6, or -(O6)2, where each R6 is independently an alkyl group containing from 1 to 4 carbon atoms and R4 is a linear or branched, saturated or unsaturated hydrocarbyl group with from zero to two double bonds and from 1 to 15 carbon atoms; X is O or CH2, with the condition that when X is OR it can only be =O; each Z is independently selected from (CH) and (CH2); and is a number selected from 1 and 2; R1 is selected from H or a branched or linear chain hydrocarbyl group, saturated or unsaturated, with from zero to two double bonds and from 1 to 15 carbon atoms;R2 is H and a linear or branched chain hydrocarbyl group, saturated or unsaturated, with from zero to three double bonds and from 1 to 15 carbon atoms; R3 is H, a linear or branched chain hydrocarbyl group, saturated or unsaturated, with from zero to three double bonds and from 1 to 15 carbon atoms, -(CH2)nOH, -C(O)OR5, -CH2C(O)OR7, -CH2C(O)R8, -C(O)NR9R10 or CH2C(O)NR11R12 wherein each of R5, R7, R8, R9, R10, R11 and R12 is independently H and a linear or branched chain hydrocarbyl group, saturated or unsaturated, with from zero to three double bonds and from 1 to 15 carbon atoms, and n is an integer n from 1 to 12; The link between positions 2 and 3 in the ring structure can be a single link or a double link;and wherein the compounds of structure (I) contain from 11 to 20 carbon atoms, except where R is =O, X =CH2 and e is 1, the compounds of structure (I) contain from 13 to 20 carbon atoms, provided that when R3 is -CH2C(O)OR, R1 and R2 must be H or a saturated hydrocarbyl group with zero double bonds. The invention also includes optical isomers, diastereomers, and enantiomers of the compounds of structure (I).

Description

INSECT CONTROL AND REPELLENCY Field of Invention This invention relates to compounds used as agents to control and repel biting mosquitoes, houseflies, ticks, ants, fleas, gnats, cockroaches, spiders, and other foul-smelling insects. Background of the Invention It is well known that insects and other pests have plagued humanity since the dawn of time, and that a wide variety of control agents, insecticides, and pesticides have been employed to try to control, repel, or eradicate them. However, most of these agents are difficult to apply or pose a danger to both humans and the environment. DDT, for example, was commonly used in World War II and has since been banned for safety reasons. A common component in many chemical insecticides used today is pyrethrin, which, while considered among the safer insecticides, is known to irritate the eyes, skin, and respiratory system in humans. Furthermore, pyrethrin is known to be particularly harmful to aquatic life. DEET®, or N,N-diethyl-m-toluamide, is widely used against a variety of insects and pests, but it is characterized by an unpleasant odor, a short duration of effect, and the ability to dissolve plastics. Furthermore, several safety concerns have been raised regarding the use of DEET®, and some governments have restricted the amount of the active ingredient that can be used in formulations. This presents an additional problem, as DEET® is subject to evaporation and must be formulated at such high doses to maintain its effectiveness. In addition, many insects and pests have developed resistance to DEET® due to its widespread use. Therefore, there is a need for an insect repellent formulation that is non-toxic to people, plants, and other animals that may be exposed to the application areas. An additional need is for a pest control formulation that provides long-lasting effects, thereby limiting the need for frequent reapplication of treated areas. Furthermore, a pest control formulation that may be toxic to certain pests but not to humans and that does not produce an undesirable effect on the environment is also required. Summary of the Invention According to this invention, the control and repellency of biting mosquitoes, houseflies, ticks, ants, fleas, gnats, cockroaches, spiders, and foul-smelling insects is obtained by the contact of the insects with at least one of the compounds of structure (I) where R is selected from -OH, -OC(O)R4, -ORe, and -(ORe)2, wherein each of R6 is independently selected from an alkyl group containing from 1 to 4 carbon atoms and R4 is a hydrocarbyl group, linear or branched chain, saturated or unsaturated with zero to two double bonds and from 1 to 15 carbon atoms; X is 0 or CH2, with the condition that when X is 0 R can only be =0; each Z is selected independently of (CH) and (CH2); and it is a number selected from 1 and 2; Ri is selected from H or a branched or linear chain hydrocarbyl group, saturated or unsaturated, with from zero to two double bonds and from 1 to 15 carbon atoms; R2 is selected from H and a linear or branched chain hydrocarbyl group, saturated or unsaturated, with from zero to three double bonds and from 1 to 15 carbon atoms; R3 is selected from H, a linear or branched chain hydrocarbyl group, saturated or unsaturated, with from zero to three double bonds and from 1 to 15 carbon atoms, (CH2)nOH, -C(O)OR5, -CH2C(0)OR7, -CH2C(O)R8, -C(0)NR9Rio, and CH2C(0)NR11R12 wherein each of R5, R7, Rs, R9, Rio, R11 and R12 is independently selected from H and a linear or branched chain hydrocarbyl group, saturated or unsaturated, with from zero to three double bonds and from 1 to 15 carbon atoms, and n is an integer from 1 to 12; The bond between positions 2 and 3 in the ring structure can be a single or a double bond; and where the compounds of structure (I) contain from 11 to 20 carbon atoms, except where R is = 0, X = CH2e and is 1, the compounds of structure (I) contain from 13 to 20 carbon atoms, provided that when R3 is -CH2C(O)OR7 Ri and R2 must be H or a saturated hydrocarbyl group with zero double bonds. The invention also includes optical isomers, diastereomers, and enantiomers of the compounds of structure (I). Thus, at all stereocenters where the stereochemistry is not explicitly defined, all possible epimers are provided. iviA / a / zuz 1 / un 41 uo Compounds of structure (I) can be used to control biting mosquitoes, houseflies, ticks, ants, fleas, gnats, cockroaches, spiders, and other foul-smelling insects. Compounds of structure (I) have been found to be toxic to ticks and cockroaches and can be used successfully to kill these and other insects by applying the compounds to areas or environments where they are known or suspected to live. For the purpose of achieving toxicity, it is preferred that compounds of structure (I) contain 11 to 17 carbon atoms, and more preferably 11 to 14 carbon atoms. Compounds of structure (I) can be used in any suitable formulation, such as solutions, oils, creams, lotions, sprays, or similar products. These formulations can be used in the form of cleaning products, wipes, etc.and can be applied to either the skin or inanimate surfaces. The compounds of this invention are long-lasting and do not require frequent reapplication. Detailed Description of the Invention Control and repellency of biting mosquitoes, houseflies, ticks, ants, fleas, gnats, cockroaches, spiders, and foul-smelling insects is achieved by contact of the insects with at least one of the compounds in structure (I) R where R is selected from -OH, -OC(O)R4, -ORg, and -(ORg)2, wherein each Rg is independently selected from an alkyl group containing from 1 to 4 carbon atoms and R4 is a branched or linear chain hydrocarbyl group, saturated or unsaturated, with from zero to two double bonds and from 1 to 15 carbon atoms; X is O or CH2, with the condition that when X is 0 R can only be =0; each Z is selected independently of (CH) and (CH2); and it is a number selected from 1 and 2; Ri is selected from H or a branched or linear chain hydrocarbyl group, saturated or unsaturated, with from zero to two double bonds and from 1 to 15 carbon atoms; R2 is selected from H and a linear or branched chain hydrocarbyl group, saturated or unsaturated, with from zero to three double bonds and from 1 to 15 carbon atoms; R3 is selected from H, a saturated or unsaturated hydrocarbyl group, linear or branched chain, with from zero to three double bonds and from 1 to 15 carbon atoms, (CH2)nOH, -C(O)OR5, -CH2C(O)OR7, -CH2C(O)R8, -C(O)NR9Rio, and CH2C(O)NR11R12 wherein each of Rs, R?, Rg, R9, Rio, Rn and R12 is independently selected from H and a saturated or unsaturated linear or branched chain hydrocarbyl group with from zero to three double bonds and from 1 to 15 carbon atoms, and n is an integer from 1 to 12; The bond between positions 2 and 3 in the ring structure can be a single or a double bond; and where the compounds of structure (I) contain from 11 to 20 carbon atoms, except where R is = 0, X = CH2e, and is 1, the compounds of structure (I) contain from 13 to 20 carbon atoms, provided that when R3 is -CH2C(O)OR7 Ri and R2 must be H or a saturated hydrocarbyl group with zero double bonds. The invention also includes optical isomers, diastereomers, and enantiomers of the aforementioned structures. Thus, at all stereocenters where the stereochemistry is not explicitly defined, all possible epimers are provided for. For the purpose of achieving toxicity, it is preferred that the compounds of structure (I) contain from 11 to 17 carbon atoms and more preferably from 11 to 14 carbon atoms. A preferred group of control and repellent compounds are those compounds of Structure (I) where R is selected from -OH and =0, X is CH2, and is 1 or 2, each Z is selected from (CH) and (CH2), the bond between positions 2 and 3 in the ring is a single bond, one from Ri and R2 is H or -CH3 and the other from R: and R2 is a branched or linear chain hydrocarbyl group, saturated or unsaturated containing 9 to 15 carbon atoms and 0 to 3 double bonds, and R3 is H. Another preferred group of control and repellent compounds are those compounds of structure (I) where R is selected from -OH and =0, more preferably =0, X is CH2, and is 1 or 2, more preferably 1, each Z is selected from (CH) and (CH2) , the bond between positions 2 and 3 in the ring is a single or a double bond, more preferably a single bond, one of Ri and R2 is H and the other of Ri and R2 is a branched or linear chain hydrocarbyl group, saturated or unsaturated, containing from 9 to 15 carbon atoms and 0 to 3 double bonds, and R3 is selected from -C(O)ORs and -CH2C(O)Rs where R5 and Rs are each selected from a linear or branched chain hydrocarbyl group, saturated or unsaturated, containing from 1 to 6 carbon atoms, and more preferably from 3 to 5 carbon atoms and even more preferably -CH3. Another preferred group of control compounds and ML / a / ZUZ 1 4 1 uo repellency are those compounds of structure (I) where R is = 0, X is 0, and y is 1 or 2, each Z is selected from (CH) and (CH2) , the bond between positions 2 and 3 of the rings is a single or double bond, more preferably a single bond, one of Ri and R2 is H and the other of Ri and R2 is a branched or linear chain hydrocarbyl group, saturated or unsaturated, containing from 9 to 15 carbon atoms and 0 to 3 double bonds, and R3 is selected from -C(O)ORs and -CH2C(O)Rs where R5 and R7 are each selected from a hydrocarbyl group containing from 1 to 6 carbon atoms, and more preferably from 3 to 5 carbon atoms and even more preferably -CH3 and wherein the total number of carbon atoms in the compounds of structure (I) is from 11 to 17, more preferably from 11 to 14 total carbon atoms. Another preferred group of control and repellent compounds are those compounds of structure (I) where R is = 0, X is 0, and Y is 1 or 2, each Z is selected from (CH) and (CH2), the bond between positions 2 and 3 on the ring is a single bond, Ri is a linear or branched chain alkyl group, saturated or unsaturated, containing from 5 to 13 carbon atoms, R2 is H or -CH3, R3 is H, and more preferably where Ri is an alkyl group from 5 to 10 carbon atoms, so that the compound of structure (I) contains from 11 to 14 total carbon atoms. Another preferred group of control and repellent compounds are those compounds of structure (I) wherein at least one compound of structure (I) is a compound selected from a compound of structure (I) wherein Ri-OH and =0, Ri and R2 are each selected from H or a saturated hydrocarbyl group with zero double bonds, X is 0, Z is selected from (CH) and (CH2) , and is 1, the bond between positions 2 and 3 of the rings is a single bond, R3 is -CH2C(O)OR7, and R7 is selected from H and a linear or branched, unsaturated or saturated hydrocarbyl group with zero or 1 double bonds and containing from 1 to 15 carbon atoms. The active compounds of structure (I) can be formulated in any of the following suitable formulations, including but not limited to solutions, oils, creams, lotions, shampoos, sprays, or similar products. Traditional inert carriers, including but not limited to alcohols, esters, and petroleum distillates, could be used to produce formulations of the active compounds for use as repellent formulations. Other carriers include, but are not limited to, biodegradable oils, including the Olestra* family of oils, isopropyl myristate, and squalane. When using the aerosol formulation, it is preferable to add a propellant. Suitable propellants include propane, butane, isobutane, dimethyl ether, carbon dioxide, nitrous oxide, nitrogen, and combinations thereof. The formulations described above can be prepared by any convenient means, for example, by mixing the active compound(s) with one or more of the other ingredients described above. Furthermore, the active components of structure (I) can be mixed with existing active repellents or toxic substances, including, but not limited to, N,ND-diethyl-m-toluamide (DEET®) and p-menthane-3,8-diol (PMD). Representative examples of compounds of structure (I) include, but are not limited to, ML / a / ZUZ 1 4 1 uo Methyl 2-(3-oxo-2-pentylcyclopentyl)acetate Chemical formula: C13H22O3 Molecular Weight: 226.31 Methyl Jasmonate Dihydro Ethyl 2-(3-oxo-2pentylcyclopentyl)acetate Chemical formula: C14H24O3 Molecular weight: 240.34 Ethyl Jasmonate Dihydro Methyl 2- (3-hydroxy-2pentylcyclopentyl)acetate Chemical formula: C13H24O3 Molecular weight: 228.33 Methyl Jasmolate Dihydro 2-(3-hydroxy-2-pentylcyclopentyl)ethyl acetate Chemical formula: C14H26O3 Molecular weight: 242.35 Ethyl Jasmonate Dihydro pentylcyclopentyl)propyl acetate Chemical formula: C15H26O3 Molecular weight: 254.37 Propyl Jasmonate Dihydro 2-(3-hydroxy-2-pentylcyclopentyl)propyl acetate Chemical Formula: C15H28O3 Molecular Weight: 256.38 Propyl Jasmolate Dihydro 2- (3-oxo-2pentylcyclopentyl)3-methylbut-2-enyl acetate Chemical formula: C17H28O3 Molecular weight: 280.40 Prenyl Jasmonate Dihydro IV l4 I uo 3-methylbut-2-enyl-2-(3-hydroxy-2-pentylcyclopentyl)acetate Chemical formula: C17H30O3 Molecular weight: 282.42 Prenyl Jasmolate Dihydro 3-(2-hydroxyethyl)-2-pentylcyclopentanol Chemical formula: C12H24O2 Molecular weight: 200.32 Methyl Jasmodiol Dihydro W / N-diethyl-í-(3-oxo-2pentylcyclopentyl)acetamide Chemical formula: C16H29O2 Molecular weight: 267.41 MDJ amide Methyl 2-(3,3-dimethoxy-2pentylcyclopentyl)acetate Chemical formula: C15H28O4 Molecular weight: 272.38 Methyl Jasmonate Dihydro Dimethyl Ketal (E) -2- (3,7-dimethylocta-2,6-dienyl)cyclopentanone Chemical formula: C15H24O Molecular weight: 220.35 Apritone (E)-2-(3,7-dimethylocta-2,6-dienyl)cyclopentanol Chemical formula: C15H26O Molecular weight: 222.37 Apritol 2-((2E,6E)-3,7-dimethylnon-2,6-dienyl)cyclopentanol Chemical formula: C16H2O Molecular weight: 234.38 Methyl Apritone 2-((2E,6E)-3,7-dimethylnone-2,6dienyl)cyclopentanol Chemical formula: C16H28O Molecular weight: 236.39 Methyl Apritol dimethylnonyl)cyclopentanone Chemical formula: CigHaoO Molecular weight: 238.41 Tetrahydromethyl apritone dimethylnonyl)cyclopentanol Chemical formula: C16H32O Molecular weight: 240.42 Tetrahydromethyl apricotol Chemical Formula: CnHigO Molecular Weight: 166.26 3-methyl-5-butyl-2-cyclohexenone X. Chemical Formula: CnHi8O Molecular Weight: 166.25 3-methyl-5-isobutyl-2-cyclohexenone Chemical Formula: C12H20O Molecular Weight: 180.29 3-methyl-5-pentyl-2-cyclohexenone Chemical Formula: C13H22O Molecular Weight:194.31 3-methyl-5-hexyl-2-cyclohexenone Chemical Formula: C14H24O Molecular Weight: 208.34 3-methyl-1,5-hepty-1,2-cyclohexenone Chemical Formula: C11H2O0 Molecular Weight: 188.28 -metí 1 - 5 - isobutyl-2-cyclohexen-l-ol -metí 1 - 5 -hept i 1-2-cyclohexen-lol Chemical Formula: C14H26O Molecular Weight: 210.36 Chemical Formula: C13H20O Molecular Weight: 192.30 3-methyl-5-(ζ-3-hexenyl)-2-cyclohexenone -me til-5-pentyl-2-c iclohexen-1ol Chemical Formula: C12H22O Molecular Weight: 182.30 5-decyldihydrofuran-2(3H)-one MΛ / a / ZUZ 1 4 1 uo Chemical Formula: C14H26O2 Molecular Weight: 226.36 Gamma-tetradecalactone 6-nonyltetrahydro-2H-pyran-2-one Chemical Formula: C14H26O2 Molecular Weight: 226.36 Delta-tetradecalactone THE Gamma-Methyldodecalactone 2(3H)-Furanone,5-octyldihydro-5-methyl19 Π eu H * M Gamma-Methyl Tridecalactone 5-methyl-5-nonyldihydrofuran-2(3H)-one 4-methyl-4-nonyl gamma butyrolactone C14 lactone IVlA / a / ZU¿ I / U14Ί uo Chemical Formula: C15H28O2 Molecular Weight: 240.38 Pentadecalactone and Gamma Gamma Heptadecalactone Chemical Formula: C17H32O2 Molecular Weight: 268.24 Especially preferred compounds of structure (I) include methyl apritone, methyl dihydrojasmonate, propyl dihydrojasmonate, gamma-dodecalactone, gamma-tridecalactone, gamma-tetradecalactone, gamma-methyl dodecalactone, gamma-methyl tridecalactone, 3-methyl-5-pentyl-2-cyclohexenone, 3-methyl1-5-pentyl1-2-cyclohexene1 and 3-methyl1-5-hepti 1-2 cyclohexenone. The pest control agents of this invention are effective control agents against biting insects, houseflies, ticks, ants, fleas, gnats, cockroaches, spiders, and malodorous insects. Biting insects include, but are not limited to, sand flies, stable flies, deer flies, horseflies, black flies, and gnats. Houseflies include, but are not limited to, common houseflies and small houseflies. Examples of ticks include, but are not limited to, deer ticks, lone star ticks, and brown dog ticks. Ants include, but are not limited to, carpenter ants, bullet ants, Jack bridge ants, Pharaoh ants, and fire ants. Cockroaches include, but are not limited to, American cockroaches, German cockroaches, Oriental cockroaches, and Tropical cockroaches.Spiders include, but are not limited to, cob-spinning spiders such as the Black Widow. Odorous insects include, but are not limited to, the brown marbled stink bug, green stink bug, wood bug, harlequin bug, and rice stink bug. The amount of the active compound of structure (I) used in any control or repellent formulation will depend on the type of formulation used and the insect or pest against which the formulation is employed, but will generally be found in the range from approximately 1% to approximately 30% by weight in an inert carrier. The active control compounds of structure (I) can be applied to, or impregnated into, clothing or fabric. The amount of active material can range from approximately 0.278 g / m² (0.025 g / ft²) to approximately 40 g / m² (3.6 g / ft²). When the compounds of structure (I) are used as tick toxicants, the compound is applied to an area or environment to provide from approximately 0.278 g / m² (0.025 g / ft²) to approximately 53.22 g / m² (4.79 g / ft²) of an area or environment where the toxic effect on ticks is desired. The invention is illustrated by, but not limited to, the following examples. Sand fly control is determined by the following protocol as generally described in J. Med. Entomol. 43 (6), 1248-1252 (2006). Volunteers wearing shorts are seated. Using a skin marking template and a washable ink marker, skin areas are represented by openings in the floor of six 3 x 4 cm cells of a K&D module. These openings are outlined on the outer, upper, and inner thighs of each volunteer. The six treated cell rectangles each represent a random block, and each volunteer has three blocks on each thigh. All treatments against the sand fly P. papatasi are pipetted onto a 4 x 5 cm rectangular area (so the skin area covered by a treatment exceeds the template markings by 0.5 cm in each direction) of the subjects' skin with 55 µL of isopropyl alcohol / treatment containing either 10% or 5% compound / µL of isopropyl alcohol. Treating a slightly larger area ensures that the areas beneath each K&D module contain only treated skin.Skin treated with isopropyl alcohol alone served as the control. In all tests, adjacent cells of the K&D module were supplied with ten sand flies. The K&D modules loaded with sand flies were placed over the skin areas, and the trap doors of the K&D module were opened above the areas. After a five-minute skin exposure, the trap doors were closed. The number of sand fly bites for each cell was recorded. The data from this test are presented in Table 1. The percentage of bites is the percentage compared to the bites of the control, which was used as a benchmark. 100%. Table 1 Compound Treatment Level -10% Treatment Level 5% Isopropyl Alcohol (control) 100% 100% Methyl apritone 0% 9.9% Methyl apritol 0% 12.5% ​​Methyl dihydrojasmonate -0% Methyl dihydrojasmolate 0% 0% At a concentration of 10%, all compounds tested showed complete repellency. At 5%, methyl dihydrojasmonate and methyl dihydrojasmolate still repelled 100% of sand flies, while methyl apritone and methyl apritol repelled 90.1% and 87.5%, respectively. The following test protocol is used to demonstrate the efficacy of the compounds of this invention in controlling or repelling stable flies. Five replicates of 100 mixed stable flies each are placed in mesh cages. The cages are positioned so that the stable flies have access to five blood-filled, warm membrane walls. The membranes are treated with methyl dihydrojasmonate, gamma-dodecactone, methyl apritone, or DEET®, all at 7% and 15% in isopropyl alcohol, or isopropyl alcohol as a control. There are five replicates tested with a positional rotation of the repellent in each replicate. Fresh batches of stable flies are used for each replicate. Thus, each test sample is placed in each of the five wells, allowing any positional bias to be eliminated. The number of stable flies exploring each well is recorded at two-minute intervals for twenty minutes.The total number of scans in each well is counted at the end of the twenty-minute observation period, and the average repellency percentage for each compound is calculated. An analysis of variance is performed to compare the average number of scans for each treatment membrane. The number of scans for the control was taken as the 100% baseline, and the percentage for the test compounds is the percentage of scans for the test compound compared to the number of scans for the control. The results are presented in Table 2. Table 2 Compound Scans in 7% of test compound Scans in 15% of test compound Isopropyl alcohol (control) 100% 100% DEET® 45.9% 16.2% Methyl apritone 28.8% 7.4% Methyl dihydroasmonate 4.5% 3.2% Gamma dodecalactone 6.2% 3.6% As shown in the table above, all treated membranes repelled the control. Methyl apritone, methyl dihydrojasmonate, and iodecalactone each repelled better than DEET® at the same concentrations. Human trials were also conducted to demonstrate the effectiveness of the inventor's repellents against stable flies. Tests were also performed with the compounds of structure (I) in combination with para-menthane-3,8-diol (PMD) to demonstrate synergistic effects. Two insect repellents per day were tested by applying them to each arm of a human subject and placing the arms into a cage containing 50 stable flies. The exposure period was five minutes at 30-minute intervals until the first confirmed bite. The stable flies were reared at room temperature, relative humidity, and photoperiod. Groups of 50 flies were aspirated from the cage and released into 454.56 cm³ (16 oz) cups with mesh lids, which were used to release the flies into the two test cages. The test subjects had a 250 cm² area on each forearm, measured and marked for treatment.The adjacent areas above and below the treated area are protected with elastic bandages and held in place with Elastikon® surgical tape. The application rate ranged from 0.65 ml to 1 ml / 250 cm² for all repellents. The actual amount of repellent used was based on the quantity that provided complete coverage of the 250 cm² treatment area. Repellent was applied using a micropipette or a syringe without the needle. The repellents were then spread evenly over the treatment area with a gloved finger. Each test subject's forearm was allowed to air dry for approximately 30 minutes before the first exposure. The study coordinator or assistant technician IVlA / a / ZU¿ I / U14Ί uo to the test subjects in the insertion of their arms into the test cages, taking care not to rub them against the cloth sleeve. Both treated arms are inserted into a cage; there are two subjects (4 arms) per cage. The test subjects were exposed, their treated forearms, to flies in the test cages for 5 minutes. Afterward, the subjects remove their arms from the cages with the help of the study coordinator or technician. The exposures of each arm are repeated every 30 minutes until it is determined that the repellent on that arm is no longer effective ('breakout') or until 8 hours have elapsed, whichever comes first. The breakthrough occurs when the first confirmed sting is observed. A confirmed sting occurs when a sting is followed by a second sting in the same exposure period or in the next subsequent exposure period. The second sting becomes the confirmed sting, and the breakthrough time is taken as the time of the first sting. When a confirmed sting occurs, the test is discontinued in that arm. The results in Table 3 below are the average of two tests on two different test subjects. The compounds were diluted in isopropyl alcohol. 1 uo Table 3 100% Sting Protection Compound: 15% p-menthane-3,8-diol (PMD) 4.25 h, 30% PMD 6.5 h, 30% propyl dihydrojasmonate (PDJ) 4 h, 15% PMD and 15% PDJ 8 h, 30% gamma-methyl tridecalactone 1.75 h, 15% PMD and 15% gamma-tridecalactone 6.25 h As shown in the table above, when combined with known repellents, such as PMD, the inventor's materials exhibit a synergistic effect. To demonstrate the effectiveness of the inventor's compounds against houseflies, three replicates of 50 houseflies each were released into cages with 0.3 x 0.3 x 0.3 m (1 x 1 x 1 ft) mesh. The bottom of each cage was lined with brown kraft paper and divided into four equal quadrants. Each quadrant contained a temporary filter paper food tray. Two of the four filter papers were treated with repellent, and two were treated with isopropanol. The control cages contained filter papers treated with isopropanol only. The number of flies landing on filter paper per quadrant was recorded every 30 minutes for a total of 6 hours. The cages were rotated to eliminate position bias. Table 4 below shows the overall repellency of the tested compounds. Each of the test samples was diluted in isopropyl alcohol. Table 4 ΙνΙΛ / α / ΖυΖΊ / U 14 1 UO Test Sample in Isopropyl Alcohol % of Overall Repellency 5% Methyl Dihydrojasmonate 52 5% Propyl Dihydrojasmonate 52 7% Propyl Dihydrojasmonate 23 5% Methyl Apritone 45 5% gamma Tridecalactone 80 5% Delta Tetradecalactone 76 7.5% gamma Dodecalactone 100 7.5% gamma Tridecalactone 94 7.5% gamma Tetradecalactone 80 7.5% gamma Pentadecalactone 87 7.5% gamma Heptadecalactone 39 Brown dog tick control was determined using the following protocol. Filter paper strips, 2.54 cm x 7.62 cm (1 x 3 in.), were placed on a sheet of aluminum foil treated with 1 ml of each of the test samples and allowed to dry. The end of each treated strip was stapled to an untreated filter paper strip of the same dimensions. The stapled strips were suspended vertically over a tray, with the treated half attached to a horizontal glass rod by a metal clip. The untreated half was lowered when the strip was positioned vertically. Brown dog ticks, *Rhipicephalus sanguinea*, of mixed sexes, were purchased from a supplier. Five replicates of five ticks each were used for each treatment regimen, plus five additional replicates for the control.Ticks sent to the test site were given at least one day to acclimate to the stress of transport before being used for testing. Tick specimens that appeared sluggish or dying were not used. Suitable ticks were removed from their containers and allowed to search over the free end of the test strip. Once present on the strip, they were observed as they crawled along it until they came into contact with the treated paper. If, once in contact with the treated area, the tick either turned away, stopped, or fell off, it was classified as repelled. If it continued crawling across the treated strip, even after briefly stopping, it was classified as not repelled.A maximum observation time of 1 minute per replicate was allowed for ticks to observe their response after reaching the treated area. However, during the trial, if more time was needed, the maximum observation time could be adjusted at the discretion of the study coordinator. At the end of the observation period, the number of ticks repelled was recorded. Tick behavior was recorded when applicable, such as whether the number of ticks affected or repelled increased in successive replicates over time. After each treatment parameter was completed, the test chamber was ventilated for five minutes by activating the exhaust fan and opening the door to the chamber. Ticks were used only once. The average number of ticks exhibiting each behavioral category was calculated and compared to the control replicates. As shown below in Table 5, in this test protocol, the control without repellent repelled 0% of the ticks. γ-dodecalactone, methyl apritone, and methyl jasmonate dihydro each repelled 100% of the ticks. Table 5 Treatment in isopropyl alcohol unless otherwise indicated. Average % Repellency Control 0 Gamma-dodecalactone (Pure) 100 Gamma Tridecalactone (7.5%) 100 Methyl apritone (Pure) 100 Methyl apritone (7.5%) 100 Methyl dihydrojasmonate (Pure) 100 7.5% Propyl dihydrojasmonate (PDJ) 96 7.5% PDJ / PDM* in a 52:48 ratio 100 * PMD = p-menthane-3,8-Diol A second repellent assay was also used to evaluate six test samples against Brown Dog Ticks. Five replicates of five ticks each were given the opportunity to search on an untreated vertical strip of filter paper and then allowed to move upward onto a second vertical strip of filter paper treated with one of the six candidate repellents or DEET®. In the control situation, the second strip was treated with isopropanol. Ticks were then observed for changes in direction or behavior in response to contact with the repellent. Ticks were recorded as either repelled or not repelled. The compounds were diluted in isopropyl alcohol. The percentages of repelled ticks are shown below in Table 6. Table 6 Treatment Average % Repellency Control 4 Gamma-Tetradecalactone (15%) 92 Methyl Dihydrojasmonate (15%) 100 Propyl Dihydrojasmonate (15%) 100 Methyl Apritone (15%) 100 DEET (7%) 96 The following protocol was used to test the compounds of this invention for toxicity (mortality) against ticks. Five replicates of five dog ticks were used for each treatment. Five replicates of five untreated ticks served as controls. Strips of filter paper were placed on a sheet of aluminum foil, and enough of each test sample was applied to fully saturate the paper. The paper was then rolled up and placed inside a glass-lidded jar, lining the sides of the jar. A small paper disc was also saturated with the test sample and placed at the bottom of the jar. The ticks Brown dog ticks (Rhipicephalus sanguinea) are then introduced into jars, which are covered with aluminum foil. The inside of the foil is painted with some of the test samples. The ticks remain in the jars, constantly exposed to the test samples, for the duration of the test. A small hole is pierced through the foil for ventilation. Each control replicate undergoes the same procedures outlined above, except that it is not treated. The controls are placed in the same area as the test replicates for the duration of the test. Mortality observations are made at 24 hours.Ticks were classified as live (able to move normally), moribund (those classified as moribund would show some movement but would not be able to crawl in a coordinated manner, or would not be able to right themselves if placed on their backs), or dead (not moving after physical stimuli). All dead ticks were confirmed by palpation or shaking to ensure they were unable to move; any ticks showing visible movement were recorded as moribund. At 24 hours, tick mortality was 0% for the control, 100% for γ-dodecalactone, 100% for methyl apritone, and 76% for the [unspecified treatment]. IV l4 1 uo methyl dihydrojasmonate. See Table 7 for tabulated results. Table 7 Treatment % mortality at 24h Control 0 Gamma-Dodecalactone (pure) 100 Methyl apritone (pure) 100 Methyl dihydrojasmonate (pure) 76 3-Methyl-5-Pentyl-2-cyclohexanol 12 (10%) (100% morbidity) Pharaoh ants were evaluated using the following protocol. The face of a 43.18 cm x 58.42 cm (17 x 23 in) rectangular sheet of cardboard was sprayed with the test sample or acetone, except for a region within a 15.24 cm (6 in) circle. The treated cardboard was allowed to dry. Five worker ants were placed in the center of the untreated 15.24 cm (6 in) circle and allowed to roam outside the circle onto the treated surface. The ant behavior at the treated-untreated interface was recorded for 5 minutes after release. The test compounds were diluted in acetone. IVlA / a / ZU¿ I / U14Ί uo Table 8 Test compound % crosses without stopping % stops at the interface % slow but crosses Acetone (control) 82 12 4 Methyl dihydroasmonate (50%) 50 32 20 Methyl apritone (50%) 66 66 2 Gamma dodecalactone (50%) 82 10 8 The effectiveness of the compounds of this invention in controlling or repelling German cockroaches is illustrated by the following protocol. Each food pellet is placed on a paper square (station) treated with one of the repellent materials. The materials are diluted 50% in acetone, and a station of pure acetone is also used. Both stations are placed on the same side of the sand. The cockroaches are kept without food for two days and then released into the sand. They are provided with a feeding option in each food pellet. A control sand with one acetone-treated station and one untreated station are also used. The distribution of cockroaches within the sand is recorded at 30-minute intervals over the course of four hours. The repellency at four hours is calculated by the number of cockroaches in the untreated station versus the total number of cockroaches in all stations.Cockroaches that do not feed are excluded. Table 9 shows the results. Table 9 Acetone treatment % repellency 4 hours Methyl apritone (50%) 100 Methyl dihydrojasmonate (50%) 72.2 Propyl dihydrojasmonate (50%) 87.50 Prenyl dihydrojasmonate (50%) 87.5 Farnesyl cyclopentanone (50%) 100 Gamma-Dodecalactone (50%) 9 6.6 Gamma-Tetradecalactone (50%) 82.4 Gamma-Tetradecalactone (50%) 75 Gamma-Heptadecalactone (50%) 100 Additionally, toxicity was determined by a forced exposure test under the following protocol. Filter paper circles were treated with the test compound. Cockroaches were released onto the treated circles, which were then covered with inverted plastic cylinders placed over the paper discs. The cockroaches were left on the substrates for 24 hours, and mortality was assessed. Table 10 Compound in acetone unless otherwise noted. Mortality @ 24h gamma-Heptadecalactone (pure) 22% gamma-Tetradecalactone (pure) 46% 3-Methyl-5-pentyl-2-cyclohexenone (2.5%) 96% 3-Methyl-5-heptyl-2-cyclohexenone (2.5%) 10% Control of Black Widow Spiders is determined using the following protocol. A test container is prepared containing two cardboard tube shelters, one half treated with a test sample and the other half treated with isopropanol. A spider is introduced into the center of the tube. The spider is then given the option to move to one end of the shelters. The following day, its location is recorded and compared to the results from a shelter containing untreated halves of the tubes. On the day of the test, one of the two shelters was sprayed with the test sample solution using a 56.83 cm³ (2 oz) pump spray bottle. Only the surfaces most likely to be contacted by the spider were treated. Therefore, only the inside of one of the shelter tubes, including the end disc, was sprayed (spiders would not be able to access the outside of the shelter). The total amount of product was weighed and recorded. The treated surface was allowed to dry for at least one hour, or until no solvent was detectable by smell. At that point, the shelter tubes were assembled. Common cardboard tube shelters are constructed from two half-letter size (13.97 cm x 21.59 cm) sheets of paper, rolled and glued together to form a short tube. One end of each is covered with a cardboard circle, while the other end is later glued to the open end of the other half-sheet, forming a long tube. Each paper circle has a hole punched in the center for viewing, and the circle is held in place with clear plastic wrap and tape and / or rubber bands. The solvent-treated half is labeled with a "C" on the inside and outside walls using a pencil or pen with solvent-resistant ink.Before forming the final tube shelter, a semicircular hole is cut into one of the margins of each sheet so that, once the two tubes are taped together, the holes correspond to the top and at the junction of the tubes for the introduction of the spiders. Twenty-five sands were prepared in this manner for each test sample. There were five replicates of five spiders each. Twenty-five additional control sands were also prepared. These were prepared in the same way, except that the areas to be sprayed were sprayed only with isopropanol. Five spider replicas are selected for each test formulation and for the control. The specimens are visually examined for their overall physical condition. Unresponsive spiders or specimens exhibiting uncoordinated movement are rejected before the test begins. The spiders are transferred directly into the containment jars using flexible tweezers or with gentle pressure from an artist's brush. Due to their cannibalistic tendencies, each jar contains only one spider. They are kept in the jar until the time of testing. At the start of the test, the spiders are placed directly into the middle of the receptacle tube through the opening at the top, and the opening is covered, with only one spider per sand. After this introduction, the spiders' movements are observed briefly to see if they exhibit signs of agitation or widespread morbidity from exposure to the test samples. They are left alone for 24 hours, after which their location within the sand is recorded. Spiders present inside the receptacle treated with the test repellent are considered tolerant. The distribution results are summarized below in the Table 11. Table 11 Compound @ 5% in isopropanol % Repellency Methyl dihydrojasmonate 87.5 Propyl dihydrojasmonate 62.5 Methyl apritone 37.5 gamma Tridecalactone 75.0 gamma Pentadecalactone 75.0 To demonstrate the repellency of the inventor's materials against brown marmorated foul-smelling insects (BMSB), five replicate sands were each set up with two semicircular filter papers (one treated and one untreated). One treated semicircular filter paper was placed at the bottom of each test sand next to one half of an untreated semicircular filter paper. The two semicircular filter papers were aligned together to completely cover the bottom of the test sand. The control sands were also set up in a similar manner, except that both were treated with acetone. Five replicates of 5 BMSBs were then introduced into both the treated and control sands. By releasing them in the center of the sand, the BMSBs were presented with a choice of treated vs. untreated substrate (or untreated vs. untreated substrate in the control sands).The repellency of the BMSBs was recorded 24 hours after treatment. The results are summarized below in Table 12. Table 12 Isopropyl alcohol formulations % Repellency at 24 hours Methyl dihydrojasmonate (2.5%) 74 Methyl dihydrojasmonate (5%) 100 Propyl dihydrojasmonate (2.5%) 80 Propyl dihydrojasmonate (5%) 100 Gamma-Dodecalactone (10%) 100 Gamma-Tridecalactone (5%) 70 Gamma-Methyl-tridecalactone (2.5%) 80 Gamma-Tetradecalactone (2.5%) 82 Gamma-Tetradecalactone (5%) 91 p-Menthane-3,8-diol (2.5%) 80 While the invention has been described herein with reference to its specific embodiments, it should be appreciated that changes, modifications, and variations may be made without departing from the spirit and scope of the inventive concept described herein. Accordingly, it is intended to encompass all such changes, modifications, and variations that fall within the spirit and scope of the appended claims. It is hereby stated that, as of this date, the best method known to the applicant for putting the aforementioned invention into practice is the one that is clear from the present description of the invention.

Claims

1. A method for the control or repelling of one or more of the insects selected from the group of biting flies, houseflies, ticks, ants, fleas, biting mosquitoes, cockroaches, spiders, and bed bugs, the method being characterized in that it comprises bringing the insects into contact with an effective inhibitory amount of at least one of the compounds selected from the group consisting of: 2-(3-hydroxy-2-pentylcyclopentyl)acetate Chemical formula: C13H24O3 Molecular weight: 228.33 Methyl Jasmolate dihydro 4 1 uo ethyl 2-(3-oxo-2-pentylcyclopentyl)acetate Chemical formula: C14H24O3 Molecular weight: 240.34 Ethyl Jasmonate Dihydro pentylcyclopentyl)acetate Chemical formula: C1SH23O3 Molecular weight: 256.38 Propyl Jasmolate Ethyl dihydro pentylcyclopentyl)acetate Chemical formula: C14H26O3 Molecular weight: 242.35 Ethyl Jasmolate Dihydro 2- (3-oxo-2pentylcyclopentyl)propyl acetate Chemical formula: C15H26O3 Molecular weight: 254.37 Propyl Jasmonate Dihydro 2 -(3 -oxo-2 pentylcyclopentyl)acetate of 3-methylbut-2-enyl Chemical formula: C17H28O3 Molecular weight: 280.40 Prenyl Jasmonate Dihydro IV l4 I uo 3-methylbut-2-enyl-2 -(3-hydroxy-2pentylcyclopentyl)acetate Chemical Formula: C17H30O3 Molecular weight: 282.42 Prenyl Jasmolate Dihydro methyl 2-(3,3-dimethoxy-2pentylcyclopentyl)acetate Chemical Formula: C15H3822. Methyl Jasmcnate Dihydro Dimethyl Cetal N,N-diethyl-2-(3-oxo-2pentylcyclopentyl)acetamide Chemical Formula: C16H29NO2 Molecular Weight: 267.41 Amide of MDJ and 3- (2-Hydroxyethyl)-2pentylpentanol Chemical Formula: C12H24O2 Molecular weight: 200.32 Methyl Jasmodiol Dihydro.

2. A method for the control or repelling of one or more of the insects selected from the group of biting flies, houseflies, ticks, ants, fleas, biting mosquitoes, cockroaches, spiders, and bed bugs, the method being characterized in that it comprises bringing the insects into contact with an effective inhibitory amount of at least one of the compounds selected from the group consisting of: 5-octyldihydrofuran-2(3H)-one Chemical Formula: C12H22O2 Molecular Weight: 198.30 Gamma-dodecalactone 5-nonyldihydrofuran-2(3H)-one Chemical Formula: C13H24O2 Molecular Weight: 212.33 Gamma-tridecalactone 5-decyldihydrofuran-2(3H)-one Chemical Formula: C14H26O2 Molecular Weight: 226.36 Gamma-tetradecalactone 6-nonyltetrahydro-2H-pyran-2-one Chemical Formula: C14H26O2 Molecular Weight: 226.36 Delta-tetradecalactone ML / a / ZUZ 1 4 1 uo Gamma Methyl Dodecalactone 2(3H)-Furanone, 5-octyldihydro-5-methyl- Gamma Methyl Tridecalactone 5-methyl-5-nonyldihydrofuran-2(3H)-one 4-methyl-4-nonyl gamma butyrolactone C14 lactone Chemical Formula C15H28O2 Molecular Weight: 240.38 Range Pentadecalactone y.

3. A method for the control or repelling of one or more insects selected from the group of biting flies, houseflies, ticks, ants, fleas, biting mosquitoes, cockroaches, spiders, and bed bugs, the method being characterized in that it comprises contacting the insects with an effective inhibitory amount of at least one of the compounds selected from the group consisting of: (E)-2-(3,7-dimethylocta-2,6-dienyl)cyclopentanone Chemical formula: C15H24O Molecular weight: 220.35 Apritone (E)-2-(3,7-dimethylocta-2,6-dienyl)cyclopentanol Chemical formula: C15H26O Molecular weight: 222.37 Apritol 2-((2E,6E)-3,7-dimethylnona-2,6-dienyl)cyclopentanone Chemical formula: CisHzsO Molecular weight: 234.38 Methyl Apritone 2-((2E,6E)- 3,7-dimethylnona-2,6-dienyl)cyclopentanol Chemical formula: CieHseO Molecular weight: 236.39 Methyl Apritone 2-(3,7-dimethylnonyl)cyclopentanone Chemical formula: C16H30O Molecular weight: 238.41 2-(3,7-dimethylnonyl)cyclopentanol Chemical formula: C16H32O Molecular weight: 240.42 Tetrahydromethyl apritone Tetrahydromethyl apritol.

4. A method for the control or repelling of one or more of the selected insects from the group of biting flies, houseflies, ticks, ants, fleas, IVIA / a / ZUZ I 41 or biting mosquitoes, cockroaches, the method is characterized by: insects in contact with a c at least one of the compounds consists of: OA> j Chemical Formula: CnHieO Molecular Weight: 166.26 3-methyl-5-butyl-2-cyclohexenone, spiders and bed bugs, in that it comprises putting the selected insects in contact with a substance that has an effective inhibitory quantity of the selected insects from the group that Chemical Formula: CnHieO Molecular Weight: 166.26 3-methyl-5-isobutyl-2-cyclohexenone Chemical Formula: Ci2H2OO Molecular Weight: 180.29 3-methyl-5-pentyl-2cyclohexenone Chemical Formula: Ci3H22O Weight Molecular:194.31 3-methyl-5-hexyl-2-cyclohexenone Chemical Formula: C14H24O Molecular Weight: 208.34 3-methyl-5-heptyl-2-cyclohexenone Chemical Formula: C13H2CO Molecular Weight:192.30 3-methyl-5-(z-3-hexenyl)-2cyclohexenone Formula Chemistry: CiiH2oO Molecular Weight:168.28 3-methyl - 5 - isobutyl-2-cyclohexen-l-ol 3 -methyl-5-pentyl-2-cyclohexen-l-ol Chemical Formula: C12H22O Molecular Weight: 182.30 3 -methyl - 5-heptyl-2-cyclohexen-l-ol Chemical Formula: Ci4H26O Molecular Weight: 210.36 2-((2E,6E)-3,7,ll-trimethyldodeca-2,6,10trienyl)cyclopentanone Chemical Formula: C20H32O Molecular Weight:288.47 Farnesylcyclopentanone 2-((2E,6E)-3,7,11-trimethyldodeca-2,6,10-trienyl)cyclopentanol Chemical Formula: C20H34O Molecular Weight:290.48 Farnesylcyclopentanol 3-(2-oxopropyl)-2-pentylcyclopentanone Chemical Formula: C13H22O2 Molecular Weight: 210.31 Amyl Cyclopentanone Propanone.

5. A method for the control or repelling of one or more of the insects selected from the group of biting flies, houseflies, ticks, ants, fleas, biting mosquitoes, cockroaches, spiders and bed bugs, the method comprising contacting the insects with an effective inhibitory amount of at least one of the compounds selected from methyl apritone, propyl dihydrojasmonate, gamma-dodecalactone, gamma-tridecalactone, gamma-tetradecalactone, gamma-methyl dodecalactone and gamma-methyl tridecalactone, 3-methyl-5-pentyl-2-cyclohexenone, 3-methyl-5-pentyl-2-cyclohexenol and 3-methyl-5-heptyl-2-cyclohexenone.

6. The method according to claim 1, characterized in that at least one of the compounds is applied to the skin in the form of wipes, lotions, creams, oils or sprays.

7. The method according to claim 1, characterized in that at least one of the compounds in combination with a compound selected from DEET® (N,N-Diethyl-toluamide) and para-menthane-3,8-diol is applied to the skin in the form of wipes, lotions, creams, oils or sprays.

8. The method according to claim 1, characterized in that at least one of the compounds is applied to a surface or impregnated into clothing or fabric, or applied to cleaning products.

9. The method according to claim 1, characterized in that contact of ticks or cockroaches with at least one of the compounds produces toxicity for the ticks or cockroaches.

10. The method according to claim 2, characterized in that at least one of the compounds is applied to the skin in the form of wipes, lotions, creams, oils or sprays.

11. The method according to claim 2, characterized in that at least one of the compounds in combination with a compound selected from DEET® (N,NDietil-m-toluamide) and para-menthane-3,8-diol is applied to the skin in the form of wipes, lotions, creams, oils or sprays.

12. The method according to claim 2, characterized in that at least one of the compounds is applied to a surface or impregnated into clothing or fabric, or applied to cleaning products.

13. The method according to claim 2, characterized in that contact of ticks or cockroaches with at least one of the compounds produces toxicity for the ticks or cockroaches.

14. The method according to claim 3, characterized in that at least one of the compounds is applied to the skin in the form of wipes, lotions, creams, oils or sprays.

15. The method according to claim 3, characterized in that at least one of the compounds in combination with a compound selected from DEET® (N,NDietil-m-toluamide) and para-menthane-3,8-diol is applied to the skin in the form of wipes, lotions, creams, oils or sprays.

16. The method according to claim 3, characterized in that at least one of the compounds is applied to a surface or impregnated into clothing or fabric, or applied to cleaning products.

17. The method according to claim 3, characterized in that contact of ticks or cockroaches with at least one of the compounds produces toxicity for the ticks or cockroaches.

18. The method according to claim 4, characterized in that at least one of the compounds is applied to the skin in the form of wipes, lotions, creams, oils or sprays.

19. The method according to claim 4, characterized in that at least one of the compounds in combination with a compound selected from DEET® (N,NDietil-m-toluamide) and para-menthane-3,8-diol is applied to the skin in the form of wipes, lotions, creams, oils or sprays.

20. The method according to claim 4, characterized in that at least one of the compounds is applied to a surface or impregnated into clothing or fabric, or applied to cleaning products.

21. The method according to claim 4, characterized in that contact of ticks or cockroaches with at least one of the compounds produces toxicity for the ticks or cockroaches.

22. The method according to claim 5, characterized in that at least one of the compounds is applied to the skin in the form of wipes, lotions, creams, oils or sprays.

23. The method according to claim 5, characterized in that at least one of the compounds in combination with a compound selected from DEET® (N,NDietil-m-toluamide) and para-menthane-3,8-diol is applied to the skin in the form of wipes, lotions, creams, oils or sprays.

24. The method according to claim 5, characterized in that at least one of the compounds is applied to a surface or impregnated into clothing or fabric, or applied to cleaning products.

25. The method according to claim 5, characterized in that contact of ticks or cockroaches with at least one of the compounds produces toxicity for the ticks or cockroaches.

26. A method for controlling or repelling one or more of the insects selected from the group of biting flies, houseflies, ticks, ants, fleas, biting mosquitoes, cockroaches, spiders, and bed bugs, the method comprising contacting the insects with an effective inhibitory amount of at least one of the compounds of structure (I). IV l4Ί uo RR; (i) wherein R is selected from the group consisting of -OH, =O, OC(O)R4, -ORg, and -(ORg)2, wherein each Re is independently selected from an alkyl group containing from 1 to 4 carbon atoms and R4 is a saturated or unsaturated linear or branched hydrocarbyl group with zero to two double bonds and from 1 to 15 carbon atoms; X is O or CH2, provided that when X is O, R can only be =O; each Z is selected independently from the group consisting of (CH) and (CH2) ; and is a number selected from 1 and 2;Ri is selected from the group consisting of H and a saturated or unsaturated linear or branched hydrocarbyl group with zero to two double bonds and from 1 to 15 carbon atoms; R2 is selected from the group consisting of H and a saturated or unsaturated linear or branched hydrocarbyl group with zero to three double bonds and from 1 to 15 carbon atoms; Ra is selected from the group consisting of H, a saturated or unsaturated linear or branched chain hydrocarbyl group with zero to three double bonds and 1 to 15 carbon atoms, -(CH2)nOH, -C(O)OR5, -CH2C(O)OR7, -CH2C(O)R8, C(O)NR9Rio and -CH2C (O)NRnRi2 wherein each of R5, R7, Rs, R9, Rio, R11 and R12 is independently selected from the group consisting of H and a saturated or unsaturated linear or branched chain hydrocarbyl group with zero to three double bonds and 1 to 15 carbon atoms, and n is an integer from 1 to 12;The bond between positions 2 and 3 in the ring structure can be a single or double bond, and where compounds of structure (I) contain 15 from 11 to 20 carbon atoms, except where R is = O, X=CH2 and ey is 1, compounds of structure (I) contain from 13 to 20 carbon atoms, with the condition that when R3 is CH2C(O)OR7 Ri and R2 must be H or a saturated hydrocarbyl group with zero double bonds.;