CROSS REFERENCE TO RELATED APPLICATION

[0001] This application claims the benefit of U.S. Provisional Patent Application Serial No. 62/237,158 filed October 5, 2015.

BACKGROUND OF THE INVENTION

[0002] The control of insects and related arthropods is of extreme importance to the agricultural industry. Insects and related arthropods annually destroy an estimated 15% of agricultural crops in the United States and even more than that in developing countries. Some of this damage occurs when plant pathogens, insects and other such soil borne pests damage a seedling. The period during germination of the seed, sprouting and initial growth of the plant is particularly critical because the roots and shoots of the growing plant are small and even a small amount of damage can kill the entire plant. Moreover, some natural plant defenses are not fully developed at this stage and the plant is vulnerable to attack.

[0003] Plants are often treated by contacting them with compositions. It may also be desired to provide methods of treating plants that result in an increase in the yield of the crop produced by those plants. In addition to yield enhancement, reducing adverse effects from various stresses may be at least partially mitigated by application(s) of certain plant growth regulator(s). Sources of stress may be from heat, cold, drought, or other chemicals. One particular stress occurs during transplant of vegetables from green house/nursery into open field.

SUMMARY OF THE INVENTION

[0004] This invention is based on the discovery that a combination of a spinosyn compound and a cyclopropene compound can greatly enhance insecticidal efficacy and/or plant's tolerance to stress. The combination provided herein can be performed in a compositional mixture, or a simultaneous or sequential application with one or more compounds of Compound A and Compound B as provided herein. In one embodiment, the insecticidal composition is used against lepidopteran. In another embodiment, the stress is associated with vegetable transplants from green house/nursery into open field. In another embodiment, the stress is associated with heat, cold, and/or drought.

[0005] In one aspect, provided is a composition comprising a mixture comprising (i) an effective amount of Compound A comprising a spinosyn compound, or an agriculturally acceptable salt, ester, or amide thereof, as described herein, and (ii) a Compound B according to Formula One, or an agriculturally acceptable salt, ester, or amide thereof, as described herein.

[0006] In one embodiment, weight ratio of Compound A and Compound B are between 1: 10 and 1000: 1 ; between 1: 10 and 1: 1 ; between 1: 1 and 1 : 100; or between 1: 10 and 1 : 1000. In another embodiment, the mixture comprises a synergistic combination for Compound A and Compound B for insecticidal efficacy. In another embodiment, the mixture comprises a synergistic combination for Compound A and Compound B for enhancing plant health and/or tolerance to stress.

[0007] In another aspect, provided is a method for controlling insect. The method comprises (i) first applying an effective amount of Compound A comprising a spinosyn compound, or an agriculturally acceptable salt, ester, or amide thereof, as described herein, to a plant or plant part; and (ii) second applying a Compound B according to Formula One, or an agriculturally acceptable salt, ester, or amide thereof, as described herein; wherein the first applying and the second applying steps can be performed in either order or simultaneously.

[0008] In one embodiment, the insect comprises lepidopteran. In another embodiment, weight ratio of Compound A and Compound B are between 1: 10 and 1000: 1; between 1: 10 and 1: 1 ; between 1: 1 and 1 : 100; or between 1 : 10 and 1 : 1000. In another embodiment, the combination of Compound A and Compound B is synergistic. In another embodiment, the first applying step is performed in an enclosed space, for example a green house or nursery. In another embodiment, the second applying step is performed in an enclosed space, for example a green house or nursery. In another embodiment, the first applying step is performed in an open space, for example open field. In another embodiment, the second applying step is performed in an open space, for example open field.

[0009] Systemic movement of pesticides in plants may be utilized to control pests on one portion of the plant by applying the pesticides to a different portion of the plant. For example, control of foliar- feeding insects or stem- feeding insects can be controlled by drip irrigation or furrow application, or by treating the seed before planting. Seed treatment can be applied to all types of seeds, including those from which plants genetically transformed to express specialized traits will germinate. Foliar and/or soil applications of insecticidal compositions are also contemplated. Such insecticidal compositions can be applied onto plants including for example corn, soybean, canola, wheat, rice, cotton, banana, and tomato.

[0010] In another aspect, provided is a method for enhancing plant health and/or tolerance to stress for plants. The method comprises (i) first applying an effective amount of Compound A comprising a spinosyn compound, or an agriculturally acceptable salt, ester, or amide thereof, as described herein, to a plant or plant part; and (ii) second applying a Compound B according to Formula One, or an agriculturally acceptable salt, ester, or amide thereof, as described herein, to the plant or plant part; wherein the first applying and the second applying steps can be performed in either order or simultaneously.

[0011] In one embodiment, weight ratio of Compound A and Compound B are between 1:10 and 1000:1; between 1: 10 and 1:1; between 1:1 and 1:100; or between 1:10 and 1:1000. In another embodiment, the combination of Compound A and Compound B is synergistic. In another embodiment, the first applying step is performed in an enclosed space, for example a green house or nursery. In another embodiment, the second applying step is performed in an enclosed space, for example a green house or nursery. In another embodiment, the first applying step is performed in an open space, for example open field. In another embodiment, the second applying step is performed in an open space, for example open field.

[0012] In one embodiment, the plant comprises vegetable. In a further embodiment, the vegetable is selected from the group consisting of tomato, peppers, celery, lettuce, broccoli, cabbage, cauliflower, artichokes, leeks, and combinations thereof. In another further embodiment, the vegetable is selected from the group consisting of tomato, potato, sweet potato, cassava, pepper, bell pepper, carrot, celery, squash, eggplant, cabbage, cauliflower, broccoli, asparagus, mushroom, onion, garlic, leek, and snap bean.

[0013] In another aspect, provided is a method for controlling insects. The method comprises applying the composition as described herein.

[0014] In another aspect, provided is a method for enhancing plant health and/or tolerance to stress for plants. The method comprises applying the composition as described herein, to a plant or plant part.

DETAILED DESCRIPTION OF THE INVENTION

Definitions

[0015] The examples given in the definitions are generally non-exhaustive and must not be construed as limiting the invention disclosed in this document. It is understood that a substituent should comply with chemical bonding rules and steric compatibility constraints in relation to the particular molecule to which it is attached.

[0016] "Alkenyl" means an acyclic, unsaturated (at least one carbon-carbon double bond), branched or unbranched, substituent consisting of carbon and hydrogen, for example, vinyl, allyl, butenyl, pentenyl, and hexenyl.

[0017] "Alkenyloxy" means an alkenyl further consisting of a carbon-oxygen single bond, for example, allyloxy, butenyloxy, pentenyloxy, hexenyloxy.

[0018] "Alkoxy" means an alkyl further consisting of a carbon-oxygen single bond, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, and feri-butoxy.

[0019] "Alkyl" means an acyclic, saturated, branched or unbranched, substituent consisting of carbon and hydrogen, for example, methyl, ethyl, (C3)alkyl which represents n- propyl and isopropyl), (C ₄ )alkyl which represents n -butyl, sec-butyl, isobutyl, and icri-butyl.

[0020] "Alkynyl" means an acyclic, unsaturated (at least one carbon-carbon triple bond), branched or unbranched, substituent consisting of carbon and hydrogen, for example, ethynyl, propargyl, butynyl, and pentynyl.

[0021] "Alkynyloxy" means an alkynyl further consisting of a carbon-oxygen single bond, for example, pentynyloxy, hexynyloxy, heptynyloxy, and octynyloxy.

[0022] "Aryl" means a cyclic, aromatic substituent consisting of hydrogen and carbon, for example, phenyl, naphthyl, and biphenyl.

[0023] "(C _x -C _y )" where the subscripts "x" and "y" are integers such as 1, 2, or 3, means the range of carbon atoms for a substituent - for example, (Ci-C ₄ )alkyl means methyl, ethyl, n-propyl, isopropyl, n-butyl, scc-butyl, isobutyl, and icri-butyl, each individually.

[0024] "Cycloalkenyl" means a monocyclic or polycyclic, unsaturated (at least one carbon-carbon double bond) substituent consisting of carbon and hydrogen, for example, cyclobutenyl, cyclopentenyl, cyclohexenyl, norbornenyl, bicyclo[2.2.2]octenyl,

tetrahydronaphthyl, hexahydronaphthyl, and octahydronaphthyl.

[0025] "Cycloalkenyloxy" means a cycloalkenyl further consisting of a carbon-oxygen single bond, for example, cyclobutenyloxy, cyclopentenyloxy, norbornenyloxy, and bicyclo[2.2.2]octenyloxy.

[0026] "Cycloalkyl" means a monocyclic or polycyclic, saturated substituent consisting of carbon and hydrogen, for example, cyclopropyl, cyclobutyl, cyclopentyl, norbornyl, bicyclo[2.2.2]octyl, and decahydronaphthyl.

[0027] "Cycloalkoxy" means a cycloalkyl further consisting of a carbon-oxygen single bond, for example, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, norbornyloxy, and bicyclo[2.2.2]octyloxy.

[0028] "Halo" means fluoro, chloro, bromo, and iodo.

[0029] "Haloalkoxy" means an alkoxy further consisting of, from one to the maximum possible number of identical or different, halos, for example, fluoromethoxy, trifluoromethoxy, 2,2-difluoropropoxy, chloromethoxy, trichloromethoxy, 1,1,2,2- tetrafluoroethoxy, and pentafluoroethoxy.

[0030] "Haloalkyl" means an alkyl further consisting of, from one to the maximum possible number of, identical or different, halos, for example, fluoromethyl, trifluoromethyl, 2,2-difluoropropyl, chloromethyl, trichloromethyl, and 1,1,2,2-tetrafluoroethyl.

[0031] "Heterocyclyl" means a cyclic substituent that may be fully saturated, partially unsaturated, or fully unsaturated, where the cyclic structure contains at least one carbon and at least one heteroatom, where said heteroatom is nitrogen, sulfur, or oxygen. In the case of sulfur, that atom can be in other oxidation states such as a sulfoxide and sulfone. Examples of aromatic heterocyclyls include, but are not limited to, benzofuranyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, benzothienyl, benzothiazolyl, cinnolinyl, furanyl, imidazolyl, indazolyl, indolyl, isoindolyl, isoquinolinyl, isothiazolyl, isoxazolyl, oxadiazolyl, oxazolinyl, oxazolyl, phthalazinyl, pyrazinyl, pyrazolinyl, pyrazolyl, pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, quinazolinyl, quinolinyl, quinoxalinyl, tetrazolyl, thiazolinyl, thiazolyl, thienyl, triazinyl, and triazolyl. Examples of fully saturated heterocyclyls include, but are not limited to, piperazinyl, piperidinyl, morpholinyl, pyrrolidinyl, oxetanyl, tetrahydrofuranyl, tetrahydrothienyl and tetrahydropyranyl. Examples of partially unsaturated heterocyclyls include, but are not limited to, 1,2,3,4-tetrahydroquinolinyl, 4,5-dihydro-oxazolyl, 4,5- dihydro-lH-pyrazolyl, 4,5-dihydro-isoxazolyl, and 2,3-dihydro-[l,3,4]-oxadiazolyl.

Additional examples include the following

thietanyl thietanyl-oxide thietanyl-dioxide.

[0032] As used herein, the phrase "plant health" and/or "tolerance to stress" may be measured according to one or more of criteria including, but not limited to, biomass, plant height, leaf length, leaf area, root growth, root length, greenness or chlorophyll content, growth rate, harvest index, root dry weight, shoot dry weight, total dry weight, specific oil or protein content, nutrient content, total yield, number of leaves, days to maturity, vigor (1-9), canopy % coverage, plant survival rate, stem diameter, root/shoot ratio, and combinations thereof. In addition, enhancing "tolerance to stress" may include one or more of criteria including, but not limited to, enhanced water use efficiency, enhanced cold tolerance, enhanced heat tolerance, enhanced salt tolerance, increased yield, enhanced nitrogen use efficiency, enhanced seed protein, enhanced seed oil, and combinations thereof.

[0033] As used herein, the phrase "plant" includes dicotyledonous plants and

monocotyledonous plants. Examples of dicotyledonous plants include tobacco, Arabidopsis, soybean, tomato, papaya, canola, sunflower, cotton, alfalfa, potato, grapevine, pigeon pea, pea, Brassica, chickpea, sugar beet, rapeseed, watermelon, melon, pepper, peanut, pumpkin, radish, spinach, squash, broccoli, cabbage, carrot, cauliflower, celery, Chinese cabbage, cucumber, eggplant, and lettuce. Examples of monocotyledonous plants include corn, rice, wheat, sugarcane, barley, rye, sorghum, orchids, bamboo, banana, cattails, lilies, oat, onion, millet, and triticale. Examples of fruit include banana, pineapple, oranges, grapes, grapefruit, watermelon, melon, apples, peaches, pears, kiwifruit, mango, nectarines, guava, persimmon, avocado, lemon, fig, and berries. Examples of flowers include baby's breath, carnation, dahlia, daffodil, geranium, gerbera, lily, orchid, peony, Queen Anne's lace, rose, snapdragon, or other cut-flowers or ornamental flowers, potted-flowers, and flower bulbs.

[0034] As used herein, plants include, but are not limited to, germinant seeds, emerging seedlings, plants emerging from vegetative propagules, immature vegetation, and established vegetation. As used herein, the phrase "vegetable" include, but not limited to, tomato, peppers, celery, lettuce, broccoli, cabbage, cauliflower, artichokes, and leeks.

[0035] As used herein, agriculturally acceptable salts and esters refer to salts and esters that exhibit pesticide activity, or that are or can be converted in plants, water, or soil to the referenced pesticide. Exemplary agriculturally acceptable esters are those that are or can be hydrolyzed, oxidized, metabolized, or otherwise converted, e.g., in plants, water, or soil, to the corresponding carboxylic acid which, depending on the pH, may be in the dissociated or undissociated form.

[0036] In some embodiment, synergism may be defined as "an interaction of two or more factors such that the effect when combined is greater than the predicted effect based on the response of each factor applied separately." Senseman, S., Ed. Herbicide Handbook. 9th ed. Lawrence: Weed Science Society of America, 2007. In some embodiments, the compositions exhibit synergy as determined by the Colby's equation (Colby, S. R. Calculation of the synergistic and antagonistic response of herbicide combinations. Weeds 1967, 15, 20-22.

[0037] As used herein, to "treat" a plant or plant part means to bring the plant or plant part into contact with a material. [0038] Among embodiments in which plants are treated using methods involving a composition of the present invention, the plants that are treated may be any plants that produce a useful product. Among embodiments in which plant parts are treated using methods involving a composition of the present invention, the plant parts that are treated may be any part of the plant that produces a useful product. In some embodiments, useful plant parts are treated with a method involving use of a composition of the present invention.

[0039] In embodiments of the present invention in which a plant or plant part is treated, a composition of the present invention is used in a way that brings Compound A and/or Compound B into contact with the plant or plant part. In some embodiments, the method involves using a composition of the present invention in a way that releases Compound B from the cyclopropene molecular encapsulating agent complex under conditions in which the cyclopropene compound then comes into contact with the plant or plant part.

Compound A

[0040] This document discloses Compound A comprising a spinosyn compound, which can be a spinosyn natural factor or semi- synthetic derivative or butenyl-spinosyn natural factor or semi-synthetic derivative. Examples of specific spinosyn compounds that can be used include Spinosad and spinetoram.

[0041] Saccharopolyspora spinosa produces a mixture of nine closely related compounds collectively called "spinosyns" or "spinosyn compounds." Within the mixture, spinosyn A and D, known as spinosad, are the major components and have the highest activity against key insect targets. Spinosyn J and L, two of the minor components within the spinosyn mixture, are the precursors for spinetoram, the second generation spinosyn insecticide.

[0042] Spinosad comprises approximately 85% spinosyn A and approximately 15% spinosyn D. Spinosyns A and D are natural products produced by fermentation of

Saccharopolyspora spinosa, as disclosed in U.S. Pat. No. 5,362,634. The spinosyn compounds consist of a 5,6,5-tricylic ring system, fused to a 12-membered macrocyclic lactone, a neutral sugar (rhamnose), and an amino sugar (forosamine). Spinosyn compounds are also disclosed in U.S. Patent Nos. 5,496,931 ; 5,670,364; 5,591,606; 5,571,901; 5,202,242; 5,767,253; 5,840,861; 5,670,486 and 5,631,155. As used herein, the term "spinosyn" includes natural factors and semi-synthetic derivatives of the naturally produced factors. A large number of chemical modifications to these spinosyn compounds have been made, as disclosed in U.S. Patent No. 6,001,981.

[0043] Spinetoram is a mixture of 5,6-dihydro-3'-ethoxy spinosyn J (major component) and 3'-ethoxy spinosyn L. The mixture can be prepared by ethoxylating a mixture of spinosyn J and spinosyn L, followed by hydrogenation. Accordingly, spinetoram is a semisynthetic spinosyn for a mixture of 50-90% (2R,3aR,5aR,5bS,9S, 13S, 14R,16aS, 16bR)-2-(6- deoxy-3-0-ethyl-2,4-di-0-methyl-a-L-mannopyranosyloxy)-13-[( R2R,5S,6R)-5- (dimethylamino)tetrahydro-6-methylpyran-2-yloxy]-9-ethyl-

2,3,3a,4,5,5a,5b,6,9,10, l l,12,13,14, 16a,16b-hexadecahydro-14-methyl-H-as-indaceno[3,2- d]oxacyclododecine-7,15-dione, and 50-10% (2R,3aR,5aS,5bS,9S,13S,14R,16aS,16b5)-2-(6- deoxy-3-0-ethyl-2,4-di-0-methyl-a-L-mannopyranosyloxy)-13-[( R2R,5S,6R)-5- (dimethylamino)tetrahydro-6-methylpyran-2-yloxy]-9-ethyl-

2,3,3a,5a,5b,6,9,10,l 1,12, 13, 14,16a,16b-tetradecahydro-4,14-dimethyl-lH-as-indaceno[3,2- d]oxacyclododecine-7,15-dione. Synthesis of the components of spinetoram is described in U.S. Patent No. 6,001,981.

[0044] In another embodiment, Compound A may comprise a macrolide insecticide, which is disclosed in U.S. Pat. No. 6,800,614. These compounds are characterized by the presence of reactive functional groups that make further modifications possible at locations where such modifications were not feasible in previously disclosed spinosyns. Natural and semi-synthetic derivatives of the butenyl spinosyns are disclosed in U.S. Pat. No. 6,919,464. The term "butenyl-spinosyn" as used herein is intended to include natural factors and semisynthetic derivatives of the naturally produced factors.

[0045] The spinosyn compound of Compound A may be a naturally produced or synthetic polyketide-derived tetracyclic macrolide. The spinosyn compound may be a fermentation product including at least one of the compounds produced by

Saccharopolyspora spinosa and disclosed in U.S. Pat. No. 5,362,634. Other spinosyn compounds are also disclosed in U.S. Patent Nos. 5,496,931, 5,670,364, 5,591,606,

5,571,901, 5,202,242, 5,767,253, 5,840,861, 5,670,486, 5,631,155, and 6,001,981.

Compound B

[0046] This document discloses molecules of Compound B representing cyclopropene compounds having the following formula ("Formula One"):

where each R ¹ , R ² , R ³ and R ⁴ is independently selected from the group consisting of H and a chemical group of the formula: -(L) _n -Z

where n is an integer from 0 to 12. Each L is a bivalent radical. Suitable L groups include, for example, radicals containing one or more atoms selected from B, C, N, O, P, S, Si, or mixtures thereof. The atoms within an L group may be connected to each other by single bonds, double bonds, triple bonds, or mixtures thereof. Each L group may be linear, branched, cyclic, or a combination thereof. In any one R group (i.e. , any one of R ¹ , R ² , R ³ and R ⁴ ) the total number of heteroatoms (i.e. , atoms that are neither H nor C) is from 0 to 6. Independently, in any one R group the total number of non-hydrogen atoms is 50 or less. Each Z is a monovalent radical. Each Z is independently selected from the group consisting of a Ci-C ₈ alkyl, hydrogen, halo, cyano, nitro, nitroso, azido, chlorate, bromate, iodate, isocyanato, isocyanido, isothiocyanato, pentafluorothio, and a chemical group G, wherein G is a 3- to 14-membered ring system.

[0047] The R ¹ , R ² , R ³ , and R ⁴ groups are independently selected from the suitable groups. Among the groups that are suitable for use as one or more of R ¹ , R ² , R ³ , and R ⁴ are, for example, aliphatic groups, aliphatic-oxy groups, alkylphosphonato groups, cycloaliphatic groups, cycloalkylsulfonyl groups, cycloalkylamino groups, heterocyclic groups, aryl groups, heteroaryl groups, halogens, silyl groups, and mixtures and combinations thereof. Groups that are suitable for use as one or more of R ¹ , R ² , R ³ , and R ⁴ may be substituted or unsubstituted.

[0048] Among the suitable R ¹ , R ² , R ³ , and R ⁴ groups are, for example, aliphatic groups. Some suitable aliphatic groups include, for example, alkyl, alkenyl, and alkynyl groups. Suitable aliphatic groups may be linear, branched, cyclic, or a combination thereof.

Independently, suitable aliphatic groups may be substituted or unsubstituted.

[0049] As used herein, a chemical group of interest is said to be "substituted" if one or more hydrogen atoms of the chemical group of interest is replaced by a substituent.

[0050] Also among the suitable R ¹ , R ² , R ³ , and R ⁴ groups are, for example, substituted and unsubstituted heterocyclyl groups that are connected to the cyclopropene compound through an intervening oxy group, amino group, carbonyl group, or sulfonyl group; examples of such R ¹ , R ² , R ³ , and R ⁴ groups are heterocyclyloxy, heterocyclylcarbonyl,

diheterocyclylamino, and diheterocyclylaminosulfonyl.

[0051] Also among the suitable R ¹ , R ² , R ³ , and R ⁴ groups are, for example, substituted and unsubstituted heterocyclic groups that are connected to the cyclopropene compound through an intervening oxy group, amino group, carbonyl group, sulfonyl group, thioalkyl group, or aminosulfonyl group; examples of such R ¹ , R ² , R ³ , and R ⁴ groups are

diheteroarylamino, heteroarylthioalkyl, and diheteroarylaminosulfonyl.

[0052] Also among the suitable R ¹ , R ² , R ³ , and R ⁴ groups are, for example, hydj fluoro, chloro, bromo, iodo, cyano, nitro, nitroso, azido, chlorate, bromate, iodate, isocyanato, isocyanido, isothiocyanato, pentafluorothio, acetoxy, carboethoxy, cyanato, nitrato, nitrito, perchlorato, allenyl, butylmercapto, diethylphosphonato, dimethylphenylsilyl, isoquinolyl, mercapto, naphthyl, phenoxy, phenyl, piperidino, pyridyl, quinolyl, triethylsilyl,

trimethylsilyl, and substituted analogs thereof.

[0053] As used herein, the chemical group G is a 3- to 14-membered ring system. Ring systems suitable as chemical group G may be substituted or unsubstituted; they may be aromatic (including, for example, phenyl and napthyl) or aliphatic (including unsaturated aliphatic, partially saturated aliphatic, or saturated aliphatic); and they may be carbocyclic or heterocyclic. Among heterocyclic G groups, some suitable heteroatoms are, for example, nitrogen, sulfur, oxygen, and combinations thereof. Ring systems suitable as chemical group G may be monocyclic, bicyclic, tricyclic, polycyclic, spiro, or fused; among suitable chemical group G ring systems that are bicyclic, tricyclic, or fused, the various rings in a single chemical group G may be all the same type or may be of two or more types (for example, an aromatic ring may be fused with an aliphatic ring).

[0054] In one embodiment, one or more of R ¹ , R ² , R ³ , and R ⁴ is hydro gen or Ci-Cio alkyl. In another embodiment, each of R ¹ , R ² , R ³ , and R ⁴ is hydrogen or Ci-C ₈ alkyl. In another embodiment, each of R ¹ , R ² , R ³ , and R ⁴ is hydrogen or C ₁ -C ₄ alkyl. In another embodiment, each of R ¹ , R ² , R ³ , and R ⁴ is hydrogen or methyl. In another embodiment, R ¹ is C ₁ -C ₄ alkyl and each of R ² , R ³ , and R ⁴ is hydrogen. In another embodiment, R ¹ is methyl and each of R ² , R ³ , and R ⁴ is hydrogen, and the cyclopropene compound is known herein as 1- methylcyclopropene or "1-MCP."

[0055] In one embodiment, the Compo B (cyclopropene compound) is of the formula:

wherein R is a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, phenyl, or naphthyl group; wherein the substituents are independently halogen, alkoxy, or substituted or unsubstituted phenoxy. In one embodiment, R is Ci-C ₈ alkyl. In another embodiment, R is methyl.

[0056] In another embodiment, the Compound B (cyclopropene compound) is of the formula:

wherein R ¹ is a substituted or unsubstituted C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, cycloalkylalkyl, phenyl, or napthyl group; and R ² , R ³ , and R ⁴ are hydrogen. In another embodiment, the cyclopropene comprises 1-methylcyclopropene (1-MCP).

[0057] In some embodiments, a cyclopropene is used that has boiling point at one atmosphere pressure of 50 °C or lower; or 25 °C or lower; or 15 °C or lower. Independently, in some embodiments, a cyclopropene is used that has boiling point at one atmosphere pressure of -100 °C or higher; -50 °C or higher; or -25 °C or higher; or 0 °C or higher.

[0058] The cyclopropenes applicable to this invention may be prepared by any method. Some suitable methods of preparation of cyclopropenes are the processes disclosed in U.S. Patents No. 5,518,988 and 6,017,849. Any compound that is not a cyclopropene is known herein as a "non-cyclopropene."

[0059] When a cyclopropene compound is used, in some embodiments the concentration of the cyclopropene compound as used in the compositions and/or methods provided is 0.5 ppb or higher; 1 ppb or higher; 10 ppb or higher; or 100 ppb or higher. In some

embodiments, the concentration of the cyclopropene compound is 100 ppm or lower; 50 ppm or lower; 10 ppm or lower; or 5 ppm or lower. In some embodiments, the concentration of the cyclopropene compound is between 5 ppm and 250 ppm; between 25 ppm and 100 ppm; between 45 ppm and 150 ppm; or between 15 ppm and 100 ppm.

[0060] In some embodiments, one or more composition of the present invention includes at least one ionic complexing reagent. An ionic complexing reagent interacts with a cyclopropene to form a complex that is stable in water. Some suitable ionic complexing reagents, for example, include lithium ion. In some embodiments, no ionic complexing reagent is used.

[0061] In some embodiments, no composition of the present invention includes any molecular encapsulating agent. In other embodiments, one or more composition of the present invention includes at least one molecular encapsulating agent. In another

embodiment, the molecular encapsulating agent is selected from the group consisting of substituted cyclodextrins, unsubstituted cyclodextrins, and combinations thereof. In a further embodiment, the molecular encapsulating agent comprises alpha-cyclodextrin.

[0062] When a molecular encapsulating agent is used, suitable molecular encapsulating agents include, for example, organic and inorganic molecular encapsulating agents. Suitable organic molecular encapsulating agents include, for example, substituted cyclodextrins, unsubstituted cyclodextrins, and crown ethers. Suitable inorganic molecular encapsulating agents include, for example, zeolites. Mixtures of suitable molecular encapsulating agents are also suitable. In some embodiments of the invention, the encapsulating agent is alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin, or a mixture thereof. In some embodiments of the invention, particularly when the cyclopropene is 1-methylcyclopropene, the encapsulating agent is alpha-cyclodextrin. The preferred encapsulating agent will vary depending upon the structure of the cyclopropene or cyclopropenes being used. Any cyclodextrin or mixture of cyclodextrins, cyclodextrin polymers, modified cyclodextrins, or mixtures thereof can also be utilized pursuant to the present invention. Some cyclodextrins are available, for example, from Wacker Biochem Inc., Adrian, MI or Cerestar USA, Hammond, IN, as well as other vendors.

[0063] In some of the embodiments in which a molecular encapsulating agent is present, at least one molecular encapsulating agent encapsulates one or more cyclopropenes. A cyclopropene or substituted cyclopropene molecule encapsulated in a molecule of a molecular encapsulating agent is known herein as a "cyclopropene molecular encapsulating agent complex." The cyclopropene molecular encapsulation agent complexes can be prepared by any means. In one method of preparation, for example, such complexes are prepared by contacting the cyclopropene with a solution or slurry of the molecular encapsulation agent and then isolating the complex, using, for example, processes disclosed in U. S. Patent No. 6,017,849. For example, in one method of making a complex in which 1-MCP is encapsulated in a molecular encapsulating agent, the 1-MCP gas is bubbled through a solution of alpha-cyclodextrin in water, from which the complex first precipitates and is then isolated by filtration. In some embodiments, complexes are made by the above method and, after isolation, are dried and stored in solid form, for example as a powder, for later addition to useful compositions.

[0064] In some embodiments, one or more molecular encapsulating agent and one or more cyclopropenes are both present in a composition; in some of such embodiments, the amount of molecular encapsulating agent can usefully be characterized by the ratio of moles of molecular encapsulating agent to moles of cyclopropene. In some embodiments, the ratio of moles of molecular encapsulating agent to moles of cyclopropene is 0.1 or larger; or 0.2 or larger; or 0.5 or larger; or 0.9 or larger. Independently, in some of such embodiments, the ratio of moles of molecular encapsulating agent to moles of cyclopropene is 2 or lower; or 1.5 or lower.

Stereoisomers

[0065] Molecules of Formula One may exist as one or more stereoisomers. Thus, certain molecules can be produced as racemic mixtures. It will be appreciated by those skilled in the art that one stereoisomer may be more active than the other stereoisomers. Individual stereoisomers may be obtained by known selective synthetic procedures, by conventional synthetic procedures using resolved starting materials, or by conventional resolution procedures. Certain molecules disclosed in this document can exist as two or more isomers. The various isomers include geometric isomers, diastereomers, and enantiomers. Thus, the molecules disclosed in this document include geometric isomers, racemic mixtures, individual stereoisomers, and optically active mixtures. It will be appreciated by those skilled in the art that one isomer may be more active than the others. The structures disclosed in the present disclosure are drawn in only one geometric form for clarity, but are intended to represent all geometric forms of the molecule.

Formulations

[0066] A pesticide is rarely suitable for application in its pure form. It is usually necessary to add other substances so that the pesticide can be used at the required

concentration and in an appropriate form, permitting ease of application, handling, transportation, storage, and maximum pesticide activity. Thus, pesticides are formulated into, for example, baits, concentrated emulsions, dusts, emulsifiable concentrates, fumigants, gels, granules, microencapsulations, seed treatments, suspension concentrates, suspoemulsions, tablets, water soluble liquids, water dispersible granules or dry flowables, wettable powders, and ultra low volume solutions. For further information on formulation types see "Catalogue of Pesticide Formulation Types and International Coding System" Technical Monograph n°2, 5th Edition by CropLife International (2002).

[0067] Pesticides are applied most often as aqueous suspensions or emulsions prepared from concentrated formulations of such pesticides. Such water-soluble, water-suspendable, or emulsifiable formulations are either solids, usually known as wettable powders, or water dispersible granules, or liquids usually known as emulsifiable concentrates, or aqueous suspensions. Wettable powders, which may be compacted to form water dispersible granules, comprise an intimate mixture of the pesticide, a carrier, and surfactants. The concentration of the pesticide is usually from about 10% to about 90% by weight. The carrier is usually selected from among the attapulgite clays, the montmorillonite clays, the diatomaceous earths, or the purified silicates. Effective surfactants, comprising from about 0.5% to about 10% of the wettable powder, are found among sulfonated lignins, condensed

naphthalenesulfonates, naphthalenesulfonates, alkylbenzenesulfonates, alkyl sulfates, and non-ionic surfactants such as ethylene oxide adducts of alkyl phenols.

[0068] Emulsifiable concentrates of pesticides comprise a convenient concentration of a pesticide, such as from about 50 to about 500 grams per liter of liquid dissolved in a carrier that is either a water miscible solvent or a mixture of water-immiscible organic solvent and emulsifiers. Useful organic solvents include aromatics, especially xylenes and petroleum fractions, especially the high-boiling naphthalenic and olefinic portions of petroleum such as heavy aromatic naphtha. Other organic solvents may also be used, such as the terpenic solvents including rosin derivatives, aliphatic ketones such as cyclohexanone, and complex alcohols such as 2-ethoxyethanol. Suitable emulsifiers for emulsifiable concentrates are selected from conventional anionic and non-ionic surfactants.

[0069] Aqueous suspensions comprise suspensions of water-insoluble pesticides dispersed in an aqueous carrier at a concentration in the range from about 5% to about 50% by weight. Suspensions are prepared by finely grinding the pesticide and vigorously mixing it into a carrier comprised of water and surfactants. Ingredients, such as inorganic salts and synthetic or natural gums may also be added, to increase the density and viscosity of the aqueous carrier. It is often most effective to grind and mix the pesticide at the same time by preparing the aqueous mixture and homogenizing it in an implement such as a sand mill, ball mill, or piston-type homogenizer.

[0070] Pesticides may also be applied as granular compositions that are particularly useful for applications to the soil. Granular compositions usually contain from about 0.5% to about 10% by weight of the pesticide, dispersed in a carrier that comprises clay or a similar substance. Such compositions are usually prepared by dissolving the pesticide in a suitable solvent and applying it to a granular carrier which has been pre-formed to the appropriate particle size, in the range of from about 0.5 to about 3 mm. Such compositions may also be formulated by making a dough or paste of the carrier and compound and crushing and drying to obtain the desired granular particle size.

[0071] Dusts containing a pesticide are prepared by intimately mixing the pesticide in powdered form with a suitable dusty agricultural carrier, such as kaolin clay, ground volcanic rock, and the like. Dusts can suitably contain from about 1% to about 10% of the pesticide. They can be applied as a seed dressing or as a foliage application with a dust blower machine.

[0072] It is equally practical to apply a pesticide in the form of a solution in an appropriate organic solvent, usually petroleum oil, such as the spray oils, which are widely used in agricultural chemistry.

[0073] Pesticides can also be applied in the form of an aerosol composition. In such compositions the pesticide is dissolved or dispersed in a carrier, which is a pressure- generating propellant mixture. The aerosol composition is packaged in a container from which the mixture is dispensed through an atomizing valve.

[0074] Pesticide baits are formed when the pesticide is mixed with food or an attractant or both. When the pests eat the bait they also consume the pesticide. Baits may take the form of granules, gels, flowable powders, liquids, or solids. They can be used in pest harborages.

[0075] Fumigants are pesticides that have a relatively high vapor pressure and hence can exist as a gas in sufficient concentrations to kill pests in soil or enclosed spaces. The toxicity of the fumigant is proportional to its concentration and the exposure time. They are characterized by a good capacity for diffusion and act by penetrating the pest's respiratory system or being absorbed through the pest's cuticle. Fumigants are applied to control stored product pests under gas proof sheets, in gas sealed rooms or buildings or in special chambers.

[0076] Pesticides can be microencapsulated by suspending the pesticide particles or droplets in plastic polymers of various types. By altering the chemistry of the polymer or by changing factors in the processing, microcapsules can be formed of various sizes, solubility, wall thicknesses, and degrees of penetrability. These factors govern the speed with which the active ingredient within is released, which in turn, affects the residual performance, speed of action, and odor of the product.

[0077] Oil solution concentrates are made by dissolving pesticide in a solvent that will hold the pesticide in solution. Oil solutions of a pesticide usually provide faster knockdown and kill of pests than other formulations due to the solvents themselves having pesticidal action and the dissolution of the waxy covering of the integument increasing the speed of uptake of the pesticide. Other advantages of oil solutions include better storage stability, better penetration of crevices, and better adhesion to greasy surfaces.

[0078] Another embodiment is an oil-in-water emulsion, wherein the emulsion comprises oily globules which are each provided with a lamellar liquid crystal coating and are dispersed in an aqueous phase, wherein each oily globule comprises at least one compound which is agriculturally active, and is individually coated with a monolamellar or oligolamellar layer comprising: (1) at least one non- ionic lipophilic surface- active agent, (2) at least one non-ionic hydrophilic surface- active agent and (3) at least one ionic surface- active agent, wherein the globules having a mean particle diameter of less than 800 nanometers. Further information on the embodiment is disclosed in U.S. patent publication 20070027034 published February 1, 2007, having Patent Application serial number

11/495,228. For ease of use, this embodiment will be referred to as "OIWE."

[0079] For further information consult "Insect Pest Management" 2nd Edition by D. Dent, copyright CAB International (2000). Additionally, for more detailed information consult "Handbook of Pest Control - The Behavior, Life History, and Control of Household Pests" by Arnold Mallis, 9th Edition, copyright 2004 by GIE Media Inc.

Other Formulation Components

[0080] Generally, when the molecules disclosed in Formula One are used in a formulation, such formulation can also contain other components. These components include, but are not limited to, (this is a non-exhaustive and non-mutually exclusive list) wetters, spreaders, stickers, penetrants, buffers, sequestering agents, drift reduction agents, compatibility agents, anti-foam agents, cleaning agents, and emulsifiers. A few components are described forthwith.

[0081] A wetting agent is a substance that when added to a liquid increases the spreading or penetration power of the liquid by reducing the interfacial tension between the liquid and the surface on which it is spreading. Wetting agents are used for two main functions in agrochemical formulations: during processing and manufacture to increase the rate of wetting of powders in water to make concentrates for soluble liquids or suspension concentrates; and during mixing of a product with water in a spray tank to reduce the wetting time of wettable powders and to improve the penetration of water into water-dispersible granules. Examples of wetting agents used in wettable powder, suspension concentrate, and water-dispersible granule formulations are: sodium lauryl sulfate; sodium dioctyl sulfosuccinate; alkyl phenol ethoxylates; and aliphatic alcohol ethoxylates.

[0082] A dispersing agent is a substance which adsorbs onto the surface of particles and helps to preserve the state of dispersion of the particles and prevents them from

reaggregating. Dispersing agents are added to agrochemical formulations to facilitate dispersion and suspension during manufacture, and to ensure the particles redisperse into water in a spray tank. They are widely used in wettable powders, suspension concentrates and water-dispersible granules. Surfactants that are used as dispersing agents have the ability to adsorb strongly onto a particle surface and provide a charged or steric barrier to reaggregation of particles. The most commonly used surfactants are anionic, non-ionic, or mixtures of the two types. For wettable powder formulations, the most common dispersing agents are sodium lignosulfonates. For suspension concentrates, very good adsorption and stabilization are obtained using polyelectrolytes, such as sodium naphthalene sulfonate formaldehyde condensates. Tristyrylphenol ethoxylate phosphate esters are also used. Non-ionics such as alkylarylethylene oxide condensates and EO-PO block copolymers are sometimes combined with anionics as dispersing agents for suspension concentrates. In recent years, new types of very high molecular weight polymeric surfactants have been developed as dispersing agents. These have very long hydrophobic 'backbones' and a large number of ethylene oxide chains forming the 'teeth' of a 'comb' surfactant. These high molecular weight polymers can give very good long-term stability to suspension concentrates because the hydrophobic backbones have many anchoring points onto the particle surfaces. Examples of dispersing agents used in agrochemical formulations are: sodium lignosulfonates; sodium naphthalene sulfonate formaldehyde condensates; tristyrylphenol ethoxylate phosphate esters; aliphatic alcohol ethoxylates; alkyl ethoxylates; EO-PO block copolymers; and graft copolymers.

[0083] An emulsifying agent is a substance which stabilizes a suspension of droplets of one liquid phase in another liquid phase. Without the emulsifying agent the two liquids would separate into two immiscible liquid phases. The most commonly used emulsifier blends contain alkylphenol or aliphatic alcohol with twelve or more ethylene oxide units and the oil- soluble calcium salt of dodecylbenzenesulfonic acid. A range of hydrophile-lipophile balance ("HLB") values from 8 to 18 will normally provide good stable emulsions. Emulsion stability can sometimes be improved by the addition of a small amount of an EO-PO block copolymer surfactant.

[0084] A solubilizing agent is a surfactant which will form micelles in water at concentrations above the critical micelle concentration. The micelles are then able to dissolve or solubilize water-insoluble materials inside the hydrophobic part of the micelle. The types of surfactants usually used for solubilization are non-ionics, sorbitan monooleates, sorbitan monooleate ethoxylates, and methyl oleate esters.

[0085] Surfactants are sometimes used, either alone or with other additives such as mineral or vegetable oils as adjuvants to spray-tank mixes to improve the biological performance of the pesticide on the target. The types of surfactants used for bioenhancement depend generally on the nature and mode of action of the pesticide. However, they are often non- ionics such as: alkyl ethoxylates; linear aliphatic alcohol ethoxylates; aliphatic amine ethoxylates.

[0086] A carrier or diluent in an agricultural formulation is a material added to the pesticide to give a product of the required strength. Carriers are usually materials with high absorptive capacities, while diluents are usually materials with low absorptive capacities. Carriers and diluents are used in the formulation of dusts, wettable powders, granules and water-dispersible granules.

[0087] Organic solvents are used mainly in the formulation of emulsifiable concentrates, oil-in-water emulsions, suspoemulsions, and ultra low volume formulations, and to a lesser extent, granular formulations. Sometimes mixtures of solvents are used. The first main groups of solvents are aliphatic paraffinic oils such as kerosene or refined paraffins. The second main group (and the most common) comprises the aromatic solvents such as xylene and higher molecular weight fractions of C9 and CIO aromatic solvents. Chlorinated hydrocarbons are useful as cosolvents to prevent crystallization of pesticides when the formulation is emulsified into water. Alcohols are sometimes used as cosolvents to increase solvent power. Other solvents may include vegetable oils, seed oils, and esters of vegetable and seed oils.

[0088] Thickeners or gelling agents are used mainly in the formulation of suspension concentrates, emulsions and suspoemulsions to modify the rheology or flow properties of the liquid and to prevent separation and settling of the dispersed particles or droplets.

Thickening, gelling, and anti-settling agents generally fall into two categories, namely water- insoluble particulates and water-soluble polymers. It is possible to produce suspension concentrate formulations using clays and silicas. Examples of these types of materials, include, but are not limited to, montmorillonite, bentonite, magnesium aluminum silicate, and attapulgite. Water-soluble polysaccharides have been used as thickening-gelling agents for many years. The types of polysaccharides most commonly used are natural extracts of seeds and seaweeds or are synthetic derivatives of cellulose. Examples of these types of materials include, but are not limited to, guar gum; locust bean gum; carrageenam; alginates; methyl cellulose; sodium carboxymethyl cellulose (SCMC); hydroxyethyl cellulose (HEC). Other types of anti-settling agents are based on modified starches, polyacrylates, polyvinyl alcohol and polyethylene oxide. Another good anti- settling agent is xanthan gum.

[0089] Microorganisms can cause spoilage of formulated products. Therefore preservation agents are used to eliminate or reduce their effect. Examples of such agents include, but are not limited to: propionic acid and its sodium salt; sorbic acid and its sodium or potassium salts; benzoic acid and its sodium salt; p-hydroxybenzoic acid sodium salt; methyl p-hydroxybenzoate; and l,2-benzisothiazolin-3-one (BIT).

[0090] The presence of surfactants often causes water-based formulations to foam during mixing operations in production and in application through a spray tank. In order to reduce the tendency to foam, anti-foam agents are often added either during the production stage or before filling into bottles. Generally, there are two types of anti-foam agents, namely silicones and non- silicones. Silicones are usually aqueous emulsions of dimethyl

polysiloxane, while the non-silicone anti-foam agents are water-insoluble oils, such as octanol and nonanol, or silica. In both cases, the function of the anti-foam agent is to displace the surfactant from the air-water interface.

[0091] "Green" agents (e.g., adjuvants, surfactants, solvents) can reduce the overall environmental footprint of crop protection formulations. Green agents are biodegradable and generally derived from natural and/or sustainable sources, e.g. plant and animal sources. Specific examples are: vegetable oils, seed oils, and esters thereof, also alkoxylated alkyl polyglucosides.

Applications

[0092] The combination or composition provided may be used in an area where plants, such as crops, are growing (e.g. pre-planting, planting, pre-harvesting). The use of combination or composition provided to benefit the plants being grown in the area. Such benefits, may include, but are not limited to, improving the health of a plant, improving the yield of a plant (e.g. increased biomass and/or increased content of valuable ingredients), improving the vigor of a plant (e.g. improved plant growth and/or greener leaves), improving the quality of a plant (e.g. improved content or composition of certain ingredients), and improving the tolerance to abiotic and/or biotic stress of the plant.

[0093] In the practice of the present invention, the composition may be contacted with a plant in a variety of ways. For example, the composition of the present invention may be a solid, a liquid, a gas, or a mixture thereof.

[0094] An embodiment of the composition of the present invention may be brought into contact with plants or plant parts directly. Some examples of methods of such contact are, for example, spraying, foaming, fogging, pouring, brushing, dipping, similar methods, and combinations thereof. In some embodiments, spraying or dipping or both is used. In some embodiments, spraying is used. Such contact may be performed indoors or outdoors. In some of such embodiments, contact is performed on all or part of a plant while it is growing in a field (i.e., outdoor applications). It is contemplated that the compositions provided can be mixed with water in a spray tank for indoor and/or outdoor (open field) applications.

[0095] Normally, a specific part of the plant forms the useful product. A plurality of useful plant parts, after removal from a plurality of plants, is known as a "crop." Some types of plants have a single type of useful plant part, while other types of plants have plural types of useful plant parts.

[0096] Among the plants and plant parts that are suitable for use in the present invention, are, for example, plants (and parts thereof) with plant parts that are edible, plants (and parts thereof) with plant parts that are non-edible but useful for some other purpose, and combinations thereof. Also contemplated as suitable plants (and parts thereof) are those from which useful materials can be extracted; such useful materials may be, for example, edible materials, raw materials for manufacturing, medicinally useful materials, and materials useful for other purposes.

[0097] Further contemplated as suitable plants (and parts thereof) are those that yield plant parts that are useful for their beauty and/or ornamental properties. Such ornamental plant parts include, for example, flowers and other ornamental plant parts such as, for example, ornamental leaves. Some of such plants produce useful bulbs. In some

embodiments, an entire ornamental plant is considered to be the useful plant part.

[0098] Plants that produce all types of edible plant parts are contemplated as suitable for use in the present invention. Also suitable are all types of edible plant parts.

[0099] Many of the plants (and parts thereof) that are suitable for use in the practice of the present invention can be usefully divided into categories or groups. One useful method for defining such groups is the "Definition and Classification of Commodities," published on or before Mar. 23, 2006, by the Food and Agriculture Organization ("FAO") of the United Nations as a "Draft." In the practice of some embodiments of the present invention, it is contemplated to treat plants that produce one or more crops that fall within any of the crop groups defined by the FAO. In some embodiments, it is contemplated to treat one or more crops that fall within one or more of those groups.

[00100] Those skilled in the art would understand certain variations can exist based on the disclosure provided. Thus, the following examples are given for the purpose of illustrating the invention and shall not be construed as being a limitation on the scope of the invention or claims. EXAMPLES

Example 1

[00101] Cabbage plants with 2-3 new-growth-true leaf stage are treated with compositions tested using a track sprayer (400 L/Ha) on day zero (0). Three second instar diamondback moth are infested onto each leaf disc.

[00102] The ratio of spinetoram against 1-MCP is calculated based on the average of 6 ppm of Radiant (spinetoram) plus 12.5 ppm 1-MCP. The plant aging is allowed under UV light and insect control is show as five days after the initial treatment (5 DAT).

[00103] Colby's expected response is calculated where the mixtures are additive. A positive number for the Observed vs. Expected indicates synergistic effect between the two tested molecules. The results are shown in Table 1 (average of three trials).