(12) United States Patent (10) Patent No.: US 6,660,690 B2 Asrar Et Al

USOO6660690B2 (12) United States Patent (10) Patent No.: US 6,660,690 B2 ASrar et al. (45) Date of Patent: Dec. 9, 2003

(54) SEED TREATMENT WITH COMBINATIONS WO WO 00/35277 6/2000 ...... AO1 N/25/10 OF INSECTICDES WO WO 01/08490 2/2001 ...... AO1 N/53/OO OTHER PUBLICATIONS (75) Inventors: Jawed Asrar, Chesterfield, MO (US); Frank C. Kohn, St. Louis, MO (US) International Search Report for International Serial No. PCT/US01/42444 dated Aug. 28, 2002. (73) Assignee: Monsanto Technology, L.L.C., St. Abstract XP-002206730, Control of seed corn maggot with Louis, MO (US) Seed treatments, 1999. Abstract XP-002206731, Synthesis and insecticidal activity (*) Notice: Subject to any disclaimer, the term of this of nitroguanidine derivatives, 1999. patent is extended or adjusted under 35 Abstract XP-002195625, Exterminate Insect Seed Specified U.S.C. 154(b) by 0 days. Insect Mix Permethrin Extend Apply Range Reduce Con taminate, Jun. 15, 1989. (21) Appl. No.: 09/968,175 Article XP-0021956.16, W. Schoberlein, Influence of com bined fungicide-insecticide treatment of winter wheat Seed (22) Filed: Oct. 1, 2001 on crop development and yield after early and normal sowing date, pp. 310-336, Oct. 22, 1999. (65) Prior Publication Data Abstract XP-002195617, The title pesticide is prepared by US 2002/0115565 A1 Aug. 22, 2002 mixing cypermethrin, phoxim, parathion, etc., Jun. 28, 1995. Abstract XP-0021956.18, Insecticide treatment and seed Related U.S. Application Data quality of corn during Storage, 1999. (60) Provisional application No. 60/238,485, filed on Oct. 6, Abstract XP-002195619, Residual efficacy of cyfluthrin 2000. applied alone or in combination with piperonyl butoxide or piperonyl butoxide and chlorpyrifoS-methyl as protectants (51) Int. Cl." ...... A01N 25/26: A01N 57/00; on stored corn, 1994. AO1N 43/46; AO1N 43/40; AO1N 43/647 Abstract XP-002195620, Evaluation of the suitability of the (52) U.S. Cl...... 504/100; 504/194; 504/227; seed insecticidal preparation Montur 190 FS for protectioin 504/252; 504/261; 504/272; 504/275; 504/280; of a Sugar beet plantation, 2000. 504/326; 504/346; 504/355 Abstract XP-002195621, Insecticides for seed treatment, (58) Field of Search ...... 514/521; 504/100, 1987. 504/194, 227, 252, 261, 272, 275, 280, Abstract XP-002195622, Novel seed treatments to control 346,355, 326 aphids and virus yellows in Sugar beet, 2001. Abstract XP-002195624. A new insecticidal seed treatment (56) References Cited for oilseed rape, 2001. U.S. PATENT DOCUMENTS * cited by examiner 3,937,813 A 2/1976 Clark, Jr...... 424/93 4,053,595 A 10/1977. Zeck et al. ... 424/216 Primary Examiner Alton N. Pryor 4,064.237 A 12/1977 Gallo et al. ... 424/200 (74) Attorney, Agent, or Firm Nelson Mullins Riley & 4,263,287 A 4/1981 Dennis ...... 424/200 Scarborough 4,382,927 A 5/1983 Sherman ...... 424/200 4,415,561 A 11/1983 Behrenz et al...... 424/219 (57) ABSTRACT 4,863,909 A 9/1989 Behrenz et al...... 514/136 5,385,926 A 1/1995 Ludwig et al...... 514/383 A method of preventing damage to the Seed and/or shoots 5,696,144 A 12/1997 Royalty et al...... 514/.404 and foliage of a plant by a pest includes treating the Seed 5,849,320 A 12/1998 Turnbladet al...... 424/410 from which the plant grows with a composition that includes 5,852,012 A 12/1998 Maienfisch et al...... 514/229.2 a combination of at least one pyrethrin or Synthetic pyre 5,876.739 A 3/1999 Turnbladet al...... 424/408 throid and at least one other insecticide Selected from the 5,952.358 A 9/1999 Meunier et al...... 514/357 group consisting of an oxadia Zine derivative, a 5,972,941 A 10/1999 Schwalge et al...... 514/239.5 chloronicotinyl, a nitroguanidine, a pyrrol, a pyrazone, a 6,022,871 A 2/2000 Maienfisch et al...... 514/229.2 diacylhydrazine, a triazole, a biological/fermentation 6,225,344 B1 5/2001 Sembo ...... 514/471 product, a phenyl pyrazole, an organophosphate and a car FOREIGN PATENT DOCUMENTS bamate. It is preferred that when the other insecticide is an oxadiazine derivative, the pyrethroid is Selected from the DE 1982.3396 A1 12/1999 ...... AO1N/43/16 DE 19939841 A1 5/2000 ...... AO1N743/54 group consisting of tauflu valinate, flumethrin, trans DE 1985.7967 A1 6/2000 ... AO1 N/53/08 cy fluthrin, kadethrin, biore Smethrin, tetramethrin, EP O194566 9/1986 ... AO1 N/57/12 phenothrin, empen thrin, cyphenothrin, prallethrin, EP 101.317O 6/2000 ... AO1N743/56 imiprothrin, allethrin and bioallethrin. The treatment is FR 2729825 8/1996 ... AO1N/43/92 applied to the unsown Seed. In another embodiment, the Seed JP 626.3606 9/1994 ... AO1N/43/653 is a transgenic Seed having at least one heterologous gene WO WO 96/23411 8/1996 ... AO1 N/51/OO encoding for the expression of a protein having pesticidal WO WO 97/22254 6/1997 ... AO1N743/88 activity against a first pest and the composition has activity WO WO 97/40691 11/1997 ...... AO1 N/51/OO against at least one Second pest. Treated Seeds are also WO WO 97/40692 11/1997 ...... AO1 N/51/OO provided. WO 9935.913 * 7/1999 WO WO 99/63829 12/1999 ...... AO1N/63/OO WO WO OO/28825 5/2000 ...... AO1 N/51/OO 49 Claims, No Drawings US 6,660,690 B2 1 2 SEED TREATMENT WITH COMBINATIONS delta-endotoxins provided the transgenic corn with OF INSECTICIDES improved resistance to European corn borer. A comprehensive report of field trials of transgenic corn CROSS REFERENCE TO RELATED PATENTS that expresses an insecticidal protein from B. thuringiensis AND PATENT APPLICATIONS has been provided by Armstrong et al., in CropScience, This application is a non-provisional of U.S. Provisional 35(2):550–557 (1995). Patent Application Serial No. 60/238,485, filed Oct. 6, 2000, At the present State of plant cellular engineering, however, and claims priority thereto. transgenic crops are typically resistant only to Specific pests for that crop, e.g., transgenic corn expressing a Bt toxin BACKGROUND OF THE INVENTION against the corn rootworm. It is frequently necessary to apply Synthetic pesticides to Such transgenic plants to con (1) Field of the Invention trol damage by other pests. This invention relates generally to the control of plant Insecticides Such as Synthetic pyrethroids, organophos pests and more particularly to the provision of protection phates and carbamates, fungicides Such as azoles and against insect damage to Seeds and plant parts by the 15 anilopyrimidines, and acaricides Such as pyrazoles, and the treatment of plant Seeds with combinations of pesticides. like, are very effective against certain above ground plant (2) Description of the Related Art pests when applied at the proper time and with proper The control of insects and related arthropods is of extreme procedures. Appropriate pesticides may be applied at the importance to the agricultural industry. Every year, these time of planting as Surface bands, “T-bands, or in-furrow, pests destroy an estimated 15% of agricultural crops in the but these applications require the additional operation of United States and even more than that in developing coun applying the pesticide at the same time as the Seeds are being tries. Some of this damage occurs in the Soil when plant Sown. This complicates the planting operation and the pathogens, insects and other Such Soil borne pests attack the additional equipment required for pesticide application is Seed after planting. Much of the rest of the damage is caused 25 costly to purchase and requires maintenance and attention by rootworms, plant pathogens that feed upon or otherwise during use. Moreover, care must be taken to incorporate the damage the plant roots, and by cutworms, European corn pesticides properly into the topmost Soil layer for optimal borers, and other pests that feed upon or damage the above activity. (See, for example, the application requirements and ground parts of the plant. General descriptions of the type precautions for use of tefluthrin that are described in the and mechanisms of attack of pests on agricultural crops are brochure titled Force 3G Insecticide, published by Zeneca provided by, for example, Metcalf, in Destructive and Useful AgProducts, Wilmington, Del. (1998)). Insects, (1962); and Agrios, in Plant Pathology, 3rd Ed., The activity of pesticides that have been applied as Academic Press (1988). in-furrow applications at the time of Sowing is usually The period during germination of the Seed, Sprouting and directed to the protection of the seed or the roots of the plant. initial growth of the plant is particularly critical because the 35 Some protection against above ground pests Such as corn roots and shoots of the growing plant are Small and even a borers has been reported, however, for Such treatments with Small amount of damage can kill the entire plant. Moreover, insecticides known to be Systemic. Keaster and Fairchild, J. Some natural plant defenses are not fully developed at this Econ. Entomol, 61(2):367–369 (1968). Since such pesticide Stage and the plant is Vulnerable to attack. Not Surprisingly, chemicals are complex molecules that are expensive to the control of pests that attack the Seed and the above ground 40 produce, purchase and use, it is desirable that their activity plant parts during this early Stage of plant growth is a well is not diluted or lost by migration away from the desired site developed area of agriculture. of action by moisture Seepage or by vaporization. Currently, the control of pests that attack post emergent After the plant has emerged from the Soil, foliar spraying crops primarily involves the application of Synthetic organic of pesticides is most often used to control those pests that pesticides to the Soil, or to the growing plants by foliar 45 attach the Shoots and foliage of the plant. However, a foliar Spraying. Because of concern about the impact of chemical Spray must be applied at a certain time that coincides with pesticides on public health and the environment, there has the presence and activity of the pest in order to have the most been much effort to reduce the amount of chemical pesti beneficial effect. Application at this time may be difficult or cides that are used. A significant portion of this effort has impossible if, for example, weather conditions limit access been expended in developing transgenic crops engineered to 50 to the field. Moreover, the plants must be monitored closely express insect toxicants from microorganisms. For example, to observe early signs of pest activity in order to apply the U.S. Pat. No. 5,877,012 to Estruch et al. discloses the pesticide at a time when the pests are most Vulnerable. cloning and expression of proteins from Such organisms as Synthetic pyrethroids have been found to give excellent Bacillus, Pseudomonas, Clavibacter and Rhizobium into control of pests of the order of Lepidoptera, Such as plants to obtain transgenic plants with resistance to Such 55 cutworms, when applied as foliar spray or as Surface pests as black cutworms, armyworms, Several borers and incorporated granules at the time of planting. However, other insect pests. Publication WO/EP97/07089 by Privalle Since this class of insecticides has very high toxicity to fish, et al. teaches the transformation of monocotyledons, Such as for example, great care must be taken to limit the runoff of corn, with a recombinant DNA sequence encoding peroxi the insecticide from either granules or spray into Surface dase for the protection of the plant from feeding by corn 60 waters. Moreover, any foliar spraying must be done at times borers, earworms and cutworms. Jansens et al., in CropSci., when there is little wind, and then only with proper equip 37(5):1616–1624 (1997), reported the production of trans ment that is carefully monitored during use. genic corn containing a gene encoding a crystalline protein It has also been found in Some cases with particular from Bacillus thuringiensis that controlled both generations pesticides and application techniques that when two or more of the European corn borer. U.S. Pat. Nos. 5,625,136 and 65 of Such pesticides are used in particular combination greater 5,859,336 to Koziel et al. reported that the transformation of efficacy results than when any one of Such pesticides is used corn with a gene from B. thuringiensis that encoded for alone. Such benefits of combining pesticides has been US 6,660,690 B2 3 4 reported for combinations of phosmet with diflubenzuron and/or shoots and foliage of a plant grown from the Seed, the (U.S. Pat. No. 4,382,927); O-ethyl-O-4-(methylthio)- method comprising treating the unsown Seed with a com phenyl-S-propyl phosphodithioate and N'-(4-chloro-o- position comprising at least one pyrethrin or Synthetic tolyl)-N,N-dimethylformamidine (U.S. Pat. No. 4,053, pyrethroid and at least one other insecticide Selected from 595); bacillus thuringiensis and chlordimeform (U.S. Pat. the group consisting of an oxadiazine derivative, a No. 3,937,813); decamethrine and dichlorvos with propoxur, chloronicotinyl, a nitroguanidine, a pyrrol, a pyrazone, a if desired, (U.S. Pat. No. 4,863,909); fenvalerate and phos diacylhydrazine, a triazole, a biological/fermentation met (U.S. Pat. No. 4,263,287); and phosalone and malathion product, a phenyl pyrazole, an organophosphate and a car (U.S. Pat. No. 4,064.237). However, each of these combi bamate. It is preferred that when the other insecticide is an nations was applied directly to the growing plant as oXadizine derivative, the pyrethroid is Selected from the described above in the form of Sprays or dusts, or applied to group consisting of tauflu valinate, flumethrin, trans the Soil around the plant in the form of, for example, cy fluthrin, kadethrin, biore Smethrin, tetramethrin, granules. phenothrin, empen thrin, cyphenothrin, prallethrin, WO9740692 discloses combinations of any one of several imiprothrin, allethrin and bioallethrin. Seeds that have been oxadiazine derivatives with one of a long list of other 15 treated by this method are also provided. insecticides. Although the application mentions that the The invention is also directed to a novel composition for combinations can be applied to plant propagation material the treatment of unsown Seed comprising at least one for its protection, as well as to plant shoots and leaves, no pyrethrin or Synthetic pyrethroid and at least one other examples are provided to demonstrate that any one of the insecticide Selected from the group consisting of an oxadi combinations listed is actually efficacious. More pesticide azine derivative, a chloronicotinyl, a nitroguanidine, a combinations are described in U.S. Pat. Nos. 4,415,561, pyrrol, a pyrazone, a diacylhydrazine, a triazole, a 5,385,926, 5,972,941 and 5,952,358. However, in the exist biological/fermentation product, a phenyl pyrazole, an orga ing art, little or no guidance has been found as methods for nophosphate and a carbamate. It is preferred that when the predicting which combinations of pesticides will result in other insecticide is an oxadizine derivative, the pyrethroid is Such unexpectedly Superior efficacy and which combina 25 Selected from the group consisting of tauflu valinate, tions will not. flumethrin, trans-cy fluthrin, kadethrin, bioresmethrin, The control of pests by applying insecticides directly to tetramethrin, phenothrin, empenthrin, cyphenothrin, plant seed is well known. For example, U.S. Pat. No. prallethrin, imiprothrin, allethrin and bioallethrin. 5,696,144 discloses that the European corn borer caused less The invention is also directed to a novel method for feeding damage to corn plants grown from Seed treated with preventing damage by a pest to a Seed and/or shoots and a 1-arylpyrazole compound at a rate of 500 g per quintal of foliage of a plant grown from the Seed, the method com Seed than control plants grown from untreated Seed. In prising treating the unsown Seed with a composition com addition, U.S. Pat. No. 5,876.739 to Turnbladet al. (and its prising a nitroguanidine and at least one other insecticide parent, U.S. Pat. No. 5,849,320) disclose a method for Selected from the group consisting of a chloronicotinyl, a controlling Soil-borne insects which involves treating Seeds 35 pyrrol, a pyrazone, a diacylhydrazine, a triazole, a with a coating containing one or more polymeric binders and biological/fermentation product, a phenyl pyrazole, an orga an insecticide. This reference provides a list of insecticides nophosphate and a carbamate. Seeds that have been treated that it identifies as candidates for use in this coating and also by this method are also provided. names a number of potential target insects. However, while The invention is also directed to a novel composition for the U.S. Pat. No. 5,876.739 patent states that treating corn 40 treatment of unsown Seed, the composition comprising a Seed with a coating containing a particular insecticide pro nitroguanidine and at least one other insecticide Selected tects corn roots from damage by the corn rootworm, it does from the group consisting of a chloronicotinyl, a pyrrol, a not indicate or otherwise Suggest that treatment of corn Seed pyrazone, a diacylhydrazine, a triazole, a biological/ with any particular combinations of insecticides provides the fermentation product, a phenyl pyrazole, an organophos Seed or the plant with Synergistic protection, or with any 45 other unexpected advantage. phate and a carbamate. Thus, although the art of protecting the shoots and The invention is also directed to a novel seed that is foliage-as well as the Seed and roots-of a plant from protected against multiple pests comprising a Seed having at damage by pests has been advancing rapidly, Several prob least one heterologous gene encoding for the expression of lems still remain. For example, it would be useful to provide 50 a protein that is active against a first pest and, in addition, a method for the control of pest damage to Shoots and foliage having adhered thereto a composition comprising at least of plants without the requirement of applying a pesticide at one pyrethrin or Synthetic pyrethroid and at least one other the time of Sowing the Seed, either as a Surface incorporated insecticide Selected from the group consisting of an oxadi band, or in-furrow, for example, or requiring a later field azine derivative, a chloronicotinyl, a nitroguanidine, a 55 pyrrol, a pyrazone, a diacylhydrazine, a triazole, a application of a pesticide during plant growth. It would also biological/fermentation product, a phenyl pyrazole, an orga be useful if the method for pest control reduced the amount of pesticide that was required to provide a certain level of nophosphate and a carbamate, where the composition is protection to the plant. Furthermore, it would be useful if present in an amount effective to provide protection to the such a method could be coupled with the biopesticidal shoots and foliage of the plant against damage by at least one activity of transgenic plants, or with the insecticidal activity 60 Second pest. of other active materials to provide a broader Scope of The invention is also directed to a novel method for protection than is provided by the transgenic elements, or the treating an unsown Seed to prevent damage by a pest to the insecticidal actives alone. Seed and/or shoots and foliage of a plant grown from the Seed, the method comprising contacting the unsown Seed SUMMARY OF THE INVENTION 65 with a composition comprising at least one pyrethrin or Briefly, therefore, the present invention is directed to a Synthetic pyrethroid and at least one other insecticide novel method for preventing damage by a pest to a Seed Selected from the group consisting of an oxadiazine US 6,660,690 B2 S 6 derivative, a chloronicotinyl, a nitroguanidine, a pyrrol, a Another advantage of the novel treatment is that it can be pyrazone, a diacylhydrazine, a triazole, a biological/ used with transgenic Seeds of the type having a heterologous fermentation product, a phenyl pyrazole, an organophoS gene encoding for the expression of a pesticidal protein in phate and a carbamate, provided that when the other insec the transgenic plant that grows from the Seed. Treating Such ticide is an oxadizine derivative, the pyrethroid is Selected a Seed with a pesticide provides the ability to protect against from the group consisting of taufluvalinate, flumethrin, one pest with the transgenic trait and to provide Surprisingly trans-cyfluthrin, kadethrin, bioresmethrin, tetramethrin, enhanced protection against the same pest, and/or to protect phenothrin, empen thrin, cyphenothrin, prallethrin, against other pests with the Subject combination of insecti imiprothrin, allethrin and bioallethrin. cides. Among the advantages found to be achieved by the As used herein, the terms “pesticidal effect” and “pesti present invention, therefore, may be noted the provision of cidal activity” mean any direct or indirect action on the a method for the control of pest damage to Seeds and/or target pest that results in reduced feeding damage on the shoots and foliage of plants without the requirement of Seeds, roots, shoots and foliage of plants grown from treated applying a pesticide at the time of Sowing the Seed, either as Seeds as compared to plants grown from untreated Seeds. a Surface incorporated band, or in-furrow, for example, or 15 The terms “active against a (first or Second) pest”, also have requiring a later field application of a pesticide during plant the same meaning. Such direct or indirect actions include growth; the provision of a method for pest control that inducing death of the pest, repelling the pest from the plant reduces the amount of pesticide that is required for the Seeds, roots, shoots and/or foliage, inhibiting feeding of the provision of a certain level of protection to the plant; and the pest on, or the laying of its eggs on, the plant Seeds, roots, provision of method that can be coupled with the biopesti shoots and/or foliage, and inhibiting or preventing repro cidal activity of transgenic plants to Selectively broaden the duction of the pest. The term “insecticidal activity” has the Scope of protection that is provided for the shoots and Same meaning as pesticidal activity, except it is limited to foliage of the transgenic. those instances where the pest is an insect. When the term DETAILED DESCRIPTION OF THE "pesticide' is used herein, it is not meant to include pesti 25 cides that are produced by the particular Seed or the plant PREFFERED EMBODIMENTS that grows from the particular Seed that is treated with the In accordance with the present invention, it has been pesticide. discovered that treatment of unsown plant Seeds with a AS used herein, the "shoots and foliage” of a plant are to composition that includes a specific combination of insec be understood to be the shoots, Stems, branches, leaves and ticides not only protects the Seeds themselves, but other appendages of the Stems and branches of the plant after Surprisingly-also provides post-emergent control of pests the Seed has Sprouted, but not including the roots of the that feed on or otherwise damage the shoots and/or foliage plant. It is preferable that the shoots and foliage of a plant of the plant. The combination of insecticides that has been be understood to be those non-root parts of the plant that found to achieve Such results is a combination of a pyrethrin have grown from the Seed and are located a distance of at or Synthetic pyrethroid as one component, and with another 35 component comprising one or more of certain other insec least one inch away from the Seed from which they emerged ticides Selected from the group consisting of an oxadiazine (outside the region of the seed), and more preferably, to be derivative, a chloronicotinyl, Such as imidacloprid, the non-root parts of the plant that are at or above the Surface acetamiprid, and nitenpyram; a nitroguanidine, a pyrrol, of the soil. As used herein, the “region of the seed” is to be understood to be that region within about one inch of the Such as chlorfeinapyr; a pyrazole, Such as tebufenpyrad; a 40 diacylhydrazine, Such as tebufenozide, methoxyfenozide, Seed. and halofenozide, a triazole, Such as triazamate; a biological/ Pesticides suitable for use in the invention include pyre fermentation product, Such as avermectin and Spinosad; a thrins and Synthetic pyrethroids, oxadizine derivatives, chlo phenyl pyrazole, Such as fipronil, an organophosphate, Such ronicotinyls, nitroguanidine derivatives, triazoles, organo as a cephate, fenamiphos, diaZinon, chlorpyrifos, 45 phosphates, pyrrols, pyrazoles; phenyl pyrazoles; chlorpyrifon-methyl and malathion; and a carbamate, Such diacylhydrazines, biological/fermentation products, and car as carbaryl, aldicarb, carbofuran, thiodicarb and oxamyl. It bamates. Further information about pesticides of the types is preferred, however, that if the other insecticide is an listed above can be found in The Pesticide Manual, 11th Ed., oxadiazine derivative, the pyrethroid should be Selected C. D. S. Tomlin, Ed., British Crop Protection Council, from the group consisting of taufluvalinate, flumethrin, 50 Farnham, Surry, UK (1997). trans-cyfluthrin, kadethrin, bioresmethrin, tetramethrin, Pyrethroids that are useful in the present composition phenothrin, empen thrin, cyphenothrin, prallethrin, include pyrethrins and Synthetic pyrethroids. The pyrethrins imiprothrin, allethrin and bioallethrin. that are preferred for use in the present method include, In preferred embodiments, the combination of the insec without limitation, 2-allyl-4-hydroxy-3-methyl-2- ticides provides unexpectedly Superior protection in that the 55 cyclopenten-1-one ester of 2,2-dimethyl-3-(2-methyl combination of the insecticides provides a level of protec propenyl)-cyclopropane carboxylic acid, and/or (2-methyl tion to the Seed and/or the plant that is Superior to the level 1-prope nyl)-2-methoxy-4-oxo-3-(2 prope nyl)-2- of protection that-based on the current State of the art cyclopenten-1-yl ester and mixtures of cis and trans isomers would be predicted from the protection provided by the thereof (Chemical Abstracts Service Registry Number individual components applied Separately. This Synergistic 60 (“CAS RN”) 8003-34-7). activity reduces the total amount of pesticide that is required Synthetic pyrethroids that are preferred for use in the to provide a certain level of protection. In addition to being present invention include (S)-cyano(3-phenoxyphenyl) more economical to use, the ability to use a reduced amount methyl 4-chloro alpha (I-methylethyl)benzeneacetate of pesticide for a given level of protection is advantageous (fenvalerate; CAS RN 51630-58-1); (S)-cyano in that Seed treatments with reduced amounts of insecticides 65 (3-phenoxyphenyl) methyl (S)-4-chloro-alpha-(1- are leSS phytotoxic to the Seed than when the insecticides are methylethyl) benzeneacetate (esfenvalerate; CAS RN used separately. 66230-04-4); (3-phenoxyphenyl)-methyl(+)-cis-trans-3-(2,2- US 6,660,690 B2 7 8 dichoroethenyl)-2,2-dimethylcyclopropane carboxylate dimethyl-3-(2-methylprop-1-enyl) cyclopropane carboxy (permethrin; CAS RN 52645-53-1); (+) alpha-cyano-(3- late (allethrin; CAS RN 584-79-2); (bioallethrin; CAS RN phenoxyphenyl) methyl(+)-cis, trans-3-(2,2- 584-79-2); and (ZXI8901; CAS RN 160791-64-0). It is dichloroethenyl)-2,2-dimethyl-cyclopropane carboxylate believed that mixtures of one or more of the aforementioned (cypermethrin; CAS RN 52315-07-8); (beta-cypermethrin; Synthetic pyrethroids can also be used in the present inven CAS RN 65731-84-2); (theta cypermethrin; CAS RN tion. 71697-59-1); S-cyano (3-phenoxyphenyl) methyl (+) cis/ In one embodiment of the present invention, particularly trans 3-(2,2-dichloroethenyl) 2,2-dimethylcyclopropane car preferred Synthetic pyrethroids are tefluthrin, lambda boxylate (Zeta-cypermethrin; CAS RN 52315-07-8); (s)- cyhalothrin, bifenthrin, permethrin and cyfluthrin. Even alpha -cyano-3-phenoxybenzyl (IR,3R)-3-(2,2- more preferred Synthetic pyrethroids are tefluthrin and dibromovinyl)-2,2-dimethyl cyclopropane carboxylate lambda cyhalothrin. (deltamethrin; CAS RN 52918-63-5); alpha-cyano-3- In another embodiment of the invention -where an phenoxybenzyl 2,2,3,3,-tetramethyl cyclopropoanecarboxy oxadiazine derivative is used as one of the combination of late (fenpropathrin; CAS RN 64257-84-7); (RS)-alpha insecticides—the preferred Synthetic pyrethroid is Selected cyano-3-phenoxybenzyl(R)-2-(2-chloro-4-(trifluoromethyl) 15 from the group consisting of tauflu valinate, flumethrin, anilinol-3-methylbutanoate (tau-fluvalinate; CAS RN trans-cyfluthrin, kadethrin, bioresmethrin, tetramethrin, 102851-06-9); (2,3,5,6-tetrafluoro-4-methylphenyl)- phenothrin, empen thrin, cyphenothrin, prallethrin, methyl-(1 alpha, 3 alpha)-(Z)-(+)-3-(2-chloro-3,3,3- imiprothrin, allethrin and bioallethrin. trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylate The pyrethrins and Synthetic pyrethroids that are useful in (tefluthrin; CAS RN 79538-32-2); (+)-cyano the present compositions can be of any grade or purity that (3-phenoxyphenyl) methyl (t)-4-(difluoromethoxy)-alpha pass in the trade as pyrethrins and Synthetic pyrethroids. (1-methyl ethyl) benzeneacetate (flucythrinate; CAS RN Other materials that accompany the pyrethrins and Synthetic 70124-77-5); cyano(4-fluoro-3-phenoxyphenyl)methyl pyrethroids in commercial preparations as impurities can be 3-2-chloro-2-(4-chlorophenyl)e the nyl-2,2- tolerated in the Subject compositions, as long as Such other dimethylcyclopropanecarboxylate (flumethrin; CAS RN 25 69770-45-2); cyano(4-fluoro-3-phenoxyphenyl) methyl materials do not destabilize the composition or significantly 3-(2,2-dichloro e the nyl)-2,2-dimethyl reduce or destroy the activity of any of the insecticide cyclopropanedarboxylate (cyfluthrin; CAS RN 68359-37 components against the target pest. One of ordinary skill in 5); (beta cyfluthrin; CAS RN 68359-37-5); (transfluthrin; the art of the production of insecticides can readily identify CAS RN 118712-89-3); (S)-alpha-cyano-3-phenoxybenzyl those impurities that can be tolerated and those that cannot. (Z)-(IR-cis)-2,2-dimethyl-3-2-(2,2,2-trifluoro Insecticides that are oxadiazine derivatives are useful as trifluoromethyl-ethoxycarbonyl) vinylcyclopropane car one of the components of the Subject composition. OXadiz ine derivatives that are preferred for use in the present boxylate (acrinathrin; CAS RN 101007-06-1); (IR cis) S and invention include 5-(2-chloropyrid-5-ylmethyl)-3-methyl-4- (IS cis) R enantiomer isomer pair of alpha-cyano-3- nitroiminoperhydro-1,3,5-oxadiaZine, 3-methyl-4- phenoxybenzyl-3-(2,2-dichloro vinyl)-2,2- 35 nitroimino-5-(1-oxido-3-pyridinomethyl) perhydro-1,3,5- dimethylcyclopropane carboxylate (alpha-cypermethrin; oxadiazine; 5-(2-chloro-1-oxido-5-pyridiniomethyl)-3- CAS RN 67375-30-8); IIR,3S)3(1 RS)(1',2',2',2'- methyl-4-nitroiminoperhydro-1,3,5-oxidiazine; and tetrabromoethyl)-2,2-dimethyl cyclopropanecarboxylic 3 - methyl-5-(2-methylpy rid-5-ylmethyl)-4- acid (S)-alpha-cyano-3-phenoxybenzyl ester (tralomethrin; nitroiminoperhydro-1,3,5-oxadiazine. CAS RN 66841-25-6); cyano-(3-phenoxyphenyl) methyl 40 2,2-dichloro-1-(4-ethoxyphenyl)cyclopropane carboxylate Chloronicotinyl insecticides are also useful as one of the (cycloprothrin; CAS RN 63935-38-6); 1C, 3C(Z)-(+)- components of the Subject composition. Chloronicotinyls cyano-(3-phenoxyphenyl)methyl 3-(2-chloro-3,3,3- that are preferred for use in the Subject composition include trifluoro-1-propenyl)-2,2-cimethylcyclopropanecarboxylate acetamiprid ((E)-N-(6-chloro-3-pyridinyl)methyl)-N'- (cyhalothrin; CAS RN 68085-85-8); 1 alpha (s), 3 alpha 45 cyano-N-methyleneimidamide; CAS RN 135410-20-7); (Z)-cyano(3-phenoxyphenyl) methyl-3-(2-chloro-3,3,3- imidacloprid (1-(6-chloro-3-pyridinyl)methol-N-nitro-2- trifluoro-1-propenyl)-2,2-dimethylcyclopropane carboxy imidazolidinimime; CAS RN 138261-41-3); and nitenpyram late (lambda cyhalothrin; CAS RN 91465-08-6); (2-methyl (N-(6-chloro-3-pyridinyl)methyl-N-ethyl-N'-methyl-2- 1,1'-biphenyl)-3-yl) methyl 3-(2-chloro-3,3,3-trifluoro-1- nitro-1,1-ethenediamine; CAS RN 120738-89-8). prope nyl)-2,2-dimethyl-cyclopropane carboxylate 50 Nitroguanidine insecticides are useful as one of the com (bifenthrin; CAS RN 82657-04-3); 5-1-benzyl-3- ponents of the present combination. Nitroguanidines that are furylmethyl-d-cis(1R,3S,E)2,2-dimethyl-3-(2-oxo-2,2,4,5 preferred for use in the present invention include MTI 446 tetrahydro thiophenylidenemethyl)cyclopropane carboxy (nidinotefuran). late (kadethrin, RU15525; CAS RN58769-20-3); 5-(phenyl Pyrrols, pyrazoles and phenyl pyrazoles that are useful in methyl)-3-furanyl-3-furanyl 2,2-dimethyl-3-(2-methyl-1- 55 the present composition include those that are described in propenyl)cyclopropane carboxylate (reSmethrin; CAS RN U.S. Pat. No. 5,952,358. Preferred pyrazoles include chlo 10453-86-8); (1R-trans)-5-(phenylmethyl)-3-furanyl rfenapyr (4-bromo-2-(4-chlorophenyl)-1-ethoxymethyl-5- methyl 2,2-dimethyl-3-(2-methyl-1-prope nyl) trifluoromethylpyrrole-3-carbonitrile; CAS RN 1224.53-73 cyclopropanecarboxylate (bioresmethrin; CAS RN 28434 0); fenpyroximate ((E)-1,1-dimethylethyl-4-(1,3- 01-7); 3,4,5,6-tetrahydro-phthalimidomethyl-(IRS)-cis 60 dimethyl-5-phenoxy-1H-pyrazole-4-yl)methylenelamino trans-chrysanthemate (tetramethrin; CAS RN 7696-12-0); oxymethylbenzoate; CAS RN 111812-58-9); and 3-phenoxybenzyl-d, I-cis, trans 2,2-dimethyl-3-(2- tebufenpyrad (4-chloro-N4-1,1-dimethylethyl)phenyl methylpropenyl) cyclopropane carboxylate (phenothrin; methyl-3-ethyl-1-methyl-1H-pyrazole-5-carboxamide; CAS RN 26002-80-2); (empenthrin; CAS RN 54406-48-3); CAS RN 119168-77-3). A preferred phenyl pyrazole is (cyphenothrin; CAS RN39515-40-7); (prallethrin; CAS RN 65 fipronil (5-amino-2,6-dichloro-4-(trifluoromethyl)phenyl 23031-36-9); (imiprothrin; CAS RN 72963-72-5); (RS)-3- 4-(1R,S)-(trifluoromethyl)sulfinyl)-1H-pyrazole-3- allyl-2-methyl-4-oxcyclopent-2-enyl-(1A,3R; 1R,3S)-2,2- carbonitrile; CAS RN 120068-37-3). US 6,660,690 B2 9 10 Diacylhydrazines that are useful in the present invention include halofenozide (4-chlorobenzoate-2-benzoyl-2-(1,1- TABLE 1-continued dimethylethyl)-hydrazide; CAS RN 112226-61-6); meth oxyfenozide (RH-2485; N-tert-butyl-N'-(3-methoxy-o- Combinations of pyrethroids and other non-pyrethroid toluoyl)-3,5-xylohydrazide; CAS RN 161050-58-4); and insecticides that provide synergistic insecticidal activity". tebufenozide (3,5-dimethylbenzoic acid 1-(1,1- COMPOSITION dimethylethyl)-2,(4-ethylbenzoyl)hydrazide; CAS RN NO. PYRETHROID OTHER INSECTICDE

112410-23-8). al a-cy la hirin nidinotefuran Triazoles, such as amitrole (CASRN 61-82-5) and triaz al a-cy la hirin chlorfenapyr amate are useful in the composition of the present invention. al a-cy la hirin fenpyroximate al a-cy la hirin tebufenpyrad A preferred triazole is tria Zamate (ethyl 1 - al a-cy la hirin fipronil (dimethylamino)carbonyl)-3-(1,1-dimethylethyl)-1H-1,2, al a-cy al hirin tebufenozide 4-triazol-5-yl)thioacetate; CAS RN 112143-82-5). al a-cy la hirin methoxyfenozide al a-cy la hirin halofenozide Biological/fermentation products, Such as avermectin 15 al a-cy la hirin triazamate (abamectin; CAS RN 71751-41-2) and spinosad (XDE-105, al a-cy la hirin avermectin CAS RN 131929-60-7) are useful in the present composi al a-cy la hirin spinosad tion. al a-cy la hirin acephate al a-cy la hirin fenamiphos Organophosphate insecticides are also useful as one of the al a-cy la hirin diazinon components of the composition of the present invention. al a-cy la hirin chlorpyrifos al a-cy la hirin chlorpyrifos-methyl Preferred organophophate insecticides include acephate al a-cy la hirin malathion (CAS RN 30560-19-1); chlorpyrifos (CAS RN 2921-88-2); al a-cy la hirin carbaryl chlorpyrifos-methyl (CAS RN 5598-13-0); diazinon (CAS al a-cy la hirin aldicarb RN 333-41-5); fenamiphos (CAS RN 22224-92-6); and al a-cy la hirin carbofuran a-cy la hirin thiodicarb malathion (CAS RN 121-75-5). 25 an a-cy la hirin Oxamyl In addition, carbamate insecticides are useful in the Sub hirin acetamiprid hirin imidacloprid ject composition. Preferred carbamate insecticides are aldi hirin nitenpyram carb (CAS RN 116-06-3); carbaryl (CAS RN 63-25-2); hirin nidinotefuran carbofuran (CAS RN 1563-66-2); oxamyl (CAS RN 23135 hirin chlorfenapyr 22-0) and thiodicarb (CAS RN 59669-26-0). hirin fenpyroximate hirin tebufenpyrad When an insecticide is described herein, it is to be hirin fipronil understood that the description is intended to include Salt hirin tebufenozide forms of the insecticide as well as any isomeric and/or hirin methoxyfenozide tautomeric form of the insecticide that exhibits the same hirin halofenozide 35 hirin triazamate insecticidal activity as the form of the insecticide that is hirin avermectin described. hirin spinosad hirin acephate One embodiment of this invention comprises treating a hirin fenamiphos Seed with a composition comprising at least one pyrethrin or hirin diazinon Synthetic pyrethroid and at least one other insecticide hirin chlorpyrifos 40 hirin chlorpyrifos-methyl Selected from the group consisting of a chloronicotinyl, a hirin malathion nitroguanidine, a pyrrol, a pyrazole, a diacylhydrazine, a hirin carbaryl triazole, a biological/fermentation product, a phenyl hirin aldicarb pyrazole, an organophosphate and a carbamate. The treat hirin carbofuran hirin thiodicarb ment is applied to the Seed prior to Sowing the Seed So that 45 hirin Oxamyl the Sowing operation is simplified. In this manner, Seeds can hirin acetamiprid be treated, for example, at a central location and then hirin imidacloprid dispersed for planting. This permits the perSon who plants hirin nitenpyram hirin nidinotefuran the Seeds to avoid the handling and use of insecticides hirin chlorfenapyr Some of which can be toxic-and to merely handle and plant 50 hirin fenpyroximate the treated Seeds in a manner that is conventional for regular hirin tebufenpyrad untreated Seeds. It is preferred, in Some combinations that at hirin fipronil hirin tebufenozide least one of the pyrethroid and the other insecticide is a hirin methoxyfenozide Systemic insecticide. hirin halofenozide In this embodiment, a Seed can be treated with any one of 55 hirin triazamate the combinations of insecticides that are shown in Table 1. Cy hirin avermectin hirin spinosad hirin acephate TABLE 1. hirin fenamiphos hirin diazinon Combinations of pyrethroids and other non-pyrethroid hirin chlorpyrifos insecticides that provide Synergistic insecticidal activity". 60 hirin chlorpyrifos-methyl hirin malathion COMPOSITION hirin carbaryl NO. PYRETHROID OTHER INSECTICDE hirin aldicarb hirin carbofuran 1. lambda-cyhalothrin acetamiprid hirin thiodicarb 2 lambda-cyhalothrin imidacloprid 65 hirin Oxamyl 3 lambda-cyhalothrin nitenpyram hirin acetamiprid US 6,660,690 B2 12

TABLE 1-continued TABLE 1-continued Combinations of pyrethroids and other non-pyrethroid Combinations of pyrethroids and other non-pyrethroid insecticides that provide synergistic insecticidal activity". insecticides that provide synergistic insecticidal activity".

COMPOSITION COMPOSITION NO. PYRETHROID OTHER INSECTICDE NO. PYRETHROID OTHER INSECTICDE 77 bi enthrin imidacloprid 50 esfenvalerate Oxamyl 78 bi enthrin nitenpyram 51 ele hirin acetamiprid 79 bi enthrin nidinotefuran 1O 52 ele hirin imidacloprid 8O bi enthrin chlorfenapyr 53 ele hirin nitenpyram 81 bi enthrin fenpyroximate 54 ele hirin nidinotefuran 82 bi enthrin tebufenpyrad 55 ele hirin chlorfenapyr 83 bi enthrin fipronil 56 ele hirin fenpyroximate 84 bi enthrin tebufenozide 57 ele hirin tebufenpyrad 85 bi enthrin methoxyfenozide 15 58 ele hirin fipronil 86 bi enthrin halofenozide 59 ele hirin tebufenozide 87 bi enthrin triazamate 60 ele hirin methoxyfenozide 88 bi enthrin avermectin 61 ele hirin halofenozide 89 bi enthrin spinosad 62 ele hirin triazamate 90 bi enthrin acephate 63 ele hirin avermectin 91 bi enthrin fenamiphos 64 ele hirin spinosad 92 bi enthrin diazinon 65 ele hirin acephate 93 bi enthrin chlorpyrifos 66 ele hirin fenamiphos 94 bi enthrin chlorpyrifos-methyl 67 ele hirin diazinon 95 bi enthrin malathion 68 ele hirin chlorpyrifos 96 bi enthrin carbaryl 69 ele hirin chlorpyrifos-methyl 97 bi enthrin aldicarb 70 ele hirin malathion 98 bi enthrin carbofuran 25 71 ele hirin carbaryl 99 bi enthrin thiodicarb 72 ele hirin aldicarb OO bi enthrin Oxamyl 73 ele hirin carbofuran O1 CWa Ca acetamiprid 74 ele hirin thiodicarb O2 CWa Ca imidacloprid 75 ele hirin Oxamyl O3 CWa Ca nitenpyram 76 cypermethrin acetamiprid O4 CWa Ca nidinotefuran 77 cypermethrin imidacloprid 05 CWa Ca chlorfenapyr 78 cypermethrin nitenpyram O6 CWa Ca fenpyroximate 79 cypermethrin nidinotefuran O7 CWa Ca tebufenpyrad 8O cypermethrin chlorfenapyr O8 eWa ea fipronil 81 cypermethrin fenpyroximate O9 CWa Ca tebufenozide 82 cypermethrin tebufenpyrad 1O CWa Ca methoxyfenozide 35 83 cypermethrin fipronil 11 CWa Ca halofenozide 84 cypermethrin tebufenozide 12 CWa Ca triazamate 85 cypermethrin methoxyfenozide 13 CWa Ca avermectin 86 cypermethrin halofenozide 14 CWa Ca spinosad 87 cypermethrin triazamate 15 CWa Ca acephate 88 cypermethrin avermectin 16 CWa Ca 89 fenamiphos 40 cypermethrin spinosad 17 CWa Ca diazinon 90 cypermethrin acephate 18 CWa Ca chlorpyrifos 91 cypermethrin fenamiphos 19 CWa Ca chlorpyrifos-methyl 92 cypermethrin diazinon 2O CWa Ca malathion 93 cypermethrin chlorpyrifos 21 CWa Ca carbaryl 94 cypermethrin chlorpyrifos-methyl 22 CWa Ca aldicarb 95 cypermethrin malathion 23 CWa Ca carbofuran 45 96 cypermethrin carbaryl 24 CWa Ca thiodicarb 97 cypermethrin aldicarb 25 CWa Ca Oxamyl 98 cypermethrin carbofuran 26 CS CWa Ca acetamiprid 99 cypermethrin thiodicarb 27 CS CWa Ca imidacloprid 2OO cypermethrin Oxamyl 28 CS CWa Ca nitenpyram 2O1 beta-cy ele hirin acetamiprid 29 CS CWa Ca nidinotefuran 50 2O2 beta-cy ele hirin imidacloprid 3O CS CWa Ca chlorfenapyr 2O3 beta-cy ele hirin nitenpyram 31 CS CWa Ca fenpyroximate 2O)4 beta-cy ele hirin nidinotefuran 32 CS CWa Ca tebufenpyrad 205 beta-cy ele hirin chlorfenapyr 33 CS CWa Ca fipronil 2O6 beta-cy ele hirin fenpyroximate 34 CS CWa Ca tebufenozide 2O7 beta-cy ele hirin tebufenpyrad 35 CS CWa Ca methoxyfenozide 55 208 beta-cy ele hirin fipronil 36 CS CWa Ca halofenozide 209 beta-cy ele hirin tebufenozide 37 CS CWa Ca triazamate 210 beta-cy ele hirin methoxyfenozide 38 CS CWa Ca avermectin 211 beta-cy ele hirin halofenozide 39 CS CWa Ca spinosad 212 beta-cy ele hirin triazamate 40 CS CWa Ca acephate 213 beta-cy ele hirin avermectin 41 CS CWa Ca fenamiphos 214 beta-cy ele hirin spinosad 60 42 CS CWa Ca diazinon 215 beta-cy ele hirin acephate 43 CS CWa Ca chlorpyrifos 216 beta-cy ele hirin fenamiphos 44 CS CWa Ca chlorpyrifos-methyl 217 beta-cy ele hirin diazinon 45 CS CWa Ca malathion 218 beta-cy ele hirin chlorpyrifos 46 CS CWa Ca carbaryl 219 beta-cy ele hirin chlorpyrifos-methyl 47 CS CWa Ca aldicarb 22O beta-cy ele hirin malathion 48 CS CWa Ca carbofuran 65 221 beta-cy ele hirin carbaryl 49 CS CWa Ca thiodicarb 222 beta-cy ele hirin aldicarb US 6,660,690 B2 13

COMPOSITION COMPOSITION NO. PYRETHROID OTHER INSECTICDE NO. PYRETHROID OTHER INSECTICDE 223 beta-cypermet hirin carbofuran 296 deltamethrin carbaryl 224 beta-cypermet hirin thiodicarb 297 deltamethrin aldicarb 225 beta-cypermet hirin Oxamyl 298 deltamethrin carbofuran 226 heta-cyperme hirin acetamiprid 299 deltamethrin thiodicarb 227 heta-cyperme hirin imidacloprid 3OO deltamethrin Oxamyl 228 heta-cyperme hirin nitenpyram 3O1 empropathrin acetamiprid 229 heta-cyperme hirin nidinotefuran 3O2 empropathrin imidacloprid 230 heta-cyperme hirin chlorfenapyr 303 empropathrin nitenpyram 231 heta-cyperme hirin fenpyroximate 15 304 empropathrin nidinotefuran 232 heta-cyperme hirin tebufenpyrad 305 empropathrin chlorfenapyr 233 heta-cyperme hirin fipronil 306 empropathrin fenpyroximate 234 heta-cyperme hirin tebufenozide 307 empropathrin tebufenpyrad 235 heta-cyperme hirin methoxyfenozide 3O8 empropathrin fipronil 236 heta-cyperme hirin halofenozide 309 empropathrin tebufenozide 237 heta-cyperme hirin triazamate 310 empropathrin methoxyfenozide 238 heta-cyperme hirin avermectin 311 empropathrin halofenozide 239 heta-cyperme hirin spinosad 312 empropathrin triazamate 240 heta-cyperme hirin acephate 313 empropathrin avermectin 241 heta-cyperme hirin fenamiphos 314 empropathrin spinosad 242 heta-cyperme hirin diazinon 315 empropathrin acephate 243 heta-cyperme hirin chlorpyrifos 316 empropathrin fenamiphos 244 heta-cyperme hirin chlorpynfos-methyl 25 317 empropathrin diazinon 245 heta-cyperme hirin malathion 318 empropathrin chlorpyrifos 246 heta-cyperme hirin carbaryl 319 empropathrin chlorpyrifos-methyl 247 heta-cyperme hirin aldicarb 32O empropathrin malathion 248 heta-cyperme hirin carbofuran 321 empropathrin carbaryl 249 heta-cyperme hirin thiodicarb 322 empropathrin aldicarb 250 heta-cyperme hirin Oxamyl 323 empropathrin carbofuran 251 Zeta-cyperme hirin acetamiprid 324 empropathrin thiodicarb 252 Zeta-cyperme hirin imidacloprid 325 empropathrin Oxamyl 253 Zeta-cyperme hirin nitenpyram 326 aufluvalinate acetamiprid 254 Zeta-cyperme hirin nidinotefuran 327 aufluvalina imidacloprid 255 Zeta-cyperme hirin chlorfenapyr 328 aufluvalina nitenpyram 256 Zeta-cyperme hirin fenpyroximate 35 329 aufluvailna nidinotefuran 257 Zeta-cyperme hirin tebufenpyrad 330 aufluvalina chlorfenapyr 258 Zeta-cyperme hirin fipronil 331 aufluvalina fenpyroximate 259 Zeta-cyperme hirin tebufenozide 332 aufluvalina tebufenpyrad 260 Zeta-cyperme hirin methoxyfenozide 333 aufluvalina fipronil 261 Zeta-cyperme hirin halofenozide 334 aufluvalina tebufenozide 262 hirin triazamate 335 aufluvalina Zeta-cyperme 40 methoxyfenozide 263 Zeta-cyperme hirin avermectin 336 aufluvalina halofenozide 264 Zeta-cyperme hirin spinosad 337 aufluvalina triazamate 265 Zeta-cyperme hirin acephate 338 auftuvalina avermectin 266 Zeta-cyperme hirin fenamiphos 339 aufluvalina spinosad 267 Zeta-cyperme hirin diazinon 340 aufluvalina acephate 268 Zeta-cyperme hirin chlorpyrifos 341 aufluvalina fenamiphos 269 Zeta-cyperme hirin chlorpyrifos-methyl 45 342 aufluvalina diazinon 270 Zeta-cyperme hirin malathion 343 aufluvalina chlorpyrifos 271 Zeta-cyperme hirin carbaryl 344 aufluvalina chlorpyrifos-methyl 272 Zeta-cyperme hirin aldicarb 345 aufluvalina malathion 273 Zeta-cyperme hirin carbofuran 346 aufluvalina carbaryl 274 Zeta-cyperme hirin thiodicarb 347 aufluvalina aldicarb 275 Zeta-cyperme hirin Oxamyl 50 348 aufluvalina carbofuran 276 amethrin acetamiprid 349 aufluvalina thiodicarb 277 amethrin imidacloprid 350 aufluvalina Oxamyl 278 amethrin nitenpyram 351 Lucy hirina acetamiprid 279 amethrin nidinotefuran 352 Lucy hirina imidacloprid 28O amethrin chlorfenapyr 353 Lucy hirina nitenpyram 281 amethrin fenpyroximate 55 354 Lucy hirina nidinotefuran 282 amethrin tebufenpyrad 355 Lucy hirina chlorfenapyr 283 amethrin fipronil 356 Lucy hirina fenpyroximate 284 amethrin tebufenozide 357 Lucy hirina tebufenpyrad 285 amethrin methoxyfenozide 358 Lucy hirina fipronil 286 amethrin halofenozide 359 Lucy hirina tebufenozide 287 amethrin triazamate 360 Lucy hirina methoxyfenozide 60 288 amethrin avermectin 361 Lucy hirina halofenozide 289 amethrin spinosad 362 Lucy hirina triazamate 290 amethrin acephate 363 Lucy hirina avermectin 291 amethrin fenamiphos 364 Lucy hirina spinosad 292 amethrin diazinon 365 Lucy hirina acephate 293 i amethrin chlorpyrifos 366 Lucy hirina fenamiphos 294 amethrin chlorpyrifos-methyl 65 367 Lucy hirina diazinon 295 amethrin malathion 368 Lucy hirina chlorpyrifos US 6,660,690 B2 15 16

COMPOSITION COMPOSITION NO. PYRETHROID OTHER INSECTICDE NO. PYRETHROID OTHER INSECTICDE

369 lucyt hirinate chlorpyrifos-methyl 42 trans-cyfluthrin diazinon 370 lucyt hirinate malathion 43 trans-cyfluthrin chlorpyrifos 371 lucyt hirinate carbaryl 44 trans-cyfluthrin chlorpyrifos-methyl 372 lucyt hirinate aldicarb 45 trans-cyfluthrin malathion 373 lucyt hirinate carbofuran 46 trans-cyfluthrin carbaryl 374 lucyt hirinate thiodicarb 47 trans-cyfluthrin aldicarb 375 lucyt hirinate Oxamyl 48 trans-cyfluthrin carbofuran 376 le hirin acetamiprid 49 trans-cyfluthrin thiodicarb 377 le hirin imidacloprid 15 50 trans-cyfluthrin Oxamyl 378 le hirin nitenpyram 51 acrinath rin acetamiprid 379 le hirin nidinotefuran 52 acrinath rin imidacloprid 38O le hirin chlorfenapyr 53 acrinath rin nitenpyram 381 le hirin fenpyroximate 54 acrinath rin nidinotefuran 382 le hirin tebufenpyrad 55 acrinath rin chlorfenapyr 383 le hirin fipronil 56 acrinath rin fenpyroximate 384 le hirin tebufenozide 57 acrinath rin tebufenpyrad 385 le hirin methoxyfenozide 58 acrinath rin fipronil 386 le hirin halofenozide 59 acrinath rin tebufenozide 387 le hirin triazamate 60 acrinath rin methoxyfenozide 388 le hirin avermectin 61 acrinath rin halofenozide 389 le hirin spinosad 62 acrinath rin triazamate 390 le hirin acephate 25 63 acrinath rin avermectin 391 le hirin fenamiphos 64 acrinath rin spinosad 392 le hirin diazinon 65 acrinath rin acephate 393 le hirin chlorpyrifos 66 acrinath rin fenamiphos 394 le hirin chlorpyrifos-methyl 67 acrinath rin diazinon 395 le hirin malathion 68 acrinath rin chlorpyrifos 396 le hirin carbaryl 69 acrinath rin chlorpyrifos-methyl 397 le hirin aldicarb 70 acrinath rin malathion 398 le hirin carbofuran 71 acrinath rin carbaryl 399 le hirin thiodicarb 72 acrinath rin aldicarb 400 le hirin Oxamyl 73 acrinath rin carbofuran O1 beta-cy hirin acetamiprid 74 acrinath rin thiodicarb O2 beta-cy hirin imidacloprid 35 75 acrinath rin Oxamyl O3 beta-cy hirin nitenpyram 76 phacy ele hirin acetamiprid O4 beta-cy hirin nidinotefuran 77 hacy ele hirin imidactoprid 05 beta-cy hirin chlorfenapyr 78 hacy ele hirin nitenpyram O6 beta-cy hirin fenpyroximate 79 hacy ele hirin nidinotefuran O7 beta-cy hirin tebufenpyrad 8O hacy ele hirin chlorfenapyr O8 hirin 81 ele hirin beta-cy fipronil 40 hacy fenpyroximate O9 beta-cy hirin tebufenozide 82 hacy ele hirin tebufenpyrad 1O beta-cy hirin methoxyfenozide 83 hacy ele hirin fipronil 11 beta-cy hirin halofenozide 84 hacy ele hirin tebufenozide 12 beta-cy hirin triazamate 85 hacy ele hirin methoxyfenozide 13 beta-cy hirin avermectin 86 hacy ele hirin halofenozide 14 beta-cy hirin spinosad 87 hacy ele hirin triazamate 15 beta-cy hirin acephate 45 88 hacy ele hirin avermectin 16 beta-cy hirin fenamiphos 89 hacy ele hirin spinosad 17 beta-cy hirin diazinon 90 hacy ele hirin acephate 18 beta-cy hirin chlorpyrifos 91 hacy ele hirin fenamiphos 19 beta-cy hirin chlorpyrifos-methyl 92 hacy ele hirin diazinon 2O beta-cy hirin malathion 93 hacy ele hirin chlorpyrifos 21 beta-cy hirin carbaryl 50 94 hacy ele hirin chlorpyrifos-methyl 22 beta-cy hirin aldicarb 95 hacy ele hirin malathion 23 beta-cy hirin carbofuran 96 hacy ele hirin carbaryl 24 beta-cy hirin thiodicarb 97 hacy ele hirin aldicarb 25 beta-cy hirin Oxamyl 98 hacy ele hirin carbofuran 26 rans-cy hirin acetamiprid 499 hacy ele hirin thiodicarb 27 rans-cy hirin imidacloprid 55 500 phacy ele hirin Oxamyl 28 rans-cy hirin nitenpyram 5O1 tralome hirin acetamiprid 29 rans-cy hirin nidinotefuran 5O2 tralome hirin imidacloprid 3O rans-cy hnin chlorfenapyr 503 tralome hirin nitenpyram 31 rans-cy hirin fenpyroximate 504 tralome hirin nidinotefuran 32 rans-cy hirin tebufenpyrad 505 tralome hirin chlorfenapyr 33 rans-cy hirin fipronil SO6 tralome hirin fenpyroximate 60 34 rans-cy hirin tebufenozide 507 tralome hirin tebufenpyrad 35 rans-cy hirin methoxyfenozide 508 tralome hirin fipronil 36 rans-cy hirin halofenozide 509 tralome hirin tebufenozide 37 rans-cy hirin triazamate 510 tralome hirin methoxyfenozide 38 rans-cy hirin avermectin 511 tralome hirin halofenozide 39 rans-cy hirin spinosad 512 tralome hirin triazamate 40 rans-cy hirin acephate 65 513 tralome hirin avermectin 41 rans-cy hirin fenamiphos 514 tralome hirin spinosad US 6,660,690 B2

COMPOSITION COMPOSITION NO. PYRETHROID OTHER INSECTICDE NO. PYRETHROID OTHER INSECTICDE 515 tralomethirmn acephate 588 resmethrin avermectin 516 tralomethrin fenamiphos 589 resmethrin spinosad 517 tralomethrin diazinon 590 resmethrin acephate 518 tralomethrin chlorpyrifos 591 resmethrin fenamiphos 519 tralomethrin chlorpyrifos-methyl 592 resmethrin diazinon 52O tralomethrin malathion 593 resmethrin chlorpyrifos 521 tralomethrin carbaryl 594 resmethrin chlorpyrifos-methyl 522 tralomethrin aldicarb 595 resmethrin malathion 523 tralomethrin carbofuran 15 596 resmethrin carbaryl 524 tralomethrin thiodicarb 597 resmethrin aldicarb 525 tralomethrin Oxamyl 598 resmethrin carbofuran 526 cyc O hirin acetamiprid 599 resmethrin thiodicarb 527 cyc O hirin imidacloprid 6OO resmethrin Oxamyl 528 cyc O hirin nitenpyram 6O1 bioresme hirin acetamiprid 529 cyc O hirin nidinotefuran 6O2 bioresme hirin imidacloprid 530 cyc O hirin chlorfenapyr 603 bioresme hirin nitenpyram 531 cyc O hirin fenpyroximate 604 bioresme hirin nidinotefuran 532 cyc O hirin tebufenpyrad 605 bioresme hirin chlorfenapyr 533 cyc O hirin fipronil 606 bioresme hirin fenpyroximate 534 cyc O hirin tebufenozide 6O7 bioresme hirin tebufenpyrad 535 cyclopro hirin methoxyfenozide 608 bioresme hirin fipronil 536 cyclopro hirin halofenozide 25 609 bioresme hirin tebufenozide 537 cyciopro hirin triazamate 610 bioresme hirin methoxyfenozide 538 cyclopro hirin avermectin 611 bioresme hirin halofenozide 539 cyclopro hirin spinosad 612 bioresme hirin triazamate 540 cyclopro hirin acephate 613 bioresme hirin avermectin 541 cyclopro hirin fenamiphos 614 bioresme hirin spinosad 542 cyclopro hirin diazinon 615 bioresme hirin acephate 543 cyclopro hirin chlorpyrifos 616 bioresme hirin fenamiphos 544 cyclopro hirin chlorpyrifos-methyl 617 bioresme hirin diazinon 545 cyclopro hirin malathion 618 bioresme hirin chlorpyrifos 546 cyclopro hirin carbaryl 619 bioresme hirin chlorpyrifos-methyl 547 cyclopro hirin aldicarb 62O bioresme hirin malathion 548 cyclopro hirin carbofuran 35 621 bioresme hirin carbaryl 549 cyclopro hirin thiodicarb 622 bioresme hirin aldicarb 550 cyclopro hirin Oxamyl 623 bioresme hirin carbofuran 551 kadethrin acetamiprid 624 bioresme hirin thiodicarb 552. kadethrin imidacloprid 625 bioresme hirin Oxamyl 553 kadethrin nitenpyram 626 etramethrin acetamiprid 554. kadethrin nidinotefuran 627 ramethrin 40 imidacloprid 555 kadethrin chlorfenapyr 628 ramethrin nitenpyram 556 kadethrin fenpyroximate 629 ramethrin nidinotefuran 557 kadethrin tebufenpyrad 630 ramethrin chlorfenapyr 558 kadethrin fipronil 631 ramethrin fenpyroximate 559 kadethrin tebufenozide 632 ramethrin tebufenpyrad 560 kadethrin methoxyfenozide 633 ramethrin fipronil 561 kadethrin halofenozide 45 634 ramethrin tebufenozide 562 kadethrin triazamate 635 ramethrin methoxyfenozide 563 kadethrin avermectin 636 ramethrin halofenozide 564 kadethrin spinosad 637 ramethrin triazamate 565 kadethrin acephate 638 ramethrin avermectin 566 kadethrin fenamiphos 639 ramethrin spinosad 567 kadethrin diazinon 50 640 ramethrin acephate 568 kadethrin chlorpyrifos 641 ramethrin fenamiphos 569 kadethrin chlorpyrifos-methyl 642 ramethrin diazinon 570 kadethrin malathion 643 ramethrin chlorpyrifos 571 kadethrin carbaryl 644 ramethrin chlorpyrifos-methyl 572 kadethrin aldicarb 645 ramethrin malathion 573 kadethrin carbofuran 55 646 ramethrin carbaryl 574. kadethrin thiodicarb 647 ramethrin aldicarb 575 kadethrin Oxamyl 648 ramethrin carbofuran 576 resmethrin acetamiprid 649 ramethrin thiodicarb 577 resmethrin imidacloprid 6SO etramethrin Oxamyl 578 resmethrin nitenpyram 651 phenothrin acetamiprid 579 resmethrin nidinotefuran 652 phenothrin imidacloprid 58O resmethrin chlorfenapyr 60 653 phenothrin nitenpyram 581 resmethrin fenpyroximate 654 phenothrin nidinotefuran 582 resmethrin tebufenpyrad 655 phenothrin chlorfenapyr 583 resmethrin fipronil 656 phenothrin fenpyroximate 584 resmethrin tebufenozide 657 phenothrin tebufenpyrad 585 resmethrin methoxyfenozide 658 phenothrin fipronil 586 resmethrin halofenozide 65 659 phenothrin tebufenozide 587 resmethrin triazamate 660 phenothrin methoxyfenozide US 6,660,690 B2 20

COMPOSITION COMPOSITION NO. PYRETHROID OTHER INSECTICDE NO. PY RETHROID OTHER INSECTICDE

661 phenot hirin halofenozide 734 a. hirin tebufenozide 662 phenot hirin triazamate 735 a. hirin methoxyfenozide 663 phenot hirin avermectin 1O 736 a. hirin halofenozide 664 phenot hirin spinosad 737 a. hirin triazamate 665 phenot hirin acephate 738 a. hirin avermectin 666 phenot hirin fenamiphos 739 a. hirin spinosad 667 phenot hirin diazinon 740 a. hirin acephate 668 phenot hirin chlorpyrifos 741 a. hirin fenamiphos 669 phenot hirin chlorpyrifos-methyl 15 742 a. hirin diazinon 670 phenot hirin malathion 743 a. hirin chlorpyrifos 671 phenot hirin carbaryl 744 a. hirin chlorpyrifos-methyl 672 phenot hirin aldicarb 745 a. hirin malathion 673 phenot hirin carbofuran 746 a. hirin carbaryl 674 phenot hirin thiodicarb 747 a. hirin aldicarb 675 phenot hirin Oxamyl 748 a. hirin carbofuran 676 e e hirin acetamiprid 749 a. hirin thiodicarb 677 e e hirin imidacloprid 750 a. hirin Oxamyl 678 e e hirin nitenpyram 751. imi brothrin acetamiprid 679 e e hirin nidinotefuran 752 imi brothrin imidacloprid 68O e e hirin chlorfenapyr 753 imi brothrin nitenpyram 681 e e hirin fenpyroximate 754. imi brothrin nidinotefuran 682 e e hirin tebufenpyrad 25 755 imi brothrin chlorfenapyr 683 e e hirin fipronil 756 imi brothrin fenpyroximate 684 e e hirin tebufenozide 757 imi brothrin tebufenpyrad 685 e e hirin methoxyfenozide 758 imi brothrin fipronil 686 e e hirin halofenozide 759 imi brothrin tebufenozide 687 e e hirin triazamate 760 imi brothrin methoxyfenozide 688 e e hirin avermectin 761 imi brothrin halofenozide 689 e e hirin spinosad 762 imi brothrin triazamate 690 e e hirin acephate 763 imi brothrin avermectin 691 e e hirin fenamiphos 764 imi brothrin spinosad 692 e e hirin diazinon 765 imi brothrin acephate 693 e e hirin chlorpyrifos 766 imi brothrin fenamiphos 694 e e hirin chlorpyrifos-methyl 35 767 imi brothrin diazinon 695 e e hirin malathion 768 imi brothrin chlorpyrifos 696 e e hirin carbaryl 769 imi brothrin chlorpyrifos-methyl 697 e e hirin aldicarb 770 imi brothrin malathion 698 e e hirin carbofuran 771 imi brothrin carbaryl 699 e e hirin thiodicarb 772 imi brothrin aldicarb 700 e e hirin 773 imi brothrin carbofuran Oxamyl 40 701 cy hemothrin acetamiprid 774 imi brothrin thiodicarb 702 cy hemothrin imidacioprid 775 imi brothrin Oxamyl 703 cy hemothrin nitenpyram 776 hirin acetamiprid 704 cy hemothrin nidinotefuran 777 hirin imidacloprid 705 cy hemothrin chlorfenapyr 778 hirin nitenpyram 7O6 cy hemothrin fenpyroximate 779 hirin nidinotefuran 707 cy hemothrin tebufenpyrad 45 78O hirin chlorfenapyr 708 cy hemothrin fipronil 781 hirin fenpyroximate 709 cy hemothrin tebufenozide 782 hirin tebufenpyrad 710 cy hemothrin methoxyfenozide 783 hirin fipronil 711 cy hemothrin halofenozide 784 hirin tebufenozide 712 cy hemothrin triazamate 785 hirin methoxyfenozide 713 cy hemothrin avermectin 50 786 hirin halofenozide 71.4 cy hemothrin spinosad 787 hirin triazamate 715 cy hemothrin acephate 788 hirin avermectin 716 cy hemothrin fenamiphos 789 hirin spinosad 717 cy hemothrin diazinon 790 hirin acephate 718 cy hemothrin chlorpyrifos 791 hirin fenamiphos 719 cy hemothrin chlorpyrifos-methyl 55 792 hirin diazinon 720 cy hemothrin malathion 793 hirin chlorpyrifos 721 cy hemothrin carbaryl 794 hirin chlorpyrifos-methyl 722 cy hemothrin aldicarb 795 hirin malathion 723 cy hemothrin carbofuran 796 hirin carbaryl 724 cy hemothrin thiodicarb 797 hirin aldicarb 725 cyphenothrin Oxamyl 798 hirin carbofuran 726 prallethrin acetamiprid 60 799 hirin thiodicarb 727 prallethrin imidacloprid 8OO hirin Oxamyl 728 prallethrin nitenpyram 8O1 io lethrin acetamiprid 729 prallethrin nidinotefuran 8O2 bioallethrin imidacloprid 730 prallethrin chlorfenapyr 803 bioallethrin nitenpyram 731 prallethrin fenpyroximate 804 bioallethrin nidinotefuran 732 prallethrin tebufenpyrad 65 805 bioallethrin chlorfenapyr 733 prallethrin fipronil 806 bioallethrin fenpyroximate US 6,660,690 B2 21 22 advantageous when an expressed transgenic gene provides a TABLE 1-continued gene product that can protect a transgenic plant from one pest, but has no activity against a Second, different pest. In Combinations of pyrethroids and other non-pyrethroid this case, a combination of insecticides of the present insecticides that provide synergistic insecticidal activity". invention can be Selected that has activity against the Second COMPOSITION pest, thus providing the Seed and plant with protection from NO. PYRETHROID OTHER INSECTICDE both pests. By way of explanation, when a “first pest and a “second” pest are referred to herein, it should be under 807 bioallethrin tebufenpyrad 808 bioallethrin fipronil stood that each of the terms can include only one pest, or can 809 bioallethrin tebufenozide include two or more pests. 810 bioallethrin methoxyfenozide It is contemplated that the present method can be used to 811 bioallethrin halofenozide protect the Seeds, roots and/or the above-ground parts of 812 bioallethrin triazamate 813 bioallethrin avermectin field, forage, plantation, glasshouse, orchard or Vineyard 814 bioallethrin spinosad crops, ornamentals, plantation or forest trees. The Seeds that 815 bioallethrin acephate 15 are useful in the present invention can be the Seeds of any 816 bioallethrin fenamiphos Species of plant. However, they are preferably the Seeds of 817 bioallethrin diazinon 818 bioallethrin chlorpyrifos plant species that are agronomically important. In particular, 819 bioallethrin chlorpyrifos-methyl the Seeds can be of corn, peanut, canola/rapeseed, Soybean, 82O bioallethrin malathion curcubits, crucifers, cotton, beets, rice, Sorghum, Sugar beet, 821 bioallethrin carbaryl wheat, barley, rye, Sunflower, tomato, Sugarcane, tobacco, 822 bioallethrin aldicarb 823 bioallethrin carbofuran oats, as well as other vegetable and leaf crops. It is preferred 824 bioallethrin thiodicarb that the Seed be corn, Soybeans, or cotton Seed; and more 825 bioallethrin Oxamyl preferred that the Seeds be corn Seeds. In one embodiment of the invention, as mentioned above, Note: "The composition comprises the two insecticides that appear on the same 25 the Seed is a transgenic Seed from which a transgenic plant line as the number of the composition. can grow. The transgenic Seed of the present invention is engineered to express a desirable characteristic and, in When the other insecticide is an oxadiazine derivative, it particular, to have at least one heterologous gene encoding has been found that it is preferred that the at least one for the expression of a protein that is pesticidally active and, pyrethroid be Selected from the group consisting of in particular, has insecticidal activity. The heterologous gene tauflu valinate, flumethrin, trans-cy fluthrin, kadethrin, in the transgenic Seeds of the present invention can be bioresmethrin, tetramethrin, phenothrin, cyphenothrin, derived from a microorganism Such as Bacillus, Rhizobium, prallethrin, imiprothrin, allethrin and Pseudomonas, Serratia, Trichoderma, Clavibacter, Glomus, In another embodiment, the Subject method comprises Gliocladium and mycorrhizal fungi. In particular, it is treating a Seed prior to Sowing with a composition compris 35 believed that the present method would be especially ben ing a nitroguanidine and at least one other insecticide eficial when the heterologous gene is one that is derived Selected from the group consisting of a chloronicotinyl, a from a Bacillus sp. microorganism and the protein is active pyrrol, a pyraZone, a diacylhydrazine, a triazole, a against corn rootworm. It is also believed that the present biological/fermentation product, a phenyl pyrazole, an orga method would be especially beneficial when the heterolo nophosphate and a carbamate. 40 gous gene is one that is derived from a Bacillus sp. micro It has also been found that a transgenic Seed can be organism and the protein is active against European corn protected against multiple pests when the Seed has at least borer. A preferred Bacillus sp. microorganism is Bacillus one heterologous gene encoding for the expression of a thuringiensis. It is particularly preferred when the heterolo protein that is active against a first pest and, in addition, gous gene encodes a modified Cry3Bb delta-endotoxin having adhered thereto a composition comprising at least 45 derived from Bacillus thuringiensis, as disclosed, for one pyrethrin or Synthetic pyrethroid and at least one other example, in U.S. Pat. No. 6,063,597. insecticide Selected from the group consisting of an oxadi The target pest for the present invention is an adult or azine derivative, a chloronicotinyl, a nitroguanidine, a larvae of any insector other pest that feeds on the Seed, roots pyrrol, a pyraZone, a diacylhydrazine, a triazole, a and/or shoots and foliage of the plant that is to be protected biological/fermentation product, a phenyl pyrazole, an orga 50 by the subject method. Such pests include but are not limited nophosphate and a carbamate. It is preferred that the com to: position containing the Synergistic combination of insecti from the order Lepidoptera, for example, cides is present in an amount effective to provide protection Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., to the shoots and foliage of the plant against damage by at Alabama argillaceae, Amylois spp., Anticarsia least one Second pest. 55 gem matalis, Archips spp., Argyrotaenia spp., When the transgenic Seed has at least one heterologous Autographa spp., BuSSeola fusca, Cadra Cautella, Car gene encoding for the expression of a protein that is active pOsina nipponensis, Chilo spp., Choristoneura spp., against a first pest, the Seed can be treated with a combina Clysia ambiguella, Cnaphalocrocis spp., Cnephasia tion of insecticides, which combination has activity against spp., Cochylis spp., Coleophora spp., Crocidolomia at least one Second pest. The present method can be used 60 binotalis, Cryptophlebia leucotreta, Cydia spp., when the first pest and the Second pest are the same, for the Diatraea spp., Diparopsis castanea, Earias spp., Ephe purpose, for example, to obtain effective control of a par stia spp., Eucosma spp., Eupoecilia ambiguella, ticularly resistant or highly damaging pest. But in a Separate Euproctis spp., Euxoa spp., Grapholita spp., Hedya embodiment, the transgenic trait protects the Seed and/or nubiferana, Heliothis spp., Hellula undalis, Hyphantria plant from a first pest and the composition of the combina 65 cunea, Keiferia lycoperSicella, Leucoptera Scitella, tion of insecticides is Selected to control a Second pest that Lithocollethis spp., LObesia bOtrana, Lymantria spp., is different from the first pest. This method is particularly Lyonetia spp., MalacoSoma spp., MameStra brassicae, US 6,660,690 B2 23 24 Manduca Sexta, Operophtera spp., Ostrinia Nubilalis, S.Sp., Oestrus spp., Orseolia spp., Oscinella frit, PegO Pammene spp., Pandemis spp., Panolis flammea, Pec myia hyOScyami, Phorbia spp., Rhagoletis pomonella, tinophora gossypiella, Phthorinaea operculella, Pieris Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. rapae, Pieris spp., Plutella xyloStella, Prays spp., Scir and Tipula spp., pophaga spp., Sesamia spp., Sparganothis spp., 5 from the order Siphonaptera, for example, Spodoptera spp., Synanthedon spp., Thaumetopoea Ceratophyllus spp. and Xenopsylla cheopis and spp., Tortrix spp., Trichoplusia ni and Yponomeuta from the order Thysanura, for example, spp., from the order Coleoptera, for example, Lepisma Saccharina. Agriotes spp., Anthonomus spp., Atomaria linearis, Cha In each embodiment of the invention, it is preferred that etOcnema tibialis, Cosmopolites spp., Curculio spp., a combination of two or more insecticides is applied to a Dermestes spp., Diabrotica spp., Epilachna spp., Erem Seed in an effective amount; that is, an amount Sufficient to nus spp., Leptinotarsa decemlineata, Lissorhoptrus provide protection to the Seed and/or shoots and foliage of spp., Melolontha spp., Orycaephilus spp., Otiorhyn the plant that grows from the Seed. AS used herein, "pro chus spp., Phlyctinus spp., Popillia spp., Psylliodes tection' is achieved if the percent of feeding damage to the spp., Rhizopertha spp., Scarabeidae, Sitophilus spp., 15 Seed and/or the shoots and foliage at 10 days after infestation Sitotroga spp., Tenebrio spp., Tribolium spp. and Tro (DAI) with the pest is reduced for treated seeds or plants goderma spp.; grown from treated Seeds as compared to untreated Seeds or from the order Orthoptera, for example, plants grown from untreated Seeds. In a preferred Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea embodiment, an unexpected advantage of the compositions of the present invention is that the component insecticides of maderae, Locusta spp., Periplaneta S.Sp., and Schisto the composition operate Synergistically. AS used here, when Cerca Spp., it is Said that a combination demonstrates “synergy', what is from the order Isoptera, for example, meant is that the degree of protection that is provided to a Reticulitemes SSp; Seed and/or the shoots and foliage of a plant that grows from from the order Psocoptera, for example, 25 a Seed, by treatment of the Seed by the present method (using Liposcelis spp.; a combination of insecticides), is Superior to the degree of from the order Anoplura, for example, protection that would be expected on the basis of the Haematopinus spp., Linognathus spp., Pediculus spp., protection provided by each of the components of the Pemphigus spp. and Phylloxera spp., composition applied Separately. from the order Mallophaga, for example, Methods for the calculation of whether a particular insec Damalinea spp. and Trichodectes spp.; ticide combination provides Synergy are described in detail from the order Thysanoptera, for example, in the Examples. Briefly stated, however, whether a combi Franklinella spp., Hercinothrips spp., Taeniothrips spp., nation of insecticides provided Synergy in protection against Thrips palmi, Thrips tabaci and Scirtothrips aurantii; cutworm damage can be calculated as described by Colby, from the order Heteroptera, for example, 35 Robert. S., in Weeds, 15(1):20–22 (1967). The threshold value (Stated as % of control) for Synergy of a combination Cimex spp., Distantiella theobroma, Dysdercus spp., was calculated as=(% of control for treatment A)*(% of Euchistus spp., Eurygaster spp., Leptocorisa spp., control for treatment B)/100(n-1); where n=number of NeZara spp., Piesma spp., Rhodnius spp., Sahlbergella active ingredients in the combination. A measured 7% of Singularis, Scotinophara spp. and Triatoma spp., 40 control value that is less than the calculated threshold value from the order Homoptera, for example, indicates Synergy of the combination. Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella When the “degree of protection” is mentioned herein, it is spp., Aphididae, Aphis spp., Aspidiotus spp., Bemisia meant to include the amount of damage caused by the target tabaci, Ceroplaster spp., ChrySOmphalus aonidium, insect to Seeds that have been treated with a given amount ChrySOmphalus dictyospermi, CoccuS hesperidum, 45 of insecticide (and the plants that Sprout therefrom) relative Empoasca spp., Eriosoma larigerum, Erythroneura to the amount of damage caused to untreated Seeds and spp., Gascardia spp., LaodelphaX spp., Lacanium COrni, plants. But “degree of protection' can also refer to the Lepidosaphes spp., Macrosiphus spp., Myzus spp., number of different types of target pests that are affected by Nehotettix spp., Nilaparvata spp., Paratoria spp., Pem the treatment and the length of the period of protection. In phigus spp., Planococcus spp., Pseudaulacaspis spp., 50 other words, a Synergistic degree of protection can include PseudococcuS spp., Psylla S.Sp., Pulvinaria aethiopica, unexpectedly effective protection at reduced levels of active Quadraspidiotus spp., Rhopalosiphum spp., Saissetia ingredient, as well as protection against an unexpectedly spp., Scaphoideus spp., Schizaphis spp., Sitobion spp., wide variety of pests, or protection for an unexpectedly long Trialeurodes vaporariorum, Trioza erytreae and Unas (or otherwise particularly effective) period of time. pis citri, 55 The amount of the insecticidal composition of the present from the order Hymenoptera, for example, invention that will provide protection to plant shoots and Acromyrmex, Afta spp., Cephus spp., Diprion spp., foliage will vary depending on the particular pesticide Diprionidae, Gilpinia polytoma, Hoplocampa spp., combination, the concentration of active ingredients in the Lasius spp., Monomorium pharaonis, Neodiprion spp., composition, the nature of the formulation in which it is Solenopsis spp. and Vespa SS.p., 60 applied, the Seed type, and the target pest(s). AS used herein, from the order Diptera, for example, an amount of the composition effective to provide protection Aedes spp., Antherigona SOccata, Bibio hortulanus, Cal to the Seed and/or shoots and foliage of the plant against liphora erythrocephala, Ceratitis spp., Chrysomyia damage by the pest is the lowest amount of Such pesticide spp., Culex spp., Cuterebra spp., Dacus spp., DroSO that will provide Such protection. ASSuming that the com phila melanogaster, Fannia spp., Gastrophilus spp., 65 position is comprised of 100% active ingredients, then, in Glossina spp., Hypoderma spp., Hyppobosca spp., Liri general, the amount of the Subject composition used will omysa spp., Lucilia spp., Melanagromyza spp., Musca range from about 0.005% to 25% of the weight of the seed, US 6,660,690 B2 25 26 and more preferably, from about 0.01% to about 10%. A yet pounds which act only below the ground; fungicides, Such as more preferred range is 0.01% to 1% of the active ingredi captan, thiram, metalXyl, fludioxonil, oxadixyl, and isomers ents relative to the weight of the Seed, and an even more of each of those materials, and the like; herbicides, including preferred range is 0.05% to 0.5%. compounds Selected from carbamates, thiocarbamates, The Subject compositions are each composed of at least acetamides, triazines, dinitroanilines, glycerol ethers, two insecticidal compounds, Such as the combinations pyridaZinones, uracils, phenoxys, ureas, and benzoic acids, described in Table 1, and in the surrounding text. When two herbicidal SafenerS Such as benzoxazine, benzhydryl components are used, the relative amounts of the two derivatives, N,N-diallyl dichloroacetamide, various insecticides can range from 1:1000 to 1000:1, by weight. It dihaloacyl, oxazolidinyl and thiazolidinyl compounds, is preferred, however, that the weight ratio of the two ethanone, naphthalic anhydride compounds, and Oxime insecticides range from 1:100 to 100:1, more preferred is a derivatives, fertilizers, and biocontrol agents Such as ratio of 1:10 to 10:1, and yet more preferred is a ratio of 1:3 naturally-occurring or recombinant bacteria and fungi from to 3:1. the genera Rhizobium, Bacillus, Pseudomonas, Serratia, In the method of the present invention, the combination of Trichoderma, Glomus, Gliocladium and mycorrhizal fungi. pesticides is applied to a Seed. Although it is believed that 15 These ingredients may be added as a separate layer on the the present method can be applied to a Seed in any physi Seed or alternatively may be added as part of the pesticide ological State, it is preferred that the Seed be in a Sufficiently composition. durable State that it incurs no damage during the treatment Preferably, the amount of the novel composition or other process. Typically, the Seed would be a Seed that had been ingredients used in the Seed treatment should not inhibit harvested from the field; removed from the plant; and generation of the Seed, or cause phytotoxic damage to the Separated from any cob, Stalk, outer husk, and Surrounding Seed. pulp or other non-Seed plant material. The Seed would The composition of the present invention can be in the preferably also be biologically stable to the extent that the form of a Suspension; emulsion; slurry of particles in an treatment would cause no biological damage to the Seed. In aqueous medium (e.g., water); wettable powder; wettable one embodiment, for example, the treatment can be applied 25 granules (dry flowable); and dry granules. If formulated as to Seed corn that has been harvested, cleaned and dried to a a Suspension or Slurry, the concentration of the active moisture content below about 15% by weight. In an alter ingredient in the formulation is preferably about 0.5% to native embodiment, the Seed can be one that has been dried about 99% by weight (w/w), preferably 5-40%. and then primed with water and/or another material and then AS mentioned above, other conventional inactive or inert re-dried before or during the treatment with the pesticide. ingredients can be incorporated into the formulation. Such Within the limitations just described, it is believed that the inert ingredients include but are not limited to: conventional treatment can be applied to the Seed at any time between Sticking agents, dispersing agents Such as methylcellulose harvest of the Seed and Sowing of the Seed. AS used herein, (Methocel A15LV or Methocel A15C, for example, serve as the term "unsown Seed' is meant to include Seed at any combined dispersant/Sticking agents for use in Seed period between the harvest of the seed and the Sowing of the 35 treatments), polyvinyl alcohol (e.g., Elvanol 51-05), lecithin Seed in the ground for the purpose of germination and (e.g., Yelkinol P), polymeric dispersants (e.g., growth of the plant. polyvinylpyrrollidone/vinyl acetate PVP/VA S-630), thick When it is said that unsown seed is “treated” with the eners (e.g., clay thickenerS Such as Van Gel B to improve composition, Such treatment is not meant to include those Viscosity and reduce Settling of particle Suspensions), emul practices in which the pesticide is applied to the Soil, rather 40 Sion Stabilizers, Surfactants, antifreeze compounds (e.g., than to the Seed. For example, Such treatments as the urea), dyes, colorants, and the like. Further inert ingredients application of the pesticide in bands, “T-bands, or useful in the present invention can be found in in-furrow, at the same time as the Seed is Sowed are not McCutcheons, vol. 1, "Emulsifiers and Detergents,” MC considered to be included in the present invention. Publishing Company, Glen Rock, N.J., U.S.A., 1996. Addi The composition comprising a combination of pesticides 45 tional inertingredients useful in the present invention can be can be applied "neat', that is, without any diluting or found in McCutcheons, vol.2, “Functional Materials,” MC additional components present. However, the composition is Publishing Company, Glen Rock, N.J., U.S.A., 1996. typically applied to the Seeds in the form of a pesticide The pesticides, compositions of pesticide combinations, formulation. This formulation may contain one or more and formulations of the present invention can be applied to other desirable components including but not limited to 50 Seeds by any Standard Seed treatment methodology, includ liquid diluents, binders to Serve as a matrix for the pesticide, ing but not limited to mixing in a container (e.g., a bottle or fillers for protecting the Seeds during StreSS conditions, and bag), mechanical application, tumbling, spraying, and plasticizers to improve flexibility, adhesion and/or spread immersion. Any conventional active or inert material can be ability of the coating. In addition, for oily pesticide formu used for contacting Seeds with pesticides according to the lations containing little or no filler, it may be desirable to add 55 present invention, Such as conventional film-coating mate to the formulation drying agents Such as calcium carbonate, rials including but not limited to water-based film coating kaolin or bentonite clay, perlite, diatomaceous earth or any materials Such as Sepiret (Seppic, Inc., Fairfield, N.J.) and other adsorbent material. Use of Such components in Seed Opacoat (Berwind Pharm. Services, Westpoint, Pa.). treatments is known in the art. See, e.g., U.S. Pat. No. The Subject combination of pesticides can be applied to a 5,876,739. The skilled artisan can readily select desirable 60 Seed as a component of a Seed coating. Seed coating components to use in the pesticide formulation depending on methods and compositions that are known in the art are the Seed type to be treated and the particular pesticide that useful when they are modified by the addition of one of the is Selected. In addition, readily available commercial for embodiments of the combination of pesticides of the present mulations of known pesticides may be used, as demon invention. Such coating methods and apparatus for their Strated in the examples below. 65 application are disclosed in, for example, U.S. Pat. NoS. The seeds may also be treated with one or more of the 5,918,413, 5,891,246, 5,554,445, 5,389,399, 5,107,787, following ingredients: other pesticides, including com 5,080,925, 4,759,945 and 4,465,017. Seed coating compo US 6,660,690 B2 27 28 sitions are disclosed, for example, in U.S. Pat. Nos. 5,939, The pesticides that are useful in the coating are those 356, 5,882,713, 5,876,739, 5,849,320, 5,834,447,5,791,084, combinations of pesticides that are described herein. The 5,661,103, 5,622,003, 5,580,544, 5,328,942, 5,300,127, amount of pesticide that is included in the coating will vary 4,735,015, 4,634,587, 4,383,391, 4,372,080, 4,339,456, depending upon the type of Seed and the type of active 4,272,417 and 4.245,432, among others. ingredients, but the coating will contain an amount of the Useful Seed coatings contain one or more binders and at combination of pesticides that is pesticidally effective. When least one of the Subject combinations of pesticides. insects are the target pest, that amount will be an amount of Binders that are useful in the present invention preferably the combination of insecticides that is insecticidally effec comprise an adhesive polymer that may be natural or tive. AS used herein, an insecticidally effective amount synthetic and is without phytotoxic effect on the seed to be means that amount of insecticide that will kill insect pests in coated. The binder may be Selected from polyvinyl acetates, the larvae or pupal State of growth, or will consistently polyvinyl acetate copolymers, polyvinyl alcohols, polyvinyl reduce or retard the amount of damage produced by insect alcohol copolymers, celluloses, including ethylcelluloses, pests. In general, the amount of pesticide in the coating will methylcelluloses, hydroxymethylcelluloses, hydroxypropy range from about 0.005 to about 50% of the weight of the lcelluloses and carboxymethylcellulose; polyvinylpyroli 15 Seed. A more preferred range for the pesticide is from about dones, polysaccharides, including Starch, modified Starch, 0.01 to about 40%; more preferred is from about 0.05 to dextrins, maltodextrins, alginate and chitosans, fats, oils, about 20%. proteins, including gelatin and Zeins, gum arabics, shellacs, The exact amount of the combination of pesticides that is Vinylidene chloride and Vinylidene chloride copolymers, included in the coating is easily determined by one of Skill calcium lignoSulfonates, acrylic copolymers, polyvinylacry in the art and will vary depending upon the Size of the Seed lates, polyethylene oxide; acrylamide polymers and copoly to be coated. The pesticides of the coating must not inhibit mers, polyhydroxyethyl acrylate, methylacrylamide mono germination of the Seed and should be efficacious in pro mers, and polychloroprene. tecting the Seed and/or the plant during that time in the target It is preferred that the binder be selected so that it can insect's life cycle in which it causes injury to the Seed or Serve as a matrix for the Subject combination of pesticides. 25 plant. In general, the coating will be efficacious for approxi While the binders disclosed above may all be useful as a mately 0 to 120 days after sowing. matrix, the Specific binder will depend upon the properties The coating is particularly effective in accommodating of the combination of pesticides. The term “matrix”, as used high pesticidal loads, as can be required to treat typically herein, means a continuous Solid phase of one or more refractory pests, Such as corn root worm, while at the same binder compounds throughout which is distributed as a time preventing unacceptable phytotoxicity due to the discontinuous phase one or more of the Subject combina increased pesticidal load. tions of pesticides. Optionally, a filler and/or other compo Optionally, a plasticizer can be used in the coating for nents can also be present in the matrix. The term matrix is mulation. Plasticizers are typically used to make the film that to be understood to include what may be viewed as a matrix is formed by the coating layer more flexible, to improve System, a reservoir System or a microencapsulated System. 35 adhesion and spreadability, and to improve the Speed of In general, a matrix System consists of a combination of processing. Improved film flexibility is important to mini pesticides of the present invention and filler uniformly mize chipping, breakage or flaking during Storage, handling dispersed within a polymer, while a reservoir System con or Sowing processes. Many plasticizers may be used, Sists of a separate phase comprising the Subject combination however, useful plasticizers include polyethylene glycol, of pesticides, that is physically dispersed within a 40 glycerol, butylbenzylphthalate, glycol benzoates and related Surrounding, rate-limiting, polymeric phase. Microencapsu compounds. The range of plasticizer in the coating layer will lation includes the coating of Small particles or droplets of be in the range of from bout 0.1 to about 20% by weight. liquid, but also to dispersions in a Solid matrix. When the combination of pesticides used in the coating is The amount of binder in the coating can vary, but will be an oily type formulation and little or no filler is present, it in the range of about 0.01 to about 25% of the weight of the 45 may be useful to hasten the drying process by drying the seed, more preferably from about 0.05 to about 15%, and formulation. This optional Step may be accomplished by even more preferably from about 0.1% to about 10%. means will known in the art and can include the addition of AS mentioned above, the matrix can optionally include a calcium carbonate, kaolin or bentonite clay, perlite, diato filler. The filler can be an absorbent or an inert filler, Such as maceous earth, or any absorbent material that is added are known in the art, and may include Woodflours, clayS, 50 preferably concurrently with the pesticidal coating layer to activated carbon, Sugars, diatomaceous earth, cereal flours, absorb the oil or exceSS moisture. The amount of calcium fine-grain inorganic Solids, calcium carbonate, and the like. carbonate or related compounds necessary to effectively ClayS and inorganic Solids which may be used include provide a dry coating will be in the range of about 0.5 to calcium bentonite, kaolin, china clay, talc, perlite, mica, about 10% of the weight of the seed. Vermiculite, Silicas, quartz powder, montmorillonite and 55 The coatings formed with the combination of pesticides mixtures thereof. Sugars which may be useful include dex are capable of effecting a slow rate of release of the pesticide trin and maltodextrin. Cereal flours include wheat flour, oat by diffusion or movement through the matrix to the Sur flour and barley flour. rounding medium. The filler is selected so that it will provide a proper The coating can be applied to almost any crop Seed that microclimate for the Seed, for example the filler is used to 60 is described herein, including cereals, vegetables, ornamen increase the loading rate of the active ingredients and to tals and fruits. adjust the control-release of the active ingredients. The filler In addition to the coating layer, the Seed may be treated can aid in the production or process of coating the Seed. The with one or more of the following ingredients: other pesti amount of filler can vary, but generally the weight of the cides including fungicides and herbicides; herbicidal Safen filler components will be in the range of about 0.05 to about 65 ers, fertilizers and/or biocontrol agents. These ingredients 75% of the seed weight, more preferably about 0.1 to about may be added as a separate layer or alternatively may be 50%, and even more preferably about 0.5% to 15%. added in the pesticidal coating layer. US 6,660,690 B2 29 30 The pesticide formulation may be applied to the Seeds Preferred embodiments of the invention are described in using conventional coating techniques and machines, Such the following examples. Other embodiments within the as fluidized bed techniques, the roller mill method, rotoStatic Scope of the claims herein will be apparent to one skilled in Seed treaters, and drum coaters. Other methods, Such as the art from consideration of the Specification or practice of Spouted beds may also be useful. The Seeds may be presized the invention as disclosed herein. It is intended that the before coating. After coating, the Seeds are typically dried Specification, together with the examples, be considered and then transferred to a sizing machine for Sizing. Such exemplary only, with the Scope and Spirit of the invention procedures are known in the art. being indicated by the claims which follow the examples. The pesticide-treated Seeds may also be enveloped with a film overcoating to protect the pesticide coating. Such REFERENCE EXAMPLE 1. overcoatings are known in the art and may be applied using This example compares the efficacy of Seed treatment conventional fluidized bed and drum film coating tech with lambda-cyhalothrin (CAS#91465-08-6) to soil granu niques. lar treatments with tefluthrin (CAS # 79538-32-2) against In another embodiment of the present invention, a pesti feeding damage by black cutworm larvae on shoots and cide can be introduced onto or into a Seed by use of Solid 15 foliage. matrix priming. For example, a quantity of the pesticide can A lambda-cyhalothrin Seed treatment formulation was be mixed with a Solid matrix material and then the Seed can prepared by diluting the WARRIOR(R) Tinsecticide (Zeneca be placed into contact with the Solid matrix material for a Ag Products, Wilmington, Del.), which contains 11.4% period to allow the pesticide to be introduced to the Seed. lambda-cyhalothrin as the active ingredient, into water as a The Seed can then optionally be separated from the Solid carrier. This formulation was applied for one minute at room matrix material and Stored or used, or the mixture of Solid temperature to twenty-five grams of Pioneer corn Seed matrix material plus Seed can be Stored or planted directly. (Cultivar PN3394) in a rotostatic seed treater at a rate of 125 Solid matrix materials which are useful in the present g, 250 g or 500 g active ingredient (Al) to 100 kg seed. The invention include polyacrylamide, Starch, clay, Silica, treated Seeds were allowed to sit uncapped for four to alumina, Soil, Sand, polyurea, polyacrylate, or any other 25 material capable of absorbing or adsorbing the pesticide for twenty-four hours before planting. a time and releasing that pesticide into or onto the Seed. It Treated and untreated seeds (Pioneer hybrid PN3394) is useful to make Sure that the pesticide and the Solid matrix were planted in a soil mix consisting of Dupo silt loam, 30% material are compatible with each other. For example, the Perlite, 20% coarse sand (WB-10 grade) in six groups of Solid matrix material should be chosen So that it can release tubs (20 in. LX 15 in. Wx8 in. D). Twelve seeds were planted the pesticide at a reasonable rate, for example over a period per tub and three tubs were planted for each treatment of minutes, hours, or dayS. regimen. Soil applications of FORCECR 3GR, which con The present invention further embodies imbibition as tains 3% tefluthrin granule as the active ingredient, were another method of treating Seed with the pesticide. For used for two sets of tubS containing untreated Seeds. The example, plant Seed can be combined for a period of time 35 FORCE 3GR was applied either in-furrow or incorporated with a solution comprising from about 1% by weight to into a 5 inch band on the Soil Surface at the time of planting. about 75% by weight of the pesticide in a solvent such as The tubs were overhead irrigated until the plants were water. Preferably the concentration of the solution is from infested with black cutworm larvae. about 5% by weight to about 50% by weight, more prefer The rate of application for the FORCE 3GR was reported ably from about 10% by weight to about 25% by weight. 40 in units of grams of the active ingredient per hectare (g/ha), During the period that the seed is combined with the while the rate of application of the WARRIORT to the seeds Solution, the Seed takes up (imbibes) a portion of the was reported in units of grams of the active ingredient per pesticide. Optionally, the mixture of plant Seed and Solution 100 kilograms of the seeds (g/100 kg). Although the con can be agitated, for example by Shaking, rolling, tumbling, version of one of these units to the other will vary somewhat or other means. After imbibition, the Seed can be separated 45 according to the type of Seed that is being used, the Size and from the Solution and optionally dried, for example by weight of the Seed, and the density of planting that is patting or air drying. used-among other things-an approximate conversion for In yet another embodiment, a powdered pesticide can be corn Seed can be carried out as follows. ASSuming a Seed mixed directly with Seed. Optionally, a Sticking agent can be application rate of lambda cyhalothrin of, for example, 125 used to adhere the powder to the Seed Surface. For example, 50 g/100 kg of Seed and a planting density of 15 lbs. Seed/ac, a quantity of Seed can be mixed with a Sticking agent and about 14.7 acres can be planted with 100 kg of the seed. This optionally agitated to encourage uniform coating of the Seed is an effective application rate of about 8.5 g of lambda with the Sticking agent. The Seed coated with the Sticking cyhalthrin per acre. At 2.47 ac/ha, the Seed treatment level agent can then be mixed with the powdered pesticide. The of 125 g/100 kg is approximately equivalent to a Surface mixture can be agitated, for example by tumbling, to encour 55 banding treatment at about 21 g/ha. age contact of the Sticking agent with the powdered At twelve days after planting (DAP) but before pesticide, thereby causing the powdered pesticide to Stick to infestation, the overall health of each plant was rated by the Seed. looking at emergence, height and appearance. This vigor The present invention also provides a Seed that has been rating gives an indication of any phytotoxicity from the Seed treated by the method described above. 60 or Soil treatment. A rating of 1 indicates extremely low vigor The treated seeds of the present invention can be used for while 10 is the highest Vigor rating. the propagation of plants in the same manner as conven The corn plants were infested at 12 DAP, which corre tional treated Seed. The treated Seeds can be stored, handled, sponds to late growth stage V1 by placing two black Sowed and tilled in the Same manner as any other pesticide cutworm larvae at % instar on the SoilSurface near the base treated Seed. Appropriate Safety measures should be taken to 65 of the plant. Plants were rated 3, 7 and 10 days after limit contact of the treated seed with humans, food or feed infestation (DAI) for the number of cut plants, as well as materials, water and birds and wild or domestic animals. damage from leaf feeding. The percent Stand reduction due US 6,660,690 B2 31 32 to plant cutting was calculated by dividing the number of cut prepared and treated as described in Example 1, except that plants into the number of plants present at infestation. The the treatment levels of the active ingredients on the Seeds foliar feeding injury was evaluated using a rating Scale of was as shown in Table 3. Treated and untreated seeds were 1=no damage and 10=complete defoliation. The mean planted in tubs and cultivated as described in Example 1. results for the three tubS for each treatment regimen are 5 The tubs were overhead irrigated until the plants were presented in Table 2 below. infested with black cutworm larvae.

TABLE 2 Efficacy of lambda-cyhalothrin seed-treatment against black Cutworm feeding damage on corn. Vigor % Stand Plant % Stand Plant % Stand Plant Treatment at Reductin Defol. Reductin Defol. Reductin Defol. Regimen 12 DAP 3 DAI 3 DA 7 DAI 7 DA 10 DA 1ODA

None 8.0 72.8 9.O 94.4 9.3 1OO.O 1.O.O w-cyhalothrin 9.O 13.9 4.3 16.7 5.0 19.4 3.3 seed 125 g/100 kg w-cyhalothrin 8.3 3.0 3.7 3.0 2.7 3.0 1.7 seed 250 g/100 kg w-cyhalothrin 8.3 O.O 2.0 O.O 2.3 O.O 1.O seed 500 g/100 kg Tefluthrin 9.O 33.9 5.0 48.0 6.O 48.0 5.3 in-furrow 30 g/ha Tefluthrin 8.7 O.O 1.7 O.O 1.7 O.O banded 30 g/ha

These results demonstrate that seed treatment with The corn plants were infested as 12 DAP, as described in lambda-cyhalothrin prior to planting provides significant Example 1. Plants were rated at 10 DAI for the number of protection of corn plants against Shoot/foliar feeding damage cut plants. The percent stand reduction due to plant cutting by black cutworm. For example, at 7 DAI with the lowest was calculated by dividing the number of cut plants into the rate tested (125 g/kg Seed), a significant reduction was 35 number of plants present at infestation. The mean results for observed for both plant cutting (16.7% for seed treatment vs. each of the Seed treatment regimens is presented in Table 3. 94% for untreated control) and foliar feeding injury (5.0 for seed treatment vs. 9.3 rating for untreated control). In Whether a combination of insecticides provided Synergy addition, tubs planted with seed treated with lambda in protection against cutworm damage was calculated as cyhalothrin at rates of 250 and 500 g/100 kg seed, showed 40 described by Colby, Robert. S., in Weeds, 15(1):20–22 essentially no stand reduction from plant cutting (3% and (1967). The threshold value (stated as % of control) for 0% for 250 and 500 g, respectively) and only low levels of Synergy of a combination was calculated as-(% of control for treatment A)*(% of control for treatment B)/100(n-1); foliar injury (2.7 and 2.3 rating for 250 and 500 g, where n=number of active ingredients in combination. A respectively). This level of protection was equal to the measured 76 of control value that is less than the threshold tefluthrin soil band treatment and Superior to tefluthrin 45 in-furrow treatment. When the tubs were evaluated at 10 value indicates Synergy of the combination. Threshold Val DAI, no increase in plant cutting and only slightly higher ues for Synergy were calculated for each of the combinations ratings for foliar feeding injury were observed with lambda of Table 3, and the threshold values for synergy of combi nations of the active ingredients at various levels are shown cyhalothrin Seed treatments as compared to evaluations at 7 in Table 4. DAI. In contrast, the untreated control tubs exhibited 100% 50 plant cutting and complete defoliation by 10 DAI. TABLE 3 EXAMPLE 2 Protection of corn plants against black cutworm This example illustrates the efficacy of corn Seed treat damage by seed treatments with tefluthrin, acephate and ment with a combination of tefluthrin and acephate against 55 combinations of the two. plant damage by black cutworm. Tefluthrin Acephate STAND Percent TREAT (gm/100 (gm/100 REDUCTION of Seed treatment formulations were prepared from MENT kg seed) kg seed) (% at 10 days) Control Synergy tefluthrin (available from Wilbur Ellis Co. under the trade name of RAZE(R) 2.5 FS) and acephate (N-methoxy RAZE 1OO 75 75 60 RAZE 2OO 1OO 1OO (methylthio)phosphinoyl)acetamide; CAS Registry No. RAZE 3OO 83 83 30560-19-1); available from Tomen Agro Inc., San ORTHENE 1OO 6.3 6.3 Francisco, Calif., or Valent USA Corp., Walnut Creek, ORTHENE 2OO 18.4 18.4 Calif., under the trade name of ORTHENE(E). RAZEf 1OO 1OO 9.4 9.4 NO ORTH In addition, Separate Seed treatment formulations were 65 RAZEf 1OO 2OO 9.4 9.4 YES prepared from each of the two insecticides alone and a ORTH Sample of untreated Seed was also prepared. Corn Seed was US 6,660,690 B2 33 34 3. The method as set forth in claim 1 wherein the pyrethrin TABLE 3-continued or Synthetic pyrethroid is Selected from the group consisting of (S)-cyano(3-phenoxyphenyl)methyl 4-chloro alpha Protection of corn plants against black cutworm (1-methylethyl)benzeneacetate (fenvalerate): (S)-cyano damage by seed treatments with tefluthrin, acephate and (3-phenoxyphenyl) methyl (S)-4-chloro-alpha-(1- combinations of the two. methylethyl) benzene acetate (esfenvale rate); Tefluthrin Acephate STAND Percent (3-phenoxyphenyl)-methyl(+) cis-trans-3-(2,2- TREAT (gm/100 (gm/100 REDUCTION of dichoroethenyl)-2,2-dimethylcyclopropanecarboxylate MENT kg seed) kg seed) (% at 10 days) Control Synergy (permethrin), (t) alpha-cyano-(3-phenoxyphenyl) methyl RAZEf 2OO 1OO 33 33 NO 1O (+)-cis, trans-3-(2,2-dichloroethenyl)-2,2-dimethyl ORTH cyclopropane carboxylate (cyperme thrin); beta RAZEf 2OO 2OO 9.4 9.4 YES cy per me thrin; the ta-cy per me thrin, S - cyano ORTH (3-phenoxyphenyl) methyl (t) cis/trans 3-(2,2- RAZEf 3OO 1OO 13.5 13.5 NO dichloroethenyl) 2,2 dimethylcyclopropane carboxylate ORTH (Zeta-cy permethrin), (S)-alpha-cyano-3-phenoxybenzyl RAZEf 3OO 2OO 7.1 7.1 YES 15 ORTH (1R,3 R)-3-(2,2-dibromovinyl)-2,2-dimethyl cyclopropan UN- O O 1OO ecarboxylate (deltamethrin); alpha-cyano-3-phenoxybenzyl TREATED 2,2,3,3-tetra methyl cyclopropoane carboxylate CONTROL (fempropathrin); (RS)-alpha-cyano-3-phenoxybenzyl(R)-2- 2-chloro-4-(trifluoromethyl)anilinol-3-methylbutanoate (tauflu valinate); (2,3,5,6-tetrafluoro-4-methylphenyl)- methyl-(1 alpha, 3 alpha)-(Z)-(+)-3-(2-chloro-3,3,3- TABLE 4 trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylate Matrix of threshold values for synergy of combination (tefluthrin); (+)-cyano (3-phenoxyphenyl) methyl (it)-4- % of control (difluoromethoxy)-alpha-(1-methyl ethyl) benzeneacetate 25 (flucythrinate); cyano(4-fluoro-3-phenoxyphenyl)methyl RAZE G 100 RAZE G 200 RAZE G 300 3-2-chloro-2-(4-chlorophenyl)e the nyl-2,2- ORTHENE (a 100 4.7 6.3 5.2 dimethylcyclopropanecarboxylate (flumethrin); cyano(4- ORTHENE (a 200 13.8 18.4 15.3 fluoro-3-phenoxyphenyl) methyl 3-(2,2-dichloroethenyl)-2, 2-dimethylcyclopropanedarboxylate (cy fluthrin); beta The results of this test showed that the pyrethroid/ cyfluthrin; transfluthrin, (S)-alpha-cyano-3-phenoxybenzyl organophosphorous-insecticide combinations of tefluthrin (Z)-(1R-cis)-2,2-dimethyl-3-2-(2,2,2-trifluoro and acephate were Synergistic against damage of the plant by trifluoromethyl-ethoxycarbonyl) vinylcyclopropane car black cutworm for all levels of tefluthrin when levels of boxylate (acrinathrin); (1R cis) S and (1S cis) Renantiomer acephate were 200 gm/100 kg of seed (or about 0.3% by isomer pair of alpha-cyano-3-phenoxybenzyl-3-(2,2- 35 dichlorovinyl)-2,2-dimethylcyclopropane carboxylate weight of the seed). (alpha cypermethrin); 1 R,3S)3(1 RS) (1,2,2,2'- In view of the above, it will be seen that the several tetrabromoethyl)-2,2-dimethyl cyclopropanecarboxylic advantages of the invention are achieved and other advan acid (S)-alpha-cyano-3-phenoxybenzyl ester (tralomethrin); tageous results attained. cyano-(3-phenoxyphenyl) methyl 2,2-dichloro-1-(4- AS Various changes could be made in the above methods 40 ethoxyphenyl)cyclopropane carboxylate (cycloprothrin); and compositions without departing from the Scope of the 1C, 3C.(Z)-(+)-cyano-(3-phenoxyphenyl)methyl 3-(2- invention, it is intended that all matter contained in the chloro-3,3,3-trifluoro-1-prope nyl)-2,2- above description and shown in the accompanying drawings cimethylcyclopropanecarboxylate (cyhalothrin); 1 alpha shall be interpreted as illustrative and not in a limiting Sense. (s), 3 alpha(Z)-cyano(3-phenoxyphenyl) methyl-3-(2- The discussion of references herein is intended merely to 45 chloro-3,3,3-trifluoro-1-prope nyl)-2,2- Summarize the assertions made by their authors and no dimethylcyclopropane carboxylate (lambda cyhalothrin); admission is made that any reference constitutes prior art. (2-methyl 1,1'-biphenyl)-3-yl) methyl 3-(2-chloro-3,3,3- Applicants reserve the right to challenge the accuracy and trifluoro-1-p rope nyl)-2,2-dimethyl pertinency of the cited references. cyclopropanecarboxylate (bifenthrin); 5-1-benzyl-3- What is claimed is: 50 furylmethyl-d-cis(1R,3S.E)2,2-dimethyl-3-(2-oxo,-2,2,4,5 1. A method for protecting a Seed and/or shoots and tetrahydro thiophenylidenemethyl)cyclopropane carboxy foliage of a plant grown from the Seed from damage by a late (kadethrin, RU15525), 5-(phenyl methyl)-3-furanyl pest, the method comprising treating an unsown Seed with a 3-furanyl 2,2-dimethyl-3-(2-methyl-1-propenyl) cyclopro composition consisting essentially of a pyrethrin or a Syn pane carboxylate (res me thrin); (1 R-trans)-5- thetic pyrethroid and an insecticide Selected from the group 55 (phenylmethyl)-3-furanyl)methyl 2,2-dimethyl-3-(2- consisting of an oxadiazine derivative, a chloronicotinyl, a methyl-1-prope nyl) cyclopropane carboxylate nitroguanidine, a pyrrol, a pyrazole, a diacylhydrazine, a (bioresmethrin); 3,4,5,6-tetra hydro-phthalimidomethyl triazole, a biological/fermentation product that is Selected (IRS)-cis-trans-chrysanthe mate (tetrame thrin); from avermectin or Spinosad, a phenyl pyrazole, an orga 3-phenoxybenzyl-d, I-cis, trans 2,2-dimethyl-3-(2- nophosphate and a carbamate, wherein the insecticide is 60 methylpropenyl) cyclopropane carboxylate (phenothrin); other than thiamethoxam or clothianidin. empenthrin; cyphenothrin, prallethrin, imiprothrin; (RS)-3- 2. The method as set forth in claim 1, wherein the allyl-2-methyl-4-oxcyclopent-2-enyl-(1A,3R; 1R,3S)-2,2- insecticide is said oxadizine derivative, and the pyrethroid is dim ethyl-3-(2-methylprop-1-enyl) cyclopropane carboxy Selected from the group consisting of tauflu valinate, late (allethrin); bioallethrin; and ZXI 8901. flumethrin, trans-cyfluthrin, kadethrin, bioresmethrin, 65 4. The method as set forth in claim 3, wherein the tetramethrin, phenothrin, empenthrin, cyphenothrin, Synthetic pyrethroid is Selected from the group consisting of prallethrin, imiprothrin, allethrin and bioallethrin. tefluthrin, lambda cyhalothrin, cyfluthrin and bifenthrin. US 6,660,690 B2 35 36 5. The method according to claim 1, wherein the insec 30. The method as set forth in claim 1, wherein the seed ticide is said oxadiazine derivative. is treated with the pyrethroid as a different time than it is 6. The method according to claim 5, wherein the oxadiz treated with the insecticide. ine derivative is an insecticide Selected from the group 31. The method as set forth in claim 28, wherein the consisting of 5-(2-chloropyrid-5-ylmethyl)-3-methyl-4- composition is in a Seed coating. nitroiminoperhydro-1,3,5-oxadiazine, 3-methyl-4- 32. An unsown Seed that has been treated with a compo nitroimino-5-(1-oxido-3-pyridinomethyl) perhydro-1,3,5- Sition consisting essentially of a pyrethrin or a Synthetic oxadiazine, 5-(2-chloro-1-oxido-5-pyridiniomethyl)-3- pyrethroid and an insecticide Selected from the group con Sisting of an oxadiazine derivative, a chloronicotinyl, a methyl-4-nitroiminoperhydro-1,3,5-oxidiazine, and nitroguanidine, a pyrrol, a pyrazole, a diacylhydrazine, a 3 - methyl-5-(2-methylpy rid-5-ylmethyl)-4- triazole, a biological/fermentation product that is Selected nitroiminoperhydro-1,3,5-oxadiazine. from avermectin or Spinosad, a phenyl pyrazole, an orga 7. The method as set forth in claim 1, wherein the nophosphate and a carbamate, wherein the insecticide is insecticide is Said chloronicotinyl. other than thiamethoxam or clothianidin. 8. The method as set forth in claim 7, wherein the 33. The seed as set forth in claim 32, wherein the seed is chloronicotinyl is Selected from the group consisting of 15 Selected from the group consisting of corn, Soybean, cotton, imidacloprid, acetamiprid and nitenpyram. rice, Sorghum, Sugar beet, wheat, barley, rye, Sunflower, 9. The method as set forth in claim 1, wherein the tomato, Sugarcane, tobacco, rape and oats. insecticide is Said nitroguanidine. 34. The seed as set forth in claim 33, wherein the seed is 10. The method as set forth in claim 9, wherein the Selected from the group consisting of corn, Soybean and nitroguanidine is nidinotefuran. cotton Seed. 11. The method as set forth in claim 1, wherein the 35. The seed as set forth in claim 34, wherein the seed is insecticide is Said pyrrol. corn Seed. 12. The method as set forth in claim 11, wherein the pyrrol 36. The seed as set forth in claim 32, wherein the seed is is chlorfeinapyr. a transgenic Seed. 13. The method as set forth in claim 1, wherein the 25 37. The seed as set forth in claim 36, wherein the insecticide is Said pyrazole. transgenic Seed is a transgenic corn Seed containing a 14. The method as set forth in claim 13, wherein the heterologous Bacillus thuringiensis gene. pyrazole is tebufenpyrad. 38. The seed as set forth in claim 37, wherein the heterologous Bacillus thuringiensis gene is one that encodes 15. The method as set forth in claim 1, wherein the for the production of a modified Cry3Bb delta-endoxin. insecticide is Said diacylhydrazine. 39. A composition for the treatment of unsown seed, the 16. The method as set forth in claim 15, wherein the composition consisting essentially of a pyrethrin or a Syn diacylhydrazine is Selected from the group consisting of thetic pyrethroid and an insecticide Selected from the group tebufenozide, methoxyfenozide and halofenozide. consisting of an oxadiazine derivative, a chloronicotinyl, a 17. The method as set forth in claim 1, wherein the nitroguanidine, a pyrrol, a pyrazole, a diacylhydrazine, a insecticide is Said triazole. 35 triazole, a biological/fermentation product that is Selected 18. The method as set forth in claim 17, wherein the from avermectin or Spinosad, a phenyl pyrazole, an orga triazole is triaZamate. nophosphate and a carbamate, wherein the ether insecticide 19. The method as set forth in claim 1, wherein the is other than thiamethoxam or clothianidin. insecticide is Said biological/fermentation product that is 40. The composition as set forth in claim 39, wherein the Selected from avermectin or Spinosad. 40 insecticide is Said oxadizine derivative, and the pyrethroid is 20. The method as set forth in claim 1, wherein the Selected from the group consisting of tauflu valinate, insecticide is Said phenyl pyrazole. flumethrin, trans-cy fluthrin, kadethrin, bioresmethrin, 21. The method as set forth in claim 20, wherein the tetramethrin, phenothrin, empenthrin, cyphenothrin, phenyl pyrazole is fiprinol. prallethrin, imiprothrin, allethrin and bioallethrin. 22. The method as set forth in claim 1, wherein the ether 45 41. A Seed that is protected against multiple pests com insecticide is Said organophosphate. prising a Seed having at least one heterologous gene encod 23. The method as set forth in claim 22, wherein the ing for the expression of a protein that is active against a first organophosphate is Selected from the group consisting of pest and, in addition, having adhered to the Seed a compo acephate, fenamiphos, diazinon, chlorpyrifos, chlorpyrifon Sition consisting essentially of a pyrethrin or a Synthetic methyl and malathion. 50 pyrethroid and an insecticide Selected from the group con 24. The method as set forth in claim 1, wherein the Sisting of an oxadiazine derivative, a chloronicotinyl, a insecticide is Said carbamate. nitroguanidine, a pyrrol, a pyrazole, a diacylhydrazine, a 25. The method as set forth in claim 24, wherein the triazole, a biological/fermentation product that is Selected carbamate is Selected from the group consisting of carbaryl, from avermectin or Spinosad, a phenyl pyrazole, an orga aldicarb, carbofuran, thiodicarb and oxamyl. 55 nophosphate and a carbamate, wherein the insecticide is 26. The method as set forth in claim 1, wherein the other than thiamethoxam or clothianidin and where the composition is in a Seed coating. composition is present in an amount effective to provide 27. The method as set forth in claim 1, wherein the protection to the shoots and foliage of the plant against pyrethroid and/or the insecticide is a Systemic insecticide. damage by at least one Second pest. 28. The method as set forth in claim 1, wherein the seed 60 42. The seed as set forth in claim 41, wherein said is treated with the composition of the pyrethroid and the heterologous gene encodes for the expression of a protein insecticide in an amount effective to provide protection to that is insecticidally active. the Seed and/or the shoots and foliage of the plant against 43. The seed as set forth in claim 42, wherein the gene is damage by the pest. one originally derived from a microorganism Selected from 29. The method as set forth in claim 1, wherein the seed 65 the group consisting of Bacillus, Rhizobium, Pseudomonas, is treated with the pyrethroid at the same time that it is Serratia, Trichoderma, Glomus, Gliocladium and mycor treated with the insecticide. rhizal fungi. US 6,660,690 B2 37 38 44. The seed as set forth in claim 43, wherein the protein insecticide Selected from the group consisting of a is active against corn root worm. chloronicotinyl, a nitroguanidine, a pyrrol, a pyrazole, a 45. The seed as set forth in claim 43, wherein the protein diacylhydrazine, a triazole, a biological/fermentation prod is active against european corn borer. uct that is Selected from avermectin or Spinosad, a phenyl 46. The seed as set forth in claim 45 wherein the gene is pyrazole, an organophosphate and a carbamate, wherein the one originally derived from Bacillus thuringiensis. insecticide is other than thiamethoxam or clothianidin. 47. The seed as set forth in claim 43, wherein the seed is Selected from the group consisting of corn, Soybean, cotton, 49. The method according to claim 1, wherein the pyre rice, Sorghum, Sugar beet, wheat, barley, rye, Sunflower, thrin or Synthetic pyrethroid and the insecticide are each tomato, Sugarcane, tobacco, rape and oats. present in an amount which, in combination, provides a level 48. A method for treating an unsown Seed to protect the of protection that is Superior to that expected on the basis of Seed and/or shoots and foliage of a plant grown from the the level of protection provided by either the pyrethrin or Seed from damage by a pest, the method comprising con Synthetic pyrethroid or the other insecticide alone. tacting the unsown Seed with a composition consisting essentially of a pyrethrin or a Synthetic pyrethroid and an