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(12) Patent Application Publication (10) Pub. No.: US 2010/0168177 A1 Qin Et Al

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(12) Patent Application Publication (10) Pub. No.: US 2010/0168177 A1 Qin Et Al US 20100168177A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2010/0168177 A1 Qin et al. (43) Pub. Date: Jul. 1, 2010 (54) STABLE INSECTICIDE COMPOSITIONS (22) Filed: Dec. 22, 2009 Related U.S. Application Data (75) Inventors: Kuide Qin, Westfield, IN (US); (60) Provisional application No. 61/203,689, filed on Dec. Raymond E. Boucher, JR., 26, 2008. Lebanon, IN (US) Publication Classification (51) Int. Cl. Correspondence Address: AOIN 43/40 (2006.01) DOWAGROSCIENCES, LLC AOIP3/00 (2006.01) ONE INDIANA SQUARE, SUITE 2800 AOIP 7/04 (2006.01) INDIANAPOLIS, IN 46204-2079 (US) (52) U.S. Cl. ......................................... 514/336; 514/357 (57) ABSTRACT (73) Assignee: Dow AgroSciences, LLC Insect controlling compositions including an N-Substituted (6-haloalkylpyridin-3-yl)alkylsulfoximine compoundandan (21) Appl. No.: 12/633,987 organic acid or a salt thereof exhibit increased stability. US 2010/01 681 77 A1 Jul. 1, 2010 STABLE INSECTICDE COMPOSITIONS their use in controlling insects and certain other invertebrates, particularly aphids and other Sucking insects. This invention CROSS-REFERENCE TO RELATED also includes new synthetic procedures for preparing the APPLICATIONS compositions and methods of controlling insects using the 0001. The present application claims priority to U.S. Pro compositions. visional Patent Application No. 61/203,689 filed Dec. 26, 0007. This invention concerns compositions useful for the 2008, the content of which is incorporated herein by reference control of insects, especially useful for the control of aphids in its entirety. and other sucking insects. More specifically, the invention FIELD OF THE INVENTION concerns compositions including an organic acid or a salt thereof and a compound of the formula (I) 0002. The invention disclosed in this document is related to the field of pesticides and their use in controlling pests. (I) BACKGROUND OF THE INVENTION RI 0003 Pests cause millions of human deaths around the (CRR)-L-S=N world each year. Furthermore, there are more than ten thou N | \ sand species of pests that cause losses in agriculture. These 6 X agricultural losses amount to billions of U.S. dollars each 2 year. Termites cause damage to various structures such as Y N homes. These termite damage losses amount to billions of U.S. dollars each year. As a final note, many stored food pests 0008 wherein eat and adulterate stored food. These stored food losses amount to billions of U.S. dollars each year, but more impor 0009 X represents NO, CN or COOR: tantly, deprive people of needed food. I0010 L represents a single bond or R', S and L taken 0004. Many pesticide compositions have been developed together represent a 4-, 5- or 6-membered ring; over time to destroy pests and alleviate the damages they 10011) R' represents (C-C) alkyl: cause. With respect to at least Some of these compositions, physical and chemical instabilities can lead to a reduction in (0012 R and Rare distinct from each other and individu pesticidal activity of the composition and/or present compli ally represent hydrogen, methyl, ethyl, fluoro, chloro or cations when it comes time to apply the composition to a bromo: locus where pest control is necessary or desired. For example, 0013 n is 1 when L represents a single bond and is 0 when physical and chemical instabilities can alter one or more R', S and L taken together represents a 4-, 5- or 6-membered properties of the composition which make it difficult or ring: impossible to prepare appropriate Solutions of the composi tion for use. More particularly, many pesticide compositions 0014 Y represents (C-C) haloalkyl, F, Cl, Br, or I; and are provided in a concentrated formulation from the manu (0015 R represents (C-C) alkyl. facturer and are subsequently diluted by an end user before 0016. In one particular embodiment, the composition their application. During the time between manufacture and includes a compound of formula (I) wherein L represents a application, liquid forms of pesticide compositions can single bond, i.e., having the following structure wherein n is solidify as a result of chemical and physical instabilities of the 1 composition. Often times, this solidification prevents or sub stantially impedes the dispersion of the composition into a Solution Suitable for application, resulting in greater user R2 R3 burden and cost and/or wasted pesticide products. Moreover, when physical and chemical instabilities lead to a reduction in N -R pesticidal activity of a composition, an increase in the con / \ centration at which the pesticide is applied and/or more fre 2 O NN quent applications of the pesticide composition are often Y N X required. As a result, user costs and the cost to consumers can escalate. Therefore, a need exists for new pesticide composi tions that exhibit increased chemical and physical stability 0017 wherein properties. 0018 X represents NO, CN or COOR: 0005 U.S. Patent Application Publication 2007/0203191 0019 R' represents (C-C) alkyl: A1 describes certain N-substituted (6-haloalkylpyridin-3-yl) (0020 R and Rare distinct from each other and individu alkyl Sulfoximine compounds and their use in controlling ally represent hydrogen, methyl, ethyl, fluoro, chloro or insects. It has now been discovered how to improve the sta bility of compositions including one or more of these com bromo: pounds over greater periods of time. 0021 Y represents (C-C) haloalkyl, F, Cl, Br, or I; and (0022) R' represents (C-C) alkyl. SUMMARY OF THE INVENTION 0023. In another particular embodiment, the composition 0006. The present invention concerns novel compositions includes a compound of formula (I) wherein R', Sand L taken including one or more N-substituted (6-haloalkylpyridin-3- together form a saturated 5-membered ring, and n is 0, i.e., yl)alkyl Sulfoximines and an organic acid or a salt thereofand having the structure US 2010/01 681 77 A1 Jul. 1, 2010 0042 “haloalkyl means an alkyl group substituted with from one to the maximum possible number of halogenatoms, all combinations of halogens included. N S M \, DETAILED DESCRIPTION OF THE INVENTION 2 O N Y N 0043. Throughout this document, all temperatures are X given in degrees Celsius, and all percentages are weight per centages unless otherwise stated. 0024 wherein 0044) The compounds of formula (Ia), wherein R. R. R. 0025 X represents NO, CN or COOR: R, X, and Y are as previously defined, L is a single bond and 0026 Y represents (C-C) haloalkyl, F, Cl, Br, or I; and n is 1, can be prepared by the methods illustrated in Scheme 0027 R represents (C-C) alkyl. A: 0028. In certain embodiments, the composition includes compounds of formula (I) in one or more of the following Scheme A classes: 0029 (1) Compounds of formula (I) wherein X is NO or 2D 3 8. CN, most preferably CN. R1-S-(CR-R). \ / Y cPBA 0030 (2) Compounds of formula (I) wherein Y is CF. N 0031 (3) Compounds of formula (I) wherein RandR are (A) distinct from each other and independently represent hydro O gen, methyl or ethyl. RI-S-(CR-R).23 \ M Y NaN, b so, I0032 (4) Compounds of formula (I) wherein R' repre N sents CH. (B) 0033. It will be appreciated by those skilled in the art that O. NH o one or more of the compositions described herein may be R\ CR2R3 y --- comprised of combinations of the above described classes of ( )n \ / BrCN, DMAP or N HNO3, AcO or the compound of formula (I). (C) CICOR",4 DMAP 0034. In one or more particular embodiments, the organic acid is a carboxylic acid selected from the group consisting of O. N. o citric acid, phthalic acid, malic acid, tartaric acid, maleic acid, malonic acid, lactic acid and Succinic acid. R\ ce-()-y 0035. In yet another embodiment, a method includes N applying to a locus where control is desired an insect-inacti (Ia) Vating amount of a pesticide composition. 0036 Still, further embodiments, forms, features, aspects, 0045. In step a of Scheme A, sulfide of formula (A) is benefits, objects, and advantages of the present invention oxidized with meta-chloroperoxybenzoic acid (mCPBA) in a shall become apparent from the detailed description and polar solvent below 0°C. to provide sulfoxide of formula (B). examples provided. In most cases, dichloromethane is the preferred solvent for oxidation. Substituents (Non-Exhaustive List) 0046. In step b of Scheme A, sulfoxide (B) is iminated with sodium azide in the presence of concentrated sulfuric 0037. The examples given for the substituents are (except acid in an aprotic solvent under heating to provide Sulfox for halo) non-exhaustive and must not be construed as limit imine of formula (C). In most cases, chloroform is the pre ing the invention disclosed in this document. ferred solvent for this reaction. 0038 'alkyl (including derivative terms such as alkoxy) 0047. In step c of Scheme A, the nitrogen of sulfoximine means straight chain, branched chain and cyclic groups (C) can be either cyanated with cyanogen bromide in the including, for example, methyl, ethyl, 1-methylethyl, propyl. presence of a base, or nitrated with nitric acid in the presence 1,1-dimethylethyl and cyclopropyl. of acetic anhydride under mildly elevated temperature, or carboxylated with alkyl (R4) chloroformate in the presence of 0039) “alkoxy' means an alkyl further consisting of a car base such as 4-dimethylaminopyridine (DMAP) to provide bon-oxygen single bond, for example, methoxy, ethoxy, pro N-substituted sulfoximine (Ia). Base is required for efficient poxy, isopropoxy, 1-butoxy, 2-butoxy, isobutoxy, tert-butoxy, cyanation and carboxylation and the preferred base is DMAP. pentoxy, 2-methylbutoxy, 1,1-dimethylpropoxy, hexoxy, whereas sulfuric acid is used as catalyst for efficient nitration heptoxy, octoxy, nonoxy, and decoxy.
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