US 20110060018A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2011/0060018 A1 L0S0 et al. (43) Pub. Date: Mar. 10, 2011 (54) INSECTICIDALN-SUBSTITUTED Related U.S. Application Data (2-SUBSTITUTED-1,3-THIAZOL)ALKYL SULFOXIMINES (62) Division of application No. 1 1/897.510, filed on Aug. 30, 2007, now Pat. No. 7,863,303. (76) Inventors: Michael R. Loso, Carmel, IN (US); Publication Classification Benjamin M. Nugent, Brownsburg, IN (US); Yuanming Zhu, Carmel, (51) Int. Cl. IN (US); Thomas L. Siddall, AOIN 43/78 (2006.01) Zionsville, IN (US); Francis E. C07D 277/30 (2006.01) Tisdell, Carmel, IN (US); Jim X. C07D 417/06 (2006.01) Huang, Carmel, IN (US); Zoltan L. AOIP 7/04 (2006.01) Benko, Indianapolis, IN (US) (52) U.S. Cl. ......................................... 514/365: 548/205 (21) Appl. No.: 12/948,886 (57) ABSTRACT N-Substituted (2-substituted-1,3-thiazol)alkyl sulfoximines (22) Filed: Nov. 18, 2010 are effective at controlling insects. US 2011/0060018 A1 Mar. 10, 2011 INSECTICIDALN-SUBSTITUTED 10011) R' represents C-C alkyl, C-C haloalkyl, C-C, (2-SUBSTITUTED-1,3-THIAZOL)ALKYL alkenyl, C-C haloalkenyl, C-C alkynyl, or —(CH2)— in SULFOXMINES cases where R', S and L taken together represent a 4-, 5-, or 6-membered ring; CROSS-REFERENCE TO RELATED (0012 R and R independently represent hydrogen, APPLICATION methyl, ethyl, cyclopropyl, fluoro, chloro, bromo, or iodo; (0013 R' represents C-C alkyl, C-C haloalkyl, aryl, 0001. This application claims priority from provisional heteroaryl, arylalkyl or heteroarylalkyl: application 60/841,938 filed in the United States Patent I0014 R represents hydrogen, C-C alkyl, C-C, Office on Sep. 1, 2006. This application also claims benefit of haloalkyl, aryl, heteroaryl: arylalkyl or heteroarylalkyl; and U.S. non-provisional application Ser. No. 1 1/897.510 filed 30 I0015I R' represents C-C alkyl, C-C haloalkyl, C-C, Aug. 2007. alkenyl, C-Chaloalkenyl or C-C alkynyl. 0016 Preferred compounds of formula (I) include the fol BACKGROUND OF THE INVENTION lowing classes: 0002 The present invention concerns novel N-substituted 0017 (1) Compounds of formula (I) wherein X is NO or (2-substituted-1,3-thiazol)alkylsulfoximines and their use in CN, most preferably CN. controlling insects, particularly aphids and other Sucking 0018 (2) Compounds of formula (I) wherein Y is C-C, insects, as well as certain other invertebrates. This invention haloalkyl, fluoro, or bromo, most preferably CF. also includes new synthetic procedures for preparing the 0019 (3) Compounds of formula (I) wherein n is either 0 compounds, pesticide compositions containing the com or 1 and R', Sand L taken together form a saturated 5-mem pounds, and methods of controlling insects using the com bered ring having the structure pounds. 0003. There is an acute need for new insecticides. Insects are developing resistance to the insecticides in current use. At Y S least 400 species of arthropods are resistant to one or more N-l pi S insecticides. The development of resistance to some of the SRM \, older insecticides, such as DDT, the carbamates, and the O N-X. organophosphates, is well known. But resistance has even developed to some of the newer pyrethroid insecticides. Therefore a need exists for new insecticides, and particularly 0020 (4) Compounds of formula (I) wherein L represents for compounds that have new or atypical modes of action. a single bond and n>0 having the structure 0004 U.S. Patent Application Publication 2005/0228027 A1 describes certain Sulfoximine compounds including some containing (2-chloro-1,3-thiazol)alkyl groups and their use in X controlling insects. It will be demonstrated that certain SN R2 (2-substituted-1,3-thiazol-4-yl)alkyl sulfoximines and Y-K -S-R (2-substituted-1,3-thiazol-5-yl)alkyl sulfoximines will have N- R3 | comparable or even greatly improved activity. SUMMARY OF THE INVENTION 0021. It will be appreciated by those skilled in the art that the most preferred compounds are generally those which are 0005. This invention concerns compounds useful for the comprised of combinations of the above preferred classes. control of insects, especially useful for the control of aphids 0022. The invention also provides new processes for pre and other Sucking insects. More specifically, the invention paring compounds of formula (I) as well as new compositions concerns compounds of the formula (I) and methods of use, which will be described in detail herein after. (I) DETAILED DESCRIPTION OF THE INVENTION X 0023 Throughout this document, all temperatures are S N R2 given in degrees Celsius, and all percentages are weight per Y-K -L-S-R centages unless otherwise stated. NJ R3 O (0024. The terms “alkyl”, “alkenyl and “alkynyl', as well as derivative terms such as “alkoxy”, “acyl”, “alkylthio’. “arylalkyl, "heteroarylalkyl and “alkylsulfonyl', as used 0006 wherein herein, include within their scope straight chain, branched 0007 X represents NO, CN, COOR or COR; chain and cyclic moieties. Thus, typical alkyl groups are 0008 L represents either a single bond or —CH(CH), methyl, ethyl, 1-methylethyl, propyl, 1,1-dimethylethyl, and where m is an integer from 1-3 in cases where R', S and L cyclopropyl. Unless specifically stated otherwise, each may taken together represent a 4-, 5-, or 6-membered ring; be unsubstituted or substituted with one or more substituents 0009 n is an integer from 0-3: selected from but not limited to halogen, hydroxy, alkoxy, 0010 Y represents C-C alkyl, C-C haloalkyl, C-C, alkylthio, C-C acyl, formyl, cyano, aryloxy or aryl, pro alkenyl, C-C haloalkenyl, C-C alkynyl, fluoro, bromo, vided that the substituents are sterically compatible and the iodo, C-C alkoxy, C-C haloalkoxy, CN, NO or RSO. rules of chemical bonding and strain energy are satisfied. The where Z is an integer from 0-2: term “haloalkyl and “haloalkenyl' includes alkyl and alk US 2011/0060018 A1 Mar. 10, 2011 enyl groups Substituted with from one to the maximum pos polar solvent below 0°C. to provide sulfoxide of formula (B). sible number of halogenatoms, all combinations of halogens In most cases, dichloromethane is the preferred solvent for included. The term “halogen' or “halo' includes fluorine, oxidation. chlorine, bromine and iodine, with fluorine being preferred. 0029. In step b of Scheme A, sulfoxide (B) is iminated The terms “alkenyl and “alkynyl are intended to include with sodium azide in the presence of concentrated sulfuric one or more unsaturated bonds. acid in an aprotic solvent under heating to provide Sulfox 0025. The term “aryl” refers to a phenyl, indanyl or naph thyl group. The term "heteroaryl” refers to a 5- or 6-mem imine of formula (C). In most cases, chloroform is the pre bered aromatic ring containing one or more heteroatoms, viz., ferred solvent for this reaction. N, O or S.; these heteroaromatic rings may be fused to other 0030. In step c of Scheme A, the nitrogen of sulfoximine aromatic systems. The aryl or heteroaryl Substituents may be (C) can be either cyanated with cyanogen bromide in the unsubstituted or substituted with one or more substituents presence of a base, or nitrated with nitric acid in the presence selected from halogen, hydroxy, nitro, cyano, aryloxy, of acetic anhydride under mildly elevated temperature, or formyl, C-C alkyl, C-C alkenyl, C-C alkynyl, C-C, carboxylated with alkyl(R) chloroformate in the presence of alkoxy, halogenated C-C alkyl, halogenated C-C alkoxy, base such as 4-dimethylaminopyridine (DMAP), or acylated C-C acyl, C-C alkylthio, C-Calkylsulfinyl, C-C alkyl with acyl halide in the presence of base such as 4-dimethy sulfonyl, aryl, C-COC(O)alkyl, C-C NHC(O)alkyl, C(O) laminopyridine (DMAP) to provide N-substituted sulfox OH, C-CC(O)Oalkyl, C(O)NH, C-CC(O)NHalkyl, or imine (Ia). Base is required for efficient cyanation, carboxy C-CC(O)N(alkyl), provided that the substituents are steri lation or acylation and the preferred base is DMAP, whereas cally compatible and the rules of chemical bonding and strain Sulfuric acid is used as catalyst for efficient nitration reaction. energy are satisfied. 0031. The compounds of formula (Ia), wherein X repre 0026. The compounds of this invention can exist as one or sents CN can be prepared by the mild and efficient method more Stereoisomers. The various stereoisomers include geo illustrated in Scheme B. metric isomers, diastereomers and enantiomers. Thus the compounds of the present invention include racemic mix tures, individual stereoisomers and optically active mixtures. It will be appreciated by those skilled in the art that one Scheme B stereoisomer may be more active than the others. Individual Stereoisomers and optically active mixtures may be obtained 2D3 1 Y 8. by selective synthetic procedures, by conventional synthetic i L-(CR-R). U M PhI(OAc), procedures using resolved starting materials or by conven R1 N tional resolution procedures. (A) 0027. The compounds of formula (Ia), wherein R',R,R, CN R. R. n, X, and Y are as previously defined and L is a single ? S b bond, can be prepared by the methods illustrated in Scheme A: S-L-(CRR), U X-y mCPBA, K2CO3 R1 N (D) Scheme A N -CN o=-|-cRR). SX-y RI U N (Ia) O S | b R!--CRR)- U/X-y HerNaN3, HSO4 0032. In step a of Scheme B, sulfide is oxidized with N iodobenzene diacetate in the presence of cyanamide at 0°C. (B) to give sulfillimine (D). The reaction can be carried out in a O NH S polar aprotic solvent like CHC1.