US008110689B2

(12) United States Patent (10) Patent No.: US 8,110,689 B2 Wada et al. (45) Date of Patent: *Feb. 7, 2012

(54) BENZANILIDES WITH INSECTICIDAL M. Waksmundzka-Hajnos, “Chromatographic Separation of Nitro ACTIVITY Phenones and Their Reduced Derivatives on Thin Layers of Polar Adsorbents”, XP-008069069, pp. 159-171. Jun-Ichi Inoh et al., “Palladium-Catalyzed Coupling Reaction of (75) Inventors: Katsuaki Wada, Tochigi (JP); Tetsuya 4-Alkylnitrobenzenes with Aryl Bromides at Their Benzylic Posi Murata, Tochigi (JP); Katsuhiko tion”, XP-004130892, Tetrahedron Letters, 1998, pp. 4673-4676. Shibuya, Tochigi (JP); Eiichi Shimojo, M. Makosza et al., “Synthesis of (p-Nitroaryl)diarylmethanes via Vicarious Nucleophilic Substitution of Hydrogen', XP-002399354. Tochigi (JP) Synthesis, No. 9, 2000, pp. 1237-1240. S. Florio et al., “Vicarious Nucleophilic Substitution of (73) Assignee: Bayer Cropsciene AG, Monheim (DE) (Chloroalkyl)heterocycles with Nitroarenes', XP-002399353, Eur, J. Org. Chem., 2004, pp. 2118-2124. (*) Notice: Subject to any disclaimer, the term of this W. Waiers, “Some Substitution Reactions of patent is extended or adjusted under 35 4-Aminodiphenylmethane', XP-008069039, pp. 1060-1064. G. Esselen, Jr., “The Splitting of Benzhydrols by the Action of Bro U.S.C. 154(b) by 403 days. mine”, XP-002399352, pp. 308-324. This patent is Subject to a terminal dis M.Z.A. Badr et al., “Molecular Rearrangements. 14. Photolysis and claimer. Thermolysis of Phenylpropionanilides”, XP-0023993.51, J. Org. Chem., vol. 44, No. 18, 1979, pp. 3244-3247. Y. Watanabe et al., “Stilbene Derivative. Its Preparation, and (21) Appl. No.: 11/917,411 Electrophotographic Photoreceptor Using Same', XP-002399363, 2000, 2 pgs. (22) PCT Filed: Jun. 2, 2006 Kyowa Hakko Kogyo Co., Ltd., “Benzylpyridine Derivatives'. XP-002399362, 1977, 1 pg. (86). PCT No.: PCT/EP2006/005299 M. Hamana et al., “Rearrangement of Anilinomethylpyridines”. XP-002399361, 1963, 1 pg. S371 (c)(1), (2), (4) Date: Oct. 21, 2009 * cited by examiner Primary Examiner — Janet Andres (87) PCT Pub. No.: WO2006/133823 Assistant Examiner — Heidi Reese PCT Pub. Date: Dec. 21, 2006 (74) Attorney, Agent, or Firm — Baker Donelson Bearman, Caldwell & Berkowitz, PC (65) Prior Publication Data (57) ABSTRACT US 201O/OO62937 A1 Mar. 11, 2010 Benzanilides of the formula: (51) Int. Cl. CO7D 23/00 (2006.01) (I) CD7C233/00 (2006.01) A6 IK3I/44 (2006.01) A6 IK3I/6 (2006.01) (52) U.S. Cl...... 546/309;564/169; 514/352: 514/621 (58) Field of Classification Search ...... None See application file for complete search history. (56) References Cited FOREIGN PATENT DOCUMENTS EP 1 OO6 107 6, 2000 EP 1671 941 6, 2006 JP 11-240857 9, 1999 JP 2001-064258 3, 2001 JP 2001-064268 3, 2001 JP 2001-131141 5, 2001 in which X represents hydrogen, halogen, nitro, C alky JP 2003-040864 2, 2003 lthio, Calkylsulfinyl, Calkylsulfonyl or Calkylsulfo WO WO96, 15118 5, 1996 nyloxy;Y represents halogen or C-alkyl, R' represents C, WO WO97, 18208 5, 1997 alkyl, Ce alkylthio-Cl alkyl, C. alkylsulfinyl-C alkyl WO WO99.62506 12/1999 or C-alkylsulfonyl-C alkyl; R represents hydrogen, C. WO WOO1/21576 3, 2001 alkyl or Ce haloalkyl; R represents hydrogen or hydroxy: WO WO 2005/030699 4/2005 W represents CH or N; and Q represents optionally substi OTHER PUBLICATIONS tuted phenyl or optionally substituted pyridyl wherein the Substituent is at least one group selected from the group Silverman, R. “The Organic Chemistry of Drug Design and Drug consisting of halogen, Chaloalkyl, Chaloalkoxy, C Action.” 2004, Elsevier, pp. 29-32.* haloalkylthio, Ce haloalkylsulfinyl and Chaloalkylsul M. Seto et al., “Orally Active CCR5 Antagonists as Anti-HIV-1 foxy; provided that when R is hydroxy, R is not Calkyl, Agents 2: Synthesis and Biological Activities of Anilide Derivatives or when R is Chaloalkyl, R is hydroxy, Wis CH, and the Containing a Pyridine N-Oxide Moiety”. Chem. Parm. Bull. No. 52, Substituents of Q are two or more Chaloalkyl. Insecticides vol. 7, 2004, pp. 818-829. E. Ikeda et al., “Preparation of Benzanilide Derivatives as Pesti comprising the benzanilides are herein provided. cides”, XP-002399360, 2005, 2 pgs. 16 Claims, No Drawings US 8,110,689 B2 1. 2 BENZANLDES WITH INSECTICDAL least one group selected from the group consisting of C. ACTIVITY haloalkylsulfinyl and Chaloalkylsulfonyl. provided that when R is hydroxy, R is not C. alkyl, or CROSS REFERECE TO RELATED when R is Chaloalkyl, R is hydroxy and W is CH, the APPLICATIONS Substituents of Q are two or more Chaloalkyl. This is a S371 National Stage Application of International Application No. PCT/EP2006/005299 filed Jun. 2, 2006, DETAILED DESCRIPTION OF A PREFERRED which claims priority from Japanese Patent Application No. EMBODIMENT 2005-175036 filed Jun. 15, 2005. 10 The compounds of the formula (I) according to the present BACKGROUND OF THE INVENTION invention may be obtained for example by any one of Meth ods (a), (b), (c), (d), (e) and (f) below: 1. Field of the Invention The present invention relates to novel benzanilide com 15 Method (a) pounds and their use as insecticides. This method comprises reacting compounds of the formula 2. Description of Related Art (II): References D1-D8 disclose that phthalamide derivatives are useful as insecticides. Reference D9 discloses that certain types of phthalamide derivatives act as medical drugs. (II) D1: JP-A-11-240857 D2: JP-A-2001-64258 D3: JP-A-2001-64268 D4: JP-A-2001-131141 25 D5: JP-A-2003-40864 D6: WO O1/21576 D7: WO O3/11028 D8: WO 05/030699 wherein R' and X are the same as identified above, D9: JP-A-59-163353 30 with compounds of the formula (III): SUMMARY OF THE INVENTION (III) There have now been found novel benzanilides of the fol lowing formula (I): 35

(I)

HN1" 40 X wherein Y. R. R. Wand Q are the same as identified above, X^n-1s in the presence of inert solvents, and if appropriate, in the - presence of an acid catalyst, 45 Method (b) This method comprises reacting compounds of the formula (IV): s :-yQ Y R3 50 (IV) O in which X represents hydrogen, halogen, nitro, Ce alky X-H N R3 lthio, Calkylsulfinyl, Calkylsulfonyl or Calkylsulfo N \ / R2 nyloxy; 55 OC-() - Y represents halogen or C. alkyl; O Y R" represents C-alkyl, C-alkylthio-Cio alkyl, C-alkyl Sulfinyl-C alkyl or C. alkylsulfonyl-C alkyl; R represents hydrogen, C. alkyl or Chaloalkyl; wherein X, Y. R. R. W and Q are the same as identified R represents hydrogen or hydroxy, 60 above, W represents CH or N; and with compounds of the formula (V): Q represents optionally Substituted phenyl or optionally Sub stituted pyridyl wherein the Substituent is at least one group R" NH, (V) Selected from the group consisting of halogen, C. haloalkyl, Chaloalkoxy and Chaloalkylthio. 65 wherein R' is the same as identified above, Q furthermore represents optionally substituted phenyl or in the presence of inert solvents, and if appropriate, in the optionally substituted pyridyl wherein the substituent is at presence of an acid catalyst, US 8,110,689 B2 3 4 Method (c) This method comprises reacting compounds of the formula Rlf (If) (VI): HN1

(VI) 21 O

NH X--S O

10 HN X-- N CO2H tSás Y -YR2 R3 wherein X and R' are the same as identified above, with the compounds the above formula (III), 15 in the presence of inert solvents, and if appropriate, in the presence of an acid catalyst, wherein RV represents C, alkylthio-C, alkyland X, Y, R, Method (d) R. Wand Q are the same as identified above, This method comprises reacting compounds of the formula with an oxidant in the presence of inert Solvents. The benzanilides of the above formula (I) according to the (VII): present invention exhibit strong insecticidal activity. The compounds of formula (I) of the present invention, (VII) though encompassed by the general formula described in D1 O above, are novel compounds which are not in any way spe 25 cifically disclosed therein, and Surprisingly show noticeably 21 remarkable insecticidal activity as compared with the com X-H O pounds as particularly recited in D1. S In the present specification, "halogen denotes fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine N 21 Nw 30 and bromine. Alkyl denotes Straight-chain or branched C- alkyl s, 8 such as methyl, ethyl, n- or iso-propyl. n-, iso-, sec- or tert Sás butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl. Y R3 R2 n-undecyl, n-dodecyl, etc., preferably Ce alkyl. 35 The alkyl part in each of “alkylthio”, “alkylsulfinyl', “alkylsulfonyl', 'alkylsulfonyloxy”, “alkylthioalkyl, wherein X, Y. R. R. W and Q are the same as identified “alkylsulfinylalkyl, "alkylsulfonylalkyl, "haloalkyl, above, “haloalkoxy” and “haloalkylthio' may similarly be exempli with the compounds of the above formula (V), fied as those examples explained in “alkyl as above. in the presence of inert solvents, and if appropriate, in the 40 Examples explained in the “halogen above may similarly presence of an acid catalyst, be the examples of the halogen part in “haloalkyl, Method (e) “haloalkoxy” and “haloalkylthio’. This method comprises reacting compounds of the formula In the formula (I) of the present invention, preferred com (VIII): pounds are those in which 45 X is halogen, nitro, C alkylthio, C alkylsulfinyl, Ca alkylsulfonyl, or C. alkylsulfonyloxy; CO (VIII) Y is halogen or C alkyl; 21 2H R" is C, alkyl, C. alkylthio-Cl alkyl, C. alkylsulfinyl X Calkyl or C alkylsulfonyl-C alkyl, S O 50 R is hydrogen, C, alkyl or Chaloalkyl; R is hydrogen or hydroxy: W is CH or N; and HN 21 Nw Q is optionally substituted phenyl or optionally substituted | Q pyridyl wherein the Substituent is at least one group Sás 55 selected from the group consisting of halogen, Ca Y haloalkyl, Chaloalkoxy and Chaloalkylthio. Q is furthermore optionally substituted phenyl or optionally substituted pyridyl wherein the substituent is at least one wherein X, Y. R. R. W and Q are the same as identified group selected from the group consisting of Chaloalkyl above, 60 Sulfinyl and Chaloalkylsulfonyl with the compounds of the above formula (V), provided that when R is hydroxy, R is not C alkyl, or in the presence of inert solvents, and if appropriate, in the when R is C, a haloalkyl, R is hydroxy and W is CH, the presence of an acid catalyst, Substituents of Q are two or more Chaloalkyl. Method (f) Among them, in the formula (I) of the present invention, When R' is C, alkylsulfinyl-C alkyl or C, alkylsul 65 particularly preferred compounds are those in which X is fonyl-C alkyl, this method comprises reacting compounds fluorine, chlorine, bromine, iodine, nitro, methylthio, meth of the formula (If): ylsulfinyl, methylsulfonyl or methylsulfonyloxy; US 8,110,689 B2 5 Y is chlorine or methyl: -continued R" is isopropyl, C-2 alkylthio-Cs. alkyl, C-2 alkylsulfinyl CH3 C. alkyl or C alkylsulfonyl-C alkyl; R’ is hydrogen, methyl or trifluoromethyl: HN R is hydrogen or hydroxy: CF W is CH or N; and CH Q is optionally substituted phenyl or optionally substituted pyridyl wherein the Substituent is at least one group 10 Selected from the group consisting of chlorine, bromine, CF C. perhaloalkyl, perhaloalkoxy and C. perhaloalky C O lthio; CH Q is furthermore optionally substituted phenyl or optionally CHSCH3 substituted pyridyl wherein the substituent is at least one 15 NH group selected from the group consisting of C perha O CH3 loalkylsulfinyl and C. perhaloalkylsulfonyl: CH3 provided that when R is hydroxy, R is not methyl, or HN when R is trifluoromethyl, R is hydroxy and W is CH, the Substituents of Q are two or more C perhaloalkyl. CF Among them, in the formula (I) of the present invention, CH very particularly preferred compounds are those in which X is fluorine, chlorine, bromine, iodine, nitro, methylthio, meth ylsulfinyl, methylsulfonyl or methylsulfonyloxy; 25 CF Y is chlorine or methyl: R" is isopropyl, C-2 alkylthio-Cs. alkyl, C-2 alkylsulfinyl Calkyl or C. alkylsulfonyl-C alkyl: Method (b) may be represented by the following reaction 30 formula when, for example, 2-4-(3,5-bis-trifluoromethyl R’ is hydrogen, methyl or trifluoromethyl: benzyl)-2-methylphenyl]-4-chloroisoindole-1,3-dione and R is hydrogen or hydroxy: (S)-1-methyl-2-methylthioethylamine are used as the starting W is CH or N; and materials. Q is optionally substituted phenyl or optionally substituted pyridyl wherein the Substituent is at least one group 35 Selected from the group consisting of chlorine, bromine, C O H3C CF trifluoromethyl, pentafluoroethyl, heptafluoro-n-propyl. heptafluoro-i-propyl. nonafluoro-n-butyl, trifluo romethoxy, trifluoromethylthio, trifluoromethylsulfinyl, 40 trifluoromethylsulfonyl, pentafluoroethylthio, pentafluo C. -R)- CH - -- roethylsulfonyl and difluorobromomethoxy provided that O CF when R is hydroxy, R is not methyl, or when R is trif CH3 luoromethyl, R is hydroxy and W is CH, the substituents V Ho of Q are two or more of the group consisting of trifluorom 45 HN-CH-CHSCH. ethyl, pentafluoroethyl, heptafluoro-n-propyl, hep C O tafluoro-i-propyl and nonafluoro-n-butyl. " The compounds of the formula (I) according to the present NH-CH-CHSCH. invention include stereoisomers (R/S coordinate) when the group R' has an asymmetric carbon. 50 O Method (a) may be represented by the following reaction formula when, for example, 4-chloro-3-(1,1-dimethyl-2-me HN thylthioethylimino)-3H-isobenzofuran-1-one and 4-(3,5-bis trifluoromethyl-benzyl)-2-methylaniline are used as the start 55 CF ing materials. H3C CH

CH3 C 60 CF N CHSCH. CH3 -- Method (c) may be represented by the following reaction O formula when, for example, 3-chloro-N-(1,1-dimethyl-2-me 65 thylthioethyl)-phthalamic acid and 4-(3,5-bis-trifluorom O ethyl-O-methylbenzyl)-2-methylaniline are used as the start ing materials. US 8,110,689 B2

-continued C O C O CH3 st NHersch, -- 5 NH-CH-CHSCH. CH O CO2H CH3 HN 10 CH3 CF3 CF CH3 CH

HN CH --- 15 CF CF Method (e) may be represented by the following reaction C O 20 formula when, for example, N-4-(3,5-bis-trifluoromethyl CH benzyl)-2-methyl-phenyl]-6-chloro-phthalamic acid and 1-methyl-2-methylthioethylamine are used as the starting NH CHSCH3 materials. O CH 25 C NH CO2H CF CH CH 30 O CH3 H3C HN -- CF 35 CF CH

Method (d) may be represented by the following reaction formula when, for example, 1-4-(4-chloro-3-oxo-3H- CF3 isobenzofuran-1-ylideneamino)-3-methyl-benzyl-3,5-bis- CH + acid binder trifluoromethyl-benzene and 1-methyl-2-methylthioethy- HN-CH-CHSCH. lamine are used as the starting materials. 45 C O C O CH NH-CH-CHSCH. O 50 O CH3 CH3 N NH --

CF 55 CF CH CH

CF 60 CF

Method (f) may be represented by the following reaction CH3 formula when, for example, N'-(1-methyl-2-methylthioet HN-CH-CHSCH. 65 hyl)-3-chloro-N'-(2-methyl-4-(3.5-bis-trifluoromethyl-ben Zyl)phenylphthalamide and m-chloroperbenzoic acid are used as the starting materials. US 8,110,689 B2 10 methanesulfonic acid 3-(1-methyl-2-methylthioethylimino)- C O 1-oxo-1,3-dihydro-isobenzofuran-4-yl ester, CH3 methanesulfonic acid 3-(1,1-dimethyl-2-methylthioeth NH-CHCHSCH. ylimino)-1-oxo-1,3-dihydro-isobenzofuran-4-yl ester, and SO. O. O Some of the compounds of the formula (III) used as the CH starting material in Method (a) are new compounds not pub HN -- lished in the prior art, but they may be obtained by, for example, the catalytic hydrogenation, a well-known method 10 CF in the art of organic chemistry, from compounds of the for CH2 mula (IX):

(IX) 15 Y CF m-chloroperbenzoic acid -- C O CH3 NH-CHCHSOCH in whichY. R. R. Wand Qare the same as identified above, O which are reduced by hydrogen in the presence of a reduc CH3 tion catalyst Such as palladium carbon, Raney nickel, plati HN num oxide, etc. 25 The catalytic hydrogenation may be carried out in a Suit CF able diluent, examples of Such diluent being ethers such as CH ethyl ether, methylethyl ether, isopropyl ether, butyl ether, dioxane, and tetrahydrofuran (THF); alcohols such as metha 30 nol, ethanol, isopropanol, butanol and ethylene glycol. Examples of the reduction catalyst are palladium carbon, CF Raney nickel, platinum oxide and the like. The reaction may be carried out generally at a temperature of about 0-100° C. The compounds of the formula (II) which are used as the preferably at room temperature to about 80° C. and under starting material in Method (a) are known compounds and 35 normal pressure and optionally under increased pressure. For may be readily produced according to, for example, JP-A-11 example, the compound of the formula (III) may be obtained 240857, JP-A-2001-131141 and so on. by adding hydrogen to the compound of The formula (IX) in Examples of the compound of the formula (II) used as the the presence of 0.1-10% w/w of palladium carbon in a diluent, starting material in Method (a) include for example ethanol. 3-isopropylimino-3H-isobenzofuran-1-one, 40 The compounds of the formula (III) may alternatively be obtained from the compounds of the formula (IX) by a reduc 4-fluoro-3-isopropylimino-3H-isobenzofuran-1-one, ing reaction using a metal or the like instead of the catalytic 4-chloro-3-isopropylimino-3H-isobenzofuran-1-one, hydrogenation. 4-bromo-3-isopropylimino-3H-isobenzofuran-1-one, As the reduction using the metal or the like, a reaction of 4-iodo-3-isopropylimino-3H-isobenzofuran-1-one, 45 iron powder in acetic acid, a reaction of Zinc dust under a 3-(1-methyl-2-methylthioethylimino)-3H-isobenzofuran-1- neutral condition (Organic Syntheses Collective, Vol. II, pp. One, 447), a reaction of Stannic chloride under an acid condition 4-fluoro-3-(1-methyl-2-methylthioethylimino)-3H-isoben (Organic Syntheses Collective, Vol. II, pp. 254), a reaction of Zofuran-1-one, titanium trichloride under a neutral condition and so on may 4-chloro-3-(1-methyl-2-methylthioethylimino)-3H-isoben 50 be mentioned. Zofuran-1-one, Novel compounds of the general formula (III) are repre 4-bromo-3-(1-methyl-2-methylthioethylimino)-3H-isoben sented by formula (III-a) Zofuran-1-one, 4-iodo-3-(1-methyl-2-methylthioethylimino)-3H-isobenzo furan-1-one, 55 (III-a) 3-(1,1-dimethyl-2-methylthioethylimino)-3H-isobenzofu HN ran-1-one, 2 n W 3-(1,1-dimethyl-2-methylthioethylimino)-4-fluoro-3H Q isobenzofuran-1-one, 6 A. 21 Z 4-chloro-3-(1,1-dimethyl-2-methylthioethylimino)-3H 60 R2 R3 isobenzofuran-1-one, 4-bromo-3-(1,1-dimethyl-2-methylthioethylimino)-3H isobenzofuran-1-one, in which 3-(1,1-dimethyl-2-methylthioethylimino)-4-iodo-3H W represents CH or N: isobenzofuran-1-one, 65 Z represents C alkyl or halogen; methanesulfonic acid 3-isopropylimino-1-oxo-1,3-dihydro R represents hydrogen, C. alkyl or Chaloalkyl; isobenzofuran-4-yl ester, R represents hydrogen or hydroxy; and US 8,110,689 B2 11 12 Q represents optionally Substituted phenyl or optionally Sub The compounds of the formula (IX), wherein R is hydro stituted pyridyl wherein the Substituent is at least one group gen and R is hydroxy; may be, obtained by oxidizing com Selected from the group consisting of Chaloalkyl, C. pounds of the formula (IX-a): haloalkoxy and Chaloalkylthio, Ce haloalkylsulfinyl and Chaloalkylsulfonyl. provided that when R is hydroxy, R is not C, alkyl, or (IX-a) when R is C, haloalkyl, R is hydroxy and W is CH, the Y Substituents of Q are two or more Chaloalkyl. -W Many of the compounds of the formula (IX) are new com pounds, and when R and R are both hydrogen, the com 10 os-()-cis pounds of the formula (IX) may be obtained, for example, by reacting compounds of the formula (X): in which Y. W and Q are the same as identified above, to obtain compounds of the formula (XII): (X) 15 (XII) Y os-()---W in which Y and W are the same as identified above and M represents chloro, bromo or methylsulfonyloxy, in which Y. W and Q are the same as identified above, with compounds of the formula (XI): followed by reducing the compounds of the formula (XII). 25 The above reaction may be carried out according to the method described in Chem. Ber. Vol. 18, 1885, pp. 2402. The compounds of the formula (IX), wherein R is C. in which Q is the same as identified above. haloalkyl and R is hydroxy, for example, R is C, perha The above reaction may be carried out according to the loalkyl and R is hydroxy, may be obtained by reacting the method described in J. Org. Chem., 1994, Vol. 59, pp. 6501. 30 compounds of the formula (XII) with compounds of the for Novel compounds of the general formula (IX) are repre mula (XIII): sented by the formula (IX-b) (CH)Si-R’ (XIII) in which R" represents C, perhaloalkyl. 2 Q (IX-b) 35 The above reaction may be carried out according to the W method described in J. Org. Chem. Vol. 56, No. 3, 1991, pp. 984. Instead of the trimethylsilyl of The formula (XIII), a so-()6 == R2- triethylsilyl may alternatively be used for the reaction. Z The compounds of the formula (IX), wherein R is C. 40 haloalkyl and R is hydrogen, for example R is C perha loalkyl and R is hydrogen, may be obtained by reacting the in which compounds of the formula (IX) in which R is C perha Z represents C alkyl, loalkyl and R is hydroxy, with methanesulfonyl chloride Z furthermore represents halogen in the 2- or 6-position of the followed by reacting it with lithium aluminum hydride. ring system; 45 The above reaction may be carried out according to the R represents hydrogen, C-alkyl or Chaloalkyl; reaction described in J. Chem. Soc. Perkin Trans., Vol. 1, R represents hydrogen or hydroxy: 1983, pp. 1267. W represents CH or N; and The compounds of the formula (XI), another starting mate Q represents optionally Substituted phenyl or optionally Sub rial for the preparation of the compounds of the formula (IX), stituted pyridyl wherein the Substituent is at least one group 50 includes publicly known compounds, for example, 3-trifluo Selected from the group consisting of halogen; C. romethylphenylboronic acid, 3,5-dichlorophenylboronic haloalkyl, Ce haloalkoxy and Ce haloalkylthio, C. acid,3,5-bis-trifluoromethylphenylboronic acid, 2-chloropy haloalkylsulfinyl and Chaloalkylsulfonyl. ridine-4-boronic acid, 2-chloropyridine-5-boronic acid, 4-tri provided that when R is hydroxy, R is not C alkyl, or fluoromethylpyridine-3-boronic acid, 5-trifluoromethylpyri when R is C, haloalkyl, R is hydroxy and W is CH, the 55 dine-2-boronic acid and so on. The boronic acids of pyridine Substituents of Q are two or more Chaloalkyl. may be obtained according to the method described in Tetra The compounds of the formula (X) above are well-known hedron, 2001, pp. 2991. compounds in the art of organic chemistry and may be readily Instead of the boronic acid of the formula (XI) above, obtained by the methods as described, for example, in J. boronic acid ester may be used for the reaction. Chem. Soc., 1967, pp. 1154-1158 and J. Amer. Chem. Soc., 60 The reaction of the compounds of the formula (X) with the Vol. 75, 1953, pp. 3830. compounds of the formula (XI) may be carried out in a Suit Representative examples of the compounds of the formula able diluent, examples of which include aliphatic, (X) are: cycloaliphatic and aromatic hydrocarbons (optionally chlori 3-methyl-4-nitrobenzyl chloride, nated), for example, pentane, hexane, cyclohexane, petro 3-methyl-4-nitrobenzyl bromide, 65 leum ether, ligroin, benzene, toluene, Xylene, dichlo methanesulfonic acid 3-methyl-4-nitrobenzyl ester, and romethane; ethers such as ethylether, methyl-ethylether, 3-chloro-4-nitrobenzyl chloride. isopropylether, butylether, dioxane, dimethoxyethane US 8,110,689 B2 13 14 (DME), tetrahydrofuran (THF) and diethyleneglycoldimeth In the above method, an ester of benzyl, methyl or ethyl ylether (DGM); ketones such as acetone, methylethylketone may be used for the tert-butyl ester of carbamic acid of the (MEK), methyl-isopropylketone and methylisobutylketone formula (XIV). In the case of benzylester, the target com (MIBK); nitriles such as acetonitrile, propionitrile and acry pound of The formula (III) may be obtained by catalytic lonitrile; esters such as ethyl acetate and amyl acetate; acid hydrogen reduction, and in the case of methylester and ethy amides such as dimethylformamide (DMF), dimethylacetoa lester, it may be obtained by reaction under alkaline condition mide (DMA), N-methylpyrrolidone, 1,3-dimethyl-2-imida (deprotection). Zolidinone and hexamethylphosphorictriamide (HMPA). The catalytic hydrogenation may be carried out according This reaction may be carried out in the presence of an acid 10 to the method described in J. Org. Chem., 1981, pp. 134. The binder. Examples of Such acid binder include, as inorganic deprotection reaction under the alkaline condition may be bases, hydrides, hydroxides, carbonates and hydrogen car carried out according to the method described in J. Am. bonates of alkali metal or alkaline earth metal Such as sodium hydride, lithium hydride, sodium hydrogen carbonate, potas Chem. Soc., 1952, pp. 1087. sium hydrogen carbonate, sodium carbonate, potassium car The compounds of the formula (XIV) above may be bonate, lithium hydride, Sodium hydroxide, potassium 15 obtained by, for example, reacting compounds of the formula hydroxide and calcium hydroxide; inorganic alkali metal (XV): amides such as lithium amide, Sodium amide and potassium amide; and as organic bases, alcoholate, tertiary amines, dialkylaminoanilines, and pyridines such as triethylamine, (XV) 1,1,4,4-tetramethylethylenediamine (TMEDA), N,N-dim tert-C4H90-N-N ethylaniline, N,N-diethylaniline, pyridine, 4-dimethylami C Sw H3C nopyridine (DMAP), 1,4-diazabicyclo[2.2.2]octane I A-4N/us O CH (DABCO) and 1,8-diazabicyclo5.4.0]undec-7-ene (DBU). Y N The above reaction may also be carried out by the use of a 25 O CH phase-transfer catalyst in the presence of a diluent. Examples H3C of the diluent are water, aliphatic, cycloaliphatic and aromatic hydrocarbons (optionally chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, tolu in which Y and W are the same as identified above, ene, xylene and the like; ethers such as ethylether, methyleth ylether, isopropylether, butylether, dioxane, dimethoxy 30 with compounds of the formula (XVI): ethane (DME), tetrahydrofuran (TI-IF) and diethyleneglycoldimethylether (DGM). Examples of the Q-CH-M (XVI) phase-transfer catalyst are quaternary ions such as tetram in which Q and Mare the same as identified above. ethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium bisSul 35 The above reaction may be carried out according to the phate, tetrabutylammonium iodide, trioctylmethylammo method described in J. Org. Chem., 1994, Vol. 59, pp. 6501. nium chloride, benzyltriethylammonium bromide, butylpyri The compound of the formula (XV) above may be obtained dinium bromide, heptylpyridinium bromide and by reacting compounds of the formula (XVII): benzyltriethylammonium chloride; and crown ethers such as dibenzo-18-crown-6, dicyclohexyle-18-crown-6 and 40 18-crown-6, cryptands Such as 2.2.2-cryptate, 2.1.1 - (XVII) cryptate, 2.2.1-cryptate, 2.2.B-cryptate and 3.2.2- ter-C4HoO cryptate. The above reaction may be carried out in a substantially 45 wide temperature range, but generally between about 0 and al about 200° C., preferably between room temperature and Y about 150° C. Desirably, the reaction should be carried out under normal pressure but optionally it may be operated in which Y and W are the same as identified above and Hal under increased or reduced pressure. represents halogen, As an alternative process for preparation of the compounds 50 of the formula (III) above, the compounds of the formula (III), with pinacolborane using a palladium catalyst. when both of R and R are hydrogen, may be readily This reaction may be carried out according to the method obtained by reacting under acid condition compounds of the described in J. Org. Chem., 2000, Vol. 65, pp. 168. formula (XIV): 55 (4-Iodo-2-methyphenyl)carbamic acid tert-butyl ester, as a representative example of the compound of the formula (XVII) above, may be easily obtained from the well-known tert CAHoO N (XIV) 4-iodo-2-methylaniline. 4rlig O The compounds of The formula (XVI) in which the sub O us 60 stituent of Q is perfluoroalkyl with two or more carbon atoms y 21 CH1 Q may be obtained by the method described in Tetrahedron, 2002, Vol. 58, pp. 3999 or Tetrahedron Lett., Vol. 32, No. 1, in which Y. W and Q are the same as identified above. 1991, pp. 91. This reaction may be carried out according to the method 65 The compounds of the formula (XIV) above may alterna described in J. Org. Chem., 1969, pp. 395, J. Med. Chem. tively be obtained by reacting compounds of the formula 1990, pp. 1153 and others. (XVIII): US 8,110,689 B2 15 16 mophthalic anhydride, 3-iodophthalic anhydride, 3-methane (XVIII) Sulfonyloxyphthalic anhydride and so on. Of the compounds exemplified above, 3-methanesulfony loxyphthalic anhydride may be obtained easily from 3-hy r droxyphthalic anhydride and methanesulfonylchloride O Y:-- according to the method described in Tetrahedron Lett., Vol. 29, pp.5595-8 (1988). Representative examples of the compounds of the formula in which Y. W. and Mare the same as identified above and L (IV) which are used as the starting material in Method (b) are represents methyl, ethyl, tert-butyl or benzyl, 10 given below: with the boronic acid of the formula (XI) above or ester 4-chloro-2-(2-methyl-4-(3.5-bis-trifluoromethylbenzyl)- thereof. phenylisoindole-1,3-dione, The compounds of the formula (XVIII) above may be 4-chloro-2-(2-methyl-4-(3.5-bis-pentafluoroethylbenzyl)- obtained according to the method described in J. Org. Chem. phenylisoindole-1,3-dione and so on. 2002, pp. 741. 15 The compounds of the formula (V) used as the starting Representative examples of the compounds of the formula material in Method (b) may either be a well-known com (III) include: pound in the art of organic chemistry or be synthesized 4-(3,5-bis-trifluoromethylbenzyl)-2-methylaniline, according to the method described in German Patent No. 4-(3,5-bis-pentafluoroethylbenzyl)-2-methylaniline, 2045905, WO 01/23350 and so on. Examples thereof include 4-(3,5-bis-perfluorobutylbenzyl)-2-methylaniline, ethylamine, diethylamine, n-propylamine, isopropylamine, 4-(3,4-bis-pentafluoroethylbenzyl)-2-methylaniline, n-butylamine, sec-butylamine, isobutylamine, t-butylamine, 4-(3,5-dichlorobenzyl)-2-methylaniline, t-amylamine, 2-(methylthio)-ethylamine, 2-(ethylthio)-ethy 4-(3,5-dibromobenzyl)-2-methylaniline, lamine, 1-methyl-2-(methylthio)-ethylamine, 1,1-dimethyl 4-(4-trifluoromethoxybenzyl)-2-methylaniline, 2-(methylthio)-ethylamine and so on. 4-(4-trifluoromethylthiobenzyl)-2-methylaniline, 25 The compounds of the formula (VI) which are used as the 4-(4-iso-perfluoropropylbenzyl)-2-methylaniline, and starting material in Method (c) encompasses publicly known 4-(2,6-bis-pentafluoroethyl-pyridin-4-yl)-methylaniline. compounds and may be readily produced according to the The compounds of the formula (IV) used as the starting method described in JP-A-11-240857, JP-A-2001-131141 material in Method (b) above are novel and may be easily and so on. The following are the examples thereof: obtained, for example, by reacting compounds of the formula 30 N-isopropyl-phthalamic acid, (XIX): 3-fluoro-N-isopropyl-phthalamic acid, 3-chloro-N-isopropyl-phthalamic acid, 3-bromo-N-isopropyl-phthalamic acid, (XIX) 3-iodo-N-isopropyl-phthalamic acid, 35 N-(1-methyl-2-methylthioethyl)-phthalamic acid, 21 3-fluoro-N-(1-methyl-2-methylthioethyl)-phthalamic acid, X-H O 3-chloro-N-(1-methyl-2-methylthioethyl)-phthalamic acid, N 3-bromo-N-(1-methyl-2-methylthioethyl)-phthalamic acid, 3-iodo-N-(1-methyl-2-methylthioethyl)-phthalamic acid, O 40 N-(1,1-dimethyl-2-methylthioethyl)-phthalamic acid, N-(1,1-dimethyl-2-methylthioethyl)-3-fluoro-phthalamic in which X is the same as identified above, acid, with the compounds of the formula (III) above, according 3-chloro-N-(1,1-dimethyl-2-methylthioethyl)-phthalamic to the method described in JP-A-61-246.161. acid, This reaction may be carried out in a suitable diluent. 45 3-bromo-N-(1,1-dimethyl-2-methylthioethyl)-phthalamic Examples of the diluent are aliphatic, cycloaliphatic and aro acid, matic hydrocarbons (optionally chlorinated), for example, N-(1,1-dimethyl-2-methylthioethyl)-3-iodo-phthalamic pentane, hexane, cyclohexane, petroleum ether, ligroin, ben acid, Zene, toluene, Xylene, dichloromethane, chloroform, carbon N-isopropyl-3-methanesulfonyloxy-phthalamic acid, tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlo 50 N-(1-methyl-2-methylthioethyl)-3-methanesulfonyloxy-ph robenzene and the like; ethers such as ethylether, methyleth thalamic acid, ylether, isopropylether, butylether, dioxane, dimethoxy N-(1-methyl-2-methylthioethyl)-3-nitro-phthalamic acid, ethane (DME), tetrahydrofuran (THF) and 3-chloro-N-(2-ethylthio-1-methyl-ethyl)-phthalamic acid, diethyleneglycoldimethylether (DGM); esters such as ethyl 3-bromo-N-(2-ethylthio-1-methyl-ethyl)-phthalamic acid, acetate and amyl acetate; acid amides Such as dimethylfor 55 N-(2-ethylthio-1-methyl-ethyl)-3-iode-phthalamic acid, mamide (DMF), dimethylacetoamide (DMA), N-methylpyr N-(2-ethylthiol-methyl-ethyl)-3-nitro-phthalamic acid, rolidone, 1,3-dimethyl-2-imidazolidinone and hexameth N-(2-ethyl-1-methyl-ethyl)-3-methanesulfonyloxy-phtha ylphosphoricamide (HMPA); acids such as acetic acid etc. lamic acid, The above reaction may be carried out in a substantially N-(1,1-dimethyl-2-methyl-ethyl)-3-methanesulfonyloxy wide temperature range, but generally between room tem 60 phthalamic acid and so on. perature and about 200° C., preferably between room tem The compounds of the formula (VI) exemplified above perature and about 150° C. Desirably, the reaction should be may be readily obtained generally by reacting the phthalamic carried out under normal pressure but optionally it may be anhydrides of the formula (XIX) above with amines of the operated under increased or reduced pressure. formula (XX): Many of the compounds of the formula (XIX) are well 65 known. Examples thereof include phthalic anhydride, 3-fluo R" NH, (XX) rophthalic anhydride, 3-chlorophthalic anhydride, 3-bro in which R" is the same as identified above. US 8,110,689 B2 17 18 The compounds of the formula (XX) above are well known The reaction between the above compounds may be con in the art of organic chemistry. Examples thereof include ducted in a suitable diluent. The diluent used therein may be, ethylamine, n-propylamine, isopropylamine, n-butylamine, for example, aliphatic, cycloaliphatic and aromatic hydrocar sec-butylamine, isobutylamine, t-butylamine, t-amylamine, bons (optionally chlorinated) Such as pentane, hexane, cyclo 2-(methylthio)ethylamine, 2-(ethylthio) ethylamine, 1-me hexane, petroleum ether, ligroin, benzene, toluene, Xylene, thyl-2-(methylthio)ethylamine, 1,1-dimethyl-2-(methylthio) dichloromethane, chloroform, carbon tetrachloride, 1,2- ethylamine and the like. dichloroethane, chlorobenzene, dichlorobenzene and the These amines may be easily obtained by the method like; ethers such as ethylether, methylethylether, isopropy described in German Patent No. 2045905, WO 01/23350 as lether, butylether, dioxane, dimethoxyethane (DME), tet well. 10 rahydrofuran (THF), diethyleneglycoldimethylether (DGM) The reaction of the compounds of the formula (XIX) above with the amines of the formula (XX) may be carried out for and so on; ketones such as acetone, methylethylketone example by the method described in J. Org. Chem. Vol. 46, (MEK), methylisopropylketone, methylisobutylketone pp. 175, 1981 and others, and it may be worked in a suitable (MIBK) and so on; nitriles such as acetonitrile, propionitrile, diluent. The diluent used therein may be for example ali 15 acrylonitrile and so on; esters such as ethyl acetate, amyl phatic, cycloaliphatic and aromatic hydrocarbons (optionally acetate and so on. chlorinated), for example pentane, hexane, cyclohexane, The above reaction may be conducted in the presence of a petroleum ether, ligroin, benzene, toluene, Xylene, dichlo base, examples of Such base being tertiary amines, dialky romethane, chloroform, carbon tetrachloride, 1,2-dichloroet laminoanilines and pyridines such as triethylamine, 1,14.4- hane, chlorobenzene, dichlorobenzene and the like; ethers tetramethylethylenediamine (TMEDA), N,N-dimethyla such as ethylether, methylethylether; isopropylether, niline, N,N-diethylaniline, pyridine, butylether, dioxane, dimethoxyethane (DME), tetrahydrofu 4-dimethylaminopyridine (DMAP), 1,4-diazabicyclo[2.2.2 ran (THF) and diethyleneglycoldimethylether (DGM); octane (DABCO), 1,8-diazabicyclo[5.4.0]undec-7-ene ketones such as acetone, methylethylketone (MEK), methyl (DBU) and so on. isopropylketon and methylisobutylketon (MIBK); nitriles 25 The above reaction may be carried out in a substantially Such as acetonitrile, propionitrile and acrylonitrile; esters wide temperature range, but generally between about -70 and Such as ethyl acetate and amyl acetate. about 100° C., preferably between about -50 and about 80°C. The above reaction may be conducted in the presence of a Desirably, the reaction should be carried out under normal base, examples of Such base being tertiary amines, dialky pressure but optionally it may be operated under increased or laminoanilines and pyridines, for example, triethylamine, 30 reduced pressure. 1,1,4,4-tetramethylethylenediamine (TMEDA), N,N-dim The following may be given as representative examples of ethylaniline, N,N-diethylaniline, pyridine, 4-dimethylami the compound of the formula (VIII) above: nopyridine (DMAP), 1,4-diazabicyclo[2.2.2]octane N-4-(3,5-bis-trifluoromethyl-benzyl)-2-methyl-phenyl]-6- (DABCO), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and iodo-phthalamic acid, SO. O. 35 6-chloro-N-4-(3,5-bis-trifluoromethyl-benzyl)-2-methyl The above reaction may be carried out in a substantially phenyl-phthalamic acid and so on. wide temperature range, but generally between about -70 and The compounds of the formula (V) used as the starting about 100° C., preferably between about -50 and about 80°C. material in Method (e) may be the same as that used in Desirably, the reaction should be carried out under normal Methods (b) and (d) above. pressure but optionally it may be operated under increased or 40 The compounds of the formula (If) which are used as the reduced pressure. starting material in Method (f) are compounds encompassed The compounds of the formula (VII) used as the starting by the formula (I) of the present invention. The compounds of material in Method (d) are a new compounds, and may be the formula (I), wherein R' corresponds to C, alkylsulfinyl easily obtained for example by reacting the compounds of the C. alkyl or C. alkylsulfonyl-C alkyl, may be obtained formula (VIII) which is the starting material in Method (e) in 45 by oxidizing C, alkylthio-C, alkyl which are R'? of for the presence of a condensing agent according to the method mula (If). described in J. Med. Chem. Vol. 10, pp. 982, 1967. The compounds of the formula (If) may be prepared The following are the representative examples of the com according to the methods as described in Method (a), (b), (c), pounds of the formula (VII): (d) and/or (e). 1-4-(4-iodo-3-oxo-3H-isobenzofuran-1-ylideneamino)-3- 50 The representative examples of the compounds of the for methyl-benzyl-3,5-bis-trifluoromethyl-benzene, mula (If) are: 1-4-(4-chloro-3-oxo-3H-isobenzofuran-1-ylideneamino)- 3-iodo-N-(1-methyl-2-methylthioethyl)-N'-(2-methyl-4- 3-methyl-benzyl-3,5-bis-trifluoromethyl-benzene, (3,5-bis-trifluoromethylbenzyl)-phenyl-phthalamide, 1-4-(4-chloro-3-oxo-3H-isobenzofuran-1-ylideneamino)- N'-(1,1-dimethyl-2-methylthioethyl)-3-iodo-N'-(2-methyl 3-methyl-benzyl-3,4-bis-pentafluoroethyl-benzene, 55 4-(3,5-bis-trifluoromethylbenzyl)-phenyl-phthalamide, 1-4-(4-iodo-3-oxo-3,1-isobenzofuran-1-ylideneamino)-3- 3-iodo-N-(1-methyl-2-methylthioethyl)-N'-(2-methyl-4- methyl-benzyl-3,5-bis-pentafluoroethyl-benzene, (3,5-bis-trifluoromethylbenzyl)-phenyl-phthalamide, 1-4-(4-chloro-3-oxo-3H-isobenzofuran-1-ylideneamino)- 3-chloro-N'-(1-methyl-2-methylthioethyl)-N'-(2-methyl-4- 3-methyl-benzyl-3,4-bis-heptafluoropropyl-benzene and (3,5-bis-trifluoromethylbenzyl)-phenyl-phthalamide, SO O. 60 3-chloro-N'-(1-methyl-2-methylthioethyl)-N'-(2-methyl-4- The compounds of the formula (V) used as the starting (3.4-bis-pentafluoroethylbenzyl)-phenyl-phthalamide, material in Method (d) are as explained in Method (b). 3-chloro-N'-(1-methyl-2-methylthioethyl)-N'2-methyl-4- The compounds of the formula (VIII) used as the starting (3,5-bis-pentafluoroethylbenzyl)-phenyl-phthalamide, material in Method (e) are novel compounds and may be 3-chloro-N'-(1-methyl-2-methylthioethyl)-N'-(2-methyl-4- easily obtained for example by reacting the phthalic anhy 65 (4-iso-perfluoropropylbenzyl)-phenyl-phthalamide, drides of the formula (XII) above with the compounds of the 3-chloro-N'-(1-methyl-2-methylthioethyl)-N'-(2-methyl-4- formula (III) above. (3,5-dichlorobenzyl)-phenyl-phthalamide, US 8,110,689 B2 19 20 3-chloro-N'-(1-methyl-2-methylthioethyl)-N'-(2-methyl-4- phatic, cycloaliphatic and aromatic hydrocarbons (optionally (2,6-bis-pentafluoroethyl-pyridin-4-ylmethyl)-phenyl chlorinated) Such as benzene, toluene, Xylene, dichlo phthalamide and so on. romethane, chloroform, carbon tetrachloride, 1,2-dichloroet The reaction of Method (a) above may be conducted in a hane, chlorobenzene, dichlorobenzene etc.; alcohols such as suitable diluent singly or in mixture. Examples of the diluent methanol, ethanol, isopropanol, butanol etc.; acids such as are water, aliphatic, cycloaliphatic and aromatic hydrocar formic acid, acetic acid and so on. bons (optionally chlorinated) Such as pentane, hexane, cyclo The oxidant used in Method (f) above may be, for example, hexane, petroleum ether, ligroin, benzene, toluene, Xylene, metachloroperbenzoic acid, peracetic acid, potassium meta dichloromethane, chloroform, carbon tetrachloride, 1,2- periodate, potassium hydrogen persulfate (Oxon), hydrogen dichloroethane, chlorobenzene, dichlorobenzene and the 10 peroxide and so on. like; ethers such as ethylether, methylethylether, isopropy Method (f) may be conducted in a substantially wide tem lether, butylether, dioxane, dimethoxyethane (DME), tet perature range, but generally between about -50 and about rahydrofuran diethyleneglycoldimethylether (DGM) and the 150° C., preferably between -10 and about 100° C. Desirably, like: nitriles such as acetonitrile, propionitrile, acrylonitrile the reaction should be carried out under normal pressure but and so on; esters such as ethyl acetate, amyl acetate and so on. 15 optionally it may be operated under increased or reduced Method (a) may be carried out in the presence of an acid pressure. catalyst, examples of such acid catalyst being inorganic acids In carrying out Method (f), the target compounds of the Such as hydrochloric acid and Sulfuric acid; organic acids formula (I) may be obtained by reacting one mol of the Such as acetic acid, trifluoro acetic acid, propionic acid, meth compounds of the formula (If) with 1-5 mol of oxidant in a anesulfonic acid, benzensulfonic acid, p-toluenesulfonic acid diluent such as dichloromethane. and the like. The reaction of Method (f) may be conducted according to Method (a) may be carried out in a substantially wide the method described in Jikken Kagaku Koza (Experimental temperature range, but generally between about -20 and Chemistry), Japan Chemical Society 4th Edition, Vol. 24, pp. about 100° C., preferably between about 0 and about 100° C. 350, 1992 published by Maruzen or pp. 365 of the same. Desirably, the reaction should be carried out under normal 25 The active compounds according to the invention are well pressure but optionally it may be operated under increased or tolerated by plants, have favourable toxicity to warm-blooded reduced pressure. species, show good environmental compatibility and are Suit In conducting Method (a), the target compounds of the able for protecting plants and plant organs, for increasing formula (I) may be obtained by, for example, reacting one mol yields, improving the quality of the yield and for controlling of the compounds of the formula (II) with one mol or a few 30 animal pests, in particular insects, arachnids, helminths, excess mols of the compounds of the formula (III) in the nematodes and molluscs, which are found in agriculture, presence of 0.01-0.1 mol of p-toluenesulfonic acid in a dilu horticulture, in animal breeding, in forests, in gardens and ent such as 1,2-dichloroethane. leisure facilities, in the protection of stored products and The reaction of Method (b) above may be carried out in a materials and in the hygiene sector. They can preferably be Suitable diluent, examples of Such diluent being aliphatic, 35 employed as plant protection agents. They are active against cycloaliphatic and aromatic hydrocarbons (optionally chlori normally sensitive and resistant species and against all or nated) Such as pentane, hexane, cyclohexane, petroleum individual developmental stages. The abovementioned pests ether, ligroin, benzene, toluene, Xylene, dichloromethane, include: chloroform, carbon tetrachloride, 1,2-dichloroethane, chlo From the order of the Anoplura (Phthiraptera), for example robenzene, dichlorobenzene and so on; ethers such as ethyl 40 Damalinia spp., Haematopinus spp., Linognathus spp., ether, methylethylether, isopropylether, butylether, dioxane, Pediculus spp., trichodectes spp. dimethoxyethane (DME), tetrahydrofuran (THF), diethyl From the class of the Arachnida, for example Acarus siro, eneglycoldimethylether (DGM) and so on; esters such as Aceria Sheldoni, Aculops spp., Aculus spp., Amblyomma spp., ethyl acetate, amyl acetate and so on; acid amides Such as Argas spp., Boophilus spp., Brevipalpus spp., Bryobia pra dimethylformamide (DMF), dimethylacetoamide (DMA), 45 etiosa, Chorioptes spp., Dermanyssus gallinae, Eotetrany N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, hex chus spp., Epitrimerus pyri, Eutetranychus spp., Eriophyes amethylphosphorictriamide (HMPA) and so on. spp., Hemitarisonemus spp., Hyalomma spp., Ixodes spp., Method (b) may be carried out in the presence of an acid Latrodectus mactans, Metatetranychus spp., Oligonychus catalyst, examples of Such acid catalyst including inorganic spp., Ornithodoros spp., Panonychus spp., Phylocoptruta acids such as hydrochloric acid and Sulfuric acid; organic 50 oleivora, Polyphagotarisonemus latus, Psoroptes spp., Rhipi acids such as acetic acid, trifluoro acetic acid, propionic acid, cephalus spp., Rhizoglyphus spp., Sarcoptes spp., Scorpio methanesulfonic acid, p-toluenesulfonic acid and the like. maurus, Stenotarisonemus spp., Tarsonemus spp., Tetrany Method (b) may be conducted in a substantially wide tem chus spp., Vasates lycopersici. perature range, but generally between about -20 and about From the class of the Bivalva, for example Dreissena spp. 150° C., preferably between room temperature and about 55 From the order of the Chilopoda, for example Geophilus 100° C. Desirably, the reaction should be carried out under spp., Scutigera spp. normal pressure but optionally it may be operated under From the order of the Coleoptera, for example Acan increased or reduced pressure. thoscelides Obtectus, Adoretus spp., Agelastica alni, Agriotes In carrying out Method (b), the target compounds of the spp., Amphimallon solstitialis, Anobium punctatum, Anoplo formula (I) may be obtained for example by reacting one mol 60 phora spp., Anthonomus spp., Anthrenus spp., Apogonia spp., of the compounds of the formula (IV) with 1-25 mol of the Atomaria spp., Attagenus spp., Bruchidius Obtectus, Bruchus compounds of the formula (V) in the presence of 0.01-0.5mol spp., Ceuthorhynchus spp., Cleonus mendicus, Conoderus of acetic acid in a diluent Such as dioxane. spp., Cosmopolites spp., Costelytra zealandica, Curculio Methods (c), (d) and (e) may be conducted under the same spp., Cryptorhynchus lapathi, Dermestes spp., Diabrotica conditions as Method (a) above. 65 spp., Epilachna spp., Faustinus cubae, Gibbium psylloides, The reaction of Method (f) above may be carried out in a Heteronychus arator, Hylamorpha elegans, Hylotrupes baju suitable diluent. Examples of such diluent may include ali lus, Hypera postica, Hypothenemus spp., Lachnosterna Con US 8,110,689 B2 21 22 sanguinea, Leptinotarsa decemlineata, Lissorhoptrus Oryzo cuna lanigera, Cercopidae, Ceroplastes spp., Chaetosiphon philus, Lixus spp., Lyctus spp., Melligethes aeneus, fragaefolii, Chionaspis tegalensis, Chlorita Onuki, Chroma Melolontha melolontha, Migdolus spp., Monochamus spp., phis juglandicola, Chrysomphalus ficus, Cicadulina mbila, Naupactus xanthographus, Niptus hololeucus, Oryctes rhi Coccomytilus halli, Coccus spp., Cryptomyzus ribis, Dalbu noceros, Oryzaephilus surinamensis, Otiorrhynchus sulca lus spp., Dialeurodes spp., Diaphorina spp., Diaspis spp., tus, Oxycetonia jucunda, Phaedon cochleariae, Phyllophaga Drosicha spp., Dysaphis spp., Dysmicoccus spp., Empoasca spp., Popillia japonica, Premnotrypes spp., Psylliodes spp., Eriosoma spp., Erythroneura spp., Euscelis bilobatus, chrysocephala, Ptinus spp., Rhizobius ventralis, Rhizopertha Geococcus coffeae, Homalodisca coagulata, Hvalopterus dominica, Sitophilus spp., Sphenophorus spp., Sternechus arundinis, Icerya spp., Idiocerus spp., IdioScopus spp., Lao spp., Symphyletes spp., Tenebrio molitor; Tribolium spp., Tro 10 delphax striatellus, Lecanium spp., Lepidosaphes spp., Lipa goderma spp., Tichius spp., Xylotrechus spp., Zabrus spp. phis erysimi, Macrosiphum spp., Mahanarva fimbriolata, From the order of the Collembola, for example Onychiurus Melanaphis sacchari, Metcalfiella spp., Metopolophium arinatti S. dirhodium, Monellia Costalis, Monelliopsis pecanis, Myzus From the order of the Dermaptera, for example Forficula spp., Nasonovia ribisnigri, Nephotettix spp., Nilaparvata auricularia. 15 lugens, Oncometopia spp., Orthezia praelonga, Parabemisia From the order of the Diplopoda, for example Blaniulus myricae, Paratrioza spp., Parlatoria spp., Pemphigus spp., guttulatus. Peregrinus maidis, Phenacoccus spp., Phloeomyzus passeri From the order of the Diptera, for example Aedes spp., nii, Phorodon humuli, Phylloxera spp., Pinnaspis aspidis Anopheles spp., Bibio hortulanus, Caliphora erythro trae, Planococcus spp., Protopulvinaria pyriformis, Pseu cephala, Ceratitis capitata, Chrysomyia spp., Cochliomyia daulacaspis pentagona, Pseudococcus spp., Psylla spp., spp., Cordylobia anthropophaga, Culex spp., Cuterebra spp., Pteromalus spp., Pyrilla spp., Ouadraspidiotus spp., Oue Dacus oleae, Dermatobia hominis, Drosophila spp., Fannia Sada gigas, Rastrococcus spp., Rhopalosiphum spp., Saisse spp., Gastrophilus spp., Hyllemyia spp., Hyppobosca spp., tia spp., Scaphoides titanus, Schizaphis graminum, Selena Hypoderma spp., Liriomyza spp., Lucilia spp., Musca spp., spidus articulatus, Sogata spp., Sogatella fircifera, Nezara spp., Oestrus spp., Oscinella frit, Pegomyia hyos 25 Sogatodes spp., Stictocephala festina, Tenalaphara malayen cyani, Phorbia spp., Stomoxys spp., Tabanus spp., Tannia sis, Tinocallis caryaefoliae, Tomaspis spp., Toxoptera spp., spp., Tipula paludosa. trialeurodes vaporariorum, trioza spp., Tiphlocyba spp., From the class of the Gastropoda, for example Anion spp., Unaspis spp., Viteus vitifolii. Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., From the order of the Hymenoptera, for example Diprion Lynnaea spp., Oncomelania spp., Succinea spp. 30 spp., Hoplocampa spp., Lasius spp., Monomorium phara From the class of the Helminths, for example Ancylostoma Onis, Vespa spp. duodenale, Ancylostoma ceylanicum, Acylostoma brazilien From the order of the Isopoda, for example Armadillidium sis, Ancylostoma spp., Ascaris lubricoides, Ascaris spp., Bru vulgare, Oniscus asellus, Porcellio scaber. gia malayi, Brugia timori, Bunostomum spp., Chabertia spp., From the order of the Isoptera, for example Reticulitermes Clonorchis spp., Cooperia spp., Dicrocoelium spp., Dictyo 35 spp. caulus filaria, Diphyllobothrium latum, Dracunculus medin From the order of the Lepidoptera, for example Acronicta ensis, Echinococcus granulosus, Echinococcus multilocu major; Aedia leucomelas, Agrotis spp., Alabama argillacea, laris, Enterobius vermicularis, Faciola spp., Haemonchus Anticarsia spp., Barathra brassicae, Bucculatrix thurberi spp., Heterakis spp., Hymenolepis nana, Hvostrongulus spp., ella, Bupalus piniarius, Cacoeciapodana, Capua reticulana, Loa Loa, Nematodirus spp., Oesophagostomum spp., 40 Carpocapsa pomonella, Chematobia brumata, Chilo spp., Opisthorchis spp., Onchocerca volvulus, Ostertagia spp., Choristoneura filmiferana, Clysia ambiguella, Cnaphalo Paragonimus spp., Schistosomen spp., Strongyloides fielle cerus spp., Earias insulana, Ephestia kuehniella, Euproctis borni, Strongyloides Stercoralis, Strongyloides spp., Taenia chrysorrhoea, Euxoa spp., Feltia spp., Galleria mellonella, saginata, Taenia solium, Trichinella spiralis, Trichinella Helicoverpa spp., Heliothis spp., Hofinannophila pseu nativa, Trichinella britovi, Trichinella nelsoni, Trichinella 45 dospretella, Homona magnanima, Hyponomeuta padella, pseudopsiralis, Tricho strongulus spp., Trichuris trichuria, Laphygma spp., Lithocolletis blancardella, Lithophane Wuchereria bancrofti. antennata, Loxagrotis albicosta, Lymantria spp., Malaco Protozoans such as Eimeria can also be controlled. Soma neustria, Mamestra brassicae, Mocis repanda, From the order of the Heteroptera, for example Anasa Mythinna separata, Oria spp., Oulema Oryzae, Panolis flam tristis, Antestiopsis spp., Blissus spp., Calocoris spp., 50 mea, Pectinophora gossypiella, Phyllocnistis citrella, Pieris Campylomma livida, Cavelerius spp., Cimex spp., Creontia spp., Plutella xylostella, Prodenia spp., Pseudaletia spp., des dilutus, Dasynus piperis, Dichelops fircatus, Dicono Pseudoplusia includens, Pyrausta nubilalis, Spodoptera coris hewetti, Dysdercus spp., Euschistus spp., Eurygaster spp., Thermesia gemmatalis, Tinea pellionella, Tineola bis spp., Heliopeltis spp., Horcias nobilellus, Leptocorisa spp., selliella, Tortrix viridana, trichoplusia spp. Leptoglossus phyllopus, Lygus spp., Macropes excavatus, 55 From the order of the Orthoptera, for example Acheta Miridae, Nezara spp., Oebalus spp., Pentomidae, Piesma domesticus, Blatta Orientalis, Blattella germanica, Gryllo quadrata, Piezodorus spp., Psalus seriatus, Pseudacy.sta talpa spp., Leucophaea maderae, Locusta spp., Melanoplus persea, Rhodnius spp., Sahlbergella singularis, Scotino spp., Periplaneta americana, Schistocerca gregaria. phora spp., Stephanitis nashi, Tibraca spp., triatoma spp. From the order of the Siphonaptera, for example Cerato From the order of the Homoptera, for example Acyrtho 60 phyllus spp., Xenopsylla cheopis. Sipon spp., Aeneolamia spp., Agonoscena spp., Aleurodes From the order of the Symphyla, for example Scutigerella spp., Aleurolobus barodensis, Aleurothrixus spp., Amrasca immaculate. spp., Anuraphis cardui, Aonidiella spp., Aphanostigma piri, From the order of the Thysanoptera, for example Balio Aphis spp., Arboridia apicalis, Aspidiella spp., Aspidiotus thrips biformis, Enneothrips flavens, Frankliniella spp., spp., Atanus spp., Aulacorthum Solani, Bemisia spp., Brachy 65 Heliothrips spp., Hercinothrips femoralis, Rhipiphorothrips caudus helichrysii, Brachycolus spp., Brevicoryne brassicae, cruentatus, Scirtothrips spp., Taeniothrips cardanoni, Thrips Calligypona marginata, Carneocephalafiulgida, Ceratova SPD. US 8,110,689 B2 23 24 From the order of the Thysanura, for example Lepisma as acetone, methyl ethyl ketone, methyl isobutyl ketone or saccharina. cyclohexanone, strongly polar solvents, such as dimethyl Sul The plant-parasitic nematodes include, for example, Aph phoxide, and water. elen.choides spp., Bursaphelenchus spp., Dity lenchus dipsaci, As solid carriers there are suitable: Globodera spp., Heterodera spp., Longidorus spp., Meloid for example ammonium salts and ground natural minerals, ogyne spp., Pratylenchus spp., Radopholus similis, tri Such as kaolins, clays, talc, chalk, quartz, attapulgite, mont chodorus spp., Tilenchulus semipenetrans, Xiphinema spp. morillonite or diatomaceous earth, and ground synthetic min In certain concentrations or application rates, the com erals, such as highly disperse silica, alumina and silicates; as pounds according to the invention can, if appropriate, also be solid carriers for granules there are suitable: for example 10 crushed and fractionated natural rocks such as calcite, used as herbicides, Safeners, growth regulators or agents for marble, pumice, Sepiolite and dolomite, and synthetic gran improving the plant characteristics, or as microbicides, for ules of inorganic and organic meals, and granules of organic example as fungicides, antimycotics, bactericides, Virucides material Such as sawdust, coconut shells, maize cobs and (including as agents against Viroids) or as agents against tobacco stalks; as emulsifiers and/or foam formers there are MLOs (Mycoplasma-like organisms) and RLOs (Rickettsia 15 Suitable: for example nonionic and anionic emulsifiers. Such like organisms). They can also be employed as intermediates as polyoxyethylene fatty acid esters, polyoxyethylene fatty or precursors for the synthesis of further active compounds if alcohol ethers, for example alkylaryl polyglycol ethers, alkyl appropriate. Sulphonates, alkyl Sulphates, arylsulphonates and protein All plants and plant parts can be treated in accordance with hydrolysates; as dispersants there are suitable: for example the invention. In this context, plants are understood as mean lignoSulphite waste liquors and methylcellulose. ing all plants and plant populations, such as desired and Adhesives such as carboxymethylcellulose and natural and undesired wild plant or crop plants (including naturally synthetic polymers in the form of powders, granules or lati occurring crop plants). Crop plants may be plants which can ces, such as gum arabic, polyvinyl alcohol and polyvinyl be obtained by conventional breeding and optimization meth acetate, and natural phospholipids. Such as cephalins and ods or by biotechnological and genetic-engineering methods 25 lecithins, and synthetic phospholipids can be used in the or by combinations of these methods, including the trans formulations. Further additives may be mineral and vegetable genic plants and including the plant varieties capable or not of oils. being protected by Plant Breeders’ Rights. Plant parts are It is possible to use colorants such as inorganic pigments, understood as meaning all aerial and Subterranean parts and for example iron oxide, titanium oxide and Prussian Blue, and 30 organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs organs of the plants, such as shoot, leaf, flower and root, and metal phthalocyanine dyestuffs, and trace nutrients such examples which may be mentioned being leaves, needles, as salts of iron, manganese, boron, copper, cobalt, molybde stalks, stems, flowers, fruit bodies, fruits and seeds, and also num and zinc. roots, tubers and rhizomes. The plant parts also include har The formulations in general comprise between 0.1 and Vested material and vegetative and generative propagation 35 95% by weight of active compound, preferably between 0.5 material, for example cuttings, tubers, rhizomes, slips and and 90%. seeds. The active compounds according to the invention, in com The treatment according to the invention of the plants and mercially available formulations and in the use forms pre plant parts with the active compounds is carried out directly pared from these formulations, can be present in a mixture or by acting on their environment, habitat or store, using 40 with other known active compounds such as insecticides, customary treatment methods, for example by immersion, attractants, sterilants, bactericides, acaricides, nematicides, spraying, vaporizing, fogging, broadcasting, painting on, fungicides, growth regulators or herbicides, Safeners, fertil injecting and, in the case of propagation material, in particular izers or semiochemicals. in the case of seeds, furthermore by coating with one or more Examples of especially advantageous components in the COats. 45 mixtures are the following: The active compounds can be converted into the customary Fungicides: formulations, such as solutions, emulsions, wettable pow 2-phenylphenol; 8-hydroxyquinoline Sulphate; acilben ders, water- and oil-based Suspensions, powders, dusts, Zolar-S-methyl; aldimorph; amidoflumet, ampropylfos; pastes, Soluble powders, soluble granules, granules, for ampropylfos-potassium; andoprim; anilazine, azaconazole; broadcasting, Suspoemulsion concentrates, natural materials 50 azoxystrobin; benalaxyl; benodanil; benomyl; benthiavali impregnated with active compounds, synthetic materials carb-isopropyl; benzamacril; benzamacril-isobutyl: impregnated with active compounds, fertilisers and microen bilanafos; binapacryl; biphenyl; bitertanol; blasticidin-S; capsulations in polymeric materials. bromuconazole; bupirimate; buthiobate; butylamine; cal These formulations are produced in a known manner, for cium polysulphide; capsimycin; captafol; captan; carbenda example by mixing the active compounds with extenders, that 55 Zim; carboxin; carpropamid; carvone; quinomethionate; is, liquid solvents and/or solid carriers, optionally with the use chlobenthiazone; chlorfenazole; chloroneb; chloro-thalonil; of Surface-active agents, that is, emulsifiers and/or dispers chloZolinate; cloZylacon; cyaZofamid; cyflufenamid; ants and/or foam formers. cymoxanil; cyproconazole, cyprodinil; cyprofuram; Dagger If water is used as extender, auxiliary solvents which can G; debacarb; dichiofluanid; dichlone; dichlorophen; diclo also be used are, for example, organic solvents. As liquid 60 cymet; diclomeZine; dicloran; diethofencarb; difenocona Solvents, there are suitable in the main: aromatics, such as Zole; diflumetorim; dimethirimol; dimethomorph; dimox Xylene, toluene or alkylnaphthalenes, chlorinated aromatics ystrobin: diniconazole; diniconazole-m; dinocap: or chlorinated aliphatic hydrocarbons, such as chloroben diphenylamine; dipyrithione; ditalimfos; dithianon; dodine; Zenes, chloroethylenes or methylene chloride, aliphatic draZOXolon; edifenphos; epoxiconazole; ethaboxam, ethiri hydrocarbons, such as cyclohexane or paraffins, for example 65 mol; etridiazole; fam-oxadone; fenamidone; fenapanil; fena mineral oil fractions, mineral and vegetable oils, alcohols, rimol; fenbuconazole; fenfuram; fenhexamid; fenitropan: Such as butanol or glycol and ethers and esters, ketones, such fenoxanil; fenpiclonil; fempropidin; fempropimorph, ferbam; US 8,110,689 B2 25 26 fluazinam; flubenzimine; fludioxonil; flumetover; flumorph; fos, chlorfenvinphos, chlormephos, chloropyrifos(-me fluoromide; fluoxastrobin: fluguinconazole; flurprimidol; thyl/-ethyl), coumaphos, cyanofenphos, cyanophos, flusilazole; flusulphamide; flutolanil; flutriafol; folpet; fos chlorfenvinphos, demeton-S-methyl, demeton-S-meth etyl-Al; fosetyl-sodium; fuberidazole; furalaxyl; furametpyr; ylsulphon, dialifos, diazinon, dichlofenthion, dichlor furcarbanil; furmecyclox, guazatline; hexachlorobenzene: vos/DDVP, dicrotophos, dimethoate, dimethylvinphos, hexaconazole; hymexaZol; imazalil; imibenconazole; imi dioxabenzofos, disulphoton, EPN, ethion, ethoprophos, noctadine triacetate; iminoctadine tris(albesilate); iodocarb; etrimfos, famphur, fenamiphos, fenitrothion, fensul ipconazole, iprobenfos: iprodione; iprovalicarb; irumamy phothion, fenthion, flupyrazofos, fonofos, formothion, cin; isoprothiolane; isovaledione; kasugamycin, kresoxim foSmethilan, fosthiazate, heptenophos, iodofenphos, methyl; mancoZeb; maneb, meferimZone; mepanipyrim, 10 mepronil; metalaxyl; metalaxyl-M; metconazole; methasul iprobenfos, isaZofos, isofenphos, isopropyl O-Salicy phocarb; methfuroxam; metiram; metominostrobin: metSul late, isoxathion, malathion, mecarbam, methacrifos, phoVax; mildiomycin; myclobutanil; mycloZolin; natamycin; methamidophos, methidathion, mevinphos, monocroto nicobifen; nitrothal-isopropyl; noviflumuron, nuarimol; ofu phos, naled, omethoate, oxydemeton-methyl, parathion race; orysastrobin, oxadixyl; oXolinic acid; Oxpo-conazole; 15 (-methyl/-ethyl), phenthoate, phorate, phosalone, phos oxycarboxin; oxyfenthiin, paclobutraZol; pefurazoate; pen met, phosphamidon, phosphocarb, phoxim, pirimiphos conazole; pencycuron; phosdiphen; phthalide; picox (-methyl/-ethyl), profenofos, propaphos, propetamphos, yStrobin, piperalin; polyoxins; polyoxorim; probenazole; prothiofos, prothoate, pyraclofos, pyridaphenthion, prochloraz; procymidone; propamocarb; propanosine-So pyridathion, quinallphos, Sebufos, Sulfotep, Sulprofos, dium; propiconazole; propineb; produinazid; prothiocona tebupirimfos, temephos, terbufos, tetrachlorvinphos, Zole; pyraclostrobin; pyrazophos; pyrifenox, pyrimethanil; thiometon, triaZophos, triclorfon, Vamidothion pyroquilon; pyroxyfur, pyrrolnitrine; quinconazole; qui Sodium Channel Modulators/Voltage-dependent Sodium noxyfen, quintoZene; Simeconazole; spiroxamine; Sulphur; Channel Blockers tebuconazole; tecloftalam, tecnaZene; tetcyclacis; tetracona pyrethroids, Zole; thiabendazole; thicyofen; thifluzamide; thiophanate 25 for example acrinathrin, allethrin (d-cis-trans, d-trans), methyl; thiram; tioxymid; tolclofos-methyl; tolylfluanid; tri beta-cyfluthrin, bifenthrin, bioallethrin, bioallethrin-S- adimefon: triadimenol; triazbutil; triazoxide; tricyclamide: cyclopentyl isomer, bioethanomethrin, biopermethrin, tricyclazole; tridemorph; trifloxystrobin; tri-flumizole; trifo bioresmethrin, chlovaporthrin, cis-cypermethrin, cis rine; triticonazole; uniconazole; validamycin A; VincloZolin; resmethrin, cis-permethrin, clocythrin, cycloprothrin, Zineb; Ziram; Zoxamide; (2S)-N-2-4-3-(4-chlorophenyl)- 30 cyfluthrin, cyhalothrin, cypermethrin (alpha-, beta-, 2-propynyloxy-3-methoxyphenylethyl-3-methyl-2-(me theta-, Zeta-), cyphenothrin, deltamethrin, empenthrin thylsulphonyl)amino-butanamide: 1-(1-naphthalenyl)-1H (1R isomer), esfenvalerate, etofenprox, fenfluthrin, fen pyrrole-2,5-dione: 2,3,5,6-tetrachloro-4-(methylsulphonyl)- propathrin, fenpyrithrin, fenvalerate, flubrocythrinate, pyridine; 2-amino-4-methyl-N-phenyl-5- flucythrinate, flufenprox, flumethrin, fluvalinate, thiazolecarboxamide: 2-chloro-N-(2,3-dihydro-1,1,3- 35 fubfenproX, gamma-cyhalothrin, imiprothrin, kade trimethyl-1H-inden-4-yl)-3-pyridincarboxamide: 3,4,5- thrin, lambda-cyhalothrin, metofluthrin, permethrin trichloro-2,6-pyridinedicarbonitrile; actinovate; cis-1-(4- (cis-, trans-), phenothrin (1R trans isomer), prallethrin, chlorophenyl)-2-(1H-1,2,4-triazole-1-yl)-cycloheptanol: profluthrin, protrifenbute, pyresmethrin, resmethrin, RU methyl 1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H 15525, silafluofen, tau-fluvalinate, tefluthrin, teral imidazole-5-carboxylate; monopotassium carbonate, N-(6- 40 lethrin, tetramethrin (1R isomer), tralomethrin, trans methoxy-3-pyridinyl)-cyclopropanecarboxamide: N-butyl fluthrin, ZXI 8901, pyrethrins (pyrethrum) 8-(1,1-dimethylethyl)-1-oxaspiro-4.5 decan-3-amine; DDT Sodium tetrathiocarbonate; and copper salts and preparations, oxadiazines, Such as Bordeaux mixture; copper hydroxide; copper naph for example indoxacarb thenate; copper oxychloride; copper Sulphate; cufraneb; 45 Acetylcholin Receptor Agonists/Antagonists cuprous oxide; mancopper, oxine-copper. Chloronicotinyls, Bactericides: for example acetamiprid, clothianidin, dinotefuran, imida bronopol, dichlorophen, nitrapyrin, nickel dimethyldithio cloprid, nitenpyram, nithiazine, thiacloprid, thia carbamate, kasugamycin, octhillinone, furancarboxylic acid, methoxam oxytetracyclin, probenazole, streptomycin, tecloftalam, cop 50 nicotine, benSultap, cartap per Sulphate and other copper preparations: Acetylcholin Receptor Modulators Insecticides/Acaricides/Nematicides: spinosyns, Acetylcholin Esterase (AChE). Inhibitors for example spinosad carbamates, GABA-controlled Chloride Channel Antagonists for example alanycarb, aldicarb, aldoxycarb, allyxycarb, 55 organochlorins, aminocarb, bendiocarb, benfuracarb, bufencarb, butac for example camphechlor, chlordane, endosulphan, arb, butocarboxim, butoxycarboxim, carbaryl, carbofu gamma-HCH, HCH, heptachlor, lindane, methoxychlor ran, carboSulphan, cloethocarb, dimetilan, ethiofencarb, fiprols, fenobucarb, fenothiocarb, formetanate, furathiocarb, for example acetoprole, ethiprole, fipronil, pyrafluprole, isoprocarb, metam-Sodium, methiocarb, methomyl, 60 pyriprole, Vaniliprole metolcarb, oxamyl, pirimicarb, promecarb, propoXur, Chloride Channel Activators thiodicarb, thiofanox, trimethacarb. XMC, xylylcarb, mectins, triazamate for example lepimectin, abamectin, avermectin, emamec organophosphates, tin, emamectin-benzoate, ivermectin, milbemycin for example acephate, azamethiphos, azinphos (-methyl, 65 Juvenile Hormone Mimetics, -ethyl), bromophos-ethyl, bromfenvinfos (-methyl), for example diofenolan, epolfenonane, fenoxycarb, hydro butathiofos, cadusafos, carbophenothion, chlorethoxy prene, kinoprene, methoprene, pyriproxifen, triprene US 8,110,689 B2 27 28 Ecdysone Agonists/Disruptors antifeedants, diacylhydrazines, for example cryolite, flonicamid, pymetrozine for example chromafenozide, halofenozide, methoxy mite growth inhibitors, fenozide, tebufenozide for example clofentezine, etoxazole, hexythiaZOX Chitin Biosynthesis Inhibitors amidoflumet, benclothiaz, benzoximate, bifenazate, bro benzoylureas, mopropylate, buprofezin, chino-methionat, chlordime for example bistrifluoron, chlofluaZuron, diflubenzuron, form, chlorobenzilate, chloropicrin, clothiazoben, fluaZuron, flucycloXuron, flufenoXuron, hexaflumuron, cycloprene, cyflumetofen, dicyclanil, fenoxacrim, fen lufenuron, novaluron, noviflumuron, penfluoron, trifanil, flubenzimine, flufenerim, flutenZin, gossyplure, teflubenzuron, triflumuron 10 hydramethylnone, japonilure, metoxadiaZone, petro buprofezin leum, piperonyl butoxide, potassium oleate, pyridalyl, cyromazine sulfluramid, tetradifon, tetrasul, triarathene, verbutin Inhibitors of Oxidative Phosphorylation, ATP Disruptors A mixture with other known active compounds such as diafenthiuron herbicides, fertilizers, growth regulators, safeners, semio organotin compounds 15 chemicals or else with agents which improve the plant char for example azocyclotin, cyhexatin, fenbutatin-oxide acteristics, is also possible. Uncouplers of Oxidative Phoshorylation by Interrupting the When used as insecticides, the active compounds accord H Proton Gradient ing to the invention can furthermore be present, in their com pyrroles, mercially available formulations and in the use forms pre for example chlorfenapyr pared from these formulations as mixtures with synergists. dinitrophenols, Synergists are compounds by which the activity of the active for example binapacyrl, dinobuton, dinocap, DNOC compound is enhanced without it being necessary for the Site-I Electron Transport Inhibitors synergist added to be active itself. METI’s, When used as insecticides, the active compounds accord for example fenaZaquin, fenpyroximate, pyrimidifen, 25 ing to the invention can furthermore be present, in their com pyridaben, tebufenpyrad, tolfenpyrad mercially available formulations and in the use forms pre hydramethylnon pared from these formulations, as mixtures with inhibitors dicofol which reduce degradation of the active compound post-appli Site-II Electron Transport Inhibitors cation in the environment of the plant, on the Surface of plant rOtenone 30 parts or in plant tissues. Site-III Electron Transport Inhibitors The active compound content of the use forms prepared aceduinocyl, fluacrypyrim from the commercially available formulations can vary Microbial Disruptors of the Insect Gut Membrane within widelimits. The active compound concentration of the Bacillus thuringiensis strains use forms can be from 0.00000001 up to 95% by weight of Fat Biosynthesis Inhibitors 35 active compound, preferably between 0.00001 and 1% by tetronic acids, weight. for example spirodiclofen, spiromesi?en Application is effected in a customary manner which is tetramic acids, adapted to Suit the use forms. for example spirotetramat (CAS-Reg.-No.: 203313-25-1) As already mentioned above, all plants and their parts can and 3-(2,5-dimethylphenyl)-8-methoxy-2-oxo-1-aza 40 be treated in accordance with the invention. In a preferred use spiro4.5 dec-3-en-4-yl ethyl carbonate (also known as: form, plant species and plant varieties, and their parts, which carbonic acid, 3-(2,5-dimethylphenyl)-8-methoxy-2- are found in the wild or which are obtained by conventional oxo-1-azaspiro4.5 dec-3-en-4-yl ethyl ester, CAS biological breeding methods, such as hybridization or proto Reg.-No.: 382608-10-8), cis-3-(2,5-dimethylphenyl)-4- plast fusion, are treated. In a further preferred embodiment, hydroxy-8-methoxy-1-aspiro4.5 dec-3-en-2-one 45 transgenic plants and plant varieties, and their parts, which carboxamide, have been obtained by genetic engineering methods, if appro for example flonicamid priate in combination with traditional methods (genetically Octopaminergic agonists, modified organisms) are treated. The terms “parts”, “parts of for example amitraz plants' or “plant parts” have been detailed above. Inhibitors of Magnesium-stimulated ATPase, 50 It is especially preferred to treat, in accordance with the propargite invention, plants of the plant varieties which are in each case benzoic acid dicarboxamides, commercially available or in use. Plant cultivars are under for example flubendiamide stood as meaning plants with new properties (“traits') which anthranilic acid amides, have been obtained by conventional cultivation, by mutagen for example Rynaxypyr 55 esis or else by recombinant DNA techniques. These may be nereistoxin analogues, cultivars, biotypes or genotypes. for example thiocyclam hydrogen oxalate, thiosultap-so Depending on the plant species or plant cultivars, their dium location and growth conditions (soils, climate, vegetation Biologicals, Hormones or Pheromones period, nutrition), the treatment according to the invention azadirachtin, Bacillus spec. Beauveria spec., codilemone, 60 may also result in superadditive (“synergistic) effects. Thus, Metarrhizium spec., Paecilomyces spec. Thuringiensin, for example, reduced application rates and/or widenings of Verticillium spec. the activity spectrum and/or an increase in the activity of the Active Compounds with Unknown or Unspecific Mecha Substances and compositions that can be used according to nisms of Action the invention, better plant growth, increased tolerance to high fumigants, 65 or low temperatures, increased tolerance of the crop plants to for example aluminium phosphide, methyl bromide, Sul drought or to water or soil salinity, increased flowering per phuryl fluoride formance, easier harvesting, accelerated maturation, higher US 8,110,689 B2 29 30 yields, better quality and/or a higher nutritional value of the The plants listed can be treated according to the invention harvested products, better storage stability and/or process in a particularly advantageous manner with the compounds of ability of the harvested products which exceed the effects the general formula I or the active compound mixtures which were actually to be expected are possible. according to the invention. The preferred ranges stated above The preferred transgenic plants or plant cultivars (i.e. those for the active compounds or mixtures also apply to the treat obtained by genetic engineering) which are to be treated ment of these plants. Particular emphasis is given to the according to the invention include all plants which, by genetic treatment of plants with the compounds or mixtures specifi modification, received genetic material which imparted par cally mentioned in the present text. ticularly advantageous useful properties (“traits”) to these The active compounds according to the invention are not 10 only active against plant pests, hygiene pests and stored plants. Examples of Such properties are better plant growth, product pests, but also, in the sector of Veterinary medicine, increased tolerance to high or low temperatures, increased against animal parasites (ecto- and endoparasites) Such as tolerance to drought or to water or soil salinity, increased hard ticks, soft ticks, Scab mites, harvest mites, flies (stinging flowering performance, easier harvesting, accelerated matu and licking), parasitic fly larvae, lice, hair lice, bird lice and ration, higher yields, better quality and/or a higher nutritional 15 flees. These parasites include: value of the harvested products, betterstorage stability and/or From the order of the Anoplurida, for example Haematopi processability of the harvested products. Further and particu nus spp., Linognathus spp., Pediculus spp., Phtirus spp., Sole larly emphasized examples of Such properties are a better nopotes spp. defense of the plants against animal and microbial pests. Such From the order of the Mallophagida and the suborders as against insects, mites, phytopathogenic fungi, bacteria Amblycerina and Ischnocerina, for example trimenopon spp., and/or viruses, and also increased tolerance of the plants to Menopon spp., trinoton spp., Bovicola spp., Werneckiella certain herbicidally active compounds. Examples of trans spp., Lepikentron spp., Damalina spp., trichodectes spp., genic plants which may be mentioned are the important crop Felicola spp. plants, such as cereals (wheat, rice), maize, soya beans, pota From the order of the Diptera and the suborders Nemato toes, Sugar beet, tomatoes, peas and other vegetables, cotton, 25 cerina and Brachycerina, for example Aedes spp., Anopheles tobacco, oilseed rape and also fruit plants (with the fruits spp., Culex spp., Simulium spp., Eusimulium spp., Phleboto apples, pears, citrus fruits and grapes), and particular empha mus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., sis is given to maize, soya beans, potatoes, cotton, tobacco Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota and oilseed rape. Traits that are emphasized in particular are spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea increased defense of the plants against insects, arachnids, 30 spp., Stomoxys spp., Haematobia spp., Morelia spp., Fannia nematodes, slugs and Snails as the result of toxins formed in spp., Glossina spp., Caliphora spp., Lucilia spp., Chry the plants, in particular those formed in the plants by the somyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus genetic material from Bacillus thuringiensis (for example by spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., the genes CryIA(a), CryIA(b), CryIA(c), Cry IIA, Cry IIIA, Lipoptena spp., Mellophagus spp. CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CryIF and also com 35 From the order of the Siphonapterida, for example Pulex binations thereof) (hereinbelow referred to as “Bt plants'). spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus Traits which are also particularly emphasized are the spp. increased defense of plants against fungi, bacteria and viruses From the order of the Heteropterida, for example Cimex by Systemic acquired resistance (SAR), Systemin, phytoalex spp., triatoma spp., Rhodnius spp., Panstrongylus spp. ins, elicitors and resistance genes and the correspondingly 40 From the order of the Blattarida, for example Blatta Orien expressed proteins and toxins. Traits that are furthermore talis, Periplaneta americana, Blattela germanica, Supella particularly emphasized are the increased tolerance of the spp. plants to certain herbicidally active compounds, for example From the subclass of the Acari (Acarina) and the orders of imidazolinones, Sulphonylureas, glyphosates or phosphino the Meta- and Mesostigmata, for example Argas spp., Orni thricin (for example the "PAT gene). The genes which impart 45 thodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., the desired traits in question can also be present in combina Boophilus spp., Dermacentor spp., Haemophysalis spp., tion with one another in the transgenic plants. Examples of Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., “Bt plants’ which may be mentioned are maize varieties, Raillietia spp., Pneumonyssus spp., Sternostoma spp., Varroa cotton varieties, soya bean varieties and potato varieties spp. which are sold under the trade names YIELD GARDR) (for 50 From the order of the Actinedida (Prostigmata) and Acari example maize, cotton, soya beans), KnockCut(R) (for dida (Astigmata), for example Acarapis spp., Cheyletiella example corn), StarLink R. (for example corn), Bollgard(R) spp., OrnithOcheyletia spp., Myobia spp., Psorergates spp., (cotton), Nucotnr (cotton) and New Leaf R (potato). Demodex spp., Trombicula spp., Listrophorus spp., Acarus Examples of herbicide-tolerant plants which may be men spp., Trophagus spp., Caloglyphus spp., Hypodectes spp., tioned are maize varieties, cotton varieties and Soya bean 55 Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes varieties which are sold under the trade names Roundup spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Ready R (tolerance to glyphosates, for example maize, cot Cytodites spp., Laminosioptes spp. ton, soya beans), Liberty Link. R (tolerance to phosphinothri The active compounds of the formula I according to the cin, for example oilseed rape), IMIR (tolerance to imidazoli invention are also suitable for controlling arthropods which nones) and STS(R) (tolerance to Sulphonylureas, for example 60 attack agricultural livestock Such as, for example, cattle, maize). Herbicide-resistant plants (plants bred in a conven sheep, goats, horses, pigs, donkeys, camels, buffaloes, rab tional manner for herbicide tolerance) which may be men bits, chickens, turkeys, ducks, geese, honeybees, other tioned also include the varieties sold under the name domestic animals such as, for example, dogs, cats, cage birds, Clearfield(R) (for example maize). Of course, these statements aquarium fish and what are known as experimental animals also apply to plant varieties having these genetic traits or 65 Such as, for example, hamsters, guinea pigs, rats and mice. By genetic traits, which will be developed in the future, which controlling these arthropods, it is intended to reduce deaths varieties will be developed and/or marketed in the future. and reduce performance (in the case of meat, milk, wool, US 8,110,689 B2 31 32 hides, eggs, honey and the like), so that more economical and Furthermore, the compounds according to the invention, simpler animal keeping is made possible by the use of the alone or in combinations with other active compounds, may active compounds according to the invention. be employed as antifouling agents. In the veterinary sector and in animal keeping, they are The active compounds are also Suitable for controlling applied in the known manner by enteral administration in the animal pests in the protection of domestic premises, in the form of for example, tablets, capsules, drinks, drenches, field of hygiene and of stored products, in particular insects, granules, pastes, boluses, the feed-through method, Supposi arachnids and mites which are found in enclosed spaces Such tories, by parenteral administration, Such as, for example, by as for example, dwellings, factory halls, offices, drivers cab injections (intramuscular, Subcutaneous, intravenous, intrap 10 ins and the like. To control these pests they can be used in eritoneal and the like), implants, by nasal application, by insecticidal products for domestic premises, either alone or in dermal application in the form of for example, bathing or combination with other active compounds and auxiliaries. dipping, spraying, pouring-on and spotting-on, Washing, They are active against sensitive and resistant species and dusting, and with the aid of active-compound-comprising 15 against all developmental stages. These pests include: shaped articles Such as collars, ear tags, tail tags, limb bands, From the order of the Scorpionidea, for example Buthus halters, marking devices and the like. OCCitanus. When used for livestock; poultry, domestic animals and the From the order of the Acarina, for example Argas persicus, like, the active compounds of the formula I can be applied as 2O Argas reflexus, Bryobia ssp., Dermanyssus gallinae, Glyci formulations (for example powders, emulsions, flowables) phagus domesticus, Ornithodorus moubat, Rhipicephalus which comprise the active compounds in an amount of from sanguineus, Trombicula alfreddugesi, Neutrombicula autum 1 to 80% by weight, either directly or after 100- to 10000-fold nalis, Dermatophagoides pteronissimus, Dermatophagoides dilution, or else as a chemical bath. forinae. Furthermore, it has been found that the active compounds 25 From the order of the Araneae, for example Aviculariidae, according to the invention have a potent insecticidal activity Araneidae. against insects which destroy industrial materials. From the order of the Opiliones, for example Pseudoscor The following insects may be mentioned by way of piones chelifer, Pseudoscorpiones cheiridium, Opiliones example and by preference, but not by limitation: 30 phalangium. Beetles such as From the order of the Isopoda, for example Oniscus asel Hylotrupes bajulus, Chlorophorus pilosis, Anobium punc lus, Porcellio scaber: tatum, Xestobium rufo villosum, Ptilinus pecticornis, Dendro From the order of the Diplopoda, for example Blaniulus bium pertinex, Ernobius mollis, Priobium carpini, Lyctus guttulatus, Polydesmus spp. brunneus, Lyctus africanus, Lyctus planicollis, Lyctus lin 35 From the order of the Chilopoda, for example Geophilus earis, Lyctus pubescens, Trogoxylon aequale, Minthes rugi spp. collis, Xvleborus spec. Tryptodendron spec. Apate monachus, From the order of the Zygentoma, for example Ctenolepi Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon Sma spp., Lepisma Saccharina, Lepismodes inquilinus. spec. Dinoderus minutus. 40 From the order of the Blattaria, for example Blatta Orien Heminoptera Such as tallies, Blattella germanica, Blattella asahinai, Leucophaea Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, maderae, Panchlora spp., Parcoblatta spp., Periplaneta aus Urocerus augur: tralasiae, Periplaneta americana, Periplaneta brunnea, Termites such as 45 Periplaneta fuliginosa, Supella longipalpa. Kalotermes flavicollis, Cryptotermes brevis, Heterotermes From the order of the Saltatoria, for example Acheta indicola, Reticulitermes flavipes, Reticulitermes Santonensis, domesticus. Reticulitermes lucifigus, Mastotermes darwiniensis, Zooter From the order of the Dermaptera, for example Forficula mopsis nevadensis, Coptotermes formosanus. auricularia. Bristletails such as Lepisma saccharina. " From the order of the Isoptera, for example Kalotermes Industrial materials are understood as meaning, in the spp., Reticulitermes spp. present context, non-live materials such as, preferably, poly From the order of the Psocoptera, for example Lepinatus mers, adhesives, glues, paper and board, leather, wood, spp., LipOscelis spp. derived timber products and paints. 55 From the order of the Coleoptera, for example Anthrenus If appropriate, the ready-to-use compositions may addi spp., Attagenus spp., Dermestes spp., Latheticus Oryzae, tionally comprise further insecticides and, if appropriate, Necrobia spp., Ptinus spp., Rhizopertha dominica, Sitophilus additionally one or more fungicides. granarius, Sitophilus Oryzae, Sitophilus zeanais, Stegobium As regards potential additional components in mixtures, paniceum. reference may be made to the abovementioned insecticides " From the order of the Diptera, for example Aedes aegypti, and fungicides. Aedes albopictus, Aedes taeniorhynchus, Anopheles spp., The compounds according to the invention can also be Caliphora erythrocephala, Chrysozona pluvialis, Culex employed for protecting growths on objects, in particular quinquefasciatus, Culex pipiens, Culex tarsalis, Drosophila ships' hulls, sieves, nets, buildings, moorings and signal sys 6s spp., Fannia canicularis, Musca domestica, Phlebotomus tems which come into contact with salt water or brackish spp., Sarcophaga carnaria, Simulium spp., Stomoxys calci Water. trans, Tipula paludosa. US 8,110,689 B2 33 34 From the order of the Lepidoptera, for example Achroia Synthesis Eample 2 grisella, Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tinea pellionella, Tineola bisselliella. From the order of the Siphonaptera, for example Cteno cephalides canis, Ctenocephalides fells, Pulex irritans, Tunga penetrans, Xenopsylla cheopis. From the order of the Hymenoptera, for example Cam ponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp., Tet 10 ramorium caespitum. O CH CF From the order of the Anoplura, for example Pediculus humanus capitis, Pediculus humanus corporis, Phthirus N pubis. From the order of the Heteroptera, for example Cimex 15 hemipterus, Cimex lectularius, Rhodinus prolixus, Triatoma CF infestans. The application in the field of the domestic insecticides may also be carried out alone or in combination with other Suitable active compounds such as phosphoric esters, car N4-(3.5-bis-trifluoromethyl-benzyl)-2-methylphenyl bamates, pyrethroids, neo-nicotinoids, growth regulators or 3-chloro-N'-(S)-1-methyl-2-methylsulfanyl-ethyl)phthala active compounds from other known classes of insecticides. mide (0.19 g) was dissolved in methylene chloride, to which The application is carried out in aerosols, unpressurized m-chloroperbenzoic acid (0.08 g) was added, and stirred at sprays, for example pump sprays and atomizer sprays, auto room temperature for 3 hours. After the reaction, it was matic misting devices, foggers, foams, gels, vaporizer prod 25 washed with a sodium thiosulfate Solution, a saturated ucts with vaporizer platelets made of cellulose or polymer, Sodium bicarbonate solution and a Saturated salt Solution, and liquid vaporizers, gel and membrane vaporizers, propeller the organic layer was dried over anhydrous magnesium Sul driven vaporizers, vaporization systems which do not con fate. Sume energy (passive vaporization systems), moth papers, The solvent was distilled off under reduced pressure and moth Sachets and moth gels in the form of granules or dusts, 30 the resultant residue was purified by silica gel column chro in baits for scattering or bait stations. matography to obtain N'-[4-(3.5-bis-trifluoromethyl-ben The preparation and the use of the substances according to Zyl)-2-methylphenyl-3-chloro-N'-(2-methanesulfinyl-(S)- the invention can be seen from the examples which follow. 1-methyl-ethyl)phthalamide (0.12 g). EXAMPLES 35 Melting point: 162-165° C. The present invention is more specifically explained using Synthesis Example 3 the following examples. The examples are not intended to limit the present invention. 40 Synthesis Example 1 CH3 (O)2

C N --- YCH, CH3 45 S O CH3 C --- NCH, N

O CH CF 50 N CF N'-[4-(3.5-bis-trifluoromethyl-benzyl)-2-methylphenyl CF 55 3-chloro-N'-(S)-1-methyl-2-methylsulfanyl-ethyl)phthala mide (0.22 g) was dissolved in methylene chloride, to which 4-Chloro-3-(S)-1-methyl-2-methylthioethylimino-3-H- m-chloroperbenzoic acid (0.20 g) was added, and stirred at isobenzofuran-1-one (0.2 g) and 4-(3,5-bis-trifluoromethyl room temperature for 3 hours. After the reaction was finished, benzyl)-2-methylaniline (0.22 g) were dissolved in acetoni it was washed with a sodium thiosulfate Solution, a Saturated trile (10 ml), to which p-toluenesulfonic acid hydrate (0.01 g) 60 Sodium bicarbonate solution and a Saturated salt Solution, and was added, and then stirred at room temperature for three the organic layer was dried over anhydrous magnesium Sul hours. After the reaction, the solvent was distilled off under fate. The solvent was distilled offunder reduced pressure and reduced pressure and the resultant residue was purified by the resultant residue was purified by silica gel column chro silica gel column chromatography to obtain N'-[4-(3.5-bis matography to obtain N'-[4-(3.5-bis-trifluoromethyl-ben trifluoromethyl-benzyl)-2-methylphenyl-3-chloro-N'-(S)- 65 Zyl)-2-methylphenyl-3-chloro-N'-(2-methanesulfonyl-(S)- 1-methyl-2-methylthioethyl)phthalamide (0.10 g). 1-methyl-ethyl)phthalamide (0.10 g) Melting point: 57-62° C. Melting point: 155-158°C..

US 8,110,689 B2 47 48 TABLE 1-continued

US 8,110,689 B2 67 68 with ethyl acetate and washed with a saturated sodium bicar Synthesis Example 10 (Material) bonate solution and a saturated salt Solution and then dried over anhydrous magnesium Sulfate. After distilling the Sol vent off, the resultant residue was purified by silica gel col 3.5-Bis-n-perfluorobutylbenzyl bromide umn chromatography to obtain 4-(3.5-bis-trifluoromethyl benzyl)-2-methylaniline (0.22 g). 'H-NMR (CDC1)8: 2.14 (3H, s), 3.53 (2H, brs), 3.98 (2H, s), 6.52-6.63 (1H, m), 6.81-6.86 (1H, m), 7.61 (2H, s), 7.69 (1H, s) 10 Synthesis Example 8 (Material)

Methyl 3,5-bis-n-perfluorobutylbenzoate 15 CHBr

Carbon tetrabromide (0.62 g) and triphenylphosphine (0.49 g) were added to a solution of 3,5-bis-n-perfluorobutyl benzyl alcohol (0.85g) in methylene chloride (10 ml) and COMe stirred for 10 hours at room temperature. After distilling off 25 the solvent under reduced pressure, the residue was purified Methyl 3,5-diiodobenzoate (1 g), copper powder (1.6 g), by silica gel column chromatography to obtain 3,5-bis-n- n-perfluorobutyl iodide (2.7 g) and DMSO (10 ml) were perfluorobutylbenzyl bromide (0.4 g). heated and stirred at 120° C. for 3 hours. After cooling, ethyl 'H-NMR (CDC1) 8: 4.56 (2H, s), 7.74 (1H, s), 7.84 (2H,s) acetate and water were added to the reaction Solution and 30 stirred, and after filtering out the insoluble matter with a celite, the organic layer was washed with a saturated salt Synthesis Example 11 (Intermediate) Solution. After drying over anhydrous magnesium sulfate, the solvent was distilled off and the residue was purified by silica Tert-butyl 2-methyl-4-(4,4,5,5-tetramethyl-1,3,2- gel column chromatography to obtain methyl 3.5-bis-n-per 35 dioxaboran-2-yl)-phenyl-carbamate fluorobutylbenzoate (0.9 g). 'H-NMR (CDC1) 8:3.99 (3H, s), 7.96 (1H, s), 8.47 (2H, s)

Synthesis Example 9 (Material) 40

HC CH3 3.5-Bis-n-perfluorobutylbenzylalcohol O HC O O CH 45 M HN B N O CH3 HC

50 CH2OH A solution of tert-butyl (4-iodo-2-methylphenyl)carbam A solution of 5-bis-n-perfluorobutylbenzoate (0.9 g) in ate (1.39 g), pinacolborane (0.8 g), triethylamine (1.27 g), THF (5 ml) was slowly added dropwise to a solution of 55 1,1'-bis-(diphenylphosphino) ferrocenepalladium (II) chlo lithium aluminum hydride (0.75 g) in THF (10 ml) in an ice ride (0.09 g) in dioxane (20 ml) was heated and stirred in an bath. After stirring for 1 hour, the reaction solution was argon atmosphere at 80°C. for 4 hours. After cooling, water diluted with ethyl ether, to which a saturated salt solution (1 was added and stirred followed by extraction with ethyl ml) was added slowly and stirred for 30 minutes. After sepa acetate and washing with a saturated Salt solution. After dry rating and removing the insoluble matter by filtration, the ing over anhydrous magnesium Sulfate, the solvent was dis result was dried over anhydrous magnesium sulfate. After tilled offunder reduced pressure and the residue was purified distilling off the solvent under reduced pressure, the residue by silica gel column chromatography to obtain tert-butyl 2 was purified by silica gel column chromatography to obtain methyl-4-(4.4.5.5-tetramethyl-1,3,2-dioxaboran-2-yl)-phe 3,5-bis-n-perfluorobutylbenzylalcohol (0.85g). 65 nyl-carbamate (0.95 g). H-NMR (CDC1) 8: 4.90 (2H, d), 7.72 (1H, s), 7.83 (2H, H-NMR (CDC1) 8: 1.33 (13H, s), 1.55 (9H, s), 2.24 (3H, s) s), 6.38 (1H, brs), 7.58 (1H, s), 7.64 (1H, d), 7.94 (1H, d). US 8,110,689 B2 69 70 Synthesis Example 12 (Intermediate) 'H-NMR (CDC1) 8:2.11 (3H, s), 3.54 (2H, brs), 3.98 (2H, s), 6.59-6.69 (1H, m), 6.77-6.80 (2H, m), 7.58-7.73 (3H, m) Tert-butyl-4-(3,5-bis-n-perfluorobutylbenzyl)-2-me thylphenyl-carbamate Synthesis Example 14 (Material) Methyl 3,4-bis-perfluoroethylbenzoate

CH3

10

CFs 15 F5C2 COMe n-FoC4

A solution of 3,5-bis-n-perfluorobutylbenzyl bromide (0.40 g), tert-butyl 2-methyl-4-(4.4.5.5-tetramethyl-1,3,2- dioxaboran-2-yl)-phenyl-carbamate (0.22 g), tetrakis(triph A solution of methyl 3,4-diiodobenzoate (1 g), perfluoro enylphosphine)-palladium (0.05 g) and sodium carbonate ethyltrimethylsilane (1.98 g), cuprous iodide (1.96 g) and (0.22 g) in water (2 ml) and 1,2-dimethoxyethane (10 ml) was 25 potassium fluoride (0.33 g) in DMF (10 ml) was heated and heated and stirred under an argon atmosphere at 85°C. for 2 stirred in a sealed tube at 100° C. for 3 hours under an argon hours. After cooling, the reaction solution was diluted with atmosphere. After cooling, the reaction mixture was diluted ethyl acetate and, by adding water, stirred for 10 minutes. The with ethyl acetate, then the insoluble matter was filtered out organic layer was dried over anhydrous magnesium Sulfate with a celite and the organic layer was washed with a satu after washing with a saturated Salt solution. The solvent was 30 rated salt Solution. After drying over anhydrous magnesium distilled off under reduced pressure and the resultant residue sulfate, the solvent was distilled off and the residue was was purified by silica gel column chromatography to obtain purified by silica gel column chromatography to obtain tert-butyl-4-(3.5-bis-n-perfluorobutylbenzyl)-2-methylphe methyl 3,4-bis-perfluoroethylbenzoate (0.55g). nyl-carbamate (0.22 g). 'H-NMR (CDC1,) 8: 4.01 (3H, s), 7.90 (1H, d), 8.37 (1H, 'H-NMR (CDC1) 8: 1.58 (9H, s), 2.29 (3H, s), 4.02 (2H, 35 d), 8.46 (1H, s) s), 6.25 (1H, brs), 6.91 (1H, s), 6.97-7.00 (1H, m), 7.61-7.64 (3H, m), 7.77-7.80 (1H, m) Synthesis Example 15 (Material) Methyl 6-in-perfluoropropylnicotinate Synthesis Example 13 (Intermediate) 40 4-(3.5-Bis-n-perfluorobutylbenzyl)-2-methylaniline

45 COMe HN ( ) ( ) n-C4Fo 50

n-FoC4 55 Methyl 6-chloronicotinate (3 g), copper powder (2.2 g), Trifluoroacetic acid (0.5 g) was added to a solution of n-perfluoropropyl iodide (9.0 g) and DMSO (10 ml) were tert-butyl-4-(3,5-bis-n-perfluorobutylbenzyl)-2-methylphe heated and stirred at 120° C. for 3 hours. After cooling, the nyl-carbamate (0.22 g) in methylene chloride (5 ml) and reaction Solution was stirred by adding ethyl acetate and stirred at room temperature for 3 hours. After the reaction, the 60 water, then the insoluble matter was separated by filtration solvent was distilled off under reduced pressure followed by with a celite and the organic layer was washed with a satu dissolving the residue into ethyl acetate, and washed with a rated salt Solution. After drying over anhydrous magnesium saturated sodium bicarbonate Solution and a saturated Salt sulfate, the solvent was distilled off and the residue was Solution. After the organic layer was dried over anhydrous purified by silica gel column chromatography to obtain magnesium sulfate, the solvent was distilled off under 65 methyl 6-n-perfluoropropylnicotinate (4.2 g). reduced pressure to obtain 4-(3,5-bis-n-perfluorobutylben H-NMR (CDC1) 8: 3.94-4.06 (3H, m), 7.80 (1H, d), 8.50 Zyl)-2-methylaniline (0.15g). (1H, d), 9.34 (1H, d) US 8,110,689 B2 71 72 Synthesis Example 16 (Intermediate) Synthesis Example 18 (Intermediate)

3',5'-Bis-trifluoromethyl-3-methyl-4-nitrobenzophe 1-(3.5-Bis-trifluoromethylphenyl)-2.2.2-trifluoro-1- O (3-methyl-4-nitrophenyl)ethanol

CH3 CF3 10 ON CH3 CF

CF ON O O 15 OH CF CF O A solution of 1Mtetrabutylammonium fluoride in tetrahy drofuran (0.2 ml) was added to a solution of 3',5'-bis-trifluo romethyl-3-methyl-4-nitrobenzophenone (1.4 g) and trifluo romethyltrimethyl-silane (1.0 g) in tetrahydrofuran (20 ml) in an ice bath and stirred at room temperature for 8 hours. The Chromic oxide (IV) (0.41 g) was added to a solution of reaction solution was diluted with ethyl acetate and washed 4-(3,5-bis-trifluoromethyl-benzyl)-2-methylnitrobenzene with water and a saturated salt Solution. After drying over (0.3 g) in acetic acid (10 ml) and stirred at room temperature 25 anhydrous magnesium sulfate, the solvent was distilled off. for 1 hour. After the reaction, the reaction solution was The residue was dissolved in tetrahydrofuran (20 ml) and, by extracted with ethyl acetate and washed with water, a satu adding 2N hydrochloric acid (2 ml), stirred at room tempera rated Sodium bicarbonate Solution and a saturated Salt Solu ture for 30 minutes. After diluting with ethyl acetate and tion. After drying over anhydrous magnesium sulfate, the washing with water and a Saturated Salt solution and after solvent was distilled off and the residue was purified by silica 30 drying over anhydrous magnesium sulfate, the solvent was gel column chromatography to obtain 3',5'-bis-trifluorom distilled off. Then the residue was purified by silica gel col ethyl-3-methyl-4-nitrobenzophenone (0.3 g). umn chromatography to obtain 1-(3,5-bis-trifluorometh 'H-NMR (CDC1) 8: 2.68 (3H, s), 7.68-7.71 (1H, m), ylphenyl)-2.2.2-trifluoro-1-(3-methyl-4-nitrophenyl)ethanol 7.76-7.80 (1H, m), 8.08 (1H, d), 8.15 (1H, s), 8.23 (2H, s) 35 (0.8 g). 'H-NMR (CDC1) 8: 2.66 (3H, s), 7.68-7.71 (1H, m), Synthesis Example 17 (Intermediate) 7.78-7.79 (1H, m), 8.08 (1H, d), 8.14 (1H, s), 8.23 (2H, s)

(3,5-Bis-trifluoromethylphenyl)(3-methyl-4-nitro Synthesis Example 19 (Intermediate) phenyl)methanol 40 1-(3.5-Bis-trifluororomethylphenyl)-2.2.2-trifluoro 1-(3-methyl-4-nitrophenyl)ethyl methanesulfonate

45 CH CF CH3 CF3

ON O O 50 CF ON O O CF OH MsO CF

55 Sodium borohydride (0.12 g) was added to a solution of Methanesulfonyl chloride (0.11 g) was added dropwise to 3',5'-bis-trifluoromethyl-3-methyl-4-nitrobenzophenone (2.2 a solution of 1-(3,5-bis-trifluoromethylphenyl)-2.2.2-trif g) in methanol (10 ml) in an ice bath. After stirring at room luoro-1-(3-methyl-4-nitrophenyl)ethanol (0.4 g) and triethy temperature for 1 hour, and diluting with ethyl acetate, it was lamine (0.11 g) in methylene chloride (10 ml) in an ice bath washed with water and a saturated Salt solution. After drying 60 and stirred at room temperature for 1 hour. After the reaction over anhydrous magnesium sulfate, the solvent was distilled and washing with water, a dilute hydrochloric acid and a off and the residue was purified by silica gel column chroma saturated salt solution, the organic layer was dried over anhy tography to obtain (3,5-bis-trifluoromethylphenyl)(3-me drous magnesium sulfate. Under reduced pressure, the Sol thyl-4-nitrophenyl)methanol (1.6 g). vent was distilled off and the residue was purified by silica gel 65 column chromatography to obtain 1-(3,5-bis-triflurorometh H-NMR (CDC1) 8: 2.60 (3H, s), 5.98 (1H, s), 7.34-7.37 ylphenyl)-2.2.2-trifluoro-1-(3-methyl-4-nitrophenyl)ethyl (2H, m), 7.83-7.84 (3H, m), 7.99 (1H, d) methanesulfonate (0.46 g). US 8,110,689 B2 73 74 'H-NMR (CDC1) 8: 2.62 (3H, s), 3.19 (3H, s), 3.73 (1H, pot. After air-drying the treated rice, the foliage was cut in s), 7.42-746 (2H, m), 7.88 (2H, s), 8.00-8.03 (2H, m) lengths of 4-5 cm and put in a Petri dish of 9 cm in diameter filled with 2 ml of water on a filter paper. Five 2nd instar Synthesis Example 20 (Intermediate) larvae of Cnaphalocrocis medinalis were released in the dish and kept at a constant 25°C. The remaining similarly cut rice 1-(3.5-Bis-trifluoromethylphenyl)-2.2.2-trifluoro-1- foliage (/3 each) was added thereto 2 and 4 days later, and the (3-methyl-4-nitrophenyl)ethane mortality was determined by counting the number of dead insects 7 days later. The present test looked at the average results of 2 Petri dishes per group. Test ResultS: 10 In the above Biological Test Examples 1 and 2, at the CH CF concentration of 20 ppm, the insect mortality was 100% with ON Compound Nos. 19, 20, 21,56, 57,58, 65,66, 67, 88, 89,90, 98, 112, 149, 212,345, 583, 584 and 635 as representative examples of the compounds according to the present inven 15 tion. CF CF Biological Test Example 3 Myzus persicae Resistant to Organophosphorous and A solution of 1-(3,5-bis-trifluoromethylphenyl)-2.2.2-trif Carbamate Insecticides luoro-1-(3-methyl-4-nitrophenyl)ethyl methanesulfonate (0.5 g) in tetrahydrofuran (5 ml) was slowly added dropwise Test Method: About 30 captive bred organophosphorous- and carbam to a solution of lithium aluminium hydride (0.04 g) in tetrahy ate-resistant Myzus persicae per seedling were inoculated to drofuran (10 ml) in an ice bath. After stirring for 30 minutes, eggplant seedlings planted in vinyl pots of 6 cm in diameter, the reaction solution was diluted with ethyl ether, and then 25 to which the active compound solution prepared as above and stirred for 30 minutes by slowly adding a saturated salt solu water-diluted to the predetermined concentration was suffi tion (1 ml). After the insoluble matter was separated by fil ciently applied using a spray gun one day after the inocula tration, the solution was dried over anhydrous magnesium tion, and left at 28°C. in a greenhouse. The insect mortality sulfate. The solvent was distilled off under reduced pressure was determined 7 days after the application. The test was and the residue was purified by silica gel column chromatog 30 repeated twice. raphy to obtain 1-(3,5-bis-trifluoromethylphenyl)-2.2.2-trif Test Results: luoro-1-(3-methyl-4-nitrophenyl)ethane (0.11 g). At the concentration of 100 ppm, the insect mortality was 'H-NMR (CDC1) 8: 2.61 (3H, s), 4.89 (1H, q), 7.34-7.36 100% with Compound Nos. 19, 152 and 635 as representative (2H, m), 7.80 (2H, s), 7.90 (1H, s), 8.02 (1H, d) examples of the compounds according to the present inven 35 tion. Biological Test Example 1 Formulation Example 1 (Granule) Spodoptera litura Larva The granular formulation was prepared by adding 25 parts Preparation of Test Solution: 40 by weight of water to the mixture of 10 parts by weight of Solvent: 3 parts by weight of dimethylformamide Compound No. 19 of the present invention, 30 parts by weight of bentonite (montmorillonite), 58 parts by weight of talc and Emulsifier: 1 part by weight of polyoxyethylene alkylphenyl 2 parts by weight of lignoSulfonate, and Sufficiently kneaded ether followed by granulating into 10-40 mesh granules using an To prepare a suitable formulation of the active compound, extruding granulator, and drying at 40-50° C. 1 part by weight of the active compound was mixed with the 45 above solvent containing the above emulsifier, and the mix Formulation Example 2 (Granule) ture was diluted with water to a predetermined concentration. Test Method: 95 Parts by weight of clay mineral particles having a par Sweet potato leaves were dipped in the test solution which ticle size distribution of 0.2-2 mm were placed in a revolving was water-diluted to the predetermined concentration, then 50 blender, which were then sprayed with 5 parts by weight of air-dried and put in a Petridish of 9 cm in diameter, in which Compound No. 20 of the present invention together with a ten 3rd instar larvae of Spodoptera litura were released, then liquid diluent during the rotation for uniform moistening kept at a constant 25°C. Additional sweet potato leaves were followed by drying at 40-50° C. to give the granular formu added 2 and 4 days later, and the mortality was determined by lation. counting the number of dead insects 7 days later. 55 The present test looked at the average results of 2 Petri Formulation Example 3 (Emulsifiable Concentrate) dishes per group. 30 Parts by weight of Compound No. 56 of the present Biological Test Example 2 invention, 55 parts by weight of xylene, 8 parts by weight of 60 polyoxyethylenealkylphenylether and 7 parts by weight of Cnaphalocrocis medinalis Larva calcium alkylbenzenesulfonic acid were mixed and stirred to give the emulsifiable concentrate. Test Method: A test solution, water-diluted to the predetermined concen Formulation Example 4 (Wettable Powder) tration of the active compound, prepared in the same manner 65 as in Biological Test Example 1 above was applied to pot 15 Parts by weight of Compound No. 65 of the present transplanted rice (Tamanishiki variety) at the rate of 50 ml per invention, 80 parts by weight of the mixture of white carbon US 8,110,689 B2 75 76 (hydroscopic amorphous silicon oxide fine powder) and clay (a) reacting at least one compound of formula (II): powder (1:5), 2 parts of sodium alkylbenzenesulfonic acid and 3 parts by weight of Sodium alkylnaphthalenesulfonic acid formalin condensate were ground and mixed to give the wettable powder. (II) Formulation Example 5 (Wettable Granule) To prepare the wettable granule formulation, 20 parts by weight of Compound No. 112 of the present invention, 30 10 parts by weight of sodium lignoSulfonate, 15 parts by weight of bentonite and 35 parts by weight of calcined diatomaceous earth powder were mixed well, and then water was added thereto followed by the extrusion using a 0.3 mm mesh screen and drying the result. 15 with at least one compound of formula (III): INDUSTRIAL APPLICABILITY As shown in the Examples above, the novel benzanilides of the present invention have Superior insecticidal activity as (III) effective insecticides.

The invention claimed is: 1. A benzanilide of the formula: 25

(I) RI HN1 in the presence of at least one inert Solvent, and if appro X 30 priate, in the presence of an acid catalyst; Xs1so (b) reacting at least one compound compounds of formula - (IV):

HN 35 (IV) C:-y Q O Y R2 R3 X-H N R3 40 NOC-()-- \ / R2 in which O Y X represents hydrogen, halogen, nitro, Calkylthio, C. alkylsulfinyl, Ce alkylsulfonyl or C. alkylsulfony loxy; 45 Y represents halogen or Ce alkyl; R" represents C, alkyl, Ce alkylthio-Cl alkyl, C. with at least one compound of formula (V): alkylsulfinyl-C alkyl or Ce alkylsulfonyl-C alkyl, R represents hydrogen, Calkyl or Chaloalkyl: R" NH (V) R represents hydrogen; 50 in the presence of at least one inert Solvent, and if appro W represents CH or N; and priate, in the presence of an acid catalyst; Q represents substituted phenyl or substituted pyridyl (c) reacting at least one compound of formula (VI): wherein the Substituent is at least one Chaloalkyl. 2. A compound according to claim 1 in which X is halogen, nitro, Calkylthio. C alkylsulfinyl, Ca 55 alkylsulfonyl, or C alkylsulfonyloxy: (VI) Y is halogen or C. alkyl; NH R" is C. alkyl, C, alkylthio-Cia alkyl, C. alkylsulfi nyl-C alkyl or C. alkylsulfonyl-C alkyl; R is hydrogen, C. alkyl or Chaloalkyl; 60 R is hydrogen; S W is CH or N; and CO2H Q is substituted phenyl or substituted pyridyl wherein the Substituent is at least Chaloalkyl. 3. Method for the preparation of compounds of the formula 65 with at least one compound said formula (III), (I) according to claim 1, comprising at least one of the fol in the presence of at least one inert Solvent, and if appro lowing reaction schemes: priate, in the presence of an acid catalyst; US 8,110,689 B2 77 78 (d) reacting at least one compound of formula (VII): wherein R represents C, alkylthio-C, alkyl, O (VII)VII with an oxidant in the presence of at least one inert Solvent. 4. An Insecticidal composition comprising, at least one 21 benzanilide of claim 1. X-- O N 5. A method for combatting harmful insects comprising allowing at least one benzanilide of claim 1 to act on harmful N insects and/or on a habitat thereof and/or on propagation 21 Nw material thereof. 10 Sás 6. A process for the preparation of an insecticidal compo Y R3 sition, comprising mixing at least one benzanilide of claim 1 with at least one extender and/or at least one surface active agent. with at least one compound of said formula (V), in the presence of at least one inert Solvent, and if appro 15 7. A composition for treating seeds comprising a com priate, in the presence of an acid catalyst; pound according to claim 1. (e) reacting at least one compound of formula (VIII): 8. A composition for treating transgenic plants comprising (VIII) a compound of claim 1. 21 CO2H 9. A composition for treating seeds of transgenic plants X comprising a compound of claim 1. N O 10. Method for treating seeds comprising treating the seeds with a composition according to claim 4. HN a Nw 11. Method for treating transgenic plants comprising 25 applying a composition according to claim 4. s,Sás 12. Method for treating the seeds of transgenic plants com Y prising treating the seeds of transgenic plants with a compo sition according to claim 4. with at least one compound of said formula (V), 30 13. Seeds treated with a composition according to claim 4. in the presence of at least one inert Solvent, and if appro 14. A compound according to claim 1 in which priate, in the presence of an acid catalyst; (f) In this reaction scheme f. R' is C, alkylsulfinyl-C- X is C1 or I: alkyl or C. alkylsulfonyl-C alkyl, and said reaction Y is methyl: Scheme foomprises reacting compounds of formula (If): 35 R" is CH(CH)CH-SCH, CH(CH)CHSOCH, O (If) Rlf CH(CH)CHSOCH: HN1 R is H or CF, R is H: 40 W is CH; and Q is substituted phenyl wherein the substituent is at least one CF, CFs. CF7, or CaFo. 15. An insecticidal composition of claim 4, wherein the 45 benzanilide is at a concentration of at least 20 ppm. 16. An insecticidal composition of claim 4, wherein the benzanilide is at a concentration of not more than 20 ppm.