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    • 专利摘要:
    The present invention relates to acylsulfimides of formula (I) Formula I Where Symbols and indices are as defined herein. The acylsulfimides are suitable for controlling animal pests.
    公开号:KR20020081469A
    申请号:KR1020027012382
    申请日:2001-03-17
    公开日:2002-10-26
    发明作者:쉐몰로비치유리그리고리에비치；될러우베；오르트오스발트；샤페르볼프강；얀스다닐라；산프트울리히；되네센마리아-테레시아；베크만마리온；바이벨유타마리아；파제노크세르기이
    申请人:바이엘 크롭사이언스 게엠베하；
    IPC主号:
    专利说明:

    Heterocyclic acylsulfimides, methods for preparing the same, preparations containing the same, and use as pesticides {HETEROCYCLIC ACYLSULFIMIDES, A METHOD FOR THEIR PRODUCTION, AGENTS CONTAINING THE SAME AND THEIR USE AS PESTICIDES}
    [2] The use of insecticides or insect repellents is still essential, due to the enormous damage caused by insects, such as eating useful plants, stored food, wood and textiles, or carrying diseases to people, livestock and useful plants. Insecticides are an important component of comprehensive pest control, and their contribution is crucial to the yield of crops and the continued securement of crops worldwide.
    [3] EP 0 580 374 discloses trifluoromethylpyridine amides for use as insecticides.
    [4] However, the ecological and economic demands on current pesticides, for example related to toxicity, selectivity, spreading rate, residue formation and preferred preparation, are constantly increasing, for example the resistance of pesticides may be further questioned, There is still a need in the art for development of novel pesticides, at least in some areas, that are advantageous over prior art pesticides.
    [5] It has been found that the compounds of formula (I, optionally as salts) have a good activity spectrum against animal pests, while also having good plant resistance and advantageous toxicological properties to mammals and aquatic animals.
    [6] Sulphimids of unsubstituted nicotinamide are described in Fiziol Biokhim Kul't Rast (1999), 31 (4), 303-307 as an emollient for herbicides. However, it cannot be derived from this document that 4-haloalkyl substituted compounds are suitable for use as pesticides.
    [7] Accordingly, the present invention provides acylsulfimides and acylsulfoxymids of formula I and salts thereof:
    [8]
    [9] Where
    [10] X is CH or N;
    [11] Y is O or S;
    [12] n is 0 or 1;
    [13] m is 0 or 1;
    [14] R 1 is C 1 -C 6 -haloalkyl;
    [15] R 2 and R 3 are the same or different and are H, halogen or branched or unbranched (C 1 -C 6 ) -alkyl group wherein one or two of the CH 2 groups in the alkyl group are -O-, -S - or -N (C 1 -C 6) - may be substituted by alkyl, with the proviso that the heteroatom can not be adjacent to each other;
    [16] R 4 and R 5 are the same or different and R 6 , -C (= W) R 7 , -C (= NOR 7 ) R 7 , -C (= NNR 7 2 ) R 7 , -C (= W) OR 7 , -C (= W) NR 7 2 , -OC (= W) R 7 , -OC (= W) OR 7 , -NR 7 C (= W) R 7 , --N [C (= W ) R 7 ] 2 , -NR 7 C (= W) OR 7 , -C (= W) NR 7 -NR 7 2 , -C (= W) NR 7 -NR 7 [C (= W) R 7 ] , -NR 7 -C (= W) NR 7 2 , -NR 7 -NR 7 C (= W) R 7 , -NR 7 -N [C (= W) R 7 ] 2 , -N [(C = W) R 7 ] -NR 7 2 , -NR 7 -NR 7 [(C = W) WR 7 ], -NR 7 [(C = W) NR 7 2 ], -NR 7 (C = NR 7 ) R 7 , -NR 7 (C = NR 7 ) NR 7 2 , -O-NR 7 2 , -O-NR 7 (C = W) R 7 , -SO 2 NR 7 2 , -NR 7 SO 2 R 7 , -SO 2 OR 7 , -OSO 2 R 7 , -OR 7 , -NR 7 2 , -SR 7 , -SiR 7 3 , -PR 7 2 , -P (= W) R 7 , -SOR 7 , -SO 2 R 7 , -PW 2 R 7 2, or -PW 3 R 7 2, or
    [17] R 4 and R 5 together with sulfur to which they are attached form a 3-8 membered saturated or unsaturated, preferably carbocyclic ring system, which ring system is optionally mono- or polysubstituted, preferably radical Optionally monosubstituted or polysubstituted by R 8 , optionally containing 1 to 4 additional hetero atoms, wherein two or more substituents optionally form one or more additional ring systems;
    [18] W is O or S;
    [19] R 6 is the same or different and is (C 1 -C 20 ) -alkyl, (C 2 -C 20 ) -alkenyl, (C 2 -C 20 ) -alkynyl, (C 3 -C 8 ) -cycloalkyl , (C 4 -C 8 ) -cycloalkenyl, (C 8 -C 10 ) -cycloalkynyl, aryl or heterocyclyl, these radicals are optionally mono- or polysubstituted, preferably the radicals R 8 Optionally mono- or polysubstituted by;
    [20] R 7 is the same or different and is H or R 6 .
    [21] Preferred symbols and indices in formula (I) above are compounds defined as follows:
    [22] X is preferably CH.
    [23] Y is preferably O.
    [24] m is preferably 0.
    [25] n is preferably 0.
    [26] R 1 is preferably (C 1 -C 6 ) -alkyl mono- or polysubstituted by F and / or Cl, particularly preferably CF 3 , CHF 2 or CF 2 Cl, most preferably CF 3 .
    [27] R 2 and R 3 are preferably H, halogen, (C 1 -C 6 ) -alkoxy, NH (C 1 -C 6 ) -alkyl, N (C 1 -C 6 ) 2 -alkyl, particularly preferably H.
    [28] R 4 and R 5 are preferably OR 7 , NR 7 2 or R 6 , particularly preferably R 6 .
    [29] Particular preference is given to compounds of the formula I in which the symbols and indices are defined as follows:
    [30] X is preferably CH.
    [31] Y is preferably O.
    [32] m is preferably 0.
    [33] n is preferably 0.
    [34] R 1 is preferably CF 3 .
    [35] R 2 and R 3 are preferably H.
    [36] R 4 and R 5 are preferably R 6 .
    [37] Preferred substituents for the radicals R 4 and R 5 are R 8 of the group defined as follows:
    [38] R 8 is the same or different and is R 9 or two radicals R 8 together with the atoms to which they are attached form a 3-8 membered saturated or unsaturated ring system optionally substituted by one or more radicals R 9 , and The ring system also contains further heteroatoms, preferably O, N, S, SO and / or SO 2 ;
    [39] R 9 is the same or different and R 10 , R 11 , -C (W) R 10 , -C (= NOR 10 ) R 10 , -C (= NNR 10 2 ) R 10 , -C (= W) OR 10 , -C (= W) NR 10 2 , -OC (= W) R 10 , -OC (= W) OR 10 , -NR 10 C (= W) R 10 , -N [C (= W) R 10 ] 2 , -NR 10 C (= W) OR 10 , -C (= W) NR 10 -NR 10 2 , -C (= W) NR 10 -NR 10 [C (= W) R 10 ],- NR 10 -C (= W) NR 10 2 , -NR 10 -NR 10 C (= W) R 10 , -NR 10 -N [C (= W) R 10 ] 2 , -N [(C = W) R 10 ] -NR 10 2 , -NR 10 -N [(C = W) WR 10 ], -NR 10 [(C = W) NR 10 2 ], -NR 10 (C = NR 10 ) R 10 ,- NR 10 (C = NR 10 ) NR 10 2 , -O-NR 10 2 , -O-NR 10 (C = W) R 10 , -SO 2 NR 10 2 , -NR 10 SO 2 R 10 , -SO 2 OR 10 , -OSO 2 R 10 , -OR 10 , -NR 10 2 , -SR 10 , -SiR 10 3 , -PR 10 2 , -P (= W) R 10 2 , -SOR 10 , -SO 2 R 10 , -PW 2 R 10 2 or -PW 3 R 10 2, or two radicals R 9 together are (= W), (= NR 10 ), (= CR 2 10 ), (= CHR 10 ) or (= CH 2 );
    [40] R 10 is the same or different and is (C 1 -C 6 ) -alkyl, (C 2 -C 6 ) -alkenyl, (C 2 -C 6 ) -alkynyl, (C 3 -C 8 ) -cycloalkyl , (C 4 -C 8 ) -cycloalkenyl, (C 3 -C 8 ) -cycloalkyl- (C 1 -C 4 ) -alkyl, (C 4 -C 8 ) -cycloalkenyl- (C 1- C 4 ) -alkyl, (C 3 -C 8 ) -cycloalkyl- (C 2 -C 4 ) -alkenyl, (C 4 -C 8 ) -cycloalkenyl- (C 2 -C 4 ) -alkenyl , (C 1 -C 6 ) -alkyl- (C 3 -C 8 ) -cycloalkyl, (C 2 -C 6 ) -alkenyl- (C 3 -C 8 ) -cycloalkyl, (C 2 -C 6 ) -Alkynyl- (C 3 -C 8 ) -cycloalkyl, (C 1 -C 6 ) -alkyl- (C 4 -C 8 ) -cycloalkenyl, (C 2 -C 6 ) -alkenyl- ( C 4 -C 8 ) -cycloalkenyl, aryl or heterocyclyl, these radicals are optionally substituted by one or more radicals R 11 , and optionally two radicals R 10 together form a ring system;
    [41] R 11 is the same or different and is halogen, cyano, nitro, hydroxy, thio, amino, formyl, (C 1 -C 6 ) -alkanoyl, (C 1 -C 6 ) -alkoxy, (C 3 -C 6 ) -alkenyloxy, (C 3 -C 6 ) -alkynyloxy, (C 1 -C 6 ) -haloalkyloxy, (C 3 -C 6 ) -haloalkenyloxy, (C 3 -C 6 ) -Haloalkynyloxy, (C 3 -C 8 ) -cycloalkoxy, (C 4 -C 8 ) -cycloalkenyloxy, (C 3 -C 8 ) -halocycloalkoxy, (C 4 -C 8 ) Halocycloalkenyloxy, (C 3 -C 8 ) -cycloalkyl- (C 1 -C 4 ) -alkoxy, (C 4 -C 8 ) -cycloalkenyl- (C 1 -C 4 ) -alkoxy, (C 3 -C 8 ) -cycloalkyl- (C 2 -C 4 ) -alkenyloxy, (C 4 -C 8 ) -cycloalkenyl- (C 1 -C 4 ) -alkenyloxy, (C 1 -C 6 ) -alkyl- (C 3 -C 8 ) -cycloalkoxy, (C 2 -C 6 ) -alkenyl- (C 3 -C 8 ) -cycloalkoxy, (C 2 -C 6 ) -alkynyl -(C 3 -C 8 ) -cycloalkoxy, (C 1 -C 6 ) -alkyl- (C 4 -C 8 ) -cycloalkenyloxy, (C 2 -C 6 ) -alkenyl- (C 4- C 8 ) -cycle Roalkenyloxy, (C 1 -C 4 ) -alkoxy- (C 1 -C 6 ) -alkoxy, (C 1 -C 4 ) -alkoxy- (C 3 -C 6 ) -alkenyloxy, carbamoyl, ( C 1 -C 6 ) -mono- or dialkylcarbamoyl, (C 1 -C 6 ) -mono- or dihaloalkylcarbamoyl, (C 3 -C 8 ) -mono- or dicycloalkylcarbamoyl, ( C 1 -C 6 ) -alkoxycarbonyl, (C 3 -C 8 ) -cycloalkoxycarbonyl, (C 1 -C 6 ) -alkanoyloxy, (C 3 -C 8 ) -cycloalkanoyloxy, ( C 1 -C 6 ) -haloalkoxycarbonyl, (C 1 -C 6 ) -haloalkanoyloxy, (C 1 -C 6 ) -alkanamido, (C 1 -C 6 ) -haloalkanamido, (C 2 -C 6 ) -alkenamido, (C 3 -C 8 ) -cycloalkanamido, (C 3 -C 8 ) -cycloalkyl- (C 1 -C 4 ) -alkanamido, (C 1 -C 6 ) -alkylthio, (C 3 -C 6 ) -alkenylthio, (C 3 -C 6 ) -alkynylthio, (C 1 -C 6 ) -haloalkylthio, (C 3 -C 6 ) -haloalkenylthio, (C 3 -C 6 ) -haloalkynylthio, (C 3 -C 8 ) -cycloalkylthio, (C 4 -C 8 ) -cycloalkenylthio, (C 3- C 8 ) -do Cyclocycloalkylthio, (C 4 -C 8 ) -halocycloalkenylthio, (C 3 -C 8 ) -cycloalkyl- (C 1 -C 4 ) -alkylthio, (C 4 -C 8 ) -cyclo alkenyl, - (C 1 -C 4) - alkylthio, (C 3 -C 8) - cycloalkyl, - (C 3 -C 4) - alkenyl, thio, (C 4 -C 8) - cycloalkenyl - ( C 3 -C 4 ) -alkenylthio, (C 1 -C 6 ) -alkyl- (C 3 -C 8 ) -cycloalkylthio, (C 2 -C 6 ) -alkenyl- (C 3 -C 8 ) -Cycloalkylthio, (C 2 -C 6 ) -alkynyl- (C 3 -C 8 ) -cycloalkylthio, (C 1 -C 6 ) -alkyl- (C 4 -C 8 ) -cycloalkenyl Thio, (C 2 -C 6 ) -alkenyl- (C 4 -C 8 ) -cycloalkenylthio, (C 1 -C 6 ) -alkylsulfinyl, (C 3 -C 6 ) -alkenylsulfinyl , (C 3 -C 6 ) -alkynylsulfinyl, (C 1 -C 6 ) -haloalkylsulfinyl, (C 3 -C 6 ) -haloalkenylsulfinyl, (C 3 -C 6 ) -halo Alkynylsulfinyl, (C 3 -C 8 ) -cycloalkylsulfinyl, (C 4 -C 8 ) -cycloalkenylsulfinyl, (C 3 -C 8 ) -halocycloalkylsulfinyl, (C 4- C 8 ) -halocycloalkenylsulfinyl , (C 3 -C 8 ) -cycloalkyl- (C 1 -C 4 ) -alkylsulfinyl, (C 4 -C 8 ) -cycloalkenyl- (C 1 -C 4 ) -alkylsulfinyl, (C 3 -C 8 ) -cycloalkyl- (C 3 -C 4 ) -alkenylsulfinyl, (C 4 -C 8 ) -cycloalkenyl- (C 3 -C 4 ) -alkenylsulfinyl, (C 1 -C 6 ) -alkyl- (C 3 -C 8 ) -cycloalkylsulfinyl, (C 2 -C 6 ) -alkenyl- (C 3 -C 8 ) -cycloalkylsulfinyl, (C 2 -C 6 ) -Alkynyl- (C 3 -C 8 ) -cycloalkylsulfinyl, (C 1 -C 6 ) -alkyl- (C 4 -C 8 ) -cycloalkenylsulfinyl, (C 2 -C 6 )- alkenyl - (C 4 -C 8) - cycloalkenyl sulfinyl, (C 1 -C 6) - alkylsulfonyl, (C 3 -C 6) - alkenyl nilseol sulfonyl, (C 3 -C 6) - alkynyl Nylsulfonyl, (C 1 -C 6 ) -haloalkylsulfonyl, (C 3 -C 6 ) -haloalkenylsulfonyl, (C 3 -C 6 ) -haloalkynylsulfonyl, (C 3 -C 8 )- Cycloalkylsulfonyl, (C 4 -C 8 ) -cycloalkenylsulfonyl, (C 3 -C 8 ) -halocycloalkylsulfonyl, (C 4 -C 8 ) -halocycloalkenylsulfonyl, (C 3- C 8) - cycloalkyl, - (C 1 -C 4) - Kilseol sulfonyl, (C 4 -C 8) - cycloalkenyl - (C 1 -C 4) - alkylsulfonyl, (C 3 -C 8) - cycloalkyl, - (C 3 -C 4) - alkenyl nilseol sulfonyl, (C 4 -C 8 ) -cycloalkenyl- (C 3 -C 4 ) -alkenylsulfonyl, (C 1 -C 6 ) -alkyl- (C 3 -C 8 ) -cycloalkylsulfonyl, (C 2 -C 6) - alkenyl, - (C 3 -C 8) - cycloalkyl, sulfonyl, (C 2 -C 6) - alkynyl, - (C 3 -C 8) - cycloalkyl, sulfonyl, (C 1 -C 6 ) -alkyl- (C 4 -C 8 ) -cycloalkenylsulfonyl, (C 2 -C 6 ) -alkenyl- (C 4 -C 8 ) -cycloalkenylsulfonyl, (C 1 -C 6 )- Dialkylamino, (C 1 -C 6 ) -alkylamino, (C 3 -C 6 ) -alkenylamino, (C 3 -C 6 ) -alkynylamino, (C 1 -C 6 ) -haloalkylamino , (C 3 -C 6 ) -haloalkenylamino, (C 3 -C 6 ) -haloalkynylamino, (C 3 -C 8 ) -cycloalkylamino, (C 4 -C 8 ) -cycloalkenyl Amino, (C 3 -C 8 ) -halocycloalkylamino, (C 4 -C 8 ) -halocycloalkenylamino, (C 3 -C 8 ) -cycloalkyl- (C 1 -C 4 ) -alkylamino , (C 4 -C 8 ) -cycloalkenyl- (C 1 -C 4 ) -alkylamino, (C 3 -C 8 ) -cycloalkyl- (C 3 -C 4 ) -alkenylamino, (C 4- C 8 ) -cycloalkenyl- (C 3 -C 4 ) -alkenylamino, (C 1 -C 6 ) -alkyl- (C 3 -C 8 ) -cycloalkylamino, (C 2 -C 6 )- alkenyl - (C 3 -C 8) - cycloalkyl, amino, (C 2 -C 6) - alkynyl, - (C 3 -C 8) - cycloalkyl, amino, (C 1 -C 6) - alkyl, - (C 4 -C 8 ) -cycloalkenylamino, (C 2 -C 6 ) -alkenyl- (C 4 -C 8 ) -cycloalkenylamino, (C 1 -C 6 ) -trialkylsilyl, aryl, aryl Oxy, arylthio, arylamino, aryl- (C 1 -C 4 ) -alkoxy, aryl- (C 3 -C 4 ) -alkenyloxy, aryl- (C 1 -C 4 ) -alkylthio, aryl- ( C 2 -C 4 ) -alkenylthio, aryl- (C 1 -C 4 ) -alkylamino, aryl- (C 3 -C 4 ) -alkenylamino, aryl- (C 1 -C 6 ) -dialkyl alkylsilyl, diaryl - (C 1 -C 6) - alkylsilyl, triarylsilyl and 5- or 6-membered, and heterocyclyl, these radicals of the cyclic radical of the last 14 The residue is optionally hydrogen, cyano, nitro, amino, hydroxy, thio, (C 1 -C 4 ) -alkyl, (C 1 -C 4 ) -haloalkyl, (C 3 -C 8 ) -cycloalkyl, (C 1 -C 4 ) -alkoxy, (C 1 -C 4 ) -haloalkoxy, (C 1 -C 4 ) -alkylthio, (C 1 -C 4 ) -haloalkylthio, (C 1 -C 4 ) -Alkylamino, (C 1 -C 4 ) -haloalkylamino, formyl and (C 1 -C 4 ) -alkanoyl.
    [42] R 11 is preferably the same or different and is hydrogen, cyano, nitro, (C 1 -C 6 ) -alkanoyl, (C 1 -C 6 ) -alkoxy, (C 1 -C 6 ) -haloalkyloxy , (C 3 -C 8 ) -cycloalkoxy, (C 3 -C 8 ) -cycloalkyl- (C 1 -C 4 ) -alkoxy, (C 1 -C 6 ) -mono- or -dialkylcarbamoyl, (C 1 -C 6 ) -alkoxycarbonyl, (C 1 -C 6 ) -haloalkoxycarbonyl, (C 1 -C 6 ) -alkylthio, (C 1 -C 6 ) -haloalkylthio, (C 3 -C 8 ) -cycloalkylthio, (C 1 -C 6 ) -alkylsulfinyl, (C 1 -C 6 ) -haloalkylsulfinyl, (C 3 -C 8 ) -cycloalkylsulfinyl, (C 1 -C 6 ) -alkylsulfonyl, (C 1 -C 6 ) -haloalkylsulfonyl, (C 3 -C 8 ) -cycloalkylsulfonyl, (C 1 -C 6 ) -dialkylamino, (C 1 -C 6 ) -alkylamino, (C 3 -C 8 ) -cycloalkylamino, (C 1 -C 6 ) -trialkylsilyl, aryl, aryloxy, arylthio, aryl- (C 1 -C 4 ) -alkyl, aryl amino, aryl - (C 1 -C 4) - alkoxy, those radicals of the cyclic radicals of the six last The residues are optionally halogen, nitro, (C 1 -C 4 ) -alkyl, (C 1 -C 4 ) -haloalkyl, (C 1 -C 4 ) -alkoxy and (C 1 -C 4 ) -haloalkoxy Substituted by one or more radicals selected from the group consisting of:
    [43] Among the radicals R 4 and R 5 , particularly preferred are radicals in which the SR 4 R 5 unit is a compound of the formulas A to E:
    [44]
    [45] [Wherein,
    [46] r is 0, 1;
    [47] D is a direct bond, branched or unbranched (C 1 -C 4 ) -alkylene, O, S (O) 0,1,2 , NR 11 ;
    [48] R 9 is the same as defined above;
    [49] R 11 is H, (C 1 -C 4 ) -alkyl, (C 1 -C 4 ) -alkanoyl, (C 1 -C 4 ) -alkoxycarbonyl, (C 1 -C 4 ) -alkyl- or- Dialkylaminocarbonyl or (C 1 -C 4 ) -alkylsulfonyl;
    [50] a and b are the same or different and are 0, 1, 2, 3 or 4, preferably 0, 1 or 2;
    [51] when r is 0, the two aryl radicals are not linked by crosslinking.]
    [52]
    [53] [Wherein,
    [54] R 12 is optionally substituted or condensed with an optionally substituted phenyl radical or (C 3 -C 6 ) -cycloalkyl radical optionally substituted with (C 1 -C 8 ) -alkyl, optionally substituted phenyl radical (C 3 -C 6 ) -cycloalkyl;
    [55] R 9 is the same as defined above;
    [56] a is 0, 1, 2, 3, 4 or 5, and preferably 0, 1 or 2.]
    [57]
    [58] [Wherein,
    [59] R 9 is the same as defined above;
    [60] a is 0, 1, 2, 3 or 4, preferably 0, 1 or 2;
    [61] R 13 is a straight or branched (C 2 -C 8 ) -alkanediyl group optionally substituted or condensed with one or two optionally substituted phenyl groups.]
    [62]
    [63] [Wherein,
    [64] R 14 and R 15 are the same or different and are (C 1 -C 8 ) -alkyl, optionally substituted phenyl optionally substituted by an optionally substituted phenyl radical or a (C 3 -C 8 ) -cycloalkyl radical (C 3 -C 6 ) -cycloalkyl optionally substituted or condensed by a radical.]
    [65]
    [66] [Wherein,
    [67] R 16 is a straight or branched (C 2 -C 8 ) -alkanediyl optionally substituted by one or two optionally substituted phenyl groups when the phenyl group is condensed with one or two optionally substituted phenyl groups It's a flag.]
    [68] The term "halogen" includes fluorine, chlorine, bromine and iodine. The expression “(C 1 -C 4 ) -alkyl” means an unbranched or branched hydrocarbon radical having 1, 2, 3 or 4 carbon atoms, for example methyl, ethyl, propyl, isopropyl, 1- It is to be understood as meaning butyl, 2-butyl, 2-methylpropyl or tert-butyl radicals. Correspondingly, an alkyl radical having a wider range of carbon atoms is to be understood as meaning an unbranched or branched saturated hydrocarbon radical containing many carbon atoms corresponding to the abovementioned range. Thus, the expression “(C 1 -C 6 ) -alkyl” includes the alkyl radicals described above and also includes, for example, pentyl, 2-methylbutyl, 1,1-dimethylpropyl or hexyl radicals. The expression "(C 1 -C 10 ) -alkyl" refers to an alkyl radical as described above, for example it should be understood to mean a nonyl, 1-decyl or 2-decyl radical.
    [69] "(C 1 -C 4 ) -haloalkyl" refers to the description of "(C 1 -C 4 ) -alkyl" in which one or more hydrogen atoms are replaced by the same or different number of halogen atoms, preferably chlorine or fluorine Mean alkyl group, for example trifluoromethyl, 1-fluoroethyl, 2,2,2-trifluoroethyl, chloromethyl, fluoromethyl, difluoromethyl and 1,1,2, It is to be understood as meaning a 2-tetrafluoroethyl group.
    [70] “(C 1 -C 4 ) -alkoxy” is to be understood as meaning an alkoxy group in which the hydrocarbon radical has the meaning defined for “(C 1 -C 4 ) -alkyl”. Thus, alkoxy groups having a wider range of carbon atoms can be understood.
    [71] The terms "alkenyl" and "alkynyl" having the above mentioned carbon number range correspond to the above range and have many carbon atoms containing one or more multiple bonds which may be located at any position of each unsaturated radical. Means a straight chain or branched hydrocarbon radical. Thus, "(C 2 -C 4 ) -alkenyl" means, for example, a vinyl, allyl, 2-methyl-2-propene or 2-butenyl group, and "(C 2 -C 6 ) -alkenyl "Means the radicals described above, for example a pentenyl, 2-methylpentenyl or hexenyl group. "(C 2 -C 4 ) -alkynyl" means, for example, an ethynyl, propargyl, 2-methyl-2-propyne or 2-butynyl group. "(C 2 -C 6 ) -alkynyl" refers to the above-mentioned radicals, for example, it should be understood to mean a 2-pentynyl or 2-hexynyl group, and "(C 2 -C 10 ) -alky "Nyl" means the radicals described above, for example, to mean a 2-octynyl or 2-decynyl group.
    [72] "(C 3 -C 8 ) -cycloalkyl" refers to monocyclic alkyl radicals such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl radicals, and bicyclic alkyl radicals such as norbornyl Means radicals.
    [73] The expression “(C 3 -C 8 ) -cycloalkyl- (C 1 -C 4 ) -alkyl” means, for example, cyclopropylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclohexylethyl and cyclohexylbutyl radicals And the expression “(C 1 -C 6 ) -alkyl- (C 3 -C 8 ) -cycloalkyl” is for example 1-methylcyclopropyl, 1-methylcyclopentyl, 1-methylcyclohexyl, 3- It is to be understood as meaning hexylcyclobutyl and 4-tert-butylcyclohexyl radicals.
    [74] "(C 1 -C 4 ) -alkoxy- (C 1 -C 6 ) -alkyloxy" means that the alkoxy group defined above is replaced with an additional alkoxy group, for example 1-ethoxyethoxy.
    [75] "(C 3 -C 8 ) -cycloalkoxy" or "(C 3 -C 8 ) -cycloalkylthio" is one of the aforementioned (C 3 -C 8 ) -cycloalkyl radicals bonded through an oxygen or sulfur atom It should be understood as meaning.
    [76] "(C 3 -C 8 ) -cycloalkyl- (C 1 -C 6 ) -alkoxy" is for example cyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclohexylethoxy Or a cyclohexylbutoxy group.
    [77] The expression “(C 1 -C 4 ) -alkyl- (C 3 -C 8 ) -cycloalkoxy” means, for example, a methylcyclopropyloxy, methylcyclobutyloxy or butylcyclohexyloxy group.
    [78] "(C 1 -C 6 ) -alkylthio" means an alkylthio group in which the hydrocarbon radical has the meaning defined for "(C 1 -C 6 ) -alkyl".
    [79] Similarly, "(C 1 -C 6 ) -alkylsulfinyl" means, for example, a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary-butyl- or tert-butylsulfinyl group , "(C 1 -C 6) - alkylsulfonyl" is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl sulfonyl means a group-butyl- or tert.
    [80] "(C 1 -C 6) - alkyl amino" refers to the nitrogen atom is substituted by one or two identical or different alkyl radicals as defined above. The expression "(C 1 -C 6 ) -mono- or -dialkylcarbamoyl" has the meaning defined for "(C 1 -C 6 -alkyl)" and may be the same or different for two hydrocarbon radicals. Carbamoyl group having one or two hydrocarbon radicals present.
    [81] Similarly, "(C 1 -C 6 ) -dihaloalkylcarbamoyl" means two (C 1 -C 6 ) -haloalkyl radicals according to the above definition or one (C 1 -C 6 ) according to the above definition. A carbamoyl group having a haloalkyl radical and one (C 1 -C 6 ) -alkyl radical. “(C 1 -C 6 ) -alkanoyl” means, for example, formyl, acetyl, propionyl, butyryl or 2-methylbutyryl groups.
    [82] “Aryl” should be understood to mean preferably carboxylic acid aromatic radicals having 6 to 14 carbon atoms, in particular 6 to 12 carbon atoms (ie consisting of carbon atoms), for example phenyl, naphthyl or biphenylyl, preferably phenyl. . Thus, "aroyl" means an aryl radical as defined above, such as a benzoyl group, bonded through a carbonyl group.
    [83] The expression "heterocyclyl" may preferably be fully saturated, partially unsaturated or fully unsaturated, and may be interrupted by one or more identical or different atoms selected from the group consisting of nitrogen, sulfur and oxygen, but two oxygen atoms may be Cyclic radicals which are not contiguous and at least one carbon atom must be present in the ring, for example thiophene, furan, pyrrole, thiazole, oxazole, imidazole, isothiazole, isoxazole, pyrazole, 1,3, 4-oxadiazole, 1,3,4-thiadiazole, 1,3,4-triazole, 1,2,4-oxadiazole, 1,2,4-thiadiazole, 1,2,4 -Triazole, 1,2,3-triazole, 1,2,3,4-tetazole, benzo [b] thiophene, benzo [b] furan, indole, benzo [c] thiophene, benzo [c] Furan, isoindole, benzoxazole, benzothiazole, benzimidazole, benzisoxazole, benzisothiazole, benzopyrazole, benzothiadiazole, benzotriazole, dibenzofuran, dibenzoti Pen, carbazole, pyridine, pyrazine, pyrimidine, pyridazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,4,5-tetraazine, quinoline, isoquinoline, quinox Saline, quinazoline, cinnoline, 1,8-naphthyridine, 1,5-naphthyridine, 1,6-naphthyridine, 1,7-naphthyridine, phthalazine, pyridopyrimidine, purine, putridine , 4H-quinolizine, piperidine, pyrrolidine, oxazoline, tetrahydrofuran, tetrahydropyran, isoxzolidine or thiazolidine radical. Thus, the expression “heteroaromatic” includes in each case a fully unsaturated aromatic heterocyclic compound, among the meanings defined above for “heterocyclyl”.
    [84] Heterocyclyl means a saturated, partially saturated or aromatic ring system particularly preferably having 3 to 6 ring elements and 1 to 4 heteroatoms selected from the group consisting of O, S and N, wherein one or more carbon atoms It must be present in the ring.
    [85] Very particularly preferably, heterocyclyl is pyridine, pyrimidine, (1,2,4) -oxadiazole, (1,3,4) -oxadiazole, pyrrole, furan, thiophene, oxazole, thia Sol, imidazole, pyrazole, isoxazole, 1,2,4-triazole, tetrazole, pyrazine, pyridazine, oxazoline, thiazolin, tetrahydrofuran, tetrahydropyran, morpholine, piperidine, pipepe Razine, pyrroline, pyrrolidine, oxazolidine, thiazolidine, oxirane and oxetane radicals.
    [86] "Aryl - (C 1 -C 4) - alkoxy" (C 1 -C 4) - aryl radical, attached through an alkoxy group, for example benzyloxy, means methoxy, phenyl or naphthyl tilme butoxy ethoxy radical in phenyl do.
    [87] "Arylthio" means an aryl radical, such as a phenylthio or 1- or 2-naphthylthio radical, bonded through a sulfur atom. Similarly, "aryloxy" means for example phenoxy or 1- or 2-naphthyloxy radicals.
    [88] "Aryl - (C 1 -C 4) - alkylthio" is an aryl radical, for example, benzylthio, naphthyl, methylthio, or phenyl ethyl means alkylthio radical attached through an alkyl thio radical.
    [89] The expression "(C 1 -C 6 ) -trialkylsilyl" means a silicon atom having three identical or different alkyl radicals according to the above definition. Similarly, the "aryl - (C 1 -C 6) - dialkyl silyl" means a silicon atom having one aryl radical and two identical or different aryl radicals according to the above definition, and "diarylamino - (C 1 -C 6 ) -alkylsilyl "means a silicon atom having one alkyl radical and two identical or different aryl radicals according to the above definition, and" triarylsilyl "means three identical or different aryl radicals according to the above definition It means the silicon atom which has.
    [90] Substituents on various aliphatic, aromatic and heterocyclic ring systems are preferably halogen, nitro, cyano, di- (C 1 -C 4 ) -alkylamino, (C 1 -C 4 ) -alkyl, (C 1- C 4 ) -trialkylsilyl, (C 1 -C 4 ) -alkoxy, (C 1 -C 4 ) -alkoxy- (C 1 -C 4 ) -alkyl, (C 1 -C 2 ) -alkoxy- [CH 2 CH 2 ] 1,2 -ethoxy, (C 1 -C 4 ) -alkylthio, (C 1 -C 4 ) -alkylsulfinyl, (C 1 -C 4 ) -alkylsulfonyl, phenyl, benzyl, phenoxy, phenylthio, halo, phenoxy, (C 1 -C 4) - alkyl, thiophenoxy, (C 1 -C 4) - alkoxy phenoxy, (C 1 -C 4) - alkyl-thiophenoxy when melted, Phenylthio, heterocyclyl, heterocyclylthio, heterocyclyloxy, haloheterocyclyloxy, alkylheterocyclyloxy or alkoxyheterocyclyloxy, wherein in the alkyl radicals and radicals derived therefrom, The above hydrogen atoms may be replaced with halogen, preferably chlorine or fluorine, Are replaced by there may be less than the maximum number.
    [91] Particularly preferred substituents are halogen, cyano, nitro, amino, hydroxy, thio, (C 1 -C 4 ) -alkyl, (C 1 -C 4 ) -haloalkyl, (C 3 -C 8 ), especially in cyclic systems -Cycloalkyl, (C 1 -C 4 ) -alkoxy, (C 1 -C 4 ) -haloalkoxy, (C 1 -C 4 ) -alkylthio, (C 1 -C 4 ) -haloalkylthio, (C 1 -C 4 ) -alkylamino, (C 1 -C 4 ) -haloalkylamino, formyl and (C 1 -C 4 ) -alkanoyl.
    [92] Depending on the nature of the substituents defined above, the compounds of formula (I) have acidic or basic properties and can form salts. For example, when the compound of formula (I) has a group such as hydroxy, carboxyl, or other group that induces acidic properties, the compound of formula (I) may react with a base to form a salt. Suitable bases are for example hydroxides, carbonates and bicarbonates of alkali metals and alkaline earth metals, especially hydroxides of sodium, potassium, magnesium and calcium, carbonates and bicarbonates, furthermore ammonia, (C 1 -C 4 )- Primary, secondary and tertiary amines with alkyl radicals, and mono-, di- and trialkanolamines of (C 1 -C 4 ) -alkanols. If the compound of formula (I) has amino, alkylamino, or other groups inducing basic properties, the compound of formula (I) may react with an acid to form salts. Suitable acids are, for example, inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as acetic acid or oxalic acid, and acidic salts such as NaHSO 4 and KHSO 4 . Likewise, salts obtainable in this way have pesticidal, acaricidal and tick eradication properties.
    [93] Compounds of formula (I) may have sulfur atoms asymmetrically substituted on a double bond and / or one or more asymmetrically substituted carbon atoms or stereoisomers. Thus, enantiomers or diastereomers may be present. The present invention includes both pure isomers and mixtures thereof. Mixtures of diastereomers can be separated from the isomers by conventional methods, for example by selective crystallization or chromatography from a suitable solvent. Racemates can be separated into enantiomers by conventional methods.
    [94] The preparation of the compounds according to the invention is carried out by methods known per se from the literature, as described in standard studies on organic synthesis (see Giltlist, CJ Moody's [ Chem. Rev. 77, 409 (1977) and Houben-Weyl (Methoden der Organischen Chemie [Methods of Organic Chemistry], Vol. E11, p. 877).
    [95] The preparation is suitable for the reactions mentioned and carried out under known reaction conditions. In addition, although not specifically mentioned herein, modifications known per se may be used.
    [96] In some cases, the starting material may be formed in situ. That is, the starting material is further reacted immediately without isolation from the reaction mixture to give a compound of formula (I).
    [97] The invention also relates to a process for preparing the compound of formula (I).
    [98] Compounds of formula I wherein R 1 , R 2 , R 3 , R 4 , R 5 , n and X are as defined for formula I, m is 0 and Y is oxygen, are R 1 , R 2 , n and The carboxamide of formula (II), wherein X is defined for formula (I), is reacted with a halogenating agent, preferably a chlorinating or brominating agent, such that R 1 , R 2 , R 3 , n and X are as defined for formula (I). Providing a compound of formula III wherein Z is halogen, preferably chlorine or bromine, and then reacting it with thioether R 4 R 5 S as defined by formula R 4 and R 5 in the presence of a base R 4 and R 5 are preferably prepared by providing the final product of formula I, which is not both aryl and / or heteroaryl.
    [99]
    [100] Suitable halogenating agents for preparing compounds of formula III include, for example, tert-butyl hypochlorite or organo- or alkali metal hypochlorite such as sodium hypochlorite or potassium hypochlorite; Alkali metal hypobromite such as sodium hypobromite or potassium hypobromite; Or halogen in the presence of a base such as an alkali metal or alkaline earth metal hydroxide or carbonate.
    [101] Chlorination of amides with chlorine is known in principle (Ind. J. Chem. V. 35B, 1996, 1117-1118): two steps describe the chlorination of nicotinamide with Cl 2 in 3N HCl. , Yield 58%).
    [102] However, CF 3 groups are known to have a very strong electron attracting effect to prevent electrophilicity and radical attack on CF 3 substituted molecules. For the pyridine ring, the CF 3 group strongly reduces the basicity so that the molecules generally cannot form salts.
    [103] Surprisingly, chlorination of 4-trifluoromethylnicotinamide with Cl 2 in an aqueous acid (eg HCl) yields N-chloro-4-trifluoromethyl-nicotinamide in very good yield and high purity. Revealed.
    [104] Accordingly, the present invention also provides for the chlorination of 4-trifluoromethylnicotinamide with Cl 2 in an aqueous acid, optionally followed by ion exchange and / or reaction with a base to produce N-chloro-4-trifluoro. Providing chloromethylnicotinamide provides a process for preparing N-chloro-4-trifluoromethylnicotinamide and its salts of Formula IIIa:
    [105]
    [106] Where
    [107] A is a non-oxidizing organic or inorganic anion.
    [108] The starting material 4-trifluoromethylnicotinamide is a known compound, the preparation of which is described, for example, in EP 0580374.
    [109] The reaction temperature is usually -5 to + 40 ° C, preferably 0 to + 25 ° C.
    [110] The process is carried out in an aqueous acid, for example HCl, H 2 SO 4 , HBF 4 , CH 3 COOH or CF 3 COOH, preferably HCl (preferably at a concentration of 3 to 10% by weight). It is also possible to use mixtures of multiple acids.
    [111] Cl 2 is preferably used in gaseous form, generally in an amount of 1 to 1.5 mol, in particular 1 to 1.3 mol, preferably 1 to 1.2 mol, based on 1 mol of 4-trifluoromethylnicotinamide.
    [112] Chlorination of 4-trifluoromethylnicotinamide provides the corresponding salts, preferably hydrochloride.
    [113] The work-up is carried out in a manner known to those skilled in the art, for example by filtration, washing and drying the precipitated product.
    [114] Subsequent ion exchange can be carried out by known methods familiar to those skilled in the art. The salts carried out in this reaction can be dissolved, for example, in a suitable solvent in which the desired salts of the following will not dissolve. Reaction with a salt containing the desired anion and likewise soluble in the solvent can give the desired salt by precipitation (since this salt is not soluble in the selected solvent).
    [115] If desired, the free N-chloro compound can be released by reacting with a base in a simple manner familiar to those skilled in the art.
    [116] Suitable bases are, for example, hydroxides, carbonates, bicarbonates and acetates of alkali and alkaline earth metals, in particular hydroxides, carbonates, bicarbonates and acetates of sodium, potassium, magnesium and calcium, moreover (C 1 -C 4 )-tertiary amine with an alkyl radical. The free base can also be isolated by treatment with water and extracted with an organic solvent.
    [117] The present invention also provides salts of N-chloro-4-trifluoromethylnicotinamide of formula IIIa:
    [118] Formula IIIa
    [119]
    [120] Where
    [121] A is a non-oxidizing organic or inorganic anion, preferably F, HF 2 , Cl, BF 4 , PF 6 , HSO 4 , 1 / 2SO 4 , CH 3 COO, CF 3 COO CF 3 SO 3 , CH 3 SO 3 , p-CH 3 -C 6 H 5 SO 3 or H 2 PO 4 .
    [122] In the present invention, 'non-oxidizing' means that the corresponding anion does not react with the N-Cl group of N-chloro-4-trifluoromethylnicotinamide.
    [123]
    [124] The reaction of the N-haloamide of formula III (optionally as a salt) to the final product of formula I is carried out at 0 to 100 ° C., preferably 20 to 50 in an inert solvent such as, for example, dichloromethane, chloroform, carbon tetrachloride or benzene. In the presence of a base at a temperature of < RTI ID = 0.0 > Suitable bases are for example alkali metal or alkaline earth metal hydroxides, carbonates or bicarbonates or organic bases such as trialkylamides or pyridine.
    [125] Furthermore, the above reaction sequence is optionally carried out as a one-pot reaction, in which R 4 and R 5 are as defined for formula I, Z is a halogen radical, preferably chlorine or bromine An intermediate of formula (IV) may occur as a reaction partner of the amide of formula (II).
    [126]
    [127] Compounds of formula (I) in which R 1 , R 2 , R 3 , R 4 , R 5 , n, m and X are as defined for formula (I) and Y is oxygen, form a carboxylic acid of formula (V) in the form of its active derivative It can be prepared by reacting with a compound of formula VI in the presence of:
    [128]
    [129] [Wherein,
    [130] R 1 , R 2 , R 3 , X and n are the same as defined for Formula (I).]
    [131]
    [132] [Wherein,
    [133] R 4 , R 5 and m are the same as defined for Formula (I).]
    [134] Suitable active derivatives of the acids which can be used are, for example, anhydrides, azolides or preferably acid chlorides. Suitable bases are, for example, amines such as triethylamine, diisopropylethylamine, pyridine or lutidine, or other alkali or alkaline earth metal hydroxides, carbonates or bicarbonates. The reaction is advantageously carried out in an inert solvent such as, for example, dichloromethane, chloroform, carbon tetrachloride, benzene, toluene, diethyl ether or tetrahydrofuran, or a mixture of the above solvents, of 0 to 100 ° C, preferably 20 to 50 ° C. Carried out at temperature.
    [135] The compound of formula (Ia) advantageously converts the amide of formula (II) to the N, N-dichloro compound of formula (VII) using a halogenating agent such as tert-butyl hypochlorite, followed by sulfur dichloride SCl 2 To a compound of formula VIII, which is reacted with at least 2 equivalents of the nucleophile HER 7 , wherein ER 7 is as defined for Formula Ia in the presence of a base:
    [136]
    [137] [Wherein,
    [138] R 1 , R 2 , R 3 , R 7 , X and n are the same as defined for Formula I,
    [139] Y is oxygen,
    [140] E corresponds to oxygen or nitrogen units.]
    [141]
    [142] [Wherein,
    [143] R 1 , R 2 , R 3 , n and X are the same as defined for Formula I.]
    [144]
    [145] [Wherein,
    [146] R 1 , R 2 , R 3 , n and X are the same as defined for Formula I.]
    [147] Suitable bases are, for example, organic bases such as triethylamine, pyridine or lutidine, or alkali metal or alkaline earth metal hydroxides, carbonates or bicarbonates, and, in the case of alcohols, alkali metal or alkaline earth metal hydrides or amides. The reaction is advantageously carried out at a temperature of from 0 to 100 ° C., preferably from 20 to 50 ° C. in an inert solvent such as dichloromethane, chloroform, carbon tetrachloride, benzene, toluene, diethyl ether or tetrahydrofuran, or a mixture of the above solvents. do.
    [148] Compounds of formula (I) wherein R 1 , R 2 , R 3 , R 4 , R 5 , n and X are as defined for formula (I), Y is oxygen and m is 0, azide of formula (IX) Can be prepared by reacting or irradiating with thioether R 4 R 5 S, wherein R 4 and R 5 are the same as defined for Formula I, in the presence of a catalyst such as 2 to obtain a nitrogen-free final product. have:
    [149]
    [150] Where
    [151] R 1 , R 2 , R 3 , X and n are the same as defined for Formula (I).
    [152] In addition, compounds of Formula I wherein R 1 , R 2 , R 3 , n and X are as defined for Formula I, R 4 and R 5 are aryl radicals, Y is oxygen, and m is 0, Formula II May be obtained by reacting an amide of with a dialkoxy-diaryl-sulfuran of formula X:
    [153]
    [154] Where
    [155] R 4 and R 5 are aryl radicals,
    [156] OR F is a fluoroalkoxy radical, preferably 1,1,1,3,3,3-hexafluoro-2-phenyl-2-propoxy radical.
    [157] In addition, compounds of formula (I) wherein R 1 , R 2 , R 3 , R 4 , R 5 , n and X are as defined for formula (I), Y is oxygen and m is 0, are sulfoxides of formula (XI) Can be prepared by reaction with an amide of formula (II) in the presence of a condensing agent to give a compound of formula (I) from which water has been removed:
    [158]
    [159] Where
    [160] R 4 and R 5 are the same as defined for Formula (I).
    [161] Suitable condensing agents are for example phosphorus oxychloride, phosphorus (V), methanesulfonyl chloride, sulfyl chloride, sulfur trichloride, boron trichloride, dicyclohexylcarbodiimide, aryl cyanate or acid anhydrides, preferably tri Fluoroacetic anhydride or trifluoromethanesulfonic anhydride.
    [162] To prepare a compound of formula (I) wherein n is 1, the pyridine nitrogen can be oxidized, preferably prior to introducing the SR 4 R 5 group (see, for example, Methode der Organischen Chemie, Vol. E7b, part 2, p.565, G. Thieme Verlag, Stuttgart (1992)]. Suitable oxidizing agents are, for example, organic peracids such as 3-chloroperbenzoic acid and H 2 O 2 .
    [163] If desired, the compounds of formula (I) prepared by the process can be oxidized in sulfur when m is 0 to give compounds of formula (I) in which m is 1 (see, eg, Huben-Whale's Methododen). der Organischen Chemie, Vol. E11, p. 1299ff, G. Thieme Verlag, Stuttgart 1985]. Suitable oxidizing agents are, for example, organic peracids such as sodium periodate or 3-chloroperbenzoic acid.
    [164] Furthermore, if desired, compounds of formula (I) wherein R 2 and / or R 3 are halogen atoms, preferably chlorine or fluorine, are reacted with alcohol, thiols or primary or secondary amines in the presence of a base to give R 2 and / or R 3 can be converted to the next compound of formula (I) which is an alkoxy, alkylthio or amine group.
    [165] Further reference preparations of the compounds according to the invention and various starting materials are described, for example, in Gilklist, Moody's, Chem. Rev. 77, 409 (1977) or by Huven-Whale, Method der Organischen Chemie, Vol. E11, p. 877] can be found in standard studies on organic synthesis.
    [166] The collection of compounds of formula (I), which can be synthesized by the above-mentioned methods, can be done in a similar manner, which can be carried out in a manual, semi-automatic or fully automated manner. In such cases it is possible, for example, to automate the reaction process, stop the reaction or purify the product or intermediate. As a whole, it is understood to mean a procedure as described, for example, in SH DeWitt, "Annual Reports in Combinatorial Chemistry and Molecular Diversity: Automated synthesis", Volume 1, Verlag Escom 1997, pages 69 to 77. Can be.
    [167] For example, Stem Corporation (UK CM9 8SE Essex Tolesbury Woodrollpe Road) or H + P Laboratories GmbH (Obershelaisheim, Germany 85764 Brookman Ring 28). A series of commercially available devices provided by the above can be used for the corresponding reaction procedures and reaction stops. For the purification of the compounds of formula (I) or intermediates obtained during the preparation, for example, the chromatography apparatus provided by ISCO Incorporated (68504 Lincoln Supero Street 4700, Nebraska, USA) can be used.
    [168] The mentioned devices have modular procedures in which each process step is automated but manual operations must be carried out between each process step. These can be prevented by using the automation module of interest, for example by using a semi-integrated or fully integrated automation system operated by a robot. Such an automated system can be obtained, for example, from Zymark Corporation (01748 Hopkinton Ziemark Center, Massachusetts, USA).
    [169] In addition to those described herein, the compounds of formula (I) may be prepared partially or completely by solid phase support methods. For this purpose, each intermediate step or all intermediate steps of the synthesis adapted to be suitable for the synthesis or target procedure are associated with the synthetic resin. Solid phase support synthesis methods are for example Berry A. It is extensively described in specialized books such as Barry A. Bunin ("The Combinatorial Index", Academic Press, 1998). The use of the solid phase supported synthesis method allows for a set of protocols known from the literature and which can be carried out by an automated method or manually. For example, the "tea-bag method" (Houghten, U.S. Pat. No. 4,631,211, in which a product by IRORI, 92037, La Jolla, North Toray Pines Road 11149) is used. Huten et al., Proc. Natl. Acad. Sci, 1985, 82, 5131-5135, may be semi-automated.Automation of solid phase supported pseudosynthesis may be accomplished, for example, by Argonaut Technologies. , Inc .; 94070, California, USA, San Carrolls Industrial Road 887) or MultiSynTech GmbH (Viten 58454, Mullenfeld 4).
    [170] The manufacturing process described herein produces a compound of formula (I) in the form of material collection, referred to as a library. The invention also relates to a library comprising two or more compounds of formula (I).
    [171] The compounds of the formula (I) are suitable for the control of animal pests, in particular insects, arachnids, worms and molluscs, and particularly preferably for the control of insects and arachnids which are encountered in the field of protection and hygiene of crops, livestock raising, forests, stored goods and materials , Good plant resistance and favorable toxicity to warm-blooded animal species. The compound is active against normal sensitive and resistant species and at both the developmental stage or at each developmental stage. The aforementioned pests in Akari or (Acarina) tree, for example aka Russ Shiro (Acarus siro), are gas (Argas) species (spp.), Ornithine Todo Ross (Ornithodoros) species, der Mani suspension Galina (Dermanyssus gallinae) , Eriophyes ribis , Phyllocoptruta oleivora , Boophilus species, Rhipicephalus species, Amblyomma species, Hyalomma species, Isophytes Ixodes species, Psoroptes species, Chorioptes species, Sarcoptes species, Tarsonemus species, Bryobia praetiosa , Panoni cheoseu (Panonychus) species, tetra you cheoseu (Tetranychus) species, eotaxin-tetrahydro you cheoseu (Eotetranychus) species, up your cheoseu (Oligonychus) species, is oil-tetrahydro cheoseu comprising (Eutetranychus) paper. Isopoda , for example Oniscus aselus , Armadium vulgare , Porcellio scaber . Deployer includes poda (Diplopoda) tree, for example Blast Niu Russ Gutu La Tuscan (Blaniulus guttulatus). Chilopoda , for example Geophilus carpophagus , Scutigera species. Symphyla neck, for example Scutigerella immaculata . Thysanura neck, for example Lepisma saccharina . Collembola neck, for example Onychiurus armatus . Orthoptera necks, eg Blatta orientalis , Periplaneta americana , Leucophaea maderae , Blattella germanica , Aceh Acheta domesticus , Gryllotalpa species, Locusta migratoria migratorioides , Melanoplus differentialis , and Schistoska gregaria Schistocerca gregaria ). Isoptera species, for example Reticulitermes species. Cyano peuruna (Anoplura) tree, for example pillow Era bath status matrix (Phylloera vastatrix), pempi Gus (Pemphigus) species, Phedi large Russ Hugh Manus Inc. lease (Pediculus humanus corporis), hippocampus toffee Nurse (Haematopinus) species, Reno By the Linognathus species. Tree Mallophaga , for example Trichodectes species, Damalinea species. Thysanoptera neck, for example Hercinothrips femoralis , Thrips tabaci . Heteroptera neck, for example Eurygaster species, Dysdercus intermedius , Piesma quadrata , Cimex lectularius , Rodney Rhodnius prolixus , Triatoma species. No. morph TB (Homoptera) to the neck, e.g., Rhodes Aru bracket (Aleurodes brassicae), bemi cyano other Bridge (Bemisia tabaci), des bar Fora Rio volume (Trialeurodes vaporariorum), Apis notice blood (Aphis gossypii) in a tree aluminate , Brevicoryne brassicae , Cryptomyzus ribis , Doralis fabae , Doralis pomi , Eriosoma lanigerum , hyaloptherus Hyalopterus arundinis , Macrosiphum avenae , Myzus species, Phorodon humuli , Rhopalosiphum padi , Empoasca species , use Sellers ratio Tuscan bar (Euscelus bilobatus), four new vertices Forte Sancti sepseu (Nephotettix cincticeps), titanium Greca Konishi (Lecanium corni), O Poinsettia between oleic (Saissetia oleae), Rao del Pax Austria Stems (Laodelphax str iatellus), Neela Parque Bata Lou Regensburg (Nilaparvata lugens), Oh sludge de Ella Augusta is T (Aonidiella aurantii), Oh Speedy five Charters header Lee (Aspidiotus hederae), pseudo Caucus (Pseudococcus) species, Silas (Psylla), including species do. Lepidoptera neck, for example Pectinophora gossypiella , Bupalus piniarius , Cheimatobia brumata , Lithocolletis blancardella ), Hyponomeuta padella , Plutella maculipennis , Malacosoma neustria , Euproctis chrysorrhoea , Lymantria species, sub Kula matrix emitter berry Ella Inn (Bucculatrix thurberiella), Philo greatest seutiseu sheet mozzarella (Phyllocnistis citrella), Agrobacterium-Tees (Agrotis) species, six children (Euxoa) species, Pell Tia (Feltia) species, Ari Earth in the Peninsula or ( Earias insulana ), Heliothis species, Laphygma exigua , Mamestra brassicae , Panolis flammea , Prodeni Ah Lee Ventura (Prodenia litura), Spokane help Terra (Spodoptera) species, tree chopeul Russia you (Trichoplusia ni), car reportage kapsa Four Monella.All (Carpocapsa pomonella), blood EPO (Pieris) species, fills (Chilo) species, Fira Worcester Pyrausta nubilalis , Ephestia kuehniella , Galleria mellonella , Cacoecia podana , Capua reticulana , Choristostona Choristoneura fumiferana , Clysia ambiguella , Homona magnanima , Tortrix viridana .
    [172] Coleoptera neck, for example Anobium punctatum , Rhizopertha dominica , Bruchidius obtectus , Acanthoscelides obtectus ), Hylotrupes bajulus , Agelastica alni , Leptinotarsa decemlineata , Phaedon cochleariae , Diabrotica Species, Psylloides chrysocephala , Epilachna varivestis , Atomaria species, Oryzaephilus surinamensis , Anthonomus species , Sitophilus spp., Otiorrhynchus sulcatus , Cosmopolites sordidus , and Seutorlichus asimos Ceuthorrynchusassimilis), high-Ferrat Force Galactica (Hypera postica), Der Metz Tess (Dermestes) species Tropez Godet reuma (Trogoderma), no trail Yunus (Anthrenus) species, tease Nurse (Attagenus) species, Richter's (Lyctus) species, Mellieha Meligethes aeneus , Ptinus species, Niptus hololeucus , Gibbium psylloides , Tribolium species, Tenebrio molito molitor ), Agriotes species, Conoderus species, Melolontha melolontha , Amphimallon solstitialis , Costelytra zealandica . Hime knob TB (Hymenoptera) tree, for example, di-prion (Diprion) species, the call flow kaempa (Hoplocampa) species, La siwooseu (Lasius) species, mono mode Solarium Pharaoh varnish (Monomorium pharaonis), Vespa (Vespa) including species do. Diptera , for example Aedes species, Anopheles species, Culex species, Drosophila melanogaster , Musca species, Pania ( Fannia species, Calliphora erythrocephala , Lucilia species, Chrysomyia species, Cuterebra species, Gastrophilus species, Hypoboska Hypobosca species, Stomoxys species, Oestrus species, Hypoderma species, Tabanus species, Tannia species, Bibio hortulanus , Oss when Nella frit (Oscinella frit), formate via (Phorbia) species, pego Mia Hi OSU when amino (Pegomyia hyoscyami), ceramide entity's copy of tartar (Ceratitis capitata), the coarse oleic Ke (Dacus oleae), tea Foulard Palu Dosa ( Tipulapaludosa ). Siphonaptera , for example Xenopsylla cheopsis , Ceratophyllus species. Arachinida , for example Scorpio maurus , Latrodectus mactans . Insects, for example Haemonchus , Trichostrongulus , Ostertagia , Cooperia , Chabertia , Strongyloides , Oesofa including high testosterone drought (Oesophagostomum), Russ me high five strong (Hyostrongulus), ansil Ross Thomas (Ancylostoma), Asuka lease (Ascaris) and H. Keith Terra (Heterakis) and Paz City (Fasciola) up.
    [173] Gastropods (Gastropoda), for example, as having seraseu (Deroceras) species, Arion (Arion) species, O (Lymnaea) species, the galvanic (Galba) species, three cine O (Succinea) species, biome Palazzo Liao (Biomphalaria) in rimna kind and disadvantages Yunus (Bulinus), including species, onko Melanie Ah (Oncomelania) species. Bivalva species, for example Dreissena species.
    [174] Plant-parasitic nematodes which can be controlled according to the invention are for example root-parasite soil-resident nematodes, such as the genus Meloidogyne (root or nematodes, such as Meloidogyne incognata ), melo Meloidogyne hapla and Meloidogyne javanica , Heterodera and Globodera ( vesicle -forming nematodes, such as Globodera rostochiensis , Globodera pallida , Heterodera trifolii and Radopholus genus such as Radopholus similis , Pratylenchus such as pretensioners Pratylenchus neglectus , Pratylenchus penetrans , and Pratylenchus curvitatus ; Tea renchul Russ (Tylenchulus), for example tea renchul Russ semi-phenethyl trans (Tylenchulus semipenetrans), styrene chorin cheoseu (Tylenchorhynchus), for example styrene chorin cheoseu Pardubice Earth (Tylenchorhynchus dubius) and styrene chorin cheoseu keulraeyi T. (Tylenchorhynchus claytoni), Loti alkylene cheoseu ( Rotylenchus ), such as Rotylenchus robustus , Heliocotylenchus , such as Heliocotylenchus multicinctus , Belonoaimus , such as Belonoaimus longgiukada Belonoaimus longicaudatus , Longidorus , such as Longidorus elongatus , Trichodorus , such as Trichodorus primitivus and Xiphinema , such as Xiphinema index .
    [175] Other nematode genera that can be controlled using the compounds according to the invention are Ditylenchus (stem parasites such as Ditylenchus dipsaci and Ditylenchus destructor ), aperene Aphelenchoides (leaf nematodes, such as Aphelenchoides ritzemabosi ) and Anguina (seed nematodes, such as Anguina tritici ).
    [176] The invention relates to compositions comprising, for example, one or more compounds of formula (I), in addition to suitable formulation aids, for example crop protection compositions, preferably insecticides, acaricides, ixodicides, nematodes, molluscs insecticides. Or fungicidal compositions, particularly preferably pesticidal and acaricidal compositions.
    [177] In general, the compositions according to the invention comprise 1 to 95% by weight of active substance of formula (I).
    [178] To prepare the compositions according to the invention, the active substances and other additives are combined or prepared in a suitable use form.
    [179] The present invention relates to compositions comprising compounds of formula (I), in particular insecticidal and acaricidal compositions, in addition to suitable formulation aids.
    [180] In general, the compositions according to the invention comprise 1 to 95% by weight of active substance of formula (I). Such compositions may be formulated in several ways depending on the biological and / or chemical-physical variables associated with the composition. Examples of possible formulations include: wettable powders (WP), emulsifiable concentrates (EC), aqueous solutions (SL), emulsions, sprayable solutions, oil- or water-based dispersions (SC), suspo emulsions (suspoemulsion (SE), dust (DP), seed-dressing products, micro granules of granules, sprayable granules, coated and adsorptive granules, water dispersible granules (WG), ULV formulations, microcapsules, waxes or handouts ( bait).
    [181] Each of these types of formulations is basically known and is described, for example, in Winnacker-Kuchler ("Chemical Technology", Volume 7, C. Hanser Verlag Munich, 4th Edition 1986); Van Falkenberg, "Pesticides Formulations", Marcel Dekker N.Y., 2nd Ed. 1972-73; K. Martens, "Spray Drying Handbook", 3rd Ed. 1979, G. Goodwin Ltd. London.
    [182] Necessary formulation auxiliaries, ie carrier materials and / or surfactant materials such as inert materials, surfactants, solvents and other additives are also known and described, for example, in Watkins, "Handbook of Insecticide Dust Diluents and Garriers. 2nd Ed., Darland Books, Caldwell NJ; H. v. Olphen, "Introduction to Clay Colloid Chemistry", 2nd Ed., J. Wiley & Sons, N.Y .; Marsden, "Solvents Guide", 2nd Ed., Interscience, N.Y. 1950; McCutcheon, "Detergents and Emulsifiers Annul", MC Publ. Corp., Ridgewood N. J .; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964; Schonfeldt, Glenzflachenaktive Athylenoxidaddukte [surfactant ethylene oxide adduct] Wiss. Verlagsgesell., Stuttgart 1967; by Chinnacker-Kuchler, Chemische Technologie, Volume 7, C Hanser Verlag Munich, 4th Edition 1986.
    [183] Based on such formulations, it is possible to prepare them in combination with other pesticidal active substances, fertilizers and / or growth regulators, for example in the form of premixed or tank mixed. Wetting powders may be used in addition to the active materials, but also with diluents or inert materials and wetting agents, for example polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, alkylsulfonates or alkylphenolsulfonates, and dispersants such as sodium lignonos It is a formulation uniformly dispersed in water, including sulfonate or sodium 2,2'-dinaphthylmethane-6,6'-disulfonate.
    [184] Emulsifiable concentrates are prepared by dissolving the active substance in an organic solvent, such as butanol, cyclohexanone, dimethylformamide, xylene or other high boiling aromatic compounds or hydrocarbons, with the addition of one or more emulsifiers. Calcium alkylarylsulfonates (eg calcium dodecylbenzenesulfonate) or nonionic emulsifiers (eg fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide / ethylene oxide condensates, alkyl as emulsifiers) Polyethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters or polyoxyethylene sorbitol esters).
    [185] Dust is obtained by grinding the active material with finely divided solid materials, for example talc or natural clay (eg kaolin, bentonite, pyrophyllite or diatomaceous earth). Granules can be applied by spraying an active substance onto an adsorbent granulating inert material, or by spraying the active substance concentrate on a carrier material (eg sand or kaolinite) or on the surface of the granulated inert material (eg polyvinyl alcohol or sodium polyacrylic). Rate) or other inorganic oils. Suitable active substances can be granulated in a manner customary for the preparation of fertilizer granules (if any as a mixture with fertilizers).
    [186] The concentration of active substance in the wettable powder is, for example, about 10 to 90% by weight and the rest up to 100% by weight consists of conventional formulation aids. In the case of emulsifiable concentrates, the concentration of active substance is about 5 to 80% by weight. Formulations in dust form generally comprise from 5 to 20% by weight of active material and the nebulizable solution contains from about 2 to 20% by weight of active material. In the case of granules, the content of the active substance depends to some extent on whether the active compound is in liquid or solid form and which granulation aids, fillers and the like are used.
    [187] In addition, the active substance formulations described above optionally include conventional thickeners, wetting agents, dispersants, emulsifiers, penetrants, solvents, fillers or carriers, respectively.
    [188] In use, concentrates, which are in commercially available form, are optionally diluted in the usual manner, for example with water, for wettable powders, emulsifiable concentrates, dispersions and for microgranules. In the form of dust, granules and nebulizable solutions, the preparation is not further diluted with other inert materials before use.
    [189] The required spreading rate varies with external conditions, for example temperature and humidity. The spreading rate varies in a wide range, for example more than 0.0005 to 10.0 kg / ha of active substance is used but is preferably 0.001 to 5 kg / ha.
    [190] The active substances according to the invention in commercially available formulations and in the form of use prepared from such formulations may be used as pesticides, attractants, sterilizers, tick insecticides, nematicides, fungicides, molluscicides, growth regulators or herbicides. It may be present as a mixture with the active substance.
    [191] Pesticides include, for example, phosphate esters, carbamates, carboxylic acids, formamidines, tin compounds and substances produced by microorganisms.
    [192] Preferred components for the mixture are as follows:
    [193] 1. From the group of phosphorus compounds
    [194] Acetate, Azametifoss, Ajinfoss-ethyl, Ajinfoss-methyl, Bromophos, Bromophos-ethyl, Cardusafoss (F-67825), Chlorethoxyfoss, Chlorfenbinfoss, Chlormephos, Chlorose Pyriphos, Chlorpyriphos-methyl, Demethone, Demethone-S-methyl, Demethone-S-methyl Sulfone, Dialilifos, Diazinon, Dichlorbose, Dicrotophos, Dimethoate, Disulfotone, EPN , Ethion, etoprofoss, estrimfoss, pampur, phenamifoss, phentriothione, pensulfothion, pention, flupyrazofoss, phonofoss, formothione, phosphiazate, heptenofoss , Isosafos, isothioate, isoxation, malathion, methacryphos, metamidose, methidadion, salityon, mevinforce, monocrotophos, naled, ometoate, oxydemethone-methyl , Parathion, Parathion-Methyl, Pentoate, Forate, Posalon, Phospholan, Phosphocarb (BA S-301), phosmet, phosphamidone, bombardment, pyrimifoss, pyrimifos-ethyl, pyrimifos-methyl, propenophos, propaphos, proetamphos, prothiophos, pyraclophos , Pyridapention, quinalforce, sulfprofos, temefos, terbufoss, tebupyrimfoss, tetrachlorbinfoss, thiomethones, triazofoss, trichlorpons, bamidothiones;
    [195] 2. From a group of carbamates
    [196] Alanicarb (OK-135), Aldicarb, 2-sec-butylphenyl methylcarbamate (BPMC), Carbaryl, Carbofuran, Carbosulphan, Cloetocarb, Benfuracarb, Ethiophencarb, Furathiocarb, HCN -801, isoprocarb, metomil, 5-methyl-m-cumenylbutyryl (methyl) carbamate, oxamyl, pyrimicab, propoxyl, thiodicarb, thiophanox, 1-methylthio (ethyl Lideneamino) -N-methyl-N- (morpholinothio) carbamate (UC 51717), triamate;
    [197] 3. from groups of carboxylic esters
    [198] Acrinatrin, alletrin, alphamethrin, 5-benzyl-3-furylmethyl (E)-(1R) -cis-2,2-dimethyl-3- (2-oxothiolane-3-ylidenemethyl) Cyclopropanecarboxylate, beta-cifluthrin, alpha-cifermethrin, beta-cifermethrin, bioallerthrin, bioallerthrin ((S) -cyclopentyl isomer), bioresmethrin, bifenthrin , (RS) -1-cyano-1- (6-phenoxy-2-pyridyl) methyl (1RS) -trans-3- (4-t-butylphenyl) -2,2-dimethylcyclopropanecarboxylate (NCI 85193), cycloprotrin, cyfluthrin, sihalothrin, citrine, cipermethrin, cifenotrine, deltamethrin, empentrin, espenvalrate, fenfluthrin, fenpropatrin, Penvalerate, Flucitrinate, Flumethrin, Fluvalinate ((D) isomer), Imiprotrin (S-41311), Lambda-Sihallotrin, Permethrin, Phenothrin ((R) isomer) , Praletrin, pyrethrin (natural products), lesme Tririne, tefluthrin, tetramethrin, theta-cifermethrin, tralomethrin, transfluthrin, zeta-cifermethrin (F-56701);
    [199] 4. From amidine group
    [200] Amitraz, chlordimeform;
    [201] 5. from tin compound groups
    [202] Cyhexatin, fenbutatin oxide;
    [203] 6. Other
    [204] Abamectin, ABG-9008, Acetamifried, Acequinosyl, Anagrapha Falcytera, AKD-1022, AKD-3059, ANS-118, Azadiractin, Bacillus thuringiensis, Buberia basianea, Ben Sultap, bifenazate, vinapacryl, BJL-932, bromopropylate, BTG-504, BTG-505, buprofezin, campechlor, catab, chlorobenzylate, chlorfenapyr, chlorfluazuron, 2- (4-chlorophenyl) -4,5-diphenylthiophene (UBI-T 930), chlorpentazine, chlorproxyfen, chromafenozide, clothianidine, 2-naphthylmethyl cyclopropanecarboxyl Rate (Ro12-0470), siroma, diaclodene (thiamethoxam), diafenthiuron, DBI-3204, ethyl 2-chloro-N- (3,5-dichloro-4- (1,1,2, 3,3,3-hexafluoro-1-propyloxy) phenyl) carbamoyl) -2-carboxymidate, DDT, dicopol, diflubenzuron, N- (2,3-dihydro-3-methyl- 1,3-thiazole-2-ylidene) -2,4-xyldine, dihydroxymethyldiha Doxypyrrolidine, dinobutone, dinocap, diophenollan, emamectin benzoate, endosulfan, etiprolol (sulfetiprole), etofenprox, ethoxazole, phenazine, phenoxycarb, fipronil, fluazuron Flumite (flufenzine, SZI-121), 2-fluoro-5- (4- (4-ethoxyphenyl) -4-methyl-1-pentyl) diphenyl ether (MTI 800), granulosis and Nuclear polyhedrosis virus, penpyroximate, penthiocarb, fluacrylpyrim, flubenzimin, flubrocitinate, flucycloroxon, flufenoxuron, flufenzine, flufenprox, fluproxyfen, gamma -HCH, halofenozide, halofenprox, hexaflumuron (DE-473), hexiaxox, HOI-9004, hydrammonone (AC 217300), IKI-220, indoxacarb, ivermectin, L-14165, imidacloprid, indoxacarb (DPX-MP062), cannemite (AKD-2023), eufenuron, M-020, methoxyphenozide, milbectin, NC-196, neemgard, knee Dinoterfuran, nitenpyram, 2-nitromethyl-4,5-dihydro-6H-thiazine (DS 52618), 2-nitromethyl-3,4-dihydrothiazole (SD 35651), 2-nitromethylene -1,2-thiazinane-3-ylcarbamaldehyde (WL 108477), novaluron, pyridaryl, progite, protrifenbate, pymetrozine, pyridaben, pyrimidifene, pyriproxyfen, NC- 196, NC-1111, NNI-9768, Novaluron (MCW-275), OK-9701, OK-9601, OK-9602, OK-9802, R-195, RH-0345, RH-2485, RYI-210 , S-1283, S-1833, SI-8601, silafluorene, silomadine (CG-177), spinosad, spirodiclofen, SU-9118, tebufenozide, tebufenpyrad, tefluben Juron, tetradipon, tetrasul, thiacloprid, thiocyclam, thiamethoxam, tolfenpyrad, triamate, triethoxyspinosine A, triflumuron, berbutin, betalec (mycotal), YI -5301.
    [205] The components for the combination are known active substances and are described in Ch. R Worthing, S.B. Walker, The Pesticide Manual, 12th Edition, British Crop Protection Council, Farnham 200.
    [206] The content of the active substance in the use form prepared from a commercially available formulation is in the range of 0.00000001 to 95% by weight of active substance, preferably 0.00001 to 1% by weight.
    [207] It is applied in a conventional manner adapted to the form of use.
    [208] The active substances according to the invention are also suitable for controlling in vivo and in vitro parasites in the field of veterinary medicine and / or animal breeding. The active substances according to the invention are for example oral administration in the form of tablets, capsules, drinks or granules, for example skin spraying in the form of dipping, spraying, pouring, spotting and dusting, And parenteral administration, for example in the form of injections.
    [209] Thus, the compounds of the formula (I) according to the invention can be advantageously used in particular for livestock raising (eg cattle, sheep, pigs, and poultry such as chickens, geese, etc.). In a preferred embodiment of the invention, the compound, if appropriate in the form of a suitable formulation, is optionally administered orally to the animal with water or food for drink. Since excretion in feces is very effective, the growth of insects in animal feces can be very easily prevented in this way. Suitable dosages and formulations in each case depend in particular on the species and stage of growth of the livestock and the risk of insect infestation and can be readily determined and set by conventional methods. For example, the compound may be used in cattle at a dose of 0.01 to 1 mg / kg body weight.
    [210] In addition to the aforementioned methods of application, the active compounds of the formula (I) according to the invention have good systemic action. Thus, the active compound may also be used in liquid or solid form, whereby the active compound is also in the immediate vicinity of the plant and / or in the immediate vicinity of the plant (e.g., granules in soil spraying, spraying into submerged paddy fields, stem injection in trees, stem bandages in perennial plants When sprayed in), it can be introduced into the plant through parts of the plant (eg roots, roots, stems, trunks, leaves) below and above the soil.
    [211] Furthermore, the active compounds according to the invention are optionally in combination with fungicides, in particular growth and reproductive plant propagation materials, for example seed treatment; For example, it is useful for the treatment of grains, vegetables, cotton, rice, sugar cane and other crops and ornamental plants, the treatment of bulbs, seeding and tubers of other crops and ornamental plants that grow like plants. The treatment may be carried out prior to sowing or before planting (eg by specific seed coating techniques, by dressing in liquid or solid form or as seed box treatment), during sowing or planting, or by a specific spraying technique (eg furrow treatment). Sowing or planting may be carried out later. The amount of active compound used can vary in relatively varying amounts depending on the sparging. Generally, the spread rate is from 1 g to 10 kg per hectare of soil area. Methods of treating plant propagation materials and plant propagation materials treated in this manner are also provided by the present invention.
    [212] The compounds of formula I can also be used to control harmful organisms in crops of known genetically engineered plants or crops of genetically engineered plants to be developed. In general, transgenic plants are characterized by particularly advantageous properties, for example resistance to certain crop protection agents, resistance to plant diseases or pathogens of plant diseases, in particular to specific microorganisms or insects such as fungi, bacteria or viruses. Other specific properties relate to, for example, the amount, quality, storage properties, composition and specific components of the harvested material. Thus, transgenic plants are known in which the starch content is increased, the starch quality is altered or the harvested material has a different fatty acid composition.
    [213] Economically important useful and ornamental plants such as wheat, barley, rye, oats, millet, rice, cassava and corn or other sugarcane, cotton, soybeans, oilseed rape, potatoes, tomatoes, beans, and It is preferably used in transgenic crops of crops of other types of vegetables.
    [214] When used in transgenic crops, in particular transgenic crops that are resistant to insects, in addition to the effects on the harmful organisms observed in other crops, certain effects, such as pests, that can be controlled when sprayed on the transgenic crop of interest are Changes or specifically magnified spectra or varying spread rates that can be used in spreading are observed.
    [215] Therefore, the present invention also relates to the use of the compounds of formula (I) for controlling harmful organisms in transgenic crop plants.
    [216] In addition to the lethal effects on these pests, the compounds of formula (I) also have a pronounced insecticidal effect.
    [217] Insect repellent agents for the purposes of the present invention are substances or mixtures of substances which have a protective or protective effect against other living organisms, in particular harmful pests and offensive pests. The term also encompasses effects such as anti-feeding effects, spawning inhibition or colony development effects in which food intake is prevented or prevented.
    [218] Accordingly, the present invention provides the use of the compounds of formula (I) to achieve the aforementioned effects, particularly in the case of pests mentioned in biological examples.
    [219] The invention also applies to areas where at least one compound of formula (I) is protected or protected from harmful organisms.
    [220] In the case of plants, spraying can mean, for example, treatment of seeds as well as plant treatment.
    [221] Note that in the effect on the colony, the effects can be observed in transition during colony development where summation can occur. In this case, the individual effects can have only less than 100% of efficacy by themselves, but a total of 100% of efficacy is achieved at the end.
    [222] Moreover, the compounds of formula (I) are characterized by the fact that, when the effects described above are used, the composition is usually more readily spread than in the case of direct control. This effect often lasts for a long time so that a duration of action of two months or more is achieved.
    [223] Uses of the compounds according to the invention include, in addition to the direct sparging of the pests, any other sparging in which the compounds of the formula I act on the pests. Such direct spraying can be for example the use of a compound in which the plant or pest in the soil degrades to or degrades a compound of formula (I).
    [224] The disclosures of German patent applications 10014006.8 and 10057911.6 and the enclosed abstracts which are preferentially claimed by the present invention are hereby incorporated by reference.
    [225] The following examples are presented to illustrate the invention.
    [1] The present invention relates to heterocyclic acylsulfimides, methods for their preparation, compositions comprising them, and their use for controlling arthropods and insects such as animal pests, in particular insects and mites.
    [226] A. Drug Examples
    [227] Preparation of Starting Material
    [228] Preparation of N-chloro-4-trifluoromethylnicotinamide (compound of Formula III)
    [229] 1.a) A mixture in 20 ml of CCl 4 of 0.01 mol of 4-trifluoromethylnicotinamide or 2,6-dichloro-4-trifluoromethylnicotinamide and 0.012 mol of tert-butyl hypochlorite is prepared at 80 ° C. ( In a water bath) for 2 hours. The reaction mixture was cooled to 15-20 ° C., the precipitated N-chloroamides were filtered off, washed with 10 ml of CCl 4 and dried at 40-50 ° C. under reduced pressure (10-15 mmHg).
    [230] N-chloro-4-trifluoromethylnicotinamide: yield 85%, m.p. 136 to 138 ° C
    [231] N-chloro-2,6-dichloro-4-trifluoromethylnicotinamide: yield 80%, m.p. 160 to 161 ° C
    [232] 1.b) 4-trifluoromethyl-N-chloronicotinamide hydrochloride
    [233] A 0.5 L four-necked flask with a glass shaft and bearing, thermometer, gas inlet tube and agitator with condenser was initially charged with 150 g of 5% HCl and 50 g of 4-trifluoromethylnicotinamide, and the mixture at room temperature. Stir for 15 minutes and introduce 20 g of Cl 2 from the gas bottle to absorb chlorine virtually completely. After adding about 10 g of chlorine, the starting material began to dissolve and the product precipitated out as a white precipitate. The crystalline product was filtered by suction and the mother liquor was kept individually. The product was washed once with 30-40 ml of ice cold water and dried. The result was 58 g of product: 92% yield (mp (decomposition) 150 ° C., active chlorine 13.7%, HCl 13.5%) The product was reacted with NaHCO 3 for N-chloro-4-trifluoromethylnicotinamide (mp 140 To 141 ° C.).
    [234] 1.c) 4-trifluoromethyl-N-chloronicotinamide hydrotetrafluoroborate
    [235] 10 g of N-chloro-4-trifluoromethylnicotinamide hydrochloride was dissolved in 30 ml of ethanol and a solution of NaBF 4 10 in 10 ml of HBF 4 was added. The mixture was stirred for 20 minutes and the crystalline product was filtered off by suction, washed once with 30-40 ml of ice cold water and dried. As a result, 12 g of 4-trifluoromethyl-N-chloronicotinamide hydrotetrafluoroborate was obtained.
    [236] 2. Synthesis of sulfoxylic acid amide (RN 2 -S-NR 2 )
    [237] At 0-5 ° C., a solution of 0.02 mol of SCl 2 in 20 ml of anhydrous diethyl ether was added dropwise with stirring to a solution of 0.08 mol of the secondary amine in 50 ml of anhydrous diethyl ether.
    [238] The reaction mixture was stirred at 20-25 ° C. for 1 hour, the precipitated amine hydrochloride was filtered off and the filtrate was concentrated under reduced pressure (10-15 mmHg, 25-30 ° C.). The dialkylamides of sulfoxylic acid are oils, which are purified by vacuum distillation (except for any further crude bisamylamides).
    [239] Me 2 NS-NMe 2 , yield 78%, bp. 35-40 ° C. (30 mmHg).
    [240] Et 2 NS-NEt 2 , yield 70%, bp. 88-90 ° C. (15 mmHg).
    [241] (i-Pr 2 ) NSN (i-Pr) 2 , yield 68%, bp. 105 to 108 ° C. (15 mmHg).
    [242] (n-Bu 2 ) NSN (n-Bu) 2 , yield 85%, bp. 118 to 120 ° C. (0.1 mmHg).
    [243] Ph (Et) N-S-NPh (Et), yield 70%, bp. 185-188 ° C. (0.04 mmHg).
    [244] (n-Am 2 ) NSN (n-Am) 2 , yield 76%.
    [245] 3. Synthesis of N, N-dichloroamide of 4-trifluoromethylnicotinic acid and N, N-dichloroamide (compound of Formula VII) of 2,6-dichloro-4-trifluoromethylnicotinic acid
    [246] A mixture of 0.02 mol of 4-trifluoromethylnicotinamide or 2,6-dichloro-4-trifluoromethylnicotinamide, 0.044 mol of t-butyl hypochlorite and 20 ml of CCl 4 was heated at 70 ° C. for 2 hours. Solvent and t-butanol were removed under reduced pressure (10-15 mmHg, 60 ° C.) and dried. The resulting N, N-dichloroamide was used as a yellow oil without further purification.
    [247] 4-trifluoromethylnicotinic acid derivative: yield 95%, 19 F-NMR (CCl 4 ): -63.25
    [248] 2,6-dichloro-4-trifluoromethylnicotinic acid derivative: yield 92%, 19 F-NMR (CCl 4 ): -63.82
    [249] 4.N-3- (4-trifluoromethyl) pyridoylimidosulfite dichloride (compound of formula VIII)
    [250] For this reaction, the solvents must all be anhydrides. From 0 to 5 ℃, CCl 4 for the above-described N, N- dichloro-amide a solution of 0.02mol of 10ml was added with stirring to a solution of sulfur dichloride 0.02mol of CCl 4 20ml. The reaction mixture was stirred at 0-5 ° C. for 15 minutes and then at 20-25 ° C. for 2 hours. A small amount of precipitate was filtered off and the filtrate was concentrated at 50-60 ° C. under reduced pressure of 10-15 mmHg. The product was a light brown oil, which was reacted without further purification.
    [251] 4-trifluoromethylnicotinic acid derivative: yield 93%, 19 F-NMR (CCl 4 ): -62.69
    [252] 2,6-dichloro-4-trifluoromethylnicotinic acid derivative: yield 94%, 19 F-NMR (CCl 4 ): -61.42
    [253] Preparation of the final product
    [254] At 20-25 ° C., a solution in 10 ml of benzene of 0.01 mol of dialkyl sulfide, alkyl aryl sulfide or sulfoxylic acid diamide and 0.01 mol of triethylamine was added dropwise to a solution of 0.01 mol of N-chloronicotinamide in 15 ml of benzene or acetonitrile. . The reaction mixture is stirred at 20-25 ° C. for 3 hours, the precipitated triethylamine hydrochloride is filtered off, and the filtrate is concentrated at 40-50 ° C. under reduced pressure (10-15 mmHg) and, optionally, chromatography on silica. It was.
    [255] As a result, the compounds of Examples 1, 2, 3, 4, 5, 7, 8, 9, 11, 12, 16, 19, and 203 were obtained.
    [256] Compound of Example 66
    [257]
    [258] 0.50 g (0.0015 mol) of methyl- (3-thienyl) -sulfide- (2,4,6-trimethylbenzenesulfonate) and 0.38 g (0.0018 mol) of 4-trifluoromethylnicotinyl chloride were added to 20 ml of dichloromethane. Was dissolved in a solution of 0.38 g (0.0038 mol) of triethylamine in 5 ml of dichloromethane at 0 ° C. The mixture was stirred at rt for 1.5 days, extracted with saturated sodium chloride solution and the organic phase was dried. Concentration gave a colorless solid, which was further purified by silica gel chromatography. As a result, 390 mg (81.6% of theory) were obtained as a colorless solid. m.p. 94 to 95 ℃
    [259] Compound of Example 464
    [260]
    [261] 0.87 g (1.2 mmol) of S, S-bis- [α, α-bis- (trifluoromethane) benzenemethanolato] diphenylsulfur (Martin sulfuran dehydrating agent available from Aldrich) and 4-trifluoromethylnicotine 0.25 g (1.3 mmol) of amide was stirred at room temperature for 6 hours. The solution was left overnight, then concentrated and the residue was stirred with heptane. The undissolved solid (unreacted amide) was filtered off and the residue was chromatographed with silica gel (ethyl acetate / heptane 9: 1). As a result, 0.12 g (25.6% of theory) were obtained as a colorless solid. m.p. 102 to 103 ° C
    [262] Conversion of Compound of Formula VIII to Final Product
    [263] At 5-10 ° C., a solution of 0.061 mol of dialkylamine in 50 ml of benzene was added to a solution of 0.015 mol of the aforementioned dichlorosulfide (compound of formula VIII) in 30 ml of benzene (dimethylamine gas in the case of dimethylamine Passed). The reaction mixture was stirred at 20-25 ° C. for 20 hours and the precipitated amine hydrochloride was filtered off. The filtrate was concentrated under reduced pressure (10-15 mmHg, 50-60 ° C.) and the final product was purified by washing or recrystallization with hexane.
    [264] In this way, the compounds of Examples 5, 6, 10, 29, 30 and 31 were obtained.
    [265] Synthesis of N- (2-amino-6-chloro-4-trifluoromethylnicotinoyl) sulfide
    [266] A mixture of 0.01 mol (2,6-dichloro-4-trifluoromethylnicotinoyl) sulfide and 0.02 mol of the corresponding amine in 15 ml of benzene was heated at 80 ° C. for 3 hours. In the case of dimethylamine, the reaction was carried out by foaming the gaseous amine in solution at 20-25 ° C. Hydrochloride of the amine was filtered and the filtrate was concentrated under reduced pressure (10-15 mmHg, 50-60 ° C.). The final product was washed with hexanes and purified by recrystallization.
    [267] In this way, the compounds of Examples 33, 35, and 36 were obtained.
    [268] Synthesis of sulfoximide
    [269]
    [270] Compound of Example 718
    [271] 500 mg (1.7 mmol) of [4- (2-cyano-3-fluorophenoxy) phenyl] methylsulfoxymid and 210 mg (2.0 mmol) of triethylamine were initially charged in 20 ml of dichloromethane, and 4 at 0 ° C. A solution of 430 mg (2.0 mmol) of trifluoromethylnicotinoyl chloride was added dropwise. The mixture was stirred at rt for 6 h and then concentrated. The residue is taken up in water / dichloromethane, the organic phase is dried and the solvent is removed. Further purification was by silica gel chromatography (ethyl acetate / heptane 9: 1). As a result, crystallization was carried out using heptane to obtain a resin.
    [272] Yield: 420 mg of colorless crystals (53.3% of theory)
    [273] m.p .: 100 to 102 ° C
    [274] Compound of Example 700
    [275]
    [276] 170 mg (0.98 mmol) of 3-chloroperbenzoic acid at 0 ° C. were added dropwise to a solution of 270 mg (0.75 mmol) of (4-trifluoromethylnicotinoyl) diphenyl-sulfide in 10 ml of dichloromethane, and the mixture was stirred at room temperature. I was. The mixture was left overnight and then extracted twice with sodium bicarbonate solution, and the organic phase was dried and concentrated. Further purification was by silica gel chromatography (ethyl acetate). As a result, 120 mg (41% of theory) were obtained as a colorless oil.
    [277]
    [278]
    [279]
    [280]
    [281]
    [282]
    [283]
    [284]
    [285]
    [286]
    [287]
    [288]
    [289]
    [290]
    [291]
    [292]
    [293]
    [294]
    [295]
    [296]
    [297]
    [298]
    [299]
    [300]
    [301]
    [302]
    [303]
    [304]
    [305]
    [306]
    [307]
    [308]
    [309]
    [310]
    [311]
    [312]
    [313]
    [314]
    [315]
    [316]
    [317]
    [318]
    [319]
    [320]
    [321]
    [322]
    [323]
    [324] In addition, the sulfimide derivatives (m = 0) shown in Tables 1 and 2 above may all exist as the corresponding sulfoximide (m = 1). Examples of some representatives of this class of materials are shown in Table 3 below.
    [325]
    [326]
    [327]
    [328] B. Formulation Examples
    [329] a) Dust is obtained by mixing 10 parts by weight of active material and 90 parts by weight of talc as inert material and grinding the mixture with a hammer mill.
    [330] b) 25 parts by weight of active material, 65 parts by weight of kaolin-containing quartz as inert material, 10 parts by weight of potassium lignosulfonate and 1 part by weight of sodium oleoylmethyl titanate as a wetting agent and dispersion, and pinned a disk polishing with a -disk mill) yields a wettable powder that can be easily dispersed in water.
    [331] c) 40 parts by weight of the active substance is mixed with 7 parts by weight of sulfosuccinic acid monoester, 2 parts by weight of sodium lignosulfonate and 51 parts by weight of water, and the mixture is mixed to a fineness of less than 5 탆 using a ball mill. Abrasive concentrates were prepared that could be easily dispersed in water by polishing.
    [332] d) An emulsifiable concentrate can be prepared from 15 parts by weight of active substance, 75 parts by weight of cyclohexane as solvent and 10 parts by weight of oxyethylated nonylphenol (10EO) as emulsifier.
    [333] e) Granules can be prepared from 2 to 15 parts by weight of active material and inert granule carrier materials such as attapulgite, pumice granules and / or quartz sand. It is convenient to use the suspension of the wettable powder of example b) above having a 30% solids content (they are directly dried and mixed), which is sprayed on the surface of the attapulgite granules. The wettable powder is approximately 5% by weight and the inert carrier material is approximately 95% by weight based on the weight of the final granules.
    [334] C. Biological Examples
    [335] Example 1
    [336] The germination kind of practical kidney beans with seed roots (field bean) seeds (non-Shia paba (Vicia faba)) transferred to brown glass bottles filled with tap water, then colony of about 100 black kidney bean aphid (Apis pabae (Aphis fabae)) Was formed. The plants and aphids were then tested for 5 seconds by immersion in an aqueous solution of the formulated formulation. After draining, the plants and animals were stored in specific climate chambers (16 hours daily, 25 ° C., 40-60% relative atmospheric humidity). After 3 and 6 days of storage, the effect of the formulation on aphids was determined. At concentrations of 300 ppm (based on the content of active compound), Examples 1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 21, 22, 23, 24, 25, 27, 28, 37, 40, 42, 53, 54, 55, 57, 64, 66, 84, 87, 89, 90, 94, 97, 108, 110, 114, 120, 121, 122, 123, 175, 181, 182, 183, 184, 185, 191, 193, 195, 196, 202, 204, 209, 217, 218, 220, 221, 222, 223, 225, 226, 227, 228, 229, 230, 231, 232, 233, 234, 235, 237, 243, 244, 245, 246, 249, 264, 356, 357, 359, 376, 378, 379, 380, 429, Formulations of 453, 455, 458, 464, 478, 484, 500, 539, 540, 541, 542, 543, 708, 709, 712, 717, 718 and 719 caused mortality of 90 to 100% for aphids. .
    [337] Example 2
    [338] Germinated seed bean seeds (Bisia baba) with seed roots were transferred to brown glass bottles filled with tap water. 4 ml of an aqueous solution of the formulated formulation tested were interpreted as the brown glass bottle. The seed kidney beans were colonized in large quantities with about 100 black kidney beans aphids (is broken apis). The plants and aphids were then stored in specific climate chambers (16 hours daily, 25 ° C., 40-60% relative atmospheric humidity). After 3 and 6 days of storage, the effect of the formulation on aphids was determined. At concentrations of 30 ppm (based on the content of active compound), Examples 1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 21, 22, 23, 24, 25, 27, 28, 37, 40, 42, 53, 54, 55, 57, 64, 66, 84, 87, 89, 90, 94, 97, 1O8, 110, 114, 120, 121, 122, 123, 175, 181, 182, 183, 184, 185, 191, 193, 195, 196, 202, 204, 209, 217, 218, 220, 221, 222, 223, 225, 226, 227, 228, 229, 230, 231, 232, 233, 234, 235, 237, 243, 244, 245, 249, 264, 356, 357, 359, 376, 378, 379, 380, 429, 453, Formulations of 455, 458, 464, 478, 484, 500, 539, 540, 541, 542, 543, 708, 709, 712, 718 and 719 cause mortality of 90 to 100% for aphids by root tissue action I was.
    [339] Example 3
    [340] Dwarf bean beans were transferred to brown glass bottles filled with tap water. After 5 days, white fly adults ( Trialeurodes vaporariorum ) were placed in kidney beans for 48 hours for spawning. The adult was then removed and an aqueous solution of the formulated formulation tested was pipetted into the brown glass bottle. Next, the colonized plants were stored in a specific climatic chamber (16 hours daily, 25 ° C., 40-60% relative atmospheric humidity). After 12 days storage, the root tissue effect of the formulation on the eggs was determined. At concentrations of 30 ppm (based on the amount of active compound), the formulations of Examples 1, 2, 3, 4, 5, 6, 7, 8, 16, 122, 196, 197, 359, and 464 are not suitable for root tissue action Causing mortality of 90 to 100% for eggs or larvae of aphids.
    [341] Example 4
    [342] Rice seeds were transferred to brown glass bottles filled with tap water. When the roots were 5-6 cm in length, an aqueous solution of the formulated formulation to be tested was pipetted into the brown glass bottle. Rice was then colonized with L3 larvae of the Nephotettix cincticeps , a rice leaf locust species. The colonized plants were then stored in a specific climate chamber (16 hours daily, 25 ° C., 40-60% relative atmospheric humidity). After 4 days storage, the root tissue effect of the formulation on the leaf grasshopper was determined. At concentrations of 30 ppm (based on the content of active compound), the formulations of Examples 2, 5 and 7 caused 90-100% mortality to aphids of leaf locusts by root tissue action.
    权利要求:
    Claims (19)
    [1" claim-type="Currently amended] Acylsulfimides of Formula I and salts thereof
    Formula I

    Where
    X is CH or N;
    Y is O or S;
    m is 0 or 1;
    n is 0 or 1;
    R 1 is C 1 -C 6 -haloalkyl;
    R 2 and R 3 are the same or different and are H, halogen or branched or unbranched (C 1 -C 6 ) -alkyl group wherein one or two of the CH 2 groups in the alkyl group are -O-, -S - or -N (C 1 -C 6) - may be substituted by alkyl, with the proviso that the heteroatom can not be adjacent to each other;
    R 4 and R 5 are the same or different and R 6 , -C (W) R 7 , -C (= NOR 7 ) R 7 , -C (= NNR 7 2 ) R 7 , -C (= W) OR 7 , -C (= W) NR 7 2 , -OC (= W) R 7 , -OC (= W) OR 7 , -NR 7 C (= W) R 7 , --N [C (= W) R 7 ] 2 , -NR 7 C (= W) OR 7 , -C (= W) NR 7 -NR 7 2 , -C (= W) NR 7 -NR 7 [C (= W) R 7 ], -NR 7 -C (= W) NR 7 2 , -NR 7 -NR 7 C (= W) R 7 , -NR 7 -N [C (= W) R 7 ] 2 , -N [(C = W ) R 7 ] -NR 7 2 , -NR 7 -NR 7 [(C = W) WR 7 ], -NR 7 [(C = W) NR 7 2 ], -NR 7 (C = NR 7 ) R 7 , -NR 7 (C = NR 7 ) NR 7 2 , -O-NR 7 2 , -O-NR 7 (C = W) R 7 , -SO 2 NR 7 2 , -NR 7 SO 2 R 7 ,- SO 2 OR 7 , -OSO 2 R 7 , -OR 7 , -NR 7 2 , -SR 7 , -SiR 7 3 , -PR 7 2 , -P (= W) R 7 , -SOR 7 , -SO 2 R 7 , -PW 2 R 7 2, or -PW 3 R 7 2, or
    R 4 and R 5 together with the sulfur to which they are attached form a 3-8 membered saturated or unsaturated ring system which is optionally mono- or polysubstituted and optionally contains 1-4 additional hetero atoms Wherein two or more substituents optionally form one or more additional ring systems;
    W is O or S;
    R 6 is the same or different and is (C 1 -C 20 ) -alkyl, (C 2 -C 20 ) -alkenyl, (C 2 -C 20 ) -alkynyl, (C 3 -C 8 ) -cycloalkyl , (C 4 -C 8 ) -cycloalkenyl, (C 8 -C 10 ) -cycloalkynyl, aryl or heterocyclyl, these radicals may optionally be mono- or polysubstituted;
    R 7 is the same or different and is H or R 6 .
    [2" claim-type="Currently amended] The method of claim 1,
    Acylsulfimides of formula I wherein X is CH.
    [3" claim-type="Currently amended] The method according to claim 1 or 2,
    Acylsulfimides of formula (I) wherein Y is O.
    [4" claim-type="Currently amended] The method according to any one of claims 1 to 3,
    Acylsulfimides of formula (I) wherein n is zero.
    [5" claim-type="Currently amended] The method according to any one of claims 1 to 4,
    Acylsulfimides of formula (I) wherein R 1 is (C 1 -C 6 ) -alkyl mono- or polysubstituted by F and / or Cl.
    [6" claim-type="Currently amended] The method according to any one of claims 1 to 5,
    Acylsulfimides of formula I in which the radicals R 4 and R 5 have at least one substituent R 8 and R 8 are defined as:
    R 8 is the same or different and is R 9 or two radicals R 8 together with the atoms to which they are attached form a 3-8 membered saturated or unsaturated ring system optionally substituted by one or more radicals R 9 , and The ring system optionally further contains heteroatoms;
    R 9 is the same or different and R 10 , R 11 , -C (W) R 10 , -C (= NOR 10 ) R 10 , -C (= NNR 10 2 ) R 10 , -C (= W) OR 10 , -C (= W) NR 10 2 , -OC (= W) R 10 , -OC (= W) OR 10 , -NR 10 C (= W) R 10 , -N [C (= W) R 10 ] 2 , -NR 10 C (= W) OR 10 , -C (= W) NR 10 -NR 10 2 , -C (= W) NR 10 -NR 10 [C (= W) R 10 ],- NR 10 -C (= W) NR 10 2 , -NR 10 -NR 10 C (= W) R 10 , -NR 10 -N [C (= W) R 10 ] 2 , -N [(C = W) R 10 ] -NR 10 2 , -NR 10 -N [(C = W) WR 10 ], -NR 10 [(C = W) NR 10 2 ], -NR 10 (C = NR 10 ) R 10 ,- NR 10 (C = NR 10 ) NR 10 2 , -O-NR 10 2 , -O-NR 10 (C = W) R 10 , -SO 2 NR 10 2 , -NR 10 SO 2 R 10 , -SO 2 OR 10 , -OSO 2 R 10 , -OR 10 , -NR 10 2 , -SR 10 , -SiR 10 3 , -PR 10 2 , -P (= W) R 10 2 , -SOR 10 , -SO 2 R 10 , -PW 2 R 10 2 or -PW 3 R 10 2, or two radicals R 9 together are = W, = NR 10 , = CR 2 10 , CHR 10 or = CH 2 ;
    R 10 is the same or different and is (C 1 -C 6 ) -alkyl, (C 2 -C 6 ) -alkenyl, (C 2 -C 6 ) -alkynyl, (C 3 -C 8 ) -cycloalkyl , (C 4 -C 8 ) -cycloalkenyl, (C 3 -C 8 ) -cycloalkyl- (C 1 -C 4 ) -alkyl, (C 4 -C 8 ) -cycloalkenyl- (C 1- C 4 ) -alkyl, (C 3 -C 8 ) -cycloalkyl- (C 2 -C 4 ) -alkenyl, (C 4 -C 8 ) -cycloalkenyl- (C 2 -C 4 ) -alkenyl , (C 1 -C 6 ) -alkyl- (C 3 -C 8 ) -cycloalkyl, (C 2 -C 6 ) -alkenyl- (C 3 -C 8 ) -cycloalkyl, (C 2 -C 6 ) -Alkynyl- (C 3 -C 8 ) -cycloalkyl, (C 1 -C 6 ) -alkyl- (C 4 -C 8 ) -cycloalkenyl, (C 2 -C 6 ) -alkenyl- ( C 4 -C 8 ) -cycloalkenyl, aryl or heterocyclyl, these radicals are optionally substituted by one or more radicals R 11 , optionally two radicals R 10 together form a ring system;
    R 11 is the same or different and is halogen, cyano, nitro, hydroxy, thio, amino, formyl, (C 1 -C 6 ) -alkanoyl, (C 1 -C 6 ) -alkoxy, (C 3 -C 6 ) -alkenyloxy, (C 3 -C 6 ) -alkynyloxy, (C 1 -C 6 ) -haloalkyloxy, (C 3 -C 6 ) -haloalkenyloxy, (C 3 -C 6 ) -Haloalkynyloxy, (C 3 -C 8 ) -cycloalkoxy, (C 4 -C 8 ) -cycloalkenyloxy, (C 3 -C 8 ) -halocycloalkoxy, (C 4 -C 8 ) Halocycloalkenyloxy, (C 3 -C 8 ) -cycloalkyl- (C 1 -C 4 ) -alkoxy, (C 4 -C 8 ) -cycloalkenyl- (C 1 -C 4 ) -alkoxy, (C 3 -C 8 ) -cycloalkyl- (C 2 -C 4 ) -alkenyloxy, (C 4 -C 8 ) -cycloalkenyl- (C 1 -C 4 ) -alkenyloxy, (C 1 -C 6 ) -alkyl- (C 3 -C 8 ) -cycloalkoxy, (C 2 -C 6 ) -alkenyl- (C 3 -C 8 ) -cycloalkoxy, (C 2 -C 6 ) -alkynyl -(C 3 -C 8 ) -cycloalkoxy, (C 1 -C 6 ) -alkyl- (C 4 -C 8 ) -cycloalkenyloxy, (C 2 -C 6 ) -alkenyl- (C 4- C 8 ) -cycle Roalkenyloxy, (C 1 -C 4 ) -alkoxy- (C 1 -C 6 ) -alkoxy, (C 1 -C 4 ) -alkoxy- (C 3 -C 6 ) -alkenyloxy, carbamoyl, ( C 1 -C 6 ) -mono- or dialkylcarbamoyl, (C 1 -C 6 ) -mono- or dihaloalkylcarbamoyl, (C 3 -C 8 ) -mono- or dicycloalkylcarbamoyl, ( C 1 -C 6 ) -alkoxycarbonyl, (C 3 -C 8 ) -cycloalkoxycarbonyl, (C 1 -C 6 ) -alkanoyloxy, (C 3 -C 8 ) -cycloalkanoyloxy, ( C 1 -C 6 ) -haloalkoxycarbonyl, (C 1 -C 6 ) -haloalkanoyloxy, (C 1 -C 6 ) -alkanamido, (C 1 -C 6 ) -haloalkanamido, (C 2 -C 6 ) -alkenamido, (C 3 -C 8 ) -cycloalkanamido, (C 3 -C 8 ) -cycloalkyl- (C 1 -C 4 ) -alkanamido, (C 1 -C 6 ) -alkylthio, (C 3 -C 6 ) -alkenylthio, (C 3 -C 6 ) -alkynylthio, (C 1 -C 6 ) -haloalkylthio, (C 3 -C 6 ) -haloalkenylthio, (C 3 -C 6 ) -haloalkynylthio, (C 3 -C 8 ) -cycloalkylthio, (C 4 -C 8 ) -cycloalkenylthio, (C 3- C 8 ) -do Cyclocycloalkylthio, (C 4 -C 8 ) -halocycloalkenylthio, (C 3 -C 8 ) -cycloalkyl- (C 1 -C 4 ) -alkylthio, (C 4 -C 8 ) -cyclo alkenyl, - (C 1 -C 4) - alkylthio, (C 3 -C 8) - cycloalkyl, - (C 3 -C 4) - alkenyl, thio, (C 4 -C 8) - cycloalkenyl - ( C 3 -C 4 ) -alkenylthio, (C 1 -C 6 ) -alkyl- (C 3 -C 8 ) -cycloalkylthio, (C 2 -C 6 ) -alkenyl- (C 3 -C 8 ) -Cycloalkylthio, (C 2 -C 6 ) -alkynyl- (C 3 -C 8 ) -cycloalkylthio, (C 1 -C 6 ) -alkyl- (C 4 -C 8 ) -cycloalkenyl Thio, (C 2 -C 6 ) -alkenyl- (C 4 -C 8 ) -cycloalkenylthio, (C 1 -C 6 ) -alkylsulfinyl, (C 3 -C 6 ) -alkenylsulfinyl , (C 3 -C 6 ) -alkynylsulfinyl, (C 1 -C 6 ) -haloalkylsulfinyl, (C 3 -C 6 ) -haloalkenylsulfinyl, (C 3 -C 6 ) -halo Alkynylsulfinyl, (C 3 -C 8 ) -cycloalkylsulfinyl, (C 4 -C 8 ) -cycloalkenylsulfinyl, (C 3 -C 8 ) -halocycloalkylsulfinyl, (C 4- C 8 ) -halocycloalkenylsulfinyl , (C 3 -C 8 ) -cycloalkyl- (C 1 -C 4 ) -alkylsulfinyl, (C 4 -C 8 ) -cycloalkenyl- (C 1 -C 4 ) -alkylsulfinyl, (C 3 -C 8 ) -cycloalkyl- (C 3 -C 4 ) -alkenylsulfinyl, (C 4 -C 8 ) -cycloalkenyl- (C 3 -C 4 ) -alkenylsulfinyl, (C 1 -C 6 ) -alkyl- (C 3 -C 8 ) -cycloalkylsulfinyl, (C 2 -C 6 ) -alkenyl- (C 3 -C 8 ) -cycloalkylsulfinyl, (C 2 -C 6 ) -Alkynyl- (C 3 -C 8 ) -cycloalkylsulfinyl, (C 1 -C 6 ) -alkyl- (C 4 -C 8 ) -cycloalkenylsulfinyl, (C 2 -C 6 )- alkenyl - (C 4 -C 8) - cycloalkenyl sulfinyl, (C 1 -C 6) - alkylsulfonyl, (C 3 -C 6) - alkenyl nilseol sulfonyl, (C 3 -C 6) - alkynyl Nylsulfonyl, (C 1 -C 6 ) -haloalkylsulfonyl, (C 3 -C 6 ) -haloalkenylsulfonyl, (C 3 -C 6 ) -haloalkynylsulfonyl, (C 3 -C 8 )- Cycloalkylsulfonyl, (C 4 -C 8 ) -cycloalkenylsulfonyl, (C 3 -C 8 ) -halocycloalkylsulfonyl, (C 4 -C 8 ) -halocycloalkenylsulfonyl, (C 3- C 8) - cycloalkyl, - (C 1 -C 4) - Kilseol sulfonyl, (C 4 -C 8) - cycloalkenyl - (C 1 -C 4) - alkylsulfonyl, (C 3 -C 8) - cycloalkyl, - (C 3 -C 4) - alkenyl nilseol sulfonyl, (C 4 -C 8 ) -cycloalkenyl- (C 3 -C 4 ) -alkenylsulfonyl, (C 1 -C 6 ) -alkyl- (C 3 -C 8 ) -cycloalkylsulfonyl, (C 2 -C 6) - alkenyl, - (C 3 -C 8) - cycloalkyl, sulfonyl, (C 2 -C 6) - alkynyl, - (C 3 -C 8) - cycloalkyl, sulfonyl, (C 1 -C 6 ) -alkyl- (C 4 -C 8 ) -cycloalkenylsulfonyl, (C 2 -C 6 ) -alkenyl- (C 4 -C 8 ) -cycloalkenylsulfonyl, (C 1 -C 6 )- Dialkylamino, (C 1 -C 6 ) -alkylamino, (C 3 -C 6 ) -alkenylamino, (C 3 -C 6 ) -alkynylamino, (C 1 -C 6 ) -haloalkylamino , (C 3 -C 6 ) -haloalkenylamino, (C 3 -C 6 ) -haloalkynylamino, (C 3 -C 8 ) -cycloalkylamino, (C 4 -C 8 ) -cycloalkenyl Amino, (C 3 -C 8 ) -halocycloalkylamino, (C 4 -C 8 ) -halocycloalkenylamino, (C 3 -C 8 ) -cycloalkyl- (C 1 -C 4 ) -alkylamino , (C 4 -C 8 ) -cycloalkenyl- (C 1 -C 4 ) -alkylamino, (C 3 -C 8 ) -cycloalkyl- (C 3 -C 4 ) -alkenylamino, (C 4- C 8 ) -cycloalkenyl- (C 3 -C 4 ) -alkenylamino, (C 1 -C 6 ) -alkyl- (C 3 -C 8 ) -cycloalkylamino, (C 2 -C 6 )- alkenyl - (C 3 -C 8) - cycloalkyl, amino, (C 2 -C 6) - alkynyl, - (C 3 -C 8) - cycloalkyl, amino, (C 1 -C 6) - alkyl, - (C 4 -C 8 ) -cycloalkenylamino, (C 2 -C 6 ) -alkenyl- (C 4 -C 8 ) -cycloalkenylamino, (C 1 -C 6 ) -trialkylsilyl, aryl, aryl Oxy, arylthio, arylamino, aryl- (C 1 -C 4 ) -alkoxy, aryl- (C 3 -C 4 ) -alkenyloxy, aryl- (C 1 -C 4 ) -alkylthio, aryl- ( C 2 -C 4 ) -alkenylthio, aryl- (C 1 -C 4 ) -alkylamino, aryl- (C 3 -C 4 ) -alkenylamino, aryl- (C 1 -C 6 ) -dialkyl alkylsilyl, diaryl - (C 1 -C 6) - alkylsilyl, triarylsilyl and 5- or 6-membered, and heterocyclyl, these radicals of the cyclic radical of the last 14 The residue is optionally hydrogen, cyano, nitro, amino, hydroxy, thio, (C 1 -C 4 ) -alkyl, (C 1 -C 4 ) -haloalkyl, (C 3 -C 8 ) -cycloalkyl, (C 1 -C 4 ) -alkoxy, (C 1 -C 4 ) -haloalkoxy, (C 1 -C 4 ) -alkylthio, (C 1 -C 4 ) -haloalkylthio, (C 1 -C 4 ) -Alkylamino, (C 1 -C 4 ) -haloalkylamino, formyl and (C 1 -C 4 ) -alkanoyl.
    [7" claim-type="Currently amended] The method according to any one of claims 1 to 6,
    Acylsulfimides of formula I in which the SR 4 R 5 unit has the structure of formulas A to E:
    Formula A

    [Wherein,
    r is 0 or 1;
    D is a direct bond, branched or unbranched (C 1 -C 4 ) -alkylene, O, S (O) 0,1,2 , NR 11 ;
    R 9 is the same as defined in claim 6;
    R 11 is H, (C 1 -C 4 ) -alkyl, (C 1 -C 4 ) -alkanoyl, (C 1 -C 4 ) -alkoxycarbonyl, (C 1 -C 4 ) -alkyl- or- Dialkylaminocarbonyl or (C 1 -C 4 ) -alkylsulfonyl;
    a and b are the same or different and are 0, 1, 2, 3 or 4.] Formula B

    [Wherein,
    R 12 is optionally substituted or condensed with an optionally substituted phenyl radical or (C 3 -C 6 ) -cycloalkyl radical optionally substituted with (C 1 -C 8 ) -alkyl, optionally substituted phenyl radical (C 3 -C 6 ) -cycloalkyl;
    R 9 is the same as defined in claim 6;
    a is 0, 1, 2, 3, 4 or 5.] Formula C

    [Wherein,
    R 9 has the meaning defined in claim 6;
    a is 0, 1, 2, 3 or 4, preferably 0, 1 or 2;
    R 13 is a straight or branched (C 2 -C 8 ) -alkanediyl group optionally substituted or condensed with one or two optionally substituted phenyl groups.] Formula D

    [Wherein,
    R 14 and R 15 are the same or different and are (C 1 -C 8 ) -alkyl, optionally substituted phenyl optionally substituted by an optionally substituted phenyl radical or a (C 3 -C 8 ) -cycloalkyl radical (C 3 -C 6 ) -cycloalkyl optionally substituted or condensed by a radical.] Formula E

    [Wherein,
    R 16 is a straight or branched (C 2 -C 8 ) -alkanediyl optionally substituted by one or two optionally substituted phenyl groups when the phenyl group is condensed with one or two optionally substituted phenyl groups It's a flag.] [8" claim-type="Currently amended] 12. Preparation of a compound of formula I according to any one of claims 1 to 7, wherein Y is oxygen, comprising reacting a carboxylic acid of formula V in the form of an activated derivative thereof with a compound of formula Way:
    Formula V

    [Wherein,
    R 1 , R 2 , R 3 , X and n are the same as defined for Formula I above.] Formula VI

    [Wherein,
    R 4 , R 5 and m are the same as defined for Formula I above.] [9" claim-type="Currently amended] A composition having insecticidal, acaricidal and / or nematicidal action comprising at least one compound of the formula (I) according to any one of claims 1 to 7.
    [10" claim-type="Currently amended] The method of claim 9,
    A composition having insecticidal, tick insecticidal and / or nematicidal action present in a mixture with a carrier and / or surfactant.
    [11" claim-type="Currently amended] In accordance with claim 9 or 10,
    A composition further comprising an active compound selected from the group consisting of tick insecticides, fungicides, preparations, insecticides, nematicides and growth regulators.
    [12" claim-type="Currently amended] Use of a compound according to any one of claims 1 to 7 or a composition according to claim 9 or 10 for the manufacture of a veterinary drug.
    [13" claim-type="Currently amended] A method for controlling harmful insects, mites and nematodes, comprising spraying an effective amount of a compound according to any one of claims 1 to 7 or a composition according to any one of claims 9 to 11 to a site of action.
    [14" claim-type="Currently amended] Harmful insects, mites and nematodes, comprising using at least one compound according to any one of claims 1 to 7 or a composition according to any one of claims 9 to 11 for treating seeds of useful plants. How to protect useful plants from the harmful effects of.
    [15" claim-type="Currently amended] Use of a compound according to any one of claims 1 to 7 or a composition according to any one of claims 9 to 11 for controlling harmful insects, mites and nematodes.
    [16" claim-type="Currently amended] 4-trifluoromethylnicotinamide is chlorinated with Cl 2 in aqueous acid, optionally subsequently ion exchanged and / or reacted with a base to give N-chloro-4-trifluoromethylnicotinamide A process for preparing N-chloro-4-trifluoromethylnicotinamide and salts thereof of Formula IIIa comprising:
    Formula IIIa

    Where
    A is a non-oxidizing organic or inorganic anion.
    [17" claim-type="Currently amended] A salt of N-chloro-4-trifluoromethylnicotinamide of formula IIIa
    Formula IIIa

    Where
    A is a non-oxidizing organic or inorganic anion.
    [18" claim-type="Currently amended] The method of claim 17,
    A is F, HF 2 , Cl, BF 4 , PF 6 , HSO 4 , 1 / 2SO 4 , CH 3 COO, CF 3 COO CF 3 SO 3 , CH 3 SO 3 , p-CH 3 -C 6 H 5 SO A salt of formula IIIa which is 3 or H 2 PO 4 .
    [19" claim-type="Currently amended] Use of N-chloro-4-trifluoromethylnicotinamide hydrochloride as intermediate in the synthesis of the sulfimide of formula I according to claim 1.
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    同族专利:
    公开号 | 公开日
    EP1274683A2|2003-01-15|
    MXPA02009313A|2005-04-19|
    WO2001070692A3|2002-03-14|
    RU2002128622A|2004-02-27|
    US20040167334A1|2004-08-26|
    HU0300406A3|2003-10-28|
    JP2003528081A|2003-09-24|
    US20020032328A1|2002-03-14|
    AU6210501A|2001-10-03|
    CA2403807A1|2002-09-20|
    AR027688A1|2003-04-09|
    CN1419542A|2003-05-21|
    BR0109473A|2003-06-03|
    HU0300406A2|2003-06-28|
    PL359666A1|2004-08-23|
    IL151823D0|2003-04-10|
    WO2001070692A2|2001-09-27|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2000-03-22|Priority to DE10014006.8
    2000-03-22|Priority to DE2000114006
    2000-11-21|Priority to DE2000157911
    2000-11-21|Priority to DE10057911.6
    2001-03-17|Application filed by 바이엘 크롭사이언스 게엠베하
    2001-03-17|Priority to PCT/EP2001/003083
    2002-10-26|Publication of KR20020081469A
    优先权:
    申请号 | 申请日 | 专利标题
    DE10014006.8|2000-03-22|
    DE2000114006|DE10014006A1|2000-03-22|2000-03-22|New heterocyclic acylsulfimide derivatives, useful as insecticides, acaricides and nematocides for plant protection or in veterinary medicine|
    DE2000157911|DE10057911A1|2000-11-21|2000-11-21|New heterocyclic acylsulfimide derivatives, useful as insecticides, acaricides and nematocides for plant protection or in veterinary medicine|
    DE10057911.6|2000-11-21|
    PCT/EP2001/003083|WO2001070692A2|2000-03-22|2001-03-17|Heterocyclic acylsulfimides, a method for their production, agents containing the same and their use as pesticides|
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