ZA200207479B - Heterocyclic acylsulfimides, processes for their preparation, compositions comprising them and their use as pesticides. - Google Patents

Heterocyclic acylsulfimides, processes for their preparation, compositions comprising them and their use as pesticides. Download PDF

Info

Publication number
ZA200207479B
ZA200207479B ZA200207479A ZA200207479A ZA200207479B ZA 200207479 B ZA200207479 B ZA 200207479B ZA 200207479 A ZA200207479 A ZA 200207479A ZA 200207479 A ZA200207479 A ZA 200207479A ZA 200207479 B ZA200207479 B ZA 200207479B
Authority
ZA
South Africa
Prior art keywords
alkyl
cycloalkyl
alkenyl
cycloalkenyl
formula
Prior art date
Application number
ZA200207479A
Inventor
Shermolovich Yuri Grigorievich
Oswald Ort
Daniela Jans
Maria-Theresia Thoenessen
Waibel Jutta Maria
Kornuta Pavel Petrovich
Uwe Doeller
Wolfgang Schaper
Ulrich Sanft
Marion Beckmann
Segiy Pazenok
Original Assignee
Bayer Cropscience Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer Cropscience Gmbh filed Critical Bayer Cropscience Gmbh
Publication of ZA200207479B publication Critical patent/ZA200207479B/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D419/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen, oxygen, and sulfur atoms as the only ring hetero atoms
    • C07D419/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen, oxygen, and sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D419/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen, oxygen, and sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pyridine Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)

Description

Description
Heterocyclic acylsulfimides, processes for their preparation, compositions comprising them and their use as pesticides
The invention relates to heterocyclic acylsulfimides, to processes for their preparation, to compositions comprising them and to their use for controlling animal pests, in particular arthropods, such as insects and acarids, and helminths.
Owing to the enormous damage caused by insects, for example by feeding on useful plants, stored food, wood and textiles, or else by transferring diseases to man, domestic animals and useful plants, the use of insecticides or repellents is still indispensable. Insecticides are an important component of integrated pest control, and their contribution is decisive with respect to harvest yield and yield continuity all over the world.
EP-A 0 580 374 discloses trifluoromethylpyridine amides for use as pesticides.
However, since the ecological and economical demands made on modern insecticides are increasing permanently, for example with respect to toxicity, selectivity, application rate, formation of residues and favorable manufacture and there can furthermore be problems, for example with resistance, there is a constant need to develop novel insecticides which, at least in some areas, have advantages over those of the prior art.
It has been found that compounds of the formula (1), if appropriate also as salts, have a good activity spectrum against animal pests and at the same time good plant tolerance and favorable toxicological properties with respect to mammals and aquatic animals.
Sulfimides of unsubstituted nicotinamide are described in Fiziol Biokhim Kul't Rast (1999), 31 (4), 303-307, as safeners for herbicides. That 4-haloalkyl-substituted compounds are suitable for use as insecticides cannot be derived from this publication.
Accordingly, the invention provides acylsulfimides and -sulfoximides of the formula (I) and salts thereof,
Ro (Pn
PO (1)
NE R® R°® (0), where the symbols and indices are as defined below:
X is CH or N;
Y isOorsS; n is 0 or 1; m isOori;
R' is Cy-Ce-haloalky!;
RZ, R® are identical or different and are H, halogen or a branched or unbranched (C;-C¢)-alky! group, where one or two CH, groups may be replaced by -O- or -S- or -N(C4-Cg)-alkyl, with the proviso that heteroatoms may not be adjacent to one another;
R* R® are identical or different and are R®, -C(=W)R’, -C(=NOR")R’, -C(=NNR;)R’, -C(=W)OR’, -C(=W)NR", -OC(=W)R’, -OC(=W)OR’, -NR’C(=W)R’, --N[C(=W)R],, -NR’C(=W)OR’, -C(=W)NR’-NR’,, -C(=W)NR’-NR’[C(=W)R"], -NR’-C(=W)NR’,, -NR’-NR’C(=W)R’, -NR’-N[C(=W)R]2, -N[(C=W)R"]-NR"2, -NR’-NR"[(C=W)WR’], -NR’[(C=W)NR’.], -NR’(C=NR’)R’, -NR’(C=NR")NR, -O-NR’», -O-NR’(C=W)R’, -SO;NR2, -NR’SO,R’, -SO,0R’, -OSO,R’, -OR’, -NR’;, -SR’, -SiR"3, -PR’3, -P(=W)R’, -SOR’, -SO.R’, -PW,R’,, -PW3R',; or
R*and R® together with the sulfur to which they are attached form a three- to eight-membered saturated or unsaturated, preferably carbocyclic ring system which is optionally mono- or polysubstituted, preferably by radicals R®, and which optionally contains 1 to 4 further heteroatoms,
where two or more of the substituents optionally form one or more further ring systems;
Ww isOorS;
R® are identical or different and are (C-Cxo)-alkyl, (C2-Cyp)-alkenyl, (C,-
Czo)-alkynyl, (C3-Cg)-cycloalkyl, (C4-Cs)-cycloalkenyl, (Cg-C1o)- cycloalkynyl, aryl or heterocyclyl, where the radicals mentioned may optionally be mono- or polysubstituted, preferably by radicals R®:
R’ are identical or different and are H or R®.
The symbols and indices in the formula (1) are preferably as defined below:
X is preferably CH.
Y is preferably O. m is preferably 0. n is preferably 0.
R' is preferably (C4-Cg)-alkyl which is mono- or polysubstituted by F and/or
Cl, particularly preferably CFs, CHF, or CF,ClI, very particularly preferably CFs.
RRS are preferably H, halogen, (C1-Cg)-alkoxy, NH(C1-Cg)-alkyl, N(C1-Ce)o- alkyl, particularly preferably H.
R* R® are preferably OR’, NR", or R®, preferably R®.
Particular preference is given to those compounds of the formula (1), in which the symbols and indices are as defined below:
X is preferably CH.
Y is preferably O. m is preferably 0. n is preferably 0.
R’ is preferably CFs.
R? R® are preferably H.
R* R® are preferably R® .
Preferred substituents on the radicals R*, R® are groups R®, which are as defined below:
R® are identical or different and are R®, or two radicals R® together with the atoms to which they are attached form a three- to eight-membered saturated or unsaturated ring system, optionally substituted by one or more radicals R®, which optionally also contains further heteroatoms, preferably O, N, S, SO and/or SO,:
R® are identical or different and are R'’, R"", -C(W)R'", -C(=NOR'®)R", -C(=NNR',)R, -C(=W)OR'®, -C(=W)NR'%,, -OC(=W)R", -OC(=W)OR', -NR"°C(=W)R"°, -N[C(=W)R'%),, -NR'°C(=W)OR'®, -C(=W)NR'-NR', -C(=W)NR'-NR"[C(=W)R%], -NR"*-C(=W)NR'’,, -NR™-NR™C(=W)R', -NR'®-N[C(=W)R%, -N[(C=W)R®]-NR?,, -NR™-N[(C=W)WR'’}, -NR"[(C=W)NR"’,], -NR'%(C=NR')R® -NR'*(C=NR')NR%, -O-NR';, -O-NR'°(C=W)R®, -SO,NR'’,, -NR™SO.R", -S0,0R, -0SO,R™, -OR", -NR'%,, -SR'®, -SiR", -PR', -P(=W)R'’,, -SOR, -SO,R, -PW,R"%, -PW,R'%,, or two radicals R® together are (=W), (=N-R'°), (=CR,'%, (=CHR), or (=CH,);
R'™ are identical or different and are (C1-Cg)-alkyl, (Co-Cs)-alkenyl, (C,-Ce)- alkynyl, (C3-Csg)-cycloalkyl, (C4-Cs)-cycloalkenyl, (C3-Cs)-cycloalkyl- (C+-Cy)-alkyl, (C4-Cg)-cycloalkenyl-(C4-Cy)-alkyl, (Cs-Cg)-cycloalkyi- (C2-Ca)-alkenyl, (C4-Cg)-cycloalkenyl-(Co-Cy4)-alkenyl, (C1-Cg)-alkyl- (Cs-Cs)-cycloalkyl, (C,-Cg)-alkenyl-(C3-Cg)-cycloalkyl, (C2-Ce)-alkynyl- (C3-Cg)-cycloalkyl, (C1-Cg)-alkyl-(C4-Cg)-cycloalkenyl, (C2-Ce)-alkenyl- (C4-Cg)-cycloalkenyl, aryl, heterocyclyl; where the radicals mentioned are optionally substituted by one or more radicals R"' and optionally two radicals R' together form a ring system;
R" are identical or different and are halogen, cyano, nitro, hydroxyl, thio, amino, formyl, (C4-Ce)-alkanoyl, (C4-Cg)-alkoxy, (C3-Ce)-alkenyloxy, (Cs-
Ce)-alkynyloxy, (C1-Cg)-haloalkyloxy, (C3-Ce)-haloalkenyloxy, (C3-Cg)- haloalkynyloxy, (Cs-Cs)-cycloalkoxy, (C4-Csg)-cycloalkenyloxy, (C3-Cg)- halocycloalkoxy, (C4-Cg)-halocycloalkenyloxy, (Cs-Cg)-cycloalkyl-(C;-
Ca)-alkoxy, (Cs-Cg)-cycloalkenyl-(C4-Cq)-alkoxy, (C3-Cg)-cycloalkyl-(C,-
Ca)-alkenyloxy, (Cs-Cs)-cycloalkenyl-(C1-C4)-alkenyloxy, (C1-Ce)-alkyl- (Cs-Cs)-cycloalkoxy, (C2-Ce)-alkenyl-(C3-Cg)-cycloalkoxy, (Co-Ce)- alkynyl-(Cs-Cg)-cycloalkoxy, (C+-Ce)-alkyl-(C4-Cs)-cycloalkenyloxy, (C,-
Ce)-alkenyl-(C4-Cg)-cycloalkenyloxy, (C1-Cy)-alkoxy-(C+-Cg)-alkoxy, (C4-
Ca)-alkoxy-(C3-Cg)-alkenyloxy, carbamoyl, (C-Cg)-mono- or dialkylcarbamoyl, (C+-Cs)-mono- or dihaloalkylcarbamoyl, (C3-Cg)- mono- or dicycloalkylcarbamoyl, (C,-Cg)-alkoxycarbonyl, (C3-Cg)- cycloalkoxycarbonyl, (C-Ce)-alkanoyloxy, (C3-Cs)-cycloalkanoyloxy, (C+-Ce)-haloalkoxycarbonyl, (C4-Cg)-haloalkanoyloxy, (C;-Cg)- 5 alkanamido, (C4-Cg)-haloalkanamido, (C,-Cs)-alkenamido, (C3-Cg)- cycloalkanamido, (Cs-Cs)-cycloalkyl-(C1-Ca)-alkanamido, (C1-Cg)- alkylthio, (Cs-Cg)-alkenylthio, (C3-Cg)-alkynylthio, (C4-Ce)-haloalkyithio, (C3-Ce)-haloalkenylthio, (Cs-Ce)-haloalkynylthio, (C3-Cs)-cycloalkyithio, (C4-Cg)-cycloalkenylthio, (Cs-Cg)-halocycloalkylthio, (C4-Cg)- halocycloalkenylthio, (C3-Cg)-cycloalkyl-(C4-Cs)-alkylthio, (C4-Cg)- cycloalkenyl-(C4-Ca)-alkylthio, (C3-Cg)-cycloalkyl-(C3-C,)-alkenylthio, (C4-Cg)-cycloalkenyl-(C3-Cy)-alkenylthio, (C1-Ce)-alkyl-(C3-Cg)- cycloalkylithio, (C2-Ce)-alkenyl-(C3-Cg)-cycloalkyithio, (C2-Cs)-alkynyl- (Cs-Cs)-cycloalkyithio, (C4-Cg)-alkyl-(C4-Cg)-cycloalkenyithio, (C2-Ce)- alkenyl-(C4-Cg)-cycloalkenylthio, (C4-Cg)-alkylsulfinyl, (C5-Ce)- alkenylsulfinyl, (Cs-Ce)-alkynyisulfinyl, (C1-Cs)-haloalkylsulfinyl, (C3-Cg)- haloalkenylsulfinyl, (Cs-Cg)-haloalkynylsulfinyl, (C3-Cs)- cycloalkylsulfinyl, (C4-Cg)-cycloalkenylsulfinyl, (Cs-Csg)- halocycloalkylsulfinyl, (C4-Cg)-halocycloalkenylsulfinyl, (Cs-Cg)- cycloalkyl-(C4-Cg)-alkylsulfinyl, (C4-Cg)-cycloalkenyl-(C1-Cy)- alkylsulfinyl, (Cs-Cg)-cycloalkyl-(C3-C,)-alkenyisulfinyl, (C4-Cs)-cycloalkenyl-(C3-C,)-alkenyisulfinyl, (C4-Cg)-alkyl-(C3-Cg)- cycloalkylsulfinyl, (C2-Ce)-alkenyl-(C3-Cg)-cycloalkylsulfinyl, (C»-Cg)- alkynyl-(Cs-Cg)-cycloalkylsulfinyl, (C4-Ce)-alkyl-(C4s-Cg)- cycloalkenyisulfinyl, (C2-Ce)-alkenyl-(C4-Cg)-cycloalkenylsulfinyl, (C;-
Ce)-alkylsulfonyl, (Ca-Ce)-alkenylsulfonyl, (Cs-Ce)-alkynyisulfonyl, (C;-
Ce)-haloalkylsulfonyl, (C3-Ce)-haloalkenyisulfonyl, (C3-Cg)- haloalkynylsulfonyl, (Cs-Cg)-cycloalkylsulfonyl, (C4-Cs)- cycloalkenylsulfonyl, (Cs-Cg)-halocycloalkylsulfonyl, (C4-Cg)- halocycloalkenyisulfonyl, (Cs-Cs)-cycloalkyl-(C4-C4)-alkylsulfonyl, (C4-Cs)-cycloalkenyl-(C4-C4)-alkylsulfonyl, (C3-Cg)-cycloalkyl-(C3-C4)- alkenylsulfonyl, (C4-Cs)-cycloalkenyl-(Cs-C.)-alkenylsulfonyl, (C1-Cg)- alkyl-(C3-Cg)-cycloalkylsulfonyl, (C,-Ce)-alkenyl-(Cs-Cg)- cycloalkylsulfonyl, (Co-Ce)-alkynyl-(Cs-Cs)-cycloalkylsulfonyl, (C;-Cg)- alkyl-(C4-Cs)-cycloalkenylsulfonyl, (C,-Ce)-alkenyl-(C4-Cg)- cycloalkenylsulfonyl, (C1-Ce)-dialkylamino, (C+-Cg)-alkylamino, (Cs-Ce)-
alkenylamino, (Cs-Cg)-alkynylamino, (C4-Cg)-haloalkylamino, (Cs-Cs)- haloalkenylamino, (Cs-Cs)-haloalkynylamino, (Cs-Cg)-cycloalkylamino, (C4-Cs)-cycloalkenylamino, (C3-Cg)-halocycloalkylamino, (C4-Cs)- halocycloalkenylamino, (Cs-Cs)-cycloalkyl-(C1-C4)-alkylamino, (C4-Cs)- cycloalkenyl-(C+-Cq)-alkylamino, (C3-Csg)-cycloalkyl-(C3-Cy)- alkenylamino, (C4-Cg)-cycloalkenyl-(Cs-C.)-alkenylamino, (C4-Ce)-alkyl- (Cs-Cg)-cycloalkylamino, (C2-Cg)-alkenyl-(C3-Cg)-cycloalkylamino, (C2-Ce)-alkynyl-(C3-Cs)-cycloalkylamino, (C4-Ce)-alkyl-(C4-Cg)- cycloalkenylamino, (C2-Ce)-alkenyl-(C4-Cg)-cycloalkenylamino, (C1-Co)- trialkylsilyl, aryl, aryloxy, arylthio, arylamino, aryl-(C4-Cq)-alkoxy, aryl- (C3-Ca)-alkenyloxy, aryl-(C1-C,4)-alkyithio, aryl-(C>-C4)-alkenylthio, aryl- (C1-C4)-alkylamino, aryl-(C3-C4)-alkenylamino, aryl-(C4-Cg)-dialkyilsilyl, diaryl-(C+-Cg)-alkylsilyl, triarylsilyl and 5- or 6-membered heterocyclyl, the cyclic moiety of the fourteen last-mentioned radicals being optionally substituted by one or more radicals selected from the group consisting of halogen, cyano, nitro, amino, hydroxyl, thio, (C1-Cy)-alkyl, (C4-Ca)-haloalkyl, (C3-Cs)-cycloalkyl, (C4-Ca)-alkoxy, (C+-Cy)-haloalkoxy, (C+-Ca)-alkylthio, (C4-Cs)-haloalkyithio, (C4-Cj4)-alkylamino, (C1-Cy)- haloalkylamino, formyl and (C4-C,)-alkanoy!.
R" are preferably identical or different and are halogen, cyano, nitro, (C1-Ce)-alkanoyl, (C1-Ce)-alkoxy, (C1-Cs)-haloalkyloxy, (C3-Cs)-cycloalkoxy, (C3-Cs)-cycloalkyl-(C1-C4)-alkoxy, (C4-Cg)-mono- or -dialkylcarbamoyl, (C1-Cs)-alkoxycarbonyl, (C+-Ce)-haloalkoxycarbonyl, (C1-Ce)-alkylthio, (C4-Ce)-haloalkylthio, (Cs-Cs)-cycloalkylthio, (C4-Ce)-alkylsulfinyl, (C1-Cg)-haloalkylsulfinyl, (Cs-Csg)-cycloalkylsulfinyl, (C4-Ce)-alkylsulfonyl, (C1-Ce)-haloalkylsulfonyl, (C3-Cg)-cycloalkyl- sulfonyl, (C1-Ce)-dialkylamino, (C;-Ce)-alkylamino, (Cs-Csg)-cycloalkyl- amino, (C4-Ce)-trialkylsilyl, aryl, aryloxy, arylthio, aryl-(C4-Cy)-alkyl, arylamino, aryl-(C4-C4)-alkoxy, where the cyclic moiety of the six lastmentioned radicals is optionally substituted by one or more radicals selected from the group consisting of halogen, nitro, (C1-C4)-alkyl, (C1-Ca4)-haloalkyl, (C+-C4)-alkoxy and (C4-C,4)-haloalkoxy.
Among the radicals R*and R®, particular preference is given to those for which the unit SR*R° is represented by the following structures:
A. 5 0),
F 1
R; S where the symbols and indices are as defined below: r is 0, 1;
D is a direct bond, (C1-C,)-alkylene, branched or unbranched, O,
S(O)o.12, NR"
R® has the meanings given above;
R" is H, (C1-Ca)-alkyl, (C4-C4)-alkanoyl, (C1-Ca)-alkoxycarbonyl, (C+-C4)-alkyl- or -dialkylaminocarbony! or (C4-C4)-alkylsulfonyl; a,b are identical or different and are 0, 1, 2, 3 or 4, preferably 0, 1 or 2.
In the case r = 0, the two aryl radicals are not linked by a bridge.
B. R° 12 3 ~~" where the symbols and indices are as defined below:
R'? is (C1-Cg)-alkyl, optionally substituted by an optionally substituted phenyl radical or (C3-Ce)-cycloalky! radical, (C3-Ce)-cycloalkyl, optionally substituted or condensed with an optionally substituted phenyl radical;
R® has the meanings given above; a is0,1,2, 3,4 or5, preferably 0, 1 or 2.
R’ S where the symbols and indices are as defined below:
R® has the meanings given above; a is 0, 1, 2, 3 or4, preferably 0, 1 or 2;
R® isa straight-chain or branched (C,-Csg)-alkanediyl group which is optionally substituted by or condensed with one or two optionally substituted phenyl groups.
D. RS _R™
S where the symbols and indices are as defined below:
R' R' are identical or different (C;-Cg)-alkyl, optionally substituted by an optionally substituted phenyl! radical or (Cs-Csg)-cycloalkyl radical, (Cs-Ce)-cycloalkyl, optionally substituted by or condensed with an optionally substituted phenyl radical.
E. YN
S R6
NE where the symbol and indices are as defined below:
R'® is a straight-chain or branched (C,-Cs)-alkanediyl group which is optionally substituted by, in the case of a phenyl group also condensed with, one or two optionally substituted phenyl groups.
The term “halogen” embraces fluorine, chlorine, bromine and iodine. The expression "(C4-Cy4)-alkyl" is to be understood as meaning an unbranched or branched hydrocarbon radical having 1, 2, 3 or 4 carbon atoms, such as, for example, the methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 2-methylpropyl or tert-butyl radical.
Correspondingly, alkyl radicals having a larger range of carbon atoms are to be understood as meaning an unbranched or branched saturated hydrocarbon radical which contains a number of carbon atoms which corresponds to this stated range.
Accordingly, the expression "(C4-Ce)-alkyl" embraces the abovementioned alkyl radicals, and also, for example, the pentyl, 2-methylbutyl, 1,1-dimethylpropyl or hexyl radical. The expression "(C4-C4p)-alkyl" is to be understood as meaning the abovementioned alkyl radicals, and also, for example, the nonyl, 1-decy! or 2-decy) radical. "(C4-C4)-Haloalky!" is to be understood as meaning an alkyl group mentioned under the expression "(C1-Ca)-alkyl" in which one or more hydrogen atoms are replaced by a J the same number of identical or different halogen atoms, preferably by chlorine or fluorine, such as the trifluoromethyl, the 1-fluoroethyl, the 2,2,2-trifluoroethyl, the chloromethyl, fluoromethyl, the difluoromethyl and the 1,1,2,2-tetrafluoroethy! group. "(C4-Cs)-Alkoxy" is to be understood as meaning an alkoxy group whose hydrocarbon radical has the meaning given under the expression "(C,-Cy)-alkyl".
Alkoxy groups having a larger range of carbon atoms are to be understood accordingly.
The terms "alkenyl" and "alkynyl" with a range of carbon atoms stated as prefix denote a straight-chain or branched hydrocarbon radical having a number of carbon atoms which corresponds to this stated range and which contains at least one multiple bond which can be located in any position of the respective unsaturated radical. "(C2-C4)-Alkenyl" accordingly denotes, for example, the vinyl, allyl, 2-methy!- 2-propene or 2-butenyl group; "(C,-Cs)-Alkenyl” denotes the abovementioned radicals and also, for example, the pentenyl, 2-methylpentenyl or the hexenyl group. "(C2-Ca)-Alkynyl" denotes, for example, the ethynyl, propargyl, 2-methyl-2-propyne or 2-butynyl group. "(C,-Ce)-Alkynyl" is to be understood as meaning the abovementioned radicals and also, for example, the 2-pentynyl or the 2-hexynyl group, and "(C2-Cyo)-alkyny!" is to be understood as meaning the abovementioned radicals and also, for example, the 2-octynyl or the 2-decynyl group. "(C3-Cg)-Cycloalkyl" denotes monocyclic alkyl radicals, such as the cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl radical, and denotes bicyclic alkyl radicals, such as the norbornyl radical.
The expression "(Cs-Cg)-cycloalkyl-(C1-Cy)-alkyl" is to be understood as meaning, for example the cyclopropylmethyl, cyclopentylmethyl, cyclohexyimethyl, cyclohexyiethyl and cyclohexylbutyl radical, and the expression "(C1-Ce)-alkyl-(C3-Cg)-cycloalkyl" is to be understood as meaning, for example, the 1-methyicyclopropyl, 1-methylcyclopentyl, 1-methyicyclohexyl, 3-hexylcyclobutyl and the 4-tert- butylcyclohexyl radical. "(C1-C4)-Alkoxy-(C+-Ce)-alkyloxy" denotes an alkoxy group as defined above which is substituted by a further alkoxy group, such as, for example, 1-ethoxyethoxy.
*(C5-Csg)-Cycloalkoxy" or "(Cs-Cg)-cycloalkylthio" is to be understood as meaning one of the abovementioned (Cs-Cs)-cycloalkyl! radicals which is attached via an oxygen or sulfur atom. "(Cs-Ce)-Cycloalkyl-(C4-Cg)-alkoxy" denotes, for example, the cyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyciohexylmethoxy, cyclohexylethoxy or the cyclohexytbutoxy group.
The expression "(C+-C4)-alkyl-(C3-Cs)-cycloalkoxy” denotes, for example, the methylcyclopropyloxy, methylcyclobutyloxy or the butyicyclohexyloxy group. "(C1-Ce)-Alkylthio" denotes an alkylthio group whose hydrocarbon radical has the meaning given under the expression "(C;-Cg)-alkyl".
Similarly, "(C4-Ce)-alkylsulfinyl" denotes, for example, the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl- or tert-butylsulfinyl group and "(C+-Ce)-alkylsulfonyl" denotes, for example, the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl- or tert-butylsulfonyl group. "(C4-Ce)-Alkylamino" denotes a nitrogen atom which is substituted by one or two identical or different alkyl radicals of the above definition.
The expression "(C4-Cs)-mono- or -dialkylcarbamoy!" denotes a carbamoyl group having one or two hydrocarbon radicals which have the meaning given under the expression "(C+-Ce-alkyl)" and which, in the case of two hydrocarbon radicals, can be identical or different.
Similarly, "(C4-Ce)-dihaloalkyicarbamoyl” denotes a carbamoyl group which carries two (C,-Ce)-haloalkyl radicals according to the above definition or one (C4-Cg)- haloalkyl! radical and one (C+-Cg)-alky! radical according to the above definition. "(C4-Ce)-Alkanoyl" denotes, for example, the formyl, acetyl, propionyl, butyryl or 2-methylbutyryl group.
The expression "aryl" is to be understood as meaning a carbocyclic, i.e. constructed of carbon atoms, aromatic radical having preferably 6 to 14, in particular 6 to 12, carbon atoms, such as, for example, phenyl, naphthyl or biphenylyl, preferably a J phenyl. "Aroyl" accordingly denotes an aryl radical as defined above which is attached via a carbonyl! group, such as, for example, the benzoyl! group.
The expression "heterocyclyl" preferably denotes a cyclic radical which can be completely saturated, partially unsaturated or completely unsaturated and which can be interrupted by at least one or more identical or different atoms selected from the group consisting of nitrogen, sulfur and oxygen, where, however, two oxygen atoms may not be directly adjacent and at least one carbon atom has to be present in the ring, such as, for example, a thiophene, furan, pyrrole, thiazole, oxazole, imidazole, isothiazoe, 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-tetrazole, benzo[b]thiophene, benzo[b}furan, indole, benzo[c}thiophene, benzo|c]furan, isoindole, benzoxazole, benzothiazole, benzimidazole, benzisoxazole, benzisothiazole, benzopyrazole, benzothiadiazole, benzotriazole, dibenzofuran, dibenzothiophene, carbazole, pyridine, pyrazine, pyrimidine, pyridazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,4,5-tetrazine, quinoline, isoquinoline, quinoxaline, quinazoline, cinnoline, 1,8-naphthyridine, 1,5-naphthyridine, 1,6-naphthyridine, 1,7-naphthyridine, phthalazine, pyridopyrimidine, purine, pteridine, 4H-quinolizine, piperidine, pyrrolidine, oxazoline, tetrahydrofuran, tetrahydropyran, isoxzolidine or thiazolidine radical. Accordingly, the expression "heteroaromatic" embraces, from among the meanings mentioned above under "heterocyclyl", in each case the completely unsaturated aromatic heterocyclic compounds.
Heterocyclyl particularly preferably denotes a saturated, partially saturated or aromatic ring system having 3 to 6 ring members and 1 to 4 heteroatoms selected from the group consisting of O, S and N, where at least one carbon atom has to be present in the ring.
Very particularly preferably, heterocyclyl denotes a pyridine, pyrimidine, (1,2,4)- oxadiazole, (1,3,4)-oxadiazole, pyrrole, furan, thiophene, oxazole, thiazole, imidazole, pyrazole, isoxazole, 1,2,4-triazole, tetrazole, pyrazine, pyridazine, oxazoline, thiazoline, tetrahydrofuran, tetrahydropyran, morpholine, piperidine, piperazine, pyrroline, pyrrolidine, oxazolidine, thiazolidine, oxirane and oxetane radical.
. @ "Aryl-(C+-C.)-alkoxy" denotes an aryl radical which is attached via a (C4-C4)-alkoxy group, for example the benzyloxy, phenylethoxy, phenylbutoxy or naphthylmethoxy radical. "Arylthio" denotes an ary! radical which is attached via a sulfur atom, for example the phenylthio or the 1- or 2-naphthylthio radical. Similarly, "aryloxy" denotes, for example, the phenoxy or 1- or 2-naphthyloxy radical. "Aryl-(C+-Ca4)-alkylthio" denotes an aryl radical which is attached via an alkylthio radical, for example the benzylthio, naphthylmethyithio or the phenylethylithio radical.
The expression "(C,-Cg)-trialkylsilyl" denotes a silicon atom which carries three identical or different alkyl radicals according to the above definition. Similarly, "aryl- (C4-Ce)-dialkylsilyl" denotes a silicon atom which carries one aryl radical and two identical or different alkyl radicals according to the above definition, "diaryl-(C4-Ce)- alkylsilyl" denotes a silicon atom which carries one alkyl radical and two identical or different aryl radicals according to the above definition and "triarylsilyl" denotes a silicon atom which carries three identical or different aryl radicals according to the above definition.
The substituents on the various aliphatic, aromatic and heterocyclic ring systems preferably include halogen, nitro, cyano, di-(C4-Cy)-alkylamino, (C1-Cy)-alkyl, (C4-Ca)-trialkylsilyl, (C1-Cq)-alkoxy, (C1-Ca)-alkoxy-(C1-Ca)-alkyl, (C1-Cy)-alkoxy- [CH2CH_2]y 2-ethoxy, (C1-Cy)-alkylthio, (C4-Cg)-alkylsulfinyl, (C4-Ca)-alkylsulfonyl, phenyl, benzyl, phenoxy, phenylthio, halophenoxy, (C+-C.)-alkylthiophenoxy, (C1-Ca)-alkoxyphenoxy, (C+-Ca)-alkylthiophenoxy, phenylthio, heterocyclyl, heterocyclylthio, heterocyclyloxy, haloheterocyclyloxy, alkylheterocyclyloxy or alkoxyheterocyclyloxy, where in the alkyl radicals and the radicals derived therefrom of one or more hydrogen atoms, in the case of fluorine also up to the maximum number, may be replaced by halogen, preferably by chlorine or fluorine.
Particularly preferred substituents are, in particular for cyclic systems, halogen, cyano, nitro, amino, hydroxyl, thio, (C4-C,)-alkyl, (C4-Ca)-haloalkyl, (C3-Cg)-cycloalkyl, (C4-Cy4)-alkoxy, (C1-Ca)-haloalkoxy, (C+-Ca)-alkylthio, (C4-C4)-haloalkylthio, (C4-Cy)-alkylamino, (C4-Cg)-haloalkylamino, formyl and (C;-C,)-alkanoyl.
. @
Depending on the nature of the substituents defined above, the compounds of the formula (1) have acidic or basic properties and are capable of forming salts. If, for example, the compounds of the formula (1) carry groups such as hydroxyl, carboxyl or other groups which induce acidic properties, these compounds can be reacted with bases to form salts. Suitable bases are, for example, hydroxides, carbonates and bicarbonates of the alkali metals and alkaline earth metals, in particular those of sodium, potassium, magnesium and calcium, furthermore ammonia, primary, secondary and tertiary amines with (C,-C,)-alkyl radicals and mono-, di- and trialkanolamines of (C+-C4)-alkanols. If, for example, the compounds of the formula (I) carry groups such as amino, alkylamino or other groups which induce basic properties, these compounds can be reacted with acids to form salts. Suitable acids are, for example, mineral acids, such as hydrochloric, sulfuric and phosphoric acid, organic acids, such as acetic acid or oxalic acid, and acidic salts, such as NaHSO, and KHSO,. The salts obtainable in this manner likewise have insecticidal, acaricidal and miticidal properties.
The compounds of the formula (I) can have an asymmetrically substituted sulfur atom and/or one or more asymmetrically substituted carbon atoms or stereoisomers on double bonds. Therefore, it is possible for enantiomers or diastereomers to be present. The invention embraces both the pure isomers and their mixtures. The mixtures of diastereomers can be separated into the isomers by customary methods, for example by selective crystallization from suitable solvents or by chromatography. Racemates can be separated into the enantiomers by customary methods.
The preparation of the compounds according to the invention is carried out by methods known per se from the literature, as described in standard works on organic synthesis (cf., for example, T. L. Gilchrist, C.J. Moody, Chem. Rev. 77, 409 (1977);
Houben-Weyl, Methoden der Organischen Chemie [Methods of Organic Chemistry],
Vol. E11, p.877).
The preparation is carried out under reaction conditions which are known and suitable for the reactions mentioned. It is also possible to use variants which are known per se but not mentioned here in detail.
If desired, the starting materials can also be formed in situ, i.e. they are not isolated from the reaction mixture but immediately reacted further to give the compounds of the formula (1).
The present invention also relates to processes for preparing compounds of the formula (I).
Compounds of the formula (I) in which R', R?, R®, R*, R®, n and X are as defined under formula (I), mis 0 and Y is oxygen are prepared, for example, by reacting a carboxamide of the formula (I), in which R', R, n and X are as defined under formula (1) with a halogenating agent, preferably a chlorinating or brominating agent, to give a compound of the formula (Ill) in which R’, R?, R®, n and X are as defined under formula (I) and Z is halogen, preferably chlorine or bromine, and this compound is then reacted with a thioether R*R®S, in which R* and R® are as defined under formula (I) in the presence of a base to give the end products of the formula (1), where R*, R® are preferably not both aryl and/or heteroaryl.
R' 0 R' 0 halogenating 3 agent PO R4RSS —-— base 7 Re? =? A ~ = > (0), (1) 0), (in)
RO ) a 5
R® R ©h
Suitable halogenating agents for preparing the compounds (lil) are, for example, organo- or alkali metal hypochlorites, such as, for example, tert-butyl hypochlorite or sodium hypochlorite or potassium hypochlorite, alkali metal hypobromites, such as sodium hypobromite or potassium hypobromite, or the elemental halogens in the presence of a base such as, for example, alkali metal or alkaline earth metal hydroxide or carbonate.
The chlorination of amides using elemental chlorine is known in principle (ind. J.
Chem. V.35B, 1966, 1117-1118: describes the chlorination of nicotinamide with Cl, in 3 N HCI in two steps with a yield of 58%).
However, it is also known that the CF3 group has a very strong electron-withdrawing effect, preventing electrophilic and radical attacks on CF3-substituted molecules. In the pyridine ring, the CF; group strongly reduces basicity so that the molecule is generally not capable of forming salts.
Surprisingly, it has now been found that chlorination of 4-trifluoromethylinicotinamide with Clz in aqueous acids (for example HCI) gives salts of N-chioro-4-trifluoromethyl- nicotinamide in very good yields and high purities.
Accordingly the invention furthermore provides a process for preparing N-chloro- 4-trifluoromethylnicotinamide and it salts of the formula (Illa)
CF, oy 7
N
HA
(Ia) in which A is a non-oxidizable, organic or inorganic anion by chlorination of 4-trifluoromethyinicotinamide with Cl, in aqueous acid and, if desired, subsequent anion exchange and/or, if desired, reaction with a base to give
N-chloro-4-trifluoromethyinicotinamide.
The starting material 4-trifluoromethylnicotinamide is known and, together with its preparation, described, for example, in EP-A 0580374.
The reaction temperature is usually from -5°C to +40°C, preferably from 0°C to +25°C.
The process is carried out in an aqueous acid, for example HCI, H,SO,, HBF,
CH3;COOH or CF3COOH, preferably HCI (preferred concentration 3-10% by weight).
It is also possible to use mixtures of a plurality of acids.
Cl, is preferably employed in gaseous form; in general in amounts of from 1 to 1.5 mol, in particular from 1 to 1.3 mol, preferably from 1 to 1.2 mol, based on 1 mol of 4-trifluoromethylnicotinamide.
Chlorination of 4-trifluoromethylnicotinamide gives the corresponding salt, preferably the hydrochloride. Work-up is carried out by methods known to the person skilled in the art; for example, the precipitated product is filtered off, washed and dried.
A subsequent anion exchange can be carried out by known methods familiar to the person skilled in the ant. The salt obtained in the reaction can be dissolved, for example, in a suitable solvent in which the salt desired later on is insoluble. Reaction with a salt which contains the desired anion and is likewise soluble in this solvent gives, by precipitation, the desired salt, since this is insoluble in the chosen solvent.
If desired, the free N-chloro compound can be released by reaction with a base in a simple manner familiar to the person skilled in the art.
Suitable bases are, for example, hydroxides, carbonates, bicarbonates, acetates of the alkali metals and alkaline earth metals, in particular those of sodium, potassium, magnesium and calcium, furthermore tertiary amines having (C1-C4)-alkyl radicals. tis furthermore possible to isolate the free base by treatment with water and extraction with organic solvents.
The invention also provides salts of N-chloro-4-trifluoromethyinicotinamide of the formula (lla):
CF, oy 7
N
HA
(lla) where A is a non-oxidizable, organic or inorganic anion, preferably F, HF, Cl, BF,
PFs, HSO4, 1/2 SO4, CH3COO, CF3COO0, CF3S03, CH3S03, p-CH3-CsHsSO; or
HyPO,.
In the context of the invention, 'non-oxidizable’ means that the corresponding anion does not react with the N-CI group of the N-chloro-4-trifluoromethyinicotinamide.
RI 0 ;
R Oo .
XTX NHzZ ~~ R“RSS R base XTX N=§ 2 = 3 | 5
RN OR PY P R
2 3
R N R
(On (my oO © ()
The reaction of the N-haloamides (lll), optionally also as salt, to the end products (I) is carried out, for example, in an inert solvent such as, for example, dichloromethane, chloroform, carbon tetrachloride or benzene, in a temperature range between 0°C and 100°C, preferably between 20°C and 50°C and in the presence of a base. Suitable bases are, for example, alkali metal or alkaline earth metal hydroxides, carbonates or bicarbonates or organic bases, such as, for example, trialkylamines or pyridine.
The reaction sequence described above can, if appropriate, also be carried out as a one-pot reaction, it also being possible for intermediates of the formula (IV) in which
R* and R® are as defined above under formula (1) and Z is a halogen radical, preferably chlorine or bromine, to occur as reaction partners of the amide (Il).
FE halogenating . (a), agent SEN +7
RiRSS ———> S Zz” base, 0)
La
R
(v)
Compounds of the formula (1), in which R', R2, R®, R*, R®, n, m and X are as defined under formula (I) and Y is oxygen can furthermore be prepared by reacting a carboxylic acid of the formula (V)
Rn 0
Sl
PW
R2 i R® (On (V) in which R", R?, R%, X and n are as defined under formula (I) in the form of an activated derivative of this acid in the presence of a base with a compound of the formula (V1), in which R*, R® and m are as defined under formula {)) 4 "Ng / NH - 7 N\ :
Rr No,
Suitable activated derivatives of the acid which may 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 else alkali metal 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 else in mixtures of these solvents, in a temperature range between 0°C and 100°C, preferably between 20°C and 50°C.
Compounds of the formula (la),
R'" 0
JER’
XT N=S_
PS —= a
R? i R3 (On (la) in which R', R? ,R®, R’, X and n are as defined in formula (I), Y is oxygen and E corresponds to an oxygen or nitrogen unit, are advantageously prepared by converting an amide of the formula (Il) with a halogenating agent, such as tert-butyl hypochlorite, into the N,N-dichloro compound (VII), in which R', R%, R®, n and X are as defined under formula (1)
RO
XT NCI,
AA
R | R (On (vin which is then converted with sulfur dichloride SCI; into a compound of the formula (VII), in which R', R?, R%, n and X are as defined under formula (I)
RO
=
ML
R? i R® (On (Vii and the latter compound is reacted with at least two equivalents of a nucleophile
HER’, in which ER’ is as defined above under formula (1a), in the presence of a base. Suitable bases are organic bases, such as, for example, triethylamine, pyridine or lutidine, or alkali metal or alkaline earth metal hydroxides, carbonates or bicarbonates and, in the case of alcohols, also alkali metal or alkaline earth metal hydrides or amides. The reaction is advantageously carried out in an inert solvent, such as dichloromethane, chloroform, carbon tetrachloride, benzene, toluene, diethyl ether or tetrahydrofuran, or in mixtures of these solvents, in a temperature range between 0°C and 100°C, preferably between 20°C and 50°C.
The compounds of the formula (I), in which R', R% R®, R* R® n and X are as defined under formula (1), Y is oxygen and m is 0 can furthermore be prepared by reacting an azide of the formula (1X),
R" 0
PO
PS ~
R? i R® (On (IX) in which R', R?, R%, X and n are as defined under formula (I) with a thioether R*R°S in which R* and R°® are as defined under formula (I) in the presence of a catalyst, such as, for example, FeCl, or with irradiation, giving the end products with elimination of nitrogen.
The compounds of the formula (1), in which R', R?, R®, n and X are as defined under formula (I), R* and R® are aryl radicals, Y is oxygen and m is 0 can furthermore be obtained by reacting an amide of the formula (lI) with a dialkoxy-diaryl-sulfurane of the formula (X), in which R* and R® are aryl radicals and OR is a fluoroalkoxy radical, preferably the 1,1,1,3,3,3-hexafluoro-2-phenyl-2-propoxy radical 4 "Ng LOR; rR” “OR, (X).
The compounds of the formula (1), in which R', R?, R%, R*, R® n and X are as defined under formula (1), Y is oxygen and m is O can furthermore be prepared by reacting a sulfoxide of the formula (XI),
.®
R?
Ngo
RS
(X1) in which R* and R® are as defined under formula (I) in the presence of a condensing agent with an amide of the formula (ll), giving the compounds of the formula (1) with elimination of water. Suitable condensing agents are, for example, phosphorus oxychloride, phosphorus(V) oxide, methanesulfonyl chloride, sulfuryl chloride, sulfur trichloride, boron trifluoride, dicyclohexylcarbodiimide, aryl cyanates or acid anhydrides, preferably trifluoroacetic anhydride or trifluoromethanesulfonic anhydride.
To produce compounds of the formula (I) in which nis 1, it is possible to oxidize the pyridine nitrogen, preferably before introducing the SR*R® group (see, for example,
Houben-Weyl, Methoden der Organischen Chemie, Vol. E 7b, part 2, p. 565,
G. Thieme Verlag, Stuttgart 1992). Suitable oxidizing agents are, for example, organic peracids, such as 3-chloroperbenzoic acid, and H,O,.
If desired, the compounds of the formula (I) prepared by the above process can, if m is 0, be oxidized at the sulfur to give the compounds of the formula (1) in which mis 1 (see, for example, Houben-Weyl. Methoden der Organischen Chemie, Vol. E11, p. 1299 ff., G. Thieme Verlag, Stuttgart 1985). Suitable oxidizing agents are, for example, sodium periodate or organic peracids, such as 3-chloroperbenzoic acid.
Furthermore, if appropriate, compounds of the formula (1) in which R? and/or R® are a halogen atom, preferably chlorine or fluorine, can be converted by reaction with alcohols, thiols or primary or secondary amines in the presence of a base to other compounds of the formula (1) in which the radical R? and/or R® denotes an alkoxy, alkylthio or amino group.
Further references concerning preparation of the compounds according to the invention and the various starting materials can be found in standard works on organic synthesis, such as, for example: T. L. Gilchrist, C.J. Moody, Chem. Rev. 77, 409 (1977) or Houben-Weyl, Methoden der Organischen Chemie, Vol. E11, p.877.
.@.
Collections of compounds of the formula (I) which can be synthesized by the abovementioned scheme may also be prepared in a parallel manner, and this may be effected manually or in a semiautomated or fully automated manner. In this case, it is possible, for example, to automate the procedure of the reaction, work-up or purification of the products or of the intermediates. In total, this is to be understood as meaning a procedure as is described, for example, by S.H. DeWitt in “Annual
Reports in Combinatorial Chemistry and Molecular Diversity: Automated Synthesis”,
Volume 1, Verlag Escom 1997, pages 69 to 77.
A series of commercially available apparatuses as are offered by, for example, Stem
Corporation, Woodrolfe Road, Tollesbury, Essex, CM9 8SE, England or H+P
Labortechnik GmbH, Bruckmannring 28, 85764 OberschleiBheim, Germany or
Radleys, Shirehill, Saffron Walden, Essex, England, may be used for the parallel procedure of the reaction and work-up. For the parallel purification of compounds of the formula (1), or of intermediates obtained during the preparation, use may be made, inter alia, of chromatography apparatuses, for example those by ISCO, Inc., 4700 Superior Street, Lincoln, NE 68504, USA.
The apparatuses mentioned lead to a modular procedure in which the individual process steps are automated, but manual operations must be performed between the process steps. This can be prevented by employing semi-integrated or fully integrated automation systems where the automation modules in question are operated by, for example, robots. Such automation systems can be obtained, for example, from Zymark Corporation, Zymark Center, Hopkinton, MA 01748, USA.
In addition to what has been described here, compounds of the formula (I) may be prepared in part or fully by solid-phase-supported methods. For this purpose, individual intermediate steps or all intermediate steps of the synthesis or of a synthesis adapted to suit the procedure in question are bound to a synthetic resin. Solid-phase-supported synthesis methods are described extensively in the specialist literature, for example Barry A. Bunin in “The Combinatorial Index”, Academic Press, 1998.
The use of solid-phase-supported synthesis methods permits a series of protocols which are known from the literature and which, in turn, can be performed manually orinan automated manner. For example, the “tea-bag method” (Houghten, US 4,631,211; Houghten et al., Proc. Natl. Acad. Sci, 1985, 82, 5131-5135), in which

Claims (1)

  1. Corresponds to amended German pages 109 to 110 1-06-2002 EP0103083 2000/M 205 WO : 91 What is claimed is:
    1. An acylsulfimide of the formula (I) and salts thereof, R' Y (fhm Rt ~~ XT N=S A Seo R? NT SR (O), where the symbols and indices are as defined below: X is CH or N; Y is OorS; m isOorf; n isOori1; R' is C-Cg-haloalkyl; R? R® are identical or different and are H, halogen or a branched or - unbranched (C4-Cs)-alkyl group, where one or two CH; groups may be replaced by -O- or -S- or -N(C4-Cg)-alkyl, with the proviso that heteroatoms may not be adjacent to one another; R* R° are identical or different and are R®, -C(W)R’, -C(=NOR")R’, -C(=NNR'3)R’, -C(=W)OR’, -C(=W)NR’5, -OC(=W)R’, - OC(=W)OR’, -NR’C(=W)R?, --N[C(=W)R]2, -NR’C(=W)OR’, -C(=W)NR’- NR’, -C(=W)NR’-NR[C(=W)R], -NR’-C(=W)NR’;, -NR’- ' NR’C(=W)R’, -NR’-N[C(=W)R]2, -N[(C=W)R]-NR’, -NR’-NR’[(C=W)WR], -NR'[(C=W)NR’3], -NR’[C=NR’]R’, -NR’(C=NR’)NR’;, -O-NR7s, -O-NR’(C=W)R’, -SO.NR’;, -NR’SO,R’, -SO,0R’, -OSO,R’, -OR®, -NR",, -SR’, -SiR3, -PR’,, -P(=W)R’, -SOR’, -SO,R’, - AMENDED SHEET
    7 92 PWR’, -PW3R';; or R*and R® together with the sulfur to which they are attached form a three- to eight-membered saturated or unsaturated ring system which is optionally mono- or polysubstituted and which optionally contains 1 to 4 further heteroatoms, where two or more of the substituents optionally form one or more further ring systems; Ww is OorsS; R® are identical or different and are (C1-Cyp)-alkyl, (C2-Cx)-alkenyl, (C2-Cyo)-alkynyl, (C3-Cs)-cycloalkyl, (C4-Cg)-cycloalkenyl, (Ce- C1o)-cycloalkynyl, aryl or heterocyclyl, where the radicals mentioned may optionally be mono- or polysubstituted; R’ are identical or different and are H or R®. AMENDED SHEET
    -OC(=W)OR', -NR'C(=W)R"’, -N[C(=W)R’], -NR'°C(=W)OR°, -C(=W)NR'-NR'%, -C(=W)NR'-NR'[C(=W)R'}, -NR'*-C(=W)NR?, -NR™-NR"°C(=W)R'®, -NR'-N[C(=W)R%],, -N[(C=W)R'’-NR"%,, -NR™-N[(C=W)WR'", -NR'[(C=W)NR%], -NR'*(C=NR'"R", -NR'(C=NR'®)NR%,, -O-NR'%, -O-NR'°(C=W)R'®, -SO,NR'’, -NR'’SO,R", -SO,0R", -0SO,R"°, OR", -NR'’,, -SR™®, -SiR"%,, -PR"%, -P(=W)R'%,, -SOR", -SO,R"°, -PW,R'%,, -PW3R'%, or two radicals R® together are =W, =N-R'°, =CR,'%, CHR'®, or =CH,; R' are identical or different and are (C;-Cg)-alkyl, (Co-Ce)-alkeny, (C2-Ce)-alkynyl, (Cs-Cs)-cycloalkyl, (C4-Cg)-cycloalkenyl, (C3-Cog)- cycloalkyl-(C4-Ca)-alkyl, (C4-Cg)-cycloalkenyl-(C1-Cy4)-alky!, (C3-Csg)- cycloalkyl-(C2-Ca)-alkenyl, (C4-Cs)-cycloalkenyl-(Co-C,)-alkenyl, (C4-Ce)- alkyl-(C3-Cs)-cycloalkyl, (C2-Ce)-alkenyl-(C3-Cg)-cycloalkyl, (C2-Cg)- alkynyl-(Cs-Cs)-cycloalkyl, (C+-Cg)-alkyl-(C4-Cs)-cycloalkeny!, (C2-Cg)- alkenyl-(C4-Csg)-cycloalkenyl, aryl, heterocyclyl; where the radicals mentioned are optionally substituted by one or more radicals R'" and optionally two radicals R'° together form a ring system; R" are identical or different and are halogen, cyano, nitro, hydroxyl, thio, amino, formyl, (C4-Ce)-alkanoyl, (C1-Ce)-alkoxy, (Cs-Ce)-alkenyloxy, (Cs- Ce)-alkynyloxy, (C4-Ce)-haloalkyloxy, (C3-Ce)-haloalkenyloxy, (Cs-Cg)- haloalkynyloxy, (Cs-Cs)-cycloalkoxy, (Cs-Cg)-cycloalkenyloxy, (Ca-Csg)- halocycloalkoxy, (C4-Cg)-halocycloalkenyloxy, (Cs-Cg)-cycloalkyi-(C+- Ca)-alkoxy, (C4-Cg)-cycloalkenyl-(C+-Cy)-alkoxy, (Cs-Cg)-cycloalkyl-(Cp- Cs)-alkenyloxy, (C4-Cs)-cycloalkenyl-(C1-C,)-alkenyloxy, (C4-Cg)-alkyl- (Cs-Cs)-cycloalkoxy, (C,-Ce)-alkenyl-(Cs-Csg)-cycloalkoxy, (C2-Cs)- alkynyl-(Cs-Cg)-cycloalkoxy, (C1-Cs)-alkyl-(C4-Cg)-cycloalkenyloxy, (Co- Ce)-alkenyl-(C4-Cg)-cycloalkenyloxy, (C1-C4)-alkoxy-(C4-Cg)-alkoxy, (Cs- C4)-alkoxy-(C3-Cs)-alkenyloxy, carbamoyl, (C-Cg)-mono- or dialkylcarbamoyl, (C4-Cg)-mono- or dihaloalkylcarbamoyl, (Ca-Cg)- mono- or dicycloalkylcarbamoyl, (C1-Cs)-alkoxycarbonyl, (C3-Cg)- cycloalkoxycarbonyl, (C1-Ce)-alkanoyloxy, (Cs-Cs)-cycloalkanoyloxy, (C4-Ce)-haloalkoxycarbonyl, (C4-Cg)-haloalkanoyloxy, (C1-Cg)- alkanamido, (C4-Cg)-haloalkanamido, (C,-Ce)-alkenamido, (Cz-Cg)- cycloalkanamido, (Cs-Cs)-cycloalkyl-(C4-C,)-alkanamido, (C1-Ce)- alkylthio, (C3-Ce)-alkenylthio, (C3-Cg)-alkynylthio, (C1-Ce)-haloalkylthio,
    . (J
    (C3-Ce)-haloalkenyithio, (C3-Ce)-haloalkynylthio, (C3-Cg)-cycloalkylthio, (C4-Cg)-cycloalkenylthio, (Cs-Cg)-halocycloalkylthio, (C4-Cs)- halocycloalkenylthio, (Cs-Cg)-cycloalkyl-(C1-Ca)-alkylthio, (C4-Cg)- cycloalkenyl-(C4-C4)-alkylthio, (C3-Cg)-cycloalkyl-(Cs-Cy4)-alkenylthio,
    (C4-Csg)-cycloalkenyl-(Cs-C4)-alkenylthio, (C1-Ce)-alkyl-(C3-Cg)- cycloalkylthio, (C2-Ce)-alkenyl-(C3-Cs)-cycloalkyithio, (Co-Ce)-alkynyl- (C3-Cs)-cycloalkylthio, (C4-Cg)-alkyl-(Cs-Cs)-cycloalkenyithio, (C2-Ce)- alkenyl-(C4-Cs)-cycloalkenyithio, (C4-Ce)-alkylsulfinyl, (C3-Cé)- alkenylsulfinyl, (Cs-Cg)-alkynylsulfinyl, (C4-Ce)-haloalkylsulfinyl, (C3-Cg)-
    haloalkenyisulfinyl, (Cs-Cg)-haloalkynylsulfinyl, (C-Cg)- cycloalkylsulfinyl, (C4-Cg)-cycloalkenylsulfinyl, (Cs-Cg)- halocycloalkylsulfinyl, (C4-Cs)-halocycloalkenyisulfinyl, (Cs-Cs)- cycloalkyl-(C+-Ca)-alkylsulfinyi, (C4-Cg)-cycloalkenyi-(C4-C4)- alkylsulfinyl, (Cs-Cg)-cycloalkyl-(C3-C,)-alkenyisulfinyl,
    (C4-Cg)-cycloalkenyl-(C3-Ca4)-alkenylsulfinyl, (C1-Cg)-alkyl-(C3-Csg)- cycloalkylsulfinyl, (C2-Ce)-alkenyl-(Cs-Cg)-cycloalkylsulfinyl, (C2-Cg)- alkynyl-(C3-Cs)-cycloalkylsulfinyl, (C1-Ce)-alkyl-(C4-Cs)- cycloalkenylsulfinyl, (C2-Cg)-alkenyl-(C4-Cg)-cycloalkenylsulfinyl, (Cs- Ce)-alkylsulfonyl, (Ca-Cs)-alkenylsulfonyl, (Cs-Cs)-alkynyisulfonyl, (C;-
    Ce)-haloalkylsulfonyl, (C3-Ce)-haloalkenylsulfonyl, (C3-Ce)- haloalkynylsulfonyl, (Cs-Cs)-cycloalkylsulfonyl, (C4-Cg)- cycloalkenylsulfonyl, (Cs-Cs)-halocycioalkyisulfonyl, (C4-Csg)- halocycloalkenylsulfonyl, (Cs-Cs)-cycloalkyl-(C1-Cg)-alkylsulfonyl, (C4-Cs)-cycloalkenyl-(C4-C4)-alkylsulfonyl, (Cs-Cg)-cycloalkyl-(Cs-Ca)-
    alkenylsulfonyl, (C4-Cg)-cycloalkenyl-(C3-C,)-alkenylsulfonyl, (C4-Ceg)- alkyl-(Cs-Cg)-cycloalkylsulfonyl, (C2-Ce)-alkenyl-(Cs-Cg)- cycloalkylsulfonyl, (C.-Cs)-alkynyl-(Cs-Cs)-cycloalkylsulfonyl, (C1-Cg)- alkyl-(C4-Cg)-cycloalkenyisulfonyl, (C2-Ce)-alkenyl-(C4-Cs)- cycloalkenylsulfonyl, (C1-Ce)-dialkylamino, (C1-Ce)-alkylamino, (C3-Ce)-
    alkenylamino, (Cs-Ce)-alkynylamino, (C4-Cg)-haloalkylamino, (C3-Ce)- haloalkenylamino, (C3-Ce)-haloalkynylamino, (Cs-Cs)-cycloalkylamino, (C4-Cg)-cycloalkenylamino, (C3-Csg)-halocycloalkylamino, (C4-Cs)- halocycloalkenylamino, (Cs-Cg)-cycioalkyl-(C1-C4)-alkylamino, (C4-Cg)- cycloalkenyl-(C4-Cg)-alkylamino, (Cs-Cg)-cycloalkyl-(C3-C4)-
    alkenylamino, (C4-Cg)-cycloalkenyl-(Cs-Cs)-alkenylamino, (C4-Cg)-alkyl- (C3-Cg)-cycloalkylamino, (C»-Cg)-alkenyl-(C3-Csg)-cycloalkylamino,
    @ (C2-Cy)-alkynyl-(C3-Cg)-cycloalkylamino, (C1-Ce)-alkyl-(C4-Cs)- cycloalkenylamino, (C2-Cg)-alkenyl-(C4-Cs)-cycloalkenylamino, (C;-Ce)- trialkylsilyl, aryl, aryloxy, arylthio, arylamino, aryl-(C4-Cs)-alkoxy, aryl- (Cs-Ca)-alkenyloxy, aryl-(C1-Ca)-alkyithio, aryl-(C»-C)-alkenylthio, aryl- (C1-C4)-alkylamino, aryl-(Cs-Ca)-alkenylamino, aryl-(C,-Cq)-dialkylsilyl, diaryl-(C+-Ce)-alkylsilyl, triarylsilyl and 5- or 6-membered heterocyclyl, the cyclic moiety of the fourteen last-mentioned radicals being optionally substituted by one or more radicals selected from the group consisting of halogen, cyano, nitro, amino, hydroxyl, thio, (C-Ca)-alkyl, (C4-Cy)-haloalkyl, (Cs-Csg)-cycloalkyl, (C-Cj)-alkoxy, (C4-Ca)-haloalkoxy, (C1-Ca)-alkylthio, (C4-C4)-haloalkylthio, (C4-C4)-alkylamino, (C1-Ca)- haloalkylamino, formyl and (C4-C,)-alkanoyl.
    7. An acylsulfimide as claimed in one or more of claims 1 to 6, where the unit SRR’ is represented by the following structures of groups A to E:
    A. (D), R® 9 TL J &) ° R: Ss where the symbols and indices are as defined below: r is 0, 1; D is a direct bond, (C4-C4)-alkylene, branched or unbranched, O, S(0)o.1.2, NR'" R® is as defined in claim 6; R" is H, (C4-Cy4)-alkyl, (C4-C4)-alkanoyl, (C1-C)-alkoxycarbonyl, (C1-C4)-alkyl- or -dialkylaminocarbonyl or (C4-Cy)-alkylsulfonyl; a,b are identical or different 0, 1, 2, 3 or 4;
    B. R’ 12 3 ~~" where the symbols and indices are as defined below:
    R' is (C4-Cg)-alkyl, optionally substituted by an optionally substituted phenyl radical or (C3-Cg)-cycloalky! radical, (C3-Cg)-cycloalkyl, optionally substituted or condensed with an optionally substituted phenyl radical, R® is as defined in claim 6; a is0,1,2,3,40r5;
    C. (o R'3 3 _/ R’ S where the symbols and indices are as defined below: R° is as defined in claim 6; a is 0,1, 2, 3 or4, preferably 0, 1 or 2; R® isa straight-chain or branched (C.-Cs)-alkanediyl group which is optionally substituted by or condensed with one or two optionally substituted phenyl groups; 15
    D. RIF" where the symbols and indices are as defined below: R" R' are identical or different (C,-Cg)-alkyl, optionally substituted by an optionally substituted phenyl radical or (C3-Cg)-cycloalkyl radical, (C3-Ce)-cycloalkyl, optionally substituted by or condensed with an optionally substituted phenyl! radical; and E/N S Re where the symbol and indices are as defined below: R' is a straight-chain or branched (C»-Cg)-alkanediy! group which is optionally substituted by, in the case of a phenyl group also condensed with, one or two optionally substituted phenyl groups.
    8. A process for preparing a compound of the formula (1) as claimed in one or more of claims 1 to 7 where Y is oxygen, which comprises reacting a carboxylic acid of the formula (V) R' 0 So PS = R? i R3 (On (V) in which R, R?, R®, X and n are as defined under formula (I) in the form of an activated derivative of this acid in the presence of a base with a compound of the formula (VI), in which R*, R® and m are as defined under formula {)) 4 "Ng / NH wn TN : Rr No,
    9. A composition having insecticidal, acaricidal and/or nematicidal action, which comprises at least one compound of the formula (1) as claimed in one or more of claims 1to 7.
    10. A composition having insecticidal, acaricidal and/or nematicidal action as claimed in claim 9 in a mixture with carriers and/or surfactants.
    11. The composition as claimed in claim 9 or 10, which comprises a further active compound selected from the group consisting of acaricides, fungicides, herbicides, insecticides, nematicides or growth-regulating substances.
    12. The use of a compound as claimed in one or more of claims 1 to 7 or of a composition as claimed in claim 9 or 10 for preparing a veterinary medicament.
    13. A method for controlling harmful insects, acarids and nematodes, which comprises applying an effective amount of a compound as claimed in one or more of claims 1 to 7 or of a composition as claimed in one or more of claims 9 to 11 to the site where the action is desired.
    14. A method for protecting useful plants against the undesirable action of harmful insects, acarids and nematodes, which comprises using at least one of the compounds as claimed in one or more of claims 1 to 7 or a composition as claimed in one or more of claims 9 to 11 for treating the seed of the useful plants.
    15. The use of compounds as claimed in one or more of claims 1 to 7 or of a composition as claimed in one or more of claims 9 to 11 for controlling harmful insects, acarids and nematodes.
    16. A process for preparing N-chloro-4-trifluoromethylinicotinamide and its salts of the formula (llla) CF, oy = N HA (lila) in which A is a non-oxidizable, organic or inorganic anion by chlorination of 4-trifluoromethyinicotinamide with Cl, in aqueous acid and, if desired, subsequent anion exchange and/or, if desired, reaction with a base, to give N-chloro-4-trifluoromethylnicotinamide.
    17. A salt of N-chioro-4-trifluoromethylnicotinamide of the formula (Illa) CF, XN CONHCI = N HA (Na)
    1 4 [= where A is a non-oxidizable, organic or inorganic anion
    18. A salt as claimed in claim 17, where A is F, HF», Cl, BF;, PFs, HSO4, 2 SOs, CH3COO, CFsCOO0, CFiSOs;, CH3SOs, p-CH3-CgHsSO3 or HoPO;.
    5 .
    19. The use of N-chloro-4-trifluoromethylinicotinamide hydrochloride as an intermediate in the synthesis of sulfimides of the formula (1) as claimed in claim 1.
    20. An acyisulfimide according to claim 1, substantially as herein described and exemplified, and/or described with reference to the accompanying figures.
    21. A process according to claim 8 or 16, substantially as herein described and exemplified, and/or described with reference to the accompanying figures.
    22. A composition according to claim 9, substantially as herein described and exemplified, and/or described with reference to the accompanying figures.
    23. Use according to claim 12, 15 or 19, substantially as herein described and exemplified, and/or described with reference to the accompanying figures.
    24. A method according to claim 13 or 14, substantially as herein described and exemplified, and/or described with reference to the accompanying figures. : 25. A salt according to claim 17, substantially as herein described and exemplified, and/or described with reference to the accompanying figures.
    2000/M 205 WO
    Abstract Heterocyclic acylsuifimides, processes for their preparation, compositions h comprising them and their use as pesticides Acylsulfimides of the formula (1) R1 O y Imes / ) GI N=S_ (1) A — RS R ! R3 (O)y where the symbols and indices are as defined in the description, are suitable for controlling animal pests.
ZA200207479A 2000-03-22 2002-09-18 Heterocyclic acylsulfimides, processes for their preparation, compositions comprising them and their use as pesticides. ZA200207479B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE2000114006 DE10014006A1 (en) 2000-03-22 2000-03-22 New heterocyclic acylsulfimide derivatives, useful as insecticides, acaricides and nematocides for plant protection or in veterinary medicine

Publications (1)

Publication Number Publication Date
ZA200207479B true ZA200207479B (en) 2003-10-09

Family

ID=7635788

Family Applications (1)

Application Number Title Priority Date Filing Date
ZA200207479A ZA200207479B (en) 2000-03-22 2002-09-18 Heterocyclic acylsulfimides, processes for their preparation, compositions comprising them and their use as pesticides.

Country Status (2)

Country Link
DE (1) DE10014006A1 (en)
ZA (1) ZA200207479B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AR031658A1 (en) 2000-12-13 2003-09-24 Aventis Cropscience Gmbh PROCEDURE FOR THE PREPARATION OF 4-HALOALQUILNICOTINONITRILOS
DE10144410A1 (en) 2001-09-11 2003-03-27 Bayer Cropscience Gmbh Preparation of alkyl 4-haloalkyl-nicotinate, useful as pesticide intermediate, comprises condensing an unsaturated aminoketone under reduced pressure with, e.g. substituted acrylate and cyclizing
DE10148290A1 (en) * 2001-09-29 2003-04-17 Bayer Cropscience Gmbh Heterocyclic amides, processes for their preparation, compositions containing them and their use
MXPA04011326A (en) 2002-05-16 2005-02-14 Bayer Cropscience Gmbh Pesticidal pyridinecarboxamide derivatives.
ES2572808T3 (en) * 2002-05-16 2016-06-02 Merial, Inc. Pyridinecarboxamide derivatives and their use as pesticides
KR20130088138A (en) 2010-06-28 2013-08-07 바이엘 인텔렉쳐 프로퍼티 게엠베하 Heteroaryl-substituted pyridine compounds for use as pesticides

Also Published As

Publication number Publication date
DE10014006A1 (en) 2001-09-27

Similar Documents

Publication Publication Date Title
WO2012018065A1 (en) Process for preparing compound having hiv integrase inhibitory activity
US6350877B1 (en) Manufacturing process
CN102321073A (en) Preparation method of nilotinib
ZA200207479B (en) Heterocyclic acylsulfimides, processes for their preparation, compositions comprising them and their use as pesticides.
JP6014912B2 (en) Process for the production of bendamustine alkyl esters, bendamustine, and their derivatives
US20230286901A1 (en) Process for the synthesis of melphalan
ES2670677T3 (en) Manufacturing process of 5-chloromethyl-2,3-dicarboxylic anhydride
JPWO2009028608A1 (en) Method for producing a phenol derivative substituted with iodine at the ortho position
AU732143B2 (en) Methods for synthesizing 2-substituted imidazoles
NO780202L (en) PROCEDURE FOR PREPARING NEW ISOKINOLIN DERIVATIVES
CN113583003A (en) Vardenafil analogue and synthetic method and application thereof
JP2004525927A (en) Method for producing lansoprazole and its intermediate
JPH01268677A (en) Production of substituted-pyridine-2, 3-dicarboxylic acid by successive oxidation of substituted-8-hydroxyquinoline
ZA200506402B (en) Process for the preparation of n-heteroaryl-n-aryl-amines by reacting an n-aryl carbamic acid ester with a haloheteroaryl and analogous process
JP2010077089A (en) Method for producing halopyrazinecarboxamide compound
AU2017209362B2 (en) Hydroquinone compound, preparation method therefor, and application in tumour resistance or immunomodulation
EP2264025B1 (en) Method for producing lansoprazole
JP2009126784A (en) Method for producing 2-iodo-3,4-dimethoxybenzonitrile
CN108997252B (en) Green synthesis method of oxadiazole derivative
JPH05331164A (en) Angiotensin ii antagonistic isoindole derivative
SU1728241A1 (en) Method of 3,6-dichloro-2-cyanopyridine synthesis
JP4444908B2 (en) Crystal of 2- (2-pyridylmethylsulfinyl) benzimidazole compound and production method thereof
CN117813304A (en) Method for preparing alfukanitai
KR810000291B1 (en) Process for preparing of 3,4-dihydro-2-methyl-4-oxo-2h-1,2-benzothiazine-3-carboxylic acid-1,1-dioxide
JP2001081074A (en) Production of arylpyridine derivative