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Title:
PROCESS FOR THE PREPARATION OF ANTHRANILAMIDE DERIVATIVES
Document Type and Number:
WIPO Patent Application WO/2008/031549
Kind Code:
A1
Abstract:
The present invention relates to a process for the preparation of a compound of formula (I), wherein the substituents are defined as in claim 1, by a) reacting a compound of formula (V) with a compound of formula (Vl) wherein hal is halogen and R1 is C1-C6alkyl in the presence of a base to a compound of formula (III); b) treating a compound of formula (Il) with said compound of formula (III) in the presence of a base to form a compound of formula (IV) and c) converting said compound of formula (IV) in the presence of an acid or a base to the compound of formula (I).

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Inventors:
VETTIGER THOMAS (CH)
STOLLER ANDRE (CH)
JACKSON DAVID ANTHONY (CH)
Application Number:
PCT/EP2007/007872
Publication Date:
March 20, 2008
Filing Date:
September 10, 2007
Export Citation:
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Assignee:
SYNGENTA PARTICIPATIONS AG (CH)
VETTIGER THOMAS (CH)
STOLLER ANDRE (CH)
JACKSON DAVID ANTHONY (CH)
International Classes:
C07D401/04
Domestic Patent References:
WO2006040113A22006-04-20
WO2005085234A22005-09-15
WO2003015519A12003-02-27
WO2003015518A12003-02-27
WO2003024222A12003-03-27
Attorney, Agent or Firm:
SYNGENTA PARTICIPATIONS AG (P.O. Box, Basel, CH)
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Claims:

What is claimed is:

1. A process for the preparation of a compound of formula

wherein

Ai, A 2 , A 3 and A 4 are each independently of the others hydrogen, halogen, nitro, cyano, hydroxy, Ci-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, d-C 6 haloalkyl, C 2 - C 6 haloalkenyl, C 2 -C 6 haloalkynyl, Cs-Cβhalocycloalkyl, Ci-C 4 alkoxy, Ci-C 4 haloalkoxy, C 1 - C 4 alkylthio, d-C 4 haloalkylthio, C 1 -C 4 haloalkylsulfinyl, C 1 -C 4 haloalkylsulfonyl, C 1 - C 4 alkylsulfinyl, Ci-C 4 alkylsulfonyl, Ci-C 4 alkylamino, C 2 -C 4 dialkylamino, C 3 -C 6 cycloalkylamino, CrC 6 alkyl-C 3 -C 6 cycloalkylamino, C 2 -C 4 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 - C 6 alkylaminocarbonyl, QrCedialkylaminocarbonyl, C 2 -C 6 alkoxycarbonyloxy, C 2 - C 6 alkylaminocarbonyloxy, Cs-Cedialkylaminocarbonyloxy or C 3 -C 6 trialkylsilyl, phenyl, benzyl or phenoxy; or phenyl, benzyl or phenoxy mono-, di- or trisubstituted by substituents independently selected from the group consisting of halogen, cyano, nitro, halogen, C 1 - C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, d-C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 - C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, Ci-C 4 alkoxy, d-C 4 haloalkoxy, Ci-C 4 alkylthio, C 1 - C 4 haloalkylthio, Ci-C 4 alkylsulfinyl, d-C 4 alkylsulfonyl, CrC 4 alkylamino, C 2 -C 4 dialkylamino, C 3 -C 6 cycloalkylamino, d-C 6 alkyl-C 3 -C 6 cycloalkylamino, C 2 -C 4 alkylcarbonyl, C 2 - C 6 alkoxycarbonyl, d-Cβalkylaminocarbonyl, Cs-Cβdialkylaminocarbonyl, C 2 - C 6 alkoxycarbonyloxy, d-Cβalkylaminocarbonyloxy, Ca-Cβdialkylaminocarbonyloxy and C 3 - C 6 trialkylsilyl; or

A 2 and A 3 together or A 3 and A 4 together are a bivalent group -J 1 -J 2 -J 3 -J 4 -; wherein

J 1 , J 2 , J 3 and J 4 form together with the two carbon atoms to which J 1 and J 4 are attached, an aromatic ring system; wherein

J 1 is nitrogen, sulfur, oxygen, a direct bond or C-R 5a ;

J 2 is nitrogen, sulfur, oxygen, a direct bond or C-R 5b ;

J 3 is nitrogen, sulfur, oxygen, a direct bond or C-R 50 ;

J 4 is nitrogen, sulfur, oxygen, a direct bond or C-R 5O ; with the provisos that a) not more than 1 substituent selected from J 1 , J 2 , J 3 and J 4 can at the same time form a direct bond, b) not more than 2 substituents selected from J 1 , J 2 , J 3 and J 4 can be oxygen or sulfur, and c) 2 substituents selected from J 1 , J 2 , J 3 and J 4 as oxygen and/or sulfur are separated by at least one carbon atom; each of R 5a , R 5b , R 5c , and R 5d which may be the same or different, represents hydrogen, halogen, nitro, cyano, hydroxy, CHO, d-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, d-C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, C 1 -C 4 BIkOXy, C 1 - C 4 alkoxy-C 1 -C 4 alkoxy-C 1 -C 4 alkyl, d-C 4 haloalkoxy, C r C 4 alkylthio, C r C 4 haloalkylthio, C 1 - C 4 haloalkylsulfinyl, d-C 4 haloalkylsulfonyl, d-C 4 alkylsulfinyl, d-C 4 alkylsulfonyl, C 1 - C 4 alkylsulfonyl-d-C 4 alkyl, d-C 4 alkylsulfoximino-d-C 4 alkyl, d-C 4 alkylamino, C 2 - C 4 dialkylamino, C3-C 6 cycloalkylamino, d-C 6 alkyl-C 3 -C 6 cycloalkylamino, C 2 -C 4 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminocarbonyl, Cs-Cedialkylaminocarbonyl, C 2 - C 6 alkoxycarbonyloxy, d-Cβalkylaminocarbonyloxy, Cs-Cβdialkylaminocarbonyloxy, C 1 - dalkoxyimino-d-C 4 alkyl, C 3 -C 6 trialkylsilyl, phenyl, benzyl or phenoxy; or phenyl, benzyl or phenoxy mono-, di- or trisubstituted by substituents independently selected from the group consisting of halogen, cyano, nitro, halogen, d-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 - C 6 cycloalkyl, d-C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, C 1 - C 4 alkoxy, d-C 4 haloalkoxy, d-C 4 alkylthio, d-C 4 haloalkylthio, d-C 4 alkylsulfinyl, C 1 - C 4 alkylsulfonyl, d-C 4 alkylamino, C 2 -C 4 dialkylamino, C 3 -C 6 cycloalkylamino, d-C 6 alkyl-C 3 - C 6 cycloalkylamino, C 2 -C 4 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminocarbonyl, C 3 - C 6 dialkylaminocarbonyl, C 2 -C 6 alkoxycarbonyloxy, CVCβalkylaminocarbonyloxy, C 3 - C 6 dialkylaminocarbonyloxy and C 3 -C 6 trialkylsilyl; A 5 is a group -A-(X)p-(Y)q-B, wherein

A is a chemical bond, or is d-C 6 alkylene, C 2 -C 6 alkenylene, C 2 -C 6 alkynylene, or is a bivalent three- to ten-membered monocyclic or fused bicyclic ring system which can be partially saturated or fully saturated and can contain 1 to 4 hetero atoms selected from the group

consisting of nitrogen, oxygen and sulfur, it not being possible for each ring system to contain more than 2 oxygen atoms and more than 2 sulfur atoms; and it being possible for the three- to ten-membered ring system itself and also for the C 1 - C 6 alkylene, C 2 -C 6 alkenylene and C 2 -C 6 alkynylene groups to be mono-, di- or trisubstituted by substituents independently selected from the group consisting of halogen, cyano, nitro, hydroxy, d-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 5 -C 7 cycloalkenyl, C 5 - C 8 cycloalkynyl, d-C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, C 5 - Cyhalocycloalkenyl, C 5 -C 8 halocycloalkynyl, d-C 4 alkoxy, d-C 4 haloalkoxy, Ci-C 4 alkylthio, C 1 - dhaloalkylthio, d-C 4 alkylsulfinyl, d-C 4 alkylsulfonyl, d-C 4 alkylamino, C 2 -C 4 dialkylamino, C 3 -C 6 cycloalkylamino, d-C 6 alkyl-C 3 -C 6 cycloalkylamino, C 2 -C 4 alkylcarbonyl, C 2 - C 6 alkoxycarbonyl, C 2 -C 6 alkylaminocarbonyl, Cs-Cβdialkylaminocarbonyl, C 2 - C 6 alkoxycarbonyloxy, d-Cβalkylaminocarbonyloxy, Cs-Cεdialkylaminocarbonyloxy, C 3 - C 6 trialkylsilyl, and a three- to ten-membered monocyclic or fused bicyclic ring system which can be aromatic, partially saturated or fully saturated and can contain 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, it not being possible for each ring system to contain more than 2 oxygen atoms and more than 2 sulfur atoms, and it being possible for the three- to ten-membered ring system itself to be mono-, di- or trisubstituted by substituents independently selected from the group consisting of halogen, cyano, nitro, hydroxy, d-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 5 -C 7 cycloalkenyl, C 5 - C 8 cycloalkynyl, d-C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, C 5 - dhalocycloalkenyl, C 5 -C 8 halocycloalkynyl, d-C 4 alkoxy, d-C 4 haloalkoxy, d-C 4 alkylthio, d- C 4 haloalkylthio, d-C 4 alkylsulfinyl, d-C 4 alkylsulfonyl, d-C 4 alkylamino, C 2 -C 4 dialkylamino, C 3 -C 6 cycloalkylamino, d-Cealkyl-Cs-CeCycloalkylamino, C 2 -C 4 alkylcarbonyl, C 2 - C 6 alkoxycarbonyl, C 2 -C 6 alkylaminocarbonyl, Cs-Cedialkylaminocarbonyl, C 2 - C 6 alkoxycarbonyloxy, C 2 -C 6 alkylaminocarbonyloxy, Cs-Cβdialkylaminocarbonyloxy, C 3 - C 6 trialkylsilyl and phenyl, it being possible for the phenyl group in turn to be substituted by substituents independently selected from the group consisting of hydroxy, d-C 6 alkyl, C 1 - C 6 haloalkyl, d-C 6 alkylthio, d-C 6 haloalkylthio, C 3 -C 6 alkenylthio, C 3 -C 6 haloalkenylthio, C 3 - C 6 alkynylthio, Ci -C S aIkOXy-C 1 -C 3 alkylthio, C 2 -C 4 alkylcarbonyl-CrC 3 alkylthio, C 2 - C 4 alkoxycarbonyl-d-C 3 aikylthio, cyano-d-C 3 alkylthio, CrCealkylsulfinyl, d-C 6 halo- alkylsulfinyl, d-C 6 alkylsulfonyl, d-C 6 haloalkylsulfonyl, aminosulfonyl, d-C 2 alkylamino- sulfonyl, N,N-di(C 1 -C 2 alkyl)aminosulfonyl, di(d-C 4 alkyl)amino, halogen, cyano and nitro; and substituents at nitrogen atoms in the ring systems being other than halogen;

X is oxygen, -N(H)- or -N(CrC 4 alkyl)-;

Y is CrC 6 alkylene, C 2 -C 6 alkenylene, C 2 -C 6 alkynylene, or a bivalent three- to ten-membered monocyclic or fused bicyclic ring system which can be partially saturated or fully saturated and can contain 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, it not being possible for each ring system to contain more than 2 oxygen atoms and more than 2 sulfur atoms; and it being possible for the three- to ten-membered ring system itself and also for the C 1 - C 6 alkylene, C 2 -C 6 alkenylene and C 2 -C 6 alkynylene groups to be mono-, di- or trisubstituted by substituents independently selected from the group consisting of halogen, cyano, nitro, hydroxy, Ci-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 5 -C 7 cycloalkenyl, C 5 - C 8 cycloalkynyl, d-C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, C 5 - Cyhalocycloalkenyl, C 5 -C 8 halocycloalkynyl, C 1 -C 4 SIkOXy 1 d-C 4 haloalkoxy, d-C 4 alkylthio, C 1 - C 4 haloalkylthio, CrC 4 alkylsulfinyl, d-C 4 alkylsulfonyl, CrC 4 alkylamino, C 2 -C 4 dialkylamino, Ca-Cecycloalkylamino, d-Cealkyl-Ca-Cecycloalkylamino, C 2 -C 4 alkylcarbonyl, C 2 - C 6 alkoxycarbonyl, C 2 -C 6 alkylaminocarbonyl, QrCedialkylaminocarbonyl, C 2 - C 6 alkoxycarbonyloxy, C 2 -C 6 alkylaminocarbonyloxy, Cs-Cβdialkylaminocarbonyloxy, C 3 - C 6 trialkylsilyl and a three- to ten-membered monocyclic or fused bicyclic ring system which can be aromatic, partially saturated or fully saturated and can contain 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, it not being possible for each ring system to contain more than 2 oxygen atoms and more than 2 sulfur atoms, and it being possible for the three- to ten-membered ring system itself to be mono-, di- or trisubstituted by substituents independently selected from the group consisting of halogen, cyano, nitro, hydroxy, d-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 5 - Cycycloalkenyl, C 5 -C 8 cycloalkynyl, d-C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 - C 6 halocycloalkyl, C 5 -C 7 halocycloalkenyl, C 5 -C 8 halocycloalkynyl, d-C 4 alkoxy, C 1 - C 4 haloalkoxy, d-C 4 alkylthio, d-C 4 haloalkylthio, d-C 4 alkylsulfinyl, d-C 4 alkylsulfonyl, C 1 - C 4 alkylamino, C 2 -C 4 dialkylamino, C 3 -C 6 cycloalkylamino, d-Cealkyl-Cs-Cecycloalkylamino, C 2 - C 4 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminocarbonyl, Ca-Cedialkylaminocarbonyl, C 2 -C 6 alkoxycarbonyloxy, C 2 -C 6 alkylaminocarbonyloxy, CrCedialkylaminocarbonyloxy, C 3 - C 6 trialkylsilyl and phenyl, it being possible for the phenyl group in turn to be substituted by substituents independently selected from the group consisting of hydroxy, d-C 6 alkyl, C 1 - C 6 haloalkyl, d-C 6 alkylthio, d-C 6 haloalkylthio, C 3 -C 6 alkenylthio, C 3 -C 6 haloalkenylthio, C 3 - C 6 alkynylthio, d-C 3 alkoxy-d-C 3 alkylthio, C 2 -C 4 alkylcarbonyl-d-C 3 alkylthio, C 2 - C^lkoxycarbonyl-d-Csalkylthio, cyano-d-C 3 alkylthio, d-C 6 alkylsulfinyl, d-C 6 halo-

alkylsulfinyl, d-C 6 alkylsulfonyl, d-C 6 haloalkylsulfonyl, aminosulfonyl, d-C 2 alkylamino- sulfonyl, N,N-di(Ci-C 2 alkyl)aminosulfonyl, (Ji(C 1 -C 4 alkyl)amino, halogen, cyano and nitro; and substituents at nitrogen atoms in the ring systems being other than halogen; p is 0 or 1 ; q is 0 or 1 ;

B is a three- to four-membered ring system which is fully or partially saturated and can contain a hetero atom selected from the group consisting of nitrogen, oxygen and sulfur, and it being possible for the three- to four-membered ring system itself to be mono-, di- or trisubstituted by substituents independently selected from the group consisting of halogen, cyano, nitro, hydroxy, Ci-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 5 - Cycycloalkenyl, C 5 -C 8 cycloalkynyl, d-C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 - C 6 halocycloalkyl, C 5 -C 7 halocycloalkenyl, C 5 -C 8 halocycloalkynyl, d-C 4 alkoxy, C 1 - C 4 haloalkoxy, Ci-C 4 alkylthio, d-C 4 haloalkylthio, d-C 4 alkylsulfinyl, d-C 4 alkylsulfonyl, C 1 - C 4 alkylamino, C 2 -C 4 dialkylamino, C 3 -C 6 cycloalkylamino, d-C 6 alkyl-C 3 -C 6 cycloalkylamino, C 2 - C 4 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminocarbonyl, CrCedialkylaminocarbonyl, C 2 -C 6 alkoxycarbonyloxy, C 2 -C 6 alkylaminocarbonyloxy, CrCedialkylaminocarbonyloxy, C 3 - C 6 trialkylsilyl and a three- to ten-membered monocyclic or fused bicyclic ring system which can be aromatic, partially saturated or fully saturated and can contain 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, it not being possible for each ring system to contain more than 2 oxygen atoms and more than 2 sulfur atoms, and it being possible for the three- to ten-membered ring system itself to be mono-, di- or trisubstituted by substituents independently selected from the group consisting of halogen, cyano, nitro, hydroxy, d-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 5 - Cycycloalkenyl, C 5 -C 8 cycloalkynyl, C 1 - C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 - C 6 halocycloalkyl, Cs-Cyhalocycloalkenyl, C 5 -C 8 halocycloalkynyl, d-C 4 alkoxy, C 1 - dhaloalkoxy, d-C 4 alkylthio, C 1 -C 4 haloalkylthio, d-C 4 alkylsulfinyl, d-C 4 alkylsulfonyl, d- C 4 alkylamino, C 2 -C 4 dialkylamino, C 3 -C 6 cycloalkylamino, d-C 6 alkyl-C 3 -C 6 cycloalkylamino, C 2 - C 4 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminocarbonyl, Cs-Cβdialkylaminocarbonyl, C 2 -C 6 alkoxycarbonyloxy, C 2 -C 6 alkylaminocarbonyloxy, Cs-Cβdialkylaminocarbonyloxy, C 3 - C 6 trialkylsilyl and phenyl, it being possible for the phenyl group in turn to be substituted by substituents independently selected from the group consisting of hydroxy, d-C 6 alkyl, C 1 - Cehaloalkyl.d-Cealkylthio, d-C 6 haloalkylthio, C 3 -C 6 alkenylthio, C 3 -C 6 haloalkenylthio, C 3 - C 6 alkynylthio, d-C 3 alkoxy-d-C 3 alkylthio, C 2 -C 4 alkylcarbonyl-d-C 3 alkylthio, C 2 - dalkoxycarbonyl-d-Csalkylthio, cyano-d-C 3 alkylthio, C r C 6 alkylsulfinyl, d-C 8 halo-

alkylsulfinyl, Ci-C 6 alkylsulfonyl, d-C 6 haloalkylsulfonyl, aminosulfonyl, d-C 2 alkylamino- sulfonyl, N,N-di(C 1 -C 2 alkyl)aminosulfonyl, di(Ci-C 4 alkyl)amino, halogen, cyano and nitro; and substituents at nitrogen atoms in the ring systems being other than halogen; or B is hydrogen, Ci-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl or C 5 -C 6 cycloalkyl; or is d-C 6 alkyl, C 2 - C 6 alkenyl, C 2 -C 6 alkynyl and C 5 -C 6 cycloalkyl substituted with one, two or three substituents independently selected from the group consisting of halogen, cyano, nitro, hydroxy, C 1 - C 4 alkyl, d-C 4 alkoxy, d-C 4 haloalkoxy, C 1 -C 4 alkylthio, Ci-C 4 alkylsulfinyl, d-C 4 alkylsulfonyl, Ci-C 4 alkylsulfoximino, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 trialkylsilyl, benzyl, phenoxy and a three- to ten-membered, monocyclic or fused bicyclic ring system which may be aromatic, partially saturated or fully saturated, wherein the six-membered aromatic ring system contains at least one heteroatom selected from the group consisting of oxygen, nitro and sulfur; it being possible for said benzyl, phenoxy and three- to ten-membered, monocyclic or fused bicyclic ring system in turn to be substituted by one to three substituents independently selected from the group consisting of d-C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 6 cycloalkyl, d-C 4 haloalkyl, C 2 -C 4 haloalkenyl, C 2 -C 4 haloalkynyl, C 3 -C 6 halocycloalkyl, halogen, cyano, nitro, d-C 4 alkoxy, d-C 4 haloalkoxy, d-C 4 alkylthio, Ci-C 4 alkylsulfinyl, d- C 4 alkylsulfonyl, d-C 4 alkylsulfoximino, d-C 4 alkylamino, C 2 -C 6 dialkylamino, C 3 - C 6 cycloalkylamino, Ci-C 4 alkyl-C 3 -C 6 cycloalkylamino, C 2 -C 4 alkylcarbonyl, C 2 - C 6 alkoxycarbonyl, C 2 -C 6 alkylaminocarbonyl, C 2 -C 8 dialkylaminocarbonyl and C 2 -C 6 trialkylsilyl; it being possible for said three- to ten-membered, monocyclic or fused bicyclic ring system to be spiro-bonded to the C 3 -C 6 cycloalkyl group; or B is Ci-C 4 alkoxy, d-C 4 alkylamino, C 2 -C 8 dialkylamino, C 3 -C 6 cycloalkylamino, C 2 - C 6 alkoxycarbonyl or C 2 -C 6 alkylcarbonyl; or A 5 is a group

Yia is a d-C 6 alkylene, C 2 -C 6 alkenylene or C 3 -C 6 alkynylene chain which may be mono-, di- or trisubstituted by R 20 , where the unsaturated bonds of the chain are not attached directly to the sulfur atom; or is C 3 -C 6 cycloalkylene, which may be mono-, di- or trisubstituted by R 21 ; or Y,a and Y 2 form together with the chain -G-Y ! b-S(=O=N-Z)- a ring system of at least 3 members; wherein Y,a and Y 2 together represent the group -CH 2 -; -CH 2 -CH 2 -; -CH 2 -CH 2 -CH 2 ; -CH 2 -CH=CH-; -CH=CH-CH 2 -; -CH 2 -G 6 -CH 2 -;

-Cη2-Cη2-G 10 -CH 2 -! -CH 2 -G 7 -CH 2 -CH 2 - or -CH 2 -Cn 2 -CaIi-CH 2 -CH 2 -; G 6 is oxygen, N(-Z 7 ) or sulfur; G 7 is oxygen, N(-Z 8 ) or sulfur; Gio is oxygen, N(-Zn) or sulfur; G 11 is oxygen, N(-Z 12 ) or sulfur;

R 20 and R 21 independently of one another are halogen, nitro, cyano, hydroxy, CrC 6 alkyl, d-Cehaloalkyl, CrC 6 alkylthio, Ci-C 6 alkylsulfinyl, C r C 6 alkylsulfonyl, C r C 6 haloalkylthio, d-Cehaloalkylsulfinyl, d-Cehaloalkylsulfonyl, d-C 6 alkoxycarbonyl, CrC 6 alkylcarbonyl, d-Cealkoxy-d-Cealkyl, d-Cealkoxy-d-Cealkyl, C r C 6 alkoxy, d-C 6 halo-alkoxy, benzyl or phenyl, where phenyl and benzyl for their part may be mono-, di- or trisubstituted by substituents independently selected from the group consisting of d-C 6 alkyl, d-C 6 haloalkyl, d-C 6 alkoxy, d-C 6 haloalkoxy, halogen, cyano, hydroxyl and nitro;

Yib is a direct bond or is a d-C 6 alkylene, C 2 -C 6 alkenylene or C 3 -C 6 alkynylene chain which may be mono-, di- or trisubstituted by R 22 , where the unsaturated bonds of the chain are not attached directly to the sulfur atom; or is C 3 -C 6 cycloalkylene, which may be mono-, di- or trisubstituted by R 23 , or is 1 ,2-, 1 ,3- or 1 ,4-phenylene;

R 22 and R 23 independently of one another are halogen, nitro, cyano, hydroxy, d-C 6 alkyl, d-C 6 haloalkyl, d-C 6 alkylthio, d-C 6 alkylsulfinyl, C r C 6 alkylsulfonyl, d-C 6 haloalkylthio, d-C 6 haloalkylsulfinyl, d-C 6 haloalkylsulfonyl, d-C 6 alkoxycarbonyl, d-C 6 alkylcarbonyl, d-Cealkoxy-d-Cealkyl, Ci-C 6 alkoxy-d-C 6 alkyl, d-C 6 alkoxy, Ci-C 6 halo-alkoxy, benzyl or phenyl, where phenyl and benzyl for their part may be mono-, di- or trisubstituted by substituents independently selected from the group consisting of d-C 6 alkyl, d-C 6 haloalkyl, d-C 6 alkoxy, d-C 6 haloalkoxy, halogen, cyano, hydroxyl and nitro;

Y 2 is a d-C 6 alkylene, C 2 -C 6 alkenylene or C 3 -C 6 alkynylene chain which may be mono-, di- or trisubstituted by R 24 , where the unsaturated bonds of the chain are not attached directly to the sulfur atom; or is C 3 -C 6 cycloalkylene, which may be mono-, di- or trisubstituted by R 25 ; R 24 and R 25 independently of one another are halogen, nitro, cyano, hydroxy, d-C 6 alkyl, d-Cehaloalkyl, d-C 6 alkylthio, d-C 6 alkylsulfinyl, d-C 6 alkylsulfonyl, d-C 6 haloalkylthio, d-Cehaloalkylsulfinyl, d-C 6 haloalkylsulfonyl, d-C 6 alkoxycarbonyl, d-C 6 alkylcarbonyl, d-C 6 alkoxy-d-C 6 alkyl, d-C 6 alkoxy-d-C 6 alkyl, d-C 6 alkoxy, d-C 6 halo-alkoxy, benzyl or phenyl, where phenyl and benzyl for their part may be mono-, di- or trisubstituted by substituents independently selected from the group consisting of d-C 6 alkyl, d-C 6 haloalkyl, d-C 6 alkoxy, d-C 6 haloalkoxy, halogen, cyano, hydroxyl and nitro; Y 3 is hydrogen, halogen, d-C 6 haloalkyl or d-C 6 alkyl;

G is a direct bond, oxygen, N^Z 1 ), sulfur or the group G 1 -CC=Ga)-G 3 ; Gi is a direct bond, oxygen, N(-Z 2 ) or sulfur; G 2 is oxygen, N(-Z 3 ) or sulfur; G 3 is a direct bond, oxygen, N(-Z 4 ) or sulfur;

Z, Z 1 , Z 2 , Z 3 and Z 4 independently of one another are hydrogen, d-C 6 alkyl, d-C 6 haloalkyl, d-C 6 cycloalkyl, CrC 6 halocycloalkyl, d-C 6 alkylthio, d-C 6 haloalkylthio or d-C 6 alkoxy-d-C 6 alkyl; or d-C 6 alkyl, d-C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, d-C 6 alkylthio, d-C 6 haloalkylthio or d-C 6 alkoxy-d-C 6 alkyl substituted by Ci-C 6 alkyl, d-C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, d-C 6 alkoxy, cyano, nitro or d-C 6 haloalkoxy; or Z, Z 1 , Z 2 , Z 3 and Z 4 independently of one another are -C(O)R 34 , -C(O)O-R 35 , -CONR 36 R 29 , -SO 2 R 30 or -P(O)(OR 31 )(OR 32 )-OR 3 3;

R 34 is CrC 6 alkyl, d-C 6 haloalkyl, C 3 -C 6 cycloalkyl, Cs-Cβhalocycloalkyl, d-C 6 alkylthio, d-C 6 haloalkylthio, d-C δ alkoxycarbonyl, d-C 6 alkylcarbonyl or d-C 6 alkoxy-d-C 6 alkyl; or d-C 6 alkyl, d-C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, d-C 6 alkylthio, d-C 6 haloalkylthio, d-C 6 alkoxycarbonyl, d-C 6 alkylcarbonyl or d-Cβalkoxy-d-Cealkyl substituted by substituents independently selected from the group consisting of d-C 6 alkyl, d-C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, d-C 6 alkoxy and d-C 6 haloalkoxy; and R29, R30, R31, R32, R33 > R35 and R 36 independently of one another are d-C 6 alkyl, d-C 6 haloalkyl, C 3 -C 6 cycloalkyl or C 3 -C 6 halocycloalkyl; or d-Cβalkyl, d-C 6 haloalkyl, C 3 -C 6 cycloalkyl or C 3 -C 6 halocycloalkyl substituted by d-C 6 alkyl, d-C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, d-C 6 alkoxy, d-C 6 haloalkoxy;

or A 5 is a group ; wherein

R 37 and R 38 , which may be the same or different, represents hydrogen, COOH 1 halogen, nitro, cyano, hydroxy, d-C 6 alkyl, d-Cehaloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 2 - C 6 haloalkenyl, C 2 -C 6 haloalkynyl, d-C 6 alkylthio, d-C 6 alkylsulfinyl, d-C 6 alkylsulfonyl, d-C 6 haloalkylthio, d-C 6 haloalkylsulfinyl, d-C 6 haloalkylsulfonyl, CrCealkoxycarbonyl, d-C 6 alkylcarbonyl, CrCealkylaminocarbonyl, Cs-Cβdialkylaminocarbonyl, d-C 6 alkoxy-d-C 6 alkyl, d-Cehaloalkoxy-CrCealkyl, C r C 6 alkoxy, d-C 6 haloalkoxy, C 1 - C 6 alkylamino, C 2 -C 6 dialkylamino, C 3 -C 6 trialkylsilyl, benzyl or phenyl; where phenyl and benzyl for their part may be mono- di- or trisubstituted by d-C 6 alkyl, d-C 6 haloalkyl, d-C 6 alkoxy, d-C 6 haloalkoxy, halogen, cyano, hydroxyl or nitro;

k is O, 1 , 2, 3 or 4;

A 8 is oxygen, sulfur, SO, SO 2 , S(O) U =N-R, C=N-OR 40 , N-R 0 , C=O or P(X)t-R 39 ;

R 39 is hydrogen, Ci-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, CrC 6 haloalkyl, d-C 6 alkoxy, hydroxy, d-C 6 cycloalkyl, Ci-C 6 cycloalkyl-Ci-C 6 alkyl, benzyl or phenyl; where phenyl and benzyl for their part may be mono- di- or trisubstituted by Ci-C 6 alkyl, Ci-C 6 haloalkyl, halogen, cyano or nitro; or R 33 is 0 ' Na + , O Li + or O K + ;

R 40 is hydrogen, CrC 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, d-C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -

C 6 haloalkynyl, d-C 6 alkoxy-d-C 6 alkyl, Ci-C 6 haloalkoxy-Ci-C 6 alkyl or benzyl;

R is hydrogen, Ci-C 6 alkyl, Ci-C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl,

Ci-C 6 alkylthio, Ci-C β haloalkylthio, d-C 6 alkoxy-d-C β alkyl or d-C 6 haloalkoxy-d-C 6 alkyl; or

R is d-C 6 alkyl, d-C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, d-C 6 alkylthio,

Ci-C 6 haloalkylthio, d-C 6 alkoxy-d-C 6 alkyl or Ci-C 6 haloalkoxy-d-C 6 alkyl substituted by d-C 6 alkyl, d-C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, d-C 6 alkoxy, or d-C 6 haloalkoxy; or R is cyano, nitro, -C(O)R 4I , -C(O)OR 42 , -CONR 43 R 44 , -SO 2 R 45 or -

P(O)(OR 46 )(OR 47 );

R 0 is hydrogen, Ci-C 6 alkyl, d-C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl,

Ci-C 6 alkylthio, d-C 6 haloalkylthio, Ci-C 6 alkoxy-d-C 6 alkyl or d-Cehaloalkoxy-d-Cealkyl; or

R 0 is d-C 6 alkyl, d-C 6 haloalkyl, C 3 -C 6 cycloalkyl, QrCehalocycloalkyl, Ci-C 6 alkylthio, d-C 6 haloalkylthio, d-C 6 alkoxy-d-C 6 alkyl or d-C 6 haloalkoxy-d-C 6 alkyl substituted by

Ci-C 6 alkyl, Ci-C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, d-C 6 alkoxy, or

Ci-C 6 haloalkoxy; or R 0 is cyano, nitro, -C(O)R 04I , -C(O)OR 042 , -CONR 043 R 044 , -SO 2 R 045 or

-P(O)(OR 046 (OR 047 ); each of R 41 and R 041 , which may be the same or different, represents hydrogen, d-C 6 alkyl,

Ci-C 6 haloalkyl, d-C 6 cycloalkyl, d-Cehalocycloalkyl, d-C 6 alkylthio, d-C 6 haloalkylthio,

Ci-Cealkoxycarbonyl, d-C 6 alkylcarbonyl or d-Cealkoxy-d-Cealkyl; or d-C 6 alkyl,

Ci-C 6 haloalkyl, d-C 6 cycloalkyl, d-Cehalocycloalkyl, d-C 6 alkylthio, d-C 6 haloalkylthio,

Ci-C 6 alkoxycarbonyl, d-C 6 alkylcarbonyl or Ci-Cealkoxy-d-Cealkyl substituted by d-C 6 alkyl, d-C 6 haloalkyl, d-C 6 cycloalkyl, d-Cβhalocycloalkyl, d-C 6 alkoxy, or d-C 6 haloalkoxy; each of R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 04 i, R 042 , R 043 , R 044 , R 045 R 046 and R 047 which may be the same or different, represents Ci-C 6 alkyl, d-C 6 haloalkyl, d-C 6 cycloalkyl or

Ci-C 6 halocycloalkyl; or d-C 6 alkyi, d-C 6 haloalkyl, d-C 6 cycloalkyl or Ci-C 6 halocycloalkyl substituted by Ci-C 6 alkyl, d-C 6 haloalkyl, d-C 6 cycloalkyl, Ci-C 6 halocycloalkyl, d-C 6 alkoxy or d-C 6 haloalkoxy;

X is oxygen or sulfur;

u is 0 or 1 ; and t is O or 1 ;

A 6 is hydrogen, d-C 6 alkyl, C 3 -C 6 cycloalkyl, Ci-C 6 haloalkyl, cyano, CrC 4 alkoxy, d-

C 4 haloalkoxy, Ci-C 4 alkylthio, C r C 4 haloalkylthio, CrC 4 alkylsulfinyl, CrC 4 alkylsulfonyl, C 1 -

C 4 haloalkylsulfinyl or d-C 4 haloalkylsulfonyl; and

A 7 is Ci-C 6 alkyl, C 3 -C 6 cycloalkyl, Ci-C 6 haloalkyl, halogen, cyano, Ci-C 4 alkoxy, d- dhaloalkoxy, d-C 4 alkylthio, Ci-C 4 haloalkylthio, C 1 -C 4 alkylsulf inyl, d-C 4 alkylsulfonyl, d-

C 4 haloalkylsulfinyl or d-dhaloalkylsulfonyl; which process comprises a) reacting a compound of formula V

wherein A 1 , A 2 , A 3 , A 4 and A 5 are as defined under formula I above, with a compound of formula Vl

wherein hal is halogen and R 1 is d-C 6 alkyl in the presence of a base to a compound of formula III

wherein A 1 , A 2 , A 3 , A 4 and A 5 are as defined under formula I above and R 1 is d-C 6 alkyl; b) treating a compound of formula Il

wherein A 6 and A 7 are as defined under formula I above, with said compound of formula

wherein A 1 , A 2 , A 3 , A 4 and A 5 are as defined under formula I above and R 1 is d-Cβalkyl, in the presence of a base to form a compound of formula IV

wherein A 1 , A 2 , A 3 , A 4 , A 5 A 6 and A 7 are as defined under formula I above and c) converting said compound of formula IV in the presence of an acid or a base to the compound of formula I.

2. A compound of formula

wherein A 1 , A 2 , A 3 , A 4 and A 5 are as defined under formula I in claim 1 and R 1 is CrC 6 alkyl.

Description:

Process for the preparation of anthranilamide derivatives

The present invention relates to a novel process for the preparation of insecticidally active anthranilamide derivatives and to novel intermediates for use in that process.

Processes for the preparation of anthranilamide derivatives are described, for example, in WO 03/015519, WO2005/085234 and WO2006/0401 13.

According to WO 03/015519, WO2006/040113 and WO2005/085234, anthranilamide derivatives of formula A,

wherein Rx, Ry and Rz are organic substituents, may be made from the ring opening of a benzoxazinone of formula B

with an amine of formula NHRxRx.

WO2005/085234 describes that Benzoxazinones of formula B may be made from amino acids of formula C,

(C)

by treatment with a carboxylic acid of formula Ry-COOH and a dehydrating reagent such as methanesulfonyl chloride (optionally in the presence of a base such as pyridine or triethylamine). Alternatively benzoxazinones of formula B may be obtained by the treatment of amino acids of formula C with an acid chloride of formula Ry-COCI under basic conditions (for example in pyridine), followed if necessary by a second cyclisation step.

However, such processes have the disadvantage that the compound Ry-COOH has to be prepared independently, using technically difficult steps such as metallation at very low temperature with strong bases, or using protecting groups such as esters.

The present invention accordingly relates to a process for the preparation of compounds of formula I

wherein

A 1 , A 2 , A 3 and A 4 are each independently of the others hydrogen, halogen, nitro, cyano, hydroxy, C r C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, Ci-C 6 haloalkyl, C 2 - C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, Ci-C 4 alkoxy, d-C^aloalkoxy, C 1 - C 4 alkylthio, C r C 4 haloalkylthio, C 1 -C 4 haloalkylsulfinyl, CrC^aloalkylsulfonyl, C 1 - C 4 alkylsulfinyl, CrC 4 alkylsulfonyl, CrC^lkylamino, C 2 -C 4 dialkylamino, C 3 -C 6 cycloalkylamino, d-Cealkyl-Cs-Cβcycloalkylamino, C 2 -C 4 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 - C 6 alkylaminocarbonyl, Ca-Cβdialkylaminocarbonyl, C 2 -C 6 alkoxycarbonyloxy, C 2 - C 6 alkylaminocarbonyloxy, CrCedialkylaminocarbonyloxy or C 3 -C 6 trialkylsilyl, phenyl, benzyl or phenoxy; or phenyl, benzyl or phenoxy mono-, di- or trisubstituted by substituents independently selected from the group consisting of halogen, cyano, nitro, halogen, C 1 -

C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, Ci-C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -

C 6 haloalkynyl, Cs-Cehalocycloalkyl, d-C 4 alkoxy, d-C 4 haloalkoxy, CrC 4 alkylthio, C 1 -

C 4 haloalkylthio, d-C 4 alkylsulfinyl, d-C 4 alkylsulfonyl, Ci-C 4 alkylamino, C 2 -C 4 dialkylamino,

C 3 -C 6 cycloalkylannino, d-Cealkyl-C-s-Cecycloalkylamino, C 2 -C 4 alkylcarbonyl, C 2 -

C 6 alkoxycarbonyl, drCedialkylaminocarbonyl, C 2 -

C 6 alkoxycarbonyloxy, QrCealkylaminocarbonyloxy, C 3 -C 6 dialkylaminocarbonyloxy and C 3 -

C 6 trialkylsilyl; or

A 2 and A 3 together or A 3 and A 4 together are a bivalent group -J 1 -J 2 -J 3 -J 4 -; wherein

J 1 , J 2 , J 3 and J 4 form together with the two carbon atoms to which J 1 and J 4 are attached, an aromatic ring system; wherein

J 1 is nitrogen, sulfur, oxygen, a direct bond or C-R 5a ;

J 2 is nitrogen, sulfur, oxygen, a direct bond or C-R 5b ;

J 3 is nitrogen, sulfur, oxygen, a direct bond or C-R 5c ;

J 4 is nitrogen, sulfur, oxygen, a direct bond or C-R 5d ; with the provisos that a) not more than 1 substituent selected from J 1 , J 2 , J 3 and J 4 can at the same time form a direct bond, b) not more than 2 substituents selected from J 1 , J 2 , J 3 and J 4 can be oxygen or sulfur, and c) 2 substituents selected from J 1 , J 2 , J 3 and J 4 as oxygen and/or sulfur are separated by at least one carbon atom; each of R 5a , Rs b , Rs 0 , and R 5d which may be the same or different, represents hydrogen, halogen, nitro, cyano, hydroxy, CHO, d-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, CrC 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, d-C 4 alkoxy, C 1 - C 4 alkoxy-d-C 4 alkoxy-d-C 4 alkyl, C r C 4 haloalkoxy, C r C 4 alkylthio, d-C 4 haloalkylthio, C 1 - C 4 haloalkylsulfinyl, CrC 4 haloalkylsulfonyl, d-C 4 alkylsulfinyl, d-C 4 alkylsulfonyl, C 1 - C 4 alkylsulfonyl-CVC 4 alkyl, d-C 4 alkylsulfoximino-d-C 4 alkyl, d-C 4 alkylamino, C 2 - C 4 dialkylamino, C 3 -C 6 cycloalkylamino, d-C 6 alkyl-C 3 -C 6 cycloalkylamino, C 2 -C 4 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, CrCβalkylaminocarbonyl, Cs-Cβdialkylaminocarbonyl, C 2 - C 6 alkoxycarbonyloxy, C^Cealkylaminocarbonyloxy, Cs-Cedialkylaminocarbonyloxy, C 1 - C 4 alkoxyimino-d-C 4 alkyl, C 3 -C 6 trialkylsilyl, phenyl, benzyl or phenoxy; or phenyl, benzyl or phenoxy mono-, di- or trisubstituted by substituents independently selected from the group consisting of halogen, cyano, nitro, halogen, d-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 - C 6 cycloalkyl, d-C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, C 1 - C 4 alkoxy, CrC^aloalkoxy, d-C 4 alkylthio, Crdhaloalkylthio, d-C 4 alkylsulfinyl, C 1 -

C 4 alkylsulfonyl, Ci-C 4 alkylamino, C 2 -C 4 dialkylamino, C 3 -C 6 cycloalkylamino, Ci-C 6 alkyl-C 3 - C 6 cycloalkylamino, C 2 -C 4 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C^Cealkylaminocarbonyl, C 3 - C 6 dialkylaminocarbonyl, C 2 -C 6 alkoxycarbonyloxy, C 3 - C 6 dialkylaminocarbonyloxy and C 3 -C 6 trialkylsilyl; A 5 is a group -A-(X)p-(Y)q-B, wherein

A is a chemical bond, or is Ci-C 6 alkylene, C 2 -C 6 alkenylene, C 2 -C 6 alkynylene, or is a bivalent three- to ten-membered monocyclic or fused bicyclic ring system which can be partially saturated or fully saturated and can contain 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, it not being possible for each ring system to contain more than 2 oxygen atoms and more than 2 sulfur atoms; and it being possible for the three- to ten-membered ring system itself and also for the C 1 - C 6 alkylene, C 2 -C 6 alkenylene and C 2 -C 6 alkynylene groups to be mono-, di- or trisubstituted by substituents independently selected from the group consisting of halogen, cyano, nitro, hydroxy, d-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 5 -C 7 cycloalkenyl, C 5 - C 8 cycloalkynyl, CrC 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, C 5 - C 7 halocycloalkenyl, C 5 -C 8 halocycloalkynyl, d-C 4 alkoxy, Ci-C 4 haloalkoxy, Ci-C 4 alkylthio, Ci- C 4 haloalkylthio, C 1 -C 4 alkylsulf inyl , C 1 -C 4 alkylsulfonyl, d-C 4 alkylamino, C 2 -C 4 dialkylamino, C 3 -C 6 cycloalkylamino, d-C 6 alkyl-C 3 -C 6 cycloalkylamino, C 2 -C 4 alkylcarbonyl, C 2 - C 6 alkoxycarbonyl, C 2 -C 6 alkylaminocarbonyl, Cs-Cedialkylaminocarbonyl, C 2 - C 6 alkoxycarbonyloxy, Cs-Cedialkylaminocarbonyloxy, C 3 - C 6 trialkylsilyl, and a three- to ten-membered monocyclic or fused bicyclic ring system which can be aromatic, partially saturated or fully saturated and can contain 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, it not being possible for each ring system to contain more than 2 oxygen atoms and more than 2 sulfur atoms, and it being possible for the three- to ten-membered ring system itself to be mono-, di- or trisubstituted by substituents independently selected from the group consisting of halogen, cyano, nitro, hydroxy, CrC 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 5 -C 7 cycloalkenyl, C 5 - C 8 cycloalkynyl, CrC 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, C 5 - C 7 halocycloalkenyl, C 5 -C 8 halocycloalkynyl, C 1 -C 4 SIkOXy, d-C 4 haloalkoxy, CrC 4 alkylthio, C 1 - C 4 haloalkylthio, Ci-C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, d-dalkylamino, C 2 -C 4 dialkylamino, C 3 -C 6 cycloalkylamino, d-C 6 alkyl-C 3 -C 6 cycloalkylamino, C 2 -C 4 alkylcarbonyl, C 2 - C 6 alkoxycarbonyl, C 2 -C 6 alkylaminocarbonyl, Cs-Cedialkylaminocarbonyl, C 2 - C 6 alkoxycarbonyloxy, C 2 -C 6 alkylaminocarbonyloxy, drCedialkylaminocarbonyloxy, C 3 -

C 6 trialkylsilyl and phenyl, it being possible for the phenyl group in turn to be substituted by substituents independently selected from the group consisting of hydroxy, d-C 6 alkyl, d- C 6 haloalkyl, Ci-C 6 alkylthio, d-C 6 haloalkylthio, C 3 -C 6 alkenylthio, C 3 -C 6 haloalkenylthio, C 3 - C 6 alkynylthio, d-C 3 alkoxy-d-C 3 alkylthio, Crdalkylcarbonyl-d-Csalkylthio, C 2 - C 4 alkoxycarbonyl-CrC 3 alkylthio, CyBnO-C 1 -C 3 alkylthio, CrC 6 alkylsulfinyl, d-C 6 halo- alkylsulfinyl, d-C 6 alkylsulfonyl, d-C 6 haloalkylsulfonyl, aminosulfonyl, d^alkylamino- sulfonyl, N,N-di(Ci-C 2 alkyl)aminosulfonyl, di(d-C 4 alkyl)amino, halogen, cyano and nitro; and substituents at nitrogen atoms in the ring systems being other than halogen; X is oxygen, -N(H)- or -N(d-C 4 alkyl)-;

Y is d-C 6 alkylene, C 2 -C 6 alkenylene, C 2 -C 6 alkynylene, or a bivalent three- to ten-membered monocyclic or fused bicyclic ring system which can be partially saturated or fully saturated and can contain 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, it not being possible for each ring system to contain more than 2 oxygen atoms and more than 2 sulfur atoms; and it being possible for the three- to ten-membered ring system itself and also for the C 1 - C 6 alkylene, C 2 -C 6 alkenylene and C 2 -C 6 alkynylene groups to be mono-, di- or trisubstituted by substituents independently selected from the group consisting of halogen, cyano, nitro, hydroxy, d-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 5 -C 7 cycloalkenyl, C 5 - C 8 cycloalkynyl, d-C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, Cs-Cβhalocycloalkyl, C 5 - C 7 halocycloalkenyl, C 5 -C 8 halocycloalkynyl, d-C 4 alkoxy, d-C 4 haloalkoxy, d-C 4 alkylthio, C 1 - dhaloalkylthio, d-C 4 alkylsulfinyl, d-C 4 alkylsulfonyl, d-C 4 alkylamino, C 2 -C 4 dialkylamino, C 3 -C 6 cycloalkylamino, d-C 6 alkyl-C 3 -C 6 cycloalkylamino, C 2 -C 4 alkylcarbonyl, C 2 - C 6 alkoxycarbonyl, C 2 -C 6 alkylaminocarbonyl, Cs-Cedialkylaminocarbonyl, C 2 - C 6 alkoxycarbonyloxy, C^Cealkylaminocarbonyloxy, Cs-Cβdialkylaminocarbonyloxy, C 3 - C 6 trialkylsilyl and a three- to ten-membered monocyclic or fused bicyclic ring system which can be aromatic, partially saturated or fully saturated and can contain 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, it not being possible for each ring system to contain more than 2 oxygen atoms and more than 2 sulfur atoms, and it being possible for the three- to ten-membered ring system itself to be mono-, di- or trisubstituted by substituents independently selected from the group consisting of halogen, cyano, nitro, hydroxy, d-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloaikyl, C 5 - C 7 cycloalkenyl, C 5 -C 8 cycloalkynyl, d-C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 - C 6 halocycloalkyl, C 5 -C 7 halocycloalkenyl, C 5 -C 8 halocycloalkynyl, d-C 4 alkoxy, C 1 - Cjhaloalkoxy, d-C 4 alkylthio, d-C 4 haloalkylthio, d-C 4 alkylsulfinyl, d-C 4 alkylsulfonyl, C 1 -

C 4 alkylamino, C 2 -C 4 dialkylamino, C 3 -C 6 cycloalkylamino, d-C 6 alkyl-C 3 -C 6 cycloalkylamino, C 2 - C 4 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, drCealkylaminocarbonyl, Cs-Cedialkylaminocarbonyl, C 2 -C 6 alkoxycarbonyloxy, CrCealkylaminocarbonyloxy, Cs-Cβdialkylaminocarbonyloxy, C 3 - C 6 trialkylsilyl and phenyl, it being possible for the phenyl group in turn to be substituted by substituents independently selected from the group consisting of hydroxy, Ci-C 6 alkyl, Ci- C 6 haloalkyl, d-C 6 alkylthio, d-C 6 haloalkylthio, C 3 -C 6 alkenylthio, C 3 -C 6 haloalkenylthio, C 3 - C 6 alkynylthio, d-Csalkoxy-d-Csalkylthio, C 2 -C 4 alkylcarbonyl-Ci-C 3 alkylthio, C 2 - C 4 alkoxycarbonyl-CrC 3 alkylthio, cyano-Ci-Csalkylthio, Ci-C 6 alkylsulfinyl, d-C 6 halo- alkylsulfinyl, Ci-C 6 alkylsulfonyl, C r C 6 haloalkylsulfonyl, aminosulfonyl, d-C 2 alkylamino- sulfonyl, N,N-di(Ci-C 2 alkyl)aminosulfonyl, di(Ci-C 4 alkyl)amino, halogen, cyano and nitro; and substituents at nitrogen atoms in the ring systems being other than halogen; p is 0 or 1 ; q is O or 1 ;

B is a three- to four-membered ring system which is fully or partially saturated and can contain a hetero atom selected from the group consisting of nitrogen, oxygen and sulfur, and it being possible for the three- to four-membered ring system itself to be mono-, di- or trisubstituted by substituents independently selected from the group consisting of halogen, cyano, nitro, hydroxy, d-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 5 - C 7 cycloalkenyl, C 5 -C 8 cycloalkynyl, C r C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 - C 6 halocycloalkyl, Cs-dhalocycloalkenyl, C 5 -C 8 halocycloalkynyl, d-C 4 alkoxy, C 1 - C 4 haloalkoxy, d-C 4 alkylthio, CrC 4 haloalkylthio, C 1 -C 4 alkylsulfinyl, Ci-C 4 alkylsulfonyl, C 1 - C 4 alkylamino, C 2 -C 4 dialkylamino, C 3 -C 6 cycloalkylamino, d-C 6 alkyl-C 3 -C 6 cycloalkylamino, C 2 - dalkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminocarbonyl, Cs-Cεdialkylaminocarbonyl, CrCβalkoxycarbonyloxy, C 2 -C 6 alkylaminocarbonyloxy, Cs-Cedialkylaminocarbonyloxy, C 3 - C 6 trialkylsilyl and a three- to ten-membered monocyclic or fused bicyclic ring system which can be aromatic, partially saturated or fully saturated and can contain 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, it not being possible for each ring system to contain more than 2 oxygen atoms and more than 2 sulfur atoms, and it being possible for the three- to ten-membered ring system itself to be mono-, di- or trisubstituted by substituents independently selected from the group consisting of halogen, cyano, nitro, hydroxy, d-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 5 - C 7 cycloalkenyl, C 5 -C 8 cycloalkynyl, Ci- C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 - C 6 halocycloalkyl, C 5 -C 7 halocycloalkenyl, C 5 -C 8 halocycloalkynyl, d-C 4 alkoxy, C r dhaloalkoxy, Ci-C 4 alkylthio, C r C 4 haloalkylthio, C 1 -C 4 alkylsulfinyl, d-C 4 alkylsulfonyl, C r

C 4 alkylamino, C 2 -C 4 dialkylamino, C 3 -C 6 cycloalkylamino, d-C 6 alkyl-C 3 -C 6 cycloalkylamino, C 2 - C 4 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminocarbonyl, Cs-Cedialkylaminocarbonyl, C 2 -C 6 alkoxycarbonyloxy, C 2 -C 6 alkylaminocarbonyloxy, Cs-Cedialkylaminocarbonyloxy, C 3 - C 6 trialkylsilyl and phenyl, it being possible for the phenyl group in turn to be substituted by substituents independently selected from the group consisting of hydroxy, CrC 6 alkyl, C 1 - Cehaloalkyl.d-Cealkylthio, d-C 6 haloalkylthio, C 3 -C 6 alkenylthio, C 3 -C 6 haloalkenylthio, C 3 - C 6 alkynylthio, d-C 3 alkoxy-d-C 3 alkylthio, C 2 -C 4 alkylcarbonyl-Ci-C 3 alkylthio, C 2 - C 4 alkoxycarbonyl-Ci-C 3 alkylthio, cyano-d-C 3 alkylthio, d-C 6 alkylsulfinyl, d-C 6 halo- alkylsulfinyl, CrC 6 alkylsulfonyl, Ci-C 6 haloalkylsulfonyl, aminosulfonyl, d-C 2 alkylamino- sulfonyl, N,N-di(Ci-C 2 alkyl)aminosulfonyl, di(CrC 4 alkyl)amino, halogen, cyano and nitro; and substituents at nitrogen atoms in the ring systems being other than halogen; or B is hydrogen, d-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl or C 5 -C 6 cycloalkyl; or is d-C 6 alkyl, C 2 - C 6 alkenyl, C 2 -C 6 alkynyl and C 5 -C 6 cycloalkyl substituted with one, two or three substituents independently selected from the group consisting of halogen, cyano, nitro, hydroxy, C 1 - C 4 alkyl, d-C 4 alkoxy, C 1 -C 4 haloalkoxy, d-C 4 alkylthio, Ci-C 4 alkylsulfinyl, d-C 4 alkylsulfonyl, d-C 4 alkylsulfoximino, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 trialkylsilyl, benzyl, phenoxy and a three- to ten-membered, monocyclic or fused bicyclic ring system which may be aromatic, partially saturated or fully saturated, wherein the six-membered aromatic ring system contains at least one heteroatom selected from the group consisting of oxygen, nitro and sulfur; it being possible for said benzyl, phenoxy and three- to ten-membered, monocyclic or fused bicyclic ring system in turn to be substituted by one to three substituents independently selected from the group consisting of d-C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 6 cycloalkyl, d-C 4 haloalkyl, C 2 -C 4 haloalkenyl, C 2 -C 4 haloalkynyl, C 3 -C 6 halocycloalkyl, halogen, cyano, nitro, d-C 4 alkoxy, d-C 4 haloalkoxy, d-C 4 alkylthio, d-C 4 alkylsulfinyl, C 1 - C 4 alkylsulfonyl, d-C 4 alkylsulfoximino, d-C 4 alkylamino, C 2 -C 6 dialkylamino, C 3 - Cecycloalkylamino, d-dalkyl-Cs-Cecycloalkylamino, C 2 -C 4 alkylcarbonyl, C 2 - C 6 alkoxycarbonyl, C 2 -C 6 alkylaminocarbonyl, C 2 -C 8 dialkylaminocarbonyl and C 2 -C 6 trialkylsilyl; it being possible for said three- to ten-membered, monocyclic or fused bicyclic ring system to be spiro-bonded to the C 3 -C 6 cycloalkyl group; or B is d-C 4 alkoxy, d-C 4 alkylamino, C 2 -C 8 dialkylamino, C 3 -C 6 cycloalkylamino, C 2 - C 6 alkoxycarbonyl or C 2 -C 6 alkylcarbonyl; or A 5 is a group

Y^ is a CrC 6 alkylene, C 2 -C 6 alkenylene or C 3 -C 6 alkynylene chain which may be mono-, di- or trisubstituted by R 2 o, where the unsaturated bonds of the chain are not attached directly to the sulfur atom; or is C 3 -C 6 cycloalkylene, which may be mono-, di- or trisubstituted by R 2 i; or Yia and Y 2 form together with the chain -G-Y 1 b-S(=O=N-Z)- a ring system of at least 3 members; wherein Y^ and Y 2 together represent the group

-CH 2 -; -CH 2 -CH 2 -; -CH 2 -CH 2 -CH 2 ; -CH 2 -CH=CH-; -CH=CH-CH 2 -; -CH 2 -Ge-CH 2 -;

-CH 2 -CH 2 -GiO-CH 2 -; -CH 2 -Ca 7 -CH 2 -CH 2 - or -CH 2 -CH 2 -Gi I -CH 2 -CH 2 -;

G 6 is oxygen, N(-Z 7 ) or sulfur;

G 7 is oxygen, N(-Z 8 ) or sulfur;

G 10 is oxygen, N(-Zn) or sulfur; di is oxygen, N(-Z 12 ) or sulfur;

R 20 and R 2 i independently of one another are halogen, nitro, cyano, hydroxy, d-C 6 alkyl,

C r C 6 haloalkyl, Ci-C 6 alkylthio, Ci-C 6 alkylsulfinyl, d-C 6 alkylsulfonyl, d-Cehaloalkylthio,

CrCehaloalkylsulfinyl, d-C 6 haloalkylsulfonyl, d-Cealkoxycarbonyl, d-C 6 alkylcarbonyl,

CrCealkoxy-CrCealkyl, d-C 6 alkoxy-Ci-C 6 alkyl, d-C 6 alkoxy, d-C 6 halo-alkoxy, benzyl or phenyl, where phenyl and benzyl for their part may be mono-, di- or trisubstituted by substituents independently selected from the group consisting of d-C 6 alkyl, d-C 6 haloalkyl, d-C 6 alkoxy, d-C 6 haloalkoxy, halogen, cyano, hydroxyl and nitro;

Y^ is a direct bond or is a d-C 6 alkylene, C 2 -C 6 alkenylene or C 3 -C 6 alkynylene chain which may be mono-, di- or trisubstituted by R 22 , where the unsaturated bonds of the chain are not attached directly to the sulfur atom; or is C 3 -C 6 cycloalkylene, which may be mono-, di- or trisubstituted by R 23 , or is 1 ,2-, 1 ,3- or 1 ,4-phenylene;

R 22 and R 23 independently of one another are halogen, nitro, cyano, hydroxy, d-C 6 alkyl,

Ci-C 6 haloalkyl, d-C 6 alkylthio, CrC 6 alkylsulfinyl, d-C 6 alkylsulfonyl, d-C 6 haloalkylthio,

Ci-C 6 haloalkylsulfinyl, d-C 6 haloalkylsulfonyl, d-C 6 alkoxycarbonyl, d-C 6 alkylcarbonyl,

Ci-Cealkoxy-d-Cealkyl, d-C 6 alkoxy-Ci-C 6 alkyl, d-C 6 alkoxy, d-C 6 halo-alkoxy, benzyl or phenyl, where phenyl and benzyl for their part may be mono-, di- or trisubstituted by substituents independently selected from the group consisting of d-C 6 alkyl, d-C 6 haloalkyl, d-Cβalkoxy, d-C 6 haloalkoxy, halogen, cyano, hydroxyl and nitro;

Y 2 is a C r C 6 alkylene, C 2 -C 6 alkenylene or C 3 -C 6 alkynylene chain which may be mono-, di- or trisubstituted by R 24 , where the unsaturated bonds of the chain are not attached directly to the sulfur atom; or is C 3 -C 6 cycloalkylene, which may be mono-, di- or trisubstituted by R 25 ;

R 24 and R 25 independently of one another are halogen, nitro, cyano, hydroxy, d-C 6 alkyl,

Ci-C 6 haloalkyl, Ci-C 6 alkylthio, Ci-C 6 alkylsulfinyl, d-C 6 alkylsulfonyl, Ci-C 6 haloalkylthio, d-C 6 haloalkylsulfinyl, d-C 6 haloalkylsulfonyl, d-C 6 alkoxycarbonyl, d-C 6 alkylcarbonyl,

CrCealkoxy-d-Cealkyl, d-C 6 alkoxy-d-C 6 alkyl, d-C 6 alkoxy, d-C 6 halo-alkoxy, benzyl or phenyl, where phenyl and benzyl for their part may be mono-, di- or trisubstituted by substituents independently selected from the group consisting of d-C 6 alkyl, d-C 6 haloalkyl, d-C 6 alkoxy, d-C 6 haloalkoxy, halogen, cyano, hydroxyl and nitro;

Y 3 is hydrogen, halogen, d-C 6 haloalkyl or d-C 6 alkyl;

G is a direct bond, oxygen, NC-Z 1 ), sulfur or the group G r C(=G 2 )-G 3 ;

Gi is a direct bond, oxygen, N(-Z 2 ) or sulfur;

G 2 is oxygen, N(-Z 3 ) or sulfur;

G 3 is a direct bond, oxygen, N^Z 4 ) or sulfur;

Z, Z 1 , Z 2 , Z 3 and Z 4 independently of one another are hydrogen, d-C 6 alkyl, d-C 6 haloalkyl,

C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, d-C 6 alkylthio, d-C 6 haloalkylthio or d-C 6 alkoxy-d-C 6 alkyl; or d-C 6 alkyl, d-C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, d-C 6 alkylthio, d-C 6 haloalkylthio or d-C 6 alkoxy-d-C 6 alkyl substituted by d-C 6 alkyl, d-C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, d-C 6 alkoxy, cyano, nitro or d-C 6 haloalkoxy; or Z, Z 1 , Z 2 , Z 3 and Z 4 independently of one another are -C(O)R 34 , -C(O)O-R 35 , -CONR 36 R 29 ,

-SO 2 R 30 or -P(O)(OR 31 )(OR 32 )-OR 33 ;

R 34 is d-C 6 alkyl, d-C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, d-C 6 alkylthio, d-C 6 haloalkylthio, d-C 6 alkoxycarbonyl, d-C 6 alkylcarbonyl or d-Cealkoxy-d-Cealkyl; or d-C 6 alkyl, d-C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, d-C 6 alkylthio,

C r C 6 haloalkylthio, d-C 6 alkoxycarbonyl, d-C 6 alkylcarbonyl or d-Cealkoxy-d-Cealkyl substituted by substituents independently selected from the group consisting of d-C 6 alkyl, d-C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, CrC 6 alkoxy and d-C 6 haloalkoxy; and

R 29 , R 30 , R 31 , R 32 , R 33 , R 35 and R 36 independently of one another are d-C 6 alkyl, d-C 6 haloalkyl, C 3 -C 6 cycloalkyl or C 3 -C 6 halocycloalkyl; or d-C 6 alkyl, d-C 6 haloalkyl,

C 3 -C 6 cycloalkyl or C 3 -C 6 halocycloalkyl substituted by d-C 6 alkyl, d-C 6 haloalkyl,

C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, d-C 6 alkoxy, d-C 6 haloalkoxy;

or A 5 is a group wherein

R 37 and R 38 , which may be the same or different, represents hydrogen, COOH, halogen, nitro, cyano, hydroxy, d-C 6 alkyl, Ci-C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 2 -

C 6 haloalkenyl, C 2 -C 6 haloalkynyl, CrC 6 alkylthio, d-C 6 alkylsulfinyl, d-C 6 alkylsulfonyl,

CrC 6 haloalkylthio, Ci-C 6 haloalkylsulfinyl, d-C 6 haloalkylsulfonyl, d-C 6 alkoxycarbonyl, d-C 6 alkylcarbonyl, Cs-Cealkylaminocarbonyl, Cs-Cedialkylaminocarbonyl,

Ci-C 6 alkoxy-Ci-C 6 alkyl, Ci-Cehaloalkoxy-Ci-Cealkyl, d-C 6 alkoxy, d-C 6 haloalkoxy, d-

C 6 alkylamino, C 2 -C 6 dialkylamino, C 3 -C 6 trialkylsilyl, benzyl or phenyl; where phenyl and benzyl for their part may be mono- di- or trisubstituted by d-C 6 alkyl, d-C 6 haloalkyl, d-C 6 alkoxy, d-C 6 haloalkoxy, halogen, cyano, hydroxyl or nitro; k is O, 1 , 2, 3 or 4;

A 8 is oxygen, sulfur, SO, SO 2 , S(O) U =N-R, C=N-OR 40 , N-R 0 , C=O or P(X) 1 -R 39 ;

R 39 is hydrogen, d-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, d-C 6 haloalkyl, d-C 6 alkoxy, hydroxy, d-C 6 cycloalkyl, d-Cβcycloalkyl-d-Cealkyl, benzyl or phenyl; where phenyl and benzyl for their part may be mono- di- or trisubstituted by d-C 6 alkyl, d-C 6 haloalkyl, halogen, cyano or nitro; or R 33 is O Na + , O Li + or O K + ;

R 40 is hydrogen, d-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, d-C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -

C 6 haloalkynyl, Ci-C 6 alkoxy-d-C 6 alkyl, d-C 6 haloalkoxy-d-C 6 alkyl or benzyl;

R is hydrogen, d-C 6 alkyl, d-C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, d-C 6 alkylthio, d-C 6 haloalkylthio, Ci-C 6 alkoxy-Ci-C 6 alkyl or d-C 6 haloalkoxy-C r C 6 alkyl; or

R is d-C 6 alkyl, d-C 6 haloalkyl, C 3 -C 6 cycloalkyl, Cs-Cehalocycloalkyl, CrC 6 alkylthio,

CrC 6 haloalkylthio, d-C 6 alkoxy-Ci-C 6 alkyl or Ci-Cehaloalkoxy-d-C 6 alkyl substituted by

Ci-C 6 alkyl, d-C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, Ci-C 6 alkoxy, or

Ci-C 6 haloalkoxy; or R is cyano, nitro, -C(O)R 4I , -C(O)OR 42 , -CONR 43 R 44 , -SO 2 R 45 or -

P(O)(OR 46 )(OR 47 );

R 0 is hydrogen, d-C 6 alkyl, d-C 6 haloalkyl, C 3 -C 6 cycloalkyl, Cs-Cehalocycloalkyl, d-C 6 alkylthio, d-C 6 haloalkylthio, d-C 6 alkoxy-d-C 6 alkyl or Ci-C 6 haloalkoxy-d-C 6 alkyl; or

R 0 is d-C 6 alkyl, Ci-C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, d-C 6 alkylthio, d-C 6 haloalkylthio, Ci -C 6 BIkOXy-C 1 -C 6 alkyl or Ci-C 6 haloalkoxy-d-C 6 alkyl substituted by

Ci-C 6 alkyl, Ci-C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, Ci-C 6 alkoxy, or

Ci-C 6 haloalkoxy; or R 0 is cyano, nitro, -C(O)R 04I , -C(O)OR 042 , -CONR 043 R 044 , -SO 2 R 045 or

-P(O)(OR 046 (OR 047 );

each of R 4 i and R 04I , which may be the same or different, represents hydrogen, Ci-C- 6 alkyl, Ci-C 6 haloalkyl, Ci-C 6 cycloalkyl, Ci-C 6 halocycloalkyl, CrC 6 alkylthio, d-C 6 haloalkylthio, Ci-C 6 alkoxycarbonyl, d-C 6 alkylcarbonyl or Ci-C 6 alkoxy-Ci-C 6 alkyl; or d-Cealkyl, CrCehaloalkyl, d-C 6 cycloalkyl, d-Cehalocycloalkyl, d-C 6 alkylthio, d-C 6 haloalkylthio, Ci-C 6 alkoxycarbonyl, Ci-C 6 alkylcarbonyl or d-C 6 alkoxy-d-C 6 alkyl substituted by d-C 6 alkyl, CrCehaloalkyl, d-C 6 cycloalkyl, d-C 6 halocycloalkyl, d-C 6 alkoxy, or d-C 6 haloalkoxy; each of R 42 , R43, R 44 , R45, R 4 6, R47, Ro4i> Ro42> Ro43> Ro 44 , R045 R046 and R 047 which may be the same or different, represents d-C 6 alkyl, d-C 6 haloalkyl, d-C 6 cycloalkyl or Ci-C 6 halocycloalkyl; or d-C 6 alkyl, d-C 6 haloalkyl, d-C 6 cycloalkyl or d-Cβhalocycloalkyl substituted by d-C 6 alkyl, d-Cβhaloalkyl, d-C 6 cycloalkyl, d-Cβhalocycloalkyl, d-C 6 alkoxy or d-C 6 haloalkoxy; X is oxygen or sulfur; u is 0 or 1 ; and t is O or 1 ;

A 6 is hydrogen, d-C 6 alkyl, C 3 -C 6 cycloalkyl, d-C 6 haloalkyl, cyano, d-C 4 alkoxy, C 1 - dhaloalkoxy, d-C 4 alkylthio, Ci-C 4 haloalkylthio, d-C 4 alkylsulfinyl, d-C 4 alkylsulfonyl, C 1 - C 4 haloalkylsulfinyl or d-C 4 haloalkylsulfonyl; and

A 7 is d-C 6 alkyl, C 3 -C 6 cycloalkyl, d-C 6 haloalkyl, halogen, cyano, d-C 4 alkoxy, d- C 4 haloalkoxy, d-C 4 alkylthio, d-C 4 haloalkylthio, CrC 4 alkylsulfinyl, Ci-C 4 alkylsulfonyl, C 1 - C 4 haloalkylsulfinyl or d-C 4 haloalkylsulfonyl; which process comprises a) reacting a compound of formula V

wherein Ai 1 A 2 , A 3 , A 4 and A 5 are as defined under f ormula I above, with a compound of formula Vl

wherein hal is halogen and R 1 is d-C 6 alkyl in the presence of a base to a compound of formula III

wherein A 1 , A 2 , A 3 , A 4 and A 5 are as defined under formula I above and R 1 is CrCealkyl,

b) treating a compound of formula Il

HN 'N (">.

wherein A 6 and A 7 are as defined under formula I above, with said compound of formula

wherein A 1 , A 2 , A 3 , A 4 and A 5 are as defined under formula I above and R 1 is d-Cealkyl, in the presence of a base to form a compound of formula IV

wherein A 1 , A 2 , A 3 , A 4 , A 5 A 6 and A 7 are as defined under formula I above and c) converting said compound of formula IV in the presence of an acid or a base to the compound of formula I.

The alkyl groups occurring in the definitions of the substituents can be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso- butyl, tert-butyl, pentyl and hexyl and their branched isomers. Alkoxy, alkenyl and alkynyl radicals are derived from the alkyl radicals mentioned. The alkenyl and alkynyl groups can be mono- or polyunsaturated.

Halogen is generally fluorine, chlorine, bromine or iodine. This also applies, correspondingly, to halogen in combination with other meanings, such as haloalkyl or halophenyl.

Haloalkyl groups preferably have a chain length of from 1 to 6 carbon atoms. Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1 ,1 -difluoro- 2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl and dichlorofluoromethyl.

Suitable haloalkenyl groups are alkenyl groups which are mono- or polysubstituted by halogen, halogen being fluorine, chlorine, bromine and iodine and in particular fluorine and chlorine, for example 2,2-difluoro-i -methylvinyl, 3-fluoropropenyl, 3-chloropropenyl, 3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl and 4,4,4-trifluorobut-2-en- 1 -yl. Among the C 3 -C 2 oalkenyl groups which are mono-, di- or trisubstituted by halogen, preference is given to those having a chain length of from 3 to 5 carbon atoms.

Suitable haloalkynyl groups are, for example, alkynyl groups which are mono- or polysubstituted by halogen, halogen being bromine, iodine and in particular fluorine and chlorine, for example 3-fluoropropynyl, 3-chloropropynyl, 3-bromopropynyl, 3,3,3-trifluoro- propynyl and 4,4,4-trifluorobut-2-yn-1 -yl. Among the alkynyl groups which are mono- or polysubstituted by halogen, preference is given to those having a chain length of from 3 to 5 carbon atoms.

Alkoxy groups preferably have a preferred chain length of from 1 to 6 carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, i-propoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy and also the isomeric pentyloxy and hexyloxy radicals; preferably methoxy and ethoxy.

Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl or tert- butoxycarbonyl; preferably methoxycarbonyl or ethoxycarbonyl. Haloalkoxy groups preferably have a chain length of from 1 to 6 carbon atoms. Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1 ,1 ,2,2- tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy and 2,2,2- trichloroethoxy; preferably difluoromethoxy, 2-chloroethoxy and trifluoromethoxy. Alkylthio groups preferably have a chain length of from 1 to 6 carbon atoms. Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert- butylthio, preferably methylthio and ethylthio. Alkylsulfinyl is, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl; preferably methylsulfinyl and ethylsulfinyl.

Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl; preferably methylsulfonyl or ethylsulfonyl.

Alkylamino is, for example, methylamino, ethylamino, n-propylamino, isopropylamino or the isomeric butylamines. Dialkylamino is, for example, dimethylamino, methylethylamino, diethylamino, n-propylmethylamino, dibutylamino and diisopropylamino. Preference is given to alkylamino groups having a chain length of from 1 to 4 carbon atoms.

Alkoxyalkyl groups preferably have a chain length of 1 to 6 carbon atoms.

Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n- propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.

Alkylthioalkyl groups preferably have from 1 to 6 carbon atoms. Alkylthioalkyl is, for example, methylthiomethyl, methylthioethyl, ethylthiomethyl, ethylthioethyl, n-propylthiomethyl, n- propylthioethyl, isopropylthiomethyl, isopropylthioethyl, butylthiomethyl, butylthioethyl or butylthiobutyl.

The cycloalkyl groups preferably have from 3 to 6 ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Phenyl, also as part of a substituent such as phenoxy, benzyl, benzyloxy, benzoyl, phenylthio, phenylalkyl, phenoxyalkyl, may be substituted. In this case, the substituents can be in ortho, meta and/or para position. The preferred substituent positions are the ortho and para positions to the ring attachment point.

According to the present invention, a three- to ten-membered, monocyclic or fused bicyclic ring system which may be partially saturated or fully saturated is, depending of the number of ring members, for example, selected from the group consisting of

cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, where said cycloalkylgroups for their part may be preferably unsubstituted or substituted by d-C^alky! or halogen, and

-< J ° o _<$

and wherein each R 26 is methyl, each R 27 and each R 28 are independently hydrogen, d-C 3 alkyl, Ci-C 3 alkoxy, Ci-C 3 alkylthio or trifluoromethyl, X 4 is oxygen or sulfur and r = 1 , 2, 3 or 4.

CH

Where no free valency is indicated in those definitions, for example as in ° , the linkage

site is located at the carbon atom labelled "CH" or in a case such as, for example, at the bonding site indicated at the bottom left. The second valence for the bivalent ring system of substituent A or Y can be located at any suitable position of the ring.

According to the present invention, a three- to ten-membered monocyclic or fused bicyclic ring system which may be aromatic, partially saturated or fully saturated is, depending of the number of ring members, for example, selected from the group consisting of

cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, where said cycloalkylgroups for their part may be preferably unsubstituted or substituted by Ci-C 6 alkyl or halogen, or is naphthyl or the following heterocyclic groups: pyrrolyl; pyridyl; pyrazolyl; pyrimidyl; pyrazinyl; imidazolyl; thiadiazolyl; quinazolinyl; furyl; oxadiazolyl; indolizinyl; pyranyl; isobenzofuranyl; thienyl; naphthyridinyl; (1 -methyl-1 H-pyrazol-3-yl)-; (1 -ethyl-1 H-pyrazol-3-yl)-; (1 -propyl-1 H-pyrazol- 3-yl)-; (1 H-pyrazol-3-yl)-; (1 ,5-dimethyl-1 H-pyrazol-3-yl)-; (4-chloro-1 -methyl-1 H-pyrazol-3- yl)-; (1 H-pyrazol-1 -yl)-; (3-methyl-1 H-pyrazol-1-yl)-; (3,5-dimethyl-1 H-pyrazol-1 -yl)-; (3- isoxazolyl)-; (5-methyl-3-isoxazolyl)-; (3-methyl-5-isoxazolyl)-; (5-isoxazolyl)-; (1 H-pyrrol-2- yl)-; (1 -methyl-1 H-pyrrol-2-yl)-; (1 H-pyrrol-1 -yl)-; (1 -methyl-1 H-pyrrol-3-yl)-; (2-furanyl)-; (5- methyl-2-furanyl)-; (3-furanyl)-; (5-methyl-2-thienyl)-; (2-thienyl)-; (3-thienyl)-; (1 -methyl-1 H- imidazol-2-yl)-; (1 H-imidazol-2-yl)-; (1 -methyl-1 H- imidazol-4-yl)-; (1 - methyl-1 H-imidazol-5- yl)-; (4-methyl-2-oxazolyl)-; (5-methyl-2-oxazolyl)-; (2-oxazolyl)-; (2-methyl-5-oxazolyl)-; (2- methyl-4-oxazolyl)-; (4-methyl-2-thiazolyl)-; (5-methyl-2-thiazolyl)-; (2-thiazolyl)-; (2-methyl-5- thiazolyl)-; (2-methyl-4-thiazolyl)-; (3-methyl-4-isothiazolyl)-; (3-methyl-5-isothiazolyl)-; (5- methyl-3-isothiazolyl)-; (1 -methyl-1 H-1 ,2,3-triazol-4-yl)-; (2-methyl-2H-1 ,2,3-triazol-4-yl)-; (4- methyl-2H-1 ,2,3-triazol-2-yl)-; (1 -methyl-1 H-1 ,2,4-triazol-3-yl)-; (1 ,5-dimethyl-1 H-1 ,2,4-triazol- 3-yl)-; (3-methyl-1 H-1 ,2,4-triazol-i -yl)-; (5-methyl-1 H-1 ,2,4-triazol-i -yl)-; (4,5-dimethyl-4H- 1 ,2,4-triazol-3-yl)-; (4-methyl-4H-1 ,2,4-triazol-3-yl)-; (4H-1 ,2,4-triazol-4-yl)-; (5-methyl-1 ,2,3- oxadiazol-4-yl)-; (1 ,2,3-oxadiazol-4-yl)-; (3-methyl-1 ,2,4-oxadiazol-5-yl)-; (5-methyl-1 ,2,4- oxadiazol-3-yl)-; (4-methyl-3-furazanyl)-; (3-furazanyl)-; (5-methyl-1 ,2,4-oxadiazol-2-yl)-; (5- methyl-1 ,2,3-thiadiazol-4-yl)-; (1 ,2,3-thiadiazol-4-yl)-; (3-methyl-1 ,2,4-thiadiazol-5-yl)-; (5- methyl-1 ,2,4-thiadiazol-3-yl)-; (4-methyl-1 ,2,5-thiadiazol-3-yl)-; (5-methyl-1 ,3,4-thiadiazol-2- yl)-; (1 -methyl-1 H-tetrazol-5-yl)-; (1 H-tetrazol-5-yl)-; (5-methyl-1 H-tetrazol-1 -yl)-; (2-methyl- 2H-tetrazol-5-yl)-; (2-ethyl-2H-tetrazol-5-yl)-; (5-methyl-2H-tetrazol-2-yl)-; (2H-tetrazol-2-yl)-; (2-pyridyl)-; (6-methyl-2-pyridyl)-; (4-pyridyl)-; (3-pyridyl)-; (6-methyl-3-pyridazinyl)-; (5-

methyl-3-pyridazinyl)-; (3-pyridazinyl)-; (4,6-dimethyl-2-pyrimidinyl)-; (4-methyl-2-pyrimidinyl)- ; (2-pyrimidinyl)-; (2-methyl-4-pyrimidinyl)-; (2-chloro-4-pyrimidinyl)-; (2,6-dimethyl-4- pyrimidinyl)-; (4-pyrimidinyl)-; (2-methyl-5-pyrimidinyl)-; (6-methyl-2-pyrazinyl)-; (2-pyrazinyl)-; (4,6-dimethyl-i ,3,5-triazin-2-yl)-; (4,6-dichloro-1 ,3,5-triazin-2-yl)-; (1 ,3,5-triazin-2-yl)-; (4- methyl-1 ,3,5-triazin-2-yl)-; (3-methyl-1 ,2,4-triazin-5-yl)-; (3-methyl-1 ,2,4-triazin-6-yl)-;

wherein each R 26 is methyl, each R 27 and each R 28 are independently hydrogen, d-C 3 alkyl, CrCaalkoxy, d-C 3 alkylthio or trifluoromethyl, X 4 is oxygen or sulfur and r is 1 , 2, 3 or 4.

Examples for a three- to ten-membered, monocyclic or fused bicyclic ring system which is

spiro-bonded to the C 3 -C 6 cycloalkyl group of the substituent R 20 are

and

CH

Where no free valency is indicated in those definitions, for example as in ° , the linkage

site is located at the carbon atom labelled "CH" or in a case such as, for example, at the bonding site indicated at the bottom left.

Examples for B as a optionally substituted three- to four-membered ring system which is fully or partially saturated and can contain a hetero atom selected from the group consisting of nitrogen, oxygen and sulfur, are cyclopropyl, methyl-cyclopropyl, cyclopropenyl, cyclobutyl,

cyclobutenyl, -< J ° , - o or _<$

Compounds of formula I that are highly suitable for preparation using the process according to the invention are those wherein

A 1 is Ci-C 4 alkyl, halogen, especially methyl;

A 2 is hydrogen;

A 3 is cyano, Ci-C 4 alkyl or halogen, especially methyl or chloro;

A 4 is hydrogen;

A 5 is a group -A-(X)p-(Y)q-B, wherein

A is a chemical bond or is d-C 6 alkylene which may be substituted by C 3 -C 6 cycloalkyl, C 2 -

C 6 alkenyl, cyano, Ci-C 4 alkylthio, CrC 4 alkylsulfonyl, Ci-C 4 alkoxy, halogen or d-C 6 haloalkyl; or A is Cs-Cβcycloalkylene. Preferably A is CrC 6 alkylene or cyclopropylene, most preferably methylene or cyclopropylene. p and/or q is 0;

X is preferably oxygen, NH; NMe or NEt.

Y is preferably C 1 -C 4 alkylene, C 2 -C 6 alkenylene or C 3 -C 6 alkinylene or, Ci-C 4 alkylene, C 2 -

C 6 alkenylene or C 3 -C 6 alkinylene substituted by halogen, C 3 -C 6 cycloalkyl, Ci-C 4 alkylsulfonyl or d-C^alkoxy.

B is Ci-C 6 alkyl, cyclopropyl or cyclobutyl, preferably cyclopropyl or methyl.

A 6 is Ci-C 4 halogenalkyl, especially trifluoromethyl; and

A 7 is chloro.

Further compounds of formula I that are highly suitable for preparation using the process according to the invention are those wherein

A 1 is hydrogen or d-C 4 alkyl, especially hydrogen or methyl;

A 2 is hydrogen;

A 3 is hydrogen;

A 4 is hydrogen;

A 5 is CrC 4 alkyl or is C 3 -C 4 cycloalkyl which can be substituted by C 3 -C 4 cycloalkyl, especially

A 5 is methyl or cyclopropyl substituted by cyclopropyl;

A 6 is CVC 4 halogenalkyl, especially trifluoromethyl; and

A 7 is chloro.

Using the process according to the invention it is possible, especially advantageously, to prepare the bisamide derivatives described in tables P1 , P2 and tables 1 to 91 of WO2005/085234 (provided that the substituent which corresponds to A 6 of formula I of the invention is not halogen) and further the anthranilamides described in the table P and the tables 1 to 57 of WO2006/061200 (provided that the substituent which corresponds to A 6 of formula I of the invention is not halogen) and further the anthranilamide derivatives described in the following tables:

Table P1 : Compounds of formula Ia:

Table P2: Compounds of formula Ib:

In the following tables, Me means the methyl group. Et means the ethyl group. tBu is tert.- butyl. If no definition for substituent X is given, then p is 0, if X is a substituent, then p is 1. If no definition for substituent Y is given, then q is 0, if Y is a substituent, then q is 1.

Table P3: Compounds of formula Ic:

The following compounds can also be advantageously prepared according to the process of the present invention:

Me means the methyl group. Et means the ethyl group. If no definition for substituent X is given, then p is 0, if X is a substituent, then p is 1. If no definition for substituent A is given, then q is 0, if A is a substituent, then q is 1. The group C(CH 2 CH 2 ) for the substituent Y means cyclopropyl with two free valences:

Table P4: Compounds of formula Id:

Table P5: Compounds of formula Ie:

Preferred bases for the treatment of a compound of formula Il with a compound of formula III are selected from alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal dialkylamides or alkali metal or alkaline earth metal alkylsilylamides, alkylamines, alkylenediamines, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines. Examples which may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N- dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N- methylmorpholine, benzyltrimethylammonium hydroxide, 1 ,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and 1 ,5-diazabicyclo[4.3.0]non-5-ene (DBN).

Especially preferred bases are selected from n-Butyl-Li, sec-Butyl-Li, tert-Butyl-Li, LiN(Si(CH 3 ) 3 ) 2> KN(Si(CH 3 ) 3 ) 2 , NaN(Si(CH 3 ) 3 ) 2 , NaH, KH 1 tert-Butyl-ONa, tert-ButylOK, 1 ,8- diazabicyclo[5.4.0]undec-7-ene (DBU) and 1 ,5-diazabicyclo[4.3.0]non-5-ene (DBN).

Preferred acids for the conversion of the formula IV to the formula I are mineral acids, especially preferred are HCI, H 2 SO 4 , HNO 3 , CF 3 COOH or CF 2 HCOOH. Preferred bases are selected from alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal dialkylamides or alkali metal or alkaline earth metal alkylsilylamides, alkylamines, alkylenediamines, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines. Examples which may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide, 1.δ-diazabicyclotδAOlundec^-ene (DBU) and 1 ,5- diazabicyclo[4.3.0]non-5-ene (DBN).

Suitable bases for the reaction step a) are N(C 2 H 5 ) 3 , 1 ,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or 1 ,5-diazabicyclo[4.3.0]non-5-ene (DBN) or imidazole. The reaction is carried out at temperatures of from O 0 C to 10O 0 C, preferably at +15°C to +3O 0 C in particular at ambient temperature. The compound of formula Vl, wherein hal is chlorine and R 1 is ethyl, is preferred for the use in reaction step a).

The compounds of formula III are novel, especially developed for the preparation of the compounds of formula I and therefore form a further object of the present invention. Especially suitable compounds of formula III are those, wherein R 1 is methyl or ethyl, preferably ethyl and A 1 , A 2 , A 3 , A 4 and A 5 have the preferred meanings given for formula I above.

The reaction steps b) and c) are preferably carried out in the presence of a solvent such as a hydrocarbon, ether or dipolar aprotic solvent. Preferred solvents are tetrahydrofurane, toluene, dioxane, diethylether, diisopropylether or methyltertbutylether and mixtures thereof. The reaction steps are preferably carried out at a temperature of from -100 0 C to +100 0 C 1 especially at from -78°C to O 0 C (step b), and at a temerature of from 0 0 C to +100 0 C, especially from +6O 0 C to +100 0 C.

In an especially preferred embodiment of the process according to the invention, the reaction steps b) and c) are carried out without isolation of intermediates, that is to say the compound of formula Vl obtained according to reaction step b) is converted in situ with acid to the compound of formula I. The possibility of carrying out the process according to the invention in a one-pot reaction constitutes a considerable advantage especially for large-scale application.

Compounds of formula Il are known or can be prepared according to known methods. A process for the preparation of compounds of formula Il is described, for example, in WO03/016282.

Compounds of formula V are described, for example, in WO2006/0401 13 or WO2006/1 11341 .

The compounds of formula V can be prepared by reacting a compound of formula VII with a compound of formula VIII in the presence of a base and an inert solvent:

Suitable bases are for example N(C 2 Hs) 3 , DBU, DBN or imidazole. Preferred solvents are tetrahydrofurane, dioxane, glyme, ethyl acetate or toluene. The reaction is carried out at temperatures of from 0 0 C to 100 0 C, preferably at +15 0 C to +30 0 C in particular at ambient

temperature. A further process for the preparation of compounds of formula V is described in WO2006/111341. Compounds of formula VII are known for example from WO2006/040113 or WO2006/061200 or can be prepared according to known methods. Compounds of formula VIII and their preparation are described in Tetrahedron Letters, 1991 , 32, 3263.

The process according to the invention is explained in greater detail by the following Examples.

Example P1 : Preparation of a compound of formula Villa:

Villa

In a flask equipped with a magnetic stirring bar, a reflux condenser and a nitrogen inlet with a bubbler outlet, 2-amino-3-methylbenzoic acid (18.56 g, 0.122 mole) was suspended in 160 ml toluene. Thionyl chloride (35.7 ml, 0.49 mole) was added and the mixture was heated at 80 0 C and stirred at that temperature until the rapid gas evolution slowed down. The resulting solution was then gradually heated to reflux temperature for an hour. The solvent was then distilled off at the rotary evaporator. After the residual solvent was removed under high vacuum, the residue was distilled under high vacuum and the 3-methyl-2- sulfinylaminobenzoyl chloride (Eb: 125°C/ 3. 10 "2 torr) was isolated as a bright yellow oil that crystallized on standing.

Example P2: Preparation of a compound of formula Va:

Bicyclopropyl-1 -ylamine hydrochloride (0.632 g, 4.64 mmole) was suspended in 4 ml of dichloromethane. Triethylamine (1.5 ml) was added, followed by a solution of 3-methyl-2- sulfinylaminobenzoyl chloride (1 .000 g, 4.64 mmole) in dichloromethane (6 ml). The reaction mixture was stirred at 2O 0 C for an hour, and then treated 0.5 ml of HCI 2N for another hour. After neutralization and extraction with dichloromethane, the crude amide was purified by column chromatography on silica gel, using a gradient of ethyl acetate / cyc/o-hexane (20%- 80% to 40%-60%). The 2-amino-3-methyl-N-(bicyclopropyl-1 -yl)-benzamide was obtained as colorless crystals with a melting point of 145-148 0 C.

Example P3: Preparation of a compound of formula Vb:

Vb

5.0 g (1.0 eq) 2-amino-3-methylbenzoic acid were suspended in 45 g toluene under argon. At 75°C, 6 g (1.5 eq) of thionylchloride were carefully added during 15 minutes. Gas evolution was observed. The suspension was held at 75°C for an additional hour. Another portion of 6g (1.5 eq) of thionylchloride was added. After one hour, the mixture was cooled to room temperature and was added carefully during 20 minutes to a solution of 31 g (4 eq) of a methylamine solution (33% in ethanol). The reaction temperature was held between 20° and 3O 0 C with sporadic cooling using an ice bath. After the addition was complete, the suspension was held for 30 minutes at room temperature.

Workup with ethylacetate (50 g) and water (24 g) gave after phase separation and evaporation of the organic solvent 6 g of crude product (LC: 65%). Recrystallisation from toluene (10 g) and washing with hexanes (5 g) gave 2.8 g 2-amino-3,N-dimethyl benzamide. MS M + +1 =165

1 H-NMR (CDCI 3 ): 2.15 (s, 3H, Ar-CH 3 ), 2.98 (d, 3H, NCH 3 ), 2.55 (s, br, 2H 1 NH 2 ) 6.05 (s, 1 H, NH), 6.55 (1 H, t), 7.12(d, 1 H), 7.2 (d, 1 H)

Example P4. Preparation of a compound of formula Ilia:

IMa

3.7 g 2-amino-3,N-dimethyl benzamide were dissolved in 45g tetrahydrofurane at room temperature. 3.5 g (1.5 eq) triethylamine were added during 10 minutes. With cooling, 3.5 g

(1 eq) of ethyloxalylchloride were added carefully, so that the reaction temperature did not exceed 30 0 C. After one hour at room temperature another 0.35 g (0.1 eq) of triethylamine and 0.35 g (0.1 eq) of ethyloxalylchloride were added during 5 minutes.

The reaction mixture was diluted with 100 ml ethylacetate and 45 g water. Phase separation, drying of the organic phase with Na 2 SO 4 and evaporation gave 5.9 g N-(2-methyl-6- methylcarbamoyl-phenyl)-oxalamic acid ethyl ester.

MS M + +1 =265

1 H-NMR (CDCI 3 ): 1 .48 (t, 3H), 2.28 (s,3H), 2.87 (d, 3H), 4.45 (q,2H) 6.48 (d, br, 1 H), 7.15 (t,

1 H), 7.2-7.35 (Cl 1 Cl, 2 H), 10.5 (s, 1 H)

Example P5: Preparation of a compound of formula If:

(If)

A solution of 0.9 g (1.0 eq) N-(3-chloro-pyridin-2-yl)-N'-[2,2,2-trifluoro-1 -methyl-ethylidene]- hydrazine in 8.1 g tetrahydrofurane was cooled to -70 0 C under argon. A solution of

lithiumdiisopropylamine (2 M in THF) was added carefully during 15 minutes. The mixture was stirred at this temperature for 40 minutes.

A solution of 1.0 g (1.0 eq) N-(2-methyl-6-methylcarbamoyl-phenyl)-oxalamic acid ethyl ester in 10ml tetrahydrofurane was added slowly during 30 minutes. The mixture was stirred at -

70 0 C for an hour, then allowed to warm to room temperature.

The reaction was treated with ca. 23ml of 2N HCI. The reaction mixture was diluted with

50ml ethylacetate, washed with water, dried with Na 2 SO 4 and evaporated to give 1.7g crude intermedate. Stirring with 14 g toluene at room temperature, filtration and drying gave 0.2 g of an intermediate which was suspended in 10ml of chlorobenzene and heated with 0.3 g of trifluoroacetic acide at 6O 0 C for ohe hour. Evaporation of the solvent, redissolving in ethylacetate and washing with 5ml of a 5% of a NaHCO 3 solution, drying and evaporation gave 200mg of 2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-ca rboxylic acid (2- methyl-6-methylcarbamoyl-phenyl)-arnide .

MS: M + +1 = 438

1 H-NMR(CDCI 3 ): 2.21 (s, 3H), 2.97 (s,3H), 6.17 (s.br, 1 H) 1 7.15 (dd,J=7.6 Hz, J=7.6 Hz, 1 H),

7.24-7.29 (m, 2H), 7.33 (s, 1 H), 7.41 (dd, J=8.1 , J= 4.7), 7.88 (dd, J=8.1 , J=1.8, 1 H), 8.48

(dd, J = 4.8, J=0.5), 10.34 (s, br, 1 H).

Example P6: Preparation of methyl anthranilamide of formula Vc:

lsatoic anhydride methylamine methyl anthranilamide

To lsatoic anhydride (6.6 g) was added 40% Methylamine in water (16.4 g) over 30mins. After stirring for 1 hour the reaction mixture was neutralised with 2M Hydrochloric acid (1 OmIs). The mixture was stirred for a further 2 hour and the product precipitated. Filtration then gave 3.8 g of methyl anthranilamide solid.

1 H NMR CDCI 3 D 7.23 (d, 1 H), 7.13 (m, 1 H), 6.61 (d, 1 H), 6.56 (m, 1 H), 6.10 (s, br, 1 H), 2.85 (d, 3H). GCMS m + 150

Example P7: Preparation of N-(2-methylcarbamoyl-phenyl)-oxalamic acid ethyl ester of formula MIb:

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To N-methyl anthranilamide (5 g) in THF (60 g) was added triethylamine (7 g). An ice bath was then used to cool the reaction to below 25 0 C and maintain this temperature while ethyloxalychloride (5mls) was added slowly. The mixture was stirred for 20 hours at room temperature. The product was then extracted into ethyl acetate and water washed at pH5. The washing was repeated 4 times to ensure complete removal of residual triethylamine. After separation, the solvent was removed by evaporation in vacuo to afford 4.9g of N-(2- methylcarbamoyl-phenyl)-oxalamic acid ethyl ester.

1 H NMR CDCI 3 □ 12.6 (s, br, 1 H 1 NH), 8.5 (d, 1 H), 7.5 (d, 1 H), 7.4 (m, 1 H), 7.05 (m, 1 H), 6.8 (s, br, 1 H), 4.3 (q, 2H), 2.9 (s, 3H, NCH 3 ), 1.3 (t, 3H). GCMS m + 250.

Example P8: Preparation of 2-(3-Chloro-pyridinyl)-5-trifluoromethyl-2H-pyrazole-3-carbo xylic acid (2-methyl carbamoyl-phenvP-amide of formula Iq:

Step L Step 2

N-(3-Chloro-pyridin-2-yl)-N'-[2,2,2-trifluoro-1 -methyl-ethylidene]-hydrazine (0.5 g) was added to THF (5mls) and cooled to -7O 0 C (dry ice/acetone bath) to this was added lithium diisopropylamide (LDA) (2M solution in THF) (5.3ml, 10.5mmol). Stirred at -7O 0 C for 40mins forming the anion. A solution of N-(2-methylcarbamoyl-phenyl)-oxalamic acid ethyl ester (0.525 g, 2.1 mmol) in THF (5ml) was then added over 20mins. Stirred for 1 hour at this temp, before allowing to warm to room temperature. To the reaction mass was added 2M Hydrochloric acid (13ml) to neutralise. The reaction mass was extracted into ethyl acetate, water washed then dried over magnesium sulphate and the solvent removed in vacuo 0.547 g recovered. The product was then purified by column chromatography (silica gel, eluent: ethyl acetate/iso-hexane 50:50) to afford purified hydroxy intermediate (0.33 g). The hydroxy intermediate was then suspended in chlorobenzene (2mls) with trifluoroacetic acid

added (0.01 g) to give a purple/red solution. This was heated to 8O 0 C for 20mins using a microwave reactor. The chlorobenzene was removed by evaporation, redissolved in ethyl acetate and washed with 5% sodium carbonate solution. Drying and evaporation of solvent gave 0.09 g of 2-(3-Chloro-pyridinyl)-5-trifluoromethyl-2H-pyrazole-3-carbo xylic acid (2- methyl carbamoyl-phenyl)-amide.

1 H NMR d6 DMSO. D 12.85 (s, 1 H), 8.93 (d, br, NHCH 3 ), 8.60 (dd, 1 H), 8.30 (dd, 1 H), 8.2 (d, 1 H) 1 7.8 (d, 1 H), 7.70 (dd, 1 H) 1 7.55 (s, 1 H), 7.50 (m, 1 H), 7.20 (m, 1 H) 1 2.83 (d, 3H, NHCH 3 ).

(Vd) Example P9: Preparation of 2-amino-N-(bicvclopropyl-1 -yl)-benzamide of formula Vd:

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To bicyclopropylamine hydrochloride (2 g) was added dichloromethane (16ml) and triethylamine (3g). To this was then added isatoic anhydride (2.22 g) in dichloromethane (20ml). The mixture was stirred for 2.5 hours at 20 0 C and then the solvent removed in vacuo to leave a waxy solid. The solid was redissolved in ethyl acetate and washed with water at pH7. The solvent layer was separated and dried over magnesium solvent. Filtration and evaporation of the solvent afforded the 2-amino-N-(bicyclopropyl-1 -yl)-benzamide product 1.49g.

1 H NMR (CDCI 3 ) D 7.2 (d, 1 H), 7.1 (dd, 1 H), 6.65 (d, 1 H), 6.55 (dd, 1 H), 6.45 (s, 1 H, NH), 5.8 (s, 2H, NH 2 ), 1.45 (m, 1 H), 0.7 (m, 2H), 0.6 (m, 2H), 0.35 (m, 2H), 0.1 (m, 2H) and GC/MS m + 216.

Example P10: Preparation of N-(2-bicvclopropyl-1yl-carbamoyl-phenvO-oxalamic acid ethyl

UTTc) ester of formula IMc:

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To 2-amino-N-(bicyclopropyl-1 -yl)-benzamide (1.25 g) in tetrahydrofuran (21 ml) was added triethylamine (1.25 g). The mixture was cooled to 0 0 C and ethyloxalylchloride (0.8 g) was added dropwise. The mixture was stirred at 0 0 C for 1 hour. A further amount of ethyloxalylchloride (0.26 g) was then added to complete the reaction. Ethyl acetate was added and the mixture was washed with water (pH5) 3 times. The organic layer was

separated and dried over magnesium sulphate, filtered and the solvent evaporated in vacuo to yield 1.68g of N-(2-bicyclopropyl-1yl-carbamoyl-phenyl)-oxalamic acid ethyl ester. The crude product was then passed through a short silica gel column (eluent: ethyl acetate/iso- hexane 70:30) to give the purified product as a cream solid (1.4g).

1 H NMR CDCI 3 P12.6 (S 1 1 H 1 NH), 8.5 (d, 1 H), 7.45 (d, 1 H), 7.32 (m, 1 H), 7.1 1 (s, br, 1 H), 6.98 (m, 1 H), 4.3 (q, 2H), 1.5 (m, 1 H), 1.35 (t, 3H), 0.73 (m, 2H), 0.6 (m, 2H), 0.34 (m, 2H), 0.12 (m, 2H).

Example P11 : Preparation of 2-(3-Chloro-pyridinyl)-5-trifluoromethyl-2H-pyrazole-3- carboxylic acid (2-bicvclopropyl-1yl-carbamoyl-phenyl)-amide of formula Ih:

N-(3-Chloro-pyridin-2-yl)-N'-[2,2,2-trifluoro-1 -methyl-ethylidene]-hydrazine (0.5 g) in THF (5mls) was cooled to -7O 0 C (dry ice/acetone bath) and lithium diisopropylamide (LDA) (in THF) (12.7ml, 10.5mmol) was added. The mixture was stirred at -70 0 C for 40min to form the anion. A solution of N-(2-bicyclopropyl-1yl-carbamoyl-phenyl)-oxalamic acid ethyl ester (0.66g, 2.1 mmol) in THF (5ml) was then added over 20mins. The mixture was stirred at - 7O 0 C for 1 hour before allowing to warm to room temperature. To the reaction mass was added 2M Hydrochloric acid (8 g) to neutralise. The reaction mass was extracted into ethyl acetate, water washed then dried over magnesium sulphate and solvent evaporated to afford the crude product 0.8 g. The crude product was then purified by column chromatography (silica gel, eluent: ethyl acetate/lso-Hexane 50:50) to afford the hydroxy intermediate 0.19 g. The hydroxy intermediate (0.05 g) was suspended in chlorobenzene (2mls) and trifluoroacetic acid added (0.01 g) to give a purple/red solution. This was heated to 8O 0 C for 20mins using a microwave reactor. The chlorobenzene was removed by evaporation, redissolved in ethyl acetate and washed with 5% sodium carbonate solution. Drying and

evaporation of solvent gave 0.05g of 2-(3-Chloro-pyridinyl)-5-trifluoromethyl-2H-pyrazole-3- carboxylic acid) 2-bicyclopropyl-1yl-carbamoyl-phenyl)-amide.

1 H NMR d6 DMSO D 12.50 (s, 1 H), 8.58 (dd, 1 H), 8.29 (dd, 1 H) 1 8.09 (d, 1 H), 7.78 (d, 1 H), 7.73 (dd, 1 H), 7.56 (s, 1 H), 7.47 (m, 1 H), 7.22 (m, 1 H), 1.44 (m, 1 H), 0.71 (m, 2H), 0.60 (m, 2H), 0.36 (m, 2H), 0.20 (m, 2H)




 
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