Insecticidal Aryl Pyrrolidines

A method for the preparation of a compound of general formula (I)

• wherein
• X which may be same or different, represents halogen, C1-12 haloalkyl, nitro, C1-12 alkyl, C1-12 alkoxy, cyano, C1-12 haloalkoxy, C1-12 alkylthio, C1-12 alkylsulfinyl, C1-12 alkylsulfonyl, C1-12 haloalkylthio, C1-12 haloalkylsulfinyl, C1-12 haloalkylsulfonyl, hydroxyl, mercapto, amino, C1-12 alkylcarbonylamino, C1-12 haloalkylcarbonylamino, benzoylamino, C1-12 alkoxy-carbonylamino, C1-12 haloalkoxy-carbonylamino, C1-12 alkylsulfonylamino or C1-12 haloalkylsulfonylamino;
• Y which may be same or different, represents halogen, C1-12 haloalkyl, nitro, C1-12 alkyl, C1-12 alkoxy, cyano, C1-12 haloalkoxy, C1-12 alkylthio, C1-12 alkylsulfinyl, C1-12 alkylsulfonyl, C1-12 haloalkylthio, C1-12 haloalkylsulfinyl, C1-12 haloalkylsulfonyl, hydroxyl, mercapto, amino, C1-12 alkylcarbonylamino, C1-12 haloalkylcarbonylamino, benzoylamino, C1-12 alkoxy-carbonylamino, C1-12 haloalkoxy-carbonylamino, C1-12 alkylsulfonylamino or C1-12 haloalkylsulfonylamino;
• R represents C1-12 alkyl or C1-12 haloalkyl;
• m represents 0, 1, 2, 3, 4 or 5;
• n represents 0, 1, 2, or 4;
• G is selected from the group consisting of
• or a group selected from G1 to G9:
• wherein
• R1 and R2 each independently represents hydrogen;
• optionally substituted C1-12 alkyl, C2-12 alkenyl, C2-12 alkynyl, C3-7 cycloalkyl;
• C1-12 alkylsulfonyl, C1-12 haloalkylsulfonyl or CH2—R7;
• or when taken together represent C2-6 alkylene;
• R3 and R4 each independently represents hydrogen, cyano;
• optionally substituted C1-12 alkyl, C2-12 alkenyl, C2-12 alkynyl, C3-7 cycloalkyl;
• or C1-12 alkoxycarbonyl;
• or when taken together represent C2-6 alkylene;
• l represents 1 or 2 or 3;
• R5 represents hydrogen;
• C1-12 alkyl;
• optionally substituted C3-7 cycloalkyl;
• C1-6 haloalkyl;
• cyano;
• C2-12 alkenyl;
• C2-12 alkynyl;
• C1-12 alkylcarbonyl;
• or CH2—R7;
• R6 represents formyl, cyano, C1-6 alkylcarbonyl, C1-12 alkylthiocarbonyl, C1-12 haloalkyl-carbonyl, C1-12 haloalkylthiocarbonyl, C1-12 alkylaminocarbonyl, C1-12 alkylaminothio-carbonyl, dialkylamino-carbonyl having from 2 to 8 carbon atoms, dialkylaminothio-carbonyl having from 2 to 8 carbon atoms, C1-12 alkoxyaminocarbonyl, C1-12 alkoxyaminothiocarbonyl, C1-12 alkoxycarbonyl, C1-12 alkoxythiocarbonyl, C1-12 thioalkoxycarbonyl, C1-12 thioalkoxythiocarbonyl, CO—R7, CS—R7, C1-12 alkylsulfonyl or C1-12 haloalkylsulfonyl;
• or
• R5 and R6 when taken together with the nitrogen to which they are attached to form a 3-6 membered ring which contains at least one N atom and, optionally at least another heteroatom selected from S and O, wherein the ring is optionally substituted with keto or thioketo;
• Z which may be same or different, represents halogen, C1-12 haloalkyl, nitro, C1-12 alkyl, C1-12 alkoxy, cyano, C1-12 haloalkoxy, C1-12 alkylsulfonyl, C1-12 haloalkylsulfonyl, hydroxyl or mercapto;
• k1 represents 0, 1, 2, 3 or 4;
• k2 represents 0, 1, 2 or 3;
• k3 represents 0 or 1;
• k4 represents 0 or 1;
• R7 represents phenyl or a heterocyclic ring, which are optionally substituted with at least one substituent selected from fluorine, chlorine, bromine, iodine and C1-12 alkyl;
• and
• A represents C or N;
• comprising reacting a compound of formula (II)
• wherein
• X, R and m are as defined above, with a compound of formula (III) or formula (III-a)
• wherein
• Y, A, G and n are as defined above, and
• L1 is halogen or a C1-C4 haloalkylsulfonyloxy group.

A compound of formula (III) or formula (III-a)

• wherein
• Y which may be same or different, represents halogen, C1-12 haloalkyl, nitro, C1-12 alkyl, C1-12 alkoxy, cyano, C1-12 haloalkoxy, C1-12 alkylthio, C1-12 alkylsulfinyl, C1-12 alkylsulfonyl, C1-12 haloalkylthio, C1-12 haloalkylsulfinyl, C1-12 haloalkylsulfonyl, hydroxyl, mercapto, amino, C1-12 alkylcarbonylamino, C1-12 haloalkylcarbonylamino, benzoylamino, C1-12 alkoxy-carbonylamino, C1-12 haloalkoxy-carbonylamino, C1-12 alkylsulfonylamino or C1-12 haloalkylsulfonylamino;
• A represents C or N;
• G is selected from the group consisting of
• or a group selected from G1 to G9:
• wherein
• R1 and R2 each independently represents hydrogen;
• optionally substituted C1-12 alkyl, C2-12 alkenyl, C2-12 alkynyl, C3-7 cycloalkyl;
• C1-12 alkylsulfonyl, C1-12 haloalkylsulfonyl or CH2—R7;
• or when taken together represent C2-6 alkylene;
• R3 and R4 each independently represents hydrogen, cyano;
• optionally substituted C1-12 alkyl, C2-12 alkenyl, C2-12 alkynyl, C3-7 cycloalkyl;
• or C1-12 alkoxycarbonyl;
• or when taken together represent C2-6 alkylene;
• l represents 1 or 2 or 3;
• R5 represents hydrogen;
• C1-12 alkyl;
• optionally substituted C3-7 cycloalkyl;
• C1-6 haloalkyl;
• cyano;
• C2-12 alkenyl;
• C2-12 alkynyl;
• C1-12 alkylcarbonyl;
• or CH2—R7;
• R6 represents formyl, cyano, C1-6 alkylcarbonyl, C1-12 alkylthiocarbonyl, C1-12 haloalkyl-carbonyl, C1-12 haloalkylthiocarbonyl, C1-12 alkylaminocarbonyl, C1-12 alkylaminothio-carbonyl, dialkylamino-carbonyl having from 2 to 8 carbon atoms, dialkylaminothio-carbonyl having from 2 to 8 carbon atoms, C1-12 alkoxyaminocarbonyl, C1-12 alkoxyaminothiocarbonyl, C1-12 alkoxycarbonyl, C1-12 alkoxythiocarbonyl, C1-12 thioalkoxycarbonyl, C1-12 thioalkoxythiocarbonyl, CO—R7, CS—R7, C1-12 alkylsulfonyl or C1-12 haloalkylsulfonyl;
• or
• R5 and R6 when taken together with the nitrogen to which they are attached to form a 3-6 membered ring which contains at least one N atom and, optionally at least another heteroatom selected from S and O, wherein the ring is optionally substituted with keto or thioketo;
• Z which may be same or different, represents halogen, C1-12 haloalkyl, nitro, C1-12 alkyl, C1-12 alkoxy, cyano, C1-12 haloalkoxy, C1-12 alkylsulfonyl, C1-12 haloalkylsulfonyl, hydroxyl or mercapto;
• k1 represents 0, 1, 2, 3 or 4;
• k2 represents 0, 1, 2 or 3;
• k3 represents 0 or 1;
• k4 represents 0 or 1;
• R7 represents phenyl or a heterocyclic ring, which are optionally substituted with at least one substituent selected from fluorine, chlorine, bromine, iodine and C1-12 alkyl;
• and
• n represents 0, 1, 2, or 4;
• and
• L1 represents halogen or a C1-C4 haloalkylsulfonyloxy group.

A method for the preparation of a compound of formula (II), comprising reacting a compound of the formula (XVI):

• wherein
• X which may be same or different, represents halogen, C1-12 haloalkyl, nitro, C1-12 alkyl, C1-12 alkoxy, cyano, C1-12 haloalkoxy, C1-12 alkylthio, C1-12 alkylsulfinyl, C1-12 alkylsulfonyl, C1-12 haloalkylthio, C1-12 haloalkylsulfinyl, C1-12 haloalkylsulfonyl, hydroxyl, mercapto, amino, C1-12 alkylcarbonylamino, C1-12 haloalkylcarbonylamino, benzoylamino, C1-12 alkoxy-carbonylamino, C1-12 haloalkoxy-carbonylamino, C1-12 alkylsulfonylamino or C1-12 haloalkylsulfonylamino;
• m represents 0, 1, 2, 3, 4 or 5;
• R represents C1-12 alkyl or C1-12 haloalkyl;
• with N-benzyl-1-methoxy-N-[(trimethylsilyl)methyl]methanamine in the presence of a catalyst to obtain a compound of formula (XVII):
• wherein X, m and R are as defined above, and debenzylating the compound of formula (XVII) to obtain the compound of the formula (II).

A compound of formula (XVI)

• wherein
• X which may be same or different, represents halogen, C1-12 haloalkyl, nitro, C1-12 alkyl, C1-12 alkoxy, cyano, C1-12 haloalkoxy, C1-12 alkylthio, C1-12 alkylsulfinyl, C1-12 alkylsulfonyl, C1-12 haloalkylthio, C1-12 haloalkylsulfinyl, C1-12 haloalkylsulfonyl, hydroxyl, mercapto, amino, C1-12 alkylcarbonylamino, C1-12 haloalkylcarbonylamino, benzoylamino, C1-12 alkoxy-carbonylamino, C1-12 haloalkoxy-carbonylamino, C1-12 alkylsulfonylamino or C1-12 haloalkylsulfonylamino;
• m represents 0, 1, 2, 3, 4 or 5;
• and
• R represents C1-12 alkyl or C1-12 haloalkyl.

A method (b) for the preparation of a compound of general formula (I),

• wherein
• X which may be same or different, represents halogen, C1-12 haloalkyl, nitro, C1-12 alkyl, C1-12 alkoxy, cyano, C1-12 haloalkoxy, C1-12 alkylthio, C1-12 alkylsulfinyl, C1-12 alkylsulfonyl, C1-12 haloalkylthio, C1-12 haloalkylsulfinyl, C1-12 haloalkylsulfonyl, hydroxyl, mercapto, amino, C1-12 alkylcarbonylamino, C1-12 haloalkylcarbonylamino, benzoylamino, C1-12 alkoxy-carbonylamino, C1-12 haloalkoxy-carbonylamino, C1-12 alkylsulfonylamino or C1-12 haloalkylsulfonylamino;
• Y which may be same or different, represents halogen, C1-12 haloalkyl, nitro, C1-12 alkyl, C1-12 alkoxy, cyano, C1-12 haloalkoxy, C1-12 alkylthio, C1-12 alkylsulfinyl, C1-12 alkylsulfonyl, C1-12 haloalkylthio, C1-12 haloalkylsulfinyl, C1-12 haloalkylsulfonyl, hydroxyl, mercapto, amino, C1-12 alkylcarbonylamino, C1-12 haloalkylcarbonylamino, benzoylamino, C1-12 alkoxy-carbonylamino, C1-12 haloalkoxy-carbonylamino, C1-12 alkylsulfonylamino or C1-12 haloalkylsulfonylamino;
• R represents C1-12 alkyl or C1-12 haloalkyl;
• m represents 0, 1, 2, 3, 4 or 5;
• n represents 0, 1, 2, or 4;
• G is selected from the group consisting of
• or a group selected from G1 to G9:
• wherein
• R1 and R2 each independently represents hydrogen;
• optionally substituted C1-12 alkyl, C2-12 alkenyl, C2-12 alkynyl, C3-7 cycloalkyl;
• C1-12 alkylsulfonyl, C1-12 haloalkylsulfonyl or CH2—R7;
• or when taken together represent C2-6 alkylene;
• R3 and R4 each independently represents hydrogen, cyano;
• optionally substituted C1-12 alkyl, C2-12 alkenyl, C2-12 alkynyl, C3-7 cycloalkyl;
• or C1-12 alkoxycarbonyl;
• or when taken together represent C2-6 alkylene;
• l represents 1 or 2 or 3;
• R5 represents hydrogen;
• C1-12 alkyl;
• optionally substituted C3-7 cycloalkyl;
• C1-6 haloalkyl;
• cyano;
• C2-12 alkenyl;
• C2-12 alkynyl;
• C1-12 alkylcarbonyl;
• or CH2—R7;
• R6 represents formyl, cyano, C1-6 alkylcarbonyl, C1-12 alkylthiocarbonyl, C1-12 haloalkyl-carbonyl, C1-12 haloalkylthiocarbonyl, C1-12 alkylaminocarbonyl, C1-12 alkylaminothio-carbonyl, dialkylamino-carbonyl having from 2 to 8 carbon atoms, dialkylaminothio-carbonyl having from 2 to 8 carbon atoms, C1-12 alkoxyaminocarbonyl, C1-12 alkoxyaminothiocarbonyl, C1-12 alkoxycarbonyl, C1-12 alkoxythiocarbonyl, C1-12 thioalkoxycarbonyl, C1-12 thioalkoxythiocarbonyl, CO—R7, CS—R7, C1-12 alkylsulfonyl or C1-12 haloalkylsulfonyl;
• or
• R5 and R6 when taken together with the nitrogen to which they are attached to form a 3-6 membered ring which contains at least one N atom and, optionally at least another heteroatom selected from S and O, wherein the ring is optionally substituted with keto or thioketo;
• Z which may be same or different, represents halogen, C1-12 haloalkyl, nitro, C1-12 alkyl, C1-12 alkoxy, cyano, C1-12 haloalkoxy, C1-12 alkylsulfonyl, C1-12 haloalkylsulfonyl, hydroxyl or mercapto;
• k1 represents 0, 1, 2, 3 or 4;
• k2 represents 0, 1, 2 or 3;
• k3 represents 0 or 1;
• k4 represents 0 or 1;
• R7 represents phenyl or a heterocyclic ring, which are optionally substituted with at least one substituent selected from fluorine, chlorine, bromine, iodine and C1-12 alkyl;
• and
• A represents C or N;
• comprising reacting a compound of formula (IV) or formula (IV-a)
• wherein X, Y, R, A, and m are as defined above, or
• reacting a compound of formula (V) or formula (V-a)
• wherein
• X, Y, R, A, m and n are as defined above;
• and
• L2 represents chlorine, bromine, C1-4 alkylcarbonyloxy, C1-4 alkoxycarbonyloxy or azolyl;
• with a compound of formula (VI):
• wherein
• R1 and R2 are as defined above;
• optionally in the presence of a condensation agent, and in the presence of base.

A compound of formula (IV) or (IV-a)

• wherein
• X which may be same or different, represents halogen, C1-12 haloalkyl, nitro, C1-12 alkyl, C1-12 alkoxy, cyano, C1-12 haloalkoxy, C1-12 alkylthio, C1-12 alkylsulfinyl, C1-12 alkylsulfonyl, C1-12 haloalkylthio, C1-12 haloalkylsulfinyl, C1-12 haloalkylsulfonyl, hydroxyl, mercapto, amino, C1-12 alkylcarbonylamino, C1-12 haloalkylcarbonylamino, benzoylamino, C1-12 alkoxy-carbonylamino, C1-12 haloalkoxy-carbonylamino, C1-12 alkylsulfonylamino or C1-12 haloalkylsulfonylamino;
• Y which may be same or different, represents halogen, C1-12 haloalkyl, nitro, C1-12 alkyl, C1-12 alkoxy, cyano, C1-12 haloalkoxy, C1-12 alkylthio, C1-12 alkylsulfinyl, C1-12 alkylsulfonyl, C1-12 haloalkylthio, C1-12 haloalkylsulfinyl, C1-12 haloalkylsulfonyl, hydroxyl, mercapto, amino, C1-12 alkylcarbonylamino, C1-12 haloalkylcarbonylamino, benzoylamino, C1-12 alkoxy-carbonylamino, C1-12 haloalkoxy-carbonylamino, C1-12 alkylsulfonylamino or C1-12 haloalkylsulfonylamino;
• R represents C1-12 alkyl or C1-12 haloalkyl;
• A represents C or N;
• m represents 0, 1, 2, 3, 4 or 5.

A compound of formula (V) or (V-a)

• wherein
• X which may be same or different, represents halogen, C1-12 haloalkyl, nitro, C1-12 alkyl, C1-12 alkoxy, cyano, C1-12 haloalkoxy, C1-12 alkylthio, C1-12 alkylsulfinyl, C1-12 alkylsulfonyl, C1-12 haloalkylthio, C1-12 haloalkylsulfinyl, C1-12 haloalkylsulfonyl, hydroxyl, mercapto, amino, C1-12 alkylcarbonylamino, C1-12 haloalkylcarbonylamino, benzoylamino, C1-12 alkoxy-carbonylamino, C1-12 haloalkoxy-carbonylamino, C1-12 alkylsulfonylamino or C1-12 haloalkylsulfonylamino;
• Y which may be same or different, represents halogen, C1-12 haloalkyl, nitro, C1-12 alkyl, C1-12 alkoxy, cyano, C1-12 haloalkoxy, C1-12 alkylthio, C1-12 alkylsulfinyl, C1-12 alkylsulfonyl, C1-12 haloalkylthio, C1-12 haloalkylsulfinyl, C1-12 haloalkylsulfonyl, hydroxyl, mercapto, amino, C1-12 alkylcarbonylamino, C1-12 haloalkylcarbonylamino, benzoylamino, C1-12 alkoxy-carbonylamino, C1-12 haloalkoxy-carbonyl amino, C1-12 alkylsulfonylamino or C1-12 haloalkylsulfonylamino;
• R represents C1-12 alkyl or C1-12 haloalkyl;
• A represents C or N;
• m represents 0, 1, 2, 3, 4 or 5;
• and
• L2 represents chlorine, bromine, C1-4 alkylcarbonyloxy, C1-4 alkoxycarbonyloxy or azolyl.

A method (e) for the preparation of a compound of formula (I)

• wherein
• X which may be same or different, represents halogen, C1-12 haloalkyl, nitro, C1-12 alkyl, C1-12 alkoxy, cyano, C1-12 haloalkoxy, C1-12 alkylthio, C1-12 alkylsulfinyl, C1-12 alkylsulfonyl, C1-12 haloalkylthio, C1-12 haloalkylsulfinyl, C1-12 haloalkylsulfonyl, hydroxyl, mercapto, amino, C1-12 alkylcarbonylamino, C1-12 haloalkylcarbonylamino, benzoylamino, C1-12 alkoxy-carbonylamino, C1-12 haloalkoxy-carbonylamino, C1-12 alkylsulfonylamino or C1-12 haloalkylsulfonylamino;
• Y which may be same or different, represents halogen, C1-12 haloalkyl, nitro, C1-12 alkyl, C1-12 alkoxy, cyano, C1-12 haloalkoxy, C1-12 alkylthio, C1-12 alkylsulfinyl, C1-12 alkylsulfonyl, C1-12 haloalkylthio, C1-12 haloalkylsulfinyl, C1-12 haloalkylsulfonyl, hydroxyl, mercapto, amino, C1-12 alkylcarbonylamino, C1-12 haloalkylcarbonylamino, benzoylamino, C1-12 alkoxy-carbonylamino, C1-12 haloalkoxy-carbonylamino, C1-12 alkylsulfonylamino or C1-12 haloalkylsulfonylamino;
• A represents C or N;
• R represents C1-12 alkyl or C1-12 haloalkyl;
• m represents 0, 1, 2, 3, 4 or 5;
• n represents 0, 1, 2, or 4;
• G represents
• wherein
• R3 and R4 each independently represents hydrogen, cyano;
• optionally substituted C1-12 alkyl, C2-12 alkenyl, C2-12 alkynyl, C3-7 cycloalkyl;
• or C1-12 alkoxycarbonyl;
• or when taken together represent C2-6 alkylene;
• l represents 1 or 2 or 3;
• R5 represents hydrogen;
• C1-12 alkyl;
• optionally substituted C3-7 cycloalkyl;
• C1-6 haloalkyl;
• cyano;
• C2-12 alkenyl;
• C2-12 alkynyl;
• C1-12 alkylcarbonyl;
• or CH2—R7;
• R6 represents formyl, cyano, C1-6 alkylcarbonyl, C1-12 alkylthiocarbonyl, C1-12 haloalkyl-carbonyl, C1-12 haloalkylthiocarbonyl, C1-12 alkylaminocarbonyl, C1-12 alkylaminothio-carbonyl, dialkylamino-carbonyl having from 2 to 8 carbon atoms, dialkylaminothio-carbonyl having from 2 to 8 carbon atoms, C1-12 alkoxyaminocarbonyl, C1-12 alkoxyaminothiocarbonyl, C1-12 alkoxycarbonyl, C1-12 alkoxythiocarbonyl, C1-12 thioalkoxycarbonyl, C1-12 thioalkoxythiocarbonyl, CO—R7, CS—R7, C1-12 alkylsulfonyl or C1-12 haloalkylsulfonyl;
• or
• R5 and R6 when taken together with the nitrogen to which they are attached to form a 3-6 membered ring which contains at least one N atom and, optionally at least another heteroatom selected from S and O, wherein the ring is optionally substituted with keto or thioketo;
• R7 represents phenyl or a heterocyclic ring, which are optionally substituted with at least one substituent selected from fluorine, chlorine, bromine, iodine and C1-12 alkyl;
• comprising reacting a compound of formula (VIII) or formula (VIII-b):
• wherein
• X, Y, R, R3, R4, A, l, m, and n are as defined above, and
• L3 represents chlorine, bromine, iodine, C1-4 alkylsulfonyloxy, C1-4 haloalkylsulfonyloxy, arylsulfonyloxy or azolyl with a compound of formula (IX):
• wherein
• R5 and R6 are as defined above, optionally in the presence of base.

A compound of formula (VIII) or formula (VIII-b):

• wherein
• X which may be same or different, represents halogen, C1-12 haloalkyl, nitro, C1-12 alkyl, C1-12 alkoxy, cyano, C1-12 haloalkoxy, C1-12 alkylthio, C1-12 alkylsulfinyl, C1-12 alkylsulfonyl, C1-12 haloalkylthio, C1-12 haloalkylsulfinyl, C1-12 haloalkylsulfonyl, hydroxyl, mercapto, amino, C1-12 alkylcarbonylamino, C1-12 haloalkylcarbonylamino, benzoylamino, C1-12 alkoxy-carbonylamino, C1-12 haloalkoxy-carbonylamino, C1-12 alkylsulfonylamino or C1-12 haloalkylsulfonylamino;
• Y which may be same or different, represents halogen, C1-12 haloalkyl, nitro, C1-12 alkyl, C1-12 alkoxy, cyano, C1-12 haloalkoxy, C1-12 alkylthio, C1-12 alkylsulfinyl, C1-12 alkylsulfonyl, C1-12 haloalkylthio, C1-12 haloalkylsulfinyl, C1-12 haloalkylsulfonyl, hydroxyl, mercapto, amino, C1-12 alkylcarbonylamino, C1-12 haloalkylcarbonylamino, benzoylamino, C1-12 alkoxy-carbonylamino, C1-12 haloalkoxy-carbonylamino, C1-12 alkylsulfonylamino or C1-12 haloalkylsulfonylamino;
• R represents C1-12 alkyl or C1-12 haloalkyl;
• R3 and R4 each independently represents hydrogen, cyano;
• optionally substituted C1-12 alkyl, C2-12 alkenyl, C2-12 alkynyl, C3-7 cycloalkyl;
• or C1-12 alkoxycarbonyl;
• or when taken together represent C2-6 alkylene;
• A represents C or N;
• l represents 1 or 2 or 3;
• m represents 0, 1, 2, 3, 4 or 5;
• n represents 0, 1, 2, or 4;
• and
• L3 represents chlorine, bromine, iodine, C1-4 alkylsulfonyloxy, C1-4 haloalkylsulfonyloxy, arylsulfonyloxy or azolyl.

A compound of formula (IX):

• wherein
• R5 represents hydrogen;
• C1-12 alkyl;
• optionally substituted C3-7 cycloalkyl;
• C1-6 haloalkyl;
• cyano;
• C2-12 alkenyl;
• C2-12 alkynyl;
• C1-12 alkylcarbonyl;
• or CH2—R7;
• R6 represents formyl, cyano, C1-6 alkylcarbonyl, C1-12 alkylthiocarbonyl, C1-12 haloalkyl-carbonyl, C1-12 haloalkylthiocarbonyl, C1-12 alkylaminocarbonyl, C1-12 alkylaminothio-carbonyl, dialkylamino-carbonyl having from 2 to 8 carbon atoms, dialkylaminothio-carbonyl having from 2 to 8 carbon atoms, C1-12 alkoxyaminocarbonyl, C1-12 alkoxyaminothiocarbonyl, C1-12 alkoxycarbonyl, C1-12 alkoxythiocarbonyl, C1-12 thioalkoxycarbonyl, C1-12 thioalkoxythiocarbonyl, CO—R7, CS—R7, C1-12 alkylsulfonyl or C1-12 haloalkylsulfonyl;
• or
• R5 and R6 when taken together with the nitrogen to which they are attached to form a 3-6 membered ring which contains at least one N atom and, optionally at least another heteroatom selected from S and O, wherein the ring is optionally substituted with keto or thioketo.

A method (f) for the preparation of a compound of formula (I)

• wherein
• X which may be same or different, represents halogen, C1-12 haloalkyl, nitro, C1-12 alkyl, C1-12 alkoxy, cyano, C1-12 haloalkoxy, C1-12 alkylthio, C1-12 alkylsulfinyl, C1-12 alkylsulfonyl, C1-12 haloalkylthio, C1-12 haloalkylsulfinyl, C1-12 haloalkylsulfonyl, hydroxyl, mercapto, amino, C1-12 alkylcarbonylamino, C1-12 haloalkylcarbonylamino, benzoylamino, C1-12 alkoxy-carbonylamino, C1-12 haloalkoxy-carbonylamino, C1-12 alkylsulfonylamino or C1-12 haloalkylsulfonylamino;
• Y which may be same or different, represents halogen, C1-12 haloalkyl, nitro, C1-12 alkyl, C1-12 alkoxy, cyano, C1-12 haloalkoxy, C1-12 alkylthio, C1-12 alkylsulfinyl, C1-12 alkylsulfonyl, C1-12 haloalkylthio, C1-12 haloalkylsulfinyl, C1-12 haloalkylsulfonyl, hydroxyl, mercapto, amino, C1-12 alkylcarbonylamino, C1-12 haloalkylcarbonylamino, benzoylamino, C1-12 alkoxy-carbonylamino, C1-12 haloalkoxy-carbonylamino, C1-12 alkylsulfonylamino or C1-12 haloalkylsulfonylamino;
• A represents C or N;
• R represents C1-12 alkyl or C1-12 haloalkyl;
• m represents 0, 1, 2, 3, 4 or 5;
• n represents 0, 1, 2, or 4;
• G is selected from the group consisting of
• or group selected from G1 to G9:
• wherein
• R1 and R2 each independently represents hydrogen;
• optionally substituted C1-12 alkyl, C2-12 alkenyl, C2-12 alkynyl, C3-7 cycloalkyl;
• C1-12 alkylsulfonyl, C1-12 haloalkylsulfonyl or CH2—R7;
• or when taken together represent C2-6 alkylene;
• R3 and R4 each independently represents hydrogen, cyano;
• optionally substituted C1-12 alkyl, C2-12 alkenyl, C2-12 alkynyl, C3-7 cycloalkyl;
• or C1-12 alkoxycarbonyl;
• or when taken together represent C2-6 alkylene;
• l represents 1 or 2 or 3;
• R5 represents hydrogen;
• C1-12 alkyl;
• optionally substituted C3-7 cycloalkyl;
• C1-6 haloalkyl;
• cyano;
• C2-12 alkenyl;
• C2-12alkynyl;
• C1-12 alkylcarbonyl;
• or CH2—R7;
• R6 represents formyl, cyano, C1-6 alkylcarbonyl, C1-12 alkylthiocarbonyl, C1-12 haloalkyl-carbonyl, C1-12 haloalkylthiocarbonyl, C1-12 alkylaminocarbonyl, C1-12 alkylaminothio-carbonyl, dialkylamino-carbonyl having from 2 to 8 carbon atoms, dialkylaminothio-carbonyl having from 2 to 8 carbon atoms, C1-12 alkoxyaminocarbonyl, C1-12 alkoxyaminothiocarbonyl, C1-12 alkoxycarbonyl, C1-12 alkoxythiocarbonyl, C1-12 thioalkoxycarbonyl, C1-12 thioalkoxythiocarbonyl, CO—R7, CS—R7, C1-12 alkylsulfonyl or C1-12 haloalkylsulfonyl;
• or
• R5 and R6 when taken together with the nitrogen to which they are attached to form a 3-6 membered ring which contains at least one N atom and, optionally at least another heteroatom selected from S and O, wherein the ring is optionally substituted with keto or thioketo;
• Z which may be same or different, represents halogen, C1-12 haloalkyl, nitro, C1-12 alkyl, C1-12 alkoxy, cyano, C1-12 haloalkoxy, C1-12 alkylsulfonyl, C1-12 haloalkylsulfonyl, hydroxyl or mercapto;
• k1 represents 0, 1, 2, 3 or 4;
• k2 represents 0, 1, 2 or 3;
• k3 represents 0 or 1;
• k4 represents 0 or 1;
• R7 represents phenyl or a heterocyclic ring, which are optionally substituted with at least one substituent selected from fluorine, chlorine, bromine, iodine and C1-12 alkyl;
• comprising reacting a compound represented by formula (X) or formula (X-a):
• wherein
• X, Y, R, R3, R4, R5, A, l, m and n are as defined above, with a compound of formula:
• R6-L4 (XI)
• wherein
• R6 is as defined above, and
• L4 represents fluorine, chlorine, bromine, C1-4 alkyl-carbonyloxy, C1-4 alkoxy-carbonyloxy, azolyl, C1-4 alkylsulfonyloxy, C1-4 haloalkylsulfonyloxy, arylsulfonyloxy, optionally, in the presence of base.

A compound of formula (X) or formula (X-a):

• wherein
• X which may be same or different, represents halogen, C1-12 haloalkyl, nitro, C1-12 alkyl, C1-12 alkoxy, cyano, C1-12 haloalkoxy, C1-12 alkylthio, C1-12 alkylsulfinyl, C1-12 alkylsulfonyl, C1-12 haloalkylthio, C1-12 haloalkylsulfinyl, C1-12 haloalkylsulfonyl, hydroxyl, mercapto, amino, C1-12 alkylcarbonylamino, C1-12 haloalkylcarbonylamino, benzoylamino, C1-12 alkoxy-carbonylamino, C1-12 haloalkoxy-carbonylamino, C1-12 alkylsulfonylamino or C1-12 haloalkylsulfonylamino;
• Y which may be same or different, represents halogen, C1-12 haloalkyl, nitro, C1-12 alkyl, C1-12 alkoxy, cyano, C1-12 haloalkoxy, C1-12 alkylthio, C1-12 alkylsulfinyl, C1-12 alkylsulfonyl, C1-12 haloalkylthio, C1-12 haloalkylsulfinyl, C1-12 haloalkylsulfonyl, hydroxyl, mercapto, amino, C1-12 alkylcarbonylamino, C1-12 haloalkylcarbonylamino, benzoylamino, C1-12 alkoxy-carbonylamino, C1-12 haloalkoxy-carbonylamino, C1-12 alkylsulfonylamino or C1-12 haloalkylsulfonylamino;
• R represents C1-12 alkyl or C1-12 haloalkyl;
• R3 and R4 each independently represents hydrogen, cyano;
• optionally substituted C1-12 alkyl, C2-12 alkenyl, C2-12 alkynyl, C3-7 cycloalkyl;
• or C1-12 alkoxycarbonyl;
• or when taken together represent C2-6 alkylene;
• R5 represents hydrogen;
• C1-12 alkyl;
• optionally substituted C3-7 cycloalkyl;
• C1-6 haloalkyl;
• cyano;
• C2-12 alkenyl;
• C2-12 alkynyl;
• C1-12 alkylcarbonyl;
• or CH2—R7;
• R7 represents phenyl or a heterocyclic ring, which are optionally substituted with at least one substituent selected from fluorine, chlorine, bromine, iodine and C1-12 alkyl;
• A represents C or N;
• l represents 1 or 2 or 3;
• m represents 0, 1, 2, 3, 4 or 5;
• and
• n represents 0, 1, 2, or 4.

A compound of formula (XXIV) or formula (XXIV-a):

• wherein
• X which may be same or different, represents halogen, C1-12 haloalkyl, nitro, C1-12 alkyl, C1-12 alkoxy, cyano, C1-12 haloalkoxy, C1-12 alkylthio, C1-12 alkylsulfinyl, C1-12 alkylsulfonyl, C1-12 haloalkylthio, C1-12 haloalkylsulfinyl, C1-12 haloalkylsulfonyl, hydroxyl, mercapto, amino, C1-12 alkylcarbonylamino, C1-12 haloalkylcarbonylamino, benzoylamino, C1-12 alkoxy-carbonylamino, C1-12 haloalkoxy-carbonylamino, C1-12 alkylsulfonylamino or C1-12 haloalkylsulfonylamino;
• Y which may be same or different, represents halogen, C1-12 haloalkyl, nitro, C1-12 alkyl, C1-12 alkoxy, cyano, C1-12 haloalkoxy, C1-12 alkylthio, C1-12 alkylsulfinyl, C1-12 alkylsulfonyl, C1-12 haloalkylthio, C1-12 haloalkylsulfinyl, C1-12 haloalkylsulfonyl, hydroxyl, mercapto, amino, C1-12 alkylcarbonylamino, C1-12 haloalkylcarbonylamino, benzoylamino, C1-12 alkoxy-carbonylamino, C1-12 haloalkoxy-carbonylamino, C1-12 alkylsulfonylamino or C1-12 haloalkylsulfonylamino;
• R represents C1-12 alkyl or C1-12 haloalkyl;
• m represents 0, 1, 2, 3, 4 or 5;
• and
• n represents 0, 1, 2, or 4.