Process for preparing anthranilamide esters and derivatives Description The present invention relates to a process for preparing compounds of formula (I) which comprises reacting a compound of formula (II) or (Ι ) with a compound of formula (III). In this context, the present invention also relates to a process, which further comprises preparing compounds of formula (Ι ) by converting a compound of formula (II) into a compound of formula (Ι ), and to a process which further comprises preparing compounds of formula (II) by reacting a compound of formula (IV) with a compound of formula (V) or by reacting a compound of formula (VI) with a compound of formula (VII) or by reacting a compound of formula (VI) with a compound of formula (VIII). Moreover, the present invention relates to a process for preparing compounds of formula (II) by reacting a compound of formula (IV) with a compound of formula (V), and to a process for preparing compounds of formula (I), which comprises said preparation of the compounds of formula (II), an optional conversion to compounds of formula (Ι ), and the reaction with compounds of formula (III). Furthermore, the present invention relates to compounds of formulae (ΙΙ.Α'), (Ι .Α'), (II.A") and (Ι .Α") as precursors for the preparation of certain compounds of formula (I). N-Pyridylpyrazole carboxanilides carrying a sulfiminocarbonyl group in the ortho position with respect to the amide group, which are represented by formula (I) below, are of great interest in terms of their high activity against

(I)

The compounds of formula (I), wherein the variables p, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are as defined hereinafter and in the claims, belong to a class of anthranilamide insecticides, for which cyan- traniliprole and chlorantraniliprole are prominent examples. Anthranilamide insecticides have e.g. been described in WO 2007/006670. The compounds of formula (I) are typically prepared by reacting a substituted isatoic anhydride compound with a sulfimine or a sulfimine salt to give an aniline compound carrying a sulfiminocarbonyl group in the ortho position with respect to the amide group, which is then reacted with a suitable pyrazole derivative to give the compound of formula (I) (see WO 2013/024008).

Nevertheless, there remains a need for a process of preparing the compounds of formula (I) as such that a N-pyridyl pyrazole carboxanilide precursor is reacted with a sulfimine or a sulfimine salt because such a process can be advantageous in terms of the possibility to combine certain N-pyridylpyrazole carboxanilide precursors with a variety sulfimines or sulfimine salts. Furthermore, there is also a need for a straightforward process for the preparation of N- pyridylpyrazole carboxanilide precursors. WO 2007/006670 discloses a process, wherein a N-(het)arylpyrazole carboxanilide compound carrying an activated carboxylic acid group is reacted with a suitable sulfimine. However, WO 2007/006670 does not refer to N-pyridylpyrazole carboxanilide compounds as specific N- (het)arylpyrazole carboxanilide compounds, when describing the process for preparing N- (het)arylpyrazole carboxanilide compounds carrying a sulfiminocarbonyl group in the ortho posi- tion with respect to the amide group. Furthermore, it is not disclosed in WO 2007/006670 how the N-(het)arylpyrazole carboxanilide compounds carrying a carboxylic acid group can be obtained. In particular, WO 2007/006670 does not disclose an N-(het)arylpyrazole carboxanilide precursor, which can be obtained by only one reaction step, and can then either be directly reacted with a suitable sulfimine or can be converted to another N-(het)aryl pyrazole carboxanilide precursor. Moreover, WO 2007/006670 omits to mention any further N-(het)arylpyrazole carboxanilide precursors apart from N-(het)aryl pyrazole carboxanilide compounds carrying an activated carboxylic acid anhydride, azolide or halide.

In view of the above, it is an object of the present invention to provide a process for the prepa- ration of compounds of formula (I), which is advantageous in terms of the possibility to combine different N-pyridylpyrazole carboxanilide precursors with a variety sulfimines or sulfimine salts, so that a library of compounds of formula (I) with different N-pyridylpyrazole carboxanilide backbones and a variety of sulfiminocarbonyl groups can easily be provided, and the sulfimine formation can be optimized in terms of the yield.

It is another object of the present invention to provide a process for the preparation of compounds of formula (I), which is advantageous in view of the fact that either N-pyridylpyrazole carboxanilide precursors can be used, which are readily available by a one step reaction procedure from easily accessible starting materials, or other N-pyridylpyrazole carboxanilide precursors can be used, which can easily be obtained from the first mentioned N-pyridylpyrazole car- boxanilide precursors.

It is yet another object of the present invention to provide a straightforward process for preparing N-pyridylpyrazole carboxanilide precursors, which may then be directly used in the preparation of compounds of formula (I) or may be converted into other N-pyridylpyrazole carboxanilide precursors, which are then used in the preparation of compounds of formula (I).

It is yet another object of the present invention to provide different types of N-pyridylpyrazole caboxanilide precursors as versatile reaction tools for the preparation of compounds of formula (I) and anthranilamide insecticides such as cyclaniliprole.

The above objects are achieved by the processes and compounds described in detail in the claims and hereinafter.

In one aspect, the present invention relates to a process for preparing a compound of formula (I)

which comprises the steps of

(i) providing a compound of formula (II) or a compound of formula (Ι )

and

(ii) reacting the compound of formula (II) or the compound of formula (Ι ) with a compound of formula (III) or a salt thereof

4

I

R ⁵ (III)

wherein the variables p, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ^x and X in formulae (I), (II), (II ^* ) and (III) are as fol- lows:

R ^x is Ci-C6-alkyl, benzyl or phenyl, wherein the phenyl radical may be substituted by one or more radicals selected from halogen and NO2;

X is halogen, OC(0)Ci-C ₆ -alkyl, OS(0) ₂ Ci-C ₆ -alkyl, OS(0) ₂ Ci-C ₆ -haloalkyl, OS(0) ₂ benzyl,

OS(0) ₂ tolyl or OH;

p is 0, 1 , 2, 3 or 4;

R ¹ is selected from H, halogen, CN, CBrF ₂ , Ci-C6-alkyl, Ci-C6-fluoroalkyl, C ₂ -C6-alkenyl, and

C ₂ -C6-fluoroalkenyl, wherein the four last mentioned radicals may be substituted by one or more radicals R ^a ;

R ² is selected from the group consisting of halogen, Ci-C6-alkyl, Ci-C6-fluoroalkyl, C ₂ -C6- alkenyl, C ₂ -C6-fluoroalkenyl, wherein the four last mentioned radicals may be substituted by one or more radicals R ^a ;

Cs-Cs-cycloalkyI, which is unsubstituted, partially or completely halogenated or carries one or more radicals R ^aa ;

phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R ^e , and a 3-, 4-, 5-, 6- or 7- membered saturated, partially unsaturated or completely unsaturated heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals R ^e ;

if present, are independently selected from the group consisting of halogen, CN , Ci-Cs- alkyl, d-Cs-haloalkyl, C2-Cs-alkenyl, C2-C8-haloalkenyl, C2-Cs-alkynyl, C2-C8-haloalkynyl, wherein the six last radicals may optionally be substituted by one or more radicals R ^a , Cs-Cs-cycloalkyI, which is unsubstituted, partially or completely halogenated or carries one or more radicals R ^aa ;

-OR ^b , -SR ^b , -S(0) _m R ^b , -N(R ^c )R ^d ,

phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R ^e , and a 3-, 4-, 5-, 6- or 7- membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N , O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals R ^e , for p > 1 it being possible that R ³ are identical or different,

or two radicals R ³ bound on adjacent carbon atoms may be together a group selected from -CH2CH2CH2CH2-, -CH=CH-CH=CH-, -N=CH-CH=CH-, -CH=N-CH=CH-, -N=CH- N=CH-, -OCH2CH2CH2-, -OCH=CHCH ₂ -, -CH ₂ OCH ₂ CH ₂ -, -OCH2CH2O-, -OCH2OCH2-, -CH2CH2CH2-, -CH=CHCH ₂ -, -CH2CH2O-, -CH=CHO-, -CH2OCH2-, -CH ₂ C(=0)0-, - C(=0)OCH ₂ -, -0(CH ₂ )0-, -SCH2CH2CH2-, -SCH=CHCH ₂ -, -CH ₂ SCH ₂ CH ₂ -, -SCH2CH2S-, -SCH2SCH2-, -CH2CH2S-, -CH=CHS-, -CH2SCH2-, -CH ₂ C(=S)S-, -C(=S)SCH ₂ -, -S(CH ₂ )S-, -CH ₂ CH ₂ N Rq-,-CH ₂ CH=N-, -CH=CH-N R ^c i-, -OCH=N- and -SCH=N-, thus forming, together with the carbon atoms to which they are bound, a 5- or 6-membered ring, where the hydrogen atoms of the above groups may be replaced by one or more substituents selected from halogen, methyl, halomethyl, hydroxyl, methoxy and halomethoxy or one or more CH2 groups of the above groups may be replaced by a C=0 group;

and R ⁵ are selected, independently of one another, from the group consisting of Ci-Cio-alkyl, Ci-Cio-haloalkyl, C2-Cio-alkenyl, C2-Cio-haloalkenyl, C2-Cio-alkynyl, C2-Cio-haloalkynyl, wherein the six last radicals may optionally be substituted by one or more radicals R ^a , C3-Cio-cycloalkyl, which is unsubstituted, partially or completely halogenated or carries one or more radicals R ^aa ;

or R ⁴ and R ⁵ together represent a C2-Cg-alkylene, C2-Cg-alkenylene or Ce-Cg-alkynylene chain forming together with the sulfur atom to which they are attached a 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-membered saturated, partially unsaturated or fully unsaturated ring, wherein 1 to 4 of the CH2 groups in the C2-Cg-alkylene chain or 1 to 4 of any of the CH2 or CH groups in the C2-Cg-alkenylene chain or 1 to 4 of any of the CH2 groups in the Ce-Cg- alkynylene chain may be replaced by 1 to 4 groups independently selected from the group consisting of C=0, O, S, N, NO, SO, SO2 and N R^, and wherein the carbon atoms in the C2-Cg-alkylene, C2-Cg-alkenylene or C6-Cg-alkynylene chain may be substituted with 1 to 5 identical or different substituents RP, and wherein the sulfur and nitrogen atoms in the C2- Cg-alkylene, C2-Cg-alkenylene or C6-Cg-alkynylene chain, independently of one another, may be oxidized;

is selected from the group consisting of Ci-C6-alkoxy, Ci-C6-haloalkoxy, Cs-Cs-cycloalkyI,

Cs-Cs-halocycloalkyl, C ₂ -C ₆ -alkenyl, -OR ^b , -SR ^b , -S(0) _m R ^b , -N(R ^c )R ^d ,

phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R ^e , and a 3-, 4-, 5-, 6- or 7- membered saturated, partially unsaturated or completely unsaturated heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals R ^e ;

or two radicals R ^a , together with the carbon atoms to which they are bound, form a 3-, 4-,

5- , 6-, 7- or 8-membered saturated or partially unsaturated carbocyclic ring or a 3-, 4-, 5-,

6- , 7- or 8-membered saturated or partially unsaturated heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members;

wherein, in the case of more than one R ^a , R ^a can be identical or different;

R ^aa is selected from the group consisting of CN, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci- C6-haloalkoxy, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, -OR ^b , - SR ^b , -S(0) _m R ^b , -N(R ^c )R ^d , C(=0)N(R ^c )R ^d ,

phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R ^e , and a 3-, 4-, 5-, 6- or 7- membered saturated, partially unsaturated or completely unsaturated heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals R ^e ;

or two geminally bound radicals R ^aa together form a group selected from =CR ^h R ^k ;

R ^b is selected from the group consisting of H, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3- Ce-cycloalkyl, C3-C8-cycloalkyl-Ci-C4-alkyl, where the five last mentioned radicals may be unsubstituted, partially or fully halogenated and/or wherein one or two CH2 groups may be replaced by a CO group; and/or may carry 1 -2 radicals selected from Ci-C6-alkoxy, C1-C6- haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Ci-C6-alkylsulfinyl, Ci-C6-haloalkylsulfinyl, Ci-C6-alkylsulfonyl, Ci-C6-haloalkylsulfonyl, phenyl, benzyl, pyridyl and phenoxy, it being possible for phenyl, benzyl, pyridyl and phenoxy to be unsubstituted, partially or fully halogenated and/or to carry 1 , 2 or 3 substituents selected from the group consisting of C1-C6- alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, and C1-C6 haloalkoxy;

R ^c , R ^d are, independently from one another, selected from the group consisting of H, CN, C1-C6- alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, C3-C8-cycloalkyl-Ci-C4-alkyl, where the five last mentioned radicals may be unsubstituted, partially or fully halogenated and/or wherein one or two CH2 groups may be replaced by a CO group; and/or may carry 1 or 2 radicals selected from Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, Ci-C6-haloalkylthio, phenyl, benzyl, pyridyl and phenoxy, it being pos- sible for phenyl, benzyl, pyridyl and phenoxy to be unsubstituted, partially or fully halogenated and/or to carry 1 , 2 or 3 substituents selected from the group consisting of C1-C6- alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, and C1-C6 haloalkoxy;

or R ^c and R ^d , together with the nitrogen atom to which they are bound, form a 3-, 4-, 5-, 6- or 7-membered saturated, partly unsaturated or completely unsaturated N-heterocyclic ring which may contain 1 or 2 further heteroatoms selected from N, O and S as ring members, where the heterocyclic ring may carry 1 , 2, 3 or 4 substituents selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy; R ^e is selected from the group consisting of halogen, CN, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl and Cs-Cs-cycloalkyl, where the four last-mentioned radicals may be unsubsti- tuted, partially or fully halogenated and/or wherein one or two CH2 groups may be replaced by a CO group, and/or may carry 1 -2 radicals selected from Ci-C4-alkoxy, C1-C6- alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Ci-C6-alkylsulfinyl, C1-C6- haloalkylsulfinyl, Ci-C6-alkylsulfonyl, Ci-C6-haloalkylsulfonyl, phenyl, benzyl, pyridyl and phenoxy, it being possible for phenyl, benzyl, pyridyl and phenoxy to be unsubstituted, partially or fully halogenated and/or to carry 1 , 2 or 3 substituents selected from the group consisting of Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, and C1-C6 haloalkoxy;

wherein, in the case of more than one R ^e , R ^e can be identical or different;

R ^f , R9 are, independently of each other and independently of each occurrence, selected from the group consisting of Ci-C4-alkyl, C3-C6-cycloalkyl, Ci-C4-alkoxy-Ci-C4-alkyl, C3-C8- cycloalkyl-Ci-C4-alkyl, phenyl and benzyl;

R ^h , R ^k are, independently from one another, selected from the group consisting of H, halogen, CN, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and Cs-Cs-cycloalkyl, where the four last mentioned radicals may be unsubstituted, partially or fully halogenated and/or oxgenated, and/or may carry 1 or 2 radicals selected from Ci-C4-alkyl; Ci-C4-haloalkyl; Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, C1-C6- haloalkylthio, -OH, -SH, phenyl, benzyl, pyridyl and phenoxy, it being possible for phenyl, benzyl, pyridyl and phenoxy to be unsubstituted, partially or fully halogenated and/or to carry 1 , 2 or 3 substituents selected from the group consisting of Ci-C6-alkyl, C1-C6- haloalkyl, Ci-C6-alkoxy, C1-C6 haloalkoxy; (Ci-C6-alkyl)amino, di-(Ci-C6-alkyl)amino;

RP is selected from the group consisting of halogen, CN, Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Cs-Cs-cycloalkyl, C3-C8- halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl and C2-C6-haloalkynyl, said substituents RP being identical or different from one another if more than one substituent RP is present;

R ^q is selected from the group consisting of H, CN, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Cs-Cs-cycloalkyl, C3-Cs-halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl and C3-Cs-cycloalkyl-Ci-C4-alkyl;

m is 1 or 2, wherein, in the case of several occurrences, m may be identical or different; n is 0, 1 or 2; wherein, in the case of several occurrences, n may be identical or different.

The process is hereinafter also referred to as "process A".

The process A is advantageous in terms of the possibility to combine different N- pyridylpyrazole carboxanilide precursors, i.e. compounds of formula (II) or (Ι ), with a variety sulfimines or sulfimine salts, i.e. compounds of formula (III), so that the sulfiminocarbonyl group can easily be varied in the compounds of formula (I), e.g. to find an optimal combination be- tween a N-pyridylpyrazole carboxanilide backbone and a sulfiminocarbonyl group in terms of the activity against invertebrate pests. Furthermore, the possibility to use different N- pyridylpyrazole carboxanilide precursors, i.e. compounds of formula (II) or (Ι ), allows an optimization of the process in terms of the yields. The use of the compounds of formula (II) as N- pyridylpyrazole carboxanilide precursors has the particular advantage that these compounds are readily available from easily accessible starting materials. On the other hand, the compounds of formula (Ι ) can be advantageous in terms of their reactivity, and can be easily obtained from compounds of formula (II).

In view of the above, certain preferred embodiments of the invention relate to a process A, wherein the compound of formula (Ι ) is provided by converting a compound of formula (II) into a compound of formula (Ι ). Furthermore, certain preferred embodiments of the invention relate to a process A, wherein the compound of formula (II) is provided by reacting a compound of formula (IV) with a compound of formula (V),

(IV) (V)

or by reacting a compound of formula (VI) with a compound of formula (VII),

(VI) (VII)

or by reacting a compound of formula (VI) with a compound of formula (VIII) in the presence of an oxidizing agent,

(VI) (VIII)

wherein the variables p, R ¹ , R ² and R ³ in the compounds of formulae (IV), (V), (VI), (VII), (VIII) are as defined above, and wherein M in the compounds of formula (V) is Li, MgY or ZnY with Y being halogen, and wherein L in the compounds of formula (VII) is halogen, OC(0)Ci-C6-alkyl, OS(0)2Ci-C6-alkyl or OH. This will be outlined in detail below. In another aspect, the present invention relates to a process for preparing a compound of formula (II)

which comprises reacting a 2-isocyanatobenzoate of formula (IV) with a pyrazole metal compound of formula (V)

(IV) (V)

wherein

M is Li, MgY or ZnY with Y being halogen;

R ^x is Ci-C6-alkyl, benzyl or phenyl, wherein the phenyl radical may be substituted by one or more radicals selected from halogen and NO2;

p is 0, 1 , 2, 3 or 4;

R ¹ is selected from H, halogen, CN, CBrF2, Ci-C6-alkyl, Ci-C6-fluoroalkyl, C2-C6-alkenyl, C2- C6-fluoroalkenyl, wherein the four last mentioned radicals may be substituted by one or more radicals R ^a ;

R ² is selected from the group consisting of halogen, Ci-C6-alkyl, Ci-C6-fluoroalkyl, C2-C6- alkenyl, C2-C6-fluoroalkenyl, wherein the four last mentioned radicals may be substituted by one or more radicals R ^a ;

Cs-Cs-cycloalkyI, which is unsubstituted, partially or completely halogenated or carries one or more radicals R ^aa ;

phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R ^e , and a 3-, 4-, 5-, 6- or 7- membered saturated, partially unsaturated or completely unsaturated heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals R ^e ;

R ³ if present, are independently selected from the group consisting of halogen, CN, Ci-Cs- alkyl, Ci-Cs-haloalkyl, C2-Cs-alkenyl, C2-C8-haloalkenyl, C2-Cs-alkynyl, C2-C8-haloalkynyl, wherein the six last radicals may optionally be substituted by one or more radicals R ^a , Cs-Cs-cycloalkyI, which is unsubstituted, partially or completely halogenated or carries one or more radicals R ^aa ;

-OR ^b , -SR ^b , -S(0) _m R ^b , -N(R ^c )R ^d ,

phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R ^e , and a 3-, 4-, 5-, 6- or 7- membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N , O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals R ^e , for p > 1 it being possible that R ³ are identical or different,

or two radicals R ³ bound on adjacent carbon atoms may be together a group selected from -CH2CH2CH2CH2-, -CH=CH-CH=CH-, -N=CH-CH=CH-, -CH=N-CH=CH-, -N=CH-

N=CH-, -OCH2CH2CH2-, -OCH=CHCH ₂ -, -CH ₂ OCH ₂ CH ₂ -, -OCH2CH2O-, -OCH2OCH2-, -CH2CH2CH2-, -CH=CHCH ₂ -, -CH2CH2O-, -CH=CHO-, -CH2OCH2-, -CH ₂ C(=0)0-, -C(=0)OCH ₂ -, -0(CH ₂ )0-, -SCH2CH2CH2-, -SCH=CHCH ₂ -, -CH ₂ SCH ₂ CH ₂ -, -SCH2CH2S-, -SCH2SCH2-, -CH2CH2S-, -CH=CHS-, -CH2SCH2-, -CH ₂ C(=S)S-, -C(=S)SCH ₂ -, -S(CH ₂ )S-, -CH ₂ CH ₂ N Rq-,-CH ₂ CH=N-, -CH=CH-N R ^c i-, -OCH=N- and -SCH=N-, thus forming, together with the carbon atoms to which they are bound, a 5- or 6-membered ring, where the hydrogen atoms of the above groups may be replaced by one or more substituents selected from halogen, methyl, halomethyl, hydroxyl, methoxy and halomethoxy or one or more CH2 groups of the above groups may be replaced by a C=0 group;

R ^a is selected from the group consisting of Ci-C6-alkoxy, Ci-C6-haloalkoxy, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, C ₂ -C ₆ -alkenyl, -OR ^b , -SR ^b , -S(0) _m R ^b , -N(R ^c )R ^d ,

phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R ^e , and a 3-, 4-, 5-, 6- or 7- membered saturated, partially unsaturated or completely unsaturated heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N , O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals R ^e ;

or two radicals R ^a , together with the carbon atoms to which they are bound, form a 3-, 4-,

5- , 6-, 7- or 8-membered saturated or partially unsaturated carbocyclic ring or a 3-, 4-, 5-,

6- , 7- or 8-membered saturated or partially unsaturated heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N , O, S, NO, SO and SO2, as ring members;

wherein, in the case of more than one R ^a , R ^a can be identical or different;

R ^aa is selected from the group consisting of CN , Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci- C6-haloalkoxy, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, -OR ^b , - SR , -S(0) _m R , -N(R ^c )R ^d , C(=0) N(R ^c )R ^d ,

phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R ^e , and a 3-, 4-, 5-, 6- or 7- membered saturated, partially unsaturated or completely unsaturated heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N , O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals R ^e ;

or two geminally bound radicals R ^aa together form a group selected from =CR ^h R ^k ;

R ^b is selected from the group consisting of H , Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs- Cs-cycloalkyl, C3-C8-cycloalkyl-Ci-C4-alkyl, where the five last mentioned radicals may be unsubstituted, partially or fully halogenated and/or wherein one or two CH2 groups may be replaced by a CO group; and/or may carry 1 -2 radicals selected from Ci-C6-alkoxy, C1-C6- haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Ci-C6-alkylsulfinyl, Ci-C6-haloalkylsulfinyl, Ci-C6-alkylsulfonyl, Ci-C6-haloalkylsulfonyl, phenyl, benzyl, pyridyl and phenoxy, it being possible for phenyl, benzyl, pyridyl and phenoxy to be unsubstituted, partially or fully halo- genated and/or to carry 1 , 2 or 3 substituents selected from the group consisting of C1-C6- alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, and C1-C6 haloalkoxy;

R ^d are, independently from one another, selected from the group consisting of H, CN, C1-C6- alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, C3-C8-cycloalkyl-Ci-C4-alkyl, where the five last mentioned radicals may be unsubstituted, partially or fully halogenated and/or wherein one or two Chb groups may be replaced by a CO group; and/or may carry 1 or 2 radicals selected from Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, Ci-C6-haloalkylthio, phenyl, benzyl, pyridyl and phenoxy, it being possible for phenyl, benzyl, pyridyl and phenoxy to be unsubstituted, partially or fully halogenated and/or to carry 1 , 2 or 3 substituents selected from the group consisting of C1-C6- alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, and C1-C6 haloalkoxy;

or R ^c and R ^d , together with the nitrogen atom to which they are bound, form a 3-, 4-, 5-, 6- or 7-membered saturated, partly unsaturated or completely unsaturated N-heterocyclic ring which may contain 1 or 2 further heteroatoms selected from N, O and S as ring members, where the heterocyclic ring may carry 1 , 2, 3 or 4 substituents selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy;

is selected from the group consisting of halogen, CN, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl and Cs-Cs-cycloalkyl, where the four last-mentioned radicals may be

unsubstituted, partially or fully halogenated and/or wherein one or two CH2 groups may be replaced by a CO group, and/or may carry 1 -2 radicals selected from Ci-C4-alkoxy, C1-C6- alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Ci-C6-alkylsulfinyl, C1-C6- haloalkylsulfinyl, Ci-C6-alkylsulfonyl, Ci-C6-haloalkylsulfonyl, phenyl, benzyl, pyridyl and phenoxy, it being possible for phenyl, benzyl, pyridyl and phenoxy to be unsubstituted, partially or fully halogenated and/or to carry 1 , 2 or 3 substituents selected from the group consisting of Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, and C1-C6 haloalkoxy;

wherein, in the case of more than one R ^e , R ^e can be identical or different;

R9 are, independently of each other and independently of each occurrence, selected from the group consisting of Ci-C4-alkyl, C3-C6-cycloalkyl, Ci-C4-alkoxy-Ci-C4-alkyl, C3-C8- cycloalkyl-Ci-C4-alkyl, phenyl and benzyl;

R ^k are, independently from one another, selected from the group consisting of H, halogen, CN, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and Cs-Cs-cycloalkyl, where the four last mentioned radicals may be unsubstituted, partially or fully halogenated and/or oxgenated, and/or may carry 1 or 2 radicals selected from Ci-C4-alkyl; Ci-C4-haloalkyl; Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, C1-C6- haloalkylthio, -OH, -SH, phenyl, benzyl, pyridyl and phenoxy, it being possible for phenyl, benzyl, pyridyl and phenoxy to be unsubstituted, partially or fully halogenated and/or to carry 1 , 2 or 3 substituents selected from the group consisting of Ci-C6-alkyl, C1-C6- haloalkyl, Ci-C6-alkoxy, C1-C6 haloalkoxy; (Ci-C6-alkyl)amino, di-(Ci-C6-alkyl)amino;

is selected from the group consisting of H, CN, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl and C3-Cs-cycloalkyl-Ci-C4-alkyl;

is 1 or 2, wherein, in the case of several occurrences, m may be identical or different; is 0, 1 or 2; wherein, in the case of several occurrences, n may be identical or different. The process is hereinafter also referred to as "process B".

The process B represents a novel straightforward process for the preparation of N- pyridylpyrazole carboxanilide compounds. The process is particularly advantageous in that the N-pyridylpyrazole carboxanilide compounds are obtained in high yields and high purity, so that they can be used, e.g., in the preparation of compounds of formula (I) without purification.

In view of the above, the present invention also relates to a process for preparing a compound of formula (I) comprising the steps of preparing a compound of formula (II) as defined above, optionally converting said compound into a compound of formula (Ι ),

and then reacting the compound of formula (II) or (ll ^* ) with a compound of formula (III) or a salt thereof to give a compound of formula (I), wherein the variables p, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and X in the compounds of formulae (Ι ), (III) and (I) are as defined above for process A.

In a ula (I I. A') or (Ι .Α')

wherein

R ^x is Ci-C6-alkyl, benzyl or phenyl, wherein the phenyl radical may be substituted by one or more radicals selected from halogen and NO2;

X is halogen, OC(0)Ci-C ₆ -alkyl, OS(0) ₂ Ci-C ₆ -alkyl, OS(0) ₂ Ci-C ₆ -haloalkyl, OS(0) ₂ benzyl, OS(0) ₂ tolyl or OH;

R ¹ is selected from H, halogen, CN, CBrF ₂ , Ci-C6-alkyl, Ci-C6-fluoroalkyl, C ₂ -C6-alkenyl, and C ₂ -C6-fluoroalkenyl, wherein the four last mentioned radicals may be substituted by one or more radicals R ^a ;

R ² is selected from the group consisting of C ₂ -C6-alkyl, Ci-C6-fluoroalkyl, C ₂ -C6-alkenyl, C ₂ - C6-fluoroalkenyl, wherein the four last mentioned radicals may be substituted by one or more radicals R ^a ; Cs-Cs-cycloalkyI, which is unsubstituted, partially or completely halogenated or carries one or more radicals R ^aa ;

phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R ^e , and a 3-, 4-, 5-, 6- or 7- membered saturated, partially unsaturated or completely unsaturated heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals R ^e ;

R ^3b are independently selected from the group consisting of halogen, CN, d-Cs-alkyl, Ci- Cs-haloalkyl, C2-Cs-alkenyl, C2-C8-haloalkenyl, C2-Cs-alkynyl, C2-C8-haloalkynyl, wherein the six last radicals may optionally be substituted by one or more radicals R ^a ,

Cs-Cs-cycloalkyI, which is unsubstituted, partially or completely halogenated or carries one or more radicals R ^aa ;

-OR ^b , -SR ^b , -S(0) _m R ^b , -N(R ^c )R ^d ,

phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R ^e , and a 3-, 4-, 5-, 6- or 7- membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals R ^e , is selected from the group consisting of Ci-C6-alkoxy, Ci-C6-haloalkoxy, Cs-Cs-cycloalkyI, Cs-Cs-halocycloalkyl, C ₂ -C ₆ -alkenyl, -OR ^b , -SR ^b , -S(0) _m R ^b , -N(R ^c )R ^d ,

phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R ^e , and a 3-, 4-, 5-, 6- or 7- membered saturated, partially unsaturated or completely unsaturated heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals R ^e ;

or two radicals R ^a , together with the carbon atoms to which they are bound, form a 3-, 4-,

5- , 6-, 7- or 8-membered saturated or partially unsaturated carbocyclic ring or a 3-, 4-, 5-,

6- , 7- or 8-membered saturated or partially unsaturated heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members;

wherein, in the case of more than one R ^a , R ^a can be identical or different;

is selected from the group consisting of CN, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci- C6-haloalkoxy, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, -Si(R ^f ) ₂ R9, -OR , -SR , -S(0) _m R , -N(R ^c )R ^d ;

phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R ^e , and a 3-, 4-, 5-, 6- or 7- membered saturated, partially unsaturated or completely unsaturated heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals R ^e ;

or two geminally bound radicals R ^aa together form a group selected from =CR ^h R ^k ;

is selected from the group consisting of H, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3- Ce-cycloalkyl, C3-C8-cycloalkyl-Ci-C4-alkyl, where the five last mentioned radicals may be unsubstituted, partially or fully halogenated and/or wherein one or two CH2 groups may be replaced by a CO group; and/or may carry 1 -2 radicals selected from Ci-C6-alkoxy, C1-C6- haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Ci-C6-alkylsulfinyl, Ci-C6-haloalkylsulfinyl, Ci-C6-alkylsulfonyl, Ci-C6-haloalkylsulfonyl, phenyl, benzyl, pyridyl and phenoxy, it being possible for phenyl, benzyl, pyridyl and phenoxy to be unsubstituted, partially or fully halogenated and/or to carry 1 , 2 or 3 substituents selected from the group consisting of C1-C6- alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, and C1-C6 haloalkoxy;

R ^d are, independently from one another, selected from the group consisting of H, CN, C1-C6- alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, C3-C8-cycloalkyl-Ci-C4-alkyl, where the five last mentioned radicals may be unsubstituted, partially or fully halogenated and/or wherein one or two Chb groups may be replaced by a CO group; and/or may carry 1 or 2 radicals selected from Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, Ci-C6-haloalkylthio, phenyl, benzyl, pyridyl and phenoxy, it being possible for phenyl, benzyl, pyridyl and phenoxy to be unsubstituted, partially or fully halogenated and/or to carry 1 , 2 or 3 substituents selected from the group consisting of C1-C6- alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and C1-C6 haloalkoxy;

or R ^c and R ^d , together with the nitrogen atom to which they are bound, form a 3-, 4-, 5-, 6- or 7-membered saturated, partly unsaturated or completely unsaturated N-heterocyclic ring which may contain 1 or 2 further heteroatoms selected from N, O and S as ring members, where the heterocyclic ring may carry 1 , 2, 3 or 4 substituents selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy;

is selected from the group consisting of halogen, CN, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl and Cs-Cs-cycloalkyl, where the four last-mentioned radicals may be

unsubstituted, partially or fully halogenated and/or wherein one or two CH2 groups may be replaced by a CO group, and/or may carry 1 -2 radicals selected from Ci-C4-alkoxy, C1-C6- alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Ci-C6-alkylsulfinyl, C1-C6- haloalkylsulfinyl, Ci-C6-alkylsulfonyl, Ci-C6-haloalkylsulfonyl, phenyl, benzyl, pyridyl and phenoxy, it being possible for phenyl, benzyl, pyridyl and phenoxy to be unsubstituted, partially or fully halogenated and/or to carry 1 , 2 or 3 substituents selected from the group consisting of Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and C1-C6 haloalkoxy;

wherein, in the case of more than one R ^e , R ^e can be identical or different;

R9 are, independently of each other and independently of each occurrence, selected from the group consisting of Ci-C4-alkyl, C3-C6-cycloalkyl, Ci-C4-alkoxy-Ci-C4-alkyl, C3-C8- cycloalkyl-Ci-C4-alkyl, phenyl and benzyl;

R ^k are, independently from one another, selected from the group consisting of H, halogen, CN, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and Cs-Cs-cycloalkyl, where the four last mentioned radicals may be unsubstituted, partially or fully halogenated and/or oxgenated, and/or may carry 1 or 2 radicals selected from Ci-C4-alkyl; Ci-C4-haloalkyl; Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, C1-C6- haloalkylthio, -Si(R ^f )2R ^g , -OH, -SH, phenyl, benzyl, pyridyl and phenoxy, it being possible for phenyl, benzyl, pyridyl and phenoxy to be unsubstituted, partially or fully halogenated and/or to carry 1 , 2 or 3 substituents selected from the group consisting of Ci-C6-alkyl, Ci- C6-haloalkyl, Ci-C6-alkoxy, C1-C6 haloalkoxy, (Ci-C6-alkyl)amino, di-(Ci-C6-alkyl)amino; is 1 or 2, wherein, in the case of several occurrences, m may be identical or different; is 0, 1 or 2; wherein, in the case of several occurrences, n may be identical or different. In y rmula (II.A") or (Ι .Α")

wherein

is Ci-C6-alkyl, benzyl or phenyl, wherein the phenyl radical may be substituted by one or more radicals selected from halogen and NO2;

is halogen, OC(0)Ci-C ₆ -alkyl, OS(0) ₂ Ci-C ₆ -alkyl, OS(0) ₂ Ci-C ₆ -haloalkyl, OS(0) ₂ benzyl, OS(0) ₂ tolyl or OH;

is selected from H, halogen, CN, CBrF ₂ , Ci-C6-alkyl, Ci-C6-fluoroalkyl, C ₂ -C6-alkenyl, and C ₂ -C6-fluoroalkenyl, wherein the four last mentioned radicals may be substituted by one or more radicals R ^a ;

is selected from the group consisting of halogen, Ci-C6-alkyl, Ci-C6-fluoroalkyl, C ₂ -C6- alkenyl, C ₂ -C6-fluoroalkenyl, wherein the four last mentioned radicals may be substituted by one or more radicals R ^a ;

Cs-Cs-cycloalkyI, which is unsubstituted, partially or completely halogenated or carries one or more radicals R ^aa ;

phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R ^e , and a 3-, 4-, 5-, 6- or 7- membered saturated, partially unsaturated or completely unsaturated heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and S0 ₂ , as ring members, where the heterocyclic ring may be substituted by one or more radicals R ^e ;

R ^3b are independently selected from the group consisting of halogen, CN, Ci-Cs-alkyl, Ci- Cs-haloalkyl, C ₂ -Cs-alkenyl, C ₂ -C8-haloalkenyl, C ₂ -Cs-alkynyl, C ₂ -C8-haloalkynyl, wherein the six last radicals may optionally be substituted by one or more radicals R ^a ,

Cs-Cs-cycloalkyI, which is unsubstituted, partially or completely halogenated or carries one or more radicals R ^aa ;

-OR ^b , -SR ^b , -S(0) _m R ^b , -N(R ^c )R ^d ,

phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R ^e , and a 3-, 4-, 5-, 6- or 7- membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and S0 ₂ , as ring members, where the heterocyclic ring may be substituted by one or more radicals R ^e , is selected from the group consisting of Ci-C6-alkoxy, Ci-C6-haloalkoxy, Cs-Cs-cycloalkyI, Cs-Cs-halocycloalkyl, C ₂ -C ₆ -alkenyl, -OR ^b , -SR ^b , -S(0) _m R ^b , -N(R ^c )R ^d ,

phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R ^e , and a 3-, 4-, 5-, 6- or 7- membered saturated, partially unsaturated or completely unsaturated heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals R ^e ;

or two radicals R ^a , together with the carbon atoms to which they are bound, form a 3-, 4-,

5- , 6-, 7- or 8-membered saturated or partially unsaturated carbocyclic ring or a 3-, 4-, 5-,

6- , 7- or 8-membered saturated or partially unsaturated heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members;

wherein, in the case of more than one R ^a , R ^a can be identical or different;

is selected from the group consisting of CN, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci- C6-haloalkoxy, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, - Si(R ^f ) ₂ R9, -OR ^b , -SR ^b , -S(0) _m R ^b , -N(R ^c )R ^d ;

phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R ^e , and a 3-, 4-, 5-, 6- or 7- membered saturated, partially unsaturated or completely unsaturated heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals R ^e ;

or two geminally bound radicals R ^aa together form a group selected from =CR ^h R ^k ;

is selected from the group consisting of H, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs- Cs-cycloalkyl, C3-C8-cycloalkyl-Ci-C4-alkyl, where the five last mentioned radicals may be unsubstituted, partially or fully halogenated and/or wherein one or two CH2 groups may be replaced by a CO group; and/or may carry 1 -2 radicals selected from Ci-C6-alkoxy, C1-C6- haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Ci-C6-alkylsulfinyl, Ci-C6-haloalkylsulfinyl, Ci-C6-alkylsulfonyl, Ci-C6-haloalkylsulfonyl, phenyl, benzyl, pyridyl and phenoxy, it being possible for phenyl, benzyl, pyridyl and phenoxy to be unsubstituted, partially or fully halogenated and/or to carry 1 , 2 or 3 substituents selected from the group consisting of C1-C6- alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, and C1-C6 haloalkoxy;

R ^d are, independently from one another, selected from the group consisting of H, CN, C1-C6- alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, C3-C8-cycloalkyl-Ci-C4-alkyl, where the five last mentioned radicals may be unsubstituted, partially or fully halogenated and/or wherein one or two CH2 groups may be replaced by a CO group; and/or may carry 1 or 2 radicals selected from Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, Ci-C6-haloalkylthio, phenyl, benzyl, pyridyl and phenoxy, it being possible for phenyl, benzyl, pyridyl and phenoxy to be unsubstituted, partially or fully halogenated and/or to carry 1 , 2 or 3 substituents selected from the group consisting of C1-C6- alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and C1-C6 haloalkoxy;

or R ^c and R ^d , together with the nitrogen atom to which they are bound, form a 3-, 4-, 5-, 6- or 7-membered saturated, partly unsaturated or completely unsaturated N-heterocyclic ring which may contain 1 or 2 further heteroatoms selected from N, O and S as ring members, where the heterocyclic ring may carry 1 , 2, 3 or 4 substituents selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy;

is selected from the group consisting of halogen, CN, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl and Cs-Cs-cycloalkyl, where the four last-mentioned radicals may be

unsubstituted, partially or fully halogenated and/or wherein one or two CH2 groups may be replaced by a CO group, and/or may carry 1 -2 radicals selected from Ci-C4-alkoxy, C1-C6- alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Ci-C6-alkylsulfinyl, C1-C6- haloalkylsulfinyl, Ci-C6-alkylsulfonyl, Ci-C6-haloalkylsulfonyl, phenyl, benzyl, pyridyl and phenoxy, it being possible for phenyl, benzyl, pyridyl and phenoxy to be unsubstituted, partially or fully halogenated and/or to carry 1 , 2 or 3 substituents selected from the group consisting of Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and C1-C6 haloalkoxy;

wherein, in the case of more than one R ^e , R ^e can be identical or different;

R ^f , R9 are, independently of each other and independently of each occurrence, selected from the group consisting of Ci-C4-alkyl, C3-C6-cycloalkyl, Ci-C4-alkoxy-Ci-C4-alkyl, C3-C8- cycloalkyl-Ci-C4-alkyl, phenyl and benzyl;

R ^h , R ^k are, independently from one another, selected from the group consisting of H, halogen, CN, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and Cs-Cs-cycloalkyl, where the four last mentioned radicals may be unsubstituted, partially or fully halogenated and/or oxgenated, and/or may carry 1 or 2 radicals selected from Ci-C4-alkyl; Ci-C4-haloalkyl; Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, C1-C6- haloalkylthio, -Si(R ^f )2R ^g , -OH, -SH, phenyl, benzyl, pyridyl and phenoxy, it being possible for phenyl, benzyl, pyridyl and phenoxy to be unsubstituted, partially or fully halogenated and/or to carry 1 , 2 or 3 substituents selected from the group consisting of Ci-C6-alkyl, Ci- C6-haloalkyl, Ci-C6-alkoxy, C1-C6 haloalkoxy, (Ci-C6-alkyl)amino, di-(Ci-C6-alkyl)amino; m is 1 or 2, wherein, in the case of several occurrences, m may be identical or different; n is 0, 1 or 2; wherein, in the case of several occurrences, n may be identical or different; with the proviso that R ^3a is not CH3 or CI.

The compounds of formulae (ΙΙ.Α'), (Ι .Α'), (II.A") and (Ι .Α") represent versatile reaction tools for the preparation of compounds of formula (I). The compounds of formulae (II.A) and (Ι .Α') may advantageously be used in the preparation of compounds of formula (I), wherein R ¹ is CI, R ² is CF ₃ , R ^3a is CH ₃ and R ^3b is CI. The compounds of formulae (II.A") and (ll ^* .A") may advantageously be used in the preparation of compounds such as cyclaniliprole, which is a well known anthranilamide insecticide.

Further embodiments of the present invention can be found in the claims, the description and the examples. It is to be understood that the features mentioned above and those still to be illustrated below of the subject matter of the invention can be applied not only in the respective given combination but also in other combinations without leaving the scope of the invention.

In the context of the present invention, the terms used generically are each defined as follows: The prefix C _x -C _y refers in the particular case to the number of possible carbon atoms.

The term "halogen" denotes in each case fluorine, bromine, chlorine or iodine, in particular fluorine, chlorine or bromine.

The term "partially or fully halogenated" will be taken to mean that 1 or more, e.g. 1 , 2, 3, 4 or 5 or all of the hydrogen atoms of a given radical have been replaced by a halogen atom, in particular by fluorine or chlorine. The term "alkyl" as used herein (and in the alkyl moieties of other groups comprising an alkyl group, e.g. alkoxy, alkylcarbonyl, alkylthio, alkylsulfinyl, alkylsulfonyl and alkoxyalkyl) denotes in each case a straight-chain or branched alkyl group having usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms and in particular from 1 to 3 carbon atoms. Examples of an alkyl group are methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2- butyl, iso-butyl, tert-butyl, n-pentyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2- dimethylpropyl, 1 -ethylpropyl, n-hexyl, 1 ,1 -dimethylpropyl, 1 ,2-dimethylpropyl, 1 -methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1 -dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3- dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1 -ethylbutyl, 2-ethylbutyl, 1 ,1 ,2-trimethylpropyl, 1 ,2,2-trimethylpropyl, 1 -ethyl-1 -methylpropyl, 1 -ethyl-2-methylpropyl, n- heptyl, 1 -methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1 - ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, n-octyl, 1 -methyloctyl, 2-methylheptyl, 1 -ethylhexyl, 2- ethylhexyl, 1 ,2-dimethylhexyl, 1 -propylpentyl and 2-propylpentyl.

The term "alkylene" (or alkanediyl) as used herein in each case denotes an alkyl radical as de- fined above, wherein one hydrogen atom at any position of the carbon backbone is replaced by one further binding site, thus forming a bivalent moiety.

The term "haloalkyl" as used herein (and in the haloalkyl moieties of other groups comprising a haloalkyl group, e.g. haloalkoxy and haloalkylthio) denotes in each case a straight-chain or branched alkyl group having usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, wherein the hydrogen atoms of this group are partially or totally replaced with halogen atoms. Preferred haloalkyl moieties are selected from Ci-C4-haloalkyl, more preferably from Ci- C2-haloalkyl, more preferably from halomethyl, in particular from Ci-C2-fluoroalkyl such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 -fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, and the like.

The term "fluoroalkyl", as used herein (and in the fluoroalkyl units of fluoroalkoxy,

fluoroalkylthio, fluoroalkylsulfinyl and fluoroalkylsulfonyl) denotes in each case straight-chain or branched alkyl groups having usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms and in particular 1 to 4 carbon atoms, wherein the hydrogen atoms of this group are partially or totally replaced with fluorine atoms. Examples thereof are fluoromethyl, difluoromethyl, trifluoromethyl, 1 -fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl,

pentafluoroethyl, 3,3,3-trifluoroprop-1 -yl, 1 ,1 ,1 -trifl uoroprop-2-yl , heptafluoroisopropyl, 1 - fluorobutyl, 2-fluorobutyl, 3-fluorobutyl, 4-fluorobutyl, 4,4,4-trifluorobutyl, fluoro-tert-butyl and the like.

The term "cycloalkyl" as used herein (and in the cycloalkyl moieties of other groups comprising a cycloalkyl group, e.g. cycloalkoxy and cycloalkylalkyl) denotes in each case a mono- or bicy- clic cycloaliphatic radical having usually from 3 to 10 carbon atoms, 3 to 8 carbon atoms or 3 to 6 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo[2.1 .1 ]hexyl, bicyclo[3.1 .1 ]heptyl, bicyclo[2.2.1]heptyl, and bicyclo[2.2.2]octyl.

The term "halocycloalkyi" as used herein (and in the halocycloalkyi moieties of other groups comprising an halocycloalkyi group, e.g. halocycloalkylmethyl) denotes in each case a mono- or bicyclic cycloaliphatic radical having usually from 3 to 10 carbon atoms, 3 to 8 carbon atoms or 3 to 6 carbon atoms, wherein at least one, e.g. 1 , 2, 3, 4 or 5 of the hydrogen atoms are replaced by halogen, in particular by fluorine or chlorine. Examples are 1 - and 2-fluorocyclopropyl, 1 ,2-, 2,2- and 2,3-difluorocyclopropyl, 1 ,2,2-trifluorocyclopropyl, 2,2,3,3-tetrafluorocyclpropyl, 1 - and 2-chlorocyclopropyl, 1 ,2-, 2,2- and 2,3-dichlorocyclopropyl, 1 ,2,2-trichlorocyclopropyl, 2,2,3,3-tetrachlorocyclpropyl, 1 -,2- and 3-fluorocyclopentyl, 1 ,2-, 2,2-, 2,3-, 3,3-, 3,4-, 2,5- difluorocyclopentyl, 1 -,2- and 3-chlorocyclopentyl, 1 ,2-, 2,2-, 2,3-, 3,3-, 3,4-,

2,5-dichlorocyclopentyl and the like.

The term "cycloalkylalkyl" as used herein denotes in each case alkyl as defined above, usually comprising 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, wherein 1 carbon atom carries a cycloalkyl radical as defined above, usually comprising from 3 to 10 carbon atoms, 3 to 8 carbon atoms or 3 to 6 carbon atoms as defined above. Examples are cyclopropylmethyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclohexylethyl and the like.

The term "fluorocylcoalkyl" as used herein, denotes a halocycloalkyl radical, as defined above, wherein the one or more halogen atoms are fluorine atoms.

The term "alkenyl" as used herein denotes in each case a singly unsaturated hydrocarbon rad- ical, i.e. a hydrocarbon radical having a carbon-carbon double bond, having usually 2 to 10, preferably 2 to 4 carbon atoms, e.g. vinyl, allyl (2-propen-1 -yl), 1 -propen-1 -yl, 2-propen-2-yl, methallyl (2-methylprop-2-en-1 -yl), 2-buten-1 -yl, 3-buten-1 -yl, 2-penten-1 -yl, 3-penten-1 -yl, 4- penten-1 -yl, 1 -methylbut-2-en-1 -yl, 2-ethylprop-2-en-1 -yl and the like.

The term "alkenylene" (or alkenediyl) as used herein in each case denotes an alkenyl radical as defined above, wherein one hydrogen atom at any position of the carbon backbone is replaced by one further binding site, thus forming a bivalent moiety.

The term "haloalkenyl" as used herein, which may also be expressed as "alkenyl which may be substituted by halogen", and the haloalkenyl moieties in haloalkenyloxy, haloalkenylcarbonyl and the like refers to unsaturated straight-chain or branched hydrocarbon radicals having 2 to 10 ("C2-Cio-haloalkenyl") or 2 to 6 ("C2-C6-haloalkenyl") carbon atoms and a double bond in any position, where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine, for example chlorovinyl, chloroallyl and the like.

The term "fluoroalkenyl" as used herein, denotes a haloalkenyl radical, as defined above, wherein the one or more halogen atoms are fluorine atoms.

The term "alkynyl" as used herein denotes unsaturated straight-chain or branched hydrocarbon radicals having usually 2 to 10, frequently 2 to 6, preferably 2 to 4 carbon atoms and one or two carbon-carbon triple bonds in any position, e.g. ethynyl, propargyl (2-propyn-1 -yl), 1 -propyn- 1 -yl, 1 -methylprop-2-yn-1 -yl), 2-butyn-1 -yl, 3-butyn-1 -yl, 1 -pentyn-1 -yl, 3-pentyn-1 -yl, 4-pentyn- 1 -yl, 1 -methylbut-2-yn-1 -yl, 1 -ethylprop-2-yn-1 -yl and the like.

The term "alkynylene" (or alkynediyl) as used herein in each case denotes an alkynyl radical as defined above, wherein one hydrogen atom at any position of the carbon backbone is replaced by one further binding site, thus forming a bivalent moiety.

The term "haloalkynyl" as used herein, which is also expressed as "alkynyl which may be sub- stituted by halogen", refers to unsaturated straight-chain or branched hydrocarbon radicals having usually 3 to 10 carbon atoms, frequently 2 to 6, preferably 2 to 4 carbon atoms, and one or two triple bonds in any position (as mentioned above), where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine.

The term "alkoxy" as used herein denotes in each case a straight-chain or branched alkyl group usually having from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, which is bound to the remainder of the molecule via an oxygen atom. Examples of an alkoxy group are methoxy, ethoxy, n-propoxy, iso-propoxy, n-butyloxy, 2-butyloxy, iso-butyloxy, tert-butyloxy, and the like.

The term "haloalkoxy" as used herein denotes in each case a straight-chain or branched alkoxy group, as defined above, having from 1 to 10 carbon atoms, frequently from 1 to 6 car- bon atoms, preferably 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, wherein the hydrogen atoms of this group are partially or totally replaced with halogen atoms, in particular fluorine atoms. Preferred haloalkoxy moieties include Ci-C4-haloalkoxy, in particular halomethoxy, and also in particular Ci-C2-fluoroalkoxy, such as fluoromethoxy, difluoromethoxy, trifluoromethoxy,

1 - fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoro-ethoxy, 2,2-dichloro-2-fluorethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy and the like.

The term "alkoxy-alkyl" as used herein denotes in each case alkyl usually comprising 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, wherein 1 carbon atom carries an alkoxy radical usually comprising 1 to 10, frequently 1 to 6, in particular 1 to 4, carbon atoms as defined above. Examples are CH ₂ OCH ₃ , CH2-OC2H5, n-propoxymethyl, CH ₂ -OCH(CH ₃ )2, n- butoxymethyl, (l -methylpropoxy)-methyl, (2-methylpropoxy)methyl, CH2-OC(CH3)3, 2- (methoxy)ethyl, 2-(ethoxy)ethyl, 2-(n-propoxy)-ethyl, 2-(1 -methylethoxy)-ethyl, 2-(n-butoxy)ethyl,

2- (1 -methylpropoxy)-ethyl, 2-(2-methylpropoxy)-ethyl, 2-(1 ,1 -dimethylethoxy)-ethyl, 2-(methoxy)- propyl, 2-(ethoxy)-propyl, 2-(n-propoxy)-propyl, 2-(1 -methylethoxy)-propyl, 2-(n-butoxy)-propyl, 2-(1 -methylpropoxy)-propyl, 2-(2-methylpropoxy)-propyl, 2-(1 ,1 -dimethylethoxy)-propyl, 3- (methoxy)-propyl, 3-(ethoxy)-propyl, 3-(n-propoxy)-propyl, 3-(1 -methylethoxy)-propyl, 3-(n- butoxy)-propyl, 3-(1 -methylpropoxy)-propyl, 3-(2-methylpropoxy)-propyl, 3-(1 ,1 -dimethylethoxy)- propyl, 2-(methoxy)-butyl, 2-(ethoxy)-butyl, 2-(n-propoxy)-butyl, 2-(1 -methylethoxy)-butyl, 2-(n- butoxy)-butyl, 2-(1 -methylpropoxy)-butyl, 2-(2-methyl-propoxy)-butyl, 2-(1 ,1 -dimethylethoxy)- butyl, 3-(methoxy)-butyl, 3-(ethoxy)-butyl, 3-(n-propoxy)-butyl, 3-(1 -methylethoxy)-butyl, 3-(n- butoxy)-butyl, 3-(1 -methylpropoxy)-butyl, 3-(2-methylpropoxy)-butyl, 3-(1 ,1 -dimethylethoxy)- butyl, 4-(methoxy)-butyl, 4-(ethoxy)-butyl, 4-(n-propoxy)-butyl, 4-(1 -methylethoxy)-butyl, 4-(n- butoxy)-butyl, 4-(1 -methylpropoxy)-butyl, 4-(2-methylpropoxy)-butyl, 4-(1 ,1 -dimethylethoxy)- butyl and the like.

The term "fluoroalkoxy-alkyl" as used herein denotes in each case alkyl as defined above, usually comprising 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, wherein 1 carbon atom carries an fluoroalkoxy radical as defined above, usually comprising 1 to 10, frequently 1 to 6, in particular 1 to 4, carbon atoms as defined above. Examples are fluoromethoxymethyl, difluoromethoxymethyl, trifluoromethoxymethyl, 1 -fluoroethoxymethyl, 2-fluoroethoxymethyl, 1 ,1 -difluoroethoxymethyl, 1 ,2-difluoroethoxymethyl, 2,2-difluoroethoxymethyl,

1 ,1 ,2-trifluoroethoxymethyl, 1 ,2,2-trifluoroethoxymethyl, 2,2,2-trifluoroethoxymethyl,

pentafluoroethoxymethyl, 1 -fluoroethoxy-1 -ethyl, 2-fluoroethoxy-1 -ethyl, 1 ,1 -difluoroethoxy-1 - ethyl, 1 ,2-difluoroethoxy-1 -ethyl, 2,2-difluoroethoxy-1 -ethyl, 1 ,1 ,2-trifluoroethoxy-1 -ethyl, 1 ,2,2- trifluoroethoxy-1 -ethyl, 2,2,2-trifluoroethoxy-1 -ethyl, pentafluoroethoxy-1 -ethyl, 1 -fluoroethoxy-2- ethyl, 2-fluoroethoxy-2-ethyl, 1 ,1 -difluoroethoxy-2 -ethyl, 1 ,2-difluoroethoxy-2-ethyl, 2,2- difluoroethoxy-2-ethyl, 1 ,1 ,2-trifluoroethoxy-2-ethyl, 1 ,2,2-trifluoroethoxy-2-ethyl, 2,2,2- trifluoroethoxy-2-ethyl, pentafluoroethoxy-2-ethyl, and the like.

The term "alkylthio" (also alkylsulfanyl or alkyl-S-)" as used herein denotes in each case a straight-chain or branched saturated alkyl group as defined above, usually comprising 1 to 10 carbon atoms, frequently comprising 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, which is attached via a sulfur atom at any position in the alkyl group. Examples are methylthio, ethylthio, n-propylthio, iso-propylthio, n-butylthio, 2-butylthio, iso-butylthio, tert-butylthio, and the like.

The term "haloalkylthio" as used herein refers to an alkylthio group as defined above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine. Examples are fluoromethylthio, difluoromethylthio, trifluoromethylthio, 1 -fluoroethylthio, 2- fluoroethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro- 2,2-difluoro-ethylthio, 2,2-dichloro-2-fluorethylthio, 2,2,2-trichloroethylthio, pentafluoroethylthio and the like

The terms "alkylsulfinyl" and "S(0) _n -alkyl" (wherein n is 1 ) are equivalent and, as used herein, denote an alkyl group, as defined above, attached via a sulfinyl [S(O)] group. For example, the term "Ci -C6-a I kylsu If i nyl " refers to a Ci-C6-alkyl group, as defined above, attached via a sulfinyl [S(O)] group. Examples are methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, 1 -methylethylsulfinyl (isopropylsulfinyl), butyl sulfinyl, 1 -methylpropylsulfinyl (sec-butylsulfinyl), 2-methylpropylsulfinyl (isobutylsulfinyl), 1 ,1 -dimethylethylsulfinyl (tert-butylsulfinyl), pentylsulfinyl, 1 -methylbutylsulfinyl,

2- methylbutylsulfinyl, 3-methylbutylsulfinyl, 1 ,1 -dimethylpropylsulfinyl, 1 ,2-dimethylpropylsulfinyl, 2,2-dimethylpropylsulfinyl, 1 -ethylpropylsulfinyl, hexylsulfinyl, 1 -methylpentylsulfinyl, 2- methylpentylsulfinyl, 3-methylpentylsulfinyl, 4-methylpentylsulfinyl, 1 ,1 -dimethylbutylsulfinyl,

1 .2- dimethylbutylsulfinyl, 1 ,3-dimethylbutylsulfinyl, 2,2-dimethylbutylsulfinyl,

2.3- dimethylbutylsulfinyl, 3,3-dimethylbutylsulfinyl, 1 -ethylbutylsulf inyl , 2-ethylbutylsulfinyl,

1 ,1 ,2-trimethylpropylsulfinyl, 1 ,2,2-trimethylpropylsulfinyl, 1 -ethyl-1 -methylpropylsulfinyl and 1 - ethyl-2-methylpropylsulfinyl.

The terms "haloalkylsulfinyl" and "S(0) _n -haloalkyl (wherein n is 1 ) as used herein refers to an alkylsulfinyl group as defined above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine. Examples are trifluormethylsulfinyl,

pentafluorethylsulfinyl and the like.

The terms "alkylsulfonyl" and "S(0) _n -alkyl" (wherein n is 2) are equivalent and, as used herein, denote an alkyl group, as defined above, attached via a sulfonyl [S(0)2] group. For example, the term "Ci-C6-alkylsulfonyl" refers to a Ci-C6-alkyl group, as defined above, attached via a sulfonyl [S(0)2] group. Examples are methylsulfonyl, ethylsulfonyl, n-propylsulfonyl,

1 -methylethylsulfonyl (isopropylsulfonyl), butylsulfonyl, 1 -methylpropylsulfonyl (sec- butylsulfonyl), 2-methylpropylsulfonyl (isobutylsulfonyl), 1 ,1 -dimethylethylsulfonyl (tert- butylsulfonyl), pentylsulfonyl, 1 -methylbutylsulfonyl, 2-methylbutylsulfonyl, 3-methylbutylsulfonyl, 1 ,1 -dimethylpropylsulfonyl, 1 ,2-dimethylpropylsulfonyl, 2,2-dimethylpropylsulfonyl,

1 -ethylpropylsulfonyl, hexylsulfonyl, 1 -methylpentylsulfonyl, 2-methylpentylsulfonyl,

3- methylpentylsulfonyl, 4-methylpentylsulfonyl, 1 ,1-dimethylbutylsulfonyl, 1 .2- dimethylbutylsulfonyl, 1 ,3-dimethylbutylsulfonyl, 2,2-dimethylbutylsulfonyl,

2.3- dimethylbutylsulfonyl, 3,3-dimethylbutylsulfonyl, 1 -ethylbutylsulfonyl, 2-ethylbutylsulfonyl,

1 ,1 ,2-trimethylpropylsulfonyl, 1 ,2,2-trimethylpropylsulfonyl, 1 -ethyl-1 -methylpropylsulfonyl and 1 - ethyl-2-methylpropylsulfonyl.

The term "haloalkylsulfonyl" and "S(0) _n -haloalkyl (wherein n is 2) as used herein refers to an alkylsulfonyl group as defined above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine. Examples are trifluormethylsulfonyl,

pentafluorethylsulfonyl and the like.

The term "alkylamino" as used herein denotes in each case a group -NHR, wherein R is a straight-chain or branched alkyl group usually having from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Examples of an alkylamino group are methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, 2-butylamino, iso-butylamino, tert-butylamino, and the like.

The term "dialkylamino" as used herein denotes in each case a group-NRR', wherein R and R', independently of each other, are a straight-chain or branched alkyl group each usually hav- ing from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Examples of a dialkylamino group are dimethylamino, diethylamino, dipropylamino, dibutylamino, methyl-ethyl-amino, methyl- propyl-amino, methyl-isopropylamino, methyl-butyl-amino, methyl-isobutyl-amino, ethyl-propyl- amino, ethyl-isopropylamino, ethyl-butyl-amino, ethyl-isobutyl-amino, and the like.

The suffix "-carbonyl" in a group denotes in each case that the group is bound to the remain- der of the molecule via a carbonyl C=0 group. This is the case e.g. in alkylcarbonyl,

haloalkylcarbonyl, alkoxycarbonyl and haloalkoxycarbonyl.

The term "aryl" as used herein refers to a mono-, bi- or tricyclic aromatic hydrocarbon radical having 6 to 14 carbon atoms. Examples thereof comprise phenyl, naphthyl, fluorenyl, azulenyl, anthracenyl and phenanthrenyl. Aryl is preferably phenyl or naphthyl and especially phenyl. The term "3-, 4-, 5-, 6-, 7- or 8-membered saturated carbocyclic ring" as used herein refers to carbocyclic rings, which are monocyclic and fully saturated. Examples of such rings include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane and the like.

The terms "3-, 4-, 5-, 6-, 7- or 8-membered partially unsaturated carbocyclic ring" and "5- or 6- membered partially unsaturated carbocyclic ring" refer to carbocyclic rings, which are monocyc- lie and have one or more degrees of unsaturation. Examples of such rings include include cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene and the like.

The term "3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or completely unsaturated heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members" [wherein "completely/fully unsaturated" includes also "aromatic"] as used herein denotes monocyclic radicals, the monocyclic radicals being saturated, partially unsaturated or fully unsaturated (including aromatic). The heterocyclic ring may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member. Examples of a 3-, 4-, 5-, 6- or 7-membered saturated heterocyclic ring include:

oxiranyl, aziridinyl, azetidinyl, tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, tetrahydrothien-2-yl, tetrahydrothien-3-yl, pyrrolidin-2-yl, pyrrolidin-3-yl, pyrazolidin-3-yl, pyrazolidin-4-yl, pyrazolidin- 5-yl, imidazolidin-2-yl, imidazolidin-4-yl, oxazolidin-2-yl, oxazolidin-4-yl, oxazolidin-5-yl, isoxa- zolidin-3-yl, isoxazolidin-4-yl, isoxazolidin-5-yl, thiazolidin-2-yl, thiazolidin-4-yl, thiazolidin-5-yl, isothiazolidin-3-yl, isothiazolidin-4-yl, isothiazolidin-5-yl, 1 ,2,4-oxadiazolidin-3-yl, 1 ,2,4- oxadiazolidin-5-yl, 1 ,2,4-thiadiazolidin-3-yl, 1 ,2,4-thiadiazolidin-5-yl, 1 ,2,4-triazolidin-3-yl, 1 ,3,4- oxadiazolidin-2-yl, 1 ,3,4-thiadiazolidin-2-yl, 1 ,3,4-triazolidin-2-yl, 2-tetrahydropyranyl,

4-tetrahydropyranyl, 1 ,3-dioxan-5-yl, 1 ,4-dioxan-2-yl, piperidin-2-yl, piperidin-3-yl, piperidin-4-yl, hexahydropyridazin-3-yl, hexahydropyridazin-4-yl, hexahydropyrimidin-2-yl, hexahydro- pyrimidin-4-yl, hexahydropyrimidin-5-yl, piperazin-2-yl, 1 ,3,5-hexahydrotriazin-2-yl and

1 ,2,4-hexahydrotriazin-3-yl, morpholin-2-yl, morpholin-3-yl, thiomorpholin-2-yl, thiomorpholin-3- yl, 1 -oxothiomorpholin-2-yl, 1 -oxothiomorpholin-3-yl, 1 ,1 -dioxothiomorpholin-2-yl, 1 ,1 - dioxothiomorpholin-3-yl, azepan-1 -, -2-, -3- or -4-yl, oxepan-2-, -3-, -4- or -5-yl, hexahydro-1 ,3- diazepinyl, hexahydro-1 ,4-diazepinyl, hexahydro-1 ,3-oxazepinyl, hexahydro-1 ,4-oxazepinyl, hexahydro-1 ,3-dioxepinyl, hexahydro-1 ,4-dioxepinyl and the like. Examples of a 3-, 4-, 5-, 6- or 7-membered partially unsaturated heterocyclic ring include: 2,3-dihydrofur-2-yl, 2,3-dihydrofur- 3-yl, 2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl, 2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,4- dihydrothien-2-yl, 2,4-dihydrothien-3-yl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-

3- yl, 2-isoxazolin-3-yl, 3-isoxazolin-3-yl, 4-isoxazolin-3-yl, 2-isoxazolin-4-yl, 3-isoxazolin-4-yl, 4- isoxazolin-4-yl, 2-isoxazolin-5-yl, 3-isoxazolin-5-yl, 4-isoxazolin-5-yl, 2-isothiazolin-3-yl, 3- isothiazolin-3-yl, 4-isothiazolin-3-yl, 2-isothiazolin-4-yl, 3-isothiazolin-4-yl, 4-isothiazolin-4-yl, 2-isothiazolin-5-yl, 3-isothiazolin-5-yl, 4-isothiazolin-5-yl, 2,3-dihydropyrazol-1 -yl,

2,3-dihydropyrazol-2-yl, 2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl, 2,3-dihydropyrazol-5- yl, 3,4-dihydropyrazol-1 -yl, 3,4-dihydropyrazol-3-yl, 3,4-dihydropyrazol-4-yl, 3,4-dihydropyrazol- 5-yl, 4,5-dihydropyrazol-1 -yl, 4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl, 4,5- dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl,

2.3- dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl,

3.4- dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 2-, 3-, 4-, 5- or 6-di- or tetrahydropyridinyl, 3-di- or tetrahydropyridazinyl, 4-di- or tetrahydropyri- dazinyl, 2-di- or tetrahydropyrimidinyl, 4-di- or tetrahydropyrimidinyl, 5-di- or tetrahydropyrimid- inyl, di- or tetrahydropyrazinyl, 1 ,3, 5-di- or tetrahydrotriazin-2-yl, 1 ,2, 4-di- or tetrahydrotriazin-3- yl, 2,3,4,5-tetrahydro[1 H]azepin-1 -, -2-, -3-, -4-, -5-, -6- or -7-yl, 3,4,5,6-tetrahydro[2H]azepin-2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,4,7-tetrahydro[1 H]azepin-1 -, -2-, -3-, -4-, -5-, -6- or -7-yl,

2,3,6,7-tetrahydro[1 H]azepin-1 -, -2-, -3-, -4-, -5-, -6- or -7-yl, tetrahydrooxepinyl, such as 2,3,4,5-tetrahydro[1 H]oxepin-2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,4,7-tetrahydro[1 H]oxepin-2-, -3-, -4- , -5-, -6- or -7-yl, 2,3,6,7-tetrahydro[1 H]oxepin-2-, -3-, -4-, -5-, -6- or -7-yl, tetrahydro-1 ,3- diazepinyl, tetrahydro-1 ,4-diazepinyl, tetrahydro-1 ,3-oxazepinyl, tetrahydro-1 ,4-oxazepinyl, tetrahydro-1 ,3-dioxepinyl and tetrahydro-1 ,4-dioxepinyl. A 3-, 4-, 5-, 6- or 7-membered completely unsaturated (including aromatic) heterocyclic ring is e.g. a 5- or 6-membered fully unsaturated (including aromatic) heterocyclic ring. Examples are: 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2- pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 4- isoxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 4-isothiazolyl, 2-imidazolyl, 4-imidazolyl, 1 ,3,4- triazol-2-yl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl,

4- pyrimidinyl, 5-pyrimidinyl and 2-pyrazinyl.

The term "a 3-, 4-, 5-, 6-, 7- or 8-membered saturated or partially unsaturated carbocyclic or heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members" as used herein denotes a saturated or unsaturated 3- to 8- membered ring system which optionally contains 1 to 3 heteroatoms selected from N, O, S, NO, SO and SO2, as defined above, with the exception of the completely unsaturated ring systems.

The remarks made below concerning preferred embodiments of the variables of the com- pounds of formulae (I), (II), (II ^* ), (III), (IV), (V), (VI), (VII) and (VIII) as well as formulae (ΙΙ.Α'), (Ι .Α'), (I I. A") and (Ι .Α"), and their subvariants are valid on their own as well as preferably in combination with each other as well as concerning the processes and the compounds according to the invention. The following remarks are made with regard to the compounds as used in the processes A and B of the present invention.

In a preferred embodiment of the invention, p in the compounds of formulae (I), (II), (Ι ), (IV) and (VI) is 0, 1 or 2, preferably 1 or 2, more preferably 2.

In another preferred embodiment of the invention, R ³ in the compounds of formulae (I), (II), (Ι ), (IV) and (VI) is selected from the group consisting of halogen, CN, Ci-C4-alkyl, and C1-C4- fluoroalkyl, for p > 1 it being possible that R ³ are identical or different. Preferably, R ³ is selected from the group consisting of halogen, CN, Ci-C4-alkyl and Ci-C4-fluoroalkyl, more preferably from halogen, CN and CH3, for p > 1 it being possible that R ³ are identical or different.

In a more preferred embodiment, p in the compounds of formulae (I), (II), (Ι ), (IV) and (VI) is 2, and one radical R ³ is located ortho with regard to the aminocarbonyl group, while the other is located para with respect to this group. Such compounds are referred to as compounds of formulae (I.A), (I I .A), (Ι .Α), (IV.A) and (VI.A), respectively. The compounds are depicted below and are preferred according to the present invention.

For the compounds of formulae (I.A), (II.A), (ΙΓ.Α), (IV.A) and (VI.A), it is preferred that R ^3a , R ^3b are independently selected from the group consisting of halogen, CN, d-Cs-alkyl, Ci- Cs-haloalkyl, C2-Cs-alkenyl, C2-C8-haloalkenyl, C2-Cs-alkynyl, C2-C8-haloalkynyl, wherein the six last radicals may optionally be substituted by one or more radicals R ^a , C3-C8-cycloalkyl, which is unsubstituted, partially or completely halogenated or carries one or more radicals R ^aa ;

-OR ^b , SR ^b , -S(0) _m R ^b , -N(R ^c )R ^d ,

phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R ^e , and

a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals R ^e .

It is particularly preferred that R ^3a and R ^3b are independently selected from halogen, CN, C1-C4- alkyl, and Ci-C4-fluoroalkyl, and even more preferred that R ^3a and R ^3b are independently selected from the the group consisting of halogen, CN and CH3. It is most preferred that R ^3a is CH3 and R ^3b is halogen, preferably CI.

In another preferred embodiment of the invention, R ² in the compounds of formulae (I), (II), (II ^* ), (V), (VII) and (VIII) is halogen, Ci-C ₄ -alkyl Ci-C ₄ -fluoroalkyl or (3,5-bis(trifluoro- methyl)pyrazol-2-yl)methyl. Preferably, R ² is Ci-C2-fluoroalkyl. Particularly preferably, R ² is CF3. Such compounds are referred to as compounds of formulae (I.CF3), (II.CF3), (IT.CFs), (V.CF3), (VII. CF3) and (VIII.CF3), respectively. The compounds are depicted below and are preferred according to the present invention.

It is particularly preferred that the compounds of formulae (I), (II) and (Ι ) are compounds of formulae (I.A), (II.A) and (Ι .Α), respectively, wherein R ² is CF3. These compounds are referred to as (I .A.CF3), (I I .A.CF3) and (IT.A.CFs). The compounds are available from the compounds of formula (IV.A) or (VI.A) as defined above and compounds of formula (V.CF3), (VII . CF3) or (VI I I .CF3) as defined above.

In another preferred embodiment of the invention, R ¹ in the compounds of formulae (I), (II), (II ^* ), (V), (VII) and (VIII) is halogen or CF ₃ . Particularly preferably, R ¹ is CI.

It is particularly preferred that the compounds of formulae (I), (II) and (Ι ) are compounds of formulae (I.A), (II.A), and (ll ^* .A) or compounds of formulae (I.CF ₃ ), (II.CF3) and (ll*.CF ₃ ) or compounds of formulae (I.A.CF3), (II.A.CF3) and (IT.A.CFs), wherein R ¹ halogen or CF3, preferably CI. Furthermore, it is particularly preferred that the compounds of formulae (V), (VII) and (VIII) are compounds of formulae (V.CF3), (VII. CF3) and (VIII.CF3), wherein R ¹ halogen or CF3, preferably CI.

In another preferred embodiment of the invention, R ⁴ and R ⁵ in the compounds of formulae (I) and (III) are independently of each other selected from the group consisting of Ci-C6-alkyl, C3- C7-cylcoalkyl and C3-C8-cycloalkyl-Ci-C4-alkyl, or

R ⁴ and R ⁵ together represent a C3-C7-alkylene or C3-C7-alkenylene forming together with the sulfur atom to which they are attached a 4-, 5-, 6-, 7- or 8-membered saturated or partially unsaturated ring, wherein 1 or 2 of the CH2 groups in the C3-C7-alkylene chain or 1 or 2 of any of the CH2 or CH groups in the C3-C7-alkenylene chain may be replaced may be replaced by 1 or 2 groups independently selected from the group consisting of O and S.

Preferably, R ⁴ and R ⁵ are independently of each other selected from Ci-C6-alkyl, more prefer- ably from Ci-C3-alkyl. Particularly preferably, R ⁴ and R ⁵ are both ethyl.

It is particularly preferred that the compounds of formulae (I) are compounds of formula (I.A) or compounds of formula (I.CF3) or compounds of formula (I.A.CF3), wherein R ⁴ and R ⁵ are as defined above. As salts of the compounds of formula (III), hydrogen sulfate salts and sulfate salts are preferred. Sulfate salts are particularly preferred. The salts of the compounds of formula (III) may be represented by the following formula (Ilia)

A® H ₂ N R

I

R ⁵ (Ilia)

wherein R ⁴ and R ⁵ are as defined above for the compounds of formula (III) and A- is HSCv or

For the compounds of formula (I), which are obtainable by the processes A and B and the sulfimines of formula (III) or the salts thereof, it is particularly preferred that the variables, if present, are selected as such that R ¹ is CI and R ² is CF3, and the remaining variables are selected as indicated in one of the rows A-1 to A-54 of Table A.

Table A

The same selections of the variables are also preferred for the compounds of formulae (II), (II ^* ), (IV), (VI), (VII) and (VIII), if the variables are present.

It is particularly preferred that the compounds of formulae (I), (II), (Ι ), (IV) and (VI) correspond to compounds of formulae (I.A), (II.A), (Ι .Α), (IV.A) and (VI.A), and that in the compounds of formulae (I.A), (II.A), (ll ^* .A), (IV.A) and (VI.A) and (III), (V), (VII) and (VIII), the variables, if present, are selected as such that R ¹ is CI, R ² is CF ₃ , R ^3a is CH ₃ , R ^3b is CI, R ⁴ and R ⁵ are both CH ₂ CH ₃ .

For the compounds of formula (V), it is preferred that M is MgY with Y being halogen, prefera- bly Br or CI.

It is particularly preferred that the compound of formula (V) is a compound of formula (V.CF ₃ ), wherein R ¹ is halogen or CF ₃ , preferably CI, and M is MgY with Y being halogen, preferably Br or CI. For the compounds of formula (VII), it is preferred that L is halogen or OH, preferably CI. It is particularly preferred that the compound of formula (VII) is a compound of formula (VII.CF3), wherein R ¹ is halogen or CF3, preferably CI, and L is halogen or OH, preferably CI. In another preferred embodiment of the invention, R ^x in the compounds of formulae (II), (IV) and (VI) is Ci-C2-alkyl, phenyl (CeH ₅ ), p-nitrophenyl ( -NO2-C6H4) or pentafluorophenyl (CeF ₅ ), preferably CH3.

It is particularly preferred that the compounds of formulae (IV) and (VI) are compounds of formulae (IV.A) and (VI. A), wherein R ^x is Ci-C2-alkyl, phenyl (CeHs), p-nitrophenyl ( -NO2-C6H4) or pentafluorophenyl (CeFs), preferably CH3, and it is particularly preferred that the compounds of formula (II) are compounds of formula (II.A) or compounds of formula (II.CF3) or compounds of formula (II.A.CF3), wherein R ¹ is halogen or CF3, preferably CI, and R ^x is Ci-C2-alkyl, phenyl (C6H5), p-nitrophenyl ( -NO2-C6H4) or pentafluorophenyl (CeF ₅ ), preferably CH3. For the compounds of formula (II), which are obtainable by or used in the processes A and B, it is particularly preferred that the variables are selected as such that R ¹ is CI and R ² is CF3, and the remaining variables are selected as indicated in one of the rows B-1 to B-30 of Table B. Table B

The same selections of the variables are also preferred for the compounds of formulae (IV) and (VI) as well as the compounds of formulae (V), (VII) and (VIII), if the substituents are present.

It is particularly preferred that the compounds of formula (II) correspond to compounds of for- mula (II.A.CFs), wherein R ¹ is CI, R ² is CF ₃ , R ^3a is CH ₃ , R ^3b is CI and R ^x is CH ₃ . The same sub- stituent definitions are also preferred for the compounds of formula (IV.A), (V), (VI.A), (VII) and (VIII), if the substituents are present.

In another preferred embodiment of the invention, X in the compounds of formula (Ι ) is OH. Such compounds are preferably activated in situ in the presence of a sulfonyl chloride. Without being bound to theory, it is assumed that compounds of formula (Ι ) are in situ formed, wherein X is e.g. any one of OS(0) ₂ Ci-C ₆ -alkyl, OS(0) ₂ Ci-C ₆ -haloalkyl, OS(0) ₂ benzyl, or OS(0) ₂ tolyl depending on the choice of the sulfonyl chloride. In another preferred embodiment, it is therefore preferred that X is any one of OS(0) ₂ Ci-C ₆ -alkyl, OS(0) ₂ Ci-C ₆ -haloalkyl, OS(0) ₂ benzyl, or OS(0) ₂ tolyl.

It is particularly preferred that the compounds of formula (Ι ) are compounds of formula (Ι .Α) or compounds of formula (IT.CFs) or compounds of formula (IT.A.CFs), wherein X is OH, which may be activated in situ as indicated above.

In another preferred embodiment of the invention, X in the compounds of formula (Ι ) is halo- gen, preferably CI.

It is particularly preferred that the compounds of formula (Ι ) are compounds of formula (Ι .Α) or compounds of formula (IT.CFs) or compounds of formula (IT.A.CFs), wherein X is CI.

For the compounds of formula (Ι ), which are preferably obtainable from the compounds of formula (II) and may be used in the processes A and B, it is particularly preferred that the variables are selected as such that R ¹ is CI and R ² is CF3, and the remaining variables are selected as indicated in one of the rows C-1 to C-12 of Table C.

Table C

X _R 3a _R 3b

C-1 CI CHs CI

C-2 OH CHs CI

C-3 CI CI CI

C-4 OH CI CI

C-5 CI CHs CN

C-6 OH CHs CN C-7 CI CI Br

C-8 OH CI Br

C-9 CI Br CI

C-10 OH Br CI

C-1 1 CI Br Br

C-12 OH Br Br

It is particularly preferred that the compounds of formula (Ι ) correspond to compounds of formula (l l*.A.CF ₃ ), wherein R ¹ is CI, R ² is CF ₃ , R ^3a is CH ₃ , R ^3b is CI and X is CI or OH, preferably CI. In addition to the above remarks, the following remarks are made with regard to the compounds as used in the process B of the present invention.

Alternative to the above preferred embodiments relating the processes A and B, it is also preferred for the compounds of formulae (I), (I I), (Ι ), (IV) and (V) in the process B, that the com- pounds of formulae (I I), (Ι ) and (IV) correspond to compounds of formulae (I I .A), (Ι .Α) and (IV.A), and that the variables in the formulae (I . A), (I I .A), (IV.A) and (V), if present, are selected as such that R ¹ is CI, R ² is Br, R ^3a is Br and R ^3b is CI. Furthermore, it is preferred for the compounds of formula (I I) and (I I.A), respectively, that R ^x is Ci-C2-alkyl, phenyl, p-nitrophenyl or pentafluorophenyl, preferably CH ₃ , and it is preferred for the compounds of formula (Ι ) and (Ι Γ.Α), respectively, that X is OH or CI.

In view of the above, process B is thus not only suitable for the preparation of compounds of formula (I), but also for the preparation of cyclaniliprole.

The following remarks are made with regard to the compounds of formulae (II .A) and (Ι .Α') as well as the compounds of formulae (I I .A") and (Ι .Α").

The compounds of formulae (II .A) and (Ι .Α') differ from the compounds of formulae (I I .A) and (Ι .Α) as defined above in terms of the definition of the substituent R ² , which does not include the option of R ² being halogen and the option of R ² being CH ₃ .

The compounds of formulae (I I.A") and (Ι .Α") differ from the compounds of formulae (I I .A) and (Ι .Α) as defined above in terms of the definition of the substituent R ^3a because it is defined that R ^3a may not be CH ₃ or CI.

In a preferred embodiment of the invention, R ² in the compounds of formulae (Ι Ι.Α') and (Ι .Α) is CF ₃ . Accordingly, the compounds of formulae (I I .A) and (Ι .Α') preferably correspond to the compounds of formulae (I I .A.CF ₃ ) and (N*.A.CF ₃ ) as defined above.

For the compounds of formulae (I I. A') and (Ι .Α), which are preferably compounds of formulae (II.A.CF3) and (ll ^* .A.CF ₃ ), R ¹ , R ^3a and R ^3b preferably have the following meanings:

R ¹ is halogen or CF3;

R ^3a is selected from the group consisting of halogen, CN, Ci-C4-alkyl and Ci-C4-fluoroalkyl; R ^3b is selected from the group consisting of halogen, CN, Ci-C4-alkyl and Ci-C4-fluoroalkyl; and preferably have the following meanings:

R ¹ is CI;

R ^3a is selected from the group consisting of halogen, CN and CH3;

R ^3b is selected from the group consisting of halogen, CN and CH3;

Particularly preferred are compounds of formulae (ΙΙ.Α') and (Ι .Α'), which are compounds of formulae (II.A.CF3) and (ll ^* .A.CF ₃ ), and wherein R ¹ is CI, R ^3a is CH ₃ and R ^3b is CI.

Accordingly, the following compounds are particularly preferred as compounds of formulae (II.A) and (ΙΙ ^* .Α').

In the compounds of formulae (I I. A') and (Ι .Α') and in particular the preferred compounds depicted above, it is preferred that R ^x is Ci-C2-alkyl, phenyl, p-nitrophenyl or pentafluorophenyl, preferably CH3, and that X is halogen or OH, preferably CI.

In a preferred embodiment of the invention, R ^3a in the compounds of formulae (II.A") and (II.A") is Br. Furthermore, it is preferred that in such compounds that R ^3b is CI and R ² is Br.

Accordingly, the following compounds are particularly preferred as compounds of formulae (II.A") and (ll ^* .A"). (H.A")preferred (I l ^* .A") _r eferred

In the compounds of formulae (I I. A") and (Ι .Α") and in particular the preferred compounds depicted above, it is preferred that R ^x is Ci-C2-alkyl, phenyl, p-nitrophenyl or pentafluorophenyl, preferably Ci-alkyl, and that X is halogen or OH, preferably CI.

The reactions of the processes of the invention as described hereinafter are performed in reaction vessels customary for such reactions, the reactions being carried out in a continuous, semi-continuous or batchwise manner.

In general, the particular reactions will be carried out under atmospheric pressure. The reac- tions may, however, also be carried out under reduced pressure.

The temperatures and the duration times of the reactions may be varied in broad ranges, which the person skilled in the art knows from analogous reactions. The temperatures often depend on the reflux temperature of the solvents. Other reactions are preferably performed at room temperature, i.e. at about 25°C, or under ice cooling, i.e. at about 0°C. The end of the re- action can be monitored by methods known to a person skilled in the art, e.g. thin layer chromatography or HPLC.

If not otherwise indicated, the molar ratios of the reactants, which are used in the reactions, are in the range of from 0.2:1 to 1 :0.2, preferably from 0.5:1 to 1 :0.5, more preferably from 0.8:1 to 1 :0.8. Preferably, equimolar amounts are used.

If not otherwise indicated, the reactants can in principle be contacted with one another in any desired sequence.

The person skilled in the art knows when the reactants or reagents are moisture sensitive, so that the reaction should be carried out under protective gases such as under a nitrogen atmosphere, and dried solvents should be used.

The person skilled in the art also knows the best work-up of the reaction mixture after the end of the reaction.

In the following, the process A is described in further detail. As already indicated above, the process A of the present invention for preparing compounds of formula (I) comprises the steps of providing a compound of formula (II) or (Ι ), and reacting the compound of formula (II) or (Ι ) with a compound of formula (III) or a salt thereof. Preferred definitions for the compounds of formulae (I), (II), (Ι ) and (III) have been provided above.

The reaction conditions for step (ii) of the process A depend on whether a compound of formula (II) or a compound of formula (Ι ) is reacted with the compound of formula (III) or a salt thereof. In one embodiment of the process A of the present invention, a compound of formula (I I) is reacted with the compound of formula (II I) or a salt thereof. Said reaction can be carried out by analogy to the reaction procedure described in Journal of Medicinal Chemistry, 45(17), 3692- 3702, 2002. In particular, the reaction may be carried out by a process, wherein the compound of formula (I I I) or a salt thereof is first reacted with a water soluble base in an aqueous solution, the resulting mixture is then dried, and the resulting dry mixture is then reacted with the compound of formula (I I) in a protic solvent.

Suitable reaction temperatures for the reaction between the compound of formula (I II) or a salt thereof with the water soluble base are in the range of from -20°C to +20°C, preferably in the range of from -10°C to +10°C, more preferably in the range of from -2°C to +2°C.

Preferably, the water soluble base is used at least in stochiometric amounts. The amount of the base is preferably in the range of 1 to 3 mole, more preferably 1 .5 to 2.5 mole, most preferably 1 .8 to 2.2 mole per mole of the compound of formula (II I).

Suitable bases include, but are not limited to oxo bases. Suitable oxo bases include but are not limited to hydroxides, in particular alkali metal hydroxides such as lithium, sodium or potassium hydroxide, and mixtures thereof. Sodium hydroxide is particularly preferred.

Preferably, the drying step is performed by freeze-drying the mixture, preferably by freeze- drying at -70°C to -90°C, preferably at -78°C.

Suitable reaction temperatures for the reaction with the pre-treated compound of formula (I II) with the compound of formula (I I) are in the range of from 20°C to 60°C, preferably from 30°C to 50°C, more preferably from 38°C to 42°C.

Suitable protic solvents are Ci-C4-alkanols such as methanol, ethanol, propanol and isopropa- nol, C2-C4-alkandiols, such as ethylene glycol or propylene glycol, and ether alkanols such as diethylene glycol, and mixtures thereof. Preferably the reaction is carried out in methanol or ethanol, preferably in methanol.

If a compound of formula (II) is reacted with a compound of formula (II I) or a salt thereof as described above, it is preferred that R ^x in the compound of formula (I I) is Ci-C6-alkyl or phenyl, wherein the phenyl radical may be substituted by one or more radicals selected from halogen and NO2. It is even more preferred that R ^x is Ci-C2-alkyl, phenyl, p-nitrophenyl or

pentafluorophenyl, and particularly preferred that R ^x is CH3. Furthermore, it is preferred that the compound of formula (I I I) is provided in the form of the salt, preferably in the form of a hydrogensulfate salt or a sulfate salt. In one embodiment of the process A of the present invention, a compound of formula (Ι ) is reacted with the compound of formula (II I) or a salt thereof.

The compounds of formula (Ι ) may have an improved reactivity compared to the compounds of formula (I I), in particular if X is halogen, OC(0)Ci-C ₆ -alkyl, OS(0) ₂ Ci-C ₆ -alkyl, OS(0) ₂ Ci-C ₆ - haloalkyi, OS(0)2benzyl, or OS(0)2tolyl. It is preferred for the process A of the present invention that X in the compound of formula (Ι ) is halogen, preferably CI. The reaction of such compounds of formula (Ι ) with the compounds of formula (II I) or the salts thereof can be carried out by analogy to the reaction procedure described in WO 2000/034368, WO 2000/034238, WO 2000/034260 or WO 2000/034237.

In particular, the reaction may be carried out by a process, wherein the compound of formula (III) or a salt thereof is reacted with a compound of formula (Ι ) in an aprotic solvent.

Suitable reaction temperatures are in the range of from 0° to 30°C, preferably from 10°C to 30°C, more preferably in the range of from 20°C to 25°C.

Suitable aprotic solvents include aliphatic hydrocarbons, cycloaliphatic hydrocarbons, halo- genated alkanes, aromatic hydrocarbons, open-chained ethers, cyclic ethers, esters, aliphatic or alicyclic carbonates. Preferred aprotic solvents are halogenated solvents, such as methylene chloride, chloroform or 1 ,2-dichlorethane. Methylenechloride is particularly preferred.

On the other hand, if X in the compounds of formula (Ι ) is OH, in situ activation of the carbox- ylic acid group is typically required in step (ii) of the process A of the present invention. In situ activation may e.g. be achieved by adding a reagent, which converts the OH group to a leaving group, such as dicyclohexylcarbodiimide (DCC), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) or the like. Optionally, the activated carboxylic acid group may then further be converted into an active ester by adding N-hydroxysuccinimide, 1 -hydroxybenzotriazole (HOBT), 1 - hydroxy-7-azabenzotriazole (HOAT), pentafluorophenol, p-nitrophenyl or the like, before the compound of formula (Ι ) is reacted with the compound of formula (III) or a salt thereof in step (ii) of the process A.

Alternatively, in situ activation may be achieved by adding a sulfonyl chloride to the reaction mixture in step (ii) of process A of the present invention. It has been found that this in situ activation is particularly effective in terms of increasing the reactivity of compounds of formula (Ι ), wherein X is OH. Accordingly, it is a preferred embodiment of the process A of the present in- vention that X in the compound of formula (Ι ) is OH, and step (ii) is performed in the presence of a sulfonyl chloride.

In situ activation of carboxylic acid groups with sulfonyl chlorides in the presence of a suitable amine to provide N-phenylpyrazole-1 -carboxamides has e.g. been described in WO

2006/062978. The reaction of compounds of formula (Ι ), wherein X is OH, with the compounds of formula (III) or a salt thereof in step (ii) of the process A of the present invention under in situ activation, can be performed analogously to the process described in WO 2006/062978. It is thus preferred that in situ activation of the compound of formula (Ι ) is performed in the presence of the compound of formula (III) or a salt thereof by mixing the compounds of formula (Ι ) and (III) in the presence of a base in a solvent, so that the amidation reaction directly takes place after the in situ activation.

Suitable reaction temperatures for this one pot reaction are in the range of from -20°C to 10°C, preferably in the range of from -10°C to 5°C.

Preferably, a sulfonyl chloride of the formula R ^S S(0)2CI is used, wherein R ^s is Ci-C6-alkyl, Ci- C6-haloalkyl, benzyl or phenyl, wherein the phenyl group may be substituted by halogen, C1-C3- alkyl or nitro. More preferably, the sulfonyl chloride is methanesulfonyl.

Preferably, the in situ activation is performed in the presence of a base, such as a tertiary amine or an optionally substituted pyridine. Both, the sulfonyl chloride and the base are preferably used in amounts in the range of 0.8 to 2 mole, more preferably 0.9 to 1 .5 mole, most preferably 1 .0 to 1 .2 mole per mole of the compound of formula (Ι ).

A suitable solvent for the in situ activation and the subsequent amidation reaction is e.g. ace- tonitrile.

In a preferred embodiment of the process A of the present invention, the compound of formula (Ι ) is provided in step (i) of the process A by converting a compound of formula (II) into a compound of formula (Ι ). Preferably, the compound of formula (Ι ) is provided by hydrolyzing a compound of formula (II), wherein R ^x is Ci-C6-alkyl or phenyl, wherein the phenyl radical may be substituted by one or more radicals selected from halogen and NO2, or by hydrogenating a compound of formula (II), wherein R ^x is benzyl, to give a compound of formula (Ι ) with X being OH, and optionally further activating said compound to give a compound of formula (Ι ), wherein X is halogen, OC(0)Ci-C ₆ -alkyl, OS(0) ₂ Ci-C ₆ -alkyl, OS(0) ₂ Ci-C ₆ -haloalkyl, OS(0) ₂ benzyl, or OS(0) ₂ tolyl.

Compounds of formula (Ι ), wherein X is OH, can preferably be provided by hydrolyzing a compound of formula (II), wherein R ^x is Ci-C ₂ -alkyl, preferably CH3, in the presence of a hydroxide.

With regard to suitable reaction conditions for the hydrolysis, reference is made to Journal of Medicinal Chemistry 56(21 ), 8332-8338, 2013. In particular, hydrolysis may be achieved by reacting a compound of formula (II) with a base in an aqueous medium.

Suitable reaction temperatures are in the range of from 0°C to 50°C, preferably in the range of from 10°C to 30°C, more preferably in the range of from 20°C to 25°C.

Preferably, the amount of the base is in the range of 1 .0 to 2.0 mole, more preferably 1.0 to 1.3 mole, most preferably 1.0 to 1.1 mole per mole of the compound of formula (II).

Suitable bases include but are not limited to hydroxides, in particular alkali metal hydroxides such as lithium, sodium or potassium hydroxide, and mixtures thereof. Sodium hydroxide is par- ticularly preferred.

Compounds of formula (Ι ), wherein X is CI, can be provided by reacting the resulting compound of formula (Ι ), wherein X is OH, with thionylchloride or oxalylchloride, preferably oxalylchloride, optionally in the presence of catalytic amounts of DMF, in an aprotic solvent. As regards suitable reaction conditions for the activation with oxalylchloride, reference is made to WO 2007/141391 .

Suitable reaction temperatures are in the range of from 0° to 30°C, preferably from 10°C to 30°C, more preferably in the range of from 20°C to 25°C.

Thionylchloride or oxalylchloride is preferably used in an amount in the range of 1.0 to 5.0 mole, more preferably 2.0 to 4.0 mole, most preferably 2.5 to 3.5 mole per mole of the compound of formula (Ι ) with X being OH. Suitable aprotic solvents include aliphatic hydrocarbons, cycloaliphatic hydrocarbons, halo- genated alkanes, aromatic hydrocarbons, open-chained ethers, cyclic ethers, esters, aliphatic or alicyclic carbonates. Preferred aprotic solvents are halogenated solvents, such as methylene chloride, chloroform or 1 ,2-dichlorethane. Methylenechloride is particularly preferred.

It is preferred that the reaction is carried in the presence of catalytic amounts of DMF.

In another preferred embodiment of the process A of the present invention, the compound of formula (II) is provided in step (i) of the process A by reacting a 2-isocyanatobenzoate of formula (IV) with a pyrazole metal compound of formula (V)

(IV) (V)

wherein p, R ¹ , R ² , R ³ and R ^x are as defined above, and M is Li, MgY or ZnY with Y being halogen. Preferably, M is MgY with Y being Br, I or CI, preferably Br or CI.

Compounds of formula (V) are available according to the methods described in EP 2 189 455 (WO 2009/022600) as well as in WO 2013/076092 and WO 2013/024007.

Compounds of formula (IV) are available from 2-amino-benzoate derivatives according to the method described in Bioorganic & Medicinal Chemistry, 15(1 ), 365-373, 2007 and in Bioorganic & Medicinal Chemistry Letters, 21 (1 1 ), 3358-3361 , 201 1.

The reaction conditions for the preparation of compounds of formula (II) according to the above isocyanate route are outlined in detail, when describing the process B.

In another preferred embodiment of the process A of the present invention, the compound of formula (II) is provided in step (i) of the process A by reacting a 2-aminobenzoate of formula (VI) with a pyrazole carboxylic acid derivative of fo

(VI) (VII)

wherein p, R ¹ , R ² , R ³ and R ^x are as defined above, and L is halogen, OC(0)Ci-C6-alkyl, OS(0)2Ci-C6-alkyl or OH. Preferably, L is halogen, particularly preferably CI. Alternatively, L may be OH, which is activated by adding a sulfonyl chloride as described above.

The compounds of formula (VII) are obtainable according to the methods described in WO 2013/076092 and WO 2013/024007.

The compounds of formula (VI) are available from the corresponding 2-aminobenzoic acid derivatives by standard esterification processes known in the art. The reaction conditions are similar to those described for the reaction between the compounds of formula (Ι ) and the compounds of formula (III). Thus, reaction temperatures in the range of from 0°C to 30°C, preferably from 10°C to 30°C , more preferably from 20°C to 25°C are typically applied, and aprotic solvents, preferably methylenechloride, are typically used, if L is CI. If L is OH, in situ activation of the carboxylic acid group may be required. Such activation may be performed as outlined above, e.g. by adding a sulfonyl chloride to the reaction mixture.

In another preferred embodiment of the process A of the present invention, the compound of formula (II) is provided in step (i) of the process A by reacting a 2-aminobenzoate of formula (VI) with a pyrazole aldehyde of formula (VIII)

(VI) (VIII)

wherein p, R ¹ , R ² , R ³ and R ^x are as defined in claim 1 , in the presence of an oxidizing agent. Preferably, the oxidizing agent is a chloro- and/or CN-substituted benzoquinone or a meta- chloroperbenzoic acid.

The synthesis of the compounds of formula (VIII) as well as the reaction conditions for the reaction of these compounds with the compounds of formula (VI) can be taken from

WO 2008/126933, EP 2143721 and EP 2143720.

Suitable reaction temperatures are above 20°C, preferably above 50°C, more preferably in the range of from 70°C to 105°C, most preferably about 100°C.

Preferred benzoquinone compounds are selected from the group consisting of 2,3-dichloro- 5,6-dicyano-1 ,4-benzoquinone, tetrachloro-1 ,2-benzoquinone, and tetrachloro-1 ,4- benzoquinone. Tetrachloro-1 ,2-benzoquinone is particularly preferred.

It is preferred that the benzoquinone compound or the meta-chloroperbenzoic acid is used in an amount in the range of 1.0 to 5.0 mole, more preferably 1 .0 to 2.0 mole, most preferably 1 .0 to 1 .5 mole per mole of the compound of formula (VIII).

Preferred solvents for the reaction with benzoquinone compounds as oxidizing agents are high boiling ether compounds such as 1 ,4-dioxane. Acetonitril is preferred as a solvent, if meta- chloroperbenzoic acid is used as oxidizing agent.

Optionally, catalytic amounts of p-toluenesulfonic acid monohydrate, camphor sulfonic acid and/or copper iodide may be added to the reaction mixture.

In the following, the process B is described in further detail.

As already indicated above, the process B of the present invention for preparing compounds of formula (II) comprises reacting a compound of formula (IV) with a compound of formula (V). The process may be extended to a process for preparing compounds of formula (I) comprising pre- paring compounds of formula (II) by reacting a compound of formula (IV) with a compound of formula (V) and, optionally converting the compound of formula (II) into a compound of formula (Ι ), and reacting the compound of formula (II) or (Ι ) with a compound of formula (III) or a salt thereof. Preferred definitions for the compounds of formulae (II), (IV) and (V) as well as formu- lae (I), (II), (Ι ) and (III) have been provided above.

According to process B of the invention, the compound of formula (II) is provided by reacting a 2-isocyanatobenzoate of formula (IV) with a pyrazole metal compound of formula (V)

(IV) (V)

wherein p, R ¹ , R ² , R ³ and R ^x are as defined above, and M is Li, MgY or ZnY with Y being halogen. Preferably, M is MgY with Y being Br, I or CI, preferably Br or CI.

Compounds of formula (V) are available according to the methods described in EP 2 189 455 (WO 2009/022600) as well as in WO 2013/076092 and WO 2013/024007.

Compounds of formula (IV) are available from 2-amino-benzoate derivatives according to the method described in Bioorganic & Medicinal Chemistry, 15(1 ), 365-373, 2007 and in Bioorganic & Medicinal Chemistry Letters, 21 (1 1 ), 3358-3361 , 201 1.

The reaction conditions for the preparation of compounds of formula (II) from the compounds of formula (IV) and (V) are as follows. It is preferred that the compounds of formula (V) are pre- pared in situ, for example by reacting a compound of formula (IXa) or (IXb) with Hal meaning halogen, preferably CI or Br, as depicted below with an organometallic reagent. The resulting compounds of formula (V) are then directly reacted with the compounds of formula (IV).

The in situ preparation of the compounds of formula (V) is typically performed at temperatures in the range of from -10°C to +5°C, preferably from -5°C to 0°C, more preferably at 0°C.

As organometallic reagents, organolithium reagents R ^Li Li with R ^Li being Ci-C6-alkyl, such as n- butyllithium, may be used. Preferably, Grignard reagents R ^M sMgY with R ^M 9 being Ci-C6-alkyl and Y being CI, Br or I, such as isopropyl magnesium chloride, are used.

It is preferred that the organometallic reagent is used in an amount in the range of 1.0 to 3.0 mole, more preferably 1.0 to 2.0 mole, most preferably 1.0 to 1.7 mole per mole of the compound of formula (IXa) or (IXb).

Suitable solvents for the in situ preparation of the compounds of formula (V) are cyclic and acyclic ethers, such as diethylether, tetrahydrofuran, 1 ,2-dimethoxyethane and the like. 1 ,2- Dimethoxyethane and tetrahydrofuran are preferred. Mixtures of 1 ,2-dimethoxyethane and tetrahydrofuran are also preferred.

Preferably, both the compound of formula (IXa) or (IXb) and the organometallic reagent are combined with each other in the form of solutions.

The addition of the compounds of formula (IV) to the in situ prepared compounds of formula (V) is then performed at a temperature in the range of from -20°C to +20°C, preferably from - 5°C to +5°C, more preferably about 0°C. After about 1 hour at this temperature, the reaction temperature may be increased to a temperature of from 20°C to 25°C.

The compound of formula (IV) is also preferably provided in solution, preferably in a solution in a cyclic or acyclic ether or an aromatic solvent or a mixture thereof. Preferably, the compound of formula (IV) is provided as a solution in tetrahydrofuran or toluene or a mixture thereof.

Any further reactions of the compounds of formula (II) to prepare compounds of formula (I) may be performed as described above for process A.

Examples I. Chemistry The characterization can be done by coupled High Performance Liquid Chromatography / mass spectrometry (HPLC/MS), by NMR or by their melting points.

Method Analytical HPLC column: Phenomenex Kinetex 1 .7 μηι XB-C18 100A; 50 x 2.1 mm; mobile phase: A: water + 0.1 % trifluoroacetic acid (TFA); B: acetonitrile + 0.1 % TFA; gradient: 5-100% B in 1.50 minutes; 100% B 0.20 min; flow: 0.8-1 .OmL/min in 1 .50 minutes at 60°C. MS-method: ESI positive.

¹ H-NMR. The signals are characterized by chemical shift (ppm) vs. tetramethylsilane, by their multiplicity and by their integral (relative number of hydrogen atoms given). The following abbreviations are used to characterize the multiplicity of the signals: m = multiplett, q = quartett, t = triplett, d = doublet and s = singulett.

Abbreviations used are: h for hour(s), min for minute(s) and room temperature for 20-25°C.

A. Synthesis examples Example P.1 : methyl 5-chloro-2-isocyanato-3-methyl-benzoate

A solution of methyl 5-chloro-2-amino-3-methyl-benzoate (2.0 g, 10 mmol, 1.3 equiv.) in toluene (25 ml.) was treated with potassium carbonate (1 .38 g, 10.0 mmol, 1.33 equiv.) followed by dropwise addition of triphosgene (1 .48 g, 7.50 mmol, 1.00 equiv.) at room temp. After 18, the solids were filtered off and discarded. The mother liquor was concentrated in vacuum to obtain the title compound (1 .70 g, 68%) which was used in the next step without further purification. An aliquot of the product was treatd with isopropyl amine which was characterized. Characterization of the corresponding isopropyl urea by ¹ H-NMR (400 MHz, CDC ): 5[delta] = 1 .20 (d, 6 H), 2.29 (s, 3H), 3.74 (m, 1 H), 3.88 (s, 3H), 3.93 (m, 1 H), 7.36 (s, 1 H), 7.74 (s, 1 H), 8.50 (br. s, 1 H). Example P.2: methyl 5-chloro-2-isocyanato-3-methyl-benzoate

To a solution of triphosgene (32 g, 0.16 mol, 1 .6 equiv.) in toluene (100 mL) was added a solution of methyl 5-chloro-2-amino-3-methyl-benzoate (20 g, 0.10 mol, 1.0 equiv.) in toluene (125 mL) at 20°C. After 2 h at room temperature, potassium carbonate was added and stirred for another 60 h. Solids were removed by filtration. The mother liquor was concentrated in vacuum to obtain the title compound (15.8 g, 66%) which was used in the next step without further purification. An aliquot of the product was treatd with isopropyl amine which was characterized.

Characterization of the corresponding isopropyl urea by ¹ H-NMR (400 MHz, CDCb): 5[delta] = 1 .20 (d, 6 H), 2.29 (s, 3H), 3.74 (m, 1 H), 3.88 (s, 3H), 3.93 (m, 1 H), 7.36 (s, 1 H), 7.74 (s, 1 H), 8.50 (br. s, 1 H).

Example P.3: methyl 5-chloro-2-isocyanato-3-methyl-benzoate

To a solution of phosgene (74.19 g of a 20% solution in toluene, 150 mmol, 3.0 equiv.) was added a solution of methyl 5-chloro-2-amino-3-methyl-benzoate (10 g, 50 mmol, 1 .0 equiv.) in toluene (100 mL) at 20°C. After 2 h at room temperature, the mixture was heated to 100°C mantle temperature and left at this temperature for 2 h. After cooling, the mixture was concentrated in vacuum to obtain the title compound (1 1 .5 g, 92%) which was used in the next step without further purification. An aliquot of the product was treatd with isopropyl amine which was characterized.

Characterization of the corresponding isopropyl urea by ¹ H-NMR (400 MHz, CDCb): 5[delta] = 1 .20 (d, 6 H), 2.29 (s, 3H), 3.74 (m, 1 H), 3.88 (s, 3H), 3.93 (m, 1 H), 7.36 (s, 1 H), 7.74 (s, 1 H), 8.50 (br. s, 1 H).

Example P.4: methyl 5-chloro-2-isocyanato-3-methyl-benzoate

To a solution of phosgene (1 1 1 g of a 20% solution in toluene, 224 mmol, 1.5 equiv.) was added a solution of methyl 5-chloro-2-amino-3-methyl-benzoate (30.1 g, 150 mmol, 1.00 equiv.) in toluene (100 mL) at 26°C. During the addition, the temperature rose to 31 °C and was stirred for an additional 2 h, before the mixture was heated to 100°C mantle temperature and left at this temperature for 2 h. After cooling, the solids were filtered off and the mother liquor was concentrated in vacuum to obtain the title compound (30.0 g, 87%) which was used in the next step without further purification. An aliquot of the product was treatd with isopropyl amine which was characterized.

Characterization of the corresponding isopropyl urea by ¹ H-NMR (400 MHz, CDCI3): 5[delta] = 1 .20 (d, 6 H), 2.29 (s, 3H), 3.74 (m, 1 H), 3.88 (s, 3H), 3.93 (m, 1 H), 7.36 (s, 1 H), 7.74 (s, 1 H), 8.50 (br. s, 1 H). Example P.5: methyl 5-chloro-2-[[2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyraz ole-3- carbonyl]amino]-3-methyl-benzoate

To a cooled solution of 3-chloro-2-[3-(trifluoromethyl)pyrazol-1 -yl]pyridine (12.4 g, 50.1 mmol, 1 .00 equiv.) in DME (125 mL) was added a solution of isopropyl magnesium chloride (30 mL of a 2 M solution in THF, 60 mmol, 1 .2 equiv.) at 0°C within 45 min. After 4 h at this temperature, a solution of methyl 5-chloro-2-isocyanato-3-methyl-benzoate (12.5 g, purity 90%, 57.8 mmol, 1 .15 equiv.) in THF (90 mL) was added at 0-3°C. After 1 h at this temperature, the cooling bath was removed and the mixture was stirred overnight. After concentration in vacuum under ice- cooling, aqueous hydrochloric acid (1 M) was used to adjust the pH to 1. Water and ethyl acetate were added and the layers were separated. The organic layer was washed with aqueous hydrochloric acid (0.1 M) twice, followed by washing with water and drying over magnesium sulfate. The mixture was concentrated to obtain the crude product (23.8 g with a 30% purity; 30% yield). Trituration with diisopropyl ether (100 mL) at 0°C yielded the pure title compound.

Characterization by H-NMR (400 MHz, CDCI ₃ ): 5[delta] = 2.21 (s, 3H), 3.94 (s, 3H), 7.27 (s, 1 H), 7.39 (s, 1 H), 7.40 (m, 1 H), 7.82 (s, 1 H), 7.90 (d, 1 H), 8.49 (d, 1 H), 10.12 (s, 1 H).

Characterization by HPLC-MS: 1.240 min, m/z = 473.0 Example P.6: methyl 5-chloro-2-[[2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyraz ole-3- carbonyl]amino]-3-methyl-benzoate

To a cooled solution of 3-chloro-2-[3-(trifluoromethyl)pyrazol-1 -yl]pyridine (12.4 g, 100 mmol, 1 .25 equiv.) in DME (100 mL) and THF (100 mL) was added a solution of isopropyl magnesium chloride (65 mL of a 2 M solution in THF, 0.13 mol, 1.63 equiv.) at 0°C within 45 min. After 4 h at this temperature, this mixture was added to a solution of methyl 5-chloro-2-isocyanato-3- methyl-benzoate (18.23 g, purity 99%, 0.08 mol, 1 .00 equiv.) in THF (180 mL) was added at - 15°C. After 1 h at 0°C, the cooling bath was removed and the mixture was stirred overnight. After concentration in vacuum under ice-cooling, aqueous hydrochloric acid (1 M) was used to adjust the pH to 1. Water and ethyl acetate were added and the layers were separated. The organic layer was washed with aqueous hydrochloric acid (0.1 M) twice, followed by washing with water and drying over magnesium sulfate. The mixture was concentrated to obtain the crude product (44.0 g with a 30% purity; 28% yield). Trituration with diisopropyl ether (100 mL) at 0°C yielded the pure title compound. Characterization by H-NMR (400 MHz, CDCI ₃ ): 5[delta] = 2.21 (s, 3H), 3.94 (s, 3H), 7.27 (s, 1 H), 7.39 (s, 1 H), 7.40 (m, 1 H), 7.82 (s, 1 H), 7.90 (d, 1 H), 8.49 (d, 1 H), 10.12 (s, 1 H).

Characterization by HPLC-MS: 1.240 min, m/z = 473.0

Example P.7: methyl 5-chloro-2-[[2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyraz ole-3- carbonyl]amino]-3-methyl-benzoate

A mixture of methyl 5-chloro-2-amino-3-methyl-benzoate (0.36 g, 1 .81 mmol, 1.00 equiv.), 2-(3- chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carbaldehyde (prepared as described in WO 2008126858, 0.50 g, 1 .81 mmol, 1.00 equiv.), 3,4,5,6-tetrachloro-1 ,2-benzoquinone (0.56 g, 2.28 mmol, 1.25 equiv.) and camphor sulfonic acid (catalytic amount) in 1 ,4-dioxane was stirred at reflux for 4 h. After cooling, saturated aqueous sodium bicarbonate solution was added and the mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate, concentrated and purified with column chromatography on silica gel to obtain the title compound (300 mg, 35%).

Characterization by H-NMR (400 MHz, CDCI ₃ ): 5[delta] = 2.21 (s, 3H), 3.94 (s, 3H), 7.27 (s, 1 H), 7.39 (s, 1 H), 7.40 (m, 1 H), 7.82 (s, 1 H), 7.90 (d, 1 H), 8.49 (d, 1 H), 10.12 (s, 1 H).

Characterization by HPLC-MS: 1.240 min, m/z = 473.0

Example P.8: 5-chloro-2-[[2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyraz ole-3- carbonyl]amino]-3-methyl-benzoic acid

To a solution of methyl 5-chloro-2-[[2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyraz ole-3- carbonyl]amino]-3-methyl-benzoate (1.50 g, 3.16 mmol, 1 .00 equiv.) in THF (10 ml.) was added aqueous sodium hydroxide (1.58 ml. of a 2 M solution, 3.16 mmol, 1.00 equiv.) at room temperature and left over night. Aqueous hydrochloric acid (2 M) was used to acidify before concentration in vacuum. The residue was taken up in water and stirred to obtain a precipitate which was filtered and washed with water. After drying of the solid, the title compound (1.29 g, 89%) was obtained.

Characterization by H-NMR (400 MHz, DMSO-d ₆ ): 5[delta] = 2.21 (s, 3H), 7.61 (s, 1 H), 7.63- 7.74 (m, 3H), 8.23 (d, 1 H), 8.55 (d, 1 H), 10.50 (br. s, 1 H), 13.05-13.50 (br. s, 1 H).

Example P.9: 5-chloro-2-[[2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyraz ole-3- carbonyl]amino]-3-methyl-benzoyl chloride

To a solution of 5-chloro-2-[[2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyraz ole-3-carbonyl]amino]- 3-methyl-benzoic acid (1.29 g, 2.81 mmol, 1 .00 equiv.) and 3 drops of DMF in dichloromethane (25 ml.) was added oxalyl chloride (0.73 ml_, 1.07 g, 8.43 mmol, 3 equiv.) at room temperature and stirred overnight. After concentration, the mixture was concentrated in vacuum to obtain the crude title compound (1 .24 , 92%) which was used in the next step without further purification.

Example P.10: N-[4-chloro-2-[(diethyl- ⁴ -sulfanylidene)carbamoyl]-6-methyl-phenyl]-2- (3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxami de

To a mixture of (diethyl- ⁴ -sulfanylidene)ammonium sulfate (0.35 g, 1 .13 mmol, 1 equiv.) and dichloromethane (5 ml.) was added a solution of 5-chloro-2-[[2-(3-chloro-2-pyridyl)-5-

(trifluoromethyl)pyrazole-3-carbonyl]amino]-3-methyl-benz oyl chloride (0.60 g, 1 .26 mmol, 1.1 1 equiv.) in dichloromethane (5 ml.) at room temperature. After 2 h, water was added and the layers were separated. The organic layer was dried over sodium sulfate, filtered and concentrated in vacuum. The residue was triturated in diisopropyl ether to obtain the title compound (0.47 g, 75%).

Characterization by HPLC ^* : 4.36 min. ^* Analytical HPLC column: RP-18 column Chromolith Speed ROD from Merck KgaA, Germany). Elution: acetonitrile + 0.1 % trifluoroacetic acid (TFA) / water + 0.1 % trifluoroacetic acid (TFA) in a ratio of from 5:95 to 95:5 in 5 minutes at 40 °C.

Characterization by H-NMR (500 MHz, DMSO) [delta]: 10.87 (s, 1 H), 8.53 (d, 1 H), 8.22 (d, 1 H), 7.75 (s, 1 H), 7.65 (m, 2H), 7.40 (s, 1 H), 3.09 (m, 2H), 2.92 (m, 2H) 1 .15 (m, 6H).

Example P.1 1 : N-[4-chloro-2-[(diethyl- ⁴ -sulfanylidene)carbamoyl]-6-methyl-phenyl]-2- (3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxami de

To an aqueous solution of sodium hydroxide (4.2 ml. of a 2 N solution, 8.4 mmol, 2.0 equiv.) was added (diethyl- ⁴ -sulfanylidene)ammonium sulfate (1 .3 g, 4.2 mmol, 1 .00 equiv) in portions at 0°C. After 30 min, the mixture was freeze dried at -78°C. The resulting residue was suspended in methanol (10 ml.) and added to a solution of methyl 5-chloro-2-[[2-(3-chloro-2-pyridyl)-5- (trifluoromethyl)pyrazole-3-carbonyl]amino]-3-methyl-benzoat e (2.00 g, 4.23 mmol, 1.00 equiv.) in methanol (10 ml.) at 40°C and stirred at room temperature overnight. After concentration in vacuum, the residue was purified via column chromatography on silica gel to obtain the title compound (160 mg, 7%).

Characterization by HPLC ^* : 4.36 min.

^* Analytical HPLC column: RP-18 column Chromolith Speed ROD from Merck KgaA, Germany). Elution: acetonitrile + 0.1 % trifluoroacetic acid (TFA) / water + 0.1 % trifluoroacetic acid (TFA) in a ratio of from 5:95 to 95:5 in 5 minutes at 40 °C.

Characterization by H-NMR (500 MHz, DMSO-d ₆ ) [delta]: 10.87 (s, 1 H), 8.53 (d, 1 H), 8.22 (d, 1 H), 7.75 (s, 1 H), 7.65 (m, 2H), 7.40 (s, 1 H), 3.09 (m, 2H), 2.92 (m, 2H) 1 .15 (m, 6H).