Process for preparing imidazole compounds

Abstract

The present invention is directed to a method for preparing a compound of formula (I) as described herein by reacting in a one-step reaction a diamine compound of formula (II) with a nitrile compound of formula (III). Also encompassed are the compounds thus obtained.

Description

[0001] PROCESS FOR PREPARING IMIDAZOLE COMPOUNDS

[0002] Field of the invention

[0003] The present invention lies in the field of organic chemistry and relates to a one-step process for preparing multi-cyclic imidazoles by reacting diamines with nitrile compounds.

[0004] Background of the invention

[0005] Bicyclic imidazoles such as benzimidazoles exhibit various biological effects, e.g. antimicrobial and antiviral effects. The motif enables high levels of functionalization and therefore offers a large substrate scope. Over the last years the application of imidazoles and specifically benzimidazoles has attracted much interest, resulting in the development of new synthesis routes (Chung, Nguyen Thi et al., “Recent achievements in the synthesis of benzimidazole derivatives.” RSC Adv., 2023,13, 32734-32771).

[0006] However due to the increased interest in such compounds, there is need in the art for simple processes, in particular one-step processes, that allow synthesis of the desired imidazoles in an efficient manner.

[0007] Summary of the invention

[0008] The present invention meets this need by providing a process that allows preparing imidazoles in a single step. It is based on the surprising finding of the inventors that complex imidazole compounds with multiple substituents can be produced in a one-step reaction using diamines and nitrile compounds as the reactants.

[0009] In a fist aspect, the present invention therefore relates to a process for preparing a compound of formula (I):

[0010]

[0011] wherein

[0012] A is a 5- to 12-membered partially or fully unsaturated mono-, bi- or tricyclic carbo- or heterocyclic ring, comprising up to 4 heteroatoms selected from N, O and S, wherein said N may be unsubstituted or substituted with RN, and said ring being unsubstituted or substituted with one or more substituents R1;

[0013] B is a 5- to 12-membered saturated or partially or fully unsaturated mono-, bi- or tricyclic carbo- or heterocyclic ring comprising up to 4 heteroatoms selected from N, O and S, wherein said Nmay be unsubstituted or substituted with RN, and said ring being unsubstituted or substituted with one or more substituents R2;

[0014] each R1independently is S(O)m-Ci-C4-alkyl, S(0)m-C3-C6-cycloalkyl, S(0)m-C3-C6-cycloalkyl-Ci- C4-alkyl, S(O)(=NH)RM, S(O)(=NRM)RM, halogen, cyano, NH2, NHRM, N(RM)2, NH-C(O)-RM, C(O)RM, C(O)ORM, ORM, Ci-C6-alkyl, C3-C6-cycloalk(en)yl, C2-C6-alkenyl, C2-C6-alkynyl, C6- Cw-aryl, a 5- to 12-membered saturated, partially unsaturated, or fully unsaturated mono-, bi- or tricyclic heterocyclic ring comprising up to 4 heteroatoms selected from N, O and S, wherein N is unsubstituted or substituted with RN,

[0015] wherein the alkyl, cycloalkyl, alkenyl, alkynyl groups are unsubstituted or substituted with one or more R11,

[0016] wherein the aryl and heterocyclic rings are unsubstituted or substituted with one or more R12; or two R1combine to form together with the atoms to which they are attached a 5- to 10- membered saturated, partially unsaturated, or fully unsaturated carbocyclic or heterocyclic ring comprising up to 4 heteroatoms selected from N, O and S, which is unsubstituted or substituted with one or more R12;

[0017] each R2independently is S(O)P-RW, halogen, cyano, NH2, NHRM, N(RM)2, NH-C(O)-RM, Si(Rs)3, wherein Rsis Ci-C4-alkyl, C(O)RM, C(O)ORM, COOH, ORM, Ci-C6-alkyl, C3-C6- cycloalk(en)yl, C2-Ce-alkenyl, C2-Ce-alkynyl, Ce-C -aryl, a 5- to 12-membered saturated, partially unsaturated, or fully unsaturated mono-, bi- or tricyclic heterocyclic ring comprising up to 4 heteroatoms selected from N, O and S, wherein N is unsubstituted or substituted with RN, or Si(Rs)3, wherein Rsis Ci-C4-alkyl,

[0018] wherein the alkyl, cycloalk(en)yl, alkenyl, alkynyl groups are unsubstituted or substituted with one or more R21,

[0019] wherein the aryl and heterocyclic rings are unsubstituted or substituted with one or more R22; or two R2combine to form together with the atoms to which they are attached a 5- to 10- membered saturated, partially unsaturated, or fully unsaturated carbocyclic or heterocyclic ring comprising up to 4 heteroatoms selected from N, O and S, wherein N is unsubstituted or substituted with RN, and wherein said ring is unsubstituted or substituted with one or more R22;

[0020] each R11independently is halogen or cyano;

[0021] each R12independently is C-i-Ce-alkyl, C2-Ce-alkenyl, C2-Ce-alkynyl, Ci-Ce-alkoxy-Ci-C4-alkyl, C3- Ce-cycloalkyl, C3-C6-cycloalkyl-Ci-C4-alkyl, C3-C6-cycloalkoxy-Ci-C4-alkyl, wherein the alkyl, alkoxy, cycloalkyl groups are unsubstituted or substituted with halogen or CN;

[0022] each R21independently is halogen or cyano or two R21combine to form a ring by a C2-Ce-alkyl bridge, which is unsubstituted or partly or fully halogenated and in which one or more carbon atoms may be replaced by O or N, wherein N is unsubstituted or substituted with RN; each R22independently is halogen, cyano, C-i-Ce-alkyl, C2-Ce-alkenyl, C2-Ce-alkynyl, C-i-Ce-alkoxy, Ci-Ce-alkoxy-Ci-C4-alkyl, Ci-C6-alkoxy-Ci-Ce-alkoxy-Ci-C4-alkyl Cs-Ce-cycloalkyl, C3-C6-cycloalkyl-Ci-C4-alkyl, C3-C6-cycloalkyl-Ci-C4-alkoxy, C3-C6-cycloalkoxy-Ci-C4-alkyl, NH- CO-RM, C(RM)2-CN, CHRM-CN, C(RM)2-(CONH2), CHRM-(CONH2), C(RM)2-(CSNH2), CHRM- (CSNH2), O-CH2-CN, O-CHRM-CN, O-C(RM)2-CN, O-C(RM)2-(CONH2), O-C(RM)2-(CSNH2), 0-C(CONH2)-C3-C6-cycloalkyl, 0-C(CSNH2)-C3-C6-cycloalkyl, O-S(O)2-RM, S(O)m-RM, S(O)(=NRM)RM, S(O)(=NH)RM, N=S(O)(RM)2, CO-N=SO(RM)2, SF5, or wherein two R22combine to form=0 (carbonyl) or=CF2(difluoromethylen); wherein the alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, and cycloalkoxy groups are unsubstituted or substituted with halogen or CN, or wherein at least one C is replaced by a heteroatom; or in case of two adjacent substituents R22, the substituents may combine to form a C2-Ce-alkylene group, which is unsubstituted or substituted with halogen and in which one or more carbon atoms may be replaced by O or N, wherein N is unsubstituted or substituted with RN;

[0023] each RMindependently is C-i-Ce-alkyl, C2-Ce-alkenyl, C2-Ce-alkynyl, Ci-Ce-alkoxy-Ci-C4-alkyl, C3- Ce-cycloalkyl, C3-C6-cycloalkyl-Ci-C4-alkyl, C3-C6-cycloalkoxy-Ci-C4-alkyl, wherein the alkyl, alkoxy, cycloalkyl groups are unsubstituted or substituted with halogen or CN or wherein at least one C is replaced by a heteroatom; or two substituents RMcombine to form a C2-Ce- alkylene group, which is unsubstituted or substituted with halogen and in which one or more carbon atoms may be replaced by O or N, wherein N is unsubstituted or substituted with RN; RNis H, Ci-C4-alkyl, Cs-Ce-cycloalkyl, or Ci-C4-alkyl-Ci-C4-alkoxy;

[0024] Rwis Ci-C4-alkyl, cyclopropyl, C3-C6-cycloalkyl-Ci-C4-alkyl;

[0025] m, p are independently 0, 1 , or 2;

[0026] and the N-oxides, stereoisomers, tautomers and agriculturally or veterinarily acceptable salts thereof;

[0027] by directly reacting, in a one-step reaction, a compound of formula (II)

[0028]

[0029] with a compound of formula (III)

[0030]

[0031] In various embodiments, said compound of formula (I) is a compound of formula (la),RVL^<O)P

[0032]

[0033] RN(la).

[0034] In such embodiments, B is unsubstituted or substituted with one or more substituents R2and R2is preferably not another group S(O)P-RW.

[0035] In various embodiments, said compound of formula (I) is a compound of formula (IV), (V) or (VI):

[0036] Rxo<>(0)p

[0037] s

[0038] (IV)

[0039] (V)

[0040]

[0041] wherein

[0042] A1, A2, A3and A4are each independently N, CH orCR1, wherein not more than two are N, wherein preferably A1, A2and A3are CH orCR1and A4is N, CH orCR1; and

[0043] B1, B2, B3and B4are each independently N, CH or CR2, wherein not more than two are N, wherein preferably B1, B2, and B3are CH or CR2and B4is N, CH or CR2.

[0044] In various embodiments, in the compound of formula (I)

[0045] (1) one of A1, A2, A3and A4is N and the others are CH or CR1, preferably

[0046] (a) A1is CH and at least one of A2and A3is CR1and the other is CH or CR1and A4is N or CH; or(b)A1and A4are CR1or CH, preferably CH, and one of A2and A3is N and the other is CH orCR1; or

[0047] (c) one of A1and A4is N and the other is CH or CR1, preferably CH, and A2and A3are CH orCR1;

[0048] and / or

[0049] (2) B1is CH and at least one of B2and B3is CR2and the other is CH or CR2and B4is N.

[0050] In various embodiments, the compound of formula (I) is a compound of formula (VII), (VIII), (IX), (X), (XI), (XII), (XIII), (XIV), (XV), or (XVI)

[0051] RVL o-^(°)P

[0052] (VII)

[0053] (VIII)

[0054]

[0055] (XI)

[0056] R

[0057] Kw

[0058] -s /

[0059]

[0060] wherein

[0061] each of RA2and RA3independently is selected from H, S(O)m-Ci-C4-alkyl, S(0)m-C3-C6-cycloalkyl, S(0)m-C3-C6-cycloalkyl-Ci-C4-alkyl, S(O)(=NH)RM, S(O)(=NRM)RM, halogen, cyano, NH2, NHRM, N(RM)2, NH-C(O)-RM, C(O)RM, C(O)ORM, ORM, Ci-C6-alkyl, C3-C6-cycloalk(en)yl, C2-Ce-alkenyl, C2-Ce-alkynyl, Ce-C -aryl, a 5- to 12-membered saturated, partially unsaturated, or fully unsaturated mono-, bi- or tricyclic heterocyclic ring comprising up to 4 heteroatoms selected from N, O and S, wherein N is unsubstituted or substituted with RN,

[0062] wherein the alkyl, cycloalkyl, alkenyl, alkynyl groups are unsubstituted or substituted with one or more R11,

[0063] wherein the aryl and heterocyclic rings are unsubstituted or substituted with one or more R12; or RA2and RA3combine to form together with the atoms to which they are attached a 5- to 6- membered partially unsaturated or fully unsaturated heterocyclic ring comprising up to 4 heteroatoms selected from N, O and S, wherein N is unsubstituted or substituted with RNwherein said ring is unsubstituted or substituted with halogen or C1-C4 alkyl, which can be substituted with halogen;

[0064] RA4and RA5are independently H or halogen, or C1-C4 alkyl, which can be substituted with halogen; each of RB2and RB3independently is selected from H, halogen, cyano, NH2, NHRM, N(RM)2, NH- C(O)-RM, C(O)RM, C(O)ORM, COOH, ORM, Ci-C6-alkyl, C3-C6-cycloalk(en)yl, C2-C6-alkenyl, C2-Ce-alkynyl, Ce-C -aryl, a 5- to 12-membered saturated, partially unsaturated, or fully unsaturated mono-, bi- or tricyclic heterocyclic ring comprising up to 4 heteroatoms selected from N, O and S, wherein N is unsubstituted or substituted with RN, or Si(Rs)3, wherein Rsis Ci-C4-alkyl,

[0065] wherein the alkyl, cycloalk(en)yl, alkenyl, alkynyl groups are unsubstituted or substituted with one or more R21,

[0066] wherein the aryl and heterocyclic rings are unsubstituted or substituted with one or more R22.

[0067] In these compounds, RNand Rwand p are as defined above. It is understood that S=(O)Pmeans S, S(=O) or S(=O)2, depending on whether p is 0, 1 or 2.

[0068] In various embodiments, one of RA2and RA3is H and the other is selected from S(O)m-Ci-C4-alkyl, S(0)m-C3-C6-cycloalkyl, S(0)m-C3-C6-cycloalkyl-Ci-C4-alkyl, S(O)(=NH)RM, S(O)(=NRM)RM, C1-C4-alkyl, C3-C6-cycloalkyl, Ci-C4-alkoxy, and C3-Ce-cycloalkoxy,

[0069] wherein the alkyl, cycloalkyl, alkoxy and cycloalkoxy groups are unsubstituted, partially halogenated, or fully halogenated;

[0070] wherein each RMis independently Ci-C3-alkyl which is unsubstituted or partially or fully halogenated; or C3-C6-cycloalkyl, or C3-C6-cycloalkyl in which at least one C is replaced by a heteroatom; or two RMcombine to form a C2-Ce-alkylene group, which is unsubstituted or partly or fully halogenated and in which one or more carbon atoms may be replaced by O or N, wherein N is unsubstituted or substituted with RN.

[0071] In various embodiments,(1) RB3is H orCi-C4-alkyl, Ci-C4-alkoxy, C3-C6-cycloalkyl, halogen, cyano, N(RM)2, NH-CO-RM; Ci-C4-alkynyl;

[0072] phenyl which is unsubstituted or substituted with at least one Ci-C4-alkyl which is unsubstituted or partially or fully halogenated, C3-Ce-cycloalkyl, halogen, O-S(O)2-RM, CN, Ci-Cs-alkoxy, which is unsubstituted or partially or fully halogenated, C3-Ce-cycloalkoxy, N=S(O)(RM)2, or

[0073] a five- or six-membered aromatic heterocycle, which is unsubstituted or substituted with at least one halogen, CN, Ci-C4-alkyl, which is unsubstituted or partially or fully halogenated, C3-Ce-cycloalkyl, Ci-Cs-alkoxy, which is unsubstituted or partially or fully halogenated;

[0074] wherein each RMis independently Ci-Cs-alkyl which is unsubstituted or partially or fully halogenated; or C3-Ce-cycloalkyl, or C3-Ce-cycloalkyl in which at least one C is replaced by a heteroatom; or two substituents RMcombine to form a Cs-Ce-alkylene group, which is unsubstituted or partly or fully halogenated and in which one or more carbon atoms may be replaced by O or N, wherein N is unsubstituted or substituted with RN; and / or

[0075] (2) RB2is H, halogen, or

[0076] (2a) Cs-Ce-cycloalkyl, which is unsubstituted or partially or fully halogenated; or halogen; or (2b) phenyl substituted with one R22, or substituted with up to 5 halogens; or (2c) 1,3-benzodioxole which is unsubstituted or partly or fully halogenated; or (2d) a six-membered saturated, partially unsaturated, or fully unsaturated heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one, two or three, same or different heteroatoms O or N which may be unsubstituted or substituted with Ci-C4- alkyl, and is unsubstituted, or substituted with one R22, or substituted with two halogens; or (2e) or Ci-C4-alkynyl, which is unsubstituted or substituted with Cs-Ce-cycloalkyl or Si(Rs)3, wherein Rsis Ci-C4-alkyl; or

[0077] (2f) a five-membered saturated, partially unsaturated, or fully unsaturated heterocyclic ring, wherein said heterocyclic ring comprises one, two or three, same or different heteroatoms selected from N, O, and S, wherein N may be unsubstituted or substituted with Ci-C4-alkyl, Cs-Ce-cycloalkyl, C-bound Ci-C4-alkoxy, Ci-C4-alkyl-Ci-C4-alkoxy; wherein the five-membered ring is unsubstituted or substituted with one R22;

[0078] wherein R22is halogen, cyano, Ci-C4-alkyl, which is unsubstituted or partially or fully halogenated; NH-CO-RM; Cs-Ce-cycloalkyl; Ci-C4-alkoxy-Ci-C4-alkyl, C3-Ce-cycloalkyl-Ci-C3-alkoxy, Ci-C4-alkoxy-Ci-C4-alkoxy-Ci-C4-alkyl; C(RM)2-CN, CHRM-CN, C(RM)2-(CONH2), CHRM-(CONH2), C(RM)2-(CSNH2), CHRM-(CSNH2), 1-cyano-C3-C6-cycloalkyl, 1-C3-C6-cycloalkyl-carboxamide, 1-C3-C6-cycloalkyl-thiocarboxamide, O-CH2-CN, O-CHRM-CN, O-C(RM)2-CN, O-C(RM)2-(CONH2), O-C(RM)2-(CSNH2), 0-1-cyano-C3-C6-cycloalkyl, 0-C(CONH2)-C3-Ce-cycloalkyl, O-C(CSNH2)-C3-Ce-cycloalkyl; O-S(O)2-RM; Ci-C3-alkoxy, which is unsubstituted or partially or fully halogenated; C3-Ce-cycloalkyl-Ci-C3-alkoxy which is unsubstituted or partially or fully halogenated, C3-Ce-cycloalkoxy, which is unsubstituted or partially or fully halogenated;S-RM, SO-RM; SO2-RM; S(O)(=NRM)RM, S(O)(=NH)RM, N=S(O)(RM)2, CO-N=SO(RM)2, SF5, or two R22combine to form carbonyl or difluoromethylen;

[0079] wherein each RMis independently C-i-Cs-alkyl which is unsubstituted or partially or fully halogenated; or Cs-Ce-cycloalkyl, or Cs-Ce-cycloalkyl in which at least one C is replaced by a heteroatom; or two substituents RMcombine to form a C2-Ce-alkylene group, which is unsubstituted or partly or fully halogenated and in which one or more carbon atoms may be replaced by O or N wherein N is unsubstituted or substituted with RN.

[0080] In various embodiments,

[0081] (1) RB3is H and RB2is a five-membered saturated, partially unsaturated, or fully unsaturated heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one, two or three, same or different heteroatoms selected from N, O, and S, wherein N may be unsubstituted or substituted with Ci-C4-alkyl; Cs-Ce-cycloalkyl, C-bound Ci-C4-alkoxy, Ci-C4-alkyl-Ci-C4-alkoxy; wherein the five-membered ring is unsubstituted or substituted with one R22, or in which the ring contains a group -C(RM)2- or the atom via which RB2is attached to the remainder of the molecule, has a further substituent RM;

[0082] wherein each R22is independently halogen, cyano, Ci-C4-alkyl, which is unsubstituted or partially or fully halogenated; Cs-Ce-cycloalkyl, or Cs-Ce-cycloalkyl, in which one C is replaced by an O, NRM, S, SO, or SO2; Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkoxy-Ci-C4-alkoxy-Ci-C4-alkyl, C3-C6-cycloalkyl-Ci-C3-alkoxy, C(RM)2-(CN), CHRM-CN, C(RM)2-(CONH2), CHRM-(CONH2), C(RM)2-(CSNH2), CHRM-(CSNH2), l-cyano-Cs-Ce-cycloalkyl, l-Cs-Ce-cycloalkyl-carboxamide, I-C3-C6-cycloalkyl-thiocarboxamide, O-CH2-CN, O-CHRM-CN, O-C(CN)(RM)2, O-C(CONH2)(RM)2, O-C(CSNH2)(RM)2,

[0083] O-1-cyano- Cs-Ce-cycloalkyl, O- C(CONH2)- Cs-Ce-cycloalkyl, O- C(CSNH2)- Cs-Ce-cycloalkyl, O-S(O)2-RM, SO2-RM, Ci-Cs-alkoxy which is unsubstituted or partially or fully halogenated, C3-C6-cycloalkyl-Ci-Cs-alkoxy which is unsubstituted or partially or fully halogenated, Cs-Ce-cycloalkoxy which is unsubstituted or partially or fully halogenated, S(O)(=NRM)RM, S(O)(=NH)RM, N=S(O)(RM)2, CO-N=SO(RM)2, or two R22combine to form carbonyl or difluoromethylen, and wherein each RMis independently Ci-Cs-alkyl which is unsubstituted or partially or fully halogenated, or Cs-Ce-cycloalkyl, or Cs-Ce-cycloalkyl in which at least one C is replaced by a heteroatom,

[0084] or in case of two adjacent substituents RM, the substituents may form a C2-Ce-alkylene group, which is unsubstituted or partly or fully halogenated and in which one or more carbon atoms may be replaced by O or N, wherein N is unsubstituted or substituted with RN; or

[0085] (2) RB3is H and RB2is

[0086] (2a) phenyl substituted with (2aa) one R22, or (2ab) substituted with one R22and one halogen, or (2ac) substituted with up to 5 halogens; or(2b) a six-membered saturated, partially unsaturated, or fully unsaturated heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one, two or three, same or different heteroatoms O or N which may be unsubstituted or substituted with C1-C4- alkyl, and is substituted with one R22, or substituted with two halogens; or a 1 ,3-benzodioxole which is unsubstituted or halogenated; or Ci-C4-alkynyl, which is unsubstituted or substituted with Si(Rs)3; wherein Rsis Ci-C4-alkyl;

[0087] wherein each R22is independently C(RM)2-(CN), CHRM-CN, C(RM)2-(CONH2), CHRM-(CONH2), C(RM)2-(CSNH2), CHRM-(CSNH2), 1-cyano-C3-C6-cycloalkyl, 1-C3-C6-cycloalkyl-carboxamide, 1-C3-C6-cycloalkyl-thiocarboxamide, O-CH2-CN, O-CHRM-CN, O-C(CN)(RM)2, O-C(CONH2)(RM)2, O-C(CSNH2)(RM)2, 0-1-cyano-C3-C6-cycloalkyl, O- C(CONH2)- C3-C6-cycloalkyl, O- C(CSNH2)- C3-Ce-cycloalkyl, O-S(O)2-RM, Ci-C3-alkoxy which is unsubstituted or partially or fully halogenated, C3-C6-cycloalkyl-Ci-C3-alkoxy which is unsubstituted or partially or fully halogenated, C3-Ce-cycloalkoxy which is unsubstituted or partially or fully halogenated, S(O)(=NRM)RM, S(O)(=NH)RM, N=S(O)(RM)2, CO-N=SO(RM)2, halogen, cyano, or two R22combine to form carbonyl or difluoromethylen; and

[0088] wherein each RMis independently Ci-C3-alkyl which is unsubstituted or partially or fully halogenated, or C3-C6-cycloalkyl, or C3-C6-cycloalkyl in which at least one C is replaced by a heteroatom,

[0089] or in case of two adjacent substituents RM, the substituents may form a C2-Ce-alkylene group, which is unsubstituted or partly or fully halogenated and in which one or more carbon atoms may be replaced by O or N, wherein N is unsubstituted or substituted with RN; or

[0090] (3) RB2and RB3are H; or

[0091] (4) RB2is Ci-Ce-alkyl or C3-C6-cycloalkyl, wherein the alkyl and cycloalkyl groups are unsubstituted or substituted with cyano, and RB3is H.

[0092] In various embodiments, p is 1 or 2, preferably 2.

[0093] In various embodiments, Rwis Ci-C4-alkyl, preferably an ethyl group.

[0094] In various embodiments, the reaction is a one-step reaction. The reaction may be carried out in the presence or absence of a Lewis acid. In various embodiments, the Lewis acid is selected from the group consisting of Cu(OTf)2, PdCI2, ZnCI2, NiCI2, MnCI2, CaCI2, CrCI2, FeCI2, FeCI3, CoCI2, CdCI2, PtCI2, CuCI2, CuCI, SnCI2, Ti(OiPr)4, Zn(OTf)2, Fe(OTf)2, (CH3)3SiOTf, (CH3)3SiCI, and combinations thereof.

[0095] In various embodiments, the process is carried out in the presence of a suitable solvent.In various embodiments, the process is carried out at elevated temperature, preferably at a temperature in the range of 100 to 160 °C and / or for 1 to 24 h. The heating may be achieved by microwaves.

[0096] In another aspect, the present invention also relates to a compound obtainable by a process according to the invention.

[0097] Detailed description

[0098] Unless otherwise indicated, all terms used therein have their common and scientifically accepted meaning.

[0099] The term "compound(s) of formula (I)" as used in the invention refers to and comprises the compound(s) as defined herein and / or stereoisomer(s), salt(s), tautomer(s) or N-oxide(s) thereof. The same applies to all formulae described herein, i.e. compound of formula (II), compound of formula (III) etc.

[0100] The compounds may be amorphous or may exist in one or more different crystalline states (polymorphs) or modifications which may have different macroscopic properties such as stability or show different biological properties such as activities.

[0101] The compounds of the formula (I) may have one or, depending on the substitution pattern, more centers of chirality, in which case they are present as mixtures of enantiomers or diastereomers. The invention provides both the single pure enantiomers or pure diastereomers of the compounds of formula (I), and their mixtures. Suitable compounds of the formula (I) also include all possible geometrical stereoisomers (cis / trans isomers) and mixtures thereof. Cis / trans isomers may be present with respect to an alkene, carbon-nitrogen double-bond or amide group. The term "stereoisomer(s)" encompasses both optical isomers, such as enantiomers or diastereomers, the latter existing due to more than one center of chirality in the molecule, as well as geometrical isomers (cis / trans isomers). The invention relates to every possible stereoisomer of the compounds of formula (I), i.e. to single enantiomers or diastereomers, as well as to mixtures thereof.

[0102] Depending on the substitution pattern, the compounds of the formula (I) may be present in the form of their tautomers. Hence the invention also encompasses the tautomers of the formula (I) and the stereoisomers, salts, tautomers and N-oxides of said tautomers.

[0103] Salts of the compounds of the formula (I) are preferably agriculturally and / or veterinary acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid ofthe anion in question if the compound of formula (I) has a basic functionality or by reacting an acidic compound of formula (I) with a suitable base.

[0104] Suitable agriculturally or veterinary useful salts are especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, do not have any adverse effect on the action of the compounds according to the invention. Suitable cations are in particular the ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium, and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium (NH4+) and substituted ammonium in which one to four of the hydrogen atoms are replaced by Ci-C4-alkyl, Ci-C4-hydroxyalkyl, Ci-C4-alkoxy, C1-C4-alkoxy-Ci-C4-alkyl, hydroxy-Ci-C4-alkoxy-Ci-C4-alkyl, phenyl or benzyl. Examples of substituted ammonium ions comprise methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2-hydroxyethoxy)ethyl-ammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzyltriethylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(Ci-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(Ci-C4-alkyl)sulfoxonium.

[0105] Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting the compounds of the formulae I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.

[0106] The term “N-oxide” includes any compound of the invention which has at least one tertiary nitrogen atom that is oxidized to an N-oxide moiety.

[0107] The organic moieties groups mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members. The prefix Cx-Cyindicates in each case the possible number of carbon atoms in the group. "Halogen" will be taken to mean F, Cl, Br, and I, preferably F, Cl, Br.

[0108] The terms compound(s) of formula (x) and compound(s) (x), wherein x is a roman orarab number are used herein interchangeably and refer to a single or several compounds as defined by the respective formula (x).The term “substituted with”, e.g. as used in "partially, or fully substituted with" means that one or more, e.g. 1 , 2, 3, 4 or 5 or all of the hydrogen atoms of a given radical have been replaced by one or more, same or different substituents as subsequently defined. Accordingly, for substituted cyclic moieties, e.g. 1 -cyanocyclopropyl, one or more of the hydrogen atoms of the cyclic moiety may be replaced by one or more, same or different substituents.

[0109] The term "Cx-Cy-alkyl" as used herein refers to a branched or unbranched saturated hydrocarbon group having n to m, e.g. 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, e.g. methyl, ethyl, propyl, 1 -methylethyl, butyl, 1 -methylpropyl, 2-methylpropyl, 1,1 -dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 -ethyl propyl, 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, heptyl, octyl, 2-ethylhexyl, nonyl and decyl and their isomers. Ci-C4-alkyl means for example methyl, ethyl, propyl, 1 -methylethyl, butyl, 1 -methylpropyl, 2-methylpropyl or 1,1 -dimethylethyl. “Alk(en)yl”, as used herein, relates to alkyl and alkenyl groups. “Alkenyl” groups correspond to the alkyl groups but contain at least one C-C double bond. Similarly, “alkynyl” groups comprise at least one C-C triple bond.

[0110] If an alkyl group is substituted by halogen, some or all of the hydrogen atoms in this group may be replaced by halogen atoms as mentioned above, e.g. may be Ci-C4-haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1 -chloroethyl, 1-bromoethyl, 1 -fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoro-ethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl and the like. Particularly comprised is Ci-C2-fluoroalkyl, which is synonym with methyl or ethyl, wherein 1, 2, 3, 4 or 5 hydrogen atoms are substituted with fluorine atoms, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 -fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl and pentafluoromethyl.

[0111] Similarly, "Cx-Cy-alkoxy" refers to straight-chain or branched alkyl groups having n to m carbon atoms, e.g. 1 to 10, in particular 1 to 6 or 1 to 4 carbon atoms (as mentioned above) bonded through oxygen at any bond in the alkyl group. Examples include Ci-C4-alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy and tert-butoxy. In such groups, the alkyl group may also be substituted by halogen as described above.

[0112] The suffix “-carbonyl” in a group or “C(=O)” denotes in each case that the group is bound to the remainder of the molecule via a carbonyl C=O group. This is the case e.g. in alkylcarbonyl,haloalkylcarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, alkylcarbonylamino, and hydroxycarbonyl. For example, a hydroxycarbonyl group would refer to a carbonic acid group -C(=O)OH, and an aminocarbonyl group would refer to an amide group -C(=O)NH2, both of which are bound to the remainder of the molecule via the carbonyl “C=O” group.

[0113] The term "aryl" as used herein refers to a mono-, bi- or tri- or multi-cyclic aromatic hydrocarbon radical such as phenyl or naphthyl, in particular phenyl (also referred as to CeHs as subsitituent).

[0114] The term "Cs-Cy-cycloalkyl" as used herein refers to a monocyclic ring of 3- to y-membered saturated cycloaliphatic radicals, e.g. cyclopropyl (CC3H5), cyclobutyl (CC4H7), cyclopentyl (CC5H9), cyclohexyl (cCeHn), cycloheptyl, cyclooctyl and cyclodecyl.

[0115] Accordingly, the term “Cs-Cy-cycloalkoxy” as used herein refers to a “C3-Cy”-cycloalkyl moiety which is bonded to the rest of the molecule via an oxygen atom, such as in cyclopropoxy, cyclobutoxy, cyclopentoxy and cyclohexoxy.

[0116] The term "cycloalkylalkyl" denotes as well as the term “alkyl which may be substituted with cycloalkyl” an alkyl group which is substituted with a cycloalkyl ring, wherein alkyl and cycloakyl are as herein defined.

[0117] The term "Cs-Cy-cycloalkenyl" as used herein refers to a monocyclic ring of 3- to y-membered partially unsaturated cycloaliphatic radicals. “Cycloalk(en)yl”, as used herein, encompasses both cycloalkyl and cycloalkenyl groups.

[0118] The term "cycloalkylcycloalkyl" denotes as well as the term “cycloalkyl which may be substituted with cycloalkyl” a cycloalkyl substitution on another cycloalkyl ring, wherein each cycloalkyl ring independently has from 3 to 7 carbon atom ring members and the cycloalkyls are linked through one single bond or have one common carbon atom. Examples of cycloalkylcycloalkyl include cyclopropylcyclopropyl (e.g. 1 , 1 -bicyclopropyl-2-yl), cyclohexylcyclohexyl wherein the two rings are linked through one single common carbon atom (e.g. 1,1'-bicyclohexyl-2-yl), cyclohexylcyclopentyl wherein the two rings are linked through one single bond (e.g. 4-cyclopentylcyclohexyl) and their different stereoisomers such as (1 R,2S)-1 , T-bicyclopropyl-2-yl and (1 R,2R)-1 ,1'-bicyclopropyl-2-yl.

[0119] The term “carbocycle” or “carbocyclyl” includes, unless otherwise indicated, in general a 3- to 12-membered, preferably a 3- to 8-membered or a 5- to 8-membered, more preferably a 5- or 6-membered mono-cyclic, ring comprising 3 to 12, preferably 3 to 8 or 5 to 8, more preferably 5 or 6carbon atoms. The carbocyclic radicals may be saturated, partially unsaturated, or fully unsaturated. Preferably, the term “carbocycle” covers cycloalkyl and cycloalkenyl groups as defined above, for example cyclopropane, cyclobutane, cyclopentane and cyclohexane rings. When it is referred to “fully unsaturated” carbocycles, this term also includes “aromatic” carbocycles. In certain preferred embodiments, a fully unsaturated carbocycle is an aromatic carbocycle as defined below, preferably a 6-membered aromatic carbocycle.

[0120] The term "hetaryl" or “aromatic heterocycle” or “aromatic heterocyclic ring” includes monocyclic 5-or 6-membered heteroaromatic radicals comprising as ring members 1, 2, 3, or 4 heteroatoms selected from N, O, and S. Examples of 5- or 6-membered heteroaromatic radicals include pyridyl, i.e. 2-, 3-, or 4-pyridyl, pyrimidinyl, i.e. 2-, 4- or 5-pyrimidinyl, pyrazinyl, pyridazinyl, i.e. 3- or 4-pyridazinyl, thienyl, i.e. 2- or 3-thienyl, furyl, i.e. 2-or3-furyl, pyrrolyl, i.e. 2- or3-pyrrolyl, oxazolyl, i.e. 2-, 3- or 5-oxazolyl, isoxazolyl, i.e. 3-, 4- or 5-isoxazolyl, thiazolyl, i.e. 2-, 3- or 5-thiazolyl, isothiazolyl, i.e. 3-, 4- or 5-isothiazolyl, pyrazolyl, i.e. 1-, 3-, 4- or 5-pyrazolyl, i.e. 1-, 2-, 4- or 5-imidazolyl, oxadiazolyl, e.g. 2- or 5-[1 ,3,4]oxadiazolyl, 4- or 5-(1,2,3-oxadiazol)yl, 3- or 5-(1 ,2,4-oxadiazol)yl, 2- or 5-(1,3,4-thiadiazol)yl, thiadiazolyl, e.g. 2- or 5-(1,3,4-thiadiazol)yl, 4- or 5-(1 ,2 ,3-thiadiazol)yl , 3- or 5-(1 ,2 ,4-thiadiazol)yl , triazolyl, e.g. 1 H-, 2H- or 3H-1 ,2 ,3-triazol-4-yl , 2H-triazol-3-yl, 1H-, 2H-, or4H-1 ,2,4-triazolyl and tetrazolyl, i.e. 1H- or 2H-tetrazolyl.

[0121] The terms “heterocycle”, "heterocyclyl" or “heterocyclic ring” includes, unless otherwise indicated, in general 3- to 12-membered, preferably 3- to 8-membered, 3- to 7-membered, or 5- to 8-membered, more preferably 5- or 6-membered, in particular 6-membered monocyclic heterocyclic radicals. The heterocyclic radicals may be saturated, partially unsaturated, or fully unsaturated. As used in this context, the term “fully unsaturated” also includes “aromatic”. In a preferred embodiment, a fully unsaturated heterocycle is thus an aromatic heterocycle, preferably a 5- or 6-membered aromatic heterocycle comprising one or more, e.g. 1, 2, 3, or 4, preferably 1, 2, or 3 heteroatoms selected from N, O and S as ring members. It is understood that depending on the saturation level, N as a ring atom may be N, NH or substituted (e.g. NRN). Examples of aromatic heterocycles are provided above in connection with the definition of “hetaryl”. Unless otherwise indicated, “hetaryls” are thus covered by the term “heterocycles”. The heterocyclic non-aromatic radicals usually comprise 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3 heteroatoms selected from N, O, and S as ring members, where S-atoms as ring members may be present as S, SO or SO2, and N-atoms may be oxidized, or non-oxidized. Examples of 5- or 6-membered heterocyclic radicals comprise saturated or unsaturated, non-aromatic heterocyclic rings, such as oxiranyl, oxetanyl, thietanyl, thietanyl-S-oxid (S-oxothietanyl), thietanyl-S-dioxid (S-dioxothiethanyl), pyrrolidinyl, pyrrolinyl, pyrazolinyl, tetrahydrofuranyl, dihydrofuranyl, 1,3-dioxolanyl, thiolanyl, S-oxothiolanyl, S-dioxothiolanyl, dihydrothienyl, S-oxodihydrothienyl, S-dioxodihydrothienyl, oxazolidinyl, oxazolinyl, thiazolinyl, oxathiolanyl, piperidinyl, piperazinyl, pyranyl, dihydropyranyl, tetrahydropyranyl, 1,3-and 1,4-dioxanyl, thiopyranyl, S-oxothiopyranyl, S-dioxothiopyranyl, dihydrothiopyranyl, S-oxodihydrothiopyranyl, S-dioxodihydrothiopyranyl, tetrahydrothiopyranyl, S-oxotetra-hydrothiopyranyl, S-dioxotetrahydrothiopyranyl, morpholinyl, thiomorpholinyl, S-oxothiomorpho-linyl, S-dioxothiomorpholinyl, thiazinyl and the like. Examples for heterocyclic ring also comprising 1 or 2 carbonyl groups as ring members comprise pyrrolidin-2-onyl, pyrrolidin-2,5-dionyl, imidazolidin-2-onyl, oxazolidin-2-onyl, thiazolidin-2-onyl and the like.

[0122] The terms “alkylene”, “alkenylene”, and “alkynylene” refer to alkyl, alkenyl, and alkynyl as defined above, respectively, which are bonded to the remainder of the molecule, via two atoms, preferably via two carbon atoms, of the respective group, so that they represent a linker between two moieties of the molecule. In particular, the term “alkylene” may refer to alkyl chains such as CH2CH2, -CH(CH3)-, CH2CH2CH2, CH(CH3)CH2, CH2CH(CH3), CH2CH2CH2CH2, CH2CH2CH2CH2CH2, CH2CH2CH2CH2CH2CH2, and CH2CH2CH2CH2CH2CH2CH2. Similarly, “alkenylene” and “alkynylene” may refer to alkenyl and alkynyl chains, respectively.

[0123] The term "5- to 6-membered carbocyclic ring" as used herein includes cyclopentane and cyclohexane rings, but also the partially or fully unsaturated rings, such as cyclopentene, cyclohexene, and benzene rings.

[0124] Examples of 5- or 6-membered saturated heterocyclic rings include: 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-pyrazo-lidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 2-oxazolidinyl, 4-oxazo-lidinyl, 5-oxazolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 2-thiazolidinyl, 4-thia-zolidinyl, 5-thiazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 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, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 3-hexahydropyridazinyl, 4-hexahydropyridazinyl, 2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl, 2-piperazinyl, 1 ,3,5-hexahydrotriazin-2-yl and 1 ,2,4-hexahydrotriazin-3-yl, 2-morpholinyl, 3-morpholinyl, 2-thiomorpholinyl, 3-thiomorpholinyl, 1-oxothiomorpholin-2-yl, 1-oxothiomorpholin-3-yl, 1 ,1-dioxothiomorpholin-2-yl, 1,1-dioxothiomorpholin-3-yl.

[0125] Examples of 5- or 6-membered partially unsaturated heterocyclyl or heterocyclic rings 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 tetrahydropyridazinyl, 2-di- or tetrahydropyrimidinyl, 4-di- or tetrahydropyrimidinyl, 5-di- or tetrahydropyrimidinyl, di- or tetrahydropyrazinyl, 1,3, 5-di- or tetrahydrotriazin-2 -yl.

[0126] Examples of 5- or 6-membered fully unsaturated heterocyclic (hetaryl) or heteroaromatic rings 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, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 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.

[0127] A "C2-Cy-alkylene" is divalent branched or preferably unbranched saturated aliphatic chain having 2 to m, e.g. 2 to 7 carbon atoms, for example CH2CH2, -CH(CH3)-, CH2CH2CH2, CH(CH3)CH2, CH2CH(CH3), CH2CH2CH2CH2, CH2CH2CH2CH2CH2, CH2CH2CH2CH2CH2CH2, and CH2CH2CH2CH2CH2CH2CH2.

[0128] The term “alkylamino” as used herein refers to a straight-chain or branched saturated alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, which is bonded via a nitrogen atom, e.g. an -NH- group.

[0129] The term “dialkylamino” as used herein refers to a straight-chain or branched saturated alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, which is bonded via a nitrogen atom, which is substituted by another straight-chain or branched saturated alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, e.g. a methylamino or ethylamino group.

[0130] The term "alkylcarbonyl" (Ci-Ce-C(=O)-) refers to a straight-chain or branched alkyl group as defined above, which is bonded via the carbon atom of a carbonyl group (C=O) to the remainder of the molecule.

[0131] The term "alkoxycarbonyl" refers to an alkoxy group as defined above, which is bonded via the carbon atom of a carbonyl group (C=O) to the remainder of the molecule.The term "alkylaminocarbonyl" (Ci-Ce-NH-C(=O)-) refers to a straight-chain or branched alkylamino group as defined above, which is bonded via the carbon atom of a carbonyl group (C=O) to the remainder of the molecule. Similarly, the term "dialkylaminocarbonyl" refers to a straight-chain or branched saturated alkyl group as defined above, which is bonded to a nitrogen atom, which is substituted with another straight-chain or branched saturated alkyl group as defined above, which nitrogen atom in turn is bonded via a carbonyl group (C=O) to the remainder of the molecule.

[0132] “One-step reaction”, as used herein, has the common meaning as understood in the field of organic chemistry. In particular, it means that to compounds directly react with each other to form the given product without having to be converted into different compounds in a separate reaction which then form the final product. In various embodiments, such a one-step reaction is also a one-pot reaction, i.e. there is no separation or purification step in between. “Directly reacting”, as used herein, means that the given compounds directly react with each other in a chemical reaction, i.e. there the compounds are not changed or modified by other chemical reactions before the reaction. It is understood that in a one-step reaction transient intermediates may be formed but that these continue the reaction to form the final product. As detailed herein below, one-step reaction and directly reacting means that the nitrile compound (III) reacts with the diamine (II), without previously being converted into a carbonyl halogenide, such as carbonyl chloride, carboxylic acid or aldehyde.

[0133] The reaction mixtures obtained can be worked up in a customary manner, for example by mixing with water, extracting with an appropriate organic solvent, separating the phases and, if appropriate, chromatographic purification of the crude products. Some of the intermediates and end products are obtained in the form of colourless or slightly brownish viscous oils which are purified or freed from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, purification can also be carried out by recrystallization or digestion.

[0134] If the synthesis yields mixtures of isomers, a separation is generally not strictly necessarily since in some cases the individual isomers can be interconverted during work-up for use or during application (for example under the action of light, acids or bases). Such conversions may also take place after use, for example in the treatment of plants in the treated plant, or in the pest to be controlled.

[0135] A skilled person will readily understand that the preferences for the variables defined herein, also in particular the ones given in the tables below for the respective substituents, given herein in connection with compounds I apply for the intermediates (compounds II and III) accordingly.Thereby, the substituents in each case have independently of each other or more preferably in combination the meanings as defined herein.

[0136] The variables have, each on their own and in combination, the following preferred meanings.

[0137] The invention generally relates to a process for preparing imidazoles of formula (I)

[0138] RN

[0139]

[0140] (I)

[0141] wherein

[0142] A is a 5- to 12-membered partially or fully unsaturated mono-, bi- or tricyclic carbo- or heterocyclic ring, comprising up to 4 heteroatoms selected from N, O and S, wherein said N may be unsubstituted or substituted with RN, and said ring being unsubstituted or substituted with one or more substituents R1;

[0143] B is a 5- to 12-membered saturated, partially unsaturated, or fully unsaturated mono-, bi- or tricyclic carbo- or heterocyclic ring comprising up to 4 heteroatoms selected from N, O and S, wherein said N may be unsubstituted or substituted with RN, and said ring being unsubstituted or substituted with one or more substituents R2;

[0144] each R1independently is S(O)m-Ci-C4-alkyl, S(0)m-C3-C6-cycloalkyl, S(0)m-C3-C6-cycloalkyl-Ci- C4-alkyl, S(O)(=NH)RM, S(O)(=NRM)RM, halogen, cyano, NH2, NHRM, N(RM)2, NH-C(O)-RM, C(O)RM, C(O)ORM, ORM, Ci-C6-alkyl, C3-C6-cycloalk(en)yl, C2-C6-alkenyl, C2-C6-alkynyl, C6- Cw-aryl, a 5- to 12-membered saturated, partially unsaturated, or fully unsaturated mono-, bi- or tricyclic heterocyclic ring comprising up to 4 heteroatoms selected from N, O and S, wherein N is unsubstituted or substituted with RN,

[0145] wherein the alkyl, cycloalkyl, alkenyl, alkynyl groups are unsubstituted or substituted with one or more R11,

[0146] wherein the aryl and heterocyclic rings are unsubstituted or substituted with one or more R12; or two R1combine to form together with the atoms to which they are attached a 5- to 10- membered saturated, partially unsaturated, or fully unsaturated carbocyclic or heterocyclic ring comprising up to 4 heteroatoms selected from N, O and S, wherein N is unsubstituted or substituted with RN, wherein said ring is unsubstituted or substituted with one or more R12; each R2independently is S(O)P-RW, halogen, cyano, NH2, NHRM, N(RM)2, NH-C(O)-RM, Si(Rs)3, wherein Rsis Ci-C4-alkyl, C(O)RM, C(O)ORM, COOH, ORM, Ci-C6-alkyl, C3-C6- cycloalk(en)yl, C2-Ce-alkenyl, C2-Ce-alkynyl, Ce-C -aryl, a 5- to 12-membered saturated, partially unsaturated, or fully unsaturated mono-, bi- or tricyclic heterocyclic ring comprisingup to 4 heteroatoms selected from N, O and S, wherein N is unsubstituted or substituted with RN, or Si(Rs)3, wherein Rsis Ci-C4-alkyl,

[0147] wherein the alkyl, cycloalk(en)yl, alkenyl, alkynyl groups are unsubstituted or substituted with one or more R21,

[0148] wherein the aryl and heterocyclic rings are unsubstituted or substituted with one or more R22; or two R2combine to form together with the atoms to which they are attached a 5- to 10- membered saturated, partially unsaturated, or fully unsaturated carbocyclic or heterocyclic ring comprising up to 4 heteroatoms selected from N, O and S, wherein N is unsubstituted or substituted with RN, and wherein said ring is unsubstituted or substituted with one or more R22;

[0149] each R11independently is halogen or cyano;

[0150] each R12independently is C-i-Ce-alkyl, C2-Ce-alkenyl, C2-Ce-alkynyl, Ci-Ce-alkoxy-Ci-C4-alkyl, C3- Ce-cycloalkyl, C3-C6-cycloalkyl-Ci-C4-alkyl, C3-C6-cycloalkoxy-Ci-C4-alkyl, wherein the alkyl, alkoxy, cycloalkyl groups are unsubstituted or substituted with halogen or CN;

[0151] each R21independently is halogen or cyano or two R21combine to form a ring by a C2-Ce-alkyl bridge, which is unsubstituted or partly or fully halogenated and in which one or more carbon atoms may be replaced by O or N, wherein N is unsubstituted or substituted with RN; each R22independently is halogen, cyano, C-i-Ce-alkyl, C2-Ce-alkenyl, C2-Ce-alkynyl, C-i-Ce-alkoxy, Ci-Ce-alkoxy-Ci-C4-alkyl, Ci-C6-alkoxy-Ci-Ce-alkoxy-Ci-C4-alkyl Cs-Ce-cycloalkyl, C3-C6- cycloalkyl-Ci-C4-alkyl, C3-C6-cycloalkyl-Ci-C4-alkoxy, C3-C6-cycloalkoxy-Ci-C4-alkyl, NH- CO-RM, C(RM)2-CN, CHRM-CN, C(RM)2-(CONH2), CHRM-(CONH2), C(RM)2-(CSNH2), CHRM- (CSNH2), O-CH2-CN, O-CHRM-CN, O-C(RM)2-CN, O-C(RM)2-(CONH2), O-C(RM)2-(CSNH2), 0-C(CONH2)-C3-C6-cycloalkyl, 0-C(CSNH2)-C3-C6-cycloalkyl, O-S(O)2-RM, S(O)m-RM, S(O)(=NRM)RM, S(O)(=NH)RM, N=S(O)(RM)2, CO-N=SO(RM)2, SF5, or wherein two R22combine to form=0 (carbonyl) or=CF2 (difluoromethylen); wherein the alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, and cycloalkoxy groups are unsubstituted or substituted with halogen or CN, or wherein at least one C is replaced by a heteroatom; or in case of two adjacent substituents R22, the substituents may combine to form a C2-Ce-alkylene group, which is unsubstituted or substituted with halogen and in which one or more carbon atoms may be replaced by O or N, wherein N is unsubstituted or substituted with RN;

[0152] each RMindependently is C-i-Ce-alkyl, C2-Ce-alkenyl, C2-Ce-alkynyl, Ci-Ce-alkoxy-Ci-C4-alkyl, C3- Ce-cycloalkyl, C3-C6-cycloalkyl-Ci-C4-alkyl, C3-C6-cycloalkoxy-Ci-C4-alkyl, wherein the alkyl, alkoxy, cycloalkyl groups are unsubstituted or substituted with halogen or CN or wherein at least one C is replaced by a heteroatom; or two substituents RMmay combine to form a C2- Ce-alkylene group, which is unsubstituted or substituted with halogen and in which one or more carbon atoms may be replaced by O or N, wherein N is unsubstituted or substituted with RN;

[0153] RNis H, Ci-C4-alkyl, Cs-Ce-cycloalkyl, or Ci-C4-alkyl-Ci-C4-alkoxy;Rwis Ci-C4-alkyl, cyclopropyl, C3-C6-cycloalkyl-Ci-C4-alkyl;

[0154] m, p are independently 0, 1 , or 2;

[0155] and the N-oxides, stereoisomers, tautomers and agriculturally or veterinarily acceptable salts thereof;

[0156] by reacting a compound of formula (II)

[0157]

[0158] with a compound of formula (III)

[0159]

[0160] (III).

[0161] The reaction is a one-step reaction. The reaction proceeds by direct conversion of diamines and nitrile compounds to the target imidazole derivatives in a single chemical reaction. This one-step protocol reduces the number of synthetic manipulations and purification steps relative to conventional multi-step procedures. The one-step nature of the process is a central technical feature, as it enables a more straightforward and efficient synthesis of structurally diverse imidazole compounds. This means that the reaction does not occur by first transforming the nitrile into an aldehyde, carboxylic acid or carbonyl halogenide, such as carbonyl chloride, or any other derivative which is then reacted with the diamine, but rather that the nitrile is directly reacted with the diamine. This means that in the processes of the invention, the nitrile compound (III) directly reacts with the diamine compound (II) in a single step to form the compound of formula (I).

[0162] In the context of this invention, A is a five- to twelve-membered saturated, preferably partially unsaturated, or fully unsaturated mono-, bi- or tricyclic carbo- heterocyclic ring, wherein said heterocyclic ring comprises one, two, three or four same or different heteroatoms selected from N, O, and S, wherein, depending on the saturation level, said N is unsubstituted or substituted with RN. This means that depending on the saturation level of the ring and the position of the N, said N may be N or NRN. When said N is indicated as being unsubstituted, this includes N (wherein N is in an aromatic ring or bound in the ring by one double bond and one single bond), and wherein N is indicated as being substituted by RNthis includes, in this particular instance, NH (wherein N is bound in the ring by two single bonds), as RNcan be H. This applies to all occurrences wherein N is indicated as being “unsubstituted or substituted with RN”.

[0163] In various embodiments, A comprises at least one nitrogen atom N in the ring, wherein said N is unsubstituted or substituted with RN. In various embodiment, the N-atom in the heterocyclic ring Ais unsubstituted, and the rest of A is unsubstituted. In other embodiments, the N-atom in the heterocyclic ring A is unsubstituted, and the rest of A is substituted with one or two R1. In various embodiment, the N-atom in the heterocyclic ring A is unsubstituted, and the ring of A contains a group -S(O)m-Ci-C4-alkyl as one R1.

[0164] In various embodiments, the N-atom in the heterocyclic ring A is substituted, preferably with C1-C4-alkyl, and the rest of A is unsubstituted. In various such embodiments, the N-atom in the heterocyclic ring A is substituted, preferably with Ci-C4-alkyl, and the rest of A is substituted with one R1. In various embodiments, the N-atom in the heterocyclic ring A is substituted, preferably with Ci-C4-alkyl, and the ring of A contains a group -S(O)m-Ci-C4-alkyl as R1.

[0165] In the context of this invention, B is a five- to twelve-membered saturated, partially unsaturated, or fully unsaturated mono-, bi- or tricyclic carbo- heterocyclic ring, wherein said heterocyclic ring comprises one, two, three or four same or different heteroatoms selected from N, O, and S, wherein N is unsubstituted or substituted with RN.

[0166] In various embodiments, B comprises at least one R2substituent which is S(O)P-RW. Said substituent is preferably in the ortho position relative to the attachment point. In various embodiments, there is also a double bond between the attachment point and the carbon atom bearing the S(O)P-RWsubstituent so that the compound is a compound of formula (la)

[0167]

[0168] All following embodiments further defining the B ring relate to compounds of formula (I) as well as those of formula (la). Accordingly, all following embodiments of compound (la) that relate to R2groups relate to R2groups present in addition to the S(O)P-RWgroup.

[0169] In various embodiments, B comprises at least one nitrogen atom N in the ring, wherein said N is unsubstituted or substituted with RN.

[0170] In various embodiments, the N-atom in the heterocyclic ring B is unsubstituted, and the rest of B is unsubstituted. In various embodiments, the N-atom in the heterocyclic ring B is unsubstituted, and the rest of B is substituted with one or two R2. In various embodiments, the N-atom in the heterocyclic ring B is unsubstituted, and the ring of B contains Br as R2.In various embodiments, the N-atom in the heterocyclic ring B is substituted, preferably with C1-C4-alkyl, and the rest of B is unsubstituted. In various such embodiments, the N-atom in the heterocyclic ring B is substituted, preferably with Ci-C4-alkyl, and the rest of B is substituted with one R2. In various embodiments, the N-atom in the heterocyclic ring B is substituted, preferably with Ci-C4-alkyl, and the ring of B contains Br as R2.

[0171] In various embodiments of the invention, R1is S(O)m-Ci-C4-alkyl, S(0)m-C3-C6-cycloalkyl, S(O)m-C3-C6-cycloalkyl-Ci-C4-alkyl, which are unsubstituted or halogenated, preferably halogenated; S(O)(=NH)RM, or S(O)(=NRM)RM.

[0172] In various embodiments of the invention, R1is S(O)m-Ci-C4-alkyl, which is halogenated, S(O)(=NH)RMor S(O)(=NRM)RM. In such embodiments of the invention, m is 0, 1 or 2, preferably 2.

[0173] In various embodiments of the invention, R1is (S=O)-CF3, SO2-CF3, SCF3, S(O)(=NH)CF3 or S(O)(=NCH3)CF3.

[0174] In various embodiments of the invention, R1is S(O)m-Ci-C4-alkyl, S(0)m-C3-C6-cycloalkyl, S(O)m-C3-C6-cycloalkyl-Ci-C4-alkyl, which are unsubstituted or halogenated, preferably halogenated. In various embodiments of the invention, R1is (S=O)-CF3, SO2-CF3, orSCFs. In various embodiments of the invention, R1is (S=O)-CF3.

[0175] In various embodiments of the invention, R1is S(O)(=NH)RMor S(O)(=NRM)RM, wherein RMis each independently Ci-Cs-alkyl which is unsubstituted or partially or fully halogenated. In various embodiments of the invention, R1is S(O)(=NH)CF3 or S(O)(=NCH3)CF3.

[0176] In various embodiments of the invention, R1is Ci-C4-alkyl, Cs-Ce-cycloalkyl, Ci-C4-alkoxy, -O-C3-Ce-cycloalkyl, all of which are unsubstituted, partially halogenated or fully halogenated.

[0177] In various embodiments of the invention, R1is C-i-Ce-alkyl, C(O)RM, C(O)ORM, ORM, C3-C6-cycloalk(en)yl, halogen, cyano, NH2, NHRM, N(RM)2, NH-CO-RM, C2-Ce-alkenyl or C2-Ce-alkynyl. In various embodiments, R1is methyl, methoxy, cyclopropyl, ethynyl, chloro, cyano, dimethylamino, acetamino (NH-CO-CH3), wherein the alkyl, alkoxy, cycloalkyl groups are unsubstituted or substituted with halogen or CN. R1can be 1 -propenyl substituted with one or more halogen, such as 2-chloro-3-trifluoro-propen-1-yl.

[0178] In various embodiments of the invention, R1is Ci-C4-alkyl. In various embodiments, R1is methyl. In various embodiments, R1is methoxy. In various embodiments, R1is cyclopropyl. In variousembodiments, R1is ethynyl. In various embodiments, R1is bromo. In various embodiments, R1is chloro. In various embodiments, R1is cyano. In various embodiments, R1is dimethylamino. In various embodiments, R1is acetamino.

[0179] In various embodiments of the invention, R1is Ce-C -aryl or phenyl, which is unsubstituted or independently substituted with one or more of C-i-Ce-alkyl, C2-Ce-alkenyl, C2-Ce-alkynyl, Ci-Ce-alkoxy-Ci-C4-alkyl, Cs-Ce-cycloalkyl, C3-C6-cycloalkyl-Ci-C4-alkyl, C3-C6-cycloalkoxy-Ci-C4-alkyl, wherein the alkyl, alkoxy, cycloalkyl groups are unsubstituted or substituted with halogen or CN.

[0180] In various embodiments of the invention, R1is a 5- to 12-membered saturated, partially unsaturated, or fully unsaturated mono-, bi- or tricyclic heterocyclic ring comprising up to 4 heteroatoms selected from N, O and S, wherein N is unsubstituted or substituted with RN, wherein the alkyl, cycloalkyl, alkenyl, alkynyl groups are unsubstituted or substituted with one or more halogen and / or cyano. The 5- to 12-membered saturated, partially unsaturated, or fully unsaturated mono-, bi- or tricyclic heterocyclic ring is unsubstituted or independently substituted with one or more of C-i-Ce-alkyl, C2-Ce-alkenyl, C2-Ce-alkynyl, Ci-Ce-alkoxy-Ci-C4-alkyl, Cs-Ce-cycloalkyl, C3-C6-cycloalkyl-Ci-C4-alkyl, C3-C6-cycloalkoxy-Ci-C4-alkyl, wherein the alkyl, alkoxy, cycloalkyl groups are unsubstituted or substituted with halogen or CN.

[0181] In various embodiments two R1combine to form together with the atoms to which they are attached a 5- to 10-membered saturated, partially unsaturated, or fully unsaturated carbocyclic or heterocyclic ring comprising up to 4 heteroatoms selected from N, O and S, which is unsubstituted or independently substituted with one or more of C-i-Ce-alkyl, C2-Ce-alkenyl, C2-Ce-alkynyl, Ci-Ce-alkoxy-Ci-C4-alkyl, Cs-Ce-cycloalkyl, C3-C6-cycloalkyl-Ci-C4-alkyl, C3-C6-cycloalkoxy-Ci-C4-alkyl, wherein the alkyl, alkoxy, cycloalkyl groups are unsubstituted or substituted with halogen or CN. Said ring may be, for example, a dioxan or dioxolan ring, such as an 1,3-dioxolan, which may be substituted, for example by Ci-C4-alkyl or halogen, such as fluoro.

[0182] It is understood that all above embodiments of R1may be combined if more than one R1is present in the ring. However, in various embodiments, there is only one substituent R1in ring A. In various other embodiments, there are two substituents R1in ring A.

[0183] In various embodiments of the invention, R2is halogen, cyano, NH2, NHRM, N(RM)2, NH-CO-RM, C(O)RM, C(O)ORM, COCH, Ci-C6-alkyl, ORM, C3-C6-cycloalk(en)yl, C2-C6-alkenyl orC2-C6-alkynyl. In various embodiments of the invention, R2is methyl, methoxy, cyclopropyl, ethynyl, chloro, cyano, dimethylamino, acetamino (NH-CO-CH3), wherein the alkyl, alkoxy, cycloalkyl groups are unsubstituted or substituted with halogen or CN.In various embodiments of the invention, R2is Ci-C4-alkyl. In various embodiments, R2is methyl. In various embodiments, R2is methoxy. In various embodiments, R2is cyclopropyl. In various embodiments, R2is ethynyl. In various embodiments, R2is bromo. In various embodiments, R2is chloro. In various embodiments, R2is cyano. In various embodiments, R2is dimethylamino. In various embodiments, R2is acetamino.

[0184] In various embodiments of the invention, R2is Ce-C -aryl or phenyl, which is unsubstituted or independently substituted with one or more of C-i-Ce-alkyl, C2-Ce-alkenyl, C2-Ce-alkynyl, Ci-Ce-alkoxy-Ci-C4-alkyl, Cs-Ce-cycloalkyl, C3-C6-cycloalkyl-Ci-C4-alkyl, C3-C6-cycloalkoxy-Ci-C4-alkyl, wherein the alkyl, alkoxy, cycloalkyl groups are unsubstituted or substituted with halogen or CN.

[0185] In various embodiments of the invention, R2is a 5- to 12-membered saturated, partially unsaturated, or fully unsaturated mono-, bi- or tricyclic heterocyclic ring comprising up to 4 heteroatoms selected from N, O and S, wherein N is unsubstituted or substituted with RN, wherein the alkyl, cycloalk(en)yl, alkenyl, alkynyl groups are unsubstituted or substituted with one or more halogen and / or cyano. The 5- to 12-membered saturated, partially unsaturated, or fully unsaturated mono-, bi- or tricyclic heterocyclic ring is unsubstituted or independently substituted with one or more of halogen, cyano, C-i-Ce-alkyl, C2-Ce-alkenyl, C2-Ce-alkynyl, C-i-Ce-alkoxy, Ci-Ce-alkoxy-Ci-C4-alkyl, Ci-C6-alkoxy-Ci-Ce-alkoxy-Ci-C4-alkyl Cs-Ce-cycloalkyl, C3-C6-cycloalkyl-Ci-C4-alkyl, C3-C6-cycloalkyl-Ci-C4-alkoxy, C3-C6-cycloalkoxy-Ci-C4-alkyl, NH-CO-RM, C(RM)2-CN, CHRM-CN, C(RM)2-(CONH2), CHRM-(CONH2), C(RM)2-(CSNH2), CHRM-(CSNH2), O-CH2-CN, O-CHRM-CN, O-C(RM)2-CN, O-C(RM)2-(CONH2), O-C(RM)2-(CSNH2), 0-C(CONH2)-C3-C6-cycloalkyl, O-C(CSNH2)-C3-C6-cycloalkyl, O-S(O)2-RM, S(O)m-RM, S(O)(=NRM)RM, S(O)(=NH)RM, N=S(O)(RM)2, CO-N=SO(RM)2, SF5, or wherein two substituents of the 5- to 12-membered saturated, partially unsaturated, or fully unsaturated mono-, bi- or tricyclic heterocyclic ring combine to form =0 (carbonyl) or =CF2 (difluoromethylen) and / or wherein the alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, and cycloalkoxy groups are unsubstituted or substituted with halogen or CN.

[0186] In various embodiments two R2combine to form together with the atoms to which they are attached a a 5- to 10-membered saturated, partially unsaturated, or fully unsaturated carbocyclic or heterocyclic ring comprising up to 4 heteroatoms selected from N, O and S, wherein N is unsubstituted or substituted with RN, wherein said ring is unsubstituted or independently substituted with one or more of halogen, cyano, C-i-Ce-alkyl, C2-Ce-alkenyl, C2-Ce-alkynyl, C-i-Ce-alkoxy, Ci-Ce-alkoxy-Ci-C4-alkyl, Ci-C6-alkoxy-Ci-Ce-alkoxy-Ci-C4-alkyl Cs-Ce-cycloalkyl, Cs-Ce-cycloalkyl-C-i-C4-alkyl, C3-C6-cycloalkyl-Ci-C4-alkoxy, C3-C6-cycloalkoxy-Ci-C4-alkyl, NH-CO-RM, C(RM)2-CN, CHRM-CN, C(RM)2-(CONH2), CHRM-(CONH2), C(RM)2-(CSNH2), CHRM-(CSNH2), O-CH2-CN, O-CHRM-CN, O-C(RM)2-CN, O-C(RM)2-(CONH2), O-C(RM)2-(CSNH2), 0-C(CONH2)-C3-C6-cycloalkyl, 0-C(CSNH2)-C3-C6-cycloalkyl, O-S(O)2-RM, S(O)m-RM, S(O)(=NRM)RM, S(O)(=NH)RM,N=S(0)(RM)2, C0-N=S0(RM)2, SFS, or wherein two substituents of the 5- to 12-membered saturated, partially unsaturated, or fully unsaturated mono-, bi- or tricyclic heterocyclic ring combine to form=0 (carbonyl) or=CF2 (difluoromethylen) and / or wherein the alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, and cycloalkoxy groups are unsubstituted or substituted with halogen or CN.

[0187] It is understood that all above embodiments of R2may be combined if more than one R2is present in the ring. However, in various embodiments, there is only one substituent R2in ring B. In various other embodiments, there are two substituents R2in ring B.

[0188] In various embodiments of the invention, Rwis Ci-C4-alkyl, cyclopropyl, C3-C6-cycloalkyl-Ci-C4-alkyl, and p is 0, 1, or 2, preferably 2. In various embodiments of the invention, Rwis Ci-C4-alkyl and p is 0, 1, or 2, preferably 2. In some embodiments of the invention, Rwis methyl, ethyl or isopropyl and p is 0, 1 , or 2, preferably 2. In various embodiments, Rwis ethyl and p is 2.

[0189] In various embodiments of the invention, RMindependently is C-i-Ce-alkyl, C2-Ce-alkenyl, C2-C6-alkynyl, Ci-Ce-alkoxy-Ci-C4-alkyl, Cs-Ce-cycloalkyl, C3-C6-cycloalkyl-Ci-C4-alkyl, C3-C6-cycloalkoxy-Ci-C4-alkyl, wherein the alkyl, alkoxy, cycloalkyl groups are unsubstituted or substituted with halogen or CN or wherein at least one C is replaced by a heteroatom. In various embodiments, if there are two adjacent substituents RM, the substituents may combine to form a C2-Ce-alkylene group, which is unsubstituted or substituted with halogen and in which one or more carbon atoms may be replaced by O or N, wherein N is unsubstituted or substituted with RN. Examples for such groups formed by combination of two substituents are further described herein below.

[0190] In various embodiments of the invention, each RMis independently Ci-Cs-alkyl which is unsubstituted or partially or fully halogenated; or Cs-Ce-cycloalkyl, or Cs-Ce-cycloalkyl in which at least one C is replaced by a heteroatom; or in case of two adjacent substituents RM, the substituents may combine to form together with the atom(s) to which they are attached a ring by a C2-Ce-alkyl bridge, which is unsubstituted or partly or fully halogenated and in which one or more carbon atoms may be replaced by O or N, wherein N is unsubstituted or substituted with RN.

[0191] In various embodiments of the invention, each RMis independently methyl, trifluoromethyl or cyclopropyl.

[0192] In various embodiments of the invention, two adjacent substituents RMcombine to form a ring by a C2-Ce-alkyl bridge, which is unsubstituted or partly or fully halogenated and in which one or more carbon atoms may be replaced by O or N, wherein N is unsubstituted or substituted with RN.Examples for such bridge substituents are shown as RM-b1 to RM-b8, without limiting to these structures:

[0193] H \ N — N |_i

[0194] Q Q Q Q Q D

[0195] ■ ■’ / '■ /

[0196]

[0197] RM-b1 RM-b2 RM-b3 RM-b4 RM-b5 RM-b6 RM-b7 RM-b8

[0198] All of these ring structures may be substituted as described herein above for RM, i.e. substituted with halogen. In some embodiments of two adjacent substituents RMforming a bridge ring, the bridge has the structure of RM-b1.

[0199] In some embodiments, two R21combine to form a ring by a C2-Ce-alkyl bridge, which is unsubstituted or partly or fully halogenated and in which one or more carbon atoms may be replaced by O or N, wherein N is unsubstituted or substituted with RN. Examples for such bridge substituents are shown as RM-b1 to RM-b8. The two R21groups may be bound to the same atom and thus form, if the atom to which they are bound is also a ring atom, a spiro connected ring. In various embodiments, such spiro-connected ring has the structure RM-b5.

[0200] In various embodiments of the invention, one R1is (S=O)-CF3, SO2-CF3, SCF3, S(O)(=NH)CF3 or S(O)(=NCH3)CF3, R2is methyl, methoxy, cyclopropyl, ethynyl, bromo, chloro, cyano, dimethylamino, acetamino (NH-CO-CH3), 2,4-difluorophenyl or difluorobenzodioxole (such as 2,2-difluoro-1 ,3-benzodioxole) and Rwis ethyl and p is 2. In such embodiments, there may only be one R1and / or one R2substituent.

[0201] In various embodiments of the invention, one R1is (S=O)-CF3, SO2-CF3 or SCF3, one R2is methyl, cyclopropyl, bromo, 2,4-difluorophenyl or difluorobenzodioxole (such as 2,2-difluoro-1 ,3-benzodioxole) , Rwis ethyl and p is 2.

[0202] In various embodiments of the invention, R1is S(O)(=NH)RMor S(O)(=NRM)RM, wherein RMis each independently Ci-Cs-alkyl which is unsubstituted or partially or fully halogenated, and Rwis ethyl, n is 2. In various embodiments of the invention, R1is S(O)(=NH)CF3 or S(O)(=NCH3)CF3, and Rwis ethyl and n is 2. In such embodiments, there may only be one or two substituent(s) R1, wherein one is as defined above and the other is a different substituent, i.e. not S(O)(=NH)RMor S(O)(=NRM)RM.

[0203] In various embodiments, R1is Ci-C4-alkyl, Cs-Ce-cycloalkyl, Ci-C4-alkoxy, -O-Cs-Ce-cycloalkyl, all of which are unsubstituted, partially halogenated or fully halogenated, and Rwis ethyl, n is 2. Invarious embodiments, R1is methyl, ethyl, cyclopropyl, methoxy or trifluoromethoxy, and Rwis ethyl, n is 2. In such embodiments, there may only be one or two substituent(s) R1on ring A.

[0204] In various embodiments of the invention, the compound of formula (I) is a compound of formula (IV), (V) or (VI):

[0205] (IV)

[0206] (V)

[0207]

[0208] (VI)

[0209] wherein

[0210] A1, A2, A3and A4are each independently N, CH or CR1, wherein not more than two are N; and B1, B2, B3and B4are each independently N, CH or CR2, wherein not more than two are N.

[0211] Alternatively, B1, B2, and B3are each independently N, NRN, CH or CR2, wherein not more than two are N and / or NRN, and B4is absent. In various such embodiments, B1is NRN, B2is CR2and B3is N.

[0212] In various embodiments, A1is CH or CR1and one of A2, A3and A4is N and the others are CH or CR1. In such embodiments, in can be preferred that at least one of A1, A2, A3and A4is CR1.

[0213] In various embodiments, A1and A4are CH or CR1and one of A2and A3is N and the other is CH or CR1. In such embodiments, in can be preferred that at least one of A1, A2, A3and A4is CR1.In various embodiments, A1, A2and A3are CH or CR1and A4is N. In such embodiments, in can be preferred that at least one of A1, A2and A3is CR1.

[0214] In various embodiments, A1, A2, A3and A4are CH orCR1. In such embodiments, in can be preferred that at least one of A1, A2, A3and A4is CR1.

[0215] In various embodiments, B1, B2, and B3are CH or CR2and B4is N, CH or CR2. In such embodiments, in can be preferred that at least one of B1, B2, B3and B4is CR2.

[0216] In various embodiments, B1, B2, and B3are CH or CR2and B4is N. In such embodiments, in can be preferred that at least one of B1, B2and B3is CR2.

[0217] In various embodiments, A1is CH and at least one of A2and A3is CR1and the other is CH or CR1and A4is N or CH. In various embodiments A1is CH, A2and A3are CR1and A4is N.

[0218] In various embodiments, B1is CH and at least one of B2and B3is CR2and the other is CH or CR2and B4is N. In various embodiments B1is CH, B2and B3are CR2and B4is N.

[0219] In various embodiments of the invention in compound VI A1is CH, A2and A3are CR1, A4is N, B1is CH, B2and B3are CR2and B4is N. In various embodiments of the invention in compound VI A1is CH, one of A2and A3is CR1and the other is CH, A4is N, B1is CH, B2and B3are CR2and B4is N. In various embodiments of the invention in compound VI A1is CH, one of A2and A3is CR1and the other is CH, A4is N, B1is CH, one of B2and B3is CR2and the other is CH, and B4is N.

[0220] In all embodiments of the compounds of formulae (IV) to (VI), R2is preferably not another group S(O)P-RW. It is generally preferred that the B ring only comprises a single group S(O)P-RW.

[0221] In various embodiments, the compound of formula (I) is a compound of formula (VII), (VIII), (IX), (X), (XI), (XII), (XIII), (XIV), (XV), or (XVI)

[0222] RW^(O)P

[0223]

[0224] (VII)RVt oc^(O)p(VIII) (IX) (X)

[0225]

[0226]

[0227] wherein

[0228] each of RA2and RA3independently is selected from H, S(O)m-Ci-C4-alkyl, S(0)m-C3-C6-cycloalkyl, S(0)m-C3-C6-cycloalkyl-Ci-C4-alkyl, S(O)(=NH)RM, S(O)(=NRM)RM, halogen, cyano, NH2, NHRM, N(RM)2, NH-C(O)-RM, C(O)RM, C(O)ORM, ORM, Ci-C6-alkyl, C3-C6-cycloalk(en)yl, C2- Ce-alkenyl, C2-Ce-alkynyl, Ce-C -aryl, a 5- to 12-membered saturated, partially unsaturated, or fully unsaturated mono-, bi- or tricyclic heterocyclic ring comprising up to 4 heteroatoms selected from N, O and S, wherein N is unsubstituted or substituted with RN,

[0229] wherein the alkyl, cycloalkyl, alkenyl, alkynyl groups are unsubstituted or substituted with one or more R11,

[0230] wherein the aryl and heterocyclic rings are unsubstituted or substituted with one or more R12; or RA2and RA3combine to form together with the atoms to which they are attached a 5- to 6- membered partially unsaturated or fully unsaturated heterocyclic ring comprising up to 4 heteroatoms selected from N, O and S, wherein N is unsubstituted or substituted with RN, wherein said ring is unsubstituted or substituted with halogen or C1-C4 alkyl, which can be substituted with halogen;

[0231] RA4and RA5are independently H or halogen, or C1-C4 alkyl, which can be substituted with halogen; each of RB2and RB3independently is selected from H, halogen, cyano, NH2, NHRM, N(RM)2, NH- C(O)-RM, C(O)RM, C(O)ORM, COOH, Ci-C6-alkyl, ORM, Ci-C6-alkyl, C3-C6-cycloalk(en)yl, C2- Ce-alkenyl, C2-Ce-alkynyl, Ce-C -aryl, a 5- to 12-membered saturated, partially unsaturated, or fully unsaturated mono-, bi- or tricyclic heterocyclic ring comprising up to 4 heteroatoms selected from N, O and S, wherein N is unsubstituted or substituted with RN, or Si(Rs)3, wherein Rsis Ci-C4-alkyl,wherein the alkyl, cycloalk(en)yl, alkenyl, alkynyl groups are unsubstituted or substituted with one or more R21,

[0232] wherein the aryl and heterocyclic rings are unsubstituted or substituted with one or more R22.

[0233] In various embodiments each of RA2and RA3independently is H, S(O)m-Ci-C4-alkyl, S(O)m-C3-C6-cycloalkyl, or S(0)m-C3-C6-cycloalkyl-Ci-C4-alkyl, which are unsubstituted or halogenated, preferably halogenated; S(O)(=NH)RM, S(O)(=NRM)RM. In various embodiments only one of RA2and RA3is H.

[0234] In various embodiments of the invention, each of RA2and RA3independently is H, S(O)m-Ci-C4-alkyl, which may be halogenated, S(O)(=NH)RMor S(O)(=NRM)RM. In various embodiments, m is 0, 1 or 2, preferably 2. In various such embodiments, only one of RA2and RA3is H.

[0235] In various embodiments of the invention, each of RA2and RA3independently is H, (S=O)-CF3, SO2-CF3, SCF3, S(O)(=NH)CF3 or S(O)(=NCH3)CF3. In various such embodiments, only one of RA2and RA3is H.

[0236] In various embodiments, each of RA2and RA3independently is selected from H, S(O)m-Ci-C4-alkyl, S(0)m-C3-C6-cycloalkyl, S(0)m-C3-C6-cycloalkyl-Ci-C4-alkyl, which are unsubstituted or halogenated, preferably halogenated. In various embodiments of the invention, each of RA2and RA3independently is (S=O)-CF3, SO2-CF3, SCF3. In various embodiments of the invention, one or both of RA2and RA3is (S=O)-CF3. In various embodiments of the invention, one or both of RA2and RA3is S(O)2-CF3. In various embodiments, it may be preferred that one of RA2and RA3is H and the other is not H and selected from the groups listed above.

[0237] In various embodiments, each of RA2and RA3independently is H, S(O)(=NH)RMor S(O)(=NRM)RM, wherein RMis each independently Ci-Cs-alkyl which is unsubstituted or partially or fully halogenated. In various embodiments of the invention, each of RA2and RA3independently is H, S(O)(=NH)CF3 or S(O)(=NCH3)CF3. In various embodiments, it may be preferred that one of RA2and RA3is H and the other is not H and selected from the groups listed above.

[0238] In various embodiments, each of RA2and RA3independently is H, Ci-C4-alkyl, C2-C4-alkenyl, C3-Ce-cycloalkyl, Ci-C4-alkoxy, -O-Cs-Ce-cycloalkyl, all of which are unsubstituted, partially halogenated or fully halogenated, such as 2-chloro-3-trifluoro-propen-1-yl. In various embodiments, it may be preferred that one of RA2and RA3is H and the other is not H and selected from the groups listed above.In various embodiments, each of RA2and RA3independently is H, C-i-Ce-alkyl, C(O)RM, C(O)ORM, ORM, C3-C6-cycloalk(en)yl, halogen, cyano, NH2, NHRM, N(RM)2, NH-CO-RM, C2-C6-alkenyl or C2-Ce-alkynyl. In various embodiments, each of RA2and RA3independently is methyl, methoxy, cyclopropyl, propenyl, ethynyl, chloro, cyano, dimethylamino, acetamino (NH-CO-CH3), wherein the alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl groups are unsubstituted or substituted with halogen or CN. In various embodiments, it may be preferred that one of RA2and RA3is H and the other is not H and selected from the groups listed above.

[0239] In various embodiments, one or both of RA2and RA3is / are Ci-C4-alkyl. In various embodiments, one or both of RA2and RA3is / are methyl. If in these embodiments only one of RA2and RA3is alkyl, the other may preferably be H.

[0240] In various embodiments, one or both of RA2and RA3is / are methoxy. In various embodiments, one or both of RA2and RA3is / are cyclopropyl. In various embodiments, one or both of RA2and RA3is / are ethynyl. In various embodiments, one or both of RA2and RA3is / are bromo. In various embodiments, one or both of RA2and RA3is / are chloro. In various embodiments, one or both of RA2and RA3is / are cyano. In various embodiments, one or both of RA2and RA3is / are dimethylamino. In various embodiments one or both of RA2and RA3is / are acetamino. If only one of RA2and RA3is selected from the above listed groups, the other is preferably H.

[0241] In various embodiments, one or both of RA2and RA3is / are Ce-C -aryl or phenyl, which is unsubstituted or independently substituted with one or more of C-i-Ce-alkyl, C2-Ce-alkenyl, C2-Ce-alkynyl, Ci-Ce-alkoxy-Ci-C4-alkyl, Cs-Ce-cycloalkyl, C3-C6-cycloalkyl-Ci-C4-alkyl, C3-C6-cycloalkoxy-Ci-C4-alkyl, wherein the alkyl, alkoxy, cycloalkyl groups are unsubstituted or substituted with halogen or CN. In such embodiments, the other may be H.

[0242] In various embodiments of the invention, one or both of RA2and RA3is / are a 5- to 12-membered saturated, partially unsaturated, or fully unsaturated mono-, bi- or tricyclic heterocyclic ring comprising up to 4 heteroatoms selected from N, O and S, wherein N is unsubstituted or substituted with RN, wherein the alkyl, cycloalkyl, alkenyl, alkynyl groups are unsubstituted or substituted with one or more halogen and / or cyano. The 5- to 12-membered saturated, partially unsaturated, or fully unsaturated mono-, bi- or tricyclic heterocyclic ring is unsubstituted or independently substituted with one or more of C-i-Ce-alkyl, C2-Ce-alkenyl, C2-Ce-alkynyl, Ci-Ce-alkoxy-Ci-C4-alkyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl-Ci-C4-alkyl, C3-C6-cycloalkoxy-Ci-C4-alkyl, wherein the alkyl, alkoxy, cycloalkyl groups are unsubstituted or substituted with halogen or CN. In such embodiments, the other may be H.In various embodiments, RA4and RA5are identical. In various embodiments, RA4and RA5are H. In various embodiments, RA4and RA5are halogen, such as fluoro. In various embodiments, RA4and RA5may be C1-C4 alkyl, such as methyl, which can be substituted with halogen, such as fluoro.

[0243] In various embodiments, each of RB2and RB3independently is H, halogen, cyano, NH2, NHRM, N(RM)2, NH-CO-RM, C(O)RM, C(O)ORM, COOH, Ci-C6-alkyl, ORM, C3-C6-cycloalk(en)yl, C2-C6-alkenyl or C2-C6-alkynyl. In various embodiments each of RB2and RB3independently is methyl, methoxy, cyclopropyl, ethynyl, chloro, cyano, dimethylamino, acetamino (NH-CO-CH3), wherein the alkyl, alkoxy, cycloalkyl groups are unsubstituted or substituted with halogen or CN. In various embodiments, it may be preferred that one of RA2and RA3is H and the other is not H and selected from the groups listed above.

[0244] In various embodiments, one or both of RB2and RB3is / are Ci-C4-alkyl. In various embodiments, one or both of RB2and RB3is / are methyl. In various embodiments, one or both of RB2and RB3is / are methoxy. In various embodiments, one or both of RB2and RB3is / are cyclopropyl. In various embodiments, one or both of RB2and RB3is / are ethynyl. In various embodiments, one or both of RB2and RB3is / are bromo. In various embodiments, one or both of RB2and RB3is / are chloro. In various embodiments, one or both of RB2and RB3is / are cyano. In various embodiments, one or both of RB2and RB3is / are dimethylamino. In various embodiments, one or both of RB2and RB3is / are acetamino. In these embodiments, if not both are the given group, the other may be H.

[0245] In various embodiments, one or both of RB2and RB3is / are Ce-C -aryl or phenyl, which is unsubstituted or independently substituted with one or more of C-i-Ce-alkyl, C2-Ce-alkenyl, C2-Ce-alkynyl, Ci-Ce-alkoxy-Ci-C4-alkyl, Cs-Ce-cycloalkyl, C3-C6-cycloalkyl-Ci-C4-alkyl, C3-C6-cycloalkoxy-Ci-C4-alkyl, wherein the alkyl, alkoxy, cycloalkyl groups are unsubstituted or substituted with halogen or CN. In these embodiments, if not both are the given group, the other may be H.

[0246] In various embodiments, one or both of RB2and RB3is / are a 5- to 12-membered saturated, partially unsaturated, or fully unsaturated mono-, bi- or tricyclic heterocyclic ring comprising up to 4 heteroatoms selected from N, O and S, N may be unsubstituted or substituted with Ci-C4-alkyl C3-Ce-cycloalkyl, C-bound Ci-C4-alkoxy, or Ci-C4-alkyl-Ci-C4-alkoxy, wherein the alkyl, cycloalk(en)yl, alkenyl, alkynyl groups are unsubstituted or substituted with one or more halogen and / or cyano. The 5- to 12-membered saturated, partially unsaturated, or fully unsaturated mono-, bi- or tricyclic heterocyclic ring is unsubstituted or independently substituted with one or more of halogen, cyano, Ci-Ce-alkyl, C2-Ce-alkenyl, C2-Ce-alkynyl, C-i-Ce-alkoxy, Ci-Ce-alkoxy-Ci-C4-alkyl, Ci-Ce-alkoxy-Ci-Ce-alkoxy-Ci-C4-alkyl Cs-Ce-cycloalkyl, C3-C6-cycloalkyl-Ci-C4-alkyl, C3-C6-cycloalkyl-Ci-C4-alkoxy, C3-C6-cycloalkoxy-Ci-C4-alkyl, NH-CO-RM, C(RM)2-CN, CHRM-CN, C(RM)2-(CONH2),CHRM-(CONH2), C(RM)2-(CSNH2), CHRM-(CSNH2), O-CH2-CN, O-CHRM-CN, O-C(RM)2-CN, O-C(RM)2-(CONH2), O-C(RM)2-(CSNH2), 0-C(CONH2)-C3-C6-cycloalkyl, O-C(CSNH2)-C3-C6-cycloalkyl, O-S(O)2-RM, S(O)m-RM, S(O)(=NRM)RM, S(O)(=NH)RM, N=S(O)(RM)2, CO-N=SO(RM)2, SFs, or wherein two substituents of the 5- to 12-membered saturated, partially unsaturated, or fully unsaturated mono-, bi- or tricyclic heterocyclic ring combine to form =0 (carbonyl) or =CF2(difluoromethylen) and / or wherein the alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, and cycloalkoxy groups are unsubstituted or substituted with halogen or CN. In these embodiments, if not both are the given group, the other may be H.

[0247] In various embodiments, RB2is selected from cyclopropyl, 1-cyano-cyclopropyl, 2-cyano-2-propyl, and bromo, and RB3is H.

[0248] In various embodiments, it is preferred that RB3is H and RB2is not H.

[0249] In various embodiments, one or both of RA2and RA3are independently S(O)m-Ci-C4-alkyl, S(0)m-C3-C6-cycloalkyl, S(0)m-C3-C6-cycloalkyl-Ci-C4-alkyl, which are unsubstituted or halogenated, preferably halogenated; S(O)(=NH)RM, S(O)(=NRM)RM. If not both are selected from the above list, the other is preferably H.

[0250] In various embodiments, one or both of RA2and RA3are independently S(O)m-Ci-C4-alkyl, which are halogenated, S(O)(=NH)RMor S(O)(=NRM)RM. In such embodiments, m is 0, 1 or 2, preferably 1 or 2, for example 1. If not both are selected from the above list, the other is preferably H.

[0251] In various embodiments, one or both of RA2and RA3independently are (S=O)-CF3, SO2-CF3, SCF3, S(O)(=NH)CF3or S(O)(=NCH3)CF3. If not both are selected from the above list, the other is preferably H.

[0252] In various embodiments, one or both of RA2and RA3independently are S(O)m-Ci-C4-alkyl, S(O)m-C3-C6-cycloalkyl, S(0)m-C3-C6-cycloalkyl-Ci-C4-alkyl, which are unsubstituted or halogenated, preferably halogenated. In various embodiments of the invention, one of RA2or RA3is (S=O)-CF3, SO2-CF3, or SCF3and the other is H. In some embodiments, one of RA2or RA3is (S=O)-CF3and the other is H.

[0253] In various embodiments, one or both of RA2and RA3independently are S(O)(=NH)RMor S(O)(=NRM)RM, wherein RMis each independently Ci-C3-alkyl which is unsubstituted or partially or fully halogenated. In various embodiments, one or both of RA2and RA3independently are S(O)(=NH)CF3or S(O)(=NCH3)CF3. If not both are selected from the above list, the other is preferably H.In various embodiments, one or both of RA2and RA3independently are Ci-C4-alkyl, C2-C4-alkenyl, Cs-Ce-cycloalkyl, Ci-C4-alkoxy, -O-Cs-Ce-cycloalkyl, all of which are unsubstituted, partially halogenated or fully halogenated. If not both are selected from the above list, the other is preferably H.

[0254] In various embodiments of the compounds of formulae (VII)-(XI), Rwis Ci-C4-alkyl, cyclopropyl, C3-C6-cycloalkyl-Ci-C4-alkyl, and n is 0, 1, or 2, preferably 2. In various embodiments, Rwis C1-C4-alkyl and n is 0, 1 , or 2, preferably 2. In various embodiments, Rwis methyl, ethyl or isopropyl and n is 0, 1 , or 2, preferably 2. In various embodiments of the invention, Rwis ethyl and n is 2.

[0255] In various embodiments, one of RA2and RA3is (S=O)-CF3, SO2-CF3, SCF3, S(O)(=NH)CF3 or S(O)(=NCH3)CF3, the other is H, Rwis ethyl, and n is 2. In various embodiments, one of RA2and RA3is (S=O)-CF3, SO2-CF3, or SCF3, the other is H, Rwis ethyl, and n is 2.

[0256] In various embodiments, the compound of formula (I) is a compound of formula (XI) wherein RA4and RA5are fluoro, RNis CH3, Rwis ethyl, p is 2, RB2is 1-cyano-1 -cyclopropyl and RB3is H. In various embodiments, the compound of formula (I) is a compound of formula (XI) wherein RA4and RA5are fluoro, RNis CH3, Rwis ethyl, p is 2, RB2is cyclopropyl and RB3is H. In various embodiments, the compound of formula (I) is a compound of formula (IX) wherein RA2is CF3, RNis methyl, Rwis ethyl, p is 2, RB2is 2-cyano-2-propyl and RB3is H. In various embodiments, the compound of formula (I) is a compound of formula (IX) wherein RA2is CF3, RNis methyl, Rwis ethyl, p is 2, RB2is cyclopropyl and RB3is H.

[0257] In various embodiments, the compound of formula (I) is one of the following compounds:

[0258]

[0259] In various embodiments, one of RA2and RA3is S(O)(=NH)RMor S(O)(=NRM)RM, the other is H, and each RMis independently Ci-Cs-alkyl which is unsubstituted or partially or fully halogenated, Rwis ethyl, and n is 2. In various embodiments, one of RA2or RA3is S(O)(=NH)CF3 or S(O)(=NCH3)CF3 and the other is H, Rwis ethyl, and n is 2.

[0260] In various embodiments, one of RA2and RA3is Ci-C4-alkyl, Cs-Ce-cycloalkyl, Ci-C4-alkoxy, -O-C3-Ce-cycloalkyl, all of which are unsubstituted, partially halogenated or fully halogenated, and the other is H, Rwis ethyl, and n is 2.

[0261] In various embodiments, RB3is H, Ci-C4-alkyl, Ci-C4-alkoxy, Cs-Ce-cycloalkyl, halogen, cyano, N(RM)2, NH-CO-RMorCi-C4-alkynyl. In various embodiments, RB3is methyl, methoxy, cyclopropyl, ethynyl, bromo, chloro, cyano, dimethylamino, acetamino (NH-CO-CH3).

[0262] In various embodiments, RB3is Ci-C4-alkyl. In various embodiments, RB3is methyl.

[0263] In various embodiments, RB3is methoxy. In various embodiments, RB3is cyclopropyl. In various embodiments, RB3is ethynyl. In various embodiments, RB3is chloro. In various embodiments, RB3is cyano. In various embodiments, RB3is dimethylamino. In various embodiments, RB3is acetamino.

[0264] In various embodiments, RB3is phenyl which is unsubstituted or substituted with at least one C1-C4-alkyl which is unsubstituted or partially or fully halogenated; Cs-Ce-cycloalkyl, halogen, O-S(O)2-RM, CN, Ci-Cs-alkoxy, which is unsubstituted or partially or fully halogenated, Cs-Ce-cycloalkoxy, N=S(O)(RM)2. In various embodiments, RB3is phenyl substituted with O-S(O)2-RM.

[0265] In various embodiments, RB3is a five- or six-membered aromatic heterocycle, which is unsubstituted or substituted with at least one halogen, CN, Ci-C4-alkyl which is unsubstituted or partially or fully halogenated; Cs-Ce-cycloalkyl, Ci-Cs-alkoxy, which is unsubstituted or partially or fully halogenated. In various embodiments, RB3is a five-membered aromatic heterocycle, which is unsubstituted or substituted with at least one halogen or Cs-Ce-cycloalkyl, in particular with one chloro, bromo or cyclopropyl. In various embodiments, RB3is pyrazole, triazole, imidazole or thiazole, which is unsubstituted or substituted with at least one halogen or Cs-Ce-cycloalkyl, in particular with one chloro, bromo or cyclopropyl.

[0266] In various embodiments, the heterocyclic ring is bound to the remainder of the molecule via a nitrogen atom (N-linked). In various embodiments of the invention, the heterocyclic ring is bound to the remainder of the molecule via a carbon atom in the ring (C-linked).

[0267] In various embodiments, RB3is selected from the following:

[0268]

[0269] In various embodiments, RB3is H. RB3can be preferably H if RB2is not H and vice versa. In various embodiments, RB2and RB3are hydrogen.

[0270] In various embodiments, RB2is Cs-Ce-cycloalkyl, which is unsubstituted or partially or fully halogenated or substituted with cyano, or halogen. In various embodiments, RB2is Cs-Ce-cycloalkyl, which is unsubstituted or partially or fully halogenated or substituted with cyano, in particular cyclopropyl.

[0271] In various embodiments, RB2is halogen, in particular chloro or bromo. In various embodiments, RB2is bromo.

[0272] In various embodiments, RB2is phenyl substituted with one R22, or substituted with up to 5 halogens.

[0273] In various embodiments, RB2is phenyl substituted with one R22, or substituted with 2 or 3 halogens. In various embodiments, RB2is difluoro- or trifluorophenyl, for example 2,4-difluorophenyl.

[0274] In various embodiments, RB2is a 5- to 12-membered, preferably 5 to 10- or 5- to 9-membered, saturated, partially unsaturated, or fully unsaturated, preferably partially or fully unsaturated, mono-, bi- or tricyclic, preferably mono- or bicyclic, heterocyclic ring comprising up to 4 heteroatoms, preferably 2 or 3, more preferably 2 heteroatoms, selected from N, O and S, wherein N is unsubstituted or substituted with RN,

[0275] and wherein the heterocyclic ring is unsubstituted or substituted with one or more R22.

[0276] In various embodiments, RB2is a benzodioxole ring, for example a difluorobenzodioxole ring of the following structure:

[0277]

[0278] In various embodiments, RB2is a six-membered saturated, partially unsaturated, or fully unsaturated heterocyclic ring or ring system, wherein said heterocyclic ring or ring systemcomprises one, two or three, same or different heteroatoms O or N, wherein N may be unsubstituted or substituted with Ci-C4-alkyl, and wherein the ring or ring system is unsubstituted, or substituted with one or more R22, optionally one R22or substituted with two halogens.

[0279] In various embodiments, RB2is

[0280] x5— x4

[0281] s /

[0282] | - ( / z

[0283] x3

[0284] « \ /

[0285]

[0286] X1— X2

[0287] wherein X1is C(R22)qor O, X2is C(R22)qor N(RN)n, X3is C(R22)q, X4is C(R22)qor N(RN)n, X5is C(R22)q, N(RN)nor O, wherein the dashed line indicates that the bond is a single or double bond, wherein q is 1 or 2, and wherein n is 0 or 1.

[0288] In various embodiments, RB2is one of the following heterocycles RB2.6.1 to RB2.6.13:

[0289] RB2.6.8

[0290] RB2.6.9

[0291] RB2.6.10

[0292] RB2.6.5 RB2.6.11

[0293] RB2.6.6 RB2.6.12

[0294] RB2.6.13

[0295]

[0296] In various embodiments, RB2is one of the heterocycles RB2.6.1 to RB2.6.13.

[0297] In various embodiments, RB2is one of the heterocycles RB2.6.1 to RB2.6.5.In various embodiments, RB2is one of the heterocycles RB2.6.4 or RB2.6.5, in particular RB2.6.4

[0298] In various embodiments, RB2is one of the pyrimidines RB2.6.7 to RB2.6.11.

[0299] In various embodiments, RB2is RB2.6.1 , RB2.6.2 or RB2.6.3, preferably RB2.6.1 or RB2.6.2.

[0300] In various embodiments, RB2is pyridyl substituted with one R22.

[0301] In various embodiments, RB2is Ci-C4-alkynyl, which is unsubstituted or substituted with C3-C6-cycloalkyl or Si(Rs)3; wherein Rsis Ci-C4-alkyl. In a particular embodiment, RB2is propargyl which is unsubstituted or substituted with Si(Rs)3; wherein Rsis Ci-C4-alkyl. In a particular embodiment, RB2is propargyl which is unsubstituted or substituted with SiMes. In various embodiments, RB2is propargyl which is substituted with cyclopropyl.

[0302] In various embodiments, RB2is a five-membered saturated, partially unsaturated, or fully unsaturated heterocyclic ring, wherein said heterocyclic ring comprises one, two or three, same or different heteroatoms selected from N, O, and S, wherein N may be unsubstituted or substituted with Ci-C4-alkyl, Cs-Ce-cycloalkyl, C-bound Ci-C4-alkoxy, Ci-C4-alkyl-Ci-C4-alkoxy; and wherein the five-membered ring is unsubstituted or substituted with one R22.

[0303] In various embodiments, RB2is a five-membered saturated, partially unsaturated, or fully unsaturated heterocyclic ring, wherein said heterocyclic ring comprises one, two or three, same or different heteroatoms selected from N, O, and S, wherein N may be unsubstituted or substituted with Ci-C4-alkyl; and wherein the five-membered ring is unsubstituted or substituted with one R22.

[0304] The five-membered ring RB2may be bound to the remainder of the molecule via a C atom of the ring (C-linked) or via a heteroatom of the ring, preferably a nitrogen atom N (N-linked). In various embodiments, RB2is bound via a C-atom of the ring (C-linked). In various embodiments, RB2is bound via a nitrogen atom of the ring (N-linked).

[0305] In various embodiments, the five-membered ring RB2comprises at least one nitrogen atom N in the ring, wherein said N may be unsubstituted or substituted with Ci-C4-alkyl, Cs-Ce-cycloalkyl, C-bound Ci-C4-alkoxy, Ci-C4-alkyl-Ci-C4-alkoxy, preferably Ci-C4-alkyl.

[0306] In various embodiments, the five-membered ring RB2is unsubstituted.

[0307] In various embodiments, the five-membered ring RB2comprises an N-atom which is unsubstituted, and wherein the ring is unsubstituted in total. In various embodiments of the invention, the five-membered ring RB2comprises an N-atom which is unsubstituted, and wherein the ring is substituted with one R22.

[0308] In various embodiments, the five-membered ring RB2comprises an N-atom which is substituted with Ci-C4-alkyl, Cs-Ce-cycloalkyl, C-bound Ci-C4-alkoxy, Ci-C4-alkyl-Ci-C4-alkoxy, preferably Ci-C4-alkyl, and wherein the ring is unsubstituted apart from that. In various embodiments of the invention, the five-membered ring RB2comprises an N-atom which is substituted with Ci-C4-alkyl, Cs-Ce-cycloalkyl, C-bound Ci-C4-alkoxy, Ci-C4-alkyl-Ci-C4-alkoxy, preferably Ci-C4-alkyl, and wherein the ring is substituted with one R22.

[0309] In various embodiments, the five-membered ring RB2is substituted with one R22.

[0310] In various embodiments, RB2is one of the following heterocycles RB2.5.1 to RB2.5.28:

[0311] R22RB2.5.7 RB2.5.8 RB2.5.9

[0312] ,R22RB2.5.11 RB2.5.12

[0313] R22RB2.5.13 RB2.5.14 RB2.5.15 _N

[0314] RB2.5.15 RB2.5.22 RB2.5.23

[0315]

[0316] RB2.5.25 RB2.5.26

[0317] RB2.5.28

[0318]

[0319] In various embodiments, RB2is a pyrazole RB2.5.1, RB2.5.2 or RB2.5.3.

[0320] In various embodiments, RB2is an isoxazole RB2.5.4 or RB2.5.5 or dihydroisoxazole RB2.5.6 or RB2.5.7. In various embodiments, RB2is an isoxazole RB2.5.4 or RB2.5.5.

[0321] In various embodiments, RB2is a thiazole RB2.5.8, RB2.5.9 or RB2.5.10.

[0322] In various embodiments, RB2is a triazole RB2.5.11 or RB2.5.12.

[0323] In various embodiments, RB2is an oxadiazole RB2.5.13, RB2.5.14 or a thiadiazole RB2.5.15.

[0324] In various embodiments of the above, R22is halogen, cyano, Ci-C4-alkyl, which is unsubstituted or partially or fully halogenated; NH-CO-RM; C3-C6-cycloalkyl; Ci-C4-alkoxy-Ci-C4-alkyl, C3-Ce-cycloalkyl-Ci-C3-alkoxy, Ci-C4-alkoxy-Ci-C4-alkoxy-Ci-C4-alkyl; C(RM)2-CN, CHRM-CN, C(RM)2-(CONH2), CHRM-(CONH2), C(RM)2-(CSNH2), CHRM-(CSNH2), 1-cyano-C3-C6-cycloalkyl, 1-C3-C6-cycloalkyl-carboxamide, 1-C3-C6-cycloalkyl-thiocarboxamide, O-CH2-CN, O-CHRM-CN, O-C(RM)2-CN, O-C(RM)2-(CONH2), O-C(RM)2-(CSNH2), 0-1-cyano-C3-C6-cycloalkyl, O-C(CONH2)-C3-C6-cycloalkyl, 0-C(CSNH2)-C3-C6-cycloalkyl; O-S(O)2-RM; Ci-C3-alkoxy, which is unsubstituted or partially or fully halogenated; C3-C6-cycloalkyl-Ci-C3-alkoxy which is unsubstituted or partially or fully halogenated, C3-C6-cycloalkoxy, which is unsubstituted or partially or fully halogenated; S-RM, SO-RM; SO2-RM;S(O)(=NRM)RM, S(O)(=NH)RM,

[0325] N=S(O)(RM)2, CO-N=SO(RM)2, SF5, or two R22(on the same carbon atom) combine to form carbonyl or difluoromethylen.

[0326] In various embodiments, R22is halogen, in particular fluoro, chloro, bromine, even more particular bromo or chloro, more particular bromo.

[0327] In various embodiments, R22is cyano.In various embodiments, R22is Ci-Cs-alkoxy, which is unsubstituted or partially or fully halogenated. Ini particular, R22is trifluoromethoxy, difluoromethoxy, methoxy.

[0328] In various embodiments, R22is Cs-Ce-cycloalkyl, in particular cyclopropyl.

[0329] In various embodiments, R22is Cs-Ce-cycloalkoxy, which is unsubstituted or partially or fully halogenated; in particular cyclopropyloxy.

[0330] In various embodiments, R22is C(RM)2-(CN), CHRM-CN, C(RM)2-(CONH2), CHRM-(CONH2), C(RM)2-(CSNH2), CHRM-(CSNH2), l-cyano-Cs-Ce-cycloalkyl, l-Cs-Ce-cycloalkyl-carboxamide, or I-C3-C6-cycloalkyl-thiocarboxamide.

[0331] In various embodiments, R22is C(CH3)2-(CN), C(CH3)2-(CONH2), 1-cyano-cyclopropyl, 1-cyclopropyl- carboxamide, preferably C(CH3)2-(CN) or 1-cyano-cyclopropyl.

[0332] In various embodiments, R22is C(RM)2-CN, in particular C(CH3)2-(CN).

[0333] In various embodiments, R22is C(RM)2-(CONH2) orC(RM)2-(CSNH2), in particular C(CH3)2-(CONH2) or C(CH3)2-(CSNH2).

[0334] In various embodiments, R22is l-cyano-Cs-Ce-cycloalkyl, in particular 1-cyano-cyclopropyl. In various embodiments, R22is l-Cs-Ce-cycloalkyl-carboxamide, l-Cs-Ce-cycloalkyl-thiocarboxamide, in particular 1-cyclopropyl-carboxamide or 1-cyclopropyl-thiocarboxamide.

[0335] In various embodiments, R22is O-C(RM)2-CN, O-C(RM)2-(CONH2), O-C(RM)2-(CSNH2), in particular O-C(CH3)2-CN or O-C(CH3)2-(CONH2).

[0336] In various embodiments, R22is O-l-cyano-Cs-Ce-cycloalkyl, 0-C(CONH2)-C3-C6-cycloalkyl, O-C(CSNH2)-C3-C6-cycloalkyl, in particular O-1-cyano-cyclopropyl, 0-C(CONH2)-cyclopropyl, O-C(CSNH2)-cyclopropyl.

[0337] In various embodiments, R22is O-S(O)2-RM; in particular O-S(O)2-CH3.

[0338] In various embodiments, R22is SF5.

[0339] In various embodiments, R22is N=S(O)(RM)2, in particular N=S(O)(CH3)2.

[0340] In various embodiments, R22is CO-N=SO(RM)2, in particular CO-N=SO(CH3)2.In various embodiments, RB3is H and RB2is a five-membered saturated, partially unsaturated, or fully unsaturated heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one, two or three, same or different heteroatoms selected from N, O, and S, wherein N may be unsubstituted or substituted with Ci-C4-alkyl; Cs-Ce-cycloalkyl, C-bound Ci-C4-alkoxy, Ci-C4-alkyl-Ci-C4-alkoxy; wherein the five-membered ring is unsubstituted or substituted with one R22, or in which the ring contains a group -C(RM)2- or the atom via which RB2is attached to the remainder of the molecule, has a further substituent RM.

[0341] The five-membered ring RB2may be bound to the remainder of the molecule via a C atom of the ring (C-linked) or via a heteroatom of the ring, preferably a nitrogen atom N (N-linked). In various embodiments, RB2is bound via a C-atom (C-linked). In various embodiments, RB2is bound via a C-atom (C-linked), and the atom via which RB2is attached to the remainder of the molecule, may have a further substituent RM.

[0342] In various embodiments, RB2is bound via a nitrogen atom (N-linked). In various embodiments, RB2is bound via a nitrogen atom (N-linked), and in certain cases, the nitrogen via which RB2is attached to the remainder of the molecule, may have a further substituent RM. This will usually cause a positive charge on the N atom, which must be balanced by a negative charge either within the molecule, or via a corresponding negative charge (anion).

[0343] In various embodiments, RB2comprises at least one nitrogen atom N in the ring, wherein said N may be unsubstituted or substituted with Ci-C4-alkyl, Cs-Ce-cycloalkyl, C-bound Ci-C4-alkoxy, Ci-C4-alkyl-Ci-C4-alkoxy, preferably Ci-C4-alkyl.

[0344] In various embodiments, the N-atom in the heterocyclic ring RB2is unsubstituted, and the rest of RB2is unsubstituted. In various embodiments, the N-atom in the heterocyclic ring RB2is unsubstituted, and the rest of RB2is substituted with one R22. In various embodiments, the N-atom in the heterocyclic ring RB2is unsubstituted, and the ring of RB2contains a group -C(RM)2.

[0345] In various embodiments, the N-atom in the heterocyclic ring RB2is substituted, preferably with Ci-C4-alkyl, and the rest of RB2is unsubstituted. In various embodiments, the N-atom in the heterocyclic ring RB2is substituted, preferably with Ci-C4-alkyl, and the rest of RB2is substituted with one R22. In various embodiments, the N-atom in the heterocyclic ring RB2is substituted, preferably with Ci-C4-alkyl, and the ring of RB2contains a group -C(RM)2.

[0346] In various embodiments of this invention, RB3is H and RB2is one of the heterocycles RB2.5.1 to RB2.5.28 shown herein above.In various embodiments of this invention, RB3is H and RB2is one of the heterocycles RB2.5.1 to RB2.5.5.

[0347] In various embodiments of this invention, RB3is H and RB2is a pyrazole RB2.5.16, RB2.5.17 or RB2.5.18.

[0348] In various embodiments of this invention, RB3is H and RB2is an isoxazole RB2.5.19 or RB2.5.20 or dihydroisoxazole RB2.5.6 or RB2.5.7. In various embodiments, RB2is an isoxazole RB2.5.19 or RB2.5.20.

[0349] In various embodiments of this invention, RB3is H and RB2is a thiazole RB2.5.8, RB2.5.9 or RB2.5.10.

[0350] In various embodiments of this invention, RB3is H and RB2is a triazole RB2.5.11 or RB2.5.12.

[0351] In various embodiments of this invention, RB3is H and RB2is an oxadiazole RB2.5.13, RB2.5.14 or a thiadiazole RB2.5.15.

[0352] In various embodiments, the five-membered ring RB2is unsubstituted.

[0353] In various embodiments, the five-membered ring RB2is substituted with one R22.

[0354] In various embodiments, the five-membered ring RB2contains a group -C(RM)2.

[0355] In various embodiments of the above, R22is halogen.

[0356] In the compounds of the present invention, halogen is preferably fluoro, chloro, bromine, more preferably fluoro or chloro, more preferably fluoro.

[0357] In various embodiments, RB3is H, RB2is pyrazole substituted with halogen (preferably bromo, chloro), RA3is H and RA2is S(O)m-Ci-C4-alkyl, S(0)m-C3-C6-cycloalkyl, S(0)m-C3-C6-cycloalkyl-Ci-C4-alkyl, which are unsubstituted or halogenated, and m is 0, 1 or 2. In various embodiments, RB3is H, RB2is pyrazole substituted with halogen (preferably bromo, chloro), and RA3is H and RA2is (S=O)-CF3, SO2-CF3, SCF3. In various embodiments, RB3is H, RB2is pyrazole RB2.5.2 substituted with halogen (preferably bromo, chloro), and RA3is H and RA2is S(O)m-Ci-C4-alkyl, S(O)m-C3-C6-cycloalkyl, S(0)m-C3-C6-cycloalkyl-Ci-C4-alkyl, which are unsubstituted or halogenated, and m is 0, 1 or 2; preferably wherein RA3is H and RA2is (S=O)-CF3, SO2-CF3, SCF3.In various embodiments of the above, R22is Ci-C4-alkyl, which is partially or fully halogenated. In various embodiments of the above, R22is CF3. In various embodiments, R22is CHF2.

[0358] In various embodiments, RB3is H, RB2is pyrazole substituted with CF3, and RA3is H and RA2is S(O)m-Ci-C4-alkyl, S(0)m-C3-C6-cycloalkyl, S(0)m-C3-C6-cycloalkyl-Ci-C4-alkyl, which are unsubstituted or halogenated, and m is 0, 1 or 2. In various embodiments, RB3is H, RB2is pyrazole substituted with CF3, and RA3is H and RA2is (S=O)-CF3, SO2-CF3, SCF3. In various embodiments, RB3is H, RB2is pyrazole RB2.5.2 substituted with CF3, RA3is H and RA2is S(O)m-Ci-C4-alkyl, S(O)m-Cs-Ce-cycloalkyl, S(0)m-C3-C6-cycloalkyl-Ci-C4-alkyl, which are unsubstituted or halogenated, and m is 0, 1 or 2; preferably wherein RA3is H and RA2is (S=O)-CF3, SO2-CF3, SCF3.

[0359] In various embodiments, RB3is H and RB2is phenyl substituted with (a) one R22, or (b) substituted with one R22and one halogen, or (c) substituted with up to 5 halogens. In various embodiments, RB2is phenyl substituted with one R22, or substituted with 2 or 3 halogens, for example fluoro, chloro or bromo.

[0360] In various embodiments of this invention, RB3is H and RB2is phenyl substituted with one R22and one fluoro atom.

[0361] In various embodiments of this invention, RB3is H and RB2is a six-membered saturated, partially unsaturated, or fully unsaturated heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one, two or three, same or different heteroatoms O or N, wherein N may be unsubstituted or substituted with Ci-C4-alkyl, and said ring / ring system is substituted with one R22, or substituted with two halogens.

[0362] In various embodiments of this invention, RB3is H and RB2is a six-membered saturated, partially unsaturated, or fully unsaturated heterocyclic ring or ring system, wherein said heterocyclic ring or ring system is bound to the remainder of the molecule by a nitrogen atom (N-bound). In various embodiments, RB2is one of the heterocycles RB2.6.1 to RB2.6.13 shown herein above.

[0363] In various embodiments of this invention, RB3is H and RB2is one of the heterocycles RB2.6.1 to RB2.6.5.

[0364] In various embodiments of this invention, RB3is H and RB2is one of the heterocycles RB2.6.1 to RB2.6.5.In various embodiments of this invention, RB3is H and RB2is one of the heterocycles RB2.6.4 or RB2.6.5.

[0365] In various embodiments of this invention, RB3is H and RB2is one of the pyrimidines RB2.6.7 to RB2.6.11.

[0366] In various embodiments of this invention, RB3is H and RB2is RB2.6.1 , RB2.6.2 or RB2.6.3, preferably RB2.6.1 or RB2.6.2.

[0367] In various embodiments of this invention, RB3is H and RB2is a 1 ,3-benzodioxole which is unsubstituted or halogenated.

[0368] In various embodiments of this invention, RB3is H and RB2is Ci-C4-alkynyl, which is unsubstituted or substituted with Si(Rs)3; wherein Rsis Ci-C4-alkyl. In a particular embodiment, RB2is propargyl which is unsubstituted or substituted with Si(Rs)3; wherein Rsis Ci-C4-alkyl. In a particular embodiment, RB2is propargyl which is unsubstituted or substituted with SiMes.

[0369] In some embodiments, both RB3and RB2are H.

[0370] In various embodiments, RB2is C-i-Ce-alkyl or Cs-Ce-cycloalkyl, wherein the alkyl and cycloalkyl groups are unsubstituted or substituted with cyano, and RB3is H. In various embodiments RB2is ethyl or isopropyl, which is unsubstituted or substituted with cyano. In various embodiments RB2is cyclopropyl or cyclohexyl, which is unsubstituted or substituted with cyano. In various embodiments, RB2is ethyl.

[0371] In various embodiments of the above, R22is cyano, Ci-C4-alkyl, which is unsubstituted; Cs-Ce-cycloalkyl, or Cs-Ce-cycloalkyl, in which one C is replaced by an O, NRM, S, SO, or SO2; Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkoxy- Ci-C4-alkoxy-Ci-C4-alkyl,C3-C6-cycloalkyl-Ci-C3-alkoxy, C(RM)2-(CN), CHRM-CN, C(RM)2-(CONH2), CHRM-(CONH2), C(RM)2-(CSNH2), CHRM-(CSNH2), 1-cyano-Cs-Ce-cycloalkyl, l-Cs-Ce-cycloalkyl-carboxamide, l-Cs-Ce-cycloalkyl-thiocarboxamide, O-CH2-CN, O-CHRM-CN, O-C(CN)(RM)2, O-C(CONH2)(RM)2, O-C(CSNH2)(RM)2, O-S(O)2-RM; SO2-RM, Ci-Cs-alkoxy, which is unsubstituted or partially or fully halogenated; S(O)(=NRM)RM, S(O)(=NH)RM, N=S(O)(RM)2, CO-N=SO(RM)2, or two R22combine to form carbonyl or difluoromethylen.

[0372] In various embodiments of the above, R22is cyano, Ci-C4-alkyl, which is unsubstituted, C1-C3-alkoxy, which is unsubstituted or partially or fully halogenated;Cs-Ce-cycloalkyl, or C3-C6-cycloalkyl, in which one C is replaced by an O, NRM, S, SO, or SO2; Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkoxy- Ci-C4-alkoxy-Ci-C4-alkyl, C3-C6-cycloalkyl-Ci-C3-alkoxy.

[0373] In various embodiments of the above, R22is cyano.

[0374] In various embodiments of the above, R22is methyl, ethyl, n-propyl or isopropyl, preferably methyl or ethyl.

[0375] In various embodiments of the above, R22is Cs-Ce-cycloalkyl, or Cs-Ce-cycloalkyl, in which one C is replaced by an O, NRM, S, SO, or SO2. In various embodiments, R22is Cs-Ce-cycloalkyl, or Cs-Ce-cycloalkyl, in which one C is replaced by an O, preferably cyclopropyl, cyclobutyl or 3-oxetanyl.

[0376] In various embodiments of the above, R22is Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkoxy-Ci-C4-alkoxy-Ci-C4-alkyl, Cs-Ce-cycloalkyl-Ci-Cs-alkoxy; preferably R22is Ci-C4-alkoxy-Ci-C4-alkyl, C1-C4-alkoxy-Ci-C4-alkoxy-Ci-C4-alkyl. In various embodiments, R22is methoxymethyl or methoxy-ethoxy-methyl.

[0377] In various embodimentsof the above, R22is C(CHs)2-(CN), C(CHs)2-(CONH2), 1-cyano-cyclopropyl, 1-cyclopropyl-carboxamide, preferably C(CHs)2-(CN) or 1-cyano-cyclopropyl.

[0378] In various embodiments of the above, R22is O-CH2-CN, O-CHRM-CN, O-C(CN)(RM)2, O-C(CONH2)(RM)2, O-C(CSNH2)(RM)2, O-1-cyano- C3-C6-cycloalkyl, O- C(CONH2)- C3-C6-cycloalkyl, O- C(CSNH2)- C3-C6-cycloalkyl. In a particular embodiment, R22is O-CH2-CN, O-CHRM-CN, O-C(CN)(RM)2, O-C(CONH2)(RM)2, O-C(CSNH2)(RM)2; preferably O-C(CN)(CH3)2.

[0379] In various embodiments of the above, R22is O-S(O)2-RM; SO2-RM, S(O)(=NRM)RM, S(O)(=NH)RM, N=S(O)(RM)2, CO-N=SO(RM)2.

[0380] In various embodiments of the above, R22is C(RM)2-(CN), CHRM-CN, C(RM)2-(CONH2), CHRM-(CONH2), C(RM)2-(CSNH2), CHRM-(CSNH2), 1-cyano-C3-C6-cycloalkyl, 1-C3-C6-cycloalkyl-carboxamide, 1-C3-C6-cycloalkyl-thiocarboxamide, O-CH2-CN, O-CHRM-CN, O-C(CN)(RM)2, O-C(CONH2)(RM)2, O-C(CSNH2)(RM)2, O-1-cyano- C3-C6-cycloalkyl, O- C(CONH2)- C3-C6-cycloalkyl, O- C(CSNH2)- C3-C6-cycloalkyl; O-S(O)2-RM; Ci-C3-alkoxy, which is unsubstituted or partially or fully halogenated; C3-C6-cycloalkyl-Ci-C3-alkoxy which is unsubstituted or partially or fully halogenated, C3-C6-cycloalkoxy which is unsubstituted or partially or fully halogenated; S(O)(=NRM)RM, S(O)(=NH)RM, N=S(O)(RM)2, CO-N=SO(RM)2, halogen, cyano, or two R22combine to form carbonyl, difluoromethylen.In various embodiments of the above, R22is C(RM)2-(CN), CHRM-CN, C(RM)2-(CONH2), CHRM-(CONH2), C(RM)2-(CSNH2), CHRM-(CSNH2), 1-cyano-C3-C6-cycloalkyl, 1-C3-C6-cycloalkyl-carboxamide, 1-C3-C6-cycloalkyl-thiocarboxamide, O-CH2-CN, O-CHRM-CN, O-C(CN)(RM)2, O-C(CONH2)(RM)2, O-C(CSNH2)(RM)2, O-S(O)2-RM; Ci-C3-alkoxy, which groups are unsubstituted or partially or fully halogenated; C3-C6-cycloalkyl-Ci-C3-alkoxy, S(O)(=NRM)RM, S(O)(=NH)RM, N=S(O)(RM)2, CO-N=SO(RM)2, halogen, cyano, or two R22combine to form carbonyl, difluoro methylen.

[0381] In various embodiments of the above, R22is C(RM)2-(CN), CHRM-CN, C(RM)2-(CONH2), CHRM-(CONH2), C(RM)2-(CSNH2), CHRM-(CSNH2), 1-cyano-C3-C6-cycloalkyl, 1-C3-C6-cycloalkyl-carboxamide, 1-C3-C6-cycloalkyl-thiocarboxamide. In a particular embodiment, R22is C(RM)2-(CN), C(RM)2-(CONH2), 1-cyano-C3-C6-cycloalkyl, or 1-C3-C6-cycloalkyl-carboxamide. In a particular embodiment, R22is C(CH3)2-(CN), C(CH3)2-(CONH2), 1-cyano-cyclopropyl, or 1 -cyclopropylcarboxamide.

[0382] In various embodiments of the above, R22is O-CH2-CN, O-CHRM-CN, O-C(CN)(RM)2, O-C(CONH2)(RM)2, O-C(CSNH2)(RM)2, O-1-cyano- C3-C6-cycloalkyl, O- C(CONH2)- C3-C6-cycloalkyl or 0-C(CSNH2)-C3-C6-cycloalkyl. In a particular embodiment, R22is O-C(CN)(RM)2, O-C(CONH2)(RM)2, or O-S(O)2-RMIn a particular embodiment, R22is O-C(CN)(CH3)2, or O-C(CONH2)(CH3)2. In a particular embodiment, R22is O-S(O)2-RM, preferably O-S(O)2-CH3.

[0383] In various embodiments of the above, R22is Ci-C3-alkoxy, which is unsubstituted or partially or fully halogenated, or C3-C6-cycloalkyl-Ci-C3-alkoxy which is unsubstituted or partially or fully halogenated, C3-Ce-cycloalkoxy which is unsubstituted or partially or fully halogenated;. In various embodiments, R22is Ci-C3-alkoxy, which is fully halogenated, preferably trifluoromethoxy.

[0384] In various embodiments of the above, R22is S(O)(=NRM)RM, S(O)(=NH)RM, N=S(O)(RM)2, or CO-N=SO(RM)2. In a particular embodiment, R22is S(O)(=NCH3)CH3S(O)(=NH)CH3, or N=S(O)(CH3)2.

[0385] In various embodiments of the above, two R22combine to form carbonyl or difluoromethylen.

[0386] In various embodiments of the above, R22is halogen, preferably fluoro or chloro, preferably fluoro.

[0387] In various embodiments of the above, R22is C(RM)2-(CN), C(RM)2-(CONH2), 1-cyano-C3-Ce-cycloalkyl, 1-C3-C6-cycloalkyl-carboxamide, O-C(CN)(RM)2, O-C(CONH2)(RM)2, O-S(O)2-RM; Ci-C3-alkoxy, which is fully halogenated; S(O)(=NRM)RM, S(O)(=NH)RM, N=S(O)(RM)2, halogen, cyano, carbonyl, difluoromethylen.In various embodiments of the above, R22is C(CH3)2-(CN), C(CH3)2-(CONH2), 1-cyano-cyclopropyl, 1-cyclopropyl-carboxamide, O-C(CN)(CH3)2, O-C(CONH2)(CH3)2, O-S(O)2-CH3; Ci-Cs-alkoxy, which is fully halogenated (preferably trifluoromethoxy), S(O)(=NCH3)CH3 S(O)(=NH)CH3, N=S(O)(CH3)2, halogen, cyano.

[0388] In various embodiments of all compounds described herein above, the index p is 1 or 2. In various embodiments the index p is 2.

[0389] In various embodiments of all compounds described herein above, RNis H orCi-C4-alkyl. In various embodiments RNis H, methyl or ethyl.

[0390] In various embodiments of all compounds described herein above, Rwis Ci-C4-alkyl. In various embodiments Rwis ethyl.

[0391] It is understood that all embodiments described above for the compounds of formula (I) and (IV) to (XI) are similarly applicable to the starting compounds of formula (II) and (III), in particular with respect to the preferred substituent options disclosed herein above.

[0392] In various embodiments, the invention relates to a process for preparation of a compound of formula (I) ora compound of any one of formula (IV), formula (V), formula (VI), formula (VII), formula (VIII), formula (IX), formula (X), or formula (XI) by reacting a compound of formula (II) with a compound of formula (III), wherein said reaction is a one-step reaction.

[0393] The compounds of formula (II) and formula (III) can be used in any suitable ratio. Typical molar ratios range from 2:1 to 1:2. Preferred ratios are from 1.5:1 to 1:1.5, such as 1.2:1 to 1:1.2. Exemplary ratio may be 1.2:1; 1.1:1, 1:1.1; 1:1.05, and 1:1.2. In various embodiments, the compound of formula (II) is used in slight molar excess relative to the compound of formula (III), typically within the ranges given above, e.g. 1.5:1 to 1.05:1.

[0394] In various embodiments the reaction is carried out in presence or absence of a Lewis acid. In various embodiments the reaction is carried out in the presence of a Lewis acid. In various embodiments the reaction is carried out in the presence of a Lewis acid and the Lewis acid is present in an amount of 1-70% of the molarity of either the compound of formula (II) or the compound of formula (III). In various embodiments the reaction is carried out in the presence of a Lewis acid and the Lewis acid is present in an amount of 10-60% of the molarity of either the compound of formula (II) or the compound of formula (III). In various embodiments the reaction is carried out in the presence of a Lewis acid and the Lewis acid is present in an amount of 20-50% of the molarity of either the compound of formula (II) or the compound of formula (III). In variousembodiments the reaction is carried out in the presence of a Lewis acid and the Lewis acid is present in 20%, 30%, 40% or 50% of the molarity of either the compound of formula (II) or the compound of formula (III). “Molarity” as used in this context, refers to the amount in mol relative to either the compound of formula (II) or (III). For example, if the compound of formula (II) is present in an amount of 1 mol, 70% of the molarity would be 0.7 mol of the Lewis acid.

[0395] In various embodiments, the one or more Lewis acids are selected from the group consisting of Cu(OTf)2, PdCI2, ZnCI2, NiCI2, MnCI2, CaCI2, CrCI2, FeCI2, FeCI3, CoCI2, CdCI2, PtCI2, CuCI2, CuCI, SnCI2, Ti(OiPr)4, Zn(OTf)2, Fe(OTf)2(CHs^SiOTf, (CHs^SiCI, and combinations thereof.

[0396] In various embodiments the reaction is carried out in presence of Cu(OTf)2. In various embodiments the reaction is carried out in presence of PdCI2. In various embodiments the reaction is carried out in presence of ZnCI2. In various embodiments the reaction is carried out in presence of N iCI2. In various embodiments the reaction is carried out in presence of MnCI2. In various embodiments the reaction is carried out in presence of CaCI2. In various embodiments the reaction is carried out in presence of CrCI2. In various embodiments the reaction is carried out in presence of FeCI2. In various embodiments the reaction is carried out in presence of FeCh. In various embodiments the reaction is carried out in presence of CoCI2. In various embodiments the reaction is carried out in presence of CdCI2. In various embodiments the reaction is carried out in presence of PtCI2. In various embodiments the reaction is carried out in presence of CuCI2. In various embodiments the reaction is carried out in presence of CuCI. In various embodiments the reaction is carried out in presence of SnCI2. In various embodiments the reaction is carried out in presence of Ti(OiPr)4. In various embodiments the reaction is carried out in presence of Zn(OTf)2. In various embodiments the reaction is carried out in presence of Fe(OTf)2. In various embodiments the reaction is carried out in presence of (CHs^SiOTf. In various embodiments the reaction is carried out in presence of (CH3)3SiCI. In various embodiments, the Lewis acid is selected from Cu(OTf)2, (CHs^SiOTf, TMSOTf, SnCI2, Zn(OTf)2, PdCI2, MnCI2, and FeCI2. In various embodiments, it can be preferred to carry out the reaction in the absence of a Lewis acid catalyst.

[0397] In various embodiments the reaction is carried out in presence of a suitable solvent. In various embodiments the suitable solvent is any of aliphatic hydrocarbons, such as pentane, hexane, cyclohexane, or petrol ether; aromatic hydrocarbons, such as benzene, toluene, o-, m-, and p-xylene; halogenated hydrocarbons, or halogenated aromatic Ce-C -hydrocarbons, such as CH2CI2, CHCI3, CCI4, CH2CICH2CI, CCI3CH3, CHCI2CH2CI, CCI2CCI2, or chlorobenzene; ethers, such as CH3CH2OCH2CH3, (CH3)2CHOCH(CH3)2, CH3OC(CH3)3(MTBE), CH3OCH3 (DME), CH3OCH2CH2OCH3, CH3OC(CH3)2CH2CH3, dioxane, anisole, 2-methyltetrahydrofuran, tetrahydrofuran (THF), and diethylene glycol; nitriles, such as CH3CN, and CH3CH2CN; alcohols, such as CH3OH, CH3CH2OH, CH3CH2CH2OH, CH3CH(OH)CH3, CH3(CH2)3OH, and C(CH3)3OH,CH2(OH)CH2(OH), and CH3CH(OH)CH2OH. Mixtures of the above solvents are also possible in presence of suitable bases such as pyrrolidine; tertiary amines, such as diisopropylethylamine, trimethylamine, triethylamine, triisopropylamine and N-methylpiperidine, imidazole, pyridine; substituted pyridines, such as collidine, lutidine and 4-dimethylaminopyridine, and polycyclic amides and amidines, such as 1,8-diazabicycloundec-7-ene (DBU) or 1,4-Diazabicyclo[2.2.2]octane (DABCO). In various embodiments the suitable solvent is chlorobenzene.

[0398] In various embodiments the process is carried out at a temperature in the range of 0°C to 250°C. In various embodiments the process is carried out at a temperature in the range of 80°C to 200°C, preferably in the range of 100 to 160 °C. Preferred temperatures may be 120-140 °C, for example about 130 or about 140°C. The heating may be achieved by microwaves. In various embodiments the process is carried out for a duration in the range of 1 to 24 h. In various embodiments the process is carried out for a duration of 1 h, 1 ,5h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 12h, 14h, 16h, 18h, or20h.

[0399] In various embodiments the process is carried out in absence of a Lewis acid at 120°C to 140°C for 1 to 6 h, for example, using chlorobenzene as solvent.

[0400] In various embodiments the invention relates to any compound obtainable / obtained by the process described herein above.

[0401] Further non-limiting embodiments are illustrated in the following examples.

[0402] Examples

[0403] Lewis acid Solvent

[0404]

[0405] Synthesis of2-(5-bromo-3-ethylsulfonyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine

[0406] To a stirred solution of N2-methyl-5-(trifluoromethyl)pyridine-2,3-diamine (0.625 g, 3.271 mmol) in dry Chlorobenzene (3 mL) were added 5-bromo-3-ethylsulfonyl-pyridine-2-carbonitrile (0.6 g, 2.181 mmol) and Cu(OTf)2 (0.158 g, 0.436 mmol) at ambient temperature under inert atmosphere inRadley vial. Then the vial was closed the reaction mixture was stirred at 140°C for 18 h under inert atmosphere. The progress of the reaction mixture was monitored by TLC. After the reaction was completed, the reaction mixture was poured into water (30 mL) and extracted with EtOAc (2 x 40 mL). Combined organic layers were dried over sodium sulphate and evaporated under reduced pressure. The crude product was purified by flash chromatography using EtOAc and heptane as eluent to offer the desired product as solid (0.240 g, 24.5% yield).

[0407] 1H NMR (300 MHz, DMSO-cfe) 69.31 (d, J = 2.2 Hz, 1H), 8.91 (dt, = 2.1, 0.8 Hz, 1H), 8.75 -8.66 (m, 2H), 3.86 (q, = 7.4 Hz, 2H), 3.79 (s, 3H), 1.24 (t, = 7.4 Hz, 3H). LC / MS: Rt: 2.16 min; m / z = 449.1 (M)+.

[0408] 2

[0409] Lewis acid Solvent

[0410]

[0411] Synthesis of 6-(5-bromo-3-ethylsulfonyl-2-pyridyl)-2,2-difluoro-7-methyl-[1,3]dioxolo[4,5-f] benzimidazole

[0412] To the mixture of 5-bromo-3-ethylsulfonyl-pyridine-2-carbonitrile (200 mg, 7.272mmol) and 2,2-difluoro-N5-methyl-1 ,3-benzodioxole-5,6-diamine (176 mg, 8.727 mmol) in 0.4 mL of chlorobenzene was added Trimethylsilyl trifluoromethanesulfonate (TMSOTf) (0.52 mL, 2.908 mmol). Reaction mixture was heated at 130°C for 1h. Reaction was monitored by LCMS. After the reaction was completed 20mL of water was added in the reaction mixture and was basified with sat. NaHCOa solution, compound was extracted with EtOAc (20 mL X 2 times). Organic layer was dried over Na2SO4 and concentrated under reduced pressure to get the crude product was purified by FCC using 40% EtOAc and n-heptane as an eluent to afford (322 mg, 97% yield) of desired product as white solid.

[0413] 1 H NMR (300 MHz, DMSO-d6) 59.25 (d, J = 2.2 Hz, 1 H), 8.64 (d, J = 2.2 Hz, 1 H), 7.87 (s, 1 H), 7.78 (s, 1H), 3.89 (q, J = 7 A Hz, 2H), 3.72 (s, 3H), 1.21 (t, J= 7.4 Hz, 3H).

[0414] LC-MS: mass calculated for C16H12BrF2N3O4S [M]+ 458.9, found 460.1 (M+1).

[0415] 3Lewis acid

[0416] Solvent

[0417]

[0418] Synthesis of2-(5-bromo-3-ethylsulfonyl-2-pyridyl)-1-methyl-5-(trifluoromethyl)benzimidazole To a stirred solution of N1-methyl-4-(trifluoromethyl)benzene-1,2-diamine (0.518 g, 2.726 mmol) in dry Chlorobenzene (2.5 mL) were added 5-bromo-3-ethylsulfonyl-pyridine-2-carbonitrile (0.500 g, 1.817 mmol) and TMSOTf (1.616 g, 7.27 mmol) at ambient temperature under inert atmosphere in Radley vial. Then the vial was closed, and the reaction mixture was stirred at 140°C for 20 h under inert atmosphere. The progress of the reaction mixture was monitored by TLC. After the reaction was completed, the reaction mixture was poured into Aq. NaHCOa solution (35 mL) and extracted with EtOAc (2 x 40 mL). Combined organic layers were dried over sodium sulphate and evaporated under reduced pressure. The crude product was purified by flash chromatography using EtOAc and heptane as eluent to offer the desired product as solid (0.715 g, 87.77% yield).

[0419] 1H NMR (500 MHz, DMSO-cfe) 69.29 (d, J = 2.2 Hz, 1H), 8.68 (d, J = 2.2 Hz, 1H), 8.14 (dd, J = 1.8, 0.9 Hz, 1 H), 7.95 (d, J = 8.6 Hz, 1 H), 7.73 (dd, J = 8.7, 1.7 Hz, 1 H), 3.89 (q, J = 7.4 Hz, 2H), 3.78 (s, 3H), 1.23 (t, J= 7.4 Hz, 3H). LC / MS: Rt: 2.19 min; m / z = 450.1 (M+2)+.

[0420] Example 4

[0421]

[0422] Step-1 Synthesis of 6-(5-cyclopropyl-3-ethylsulfonyl-2-pyridyl)-2, 2-difluoro-7-methyl-[ 1, 3]dioxolo[4, 5-f]benzimidazole

[0423] To the mixture of 5-cyclopropyl-3-ethylsulfonyl-pyridine-2-carbonitrile (100 mg, 0.423mmol) and 2,2-difluoro-N5-methyl-1 ,3-benzodioxole-5,6-diamine (103 mg, 0.507 mmol) in 0.2mL of chlorobenzene was added Trimethylsilyl trifluoromethanesulfonate (0.31 mL, 1.693 mmol). Reaction mixture was heated at 130°C for 1h. Reaction was monitored by LCMS. After the reaction was completed 20mL of water was added in the reaction mixture and was basified with sat. NaHCOa solution, compound was extracted with EtOAc (2 X 20 mL). Organic layer was dried over Na2SO4 and concentrated under reduced pressure to get the crude product was purified by FCCusing 40% EtOAc and n-heptane as an eluent to afford (178 mg, 99% yield) of desired product as white solid.

[0424] 1H NMR (300 MHz, DMSO-d6) 58.84 (d, J = 2.1 Hz, 1H), 8.09 (d, J = 2.1 Hz, 1H), 7.85 (s, 1H), 7.75 (s, 1H), 3.81 (q, = 7.4 Hz, 2H), 3.67 (s, 3H), 2.28 (m, 1H), 1.19 (m, 5H), 1.04 - 0.95 (m, 2H). LC / MS: Rt = 2.13 min; m / z = 422.3 (M+1).

[0425] Example 5

[0426] Lewis acid Solvent

[0427]

[0428] Step-1 Synthesis of 2-(5-cyclopropyl-3-ethylsulfonyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4!5-b]pyridine

[0429] To a stirred solution of N2-methyl-5-(trifluoromethyl)pyridine-2,3-diamine (0.097 g, 0.508 mmol) in Chlorobenzene (0.5 mL) were added 5-cyclopropyl-3-ethylsulfonyl-pyridine-2-carbonitrile (0.100 g, 0.423 mmol) and Cu(OTf)2 (0.031 g, 0.085 mmol) at ambient temperature under innert atmosphere in a Radley tube. Then the tube was closed, and the reaction mixture was stirred at 140°C for 18 h. The progress of the reaction mixture was monitored by TLC. After the reaction was completed, the reaction mixture was poured into water (10 mL) and extracted with EtOAc (2 x 15 mL). Combined organic layers were dried over sodium sulphate and evaporated under reduced pressure. The crude product was purified by flash chromatography using EtOAc and heptane as eluent to offer the desired product as solid (0.096 g, 54.68% yield).

[0430] 1H NMR (300 MHz, DMSO-cfe) 68.93 - 8.84 (m, 2H), 8.65 (dt, J = 2.0, 0.7 Hz, 1 H), 8.14 (d, J = 2.1 Hz, 1H), 3.80 (t, J= 7.4 Hz, 2H), 3.75 (s, 3H), 2.30 (tt, J= 8.4, 5.0 Hz, 1H), 1.20 (t, J= 7.4 Hz, 5H), 1.03 (dt, J = 7.1 , 4.6 Hz, 2H). LC / MS: Rt = 2.12 min; m / z = 411.2 (M+1)+.

[0431] Example 6

[0432] cPrB(OH)2

[0433]

[0434] Step-2: Synthesis of 6-(5-cyclopropyl-3-ethylsulfonyl-2-pyridyl)-2,2-difluoro-7-methyl- [ 1, 3]dioxolo[4, 5-f]benzimidazole

[0435] To a stirred solution of 6-(5-bromo-3-ethylsulfonyl-2-pyridyl)-2,2-difluoro-7-methyl-[1 ,3]dioxolo[4,5-f]benzimidazole (0.1g, 0.217 mmol) in a mixture of 1 ,4-dioxane (4 mL) and H2O (0.4 mL) was addedpotassium carbonate (0.075 g, 0.543 mmol) and cyclopropylboronic acid (0.028 g, 0.326mmol). The reaction mixture was degassed with nitrogen gas for 10 mins followed by addition of [1,1' -Bis(diphenylphosphino)ferrocene] dichloropalladium (II) (0.016 g, 0.022 mmol) and degassing was continued for another 5 mins. After the degassing was completed reaction mixture was heated at 100 °C for 2 h. The progress of the reaction was monitored by TLC. After the reaction was completed, it was added with 20mL of water and compound was extracted with 40mL of EtOAc (2 x 20 mL), the combined organic layer was dried over Na2SC>4, concentrated under reduced pressure to get the crude product which was purified by column chromatography using 60% EtOAc in n-heptane as an eluent to afford desired product as beige solid (0.083 g, 91.2% yield).

[0436] 1H NMR (500 MHz, DMSO-d6) 58.85 (d, J = 2.1 Hz, 1H), 8.09 (d, J = 2.1 Hz, 1H), 7.86 (s, 1H), 7.76 (s, 1 H), 7.27 (s, 2H), 3.81 (q, J = 7.4 Hz, 2H), 3.68 (s, 3H), 2.28 (m, 1 H), 1.23 - 1.12 (m, 5H), 1.05 - 0.97 (m, 2H). LC / MS: Rt = 2.13 min; m / z = 422.3 (M+1).

[0437] Example 7

[0438] K2CO3, DMF

[0439]

[0440] Step-2: Synthesis of ethyl 2-cyano-2-[6-(2,2-difluoro-7-methyl-[1,3]dioxolo[4,5-f]benzimidazol-6-yl)-5-ethylsulfonyl-3-pyridyl]acetate

[0441] To a solution of 6-(5-bromo-3-ethylsulfonyl-2-pyridyl)-2,2-difluoro-7-methyl-[1 ,3] dioxolo-[4,5-f] benzimidazole (1.0 g, 2.164 mmol) in dry DMF (10 mL) was added powdered potassium carbonate (0.746 g, 5.411 mmol). The resulting suspension was then heated at 100 °C and ethyl cyanoacetate (0.345 mL, 3.24 mmol) was dozed over a period of 5 min. After full consumption of starting material, the reaction mixture was cooled to room temerature, the reaction mixture was neutralized using aqueous 2N HCI and the resulting mixture was extracted with ethyl acetate. The organic layer was washed with brine solution, dried over sodium sulfate and evaporated under reduced pressure. The crude residue was purified using flash chromatography using (40% ethyl acetate and n-heptane) as an eluent to afford the ethyl 2-cyano-2-[6-(2,2-difluoro-7-methyl-[1 ,3]dioxolo[4,5-f] benzimidazol-6-yl)-5-ethylsulfonyl-3-pyridyl] acetate (0.6 g, 56.06% yield) as a brown oily mass.

[0442] LC / MS: Rt = 2.03 min; m / z = 493 (M+1)

[0443] Example 8

[0444]

[0445] Step-3: Synthesis of 2-[6-(2,2-difluoro-7-methyl-[1,3]dioxolo[4,5-f]benzimidazol-6-yl)-5-ethylsulfonyl-3-pyridyl]acetonitrile

[0446] To a solution of ethyl 2-cyano-2-[6-(2,2-difluoro-7-methyl-[1 ,3] dioxolo [4,5-f] benzimidazol-6-yl)-5-ethylsulfonyl-3-pyridyl] acetate (0.5 g, 1.014 mmol) in a mixture of acetic acid (6 mL) and water (3 mL) was added sodium chloride (0.598 g, 10.14 mmol). The reaction mixture was then stirred at 100 °C until the full consumption of starting material. The reaction mixture was cooled to room temperature, and cold water (40 mL) was added. The resulting mixture was then neutralized by the portion wise addition of solid NaHCOs under vigorous stirring and the neutralized solution was extracted with ethyl acetate. The combined organic layer was washed with brine solution, dried over sodium sulfate, filtered, and evaporated under reduced pressure. The crude residue was purified using flash chromatography using (45 % ethyl acetate and n-heptane) as an eluent to afford the 2-[6-(2,2-difluoro-7-methyl-[1 ,3] dioxolo[4,5-f] benzimidazol-6-yl)-5-ethylsulfonyl-3-pyridyl] acetonitrile (0.21g, 41% yield) as a brown solid.

[0447] 1H NMR (500 MHz, CDCI3) 58.91 (d, = 2.1 Hz, 1H), 8.42 (d, J = 2.2 Hz, 1H), 7.37 (s, 1H), 7.07 (s, 1 H), 3.93 (s, 2H), 3.82 (q, J = 7.4 Hz, 2H), 3.69 (s, 3H), 1.30 (t, J = 7.5 Hz, 3H).

[0448] LC / MS: Rt = 2.0; m / z = 421 (M+1)

[0449]

[0450] Step-4: Synthesis of 2-[6-(2,2-difluoro-7-methyl-[1,3]dioxolo[4,5-f]benzimidazol-6-yl)-5-ethylsulfonyl-3-pyridyl]-2-methyl-propanenitrile

[0451] To a solution of 2-[6-(2,2-difluoro-7-methyl-[1,3] dioxolo[4,5-f] benzimidazol-6-yl)-5-ethylsulfonyl-3-pyridyl] acetonitrile (0.12 g, 0.2850 mmol) in DMF (2.0 mL) was added CS2CO3 (0.231 g, 0.7125 mmol) followed by iodomethane (0.045 mL, 0.627 mmol) and the reaction mixture was stirred at room temperature for overnight. After full consumption of the starting material, the reaction mixture was quenched by addition of water. The resulting mixture was extracted with EtOAc, and the combined organic layers washed with brine, dried over sodium sulfate and concentrated under reduced pressure. The crude material was purified by flash chromatography using n-heptane and EtOAc as an eluent to yield the 2-[6-(2,2-difluoro-7-methyl-[1 ,3] dioxolo[4,5-f] benzimidazol-6-yl)-5-ethylsulfonyl-3-pyridyl]-2-methyl-propanenitrile (0.6 g, 47% yield).1H NMR (300 MHz, DMSO-cfc) 6 9.27 (d, J = 2.4 Hz, 1H), 8.52 (d, J = 2.3 Hz, 1H), 7.88 (s, 1H), 7.79 (s, 1H), 3.89 (q, J= 7.4 Hz, 2H), 3.72 (s, 3H), 1.89 (s, 6H), 1.22 (t, J= 7.5 Hz, 4H).

[0452] LC / MS: Rt = 2.10; m / z = 449 (M+1)

[0453] Example 10

[0454]

[0455] Step-1 a: Synthesis of ethyl 2-cyano-2-(6-cyano-5-ethylsulfanyl-3-pyridyl) acetate

[0456] To a solution of 5-bromo-3-ethylsulfanyl-pyridine-2-carbonitrile (2.5 g, 10.28 mmol) in dry DMF (30 mL) was added powdered potassium carbonate (3.54 g, 25.72 mmol). The resulting suspension was then heated at 100 °C and ethyl cyanoacetate (1.63 mL, 15.43 mmol) was dosed over a period of 1 h. After full consumption of starting material, the reaction mixture was cooled to rt, diluted with EtOAc and the precipitate (inorganic salts) was filtered off. The filtrate was neutralized using aqueous 2 N HCI and the resulting mixture was extracted with EtOAc. The combined organic layer was washed with water, dried over sodium sulfate and evaporated under reduced pressure. The crude residue was purified using by flash chromatography using EtOAc and n-heptane as an eluent to afford the title compound (2.4 g, 84 % yield) as an orange liquid.

[0457] LC / MS: Rt = 1.94; m / z = 276 (M+1)

[0458] Example 11

[0459] AcOH, H2O

[0460] Step-2a

[0461]

[0462] Step-2a: Synthesis of 5-(cyanomethyl)-3-ethylsulfanyl-pyridine-2-carbonitrile

[0463] To a solution of ethyl 2-cyano-2-(6-cyano-5-ethylsulfanyl-3-pyridyl) acetate (1.5 g, 5.43 mmol) in a mixture of acetic acid (5 mL) and water (3 mL) was added sodium chloride (3.1 g, 54.34 mmol). The reaction mixture was then stirred at 100 °C until the full consumption of starting material. The reaction mixture was the cooled to rt and cold water (50 mL) was added. The resulting mixture was then neutralized by the portion wise addition of solid NaHCOa under vigorous stirring and the neutralized solution was extracted with EtOAc. The combined organic layer was washed with water, dried over sodium sulfate, filtered, and evaporated under reduced pressure. The crude residue waspurified by flash chromatography using (45 % ethyl acetate and n-heptane) as an eluent to afford the yellow sticky compound (0.51 g, 98.64% yield).

[0464] 1H NMR (500 MHz, DMSO-c / 6) 5 8.51 (d, J = 1.8 Hz, 1H), 8.06 (d, J = 1.8 Hz, 1H), 4.22 (s, 2H), 3.19 (q, J = 7.3 Hz, 2H), 1.31 (t, J= 7.3 Hz, 3H).

[0465] LC / MS: Rt = 1.87; m / z = 204 (M+1)

[0466] Example 12

[0467] Mel, Cs2CO3

[0468] Step-3a

[0469]

[0470] Step-3a: Synthesis of 5-( 1-cyano-1-methyl-ethyl)-3-ethylsulfanyl-pyridine-2-carbonitrile

[0471] To a solution of 5-(cyanomethyl)-3-ethylsulfanyl-pyridine-2-carbonitrile (0.7 g, 3.43 mmol) in acetonitrile (15 mL) was added CS2CO3 (2.7 g., 8.57 mmol) followed by iodomethane (0.6 mL, 7.54 mmol) and the reaction mixture was stirred at 80 °C for 1 hr. After full consumption of starting material, the reaction mixture was cooled to rt and quenched by addition of water. The resulting mixture was extracted with EtOAc, and the combined organic layers washed with brine, dried over sodium sulfate and concentrated under reduced pressure. The crude residue was purified by flash chromatography using (45 % ethyl acetate and n-heptane) as an eluent to afford the yellow solid compound (0.545 g, 68% yield).

[0472] 1H NMR (300 MHz, DMSO-cfc) 68.70 (d, J = 2.1 Hz, 1H), 8.04 (d, J = 2.1 Hz, 1H), 3.26 (q, J = 7.3 Hz, 2H), 1.78 (s, 6H), 1.30 (t, J= 7.3 Hz, 3H).

[0473] LC / MS: Rt = 2.02; m / z = 232 (M+1)

[0474] Lewis acid

[0475] Solvent

[0476] Step-4a

[0477]

[0478] Synthesis of 2-[5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]- 2-methyl-propanenitrile

[0479] In a 10 ml Microwave vial dissolved 5-(1-cyano-1-methyl-ethyl)-3-ethylsulfanyl-pyridine-2- carbonitrile (0.2 g, 0.86 mmol, 1 eq) & N2-methyl-5-(trifluoromethyl) pyridine-2,3-diamine (0.166 g, 0.86 mmol) in chlorobenzene (4.0 mL), then added TMSOTf (0.588 ml, 3.44 mmol, 4.0 eq). The reaction mixture was heated to 140 °C for 2.5 h. Having monitored the reaction mixture by TLC and LCMS, it was quenched with water (20 mL) and with solid sodium bicarbonate, it was then extractedwith ethyl acetate (2 x 20 mL), then organic layers dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The crude was purified through a flash chromatography over silica gel (55% EtOAc I n-heptane as an eluent) to get 2-[5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl) imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]-2-methyl-propanenitrile (0.114 g, 32% yield).

[0480] 1H N MR (500 MHz, DMSO-cfc) 68.89 - 8.85 (m, 1H), 8.74 (d, J = 2.1 Hz, 1H), 8.69 (dd, J = 10.2, 2.1 Hz, 1H), 8.04 (d, J= 2.1 Hz, 1H), 3.95 (s, 3H), 3.11 (q, J = 7.3 Hz, 2H), 1.85 (s, 6H), 1.23 (t, J = 7.3 Hz, 3H).

[0481] LC / MS: Rt = 2.23; m / z = 406 (M+1)

[0482] Example 14

[0483]

[0484] Step-5a: Synthesis of 2-[5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4, 5-b]pyridin-2-yl]-3-pyridyl]-2-methyl-propanenitrile

[0485] 2-[5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]-2-methyl-propanenitrile (0.1 g, 0.246 mmol) was dissolved in dichloromethane (5.0 mL), and the solution was cooled to 0 °C. and stirred for 5 min, 77% m-chloroperbenzoic acid (0.094 g, 0.541 mmol, 5 eq) was added in to the reaction mixture. It was then stirred overnight at 0 °C to room temperature. Having monitored the reaction mixture by TLC and LCMS, the reaction mixture was poured to a mixed solution (20 mL) of a saturated aqueous solution of sodium bicarbonate and a saturated aqueous solution of sodium thiosulfate (1:1), followed by extraction with dichloromethane (2 x 15 mL). The obtained organic layer was washed with brine solution (20 mL), dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The crude was purified through a flash chromatography over silica gel (60% EtOAc / n-heptane as an eluent) to afford title compound (0.07 g, 65 % yield).

[0486] 1H NMR (300 MHz, DMSO-d6) 69.33 (d, J = 2.3 Hz, 1 H), 8.92 (dd, J = 2.1 , 0.8 Hz, 1 H), 8.74 - 8.67 (m, 1 H), 8.57 (d, J = 2.3 Hz, 1 H), 3.86 (q, J = 7.4 Hz, 2H), 3.79 (s, 3H), 1.90 (s, 7H), 1.25 (q, J = 7.4 Hz, 3H).

[0487] LC / MS: Rt = 2.09; m / z = 438 (M+1)

[0488] Example 15

[0489]

[0490] Step-1: Synthesis of 5-( 1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carbonitrile

[0491] To a solution of 5-(cyanomethyl)-3-ethylsulfanyl-pyridine-2-carbonitrile (0.5 g, 2.45 mmol) in acetonitrile (10 mL) was added CS2CO3 (1.99 g., 6.127 mmol) followed by dibromoethane (1.03 g, 5.39 mmol) and the reaction mixture was stirred at 80 °C for 1 hr. After full consumption of starting material, the reaction mixture was cooled to rt and quenched by addition of water. The resulting mixture was extracted with EtOAc, and the combined organic layers washed with brine, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The crude residue was purified using silica gel chromatography using (40 % ethyl acetate and n-heptane) as an eluent to afford the yellow solid compound (0.250 g, 44% yield).

[0492] 1H NMR (300 MHz, DMSO-cfc) 68.51 (d, = 2.1 Hz, 1H), 7.78 (d, = 2.1 Hz, 1H), 3.24 (q, = 7.3 Hz, 2H), 1.97 - 1.87 (m, 2H), 1.85 - 1.75 (m, 2H), 1.28 (t, J = 7.3 Hz, 3H).

[0493] LC / MS: Rt= 1.98; m / z = 230 (M+1)

[0494] Example 16

[0495] Lewis acid Solvent

[0496] Step-2

[0497]

[0498] Step-2: Synthesis of 1-[5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4, 5-b]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile

[0499] In a 10 mL Microwave vial dissolved 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carbonitrile (0.2 g, 0.869 mmol, 1 eq) and N2-methyl-5-(trifluoromethyl) pyridine-2,3-diamine (0.166 g, 0.869 mmol, 1 eq) in chlorobenzene (4 mL), then added TMSOTf (0.588 mL, 3.44 mmol, 4 eq) in to the reaction mixture, heat the reaction mixture to 140 °C for 2.5 h. After Monitor the reaction mixture by TLC and LCMS, it was quenched with water (20 mL) and solid NaHCOa extracted it with ethyl acetate (40 mL), then organic layers dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The crude was purified through a flash chromatography over silica gel (55% EtOAc / n-heptane as an eluent) to get 1-[5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl) imidazo [4,5-b] pyridin-2-yl]-3-pyridyl] cyclopropane carbonitrile (0.16 g, 45 % yield).1H NMR (300 MHz, DMSO-cfc) 68.90 - 8.83 (m, 1 H), 8.68 (d, J = 2.0 Hz, 1 H), 8.58 (d, J = 2.1 Hz, 1H), 7.80 (d, J = 2.1 Hz, 1H), 3.93 (s, 3H), 3.08 (q, J = 7.4 Hz, 2H), 1.97 - 1.88 (m, 2H), 1.88 -1.76 (m, 2H), 1.22 (t, J = 7.3 Hz, 4H).

[0500] LC / MS: Rt = 2.19; m / z = 404 (M+1)

[0501] Example 17

[0502]

[0503] Step-3: Synthesis of 1-[5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4, 5-blpyridin-2-yll-3-pyridyllcyclopropanecarbonitrile

[0504] The starting material, 1-[5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl) imidazo[4,5-b]pyridin-2-yl]-3-pyridyl] cyclopropane carbonitrile (0.14 g, 0.346 mmol, 1.0 eq) was dissolved in dichloromethane (5 mL), and the solution was cooled to 0 °C. and stirred for 5 min, 77% m-chloroperbenzoic acid (0.238 g, 1.38 mmol, 4.0 eq) was added in to the reaction mixture. The reaction mixture was stirred overnight at 0 °C at room temperature. Having monitored the reaction mixture by TLC and LCMS, the reaction mixture was poured to a mixed solution (20 mL) of a saturated aqueous solution of sodium bicarbonate and a saturated aqueous solution of sodium thiosulfate (1:1), followed by extraction with dichloromethane (40 mL). The obtained organic layer was washed with brine solution (20 mL), dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The crude was purified through a flash chromatography over silica gel (70% EtOAc / n-heptane as an eluent) to afford 1-[5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl) imidazo [4,5-b] pyridin-2-yl]-3-pyridyl] cyclopropane carbonitrile (0.11 g, 73.3 % yield).

[0505] 1H NMR (500 MHz, DMSO-cfc) 69.04 (d, J = 2.3 Hz, 1 H), 8.93 - 8.89 (m, 1 H), 8.70 (d, J = 2.1 Hz, 1H), 8.41 (d, J = 2.3 Hz, 1H), 3.85 (q, J = 7.4 Hz, 2H), 3.77 (s, 3H), 2.07 - 2.01 (m, 2H), 1.98 -1.90 (m, 2H), 1.23 (t, J = 7.4 Hz, 3H).

[0506] LC / MS: Rt = 2.06; m / z = 436 (M+1)

[0507] Example 18

[0508]

[0509] Step-1: Synthesis of 1-[6-(2,2-difluoro-7-methyl-[1,3]dioxolo[4,5-f]benzimidazol-6-yl)-5-ethylsulfanyl-3-pyridyl]cyclopropanecarbonitrileIn a 10 mL Microwave vial dissolved 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carbonitrile (0.129 g, 0.594 mmol, 1.0 eq) and 2,2-difluoro-N5-methyl-1 ,3-benzodioxole-5,6-diamine (0.136 g, 0.594 mmol, 1.0 eq) in chlorobenzene (4.0 mL), then added TMSOTf (0.248 mL, 2.37 mmol, 4 eq) in to the reaction mixture, heat the reaction mixture to 140 °C for 1 h. Having monitored the reaction mixture by TLC and LCMS, it was quenched with water (20 mL) and solid NaHCOa. The mixture was then extracted with ethyl acetate (20 mL x 2), then organic layers dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The crude was purified through a flash chromatography over silica gel (40% EtOAc / n-heptane as an eluent) to get 1-[6-(2,2-difluoro-7-methyl-[1 ,3] dioxolo[4,5-f]benzimidazol-6-yl)-5-ethylsulfanyl-3-pyridyl] cyclopropane carbonitrile (0.11 g, 44.27 % yield).

[0510] 1H NMR (300 MHz, DMSO-d6) 68.52 (d, = 2.1 Hz, 1H), 7.83 (s, 1H), 7.78 (s, 1H), 7.74 (d, = 2.1 Hz, 1 H), 3.83 (s, 3H), 3.05 (q, J = 7.3 Hz, 2H), 1.93 - 1.84 (m, 2H), 1.84 - 1.74 (m, 2H), 1.21 (t, J = 7.4 Hz, 3H).

[0511] LC / MS: Rt = 2.17; m / z = 415 (M+1)

[0512] mCPBA,

[0513] DCM

[0514] Step-2

[0515]

[0516] Step-2: Synthesis of 1-[6-(2, 2-difluoro-7-methyl-[ 1, 3]dioxolo[4, 5-f]benzimidazol-6-yl)-5-ethylsulfonyl-3-pyridyl]cyclopropanecarbonitrile

[0517] 1-[6-(2,2-difluoro-7-methyl-[1 ,3] dioxolo[4,5-f] benzimidazol-6-yl)-5-ethylsulfanyl-3-pyridyl] cyclopropane carbonitrile (0.11 g, 0.265 mmol, 1.0 eq) was dissolved in dichloromethane (5.0 mL), and the solution was cooled to 0° C. and stirred for 5 min, 75-77% m-chloroperbenzoic acid (0.244 g, 1.062 mmol, 4.0 eq) was added in to the, a reaction mixture. The reaction mixture was stirred overnight at 0 °C to room temperature. Having monitored the reaction mixture by TLC and LCMS, the reaction mixture was poured to a mixed solution (20 mL) of a saturated aqueous solution of sodium bicarbonate and a saturated aqueous solution of sodium thiosulfate (1:1), followed by extraction with dichloromethane (20 mL x 2). The obtained organic layer was washed with brine solution (20 mL), dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The crude was purified through a flash chromatography over silica gel (70% EtOAc / n-heptane as an eluent) to afford 1-[6-(2,2-difluoro-7-methyl-[1,3] dioxolo[4,5-f]benzimidazol-6-yl)-5-ethylsulfonyl-3-pyridyl] cyclopropane carbonitrile (0.08 g, 64.14 % yield).1H NMR (500 MHz, DMSO-cfc) 68.98 (d, J = 2.3 Hz, 1 H), 8.44 - 8.33 (m, 1 H), 7.88 (s, 1 H), 7.79 (s, 1 H), 3.89 (q, J = 7.4 Hz, 2H), 3.70 (s, 3H), 2.05 - 1.96 (m, 2H), 1.93 - 1.85 (m, 2H), 1.21 (t, J = 7.4 Hz, 3H).

[0518] LC / MS: Rt = 2.08; m / z = 447 (M+1)

[0519] Example 20

[0520] (COCI)2, aq NH3

[0521] DMF. DCM Dioxane

[0522] Step- 1 Step-2

[0523]

[0524] Step-1: Synthesis of 2-bromo-5-ethylsulfanyl-1 -methyl-imidazole-4-carbonyl chloride

[0525] To the solution of 2-bromo-5-ethylsulfanyl-1-methyl-imidazole-4-carboxylic acid (CAS: 2234901-67-6, 200 mg, 0.754 mmol) in DCM (4.0 mL) was added N,N-Dimethylformamide (0.006 mL, 0.075 mmol) and reaction mixture was cooled to 0 °C followed by dropwise addition of oxalyl chloride (0.246 mL, 3.018 mmol). The reaction mixture was allowed to stir at RT for 2 h. Reaction was monitored by TLC. After the reaction was completed reaction mixture was concentrated under reduced pressure and crude product was used as such for next step without characterization.

[0526] Step-2: Synthesis of 2-bromo-5-ethylsulfanyl-1-methyl-imidazole-4-carboxamide

[0527] To the solution of aqueous NH3 (5.0 mL) in 1 ,4-Dixoane (5mL) at 0 °C was added a solution of 2-bromo-5-ethylsulfanyl-1-methyl-imidazole-4-carbonyl chloride (0.21 g, 0.741 mmol) in 2.0 mL of 1 ,4-dioxane dropwise. After the addition was completed reaction mixture was allowed to stir at RT for 1 h. Reaction was monitored by TLC. After the reaction was completed 20 mL of water was added in the reaction mixture and was basified with sat. NaHCOa solution, compound was extracted with EtOAc (20 mL x 2). Organic layer was dried over Na2SO4 and concentrated under reduced pressure to get the crude product was purified by flash chromatography using 60% EtOAc and n-heptane as an eluent to afford (0.11 g, 56% yield) of desired product as white solid.

[0528] 1H NMR (500 MHz, DMSO-cfc) 67.48 (s, 1 H), 7.26 (s, 1 H), 3.67 (s, 3H), 2.96 (q, J = 7.3 Hz, 2H), 1.14 (t, J= 7.4 Hz, 3H).

[0529] LC / MS: Rt = 1.46; m / z = 266.0 (M+2).

[0530] Example 21

[0531] (CF3CO)2O,

[0532] Et3N, THF

[0533] - *-

[0534]

[0535] Step-3

[0536] Step-3: Synthesis of 2-bromo-5-ethylsulfanyl-1-methyl-imidazole-4-carbonitrileTo the solution of 2-bromo-5-ethylsulfanyl-1-methyl-imidazole-4-carboxamide (0.55g, 2.083 mmol) in THF (10 mL) at 0 °C was added triethylamine (0.87 mL, 6.25 mmol) and reaction mixture was cooled to 0 °C followed by addition of trifluoroacetic anhydride (0.57 mL, 4.166 mmol) dropwise. After the addition was completed reaction mixture was allowed to stir at 0 °C for 2 h. Reaction was monitored by TLC. After the reaction was completed 50 mL of water was added in the reaction mixture and it was basified with sat. NaHCOa solution, compound was extracted with EtOAc (30 mL x 2). Organic layer was dried over Na2SO4 and concentrated under reduced pressure to get the crude product was purified by flash chromatography using 60% EtOAc and n-heptane as an eluent to afford (0.4g, 78% yield) of desired product as white solid.

[0537] 1H NMR (500 MHz, DMSO-cfc) 63.65 (s, 3H), 2.90 - 2.83 (m, 2H), 1.18 (td, J= 7.3, 3.7 Hz, 3H). LC / MS: Rt = 1.90; m / z = 248.1 (M+2).

[0538] Example 22

[0539] TMSOTf, Chlorobenzene

[0540] Step-4

[0541]

[0542] Step-4: 2-(2-bromo-5-ethylsulfanyl-1-methyl-imidazol-4-yl)-3-methyl-6- (trifluoromethyl)imidazo[4,5-b]pyridine

[0543] To the solution of 2-bromo-5-ethylsulfanyl-1-methyl-imidazole-4-carbonitrile (0.50 g, 0.203 mmol) in chlorobenzene (0.1 mL) was added N2-methyl-5-(trifluoromethyl)pyridine-2,3-diamine (0.057 g, 0.305 mmol) and trimethylsilyl trifluoromethanesulfonate (0.15 mL, 0.813 mmol), reaction mixture was then irradiated in microwave at 140 °C for 4 h. The reaction was monitored by TLC. After the reaction was completed 20 mL of water was added in the reaction mixture and it was basified with sat. NaHCOa solution, compound was extracted with EtOAc (20 mL x 2). Organic layer was dried over Na2SO4 and concentrated under reduced pressure to get the crude product purified by flash chromatography using 40% EtOAc and n-heptane as an eluent to afford (0.05 g, 58.8% yield) as white solid.

[0544] 1H NMR (500 MHz, DMSO-d6) 68.79 - 8.76 (m, 1 H), 8.55 (m, 1 H), 4.06 (s, 3H), 3.76 (s, 3H), 3.03 (m, 2H), 1.12 (m, 3H).

[0545] LC / MS: Rt = 2.25; m / z = 422.1 (M+2).

[0546] Example 23

[0547] HCO2H,

[0548] H2O2, DCM

[0549] Step-5

[0550]

[0551] Step-5: 2-(2-bromo-5-ethylsulfonyl-1-methyl-imidazol-4-yl)-3-methyl-6- (trifluoromethyl)imidazo[4,5-b]pyridine

[0552] To the solution of 2-(2-bromo-5-ethylsulfanyl-1-methyl-imidazol-4-yl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine (0.50 g, 1.190 mmol) in dichloromethane (5.0 mL) at 0 °C was added formic acid (0.22 mL, 5.952 mmol) followed by dropwise addition of H2O2 (30% in H2O, 0.944 mL, 8.33 mmol). After the addition was completed reaction mixture was allowed to stir at RT for 12 h. The reaction was monitored by TLC. After the reaction was completed 20 mL of waterwas added in the reaction mixture and it was then basified with sat. NaHCOa solution, compound was extracted with EtOAc (20 mL x 2). Organic layer was dried over Na2SO4 and concentrated under reduced pressure to get the crude product was purified by FCC using 60% EtOAc and n-heptane as an eluent to afford (0.53 g, quantitative yield) as white solid.

[0553] 1H NMR (300 MHz, DMSO-d6) 6 8.86 (d, J = 1.3 Hz, 1H), 8.63 (d, J = 1.6 Hz, 1H), 3.93 (s, 3H), 3.86 (s, 3H), 3.77 (q, J = 7.4 Hz, 2H), 1.28 (t, J = 7.4 Hz, 3H).

[0554] LC / MS: Rt = 2.03; m / z = 454.1 (M+2).

[0555] Example 24

[0556] TMSOTf,

[0557] Chlorobenzene

[0558]

[0559] Step-1

[0560] Step-1: 6-(2-bromo-5-ethylsulfanyl-1-methyl-imidazol-4-yl)-2,2-difluoro-7-methyl-[1,3]dioxolo[4,5-f]benzimidazole

[0561] To the solution of 2-bromo-5-ethylsulfanyl-1-methyl-imidazole-4-carbonitrile (0.1 g, 0.406 mmol) in chlorobenzene (0.2 mL) was added 2,2-difluoro-N5-methyl-1 ,3-benzodioxole-5,6-diamine (0.123 g, 0.609 mmol) and trimethylsilyl trifluoromethanesulfonate (0.3 mL, 1.62 mmol), reaction mixture was heated at 130 °C for 1 h. The reaction was monitored by TLC. After the reaction was completed 20 mL of water was added in the reaction mixture and was basified with sat. NaHCOa solution, compound was extracted with EtOAc (20 mL x 2). Organic layer was dried over Na2SO4 and concentrated under reduced pressure to get the crude product purified by flash chromatography using 40% EtOAc and n-heptane as an eluent to afford (0.170 g, 97% yield) as white solid.

[0562] 1H NMR (500 MHz, DMSO-cfc) 67.78 (s, 1 H), 7.71 (s, 1 H), 3.94 (s, 3H), 3.73 (s, 3H), 3.02 - 2.93 (m, 2H), 1.10 (m, 3H).

[0563] LC / MS: Rt = 2.16; m / z = 433.1 (M+2).

[0564] Example 25HCO2H,

[0565] H2O2, DCM

[0566] Step-2

[0567]

[0568] To the solution of 6-(2-bromo-5-ethylsulfanyl-1-methyl-imidazol-4-yl)-2,2-difluoro-7-methyl- [1,3]dioxolo[4,5-f]benzimidazole (0.17 g, 0.394 mmol) in dichloromethane (10 mL) at 0 °C was added formic acid (0.1 mL, 2.76 mmol) followed by dropwise addition of H2O2 (30% in H2O, 0.223 mL, 1.97 mmol). After the addition was completed reaction mixture was allowed to stir at RT for 12 h. Reaction was monitored by TLC. After the reaction was completed 20 mL of water was added in the reaction mixture and was basified with sat. NaHCOa solution. The reaction mixture was then extracted with EtOAc (20 mL x 2). Organic layer was dried over Na2SO4 and concentrated under reduced pressure to get the crude product purified by flash chromatography using 60% EtOAc and n-heptane as an eluent to afford ( 0.17 g, 96% yield) of as white solid.

[0569] 1H NMR (500 MHz, DMSO-cfc) 67.87 (s, 1 H), 7.79 (s, 1 H), 3.95 (s, 3H), 3.85 (s, 3H), 3.84 - 3.80 (m, 2H), 1.33 (t, = 7.4 Hz, 3H).

[0570] LC / MS: Rt = 2.02; m / z = 465.1 (M+2).

Claims

Claims1. A process for preparing a compound of formula (I)RN(I)whereinA is a 5- to 12-membered partially or fully unsaturated mono-, bi- or tricyclic carbo- or heterocyclic ring, comprising up to 4 heteroatoms selected from N, O and S, wherein said N may be unsubstituted or substituted with RN, and said ring being unsubstituted or substituted with one or more substituents R1;B is a 5- to 12-membered saturated, partially unsaturated, or fully unsaturated mono-, bi- or tricyclic carbo- or heterocyclic ring comprising up to 4 heteroatoms selected from N, O and S, wherein said N may be unsubstituted or substituted with RN, and said ring being unsubstituted or substituted with one or more substituents R2;each R1independently is S(O)m-Ci-C4-alkyl, S(0)m-C3-C6-cycloalkyl, S(0)m-C3-C6-cycloalkyl-Ci- C4-alkyl, S(O)(=NH)RM, S(O)(=NRM)RM, halogen, cyano, NH2, NHRM, N(RM)2, NH-C(O)-RM, C(O)RM, C(O)ORM, ORM, Ci-C6-alkyl, C3-C6-cycloalk(en)yl, C2-C6-alkenyl, C2-C6-alkynyl, C6- Cw-aryl, a 5- to 12-membered saturated, partially unsaturated, or fully unsaturated mono-, bi- or tricyclic heterocyclic ring comprising up to 4 heteroatoms selected from N, O and S, wherein N is unsubstituted or substituted with RN,wherein the alkyl, cycloalkyl, alkenyl, alkynyl groups are unsubstituted or substituted with one or more R11,wherein the aryl and heterocyclic rings are unsubstituted or substituted with one or more R12; or two R1combine to form together with the atoms to which they are attached a 5- to 10- membered saturated, partially unsaturated, or fully unsaturated carbocyclic or heterocyclic ring comprising up to 4 heteroatoms selected from N, O and S, wherein N is unsubstituted or substituted with RN, wherein said ring is unsubstituted or substituted with one or more R12; each R2independently is S(O)P-RW, halogen, cyano, NH2, NHRM, N(RM)2, NH-C(O)-RM, Si(Rs)3, wherein Rsis Ci-C4-alkyl, C(O)RM, C(O)ORM, COOH, ORM, Ci-C6-alkyl, C3-C6- cycloalk(en)yl, C2-Ce-alkenyl, C2-Ce-alkynyl, Ce-C -aryl, a 5- to 12-membered saturated, partially unsaturated, or fully unsaturated mono-, bi- or tricyclic heterocyclic ring comprising up to 4 heteroatoms selected from N, O and S, wherein N is unsubstituted or substituted with RN, or Si(Rs)3, wherein Rsis Ci-C4-alkyl,wherein the alkyl, cycloalk(en)yl, alkenyl, alkynyl groups are unsubstituted or substituted with one or more R21,wherein the aryl and heterocyclic rings are unsubstituted or substituted with one or more R22; or two R2combine to form together with the atoms to which they are attached a 5- to 10- membered saturated, partially unsaturated, or fully unsaturated carbocyclic or heterocyclic ring comprising up to 4 heteroatoms selected from N, O and S, wherein N is unsubstituted or substituted with RN, and wherein said ring is unsubstituted or substituted with one or more R22;each R11independently is halogen or cyano;each R12independently is C-i-Ce-alkyl, C2-Ce-alkenyl, C2-Ce-alkynyl, Ci-Ce-alkoxy-Ci-C4-alkyl, C3- Ce-cycloalkyl, C3-C6-cycloalkyl-Ci-C4-alkyl, C3-C6-cycloalkoxy-Ci-C4-alkyl, wherein the alkyl, alkoxy, cycloalkyl groups are unsubstituted or substituted with halogen or CN;each R21independently is halogen or cyano or two R21combine to form a ring by a C2-Ce-alkyl bridge, which is unsubstituted or partly or fully halogenated and in which one or more carbon atoms may be replaced by O or N, wherein N is unsubstituted or substituted with RN; each R22independently is halogen, cyano, C-i-Ce-alkyl, C2-Ce-alkenyl, C2-Ce-alkynyl, C-i-Ce-alkoxy, Ci-Ce-alkoxy-Ci-C4-alkyl, Ci-C6-alkoxy-Ci-Ce-alkoxy-Ci-C4-alkyl Cs-Ce-cycloalkyl, C3-C6- cycloalkyl-Ci-C4-alkyl, C3-C6-cycloalkyl-Ci-C4-alkoxy, C3-C6-cycloalkoxy-Ci-C4-alkyl, NH- CO-RM, C(RM)2-CN, CHRM-CN, C(RM)2-(CONH2), CHRM-(CONH2), C(RM)2-(CSNH2), CHRM- (CSNH2), O-CH2-CN, O-CHRM-CN, O-C(RM)2-CN, O-C(RM)2-(CONH2), O-C(RM)2-(CSNH2), 0-C(CONH2)-C3-C6-cycloalkyl, 0-C(CSNH2)-C3-C6-cycloalkyl, O-S(O)2-RM, S(O)m-RM, S(O)(=NRM)RM, S(O)(=NH)RM, N=S(O)(RM)2, CO-N=SO(RM)2, SF5, or wherein two R22combine to form=0 (carbonyl) or=CF2 (difluoromethylen); wherein the alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, and cycloalkoxy groups are unsubstituted or substituted with halogen or CN, or wherein at least one C is replaced by a heteroatom; or in case of two adjacent substituents R22, the substituents may combine to form a C2-Ce-alkylene group, which is unsubstituted or substituted with halogen and in which one or more carbon atoms may be replaced by O or N, wherein N is unsubstituted or substituted with RN;each RMindependently is C-i-Ce-alkyl, C2-Ce-alkenyl, C2-Ce-alkynyl, Ci-Ce-alkoxy-Ci-C4-alkyl, C3- Ce-cycloalkyl, C3-C6-cycloalkyl-Ci-C4-alkyl, C3-C6-cycloalkoxy-Ci-C4-alkyl, wherein the alkyl, alkoxy, cycloalkyl groups are unsubstituted or substituted with halogen or CN or wherein at least one C is replaced by a heteroatom; or in case of two adjacent substituents RM, the substituents may combine to form a C2-Ce-alkylene group, which is unsubstituted or substituted with halogen and in which one or more carbon atoms may be replaced by O or N, wherein N is unsubstituted or substituted with RN;RNis H, Ci-C4-alkyl, Cs-Ce-cycloalkyl, or Ci-C4-alkyl-Ci-C4-alkoxy;Rwis Ci-C4-alkyl, cyclopropyl, C3-C6-cycloalkyl-Ci-C4-alkyl;m, p are independently 0, 1 , or 2;and the N-oxides, stereoisomers, tautomers and agriculturally or veterinarily acceptable salts thereof;by directly reacting, in a one-step reaction, a compound of formula (II)with a compound of formula (III)2. The process according to claim 1, wherein the compound of formula (I) is a compound of formula (la)3. The process according to claim 1 or 2, wherein the compound of formula (I) is a compound of formula (IV), (V) or (VI)(IV)R^sox>(°)P(V)whereinA1, A2, A3and A4are each independently N, CH or CR1, wherein not more than two are N, wherein preferably A1, A2and A3are CH or CR1and A4is N, CH or CR1; andB1, B2, B3and B4are each independently N, CH or CR2, wherein not more than two are N, wherein preferably B1, B2, and B3are CH orCR2and B4is N, CH orCR2.

4. The process according to claim 3, wherein(1) one of A1, A2, A3and A4is N and the others are CH or CR1, preferably(a) A1is CH and at least one of A2and A3is CR1and the other is CH or CR1and A4is N or CH; or(b)A1and A4are CR1or CH, preferably CH, and one of A2and A3is N and the other is CH orCR1; or(c) one of A1and A4is N and the other is CH or CR1, preferably CH, and A2and A3are CH orCR1;and / or(2) B1is CH and at least one of B2and B3is CR2and the other is CH or CR2and B4is N.

5. The process according to any one of claims 1 to 4, wherein the compound of formula (I) is a compound of formula (VII), (VIII), (IX), (X), (XI), (XII), (XIII), (XIV), (XV), or (XVI)(VII)RW o ^(0)p(VIII)whereineach of RA2and RA3independently is selected from H, S(O)m-Ci-C4-alkyl, S(O)m-C3-C6-cycloalkyl, S(0)m-C3-C6-cycloalkyl-Ci-C4-alkyl, S(O)(=NH)RM, S(O)(=NRM)RM, halogen, cyano, NH2, NHRM, N(RM)2, NH-C(O)-RM, C(O)RM, C(O)ORM, ORM, Ci-C6-alkyl, C3-C6-cycloalk(en)yl, C2-Ce-alkenyl, C2-Ce-alkynyl, Ce-C -aryl, a 5- to 12-membered saturated, partially unsaturated, or fully unsaturated mono-, bi- or tricyclic heterocyclic ring comprising up to 4 heteroatoms selected from N, O and S, wherein N is unsubstituted or substituted with RN,wherein the alkyl, cycloalkyl, alkenyl, alkynyl groups are unsubstituted or substituted with one or more R11,wherein the aryl and heterocyclic rings are unsubstituted or substituted with one or more R12; or RA2and RA3combine to form together with the atoms to which they are attached a 5- to 6-membered partially unsaturated or fully unsaturated heterocyclic ring comprising up to 4 heteroatoms selected from N, O and S, wherein N is unsubstituted or substituted with RN, wherein said ring is unsubstituted or substituted with halogen or C1-C4 alkyl, which can be substituted with halogen;RA4and RA5are independently H or halogen, or C1-C4 alkyl, which can be substituted with halogen;each of RB2and RB3independently is selected from H, halogen, cyano, NH2, NHRM, N(RM)2, NH-C(O)-RM, C(O)RM, C(O)ORM, COOH, Ci-C6-alkyl, ORM, Ci-C6-alkyl, C3-C6-cycloalk(en)yl, C2-Ce-alkenyl, C2-Ce-alkynyl, Ce-C -aryl, a 5- to 12-membered saturated, partially unsaturated, or fully unsaturated mono-, bi- or tricyclic heterocyclic ring comprising up to 4 heteroatoms selected from N, O and S, wherein N is unsubstituted or substituted with RN, or Si(Rs)3, wherein Rsis Ci-C4-alkyl,wherein the alkyl, cycloalk(en)yl, alkenyl, alkynyl groups are unsubstituted or substituted with one or more R21,wherein the aryl and heterocyclic rings are unsubstituted or substituted with one or more R22.

6. The process according to claim 4, wherein one of and RA3is H and the other is selected from S(O)m-Ci-C4-alkyl, S(0)m-C3-C6-cycloalkyl, S(0)m-C3-C6-cycloalkyl-Ci-C4-alkyl, S(O)(=NH)RM, S(O)(=NRM)RM, Ci-C4-alkyl, C3-C6-cycloalkyl, Ci-C4-alkoxy, and C3-C6- cycloalkoxy,wherein the alkyl, cycloalkyl, alkoxy and cycloalkoxy groups are unsubstituted, partially halogenated, or fully halogenated;wherein each RMis independently Ci-Cs-alkyl which is unsubstituted or partially or fully halogenated; or Cs-Ce-cycloalkyl, or Cs-Ce-cycloalkyl in which at least one C is replaced by a heteroatom; or in case of two adjacent substituents RM, the substituents may form a C2-C6- alkylene group, which is unsubstituted or partly or fully halogenated and in which one or more carbon atoms may be replaced by O or N, wherein N is unsubstituted or substituted with RN.

7. The process according to claim 5 or 6, wherein(1) RB3is H or Ci-C4-alkyl, Ci-C4-alkoxy, Cs-Ce-cycloalkyl, halogen, cyano, N(RM)2, NH-CO- RM; Ci-C4-alkynyl;phenyl which is unsubstituted or substituted with at least one Ci-C4-alkyl which is unsubstituted or partially or fully halogenated, Cs-Ce-cycloalkyl, halogen, O-S(O)2-RM, CN, Ci-Cs-alkoxy, which is unsubstituted or partially or fully halogenated, Cs-Ce-cycloalkoxy, N=S(O)(RM)2, ora five- or six-membered aromatic heterocycle, which is unsubstituted or substituted with at least one halogen, CN, Ci-C4-alkyl which is unsubstituted or partially or fully halogenated, Cs-Ce-cycloalkyl, C-i-Cs-alkoxy, which is unsubstituted or partially or fully halogenated; wherein each RMis independently Ci-Cs-alkyl which is unsubstituted or partially or fully halogenated; or Cs-Ce-cycloalkyl, or Cs-Ce-cycloalkyl in which at least one C is replaced by a heteroatom; or in case of two adjacent substituents RM, the substituents may form a C2-C6- alkylene group, which is unsubstituted or partly or fully halogenated and in which one or more carbon atoms may be replaced by O or N, wherein N is unsubstituted or substituted with RN, wherein said ring; and / or(5) RB2is H, halogen, or(2a) Cs-Ce-cycloalkyl, which is unsubstituted or partially or fully halogenated; or halogen; (2b) phenyl substituted with one R22, or substituted with up to 5 halogens; (2c) 1,3-benzodioxole which is unsubstituted or partly or fully halogenated; (2d) a six-membered saturated, partially unsaturated, or fully unsaturated heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one, two or three, same or different heteroatoms O or N, wherein N is unsubstituted or substituted with Ci-C4-alkyl, and said ring / ring system is unsubstituted, or substituted with one R22, or substituted with two halogens;(2e) or Ci-C4-alkynyl, which is unsubstituted or substituted with C3-C6-cycloalkyl or Si(Rs)3, wherein Rsis Ci-C4-alkyl; or(2f) a five-membered saturated, partially unsaturated, or fully unsaturated heterocyclic ring, wherein said heterocyclic ring comprises one, two or three, same or different heteroatoms selected from N, O, and S, wherein N may be unsubstituted or substituted with Ci-C4-alkyl, C3-C6-cycloalkyl, C-bound Ci-C4-alkoxy, or Ci-C4-alkyl-Ci-C4-alkoxy; wherein the five-membered ring is unsubstituted or substituted with one R22; wherein R22is halogen, cyano, Ci-C4-alkyl, which is unsubstituted or partially or fully halogenated; NH-CO-RM; C3-C6-cycloalkyl; Ci-C4-alkoxy-Ci-C4-alkyl, C3-C6-cycloalkyl-Ci- C3-alkoxy, Ci-C4-alkoxy-Ci-C4-alkoxy-Ci-C4-alkyl; C(RM)2-CN, CHRM-CN, C(RM)2-(CONH2), CHRM-(CONH2), C(RM)2-(CSNH2), CHRM-(CSNH2), 1-cyano-C3-C6-cycloalkyl, 1-C3-C6- cycloalkyl-carboxamide, 1-C3-C6-cycloalkyl-thiocarboxamide, O-CH2-CN, O-CHRM-CN, O- C(RM)2-CN, O-C(RM)2-(CONH2), O-C(RM)2-(CSNH2), 0-1-cyano-C3-C6-cycloalkyl, O- C(CONH2)-C3-C6-cycloalkyl, 0-C(CSNH2)-C3-C6-cycloalkyl; O-S(O)2-RM; Ci-C3-alkoxy, which is unsubstituted or partially or fully halogenated; C3-C6-cycloalkyl-Ci-C3-alkoxy which is unsubstituted or partially or fully halogenated, C3-C6-cycloalkoxy, which is unsubstituted or partially or fully halogenated; S-RM, SO-RM; SO2-RM;S(O)(=NRM)RM, S(O)(=NH)RM, N=S(O)(RM)2, CO-N=SO(RM)2, SFS, or two R22combine to form carbonyl ordifluoromethylen; wherein each RMis independently Ci-C3-alkyl which is unsubstituted or partially or fully halogenated; or C3-C6-cycloalkyl, or C3-C6-cycloalkyl in which at least one C is replaced by a heteroatom; or in case of two adjacent substituents RM, the substituents may form a C2-Ce- alkylene group, which is unsubstituted or partly or fully halogenated and in which one or more carbon atoms may be replaced by O or N, wherein N is unsubstituted or substituted with RN.

8. The process of any one of claims 5 to 7, wherein(1) RB3is H and RB2is a five-membered saturated, partially unsaturated, or fully unsaturated heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one, two or three, same or different heteroatoms selected from N, O, and S, wherein N may be unsubstituted or substituted with Ci-C4-alkyl; C3-C6-cycloalkyl, C-bound Ci-C4-alkoxy, C1-C4- alkyl-Ci-C4-alkoxy;wherein the five-membered ring is unsubstituted or substituted with one R22, or in which the ring contains a group -C(RM)2- or the atom via which RB2is attached to the remainder of the molecule, has a further substituent RM;wherein each R22is independently halogen, cyano, Ci-C4-alkyl, which is unsubstituted or partially or fully halogenated; C3-C6-cycloalkyl, orC3-C6-cycloalkyl, in which one C is replaced by an O, NRM, S, SO, or SO2; Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkoxy-Ci-C4-alkoxy-Ci-C4- alkyl, C3-C6-cycloalkyl-Ci-C3-alkoxy, C(RM)2-(CN), CHRM-CN, C(RM)2-(CONH2), CHRM-(CONH2), C(RM)2-(CSNH2), CHRM-(CSNH2), 1-cyano-C3-C6-cycloalkyl, 1-C3-C6-cycloalkyl-carboxamide, 1-C3-C6-cycloalkyl-thiocarboxamide, O-CH2-CN, O-CHRM-CN, O-C(CN)(RM)2, O-C(CONH2)(RM)2, O-C(CSNH2)(RM)2, 0-1-cyano-C3-C6-cycloalkyl, O- C(CONH2)- C3-C6-cycloalkyl, O- C(CSNH2)- C3-C6-cycloalkyl, O-S(O)2-RM, SO2-RM, Ci-C3-alkoxy which is unsubstituted or partially or fully halogenated, C3-C6-cycloalkyl-Ci-C3-alkoxy which is unsubstituted or partially or fully halogenated, C3-Ce-cycloalkoxy which is unsubstituted or partially or fully halogenated, S(O)(=NRM)RM, S(O)(=NH)RM, N=S(O)(RM)2, CO-N=SO(RM)2, or two R22combine to form carbonyl or difluoromethylen, andwherein each RMis independently Ci-C3-alkyl which is unsubstituted or partially or fully halogenated, or C3-C6-cycloalkyl, or C3-C6-cycloalkyl in which at least one C is replaced by a heteroatom, or in case of two adjacent substituents RM, the substituents may form a C2-Ce-alkylene group, which is unsubstituted or partly or fully halogenated and in which one or more carbon atoms may be replaced by O or N, wherein N is unsubstituted or substituted with RN; or(2) RB3is H and RB2is(2a) phenyl substituted with (1) one R22, or (2) substituted with one R22and one halogen, or (3) substituted with up to 5 halogens; or(2b) a six-membered saturated, partially unsaturated, or fully unsaturated heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one, two or three, same or different heteroatoms O or N, wherein N is unsubstituted or substituted with Ci-C4-alkyl, and said ring / ring system is substituted with one R22, or substituted with two halogens; or a 1,3-benzodioxole which is unsubstituted or halogenated; or Ci-C4-alkynyl, which is unsubstituted or substituted with Si(Rs)3; wherein Rsis Ci-C4-alkyl;wherein each R22is independently C(RM)2-(CN), CHRM-CN, C(RM)2-(CONH2), CHRM-(CONH2), C(RM)2-(CSNH2), CHRM-(CSNH2), 1-cyano-C3-C6-cycloalkyl, 1-C3-C6-cycloalkyl-carboxamide, 1-C3-C6-cycloalkyl-thiocarboxamide, O-CH2-CN, O-CHRM-CN, O-C(CN)(RM)2, O-C(CONH2)(RM)2, O-C(CSNH2)(RM)2, 0-1-cyano-C3-C6-cycloalkyl, O- C(CONH2)- C3-C6-cycloalkyl, O- C(CSNH2)- C3-C6-cycloalkyl, O-S(O)2-RM, Ci-C3-alkoxy which is unsubstituted or partially or fully halogenated, C3-C6-cycloalkyl-Ci-C3-alkoxy which is unsubstituted or partially or fully halogenated, C3-Ce-cycloalkoxy which is unsubstituted or partially or fully halogenated, S(O)(=NRM)RM, S(O)(=NH)RM, N=S(O)(RM)2, CO-N=SO(RM)2, halogen, cyano, or two R22combine to form carbonyl or difluoromethylen; andwherein each RMis independently Ci-C3-alkyl which is unsubstituted or partially or fully halogenated, or C3-C6-cycloalkyl, or C3-C6-cycloalkyl in which at least one C is replaced by a heteroatom, or in case of two adjacent substituents RM, the substituents may form a C2-Ce-alkylene group,which is unsubstituted or partly or fully halogenated and in which one or more carbon atoms may be replaced by O or N, wherein N is unsubstituted or substituted with RN; or(6) RB2and RB3are H; or(7) RB2is Ci-Ce-alkyl or Cs-Ce-cycloalkyl, wherein the alkyl and cycloalkyl groups are unsubstituted or substituted with cyano, and RB3is H.

9. The process according to any one of claims 1 to 8, wherein p is 1 or 2, preferably 2.

10. The process according to any one of claims 1 to 9, wherein Rwis Ci-C4-alkyl, preferably an ethyl group.11 . The process according to any of claims 1 to 10, wherein the compound of formula (I) is one of the following compounds:

12. The process according to any one of claims 1 to 11 , wherein the reaction is carried out in the absence of a Lewis acid.

13. The process according to any one of claims 1 to 11 , wherein the reaction is carried out in the presence of a Lewis acid and the Lewis acid is optionally selected from the group consisting of Cu(OTf)2, PdCI2, ZnCI2, NiCI2, MnCI2, CaCI2, CrCI2, FeCI2, FeCI3, CoCI2, CdCI2, PtCI2,CuCh, CuCI, SnCh, Ti(0iPr)4, Zn(0Tf)2, Fe(0Tf)2 (CHs^SiOTf, (CHs^SiCI, and combinations thereof.

14. The process of any one of claims 1 to 13, wherein the process is carried out in the presence of a suitable solvent.

15. The process of any one of claims 1 to 14, wherein the process is carried out at elevated temperature, preferably at a temperature in the range of 100 to 160 °C, wherein heating is optionally by microwave, and / or for 1 to 24 h.

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