WO2023275705A1 - A process for the preparation of pyrazolopyridine-diamides of formula (i) and intermediates thereof - Google Patents

Abstract

The present invention provides a process for the preparation of bicyclic anthranilic diamides of formula (I) or of salts thereof, wherein, R¹, R², R^a, R^b and R³ are as described in the description. More particularly, the present invention relates to a process for preparing bicyclic anthranilic diamides of formula (I), comprising the step of preparing a substituted 2-(5-(2-cyanoprop-1-en-1-yl)-1H-pyrazol-1-yl)acetate of formula (VII) or of salts thereof by reacting a substituted 2-(5-formyl-1H-pyrazol-1-yl)acetate of formula (VIII) or of salts thereof with a substituted (1-cyanoethyl)phosphonate of formula (IX) or of salts thereof. The invention further relates to a process for preparing intermediate compounds of formula (Z) or of salts thereof, which are useful in the preparation of compound of formula (I) or of salts thereof.

Description

A PROCESS FOR THE PREPARATION OF PYRAZOLOPYRIDINE-DIAMIDES OF FORMULA (I) AND INTERMEDIATES THEREOF

FIELD OF THE INVENTION

The present invention relates to a process for the preparation of bicyclic anthranilic diamides of formula (I) and salts thereof. More particularly, the present invention relates to a process for preparing bicyclic anthranilic diamides of formula (I), comprising the step of preparing a substituted 2-(5-(2-cyanoprop- l-en-l-yl)-lH-pyrazol-l-yl)acetate of formula (VII) or salts thereof by reacting a substituted 2-(5- formyl-lH-pyrazol-l-yl)acetate of formula (VIII) or salts thereof with a substituted (1- cyanoethyl)phosphonate of formula (IX) or salts thereof. The invention further relates to a process for preparing intermediates of formula (Z) or salts thereof, which are useful in the preparation of compound of formula (I) or salts thereof.

BACKGROUND OF THE INVENTION

Fused bicyclic anthranilic diamides are reported in the article titled “Bicyclic heterocyclic anthranilic diamides as ryanodine receptor modulators with insecticidal activity” published in Bioorganic and Medicinal Chemistry 24 (2016) 403-427.

WO2019123195 discloses a compound of the following formula I

providing bicyclic anthranilic diamides based on pyrazolo[l,5-a]pyridine-7-carboxamide derivatives, effective as insecticidal agents against harmful pests and useful as crop protecting agents.

WO2019123195 discloses a process that uses 2-(triphenylphosphanylidene)acetonitrile as a source of cyanoethylene and sodium hexamethyl disilazane (NaHMDS) as a base in the preparation of a certain alkyl 2-(5-(2-cyanoprop-l-en-l-yl)-lH-pyrazol-l-yl)acetate with 52% yield. The said alkyl 2-(5-(2- cyanoprop-l-en-l-yl)-lH-pyrazol-l-yl)acetate is a key intermediate in the construction of the pyrazolo[l,5-a]pyridine core. Therefore, any process giving only low yields of this intermediate would impact the overall cost effectiveness of the entire process. Further, there are no straightforward high yielding methods available in the prior art for the preparation of pyrazolo[1,5-a]pyridine-7-carboxamide based bicyclic anthranilic diamides. Hence, there is an unmet need for simple, efficient, industrially feasible and economic methods for the preparation of pyrazolo[1,5-a]pyridine-7-carboxamide based bicyclic anthranilic diamides. Accordingly, the present invention provides a simple, environment-friendly, and cost-effective process for the preparation of bicyclic anthranilic diamide compounds and intermediates thereof, based on readily available starting materials. OBJECTIVE OF THE INVENTION An objective of the present invention is to provide a simple, environment-friendly and cost-effective process for the preparation of bicyclic anthranilic diamides of formula (I) or of salts thereof. Another objective of the present invention is to provide a process for preparing bicyclic anthranilic diamides of formula (I) or of salts thereof, comprising the step of preparing a substituted 2-(5-(2- cyanoprop-1-en-1-yl)-1H-pyrazol-1-yl)acetate of formula (VII) or a salt thereof by reacting a substituted 2-(5-formyl-1H-pyrazol-1-yl)acetate of formula (VIII) or a salt thereof with a substituted (1-cyanoethyl)phosphonate of formula (IX) or a salt thereof. Yet another objective of the present invention is to provide a process for the preparation of compounds of formula (Z), that are useful intermediates in the preparation of bicyclic anthranilic diamide compounds of formula (I) or of salts thereof. SUMMARY OF INVENTION Accordingly, the present invention provides a process for preparing bicyclic anthranilic diamides of formula (I) or of salts thereof,

wherein, R¹ and R^1a are independently selected from the group consisting of hydrogen, halogen, C₁-C₄- alkyl, C₁-C₄-haloalkyl, C₂-C₄-alkenyl and C₃-C₆-cycloalkyl; R^a and R^b are independently selected from the group consisting of hydrogen, C₁-C₆-alkyl, C₂- C₆-alkenyl, C₃-C₆-cycloalkyl, C₁-C₆-haloalkyl, C₃-C₆-halocycloalkyl, and C₃-C₆-cycloalkyl- C₁-C₆-alkyl; R² is selected from the group consisting of halogen, CHF₂, CF₃, OCF₂H, OCH₂CF₃ and ; wherein A represents CR^cR^c, NR^c, O or S(O)_0-2; R^c is selected from the group consisting of hydrogen and C₁-C₄-alkyl; R³ is selected from the group consisting of hydrogen, halogen, C₁-C₄-alkyl and C₁-C₄-haloalkyl; and n is an integer, selected from 1to 3; comprising the steps of: a) reacting a substituted acetonitrile (R¹CH₂-CN) of formula (X) with a phosphorochloridate of formula (XI) or a salt thereof,

in the presence of a suitable base, a suitable reagent and a suitable solvent to obtain (R¹ substituted) cyanomethylphosphonate of formula (IX) or a salt thereof,

wherein, R⁴ and R⁵ are each independently selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-haloalkyl and C₁-C₄-alkenyl; or R⁴ and R⁵ together with the O atom to which they are attached may from a 5-8-membered ring and R¹ is as defined herein above; b) condensing the compound of formula (IX) or a salt thereof with a compound of formula (VIII) or a salt thereof,

in the presence of a suitable base and a suitable solvent to obtain a compound of formula (VII) or a salt thereof,

wherein, R⁶ is selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-haloalkyl and C₂-C₄- alkenyl; R¹ and R^1a are as define herein above; c) cyclising the compound of formula (VII) or a salt thereof in the presence of a suitable base and a suitable solvent to obtain a compound of formula (VI) or a salt thereof,

wherein, R¹, R^1a and R⁶ are as define herein above; optionally, d) hydrolysing the compound of formula (VI) or a salt thereof in the presence of a suitable hydrolysing reagent and a suitable solvent to obtain a compound of formula (V) or a salt thereof,

wherein, R¹ and R^1a are as define herein above; optionally, e) amidating the compound of formula (VI) or the compound of formula (V) or a salt thereof with an amine (NHR^aR^b) of formula (II) to obtain a compound of formula (XII) or a salt thereof,

wherein, R¹, R^1a, R^a and R^b are as define herein above; f) reacting the compound of formula (V) or the compound of formula (VI) or a salt thereof with a compound of formula (IV) or a salt thereof,

in the presence of a suitable reagent, a suitable base and a suitable solvent to obtain a compound of formula (III) or a salt thereof,

wherein, R , R , R , R and n are as define herein above; and g) amidating the compound of formula (III ) or a salt thereof with an amine (NHR^aR^b) of formula (II) to obtain a compound of formula (I) or a salt thereof,

wherein, R¹, R^1a, R^a, R^b, R², R³ and n are as define herein above; optionally, h) reacting the compound of formula (XII) or a salt thereof,

with a compound of formula (IV) or a salt thereof,

in the presence of a suitable reagent, a suitable base and a suitable solvent to obtain a compound of formula (I) or a salt thereof,

wherein, R¹, R^1a, R^a, R^b, R², R³ and n are as define herein above. In another aspect, the present invention provides a process for preparing the intermediate of formula (Z) or a salt thereof,

wherein, R is selected from the group consisting of OR⁶ and NHR^aR^b; R⁶ is selected from the group consisting of hydrogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, and C₂-C₄- alkenyl; R^a and R^b are independently selected from the group consisting of hydrogen, C₁-C₆-alkyl, C₂- C6-alkenyl, C₃-C₆-cycloalkyl, C₁-C₆-haloalkyl, C₃-C₆-halocycloalkyl and C₃-C₆-cycloalkyl-C1- C6-alkyl; R¹ and R^1a are independently selected from the group consisting of hydrogen, halogen, C₁-C₄- alkyl, C₁-C₄-haloalkyl, C₂-C₄-alkenyl and C₃-C₆-cycloalkyl; comprising the steps of: a) reacting a substituted acetonitrile (R¹CH₂-CN) of formula (X) with a phosphorochloridate of formula (XI) or a salt thereof,

in the presence of a suitable base, a suitable reagent and a suitable solvent to obtain a (substituted) cyanomethylphosphonate of formula (IX) or a salt thereof,

wherein, R⁴ and R⁵ are each independently selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-haloalkyland C₂-C₄-alkenyl; or R⁴ and R⁵ together with the O atom to which they are attached may from a 5-8-membered ring and R¹ is as defined herein above; b) condensing the compound of formula (IX) or a salt thereof with a compound of formula (VIII) or a salt thereof,

in the presence of a suitable base and a suitable solvent to obtain a compound of formula (VII) or a salt thereof,

wherein, R⁶ is selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-haloalkyl and C₂-C₄- alkenyl; R¹ and R^1a are as define herein above; c) cyclising the compound of formula (VII) or a salt thereof in the presence of a suitable base and a suitable solvent to obtain a compound of formula (VI) or a salt thereof,

wherein, R¹, R^1a and R⁶ are as define herein above; d) hydrolysing the compound of formula (VI) or a salt thereof in the presence of a suitable hydrolysing reagent and a suitable solvent to obtain a compound of formula (V) or a salt thereof,

wherein, R¹ and R^1a are as define herein above; e) amidating the compound of formula (VI) or the compound of formula (V) or a salt thereof with an amine (NHR^aR^b) of formula (II) to obtain a compound of formula (XII) or a salt thereof,

, wherein, R¹, R^1a, R^a and R^b are as defined herein above. DETAILED DESCRIPTION OF THE INVENTION The definitions provided herein for the terminologies used in the present disclosure are for illustrative purpose only and in no manner limit the scope of the present invention disclosed in the present disclosure. As used herein, the terms “comprises”, “comprising”, “includes”, “including”, “has”, “having”, “contains”, “containing”, “characterized by” or any other variation thereof, are intended to cover a non- exclusive inclusion, subject to any limitation explicitly indicated. For example, a composition, mixture, process or method that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, mixture, process or method. As used herein, the term “reacting” or “condensing” or “cyclising” or “hydrolysing” or “coupling” or “amidating” refers to a process of combining reactant(s) in a suitable medium or a solvent, wherein the reactants gets converted into desirable product(s) under reaction condition described. The transitional phrase “consisting of” excludes any element, step or ingredient not specified. If in the claim, such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase “consisting of” appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole. The transitional phrase “consisting essentially of” is used to define a composition or method that includes materials, steps, features, components or elements, in addition to those literally disclosed, provided that these additional materials, steps, features, components or elements do not materially affect the basic and novel characteristic(s) of the claimed invention. The term “consisting essentially of” occupies a middle ground between “comprising” and “consisting of”. Further, unless expressly stated to the contrary, “or” refers to an inclusive “or” and not to an exclusive “or”. For example, a condition A “or” B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B is true (or present). Also, the indefinite articles “a” and “an” preceding an element or component of the present invention are intended to be non-restrictive regarding the number of instances (i.e. occurrences) of the element or component. Therefore “a” or “an” should be read to include one or at least one, and the singular word form of the element or component also includes the plural unless the number is obviously meant to be singular. The meaning of various terms used in the description shall now be illustrated. The term “alkyl”, as used herein means a straight-chain or branched-chain C1 to C6 alkyl group and the representative examples include methyl, ethyl, propyl, isopropyl, butyl or the different isomers. The term “alkenyl”, as used herein means a straight-chain or branched C2 to C6 alkenes and the representative examples include ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl or the different isomers. The term “cycloalkyl” as used herein means alkyl closed to form a ring. Representative examples include but are not limited to cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. This definition also applies to cycloalkyl as a part of a composite substituent, for example cycloalkylalkyl etc., unless specifically defined elsewhere. This definition also applies to cycloalkyl as a part of a composite substituent, for example halocycloalkyl group, wherein; a cycloalkyl group is partially or fully substituted with halogen atoms which may be the same or different. The term “halogen”, includes fluorine, chlorine, bromine or iodine and the term “haloalkyl”, as used herein means an alkyl group is partially or fully substituted with halogen atoms which may be the same or different. Non-limiting examples of “haloalkyl” include 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-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro- 2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 1,1-dichloro-2,2,2-trifluoroethyl, and 1,1,1- trifluoroprop-2-yl. The description of the specific embodiments will so fully reveal the general nature of the embodiments herein that others can, by applying current knowledge, readily modify and/or adapt for various applications such specific embodiments without departing from the generic concept, and, therefore, such adaptations and modifications should and are intended to be comprehended within the meaning and range of equivalents of the disclosed embodiments. It is to be understood that the phraseology or terminology employed herein is for the purpose of description and not of limitation. Therefore, while the embodiments herein have been described in terms of preferred embodiments, those skilled in the art will recognize that the embodiments herein can be practiced with modification within the spirit and scope of the embodiments as described herein. Any discussion of documents, acts, materials, devices, articles and the like that has been included in this specification is solely for the purpose of providing a context for the disclosure. It is not to be taken as an admission that any or all of these matters form a part of the prior art base or were common general knowledge in the field relevant to the disclosure as it existed anywhere before the priority date of this application. The numerical values mentioned in the description and the description/claims though might form a critical part of the present invention of the present disclosure, any deviation from such numerical values shall still fall within the scope of the present disclosure if that deviation follows the same scientific principle as that of the present invention disclosed in the present disclosure. The compounds synthesized by the novel and inventive process of the present invention may, if appropriate, be present as mixtures of different possible isomeric forms, especially of stereoisomers, for example E and Z, threo and erythro, and also optical isomers, but if appropriate also of tautomers. Both the E and the Z isomers, and also the threo and erythro isomers, and the optical isomers, any desired mixtures of these isomers and the possible tautomeric forms are disclosed and claimed. In view of the above, defined objectives, the present invention provides a process for preparing bicyclic anthranilic diamides of formula (I) or a salt thereof,

wherein, R¹ and R^1a are independently selected from the group consisting of hydrogen, halogen, C₁-C₄- alkyl, C₁-C₄-haloalkyl, C₂-C₄-alkenyl and C₃-C₆-cycloalkyl; R^a and R^b are independently selected from the group consisting of hydrogen, C₁-C₆-alkyl, C₂- C₆-alkenyl, C₃-C₆-cycloalkyl, C₁-C₆-haloalkyl, C₃-C₆-halocycloalkyl, and C₃-C₆-cycloalkyl- C₁-C₆-alkyl; R² is selected from the group consisting of halogen, CHF₂, CF₃, OCF₂H, OCH₂CF₃, and ; wherein A represents CR^cR^c, NR^c, O or S(O)_0-2; R^c is selected from the group consisting of hydrogen and C₁-C₄-alkyl; R³ is selected from the group consisting of hydrogen, halogen, C₁-C₄-alkyl and C₁-C₄-haloalkyl; and n is an integer, selected from 1to 3; comprising the steps of: a) reacting a substituted acetonitrile (R¹CH₂-CN) of formula (X) with a phosphorochloridate of formula (XI) or a salt thereof,

in the presence of a suitable base, a suitable reagent and a suitable solvent to obtain a (R¹ substituted) cyanomethylphosphonate of formula (IX) or a salt thereof,

wherein, R⁴ and R⁵ are each independently selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-haloalkyl and C₁-C₄-alkenyl or R⁴ and R⁵ together with the O atom to which they are attached may form a 5-8-membered ring and R¹ is as defined herein above; b) condensing the compound of formula (IX) or a salt thereof with a compound of formula (VIII) or a salt thereof,

in the presence of a suitable base and a suitable solvent to obtain a compound of formula (VII) or a salt thereof,

wherein, R⁶ is selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-haloalkyl and C₂-C₄- alkenyl; R¹ and R^1a are as define herein above; c) cyclising the compound of formula (VII) or a salt thereof in the presence of a suitable base and a suitable solvent to obtain a compound of formula (VI) or a salt thereof,

wherein, R¹, R^1a and R⁶ are as define herein above; optionally, d) hydrolysing the compound of formula (VI) or a salt thereof in the presence of a suitable hydrolysing reagent and a suitable solvent to obtain a compound of formula (V) or a salt thereof,

wherein, R¹ and R^1a are as define herein above; optionally, e) amidating the compound of formula (VI) or compound of formula (V) or a salt thereof with an amine (NHR^aR^b) of formula (II) to obtain a compound of formula (XII) or a salt thereof,

wherein, R¹, R^1a, R^a and R^b are as define herein above; f) reacting the compound of formula (V) or the compound formula (VI) or a salt thereof with a compound of formula (IV) or a salt thereof,

in the presence of a suitable reagent, a suitable base and a suitable solvent to obtain a compound of formula (III) or a salt thereof,

wherein, R , R , R , R and n are as define herein above; and g) amidating the compound of formula (III) or a salt thereof with an amine (NHR^aR^b) of formula (II) to obtain a compound of formula (I) or a salt thereof,

wherein, R¹, R^1a, R^a, R^b, R², R³ and n are as define herein above; optionally, h) reacting the compound of formula (XII) or a salt thereof,

with a compound of formula (IV) or a salt thereof,

in the presence of a suitable reagent, a suitable base and a suitable solvent to obtain a compound of formula (I) or a salt thereof,

wherein, R¹, R^1a, R^a, R^b, R², R³ and n are as define herein above. In one embodiment, the present invention provides a process for the synthesis of a compound of formula (I) comprising the steps of: Reacting a compound of formula (VI) with a compound of formula (IV) in the presence of a suitable reagent to obtain a compound of formula (IIIA). Reacting the compound of formula (IIIA) with a suitable amine to obtain a compound of formula (I) as shown in the scheme below:

. In another aspect, the present invention provides a process for preparing the intermediate of formula (Z) or a salt thereof,

wherein, R is selected from the group consisting of OR⁶ and NHR^aR^b; R⁶ is selected from the group consisting of hydrogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, and C₂-C₄- alkenyl; R^a and R^b are independently selected from the group consisting of hydrogen, C₁-C₆-alkyl, C₂-C₆- alkenyl, C₃-C₆-cycloalkyl, C₁-C₆-haloalkyl, C₃-C₆-halocycloalkyl and C₃-C₆-cycloalkyl-C₁-C₆-alkyl; R¹ and R^1a are independently selected from the group consisting of hydrogen, halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₂-C₄-alkenyl and C₃-C₆-cycloalkyl; comprising the steps of: a) reacting a substituted acetonitrile (R¹CH₂-CN) of formula (X) with a phosphorochloridate of formula (XI) or a salt thereof,

in the presence of a suitable base, a suitable reagent and a suitable solvent to obtain a (R¹ substituted) cyanomethylphosphonate of formula (IX) or a salt thereof,

wherein, R⁴ and R⁵ are each independently selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-haloalkyl and C₂-C₄-alkenyl; or R⁴ and R⁵ together with the O atom to which they are attached may form a 5-8-membered ring and R¹ is as defined herein above; b) condensing the compound of formula (IX) or a salt thereof with a compound of formula (VIII) or a salt thereof,

in the presence of a suitable base and a suitable solvent to obtain a compound of formula (VII) or a salt thereof,

wherein, R⁶ is selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-haloalkyl and C₂-C₄- alkenyl; R¹ and R^1a are as define herein above; c) cyclising the compound of formula (VII) or a salt thereof in the presence of a suitable base and a suitable solvent to obtain a compound of formula (VI) or a salt thereof,

wherein, R¹, R^1a and R⁶ are as define herein above; d) hydrolysing the compound of formula (VI) or a salt thereof in the presence of a suitable hydrolysing reagent and a suitable solvent to obtain a compound of formula (V) or a salt thereof,

wherein, R¹ and R^1a are as define herein above; e) amidating the compound of formula (VI) or the compound of formula (V) or a salt thereof with an amine (NHR^aR^b) of formula (II) to obtain a compound of formula (XII) or a salt thereof,

, wherein, R¹, R^1a, R^a and R^b are as defined herein above. In another aspect, the present invention provides an alternative process for preparing the compound of formula (V) comprising the steps of: cyclizing the compound of formula (VII) or a salt thereof, in the presence of a suitable base, and a suitable solvent to obtain a compound of formula (VI) or a salt thereof; which is reacted in situ with a suitable hydrolysing agent to obtain a compound of formula (V) or a salt thereof as shown in the scheme below:

, wherein, R¹, R^1a, R⁶, are each as defined above. In yet another aspect, the present invention provides an alternative process for preparing the compound of formula (V) comprising the steps of: condensing the compound of formula (IX) or a salt thereof with a compound of formula (VIII) or a salt thereof, in the presence of a suitable base, and a suitable solvent to obtain a compound of formula (VII) or a salt thereof; which is reacted in situ with a suitable base to obtain a compound of formula (VI) or a salt thereof; which is reacted in situ with a suitable hydrolysing agent to obtain the compound of formula (V) or a salt thereof; as shown in the scheme below:

, wherein, R¹, R^1a, R⁶, are each as defined above. In one embodiment, the present invention provides a compound of formula (IIIA)

wherein, R¹ and R^1a are independently selected from the group consisting of hydrogen, halogen, C₁-C₄- alkyl, C₁-C₄-haloalkyl, C₂-C₄-alkenyl and C₃-C₆-cycloalkyl; R² is selected from the group consisting of halogen, CHF₂, CF₃, OCF₂H, OCH₂CF₃, and ; wherein A represents CR^cR^c, NR^c, O or S(O)_0-2; R^c is selected from the group consisting of hydrogen and C_1-C₄-alkyl; R³ is selected from the group consisting of hydrogen, halogen, C₁-C₄-alkyl and C₁-C₄-haloalkyl; R⁶ is selected from the group consisting of hydrogen and C₁-C₄-alkyl; n is an integer, selected from 1 to 3. In one embodiment, the present invention provides a process for preparing bicyclic anthranilic diamides of formula (I), comprising the step of preparing a substituted 2-(5-(2-cyanoprop-1-en-1-yl)-1H-pyrazol- 1-yl)acetate of formula (VII) or a salt thereof, by reacting a substituted 2-(5-formyl-1H-pyrazol-1- yl)acetate of formula (VIII) or a salt thereof, with a substituted (1-cyanoethyl)phosphonate of formula (IX) or a salt thereof, in the presence of a suitable base and a suitable solvent. According to a preferred embodiment, the substituted acetonitrile of formula (X) is (R¹CH₂-CN) wherein R¹ is selected from the group consisting of hydrogen, C₁-C₃-alkyl and C₁-C₃-haloalkyl. In another embodiment, the present invention provides a phosphorochloridate of formula (XI) or a salt thereof, wherein the preferred groups R⁴ and R⁵ are each independently selected as C₁-C₃-alkyl or R⁴ and R⁵ together with the O atom to which they are attached may form a 5-8-membered ring. In yet another embodiment, the present invention provides a compound of formula (IX) or a salt thereof, wherein the preferred group R¹ is selected from the group consisting of hydrogen, C₁-C₃-alkyl, C₁-C₃- haloalkyl and C₃-C₄-cycloalkyl and R⁴ and R⁵ are each independently selected as C₁-C₃-alkyl or R⁴ and R⁵ together with the O atom to which they are attached may form a 5-8-membered ring. In another embodiment, the compound of formula (VIII) can be prepared according to the procedure as reported in WO2019123195. In yet another preferred embodiment, the present invention provides a compound of formula (VIII) or a salt thereof, wherein R⁶ is C₁-C₄-alkyl. Yet another preferred embodiment of the present invention provides a compound of formula (VII) or a salt thereof, wherein R¹ is selected from the group consisting of hydrogen, C₁-C₃-alkyl, C₁-C₃-haloalkyl and C₃-C₄-cycloalkyl; and R⁶ is C₁-C₃-alkyl. Yet another preferred embodiment of the present invention provides a compound of formula (VI) or a salt thereof, wherein R¹ is selected from the group consisting of hydrogen, C₁-C₃-alkyl, C₁-C₃-haloalkyl and C₃-C₄-cycloalkyl; and R⁶ is C₁-C₃-alkyl. Still another preferred embodiment of the present invention provides a compound of formula (V) or a salt thereof, wherein R¹ is selected from the group consisting of hydrogen, C₁-C₃-alkyl, C₁-C₃-haloalkyl and C₃-C₄-cycloalkyl. Still another preferred embodiment of the present invention provides a compound of formula (IV) or a salt thereof, wherein R² is selected from the group consisting of halogen, CHF₂, CF₃, OCF₂H, OCH₂CF₃ and

; wherein A represents CR^cR^c, NR^c, O or S(O)_0-2; wherein R^c is selected from the group consisting of hydrogen and C₁-C₄-alkyl; R³ is selected from the group consisting of hydrogen, halogen, C₁-C₃-alkyl and C₁-C₃-haloalkyl; and n is 0-3; Yet another preferred embodiment of the present invention provides a compound of formula (III) or a salt thereof, wherein R¹ is selected from the group consisting of hydrogen, C₁-C₃-alkyl, C₁-C₃-haloalkyl and C₃-C₄-cycloalkyl; R² is selected from the group consisting of halogen, CHF₂, CF₃, OCF₂H, OCH₂CF₃ and

; wherein A represents CR^cR^c, NR^c, O or S(O)_0-2; wherein R^c is selected from the group consisting of hydrogen and C_1-C₄-alkyl; and R³ is selected from the group consisting of hydrogen, halogen, C₁-C₃-alkyl and C₁-C₃-haloalkyl. Yet another embodiment of the present invention provides a compound of formula (II) or a salt thereof, wherein R^a and R^b are independently selected from the group consisting of hydrogen, C₁-C₄-alkyl, C₃- C₆-cycloalkyl, C₁-C₄-haloalkyl, C₃-C₆-halocycloalkyl and C₃-C₆-cycloalkyl-C₁-C₄-alkyl. Yet another embodiment of the present invention provides a compound of formula (I) or a salt thereof, wherein R¹, R^a and R^b, R² and R³ are as defined above. In one particular embodiment, the present invention provides a process for preparing bicyclic anthranilic diamides of the formula (Ia) or a salt thereof,

wherein, R¹ is selected from the group consisting of methyl, trifluromethyl, or halogen; R^a is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-, iso- or tert-butyl; and R^b is selected from the group consisting of hydrogen or methyl; comprising the steps of: a) reacting an acetonitrile (CH₃CH₂-CN) of formula (Xa) with a phosphorochloridate of formula (XIa) or a salt thereof,

in the presence of a suitable base, a suitable reagent and a suitable solvent, to obtain a diethyl (R¹ substituted) cyanomethylphosphonate of formula (IXa) or a salt thereof;

wherein R¹ is as defined herein above; b) condensing the compound of formula (IXa) or a salt thereof, with a compound of formula (VIIIa) or a salt thereof,

in the presence of a suitable base and a suitable solvent, to obtain a compound of formula (VIIa) or a salt thereof;

wherein R¹ is as defined herein above; c) cyclising the compound of formula (VIIa) or a salt thereof, in the presence of a suitable base and a suitable solvent, to obtain a compound of formula (VIa) or a salt thereof;

wherein R¹ is as defined herein above; d) hydrolysing the compound of formula (VIa) or a salt thereof, in the presence of a suitable hydrolysing reagent and a suitable solvent, to obtain a compound of formula (Va) or a salt thereof;

wherein R¹ is as defined herein above; optionally, e) amidating the compound of formula (VIa) or compound of formula (Va) or a salt thereof, with a suitable amine [(CH3)2CH-NH₂] of formula (IIa), to obtain a compound of formula (XIIa) or a salt thereof.

wherein R¹, R^a and R^b are as defined herein above; f) coupling the compound of formula (Va) or a salt thereof, with a compound of formula (IVa) or a salt thereof,

in the presence of a suitable coupling reagent, a suitable base and a suitable solvent, to obtain a compound of formula (IIIa) or a salt there of

wherein R¹ is as defined herein above and; g) amidating the compound of formula (IIIa) or a salt thereof, with a suitable amine [(CH₃)₂CH- NH₂] of formula (IIa), to obtain a compound of formula (Ia) or a salt thereof.

wherein R¹, R^a and R^b are as defined herein above; optionally, h) coupling the compound of formula (XIIa) or a salt thereof,

wherein R¹, R^a and R^b are as defined herein above; with a compound of formula (IVa) or a salt thereof,

in the presence of a suitable reagent, a suitable base and a suitable solvent, to obtain a compound of formula (Ia) or a salt there of;

wherein R¹, R^a and R^b are as defined herein above;. In one embodiment of the present invention, the reaction step (a) of the above described process for the preparation of anthranilic diamides of formula (I) or a salt thereof, can be performed at a temperature ranging from -100 °C to 100 °C for a period of few minutes to several hours, optionally under an inert atmosphere to afford a compound of formula (IX). Preferably, the reaction temperature ranges from - 80 °C to 40 °C for a period of few minutes to 24 hours under an inert atmosphere. In one embodiment, the process is performed in the presence of a base selected from organic, inorganic or organometallics bases. The inorganic base is selected from alkali metal hydroxide for example lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide; alkaline earth metal hydroxides for example, calcium hydroxide, barium hydroxide, magnesium hydroxide; alkali carbonate for example lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate; alkaline earth carbonate for example magnesium carbonate, calcium carbonate, barium carbonate; alkali hydride for example lithium hydride, sodium hydride, potassium hydride; alkaline hydride for example magnesium hydride, calcium hydride, barium hydride; metal phosphates for example sodium diphosphate, sodium phosphate, potassium diphosphate, potassium phosphate and the like. The organic base is selected from amines which includes but is not limited to ethylamine, triethylamine, isopropylamine diisopropylamine, triisopropylamine, pyridine, piperidine, N,N- (dimethylamino)pyridine (DMAP), tetramethylammonium hydroxide, tetrabutylammonium hydroxide, choline hydroxide; amidine base for example, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, (TBD), 2,3,4,6,7,8,9,10-octahydropyrimidol[1,2-a]azepine (DBU), 1,8-diazabicyclo(5.4.0)undec-7-ene, 1,5- diazabicyclo[4.3.0]non-5-ene (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO) or triethylenediamine). The organometallic base is selected from metal alkoxide which include but is not limited to lithium alkoxide, for example, lithium methoxide, lithium ethoxide, lithium isopropoxide; sodium alkoxide for example, sodium methoxide, sodium ethoxide, sodium isopropoxide; potassium alkoxide, for example potassium methoxide, potassium ethoxide, potassium isopropoxide, potassium tert-butoxide; magnesium alkoxide, for example, magnesium ethoxide, magnesium tert-butoxide, magnesium isopropoxide; aluminium alkoxide, for example, aluminium ethoxide, aluminum isopropoxide; titanium alkoxide, for example, titanium(IV) ethoxide titanium(IV) isopropoxide and the like or a mixture thereof. Suitable solvents for carrying out the process according to the present invention are all inert organic solvents. These preferably include aliphatic, alicyclic or aromatic hydrocarbons such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons such as, chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2- dimethoxyethane, 1,2-diethoxyethane or anisole; ketones, such as acetone, butanone, methyl isobutyl ketone or cyclohexanone; nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide, N- methylpyrrolidone, N, N′-Dimethylpropyleneurea or hexamethylphosphoramide; esters such as methyl acetate or ethyl acetate; sulphoxides, such as dimethyl sulphoxide, sulphones, such as sulpholane, or dimethyl sulfone, alcohols such as methanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water. In one embodiment, the reaction step (a) is performed in the presence of a suitable reagent selected from organolithium compounds, preferably the reagent is alkyllithium such as n-butyllithium and as suitable organic base such as diisopropylamine. In one embodiment, the reaction step (a) is performed in a solvent selected from aliphatic, alicyclic or aromatic hydrocarbons, for example petroleum ether, n-hexane, n-heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; ethers such as diethyl ether, diisopropyl ether, methyl tert -butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 2-methyl tetrahydrofuran, 1,2-dimethoxyethane, 1,2- diethoxyethane, cyclopentylmethylether or anisole; amides such as N,N- dimethylformamide, N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone, N,N′- dimethylpropyleneurea or hexamethylphosphoramide; sulphoxides such as dimethyl sulphoxide; sulphones such as dimethyl sulfone or sulpholane; Preferably, the solvent is selected from ethers, more preferably, tetrahydrofuran, 2-methyl tetrahydrofuran, or a mixture thereof. In one embodiment of the present invention, the reaction step (a) of the above described process can be performed at a temperature ranging from -100 °C to 50 °C for a period of few minutes to several hours, In one embodiment, the reaction step (a) is performed under atmospheric pressure, but can also be carried out under increased or reduced pressure. In one embodiment, after completion of the reaction, the reaction step (a) can be continued to the next step (b) with or without isolation of the intermediate product of formula (IX). In one embodiment, the suitable base for performing the reaction step (b) is selected from the suitable bases as provided above. Preferably, the suitable base is selected from alkali carbonate, alkali hydride, amidine, organic amine, or a mixture thereof. More preferably, the base is selected from alkali carbonate, amidine or organic amines; such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, 2,3,4,6,7,8,9,10-octahydropyrimidol[1,2-a]azepine (DBU), 1,8- diazabicyclo(5.4.0)undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,4- diazabicyclo[2.2.2]octane (DABCO), ethylamine, triethylamine, isopropylamine diisopropylamine, triisopropylamine, pyridine, piperidine, N,N-(dimethylamino)pyridine (DMAP) or a mixture thereof. In one embodiment, the suitable solvent for performing the reaction step (b) is selected from the suitable solvents as provided for the reaction step above. Preferably, the suitable solvent is selected from ethers, nitriles, amides, sulfoxides or a mixture thereof. More preferably, the solvent is selected from ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; ketones, such as acetone, butanone, methyl isobutyl ketone or cyclohexanone; nitriles, such as acetonitrile, propionitrile, n- or i- butyronitrile or benzonitrile; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N- methylformanilide, N-methylpyrrolidone, N,N′-Dimethylpropyleneurea or hexamethylphosphoramide; esters such as methyl acetate or ethyl acetate; sulphoxides, such as dimethyl sulphoxide, sulphones, such as sulpholane, or dimethyl sulfone or a mixture thereof. In one embodiment of the present invention, the reaction step (b) of the above described process can be performed at a temperature ranging from -25 °C to 150 °C for a period of few minutes to several hours, Preferably, the reaction temperature ranges from 0 °C to 100 °C for a period of few minutes to 36 hours. In one embodiment, the reaction step (b) is performed under atmospheric pressure, but can also be carried out under increased or reduced pressure. In one embodiment, after completion of the reaction, the reaction step (b) can be continue to the next step (c) with or without isolation of the intermediate product of formula (VII). In one embodiment, after completion of the reaction, the reaction step (b) can be continue to the next step (d) with or without isolation of the intermediate of formula (VII) and (VI). In one embodiment, the compound of formula (VII) is optionally isolated. In one embodiment, the base for performing the reaction step (c) is selected from the suitable bases as provided above. Preferably, the suitable base is selected alkali carbonate for example lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate; alkaline earth carbonate for example magnesium carbonate, calcium carbonate, barium carbonate; alkali hydride for example lithium hydride, sodium hydride, potassium hydride; alkaline hydride for example magnesium hydride, calcium hydride, barium hydride; metal phosphates for example sodium diphosphate, sodium phosphate, potassium diphosphate, potassium phosphate and the like; metal alkoxide which include but is not limited to lithium alkoxide, for example, lithium methoxide, lithium ethoxide, lithium isopropoxide; sodium alkoxide for example, sodium methoxide, sodium ethoxide, sodium isopropoxide; potassium alkoxide, for example potassium methoxide, potassium ethoxide, potassium isopropoxide, potassium tert-butoxide; or a mixture thereof. More preferably, the suitable base is selected from metal carbonate, metal alkoxide, such potassium tert-butoxide or a mixture thereof. In one embodiment, the solvent for carrying out the reaction step (c) is selected from the suitable solvents as provided above. Preferably, the suitable solvent is selected from ethers, nitriles, amides, sulfoxides or a mixture thereof. More preferably, the solvent is selected from ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2- dimethoxyethane, 1,2-diethoxyethane or anisole; ketones, such as acetone, butanone, methyl isobutyl ketone or cyclohexanone; nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide, N- methylpyrrolidone, N,N′-dimethylpropyleneurea or hexamethylphosphoramide; esters such as methyl acetate or ethyl acetate; sulphoxides, such as dimethyl sulphoxide, sulphones, such as sulpholane, or dimethyl sulfone or a mixture thereof. In one embodiment of the present invention, the reaction step (c) of the above described process can be performed at a temperature ranging from -50 °C to 150 °C for a period of few minutes to several hours, optionally under inert atmosphere to afford a compound of formula (VI). Preferably, the reaction temperature ranges from -25 °C to 100 °C for a period of few minutes to 24 hours. In one embodiment, the reaction step (c) is performed under atmospheric pressure, but can also be carried out under increased or reduced pressure. In one embodiment, after completion of the reaction, the reaction step (c) can be continued to the next step (d) with or without isolation of the intermediate product of formula (VI). In one embodiment, the compound of formula (VI) is optionally isolated. In one embodiment, the reaction step (d) is performed in the presence of a suitable hydrolysing reagent selected from metal hydroxide, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, calcium hydroxide, barium hydroxide, magnesium hydroxide; metal carbonate, for example lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, barium carbonate; metal alkoxides, for example lithium methoxide, lithium ethoxide, lithium isopropoxide, sodium methoxide, sodium ethoxide, sodium isopropoxide, potassium methoxide, potassium ethoxide, potassium isopropoxide, potassium tert- butoxide, magnesium ethoxide, magnesium tert-butoxide, magnesium isopropoxide, aluminium ethoxide, aluminum isopropoxide; titanium(IV) ethoxide titanium(IV) isopropoxide or a mixture thereof. Preferably, the suitable hydrolysing agent is selected from metal hydroxides, metal carbonate or a mixture thereof. More preferably, the suitable hydrolysing agent is selected from lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate or a mixture thereof. In one embodiment, the suitable solvent for carrying out the reaction step (d) is selected from suitable solvents as provided above. Preferably, the suitable solvent is selected from alcohol, ethers, nitriles or a mixture thereof. More preferably, the suitable solvent is selected from diisopropyl ether, methyl t- butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane; alcohols such as methanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol, ethanediol, propane- 1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, water or mixtures thereof. In one embodiment of the present invention, the reaction step (d) of the above described process can be performed at a temperature ranging from -20 °C to 100 °C for a period of few minutes to several hours, optionally under inert atmosphere to afford compound of formula (V). Preferably, the reaction temperature ranges from -20 °C to 75 °C for a period of few minutes to 24 hours. In one embodiment, the reaction step (d) is performed under atmospheric pressure, but can also be carried out under increased or reduced pressure. In one embodiment, after completion of the reaction, the reaction step (d) can be continued to the next step (e) with or without isolation of the intermediate product of formula (V). In one embodiment, the reaction steps (e, f or h) are performed in presence of a suitable base selected from organic amine bases for example, ethylamine, triethylamine, isopropylamine diisopropylamine, triisopropylamine, pyridine, 3-methylpyridine, piperidine, N,N-(dimethylamino)pyridine (DMAP); amidine for example, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, (TBD), 2,3,4,6,7,8,9,10- octahydropyrimidol[1,2-a]azepine (DBU) 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,4- diazabicyclo[2.2.2]octane (DABCO, triethylenediamine) or a mixture thereof or the inorganic base is selected from alkali carbonate for example lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate; alkaline earth carbonate for example magnesium carbonate, calcium carbonate, barium carbonate. Preferably, the suitable base is selected from amine base and alkali carbonate; more preferably, the suitable base is selected from triethylamine, diisopropylamine, 3-methylpyridine, pyridine, piperidine, lithium carbonate, sodium carbonate, potassium carbonate or a mixture thereof. The reaction could also be performed without additional base. In one embodiment, the solvent for carrying out the reaction steps (e, f or h) is selected from the suitable solvents as provided above. Preferably, the suitable solvent is usually selected from ethers, nitriles, ketones, halogenated hydrocarbons, amides or a mixture thereof. More preferably the suitable solvent is selected from ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; ketones, such as acetone, butanone, methyl isobutyl ketone or cyclohexanone; nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; halogenated hydrocarbons such as, chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; or a mixture thereof. The reaction can also be carried out in the absence of a solvent. In one embodiment, the reaction steps (e, f or h) are performed under atmospheric pressure, but can also be carried out under increased or reduced pressure. In one embodiment of the present invention, the reaction steps (e, f or h) can be performed at a temperature ranging from 0 °C to 150 °C for a period of few minutes to several hours. Preferably, the reaction temperature ranges from 0 °C to 75 °C for a period of few minutes to 24 hours. The suitable reagent for steps (e, f or h) include but are not limited to oxalyl chloride, sulphonyl chloride, for example thionyl chloride, methanesulphonyl chloride, benzenesulfonyl chloride; carbodiimides, for example N,N′-dicyclohexylcarbodiimide (DCC), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDAC); aminium compounds, for example (2-(1H-benzotriazol-1-yl)-1,1,3,3-tetramethyluronium hexafluorophosphate (HBTU), 2-(1H-Benzotriazole-1-yl)-1,1,3,3-tetramethylaminium tetrafluoroborate (TBTU), 1-[Bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3- oxid hexafluorophosphate (HATU), 1-[(dimethylamino)(morpholino)methylene]-1H- [1,2,3]triazolo[4,5-b]pyridine-1-ium 3-oxide hexafluorophosphate (HDMA); phosphonium compound, for example, (benzotriazol-1-yloxy)tris(dimethylamino)phosphonium hexafluorophosphate (BOP), benzotriazole-1-yl-oxy-tris-pyrrolidino-phosphonium hexafluorophosphate (PyBOP) or a mixture thereof. Preferably, the suitable reagent is selected from sulphonyl chloride, carbodiimides or mixture thereof. More preferably, the suitable reagent is selected from sulphonyl chloride such as oxalyl chloride or methanesulphonyl chloride. In one embodiment, after completion of the reaction, the reaction step (f) can be continued to the next step (g) with or without isolation of the intermediate product of formula (III). In one embodiment, the solvent used for carrying out the reaction step (g) is selected from suitable solvents as provided above. Preferably, the suitable solvent is selected from ethers, nitriles, amides, sulfoxides or a mixture thereof. More preferably, the suitable solvent is selected from ether, nitriles, amides or a mixture thereof. The reaction can also be carried out in the absence of a solvent. In one embodiment of the present invention, the reaction step (g) of the above described process can be performed at a temperature ranging from 0 °C to 150 °C for a period of few minutes to several hours, optionally under inert atmosphere to afford the compound of formula (I). Preferably, the reaction temperature ranges from 0 °C to 100 °C for a period of few minutes to 24 hours. In one embodiment, the reaction step (g) is performed under atmospheric pressure, but can also be carried out under increased or reduced pressure. The processes as disclosed in the present invention are preferably carried out batch-wise. However, semi-continuous or continuous reaction passages, e.g., under flow conditions, are also possible. The processes as disclosed in the present invention can be carried out in the absence of a suitable solvent or in the presence of one or more suitable solvent. The optional suitable solvent should be resistant against oxidation (i.e. a solvent will be preferred whose rate of oxidation is substantially lower than that of the compounds of formula I to XI) and suitable for suspending, or preferably dissolving the reactants. The isolation of the reaction product can be carried out by a technique which includes but is not limited to decantation, centrifugation, evaporation, liquid-liquid extraction, distillation, recrystallization, chromatography and the like or a combination thereof. The process steps according to the invention are generally carried out under atmospheric pressure. Alternatively, however, it is also possible to work under or increased pressure. The reaction time is not critical and depends on the batch size, temperature, reagent and solvent employed. Typically, the reaction time may vary from a few minutes to several hours. Any person skilled in the art knows the best work-up of the reaction mixtures after the end of the respective reactions. In one embodiment, the work-up is usually carried out by isolation of the product, and optionally washing with suitable solvent, and further optionally drying of the product if useful or required. The isolation of the reaction product can be carried out by a technique which includes but is not limited to decantation, filtration, centrifugation, evaporation, liquid-liquid extraction, distillation, recrystallization, chromatography and the like or a combination thereof. The process steps according to the invention are generally carried out under atmospheric pressure. Alternatively, however, it is also possible to work under reduced pressure or under pressure. In the context of the present invention, the term “optionally” when used in reference to any element, intermediates, reagents or conditions; including a process step e.g. isolation of intermediates; it is intended to mean that the subject element is isolated, or alternatively, is not isolated from the reaction mixture and directly used for the further chemical reaction. Without further elaboration, it is believed that any person skilled in the art who is using the preceding description can utilize the present invention to its fullest extent. The following examples are therefore to be interpreted as merely illustrative and not limiting of the disclosure in any way whatever. EXAMPLES The invention is further illustrated with reference to the following schematic representation as provided in scheme 1. It is apparent to those skilled in the art that many modifications, both to materials, methods and various reaction parameters, may be practiced without departing from the scope of the invention. The starting materials according to the present invention are known compounds that are commercially available or can be prepared in a known manner. Following examples are given by way of illustration and therefore should not be construed to limit the scope of the invention. Scheme-1

Examples 1: Preparation of 6-(3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxamido)- N-isopropyl-5-methylpyrazolo[1,5-a]pyridine-7-carboxamide (Ia) Step (a): Preparation of diethyl (1-cyanoethyl)phosphonate (IXa) To a stirred solution of diisopropylamine (8.26 mL, 58.0 mmol) in tetrahydrofuran (30 mL), n- butyllithium (29.0 mL, 58.0 mmol, 2M in cyclohexane) was charged at -78 °C under nitrogen atmosphere. The reaction mixture was stirred for 30 min at -78°C, then allowed to warm up to 0 °C and further stirred for 30 min. Then, a solution of propionitrile (Xa, 2.02 mL, 29.0 mmol) in tetrahydrofuran (20 mL) was charged at -78 °C, and the resulting mixture was stirred for 15 min. A solution of diethyl phosphorochloridate (XIa, 4.20 mL, 29.0 mmol) in tetrahydrofuran (10 mL) was added slowly to this reaction mixture which was stirred for 45 min at -78°C. The reaction mixture was allowed to warm up to 25 °C and further stirred for 15 min. After completion of the reaction, the reaction mixture was quenched with aqueous 2M hydrochloric acid solution (25 mL) and extracted with methyl tert-butyl ether (2 x 50 mL). The organic layer was concentrated to afford diethyl (1-cyanoethyl)phosphonate (IXa, 5 g, 26.2 mmol, 90% yield) as a pale yellow liquid. ¹H-NMR (400 MHz, CHLOROFORM-D) δ 4.19-4.29 (m, 4H), 4.00-4.13 (m, 1H), 2.96 (dq, J = 23.4, 7.3 Hz, 1H), 1.53-1.59 (m, 3H), 1.35-1.43 (m, 6H) Step (b): Preparation of ethyl 2-(5-(2-cyanoprop-1-en-1-yl)-1H-pyrazol-1-yl)acetate (VIIa). Method-1 To a stirred a solution of ethyl 2-(5-formyl-1H-pyrazol-1-yl)acetate (VIIIa, 178 g, 977 mmol) and diethyl (1-cyanoethyl)phosphonate (IXa, 187 g, 977 mmol) in tetrahydrofuran (1200 mL), 1,8- diazabicyclo(5.4.0)undec-7-ene (177 mL, 1172 mmol) was added drop wise at 0 °C. After complete addition, the reaction mixture was warmed to 25 °C and stirred for 2 h. After completion of the reaction, the reaction mixture was diluted with saturated aq. ammonium chloride solution (800 mL) and extracted with ethylacetate (2 x 800 mL). The combined organic layer was washed with brine (800 mL) and concentrated under reduced pressure to obtain a residue. The residue was taken up in 10% dichloromethane/hexane (1 L), the obtained mixture was stirred for 1 h and filtered to afford a 1:1 cis/trans mixture of ethyl 2-(5-(2-cyanoprop-1-en-1-yl)-1H-pyrazol-1-yl)acetate (VIIa, 159 g, 725 mmol, 74.2% yield) as an off white solid. ¹H-NMR (400 MHz, CHLOROFORM-D) δ 7.59 (d, J = 8.2 Hz, 1H), 6.49-7.16 (m, 2H), 4.97 (s, 2H), 4.21-4.27 (m, 2H), 2.17 (s, 3H), 1.26-1.31 (m, 3H). MS: m/z calcd for C₁₁H₁₃N₃O₂: 219.10; found 220.40 (M+1) Method-2 To a stirred solution of ethyl 2-(5-formyl-1H-pyrazol-1-yl)acetate (VIIIa, 200 g, 1010 mmol) and diethyl (1-cyanoethyl)phosphonate (IXa, 252 g, 1212 mmol) in acetonitrile (600 mL), potassium carbonate (209 g, 1515 mmol) was added at 15 °C. The reaction mixture was stirred at 25 °C for 12 h. After completion of the reaction, the reaction mixture was cooled to 10°C and diluted with water (3 L). The slurry mass was stirred further for 4 h at 25 ° and then filtered to obtain a solid cake, which was dried under reduced pressure to obtain a 1:1 cis/trans mixture of ethyl 2-(5-(2-cyanoprop-1-en-1-yl)- 1H-pyrazol-1-yl)acetate (VIIa, 196 g, 894 mmol, 89% yield) as an off white solid. ¹H-NMR (400 MHz, CHLOROFORM-D) δ 7.59 (d, J = 8.2 Hz, 1H), 6.49-7.16 (m, 2H), 4.97 (s, 2H), 4.21-4.27 (m, 2H), 2.17 (s, 3H), 1.26-1.31 (m, 3H). MS: m/z calcd for C₁₁H₁₃N₃O₂: 219.10; found 220.05 (M+1). Method-3 To a stirred a solution of ethyl 2-(5-formyl-1H-pyrazol-1-yl)acetate (VIIIa, 1 g, 5.49 mmol) and diethyl (1-cyanoethyl)phosphonate (IXa, 1.05 g, 5.49 mmol) in tetrahydrofuran (10 mL) at 25 °C, potassium carbonate (3.79 g, 27.4 mmol) was added at 25 °C. The reaction mixture was stirred at 25 °C for 16 h. After completion of the reaction, the reaction mixture was diluted in saturated aq. ammonium chloride solution (10 mL) and extracted with ethyl acetate (2 x 10 mL). The combined organic layer was washed with brine (10 mL), dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to obtain ethyl 2-(5-(2-cyanoprop-1-en-1-yl)-1H-pyrazol-1-yl)acetate (VIIa, 1.0 g, 4.56 mmol, 83% yield) as an off white solid. ¹H-NMR (400 MHz, CHLOROFORM-D) δ 7.59 (d, J = 8.2 Hz, 1H), 6.49-7.16 (m, 2H), 4.97 (s, 2H), 4.21-4.27 (m, 2H), 2.17 (s, 3H), 1.26-1.31 (m, 3H). MS: m/z calcd for C₁₁H₁₃N₃O₂: 219.10; found 220.05 (M+1). Method-4 To a stirred solution of ethyl 2-(5-formyl-1H-pyrazol-1-yl)acetate (VIIIa, 1 g, 5.49 mmol) and diethyl (1-cyanoethyl)phosphonate (IXa, 1.259 g, 6.59 mmol) in 2-methyl tetrahydrofuran (20 mL), potassium carbonate (1.517 g, 10.98 mmol) was added at 0 °C. The reaction mixture was slowly warmed to 25 °C and stirred further for 16 h. After completion of the reaction, the reaction mixture was filtered. The obtained filtrate was concentrated to obtain ethyl 2-(5-(2-cyanoprop-1-en-1-yl)-1H-pyrazol-1- yl)acetate (VIIa, 1.1 g, 5.02 mmol, 91% yield) as an off white solid. ¹H-NMR (400 MHz, CHLOROFORM-D) δ 7.59 (d, J = 8.2 Hz, 1H), 6.49-7.16 (m, 2H), 4.97 (s, 2H), 4.21-4.27 (m, 2H), 2.17 (s, 3H), 1.26-1.31 (m, 3H). MS: m/z calcd for C₁₁H₁₃N₃O₂ : 219.10; found 220.05 (M+1). Method-5 To a stirred solution of ethyl 2-(5-formyl-1H-pyrazol-1-yl)acetate (VIIIa, 0.5 g, 2.74 mmol) and diethyl (1-cyanoethyl)phosphonate (IXa, 0.630 g, 3.29 mmol) in N,N-dimethylformamide (2.5 mL) at 25 °C, potassium carbonate (1.897 g, 13.72 mmol) was added at 25 °C. The reaction mixture was stirred further for 12 h at 25 °C. After completion of the reaction, the reaction mixture was diluted with water (15 mL), cooled to 10 °C, stirred for 1 h and filtered. The resulting solid cake was washed with n-hexane and dried under reduced pressure to obtain ethyl 2-(5-(2-cyanoprop-1-en-1-yl)-1H-pyrazol-1-yl)acetate (VIIa, 0.4 g, 1.824 mmol, 66.5% yield) as an off white solid. ¹H-NMR (400 MHz, CHLOROFORM-D) δ 7.59 (d, J = 8.2 Hz, 1H), 6.49-7.16 (m, 2H), 4.97 (s, 2H), 4.21-4.27 (m, 2H), 2.17 (s, 3H), 1.26-1.31 (m, 3H). MS: m/z calcd for C₁₁H₁₃N₃O₂: 219.10; found 220.30 (M+1). Step (c): Preparation of ethyl 6-amino-5-methylpyrazolo[1,5-a]pyridine-7-carboxylate (VIa) Method-1 To a stirred solution of ethyl 2-(5-(2-cyanoprop-1-en-1-yl)-1H-pyrazol-1-yl)acetate (VIIa, 100 g, 447 mmol) in dry tetrahydrofuran (800 mL), potassium tert-butoxide (100 g, 894 mmol) was added portion wise at -20 °C. The reaction mixture was stirred for 1.5 h at -20 °C to -10°C. After completion of the reaction, the reaction mixture was diluted with ethyl acetate (250 mL) and quenched with saturated aqueous ammonium chloride solution (250 mL). The organic layer was separated and the aqueous layer was extracted again with ethyl acetate (2 x 250 mL). The combined organic layers were washed with water (250 mL), brine solution (250 mL) and concentrated to afford ethyl 6-amino-5- methylpyrazolo[1,5-a]pyridine-7-carboxylate (VIa, 92 g, 420 mmol, 92% yield) as a light green oil. ¹H-NMR (400 MHz, DMSO-D6) δ 7.67 (d, J = 2.4 Hz, 1H), 7.50 (s, 1H), 6.38 (d, J = 2.4Hz, 1H), 6.23 (brs, 2H), 4.35 (q, J = 7.0 Hz, 2H), 2.14-2.22 (m, 3H), 1.28 (t, J =7.0 Hz, 3H). MS: m/z calcd for C₁₁H₁₃N₃O₂: 219.10; found 220.05 (M+1). Method-2 To a stirred solution of ethyl 2-(5-(2-cyanoprop-1-en-1-yl)-1H-pyrazol-1-yl)acetate (VIIa, 95 g, 433 mmol) in dry tetrahydrofuran (750 mL), potassium tert-butoxide (97 g, 867 mmol) was added portion wise at 0 °C. The reaction mixture was stirred for 15 min at 0 °C. After completion of the reaction, the reaction mixture was diluted with dichloromethane (200 mL) and quenched with saturated aqueous ammonium chloride solution (200 mL). The organic layer was separated; the aqueous layer was extracted again with dichloromethane (2 x 250 mL). The combined organic extract was washed with water (250 mL) and brine solution (50 mL), dried over sodium sulphate and concentrated to afford ethyl 6-amino-5-methylpyrazolo[1,5-a]pyridine-7-carboxylate (VIa, 58.5 g, 267 mmol, 62% yield) as a light green oil. ¹H-NMR (400 MHz, DMSO-D6) δ 7.67 (d, J = 2.4 Hz, 1H), 7.50 (s, 1H), 6.38 (d, J = 2.4Hz, 1H), 6.23 (brs, 2H), 4.35 (q, J = 7.0 Hz, 2H), 2.14-2.22 (m, 3H), 1.28 (t, J =7.0 Hz, 3H). MS: m/z calcd for C₁₁H₁₃N₃O₂: 219.10; found 220.35 (M+1) Method-3 To a stirred solution of ethyl 2-(5-(2-cyanoprop-1-en-1-yl)-1H-pyrazol-1-yl)acetate (VIIa, 0.2 g, 0.912 mmol) in acetonitrile (6 mL), sodium ethoxide (0.186 g, 2.74 mmol) was added at 0°C under nitrogen atmosphere. The reaction mixture was stirred for 3 h at 0 °C to 25 °C. After completion of the reaction, the reaction mixture was diluted with dichloromethane (5 mL) and quenched with saturated ammonium chloride solution (3 mL). The organic layer was separated and the aqueous layer extracted with dichloromethane (2 x 10 mL). The combined organic layer was dried over sodium sulphate and concentrated to afford ethyl 6-amino-5-methylpyrazolo[1,5-a]pyridine-7-carboxylate (VIa, 0.120 g, 0.547 mmol, 60% yield) as a light green oil. ¹H-NMR (400 MHz, DMSO-D6) δ 7.67 (d, J = 2.4 Hz, 1H), 7.50 (s, 1H), 6.38 (d, J = 2.4Hz, 1H), 6.23 (brs, 2H), 4.35 (q, J = 7.0 Hz, 2H), 2.14-2.22 (m, 3H), 1.28 (t, J =7.0 Hz, 3H). MS: m/z calcd for C₁₁H₁₃N₃O₂: 219.10; found 220.35 (M+1) Method-4 To a stirred solution of ethyl 2-(5-(2-cyanoprop-1-en-1-yl)-1H-pyrazol-1-yl)acetate (VIIa, 0.2 g, 0.912 mmol) in dry tetrahydrofuran (7 mL), sodium ethoxide (0.186 g, 2.74 mmol) was added at 0 °C. The reaction mixture was stirred for 3 h at 0 °C-25 °C. After completion of the reaction, the reaction mixture was diluted with dichloromethane (5 mL) and quenched with saturated aqueous ammonium chloride solution (3 mL). The organic layer was separated and the aqueous layer extracted with dichloromethane (2 x 10 mL). The combined organic layer was dried over sodium sulphate and concentrated to afford ethyl 6-amino-5-methylpyrazolo[1,5-a]pyridine-7-carboxylate (VIa, 0.120 g, 0.547 mmol, 60% yield) as a light green oil. ¹H-NMR (400 MHz, DMSO-D6) δ 7.67 (d, J = 2.4 Hz, 1H), 7.50 (s, 1H), 6.38 (d, J = 2.4Hz, 1H), 6.23 (brs, 2H), 4.35 (q, J = 7.0 Hz, 2H), 2.14-2.22 (m, 3H), 1.28 (t, J =7.0 Hz, 3H). MS: m/z calcd for C₁₁H₁₃N₃O₂: 219.10; found 220.35 (M+1) Method-5 To a stirred solution of ethyl 2-(5-(2-cyanoprop-1-en-1-yl)-1H-pyrazol-1-yl)acetate (VIIa, 1 g, 4.56 mmol) in 1,4-dioxane (15 mL), cesium carbonate (4.46 g, 13.68 mmol) was added at 25 °C under nitrogen atmosphere. The reaction mixture was stirred for 15 h at 100 °C. After completion of the reaction, the reaction mixture was filtered and the filtrate was concentrated to afford ethyl 6-amino-5- methylpyrazolo[1,5-a]pyridine-7-carboxylate (VIa, 0.38 g, 1.733 mmol, 38% yield) as a light green oil. ¹H-NMR (400 MHz, DMSO-D6) δ 7.67 (d, J = 2.4 Hz, 1H), 7.50 (s, 1H), 6.38 (d, J = 2.4Hz, 1H), 6.23 (brs, 2H), 4.35 (q, J = 7.0 Hz, 2H), 2.14-2.22 (m, 3H), 1.28 (t, J =7.0 Hz, 3H). MS: m/z calcd for C₁₁H₁₃N₃O₂: 219.10; found 220.35 (M+1) Method-6 To a stirred solution of ethyl 2-(5-(2-cyanoprop-1-en-1-yl)-1H-pyrazol-1-yl)acetate (VIIa, 10.0 g, 45.2 mmol) in 2-methyltetrahydrofuran (150 mL), potassium tert-butoxide (10.13 g, 90.0 mmol) was added portion wise at -5 °C. The reaction mixture was stirred for 50 min at 0 °C. After completion of the reaction, the reaction mixture was diluted with 2-methyltetrahydrofuran (30 mL) and quenched with saturated aq. ammonium chloride solution (30 mL). The organic layer was separated and the aqueous layer was extracted again with 2-methyltetrahydrofuran (2 × 30 mL). The combined organic layers were washed with water (30 mL), brine solution (30 mL) and concentrated to afford ethyl 6-amino-5- methylpyrazolo[1,5-a]pyridine-7-carboxylate (VIa, 8.0 g, 36.5 mmol, 81% yield) as a light green oil. ¹H-NMR (400 MHz, DMSO-D6): δ 7.67 (d, J = 2.4 Hz, 1H), 7.50 (s, 1H), 6.38 (d, J = 2.4Hz, 1H), 6.23 (brs, 2H), 4.35 (q, J = 7.0 Hz, 2H), 2.14-2.22 (m, 3H), 1.28 (t, J =7.0 Hz, 3H). MS: m/z 220.00 [M+1]⁺ Step (d): Preparation of 6-amino-5-methylpyrazolo[1,5-a]pyridine-7-carboxylic acid (Va) Method-1 To a stirred solution of ethyl 6-amino-5-methylpyrazolo[1,5-a]pyridine-7-carboxylate (VIa, 93 g, 424 mmol) in tetrahydrofuran (930 mL), water (150 mL) and methanol (80 mL), lithium hydroxide monohydrate hydrate (35.6 g, 848 mmol) was added at 25°C and stirred for 1 h. After completion of the reaction, the reaction mixture was concentrated under reduced pressure. The resulting residue was diluted with water (100 mL) and washed with ethyl acetate (200 mL). The pH of aqueous layer was adjusted to 4-5 using 20% aq. citric acid solution. The precipitate obtained was stirred for further 30 min and then filtered. The resulting wet cake was washed with water (50 mL) and dried under reduced pressure to afford 6-amino-5-methylpyrazolo[1,5-a]pyridine-7-carboxylic acid (Va, 55 g, 288 mmol, 67.8% yield) as an off white solid. ¹H-NMR (400 MHz, DMSO-D6) δ 15.66 (brs, 1H), 7.90 (d, J = 2.4 Hz, 1H), 7.67 (s, 1H), 7.40 (s, 2H), 6.60 (d, J = 2.4 Hz, 1H), 2.24 (s, 3H) MS: m/z calcd for C₁₁H₁₃N₃O₂: 191.07; found 191.85 (M+1) Method-2 To a stirred solution of ethyl 6-amino-5-methylpyrazolo[1,5-a]pyridine-7-carboxylate (VIa, 135 g, 585 mmol) in ethanol (1000 mL), aqueous 3 M sodium hydroxide solution (195 mL, 585 mmol) was added at 15 °C. The reaction mixture was slowly warmed to 25 °C and stirred for 2.5 h. After completion of the reaction, the reaction mixture was concentrated under reduced pressure. The resulting residue was diluted with water (1.5 L), pH was adjusted to 4-5 by using 40% aq. solution of citric acid. The obtained precipitate was stirred for further 1 h and filtered. The wet cake which was obtained was washed with water (200 mL) and dried under reduced pressure to afford 6-amino-5-methylpyrazolo[1,5-a]pyridine- 7-carboxylic acid (Va, 100 g, 523 mmol, 89% yield) as an off white solid. ¹H -NMR (400 MHz, DMSO-D6) δ 15.66 (brs, 1H), 7.90 (d, J = 2.4 Hz, 1H), 7.67 (s, 1H), 7.40 (s, 2H), 6.60 (d, J = 2.4 Hz, 1H), 2.24 (s, 3H) MS: m/z calcd for C₁₁H₁₃N₃O₂: 191.07; found 191.60 (M+1) Method-3 To a stirred solution of ethyl 6-amino-5-methylpyrazolo[1,5-a]pyridine-7-carboxylate (VIa, 10.0 g, 43.3 mmol) in 2-methyltetrahydrofuran (100 mL) was added aqueous 2M NaOH solution (32.5 mL, 65.0 mmol) at 15 °C. The reaction mixture was stirred for 12 h at 25 °C. After completion of the reaction, the reaction mixture was diluted with water (50 mL), the aqueous layer was separated and pH was adjusted to 4-5 using 20% aq. citric acid solution. The obtained precipitate was stirred further for 30 min and filtered. The resulting wet cake was washed with water (5 mL) and dried under reduced pressure to afford 6-amino-5-methylpyrazolo[1,5-a]pyridine-7-carboxylic acid (Va, 7.6 g, 39.8 mmol, 92% yield) as an off white solid. ¹H-NMR (400 MHz, DMSO-D6): δ 15.66 (brs, 1H), 7.90 (d, J = 2.4 Hz, 1H), 7.67 (s, 1H), 7.40 (s, 2H), 6.60 (d, J = 2.4 Hz, 1H), 2.24 (s, 3H) MS: m/z 192.00 [M+1]⁺ Method 4 To a stirred solution of ethyl 2-(5-formyl-1H-pyrazol-1-yl)acetate (VIIIa, 10.0 g, 52.1 mmol) and diethyl (1-cyanoethyl)phosphonate (IXa, 11.92 g, 57.4 mmol) in 2-methyltetrahydrofuran (100 mL), potassium carbonate (18.02 g, 130.0 mmol) was added at 15 °C. The reaction mixture was slowly warmed to 25 °C and stirred further for 16 h. After completion of the reaction, the reaction mixture was filtered. Potassium tert-butoxide (17.55 g, 156.0 mmol) was added to the filtrate portion wise at 0-3 °C. The reaction mixture was then stirred for 60 min at 4-10 °C. After completion of the reaction, the reaction mixture was diluted with water (100 mL) followed by the addition of aq.2M NaOH solution (52.1 mL, 104.0 mmol) at 5 °C and continued to stir further for 16 h at 25 °C. The reaction mixture was diluted with water (50 mL), aqueous layer was separated and pH was adjusted to 4-5 using 20% aq. citric acid solution. The obtained precipitate was stirred for further 1 h and filtered. The wet cake which was obtained was washed with water (5 mL) and dried under reduced pressure to afford 6-amino-5- methylpyrazolo[1,5-a]pyridine-7-carboxylic acid (Va, 5.51 g, 28.8 mmol, 55.3% yield) as an off white solid. ¹H-NMR (400 MHz, DMSO-D6): δ 15.66 (brs, 1H), 7.90 (d, J = 2.4 Hz, 1H), 7.67 (s, 1H), 7.40 (s, 2H), 6.60 (d, J = 2.4 Hz, 1H), 2.24 (s, 3H) MS: m/z 192.00 [M+1]⁺ Method 5: To a stirred solution of ethyl 2-(5-(2-cyanoprop-1-en-1-yl)-1H-pyrazol-1-yl)acetate (VIIa, 20 g, 90.0 mmol) in 2-methyltetrahydrofuran (200 mL), potassium tert-butoxide (20.27 g, 181 mmol) was added portion wise at 4 °C. The reaction mixture was stirred for 1 h at a temperature between 4 °C to 10 °C. After completion of the reaction, water (250 mL) and aq. 2M NaOH solution (90 mL, 181.0 mmol) were added at 5 °C. The reaction mixture was stirred further for 16 h at 25°C and then diluted with water (150 mL). Aqueous layer was separated and pH was adjusted to 4-5 using 20% aq. citric acid solution. The precipitate obtained was stirred for further 1 h and then filtered. The wet cake which was obtained was washed with water (10 mL) and dried under reduced pressure to afford 6-amino-5- methylpyrazolo[1,5-a]pyridine-7-carboxylic acid (Va, 13.75 g, 71.9 mmol, 80% yield) as an off white solid. ¹H-NMR (400 MHz, DMSO-D6): δ 15.66 (brs, 1H), 7.90 (d, J = 2.4 Hz, 1H), 7.67 (s, 1H), 7.40 (s, 2H), 6.60 (d, J = 2.4 Hz, 1H), 2.24 (s, 3H) MS: m/z 192.00 [M+1]⁺ Step (e ): Preparation of 7-(3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl)-5-methyl-9H- pyrazolo[1',5':1,6]pyrido[3,2-d][1,3]oxazin-9-one (III) Method-1 A solution of methanesulfonyl chloride (122 mL, 1569 mmol) in acetonitrile (400 mL) was cooled to 0 °C, and a solution of 3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxylic acid (IV, 237 g, 785 mmol) and pyridine (127 mL, 1569 mmol) in acetonitrile (600 mL) was added to it in a drop wise manner over a period of 10 min. The resulting slurry mixture was stirred for 15 minutes, and then a solution of 6-amino-5-methylpyrazolo[1,5-a]pyridine-7-carboxylic acid (Va, 150 g, 785 mmol) and pyridine (127 mL, 1569 mmol) in acetonitrile (700 mL) was added. The reaction mixture was further stirred for 10 min, after which a solution of methanesulfonyl chloride (122 mL, 1569 mmol) in acetonitrile (200 ml) was added in a drop wise manner during 5 min. The reaction mixture was further stirred for 2 h at 0 °C and then warmed slowly to 25 °C while stirring further for 16 h. After completion of the reaction, the reaction mixture was diluted with water (2000 mL) and stirred for 30 min. The resulting slurry mass was filtered and the solid cake was washed with water and dried under reduced pressure to afford 7-(3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl)-5-methyl-9H- pyrazolo[1',5':1,6]pyrido[3,2-d][1,3]oxazin-9-one (IIIa, 320 g, 699 mmol, 89% yield) as a light green solid. ¹H-NMR (400 MHz, DMSO-D6) δ 8.64 (dd, J = 4.7, 1.5 Hz, 1H), 8.36 (dd, J = 8.1, 1.5 Hz, 1H), 8.18 (d, J = 2.1 Hz, 1H), 7.93-7.97 (s, 1H), 7.77 (dd, J = 8.1, 4.7 Hz, 1H), 7.57 (s, 1H), 6.79 (d, J = 2.1 Hz, 1H), 1.67 (s, 3H) MS: m/z calcd for C₁₈H₁₀BrClN₆O₂: 455.97; found 458.95 Method-2 A solution of methanesulfonyl chloride (0.408 mL, 5.23 mmol) in acetonitrile (3 mL) was cooled to 0 °C. To that, a solution of 3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxylic acid (IV, 0.791 g, 2.62 mmol) and 3-methylpyridine (0.487 g, 5.23 mmol) in acetonitrile (5 mL) was added drop wise and under stirring during 2 minutes at 0 °C. The resulting slurry mixture was stirred for further 15 minutes at the same temperature. A solution of 6-amino-5-methylpyrazolo[1,5-a]pyridine-7-carboxylic acid (Va, 0.5 g, 2.62 mmol), 3-methylpyridine (0.507 mL, 5.23 mmol) in acetonitrile (5 mL) was added to the reaction mixture, which was stirred for further 5 min at 0 °C, followed by adding drop wise a solution of methanesulfonyl chloride (0.408 mL, 5.23 mmol) in acetonitrile (3 mL) during 1 min. The reaction mixture was stirred for 2 h at 0 °C, allowed to slowly warm up to 25 °C and stirred further for 16 h. The reaction mixture was diluted with water (10 mL) and stirred for 30 min. The resulting slurry mass was filtered to obtained a solid cake, which was washed with water and dried under reduced pressure to obtain 7-(3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl)-5-methyl-9H- pyrazolo[1',5':1,6]pyrido[3,2-d][1,3]oxazin-9-one (IIIa, 0.9 g, 1.966 mmol, 75% yield) as a light green solid. ¹H-NMR (400 MHz, DMSO-D6) δ 8.64 (dd, J = 4.7, 1.5 Hz, 1H), 8.36 (dd, J = 8.1, 1.5 Hz, 1H), 8.18 (d, J = 2.1 Hz, 1H), 7.93-7.97 (s, 1H), 7.77 (dd, J = 8.1, 4.7 Hz, 1H), 7.57 (s, 1H), 6.79 (d, J = 2.1 Hz, 1H), 1.67 (s, 3H) MS: m/z calcd for C₁₈H₁₀BrClN₆O₂: 455.97; found 459.25 Step (f): Preparation of 6-(3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxamido)-N- isopropyl-5-methylpyrazolo[1,5-a]pyridine-7-carboxamide (Ia) Method-1 To a stirred solution of 7-(3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl)-5-methyl-9H- pyrazolo[1',5':1,6]pyrido[3,2-d][1,3]oxazin-9-one (IIIa, 590 g, 1289 mmol) in acetonitrile (4000 mL), propan-2-amine (II, 167 mL, 1934 mmol) was added in drop wise manner at 15 °C. The reaction mixture was allowed to warm up to 25 °C and stirred for 2 h. After completion of the reaction, the reaction mixture was diluted with water (4 L) and stirred for 1 h. The resulting slurry mass was filtered to obtain a solid cake, which was washed with water (0.5 L) and dried under reduced pressure to afford 6-(3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxamido)-N-isopropyl-5- methylpyrazolo[1,5-a]pyridine-7-carboxamide (Ia, 600 g, 1161 mmol, 90% yield) as an off white solid. ¹H-NMR (400 MHz, DMSO-D6) δ 10.40 (s, 1H), 8.42-8.49 (m, 2H), 8.17 (dd, J = 7.9, 1.5 Hz, 1H), 7.99 (d, J = 2.3 Hz, 1H), 7.56-7.61 (m, 2H), 7.42 (s, 1H), 6.56 (d, J = 2.3 Hz, 1H), 3.99-4.07 (m, 1H), 2.13 (s, 3H), 1.05-1.14 (m, 6H) MS: m/z calcd for C₂₁H₁₉BrClN₇O₂: 515.05; found 516.60 (M+1) Method-2 To a stirred solution of 7-(3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl)-5-methyl-9H- pyrazolo[1',5':1,6]pyrido[3,2-d][1,3]oxazin-9-one (IIIa, 330 g, 721 mmol) in tetrahydrofuran (2000 mL), propan-2-amine (II, 85 g, 1442 mmol) was added in a drop wise manner at 15-20 °C. The reaction mixture was allowed to warm up to 25 °C and stirred for 2 h. After completion of the reaction, the reaction mixture was diluted with water (1000 mL) and extracted with ethyl acetate (2 x 500 mL). The organic layer was concentrated to obtain a residue, which was subjected to a solution of acetonitrile (400 mL) in water (1600 mL), which was stirred for 1 h at 25 °C. The resulting slurry mass was filtered to obtained a wet cake which was again taken up in methanol (1000 mL), stirred at 60 °C, cooled to 25 °C, filtered and dried under reduced pressure to afford 6-(3-bromo-1-(3-chloropyridin-2-yl)-1H- pyrazole-5-carboxamido)-N-isopropyl-5-methylpyrazolo[1,5-a]pyridine-7-carboxamide (Ia, 275 g, 532 mmol, 83% yield) as an off white solid. ¹H-NMR (400 MHz, DMSO-D6) δ 10.40 (s, 1H), 8.42-8.49 (m, 2H), 8.17 (dd, J = 7.9, 1.5 Hz, 1H), 7.99 (d, J = 2.3 Hz, 1H), 7.56-7.61 (m, 2H), 7.42 (s, 1H), 6.56 (d, J = 2.3 Hz, 1H), 3.99-4.07 (m, 1H), 2.13 (s, 3H), 1.05-1.14 (m, 6H) MS: m/z calcd for C₂₁H₁₉BrClN₇O₂: 515.05; found 516.35 (M+1) Method-3 A mixture of 7-(3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl)-5-methyl-9H- pyrazolo[1',5':1,6]pyrido[3,2-d][1,3]oxazin-9-one (IIIa, 0.2 g, 0.437 mmol) in propan-2-amine (II, 1 mL, 12.21 mmol) was stirred at 25 °C for 2 h. After completion of the reaction, the reaction mixture was evaporated to obtain 6-(3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxamido)-N- isopropyl-5-methylpyrazolo[1,5-a]pyridine-7-carboxamide (Ia, 0.160 g, 0.310 mmol, 71% yield) as an off white solid. ¹H-NMR (400 MHz, DMSO-D6) δ 10.40 (s, 1H), 8.42-8.49 (m, 2H), 8.17 (dd, J = 7.9, 1.5 Hz, 1H), 7.99 (d, J = 2.3 Hz, 1H), 7.56-7.61 (m, 2H), 7.42 (s, 1H), 6.56 (d, J = 2.3 Hz, 1H), 3.99-4.07 (m, 1H), 2.13 (s, 3H), 1.05-1.14 (m, 6H) MS: m/z calcd for C₂₁H₁₉BrClN₇O₂: 515.05; found 516.45 (M+1) Scheme 2:

Step (1): Preparation of 6-(3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxamido)-5- methylpyrazolo[1,5-a]pyridine-7-carboxylate (IIIA) To a solution of methanesulfonyl chloride (1.21 mL, 15.51 mmol) in acetonitrile (3 mL) that was cooled to 0 °C, a solution of 3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxylic acid (IV, 2.346 g, 7.75 mmol) and pyridine (0.487 g, 5.23 mmol) in acetonitrile (3 mL) was added drop wise, under stirring over a period of 2 min at 0 °C. The resulting slurry mixture was stirred for further 15 min at 0 °C. A solution of ethyl 6-amino-5-methylpyrazolo[1,5-a]pyridine-7-carboxylate (VI, 2.0 g, 7.75 mmol) and pyridine (1.254 mL, 15.51 mmol) in acetonitrile (3 mL) was added to the reaction mixture at 0 °C. The reaction mixture was stirred further for 2 h at 0 °C and then allowed to slowly warm up to 25 °C and stirred further for 16 h. The reaction mixture was diluted with water (10 mL) and extracted in DCM (2 × 20 mL). The combined organic layers were concentrated under reduced pressure to obtain a crude product which was purified by column chromatography using 100-200 mesh silica gel and 35% ethyl acetate in n-hexane as eluent to obtain 6-(3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5- carboxamido)-5-methylpyrazolo[1,5-a]pyridine-7-carboxylate (IIIA, 3.6 g, 7.15 mmol, 92% yield) as a light orange solid. ¹H-NMR (400 MHz, CHLOROFORM-D): δ 8.53 (s, 1H), 8.45 (dd, J = 4.6, 1.7 Hz, 1H), 7.96 (d, J = 2.4 Hz, 1H), 7.86 (dd, J = 8.1, 1.7 Hz, 1H), 7.38 (dd, J = 8.1, 4.6 Hz, 1H), 7.29 (s, 1H), 7.06 (s, 1H), 6.44 (d, J = 2.4 Hz, 1H), 4.52 (q, J = 7.1 Hz, 2H), 2.12 (s, 3H), 1.37 (t, J = 7.1 Hz, 3H) MS: m/z 504.95 Step (2): Preparation of 6-(3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxamido)-N- isopropyl-5-methylpyrazolo[1,5-a]pyridine-7-carboxamide (Ia) A mixture of ethyl 6-(3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxamido)-5- methylpyrazolo[1,5-a]pyridine-7-carboxylate (IIIa, 0.2 g, 0.40 mmol) in propan-2-amine (II, 4 mL) was stirred at 50 °C for 16 h. After completion of the reaction, the reaction mixture was concentrated to obtain 6-(3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxamido)-N-isopropyl-5- methylpyrazolo[1,5-a]pyridine-7-carboxamide (Ia, 0.100 g, 0.210 mmol, 48.7% yield) as an off white solid. ¹H-NMR (400 MHz, DMSO-D6): δ 10.40 (s, 1H), 8.42-8.49 (m, 2H), 8.17 (dd, J = 7.9, 1.5 Hz, 1H), 7.99 (d, J = 2.3 Hz, 1H), 7.56-7.61 (m, 2H), 7.42 (s, 1H), 6.56 (d, J = 2.3 Hz, 1H), 3.99-4.07 (m, 1H), 2.13 (s, 3H), 1.05-1.14 (m, 6H) MS: m/z 517.95

Claims

CLAIMS: 1. A process for preparing the intermediate of formula (Z) or a salt thereof,

wherein, R is selected from the group consisting of OR⁶ and NHR^aR^b; R⁶ is selected from the group consisting of hydrogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, and C₂-C₄- alkenyl; R^a and R^b are independently selected from the group consisting of hydrogen, C₁-C₆-alkyl, C2- C6-alkenyl, C₃-C₆-cycloalkyl, C₁-C₆-haloalkyl, C₃-C₆-halocycloalkyl and C₃-C₆-cycloalkyl-C1- C6-alkyl; R¹ and R^1a are independently selected from the group consisting of hydrogen, halogen, C₁-C₄- alkyl, C₁-C₄-haloalkyl, C₂-C₄-alkenyl and C₃-C₆-cycloalkyl; comprising the steps of: a) reacting a substituted acetonitrile (R¹CH₂-CN) of formula (X) with a phosphorochloridate of formula (XI) or a salt thereof,

in the presence of a suitable base, a suitable reagent and a suitable solvent to obtain a (substituted) cyanomethylphosphonate of formula (IX) or a salt thereof,

wherein, R⁴ and R⁵ are each independently selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-haloalkyl and C₂-C₄-alkenyl; or R⁴ and R⁵ together with the O atom to which they are attached may form a 5-8-membered ring; and R¹ is as defined herein above; b) condensing the compound of formula (IX) or a salt thereof with a compound of formula (VIII) or a salt thereof,

in the presence of a suitable base and a suitable solvent to obtain a compound of formula (VII) or a salt thereof,

wherein, R⁶ is selected form the group consisting of C₁-C₄-alkyl, C₁-C₄-haloalkyl and C₂-C₄- alkenyl; R¹ and R^1a are as define herein above; c) cyclising the compound of formula (VII) or a salt thereof in the presence of a suitable base and a suitable solvent to obtain a compound of formula (VI) or a salt thereof,

wherein, R¹, R^1a and R⁶ are as define herein above; d) hydrolysing the compound of formula (VI) or a salt thereof in the presence of a suitable hydrolysing reagent and a suitable solvent to obtain a compound of formula (V) or a salt thereof,

wherein, R¹ and R^1a are as define herein above; e) amidating the compound of formula (VI) or compound of formula (V) or a salt thereof with an amine (NHR^aR^b) of formula (II) to obtain a compound of formula (XII) or a salt thereof,

, wherein, R¹, R^1a, R^a and R^b are as defined herein above.

2. The process as claimed in claim 1, wherein said process for preparing the compound of formula (V) comprises the step of: cyclizing the compound of formula (VII) or a salt thereof, in the presence of a suitable base, and a suitable solvent to obtain the compound of formula (VI) or a salt thereof; which is reacted in situ with a suitable hydrolysing agent to obtain the compound of formula (V) or a salt thereof; as shown in below scheme:

, wherein, R¹, R^1a and R⁶ are as defined in claim1.

3. The process as claimed in claim 1, wherein said process for preparing the compound of formula (V) comprises the step of: condensing the compound of formula (IX) or a salt thereof with a compound of formula (VIII) or a salt thereof, in the presence of a suitable base, and a suitable solvent to obtain a compound of formula (VII) or a salt thereof; which is reacted in situ with a suitable base to obtain the compound of formula (VI) or a salt thereof; which is reacted in situ with a suitable hydrolysing agent to obtain the compound of formula (V) or a salt thereof; as shown in below scheme:

, wherein, R¹, R^1a and R⁶, are as defined in claim 1.

4. The process as claimed in claim 1, wherein said process further comprises a process for preparing a compound of formula (I),

wherein, R¹ and R^1a are independently selected from the group consisting of hydrogen, halogen, C₁-C₄- alkyl, C₁-C₄-haloalkyl, C₂-C₄-alkenyl and C₃-C₆-cycloalkyl; R^a and R^b are independently selected from the group consisting of hydrogen, C₁-C₆-alkyl, C2- C6-alkenyl, C₃-C₆-cycloalkyl, C₁-C₆-haloalkyl, C₃-C₆-halocycloalkyl, and C₃-C₆-cycloalkyl- C₁-C₆-alkyl; R² is selected from the group consisting of halogen, CHF₂, CF₃, OCF₂H, OCH₂CF₃ and ; wherein A represents CR^cR^c, NR^c, O or S(O)_0-2; R^c is selected from the group consisting of hydrogen and C_1-C₄-alkyl; R³ is selected from the group consisting of hydrogen, halogen, C₁-C₄-alkyl and C₁-C₄-haloalkyl; and n is an integer, selected from 1 to 3; f) reacting the compound of formula (V) or the compound formula (VI) or a salt thereof with a compound of formula (IV) or a salt thereof,

in the presence of a suitable reagent, a suitable base and a suitable solvent to obtain a compound of formula (III) or a salt thereof;

wherein, R¹, R^1a, R², R³ and n are as define herein above; and g) amidating the compound of formula (III) or a salt thereof, with an amine (NHR^aR^b) of formula (II) to obtain a compound of formula (I) or a salt thereof;

wherein, R¹, R^1a, R^a, R^b, R², R³ and n are as define herein above; optionally, h) reacting the compound of formula (XII) or a salt thereof,

with a compound of formula (IV) or a salt thereof,

in the presence of a suitable reagent, a suitable base and a suitable solvent, to obtain a compound of formula (I) or a salt thereof;

wherein, R¹, R^1a, R^a, R^b, R², R³ and n are as define herein above.

5. A process for preparing a compound of the formula (Ia) or a salt thereof,

wherein, R¹ is selected from the group consisting of methyl, trifluromethyl, or halogen; R^a is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-, iso- or tert-butyl; and R^b is selected from the group consisting of hydrogen or methyl; comprising the steps of: a) reacting an acetonitrile (CH₃CH₂-CN) of formula (Xa) with a phosphorochloridate of formula (XIa) or a salt thereof,

in the presence of a suitable base, a suitable reagent and a suitable solvent, to obtain a diethyl (substituted) cyanomethylphosphonate of formula (IXa) or a salt thereof,

wherein R¹ is as defined herein above; b) condensing the compound of formula (IXa) or a salt thereof, with a compound of formula (VIIIa) or a salt thereof,

in the presence of a suitable base and a suitable solvent, to obtain a compound of formula (VIIa) or a salt thereof,

wherein R¹ is as defined herein above; c) cyclising the compound of formula (VIIa) or a salt thereof, in the presence of a suitable base and a suitable solvent, to obtain a compound of formula (VIa) or a salt thereof,

wherein R¹ is as defined herein above; d) hydrolysing the compound of formula (VIa) or a salt thereof, in the presence of a suitable hydrolysing reagent and a suitable solvent, to obtain a compound of formula (Va) or a salt thereof,

wherein R¹ is as defined herein above; optionally, e) amidating the compound of formula (VIa) or compound of formula (Va) or a salt thereof, with a suitable amine [(CH₃)₂CH-NH₂] of formula (IIa), to obtain a compound of formula (XIIa) or a salt thereof,

wherein R¹, R^a and R^b are as defined herein above; f) coupling the compound of formula (Va) or a salt thereof, with a compound of formula (IVa) or a salt thereof,

in the presence of a suitable coupling reagent, a suitable base and a suitable solvent, to obtain a compound of formula (IIIa) or a salt there of,

wherein R¹ is as defined herein above; and g) amidating the compound of formula (IIIa) or a salt thereof, with a suitable amine [(CH3)2CH- NH₂] of formula (IIa), to obtain a compound of formula (Ia) or a salt thereof,

wherein R¹, R^a and R^b are as defined herein above; optionally, h) coupling the compound of formula (XIIa) or a salt thereof,

with a compound of formula (IVa) or a salt thereof,

in the presence of a suitable reagent, a suitable base and a suitable solvent, to obtain a compound of formula (Ia) or a salt there of,

wherein R¹, R^a and R^b are as defined herein above. 6. The process as claimed in claim 1 or 5, wherein i. the suitable solvent in the process step (a) is an ether, selected from the group consisting of diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 2-methyl tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, cyclopentylmethylether or a mixture thereof; ii. the suitable base used in the process step (a) is diisopropylamine; iii. the suitable reagent used in the process step (a) is n-butyllithium; and iv. the process step (a) is performed within a temperature range from -100 °C to 50 °C. 7. The process as claimed in claim 1 or 5, wherein i. the suitable solvent used in the process step (b) is selected from the group consisting of diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2- dimethoxyethane, 1,2-diethoxyethane, acetone, butanone, methyl isobutyl ketone, cyclohexanone, acetonitrile, propionitrile, n- or i-butyronitrile, benzonitrile, N,N- dimethylformamide, N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone, N′, N′-dimethylpropyleneurea, hexamethylphosphoramide, methyl acetate, ethyl acetate, dimethyl sulphoxide, sulpholane, dimethyl sulfone or a mixture thereof; ii. the suitable base used in the process step (b) is selected from the group consisting of lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, 2,3,4,

6,

7,8,9,10- octahydropyrimidol[1,2-a]azepine (DBU), 1,8-diazabicyclo(5.4.0)undec-7-ene, 1,5- diazabicyclo[4.3.0]non-5-ene (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), ethylamine, triethylamine, isopropylamine diisopropylamine, triisopropylamine, pyridine, piperidine, N,N-(dimethylamino)pyridine (DMAP) or a mixture thereof; and iii. the process step (b) is performed within a temperature range from 0 °C to 50 °C.

8. The process as claimed in claim 1 or 5, wherein i. the suitable solvent used in the process step (c) is selected from the group consisting of diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2- dimethoxyethane, 1,2-diethoxyethane, acetone, butanone, methyl isobutyl ketone, cyclohexanone, acetonitrile, propionitrile, n- or i-butyronitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone, N,N′- dimethylpropyleneurea or hexamethylphosphoramide, methyl acetate, ethyl acetate, dimethyl sulphoxide, sulpholane, an dimethyl sulfone or a mixture thereof; ii. the suitable base used in the process step (c) is selected from the group consisting of metal carbonate, metal alkoxide, alkali hydride or a mixture thereof; and iii. the process step (c) is performed within a temperature range from -50 °C to 50 °C.

9. The process as claimed in claim 1 or 5, wherein i. the suitable solvent used in the process step (d) is selected from the group consisting of diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2- dimethoxyethane, 1,2-diethoxyethane; alcohols such as methanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, water or a mixture thereof; ii. the hydrolysing agent used in the process step (d) is selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate or a mixture thereof; and iii. the process step (d) is performed within a temperature range from -0 °C to 50 °C.

10. The process as claimed in claim 4 or 5, wherein i. the suitable solvent used in the process step (e or f or h) is selected from the group consisting of diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, acetone, butanone, methyl isobutyl ketone, cyclohexanone, acetonitrile, propionitrile, n- or i-butyronitrile, chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane or a mixture thereof; ii. the suitable reagent used in the process step (e or f or h) is selected from the group consisting of oxalyl chloride and methanesulphonyl chloride; iii. the suitable base in the process step (e or f or h) is selected from the group consisting of triethylamine, diisopropylamine, 3-methylpyridine, pyridine, piperidine, lithium carbonate, sodium carbonate, potassium carbonate and a mixture thereof; and iv. the process step (e or f or h) is performed within a temperature range from 0 °C to 100 °C.

11. The process as claimed in claim 4 or 5, wherein i. the suitable solvent used in the process step (g) is selected from the group consisting of diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2- dimethoxyethane, 1,2-diethoxyethane, acetone, butanone, methyl isobutyl ketone, cyclohexanone, acetonitrile, propionitrile, n- or i-butyronitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone, N,N′- dimethylpropyleneurea or hexamethylphosphoramide, methyl acetate, ethyl acetate, dimethyl sulphoxide, sulpholane, dimethyl sulfone or a mixture thereof. ii. the process step (g) is performed within a temperature range from 0 °C to 100 °C.

12. A compound of formula (IIIA)

wherein, R¹ and R^1a are independently selected from the group consisting of hydrogen, halogen, C₁-C₄- alkyl, C₁-C₄-haloalkyl, C₂-C₄-alkenyl and C₃-C₆-cycloalkyl; R² is selected from the group consisting of halogen, CHF₂, CF₃, OCF₂H, OCH₂CF₃, and ; wherein A represents CR^cR^c, NR^c, O or S(O)_0-2; R^c is selected from the group consisting of hydrogen and C_1-C₄-alkyl; R³ is selected from the group consisting of hydrogen, halogen, C₁-C₄-alkyl and C₁-C₄-haloalkyl; R⁶ is selected from the group consisting of hydrogen and C₁-C₄-alkyl; n is an integer, selected from 1 to 3.