WO2016071243A1

WO2016071243A1 - Process for preparing halogenated alkenone ethers and their use in the synthesis of anthranilamide pesticides

Info

Publication number: WO2016071243A1
Application number: PCT/EP2015/075346
Authority: WO
Inventors: Stefan BENSON; Thomas Zierke; Roland Goetz; Bernhard WALK; Monika DOMRES
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2014-11-05
Filing date: 2015-10-30
Publication date: 2016-05-12
Anticipated expiration: 2017-05-05

Abstract

The present invention relates to a process for preparing a compound of formula (III) starting from the vinyl ether (IlIa) and the compound (IIIb) with a reagent (lllc) selected from the group of sulfonylhalides or sulfonylanhydrides, e.g. methanesulfonyl chloride or p-toluenesulfonyl chloride, in the presence of a base. The present invention relates also to processes comprising further preceding and/or subsequent reaction steps, leading to anthranilamide pesticides or to precursors for them.

Description

Process for preparing halogenated alkenone ethers and their use in the synthesis of

anthranilamide pesticides

Description

The present invention relates to a process for preparing vinyl ether compounds which are useful precursors for pyridylpyrazole compounds and derivatives thereof, in particular pyridylpyrazole carbonyl compounds. It also relates to the use of these pyridylpyrazole carbonyl compounds for preparing anthranilamide derivatives that are useful pesticides. Therefore, vinyl ether compounds and pyridylpyrazole compounds are important precursors for anthranilamide derivates. Such compounds find use as pesticides, especially as insecticides, which are disclosed, for example, in WO 01/70671 , WO 03/015518, WO 03/015519, WO 03/016284, WO 03/016300, WO 03/024222, WO2003/062221 , WO2003/027099, WO2004/067528,

WO2003/106427, WO 06/000336; WO 06/068669, WO 07/043677, WO2008/126933,

WO2008/126858, and WO2008/130021 , and in WO2007/006670, WO2013/024009,

WO2013/024010, WO2013/024003, WO2013/024004, WO2013/024005, WO2013/024006, WO2013/024169, WO2013/024170, WO2013/024171 .

It is an object of the present invention to provide alternative or improved processes for preparing vinyl ether compounds and for preparing pyridylpyrazole compounds,

pyrazolecarboxamides or anthranilamides derived therefrom. These processes should be simple to carry out, require only few steps and be suitable for the industrial scale production. The processes should have good yields and good product purity, and start from readily available starting materials. They should also use as few starting materials as possible. They should additionally be inexpensive and safe and be based on selective reactions.

The object is achieved by the processes described in detail hereinafter.

In a first aspect, the present invention relates to a process for preparing a compound of formula

(III)

in which

R¹ is selected from CF3 and CHF2; and

R² is selected from Ci-C6-alkyl, C2-C6-cycloalkyl, aralkyl and aryl; by reacting the vinyl ether (Ilia)

in which R² is as defined above; and the compound (Illb)

O

H O^R¹ (Illb)

in which R¹ is as defined above; with a reagent (III c) selected from the group of sulfonylhalides of formula (lllc-1 ) or sulfonylanhydrides of formula (lllc-2):

" M

(lllc-1 ) (lllc-2) in which

R^Y is independently selected from Ci-C6-alkyl, aryl, Ci-C6-alkyl-aryl and CF3, and

Y is selected from fluoro, chloro, bromo; in the presence of a base. This process is hereinafter also referred to as step (i).

In literature, some approaches for the synthesis of halogenated alkenone ethers like

compounds of formula (III) are already known.

For example, the direct conversion of trifluoracetic acid anhydride with ethylvinylether for the synthesis of ETFBO is described in Chem. Lett. 1976, 499-502, and a similar reaction using catalytic amounts of dimethylaminopyridine DMAP is reported by Buback and Tietze in Chem. Ber. 1989, 1 179 - 1 186. Due to the formation of equimolar amounts trifluoroacetate, this synthetic strategy cannot be used as an efficient process route on industrial scale.

In EP0744400, the conversion of trifluoroacetylhalogenide CFsCOHal with a vinylether in the presence of a base, is described, yielding a halogenated alkenone ether. A similar process in the absence of base is described in US2006084813. Due to the low boiling point of -30 °C, such reactions using trifluoroacetylchlorides have to be performed at low temperature or at higher pressure, causing extra costs and equipment and maybe even safety concerns.

In Org Lett. 2014, 16, 1724, a sequential one-pot-synthesis of ETFBO in dichloromethane was described. This reaction involves release of SO2, which is undesirable both for environment and cost reasons, due to need for gas scrubbing, and also involves dichloromethane as solvent, which is not favorable in chemical production at industrial scale, due to low boiling point and toxicity.

CN 104072347 describes processes for providing halogenated alkenone ethers starting from trifluoroacetic acid, vinylalkylether and phosgene.

WO20100871 describes a process for providing alkenones starting from acid halides and vinyl ethers.

None of the known processes therefore provides a process for halogenated alkenone ethers suitable for industrial scale under mild conditions and easy to handle, starting from di- or trifluoroacetic acid itself.

WO20100871 is considered as closest state of the art.

The present invention differs from WO20100871 by the fact that the reaction starts from di- or trifluoroacetic acid itself, not the acid halide.

The technical effect achieved by this difference is that less effort is needed (while the same result is achieved) to handle the acids than the acid chlorides on a technical level, because trifluoroacetic chloride is a gas.

The technical problem was therefore to find a process with easier technical handling, while the same result is achieved.

This problem is solved by the present invention. There was no hint in the state of the art to start from the acid itself in a one-pot-procedure, and benefit from easy technical handling. Therefore, the problem of the present invention is the development of an economic and scalable process for the synthesis of halogenated alkenone ethers and further of anthranilamide pesticides. This problem is solved by the processes according to the invention.

The compounds of formula (III) are useful for preparing pyridylpyrazole compounds and anthranilamide pesticides therefrom.

Therefore, in a further embodiment, the invention relates to a process for preparing a

pyridylpyrazole compound of the formula (I)

in which R¹ is selected from CF3 and CHF2;

The processes of the invention are associated with a series of advantages as they overcome the aforementioned shortcomings of the prior art processes. The processes of the invention provide the vinyl ether compounds (III) and the pyridylpyrazole compounds of formula (I) in high yields and in excellent regioselectivity. Undesired side reactions leading to unwanted by-products are minimized. This makes purification easier, which can be done e.g. by distillation (or distillation / crystallization later in the process steps). Sometimes, the product can be employed in the next reaction step without purification. This prevents losses during work-up or purification, and this also saves time, resources and/or energy. Further advantages of the processes of the present invention are that the processes can be run at moderate temperatures. The solvents can be recovered and be re-used. The reagents to be used are safe and inexpensive, which is favourable in view of costs and safety aspects. The reactants are cheap and readily available or can be easily manufactured. Due to these properties, the processes are therefore suitable for production on an industrial scale, which is a further advantage.

Vinyl ethers of formula (Ilia) are commercially available (e.g. Merck Millipore) or can be synthesized according to literature.

Difluoroacetic acid can be purchased e.g. at Acros Organics, or trifluoroacetic acid e.g. at Merck Millipore.

The reagent (lllc) is selected from the group of sulfonylhalides of formula (lllc-1 ) or

sulfonylanhydrides of formula (lllc-2):

9 o I I

Y 1 1

R Y

o ^K ~ O ⁰ O

(lllc-1 ) (lllc-2) in which

Y is selected from fluoro, chloro, bromo.

In one embodiment, the reagent (lllc) is a compound of formula (lllc-1 ), in which Y is chloro. In one embodiment, the reagent (lllc) is a compound of formula (lllc-1 ), in which R^Y is methyl, CF3 or methylaryl, e.g. 4-tolyl. In one embodiment, the reagent (lllc) is a compound of formula (lllc-1 ), in which R^Y is CH3, CF3 or methylaryl, e.g. 4-tolyl, and in which Y is chloro.

In one embodiment, the reagent (lllc) is methanesulfonylchloride, also called sometimes mesyl chloride, i.e. a compound of formula (lllc-1 ), in which R^Y is CH3 and Y is chloro:

O

H sC^ CI In another embodiment, the reagent (lllc) is para-toluenesulfonylchloride, also known as tosyl chloride, i.e. a compound of formula (lllc-1 ), in which R^Y is 4-methyl-phenyl and Y is chloro:

In another embodiment, the reagent (lllc) is triflyl chloride, i.e. a compound of formula (lllc-1 ), in which R^Y is CF3 and Y is chloro:

O

F₃C^ CI In one embodiment, the reagent (lllc) is the anhydride (lllc-2) and is a mixed anhydride, i.e. the two moieties R^Y are different.

In another embodiment, the reagent (lllc) is the anhydride (lllc-2) and is a symmetric anhydride; i.e. the two moieties R^Y are identical. In a further embodiment, the anhydride (lllc-2) is methanesulfonic anhydride MS2O.

Many reagents of formula (lllc) are commercially available, e.g. methanesulfonyl chloride (mesyl chloride), para-toluenesulfonylchloride (tosyl chloride), which are both available from e.g. Aldrich and Acros Organics. If not available, they can be synthesized according to literature. In general, a base is used during activation. For use as a base, nitrogen bases are preferred, and in particular N-heterocycles, and in particular pyridine compounds, which may also be substituted.

In one embodiment of the invention, the base is therefore a pyridine compound, which is optionally substituted. If the pyridine base carries substituents, these are preferably selected from the group of Ci-C6-alkyl, halogen. In a particular embodiment of the invention, the base is pyridine itself, or a substituted pyridine, preferably ethylmethylpyridine (e.g. 2-methyl-5-ethyl- pyridine), 2-, 3-, or 4-methyl-pyridine (also called 2-, 3-, or 4-picoline), 2,6-dimethylpyridine, 2,6- bis(1 ,1 -dimethylethyl)-pyridine, or 2- chloropyridine, 3-chloropyridine, 4-chloropyridine, 2,6- dichloropyridine.

In another embodiment of the invention, the base is a N-heterocycle, which is optionally substituted. In a particular embodiment of the invention, the base is imidazole, or a substituted imidazole e.g. 1 -methylimidazole.

A wide variety of these bases is known and commercially available, e.g. from Aldrich.

The base is employed in a certain equivalent amount in relation to the carboxylic acid:

In one embodiment, at least one equivalent of base is used.

In another embodiment, at least two equivalents of base are used.

In one embodiment, the base is used in the range of 1 to 20 equivalents, or 1 to 10 equivalents, o 2 to 10 equivalents, or 1 to 5 equivalents, or 2 to 5 equivalents.

In one embodiment, the base is used in the range of 2 to 4 equivalents. In another embodiment, 2 to 2.5 equivalents are used.

The reaction is performed in a temperature range between -30 °C and 40 °C. In one

embodiment, the temperature range is -10 to 30 °C, or 0 to 30°C, or 10 to 30°C, or 0 to 25°C, or 10 to 25°C. The reaction can be performed under normal or higher pressure.

In one embodiment, the reaction step (i) is carried out in a solvent. In one embodiment, the reaction is carried out in an organic solvent, which includes but is not limited to

dichloromethane, dichloroethane, dioxane, tetrahydrofuran, methyl-tetrahydrofuran, or also a hydrocarbon solvent or an aromatic solvent.

In one embodiment, the reaction is carried out in an organic solvent which is selected from toluene, ethylbenzene, o-xylene, m-xylene, p-xylene, chlorobenzene, (trifluoromethyl)benzene, hexane, cyclohexane, methylcyclohexane, heptane or a mixture thereof.

In one embodiment, the reaction is carried out in a solvent which is an aromatic solvent. In one embodiment, the aromatic solvent is selected from from toluene, ethylbenzene, o-xylene, m- xylene, p-xylene, chlorobenzene, (trifluoromethyl)benzene or a mixture thereof, preferably toluene. In one embodiment, the reaction is carried out in a non-aromatic organic solvent. In one embodiment, the non-aromatic organic solvent is selected from hexane, cyclohexane, methylcyclohexane or a mixture thereof.

In one embodiment of the invention, 2,6-dimethylaminopyridine (DMAP) is added as catalyst. DMAP is usually employed in substoichiometric amounts, often in the range of 0.01 mol% to 30 mol%.

Regarding the sequence of reagent addition, the person skilled in the art knows how to determine the order of the reagent addition. Preferably, vinylether and base are dissolved in the solvent, followed by the addition of carboxylic acid. In one embodiment, the activation reagent is added as last component. In another embodiment, the acid is added to the base, then the vinyl ether is added, then the sulfonylhalide or sulfonylanhydride.

The described procedure for the activation of a carboxylic acid in the presence of a vinylether has not been reported in literature. The result of this invention is surprising, since carboxylic acids are generally converted to the corresponding acid halides (i.e. with SOC ) or a

comparable activated intermediate, prior to the reaction with any (C)-nucleophile (here vinylether). It is known that vinylethers tend to polymerise, especially in acidic media (presence of carboxylic acids). Additionally, it is surprising that high yields can be obtained with little excess of vinylether, using the process according to the invention.

In one embodiment the suspension can be filtered (removal of salts i.e. in a toluene suspension) and used in the following reaction step without further purification or isolation. In another embodiment, the product mixture is subjected to a workup (e.g. aqueous extraction) and the ETFBO solution can directly be used in the following step. In another embodiment, ETFBO is purified, e.g. ETFBO can be destilled and be used in the following step, optionally preceded by a workup (e.g. aqueous extraction) and removal of solvent.

In one embodiment, the reaction product containing the alkenone compound, e.g. ETFBO, can be employed as such in the following reaction step, without any purification.

This procedure is advantageous compared to the known processes, where the carboxylic is activated first (i.e. thionylchloride) and thereby transformed to the active intermediate. This conversion usually needs to be confirmed analytically - generally though derivatizations (amide formation etc.), prior to introduction of the nucleophile of choice.

Furthermore, the described procedure can be performed in toluene. From a technical point of view, this is preferred in comparison to the use of halogenated solvents e.g. dichloromethane, for the reason of toxicity and sustainability.

In comparison to the direct use of trifluoroacetylchloride, no intensive cooling to -30 °C for condensation or the use of pressure vessels for the reaction at higher pressures is needed. In a production concept, this results in lower energy costs as well as in less technical complexity.

In a further embodiment, the invention relates to said process according to the invention, which goes in step (i) via the primary conversion products of formula (III' )

in which Y is selected from fluoro, chloro and bromo, and R¹ and R² are as defined above.

In a further embodiment, the invention relates to said process according to the invention, in which in the compound of formula (III), R¹ is CF3.

The compound of formula (III), in which R² is ethyl, and R¹ is trifluoromethyl, is of special interest and is 4-ethoxy-1 ,1 ,1 -trifluoro-but-3-en-2-one, often referred to as " ETFBO" .

As mentioned above, the invention also relates to processes in which the compounds of formula (III) are employed as reactants, and which are useful in the synthesis of anthranilamide pesticides. Therefore, a further aspect of the present invention relates to combinations of the abovementioned process step (i) with subsequent process steps in which the product of fomula (III) is converted to further products, or to a combination of the abovementioned process with subsequent process steps or also preceding process steps. The advantages mentioned for the process of step (ii) are also present for the combination of these process steps.

Therefore, in one embodiment, the invention relates to a process for preparing a pyridylpyrazol compound of the formula (I)

in which

R¹ is selected from CF3 and CHF2; comprising the steps of

(i) preparing a compound of formula (III) as described herein;

wherein

R¹ is as defined as herein; and

R² is selected from Ci-C6-alkyl, C2-C6-cycloalkyl, aralkyl and aryl; and

(iia) reacting the compound of formula III with a compound of the formula (II) in the

presence of an acid (referred to herein as step (iia)

, H ₂

The reaction step (iia) is described in the unpublished application PCT/EP2014/062709 in more detail. In this context, the acid employed in the reaction referred to as step (iia) is a protonic acid and may be selected from inorganic or organic acids. In one embodiment, the acid may be selected from concentrated HCI, concentrated sulfuric acid, concentrated phosphoric acid, benzene sulfonic acid and p-toluene sulfonic acid. In one embodiment, the acid is selected from hydrochloric acid HCI, sulfuric acid H2SO4 and phosphoric acid H3PO4, preferably hydrochloric acid HCI and sulfuric acid H2SO4. In another embodiment, the acid may be selected from concentrated HCI and concentrated sulfuric acid H2SO4. In another embodiment, the acid is gaseous HCI.

In one embodiment, the acid is an aqueous acid. Aqueous acid means a mixture of the respective acid with water. In one embodiment, where the respective acid is HCI, the amount of water may be from 63 to 75 % or from 63 to 70 %.

In one embodiment, the acid is concentrated hydrochloric acid. Concentrated hydrochloric acid may be understood as a concentration up to the saturated solution, which means at 20°C that one liter of saturated HCI aqueous solution contains 720 g HCI. In another embodiment, the acid is concentrated sulfuric acid. Concentrated sulfuric acid may contain up to 98% sulfuric acid.

The amount of acid can be varied in broad ranges. It may e.g. be varied from 0.05 to 10 equivalents [=" eq" , in relation to the compound (II)], or from 0.1 to 5 eq, or from 0.1 to 3 eq, or from 0.15 to 3 eq, or from 0.15 to 2 eq. For example, it may e.g. be 0.15 to 1 eq in the case of sulfuric acid and up to 2 equivalents in the case of concentrated hydrochloric acid. In one embodiment, the acid is employed in an under-stoichiometric ratio with regard to compound (II). " Under-stoichiometric" ratio means that the number of equivalents is smaller than 1 , e.g. 0.05 eq, 0.1 eq, 0.15 eq, 0.2 eq, 0.25 eq, 0.3 eq, 0.35 eq, 0.5 eq, 0.6 eq, 0.7 eq, 0.75 eq, 0.8 eq, 0.9 eq. In one embodiment, the number of equivalents is smaller than 0.5.

In one embodiment, the reaction step (iia) is carried out in a solvent. In one embodiment, the reaction is carried out in an organic solvent which is selected from toluene, ethylbenzene, o- xylene, m-xylene, p-xylene, chlorobenzene, hexane, cyclohexane, methylcyclohexane, or a mixture thereof.

In one embodiment, the reaction is carried out in a solvent which is an aromatic solvent. In one embodiment, the aromatic solvent is selected from from toluene, ethylbenzene, o-xylene, m- xylene, p-xylene, chlorobenzene, or a mixture thereof, preferably toluene. In one embodiment, the reaction is carried out in a non-aromatic organic solvent. In one embodiment, the non- aromatic organic solvent is selected from hexane, cyclohexane, methylcyclohexane or a mixture thereof.

The temperature at which the reaction step (iia) is carried out (reaction temperature) may be varied in broad ranges, which the person skilled in the art knows, often depends from the reflux temperature of the solvent to be used. In one embodiment, the reaction is carried out at a temperature between 15 to 150°C, or 20 to 150°C, or 20 to 120°C, or 25 to 120°C, or 30 to 120°C, or 40 to 120°C, or 50 to 120°C, or 60 to 120°C, or 70 to 120°C.

The duration time of the reaction varies depending on the amount of acid and depending on the reaction temperature. The end of the reaction can be monitored by methods known to the person skilled in the art, e.g. thin layer chromatography, HPLC. In one embodiment, the reaction is carried out under heating to reflux for up to 20 hours.

As always, the person skilled in the art knows the best work-up of the reaction mixture after the end of the reaction. After cooling, the phase of reaction water, which usually contains the acid, is removed. The organic phase is washed with water, possibly under use of bases such as NaHC03, Na2CC"3 oder NaOH, to achieve neutralization. Upon removal of the solvent

(distillation, e.g. at low temperatures, under reduced pressure, possibly azeotropic removal of water), the compound of formula (I) is obtained in high yield as crude product.

The compound of formula (I) may be employed as crude product in the next reaction step towards the insecticidal compounds described in the beginning. Alternatively, the compound of formula (I) may be purified by methods known to the person skilled in the art and may be employed as a pure compound in the next reaction step towards the insecticidal compounds described in the beginning.

In an alternative embodiment, the invention relates to a process for preparing a pyridylpyrazol compound of the formula (I)

in which

R¹ is selected from CF3 and CHF2; comprising the steps of

(i) preparing a compound of formula (III) as described herein;

wherein

R¹ is as defined as herein; and R² is selected from Ci-C6-alkyl, C2-C6-cycloalkyl, aralkyl and aryl; and

(iib-1 )preparing an NH-pyrazole of formula (IV) by reacting the compound of formula (I I I) with hydrazine,

wherein

R¹ is as defined herein;

and (iib-2)reacting the NH-pyrazole of formula (IV) with 2,3-dichloropyridin (V)

The reaction sequence of step (iib-1 ) and step (iib-2) is e.g. described in WO2013024008 and WO2013/076092. Further experimental details and preferences can be found there.

In a further embodiment, the present invention relates to processes for subsequent reaction of the compounds of formula (I). Derivatives of compounds of formula (I) are e.g. substituted 1 - pyridin-2-yl-1 H-pyrazole-5-carbonyl compounds of formula (l-A), which are useful in the synthesis of anthranilamide insecticides, especially the carbonyl chlorides. For preparation of substituted 1 -pyridin-2-yl-1 H-pyrazole-5-carbonylchlorides, a process described in WO 02/070483, WO03/015519, WO 07/043677 and WO 08/130021 has been found to be useful. Especially useful preparation methods are described in WO2013/024007 and in

WO2013/076092.

Accordingly, in a further aspect, the present invention relates to a process for

preparing a compound of formula (l-A)

wherein

R¹ is as defined herein;

X is selected from halogen, preferably CI, OH, O-Mg-CI, O-Mg-Br, imidazole, -O-CO- R^x, -0-CO-OR^x, -OS0₂R^x, -SR^y, in which

R^x is independently selected from Ci-C6-alkyl, trifluoromethyl and phenyl which is

optionally substituted with Ci-C6-alkyl (preferably as o-toluene, m-toluene, p-toluene, o-xylene, m-xylene, p-xylene) or halogen, and

R^y is independently selected from Ci-C6-alkyl and phenyl which is optionally substituted with Ci-C6-alkyl (preferably as o-toluene, m-toluene, p-toluene, o-xylene, m-xylene, p-xylene) or halogen; the process comprising:

a) providing the compound of the formula (I) by a process as described herein [step (ii), optionally with a preceding ste

wherein R¹ is as defined above;

b) reacting the compound of formula (I) in a step (iii) to the corresponding carbonyl

compound of formula (l-A).

In one embodiment, the invention relates to the process, wherein the carbonyl compound of formula (l-A) is an acid chloride, in which X is CI.

In a further embodiment, the invention relates to a process as described above, comprising the steps of

iii-a) deprotonating a compound of the formula (I)

in which R¹ is as defined above,

with a magnesium-organic base having a carbon bound magnesium, or with a magnesium amide having a nitrogen bound magnesium which is derived from a secondary amine, in the presence of a lithium halide, where the base is used in an amount sufficient to achieve at least 80 % deprotonation of the compound of formula (I); and iii-b) subjecting the product obtained in step (iii-a) to a carboxylation by reacting it with a reagent selected from phosgene and carbon dioxide, to obtain a compound of formula (l-A) as defined above.

In a further embodiment, the invention relates to the process as described above, wherein the conversion of a compound of formula (I) to a carbonyl compound of formula (l-A) (step iii) is done in an aprotic organic solvent or aprotic solvent mixture comprising an aprotic solvent having an ether moiety.

The details of the process step (iii), together with preferences and examples, can be found in WO2013/024007 and WO2013/076092.

As said above, the invention relates to combinations of process steps, comprising step (ii). Accordingly, in a further aspect, the present invention relates to a process for preparing an anthranilamide compound of formula (l-B):

wherein R¹ is as defined herein;

R^2a is selected from the group consisting of hydrogen, halogen, halomethyl and cyano; R^2b is selected from the group consisting of halogen, methyl and halomethyl;

R³ is selected from hydrogen, C1-C6 alkyl;

R⁵, R⁶ are selected independently of one another from the group consisting of hydrogen, Ci-Cio-alkyl, Cs-Cs-cycloalkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, wherein the

aforementioned aliphatic and cycloaliphatic radicals may be substituted with 1 to 10 substituents R^e, and phenyl, which is unsubstituted or carries 1 to 5 substituents R^f; or

R⁵ and R⁶ together represent a C2-C7-alkylene, C2-C7-alkenylene or

C6-Cg-alkynylene chain forming together with the sulfur atom to which they are attached a 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-membered saturated, partially unsaturated or fully unsaturated ring, wherein 1 to 4 of the CH2 groups in the C2-C7-alkylene chain or 1 to 4 of any of the CH2 or CH groups in the C2-C7-alkenylene chain or 1 to 4 of any of the CH2 groups in the C6-Cg-alkynylene chain may be replaced by 1 to 4 groups independently selected from the group consisting of C=0, C=S, O, S, N, NO, SO, SO2 and NH, and wherein the carbon and/or nitrogen atoms in the C2- C7-alkylene, C2-C7-alkenylene or Ce-Cg-alkynylene chain may be substituted with 1 to 5 substituents independently selected from the group consisting of halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Cs-Cs-cycloalkyl, C3-Cs-halocycloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkynyl and C2-C6-haloalkynyl; said substituents being identical or different from one another if more than one substituent is present;

R^a is selected from the group consisting of Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, Cs- Cs-cycloalkyl, Ci-C6-alkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, wherein one or more CH2 groups of the aforementioned radicals may be replaced by a C=0 group, and/or the aliphatic and cycloaliphatic moieties of the aforementioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 substituents selected from C1-C4 alkoxy;

phenyl, benzyl, pyridyl and phenoxy, wherein the last four radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, (C1-C6- alkoxy)carbonyl, Ci-C6-alkylamino and di-(Ci-C6-alkyl)amino,

R^b is selected from the group consisting of Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, Cs- Cs-cycloalkyl, Ci-C6-alkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, wherein one or more CH2 groups of the aforementioned radicals may be replaced by a C=0 group, and/or the aliphatic and cycloaliphatic moieties of the aforementioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 substituents selected from Ci-C4-alkoxy;

phenyl, benzyl, pyridyl and phenoxy, wherein the last four radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy and (Ci- C6-alkoxy)carbonyl;

R^c, R^d are, independently from one another and independently of each occurrence,

selected from the group consisting of hydrogen, cyano, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, Cs-Cs-cycloalkyl, wherein one or more Chb groups of the

aforementioned radicals may be replaced by a C=0 group, and/or the aliphatic and cycloaliphatic moieties of the aforementioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals selected from C1-C4- alkoxy;

Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, C1-C6- alkylsulfonyl, Ci-C6-haloalkylthio, phenyl, benzyl, pyridyl and phenoxy, wherein the four last mentioned radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy, C1-C6 haloalkoxy and (Ci-C6-alkoxy)carbonyl; or

R^c and R^d, together with the nitrogen atom to which they are bound, may form a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or fully unsaturated heterocyclic ring which may additionally contain 1 or 2 further heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may optionally be substituted with halogen, C1-C4- haloalkyl, Ci-C4-alkoxy or Ci-C4-haloalkoxy;

R^e is independently selected from the group consisting of halogen, cyano, nitro, -OH, -

SH, -SCN, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, Cs-Cs-cycloalkyl, wherein one or more CH2 groups of the aforementioned radicals may be replaced by a C=0 group, and/or the aliphatic and cycloaliphatic moieties of the aforementioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals selected from C1-C4 alkoxy;

Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, C1-C6- alkylsulfonyl, Ci-C₆-haloalkylthio, -OR^a, -NR^cR^d, -S(0)_nR^a, -S(0)_nNR^cR^d,

-C(=0)R^a, -C(=0)NR^cR^d, -C(=0)OR^b, -C(=S)R^a, -C(=S)NR^cR^d, -C(=S)OR^b,

-C(=S)SR^b, -C(=NR^c)R^b, -C(=NR^c)NR^cR^d, phenyl, benzyl, pyridyl and phenoxy, wherein the last four radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy and Ci-C6-haloalkoxy; or

two vicinal radicals R^e together form a group =0, =CH(Ci-C4-alkyl), =C(Ci-C₄- alkyl)Ci-C₄-alkyl, =N(Ci-C₆-alkyl) or =NO(Ci-C₆-alkyl);

R^f is independently selected from the group consisting of halogen, cyano, nitro, -OH, -

-C(=0)R^a, -C(=0)NR^cR^d, -C(=0)OR , -C(=S)R^a, -C(=S)NR^cR^d, -C(=S)OR ,

-C(=S)SR , -C(=NR^c)R , and -C(=NR^c)NR^cR^d; k is O or l ;

n is 0, 1 or 2; or a stereoisomer, salt, tautomer or N-oxide, or a polymorphic crystalline form, a co-crystal or a solvate of a compound or a stereoisomer, salt, tautomer or N-oxide thereof; the process comprising

a) providing a compound of the formula (I) by a process as described herein,

b) converting the compound of formula (I) to a compound of formula (l-B), optionally via the corresponding carbonyl compound of formula (l-A) as described herein.

In one embodiment, the compound of formula (l-B) is a compound of formula (I-B1 ). Therefore, the invention relates to a process for preparing an anthranilamide compound of formula (I-B1 ):

wherein

R¹ is as defined herein;

R^2a is selected from the group consisting of H, F, CI, Br and CN;

R^2b is selected from the group consisting of F, CI, Br, I, CH3;

R⁵, R⁶ are selected independently of one another from the group consisting of hydrogen, Ci-C4-alkyl, Cs-Cs-cycloalkyl, or

R⁵ and R⁶ together represent a C2-C7-alkylene, C2-C7-alkenylene or

C6-Cg-alkynylene chain forming together with the sulfur atom to which they are attached a 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-membered saturated, partially unsaturated or fully unsaturated ring,

k is O or l ; or a stereoisomer, salt, tautomer or N-oxide, or a polymorphic crystalline form, a co-crystal or a solvate of a compound or a stereoisomer, salt, tautomer or N-oxide thereof; the process comprising

a) providing a compound of the formula (I) by a process as described herein [step (ii), optionally with a preceding step (i) and/or step (ib)], b) converting the compound of formula (I) to a compound of formula (l-B), optionally via the corresponding carbonyl compound of formula (l-A) as described herein.

In one embodiment, the invention relates to a process as described above for preparing an anthranilamide compound of formula (I-B1 ), wherein the compound of formula (I-B1 ) is selected from the group consisting of the following compounds 1-1 1 , 1-16, 1-21 , I-26, 1-31 :

In a further aspect, the present invention relates to a process for preparing an anthranilamide compound of formula (l-B) or (I-B1 ) as described herein, wherein the process comprises

a) providing a compound of the formula (I) by a process as described herein [step (ii), optionally with a preceding step (i) and/or step (ib)],

b) reacting the compound of formula (I) in a step (iii) to the corresponding carbonyl compound of formula (l-A) as described herein,

c) converting the compound of formula (l-A) in a step (iv) to a compound of formula (l-B) as described herein.

In a further aspect, the present invention relates to a process for preparing an anthranilamide compound of formula (l-B) or (I-B1 ) as described herein, wherein the process step (iv) in c) comprises

iv) reacting the compound of the formula (l-A) as described herein with a compound of the formula (V)

in which the variables R^2a, R^2b, R³, R⁵, R⁶ and k are each as defined herein, in the presence of a base, to obtain a compound of the formula (l-B) or (I-B1 )as defined herein.

In a further aspect, the present invention relates to a process for preparing an anthranilamide compound of formula (l-B), wherein in the compound of formula (l-B)

R¹ is as defined herein,

R^2a is CI, Br, cyano; R^2b is methyl, CI, Br;

R³ is hydrogen, methyl;

R⁵ and R⁶ are identical and selected from methyl, ethyl, isopropyl;

k is 0.

In the context of the present invention, the terms used generically are each defined as follows:

The prefix C_x-C_y refers in the particular case to the number of possible carbon atoms. The term "halogen" denotes in each case fluorine, bromine, chlorine or iodine, in particular fluorine, chlorine or bromine.

The term "partially or fully halogenated" will be taken to mean that 1 or more, e.g. 1 , 2, 3, 4 or 5 or all of the hydrogen atoms of a given radical have been replaced by a halogen atom, in particular by fluorine or chlorine.

The term "alkyl" as used herein (and in the alkyl moieties of other groups comprising an alkyl group, e.g. alkoxy, alkylcarbonyl, alkylthio, alkylsulfinyl, alkylsulfonyl and alkoxyalkyl) denotes in each case a straight-chain or branched alkyl group having usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms and in particular from 1 to 3 carbon atoms. Examples of an alkyl group are methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, iso-butyl, tert-butyl, n-pentyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 -ethylpropyl, n-hexyl, 1 ,1 -dimethylpropyl, 1 ,2-dimethylpropyl, 1 - methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1 -dimethylbutyl, 1 ,2- dimethylbutyl, 1 ,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1 - ethylbutyl, 2-ethylbutyl, 1 ,1 ,2-trimethylpropyl, 1 ,2,2-trimethylpropyl, 1 -ethyl-1 -methylpropyl, 1 -ethyl-2-methylpropyl, n-heptyl, 1 -methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5- methylhexyl, 1 -ethyl pentyl, 2-ethylpentyl, 3-ethylpentyl, n-octyl, 1 -methyloctyl, 2-methylheptyl, 1 - ethylhexyl, 2-ethylhexyl, 1 ,2-dimethylhexyl, 1 -propylpentyl and 2-propylpentyl.

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

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

The term "fluoroalkyl", as used herein (and in the fluoroalkyl units of fluoroalkoxy, fluoroalkylthio, fluoroalkylsulfinyl and fluoroalkylsulfonyl) denotes in each case straight-chain or branched alkyl groups having usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms and in particular 1 to 4 carbon atoms, wherein the hydrogen atoms of this group are partially or totally replaced with fluorine atoms. Examples thereof are fluoromethyl,

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

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

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

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

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

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

The term "haloalkenyl" as used herein, which may also be expressed as "alkenyl which may be substituted by halogen", and the haloalkenyl moieties in haloalkenyloxy,

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

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

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

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

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

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

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

halomethoxy, and also in particular Ci-C2-fluoroalkoxy, such as fluoromethoxy, difluoromethoxy, trifluoromethoxy, 1 -fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2- chloro-2-fluoroethoxy, 2-chloro-2,2-difluoro-ethoxy, 2,2-dichloro-2-fluorethoxy, 2,2,2- trichloroethoxy, pentafluoroethoxy and the like.

The term "alkoxy-alkyl" as used herein denotes in each case alkyl usually comprising 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, wherein 1 carbon atom carries an alkoxy radical usually comprising 1 to 10, frequently 1 to 6, in particular 1 to 4, carbon atoms as defined above. Examples are CH₂OCH₃, CH2-OC2H5, n-propoxymethyl, CH₂-OCH(CH₃)2, n- butoxymethyl, (l -methylpropoxy)-methyl, (2-methylpropoxy)methyl, CH2-OC(CH3)3, 2- (methoxy)ethyl, 2-(ethoxy)ethyl, 2-(n-propoxy)-ethyl, 2-(1 -methylethoxy)-ethyl, 2-(n-butoxy)ethyl, 2-(1 -methylpropoxy)-ethyl, 2-(2-methylpropoxy)-ethyl, 2-(1 ,1 -dimethylethoxy)-ethyl, 2-(methoxy)- propyl, 2-(ethoxy)-propyl, 2-(n-propoxy)-propyl, 2-(1 -methylethoxy)-propyl, 2-(n-butoxy)-propyl, 2-(1 -methylpropoxy)-propyl, 2-(2-methylpropoxy)-propyl, 2-(1 ,1 -dimethylethoxy)-propyl, 3- (methoxy)-propyl, 3-(ethoxy)-propyl, 3-(n-propoxy)-propyl, 3-(1 -methylethoxy)-propyl, 3-(n- butoxy)-propyl, 3-(1 -methylpropoxy)-propyl, 3-(2-methylpropoxy)-propyl, 3-(1 ,1 -dimethylethoxy)- propyl, 2-(methoxy)-butyl, 2-(ethoxy)-butyl, 2-(n-propoxy)-butyl, 2-(1 -methylethoxy)-butyl, 2-(n- butoxy)-butyl, 2-(1 -methylpropoxy)-butyl, 2-(2-methyl-propoxy)-butyl, 2-(1 ,1 -dimethylethoxy)- butyl, 3-(methoxy)-butyl, 3-(ethoxy)-butyl, 3-(n-propoxy)-butyl, 3-(1 -methylethoxy)-butyl, 3-(n- butoxy)-butyl, 3-(1 -methylpropoxy)-butyl, 3-(2-methylpropoxy)-butyl, 3-(1 ,1 -dimethylethoxy)- butyl, 4-(methoxy)-butyl, 4-(ethoxy)-butyl, 4-(n-propoxy)-butyl, 4-(1 -methylethoxy)-butyl, 4-(n- butoxy)-butyl, 4-(1 -methylpropoxy)-butyl, 4-(2-methylpropoxy)-butyl, 4-(1 ,1 -dimethylethoxy)- butyl and the like.

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

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

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

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

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

The terms "alkylsulfinyl" and "S(0)_n-alkyl" (wherein n is 1 ) are equivalent and, as used herein, denote an alkyl group, as defined above, attached via a sulfinyl [S(O)] group. For example, the term "C i -C6-a I ky Is u If i nyl" refers to a Ci-C6-alkyl group, as defined above, attached via a sulfinyl [S(O)] group. Examples are methylsulfinyl, ethylsulfinyl, n-propylsulfinyl,

1 -methylethylsulfinyl (isopropylsulfinyl), butylsulfinyl, 1 -methylpropylsulfinyl (sec-butylsulfinyl), 2- methylpropylsulfinyl (isobutylsulfinyl), 1 ,1 -dimethylethylsulfinyl (tert-butylsulfinyl), pentylsulfinyl,

1 - methylbutylsulfinyl, 2-methylbutylsulfinyl, 3-methylbutylsulfinyl, 1 ,1 -dimethylpropylsulfinyl,

1 .2- dimethylpropylsulfinyl, 2,2-dimethylpropylsulfinyl, 1 -ethylpropylsulfinyl, hexylsulfinyl, 1 - methylpentylsulfinyl, 2-methylpentylsulfinyl, 3-methylpentylsulfinyl, 4-methylpentylsulfinyl, 1 ,1 - dimethylbutylsulfinyl, 1 ,2-dimethylbutylsulfinyl, 1 ,3-dimethylbutylsulfinyl, 2,2- dimethylbutylsulfinyl, 2,3-dimethylbutylsulfinyl, 3,3-dimethylbutylsulfinyl, 1 -ethylbutylsulfinyl,

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

The terms "alkylsulfonyl" and "S(0)_n-alkyl" (wherein n is 2) are equivalent and, as used herein, denote an alkyl group, as defined above, attached via a sulfonyl [S(0)2] group. For example, the term "Ci-C6-alkylsulfonyl" refers to a Ci-C6-alkyl group, as defined above, attached via a sulfonyl [S(0)2] group. Examples are methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, 1 -methylethylsulfonyl (isopropylsulfonyl), butylsulfonyl, 1 -methylpropylsulfonyl (sec- butylsulfonyl), 2-methylpropylsulfonyl (isobutylsulfonyl), 1 ,1 -dimethylethylsulfonyl (tert- butylsulfonyl), pentylsulfonyl, 1 -methylbutylsulfonyl, 2-methylbutylsulfonyl, 3-methylbutylsulfonyl,

1 .1 - dimethylpropylsulfonyl, 1 ,2-dimethylpropylsulfonyl, 2,2-dimethylpropylsulfonyl,

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

3- methylpentylsulfonyl, 4-methylpentylsulfonyl, 1 ,1-dimethylbutylsulfonyl,

1 .2- dimethylbutylsulfonyl, 1 ,3-dimethylbutylsulfonyl, 2,2-dimethylbutylsulfonyl, 2,3-dimethylbutylsulfonyl, 3,3-dimethylbutylsulfonyl, 1 -ethylbutylsulfonyl, 2-ethylbutylsulfonyl, 1 ,1 ,2-trimethylpropylsulfonyl, 1 ,2,2-trimethylpropylsulfonyl, 1 -ethyl-1 -methylpropylsulfonyl and 1 - ethyl-2-methylpropylsulfonyl.

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

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

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

The term "aryl" as used herein refers to a mono-, bi- or tricyclic aromatic hydrocarbon radical having 6 to 14 carbon atoms. Examples thereof comprise phenyl, naphthyl, fluorenyl, azulenyl, anthracenyl and phenanthrenyl. Aryl is preferably phenyl or naphthyl and especially phenyl.

The term "3-, 4-, 5-, 6-, 7- or 8-membered saturated carbocyclic ring" as used herein refers to carbocyclic rings, which are monocyclic and fully saturated. Examples of such rings include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane and the like.

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

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

Examples of a 3-, 4-, 5-, 6- or 7-membered saturated heterocyclic ring include: oxiranyl, aziridinyl, azetidinyl, tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, tetrahydrothien-2-yl,

tetrahydrothien-3-yl, pyrrolidin-2-yl, pyrrolidin-3-yl, pyrazolidin-3-yl, pyrazolidin-4-yl, pyrazolidin- 5-yl, imidazolidin-2-yl, imidazolidin-4-yl, oxazolidin-2-yl, oxazolidin-4-yl, oxazolidin-5-yl, isoxazolidin-3-yl, isoxazolidin-4-yl, isoxazolidin-5-yl, thiazolidin-2-yl, thiazolidin-4-yl, thiazolidin- 5-yl, isothiazolidin-3-yl, isothiazolidin-4-yl, isothiazolidin-5-yl, 1 ,2,4-oxadiazolidin-3-yl, 1 ,2,4- oxadiazolidin-5-yl, 1 ,2,4-thiadiazolidin-3-yl, 1 ,2,4-thiadiazolidin-5-yl, 1 ,2,4-triazolidin-3-yl, 1 ,3,4- oxadiazolidin-2-yl, 1 ,3,4-thiadiazolidin-2-yl, 1 ,3,4-triazolidin-2-yl, 2-tetrahydropyranyl, 4-tetrahydropyranyl, 1 ,3-dioxan-5-yl, 1 ,4-dioxan-2-yl, piperidin-2-yl, piperidin-3-yl, piperidin-4-yl, hexahydropyridazin-3-yl, hexahydropyridazin-4-yl, hexahydropyrimidin-2-yl, hexahydropyrimidin- 4-yl, hexahydropyrimidin-5-yl, piperazin-2-yl, 1 ,3,5-hexahydrotriazin-2-yl and

1 ,2,4-hexahydrotriazin-3-yl, morpholin-2-yl, morpholin-3-yl, thiomorpholin-2-yl, thiomorpholin-3- yl, 1 -oxothiomorpholin-2-yl, 1 -oxothiomorpholin-3-yl, 1 ,1 -dioxothiomorpholin-2-yl, 1 ,1 - dioxothiomorpholin-3-yl, azepan-1 -, -2-, -3- or -4-yl, oxepan-2-, -3-, -4- or -5-yl, hexahydro-1 ,3- diazepinyl, hexahydro-1 ,4-diazepinyl, hexahydro-1 ,3-oxazepinyl, hexahydro-1 ,4-oxazepinyl, hexahydro-1 ,3-dioxepinyl, hexahydro-1 ,4-dioxepinyl and the like.

Examples of a 3-, 4-, 5-, 6- or 7-membered partially unsaturated heterocyclic ring include: 2,3- dihydrofur-2-yl, 2,3-dihydrofur-3-yl, 2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl, 2,3-dihydrothien-2-yl,

2.3- dihydrothien-3-yl, 2,4-dihydrothien-2-yl, 2,4-dihydrothien-3-yl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl,

3- pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-isoxazolin-3-yl, 3-isoxazolin-3-yl, 4-isoxazolin-3-yl, 2-isoxazolin-

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

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

3.4- dihydropyrazol-5-yl, 4,5-dihydropyrazol-1 -yl, 4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4- yl, 4,5-dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4- yl, 2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4- yl, 3,4-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4- yl, 2-, 3-, 4-, 5- or 6-di- or tetrahydropyridinyl, 3-di- or tetrahydropyridazinyl, 4-di- or

tetrahydropyridazinyl, 2-di- or tetrahydropyrimidinyl, 4-di- or tetrahydropyrimidinyl, 5-di- or tetrahydropyrimidinyl, di- or tetrahydropyrazinyl, 1 ,3, 5-di- or tetrahydrotriazin-2-yl, 1 ,2, 4-di- or tetrahydrotriazin-3-yl, 2,3,4,5-tetrahydro[1 H]azepin-1 -, -2-, -3-, -4-, -5-, -6- or -7-yl,

3,4,5,6-tetrahydro[2H]azepin-2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,4,7-tetrahydro[1 H]azepin-1 -, -2-, -3- , -4-, -5-, -6- or -7-yl, 2,3,6,7-tetrahydro[1 H]azepin-1 -, -2-, -3-, -4-, -5-, -6- or -7-yl,

tetrahydrooxepinyl, such as 2,3,4,5-tetrahydro[1 H]oxepin-2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,4,7- tetrahydro[1 H]oxepin-2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,6,7-tetrahydro[1 H]oxepin-2-, -3-, -4-, -5-, - 6- or -7-yl, tetrahydro-1 ,3-diazepinyl, tetrahydro-1 ,4-diazepinyl, tetrahydro-1 ,3-oxazepinyl, tetrahydro-1 ,4-oxazepinyl, tetrahydro-1 ,3-dioxepinyl and tetrahydro-1 ,4-dioxepinyl.

A 3-, 4-, 5-, 6- or 7-membered completely unsaturated (including aromatic) heterocyclic ring is e.g. a 5- or 6-membered fully unsaturated (including aromatic) heterocyclic ring. Examples are: 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2- oxazolyl, 4-oxazolyl, 5-oxazolyl, 4-isoxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 4-isothiazolyl, 2- imidazolyl, 4-imidazolyl, 1 ,3,4-triazol-2-yl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4- pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl and 2-pyrazinyl.

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

The compounds can be characterized e.g. by High Performance Liquid Chromatography, Gas Chromatography, by ¹H-/¹³C-NMR and/or by their melting or boiling points. The following analytical procedures were employed:

Analytical HPLC column: Zorbax Eclipse XDB-C18 Ι ,δμηι 50^*4, 6mm von Agilent®Elution: acetonitrile + 0,1 Vol% H₃P0₄ / water + 0,1 Vol% H₃P0₄in a ratio of from 20:80 to 80:20 in 1 1 minutes at 40 °C, UV detection at 212 nm.

1H-/¹³C-NMR. The signals are characterized by chemical shift (ppm) vs. tetramethylsilane, by their multiplicity and by their integral (relative number of hydrogen atoms given). The following abbreviations are used to characterize the multiplicity of the signals: m = multiplett, q = quartett, t = triplett, d = doublet and s = singulett.

m.p. is melting point, b.p. is boiling point.

Room temperature means usually 20-25°C.

Starting materials

2,3-Dichloropyridine was purchased from Aldrich.

Trifluoroacetic acid TFA and ethyl vinyl ether were purchased from Merck Millipore.

Pyridine was purchased from Bernd Kraft.

(3-Chloro-2-pyridyl)hydrazine (II) was prepared according to JOC 35 S.810 (1970) from reaction of 2,3-dichloropyridine with hydrazine hydrate. Purity was from 95,9 wt-% to 99.3 wt-% and usually is indicated in the example description.

ETFBO ( 4-ethoxy-1 ,1 ,1 -trifluoro-but-3-en-2-one) as prepared according to the invention has the same properties and at least the same purity as ETFBO synthesized according to Chem. Lett., pp. 499-502, 1976, or as purchased e.g. from Solvay.

Quantitative analysis of ETFBO, toluene and pyridine:

Instrument: Agilent- 6890 N; carrier gas: nitrogen;

column: HP / 30m HP-1701 / ID = 0,25 mm, FD = 0,25 μπι;

injector system: HP- Split / Splitless Injector / Modus Split 1 : 100; injection: HP-6890 Series

Injector / volume = 1 μΙ; detection: HP- FID

Temperatures + Pressures:

detector: 310°C; injector: 250°C; start temperature: 50°C ; retention time 1 : 5 min

rate 1 : 2°C / min; end temp. 1 : 120°C ;

rate 2: 30°C / min, end temp. 2: 240°C ;

run time total: 44 min

pressure (prgm): const, flow: 0.6 ml / min, AV: 17 cm / sec, 7,45 psi; septum purge: 2 ml / min Compounds are analyzed via the wt.%-method using DMF as an internal standard.

Retention times:

Toluene: 7.53 min Pyridine: 8.03 min

DMF: 13.01 min

ETFBO: 14.14 min Example 1 :

Ethylvinylether (32.0 g, 0.43 mol) and pyridine (70.0 g, 0.88 mol) were dissolved in toluene (300 g) at 10 °C. At this temperature trifluoroacetic acid TFA (46.0 g, 0.40 mol) was added slowly, followed by addition of toluene (5.0 g). The mixture was stirred for 30 min at 10 °C. Following, methanesulfonylchloride (50.4 g, 0.44 mol) was added in a temperature range of 10 - 15 °C. The suspension was stirred for 18 h at RT, and then the reaction was stopped by addition of water (100 g). After phase-separation (aq. phase: 226 g, pH: 2.7), the organic layer was treated with 2% phosphoric acid (100 g). Phases were separated (aq. phase: 102 g, pH: 3.31 ). The organic layer was washed with Na2HP04-solution (2%) (aq. phase: 101 g, pH:6.93). The organic layer (370 g, clear yellow solution) was analyzed via quantitative GC (15.85 wt% ETFBO).

Yield: 87.3 % of ETFBO, which was analyzed by GC as described above.

Example 2:

Pyridine (139.2 g, 1.76 mol) was dissolved in toluene (600 g) at 20 °C. Trifluoroacetic acid TFA (92 g, 0,81 mol) was added slowly at 15 °C, followed by addition of toluene (5 g). Ethylvinylether (64 g, 0.89 mol) was added, followed by addition of toluene (5 g). The mixture was stirred for 30 min at 20 °C, before adding methanesulfonylchloride (100.8 g, 0,88 mol) within 30 min at 15 °C, followed by addition of toluene (5 g). The mixture was stirred at 20 °C for 3 h. The suspension was filtered and the solid was washed 3 times with toluene (100 g each). The combined organic phases were washed with a solution of pH 7 - buffer (200 g) and Na2HP04 (5 g). After phase separation, the organic layer was washed with pH 7 - buffer (200 g) and with an aqueous solution of Na2HP04. The crude product solution was treated with saturated NaCI - solution (5 g). After phase separation, 948 g of the product solution (orange) was isolated; ETFBO (12.15 wt.-%); yield: 85 % of ETFBO, which was analyzed by GC as described above. Example 3:

Ethylvinylether (18.8 g, 0.26 mol) and 2-methyl-pyridine (34.2 g, 0.36 mol) were dissolved in toluene (150 g) at 20 °C. TFA (19.6 g, 0.17 mol) was slowly added at this temperature. The mixture was stirred for 30 min at this temperature. Methanesulfonylchloride (21.7 g, 0.19 mol) was added slowly. The suspension was stirred for 15 hours at 20 to 25 °C. Water (125 ml) was added. Phases were separated and the organic phase was washed with H3PO4 (5 %, 2x100 g) and with an aqueous solution of Na2HP04. (2.5 %, 1 x100 g). The organic phase was

concentrated in vacuum. The crude product (36 g, 63 wt.-% ETFBO) was analyzed via quant. GC (as described above) and ETFBO is isolated as an orange oil in 80 % yield. Example 4:

Ethylvinylether (32.4 g, 0.44 mol) and 3-methyl-pyridine (82.8 g, 0.88 mol) were dissolved in toluene (300 g) at 20 °C. TFA (46 g, 0.40 mol) was slowly added at this temperature. The mixture was stirred for 30 min at this temperature. Methanesulfonylchloride (50.4 g, 0.44 mol) was added slowly. The suspension was stirred for 15 hours at 20 to 25 °C. Water (100 ml) was added. Phases were separated and the organic phase was washed with H3PO4 (5 %, 2x100 g) and with an aqueous solution of Na2HP0₄ (1 %, 1x100 g). The organic phase was concentrated in vacuum. The crude product (71 g, 67 wt.-% ETFBO) was analyzed via quant. GC (as described above) and ETFBO was isolated as an orange oil in 71 % yield.

Example 5:

Ethylvinylether (55.2 g, 0.75 mol) and 2-methyl-5-ethyl-pyridine (134.6 g, 1.1 mol) were dissolved in toluene (375 g) at 20 °C. TFA (57.6 g, 0.50 mol) was slowly added at this temperature. The mixture was stirred for 30 min at this temperature. Methanesulfonylchloride (63.6 g, 0.55 mol) was added slowly. The suspension was stirred for 15 hours at 20 to 25 °C. Water (125 ml) was added. Phases were separated and the organic phase was washed with H3PO4 (5 %, 2x100 g) and with an aqueous solution of Na₂HP0₄ (2.5%, 1 x100 g). The organic phase was concentrated in vacuum. The crude product (98.5 g, 60.8 wt.-% ETFBO) was analyzed via quant. GC (as described above) and ETFBO was isolated as an orange oil in 71 % yield.

Example 6:

Ethylvinylether (2.2 g, 30 mmol) and pyridine (4.75 g, 60 mmol) were dissolved in toluene (30 g) at rt. TFA (2.3 g, 20 mmol) was added and the mixture was stirred for 1 hours at 20 to 25 °C. Methanesulfonic anhydride MS2O (3.5 g, 20 mmol) was added as a suspension in toluene (20 g). The mixture was stirred for 20 hours at 20 to 25 °C. The mixture was diluted with toluene and water (20 g) is added at 5 °C. Phases were separated and the organic layer was washed with water (20 g) followed by 5% NaHC03-solution. The organic phase was dried, filtered and concentrated in vacuum to yield 50.4 % ETFBO (combination of 10 g residue (31.7 wt%

ETFBO) and 1 15 g distillate (18.7 wt% ETFBO) as a red oil.

Further use of vinyl ether compounds

Example I - Synthesis of 3-chloro-2-[3-(trifluoromethyl)pyrazol-1 -yl]pyridine with ETFBO (by conversion of TFA with Ethylvinylether, and activation with MsCI):

3-chloro-2-hydazinylpyridine (99.0 g, 0.69 mol) was dissolved in toluene (400 g). Gaseous HCI (28.0 g, 0.77 mol) was slowly added at 20 °C and the suspension was heated to 85 °C. ETFBO (722 g, 0.64 mol, 15 wt.%) as a solution in toluene was added within 30 minutes at 85 °C. The mixture was stirred for 1 hour at this temperature. Water (32 g) was added and the mixture was allowed to cool to RT. Phases were separated and the organic layer was washed with saturated NaHC03-solution (400 g) and water (400 g), then concentrated in vacuum to yield the product (orange oil) in 97.5% together with 0.5.% of the undesired isomer 3-chloro-2-[5- (trifluoromethyl)pyrazol-l -yl]pyridine.

A detailed description, how the compounds of formula (I) can be converted to the compounds of formula (l-A), (l-B), and necessary intermediates, can be found e.g. in WO2013/076092. Following the procedures given there, and analogous methods, the following compounds of formula (I-B1 ) can be synthesized,which are are compounds of the formula (l-B) with k = 0 and 3 = H.

or the details of the insecticidal properties of the compounds of formula (l-B-1 ), see e.g. O2007/006670, WO2013/024009, and WO2013/024010.

Claims

A process for preparing a compound of formula

in which

R¹ is selected from CF3 and CH F2; and

in which R² is as defined above; and the compound (1Mb)

O

H O ^R (1Mb)

in which R¹ is as defined above; with a reagent (lllc) selected from the group of sulfonylhalides of formula (III sulfonylanhydrides of formula (lllc-2):

(lllc-1 ) (lllc-2) in which

R^Y is independently selected from Ci-C6-alkyl, aryl, Ci-C6-alkyl-aryl and CF3, and Y is selected from fluoro, chloro, bromo; in the presence of a base.

2. A process according to claim 1 , in which the reagent (lllc) is selected from

methanesulfonyl chloride and p-toluenesulfonyl chloride.

3. A process according to claim 1 or 2, which goes via the primary conversion products of formula (III' )

A process according to any one of claims 1 to 3, in which

R¹ is CF₃.

A process for preparing a pyridylpyrazole compound of the formula (I)

in which

R¹ is selected from CF3 and CHF2; comprising the steps of

(i) preparing a compound of formula (III) according to the process of any one of claims 1 to 4;

wherein

R¹ is as defined in any of claims 1 to 4; and

R² is selected from Ci-C6-alkyl, C2-C6-cycloalkyl, aralkyl and aryl;

and

presence of an acid.

The process according to claim 5, in which the acid is selected from hydrochloric acid HCI, sulfuric acid H2SO4 and phosphoric acid H3PO4, preferably hydrochloric acid HCI and sulfuric acid H2SO4.

The process according to claim 5 or 6, in which the acid is an aqueous acid. A process for preparing a pyridylpy e formula (I)

in which

R¹ is selected from CF3 and CHF2; prising the steps of

preparing a compound of formula (III) according to the process of any of claims 1 to

4;

wherein

R¹ is as defined in any of claims 1 to 4; and

R² is selected from Ci-C6-alkyl, C2-C6-cycloalkyl, aralkyl and aryl;

and

(iib-1 )preparing an NH-pyrazole of formula (IV) by reacting the compound of formula III with hydrazine,

wherein

R¹ is as defined in any of claims 1 to 4;

and

(iib-2)reacting the NH-pyrazole of formula (IV) with 2,3-dichloropyridin (V)

CI

A process for preparing a co

wherein

R¹ is as defined in any one of the preceding claims;

X is selected from halogen, preferably CI, OH, O-Mg-CI, O-Mg-Br, imidazole, -O-CO-

R^x, -0-CO-OR^x, -OS0₂R^x, -SR^y, in which

c) providing the compound of the formula (I) by a process according to any of claims 5 to 8,

wherein R¹ is as defined in any one of the preceding claims;

reacting the compound of formula (I) in a step (iii) to the corresponding carbonyl compound of formula (l-A).

0. The process according to claim 9, comprising the steps of

iii-a) deprotonating a compound of the formula (I)

in which R¹ is as defined in any one of the preceding claims,

with a magnesium-organic base having a carbon bound magnesium, or

with a magnesium amide having a nitrogen bound magnesium which is derived from a secondary amine, in the presence of a lithium halide, where the base is used in an amount sufficient to achieve at least 80 % deprotonation of the compound of formula (I); and

-b) subjecting the product obtained in step (iii-a) to a carboxylation by reacting it with a reagent selected from phosgene and carbon dioxide, to obtain a compound of formula (l-A) as defined above. A process for preparing an anthranilamide compound of formula (l-B):

in which

R¹ is as defined in any of the preceding claims;

R³ is selected from hydrogen, C1-C6 alkyl;

R⁵ and R⁶ together represent a C2-C7-alkylene, C2-C7-alkenylene or

C6-Cg-alkynylene chain forming together with the sulfur atom to which they are attached a 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-membered saturated, partially unsaturated or fully unsaturated ring, wherein 1 to 4 of the Chb groups in the C2-C7-alkylene chain or 1 to 4 of any of the Chb or CH groups in the C2-C7-alkenylene chain or 1 to 4 of any of the Chb groups in the C6-Cg-alkynylene chain may be replaced by 1 to 4 groups independently selected from the group consisting of C=0, C=S, O, S, N, NO, SO, SO2 and NH, and wherein the carbon and/or nitrogen atoms in the C2- C7-alkylene, C2-C7-alkenylene or Ce-Cg-alkynylene chain may be substituted with 1 to 5 substituents independently selected from the group consisting of halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Cs-Cs-cycloalkyl, C3-Cs-halocycloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkynyl and C2-C6-haloalkynyl; said substituents being identical or different from one another if more than one substituent is present; is selected from the group consisting of Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, Cs- Cs-cycloalkyl, Ci-C6-alkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, wherein one or more CH2 groups of the aforementioned radicals may be replaced by a C=0 group, and/or the aliphatic and cycloaliphatic moieties of the aforementioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 substituents selected from C1-C4 alkoxy;

is selected from the group consisting of Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, Cs- Cs-cycloalkyl, Ci-C6-alkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, wherein one or more CH2 groups of the aforementioned radicals may be replaced by a C=0 group, and/or the aliphatic and cycloaliphatic moieties of the aforementioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 substituents selected from Ci-C4-alkoxy;

R^d are, independently from one another and independently of each occurrence, selected from the group consisting of hydrogen, cyano, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, Cs-Cs-cycloalkyl, wherein one or more CH2 groups of the

R^e is independently selected from the group consisting of halogen, cyano, nitro, -OH, - SH, -SCN, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, Cs-Cs-cycloalkyl, wherein one or more CH2 groups of the aforementioned radicals may be replaced by a C=0 group, and/or the aliphatic and cycloaliphatic moieties of the aforementioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals selected from C1-C4 alkoxy;

Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, C1-C6- alkylsulfonyl, Ci-C₆-haloalkylthio, -OR^a, -NR^cR^d, -S(0)_nR^a, -S(0)_nNR^cR^d, -C(=0)R^a, -C(=0)NR^cR^d, -C(=0)OR^b, -C(=S)R^a, -C(=S)NR^cR^d, -C(=S)OR^b, -C(=S)SR^b, -C(=NR^c)R^b, -C(=NR^c)NR^cR^d, phenyl, benzyl, pyridyl and phenoxy, wherein the last four radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy and Ci-C6-haloalkoxy; or

R^f is independently selected from the group consisting of halogen, cyano, nitro, -OH, - SH, -SCN, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, Cs-Cs-cycloalkyl, wherein one or more CH2 groups of the aforementioned radicals may be replaced by a C=0 group, and/or the aliphatic and cycloaliphatic moieties of the aforementioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals selected from C1-C4 alkoxy;

Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, C1-C6- alkylsulfonyl, Ci-C₆-haloalkylthio, -OR^a, -NR^cR^d, -S(0)_nR^a, -S(0)_nNR^cR^d, -C(=0)R^a, -C(=0)NR^cR^d, -C(=0)OR , -C(=S)R^a, -C(=S)NR^cR^d, -C(=S)OR , -C(=S)SR , -C(=NR^c)R , and -C(=NR^c)NR^cR^d; k is O or l ;

n is 0, 1 or 2;

or a stereoisomer, salt, tautomer or N-oxide, or a polymorphic crystalline form, a co-crystal or a solvate of a compound or a stereoisomer, salt, tautomer or N-oxide thereof; the process comprising

c) providing a compound of the formula (I) by a process using a process step according to any of claims 1 to 10, in particular according to any of claims 5 to 8,

d) converting the compound of formula (I) to a compound of formula (l-B), optionally via the corresponding carbonyl compound of formula (l-A) as defined in claim 9.

12. The process according to claim 1 1 , wherein the process comprises

a) providing a compound of the formula (I) by a process according to any of claims 5 to 8, b) reacting the compound of formula (I) in a step (iii) to the corresponding carbonyl compound of formula (l-A) according to claim 9,

c) converting the compound of formula (l-A) in a step (iv) to a compound of formula (l-B) as defined in claim 1 1 .

13. The process according to claim 12, wherein step (iv) in c) comprises

iv) reacting the compound of the formula (l-A) as defined in claim 9 with a compound of the formula (V)

in which the variables R^2a, R^2b, R³, R⁵, R⁶ and k are each as defined in claim 1 1 , in the presence of a base, to obtain a compound of the formula (l-B) as defined in claim 1 1 .

The process according to any of claims 1 1 to 13, wherein the compound of formula (l-B) selected from the the group consisting of the following compounds 1-1 1 , 1-16, 1-21 , I-26, I 31 :