The present invention concerns new halogen substituted diketone compounds, new pyrazole compounds, processes for the manufacture of pyrazole compounds and processes for the manufacture of agrochemical or

pharmaceutical compounds.

3-halomethylpyrazole-4-yl carboxylic acids and esters are valuable intermediates in the synthesis of agrochemical and pharmaceutical active ingredients. Agrochemical active ingredients which contain such pyrazole building blocks are, for example, 2'-[l,l'-bicycloprop-2-yl]-3-(difluoromethyl)-l-methylpyrazole-4-carboxanilide (Sedaxane), as described, for example, in WO2006015866, 3-(difluoromethyl)-l-methyl-N-[2-(3',4',5'-trifluorophenyl)phenyl]pyrazole-4-carboxamide (Fluxapyroxad), as described, for example, in WO2006087343, N-(3\4'-Dichloro-5-fluorobiphenyl-2-yl)-3-(difluoromethyl)-l-methylpyrazole-4-carboxamide (Bixafen), as described, for example, in WO2003070705, 3-(Difluoromethyl)-l-methyl-N-[l,2,3,4-tetrahydro-9-(l-methylethyl)-l,4-methanonaphthalen-5-yl]-lH-pyrazole-4-carboxamide (Isopyrazam), as described, for example, in WO2004035589, (RS)-N-[9-(Dichloromethylen)-l,2,3,4-tetrahydro-l,4-methanonaphthalin-5-yl]-3-(difluoromethyl)- 1-methyl- lH-pyrazole-4-carboxamide (Benzovindiflupyr), as described, for example, in WO07048556. Generally, 3-halomethylpyrazole-4-yl carboxylic acids, often obtained by hydrolysis of their esters, are converted into the carboxamides, for example after conversion into the 3-halomethylpyrazole-4-yl carboxylic acid halide. Other conversions, wherein the carboxamide is generated directly from the ester or acid, have also been described, such as in WO2012055864 and WO 2007/031323. All foregoing cited patent applications are hereby incorporated for all purposes.

EP2297111 Bl describes the manufacture of 3-halomethylpyrazole-4-yl carboxylic esters starting from 2-(aminomethylidene)-3-oxobutyric esters.

The invention concerns thus a compound according to formula (I)

The residues R1, R2, R4, R5 and Y will be defined in the subsequent description.

The invention relates further to a process for manufacturing a compound according to formula (II)

which comprises the step of reacting a compound of formula (I) with a compound of formula (III), (VIII) or (V)

H2N— NH R3 (HI)

wherein R 3 and R 10 will be described in detail in the subsequent description, and R1 and R4 are the same as described for the compounds of formula (I) in the subsequent description.

The invention further concerns a compound of formula (VII)

(VII)

wherein R1, R2, R3 and R4 are defined in the subsequent description, and a process for manufacturing the same.

In another aspect, the invention concerns the process for the manufacture of an agrochemical or pharmaceutical compound, which comprises the process for the manufacture of the compounds of formula (II) or (VII), or both processes, mentioned above. In particular, when R10 is H in (II), often the carboxylic function is activated by formation of the carboxylic acid halide or anhydride, and subsequent reaction with an amine of formula (VI) NHR 12 Q, wherein R 12 is selected from the group consisting of H, Ci-C i2-alkyl, C2-C6 alkenyl or C3-C8-cycloalkyl group, wherein H and Ci-C4-alkyl are preferred, wherein Q is an optionally substituted aryl or heteroaryl group. In another process for the manufacture of an agrochemical or pharmaceutical compound, which comprises the process for the manufacture of the compounds of formula (II), when R10 is selected from the group consisting of Ci-Ci2-alkyl, C2-C6 alkenyl or C3-C8-cycloalkyl group, especially when R10 is Ci - C4-alkyl, is described in

WO2012055864, wherein the compound of formula (II) is contacted with an amine of formula (VI) NR 12 HQ, wherein R 12 is defined as above, wherein Q is an optionally substituted aryl or heteroaryl group, in the presence of at least one base. In yet another process for the manufacture of an agrochemical or pharmaceutical compound, the process comprises a step of reacting (VII) with an amine of formula (VI) NR 12 HQ, optionally after a step of converting (VII) into (II) and optionally activation of (II) when R10 is H, for example by conversion into the halide or anhydride. Such a process can also comprise a step of manufacturing a compound of formula (VII) from (I). In one particular embodiment, (VII) is used for the manufacture of an agrochemical or

pharmaceutical compound without intermediate conversion onto the

corresponding carboxylic acid and/or carboxylic acid halide or anhydride, by reaction with (VI), optionally in the presence of at least one base which is not (VI). The at least one base which is not (VI) preferably is a dialkylamine or trialkylamine, for example triethylamine.

In the present invention, designations in singular are in intended to include the plural; for example, "a solvent" is intended to denote also "more than one solvent" or "a plurality of solvents".

In the context of the present invention, the term "comprising" is intended to include the meaning of "consisting of.

When a double bond is depicted in a particular E/Z geometry, this is intended to also denote the other geometric form as well as mixtures thereof. A wavy bond is intended to denote the E geometry, the Z geometry and any mixture thereof.

The first compounds of the invention have the formula (I)

R1 is selected from the group consisting of CF2C1, CF2H, CFC12, CFC1H, CF2Br, CCI3 , CF3, CBr3, and CI3. Preferably, R1 is selected from the group consisting of CF2C1, CF2H, CFC12, CFC1H and CF2Br. More preferably, R1 is selected from the group consisting of CF2C1, CF2H, CFC12 and CFC1H. Even more preferably, R1 is selected from the group consisting of CF2C1 and CF2H. In a most preferred aspect, R1 is CF2H.

R is CHal3 wherein Hal is a halogen and each Hal is selected independently; wherein, when R 2 is CF3, R 1 contains two, one or zero fluorine atoms or, when R 2 1

is CCl3, R contains two, one or zero chlorine atoms;

preferably, all the Hal in CHal3 are the same Hal species; thus CHal3 preferably is selected from the group consisting of CCI3, CF3, CBr3, and CI3 ; R often is selected from the group consisting of CCI3, CF3, CBr3, and CI3 ; preferably, R is selected from the group consisting of CCI3, CF3 and CBr3. More preferably, R is selected from the group consisting of CCI3 and CF3. In one very preferred aspect, R 2 is 2

CCI3. In another very preferred aspect, R is CF3.

Y is selected from the group consisting of S, O and NR6, wherein O and NR6 are preferred

R4 is selected from the group consisting of H, X', OR', SR', COOR', C(0)NR'2, wherein R' are selected independently in C(0)NR'2, wherein R' is hydrogen or a Ci-Ci2-alkyl group, CN, Ci-Ci2-alkyl, C2-C6 alkenyl, aryl, cycloalkyl, aralkyl, heteroaryl, each of which is optionally substituted by one or more groups selected from the group consisting of -R', -X', -OR', -SR', -NR'2, -SiR'3, -COOR', -(C-O)R', -CN and -CONR'2, in which R' are selected independently, wherein R' is hydrogen or a Ci-Ci2-alkyl group and X' is F, CI, Br, or I ; when R4 is a Ci-C i2-alkyl group, methyl, ethyl, n-propyl, isopropyl, n-, iso-, sec- and t-butyl are preferred, and methyl and ethyl are most preferred;

R5 and R6 independently are selected from the group consisting of Ci-C12-alkyl, C2-C6 alkenyl or C3-Cio-cycloalkyl group, each of which is optionally substituted by one or more groups selected from the group consisting of -R', -X', -OR', -SR', -NR'2, -SiR'3, -COOR', -CN and -CONR'2, wherein R' is hydrogen or a Ci-Ci2-alkyl group, which is preferably selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-, iso-, sec- and t-butyl, and X' is F, CI, Br, or I,

or, when Y = NR6, R5 together with R6 and the nitrogen atom to which the two radicals are attached are an optionally substituted 5- to 10-membered heterocyclic radical which, in addition to the nitrogen atom, may contain a further 1, 2 or 3 heteroatoms selected from the group consisting of O, N and S as ring members.

In one particular aspect, Y is S, wherein R5 is hydrogen or a Ci-Ci2-alkyl group, preferably a Ci-C4-alkyl-group.

For the purpose of the present invention, the definition Ci-Ci2-alkyl comprises the largest range defined herein for an alkyl group. Specifically, this definition comprises, for example, the meanings methyl, ethyl, n-propyl, isopropyl, n-, iso-, sec- and t-butyl, n-pentyl, n-hexyl, 1,3-dimethylbutyl, 3,3-dimethylbutyl, n-heptyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl. Often, methyl, ethyl, n-propyl, isopropyl, n-, iso-, sec- and t-butyl are most preferred residues selected from the group Ci-Ci2-alkyl.

The term "C3-Cio-cycloalkyl", as used in this invention, denotes mono-, bi- or tricyclic hydrocarbon groups comprising 3 to 10 carbon atoms, especially 3 to 6 carbon atoms. Examples of monocyclic groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl. Examples of bicyclic groups include bicyclo[2.2.1]heptyl, bicyclo[3.1.1]heptyl,

bicyclo[2.2.2]octyl and bicyclo[3.2.1]octyl. Examples of tricyclic groups are adamantyl and homoadamantyl.

The term "C2-C6-alkenyl group "denotes a group comprising a carbon chain and at least one double bond. Alkenyl group are, for example, ethenyl, propenyl, butenyl, pentenyl or hexenyl.

In connection with the definition of the group -NR5R6, the term "5- to 10-membered heterocyclic radical" denotes a nitrogenous mono- or bicyclic group having 5, 6, 7, 8, 9 or 10 ring members, which is attached via the nitrogen atom to the remainder of the compound of the formula (I) or (II), which, in addition to the nitrogen atom, may have a further 1, 2 or 3 heteroatoms selected from the group consisting of O, N and S as ring members and which is unsubstituted or may have 1, 2 or 3 substituents. The substituents, provided they are attached to a carbon atom of the heterocyclic radical, are preferably selected from the group consisting of halogen, CN, C1 -C4 alkyl, C 1-C4- haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy and, provided they are attached to a further nitrogen atom of the heterocyclic radical, are preferably selected from the group consisting of C 1-C4-alkyl and Ci-C4-haloalkyl. Examples of 5- to 10-membered heterocyclic radicals are pyrrol- 1-yl, pyrrolidin-l-yl, oxazolidin-3-yl, thiazolidin-3-yl, imidazol-l-yl, imidazolin-l-yl, 3-methylimidazolin-l-yl, 3-ethylimidazolin-l-yl, 3-propylimidazolin- 1 -yl, 3 - ( 1 -methylethyl)imidazolin- 1-yl, 3-butylimidazolin- 1-yl, 3-(l,l- dimethylethyl)imidazolin-l-yl, pyrazol-l-yl, pyrazolidin-l-yl, 2-methylpyrazolidin-l-yl, 2- ethylpyrazolidin-l-yl, 2-prop yip yrazolidin- 1-yl, 2-(l-methylethyl)pyrazolidin-l-yl, 2- butylp yrazolidin- 1-yl, 2- (1,1-dimethylethyl)pyrazolidin-l-yl, piperidin-l-yl, morpholin-4-yl, thiamorpholin-4-yl, piperazin-l-yl, 4-methylpiperazin-l-yl, 4-ethylpiperazin-l-yl, 4-propylpiperazin-l-yl, 4-(l-methylethyl)piperazin-l-yl, 4-butylpiperazin-l-yl, 4-(1,1- dimethylethyl)piperazin-l-yl, indol-l-yl, indolin-l-yl, isoindol-l-yl, isoindolin-l-yl, indazol-l-yl, indazolin-l-yl, 2-methylindazolin-l-yl, indazolin-2-yl and 1-methylindazolin- 1-yl, where the heterocyclic groups mentioned above are unsubstituted, or 1, 2 or 3 of the ring carbon atoms carry a substituent selected from the group consisting of halogen, CN, nitro, Ci-C4-alkyl, C1 -C4-alkoxy and Ci-C4-haloalkoxy. Preferred heterocyclic radicals are optionally substituted piperidinyl and optionally substituted morpholinyl.

In the context of the present invention, aryl groups are, unless defined otherwise, aromatic hydrocarbon groups which may contain one, two or more heteroatoms selected from the group consisting of O, N, P and S and which may optionally be substituted by further groups selected from the group consisting of R', -X', -OR', -SR', -NR'2, -SiR'3, -COOR', -(C-O)R', -CN and -CONR'2, where R' and X' are defined as above.

In one aspect, the term "aryl" is a Cs-Cig-aryl. The term "Cs-Cig-aryl" denotes the largest range defined herein for an aryl groups having 5 to 18 skeleton atoms, where the carbon atoms may be replaced by heteroatoms, thus forming a heteroaryl. Specifically, this definition comprises, for example, the meanings cyclopentadienyl, phenyl, cycloheptatrienyl, cyclooctatetraenyl,

naphthyl and anthracenyl; 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-oxadiazol-3-yl, l,2,4-oxadiazol-5-yl, l,2,4-thiadiazol-3-yl, l,2,4-thiadiazol-5-yl, l,2,4-triazol-3-yl, l,3,4-oxadiazol-2-yl, l,3,4-thiadiazol-2-yl and l,3,4-triazol-2-yl; 1-pyrrolyl, 1-pyrazolyl, 1,2,4-triazol-l-yl, 1-imidazolyl, 1,2,3-triazol-l-yl, 1,3,4-triazol-l-yl; 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, l,3,5-triazin-2-yl and l,2,4-triazin-3-yl.

In the context of the present invention, arylalkyl groups (aralkyl groups) are, unless defined otherwise, alkyl groups which are substituted by aryl groups, which may have a Ci-g-alkylene chain and which may be substituted in the aryl skeleton or the alkylene chain by one or more heteroatoms selected from the group consisting of O, N, P and S and optionally by further groups selected from the group consisting of R', -X', -OR', -SR', -NR'2, -SiR'3, -COOR', -(C-O)R', -CN and -CONR'2, where R', which may further contain one or more heteroatoms selected from the group consisting of N, O, P and S, and X' are defined as above.

The definition C7-C 19 -aralkyl group comprises the largest range defined herein for an arylalkyl group having a total of 7 to 19 atoms in the skeleton and the alkylene chain. Specifically, this definition comprises, for example, the meanings benzyl and phenylethyl.

In the context of the present invention, alkylaryl groups (alkaryl groups) are, unless defined otherwise, aryl groups which are substituted by alkyl groups, which may have a Ci-Cg -alkylene chain and which may be substituted in the aryl skeleton or the alkylene chain by one or more heteroatoms selected from the groups consisting of O, N, P and S and optionally by further groups selected from the group consisting of R', -X', -OR', -SR', -NR'2, -SiR'3, -COOR', -(C-0)R', -CN and -CONR'2, where R', which may further contain one or more heteroatoms selected from the group consisting of N, O, P and S, and X' are defined as above.

The definition C7-C 19 -alkylaryl group comprises the largest range defined herein for an alkylaryl group having a total of 7 to 19 atoms in the skeleton and the alkylene chain. Specifically, this definition comprises, for example, the meanings tolyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethylphenyl.

In a first preferred embodiment in relation to the compound of formula (I),

Y is O, R1 is CF2C1, R2 is CC13, R4 is H and R5 is ethyl.

In a second preferred embodiment in relation to the compound of formula (I), Y is O, R1 is CF2C1, R2 is CF3, R4 is H and R5 is ethyl.

In a third preferred embodiment in relation to the compound of formula (I), Y is O, R1 is CF2H, R2 is CC13 , R4 is H are R5 is ethyl.

In a fourth preferred embodiment in relation to the compound of formula (I), Y is O, R1 is CF2H, R2 is CF3, R4 is H are R5 is ethyl.

In a fifth preferred embodiment in relation to the compound of formula (I),

Y is O, R1 is CF2H, R2 is CBr3, R4 is H and R5 is ethyl.

In a sixth preferred embodiment in relation to the compound of formula (I),

Y is O, R1 is CF2C1, R2 is CF3, R4 is H and R5 is ethyl.

In a seventh preferred embodiment in relation to the compound of formula (I), Y is NR6, R1 is CF2C1, R2 is CC13, R4 is H and R5 and R6 are CH3.

In an eighth preferred embodiment in relation to the compound of formula (I), Y is NR6, R1 is CF2C1, R2 is CF3 , R4 is H and R5 and R6 are CH3.

In a ninth preferred embodiment in relation to the compound of formula (I), Y is NR6, R1 is CF2H, R2 is CC13, R4 is H and are R5 and R6 are CH3.

In a tenth preferred embodiment in relation to the compound of formula (I),

Y is NR6, R1 is CF2H, R2 is CF3, R4 is H are R5 and R6 are CH3.

In an eleventh preferred embodiment in relation to the compound of formula (I), Y is NR6, R1 is CF2H, R2 is CBr3, R4 is H and R5 and R6 are CH3.

In a twelfth preferred embodiment in relation to the compound of formula (I), Y is NR6, R1 is CF2C1, R2 is CF3, R4 is H and R5 and R6 are CH3.

In a thirteenth preferred embodiment in relation to the compound of formula (I), Y is O, R1 is CF3 , R2 is CC13 , R4 is H and R5 is ethyl.

In a fourteenth preferred embodiment in relation to the compound of formula (I), Y is NR6, R1 is CF3, R2 is CC13, R4 is H and R5 and R6 are CH3.

In a fifteenth preferred embodiment in relation to the compound of formula (I), one methyl group R5of embodiments seven to twelve is replaced by C2-C12-alkyl, C3-Cio-cycloalkyl, aryl or aralkyl.

In a sixteenth preferred embodiment in relation to the compound of formula (I), the other methyl group in R6 of embodiment thirteen is replaced by C2-Ci2-alkyl, C3-Cio-cycloalkyl, aryl or aralkyl.

In a seventeenth preferred embodiment in relation to the compound of formula (I), the ethyl group R5 of the first to sixth or thirteenth preferred embodiment in relation to the compound of formula (I), is replaced by methyl, C3 -C i2-alkyl, C3-Cio-cycloalkyl, aryl or aralkyl.

In an eighteenth preferred embodiment in relation to the compound of formula (I), the ethyl group R5 of the first to sixth or thirteenth preferred embodiment in relation to the compound of formula (I), is replaced by methyl, C3 -C i2-alkyl, C3-Cio-cycloalkyl, aryl or aralkyl.

In a nineteenth preferred embodiment in relation to the compound of formula (I), R5 and R6 of the seventh to seventeenth preferred embodiment in relation to the compound of formula (I), together with the nitrogen atom to which the two radicals are attached, are an optionally substituted 5- to 10-membered heterocyclic radical which, in addition to the nitrogen atom, can contain a further 1, 2 or 3 heteroatoms selected from the group consisting of O, N and S as ring members.

The above preferred residues Y, R1, R2, R4, R5 and R6 also apply to the other compounds of the present invention, in particular to (II), (VII), (XIII), (IVa), (IVb), (IX) and (XII).

The compounds of formula (I) have been found to be particularly useful as starting materials or intermediates in the manufacture of compound of formula (II) or (VII), which are valuable intermediates for the manufacture of

agrochemical or pharmaceutical active ingredients. When reacted with a compound of formula (III), (VIII) or (V), the -C(0)R group can, for example, be simultaneously with the cyclization converted into a C(0)OR10 group under the reaction conditions required for the cyclization. In one preferred aspect, the reaction is carried out in the presence of at least one base other than (III), (VIII) and (V). Compound (II) can also be obtained by cyclization of (I) to (VII), with subsequent conversion of the C(0)R 2 group into the COOR 10 group as will be explained later. The compounds of formula (VII) can also be converted into compounds of formula (IX), as will be explained later.

The invention concerns thus a process for manufacturing a compound according to formula (II)

which comprises the step of reacting a compound of formula (I) with a compound of formula (III), (VIII) or (V)

H2N— NH R3 (III)

wherein R 3 in (III) and (V) is, or R 3 , R 3' and R 3 " independently from each other in (VIII) are, selected from the group consisting of Ci-Ci2-alkyl, C2-C6 alkenyl, cycloalkyl, aryl, heteroaryl, aralkyl, and, for R 3 ' and R 3 " , H,

each of which is optionally substituted by one or more groups selected from the group consisting of -R', -X', -OR', -SR', -NR'2, -SiR'3, -COOR", -CN and -CONR'2, where R' is hydrogen or a Ci-Ci2-alkyl group which are the same or different in - CONR'2, and X' is F, CI, Br, or I;

R10 is selected from the group consisting of H, Ci-Ci2-alkyl, C2-C6 alkenyl or C3-Cg-cycloalkyl group, each of which is optionally substituted by one or more groups selected from the group consisting of -R', -X', -OR', -SR', -NR'2, -SiR'3, -COOR', -(C-O)R', -CN and -CONR'2, where R' is hydrogen or a Ci-C12-alkyl group which are the same or different in - CONR'2, and X' is F, CI, Br, or I, wherein it is preferred that R10 is selected from H and Ci-C4-alkyl, and R10 = H is most preferred;

and wherein (I) is as defined as above.

The N-alkylhydrazones of the formula (VIII) have been described in the literature (Zhurnal Organicheskoi Khimii (1968), 4(6), 986-92) and can be obtained by reacting commercially available hydrazines of the formula (III) with carbonyl compounds of the formula R 3 ' R 3 " C=0.

selected from the group consisting of R9, wherein R9 denotes Ci

Ci2-alkyl, OR9 and NRURU , wherein R11 and R11' independently are selected from the group consisting of Ci-Ci2-alkyl and H. Compounds of formula (V) have been described in WO2015097658, which is hereby incorporated by reference for all purposes.

The compound of formula (III) and (VIII) are preferred in the manufacture of compound (II) from compound (I).

In one other preferred aspect, compound of formula (VIII) is preferred in the manufacture of compound (II), (VII) and/or (IX) from compound (I). The use of compound (VIII) in the manufacture of (II), (VII) and/or (IX) from compound (I) can result in an improved regio selectivity in the cyclization to obtain (II), (VII) and/or (IX). As stated above, R3 and R3" in formula (VIII) are

independently selected from the group consisting of Ci-Ci2-alkyl, C2-C6 alkenyl, cycloalkyl, aryl, heteroaryl, aralkyl and H. In a preferred aspect, R 3 ' is H and R " is selected from the group consisting of Ci-Ci2-alkyl, C2-C6 alkenyl, cycloalkyl, aryl, heteroaryl, aralkyl, wherein methyl, ethyl, i-prop, and aryl is preferred, and aryl = benzene is more preferred. In one aspect, the aryl, preferably benzene, residue is optionally substituted, preferably by one or more groups of NR 3 ' R 3 ", wherein NH2 is preferred, for example in p-position to the attachment position of the C-atom in 3-Position of (VIII). The p-amino-benzaldehyde which is released during the reaction of (VIII) with (I) can easily be recovered by acidic/basic extraction methods for convenient recycling. When compound of formula (VIII) is preferred in the manufacture of compound (II), (VII) and/or (IX) from compound (I), the reaction between (VIII) and (I) preferably is carried out in the presence of a catalyst, more preferably an acidic catalyst. Suitable catalysts are, for example, CH3COOH, CF3COOH, KHS04, H2SO4, NaHS04 and HC1. The catalyst can be employed in up to stoichiometric amounts in relation to compound (I), such as 0.95 or 1 eq.

In another preferred aspect, the reaction between (VIII) and (I) preferably is carried out in the absence of a catalyst.

When a compound of formula (VIII) is reacted with (I), a desired intermediate (XIV) generally forms, as described below. When (XIV) is contacted with an acid, as described below, generally a compound of formula

R 3 ' R 3 " C(O) is released. The compound, for example benzaldehyde, can be removed from the reaction mixture, for example by extraction or, preferably, distillation such as falling film distillation. The compound of formula

R 3J 'R 3J " C(O) can also be removed after the intermediate is contacted with the acid and base to obtain a compound of formula (XIII). In this case, R 3J ' R 3J " C(O) can be removed, for example, by organic extraction of the aqueous phase containing (XIII). R3 R3 'C(O) can thus be effectively recycled.

In a first preferred embodiment in relation to the manufacture of the compound of formula (II) from a compound of formula (I), Y is O, R1 is CF2C1,

R 2 is CCl3, R 4 is H and R 5 is ethyl in the compound of formula (I).

In a second preferred embodiment in relation to the manufacture of the compound of formula (II) from a compound of formula (I), Y is O, R1 is CF2C1, R 2 is CF3, R 4 is H and R 5 is ethyl in the compound of formula (I).

In a third preferred embodiment in in relation to the manufacture of the compound of formula (II) from a compound of formula (I), Y is O, R1 is CF2H,

R 2" is CCl3, R 4" is H are R 5 is ethyl in the compound of formula (I).

In a fourth preferred embodiment in relation to the manufacture of the compound of formula (II) from a compound of formula (I), Y is O, R1 is CF2H,

R 2" is CF3, R 4" is H are R 5 is ethyl in the compound of formula (I).

In a fifth preferred embodiment in relation to the manufacture of the compound of formula (II) from a compound of formula (I), Y is O, R1 is CF2H,

R 2 is CBr3, R 4 is H and R 5 is ethyl in the compound of formula (I).

In a sixth preferred embodiment in relation to the manufacture of the compound of formula (II) from a compound of formula (I), Y is O, R1 is CF2C1,

R 2 is CF3, R 4 is H and R 5 is ethyl in the compound of formula (I).

In a seventh preferred embodiment in relation to the manufacture of the compound of formula (II) from a compound of formula (I), Y is O, R 1 is CF3, R 2 is CC13, R4 is H and R5 is ethyl in the compound of formula (I).

In the abovementioned preferred embodiments in relation to the manufacture of the compound of formula (II) from a compound of formula (I), R in the compound of formula (III) preferably is Methyl.

In an eighth preferred in relation to the manufacture of the compound of formula (II) from a compound of formula (I), Y is NR6, R1 is CF2C1, R2 is CC13 , R4 is H and R5 and R6 are CH3.

In a ninth preferred in relation to the manufacture of the compound of formula (II) from a compound of formula (I), Y is NR6, R1 is CF2C1, R2 is CF3, R4 is H and R5 and R6 are CH3.

In a tenth preferred in relation to the manufacture of the compound of formula (II) from a compound of formula (I), Y is NR6, R1 is CF2H, R2 is CC13, R4 is H are R5 and R6 are CH3.

In an eleventh preferred embodiment in relation to the manufacture of the compound of formula (II) from a compound of formula (I), Y is NR6, R1 is CF2H, R2 is CF3 , R4 is H are R5 and R6 are CH3.

In a twelfth preferred embodiment in relation to the manufacture of the compound of formula (II) from a compound of formula (I), Y is NR6, R1 is CF2H, R2 is CBr3, R4 is H and R5 and R6 are CH3.

In a thirteenth preferred in relation to the manufacture of the compound of formula (II) from a compound of formula (I), Y is NR6, R1 is CF2C1, R2 is CF3, R4 is H and R5 and R6 are CH3.

In a fourteenth preferred in relation to the manufacture of the compound of formula (II) from a compound of formula (I), Y is NR6, R1 is CF3, R2 is CC13, R4 is H and R5 and R6 are CH3.

In a fifteenth preferred embodiment in relation to the manufacture of the compound of formula (II) from a compound of formula (I), one methyl group R5 in (I) of embodiments eight to fourteen is replaced by C2-Ci2-alkyl, C3-C KT cycloalkyl, aryl or aralkyl.

In a sixteenth preferred embodiment in relation to the manufacture of the compound of formula (II) from a compound of formula (I), the other methyl group R6 of embodiment fifteen is replaced by C2-Ci2-alkyl, C3-Cio-cycloalkyl, aryl or aralkyl.

In a seventeenth preferred embodiment in relation to the manufacture of the compound of formula (II) from a compound of formula (I), the ethyl group R5 of the first to sixth preferred embodiment in relation to the manufacture of the compound of formula (II) from a compound of formula (I), is replaced by methyl, C3-Ci2-alkyl, C3-Cio-cycloalkyl, aryl or aralkyl.

In an eighteenth preferred embodiment in relation to the manufacture of the compound of formula (II) from a compound of formula (I), R5 and R6 of the eight to seventeenth preferred embodiment in relation to the manufacture of the compound of formula (II) from a compound of formula (I), together with the nitrogen atom to which the two radicals are attached, are an optionally substituted 5- to 10-membered heterocyclic radical which, in addition to the nitrogen atom, may contain a further 1, 2 or 3 heteroatoms selected from the group consisting of O, N and S as ring members.

The above preferred residues of the preferred embodiments in relation to the manufacture of the compound of formula (II) from a compound of formula (I), such as Y, R1, R2, R4, R5 and R6, also apply to the other compounds of the present invention, in particular to (I), (VII), (XIII), (IVa), (IVb), (IX) and (XII), and the manufacture of any of those compounds from (II) or (I).

In the process according to the present invention, the compound of formula (III), (VIII) or (V) is often used in an amount of equal to or greater than 0.8 mol, preferably equal to or greater than 0.9 mol and more preferably equal to or greater than 0.95 mol based on 1 mol of formula (I). Often, the compound of formula (III), (VIII) or (V) is used in an amount of equal to or less than 1.2 mol, preferably equal to or less than 1.1 mol and more preferably equal to or less than 1.05 mol based on 1 mol of formula (I). In one aspect, Compound (III) is preferred.

The compound of formula (III) or (V), preferably (III), can also be employed in its hydrate form, or in a salt, more particularly a halide, form. In another aspect, the compound of formula (III) is used in its anhydrous form. In yet still another aspect, the compound of formula (III) is used as aqueous solution, or in a mixture of a solvent and water. This often has the advantage that the formula (III) is provided in a less hazardous form.

C L A I M S

1. Compound according to formula (I)

wherein

R1 is selected from the group consisting of CF2C1, CF2H, CFC12, CFC1H,

CF2Br, CC13, CF3, CBr3, and CI3;

R is CHal3 wherein Hal is a halogen and each Hal is selected independently; wherein, when R 2 is CF3, R 1 contains two, one or zero fluorine atoms or, when R 2 is CCl3, R 1 contains two, one or zero chlorine atoms,

Y is selected from the group consisting of S, O and NR6, wherein O and NR6 are preferred,

R4 is selected from the group consisting of H, X', COOR', OR', SR', C(0)NR'2, wherein R' are selected independently in C(0)NR'2 where R' is hydrogen or a Ci-Ci2-alkyl group, CN, Ci-Ci2-alkyl, C2-C6 alkenyl, aryl, cycloalkyl, aralkyl, heteroaryl, each of which is optionally substituted, and X' is F, CI, Br, or I;

R5 and R6 independently are selected from the group consisting of Ci-C12-alkyl, C2-C6 alkenyl or C3-Cio-cycloalkyl group, each of which is optionally substituted

or, when Y = NR6, R5 together with R6 and the nitrogen atom to which the two radicals are attached are an optionally substituted 5- to 10-membered heterocyclic radical which, in addition to the nitrogen atom, may contain a further 1, 2 or 3 heteroatoms selected from the group consisting of O, N and S as ring members.

2. Compound according to claim 1, wherein R is selected from the group consisting of CC13, CF3, CBr3, and CI3.

3. Compound according to claim 1 or 2, wherein

RHs CF2C1, Y is O, R2 is CC13 , R4 is H, R5 is ethyl or

Rxis CF2C1, Y is O, R2 is CF3, R4 is H, R5 is ethyl or

Rxis CF2H, Y is O, R2 is CC13, R4 is H, R5 is ethyl or

Rxis CF2H, Y is O, R2 is CF3, R4 is H, R5 is ethyl or

Rxis CF2H, Y is O, R2 is CBr3, R4 is H, R5 is ethyl or

Rxis CF2C1, Y is O, R2 is CF3, R4 is H, R5 is ethyl, or

Rxis CF2C1, Y is NR6, R2 is CC13, R4 is H, R5 and R6 are CH3 or

Rxis CF2C1, Y is NR6, R2 is CF3, R4 is H, R5 and R6 are CH3 or

Rxis CF2H, Y is NR6, R2 is CC13, R4 is H, R5 and R6 are CH3 or

Rxis CF2H, Y is NR6, R2 is CF3, R4 is H, R5 and R6 are CH3 or

Rxis CF2H, Y is NR6, R2 is CBr3, R4 is H, R5 and R6 are CH3 or

Rxis CF3, Y is O, R2 is CC13, R4 is H, R5 is ethyl, or

Rxis CF3, Y is NR6, R2 is CC13, R4 is H, R5 and R6 are CH3 or

Rxis CF2C1, Y is NR6, R2 is CF3, R4 is H, R5 and R6 are CH3.

4. Process for manufacturing a compound according to formula (II)

which comprises the step of reacting a compound of formula (I) with a compound of formula (III), (VIII) or (V)

H2N— NH R3 (HI)

wherein R 3 in (III) and (V) is, or R 3 , R 3' and R 3 " independently from each other in (VIII) are, selected from the group consisting of Ci-Ci2-alkyl, C2-C6 alkenyl, cycloalkyl, aryl, heteroaryl, aralkyl, and for R 3 ' and R 3 " H, each of which is optionally substituted,

R10 is selected from the group consisting of H, Ci-Ci2-alkyl, C2-C6 alkenyl or

C3-Cg-cycloalkyl group, each of which is optionally substituted,

R8 is selected from the group consisting of
OR9 and NRnRi r,

Ν,Ν-diisopropylethylamine wherein Ruand R11 independently are selected from the group consisting of Ci-Ci2-alkyl and H.

and wherein (I) is as defined according to anyone of claims 1 to 3.

5. Process according to claim 4, wherein the process is performed presence of at least one base.

6. Compound of formula (VII)

wherein R1, R2, R3 and R4 are as defined as in anyone of claims 1 to 4.

7. Process for manufacturing a compound according to formula (VII)

which comprises the step of reacting a compound of formula (I) with a compound of formula (III), (VIII) or (V)

H2N— NH R3 (HI)

(VIII)

wherein R 3 in (III) and (V) is, or R 3 , R 3' and R 3 " independently from each other in (VIII) are, selected from the group consisting of Ci-Ci2-alkyl, C2-C6 alkenyl, cycloalkyl, aryl, heteroaryl, aralkyl, and for R 3 ' and R 3 " H, each of which is optionally substituted,

R10 is selected from the group consisting of H, Ci-Ci2-alkyl, C2-C6 alkenyl or C3-Cg-cycloalkyl group, each of which is optionally substituted,

R8 is selected from the group consisting of R9= Ci-Ci2-alkyl, OR9 and NRnRi r, wherein Ruand R11 independently are selected from the group consisting of Ci-Ci2-alkyl and H,

and wherein (I) is as defined according to anyone of claims 1 to 3.

8. Process for the manufacture of a compound of formula (II), which comprises the step of contacting a compound of formula (VII) with a base, wherein the compound (II) is defined according to claim 4, and the compound of formula (VII) is defined according to claim 5.

9. Process according to anyone of claims 4, 5 or 8, wherein the compound of formula (II) is present in the form of a carboxylate (XIII), and wherein the reaction mixture comprising the compound of formula (XIII) is subjected to acidification to obtain the free carboxylic acid (II) with R10 =H.

10. Process according to claim 4, 5, 7, 8 or 9, wherein R is selected from the group consisting of CF2C1, CF2H, CFC12, CFC1H, CF3 and CF2Br.

11. Process according to claim 10, wherein R is selected from the group consisting of CC13, CF3 and CBr3.

12. Process according to anyone of claims 4, 5 or 7 to 11, which comprises the step of reacting a compound of formula (IVa) with a compound of formula (Va) or (Vb) to obtain compound (I)

(IVa) (I)

or which comprises the step of reacting a compound of formula (IVb) with a compound of formula (Vc) or (Vd) to obtain compound (I)

(IVb) (I)

wherein R1, R2, R4 and R5 are defined as in any of the preceding claims.

13. Process according to claim 12, wherein the step of reacting a compound of formula (IVa) with a compound of formula (Va) or (Vb) or the step of reacting a compound of formula (IVb) with a compound of formula (Vc) or (Vd) is performed in the presence of at least one base.

14. Process according to claim 12 or 13, which further comprises the step of reacting a compound of formula (Via) or (VIb) to obtain a compound of formula (IVa) or (IVb), wherein in (IVa) and (IVb), Y = NR6, wherein LG is a suitable leaving group, and R4, R1, R5 and R6 are as defined according to anyone of claims 1 to 3, according to the following reaction scheme

(VIb)

(IVb)

15. Process for the manufacture of an agrochemical or pharmaceutical compound, which comprises the use of the compound according to anyone of claim 1, 2, 3 or 6 or which comprises the process according to anyone of claims 4, 5 or 7 to 14.

16. Process for the manufacture of an agrochemical or pharmaceutical compound, wherein the compound (VII) of claim 6 is reacted with at least one amine of formula (VI) NR 12 HQ, wherein R 12 is selected from the group consisting of H, Ci-Ci2-alkyl, C2-C6 alkenyl or C3-Cg-cycloalkyl group, wherein H and Ci-C4-alkyl are preferred, and wherein Q is an optionally substituted aryl or heteroaryl group.

17. Process according to claim 15 or 16, wherein R1 is selected from the group consisting of CF2H, CF3 and CC12H.

18. Compound of formula (XII),

wherein R1, R2, R4, Y, R5 and R6 are defined as above.

19. Use of a compound of formula (XII) for the manufacture of a compound of formula (II), (VII) or (XIII) .

20. Process for the manufacture of a compound of formula (II), (VII) or (XIII), which comprises the step of reacting a compound of formula (XII) with a compound of formula (III), (VIII) or (V), which is optionally performed in the presence of a base, and which optionally comprises a step of acidification of a reaction mixture comprising a compound of formula (XIII).

21. Process for the manufacture of an agrochemical or pharmaceutical compound, which comprises the use of the compound according to claim 18 or which comprises the process according to claim 20.

22. Compound of formula (XIV),

(XIV)

wherein R 1 , R 2", R 4", R 3J, R 3J ' and R 3J " are defined as above.

21. Use of a compound of formula (XIV) for the manufacture of a compound of formula (II), (VII) or (XIII).