WO2012146598A1 - Process for the preparation of 2-substituted 4-amino-2,4-dihydro-[1,2,4]triazole-3-thiones - Google Patents

Abstract

Preparation of 2-substituted 4-amino-2,4-dihydro-[1,2,4]triazole 3-thiones of the formula (I), by reacting 1-substituted 4-amino-4H-[1,2,4]-triazolium salts with sulfur in water or in a protic organic solvent or mixtures of such solvents in the presence of a base.

Description

Process for the preparation of 2-substituted 4-amino-2,4-dihydro-[1 ,2,4]triazole-3- thiones

The present invention relates to a process for preparing 2-substituted 4-amino-2,4- dihydro-[1 ,2,4]triazole-3-thiones, in particular pesticidal compounds of this triazole class with phytopathogenic activity. The invention also relates to specific 2-substituted 4-amino-2,4-dihydro-[1 ,2,4]triazole-3-thiones and to intermediates that are obtained during the reaction sequence. Important pesticidal compounds carry a mercapto-triazole group. Specific thio-triazole compounds are known as active ingredients having pesticidal, in particular fungicidal activity, for example, from WO 96/38440 (A1 ). Also WO 2009/077471 (A2), WO 2009/077443 (A2), WO 2009/077500 (A2), WO 2009/077497 (A2), EP 09178224 (A1 ), EP 09178291 (A1 ), E P 09178288 (A1 ) describe further specific mercapto-triazole compounds and provide routes for the preparation of disclosed compounds. However, prepa ration of such 2,4-dihydro-[1 ,2,4]triazole-3-thione derivatives is often cumbersome and not high yielding.

In particular it is known to introduce the thio-group into triazole compounds using a strong base such as n-BuLi and sulfur powder. Alternatively triazole compounds are heated with sulfur in the presence of an aprotic polar solvent, such as, for example, Ν,Ν-dimethylformamide. S e e a l s o W O 99/19307 (A1 ), WO 97/06151 (A1 ), WO 97/051 19 (A1 ) and WO 96/41804 (A1 ). The disadvantages of these methods are that the yield of the desired products is often not satisfying, high amounts of side products are produced and that the reaction conditions often do not allow for the application on technical scales. Regarding the reaction using n-BuLi, a further disadvantage is that the reagent is quite expensive and that the reaction has to be carried out at very low temperatures, which necessitates special cooling equipment. Upscales are thus elaborate and expensive.

DE 19744401 (A1 ) describes the process for the preparation of certain 2-substituted 2,4-dihydro-[1 ,2,4]triazole-3-thiones using a hydrazine derivative with a carbonyl compound and thiocyanate to provide an intermediate triazolidinethione which is, in a second step, treated with formic acid to provide the corresponding 2,4-dihydro- [1 ,2,4]triazole-3-thiones. In analogy to this transformation DE 19839688 (A1 ) describes the reaction of a hydrazine derivative with formaldehyde und thiocyanate to give an intermediate triazolidinethione, which can be reacted with formic acid or an oxidizing agent to give corresponding 2,4-dihydro-[1 ,2,4]triazole-3-thione derivatives.

This type of process suffers from the disadvantage that hydrazine derivatives are often not readily available. Moreover yields of the transformations are low. An alternative synthetic route to obtain 2-substituted 4-amino-2,4-dihydro- [1 ,2,4]triazole-3-thiones compounds is described in the literature (H. G. O. Becker, D. Nagel , H .-J. Timpe J. Prakt. Chem. 1973, 315, 97-105) where thiolation of corresponding amino-triazolium salts is carried out by way of treatment with sulfur in the presence of triethylamine in pyridine as the solvent. The same procedure is described for the thiolation of analog structural isomers, 4-substituted 1 -amino-1 ,2,4- triazolthiones by G . La u s a n d W. Klotzer in Synthesis 1990, 707-717. The disadvantages of the protocol are moderate yields and long reaction times. Moreover pyridine is an expensive and toxic solvent and therefore poses risks to the environment and is problematic with regards to worker exposure. Since pyridine has a low vapor pressure (18 mm Hg), and its flash point of 21 °C implies that it can be ignited under almost all ambient temperature conditions, it is not a suitable solvent to be used in industrial scale production processes. The methods known from the prior art for the efficient synthesis of substituted thiono- triazoles are disadvantageous because the yields are insufficient and/or the reaction conditions and parameters such as temperature and/or reactants are not suitable for the industrial scale. It is therefore an objective of the present invention to provide an efficient process for the preparation of 4-amino-2,4-dihydro-[1 ,2, 4]triazole-3-thiones, which affords the desired compounds with high yields and is suitable for the industrial scale.

It has now surprisingly been found a highly efficient general protocol for the introduction of sulfur into 1 -substituted 4-amino-[1 ,2,4]-triazolium salts to provide corresponding 4- amino-2,4-dihydro-[1 ,2,4]triazole-3-thione compounds. These can be efficiently deami- nated to give desired 2,4-dihydro-[1 ,2,4]triazole-3-thiones which have an enormous economic significance as fungicidally active compounds. For these reasons, inter alia, there is an ongoing need for improved processes that easily make the mercapto- triazole compounds available.

Accordingly, one aspect of the present invention is a process for the preparation of a compound of the formula (I)

wherein

R is a group (1 )

wherein # shall mean the point of attachment to the triazolo group, and A and B are defined as follows:

A or B is a three-, four-, five-, six-, seven-, eight-, nine- or ten-membered saturated or partially unsaturated heterocycle or five-, six-, seven-, eight-, nine- or ten-membered aromatic heterocycle, where the heterocycle contains in each case one, two, three or four heteroatoms from the group consisting of O, N and S; is naphthyl or phenyl; and the respective other variable B or A has one of the meanings mentioned above for A or B or is Ci-Cs-alkyl, Ci-Cs-haloalkyl, C2-C8-alkenyl, C2-C8- haloalkenyl, C2-Cs-alkynyl, C2-C8-haloalkynyl, Cs-Cs-cycloalkyl, C3-C8- halocycloalkyl, or benzodioxolyl; where A and/or B independently of one another are unsubstituted or substituted by one, two, three or four independently selected substituents L; wherein

L is halogen, cyano, nitro, cyanato (OCN), Ci-Cs-alkyl, Ci-Cs-haloalkyl, phenyl-Ci-C6-alkyloxy, C2-Cs-alkenyl, C2-C8-haloalkenyl, C2-Cs-alkynyl, C2- Cs-haloalkynyl, C4-Cio-alkadienyl, C4-Cio-haloalkadienyl, Ci-Cs-alkoxy, Ci- Cs-haloalkoxy, Ci-Cs-alkylcarbonyloxy, d-Cs-alkylsulfonyloxy, C2-C8- alkenyloxy, C2-C8-haloalkenyloxy, C2-C8-alkynyloxy, C2-C8-haloalkynyloxy, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, Cs-Cs-cycloalkenyl, Cs-Cs-halocyclo- alkenyl, Cs-Cs-cycloalkoxy, C3-C6-cycloalkenyloxy, hydroxyimino-Ci-Cs- alkyl, Ci-C6-alkylene, oxy-C2-C4-alkylene, oxy-Ci-C3-alkyleneoxy, Ci-Cs- a I koxi m i no-Ci-Cs-a I kyl , C2-Cs-a I kenyloxi m i no-Ci-Cs-a I kyl , C2-Cs-a I kynyl- oximino-CrCe-alkyl, S(=0)_nA¹, C(=0)A², C(=S)A², NA³A⁴, phenyl-Ci-C₈- alkyl, phenyl , phenyloxy or a five- or six-membered saturated, partially unsaturated or aromatic heterocycle which contains one, two, three or four heteroatoms from the group consisting of O, N and S; where n, A¹, A², A⁵, A⁶ are: n is 0, 1 or 2;

A¹ is hydrogen, hydroxyl, Ci-Cs-alkyl, Ci-Cs-haloalkyl, amino, Ci-Cs- alkylamino or di-Ci-Cs-alkylamino,

A² is one of the groups mentioned for A¹ or C2-Cs-alkenyl, C2-C8- haloalkenyl, C2-C8-alkynyl, C2-C8-haloalkynyl, Ci-Cs-alkoxy, Ci-Cs- haloalkoxy, C2-C8-alkenyloxy, C2-C8-haloalkenyloxy, C2-C8-alkynyloxy, C2-C8-haloalkynyloxy, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, C3-C8- cycloalkoxy or Cs-Cs-halocycloalkoxy;

A⁵, A⁶ independently of one another are hydrogen, d-Cs-alkyl,

Ci-Cs-haloalkyl, C2-Cs-alkenyl, C2-C8-haloalkenyl, C2-Cs-alkynyl, C2- Cs-haloalkynyl, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, C3-Cs-cyclo- alkenyl or C3-Cs-halocycloalkenyl; where the aliphatic and/or alicyclic and/or aromatic groups of the radical definitions of L for their part may carry one, two, three or four identical or different groups R^L: is halogen, cyano, nitro, d-Cs-alkyl, Ci-Cs-haloalkyl, Ci-Cs-alkoxy, Ci- Cs-haloalkoxy, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, C3-C8- cycloalkenyl, C3-Cs-cycloalkoxy, Cs-Cs-halocycloalkoxy, Ci-Cs- alkylcarbonyl, Ci-Cs-alkylcarbonyloxy, Ci-Cs-alkoxycarbonyl, amino, Ci-Ce-alkylamino, di-Ci-Cs-alkylamino; or roup (2)

\ 1 1

R (2)

OH

wherein

# shall mean the point of attachment to the triazolo group and R¹¹ and R²² have the following meanings:

R¹¹, R²² independently of one another Ci-C6-alkyl, Ci-C6-haloalkyl, C3-C6- cycloalkyl, C3-C6-halocycloalkyl or phenyl, wherein the alkyl, cy- cloalkyl and phenyl moieties may be unsubstituted or substituted by one, two, three or four substituents L;

R¹¹ and R²², together with the carbon atom to which they are attached, form a five- or six-membered saturated or partially unsaturated ring, that can be unsubstituted or substituted by one, two, three, four or five substituents L', wherein L' stands for L as defined above or stands for a group

_R33

F

R⁴⁴

wherein R³³ and R⁴⁴ independently are selected from the group of hydrogen and the meaning for L as defined above; or R is a group (3)

wherein

# shall mean the point of attachment to the triazolo group and R⁵⁵, R⁶⁶ and R^; have the following meanings: phenyl-Ci-Cs-alkyI, phenyl or a five- or six-membered saturated, partially unsaturated or aromatic heterocycle which contains one, two, three or four heteroatoms from the group consisting of O, N and S; where the aliphatic and/or aromatic and/or heterocyclic groups for their part may carry one, two, three or four identical or different groups selected from halogen, cyano, nitro, Ci-Cs-alkyl, Ci-Cs-haloalkyl, d-Cs-alkoxy, Ci-Cs- haloalkoxy, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, Cs-Cs-cycloalkenyl, C3-C8-cycloalkoxy, Cs-Cs-halocycloalkoxy, d-Cs-alkylcarbonyl, d-Cs- alkylcarbonyloxy, d-Cs-alkoxycarbonyl, amino, d-Cs-alkylamino, di-d- Cs-alkylamino, phenyl, halophenyl, phenyloxy, halophenyloxy;

R⁶⁶, R⁷⁷ independently of one another are hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl or phenyl, wherein the alkyl, cycloalkyi or phenyl moieties may be unsubstituted or substituted by one, two or three substituents selected from halogen, cyano, nitro, d- Cs-alkyl, Ci-Cs-haloalkyl, Ci-Cs-alkoxy, d-Cs-haloalkoxy; by reacting a compound of formula (II)

wherein the variables are defined as follows:

R is as defined above, and Χ- is halide, arylsulfonate, alkylsulfonate, haloalkylsulfonate or X⁰¹OSO3, in which X⁰¹ is d-Cs-alkyl, C-i-Cs-haloalkyl or Cs-Cs-cycloalkyl where above mentioned alkyl, haloalkyl or aryl groups are unsubstituted or substituted by one, two, three or four independently selected inert substituents, with sulfur in a solvent in the presence of a base characterized in that as solvent water or a protic, organic solvent is used or a mixture of such solvents.

In the following, the meaning of the substituents of the compounds used according to the invention is further defined. Thereby, in each case the substituents are meant to have the given meanings and preferred meaning on their own or in any combination with the meanings or preferred meanings of any other substituent.

The finding of the present invention is that, ultimately, it offers a very general method for introducing sulfur into triazole groups. If necessary, some reactive groups within the group R can be protected via suitable protecting groups. It is within the skill of a person of the art to choose suitable groups and it is general knowledge of the skilled person how to insert and remove such groups.

According to one embodiment of the present invention, the group R in the compounds (I) and the precursors thereof carries an epoxide group. In a particular embodiment thereof, R is a group of the formula (1 ).

In group (1 ) particular preference is given to the following meanings of the substituents, in each case on their own or in combination.

According to one embodiment, A and B independently are unsubstituted phenyl or sub- stituted phenyl containing one, two, three or four independently selected substituents L.

According to one specific embodiment, A is unsubstituted phenyl.

According to a further embodiment, A is phenyl, containing one, two, three or four, in particular one or two, independently selected substituents L, wherein L is as defined or as preferably defined herein. According to one aspect of this embodiment, one of the substituents is in 4-position (para) of the phenyl ring. According to a further aspect, L is in each case independently selected from F, CI, Br, nitro, phenyl, phenoxy, methyl, ethyl, iso-propyl, tert-butyl, methoxy, ethoxy, trifluoromethyl, trichloromethyl, difluoro- methyl, difluorochloromethyl, trifluoromethoxy, difluoromethoxy and trifluorochloro- methyl. According to another specific aspect, L is in each case independently selected from F, CI and Br, in particular F and CI. According to another embodiment, A is monosubstituted phenyl, containing one substituent L, wherein L is as defined or as preferably defined herein. According to one aspect, said substituent is in para-position.

According to a specific embodiment, A is 3-fluorophenyl.

According to another embodiment, A is phenyl, containing two or three independently selected substituents L.

According to another preferred embodiment of the invention, A is phenyl which is substituted by one F and contains a further substituent L, where the phenyl may additionally contain one or two substituents L selected independently of one another, wherein L is as defined or preferably defined herein. According to a preferred embodiment, A is a group

in which # is the point of attachment of the phenyl ring to the oxirane ring; and

L² is selected from the group consisting of F, CI, NO2, phenyl, halogenphenyl, phenoxy, halogenphenoxy, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, C1-C4- haloalkoxy and Ci-C4-haloalkylthio;

L³ is independently selected from the group consisting of F, CI, Br, NO2, phenyl, halogenphenyl, phenoxy, halogenphenoxy, Ci-C4-alkyl, Ci-C4-haloalkyl, C1-C4- alkoxy, Ci-C4-haloalkoxy and Ci-C4-haloalkylthio; and

m is 0, 1 or 2.

In one embodiment, L² is selected from the group consisting of F, CI, methyl, methoxy, CF3, CHF2, OCF3, OCF3 and OCHF2. According to a more specific embodiment, L² is F or CI. In one embodiment, L³ is independently selected from the group consisting of F, CI, methyl, methoxy, CF3, CHF2, OCF3, OCF3 or OCHF2. According to a more specific embodiment, L³ is independently F or CI.

According to a preferred embodiment, m = 0. According to a further preferred embodiment, m = 1.

In the formula A-1 , the fluorine substituent is, according to a preferred embodiment, in the 4-position. According to still another embodiment, A is disubstituted phenyl, containing exactly two substituents L that are independently selected from each other, wherein L is as defined or as preferably defined herein. In particular, L is in each case independently selected from F, CI, Br, Ci-C4-alkyl, Ci-C4-haloalkyl and Ci-C4-alkoxy, in particular selected from F, CI, Ci-C4-alkyl, Ci-C4-haloalkyl and Ci-C4-alkoxy, in particular selected from F, CI, methyl, trifluoromethyl and methoxy. According to a further aspect of this embodiment, the second substituent L is selected from methyl, methoxy and chloro. According to another aspect, one of the substituents is in the 4-position of the phenyl ring. According to another specific aspect, A is phenyl containing one F and exactly one further substituent L as defined or preferably defined herein.

According to yet a further preferred embodiment, A is disubstituted phenyl which contains one F and a further substituent L selected from the group consisting of CI, C1-C4- alkyl, Ci-C4-haloalkyl and Ci-C4-alkoxy, in particular selected from the group consisting of CI, methyl, trifluoromethyl and methoxy. The second substituent L is specifically selected from the group consisting of methyl, methoxy and chlorine. According to one aspect thereof, one of the substituents is located in the 4-position of the phenyl ring. According to another specific embodiment, A is 2,4-disubstituted phenyl. According to still another specific embodiment, A is 2,3-disubstituted phenyl. According to still another specific embodiment, A is 2,5-disubstituted phenyl. According to still another specific embodiment, A is 2,6-disubstituted phenyl. According to still another specific embodiment, A is 3,4-disubstituted phenyl. According to still another specific embodiment, A is 3,5-disubstituted phenyl.

According to a further preferred embodiment of the invention, A is phenyl which is substituted by exactly two F. According to one aspect, A is 2,3-difluoro-substituted. According to a further aspect, A is 2,4-difluoro-substituted. According to yet a further aspect, A is 2,5-difluoro-substituted. According to yet a further aspect, A is 2,6-difluoro- substituted. According to yet a further aspect, A is 3,4-difluoro-substituted. According to yet a further aspect, A is 3,5-difluoro-substituted.

According to a further embodiment, A is trisubstituted phenyl containing exactly three independently selected substituents L, wherein L is as defined or preferably defined herein. According to yet a further embodiment, A is phenyl which is substituted by exactly three F. According to one aspect, A is 2,3,4-trisubstituted, in particular 2,3,4- trifluoro-substituted. According to another aspect, A is 2,3,5-trisubstituted, in particular 2,3,5-trifluoro-substituted. According to still another aspect, A is 2,3,6-trisubstituted, in particular 2,3, 6-trifluoro-substituted. According to stil l another aspect, A is 2 ,4,6- trisubstituted, in particular 2,4, 6-trifluoro-substituted. According to still another aspect, A is 3,4,5-trisubstituted, in particular 3,4,5-trifluoro-substituted. According to still another aspect, A is 2,4,5-trisubstituted, in particular 2, 4, 5-trifluoro-substituted.

According to a preferred embodiment, B is phenyl, that is unsubstituted or phenyl which contains one, two, three or four independently selected substituents L, wherein L is as defined or preferably defined herein.

According to one embodiment of the invention, B is unsubstituted phenyl. According to a further embodiment, B is phenyl which contains one, two, three or four independently selected substituents L, wherein L is as defined or preferably defined herein.

According to a further embodiment, B is phenyl which contains one, two or three, preferably one or two, independently selected substituents L, wherein L is as defined or preferably defined herein. Accord i ng to a specific aspect, L is i n each case independently selected from F, CI, Br, methyl, methoxy and trifluoromethyl. According to still another embodiment, B is phenyl, which contains one, two or three, preferably, one or two, halogen substituents.

According to a further embodiment, B is phenyl which contains one, two, three or four substituents L, wherein L is independently selected from F, CI, Br, methyl, ethyl, iso- propyl, tert-butyl, methoxy, ethoxy, trifluoromethyl, trichloromethyl, difluoromethyl, di- fluorochloromethyl, trifluoromethoxy, difluoromethoxy and difluorochloromethyl. Accord- ing to a specific aspect, L is in each case independently selected from F, CI and Br.

According to still a further embodiment, B is unsubstituted phenyl or phenyl which contains one, two or three substituents independently selected from halogen, NO2, amino, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkyl, Ci-C4-haloalkoxy, Ci-C4-alkylamino, Ci-C4-dialkylamino, thio and Ci-C4-alkylthio.

According to a further embodiment, B is a phenyl ring that is monosubstituted by one substituent L, where according to a special aspect of this embodiment, L is located in the ortho-position to the point of attachment of the phenyl ring to the oxirane ring. L is as defined or preferably defined herein. According to a further specific embodiment, B is monochloro-substituted phenyl, in particular 2- chlorophenyl.

According to a further embodiment, B is phenyl, which contains two or three, in particular two, independently selected substituents L, wherein L is as defined or preferably defined herein. According to a further embodiment of the invention, B is a phenyl ring which contains a substituent L in the ortho-position and furthermore has one further independently selected substituent L. According to one aspect, the phenyl ring is 2,3-disubstituted. According to a further aspect, the phenyl ring is 2,4-disubstituted. According to yet a further aspect, the phenyl ring is 2,5-disubstituted. According to yet a further aspect, the phenyl ring is 2,6-disubstituted.

According to a further embodiment of the invention, B is a phenyl ring which contains a substituent L in the ortho-position and furthermore contains two further independently selected substituents L. According to one aspect, the phenyl ring is 2,3,5-trisubstituted. According to a further aspect, the phenyl ring is 2,3,4-trisubstituted. According to yet a further aspect, the phenyl ring is 2,4,5-trisubstituted.

In a further embodiment, B is phenyl which contains one substituent L in the 2-position and one, two or three further independently selected substituents L. According to a preferred embodiment, B is a group B-1

in which # denotes the point of attachment of the phenyl ring to the oxirane ring; and L¹ is selected from the group consisting of halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy and Ci-C4-haloalkylthio, preferably selected from the group consisting of F, CI, methyl, ethyl, methoxy, ethoxy, CF3, CHF2, OCF3,

L² is selected from the group consisting of halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy and Ci-C4-haloalkylthio, preferably selected from the group consisting of F, CI, methyl, ethyl, methoxy, ethoxy, CF3, CHF2, OCF3,

L³ is independently selected from the group consisting of halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy and Ci-C4-haloalkylthio, preferably selected from the group consisting of F, CI, methyl, ethyl, methoxy, ethoxy, CF₃, CHF₂, OCF₃, OCHF₂ and SCF₃; and

m is 0, 1 or 2.

According to a preferred embodiment, L¹ is F. According to another preferred embodiment, L¹ is CI. According to a further preferred embodiment, L¹ is methyl. According to yet a further preferred embodiment, L¹ is methoxy. According to yet a further preferred embodiment, L¹ is CF3. According to yet a further preferred embodiment, L¹ is OCF3 or OCHF2. According to a preferred embodiment, in the compounds of the formula I according to the invention, B is thus phenyl which contains a substituent selected from the group consisting of F, CI, CH3, OCH3, CF3, CHF2, OCF3 and OCHF2 in the 2-position and one or two further independently selected substituents L. According to a further preferred embodiment, L² is F. According to another preferred embodiment, L² is CI. According to a further preferred embodiment, L² is methyl. According to yet a further preferred embodiment, L² is methoxy. According to yet a further preferred embodiment, L² is CF3. Accord i ng to yet a further preferred embodiment, L² is OCF₃ or OCHF₂.

According to a preferred embodiment, L³ is F. According to another preferred embodiment, L³ is CI. According to a further preferred embodiment, L³ is methyl. According to yet a further preferred embodiment, L³ is methoxy. According to yet a further preferred embodiment, L³ is CF3. According to yet a further preferred embodiment, L³ is OCF₃ or OCHF₂.

According to a preferred embodiment, m = 0; i.e. B is a disubstituted phenyl ring. According to a preferred aspect, B is a 2,3-disubstituted phenyl ring. According to a further preferred aspect, the pheny ring B is 2,4-disubstituted. According to yet a further preferred aspect, the phenyl ring B is 2,5-disubstituted. According to yet a further preferred aspect, the phenyl ring is 2,6-disubstituted.

According to a further preferred embodiment, m = 1 ; i.e. B is a trisubstituted phenyl ring . Accordi ng to a preferred aspect, the phenyl ring B is 2 ,3 ,5-trisubstituted. According to another preferred further aspect, the phenyl ring B is 2,3,4-trisubstituted. Accord i ng to yet a further preferred em bod iment, the phenyl ring B is 2 ,4 ,5- trisubstituted.

Unless indicated otherwise, in group (1 ) L independently has the following preferred meanings:

According to one embodiment, L is independently selected from the group consisting of halogen, cyano, nitro, cyanato (OCN), Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci- C₄-haloalkoxy, C₃-C₆-cycloalkyl, C₃-C₆-halocycloalkyl, S-A¹, C(=0)A², C(=S)A², NA³A; where A¹, A², A⁵, A⁶ are as defined below:

A¹ is hydrogen, hydroxy, Ci-C₄-alkyl, Ci-C₄-haloalkyl; is one of the groups mentioned under A¹ or Ci-C₄-alkoxy, C1-C4- haloalkoxy, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C3-C6-cycloalkoxy or C3-C6-halocycloalkoxy; A⁵,A⁶ independently of one another are hydrogen, Ci-C4-alkyl, Ci-C4-halo- alkyl; where the aliphatic and/or alicyclic groups of the radical definitions of L for their part may carry one, two, three or four identical or different groups R^L:

R^L is halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, amino, Ci-Cs- alkylamino, di-Ci-Cs-alkylamino.

Furthermore preferably, L is independently selected from the group consisting of halogen, NO2, amino, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci- C4-alkylamino, di-Ci-C4-alkylamino, thio and Ci-C4-alkylthio. Furthermore preferably, L is independently selected from the group consisting of halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy and C1-C4- haloalkylthio, in particular halogen, Ci-C4-alkyl and Ci-C4-haloalkyl.

According to a further preferred embodiment, L is independently selected from the group consisting of F, CI, Br, CH₃, C₂H₅, i-C₃H₇, t-C₄H₉, OCH₃, OC2H5, CF₃, CCI₃, CHF2, CCIF2, OCF3, OCHF2 and SCF3, in particular selected from the group consisting of F, CI, CH₃, C2H5, OCH3, OC2H5, CF₃, CHF₂, OCF3, OCH F2 and SCF₃. According to one aspect, L is independently selected from the group consisting of F, CI, CH3, OCH3, CF3, OCF3 and OCHF2. It may be preferred for L to be independently F or CI.

According to one preferred embodiment, A and B are as defined as follows:

A phenyl, which is unsubstituted or substituted by one, two or three substituents L that may be the same or different, independently selected from F, CI, Br, nitro, phenyl, phenoxy, methyl, ethyl, tert-butyl, methoxy, ethoxy, trifluoromethyl, trichloromethyl, di- fluoromethyl, difluorochloromethyl, trifluoromethoxy, difluoromethoxy and trifluoro- methylthio; and

B phenyl, that is substituted by one, two or three substituents L that may be the same or different, independently selected from F, CI, Br, methyl, ethyl, iso-propyl, tert- butyl, methoxy, ethoxy, trifluoromethyl, trichloromethyl, difluoromethyl, difluorochloromethyl, trifluoromethoxy, difluoromethoxy and trifluoromethylthio.

In specific groups (1 ) A and B are defined as follows: A i s ph enyl , 4-chlorophenyl, 2,4-chlorophenyl, 2-chlorophenyl, 2-fluorophenyl, 4- fluorophe n y l , 4-methylphenyl, 3-bromo-4-fluorophenyl, 4-bromophenyl, 3,4- dichlorophenyl, 4-tert-butyl-phenyl, 3-chlorophenyl, 3,5-dichlorophenyl or 4- trifluoromethoxypghenyl and B is 2-chlorophenyl. In one specific group (1 ) A is 4- flourphenyl and B is 2-chlorophenyl.

A is 4-fluorophenyl and B is 2-difluoromethoxyphenyl.

A i s ph enyl , 4-chlorophenyl, 2,4-chlorophenyl, 2-chlorophenyl, 2-fluorophenyl, 4- methylphenyl, 4-fluorophenyl, 3-bromo-4-fluorophenyl, 4-bromophenyl, 3,4- dichlorophenyl, 4-tert-butyl-phenyl, 3-chlorophenyl, 3,5-dichlorophenyl or 4- trifluoromethoxyphenyl, and B is 2-fluorophenyl.

A i s ph enyl , 4-chlorophenyl, 2,4-chlorophenyl, 2-chlorophenyl, 2-fluorophenyl, 4- methylphenyl, 4-fluorophenyl, 3-bromo-4-fluorophenyl, 4-bromophenyl, 3,4- dichlorophenyl, 4-tert-butyl-phenyl, 3-chlorophenyl, 3,5-dichlorophenyl or 4- trifluoromethoxyphenyl, and B is 2-bromophenyl.

In further specific groups (1 ) A and B are defined as follows:

A is 2,4-difluorophenyl and B is 2-chlorophenyl.

A is 3,4-difluorophenyl and B is 2-chlorophenyl.

A is 2,4-difluorophenyl and B is 2-fluorophenyl.

A is 3,4-difluorophenyl and B is 2-fluorophenyl.

A is 2,4-difluorophenyl and B is 2-trifluoromethylphenyl.

A is 3,4-difluorophenyl and B is 2-trifluoromethylphenyl.

A is 3,4-difluorophenyl and B is 2-methylphenyl

In further specific groups (1 ) A and B are defined as follows:

A is phenyl and B is 2,4-dichlorophenyl.

A is phenyl and B is 2-fluoro-3-chlorophenyl.

A is phenyl and B is 2,3,4-trichlorophenyl.

A is 4-fluorophenyl and B is 2,4-dichlorophenyl.

A is 4-fluorophenyl and B is 2-fluoro-3-chlorophenyl.

A is 4-fluorophenyl and B is 2,3,4-trichlorophenyl.

A is 2-chlorophenyl and B is 2,4-dichlorophenyl.

A is 2-chlorophenyl and B is 2-fluoro-3-chlorophenyl.

A is 2-chlorophenyl and B is 2,3,4-trichlorophenyl.

The meanings described above of the variables A, B and L for groups (1 ) apply for R = group (1 ) in compounds (I) and, unless indicated otherwise, correspondingly to the precursors of the compounds (I) and side products. According to the inventive process, the pure enantiomers or a mixture of enantiomers (racemic or enantiomerically enriched) of the reactants, in particular of compounds of the formula (V) , can be used. According to a preferred embodiment, the racemic mixture is used. Depending on the use of the respective reactant, in particular of compound of the formula (V), it is possible to obtain compounds of the formula (I) having a certain stereochemistry. For example, the following different stereoisomers of compounds (l)-(1 ) can be obtained using the inventive process: compound (l)-(1 )-a1 ):

Formula (l)-(1 ), wherein A is 4-fluoro-phenyl and B is 2-chlorophenyl

4-amino-2-[(2S,3S)-3-(2-Chloro-phenyl)-2-(4-fluoro-phenyl)-oxiranylmethyl]-2H- [1 ,2,4]triazole-3-thione ("cis")

compound (l)-(1 )-a2):

Formula (l)-(1 ), wherein A is 4-fluoro-phenyl and B is 2-chlorophenyl

4-amino-2-[(2R,3R)-3-(2-Chloro-phenyl)-2-(4-fluoro-phenyl)-oxiranylmethyl]-2H- [1 ,2,4]triazole-3-thione ("cis")

compound (l)-(1 )-a3):

Formula (l)-(1 ), wherein A is 4-fluoro-phenyl and B is 2-chlorophenyl

4-amino-2-[(2S,3R)-3-(2-Chloro-phenyl)-2-(4-fluoro-phenyl)-oxiranylmethyl]-2H- [1 ,2,4]triazole-3-thione ("trans")

compound (l)-(1 )-a4):

Formula (l)-(1 ), wherein A is 4-fluoro-phenyl and B is 2-chlorophenyl

4-amino-2-[(2R,3S)-3-(2-Chloro-phenyl)-2-(4-fluoro-phenyl)-oxiranylmethyl]-2H-

[1 ,2,4]triazole-3-thione ("trans")

compound (l)-(1 )-b1 ):

Formula (l)-(1 ), wherein A is 2,4-difluoro-phenyl and B is 2-chlorophenyl

4-amino-2-[(2S,3S)-3-(2-Chloro-phenyl)-2-(2,4-difluoro-phenyl)-oxiranylmethyl]-2H-

[1 ,2,4]triazole-3-thione ("cis")

compound (l)-(1 )-b2):

Formula (l)-(1 ), wherein A is 2,4-difluoro-phenyl and B is 2-chlorophenyl

4-amino-2-[(2R,3R)-3-(2-Chloro-phenyl)-2-(2,4-difluoro-phenyl)-oxiranylmethyl]-2H-

[1 ,2,4]triazole-3-thione ("cis")

compound (l)-(1 )-b3):

Formula (l)-(1 ), wherein A is 2,4-difluoro-phenyl and B is 2-chlorophenyl

4-amino-2-[(2S,3R)-3-(2-Chloro-phenyl)-2-(2,4-difluoro-phenyl)-oxiranylmethyl]-2H- [1 ,2,4]triazole-3-thione ("trans")

compound (l)-(1 )-b4):

Formula (l)-(1 ), wherein A is 2,4-difluoro-phenyl and B is 2-chlorophenyl

4-amino-2-[(2R,3S)-3-(2-Chloro-phenyl)-2-(2,4-difluoro-phenyl)-oxiranylmethyl]-2H- [1 ,2,4]triazole-3-thione ("trans") With respect to the fungicidal activity of the end products, it may be preferred, if the "trans" diastereomers are synthesized in the inventive process.

Specific compounds (l)-(1 ) and compounds (V) are such compounds, wherein A and B have the meaning as defined in tables 1 a to 257a in combination with table A below (there, A and B are defined for compounds (X)-(1 ).

According to another embodiment of the present invention, the organic group R in the compounds (I) and the precursors thereof carries a free hydroxy group and compounds (I) are from the triazole class of fungicides. In a particular embodiment thereof, R is a group of the formula (2).

According to one embodiment, R¹¹ and R²² are preferably independently selected from Ci-C4-alkyl and phenyl, wherein the alkyl and phenyl group independently may contain one, two, three or four substituents , independently selected from F, CI, Br, methoxy, ethoxy, propoxy, isopropoxy, Ci-C2-alkoximino, cyclopropyl, cyclobutyl, cyclopentyl and/or cyclohexyl. Specifically, R¹¹ stands for Ci-C4-alkyl that is substituted by one or two substituents independently selected from F, CI, methoxy, cyclopropyl, cyclopentyl and/or cyclohexyl and R²² stands for phenyl, that is substituted by one, two, three or four substituents independently selected from F, CI, Br and methoxy. In one specific embodiment, R¹¹ i s 1 -ethyl that is 1 -substituted by cyclopropyl and R²² is 4- chlorophenyl. According to another specific embodiment, R¹¹ is n-butyl and R²² is 2,4- dichlorophenyl. According to another embodiment, R¹¹ and R²² are preferably independently selected from Ci-C4-alkyl, phenyl-Ci-C4-alkyl and C3-C6-cycloalkyl, preferably phenyl-Ci-C4-alkyl and C3-C6-cycloalkyl, wherein the alkyl, phenyl and cycloalkyl groups independently may contain one, two, three or four substituents , independently selected from F, CI, Br, CN, methyl, ethyl, propyl, isopropyl and/or tert-butyl. Specifically, R¹¹ stands for phenyl- Ci-C4-alkyl that is substituted in the phenyl moiety by one, two, three or four substituents independently selected from F, CI and methoxy and R²² stands for C3-C6- cycloalkyl, that is substituted by one, two, three or four substituents independently selected from F, CI, Br and methoxy. In one specific embodiment, R¹¹ i s 2- chlorophenylmethyl and R²² is 1 -chlorocyclopropyl.

According to still another embodiment, R¹¹ and R²² are preferably independently selected from Ci-C4-alkyl and phenyl-Ci-C4-alkyl, wherein the alkyl and phenyl groups may contain one, two, three or four substituents , independently selected from F, CI, Br, CN, methyl, ethyl, propyl, isopropyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoro- methyl, trifluoromethoxy, trifluoromethylthio, chlorodifluoromethoxy, difluoromethoxy, chlorodifluoromethylthio, methoxycarbonyl, ethoxycarbonyl, methoxyiminomethyl, 1 - methoximinoethyl and nitro. Specifically, R¹¹ stands for Ci-C4-alkyl that may be substi- tuted by one or two substituents, independently selected from methyl, ethyl, propyl, isopropyl and tert-butyl and R²² stands for phenyl-Ci-C4-alkyl, that is substituted in the phenyl moiety by one, two, three or four substituents independently selected from F, CI, Br, CN, methyl, trifluoromethyl and methoxy. In one specific embodiment R¹¹ is tert- butyl and R²² is 2-(4-chlorophenyl)-1 -ethyl.

According to still another embodiment, R¹¹ and R²² are preferably independently selected from phenyl, wherein the phenyl moieties may contain one, two, three or four substituents , independently selected from F, CI, Br, CN, methyl, ethyl, propyl, isopro- pyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoro- methylthio, chlorodifluoromethoxy, difluoromethoxy, chlorodifluoromethylthio, methoxy- carbonyl, ethoxyvarbonyl, methoxyiminomethyl, 1-methoximinoethyl and nitro. Specifically, R¹¹ and R²² independently stand for phenyl, that may contain one, two or three substituents , independently selected from F, CI and Br. In one specific embodiment R¹¹ is 2-fluorophenyl and R²² is 4-fluorophenyl.

According to still another embodiment, preferably R¹¹ and R²², together with the carbon atom to which they are attached, form a five- or six-membered saturated ring, that can be unsubstituted or substituted by one, two or three substituents L', wherein L' stands for L as defined above or stands for a group

R³³ and R⁴⁴ independently are selected from the group of hydrogen, Ci-C4-alkyl and phenyl, wherein the alkyl and phenyl groups may contain one, two, three or four substituents , independently selected from F, CI, Br, CN, methyl, ethyl, propyl, isopropyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, chlorodifluoro- methoxy, difluoromethoxy and nitro. Specifically, R¹¹ and R²², together with the carbon atom to which they are attached, form a five-membered saturated ring, that is substituted tituents L', wherein L' stands for Ci-C4-alkyl or for a group

R⁴⁴ independently are selected from the group of hydrogen, Ci-C4-alkyl and phenyl, wherein the alkyl and phenyl groups may contain one, two, three or four substituents , independently selected from F, CI, CN, methyl, isopropyl, tert-butyl and methoxy. In one specific embodiment R¹¹ and R²², together with the carbon atom to which they are attached, form a five-membered saturated ring, that is

substituted in 5-position by two methyl groups and contains a group

wherein R³³ is hydrogen and R⁴⁴ is 4-chlorophenyl in 2-position.

According to still another embodiment, R¹¹ and R²², together with the carbon atom to which they are attached, form a five- or six-membered saturated ring, that can be un- substituted or substituted by one, two or three substituents, independently selected from F, CI, Br, CN, methyl, ethyl, propyl, isopropyl, tert-butyl, methoxy, ethoxy, methyl- thio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, chlorodifluoromethoxy, di- fluoromethoxy, nitro, benzyl, wherein the phenyl moiety itself may contain on, two, three or four substituents, independently selected from F, CI, CN, methyl, isopropyl, tert-butyl and methoxy. In one specific embodiment R¹¹ and R²², together with the carbon atom to which they are attached, form a five-membered saturated ring, that is substituted in 5-position by two methyl groups and contains a 4-chlorobenzyl group in 2- position. Regarding compounds (l)-(2) and the synthesis of precursors thereof see also WO 96/16048 (A1 ), WO 96/38423 (A1 ), EP 378953 (B1 ), EP 655443 (A2), DE 4030039 (A1 ), DE 3337937 (A), DE 3315681 (A1 ), US 4414210 (A).

According to another embodiment of the present invention, the organic group R in the compounds (I) and the precursors thereof is a group of the formula (3).

According to one preferred embodiment, R⁵⁵ is phenyl, that is unsubstituted or substituted by one, two, three or four substituents independently selected from halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, phenoxy-Ci-C6-alkyl and halophenyloxy, and R⁶⁶ and R⁷⁷ are independently selected from hydrogen, methyl, ethyl, n-propyl and n-butyl. Specifically, R⁵⁵ is phenyl, that contains one, two or three substituents independently selected from F, CI and halophenoxy, wherein the phenoxy moiety contains one or two halogen atoms selected from CI and F; and R⁶⁶ is hydrogen and R⁷⁷ is Ci-C4-alkyl. In one specific embodiment R⁵⁵ is 4-(4-chlorophenoxy)-2-chlorophenyl, R⁶⁶ is hydrogen and R⁷⁷ is methyl. In another specific embodiment R⁵⁵ is 2,4-dichlorophenyl, R⁶⁶ is hydrogen and R⁷⁷ is n-propyl.

Regarding compounds (l)-(3) and the synthesis of precursors thereof see also WO 96/41804 (A1 ) and Pestic. Sci. 1980, 11, 95 and Research Disclosure 1989, 297,13. In some of the definitions of the symbols in the formulae given herein, collective terms are used which are generally representative of the following substituents: halogen: fluorine, chlorine, bromine and iodine; alkyl and the alkyl moieties of composite groups such as, for example, alkylamino: saturated straight-chain or branched hydrocarbon radicals having 1 to 4, 6, 8 or 12 carbon atoms, for example Ci-C6-alkyl, such as methyl, ethyl, propyl, 1 -methylethyl, butyl, 1 -methylpropyl, 2-methylpropyl, 1 ,1 -dimethylethyl, pentyl, 1 -methylbutyl, 2-me- thylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 -ethylpropyl, 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-dime- thylbutyl, 3,3-dimethylbutyl, 1 -ethylbutyl, 2-ethylbutyl, 1 ,1 ,2-trimethylpropyl, 1 ,2,2-tri- methylpropyl, 1 -ethyl-1 -methylpropyl and 1 -ethyl-2-methylpropyl;

haloalkyi: alkyl as mentioned above, where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above; in particular C1-C2- haloalkyi, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1 -chloroethyl, 1 -bromoethyl, 1 -fluoroethyl, 2-fluoroethyl, 2,2- difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2- dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl or 1 ,1 ,1 -trifluoroprop-2-yl alkenyl and also the alkenyl moieties in composite groups, such as alkenyloxy:

unsaturated straight-chain or branched hydrocarbon radicals having 2 to 4, 2 to 6 or 2 to 8 carbon atoms and one double bond in any position. According to the invention, it may be preferred to use small alkenyl groups, such as (C2-C4)-alkenyl; on the other hand, it may also be preferred to employ larger alkenyl groups, such as (C5-C8)-alkenyl. Examples of alkenyl groups are, for example, C2-C6-alkenyl, such as ethenyl, 1 - propenyl, 2-propenyl, 1 -methylethenyl, 1 -butenyl, 2-butenyl, 3-butenyl, 1 -methyl-1 - propenyl, 2-methyl-1 -propenyl, 1 -methyl-2-propenyl, 2-methyl-2-propenyl, 1 -pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1 -methyl-1 -butenyl, 2-methyl-1 -butenyl, 3-methyl-1 - butenyl, 1 -methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1 -methyl-3- butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1 ,1 -dimethyl-2-propenyl, 1 ,2-dimethyl-

1 - propenyl, 1 ,2-dimethyl-2-propenyl, 1 -ethyl-1 -propenyl, 1 -ethyl-2-propenyl, 1 -hexenyl,

2- hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1 -methyl-1 -pentenyl, 2-methyl-1 -pentenyl,

3- methyl-1 -pentenyl, 4-methyl-1 -pentenyl, 1 -methyl-2-pentenyl, 2-methyl-2-pentenyl, 3- methyl-2-pentenyl, 4-methyl-2-pentenyl, 1 -methyl-3-pentenyl, 2-methyl-3-pentenyl, 3- methyl-3-pentenyl, 4-methyl-3-pentenyl, 1 -methyl-4-pentenyl, 2-methyl-4-pentenyl, 3- methyl-4-pentenyl, 4-methyl-4-pentenyl, 1 ,1 -dimethyl-2-butenyl, 1 ,1 -dimethyl-3-butenyl, 1 ,2-dimethyl-1 -butenyl, 1 ,2-dimethyl-2-butenyl, 1 ,2-dimethyl-3-butenyl, 1 ,3-dimethyl-1 - butenyl, 1 ,3-dimethyl-2-butenyl, 1 ,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3- dimethyl-1 -butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1 - butenyl, 3,3-dimethyl-2-butenyl, 1 -ethyl-1 -butenyl, 1 -ethyl-2-butenyl, 1 -ethyl-3-butenyl, 2-ethyl-1 -butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1 ,1 ,2-trimethyl-2-propenyl, 1 - ethyl-1 -methyl-2-propenyl, 1 -ethyl-2-methyl-1 -propenyl and 1 -ethyl-2-methyl-2- propenyl; haloalkenyl: alkenyl as defined above, where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as described above under haloalkyi, in particular by fluorine, chlorine or bromine; alkadienyl: unsaturated straight-chain or branched hydrocarbon radicals having 4 to 6 or 4 to 8 carbon atoms and two double bonds in any position; alkynyl and the alkynyl moieties in composite groups: straight-chain or branched hydrocarbon groups having 2 to 4, 2 to 6 or 2 to 8 carbon atoms and one or two triple bonds in any position, for example C2-C6-alkynyl, such as ethynyl, 1 -propynyl, 2- propynyl, 1 -butynyl, 2-butynyl, 3-butynyl, 1 -methyl-2-propynyl, 1 -pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1 -methyl-2-butynyl, 1 -methyl-3-butynyl, 2-methyl-3-butynyl, 3- methyl-1 -butynyl, 1 ,1 -dimethyl-2-propynyl, 1 -ethyl-2-propynyl, 1 -hexynyl, 2-hexynyl, 3- hexynyl, 4-hexynyl, 5-hexynyl, 1 -methyl-2-pentynyl, 1 -methyl-3-pentynyl, 1 -methyl-4- pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1 -pentynyl, 3-methyl-4- pentynyl, 4-methyl-1 -pentynyl, 4-methyl-2-pentynyl, 1 ,1 -dimethyl-2-butynyl, 1 ,1 - dimethyl-3-butynyl, 1 ,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1 - butynyl, 1 -ethyl-2-butynyl, 1 -ethyl-3-butynyl, 2-ethyl-3-butynyl and 1 -ethyl-1 -methyl-2- propynyl; haloalkynyl: alkynyl as defined above, where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as described above under haloalkyl, in particular by fluorine, chlorine or bromine; cycloalkyi and also the cycloalkyi moieties in composite groups: mono- or bicyclic saturated hydrocarbon groups having 3 to 8, in particular 3 to 6, carbon ring members, for example C3-C6-cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl; halocydoalkyi: cycloalkyi as defined above, where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as described above under haloalkyl, in particular by fluorine, chlorine or bromine; cycloalkenyl: monocyclic monounsaturated hydrocarbon groups having preferably 3 to 8 or 4 to 6, in particular 5 to 6, carbon ring members, such as cyclopenten-1 -yl, cyclopenten-3-yl, cyclohexen-1 -yl, cyclohexen-3-yl, cyclohexen-4-yl and the like;

halocycloalkenyl: cycloalkenyl as defined above, where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as described above under haloalkyl, in particular by fluorine, chlorine or bromine; alkoxy: an alkyl group as defined above which is attached via an oxygen, preferably having 1 to 8, more preferably 2 to 6, carbon atoms. Examples are: methoxy, ethoxy, n- propoxy, 1 -methylethoxy, butoxy, 1 -methylpropoxy, 2-methylpropoxy or 1 ,1 - dimethylethoxy, and also for example, pentoxy, 1 -methylbutoxy, 2-methylbutoxy, 3- methylbutoxy, 1 ,1 -dimethylpropoxy, 1 ,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1 - ethylpropoxy, hexoxy, 1 -methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4- methylpentoxy, 1 ,1 -dimethylbutoxy, 1 ,2-dimethylbutoxy, 1 ,3-dimethylbutoxy, 2,2- dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1 -ethylbutoxy, 2-ethylbutoxy, 1 ,1 ,2-trimethylpropoxy, 1 ,2,2-trimethylpropoxy, 1 -ethyl-1 -methylpropoxy or 1 -ethyl-2- methylpropoxy; haloalkoxy: alkoxy as defined above, where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as described above under haloalkyl, in particular by fluorine, chlorine or bromine. Examples are OCH2F, OCHF2, OCF3, OCH2CI, OCHCI2, OCCI3, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoro- methoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2- difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2- difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, OC2F5, 2- fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2- chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bromopropoxy, 3- bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH2-C2F5, OCF2-C2F5, 1 -(CH₂F)-2-fluoroethoxy, 1 -(CH₂CI)-2-chloroethoxy, 1 -(CH₂Br)-2-bromoethoxy, 4- fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy; and also 5- fluoropentoxy, 5-chloropentoxy, 5-bromopentoxy, 5-iodopentoxy, undecafluoropentoxy, 6-fluorohexoxy, 6-chlorohexoxy, 6-bromohexoxy, 6-iodohexoxy or dodecafluorohexoxy. alkylene: divalent unbranched chains of CH2 groups. Preference is given to (C1-C6)- alkylene, more preference to (C2-C4)-alkylene; furthermore, it may be preferred to use (Ci-C3)-alkylene groups. Examples of preferred alkylene radicals are CH2, CH2CH2, CH2CH2CH2, CH₂(CH₂)2CH2, CH₂(CH₂)3CH₂ and CH₂(CH₂)4CH₂; a 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-membered saturated or partially unsaturated heterocycle which contains 1 , 2, 3 or 4 heteroatoms from the group consisting of O, N and S, where the heterocycle in question may be attached via a carbon atom or, if present, via a nitrogen atom. According to the invention, it may be preferred for the heterocycle in question to be attached via carbon, on the other hand, it may also be preferred for the heterocycle to be attached via nitrogen. In particular: a three- or four-membered saturated heterocycle (hereinbelow also referred to as heterocyclyl) which contains one or two heteroatoms from the group consisting of O, N and S as ring members; a five- or six-membered saturated or partially unsaturated heterocycle which contains one, two, three or four heteroatoms from the group consisting of O, N and S as ring members: for example monocyclic saturated or partially

unsaturated heterocycles which, in addition to carbon ring members, contain one, two or three nitrogen atoms and/or one oxygen or sulfur atom or one or two oxygen and/or sulfur atoms, for example 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3- isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4- isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl,

2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5- thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 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, 2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl, 2 ,4-d i hyd rofu r-2-y I , 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-dihydro- oxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4- yl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 1 ,3-dioxan-5-yl, 2-tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrothienyl, 3-hexahydropyridazinyl, 4-hexa- hydropyridazinyl, 2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl, 5-hexahydro- pyrimidinyl, 2-piperazinyl, 1 ,3,5-hexahydrotriazin-2-yl and 1 ,2,4-hexahydrotriazin- 3-yl and also the corresponding -ylidene radicals; a seven-membered saturated or partially unsaturated heterocycle which contains one, two, three or four heteroatoms from the group consisting of O, N and S as ring members: for example mono- and bicyclic heterocycles having 7 ring members which, in addition to carbon ring members, contain one, two or three nitrogen atoms and/or one oxygen or sulfur atom or one or two oxygen and/or sulfur atoms, for example tetra- and hexahydroazepinyl, such as 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, hexahydroazepin-1 -,-2-,- 3- or-4-yl, tetra- and hexahydrooxepinyl 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, hexahydroazepin-1 -,-2-,-3- or-4-yl, tetra- and hexahydro-1 ,3-diazepinyl, tetra- and hexahydro-1 ,4-diazepinyl, tetra- and hexahydro-1 ,3-oxazepinyl, tetra- and hexahydro-1 ,4-oxazepinyl, tetra- and hexahydro-1 ,3-dioxepinyl, tetra- and hexahydro-1 ,4-dioxepinyl and the corresponding ylidene radicals; a 5-, 6-, 7-, 8-, 9- or 10-membered aromatic heterocycle which contains 1 , 2, 3 or 4 heteroatoms from the group consisting of O, N and S: in particular a five- or six- membered aromatic mono- or bicyclic heterocycle which contains one, two, three or four heteroatoms from the group consisting of O, N and S: the heterocycle in question may be attached via a carbon atom or, if present, via a nitrogen atom. According to the invention, it may be preferred for the heterocycle in question to be attached via carbon, on the other hand, it may also be preferred for the heterocycle to be attached via nitrogen. The heterocycle is in particular: a 5-membered heteroaryl which contains one, two, three or four nitrogen atoms or one, two or three nitrogen atoms and/or one sulfur or oxygen atom, where the heteroaryl may be attached via carbon or nitrogen, if present: 5-membered heteroaryl groups which, in addition to carbon atoms, may contain one to four nitrogen atoms or one, two or three nitrogen atoms and/or one sulfur or oxygen atom as ring members, for example furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl (1 ,2,3-; 1 ,2,4-triazolyl), tetrazolyl, oxazolyl, isoxazolyl, 1 ,3,4-oxadiazolyl, thiazolyl, isothiazolyl and thiadiazolyl, in particular 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, 1 ,2,4-oxadiazol-5-yl, 1 ,2,4-thiadiazol-3-yl,

1 .2.4- thiadiazol-5-yl, 1 ,2,4-triazol-3-yl, 1 ,3,4-oxadiazol-2-yl, 1 ,3,4-thiadiazol-2-yl and 1 ,3,4-triazol-2-yl; a 6-membered heteroaryl which contains one, two, three or four, preferably one, two or three, nitrogen atoms, where the heteroaryl may be attached via carbon or nitrogen, if present: 6-ring heteroaryl groups which, in addition to carbon atoms, may contain one to four or one, two or three nitrogen atoms as ring members, for example pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, 1 ,2,3-triazinyl, 1 ,2,4-triazinyl,

1 .3.5- triazinyl, in particular 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4- pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1 ,3,5-triazin-2- yl and 1 ,2,4-triazin-3-yl. optionally substituted heterocycle: a saturated heterocycle which is bonded via a ring nitrogen atom and has 5, 6, 7 or 8 ring atoms, where, as well as the nitrogen atom, the ring atoms also further which is unsubstituted or bears 1 , 2, 3, 4 or 5 and especially 1 , 2 or 3 substituents which are inert under the conditions of the reaction. Examples of inert substituents are CN, Ci-C6-alkyl, Ci-C6-alkylthio, Ci-C6-alkylsulfonyl, C1-C4- haloalkyl, Ci-C6-alkoxy, C3-C6-cycloalkyl, and Ci-C4-alkoxy-Ci-C6-alkyl. The heterocycle may, as well as the nitrogen atom in position 1 and the ring carbon atoms, also comprise 1 or 2 further heteroatoms selected from N, O and S as ring atoms. Examples of N-bonded, 5- to 8-membered, saturated, optionally substituted heterocycles are pyrrolidine -yl, piperdin-1 -yl, morpholin-4-yl, piperazin-1 -yl and N-methylpiperazin-1 -yl; alkylthio: alkyl as defined above which is attached via an S atom; amino: NR^1NR^2N group, in which R^1N and R^2N can be alkyl, aryl or heteroaryl as defined above, which is attached via an N atom alkylamino: alkyl as defined above which is attached via N atom; haloalkylthio: haloalkyl as defined above which is attached via an S atom; hydroxy: OH group which is attached via an O atom; carbonitrile: CN group which is attached via an C atom; aldehyde: CHO group, which is attached via an C atom; carboxylic ester: COOR¹⁰ group, in which R¹° can be alkyl, aryl or heteroaryl as defined above, which is attached via an C atom; mercapto: SH group which is attached via an S atom.

The thiolation step according to the invention is carried out in water or in a protic organic solvent or a mixture of such solvents.

Possible solvents in the thiolation step are, for example, water or d-Cs-alkanols such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, 2-butanol, iso-butanol, tert- butanol, n-pentanol and 2-ethylhexanol.

According to another preferred embodiment the present invention relates to solvents in the thiolation step that are water, n-butanol, iso-butanol or tert-butanol.

According to another preferred embodiment the present invention relates to solvents in the thiolation step that are iso-butanol or n-butanol.

Furthermore, it may also be suitable conduct the thiolation step in combinations of two or more different solvents, such as, for example, any combination of the solvents listed above.

Suitable bases in the thiolation step are, in general, inorganic compounds, for example alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hy- droxide, potassium hydroxide and calcium hydroxide or alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, potassium oxide and calcium oxide or alkali metal and alkaline earth metal phosphates such as lithium phosphate, sodium phosphate, potassium phosphate and calcium phosphate or alkali metal amides such as lithium amide, sodium amide and potassium amide or alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride or alkali metal and alkaline earth metal carbonates such as lithium carbonate, potassium carbonate, cesium carbonate and calcium carbonate or alkali metal bicar- bonates such as sodium bicarbonate and potassium bicarbonate, moreover organic bases, for example primary amines such as methylamine, ethylamine, 1 -propylamine or secondary amines such as dimethylamine, diethylamine or tertiary amines such as trimethylamine, triethylamine, tributylamine, diisopropylethylamine, N,N- dimethylcyclohexylamine or N-methyl-2-pyrrolidone, ammonia, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine, and also bicyclic amines such as 1 ,8-diazabicyclo[5.4.0]undec-7-en and 1 ,4-diazabicyclo[2.2.2]octan or mixtures thereof. Particular preference is given to bases such as alkali metal and alkaline earth metal carbonates, alkali metal bicarbonates sodium hydroxide, alkali metal and alkaline earth metal hydroxides, ammonia, Ν,Ν-dimethylcyclohexylamine and triethylamine or mixtures thereof. Another embodiment of the invention is that preferably in the thiolation step the base is triethylamine.

Another embodiment of the invention is that preferably in the thiolation step the base is sodium bicarbonate and potassium bicarbonate.

The reaction components in carrying out the thiolation of compounds of the formula (II) are usually employed in amounts such that 0.9 to 10 moles, in particular 1 to 5, more particularly 1 to 3 moles of base are used per mole of the compound (II). It may be preferred if 1 to 2.5 moles of base are used per mole of the compound (II).

The reaction components in carrying out the thiolation of compounds of the formula (II) are usually employed in amounts such that 0.9 to 10 moles, in particular 1 to 5, more particularly 1 to 3 moles of sulfur are used per mole of the compound (II). It may be preferred if 1 to 2.5 moles of sulfur are used per mole of the compound (II).

One advantage of the inventive process is, that it can be carried out at moderate temperatures. Suitable temperature ranges are 0 °C to 120 °C, in particular 40 °C to 80 °C. It may be also preferred to work at temperatures of 50 °C to 70 °C. The educts for preparation of compounds of the formula (II) can be prepared for example in analogy to methods described in WO 20004/000835, wherein the preparation of triazolium salts, which are substituted in the 1 -position by a methyloxirane group is described. The process of this invention is generally applicable to the preparation of 1 -substituted 4-amino-4H-[1 ,2,4]-triazolium salts.

Therefore the preparation of a compound of the formula (II) via alkylation of 4-amino- 4H-[1 ,2,4]-triazole of the formula (IV) can be achieved with suitable alkylating agents of the formula (V),

(IV) (V) wherein R and X are defined as described above and R is preferably a substituted Ci -C₄-alkyl group, for example a substituted methylene group.

The alkylation step is carried out through a nucleophilic substitution in which X represents a leaving group. Suitable leaving groups are known to a person skilled in the art as well as the conditions under which such substitutions are commonly and advantageously conducted. X can be chosen from a group consisting of well known leaving groups, for example halides such as chloride, bromide, iodide or arylsulfonates such as benzenesulfonate, p-tolylsulfonate, 2-nitrophenylsulfonate, 4-nitrophenylsulfonate, 4- bromophenylsulfonate or alkylsulfonates such as methanesulfonate or haloalkylsul- fonates such as trifluoromethylsulfonate, nonafluorobutylsulfonate or alkyl- and haloal- kylsulfates such as methylsulfate where above mentioned alkyl, haloalkyi or aryl groups are unsubstituted or substituted by one, two, three or four independently selected inert substituents. Particularly useful leaving groups X are halogen, in particular chloride and bromide.

Other particularly useful leaving groups X are Ci-C₄-alkylsulfonate, in particular methanesulfonate. The reaction components in the alkylation step are usually employed in amounts that the molar ratio of compound (IV) to compounds of the formula (V) is 0.9 to 10, in particular 1 to 5, more particularly 1 to 3. It is also preferred if the molar ratio is 1 to 2.5.

Generally such alkylations are carried out in suitable organic solvents, for example, water, d-Cs-alkanols such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, 2-butanol, iso-butanol, tert-butanol, n-pentanol and 2-ethylhexanol or Ci-C₄- alkyleneglykoles such as methyenelglykol, ethyleneglykol, n-propyleneglykol, n- butyleneglykol or branched or unbranched Ci-Cio-alkanes such as pentane, n-hexane, n-pentane, and petrol ether or alicyclic hydrocarbons, for example cyclohexane or aro- matic hydrocarbons, for example benzene substituted by 1 to 4 residues such as toluene, 0-, m- and p-xylene or cumene and chlorobenzene or halogenated hydrocarbons, for example branched or unbranched Ci-Cio-alkanes substituted by halogen such as dichloromethane, chloroform, carbon tetrachloride or dialkyl ethers, for example di-Ci- C6-alkyl ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, cyclo- pentyl methyl ether or aryl alkyl ethers, for example substituted phenyl alkyl ethers such as anisole, cyclic ethers such as dioxane and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones, for example di-Ci-C6-alkyl ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone or dimethyl sul- foxide, sulfolan, N,N-dimethylformamide, Ν,Ν-dimethyl acetamide, N-methyl-

2-pyrrolidone, N-ethyl-2-pyrrolidone, tetramethylurea or esters of carboxylis acids such as Ci-Cio-alkyl acetate, Ci-Cio-alkyl propanoate, Ci-Cio-alkylbutanoate are used or mixtures of such solvents with water. It is preferred to use solvents selected from the group consisting of d-Cs-alkanols or Ci-C4-alkyleneglykoles or mixtures of these solvents with toluene.

The reaction temperature for such transformations can be chosen in the range from 0 to 200°C, in particular from 50°C to 150 °C.

The reaction can be facilitated and reaction time can be reduced by addition of quaternary ammonium- and phosphoniumsalts, such as tetra-n-butylammoniumchloride, be- taines such as 4-dimethylsulfoniumphenolate, cyanide salts, iodide salts, fluoride salts and amines such as collidine, lutidine, Ν,Ν-dimethylcyclohexylamin, tri-n-butylamin, triethylamin or 1 ,8-diazabicyclo[5.4.0]undec-7-en (DBU) and 1 ,4- diazabicyclo[2.2.2]octan (DABCO). The reaction components facilitating the alkylation step are usually employed in amounts that range between 0.1 % to 10% (w/w).

The resulting 1 -substituted 4-amino-[1 ,2,4]-triazolium salts of the formula (II) can be obtained from the reaction mixture by means of methods that are common knowledge to the skilled person. The product may crystallize from the reaction mixture and can be isolated by filtration. Purification can be achieved through washing with suitable solvents and/or recrystallisation. The synthesis of 4-amino-[1 ,2,4]-triazole of the formula (IV) is described in literature. For example one can obtain it by reaction of hydrazine and or by reaction of hydrazine and formic acid as described in EP 841328 (A1 ) .

In one preferred embodiment of the invention the preparation of a compound of the formula (I) is carried out via alkylation of a 4-amino-1 ,2,4-triazole (IV) to give a compound of the formula (II), which is then, in situ, converted to compounds of the formula (I). This procedure allows for using one reaction vessel for both steps while the same solvent, or mixture of solvents is used as described above for the preparation of compounds of the formula (I) from compounds of the formula (II). Preferably additional solvents can be added to the reaction mixture after the alkylation of 4-amino-1 ,2,4-triazole (IV), to mitigate precipitation of the intermediate triazolium salt and provide homogene- ous reaction conditions to ensure best efficiency of the subsequent thiolation step that ultimately provides a compound of the formula (I).

Generally thus formed 2-substituted 4-amino-2,4-dihydro-[1 ,2,4]triazole-3-thiones can be conveniently obtained in crystalline form upon cooling of the reaction mixture, filtration and washing of the precipitate. Yields that are obtained are generally high when following this two-step procedure, i.e. on average more than 90% per single step.

Compounds of the formula (I) can be transformed to 2-substituted 2,4-dihydro- [1 ,2,4]triazole-3-thiones of the formula (III), which are useful for crop protection against phytopathogenic fungi, by reductive removal of the amino group

through diazotation/reduction sequences that are generally known to the skilled person.

The mercapto-triazole groups of the general formula (III) can be present in two tautomeric forms - the "thiol" form of the formula (Ilia) or in the "thiono" form of the formula (1Mb).

In conventional diazotation/reduction sequences sometimes strong acidic conditions do not allow for the presence of sensitive functional groups in other parts of the molecule. Under such conditions it is therefore often found, that besides the desired compounds of the formula (III) other products are formed such as desulfurized triazoles of the formula (VI) and dimeric compounds of the formula (VII), that contain a disulfide group.

(VI) (VII)

In search of an efficient process to prepare compounds of the formula (I II) a general protocol for their preparation has now surprisingly been found, by way of treating 2- substituted 4-amino-2,4-dihydro-[1 ,2,4]triazole-3-thiones of the formula (I)

with inorganic or organic nitrites in the presence of a reducing agent in suitable organic solvents.

When using alkyl nitrites in excess preferably the disulfide (VII) is formed and can thus be produced in a directed synthesis. This approach provides several advantages, as the disulfides of the formula (VI I) are obtained in yields that are greater than 80% without residual starting material and with very limited amounts of desulfurized compounds of the formula (VI).

The disulfides of formula (VII) can be reduced to provide corresponding compounds of the formula (II I) in a subsequent reduction step using methods that are well known to the skilled person. Disulfides of the formula (VII) are known to possess microbicidal activity and a process for their preparation by way of oxidation of 2,4-dihydro-[1 ,2,4]triazole-3-thiones has been described in WO 97/43269 (A1 ). However, this process, as it starts from thiono- triazoles, suffers from the disadvantages associated with the preparation of the starting material, as pointed out above. Because certain disulfide compounds of the formula (VII) have fungicidal activity, they are relevant with regards to their use for pathogen control in the agrochemical industry. For that reason there is an ongoing need for improved processes that make disulfides of the formula (VII) available on an industrial scale. 2-Substituted 2,4-dihydro-[1 ,2,4]triazole-3-thiones of the formula (III) can be prepared by a process comprising the steps i) diazotation of 2-substituted 4-amino-2,4-dihydro-[1 ,2,4]triazole-3-thiones of formula (I)

wherein

R is defined as above by treatment with inorganic nitrites and an acid or in the presence of organic nitrites in an organic solvent or water or mixtures thereof giving the corresponding compound of formula (VIII).

wherein

R is defined as above and is an anion selected from fluoride, chloride, bromide, iodide, arylsul- fonate, alkylsulfonate, haloalkylsulfonate or X⁰¹OSO₃, in which X⁰¹ is d-Cs-alkyl, CrC₈-haloalkyl or C₃-C₈-cycloalkyl where above mentioned alkyl, haloalkyl or aryl groups are unsubstituted or substituted by one, two, three or four independently selected inert substituents- sulfate, sulfonate, phosphate, phosponate, tetrafluoroborate, tetra- phenylborate, hexafluorophosphate, hexafluoroarsenate, hex- afluoroantimonate, trifluoroacetate, trichloroacetate, perchlorate, alkoxide or hydroxide; ii) reduction of a compound of the formula (VIII) to provide mixtures of compounds of the formula (III) and c II),

(VII)

wherein R is defined as above, by means of a reducing agent; iii) treating the reaction mixture with a reducing reagent suitable to cleave disulfide groups. In view of a concise and efficient preparation of compounds of the formula (III) the process for the deamination of compounds of the formula (I) can be achieved by way of conducting step i), step ii) and step iii) in one vessel (one-pot procedure) with successive addition of reagents or solvents.

The diazotation of an aromatic amine and replacement of the diazo group by hydrogen is well known to the skilled person and can be achieved as previously described in prior art (Organic Reactions 1944, 2, 262; Organic Reactions 1953, 7, 263; Comprehensive Organic Synthesis 1991 , 8, 81 1 ). One suitable way is to treat compounds of the for- mula (I) with inorganic nitrites or organic nitrites. Suitable inorganic nitrites can be, for example, alkali metal nitrites or alkaline earth metal nitrites. Preferably sodium nitrite and potassium nitrite are used. Ci-Cio-alkylnitrites, for example n-butyl nitrite, iso-butyl nitrite, tert-butyl nitrite and isoamyl nitrite are suitable as well. The diazotation step i) with inorganic nitrites requires the addition of an acid, preferably a strong acid such as hydrochloric acid, sulfuric acid, phosphoric acid or hypophos- phoric acid. The reaction is carried out at temperatures from -10 to 60 "Cpreferably at temperatures from 0 to 30 °C. The diazotation step i) with organic nitrites is preferably carried out at temperatures from 0 to 60°C, preferably the reaction is carried out at temperatures from 10 to 40°C.

Suitable reducing agents in step ii) are, for example, Ci-Cio-alkanols such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, 2-butanol, iso-butanol, pentanol, 2-ethyl- hexanol or formic acid and its salts such as ammonium formate, esters of C1-C4- alkanoles with formic acid, formic amides such as formamide or mercaptanes or alkaline metal borohydrides or tin(ll) salts, phosphonic acid, hypophosponic acid can be used. The use of Ci-Cio-alkanols is preferred, particularly n-butanol and iso-butanol are preferred.

The reaction components in carrying out the diazotation of compounds of the formula (I) are usually employed in amounts such that 1 to 10 moles, in particular 1 to 3, more particularly 1 to 2 moles of inorganic nitrite are used per mole of the compound (I) while at least the same amount of reducing agent is added with the inorganic nitrite. It may be preferred if 1 to 1.5 moles of inorganic nitrite are used per mole of the compound (I) while the same amount of reducing agent is added with the inorganic nitrite.

Preferably 1 to 5 moles of alkyl nitrite are used per mole of the compound (I). More preferably 1 to 2 moles of alkyl nitrite are used per mole of the compound (I). It is also possible to use an inorganic nitrite for the diazotation, 0.1 to 1 moles of a strong acid are used per mole of the compound (I). Preferably 0.5 to 1 moles of a strong acid are used per mole of the compound (I). Solvents that can be employed in such diazotation/reduction sequences provide appropriate solubility of the starting materials, i.e. compounds of the formula (I), and are also suitable to at least partially dissolve the nitrite and/or the reducing agent. Preferably water or aqueous mixtures of water soluble solvents can be used. Examples for such solvents are Ci-C6-alkanols such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, 2-butanol, iso-butanol, tert-butanol, n-pentanol and 2-ethylhexanol or dimethyl sulfoxide, N,N-dimethylformamide, Ν,Ν-dimethylacetamide, N-methyl- 2-pyrrolidone, N-ethyl-2-pyrrolidone or cyclic ethers such as dioxane and tetra- hydrofuran, 2-methyltetrahydrofuran, or nitriles such as acetonitrile and propionitrile or ketones, for example di-Ci-C6-alkyl ketones such as acetone, methyl ethyl ketone, di- ethyl ketone and tert-butyl methyl ketone are used. Solvents such as water, C1-C6- alkanols, tetrahydrofuran, dioxane and N-methylpyrrolidon are particularly preferred.

Suitable solvents in the diazotation/reduction sequences are water or protic solvents or mixtures of water and protic solvents.

Other suitable solvents in the diazotation/reduction sequences are water, n-butanol, iso-butanol, tert-butanol, tetrahydrofuran and toluene.

Also suitable solvents in the diazotation/reduction sequences are water, n-butanol, iso- butanol or tert-butanol,.

Also suitable as solvent tetrahydrofuran can be used in the diazotation/reduction sequences. Another suitable solvent system in the diazotation/reduction sequences are water or toluene.

Suitable counterions Y^_ of said diazonium compounds of the formula (VIII) are halides, for example chloride, bromide, iodide or arylsulfonates, for example benzenesulfonate, p-tolylsulfonate, 2-nitrophenylsulfonate, 4-nitrophenylsulfonate, 4- bromophenylsulfonate or alkylsulfonates, for example methanesulfonate or haloalkyl- sulfonates, for example trifluoromethylsulfonate, nonafluorobutylsulfonate or alkyl- and haloalkylsulfates, for example methylsulfate where above mentioned alkyl, haloalkyi or aryl groups are unsubstituted or substituted by one, two, three or four independently selected inert substituents, sulfate, sulfonate, phosphate, phosponate, tetrafluorobo- rate, tetraphenylborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroanti- monate, trifluoroacetate, trichloroacetate, perchlorate, Ci-Cio-alkoxide or hydroxide. Preferably the counterion Y- is an anion selected from fluoride, chloride, bromide, sulfate, sulfonate, phosphate, phosponate, tetrafluoroborate, tetraphenylborate, hex- afluorophosphate, hexafluoroarsenate, hexafluoroantimonate.

Preferably the counterion Y- is an anion selected from Ci-Cio-alkoxide or hydroxide.

Typically the duration of diazotation reactions as described in step i) of the process is between 5 and 60 minutes and is accompanied by the formation of IS O-gas.

The reductive cleavage of disulfide compounds of the formula (VII) to provide compounds of the formula (III) according to step iii) can be achieved as previously described in the literature (J. L. Wardell, S. Patai The Chemistry of the Thiol Group 1974, Wiley, New York). The use of sodium dithionite for the cleavage of disulfides has been described in Journal of Organic Chemistry 1945, 10, 381 -335. The reducing agent of step (iii) is preferably selected from the group comprising alkali metal or alkaline earth metal dithionite, alkali metal formate, sulfur dioxide, hydrazine, zinc/ammonium chloride, alkali metal alanate, tin(ll) salts or mixtures thereof. The use of sodium dithionite is particularly preferred.

I n view of a concise and efficient preparation of compounds of the formula (I I I) compounds of the formula (II I) can be prepared by way of alkylation of compounds of the formula (V) and subsequent thiolation to provide compounds of the formula (I) as described above, followed by the diazotation/reduction sequence as described above, comprising step i), step ii) and step iii). All steps, starting from compounds of the formula (V) to the preparation of compounds of the formula (II I), are conducted in one vessel (one-pot procedure) with successive addition of reagents or solvents.

2-Substituted 2,4-dihydro-[1 ,2,4]triazole-3-thiones of the formula (III) usually precipitate from concentrated solutions and the product can be separated from the reaction mixture by filtration. Purification of thus obtained material can be achieved by washing of the precipitate and/or recrystallization.

The novel compounds according to the invention contain chiral centers and are generally obtained in the form of racemates or as diastereomeric mixtures of erythro and threo forms. The erythro and threo diastereomers of the compounds according to the invention can be separated and isolated in pure form, for example, on the basis of their different solubilities or by column chromatography. Using known methods, such uniform pairs of diastereomers can be used to obtain uniform enantiomers.

Accordingly, the invention provides both the pure enantiomers or diastereomers and mixtures thereof. This applies to the compounds according to the invention. The scope of the present invention includes in particular the (R) and (S) isomers and the racemates of the compounds according to the invention, which have centers of chirality. Suitable compounds according to the invention also include all possible stereoisomers (cis/trans isomers) and mixtures thereof.

The compounds according to the invention may be present in various crystal modifications. They are likewise provided by the present invention.

Furthermore, in the inventive process, the reactants used, contain chiral centers and are generally used in the form of racemates or as diastereomeric mixtures of erythro and threo forms. The erythro and threo diastereomers of these compounds can be separated and isolated in pure form, for example, on the basis of their different solubilities or by column chromatography. Using known methods, such uniform pairs of diastereomers can be used to obtain uniform enantiomers.

Accordingly, the invention provides both the use of pure enantiomers or diastereomers and mixtures thereof. The scope of the present invention includes in particular the use of the (R) and (S) isomers and the racemates of the rspective reactants, which have centers of chirality. Suitable compounds used according to the invention also include all possible stereoisomers (cis/trans isomers) and mixtures thereof.

The compounds used according to the invention may be present in various crystal modifications. They are likewise possible to be used in the inventive process. Another aspect of the present invention is triazolium salts of the formula (II) in which the organic group R is a group of the formula (2) as defined above.

Another aspect of the present invention is triazolium salts of the formula (II) in which the organic group R is a group of the formula (3) as defined above.

Another aspect of the present invention is 2-substituted 4-amino-2,4-dihydro-[1 ,2,4]- triazole-3-thiones of the formula (I) in which R is a group of the formula (1 ) as defined above. Another aspect of the present i nvention is 2-substituted 4-amino-2,4-dihydro- [1 ,2,4]triazole-3-thiones of the formula (I) in which R is a group of the formula (2) as defined above.

Another aspect of the present invention is 2-substituted 4-amino-2,4-dihydro-[1 ,2,4]- triazole-3-thiones of the formula (I) in which R is a group of the formula (3) as defined above. Following the diazotation steps described above, compounds of the formula (VIII) can be prepared in which R is a group of the formula (1 ) as defined above.

Following the diazotation steps described above, compounds of the formula (VIII) can be prepared in which R is a group of the formula (2) as defined above.

Following the diazotation steps described above, compounds of the formula (VIII) can be prepared in which R is a group of the formula (3) as defined above. According to one specific embodiment of the present invention, R in compounds (I) is a group (1 ) as defined above, including the specific embodiments thereof. In particular, compounds (X)-(1 ),

according to the invention compiled in tables 1 a to 257a in combination with rows 1 to 514 of table A below are suitable for the synthesis of the respective fungicides of formula (III) and are obtained by the inventive process. The groups mentioned for a sub- stituent in the tables are furthermore per se, independently of the combination in which they are mentioned, a particularly preferred aspect of the substituent in question. table 1 a

Compounds (X)-(1 ), wherein A is 2,3-difluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).1 aA-1 to (X)-(1 ).1 aA-514)

table 2a

Compounds (X)-(1 ), wherein A is 2,4-difluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).2aA-1 to (X)-(1 ).2aA-514)

table 3a

Compounds (X)-(1 ), wherein A is 2,5-difluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).3aA-1 to (X)-(1 ).3aA-514)

table 4a

Compounds (X)-(1 ), wherein A is 2,6-difluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).4aA-1 to (X)-(1 ).4aA-514)

table 5a

Compounds (X)-(1 ), wherein A is 3,4 ^■difluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).5aA-1 to (X)-(1 ).5aA-514) table 6a

Compounds (X)-(1), wherein A is 3,5-difluorophenyl and B corresponds to one row of table A (Compounds (X)-(1).6aA-1 to (X)-(1).6aA-514)

table 7a

Compounds (X)-(1), wherein A is 2-fluoro-3-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1).7aA-1 to (X)-(1).7aA-514)

table 8a

Compounds (X)-(1), wherein A is 2-fluoro-4-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1).8aA-1 to (X)-(1).8aA-514)

table 9a

Compounds (X)-(1), wherein A is 2-fluoro-5-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1).9aA-1 to (X)-(1).9aA-514)

table 10a

Compounds (X)-(1), wherein A is 2-fluoro-6-chlorophenyl I and B corresponds to one row of table A (Compounds (X)-(1).10aA-1 to (X)-(1).10aA-514)

table 11a

Compounds (X)-(1), wherein A is 3-fluoro-4-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1).11aA-1 to (X)-(1).11aA-514)

table 12a

Compounds (X)-(1), wherein A is 3-fluoro-5-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1).12aA-1 to (X)-(1).12aA-514)

table 13a

Compounds (X)-(1), wherein A is 2-chloro-3-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1).13aA-1 to (X)-(1).13aA-514)

table 14a

Compounds (X)-(1), wherein A is 2-chloro-4-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1).14aA-1 to (X)-(1).14aA-514)

table 15a

Compounds (X)-(1), wherein A is 2-chloro-5-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1).15aA-1 to (X)-(1).15aA-514)

table 16a

Compounds (X)-(1), wherein A is 3-chloro-4-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1).16aA-1 to (X)-(1).16aA-514)

table 17a

Compounds (X)-(1), wherein A is 2-methyl-3-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1).17aA-1 to (X)-(1).17aA-514)

table 18a

Compounds (X)-(1), wherein A is 2-methyl-4-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1).18aA-1 to (X)-(1).18aA-514)

table 19a

Compounds (X)-(1), wherein A is 2-methyl-5-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1).19aA-1 to (X)-(1).19aA-514) table 20a

Compounds (X)-(1 ), wherein A is 2-methyl-6-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).20aA-1 to (X)-(1 ).20aA-514)

table 21 a

Compounds (X)-(1 ), wherein A is 3-methyl-4-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).21 aA-1 to (X)-(1 ).21 aA-514)

table 22a

Compounds (X)-(1 ), wherein A is 3-methyl-5-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).22aA-1 to (X)-(1 ).22aA-514)

table 23a

Compounds (X)-(1 ), wherein A is 2-fluoro-3-methylphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).23aA-1 to (X)-(1 ).23aA-514)

table 24a

Compounds (X)-(1 ), wherein A is 2-fluoro-4-methylphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).24aA-1 to (X)-(1 ).24aA-514)

table 25a

Compounds (X)-(1 ), wherein A is 2-fluoro-5-methylphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).25aA-1 to (X)-(1 ).25aA-514)

table 26a

Compounds (X)-(1 ), wherein A is 3-fluoro-4-methylphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).26aA-1 to (X)-(1 ).26aA-514)

table 27a

Compounds (X)-(1 ), wherein A is 2-ethyl-3-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).27aA-1 to (X)-(1 ).27aA-514)

table 28a

Compounds (X)-(1 ), wherein A is 2-ethyl-4-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).28aA-1 to (X)-(1 ).28aA-514)

table 29a

Compounds (X)-(1 ), wherein A is 2-ethyl-5-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).29aA-1 to (X)-(1 ).29aA-514)

table 30a

Compounds (X)-(1 ), wherein A is 2-ethyl-6-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).30aA-1 to (X)-(1 ).30aA-514)

table 31 a

Compounds (X)-(1 ), wherein A is 3-ethyl-4-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).31 aA-1 to (X)-(1 ).31 aA-514)

table 32a

Compounds (X)-(1 ), wherein A is 3-ethyl-5-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).32aA-1 to (X)-(1 ).32aA-514)

table 33a

Compounds (X)-(1 ), wherein A is 2-fluoro-3-ethylphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).33aA-1 to (X)-(1 ).33aA-514) table 34a

Compounds (X)-(1 ), wherein A is 2-fluoro-4-ethylphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).34aA-1 to (X)-(1 ).34aA-514)

table 35a

Compounds (X)-(1 ), wherein A is 2-fluoro-5-ethylphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).35aA-1 to (X)-(1 ).35aA-514)

table 36a

Compounds (X)-(1 ), wherein A is 3-fluoro-4-ethylphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).36aA-1 to (X)-(1 ).36aA-514)

table 37a

Compounds (X)-(1 ), wherein A is 2-methoxy-3-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).37aA-1 to (X)-(1 ).37aA-514)

table 38a

Compounds (X)-(1 ), wherein A is 2-methoxy-4-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).38aA-1 to (X)-(1 ).38aA-514)

table 39a

Compounds (X)-(1 ), wherein A is 2-methoxy-5-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).39aA-1 to (X)-(1 ).39aA-514)

table 40a

Compounds (X)-(1 ), wherein A is 2-methoxy-6-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).40aA-1 to (X)-(1 ).40aA-514)

table 41 a

Compounds (X)-(1 ), wherein A is 3-methoxy-4-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).41 aA-1 to (X)-(1 ).41 aA-514)

table 42a

Compounds (X)-(1 ), wherein A is 3-methoxy-5-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).42aA-1 to (X)-(1 ).42aA-514)

table 43a

Compounds (X)-(1 ), wherein A is 2-fluoro-3-methoxyphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).43aA-1 to (X)-(1 ).43aA-514)

table 44a

Compounds (X)-(1 ), wherein A is 2-fluoro-4-methoxyphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).44aA-1 to (X)-(1 ).44aA-514)

table 45a

Compounds (X)-(1 ), wherein A is 2-fluoro-5-methoxyphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).45aA-1 to (X)-(1 ).45aA-514)

table 46a

Compounds (X)-(1 ), wherein A is 3-fluoro-4-methoxyphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).46aA-1 to (X)-(1 ).46aA-514)

table 47a

Compounds (X)-(1 ), wherein A is 3-fluoro-5-methoxyphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).47aA-1 to (X)-(1 ).47aA-514) table 48a

Compounds (X)-(1 ), wherein A is 2-(trifluoromethyl)-3-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).48aA-1 to (X)-(1 ).48aA-514) table 49a

Compounds (X)-(1 ), wherein A is 2-(trifluoromethyl)-4-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).49aA-1 to (X)-(1 ).49aA-514) table 50a

Compounds (X)-(1 ), wherein A is 2-(trifluoromethyl)-5-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).50aA-1 to (X)-(1 ).50aA-514) table 51 a

Compounds (X)-(1 ), wherein A is 2-(trifluoromethyl)-6-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).51 aA-1 to (X)-(1 ).51 aA-514) table 52a

Compounds (X)-(1 ), wherein A is 3-(trifluoromethyl)-4-fluorophenyl and B corre- sponds to one row of table A (Compounds (X)-(1 ).52aA-1 to (X)-(1 ).52aA-514) table 53a

Compounds (X)-(1 ), wherein A is 3-(trifluoromethyl)-5-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).53aA-1 to (X)-(1 ).53aA-514) table 54a

Compounds (X)-(1 ), wherein A is 2-fluoro-3-(trifluoromethyl)phenyl and B corresponds to one row of table A (Compounds (X)-(1 ).54aA-1 to (X)-(1 ).54aA-514) table 55a

Compounds (X)-(1 ), wherein A is 2-fluoro-4-(trifluoromethyl)phenyl and B corresponds to one row of table A (Compounds (X)-(1 ).55aA-1 to (X)-(1 ).55aA-514) table 56a

Compounds (X)-(1 ), wherein A is 2-fluoro-5-(trifluoromethyl)phenyl and B corresponds to one row of table A (Compounds (X)-(1 ).56aA-1 to (X)-(1 ).56aA-514) table 57a

Compounds (X)-(1 ), wherein A is 3-fluoro-4-(trifluoromethyl)phenyl and B corre- sponds to one row of table A (Compounds (X)-(1 ).57aA-1 to (X)-(1 ).57aA-514) table 58a

Compounds (X)-(1 ), wherein A is 2-(trifluoromethoxy)-3-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).58aA-1 to (X)-(1 ).58aA-514) table 59a

Compounds (X)-(1 ), wherein A is 2-(trifluoromethoxy)-4-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).59aA-1 to (X)-(1 ).59aA-514) table 60a

Compounds (X)-(1 ), wherein A is 2-(trifluoromethoxy)-5-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).60aA-1 to (X)-(1 ).60aA-514) table 61 a

Compounds (X)-(1 ), wherein A is 2-(trifluoromethoxy)-6-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).61 aA-1 to (X)-(1 ).61 aA-514) table 62a

Compounds (X)-(1 ), wherein A is 3-(trifluorome hoxy)-4-fluorophenyl and B corre- sponds to one row of table A (Compounds (X)- 1 ).62aA-1 to (X)-(1 ).62aA-514) table 63a

Compounds (X)-(1 ), wherein A is 3-(trifluorome hoxy)-5-fluorophenyl and B co re- sponds to one row of table A (Compounds (X)- 1 ).63aA-1 to (X)-(1 ).63aA-514 table 64a

Compounds (X)-(1 ), wherein A is 2-fluoro-3-(tri luoromethoxy)phenyl and B co re- sponds to one row of table A (Compounds (X)- 1 ).64aA-1 to (X)-(1 ).64aA-514 table 65a

Compounds (X)-(1 ), wherein A is 2-fluoro-4-(tri luoromethoxy)phenyl and B co re- sponds to one row of table A (Compounds (X)- 1 ).65aA-1 to (X)-(1 ).65aA-514 table 66a

Compounds (X)-(1 ), wherein A is 2-fluoro-5-(tri luoromethoxy)phenyl and B co re- sponds to one row of table A (Compounds (X)- 1 ).66aA-1 to (X)-(1 ).66aA-514 table 67a

Compounds (X)-(1 ), wherein A is 3-fluoro-4-(tri luoromethoxy)phenyl and B co re- sponds to one row of table A (Compounds (X)- 1 ).67aA-1 to (X)-(1 ).67aA-514 table 68a

Compounds (X)-(1 ), wherein A is 2-(difluorome hoxy)-3-fluorophenyl and B co re- sponds to one row of table A (Compounds (X)- 1 ).68aA-1 to (X)-(1 ).68aA-514 table 69a

Compounds (X)-(1 ), wherein A is 2-(difluorome hoxy)-4-fluorophenyl and B co re- sponds to one row of table A (Compounds (X)- 1 ).69aA-1 to (X)-(1 ).69aA-514 table 70a

Compounds (X)-(1 ), wherein A is 2-(difluorome hoxy)-5-fluorophenyl and B co re- sponds to one row of table A (Compounds (X)- 1 ).70aA-1 to (X)-(1 ).70aA-514 table 71 a

Compounds (X)-(1 ), wherein A is 2-(difluorome hoxy)-6-fluorophenyl and B co re- sponds to one row of table A (Compounds (X)- 1 ).71 aA-1 to (X)-(1 ).71 aA-514 table 72a

Compounds (X)-(1 ), wherein A is 3-(difluorome hoxy)-4-fluorophenyl and B co re- sponds to one row of table A (Compounds (X)- 1 ).72aA-1 to (X)-(1 ).72aA-514 table 73a

Compounds (X)-(1 ), wherein A is 3-(difluorome hoxy)-5-fluorophenyl and B co re- sponds to one row of table A (Compounds (X)- 1 ).73aA-1 to (X)-(1 ).73aA-514 table 74a

Compounds (X)-(1 ), wherein A is 2-fluoro-3-(d luoromethoxy)phenyl and B co re- sponds to one row of table A (Compounds (X)- 1 ).74aA-1 to (X)-(1 ).74aA-514 table 75a

Compounds (X)-(1 ), wherein A is 2-fluoro-4-(d luoromethoxy)phenyl and B co re- sponds to one row of table A (Compounds (X)- 1 ).75aA-1 to (X)-(1 ).75aA-514 table 76a

Compounds (X)-(1 ), wherein A is 2-fluoro-5-(difluoromethoxy)phenyl and B corresponds to one row of table A (Compounds (X)-(1 ).76aA-1 to (X)-(1 ).76aA-514) table 77a

Compounds (X)-(1 ), wherein A is 3-fluoro-4-(difluoromethoxy)phenyl and B corresponds to one row of table A (Compounds (X)-(1 ).77aA-1 to (X)-(1 ).77aA-514) table 78a

Compounds (X)-(1 ), wherein A is 2-(trifluoromethylthio)-3-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).78aA-1 to (X)-(1 ).78aA-514) table 79a

Compounds (X)-(1 ), wherein A is 2-(trifluoromethylthio)-4-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).79aA-1 to (X)-(1 ).79aA-514) table 80a

Compounds (X)-(1 ), wherein A is 2-(trifluoromethylthio)-5-fluorophenyl and B corre- sponds to one row of table A (Compounds (X)-(1 ).80aA-1 to (X)-(1 ).80aA-514) table 81 a

Compounds (X)-(1 ), wherein A is 2-(trifluoromethylthio)-6-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).81 aA-1 to (X)-(1 ).81 aA-514) table 82a

Compounds (X)-(1 ), wherein A is 3-(trifluoromethylthio)-4-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).82aA-1 to (X)-(1 ).82aA-514) table 83a

Compounds (X)-(1 ), wherein A is 3-(trifluoromethylthio)-5-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).83aA-1 to (X)-(1 ).83aA-514) table 84a

Compounds (X)-(1 ), wherein A is 2-fluoro-3-(trifluoromethylthio)phenyl and B corresponds to one row of table A (Compounds (X)-(1 ).84aA-1 to (X)-(1 ).84aA-514) table 85a

Compounds (X)-(1 ), wherein A is 2-fluoro-4-(trifluoromethylthio)phenyl and B corre- sponds to one row of table A (Compounds (X)-(1 ).85aA-1 to (X)-(1 ).85aA-514) table 86a

Compounds (X)-(1 ), wherein A is 2-fluoro-5-(trifluoromethylthio)phenyl and B corresponds to one row of table A (Compounds (X)-(1 ).86aA-1 to (X)-(1 ).86aA-514) table 87a

Compounds (X)-(1 ), wherein A is 3-fluoro-4-(trifluoromethylthio)phenyl and B corresponds to one row of table A (Compounds (X)-(1 ).87aA-1 to (X)-(1 ).87aA-514) table 88a

Compounds (X)-(1 ), wherein A is 2,3,4-trifluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).88aA-1 to (X)-(1 ).88aA-514)

table 89a

Compounds (X)-(1 ), wherein A is 2,3,5-trifluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).89aA-1 to (X)-(1 ).89aA-514) table 90a

Compounds (X)-(1 ), wherein A is 2,3,6-trifluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).90aA-1 to (X)-(1 ).90aA-514)

table 91 a

Compounds (X)-(1 ), wherein A is 2,4,5-trifluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).91 aA-1 to (X)-(1 ).91 aA-514)

table 92a

Compounds (X)-(1 ), wherein A is 2,4,6-trifluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).92aA-1 to (X)-(1 ).92aA-514)

table 93a

Compounds (X)-(1 ), wherein A is 3,4,5-trifluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).93aA-1 to (X)-(1 ).93aA-514)

table 94a

Compounds (X)-(1 ), wherein A is phenyl and B corresponds to one row of table A (Compounds (X)-(1 ).94aA-1 to (X)-(1 ).94aA-514)

table 95a

Compounds (X)-(1 ), wherein A is 2-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).95aA-1 to (X)-(1 ).95aA-514)

table 96a

Compounds (X)-(1 ), wherein A is 3-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).96aA-1 to (X)-(1 ).96aA-514)

table 97a

Compounds (X)-(1 ), wherein A is 4-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).97aA-1 to (X)-(1 ).97aA-514)

table 98a

Compounds (X)-(1 ), wherein A is 2-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).98aA-1 to (X)-(1 ).98aA-514)

table 99a

Compounds (X)-(1 ), wherein A is 3-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).99aA-1 to (X)-(1 ).99aA-514)

table 100a

Compounds (X)-(1 ), wherein A is 4-fluorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).100aA-1 to (X)-(1 ).100aA-514)

table 101 a

Compounds (X)-(1 ), wherein A is 2-methylphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).101 aA-1 to (X)-(1 ).101 aA-514)

table 102a v

Compounds (X)-(1 ), wherein A is 3-methylphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).102aA-1 to (X)-(1 ).102aA-514)

table 103a

Compounds (X)-(1 ), wherein A is 4-methylphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).103aA-1 to (X)-(1 ).103aA-514) table 104a

Compounds (X)-(1), wherein A is 2-ethylphenyl and B corresponds to one row of table A (Compounds (X)-(1).104aA-1 to (X)-(1).104aA-514)

table 105a

Compounds (X)-(1), wherein A is 3-ethylphenyl and B corresponds to one row of table A (Compounds (X)-(1).105aA-1 to (X)-(1).105aA-514)

table 106a

Compounds (X)-(1), wherein A is 4-ethylphenyl and B corresponds to one row of table A (Compounds (X)-(1).106aA-1 to (X)-(1).106aA-514)

table 107a

Compounds (X)-(1), wherein A is 2-methoxyphenyl and B corresponds to one row of table A (Compounds (X)-(1).107aA-1 to (X)-(1).107aA-514)

table 108a

Compounds (X)-(1), wherein A is 3-methoxyphenyl and B corresponds to one row of table A (Compounds (X)-(1).108aA-1 to (X)-(1).108aA-514)

table 109a

Compounds (X)-(1), wherein A is 4-methoxyphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).109aA-1 to (X)-(1 ).109aA-514)

table 110a

Compounds (X)-(1), wherein A is 2-trifluoromethylphenyl and B corresponds to one row of table A (Compounds (X)-(1).110aA-1 to (X)-(1).110aA-514)

table 111a

Compounds (X)-(1), wherein A is 3-trifluoromethylphenyl and B corresponds to one row of table A (Compounds (X)-(1).111aA-1 to (X)-(1).111aA-514)

table 112a

Compounds (X)-(1), wherein A is 4-trifluoromethylphenyl and B corresponds to one row of table A (Compounds (X)-(1).112aA-1 to (X)-(1).112aA-514)

table 113a

Compounds (X)-(1), wherein A is 2-trifluoromethoxyphenyl and B corresponds to one row of table A (Compounds (X)-(1).113aA-1 to (X)-(1).113aA-514)

table 114a

Compounds (X)-(1), wherein A is 3-trifluoromethoxyphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).114aA-1 to (X)-(1 ).114aA-514)

table 115a

Compounds (X)-(1), wherein A is 4-trifluoromethoxyphenyl and B corresponds to one row of table A (Compounds (X)-(1).115aA-1 to (X)-(1).115aA-514)

table 116a

Compounds (X)-(1), wherein A is 2-difluoromethoxyphenyl and B corresponds to one row of table A (Compounds (X)-(1).116aA-1 to (X)-(1).116aA-514)

table 117a

Compounds (X)-(1), wherein A is 3-difluoromethoxyphenyl and B corresponds to one row of table A (Compounds (X)-(1).117aA-1 to (X)-(1).117aA-514) table 118a

Compounds (X)-(1), wherein A is 4-difluoromethoxyphenyl and B corresponds to one row of table A (Compounds (X)-(1).118aA-1 to (X)-(1).118aA-514)

table 119a

Compounds (X)-(1), wherein A is 2-trifluoromethylthiophenyl and B corresponds to one row of table A (Compounds (X)-(1).119aA-1 to (X)-(1).119aA-514)

table 120a

Compounds (X)-(1), wherein A is 3-trifluoromethylthiophenyl and B corresponds to one row of table A (Compounds (X)-(1).120aA-1 to (X)-(1).120aA-514)

table 121a

Compounds (X)-(1), wherein A is 4-trifluoromethylthiophenyl and B corresponds to one row of table A (Compounds (X)-(1).121aA-1 to (X)-(1).121aA-514)

table 122a

Compounds (X)-(1), wherein A is 2,3-dichlorophenyl and B corresponds to one row of table A (Compounds (X)-(1).122aA-1 to (X)-(1).122aA-514)

table 123a

Compounds (X)-(1), wherein A is 2,4-dichlorophenyl and B corresponds to one row of table A (Compounds (X)-(1).123aA-1 to (X)-(1).123aA-514)

table 124a

Compounds (X)-(1), wherein A is 2,5-dichlorophenyl and B corresponds to one row of table A (Compounds (X)-(1).124aA-1 to (X)-(1).124aA-514)

table 125a

Compounds (X)-(1), wherein A is 2,6-dichlorophenyl and B corresponds to one row of table A (Compounds (X)-(1).125aA-1 to (X)-(1).125aA-514)

table 126a

Compounds (X)-(1), wherein A is 3,4-dichlorophenyl and B corresponds to one row of table A (Compounds (X)-(1).126aA-1 to (X)-(1).126aA-514)

table 127a

Compounds (X)-(1), wherein A is 3,5-dichlorophenyl and B corresponds to one row of table A (Compounds (X)-(1).127aA-1 to (X)-(1).127aA-514)

table 128a

Compounds (X)-(1), wherein A is 2,3-dimethylphenyl and B corresponds to one row of table A (Compounds (X)-(1).128aA-1 to (X)-(1).128aA-514)

table 129a

Compounds (X)-(1), wherein A is 2,4-dimethylphenyl and B corresponds to one row of table A (Compounds (X)-(1).129aA-1 to (X)-(1).129aA-514)

table 130a

Compounds (X)-(1), wherein A is 2,5-dimethylphenyl and B corresponds to one row of table A (Compounds (X)-(1).130aA-1 to (X)-(1).130aA-514)

table 131a

Compounds (X)-(1), wherein A is 2,6-dimethylphenyl and B corresponds to one row of table A (Compounds (X)-(1).131aA-1 to (X)-(1).131aA-514) table 132a

Compounds (X)-(1 ), wherein A is 3,4-dimethylphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).132aA-1 to (X)-(1 ).132aA-514)

table 133a

Compounds (X)-(1 ), wherein A is 3,5-dimethylphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).133aA-1 to (X)-(1 ).133aA-514)

table 134a

Compounds (X)-(1 ), wherein A is 2,3-diethylphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).134aA-1 to (X)-(1 ).134aA-514)

table 135a

Compounds (X)-(1 ), wherein A is 2,4-diethylphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).135aA-1 to (X)-(1 ).135aA-514)

table 136a

Compounds (X)-(1 ), wherein A is 2,5-diethylphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).136aA-1 to (X)-(1 ).136aA-514)

table 137a

Compounds (X)-(1 ), wherein A is 2,6-diethylphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).137aA-1 to (X)-(1 ).137aA-514)

table 138a

Compounds (X)-(1 ), wherein A is 3,4-diethylphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).138aA-1 to (X)-(1 ).138aA-514)

table 139a

Compounds (X)-(1 ), wherein A is 3,5-diethylphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).139aA-1 to (X)-(1 ).139aA-514)

table 140a

Compounds (X)-(1 ), wherein A is 2,3-dimethoxyphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).140aA-1 to (X)-(1 ).140aA-514)

table 141 a

Compounds (X)-(1 ), wherein A is 2,4-dimethoxyphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).141 aA-1 to (X)-(1 ).141 aA-514)

table 142a

Compounds (X)-(1 ), wherein A is 2,5-dimethoxyphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).142aA-1 to (X)-(1 ).142aA-514)

table 143a

Compounds (X)-(1 ), wherein A is 2,6-dimethoxyphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).143aA-1 to (X)-(1 ).143aA-514)

table 144a

Compounds (X)-(1 ), wherein A is 3,4-dimethoxyphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).144aA-1 to (X)-(1 ).144aA-514)

table 145a

Compounds (X)-(1 ), wherein A is 3,5-dimethoxyphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).145aA-1 to (X)-(1 ).145aA-514) table 146a

Compounds (X)-(1 ), wherein A is 2,3-di(trifluoromethyl)phenyl and B corresponds to one row of table A (Compounds (X)-(1 ).146aA-1 to (X)-(1 ).146aA-514) table 147a

Compounds (X)-(1 ), wherein A is 2,4-di(trifluoromethyl)phenyl and B corresponds to one row of table A (Compounds (X)-(1 ).147aA-1 to (X)-(1 ).147aA-514) table 148a

Compounds (X)-(1 ), wherein A is 2,5-di(trifluoromethyl)phenyl and B corresponds to one row of table A (Compounds (X)-(1 ).148aA-1 to (X)-(1 ).148aA-514) table 149a

Compounds (X)-(1 ), wherein A is 2,6-di(trifluoromethyl)phenyl and B corresponds to one row of table A (Compounds (X)-(1 ).149aA-1 to (X)-(1 ).149aA-514) table 150a

Compounds (X)-(1 ), wherein A is 3,4-di(trifluoromethyl)phenyl and B corresponds to one row of table A (Compounds (X)-(1 ).150aA-1 to (X)-(1 ).150aA-514) table 151 a

Compounds (X)-(1 ), wherein A is 3,5-di(trifluoromethyl)phenyl and B corresponds to one row of table A (Compounds (X)-(1 ).151 aA-1 to (X)-(1 ).151 aA-514) table 152a

Compounds (X)-(1 ), wherein A is 2,3-di(trifluoromethoxy)phenyl and B correspond to one row of table A (Compounds (X)-(1 ).152aA-1 to (X)-(1 ).152aA-514) table 153a

Compounds (X)-(1 ), wherein A is 2,4-di(trifluoromethoxy)phenyl and B correspond to one row of table A (Compounds (X)-(1 ).153aA-1 to (X)-(1 ).153aA-514) table 154a

Compounds (X)-(1 ), wherein A is 2,5-di(trifluoromethoxy)phenyl and B correspond to one row of table A (Compounds (X)-(1 ).154aA-1 to (X)-(1 ).154aA-514) table 155a

Compounds (X)-(1 ), wherein A is 2,6-di(trifluoromethoxy)phenyl and B correspond to one row of table A (Compounds (X)-(1 ).155aA-1 to (X)-(1 ).155aA-514) table 156a

Compounds (X)-(1 ), wherein A is 3,4-di(trifluoromethoxy)phenyl and B correspond to one row of table A (Compounds (X)-(1 ).156aA-1 to (X)-(1 ).156aA-514) table 157a

Compounds (X)-(1 ), wherein A is 3,5-di(trifluoromethoxy)phenyl and B correspond to one row of table A (Compounds (X)-(1 ).157aA-1 to (X)-(1 ).157aA-514) table 158a

Compounds (X)-(1 ), wherein A is 2,3-di(difluoromethoxy)phenyl and B correspond to one row of table A (Compounds (X)-(1 ).158aA-1 to (X)-(1 ).158aA-514) table 159a

Compounds (X)-(1 ), wherein A is 2,4-di(difluoromethoxy)phenyl and B correspond to one row of table A (Compounds (X)-(1 ).159aA-1 to (X)-(1 ).159aA-514) table 160a

Compounds (X)-(1), wherein A is 2,5-di(difluoromethoxy)phenyl and B correspond to one row of table A (Compounds (X)-(1).160aA-1 to (X)-(1).160aA-514) table 161a

Compounds (X)-(1), wherein A is 2,6-di(difluoromethoxy)phenyl and B correspond to one row of table A (Compounds (X)-(1).161aA-1 to (X)-(1).161aA-514) table 162a

Compounds (X)-(1), wherein A is 3,4-di(difluoromethoxy)phenyl and B correspond to one row of table A (Compounds (X)-(1).162aA-1 to (X)-(1).162aA-514) table 163a

Compounds (X)-(1), wherein A is 3,5-di(difluoromethoxy)phenyl and B correspond to one row of table A (Compounds (X)-(1).163aA-1 to (X)-(1).163aA-514) table 164a

Compounds (X)-(1), wherein A is 2,3-di(trifluoromethylthio)phenyl and B corre- spondstoone row of table A (Compounds (X)-(1).164aA-1 to (X)-(1).164aA-514) table 165a

Compounds (X)-(1), wherein A is 2,4-di(trifluoromethylthio)phenyl and B corresponds to one row of table A (Compounds (X)-(1).165aA-1 to (X)-(1).165aA-514) table 166a

Compounds (X)-(1), wherein A is 2,5-di(trifluoromethylthio)phenyl and B corresponds to one row of table A (Compounds (X)-(1).166aA-1 to (X)-(1).166aA-514) table 167a

Compounds (X)-(1), wherein A is 2,6-di(trifluoromethylthio)phenyl and B corresponds to one row of table A (Compounds (X)-(1).167aA-1 to (X)-(1).167aA-514) table 168a

Compounds (X)-(1), wherein A is 3,4-di(trifluoromethylthio)phenyl and B corresponds to one row of table A (Compounds (X)-(1).168aA-1 to (X)-(1).168aA-514) table 169a

Compounds (X)-(1), wherein A is 3,5-di(trifluoromethylthio)phenyl and B corre- spondstoone row of table A (Compounds (X)-(1).169aA-1 to (X)-(1).169aA-514) table 170a

Compounds (X)-(1), wherein A is 2-methyl-3-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).170aA-1 to (X)-(1 ).170aA-514) table 171a

Compounds (X)-(1), wherein A is 2-methyl-4-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1).171aA-1 to (X)-(1).171aA-514) table 172a

Compounds (X)-(1), wherein A is 2-methyl-5-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1).172aA-1 to (X)-(1).172aA-514) table 173a

Compounds (X)-(1), wherein A is 2-methyl-6-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1).173aA-1 to (X)-(1).173aA-514) table 174a

Compounds (X)-(1 ), wherein A is 3-methyl-4-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).174aA-1 to (X)-(1 ).174aA-514) table 175a

Compounds (X)-(1 ), wherein A is 3-methyl-5-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).175aA-1 to (X)-(1 ).175aA-514) table 176a

Compounds (X)-(1 ), wherein A is 2-chloro-3-methylphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).176aA-1 to (X)-(1 ).176aA-514) table 177a

Compounds (X)-(1 ), wherein A is 2-chloro-4-methylphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).177aA-1 to (X)-(1 ).177aA-514) table 178a

Compounds (X)-(1 ), wherein A is 2-chloro-5-methylphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).178aA-1 to (X)-(1 ).178aA-514) table 179a

Compounds (X)-(1 ), wherein A is 3-chloro-4-methylphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).179aA-1 to (X)-(1 ).179aA-514) table 180a

Compounds (X)-(1 ), wherein A is 2-ethyl-3-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).180aA-1 to (X)-(1 ).180aA-514)

table 181 a

Compounds (X)-(1 ), wherein A is 2-ethyl-4-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).181 aA-1 to (X)-(1 ).181 aA-514)

table 182a

Compounds (X)-(1 ), wherein A is 2-ethyl-5-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).182aA-1 to (X)-(1 ).182aA-514)

table 183a

Compounds (X)-(1 ), wherein A is 2-ethyl-6-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).183aA-1 to (X)-(1 ).183aA-514)

table 184a

Compounds (X)-(1 ), wherein A is 3-ethyl-4-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).184aA-1 to (X)-(1 ).184aA-514)

table 185a

Compounds (X)-(1 ), wherein A is 3-ethyl-5-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).185aA-1 to (X)-(1 ).185aA-514)

table 186a

Compounds (X)-(1 ), wherein A is 2-chloro-3-ethylphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).186aA-1 to (X)-(1 ).186aA-514)

table 187a

Compounds (X)-(1 ), wherein A is 2-chloro-4-ethylphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).187aA-1 to (X)-(1 ).187aA-514) table 188a

Compounds (X)-(1 ), wherein A is 2-chloro-5-ethylphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).188aA-1 to (X)-(1 ).188aA-514)

table 189a

Compounds (X)-(1 ), wherein A is 3-chloro-4-ethylphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).189aA-1 to (X)-(1 ).189aA-514)

table 190a

Compounds (X)-(1 ), wherein A is 2-methoxy-3-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).190aA-1 to (X)-(1 ).190aA-514) table 191 a

Compounds (X)-(1 ), wherein A is 2-methoxy-4-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).191 aA-1 to (X)-(1 ).191 aA-514) table 192a

Compounds (X)-(1 ), wherein A is 2-methoxy-5-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).192aA-1 to (X)-(1 ).192aA-514) table 193a

Compounds (X)-(1 ), wherein A is 2-methoxy-6-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).193aA-1 to (X)-(1 ).193aA-514) table 194a

Compounds (X)-(1 ), wherein A is 3-methoxy-4-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).194aA-1 to (X)-(1 ).194aA-514) table 195a

Compounds (X)-(1 ), wherein A is 3-methoxy-5-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).195aA-1 to (X)-(1 ).195aA-514) table 196a

Compounds (X)-(1 ), wherein A is 2-chloro-3-methoxyphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).196aA-1 to (X)-(1 ).196aA-514) table 197a

Compounds (X)-(1 ), wherein A is 2-chloro-4-methoxyphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).197aA-1 to (X)-(1 ).197aA-514) table 198a

Compounds (X)-(1 ), wherein A is 2-chloro-5-methoxyphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).198aA-1 to (X)-(1 ).198aA-514) table 199a

Compounds (X)-(1 ), wherein A is 3-chloro-4-methoxyphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).199aA-1 to (X)-(1 ).199aA-514) table 200a

Compounds (X)-(1 ), wherein A is 2-(trifluoromethyl)-3-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).200aA-1 to (X)-(1 ).200aA-514) table 201 a

Compounds (X)-(1 ), wherein A is 2-(trifluoromethyl)-4-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).201 aA-1 to (X)-(1 ).201 aA-514) table 202a

Compounds (X)-(1 ), wherein A is 2-(trifluoromethyl)-5-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).202aA-1 to (X)-(1 ).202aA-514) table 203a

Compounds (X)-(1 ), wherein A is 2-(trifluoromethyl)-6-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).203aA-1 to (X)-(1 ).203aA-514) table 204a

Compounds (X)-(1 ), wherein A is 3-(trifluoromethyl)-4-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).204aA-1 to (X)-(1 ).204aA-514) table 205a

Compounds (X)-(1 ), wherein A is 3-(trifluoromethyl)-5-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).205aA-1 to (X)-(1 ).205aA-514) table 206a

Compounds (X)-(1 ), wherein A is 2-chloro-3-(trifluoromethyl)phenyl and B corre- sponds to one row of table A (Compounds (X)-(1 ).206aA-1 to (X)-(1 ).206aA-514) table 207a

Compounds (X)-(1 ), wherein A is 2-chloro-4-(trifluoromethyl)phenyl and B corresponds to one row of table A (Compounds (X)-(1 ).207aA-1 to (X)-(1 ).207aA-514) table 208a

Compounds (X)-(1 ), wherein A is 2-chloro-5-(trifluoromethyl)phenyl and B corresponds to one row of table A (Compounds (X)-(1 ).208aA-1 to (X)-(1 ).208aA-514) table 209a

Compounds (X)-(1 ), wherein A is 3-chloro-4-(trifluoromethyl)phenyl and B corresponds to one row of table A (Compounds (X)-(1 ).209aA-1 to (X)-(1 ).209aA-514) table 210a

Compounds (X)-(1 ), wherein A is 2-(trifluoromethoxy)-3-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).210aA-1 to (X)-(1 ).210aA-514) table 21 1 a

Compounds (X)-(1 ), wherein A is 2-(trifluoromethoxy)-4-chlorophenyl and B corre- sponds to one row of table A (Compounds (X)-(1 ).21 1 aA-1 to (X)-(1 ).21 1 aA-514) table 212a

Compounds (X)-(1 ), wherein A is 2-(trifluoromethoxy)-5-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).212aA-1 to (X)-(1 ).212aA-514) table 213a

Compounds (X)-(1 ), wherein A is 2-(trifluoromethoxy)-6-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).213aA-1 to (X)-(1 ).213aA-514) table 214a

Compounds (X)-(1 ), wherein A is 3-(trifluoromethoxy)-4-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).214aA-1 to (X)-(1 ).214aA-514) table 215a

Compounds (X)-(1 ), wherein A is 3-(trifluoromethoxy)-5-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).215aA-1 to (X)-(1 ).215aA-514) table 216a

Compounds (X)-(1 ), wherein A is 2-chloro-3-(trifluoromethoxy)phenyl and B corresponds to one row of table A (Compounds (X)-(1 ).216aA-1 to (X)-(1 ).216aA-514) table 217a

Compounds (X)-(1 ), wherein A is 2-chloro-4-(trifluoromethoxy)phenyl and B corresponds to one row of table A (Compounds (X)-(1 ).217aA-1 to (X)-(1 ).217aA-514) table 218a

Compounds (X)-(1 ), wherein A is 2-chloro-5-(trifluoromethoxy)phenyl and B corresponds to one row of table A (Compounds (X)-(1 ).218aA-1 to (X)-(1 ).218aA-514) table 219a

Compounds (X)-(1 ), wherein A is 3-chloro-4-(trifluoromethoxy)phenyl and B corresponds to one row of table A (Compounds (X)-(1 ).219aA-1 to (X)-(1 ).219aA-514) table 220a

Compounds (X)-(1 ), wherein A is 2-(difluoromethoxy)-3-chlorophenyl and B corre- sponds to one row of table A (Compounds (X)-(1 ).220aA-1 to (X)-(1 ).220aA-514) table 221 a

Compounds (X)-(1 ), wherein A is 2-(difluoromethoxy)-4-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).221 aA-1 to (X)-(1 ).221 aA-514) table 222a

Compounds (X)-(1 ), wherein A is 2-(difluoromethoxy)-5-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).222aA-1 to (X)-(1 ).222aA-514) table 223a

Compounds (X)-(1 ), wherein A is 2-(difluoromethoxy)-6-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).223aA-1 to (X)-(1 ).223aA-514) table 224a

Compounds (X)-(1 ), wherein A is 3-(difluoromethoxy)-4-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).224aA-1 to (X)-(1 ).224aA-514) table 225a

Compounds (X)-(1 ), wherein A is 3-(difluoromethoxy)-5-chlorophenyl and B corre- sponds to one row of table A (Compounds (X)-(1 ).225aA-1 to (X)-(1 ).225aA-514) table 226a

Compounds (X)-(1 ), wherein A is 2-chloro-3-(difluoromethoxy)phenyl and B corresponds to one row of table A (Compounds (X)-(1 ).226aA-1 to (X)-(1 ).226aA-514) table 227a

Compounds (X)-(1 ), wherein A is 2-chloro-4-(difluoromethoxy)phenyl and B corresponds to one row of table A (Compounds (X)-(1 ).227aA-1 to (X)-(1 ).227aA-514) table 228a

Compounds (X)-(1 ), wherein A is 2-chloro-5-(difluoromethoxy)phenyl and B corresponds to one row of table A (Compounds (X)-(1 ).228aA-1 to (X)-(1 ).228aA-514) table 229a

Compounds (X)-(1 ), wherein A is 3-chloro-4-(difluoromethoxy)phenyl and B corresponds to one row of table A (Compounds (X)-(1 ).229aA-1 to (X)-(1 ).229aA-514) table 230a

Compounds (X)-(1 ), wherein A is 2-(trifluoromethylthio)-3-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).230aA-1 to (X)-(1 ).230aA-514) table 231 a

Compounds (X)-(1 ), wherein A is 2-(trifluoromethylthio)-4-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).231 aA-1 to (X)-(1 ).231 aA-514) table 232a

Compounds (X)-(1 ), wherein A is 2-(trifluoromethylthio)-5-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).232aA-1 to (X)-(1 ).232aA-514) table 233a

Compounds (X)-(1 ), wherein A is 2-(trifluoromethylthio)-6-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).233aA-1 to (X)-(1 ).233aA-514) table 234a

Compounds (X)-(1 ), wherein A is 3-(trifluoromethylthio)-4-chlorophenyl and B cor- responds to one row of table A (Compounds (X)-(1 ).234aA-1 to (X)-(1 ).234aA-514) table 235a

Compounds (X)-(1 ), wherein A is 3-(trifluoromethylthio)-5-chlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).235aA-1 to (X)-(1 ).235aA-514) table 236a

Compounds (X)-(1 ), wherein A is 2-chloro-3-(trifluoromethylthio)phenyl and B corresponds to one row of table A (Compounds (X)-(1 ).236aA-1 to (X)-(1 ).236aA-514) table 237a

Compounds (X)-(1 ), wherein A is 2-chloro-4-(trifluoromethylthio)phenyl and B corresponds to one row of table A (Compounds (X)-(1 ).237aA-1 to (X)-(1 ).237aA-514) table 238a

Compounds (X)-(1 ), wherein A is 2-chloro-5-(trifluoromethylthio)phenyl and B corresponds to one row of table A (Compounds (X)-(1 ).238aA-1 to (X)-(1 ).238aA-514) table 239a

Compounds (X)-(1 ), wherein A is 3-chloro-4-(trifluoromethylthio)phenyl and B cor- responds to one row of table A (Compounds (X)-(1 ).239aA-1 to (X)-(1 ).239aA-514) table 240a

Compounds (X)-(1 ), wherein A is 2,3,4-trichlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).240aA-1 to (X)-(1 ).240aA-514)

table 241 a

Compounds (X)-(1 ), wherein A is 2,3,5-trichlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).241 aA-1 to (X)-(1 ).241 aA-514)

table 242a

Compounds (X)-(1 ), wherein A is 2,3,6-trichlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).242aA-1 to (X)-(1 ).242aA-514)

table 243a

Compounds (X)-(1 ), wherein A is 2,4,5-trichlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).243aA-1 to (X)-(1 ).243aA-514) table 244a

Compounds (X)-(1 ), wherein A is 2,4,6-trichlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).244aA-1 to (X)-(1 ).244aA-514)

table 245a

Compounds (X)-(1 ), wherein A is 3,4,5-trichlorophenyl and B corresponds to one row of table A (Compounds (X)-(1 ).245aA-1 to (X)-(1 ).245aA-514)

table 246a

Compounds (X)-(1 ), wherein A is 2,3,4-trimethylphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).246aA-1 to (X)-(1 ).246aA-514)

table 247a

Compounds (X)-(1 ), wherein A is 2,3,5-trimethylphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).247aA-1 to (X)-(1 ).247aA-514)

table 248a

Compounds (X)-(1 ), wherein A is 2,3,6-trimethylphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).248aA-1 to (X)-(1 ).248aA-514)

table 249a

Compounds (X)-(1 ), wherein A is 2,4,5-trimethylphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).249aA-1 to (X)-(1 ).249aA-514)

table 250a

Compounds (X)-(1 ), wherein A is 2,4,6-trimethylphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).250aA-1 to (X)-(1 ).250aA-514)

table 251 a

Compounds (X)-(1 ), wherein A is 3,4,5-trimethylphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).251 aA-1 to (X)-(1 ).251 aA-514)

table 252a

Compounds (X)-(1 ), wherein A is 2,3,4-trimethoxyphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).252aA-1 to (X)-(1 ).252aA-514)

table 253a

Compounds (X)-(1 ), wherein A is 2,3,5-trimethoxyphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).253aA-1 to (X)-(1 ).253aA-514)

table 254a

Compounds (X)-(1 ), wherein A is 2,3,6-trimethoxyphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).254aA-1 to (X)-(1 ).254aA-514)

table 255a

Compounds (X)-(1 ), wherein A is 2,4,5-trimethoxyphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).255aA-1 to (X)-(1 ).255aA-514)

table 256a

Compounds (X)-(1 ), wherein A is 2,4,6-trimethoxyphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).256aA-1 to (X)-(1 ).256aA-514)

table 257a

Compounds (X)-(1 ), wherein A is 3,4,5-trimethoxyphenyl and B corresponds to one row of table A (Compounds (X)-(1 ).257aA-1 to (X)-(1 ).257aA-514) table A

row B row B

A-1 phenyl A-40 3,5-difluorophenyl

A-2 2-chlorophenyl A-41 2,3-dimethylphenyl

A-3 3-chlorophenyl A-42 2,4-dimethylphenyl

A-4 4-chlorophenyl A-43 2,5-dimethylphenyl

A-5 2-fluorophenyl A-44 2,6-dimethylphenyl

A-6 3-fluorophenyl A-45 3,4-dimethylphenyl

A-7 4-fluorophenyl A-46 3,5-dimethylphenyl

A-8 2-methylphenyl A-47 2,3-diethylphenyl

A-9 3-methylphenyl A-48 2,4-diethylphenyl

A-10 4-methylphenyl A-49 2,5-diethylphenyl

A-1 1 2-ethylphenyl A-50 2,6-diethylphenyl

A-12 3-ethylphenyl A-51 3,5-diethylphenyl

A-13 4-ethylphenyl A-52 3,4-diethylphenyl

A-14 2-methoxyphenyl A-53 2,3-dimethoxyphenyl

A-15 3-methoxyphenyl A-54 2,4-dimethoxyphenyl

A-16 4-methoxyphenyl A-55 2,5-dimethoxyphenyl

A-17 2-trifluoromethylphenyl A-56 2,6-dimethoxyphenyl

A-18 3-trifluoromethylphenyl A-57 3,4-dimethoxyphenyl

A-19 4-trifluoromethylphenyl A-58 3,5-dimethoxyphenyl

A-20 2-trifluoromethoxyphenyl A-59 2,3-di(trifluoromethyl)phenyl

A-21 3-trifluoromethoxyphenyl A-60 2,4-di(trifluoromethyl)phenyl

A-22 4-trifluoromethoxyphenyl A-61 2,5-di(trifluoromethyl)phenyl

A-23 2-difluoromethoxyphenyl A-62 2,6-di(trifluoromethyl)phenyl

A-24 3-difluoromethoxyphenyl A-63 3,4-di(trifluoromethyl)phenyl

A-25 4-difluoromethoxyphenyl A-64 3,5-di(trifluoromethyl)phenyl

A-26 2-trifluoromethylthiophenyl A-65 2,3-di(trifluoromethoxy)phenyl

A-27 3-trifluoromethylthiophenyl A-66 2,4-di(trifluoromethoxy)phenyl

A-28 4-trifluoromethylthiophenyl A-67 2,5-di(trifluoromethoxy)phenyl

A-29 2,3-dichlorophenyl A-68 2,6-di(trifluoromethoxy)phenyl

A-30 2,4-dichlorophenyl A-69 3,4-di(trifluoromethoxy)phenyl

A-31 2,5-dichlorophenyl A-70 3,5-di(trifluoromethoxy)phenyl

A-32 2,6-dichlorophenyl A-71 2,3-di(difluoromethoxy)phenyl

A-33 3,4-dichlorophenyl A-72 2,4-di(difluoromethoxy)phenyl

A-34 3,5-dichlorophenyl A-73 2,5-di(difluoromethoxy)phenyl

A-35 2,3-difluorophenyl A-74 2,6-di(difluoromethoxy)phenyl

A-36 2,4-difluorophenyl A-75 3,4-di(difluoromethoxy)phenyl

A-37 2,5-difluorophenyl A-76 3,5-di(difluoromethoxy)phenyl

A-38 2,6-difluorophenyl A-77 2,3-

A-39 3,4-difluorophenyl di(trifluoromethylthio)phenyl row B row B

A-78 2,4- A-1 13 2-chloro-3-ethylphenyl di(trifluoromethylthio)phenyl A-1 14 2-chloro-4-ethylphenyl

A-79 2,5- A-1 15 2-chloro-5-ethylphenyl di(trifluoromethylthio)phenyl A-1 16 3-chloro-4-ethylphenyl

A-80 2,6- A-1 17 2-ethyl-3-chlorophenyl di(trifluoromethylthio)phenyl A-1 18 2-ethyl-4-chlorophenyl

A-81 3,4- A-1 19 2-ethyl-5-chlorophenyl di(trifluoromethylthio)phenyl A-120 2-ethyl-6-chlorophenyl

A-82 3,5- A-121 3-ethyl-4-chlorophenyl di(trifluoromethylthio)phenyl A-122 3-ethyl-5-chlorophenyl

A-83 2-fluoro-3-chlorophenyl A-123 2-ethyl-3-fluorophenyl

A-84 2-fluoro-4-chlorophenyl A-124 2-ethyl-4-fluorophenyl

A-85 2-fluoro-5-chlorophenyl A-125 2-ethyl-5-fluorophenyl

A-86 2-fluoro-6-chlorophenyl A-126 2-ethyl-6-fluorophenyl

A-87 3-fluoro-4-chlorophenyl A-127 3-ethyl-4-fluorophenyl

A-88 3-fluoro-5-chlorophenyl A-128 3-ethyl-5-fluorophenyl

A-89 2-chloro-3-fluorophenyl A-129 2-fluoro-3-ethylphenyl

A-90 2-chloro-4-fluorophenyl A-130 2-fluoro-4-ethylphenyl

A-91 2-chloro-5-fluorophenyl A-131 2-fluoro-5-ethylphenyl

A-92 3-chloro-4-fluorophenyl A-132 3-fluoro-4-ethylphenyl

A-93 2-methyl-3-chlorophenyl A-133 2-methoxy-3-chlorophenyl

A-94 2-methyl-4-chlorophenyl A-134 2-methoxy-4-chlorophenyl

A-95 2-methyl-5-chlorophenyl A-135 2-methoxy-5-chlorophenyl

A-96 2-methyl-6-chlorophenyl A-136 2-methoxy-6-chlorophenyl

A-97 3-methyl-4-chlorophenyl A-137 3-methoxy-4-chlorophenyl

A-98 3-methyl-5-chlorophenyl A-138 3-methoxy-5-chlorophenyl

A-99 2-chloro-3-methylphenyl A-139 2-chloro-3-methoxyphenyl

A-100 2-chloro-4-methylphenyl A-140 2-chloro-4-methoxyphenyl

A-101 2-chloro-5-methylphenyl A-141 2-chloro-5-methoxyphenyl

A-102 3-chloro-4-methylphenyl A-142 3-chloro-4-methoxyphenyl

A-103 2-methyl-3-fluorophenyl A-143 2-methoxy-3-fluorophenyl

A-104 2-methyl-4-fluorophenyl A-144 2-methoxy-4-fluorophenyl

A-105 2-methyl-5-fluorophenyl A-145 2-methoxy-5-fluorophenyl

A-106 2-methyl-6-fluorophenyl A-146 2-methoxy-6-fluorophenyl

A-107 3-methyl-4-fluorophenyl A-147 3-methoxy-4-fluorophenyl

A-108 3-methyl-5-fluorophenyl A-148 3-methoxy-5-fluorophenyl

A-109 2-fluoro-3-methylphenyl A-149 2-fluoro-3-methoxyphenyl

A-1 10 2-fluoro-4-methylphenyl A-150 2-fluoro-4-methoxyphenyl

A-1 1 1 2-fluoro-5-methylphenyl A-151 2-fluoro-5-methoxyphenyl

A-1 12 3-fluoro-4-methylphenyl A-152 3-fluoro-4-methoxyphenyl row B row B

A-153 3-fluoro-5-methoxyphenyl A-174 2-(trifluoromethoxy)-3-

A-154 2-(trifluoromethyl)-3- chlorophenyl

chlorophenyl A-175 2-(trifluoromethoxy)-4-

A-155 2-(trifluoromethyl)-4- chlorophenyl

chlorophenyl A-176 2-(trifluoromethoxy)-5-

A-156 2-(trifluoromethyl)-5- chlorophenyl

chlorophenyl A-177 2-(trifluoromethoxy)-6-

A-157 2-(trifluoromethyl)-6- chlorophenyl

chlorophenyl A-178 3-(trifluoromethoxy)-4-

A-158 3-(trifluoromethyl)-4- chlorophenyl

chlorophenyl A-179 3-(trifluoromethoxy)-5-

A-159 3-(trifluoromethyl)-5- chlorophenyl

chlorophenyl A-180 2-chloro-3-

A-160 2-chloro-3- (trifluoromethoxy)phenyl

(trifluoromethyl)phenyl A-181 2-chloro-4-

A-161 2-chloro-4- (trifluoromethoxy)phenyl

(trifluoromethyl)phenyl A-182 2-chloro-5-

A-162 2-chloro-5- (trifluoromethoxy)phenyl

(trifluoromethyl)phenyl A-183 3-chloro-4-

A-163 3-chloro-4- (trifluoromethoxy)phenyl

(trifluoromethyl)phenyl A-184 2-(trifluoromethoxy)-3-

A-164 2-(trifluoromethyl)-3- fluorophenyl

fluorophenyl A-185 2-(trifluoromethoxy)-4-

A-165 2-(trifluoromethyl)-4- fluorophenyl

fluorophenyl A-186 2-(trifluoromethoxy)-5-

A-166 2-(trifluoromethyl)-5- fluorophenyl

fluorophenyl A-187 2-(trifluoromethoxy)-6-

A-167 2-(trifluoromethyl)-6- fluorophenyl

fluorophenyl A-188 3-(trifluoromethoxy)-4-

A-168 3-(trifluoromethyl)-4- fluorophenyl

fluorophenyl A-189 3-(trifluoromethoxy)-5-

A-169 3-(trifluoromethyl)-5- fluorophenyl

fluorophenyl A-190 2-fluoro-3-

A-170 2-fluoro-3- (trifluoromethoxy)phenyl

(trifluoromethyl)phenyl A-191 2-fluoro-4-

A-171 2-fluoro-4- (trifluoromethoxy)phenyl

(trifluoromethyl)phenyl A-192 2-fluoro-5-

A-172 2-fluoro-5- (trifluoromethoxy)phenyl

(trifluoromethyl)phenyl A-193 3-fluoro-4-

A-173 3-fluoro-4- (trifluoromethoxy)phenyl

(trifluoromethyl)phenyl A-194 2-(difluoromethoxy)-3- row B row B

chlorophenyl A-215 2-(trifluoromethylthio)-4-

A-195 2-(difluoromethoxy)-4- chlorophenyl

chlorophenyl A-216 2-(trifluoromethylthio)-5-

A-196 2-(difluoromethoxy)-5- chlorophenyl

chlorophenyl A-217 2-(trifluoromethylthio)-6-

A-197 2-(difluoromethoxy)-6- chlorophenyl

chlorophenyl A-218 3-(trifluoromethylthio)-4-

A-198 3-(difluoromethoxy)-4- chlorophenyl

chlorophenyl A-219 3-(trifluoromethylthio)-5-

A-199 3-(difluoromethoxy)-5- chlorophenyl

chlorophenyl A-220 2-chloro-3-

A-200 2-chloro-3- (trifluoromethylthio)phenyl

(difluoromethoxy)phenyl A-221 2-chloro-4-

A-201 2-chloro-4- (trifluoromethylthio)phenyl

(difluoromethoxy)phenyl A-222 2-chloro-5-

A-202 2-chloro-5- (trifluoromethylthio)phenyl

(difluoromethoxy)phenyl A-223 3-chloro-4-

A-203 3-chloro-4- (trifluoromethylthio)phenyl

(difluoromethoxy)phenyl A-224 2-(trifluoromethylthio)-3-

A-204 2-(difluoromethoxy)-3- fluorophenyl

fluorophenyl A-225 2-(trifluoromethylthio)-4-

A-205 2-(difluoromethoxy)-4- fluorophenyl

fluorophenyl A-226 2-(trifluoromethylthio)-5-

A-206 2-(difluoromethoxy)-5- fluorophenyl

fluorophenyl A-227 2-(trifluoromethylthio)-6-

A-207 2-(difluoromethoxy)-6- fluorophenyl

fluorophenyl A-228 3-(trifluoromethylthio)-4-

A-208 3-(difluoromethoxy)-4- fluorophenyl

fluorophenyl A-229 3-(trifluoromethylthio)-5-

A-209 3-(difluoromethoxy)-5- fluorophenyl

fluorophenyl A-230 2-fluoro-3-

A-210 2-fluoro-3- (trifluoromethylthio)phenyl

(difluoromethoxy)phenyl A-231 2-fluoro-4-

A-21 1 2-fluoro-4- (trifluoromethylthio)phenyl

(difluoromethoxy)phenyl A-232 2-fluoro-5-

A-212 2-fluoro-5- (trifluoromethylthio)phenyl

(difluoromethoxy)phenyl A-233 3-fluoro-4-

A-213 3-fluoro-4- (trifluoromethylthio)phenyl

(difluoromethoxy)phenyl A-234 2,3,4-trichlorophenyl

A-214 2-(trifluoromethylthio)-3- A-235 2,3,5-trichlorophenyl chlorophenyl A-236 2,3,6-trichlorophenyl row B row B

A-237 2,4,5-trichlorophenyl A-277 2-trifluoromethoxyphenyl

A-238 2,4,6-trichlorophenyl A-278 3-trifluoromethoxyphenyl

A-239 3,4,5-trichlorophenyl A-279 4-trifluoromethoxyphenyl

A-240 2,3,4-trifluorophenyl A-280 2-difluoromethoxyphenyl

A-241 2,3,5-trifluorophenyl A-281 3-difluoromethoxyphenyl

A-242 2,3,6-trifluorophenyl A-282 4-difluoromethoxyphenyl

A-243 2,4,5-trifluorophenyl A-283 2-trifluoromethylthiophenyl

A-244 2,4,6-trifluorophenyl A-284 3-trifluoromethylthiophenyl

A-245 3,4,5-trifluorophenyl A-285 4-trifluoromethylthiophenyl

A-246 2,3,4-trimethylphenyl A-286 2,3-dichlorophenyl

A-247 2,3,5-trimethylphenyl A-287 2,4-dichlorophenyl

A-248 2,3,6-trimethylphenyl A-288 2,5-dichlorophenyl

A-249 2,4,5-trimethylphenyl A-289 2,6-dichlorophenyl

A-250 2,4,6-trimethylphenyl A-290 3,4-dichlorophenyl

A-251 3,4,5-trimethylphenyl A-291 3,5-dichlorophenyl

A-252 2,3,4-trimethoxyphenyl A-292 2,3-difluorophenyl

A-253 2,3,5-trimethoxyphenyl A-293 2,4-difluorophenyl

A-254 2,3,6-trimethoxyphenyl A-294 2,5-difluorophenyl

A-255 2,4,5-trimethoxyphenyl A-295 2,6-difluorophenyl

A-256 2,4,6-trimethoxyphenyl A-296 3,4-difluorophenyl

A-257 3,4,5-trimethoxyphenyl A-297 3,5-difluorophenyl

A-258 phenyl A-298 2,3-dimethylphenyl

A-259 2-chlorophenyl A-299 2,4-dimethylphenyl

A-260 3-chlorophenyl A-300 2,5-dimethylphenyl

A-261 4-chlorophenyl A-301 2,6-dimethylphenyl

A-262 2-fluorophenyl A-302 3,4-dimethylphenyl

A-263 3-fluorophenyl A-303 3,5-dimethylphenyl

A-264 4-fluorophenyl A-304 2,3-diethylphenyl

A-265 2-methylphenyl A-305 2,4-diethylphenyl

A-266 3-methylphenyl A-306 2,5-diethylphenyl

A-267 4-methylphenyl A-307 2,6-diethylphenyl

A-268 2-ethylphenyl A-308 3,5-diethylphenyl

A-269 3-ethylphenyl A-309 3,4-diethylphenyl

A-270 4-ethylphenyl A-310 2,3-dimethoxyphenyl

A-271 2-methoxyphenyl A-31 1 2,4-dimethoxyphenyl

A-272 3-methoxyphenyl A-312 2,5-dimethoxyphenyl

A-273 4-methoxyphenyl A-313 2,6-dimethoxyphenyl

A-274 2-trifluoromethylphenyl A-314 3,4-dimethoxyphenyl

A-275 3-trifluoromethylphenyl A-315 3,5-dimethoxyphenyl

A-276 4-trifluoromethylphenyl A-316 2,3-di(trifluoromethyl)phenyl row B row B

A-317 2,4-di(trifluoromethyl)phenyl A-351 2-methyl-4-chlorophenyl

A-318 2,5-di(trifluoromethyl)phenyl A-352 2-methyl-5-chlorophenyl

A-319 2,6-di(trifluoromethyl)phenyl A-353 2-methyl-6-chlorophenyl

A-320 3,4-di(trifluoromethyl)phenyl A-354 3-methyl-4-chlorophenyl

A-321 3,5-di(trifluoromethyl)phenyl A-355 3-methyl-5-chlorophenyl

A-322 2,3-di(trifluoromethoxy)phenyl A-356 2-chloro-3-methylphenyl

A-323 2,4-di(trifluoromethoxy)phenyl A-357 2-chloro-4-methylphenyl

A-324 2,5-di(trifluoromethoxy)phenyl A-358 2-chloro-5-methylphenyl

A-325 2,6-di(trifluoromethoxy)phenyl A-359 3-chloro-4-methylphenyl

A-326 3,4-di(trifluoromethoxy)phenyl A-360 2-methyl-3-fluorophenyl

A-327 3,5-di(trifluoromethoxy)phenyl A-361 2-methyl-4-fluorophenyl

A-328 2,3-di(difluoromethoxy)phenyl A-362 2-methyl-5-fluorophenyl

A-329 2,4-di(difluoromethoxy)phenyl A-363 2-methyl-6-fluorophenyl

A-330 2,5-di(difluoromethoxy)phenyl A-364 3-methyl-4-fluorophenyl

A-331 2,6-di(difluoromethoxy)phenyl A-365 3-methyl-5-fluorophenyl

A-332 3,4-di(difluoromethoxy)phenyl A-366 2-fluoro-3-methylphenyl

A-333 3,5-di(difluoromethoxy)phenyl A-367 2-fluoro-4-methylphenyl

A-334 2,3- A-368 2-fluoro-5-methylphenyl di(trifluoromethylthio)phenyl A-369 3-fluoro-4-methylphenyl

A-335 2,4- A-370 2-chloro-3-ethylphenyl di(trifluoromethylthio)phenyl A-371 2-chloro-4-ethylphenyl

A-336 2,5- A-372 2-chloro-5-ethylphenyl di(trifluoromethylthio)phenyl A-373 3-chloro-4-ethylphenyl

A-337 2,6- A-374 2-ethyl-3-chlorophenyl di(trifluoromethylthio)phenyl A-375 2-ethyl-4-chlorophenyl

A-338 3,4- A-376 2-ethyl-5-chlorophenyl di(trifluoromethylthio)phenyl A-377 2-ethyl-6-chlorophenyl

A-339 3,5- A-378 3-ethyl-4-chlorophenyl di(trifluoromethylthio)phenyl A-379 3-ethyl-5-chlorophenyl

A-340 2-fluoro-3-chlorophenyl A-380 2-ethyl-3-fluorophenyl

A-341 2-fluoro-4-chlorophenyl A-381 2-ethyl-4-fluorophenyl

A-342 2-fluoro-5-chlorophenyl A-382 2-ethyl-5-fluorophenyl

A-343 2-fluoro-6-chlorophenyl A-383 2-ethyl-6-fluorophenyl

A-344 3-fluoro-4-chlorophenyl A-384 3-ethyl-4-fluorophenyl

A-345 3-fluoro-5-chlorophenyl A-385 3-ethyl-5-fluorophenyl

A-346 2-chloro-3-fluorophenyl A-386 2-fluoro-3-ethylphenyl

A-347 2-chloro-4-fluorophenyl A-387 2-fluoro-4-ethylphenyl

A-348 2-chloro-5-fluorophenyl A-388 2-fluoro-5-ethylphenyl

A-349 3-chloro-4-fluorophenyl A-389 3-fluoro-4-ethylphenyl

A-350 2-methyl-3-chlorophenyl A-390 2-methoxy-3-chlorophenyl row B row B

A-391 2-methoxy-4-chlorophenyl A-421 2-(trifluoromethyl)-3-

A-392 2-methoxy-5-chlorophenyl fluorophenyl

A-393 2-methoxy-6-chlorophenyl A-422 2-(trifluoromethyl)-4-

A-394 3-methoxy-4-chlorophenyl fluorophenyl

A-395 3-methoxy-5-chlorophenyl A-423 2-(trifluoromethyl)-5-

A-396 2-chloro-3-methoxyphenyl fluorophenyl

A-397 2-chloro-4-methoxyphenyl A-424 2-(trifluoromethyl)-6-

A-398 2-chloro-5-methoxyphenyl fluorophenyl

A-399 3-chloro-4-methoxyphenyl A-425 3-(trifluoromethyl)-4-

A-400 2-methoxy-3-fluorophenyl fluorophenyl

A-401 2-methoxy-4-fluorophenyl A-426 3-(trifluoromethyl)-5-

A-402 2-methoxy-5-fluorophenyl fluorophenyl

A-403 2-methoxy-6-fluorophenyl A-427 2-fluoro-3-

A-404 3-methoxy-4-fluorophenyl (trifluoromethyl)phenyl

A-405 3-methoxy-5-fluorophenyl A-428 2-fluoro-4-

A-406 2-fluoro-3-methoxyphenyl (trifluoromethyl)phenyl

A-407 2-fluoro-4-methoxyphenyl A-429 2-fluoro-5-

A-408 2-fluoro-5-methoxyphenyl (trifluoromethyl)phenyl

A-409 3-fluoro-4-methoxyphenyl A-430 3-fluoro-4- o-5-methoxyphenyl (trifluoromethyl)phenyl

A-410 3-fluor

A-41 1 2-(trifluoromethyl)-3- A-431 2-(trifluoromethoxy)-3- chlorophenyl chlorophenyl

A-412 2-(trifluoromethyl)-4- A-432 2-(trifluoromethoxy)-4- chlorophenyl chlorophenyl

A-413 2-(trifluoromethyl)-5- A-433 2-(trifluoromethoxy)-5- chlorophenyl chlorophenyl

A-414 A-434

2-(trifluoromethyl)-6- 2-(trifluoromethoxy)-6- chlorophenyl chlorophenyl

A-415 3-(trifluoromethyl)-4- A-435 3-(trifluoromethoxy)-4- chlorophenyl chlorophenyl

A-416 3-(trifluoromethyl)-5- A-436 3-(trifluoromethoxy)-5- chlorophenyl chlorophenyl

A-417 2-chloro-3- A-437 2-chloro-3-

(trifluoromethyl)phenyl (trifluoromethoxy)phenyl

A-418 2-chloro-4- A-438 2-chloro-4-

(trifluoromethyl)phenyl (trifluoromethoxy)phenyl

A-419 2-chloro-5- A-439 2-chloro-5-

(trifluoromethyl)phenyl (trifluoromethoxy)phenyl

A-420 3-chloro-4- A-440 3-chloro-4-

(trifluoromethyl)phenyl (trifluoromethoxy)phenyl

A-441 2-(trifluoromethoxy)-3- row B row B

fluorophenyl A-462 2-(difluoromethoxy)-4-

A-442 2-(trifluoromethoxy)-4- fluorophenyl

fluorophenyl A-463 2-(difluoromethoxy)-5-

A-443 2-(trifluoromethoxy)-5- fluorophenyl

fluorophenyl A-464 2-(difluoromethoxy)-6-

A-444 2-(trifluoromethoxy)-6- fluorophenyl

fluorophenyl A-465 3-(difluoromethoxy)-4-

A-445 3-(trifluoromethoxy)-4- fluorophenyl

fluorophenyl A-466 3-(difluoromethoxy)-5-

A-446 3-(trifluoromethoxy)-5- fluorophenyl

fluorophenyl A-467 2-fluoro-3-

A-447 2-fluoro-3- (difluoromethoxy)phenyl

(trifluoromethoxy)phenyl A-468 2-fluoro-4-

A-448 2-fluoro-4- (difluoromethoxy)phenyl

(trifluoromethoxy)phenyl A-469 2-fluoro-5-

A-449 2-fluoro-5- (difluoromethoxy)phenyl

(trifluoromethoxy)phenyl A-470 3-fluoro-4-

A-450 3-fluoro-4- (difluoromethoxy)phenyl

(trifluoromethoxy)phenyl A-471 2-(trifluoromethylthio)-3-

A-451 2-(difluoromethoxy)-3- chlorophenyl

chlorophenyl A-472 2-(trifluoromethylthio)-4-

A-452 2-(difluoromethoxy)-4- chlorophenyl

chlorophenyl A-473 2-(trifluoromethylthio)-5-

A-453 2-(difluoromethoxy)-5- chlorophenyl

chlorophenyl A-474 2-(trifluoromethylthio)-6-

A-454 2-(difluoromethoxy)-6- chlorophenyl

chlorophenyl A-475 3-(trifluoromethylthio)-4-

A-455 3-(difluoromethoxy)-4- chlorophenyl

chlorophenyl A-476 3-(trifluoromethylthio)-5-

A-456 3-(difluoromethoxy)-5- chlorophenyl

chlorophenyl A-477 2-chloro-3-

A-457 2-chloro-3- (trifluoromethylthio)phenyl

(difluoromethoxy)phenyl A-478 2-chloro-4-

A-458 2-chloro-4- (trifluoromethylthio)phenyl

(difluoromethoxy)phenyl A-479 2-chloro-5-

A-459 2-chloro-5- (trifluoromethylthio)phenyl

(difluoromethoxy)phenyl A-480 3-chloro-4-

A-460 3-chloro-4- (trifluoromethylthio)phenyl

(difluoromethoxy)phenyl A-481 2-(trifluoromethylthio)-3-

A-461 2-(difluoromethoxy)-3- fluorophenyl

fluorophenyl A-482 2-(trifluoromethylthio)-4- row B row B

fluorophenyl A-495 2,4,6-trichlorophenyl

A-483 2-(trifluoromethylthio)-5- A-496 3,4,5-trichlorophenyl

fluorophenyl A-497 2,3,4-trifluorophenyl

A-484 2-(trifluoromethylthio)-6- A-498 2,3,5-trifluorophenyl

fluorophenyl A-499 2,3,6-trifluorophenyl

A-485 3-(trifluoromethylthio)-4- A-500 2,4,5-trifluorophenyl

fluorophenyl A-501 2,4,6-trifluorophenyl

A-486 3-(trifluoromethylthio)-5- A-502 3,4,5-trifluorophenyl

fluorophenyl A-503 2,3,4-trimethylphenyl

A-487 2-fluoro-3- A-504 2,3,5-trimethylphenyl

(trifluoromethylthio)phenyl A-505 2,3,6-trimethylphenyl

A-488 2-fluoro-4- A-506 2,4,5-trimethylphenyl

(trifluoromethylthio)phenyl A-507 2,4,6-trimethylphenyl

A-489 2-fluoro-5- A-508 3,4,5-trimethylphenyl

(trifluoromethylthio)phenyl A-509 2,3,4-trimethoxyphenyl

A-490 3-fluoro-4- A-510 2,3,5-trimethoxyphenyl

(trifluoromethylthio)phenyl A-51 1 2,3,6-trimethoxyphenyl

A-491 2,3,4-trichlorophenyl A-512 2,4,5-trimethoxyphenyl

A-492 2,3,5-trichlorophenyl A-513 2,4,6-trimethoxyphenyl

A-493 2,3,6-trichlorophenyl A-514 3,4,5-trimethoxyphenyl

A-494 2,4,5-trichlorophenyl

Experimental Procedures

The following examples further illustrate the present invention and do not restrict the invention in any manner.

Synthesis of (2RS, 3SR)-4-amino-1-[3-(2-chloro^henyl)-2-(2,4-difluoro-phenyl)- oxiranylmethyl]-4H-[1,2,4]triazol-1-ium methanesulfonate

A mixture of methanesulfonic acid 3-(2-chloro-phenyl)-2-(2,4-difluoro-phenyl)- oxiranylmethyl ester (50.0 g, 133 mol) and 4-amino-1 ,2,4-triazole (1 1.1 g, 132 mmol) in 130 mL of n-butanol was heated to reflux for 48 h. Then, all volatiles were removed under reduced pressure and the residue was taken up in 100 mL of water and 100 mL of toluene. The organic phase was extracted with water. The combined aqueous phases were extracted with toluene twice (both 50 mL). The aqueous phase was then concentrated under reduced pressure und the residue further dried by freeze drying. The product was obtained as a colorless solid (48.9 g, 86% purity by NMR, 91.2 mmol, 69% yield) containing about 10% of 4-aminotriazole.

H NMR (DMSO-d₆, 500 MHz): δ (ppm) = 10.12 (s, 1 H); 9.12 (s, 1 H); 7.58-7.62 (m, 2 H); 7.49-7.52 (m, 2 H); 7.36-7.41 (m, 2 H); 7.10-7.14 (m, 1 H); 6.99-7.02 (bs, 2 H); 4.91 (d, J = 15.0 Hz, 1 H); 4.54 (s, 1 H); 4.21 (d, J = 15.0 Hz, 1 H); 2.32 (s, 3 H). ³C NMR (DMSO-cfe 500 MHz): δ (ppm) = 162.6 (dd, J = 247 Hz, J = 12.0 Hz); 160.1 (dd, J = 248 Hz, J = 12.6 Hz); 145.2; 143.5; 132.4; 130.8; 130.5; 130.0 (dd, J =

10.3 Hz, J = 5.0 Hz); 129.4; 128.2; 127.6; 1 19.3 (dd, J = 14.4 Hz, J = 3.6 Hz); 1 12.0 (dd, J = 21 .5 Hz, J = 3.3 Hz); 104.4 (t, J = 25.5 Hz); 62.6; 61 .2; 53.4 (d, J = 2.3 Hz). Melting point: 162 °C

Synthesis of (2RS, 3SR)-4-amino-2-[3-(2-chloro-phenyl)-2-(2,4-difluoro-phenyl)- oxiranylmethyl]-2,4-dihydro-[1,2,4]triazole-3-thione from the azolium salt in pyridine with triethylamine (Comparative example)

A mixture of (2 RS, 3SR)-4-amino-1 -[3-(2-chloro-phenyl)-2-(2,4-difluoro-phenyl)- oxiranylmethyl]-4H-[1 ,2,4]triazol-1 -ium methanesulfonate (2.0 g, 4.3 mmol), sulfur (166 mg, 5.2 mmol) and triethylamine (314 mg, 3.1 mol) was stirred in 4.3 ml. of dry pyridine at 90 °C for 4 h whereupon all solid material had gone into solution. To this mixture was added 12 ml. aqueous hydrocholoric acid (10%) and 20 ml. of tert-butyl methyl ether. The aqueous phase was re-extracted with 10 mL of tert-butyl methyl ether and the combined organic phases were successively washed with 10% Hydrocholoric acid, water and saturated NaCI solution (all 10 mL) and dried over Na2S0₄. The crude product was obtained after evaporation of all volatiles. Flash column chromatography (silica, cyclohexanes/ethyl acetate mixtures) gave the product as a tan solid (1.2 g, >95% purity by HPLC, 3.1 mmol, 72% yield).

H NMR (CDCIs, 500 MHz): δ (ppm) = 7.84 (s, 1 H); 7.64 (d, J = 7.0 Hz, 1 H); 7.45 (d, J = 7.0 Hz, 1 H); 7.32-7.41 (m, 3 H); 6.78-6.85 (m, 2 H); 4.82 (bs, 1 H); 4.78 (d, J = 14.5 Hz, 1 H); 4.25 (s, 1 H); 4.05 (d, J = 14.5 Hz, 1 H).

3C NMR (CDCIs, 125 MHz): δ (ppm) = 167.8; 163.1 (dd, J = 248 Hz, J = 1 1.9 Hz); 160.9 (dd, J = 248 Hz, J = 9.8 Hz); 140.1 ; 133.5; 131 .7; 129.8 (dd, J = 9.8 Hz, J =

5.4 Hz); 129.7; 129.4; 128.3; 126.9; 120.8 (dd, J = 14.6 Hz, J = 3.8 Hz); 1 1 1 .2 (dd, J = 21 .1 Hz, J = 3.5 Hz); 104.0 (t, J = 25 Hz); 62.4; 62.3; 50.5 (d, J = 2.5 Hz).

Melting point: 167 °C Synthesis of (2RS, 3SR)-4-amino-2-[3-(2-chloro-phenyl)-2-(2,4-difluoro-phenyl)- oxiranylmethyl]-2,4-dihydro-[1,2,4]triazole-3-thione from the azolium salt in n-butanol with sodium bicarbonate

To a suspension of (2RS, 3SR)-4-amino-1 -[3-(2-chloro-phenyl)-2-(2,4-difluoro-phenyl)- oxiranylmethyl]-4/-/-[1 ,2,4]triazol-1 -ium methanesulfonate (20 mmol, 1 :10 mixture of cis/trans isomers) and sulfur (640 mg, 20 mmol) in a mixture of 10 g of n-butanol and 10 g of water at 60 °C was added a solution of sodium bicarbonate in water (8.6% in water, 21.5 g, 22 mmol). The suspension was stirred at 60 °C for 90 min and then cooled to 0 °C. The precipitate was filtered off and washed with n-butanol and water. Drying at 50 °C at 20 mbar yielded the product as a tan solid (6.2 g, 91 wt.-% of the trans isomer by HPLC, 14.2 mmol, 79% yield). Synthesis of (2RS, 3SR)-4-amino-2-[3-(2-chloro-phenyl)-2-(2,4-difluoro-phenyl)- oxiranylmethyl]-2,4-dihydro-[1,2,4]triazole-3-thione from the azolium salt in n-butanol with sodium carbonate

To a suspension of (2RS, 3SR)-4-amino-1 -[3-(2-chloro-phenyl)-2-(2,4-difluoro-phenyl)- oxiranylmethyl]-4H-[1 ,2,4]triazol- i-/um methanesulfonate (20 mmol, 1 :10 mixture of cis/trans isomers) and sulfur (640 mg, 20 mmol) in a mixture of 20 g of n-butanol and 30 g of water at 60 °C was added a solution of sodium carbonate in water (17.9% in water, 13.0 g, 22 mmol). The suspension was stirred at 60 °C for 90 min and then cooled to 0 °C. The precipitate was filtered off and washed with n-butanol and water. Drying at 50 °C at 20 mbar yielded the product as a tan solid (6.0 g, 92% wt.-% of the trans isomer by HPLC, 13.9 mmol, 78% yield).

Synthesis of (2RS, 3SR)-4-amino-2-[3-(2-chloro-phenyl)-2-(2,4-difluoro-phenyl)- oxiranylmethyl]-2,4-dihydro-[1,2,4]triazole-3-thione from the azolium salt in n-butanol with potassium bicarbonate

To a suspension of (2RS, 3SR)-4-amino-1 -[3-(2-chloro-phenyl)-2-(2,4-difluoro-phenyl)- oxiranylmethyl]-4/-/-[1 ,2,4]triazol-1 -ium methanesulfonate (20 mmol, 1 :10 mixture of cis/trans isomers) and sulfur (640 mg, 20 mmol) in a mixture of 10 g of n-butanol and 30 g of water at 60 °C was added a solution of potassium bicarbonate in water (25.0% in water, 8.9 g, 22 mmol). The suspension was stirred at 60 °C for 90 min and then cooled to 0 °C. The precipitate was filtered off and washed with n-butanol and water. Drying at 50 °C at 20 mbar yielded the product as a tan solid (6.5 g, 91 % wt.-% of the trans isomer by HPLC, 14.9 mmol, 83% yield).

Synthesis of (2RS, 3SR)-4-amino-2-[3-(2-chloro-phenyl)-2-(2,4-difluoro-phenyl)- oxiranylmethyl]-2,4-dihydro-[1,2,4]triazole-3-thione from the azolium salt in n-butanol with potassium carbonate

To a suspension of (2RS, 3SR)-4-amino-1 -[3-(2-chloro-phenyl)-2-(2,4-difluoro-phenyl)- oxiranylmethyl]-4/-/-[1 ,2,4]triazol-1 -ium methanesulfonate (20 mmol, 1 :10 mixture of cis/trans isomers) and sulfur (640 mg, 20 mmol) in a mixture of 10 g of n-butanoland 10 g of water at 60 °C was added a solution of potassium carbonate in water (50.0% in water, 6.1 g, 22 mmol). The suspension was stirred at 60 °C for 90 min and then cooled to 0 °C. The precipitate was filtered-off and washed with n-butanol and water. Drying at 50 °C at 20 mbar yielded the product as a tan solid (6.1 g, 92% wt.-% of the trans isomer by HPLC, 14.2 mmol, 79% yield).

Synthesis of (2RS, 3SR)-4-amino-2-[3-(2-chloro-phenyl)-2-(2,4-difluoro-phenyl)- oxiranylmethyl]-2,4-dihydro-[1,2,4]triazole-3-thione from the azolium salt in n-butanol with triethylamine

To a suspension of (2RS, 3SR)-4-amino-1 -[3-(2-chloro-phenyl)-2-(2,4-difluoro-phenyl)- oxiranylmethyl]-4/-/-[1 ,2,4]triazol-1 -ium methanesulfonate (20 mmol, 1 :10 mixture of cis/trans isomers) and sulfur (640 mg, 20 mmol) in a mixture of 10 g of n-butanoland 20 g of water at 60 °C was added triethylamine (2.2 g, 22 mmol). The suspension was stirred at 60 °C for 90 min and then cooled to 0 °C. The precipitate was filtered-off and washed with n-butanol and water. Drying at 50 °C at 20 mbar yielded the product as a tan solid (6.3 g, 91 % wt.-% of the trans isomer by HPLC, 14.4 mmol, 81 % yield).

Synthesis of (2RS, 3SR)-4-amino-2-[3-(2-chloro-phenyl)-2-(2,4-difluoro-phenyl)- oxiranylmethyl]-2,4-dihydro-[1,2,4]triazole-3-thione from the azolium salt in n-butanol with N, N-dimethylcyclohexylamine

To a suspension of (2RS, 3SR)-4-amino-1 -[3-(2-chloro-phenyl)-2-(2,4-difluoro-phenyl)- oxiranylmethyl]-4/-/-[1 ,2,4]triazol-1 -ium methanesulfonate (20 mmol, 1 :10 mixture of cis/trans isomers) and sulfur (640 mg, 20 mmol) in a mixture of 10 g of n-butanol and 10 g of water at 60 °C was added N, N-dimethylcyclohexylamine (2.8 g, 22 mmol). The suspension was stirred at 60 °C for 90 min and then cooled to 0 °C. The precipitate was filtered-off and washed with n-butanol and water. Drying at 50 °C at 20 mbar yield- ed the product as a tan solid (6.2 g, 94% wt.-% of the trans isomer by HPLC,

14.7 mmol, 81 % yield).

One-pot, two-step synthesis of (2RS, 3SR)-4-amino-2-[3-(2-chloro-phenyl)-2-(2,4- difluoro-phenyl)-oxiranylmethyl]-2,4-dihydro-[1,2,4]triazole-3-thione from 4-amino-1 ,2,4- triazole in iso-butanol

A mixture of methanesulfonic acid 3-(2-chloro-phenyl)-2-(2,4-difluoro-phenyl)- oxiranylmethyl ester (50.0 g, 98.0% purity, 131 mmol) and 4-amino-1 ,2,4-triazole (12.5 g, 149 mmol) in 80 g of iso-butanol was heated to reflux (108 °C) for 20 h. The solution was cooled to 60 °C and 100 ml. of water and sulfur (4.2 g, 131 mmol) were added. Then, triethylamine (18.2 g, 180 mmol) was added over the course of 10 min. Upon completion of the addition of triethylamine the reaction was stirred at 60 °C for further 30 min and then slowly cooled to 0 °C. The precipitate thus formed was filtered off and washed with water and toluene. The solid was dried at p<25 mbar and 60 °C overnight. The product was obtained as a tan solid (45.4 g, 1 15 mmol, 86% yield).

One-pot, two-step synthesis of (2RS, 3SR)-4-amino-2-[3-(2-chloro-phenyl)-2-(2,4- difluoro-phenyl)-oxiranylmethyl]-2,4-dihydro-[1,2,4]triazole-3-thione in n-butanol A mixture of methanesulfonic acid 3-(2-chloro-phenyl)-2-(2,4-difluoro-phenyl)- oxiranylmethyl ester (50.0 g, 98.0% purity, 131 mmol) and 4-amino-1 ,2,4-triazole (12.2 g, 145 mmol) in 120 g of n-butanol was heated to reflux (1 18 °C) for 20 h. The solution was cooled to 60 °C and 100 ml. of water and sulfur (4.6 g, 144 mmol) were added. Then, triethylamine (19.7 g, 195 mmol) was added over the course of 10 min. Upon completion of the addition of triethylamine the reaction was stirred at 60 °C for further 30 min and then slowly cooled to 0 °C. The precipitate thus formed was filtered off and washed with water and toluene. The solid was dried at p<25 mbar and 60 °C overnight. The product was obtained as a tan solid (45.1 g, 98% wt.-% of the trans isomer by HPLC, 105 mmol, 80% yield). One-pot, two-step synthesis of (2RS, 3SR)-4-amino-2-[3-(2-chloro-phenyl)-2-(2,4- difluoro-phenyl)-oxiranylmethyl]-2,4-dihydro-[1,2,4]triazole-3-thione using crude 4- amino-1 ,2,4-triazole in n-butanol

A mixture of methanesulfonic acid 3-(2-chloro-phenyl)-2-(2,4-difluoro-phenyl)- oxiranylmethyl ester (50.0 g, 98.0% purity, 131 mmol) and 4-amino-1 ,2,4-triazole (13.4 g, 90% purity, 143 mmol) in 120 g of iso-butanol was heated to reflux (108 °C) for 20 h. The solution was cooled to 60 °C and 100 mL of water and sulfur (4.6 g,

144 mmol) were added. Then, triethylamine (19.7 g, 195 mmol) was added over the course of 10 min. Upon completion of the addition of triethylamine the reaction was stirred at 60 °C for further 30 min and then slowly cooled to 0 °C. The precipitate thus formed was filtered off and washed with water and toluene. The solid was dried at p<25 mbar and 60 °C overnight. The product was obtained as a tan solid (45.5 g, 98% wt.-% of the trans isomer by HPLC, 1 13 mmol, 86% yield).

Syn th esis of bis-{1 -[3-(2-chloro-phenyl)-2-(2,4-difluoro-phenyl)-oxiranylmethyl]- 1 H- [1,2,4]triazole-5-yl}-disulfide

To a suspension of (2RS, 3SR)-4-amino-2-[3-(2-chloro-phenyl)-2-(2,4-difluoro-phenyl)- oxiranylmethyl]-2,4-dihydro-[1 ,2,4]triazole-3-thione (10.0 g, 25.3 mmol) in a mixture of 40 mL n-butanol and 40 mL of n-butyl acetate was added n-butylnitrite (5.0 g, 48.5 mmol). The mixture was stirred overnight (16 h) at room temperature. Then, the formed precipitate was filtered off and the washed with cold n-butanol and dried under reduced pressure (p<20 mbar) at 50 °C overnight. The product was obtained as a 1 :1 mixture of diastereomers in the form of a colorless solid (9.0 g, 1 1.9 mmol, 94% yield)

1 H NMR (CDCI3, 500 MHz): δ (ppm) = 7.67 (s, 2 H); 7.56-7.60 (m, 2 H); 7.42-7.48 (m, 2 H); 7.31 -7.38 (m, 4 H); 7.18 (t, J = 10.5 Hz, 1 H); 7.16 (t, J = 10.5 Hz, 1 H); 6.75-6.86 (m, 4 H); 4.79 (d, J = 18.5 Hz, 2 H); 4.25 (s, 2 H); 4.04-4.14 (m, 2 H).

Melting point: 140 °C Synthesis of (2RS, 3SR)-2-[3-(2-chloro-phenyl)-2-(2,4-difluoro-phenyl)-oxiranylmethyl]- 2,4-dihydro-[1,2,4]triazole-3-thione from the disulfide with sodium dithionite in ethyl acetate /water

A s o l ut i o n of b i s-{1 -[3-(2-chloro-phenyl)-2-(2,4-difluoro-phenyl)-oxiranylmethyl]-1 H- [1 ,2,4]triazole-5-yl}-disulfide (5.0 g, 6.6 mmol) in 50 mL of ethyl acetate was treated with a solution of sodium dithionite (10% solution in water, 20 mL) at room temperature. Stirring was continued for 60 min, then the phases were separated and the organic phase dried with sodium sulfate. Evaporation of all volatiles under reduced pressure gave the desired compound as a colorless solid (4.8 g, 12.6 mmol, 95% yield).

1 H NMR (DMSO-d6, 500 MHz): δ (ppm) = 13.31 (bs, 1 H); 8.23 (s, 1 H); 7.56-7.60 (m, 2 H); 7.44-7.49 (m, 2 H); 7.35 (q, J = 8.0 Hz, 1 H); 7.26 (dt, J = 2.5 Hz, J = 9.5 Hz, 1 H); 7.01 -7.06 (m, 1 H); 4.47 (d, J = 14.5 Hz, 1 H); 4.39 (s, 1 H); 4.13 (d, J = 14.5 Hz, 1 H). 13C NMR (DMSO-d6, 125 MHz): δ (ppm) = 166.0; 162.4 (dd, J = 12.1 Hz, J = 246 Hz); 160.6 (dd, J = 13.0 Hz, J = 249 Hz); 139.2; 132.7; 131 .5; 130.1 (dd, J = 7.8 Hz, J = 15.8 Hz); 130.0; 129.3; 128.0; 127.1 ; 120.9 (dd, J = 5.4 Hz, J = 13.3 Hz); 1 1 1.1 (dd, J = 6.0 Hz, J = 19.1 Hz); 103.9 (t, J = 25.4 Hz); 62.1 ; 61.2; 47.5.

Melting point: 180 °C

Synthesis of (2RS, 3SR)-2-[3-(2-chloro-phenyl)-2-(2,4-difluoro-phenyl)-oxiranylmethyl]- 2,4-dihydro-[1,2,4]triazole-3-thione from the disulfide with sodium borohydride and acetic acid in iso-butanol/tetrahydrofuran

A s l u r r y o f b i s-{1 -[3-(2-chloro-phenyl)-2-(2,4-difluoro-phenyl)-oxiranylmethyl]-1 H- [1 ,2,4]triazole-5-yl}-disulfide (7.6 g, 10.0 mmol) and acetic acid (2.4 g, 40.0 mmol) in 50 mL of ethanol was treated portionwise with sodium borohydride (0.4 g, 10.6 mmol). Upon complete addition the mixture was stirred for another 2 h at room temperature. Then, 50 mL of a saturated sodium bicarbonate solution in water were added, followed by 50 mL of ethyl acetate. The phases were separated and the aqueous phase was extracted with 50 mL of ethyl acetate. The combined organic phases were successively washed with water and saturated aqueous sodium chloride solution. The crude material was obtained after evaporation of all volatiles. The residue was recrystallized from o- xylene (20 mL) to give the product as a colorless solid (3.1 g, 8.2 mmol, 41 % yield).

One-pot synthesis of bis-{ 1 -[3-(2-chloro-phenyl)-2-(2,4-difluoro-phenyl)-oxiranylmethyl]- 1 H-[1 ,2,4]triazole-5-yl}-disulfide from the aminotriazolethione

(2RS, 3SR)-4-amino-2-[3-(2-chloro-phenyl)-2-(2,4-difluoro-phenyl)-oxiranylmethyl]-2,4- dihydro-[1 ,2,4]triazole-3-thione (25.0 g, 63.3 mmol) was dissolved in 75 g of tetrahydro- furan at 30 °C. To the clear solution was added 75 g of iso-butanol, followed by the dropwise addition of iso-butylnitrite (7.2 g, 66.5 mmol). Upon complete addition, the solution was kept at 30 °C for 3 h. Then sodium dithionite (10% solution in water, 1 10 g) was added and the biphasic mixture was stirred for 10 min. The phases were separated and the organic phase was successively washed with water and saturated aque- ous sodium chloride solution (both 50 g). Then, 75 g of iso-butanol were added and the solution was stepwise warmed to 80 °C with concomitant lowering of the pressure to 300 mbar. The solution was concentrated to an end volume of 120 mL and then cooled to 0 °C. The precipitated solid was filtered off, washed with cold iso-butanol and dried at 60 °C and p<20 mbar overnight. The product was obtained as a colorless solid (19.7 g, 92% wt.-% by HPLC, 76% yield).

One-pot synthesis of (2RS, 3SR)-2-[3-(2-chloro-phenyl)-2-(2,4-difluoro-phenyl)- oxiranylmethyl]-2,4-dihydro-[1,2,4]triazole-3-thione from methanesulfonic acid

(2RS, 3SR)-3-(2-chloro-phenyl)-2-(2,4-difluoro-phenyl)-oxiranylmethyl ester without iso la tion of any in termed ia tes

A mixture of methanesulfonic acid (2RS, 3SR)-3-(2-chloro-phenyl)-2-(2,4-difluoro- phenyl)-oxiranylmethyl ester (24.3 g, 64.8 mol) and 4-amino-1 ,2,4-triazole (6.0 g, 71 .4 mmol) in 10.7 g of n-butanol was heated to reflux for 5.5 h. Then, additional n- butanol (39 g) was added and the solution was cooled to 60 °C. Tetrahydrofuran (70 g) and powdered sulfur (2.1 g, 65.5 mmol) were added, followed by the slow addition of an aqueous solution of potassium carbonate (25% in water, 39.4 g, 71.3 mmol). The biphasic mixture was stirred at 60 °C for 1 h and then cooled to room temperature. The phases were separated and the organic layer washed with saturated sodium chloride solution (40 g). The mixture was then warmed to 30 °C and n-butyl nitrite (8.5 g, 74.4 mmol) was added over 10 min and stirring at 30 °C was continued for 3 h and then cooled to room temperature. An aqueous solution of sodium dithionite (4% in wa- ter, 35.2 g, 8.1 mmol) was added and stirring continued for 15 min. The organic phase was then washed with water twice (both 50 g). Then, 50 g of o-xylene were added and the solution warmed to 60 °C. The pressure was stepwise reduced to 200 mbar. Then, another 100 g of o-xylene were added and distillation continued to a pressure of 40 mbar. The suspension was then cooled to 0 °C, filtered and washed with o-xylene (50 g). The solid was dried overnight at 60 °C under reduced pressure to give the product as a colorless solid (19.2 g, 96% purity by HPLC, 48.3 mmol, 75% yield).

Claims

Claims

A process for the preparation of 2-substituted 4-amino-2,4-dihydro-[1 ,2,4]triazole- 3-thiones of the formula (I)

wherein

R is a group (1 )

wherein # shall mean the point of attachment to the triazolo group, and A and B are defined as follows:

A or B is a three-, four-, five-, six-, seven-, eight-, nine- or ten-membered saturated or partially unsaturated heterocycle or five-, six-, seven-, eight-, nine- or ten-membered aromatic heterocycle, where the heterocycle contains in each case one, two, three or four heteroatoms from the group consisting of O, N and S; is naphthyl or phenyl; and the respective other variable B or A has one of the meanings mentioned above for A or B or is Ci-Cs-alkyl, Ci-Cs-haloalkyl, C2-C8-alkenyl, C2-C8- haloalkenyl, C2-Cs-alkynyl, C2-C8-haloalkynyl, Cs-Cs-cycloalkyl, C3-C8- halocycloalkyl, or benzodioxolyl; where A and/or B independently of one another are unsubstituted or substituted by one, two, three or four independently selected substituents L; wherein

L is halogen, cyano, nitro, cyanato (OCN), Ci-Cs-alkyl, Ci-Cs-haloalkyl, phenyl-Ci-C6-alkyloxy, C2-Cs-alkenyl, C2-C8-haloalkenyl, C2-Cs-alkynyl,

C2-C8-haloalkynyl, C4-Cio-alkadienyl, C4-Cio-haloalkadienyl, Ci-Cs-alk- oxy, Ci-Cs-haloalkoxy, Ci-Cs-alkylcarbonyloxy, Ci-Cs-alkylsulfonyloxy, C2-C8-al kenyloxy, C2-C8-haloalkenyloxy, C2-C8-alkynyloxy, C2-C8- haloalkynyloxy, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, C3-C8- cycloalkenyl, Cs-Cs-halocycloalkenyl, Cs-Cs-cycloalkoxy, C3-C6-cyclo- alkenyloxy, hydroxyimino-Ci-Cs-alkyl, Ci-C6-alkylene, oxy-C2-C₄- alkylene, oxy-Ci-C3-alkyleneoxy, Ci-Cs-alkoximino-Ci-Cs-alkyl, C2-C8- alkenyloximino-Ci-C8-a I k y I , C2-C8-alkynyloximino-Ci-C8-alkyl, S(=0)nA¹ , C(= 0)A², C(=S)A², NAW, phenyl-Ci-Ce-alkyl , phenyl, phenyloxy or a five- or six-membered saturated, partially unsaturated or aromatic heterocycle which contains one, two, three or four heteroatoms from the group consisting of O, N and S; where n, A¹ , A², A⁵, A⁶ are: is 0, 1 or 2; is hydrogen, hydroxyl, Ci-Cs-alkyl, Ci-Cs-haloalkyl, amino, Ci-Cs alkylamino or di-Ci-Cs-alkylamino,

A² is one of the groups mentioned for A¹ or C2-Cs-alkenyl, C2-C8- haloalkenyl, C2-Cs-alkynyl, C2-C8-haloalkynyl, Ci-Cs-alkoxy, Ci-

Cs-haloalkoxy, C2-C8-alkenyloxy, C2-C8-haloalkenyloxy, C2-C8- alkynyloxy, C2-C8-haloalkynyloxy, Cs-Cs-cycloalkyl, C3-C8- halocycloalkyl, C3-Cs-cycloalkoxy or Cs-Cs-halocycloalkoxy;

A⁵, A⁶ independently of one another are hydrogen, Ci-Cs-alkyl, Ci-Cs-haloalkyl, C2-Cs-alkenyl, C2-C8-haloalkenyl, C2-Cs-alkynyl, C2-C8-haloalkynyl, Cs-Cs-cycloalkyl, C3-Cs-halocycloalkyl, C3-C8- cycloalkenyl or C3-Cs-halocycloalkenyl; where the aliphatic and/or alicyclic and/or aromatic groups of the radical definitions of L for their part may carry one, two, three or four identical or different groups R^L: is halogen, cyano, nitro, Ci-Cs-alkyl, Ci-Cs-haloalkyl, Ci-Cs- alkoxy, Ci-Cs-haloalkoxy, Cs-Cs-cycloalkyl, C3-Cs-halocycloalkyl, C3-Cs-cycloalkenyl, C3-Cs-cycloalkoxy, Cs-Cs-halocycloalkoxy, Ci- Cs-alkylcarbonyl, Ci-Cs-alkylcarbonyloxy, Ci-Cs-alkoxycarbonyl, amino, Ci-Cs-alkylamino, di-Ci-Cs-alkylamino; or is a group (2)

wherein

# shall mean the point of attachment to the triazolo group and R¹¹ and R²² have the following meanings: R¹¹, R²² independently of one another Ci-C6-alkyl, Ci-C6-haloalkyl, C3-C6- cycloalkyl, C3-C6-halocycloalkyl or phenyl, wherein the alkyl, cy- cloalkyl and phenyl moieties may be unsubstituted or substituted by one, two, three or four substituents L;

R¹¹ and R²², together with the carbon atom to which they are attached, form a five- or six-membered saturated or partially unsaturated ring, that can be unsubstituted or substituted by one, two, three, four or five substituents L', wherein L' stands for L as defined above or stands for a group

_R33

F

R⁴⁴

wherein R³³ and R⁴⁴ independently are selected from the group of hydrogen and the meaning for L as defined above; or is a group (3)

wherein

# shall mean the point of attachment to the triazolo group and R⁵⁵, R⁶⁶ and R⁷⁷ have the following meanings:

R⁵⁵ phenyl-Ci-Ce-alkyl, phenyl or a five- or six-membered saturated, partially unsaturated or aromatic heterocycle which contains one, two, three or four heteroatoms from the group consisting of O, N and S; where the aliphatic and/or aromatic and/or heterocyclic groups for their part may carry one, two, three or four identical or different groups selected from halogen, cyano, nitro, Ci-Cs-alkyl, Ci-Cs-haloalkyl, d-Cs-alkoxy, d-Cs-haloalkoxy, Cs-Cs-cycloalkyl, C3-C8-halocycloalkyl, Cs-Cs-cycloalkenyl, Cs-Cs-cycloalkoxy, C3-C8- halocycloalkoxy, d-Cs-alkylcarbonyl, d-Cs-alkylcarbonyloxy, d-

Cs-alkoxycarbonyl, amino, d-Cs-alkylamino, di-d-Cs-alkylamino, phenyl, halophenyl, phenyloxy, halophenyloxy;

R⁶⁶, R⁷⁷ independently of one another are hydrogen, Ci-C6-alkyl, d-dr haloalkyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl or phenyl, wherein the alkyl, cycloalkyl or phenyl moieties may be unsubstituted or substituted by one, two or three substituents selected from halogen, cyano, nitro, Ci-Cs-alkyl, Ci-Cs-haloalkyl, Ci-Cs-alkoxy, Ci-Cs-haloalkoxy; by reacting a compound of the formula (II)

wherein the variables are defined as follows: R is as defined above, and

X^" is halide, arylsulfonate, alkylsulfonate, haloalkylsulfonate or X⁰¹OSO3, in which X⁰¹ is Ci-Cs-alkyl, Ci-Cs-haloalkyl or Cs-Cs-cycloalkyl where above mentioned alkyl, haloalkyl or aryl groups are unsubstituted or substituted by one, two, three or four independently selected inert

with sulfur in a solvent in the presence of a base characterized in that as solvent water or a protic, organic solvent is used or a mixture of such solvents.

The process according to claim 1 , wherein the solvent is water or Ci-Cs-alkanols or mixtures thereof.

The process according to claim 1 or 2, wherein the solvent is water, n-butanol, iso-butanol or mixtures thereof.

The process according to any one of claims 1 to 3, wherein the base is alkali metal and alkaline earth metal hydroxides, alkali metal and alkaline earth metal phosphates, alkali metal and alkaline earth metal carbonates, alkali metal bicar- bonates, primary amines, secondary amines, tertiary amines, ammonia or mixtures thereof.

The process according to any one of claims 1 to 4, wherein the base is an alkali metal and alkaline earth metal carbonate or an alkali metal bicarbonate.

6. The process according to any one of claims 1 to 5, wherein the reaction is carried out at a temperature from 40 to 80°C.

The process according to any one of claims 1 to 6, wherein R is a group (1 ) defined in claim 1.

8. The process according to any one of claims 1 to 6, wherein R is a group (2) as defined in claim 1 . 9. The process according to any one of claims 1 to 6, wherein R is a group (3) as defined in claim 1.

10. The process according to any one of claims 1 to 9, wherein the compound of the formula (II) is prepared via alkylation of a 4-amino-1 ,2,4-triazole, which is, in situ, converted to compounds of formula (I).

1 1 . Compounds of the formula (I), in which R is a group (1 ) as defined in claim 1.

12. Compounds of the formula (I), in which R is a group (2) or (3) as defined in

claim 1 .

13. Compounds of the formula (II), in which R is a group (2) or (3) as defined in claim 1 .