Herbicidal active thiadiazol compounds

Abstract

The present invention relates to novel herbicidally active thiadiazol compounds and in particular chlorinated thiadiazol compounds, methods for producing these compounds, as well as to compositions comprising them. In addition, the present invention relates to the use of these compounds and composition comprising these compounds in agriculture or horticulture, in particular as a herbicide.

Description

[0001] HERBICIDAL ACTIVE THIADIAZOL COMPOUNDS

[0002] FIELD OF THE INVENTION

[0003] The present invention relates to novel herbicidally active thiadiazol compounds and in particular chlorinated thiadiazol compounds, methods for producing these compounds, as well as to compositions comprising them. In addition, the present invention relates to the use of these compounds and composition comprising these compounds in agriculture or horticulture, in particular as a herbicide. BACKGROUND OF THE INVENTION

[0004] In view of the increasing world population and the associated increased demand for nourishments, the productivity of cultivated growth needs to be improved. However, unwanted plants reduce crop yield due to resource competition and are considered to also alter developmental trajectories of crops early in the growing season. Therefore, herbicides are used to control the growth of unwanted plants.

[0005] The present invention therefore aims for the provision of herbicidally active compounds and to compositions comprising the same which are useful in agriculture or horticulture. In particular, the present invention aims to have selective herbicides that reduce unwanted damage and / or have a toxicologically favourable profile, particularly in crop plants, especially in cereal crops such as maize, barley and / or wheat.

[0006] It is also an aim of the present invention to provide a broad-spectrum herbicide - preferably a broadspectrum, pre-emergence or post-emergence herbicide - which exhibits improved or comparable efficacy to flufenacet ( / V-(4-fluorophenyl)- / V-(propan-2-yl)-2-{[5-(trifluoromethyl)-1 ,3,4-thiadiazol-2-yl]oxy}acetamide) against monocotyledonous plants (i.e. from the plant clade Monocots) and / or dicotyledonous plants (i.e. from the plant clade Eudicots).

[0007] It is another aim of the present invention to provide a herbicide - preferably a pre-emergence herbicide - which provides broad-spectrum efficacy against perennial monocotyledonous plants which is comparable to flufenacet, but is more effective against dicotyledonous plants, especially plants from the clade Eudicotidae such as the pests Chenopodium album, Solanum nigrum and / or Geranium dissectum. It is another aim of the present invention to provide a pre-emergence herbicide which is effective against Lolium multiflorum and / or Alopecurus myosuroides, but is also more effective against monocotyledonous plants than flufenacet, especially against Apera spica-venti, Digitaria sanguinalis and / or Echinochloa crus-galli, particularly at lower application rates.

[0008] Another aim of the present invention is to provide a post-emergence herbicide which is more selective for monocotyledonous plants than is flufenacet (i.e. it exhibits lower post-emergence herbicidal activity against dicotyledonous plants than does flufenacet).

[0009] It is another aim of the present invention to provide a post-emergence herbicide which is more effective than flufenacet against Lolium multiflorum, Apera spica-venti and / or Setaria viridis.

[0010] It is also an aim of the present invention to provide a herbicide which exhibits reduced levels of damage to crops (phytotoxicity) when applied pre-emergence or post-emergence.

[0011] It is additionally an aim of the present invention to provide a herbicide that is stable and does not break down into metabolites which are harmful to the environment or organisms therein.SUMMARY OF THE INVENTION

[0012] The present invention is based on the finding that the above object can be solved by novel compounds having a specific structure that includes a chlorinated thiadiazol moiety.

[0013] Specifically, according to a first aspect of the invention, the present invention provides a compound corresponding to the following formula I, or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof:

[0014]

[0015] [Formula I]

[0016] wherein

[0017] each of R1aand R1bis H;

[0018] R2is selected from C1-3 alkyl, C4-8 alkyl, C9-19 alkyl, C1-6 alkoxy, C2-6 alkenyl, C2-ealkynyl, C3-6 cycloalkyl, (C3-6 cycloalkyl)Ci-3 alkyl, C1-6 alkylsulfonyl, C2-8 heterocyclyl and (C2-8 heterocyclyl)Ci-3 alkyl, each of which may be optionally substituted; and

[0019] R3is selected from C6-10 aryl, and C3-7 heteroaryl, each of which may be optionally substituted; or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof,

[0020] wherein:

[0021] when R1a= H, R1b= H and R2= isopropyl, R3is not phenyl, 4-fluorophenyl, 2-chlorophenyl, 3- chlorophenyl, 4-chlorophenyl, 3-methylphenyl, 4-methylphenyl, 2-methoxyphenyl, 4- methoxyphenyl, 4-ethoxyphenyl, 4-thiomethylphenyl, 3-chloro-4-thiomethylphenyl, 3,5- dimethylphenyl, 3,5-dichlorophenyl, 3-chloro-4-methoxyphenyl, 3,5-di(trifluoromethyl)phenyl, 3,4-dichlorophenyl, 5-chloro-2-methylphenyl; or

[0022] when R1a= H, R1b= H and R2= methyl, R3is not phenyl, 4-(trifluoromethyl)phenyl, 3- (trifluoromethyl)phenyl, 2-methyl-5-nitrophenyl, 2-thiophenyl, 3-thiophenyl, 4-thiophenyl, 4- thiomethylphenyl, 3-thiomethylphenyl, 4-fluorophenyl, 3-fluorophenyl, 3,4-dichlorophenyl, 2- methylphenyl, 3-methylphenyl, 4-methylphenyl, 3-chlorophenyl.

[0023] The present invention also covers compounds which include isotopes of the above-mentioned groups, and it specifically includes deuterated compounds of the above defined compound of formula I and any of the compounds defined in the following.

[0024] In a second aspect, the present invention provides a composition comprising a compound according to the first aspect.

[0025] In a third aspect, the present invention provides the use of the compound according to the first aspect or a composition according to the second aspect in agriculture or horticulture.

[0026] In a fourth aspect, the present invention provides methods for producing a compound according to the first aspect.In a fifth aspect, the present invention provides compounds which may be useful intermediates in the preparation of the compounds according to the first aspect, as well as the use of any of these compounds in the preparation of a compound according to the first aspect, and processes for preparing a compound according to the first aspect that involves any of these compounds.

[0027] In a further aspect, the present invention also provides combinations comprising a compound according to the first aspect or a composition according to the second aspect and one or more additional herbicides and / or plant growth regulators. These compositions and agrochemical combinations may also be used in accordance with the third aspect.

[0028] In another aspect, the present invention further provides a plant propagation material which comprises or is treated with or adheres thereto a compound according to the first aspect or a corresponding composition.

[0029] In the following, the present invention and definitions as used herein to describe the present invention will be set out in more detail.

[0030] DEFINITIONS

[0031] In the present disclosure, the following definitions are applicable.

[0032] The term "Cn-Cmalkyl” as used herein refers to a saturated straight-chain or branched hydrocarbon radical attached via any of the carbon atoms having n to m carbon atoms (herein n and m is each a natural number independently selected from 1 to 10 or from 8 to 20, where n<m), for example, any one of the radicals methyl, ethyl, n-propyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 -ethylpropyl, n-hexyl, n-pentyl, 1 ,1 -dimethylpropyl, 1 ,2-dimethylpropyl, 1 -methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1 -dimethylbutyl, 1 ,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1 -ethylbutyl, 2-ethylbutyl, 1 ,1 ,2-trimethylpropyl, 1 ,2,2-trimethylpropyl, 1-ethyl-1 -methylpropyl, or 1-ethyl-2-methylpropyl, or any one of the radicals n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nondecyl or n-eicosyl, but are not limited thereto.

[0033] The term "Cn-Cmalkoxy" as used herein refers to a straight-chain or branched saturated alkyl radical having n to m carbon atoms (as mentioned above) which is attached via an oxygen atom, i.e., for example, any one of the radicals methoxy, ethoxy, n-propoxy, 1 -methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy or 1 ,1 -dimethylethoxy, but are not limited thereto.

[0034] The term “(Cn-Cmalkoxy)Cn-Cmalkyl” refers to an alkyl group where one or more of the hydrogens is substituted by an alkoxy group, n and m in the alkoxy group and the alkyl group are independently selected as appropriate.

[0035] The term “Cn-Cm(cyano)alkyl” as used herein refers to a straight chain or branched saturated Cn-Cmalkyl radical having n to m carbon atoms (as mentioned above), where one or more of the hydrogen atoms in these radicals is replaced by a cyano group: for example, cyanomethyl, 2-cyanoethyl, 2-cyanopropyl, 3-cyanopropyl, 1-(cyanomethyl)-2-ethyl, 1-(methyl)-2-cyanoethyl, 4-cyanobutyl, and the like.

[0036] The term “C3-Cmcycloalkyl” as used herein refers to 3 to m membered cycloalkyl groups such as cyclopropane, cyclobutane, cyclopentane, cyclohexane and the like.

[0037] The term “C2-Cmalkenyl” as used herein refers to a straight or branched alkenyl chain having from two to m carbon atoms and one or more double bonds, for example, ethenyl, prop-1 -enyl, and but-2-enyl, but are not limited thereto.The term “C2-Cmalkynyl” as used herein refers to a straight or branched alkynyl chain having from two to m carbon atoms and one or more triple bond, for example, ethynyl, prop-2-ynyl, but-3-ynyl.

[0038] The term “Ce-Cio aryl” as used herein refers to a carbocyclic ring system comprising 6 to 10 carbon atoms and at least one aromatic ring. For purposes of embodiments of this invention, the aryl group is a monocyclic or bicyclic ring system. Aryl groups include, but are not limited to, aryl residues derived from benzene or naphthalene (i.e., phenyl or naphthyl). Unless stated otherwise specifically in the specification, the term “aryl” or the prefix “ar“ (such as in “aralkyl”) is meant to include aryl groups that are optionally substituted.

[0039] The term “C3-7 heteroaryl” as used herein refers to a carbocyclic ring system comprising 3 to 7 carbon atoms, at least one heteroatom selected from O, N and S, preferably selected from N and S, and at least one aromatic ring. For purposes of embodiments of this invention, the heteroaryl group is a monocyclic or bicyclic ring system. Heteroaryl groups include, but are not limited to, residues derived from heteroaromatic compounds such as pyridine, thiophene, thiazole and benzothiazole (i.e. pyridinyl, thiophenyl, thiazolyl and benzothiazolyl). Unless stated otherwise specifically in the specification, the term “heteroaryl” is meant to include heteroaryl groups that are optionally substituted.

[0040] The term “carbocyclic group” as used herein refers to a closed ring structure which consists of carbon atoms and hydrogen atoms. The term “heterocyclic group” as used herein refers to closed ring structures analogous to carbocyclic groups in which one or more of the carbon atoms in the ring is an element other than carbon, for example, nitrogen (N), sulfur (S) or oxygen (O).

[0041] The term “heterocyclyl” as used herein refers to a radical of a heterocyclic group which is attached via any of the carbon atoms. Analogous to the foregoing, “heterocyclyl(alkyl)” refers to heterocyclyl which is substituted with an alkyl group.

[0042] The term "oxo" as used herein means an oxygen atom that is double bonded to a carbon atom or to another element.

[0043] Halogen or “halo” generally refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I). This also applies, correspondingly, to halogen in combination with other meanings, such as haloalkyl.

[0044] The term “optionally substituted” as used herein means that the group referenced is either unsubstituted or is substituted by one or more substituents. For example, “C1-C3 alkyl is optionally substituted with one or two F” means a group selected from C1-C3 alkyl, C1-C3 alkyl substituted with one F, and C1-C3 alkyl substituted with two F.

[0045] Unless specified otherwise, the term “substituted” as used herein means substitution by any of the above or other groups (e.g., alkyl, alkylene, alkylcycloalkyl, alkoxy, alkylphosphoryl, alkylphosphorylaminyl, amidinylalkyloxy, guanidinylalkyloxy, alkylcarbonylaminylalkyloxy, heterocyclylalkyloxy, heteroarylalkyloxy, aminylalkyloxy, alkoxyalkyl, alkoxycarbonyl, haloalkylaminyl, hydroxylalkylaminyl, amidinylalkylaminyl, guanidinylalkylaminyl, aminylalkyl, aminylalkylaminyl, aminylalkoxy, alkylaminylalkoxy aryloxy, alkylaminyl, alkylcarbonylaminyl, alkylaminylalkyl, aminylcarbonyl, alkylaminylcarbonyl, alkylcarbonylaminylalkoxy, aminylcarbonylalkyl, aminylcarbonycycloalkylalkyl, thioalkyl, aryl, aralkyl, arylalkyloxy, arylalkylaminyl, carboxyalkyl, cyanoalkyl, cycloalkyl, cycloalkyloxy, cycloalkylaminyl, cyanocycloalkyl, cycloalkylaminylcarbonyl, cycloalkylalkyl, haloalkyl, haloalkoxy, heterocyclyl, heterocyclyloxy, heterocyclylaminyl, / V-heterocyclyl, heterocyclylalkyl, heterocyclylalkyloxy, heterocyclylalkylaminyl, heteroaryl, / V-heteroaryl, heteroarylalkyl, heteroarylalkyloxy, heteroarylalkylaminyl, hydroxylalkylaminyl, phosphoalkoxy and / or hydroxylalkyl) wherein at least one hydrogen atom (e.g., 1 , 2, 3 or more or all hydrogen atoms) is replaced by a bond to a non-hydrogen atom such as, but not limited to: a halogen atom such as F, Cl, Br, and I; an oxygen atom in groups such as hydroxyl groups, alkoxy groups, and ester groups; a sulfur atom in groups such as thiol groups, thioalkyl groups, sulfonyl groups, and sulfoxide groups; a nitrogen atom in groups suchas amines, amides, alkylamines, dialkylamines, arylamines, alkylarylamines, diarylamines, / V-oxides, imides, and enamines; a silicon atom in groups such as trialkylsilyl groups, dialkylarylsilyl groups, alkyldiarylsilyl groups, and triarylsilyl groups; and other heteroatoms in various other groups. “Substituted” also means any of the above groups in which one or more hydrogen atoms are replaced by a higher-order bond (e.g., a double- or triple-bond) to a heteroatom such as oxygen in oxo, carbonyl, carboxyl, and ester groups; and nitrogen in groups such as imines, oximes, hydrazones, and nitriles. For example, “substituted” includes any of the above groups in which one or more hydrogen atoms are replaced with -NRgRh, -NRgC(=O)Rh, -NRgC(=O)NRgRh, -NRgC(=O)ORh, -NRgSO2Rh, -OC(=O)NRgRh, -ORg, -SRg, -SORg, -SO2Rg, -OSO2Rg, -SO2ORg, =NSO2Rg, and -SO2NRgRh. “Substituted” also means any of the above groups in which one or more hydrogen atoms are replaced with -C(=O)Rg, -C(=O)ORg, -C(=O)NRgRh, -CH2SO2Rg, -CH2SO2NRgRh. In the foregoing, Rgand Rh are the same or different and independently hydrogen, alkyl, alkoxy, alkylaminyl, thioalkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, haloalkyl, heterocyclyl, N-heterocyclyl, heterocyclylalkyl, heteroaryl, / V-heteroaryl and / or heteroarylalkyl. “Substituted” further means any of the above groups in which one or more hydrogen atoms are replaced by a bond to an aminyl, cyano, hydroxyl, imino, nitro, oxo, thioxo, halo, alkyl, alkoxy, alkylaminyl, thioalkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, haloalkyl, heterocyclyl, / V-heterocyclyl, heterocyclylalkyl, heteroaryl, N-heteroaryl and / or heteroarylalkyl group. In addition, each of the foregoing substituents may also be optionally substituted with one or more of the above substituents.

[0046] The term “leaving group” as used herein refers to a group capable of being displaced from a molecule when said molecule undergoes reaction with a nucleophile.

[0047] The term “stereoisomer” as used herein includes any enantiomer, diastereomer, geometric isomer (E / Z) or tautomer of a given compound.

[0048] The term “deuteromer” as used herein, refers to a given compound in which at least one hydrogen atom (1H), preferably at least two, more preferably 3, 4, 5, and most preferably all hydrogen atoms are replaced with a deuterium isotope (2H or D). For example, one or both H-atoms of a -CH2- moiety in a given compound may be replaced with D (i.e. -CHD- orCD2-).

[0049] As used herein, the term “agrochemically acceptable salt” refers to a salt which can be applied as an agrochemical. As also used herein, the term “agrochemical” refers to a chemical applied in agriculture and / or horticulture.

[0050] As used herein, the term "herbicide" refers to an active ingredient that kills, controls or otherwise inhibits plant growth. The preferred amount or concentration of the herbicide is an “effective amount” or “effective concentration”.

[0051] As used herein, the term "controlling" means killing, reducing or retarding growth or preventing or reducing germination of plants. Generally, the plants to be controlled are unwanted plants, also called weeds. “Locus” means the area in which the plants are growing or will grow.

[0052] As used herein, the term “pre-emergence” refers to the period of time before the germinated plant is established (i.e. before the germinated plant emerges from the soil). On the other hand, “postemergence” refers to the period of time once the germinated plant has established itself (i.e. once the germinated plant emerges from the soil).

[0053] As used herein, the terms "effective amount" and “effective concentration” refer to the amount or concentration of the compound, respectively, or an agrochemically acceptable salt thereof, which, upon single or multiple applications provides the desired effect.

[0054] An effective amount or an effective concentration is readily determined by the skilled person in the art, by the use of known techniques and by observing results obtained under analogous circumstances. Indetermining the effective amount or the effective concentration, a number of factors are considered including, but not limited to, the type of plant or derived product to be applied; the unwanted plants to be controlled and its lifecycle; the particular compound applied; the type of application; and other relevant circumstances.

[0055] In each of the following aspects and embodiments of the invention, "consisting essentially" and inflections thereof are a preferred embodiment of "comprising" and its inflections, and "consisting of’ and inflections thereof are a preferred embodiment of "consisting essentially of’ and its inflections. DETAILED DESCRIPTION OF THE INVENTION

[0056] Embodiments according to the invention are provided as set out below. The disclosure in the present application makes available each and every combination of these embodiments disclosed in the following.

[0057] 1. A compound of formula I:

[0058]

[0059] [Formula I]

[0060] wherein each of R1aand R1bis H;

[0061] R2is selected from C1-3 alkyl, C4-8 alkyl, C9-19 alkyl, C1-6 alkoxy, C2-6 alkenyl, C2-ealkynyl, C3-6 cycloalkyl, (C3-6 cycloalkyl)Ci-3 alkyl, C1-6 alkylsulfonyl, C2-8 heterocyclyl and (C2-8 heterocyclyl)Ci-3 alkyl, each of which may be optionally substituted; and

[0062] R3is selected from C6-10 aryl, and C3-7 heteroaryl, each of which may be optionally substituted; or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof,

[0063] wherein when:

[0064] R1a= H, R1b= H and R2= isopropyl, R3is not phenyl, 4-fluorophenyl, 2-chlorophenyl, 3- chlorophenyl, 4-chlorophenyl, 3-methylphenyl, 4-methylphenyl, 2-methoxyphenyl, 4- methoxyphenyl, 4-ethoxyphenyl, 4-thiomethylphenyl, 3-chloro-4-thiomethylphenyl, 3,5- dimethylphenyl, 3,5-dichlorophenyl, 3-chloro-4-methoxyphenyl, 3,5-di(trifluoromethyl)phenyl, 3,4-dichlorophenyl, 5-chloro-2-methylphenyl; or

[0065] R1a= H, R1b= H and R2= methyl, R3is not phenyl, 4-(trifluoromethyl)phenyl, 3- (trifluoromethyl)phenyl, 2-methyl-5-nitrophenyl, 2-thiophenyl, 3-thiophenyl, 4-thiophenyl, 4- thiomethylphenyl, 3-thiomethylphenyl, 4-fluorophenyl, 3-fluorophenyl, 3,4-dichlorophenyl, 2- methylphenyl, 3-methylphenyl, 4-methylphenyl, 3-chlorophenyl.

[0066] 2. The compound of item 1 , wherein:

[0067] each of the groups listed for R2is optionally substituted by one or more substituents selected from F, Cl, Br, I, CN, oxo, C1-6 alkyl, C1-6 alkoxy, C1-6 alkylthio, (Ci-6alkoxy)Ci-6alkyl, SO2R, C(O)R, CO2R, C(O)NR2, NR2 and SiRs, wherein each R is independently selected from H, OH, C1-6 alkoxy and C1-6 alkyl, and wherein two Rs and the atom to which they are bound may form a cyclic group;each of the groups listed for R3is substituted by one or more substituents selected from F, Cl, Br, I, CN, NO2, C1-6 alkyl, C1-6 alkoxy, C1-6 alkylthio, C3-6 cycloalkyl, (cyano)Ci-e alkyl, NR42, SO2R5, and CO2R6, wherein each R4is independently selected from C1-3 alkyl, wherein optionally the two R4and the N atom to which they are bound may form a 3- to 6-membered heterocyclic group, each R5is independently selected from C1-6 alkyl and C1-6 alkoxy, and each R6is independently selected from H and C1-6 alkyl; or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof.

[0068] 3. The compound of item 1 , with the proviso that R3is Ce aryl that is substituted or C3-7 heteroaryl that is unsubstituted or substituted, wherein the substituent is selected from at least one of halogen, CN, NO2, C1-6 alkyl, halogeno-Ci-6 alkyl, C1-6 alkoxy, halogeno-Ci-6 alkoxy, C1-6 alkylthio and halogeno-Ci-6 alkylthio, (cyano)methyl, NMe2, SO2Me, and CO2Me, preferably Ce aryl substituted by at least one of F, Cl, CH3, OCH3, OC2H5, SCH3 and CF3 or C3-7 heteroaryl that is unsubstituted or substituted by at least one F;

[0069] or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof.

[0070] 4. The compound of any one of items 1 to 3, wherein R2is selected from C4-8 alkyl, C9-19 alkyl, (cyano)Ci-6 alkyl, C1-6 alkoxy, C2-6 alkenyl, C2-ealkynyl, C3-6 cycloalkyl, (C3-6 cycloalkyl)Ci-3 alkyl, C2-8 heterocyclyl and (C2-8 heterocyclyl)Ci-3 alkyl, each of which may be optionally substituted by one or more groups selected from F, Cl, Br, I, CN, oxo, C1-6 alkyl, C1-6 alkoxy, (Ci-6alkoxy)Ci-6alkyl, SO2R, C(O)R, CO2R, C(O)NR2, NR2 and SiRs, wherein each R is independently selected from H, OH and C1-6 alkyl,

[0071] or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof.

[0072] 5. The compound of any one of items 1 to 4, wherein R2is selected from C4-8 alkyl, (cyano)Ci-6 alkyl, C2-6 alkenyl, C2-ealkynyl, (C3-6 cycloalkyl)Ci-3 alkyl and C3-6 cycloalkyl, each of which may be optionally substituted by one or more groups selected from F, Cl, Br, I, CN, oxo, C1-6 alkyl, C1-6 alkoxy, (Ci-6alkoxy)Ci-6alkyl, SO2R, C(O)R, CO2R, C(O)NR2, NR2 and SiRs, wherein each R is independently selected from H, OH and C1-6 alkyl; or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof.

[0073] 6. The compound of any one of items 1 to 5, wherein R2is selected from R2-1 to R2-63 as defined in Table 1 below; or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof.

[0074] 7. The compound of any one of items 1 to 6, wherein R2is selected from cyanomethyl, cyclopropyl, sec-butyl, 1-butyn-4-yl, 2-butyn-1-yl, prop-1 -yl, 3-methyl-1-butyn-3-yl, cyclopropylmethyl, 1-trimethylsilyl-2-butyn-4-yl, 1-buten-4-yl, 1-buten-3-yl, 2-methyl-1-propen-3-yl, allyl, tert-butyl, cyclopentyl, propargyl, iso-butyl, iso-propyl, 1-butyn-3-yl and 3-methylbut-2-yl; or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof.

[0075] 8. The compound of any one of items 1 to 7, wherein R2is selected from cyanomethyl, cyclopropyl, sec-butyl, 1-butyn-4-yl, 2-butyn-1-yl, prop-1 -yl, 3-methyl-1-butyn-3-yl, cyclopropylmethyl, 1-trimethylsilyl-2-butyn-4-yl, 1-buten-4-yl, 1-buten-3-yl, 2-methyl-1-propen-3-yl, allyl, tert-butyl, cyclopentyl, propargyl, iso-butyl, 1-butyn-3-yl and 3-methylbut-2-yl; or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof.9. The compound of any one of items 1 to 4, wherein R2is selected from C2-8 alkyl, (cyano)Ci-6 alkyl, C2-6 alkenyl, C2-ealkynyl, (C3-6 cycloalkyl)Ci-3 alkyl and C3-6 cycloalkyl, each of which may be optionally substituted by one or more groups selected from F, Cl, Br, I, CN, oxo, C1-6 alkyl, C1-6 alkoxy, (Ci-6alkoxy)Ci-6alkyl, SO2R, C(O)R, CO2R, C(O)NR2, NR2 and SiRs, wherein each R is independently selected from H, OH and C1-6 alkyl; or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof.

[0076] 10. The compound of any one of items 1 to 9, wherein R3is C6-10 aryl substituted by at least one F or C3-7 heteroaryl that is unsubstituted or substituted by at least one F, preferably R3is C6-10 aryl substituted by at least one F in the 3-position or 4-position relative to the attachment point of R3to the remainder of the molecule, and optionally further substituted by one or more groups selected from F, Cl, Br, I, CN, NO2, C1-6 alkyl, C1-6 alkoxy and C3-6 cycloalkyl; or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof.

[0077] 11. The compound of any one of items 1 to 10, wherein R3is Ce aryl substituted by at least one F or C3-7 heteroaryl that is unsubstituted or substituted by at least one F, preferably R3is Ce aryl substituted by at least one F in the 3-position or 4-position relative to the attachment point of R3to the remainder of the molecule, and optionally further substituted by one or more groups selected from F, Cl, Br, I, CN, NO2, C1-6 alkyl, C1-6 alkoxy and C3-6 cycloalkyl; or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof.

[0078] 12. The compound of any one of items 1 to 11 , wherein R3is selected from R3-1 to R3-92 as defined in Table 2 below; or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof.

[0079] 13. The compound of any of items 1 to 12, wherein R3is selected from 4-fluorophenyl, 4-chlorophenyl, 4-nitrophenyl, 4-(trifluoromethoxy)phenyl, 2-fluorophenyl, 3-fluorophenyl, 2,5-difluorophenyl, 3,4-difluorophenyl, 2,4-difluorophenyl, 2,3-difluorophenyl, 3,5-difluorophenyl, 2,6-difluorophenyl, 3-fluoro-4-chlorophenyl, 3-chloro-4-fluorophenyl, 2-chloro-4-fluorophenyl, 4-fluoro-2-nitrophenyl, 4-fluoro-2-methylphenyl, 4-fluoro-2-methoxyphenyl, 2,4,5-trifluorophenyl, 2,3,4-trifluorophenyl, 2,4,6-trifluorophenyl, 2-chloro-4,6-difluorophenyl, 3-chloro-2,4-difluorophenyl, 2,6-dichloro-4-fluorophenyl and 2-chloro-4-fluoro-6-methylphenyl; or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof.

[0080] 14. The compound of any one of items 1 to 13, wherein R3is selected from 4-fluorophenyl, 3,4-difluorophenyl, 2,4-difluorophenyl, 3-fluoro-4-chlorophenyl, 3-chloro-4-fluorophenyl, 4-chlorophenyl, 4-nitrophenyl, 4-(trifluoromethoxy)phenyl, 2,5-difluorophenyl, 4-fluoro-2-nitrophenyl, 4-fluoro-2-methylphenyl, 4-fluoro-2-methoxyphenyl, 2,4,5-trifluorophenyl, 2,3,4-trifluorophenyl, 2,4,6-trifluorophenyl, 2-chloro-4,6-difluorophenyl, 3-chloro-2,4-difluorophenyl, 2,6-dichloro-4-fluorophenyl and 2-chloro-4-fluoro-6-methylphenyl; or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof.

[0081] 15. The compound of any one of items 1 to 14, wherein R2is selected from iso-butyl, tert-butyl, cyclopentyl and propargyl, preferably propargyl; or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof.

[0082] 16. The compound of any one of items 1 to 14, wherein R2is selected from C1-3 alkyl; or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof.

[0083] 17. The compound of any one of items 1 to 14 and 16, wherein R2is isopropyl; or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof.18. The compound of any one of items 1 to 14, wherein R2is selected from C1-3 alkyl, C4-8 alkyl, (cyano)Ci-6 alkyl, C2-6 alkenyl, C2-ealkynyl, (C3-6 cycloalkyl)Ci-3 alkyl and C3-6 cycloalkyl, each of which may be optionally substituted; and R3is 4-fluorophenyl; or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof.

[0084] 19. The compound of any one of items 1 to 14 and 18, wherein R2is selected from C4-8 alkyl, (cyano)Ci-6 alkyl, C2-6 alkenyl, C2-ealkynyl, (C3-6 cycloalkyl)Ci-3 alkyl and C3-6 cycloalkyl, each of which may be optionally substituted; and R3is 4-fluorophenyl; or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof.

[0085] 20. The compound of any one of items 1 to 14 and 18, wherein R2is selected from cyanomethyl, cyclopropyl, sec-butyl, 1-butyn-4-yl, 2-butyn-1-yl, prop-1 -yl, 3-methyl-1-butyn-3-yl, cyclopropylmethyl, 1-trimethylsilyl-2-butyn-4-yl, 1-buten-4-yl, 1-buten-3-yl, 2-methyl-1-propen-3-yl, allyl, tert-butyl, cyclopentyl, propargyl, iso-butyl, iso-propyl, 1-butyn-3-yl and 3-methylbut-2-yl, and R3is 4-fluorophenyl; or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof.

[0086] 21. The compound of any one of items 1 to 14, 18 and 20, wherein R2is selected from cyanomethyl, cyclopropyl, sec-butyl, 1-butyn-4-yl, 2-butyn-1-yl, prop-1 -yl, 3-methyl-1-butyn-3-yl, cyclopropylmethyl, 1-trimethylsilyl-2-butyn-4-yl, 1-buten-4-yl, 1-buten-3-yl, 2-methyl-1-propen-3-yl, allyl, tert-butyl, cyclopentyl, propargyl, iso-butyl, 1-butyn-3-yl and 3-methylbut-2-yl, and R3is 4-fluorophenyl; or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof.

[0087] 22. The compound of any one of items 1 to 21, having a structure selected from Table 3; or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof, with the proviso that said compound is not compound I-9, I-20, 1-108, I-141 , 1-174, I-900, 1-1483, 1-1494, 1-1505, VII-1, VII-12, VII-100, VII-419, VII-1365, VII-1475 or VII-1497, preferably with the proviso that said compound is not compound I-9, I-20, 1-108, 1-141 , 1-174, I-900, I-1483, 1-1494, 1-1505, VII-1 , VII-12, VII-100, VII-419, VII-1365, VII-1475, VII-1497, 1-11 , 1-1197, 1-1461 , 1-1516, VII-2, VII-3 or VII-4, and more preferably with the proviso that said compound is not compound I-9, I-20, 1-108, 1-141 , 1-174, I-900, 1-1483, 1-1494, 1-1505, VII-1 , VII-12, VII-100, VII-419, VII-1365, VII-1475, VII-1497, I-3, I-427, I-438, I-460, 1-515, I-702, 1-1219, 1-1131 , 1-1472, V-5, 1-11 , 1-1197, 1-1461 , I-1516, VII-2, VII-3, VII-4.

[0088] 23. The compound of any one of items 1 to 22, represented by the following Formula la’,

[0089]

[0090] [Formula la’]

[0091] wherein R2is: (i) allyl; (ii) propargyl; (iii) 1-butyn-3-yl; (iv) 1-butyn-4-yl; (v) 2-butyn-1-yl; (vi) prop-1 -yl; (vii) 3-methyl-1-butyn-3-yl; or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof.

[0092] 24. The compound of any one of items 1 to 23, represented by the following Formula la’,

[0093]

[0094] [Formula la’]

[0095] wherein R2is:

[0096] (i) 1-butyn-4-yl;

[0097] (ii) 2-butyn-1-yl;

[0098] (iii) propargyl; or

[0099] (iv) allyl;

[0100] or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof.

[0101] 25. A composition comprising a compound according to any one of items 1 to 24 or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof, and one or more auxiliary and / or adjuvant, and optionally one or more further active ingredients.

[0102] 26. The composition of item 25, which is an agrochemical composition.

[0103] 27. Use of a compound according to any one of items 1 to 24 or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof, or a composition according to item 25 or 26 in agriculture or horticulture.

[0104] 28. Use of the compound of any one of items 1 to 24 or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof, or a composition according to item 25 or 26 as a herbicide on crops selected from cereals including barley and wheat, cotton, oilseed rape, sunflower, maize, rice, soybeans, sugar beet, sugar cane, turf, trees including fruit trees, palm trees, coconut trees or other nuts, vines including grapes, fruit bushes, fruit plants, and vegetables including potatoes and tomatoes.

[0105] 29. The use of item 28, wherein the compound or composition is used against a monocotyledonous plant (i.e. a plant from the clade Monocots) and / or a dicotyledonous plant (i.e. a plant from the clade Eudicot), preferably against a species selected from blackgrass, wild oat, Fat Hen, Crabgrass, Barnyard grass, cut-leaved crane's-bill, Italian ryegrass, Common Millet, green bristlegrass and Black nightshade.

[0106] 30. The use of item 28 or 29 wherein the compound or composition is used against a monocotyledonous plant (i.e. a plant from the clade Monocots) and / or a dicotyledonous plant (i.e. a plant from the clade Eudicot), preferably against a species selected from Abutilon theophrasti, Alopecurus myosuroides, Amaranthus albus, Amaranthus blitoides, Amaranthus blitum, Amaranthus hybridus, Amaranthus palmeri, Amaranthus powellii, Amaranthus retroflexus, Amaranthus sp. (herein sp. or spp. refers to species), Amaranthus spinosus, Amaranthus tuberculatus, Amaranthus viridis, Ambrosia artemisiifolia, Ambrosia trifida, Apera spica-venti, Avena fatua, Brachiaria platy phylla, Brassica napus, Brassica rapa, Brassica sp., Bromus catharticus, Bromus tectorum, Capsella bursa-pastoris, Caucalis platycarpos, Chenopodiastrum murale, Chenopodium album, Chenopodium vulvaria, Chloris sp., Chrozophora tinctoria, Cirsium arvense, Commelina benghalensis, Commelina erecta, Consolida regalis, Convolvulus arvensis, Conyza bonariensis, Conyza sp., Conyza sumatrensis, Cynodon dactylon, Cynodon hirsutus, Cynodon sp., Cy perus esculentus, Cy perus rotund us, Datura stramonium, Descurainia pinnata, Descurainia sophia, Digitaria sanguinalis, Digitaria sanquinalis, Echinochloacolona, Echinochloa coIonum, Echinochloa crus-galli, Echinochloa sp., Eleusine indica, Elymus repens, Elytrigia repens, Equisetum arvense, Erigeron annuus, Erigeron bonariensis, Erigeron canadensis, Erigeron floribundus, Fallopia convolvulus, Fumaria officinalis, Galeopsis spp., Galinsoga parviflora, Galinsoga quadriradiata, Galium aparine, Galium spurium, Galium tricomutum, Geranium dissectum, Gomphrena sp., Helianthus annuus, Hibiscus trionum, Hirschfeldia incana, Humulus lupulus, Ipomoea cordatotriloba, Ipomoea hederacea, Ipomoea heptaphylla, Ipomoea lacunosa, Ipomoea muricata, Ipomoea purpurea, Ipomoea tricolor, Kochia sp., Lamium hybrid urn, Lamium spp., Lapsana communis, Linaria vulgaris, Lolium multiflorum, Lolium perenne, Lolium sp., Malva sylvestris, Matricaria discoidea, Myosotis arvensis, Panicum miliaceum, Papaver rhoeas, Persicaria lapathifolia, Persicaria maculosa, Phalaris brachystachys, Phalaris minor, Phalaris paradoxa, Phragmites australis, Physalis acutifolia, Phytolacca americana, Plantago lanceolata, Plantago major, Poa annua, Poa trivialis, Polygonum aviculare, Polygonum persicaria, Portulaca oleracea, Ranunculus repens, Raphanus sativus, Rapistrum rugosum, Rumex acetosella, Rumex crispus, Rumex obtusifolius, Senecio vulgaris, Senna tora, Setaria faberi, Setaria magna, Setaria pumila, Setaria pumila, Setaria verticillata, Setaria viridis, Sinapis arvensis, Sisymbrium altissimum, Solanum americanum, Solanum carolinense, Solanum nigrum, Sonchus arvensis, Sonchus oleraceus, Sorghum halepense, Spermacoce sp., Stellaria media, Taraxacum officinale, Toxicodendron radicans, Tribulus terrestris, Tripleurospermum inodorum, Tussilago farfara, Urochloa panicoides, Urochloa texana, Urtica dioica, Veronica arvensis, Veronica hederifolia, Veronica persica, Viola arvensis, and Xanthium spinosum, preferably wherein the compound is used against species selected from Alopecurus myosuroides, Avena fatua, Chenopodium album, Digitaria sanguinalis, Echinochloa crus-galli, Geranium dissectum, Lolium multiflorum, Panicum miliaceum, Setaria viridis and Solanum nigrum, more preferably against both a monocotyledonous plant and a dicotyledonous plant, the latter preferably selected from Chenopodium album, Geranium dissectum and Solanum nigrum.

[0107] 31. Agrochemical combination comprising the compound of any one of items 1 to 24 or the composition of item 25 or 26 and one or more additional herbicides and / or plant growth regulators. 32. Use of the compound of any one of items 1 to 24 or the composition of item 25 or 26 in combination with one or more additional herbicides.

[0108] 33. A composition comprising the compound of any one of items 1 to 24 and one or more additional herbicides and / or plant growth regulators.

[0109] 34. A method for producing compound according to any one of items 1 to 24, comprising a step selected from the following (i) to (iv):

[0110] (i)

[0111]

[0112]

[0113] wherein L, LG and LGXare each independently leaving groups, and the remaining groups are as defined hereinabove.

[0114] 35. An intermediate selected from:

[0115]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

[0122]

[0123] 36. The intermediate of item 35, wherein the intermediate is selected from:

[0124]

[0125]

[0126]

[0127] 37. A method for producing a compound according to item 1 to 24, involving using one or more intermediates according to item 35 in at least one step.

[0128] 38. A plant propagation material, such as a seed, comprising, or treated with or adhered thereto, a compound of any one of items 1 to 24 or a composition of item 25 or 26.

[0129] Compounds of formula I

[0130] According to a first aspect of the invention, there is provided a compound of formula I:

[0131]

[0132] [Formula I]

[0133] wherein each of R1aand R1bis H;

[0134] R2is selected from C1-3 alkyl, C4-8 alkyl, C9-19 alkyl, C1-6 alkoxy, C2-6 alkenyl, C2-ealkynyl, C3-6 cycloalkyl, (C3-6 cycloalkyl)Ci-3 alkyl, C1-6 alkylsulfonyl, C2-8 heterocyclyl and (C2-8 heterocyclyl)Ci-3 alkyl, each of which may be optionally substituted; and

[0135] R3is selected from Ce-io aryl, and C3-7 heteroaryl, each of which may be optionally substituted, wherein:

[0136] when R1a= H, R1b= H and R2= isopropyl, R3is not phenyl, 4-fluorophenyl, 2-chlorophenyl, 3- chlorophenyl, 4-chlorophenyl, 3-methylphenyl, 4-methylphenyl, 2-methoxyphenyl, 4- methoxyphenyl, 4-ethoxyphenyl, 4-thiomethylphenyl, 3-chloro-4-thiomethylphenyl, 3,5- dimethylphenyl, 3,5-dichlorophenyl, 3-chloro-4-methoxyphenyl, 3,5-di(trifluoromethyl)phenyl, 3,4-dichlorophenyl, 5-chloro-2-methylphenyl; or

[0137] when R1a= H, R1b= H and R2= methyl, R3is not phenyl, 4-(trifluoromethyl)phenyl, 3-(trifluoromethyl)phenyl, 2-methyl-5-nitrophenyl, 2-thiophenyl, 3-thiophenyl, 4-thiophenyl, 4- thiomethylphenyl, 3-thiomethylphenyl, 4-fluorophenyl, 3-fluorophenyl, 3,4-dichlorophenyl, 2- methylphenyl, 3-methylphenyl, 4-methylphenyl, 3-chlorophenyl.

[0138] In a preferred embodiment, each of the groups listed for R2is optionally substituted by one or more substituents selected from F, Cl, Br, I, CN, oxo, C1-6 alkyl, C1-6 alkoxy, C1-6 alkylthio, (C1-6 alkoxy)Ci-6alkyl, SO2R, C(O)R, CO2R, C(O)NR2, NR2 and SiRs, wherein each R is independently selected from H, OH, C1-6 alkoxy and C1-6 alkyl, and wherein two Rs and the atom to which they are bound may form a cyclic group.

[0139] In another preferred embodiment, R3is substituted by one or more substituents selected from F, Cl, Br, I, CN, NO2, C1-6 alkyl, C1-6 alkoxy, C1-6 alkylthio, C3-6 cycloalkyl, (cyano)Ci-e alkyl, NR42, SO2R5, and CO2R5, wherein each R4is independently selected from C1-3 alkyl and each R5is independently selected from H and C1-6 alkyl.

[0140] In another embodiment, the present invention provides a compound of any of the preceding embodiments with the proviso that R3is Ce aryl that is substituted or C3-7 heteroaryl that is unsubstituted or substituted, wherein the substituent is selected from at least one of halogen, CN, NO2, C1-6 alkyl, halogeno-Ci-6 alkyl, C1-6 alkoxy, halogeno-Ci-6 alkoxy, C1-6 alkylthio, halogeno-Ci-6 alkylthio, (cyano)methyl, NMe2, SO2Me, and CO2Me, preferably Ce aryl substituted by at least one of F, Cl, CH3, OCH3, OC2H5, SCH3 and CF3 or C3-7 heteroaryl that is unsubstituted or substituted by at least one F. In a further embodiment, the present invention provides a compound of any of the precedinge m bodiments wherein R2is selected from C4-8 alkyl, C9-19 alkyl, (cyano)Ci-e alkyl, C1-6 alkoxy, C2-6 alke nyl, C2-ealkynyl, C3-6 cycloalkyl, (C3-6 cycloalkyl)Ci-3 alkyl, C2-8 heterocyclyl and (C2-8 heterocyclyl)Ci-3 alkyl, each of which may be optionally substituted by one or more groups selected from F, Cl, Br, I, CN, oxo, C1-6 alkyl, C1-6 alkoxy, (Ci-6alkoxy)Ci-6alkyl, SO2R, C(O)R, CO2R, C(O)NR2, NR2 and SiRs, wherein each R is independently selected from H, OH and C1-6 alkyl. Preferably, R2may be selected from C4-8 alkyl, (cyano)Ci-e alkyl, C2-6 alkenyl, C2-ealkynyl and C3-6 cycloalkyl.

[0141] In a preferred embodiment, R2is selected from R2-1 to R2-73 as defined in Table 1 below, and R1a, R1band R3are defined as in the preceding embodiments.

[0142] Table 1. Preferred R2groups

[0143] "

[0144] <

[0145]

[0146] "

[0147] >

[0148]

[0149] In a further preferred embodiment, R2is selected from cyanomethyl, cyclopropyl, sec-butyl, 1-butyn-4-yl, 2-butyn-1-yl, prop-1 -yl, 3-methyl-1-butyn-3-yl, cyclopropylmethyl, 1 -trimethylsilyl-2-butyn-4-yl, 1-buten-4-yl, 1-buten-3-yl, 2-methyl-1-propen-3-yl, allyl, tert-butyl, cyclopentyl, propargyl, iso-butyl, iso

[0150] propyl, 1-butyn-3-yl and 3-methylbut-2-yl, and R1a, R1band R3are defined as in the prec eding embodiments. More preferably, R2is selected from allyl, propargyl, 1-butyn-3-yl, 1-butyn-4-yl, 2-butyn-1 -yl and 3-methyl-1-butyn-3-yl.

[0151] In a further more preferred embodiment, R3is 4-fluorophenyl and R2is selected from R2is selected from cyanomethyl, cyclopropyl, sec-butyl, 1-butyn-4-yl, 2-butyn-1-yl, prop-1 -yl, 3-methyl-1-butyn-3-yl, cyclopropylmethyl, 1 -trimethylsilyl-2-butyn-4-yl, 1-buten-4-yl, 1-buten-3-yl, 2-methyl-1-propen-3-yl, allyl, tert-butyl, cyclopentyl, propargyl, iso-butyl, iso-propyl, 1-butyn-3-yl and 3-methylbut-2-yl, and R1a, R1band R3are defined as in the preceding embodiments. Even more preferably, R3is 4-fluorophenyl and R2is selected from allyl, propargyl, 1-butyn-3-yl, 1-butyn-4-yl, 2-butyn-1-yl and 3-methyl-1-butyn-3-yl. In the compound of any of the preceding embodiments, R3is preferably Ce-io aryl substituted by at least one F or C3-7 heteroaryl that is unsubstituted or substituted by at least one F. More preferably, R3is Ce aryl and the substituent is present in the 2-position, 3-position or 4-position relative to the attachment point of R3to the remainder of the molecule. R3may optionally be further substituted by one or more groups selected from F, Cl, Br, I, CN, NO2, C1-6 alkyl, C1-6 alkoxy and C3-6 cycloalkyl.

[0152] In a preferred embodiment, R3is Ce aryl substituted by at least one F, preferably in the 3-position or 4-position relative to the attachment point of R3to the remainder of the molecule, and optionally further substituted by one or more groups selected from F, Cl, Br, I, CN, NO2, C1-6 alkyl, C1-6 alkoxy and C3-6 cycloalkyl.In another preferred embodiment, R3is Ce aryl substituted by at least one F, preferably in the 3-position or 4-position relative to the attachment point of R3to the remainder of the molecule, and optionally fu rther substituted by one or more groups selected from halogen, CN, NO2, C1-6 alkyl, halogeno-Ci-6 alkyl, C1-6 alkoxy, halogeno-Ci-6 alkoxy, C1-6 alkylthio and halogeno-Ci-6 alkylthio, preferably wherein R3is unsubstituted Ce aryl or Ce aryl substituted by at least one of F, Cl, CH3, OCH3, OC2H5, SCH3 and CF3, and

[0153] R2is selected from C4-8 alkyl, (cyano)Ci-e alkyl, C1-6 alkoxy, C2-6 alkenyl, Cs ealkynyl, C3-6 cycloalkyl, (C3-6 cycloalkyl)Ci-3 alkyl, C2-8 heterocyclyl and (C2-8 heterocyclyl)Ci-3 alkyl, each of which may be optionally substituted by one or more groups selected from F, Cl, Br, I, CN, oxo, C1-6 alkyl, C1-6 alkoxy, (C1-ealkoxy)Ci-ealkyl, SO2R, C(O)R, CO2R, C(O)NR2, NR2 and SiRs, wherein each R is independently selected from H and C1-6 alkyl.

[0154] In another preferred embodiment, R3may be Ce aryl substituted by at least one F, preferably the substitution is in the 3-position or 4-position relative to the attachment point of R3to the remainder of the molecule, and R3may be optionally further substitute d by one or more groups selected from F, Cl, Br, I, CN, NO2, C1-6 alkyl, C1-6 alkoxy and C3-6 cycloalk yl, and R2is selected from C4-8 alkyl, (cyano)Ci-6 alkyl, C1-6 alkoxy, C2-6 alkenyl, Cs ealkynyl, C3-6 cycloalkyl, (C3-6 cycloalkyl)Ci-3 alkyl, C2-8 heterocyclyl and (C2-8 heterocyclyl)Ci-3 alkyl, each of which may b e optionally substituted by one or more groups selected from F, Cl, Br, I, CN, oxo, C1-6 alkyl, C1-6 alkoxy , (Ci-6alkoxy)Ci-6alkyl, SO2R, C(O)R, CO2R, C(O)NR2, NR2 and SiRs, wherein each R is independently selected from H, OH and C1-6 alkyl.

[0155] In a preferred embodiment, R3is selected from R3-1 to R3-139 as defined in Table 2, and R2, R1aand R1bare defined as in any of the preceding embodiments.

[0156] Table 2. Preferred R3group s

[0157]

[0158] <

[0159] "

[0160] <

[0161]

[0162] >

[0163] >

[0164]

[0165] ""

[0166] >

[0167]

[0168]

[0169] More preferably, R3is 4-fluorophenyl and R1a, R1band R2are defined as in any of the preceding embodiments.

[0170] In one preferred embodiment, R3is selected from 4-fluorophenyl, 4-chlorophenyl, 4-nitrophenyl, 4-(trifluoromethoxy)phenyl, 3,4-difluorophenyl, 2,4-difluorophenyl, 3-fluoro-4-chlorophenyl, 3-chloro-4-fluorophenyl, 4-fluoro-2-nitrophenyl, 4-fluoro-2-methylphenyl, 4-fluoro-2-methoxyphenyl, 2,4,5-trifluorophenyl, 2,3,4-trifluorophenyl, 2,4,6-trifluorophenyl, 2-chloro-4,6-difluorophenyl, 3-chloro-2,4-difluorophenyl, 2,6-dichloro-4-fluorophenyl and 2-chloro-4-fluoro-6-methylphenyl, preferably R3is selected from 4-fluorophenyl, 4-chlorophenyl, 4-nitrophenyl, 4-(trifluoromethoxy)phenyl, 3,4-difluorophenyl, 2,4-difluorophenyl, 3-fluoro-4-chlorophenyl and 3-chloro-4-fluorophenyl, more preferably R3is selected from 4-fluorophenyl, 3,4-difluorophenyl, 2,4-difluorophenyl, 3-fluoro-4-chlorophenyl and 3-chloro-4-fluorophenyl, and

[0171] R2is selected from C4-8 alkyl, (cyano)Ci-e alkyl, C1-6 alkoxy, C2-6 alkenyl, C2-6 alkynyl, C3-6 cycloalkyl, (C3-6 cycloalkyl)Ci-3 alkyl, C2-8 heterocyclyl and (C2-8 heterocyclyl)Ci-3 alkyl, each of which may be optionally substitut e d by one or more groups selected from F, Cl, Br, I, CN, oxo, C1-6 alkyl, C1-6 alkoxy, (C1-6alko xy)Ci-6alkyl, SO2R, C(O)R, CO2R, C(O)NR2, NR2 and SiRs, wherein each R is independently selected from H and C1-6 alkyl, and R1aand R1bare defined as in any of the preceding embodiments. In another embodiment, R3is 4-fluorophenyl, and R2is defined as in any of the preceding embodiments. In one embodiment, R2is selected from C4-8 alkyl, (cyano)Ci-e alkyl, C1-6 alkoxy, C2-6 alkenyl, C2-6 alkynyl, C3-6 cycloalkyl, (C3-6 cycloalkyl)Ci-3 alkyl, C2-8 heterocyclyl and (C2-8 heterocyclyl)Ci-3 alkyl, each of which may be optionally substituted by one or more groups selected from F, Cl, Br, I, CN, oxo, C1-6 alkyl, C1-6 alkoxy, (Ci-6alkoxy)Ci-6alkyl, SO2R, C(O)R, CO2R, C(O)NR2, NR2 and SiRs, wherein each R is independently selected from H and C1-6 alkyl, and R3is selected from 4-fluorophenyl, 3,4-difluorophenyl, 2,4-difluorophenyl, 3-fluoro-4-chlorophenyl and 3-chloro-4-fluorophenyl, preferably 4-fluorophenyl. In another embodiment, R2is selected from C4-8 alkyl, (cyano)Ci-e alkyl, C2-6 alkenyl, C2-6 alkynyl, (C3-6 cycloalkyl)Ci-3 alkyl and C3-6 cycloalkyl, preferably R2is selected from C4-8 alkyl, C2-6 alkenyl and C2-6 alkynyl, and R3is defined as in any of the preceding embodiments. More preferably, R2is selected from cyanomethyl, cyclopropyl, sec-butyl, 1-butyn-4-yl, 2-butyn-1-yl, prop-1 -yl, 3-methyl-1-butyn-3-yl, cyclopropylmethyl, 1 -trimethylsilyl-2-butyn-4-yl, 1-buten-4-yl, 1-buten-3-yl, 2-methyl-1-propen-3-yl, allyl, iso-butyl, tert-butyl, cyclopentyl, propargyl and 1-butyn-3-yl, even more preferably R2is selected from 1-butyn-4-yl, 2-butyn-1-yl, prop-1 -yl, 3-methyl-1-butyn-3-yl, allyl and propargyl, and R3is defined as in any of the preceding embodiments. Alternatively, R2is selected from C1-3 alkyl and R3is defined as in anyof the preceding embodiments. For example, R2is isopropyl and R3is defined as in any of the preceding embodiments.

[0172] In one embodiment, R2is selected from C1-3 alkyl, C4-8 alkyl, (cyano)Ci-e alkyl, C2-6 alkenyl, C2-ealkynyl, (C3-6 cycloalkyl)Ci-3 alkyl and C3-6 cycloalkyl, R3is selected from 4-fluorophenyl, 4-chlorophenyl, 4-nitrophenyl, 4-(trifluoromethoxy)phenyl, 3,4-difluorophenyl, 2,4-difluorophenyl, 3-fluoro-4-chlorophenyl, 3-chloro-4-fluorophenyl, 4-fluoro-2-nitrophenyl, 4-fluoro-2-methylphenyl, 4-fluoro-2-methoxyphenyl, 2,4,5-trifluorophenyl, 2,3,4-trifluorophenyl, 2,4,6-trifluorophenyl, 2-chloro-4,6-difluorophenyl, 3-chloro-2,4-difluorophenyl, 2,6-dichloro-4-fluorophenyl and 2-chloro-4-fluoro-6-methylphenyl, preferably R3is selected from 4-fluorophenyl, 4-chlorophenyl, 4-nitrophenyl, 4-(trifluoromethoxy)phenyl, 3,4-difluorophenyl, 2,4-difluorophenyl, 3-fluoro-4-chlorophenyl and 3-chloro-4-fluorophenyl, more preferably R3is selected from 4-fluorophenyl, 3,4-difluorophenyl, 2,4-difluorophenyl, 3-fluoro-4-chlorophenyl and 3-chloro-4-fluorophenyl. For example, in one embodiment, (i) R2is selected from cyanomethyl, cyclopropyl, sec-butyl, 1-butyn-4-yl, 2-butyn-1-yl, 3-methyl-1-butyn-3-yl, allyl, tert-butyl, cyclopentyl, propargyl, iso-butyl, 1-butyn-3-yl and 3-methylbut-2-yl, preferably R2is selected from 1-butyn-4-yl, 2-butyn-1-yl, 3-methyl-1-butyn-3-yl, allyl, propargyl and 1-butyn-3-yl, and R3is 4-fluorophenyl; or (ii) R2is isopropyl, and R3is selected from 3,4-difluorophenyl, 2,4-difluorophenyl, 3-fluoro-4-chlorophenyl and 3-chloro-4-fluorophenyl.

[0173] In a preferred embodiment, R2is selected from C4-8 alkyl, (cyano)Ci-e alkyl, C2-6 alkenyl, C2-ealkynyl, (C3-6 cycloalkyl)Ci-3 alkyl and C3-6 cycloalkyl, R3is selected from 4-fluorophenyl, 4-chlorophenyl, 4-nitrophenyl, 4-(trifluoromethoxy)phenyl, 3,4-difluorophenyl, 2,4-difluorophenyl, 3-fluoro-4-chlorophenyl, 3-chloro-4-fluorophenyl, 4-fluoro-2-nitrophenyl, 4-fluoro-2-methylphenyl, 4-fluoro-2-methoxyphenyl, 2,4,5-trifluorophenyl, 2,3,4-trifluorophenyl, 2,4,6-trifluorophenyl, 2-chloro-4,6-difluorophenyl, 3-chloro-2,4-difluorophenyl, 2,6-dichloro-4-fluorophenyl and 2-chloro-4-fluoro-6-methylphenyl, preferably R3is selected from 4-fluorophenyl, 4-chlorophenyl, 4-nitrophenyl, 4-(trifluoromethoxy)phenyl, 3,4-difluorophenyl, 2,4-difluorophenyl, 3-fluoro-4-chlorophenyl and 3-chloro-4-fluorophenyl, more preferably R3is selected from 4-fluorophenyl, 3,4-difluorophenyl, 2,4-difluorophenyl, 3-fluoro-4-chlorophenyl and 3-chloro-4-fluorophenyl. For example, R2is selected from cyanomethyl, cyclopropyl, sec-butyl, 1-butyn- 4-yl, 2-butyn-1-yl, 3-methyl-1-butyn-3-yl, allyl, tert-butyl, cyclopentyl, propargyl, iso-butyl, 1-butyn-3-yl and 3-methylbut-2-yl, preferably R2is selected from 1-butyn-4-yl, 2-butyn-1-yl, 3-methyl-1-butyn-3-yl, allyl, propargyl and 1-butyn-3-yl, and R3is 4-fluorophenyl.

[0174] In another preferred embodiment, the compound of formula I corresponds to Formula la and has a structure selected from the following Table 3, wherein the 16 compounds identified by * are excluded from the scope of the present invention, more preferably wherein the 16 compounds identified by * and the 7 compounds identified byAare excluded from the scope of the present invention, and most preferably wherein the 16 compounds identified by *, the 7 compounds identified byAand the 11 compounds identified by$are excluded from the scope of the present invention.

[0175]

[0176] [Formula la]

[0177] Table 3. Preferred compounds of Formula la.

[0178]

[0179]

[0180]

[0181]

[0182]

[0183]

[0184]

[0185]

[0186]

[0187]

[0188]

[0189]

[0190]

[0191]

[0192]

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203]

[0204]

[0205]

[0206]

[0207] In another preferred embodiment, the compound of formula I is any of the compounds of Example 1 to 132, such as any of the compounds of Example 1 to 126, or any of the compounds of Example 1 to 26.

[0208] In a preferred embodiment, the compound of formula la corresponds to the following compound of Formula la’:

[0209]

[0210] [Formula la‘]

[0211] wherein R2is selected from (i) allyl, (ii) propargyl, (iii) 1-butyn-3-yl (iv) 1-butyn-4-yl, (v) 2-butyn-1-yl, (vi) prop-1 -yl and (vii) 3-methyl-1-butyn-3-yl.

[0212] Alternatively, the compound of formula la corresponds to the following compound:

[0213]

[0214] [Formula la‘]

[0215] wherein R2is selected from: (i) allyl, (ii) propargyl, (iii) 1-butyn-4-yl and (iv) 2-butyn-1-yl.

[0216] In another preferred embodiment, the compound is represented by the Formula I, wherein:

[0217] - R2is isopropyl, propargyl, allyl or methyl;

[0218] and

[0219] R3 is selected from:

[0220] (i) 3,4-difluorophenyl;

[0221] (ii) 2,4-difluorophenyl;(iii) 3-fluoro-4-chlorophenyl;

[0222] (iv) 3-chloro-4-fluorophenyl;

[0223] (v) 4-fluorophenyl;

[0224] (vi) 3-methyl-4-fluorophenyl;

[0225] (vii) 2,4,5-trifluorophenyl;

[0226] (viii) 2,3,4-trifluorophenyl;

[0227] (ix) 3,4,5-trifluorophenyl;

[0228] (x) 3-fluoro-4-methylphenyl;

[0229] (xi) 3-bromo-4-fluorophenyl;

[0230] (xii) 2-fluoro-4-chlorophenyl;

[0231] (xiii) 2-methyl-4-fluorophenyl;

[0232] (xiv) 3-methoxy-4-fluorophenyl;

[0233] (xv) 2-fluoro-4-methylphenyl; and

[0234] (xvi) 3-fluoro-4-cyanophenyl,

[0235] or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, or a tautomer thereof.

[0236] Most preferably, the compound of formula I corresponds to a compound of formula la where:

[0237] R2is propargyl (R2-7) and R3is 4-fluorophenyl (R3-1) (i.e. compound I-7);

[0238] R2is isopropyl (R2-9) and R3is 2,4-difluorophenyl (R3-26) (i.e. compound I-284);

[0239] R2is methyl (R2-64) and R3is 3,4-difluorophenyl (R3-4) (i.e. compound VII-34);

[0240] R2is propargyl (R2-7) and R3is 3,4-difluorophenyl (R3-4) (i.e. compound I-40);

[0241] R2is allyl (R2-4) and R3is 3,4-difluorophenyl (R3-4) (i.e. compound I-37);

[0242] R2is methyl (R2-64) and R3is 2-methyl-4-fluorophenyl (R3-29) (i.e. compound VII-309);

[0243] R2is isopropyl (R2-9) and R3is 3-methyl-4-fluorophenyl (R3-9) (i.e. compound I-97);

[0244] R2is propargyl (R2-7) and R3is 3-methyl-4-fluorophenyl (R3-9) (i.e. compound I-95);

[0245] R2is allyl (R2-4) and R3is 3-methyl-4-fluorophenyl (R3-9) (i.e. compound I-92);

[0246] R2is isopropyl (R2-9) and R3is 2,4,5-trifluorophenyl (R3-31) (i.e. compound I-339); or

[0247] R2is methyl (R2-64) and R3is 2,4,5-trifluorophenyl (R3-31) (i.e. compound VI 1-331 ), for example I-7 or I-284.

[0248] In some embodiments, the compound of formula I may contain asymmetric centres and may be present as a single enantiomer, a pair of enantiomers in any proportion or, where more than one asymmetric center is present, contain diastereomers in all possible ratios. In case the compound of formula I contains one or more double bonds, the one or more double bonds may each independently exist in (E)- or (Z)-configuration. Any stereoisomers, enantiomers, geometric isomers, as well as tautomers of the compound of formula I are also encompassed by the present invention.

[0249] In addition, the compound of formula I may form agrochemically acceptable salts which are also covered by the present invention. Suitable salts include, but are not limited to, salts of acceptable inorganic acids such as hydrochloric, sulfuric, phosphoric, nitric, carbonic, boric, sulfamic, and hydrobromic acids, or salts of agronomically, agriculturally or horticulturally acceptable organic acids such as acetic, propionic, butyric, tartaric, maleic, hydroxymaleic, fumaric, malic, citric, lactic, mucic, gluconic, benzoic, succinic, oxalic, phenylacetic, methanesulfonic, toluenesulfonic, benzenesulfonic, salicylic, sulfanilic, aspartic, glutamic, edetic, stearic, palmitic, oleic, lauric, pantothenic, tannic, ascorbic and valeric acids. Suitable salts also include salts of inorganic and organic bases, e.g. counterions such as Na, Ca, K, Li, Mg,ammonium, and trimethylsulfonium. In addition, any isotopes including deuterated compounds are covered by the compound of formula I.

[0250] Compositions comprising one or more compounds of formula I

[0251] The compounds of formula I according to the invention can be used as herbicides by themselves, but they can also be formulated into compositions. Therefore, in a second aspect, the present invention provides a composition comprising one or more compounds of formula I or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof or a tautomer thereof, and one or more auxiliary and / or adjuvant, and optionally one or more further active ingredients. In a certain embodiment, the composition comprising one or more compounds of formula I is an agrochemical composition.

[0252] The compositions can be in various physical forms, e.g., in the form of dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent pellets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, oil-flowables, aqueous dispersions, oily dispersions, suspo-emulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates. Such compositions can either be used directly or diluted prior to use. The dilutions can be made, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.

[0253] The compositions according to the second aspect of the invention are prepared in a known manner, by mixing the compounds of the formula I with the one or more adjuvants, and optionally one or more other active ingredients. In addition, the composition may comprise further additives that are conventional in this technical field, including but not limited to colorants, wetting agents, dispersants, emulsifiers, antifoams, preservatives, secondary thickeners, adhesives, gibberellins and water.

[0254] For example, the compositions can be prepared e.g., by mixing a compound according the first aspect of the present invention as the active ingredient with the adjuvants) in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions. The active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof. The active ingredients can also be contained in very fine microcapsules. Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g., slow-release).

[0255] Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95% by weight of the capsule weight. The active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution. The encapsulating membranes can comprise, for example, natural or synthetic rubbers, cellulose, styrene / butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art. Alternatively, very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated.

[0256] (a) Adjuvants

[0257] The adjuvants that are suitable for the preparation of the compositions according to the second aspect of the present invention are known in this technical field.

[0258] As liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid,diacetone alcohol, 1 ,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, / V, / V-dimethylformamide, dimethyl sulfoxide, 1 ,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1 ,1 ,1 -trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxy-propanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and alcohols of higher molecular weight, such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone and the like.

[0259] Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances.

[0260] A large number of surface-active substances can be used in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier prior to use. Surface-active substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol / alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol / alkylene oxide addition products, such as tridecylalcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and di-alkylphosphate esters; and also further substances described e.g., in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood New Jersey (1981).

[0261] Further adjuvants that can be used in herbicidal formulations include crystallisation inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides, and liquid and solid fertilisers.

[0262] The compositions according to the second aspect of the present invention can further include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives. The amount of oil additive in the composition according to the invention is generally from 0.01 to 10%, based on the mixture to be applied. For example, the oil additive can be added to a spray tank in the desired concentration after a spray mixture has been prepared. Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow. Preferred oil additives comprise alkyl esters of C8-C22 fatty acids, especially the methyl derivatives of C12-C18 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyloleate, respectively). Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10thEdition, Southern Illinois University, 2010.

[0263] The inventive compositions generally comprise from 0.1 to 99% by weight, especially from 0.1 to 95% by weight, of compounds of the present invention and from 1 to 99.9% by weight of a formulation adjuvant which preferably includes from 0 to 25% by weight of a surface-active substance.

[0264] Formulation types for the composition of the invention include an emulsion concentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EG), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP), a soluble granule (SG) or any technically feasible formulation in combination with agriculturally or horticulturally acceptable adjuvants. Whereas commercial products may preferably be formulated as concentrates, the end user will normally employ dilute formulations.

[0265] The rates of application vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the species to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop. As a general guideline, compounds may be applied at a rate of from 1 to 2000 l / ha, especially from 10 to 1000 l / ha.

[0266] Agrochemical combinations

[0267] The compounds according to the first aspect of the present invention and the composition according to the second aspect of the present invention may also be used with further active ingredients. Therefore, in another aspect of the present invention, it is provided an agrochemical combination comprising the compound according to the first aspect of the present invention or the composition according to the second aspect of the present invention and one or more additional herbicides and / or plant growth regulators.

[0268] Examples of such additional herbicides or plant growth regulators include acetochlor, acifluorfen (including acifluorfen-sodium), aclonifen, ametryn, amicarbazone, aminopyralid, aminotriazole, atrazine, beflubutamid-M, benquitrione, bensulfuron (including bensulfuron-methyl), bentazone, bicyclopyrone, bifenox, bilanafos, bipyrazone, bispyribac-sodium, bixlozone, bromacil, bromoxynil, butachlor, butafenacil, carfentrazone (including carfentrazone-ethyl), cloransulam (including cloransulam-methyl), chlomethoxyfen, chlorimuron (including chlorimuron-ethyl), chlorotoluron, chlorsulfuron, cinmethylin, cinflubrolin, clacyfos, clethodim, clodinafop (including clodinafop-propargyl), clomazone, clopyralid, cyclopyranil, cyclopyrimorate, cyclosulfamuron, cyhalofop (including cyhalofop-butyl), 2,4-D (including the choline salt and 2-ethylhexyl ester thereof), 2,4-DB, desmedipham, dicamba (including the aluminium, aminopropyl, bis-aminopropylmethyl, choline, dichloroprop, diglycolamine, dimethylamine, dimethylammonium, potassium and sodium salts thereof) diclosulam, diflufenican, diflufenzopyr, dimethachlor, dimethenamid-P, dioxopyritrione, diquat dibromide, diuron, epyrifenacil, ethalfluralin.ethofumesate, fenoxaprop (including fenoxaprop-P-ethyl), fenoxasulfone, fenpyrazone, fenquinotrione, fentrazamide, feproxydim, flazasulfuron, florasulam, florpyrauxifen (including florpyrauxifen-benzyl), fluazifop (including fluazifop-P-butyl), flucarbazone (including flucarbazone-sodium), , flumetsulam, flumioxazin, fluometuron, fomesafen flupyrsulfuron (including flupyrsulfuron-methyl-sodium), fluroxypyr (including fluroxypyr-meptyl), fomesafen, foramsulfuron, glufosinate (including L-glufosinate and the ammonium salts of both), glyphosate (including the diammonium, isopropylammonium and potassium salts thereof), halauxifen (including halauxifen-methyl), haloxyfop (including haloxyfop-methyl), hexazinone, hydantocidin, imazamox (including R-imazamox), imazapic, imazapyr, imazethapyr, indaziflam, iodosulfuron (including iodosulfuron-methyl-sodium), iofensulfuron (including iofensulfuron-sodium), ioxynil, isoproturon, isoxafenacil, isoxaflutole, lancotrione, MCPA, MCPB, mecoprop-P, mesosulfuron (including mesosulfuron-methyl), mesotrione, metamitron,metazachlor, methiozolin, metolachlor, metosulam, metribuzin, metsulfuron, napropamide, nicosulfuron, nonanoic acid, norflurazon, oxadiazon, oxasulfuron, oxyfluorfen, paraquat dichloride, pendimethalin, penoxsulam, phenmedipham, picloram, pinoxaden, pretilachlor, primisulfuron-methyl, prometryne, propanil, propaquizafop, propyrisulfuron, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen (including pyraflufen-ethyl), pyraquinate, pyrasulfotole, pyridate, pyriflubenzoxim, pyriftalid, pyrimisulfan, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quizalofop (including quizalofop-P-ethyl and quizalofop-P-tefuryl), rimisoxafen, rimsulfuron, saflufenacil, sethoxydim, simazine, S-metalochlor, sulfentrazone, sulfosulfuron, tebuthiuron, tefuryltrione, tembotrione, terbuthylazine, terbutryn, tetflupyrolimet, thiencarbazone, thifensulfuron, tiafenacil, tolpyralate, topramezone, tralkoxydim, triafamone, triallate, triasulfuron, tribenuron (including tribenuron-methyl), triclopyr, trifloxysulfuron (including trifloxysulfuron-sodium), trifludimoxazin, trifluralin, triflusulfuron, tripyrasulfone, 3-(2- chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenyl)-5-methyl-4,5-dihydroisoxazole-5-carboxylic acid ethyl ester, 4-hydroxy-1 -methoxy-5-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 4-hydroxy-1 ,5-dimethyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 5-ethoxy-4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 4-hydroxy-1 ,5-dimethyl-3-[1 -methyl-5- (trifluoromethyl)pyrazol-3-yl]imidazolidin-2-one, (4R)1-(5-tert-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl-imidazolidin-2-one, 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid (including agrochemically acceptable esters thereof, for example, methyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1 H-indol-6-yl)pyridine-2-carboxylate, prop-2-ynyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1 H-indol-6-yl)pyridine-2-carboxylate and cyanomethyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1 H-indol-6-yl)pyridine-2-carboxylate), 3-ethylsulfanyl-N-(1 ,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)- [1 ,2,4]triazolo[4,3-a]pyridine-8-carboxamide, 3-(isopropylsulfanylmethyl)-N-(5-methyl-1 ,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide, 3-(isopropylsulfonylmethyl)-N-(5-methyl-'l,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1 ,2,4]triazolo[4,3-a]pyridine-8-carboxamide, 3-(ethylsulfonylmethyl)-N-(5-methyl-1 ,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1 ,2,4]triazolo[4,3-a]pyridine-8-carboxamide, ethyl-2-[[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]acetate,6-chloro-4-(2,7-dimethyl-1-naphthyl)-5-hydroxy-2-methyl-pyridazin-3-one, tetrahydrofuran-2-ylmethyl (2R)-2-[(4-amino-3,5-dichloro-6-fluoro-2-pyridyl)oxy]propanoate, tetrahydrofuran-2-ylmethyl (2R)-2-[(4-amino-3,5-dichloro-6-fluoro-2-pyridyl)oxy]propanoate, tetrahydrofuran-2-ylmethyl 2-[(4-amino-3,5-dichloro-6-fluoro-2-pyridyl)oxy]propanoate, 2-[(4-amino-3,5-dichloro-6-fluoro-2-pyridyl)oxy]propanoic acid, 2-fluoro-N-(5-methyl-1 ,3,4-oxadiazol-2-yl)-3-[(R)-propylsulfinyl]-4-(trifluoromethyl)benzamide, 2-fluoro-N-(5-methyl-1 ,3,4-oxadiazol-2-yl)-3-propylsulfinyl-4-(trifluoromethyl)benzamide, (2-fluorophenyl)methyl 6-amino-5-chloro-2-(4-chloro-2-fluoro-3-methoxy-phenyl)pyrimidine-4-carboxylate and 6-amino-5-chloro-2-(4-chloro-2-fluoro-3-methoxy-phenyl)pyrimidine-4-carboxylic acid.

[0269] Use of the compounds and compositions

[0270] It was surprisingly found that compounds of formula I exhibit a desirable effect acting as a herbicide. Therefore, in a third aspect, the present invention provides the use of the compound according to the first aspect or the composition according to the second aspect in agriculture or horticulture, preferably as a herbicide.

[0271] For example, the compound of the first aspect or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof or a tautomer thereof, or a composition according to the second aspect may be used as a herbicide on crops selected from cereals including barley (e.g. winter barley, HORVW) and wheat (e.g. winter wheat, TRAZW), cotton, oilseed rape, sunflower, maize (e.g. Zea mays, ZEAMX), rice, soybeans, sugar beet, sugar cane, turf, trees including fruit trees, palm trees, coconut trees or other nuts, vines including grapes, fruit bushes, fruit plants, and vegetables including potatoes and tomatoes.

[0272] Preferably, the compound of the first aspect or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof or a tautomer thereof, or acomposition according to the second aspect is used as a herbicide, more preferably a pre-emergence herbicide, even more preferably a broad-spectrum herbicide, against a monocotyledonous plant (i.e. from the plant clade Monocots) and / or a dicotyledonous plant (i.e. from the plant clade Eudicots). In an exemplary embodiment, the compound of the first aspect or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof or a tautomer thereof, ora composition according to the second aspect is used against species selected from blackgrass, wild oat, Fat Hen, Crabgrass, Barnyard grass, cut-leaved crane's-bill, Italian ryegrass, Common Millet, green foxtail and Black nightshade. For example, it may be used against species selected from Alopecurus myosuroides (ALOMY), Apera spica-venti (APESV), Avena fatua (AVEFA), Chenopodium album (CHEAL), Digitaria sanguinalis (DIGSA), Echinochloa crus-galli (ECHCG), Geranium dissectum (GERDI), Lolium multiflorum (LOLMU), Panicum miliaceum (PANMI), Poa annua (POAAN), Setaria viridis (SETVI) and Solanum nigrum (SOLN I).

[0273] In a more preferred embodiment, the compound of the first aspect or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof or a tautomer thereof, ora composition according to the second aspect is used against a species from a genus selected from the group consisting of: Abutilon, Alopecurus, Amaranthus, Ambrosia, Apera, Avena, Brachiaria, Brassica, Bromus, Capsella, Caucalis, Chenopodiastrum, Chenopodium, Chloris, Chrozophora, Cirsium, Commelina, Consolida, Convolvulus, Conyza, Cynodon, Cyperus, Datura, Descurainia, Digitaria, Echinochloa, Eleusine, Elymus, Elytrigia, Equisetum, Erigeron, Fallopia, Fumaria, Galeopsis, Galinsoga, Galium, Geranium, Gomphrena, Helianthus, Hibiscus, Hirschfeldia, Humulus, Ipomoea, Kochia, Lamium, Lapsana, Linaria, Lolium, Malva, Matricaria, Myosotis, Panicum, Papaver, Persicaria, Phalaris, Phragmites, Physalis, Phytolacca, Plantago, Poa, Polygonum, Portulaca, Ranunculus, Raphanus, Rapistrum, Rumex, Senecio, Senna, Setaria, Sinapis, Sisymbrium, Solanum, Sonchus, Sorghum, Spermacoce, Stellaria, Taraxacum, Toxicodendron, Tribulus, Tripleurospermum, Tussilago, Urochloa, Urtica, Veronica, Viola, and Xanthium.

[0274] More preferably, the compound of the first aspect or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof or a tautomer thereof, or a composition according to the second aspect is used against a species selected from the group consisting of Abutilon theophrasti (ABUTH), Alopecurus myosuroides (ALOMY), Amaranthus albus (AMAAL), Amaranthus blitoides (AMABL), Amaranthus blitum (AMALI), Amaranthus hybridus (AMACH), Amaranthus palmeri (AMAPA), Amaranthus powellii (AM APO), Amaranthus retroflexus (AMARE), Amaranthus sp. (AMASS), Amaranthus spinosus (AM ASP), Amaranthus tuberculatus (AMATU), Amaranthus viridis (AM AVI), Ambrosia artemisiifolia (AMBEL), Ambrosia trifida (AMBTR), Apera spica-venti (APESV), Avena fatua (AVEFA), Brachiaria platyphylla (BRAPP), Brassica napus (BRSNN), Brassica rapa (BRSRR), Brassica sp. (BRSSS), Bromus catharticus (BROCA), Bromus tectorum (BROTE), Capsella bursa-pastoris (CAPBP), Caucalis platycarpos (CUCLA), Chenopodiastrum murale (CHEMU), Chenopodium album (CHEAL), Chenopodium vulvaria (CHEVU), Chloris sp. (CHRSS), Chrozophora tinctoria (CRZTI), Cirsium arvense (CIRAR), Commelina benghalensis (COMBE), Commelina erecta (COMER), Consolida regalis (CONRE), Convolvulus arvensis (CONAR), Conyza bonariensis (ERIBO), Conyza sp. (CNDSS), Conyza sumatrensis (ERISU), Cynodon dactylon (CYNDA), Cynodon hirsutus (CYNHI), Cynodon sp. (CYNSS), Cyperus esculentus (CYPES), Cyperus rotundus (CYPRO), Datura stramonium (DATST), Descurainia pinnata (DESPI), Descurainia sophia (DESSO), Digitaria sanguinalis (DIGSA), Digitaria sanquinalis (DIGSA), Echinochloa colona (ECHCO), Echinochloa coIonum (ECHCO), Echinochloa crus-galli (ECHCG), Echinochloa sp. (ECHSS), Eleusine indica (ELEIN), Elymus repens (ELYRE), Elytrigia repens (AGRRE), Equisetum arvense (EQUAR), Erigeron annuus (ERIAN), Erigeron bonariensis (ERIBO), Erigeron canadensis (ERICA), Erigeron floribundus (ERIFL), Fallopia convolvulus (FALCO), Fumaria officinalis (FUMOF), Galeopsis spp. (GALSP), Galinsoga parviflora (GASPA), Galinsoga quadriradiata (GASCI), Galium aparine (GALAP), Galium spurium (GALSU), Galium tricornutum (GALTC), Geranium dissectum (GERDI), Gomphrena sp. (GOMSS), Helianthus annuus (HELAN), Hibiscus trionum (HIBTR), Hirschfeldia incana (HISIN), Humulus lupulus (HUMLU), Ipomoea cordatotriloba (IPOTC), Ipomoea hederacea (IPOHE), Ipomoea heptaphylla (IPOWR), Ipomoealacunosa (IPOLA), Ipomoea muricata (CLYMU), Ipomoea purpurea (PHBPU), Ipomoea tricolor (IPOTO), Kochia sp. (KCHSS), Lamium hybridum (LAMHY), Lamium spp. (LAMSP), Lapsana communis (LAPCO), Linaria vulgaris (LINVU), Lolium multiflorum (LOLMU), Lolium perenne (LOLPE), Lolium sp. (LOLSS), Malva sylvestris (MALSY), Matricaria discoidea (MATDI), Myosotis arvensis (MYOAR), Panicum miliaceum (PANMI), Papaver rhoeas (PAPRH), Persicaria lapathifolia (PERLA), Persicaria maculosa (PERMA), Phalaris brachystachys (PHABR), Phalaris minor (PHAMI), Phalaris paradoxa (PHAPA), Phragmites australis (PHRAU), Physalis acutifolia (PHYWR), Phytolacca americana (PHUAM), Plantago lanceolata (PLALA), Plantago major (PLAMA), Poa annua (POAAN), Poa trivialis (POATR), Polygonum aviculare (POLAV), Polygonum persicaria (POLPE), Portulaca oleracea (POROL), Ranunculus repens (RANRE), Raphanus sativus (RAPSR), Rapistrum rugosum (RASRU), Rumex acetosella (RUMAC), Rumex crispus (RUMCR), Rumex obtusifolius (RUMOB), Senecio vulgaris (SENVU), Senna tora (CASTO), Setaria faberi (SETFA), Setaria magna (SETMG), Setaria pumila (SETLU), Setaria pumila (SETPU), Setaria verticillata (STEVE), Setaria viridis (SETVI), Sinapis arvensis (SINAR), Sisymbrium altissimum (SSYAL), Solanum americanum (SOLAM), Solanum carolinense (SOLCA), Solanum nigrum (SOLNI), Sonchus arvensis (SONAR), Sonchus oleraceus (SONOL), Sorghum halepense (SORHA), Spermacoce sp. (SPCSS), Stellaria media (STEME), Taraxacum officinale (TAROF), Toxicodendron radicans (TOXRA), Tribulus terrestris (TRBTE), Tripleurospermum inodorum (MATIN), Tussilago farfara (TUSFA), Urochloa panicoides (UROPA), Urochloa texana (PANTE), Urtica dioica (URTDI), Veronica arvensis (VERAR), Veronica hederifolia (VERHE), Veronica persica (VERPE), Viola arvensis (VIOAR), and Xanthium spinosum (XANSP). More preferably, the compound of the first aspect or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof or a tautomer thereof, or a composition according to the second aspect is used against a species selected from the group consisting of Alopecurus myosuroides (ALOMY), Apera spica-venti (APESV), Avena fatua (AVEFA), Chenopodium album (CHEAL), Digitaria sanguinalis (DIGSA), Echinochloa crus-galli (ECHCG), Geranium dissectum (GERDI), Lolium multiflorum (LOLMU), Panicum miliaceum (PANMI), Poa annua (POAAN), Setaria viridis (SETVI), and Solanum nigrum (SOLNI).

[0275] In a more preferred embodiment on European territory, the compound of the first aspect or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof or a tautomer thereof, or a composition according to the second aspect is used against a species from a genus selected from the group consisting of: Abutilon, Alopecurus, Amaranthus, Ambrosia, Apera, Capsella, Caucalis, Chenopodium, Chrozophora, Cirsium, Consolida, Convolvulus, Cyperus, Datura, Echinochloa, Eleusine, Elymus, Elytrigia, Fallopia, Fumaria, Galeopsis, Galium, Helianthus, Hibiscus, Humulus, Lamium, Lapsana, Linaria, Lolium, Malva, Matricaria, Myosotis, Panicum, Papaver, Persicaria, Phalaris, Phragmites, Phytolacca, Plantago, Poa, Polygonum, Portulaca, Ranunculus, Rumex, Senecio, Setaria, Sinapis, Sonchus, Sorghum, Stellaria, Taraxacum, Tribulus, Tripleurospermum, Tussilago, Urtica, Veronica, Viola, and Xanthium.

[0276] In a more preferably first alternative of the preferred embodiment on European territory, the compound of the first aspect or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof or a tautomer thereof, or a composition according to the second aspect is used against a species selected from the group consisting of Abutilon theophrasti (ABUTH), Alopecurus myosuroides (ALOMY), Amaranthus powellii (AM APO), Amaranthus retroflexus (AM ARE), Amaranthus viridis (AMAVI), Ambrosia artemisiifolia (AMBEL), Apera spica-venti (APESV), Avena fatua (AVEFA), Capsella bursa-pastoris (CAPBP), Caucalis platycarpos (CUCLA), Chenopodium album (CHEAL), Chenopodium vulvaria (CHEVU), Chrozophora tinctoria (CRZTI) Cirsium arvense (CIRAR), Consolida regalis (CONRE), Convolvulus arvensis (CONAR), Cyperus rotundus (CYPRO), Datura stramonium (DATST), Digitaria sanguinalis (DIGSA), Echinochloa crus-galli (ECHCG), Elymus repens (ELYRE), Elytrigia repens (AGRRE), Fallopia convolvulus (FALCO), Fumaria officinalis (FUMOF), Galeopsis spp. (GALSP), Galium aparine (GALAP), Galium spurium (GALSU), Galium tricornutum (GALTC), Geranium dissectum (GERDI), Helianthus annuus (HELAN), Hibiscus trionum (HIBTR), Humulus lupulus (HUMLU), Lamium hybridum (LAMHY), Lamium spp. (LAMSP), Lapsana communis (LAPCO), Linariavulgaris (LINVU), Lolium multiflorum (LOLMU), Lolium spp. (LOLOL), Malva sylvestris (MALSY), Matricaria discoidea (MATDI), Myosotis arvensis (MYOAR), Panicum miliaceum (PAN Ml), Papaver rhoeas (PAPRH), Persicaria lapathifolia (PERLA), Persicaria maculosa (PERMA), Phalaris brachystachys (PHABR), Phalaris minor (PHAMI), Phalaris paradoxa (PHAPA), Phragmites australis (PHRAU), Phytolacca americana (PHUAM), Plantago lanceolata (PLALA), Plantago major (PLAMA), Poa annua (POAAN), Poa trivialis (POATR), Polygonum aviculare (POLAV), Polygonum persicaria (POLPE), Portulaca oleracea (POROL), Ranunculus repens (RANRE), Rumex acetosella (RUMAC), Rumex crispus (RUMCR), Rumex obtusifolius (RUMOB), Senecio vulgaris (SENVU), Setaria pumila (SETLU), Setaria viridis (SETVI), Sinapis arvensis (SINAR), Solanum nigrum (SOLNI), Sonchus arvensis (SONAR), Sorghum halepense (SORHA), Stellaria media (STEME), Taraxacum officinale (TAROF), Tribulus terrestris (TRBTE), Tripleurospermum inodorum (MATIN), Tussilago farfara (TUSFA), Urtica dioica (URTDI), Veronica arvensis (VERAR), Veronica hederifolia (VERHE), Veronica persica (VERPE), Viola arvensis (VIOAR), and Xanthium spinosum (XANSP). In an even more preferably first alternative of the preferred embodiment on European territory, the compound of the first aspect or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof or a tautomer thereof, or a composition according to the second aspect is used against a species selected from the group consisting of Alopecurus myosuroides (ALOMY), Apera spica-venti (APESV), Avena fatua (AVEFA), Chenopodium album (CHEAL), Digitaria sanguinalis (DIGSA), Echinochloa crus-galli (ECHCG), Geranium dissectum (GERDI), Lolium multiflorum (LOLMU), Panicum miliaceum (PANMI), Poa annua (POAAN), Setaria viridis (SETVI), and Solanum nigrum (SOLNI).

[0277] In a more preferably second alternative of the preferred embodiment on European territory, the compound of the first aspect or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof or a tautomer thereof, or a composition according to the second aspect is used against a species selected from the group consisting of Abutilon theophrasti (ABUTH), Alopecurus myosuroides (ALOMY), Amaranthus powellii (AMAPO), Amaranthus retroflexus (AMARE), Amaranthus viridis (AMAVI), Ambrosia artemisiifolia (AMBEL), Apera spica-venti (APESV), Capsella bursa-pastoris (CAPBP), Caucalis platycarpos (CUCLA), Chenopodium album (CHEAL), Chenopodium vulvaria (CHEVU), Chrozophora tinctoria (CRZTI) Cirsium arvense (CIRAR), Consolida regalis (CONRE), Convolvulus arvensis (CONAR), Cyperus rotundus (CYPRO), Datura stramonium (DATST), Echinochloa crus-galli (ECHCG), Elymus repens (ELYRE), Elytrigia repens (AGRRE), Fallopia convolvulus (FALCO), Fumaria officinalis (FUMOF), Galeopsis spp. (GALSP), Galium aparine (GALAP), Galium spurium (GALSU), Galium tricornutum (GALTC), Geranium dissectum (GERDI), Helianthus annuus (HELAN), Hibiscus trionum (HIBTR), Humulus lupulus (HUMLU), Lamium hybridum (LAMHY), Lamium spp. (LAMSP), Lapsana communis (LAPCO), Linaria vulgaris (LINVU), Lolium spp. (LOLOL), Malva sylvestris (MALSY), Matricaria discoidea (MATDI), Myosotis arvensis (MYOAR), Panicum miliaceum (PANMI), Papaver rhoeas (PAPRH), Persicaria lapathifolia (PERLA), Persicaria maculosa (PERMA), Phalaris brachystachys (PHABR), Phalaris minor (PHAMI), Phalaris paradoxa (PHAPA), Phragmites australis (PHRAU), Phytolacca americana (PHUAM), Plantago lanceolata (PLALA), Plantago major (PLAMA), Poa annua (POAAN), Poa trivialis (POATR), Polygonum aviculare (POLAV), Polygonum persicaria (POLPE), Portulaca oleracea (POROL), Ranunculus repens (RANRE), Rumex acetosella (RUMAC), Rumex crispus (RUMCR), Rumex obtusifolius (RUMOB), Senecio vulgaris (SENVU), Setaria pumila (SETLU), Sinapis arvensis (SINAR), Sonchus arvensis (SONAR), Sorghum halepense (SORHA), Stellaria media (STEME), Taraxacum officinale (TAROF), Tribulus terrestris (TRBTE), Tripleurospermum inodorum (MATIN), Tussilago farfara (TUSFA), Urtica dioica (URTDI), Veronica arvensis (VERAR), Veronica hederifolia (VERHE), Veronica persica (VERPE), Viola arvensis (VIOAR), and Xanthium spinosum (XANSP). In an even more preferably first alternative of the preferred embodiment on European territory, the compound of the first aspect or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof or a tautomer thereof, or a composition according to the second aspect is used against a species selected from the group consisting of Alopecurus myosuroides (ALOMY), Apera spica-venti (APESV), Chenopodium album (CHEAL), Echinochloa crus-galli (ECHCG), Geranium dissectum (GERDI), Panicum miliaceum (PANMI), and Poa annua (POAAN).In a more preferred embodiment on North American territory, the compound of the first aspect or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof or a tautomer thereof, or a composition according to the second aspect is used against a species from a genus selected from the group consisting of: Amaranthus, Ambrosia, Avena, Brachiaria, Brassica, Bromus, Chenopodiastrum, Chenopodium, Cirsium, Commelina, Convolvulus, Cyperus, Descurainia, Digitaria, Echinochloa, Eleusine, Equisetum, Erigeron, Galinsoga, Ipomoea, Kochia, Physalis, Portulaca, Senna, Setaria, Sinapis, Sisymbrium, Solanum, Sorghum, Taraxacum, Toxicodendron, and Urochloa.

[0278] In a more preferably first alternative of the preferred embodiment on North American territory, the compound of the first aspect or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof or a tautomer thereof, or a composition according to the second aspect is used against a species selected from the group consisting of Amaranthus albus (AMAAL), Amaranthus blitoides (AMABL), Amaranthus hybridus (AMACH), Amaranthus blitum (AMALI), Amaranthus blitum (AMALI), Amaranthus palmeri (AMAPA), Amaranthus powellii (AMAPO), Amaranthus retroflexus (AMARE), Amaranthus spinosus (AMASP), Amaranthus tuberculatus (AMATU), Ambrosia artemisiifolia (AMBEL), Ambrosia trifida (AMBTR), Alopecurus myosuroides (ALOMY), Apera spica-venti (APESV), Avena fatua (AVEFA), Brachiaria platyphylla (BRAPP), Bromus tectorum (BROTE), Brassica napus (BRSNN), Senna tora (CASTO), Chenopodium album (CHEAL), Chenopodiastrum murale (CHEMU), Cirsium arvense (CIRAR), Ipomoea muricata (CLYMU), Commelina benghalensis (COMBE), Convolvulus arvensis (CONAR), Cyperus esculentus (CYPES), Cyperus rotundus (CYPRO), Descurainia pinnata (DESPI), Descurainia pinnata (DESPI), Descurainia sophia (DESSO), Digitaria sanguinalis (DIGSA), Echinochloa crus-galli (ECHCG), Echinochloa coIonum (ECHCO), Eleusine indica (ELEIN), Equisetum arvense (EQUAR), Erigeron annuus (ERIAN), Erigeron bonariensis (ERIBO), Erigeron canadensis (ERICA), Erigeron floribundus (ERIFL), Galinsoga quadriradiata (GASCI), Galinsoga parviflora (GASPA), Geranium dissectum (GERDI), Lolium multiflorum (LOLMU), Ipomoea hederacea (IPOHE), Ipomoea lacunosa (IPOLA), Ipomoea cordatotriloba (IPOTC), Ipomoea tricolor (IPOTO), Ipomoea heptaphylla (IPOWR), Kochia sp. (KCHSS), Urochloa texana (PANTE), Ipomoea purpurea (PHBPU), Panicum miliaceum (PANMI), Physalis acutifolia (PHYWR), Poa annua (POAAN), Portulaca oleracea (POROL), Setaria faberi (SETFA), Setaria magna (SETMG), Setaria pumila (SETPU), Setaria viridis (SETVI), Sinapis arvensis (SINAR), Solanum americanum (SOLAM), Solanum carolinense (SOLCA), Solanum nigrum (SOLNI), Sorghum halepense (SORHA), Sisymbrium altissimum (SSYAL), Setaria verticillata (STEVE), Taraxacum officinale (TAROF), and Toxicodendron radicans (TOXRA). In an even more preferably first alternative of the preferred embodiment on North American territory, the compound of the first aspect or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof or a tautomer thereof, or a composition according to the second aspect is used against a species selected from the group consisting of Alopecurus myosuroides (ALOMY), Apera spica-venti (APESV), Avena fatua (AVEFA), Chenopodium album (CHEAL), Digitaria sanguinalis (DIGSA), Echinochloa crus-galli (ECHCG), Geranium dissectum (GERDI), Lolium multiflorum (LOLMU), Panicum miliaceum (PANMI), Poa annua (POAAN), and Setaria viridis (SETVI). In a more preferably second alternative of the preferred embodiment on North American territory, the compound of the first aspect or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof or a tautomer thereof, or a composition according to the second aspect is used against a species selected from the group consisting of Amaranthus albus (AMAAL), Amaranthus blitoides (AMABL), Amaranthus hybridus (AMACH), Amaranthus blitum (AMALI), Amaranthus blitum (AMALI), Amaranthus palmeri (AMAPA), Amaranthus powellii (AMAPO), Amaranthus retroflexus (AMARE), Amaranthus spinosus (AMASP), Amaranthus tuberculatus (AMATU), Ambrosia artemisiifolia (AMBEL), Ambrosia trifida (AMBTR), Avena fatua (AVEFA), Brachiaria platyphylla (BRAPP), Bromus tectorum (BROTE), Brassica napus (BRSNN), Senna tora (CASTO), Chenopodium album (CHEAL), Chenopodiastrum murale (CHEMU), Cirsium arvense (CIRAR), Ipomoea muricata (CLYMU), Commelina benghalensis (COMBE), Convolvulus arvensis (CONAR), Cyperus esculentus (CYPES), Cyperus rotundus (CYPRO), Descurainia pinnata (DESPI), Descurainia pinnata (DESPI), Descurainia sophia (DESSO), Digitaria sanguinalis (DIGSA), Echinochloa crus-galli (ECHCG), Echinochloa coIonum(ECHCO), Eleusine indica (ELEIN), Equisetum arvense (EQUAR), Erigeron annuus (ERIAN), Erigeron bonariensis (ERIBO), Erigeron canadensis (ERICA), Erigeron floribundus (ERIFL), Galinsoga quadriradiata (GASCI), Galinsoga parviflora (GASPA), Geranium dissectum (GERDI), Ipomoea hederacea (IPOHE), Ipomoea lacunosa (IPOLA), Ipomoea cordatotriloba (IPOTC), Ipomoea tricolor (IPOTO), Ipomoea heptaphylla (IPOWR), Kochia sp. (KCHSS), Urochloa texana (PANTE), Ipomoea purpurea (PHBPU), Physalis acutifolia (PHYWR), Portulaca oleracea (POROL), Setaria faberi (SETFA), Setaria magna (SETMG), Setaria pumila (SETPU), Setaria viridis (SETVI), Sinapis arvensis (SINAR), Solanum americanum (SOLAM), Solanum carolinense (SOLCA), Solanum nigrum (SOLNI), Sorghum halepense (SORHA), Sisymbrium altissimum (SSYAL), Setaria verticillata (STEVE), Taraxacum officinale (TAROF), and Toxicodendron radicans (TOXRA). In an even more preferably second alternative of the preferred embodiment on North American territory, the compound of the first aspect or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof or a tautomer thereof, or a composition according to the second aspect is used against a species selected from the group consisting of Avena fatua (AVEFA), Chenopodium album (CHEAL), Digitaria sanguinalis (DIGSA), Echinochloa crus-galli (ECHCG), Geranium dissectum (GERDI), Setaria viridis (SETVI), and Solanum nigrum (SOLNI).

[0279] In an even more preferred embodiment, the compound of the first aspect or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof or a tautomer thereof, or a composition according to the second aspect is used as a broad-spectrum herbicide, preferably a preemergence herbicide, against monocotyledonous plants, and as a specific herbicide against Chenopodium album (CHEAL), Geranium dissectum (GERDI), and / or Solanum nigrum (SOLNI). In one specific embodiment, there is the use of a compound of formula I, wherein R2is selected from 1-butyn-4-yl, 2-butyn-1-yl, propargyl, 1-butyn-3-yl, prop-1 -yl, 3-methyl-1-butyn-3-yl and allyl, and R3is 4-fluorophenyl, or wherein R2is isopropyl, and R3is selected from 4-chlorophenyl, 4-nitrophenyl, 4-(trifluoromethyl)phenyl, 3,4-difluorophenyl, 2,4-difluorophenyl, 3-fluoro-4-chlorophenyl and 3-chloro-4-fluorophenyl, against species selected from Alopecurus myosuroides (ALOMY), Apera spica-venti (APESV), Avena fatua (AVEFA), Chenopodium album (CHEAL), Digitaria sanguinalis (DIGSA), Echinochloa crus-galli (ECHCG), Geranium dissectum (GERDI), Lolium multiflorum (LOLMU), Panicum miliaceum (PANMI), Poa annua (POAAN), Setaria viridis (SETVI) and Solanum nigrum (SOLNI). Preferably, there is the use of a compound of formula I, wherein R2is selected from 1-butyn-4-yl, 2-butyn-1-yl, propargyl, 1-butyn-3-yl, prop-1 -yl, 3-methyl-1-butyn-3-yl and allyl, and R3is 4-fluorophenyl against one or more species selected from ALOMY, APESV, AVEFA, DIGSA, ECHCG, LOLMU, PANMI, POAAN and SETVI, and optionally also against CHEAL, GERDI and / or SOLNI. More preferably, there is the use of said compound of formula I against ALOMY, LOLMU and APESV, and as a pre-emergence herbicide against monocotyledonous plants, and as a specific herbicide against Chenopodium album (CHEAL), Geranium dissectum (GERDI), and / or Solanum nigrum (SOLNI).

[0280] In another embodiment, there is the use of a compound of formula I, wherein R2is iso-propyl and R3is selected from 3,4-difluorophenyl, 2,4-difluorophenyl, 3-fluoro-4-chlorophenyl and 3-chloro-4-fluorophenyl against species selected from ALOMY, APESV, AVEFA, DIGSA, ECHCG, GERDI, LOLMU, PANMI, POAAN and SETVI, and optionally also against CHEAL, GERDI and / or SOLNI. In a further embodiment, there is the use of a compound of formula I, wherein R2is iso-butyl and R3is 4-fluorophenyl against one or more species selected from ALOMY, APESV, AVEFA, CHEAL, DIGSA, ECHCG, GERDI, LOLMU, PANMI, POAAN, SETVI and SOLNI, preferably against one or more species selected from ALOMY, AVEFA, CHEAL, DIGSA, ECHCG, LOLMU, PANMI and SOLNI, more preferably against one or more species selected from AVEFA, DIGSA, ECHCG and LOLMU, even more preferably one or more species selected from DIGSA, ECHCG and LPLMU.

[0281] In yet another embodiment, there is the use of a compound of formula I, wherein R2is propargyl and R3is 4-fluorophenyl against one or more species selected from ALOMY, APESV, AVEFA, CHEAL, DIGSA, ECHCG, GERDI, LOLMU, PANMI, POAAN, SETVI and SOLNI, preferably against one or more speciesselected from ALOMY, APESV, AVEFA, CHEAL, DIGSA, ECHCG, GERDI, LOLMU, PANMI, POAAN, SETVI and SOLNI, more preferably against one or more species selected from ALOMY, APESV, CHEAL, DIGSA, ECHCG, LOLMU, PANMI, POAAN, SETVI and SOLNI, even more preferably one or more species selected from CHEAL, LOLMU and SOLNI.

[0282] In yet another embodiment, there is the use of a compound of formula I, wherein R2is cyclopentyl and R3is 4-fluorophenyl against one or more species selected from ALOMY, APESV, AVEFA, CHEAL, DIGSA, ECHCG, GERDI, LOLMU, PANMI, POAAN, SETVI and SOLNI, preferably against one or more species selected from AVEFA, CHEAL, DIGSA, ECHCG, LOLMU, PANMI and SOLNI, more preferably against one or more species selected from DIGSA and ECHCG.

[0283] In a further embodiment, there is the use of a compound of formula I, wherein R2is tert-butyl and R3is 4-fluorophenyl against one or more species selected from ALOMY, APESV, AVEFA, CHEAL, DIGSA, ECHCG, GERDI, LOLMU, PANMI, POAAN, SETVI and SOLNI, preferably against one or more species selected from AVEFA, CHEAL, DIGSA, ECHCG, LOLMU, PANMI and SOLNI, more preferably against one or more species selected from CHEAL, DIGSA and ECHCG, even more preferably against the species ECHCG.

[0284] In another embodiment, there is the use of a compound of formula I, wherein R2is allyl and R3is 4-fluorophenyl against one or more species selected from ALOMY, APESV, AVEFA, CHEAL, DIGSA, ECHCG, GERDI, LOLMU, PANMI, POAAN, SETVI and SOLNI, preferably ALOMY, APESV, DIGSA, ECHCG, GERDI, LOLMU, PANMI, POAAN, SETVI and SOLNI, more preferably against one or more species selected from ALOMY, APESV, DIGSA, LOLMU, POAAN, SETVI and SOLNI, even more preferably against one or more species selected from ALOMY and LOLMU.

[0285] In yet a further embodiment, there is the use of a compound of formula I, wherein R2is sec-butyl and R3is 4-fluorophenyl against one or more species selected from ALOMY, APESV, AVEFA, CHEAL, DIGSA, ECHCG, GERDI, LOLMU, PANMI, POAAN, SETVI and SOLNI, preferably against one or more species selected from ALOMY, AVEFA, CHEAL, DIGSA, ECHCG, LOLMU and PANMI, more preferably against the species ALOMY.

[0286] In another embodiment, there is the use of a compound of formula I, wherein R2is cyclopropyl and R3is 4-fluorophenyl against one or more species selected from ALOMY, APESV, AVEFA, CHEAL, DIGSA, ECHCG, GERDI, LOLMU, PANMI, POAAN, SETVI and SOLNI, preferably against one or more species selected from ALOMY, AVEFA, CHEAL, DIGSA, ECHCG, LOLMU and PANMI, more preferably against one or more species selected from ALOMY, DIGSA, ECHCG, LOLMU and PANMI.

[0287] Also, in a further embodiment, there is the use of a compound of formula I, wherein R2is cyanomethyl and R3is 4-fluorophenyl against one or more species selected from ALOMY, APESV, AVEFA, CHEAL, DIGSA, ECHCG, GERDI, LOLMU, PANMI, POAAN, SETVI and SOLNI, preferably against one or more species selected from ALOMY, AVEFA, CHEAL, DIGSA, ECHCG, LOLMU and PANMI, more preferably against one or more species selected from ALOMY, DIGSA and LOLMU, and even more preferably against the species DIGSA.

[0288] In another embodiment, there is the use of a compound of formula I, wherein R2is 1-butyn-4-yl and R3is 4-fluorophenyl against one or more species selected from ALOMY, APESV, AVEFA, CHEAL, DIGSA, ECHCG, GERDI, LOLMU, PANMI, POAAN, SETVI and SOLNI, preferably against one or more species selected from ALOMY, APESV, CHEAL, DIGSA, ECHCG, LOLMU, PANMI, POAAN, SETVI and SOLNI, more preferably against one or more species selected from ALOMY, APESV, CHEAL, DIGSA, PANMI, POAAN, SETVI and SOLNI, even more preferably against one or more species selected from ALOMY and SOLNI.

[0289] In another embodiment, there is the use of a compound of formula I, wherein R2is 2-butyn-1-yl and R3is 4-fluorophenyl against one or more species selected from ALOMY, APESV, AVEFA, CHEAL, DIGSA,ECHCG, GERDI, LOLMU, PANMI, POAAN, SETVI and SOLNI, preferably against one or more species selected from ALOMY, APESV, AVEFA, CHEAL, DIGSA, ECHCG, LOLMU, PANMI, POAAN, SETVI and SOLNI, more preferably against one or more species selected from ALOMY, APESV, DIGSA, ECHCG, POAAN, SETVI and SOLNI.

[0290] In another embodiment, there is the use of a compound of formula I, wherein R2is isopropyl and R3is 3.4-difluorophenyl against one or more species selected from ALOMY, APESV, AVEFA, CHEAL, DIGSA, ECHCG, GERDI, LOLMU, PANMI, POAAN, SETVI and SOLNI, preferably against one or more species selected from ALOMY, APESV, CHEAL, DIGSA, ECHCG, GERDI, PANMI, POAAN, SETVI and SOLNI, more preferably against one or more species selected from APESV, CHEAL, DIGSA, ECHCG, GERDI, PANMI, SETVI and SOLNI, even more preferably against one or more species selected from CHEAL and GERDI.

[0291] In another embodiment, there is the use of a compound of formula I, wherein R2is isopropyl and R3is 2.4-difluorophenyl against one or more species selected from ALOMY, APESV, DIGSA, ECHCG, GERDI, LOLMU, PANMI, POAAN, SETVI and SOLNI, preferably against one or more species selected from ALOMY, APESV, DIGSA, ECHCG, LOLMU, PANMI, POAAN, SETVI and SOLNI, more preferably against one or more species selected from APESV, DIGSA, ECHCG, LOLMU, PANMI, POAAN, SETVI and SOLNI, even more preferably against LOLMU.

[0292] In another embodiment, there is the use of a compound of formula I, wherein R2is isopropyl and R3is 3-fluoro-4-chlorophenyl against one or more species selected from ALOMY, APESV, AVEFA, CHEAL, DIGSA, ECHCG, GERDI, LOLMU, PANMI, POAAN, SETVI and SOLNI, preferably against one or more species selected from ALOMY, AVEFA, DIGSA, ECHCG, PANMI, POAAN and SETVI, more preferably against one or more species selected from DIGSA, ECHCG, PANMI, POAAN and SETVI.

[0293] In another embodiment, there is the use of a compound of formula I, wherein R2is isopropyl and R3is 3-chloro-4-fluorophenyl against one or more species selected from ALOMY, APESV, AVEFA, CHEAL, DIGSA, ECHCG, GERDI, LOLMU, PANMI, POAAN, SETVI and SOLNI, preferably against one or more species selected from ALOMY, CHEAL, DIGSA, ECHCG, LOLMU, PANMI and POAAN, more preferably against one or more species selected from CHEAL and LOLMU.

[0294] In another embodiment, there is the use of a compound of formula I, wherein R2is prop-1 -yl and R3is 4-fluorophenyl against one or more species selected from ALOMY, APESV, AVEFA, CHEAL, DIGSA, ECHCG, GERDI, LOLMU, PANMI, POAAN, SETVI and SOLNI, preferably against one or more species selected from ALOMY and LOLMU, more preferably against LOLMU.

[0295] In another embodiment, there is the use of a compound of formula I, wherein R2is 1-butyn-3-yl and R3is 4-fluorophenyl against one or more species selected from ALOMY, APESV, AVEFA, CHEAL, DIGSA, ECHCG, GERDI, LOLMU, PANMI, POAAN, SETVI and SOLNI, preferably against one or more species selected from ALOMY and LOLMU, more preferably against ALOMY.

[0296] In another embodiment, there is the use of a compound of formula I, wherein R2is 3-methyl-1-butyn-3-yl and R3is 4-fluorophenyl against one or more species selected from ALOMY, APESV, AVEFA, CHEAL, DIGSA, ECHCG, GERDI, LOLMU, PANMI, POAAN, SETVI and SOLNI, preferably against one or more species selected from ALOMY and LOLMU, more preferably against ALOMY.

[0297] In another embodiment, there is the use of a compound of formula I, wherein R2is isopropyl and R3is 3-cyano-4-fluorophenyl against one or more species selected from ALOMY, AVEFA, CHEAL, ECHCG, LOLMU, PANMI and POAAN, preferably against one or more species selected from ALOMY, CHEAL, LOLMU and PANMI, even more preferably against ALOMY.

[0298] In another embodiment, there is the use of a compound of formula I, wherein R2is 3 isopropyl and R3is 4-cyano-3-fluorophenyl against one or more species selected from ALOMY, AVEFA, CHEAL, ECHCG,LOLMU, PANMI and POAAN, preferably against one or more species selected from ALOMY, CHEAL, ECHCG, LOLMU and POAAN, more preferably against ALOMY, CHEAL and POAAN.

[0299] In another embodiment, there is the use of a compound of formula I, wherein R2is propargyl and R3is 2.4-difluorophenyl against one or more species selected from ALOMY, AVEFA, CHEAL, ECHCG, LOLMU, PANMI and POAAN, preferably against one or more species selected from ALOMY, CHEAL, ECHCG, LOLMU, PANMI and POAAN, more preferably against ALOMY, CHEAL, ECHCG and POAAN. In another embodiment, there is the use of a compound of formula I, wherein R2is 2-butyn-1-yl and R3is 2,4-difluorophenyl against one or more species selected from ALOMY, AVEFA, CHEAL, ECHCG, LOLMU, PANMI and POAAN, preferably against one or more species selected from ALOMY, CHEAL, ECHCG, LOLMU and POAAN, more preferably against one or more species selected from ALOMY, ECHCG and POAAN, even more preferably against ALOMY and POAAN.

[0300] In another embodiment, there is the use of a compound of formula I, wherein R2is allyl and R3is 2,4-difluorophenyl against one or more species selected from ALOMY, AVEFA, CHEAL, ECHCG, LOLMU, PANMI and POAAN, preferably against one or more species selected from ALOMY, AVEFA, CHEAL, ECHCG, LOLMU and POAAN, more preferably against one or more species selected from ALOMY, CHEAL, ECHCG, LOLMU and POAAN, even more preferably against ALOMY and CHEAL.

[0301] In another embodiment, there is the use of a compound of formula I, wherein R2is isopropyl and R3is 2.3.4-trifluorophenyl against one or more species selected from ALOMY, AVEFA, CHEAL, ECHCG, LOLMU, PANMI and POAAN, preferably against one or more species selected from ALOMY, CHEAL, ECHCG, LOLMU, PANMI and POAAN, more preferably against ALOMY, ECHCG, PANMI and POAAN. In another embodiment, there is the use of a compound of formula I, wherein R2is isopropyl and R3is 4-chloro-2-fluorophenyl against one or more species selected from AVEFA, ECHCG, LOLMU, PANMI and POAAN, preferably against one or more species selected from ECHCG, LOLMU, PANMI and POAAN.

[0302] In another embodiment, there is the use of a compound of formula I, wherein R2is isopropyl and R3is 2.4-chlorophenyl against one or more species selected from AVEFA, ECHCG, LOLMU, PANMI and POAAN, preferably against one or more species selected from ECHCG, LOLMU and POAAN, or from AVEFA, LOLMU and POAAN.

[0303] In another embodiment, there is the use of a compound of formula I, wherein R2is isopropyl and R3is 2-methyl-4-fluorophenyl against one or more species selected from AVEFA, ECHCG, LOLMU, PANMI and POAAN, preferably against one or more species selected from ECHCG, LOLMU, PANMI and POAAN, more preferably against ECHCG, LOLMU and PANMI and.

[0304] In another embodiment, there is the use of a compound of formula I, wherein R2is isopropyl and R3is 2,4,5-trifluorophenyl against one or more species selected from AVEFA, ECHCG, LOLMU, PANMI and POAAN, preferably against one or more species selected from AVEFA, ECHCG, LOLMU and PANMI, more preferably against AVEFA, ECHCG and PANMI.

[0305] In another embodiment, there is the use of a compound of formula I, wherein R2is isopropyl and R3is 3-bromo-4-fluorophenyl against one or more species selected from AVEFA, ECHCG, LOLMU, PANMI and POAAN, preferably against one or more species selected from AVEFA, ECHCG, LOLMU and POAAN, or from ECHCG, LOLMU, PANMI and POAAN.

[0306] In some embodiments, the compound of formula I is applied pre-emergence at no more than 250 g / ha, preferably at no more than 125 g / ha or at no more than 63 g / ha (i.e. about 62.5 g / ha).In one embodiment, the compound according to the first aspect of the present invention or the composition according to the second aspect are used in combination with one or more additional herbicides and / or plant growth regulators as listed above, for example, on the above-mentioned crops and / or against the above-mentioned species. The compound according to the first aspect of the present invention or the composition according to the second aspect and the one or more additional herbicides and / or plant growth regulators may either be used separately or may be formulated into an agrochemical composition.

[0307] As the compounds of the present invention are useful as herbicides, the present invention further provides a method for controlling unwanted plants comprising applying to said plants or a locus comprising them, an effective amount of the compound of formula (I) or a herbicidal composition containing said compound.

[0308] In another exemplary embodiment, a plant propagation material, such as a seed, comprises or is treated with or adhered to a compound according to the first aspect of the present invention or the composition according to the second aspect of the present invention.

[0309] Preparation of compounds of formula I

[0310] In a fourth aspect, the present invention further provides methods for producing the compound according to the first aspect of the invention, i.e., compounds of formula I.

[0311] In a particular embodiment, the method for producing a compound of formula I comprises a step which is selected from the following (i) to (iv):

[0312] >

[0313]

[0314] wherein L, LG and LGXare each independently leaving groups such as the ones described below, and the remaining groups are as defined for the compound of formula I above.Exemplary methods for producing exemplary compounds will be set out in the following. The skilled person will appreciate that these methods for the manufacture of the compounds of the present invention, as well as the methods for producing intermediates used for preparing the compounds of the present invention may be adapted depending on the compound to be synthesized.

[0315] For example, the skilled person will be immediately familiar with standard textbooks such as “Comprehensive Organic Transformations - A Guide to Functional Group Transformations”, RC Larock, Wiley- VCH (1999 or later editions); “March's Advanced Organic Chemistry - Reactions, Mechanisms and Structure”, MB Smith, J. March, Wiley, (5th edition or later editions); “Advanced Organic Chemistry, Part B, Reactions and Synthesis”, FA Carey, RJ Sundberg, Kluwer Academic / Plenum Publications, (2001 or later editions); “Organic Synthesis - The Disconnection Approach”, S Warren (Wiley), (1982 or later editions); “Designing Organic Syntheses” S Warren (Wiley) (1983 or later editions); “Heterocyclic Chemistry”, J. Joule (Wiley 2010 edition or later editions); “Guidebook To Organic Synthesis" RK Mackie and DM Smith (Longman) (1982 or later editions), etc., and the references therein as a guide.

[0316] The skilled person is familiar with a range of strategies for synthesising organic and particularly heterocyclic molecules and these represent common general knowledge as set out in textbooks such as Warren “Organic Synthesis: The Disconnection Approach”; Mackie and Smith “Guidebook to Organic Chemistry”; and Clayden, Greeves, Warren and Wothers “Organic Chemistry”.

[0317] The skilled person will exercise his / her judgement and skill as to the most efficient sequence of reactions for the synthesis of a given target compound and will employ protecting groups as necessary. This will depend inter alia on factors such as the nature of other functional groups present in a particular substrate. Clearly, the type of chemistry involved will influence the choice of reagent that is used in the said synthetic steps, the need, and type, of protecting groups that are employed, and the sequence for accomplishing the protection / deprotection steps. These and other reaction parameters will be evident to the skilled person by reference to standard textbooks and to the examples provided herein.

[0318] Sensitive functional groups may need to be protected and deprotected during synthesis of a compound of the invention. This may be achieved by conventional methods using protecting groups (sometimes abbreviated as “PG” hereinafter), for example as described in “Protective Groups in Organic Synthesis” by TW Greene and PGM Wuts, John Wiley & Sons Inc. (1999), and references therein. For example, compounds of formula I can be made, as shown in Scheme 1 below by coupling a carboxylic acid derivative with an amine. In the carboxylic acid derivative shown below, L is a suitable leaving group which can include: OH, halogen, Oalkyl, Oaryl, OCOalkyl or OCOaryl. A suitable amide forming procedure involves treatment of the carboxylic acid derivative with a secondary amine at 0 - 120 °C in a suitable solvent. The presence of a base, or, when L = OH, a coupling agent, may also be necessary for the reaction to occur. Suitable bases for the reaction include 4-( / V, / V-dimethylamino)pyridine, pyridine, triethylamine or A / , / V-diisopropylethylamine. Suitable coupling agents, when L = OH include: carbodiimides, for example 1 ,3-dicyclohexylcarbodiimide or 1-(3-dimethylaminopropyl-3-ethylcarbodiimide hydrochloride; phosphonium reagents, for example (benzotriazol-1-yloxy)tris(dimethylamino)phosphonium hexafluorophosphate or benzotriazol-1-yloxytripyrrolidinophosphonium hexafluorophosphate; and uronium reagents, for example O-(benzotriazol-l-ylj-A / . / V. / VW-tetramethyluronium tetrafluoroborate. Suitable solvents for the reaction include / V, / V-dimethylformamide, dimethyl sulfoxide or acetonitrile.

[0319]

[0320] Scheme 1

[0321] A preferred embodiment of this method is shown in the below Scheme 2:

[0322]

[0323] Scheme 2

[0324] Secondary amines can be made, for example, as shown in Scheme 3 below by reductive amination of an amine derivative with a ketone or aldehyde derivative. A suitable secondary amine forming procedure involves treatment of an amine compound with a ketone or aldehyde compound in the presence of a reducing agent, for example, sodium triacetoxyborohydride, sodium cyanoborohydride or hydrogen and a metal catalyst, for example, palladium on carbon (10 wt.%) at 0 - 120 °C in a suitable solvent. Suitable solvents for the reaction include methanol or toluene.

[0325] o-R2

[0326]

[0327] Scheme 3

[0328] Alternatively, secondary amines can be made, for example, as shown in Scheme 4 below by substitution of an alkyl derivative, where LGXis a suitable leaving group, for example, Cl, Br, I, OTf, with an amine derivative. A suitable secondary amine forming procedure involves treatment of an amine compound with an alkyl derivative at 0 - 120 °C in a suitable solvent. The presence of a base may also be necessary for the reaction to occur. Suitable bases for the reaction include sodium hydroxide, potassium tert-butoxide or potassium carbonate. Suitable solvents for the reaction include / V, / V-dimethylformamide, dimethyl sulfoxide or acetonitrile.

[0329]

[0330] Scheme 4

[0331] Secondary amines can be made, for example, as shown in Scheme 5 below by Smiles rearrangement of an amide. A suitable secondary amine forming procedure involves treatment of an amide with a base, for example, potassium hydroxide, or potassium tert-butoxide at 0 - 120 °C in a suitable solvent. Suitable solvents for the reaction include / V, / V-dimethylformamide, A / -methyl-2-pyrrolidone or toluene.

[0332]

[0333] Scheme 5

[0334] Secondary amides can be made, for example, as shown in Scheme 6 below by substitution of an amide derivative, where LG is a suitable leaving group which can include: OH, halogen, Oalkyl, Oaryl,OCOalkyl, SO2alkyl, SO2aryl or OCOaryl, with a phenol derivative. A suitable ether forming procedure involves treatment of a phenol derivative with an amide derivative at 0 - 120 °C in a suitable solvent. The presence of a base, or, when LG = OH, a coupling agent, may also be necessary for the reaction to occur. Suitable bases for the reaction include sodium hydroxide or potassium carbonate among others. Suitable coupling agents when LG = OH include: azodicarboxylates, for example diethyl azodicarboxylate or diisopropyl azodicarboxylate, alongside a trisubstituted phosphine reagent, for example triphenylphosphine; and phosphorane ylides, for example, (cyanomethylene)trimethylphosphorane or (cyanomethylene)tributylphosphorane. Suitable solvents for the reaction include acetone, water, toluene or isopropyl alcohol.

[0335]

[0336] Scheme 6

[0337] Secondary amines can be made, for example, as shown in Scheme 7 below by a metal-catalysed crosscoupling reaction of an amine derivative and an aryl-halide derivative, where X is a halogen, or pseudohalogen including: Cl, Br, I, OTs. A suitable metal-catalysed cross-coupling procedure involves treatment of an aryl-(pseudo)halide compound and an amine with a suitable catalyst, for example, copper (I) iodide, copper (I) oxide or copper (I) bromide and a suitable base, for example, potassium carbonate, potassium te / Y-butoxide, tripotassium phosphate or caesium carbonate at 0 - 120 °C in a suitable solvent. Suitable solvents for the reaction include / V, / V-dimethylformamide, dimethyl sulfoxide or acetonitrile. The presence of a ligand may also be required. Suitable ligands include: 2-(diphenylphosphinyl)benzaldehyde oxime or A / ),A / 2-bis(2,4,6-trimethoxyphenyl)ethanediamide.

[0338] D2

[0339] "

[0340]

[0341] Scheme 7

[0342] Alkoxy-thiadiazole derivatives can be made, for example, as shown in Scheme 8 below by nucleophilic aromatic substitution of a thiadiazole derivative where L is a suitable leaving group which can include: OH, halogen, Oalkyl, Oaryl, OCOalkyl, SO2alkyl, SO2aryl or OCOaryl, with an alcohol derivative, where LG is a suitable leaving group which can include: OH, halogen, Oalkyl, Oaryl, OCOalkyl, SO2alkyl, SO2aryl or OCOaryl.. A suitable ether forming procedure involves treatment of an alkoxy-thiadiazole with an alcohol in the presence of a base, for example, sodium hydroxide, potassium carbonate or potassium te / Y-butoxide at 0 - 120 °C in a suitable solvent. Suitable solvents for the reaction include acetone, water, acetonitrile or toluene.

[0343]

[0344] Scheme 8Sulfone derivatives, where Rxis defined as Ci-nalkyl, can be made, for example, as shown in Scheme 9 below by oxidation of a thioether derivative, where Rxis defined as Ci-nalkyl. A suitable oxidation procedure involves treatment of a thioether derivative with a suitable oxidising agent, for example, hydrogen peroxide, mefa-chloroperbenzoic acid or potassium persulfate at 0 - 120 °C in a suitable solvent. Suitable solvents for the reaction include methanol, water or toluene.

[0345]

[0346] Scheme 9

[0347] Chlorinated thiadiazoles, where Rxis defined as Ci-nalkyl, can be made, for example, as shown in Scheme 10 below by Sandmeyer reaction of an amine derivative, where Rxis defined as Ci-nalkyl. A suitable Sandmeyer reaction procedure involves treatment of an amine derivative with a suitable diazonium forming reagent, for example, sodium nitrite or tert-buty I nitrite and a suitable halogen source, for example, hydrochloric acid or copper (I) chloride at 0 - 120 °C in a suitable solvent. Suitable solvents for the reaction include acetonitrile or water.

[0348]

[0349] Scheme 10

[0350] Thioether derivatives, where Rxis defined as Ci-nalkyl can be made, for example, as shown in Scheme 11 below by alkylation of a thiol derivative, with an alkylating agent of, where Rxis defined as Ci-nalkyl and where LGXis a suitable leaving group which can include: halogen, Oalkyl, Oaryl, OCOalkyl, SO2alkyl, SO2aryl or OCOaryl. A suitable alkylation procedure involves treatment of a thiol derivative with an alkylating agent in the presence of a base, for example, potassium hydroxide or potassium carbonate at 0 - 120 °C in a suitable solvent. Suitable solvents for the reaction include N,N-dimethylformamide, water or isopropyl alcohol.

[0351]

[0352] Scheme 11

[0353] Alternatively, ether derivatives can be made, for example, as shown in Scheme 12:

[0354]

[0355] Scheme 12

[0356] A preferred embodiment of this method is shown in the below Scheme 13 below by nucleophilic aromatic substitution of a thiadiazole derivative, where LGXis a suitable leaving group which can include: OH, halogen, Oalkyl, Oaryl, OCOalkyl, SO2alkyl, SO2aryl or OCOaryl, with an alcohol derivative. A suitable ether forming procedure involves treatment of a thiadiazole derivative with an alcohol derivative at -50 - 120 °C in a suitable solvent. The presence of a base, or, when L = OH, a coupling agent, may also be necessary for the reaction to occur. Suitable bases for the reaction include sodium hydroxide orpotassium carbonate among others. Suitable coupling agents when L = OH include: azodicarboxylates, for example diethyl azodicarboxylate or diisopropyl azodicarboxylate, alongside a trisubstituted phosphine reagent, for example triphenylphosphine; and phosphorane ylides, for example, (cyanomethylene)trimethylphosphorane or (cyanomethylene)tributylphosphorane. Suitable solvents for the reaction include acetone, water, toluene or isopropyl alcohol.

[0357]

[0358] Scheme 13

[0359] Alcohol derivatives can be made, for example, as shown in Scheme 14 below by hydrolysis of an ester derivatives where Rxis defined as Ci-nalkyl. A suitable hydrolysis procedure involves treatment of an ester derivative with a base, for example, sodium hydroxide or potassium carbonate at 0 - 120 °C in a suitable solvent. Suitable solvents for the reaction include methanol or water.

[0360]

[0361] Scheme 14

[0362] Ester derivatives can be made, for example, as shown in Scheme 15 below by substitution of amide derivative, where LGXis a suitable leaving group which can include: OH, halogen, Oalkyl, Oaryl, OCOalkyl, SO2alkyl, SO2aryl or OCOaryl, with a carboxylic acid derivative, where Rxis defined as Ci-nalkyl. A suitable carbon-oxygen bond forming procedure involves treatment of an amide derivative with a carboxylic acid derivative at 0 - 120 °C in a suitable solvent. The presence of a base or, when L = OH, a coupling agent, may also be necessary for the reaction to occur. Suitable bases for the reaction include sodium hydroxide, potassium te / Y-butoxide or potassium carbonate. Suitable coupling agents when L = OH include: azodicarboxylates, for example diethyl azodicarboxylate or diisopropyl azodicarboxylate, alongside a trisubstituted phosphine reagent, for example triphenylphosphine; and phosphorane ylides, for example, (cyanomethylene)trimethylphosphorane or (cyanomethylene)tributylphosphorane. Suitable solvents for the reaction include N,N-dimethylformamide, toluene or acetonitrile.

[0363]

[0364] Scheme 15

[0365] Amides can be made, for example, as shown in Scheme 16 below by coupling a carboxylic acid derivative with an aniline. In the carboxylic acid derivative, LG and LGXare a suitable leaving group which can include: OH, halogen, Oalkyl, Oaryl, OCOalkyl or OCOaryl. A suitable amide forming procedure involves treatment of a carboxylic acid derivative with an aniline at 0 - 120 °C in a suitable solvent. The presence of a base, or, when L = OH, a coupling agent, may also be necessary for the reaction to occur. Suitable bases for the reaction include 4-( / V, / V-dimethylamino)pyridine, pyridine, triethylamine or A / , / V-diisopropylethylamine. Suitable coupling agents when L = OH include: carbodiimides, for example 1 ,3-dicyclohexylcarbodiimide or 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride; phosphonium reagents, for example (benzotriazol-1-yloxy)tris(dimethylamino)phosphonium hexafluorophosphate or benzotriazol-1-yloxytripyrrolidinophosphonium hexafluorophosphate; and uronium reagents, for example O-(benzotriazol-l-yO' / V. / V. / V. / V-tetramethyluronium tetrafluoroborate. Suitable solvents for the reaction include / V, / V-dimethylformamide, dimethyl sulfoxide or dichloromethane.

[0366]

[0367] Scheme 16

[0368] Alternatively, chlorinated thioethers, where Rxis defined as Ci-nalkyl, can be made, for example, as shown in Scheme 17 below by chlorination of a thiadiazole derivative. A suitable chlorination procedure involves treatment of a thiadiazole derivative with a suitable chlorinating agent, for example, chlorine, / V-chlorosuccinimide, thionyl chloride or 1 ,3-dichloro-5,5-dimethylhydantoin at 0 - 120 °C in a suitable solvent. Suitable solvents for the reaction include / V, / V-dimethylformamide, acetic acid or N,N-dimethylacetamide.

[0369]

[0370] Scheme 17

[0371] Thioether derivatives, where Rxare defined as Ci-nalkyl can be made, for example, as shown in Scheme 18 below by alkylation of a thiol derivative, with an alkylating agent, where Rxis defined as Ci-nalkyl, and where LGXis a suitable leaving group which can include: halogen, Oalkyl, Oaryl, OCOalkyl, SO2alkyl, SC>2aryl or OCOaryl. A suitable alkylation procedure involves treatment of a thiol derivative with an alkylating agent in the presence of a base, for example, potassium hydroxide or potassium carbonate at 0 - 120 °C in a suitable solvent. Suitable solvents for the reaction include N,N-dimethylformamide, water or isopropyl alcohol.

[0372]

[0373] Scheme 18

[0374] Thio derivatives can be made, for example, as shown in Scheme 19 below by cyclisation of a hydrazine derivative, with carbon disulfide. A suitable cyclisation procedure involves treatment of a hydrazine derivative with carbon disulfide in the presence of a base, for example, potassium hydroxide or potassium carbonate at 0 - 120 °C in a suitable solvent followed by treatment with a suitable acid, for example sulfuric acid or hydrochloric acid, at 0 - 120 °C in a suitable solvent. Suitable solvents for the reaction include ethanol, water or isopropyl alcohol.

[0375]

[0376] Scheme 19

[0377] Sulfone derivatives can be made, for example, as shown in Scheme 20 below by oxidation of a thioether derivative, where Rxis defined as Ci-nalkyl. A suitable oxidation procedure involves treatment of a thioether derivative with a suitable oxidising agent, for example, hydrogen peroxide, meta-chloroperbenzoic acid (mCBPA) or potassium persulfate at 0 - 120 °C in a suitable solvent. Suitable solvents for the reaction include methanol, water or toluene.

[0378]

[0379] Scheme 20

[0380] Amide derivatives can be made, for example, as shown in Scheme 21 below by nucleophilic aromatic substitution of thiadiazole derivative, where LGXis a suitable leaving group which can include: OH, halogen, Oalkyl, Oaryl, OCOalkyl, SO2alkyl, SO2aryl or OCOaryl, with an alcohol derivative, where R1a, R1band R2are defined as above. A suitable ether forming procedure involves treatment of a thiadiazole derivative with an alcohol at 0 - 120 °C in a suitable solvent. The presence of a base, or, when LGX= OH, a coupling agent, may also be necessary for the reaction to occur. Suitable bases for the reaction include sodium hydroxide or potassium carbonate among others. Suitable coupling agents when LGX= OH include: azodicarboxylates, for example diethyl azodicarboxylate or diisopropyl azodicarboxylate, alongside a trisubstituted phosphine reagent, for example triphenylphosphine; and phosphorane ylides, for example, (cyanomethylene)trimethylphosphorane or (cyanomethylene)tributylphosphorane. Suitable solvents for the reaction include acetone, water, toluene or isopropyl alcohol.

[0381]

[0382] Scheme 21

[0383] Chlorinated thiadiazoles can be made, for example, as shown in Scheme 22 below, by chlorination of a thiadiazole derivative:

[0384] >

[0385]

[0386] Scheme 22

[0387] A suitable chlorination procedure involves treatment of a thiadiazole derivative with a suitable chlorinating agent, for example, chlorine, / V-chlorosuccinimide, thionyl chloride or 1 ,3-dichloro-5,5-dimethylhydantoin at 0 - 120 °C in a suitable solvent. Suitable solvents for the reaction include N,N-dimethylformamide, acetic acid or A / . / V-dimethylacetamide. A preferred embodiment of this method is shown in Scheme 23 below.

[0388]

[0389] Scheme 23

[0390] Ester derivatives can be made, for example, as shown in Scheme 24 below by nucleophilic aromatic substitution of a thiadiazole derivative, where L is a suitable leaving group which can include: OH, halogen, Oalkyl, Oaryl, OCOalkyl, SO2alkyl, SO2aryl orOCOaryl, with an alcohol derivative, where R is defined as Ci-nalkyl. A suitable ether forming procedure involves treatment of a thiadiazole derivative with an alcohol in the presence of a base, for example, sodium hydroxide, potassium carbonate or potassium te / Y-butoxide at 0 - 120 °C in a suitable solvent. Suitable solvents for the reaction include acetone, water, acetonitrile or toluene.

[0391]

[0392] Scheme 24

[0393] Chlorinated thiadiazoles can be made, for example, as shown in Scheme 25 below by chlorination of a thiadiazole derivative, where R is defined as Ci-nalkyl. A suitable chlorination procedure involves treatment of a thiadiazole derivative with a suitable chlorinating agent, for example, chlorine, N-chlorosuccinimide (NCS), thionyl chloride or 1 ,3-dichloro-5,5-dimethylhydantoin at 0 - 120 °C in a suitable solvent. Suitable solvents for the reaction include / V, / V-dimethylformamide, acetic acid or N,N-dimethylacetamide.

[0394]

[0395] Scheme 25

[0396] Carboxylic acids can be made, for example, as shown in Scheme 26 below by hydrolysis of ester derivatives, where R is defined as Ci-nalkyl. A suitable hydrolysis procedure involves treatment of an ester derivative with a base, for example, sodium hydroxide or potassium carbonate at 0 - 120 °C in a suitable solvent. Suitable solvents for the reaction include methanol or water.

[0397]

[0398] Scheme 26

[0399] Aryl chlorides can be made, for example, as shown in Scheme 27 below by chlorination of a thiadiazole derivative, where R is defined as H. A suitable chlorination procedure involves treatment of a thiadiazole derivative with a suitable chlorinating agent, for example, chlorine, oxalyl chloride or thionyl chloride at 0- 120 °C in a suitable solvent. Suitable solvents for the reaction include / V, / V-dimethylformamide, acetic acid or A / . / V-dimethylacetamide.

[0400]

[0401] Scheme 27

[0402] Chlorinated thiadiazoles can be made, for example, as shown in Scheme 28 below by chlorination of a thiadiazole derivative, where Rxis defined as C1-3 alkyl, chloro or OH. A suitable chlorination procedure involves treatment of a thiadiazole derivative with a suitable chlorinating agent, for example, chlorine, oxalyl chloride or thionyl chloride at 0 - 120 °C in a suitable solvent. Suitable solvents for the reaction include / V, / V-dimethylformamide, acetic acid or A / . / V-dimethylacetamide.

[0403]

[0404] Scheme 28

[0405] Chlorinated thiadiazoles can be made, for example, as shown in Scheme 29 below by chlorination of a thiadiazole derivative. A suitable chlorination procedure involves treatment of a thiadiazole compound with a suitable chlorinating agent, for example, chlorine, oxalyl chloride or thionyl chloride at 0 - 120 °C in a suitable solvent. Suitable solvents for the reaction include / V, / V-dimethylformamide or toluene.

[0406]

[0407] Scheme 29

[0408] Thioethers can be made, for example, as shown in Scheme 30 below by alkylation of a thiadiazole derivative, with an alkylating agent, where Rxis C1-3 alkyl and where LGXis a suitable leaving group which can include: halogen, Oalkyl, Oaryl, OCOalkyl, SO2alkyl, SO2aryl or OCOaryl. A suitable alkylation procedure involves treatment of a thiadiazole derivative with an alkylating agent in the presence of a base, for example, potassium hydroxide or potassium carbonate at 0 - 120 °C in a suitable solvent. Suitable solvents for the reaction include / V, / V-dimethylformamide, water or isopropyl alcohol.

[0409]

[0410] Scheme 30

[0411] Dichlorothiadiazoles can be made, for example, as shown in Scheme 31 below by chlorination of a thiadiazole derivative. A suitable chlorination procedure involves treatment of a thiadiazole derivative with a suitable chlorinating agent, for example, chlorine, oxalyl chloride, thionyl chloride, N-chlorosuccinimide, DCDMH 1 ,3-dichloro-5,5-dimethylhydantoin, trichloroisocyanuric acid, or thionyl chloride / hydrogen peroxide at 0 - 120 °C in a suitable solvent. Suitable solvents for the reaction include / V, / V-dimethylformamide, toluene or acetonitrile.

[0412]

[0413] Scheme 31

[0414] Thiols can be made, for example, as shown in Scheme 32 below by cyclisation of carbon disulfide, with hydrazine hydrate. A suitable cyclisation procedure involves treatment of carbon disulfide with hydrazine hydrate or hydrazine in the presence of a base, for example, sodium hydroxide or potassium hydroxide at 0 - 120 °C in a suitable solvent followed by treatment with a suitable acid, for example sulfuric acid or hydrochloric acid at 0 - 120 °C in a suitable solvent. Suitable solvents for the reaction include ethanol, water or pyridine.

[0415] N2H2.H2O

[0416] CS2

[0417]

[0418] Scheme 32

[0419] Ether derivatives can be made, for example, as shown in Scheme 33 below by substitution of an amide derivative:

[0420]

[0421] Scheme 33

[0422] In the amide, LG is a suitable leaving group which can include: OH, halogen, Oalkyl, Oaryl, OCOalkyl, SO2alkyl, SO2aryl or OCOaryl. A suitable ether forming procedure involves treatment of an amide derivative with an alcohol at 0 - 120 °C in a suitable solvent. The presence of a base, or, when LG = OH, a coupling agent, may also be necessary for the reaction to occur. Suitable bases for the reaction include sodium hydroxide or potassium carbonate among others. Suitable coupling agents when L = OH include: azodicarboxylates, for example diethyl azodicarboxylate or diisopropyl azodicarboxylate, alongside a trisubstituted phosphine reagent, for example triphenylphosphine; and phosphorane ylides, for example, (cyanomethylene)trimethylphosphorane or (cyanomethylene)tributylphosphorane. Suitable solvents for the reaction include acetone, water, toluene or isopropyl alcohol.

[0423] A preferred embodiment of this method is shown in Scheme 34 below:

[0424]

[0425] Scheme 34

[0426] Chlorinated thiadiazole derivates can be made, for example, as shown in Scheme 35 below by chlorination of a thiadiazole derivative. A suitable chlorination procedure involves treatment of acompound thiadiazole derivative with a suitable chlorinating agent, for example, chlorine or / V-chlorosuccinimide at 0 - 120 °C in a suitable solvent. Suitable solvents for the reaction include N,N-dimethylformamide, acetic acid or A / . / V-dimethylacetamide.

[0427]

[0428] Scheme 35

[0429] Thioethers can be made, for example, as shown in Scheme 36 below by alkylation of a thiadiazole derivative, with an alkylating agent of, where Rxare defined as C1-3 alkyl and where LGXis a suitable leaving group which can include: halogen, Oalkyl, Oaryl, OCOalkyl, SO2alkyl, SO2aryl or OCOaryl. A suitable alkylation procedure involves treatment of a thiadiazole derivative with an alkylating agent in the presence of a base, for example, potassium hydroxide or potassium carbonate at 0 - 120 °C in a suitable solvent. Suitable solvents for the reaction include / V, / V-dimethylformamide, water or isopropyl alcohol.

[0430]

[0431] Scheme 36

[0432] Thiadiazole sulfone derivatives can be made, for example, as shown in Scheme 37 below by oxidation of thioether derivatives, where Rxare defined as H or C1-5 alkyl. A suitable oxidation procedure involves treatment of a thioether derivative with a suitable oxidising agent, for example, hydrogen peroxide, meta-chloroperbenzoic acid (mCBPA) or potassium persulfate at 0 - 120 °C in a suitable solvent. Suitable solvents for the reaction include methanol, water or toluene.

[0433]

[0434] Scheme 37

[0435] Dichlorothiadiazole compounds can be made, for example, as shown in Scheme 38 below by chlorination of a thiadiazole derivative where Rxare defined as OH (sulfonic acid) or Cl (sulfonyl chloride). A suitable chlorination procedure involves treatment of a thiadiazole derivative with a suitable chlorinating agent, for example, sulfuryl chloride, thionyl chloride or HCI at 0 - 120 °C in a suitable solvent. Suitable solvents for the reaction include / V, / V-dimethylformamide, acetic acid or toluene.

[0436]

[0437] Scheme 38

[0438] Sulfonic acids or sulfonyl chlorides can be made, for example, as shown in Scheme 39 below by oxidation of thiol derivatives where Rxare defined as OH (sulfonic acid) or Cl (sulfonyl chloride). Asuitable oxidation procedure involves treatment of a thiol derivative with a suitable oxidising agent, for example, N-chlorosuccinimide (NCS), 1 ,3-dichloro-5,5-dimethylhydantoin, permanganic acid or trichloroisocyanuric acid at 0 - 120 °C in a suitable solvent. Suitable solvents for the reaction include dichloromethane, water or toluene.

[0439]

[0440] Scheme 39

[0441] Ether compounds can be made, for example, as shown in Scheme 40 below by cyclisation of a hydrazinecarbothioate derivative with a suitable reagent. A suitable cyclisation procedure involves treatment of a hydrazinecarbothioate compound with phosgene or oxalyl chloride at 0 - 120 °C in a suitable solvent. Suitable solvents for the reaction include dichloromethane, toluene or N,N-dimethylformamide.

[0442]

[0443] Scheme 40

[0444] Chlorothiadiazolone compounds can be made, for example, as shown in Scheme 41 below by demethylation of an ether derivative. A suitable demethylation procedure involves treatment of an ether compound with a suitable reagent, for example, boron tribromide, hydrogen bromide, aluminium bromide at 0 - 120 °C in a suitable solvent. Suitable solvents for the reaction include dichloromethane or water.

[0445]

[0446] Scheme 41

[0447] ThiadiazoIone compounds can be made, for example, as shown in Scheme 42 below by demethylation of an alkylated thiadiazoIone derivative A suitable demethylation procedure involves treatment of an O- alkylated thiadiazoIone compound with a suitable reagent, for example, boron tribromide, hydrogen chloride, hydrogen iodide at 0 - 120 °C in a suitable solvent. Suitable solvents for the reaction include 1 ,4-dioxane or water.

[0448]

[0449] Scheme 42

[0450] Dichlorothiadiazole compounds can be made, for example, as shown in Scheme 43 below by chlorination of a thiadiazoIone derivative. A suitable chlorination procedure involves treatment of a thiadiazoIone compound with a suitable chlorinating agent, for example, phosphorus oxychloride, oxalyl chloride orthionyl chloride at 0 - 120 °C in a suitable solvent. Suitable solvents for the reaction include / V, / V-dimethylformamide, water or toluene.

[0451]

[0452] Scheme 43

[0453] In a further aspect, the present invention also relates to novel compounds which are intermediates in the preparation of compounds according to formula I. Preferred intermediates useful in methods for producing compounds of formula I, preferably useful in one or more of the above methods, include:

[0454]

[0455]

[0456]

[0457]

[0458]

[0459]

[0460]

[0461]

[0462]

[0463] More preferred intermediates include:

[0464]

[0465]

[0466]

[0467] In one embodiment, a method for producing a compound according to the first aspect of the invention involves using one or more intermediates as depicted above in at least one step.

[0468] In another aspect of the invention, it is provided the use of any of the above intermediate compounds in the preparation of a compound according to the first aspect of the invention or any other uses and it is further provided a process for preparing a compound according to the first aspect of the invention involving any of the above intermediate compounds.

[0469] EXAMPLES

[0470] The present invention will be demonstrated in more detail by way of examples which are not intended to be limiting.

[0471] General Methods

[0472] Flash chromatography was carried out using a CombiFlash® NextGen 100 (flow rate 1 to 100 mL / min) with RediSep® cartridges packed with 40 - 63 pm silica particles with a surface area of 500 m2 / g. Visualization was carried out with UV light (254 nm) and by staining with either potassium permanganate, phosphomolybdic acid (PMA) or ninhydrin solutions.

[0473] LCMS Methods:

[0474] Method A (5 min acidic pH)

[0475] Spectra were recorded on a Waters HCIass UPLC-QDA UV-MS Mass Spectrometerequipped with a column: Waters XSelect HSS T3 Column, 100 A, 2.5 pm, 3 mm x 50 mm. Injection volume: 3 pL. Temperature: 37 °C. Mobile phases: Water (A) / Acetonitrile (B) 149.5% Water, 49.5% Acetonitrile, 1% Formic acid (C)

[0476]

[0477] Method B (5 min basic pH)

[0478] Spectra were recorded on a Mass Spectrometer from Applied Biosystems (API 2000, triple quadrupole mass spectrometer) equipped with electrospray ionisation using an atmospheric pressure ionisation source (Polarity: positive or negative ions, Declustering Potential: 50 V, Ion Source: Turbo spray, Ion Spray Voltage: 5500 V [positive], -4500 V [negative], Source Temperature: 200 °C, Mass range: 200 to 1700 Da and a Prominence HPLC from Shimadzu equipped with a column: Waters XBridge C18, 5.0 pm, 50 x 4.6 mm, UV Wavelengths: 220 and 260 nm. Mobile phases: 10 mM Ammonium Acetate in Water (A) / Acetonitrile (B):

[0479]

[0480]

[0481] Method C (12 min basic pH):

[0482] Spectra were recorded on a Mass Spectrometer from Waters (SQ Detector 2, single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.50 kV, Cone: 25.00 V, Source Temperature: 150 °C, Desolvation Temperature: 350 °C, Cone Gas Flow: 50 L / Hr, Desolvation Gas Flow: 750 L / Hr, Mass range: 100 to 900 Da) and an Acquity H-Class UPLC from Waters equipped with a column: Waters XBridge C18, 3.5 pm, 50 x 3.0 mm, Temp: 40 °C, DAD Wavelength range: 200 to 400 nm. Mobile phases: 5 mM Ammonium Acetate in Water (A) I 5 mM Ammonium Acetate in Acetonitrile:Water (9:1) (B):

[0483]

[0484] Method D (7 min acidic pH):

[0485] Spectra were recorded on an Alliance Waters e2695 series separation module HPLC System with 2998 PDA Detector with an Acquity QDa equipped with a column: Agilent, Zorbax Eclipse XDB C18, 5 pm, 4.6 mm x 50 mm. Injection volume: 5 pL. Temperature: 35 °C. Mobile phases: Formic acid (0.1%) in water (A) / Acetonitrile:Methanol (9:1) (B)

[0486]

[0487] GCMS Method

[0488] Method E (15 min):

[0489] GC-Mass was recorded on an Agilent 7890B series instrument with MSD 5977B. Column: HP-5MS (30 m x 250 pm x 0.25 pm). Carrier Gas: Helium. Inlet Temperature: 250 °C. Split ratio: 30:1. Gas flow: 1.0 mL / min. Ramp Profile: Oven temperature initial from 60 °C held for 2 min, then to 100 °C increasing at the rate of 20 °C and held for 2 min, then to 310 °C increasing at the rate of 40 °C and held for 4 min. Total run time is 15.25 min.

[0490] All reagents were obtained from commercial suppliers and used as supplied unless otherwise stated. All compounds are named using ChemDraw Professional 23.0.1.10.The abbreviations used in the following are the abbreviations commonly used in this technical field. For example, the following abbreviations are used:

[0491] BrettPhos 2-(Dicyclohexylphosphino)3,6-dimethoxy-2',4',6'-triisopropyl-1 ,1'-biphenyl

[0492] dba dibenzylideneacetone

[0493] DCM Dichloromethane

[0494] DEAD Diethyl Azodicarboxylate

[0495] DIPEA A / , / V-Diisopropylethylamine

[0496] DMF / V, / V-Dimethylformamide

[0497] DMSO Dimethyl Sulfoxide

[0498] equiv. equivalents

[0499] HPLC High-performance Liquid Chromatography

[0500] MeOH Methanol

[0501] NMP A / -Methyl-2-pyrrolidone

[0502] STAB Sodium Triacetoxyborohydride

[0503] THF Tetrahydrofuran

[0504] Rt Retention time

[0505] Synthesis of Exemplary Compounds of Formula I

[0506] General Procedure A: Aniline Alkylation

[0507] To a stirred solution of an aniline and an alkyl halide in DMF at 0 °C was added potassium carbonate. The reaction mixture was warmed to ambient temperature and stirred for 4 h. The reaction mixture was diluted with water and extracted with EtOAc. The organic layer was washed with water and brine, dried over sodium sulfate and concentrated under reduced pressure. The crude material was purified by column chromatography (silica gel, ethyl acetate in hexane) to afford the product.

[0508] General Procedure B: Reductive Amination

[0509] To a stirred solution of an aniline and acetone in DCM or THF at 0 °C was added acetic acid. STAB was then added portion wise. The reaction mixture was allowed to warm to ambient temperature and stirred for 3 h. After cooling to 0 °C, the reaction mixture was quenched with water and extracted with DCM. The combined organic phases were washed with water and aqueous potassium carbonate and concentrated under reduced pressure to afford the product.

[0510] General Procedure C: Acetamide Synthesis

[0511] To a stirred solution of an aniline in DCM, THF ortoluene at 0 °C was added triethylamine. After stirring for 5 min, 2-chloroacetyl chloride was added dropwise and the resulting reaction mixture was warmed to ambient temperature and was allowed to stir for a further 2 h. The reaction mixture was diluted with water and extracted with DCM. The organic layer was washed with water and brine, dried over sodiumsulfate and concentrated under reduced pressure. The crude material was purified by column chromatography (silica gel, ethyl acetate in hexane) to afford the product.

[0512] General Procedure D: Acetamide Synthesis

[0513] To a stirred solution of an aniline in DMF at 0 °C was added sodium hydride (60% dispersion in mineral oil). After stirring for 10 min, 2-chloroacetyl chloride was added dropwise and the resulting reaction mixture was allowed to stir for a further 10 min. The reaction mixture was diluted with saturated aqueous sodium hydrogen carbonate and extracted with EtOAc. The organic layer was washed with water and brine, dried over sodium sulfate and concentrated under reduced pressure afford the product.

[0514] General Procedure E: Acetate Synthesis

[0515] To a stirred solution of an alkyl chloride in DMF at ambient temperature was added sodium acetate. The resulting reaction mixture was warmed to 80 °C and was allowed to stir for 2 h. After completion, the reaction mixture was allowed to cool to ambient temperature and was diluted with water. The aqueous phase was extracted with EtOAc and the organic layer was then washed with water. The organic phase was dried over sodium sulfate and concentrated under reduced pressure. The crude material was purified by column chromatography (silica gel, ethyl acetate in hexane) to afford the product.

[0516] General Procedure F: Ester Hydrolysis

[0517] To a stirred solution of an acetate in MeOH or THF at ambient temperature was added a solution of lithium or sodium hydroxide in water. The resulting reaction mixture was warmed to 80 °C and stirred for 2 h. After cooling, the reaction mixture was concentrated under reduced pressure. The crude residue was diluted with water and extracted with ethyl acetate. The organic phase was washed with brine, dried over sodium sulfate and concentrated under reduced pressure. The crude material was purified by column chromatography (silica gel, ethyl acetate in hexane) to afford the product.

[0518] General Procedure G: Ester Hydrolysis

[0519] To a stirred solution of an acetate in MeOH at ambient temperature was added potassium carbonate and water. The resulting reaction mixture was stirred at ambient temperature for 3 h and then concentrated under reduced pressure. The crude residue was diluted with EtOAc and washed with aqueous HCI. The organic phase was concentrated under reduced pressure to afford the product. General Procedure H: Ester Hydrolysis

[0520] To a stirred solution of an acetate in MeOH at ambient temperature was added sodium methoxide. The resulting reaction mixture was stirred at ambient temperature for 1 h. The reaction mixture was concentrated under reduced pressure. The organic phase was concentrated under reduced pressure to afford the product. The crude material was purified by column chromatography (silica gel, ethyl acetate in hexane) to afford the product.

[0521] General Procedure I: Nucleophilic Aromatic Substitution of 2,5-dichloro-1 ,3,4-thiadiazole

[0522] To a stirred solution of an alcohol and 2,5-dichloro-1 ,3,4-thiadiazole in isopropanol at -10 °C was added dropwise a solution of sodium or potassium hydroxide in water over 30 minutes. The resulting reaction mixture was stirred at -10 °C and then warmed to ambient temperature. The reaction was concentrated under reduced pressure. The crude material was purified by column chromatography (silica gel, ethyl acetate in hexane) to afford the product.

[0523] General Procedure J: Nucleophilic Aromatic Substitution of 2, 5-dichloro-1 ,3,4-thiadiazoleTo a stirred solution of an alcohol and sodium hydride (60% dispersion in mineral oil) in toluene at 0 °C was added 2,5-dichloro-1 ,3,4-thiadiazole. The resulting reaction mixture was warmed to ambient temperature and stirred for 30 min. The reaction mixture was quenched with water and extracted with EtOAc. The organic phase was washed with water and brine, dried over sodium sulfate and concentrated under reduced pressure. The crude material was purified by Prep HPLC (Cia-silica, acetonitrile in water) to afford the product.

[0524] General Procedure K: Nucleophilic Aromatic Substitution of 2-chloro-5-(ethylsulfonyl)-1 ,3,4-thiadiazole To a stirred solution of an alcohol and 2-chloro-5-(ethylsulfonyl)-1 ,3,4-thiadiazole in isopropanol at -10 °C was added dropwise a solution of sodium hydroxide in water over 30 min. The resulting reaction mixture was stirred at -10 °C and then warmed to ambient temperature. The reaction was concentrated under reduced pressure. The crude material was purified by column chromatography (silica gel, ethyl acetate in hexane) to afford the product.

[0525] General Procedure L: Nucleophilic Aromatic Substitution of 2-chloro-5-(methylsulfonyl)-1 ,3,4-thiadiazole

[0526] To a stirred solution of an alcohol and potassium hydroxide in isopropanol at ambient temperature was added 2-chloro-5-(methylsulfonyl)-1 ,3,4-thiadiazole. The resulting reaction mixture was stirred at 80 °C for 2 h. The reaction was quenched with water and extracted with EtOAc. The organic phase was washed with water and brine, dried over sodium sulfate and concentrated under reduced pressure. The crude material was purified by Prep HPLC (Cis-silica, acetonitrile in water) to afford the product.

[0527] General Procedure M: Nucleophilic Aromatic Substitution of 2, 5-dichloro-1 ,3,4-thiadiazole

[0528] To a stirred solution of an alcohol and 2, 5-dichloro-1 ,3,4-thiadiazole in isopropanol at 0 °C was added sodium hydroxide (2 M aqueous solution) dropwise. The reaction mixture was allowed to stir for 2 h at 0 °C. After warming to ambient temperature, the solvent was removed under reduced pressure and the crude residue was diluted with water, extracted with EtOAc. The aqueous phase was then acidified to pH 1 with HCI (2 M, aqueous solution) which was extracted with EtOAc. The organic phase was washed with brine, dried over magnesium sulfate and concentrated under reduced pressure to afford the product.

[0529] General Procedure N: Amide Coupling

[0530] To a stirred solution of a carboxylic acid, / V-methylmorpholine and propylphosphonic anhydride (as a 50 wt% solution in EtOAc) in acetonitrile at ambient temperature was added an amine. The resulting reaction mixture was stirred at ambient temperature for 18 h. The solvent was removed under reduced pressure, and the crude residue was taken up in EtOAc and washed with water, HCI (1 M) and brine. The organic phase was dried over magnesium sulfate and concentrated under reduced pressure. The crude material was purified by column chromatography (silica gel, ethyl acetate in hexane) to afford the product.

[0531] General Procedure O: te / Y-Butyloxycarbonyl deprotection

[0532] To a stirred solution of a te / Y-Butyloxycarbonyl protected amine in diethyl ether at ambient temperature was added hydrochloric acid (2 M solution in diethyl ether). The reaction was allowed to stir at ambient temperature for 3 days after which the solvent was removed to yield the product as a hydrochloride salt. General Procedure P: Amide Formation

[0533] To a stirred solution of an aniline in DMF at 0 °C was added sodium hydride and acetoxyacetyl chloride. The reaction mixture was allowed to warm to ambient temperature and was stirred for 12 h. The reactionmixture was quenched with water and extracted with EtOAc. The organic phase was washed with water and brine, dried over sodium sulfate and concentrated under reduced pressure. The crude material was purified by column chromatography (silica gel, ethyl acetate in hexane) to afford the product.

[0534] Table 4

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[0539]

[0540]

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[0542]

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[0544] "

[0545]

[0546]

[0547]

[0548]

[0549] "

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[0551]

[0552]

[0553]

[0554]

[0555]

[0556] Example 1: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluorophenyl)- / V-(prop-2-yn-1-yl)acetamide (I-7).

[0557] Step 1 : Preparation of intermediate l-7a, 4-fluoro- / V-(prop-2-yn-1-yl)aniline.

[0558] Prepared according to general procedure A using 4-fluoroaniline (2.00 g, 18.0 mmol) and 3-bromoprop-1-yne (2.30 mL, 27.0 mmol), DMF (20 mL) and potassium carbonate (2.90 g, 21.3 mmol) to yield 4-fluoro- / V-(prop-2-yn-1-yl)aniline (1.80 g). GCMS (Method E): Rt (retention time) = 9.04 min, m / z = 148.1 [M+H]+.

[0559] Step 2: Preparation of intermediate l-7b, 2-chloro- / V-(4-fluorophenyl)- / V-(prop-2-yn-1-yl)acetamide. Prepared according to general procedure C using 4-fluoro- / V-(prop-2-yn-1-yl)aniline (1.80 g, 12.1 mmol), triethylamine (2.88 mL, 20.5 mmol), DCM (20 mL) and 2-chloroacetyl chloride (1.30 mL, 16.9 mmol) to yield 2-chloro- / V-(4-fluorophenyl)- / V-(prop-2-yn-1-yl)acetamide (1.40 g). LCMS (Method B): Rt = 3.17 min, m / z = 226.0 [M+H]+.

[0560] Step 3: Preparation of intermediate l-7c, 2-((4-fluorophenyl)(prop-2-yn-1-yl)amino)-2-oxoethyl acetate. Prepared according to general procedure E using 2-chloro- / V-(4-fluorophenyl)- / V-(prop-2-yn-1-yl)acetamide (1.40 g, 6.22 mmol), DMF (15 mL) and sodium acetate (0.67 g 8.09 mmol) to yield 2-((4-fluorophenyl)(prop-2-yn-1-yl)amino)-2-oxoethyl acetate (0.90 g). LCMS (Method B): Rt = 3.07 min, m / z = 250.2 [M+H]+.

[0561] Step 4: Preparation of intermediate l-7d, / V-(4-fluorophenyl)-2-hydroxy- / V-(prop-2-yn-1-yl)acetamide. Prepared according to general procedure F using 2-((4-fluorophenyl)(prop-2-yn-1-yl)amino)-2-oxoethyl acetate (0.90 g, 3.63 mmol), MeOH (10 mL), sodium hydroxide (0.72 g, 18.2 mmol) and water (4.0 mL) to yield / V-(4-fluorophenyl)-2-hydroxy- / V-(prop-2-yn-1-yl)acetamide (0.60 g). LCMS (Method B): Rt = 2.61 min, m / z = 208.2 [M+H]+.

[0562] Step 5: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluorophenyl)- / V-(prop-2-yn-1-yl)acetamide (I-7).

[0563] Prepared according to general procedure K using A / -(4-fluorophenyl)-2-hydroxy- / V-(prop-2-yn-1-yl)acetamide (0.10 g, 0.48 mmol), 2-chloro-5-(ethylsulfonyl)-1 ,3,4-thiadiazole (0.10 g, 0.48 mmol), isopropanol (2.0 mL), potassium hydroxide (0.08 g, 1.45 mmol) and water (0.6 mL) to yield 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluorophenyl)- / V-(prop-2-yn-1-yl)acetamide (0.02 g). LCMS (Method C): Rt = 2.53 min, m / z = 326.1 [M+H]+.

[0564] Example 2: Preparation of A / -allyl-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluorophenyl)acetamide (I-4).

[0565] Step 1 : Preparation of intermediate l-4a, A / -allyl-4-fluoroaniline.

[0566] Prepared according to general procedure A using 4-fluoroaniline (1.00 g, 9.00 mmol), allyl bromide (1.20 g, 9.92 mmol), DMF (10 mL) and potassium carbonate (1.24 g, 8.97 mmol) to yield / V-ally l-4-fluoroan Hi ne (0.25 g). LCMS (Method B): Rt = 1.37 min, m / z = 152.2 [M+H]+.

[0567] Step 2: Preparation of intermediate l-4b, / V-allyl-2-chloro- / V-(4-fluorophenyl)acetamide.

[0568] Prepared according to general procedure C using A / -allyl-4-fluoroaniline (0.24 g, 1.59 mmol), DCM (5.0 mL), triethylamine (0.33 mL, 2.37 mmol) and 2-chloroacetyl chloride (0.23 mL, 2.89 mmol) to yield / V-allyl-2-chloro- / V-(4-fluorophenyl)acetamide (0.30 g). LCMS (Method B): Rt = 1.81 min, m / z = 228.3 [M+H]+.

[0569] Step 3: Preparation of intermediate l-4c, 2-(allyl(4-fluorophenyl)amino)-2-oxoethyl acetate.

[0570] Prepared according to general procedure E using / V-allyl-2-chloro- / V-(4-fluorophenyl)acetamide (0.38 g, 1.67 mmol), DMF (3.0 mL) and sodium acetate (0.13 g, 1.58 mmol) to yield 2-(allyl(4-fluorophenyl)amino)-2-oxoethyl acetate (0.25 g). LCMS (Method B): Rt = 3.07 min, m / z = 252.2 [M+H]+. Step 4: Preparation of intermediate l-4d, / V-allyl- / V-(4-fluorophenyl)-2-hydroxyacetamide.

[0571] Prepared according to general procedure F using 2-(allyl(4-fluorophenyl)amino)-2-oxoethyl acetate (0.25 g, 0.99 mmol), MeOH (3.0 mL), sodium hydroxide (0.20 g, 4.98 mmol) and water (1.0 mL) to yield / V-allyl- / V-(4-fluorophenyl)-2-hydroxyacetamide (0.10 g). LCMS (Method B): Rt = 2.77 min, m / z = 209.9 [M+H]+.

[0572] Step 5: Preparation of A / -allyl-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluorophenyl)acetamide (I-4). Prepared according to general procedure K using / V-allyl- / V-(4-fluorophenyl)-2-hydroxyacetamide (0.13 g, 0.62 mmol), 2-chloro-5-(ethylsulfonyl)-1 ,3,4-thiadiazole (0.13 g, 0.62 mmol), isopropanol (2.6 mL), potassium hydroxide (0.10 g, 1.85 mmol) and water (1.0 mL) to yield A / -allyl-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluorophenyl)acetamide (0.10 g). LCMS (Method B): Rt = 2.63 min, m / z = 328.1 , 330.1 [M+H]+.Example 3: Preparation of A / -(but-3-yn-1-yl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluorophenyl)acetamide (IV-11).

[0573] Step 1 : Preparation of intermediate IV-11 a, A / -(but-3-yn-1-yl)-4-fluoroaniline.

[0574] Prepared according to general procedure A using 4-fluoroaniline (2.00 g, 18.0 mmol), 4-bromobut-1-yne (2.8 g, 21.6 mmol), DMF (40 mL) and potassium carbonate (3.7 g, 27.0 mmol) to yield A / -(but-3-yn-1-yl)-4-fluoroaniline (1.8 g).

[0575] Step 2: Preparation of intermediate IV-11 b, / V-(but-3-yn-1-yl)-2-chloro- / V-(4-fluorophenyl)acetamide. Prepared according to general procedure D using A / -(but-3-yn-1-yl)-4-fluoroaniline (1.8 g, 11.0 mmol), DMF (18 mL), sodium hydride (0.66 mg, 16.5 mmol) and 2-chloroacetyl chloride (1.06 mL, 13.2 mmol) to yield / V-(but-3-yn-1-yl)-2-chloro- / V-(4-fluorophenyl)acetamide (1.9 g).

[0576] Step 3: Preparation of intermediate IV-11c, 2-(but-3-yn-1-yl(4-fluorophenyl)amino)-2-oxoethyl acetate. Prepared according to general procedure E using A / -(but-3-yn-1-yl)-2-chloro- / V-(4-fluorophenyl)acetamide (1.9 g, 7.92 mmol), DMF (19 mL) and sodium acetate (0.98 g, 11.9 mmol) to yield 2-(but-3-yn-1-yl(4-fluorophenyl)amino)-2-oxoethyl acetate (0.60 g).

[0577] Step 4: Preparation of intermediate IV-11d, / V-(but-3-yn-1-yl)- / V-(4-fluorophenyl)-2-hydroxyacetamide. Prepared according to general procedure H using 2-(but-3-yn-1-yl(4-fluorophenyl)amino)-2-oxoethyl acetate (0.60 g, 2.27 mmol), MeOH (6.0 mL) and sodium methoxide (0.18 g, 3.41 mmol) to yield A / -(but-3-yn-1-yl)- / V-(4-fluorophenyl)-2-hydroxyacetamide (0.25 g).

[0578] Step 5: Preparation of A / -(but-3-yn-1-yl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluorophenyl)acetamide (IV-11)

[0579] Prepared according to general procedure L using A / -(but-3-yn-1-yl)- / V-(4-fluorophenyl)-2-hydroxyacetamide (0.25 g, 1.13 mmol), 2-chloro-5-(methylsulfonyl)-1 ,3,4-thiadiazole (0.22 g, 1.13 mmol), isopropanol (2.5 mL) and potassium hydroxide (0.10 g, 1.69 mmol) to yield A / -(but-3-yn-1-yl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluorophenyl)acetamide (0.05 g). LCMS (Method D): Rt = 3.11 min, m / z = 339.9, 341.9 [M+H]+.

[0580] Example 4: Preparation of A / -(but-2-yn-1-yl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluorophenyl)acetamide (II-6).

[0581] Step 1 : Preparation of intermediate ll-6a, A / -(but-2-yn-1-yl)-4-fluoroaniline.

[0582] Prepared according to general procedure A using 4-fluoroaniline (2.0 g, 18.0 mmol), 1-bromobut-2-yne (2.8 g, 21.6 mmol), DMF (40 mL) and potassium carbonate (3.7 g, 27.0 mmol) stirring for 3 h to yield N-(but-2-yn-1-yl)-4-fluoroaniline (2.4 g).

[0583] Step 2: Preparation of intermediate ll-6b, / V-(but-2-yn-1-yl)-2-chloro- / V-(4-fluorophenyl)acetamide. Prepared according to general procedure D using A / -(but-2-yn-1-yl)-4-fluoroaniline (2.4 g, 14.7 mmol), DMF (24 mL), sodium hydride (0.88 g, 22.1 mmol) and 2-chloroacetyl chloride (1.41 mL, 17.6 mmol) to yield / V-(but-2-yn-1-yl)-2-chloro- / V-(4-fluorophenyl)acetamide (2.6 g). LCMS (Method D): Rt = 3.09 min, m / z = 239.9, 241.9 [M+H]+.

[0584] Step 3: Preparation of intermediate ll-6c, 2-(but-2-yn-1-yl(4-fluorophenyl)amino)-2-oxoethyl acetate.Prepared according to general procedure E using A / -(but-2-yn-1-yl)-2-chloro- / V-(4-fluorophenyl)acetamide (2.6 g, 10.8 mmol), DMF (26 mL) and sodium acetate (1.0 g, 16.3 mmol) to yield 2-(but-2-yn-1-yl(4-fluorophenyl)amino)-2-oxoethyl acetate (1.2 g).

[0585] Step 4: Preparation of intermediate ll-6d, / V-(but-2-yn-1-yl)- / V-(4-fluorophenyl)-2-hydroxyacetamide. Prepared according to general procedure H using 2-(but-2-yn-1-yl(4-fluorophenyl)amino)-2-oxoethyl acetate (1.2 g, 4.55 mmol), MeOH (12 mL) and sodium methoxide (0.27 g, 6.83 mmol) to yield A / -(but-2-yn-1-yl)- / V-(4-fluorophenyl)-2-hydroxyacetamide (0.80 g).

[0586] Step 5: Preparation of A / -(but-2-yn-1-yl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluorophenyl)acetamide (II-6)

[0587] Prepared according to general procedure L using A / -(but-2-yn-1-yl)- / V-(4-fluorophenyl)-2-hydroxyacetamide (0.30 g, 1.35 mmol), 2-chloro-5-(methylsulfonyl)-1 ,3,4-thiadiazole (0.27 g, 1.35 mmol), isopropanol (3.0 mL) and potassium hydroxide (0.13 g, 2.02 mmol) to yield A / -(but-2-yn-1-yl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluorophenyl)acetamide (0.05 g). LCMS (Method D): Rt = 3.09 min, m / z = 340.0 [M+H]+.

[0588] Example 5: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(3,4-difluorophenyl)- / V-isopropylacetamide (I-42).

[0589] Step 1 : Preparation of intermediate l-42a, 3,4-difluoro- / V-isopropylaniline.

[0590] Prepared according to general procedure B using 3,4-difluoroaniline (2.0 g, 15.5 mmol), acetone (3.44 mL, 46.5 mmol), acetic acid (1.71 mL, 30.9 mmol), STAB (4.9 g, 23.2 mmol) and DCM (20 mL) stirring for 24 h. Extraction was performed with EtOAc, washing with water and brine. The crude material was purified by column chromatography (silica gel, ethyl acetate in hexane) to yield 3,4-difluoro-A / -isopropylaniline (2.3 g). LCMS (Method D): Rt = 3.19 min, m / z = 172.0 [M+H]+.

[0591] Step 2: Preparation of intermediate l-42b, 2-chloro- / V-(3,4-difluorophenyl)- / V-isopropylacetamide. Prepared according to general procedure C using 3,4-difluoro- / V-isopropylaniline (2.3 g, 13.4 mmol), DCM (23 mL), triethylamine (2.75 mL, 20.1 mmol) and 2-chloroacetyl chloride (1.76 mL, 22.8 mmol) stirring for 30 min at ambient temperature and quenching with a saturated solution of sodium hydrogen carbonate to yield 2-chloro- / V-(3,4-difluorophenyl)- / V-isopropylacetamide (1.4 g).

[0592] Step 3: Preparation of intermediate l-42c, 2-((3,4-difluorophenyl)(isopropyl)amino)-2-oxoethyl acetate. Prepared according to general procedure E using 2-chloro- / V-(3,4-difluorophenyl)- / V-isopropylacetamide (1.4 g, 5.65 mmol), DMF (14 mL) and sodium acetate (0.56 g, 6.78 mmol) stirring for 1 h to yield 2-((3,4-difluorophenyl)(isopropyl)amino)-2-oxoethyl acetate (1.5 g). LCMS (Method D): Rt = 3.02 min, m / z = 272.0 [M+H]+.

[0593] Step 4: Preparation of intermediate l-42d, / V-(3,4-difluorophenyl)-2-hydroxy- / V-isopropylacetamide. Prepared according to general procedure H using 2-((3,4-difluorophenyl)(isopropyl)amino)-2-oxoethyl acetate (1.5 g, 5.52 mmol), MeOH (15 mL) and sodium methoxide (0.45 g, 8.29 mmol) to yield A / -(3,4-difluorophenyl)-2-hydroxy- / V-isopropylacetamide (1.2 g). LCMS (Method D): Rt = 2.75 min, m / z = 230.0 [M+H]+.

[0594] Step 5: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(3,4-difluorophenyl)- / V-isopropylacetamide (I-42).Prepared according to general procedure I using A / -(3,4-difluorophenyl)-2-hydroxy- / V-isopropylacetamide (1.28 g, 5.57 mmol), 2,5-dichloro-1 ,3,4-thiadiazole (0.87 g, 5.57 mmol), isopropanol (24 mL), potassium hydroxide (0.31 g, 5.57 mmol) and water (6 mL) stirring for 30 min at -10 °C and then for 2 h at ambient temperature. The reaction mixture was quenched with water and extracted with EtOAc. The organic layer was washed with water, brine, dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude material was purified by Prep HPLC (Cis-silica, acetonitrile in water) to yield 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(3,4-difluorophenyl)- / V-isopropylacetamide (0.05 g). LCMS (Method D): Rt = 3.34 min, m / z = 347.9, 349.9 [M+H]+.

[0595] Example 6: 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(2,4-difluorophenyl)- / V-isopropylacetamide (I-284). Step 1 : Preparation of intermediate l-284a, 2,4-difluoro- / V-isopropylaniline.

[0596] Prepared according to general procedure B using 2,4-difluoroaniline (3.0 g, 23.2 mmol), acetone (6.89 mL, 92.9 mmol), acetic acid (2.67 mL, 46.5 mmol), STAB (11.8 g, 55.8 mmol) and DCM (30 mL) stirring for 24 h. Extraction was performed with EtOAc, washing with water and brine. The crude material was purified by column chromatography (silica gel, ethyl acetate in hexane) to yield 2,4-difluoro-A / -isopropylaniline (2.3 g).

[0597] Step 2: Preparation of intermediate l-284b, 2-chloro- / V-(2,4-difluorophenyl)- / V-isopropylacetamide. Prepared according to general procedure C using 2,4-difluoro- / V-isopropylaniline (2.3 g, 13.4 mmol), DCM (23 mL), triethylamine (2.75 mL, 20.1 mmol) and 2-chloroacetyl chloride (1.76 mL, 22.8 mmol) stirring for 30 min at ambient temperature and quenching with a saturated solution of sodium hydrogen carbonate to yield 2-chloro- / V-(2,4-difluorophenyl)- / V-isopropylacetamide (1.9 g).

[0598] Step 3: Preparation of intermediate l-284c, 2-((2,4-difluorophenyl)(isopropyl)amino)-2-oxoethyl acetate. Prepared according to general procedure E using 2-chloro- / V-(2,4-difluorophenyl)- / V-isopropylacetamide (1.9 g, 7.67 mmol), DMF (19 mL) and sodium acetate (0.76 g, 9.2 mmol) stirring for 1 h to yield 2-((2,4-difluorophenyl)(isopropyl)amino)-2-oxoethyl acetate (1.8 g). LCMS (Method D): Rt = 3.01 min, m / z = 272.0 [M+H]+.

[0599] Step 4: Preparation of intermediate l-284d, / V-(2,4-difluorophenyl)-2-hydroxy- / V-isopropylacetamide. Prepared according to general procedure H using 2-((2,4-difluorophenyl)(isopropyl)amino)-2-oxoethyl acetate (1.8 g, 6.63 mmol), MeOH (18 mL) and sodium methoxide (0.54 g, 9.95 mmol) to yield A / -(2,4-difluorophenyl)-2-hydroxy- / V-isopropylacetamide (1.5 g).

[0600] Step 5: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(2,4-difluorophenyl)- / V-isopropylacetamide (I-284).

[0601] Prepared according to general procedure J using A / -(2,4-difluorophenyl)-2-hydroxy- / V-isopropylacetamide (0.15 g, 0.69 mmol), 2, 5-dichloro-1 ,3,4-thiadiazole (0.11 g, 0.69 mmol), toluene (1.5 mL) and sodium hydride (0.04 g, 1.03 mmol) to yield 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(2,4-difluorophenyl)- / V-isopropylacetamide (0.10 g). LCMS (Method D): Rt = 3.34 min, m / z = 347.9, 349.9 [M+H]+.

[0602] Example 7: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-chloro-3-fluorophenyl)- / V-isopropylacetamide (I-53).

[0603] Step 1 : Preparation of intermediate l-53a, 4-chloro-3-fluoro- / V-isopropylaniline.Prepared according to general procedure B using 4-chloro-3-fluoroaniline (0.50 g, 3.44 mmol), acetone (1.02 mL, 13.70 mmol), acetic acid (0.39 mL, 6.87 mmol), STAB (1.75 g, 8.24 mmol) and DCM (8.0 mL) to yield 4-chloro-3-fluoro- / V-isopropylaniline (0.57 g). LCMS (Method A): Rt = 2.77 min, m / z = 188.1 , 190.1 [M+H]+.f

[0604] Step 2: Preparation of intermediate l-53b, 2-chloro- / V-(4-chloro-3-fluorophenyl)- / V-isopropylacetamide. Prepared according to general procedure C using 4-chloro-3-fluoro- / V-isopropylaniline (0.57 g, 3.02 mmol), toluene (6.1 mL), triethylamine (1.26 mL, 9.06 mmol) and 2-chloroacetyl chloride (0.48 mL, 6.04 mmol) to yield 2-chloro- / V-(4-chloro-3-fluorophenyl)- / V-isopropylacetamide (0.71 g). LCMS (Method A): Rt = 2.55 min, m / z = 264.0, 266.0 [M+H]+.

[0605] Step 3: Preparation of intermediate l-53c, 2-((4-chloro-3-fluorophenyl)(isopropyl)amino)-2-oxoethyl acetate.

[0606] Prepared according to general procedure E using 2-chloro- / V-(4-chloro-3-fluorophenyl)- / V-isopropylacetamide (0.71 g, 2.67 mmol), DMF (4.0 mL) and sodium acetate (0.24 g, 2.94 mmol) stirring for 3 h to yield 2-((4-chloro-3-fluorophenyl)(isopropyl)amino)-2-oxoethyl acetate (0.68 g). LCMS (Method A): Rt = 2.36 min, m / z = 288.1 [M+H]+.

[0607] Step 4: Preparation of intermediate l-53d, / V-(4-chloro-3-fluorophenyl)-2-hydroxy- / V-isopropylacetamide. Prepared according to general procedure G using 2-((4-chloro-3-fluorophenyl)(isopropyl)amino)-2-oxoethyl acetate (0.68 g, 2.36 mmol), MeOH (6.5 mL), potassium carbonate (0.06 g, 0.43 mmol) and water (0.15 mL) to yield / V-(4-chloro-3-fluorophenyl)-2-hydroxy- / V-isopropylacetamide (0.26 g). LCMS (Method A): Rt = 2.11 min, m / z = 246.1 , 248.1 [M+H]+.

[0608] Step 5: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-chloro-3-fluorophenyl)- / V-isopropylacetamide (I-53).

[0609] Prepared according to general procedure I using / V-(4-chloro-3-fluorophenyl)-2-hydroxy- / V-isopropylacetamide (0.13 g, 0.51 mmol), 2,5-dichloro-1 ,3,4-thiadiazole (0.08 g, 0.51 mmol), isopropanol (1.5 mL), sodium hydroxide (0.06 g, 1.52 mmol) and water (0.76 mL) stirring for 30 min at -10 °C and 3.5 h at ambient temperature to yield 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-chloro-3-fluorophenyl)- / V-isopropylacetamide (0.08 g). LCMS (Method A): Rt = 2.67 min, m / z = 364.0, 366.0, 368.0 [M+H]+.

[0610] Example 8: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(3-chloro-4-fluorophenyl)- / V-isopropylacetamide (1-31).

[0611] Step 1 : Preparation of intermediate 1-31 a, 3-chloro-4-fluoro- / V-isopropylaniline.

[0612] Prepared according to general procedure B using 3-chloro-4-fluoroaniline (0.50 g, 3.44 mmol), acetone (1.02 mL, 13.70 mmol), acetic acid (0.39 mL, 6.87 mmol), STAB (1.75 g, 8.24 mmol) and DCM (8 mL) to yield 3-chloro-4-fluoro- / V-isopropylaniline (0.57 g). LCMS (Method A): Rt = 2.53 min, m / z = 188.1 , 190.1 [M+H]+.

[0613] Step 2: Preparation of intermediate 1-31 b, 2-chloro- / V-(3-chloro-4-fluorophenyl)- / V-isopropylacetamide. Prepared according to general procedure C using 3-chloro-4-fluoro- / V-isopropylaniline (0.57 g, 3.03 mmol), toluene (6.1 mL), triethylamine (0.84 mL, 6.05 mmol) and 2-chloroacetyl chloride (1.33 mL, 9.08 mmol) to yield 2-chloro- / V-(3-chloro-4-fluorophenyl)- / V-isopropylacetamide (0.80 g). LCMS (Method A): Rt = 2.52 min, m / z = 264.0, 266.0 [M+H]+.Step 3: Preparation of intermediate 1-31 c, 2-((3-chloro-4-fluorophenyl)(isopropyl)amino)-2-oxoethyl acetate.

[0614] Prepared according to general procedure E using 2-chloro-A / -(3-chloro-4-fluorophenyl)-A / -isopropylacetamide (0.80 g, 2.86 mmol), DMF (4.0 mL) and sodium acetate (0.26 g, 3.15 mmol) stirring for 3 h to yield 2-((3-chloro-4-fluorophenyl)(isopropyl)amino)-2-oxoethyl acetate (0.69 g). LCMS (Method A): Rt = 2.32 min, m / z = 288.1 [M+H]+.

[0615] Step 4: Preparation of intermediate 1-31 d, / V-(3-chloro-4-fluorophenyl)-2-hydroxy- / V-isopropylacetamide. Prepared according to general procedure G using 2-((3-chloro-4-fluorophenyl)(isopropyl)amino)-2-oxoethyl acetate (0.21 g, 0.39 mmol), MeOH (6.5 mL), potassium carbonate (0.01 g, 0.08 mmol) and water (0.15 mL) to yield / V-(3-chloro-4-fluorophenyl)-2-hydroxy- / V-isopropylacetamide (0.16 g). LCMS (Method A): Rt = 2.08 min, m / z = 246.1 , 248.1 [M+H]+.

[0616] Step 5: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(3-chloro-4-fluorophenyl)- / V-isopropylacetamide (1-31).

[0617] Prepared according to general procedure I using / V-(3-chloro-4-fluorophenyl)-2-hydroxy- / V-isopropylacetamide (0.08 g, 0.31 mmol), 2,5-dichloro-1 ,3,4-thiadiazole (0.05 g, 0.31 mmol), isopropanol (1.5 mL), sodium hydroxide (0.04 g, 0.93 mmol) and water (0.46 mL) stirring for 30 min at -10 °C and 4.5 h at ambient temperature to yield 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(3-chloro-4-fluorophenyl)- / V-isopropylacetamide (0.08 g). LCMS (Method A): Rt = 2.62 min, m / z = 364.0, 366.0, 368.0 [M+H]+.

[0618] Example 9: Preparation of A / -(te / Y-butyl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluorophenyl)acetamide (I-5).

[0619] Step 1 : Preparation of intermediate l-5a, / V-(te / Y-butyl)-2-(4-fluorophenoxy)acetamide.

[0620] To a stirred solution of 4-fluorophenol (2.00 g, 17.85 mmol) and / V-te / Y-butyl-2-chloroacetamide (3.20 g, 21.41 mmol) in DMF (20 mL) at 0 °C was added potassium carbonate (4.90 g, 35.46 mmol). The resulting reaction mixture was heated to 110 °C and allowed to stir for 8 h. The reaction mixture was diluted with water and extracted with ethyl acetate. The organic layer was washed water and brine, dried over sodium sulfate and concentrated under reduced pressure. The crude material was purified by column chromatography (silica gel, ethyl acetate in hexane) to afford A / -(te / Y-butyl)-2-(4-fluorophenoxy)acetamide (3.20 g). LCMS (Method B): Rt = 3.23 min, m / z = 226.2 [M+H]+.

[0621] Step 2: Preparation of intermediate l-5b, A / -(te / Y-butyl)-4-fluoroaniline.

[0622] To a stirred solution of / V-(te / Y-butyl)-2-(4-fluorophenoxy)acetamide (3.20 g, 14.21 mmol) in NMP:toluene (1 :2) (50 mL) at ambient temperature was added potassium hydroxide (2.90 g, 51.69 mmol). The reaction mixture was heated to 120 °C and stirred for 16 h. The reaction mixture was diluted with water and extracted with EtOAc. The organic layer was washed with water and brine, dried over sodium sulfate and concentrated under reduced pressure. The crude material was purified by column chromatography (silica gel, ethyl acetate in hexane) to afford A / -(te / Y-butyl)-4-fluoroanili ne (0.60 g). LCMS (Method B); Rt = 3.42 min, m / z = 168.0 [M+H]+.

[0623] Step 3: Preparation of intermediate l-5c, / V-(te / Y-butyl)-2-chloro- / V-(4-fluorophenyl)acetamide.

[0624] Prepared according to general procedure C using A / -(te / Y-butyl)-4-fluoroaniline (0.60 g, 3.59 mmol), DCM (15 mL), triethylamine (0.85 mL, 6.10 mmol) and 2-chloroacetyl chloride (0.30 mL, 3.77 mmol) to yield / V-(te / Y-butyl)-2-chloro- / V-(4-fluorophenyl)acetamide (0.40 g). LCMS (Method B): Rt = 3.48 min, m / z = 244.2 [M+H]+.Step 4: Preparation of intermediate l-5d, 2-(te / Y-butyl(4-fluorophenyl)amino)-2-oxoethyl acetate.

[0625] Prepared according to general procedure E using / V-te / Y-butyl-2-chloro- / V-(4-fluorophenyl)acetamide (0.40 g, 1.64 mmol), DMF (3 mL) and sodium acetate (0.20 g, 2.46 mmol) to yield 2-(te / Y-butyl(4-fluorophenyl)amino)-2-oxoethyl acetate (0.27 g). LCMS (Method B): Rt = 3.18 min, m / z = 268.2 [M+H]+. Step 5: Preparation of intermediate l-5e, / V-(te / Y-butyl)- / V-(4-fluorophenyl)-2-hydroxyacetamide.

[0626] Prepared according to general procedure F using 2-(te / Y-butyl(4-fluorophenyl)amino)-2-oxoethyl acetate (0.27 g, 1.01 mmol), MeOH (2.5 mL), sodium hydroxide (0.20 g, 5.05 mmol) and water (0.6 mL) to yield / V-(te / Y-butyl)- / V-(4-fluorophenyl)-2-hydroxyacetamide (0.20 g). LCMS (Method B): Rt = 3.30 min, m / z = 226.2 [M+H]+.

[0627] Step 6: Preparation of A / -(te / Y-butyl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluorophenyl)acetamide (I-5).

[0628] Prepared according to general procedure K using / V-(te / Y-butyl)- / V-(4-fluorophenyl)-2-hydroxyacetamide (0.20 g, 0.89 mmol), 2-chloro-5-(ethylsulfonyl)-1 ,3,4-thiadiazole (0.19 g, 0.89 mmol), isopropanol (3 mL), potassium hydroxide (0.15 g, 2.67 mmol) and water (0.6 mL) stirring for 30 min at -10 °C to yield A / -(te / Y-butyl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluorophenyl)acetamide (0.12 g). LCMS (Method C): Rt = 2.83 min, m / z = 344.1 [M+H]+.

[0629] Example 10: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluorophenyl)- / V-isobutylacetamide (I-8).

[0630] Step 1 : Preparation of intermediate l-8a, 4-fluoro- / V-isobutylaniline.

[0631] Prepared according to general procedure B using 4-fluoroaniline (2.00 g, 18.0 mmol), isobutyl aldehyde (1.20 g, 18.0 mmol), THF (20 mL) and STAB (5.70 g, 27.0 mmol) to yield 4-fluoro- / V-isobutylaniline (1.50 g). LCMS (Method B): Rt = 3.67 min, m / z = 168.1 [M+H]+.

[0632] Step 2: Preparation of intermediate l-8b, 2-chloro- / V-(4-fluorophenyl)- / V-isobutylacetamide.

[0633] Prepared according to general procedure C using 4-fluoro- / V-isobutylaniline (1.50 g, 8.97 mmol), DCM (15 mL), triethylamine (2.13 mL, 15.25 mmol) and 2-chloroacetyl chloride (0.92 mL, 12.57 mmol) to yield 2-chloro- / V-(4-fluorophenyl)- / V-isobutylacetamide (1.20 g). LCMS (Method B): Rt = 3.46 min, m / z = 244.0 [M+H]+.

[0634] Step 3: Preparation of intermediate l-8c, 2-((4-fluorophenyl)(isobutyl)amino)-2-oxoethyl acetate.

[0635] Prepared according to general procedure E using 2-chloro- / V-(4-fluorophenyl)- / V-isobutylacetamide (1.20 g, 4.94 mmol), DMF (20 mL) and sodium acetate (0.50 g, 6.41 mmol) to yield 2-((4-fluorophenyl)(isobutyl)amino)-2-oxoethyl acetate (1.00 g). LCMS (Method B): Rt = 3.24 min, m / z = 268.1 [M+H]+.

[0636] Step 4: Preparation of intermediate l-8d, / V-(4-fluorophenyl)-2-hydroxy- / V-isobutylacetamide.

[0637] Prepared according to general procedure F using 2-((4-fluorophenyl)(isobutyl)amino)-2-oxoethyl acetate (1.00 g, 3.73 mmol), MeOH (10 mL), sodium hydroxide (0.76 g, 18.17 mmol) and water (4 mL) to yield / V-(4-fluorophenyl)-2-hydroxy- / V-isobutylacetamide (0.80 g). LCMS (Method B): Rt = 3.09 min, m / z = 226.2 [M+H]+.

[0638] Step 5: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluorophenyl)- / V-isobutylacetamide (I-8).Prepared according to general procedure K using / V-(4-fluorophenyl)-2-hydroxy- / V-isobutylacetamide (0.25 g, 1.11 mmol), 2-chloro-5-(ethylsulfonyl)-1 ,3,4-thiadiazole (0.24 g, 1.11 mmol), isopropanol (2 mL), potassium hydroxide (0.19 g, 3.33 mmol) and water (1 mL) at -20 °C for 2 h to yield 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluorophenyl)- / V-isobutylacetamide (0.14 g). LCMS (Method B): Rt = 2.80 min, m / z = 344.1 [M+H]+.

[0639] Example 11: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-cyclopentyl- / V-(4-fluorophenyl)acetamide (I-6).

[0640] Step 1 : Preparation of intermediate l-6a, N-cyclopentyl-4-fluoroaniline.

[0641] To a degassed, stirred solution of 1-chloro-4-fluorobenzene (1.00 g, 7.66 mmol) and cyclopentamine (0.98 g, 11.49 mmol) in DMSO (4 mL), copper iodide (0.22 g, 1.15 mmol), A / 1,A / 2-bis(2,4,6-trimethoxyphenyl)ethanediamide (0.48 g, 1.14 mmol) and potassium phosphate tribasic (4.88 g, 22.98 mmol) were added. The reaction mixture was heated to 120 °C and stirred for 24 h. The reaction mixture was cooled to ambient temperature, diluted with water and extracted with EtOAc. The organic phase was dried over sodium sulfate and concentrated under reduced pressure. The crude material was purified by column chromatography (silica gel, ethyl acetate in petroleum ether) to afford / V-cyclopentyl-4-fluoroaniline (0.60 g). LCMS (Method C): Rt = 3.69 min, m / z = 179.8 [M+H]+.

[0642] Step 2: Preparation of intermediate l-6b, 2-chloro- / V-cyclopentyl- / V-(4-fluorophenyl)acetamide.

[0643] Prepared according to general procedure C using A / -cyclopentyl-4-fluoroaniline (0.60 g, 3.35 mmol), DCM (10 mL), triethylamine (0.75 mL, 5.36 mmol) and 2-chloroacetyl chloride (0.32 mL, 4.02 mmol) to yield 2-chloro- / V-cyclopentyl- / V-(4-fluorophenyl)acetamide (0.55 g). LCMS (Method B): Rt = 3.33 min, m / z = 256.1 [M+H]+.

[0644] Step 3: Preparation of intermediate l-6c, 2-(cyclopentyl(4-fluorophenyl)amino)-2-oxoethyl acetate. Prepared according to general procedure E using 2-chloro- / V-cyclopentyl- / V-(4-fluorophenyl)acetamide (0.55 g, 2.16 mmol), DMF (4 mL) and sodium acetate (0.21 g, 2.56 mmol) to yield 2-(cyclopentyl(4-fluorophenyl)amino)-2-oxoethyl acetate (0.50 g). LCMS (Method B): Rt = 3.35 min, m / z = 280.2 [M+H]+. Step 4: Preparation of intermediate l-6d, / V-cyclopentyl- / V-(4-fluorophenyl)-2-hydroxyacetamide.

[0645] Prepared according to general procedure F using 2-(cyclopentyl(4-fluorophenyl)amino)-2-oxoethyl acetate (0.50 g, 1.79 mmol), MeOH (6 mL), sodium hydroxide (0.36 g, 8.95 mmol) and water (4 mL) to yield / V-cyclopentyl- / V-(4-fluorophenyl)-2-hydroxyacetamide (0.35 g). LCMS (Method B): Rt = 3.13 min, m / z = 238.2 [M+H]+.

[0646] Step 5: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-cyclopentyl- / V-(4-fluorophenyl)acetamide (I-6).

[0647] Prepared according to general procedure K using A / -cyclopentyl- / V-(4-fluorophenyl)-2-hydroxyacetamide (0.15 g, 0.63 mmol), 2-chloro-5-(ethylsulfonyl)-1 ,3,4-thiadiazole (0.13 g, 0.63 mmol), isopropanol (2 mL), potassium hydroxide (0.10 g, 1.85 mmol) and water (1 mL) at -20 °C for 2 h to yield 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-cyclopentyl- / V-(4-fluorophenyl)acetamide (0.10 g). LCMS (Method C): Rt = 2.80 min, m / z = 356.1 [M+H]+.

[0648] Example 12: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(cyanomethyl)- / V-(4-fluorophenyl)acetamide (1-1).

[0649] Step 1 : Preparation of intermediate 1-1 a, 2-((4-fluorophenyl)amino)acetonitrile.To a solution 4-fluoroaniline (1.00 g, 9.00 mmol) and bromoacetonitrile (1.08 g, 9.00 mmol) in anhydrous EtOH (10 mL) at ambient temperature was added sodium acetate (1.23 g, 14.99 mmol). The resulting reaction mixture was heated to 80 °C and stirred for 4 h. After cooling, the solvent was removed under reduced pressure and the crude residue was diluted with water. The aqueous phase was extracted with EtOAc and the organic phase was dried over sodium sulfate and concentrated under reduced pressure. The crude material was purified by column chromatography (silica gel, ethyl acetate in hexane) to afford 2-((4-fluorophenyl)amino)acetonitrile (1.00 g). LCMS (Method B): Rt = 1.81 min, m / z = 151.1 [M+H]+. Step 2: Preparation of intermediate 1-1 b, 2-chloro- / V-(cyanornethyl)- / V-(4-fluorophenyl)acetamide. Prepared according to general procedure C using 2-((4-fluorophenyl)amino)acetonitrile (1.00 g, 6.66 mmol), DCM (10 mL), triethylamine (1.38 mL, 9.89 mmol) and 2-chloroacetyl chloride (0.58 mL, 7.29 mmol) to yield 2-chloro- / V-(cyanornethyl)- / V-(4-fluorophenyl)acetamide (0.90 g). LCMS (Method B): Rt = 2.98 min, m / z = 227.0 [M+H]+.

[0650] Step 3: Preparation of intermediate 1-1 c, 2-((cyanomethyl)(4-fluorophenyl)amino)-2-oxoethyl acetate. Prepared according to general procedure E using 2-chloro- / V-(cyanomethyl)- / V-(4-fluorophenyl)acetamide (0.90 g, 3.97 mmol), DMF (10 mL) and sodium acetate (0.36 g, 4.36 mmol) stirring for 1 h at 80 °C to yield 2-((cyanomethyl)(4-fluorophenyl)amino)-2-oxoethyl acetate (0.80 g). LCMS (Method B): Rt = 2.87 min, m / z = 251.0 [M+H]+.

[0651] Step 4: Preparation of intermediate l-1d, / V-(cyanomethyl)- / V-(4-fluorophenyl)-2-hydroxyacetamide. Prepared according to general procedure G using 2-((cyanomethyl)(4-fluorophenyl)amino)-2-oxoethyl acetate (0.80 g, 3.20 mmol), MeOH (30 mL), potassium carbonate (0.53 g, 3.83 mmol) stirring at 0 °C for 15 min to yield / V-(cyanomethyl)- / V-(4-fluorophenyl)-2-hydroxyacetamide (0.15 g). LCMS (Method B): Rt = 2.33 min, m / z = 209.2 [M+H]+.

[0652] Step 5: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(cyanomethyl)- / V-(4-fluorophenyl)acetamide (1-1).

[0653] Prepared according to general procedure K using / V-(cyanomethyl)- / V-(4-fluorophenyl)-2-hydroxyacetamide (0.15 g, 0.72 mmol), 2-chloro-5-(ethylsulfonyl)-1 ,3,4-thiadiazole (0.15 g, 0.72 mmol), isopropanol (6 mL), potassium hydroxide (0.12 g, 2.16 mmol) and water (0.5 mL) at -20 °C for 45 min to yield 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(cyanomethyl)- / V-(4-fluorophenyl)acetamide (0.02 g). LCMS (Method C): Rt = 2.45 min, m / z = 327.0, 329.0 [M+H]+.

[0654] Example 13: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-cyclopropyl- / V-(4-fluorophenyl)acetamide (I-2).

[0655] Step 1 : Preparation of intermediate l-2a, A / -cyclopropyl-4-fluoroaniline.

[0656] A solution of 1-bromo-4-fluorobenzene (1.00 g, 5.71 mmol) and cyclopropylamine (0.79 mL, 11.40 mmol) in toluene (10.0 mL) was degassed with argon for 20 min. Potassium te / Y-butoxide (2.53 g, 22.55 mmol) followed by BrettPhos (0.27 g, 0.50 mmol) and Pd(dba)2(0.03 g, 0.06 mmol) were then added and the reaction was warmed to 90 °C and stirred for 18 h. After cooling, the reaction mixture was diluted with water and extracted with EtOAc. The organic phase was washed with brine, dried over sodium sulfate and concentrated under reduced pressure. The crude material was purified by column chromatography (silica gel, ethyl acetate in hexane) to afford A / -cyclopropyl-4-fluoroaniline (0.80 g). LCMS (Method C): Rt = 8.30 min, m / z = 150.2 [MH]’.

[0657] Step 2: Preparation of intermediate l-2b, 2-chloro- / V-cyclopropyl- / V-(4-fluorophenyl)acetamide.Prepared according to general procedure C using A / -cyclopropyl-4-fluoroaniline (0.80 g, 5.29 mmol), DCM (10 mL), triethylamine (1.20 mL, 8.60 mmol) and 2-chloroacetyl chloride (0.56 mL, 7.04 mmol) to yield 2-chloro- / V-cyclopropyl- / V-(4-fluorophenyl)acetamide (0.81 g). LCMS (Method B): Rt = 3.02 min, m / z = 228.2 [MH]’.

[0658] Step 3: Preparation of intermediate l-2c, 2-(cyclopropyl(4-fluorophenyl)amino)-2-oxoethyl acetate. Prepared according to general procedure E using 2-chloro- / V-cyclopropyl- / V-(4-fluorophenyl)acetamide (0.81 g, 3.56 mmol), DMF (10 mL) and sodium acetate (0.38 g, 4.63 mmol) stirring for 1 h at 80 °C to yield 2-(cyclopropyl(4-fluorophenyl)amino)-2-oxoethyl acetate (0.55 g). LCMS (Method B): Rt = 3.05 min, m / z = 252.2 [M+H]+.

[0659] Step 4: Preparation of intermediate l-2d, / V-cyclopropyl- / V-(4-fluorophenyl)-2-hydroxyacetamide.

[0660] Prepared according to general procedure F using 2-(cyclopropyl(4-fluorophenyl)amino)-2-oxoethyl acetate (0.55 g, 2.19 mmol), MeOH (10 mL), sodium hydroxide (0.44 g, 10.93 mmol) and water (3 mL) to yield / V-cyclopropyl- / V-(4-fluorophenyl)-2-hydroxyacetamide (0.28 g). LCMS (Method B): Rt = 1.48 min, m / z = 210.3 [M+H]+.

[0661] Step 5: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-cyclopropyl- / V-(4-fluorophenyl)acetamide (I-2).

[0662] Prepared according to general procedure K using A / -cyclopropyl- / V-(4-fluorophenyl)-2-hydroxyacetamide (0.15 g, 0.72 mmol), 2-chloro-5-(ethylsulfonyl)-1 ,3,4-thiadiazole (0.15 g, 0.72 mmol), isopropanol (6 mL), potassium hydroxide (0.12 g, 2.16 mmol) and water (0.5 mL) at -20 °C for 45 min to yield 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-cyclopropyl- / V-(4-fluorophenyl)acetamide (0.02 g). LCMS (Method C): Rt = 2.54 min, m / z = 328.1 , 330.1 [M+H]+.

[0663] Example 14: Preparation of A / -(but-3-yn-2-yl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluorophenyl)acetamide (1-10).

[0664] Step 1 : Preparation of intermediate 1-10a, A / -(but-3-yn-2-yl)-4-fluoroaniline.

[0665] To a stirred solution of triphenylphosphine (8.50 g, 32.41 mmol) in THF (10 mL) at 0 °C under an argon atmosphere was added DEAD (5.03 mL, 32.06 mmol) in THF (5 mL). The mixture was allowed to stir at 0 °C for 20 min, after which but-3-yn-2-ol (2.11 mL, 26.91 mmol) in THF (5 mL) was added. The resulting reaction mixture was stirred for 10 min at 0 °C, followed by the addition of a solution of 4-fluoroaniline (2.0 g, 18.00 mmol) and DIPEA (3.76 mL, 21.59 mmol) in THF (5 mL). The reaction mixture was stirred for 20 min at 0 °C. The reaction mixture was allowed to warm to ambient temperature and was stirred for 2 h. The reaction mixture was diluted with water and extracted with EtOAc. The organic phase was washed with water and brine, dried over sodium sulfate and concentrated under reduced pressure. The crude material was purified by column chromatography (silica gel, ethyl acetate in hexane) to afford N-(but-3-yn-2-yl)-4-fluoroaniline (0.51 g). GCMS (Method E): Rt = 8.27 min, m / z = 163.2 [MH]-.

[0666] Step 2: Preparation of intermediate 1-10b, / V-(but-3-yn-2-yl)-2-chloro- / V-(4-fluorophenyl)acetamide. Prepared according to general procedure C using A / -(but-3-yn-2-yl)-4-fluoroaniline (0.51 g, 3.13 mmol), DCM (10 mL), triethylamine (0.74 mL, 5.31 mmol) and 2-chloroacetyl chloride (0.33 mL, 4.15 mmol) to yield / V-(but-3-yn-2-yl)-2-chloro- / V-(4-fluorophenyl)acetamide (0.38 g). LCMS (Method B): Rt = 3.27 min, m / z = 240.0 [M+H]+.

[0667] Step 3: Preparation of intermediate 1-10c, 2-(but-3-yn-2-yl(4-fluorophenyl)amino)-2-oxoethyl acetate. Prepared according to general procedure E using A / -(but-3-yn-2-yl)-2-chloro- / V-(4-fluorophenyl)acetamide (0.38 g, 1.59 mmol), DMF (4 mL) and sodium acetate (0.17 g, 2.06 mmol)stirring for 1 h at 80 °C to yield 2-(but-3-yn-2-yl(4-fluorophenyl)amino)-2-oxoethyl acetate (0.36 g). LCMS (Method B): Rt = 3.15 min, m / z = 264.2 [M+H]+.

[0668] Step 4: Preparation of intermediate 1-1 Od, / V-(but-3-yn-2-yl)- / V-(4-fluorophenyl)-2-hydroxyacetamide. Prepared according to general procedure F using 2-(but-3-yn-2-yl(4-fluorophenyl)amino)-2-oxoethyl acetate (0.36 g, 1.37 mmol), MeOH (6 mL), sodium hydroxide (0.27 g, 6.83 mmol) and water (1 mL) stirring at 60 °C for 30 min to yield / V-(but-3-yn-2-yl)- / V-(4-fluorophenyl)-2-hydroxyacetamide (0.28 g). LCMS (Method B): Rt = 2.85 min, m / z = 222.0 [M+H]+.

[0669] Step 5: Preparation of A / -(but-3-yn-2-yl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluorophenyl)acetamide (1-10).

[0670] Prepared according to general procedure K using A / -(but-3-yn-2-yl)- / V-(4-fluorophenyl)-2-hydroxyacetamide (0.28 g, 1.27 mmol), 2-chloro-5-(ethylsulfonyl)-1 ,3,4-thiadiazole (0.27 g, 1.29 mmol), isopropanol (6 mL), potassium hydroxide (0.21 g, 3.81 mmol) and water (1 mL) at -20 °C for 30 min to yield A / -(but-3-yn-2-yl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluorophenyl)acetamide (0.14 g). LCMS (Method B): Rt = 2.66 min, m / z = 340.1 , 342.1 [M+H]+.

[0671] Example 15: Preparation of A / -(sec-butyl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluorophenyl)acetamide (I-3).

[0672] Step 1 : Preparation of intermediate 13-a, A / -(sec-butyl)-4-fluoroaniline.

[0673] Prepared according to general procedure A using 4-fluoroaniline (1.50 g, 13.50 mmol), 2-bromobutane (2.30 mL, 20.25 mmol), DMF (15 mL) and potassium carbonate (2.90 g, 20.98 mmol) stirring at 70 °C for 4 h to yield A / -(sec-butyl)-4-fluoroaniline (0.90 g). LCMS (Method B): Rt = 3.59 min, m / z = 168.1 [M+H]+.

[0674] Step 2: Preparation of intermediate l-3b, / V-(sec-butyl)-2-chloro- / V-(4-fluorophenyl)acetamide.

[0675] Prepared according to general procedure C using A / -(sec-butyl)-4-fluoroaniline (0.90 g, 5.38 mmol), DCM (10 mL), triethylamine (1.09 mL, 7.81 mmol) and 2-chloroacetyl chloride (0.40 mL, 5.03 mmol) to yield / V-(sec-butyl)-2-chloro- / V-(4-fluorophenyl)acetamide (0.80 g). LCMS (Method B): Rt = 1.90 min, m / z = 244.3 [M+H]+.

[0676] Step 3: Preparation of intermediate l-3c, 2-(sec-butyl(4-fluorophenyl)amino)-2-oxoethyl acetate.

[0677] Prepared according to general procedure E using / V-(sec-butyl)-2-chloro- / V-(4-fluorophenyl)acetamide (0.80 g, 3.28 mmol), DMF (10 mL) and sodium acetate (0.35 g, 4.27 mmol) to yield 2-(sec-butyl(4-fluorophenyl)amino)-2-oxoethyl acetate (0.80 g). GCMS (Method E): Rt = 8.30 min.

[0678] Step 4: Preparation of intermediate l-3d, / V-(sec-butyl)- / V-(4-fluorophenyl)-2-hydroxyacetamide.

[0679] Prepared according to general procedure F using 2-(sec-butyl(4-fluorophenyl)amino)-2-oxoethyl acetate (0.80 g, 2.99 mmol), MeOH (10 mL), sodium hydroxide (0.57 g, 14.25 mmol) and water (3 mL) stirring at 60 °C for 30 min to yield / V-(sec-butyl)- / V-(4-fluorophenyl)-2-hydroxyacetamide (0.65 g). LCMS (Method B): Rt = 3.12 min, m / z = 226.1 [M+H]+.

[0680] Step 5: Preparation of A / -(sec-butyl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluorophenyl)acetamide (I-3).

[0681] Prepared according to general procedure K using / V-(sec-butyl)- / V-(4-fluorophenyl)-2-hydroxyacetamide (0.30 g, 1.33 mmol), 2-chloro-5-(ethylsulfonyl)-1 ,3,4-thiadiazole (0.28 g, 1.33 mmol), isopropanol (6 mL), potassium hydroxide (0.22 g, 3.97 mmol) and water (1.5 mL) at -20 °C for 30 min to yield / V-(sec-butyl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluorophenyl)acetamide (0.29 g). LCMS (Method B): Rt = 2.76 min, m / z = 344.2 [M+H]+.

[0682] Example 16: 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(3-cyano-4-fluorophenyl)- / V-isopropylacetamide (1-1054).

[0683] Step 1 : Preparation of intermediate 1-1054a, 2-fluoro-5-(isopropylamino)benzonitrile.

[0684] Prepared according to general procedure B using 5-amino-2-fluorobenzonitrile (3.0 g, 22.0 mmol), acetone (6.53 mL, 88.2 mmol), acetic acid (2.65 mL, 44.1 mmol), STAB (11.2 g, 52.9 mmol) and DCM (30 mL) stirring for 24 h. Extraction was performed with EtOAc, washing with water and brine. The crude material was purified by column chromatography (silica gel, ethyl acetate in hexane) to yield 2-fluoro-5-(isopropylamino)benzonitrile (1.8 g).

[0685] Step 2: Preparation of intermediate 1-1054b, 2-chloro- / V-(3-cyano-4-fluorophenyl)- / V-isopropylacetamide.

[0686] Prepared according to general procedure C using 2-fluoro-5-(isopropylamino)benzonitrile (1.5 g, 8.42 mmol), DCM (15 mL), triethylamine (1.76 mL, 12.6 mmol) and 2-chloroacetyl chloride (1.14 mL, 14.3 mmol) stirring for 30 min at ambient temperature and quenching with a saturated solution of sodium hydrogen carbonate to yield 2-chloro- / V-(3-cyano-4-fluorophenyl)- / V-isopropylacetamide (2.1 g).

[0687] Step 3: Preparation of intermediate 1-1054c, 2-((3-cyano-4-fluorophenyl)(isopropyl)amino)-2-oxoethyl acetate.

[0688] Prepared according to general procedure E using 2-chloro- / V-(3-cyano-4-fluorophenyl)- / V-isopropylacetamide (1.0 g, 3.93 mmol), DMF (10 mL) and sodium acetate (0.32 g, 3.93 mmol) stirring for 1 h at 50 °C to yield 2-((3-cyano-4-fluorophenyl)(isopropyl)amino)-2-oxoethyl acetate (0.9 g).

[0689] Step 4: Preparation of intermediate l-1054d, A / -(3-cyano-4-fluorophenyl)-2-hydroxy- / V-isopropylacetamide.

[0690] Prepared according to general procedure F using 2-((3-cyano-4-fluorophenyl)(isopropyl)amino)-2-oxoethyl acetate (1.00 g, 3.59 mmol), THF (4.5 mL) and lithium hydroxide monohydrate (0.15 g, 3.59 mmol) stirring for 10 min at ambient temperature to yield A / -(3-cyano-4-fluorophenyl)-2-hydroxy- / V-isopropylacetamide (0.80 g).

[0691] Step 5: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(3-cyano-4-fluorophenyl)- / V-isopropylacetamide (1-1054).

[0692] Prepared according to general procedure J using A / -(3-cyano-4-fluorophenyl)-2-hydroxy- / V-isopropylacetamide (0.25 g, 1.06 mmol), 2,5-dichloro-1 ,3,4-thiadiazole (0.25 g, 1.59 mmol), toluene (2.5 mL) and sodium hydride (0.06 g, 1.38 mmol) stirring for 1 h to yield 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(3-cyano-4-fluorophenyl)- / V-isopropylacetamide (0.04 g). LCMS (Method D): Rt = 3.19 min, m / z = 354.9, 356.9 [M+H]+.

[0693] Example 17: 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-cyano-3-fluorophenyl)- / V-isopropylacetamide (I-207).

[0694] Step 1 : Preparation of intermediate l-207a, 2-fluoro-4-(isopropylamino)benzonitrile.

[0695] Prepared according to general procedure B using 4-amino-2-fluorobenzonitrile (3.0 g, 22.0 mmol), acetone (6.53 mL, 88.2 mmol), acetic acid (2.65 mL, 44.1 mmol), STAB (11.2 g, 52.9 mmol) and DCM (30 mL) stirring for 24 h. Extraction was performed with EtOAc, washing with water and brine. The crudematerial was purified by column chromatography (silica gel, ethyl acetate in hexane) to yield 2-fluoro-4-(isopropylamino)benzonitrile (1.8 g).

[0696] Step 2: Preparation of intermediate l-207b, 2-chloro- / V-(4-cyano-3-fluorophenyl)- / V-isopropylacetamide. Prepared according to general procedure C using 2-fluoro-4-(isopropylamino)benzonitrile (1.5 g, 8.42 mmol), DCM (15 mL), triethylamine (1.76 mL, 12.6 mmol) and 2-chloroacetyl chloride (1.14 mL, 14.3 mmol) stirring for 30 min at ambient temperature and quenching with a saturated solution of sodium hydrogen carbonate to yield 2-chloro- / V-(4-cyano-3-fluorophenyl)- / V-isopropylacetamide (2.1 g).

[0697] Step 3: Preparation of intermediate l-207c, 2-((4-cyano-3-fluorophenyl)(isopropyl)amino)-2-oxoethyl acetate.

[0698] Prepared according to general procedure E using 2-chloro- / V-(4-cyano-3-fluorophenyl)- / V-isopropylacetamide (2.1 g, 8.25 mmol), DMF (21 mL) and sodium acetate (0.81 g, 9.89 mmol) stirring for 1 h to yield 2-((4-cyano-3-fluorophenyl)(isopropyl)amino)-2-oxoethyl acetate (0.3 g).

[0699] Step 4: Preparation of intermediate l-207d, / V-(2,4-difluorophenyl)-2-hydroxy- / V-isopropylacetamide. Prepared according to general procedure F using 2-((4-cyano-3-fluorophenyl)(isopropyl)amino)-2-oxoethyl acetate (0.35 g, 1.30 mmol), THF (1.75 mL) and lithium hydroxide monohydrate (0.05 g, 1.30 mmol) stirring for 10 min at ambient temperature to yield A / -(4-cyano-3-fluorophenyl)-2-hydroxy- / V-isopropylacetamide (0.22 g).

[0700] Step 5: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-cyano-3-fluorophenyl)- / V-isopropylacetamide (I-207).

[0701] Prepared according to general procedure J using A / -(4-cyano-3-fluorophenyl)-2-hydroxy- / V-isopropylacetamide (0.30 g, 1.27 mmol), 2,5-dichloro-1 ,3,4-thiadiazole (0.30 g, 1.90 mmol), toluene (3 mL) and sodium hydride (0.07 g, 1.65 mmol) stirring for 1 h to yield 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-cyano-3-fluorophenyl)- / V-isopropylacetamide (0.08 g). LCMS (Method D): Rt = 3.15 min, m / z = 354.9, 356.9 [M+H]+.

[0702] Example 18: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(2,4-difluorophenyl)- / V-(prop-2-yn-1-yl)acetamide (I-282).

[0703] Step 1 : Preparation of intermediate l-282a, 2,4-difluoro- / V-(prop-2-yn-1-yl)aniline.

[0704] Prepared according to general procedure A using 2,4-difluoroaniline (0.39 mL, 3.87 mmol), propargyl bromide (0.43 mL, 3.87 mmol), DMF (5 mL) and potassium carbonate (0.64 g, 4.65 mmol) to yield 2,4-difluoro- / V-(prop-2-yn-1-yl)aniline (0.46 g). LCMS (Method A): Rt = 2.50 min, m / z = 168.0 [M+H]+. Step 2: Preparation of intermediate l-282b, 2-chloro- / V-(2,4-difluorophenyl)- / V-(prop-2-yn-1-yl)acetamide.

[0705] Prepared according to general procedure C using 2,4-difluoro- / V-(prop-2-yn-1-yl)aniline (0.37 g, 2.24 mmol), triethylamine (0.34 mL, 2.47 mmol), DCM (5 mL) and 2-chloroacetyl chloride (0.20 mL, 2.47 mmol) to yield 2-chloro- / V-(2,4-difluorophenyl)- / V-(prop-2-yn-1-yl)acetamide (0.52 g). LCMS (Method A): Rt = 2.46 min, m / z = 244.1 [M+H]+.

[0706] Step 3: Preparation of intermediate l-282c, 2-((2,4-difluorophenyl)(prop-2-yn-1-yl)amino)-2-oxoethyl acetate.Prepared according to general procedure E using 2-chloro-A / -(2,4-difluorophenyl)-A / -(prop-2-yn-1-yl)acetamide (0.52 g, 2.14 mmol), DMF (5 mL) and sodium acetate (0.19 g, 2.36 mmol) to yield 2-((2,4-difluorophenyl)(prop-2-yn-1-yl)amino)-2-oxoethyl acetate (0.57 g). LCMS (Method A): Rt = 2.32 min. Step 4: Preparation of intermediate l-282d, A / -(2,4-difluorophenyl)-2-hydroxy- / V-(prop-2-yn-1-yl)acetamide.

[0707] Prepared according to general procedure G using 2-((2,4-difluorophenyl)(prop-2-yn-1-yl)amino)-2-oxoethyl acetate (0.46 g, 1.71 mmol), MeOH (5 mL) and potassium carbonate (0.05 g, 0.36 mmol) to yield / V-(2,4-difluorophenyl)-2-hydroxy- / V-(prop-2-yn-1-yl)acetamide (0.26 g). LCMS (Method A): Rt = 1.98 min, m / z = 226.1 [M+H]+.

[0708] Step 5: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(2,4-difluorophenyl)- / V-(prop-2-yn-1-yl)acetamide (I-282).

[0709] Prepared according to general procedure J using A / -(2,4-difluorophenyl)-2-hydroxy- / V-(prop-2-yn-1-yl)acetamide (0.26 g, 1.13 mmol), 2,5-dichloro-1 ,3,4-thiadiazole (0.18 g, 1.13 mmol), toluene (2 mL) and sodium hydride (0.07 g, 1.70 mmol) to yield 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(2,4-difluorophenyl)- / V-(prop-2-yn-1-yl)acetamide (0.18 g). LCMS (Method C): Rt = 2.63 min, m / z = 344.0 [M+H]+.

[0710] Example 19: Preparation of A / -(but-2-yn-1-yl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(2,4-difluorophenyl)acetamide (11-281).

[0711] Step 1 : Preparation of intermediate ll-281a, A / -(but-2-yn-1-yl)-2,4-difluoroaniline.

[0712] Prepared according to general procedure A using 2,4-difluoroaniline (0.39 mL, 3.87 mmol), 1-bromobut-2-yne (0.34 mL, 3.87 mmol), DMF (5 mL) and potassium carbonate (0.64 g, 4.65 mmol) to yield / V-(but-2-yn-1-yl)-2,4-difluoroaniline (0.57 g). LCMS (Method A): Rt = 2.68 min, m / z = 182.1 [M+H]+.

[0713] Step 2: Preparation of intermediate 11-281 b, / V-(but-2-yn-1-yl)-2-chloro- / V-(2,4-difluorophenyl)acetamide. Prepared according to general procedure C using 2,4-difluoro- / V-(prop-2-yn-1-yl)aniline (0.57 g, 3.12 mmol), triethylamine (0.61 mL, 4.37 mmol), DCM (5 mL) and 2-chloroacetyl chloride (0.35 mL, 4.37 mmol) stirring for 20 min to yield / V-(but-2-yn-1-yl)-2-chloro- / V-(2,4-difluorophenyl)acetamide (0.49 g). LCMS (Method A): Rt = 2.57 min, m / z = 258.1 [M+H]+.

[0714] Step 3: Preparation of intermediate 11-281 c, 2-(but-2-yn-1-yl(2,4-difluorophenyl)amino)-2-oxoethyl acetate.

[0715] Prepared according to general procedure E using A / -(but-2-yn-1-yl)-2-chloro- / V-(2,4-difluorophenyl)acetamide (0.49 g, 1.90 mmol), DMF (5 mL) and sodium acetate (0.33 g, 3.99 mmol) stirring for 38 h to yield 2-(but-2-yn-1-yl(2,4-difluorophenyl)amino)-2-oxoethyl acetate (0.85 g). LCMS (Method A): Rt = 2.43 min, m / z = 282.1 [M+H]+.

[0716] Step 4: Preparation of intermediate 11-281 d, A / -(but-2-yn-1-yl)- / V-(2,4-difluorophenyl)-2-hydroxyacetamide.

[0717] Prepared according to general procedure G using 2-(but-2-yn-1-yl(2,4-difluorophenyl)amino)-2-oxoethyl acetate (0.47 g, 1.69 mmol), MeOH (5 mL) and potassium carbonate (0.05 g, 0.36 mmol) to yield N-(but-2-yn-1-yl)- / V-(2,4-difluorophenyl)-2-hydroxyacetamide (0.40 g). LCMS (Method A): Rt = 2.19 min, m / z = 240.1 [M+H]+.

[0718] Step 5: Preparation of A / -(but-2-yn-1-yl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(2,4-difluorophenyl)acetamide (11-281).Prepared according to general procedure J using A / -(but-2-yn-1-yl)- / V-(2,4-difluorophenyl)-2-hydroxyacetamide (0.37 g, 1.55 mmol), 2,5-dichloro-1 ,3,4-thiadiazole (0.24 g, 1.55 mmol), toluene (2 mL) and sodium hydride (0.09 g, 1.70 mmol) to yield A / -(but-2-yn-1-yl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(2,4-difluorophenyl)acetamide (0.28 g). LCMS (Method A): Rt = 2.76 min, m / z = 358.0 [M+H]+.

[0719] Example 20: Preparation of A / -allyl-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(2,4-difluorophenyl)acetamide (I-279).

[0720] Step 1 : Preparation of intermediate l-279a, A / -allyl-2,4-difluoroaniline.

[0721] Prepared according to general procedure A using 2,4-difluoroaniline (0.39 mL, 3.87 mmol), allyl bromide (0.40 mL, 4.65 mmol), DMF (5 mL) and potassium carbonate (0.64 g, 4.65 mmol) stirring to 42 h to yield A / -allyl-2,4-difluoroaniline (0.42 g). LCMS (Method A): Rt = 2.73 min, m / z = 170.1 [M+H]+.

[0722] Step 2: Preparation of intermediate l-279b, / V-allyl-2-chloro- / V-(2,4-difluorophenyl)acetamide.

[0723] Prepared according to general procedure C using A / -allyl-2,4-difluoroaniline (0.42 g, 2.49 mmol), triethylamine (0.38 mL, 2.74 mmol), DCM (5 mL) and 2-chloroacetyl chloride (0.22 mL, 2.74 mmol) stirring for 10 min to yield / V-allyl-2-chloro- / V-(2,4-difluorophenyl)acetamide (0.36 g). LCMS (Method A): Rt = 2.54 min, m / z = 246.1 [M+H]+.

[0724] Step 3: Preparation of intermediate l-279c, 2-(allyl(2,4-difluorophenyl)amino)-2-oxoethyl acetate. Prepared according to general procedure E using / V-allyl-2-chloro- / V-(2,4-difluorophenyl)acetamide (0.34 g, 1.36 mmol), DMF (5 mL) and sodium acetate (0.24 g, 2.87 mmol) stirring for 18 h to 2-(allyl(2,4-difluorophenyl)amino)-2-oxoethyl acetate (0.36 g). LCMS (Method A): Rt = 2.43 min, m / z = 270.1 [M+H]+.

[0725] Step 4: Preparation of intermediate l-279d, / V-allyl- / V-(2,4-difluorophenyl)-2-hydroxyacetamide.

[0726] Prepared according to general procedure G using 2-(allyl(2,4-difluorophenyl)amino)-2-oxoethyl acetate (0.36 g, 1.33 mmol), MeOH (5 mL) and potassium carbonate (0.04 g, 0.30 mmol) stirring for 2 h to yield / V-allyl- / V-(2,4-difluorophenyl)-2-hydroxyacetamide (0.20 g). LCMS (Method A): Rt = 2.17 min, m / z = 228.1 [M+H]+.

[0727] Step 5: Preparation of A / -allyl-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(2,4-difluorophenyl)acetamide fl-279) .

[0728] Prepared according to general procedure J using / V-allyl- / V-(2,4-difluorophenyl)-2-hydroxyacetamide (0.22 g, 0.96 mmol), 2, 5-dichloro-1 ,3,4-thiadiazole (0.15 g, 0.96 mmol), toluene (2 mL) and sodium hydride (0.06 g, 1.44 mmol) to yield A / -allyl-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(2,4-difluorophenyl)acetamide (0.15 g). LCMS (Method A): Rt = 2.70 min, m / z = 346.0 [M+H]+.

[0729] Example 21: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-isopropyl- / V-(2,3,4-trifluorophenyl)acetamide (1-361).

[0730] Step 1 : Preparation of intermediate 1-361 a, 2,3,4-trifluoro- / V-isopropylaniline.

[0731] Prepared according to general procedure B using 2,3,4-trifluoroaniline (0.36 mL, 3.40 mmol), acetone (1.01 mL, 13.6 mmol), acetic acid (0.39 mL, 6.80 mmol), STAB (1.73 g, 8.16 mmol) and DCM (6 mL) to yield 2,3,4-trifluoro- / V-isopropylaniline (0.61 g). LCMS (Method A): Rt = 2.99 min, m / z = 190.1 [M+H]+. Step 2: Preparation of intermediate 1-361 b, 2-chloro- / V-isopropyl- / V-(2,3,4-trifluorophenyl)acetamide.Prepared according to general procedure C using 2,3,4-trifluoro- / V-isopropylaniline (0.61 g, 3.21 mmol), DCM (6 mL), triethylamine (1.34 mL, 9.63 mmol) and 2-chloroacetyl chloride (0.77 mL, 9.63 mmol) stirring for 70 min at ambient temperature, washing with 6 M HCI (aqueous) to yield 2-chloro- / V-isopropyl-A / -(2,3,4-trifluorophenyl)acetamide (0.72 g). LCMS (Method A): Rt = 2.72 min, m / z = 266.1 [M+H]+. Step 3: Preparation of intermediate 1-361 c, 2-(isopropyl(2,3,4-trifluorophenyl)amino)-2-oxoethyl acetate. Prepared according to general procedure E using 2-chloro- / V-isopropyl- / V-(2,3,4-trifluorophenyl)acetamide (0.73 g, 2.73 mmol), DMF (8 mL) and sodium acetate (0.34 g, 4.01 mmol) stirring for 22 h to yield 2-(isopropyl(2,3,4-trifluorophenyl)amino)-2-oxoethyl acetate (0.52 g). LCMS (Method D): Rt = 2.55 min, m / z = 290.1 [M+H]+.

[0732] Step 4: Preparation of intermediate l-361d, 2-hydroxy- / V-isopropyl- / V-(2,3,4-trifluorophenyl)acetamide. Prepared according to general procedure G using 2-(isopropyl(2,3,4-trifluorophenyl)amino)-2-oxoethyl acetate (0.52 g, 1.81 mmol), potassium carbonate (0.05 g, 0.36 mmol), MeOH (6.5 mL) and water (0.15 mL) to yield 2-hydroxy- / V-isopropyl- / V-(2,3,4-trifluorophenyl)acetamide (0.40 g). LCMS (Method A): Rt = 2.32 min, m / z = 248.1 [M+H]+.

[0733] Step 5: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-isopropyl- / V-(2,3,4-trifluorophenyl)acetamide (1-361).

[0734] Prepared according to general procedure I using 2-hydroxy- / V-isopropyl- / V-(2,3,4-trifluorophenyl)acetamide (0.26 g, 1.04 mmol), 2,5-dichloro-1 ,3,4-thiadiazole (0.16 g, 1.04 mmol), isopropanol (1.5 mL), sodium hydroxide (0.13 g, 3.13 mmol) and water (1.6 mL) stirring for 30 min at -10 °C and then for 3.5 h at ambient temperature to yield 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-isopropyl- / V-(2,3,4-trifluorophenyl)acetamide (0.19 g). LCMS (Method A): Rt = 2.85 min, m / z = 366.0, 368.0 [M+H]+.

[0735] Example 22: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-chloro-2-fluorophenyl)- / V-isopropylacetamide (I-273).

[0736] Step 1 : Preparation of intermediate l-273a, 4-chloro-2-fluoro- / V-isopropylaniline.

[0737] Prepared according to general procedure B using 4-chloro-2-fluoroaniline (0.38 mL, 3.44 mmol), acetone (1.02 mL, 13.7 mmol), acetic acid (0.39 mL, 6.87 mmol), STAB (1.76 g, 8.24 mmol) and DCM (6 mL) to yield 4-chloro-2-fluoro- / V-isopropylaniline (0.61 g). LCMS (Method A): Rt = 3.12 min, m / z = 188.1 , 190.1 [M+H]+.

[0738] Step 2: Preparation of intermediate l-273b, 2-chloro- / V-isopropyl- / V-(2,3,4-trifluorophenyl)acetamide. Prepared according to general procedure C using 4-chloro-2-fluoro- / V-isopropylaniline (0.60 g, 3.21 mmol), DCM (6 mL), triethylamine (1.79 mL, 12.84 mmol) and 2-chloroacetyl chloride (0.77 mL, 9.63 mmol) stirring for 20 min at ambient temperature, washing with HCI (aqueous) to yield 2-chloro- / V-(4-chloro-2-fluorophenyl)- / V-isopropylacetamide (0.54 g). LCMS (Method A): Rt = 2.79 min, m / z = 264.0, 266.0 [M+H]+.

[0739] Step 3: Preparation of intermediate l-273c, 2-((4-chloro-2-fluorophenyl)(isopropyl)amino)-2-oxoethyl acetate.

[0740] Prepared according to general procedure E using 2-chloro- / V-(4-chloro-2-fluorophenyl)- / V-isopropylacetamide (0.51 g, 1.94 mmol), DMF (4 mL) and sodium acetate (0.24 g, 2.91 mmol) stirring for 63 h to yield 2-((4-chloro-2-fluorophenyl)(isopropyl)amino)-2-oxoethyl acetate (0.54 g). LCMS (Method A): Rt = 2.61 min, m / z = 288.1 [M+H]+.Step 4: Preparation of intermediate l-273d, / V-(4-chloro-2-fluorophenyl)-2-hydroxy- / V-isopropylacetamide.

[0741] Prepared according to general procedure G using 2-(isopropyl(2,3,4-trifluorophenyl)amino)-2-oxoethyl acetate (0.52 g, 1.81 mmol), potassium carbonate (0.31 g, 2.24 mmol), MeOH (6.5 mL) and water (0.15 mL) to yield / V-(4-chloro-2-fluorophenyl)-2-hydroxy- / V-isopropylacetamide (0.23 g). LCMS (Method A): Rt = 2.37 min, m / z = 246.1 , 248.1 [M+H]+.

[0742] Step 5: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-chloro-2-fluorophenyl)- / V-isopropylacetamide (I-273).

[0743] Prepared according to general procedure I using / V-(4-chloro-2-fluorophenyl)-2-hydroxy- / V-isopropylacetamide (0.22 g, 0.91 mmol), 2,5-dichloro-1 ,3,4-thiadiazole (0.14 g, 0.91 mmol), isopropanol (1.5 mL), sodium hydroxide (0.11 g, 2.73 mmol) and water (1.4 mL) stirring for 30 min at -10 °C and then for 5 h at ambient temperature to yield 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-chloro-2-fluorophenyl)- / V-isopropylacetamide (0.18 g). LCMS (Method A): Rt = 2.91 min, m / z = 364.0, 366.0 [M+H]+.

[0744] Example 23: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(2,4-dichlorophenyl)- / V-isopropylacetamide (I-295).

[0745] Step 1 : Preparation of intermediate l-295a, 2,4-dichloro- / V-isopropylaniline.

[0746] Prepared according to general procedure B using 2,4-dichloroaniline (0.50 g, 3.09 mmol), acetone (0.92 mL, 12.3 mmol), acetic acid (0.35 mL, 6.17 mmol), STAB (1.57 g, 7.41 mmol) and DCM (5 mL) to yield 2,4-dichloro- / V-isopropylaniline (0.54 g). LCMS (Method A): Rt = 3.37 min, m / z = 204.1, 206.1 , 208.1 [M+H]+.

[0747] Step 2: Preparation of intermediate l-295b, 2-chloro- / V-(2,4-dichlorophenyl)- / V-isopropylacetamide. Prepared according to general procedure C using 2,4-dichloro- / V-isopropylaniline (0.54 g, 2.67 mmol), DCM (5 mL), triethylamine (1.49 mL, 10.68 mmol) and 2-chloroacetyl chloride (0.85 mL, 10.68 mmol) stirring for 30 min at ambient temperature, washing with HCI (aqueous) to yield 2-chloro- / V-(2,4-dichlorophenyl)- / V-isopropylacetamide (0.49 g). LCMS (Method A): Rt = 2.92 min, m / z = 280.0, 284.0 [M+H]+.

[0748] Step 3: Preparation of intermediate l-295c, 2-((2,4-dichlorophenyl)(isopropyl)amino)-2-oxoethyl acetate. Prepared according to general procedure E using 2-chloro- / V-(2,4-dichlorophenyl)- / V-isopropylacetamide (0.49 g, 1.74 mmol), DMF (6 mL) and sodium acetate (0.30 g, 3.65 mmol) stirring for 18 h to yield 2-((2,4-dichlorophenyl)(isopropyl)amino)-2-oxoethyl acetate (0.44 g). LCMS (Method A): Rt = 2.77 min, m / z = 304.0 [M+H]+.

[0749] Step 4: Preparation of intermediate l-295d, / V-(2,4-dichlorophenyl)-2-hydroxy- / V-isopropylacetamide. Prepared according to general procedure G using 2-((2,4-dichlorophenyl)(isopropyl)amino)-2-oxoethyl acetate (0.44 g, 1.44 mmol), potassium carbonate (0.04 g, 0.29 mmol) and MeOH (6.5 mL) to yield N-(2,4-dichlorophenyl)-2-hydroxy- / V-isopropylacetamide (0.29 g). LCMS (Method A): Rt = 2.52 min, m / z = 262.1 , 264.0, 266.0 [M+H]+.

[0750] Step 5: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(2,4-dichlorophenyl)- / V-isopropylacetamide (I-295).

[0751] Prepared according to general procedure J using A / -(2,4-dichlorophenyl)-2-hydroxy- / V-isopropylacetamide (0.22 g, 0.83 mmol),2,5-dichloro-1 ,3,4-thiadiazole (0.13 g, 0.83 mmol), toluene (2 mL) and sodium hydride (0.05 g, 1.25 mmol) to yield 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(2,4-dichlorophenyl)- / V-isopropylacetamide (0.14 g). LCMS (Method A): Rt = 3.01 min, m / z = 382.0, 384.0, 386.0 [M+H]+.

[0752] Example 24: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluoro-2-methylphenyl)- / V-isopropylacetamide (1-317).

[0753] Step 1 : Preparation of intermediate 1-317a, 4-fluoro- / V-isopropyl-2-methylaniline.

[0754] Prepared according to general procedure B using 4-fluoro-2-methylaniline (0.44 mL, 4.00 mmol), acetone (1.18 mL, 16.0 mmol), acetic acid (0.46 mL, 7.99 mmol), STAB (2.03 g, 9.59 mmol) and DCM (5 mL) stirring for 2 h to yield 4-fluoro- / V-isopropyl-2-methylaniline (0.52 g). LCMS (Method A): Rt = 1.68 min, m / z = 168.0 [M+H]+.

[0755] Step 2: Preparation of intermediate 1-317b, 2-chloro- / V-(4-fluoro-2-methylphenyl)- / V-isopropylacetamide. Prepared according to general procedure C using 4-fluoro- / V-isopropyl-2-methylaniline (0.55 g, 3.26 mmol), toluene (5 mL), triethylamine (0.91 mL, 6.52 mmol) and 2-chloroacetyl chloride (0.52 mL, 6.52 mmol) stirring for 20 min at ambient temperature, washing with HCI (aqueous) to yield 2-chloro- / V-(4-fluoro-2-methylphenyl)- / V-isopropylacetamide (0.66 g). LCMS (Method A): Rt = 2.67 min, m / z = 244.1 , 246.1 [M+H]+.

[0756] Step 3: Preparation of intermediate 1-317c, 2-((4-fluoro-2-methylphenyl)(isopropyl)amino)-2-oxoethyl acetate.

[0757] Prepared according to general procedure E using 2-chloro- / V-(4-fluoro-2-methylphenyl)- / V-isopropylacetamide (0.66 g, 2.69 mmol), DMF (6 mL) and sodium acetate (0.46 g, 5.64 mmol) stirring for 18 h to yield 2-((4-fluoro-2-methylphenyl)(isopropyl)amino)-2-oxoethyl acetate (0.45 g). LCMS (Method A): Rt = 2.51 min, m / z = 268.1 [M+H]+.

[0758] Step 4: Preparation of intermediate 1-317d, / V-(4-fluoro-2-methylphenyl)-2-hydroxy- / V-isopropylacetamide.

[0759] Prepared according to general procedure G using 2-((4-fluoro-2-methylphenyl)(isopropyl)amino)-2-oxoethyl acetate (0.45 g, 1.69 mmol), potassium carbonate (0.05 g, 0.38 mmol) and MeOH (5 mL) stirring for 4 h to yield / V-(4-fluoro-2-methylphenyl)-2-hydroxy- / V-isopropylacetamide (0.20 g). LCMS (Method A): Rt = 2.29 min, m / z = 226.0 [M+H]+.

[0760] Step 5: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluoro-2-methylphenyl)- / V-isopropylacetamide (1-317).

[0761] Prepared according to general procedure J using / V-(4-fluoro-2-methylphenyl)-2-hydroxy- / V-isopropylacetamide (0.20 g, 0.89 mmol), 2, 5-dichloro-1 ,3,4-thiadiazole (0.14 g, 0.89 mmol), toluene (2 mL) and sodium hydride (0.05 g, 1.34 mmol) to yield 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluoro-2-methylphenyl)- / V-isopropylacetamide (0.17 g). LCMS (Method A): Rt = 3.86 min, m / z = 344.0, 346.0 [M+H]+.

[0762] Example 25: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-isopropyl- / V-(2,4,5-trifluorophenyl)acetamide (I-339).

[0763] Step 1 : Preparation of intermediate l-339a, 2,4,5-trifluoro- / V-isopropylaniline.

[0764] Prepared according to general procedure B using 2,4,5-trifluoroaniline (0.50 g, 3.40 mmol), acetone (1.01 mL, 13.6 mmol), acetic acid (0.39 mL, 6.80 mmol), STAB (1.74 g, 8.16 mmol) and DCM (6 mL) to yield 2,4,5-trifluoro- / V-isopropylaniline (0.58 g). LCMS (Method A): Rt = 2.96 min, m / z = 190.1 [M+H]+.Step 2: Preparation of intermediate l-339b, 2-chloro-A / -isopropyl-A / -(2,4,5-trifluorophenyl)acetamide. Prepared according to general procedure C using 2,4,5-trifluoro-A / -isopropylaniline (0.60 g, 3.18 mmol), DCM (5 mL), triethylamine (1.33 mL, 9.55 mmol) and 2-chloroacetyl chloride (0.76 mL, 9.55 mmol) stirring for 10 min at ambient temperature, washing with HCI (aqueous) to yield 2-chloro- / V-isopropyl- / V-(2,4,5-trifluorophenyl)acetamide (0.65 g). LCMS (Method A): Rt = 2.65 min, m / z = 266.1 [M+H]+.

[0765] Step 3: Preparation of intermediate l-339c, 2-(isopropyl(2,4,5-trifluorophenyl)amino)-2-oxoethyl acetate. Prepared according to general procedure E using 2-chloro- / V-isopropyl- / V-(2,4,5-trifluorophenyl)acetamide (0.61 g, 2.30 mmol), DMF (4 mL) and sodium acetate (0.28 g, 3.45 mmol) to yield 2-(isopropyl(2,4,5-trifluorophenyl)amino)-2-oxoethyl acetate (0.62 g). LCMS (Method A): Rt = 2.52 min, m / z = 290.1 [M+H]+.

[0766] Step 4: Preparation of intermediate l-339d, 2-hydroxy- / V-isopropyl- / V-(2,4,5-trifluorophenyl)acetamide. Prepared according to general procedure G using 2-(isopropyl(2,4,5-trifluorophenyl)amino)-2-oxoethyl acetate (0.62 g, 2.13 mmol), potassium carbonate (0.06 g, 0.43 mmol), MeOH (6.5 mL) and water (0.15 mL) stirring for 1 h to yield 2-hydroxy- / V-isopropyl- / V-(2,4,5-trifluorophenyl)acetamide (0.32 g). LCMS (Method A): Rt = 2.31 min, m / z = 248.1 [M+H]+.

[0767] Step 5: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-isopropyl- / V-(2,4,5-trifluorophenyl)acetamide (I-339).

[0768] Prepared according to general procedure I using 2-hydroxy- / V-isopropyl- / V-(2,4,5-trifluorophenyl)acetamide (0.32 g, 1.28 mmol), 2,5-dichloro-1 ,3,4-thiadiazole (0.20 g, 1.28 mmol), isopropanol (1.5 mL), sodium hydroxide (0.15 g, 3.85 mmol) and water (1.9 mL) stirring for 3.5 h to yield 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-isopropyl- / V-(2,4,5-trifluorophenyl)acetamide (0.23 g). LCMS (Method A): Rt = 2.80 min, m / z = 366.0, 368.0 [M+H]+.

[0769] Example 26: Preparation of A / -(3-bromo-4-fluorophenyl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-isopropylacetamide (1-1032).

[0770] Step 1 : Preparation of intermediate 1-1032a, 3-bromo-4-fluoro- / V-isopropylaniline.

[0771] Prepared according to general procedure B using 3-bromo-4-fluoroaniline (0.70 g, 3.68 mmol), acetone (1.09 mL, 14.7 mmol), acetic acid (0.42 mL, 7.37 mmol), STAB (1.88 g, 8.44 mmol) and DCM (6 mL) to yield 3-bromo-4-fluoro- / V-isopropylaniline (0.81 g). LCMS (Method A): Rt = 2.77 min, m / z = 232.0 [M+H]+. Step 2: Preparation of intermediate 1-1032b, / V-(3-bromo-4-fluorophenyl)-2-chloro- / V-isopropylacetamide.

[0772] Prepared according to general procedure C using 3-bromo-4-fluoro- / V-isopropylaniline (0.80 g, 3.43 mmol), DCM (6 mL), triethylamine (1.91 mL, 13.72 mmol) and 2-chloroacetyl chloride (1.10 mL, 13.72 mmol), washing with HCI (aqueous) to yield / V-(3-bromo-4-fluorophenyl)-2-chloro- / V-isopropylacetamide (1.07 g). LCMS (Method A): Rt = 2.80 min, m / z = 308.0, 310.0, 312.0 [M+H]+.

[0773] Step 3: Preparation of intermediate 1-1032c, 2-((3-bromo-4-fluorophenyl)(isopropyl)amino)-2-oxoethyl acetate.

[0774] Prepared according to general procedure E using / V-(3-bromo-4-fluorophenyl)-2-chloro- / V-isopropylacetamide (0.96 g, 3.11 mmol), DMF (4 mL) and sodium acetate (0.38 g, 4.67 mmol) stirring for 3 h to yield 2-((3-bromo-4-fluorophenyl)(isopropyl)amino)-2-oxoethyl acetate (0.78 g). LCMS (Method A): Rt = 2.62 min, m / z = 332.0 [M+H]+.Step 4: Preparation of intermediate l-1032d, / V-(3-bromo-4-fluorophenyl)-2-hydroxy- / V-isopropylacetamide.

[0775] Prepared according to general procedure G using 2-((3-bromo-4-fluorophenyl)(isopropyl)amino)-2-oxoethyl acetate (0.58 g, 1.76 mmol), potassium carbonate (0.05 g, 0.35 mmol), MeOH (6.5 mL) and water (0.15 mL) stirring for 1 h to yield / V-(3-bromo-4-fluorophenyl)-2-hydroxy- / V-isopropylacetamide (0.43 g). LCMS (Method A): Rt = 2.39 min, m / z = 290.0, 292.0 [M+H]+.

[0776] Step 5: Preparation of A / -(3-bromo-4-fluorophenyl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-isopropylacetamide (1-1032).

[0777] Prepared according to general procedure I using / V-(3-bromo-4-fluorophenyl)-2-hydroxy- / V-isopropylacetamide (0.31 g, 1.08 mmol), 2,5-dichloro-1 ,3,4-thiadiazole (0.17 g, 1.08 mmol), isopropanol (1.5 mL), sodium hydroxide (0.13 g, 3.24 mmol) and water (1.6 mL) stirring for 3.5 h to yield A / -(3-bromo-4-fluorophenyl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-isopropylacetamide (0.19 g). LCMS (Method A): Rt = 2.94 min, m / z = 408.0, 410.0, 412.0 [M+H]+.

[0778] Example 27: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(4-cyanophenyl)-N-isopropylacetamide (1-185).

[0779] The title compound was prepared from the corresponding 4-(isopropylamino)benzonitrile by the general methods C, E, F and K . LCMS (Method D): Rt = 3.03 min, m / z = 337.0 [M+H]+

[0780] Example 28: Preparation of N-ally l-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(4-cyanophenyl)acetamide (1-180)

[0781] The title compound was prepared from the corresponding 4-aminobenzonitrile by the general methods A, P and M . LCMS (Method D): Rt = 2.48 min, m / z = 334.9 [M+H]+

[0782] Example 29: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(4-cyanophenyl)-N-(prop-2-yn-1-yl)acetamide (1-183)

[0783] The title compound was prepared from the corresponding 4-aminobenzonitrile by the general methods A, P and M . LCMS (Method D): Rt = 2.55 min, m / z = 332.9 [M+H]+

[0784] Example 30: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(4-cyanophenyl)-N-methylacetamide (VI-177)

[0785] The title compound was prepared from the corresponding 44-(methylamino)benzonitrile by the general methods P and M . LCMS (Method D): Rt = 2.23 min, m / z = 308.9 [M+H]+

[0786] Example 31: Preparation of N-allyl-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(3,4-difluorophenyl)acetamide (I-37)

[0787] The title compound was prepared from the corresponding N-allyl-3,4-difluoroaniline by the general method N. LCMS (Method C): Rt = 6.03 min, m / z = 346.0 [M+H]+

[0788] Example 32: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(3,4-difluorophenyl)-N-(prop-2-yn-1-yl)acetamide (I-40)

[0789] The title compound was prepared from the corresponding 3,4-difluoro-N-(prop-2-yn-1-yl)aniline by the general method N. LCMS (Method C): Rt = 6.33 min, m / z = 345.0 [M+H]+Example 33: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(3,4-difluorophenyl)-N-methylacetamide (VII-34)

[0790] The title compound was prepared from the corresponding 3,4-difluoro-N-methylaniline by the general method N. LCMS (Method C): Rt = 6.42 min, m / z = 320.0 [M+H]+

[0791] Example 34: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(2,6-difluorophenyl)-N-isopropylacetamide (I-460)

[0792] The title compound was prepared from the corresponding 2,6-difluoro-N-isopropylaniline by the general methods C, E, F and K . LCMS (Method D): Rt = 4.33 min, m / z = 348.0 [M+H]+

[0793] Example 35: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(2,4-difluorophenyl)-N-methylacetamide (VI-276).

[0794] The title compound was prepared from the corresponding 2,4-difluoro-N-methylaniline by the general method N. LCMS (Method C): Rt = 6.38 min, m / z = 320.0 [M+H]+

[0795] Example 36: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(2,5-difluorophenyl)-N-isopropylacetamide (I-867)

[0796] The title compound was prepared from the corresponding 2,5-difluoro-N-isopropylaniline by the general methods C, E, F and K . LCMS (Method D): Rt = 3.34 min, m / z = 348.0 [M+H]+

[0797] Example 37: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(3,5-difluorophenyl)-N-isopropylacetamide (1-119)

[0798] The title compound was prepared from the corresponding 3,5-difluoro-N-isopropylaniline by the general methods C, E, F and K . LCMS (Method D): Rt = 3.38 min, m / z = 370.0 [M+Na]+

[0799] Example 38: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(2-chloro-4-fluorophenyl)-N-isopropylacetamide (I-262)

[0800] The title compound was prepared from the corresponding N-(2-chloro-4-fluorophenyl)-2-hydroxy-N-isopropylacetamide by the general method M. LCMS (Method C): Rt = 6.43 min, m / z = 365.0 [M+H]+Example 39: Preparation of N-allyl-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(4-chloro-3-fluorophenyl)acetamide (I-48)

[0801] The title compound was prepared from the corresponding N-allyl-N-(4-chloro-3-fluorophenyl)-2-hydroxyacetamide by the general method M. LCMS (Method C): Rt = 8.66 min, m / z = 364.0 [M+H]+Example 40: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(4-chloro-3-fluorophenyl)-N-(prop-2-yn-1- yl)acetamide (1-51)

[0802] The title compound was prepared from the corresponding N-(4-chloro-3-fluorophenyl)-2-hydroxy-N-(prop-2-yn-1-yl)acetamide by the general method M. LCMS (Method C): Rt = 7.79 min, m / z = 362.0 [M+H]+

[0803] Example 41: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(4-chloro-3-fluorophenyl)-N-methylacetamide (VII-45)

[0804] The title compound was prepared from the corresponding 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)acetic acid by the general method M. LCMS (Method C): Rt = 7.22 min, m / z = 338.0 [M+H]+Example 42: Preparation of N-allyl-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(3-chloro-4-fluorophenyl)acetamide (I-26)

[0805] The title compound was prepared from the corresponding N-allyl-3-chloro-4-fluoroaniline by the general method N. LCMS (Method C): Rt = 7.32 min, m / z = 362.0, 364.0 [M+H]+

[0806] Example 43: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(3-chloro-4-fluorophenyl)-N-(prop-2-yn-1-yl)acetamide (I-29)

[0807] The title compound was prepared from the corresponding N-(3-chloro-4-fluorophenyl)-2-hydroxy-N-(prop-2-yn-1-yl)acetamide by the general method M. LCMS (Method C): Rt = 7.86 min, m / z = 362.0, 364.0 [M+H]

[0808] Example 44: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(3-chloro-4-fluorophenyl)-N-methylacetamide (VII-23)

[0809] The title compound was prepared from the corresponding 3-chloro-4-fluoro-N-methylaniline by the general method N. LCMS (Method C): Rt = 7.22 min, m / z = 336.0, 338.0 [M+H]+

[0810] Example 45: Preparation of N-allyl-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(4-chloro-2-fluorophenyl)acetamide (I-268)

[0811] The title compound was prepared from the corresponding N-allyl-4-chloro-2-fluoroaniline by the general method N. LCMS (Method C): Rt = 7.18 min, m / z = 362.0, 364.0 [M+H]+

[0812] Example 46: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(4-chloro-2-fluorophenyl)-N-(prop-2-yn-1-yl)acetamide (1-271)

[0813] The title compound was prepared from the corresponding 4-chloro-2-fluoro-N-(prop-2-yn-1-yl)aniline by the general method N. LCMS (Method C): Rt = 6.73 min, m / z = 360.0, 362.0 [M+H]+

[0814] Example 47: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(4-chloro-2-fluorophenyl)-N-methylacetamide (VII-265)

[0815] The title compound was prepared from the corresponding 4-chloro-2-fluoro-N-methylaniline hydrochloride by the general method N. LCMS (Method C): Rt = 5.42 min, m / z = 336.0, 338.0 [M+H]+Example 48: Preparation of N-allyl-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(4-fluoro-2-methylphenyl)acetamide (1-312)

[0816] The title compound was prepared from the corresponding N-allyl-4-fluoro-2-methylaniline trifluoroacetic acid by the general method N. LCMS (Method C): Rt = 6.88 min, m / z = 342.0, 344.0 [M+H]+Example 49: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(4-fluoro-2-methylphenyl)-N-(prop-2-yn-1 -yl)acetamide (1-315)

[0817] The title compound was prepared from the corresponding 4-fluoro-2-methyl-N-(prop-2-yn-1-yl)aniline trifluoroacetic acid by the general method N. LCMS (Method C): Rt = 5.72 min, m / z = 340.1 [M+H]+Example 50: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(4-fluoro-2-methylphenyl)-N-methylacetamide (VII-309)

[0818] The title compound was prepared from the corresponding 4-fluoro-N,2-dimethylaniline by the general method N. LCMS (Method C): Rt = 5.09 min, m / z = 316.0 [M+H]+Example 51 : 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(2-fluoro-4-methylphenyl)- / V-isopropylacetamide (1-1285)

[0819] Step 1: Preparation of intermediate 1-1285a, 2-fluoro- / V-isopropyl-4-methylaniline

[0820] Prepared according to general procedure B using 2-fluoro-4-methylaniline (0.50 g, 4.0 mmol), acetone (1.18 mL, 16.0 mmol), acetic acid (0.46 mL, 7.99 mmol), STAB (2.03 g, 9.59 mmol) and DCM (5 mL), stirring for 2 h to yield 2-fluoro- / V-isopropyl-4-methylaniline (0.48 g).

[0821] Step 2: Preparation of intermediate 1-1285b, 2-chloro- / V-(2-fluoro-4-methylphenyl)- / V-isopropylacetamide

[0822] Prepared according to general procedure C using 2-fluoro- / V-isopropyl-4-methylaniline (0.48 g, 2.90 mmol), toluene (5 mL), triethylamine (0.81 mL, 5.79 mmol) and 2-chloroacetyl chloride (0.46 mL, 5.79 mmol) stirring for 10 mins. The reaction mixture was quenched with water then HCI (1 M, aqueous) before the organic phase was washed with potassium carbonate (1 M, aqueous). The organic phase was concentrated under reduced pressure to yield 2-chloro- / V-(2-fluoro-4-methylphenyl)- / V-isopropylacetamide (0.48 g).

[0823] Step 3: Preparation of intermediate 1-1285c, 2-((2-fluoro-4-methylphenyl)(isopropyl)amino)-2-oxoethyl acetate

[0824] Prepared according to general procedure E using 2-chloro- / V-(2-fluoro-4-methylphenyl)- / V-isopropylacetamide (0.48 g, 1.86 mmol), DMF (6 mL) and sodium acetate (0.32 g, 3.92 mmol) stirred for 18 h. After work up, no chromatography was conducted to yield 2-((2-fluoro-4-methylphenyl)(isopropyl)amino)-2-oxoethyl acetate (0.36 g).

[0825] Step 4: Preparation of intermediate l-1285d, / V-(2-fluoro-4-methylphenyl)-2-hydroxy- / V-isopropylacetamide.

[0826] Prepared according to general procedure G using 2-((2-fluoro-4-methylphenyl)(isopropyl)amino)-2-oxoethyl acetate (0.36 g, 1.29 mmol), MeOH (5 mL), potassium carbonate (0.04 g, 0.26 mmol) and water (0.10 mL), stirring for 2 h. The solvent was removed, and the crude material was purified by column chromatography (silica gel, ethyl acetate in hexane) to yield A / -(2-fluoro-4-methylphenyl)-2-hydroxy- / V-isopropylacetamide (0.16 g).

[0827] Step 5: Preparation of A / -(2-bromo-4-fluorophenyl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-isopropylacetamide (1-1285).

[0828] Prepared according to general procedure J using A / -(2-fluoro-4-methylphenyl)-2-hydroxy-N-isopropylacetamide (0.16 g, 0.71 mmol), 2,5-dichloro-1 ,3,4-thiadiazole (0.11 g, 0.71 mmol), toluene (2 mL) and sodium hydride (0.04 g, 1.07 mmol) purifying by column chromatography (silica gel, ethyl acetate in hexane) to yield 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(2-fluoro-4-methylphenyl)- / V-isopropylacetamide (0.13 g).

[0829] Example 52: A / -allyl-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(2-fluoro-4-methylphenyl)acetamide (I-1280)

[0830] Step 1: Preparation of intermediate 1-1280a, A / -allyl-2-fluoro-4-methylaniline.

[0831] Prepared according to general procedure A using 2-fluoro-4-methylaniline (0.50 g, 4.00 mmol), allyl bromide (0.35 mL, 4.00 mmol), DMF (6.7 mL) and potassium carbonate (0.66 g, 4.79 mmol) stirring for 4 h to yield A / -allyl-2-fluoro-4-methylaniline (0.19 g).Step 2: Preparation of / V-allyl-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(2-fluoro-4-methylphenyl)acetamide (1-1280).

[0832] Prepared according to general procedure N using 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)acetic acid (0.20 g, 1.03 mmol), / V-methylmorpholine (0.45 mL, 4.15 mmol), propylphosphonic anhydride 50 wt% in EtOAc (1.8 mL, 3.14 mmol), A / -allyl-2-fluoro-4-methylaniline (0.17 g, 1.03 mmol) and acetonitrile (1.9 mL) to yield / V-allyl-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(2-fluoro-4-methylphenyl)acetamide (0.26 g). Example 53: 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(2-fluoro-4-methylphenyl)- / V-(prop-2-yn-1 -yl)acetamide (1-1283)

[0833] Step 1 : Preparation of intermediate 1-1283a, 2-fluoro-4-methyl- / V-(prop-2-yn-1-yl)aniline.

[0834] Prepared according to general procedure A using 2-fluoro-4-methylaniline (0.50 g, 4.00 mmol), propargyl bromide (0.45 mL, 4.00 mmol), DMF (6 mL) and potassium carbonate (0.66 g, 4.79 mmol) stirring for 24 h to yield 2-fluoro-4-methyl- / V-(prop-2-yn-1-yl)aniline (0.46 g).

[0835] Step 2: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(2-fluoro-4-methylphenyl)- / V-(prop-2-yn-1-yl)acetamide (1-1283).

[0836] Prepared according to general procedure N using 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)aceticacid (0.10 g, 0.51 mmol), / V-methylmorpholine (0.23 mL, 2.07 mmol), propylphosphonic anhydride 50 wt% in EtOAc (0.92 mL, 1.54 mmol), 2-fluoro-4-methyl- / V-(prop-2-yn-1-yl)aniline (0.08 g, 0.51 mmol) and acetonitrile (1.9 mL) to yield / V-(2-fluoro-4-methylphenyl)-2-hydroxy- / V-(prop-2-yn-1-yl)acetamide (0.09 g).

[0837] Example 54: N-allyl-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(3,4,5-trifluorophenyl)acetamide (1-1225) Step 1 : Preparation of intermediate 1-1225a, N-allyl-3,4,5-trifluoroaniline.

[0838] Prepared according to general procedure A using 3,4,5-trifluoroaniline (0.28 g, 1.90 mmol), allyl bromide (0.17 mL, 1.90 mmol), DMF (3 mL) and potassium carbonate (0.32 g, 2.28 mmol) stirring for 24 h to yield N-allyl-3,4,5-trifluoroaniline (0.06 g). LCMS (Method A): Rt = 2.58 min, m / z = 188.1 [M+H]+. Step 2: Preparation of N-allyl-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(3,4,5-trifluorophenyl)acetamide (1-1225).

[0839] Prepared according to general procedure N using 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)acetic acid (0.06 g, 0.31 mmol), / V-methylmorpholine (0.14 mL, 1.25 mmol), propylphosphonic anhydride 50 wt% in EtOAc (0.56 mL, 0.94 mmol), N-allyl-3,4,5-trifluoroaniline (0.06 g, 0.31 mmol) and acetonitrile (1.0 mL) to yield N-allyl-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(3,4,5-trifluorophenyl)acetamide (0.06 g). LCMS (Method A): Rt = 2.51 min, m / z = 363.9, 365.9 [M+H]+.

[0840] Example 55: 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-methyl-N-(3,4,5-trifluorophenyl)acetamide (VII-1222)

[0841] Step 1 : Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-methyl-N-(3,4,5-trifluorophenyl)acetamide (VI 1-1222)

[0842] Prepared according to general procedure N using 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)acetic acid (0.07 g, 0.37 mmol), / V-methylmorpholine (0.20 mL, 1.85 mmol), propylphosphonic anhydride 50 wt% in EtOAc (0.66 mL, 1.11 mmol), 3,4,5-trifluoro-N-methylaniline hydrochloride (0.07 g, 0.37 mmol) and acetonitrile (1.0 mL) to yield 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-methyl-N-(3,4,5-trifluorophenyl)acetamide (0.07 g). LCMS (Method A): Rt = 2.26 min, m / z = 337.9, 339.9 [M+H]+.Example 56: A / -(3-bromo-4-fluorophenyl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(prop-2-yn-1 -yl)acetamide (1-1030)

[0843] Step 1 : Preparation of intermediate X, 3-bromo-4-fluoro- / V-(prop-2-yn-1-yl)aniline.

[0844] Prepared according to general procedure A using 3-bromo-4-fluoroaniline (0.29 g, 1.51 mmol), propargyl bromide (0.17 g, 1.51 mmol), DMF (2.5 mL) and potassium carbonate (0.25 g, 1.81 mmol) stirring for 24 h at ambient temperature, 3 h at 40 °C and 4 h at 60 °C to yield 3-bromo-4-fluoro- / V-(prop-2-yn-1-yl)aniline (0.16 g).

[0845] Step 2: Preparation of A / -(3-bromo-4-fluorophenyl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(prop-2-yn-1-yl)acetamide (1-1030).

[0846] Prepared according to general procedure N using 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)aceticacid (0.10 g, 0.51 mmol), / V-methylmorpholine (0.23 mL, 2.08 mmol), propylphosphonic anhydride 50 wt% in EtOAc (0.92 mL, 1.54 mmol), 3-bromo-4-fluoro- / V-(prop-2-yn-1-yl)aniline (0.12 g, 0.51 mmol) and acetonitrile (1.9 mL) to yield A / -(3-bromo-4-fluorophenyl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(prop-2-yn-1-yl)acetamide (0.21 g).

[0847] Example 57: A / -(3-bromo-4-fluorophenyl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-methylacetamide (VI 1-1024)

[0848] Step 1 : Preparation of te / Y-butyl (3-bromo-4-fluorophenyl)(methyl)carbamate (VII-1024a).

[0849] Prepared according to general procedure A using te / Y-butyl (4-bromo-3-fluorophenyl)(methyl)carbamate (0.31 g, 1.08 mmol), sodium hydride (60% dispersion in mineral oil, 0.05 g, 1.29 mmol), THF (3 mL) and methyl iodide (0.10 mL, 1.61 mmol) stirring for 16 h at ambient temperature. After work up the reaction was taken forward crude to yield te / Y-butyl (3-bromo-4-fluorophenyl)(methyl)carbamate (0.16 g).

[0850] Step 2: Preparation of intermediate VII-1024b, 3-bromo-4-fluoro- / V-methylaniline hydrochloride.

[0851] Prepared according to general procedure O using te / Y-butyl (4-bromo-3-fluorophenyl)(methyl)carbamate (0.32 g, 1.06 mmol), hydrochloric acid (2 M in diethyl ether, 5.29 g, 10.6 mmol) and diethyl ether (3.5 mL) to yield 3-bromo-4-fluoro- / V-methylaniline hydrochloride (0.25 g).

[0852] Step 3: Preparation of A / -(3-bromo-4-fluorophenyl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-methylacetamide (VII-1024).

[0853] Prepared according to general procedure N using 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)aceticacid (0.17 g, 0.86 mmol), / V-methylmorpholine (0.47 mL, 4.30 mmol), propylphosphonic anhydride 50 wt% in EtOAc (1.54 mL, 2.58 mmol), 3-bromo-4-fluoro-N-methylaniline hydrochloride (0.21 g, 0.86 mmol) and acetonitrile (3 mL) stirring for 1 h which was purified directly by column chromatography (silica gel, ethyl acetate in hexane) to yield / V-(3-bromo-4-fluorophenyl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-methylacetamide (0.13 g).

[0854] Example 58: 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluoro-3-methoxyphenyl)- / V-isopropylacetamide (1-1296)

[0855] Step 1 : Preparation of intermediate 1-1296a, 4-fluoro- / V-isopropyl-3-methoxyaniline

[0856] Prepared according to general procedure B using 4-fluoro-3-methoxyaniline (0.10 g, 0.71 mmol), acetone (0.21 mL, 2.83 mmol), acetic acid (0.12 mL, 2.13 mmol), STAB (0.41 g, 2.41 mmol) and DCM (6 mL), stirring at ambient temperature for 21 h to yield 4-fluoro- / V-isopropyl-3-methoxyaniline (0.08 g).Step 2: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluoro-3-methoxyphenyl)- / V-isopropylacetamide (1-1296).

[0857] Prepared according to general procedure N using 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)acetic acid (0.08 g, 0.43 mmol), / V-methylmorpholine (0.10 mL, 0.94 mmol), propylphosphonic anhydride 50 wt% in EtOAc (0.51 mL, 0.86 mmol), 4-fluoro- / V-isopropyl-3-methoxyaniline (0.11 g, 0.43 mmol) and acetonitrile (1 mL) stirring for 1 h to yield 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluoro-3-methoxyphenyl)- / V-isopropylacetamide (0.03 g).

[0858] Example 59: / V-allyl-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluoro-3-methoxyphenyl)acetamide (I-1291)

[0859] Step 1 : Preparation of intermediate 1-1291 a, A / -allyl-4-fluoro-3-methoxyaniline.

[0860] Prepared according to general procedure A using 4-fluoro-3-methoxyaniline (0.50 g, 3.54 mmol), allyl bromide (0.37 mL, 4.00 mmol), DMF (5 mL) and potassium carbonate (0.59 g, 4.25 mmol) stirring for 16 h and taken forward crude to yield A / -allyl-4-fluoro-3-methoxyaniline (0.10 g).

[0861] Step 2: Preparation of / V-allyl-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluoro-3-methoxyphenyl)acetamide (1-1291).

[0862] Prepared according to general procedure N using 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)aceticacid (0.12 g, 0.57 mmol), / V-methylmorpholine (0.25 mL, 2.26 mmol), propylphosphonic anhydride 50 wt% in EtOAc (1.01 mL, 1.70 mmol), / V-allyl-4-fluoro-3-methoxyaniline (0.10 g, 0.57 mmol) and acetonitrile (1 mL) to yield / V-allyl-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluoro-3-methoxyphenyl)acetamide (0.06 g). Example 60: 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluoro-3-methoxyphenyl)- / V-(prop-2-yn-1 -yl)acetamide (1-1264)

[0863] Step 1 : Preparation of intermediate 1-1264a, 4-fluoro-3-methoxy- / V-(prop-2-yn-1-yl)aniline.

[0864] Prepared according to general procedure A using 4-fluoro-3-methoxyaniline (0.50 g, 3.54 mmol), propargyl bromide (0.27 g, 3.54 mmol), DMF (5 mL) and potassium carbonate (0.59 g, 4.25 mmol) stirring for 20 h and taken forward crude to yield 4-fluoro-3-methoxy- / V-(prop-2-yn-1-yl)aniline (0.39 g). Step 2: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluoro-3-methoxyphenyl)- / V-(prop-2-yn-1-yl)acetamide (1-1264).

[0865] Prepared according to general procedure N using 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)acetic acid (0.44 g, 2.20 mmol), / V-methylmorpholine (0.97 mL, 8.81 mmol), propylphosphonic anhydride 50 wt% in EtOAc (3.93 mL, 6.61 mmol), 4-fluoro-3-methoxy- / V-(prop-2-yn-1-yl)aniline (0.39 g, 2.20 mmol) and acetonitrile (1 mL) stirring for 1 h to yield 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluoro-3-methoxyphenyl)- / V-(prop-2-yn-1-yl)acetamide (0.33 g).

[0866] Example 61: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluorophenyl)- / V-(3-methyl-butan-2-yl)acetamide (1-11)

[0867] The title compound was prepared in the same manner as I-5 (Example 9), replacing the / V-te / Y-butyl-2-chloroacetamide for an equivalent molar amount of / V-(3-methyl-butan-2-yl)-2-chloroacetamide. LCMS (Method C): Rt = 2.8 min, m / z = 358.1 [M+H]+

[0868] Example 62: / V-(2-bromo-4-fluorophenyl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-isopropylacetamide (1-1043)

[0869] Step 1 : Preparation of intermediate 1-1043a, 2-bromo-4-fluoro- / V-isopropylanilinePrepared according to general procedure B using 2-bromo-4-fluoroaniline (0.50 g, 2.63 mmol), acetone (0.78 mL, 10.5 mmol), acetic acid (0.30 mL, 5.26 mmol), STAB (1.34 g, 6.32 mmol) and DCM (5 mL), stirring for 2 h to yield 2-bromo-4-fluoro- / V-isopropylaniline (0.42 g).

[0870] Step 2: Preparation of intermediate 1-1043b, / V-(2-bromo-4-fluorophenyl)-2-chloro- / V-isopropylacetamide

[0871] Prepared according to general procedure C using 2-bromo-4-fluoro- / V-isopropylaniline (0.42 g, 1.81 mmol), toluene (5 mL), triethylamine (0.76 mL, 5.43 mmol) and 2-chloroacetyl chloride (0.43 mL, 5.43 mmol) stirring for 18 h. The reaction mixture was quenched with water then HCI (1 M, aqueous) before the organic phase was washed with potassium carbonate (1 M, aqueous). The organic phase was concentrated under reduced pressure to yield / V-(2-bromo-4-fluorophenyl)-2-chloro- / V-isopropylacetamide (0.63 g).

[0872] Step 3: Preparation of intermediate 1-1043c, 2-((2-bromo-4-fluorophenyl)(isopropyl)amino)-2-oxoethyl acetate

[0873] Prepared according to general procedure E using N-(2-bromo-4-fluorophenyl)-2-chloro-N-isopropylacetamide (0.63 g, 1.83 mmol), DMF (6 mL) and sodium acetate (0.94 g, 5.67 mmol) stirred for 18 h to yield 2-((2-bromo-4-fluorophenyl)(isopropyl)amino)-2-oxoethyl acetate (0.49 g).

[0874] Step 4: Preparation of intermediate 1-1043d, / V-(2-bromo-4-fluorophenyl)-2-hydroxy- / V-isopropylacetamide

[0875] Prepared according to general procedure G using 2-((2-bromo-4-fluorophenyl)(isopropyl)amino)-2-oxoethyl acetate (0.36 g, 1.04 mmol), MeOH (5 mL), potassium carbonate (0.03 g, 0.21 mmol) and water (0.10 mL), stirring for 2 h. The solvent was removed and the crude material was purified by column chromatography (silica gel, ethyl acetate in hexane) to yield / V-(2-bromo-4-fluorophenyl)-2-hydroxy- / V-isopropylacetamide (0.20 g).

[0876] Step 5: Preparation of A / -(2-bromo-4-fluorophenyl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-isopropylacetamide (1-1043).

[0877] Prepared according to general procedure J using A / -(2-bromo-4-fluorophenyl)-2-hydroxy-N-isopropylacetamide (0.20 g, 0.66 mmol), 2,5-dichloro-1 ,3,4-thiadiazole (0.10 g, 0.66 mmol), toluene (2 mL) and sodium hydride (0.04 g, 0.99 mmol) to yield A / -(2-bromo-4-fluorophenyl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-isopropylacetamide (0.15 g).

[0878] Example 63: 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluoro-2-methoxyphenyl)- / V-isopropylacetamide (I-383)

[0879] Step 1 : Preparation of intermediate l-383a, 4-fluoro- / V-isopropyl-2-methoxyaniline

[0880] Prepared according to general procedure B using 4-fluoro-2-methoxyaniline (0.25 g, 1.77 mmol), acetone (0.53 mL, 7.08 mmol), acetic acid (0.20 mL, 3.54 mmol), STAB (0.91 g, 4.25 mmol) and DCM (6 mL), stirring at ambient temperature for 16 h. Extraction was performed with DCM to yield 4-fluoro- / V-isopropyl-2-methoxyaniline (0.24 g).

[0881] Step 2: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluoro-2-methoxyphenyl)- / V-isopropylacetamide (I-383).

[0882] Prepared according to general procedure N using 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)acetic acid (0.24 g, 1.23 mmol), / V-methylmorpholine (0.30 mL, 2.71 mmol), propylphosphonic anhydride 50 wt% in EtOAc (0.81 mL, 1.36 mmol), 4-fluoro- / V-isopropyl-2-methoxyaniline (0.24 g, 1.23 mmol) and acetonitrile (1 mL)stirring for 2 h to yield 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-A / -(4-fluoro-2-methoxyphenyl)-A / -isopropylacetamide (0.14 g).

[0883] Example 64: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(2-chloro-4,5-difluorophenyl)-N-isopropylacetamide (1-1197)

[0884] The title compound was prepared from the corresponding 2-chloro-4,5-difluoro-N-isopropylaniline by the general method N. LCMS (Method C): Rt = 9.39 min, m / z = 384.0 [M+H]+

[0885] Example 65: 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluoro-3-methoxyphenyl)- / V-methylacetamide (VI 1-1288)

[0886] Step 1 : Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluoro-3-methoxyphenyl)- / V-methylacetamide VII-1288).

[0887] Prepared according to general procedure N using 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)aceticacid (0.10 g, 0.50 mmol), / V-methylmorpholine (0.22 mL, 2.01 mmol), propylphosphonic anhydride 50 wt% in EtOAc (0.90 mL, 1.51 mmol), 4-fluoro-3-methoxy- / V-methylaniline (0.86 g, 0.56 mmol) and acetonitrile (1 mL) stirring for 1 h which was purified directly by column chromatography (silica gel, ethyl acetate in hexane) to yield 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluoro-3-methoxyphenyl)- / V-methylacetamide (0.10 g).

[0888] Example 66: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(5-chloro-2,4-difluorophenyl)-N-isopropylacetamide (1-1197)

[0889] The title compound was prepared from the corresponding 5-chloro-2,4-difluoro-N-isopropylaniline by the general methods P and M . LCMS (Method D): Rt = 3.43 min, m / z = 381.94 [M+H]

[0890] Example 67: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(2,6-dichloro-4-fluorophenyl)- / V-isopropylacetamide (1-515)

[0891] The title compound was prepared from the corresponding 2,6-dichloro-4-fluoro-N-isopropylaniline by the general methods P and M. LCMS (Method D): Rt = 3.04 min, m / z = 399.85 [M+H]+

[0892] Example 68: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(2-chloro-3,4-difluorophenyl)- / V-isopropylacetamide (1-1175)

[0893] The title compound was prepared was prepared from the corresponding 2-chloro-3,4-difluoro-N-isopropylaniline by the general methods P and M. LCMS (Method D): Rt = 2.91 min, m / z = 381.9 [M+H]+

[0894] Example 69: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(3-chloro-4,5-difluorophenyl)- / V-isopropylacetamide (1-1164)

[0895] The title compound was prepared from the corresponding 3-chloro-4,5-difluoro-N-isopropylaniline by the general methods P and M. LCMS (Method D): Rt = 2.93 min, m / z = 381.9 [M+H]+

[0896] Example 70: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(2,3-dichloro-4-fluorophenyl)- / V-isopropylacetamide (1-1153)

[0897] The title compound was prepared from the corresponding 2,3-dichloro-4-fluoro-N-isopropylaniline by the general methods P and M. LCMS (Method D): Rt = 4.51 min, m / z = 399.85 [M+H]+

[0898] Example 71: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(3,5-dichloro-4-fluorophenyl)- / V-isopropylacetamide (1-1142)The title compound was prepared from the corresponding 3,5-dichloro-4-fluoro-N-isopropylaniline by the general methods P and M. LCMS (Method D): Rt = 4.58 min, m / z = 399.85 [M+H]+

[0899] Example 72: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-A / -(2,5-dichloro-4-fluorophenyl)-A / -isopropylacetamide (1-1131)

[0900] The title compound was prepared from the corresponding 2,5-dichloro-4-fluoro-N-isopropylaniline by the general methods P and M. LCMS (Method D): Rt = 4.49 min, m / z = 399.85 [M+H]+

[0901] Example 73: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(2-chloro-4,6-difluorophenyl)- / V-isopropylacetamide (I-504)

[0902] The title compound was prepared from the corresponding 2-chloro-4,6-difluoro-N-isopropylaniline by the general methods P and M. LCMS (Method D): Rt = 3.04 min, m / z = 381 .95 [M+H]+

[0903] Example 74: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(4-fluoro-3-methylphenyl)-N-isopropylacetamide (I-97)

[0904] Step 1 : Preparation of intermediate l-97a, 4-fluoro- / V-isopropyl-3-methylaniline

[0905] Prepared according to general procedure B using 4-fluoro-3-methylaniline (0.20 g, 1.60 mmol), acetone (0.47 mL, 6.39 mmol), acetic acid (0.18 mL, 3.20 mmol), STAB (0.81 g, 3.84 mmol) and DCM (2.1 mL), stirring at ambient temperature for 16 h. Extraction was performed with DCM, washing with sodium hydroxide (1 M) and brine, dried with magnesium sulphate and concentrated under reduced pressure to yield 4-fluoro- / V-isopropyl-3-methylaniline (0.19 g).

[0906] Step 2: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluoro-3-methylphenyl)- / V-isopropylacetamide (I-97).

[0907] Prepared according to general procedure N using 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)aceticacid (0.11 g, 0.60 mmol), / V-methylmorpholine (0.30 mL, 2.73 mmol), propylphosphonic anhydride 50 wt% in EtOAc (1.62 mL, 2.73 mmol), 4-fluoro- / V-isopropyl-3-methylaniline (0.19 g, 0.91 mmol) and acetonitrile (3 mL) stirring for 3 h to yield 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-fluoro-3-methylphenyl)- / V-isopropylacetamide (0.09 g). LCMS (Method C): Rt = 7.25 min, m / z = 344.0, 346.0 [M+H]+Example 75: 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(4-(cyanomethyl)phenyl)- / V-isopropylacetamide (1-1307)

[0908] Step 1 : Preparation of intermediate 1-1307a, 2-(4-(isopropylamino)phenyl)acetonitrile.

[0909] Prepared according to general procedure B using 2-(4-aminophenyl)acetonitrile (0.20 g, 1.51 mmol), acetone (0.45 mL, 6.05 mmol), acetic acid (0.17 mL, 3.03 mmol), STAB (0.77 g, 3.63 mmol) and DCM (2 mL). Extraction was performed with DCM, washing with sodium hydroxide (1 M) and brine, drying with magnesium sulfate and concentrating under reduced pressure to yield 2-(4-(isopropylamino)phenyl)acetonitrile (0.23 g).

[0910] Step 2: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-(cyanomethyl)phenyl)- / V-isopropylacetamide (1-1307).

[0911] Prepared according to general procedure N using 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)acetic acid (0.23 g, 1.19 mmol), / V-methylmorpholine (0.39 mL, 3.56 mmol), propylphosphonic anhydride 50 wt% in EtOAc (2.12 mL, 3.56 mmol), 2-(4-(isopropylamino)phenyl)acetonitrile (0.23 g, 1.19 mmol) and acetonitrile (2 mL) to yield 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(4-(cyanomethyl)phenyl)- / V-isopropylacetamide (0.08 g).Example 76: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(3-fluoro-4-methoxyphenyl)- / V-isopropylacetamide (1-1318)

[0912] Step 1 : Preparation of intermediate 1-1318a, 3-fluoro- / V-isopropyl-4-methoxyaniline

[0913] Prepared according to general procedure B using 3-fluoro-4-methoxyaniline (0.50 g, 3.54 mmol), acetone (1.00 mL, 14.12 mmol), acetic acid (0.50 mL, 8.66 mmol), STAB (1.80 g, 8.49 mmol) and DCM (5 mL), stirring at ambient temperature for 2 h. Extraction was performed with DCM, washing with sodium hydroxide (1 M) and brine, dried by passing through a phase separator and concentrated under reduced pressure to yield 3-fluoro- / V-isopropyl-4-methoxyaniline (0.27 g).

[0914] Step 2: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(3-fluoro-4-methoxyphenyl)- / V-isopropylacetamide (1-1318).

[0915] Prepared according to general procedure N using 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)aceticacid (0.10 g, 0.51 mmol), / V-methylmorpholine (0.16 mL, 1.58 mmol), propylphosphonic anhydride 50 wt% in EtOAc (0.92 mL, 1.54 mmol), 3-fluoro- / V-isopropyl-4-methoxyaniline (0.09 g, 0.51 mmol) and acetonitrile (1.7 mL) to yield 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(3-fluoro-4-methoxyphenyl)- / V-isopropylacetamide (0.12 g).

[0916] Example 77: 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(2-fluoro-4-methoxyphenyl)- / V-isopropylacetamide (1-1329)

[0917] Step 1 : Preparation of intermediate 1-1329a, 2-fluoro- / V-isopropyl-4-methoxyaniline

[0918] Prepared according to general procedure B using 2-fluoro-4-methoxyaniline (1.00 g, 7.08 mmol), acetone (2.10 mL, 28.3 mmol), acetic acid (0.81 mL, 14.2 mmol), STAB (3.60 g, 17.0 mmol) and DCM (10 mL), stirring at ambient temperature for 16 h. Extraction was performed with DCM, washing with sodium hydroxide (1 M) and brine, dried by passing through a phase separator and concentrated under reduced pressure to yield 2-fluoro- / V-isopropyl-4-methoxyaniline (1.13 g).

[0919] Step 2: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(2-fluoro-4-methoxyphenyl)- / V-isopropylacetamide (1-1329).

[0920] Prepared according to general procedure N using 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)aceticacid (0.10 g, 0.51 mmol), / V-methylmorpholine (0.16 mL, 1.58 mmol), propylphosphonic anhydride 50 wt% in EtOAc (0.92 mL, 1.54 mmol), 2-fluoro- / V-isopropyl-4-methoxyaniline (0.09 g, 0.51 mmol) and acetonitrile (1.9 mL) to yield 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(2-fluoro-4-methoxyphenyl)- / V-isopropylacetamide (0.08 g).

[0921] Example 78: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(4-cyano-2-fluorophenyl)-N-isopropylacetamide (1-1120)

[0922] The title compound was prepared from the corresponding 3-fluoro-4-(isopropylamino)benzonitrile by the general methods P and M. LCMS (Method D): Rt = 2.64 min, m / z = 355.0 [M+H]+

[0923] Example 79: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(4-cyano-2,6-difluorophenyl)-N-isopropylacetamide (I-636)

[0924] The title compound was prepared from the corresponding 3,5-difluoro-4-(isopropylamino)benzonitrile by the general methods P and M. LCMS (Method D): Rt = 3.21 min, m / z = 373.0 [M+H]+Example 80: 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(3-(cyanomethyl)phenyl)- / V-isopropylacetamide (1-1340).

[0925] Step 1 : Preparation of intermediate 1-1340a, 2-(3-(isopropylamino)phenyl)acetonitrile.

[0926] Prepared according to general procedure B using 2-(3-aminophenyl)acetonitrile (0.25 g, 1.89 mmol), acetone (0.56 mL, 7.57 mmol), acetic acid (0.22 mL, 3.78 mmol), STAB (0.96 g, 4.54 mmol) and DCM (2 mL) stirring for 2 h. Extraction was performed with DCM, washing with sodium hydroxide (1 M) and brine, drying with magnesium sulfate and concentrating under reduced pressure to yield 2-(3-(isopropylamino)phenyl)acetonitrile (0.25 g).

[0927] Step 2: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)acetic acid (1-1340b)

[0928] Prepared according to general procedure M using tert-butyl 2-hydroxyacetate (1.40 g, 10.6 mmol), 2,5-dichlor-1 ,3,4-thiadiazole (1.64 g, 10.6 mmol), isopropanol (15 mL) and sodium hydroxide (7.41 mL, 14.8 mmol) to yield 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)acetic acid (0.70 g).

[0929] Step 3: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(3-(cyanomethyl)phenyl)- / V-isopropylacetamide (1-1340).

[0930] Prepared according to general procedure N using 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)aceticacid (0.10 g, 0.51 mmol), / V-methylmorpholine (0.17 mL, 1.54 mmol), propylphosphonic anhydride 50 wt% in EtOAc (0.92 mL, 1.54 mmol), 2-(3-(isopropylamino)phenyl)acetonitrile (0.1 g, 0.51 mmol) and acetonitrile (2 mL) to yield 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(3-(cyanomethyl)phenyl)- / V-isopropylacetamide (0.03 g).

[0931] Example 81: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(2,6-dibromo-4-fluorophenyl)-N-isopropylacetamide (1-1109)

[0932] The title compound was prepared from the corresponding 2,6-dibromo-4-fluoro-N-isopropylaniline by the general methods P and M . LCMS (Method D): Rt = 3.20 min, m / z = 487.8 [M+H]+Example 82: Preparation of N-(2-bromo-4,6-difluorophenyl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-isopropylacetamide (1-1098)

[0933] The title compound was prepared from the corresponding 2-bromo-4,6-difluoro-N-isopropylaniline by the general methods P and M . LCMS (Method D): Rt = 3.03 min, m / z = 427.9 [M+H]+

[0934] Example 83: 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(3-fluoro-4-methylphenyl)- / V-isopropylacetamide (I-64)

[0935] Step 1 : Preparation of intermediate l-64a, 3-fluoro- / V-isopropyl-4-methylaniline

[0936] Prepared according to general procedure B using 3-fluoro-4-methylaniline (0.35 g, 2.80 mmol), acetone (0.83 mL, 11.19 mmol), acetic acid (0.32 mL, 5.66 mmol), STAB (1.40 g, 6.61 mmol) and DCM (5 mL), stirring at ambient temperature for 16 h. Extraction was performed with DCM, washing with sodium carbonate (1 M) and brine, dried by passing through a phase separator and concentrated under reduced pressure to yield 3-fluoro- / V-isopropyl-4-methylaniline (0.62 g).

[0937] Step 2: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(3-fluoro-4-methylphenyl)- / V-isopropylacetamide (I-64).

[0938] Prepared according to general procedure N using 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)aceticacid (0.10 g, 0.51 mmol), / V-methylmorpholine (0.21 mL, 2.08 mmol), propylphosphonic anhydride 50 wt% in EtOAc(0.98 mL, 1.54 mmol), 3-fluoro- / V-isopropyl-4-methylaniline (0.12 g, 0.51 mmol) and acetonitrile (1.9 mL) to yield 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-(3-fluoro-4-methylphenyl)- / V-isopropylacetamide (0.10 g).

[0939] Example 84: A / -(4-bromo-3-fluorophenyl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-isopropylacetamide (1-1351)

[0940] Step 1 : Preparation of intermediate 1-1351 a, 4-bromo-3-fluoro- / V-isopropylaniline

[0941] Prepared according to general procedure B using 4-bromo-3-fluoroaniline (0.50 g, 2.60 mmol), acetone (0.78 mL, 10.5 mmol), acetic acid (0.30 mL, 5.26 mmol), STAB (1.30 g, 6.32 mmol) and DCM (5 mL), stirring for 16 h. Extraction was performed with DCM, washing with sodium carbonate (1 M), dried by passing through a phase separator and concentrated under reduced pressure to yield 4-bromo-3-fluoro- / V-isopropylaniline (0.47 g).

[0942] Step 2: Preparation of A / -(4-bromo-3-fluorophenyl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-isopropylacetamide (1-1351).

[0943] Prepared according to general procedure N using 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)aceticacid (0.10 g, 0.51 mmol), / V-methylmorpholine (0.23 mL, 2.08 mmol), propylphosphonic anhydride 50 wt% in EtOAc (0.92 mL, 1.54 mmol), 4-bromo-3-fluoro- / V-isopropylaniline (0.12 g, 0.51 mmol) and acetonitrile (1.8 mL) to yield A / -(4-bromo-3-fluorophenyl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-isopropylacetamide (0.14 g).

[0944] Example 85: A / -(4-bromo-2-fluorophenyl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-isopropylacetamide (1-1362)

[0945] Step 1 : Preparation of intermediate 1-1362a, 4-bromo-2-fluoro- / V-isopropylaniline

[0946] Prepared according to general procedure B using 4-bromo-2-fluoroaniline (0.50 g, 2.60 mmol), acetone (0.78 mL, 11.0 mmol), acetic acid (0.30 mL, 5.30 mmol), STAB (1.30 g, 6.30 mmol) and DCM (5 mL), stirring for 16 h. Extraction was performed with DCM, washing with sodium carbonate (1 M), drying by passing through a phase separator and concentrating under reduced pressure to yield 4-bromo-2-fluoro- / V-isopropylaniline (0.42 g).

[0947] Step 2: Preparation of A / -(4-bromo-2-fluorophenyl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-isopropylacetamide (1-1362).

[0948] Prepared according to general procedure N using 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)aceticacid (0.10 g, 0.51 mmol), / V-methylmorpholine (0.26 mL, 2.27 mmol), propylphosphonic anhydride 50 wt% in EtOAc (1.38 mL, 2.27 mmol), 4-bromo-2-fluoro- / V-isopropylaniline (0.12 g, 0.51 mmol) and acetonitrile (1.8 mL) to yield / V-(4-bromo-2-fluorophenyl)-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)- / V-isopropylacetamide (0.12 g).

[0949] Example 86: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(2,4,6-trifluorophenyl)-N-isopropylacetamide (I-394)

[0950] The title compound was prepared from the corresponding 2,4,6-trifluoro-N-isopropylaniline by the general methods P and M. LCMS (Method D): Rt = 3.28 min, m / z = 365.9 [M+H]+

[0951] Example 87: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(2,3,6-trifluorophenyl)-N-isopropylacetamide (1-1219)

[0952] The title compound was prepared from the corresponding 2,3,6-trifluoro-N-isopropylaniline by the general methods P and M. LCMS (Method D): Rt = 2.81 min, m / z = 365.9 [M+H]+Example 88: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(3,4,5-trifluorophenyl)-N-isopropylacetamide (1-1230)

[0953] The title compound was prepared from the corresponding 3,4,5-trifluoro-N-isopropylaniline by the general methods P and M. LCMS (Method D): Rt = 2.84 min, m / z = 366.0 [M+H]+

[0954] Example 89: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(2,3,5-trifluorophenyl)-N-isopropylacetamide (1-1241)

[0955] The title compound was prepared from the corresponding 2,3,5-trifluoro-N-isopropylaniline by the general methods P and M. LCMS (Method D): Rt = 3.28 min, m / z = 365.9 [M+H]+

[0956] Example 90: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(4-(dimethylamino)phenyl)-N-isopropylacetamide (1-1252)

[0957] The title compound was prepared from the corresponding N1-isopropyl-N4,N4-dimethylbenzene-1 ,4-diamine, by the general method N. LCMS (Method C): Rt = 6.25 min, m / z = 355.0, 357.2 [M+H]+Example 91 : 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(3-(dimethylamino)-4-fluorophenyl)-N-isopropylacetamide (1-1263)

[0958] Step 1 : Preparation of 4-fluoro-N1-isopropyl-N3,N3-dimethylbenzene-1 ,3-diamine (l-1263a) Prepared according to general procedure B using 6-fluoro-N1 ,N1-dimethylbenzene-1 ,3-diamine (0.13 g, 0.75 mmol), acetone (0.22 mL, 2.99 mmol), acetic acid (0.09 mL, 1.49 mmol), STAB (0.38 g, 1.79 mmol) and DCM (5 mL), stirring for 16 h to yield 4-fluoro-N1-isopropyl-N3,N3-dimethylbenzene-1 ,3-diamine (0.11 g).

[0959] Step 2: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(3-(dimethylamino)-4-fluorophenyl)-N-isopropylacetamide (1-1263)

[0960] Prepared according to general procedure N using 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)acetic acid (0.09 g, 0.49 mmol), / V-methylmorpholine (0.27 mL, 2.43 mmol), propylphosphonic anhydride 50 wt% in EtOAc (0.87 mL, 1.46 mmol), 4-fluoro-N1-isopropyl-N3,N3-dimethylbenzene-1 ,3-diamine (0.11 g, 0.49 mmol) and acetonitrile (2.0 mL) to yield 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(3-(dimethylamino)-4-fluorophenyl)-N-isopropylacetamide (0.10 g). LCMS (Method B): Rt = 2.48 min, m / z = 373.0, 375.0 [M+H]+.

[0961] Example 92: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-isopropyl-N-(thiophen-2-yl)acetamide (1-1373)

[0962] The title compound was prepared from the corresponding N-isopropylthiophen-2-amine by the general methods P and M. LCMS (Method D): Rt = 2.28 min, m / z = 318.0 [M+H]+

[0963] Example 93: Preparation of N-allyl-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(thiophen-2-yl)acetamide (1-1368)

[0964] The title compound was prepared from the corresponding N-allylthiophen-2-amine by the general methods P and M. LCMS (Method D): Rt = 2.0 min, m / z = 316.0 [M+H]+

[0965] Example 94: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(prop-2-yn-1-yl)-N-(thiophen-2-yl)acetamide (1-1371)

[0966] The title compound was prepared from the corresponding N-(prop-2-yn-1-yl)thiophen-2-amine by the general methods P and M. LCMS (Method D): Rt = 2.0 min, m / z = 314.0 [M+H]+Example 95: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-isopropyl-N-(4-nitrophenyl)acetamide (1-1384)

[0967] The title compound was prepared from the corresponding N-isopropyl-4-nitroaniline by the general methods C, E, F and M. LCMS (Method D): Rt = 4.26 min, m / z = 357.0 [M+H]+

[0968] Example 96: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-isopropyl-N-(thiazol-5-yl)acetamide (1-1076)

[0969] The title compound was prepared from the corresponding N-isopropylthiazol-5-amine by the general methods P and M. LCMS (Method D): Rt = 2.36 min, m / z = 318.95 [M+H]+

[0970] Example 97: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-methyl-N-(4-nitrophenyl)acetamide (VI 1-1068)

[0971] The title compound was prepared from the corresponding N-methyl-4-nitroaniline by the general methods P and M. LCMS (Method D): Rt = 2.39 min, m / z = 328.95 [M+H]+

[0972] Example 98: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-isopropyl-N-(benzothiazol-6-yl)acetamide (1-1395)

[0973] The title compound was prepared from the corresponding N-isopropylbenzothiazol-6-amine by the general methods P and M. LCMS (Method D): Rt = 2.8 min, m / z = 369.0 [M+H]+

[0974] Example 99: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-isopropyl-N-(thiophen-3-yl)acetamide (1-1406)

[0975] The title compound was prepared from the corresponding N-isopropylthiophen-3-amine by the general methods P and M. LCMS (Method D): Rt = 2.3 min, m / z = 318.0 [M+H]+

[0976] Example 100: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-isopropyl-N-(thiazol-2-yl)acetamide (1-1417)

[0977] The title compound was prepared from the corresponding N-isopropylthiazol-2-amine by the general methods P and M. LCMS (Method D): Rt = 2.3 min, m / z = 318.96 [M+H]+

[0978] Example 101: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-isopropyl-N-(3,5-difluoropyridin-2-yl)acetamide (1-1428)

[0979] The title compound was prepared from the corresponding N-isopropyl-3,5-difluoropyridin-2-amine by the general methods P and M. LCMS (Method D): Rt = 2.3 min, m / z = 318.96 [M+H]+

[0980] Example 102: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-isopropyl-N-pyridin-3-ylacetamide (1-1439)

[0981] The title compound was prepared from the corresponding N-isopropylpyridin-3-amine by the general methods P and M. LCMS (Method D): Rt = 2.3 min, m / z = 318.96 [M+H]+

[0982] Example 103: Preparation of N-allyl-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(2,3,4-trifluorophenyl)acetamide (I-356)

[0983] The title compound was prepared from the corresponding N-allyl-2,3,4-trifluoroaniline by the general methods P and M. LCMS (Method D): Rt = 2.78 min, m / z = 363.85 [M+H]+Example 104: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(2,3,4-trifluorophenyl)-N-(prop-2-yn-1-yl)acetamide (I-359)

[0984] The title compound was prepared from the corresponding 2,3,4-trifluoro-N-(prop-2-yn-1-yl)aniline by the general methods P and M. LCMS (Method D): Rt = 2.65 min, m / z = 361 .85 [M+H]+

[0985] Example 105: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(2,3,4-trifluorophenyl)-N-methylacetamide (VII-353)

[0986] The title compound was prepared from the corresponding 2,3,4-trifluoro-N-methylaniline by the general methods P and M. LCMS (Method D): Rt = 2.54 min, m / z = 337.85 [M+H]+

[0987] Example 106: Preparation of N-allyl-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(2,4,5-trifluorophenyl) acetamide (I-334)

[0988] The title compound was prepared from the corresponding A / -allyl-2,4,5-trifluoroaniline by the general methods P and M. LCMS (Method D): Rt = 2.74 min, m / z = 363.9 [M+H]+

[0989] Example 107: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(2,4,5-trifluorophenyl)-N-(prop-2-yn-1-yl)acetamide (I-337)

[0990] The title compound was prepared from the corresponding 2,4,5-trifluoro-N-(prop-2-yn-1-yl)aniline by the general methods P and M. LCMS (Method D): Rt = 2.63 min, m / z = 361 .85 [M+H]+

[0991] Example 108: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(2,4,5-trifluorophenyl)-N-methylacetamide (VII-331)

[0992] The title compound was prepared from the corresponding 2,4,5-trifluoro-N-methylaniline by the general methods P and M. LCMS (Method D): Rt = 2.51 min, m / z = 337.90 [M+H]+

[0993] Example 109: Preparation of N-allyl-2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(4-fluoro-3-methylphenyl)-acetamide (I-92)

[0994] The title compound was prepared from the corresponding A / -allyl-4-fluoro-3-methyl-aniline by the general methods P and M. LCMS (Method D): Rt = 2.82 min, m / z = 342.05 [M+H]+

[0995] Example 110: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(4-fluoro-3-methylphenyl)-N-(prop-2-yn-1-yl)acetamide (I-95)

[0996] The title compound was prepared from the corresponding 4-fluoro-3-methyl-N-(prop-2-yn-1-yl)aniline by the general methods P and M . LCMS (Method D): Rt = 2.71 min, m / z = 340.0 [M+H]+Example 111: 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(4-fluoro-3-methylphenyl)-N-methylacetamide (VII-89)

[0997] Step 1 : Preparation of intermediate VI l-89a 4-fluoro-N,3-dimethylaniline.

[0998] Prepared according to general procedure A using 4-fluoro-3-methylaniline (0.50 g, 4.00 mmol) in a solution of MeCN (8 mL) methyl iodide (0. 254 mL, 4.00 mmol) was added at OoC and the reaction was warmed to room temperature and stirred for 6 h at ambient temperature. After work up the reaction was taken forward crude to yield 4-fluoro-N,3-dimethylaniline (0.18 g).

[0999] Step 2: Preparation of intermediate Vll-89b, 2-((4-fluoro-3-methylphenyl)(methyl)amino)-2-oxoethyl acetate.Prepared according to general procedure P using 4-fluoro-3-methylaniline (0.17 g, 1 .22 mmol), sodium hydride (0.06 g, 1.46 mmol), acetoxyacetyl chloride (0.20 g, 1.46 mmol) and DMF (1.7 mL) to yield -((4-fluoro-3-methylphenyl)(methyl)amino)-2-oxoethyl acetate (0.25 g).

[1000] Step 3: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(4-fluoro-3-methylphenyl)-N-methylacetamide (VII-89)

[1001] Prepared according to general procedure I -((4-fluoro-3-methylphenyl)(methyl)amino)-2-oxoethyl acetate (0.20 g, 0.83 mmol), 2,5-dichloro-1 ,3,4-thiadiazole (0.14 g, 0.92 mmol), isopropanol (1.5 mL), potassium hydroxide (0.11 g, 2.02 mmol) and water (1.4 mL) stirring for 30 min at 0 °C and then for 5 h at ambient temperature to yield 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(4-fluoro-3-methylphenyl)-N-methylacetamide (0.09 g). LCMS (Method D): Rt = 2.59 min, m / z = 316.0 [M+H]+.

[1002] Example 112: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(2-cyanopropan-2-yl)-N-(4-fluorophenyl)acetamide (VII-2)

[1003] The title compound was prepared from the corresponding 2-((4-fluorophenyl)amino)-2-methylpropanenitrile by the general method N. LCMS (Method C): Rt = 7.01 min, m / z = 355.0 [M+H]+Example 113: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(1-cyanocyclopropyl)-N-(4-fluorophenyl)acetamide (VII-3)

[1004] The title compound was prepared from the corresponding 1-((4-fluorophenyl)amino)cyclopropane-1-carbonitrile by the general method N. LCMS (Method C): Rt = 7.33 min, m / z = 351.1 , 353.0 [M+H]+Example 114: 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(3-fluoro-4-methylphenyl)-N-methylacetamide (VII-56)

[1005] Step 1 : Preparation of 2-((3-fluoro-4-methylphenyl)(methyl)amino)-2-oxoethyl acetate (Vll-56a) Prepared according to general procedure P using 3-fluoro-N,4-dimethylaniline (0.17 g, 1.22 mmol), sodium hydride (0.06 g, 1.46 mmol), acetoxyacetyl chloride (0.20 g, 1.46 mmol) and DMF (1.7 mL) to yield 2-((3-fluoro-4-methylphenyl)(methyl)amino)-2-oxoethyl acetate (0.24 g).

[1006] Step 2: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(3-fluoro-4-methylphenyl)-N-methylacetamide (VII-56)

[1007] Prepared according to general procedure I using 2-((3-fluoro-4-methylphenyl)(methyl)amino)-2-oxoethyl acetate (0.20 g, 0.83 mmol), 2, 5-dichloro-1 ,3,4-thiadiazole (0.14 g, 0.92 mmol), isopropanol (1.5 mL), potassium hydroxide (0.11 g, 2.02 mmol) and water (1.4 mL) stirring for 30 min at 0 °C and then for 5 h at ambient temperature to yield 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(3-fluoro-4-methylphenyl)-N-methylacetamide (0.10 g). LCMS (Method D): Rt = 2.60 min, m / z = 316.0 [M+H]+.

[1008] Example 115: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-isopropyl-N-(2-fluorophenyl)acetamide (I-438)

[1009] The title compound was prepared from the corresponding N-isopropyl-2-fluoroaniline by the general methods C, E and M. LCMS (Method D): Rt = 2.77 min, m / z = 330.05 [M+H]+

[1010] Example 116: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-isopropyl-N-(3-fluorophenyl)acetamide (I-427)

[1011] The title compound was prepared from the corresponding N-isopropyl-3-fluoroaniline by the general methods C, E and M. LCMS (Method D): Rt = 3.26 min, m / z = 330.05 [M+H]+Example 117: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-isopropyl-N-(4-bromophenyl)acetamide (1-1450)

[1012] The title compound was prepared from the corresponding N-isopropyl-4-bromoaniline by the general methods C, E and M. LCMS (Method D): Rt = 3.58 min, m / z = 391.95 [M+H]+

[1013] Example 118: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-pent-3-yl-N-(4-fluorophenyl)acetamide (V-5)

[1014] The title compound was prepared from the corresponding 4-fluoro-N-pent-3-yl-aniline by the general methods C, E and M. LCMS (Method D): Rt = 3.65 min, m / z = 349.1 [M+H]+

[1015] Example 119: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-isopropyl-N-(4-iodophenyl)acetamide (1-1461)

[1016] The title compound was prepared from the corresponding N-isopropyl-4-iodooaniline by the general methods C, E and M. LCMS (Method D): Rt = 3.61 min, m / z = 437.81 [M+H]+

[1017] Example 120: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-isopropyl-N-(4-trifluoromethoxyphenyl)acetamide (1-1087)

[1018] The title compound was prepared from the corresponding N-isopropyl-4-trifluoromethoxyaniline by the general methods C, E and M. LCMS (Method D): Rt = 3.59 min, m / z = 395.95 [M+H]+

[1019] Example 121: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-isopropyl-N-(2,3-difluorophenyl)acetamide (I-702)

[1020] The title compound was prepared from the corresponding N-isopropyl-2,3-difluoroaniline by the general methods C, E and M. LCMS (Method D): Rt = 3.32 min, m / z = 347.9 [M+H]+

[1021] Example 122: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(2-methyl-but-3-yn-2-yl)-N-(4-fluorophenyl)acetamide (II-8)

[1022] The title compound was prepared from the corresponding N-(2-methyl-but-3-yn-2-yl)-4-fluoroaniline by the general methods C, E and M. LCMS (Method D): Rt = 3.99 min, m / z = 509.25 [M+H]+Example 123: Preparation of methyl 4-(2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-isopropylacetamido)benzoate (1-1472)

[1023] The title compound was prepared from the corresponding . 1 methyl 4-(isopropylamino)benzoate by the general method C, E, and M. LCMS (Method D): Rt = 3.22 min, m / z = 370.0 [M+H]+

[1024] Example 124: 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(4-fluorophenyl)-N-pentadecylacetamide (VII-4) Step 1 : Preparation of 4-fluoro-N-pentadecylaniline (Vll-4a)

[1025] Prepared according to general procedure B using 4-fluoroaniline (0.10 g, 0.90 mmol), pentadecanal (0.82 g, 3.60 mmol), acetic acid (0.10 mL, 1.80 mmol), STAB (0.21 g, 0.99 mmol) and DCM (1.8 mL), stirring for 16 h to yield 4-fluoro-N-pentadecylaniline (0.11 g). LCMS (Method B): Rt = 4.38 min.

[1026] Step 2: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(4-fluorophenyl)-N-pentadecylacetamide (VII-4)Prepared according to general procedure N using 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)acetic acid (0.06 g, 0.29 mmol), / V-methylmorpholine (0.13 mL, 1.16 mmol), propylphosphonic anhydride 50 wt% in EtOAc (0.52 mL, 0.87 mmol), 4-fluoro-N-pentadecylaniline (0.11 g, 0.29 mmol) and acetonitrile (1.0 mL) to yield 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(4-fluorophenyl)-N-pentadecylacetamide (0.01 g). LCMS (Method B): Rt = 4.14 min.

[1027] Example 125: 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(4-fluorophenyl)-N-(2-methoxyethyl)acetamide (HI-8)

[1028] Step 1 : Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(4-fluorophenyl)-N-(2-methoxyethyl)acetamide (HI-8)

[1029] Prepared according to general procedure N using 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)aceticacid (0.10 g, 0.51 mmol), / V-methylmorpholine (0.23 mL, 2.10 mmol), propylphosphonic anhydride 50 wt% in EtOAc (0.92 mL, 1.50 mmol), 4-fluoro-N-(2-methoxyethyl)aniline (0.09 g, 0.51 mmol) and acetonitrile (1.8 mL) to yield 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(4-fluorophenyl)-N-(2-methoxyethyl)acetamide (0.09 g). LCMS (Method A): Rt = 2.15 min.

[1030] Example 126: Preparation of 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(4-fluoro-3-methylphenyl)-N-isopropylacetamide adiazol-2-yl)oxy)-N-(2-fluoro-4-methylphenyl)-N-methylacetamide (VI 1-1277) Prepared according to general procedure N using 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)aceticacid (0.13 g, 0.68 mmol), N-methylmorpholine (0.30 mL, 2.73 mmol), propylphosphonic anhydride 50 wt% in EtOAc (1.22 mL, 2.05 mmol), 2-fluoro-N,4-dimethylaniline hydrochloride (0.12 g, 0.68 mmol) and acetonitrile (1 mL) stirring for 3 h to yield 2-((5-chloro-1 ,3,4-thiadiazol-2-yl)oxy)-N-(4-fluoro-3-methylphenyl)-N-isopropylacetamide (0.15 g). LCMS (Method C): Rt = 5.90 min, m / z = 316.0, 318.0 [M+H]+.

[1031] Stability Examples

[1032] Aqueous buffer solutions were prepared at pH 1 (aqueous HCI, 0.9 mol / L), pH 4 (acetic acid, 93 mg and sodium acetate 232 mg in 50 mL water), pH 7 (water), pH 9 (sodium bicarbonate 382 mg and sodium carbonate 48 mg in 50 mL water) and pH 14 (aqueous NaOH, 1 mol / L).

[1033] A random selection of the synthesised compounds was sampled, including e.g. compound I-7. 5 flasks were used per compound, whereby to each flask was added said compound (1 mg) and methanol (1 mL). Each flask was treated with a different aqueous buffer solution (1 mL) from those prepared above (T = 0). Each flask was stored at 20 °C for 68 days (T=0-68 days), after which time, it was warmed to 50 °C for 14 days (T=69-82 days).

[1034] LCMS analysis was performed at T=0, 1 , 4, 30, 48, 68, 70, 75 and 82 days. Samples were unstable at pH 14 at T=0.

[1035] None of the tested compounds decomposed to trifluoroacetic acid over the course of testing.

[1036] Biological Examples

[1037] The herbicidal effect of some of the above synthesized compounds was tested in greenhouse experiments on different plants.

[1038] For the plants employed in these experiments, the following abbreviations are used:

[1039] ALOMY: Alopecurus myosuroides

[1040] APESV: Apera spica-ventiAVEFA: Avena fatua

[1041] CHEAL: Chenopodium album

[1042] DIGSA: Digitaria sanguinalis

[1043] ECHCG: Echinochloa crus-galli

[1044] GERDI: Geranium dissectum

[1045] LOLMU: Lolium multiflorum

[1046] PANMI: Panicum miliaceum

[1047] POAAN: Poa annua

[1048] SET VI: Setaria viridis

[1049] SOLN I: Solanum nigrum

[1050] Herbicidal Effect in Pre-Emergence

[1051] Seeds of monocotyledonous or dicotyledonous weeds and crop plants are designed in plastic trays and covered with soil. Aqueous solutions are then pipetted onto each individual plant cells (within plastic trays), each derived from the formulation of the technical active ingredient in acetone I water (3.5% Acetone) solution containing (0.1%) Tween 20 (polyoxyethelyene (20) sorbitan monolaurate, CAS RN 9005-64-5). Compound(s) are applied pre-emergence at 250 g / ha (Table 5.1), 125 g / ha (Table 6.1) or 62.5 g / ha (Table 7.1).

[1052] The test plants are then grown in a glasshouse under controlled conditions (at 20 °C / 12 °C, day / night; photoperiod 16:8 hours light:dark; 65 % humidity) and watered daily. After 14 or 21 days the test is evaluated for the percentage damage caused to the plant. The biological activities are shown in the following Tables on a five-point scale (5 = 81-100%; 4 = 61-80%; 3=41-60%; 2=21-40%; 1=0-20%; - = not tested) and for some compounds are listed in parentheses.

[1053] Table 5.I

[1054]

[1055]

[1056]

[1057]

[1058]

[1059]

[1060]

[1061]

[1062] As can be seen from Table 5.1, compounds 1-8, 1-7, 1-6, 1-5, 1-4, 1-3, 1-2, 1-10, I-438, I-427, 1-1450, 1-185, V-5, IV- 11 , II-6, I-42, I-460, 1-1461 , 1-1076, 1-1087, I-702, I-284, II-8, 1-1516, I-867, 1-1472, 1-119, I-262, I-53, 1-31 , 1-1054, I-207, I-282, 11-281 , I-279, 1-361 , I-273, I-295, 1-317, I-339, 1-1285, 1-1032, 1-1296, VII-276, VII-23, 1-1043, I-383, 1-1439, 1-1428, 1-1373, 1-1417, VII-34, VII-45, 1-51 , 1-26, 1-1406, I-29, VII-1288, 1-1186, 1-515, 1-1175, 1-1164, I-48, 1-1153, 1-1142, 1-1131 , 1-1291 , I-504, 1-1264, I-40, I-97, I-37, 1-1307, 1-1395, VII-177, 1-180, 1-312, 1-315, 1-1318, 1-1329, 1-183, 1-1120, I-636, VII-1024, VII-309, 1-1340, VII-265, 1-271 , I-268, 1-1030, 1-1109, VII-1068, 1-1098, I-64, 1-1351 , 1-1362, 1-1384, I-394, 1-1283, 1-1280, I-1219, 1-1230, 1-1241 , VII-353, I-356, I-359, VII-331 , I-334, I-337, VII-1277, VII-89, I-92, I-95, VII-56, III-8, 1-1263, I-59, I-62, VII-1222, 1-1225 and 1-1 gave an effect of at least 61% and up to 80% against at least one of the test plants. Even more, compounds I-9, I-8, I-7, I-6, I-4, I-3, I-2, 1-10, I-438, I-427, I-1450, 1-185, V-5, IV-11, II-6, I-42, I-460, 1-1461 , 1-1076, 1-1087, I-702, I-284, II-8, I-867, 1-1472, 1-119, I-262, I-53, 1-31 , 1-1296, VII-276, VII-23, 1-1043, I-383, 1-1439, 1-1428, 1-1373, 1-1417, VII-34, VII-45, 1-51 , I-26, 1-1406, I-29, VII-1288, 1-1186, 1-515, 1-1175, 1-1164, I-48, 1-1153, 1-1142, 1-1131 , 1-1291 , I-504, I-1264, I-40, I-97, I-37, 1-1307, 1-1395, VII-177, 1-180, 1-312, 1-315, 1-1318, 1-1329, 1-183, 1-1120, I-636, VII-1024, VII-309, 1-1340, VII-265, 1-271 , I-268, 1-1030, 1-1109, VII-1068, I-64, 1-1351 , 1-1362, 1-1384, I- 394, 1-1283, 1-1280, 1-1219, 1-1230, 1-1241 , VII-353, I-356, I-359, VII-331 , I-334, I-337, VII-1277, VII-89, I-92, I-95, VII-56, HI-8, 1-1263, I-59, I-62, VII-1222, 1-1225 and 1-1 gave an effect of at least 81% against at least one of the test plants.

[1063] Table 6.I

[1064]

[1065]

[1066]

[1067]

[1068]

[1069]

[1070]

[1071]

[1072] As can be seen from Table 6.1, compounds 1-8, 1-7, 1-5, 1-4, 1-3, 1-2, 1-1 , 1-10, I-427, 1-1450, 1-185, IV- 11 , II-6, I-42, I-460, 1-1461 , 1-1076, 1-1087, I-702, I-284, II-8, 1-1516, I-867, 1-1472, 1-119, I-262, I-53, 1-31 , V-2, 1-10, 1-1054, I-207, I-282, 11-281 , I-279, 1-361 , I-273, I-295, 1-317, I-339, 1-1285, 1-1032, II-8, 1-1296, VII-276, VII-23, 1-1043, I-383, 1-1439, 1-1428, 1-1373, VII-34, VII-45, 1-51 , I-26, 1-1406, I-29, VII-1288, I-1186, 1-1175, 1-1164, I-48, 1-1153, 1-1142, 1-1131 , 1-1291 , I-504, 1-1264, I-40, I-97, I-37, 1-1307, 1-1395, VII-177, 1-180, 1-312, 1-315, 1-1318, 1-1329, 1-183, 1-1120, I-636, VII-1024, VII-309, 1-1340, VII-265, 1-271 , I-268, 1-1030, 1-1109, VII-1068, 1-1098, I-64, 1-1351 , 1-1362, 1-1384, I-394, 1-1283, 1-1280, 1-1219, 1-1230, 1-1241 , VII-353, I-356, I-359, VII-331 , I-334, I-337, VII-1277, VII-89, I-92, I-95, VII-56, HI-8, 1-1263, I-59, I-62, VII-1222 and 1-1225 gave an effect of at least 61% and up to 80% against at least one of the test plants at an application rate of 125 g / ha. Even more, compounds I-7, I-4, I-2, 1-1 , 1-10, I-427, 1-1450, I-185, IV- 11 , II-6, I-42, I-460, 1-1461 , 1-1076, 1-1087, I-702, I-284, II-8, I-867, 1-1472, 1-119, I-262, I-53, I-31 , V-2, 1-10, 1-1054, I-207, I-282, 11-281 , I-279, 1-361 , I-273, I-295, 1-317, I-339, 1-1285, 1-1032, II-8, I-1296, VII-276, VII-23, 1-1043, I-383, 1-1439, 1-1373, VII-34, VII-45, 1-1406, 1-51 , I-26, I-29, VII-1288, I-1186, 1-1175, 1-1164, I-48, 1-1153, 1-1142, 1-1131 , VII-2, VII-3, 1-1291 , I-504, 1-1264, I-40, I-97, I-37, I-1307, 1-1395, VII-177, 1-180, 1-312, 1-315, 1-1318, 1-1329, 1-183, 1-1120, I-636, VII-1024, VII-309, 1-1340, VII-265, 1-271 , 1-268, 1-1030, 1-1109, VII-1068, 1-1098, I-64, 1-1351 , 1-1362, 1-1384, I-394, 1-1283, 1-1280, 1-1219, 1-1230, 1-1241 , VII-353, I-356, I-359, VII-331 , I-334, I-337, VII-1277, VII-89, I-92, I-95, VII-56, III-8, 1-1263, I-59, I-62, VI 1-1222 and 1-1225 gave an effect of at least 81% against at least one of the test plants at an application rate of 125 g / ha.

[1073] Table 7.I

[1074]

[1075]

[1076]

[1077]

[1078]

[1079]

[1080] As can be seen from Table 7.1, compounds 1-7, 1-4, 1-1 , 1-10, I-427, 1-1450, 1-185, IV-11 , II-6, I-42, I-460, 1-1461 , 1-1076, 1-1087, I-284, II-8, I-867, 1-119, I-262, I-53, 1-31 , 1-1054, I-207, I-282, 11-281 , I-279, 1-361 , I-273, I-295, 1-317, I-339, 1-1285, 1-1032, 1-1296, VII-276, VII-23, 1-1043, I-383, 1-1439, 1-1428, 1-1373, VII-34, VII-45, 1-51 , I-26, 1-1406, I-29, VII-1288, 1-1186, 1-1175, 1-1164, I-48, 1-1153, 1-1142, 1-1131 , VII-3, 1-1291 , 1-504, 1-1264, I-40, I-97, I-37, 1-1307, VII-177, 1-180, 1-312, 1-315, 1-1318, 1-1329, 1-183, 1-1120, I-636, VII-1024, VII-309, 1-1340, VII-265, 1-271 , I-268, 1-1030, 1-1109, VII-1068, 1-1098, I-64, 1-1351 , I-1362, I-394, 1-1283, 1-1280, 1-1230, 1-1241 , VII-353, I-356, I-359, VII-331 , I-334, I-337, VII-1277, VII-89, I-92, I-95, VII-56, HI-8, 1-1263, I-59, I-62, VII-1222 and 1-1225 gave an effect of at least 61% and up to 80% against at least one of the test plants at an application rate of 62.5 g / ha. Even more, compoundsI-7, I-4, 1-1, 1-10, I-427, 1-1450, IV-11 , II-6, I-42, I-460, 1-1461 , 1-1076, 1-1087, I-284, II-8, I-867, 1-119, I-262, I-53, 1-31 , 1-1054, I-207, I-282, 11-281 , I-279, 1-361 , 1-273, 1-295, 1-317, I-339, 1-1285, 1-1032, 1-1296, VII-276, VII-23, 1-1043, I-383, 1-1439, 1-1428, 1-1373, VII-34, VII-45, 1-51 , I-26, I-29, VII-1288, 1-1186, I-1175, 1-1164, I-48, 1-1153, 1-1142, 1-1131 , VII-3, 1-1291 , I-504, 1-1264, I-40, I-97, I-37, 1-1307, 1-180, I-312, 1-315, 1-1318, 1-1329, 1-183, 1-1120, I-636, VII-1024, VII-309, 1-1340, VII-265, 1-271 , I-268, 1-1030, 1-1109, VII-1068, I-64, 1-1351 , 1-1362, I-394, 1-1283, 1-1280, 1-1230, 1-1241 , VII-353, I-356, I-359, VII-331 , I-334, I-337, VII-1277, VII-89, I-92, I-95, VII-56, 1-1263, I-59, I-62, VII-1222 and 1-1225 gave an effect of at least 81% against at least one of the test plants at an application rate of 62.5 g / ha.

[1081] Pre-Emergence Crop Safety

[1082] Pre-Emergence Crop Safety assay was performed in an identical manner to the pre-emergence assay on herbicidal effect, using a seed of the relevant crop (winter barley, HORVW; winter wheat, TRAZW; or Zea mays, ZAEMX: the seed was planted in the same trays as that of a weed). Safety was assessed on a scale (relative to flufenacet) identical to that used for assessing herbicidal effect, whereby compounds which showed lowest herbicidal effect (0%, i.e. a value of 1) against a given crop are considered safest for use in said crop [conversely, comounds which showed highest herbicidal effect (100%, i.e. a value of 5) against a given crop are considered least safe for use in said crop], Compound(s) are applied pre-emergence at 250 g / ha (Table 5. II), 125 g / ha (Table 6. II) or 62.5 g / ha (Table 7. II).

[1083] Table 5.II

[1084]

[1085]

[1086]

[1087] As can be seen from Table 5.11, compounds 1-7, 1-4, 1-284, 1-119, I-53, 1-31 , 1-1054, I-207, I-282, 11-281 , I-279, 1-361 , I-273, I-295, 1-317, I-339, 1-1285, 1-1032, 1-1296, VII-276, VII-23, 1-1043, I-383, 1-1439, I-1428, 1-1373, 1-1417, VII-34, 1-1197, 1-51 , 1-26, 1-1406, I-29, VII-1288, 1-1186, 1-515, 1-1175, I-48, 1-1142, 1-1131 , VII-2, VII-3, 1-1291 , I-504, 1-1264, I-40, I-97, I-37, 1-1307, 1-1395, VII-177, 1-180, 1-312, 1-315, I-1318, 1-1329, 1-183, 1-1120, I-636, VII-1024, VII-309, 1-1340, VII-265, 1-271 , I-268, 1-1030, 1-1109, VII- 1068, 1-1098, I-64, 1-1351 , 1-1362, 1-1384, I-394, 1-1283, 1-1280, 1-1219, 1-1230, 1-1241 , VII-353, I-356, I-359, VII-331 , I-334, I-337, VII-1277, VII-89, I-92, I-95, VII-56, VII-4, HI-8, 1-1263, I-59, I-62, VII-1222 and 1-1225 gave an improved crop safety effect over flufenacet in at least one of the test crop plants at an application rate of 250 g / ha.

[1088] Table 6.II

[1089]

[1090]

[1091]

[1092] As can be seen from Table 6.11, compounds 1-7, 1-284, 1-867, 1-262, 1-53, 1-31 , 1-1054, I-207, I-282, II-281 , I-279, 1-361 , 1-273, 1-295, 1-317, I-339, 1-1285, 1-1032, 1-1296, VII-276, VII-23, 1-1043, I-383, 1-1439, 1-1428, 1-1373, 1-1417, VII-34, VII-45, 1-1197, 1-51 , I-26, 1-1406, I-29, VII-1288, 1-515, 1-1175, 1-1164, I-48, 1-1142, 1-1131 , VII-2, VII-3, 1-1291 , I-504, 1-1264, I-40, I-97, I-37, 1-1307, 1-1395, VII-177, 1-180, I-312, 1-315, 1-1318, 1-1329, 1-183, 1-1120, I-636, VII-309, 1-1340, VII-265, 1-271 , 1-268, 1-1030, 1-1109, VII- 1068, 1-1098, I-64, 1-1351 , 1-1362, 1-1384, I-394, 1-1283, 1-1280, 1-1219, 1-1230, 1-1241 , VII-353, I-356, I-359, I-334, I-337, VII-1277, VII-89, I-92, I-95, VII-56, VII-4, HI-8, 1-1263, I-59, I-62, VII-1222 and 1-1225 gave an improved crop safety effect overflufenacet in at least one of the test crop plants at an application rate of 125 g / ha.

[1093] Table 7.II

[1094]

[1095]

[1096]

[1097] As can be seen from Table 7.11, compounds 1-7, 1-11, II-6, 1-1472, 1-119, I-53, 1-31 , 1-1054, I-207, I-282, 11-281 , I-279, 1-361 , I-273, I-295, 1-317, I-339, 1-1285, 1-1032, 1-1296, VII-276, VII-23, 1-1043, I-383, I-1439, 1-1428, 1-1373, 1-1417, VII-34, VII-45, 1-1197, 1-51 , I-26, 1-1406, I-29, VII-1288, 1-1186, 1-515, I-1175, 1-1164, I-48, 1-1153, 1-1142, 1-1131 , VII-2, VII-3, 1-1291 , I-504, 1-1264, I-40, I-97, I-37, 1-1307, I-1395, VII-177, 1-180, 1-312, 1-315, 1-1318, 1-1329, 1-183, 1-1120, I-636, VII-1024, VII-309, 1-1340, VII-265, 1-271 , I-268, 1-1030, 1-1109, VII-1068, 1-1098, I-64, 1-1351 , 1-1362, 1-1384, I-394, 1-1283, 1-1280, 1-1219, 1-1230, 1-1241 , VII-353, I-356, I-359, VII-331 , I-334, I-337, VII-1277, VII-89, I-92, I-95, VII-56, VI , III- 8, 1-1263, I-59, I-62, VII-1222 and 1-1225 gave an improved crop safety effect over flufenacet in at least one of the test crop plants at an application rate of 62.5 g / ha.

[1098] Herbicidal Effect in Post-Emergence

[1099] Monocotyledonous or dicotyledonous weeds and crop test plants are grown in a glasshouse in plastic trays under controlled conditions (at 20 °C / 12 °C, day / night; photoperiod 16:8 hours light:dark; 65 % humidity) and watered daily. Individual plant cells (within plastic trays) are then sprayed with aqueous solutions, each derived from the formulation of the technical active ingredient in acetone I water (3.5% Acetone) solution containing (0.1%) Tween 20 (polyoxyethelyene (20) sorbitan monolaurate, CAS RN 9005-64-5). Compound(s) are applied post-emergence at 250 g / ha (Table 8.1), 125 g / ha (Table 9.1) or 62.5 g / ha (Table 10.1) and are evaluated after 14 days for the percentage damage caused to the plant. The biological activities are shown in the following Tables on a five-point scale (5 = 81-100%; 4 = 61-80%; 3=41-60%; 2=21-40%; 1=0-20%; - = not tested) and for some compounds are listed in parentheses.

[1100] Table 8.I

[1101]

[1102]

[1103]

[1104] As can be seen from Table 8.1, compounds 1-7, 1-4, 1-11 , 1-10, I-438, I-427, 1-1450, 1-185, IV- 11 , I-42, I-1076, 1-1087, I-284, I-53, 1-31 , I-282, 1-361 , I-273, I-339, 1-1032, VII-23 and VII-34 gave an improved herbicidal effect over flufenacet against at least one of the test plants at an application rate of 250 g / ha.

[1105] Table 9.I

[1106]

[1107]

[1108]

[1109] As can be seen from Table 9.1, compounds 1-7, 1-4, 1-10, I-427, 1-1450, 1-185, IV-11 , I-42, 1-1087, I-284, I-53, 1-361 , I-273, I-339, 1-1285, 1-1032, 1-1296, VII-276, VII-23, 1-1373, VII-34 and VII-45 gave an improved herbicidal effect over flufenacet against at least one of the test plants at an application rate of 125 g / ha.

[1110] Table 10.1

[1111]

[1112]

[1113]

[1114]

[1115] As can be seen from Table 10.1, compounds 1-7, 1-4, 1-10, I-427, IV- 11 , I-42, 1-1087, I-284, I-53, 1-361 , I-273, I-339, 1-1285, 1-1032, 1-1296 and VII-23 gave an improved herbicidal effect over flufenacet against at least one of the test plants at an application rate of 62.5 g / ha.

[1116] Post-Emergence Crop Safety

[1117] Post-Emergence Crop Safety assay was performed in an identical manner to the post-emergence assay on herbicidal effect, using a plant of the relevant crop (winter barley, HORVW; winter wheat, TRAZW; or Zea mays, ZAEMX: the plant was grown in the same trays as that of a weed). Safety was assessed on a scale (relative to flufenacet) identical to that used for assessing herbicidal effect, whereby compounds which showed lowest herbicidal effect (0%, i.e. a value of 1) against a given crop are considered safest for use in said crop [conversely, comounds which showed highest herbicidal effect (100%, i.e. a value of 5) against a given crop are considered least safe for use in said crop], Compound(s) are applied pre-emergence at 250 g / ha (Table 8. II), 125 g / ha (Table 9. II) or 62.5 g / ha (Table 10.11).

[1118] Table 8.11

[1119]

[1120]

[1121] As can be seen from Table 8.11, compounds IV- 11 , I-42, 1-1076, 1-1087, I-284, I-53, 1-1054, 1-31 , I-207, I-282, 11-281 , I-279, 1-361 , I-273, 1-317, I-339, 1-1285, 1-1032, 1-1296, VII-276, VII-23, 1-1373, VII-34 and VII-45 gave an equivalent crop safety effect to flufenacet in all of the test crop plants at an application rate of 250 g / ha.

[1122] Table 9.II

[1123]

[1124] As can be seen from Table 9.11, compounds IV- 11 , I-42, 1-1076, 1-1087, I-284, I-53, 1-1054, 1-31 , I-207, I-282, 11-281 , I-279, 1-361 , I-273, 1-317, I-339, 1-1285, 1-1032, 1-1296, VII-276, VII-23, 1-1373, VII-34 and VII-45 gave an improved crop safety effect over flufenacet in at least one of the test crop plants at an application rate of 125 g / ha.

[1125] Table 10.11

[1126]

[1127] As can be seen from Table 10.11, compounds IV- 11 , I-42, 1-1076, 1-1087, I-284, I-53, 1-1054, 1-31 , I-207, I-282, 11-281 , I-279, 1-361 , I-273, 1-317, I-339, 1-1285, 1-1032, 1-1296, VII-276, VII-23, 1-1373, VII-34 and VII-45 gave an improved crop safety effect over flufenacet in at least one of the test crop plants at an application rate of 62.5 g / ha.

Claims

CLAIMS1. A compound of formula I:[Formula I]whereineach of R1aand R1bis H;R2is selected from C1-3 alkyl, C4-8 alkyl, C9-19 alkyl, C1-6 alkoxy, C2-6 alkenyl, C2-ealkynyl, C3-6 cycloalkyl, (C3-6 cycloalkyl)Ci-3 alkyl, C1-6 alkylsulfonyl, C2-8 heterocyclyl and (C2-8 heterocyclyl)Ci-3 alkyl, each of which may be optionally substituted; andR3is selected from C6-10 aryl, and C3-7 heteroaryl, each of which may be optionally substituted;or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof,wherein:when R1a= H, R1b= H and R2= isopropyl, R3is not phenyl, 4-fluorophenyl, 2- chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 3-methylphenyl, 4-methylphenyl, 2- methoxyphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-thiomethylphenyl, 3-chloro-4- thiomethylphenyl, 3,5-dimethylphenyl, 3,5-dichlorophenyl, 3-chloro-4-methoxyphenyl, 3,5- di(trifluoromethyl)phenyl, 3,4-dichlorophenyl, 5-chloro-2-methylphenyl; orwhen R1a= H, R1b= H and R2= methyl, R3is not phenyl, 4-(trifluoromethyl)phenyl, 3- (trifluoromethyl)phenyl, 2-methyl-5-nitrophenyl, 2-thiophenyl, 3-thiophenyl, 4-thiophenyl, 4- thiomethylphenyl, 3-thiomethylphenyl, 4-fluorophenyl, 3-fluorophenyl, 3,4-dichlorophenyl, 2- methylphenyl, 3-methylphenyl, 4-methylphenyl, 3-chlorophenyl.

2. The compound of claim 1, wherein:each of the groups listed for R2is optionally substituted by one or more substituents selected from F, Cl, Br, I, CN, oxo, C1-6 alkyl, C1-6 alkoxy, C1-6 alkylthio, (Ci-6alkoxy)Ci-6alkyl, SO2R, C(O)R, CO2R, C(O)NR2, NR2 and SiRs, wherein each R is independently selected from H, OH, C1-6 alkoxy and C1-6 alkyl, and wherein two Rs and the atom to which they are bound may form a cyclic group;each of the groups listed for R3is substituted by one or more substituents selected from F, Cl,Br, I, CN, NO2, C1-6 alkyl, Ci-ealkoxy, C1-6 alkylthio, C3-6 cycloalkyl, (cyano)Ci-e alkyl, NR42, SO2R5, and CO2R6, wherein each R4is independently selected from C1-3 alkyl, wherein optionally the two R4and the N atom to which they are bound may form a 3- to 6-membered heterocyclic group, each R5is independently selected from C1-6 alkyl and C1-6 alkoxy, and each R6is independently selected from H and C1-6 alkyl;or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof.

3. The compound of claim 1 , with the proviso that R3is Ce aryl that is substituted or C3-7 heteroaryl that is unsubstituted or substituted, wherein the substituent is selected from at least one of halogen, CN, NO2, C1-6 alkyl, halogeno-Ci-6 alkyl, C1-6 alkoxy, halogeno-Ci-6 alkoxy, C1-6 alkylthio, halogeno-Ci-6 alkylthio, (cyano)methyl, NMe2, SO2Me, and CO2Me, preferably Ce aryl substituted by at least one of F, Cl, CH3, OCH3, OC2H5, SCH3 and CF3 or C3-7 heteroaryl that is unsubstituted or substituted by at least one F;or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof.

4. The compound of any one of claims 1 to 3, wherein R2is selected from C4-8 alkyl, C9-19 alkyl, (cyano)Ci-6 alkyl, C1-6 alkoxy, C2-6 alkenyl, C2-ealkynyl, C3-6 cycloalkyl, (C3-6 cycloalkyl)Ci-3 alkyl, C2-8 heterocyclyl and (C2-8 heterocyclyl)Ci-3 alkyl, each of which may be optionally substituted by one or more groups selected from F, Cl, Br, I, CN, oxo, C1-6 alkyl, C1-6 alkoxy, (Ci-ealkoxy)Ci- salkyl, SO2R, C(O)R, CO2R, C(O)NR2, NR2 and SiRs, wherein each R is independently selected from H, OH and C1-6 alkyl,or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof.

5. The compound of any one of claims 1 to 3, wherein R2is selected from cyanomethyl, cyclopropyl, sec-butyl, 1-butyn-4-yl, 2-butyn-1-yl, prop-1 -yl, 3-methyl-1-butyn-3-yl, cyclopropylmethyl, 1 -trimethylsilyl-2-butyn-4-yl, 1-buten-4-yl, 1-buten-3-yl, 2-methyl-1-propen- 3-yl, allyl, tert-butyl, cyclopentyl, propargyl, iso-butyl and 1-butyn-3-yl,or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof.

6. The compound of claims 1 to 5, wherein R3is Ce aryl substituted by at least one F or C3- 7 heteroaryl that is unsubstituted or substituted by at least one F, preferably R3is Ce aryl substituted by at least one F in the 3-position or 4-position relative to the attachment point of R3to the remainder of the molecule, and optionally further substituted by one or more groupsselected from F, Cl, Br, I, CN, NO2, C1-6 alkyl, C1-6 alkoxy and C3-6 cycloalkyl;or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof.

7. The compound of any one of claims 1 to 6, whereinR2is selected from C4-8 alkyl, (cyano)Ci-e alkyl, C2-6 alkenyl, C2-ealkynyl, (C3-6 cycloalkyl)Ci- 3 alkyl and C3-6 cycloalkyl, each of which may be optionally substituted by one or more groups selected from F, Cl, Br, I, CN, oxo, C1-6 alkyl, C1-6 alkoxy, (Ci-6alkoxy)Ci-6alkyl, SO2R, C(O)R, CO2R, C(O)NR2, NR2 and SiRs, wherein each R is independently selected from H, OH and C1- 6 alkyl;or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof.

8. The compound of claim 7, whereinR3is selected from 4-fluorophenyl, 2,5-difluorophenyl, 3,4-difluorophenyl, 2,4-difluorophenyl, 3- fluoro-4-chlorophenyl, 3-chloro-4-fluorophenyl, 4-fluoro-2-nitrophenyl, 4-fluoro-2-methylphenyl, 4-fluoro-2-methoxyphenyl, 2,4,5-trifluorophenyl, 2,3,4-trifluorophenyl, 2,4,6-trifluorophenyl, 2- chloro-4,6-difluorophenyl,3-chloro-2,4-difluorophenyl, 2,6-dichloro-4-fluorophenyl and 2-chloro- 4-fluoro-6-methylphenyl,preferably, wherein:R2is selected from cyanomethyl, cyclopropyl, sec-butyl, 1-butyn-4-yl, 2-butyn-1-yl, 3- methyl-1-butyn-3-yl, allyl, tert-butyl, cyclopentyl, propargyl, iso-butyl, 1-butyn-3-yl and 3- methylbut-2-yl, andR3is 4-fluorophenyl,more preferably, wherein:R2is selected from 1-butyn-4-yl, 2-butyn-1-yl, propargyl, allyl, 3-methyl-1-butyn-3-yl and 1-butyn-3-yl, andR3is 4-fluorophenyl;or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof.

9. The compound of any one of claims 1 to 8, having a structure selected from Table 3;or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, ora tautomer thereof, with the proviso that said compound is not compound I-9, I-20, 1-108, 1-141 , 1-174, I-900, 1-1483, 1-1494, 1-1505, VII-1 , VII-12, VII-100, VII-419, VII- 1365, VII-1475 or VII-1497, preferably with the proviso that said compound is not compound I- 9, I-20, 1-108, 1-141 , 1-174, I-900, 1-1483, 1-1494, 1-1505, VII-1 , VII-12, VII-100, VII-419, VII-1365, VII-1475, VII-1497, 1-11 , 1-1197, 1-1461 , 1-1516, VII-2, VII-3 or VII-4, and more preferably with the proviso that said compound is not compound I-9, I-20, 1-108, 1-141 , 1-174, I-900, 1-1483, I- 1494, 1-1505, VII-1, VII-12, VII-100, VII-419, VII-1365, VII-1475, VII-1497, I-3, I-427, I-438, I- 460, 1-515, I-702, 1-1219, 1-1131 , 1-1472, V-5, 1-11 , 1-1197, 1-1461 , 1-1516, VII-2, VII-3, VII-4.

10. The compound of any one of claims 1 to 9, represented by the following Formula la’,[Formula la’]wherein R2is:(i) 1-butyn-4-yl;(ii) 2-butyn-1-yl;(iii) propargyl; or(iv) allyl;or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof.

11. The compound of any one of claims 1 to 3, 6 and 9, whereinR2is isopropyl, andR3is selected from 3,4-difluorophenyl, 2,4-difluorophenyl, 3-fluoro-4-chlorophenyl, 3- chloro-4-fluorophenyl, 4-chlorophenyl, 4-nitrophenyl, 4-(trifluoromethoxy)phenyl, 2,5- difluorophenyl, 2-fluorophenyl, 3-fluorophenyl, 2,3-difluorophenyl, 2,5-difluorophenyl, 3,5- difluorophenyl, 2,6-difluorophenyl, 2-chloro-4-fluorophenyl, 4-fluoro-2-nitrophenyl, 4-fluoro-2- methylphenyl, 4-fluoro-2-methoxyphenyl, 2,4,5-trifluorophenyl, 2,3,4-trifluorophenyl, 2,4,6- trifluorophenyl, 2-chloro-4,6-difluorophenyl, 3-chloro-2,4-difluorophenyl, 2,6-dichloro-4- fluorophenyl and 2-chloro-4-fluoro-6-methylphenyl,preferably wherein R3is selected from 3,4-difluorophenyl, 2,4-difluorophenyl, 3-fluoro- 4-chlorophenyl, 3-chloro-4-fluorophenyl, 4-chlorophenyl, 4-nitrophenyl, 4-(trifluoromethoxy)phenyl, 2,5-difluorophenyl, 4-fluoro-2-nitrophenyl, 4-fluoro-2-methylphenyl, 4- fluoro-2-methoxyphenyl, 2,4,5-trifluorophenyl, 2,3,4-trifluorophenyl, 2,4,6-trifluorophenyl, 2- chloro-4,6-difluorophenyl, 3-chloro-2,4-difluorophenyl, 2,6-dichloro-4-fluorophenyl and 2- chloro-4-fluoro-6-methylphenyl,more preferably wherein R3is selected from 3,4-difluorophenyl, 2,4-difluorophenyl, 3- fluoro-4-chlorophenyl, 3-chloro-4-fluorophenyl and 4-chlorophenyl,orR2is prop-1 -yl, andR3is selected from 4-fluorophenyl, 3,4-difluorophenyl, 2,4-difluorophenyl, 3-fluoro-4- chlorophenyl, 3-chloro-4-fluorophenyl, 4-fluoro-2-nitrophenyl, 4-fluoro-2-methylphenyl, 4-fluoro- 2-methoxyphenyl, 2,4,5-trifluorophenyl, 2,3,4-trifluorophenyl, 2,4,6-trifluorophenyl, 2-chloro-4,6- difluorophenyl, 3-chloro-2,4-difluorophenyl, 2,6-dichloro-4-fluorophenyl and 2-chloro-4-fluoro-6- methylphenyl, preferably wherein R3is selected from 3,4-difluorophenyl, 2,4-difluorophenyl, 3- fluoro-4-chlorophenyl, 3-chloro-4-fluorophenyl and 4-chlorophenyl;or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof.

12. Use of the compound of any one of claims 1 to 11 or an agrochemically acceptable salt thereof, a stereoisomer thereof, an enantiomer thereof, a deuteromer thereof, or a tautomer thereof as a herbicide, for example on cereals including barley and wheat, cotton, oilseed rape, sunflower, maize, rice, soybeans, sugar beet, sugar cane, turf, trees including fruit trees, palm trees, coconut trees or other nuts, vines including grapes, fruit bushes, fruit plants and vegetables including potatoes and tomatoes.

13. The use of claim 12, wherein the compound is used against species selected from Abutilon theophrasti, Alopecurus myosuroides, Amaranthus albus, Amaranthus blitoides, Amaranthus blitum, Amaranthus hybridus, Amaranthus palmeri, Amaranthus powellii, Amaranthus retroflexus, Amaranthus sp., Amaranthus spinosus, Amaranthus tuberculatus, Amaranthus viridis, Ambrosia artemisiifolia, Ambrosia trifida, Apera spica-venti, Avena fatua, Brachiaria platy phylla, Brassica napus, Brassica rapa, Brassica sp., Bromus catharticus, Bromus tectorum, Capsella bursa-pastoris, Caucalis platycarpos, Chenopodiastrum murale, Chenopodium album, Chenopodium vulvaria, Chloris sp., Chrozophora tinctoria, Cirsium arvense, Commelina benghalensis, Commelina erecta, Consolida regalis, Convolvulus arvensis, Conyza bonariensis, Conyza sp., Conyza sumatrensis, Cynodon dactylon, Cynodon hirsutus, Cynodon sp., Cy perus esculentus, Cy perus rotund us, Datura stramonium, Descurainia pinnata, Descurainia sophia, Digitaria sanguinalis, Digitaria sanquinalis, Echinochloa colona, Echinochloa coIonum, Echinochloa crus-galli, Echinochloa sp., Eleusine indica, Elymus repens,Elytrigia repens, Equisetum arvense, Erigeron annuus, Erigeron bonariensis, Erigeron canadensis, Erigeron floribundus, Fallopia convolvulus, Fumaria officinalis, Galeopsis spp., Galinsoga parviflora, Galinsoga quadriradiata, Galium aparine, Galium spurium, Galium tricornutum, Geranium dissectum, Gomphrena sp., Helianthus annuus, Hibiscus trionum, Hirschfeldia incana, Humulus lupulus, Ipomoea cordatotriloba, Ipomoea hederacea, Ipomoea heptaphylla, Ipomoea lacunosa, Ipomoea muricata, Ipomoea purpurea, Ipomoea tricolor, Kochia sp., Lamium hybrid urn, Lamium spp., Lapsana communis, Linaria vulgaris, Lolium multiflorum, Lolium perenne, Lolium sp., Malva sylvestris, Matricaria discoidea, Myosotis arvensis, Panicum miliaceum, Papaver rhoeas, Persicaria lapathifolia, Persicaria maculosa, Phalaris brachystachys, Phalaris minor, Phalaris paradoxa, Phragmites australis, Physalis acutifolia, Phytolacca americana, Plantago lanceolata, Plantago major, Poa annua, Poa trivialis, Polygonum aviculare, Polygonum persicaria, Portulaca oleracea, Ranunculus repens, Raphanus sativus, Rapistrum rugosum, Rumex acetosella, Rumex crispus, Rumex obtusifolius, Senecio vulgaris, Senna tora, Setaria faberi, Setaria magna, Setaria pumila, Setaria pumila, Setaria verticillata, Setaria viridis, Sinapis arvensis, Sisymbrium altissimum, Solanum americanum, Solanum carolinense, Solanum nigrum, Sonchus arvensis, Sonchus oleraceus, Sorghum halepense, Spermacoce sp., Stellaria media, Taraxacum officinale, Toxicodendron radicans, Tribulus terrestris, Tripleurospermum inodorum, Tussilago farfara, Urochloa panicoides, Urochloa texana, Urtica dioica, Veronica arvensis, Veronica hederifolia, Veronica persica, Viola arvensis, and Xanthium spinosum, preferably wherein the compound is used against species selected from Alopecurus myosuroides, Avena fatua, Chenopodium album, Digitaria sanguinalis, Echinochloa crus-galli, Geranium dissectum, Lolium multiflorum, Panicum miliaceum, Setaria viridis and Solanum nigrum.

14. An intermediate selected from:

15. The intermediate of claim 14, wherein the intermediate is selected from:

16. A method for producing a compound according to any one of claims 1 to 11 , involving using one or more intermediates according to claim 14 in at least one step.

17. A method for producing compound according to any one of claims 1 to 11 , comprising a step selected from the following (i) to (iv):(i)wherein L, LG and LGXare each independently leaving groups, and the remaining groups are as defined hereinabove.

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