Ortho-heterocyclic substituted aryl amides for controlling invertebrate pests

The present invention relates to o-heterocyclic substituted arylamides, their N-oxides, salts and compositions suitable for agricultural and non-agricultural applications, including those listed below, and in both agricultural and non-agricultural environments. Regarding how to use them to control inverteous pests.

Invertebrate pest control is very important for achieving high yield rates. Damage to growing and stored crops by invertebrate pests significantly reduces productivity and, as a result, increases costs to consumers. Control of invertebrate pests in forestry, greenhouse crops, ornamental plants, seedlings, stored foods and textiles, livestock, home and public health and animal hygiene is also important. Although many products are commercially available for these purposes, there is still a need for new compounds that are more effective, less costly, less toxic, environmentally safe or have different modes of action.

In Patent Document 1, the formula ii: as an insecticide

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(In the formula, in particular R is H, alkyl or alkoxycarbonyl; X is halo, CN, NO₂, C₃~ C₆Halocycloalkyl; Y is halo, CN, NO₂, C₃~ C₆Halocycloalkyl; Z¹Is O or S; B₁~ B₄Are independently N or C; m is 1-5; n is 0-4) 2-heterocyclylbenzamide derivatives are disclosed.

<patcit num="1"><text>International Publication No. 01/00593 Pamphlet</text></patcit>

The present invention describes the formula I:

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(In the formula, A is O or S; G is C (= O), SO or S (O)₂A 5- or 6-membered aromatic heterocycle or a 5- or 6-membered non-aromatic heterocycle, optionally containing one or two ring members selected independently of the group consisting of, each ring optionally. 1 to 4 R²Replaced by; J is an independently phenyl ring, 5- or 6-membered aromatic heterocycle or 8-membered, 9- or 10-membered carbon bicyclic or heterobicyclic aromatic fused ring system, each ring or ring system. In some cases 1 to 4 R³Replaced by; R¹Is H; or C₁~ C₆Alkyl, C₂~ C₆Alkenyl, C₂~ C₆Alkyne or C₃~ C₆Cycloalkyl, each optionally halogen, CN, NO₂, Hydroxy, C₁~ C₄Alkoxy, C₁~ C₄Alkylthio, C₁~ C₄Alkyl sulfinyl, C₁~ C₄Alkylsulfonyl, C₂~ C₄Alkoxycarbonyl, C₁~ C₄Alkylamino, C₂~ C₈Dialkylamino and C₃~ C₆Substituent with one or more substituents independently selected from the group consisting of cycloalkylamino; or R¹Is C₂~ C₆Alkylcarbonyl, C₂~ C₆Alkoxycarbonyl, C₂~ C₆Alkylaminocarbonyl, C₃~ C₈Dialkylaminocarbonyl or C (= A) J; R²Or R³Are independently H and C₁~ C₆Alkyl, C₂~ C₆Alkenyl, C₂~ C₆Alkyne, C₃~ C₆Cycloalkyl, C₁~ C₆Haloalkyl, C₂~ C₆Haloalkenyl, C₂~ C₆Halo alkynyl, C₃~ C₆Halocycloalkyl, halogen, CN, CO₂H, CONH₂, NO₂, Hydroxy, C₁~ C₄Alkoxy, C₁~ C₄Haloalkoxy, C₁~ C₄Alkylthio, C₁~ C₄Alkyl sulfinyl, C₁~ C₄Alkylsulfonyl, C₁~ C₄Haloalkylthio, C₁~ C₄Haloalkyl sulfinyl, C₁~ C₄Haloalkylsulfonyl, C₁~ C₄Alkylamino, C₂~ C₈Dialkylamino, C₃~ C₆Cycloalkylamino, C₂~ C₆Alkylcarbonyl, C₂~ C₆Alkoxycarbonyl, C₂~ C₆Alkylaminocarbonyl, C₃~ C₈Dialkylaminocarbonyl or C₃~ C₆Trialkylsilyl; or R²Or R³Are independently phenyl, benzyl, benzoyl, phenoxy or 5- or 6-membered aromatic heterocycles, naphthyl ring systems, or aromatic or non-aromatic 8-membered, 9- or 10-membered heterobicyclic fused ring systems. There, each ring or ring system is R⁵Substituent with 1 to 3 substituents selected independently of; Two R³Together if they bond to adjacent carbon atoms-OCF₂O-, -CF₂CF₂O- or -OCF₂CF₂Can be O-; R⁴Are independent C₁~ C₆Alkyl, C₂~ C₆Alkenyl, C₂~ C₆Alkyne, C₃~ C₆Cycloalkyl, C₁~ C₆Haloalkyl, C₂~ C₆Haloalkenyl, C₂~ C₆Halo alkynyl, C₃~ C₆Halocycloalkyl, halogen, CN, NO₂, Hydroxy, C₁~ C₄Alkoxy, C₁~ C₄Haloalkoxy, C₁~ C₄Alkylthio, C₁~ C₄Alkyl sulfinyl, C₁~ C₄Alkylsulfonyl, C₁~ C₄Haloalkylthio, C₁~ C₄Haloalkyl sulfinyl, C₁~ C₄Haloalkylsulfonyl, C₁~ C₄Alkylamino, C₂~ C₈Dialkylamino, C₃~ C₆Cycloalkylamino, or C₃~ C₆Trialkylsilyl; or R⁴Are independently phenyl, benzyl or phenoxy rings, each ring being R⁵Substituted with 1-3 substituents selected independently of; R⁵Are independently H and C₁~ C₄Alkyl, C₂~ C₄Alkenyl, C₂~ C₄Alkyne, C₃~ C₆Cycloalkyl, C₁~ C₄Haloalkyl, C₂~ C₄Haloalkenyl, C₂~ C₄Halo alkynyl, C₃~ C₆Halocycloalkyl, halogen, CN, NO₂, C₁~ C₄Alkoxy, C₁~ C₄Haloalkoxy, C₁~ C₄Alkylthio, C₁~ C₄Alkyl sulfinyl, C₁~ C₄Alkylsulfonyl, C₁~ C₄Alkylamino, C₂~ C₈Dialkylamino, C₃~ C₆Cycloalkylamino, C₄~ C₇(Alkyl) Cycloalkylamino, C₂~ C₄Alkylcarbonyl, C₂~ C₆Alkoxycarbonyl, C₂~ C₆Alkylaminocarbonyl, C₃~ C₈Dialkylaminocarbonyl or C₃~ C₆Trialkylsilyl; n is an integer from 1 to 4) And its N-oxides and salts thereof.

The present invention presents invertebrate pests or their environment in biologically effective amounts with compounds of formula I, their N-oxides or suitable salts of the compounds (eg, as compositions described herein). It also relates to methods of controlling invertebrate pests, including contact. The present invention applies a biologically effective amount of a compound of formula I, an N-oxide or a suitable salt thereof, or a compound thereof, an N-oxide or a suitable salt thereof, to an invertent pest or its environment. It also relates to a composition comprising, and such a method of contacting with at least one other compound or agent in a biologically effective amount for controlling invertent pests.

The present invention is at least one selected from the group consisting of a biologically effective amount of a compound of formula I, its N-oxide or a suitable salt of the compound, and a surfactant, a solid diluent and a liquid diluent. It also relates to compositions for controlling invertent pests, which consist of other components of the species. The present invention comprises a biologically effective amount of a compound of formula I, an N-oxide thereof or a suitable salt of the compound, and an effective amount of at least one other bioactive compound or substance. Also related to.

Details of the invention In the above description, "alkyl" used alone or in the word compound such as "alkylthio" or "haloalkyl" refers to a straight chain or branched chain such as methyl, ethyl, n-propyl, i-propyl. Includes alkyl, or different butyl, pentyl or hexyl isomers. "Alkenes" include straight or branched alkenes such as 1-propenyl, 2-propenyl, and different butenyl, pentenyl and hexenyl isomers. "Alkenyl" also includes 1,2-propazienyl and 2,4-hexadienyl. "Alkynyl" includes linear or branched alkynes such as 1-propynyl, 2-propynyl, and different butynyl, pentynyl and hexynyl isomers. "Alkynyl" also includes moieties composed of multiple triple bonds such as 2,5-hexadynyl. "Alkoxy" includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy, and different butoxy, pentoxy and hexyloxy isomers. "Alkylthio" includes branched or linear alkylthio moieties such as methylthio, ethylthio, and different propylthio and butylthio isomers. "Cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. For "trialkylsilyl", (CH₃)₃Si, (CH₃CH₂)₃Si and [(CH₃)₃C] (CH₃)₂Si is included.

The term "aromatic" means that each atom in the ring is essentially coplanar, has a p-orbital perpendicular to the surface of the ring, and is a (4n + 2) π-electron (n is 0 or positive). Indicates that (integer) is associated with the ring according to Hückel's law. The term "aromatic ring system" refers to completely unsaturated carbocycles and heterocycles in which at least one ring of the polycyclic ring system is aromatic. Aromatic carbocyclic or bicyclic fused ring systems include fully aromatic carbocycles and carbocycles in which at least one ring of the polycyclic ring system is aromatic (eg, phenyl, naphthyl and). 1,2,3,4-tetrahydronaphthyl) is included. The term "non-aromatic carbocyclic ring" refers to a fully saturated carbocyclic ring as well as a partially or completely unsaturated carbocyclic ring, and the Hückel's rule is not filled by the ring. The term "hetero" with respect to a ring or ring system means that at least one ring atom is not carbon and each ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs. As a condition, it means a ring or ring system that can contain 1 to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur. The terms "aromatic heterocycle or ring system" and "aromatic heterobicyclic fused ring system" refer to a complex in which at least one ring of a fully aromatic heterocycle and a polycyclic ring system is aromatic. Contains rings (aromatic means that Hückel's law is satisfied). The term "non-aromatic heterocyclic ring or ring system" refers to a fully saturated heterocycle and a partially or completely unsaturated heterocycle in which the Hückel's rule is not satisfied by any of the rings of the ring system. The heterocyclic ring or ring system can be attached by substitution to hydrogen on the carbon or nitrogen via any of the available carbons or nitrogens.

"Halogen", used alone or in the word compound such as "haloalkyl", includes fluorine, chlorine, bromine or iodine. Further, when used in the term compound such as "haloalkyl", the alkyl can be partially or completely substituted with the same or different halogen atoms. An example of "haloalkyl" is F₃C, ClCH₂, CF₃CH₂And CF₃CCl₂Can be mentioned. Haloalkenyl, haloalkynyl, haloalkoxy and the like are defined in the same manner as the term haloalkyl. An example of "haloalkenyl" is (Cl)₂C = CHCH₂And CF₃CH₂CH = CHCH₂Can be mentioned. Examples of "haloalkynyl" are HCCCHCl, CF₃CC, CCl₃CC and FCH₂CCCH₂Can be mentioned. An example of "haloalkoxy" is CF₃O, CCl₃CH₂O, HCF₂CH₂CH₂O and CF₃CH₂O is mentioned.

An example of an "alkylcarbonyl" is C (O) CH₃, C (O) CH₂CH₂CH₃And C (O) CH (CH)₃)₂Can be mentioned. An example of "alkoxycarbonyl" is CH₃OC (= O), CH₃CH₂OC (= O), CH₃CH₂CH₂OC (= O), (CH₃)₂CHOC (= O) and different butoxy or pentoxycarbonyl isomers can be mentioned. An example of an "alkylaminocarbonyl" is CH₃NHC (= O), CH₃CH₂NHC (= O), CH₃CH₂CH₂NHC (= O), (CH₃)₂CHNHC (= O) and different butylamino or pentylaminocarbonyl isomers can be mentioned. As an example of "dialkylaminocarbonyl", (CH₃)₂NC (= O), (CH₃CH₂)₂NC (= O), CH₃CH₂(CH₃) NC (= O), CH₃CH₂CH₂(CH₃) NC (= O) and (CH₃)₂CHN (CH₃) C (= O).

The total number of carbon atoms in the substituent is "C_i~ C_j(In the formula, i and j are integers from 1 to 8). For example, C₁~ C₃Alkylsulfonyl represents methylsulfonyl to propylsulfonyl.

In the above description, if the compound of formula I contains a heterocyclic ring, all substituents will be subjected to this by substitution of hydrogen on the carbon or nitrogen via any available carbon or nitrogen. It is bound to a ring.

When a compound is substituted with a substituent having a substituent indicating that the number of substituents can exceed 1, the substituents (if they exceed 1) are independent of the defined group of substituents. Is selected. In addition, the subscript is a range, eg (R)_{i ~ j}In the case of, the number of substituents is selected from the integers of i to j.

The term "possibly substituted" means that the group may or may not be substituted. "In some cases substituted with 1 to 3 substituents" etc. means that the group is unsubstituted or 1 to 3 of its available positions may be substituted. Substituents in which the group can be hydrogen, such as R¹Or R⁵If the substituent is then hydrogen, it is considered to correspond to the unsubstituted group.

The compounds of the present invention may exist as one or more stereoisomers. Various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. Those skilled in the art will appreciate that one of the stereoisomers is fortified against the other stereoisomer (s) or is separated from the other (s). It will be appreciated that it may be more active and / or may have a beneficial effect. In addition, those skilled in the art will know how to separate, fortify, and / or selectively produce the stereoisomers. Thus, the compounds of the invention can exist as a mixture of steric isomers, individual steric isomers, or in a state of optically active. Some compounds of the invention can exist as one or more tautomers, and all tautomers of such compounds are part of the invention. Thus, the compounds of the invention can exist as a mixture of tautomers or as individual tautomers.

The present invention comprises a compound selected from Formula I, its N-oxide and its agriculturally suitable salt. Those skilled in the art will understand that not all nitrogen-containing heterocycles form N-oxides, as nitrogen requires lone pairs of electrons available to oxidize to its oxides; Those skilled in the art will understand nitrogen-containing heterocycles capable of forming N-oxides. Those skilled in the art will also appreciate that tertiary amines can form N-oxides. Synthetic methods for the production of N-oxides of heterocyclic and tertiary amines are very well known to those skilled in the art and are peracetic acids and peroxy acids such as m-chloroperbenzoic acid (MCPBA). Oxidation of heterocycles and tertiary amines with hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, dioxylans such as sodium perborate, and dimethyldioxirane can be mentioned. These methods of producing N-oxides have been extensively described and studied in the literature. For example, TLGilchrist in Comprehensive Organic Synthesis, vol.7, pp748-750, SVLey, Ed., Pergamon Press; M.Tisler and B.Stanovnik in Comprehensive Heterocyclic Chemistry, Vol.3, pp18-19, AJBoulton and A.McKillop, Eds., Pergamon Press; BRTKeene in Advances in Heterocyclic Chemistry, Vol.43, pp139-151, ARKatritzky, Ed., Academic Press; M.Tisler and B.Stanovnik in Advances in Heterocyclic Chemistry, Vol.9, pp285-291, ARKatritzky and AJBoulton, Eds. , Academic Press; GWH See Cheeseman and ESGWerstiuk in Advances in Heterocyclic Chemistry, Vol.22, pp390-392, ARKatritzky and AJBoulton, Eds., Academic Press.

The salts of the compounds of the present invention include inorganic or organic acids such as hydrobromic acid, hydrochlorite, nitrate, phosphoric acid, sulfuric acid, acetic acid, butyric acid, fumaric acid, lactic acid, maleic acid, malonic acid, oxalic acid, propion. Includes acid addition salts with acids, salicylic acid, tartaric acid, 4-toluenesulfonic acid or valerate. The salts of the compounds of the present invention include organic bases (eg, pyridine, ammonia, or triethylamine) or inorganic bases (eg, sodium, potassium, lithium, calcium, etc.) when the compound contains acidic groups such as carboxylic acids or phenols. Includes salts formed from magnesium or barium hydrides, hydroxides, or carbon salts).

As mentioned above, R¹Is (especially) C₁~ C₆Alkyl, C₂~ C₆Alkenyl, C₂~ C₆Alkyne or C₃~ C₆Can be cycloalkyl, each optionally halogen, CN, NO₂, Hydroxy, C₁~ C₄Alkoxy, C₁~ C₄Alkylthio, C₁~ C₄Alkyl sulfinyl, C₁~ C₄Alkylsulfonyl, C₂~ C₄Alkoxycarbonyl, C₁~ C₄Alkylamino, C₂~ C₈Dialkylamino and C₃~ C₆Substituents are substituted with one or more substituents independently selected from the group consisting of cycloalkylaminos. These R¹The term "possibly substituted" with respect to a group is R which is unsubstituted or has at least one non-hydrogen substituent.¹Means a group. R to be replaced in some cases¹As an example of the group, R¹One or more hydrogens on the carbon atom of the group selected independently of the substituents listed above (specific R)¹A group that is optionally substituted by substitution with a substituent (up to the total number of hydrogens available for substitution at the group). Note that these substituents are listed in the example above, but they do not need to be present as they are arbitrary substituents. Unreplaced R¹The group is noteworthy. R substituted with 1-5 substituents¹The group is noteworthy. R substituted with one substituent¹The group is also noteworthy.

As mentioned above, J is an independently phenyl ring, 5- or 6-membered aromatic heterocycle or aromatic 8-membered, 9- or 10-membered carbon bicyclic or heterobicyclic aromatic fused ring system, respectively. Each ring or ring system may have 1 to 4 Rs.³Replaced by. The term "optionally substituted" with respect to these J groups means a group that is unsubstituted or has at least one non-hydrogen substituent. 1 to 4 R³An example of a phenyl optionally substituted in is the ring (R) shown as U-1 in Presentation 1.^vIs R³And r is an integer from 1 to 4). Examples of aromatic 8-membered, 9- or 10-membered carbon bicyclic fused ring systems are 1-3 Rs shown as U-85 in Presentation 1.³A naphthyl group optionally substituted with, and a 1,2,3,4-tetrahydronaphthyl group (R) shown as U-89 in Presentation 1.^vIs R³And r is an integer from 1 to 4). 1 to 4 R³An example of a 5- or 6-membered aromatic heterocycle optionally substituted in is the ring (R) of U-2 to U-53 shown in Presentation 1.^vIs R³And r is an integer from 1 to 4). Note that J-1 to J-4 below also show 5- or 6-membered aromatic heterocycles. U-2 to U-20 are examples of J-1, U-21 to U-35 and U-40 are examples of J-2, and U-41 to U-48 are examples of J-3. Note that U-49 to U-53 are examples of J-4. 1 to 4 R³Examples of aromatic 8-membered, 9- or 10-membered complex bicyclic fused ring systems that are optionally substituted in are U-54 to U-84 (R) shown in Presentation 1.^vIs R³And r is an integer from 1 to 4).

R^vNote that the groups are shown in structures U-1 to U-89, but they do not need to be present as they are arbitrary substituents. When binding to an atom, R^vNote that if is H, this is as if the atom was unsubstituted. Nitrogen atoms that require substitution to satisfy their valence are H or R^vReplaced by. Only some U groups have less than 4 R^vOnly one R can be substituted with a group (eg, U-14, U-15, U-18 to U-21 and U-32 to U-34)^vNote that it can be replaced with). (R^v)_rIf the bond point between the and U groups is shown as floating, then (R^v)_rNote that can be attached to any of the available carbon atoms of the U group. Note that if the bond point on the U group is shown as floating, the U group can be attached to the rest of formula I via any of the available carbons of that U group by substitution of a hydrogen atom. thing.

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<chemistry num="4"><img file="JP4445751B2_D0004.tif" /></chemistry>

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As mentioned above, G is C (= O), SO or S (O)₂A 5- or 6-membered aromatic heterocycle or a 5- or 6-membered non-aromatic heterocyclic ring, each of which optionally comprises one or two ring members selected independently of the group consisting of. 1 to 4 Rs in some cases²Replaced by. The term "optionally substituted" with respect to these G groups means a group that is unsubstituted or has at least one non-hydrogen substituent. 1 to 4 R²Examples of 5- or 6-membered aromatic heterocycles optionally substituted with are rings U-2 to U-53 (R) shown in Presentation 1.^vIs R²And r is an integer from 1 to 4). Note that the following G-1 to G-5 also exhibit 5- or 6-membered aromatic heterocycles. U-2 to U-20 are examples of G-1, U-21 to U-35 and U-40 are examples of G-2, and U-36 to U-39 are examples of G-3. Note that U-41 to U-48 are examples of U-4 and U-49 to U-53 are examples of G-5.

C (= O), SO or S (O)₂Contains one or two ring members selected independently of the group consisting of 1 to 4 Rs²An example of G as a 5- or 6-membered non-aromatic heterocyclic ring, optionally substituted with, is shown in Presentation 2. Note that if the bond points on these G groups are shown as floating, the G group can be attached to the rest of formula I via the available carbon or nitrogen of the G group by substitution of a hydrogen atom. The optional substituent can be attached to an available carbon or nitrogen by substituting a hydrogen atom. If G contains a ring selected from G-31 to G-346 and G-39 to G-42, then Q is O, S or NR.²Please note that it will be selected from. When G is G-10, G-12, G-14, G-16, G-23, G-24, G-25, G-30 ~ G-36 and G-39 ~ G-42 (Q) Is NR²If), the nitrogen atoms that need to be substituted to satisfy their valences are H or R.²Note that it is replaced by. Also note that the following G-6, G-7 and G-43 also mean 5- or 6-membered non-aromatic heterocyclic rings. Note that G-19, G-20 and G-23 are examples of G-6 if their binding points are in the 2-position. Note that G-25, G-26 and G-27 are examples of G-7 if the binding point is in the 2-position. Note that G-40 is an example of G-43 if its binding point is in the 2-position.

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<chemistry num="8"><img file="JP4445751B2_D0008.tif" /></chemistry>

As mentioned above, each R²And each R³Independently (especially) phenyl, benzyl, benzoyl, phenoxy, or 5- or 6-membered aromatic heterocycles, naphthyl cyclics, or aromatic or non-aromatic 8-membered, 9- or 10-membered heterobicyclic condensations. It can be a ring system, and each ring or ring system is R⁵Substituents are substituted with 1 to 3 substituents selected independently of. Such R²And R³Examples of the rings U-1 (phenyl), U-87 (benzyl), U-88 (benzoyl), U-86 (phenoxy), U-85 (naphthyl), U-2 ~ shown in Presentation 1. U-53 (5- or 6-membered aromatic heterocycle) and U-54 to U-84 (aromatic or non-aromatic 8-membered, 9- or 10-membered heterobicyclic fused ring system) (R)^vIs R⁵And r is an integer from 1 to 3).

As mentioned above, R⁴Can be independently (among others) phenyl, benzyl, or phenoxy rings, each ring being R.⁵Substituents are substituted with 1 to 3 substituents selected independently of. Such R⁴Examples of groups are the rings U-1 (phenyl), U-87 (benzyl) and U-86 (phenoxy) (R) shown in Presentation 1.^vIs R⁵And r is an integer from 1 to 3).

Preferred compounds because of their better activity and / or ease of synthesis: Preferred compounds 1. Compounds of formula I In the formula, A is O; G is selected from the group consisting of G-1, G-2, G-3, G-4, G-5, G-6, G-7 and G-43, and each G is 1 to 4 Rs.²Replaced in some cases

<chemistry num="9"><img file="JP4445751B2_D0009.tif" /></chemistry>

Q is O, S or NR²Is; W, X, Y and Z are independently N or CR²However, in G-4 and G-5, at least one of W, X, Y or Z is N; J is a phenyl ring or a 5- or 6-membered aromatic heterocycle selected from the group consisting of J-1, J-2, J-3 and J-4, with each J ring having 1 to 3 Rs.³Replaced in some cases

<chemistry num="10"><img file="JP4445751B2_D0010.tif" /></chemistry>

Q¹Is O, S or NR³Is; W¹, X¹, Y¹And Z¹Is independently N or CR³However, in J-3 and J-4, W¹, X¹, Y¹Or Z¹At least one of is N; R³Are independently H and C₁~ C₄Alkyl, C₁~ C₄Haloalkyl, halogen, CN, NO₂, C₁~ C₄Alkoxy, C₁~ C₄Haloalkoxy, C₁~ C₄Alkylthio, C₁~ C₄Alkyl sulfinyl, C₁~ C₄Alkylsulfonyl, C₁~ C₄Haloalkylthio, C₁~ C₄Haloalkyl sulfinyl, C₁~ C₄Haloalkylsulfonyl, C₂~ C₄Alkoxycarbonyl, C₂~ C₆Alkylaminocarbonyl or C₃~ C₈Dialkylaminocarbonyl; or R³Are independently phenyl, benzyl or 5- or 6-membered aromatic heterocycles, each ring being R⁵Substituentally substituted with 1 to 3 substituents selected independently of; Two R³Together if they bond to adjacent carbon atoms-OCF₂O-, -CF₂CF₂O- or -OCF₂CF₂Can be O-; 1 R⁴The group is attached to the rest of formula I at either the 2- or 5-position of the phenyl ring and said R⁴Is C₁~ C₄Alkyl, C₁~ C₄Haloalkyl, halogen, CN, NO₂, C₁~ C₄Alkoxy, C₁~ C₄Haloalkoxy, C₁~ C₄Alkylthio, C₁~ C₄Alkyl sulfinyl, C₁~ C₄Alkylsulfonyl, C₁~ C₄Haloalkylthio, C₁~ C₄Haloalkylsulfinyl or C₁~ C₄Haloalkylsulfonyl; m is an integer from 0 to 4.

Preferred compound 2. Compound of preferred compound 1 In the formula, R¹Is H or C₂~ C₆Alkyl; One R that joins J in the ortho position with respect to the C = A part³Group, and possibly one or two additional Rs³Exists and R³The groups are independent H and C₁~ C₄Alkyl, C₁~ C₄Haloalkyl, halogen, CN, NO₂, C₁~ C₄Alkoxy, C₁~ C₄Haloalkoxy, C₁~ C₄Alkylthio, C₁~ C₄Alkyl sulfinyl, C₁~ C₄Alkylsulfonyl, C₁~ C₄Haloalkylthio, C₁~ C₄Haloalkyl sulfinyl, C₁~ C₄Haloalkylsulfonyl, C₂~ C₄Alkoxycarbonyl, C₂~ C₆Alkylaminocarbonyl, C₃~ C₈Dialkylaminocarbonyl; or phenyl, benzyl, or 5- or 6-membered aromatic heterocycle, each ring of halogen, CN, NO₂, C₁~ C₄Alkyl, C₂~ C₄Alkenyl, C₂~ C₄Alkyne, C₃~ C₆Cycloalkyl, C₁~ C₄Haloalkyl, C₁~ C₄Alkoxy or C₁~ C₄Occasionally replaced with haloalkoxy; n is 1 or 2.

Preferred compound 3. Preferred compound 2 compound In the formula, J is a phenyl, pyrazole, pyrrole, pyridine or pyrimidine ring, each with one R attached to J at the ortho position with respect to the C = A moiety.³And in some cases one or two additional Rs³Replaced by;

Preferred compound 4. Preferred compound 3 compound In the formula, R¹Is H; 1 R⁴Is NR¹Bonded to the rest of formula I at the 2-position of the ortho phenyl ring with respect to the C (= A) J moiety and C₁~ C₃Alkyl, CF₃, OCF₃, OCHF₂, S (O)_pCF₃, S (O)_pCHF₂And optionally a second R selected from the group consisting of halogens⁴Is NR¹Bonded to the C (= A) J moiety at the 4-position of the para-phenyl ring and halogen, C₁~ C₃Alkyl and C₁~ C₃Selected from the group consisting of haloalkyl; p is 0, 1 or 2.

Preferred compound 5. Preferred compound 4 compound In the formula, J is a pyrazole or pyrrole ring selected from the group consisting of J-5, J-6, J-7, J-8, J-9 and J-10, and each ring is R.³Replaced by, and in some cases R⁶And R⁷Replaced by;

<chemistry num="11"><img file="JP4445751B2_D0011.tif" /></chemistry>

R³Is H, C₁~ C₄Alkyl, C₁~ C₄Haloalkyl, or

<chemistry num="12"><img file="JP4445751B2_D0012.tif" /></chemistry>

V is N, CH, CF, CCl, CBr or CI; Each R⁵And each R⁶Are independently H, C₁~ C₆Alkyl, C₃~ C₆Cycloalkyl, C₁~ C₆Haloalkyl, halogen, CN, C₁~ C₄Alkoxy, C₁~ C₄Haloalkoxy or C₁~ C₄Haloalkylthio; R⁷Is H, C₁~ C₆Alkyl, C₁~ C₆Haloalkyl, C₃~ C₆Alkenyl, C₃~ C₆Haloalkenyl, C₃~ C₆Alkyne or C₃~ C₆It is haloalkynyl.

R⁶And R⁷Is R³Note that it is a subset of. The F, Cl, Br or I atoms contained within V are R⁵Note that it is a subset of. R³Note that the part shown for joins to J via the join highlighted by the dashed line.

Preferred Compound 6. Preferred Compound 5 Compound In the formula, V is N.

Preferred compound 7. Compound of preferred compound 5 In the formula, V is CH, CF, CCl or CBr.

Preferred compound 8. Compound of preferred compound 6 or preferred compound 7 In the formula, R⁵Is H, C₁~ C₄Alkyl, C₁~ C₄Haloalkyl, halogen or CN; R⁶Is H, CH₃, CF₃, OCH₂CF₃, OCHF₂Or halogen; R⁷Is CH₂CF₃, CHF₂Or CF₃Is.

Preferred Compound 9. Preferred Compound 8 Compound In the formula, R³Replaced by, and optionally R⁶J replaced by is J-5; R⁵Is Cl or Br; R⁶Is halogen, OCH₂CF₃, OCHF₂Or CF₃Is.

Preferred Compound 10. Preferred Compound 8 Compound In the formula, R³Replaced by, and optionally R⁷J replaced by is J-6; R⁹Is Cl or Br; R⁷Is CH₂CF₃, CHF₂Or CF₃Is.

Preferred Compound 11. Preferred Compound 8 Compound In the formula, R³Replaced by, and optionally R⁷J replaced by is J-7; R⁹Is Cl or Br; R⁷Is CH₂CF₃, CHF₂Or CF₃Is.

Preferred Compound 12. Preferred Compound 8 Compound In the formula, R³Replaced by, and optionally R⁶J replaced by is J-8; R⁵Is Cl or Br; R⁶Is halogen, OCH₂CF₃, OCHF₂Or CF₃Is.

Preferred Compound 13. Preferred Compound 8 Compound In the formula, R³Replaced by, and optionally R⁶And R⁷J replaced by is J-9; R⁵Is Cl or Br; R⁶Is halogen, OCH₂CF₃, OCHF₂Or CF₃Is; R⁷Is CH₂CF₃, CHF₂Or CF₃Is.

Preferred Compound 14. Preferred Compound 8 Compound In the formula, R³Replaced by, and optionally R⁷J replaced by is J-10; R⁹Is Cl or Br; R⁷Is CH₂CF₃, CHF₂Or CF₃Is.

Of note are the compounds of preferred compounds 6 to 14 (where G is G-1, G-2, G-6 or G-43 in the formula).

Most preferred: 1- (3-Chloro-2-pyridinyl) -N- [2- (1H-imidazol-2-yl) -6-methylphenyl] -3- (trifluoromethyl) -1H-pyrazole-5-carboxamide, 1-(2-Chloromethyl-N- [2-Methyl-6- (1-Methyl-1H-imidazol-2-yl) phenyl] -3- (trifluoromethyl) -1H-pyrazole-5-carboxamide, 1- (2-Chlorophenyl) -N- [2- (4,5-dihydro-1-methyl-1H-imidazol-2-yl) -6-methylphenyl] -3- (trifluoromethyl) -1H-pyrazole -5-Carboxamide, 1- (3-Chloro-2-pyridinyl) -N- [2- (4,5-dihydro-1-methyl-1H-imidazol-2-yl) -6-methylphenyl] -3- (trifluoromethyl) -1H-pyrazole-5-carboxamide, N- [4-Bromo-2- (4,5-dihydro-1-methyl-1H-imidazol-2-yl) -6-methylphenyl] -1- (2-chlorophenyl) -3- (trifluoromethyl) -1H-pyrazole-5-carboxamide, N- [4-Bromo-2- (4,5-dihydro-1-methyl-1H-imidazol-2-yl) -6-methylphenyl] -1- (3-chloro-2-pyridinyl) -3- ( Trifluoromethyl) -1H-pyrazole-5-carboxamide, 1- (3-Chloro-2-pyridinyl) -N- [2- (4,5-dihydro-2-oxazolyl) -6-methylphenyl] -3- (trifluoromethyl) -1H-pyrazole-5-carboxamide ,and 1- (3-Chloro-2-pyridinyl) -N- [2,4-dichloro-6- (4,5-dihydro-1H-imidazol-2-yl) phenyl] -3- (trifluoromethyl) -1H -A compound of formula I selected from the group consisting of pyrazole-5-carboxamide.

The present invention also relates to compositions for controlling invertebrate pests comprising biologically effective amounts of compounds of formula I, their N-oxides or suitable salts of the compounds. A preferred composition is a composition comprising the compounds of formula I preferred in the preferred compounds 1-14 and the above compounds particularly preferred.

The present invention relates to a biologically effective amount of a compound of formula I, its N-oxide or a suitable salt of the compound (eg, as the composition described herein) and an invertebrate pest or an invertebrate pest thereof or the like. It also relates to methods of controlling invertebrate pests, including contact with the environment. The preferred method comprises the compounds of formula I preferred in the preferred compounds 1-14, and the particularly preferred compounds described above.

Expression Ie:

<chemistry num="13"><img file="JP4445751B2_D0013.tif" /></chemistry>

(In the formula, A is O or S; G is C (= O), SO or S (O)₂A 5- or 6-membered aromatic heterocycle or a 5- or 6-membered non-aromatic heterocycle, optionally containing one or two ring members selected from the group consisting of, each ring optionally having 1 to 4 members. Two R²Replaced by; J is independently a phenyl ring, a naphthyl ring system, a 5- or 6-membered aromatic heterocycle or an 8-membered, 9- or 10-membered heterobicyclic aromatic condensed ring system, and each ring or ring system is 1 to 4 Rs in some cases³Replaced by; R¹Is H; or C₁~ C₆Alkyl, C₂~ C₆Alkenyl, C₂~ C₆Alkyne or C₃~ C₆Cycloalkyl, each optionally halogen, CN, NO₂, Hydroxy, C₁~ C₄Alkoxy, C₁~ C₄Alkylthio, C₁~ C₄Alkyl sulfinyl, C₁~ C₄Alkylsulfonyl, C₂~ C₄Alkoxycarbonyl, C₁~ C₄Alkylamino, C₂~ C₈Dialkylamino and C₃~ C₆Substituent with one or more substituents selected from the group consisting of cycloalkylamino; or R¹Is C₂~ C₆Alkylcarbonyl, C₂~ C₆Alkoxycarbonyl, C₂~ C₆Alkylaminocarbonyl, C₃~ C₈Dialkylaminocarbonyl or C (= A) J; R²Or R³Are independently H and C₁~ C₆Alkyl, C₂~ C₆Alkenyl, C₂~ C₆Alkyne, C₃~ C₆Cycloalkyl, C₁~ C₆Haloalkyl, C₂~ C₆Haloalkenyl, C₂~ C₆Halo alkynyl, C₃~ C₆Halocycloalkyl, halogen, CN, CO₂H, CONH₂, NO₂, Hydroxy, C₁~ C₄Alkoxy, C₁~ C₄Haloalkoxy, C₁~ C₄Alkylthio, C₁~ C₄Alkyl sulfinyl, C₁~ C₄Alkylsulfonyl, C₁~ C₄Haloalkylthio, C₁~ C₄Haloalkyl sulfinyl, C₁~ C₄Haloalkylsulfonyl, C₁~ C₄Alkylamino, C₂~ C₈Dialkylamino, C₃~ C₆Cycloalkylamino, C₂~ C₆Alkylcarbonyl, C₂~ C₆Alkoxycarbonyl, C₂~ C₆Alkylaminocarbonyl, C₃~ C₈Dialkylaminocarbonyl, C₃~ C₆Trialkylsilyl; or R²Or R³Are independently phenyl, benzyl, benzoyl, phenoxy, 5- or 6-membered aromatic heterocycles, naphthyl ring systems, or aromatic or non-aromatic 8-membered, 9- or 10-membered heterobicyclic fused ring systems. There, each ring or ring system is C₁~ C₄Alkyl, C₂~ C₄Alkenyl, C₂~ C₄Alkyne, C₃~ C₆Cycloalkyl, C₁~ C₄Haloalkyl, C₂~ C₄Haloalkenyl, C₂~ C₄Halo alkynyl, C₃~ C₆Halocycloalkyl, halogen, CN, NO₂, C₁~ C₄Alkoxy, C₁~ C₄Haloalkoxy, C₁~ C₄Alkylthio, C₁~ C₄Alkyl sulfinyl, C₁~ C₄Alkylsulfonyl, C₁~ C₄Alkylamino, C₂~ C₈Dialkylamino, C₃~ C₆Cycloalkylamino, C₃~ C₆(Alkyl) Cycloalkylamino, C₂~ C₄Alkylcarbonyl, C₂~ C₆Alkoxycarbonyl, C₂~ C₆Alkylaminocarbonyl, C₃~ C₈Dialkylaminocarbonyl or C₃~ C₆Optionally substituted with 1-3 substituents independently selected from the group consisting of trialkylsilyls; or (R³)₂Together when bonded to adjacent carbon atoms-OCF₂O-, -CF₂CF₂O- or -OCF₂CF₂Can be O-; R⁴Are independently H and C₁~ C₆Alkyl, C₂~ C₆Alkenyl, C₂~ C₆Alkyne, C₃~ C₆Cycloalkyl, C₁~ C₆Haloalkyl, C₂~ C₆Haloalkenyl, C₂~ C₆Halo alkynyl, C₃~ C₆Halocycloalkyl, halogen, CN, NO₂, Hydroxy, C₁~ C₄Alkoxy, C₁~ C₄Haloalkoxy, C₁~ C₄Alkylthio, C₁~ C₄Alkyl sulfinyl, C₁~ C₄Alkylsulfonyl, C₁~ C₄Haloalkylthio, C₁~ C₄Haloalkyl sulfinyl, C₁~ C₄Haloalkylsulfonyl, C₁~ C₄Alkylamino, C₂~ C₈Dialkylamino, C₃~ C₆Cycloalkylamino, or C₃~ C₆Trialkylsilyl; or R⁴Are independently phenyl, benzyl or phenoxy, each C₁~ C₄Alkyl, C₂~ C₄Alkenyl, C₂~ C₄Alkyne, C₃~ C₆Cycloalkyl, C₁~ C₄Haloalkyl, C₂~ C₄Haloalkenyl, C₂~ C₄Halo alkynyl, C₃~ C₆Halocycloalkyl, halogen, CN, NO₂, C₁~ C₄Alkoxy, C₁~ C₄Haloalkoxy, C₁~ C₄Alkylthio, C₁~ C₄Alkyl sulfinyl, C₁~ C₄Alkylsulfonyl, C₁~ C₄Alkylamino, C₂~ C₈Dialkylamino, C₃~ C₆Cycloalkylamino, C₃~ C₆(Alkyl) Cycloalkylamino, C₂~ C₄Alkylcarbonyl, C₂~ C₆Alkoxycarbonyl, C₂~ C₆Alkylaminocarbonyl, C₃~ C₈Dialkylaminocarbonyl or C₃~ C₆Occasionally replaced with trialkylsilyl; n is 1 ~ 4) The compounds of, its N-oxides or their agriculturally suitable salts are notable.

The selected compound of formula Ie is also noteworthy: Selection A. Compound of formula Ie In the formula, A is O; G is selected from the group consisting of G-1, G-2, G-3, G-4, G-5, G-6, G-7 and G-43, where G is 1 to 4 Rs, respectively.²Replaced in some cases

<chemistry num="14"><img file="JP4445751B2_D0014.tif" /></chemistry>

Q is O, S or NR²Is; W, X, Y and Z independently N or CR²However, in G-4 and G-5, at least one of W, X, Y or Z is N; J is a phenyl ring or a 5- or 6-membered aromatic heterocycle selected from the group consisting of J-1, J-2, J-3 and J-4, where J is an independent 1-3 R.³Replaced by

<chemistry num="15"><img file="JP4445751B2_D0015.tif" /></chemistry>

Q¹Is O, S or NR²Is; W¹, X¹, Y¹And Z¹Is independently N or CR³However, in J-3 and J-4, W¹, X¹, Y¹Or Z¹At least one of is N; m is 0-4.

Selection B. Compound of Selection A In the formula, n is 1-2; R¹Is H or C₂~ C₆Alkyl; 1 R³The group is attached to J at the ortho position with respect to the C = A moiety, and the R³But C₁~ C₄Alkyl, C₁~ C₄Haloalkyl, halogen, CN, NO₂, C₁~ C₄Alkoxy, C₁~ C₄Haloalkoxy, C₁~ C₄Alkylthio, C₁~ C₄Alkyl sulfinyl, C₁~ C₄Alkylsulfonyl, C₁~ C₄Haloalkylthio, C₁~ C₄Haloalkyl sulfinyl, C₁~ C₄Haloalkylsulfonyl, or C₂~ C₄Alkoxycarbonyl, C₃~ C₈Dialkylaminocarbonyl or phenyl, benzyl, or 5- or 6-membered aromatic heterocycle, each ring of halogen, CN, NO₂, C₁~ C₄Alkyl, C₂~ C₄Alkenyl, C₂~ C₄Alkyne, C₃~ C₆Cycloalkyl, C₁~ C₄Haloalkyl, C₁~ C₄Alkoxy or C₁~ C₄Occasionally replaced with haloalkoxy; Any second R³Group independently C₁~ C₄Alkyl, C₁~ C₄Haloalkyl, halogen, CN, NO₂, C₁~ C₄Alkoxy, C₁~ C₄Haloalkoxy, C₁~ C₄Alkylthio, C₁~ C₄Alkyl sulfinyl, C₁~ C₄Alkylsulfonyl, C₁~ C₄Haloalkylthio, C₁~ C₄Haloalkyl sulfinyl, C₁~ C₄Haloalkylsulfonyl, or C₂~ C₄Alkoxycarbonyl, C₃~ C₈Dialkylaminocarbonyl or phenyl, benzyl, or 5- or 6-membered aromatic heterocycle, each ring of halogen, CN, NO₂, C₁~ C₄Alkyl, C₂~ C₄Alkenyl, C₂~ C₄Alkyne, C₃~ C₆Cycloalkyl, C₁~ C₄Haloalkyl, C₁~ C₄Alkoxy or C₁~ C₄It is optionally replaced with haloalkoxy.

Selection C. Selection B compound In the formula, J is phenyl, pyrazole, pyrrole, pyridine or pyrimidine, one R that binds to J at the ortho position with respect to the nitrogen atom connecting J and C = A, respectively.³And any second R³Replaced by.

Selection D. Selection C compound In the formula, R¹Is H; one R⁴Is NR¹It is connected to the C (= A) J part at the 2nd position of the ortho, and C₁~ C₃Alkyl, CF₃, OCF₃, OCHF₂, S (O)_pCF₃, S (O)_pCHF₂And any second R selected from the group consisting of halogens⁴Is NR¹Bonded to the C (= A) J part at the 4-position of the para, and halogen, C₁~ C₃Alkyl and C₁~ C₃Selected from the group consisting of haloalkyl; p is 0, 1 or 2.

Selection E. Selection D compound In the formula, J is J-1; Q¹Is NR^3aIs; X¹Is N or CH; Y¹Is CH; Z¹Is CR^3bIs; R^3aIs halogen, C₁~ C₄Alkyl, C₁~ C₄Haloalkyl or C₁~ C₄Phenyl or 2-pyridyl substituted with one or two substituents selected from haloalkoxy; R^3bIs halogen or CF₃Is.

Selection F. Selection D compound In the formula, G is G-1, G-2, G-6 or G-43.

The compounds of formula I can be prepared using one or more of the following methods and variants described in Schemes 1-45. A, G, J, R in the compounds of the following formulas 2 to 108¹, R², R³, R⁴, R⁵, R⁶, R⁷The definitions of, V and n are as defined above. The compounds of formulas Ia ~ e, 2a ~ 2b, 4a ~ v and 5a ~ y are various subsets of the compounds of formulas I, 2, 4 and 5, respectively. R^2a~ R^2eIs R²Is a subset of R³(c) and R³(d) is R³Is a subset of.

The usual procedure is described in Scheme 1 and involves coupling the amine of formula 2 with the acid chloride of formula 3 in the presence of an acid scavenger or base to provide the compound of formula Ia. Common acid traps include amine bases such as triethylamine, diisopropylethylamine and pyridine; other traps include hydroxides such as sodium hydroxide and potassium hydroxide and carbonates such as sodium carbonate and potassium carbonate. Salt is mentioned. In certain examples, it is effective to use polymer-bearing acid scavengers such as polymer-linked diisopropylethylamine and polymer-linked dimethylaminopyridine. Coupling can be carried out in a suitable inert solvent such as tetrahydrofuran, dioxane, diethyl ether or dichloromethane to give the anilide of formula Ia.

<chemistry num="16"><img file="JP4445751B2_D0016.tif" /></chemistry>

An alternative procedure for producing compounds of formula Ia is to use the amine of formula 2 with the acid of formula 4 and dicyclohexylcarbodiimide (DCC), 1,1'-carbonyldiimidazole, bis (2-oxo-3-oxazolidinyl). -Coupling in the presence of dehydrating agents such as phosphine chloride or benzotriazol hexafluorophosphate-1-yloxy-tris (dimethylamino) phosphonium. The coupling can be carried out in a suitable inert solvent such as dichloromethane or N, N-dimethylformamide. Here, polymer-supporting reagents such as polymer-bound cyclohexylcarbodiimides are again useful. Since the literature on synthesis is extensive for this type of reaction, the synthetic procedures of Schemes 1 and 2 are merely representative of methods useful for producing compounds of formula I.

<chemistry num="17"><img file="JP4445751B2_D0017.tif" /></chemistry>

Those skilled in the art will also appreciate that a number of known methods can be used to produce the acid chloride of formula 3 from the acid of formula 4. For example, the acid chloride of formula 3 is produced by reacting carboxylic acid 4 with thionyl chloride or oxalyl chloride in the presence of a catalytic amount of N, N-dimethylformamide in an inert solvent such as toluene or dichloromethane. Easily made from the carboxylic acid of formula 4.

The heterocyclic substituted aniline of formula 2a can usually be obtained from the corresponding 2-nitrobenzene of formula 5 by catalytic hydrogenation of the nitro group (Scheme 3). The usual procedure involves reduction with hydrogen in a hydroxy solvent such as ethanol and isopropanol in the presence of a metal catalyst such as carbon oxide or platinum oxide. They can also be produced by reducing with zinc in acetic acid. These procedures are detailed in the chemical literature. The substituted phenyl heterocycles of Equation 5 are Rodd's Chemistry of Organic Compounds: Heterocyclic Compounds, Volume IV, parts C, F and IJ 1989, Comprehensive Heterocyclic Chemistry, Volumes 2,3,4,5 and 6 (1984) and Heterocyclic Chemistry. II, General methods such as those described in Volumes 3,4,5 and 6 1996, International Publication (PCT International Application) No. 98 / 56,789 (1998) and International Publication (PCT International Application) No. 96 / 06,096 (1996). It can be manufactured according to the method. R of alkyl, substituted alkyl, etc.¹Substituents can generally be introduced at this stage by known procedures involving any direct alkylation or by generally preferred methods of reductive alkylation of aniline. A commonly used procedure is to combine aniline 2a with an aldehyde in the presence of a reducing agent such as sodium cyanoborohydride and formula 2b (in formula, R).¹Is an alkyl, alkenyl, alkynyl or a substituted derivative thereof).

<chemistry num="18"><img file="JP4445751B2_D0018.tif" /></chemistry>

In Scheme 4, the compounds of formula Ib are placed in the presence of a base such as sodium hydride or n-butyllithium in an inert solvent such as tetrahydrofuran or N, N-dimethylformamide, suitable such as alkyl halides. Alkylated with an alkylating agent, formula Ic (in formula, R)¹Shows that anilide (other than hydrogen) can be obtained. This procedure is based on the formula Ic (in the formula, R).¹Is particularly useful for making compounds of alkyl, alkenyl or alkynyl).

<chemistry num="19"><img file="JP4445751B2_D0019.tif" /></chemistry>

Expression Id (in expression, R¹Will outline the production of hydrogen or other substituents as defined in the outline of the invention) in Scheme 5. The thioaniline of formula Id is obtained by reacting the anilide of formula Ia with phosphorus pentasulfide or Lawesson's reagent in a suitable solvent such as pyridine at room temperature or by heating.

<chemistry num="20"><img file="JP4445751B2_D0020.tif" /></chemistry>

Benzoic acids of formula 4a (compounds of formula 4 (where J is the optionally substituted phenyl ring)) are well known in the art. The method for producing the specific acid of Formula 4 is described in Schemes 6-11. Various heterocyclic acids and general methods for synthesizing them are described in WO 98/57397.

The synthesis of a typical pyridine acid (4b) is shown in Scheme 6. This procedure involves the known synthesis of pyridine from β-ketoester and 4-aminobutenone (9). Substituent R³(c) and R³(d) includes, for example, alkyl, haloalkyl, and optionally substituted aromatic and aromatic heterocycles.

<chemistry num="21"><img file="JP4445751B2_D0021.tif" /></chemistry>

Scheme 7 shows the synthesis of a typical pyrimidine acid (4c). This procedure involves the known synthesis of pyrimidines from vinylidene-β-ketoester (12) and amidine. Substituent R³(c) and R³(d) includes, for example, alkyl, haloalkyl, and optionally substituted aromatic and aromatic heterocycles.

<chemistry num="22"><img file="JP4445751B2_D0022.tif" /></chemistry>

The synthesis of typical pyrazole acid (4d ~ 4h) is shown in Schemes 8-11. Pyrazole 4d is shown in Scheme 8. The synthesis of 4d in Scheme 8 is, as an important step, R by alkylation of pyrazole.³(c) Including introduction of substituents. Alkylating agent R³(c) -Lg (in the formula, Lg is a leaving group, eg, a sulfonate such as Cl, Br, I, p-toluenesulfonate or methanesulfonate, -SO.₂OR³(Sulfate such as (c)) is C₁~ C₆Alkyl, C₂~ C₆Alkenyl, C₂~ C₆Alkyne, C₃~ C₆Cycloalkyl, C₁~ C₆Haloalkyl, C₂~ C₆Haloalkenyl, C₂~ C₆Halo alkynyl, C₃~ C₆Halocycloalkyl, C₂~ C₆Alkylcarbonyl, C₂~ C₆Alkoxycarbonyl, C₃~ C₈Dialkylaminocarbonyl, C₃~ C₆R such as trialkylsilyl³(c) Group; or phenyl, benzyl, benzoyl, 5- or 6-membered aromatic heterocycle or aromatic 8-membered, 9- or 10-membered heterobicyclic aromatic condensed ring system (if each ring or ring system is used) Replaced by). Oxidation of the methyl group gives pyrazole carboxylic acid. More preferred R³(d) Some of the groups include haloalkyl and halogen.

<chemistry num="23"><img file="JP4445751B2_D0023.tif" /></chemistry>

The synthesis of pyrazole of formula 4e is illustrated in Scheme 9. These pyrazole acids can be produced by metalation and carboxylation of formula 18 as an important step. R³(c) The group is based on the same method as Scheme 8, that is, R.³(c) Introduced by alkylation with an alkylating agent. Typical R³The (d) group includes, for example, cyano and haloalkyl.

<chemistry num="24"><img file="JP4445751B2_D0024.tif" /></chemistry>

This procedure is particularly useful for producing the 1- (2-pyridinyl) pyrazole carboxylic acid of formula 4h, which is associated with the preferred moiety J-5 shown in Scheme 9a. The reaction of pyrazole of formula 17 with 2,3-dihalopyridine of formula 15a yields 1-pyridylpyrazole of formula 18a with good specificity for the desired position chemistry in good yield. Metalation of 18a with lithium diisopropylamide (LDA) followed by quenching of the lithium salt with carbon dioxide gives the 1- (2-pyridinyl) pyrazole carboxylic acid of formula 4h.

<chemistry num="25"><img file="JP4445751B2_D0025.tif" /></chemistry>

The method for producing pyrazole of formula 4f is shown in Scheme 10. These can be prepared by reacting the optionally substituted phenylhydrazine 19 with ketopyrbate 20 to give the pyrazole ester 21. Hydrolysis of the ester produces pyrazole acid 4f. This procedure is R³(c) is the optionally substituted phenyl, R³It is particularly useful for producing compounds in which (d) is haloalkyl.

<chemistry num="26"><img file="JP4445751B2_D0026.tif" /></chemistry>

The pyrazole acid of formula 4g is described in Scheme 11. These can be prepared by 3 + 2 cycloaddition of appropriately substituted nitrile imines of formula 22 with either substituted propiolate (23) or acrylate (26). Cycloaddition with acrylate requires the further oxidation of the intermediate pyrazoline to pyrazole. By hydrolyzing the ester, 4 g of pyrazole acid is obtained. Preferred imino halides for this reason include trifluoromethyliminochloride (28) and iminodibromide (29). Compounds such as 28 are known (J. Heterocycl. Chem. 1985, 22 (2), 565-8). Compounds such as 29 are available by known methods (Tetrahedron Letters, 1999, 40, 2605). These steps are described in the formula R³(c) is the optionally substituted phenyl, R³It is particularly useful for producing compounds in which (d) is a haloalkyl or halogen.

<chemistry num="27"><img file="JP4445751B2_D0027.tif" /></chemistry>

The production of a substituted 2-nitrophenyl oxazoline of formula 5a from 2-nitrobenzoic acid of formula 30 is outlined in Scheme 12.

<chemistry num="28"><img file="JP4445751B2_D0028.tif" /></chemistry>

Conversion of nitrobenzoic acid of formula 30 to the acid chloride of formula 31 involves treating 30 with a suitable acid chloride-producing reagent such as thionyl chloride, oxalyl chloride, or phosgene in a solvent such as toluene or dichloromethane. Can be achieved by. The nitrophenyl amide of formula 33 by treating the acid chloride of formula 31 with the substituted amino alcohol of formula 32 in a solvent such as tetrahydrofuran, dioxane or dichloromethane in the presence of a base such as a tertiary amine or pyridine. Is obtained. An intermediate of formula 5a is obtained by dehydrating the appropriate amide of formula 33 as is, with a dehydrating agent such as thionyl chloride, oxalyl chloride or phosphorus oxychloride, or in a solvent such as dichloromethane or toluene.

Scheme 13 outlines the production of a substituted 2-nitrophenyloxazole of formula 5b from 2-nitrobenzoyl chloride of formula 31. In the presence of a base, such as a tertiary amine, pyridine, in a solvent such as tetrahydrofuran, dioxane or dichloromethane, formula 34 (in formula, R).^2bSubstituted aldoamine (where is hydrogen) or formula 34 (in formula, R)^2bTreatment of the acid chloride of Substitution 31 with a ketoamine of (other than hydrogen) gives the nitrophenyl aldamide and ketoamide of formula 35. The intermediate of formula 5b is produced by dehydrating the aldamides and ketoamides of formula 35, either as is or in a solvent such as dichloromethane or toluene, with a dehydrating agent such as thionyl chloride, oxalyl chloride or phosphorus oxychloride. Toluene.

<chemistry num="29"><img file="JP4445751B2_D0029.tif" /></chemistry>

The production of a substituted 2-nitrophenyl oxadiazole of formula 5c from 2-nitrobenzoyl chloride of formula 31 is outlined in Scheme 14. In the presence of a base, such as a tertiary amine, pyridine, in a solvent such as tetrahydrofuran, dioxane or dichloromethane, formula 36 (in formula, R).^2bHydroxyform amidine (where is hydrogen) or formula 36 (in formula, R)^2bTreatment of the acid chloride of formula 31 with hydroxyacetamide of (other than hydrogen) gives an intermediate of formula 37, which is a suitable dehydrating agent, either as is or in a solvent such as dichloromethane or toluene. , Thionyl chloride, oxalyl chloride or phosphorus oxychloride to give an intermediate of formula 5c.

<chemistry num="30"><img file="JP4445751B2_D0030.tif" /></chemistry>

Substitution 2-nitrophenyl oxadiazole synthesis of formula 5d from 2-nitrobenzoyl chloride of formula 31 is outlined in Scheme 15. Treatment of the acid chloride of formula 31 with the hydrazide of formula 38 in a solvent such as tetrahydrofuran, dioxane or dichloromethane in the presence of a base such as tertiary amine, pyridine produces an intermediate of formula 39. And when it is dehydrated as it is or in a solvent such as dichloromethane or toluene with a suitable dehydrating agent, thionyl chloride, oxalyl chloride or phosphorus oxychloride, an intermediate of formula 5d is obtained.

<chemistry num="31"><img file="JP4445751B2_D0031.tif" /></chemistry>

The production of a substituted 2-nitrophenyl oxadiazole of formula 5e from 2-nitrobenzonitrile of formula 40 is outlined in Scheme 16. Treatment of the benzonitrile of formula 40 with hydroxylamine in a suitable solvent such as methanol, ethanol or acetonitrile gives the hydroxybenzamidine of formula 41. Formula (R) in a solvent such as tetrahydrofuran, dioxane or pyridine²CO)₂The reaction of 41 with the anhydride of O produces an intermediate of formula 5e.

<chemistry num="32"><img file="JP4445751B2_D0032.tif" /></chemistry>

The production of a substituted 2-nitrophenyl thiazole of formula 5f from 2-nitrobenzonitrile of formula 40 is outlined in Scheme 17. Treatment of benzonitrile of formula 40 with hydrogen sulfide in a solvent such as pyridine gives thiobenzamide of formula 42. The intermediate of formula 5f is produced by reacting 42 with α-haloaldehyde or α-haloketone of formula 43 in a solvent such as a lower alkyl alcohol with a solvent such as trialkylamine.

<chemistry num="33"><img file="JP4445751B2_D0033.tif" /></chemistry>

Scheme 18 outlines the production of a substituted 2-nitrophenyl thiadiazole of formula 5 g from 2-nitrobenzoyl chloride of formula 31. Treatment of the acid chloride of formula 31 with hydrazine in a solvent such as ethanol, tetrahydrofuran, dioxane or acetonitrile produces the hydrazine of formula 44, which is reacted with phosphorus pentasulfide or Lawesson's reagent in a solvent such as pyridine. Then, the thiohydrazide of the formula 45 is obtained. Formula (R) in a suitable solvent such as tetrahydrofuran, dioxane, acetonitrile or pyridine²CO)₂Reaction of 45 with the anhydride of O produces an intermediate of formula 5g.

<chemistry num="34"><img file="JP4445751B2_D0034.tif" /></chemistry>

Scheme 19 outlines the production of substituted 2-nitrophenyltriazoles of formulas 5h and 5i from 2-nitrobenzoyl chloride of formula 31.

<chemistry num="35"><img file="JP4445751B2_D0035.tif" /></chemistry>

Treatment of the acid chloride of formula 31 with ammonia in a solvent such as ethanol, tetrahydrofuran, dioxane or diethyl ether gives the benzamide of formula 46. Expression (MeO)₂CR^2aNMe₂N, N-Dimethylformamide dimethylacetal or dimethylamide dimethylacetal of formula 46 benzamide as is or heated with a solvent such as toluene gives an intermediate of formula 47. Formula R in a suitable solvent such as lower alkyl alcohol or acetonitrile^2bNHNH₂By reacting hydrazine with 47, equations 5h and 5i are obtained.

Scheme 20 shows the production of substituted 2-nitrophenyltetrazole of formulas 5j, 5k and 5l from 2-nitrobenzonitrile of formula 40. Treatment of the benzonitrile of formula 40 with sodium azide in N, N-dimethylformamide or acetonitrile gives the tetrazole of formula 5j. In the presence of a suitable base such as potassium carbonate, in a solvent such as N, N-dimethylformamide, formula R²Lg (in the formula, R²Alkylation of formula 5j with an alkylating agent (where is unsubstituted or substituted alkyl or haloalkyl and Lg is a leaving group such as halogen or tosylate) yields intermediates of formulas 5k and 5l.

<chemistry num="36"><img file="JP4445751B2_D0036.tif" /></chemistry>

Scheme 21 shows a method for producing 2-nitrophenyl imidazoline of the formulas 5m, 5n and 5o. Heating methyl 2-nitrobenzoate of formula 49 with substituted 1,2-diaminoethane of formula 50 at a temperature of 100-250 ° C, either as is or in a suitable solvent such as toluene, xylene or dichlorobenzene, 2-Nitrophenylimidazoline of formula 5 m is obtained. Formula R in a solvent such as tetrahydrofuran, dioxane or N, N-dimethylformamide in the presence of a suitable base such as potassium carbonate or sodium hydride.^2eAlkylation of 5 m with an alkylating agent of Lg (where Lg is a leaving group such as halogen or tosylate) produces intermediates of formulas 5n and 5o.

<chemistry num="37"><img file="JP4445751B2_D0037.tif" /></chemistry>

Scheme 22 outlines methods for producing 2-nitrophenylimidazoles of formulas 5p, 5q and 5r.

<chemistry num="38"><img file="JP4445751B2_D0038.tif" /></chemistry>

In a solvent such as dichloromethane or N, N-dimethylformamide, formula 5 m (in formula, R)^2cAnd R^2dOxidation of nitrophenyl imidazoline (both hydrogen) with a suitable oxidizing agent such as manganese dioxide or pyridinium dichromate gives nitrophenyl imidazole of formula 5p. In the presence of a suitable base such as potassium carbonate or sodium hydride, in a solvent such as tetrahydrofuran, dioxane or N, N-dimethylformamide, formula R^2eAlkylation of 5p with an alkylating agent of Lg (where Lg is a leaving group such as halogen or tosylate) gives intermediates of formulas 5q and 5r.

Scheme 23 shows a method for producing 2-nitrophenyltetrahydropyrimidines of formulas 5s, 5t and 5u. When heated as-is or in a suitable solvent such as toluene, xylene or dichlorobenzene at a temperature of 100-250 ° C, methyl 2-nitrobenzoate of formula 49 with the substituted 1,3-diaminopropane, the formula 5s of nitrophenyltetrahydropyrimidine is obtained. In the presence of a suitable base such as potassium carbonate or sodium hydride, in a solvent such as tetrahydrofuran, dioxane or N, N-dimethylformamide, formula R^2gBy alkylating 5s with an alkylating agent of Lg (where Lg is a leaving group such as halogen or tosylate), intermediates of formulas 5t and 5u are obtained.

<chemistry num="39"><img file="JP4445751B2_D0039.tif" /></chemistry>

The synthesis of 2-nitrophenylpyrimidine of formula 5v is shown in Scheme 24. Reacting gaseous HCl with nitrobenzonitrile of formula 40 in methanol with or without a co-solvent such as diethyl ether or tetrahydrofuran gives the imidated hydrochloride of formula 52. Treatment of the imitation of formula 52 with ammonium chloride in methanol gives the nitrobenzamidine hydrochloride of formula 53. The compound of formula 53 can be condensed with the aldoketone or diketone of formula 54 in the presence of a base such as sodium methylated or potassium carbonate in a suitable solvent, preferably a lower alkyl alcohol, to give an intermediate of formula 5v. ..

<chemistry num="40"><img file="JP4445751B2_D0040.tif" /></chemistry>

The synthesis of 2-nitrophenyltriazine of formula 5w is shown in Scheme 25. By condensing the nitrobenzamidine hydrochloride of formula 53 with the acylimide of formula 55 in the presence of a base, such as sodium methylated or potassium carbonate, in a suitable solvent, preferably a lower alcohol, of formula 5w. An intermediate is obtained.

<chemistry num="41"><img file="JP4445751B2_D0041.tif" /></chemistry>

The production of 2-nitrophenyltetrahydropyrimidinone of formula 5x is outlined in Scheme 26. In the presence of a base, such as sodium methylated or potassium carbonate, in a suitable solvent, preferably a lower alcohol, by condensing the nitrophenyl imidazole of formula 52 with the substituted β-alanine ester of formula 56, the formula 5x Intermediate is obtained.

<chemistry num="42"><img file="JP4445751B2_D0042.tif" /></chemistry>

The production of the nitrophenyl-substituted azole of formula 5y is shown in Scheme 27. In the presence of a suitable base such as potassium carbonate or sodium hydride, in a solvent such as N, N-dimethyl-formamide, acetonitrile or dioxane, formula 57 (Hal is halogen, preferably fluorine in the formula). Substitution of 2-halonitrobenzene is reacted with the azole of formula 58 to give an intermediate of formula 5y.

<chemistry num="43"><img file="JP4445751B2_D0043.tif" /></chemistry>

Equation 17 (in equation, R³(d) is CF₃, Cl or Br) is a known compound. Pyrazole 17 (R³(d) is CF₃Can be produced according to the procedures in the literature (J. Fluorine Chem. 1991, 53 (1), 61-70). Equation 17 (in equation, R³Pyrazole (where (d) is Cl or Br) can also be produced according to the procedures in the literature (H. Reimlinger and A. Van Overstraeten, Chem. Ber. 1966, 99 (10), 3350-7). Equation 17 (in equation, R³Scheme 28 shows a useful alternative method for producing pyrazoles (where (d) is Cl or Br). Metalate sulfamoylpyrazole of formula 58 with n-butyllithium, followed by its anion with hexachloroethane (R).³(d) is Cl) or 1,2-dibromotetrachloroethane (R)³The halogenated derivative 59 is obtained by direct halogenation with any of ((d) is Br). Trifluoroacetic acid (TFA) is used to cleanly remove sulfamoyl groups, thereby giving good yields in formula 17b (in formula, R).³(D) is Cl or Br, respectively) to obtain pyrazole. Those skilled in the art will appreciate that formula 17c is a tautomer of formula 17b.

<chemistry num="44"><img file="JP4445751B2_D0044.tif" /></chemistry>

The typical pyrazole acid synthesis of formula 4i is shown in Scheme 29. The pyrazole of formula 63 is obtained by reacting the dimethylaminoiridenketoester of formula 61 with the substituted hydrazine (62). Preferred R³Examples of the (d) substituent include alkyl and haloalkyl, with 2,2,2-trifluoroethyl being particularly preferred. The ester of formula 63 is converted to the acid of formula 4i by standard hydrolysis.

<chemistry num="45"><img file="JP4445751B2_D0045.tif" /></chemistry>

Preferred part J-6 (R³Is the substituted 2-pyridyl moiety that binds to the 5-position of the pyrazole ring), and the synthesis of pyrazole acid of formula 4j is shown in Scheme 30. This synthesis is performed according to the general synthesis described for Scheme 29.

<chemistry num="46"><img file="JP4445751B2_D0046.tif" /></chemistry>

Scheme 31 shows the synthesis of a representative pyrazole acid of formula 4k and the alternative synthesis of formula 4i.

<chemistry num="47"><img file="JP4445751B2_D0047.tif" /></chemistry>

Pyrazole of formula 66 is obtained by reacting the dimethylaminoylideneketoester of formula 61 with hydrazine. Reaction of pyrazole 66 with an alkylating agent of formula 15 (see Scheme 8) gives a mixture of pyrazoles of formulas 67 and 65. This mixture of pyrazole isomers is readily separated by chromatography and converted to the corresponding acids 4k and 4i, respectively. Preferred R³(d) Substituents include alkyl and haloalkyl groups.

Preferred part J-7 (in the formula, R³Scheme 32 shows the synthesis of pyridinylpyrazolic acid of formula 4m, as well as the alternative synthesis of formula 4j, which is associated with the substitution 2-pyridinyl and binds to the 3-position of the pyrazole ring). This synthesis is performed according to the general synthesis described for Scheme 31.

<chemistry num="48"><img file="JP4445751B2_D0048.tif" /></chemistry>

The general synthesis of pyrrole acid of formula 22 is shown in Scheme 33. Treatment of the compound of formula 71 with 2,5-dimethoxytetrahydrofuran (72) gives pyrrole of formula 73. Formylation of pyrrole 73 to obtain the aldehyde of formula 74 was achieved using Vilsmeier-Haack formylation standard conditions, including treatment with N, N-dimethylformamide (DMF) and phosphorus oxychloride. can do. Halogenation of compounds of formula 74 with N-halosuccinimide (NXS), such as N-chlorosuccinimide or N-bromosuccinimide, occurs preferentially at the 4-position of the pyrrole ring. Oxidation of the halogenated aldehyde gives the pyrrole acid of formula 4n. The oxidation can be achieved using various standard oxidation conditions.

<chemistry num="49"><img file="JP4445751B2_D0049.tif" /></chemistry>

Preferred part J-4 (in the formula, R⁵The synthesis of a particular pyridinylpyrolic acid of formula 4o is shown in Scheme 34, which is associated with the substitution 2-pyridinyl and binds to the nitrogen of the pyrrole ring). This synthesis is performed according to the general synthesis described for Scheme 33. The compound of formula 71a, 3-chloro-2-aminopyridine, is a known compound (see J. Heterocycl. Chem. 1987, 24 (5), 1313-16).

<chemistry num="50"><img file="JP4445751B2_D0050.tif" /></chemistry>

The synthesis of pyrrole acid of formula 4p is shown in Scheme 35. Cycloaddition of allen of formula 80 with the phenylsulfonyl hydrazide of formula 79 (see Pavri, NP; Trudell, MLJ Org. Chem. 1997, 62, 2649-2651) gives pyrroline of formula 81. Treatment of pyrroline of formula 81 with tetrabutylammonium fluoride (TBAF) gives pyrrole of formula 82. Pyrrole 82 alkylating agent R³(d) -Lg (in the formula, Lg is a leaving group defined above) is reacted and hydrolyzed to obtain the pyrrole acid of the formula 4p.

<chemistry num="51"><img file="JP4445751B2_D0051.tif" /></chemistry>

Preferred part J-5 (in the formula, R⁵Is phenyl or 2-pyridyl and binds to the 2-position of the pyrrole ring), the synthesis of pyrrole acid of formula 4q is shown in Scheme 36. The synthesis is carried out according to the general method described for Scheme 35.

<chemistry num="52"><img file="JP4445751B2_D0052.tif" /></chemistry>

The synthesis of pyrrole acid of formula 4r is shown in formula 37. The reaction of the α, β-unsaturated ester of formula 88 with p-tolylsulfonylmethyl isocyanide (TosMIC) gives the pyrrole of formula 90. See Xu, Z. et al., J. Org. Chem., 1988, 63, 5031-5041 for key references. Alkylating agent R for pyrrole of formula 90³Reaction with (d) -Lg (Lg is the leaving group defined above) followed by hydrolysis gives the pyrrole acid of formula 4r.

<chemistry num="53"><img file="JP4445751B2_D0053.tif" /></chemistry>

Preferred part J-10 (in the formula, R⁵Is a substituted phenyl or substituted 2-pyridinyl ring), the synthesis of pyrrole acid of formula 4s is shown in Scheme 38. The synthesis is carried out according to the general method described for Scheme 37.

<chemistry num="54"><img file="JP4445751B2_D0054.tif" /></chemistry>

The synthesis of a specific pyrazole amide analog of formula Ie is shown in Scheme 39.

<chemistry num="55"><img file="JP4445751B2_D0055.tif" /></chemistry>

This procedure utilizes the lithiotized derivative of formula 93. Treatment of the compound of formula 93 with lithium diisopropylamide (LDA) followed by quenching of the lithium salt with arylisocyanate of formula 94 gives a compound of formula Ic, a subset of the compound of formula I. Aryl isocyanates can be prepared from compounds of formula 2a (see Scheme 3) by treatment with phosgenes or phosgene equivalents, for example diphosgene or triphosgene. The main references for producing isocyanates are "March, Advanced Organic Chemistry: Reactions, Mechanisms and Structure, Third Edition", John Wiley &amp; See Sons, New York, 1985; p.370.

Equation 4t (in equation, R³Is CF₃The pyrazole carboxylic acid (is) can be prepared by the method outlined in Scheme 8.

<chemistry num="56"><img file="JP4445751B2_D0056.tif" /></chemistry>

Equation 95 (in equation, R⁸Is C₁~ C₄By reacting the compound (which is alkyl) with the appropriate base in the appropriate organic solvent, the cyclization product of formula 96 is obtained after neutralization with an acid such as acetic acid. Suitable salts include, but are not limited to, sodium hydride, potassium t-butoxide, sodium gymsyl (CH).₃S (O) CH₂^-Na⁺), Alkali metals (such as lithium, sodium or potassium) carbonates or hydroxides, tetraalkyls (such as methyl, ethyl or butyl) ammonium fluorides or hydroxides, or 2-t-butylimino-2-diethylamino-1 , 3-Dimethyl-perhydro-1,3,2-diazaphosphonin. Suitable organic solvents include, but are not limited to, for example, acetone, acetonitrile, tetrahydrofuran, dichloromethane, dimethyl sulfoxide, or N, N-dimethylformamide. The cyclization reaction is usually carried out in the temperature range of about 0 to 120 ° C. The effects of solvent, base temperature and addition time are all dependent on each other and the choice of reaction conditions is important to minimize the formation of by-products. A preferred base is tetrabutylammonium fluoride.

The compound of formula 96 is dehydrated to obtain the compound of formula 97, and the carboxylic acid ester functional group thereof is subsequently converted to a carboxylic acid to obtain the compound of formula 4t. The dehydration is carried out by treating with a catalytic amount of an appropriate acid. The acid that exerts this catalytic action includes, but is not limited to, sulfuric acid. The reaction is generally carried out using an organic solvent. As will be appreciated by those skilled in the art, the dehydration reaction is carried out in a wide variety of solvents over a temperature range of about 0 to 200 ° C, more preferably about 0 to 100 ° C. For dehydration in the scheme 40 method, a solvent comprising acetic acid and a temperature of about 65 ° C. are preferred. Carboxylate ester compounds can be converted to carboxylic acid compounds by a number of methods involving nucleophilic cleavage under anhydrous conditions and hydrolysis methods involving the use of acids or bases (for an overview of the methods, TWGreene and PGM Nuts). , Protective Groups in Organic Synthesis, 2nd ed., John Wiley &amp; Sons, Inc., New See York, 1991, pp.224-269). As for the method of Scheme 40, the base-catalyzed hydrolysis method is preferable. Suitable bases include alkali metal (such as lithium, sodium or potassium) hydroxides. For example, the ester can be dissolved in a mixture of water and an alcohol such as ethanol. Treatment with sodium hydroxide or potassium hydroxide will saponify the ester to give the sodium or potassium salt of the carboxylic acid. By acidifying with a strong acid such as hydrochloride or sulfuric acid, a carboxylic acid of formula 4t can be obtained. The carboxylic acid can be isolated by methods known to those of skill in the art, including crystallization, extraction and distillation.

The compound of formula 95 can be prepared by the method outlined in Scheme 41.

<chemistry num="57"><img file="JP4445751B2_D0057.tif" /></chemistry>

Treatment of the hydrazine compound of formula 98 with the ketone of formula 99 in a solvent such as water, methanol or acetic acid gives the hydrazone of formula 100. Those skilled in the art will appreciate that this reaction may require catalysis with any acid and may also require high temperatures depending on the molecular substitution pattern of the hydrazone of formula 100. By reacting a hydrazone of formula 100 with a compound of formula 101 in the presence of an acid scavenger such as triethylamine in a suitable solvent such as, but not limited to, dichloromethane or tetrohydrofuran, the compound of formula 95 can be obtained. can get. The reaction is usually carried out at a temperature of about 0-100 ° C. The hydrazine compound of formula 98 can be prepared by standard methods, for example by treating the corresponding halo compound of formula 15a (Scheme 9a) with hydrazine.

Equation 4u (in equation, R³The pyrazole carboxylic acid (which is Cl or Br) can be prepared by the method outlined in Scheme 42.

<chemistry num="58"><img file="JP4445751B2_D0058.tif" /></chemistry>

The compound of formula 4u is obtained by optionally oxidizing the compound of formula 102 in the presence of an acid to produce the compound of formula 103, followed by the conversion of the carboxylic acid ester functional group to a carboxylic acid. Examples of the oxidizing agent include hydrogen peroxide, organic peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, potassium monosulfate (for example, Oxone®) or potassium permanganate. .. For complete conversion, at least 1 equivalent of oxidant should be used for the compound of formula 102, preferably about 1-2 equivalents. This oxidation is usually carried out in the presence of a solvent. Examples of the solvent include ethers such as tetrahydrofuran and p-dioxane, organic esters such as ethyl acetate and dimethyl carbonate, and polar aprotic solvents such as N, N-dimethylformamide and acetonitrile. Examples of acids suitable for use in the oxidation step include inorganic acids such as sulfuric acid and phosphoric acid, and organic acids such as acetic acid and benzoic acid. When used, the acid should be used in an amount greater than 0.1 equivalent relative to the compound of formula 102. 1-5 equivalents of acid can be used for complete conversion. A preferred oxidizing agent is potassium persulfate, and its oxidation is preferably carried out in the presence of sulfuric acid. The reaction can be carried out by mixing the compound of formula 102 in the desired solvent and, if used, an acid. The oxidizing agent can then be added in an appropriate proportion. The reaction temperature usually varies from as low as about 0 ° C to the boiling point of the solvent to obtain a reasonable reaction time to complete the reaction, preferably less than 8 hours. The desired product, the compound of formula 103, can be isolated by methods known to those of skill in the art, including crystallization, extraction and distillation. A suitable method for converting an ester of formula 103 to a carboxylic acid of formula 4u has already been described in Scheme 40.

The compound of formula 102 can be prepared from the corresponding compound of formula 104 represented by Scheme 43.

<chemistry num="59"><img file="JP4445751B2_D0059.tif" /></chemistry>

Treatment of the compound of formula 104 with a halogenating agent, usually in the presence of a solvent, gives the corresponding halo compound of formula 102. Examples of the halogenating agent that can be used include phosphorus oxyhalide, phosphorus trihalogenate, phosphorus pentahalogenate, thionyl chloride, dihalotrialkylphosphoran, dihalodiphenylphosphoran, oxalyl chloride and phosgene. Phosphorus oxyhalides and phosphorus pentahalides are preferred. For complete conversion, at least 0.33 equivalents of phosphorus oxyhalide should be used for the compound of formula 104, preferably about 0.33 to 1.2 equivalents. For complete conversion, at least 0.20 equivalents of phosphorus pentahalide should be used for the compound of formula 104, preferably about 0.20 to 1.0 equivalents. Equation 104 (in equation, R⁶Is C₁~ C₄(Alkyl) compounds are preferred for this reaction. Common solvents used for this halogenation include halogenated alkanes such as dichloromethane, chloroform and chlorobutane, aromatic solvents such as benzene, xylene and chlorobenzene, ethers such as tetrahydrofuran, p-dioxane and diethyl ether, and acetonitrile. Polar aprotic solvents such as N, N-dimethylformamide can be mentioned. In some cases, organic bases such as triethylamine, pyridine, N, N-dimethylaniline and the like may be added. The addition of catalysts such as N, N-dimethylformamide, etc. is also optional. A process in which the solvent is acetonitrile and the absence of a base is preferable. Generally, no base or catalyst is required when using an acetonitrile solvent. The preferred process is carried out by mixing the compounds of formula 104 in acetonitrile. The halogenating agent is then added over an appropriate period of time and then the mixture is maintained at the desired temperature until the reaction is complete. The reaction temperature is usually from 20 ° C to the boiling point of acetonitrile and the reaction time is usually less than 2 hours. The reaction is then neutralized with an inorganic base such as sodium bicarbonate, sodium hydroxide, or an organic base such as sodium acetate. The desired product, the compound of formula 102, can be isolated by methods known to those of skill in the art, including crystallization, extraction and distillation.

Alternatively, Equation 102 (in Equation, R³Compounds of formula 102 (in formula, R)³Halogen with different (eg, equation 102 (R)³Is Br), it can be produced by treating the corresponding compound of Cl) or a sulfonate group such as p-toluenesulfonate) with hydrogen bromide or hydrogen chloride, respectively. By this method, the starting compound R of formula 102³Halogen or sulfonate substituents are substituted with Br or Cl from hydrogen bromide or hydrogen chloride, respectively. The reaction is carried out in a suitable solvent such as dibromomethane, dichloromethane or acetonitrile. This reaction can be carried out at or near atmospheric pressure in a pressure vessel or at pressures above atmospheric pressure. R in the starting compound of formula 102³However, if it is a halogen such as Cl, it is preferable to carry out the reaction so that the hydrogen halide generated from the reaction is removed by sparging or other suitable means. This reaction can be carried out at a temperature of about 0-100 ° C, most preferably near ambient temperature (eg, about 10-40 ° C), more preferably 20-30 ° C. Lewis acid catalyst (Equation 102 (R)³Is Br), the reaction can be accelerated by adding aluminum bromide, etc.). The product of formula 102 is isolated by conventional methods known to those of skill in the art, including extraction, distillation and crystallization.

Equation 102 (in equation, R³The starting compound of (is Cl or Br) can be prepared from the corresponding compound of formula 104 already shown. Equation 102 (in equation, R³Similarly, the starting compound of (which is a sulfonate group) is also treated with a base such as sulfonyl chloride (eg, p-toluenesulfonyl chloride) and tertiary amine (eg, triethylamine) in a suitable solvent such as dichloromethane. It can be prepared from the corresponding compound of formula 104 by the standard method of.

Equation 4v (in equation, R³Is OCH₂CF₃The pyrazole carboxylic acid (is) can be prepared by the method outlined in Scheme 44.

<chemistry num="60"><img file="JP4445751B2_D0060.tif" /></chemistry>

In this method, instead of halogenating as shown in Scheme 43, the compound of formula 104 is oxidized to the compound of formula 105. The reaction conditions for this oxidation have already been described for the conversion of compounds of formula 102 to compounds of formula 103 in Scheme 42.

Then, in the presence of the base, the alkylating agent CF₃CH₂Contact with Lg (106) alkylates the compound of formula 105 to form the compound of formula 107. In the alkylating agent 106, Lg is halogen (eg Br, I), OS (O).₂CH₃(Methane sulfonate), OS (O)₂CF₃, OS (O)₂Ph-p-CH₃It is a nucleophilic reaction leaving group such as (p-toluenesulfonate); methanesulfonate works well. The reaction is carried out in the presence of at least 1 equivalent of base. Suitable bases include inorganic bases such as alkali metal (eg, lithium, sodium or potassium) carbonates and hydroxides, and triethylamine, diisopropylethylamine and 1,8-diazabicyclo [5.4.0] undec-7-ene. Organic bases can be mentioned. The reaction is generally alcoholic such as methanol and ethanol, alkane halides such as dichloromethane, aromatic solvents such as benzene, toluene and chlorobenzene, ethers such as tetrahydrofuran, and polar aprotic such as acetonitrile, N, N-dimethylformamide. It is carried out in a solvent which may contain a solvent or the like. Alcohols and polar aprotic solvents are preferred for use with inorganic bases. Potassium carbonate is preferred as the base and acetonitrile is preferred as the solvent. The reaction is generally carried out at about 0 to 150 ° C, most commonly at ambient temperature to 100 ° C. The product of formula 107 can be isolated by prior art techniques such as extraction. The ester of formula 107 can then be converted to the carboxylic acid of formula 4v by the method already described for the conversion of formula 97 to formula 4t in Scheme 40.

The compound of formula 104 can be prepared from the compound of formula 98 outlined in Scheme 45.

<chemistry num="61"><img file="JP4445751B2_D0061.tif" /></chemistry>

In this method, the hydrazine compound of formula 98 is contacted with the compound of formula 108 (fumaric acid ester or maleic acid ester or a mixture thereof can be used) in the presence of bases and solvents. The base is usually a metal alkoxide salt such as sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, potassium t-butoxide, lithium t-butoxide and the like. More than 0.5 equivalents of base should be used for the compound of formula 108, preferably 0.9 to 1.3 equivalents. Compounds of formula 108 greater than 1.0 equivalent should be used, preferably 1.0 to 1.3 equivalents. Polar protic and polar aprotic brave solvents such as alcohol, acetonitrile, tetrahydrofuran, N, N-dimethylformamide, dimethyl sulfoxide can be used. Preferred solvents are alcohols such as methanol and ethanol. It is particularly preferred that the alcohol be the same as that constituting the fumaric acid ester or maleic acid ester and the alkoxide base. The reaction is usually carried out by mixing the compound of formula 108 with a base in a solvent. The mixture is heated or cooled to the desired temperature and the compound of formula 108 is added over a period of time. Normally, the reaction temperature is 0 ° C to the boiling point of the solvent used. The reaction is carried out under pressure above atmospheric pressure to raise the boiling point of the solvent. A temperature of about 30-90 ° C is generally preferred. The addition time is as fast as heat transfer allows. The usual addition time is 1 minute to 2 hours. The optimum temperature and addition time will vary depending on the individuality of the compounds of formulas 98 and 108. After the addition, the reaction mixture is kept at the reaction temperature for a period of time. Depending on the reaction temperature, the retention time required is 0-2 hours. The normal holding time is 10 to 60 minutes. The reaction is then acidified by adding an organic acid such as acetic acid or an inorganic acid such as hydrochloric acid or sulfuric acid. -CO of the compound of formula 104, depending on the reaction conditions and the means of isolation₂R⁸Functional group is -CO₂Hydrolyzed to H; for example, the presence of water in the reaction mixture facilitates such hydrolysis. Carboxylic acid (-CO₂Once H) is formed, it is converted to -CO using an esterification method known in the art.₂R⁸(In the formula, R⁸Is C₁~ C₄(Alkyl) is converted back. The desired product, the compound of formula 104, is isolated by methods known to those of skill in the art, such as crystallization, extraction or distillation.

It should be understood that some of the reagents and reaction conditions described above for making compounds of formula I may not be compatible with the particular functional groups present in the intermediate. In these cases, incorporating a protected / deprotected sequence or interconversion of functional groups into the synthesis will help to obtain the desired product. The use and selection of protecting groups will be apparent to those skilled in the art in chemical synthesis (see, eg, Greene, TW; Wuts, PGM Protective Groups in Organic Synthesis, 2nd ed .; Wiley: New York, 1991). One of ordinary skill in the art, in some cases, after introducing the prescribed reagents as shown in the individual schemes, to complete the synthesis of the compounds of formula I, other routines not described in detail. It will be understood that it is necessary to carry out a synthetic step. Those skilled in the art may need to perform the combination of steps shown in the above scheme in an order other than that implied by the particular order shown to produce the compounds of formula I. It will also be understood that there is.

If you are a skilled person, will the compounds of formula I and the intermediates described herein be subjected to various electrophilic, nucleophilic, radical, organic metal, oxidation and reduction reactions to add substituents? It will also be appreciated that, or existing substituents can be modified.

Without further detail, it is believed that one of ordinary skill in the art can make full use of the present invention using the above description. Therefore, the following examples should be construed as merely exemplary and by no means limiting the specification. Percentages are by weight, except in the case of chromatographic solvent mixtures or unless otherwise specified. Chromatograph solvent mixture parts and percentages are by volume unless otherwise specified.¹The H NMR spectrum is shown in ppm low magnetic field from tetramethylsilane; s is singlet, d is doublet, t is triplet, q is quadruple, and m is multiple. The term, dd is the doublet of the doublet, dt is the doublet of the triplet, and br s is the broad singlet.

Example 1 N- [4-Bromo-2- (4,5-dihydro-1H-imidazol-2-yl) -6-methylphenyl] -1- (3-chloro-2-pyridinyl) -3- (trifluoromethyl) Production of -1H-pyrazole-5-carboxamide Step A: Production of 4,5-dihydro-2- (3-methyl-2-nitrophenyl) -1H-imidazole A solution of 3.13 g (16.1 mmol) of methyl 3-methyl-2-nitrobenzoate in ethylenediamine (15 mL) was heated to reflux for 1.5 hours, at which point the solvent was removed under reduced pressure at 130 ° C. The residue is then heated at 190 ° C. for 1.25 hours and purified by flash column chromatography (silica gel, 1% to 10% methanol in dichloromethane) prior to cooling with ice to give the title compound of step A (0.35 g). Was obtained as brown oil.¹1 H NMR (CDCl₃) δ 7.52 (m, 1H), 7.39 (t, 1H), 7.35 (m, 1H), 3.74 (s, 4H), 2.33 (s, 3H).

Step B: 2- (4,5-dihydro-1H-imidazol-2-yl) -6-methylbenzeneamine Palladium hydroxide ((50 mg, 20 wt% on carbon). To a solution of the title compound (0.5 g, 2.44 mmol) of step A in ethanol (50 mL). Exhaust the flask twice, flush with nitrogen, then Exhausted twice and flushed with hydrogen. Prior to exhausting, the mixture was vigorously agitated under a hydrogen balloon for 3 hours, exposed to air and filtered through a Celite® pad. The solution was concentrated, filtered through a pad of silica gel and eluted with 5% methanol in dichloromethane, then 10% methanol, then 5% triethylamine, 10% methanol, 85% dichloromethane. Elution in triethylamine / methanol / dichloromethane. The substance was concentrated to give the title compound of step B (0.38 g) as a light brown oil.¹1 H NMR (CDCl₃) δ 7.3-7.2 (d, 1H), 7.1 (d, 1H), 6.57 (t, 1H), 3.76 (s, 4H), 2.18 (s, 3H).

Step C: Preparation of 4-bromo-2- (4,5-dihydro-1H-imidazol-2-yl) -6-methylbenzeneamine To a solution of the title compound (0.38 g, 2.17 mmol) of step B in N, N-dimethylformamide (10 mL) was added N-bromosuccinimide (0.38 g, 2.13 mmol) and the mixture was allowed to cool at ambient temperature for 1 hour. Stirred. Further N-Bromosuccinimide (0.06 g, 0.34 mmol) was added and the mixture was stirred for an additional 0.5 hours before diluting with ethyl acetate and washed 3 times with water. The combined aqueous fraction was extracted with ethyl acetate and the organic phase was washed with water. The combined organic fractions were dried (magnesium sulphate), concentrated and purified by flash column chromatography (silica gel, 2% in dichloromethane, then 5% methanol) to give the title compound of step C (94 mg) as a light brown oil. Got¹1 H NMR (CDCl₃) δ 7.33 (d, 1H), 7.18 (d, 1H), 3.76 (s, 4H), 2.15 (s, 3H).

Step D: N- [4-Bromo-2- (4,5-dihydro-1H-imidazol-2-yl) -6-methylphenyl] -1- (3-chloro-2-pyridinyl) -3- (tri) Production of Fluoromethyl) -1H-Pyrazole-5-Carboxamide Of 1- (3-chloro-2-pyridinyl) -3- (trifluoromethyl) -1H-pyrazol-5-carboxylic acid (119 mg, 0.41 mol) in dichloromethane (10 mL) containing dimethylformamide (1 drop) Oxalyl chloride (390 μL, 0.48 mmol) was added to the solution. The mixture was stirred at ambient temperature for 2 hours before concentrating under reduced pressure. The mixture is dissolved in dichloromethane (5 mL) and the title compound of step C (94 mg, 0.37 mmol) in dichloromethane (5 mL), dimethylaminopyridine (weighed as the amount covering the tip of a small experimental spatula) and triethylamine (77 μL). , 0.56 mmol) was added to the solution. The mixture was stirred at ambient temperature overnight before adding a saturated solution of sodium bicarbonate. Filter through a column of Celite® filtration aids, concentrate and flash column chromatography (silica gel, 5% in chloroform, then 20% acetone, then 1% in dichloromethane, then 2%, then 5%. Purification with methanol) gave the title compound of Example 1, the compound of the present invention, as a white solid (22 mg).¹1 H NMR (CDCl₃) δ 8.5 (dd, 1H), 7.9 (dd, 1H), 7.5 (dd, 1H), 7.4 (m, 2H), 7.30 (s, 1H), 3.79 (s, 4H), 2.20 (s, 3H) ..

Example 2 Production of 1- (3-chloro-2-pyridinyl) -N- [2-1H-imidazol-2-yl) -6-methylphenyl] -3- (trifluoromethyl) -1H-pyrazol-5-carboxamide Step A: Preparation of 2- (3-methyl-2-nitrophenyl) -1H-imidazole To a solution of the title compound of Example 1 in dimethylformamide (20 mL), step A (0.35 g, 1.71 mmol), active manganese dioxide (4.46 g, 51.3 mmol) was added and the mixture was mixed at 120 ° C. for 2 hours. It was heated. After cooling, the mixture was diluted with ethyl acetate, filtered through a pad of Celite®, washed 3 times with water and once with a saturated solution of sodium chloride. The organic phase is dried (magnesium sulphate), concentrated and purified by flash column chromatography (silica gel, 60% in hexanes, then 80% ethyl ether, then ethyl ether) to give the title compound of step A (0.1 g). Obtained as a white solid.¹1 H NMR (CDCl₃) δ 7.76 (d, 1H), 7.46 (t, 1H), 7.33 (d, 1H), 7.3-7.1 (2 x bs, 2H), 2.37 (s, 3H).

Step B: Preparation of 2- (1H-imidazol-2-yl) -6-methylbenzeneamine Palladium hydroxide (20 wt% on carbon) (measured to cover the tip of a small experimental spatula) is added to a solution of the title compound (0.1 g, 0.49 mmol) of step A in ethanol (20 mL). did. The flask was evacuated twice, flushed with nitrogen, then evacuated twice and flushed with hydrogen. Prior to exhaust, the mixture was vigorously agitated under a hydrogen balloon for 0.45 hours, exposed to air and filtered through a Celite® pad. Concentration gave the title compound of step B as an off-white solid (82 mg).¹1 H NMR (CDCl₃) δ 7.3-7.2 (m, 2H), 7.1 (m, 2H), 6.67 (t, 1H), 6.0 (bs), 2.23 (s, 3H).

Step C: 1- (3-chloro-2-pyridinyl) -N- [2-1H-imidazol-2-yl) -6-methylphenyl] -3- (trifluoromethyl) -1H-pyrazol-5-carboxamide Manufacturing of Of 1- (3-chloro-2-pyridinyl) -3- (trifluoromethyl) -1H-pyrazol-5-carboxylic acid (165 mg, 0.57 mmol) in dichloromethane (5 mL) containing dimethylformamide (1 drop) Oxalyl chloride (54 μL, 0.61 mmol) was obtained in the solution. The mixture was stirred at ambient temperature for 2 hours before concentration under reduced pressure and dissolved in dichloromethane (5 mL). Diisopropylethylamine (127 μL, 0.71 mmol) was added, followed by the title compound of step B (82 mg, 0.47 mmol) and the mixture was stirred at ambient temperature for 4 hours. Dimethylaminopyridine (weighed as an amount covering the tip of a small experimental spatula) was then added and the mixture was stirred at ambient temperature overnight. A saturated solution of sodium bicarbonate was then added and the mixture was filtered through a column of Celite®. The title compound of Example 2, the compound of the present invention, was subjected to a melting point of 224 to 226 ° C by concentration and purification by flash column chromatography (silica gel, 60% in hexane, then 80% ethyl ether, then ethyl ether). Obtained as a white solid (0.12 g).

Example 3 Step A: N- [2- (4-Bromo-1H-imidazol-2-yl) -6-methylphenyl] -1- (3-chloro-2-pyridinyl) -3- (trifluoromethyl) -1H- Production of pyrazole-5-carboxamide N-Bromosuccinimide (16 mg, 0.09 mmol) was added to a solution of the title compound (0.04 g, 0.09 mmol) of Example 2 in dichloromethane (3 mL) and the mixture was stirred at ambient temperature for 1 hour. Purification by flash column chromatography (silica gel, 40% in hexanes, then 60%, then 80% ethyl ether) gave the title compound of Example 3, the compound of the invention, as a white solid (52 mg).¹1 H NMR (CDCl₃) δ 11.2 (s, 1H), 10.9 (bs, 1H), 8.5 (dd, 1H), 8.2 (bs, 1H), 8.0-7.9 (dd, 1H), 7.53 (s, 1H), 7.5 (dd, dd, 1H), 7.01 (bd, 1H), 6.70 (t, 1H), 6.63 (bd, 1H), 2.30 (s, 3H).

Example 4 1- (3-Chloro-2-pyridinyl) -N- [2,4-dichloro-6- (4,5-dihydro-1H-imidazol-2-yl) phenyl] -3- (trifluoromethyl) -1H -Manufacture of pyrazole-5-carboxamide Step A: Preparation of 2,4-dichloro-6- (4,5-dihydro-1H-imidazol-2-yl) benzeneamine To a solution of ethylenediamine (1.2 mL, 18 mmol) in ethyl ether (50 mL) at -20 ° C, n-butyllithium (6.4 mL, 2.5 M, 16 mmol in hexane) was added. The mixture was stirred at 0 ° C. for 0.3 hours before adding 2,4-dichloro-6-trifluoromethylaniline (0.92 g, 4.2 mmol). The mixture was stirred at 0 ° C. for an additional 1.5 hours, at which point water (0.36 mL, 20 mmol) was added and the solvent was removed under reduced pressure. Purification by flash column chromatography (silica gel, 1% to 10% methanol in dichloromethane) gave the title compound of step A (0.35 g) as a yellow solid.¹1 H NMR (CDCl₃) δ 7.30 (d, 1H), 7.23 (d, 1H), 6.8 (bs, 2H), 4.7-4.6 (bs, 1H), 3.77 (bs, 4H).

Step B: 1- (3-chloro-2-pyridinyl) -N- [2,4-dichloro-6- (4,5-dihydro-1H-imidazol-2-yl) phenyl] -3- (trifluoromethyl) )-1H-Pyrazole-5-Carboxamide production 1- (3-Chloro-2-pyridinyl) -3- (trifluoromethyl) -1H-pyrazol-5-carboxylic acid (0.6 g, 2.02 mol) in dichloromethane (10 mL) containing dimethylformamide (1 drop) Oxalyl chloride (198 μL, 2.22 mmol) was added to the solution of. The mixture was stirred at ambient temperature for 2 hours before concentration under reduced pressure and dissolved in dichloromethane (5 mL). Seven tenths of this solution is added to a solution of the title compound of step A (0.3 g, 1.3 mmol), triethylamine (272 mL, 1.95 mmol) and dimethylaminopyridine (16 mg, 0.13 mmol) in dichloromethane (5 mL). , The mixture was stirred at ambient temperature overnight. A saturated solution of sodium bicarbonate was then added and the mixture was filtered through a column of Celite®. By concentrating and purifying by flash column chromatography (silica gel, 1% in dichloromethane, then 2%, then 5% methanol, then again 10% in chloroform, then 20% acetone, then 5% methanol in dichloromethane). The title compound of Example 4, the compound of the present invention, was obtained as a yellow solid (31 mg).¹1 H NMR (CDCl₃) δ 8.5-8.4 (d, 1H), 7.9 (d, 1H), 7.46 (d, 1H), 7.41 (d, 1H), 7.4 (dd, 1H), 7.31 (s, 1H), 3.77 (s, 4H).

Example 5 1- (2-Chlorophenyl) -N- [2- (4,5-dihydro-1-methyl-1H-imidazol-2-yl) -6-methylphenyl] -3- (trifluoromethyl) -1H-pyrazole -5-Manufacture of carboxamide Step A: Production of 4,5-dihydro-1-methyl-2- (3-methyl-2-nitrophenyl) -1H-imidazole A solution of methyl 3-methyl-2-nitrobenzoate (3.0 g, 15.4 mmol) in N-methylethylenediamine (5 g, 68 mmol) is heated at reflux for 1.5 hours, at which point the solvent is heated under reduced pressure at 130 ° C. Removed. The residue was then heated at 190 ° C. for 1.25 hours before cooling with ice to give the title compound of step A (75% purity) as a brown oil.¹1 H NMR (CDCl₃) δ 7.5 (m, 1H), 7.4 (m, 2H), (3.90 (t, 2H), 3.51 (t, 2H), 2.74 (s, 3H), 2.43 (s, 3H).

Step B: 2- (4,5-dihydro-1-methyl-1H-imidazol-2-yl) -6-methylbenzeneamine Palladium hydroxide (170 mg, 20% by weight on carbon) was added to a solution of the title compound of step A (3.37 g, purity 75%) in ethanol (15 mL). The flask was evacuated twice, flushed with nitrogen, then evacuated twice and flushed with hydrogen. The mixture was vigorously agitated under a hydrogen balloon for 3 hours prior to exhaust, exposed to air and filtered through a Celite® pad. The solution was concentrated, filtered through a pad of silica gel and eluted with 1% in dichloromethane, then 5%, then 10% methanol, then 5% triethylamine, 10% methanol, 85% dichloromethane. The elution material was concentrated in triethylamine / methanol / dichloromethane to give the title compound of step B (1.5 g) as an off-white solid.¹1 H NMR (CDCl₃) δ 7.3 (d, 1H), 7.1 (d, 1H), 6.9 (bs, 1H), 6.6 (t, 1H), 5.6 (bs, 1H), 3.6-3.5 (m, 2H), 2.9 (t, 2H), 2.47 (s, 3H), 2.16 (s, 3H).

Step C: 1- (2-chlorophenyl) -N- [2- (4,5-dihydro-1-methyl-1H-imidazol-2-yl) -6-methylphenyl] -3- (trifluoromethyl)- Production of 1H-pyrazole-5-carboxamide In a solution of 1- (2-chlorophenyl) -3- (trifluoromethyl) -1H-pyrazol-5-carboxylic acid (1.2 g, 4.13 mol) in dichloromethane (10 mL) containing dimethylformamide (1 drop) Oxalyl chloride (390 μL, 4.47 mmol) was added. The mixture was stirred at ambient temperature for 1 hour before concentrating under reduced pressure. The mixture is dissolved in dichloromethane (5 mL) and added to a solution of step B title compound (0.65 g, 3.44 mmol), dimethylaminopyridine (42 mg, 0.34 mmol) and triethylamine (766 μL, 5.50 mmol) in dichloromethane (10 mL). did. The mixture was stirred at ambient temperature for 3 days before adding the saturated solution of sodium bicarbonate. The mixture was extracted twice with dichloromethane, the combined organic phases were dried (magnesium sulphate), concentrated and flash column chromatography (silica gel, ethyl ether, then ethyl acetate, then 2% in dichloromethane, then 5% methanol). Purified by. Concentrate the substance that elutes in 5% methanol / dichlorometh, dissolve in dichloromethane, and 1,5,7-triazabicyclo- [4.4.0] -deca- on polystyrene resin (Fluka Catalog No. 90603). Shake with 1 g of 5-en for 0.5 hour. By filtering and concentrating, the title compound of Example 5, the compound of the present invention (0.16 g) was obtained.¹1 H NMR (CDCl₃) δ 7.6-7.5 (m, 1H), 7.4 (m, 3H), 7.2 (m, 4H), 3.85 (t, 2H), 3.4 (bm, 2H), 2.71 (s, 3H), 2.17 (s, 3H).

Example 6 Production of 1- (2-chlorophenyl) -N- [2-methyl-6- (1-methyl-1H-imidazol-2-yl) phenyl] -3- (trifluoromethyl) -1H-pyrazol-5-carboxamide To a solution of the title compound (35 mg, 76 μmol) of Example 5 in toluene (20 mL) was added active manganese dioxide (132 mg, 1.52 mmol) and the mixture was filtered through a pad of Celite®. It was heated to reflux for 3 days. Concentration and purification by flash column chromatography (silica gel, 60% in hexane, then 80% ethyl ether, then ethyl ether) gave the title compound of Example 6, the compound of the invention (19 mg).¹1 H NMR (CDCl₃) δ 10.5 (bs, 1H), 7.5 (m, 1H), 7.4 (m, 3H), 7.3-7.2 (m, 4H, 7.13 (d, 1H), 6.95 (d, 1H), 3.65 (s, 3H) ), 2.26 (s, 3H).

Example 7 N- [4-Bromo-2- (4,5-dihydro-1-methyl-1H-imidazol-2-yl) -6-methylphenyl] -1- (2-chlorophenyl) -3- (trifluoromethyl) Production of -1H-pyrazole-5-carboxamide N-Bromosuccinimide (26 mg, 0.15 mmol) was added to a solution of the title compound (68 mg, 0.15 mmol) of Example 5 in dichloromethane (3 mL). The mixture was stirred overnight at ambient temperature before purification by flash column chromatography (silica gel, 2% in dichloromethane, then 5% methanol), the title compound of Example 7, the compound of the invention (36 mg). Got¹1 H NMR (CDCl₃) δ 8.02 (s, 1H), 7.7-7.6 (d, 1H), 7.5-7.4 (m, 4H), 7.3 (d, 1H), 4.0-3.8 (bm, 4H), 2.94 (s, 3H), 2.34 (s, 3H).

Example 8 1- (3-Chloro-2-pyridinyl) -N- [2-methyl-6- (1,4,5,6-tetrahydro-4-oxo-2-pyrimidinyl) phenyl] -3- (trifluoromethyl) -1H-pyrazole-5-carboxamide Step A: Preparation of 3-methyl-2-nitrobenzamide Methyl 3-methyl-2-nitrobenzoate (10.02 g, 51.3 mmol) was added to a 7N solution of ammonia in methanol (50 mL) and the mixture was placed at 100 ° C. in Fisher-Porter tubing. Heated in C for 3 hours. The solution was then cooled, concentrated and milled with dichloromethane to give the title compound of step A as a white solid (1.4 g).¹1 H NMR (CDCl₃) δ 8.2 (bs, 1H), 7.7 (bs, 1H), 7.6 (m, 3H), 2.28 (s, 3H).

Step B: Preparation of methyl 3-methyl-2-nitrobenzenecarboxyimidate tetrafluoroborate To a solution of the title compound of step A (1.07 g, 5.9 mmol) in dichloromethane (15 mL) was added trimethyloxonium tetrafluoroborate (1.06 g, 7.1 mmol) and the mixture was stirred at ambient temperature overnight. Concentration gave the title compound of step B as a white solid (1.7 g).¹H NMR (DMSO-d₆) δ 7.8 (m, 3H), 7.1 (t, 1H), 4.00 (s, 3H), 2.41 (s, 3H).

Step C: Production of 5,6-dihydro-2- (3-methyl-2-nitrophenyl) -4 (1H) -pyrimidinone To a solution of the title compound (1.7 g, 5.9 mmol) of step B in methanol (20 mL) was added β-alanine methyl ester hydrochloride (832 mg, 5.9 mmol), followed by sodium methoxide (2.7 mL, in methanol). 25 wt%, 11.8 mmol) was added and the mixture was heated at reflux for 1.5 hours. The mixture was then cooled, stirred overnight at ambient temperature and heated again at reflux for 3 hours. The mixture was then cooled, concentrated and triturated with dichloromethane. The soluble fraction was then purified by flash column chromatography (silica gel, ethyl ether) to give the title compound of step C as a white solid (0.12 g).¹1 H NMR (CDCl₃) δ 8.4-8.2 (bs, 1H), 7.6-7.4 (m, 3H), 3.80 (t, 2H), 2.53 (t, 2H), 2.40 (s, 3H).

Step D: 2- (2-amino-3-methylphenyl) -5,6-dihydro-4 (1H) -pyrimidinone Palladium hydroxide (20 wt% on carbon) (measured to cover the tip of a small experimental spatula) is added to a solution of the title compound (0.12 g, 0.52 mmol) of step C in ethanol (10 mL). did. The flask was evacuated twice, flushed with nitrogen, then evacuated twice and flushed with hydrogen. Prior to exhaust, the mixture was vigorously agitated under a hydrogen balloon for 2 hours, exposed to air and filtered through a Celite® pad. The solution was concentrated to give the title compound of step D (0.11 g).¹1 H NMR (CDCl₃) δ 8.0 (bs, 1H), 7.2-7.1 (m, 2H), 6.7-6.6 (t, 1H), 6.2 (bs, 2H), 3.91 (t, 2H), 2.56 (t, 2H), 2.19 ( s, 3H).

Step E: 1- (3-chloro-2-pyridinyl) -N- [2-methyl-6- (1,4,5,6-tetrahydro-4-oxo-2-pyrimidinyl) phenyl] -3- (tri) Production of Fluoromethyl) -1H-Pyrazole-5-Carboxamide In a solution of 1- (2-chlorophenyl) -3- (trifluoromethyl) -1H-pyrazol-5-carboxylic acid (0.6 g, 2.02 mol) in dichloromethane (10 mL) containing dimethylformamide (1 drop), Oxalyl chloride (198 μL, 2.22 mmol) was added. Before concentrating under reduced pressure, the mixture was stirred at ambient temperature for 2 hours and dissolved in dichloromethane (5 mL). Three-tenths of this solution is added to a solution of the title compound of step D (0.11 g, 0.54 mmol), triethylamine (113 mL, 0.81 mmol) and dimethylamino-pyridine (7 mg, 0.05 mmol) in dichloromethane (5 mL). The mixture was then stirred at ambient temperature overnight. A saturated solution of sodium bicarbonate was then added and the mixture was filtered through a column of Celite®. It was concentrated and purified by flash column chromatography (silica gel, 1% in chloroform, then 5%, then 10%, then 20% acetone) to give the title compound of Example 8, the compound of the invention, a white solid (64 mg). Obtained as.¹1 H NMR (CDCl₃) δ 11.3 (bs, 1H), 8.5 (dd, 1H), 7.9 (dd, 1H), 7.5-7.4 (m, 1H), 7.4-7.2 (m, 3H), 7.18 (s, 1H), 3.85 ( t, 3H), 2.54 (t, 2H), 2.23 (s, 3H).

The following compounds in Tables 1-37 can be prepared by the procedures described herein along with methods known in the art. The following abbreviations are used in the table: Me for methyl, Et for ethyl, Ph for phenyl.

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<tables num="103"><img file="JP4445751B2_D0164.tif" /></tables>

<tables num="104"><img file="JP4445751B2_D0165.tif" /></tables>

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Formulation / use The compounds of the present invention will generally be used as formulations or formulations with agriculturally suitable carriers comprising at least one liquid diluent, solid diluent or surfactant. The ingredients of the formulation or formulation are selected to match the physical properties of the active ingredient, the mode of use, and environmental factors such as soil type, moisture and temperature. Useful formulations include liquids that can optionally be concentrated into gels, such as solutions (including emulsions), suspensions, solutions such as emulsions (including microemulsions and / or saspo emulsions). Can be mentioned. Useful formulations also include water-dispersible (hydrable) or water-soluble solids such as fine powders, powders, granules, pellets, tablets and films. The active ingredient can be (micro) encapsulated and further formed into a suspension or solid formulation; or the entire formulation form of the active ingredient can be encapsulated (or "overcoated"). Encapsulation can control or delay the release of the active ingredient. The spray formulation is diluted in a suitable medium and used in a spray volume of about hundreds to hundreds of liters per hectare. High concentrations of formulations are primarily used as intermediates for further formulations.

The formulation will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate range totaling 100% by weight:

<tables num="109"><img file="JP4445751B2_D0170.tif" /></tables>

Common solid diluents are described in Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey. Common liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950. Surfactants and Recommended for McCutcheon's Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, and Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964. Uses are shown. All formulations may contain small amounts of additives to reduce foaming, solidification, corrosion, bacterial growth, etc., or thickeners to increase viscosity.

Surfactants include, for example, polyethoxylated alcohol, polyethoxylated alkylphenol, polyethoxylated sorbitan fatty acid ester, dialkylsulfosuccinate, alkylsulfate, alkylbenzenesulfonate, organic silicone, N, N-dialkyltaurine salt, ligninsulfonate, naphthalenesulfonate. Included are formaldehyde condensates, polycarboxylates, and polyoxyethylene / polyoxypropylene block copolymers. Solid diluents include, for example, clays such as bentonite, montmorillonite, attapargite and kaolin, starch, sugar, silica, talc, diatomaceous soil, urea, calcium carbonate, sodium carbonate and sodium bicarbonate, and sodium sulfate. Is done. Liquid diluents include, for example, water, N, N-dimethylformamide, dimethylsulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffin, alkylbenzene, alkylnaphthalene, olive oil, castor oil, flaxseed oil, millet oil, sesame oil, Corn oil, lacquer oil, cottonseed oil, soybean oil, rapeseed oil and coconut oil, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, and alcohols such as methanol, cyclo Includes hexanols, decanols and tetrahydrofurfuryl alcohols.

A solution containing an emulsion can be prepared by simply mixing the ingredients. Fine powders and powders can be prepared by blending and pulverizing with a hammer mill, a fluid energy mill, or the like. Suspensions are usually prepared by wet grinding; see, for example, US Pat. No. 3,060,084. Granules and pellets can be prepared by spraying the active agent onto a preformed granular carrier or by agglomeration techniques. Browning, Agglomeration, Chemical Engineering, December 4,1967, pp147-148, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New See York, 1963, pp8-57, and below and WO 91/13546. Pellets can be prepared as described in US Pat. No. 4,172,714. Water-dispersible and water-soluble granules can be prepared as described in US Pat. Nos. 4,144,050, 3,920,442 and DE3,246,493. Tablets can be prepared as described in US Pat. Nos. 5,180,587, 5,232,701 and 5,208,030. Films can be prepared as described in GB2,095,558 and US Pat. No. 3,299,566.

For more information on the technical field of formulation, see TS Woods, The Formulator's Toolbox --Product Forms for Modern Agriculture in Pesticide Chemistry and Bioscience, The Food-Environment Challenge, T. Brooks and TRRoberts, Eds., Proceedings of the 9th International. Congress on Pesticide Chemistry, The Royal Society of See Chemistry, Cambridge, 1999, pp.120-133. U.S. Pat. No. 3,235,361, column 6, columns 16 to 7, lines 19 and Examples 10 to 41; U.S. Pat. No. 3,309,192, column 5, columns 43 to 7, lines 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S. Pat. No. 2,891,855, column 3, lines 66-5, lines 17 and Examples 1-4; Klingman, Weed Control See as a Science, John Wiley and Sons, Inc., New York, 1961, pp81-96; Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989.

In the following examples, all percentages are by weight and all formulations are prepared by conventional methods. Compound numbers indicate compounds in Index Table A.

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<tables num="111"><img file="JP4445751B2_D0172.tif" /></tables>

<tables num="112"><img file="JP4445751B2_D0173.tif" /></tables>

<tables num="113"><img file="JP4445751B2_D0174.tif" /></tables>

<tables num="114"><img file="JP4445751B2_D0175.tif" /></tables>

The compounds of the present invention are characterized by favorable metabolic and / or soil residue patterns and exhibit activity to control areas of agricultural or non-agricultural invertebrate pests. (In the context of this specification, "invertebrate pest control" refers to the occurrence (withering amount) of invertebrate pests that significantly reduces supply or causes other damage or damage caused by invertebrate pests. Means to suppress); As referred herein, the term "invertebrate pest" includes arthropods, abdominal animals, and nematodes that are economically important as pests. The term "arthropod" includes insects, mites, spiders, scorpions, centipedes, millipedes, isopos and conjugates. The term "gastropods" includes snails, slugs and other stylommatophora. The term "nematode" includes helminths such as roundworms, cardworms, and phytonematodes (Nematoda), trematodes (Tematoda), tapeworms and tapeworms (Cestoda). Those skilled in the art will appreciate that not all compounds are equally effective against all pests. The compounds of the present invention are active against economically important agricultural and non-agricultural pests. The term "agricultural" refers to the production of crops such as food and fiber, including cereals (eg wheat, wheat, barley, limewood, rice, corn), soybeans, vegetables (eg lettuce, cabbage, tomatoes, beans). ), Potatoes, sweet potatoes, grapes, cotton, and tree-growing fruits (eg, pear-like fruits, stone fruits, citrus fruits). The term "non-agricultural" is used in other horticultures (eg, non-cultivated seedlings or ornamental plants in forests, greenhouses, fields), public health (human) and animal hygiene, domestic and commercial structures, household and preserved. Refers to the intended use or pest of the product. For reasons of invertebrate pest control area and economic importance, cotton, corn, soybean, rice, vegetables, potatoes, sweet potatoes, vines and trees by controlling invertebrate pests (tree) Protection of fruit) (from damage or damage caused by invertebrate pests) is a preferred embodiment of the present invention. Agricultural or non-agricultural pests include Lepidoptera larvae, such as armyworms, cutworms, loopers, and heliothine (eg, fall army). Worm (fall armyworm) (Spodoptera fugiperda JESmith), Beet armyworm (Spodoptera exigua Huebner), Dark swordgrass (black cutworm) (Agrotis ipsilon Hufnagel), Iraqi sakin worm (cabbage looper) tobacco budworm) (Heliothis virescens Fabricius); perforated animals (borer), swordgrass (casebearer), lepidopteran larvae (webworm), cornworm (coneworm), worm (cabbageworm) and larvae of the family Meiga (skeletonizer) ) (For example, European corn borer) (Ostrinia nubilalis Huebner), navel orangeworm (Amyelois transitella Walker), corn root webworm (Crambus caliginosellus Clemens), black swordgrass (sod) ) (Herpetogramma licarsisalis Walker)); Flea beetle, Cucumber beetle of the family Chrysomelidae, rootworm, leaf beetle, potato beetle, and Chrysomelidae Leaf miner (eg, Colorado potato beetle (Leptinotarsa decemlineata Say), western corn rootworm (Diabrotica virgifera virgifera Le Conte)); Insects (eg, Japanese beetle (Popillia japonica Newman) and a species of Coleoptera (European chafer) (Rhizotrogus majalis Razoumowsky)); Wireworms; include the bark beetle of the family Coleoptera (Scolytidae) and the coleoptera (flour beetle) of the family Coleoptera (Tenebrionidae). In addition, as agricultural and non-agricultural pests: ) And other seed bugs, the froghopper (Cercopidae) froghopper (spittle bug), the leaf-footed bugs (Coreidae) various froghoppers (squash bugs), and the red bugs (Pyrrhocoridae) froghoppers (red bugs) and red bugs. cotton stainer). Adults and larvae of the order Acari (mites), such as spider mite of the family Spider mite (Tetranychidae) (eg, European red mite (Panonychus ulmi Koch), two spotted spider mite (Tetranychus) urticae Koch), McDaniel mite (Tetranychus mcdanieli McGregor), flat mite of Tenuipalpidae (for example, citrus flat mite (Brevipalpus lewisi McGregor)), Fushidani (Eriophyidae) rust mite and bud mite, other foliar-feeding mites and ticks important for human and animal health, namely the leopard mite (Epider moptidae) dust mite, spider mite (Demod Flea (Siphonoptera) pests, such as keops flea (oriental rat flea) (Xenopsylla cheopis Rothschild), cat flea (Ctenocephalides felis Bouche), dog flea (dog flea) (Ctenocephalides canis Curtis), chicken flea (hen) Also included are flea (Ceratophyllus gallinae Schrank), sticktight flea (Echidnophaga gallinacea Westwood), human flea (Pulex irritans Linnaeus) and other fleas that plague animals and birds. Other arthropod pests included as targets include: Authentic spiders (Araneae) spiders, such as brown recluse spiders (Loxosceles reclusa Gertsch &amp; Includes Mulaik and black widow spiders (Latrodectus mactans Fabricius), and centipedes of the order Centipede, such as house centipede (Scutigera coleoptrata Linnaeus). The compounds of the present invention are members of nematodes (Nematoda), ascarids (Cestoda), ascarids (Trematoda), and ascarids (Acanthocephala), such as economically important roundworms (Strongylida), Kaichu. Members of the order Ascaridida, Oxyurida, Rhabditida, Spirurida, and Enoplida, such as, but not limited to, economically important agricultural pests (ie, Kitanekobu nematodes). (Meloidogyne) root knot nematode, Trichodorus nematode, stubby root nematode, etc.), animal and human hygiene pests ( That is, all economically important nematodes, nematodes, and roundworms, such as the horse-parasitic nematode (Strongylus vulgaris), the dog-parasitic canine roundworm (Toxocara canis), and the sheep-parasitic nematode (Toxocara canis). Haemonchus contortus), canine filamentous insects (Dirofilaria immitis Leidy), horses (Anoplocephala perfoliata), ascarids (Fasciola hepatica Linnaeus), etc. ..

The compounds of the present invention are Lepidoptera pests (Alabama argillacea Huebner, Archips argyrospila Walker, A. rosana Linnaeus and other Archips species, Nikameichu (Archips). Chilo suppressalis Walker), Cnaphalocrosis medinalis Guenee, Crambus caliginosellus Clemens, Crambus teterrellus Zincken, Codling moth (Cydia pomonella Linnaeus), Codling moth (Cydia pomonella Linnaeus) , Helicoverpa armigera Huebner, Helicoverpa zea Boddie, Heliothis virescens Fabricius, Herpetogramma licarsisalis Walker, Lobesia botrana Denis &amp; Schiffermueller, Pectinophora gossypiella Saunders, Pectinophora gossypiella Saunders brassicae Linnaeus, Cabbage White (Pieris rapae Linnaeus), Diamondback Moth (Plutella xylostella Linnaeus), Beet Armyworm (Spodoptera exigua Huebner), Spodoptera litura Fabricius, Spodoptera litura Fabricius, Spodoptera litura Fabricius It is particularly active against Huebner) and a species of Twirler moth (Tuta absoluta Meyrick). The compounds of the present invention are members of the order Homoptera, such as: Acyrthisiphon pisum Harris, Aphis craccivora Koch, Aphis fabae Scopoli, Aphis gossypii Glover. , Ringo aphid (Aphis pomi De Geer), Yukiyanagi aphid (Aphis spiraecola Patch), Potato aphid (Aulacorthum solani Kaltenbach), Strawberry aphid (Chaetosiphon fragaefolii Cockerell) Aphids (Dysaphis plantaginea) Paaserini), apple aphid (Eriosoma lanigerum Hausmann), peach aphid (Hyalopterus pruni Geoffroy), fake aphid (Lipaphis erysimi Kaltenbach), grain aphid (Metopolophium dirrhodum Walker), tulip aphid (Metopolophium dirrhodum Walker) Aphid (Myzus persicae Sulzer), Lettuce aphid Nasonovia ribisnigri Mosley, Kobu aphid (Pemphigus spp.), Corn aphid (Rhopalosiphum maidis Fitch), Wheat aphid (Rhopalosiphum padi Linnaeus), Wheat aphid (Rhopalosiphum padi Linnaeus) Aphid (Sitobion avenae) Fabricius, Therioaphis maculata Buckton, Whitefly aphid (Toxoptera aurantii Boyer de Fonscolombe) and Greenhouse whitefly (Toxoptera citricida Kirkaldy), Casa aphid (Adelges spp.), Pecanne aphid (Phyllera) Whitefly (Bemisia tabaci Gennadius), Silverleaf Whitefly (Bemisia argentifolii Bellows &amp; Perring), Whitefly (Dialeurodes citri Ashmead) and Greenhouse Whitefly (Trialeurodes vaporariorum Westwood) Fallen, leafhopper (Macrolestes quadrilineatus Forbes), green leafhopper (Nephotettix cinticeps Uhler), green leafhopper (Nephotettix nigropictus Stal), brown planthopper (Nilaparvata lugens Stal), corn planthopper (Peregrinus) Ineunka (Sogatodes orizicola Muir), White apple leafhopper (Typhlocyba pomaria McAtee), Chimadarahimeyokobai (Erythroneoura spp.), Seventeenth year seminar (Magcidada septendecim Linnaeus), Iseriya scale insect (Icerya purchasi Maskell) It also has commercially significant activity against Comstock, Pseudococcus citri Risso, other Pseudococcus spp., Cacopsylla pyricola Foerster, and Trioza diospyri Ashmead. These compounds are members of the Hemiptera: for example, the stink bug (Acrosternum hilare Say), the stink bug (Anasa tristis De Geer), the stink bug (Blissus leucopterus leucopterus Say), the cotton lace bug (Corythuca). gossypii Fabricius), tomato bug (Cyrtopeltis modesta Distant), red stink bug (Dysdercus suturellus Herrich-Schaeffer), a kind of brown stink bug (Euchistus servus) Say, Itten stink bug (Euchistus variolarius Palisot de Beauvois), Himemadara stink bug (Graptosthetus spp.), Pentatomidae helicopter bug (Leptoglossus corculus Say), Midorimekuragame (Lygus lineolaris Palisot de Beauvois), Southern green stink bug ), Stink bug (Oebalus pugnax Fabricius), Stink bug (Oncopeltus fasciatus Dallas), and Southern green stink bug (Pseudatomoscelis seriatus Reuter). Other types of insects controlled by the compounds of the present invention include Thysanoptera (eg Frankliniella occidentalis Pergande), Scirthothrips citri. Moulton, Soybean thrips (Sericothrips variabilis Beach) and Negia thrips (Thrips tabaci Lindeman); and Coleoptera (eg, Colorado potato beetle (Leptinotarsa decemlineata Say), Mexican bean beetle (Epilachna varivestis Mulsant) Includes click beetle larvae of the genus Athous or Limonius.

The compounds of the present invention include insecticides, bactericides, anti-nematode agents, acaricides, growth modifiers such as rooting stimulants, chemical fertility agents, information chemicals, repellents, attractants, pheromones, feeding stimulants. , Other bioactive compounds or other bioactive compounds or bioactive agents, including one or more other bioactive compounds or agents, including insectogenic bacteria, viruses or fungi, to confer a broader range of agricultural utility. Ingredient pesticides can also be formed. Thus, the compounds of the invention can further comprise a biologically effective amount of at least one additional bioactive compound or agent. Examples of such bioactive compounds or agents that can be combined with them are: pesticides such as abamectin, acephate, acetamipride, avelmectin, azadilactin, azinphosmethyl, bifenthrin, binfenazate, buprofezin, carbofuran, chlorphenazate, chlorfluthrin. Azin, chlorpyrifos, chlorpyrifos methyl, chromaphenozide, clothianidin, cyhalothrin, β-cyhalothrin, cyhalothrin, λ-cyhalothrin, Acaricides such as amidoflumeth, amitratz, tynomethionate, chlorobenzilate, sihexatin, dicofol, dienochlor, etoxazole, phenazakin, fenbutatin oxide, fenpropatrin, fenpyroximate, hexithiazox, propargit, pyridaben and tebufenpyrad; and biological agents such as isawai Includes Bacillus thuringiensis, including (aizawai) and kurstaki strains, δ-endotoxin of Bacillus thuringiensis, baculovirus, and insectogenic bacteria, viruses and fungi. .. The compounds of the present invention and their compositions can be applied to genetically transformed plants to express proteins that are toxic to invertebrate pests (such as Bacillus tulingensis toxin). ). The effects of the extrinsically applied invention invertebrate pest control compounds can be synergistic with the expressed toxic proteins.

Common references for these crop protectants include The Pesticide Manual, 12th Edition, CDSTomlin, Ed., British Crop Protection Council, Farnham, Surrey, UK, 2000.

Preferred insecticides and acaricides for mixing with the compounds of the invention include pyrethroids such as cipermethrin, cyfluthrin, cyfluthrin and β-cyfluthrin, esphenvalerate, fenvalerate and tralomethrin; And thiodicalbu; neonicotinoids such as clothianidin, imidacloprid and thiacloprid; neuronal sodium channel blockers such as indoxacarb; insecticidal macrocyclic lactones such as spinosad, abamectin, avelmectin and emamectin; γ-aminobutyric acid (GABA) antagonists such as Includes endosulfane, etiprol and fipronil; insecticidal ureas such as fluphenoxlon and triflumron; mimic larva hormones such as diophenolan and pyriproxyfen; pimetrodin; and amitraz. Preferred biological agents to mix with the compounds of the invention include the δ-endotoxins of Bacillus tulingensis and Bacillus tulingensis and naturally occurring and genetically modified viral insecticides such as the Baculoviridae (Baculoviridae). Includes members of Baculoviridae) as well as insecticidal fungi.

The most preferred mixture is a mixture of the compound of the present invention and sihalothrin; a mixture of the compound of the present invention and β-cifluthrin; a mixture of the compound of the present invention and esphenvalerate; a mixture of the compound of the present invention and metmil; A mixture of the compound of the present invention and imidacloprid; a mixture of the compound of the present invention and thiacloprid; a mixture of the compound of the present invention and indoxacarb; a mixture of the compound of the present invention and abamectin; Mixtures; Mixtures of compounds of the invention with etiprol; Mixtures of compounds of the invention with fipronil; Mixtures of compounds of the invention with fluphenoxlon; Mixtures of compounds of the invention with pyriproxyfen; And pimetrodin; a mixture of the compound of the present invention and Amitraz; a mixture of the compound of the present invention and Bacillus tulingensis and a mixture of the compound of the present invention and δ-endotoxin of Bacillus tulingensis. Is included.

In certain cases, other invertebrate pest control compounds or agents that have different modes of action but have similar control ranges will be particularly advantageous for resistance management. Thus, the compositions of the present invention further comprise a biologically effective amount of at least one additional invertebrate pest control compound having a different mode of action but with a similar control range. be able to. A wide range of plant protection is provided by contacting a plant or the location of the plant that has been genetically modified to express a plant protection compound (eg, a protein) with a biologically effective amount of the compound of the invention. And it will be advantageous for resistance management.

Apply one or more compounds of the invention in effective amounts to the environment of pests, including agricultural and non-agricultural sites, to areas to be protected, or directly to pests to be controlled. By doing so, invertent pests are controlled in agricultural and non-agricultural applications. Thus, the invention is further a method of controlling invertent pests in agricultural and / or non-agricultural applications, with a biologically effective amount of one or more compounds of the invention, or A composition containing at least one such compound, or a composition containing at least one such compound and an effective amount of at least one additional bioactive compound or agent, and an invertent pest or its environment. Includes methods that include contacting. In an example of a suitable composition comprising a compound of the invention and an effective amount of at least one additional bioactive compound or agent, the additional bioactive compound or agent is on the same granules as the compound of the invention. Includes granular compositions that are present or present on granules that are separate from the compounds of the invention.

The preferred contact method is the spray method. Alternatively, the granular composition containing the compound of the present invention can be applied to plant leaves or soil. The compound of the present invention is also a composition containing the compound of the present invention applied as a granular formulation, which is applied to the soil by immersing the soil as a liquid formulation in the treatment of a seedling box or in the depression of a transplanted seedling. Is effectively delivered via uptake by the plant by contacting the plant. Compounds are also effective by topically applying compositions containing the compounds of the invention to the site of origin. Other contact methods include direct and residual sprays, aerial sprays, gels, seed coatings, microencapsulations, penetrating uptakes, baits, earmarks, boluses, atomizers, smokers, aerosols, fine powders and many others. The application of the compound or composition of the present invention according to the above. The compounds of the present invention may also be impregnated into materials (eg, Insecta) used to make invertebrate pest control devices.

The compounds of the present invention can be incorporated into food ingested by invertebrate pests or in devices such as traps. Granules or baits containing 0.01-5% active ingredient, 0.05-10% water-retaining agent (s) and 40-99% vegetable flour at very low doses, especially in direct contact. It is effective in controlling insects in the soil at doses of active ingredients that are lethal by ingestion.

The compounds of the invention can be applied in pure form, but in most cases formulations containing one or more compounds, along with suitable carriers, diluents, and surfactants, or intended end use. Will be applied in combination with food depending on the condition. Preferred application methods include spraying an aqueous dispersion or purified oil solution of the compound. Combinations with spray oils, spray oil concentrates, spreading agents, adjuvants, other solvents, and cooperating agents, such as piperonyl butoxide, often enhance the potency of the compound.

The dosage required for effective control (ie, the "biologically effective amount") is the type of invertent pest to be controlled, the life cycle of the pest, its life stage, its size, location, timing, It will vary depending on factors such as host crop or host animal, feeding behavior, mating behavior, ambient humidity, temperature, etc. Under normal circumstances, a dose of about 0.01-2 kg / hectare of active ingredient may be sufficient to control pests in agroecosystems, but a small amount of 0.0001 kg / hectare may be sufficient. Alternatively, high doses of 8 kg / hectare may be required. For non-agricultural applications, effective doses vary from about 1.0 to 50 mg / sqm, but small doses of 0.1 mg / sqm may be sufficient, or higher doses of 150 mg / sqm are required. In some cases. One of ordinary skill in the art can readily determine the biologically effective amount required to control the desired level of invertebrate pests.

The following tests demonstrate the control effectiveness of the compounds of the invention against specific pests. Control efficacy refers to suppression of invertebrate pest development (including mortality) that significantly reduces feeding. However, the pest control protection provided by the compounds of the present invention is not limited to these types. See index tables A through F for compound details. The following abbreviations are used in the index table below: Me is methyl. The abbreviation "Ex" stands for "Example" and is followed by a number indicating the example in which the compound is prepared.

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Biological examples of the present invention Exam A In the evaluation of diamondback moth (Plutella xylostella) control, the test unit consists of a small open container with radish plants of days 12-14 inside. Using a core sampler, pre-populate this with 10 to 15 larvae on a piece of insect diet, remove the plug from the hardened insect diet sheet with many larvae growing on it, and larvae. And transfer the plug containing the food to the test unit. As the dietary plug dries, the larvae move onto the test plant.

Unless otherwise specified, X-77® Spreader Lo-Form Formula (Lo) containing 10% acetone, 90% water and alkylarylpolyoxyethylene, free fatty acids, glycols and isopropanol. -Foam Formula) A test compound was formulated using a solution containing 300 ppm of a nonionic surfactant (Loveland Industries, Inc.). The compounded compound was applied in 1 ml of liquid through a SUJ2 sprayer nozzle (Spraying Systems Co.) with a 1 / 8JJ custom body located 1.27 cm (0.5 inch) above the top of each test unit. .. All experimental compounds on this screen were sprayed at 250 ppm (or less) and repeated 3 times. After spraying the compounded test compound, each test unit was dried for 1 hour, then a black mesh lid was placed on top. The test unit was held in a growth chamber at 25 ° C and 70% relative humidity for 6 days. The feeding damage of plants was visually evaluated.

Among the compounds tested, the following compounds:^*、2^*、3、4^*、5^*、6、7^*、8、10^*、11^*、12^*、13^*、14^*、15^*And 17^*Provided an excellent level of plant protection (less than 20% feeding damage).

Exam B In the evaluation of fall armyworm (Spodoptera frugiperda) control, the test unit consists of a small open container with a 4-5 day corn plant inside. As described for Test A, a core sampler was used to pre-populate it with 10 to 15 1-day-old larvae on a piece of insect diet.

As described for Test A, the test compounds were compounded and sprayed at 250 ppm (or below). The application was repeated 3 times. After spraying, the test unit was held in the growth chamber as described in Test A and evaluated visually.

Among the compounds tested, the following compounds: 7^*、10、12^*、13^*、14^*And 17^*Provided an excellent level of plant protection (less than 20% feeding damage).

Exam C For the evaluation of control of Heliothis virescens, the test unit consists of a small open container with a cotton plant on days 6-7. As described for Test A, a core sampler was used to pre-populate it with eight 2-day-old larvae on a piece of insect diet.

As described for Test A, the test compounds were compounded and sprayed at 250 ppm (or below). The application was repeated 3 times. After spraying, the test unit was held in the growth chamber as described in Test A and evaluated visually.

Among the compounds tested, the following compounds: 7^*、10^*、11^*、12^*、13、14^*And 17^*Provided an excellent level of plant protection (less than 20% feeding damage).^*Tested at 50 ppm.<u style="single">The features or main aspects of the present invention are as follows.</u><u style="single">1.</u><u style="single">Expression I:</u><chemistry num="62"><img file="JP4445751B2_D0182.tif" /></chemistry><u style="single">(In the formula, A is O or S;</u><u style="single">G is C (= O), SO or S (O)</u>_{<u style="single">2</u>}<u style="single">One selected independently of the group consisting of</u><u style="single">5- or 6-membered aromatic heterocycles or 5- or 6-membered non-members, sometimes including two ring members</u><u style="single">It is an aromatic heterocycle, and each ring may have 1 to 4 Rs.</u>^{<u style="single">2</u>}<u style="single">Replaced by;</u><u style="single">J is selected from the group consisting of J-5, J-6, J-7, J-8, J-9 and J-10</u><u style="single">Pyrazole or pyrrole rings, each ring being R</u>^{<u style="single">3</u>}<u style="single">Replaced by, and optionally R</u>^{<u style="single">6</u>}<u style="single">O</u><u style="single">And R</u>^{<u style="single">7</u>}<u style="single">Replaced by;</u><chemistry num="63"><img file="JP4445751B2_D0183.tif" /></chemistry><u style="single">R</u>^{<u style="single">1</u>}<u style="single">Is H; or C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Alkyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Alkenyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Alkyne or C</u>_{<u style="single">3</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Cycloalkyl, each optionally halogen, CN, NO</u>_{<u style="single">2</u>}<u style="single">, Hydroxy, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkoxy, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkylthio, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkyl sulfinyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkylsulfonyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkoxycarbonyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkylamino, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">8</u>}<u style="single">Dialkylamino and C</u>_{<u style="single">3</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Substituent with one or more substituents independently selected from the group consisting of cycloalkylamino; or</u><u style="single">R</u>^{<u style="single">1</u>}<u style="single">Is C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Alkylcarbonyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Alkoxycarbonyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Alkylaminocarbonyl, C</u>_{<u style="single">3</u>}<u style="single">~ C</u>_{<u style="single">8</u>}<u style="single">Dialkylaminocarbonyl or C (= A) J;</u><u style="single">R</u>^{<u style="single">2</u>}<u style="single">Or R</u>^{<u style="single">3</u>}<u style="single">Are independently H and C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Alkyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Alkenyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Alkyne, C</u>_{<u style="single">3</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Cycloalkyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Haloalkyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Haloalkenyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Halo alkynyl, C</u>_{<u style="single">3</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Halocycloalkyl, halogen, CN, CO</u>_{<u style="single">2</u>}<u style="single">H, CONH</u>_{<u style="single">2</u>}<u style="single">, NO</u>_{<u style="single">2</u>}<u style="single">, Hydroxy, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkoxy, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Haloalkoxy, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkylthio, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkyl sulfinyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkylsulfonyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Haloalkylthio, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Haloalkyl sulfinyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Haloalkylsulfonyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkylamino, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">8</u>}<u style="single">Dialkylamino, C</u>_{<u style="single">3</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Cycloalkylamino, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Alkylcarbonyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Alkoxycarbonyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Alkylaminocarbonyl, C</u>_{<u style="single">3</u>}<u style="single">~ C</u>_{<u style="single">8</u>}<u style="single">Dialkylaminocarbonyl or C</u>_{<u style="single">3</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Trialkylsilyl; or</u><u style="single">R</u>^{<u style="single">2</u>}<u style="single">Or R</u>^{<u style="single">3</u>}<u style="single">Are independently phenyl, benzyl, benzoyl, phenoxy or 5- or 6-membered aromatic heterocycles, naphthyl ring systems, or aromatic or non-aromatic 8-membered, 9- or 10-membered heterobicyclic fused ring systems. There, each ring or ring system is R</u>^{<u style="single">5</u>}<u style="single">Substituted with 1-3 substituents selected independently of;</u><u style="single">R</u>^{<u style="single">4</u>}<u style="single">Are independent C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Alkyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Alkenyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Alkyne, C</u>_{<u style="single">3</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Cycloalkyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Haloalkyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Haloalkenyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Halo alkynyl, C</u>_{<u style="single">3</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Halocycloalkyl, halogen, CN, NO</u>_{<u style="single">2</u>}<u style="single">, Hydroxy, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkoxy, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Haloalkoxy, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkylthio, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkyl sulfinyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkylsulfonyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Haloalkylthio, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Haloalkyl sulfinyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Haloalkylsulfonyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkylamino, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">8</u>}<u style="single">Dialkylamino, C</u>_{<u style="single">3</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Cycloalkylamino, or C</u>_{<u style="single">3</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Trialkylsilyl; or</u><u style="single">R</u>^{<u style="single">4</u>}<u style="single">Are independently phenyl, benzyl or phenoxy rings, each ring being R</u>^{<u style="single">5</u>}<u style="single">Substituted with 1-3 substituents selected independently of;</u><u style="single">R</u>^{<u style="single">5</u>}<u style="single">Are independently H and C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkenyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkyne, C</u>_{<u style="single">3</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Cycloalkyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Haloalkyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Haloalkenyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Halo alkynyl, C</u>_{<u style="single">3</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Halocycloalkyl, halogen, CN, NO</u>_{<u style="single">2</u>}<u style="single">, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkoxy, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Haloalkoxy, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkylthio, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkyl sulfinyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkylsulfonyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkylamino, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">8</u>}<u style="single">Dialkylamino, C</u>_{<u style="single">3</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Cycloalkylamino, C</u>_{<u style="single">4</u>}<u style="single">~ C</u>_{<u style="single">7</u>}<u style="single">(Alkyl) Cycloalkylamino, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkylcarbonyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Alkoxycarbonyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Alkylaminocarbonyl, C</u>_{<u style="single">3</u>}<u style="single">~ C</u>_{<u style="single">8</u>}<u style="single">Dialkylaminocarbonyl or C</u>_{<u style="single">3</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Trialkylsilyl;</u><u style="single">R</u>^{<u style="single">6</u>}<u style="single">Are independently H and C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Alkyl, C</u>_{<u style="single">3</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Cycloalkyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Haloalkyl, halogen, CN, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkoxy, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Haloalkoxy, or C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Haloalkylthio;</u><u style="single">R</u>^{<u style="single">7</u>}<u style="single">Is H, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Alkyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Haloalkyl, C</u>_{<u style="single">3</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Alkenyl, C</u>_{<u style="single">3</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Haloalkenyl, C</u>_{<u style="single">3</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Alkyne or C</u>_{<u style="single">3</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Halo alkynyl;</u><u style="single">n is an integer from 1 to 4)</u><u style="single">Compounds, and their N-oxides and salts thereof.</u><u style="single">2.</u><u style="single">A is O;</u><u style="single">G consists of G-1, G-2, G-3, G-4, G-5, G-6, G-7 and G-43.</u><u style="single">Each G is selected from the group of 1 to 4 R</u>^{<u style="single">2</u>}<u style="single">Replaced in some cases</u><chemistry num="64"><img file="JP4445751B2_D0184.tif" /></chemistry><u style="single">Q is O, S or NR</u>^{<u style="single">2</u>}<u style="single">Is;</u><u style="single">W, X, Y and Z are independently N or CR</u>^{<u style="single">2</u>}<u style="single">However, to G-4 and G-5</u><u style="single">At least one of W, X, Y or Z is N;</u><u style="single">Q</u>^{<u style="single">1</u>}<u style="single">Is O, S or NR</u>^{<u style="single">3</u>}<u style="single">Is;</u><u style="single">W</u>^{<u style="single">1</u>}<u style="single">, X</u>^{<u style="single">1</u>}<u style="single">, Y</u>^{<u style="single">1</u>}<u style="single">And Z</u>^{<u style="single">1</u>}<u style="single">Is independently N or CR</u>^{<u style="single">3</u>}<u style="single">However, in J-3 and J-4, W</u>^{<u style="single">1</u>}<u style="single">, X</u>^{<u style="single">1</u>}<u style="single">, Y</u>^{<u style="single">1</u>}<u style="single">Or Z</u>^{<u style="single">1</u>}<u style="single">At least one of is N;</u><u style="single">R</u>^{<u style="single">3</u>}<u style="single">Are independently H and C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Haloalkyl, halogen, CN, NO</u>_{<u style="single">2</u>}<u style="single">, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkoxy, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Haloalkoxy, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkylthio, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkyl sulfinyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkylsulfonyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Haloalkylthio, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Haloalkyl sulfinyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Haloalkylsulfonyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkoxycarbonyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Alkylaminocarbonyl or C</u>_{<u style="single">3</u>}<u style="single">~ C</u>_{<u style="single">8</u>}<u style="single">Dialkylaminocarbonyl; or</u><u style="single">R</u>^{<u style="single">3</u>}<u style="single">Are independently phenyl, benzyl or 5- or 6-membered aromatic heterocycles.</u><u style="single">Each ring is R</u>^{<u style="single">5</u>}<u style="single">Substituted with 1-3 substituents selected independently of;</u><u style="single">1 R</u>^{<u style="single">4</u>}<u style="single">The group is attached to the rest of formula I at either the 2- or 5-position of the phenyl ring and is pre-linked.</u><u style="single">Note R</u>^{<u style="single">4</u>}<u style="single">Is C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Haloalkyl, halogen, CN, NO</u>_{<u style="single">2</u>}<u style="single">, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkoxy, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Haloalkoxy, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkylthio, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkyl sulfinyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkylsulfonyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Haloalkylthio, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Haloalkylsulfinyl or C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Haloalkylsulfonyl;</u><u style="single">m is an integer from 0 to 4,</u><u style="single">The compound according to the first item.</u><u style="single">3.</u><u style="single">R</u>^{<u style="single">1</u>}<u style="single">Is H or C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Alkyl;</u><u style="single">R</u>^{<u style="single">3</u>}<u style="single">The groups are independent H and C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Haloalkyl, halogen, CN, NO</u>_{<u style="single">2</u>}<u style="single">, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkoxy, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Haloalkoxy, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkylthio, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkyl sulfinyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkylsulfonyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Haloalkylthio, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Haloalkyl sulfinyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Haloalkylsulfonyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkoxycarbonyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Alkylaminocarbonyl, C</u>_{<u style="single">3</u>}<u style="single">~ C</u>_{<u style="single">8</u>}<u style="single">Dialkylaminocarbonyl; or phenyl, benzyl, or 5- or 6-membered aromatic heterocycle, each ring of halogen, CN, NO</u>_{<u style="single">2</u>}<u style="single">, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkenyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkyne, C</u>_{<u style="single">3</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Cycloalkyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Haloalkyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkoxy or C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Occasionally replaced with haloalkoxy;</u><u style="single">n is 1 or 2,</u><u style="single">The compound according to the second item.</u><u style="single">4.</u><u style="single">R</u>^{<u style="single">1</u>}<u style="single">Is H;</u><u style="single">1 R</u>^{<u style="single">4</u>}<u style="single">Is NR</u>^{<u style="single">1</u>}<u style="single">Bonded to the rest of formula I at the 2-position of the ortho phenyl ring with respect to the C (= A) J moiety and C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">3</u>}<u style="single">Alkyl, CF</u>_{<u style="single">3</u>}<u style="single">, OCF</u>_{<u style="single">3</u>}<u style="single">, OCHF</u>_{<u style="single">2</u>}<u style="single">, S (O)</u>_{<u style="single">p</u>}<u style="single">CF</u>_{<u style="single">3</u>}<u style="single">, S (O)</u>_{<u style="single">p</u>}<u style="single">CHF</u>_{<u style="single">2</u>}<u style="single">And optionally a second R selected from the group consisting of halogens</u>^{<u style="single">4</u>}<u style="single">Is NR</u>^{<u style="single">1</u>}<u style="single">Bonded to the C (= A) J moiety at the 4-position of the para-phenyl ring and halogen, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">3</u>}<u style="single">Alkyl and C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">3</u>}<u style="single">Selected from the group consisting of haloalkyl;</u><u style="single">p is 0, 1 or 2,</u><u style="single">The compound according to the third item.</u><u style="single">5.</u><u style="single">R</u>^{<u style="single">3</u>}<u style="single">Is H, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Haloalkyl, or</u><chemistry num="65"><img file="JP4445751B2_D0185.tif" /></chemistry><u style="single">Is;</u><u style="single">V is N, CH, CF, CCl, CBr or CI;</u><u style="single">R</u>^{<u style="single">5</u>}<u style="single">Are independently H and C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Alkyl, C</u>_{<u style="single">3</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Cycloalkyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">Haloalkyl, halogen, CN, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkoxy, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Haloalkoxy or C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">The compound according to the above item 4, which is a haloalkylthio.</u><u style="single">6.</u><u style="single">The compound according to item 5, wherein V is N.</u><u style="single">7.</u><u style="single">The compound according to the above item 5, wherein V is CH, CF, CCl or CBr.</u><u style="single">8.</u><u style="single">R</u>^{<u style="single">5</u>}<u style="single">Is H, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Alkyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">4</u>}<u style="single">Haloalkyl, halogen or CN;</u><u style="single">R</u>^{<u style="single">6</u>}<u style="single">Is H, CH</u>_{<u style="single">3</u>}<u style="single">, CF</u>_{<u style="single">3</u>}<u style="single">, OCH</u>_{<u style="single">2</u>}<u style="single">CF</u>_{<u style="single">3</u>}<u style="single">, OCHF</u>_{<u style="single">2</u>}<u style="single">Or halogen;</u><u style="single">R</u>^{<u style="single">7</u>}<u style="single">Is CH</u>_{<u style="single">2</u>}<u style="single">CF</u>_{<u style="single">3</u>}<u style="single">, CHF</u>_{<u style="single">2</u>}<u style="single">Or CF</u>_{<u style="single">3</u>}<u style="single">Is,</u><u style="single">The compound according to the sixth or seventh item.</u><u style="single">9.</u><u style="single">R</u>^{<u style="single">3</u>}<u style="single">Replaced by, and optionally R</u>^{<u style="single">6</u>}<u style="single">J replaced by is J-5; R</u>^{<u style="single">5</u>}<u style="single">Is Cl or Br; R</u>^{<u style="single">6</u>}<u style="single">Is halogen, OCH</u>_{<u style="single">2</u>}<u style="single">CF</u>_{<u style="single">3</u>}<u style="single">, OCHF</u>_{<u style="single">2</u>}<u style="single">Or CF</u>_{<u style="single">3</u>}<u style="single">The compound according to the above item 8.</u><u style="single">10.</u><u style="single">R</u>^{<u style="single">3</u>}<u style="single">Replaced by, and optionally R</u>^{<u style="single">7</u>}<u style="single">J replaced by is J-6; R</u>^{<u style="single">9</u>}<u style="single">Is Cl or Br; R</u>^{<u style="single">7</u>}<u style="single">Is CH</u>_{<u style="single">2</u>}<u style="single">CF</u>_{<u style="single">3</u>}<u style="single">, CHF</u>_{<u style="single">2</u>}<u style="single">Or CF</u>_{<u style="single">3</u>}<u style="single">The compound according to the above item 8.</u><u style="single">11.</u><u style="single">R</u>^{<u style="single">3</u>}<u style="single">Replaced by, and optionally R</u>^{<u style="single">7</u>}<u style="single">J replaced by is J-7; R</u>^{<u style="single">9</u>}<u style="single">Is Cl or Br; R</u>^{<u style="single">7</u>}<u style="single">Is CH</u>_{<u style="single">2</u>}<u style="single">CF</u>_{<u style="single">3</u>}<u style="single">, CHF</u>_{<u style="single">2</u>}<u style="single">Or CF</u>_{<u style="single">3</u>}<u style="single">The compound according to the above item 8.</u><u style="single">12.</u><u style="single">R</u>^{<u style="single">3</u>}<u style="single">Replaced by, and optionally R</u>^{<u style="single">6</u>}<u style="single">J replaced by is J-8; R</u>^{<u style="single">5</u>}<u style="single">Is Cl or Br; R</u>^{<u style="single">6</u>}<u style="single">Is halogen, OCH</u>_{<u style="single">2</u>}<u style="single">CF</u>_{<u style="single">3</u>}<u style="single">, OCHF</u>_{<u style="single">2</u>}<u style="single">Or CF</u>_{<u style="single">3</u>}<u style="single">The compound according to the above item 8.</u><u style="single">13.</u><u style="single">R</u>^{<u style="single">3</u>}<u style="single">Replaced by, and optionally R</u>^{<u style="single">6</u>}<u style="single">And R</u>^{<u style="single">7</u>}<u style="single">J replaced by is J-9; R</u>^{<u style="single">5</u>}<u style="single">Is Cl or Br; R</u>^{<u style="single">6</u>}<u style="single">Is halogen, OCH</u>_{<u style="single">2</u>}<u style="single">CF</u>_{<u style="single">3</u>}<u style="single">, OCHF</u>_{<u style="single">2</u>}<u style="single">Or CF</u>_{<u style="single">3</u>}<u style="single">Is; R</u>^{<u style="single">7</u>}<u style="single">Is CH</u>_{<u style="single">2</u>}<u style="single">CF</u>_{<u style="single">3</u>}<u style="single">, CHF</u>_{<u style="single">2</u>}<u style="single">Or CF</u>_{<u style="single">3</u>}<u style="single">The compound according to the above item 8.</u><u style="single">14.</u><u style="single">R</u>^{<u style="single">3</u>}<u style="single">Replaced by, and optionally R</u>^{<u style="single">7</u>}<u style="single">J replaced by is J-10; R</u>^{<u style="single">9</u>}<u style="single">Is Cl or Br; R</u>^{<u style="single">7</u>}<u style="single">Is CH</u>_{<u style="single">2</u>}<u style="single">CF</u>_{<u style="single">3</u>}<u style="single">, CHF</u>_{<u style="single">2</u>}<u style="single">Or CF</u>_{<u style="single">3</u>}<u style="single">The compound according to the above item 8.</u><u style="single">15.</u><u style="single">1- (3-Chloro-2-pyridinyl) -N- [2- (1H-imidazol-2-yl)</u><u style="single">-6-Methylphenyl] -3- (Trifluoromethyl) -1H-Pyrazole-5-Carbo</u><u style="single">Kisamide,</u><u style="single">1-(2-Methyl-N- [2-Methyl-6- (1-Methyl-1H-Imidazole-</u><u style="single">2-Il) Phenyl] -3- (Trifluoromethyl) -1H-pyrazole-5-carboki</u><u style="single">Samide,</u><u style="single">1- (2-Chlorophenyl) -N- [2- (4,5-dihydro-1-methyl-1H-Imi</u><u style="single">Dazole-2-yl) -6-methylphenyl] -3- (trifluoromethyl) -1H-pi</u><u style="single">Razole-5-carboxamide,</u><u style="single">1- (3-Chloro-2-pyridinyl) -N- [2- (4,5-dihydro-1-methyl-1)</u><u style="single">H-imidazol-2-yl) -6-methylphenyl] -3- (trifluoromethyl)-</u><u style="single">1H-pyrazole-5-carboxamide,</u><u style="single">N- [4-Bromo-2- (4,5-dihydro-1-methyl-1H-imidazol-2-i)</u><u style="single">Le) -6-methylphenyl] -1- (2-chlorophenyl) -3- (trifluoromethyl)</u><u style="single">) -1H-pyrazole-5-carboxamide,</u><u style="single">N- [4-Bromo-2- (4,5-dihydro-1-methyl-1H-imidazol-2-i)</u><u style="single">Lu) -6-methylphenyl] -1- (3-chloro-2-pyridinyl) -3- (trifluo)</u><u style="single">Lomethyl) -1H-pyrazole-5-carboxamide,</u><u style="single">1- (3-Chloro-2-pyridinyl) -N- [2- (4,5-dihydro-2-oxazoli)</u><u style="single">Le) -6-methylphenyl] -3- (trifluoromethyl) -1H-pyrazole-5-ca</u><u style="single">Luboxamide, and</u><u style="single">1- (3-chloro-2-pyridinyl) -N- [2,4-dichloro-6- (4,5-dichloromethane)</u><u style="single">B-1H-imidazol-2-yl) phenyl] -3- (trifluoromethyl) -1H-</u><u style="single">The compound according to the above item 1, which is selected from the group consisting of pyrazole-5-carboxamide.</u><u style="single">16.</u><u style="single">A method for controlling an invertebrate pest, which comprises contacting the invertebrate pest or its environment with a biologically effective amount of the compound according to the first paragraph, its N-oxide or an appropriate salt thereof.</u><u style="single">17.</u><u style="single">Apply at least one additional compound or drug to control invertebrate pests</u><u style="single">The method according to the above paragraph 16, further comprising the above.</u><u style="single">18.</u><u style="single">An invertebrate comprising a biologically effective amount of the compound according to paragraph 1 and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents. A composition for controlling pests.</u><u style="single">19.</u><u style="single">Further containing at least one additional compound or drug for controlling invertebrate pests</u><u style="single">The composition according to item 18 above.</u>