To provide novel carboxamides which exhibit an excellent pesticidal activity as pesticides. Carboxamides represented by the following Formula (I) and use thereof as pesticides and an animal parasite control agent:wherein each substituent is as defined in the specification.

TECHNICAL FIELD

The present invention relates to pesticidal carboxamides and their use as a pesticide.

BACKGROUND ART

In Patent Documents 1 to 17, it is described that pesticidal carboxamide compounds are useful as an agent for controlling harmful organisms.

PRIOR ART LITERATURES

Patent Documents

SUMMARY OF THE INVENTION

Inventors of the present invention extensively studied to develop novel compounds which are highly active as pesticides and have a broad spectrum use. As a result, the inventors found that the novel carboxamides represented by the following Formula (I) have a high activity, a broad spectrum use and safety, and also are effective against harmful pests that are resistant to organic phosphorous agents or carbamate agents.

wherein,D represents a 6-membered aromatic carbon ring which may be substituted or a 5- to 6-membered aromatic heterocycle which may be substituted;A1, A2, A3and A4each independently represent nitrogen, C—X2or the following Formula (E):

The compounds of the Formula (I) of the present invention can be obtained according to the following preparation methods (a) to (f), for example.

Preparation Method (a)

A method in which compounds represented by the Formula (II):

wherein, X1, m and D are as defined above, A1-1, A2-1A3-1and A4-1represent nitrogen, C—X2or C—C(═O)-L1, at least one of A1-1, A2-1, A3-1and A4-1represents C—C(═O)-L1, X2is as defined above, and L1represents hydroxy or an appropriate leaving group, for example, chlorine, bromine, a C1-4alkyl-carbonyloxy group, a C1-4alkoxy-carbonyloxy group, an azolyl group, a C1-4alkylsulfonyloxy group, a C1-4haloalkylsulfonyloxy group, or an arylsulfonyloxy groupare reacted with compounds represented by the Formula (III):

wherein, B1to B5are as defined abovein the presence of a condensing agent, a base, or an appropriate diluent, if necessary.
Preparation Method (b)

A method in which compounds represented by the Formula (I-a):

wherein, A1to A4, X1, m, and D are as defined above, L represents 1, 2, 3 or 4, Hal represents halogen, for example, iodine, chlorine, bromine.are reacted with a cyanation reagent in the presence of an appropriate catalyst to obtain the compounds represented by the following Formula (I-b):

wherein, A1to A4, X1, m, L and D are as defined above and NC represents a cyano group.
Preparation Method (c-1)

A method in which compounds represented by the Formula (I-c-1):

wherein, A1to A4and X1are as defiled above.are reacted with a halogenation reagent to obtain the compounds represented by the following Formula (I-d-1) and/or Formula (I-d-2):

wherein, A1to A4and X1are as defined above and Hal represents halogen.
Preparation Method (c-2)

A method in which compounds represented by the Formula (I-c-2):

wherein, A1to A4and X1are as defined above, with the proviso that X1is not hydrogen.are reacted with a halogenation reagent to obtain the compounds represented by the following Formula (I-d-3):

wherein, A1to A4and X1are as defined above and Hal represents halogen, with the proviso that X1is not hydrogen.
Preparation Method (c-3)

A method in which compounds represented by the Formula (I-c-3):

wherein, A1to A4and X1are as defined above, with the proviso that X1is not a hydrogen atom.are reacted with a halogenation reagent to obtain the compounds represented by the following Formula (I-d-4):

wherein, A1to A4and X1are as defined above and Hal represents halogen, with the proviso that X1is not a hydrogen atom.
Preparation Method (c-4)

A method in which compounds represented by the Formula (I-c-4):

wherein, A2to A4and X1are as defined above.are reacted with a halogenation reagent to obtain the compounds represented by the following Formula (I-d-5):

wherein, A2to A4and X1are as defined above and Hal represents halogen.
Preparation Method (d)

A method in which compounds represented by the Formula (I-c-2):

wherein, A1to A4and X1are as defined above.are reacted with a cyanation reagent in the presence of an appropriate diluent to obtain the compounds represented by the following Formula (I-e):

wherein, A1to A4and X1are as defined above and NC represents a cyano group.
Preparation Method (e)

A method in which compounds represented by the Formula (I-f):

at least one of A1-2, A2-2, A3-2and A4-2represents the Formula (E1),and X2, G and B1to B5are as defined aboveare reacted with compounds represented by the following Formula (FV):
Q-L2(IV)
wherein, Q is as defined above, and L2represents fluorine, chlorine, bromine, a C1-4alkyl-carbonyloxy group, a C1-4alkoxy-carbonyloxy group, an azolyl group, a C1-4alkylsulfonyloxy group, a C1-4haloalkylsulfonyloxy group, or an arylsulfonyloxy groupin the presence of a base and an appropriate diluent, if necessary.
Preparation Method (f)

A method in which compounds represented by the Formula (I-g):

wherein, X1, m and D are as defined above and A1-2, A2-2, A3-2and A4-2represent nitrogen, C—X2or the following Formula (E2):

at least one of A1-2, A2-2, A3-2and A4-2represents the Formula (E2) and X2, Q and B1to B5are as defined above are reacted with an appropriate sulfurization reagent in the presence of an appropriate diluent.
Preparation Method (g)

A method in which compounds represented by the Formula (V):

wherein, A1to A4are as defined above and Hal′ stands for bromo or Iodo,is reacted with CuI to obtain the compounds represented by the following Formula (I-g-1):

According to the present invention, carboxamides of the Formula (I) of the present invention have a potent pesticidal activity.

In the present specification, “alkyl” represents linear or branched C1-12alkyl such as methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl. Preferably, it represents C1-6alkyl, and more preferably C1-4alkyl. Further, for each alkyl moiety included in a group which includes the alkyl as a part of its constitution, those that are the same as “alkyl” described above can be exemplified.

“Haloalkyl” represents carbon chains in which at least one hydrogen of linear or branched C1-12alkyl, preferably C1-6alkyl, more preferably C1-4alkyl is substituted with halogen, for example, CH2F, CHF2, CF3, CF2Cl, CFCl2, CF2Br, CF2CF3, CFHCF3, CH2CF3, CFClCF3, CCl2CF3, CF2CH3, CF2CH2F, CF2CHF2, CF2CF2Cl, CF2CF2Br, CFHCH3, CFHCHF2, CFHCHF2, CHFCF3, CHFCF2Cl, CHFCF2Br, CFClCF3, CCl2CF3, CF2CF2CF3, CH2CF2CF3, CF2CH2CF3, CF2CF2CH3, CHFCF2CF3, CF2CHFCF3, CF2CF2CHF2, CF2CF2CH2F, CF2CF2CF2Cl, CF2CF2CF2Br, CH(CF3)CF3, CF(CF3)CF3, CF(CF3)CF2Br, CF2CF2CF2CF3, CH(CF3)CF2CF3or CF(CF3)CF2CF3. It also includes perfluoroalkyl in which every substitutable hydrogen on alkyl is substituted with fluorine. Furthermore, monobromoperfluoroalkyl is also included in haloalkyl, and it represents an alkyl in which one of the substitutable hydrogens is substituted by bromo while all the remaining substitutable hydrogens are substituted by fluoro. The haloalkyl may be also substituted with any substituent.

“Alkoxy” represents alkoxy of linear or branched C1-12, preferably C1-6, more preferably C1-4, for example, methoxy, ethoxy, n-propoxy, i-propoxy, n-, iso-, sec- or tert-butoxy, pentyloxy or hexyloxy. The alkoxy may be also substituted with any substituent.

Each “halogen” and a halogen moiety included in a group substituted with halogen represent fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.

“Cycloalkyl” represents C3-8cycloalkyl including cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, preferably C3-7cycloalkyl, and more preferably C3-6cycloalkyl. Further, for each cycloalkyl moiety included in a group which has cycloalkyl as a part of constitution, those that are the same as “cycloalkyl” described above can be exemplified.

“Heterocycle” represents a 3-, 4-, 5- or 6-membered heterocyclic group which includes at least one of heteroatoms N, O and S, or the cycle represents a fused heterocyclic group which may be benzo-fused. The carbon atom included in the cycle may be substituted with oxo or thioxo.

Among the compounds of the Formula (I) of the present invention, the compounds which satisfy the followings can be mentioned as preferred examples.D represents any one of the following Formulae D-1 to D-16, preferably stands for D-9, D-10 or D-16:

which may be substituted by (X1)m,A1, A2, A3and A4each independently represent nitrogen, C—X2or the following Formula (E), preferably A1, A2and A4each independently represent nitrogen or C—X2and A3stands for the following Formula (E):

More preferably J stands for one of groups:

m and n each independently represent an integer from 1 to 4; and

Each group defined above may be further substituted with any substituent.

Among these compounds represented by the Formula (I), the compounds which satisfy the followings can be mentioned as more preferred examples:D represents any one of the following Formulae D-1 to D-16, preferably stands for D-9, D-10 or D-16:

which may be substituted by (X1)m,A1, A2, A3and A4each independently represent nitrogen, C—X2or the following Formula (E), preferably A1, A2and A4each independently represent C—X2and A3stands for the following Formula (E):

More preferably J stands for one of groups:

m and n each independently represent an integer from 1 to 4; and

Each group defined above may be further substituted with any substituent.

Among the compounds of the Formula (I) of the present invention, the compounds which satisfy the followings can be mentioned as another preferred aspect of the invention.D stands for D-9, D-10 or D-16:

which may be substituted by (X1)m,A1, A2and A4each independently represent C—X2and A3stands for the following Formula (E):

Z each independently represents halogen,k is an integer from 1 to 4,J4represents C1-4alkyl, or phenyl,m and n each independently represent an integer from 1 to 4; andeach group defined above may be further substituted with any substituent.

Following groups of the novel carboxamides are also preferred, and in any case they are understood as subgroups of the compounds of the Formula (I) described above.

Group 1: Carboxamides Represented by the Formula (I-I):

wherein, X2, Q and J are as defined above, R1, R2, R4and R5each independently have the same meaning as X3described above, R7, R8, R9and R10each independently have the same meaning as X1described above and n″ stands for 1, 2 or 3.
Group 2: Carboxamides Represented by the Formula (I-II):

wherein, X2, Q, J and n″ are as defined above, R1, R2, R4and R5each independently have the same meaning as X3described above, R7, R8and R9each independently have the same meaning as X1described above and n′ is 0 or 1.

The compounds of the Formula (I) of the present invention may have an asymmetric carbon, and therefore optical isomers are included in such compounds.

Group 4: Carboxamides Represented by the Formula (I-IV):

wherein, X2, Q and J are as defined above, R1, R2, R4and R5each independently have the same meaning as X3described above, R9each independently have the same meaning as X1described above and n″ stands for 1, 2 or 3.

Preparation method (a) can be depicted as the following reaction formula when 6-bromo-2-naphthoyl chloride and 2-ethyl-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-methylaniline are used as reacting materials.

Preparation method (b) can be depicted as the following reaction formula when 6-bromo-N-[2-ethyl-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-methylphenyl]-2-naphthamide, zinc cyanide and tetrakis(triphenylphosphine)palladium (0) are used as reacting materials.

Preparation method (c-1) can be depicted as the following reaction formula when N-[4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2,6-dimethyl-phenyl]quinoline-6-carboxamide-1-oxide and phosphorus oxychloride are used as reacting materials.

Preparation method (d) can be depicted as the following reaction formula when N-[4-(1,1,1,2,2,3,3-heptafluoropropan-2-yl)-2,6-dimethyl-phenyl]quinoline-6-carboxamide-1-oxide and trimethylsilylnitrile are used as reacting materials.

Preparation method (e) can be depicted as the following reaction formula when 6-bromo-N-[2-ethyl-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl-2-yl)-6-methylphenyl]-2-naphthamide and methyl iodide are used as reacting materials.

Preparation method (f) can be depicted as the following reaction formula when 6-bromo-N-[2-ethyl-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-methylphenyl]-2-naphthamide and a Lawesson reagent are used as reacting materials.

Preparation method (g) can be depicted as the following reaction formula when 3-bromo-4-[(4-chloro-5H-1,2,3-dithiazol-5-yl)amino]-N-[2-ethyl-6-methyl-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)phenyl]cyclohexa-1,5-diene-1-carboxamide and CuI are used as reacting materials.

Descriptions about Each Preparation Method and Intermediates

When L1represents hydroxy in the starting materials of the Formula (II) for the Preparation method (a), they can be reacted with the compounds of the Formula (III) in the presence of a condensing agent.

When L1represents hydroxy in the starting materials of the Formula (II) for the Preparation method (a), L1can be easily converted to an appropriate substituent by several methods including, pre-reacting with a chlorination agent such as thionyl chloride, oxalyl chloride or phosphorous pentachloride, reacting with an organic acid halide such as pyvaloyl chloride, or reacting with carbonyldiimidazole or sulfonylimidazole and the like.

As a reacting material for the Preparation method (a), some of the compounds having the Formula (III) are known and they can be synthesized according to the methods that are described in US2002/0198399A1, EP1006102A, JP2003-335735A, WO2005/021488A1, WO2005/073165A1, WO2006/137395A, JP2004-161767A or WO2006/024412A2. As a representative example of the known compounds, the followings can be mentioned.4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2,6-dimethylaniline,2-ethyl-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-methylaniline,2,6-diethyl-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)aniline,2-bromo-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-methylaniline,2-bromo-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-ethylaniline,2,6-dichloro-4-(1,1,1,2,3,3,3-heptafluoroptopan-2-yl)aniline,2,6-dibromo-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)aniline,4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2,6-diiodoaniline,4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2-(trifluoromethyl)aniline,2-chloro-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-(trifluoromethyl)aniline,2-bromo-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-(trifluoromethyl)aniline,4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2-iodo-6-(trifluoromethyl)aniline,4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2-(trifluoromethyl)aniline,2-chloro-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-(trifluoromethoxy)aniline,2-bromo-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-(trifluoromethoxy)aniline,4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2-iodo-6-(trifluoromethoxy)aniline,4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2-[(trifluoromethyl)sulfanyl]aniline,4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2-[(trifluoromethyl)sulfinyl]aniline,4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2-yl)-6-[(trifluoromethyl)sulfonyl]aniline,2-chloro-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-[(trifluoromethyl)sulfanyl]aniline,2-chloro-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-[(trifluoromethyl)sulfinyl]aniline,2-chloro-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-[(trifluoromethyl)sulfonyl]aniline.2-bromo-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-[(trifluoromethyl)sulfanyl]aniline,2-bromo-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-[(trifluoromethyl)sulfinyl]aniline,2-bromo-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-[trifluoromethyl)sulfonyl]aniline,4-(1,1,1,2,3,3,3-heptafluoroproan-2-yl)-2-iodo-6-[(trifluoromethyl)sulfanyl]aniline,4-(1,1,1,2,3,3,3-heptafluoroproan-2-yl)-2-iodo-6-[(trifluoromethyl)sulfinyl]aniline,4-(1,1,1,2,3,3,3-heptafluoroproan-2-yl)-6-iodo-4-[(trifluoromethyl)sulfonyl]aniline,2-ethyl-4-(2-ethoxy-1,1,1,3,3,3-hexafluoropropan-2-yl)-6-methylaniline4-[2-(4-chlorophenoxy)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-ethyl-6-methylaniline,4-[2-(4-chloro-1H-pyrazole-1-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-ethyl-6-methylaniline,4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-2,6-dimethylaniline,2-ethyl-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-6-methylaniline,2,6-dichloro-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)aniline,2,6-dibromo-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)aniline,4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-2,6-diiodoaniline4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-2-(trifluoromethyl)aniline,2-chloro-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-6-(trifluoromethyl)aniline,2-bromo-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-6-(trifluoromethyl)aniline,4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-2-iodo-6-(trifluoromethyl)aniline,4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-2-(trifluoromethoxy)aniline,2-chloro-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-6-(trifluoromethoxy)aniline,2-bromo-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-6-(trifluoromethoxy)aniline,4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2-iodo-6-(trifluoromethoxy)aniline,4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-2-[(trifluoromethyl)sulfanyl]aniline,4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-2-[(trifluoromethyl)sulfinyl]aniline,4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-2-[(trifluoromethyl)sulfonyl]aniline,2-chloro-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-6-[(trifluoromethyl)sulfanyl]aniline,2-chloro-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-6-[(trifluoromethyl)sulfinyl]aniline,2-chloro-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-6-[(trifluoromethyl)sulfonyl]aniline,2-bromo-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-6-[(trifluoromethyl)sulfanyl]aniline,2-bromo-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-6-[(trifluoromethyl)sulfinyl]aniline,2-bromo-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-6-[(trifluoromethyl)sulfonyl]aniline,4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-2-iodo-6-[(trifluoromethyl)sulfanyl]aniline,4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-2-iodo-6-[(trifluoromethyl)sulfinyl]aniline,4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-2-iodo-6-[(trifluoromethyl)sulfonyl]aniline,2-ethyl-4-[2-ethoxy-1,1,1,3,3,4,4,4-octafluorobutan-2-yl]-6-methylaniline,4-[2-(4-chlorophenoxy)-1,1,1,3,3,4,4,4-octafluorobutan-2-yl]-2-ethyl-6-methylaniline,4-[2-(4-chloro-1H-pyrazol-1-yl)-1,1,1,3,3,4,4,4-octafluorobutan-2-yl]-2-ethyl-6-methylaniline,2,6-dibromo-4-(trifluoromethoxy)aniline,2,6-dibromo-4-[(trifluoromethyl)sulfanyl]aniline,2,6-dibromo-4-[(trifluoromethyl)sulfinyl]aniline,2,6-dibromo-4-[(trifluoromethyl)sulfonyl]aniline,2,6-dibromo-4-[(pentafluoroethyl)sulfanyl]aniline,2,6-dibromo-4-[(heptafluoropropyl)sulfanyl]aniline,2,6-dibromo-4-[(nonafluorobutyl)sulfanyl]aniline,4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)aniline,4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-2-methylaniline, and the like.

Furthermore, with respect to the compounds having the Formula (III) as a reacting material for the Preparation method (a), those that fall within the concept of the patent literatures, i.e., JP2004-161767A and WO2006/024412A2, but can be mentioned as a novel compound are as follows.4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-2,6-dimethylaniline4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-2-ethyl-6-methylaniline2,6-dichloro-4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)aniline2,6-dichloro-4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)aniline4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-2,6-diiodoaniline,4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-2-(difluoromethyl)aniline,2-chloro-4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-6-(difluoromethyl)aniline,2-bromo-4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-6-(difluoromethyl)aniline,4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-2-iodo-6-(difluoromethyl)aniline,4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-2-trifluoromethyl)aniline,2-chloro-4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-6-(trifluoromethyl)aniline,2-bromo-4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-6-(rifluoromethyl)aniline,4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-2-iodo-6-(trifluoromethyl)aniline,4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-2(difluoromethoxy)aniline,2-(difluoromethoxy))-4-(1-bromo-1,1,2,3,3,3-hexafloropropan-2-yl)-6-methylaniline,2-chloro-4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-6-(difluoromethoxy)aniline,2-bromo-4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-6-(difluoromethoxy)aniline,4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-2-iodo-6-(difluoromethoxy)aniline,4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-2-(trifluoromethoxy)aniline,2-chloro-4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-6-(trifluoromethoxy)aniline,2-bromo-4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-6-(trifluoromethoxy)aniline,4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-2-iodo-6-(trifluoromethoxy)aniline,4-(1-bromo-1,2,3,3,3-hexafluoropropan-2-yl)-2-[(difluoromethyl)sulfanyl]aniline,4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-2-[(difluoromethyl)sulfinyl]aniline,4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-2-[(difluoromethyl)sulfonyl]aniline,2-chloro-4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-6-[(difluoromethyl)sulfanyl]aniline,2-chloro-4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-6-[(difluoromethyl)sulfinyl]aniline,2-chloro-4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-6-[(difluoromethyl)sulfonyl]aniline,2-bromo-4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-6-[(difluoromethyl)sulfanyl]aniline,2-bromo-4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-6-[(difluoromethyl)sulfinyl]aniline,2-bromo-4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-6-[(difluoromethyl)sulfonyl]aniline,4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-2-iodo-6-[(difluoromethyl)sulfanyl]aniline,4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-2-iodo-6-[(difluoromethyl)sulfinyl]aniline,4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-2-iodo-6-[(difluoromethyl)sulfonyl]aniline,4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-2-[(trifluoromethyl)sulfanyl]aniline,4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-2-[(trifluoromethyl)sulfinyl]aniline,4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-2-[(trifluoromethyl)sulfonyl]aniline,2-chloro-4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-6-[(trifluoromethyl)sulfanyl]aniline,2-chloro-4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-6-[(trifluoromethyl)sulfinyl]aniline,2-chloro-4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-6-[(trifluoromethyl)sulfonyl]aniline,2-bromo-4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-6-[(trifluoromethyl)sulfanyl]aniline,2-bromo-4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-6-[(trifluoromethyl)sulfinyl]aniline,2-bromo-4 (1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-6-[(trifluoromethyl)sulfonyl]aniline,4-(1-bromo-1,1,2,3,3-hexafluoropropan-2-yl)-2-iodo-6-[(trifluoromethyl)sulfanyl]aniline,4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-2-iodo-6-[(trifluoromethyl)sulfinyl]aniline,4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-6-iodo-4-[(trifluoromethyl)sulfonyl]aniline.

It is expressed as follows:

wherein, R1-1and R5-1each independently represent hydrogen, halogen, C1-4alkyl, C1-4haloalkyl, C1-4haloalkoxy, C1-4haloalkylsulfanyl, C1-4haloalkylsulfinyl, C1-4haloalkylsulfonyl, with the proviso that the case is excluded where R1-1is hydrogen and R5-1is hydrogen, R1-1is hydrogen and R5-1is methyl, R1-1is hydrogen and R5-1is fluoro, R1-1is hydrogen and R5-1is chloro, or R1-1is hydrogen and R5-1is bromo. They can be synthesized according to the methods that are described in JP2004-161767A as shown below.

Furthermore, with respect to the compounds having the Formula (III) as a reacting material for the Preparation method (a), those that fall within the concept of the patent literatures, i.e. US2002/0198399A1, EP1006102A and JP2003-335735A, but can be mentioned as a novel compound are as follows.4-(1,1,1,2,3,3-heptafluoropropan-2-yl)-2-(difluoromethyl)aniline,2-chloro-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-(difluoromethyl)aniline,2-bromo-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-(difluoromethyl)aniline,4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2-iodo-6-(difluoromethyl)aniline,4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2-(difluoromethoxy)aniline,2-(difluoromethoxy)-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-methylaniline,2-chloro-4-(1,1,2,3,3,3-heptafluoropropan-2-yl)-6-(difluoromethoxy)aniline,2-bromo-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-(difluoromethoxy)aniline,4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2-iodo-6-(difluoromethoxy)aniline,4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2-[(difluoromethyl)sulfanyl]aniline,4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2-[(difluoromethyl)sulfinyl]aniline,4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2-[(difluoromethyl)sulfonyl]aniline2-chloro-4-(1,1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-[(difluoromethyl)sulfanyl]aniline,2-chloro-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-[(difluoromethyl)sulfinyl]aniline,2-chloro 4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-[(difluoromethyl)sulfonyl]aniline,2-bromo-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-[(difluoromethyl)sulfanyl]aniline,2-bromo-4-(1,1,1,2,3,3-heptafluoropropan-2-yl)-6-[(difluoromethyl)sulfinyl]aniline,2-bromo-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-[(difluoromethyl)sulfonyl]aniline,4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2-iodo-6-[(difluoromethyl)sulfanyl]aniline,4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2-iodo-6-[(difluoromethyl)sulfinyl]aniline,4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2-iodo-6-[(difluoromethyl)sulfonyl]aniline,4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-2-(difluoromethyl)aniline,2-chloro-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-6-(difluoromethyl)aniline,2-bromo-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-6-(difluoromethyl)aniline,4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-2-iodo-6-(difluoromethyl)aniline,4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-2-(difluoromethoxy)aniline,2-(difluoromethoxy)-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-6-methylaniline,2-chloro-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-6-(difluoromethoxy)aniline,2-bromo-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-6-(difluoromethoxy)aniline,4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-2-iodo-6-(difluoromethoxy)aniline,4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-2-[(difluoromethyl)sulfanyl]aniline,4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-2-[(difluoromethyl)sulfinyl]aniline,4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-2-[(difluoromethyl)sulfonyl]aniline,2-chloro-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-6-[(difluoromethyl)sulfanyl]aniline,2-chloro-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-6-[(difluoromethyl)sulfinyl]aniline,2-chloro-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-6-[(difluoromethyl)sulfonyl]aniline,2-bromo-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-6-[(difluoromethyl)sulfanyl]aniline,2-bromo-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-6-[(difluoromethyl)sulfinyl]aniline,2-bromo-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-6-[(difluoromethyl)sulfonyl]aniline,4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-2-iodo-6-[(difluoromethyl)sulfanyl]aniline,4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-2-iodo-6-[(difluoromethyl)sulfinyl]aniline,4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-2-iodo-6-[(difluoromethyl)sulfonyl]aniline

It is expressed as follows:

Furthermore, as novel compounds of the Formula (Ill), the followings can be mentioned,2,6-dimethyl-4-(undecafluorocyclohexyl)aniline2-ethyl-6-methyl-4-(undecafluorocyclohexyl)aniline2,6-dichloro-4-(undecafluorocyclohexyl)aniline2,6-dibromo-4-(undecafluorocyclohexyl)aniline2,6-diiodo-4-(undecafluorocyclohexyl)aniline, etc.,
and they are represented by the following formula:

The Preparation method (a) can be carried out within substantially wide temperature range. It may be generally carried out at the temperature between about −78° C. and about 200° C., preferably between −10° C. and about 150° C. Said reaction is preferably carried out at normal pressure although it may be carried out under elevated or reduced pressure. The reaction time is 0.1 to 72 hours, preferably 0.1 to 24 hours. For carrying out the Preparation method (a), for example, when L1represents hydroxy, 1 mol of the compound of the Formula (II) can be reacted with 1 to 3 mol of the compound of the Formula (III) using 1 to 3 mol of a condensing agent in a diluent, e.g., DMF to obtain the compounds of the Formula (I).

For carrying out the Preparation method (a), for example, when L1represents an appropriate leaving group, 1 mol of the compound of the Formula (II) can be reacted with 1 to 3 mol of the compound of the Formula (III) it the presence of an appropriate base, e.g., pyridine, to obtain the compounds of the Formula (I).

The compounds of the Formula (I-a) as reacting materials for the Preparation method (b) are encompassed by the compounds of the Formula (I) of the present invention and their representative examples are as follows:6-bromo-N-[2-ethyl-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-methylphenyl]-2-naphthamide,2-chloro-N-[4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2,6-dimethylphenyl]quilioline-6-carboxamide,2-chloro-N-[2-ethyl-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-methylphenyl]quinoline-6-carboxamide,4-bromo-N-[4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2,6-dimethylphenyl]quinoline-6-carboxamide, etc.

The reaction of the Preparation method (b) can be carried out in the presence of an appropriate diluent, and examples of the diluent which can be used are the same as the diluents exemplified for the Preparation method (a). Preferably, dimethylformamide (DMF) can be mentioned.

The reaction of the Preparation method (b) can be carried out in the presence of an appropriate catalyst, and examples of the catalyst which can be used include a transition metal, etc. such as Pd(PPh3)4, Pd2(dba)3, Pd2(dba)3CHCl3, (dba=dibenzylideneacetone), Pd(PPh3)2Cl2, Pd(OAc)2, CuI, CuCN, etc. Further if necessary, the reaction can be carried out by using a phosphine type ligand such as triphenylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,1′-bis(diphenylphosphino)ferrocene, 2,2′-bis(diphenylphosphino)-1,1′-binaphthalen (BINAP), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (Xantphos), tributylphosphine, etc.

Among cyanation reagents which can be used for the reaction of the Preparation method (b), representative examples include zinc cyanide, sodium cyanide, potassium cyanide, silver (I) cyanide, copper (I) cyanide, trimethylsilyl cyanide, potassium hexacyanoiron (II) acid trihydrate,

The Preparation method (b) can be carried out within substantially wide temperature range. It may be generally carried out at the temperature between about 0° C. and about 200° C., preferably between 30° C. and about 180° C. Said reaction is preferably carried out at normal pressure although it may be carried out under elevated or reduced pressure. The reaction time is 0.1 to 72 hours, preferably 0.1 to 24 hours.

For carrying out the Preparation method (b), for example, 1 mol of the compound of the Formula (I-a) can be reacted With 0.5 to 3 mol of a cyanation reagent, e.g., zinc cyanide, in the presence of catalytic amount of Pd(PPh3)4in a diluent such as DMF to obtain the compounds of the Formula (I-h) that are encompassed by the compounds of the Formula (I) of the present invention.

Preparation methods (c-1), (c-2) and (c-3) can be carried out according to the methods described in the literatures (Bioorganic & Medicinal Chemistry 2005, 13, 1487-1496 or WO 2007/133637 A2).

The compounds of the Formula (I-c-1) as reacting materials for the Preparation method (c-1) can be obtained by oxidizing the compounds represented by the following Formula (I-c-5):

with an appropriate oxidizing agent, for example, 3-chloroperbenzoic acid, a combination of trifluoroacetic anhydride and urea-hydrogen peroxide adduct (literature; Tetrahedron Letters, 2000, 41, 2299-2302) and the like.

The compounds of the Formula (I-c-5) are encompassed by the compounds of the Formula (I) of the present invention and they can be synthesized according to the Preparation method (a). Representative examples of the compounds of the Formula (I-c-5) are as ibilows:N-[4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2,6-dimethylphenyl]quinoline-6-carboxamide,N-[2-ethyl-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-methylphenyl]quinoline-6-carboxamide,N-[2,6-dibromo-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)phenyl]quinoline-6-carboxamide,N-[4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2,6-diiodophenyl]quinoline-6-carboxamide, etc.

Among halogenation reagents which can be used for the reaction of the Preparation method (c-1), representative examples include phosphorus oxychloride, phosphorus pentachloride, and phosphorus oxybromide.

Temperature range, pressure and time for the reaction of the Preparation method (c-1) are the same as the Preparation method (b).

For carrying out the Preparation method (c-1), for example, 1 mol of the compounds of the Formula (I-c-1) can be reacted with 1 to 10 mol of a halogenation reagent, e.g., phosphorus oxychloride, to obtain the compounds of the Formula (I-d-1) and/or the compounds of the Formula (I-d-2) that are encompassed by the compounds of the Formula (I) of the present invention.

The compounds of the Formula (I-d-1) and the Formula (I-d-2) can be easily isolated according to a general isolation method used in organic chemistry, for example, column chromatography.

The Preparation methods (c-2), (c-3) and (c-4) can be carried out in accordance with the Preparation method (c-1).

The Preparation method (d) can be carried out according to the method described in the following literatures:The Journal of Organic Chemistry 1983, 48, 1375-1377,HETEROCYCLES, 1992, 33, 211-218,Bioorganic & Medicinal Chemistry 2006, 14, 6570-6580,WO 2007/133637A2.

Among cyanation reagents of the Preparation method (d), representative examples include trimethylsilyl cyanide, sodium cyanide, potassium cyanide, and diethyl cyanophosphate.

The reaction of the Preparation method (d) can be carried out in the presence of an appropriate diluent, and examples of the diluent which can be used are the same as the diluents exemplified for the Preparation method (a). Preferably; tetrahydrofuran can be mentioned.

Reaction of the Preparation method (d) can be carried out in the presence of an appropriate base and/or acyl chloride, and examples of the base which can be used are the same as the bases exemplified for the Preparation method (a). Preferred examples include organic bases such as trimethylamine, triethylamine, diisopropylethylamine, tributylamine, N-methylmorpholine, diazabicycloundecene (1,8-diazabicyclo[5.4.0]undec-7-ene), and diazabicyclooctane. Particularly preferred examples include 1,8-diazabicyclo[5.4.0]undec-7-ene

Further, examples of an appropriate acyl chloride include benzoyl chloride, dimethyl carbamoyl chloride, chloroethyl carbonate and the like.

Temperature range, pressure and time for the reaction of the Preparation method (d) are the same as the Preparation method (b).

For carrying out the Preparation method (d), for example, 1 mol of the compound of the Formula (I-c-2) can be reacted with 1 to 5 mol of a cyanation reagent, e.g., trimethylsilyl cyanide, in the presence of 1 to 5 mol of a base, e.g., 1,8-diazabicyclo[5.4.0]undec-7-ene, to obtain the compounds of the Formula (I-e) that are encompassed by the compounds of the Formula (I) of the present invention.

The compounds of the Formula (I-f) as reacting materials for the Preparation method (e) are encompassed by the compounds of the Formula (I) of the present invention and their representative examples are as follows:6-cyano-N-[2-ethyl-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-methylphenyl]-2-naphthamide,2-cyano-N-[4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2,6-dimethylphenyl]quinoline-6-carboxamide,2-cyano-N-[2-ethyl-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-methylphenyl]quinoline-6-carboxamide, etc.

The compounds of the Formula (IV) as reacting materials for the Preparation method (e) are known compounds, and representative examples include methyl iodide, ethyl iodide, benzyl bromide, dimethyl sulfate, diethyl sulfate, etc.

The reaction of the Preparation method (e) can be carried out in the presence of an appropriate diluent, and examples of the diluent which can be used are the same as the diluents exemplified for the Preparation method (a). Preferably, DMF can be mentioned.

The reaction of the Preparation method (e) can be carried out in the presence of an appropriate base, and examples of the base which can be used are the same as the base exemplified for the Preparation method (a). Preferably, sodium hydride can be mentioned.

Temperature range, pressure and time for the react on of the Preparation method (e) are the same as the Preparation method (b).

For carrying out the Preparation method (e), for example, 1 mol of the compound of the Formula (I-f) can be reacted with 1 to 3 mol of the compound of the Formula (IV), e.g., methyl iodide, in the presence of an appropriate base, e.g., sodium hydride, in an appropriate diluent, e.g., DMF, to obtain the compounds of the Formula (I) of the present invention.

The compounds of the Formula (I-g) as reacting materials for the Preparation method (f) are encompassed by the compounds of the Formula (I) of the present invention and their representative examples are as follows:6-bromo-N-[2-ethyl-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-methylphenyl]-2-naphthamide,N-[4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2,6-dimethylphenyl]quinoline-6-carboxamide,N-[2-ethyl-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-methylphenyl]quinoline-6-carboxamide, etc.

Among sulfurizing agents which can be used for the Preparation method (f), representative examples include phosphorus pentasulfide, Lawesson reagent, etc.

The reaction of the Preparation method (f) can be carried out in the presence of an appropriate diluent, and examples of the diluent which can be used are the same as the diluents exemplified for the Preparation method (a). Preferably, toluene can be mentioned.

Temperature range, pressure and time for the reaction of the Preparation method (f) are the same as the Preparation method (b).

For carrying out the Preparation method (f), for example, 1 mol of the compound of the Formula (I-g) can be reacted with 0.5 to 3 mol of a Lawesson reagent in an appropriate diluent, e.g., toluene, to obtain the compounds of the Formula (I).

The reaction of the Preparation method (g) and the preparation of the compounds of formula (VI) can be carried out by following procedure desclived in the literature: Tetrahedron, 2003, 59, 773-779.

The starting material (V) of the reaction method (g) is prepared by reaction of the compounds Formula (Vi):

wherein, A1to A4are as defined above,
with a reagent represented by the following formula:

The compounds of formula (VI) can be prepared by the method desclived in the Japanese patent application: Japanese patent application number 2010-055470.

The active compounds according to the invention may be used in combination with suitable synergists or other active compounds, such as for example insecticides, acaricides, nematicides, fungicides, biological control agents, and bacterizides. Such combinations can also result in a synergistic effect, i.e. the biological activity of such a combination is synergistically increased. Examples of such combination partners are the following insecticides, acaricides, nematicides:

The compounds according to the present invention show a potent insecticidal action and can, therefore, be used as an insecticide. Furthermore, the compounds according to the present invention exhibit a strong control effect against harmful animal pests, in particular arthropods and/or insects, particularly to agricultural pests, without imposing any harmful side effects of drug to the animal or the cultivated plants. The compounds of the present invention can thus be used for the control of a wide range of pest species, for example, harmful sucking insects, chewing insects, as well as other plant parasitic pests, storage insects, hygiene pests and the like, and can be applied for the purpose of disinfestations and extermination thereof. The active compounds and active compound combinations according to the invention, in combination with good plant tolerance and favourable toxicity to warm-blooded animals and being tolerated well by the environment, are suitable for protecting plants and plant organs, for increasing harvest yields, for improving the quality of the harvested material and for controlling animal pests, in particular insects, arachnids, helminths, nematodes and molluscs, which are encountered in agriculture, in horticulture, in animal husbandry in forests, in gardens and leisure facilities, in the protection of stored products and of materials, and in the hygiene sector. They can be preferably employed as plant protection agents. They are active against normally sensitive and resistant species and against all or some stages of development. The abovementioned pests include:

From the order of the Chilopoda, for example,Geophilusspp.,Scutigeraspp.

From the order of the Collembola, for example,Onychiurus armatus.

From the order of the Diplopoda, for example,Blaniulus guttulatus.

From the order of the Symphyla, for example,Scutigerellaspp.

From the order of the Zygentoma (=Thysanura), for example,Lepisma saccharina, Thermobia domestica.

From the class of the Bivalvia, for example,Dreissenaspp,

From the class of the Gastropoda, for example,Arionspp.,Biomphalariaspp.,Bulinusspp.,Derocerasspp.,Galbaspp.,Lymnaeaspp.,Oncomelaniaspp.,Pomaceaspp.,Succineaspp.

From the group of the phytoparasitic nematodes, for example,Aphelenchoidesspp.,Bursaphelenchusspp.,Ditylenchusspp.,Globoderaspp.,Heteroderaspp.,Longidorusspp.,Meloidogynespp.,Pratylenchusspp.,Radopholus similis, Trichodorusspp.,Tylenchulus semipenetrans, Xiphinemaspp.

It is furthermore possible to control protozoa, such as Eimeria.

All plants and plant parts can be treated in accordance with the invention. Plants are to be understood as meaning in the present context all plants and plant populations such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants can be plants which can be obtained by conventional plant breeding and optimization methods or by biotechnological and genetic engineering methods or by combinations of these methods, including the transgenic plants and including the plant cultivars protectable or not protectable by plant breeders' rights. Plant parts are to be understood as meaning all parts and organs of plants above and below the ground, such as shoot, leaf, flower and root, examples which may be mentioned being leaves, needles, stalks, stems, flowers, fruit bodies, fruits, seeds, roots, tubers and rhizomes. The plant parts also include harvested material, and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offshoots and seeds.

Treatment according to the invention of the plants and plant parts with the active compounds is carried out directly or by allowing the compounds to act on their surroundings, habitat or storage space by the customary treatment methods, for example by immersion, spraying, evaporation, fogging, scattering, painting on, injecting and, in the case of propagation material, in particular in the case of seed, also by applying one or more coats.

The compounds according to the present invention show a systemic action which means that the compounds can permeate plants body and translocate from the underground part of plants to the aerial part of plants.

As already mentioned above, it is possible to treat all plants and their parts according to the invention. In a preferred embodiment, wild plant species and plant cultivars, or those obtained by conventional biological breeding methods, such as crossing or protoplast fusion, and parts thereof, are treated. In a further preferred embodiment, transgenic plants and plant cultivars obtained by genetic engineering methods, if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof, are treated.

The terms “parts”, “parts of plants” and “plant parts” have been explained above.

Particularly preferably, plants of the plant cultivars which are in each case commercially available or in use are treated according to the invention. Plant cultivars are understood as meaning plants having novel properties (“traits”) which have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be cultivars, bio- or genotypes.

Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, vegetation period, diet), the treatment according to the invention may also result in superadditive “synergistic” effects. Thus, for example, reduced application rates and/or a widening of the activity spectrum and/or an increase in the activity of the substances and compositions which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, higher quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products are possible, which exceed the effects which were actually to be expected.

The preferred transgenic plants or plant cultivars (obtained by genetic engineering) which are to be treated according to the invention include all plants which, by virtue of the genetic modification, received genetic material which imparts particularly advantageous, useful traits to these plants. Examples of such traits are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, higher quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products. Further and particularly emphasized examples of such traits are a better defence of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and/or viruses, and also increased tolerance of the plants to certain herbicidally active compounds. Examples of transgenic plants which may be mentioned are the important crop plants, such as cereals (wheat, rice), maize, soya beans, potatoes, sugar beet, tomatoes, peas and other vegetable varieties, cotton, tobacco, oilseed rape and also fruit plants (with the fruits apples, pears, citrus fruits and grapes), and particular emphasis is given to maize, soya beans, potatoes, cotton, tobacco and oilseed rape. Traits that are emphasized in particular are the increased defence of the plants against insects, arachnids, nematodes and slugs and snails by virtue of toxins formed in the plants, in particular those formed in the plants by the genetic material fromBacillus thuringiensis(for example by the genes CryIA(a), CryIA(b), CryIA(c), CryIIA, CryIIIA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CryIF and also combinations thereof) (referred to hereinbelow as “Bt plants”). Traits that are also particularly emphasized are the increased defence of the plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins. Traits that are furthermore particularly emphasized are the increased tolerance of the plants to certain herbicidally active compounds, for example imidazolinones, sulphonylureas, glyphosate or phosphinotricin (for example the “PAT” gene). The genes which impart the desired traits in question can also be present in combination with one another in the transgenic plants. Examples of “Bt plants” which may be mentioned are maize varieties, cotton varieties, soya bean varieties and potato varieties which are sold under the trade names YIELD GARD® (for example maize, cotton, soya beans), KnockOut® (for example maize), StarLink® (for example maize), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf® (potato). Examples of herbicide-tolerant plants which may be mentioned are maize varieties, cotton varieties and soya bean varieties which are sold under the trade names Roundup Ready® (tolerance to glyphosate, for example maize, cotton, soya beans), Liberty Link® (tolerance to phosphinotricin, for example oilseed rape), IMI® (tolerance to imidazolinones) and STS® (tolerance to sulphonylureas, for example maize). Herbicide-resistant plants (plants bred in a conventional manner for herbicide tolerance) which may be mentioned include the varieties sold under the name Clearfield® (for example maize). Of course, these statements also apply to plant cultivars having these genetic traits or genetic traits still to be developed, which plant cultivars will be developed and/or marketed in the future.

The plants listed can be treated according to the invention in a particularly advantageous manner with the compounds according to the invention at a suitable concentration.

In veterinary medicine field, i.e., veterinary science, the active compounds of the present invention can be effectively used against various harmful animal parasites, particularly, endoparasites and ectoparasites. The term “endoparasites” include in particular worms (tapeworm, eelworm, trematode and the like) andplasmodium(coccidium and the like). The term “ectoparasites” include in general and preferably an arthropod, in particular insects (fly (a fly which can sting and suck), larva of parasitic fly, sucking lice, crab lice, bird lice, flea and the like) or acaroid mites (ticks and the like, for example, hard tick and soft tick) or mites (itch mite, chigger mite, bird mite and the like).

These parasites are as follows:

from Heteropterida, for example,Cimexspp.,Triatomaspp.,Rhodniusspp.,Panstrongylusspp.;

The active compounds of the present invention are also useful for controlling an arthropod, a worm and aplasmodiumwhich attacks an animal. Examples of the animal include an agricultural animals such as a cow, a sheep, a goat, a horse, a pig, a donkey, a camel, a buffalo, a rabbit, a chicken, a turkey, a duck, a goose, a nursery fish, a honey bee, etc. In addition, a pet which is also called as a companion animal, for example, a dog, a cat, a caged bird, an aquarium fish, and an animal for experimental testing (e.g., a hamster, a guinea pig, a rat, a mouse and the like) is also included.

With control of the arthropod, worm and/orplasmodiumby using the active compounds of the present invention, death ratio of a host animal can be reduced and productivity (for meat, milk, wool, leather, egg, and honey) and health of the animal can be improved. As a result, it is intended to achieve economically more favorable and simple animal breeding.

For example, it is preferable that introduction of blood from a parasite to a host is either prevented or inhibited (if possible). Parasite control can be useful for preventing infection which is caused by inflammatory pathogens.

The term “control” that is used in the present specification regarding a veterinary medicine field means that the active compounds are effective for reducing the occurrence ratio of each parasite in the animal infected with it to an innoxious level. More specifically, the term “to control” means that the active compounds of the present invention are effective for destroying parasites, inhibiting growth or propagation thereof.

In the present invention, substances having pesticidal effects against harmful pests encompassing all of such pests are referred to as pesticides.

When used as a pesticide, the active compounds of the present invention can be prepared in a form of a common preparation. Such preparation form may include, for example, liquids, emulsions, wettable powders, granulated wettable powders, suspensions, powders, foams, pastes, tablets, granules, aerosols, natural or synthetic agents impregnated with the active compounds, microcapsules, coating agents for seeds, formulations equipped with a combustion device (the combustion device can be a smoke or fog cartridge, a can or a coil, etc.) and ULV (cold mist, warm mist), and the like.

These formulations can be produced by known methods per se. For example, they can be prepared by mixing the active compounds with extenders, namely, liquid diluents or carriers; liquefied gas diluents or carriers; solid diluents or carriers and, optionally, with surfactants, namely, emulsifiers and/or dispersants and/or foam formers and the like.

In case of using water as an extender, for example, organic solvents can be used as auxiliary solvents.

Liquefied gas diluent or carrier may include those present as gas at atmospheric pressure and temperature, for example, bulan, propane, nitrogen gas, carbon dioxide, and aerosol propellant such as halogenated hydrocarbons.

Examples of the solid diluents may include ground natural minerals (for example, kaolins, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, etc.) and ground synthetic minerals (for example, highly dispersed silicic acid, alumina and silicate, etc.) and the like.

Examples of the solid carriers for granules may include crushed and fractionated rocks (for example, calcite, marble, pumice, sepiolite and dolomite, etc.), synthetic granules of inorganic or organic powders, and fine granules of organic materials (for example, sawdust, coconut shells, maize cobs and tobacco stalks, etc.) and the like.

Examples of the emulsifiers and/or foam formers may include nonionic and anionic emulsifiers [for example, polyoxyethylene fatty acid esters, polyoxyethylene fatty acid alcohol ethers (for example, alkylaryl polyglycol ether), alkyl sulfonates, alkyl sulfates and aryl sulfonates] and albumin hydrolysates and the like. The dispersants include lignin sulfite waste liquor and methylcellulose.

Binders may also be used in the formulations (powders, granules and emulsion). Examples of the binders may include carboxymethyl cellulose, natural or synthetic polymers (for example, gum arabic, polyvinyl alcohol and polyvinyl acetate, etc).

Colorants may also be used. Examples of the colorants may include inorganic pigments (for example, iron oxide, titanium oxide and Prussian blue, etc.), organic dyes such as Alizarin dyes, azo dyes or metal phthalocyanine dyes, and further, trace elements such as salts of iron, manganese, boron, copper, cobalt, molybdenum or zinc.

The formulation may include the above active components in an amount of 0.1 to 95 wt %, preferably 0.5 to 90 wt %.

The active compounds of the Formula (I) of the present invention can be provided as mixtures with other active compounds such as pesticides, poison baits, sterilizing agents, acaricidal agents, nematocides, fungicides, growth regulating agents, herbicides, and the like in a form of commercially useful formulation or an application form prepared from formulation thereof. The amount of the active compounds of the Formula (I) of the present invention in a commercially useful form may vary over a broad range. The concentration of the active compounds of the Formula (I) of the present invention for actual use can be, for example, between 0.0000001 and 100% by weight, preferably between 0.00001 and 1% by weight.

The compounds of the Formula (I) of the present invention can be used according to any common methods that are appropriate for an application form.

The active compounds of the present invention have stability that is effective for alkaline substances present in lime materials when the compounds are used against hygienic pests and storage pests. In addition, they exhibit excellent residual effectiveness in woods and soils.

Generally, when the active compounds of the present invention are used for the treatment of animals, they can be directly applied to the animal. Preferably, the compounds are applied in a form of pharmaceutical composition which may include a vehicle, an auxiliary agent, or both, that are known in the field and pharmaceutically acceptable.

For a veterinary medicine field and animal breeding, the active compounds can be applied (administered) according to various known ways, for example; intraintestinal administration with a tablet, a capsule, a drink, a drinkable medicine, granules, paste, and bolus administration, feed-through method, suppository; non-intraintestinal administration based on skin application such as injection (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.), embedding, intranasal application, bathing or immersion, spray, pouring, dropping, washing and scattering, and by using a molding article containing the active compounds such as a necklace, an earnmark, a tag a leg brace, a net, a marking device and the like. The active compounds of the present invention can be formulated into an appropriate formulation form that can be applied with a shampoo, aerosol, a non-pressurized spray, for example a pump spray and a vaporizer spray, etc.

When used for livestock, fouls, pets and the like, the active compounds of the present invention can be used as a formulation which includes them in an amount of 1 to 80 wt % (for example, powders, wettable powders (WP), emulsion, emulsifiable concentrate (EC), fluid, homogeneous solution and suspension concentrate (SC)), and the formulation can be applied as it is or after dilution (for example, dilution of 100 to 10,000 times), or as a chemical shower as an alternative method.

When used in a veterinary medicine field, the active compounds of the present invention can be used in combination with other appropriate synergistic agents or other active compounds, for example, acaricides, insecticides, parasticides, anti-plasmodiumagents, etc.

The active compounds of the present invention have low toxicity and can be safely used for warm-blooded animals.

EXAMPLES

Herein below, the present invention is described in greater detail with reference to the following examples.

However, it is evident that the present invention is not limited thereto only

Synthetic Example 1

To methylene chloride solution including 6-bromo-2-naphthonic acid (0.42 g) and N,N-dimethylformamide (300 μL), oxalyl dichloride (2.6 ml) was added under stirring at room temperature (18 to 30° C., the same shall apply hereinafter) followed by further stirring for 2 hours. Subsequently, the solvent was distilled off under the reduced pressure (760 to 20 mmHg, the same shall apply hereinafter). Resulting 6-bromo-2-naphthoyl chloride was dissolved in methylene chloride, added with pyridine (2.1 ml) and 2-ethyl-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-methylaniline (0.45 g), followed by stirring for 5 hours. After dilution with methylene chloride and water, the organic phase was separated and dried over magnesium sulfate. The drying agent (magnesium sulfate) was removed by filtration and the solvent was distilled off under the reduced pressure. The residue was separated and purified by column chromatography to obtain 6-bromo-N-[2-ethyl-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl-2-yl)-6-methylphenyl]-2-naphthamide (0.75 g, yield 84%).

Step 1-2: Synthesis of 6-cyano-N-[2-ethyl-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-methylphenyl]-2-naphthamide

6-Bromo-N-[2-ethyl-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-methylphenyl]-2-naphthamide (0.49 g) was dissolved in N,N-dimethylformamide (4 ml), and deaeration was carried out three times under argon atmosphere (i.e., the reaction solution was de-pressurized to 20 mmHg and brought back to atmospheric pressure under argon atmosphere). Zinc cyanide (0.07 g) and tetrakis (triphenylphosphine) palladium(0) (0.11 g) were added thereto and stirred with heating at 80° C. for 7 hours under argon atmosphere. After cooling to room temperature, the reaction solution was diluted with ethyl acetate, and washed with water and saturated brine. The organic phase was dried over anhydrous magnesium sulfate. The drying agent (anhydrous magnesium sulfate) was removed by filtration and the solvent was distilled off under the reduced pressure. The residue was purified by silica gel chromatography to obtain 6-cyano-N-[2-ethyl-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-methylphenyl]-2-naphthamide (0.04 g, yield 9%).

Synthetic Example 2

Quinoline-6-carboxylic acid (1.0 g) was dissolved in dichloromethane. N,N-dimethylformamide (300 μL) and oxalyl chloride (1.2 g) were added to this solution at room temperature and stirred for two hours followed by reflux for 20 minutes. The solvent was removed under the reduced pressure, and quinoline-6-carbonyl chloride was obtained as a crude product, which was then dissolved in dichloromethane. To this solution, 4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2,6-dimethylaniline (1.6 g) dissolved in dichloromethane and pyridine (1.2 g) were added and stirred at room temperature for 5 hours. The reaction solution was diluted with water and extracted twice with ethyl acetate. The organic phases were combined and washed with 1N hydrochloric acid and water, and dried over anhydrous magnesium sulfate. The drying agent (anhydrous magnesium sulfate) was removed by filtration and the solvent was distilled off under the reduced pressure. The residue was purified by column chromatography to obtain N-[4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2,6-dimethylphenyl]quinoline-6-carboxamide (2.0 g, yield 78%).

Dichloromethane was added to N-[4-(1,2,3,3,3-heptafluoropropan-2-yl)-2,6-dimethylphenyl]quinoline-6-carboxamide (1.9 g). To the resulting solution, 3-chloroperbenzoic acid (purity 70%) (1.4 g) was added and the mixture was stirred at room temperature for 3 hours. The solvent was distilled off under the reduced pressure and the residue was dissolved in ethyl acetate. Sodium hydrocarbonate solution and potassium carbonate were added thereto. After extracting the mixture twice with ethyl acetate, the organic phases were combined and washed with water, and dried over anhydrous magnesium sulfate. The drying agent (anhydrous magnesium sulfate) was removed by filtration and the solvent was distilled off under the reduced pressure to obtain N-[4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2,6-dimethylphenyl]quinoline-6-carboxyamide-1-oxide as a crude product (2.0 g). Without further purification, the compound was used for the next reaction.

To crude product of N-[4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2,6-dimethylpheyl]quinoline-6-carboxamide-1-oxide (97 mg), phosphorus oxychloride (3.0 g) was added and the mixture was stirred under heating at 100° C. for 1 hour. The reaction solution was poured into ice water, neutralized with potassium carbonate and extracted twice with ethyl acetate. The organic phases were combined and washed with water, and dried over anhydrous magnesium sulfate. The drying agent (anhydrous magnesium sulfate) was removed by filtration and the solvent was distilled off under the reduced pressure. The residue was purified by column chromatography to obtain 2-chloro-N-[4-(,1,1,2,3,3,3-heptafluoropropan-2-yl)-2,6-dimethylphenyl]quinoline-6-carboxamide (35 mg, yield 35%) and 4-chloro-N-[4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2,6-dimethylphenyl]quinoline-6-carboxamide (23 mg, yield 23%).

Synthetic Example 3

Crude product of N-[4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2,6-dimethylphenyl]quinoline-6-carboxamide-1-oxide (0.18 g) was dissolved in tetrahydrofuran. Trimethylsilylnitrile (0.14 g) and 1,8-diazacyclo[5.4.0]undec-7-ene (0.24 g) were added to this solution and stirred for 5 hours under heating at 70° C. Water was added to the reaction solution and extraction was carried out twice using ethyl acetate. The organic phases were combined and washed with water, and dried over anhydrous magnesium sulfate. The drying agent (anhydrous magnesium sulfate) was removed by filtration and the solvent was distilled off under the reduced pressure. The residue was purified by column chromatography to obtain 2-cyano-N-[4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2,6-dimethylphenyl]quinoline-6-carboxamide (0.13 g, yield 72%).

Synthetic Example 4

The reaction material of 2-(trifluoromethyl)quioline-6-carboxylic acid can be synthesized according to the method described in the patent document (International Publication No. 08/059370).

2-(Trifluoromethyl)quinoline-6-carboxylic acid (0.20 g) was dissolved in dichloromethane. To this solution, a small amount of N,N-dimethylformamide (300 μL) and oxalyl chloride (0.17 g) were added at room temperature and stirred for two hours. After refluxing for 20 minutes, the solvent was distilled off under the reduced pressure and 2-(trifluoromethyl)quinoline-6-carbonyl chloride was obtained as a crude product. To this crude product, 4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2,6-dimethylaniline (0.49 g) dissolved in pyridine was added and refluxed for 5 hours. The reaction solution was diluted with water and extracted twice with ethyl acetate. The organic phases were combined and washed with 1N hydrochloric acid and water, and dried over anhydrous magnesium sulfate. The drying agent (anhydrous magnesium sulfate) was removed by filtration and the solvent was distilled off under the reduced pressure. The residue was purified by column chromatography to obtain N-[4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2,6-dimethylphenyl]-2-(trifluoromethyl)quinoline-6-carboxamide (0.10 g, yield 24%).

Synthetic Example 5

N-[4-(1,1,1,2,3,3,3-Heptafluoropropan-2-yl)-2,6-dimethylphenyl]quinoline-6-carboxamide (250 mg) was dissolved in acetic acid (20 ml), added with N-chlorosuccinimide (160 mg), and stirred at 110° C. for hours. After cooling to room temperature, the reaction solution was added with water and extracted twice with ethyl acetate. The organic layer was combined, neutralized with aqueous solution of sodium hydrogen carbonate, and dried over anhydrous magnesium sulfate. The drying agent was filtered off and the solvent was removed by distillation under the reduced pressure. The resulting residues were purified by column chromatography to obtain 3-chloro-N-[4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2,6-dimethylphenyl]quinoline-6-carboxamide (90 mg, 33%) and 3,8-dichloro-N-[4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2,6-dimethylphenyl]quinoline-6-carboxamide (25 mg, 8%).

Synthetic Example 6

2-(Difluoromethoxy)aniline (1280 mg) and 1,2-dibromo-1,1,2,3,3,3-hexafluoropropane (8610 mg) were dissolved in tert-butylmethyl ether (30 ml) and water (30 ml), and added with tetrabutylammonium hydrogen sulfate salt (270 mg), sodium hydrogen carbonate (2030 mg) and sodium dithionite (4200 mg) in order. The mixture was stirred vigorously at room temperature for 2 days. The reaction solution was extracted twice with ethyl acetate. The organic phases were combined and washed with water, and dried over anhydrous magnesium sulfate. The drying agent was filtered off and the solvent was removed by distillation under the reduced pressure. The resulting residues were purified by column chromatography to obtain 1-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-6-(difluoromethoxy)aniline (810 mg, 26%).

4-(1-Bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-6-(difluoromethoxy)aniline (810 mg) was dissolved in acetic acid, added with N-bromosuccinimide (390 mg), and stirred at 70° C. for 3 hours. Water was added to the reaction solution and extraction was carried out twice using ethyl acetate. The organic phases were combined and neutralized with sodium hydrogen carbonate solution and dried over anhydrous magnesium sulfate. The drying agent was filtered off and the solvent was removed by distillation under the reduced pressure. The resulting residues were purified by column chromatography to obtain 2-bromo-4-(1-bromo-1,1,2,3,3,3-hexafluoroprop-2-yl)-6-(difluoromethoxy)aniline (730 mg, 75%).

Quinoline-6-carboxylic acid (1.4 g) was dissolved in dichloromethane (50 ml). N,N-dimethylformamide (100 μL) and oxalyl chloride (1.6 g) were added to this solution at room temperature and stirred for two hours followed by reflux for 20 minutes. The solvent was removed by distillation under the reduced pressure to obtain crude quinoline-6-carbonyl chloride. It was dissolved in pyridine and added to 2-bromo-4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-6-(difluoromethoxy)aniline (0.73 g) also dissolved in pyridine, and the resulting mixture was heated under reflux for 5 hours. After cooling to room temperature, the reaction solution was diluted with 1 N hydrochloric acid and extracted twice with ethyl acetate. The solvent was removed by distillation under the reduced pressure. The resulting residues were dissolved in tetrahydrofiaran (30 ml), added with 1 M aqueous solution of lithium hydroxide (50 ml), and stirred at room temperature for 2 hours. The reaction solution was extracted twice with ethyl acetate. The organic phases were combined, washed with water, and dried over anhydrous magnesium sulfate. The drying agent (anhydrous magnesium sulfate) was removed by filtration and the solvent was distilled off under the reduced pressure. The resulting residues were purified by column chromatography to obtain N-[2-bromo-4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-6-(difluoromethoxy)phenyl]quinoline-6-carboxamide (0.84 g, 86%).

N-[2-Bromo-4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-6-(difluoromethoxy)phenyl]-quinoline-6-carboxamide (0.73 g) was dissolved in dichloromethane (50 ml), added with 3-chloroperbenzoic acid (purity 70%, 0.48 g), and sited at room temperature for S hours. The solvent was distilled off under the reduced pressure and the residue was dissolved in ethyl acetate, Sodium hydrocarbonate solution and potassium carbonate were added thereto. After extracting the mixture twice with ethyl acetate, the organic phases were combined and washed with water, and dried over anhydrous magnesium sulfate. The drying agent (anhydrous magnesium sulfate) was filtered off and the solvent was removed by distillation under the 1.5 reduced pressure to obtain N-[2-bromo-4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-6-(difluoromethoxy)phenyl]quinoline-6-carboxamide-1-oxide (0.81 g, 98%).

N-[2-Bromo-4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-6-(difluoromethoxy)phenyl]-quinoline-6-carboxamide-1-oxide (0.41 g) was dissolved in tetrahydrofuran (50 ml), added with trimethylsilylnitrile (0.23 g) and 1,8-diazabicyclo[5.4.0]undec-7-ene (0.39 g), and stirred at 60° C. for 5 hours. Water was added to the reaction solution and extraction was carried out twice using ethyl acetate. The organic phases were combined and washed with water, and dried over anhydrous magnesium sulfate. The drying agent (anhydrous magnesium sulfate) was removed by filtration and the solvent was distilled off under the reduced pressure. The resulting residues were purified by column chromatography to obtain N-[2-bromo-4-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-6-(difluoromethoxy)phenyl]-2-cyanoquinoline-6-carboxamide (0.15 g, 36%).

Synthetic Example 7

The title compound was obtained from 4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-6-(difluoromethoxy)aniline, which had been obtained in Step 7-1, according to the method of Step 6-2 of Synthetic example 6.

The title compound was obtained from 2-bromo-4-(1,1,1,2,3,4,4,4-nonafluorobutan-2-yl)-6-(difluoromethoxy)aniline, which had been obtained in Step 7-2, according to the method of Step 6-3 of Synthetic example 6.

The title compound was obtained from N-[2-bromo-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-6-(difluoromethoxy)phenyl]quinoline-6-carboxamide, which had been obtained in Step 7-3, according to the method of Step 6-4 of Synthetic example 6.

The title compound was obtained from N-[2-bromo-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)-6-(difluoromethoxy)phenyl]quinoline-6-carboxamide 1-oxide, which had been obtained in Step 7-4, according to the method of Step 6-5 of Synthetic example 6.

Synthetic Example 8

By using N-iodosuccinimide instead of N-bromosuccinimide, the title compound was obtained from 4-(1,1,1,2,3,3,3,4,4,4-nonafluorobutan-2-yl)-6-(difluoromethoxy)aniline, which had been obtained in Step 7-1 of Synthetic example 7, according to the method of Step 6-2 of Synthetic example 6.

The title compound was obtained from 2-(difluoromethoxy)-6-iodo-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)aniline, which had been obtained in Step 8-1, according to the method of Step 6-3 of Synthetic example 6.

The title compound was obtained from N-[2-(difluoromethoxy)-6-iodo-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)phenyl]quinoline-6-carboxamide, which had been obtained in Step 8-2, according to the method of Step 6-4 of Synthetic example 6.

The title compound was obtained from N-[2-(difluoromethoxy)-6-iodo-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)phenyl]-quinoline-6-carboxamide N-oxide, which had been obtained in Step 8-3, according to the method of Step 6-5 of Synthetic example 6.

Synthetic Example 9

By using 1,1,1,2,3,3,3-heptafluoro-2-iodopropane instead of 1,2-dibromo-1,1,2,3,3,3-hexafluoropropane, the title compound was obtained according to the method of Step 6-1 of Synthetic example 6.

The title compound was obtained from 4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-(difluoromethoxy)aniline, which had been obtained in Step 9-1, according to the method of Step 6-2 of Synthetic example 6.

The title compound was obtained from 2-bromo-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-(difluoromethoxy)aniline, which had been obtained in Step 9-2, according to the method of Step 6-3 of Synthetic example 6.

The title compound was obtained from N-[2-bromo-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-(difluoromethoxy)phenyl]quinoline-6-carboxamide, which had been obtained in Step 9-3, according to the method of Step 6-4 of Synthetic example 6.

The title compound was obtained from N-[2-bromo-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-(difluoromethoxy)phenyl]quinoline-6-carboxamide 1-oxide, which had been obtained in Step 9-4, according to the method of Step 6-5 of Synthetic example 6.

Synthetic Example 10

By using chlorosuccinimide instead of bromosuccinimide, the title compound was obtained from 4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-(difluoromethoxy)aniline, which had been obtained in Step 9-1 of Synthetic example 9, according to the method of Step 6-2 of Synthetic example 6.

The title compound was obtained irom 2-chloro-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-(difluoromethoxy)aniline, which had been obtained in Step 10-1, according to the method of Step 6-3 of Synthetic example 6.

The title compound was obtained from N-[2-chloro-(1,1,1,2,3,3,3-heptafluoropropan-2-yl) 6-(difluoromethoxy)phenyl]quinoline-6-carboxamide, which had been obtained in Step 10-2, according to the method of Step 6-4 of Synthetic example 6.

The title compound was obtained from N-[2-chloro-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-(difluoromethoxy)phenyl]quinoline-6-carboxamide 1-oxide, which had been obtained in Step 10-3, according to the method of Step 6-5 of Synthetic example 6.

Synthetic Example 11

2-Cyano-N-[2-ethyl-6-methyl-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)phenyl]quinoline-6-carboxamide (240 mg) was dissolved in dichloromethane, added with urea-hydrogen peroxide adduct (85 mg) and trifluoroacetic anhydride (190 mg), and stirred at room temperature for 20 hours. The reaction solution was concentrated under the reduced pressure, and the resulting residues were dissolved in ethyl acetate. The solution was washed with water and dried over anhydrous magnesium sulfate. The drying agent was filtered off and the solvent was removed by distillation under the reduced pressure. The resulting residues were purified by column chromatography to obtain 2-cyano-N-[2-ethyl-6-methyl-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)phenyl]quinoline-6-carboxamide-1-oxide (0.20 g, 81%).

2-Cyano-N-[2-ethyl-6-methyl-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)phenyl]-quinoline-6-carboxamide-1-oxide (96 mg) was dissolved in acetonitrile, added with phosphoryl bromide (250 mg), and stirred at 100° C. for 5 hours. After cooling to room temperature, the reaction solution was poured into ice water and neutralized with sodium hydrogen carbonate. After extracting the mixture twice with ethyl acetate, the organic phases were combined and washed with water, and dried over anhydrous magnesium sulfate. The drying agent was filtered off and the solvent was removed by distillation under the reduced pressure. The resulting residues were purified by column chromatography to obtain 4-bromo-2-cyano-N-[2-ethyl-6-methyl-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)phenyl]quinoline-6-carboxamide (46 mg, 43%).

Synthetic Example 12

Synthesis of 3-bromo-4-{[4-chloro-5H-1,2,3-dithiazol-5-ylidene]amino}-N-[2-ethyl-6-methyl-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)phenyl]benzamide

4-amino-3-bromo-N-[2-ethyl-6-methyl-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)phenyl]benzamide (0.254 g) was dissolved in tetrahydrofuran (20 ml). To the mixture was added 4,5-dichloro-1,2,3-dithiazol-1-ium chloride (0.106 g), and stirred at room temperature for 2 hours. To the reaction mixture was added pyridine (0.091 g) in dichloromethane, and stirred at room temperature for 1 hour. The solvent was removed under reduced pressure. To the residue was added water and extracted twice with ethyl acetate. The organic phases were combined and washed with water, and dried over anhydrous magnesium sulfate. The drying agent (anhydrous magnesium sulfate) was removed by filtration and the solvent was distilled off under the reduced pressure. The residue was purified by column chromatography to obtain 3-bromo-4-{[4-chloro-5H-1,2,3-dithiazol-5-ylidene]amino}-N-[2-ethyl-6-methyl-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)phenyl]benzamide (0.270 g, 85%).

Synthesis of 2-cyano-N-[2-ethyl-6-methyl-4-(1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)phenyl]-1,3-benzothiazole-6-carboxamide

3-bromo-4-{[4-chloro-5H-1,2,3-dithiazol-5-ylidene]amino}-N-[2-ethyl-6-methyl-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)phenyl]benzamide (0.195 g) and copper(I) iodide (0.057 g) were suspended in pyridine (5 ml), and irradiated(150° C., 20 minutes). After cooling, to the reaction mixture was added ethyl acetate. The mixture was washed with 1N hydrochloric acid and water, and dried over anhydrous magnesium sulfate. The drying agent (anhydrous magnesium sulfate) was removed by filtration and the solvent was distilled off under the reduced pressure. The residue was purified by column chromatography to obtain 2-cyano-N-[2-ethyl-6-methyl-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)phenyl]-1,3-benzothiazole-6-carboxamide (0.076 g, 49%).

Synthesis Examples for Novel Intermediates

Aniline (1.0 g) was dissolved in tert-butylmethyl ether (15 ml) and water (15 ml), and added with undecafluoroiodocyclohexane (5.5 g), sodium dithionite (2.3 g), sodium hydrogen carbonate (1.1 g) and tetrabutylammonium hydrogen sulfate (0.46 g) in order. The resulting mixture was stirred vigorously at room temperature for 18 hours. After separating the reaction solution, the aqueous phase was extracted twice with ethyl acetate. The organic phases were combined and washed with 2N hydrochloric acid and sodium hydrogen carbonate solution in order, and dried over anhydrous magnesium sulfate, The drying agent (anhydrous magnesium sulfate) was removed by filtration and the solvent was distilled off under the reduced pressure. The residue was purified by column chromatography to obtain 4-(undecafluorocyclohexyl)aniline (2.7 g, yield 68%).

4-(Undecafluorocyclohexyl)aniline (2.7 g) was dissolved in acetic acid (30 ml), and then N-bomosuccinimide (2.4 g) was added thereto, followed by stirring the reaction solution for 2 hours at 60° C. After cooling down to room temperature, the reaction solution was poured into water and extracted twice with ethyl acetate. The organic phases were combined and washed with water and sodium hydrogen carbonate solution, and dried over anhydrous magnesium sulfate. The drying agent (anhydrous magnesium sulfate) was removed by filtration and the solvent was distilled off under the reduced pressure. The residue was purified by column chromatography to obtain 4-(undecafluorocyclohexyl)-2,6-dibromoaniline (3.7 g, yield 96%).

The compounds of the Formula (I) and the intermediates of the present invention that are obtained by the same methods as those of the above synthetic examples and according to the methods described above in detail, as well as their physical values are given in Table 1 to 6. Each compound obtained in the above synthetic examples is also shown in a corresponding table.

Abbreviations included in the tables are as follows.

Unless not mentioned otherwise, the test solutions were prepared as follows:

Containing as solvent: Dimethylformamide, 3 parts by weight; and as emulsifier: Polyoxyethylene alkyl phenyl ether, 1 part by weight

To prepare the test solution, 1 part by weight of an active compound is mixed with the above-mentioned amount of solvent containing the above-mentioned amount of emulsifier, and the mixture is diluted with water to the desired concentration.

Biological Test Example 1

Leaves of sweet potato were immersed in the test solution at the appropriate concentration, and the leaves were dried in air. The leaves were then placed in a petri dish having a diameter of 9 cm, and tenSpodoptera lituraat third instar larvae were released therein. The petri dishes were placed in a temperature-controlled chamber at 25° C. After 2 days and 4 days more sweet potato leaves were added. After 7 days, the number of dead larvae was counted to calculate the insecticidal activity. An insecticidal activity of 100% means that all larvae were killed, whereas an insecticidal activity of 0% means that no larva was killed. In the current test, the results of two petri dishes for each treatment were averaged.

Biological Test Example 2

50 to 100 adult mites ofTetranychus urticaewere inoculated to leaves of kidney bean at two-leaf stage planted in a pot of 6 cm in diameter. After one day, test solution at the appropriate concentration was sprayed thereon in a sufficient amount using a spray gun. After the spraying, the plant pot was placed inside a greenhouse, and after 7 days, the acaricidal activity was calculated. An acaricidal activity of 100% means that all mites were killed, whereas an acaricidal activity of 0% means that no mite was killed.

Biological Test Example 3

Leaves of cucumber were immersed in the test solution at the appropriate concentration, and the leaves were dried in air. The leaves were then put in a plastic cup containing sterilized black soil and fiveAulacophora femoralisat second instar larvae were released in the cup. The cups were placed in a temperature-controlled chamber at 25° C. After 7 days, the number of dead larvae was counted, and thus the insecticidal activity was calculated. An insecticidal activity of 100% means that all larvae were killed, whereas an insecticidal activity of 0% means that no larva was killed.

Biological Test Example 4

10 mg active compound are dissolve in 0.5 ml dimethyl sulfoxide. Serial dilutions are made to obtain the desired rates. Approximately 20Luciliacuprina 1stinstar larvae are transferred into a test tube containing 1 cm3of minced horse meat and 0.5 ml aqueous dilution of test compound. After 48 hrs percentage of larval mortality are recorded. 100% efficacy all larvae are killed, % efficacy normally developed larvae after 48 hrs.

In this test for example, the following compounds from the preparation examples showed good activity of 80% at application rate of 100 ppm: 2-3

In this test for example, the following compounds from the preparation examples showed good activity of 90% at application rate of 100 ppm: 2-214

Biological Test Example 5

To produce a suitable preparation of active compound, 10 mg of active compound are dissolved in 0.5 ml solvent, and the concentrate is diluted with cattle blood to the desired concentration. Approximately 20 adult unfed (Ctenocepahlides felis) are placed in flea chambers. The blood chamber, sealed with parafilm on the bottom, are filled with cattle blood supplied with compound solution and placed on top of the flea chamber, so that the fleas are able to suck the blood. The blood chamber is heated to 37° C. whereas the flea chamber is kept at room temperature. After 2 days mortality in % is determined. 100% means that all the fleas have been killed; 0% means that none of the fleas have been killed.

In this test for example, the following compounds from the preparation examples showed good activity of 80% at application rate of 100 ppm: 2-108

In this test for example, the following compounds from the preparation examples showed good activity of 90% at application rate of 100 ppm: 2-3, 2-133, 2-176

In this test for example, the following compounds from the preparation examples showed good activity of 95% at application rate of 100 ppm: 2-40, 2-49, 2-88, 2-108, 2-202

Biological Test Example 6

To produce a suitable preparation of active compound, 10 mg of active compound are dissolved in 0.5 ml solvent, and the concentrate is diluted with solvent to the desired concentration. Five adult engorged female ticks (Boophilus microplus) are injected with 1 μl compound solution into the abdomen. Ticks are transferred into replica plates and incubated in a climate chamber for a period of time. Egg deposition of fertile eggs is monitored.

After 7 days mortality in % is determined. 100% means that all eggs are infertile; 0% means that all eggs are fertile.

In this test for example, the following compounds from the preparation examples showed good activity of 80% at application rate of 20 μg/animal: 2-9

Biological Test Example 7

To produce a suitable preparation of active compound, 10 mg of active compound are dissolved in 0.5 ml solvent, and the concentrate is diluted with water to the desired concentration. Eight to ten adult engorged femaleBoophilus microplusticks are placed in perforated plastic beakers and immersed in aqueous compound solution for one minute. Ticks are transferred to a filter paper in a plastic tray. Egg deposition of fertile eggs is monitored after. After 7 days mortality in % is determined. 100% means that all the ticks have been killed; 0% means that none of the ticks have been killed. In this test for example, the following compounds from the preparation examples showed good activity of 90% at application rate of 100 ppm: 2-154

In this test for example, the following compounds from the preparation examples showed good activity of 100% at application rate of 100 ppm: 2-69, 2-173, 2-176, 2-203

Biological Test Example 8

To produce a suitable preparation of active compound, 10 mg of active compound are dissolved in 0.5 ml solvent, and the concentrate is diluted with water to the desired concentration. Prior to the assay, a piece of kitchen sponge is soaked with a mixture of sugar and compound solution and placed into a container. 10 adults (Musca domestica) are placed into the container and closed with a perforated lid. After 2 days mortality in % is determined. 100% means that all the flies have been killed; 0% means that none of the flies have been killed.

In this test for example, the following compounds from the preparation examples showed good activity of 80% at application rate of 100 ppm: 2-90, 2-108, 2-213

In this test for example, the following compounds from the preparation examples showed good activity of 95% at application rate of 100 ppm: 2-20

Preparation Example 1

Granule Formulations

To a mixture including the compound of the present invention (10 parts by weight) (No, 2-17), bentonite (montmorillonite; 30 parts by weight), talc (58 parts by weight) and lignin sulfonate (2 parts by weight), water (25 parts by weight) is added and the resulting mixture is kneaded well, B using an extrusive granulator, granules of 10 to 40 mesh are formed and granule formulations are obtained after drying at 40 to 50° C.

Preparation Example 2

Granule Formulations

Clay Mineral having a size distribution in the range of 0.2 to 2 ram (95 parts by weight) is added to a rotary mixer. By spraying the compound of the present invention (5 parts by weight) (No. 2-17) together with a liquid diluent under rotation, the clay is moistened followed by drying at 40 to 50° C. to obtain granule formulations.

Preparation Example 3

By mixing the compound of the present invention (30 parts by weight) (No. 2-17), xylene (55 parts by weight), polyoxyethylenealkylphenyl ether (8 parts by weight) and calcium alkylbenzene sulfonate (7 parts by weight) with stirring, emulsion are obtained.

Preparation Example 4

Wettable Agents

By mixing and pulverization of the compound of the present invention (15 parts by weight) (No. 2-17), a mixture including white carbon (fine powders of hydrous non-crystalline silicon oxide) and powder clay (1:5 mixture; 80 parts by weight), and a condensate of sodium alkylnaphthalene sulfonate formalin (3 parts by weight) and sodium alkylbenzene sulfonate (2 parts by weight), wettable agents are obtained.

Preparation Example 5

The compound of the present invention (20 parts by weight) (No, 2-17), lignin sodium sulfonate (30 parts by weight), bentonite (15 parts by weight) and calcined diatomite powder (35 parts by weight) are thoroughly mixed, After adding water thereto, the mixture is extruded through 0.3 mm screen followed by drying to obtain wettable granules.

Industrial Applicability

The novel pesticidal carboxamides of the present invention have an excellent pesticidal activity as pesticides as shown in the above examples.